Technical Activities 1981

Office of Recycled Materials

U S. DEPARTMENT OF COMMERCE

National Bureau of Standards

National Measurement Laboratory

Office of Recycled Materials

Washington, DC 20234

November 1981

Prepared for

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National Bureau of Standards

Department of Commerce

A/ashIngton, DC 20234

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NBSIR 81-2417

TECHNICAL ACTIVITIES 1981

OFFICE OF RECYCLED MATERIALS

Donald A. Becker, Joseph G. Berke, Eugene S. Domalski,

Rosalie T. Matthews, and Harvey Yakowitz, editors

U S. DEPARTMENT OF COMMERCE

National Bureau of Standards

National Measurement Laboratory

Office of Recycled Materials

Washington, DC 20234

November 1 981

Prepared for National Bureau of Standards

Department of Commerce

Washington, DC 20234

U.S. DEPARTMENT OF COMMERCE, Malcolm Baldrige, Secretary

NATIONAL BUREAU OF STANDARDS, Ernest Ambler, Director
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TABLE OF CONTENTS

Page

Technical Activities

The Recycled Oil Program 1

I. Introduction 2

II. The NBS Role in Recycled Oil 4

III. The Current NBS Program 6

IV. Plan 8

V. Implementation 15

VI. Discussion 23

The Resource Conservation Program 27

I. Goal and Objectives 28

II. Introduction 30

III. Needs 33

IV. Current Activities 34

A. Resource Recovery Program 35

B. Technical Advisory Center 100

IV. Discussion 110

APPENDICES 112

The Recycled Oil Program

The NBS Recycled Oil Program was established in 1976, in direct

response to passage of the Energy Policy and Conservation Act of 1975

(EPCA, Public Law 94-163; 42 U.S.C. 6201 et seq.). Section 383(c) of this

law requires NBS to "...develop test procedures for the determination of

substantial equivalency of re-refined or otherwise processed used oil or blend of oil... with new oil for a particular end use."

This article is divided into five sections, and includes a description of the past problems and the current situation in the oil

recycling industry as well as the past and present endeavors of the NBS

Recycled Oil Program itself.

The stated GOAL of the Recycled Oil Program Program is: to provide

the measurement methods and standards required for effective utilization

of recycled petroleum products. This GOAL is being achieved through:

(1) establishng the scientific and technical basis for

characterization of recycled petroleum products;

(2) developing and evaluating test procedures for establishing the

substantial equivalency between recycled and virgin petroleum

products; and

(3) providing technical information and support for the effective

utilization of recycled petroleum products.

These goals are being implemented through research and development

activities both within NBS and at several outside institutions.

1
I. Introduction

Oil recycling is not a new idea but in fact dates back to about 1920.

At that time lubricating oils had few or no additivies, (i.e., chemical

compounds added to oils to improve lubrication characteristics such as wear, oxidation, corrosion) and recycling these oils required only limited

processing which included heating (to remove volatile components),

settling (to separate water, dirt and sludge), and finally centrifuging or filtering to remove most of the remaining insoluble contaminants. With

this limited processing, lubricating oils could be brought back to

essentially original oil quality. In the years following, the types of

lubricating oils in the marketplace have expanded until they include a wide variety of different kinds and qualities of oils, many containing

high levels of additives which can make recycling the used oils a much more difficult problem.

In 1980, new lubricating oil sales in the U.S. were estimated at

9.5 X 10^ cubic meters (2.5 x 10^ gallons) per year. Of this, automotive

lubricants represented 4.5 x 10^ cubic meters (1.2 x 10^ gallons), and

industrial lubricants the remainder or approximately 5 x 10^ cubic meters

(1.3 X 10^ gallons). These industrial lubricants include hydraulic oils,

quenching oils, cutting oils, metal working oils, electrical oils and

process oils.

From the 9.5 x 10^ cubic meters of lubricating oils sold, about onehalf or approximately 4.8 x 10^ cubic meters of collectable used oil are generated annually in the U.S. It is estimated that, of the used oil

which is collected each year, about 1% is re-refined into motor oil, 17%

is reclaimed into industrial oil, approximately 50% burned for fuel or used in road oiling and dust control (often with little processing to remove contaminants), with the fate of the remaining 25% (approximately

1.2 X 10^ cubic meters each year) unknown.

At the present time there are a relatively small number of oil

recyclers in the U.S., with estimates ranging between 30 to 50. Of these,

only 10-20 are re-refiners, who produce a high quality lubricating oil

basestock from the used oil. The individual companies involved in oil

recycling usually are small, averaging only 10 - 15 employees. These

recyclers fall into three categories: processors (processing used oil for reuse as a fuel, often only removing free-standing water and larger pieces

of dirt or rust); reclaimers (generally applying a variety of relatively

simple chemical and/or physical processes to the used oil for reuse as an industrial oil); and re-refiners (employing a number of different high

technologies, generally with acid/clay or distillation/finishing

treatment, to remove essentially all of the impurities and contaminants in

the oil, yielding clean, high quality lubricating base oils). In many

cases an oil recycler may be involved with more than one of these

categories, and at times with all three.

2
In the past there has been a number of regulatory obstacles to

increased recycling of used oils in the U.S. Two of the most significant

of these were: (1) a 1965 Federal Trade Commission (FTC) trade

regulation rule, and (2) the exclusionary clauses in various Federal and

military specifications. The first of these, the FTC trade regulation

rule, required that all recycled motor oils contain the label "...made

from previously used oils..." This requirement was harmful to the

image of re-refined oils, and was recently modified by the Used Oil

Recycling Act of 1980 (P. L. 96-463). This law now removes the FTC

requirement of labeling as to origin until future labeling standards

directed by the Energy Policy and Conservation Act (P.L. 94-163, Section

383) become effective (i.e., NBS test procedures as provided to the FTC).

A second obstacle to increased recycling of used oils had been the

specific prohibition on the use of recycled petroleum products found in a number of Federal and military specifications (e.g., burner fuels and

engine oils), regardless of the quality of the recycled products. In

response to requirements in the Resource Conservation and Recovery Act

(P.L. 94-580) and after a substantial study^ , the Department of Defense

(DoD) has recently issued revised specifications for both burner fuel oil

(Federal specification VV-F-815d) and engine oils used in administrative

vehicles (passenger cars and light trucks; MIL-L-46152B) . These revised

DoD specifications now allow the use of recycled oils in products

submitted for their use, provided these recycled products meet all other

requirements.

Technically, recycled lubricating oil products appear to be

potentially suitable for all end uses with proper clean-up and additive

treatment, since the basic hydrocarbon structure is not significantly

altered during use. While non-technical factors (such as economics and

availability) will obviously determine whether all potential end uses for

recycled oil can be made available on a realistic basis, the national

goals of energy conservation, resource conservation, pollution control,

and balance of payments certainly suggest that a strong effort should be

made in persuing the goal of effective oil recycling in the United

States.

3
II. The NBS Role in Recycled Oil

There are three areas of legislation which provide the framework

outlining NBS responsibilities in oil recycling. These include (1) the

National Bureau of Standards (NBS) organic act and its amendments, (2)

the Energy Policy and Conservation Act and (3) the Resource Conservation

and Recovery Act. The model "States Used Oil Recycling Act," while not a specific article of legislation, also has an influence on the NBS

responsibi 1 ites, and will be discussed briefly.

The NBS organic act (particularly 15 U.S.C. 272) states that the NBS

responsibilities include in part "...the development of methods for

testing materi al s. . .cooperation with other governmental agencies and with

private organizations in the establishment of standard practices. . .the

preparation and distribution of standard samples. . .the development of

methods of chemical analysis...". While these functions do not

specifically consider the subject of recycled oil, they are consistent

with the efforts required of the Recycled Oil Program as described in

Sections III and IV.

The Energy Policy and Conservation Act (EPCA, Public Law 94-163;

42 U.S.C. 6201 et seq .) was the primary force in establishing the Recycled

Oil Program at NBS in September 1976. Section 383 (c) of this law

requires the National Bureau of Standards to "...develop test procedures

for the determination of substantial equivalency of re-refined or otherwise processed used oil or blend of oil... with new oil for a particular end use." It also requires that after development of these

test procedures they be reported to the FTC. The stated purposes of this

legislation were (1) to encourage the recycling of used oil; (2) to

promote the use of recycled oil; (3) to reduce the consumption of new oil;

and (4) to reduce the environmental hazards associated with disposal of

used oils. This law implies that all potential end uses of recycled oil

should be addressed including reuse as fuel, motor oils, hydraulic and

industrial oils.

The Resource Conservation and Recovery Act (Public Law 94-580,

42 U.S.C. 3251), in Section 6002, states that each Federal agency shall

procure items with the highest percentage of recovered materials

practicable. It further states that any decision not to procure such

recycled material must be based on one or more of the following:

unavailability; unreasonable price; or failure to meet NBS performance

standards (when available). This Act includes recycled oils as well as other recycled materials, and when taken in combination with the EPCA,

requires that NBS address the problem of performance standards for

recycled oils. In addition, this law requires that exclusionary clauses

in Federal and Military specifications be reviewed by the appropriate

Federal agency, and revised to encourage the use of recycled materials.

Finally, a model state "Used Oil Recycled Act" was sponsored by the

Federal Agency Administration in 1976 and published in the Federal

Register. This model Act was designed to assist individual states in

establishing control over used oil disposal, and clearly encourages

recycling as a superior method of disposal. This model Act refers

4
directly to Section 383 of EPCA for the determination of substantial

equivalency for recycled petroleum products. Used oil recycling laws at

present have been passed by at least eight states, and in many cases these

laws are similar to the model Act. Several additional states have also

introduced legislation based on this model Act.

The NBS role was recently confirmed by passage of the "Used Oil

Recycling Act of 1980" (P.L. 96-163). This Act was passed late in 1980 to

alleviate the problem oil recyclers were having as a result of the FTC

labelling requirements, but is to be in effect only until the NBS test

procedures become available. The U. S. Congress Committee report further

stated "...the Committee believes that the work of the Bureau (of

Standards) should continue The Committee expects the Bureau to give

this work a high priority."^

An important reason why recycled lubricating products have not yet

met with widespread consumer acceptance, both by the Federal Government as well as by the public, is the lack of reliable test procedures and

standards on which realistic performance criteria can be based. In the

above legislation, particularly EPCA, NBS is directed to develop such test

procedures and standards, and these procedures will provide the basis for

FTC trade regulation rules for industry-wide performance standards and

labelling requirements for recycled oil.

The resolution of this problem by NBS is particularly appropriate

because it involves both the development and evaluation of measurement

methods and standards, and because it requires an independent third party

role for acceptance by all concerned parties (virgin oil refining

industry, oil recycling industry, user industries, and government

regulators). The alternative to increased recycling of petroleum oils is

the continued contamination of the environment and loss of a valuable

resource. Recent published data indicate that, of all crude petroleum and

petroleum products reaching the ocean, over 40 percent is due to used

lubricating oils.

5
III. The Current NBS Program

This section describes the current NBS Recycled Oil Program, its

goal, objectives, program plan, and progress made to date.

A. Goal

The Goal of the NBS Recycled Oil Program is: TO PROVIDE THE

MEASUREMENT METHODS AND STANDARDS REQUIRED FOR EFFECTIVE UTILIZATION OF

RECYCLED PETROLEUM PRODUCTS.

B. Objectives

In order to reach the above goal, the three following objectives

should be met:

(1) ESTABLISH THE SCIENTIFIC AND TECHNICAL BASIS FOR

CHARACTERIZATION OF RECYCLED PETROLEUM PRODUCTS.

(2) DEVELOP AND EVALUATE TEST PROCEDURES FOR ESTABLISHING THE

SUBSTANTIAL EQUIVALENCY BETWEEN RECYCLED AND VIRGIN PETROLEUM

PRODUCTS.

(3) PROVIDE TECHNICAL INFORMATION AND SUPPORT FOR THE EFFECTIVE

UTILIZATION OF RECYCLED PETROLEUM PRODUCTS.

The first objective covers the research that is required to

effectively utilize recycled lubricating oils. At the present time, there

is a concern among user industries, especially the automotive industry,

that the quality and batch-to-batch variability of recycled oils are not

sufficiently well known to assure a continuous supply of high quality

recycled oil. In addition, the various impurities and contaminants which

can occur in a used or recycled petroleum product may have effects on the

final product which are not well established. A sound scientific and

technical data base is crucial for the test procedures developed by NBS to

be widely accepted by industry. This basic understanding has not been

completely developed at present.

The second objective, to develop and evaluate test procedures for

substantial equivalency, is the basic requirements as set forth in EPCA.

This requirement is complicated by the current testing methods used.

These current tests (called "engine sequence tests") consist of

automobile/truck engines and/or special test engines on laboratory

dynamometer test stands, and are run in sequence with different loads,

speeds, temperatures, controlled blowby (gases bypassing the piston

rings), etc., usually requiring special fuels. The controlled variables

must be within prescribed limits for acceptable test results to be

reported. For the API SF classification (i.e., the oil quality currently

necessary to maintain 1981 automobile warranties), four different engine

tests must be passed. For military specifications for administrative

vehicles (MIL-L-46152B, approximately equivalent to API classification

SF/CC), five engine sequence tests are needed. The minimum cost of a set

6
of these tests for a single oil is at least $30,000. Since there is no alternative set of commonly accepted test procedures or specifications for

physical and chemical laboratory tests on oil basestocks or formulated

oils, the small re-refining companies have had a difficult time entering

the quality lubricating oil market.

The third objective, to provide technical information and support for

the effective utilization of recycled petroleum products, is important in

accommodating recycled products for each end use. This objective includes

providing technical support to the FTC as required for the NBS test

procedures, as well as to disseminate the NBS research and evaluation

results and other technical information on used and recycled petroleum

products to the industry and the consumer public. Both the EPCA and RCRA

legislation contain sectioris which emphasize the necessity for Federal

agencies to encourage the utilization of recycled products, and to educate

the public in the proper reuse and disposal of these products.

7
IV. Plan

The initial emphasis of the NBS Program from 1976 to 1978 was on used

oil recycled to be used as fuel. This choice was made for a number of

reasons:

As described in Section I, the primary fate of used oil at present

is through burning for fuel, and is largely uncontrolled;

There appear to be operational and environmental problems from

uncontrolled burning of used and minimally processed recycled

oils; and

This end use could be addressed with the limited resources

available at that time.

In November of 1978, the official report on Phase I of the Recycled

Oil Program, "Test Procedures for Recycled Oil Used as Burner Fuel," was transmitted to the Federal Trade Commission (NBSIR 78-1453; later issued

as NBS Technical Note 1130). This report contains test procedures for the

operational performance of recycled oils used as burner fuel oils.

Simultaneously, Phase II of the NBS Program, "Test Procedures for Recycled

Oil Used as Motor Oil", was initiated.

There has been sufficient engine testing on re-refined oils to

establish that: (1) a high quality re-refined lubricating oil which has

been formulated with a high quality additive package can be comparable to

a virgin oil similarly formulated, and (2) that both will provide adequate

performance in most types of automotive service. The problem which exists

at the present time is the lack of technical information and data to

determine which tests are necessary and how often they should be applied

in order to assure that the re-refined oil basestock is consistent

inbetween the engine testing. The user industries have made it clear that

they are concerned about the potential lack of consistency of re-refined

oil products, and about the potential effects of unusual or unknown

contaminants in the used oil feedstock to re-ref ineries. These potential

problems are of particular concern when warranty questions are involved.

The most important requirement for assuring the quality of re-refined

motor oil is development of a set of test procedures capable of

monitoring the quality, consistency, and additive response of the oil

basestock inbetween qualifications by means of the very expensive engine

sequence tests. These evaluated test procedures are crucial in order to

allow accommodation of the re-refined oils within the existing

API-SAE-ASTM classification system. (Note: API = American Petroleum

Institute; SAE = Society of Automotive Engineers; ASTM = American Society

for Testing and Materials.) Development and evaluation of these tests by

NBS is significantly more difficult because no such set of test procedures

exists for virgin lubricating oils. Historically, virgin oil producers were instead required to control the crude source and refining technology

in order to assure a constant lubricating oil basestock, particularly for

the U.S. military specifications. This option is not available to oil

recyclers.

8
The question of the consistency of re-refined oil has been addressed

in the recently completed cooperative ASTM/NBS study. In this one-year

study, four virgin oil producers and six re-refined oil producers

submitted monthly samples of their regular production basestock for

analysis by a group of 14 laboratories, including NBS (Table 1). These

laboratories analyzed the coded samples using over 40 different chemical,

physical, and performance tests (Tables 2 - 4)^,^. It is expected that

the evaluated data from this study will provide much of the information

necessary to indicate an appropriate set of test procedures to monitor re- refined basestock consistency. In addition to the consistency study

described above, the NBS Program is currently evaluating the chemical and

physical test procedures used on lubricating oil basestocks, as well as performing research and development on bench-scale performance tests for

establishing basestock additive response. Development of effective and

economical test(s) for additive response appears to be crucial to the success of our efforts.

Therefore, the strategy NBS has adopted for engine oils is to attempt

to provide a set of test procedures capable of adequately monitoring the

consistency and additive response characteristics of the re-refined

petroleum lubricating oil basestocks. A diagram of this strategy is shown

in Figure 1. This set of basestock tests will then be coupled to the

appropriate engine sequence testing as shown. Subsequent samples can then

be monitored using the NBS tests, without the engine testing, for some period of time yet to be established. If successful and implemented, this

strategy should provide the methodology to assure a consistently high

quality product with a minimum of subsequent engine testing.

9
“SUBSTANTIAL

EQUIVALENCY'

FIGURE 1. DIAGRAM OF EQUIVALENCY TEST STRATEGY

10
Table 1

Laboratories Cooperating in the ASTM/NBS

Basestock Consistency Study

Bartlesville Energy Technology Center Chevron, USA

National Research Council of Canada Suntech, Inc.

Motor Oils Refining Co. SAVANT, Inc.

Mobil Oil Corporation Texaco

U.S. Army MERADCOM Lubri zol

National Bureau of Standards Gulf R & D

Shell Research/Thornton (U.K.) Fi Imi te

11
Table 2

Physical Property Tests

Test Method

API Gravity ASTM 0287

Aromatics Low Resolution Mass Spec

UV

Boiling Point Range ASTM 02287 (GC)

Brookfield Viscosities

(a o“ to -40° F ASTM 02983

Carbon residue ASTM 0524

Color ASTM 01500

Demulsibi 1 ity ASTM 01401

Fi 1 terabi 1 ity (1)

Foam ASTM 0892

Oxidation (1)

Pour Point ASTM 097

Refractive Index ASTM 01218

Sulfated Ash ASTM 0374

Viscosities 0 40°C and 100° C ASTM 0445

Viscosity Index ASTM 02270

(1) Proprietary

12
Table 3

Chemical Property Tests

Test

Acid Number

Bromi ne

Chlorine

Ethylene Glycol

Metals

Nitrogen

Oxygen

Potassium

Saponification Number

Sodium

Sulfur

Water

Carbon-13 NMR Analysis

Polycyclic Aromatics by DMSO

Extraction

Hydrocarbon Types by TLC/FID

High Resolution Mass

Spectrometry

Method

ASTM D664

Neutron Activation

Neutron Activation

( 1 )

Emission Spectrograph

Chemi 1 umi nescent

Modified UOP

Neutron Activation

ASTM D94

Neutron Activation

ASTM D1551

ASTM D1744

IP 346

( 1 )

(1) Proprietary

13
Table 4

Bench Tests

Test Method

Anti -Oxidant Response (1)

Cold Crank Simulator 0 0° to -40°C ASTM D2602

Differential Scanning Calorimeter —

Ford Anti -Oxidant Capacity —

Load Wear Index ASTM D2783

Mini -Rotary Viscometry ASTM D3829

RBOT ASTM 02272

Rust Tendency ASTM D665

Sequence III Simulator (1)

Stability in Sunlight plus —

Various Temperatures

TOST ASTM D943

(1) Proprietary

14
V. Implementation

In the past year, there has been significant progress in the NBS

Program. The ASTM/NBS Basestock Consistency Study has already been

discussed, and the data from this study have already proved immensely

helpful to us in our efforts. Further evaluation and correlation of the

very large amount of data generated in this study will provide even greater rewards in our understanding of lubricating base oil in general

and, in particular, re-refined oils.

Progress in the evaluation of chemical and physical test procedures

has also been steady. It is felt that the most important of these tests

for re-refined oil will include the following: (1) visual inspection,

(2) viscosity/VI, (3) density (API gravity), (4) flash point, (5) pour

point, (6) sulfated ash (modified), (7) total acid number,

(8) saponification number, and (9) copper corrosion. Additional tests of

great interest at this time, although no decision has been made at present

about their need, include boiling point distribution, metals analysis,

differential IR, chlorine, hydrocarbon types by clay-gel chromatography,

and a corrosion/rust test. Of course, it must be understood that the

above lists are preliminary, and additional information from the Basestock

Consistency Study will be utilized before completing these evaluations.

Significant progress has also been made in research on test

procedures for additive response, and some of this work will be briefly

described. Dr. Stephen Hsu and other members of the Tribochemistry Group

at NBS have modified and evaluated several tests which, at this time,

suggest they may be capable of monitoring the additive response of

lubricating basestocks, yet are simple enough to be run on a routine

basis.

The first test to be described is a modification of a bench test for

oxidation stability named the Rotating Bomb Oxidation Test, or RBOT

(ASTM D2272). While this test was originally developed to estimate the

oxidation stability of steam turbine oils, it has also been used with

varying success with many types of oils. Modifications to this test

include: (1) use of a high accuracy pressure gauge in the initial oxygen

charge; (2) use of an aluminum insert and modified sample beaker to

acommodate a 1.5 gram oil sample vs. 50 grams in the original procedure;

(3) use of both steel and copper wire catalysts; (4) addition of only 2%

water to the oil; and (5) operation at 160°C. The results from this

modified RBOT on six engine oils with substantial engine test data are

shown in Table 5. Additional development of this test using a soluble

metal catalyst package (Fe, Pb, Cu, Mn, Sn) along with a synthetic fuel

blow-by catalyst provided the improved results shown in Table 6. These

results indicate the test is capable of good separation between differing

performance levels of the total set of III-D ASTM Reference Engine Oils,

and in addition averaged only 4% standard deviation between duplicate runs

on each sample.

This test was also run on samples of re-refined and virgin oil from

the Environment Canada/RCMP Fleet Test, and results from engine test data

and the modified RBOT test are shown in Table 7. Since tiiese two oils were formulated with exactly the same additive package at the identical

treat level, these results suggest that this modified RBOT test may be

15
Table 5

Results from the Modified RBOT Test Using Wire Catalysts^

Reference Oil Engine Test Results (hours)*^ RBOT Break Point (i

A Pass (64) 590, 590

B Pass (56) 395, 487

C Pass (40) 250, 258

D Fail (24) 240, 250

E Fail (16) 193, 168

F Fail (16) 198, 176

^For a description of modifications, see test.

*^Hours = no. of hours to 375% viscosity increase in the III-D Test.

16
Table 6

Results from the Modified RBOT Test Using

Soluble/Synthetic Catalysts^

Reference Oil Engine Test Results (hours)^ RBOT Break Point (min)

A Pass (64) 268, 278

B Pass (56) 200, 186

C Pass (40) 154, 150

D Fail (24) 58, 60

E Fail (16) 43, 45

F Fail (16) 40, 38

^For a description of

^Hours = no. of hours

modifications, see test,

to 375% viscosity increase in the III-D Test

17
Table 7

Results from the Modified RBOT on Oil Samples from the

Environment Canada/RCMP Fleet Test^

Oil Identification Engine Test Results

(hours)^

FLO 79038 (Virgin) Pass (40); Fail (64)

Pass (40); Fail (64)

FLO 79034 (Re-refined) Pass (40); Pass (64) 222

^Both oils performed satisfactorily in the fleet test.

^Both oils satisfactorily met the design criteria for that additive

package (MIL-L-46152A; pass at 40 hours).

RBOT Break Point

(min)

186

18
capable of discriminating between different lubricating oil basestocks,

and possibly, between differing quality levels of the same basestock.

Another bench test being evaluated with respect to lubricating oil

additive response characteristics is a test for metallic wear. After

substantial research, a step loading seizure test (SLST) using a 4-ball wear test rig has been developed which successfully discriminated between

the six high/low wear III-D Reference Engine Oils. This test is run at

slow speed (200 RPM), with 9 kilogram (20 pound) increments every 5 minutes until seizure. The results from this test are shown in Table 8,

and suggest the SLST can successfully differentiate between the III-D high wear and low wear reference oils.

In addition, a variation of this test was developed which uses very

small oil samples (6 microliters), which is called the micro-sample SLST.

When applied to the set of III-D reference oils, this test also was able

to successfully differentiate between the high/low wear reference oils.

When both of these tests were used to look at the Environment Canada/RCMP

fleet test oils, they could see no difference between the virgin and re- refined oils while indicating good wear characteristics for these two

oils. These results agree with the fleet test and engine test results for

these oils, which showed no significant differences between them for wear characteristics.

19
Table 8

Results from the 4-Ball Step Loading Seizure Test

Reference Oil

Engine Test 4-Ball Test Results

Wear Rating (Wear)

Seizure Load (Kg) Average (j

A Low (48) 200,200 200

B Low (46) 227,191,209,209 209

C Low (48) 218,218 218

D High (287) 145,163,181,172, 168

172,172,163

E High (277) 127,136 132

F High (256) 127,136 132

^Wear values = Average cam and lifter wear (cm x 10"'+)

20.
Additional research projects which were funded by the Recycled Oil

Program during FY-1981 include the following:

“ Bench Test for Wear (Metallurgy Division/CMS) This test utilized

the Sun Tech modification of the Yimkin ring and block test.

While the results were able to discriminate between various ASTM

reference oils, the test procedure was judged more difficult to

quantitate than the 4-ball SLST test, and also required numerous

test runs to evaluate a single oil. Funding for this project had

been decreasing and was dropped at the end of FY-1981.

® Ford Anti -oxidant Titration (Chemical Thermodynamics

llivision/CCP) Whi le found to be highly reproducible and useful

for the evaluation of formulated products, this test was judged

not suitable for the routine evaluation of lubricating oil

basestocks. Funding for this project was terminated after

comletion of the ASTM/NBS Basestock Consistency Study (BCS)

samples, about 3/4 through the FY-1981 year. However, the

equipment was transferred to the Tri bochemi stry Group, and some

use is being made of the test in their on-going research program.

Differential Scanning Calorimetry (Chemical Kinetics Pi vision/CCP)

This technique is felt to be extremely useful in the investigation

of lubricants and basestock-additive interactions, but was judged

too difficult for routine use, especially since the modified RBOT

test was developed. The project is being funded again in FY-1982

at a somewhat reduced level, primarily for research on the

technique and for evaluation of research samples generated by the

Tri bochemi stry Group.

“ Polychlorinated Biphenyls (Organic Analytical Research

Divi sion/CAC ) A relfaole method for the determination of PCBs in

lubricating oil was developed, and a PCB in Oil Standard Reference

Material (SRM) is being produced. The SRM should be available

early in 1982. This group is also cooperating in the production

of samples for an ASTM/NBS round-robin on the analysis of PCBs in

oils.

Halogen Analysis by Neutron Activation (Inorganic Analytical

Research Divi sion/CAC]I he neutron activation analysis (NAA)

technique is very sensitive and highly reliable for the

determination of chlorine and bromine in petroleum oils. This

method provided excellent results for the BCS samples, and is of

continuing benefit in the on-going research program of the

Tribochemistry Group. Additional efforts in FY-1982 will

concentrate on speciation studies of the chlorine-containing

compounds, in order to better understand their source(s) and

effects on lubrication performance.

Pennsylvania State University Micro-Oxidation Test Research on this test for oxidation stability is rapidly concluding, and they

are now running a variety of lubricating oil samples to establish

21
the limits of the technique. This project will be completed in

mid-1982.

“ U.S. Army MERADCOM Deposits Study In a cooperative research

effort, the U.S. Army lubrication laboratory at Southwest Research

Institute (SWRI) has been evaluating virgin and re-refined oils

for their comparative sludge and deposits tendencies. This work

is essentially completed and a report on this two year project

will be forthcoming shortly.

° U.S. Army MERADCOM/Frankl in Research Center/NBS Bench Engine

Screening lest Ueve (opmefTT A cooperative agreement on this

cfeveTopment project was signed near the end of FY-1981. The

purpose of this project is attempt to develop an apparatus

utilizing bench scale hardware to simulate the V-D engine sequence

test. This apparatus will utilize actual engine hardware along

with an auxiliary power source and blowby generator. It is

expected that a decision on the success of this approach can be

made by mid-FY 1982.

In conclusion, the program described above is felt to be a comprehensive and responsible effort by NBS to address a challenging and

technically very difficult legislative mandate. At this point in time, we perceive a very real possibility of success in this endeavor, with

approximately two more years required for completion.

22
VI. Discussion

In the past five years, the Recycled Oil Program has made substantal

progress towards fulfilling its responsibilities under the Energy Policy

and Conservation Act. In addition, it has established itself as one of

the leading laboratories in the country in the area of test procedures and

evaluation of recycled petroleum products and lubricating oils. Specific

items indicating progress in the Recycled Oil Program are:

“ Organized and held the first conference on Measurements and

Standards for Recycled Oil (November 1976). Proceedings published

as SP 488 (149 pages).

° Established an extensive oil characterization laboratory.

Was instrumental in creating the new ASTM Technical Division P, on Recycled Petroleum Products and Lubricants. ROP senior staff

member was appointed divisional vice-chairman, and chairman of one

of the sections.

Organized and held the second conference on Measurements and

Standards for Recycled Oil (November 1977). Had over 170

attendees representing all aspects of industry and government.

Proceedings published as SP 556 (225 pages).

Obtained an Industrial Research Associate from the Association of

Petroleum Re-refiners (APR) to work at NBS on recycled oil test

procedures (1977-79). Person selected was the chief chemist of

the largest re-refiner in the U.S.

Completed Phase I of the NBS Recycled Oil Program on the test

procedures for the operational performance of recycled oils used

as burner fuel. Report transmitted to the FTC in November 1978,

and published as NBSIR 78:1453 and NBS Tech. Note 1130.

Received FY 1978 supplemental appropriation in September of 1978,

initiating the appropriated funding for recycled oil. Funding

plan included amounts for facilities modifications, equipment, and

certification of related Standard Reference Materials.

Initiated Phase II of the NBS Program, on motor oils (November

1978).

Obtained a senior staff member from a large additive company to

head projects on performance testing. Became Group Leader of the

Tribochemistry Group, formerly the Recycled Oil Laboratory.

Established a lubricated wear laboratory for development and

evaluation of test procedures on friction and wear.

Obtained space and initiated required modifications for a storage

area and blending faacility for producing formulated re-refined

oils for testing and evaluation.

23
° Established an extensive oxidation/deposit performance testing

1 aboratory.

° Successfully completed the sampling and analyses phases of a cooperative ASTM/NBS re-refined oil basestock consistency study.

This study utilized monthly oil samples from six re-refiners plus

four virgin oil refiners, and after subsampling and coding at NBS,

these samples were analyzed for 43 different characteristics by 14

laboratories. After final data reduction and correlations are comleted, this study is expected to provide the data necessary to

determine which characteristics should be monitored for re-refined

oil basestocks, a crucial question.

Testified as an expert witness at three Congressional Hearings on

Oil Recycling.

Provided cooperative efforts in support of two important non-NBS

recycled oil programs:

-- U.S. Army MERADCOM's development of the MIL-L-46152A revised

specification, which now allows use of re-refined basestock.

-- Environment/Canada's fleet test evaluation of re-refined oil

in Royal Canadian Mounted Police vehicles.

° In addition to the above, the Program Manager has been an invited

speaker at national and/or international meetings of the

Association of Petroleum Re-refiners, the Society for Automotive

Engineers, the American Society of Lubrication Engineers, the

American Petroleum Institute, the National Petroleum Refiners

Association, the Independent Oil Compounders Association, the AllIndia Re-refining Conference, the Second European Congress on Recycling of Used Oil, and others.

The above specific items of efforts within the Recycled Oil Program

indicate to some extent the activity which has occurred in this program

during the past years. At the present time, the Recycled Oil Program

funds efforts consisting of approximately 15 staff-years within the NBS

technical divisions, plus three projects located outside NBS. These

efforts have contributed greatly to the recent advances in oil recycling.

24
The Future

The future of the Recycled Oil Program during FY-1982 and beyond is

difficult to predict. We currently estimate that the test procedures for

re-refined engine oil, if current progress can be successfully maintained,

can be completed by the end of FY-1983. Additional work on re-refined

automotive transmission oils, re-refined hydraulic oils and re-refined or reclaimed industrial oils would require additional time, probably ranging

from 1-3 years all told.

On the other hand, current contractions in government funding may

seriously affect the Recycled Oil Program in the future, requiring

curtailment and/or cessation of these activities. At present, FY-1982

funding appears to be firm, and we are continuing our efforts on completion of the tests for engine oils.

25
References

1. E. A. Frame and T.C. Bowern, Jr., "U.S. Army/Environmental

Protection Agency Re-refined Oil Program," AFLRL Report No. 98,

May 1978 (Available from Defense Documentation Center, Cameron

Station, Alexandria, VA 22314).

2. House of Representatives, "Used Oil Recycling Act of 1980," Report

No. 96-1415, 96th Congress, Government Printing Office,

Washington, D.C.

3. K. Frassa, "ASTM/NBS Base Stock Consistency Study," in

Proceedings, Joint Conference on Measurements and Standards for

Recycled Oil /Systems Performance and Durability, edited by

D. A. Becker, NBS Spec. Publ . 584, U. S. Department of Commerce

(Nov. 1980).

4. W. C. Starr, "Consistency of Base Stock Production - An ASTM/NBS

Study," to be published in Proceedings, 4th International

Conference on Used Oil Recovery and Reuse, Association of

Petroleum Re-refiners, Washington, D.C. (In Press).

26
THE RESOURCE CONSERVATION AND RECOVERY PROGRAM

27
II

The Resource Conservation and Recovery Program

I. Goal and Objectives:

NBS involvement with recycled materials spans several decades.

However, the program described here dates from 1973 when data concerning

reactions from incineration of municipal solid waste were obtained by the

Physical Chemistry Division. In 1976, the Congress via the Resource

Conservation and Recovery Act (RCRA), assigned DoC and NBS direct

responsibilities for research concerning recycling. The Office of

Recycled Materials within NBS is the Departmental focal point for

fulfilling these legal mandates. The goals and objectives of the RCRA

program are as follows:

Goal :

To improve the Nation's productivity and innovation by providing a framework for fostering the advances required to optimize the mix of

economic and environmental factors associated with the disposal and

subsequent recovery and/or reuse of resources contained in municipal,

industrial, commercial and hazardous solid wastes.

Objectives :

(1) To develop methodologies for the economic assessment of current and

potential technologies, market potentials, and institutional barriers

relative to resource conservation and recovery, and to assist public and

private sectors to fully utilize both the methodologies and information

derived therefrom; (2) to evaluate current and innovative technologies for

the conservation of materials, as well as the recovery, reuse, and

recycling of waste materials from all potential sources including

industrial processes; (3) to provide for the economic retention and

development of businesses and industries through mitigation of the impact

of federal regulatory policies, particularly environmental actions, and

by utilizing the potential for new business opportunities and growth.

Sections 5002 and 6002 of RCRA mandate NBS actions concerning

guidelines for specifications for recovered materials and governmental

procurement of recycled goods. Note that NBS will be the only federal

laboratory carrying out research involving resource recovery after FY

1981. The Environmental Protection Agency (EPA) announced in April 1980

that it would have to devote all of its research resources to hazardous

waste problems in FY 1981 and thereafter. The Department of Energy has

effectively left the field as well.

The NBS efforts fall into three main categories:

(1) Direct 1 aboratory-based research aimed at achieving the goals of

RCRA;

(2) Examination of governmental policies with respect to procurement

of products containing recovered materials; and

28
(3) Identification and assessment of the need for uniform physical

and chemical measurements which derive from laws, regulations

and policies at the state and local level. (Note that the

Resource Recovery portion of this effort is part of a larger NBS

effort to define state measurement needs in detail.) Current

activities and some plans for the future in each of these

categories are discussed in detail.

The Technical Advisory Center (TAC) works to improve the Nation's

productivity and innovation by providing a framework for fostering the

advances required to optimize the mix of economic and environmental

factors associated with the disposal and subsequent recovery and/or reuse

of resources contained in municipal, industrial, commercial and hazardous

solid wastes. The TAC accomplishes these goals by developing

methodologies for the economic assessment of current and potential

technologies, market potentials, and institutional barriers to resource conservation and recovery; to assist public and private sectors to utilize

fully the methodologies and information; and, by identifying the potential

for new business opportunities and growth. In short, TAC's primary

function is to assure implementation of RCRA responsibilities of the

Department, which are (i) encouragement of the commercialization of proven

technology; (ii) stimulation of the development of markets for recovered

materials, and (iii) evaluation of the commercial feasibility of resource recovery facilities as well as the development of an information base to

assist communities and other entities in selection of a recovery system.

The TAC currently interacts with a wide variety of parties affected

by RCRA including private industry, intergovernmental entities such as the

Great Lakes Basin Commission, state and local government, universities,

public interest groups, other federal agencies, and interested entities

within DoC.

29
RESOURCE CONSERVATION AND RECOVERY PROGRAM

II. Introduction

The Resource Conservation and Recovery Act of 1976 (P.L. 94-580)

enacted October 21, 1976, directs the Secretary of Commerce, acting

through NBS, to hold public hearings and publish guidelines for the

development of specifications. These specifications are needed for the

classification of materials which can be recovered from waste now destined

for disposal. NBS is authorized to undertake work of this nature by

15 use 272 which describes functions of the Secretary of Commerce to

include "the determination of physical constants and properties of

materials when such data are of great importance to scientific or manufacturing interests and are not to be obtained of sufficient accuracy

elsewhere."

The Nation generates about 145 million tons of municipal solid waste

per year. Currently, over 93 percent of this waste is disposed by open

dumping, "sanitary" landfilling, incineration or ocean dumping, all

environmentally unsound methods. Alternatives to land disposal methods

must be found since many cities in the U.S. may run out of suitable solid

waste disposal sites in the near future. A method to do this is to

separate metals, glass and the organic fraction of this refuse from one another thus providing a potentially marketable set of commodities.

Large quantities of potential resources are being discarded in the

waste. According to figures compiled by EPA, we annually discard about

20 percent of the Nation's tin and aluminum requirements, 10 percent of

its ferrous metal requirements, enough glass to replace a year's needs for

glass containers, and enough organic material, which if converted to

energy could provide up to 2 percent of current energy needs.

In enacting P.L. 94-580, the Congress stated that:

(1) Millions of tons of recoverable material which could be used are needlessly buried each year.

(2) Methods are available to separate usable materials from solid

waste.

(3) The recovery and conservation of such materials can reduce the

dependence of the United States on foreign resources and reduce

the deficit in its balance of programs.

In order to reclaim materials and energy from municipal solid waste

in an economically acceptable way, markets for these commodities must

exist. Energy can be reclaimed from the organic fraction of the refuse

(80 percent), but, unless a stable long-term market for this energy is

found, large scale reclamation of energy and materials is not financially

feasible. The organic fraction is usually converted to refuse derived

30
fuels (RDF) which can take several physical forms: fluff, pellets,

powder, gas, liquid, or solid char. In the absence of characteri zation

and specifications for all of these forms of RDF, marketing of this

commodity has proven very difficult. Hence, a necessary first step is

selecting the form of RDF best matched to the market in the region of the resource recovery facility. For example, in a 40,000 square mile

tri -state region in the midwestern U.S., a market was found to exist if

RDF meeting a certain specification could be produced. This market would

enable 82 percent of the region's waste to go to resource recovery.

Otherwise, in the absence of the market, virtually all of the waste would

be landfilled. The NBS program under P.L. 94-580 will place heavy

emphasis on the characterization of RDF in order to have a firm basis

(specification) for marketing.

Once the crucial energy marketing step is completed, it becomes

economically feasible to recover other materials such as metals and glass.

Again, specifications will tend to dictate whether the materials emerging

from the resource recovery facility can be sold at a suitable price.

Since the beginning of 1981, ORM has been dealing in far greater

detail with problems faced by the private sector, i.e., non-hazardous

industrial wastes. In calendar year 1981, ORM has taken the following

actions with regard to industrial wastes:

A major study in the Great Lakes Region concerning business

response to hazardous waste regulations.

Agreement to cooperate with the tanning industry on recovery of

chromium and reduction of waste from tanning processes.

Close cooperation with the petroleum industry concerning uses for

waste oils.

Agreement to work with the steel industry concerning recycling or reuse of mill sludges and pickle liquors.

In addition, ORM has become increasingly involved with

characterization of discards which may be deemed hazardous. With

cooperation from the Department of Energy (DoE), the Environmental

Protection Agency (EPA), the Department of Defense (DoD), and the American

Iron and Steel Institute (AISI), ORM has begun to characterize such

materials. Among the reasons for doing so are that some 50 million metric

tons of potentially hazardous wastes are produced annually in the United

States. That amount grows at a projected rate of about 3.5 percent a year. And less than 10 percent is probably being disposed of in an environmentally sound manner. Furthermore, the number of actors who are involved with hazardous waste is immense:

Over 750,000 businesses generate some amount of hazardous waste.

Over 10,000 transporters are involved in shipping it.

Over 30,000 sites are used for treatment, disposal, or storage--

some on the premises of the generator, others located elsewhere.

31
Hazardous wastes--whether from a chemical plant, battery producer, or electroplater, to cite three examples--are either disposed of at the

factory or off-site. In either case, the disposal options are nearly

identical

° Disposal on the land

“ Incineration

^ Placement in lagoons

Injection wells

Recycling or reclaiming

If wastes are not retained on-site, they are transported elsewhere by

truck, barge, or rai 1

Safe waste management should embody the best technologies that can be

developed. Yet without rules and regulations to ensure protection of

public health and the environment, the costs of disposal have been low.

As a result, industry has had little incentive to apply resources or brainpower to developing better, safer technologies for managing wastes.

Waste storers, treaters and disposers will seek out more

sophisticated technological processes to properly handle their wastes.

And the costs of environmentally sound waste management will rise,

producing a powerful incentive for generators to change methods of

production so as to minimize their output of hazardous wastes.

32
III. Needs

The duties of the Secretary of Commerce are set forth in

Sections 5001 to 5004 (42 U.S.C. 6951 et. seq.) of P.L. 94-580.

Section 5001 (42 U.S.C. 6951) requires the Secretary to encourage

greater commercialization of proven resource recovery technology. Four

specific tasks are indicated:

(1) Provision of accurate specifications for recovered materials;

(2) Market development stimulation for these materials;

(3) Promotion of proven technology; and

(4) A foriffn for the exchange of both technical and economic data

relating to resource recovery faci 1 ities--presumably high

technology plants designed to recover materials and/or energy

from municipal waste.

Section 5002 (42 U.S.C. 6952) specifically directs the Secretary,

acting through NBS, "to publish guidelines for the development of

specifications for the classification of materials recovered from waste

which were destined for disposal. The specifications shall pertain to the

physical and chemical properties and characteristics of such materials in

various industrial, commercial and governmental uses." In addition,

P.L. 94-580 directs NBS to hold public hearings on these guidelines and to

publish the guidelines. These guidelines will: (1) Aid in conserving

valuable material and energy resources, (2) increase the rate at which

resource recovery from municipal solid waste will occur in the U.S., and

(3) serve in the settlement of possible disputes involving the use of

recyclables in items purchased by the Federal Government (Section 6002

(42 U.S.C. 6962) of P.L. 94-580.

33
IV. Current Activities

Several projects were completed since the Panel meeting last May.

Appendix I is the Executive Summary of the final report concerning

procurement of products containing recovered materials. The State

Measurement Needs Study was also completed, and Appendix II contains the

title page and Executive Summary of this report. A number of directly

supported research projects also issued reports. These are included in

Appendices III - IX. Finally, what follows is a summary of ongoing

research which is being carried out in fulfillment of the mandates of the

Resource Conservation and Recovery Act.

34
A. RESOURCE RECOVERY PROGRAM

35
Project Title: Combustion Calorimetry of Refuse and Refuse-DerivedFuel (RDF)

Goal: (1) To provide a consensus test method for determining the heating

value of minimally processed refuse so that engineers can evaluate the performance and design specifications of an incinerator or boiler with enhanced confidence.

(2) To provide test methods for determining the heating value of

RDF so that it can be established as an article of commerce.

Technical

Areas at

NBS:

Center for Chemical Physics

Chemical Thermodynamics Division

Personnel: E. S. Domalski, D. R. Kirklin, J. Colbert, K L. Churney, M. L. Reilly,* A. E Ledford, R. Kelly, S. Abramowitz, and R.V. Ryan.

Other

Agency

Support:

U. S. Department of Energy

Office of Energy from Municipal Waste

D. Walter, B. Greenglass, C. Kouts, and L. Lehr

Compatible with the Resource Conservation and Recovery Act of 1976 is

the national aim to expand our technology to produce useable energy from

solid waste. One of the greatest needs is to develop test methods for the

determination of the heat of combustion of refuse and refuse-derived-fuels

(RDF). Evaluating the design specifications of an incinerator or a boiler

and the buying and selling of RDF will be done on the basis of the heats

of combustion of RDF samples. At present, commercial laboratories use conventional bomb calorimetric techniques on gram-size samples. There is

a dispute about the reliabiity of the current techniques for measuring the

heat of combustion of the input waste stream. Many combustion engineers

believe that the input waste stream to an incinerator installation cannot

be sampled and processed to produce gram-size amounts of material whose

heating value is representative of the original waste. Those engineers

argue that the original heterogeneity of the waste stream and changes in

composition caused by processing to gram-size samples dictate that the

test sample should be minimally processed and of kilogram size. At

present, insufficient quantitative data exist to resolve the problem.

Establishment of a consensus method requires calorimetric measurements of

grams to kilogram-size samples.

The NBS effort in the development of test methods to determine heats

of combustion of refuse and refuse-derived-fuel dates back to April 1977,

shortly after Congress passed the Resource Conservation and Recovery Act

of 1976. The initial effort involved the determination of whether a 25-

gram capacity bomb calorimeter could provide heats of combustion which more accurately represented a gross RDF sample than did the heat of

combustion determined in the conventional -si ze (2.5 gram capacity) bomb

* Center for Absolute Physical Quantities

Temperature and Pressure Measurements and Standard Division

36
calorimeter.

Comparative studies involving calorimeters with sample capacities

of 2.5 gram, 25 grams and 2.5 kilogram are being carried out to determine

the sample size necessary to produce heats of combustion that accurately

represent a gross RDF sample. From April 1977 to the present time, more

than 20 different RDF samples have been studied in the NBS calorimeters.

Accomplishments in FY 1981

Five lines of work have been emphasized during the past year:

(A) Oxygen flow calorimetry of solids, (B) Oxygen bomb calorimetry of

solids, (C) Metals in RDF, (D) Variability of municipal solid

waste, (E) Ash content of RDF, coal, and RDF/coal mixtures as a function

of temperature.

A. Oxygen Flow Calorimetry of Solids

A 2.5 kilogram-capacity flow calorimeter, shown in figure 1, has been

designed for burning pellets of minimally processed municipal solid waste

(MSW). The calorimeter vessel is 3 feet in diameter, 8 feet high, and

will contain 983 liters of water (1 ton). The calorimeter design was based on the results obtained using a trial combustor, 30 inches in

diameter and 6 feet high. Eighteen trial combustions were carried out

using various sample and oxygen supply configurations. Pellets of up to

2.2 kg of minimally processed RDF were successfully burned at rates of 15

minutes per kilogram with CO/CO 2 ratios of less than 0.1%. The component

parts of the 2.5 kg capacity flow calorimeter are being fabricated by

various vendors. We expect calorimeter assembly to begin before the end

of FY 1981.

B. Oxygen Bomb Calorimetry of Solids

(1) ASTM Round Robin Testing of RDF-3

RDF-3 is defined as a shredded fuel derived from municipal solid

waste processed for the removal of metal, glass, and other entrained

inorganic materials. This matrial has a particle size such that 95

weight percent passes through a 2 inch square mesh screen.

A round robin was conducted to compare two ash content procedures

being drafted by ASTM Subcommittee E38.01. Five laboratories

participated. One procedure is the ash furnace method and is similar to

that used for coal and coke (ASTM D-3174-73). The other is based upon the

ash residue remaining in the combustion bomb after a calorimetric

determination has been carried out. The assumption that ash-content data

on a twin or equivalent analysis sample which has been determined using

ASTM D-3174-73 is applicable to combustion bomb calorimetric data is not

completely valid. Ash was measured in a furnace at 575°C and 725“C. Ash was also determined as the bomb residue of a combustion experiment where

temperatures are in excess of 1500°C. The ash content is an important

parameter since it is used with calorimetric data to calculate higher

heating values on a moisture and ash-free basis. The temperatures 575°C

and 725°C were selected because they are the ASTM ashing temperatures for

cellulose and coal, respectively. The bomb residue method is important

37
h 1 METER H

Figure 1. The 2.5 Kilogram Capacity Flow Calorimeter.

A. Combustor

B. Combustor enclosure

C. Exhaust cooling coils

0. Exhaust condenser 38

E. Flow shied

F. Calorimeter vessel

G. Stirrer

H. Water-wall jacket
because it relates directly with the calorimetric data obtained in the

RDF-3 combustion measurement. Within experimental uncertainties, as determined from the standard deviation of a measurement, the ash contents

compared well between the laboratories. However, in four out of the five

laboratories, the bomb ash method had the highest precision. Although

fuel ashing methods are traditionally carried out in combustion furnaces,

we have written an ASTM subcommittee E38.01 draft standard using the bomb

ashing technique as an alternate ashing method because of its higher

precision and its direct traceability to the actual combustion data. This

draft standard has been reviewed by subcommittee E38.01 members and is

ready for balloting for acceptance as an ASTM standard.

(2) Interlaboratory Tests on RDF-3

The ASTM round robin testing of RDF-3 began in June 1978 and ended in

September 1980. Concern over the apparent dispersion of test data on the

residual moisture, ash content, and higher heating values led to the re- determination of these properties at NBS using ASTM processed RDF-3

samples which were obtained from some of the participating laboratories.

During the ASTM testing program from June 1978 to September 1980, the

i nterl aboratory reproducibility for RDF-3-samples was two to three times

lower than the interlaboratory reproducibi 1 ity for test on coal samples.

To determine if the variability was due to the sample or to the individual

laboratory procedures, NBS obtained eight previous round robin samples

from four of the participating laboratories. Higher heating values,

moisture contents and ash contents were measured in the NBS laboratory and were compared to the previous results that were submitted by the

participating laboratories during the round robin testing studies. The

new results differed only slightly from the previous reported ASTM round

robin results.

(3) Processing Effects in RDF-3

A study was designed to determine the effect of sample processing on the higher heating values and ash contents of RDF-3 samples. Teledyne

National RDF-3 before (RDF-3 Fluff) and after (RDF-3 extrusion)

pelletizing were obtained for this study. The samples were coned and

quartered with quarters I and III to be milled to pass a 1.6mm (1/16 inch) screen and quarters II and IV to be studied as received. The RDF-3 fluff

was pressed into pellets for measurement of the heating value. The

heating values are being measured in the 25 gram-capacity bomb

calorimeter. At the conclusion of this study (1 September 1981), data

will be compared for RDF-3 fluff and RDF-3 extrusion which will provide

information on the effect of pelletizing samples at the Teledyne National

Resource Recovery Facility. Data will also be available on the RDF-3

fluff and RDF-3 extrusions after these materials have been milled to

provide information on the effect of laboratory processing of RDF-3

samples. In both the extrusion and milling processes, significant

quantities of heat are liberated and this study will identify if any

sample degradation has occurred during these processes. Together with the

moisture and ash data, heating values can be compared on an as-received,

moisture-free, and moisture and ash-free basis.

39
c. Metals in RDF-3

The Aluminim (Al) and iron (Fe) content of RDF-3 has been found to be

of the order of 0.5 percent each. Conventional heating value measurements

are made on milled samples where finely divided Al and Fe may burn and

conribute to the measured heating value. In a preliminary study during

fiscal year 1980, a synthetic RDF was prepared containing 80% cellulose

and 20% non-combustible (silica, alumina, and iron oxide) and was doped

with 3% Al or 3% Fe. Based on known heats of combustion of the starting

materials, it was found that 60% of the Al and none of the Fe burned.

This may have been due to the particle size of the metals and therfore a study was planned to investigate the effect of metals in RDF further. A

synthetic RDF of the previous composition was prepared. Al and Fe powders

of 40, 150, and 350 micrometers were obtained to dope the synthetic RDF so that it would have a metal content of 0.5% separately and 1.0% combined.

Heating values, moisture content, and ash contents have been measured for

the undoped synthetic RDF and the synthetic RDF which has been doped with

the 40 and 150 micrometer metals. Values are presently being measured for

samples doped with 350 micrometer particle size metals. At the completion

of this study (1 September 1981), the data will be compared to the

theoretical heats of combustion which are based on the heats of combustion

of the starting materials. Theoretically, the heat of combustion will be

significantly lowered if none of the metal burns, moderately lowered if

the Fe burn to either FeO, Fe203 , or Fe 30^ and significantly higher if the

Al burns to AI 2 O

3

.

D. Variability of Municipal Solid Waste

During fiscal year 1980, a study was carried out to determine the

variability of municipal solid waste (MSW) examined over a two-week period

at the Baltimore County Resource Recovery Facility in Cockeysvi 1 1 e, MD.

Municipal solid waste was processed through a primary shredder and samples were collected daily for two weeks. After the total moisture content was determined, the samples were reduced in particle size to 2 mm or less. A

total of 40 samples were prepared for measurements. Testing was carried

out for residual moisture, furnace ash, bomb ash, and higher heating value

(HHV).

During fiscal year 1981, the results were analyzed and showed that

the daily variability of MSW is large and is demonstrated by the data

obtained for moisture, ash, and HHV determinations. Statistical analysis

of the data suggests that the day to day variability of MSW constitutes 70

to 80 percent of the overall variability, with the other variables being errors in measurement techniques, sampling, and systematic errors.

The study was performed to determine the merits of making measurements on RDF samples of the order of 2.5 kilograms in order to increase the

confidence for a higher heating value of a fuel derived from the variable

municipal solid waste (MSW). The development of a 2.5 kg capacity

combustion calorimeter is not expected to reduce the overall variability

(precision) of data on HHV beyond what is currently available from

conventional combustion calorimeters which accommodate gram-size samples.

Unfortunately, test procedures which require gram-size samples of MSW or

40
RDF introduce uncertainties into the measurement results because they so poorly represent the large multi-ton array of refuse. This representation

maybe poor not only because of the high heterogeneity of refuse but also

because of the large amount of processing necessary to produce an analysis

sample.

One can expect to have more confidence in data on HHV's which are determined in a 2.5 kg capacity combustion calorimeter because a larger

sample is being used. The use of a larger sample should lead to an average HHV which is closer to the true mean of the refuse population than

one would obtain from using gram-size samples. Such HHV's should be more

accurate, but may not be any more precise.

E. Ash Content of RDF, Coal and RDF/Coal Mixtures as a Function of

Temperature

The purpose of the study was to find out whether recommended ashing

temperatures which are to be used in proposed ASTM protocols or which are used in existing ASTM protocols are sensitive to small temperature

fluctuations. The mineral matter present in ash residues from RDF or coal

contains carbonates, sulfates, and finely divided metals. The

decomposition of carbonates or sulfates can be responsible for marked

fluctuations in the mass determined for an ash residue if the ashing

temperature lies in the range in which such decomposition is significant.

The oxidation of finely divided metals can produce an increase in the mass

of an ash residue within a specified temperature range.

The ash content was determined for four selected refuse-derived-fuel

(RDF) and four coal samples at 100°C intervals over the temperature range

from 575 to 1225°C. A 50/50 mixture of RDF/coal is presently being

studied over the same temperature range. X-ray diffraction analysis of

these ash samples which were obtained at elevated temperatures reveals the

presence of the more prominent crystalline phases present. These phases

suggest which chemical reactions may be taking place at the various ashing

temperatures. The phase assemblage for the RDF ash samples are remarkably

similar over the entire range of temperatures studied. This is also true

for the coal ash samples, although to a lesser extent. Data on the higher

heating value and ash content of 50/50 mixtures of RDF with coal show that

these properties are additive.

F. Enthalpy of Combustion of Microcrystalline Cellulose

A test substances with characteristics and properties similar to

those of cellulose-based solid waste products is needed to calibrate

calorimeters and combustors which will be routinely burning refuse or RDF

to determine their calorific values precisely for use in commerce. Microcrystl 1 ine celluose was found to be a good calibrant for this

purpose. The enthalpy of combustion of microcrystalline cellulose, AH°,

at (25“C), was determined to be -2812.40 ±0.56 KJ/mol (2 sdm) based upon

the sample mass.

Plans for FY 1982

(A) Oxygen flow calorimetry of solids

41
Construction of components of the 2.5 kilogram capacity flow

calorimeter will be completed early in FY 1982. Assembly and testing will

follow. Calibration will be carried out using mi crocrystal 1 i ne cellulose.

Calorimetric measurements are planned for both minimally processed and

highly processed RDF.

(B) Oxygen bomb calorimetry of solids

Calorimetric measurements will be carried out to establish the

comparison between bomb and flow experiments. Continued work on the

synthetic RDF is planned in coordination with ASTM Subcommittee E-38.01 on Energy. Also, provide this Subcommittee with results of betweenlaboratory study on furnace ash and bomb ash procedures. Calculate

results and prepare a manuscript on measurements performed in the 25 gram

capacity bomb calorimeter on Teledyne National (RDF-3 fluff) and (RDF-3

extrusions)

(C) Metals in RDF

A manuscript will be prepared describing the results of calorimetric

studies on the doping of the synthetic RDF sample with finely-divided

aluminum and iron.

(D) Variability of municipal solid waste

A manuscript will be prepared for publication on the variability of

municipal solid waste and its impact upon the development of test

procedures for the determination of higher heating value.

(E) RDF, coal, and RDF-coal mixtures

Ash content studies and combustion calorimetry of RDF-coal mixtures

will be continued. If possible, the comparison of combustion of RDF-coal

mixtures in pure oxygen and air will be carried out.

42
Project Title: Research in Thermometry Applicable to Resource Recovery

Goal: (1) To provide technical assistance in the design and development

of a large sample constant pressure flow calorimeter.

(2) To develop high temperature instrumentation for thermometry.

Technical

Areas at

NBS:

Center for Absolute Physical Quantities

Temperature and Pressure Measurements and Standards Division

Personnel: M. L. Reilly, G. W. Burns, W. S. Hurst, G. T. Furukawa,

J. P. Evans, and L. A. Guildner.

Accomplishments in FY 1981

A. Design and Development of a Large-Sample Flow Calorimeter

During FY 81, now ending, the following staff on the CAPQ have been

directly involved in the development of a large-scale calorimeter for use

in the NBS Resource Recovery Program: M. L. Reilly, G. W. Burns, W. S. Hurst, and G. T. Furukawa. Mr. Reilly, in collaboration with Dr. K. Churney and other colleagues in the Center for Chemical Physics, has

participated in nearly every phase of the development work this year.

The first quarter of FY81 was devoted to the analysis of data

obtained in 18 experiments using a prototype combustor in which samples of

up to 2.2 kg of RDF or cellulose had been burned in Flowing oxygen. A

detailed understanding of the performance of the combustor was a prerequisite for the design of the large-scale calorimeter.

The final design of the 2.5 kg capacity flow calorimeter was completed in the second quarter of FY31. The first draft of a manuscript

describing the experiments with the prototype combustor and the analysis

of the experimental data was finished. Because accurate flow measurements

are essential to the success of the program, Reilly attended the Second

International Symposium on Flow, Its Measurement and Control in Science

and Industry wnich was held in St. Louis in March.

Much of the third quarter was spent in preparation of a manuscript

for the Second International Symposium on Materials and Energy from Refuse

(Antwerp, Belgium on Oct. 20-22, 1981). Assembly of the final version of

the 25 gram flow calorimeter was begun. Several trial burns were conducted to test the performance of the new cooling coils and water

condenser/trap. Additional software was developed to support the

instrumentation added particularly for flow measurements and infrared

analysis of trace constituents of the exhaust gas steam.

During the last quarter of FY81 the heat of combustion of pure

cellulose will be determined using the final version of the 25-gram

capacity flow calorimeter. Cellulose is to be used as a chemical

calibrant for the 2.5 kg capacity calorimeter. The purpose of these

43
experiments is to establish a correspondence between the flow result and

that obtained recently using the combustion bomb. A major feature of

these experiments will be the electrical calibration of the flow

calorimeter as well as calibration using a methane-oxygen combustion

reaction.

As noted above, individual contributions to the success of the

calorimetery project were made by other CAPQ personnel. Included in this

group are the following:

George Burns provided advice about the selection and use of

thermocouples for the final version of the 25 gram capacity flow

calorimeter. A significant improvement was made in the measurement of the

temperature of moist flowing gases. This technique will also be used in

the large-scale flow calorimeter.

Wilbur Hurst, although not officially reprogrammed into the resource

recovery area, has contributed signficantly to our data acquisition

capability through his developmental work with the S-100 minicomputer

systems. He provided new operating systems which interface our system

with a real-time clock and the IEEE bus.

George Furukawa has prepared shop drawings for an assembly in which

the quartz crystal thermometers to be used to measure temperatures in the

flow calorimeter can be calibrated through comarison with standard

platinum resistance thermometers.

One paper and one report on the calorimeter project resulted from

work performed in part by personnel from this Center. These are:

Paper

Churney, K. L., Reilly, M. L., Ledford, A. E., Ryan, R. V., and

Domalski, E. S. , "An Oxygen Flow Calorimeter for Determining the

Heating Value of Kilogram-Size Samples of Solid Muncipal Waste," (to

be published in the proceedings of the Antwerp Conference).

Report to Sponsor

Kirklin, D. R., Colbert, J., Churney, K. L., Reilly, M. L., Ledford,

A. E., Ryan, R. V., Kelly, R. V., and Domalski, E. S., "Test

Procedures for the Determination of the Gross Calorific Value of

Refuse and Refuse-Derived Fuel of Kilogram-Size Samples Using

Constant Pressure Flow Calorimetry" (in press).

B. Development of High-Temperature Instrumentation for Thermometry

During FY81, the following staff of CAPQ have been involved in the

development of thermometry appropriate for use at the temperatures

commonly found in combustion processes: G. W. Burns, G. A. Evans,

J. P. Evans, and L. A. Guildner. This work was separated into three

component projects this year.

44
The first project had as a major output the evaluation of

thermometry feasibility in systems containing molten metal components.

Its accomplishments include the following, produced by G. W. Burns and

G. A. Evans:

1. Design of thermocouple test probe for first measurements of

lifetime in molten metal. The design objectives include:

a) Probe life of 15-20 minutes;

b) Temperature range 1400 °C - 1650 °C;

c) Suitability as prototype for reference thermometer in

evaluating disposable immersion thermocouple thermometers

in an experimental 8-ton arc furnace at the Homer Research

Laboratory of the Bethlehem Steel Company.

2. Acquisition of component parts and minerals sufficient to

fabricate six probes.

3. Construction of two probes of the chosen design. These probes

utilize Type B (PI atinum-30% Rhodium vs. Platinum-6% Rhodium)

thermocouples insulated with high-purity aluminum oxide and

protected by a self-bonded Type KT silicon carbide sheath

13 mm o.d., 0.6 m long. The silicon carbide sheath, which is

immersed directly into the molten metal, is joined

mechanically to a 2.2 m long connecting extension wire of

stainless steel. The stainless steel extension is protected

by a multi-layer wrap of Fiberfrax 800 ceramic fiber paper and

is of a concentric tube design to allow for forced air

cool ing.

4. Design and construction of a preliminary test crucible to be

utilized in the NBS laboratory for preliminary probe

evaluation. The test crucible was fabricated from A. P. Green

Refractories Company castable AP-96.

5. Experimental test of thermocouple probe sheaths. The

durability of two types of silicon carbide sheaths in molten

iron was evaluated. Sheaths of the self-bonded type KT

silicon carbide and of a chemically vapor-deposited silicon

carbide were tested. In these tests, a batch of scrap iron was heated inductively in the laboratory crucible in air at

1350°C to 1450°C until a heavy slag layer formed. The sheaths

were then immersed rapidly into the molten iron. After

immersion for 3-6 minutes, the sheaths were withdrawn and

inspected. Both types of sheath suffered gross chemical — - attack and erosion by the iron-rich oxide slag at the melt-air

interface. The 3 mm thick wall of the sheaths was nearly

eroded through after 5 minutes exposure to the slag.

The results of this test indicated a need for more durable

sheath material to protect the test probe thermocouples.

Another DoE contractor, T. Negas, recently completed

investigation of several graded cermet-oxide ceramic coatings

on molybdenum as protective covers in harsh chemical

environments. Their results include a total time to failure

45
in excess of 5 hours in molten gray iron for an arc plasma

spray coating of MgAl20i^ on Mo tubes.

6. Redesign of the protective sheaths based on coated Mo tubing

has been completed. Mo tubing ordered, and a local coating

source has been contacted.

7. Progress reports presented at November 1980 and May 1981

meetings of American Society for Testing and Materials

E-20.04, which has been organized for the purpose of

facilitating development of test methods for molten ferrous

thermometry.

The second project was initiated by Drs. Wing Tsang and Walter Shaub.

It concerns the direct monitoring of reactions and temperatures in a combustion environment. The present activity involves the construction of

a high-temperature furnace and the measurement of its temperature profile.

The work accomplished so far this fiscal year includes the design of the

furnace and the instrumentation. The CAPA portion of this project

currently consists of a part-time effort on the part of G. W. Burns, who

is providing design guidance to Dr. Shaub.

The third project is the continuing development and testing of

special high-temperature resistance thermometers for optimum accuracy use

at temperatures to 1100 °C. This work is taking place in the hands of

J. P. Evans and of L. A. Guildner. During FY81, nine thermometers have

been built and evaluated. Six of these experienced diminished alphacoefficients after relatively short exposures of 1100 °C; analysis of the

resistor elements indicated the presence of Pd and Cu contaminants at

levels which could easily cause such effects. Of the other thermometers,

one has showed excellent resistance to the effects of high-temperature

exposure of several hundreds of hours. Its alpha-coefficient remained

above 3925 after heating for more than 300 hours. Work on this project is

continuing with the following directions:

1. Emphasis on methods of thermometer assembly to avoid

contami nation;

2. Study of mechanical modes of failure, including separation of

leads from the resistor, shorting of turns of the resistor,

and separation of the resistor from its support;

3. Evaluation of the feasibility of electrical guarding of

nominal 2.5-ohm thermometers as opposed to utilizing heavier

resistor wire for greater strength at the expense of reduced

sensitivity and poorer thermal equilibrium properties.

Plans for FY 1982

Mr. Reilly will continue to work full time on the design and

development of the large-sample flow calorimeter. Interaction by other

members of the staff of the Temperature and Pressure Measurements and

Standards Division will be based upon the specific need of the program as

it develops.

46
The work of Guildner, Burns, and Evans on the development of high

temperature instrumentation for thermometry will be continued.

47
Project Title: Applied Research on Combustion Characterization of

Refuse-Derived-ruel (RDf^)~~

Goal: Phase I

(1) To perform tests on RDF using static measurements (bomb

calorimetry, elemental analysis, ash content, moisture

content, etc.) and dynamic measurements (TGA, DSC EGA(*),

etc. )

(2) To study the entrained combustion of RDF particles in a specially designed laboratory furnace.

Phase II

(3) To validate the results obtained in the test laboratory

characterization of RDF developed in Phase I through a study

of RDF combustion in a combined fixed-bed/entrained-flow

industrial facility.

Answers to the following questions are expected from this

study:

(a) What particle size range of the fuel is entrained under a given set of boiler parameters (excess air, temperature gas

velocity)?

(b) Is the fraction of the fuel settling (under specified

conditions) such that a grate is necessary?

(c) What are the devolatilization and combustion times of the

entrained material (as function of excess air, etc.)? How do

these compare with the analogous parameters for pulverized

coal?

(d) What are the ignition times and temperatures for the entrained

fraction?

(e) How do the ignition and heat release parameters in fixed-bed

(grate) firing of RDF compare?

(f) Are the corrosion problems and boiler emissions (NOx, SOx,

chlorine, etc.) significantly different than in the case of

coal ?

(*) TGA, Thermal Gravimetric Analysis

DSC, Differential Scanning Calorimetry

EGA, Evolved Gas Analysis

48
Technical

Areas at

NBS and

Personnel

Center for Chemical Physics

Chemical Thermodynamics Division

E. S. Domalski, D. R. Kirklin, J. C Colbert,

A. E. Ledford, R. V. Ryan, R. Kelly

Center for Chemical Physics

Chemical Kinetics Division

W. Tsanq, W. Schaub, -1. A, Walker, S. Stein

Center for Chemical Engineering

Thermal Processes Division

A. Macek, C. Bulik, S. R. Charagundla

Other U. S. Department of Energy

Agency Office of Energy from Municipal Waste

Support D. Walter, B. Greenglass, C. Kouts, and L. Lehr

Accomplishments in FY 1981

A. High Pressure Differential Scanning Calorimetry of

Refused-Derived-Fuel (RDF)

(to be presented at the Eleventh North American Thermal Analysis

Society Conference in October 1981)

The results of an investigation by W. Tsang and J. A. Walker are described on the properties of the organic portions of municipal solid

waste as determined by high pressure differential scanning calorimetry

under oxidative and pyrolytic conditions. It is part of the program of

the Office of Recycled Materials at the National Bureau of Standards under

the Resource Conservation and Recovery Act of 1976 (PL 94-580). More

specifically, the present work is a response to the current interest in

the use of municipal solid waste as an alternative fuel and addresses the

need for defining the nature of the substance, determining methods for

characterization and provide information with respect to end use contexts.

The heterogenous nature of the substance, determining methods for

characterization and provide information with respect to end use contexts.

The hetergeneous nature of municipal solid waste in general and the

organic fraction in particular makes thermo-analytical methods

particularly useful since the thermograms may permit a degree of

differentiation greater than that derivable from standard ASTM methods,

but without the detail [which would be difficult to interpret] if

molecular specific detection is employed. Furthermore, the heat released

under controlled oxidative or pyrolytic conditions, represents an important combustion property. Nevertheless, the rates are much slower

than the flaming combustion of pertinence to alternative fuel

applications. The physical phenomena that is being simulatd is probably

more akin to smoldering combustion. However, there are marked

similarities and a certain degree of correlation can be expected.

Finally, we arc particularly interested in comparing those results with

the correspondi ng data for coal as well as the specific organic compounds

presumed to be in municipal solid waste.

49
Typical organic composition of municipal waste in the "as received"

state contains paper, yard and food waste, as well as plastics, rubber,

textile etc. (1). For fuel applications. Table I summarizes the present

classification system (2).

Table I

Definitions for Refuse £erived F_uels

(RDF-1) municipal solid waste with white goods removed.

(RDF-2) municipal solid waste with or without ferrous metal

separation, and minimally processed to reduce particle size.

This material has a particle size such that 95 weight percent

passes through a 6 inch square mesh screen.

(RDF-3) shredded fuel derived from municipal solid waste processed

for the removal of metal, glass, and other entrained inorganic

materials. This material has a particle size such that 95 weight

percent passes through a 2 inch square mesh screen.

(RDF-4 ) powdered fuel in which the combustible fraction of the refuse

has been processed. This material has a particle size such that 95

weight percent passes through 10 mesh (0.035 inch square) screen.

(RDF-5) solid fuel in which the processed combustible fraction is

densif led (compressed) into the form of pellets, slugs, cubettes,

or briquettes.

All of the samples that will be discussed in this work can be considered

to be in the RDF-4 category. It should be realized however, that as received they are in the RDF-3 to 5 ranges, but the requirements of the

experimental apparatus necessitates reduction to the powdered form. The

higher heating value of refuse derived fuels of the type considered here

are in the range of 8000-10,000 BTU/lb (3). This is in the range of

values for lignite and is considerably lower than that for other types of

coal. There have been several direct studies on the combustion properties

of refuse derived fuels (4,5). The complex interplay of physicochemical

parameters makes such experiments difficult to interpret. It does appear

however, that refuse derived fuel samples are more readily ignitable in

comparison to coal.

EXPERIMENTAL

All of the experiments were carried out with the DuPont 1090 Thermal

Analysis system associated with a High Pressure Differential Scanning

Calorimeter (DSC) and a Thermal Gravimetric Analyzer (T6A). The majority

of the samples used in these experiments have been prepared by members of

the Chemical Thrmodynamics Division at the National Bureau of Standards.

They have been engaged in an active program to determine the heating

values of refuse derived fuels. In general, the prior preparation

involved grinding and sizing the "as received" fuels into a form that can

be used for the present investigation. The specific samples that have

been tested are as follows:

50
(a) RDF-5 from Teledyne; (b) RDF-3 from Teledyne; (c) RDF-4 from

Combustion Equipment (Eco-Fuel II); (d) RDF-3 from Bureau of Mines

(College Park, Maryland); (e) RDF-4 from National Center for Resource

Recovery [low ash] and (f) RDF-3 from Americology (Milwaukee, Wisconsin).

Most of the work has been carried out with Teledyne samples since

they were readily available. As a basis for comparison, studies have also

been carried out with (a) bituminous coal Standard Reference Material,

(b) newsprint and (c) polyethylene.

For the last two substances, except for shredding, no prior treatment

was employed. All experiments were carried out in a dynamic mode with

flow rates of the order of 50-100 cc/min (NTP), and at a pressure of 700K

Pa (100 psi). The former assures the removal of volatile products and has

been found to be an important factor in assuring reproducibi 1 i ty. All

experiments have been carried out with open pans. The possibility of the

samples igniting and thereby undergoing flaming combustion resulting in

processes too fast to be followed, sets a limit on the oxidizing

conditions that can be employed. This was apparently more serious for the

RDF samples than coal.

RESULTS

Thermograms of the various samples under oxidative and pyrolytic

conditions are summarized in the accompanying figures. They are divided

into several broad categories. Figures II-IV represent data on the effect

of process variables. They include the results of size changes, variation

of heating rates and effect of pressure. We have also established that

weight changes from 1-4 mgs have no effect on the thermograms. The second

set of experiments as seen in Figure V show the variation of four

Teledyne samples that had been collected over a ten day period. Figure VI

represent data which display the variation in the different types of

refuse derived fuels listed earlier. The data in Figure VII represent

experiments with "pure" samples as well as with the coal SRM. Finally in

Figure Vlll-Xwe display thermal gravimetric results for selected samples.

DISCUSSION

An examination of the thermograms given in the earlier section

demonstrate that the fu'^damental signature from refuse-derived-fuel

samples of the type studie::; here involves four distinct peaks. The

differences between this and thermograms of bituminous coal are clear cut

[we have also carried out similar studies with other coal samples. They

have similar thermograms] and is undoubtedly a reflection of the

differences in chemical constitution. It should be noted that our problems with regard to the ready ignitability of refuse-derived-fuel

samples in comparison with coal is in line with other evidence. In actual

use contexts it should be recalled that this will be compensated by the

higher heat of combustion of coal. The stimulus for coal ignition is in

fact stronger.

The four peaks that are characteristic of refuse-derived-fuel

combustion in a high pressure differential scanning calorimeter can be

51
Figure II. Effect of Heating Rates

\\ 52
sc

(M^) ^°Td

Figure III. Effect of Pressure

53

160

200

240

280

320

360

400

440

480

520

560

600

Temperature

(°C)
I

(M^) ^°Td

Figure IV. Effect of Particle Size

\\ 54

160

200

240

280

320

360

400

440

480

520

560

600

Temperature
1 :

Figure V.

(M>") "'°Td

Day to Day Variation of RDF from Same Site
sc

Figure VI

1 I

DSC Thermograms of RDF Samples from Various Sources

56

160

200

240

280

320

360

400

440

480

520

560

600

Temperature

(®C)
DSC

<M")

f^igure VII. DSC Thermograms for Various "Pure" Compounds

57

160

200

240

280

320

360

400

440

480

520

560

600

Temperature

C®C)
TGA

(UTui/;^;) [ ]

Figure VIII. TGA Thermograms for Polyethylene

(dotted curver = DGTA)

58

100

200

300

400

500

600

700

600

900

1000

1100

Temperature

C®C)
oat^oat-ioq [ 3

a) c—-3

Figure IX. TGA Thermograms for Newsprint (dotted curve = DTGA)

(See previous page. Figures XIII and IX are combined)

59

200

300

400

500

600

700

000

900

1000

1100

Tttnnpcrai:^ur«i

(®C)
(UTUJ/^) SAXt^DAIUSg [ ] ^ CM Q1—1 CO (O ^ C\l s

(%) c ]

Figure X. TGA Thermogram for Teledyne RDF-5 (Dotted curve - DTGA)

fin

100

200

300

400

500

600

700

800

900

1000

1100

Temperature

(®C)
identified with the reactions of plastic [polyethylene], cellulosic

products [mostly from newspaper] and apparently two different types of

char. The phenomenological processes are:

plastics products [CO2 ], oxidation

char II, pyrolysis

cellulosics products [CO2 ], oxidation

char I, II, pyrolysis

char I, II products [CO2 ], oxidation

Of considerable interest is a comparison of the thermogram for the "pure"

substances and the refuse-deri ved-fuel mixtures. It would appear that

under our conditions there is a considerable degree of orthogonality

between the processes. With regard to polyethylene it is interesting to

note that while smoldering under oxidation occurs in the 220°C region, the

main weight lose under pyrolysis occurs at a much higher temperature. In contrast, the combustion and main weight loss peaks for cellulosic

substances center about 325-350°C. The interesting consequence is that

when one compares the high pressure DSC tracings of refuse-derived-fuel

oxidation and the TGA results under pyrolysis, there is a switch in the

relative position of the peaks. Under actual boiler conditions

temperature stresses are much more severe and the time scales are vastly

compressed. An important question will be the extent to which this

general mechanism can be carried over. With the present equipment it is

not possible to test for tnis possibility. However, a feasible approach

is to extract from combustion devices partially combusted samples and

subject them to thermal analysis. We are currently planning experiments

in this direction.

An examination of the thermograms for refuse-derived-fuels carried

out under similar ccr.di tions demonstrate that there is considerable

variation, especially with samples from different sources. Of some consequence are the data in Figure VI. It has been established (3) that

for these samoles there are significant variations in heating value and in

ash content. We are in the process of correlating these results. Also of

interest is the rather characteri stic thermogram derived from ECO-Fuel, see Figure VI. Densified refuse derived fuel sample from Teledyne has

almost the same thermogram An interesting question arises as to whether

treatment to the RDF-4 and RDF-5 level may in fact change some of the

combustion properties. Overall, the present results suggest that thermoanalytical techniques can play an important role in providing for quality

control in the processing, handling and use of refuse derived fuels. At

the same time, it is clear that important information on the nature of the

combustion processes can be derived through careful experimental work.

61
REFERENCES

1. H. Alter, Symposium on Materials from the Chemical Viewpoint, Joint

Board-Council Committee on Chemistry and Public Affairs and Division

of Industrial and Engineering Chemistry, 173rd National Meeting

American Chemical Society, New Orleans, Louisiana, 1977.

2. ASTM E-38.01 - Editorial Draft Standard EDS-19 Standard Definition

of Terms Relating to Resource Recovery (in progress).

3. D. R. Kirklin, J. Colbert, P. Decker, S. Abramowitz and

E. S. Domalski, Test Procedures for the Determination of the

Gross Calorific Value of Refuse and Refuse Derived Fuel by

Conventional and Large Bomb Calorimetry, NBSIR 81-2278, National

Bureau of Standards, Washington, DC 1981.

4. S. A. Hathaway anJ J. S. Lin, Thermogravimetric Analysis of

Solid Refuse Derived Fuels and Coal, U. S. Army Corp. of Engineers

Technical Report E-149, Construction Engineering Research Laboratory

P. 0. Box 4005, Champaign, Illinois 61820, 1979.

5. J.E.L. Rogers, A. F. Sarofim, J. B. Howard, G. C. Williams and

D. H. Fine, 15th Symposium on Combustion, Combustion Institute,

Pittsburg, Pennsylvania, 1974, pg. 1137.

B. Entrained Combustion of RDF Particles

(A. Macek, C. Bulik, S. R. Charagundla)

Phase I. The cold-flow elutriation apparatus (CFEA), designed at NBS, has

been assembled and tested. The apparatus is designed to obtained data

needed for determination of RDF particle size range which can be studied

in suspension in the NBS 6-inch laboratory furnace. It has been found

that CFEA is adequate for quantitative determination of settling

velocities of particles having a wide range of shapes and densities in the

size range of interest (up to about 0.5 inch). It has also been

demonstrated that samples of finely ground RDF can be injected into the

laboratory furnance by means of the fluidized feeder, developed and used

earlier in this project for injecion of pulverized coal. RDF injected

into the furnace in this fashion ignites readily at gas temperatures of

1200-1300°F without oxygen-enrichment of the furnace gas.

A fluidized feeder for injection of RDF into the furnace has been

constructed based on the experience obtained earlier in this project

during the preliminary tests with pulverized coal. The major difference

is that while the coal feeder was designed for and used with particles up

to about 150 ym only, the RDF feeder is designed for particles up to at

least 3 mm.

Terminal air-flow velocities for a variety of particles having

different sizes and shapes have been determined by the Cold Flow

Elutriation Apparatus, constructed recently in this project. Two

62
examples: 200 cm/sec for 6 mm newsprint shreds and 800 cm/sec for 1 mm

glass spheres. The apparatus has also been found promising for

aerodynamic discrimination of components of a given heterogeneous sample,

such as shredded RDF.

Phase II. As a result of the survey of industrial test furnaces for a subscale study of RDF combustion, reported earlier, it has been decided

that three test units may be applicable to this task: two at Combustion

Engineering, Inc., Windsor, Connecticut, and one at Foster Wheeler

Development Corp., Livingston, New Jersey. Requests for Phase II test

plans have been sent to these two industrial concerns. The requests were accompanied by a set of instructions for preparation of test plans

(enclosed). The instructions incorporate the NBS conceptual outline of

the subscale program.

Plans for FY 1982

k

In the Chemical Kinetics Division, we intend to continue thermal

analytical studies on RDF and coal samples. The basic thrusts will

involve (a) quantitation of the "fingerprint" data that we have obtained

in fiscal 1981 (b) development and application of Evolved Gas Analytical

techniques. The latter will in time permit studies at much higher heating

rates and lead to investigations in a small research type furnace that is

under construction. At the same time work on the combustion of large size

samples of densified RDF will be carried out by T. Kashiwagi in the Center

for Fire Research.

In the Thermal Processes Division, studies on RDF and coal samples

will be carried out in the two aboratory units constructed during fiscal

1981: th'^ cold-flow elutric.^ion apparatus and the 6-inch furnace. Two

results are expected from the work with the elutriation apparatus: (a)

physical separation of RDF samples according to their entrainment

characteri sties for subsequent laboratory combustion; (b) generation of

data allowing estimates of settling velocities of RDF samples for applied

(pilot and field) combustion. The furnace will be used to obtain burningtime data for a pulverized bituminous coal, lignites, and RDF samples

consisting of sizes entrainable by furnace gases up to about 5 ft/sec.

The plan for industrial (Phase II) studies of RDF combustion is

nearly complete and a draft is expected to be submitted to DoE by

November 13, 1981.

63
Project Title: Chemistry of Hazardous Waste Incineration

Goal: (1) To develop strategies and techniques for the destruction of

hazardous waste by incineration using chemical thermodynamics

and chemical kinetics.

(2) To examine the available physical and chemical properties on important hazardous waste components and utilize these data to

develop useful predictive schemes for various properties.

Technical Center for Chemical Physics

Areas at Chemical Kinetics Division

NBS:

Personnel: W. Tsang and W. Schaub

Other U. S. Air Force, Tyndall AFB Florida

Agency Air Force Engineering and Services Center

Support: S. A. Hathaway

Incineration has traditionally been a technological area dominated by

physical considerations. Recent events mandating the destruction of

hazardous organic wastes by incineration and increasing evidence that such

substances may be formed during combustion process have made necessary a more "chemical" approach to these problems. Our work has been

concentrated on building a conceptual frame work with regard to the role

of chemical kinetics in these problems. Our analysis has identified

unimolecular decomposition, as well as OH radical and H-atom attack as the

important processes in hazardous waste destruction. On that basis a scale

of incinerabi 1 ity has been devised and chlorinated aromatics identified as among the most difficult compounds to destroy. Thermochemical properties

of most of these compounds have been estimated and JANAF type tables

prepared. Equilibrium calculations have demonstrated that there are no thermodynamic constraints on their destruction at temperatures in excess

of 700K. Several papers have been prepared. We are in the process of

developing an experimental program for the verification of our predictions

and it would appear that the key questions involve chlorination of

aromatics, the stability of such compounds to hydroxide radicals and the

important processes involved in aromati zation.

Accomplishments in FY 1981

Papers have been prepared on the following topics and are in the editorial

review process:

(1) Chemical Processes in the Incineration of Hazardous Wastes by

W. Tsang and W, Schaub, Chapter in text on: Detoxification of

Hazardous Waste, Ann Arbor Press, Ann Arbor Michigan. (In press)

(2) Procedures for Estimating the Heats of Formation of Aromatic

Compounds, Chlorinated Benzenes, Phenols and Dioxins, by

W. Schaub; in review for Thermochimica Acta.

64
/

(3) Estimated Thermodynamic Functions for Some Chlorinated

Benzenes, Phenols, and Dioxins by W. Schaub; in review for

Thermochimica Acta.

Plans for FY 1982

We plan to proceed with work to develop scales of incinerabi 1 ity for

the list of 238 hazardous wastes tabulated by the U. S. Environmental

Protection Agency. Construction will begin on a small scale laboratory

furnace needed to simulate incinerator behavior. Rates of chemical

reactions will be studied help implement and verify an i nci nerabi 1 i ty

scale for hazardous wastes.

Technical Center for Chemical Physics

Areas at Chemical Thermodynamics Division

NBS

Personnel: E. S. Domalski

Accomplishments in FY 1981

Eugene S. Domalski is a member of the Research Committee on Industrial and Municipal Wastes of the American Society of Mechanical

Engineers (ASME) and was part of a special Ad Hoc Committee on Trace

Organic Emissions. The Ad Hoc Committee was convened early in FY 1981

from the Research Committee membership for the purpose of bring together

in one document the state-of-the-art regarding the chemistry, sampling,

identification, quantification, and toxicology of chlorinated dioxins to

assist in identifying and prioritizing research needs in this field. This

study was contracted to A. D. Little, Inc. and is available from ASME (New

York) under the title: Study on State-of-the-Art of Dioxin from

Combustion sources.

Plans for FY 1982

Methods will be examined which can be used to predict the

thermodynamic properties of hazardous materials. An overall predictive

reliability of 1 to 2 kcal mol"^ for the enthalpy of combustion (related

to the calorific value) and enthalpy of formation will be sought for the

estimation methods. Similarly, an overall predictive reliability of 2 to

3 cal deg“^ mol"^ would be sought for estimating heat capacities and

entropies.

65
Project Title: Research on the Corrosion of Materials Used in Muncipal

Waste-to-Energy Incinerator System's

Goal: (1) To develop a data base of degradation characteristics of

various metals as a function of combustion conditions,

temperature, and gas composition leading to a better

understanding of the degradation procedures occurring.

(2) To determine the possibility of developing a valid short term

degradation test(s) for various metals over a variety of

commonly used operating procedures, firing profiles, and fuel

mi xes.

Technical

Areas at

NBS:

Center for Materials Science

Chemical Stability and Corrosion Division

Personnel

E. Escalante and J. Fink

Other

Agency

Support:

U. S. Department of Energy

Office of Energy from Municipal Waste, and

D. Walter, B. Greenglass, C. Kouts and L. Lehr

U. S. Air Force, Tyndall AFB, '^lorida

Air Force Engineering and Services Center

S. A. Hathaway

Accomplishments in FY 1981

The entire corrosion project was restructed. The project became

effective on July 1, 1981 and will end on September 30, 1983. A visit to

the NASA Langley Research Center Incinerator Facility in Hampton, VA on June 30, 1981 established the cooperative relations needed to carry out

the work. NBS will conduct the corrosion study on candidate alloys

exposed to the fire stream of the NASA Langley Incinerator Facility. The

investigation will be conducted according to the tasks listed below:

Tasks

Task 1: Probe Implementation. NBS shall develop a suitable test

probe to support the analytical effort carried out in Task 6 below. NBS

shall install a test probe in the combustion chamber of the RDF-fired

boiler, and provide written instruction at the time of installation on the

routine inspection and maintenance of the probes.

Task 2: Combustion Gas Analysis. The NASA Langley Research Center

Facility, in cooperation with NBS, shall take samples of the combustion

gases in the region of the probe and determine the chemical content of

these samples.

Task 3: Thermal Profiles. NBS shall measure the temperature of the

probe at several points along its length.

66
Task 4: Deposit Analysis. NBS shall analyze deposits accumulated on the probe materials resulting from exposure to the furnace environment

with emphasis on deposit-metal interfaces.

Task 5: Fuel Profile. NBS shall be provided with the fuel use profile of the RDF fired boiler. Fuel properties and consumption data

presently being accumulated by the NASA Langley Incinerator Facility shall

be made available to NBS.

Task 6: Material Characterization. NBS shall characterize test

materials before and after long term exposure to the furnace environment

and, based on this characterization, recommend appropriate materials for

application in RDF-using heating and power plants. The characterization

shall include but not be limited to: sample surface evaluation,

metal lographic examination, identification of the type of degradation

involved, physical measurements (including weight loss, wall thickness

reduction, pit depth), weld or other fabrication-related phenomena

(including protective coatings or other material protection systems), and

other determinations required to evaluate the materials with respect to

their tolerance to the furnace environment.

Task 7: Reporting. NBS shall provide a written interim letter

report and a final technical report as stipulated below.

Plans for FY 1982 (also includes last quarter of FY 1981)

July 1 - Sept. 30: Complete examination and analysis of Probe I specimens. Remove Probe II from the incinerator envirionment and install

Probe III. Obtain the combustion gas analysis data during exposure of

Probe II from NASA Langley Research Facility personnel. Similarly, obtain

the fuel profile data from the NASA Langley Incinerator Facility

operators. Develop a preliminary evaluation of the durability of the

various alloys exposed to the incinerator environment. Provide an annotated bibliography on the degradation characteristics of various

metals to obtain an understanding of previous efforts. The bibliography

will include information on the known failures of incinerators due to

corrosion. Submit an annual report to DoE. Oct. 1 - Dec. 31: Perform a preliminary examination of Probe II specimens, and gather data on Probe

III during exposure.

1983

Jan. 1 - March 31: Complete examination and analysis of Probe II specimens . Remove Probe III from the incinerator environment, and obtain

the gas analysis data taken during exposure of Probe III from NASA Langley

Research Center personnel. Similarly, obtain the fuel profile data taken

during exposure of Probe III from the NASA Langley Incinerator Facility

operators.

April 1 - June 30: Perform a preliminary examination of Probe III, and

begin a more complete evaluation of all data obtained related to the

durability of the specimen alloys in the incinerator environment.

67
I July 1 - Sept, 30: Complete analysis of all data including a -) characterization of the durability of the various alloys exposed to the

incinerator environment. Submit a final report to DOE. ,

Plans for FY 1982

A visit will be made to Wright-Patterson Air Force Base, Ohio to

initate a testing schedule for FY 1982 on their coal (RDF) - fired boilers

which will to study corrosion on candidate alloy probes.

68
Project Title: DoE/NBS Workshop on Environmental Sped at ion and

Monitoring Needs for Trace M^tal -Contai ni ng Substance

from Energy Related Processes

Goal: To convene a workshop on environmental speciation and monitoring

and needs for trace metal -containing substances from energy-rel ated

processes

Technical Center for Materials Science

Areas at Chemical Stability and Corrosion

NBS:

Personnel: F. E. Brinckman

Other U. S. Department of Energy

Agency Office of Health and Environmental Research

Support: G. Goldstein

Accomplishments in FY 1981

Increased national reliance on alternate sources for extracting fuels

and oils either from fossil deposits or from recycled materials directs

attention to the processing and environmental hazards shared by both

technologies and their common measurement solutions. These joint concerns

are raised because it is already clear that fossil sources, such as oil

shale (kerogen) or coal, contain significant accumulations of many toxic

elements, including arsenic, mercury, selenium, uranium, and cadmium.

Dependence upon recycled materai’s as prospective sources for organic

feedstocks requires consideration of the anthropogenic incorporation of

the same toxic elements during prior use. Underlying both technologies,

is a major requirement for reliable trace measurement methods and

standards

Assessing or monitoring environmental hazards or impacts of such

processes and their effluents, is inhibited by many unsolved problems:

(1) What are the relationships between the source matrix (coal, shale,

sludge, sediment) and the potential for release of toxic metal - or metalloid-containing substances during processing, disposal, or recycling?

(2) What are the specific molecular forms of the toxic elements and their

dosage effect(s) upon specific or diagnostic organisms? (3) What are

(will be) the best means for detecting and quantitating these toxicants in

the dynamic process environment as a real-time monitoring control?

At the request of the Office of Health and Environmental Research,

Department of Energy, NBS organized a specialist workshop to address these

timely questions and appraise the routes by which new relevant research

could be most effectively performed. Twenty-four experts gave invited

papers at the DoE/NBS Workshop o "Environmental Speciation and Monitoring

Needs for Trace Metal -Contai ni ng Substances from Energy-Rel ated

Processes," at NBS, Gai thersburg, 18-20 May, 1981. Some 45 additional

invited specialists from industry. Government, and academic participated

in a full discussion of the issues cited above. The papers and edited

69
discussion are currently in preparation

in the NBS Special Publication series,

and the NBS Office of Recycled Materials

as a Proceedings for publication

The Workshop was sponsored by DoE
Project Title: Determination of Trace Inorganic Components in Wastes and

F^ecyc I ed Mater i aTs

Goal: To develop test methods for the determination of trace metallic

components in solid wastes and recycled materials.

Technical Center for Analytical Chemistry

Areas at Inorganic Analytical Research Division

NBS:

Personnel: E. Garner and R. W, Burke

Accomplishments in FY 1981

A. Inductively Coupled Plasma (ICP) Spectrometry

The ICP system being developed in CAC has demonstrated a great

utility in the analysis of a wide variety of samples. The present

instrument currently has a capability for determining up to 10 elements

simultaneously with high sensitivity and wide linear dynamic range. This

instrument has been specifically designed to offer complete freedom of

spectral line selection while maintaining a high degree of resolution.

Most instrument control functions, including background correction and

signal integration time, are computer controlled. During the past year,

much of the activity was focused on improving the accuracy of this

multielement technique. One of the most significant sources of error is

the observation that the accuracy of trace element measurements is

affected by matrix constituents. The extent of this problem is a function

of several instrumental parameters. In order to characterize and correct

for matrix effects, the instrument computer has been connected to the NBS

computer via the NBS network. This data transfer capability represents a significant effort in hardware and software development and should provide

the means necessary to improve the accuracy of ICP analyses.

B. Metal Sped at ion

Interest in metal speciation measurements is growing rapidly

throughout the world. The key analytical question being asked, with

increasing frequency, is not how much of a given element is present but

rather in what form(s) it is present. Such speciation information is of

critical importance to toxicological, nutritional, and biochemical

research, to environmental science, and to industrial research. To

develop a speciation measurement capability in CAC, the Group has

initiated research for developing analytical systems for this purpose.

During the past year, a high performance liquid chromatograph (HPLC) has

been coupled to an atomic asorption spectrometer (AAS) and has been used

for determining the various alkyl lead species in leaded petroleum

products. A summary of this work has been submitted for publication in

Analytical Chemistry.

A speciation problem of current interest is the determination of

chromium (VI) in the presence of chromium (III). Because chromium (VI) is

the toxic form, ERA has recently modified its hazardous waste regulations

71
to acknowledge this fact. Using the same HPLC-AAS* system employed for

lead, we have been able to determine chromium (VI) and total chromium in a variety of liquid samples, including the pH 5 acetic acid extraction

system employed in the EPA leach test.

C. Laser Enhanced Flame Ionization

Control of storage and dumping of chemical waste cannot be done

without some means of monitoring the integrity of the storage site. For

this purpose, the ultimate in low concentration analytical techniques is

required. With such a capacity, very small leaks in the storage system

can be discovered and remedied before a serious contamination occurs. If

a clandestine storage area begins to leak into ground and/or estuarine

water, it may be best located by using an ultra-trace technique. In fact,

such methods prove most useful in general survey testing because rivers

can be tested for the presence of chemical leakage hundreds of miles back

into its tributaries. Conventional analyses would be hard pressed to

overcome the high dilution factor. This need for ultra-trace quantitative

analysis of water may benefit from some research on laser atomic

spectroscopy that our group has been doing.

A new analytical method called laser enhanced flame ionization holds

promise for direct analysis of water w/o preconcentration at the ten parts

per trillion level, 1/10^^, for a number of the important elements

associated with toxic effects. In addition, the method which is explained

in the enclosed publication has high selectivity from the presence of

elements other than those being analyzed. This minimizes the number of

false positives on a screening test. The selectivity is derived from the

use of atomic excitation using two photons of different wavelength tuned

between successive levels of excitation in the atom.

Plans for FY 1982

FY 1982 research efforts in the Inorganic Analytical Research

Division will be directed toward activities in atomic spectrometry

research. Studies with the inductively coupled plasma (ICP) will be

pursued to identify and to develop schemes for correcting for matrix

effects which can seriously affect the accuracy of this promising

multielement technique. In the case of DC pi asma/echel le spectrometry,

research will be directed towards modifying the plasma system to process

transient signals, using real-time background correction and synchronous

detection. This modification will permit the interfacing of several

adjunct preconcentration/separation methods (i.e., hydraulic generation

for arsenic and selenium, cold vapor generating of mercury and high

performance liquid chromatography for other priority pollutant elements)

to enhance the applicability, selectivity, and sensitivity of the DC

plasma technique. The transient signal processing will also permit the

utilization of microsampling devices to increase the sample throughout

this instrument. The third activity is in atomic absorption spectrometry

and will support work in two specific areas. One is concerned with the

*HPLC-AAS High Performance Liquid Chromatography - Atomic Absorption

Spectroscopy

72
selection and systematic evaluation of various compounds which, when added

as a matrix modifier, have been shown to greatly alleviate the effects of

chemical interferences in the determination of a particular analyte

element by graphite furnace - atomic absorption spectrometry. The other

area of interest is concerned with the development of a high performance

chromatographic separation - atomic absorption procedure for accurately

determining chromium VI - chromium (III) speciation in aqueous system such

as for example, solid waste leachates.

73
Project Title: Analysis of Trace Organic Constituents

Goal: To develop test methods for the quantitative analysis of trace

organic constituents in recycled materials. Although there has

not been any direct application to recycled materials or waste

streams, the basic research in these areas offers great potential

for .improved analytical methods in the future.

Technical Center for Analytical Chemistry

Areas at Organic Analytical Research Division

NBS:

Personnel: H. S. Hertz, D. J. Reeder, L. R. Hilpert, and R. G.

Chri stensen

Accomplishments in FY 1981

A. FI uoroimmunoassay for the Detection of Toxic Organics in Water

Immunoassays have been used extensively in the clinical laboratory

because they afford rapid, selective and precise methods of analysis for

analytes in complex mixtures, such as human serum. These features of

immunoassay procedures have attracted our attention and caused us to

examine the potential of these assay procedures for utility as rapid

screening procedures in the recycled material and environmental analytical

areas. Since some prior research had been performed on the preparation of

antibodies to 2,4-dinitrophenol , this was chosen as a model system.

Detection of trace amounts of the toxic pollutant 2,4-dinitrophenol

(DNP) in water is an analytical problem tht presents many challenges to

the analytical chemist. Laboratory investigations have shown that gas

chromatography and high-performance liquid chromatography, while suited

for analytical determinations of most of the toxic pollutants, are not as efficient in the separation and identification of the nitrophenols. The

development of an immunochemical procedure for detection and quantitation

of di nitrophenols in water has been the focus of efforts during the past

year.

Previous work included optimization of the material (immunogen) to be

injected into rabbits for production of suitable antiserum. If DNP is

injected alone, no antibodies will be produced. Thus, a suitable

"foreign" carrier protein (bovine serum albumin) was labeled with DNP (23

groups per mole of protein) and sent to a commercial supplier who

immunized rabbits with this conjugate. When suitable antibody levels were attained, the rabbit antiserum was sent to NBS where we separated and

purified the specific antibody-bearing immunoglobulin (IgG) fraction.

This IgG was then covalently bound to solid-phase polymeric beads by

coupling with a carbodiimide reagent.

The antibody, thus attached to the beads, was able to bind 2,4-

dinitrophenol. However, in order to use this capability in a quantitative

assay, a compound that could act as a tracer needed to be synthesized. In

74
order to be suitable in the assay, the tracer required dual functionality,

i.e., dinitrophenol reactivity as well as having a physical property that

can be measured, such as radioactivity or fluorescence.

The first quantitative competitive assay with which we had success utilized a tracer consisting of a double-labeled rabbit albumin molecule

to which both dinitrophenol groups and fluorescein isothiocyanate

chromophores were covalently bound. In the competitive assay, the tracer

and free dinitrophenol compete for antibody sites on the specific antibody

solid-phase beads. Maximum sensitivity of the assay is determined by the

amount of antibody-bound beads added, the quantity of the competing tracer

in the mixture, and the time and temperature of assay incubation.

While the first assays were linear over two orders of magnitude at

the microgram level, the sensitivity of the assay was not as great as desired. Achieving a sensitive assay capable of detecting part-permillion or part-per-bi 1 1 ion level DNP in water required use of a different, more efficient tracer.

Considerable effort has gone into the organic synthesis of a tracer

compound that has both a fluorescent moiety and a dinitrophenol structure.

Pilot batches of such a tracer were prepared by reacting f 1 uorescei nami ne (Isomer I) and 2, 4-di nitrobenzene sulfonylchloride in a 1:3 (mol/mol)

ratio in dry pyridine at room temperature. The reaction is stopped after

30 minutes with 1 mol/L HCl until a slight precipitate appears. Water

(0.1 volume of reaction mixture) is added to precipitate more of the

sulfonamide product. After centrifugation at 5000 x g for 10 minutes, the

precipitate is collected and dissolved in acetone. Several crystalline

crops of this compound were examined by thn-layer chromatography (TLC)

(using methylene chloride: methanol, 85:15 as the developing solvent), as well as by ultraviolet, fluorescence, infrared, proton magnetic resonance

spectrometry, NMR, and mass spectrometry. Although the compound is still

not pure, there is good evidence that this synthetic procedure produces

sufficient tracer to make it useful in an immunoassay. Work is continuing

to improve yield and decrease impurities.

Work has also been focused on the selection and purification of

specific antibodies from recently immunized rabbits by means of affinity

column purification methods. We have also upgraded the capabilities of

the flow-through fluorometer used in the assays and are currently

developing more solid-phase reagents. During the remainder of the fiscal

year, we will be directing our efforts toward increasing the

reproduci bi 1 ity and sensitivity of the immunoassay system.

By combining the specificity of the assay with capabilities of

concentrating di ni trophenol s with an affinity "accumulator" column,

detection of trace amounts of dinitrophenol in water should be achieved.

This will be of importance in the monitoring of effluents from waste

sites.

Plans for FY 1982

We plan to explore methods for optimizing the immunoassay procedures

developed to extend sensitivities to the nanogram/mL range. To do so will

75
require further production of antiserum in rabbits using the recently

produced conjugates (see progress report). Further work is required to

synthesize, purify, and characterize the proper tracer molecule and use it

in the solid phase assay system now opeating. Further studies with

affinity-column purified antibodies will be performed to measure their

acidity and cross-reactivity. Development of "accumulator" columns will

require binding of the purified antibody (produced from rabbits) to solid

phase supports and developing methods for binding, elution, and

preservation of activity. Initial application of the improved system to some waste waters is anticipated.

B. Negative Chemical Ionization Mass Spectrometry

Negative chemical ionization (NCI) mass spectrometry is a sensitive

state-of-the-art technique which involves the formation, mass separation,

and detection of anions, in the gas phase. It is a technique which should

allow greatly increased sensitivity of detection for certain types of

environmentally significant molecules. Production of negative molecular

ions by electron attachment in the gas phase requires (1) sample

compounds which are electronegative or which have electronegative groups

attached, and (2) a large population of thermal electrons*. Compounds

with high electron affinities such as halogenated pesticides,

polychlorinated biphenyls, dioxins, etc., should yield high sensitivities

in the negative ion mode.

A quadrupole mass spectrometer with a chemical ionization source and

capability for detecting negative ions has been installed in the Organic

Analytical Research Division. In preparation for conducting experiments in

this field, a literature search of research papers dealing with negative

ionization was conducted.

Initial experiments were performed to indicate which compounds or classes of compounds would yield intense molecular ions in the NCI mode.

The first compounds studied were a series of phenols (phenol, o-cresol, pcresol ; 2-chlorophenol ) and _N-heterocycles (acridine and carbazole).

Neither the phenols nor the _N-heterocycles gave enhanced sensitivity in

the NCI mode over the positive chemical ionization (PCI) or electron

impact. However, the phenols produced interesting spectra with methane as the reagent gas. Intense ions apear at (M-H)“ and at a mass 12 amu higher

than the molecular weight, possibly an (M + C2H5-0H)" ion. Addition of one halogen atom, as in the 2-chlorophenol, did not significantly improve

the sensitivity (the same interesting adduct ions were still observed

though)

A mixture of Arochlors 1254 and 1260 was run in both the positive

and negative chemical ionization modes using methane as the reagent gas.

The Arochlors are mixtures of polychlorinated biphenyl isomers and should

give

*Szulejko, J. E., Howe, I., Beynon, J. H., and Schluneager, U. P. Negative

Ion Mass Spectrometry : The Generation of High Concentrations of Low

Energy Molecular Negative Ions at High Source Pressures, Org. Mass Spec.

15 (5), 263 (1980).

76
greatly enhanced sensitivity in the NCI mode. The sensitivity was observed to be greater in the NCI mode than in the PCI mode. Also,

different compounds in the mixture were detected with different relative

sensitivities in each mode. In the positive ion mode, the Cl^, Cl 5

, and

Clg polychlorinated biphenyl isomers are the predominant species detected;

in the negative ion mode, isomers with as many as seven chlorines are detected.

Plans for FY 1982

During the next year, work will continue on determining which types

of compounds give enhanced sensitivity in the NCI mode. The fragmentation

of negative ions is often straightforward, making spectrum i nterpretation

easy. This negative ion information should be complementary to that

obtained by conventional electron impact iniation, providing an additional

tool for the identification of organic compounds in complex samples. Gas

chromatography with selected negative ion detection will be explored for

sensitivity and precision in quantitative trace analysis. The use of

different reagent gases (Ar, N

2 , N2 O) to improve the production of

molecular anions will also be studied.

C. Combined Liquid Chromatoqraphy/Mass Spectrometry

Liquid chromatography (LC) can be used for the separation of many

nonvolatile and polar molecules that are not amenable to gas

chromatography (GC), and can handle many samples in matrices not amenable

to gas chromatography, such a** water or heavy oil. Therefore, the

coupling of a mass spectrometer (MS) to a liquid chromatograph has

generated a great deal of interest. If this could be accomplished, many

of the advantages of GC/MS could be realized in an LC separation.

Numerous publications have appeared and two methods have been used in

commercial instrumentation. However, neither of these instruments has

been used for quantitative analysis.

We have constructd a unique LC/MS interface that operates by removing

most of the excess solvent from the effluent stream as it flows down a heated wire. The residual concentrated solution is drawn into the vacuum

of the mass spectrometer and volitilized into the ion source. This

interface and some applications of normal -phase chromatography are described in Christensen et al . , Anal. Chem. 53 , 171 (1981).

A large fraction of analytical LC is now performed using reversedphase chromatog'^aphy . Therefore, it is desirable to have an LC/MS

interface which will accomodate the aqueous solutions used in that mode.

The only part of our system which did not operate well with water was the

probe which introduced the concentrated stream into the ion source. The

difficulties arose because of the high surface tension and heat of

vaporization of water. Attempts to overcome these problems by heating the

tip of the probe either by radiation of conduction were not successful. A

sonic-powered spraying device was therefo'^e developed, using a solenoid

coil around the exterior part or the solvent introduction capillary. The

capillary being made of nickel, is magnetostricti ve, so that an alternating field causes it to vibrate. When tuned to resonance, the

vibration is strong enough to atomize water droplets from the surface at

77
the end of the probe. Concentrated buffer solutions can be sprayed

without clogging the 8-10 ym orifice; adenosine, a test compound of low

volatility could be dispersed well enough to observe molecular ion peaks.

The first reversed-phase application using an actual analysis from a complex matrix was that of measuring the polar molecule, valproic acid (in

serum), by a direct injection of serum onto the column. Preliminary

trials suggest that quantitation better than 10 percent (relative standard

deviation) can be obtained for 100 ppm valproic acid in serum. If

somewhat better precision can be attained, it is an attractive method for

certifying trace level constituents in complex Standard Reference

Materi al s

Although we propose to use labeled valproic acid as an isotope

dilution internal standard in the above analysis, the good stability of

the spray should allow quantitation by external standard for other

compounds such as the aromatic and phenolic compounds mentioned in the

paper referred to above, and present in waste waters.

Plans for FY 1982

In the next fiscal year, we plan to extend reversed-phase

applications to quantitative analyses in complex waste samples, making

use of the sonic-probe introduction method. Improvements and

modifications of the instrument will be made only as they appear necessary

to accomplish the applications.

The general features of a feedback circuit for controlling the

evaporation rate of solvent from the concentrator wire have been decided.

This device will be designed, constructed, and tried out if time is

available. The envisioned principle of operation is droplet observation

as droplets move down the lower, smal 1 -di ameter, portion of the

concentrator wire. The current flowing in the wire would decay at a settable rate, while each observed droplet would increment the current by

a settable amount.

D. Chemically Modified Electrode Detectors for Halogenated Hydrocarbons.

Halogenated hydrocarbons are presently determined by gas

chromatography following solvent extraction to separate and concentrate

the analytes. An electroanalytical method has been proposed, which may be

applied directly to the sample. Elimination of the preseparation/concentration steps is one advantage among several possible

advantages offered by Chemically Modified Electrodes (CME).

We are interested in the development of chemically modified

electrodes, which will electrocatalytical ly detect organohalide

compounds. These chemically modified electrode sensors could allow the

selective and sensitive detection of organohalide compounds in the

presence of complex matric interferences.

We are conducting this study by pursuing two routes of investigation.

Both of these involve attachment of electrocatalytic polymer films to

metal electrode substrates (Au, Pt).

78
During FY 1981, we accomplished the following: (1) synthesis of

Schiff-base ligands, (2) formation of the nickel Schiff-base complexes,

and (3) attachment of a nolyphenyl oxide polymer film to the electrode

surface.

Plans for FY 1982

Further work for FY 1982 involves: (1) further film

characterization via surface analysis, (2) electrochemical evaluation of

these derivatized polymer films, (3) evaluation of the stability

associated with these polymer films, and (4) the electrocatalytic

efficiency as a function of film thickness and chemical composi

An added consideration for the ferrocene polymer modified

is the construction of a specially designed cell which will all

radiation to impinge on a modified electrode.

tion

electrode

ow light

79
Project Title: Characterization of Ash from Refuse-Derived-Fuels (RDF)

Goal: To develop test methods for the characterization of RDF and RDF ash

using x-ray powder diffractometry.

Technical Center for Materials Science

Area at Ceramics, Glass, and Solid State Science Division

NBS:

Personnel: C. R. Robbins

Accomplishments in FY 1981

(1) Three refuse-derived-fuels, four coals and their inorganic

residues after heating were characterized by X-ray powder

diffractometry in order to identify the crystalline phases

present at the various ashing temperatures. Observation of

the sequential changes in phase assemblages with increasing

temperatues show the dominant chemical reactions taking place

in the inorganic fractions of the fuels. Specimens were heated in air at 100°C intervals over the temperature range

475° - 1225 °C. On the order of sixty X-ray patterns were obtained and analyzed. This work is completed. It is part of

a collaborative effort with the Chemical Thermodynamics

Division (E.S. Domalski). A paper entitled "Ash Content and

X-ray Analysis of Selected RDF and Coal Samples as a Function

of Temperature" (D. R. Kirk1in,E. S. Domalski, R. V. Kelly, C. R. Robbins) will be presented at the symposium on Resource Recovery

and Environmental Issues of Industrial Solid Wastes in October

1981 in Gatl inburg, TN, and submitted to the journal: Resource

Recovery and Conservation for publication.

(2) An abstract entitled "Characterization of Ash Residues from a Refuse Derived Fuel/Oil Combustion Study" (with F. Hasselriis) has

been accepted for presentation at the ASTM symposium "Alternative

Fuels and Future Fuels Specifications," to be held in Phoenix,

Arizona (December, 1981).

(3) Work has been initiated on a suite of samples from a coal-RDF test

burn. Fuel, fly ash and bottom ash will be included in the study.

The samples are quite well documented with regard to conditions of

burn and sample collection.

(4) Some of the work period during FY 81 has been spent on construction

and testing of an NBS spray dryer for preparation of samples for

quantitative X-ray powder analysis. One of the major sources of error in X-ray quantitative analysis is crystallite orientation.

This is eliminated by converting the samples (which may be a mixture of fine powders) to spheres on the order of 10-30 m or less by grinding the powders in a special grinder, adding an appropriate vehicle, a binder and a dispersant to form a slurry.

The slurry is then sprayed into the dryer in atomized or aerosol

80
form, and the spherical particles are formed. This equipment has

been completed, tested and is now operational.

(5) Some of the work period has also been spent in preparing spray dried

pure reference compounds (or mixtures of compounds) for testing four

computer programs recently completed for use with this project and

another related one. Application of one program to a spray dried

synthetic mixture of quartz (Si 02 ), hematite (Fe^Og) and mullite

(AlgSi 20 i 3 ) was quite successful. Results of this preliminary test

are given in the following table.

TEST OF NBS INTERNAL STANDARD METHOD FOR

QUANTITATIVE X-RAY ANALYSIS

Compound Weight Fraction Weight Fraction

(Formulated) (By X-ray Analysis)

FeoOo

Si02

AlgSioOj,

AI 2 O

3 (i nternal

standard)

10 . 00°/ 30.00°/

40.00°/

20.00°/

10.07°/

30.24°/

42.38°/

The test data were taken with one scan, where normally, three scans would

be taken and the results averaged.

Plans for FY 1982

(1) Ash residues from a laboratory study of the combustion of

coal-RDF mixtures, ashed at various temperatures under

controlled conditions, will be characterized by x-ray powder

diffractometry, scanning electron microscopy (including energy

dispersive analysis) and by light microscopy. Other

analytical methods may be employed if desirable.

(2) Work will be completed on the characterization of fuel, fly

ash and bottom ash from a coal-RDF plant test burn.

Analytical results will be correlated with those from item 1.

(3) A study of ash variability as a function of fuel type,

particle size, and combustion conditions will be initiated

during FY 1982.

(4) Additional studies of RDF-fuels, ashed under known laboratory

conditions, will be performed as specimens are received.

81
Project Title: Fly Ash Utilization in Cement and Concrete Products

Goal: (1) To review the nature of fly ashes and their levels of

production and use in various countries.

(2) To estimate the potential achievable level of the use of fly

ash in cement and concrete in the USA.

Technical

Area

at NBS:

Center for Building Technology

Structures and Materials Division

Personnel: J. R. Clifton

The stockpiling and disposal of fly ash is becoming increasingly more objectionable and subject to governmental regulations because of its

effect on the environment. Over 60 million tons of fly ash are being

generated in 1981. About 300 million tons of fly ash have already been

stockpiled. Use of fly ash in cement, concrete and related products can potentially consume large amounts of fly ash. At present less than 7 million tons/year of fly ash are being used in cement and concrete

products, whereas 18 million tons/years seems a realistic goal. The

purpose of this project is to identify technical obstacles to the

increased use of fly ash in cement and concrete products and to develop a research plan to overcome these obstacles.

Accomplishments in FY 1981

In fiscal year 1981, the opportunities for increased use of fly ash

in cements and concretes were addressed. An estimate was made of the

potentially achievable level of use of fly ash in cement and concrete in

the United States. The estimate assumes that 20 percent of the mass of

all the Portland cement used in the United States could be replaced by the same mass of fly ash; it ignores possible competition from granulated

blast-furnace slag as a finely-divided mineral admixture for concrete. It

appears that about 16 million tonnes (18 million tons) per year of fly ash

could be consumed in cement and concrete, provided there were fly ash

sufficient ash of suitable quality and a general understanding of the

technical requirements for satisfactory fly ash use. This information was given in the report "Fly Ashes in Cements and Concretes: Technical Needs

and Opportunities," NBSIR 81-2239. Included in the report are requirements for fly ashes for use in cements and concretes, and barriers

to increased use of fly ashes in cements and concretes. A research plan was developed for facilitating the use of fly ashes in cements and

concretes. The main research needs, in order of priority, are a)

development of methods for characterizing fly ashes, b) development of

methods for determining or predicting the performances of fly ashes in

concretes, c) development of standards for fly ashes; and d) development

of methods for benef ici ating fly ashes.

In another phase of the study, an assessment of the potential use of

fly ashes in other building material has been undertaken. These uses

82
include the manufacture of lightweight aggregates, lime-fly ash-aggregate

highway bases and sub-bases, filler in asphalt, granules for roofing

shingles, and brick manufacture.

We have been participating on ASTM Committees dealing with

specifications for fly ashes in order to improve the fly ash standards.

Dr. Frohnsdorff is the chairman of a task group which has the

responsibi 1 i ty for improving the existing standards and developing new standards for fly ashes used in hydraulic cements.

Plans for FY 1982

In FY 81 the opportunities for increased use of fly ash in cements

and concretes were evaluated and barriers to their increased use were identified. In addition, a p^an was developed for research needed to

facilitate the increased use of fly ash in cements and concrete. A

similar approach will be taken in FY 82 in assessing the potential uses of

fly ash in other building materials. The potential amounts of fly ash

which it appears can be used in producing technically and economically

viable building materials will be determined. These materials will

include lightweight aggregates, lime-fly ash-aggregate, roofing granules,

and brick, as well as innovated materials. Technical obstacles to the

increased use of fly ash in these materials will be identified and a research plan for overcoming the obstacles will be developed. The results

of the study will be published either as an NBSIR, or in an appropriate

non-NBS journal.

83
Project Title: DurabilHy of Polymeric Liner Materials Used in Waste

Di sposaV

Goal: To characterize polymeric materials for applications as liners for

solid and hazardous wastes

Technical Center for Materials Science

Areas at Polymer Science and Standards Division

NBS:

Personnel: J. C. Phillips and B. M. Fanconi

Accomplishments in FY 1981

A report was prepared on the Transport of Acetic Acid in Polyethylene

(by J. C. Phillips). This report descVibes the mass loss and

sorption/desorption of Acetic Acid (HAc) in polyethylene of different

densities at various temperatures. Mass loss for a mixture of HAc and

H

2 0 three concentrations were also done at the highest temperature used.

Experimental data for mass loss were obtained at temperatures of

approximately 40°C, 60°C, and for a low density bottle (LDPE, p~.92

g/cm^) and a high density bottle (HOPE, p~.94 g/cm^). At t=78 “C a mixture

of HAC/H 2 O consisting of 100% HAc, 75% HAc, and 25% HAc by volume was used

as permeant in the LDPE and HDPE bottles. From the mass loss data, the

loss rate and diffusivity were determined.

Data for sorption/desorption were obtained at temperatures of

approximately 30“C, 50°C, and 70‘’C at a vapor pressure of p~17mm Hg. The

polyethylene film had a density of p~.906 g/cm^ and a thickness of 4 mil

(10.16xl0“^cm) . From the sorption and desorption measurements,

diffusivity, solubility, and permeability were determined.

Plans for FY 1982

We plan to continue work in the area of stress crack resistance of common plastic liner materials for applications in hazardous waste

containment. A successful polymeric liner must retain its mechanical and

barrier properties in the presence of permanent contact with water

containing diluted hydrophilic or suspended hydrophobic substances or solid particles. The first two kinds of material may diffuse into the

polymer and eventually transform into a soft rubbery material or even disintegrate it by chemical attack. Solid particles may abrade the

polymer surface and thus gradually degrade the useful properties of the

polymer

Hence, a special study is needed for the selection of the proper

polymeric materials to be used as a liner for a given industrial or any

other kind of effluent waste. Three types of action have to be

considered: (1) diffusion with the ensuing lowering of the glass

transition of the swollen polymer; (2) oxidative or any other type of

chemical action which may lead to the disintegration or at least softening

of the polymer; and (3) mechanical stress or abrasion. The effects are

84
not independent. They may be strongly synergistic. As a polymer softens

it becomes much less abrasion resistant. The softened or disintegrated

material as a rule permits a much faster diffusion of penetrants than the

unaffected material.
Project Title: Glass Recovery from Municipal Solid Waste

Goal: To characterize glass (cullet) which is recovered from the

municipal solid waste stream so that market development for cullet

can be facilitated.

Technical Center for Materials Science

Areas at Ceramics, Glass, and Solid State Science Division

NBS:

Personnel: W. Haller and M. Cellarosi

Glass manufacturers use cullet (broken glass) as a percent of the

charge to their furnaces. This long established practiced promotes the

melting of raw materials and permits the reduction of furnace

temperatures. Benefits of such practice translate into energy savings,

extension of furnace linings life, and greater productivity. Most of the

recycled cullet so far has been scrap glass from the manufacturing plant

itself.

A potential new source of cullet is the glass contained in the

municipal solid waste stream (about 12%). Several large-scale reclamation

facilities have been built and others are planned. These facilities will

separate the glass fraction from the other components. The glass so reecovered must meet stringent standards for quality and consistency

(e.g., color, contamination, etc.). Targets for reclaimed glass

specifications and test methods have been set for reuse in container

manufacture. Tentative standards applicable to the manufacture of glass

wool insulation are currently under review.

NBS is cooperating with ASTM Committee E-38 on Resource Recovery, the

glass industry, reclamation facilities, and various resource recovery

facilities. These activities so far have generated two standards for

recovered glass specifically, for reuse in container manufacturing.

Accomplishments in FY 1981

During FY 1981, our laboratory carried out testing of samples from

initial recovery operations. Test methods cover determinations of

moisture content, organic contamination, magnetic/non-magnetic

contamination, color fraction, particle size, refractory content, and melt

evaluations. Results of these tests indicate that the overall quality of

recovered glass has improved, however, still falls short of meeting

established acceptance standards. Current projections made by companies

involved in recovery operations are that the glass will meet the

specifications for quality, and also that it will be placed in the

marketplace at prices competitive with the raw materials that it replaces.

Plans for FY 1982

A detailed report will be prepared which describes the tests carried

out on cullet in FY 1981.

86
Project Title: Research in Ferrous Recovery Through ASTM Committee E-38

Goal: (1) To cooperate with ASTM Committee E-38 through the review of

technical proposals in resource recovery, provide support and

assistance to NBS staff in areas such as standarads writing

activities, and promulgate the development of test protocols

in resource recovery.

Technical Center for Materials Science

Areas at Fracture and Deformation Division

NBS:

Personnel: J. Early

Accomplishments in FY 1981

Offices held and activity pursued:

(1) Secretary of E38 and Member of Executive Committee

Support was provided to the ORM and those NBS researchers associated

with the technical program of ORM on an as-request basis in those aareas involving Committee E38, its various technical subcommittees, and their

standards writing activities.

(2) Secretary of E38 ASTM/EPA Contract Management Board

As a voting member(J. Early) of the ASTM/EPA Contract Management

Board, the responsibility was shared for reviewing the technical proposals

submitted by the E38 subcommittees and approving those consistent with the

contract goals of developing draft standards and specifications for

resource recovery, approving the project directors and the project

budgets, and reviewing for acceptance the final report for each project.

At total of 15 research projects have been approved and funded in the areas of energy recovery from wastes, glass, processing and unit

operations, construction materials, ferrous metals, and a Thesaurus of

resource recovery terms. During FY 81, nine voluntary, national consensus

standards were adopted by ASTM Based n part on the results of these

research efforts. Current funded projects include sampling of refusederived fuels (RDF), round robin testing of ferrous metals, and use of

waste glass in brick manufacture.

(3)

Vice-Chairman of Subcommittee E38.02, Ferrous Metals

During FY 81, a proposal for a round robin test program was submitted

to the E38 ASTM/EPA Management Board for funding. The Chairman of E38.02

and Mr. Early, as director and assistant project directors, developed the

test matrix for this effort. The raw materials for the standard samples

to be distributed among the participating laboratories have been assembled

at the Ontario, Canada, Ministry of the Environment Test Facility in

Toronto, Canada. At the present, six laboratories will be involved and

distribution of the round robin samples is expected in September 1981.

87
Plans for FY 1982

Mr. Early will continue to serve as a voting member of the ASTM/EPA

Contract Management Board. He will also serve as Assistant Project

Director for the ferrous rcovery round robin testing effort which was initiated in FY 1981 but will not be completed until FY 1982. In addition, Mr. Early is writing a review of ferrous scrap recycling in the

U.S. both municipal and industrial, with respect its history, current

status, and future trends. The review will be issued as an NBSIR in FY

1982.

88
Project Title: Hazardous Waste Standard Reference Material Program

Goal: To develop standard reference materials which can used by test

laboratories and related facilities to characterize hazardous

materi al s

Location

at NBS

and

Personnel

Coordinated through the Office of Recycled Materials

by

J. G. Berke and E. S. Domalski

for the

Center for Analytical Chemistry

Inorganic Analytical Research Division

Ernest L. Garner

and the

Center for Analytical Chemistry

Organic Analytical Research Division

Harry L. Hertz

Other U. S. Environmental Protection Agency

Agency Environmental Monitoring Systems Laboratory

Support: Quality Assurance Division

Dr. Eugene P. Meier

Over the past few years a need for basic information on how to test

for hazardous materials in the environment has emerged. Regulatory and

enforcement agencies at all levels of government agree that technically

sound measurement systems must be developed on a national scale to ensure

that both the regulators and the regulated are measuring and testing in

the same way. The EPA Environmental Monitoring Sysems Laboratory, Las

Vegas, is responsible for providing standard reference materials to

support their hazardous waste programs. These materials include:

standard solutions of pure chemicals; mixtures of chemicals in solutions;

characterized reference materials such as wastes with known concentrations

of chemicals; and synthetic mixtures of materials which represent a variety of wastes. Because of the nature of the problems inherent in

preparation of these materials for use as references, the EPA joins in an agreement with the National Bureau of Standards for the NBS's experts to

provide technical advice and prepare materials. Materials of interest are sludges and sludge-like composites.

Inorganic Analytical Research Division, TASKS for FY 1981

Continue studies on candidate sludges and sludge-like materials in

order to ascertain their suitability for issuance as quality assurance

standards. Significant outputs of this task are:

A. Complete evaluation of candidate sludges now under study.

B. Obtain profile leachate data for priority inorganics in any

additional candidate sludges that can be identified and

obtained in sufficient quantity before August 1, 1981.

89
C. Investigate methods for improving the sampling reproduci bi 1 i ty

and stability of the candidate sludges.

D. Conduct concurrent studies on several simulated sludges as a back-up approach to developing a quality assurance sludge

material possessing more desirble characteristics for multi

laboratory testing than unstable real-world samples.

E. Select the best material and report on its suitability as a quality assurance standard.

F. Depending on the acceptability of the selected material as a qualty assurance standard, package, label, and deliver to

EMSL-LV 500 units (100-105 grams/unit) of the standard sludge,

characterized for the chemicals of interest by ERA procedures.

Accomplishments in FY 1981

Tasks A, B, D, E, and F was completed in FY 1981. Task C was begun

and will continue in FY 1982.

Plans for FY 1982

A. Prepare a final report giving details of the acquisition,

packaging, blending, and characterization of the standard

sludge.

B. Monitor stability of the standard sludge from at least 1 year

following its release to EMSL-LV. This would go beyond FY 1982.

Organic Analytical Research Division

^ Tasks' T6fT'{Tm

Inititate studies on a sludge or sludge-like material chosen by NBS

and EPA for possible future (FY 1982) issuance as a complex type of

quality assurance standard. The outputs of this task include:

A. Perform pilot leaching experiments using the EP procedure to

see if sufficient concentrations of organic componds are leached to justify further examination of the material.

B. Collect, blend, sieve, and homogenize 50 kg of the chosen

materi al

C. Perform gross homogeneity tests on the blended material using

solvent extraction/gas chromatography and total organic carbon

analysis.

D. Further establish homogeneity of the material on the basis of

an organic solvent extraction of representative aliquots of

90
the material with quantitative analysis of 3-5 priority

organic compounds.

E. Leach representative samples of the blended material using the

EP procedure and perform quantitative analysis on 3-5 priority

organic compounds in the leachate (additional compounds will

be analyzed quantitatively as feasible).

F. Determine the extraction and analysis variability on the

leachates derived from his blended material using the proposed

EP procedure and the extractor built at NBS in FY 1979.

G. It Step F is successful, carry out more detailed sample

storage, stability, and homogeneity tests on the 50 kg of the

selected sludge.

H. Obtain leachate data for EPA on an expanded series of priority

organic pollutants using the proposed EP and the extractor

built at NBS in FY 79.

Completion of all the above tasks is dependent on continuing observation

of material stability for organic compounds and upon repeated

chromatographic characterization of the gross organic compound content.

Result of the "total characterization" of the organic compound content of

a chosen sample will be solvent dependent and therefore, quantitative

analyses will be dependent upon the extraction procedure specified.

91
Project Title: Fossil Fuel Technology Waste Sampling and Characterization

Program

'

Goal: NBS proposes to assist the Department of Energy Laramie Energy

Technology Center to develop a definitive and authoritative body of

data on the physical and chemical proprties of fossil technology

residues from the variety of combustion and conversion systems.

The data protocols and test methods developed will assist DoE in

the environmental management of waste streams from coal combustion

and fossil energy conversion processes in a technically sound and

economically acceptable manner.

Technical Office of Recycled Materials

Area Resource Recovery Program

NBS:

Personnel: J. G. Berke and E. S. Domalski

Other

Agency

Support:

U. S. Department of Energy

Larmie Energy Technology Center

Dr. Larry P. Jackson

This effort has been sub-divided into the following tasks:

Task 1 Statistical Services

National Measurement Laboratory

J. Mandel and R. Paule

Task 2 Organic Analysis

Center for Analytical Chemistry

Organic Analytical Research Division

H. Hertz

Task 3 Physical and Chemical Characterization

Center for Materials Science

Ceramics, Glass, and Solid Science Division

C. R. Robbins

Task 4 Advanced Analytical Techniques

Center for Analytical Chemistry

Gas and Particulate Science Division

H. Rook

Task 5 Quality Assurance Ash Materials

Center for Analytical Chemistry

Inorganic Analytical Research Division

R. Burke and B. Diamondstone

92
Task 6 Inorganic Analysis

Center for Analytical Chemistry

Inorganic Analytial Research Division

E. Garner, R. W. Burke, and B. Diamondstone

General Approach

1. Representative samples of fuel feedstock, fly ash, bottom ash

and boiler slags will be collected. Feedstocks will include

coal, blended coals, RDF-coal mixtures and RDF-oil mixtures.

2. Type of plant equipment and conditions of operation will be

documented for each fuel feedstock and resulting ash and slag.

3. Feedstock will be characterized by quantitative elemental and

phase analysis.

4. Fly ash specimens will be size fractionated for detailed

study. Neutron activation analysis and atomic absorption

methods will be used for quantitative elemental analyses for

both major and minor elements.

5. Quantitative x-ray powder diffractometry methods will be used

to identify and determine amounts of crystalline phases

present, the ratio of crystals to glassy matrix and the

average crystallite size.

6. The scanning electron microscope (SEM) and electron microprobe

will be used to establish the locations or hosts of elements

observed in (4) (whether in glass or crystalline phases

present). Fine crystals on the surface of the particles will

be of interest.

7. Coarse fractions wll be studied by optical microscopy, SEM

and x-ray microdiffractometry.

8. Bulk quantitative chemical analyses would be obtained for all

samples. Surface areas of the various fly ash fractions would

be determined.

Accomplishments in FY 1981

Delays encountred in the implementation of the sample collection

effort have moved the schedule of work into late FY 1981 and throughout FY 1982.

Plans for FY 1982 -- Activities and Deliverables

Phase I site visits to five utilities

1. General sampling guidelines

9/81

11/81

93
11/81 2. Five sample sets

11/81 Phase II site visits to 10 utilities

1/82 1. Six "Best" quality sample sets (4 ea.)

1/82 2. Four sample sets

9/81 Commercial laboratory QA/QC evaluation tests

11/81 National Bureau of Standards R & D Projects

1. Inorganic particle analysis

2. Analysis of organics in leachates

3. Statistical support of FE waste characterization project

5/82 Detailed report of progress through 4/82

11/81 Two commercial labs conducting routine waste analysis

6/82 Final results from analytical program

3/82 Ten commercial labs doing "precision" waste analysis

4/82 Test results from analytical program

4/82 Phase III site visits (#TBD - MAX 17)

5/82 Remaining sample sets

5/82 NBS inorganic analysis of "Best" sample set

8/82 Report on "Absolute Value" on waste leachates

6/82 NBS statistical analysis of all analytical data

10/82 Report on precision and accuracy of various lab groups in analyzing

LE wastes

8/82 Commercial laboratory QA/QC review

9/82 Report on performance of leach tests and analysis

8/82 Versar Project Summary

9/82 1. Finalized general sampling guidelines

2. Thirty two case study reports

3/82 Overall projects management

10/81 Report on QA/QC performance of Commercial Labs

8/82 Decision on out year level of effort

94
3/82 LETC analysis of all sample leachates

7/82 Report on "Single Lab" analysis of leachates

2/82 Establish DoE archive of FE wastes

7/82 Archive inventory list

4/82 DoE (ETC's/NL's) inorganic sample analysis of "Best" sample

6/82 Report on results from "High Quality" laboratories

3/82 LETC management of ASTM D34.02.02

9/82 Decision on out year level of effort

11/81 Phase I DoE study with ETC's and NL's on GC/MS quantification of

organics in leachate

1/82 Decision on overall project goals and level of effort

10/81 Analytical method development

12/81 Report comparing results of sequencial batch extraction vs. column

extraction on reference fly ash

10/81 Sample homogeneity study on waste samples

1/82 Report

10/81 Generate reference fossil energy leachate for organics

11/81 Standard reference sample

3/82 Impact on leachate quality by co-disposal of report water on spent

same

8/82 Report

5/82 Phase II DoE study on GC/MS analysis of leachates applied to oil

shale residues

7/82 Decision on integration with ASTM effort

4/82 Comparison of organic material on retorted shale vs. organics in

1 eachates

6/82 Decision on value to LETC

95
Project Title: Federal and State Level Procurement of Products Containing

Recovered Materials

Goal: This program, in cooperation with seven states--Washi ngton,

Colorado, Minnesota, Florida, New York, New Jersey and Michigan

will identify the technical barriers to the procurement of products

containing recovered materials. The project will examine state

statutes and policies regarding such procurements, identify

successful or unsuccessful procurement experience, identify

potential products and examine purchasing specifications for

exclusionary citations, test methods or performance criteria on the

use of recovered materials.

Technical Office of Recycled Materials

Area at

NBS:

Personnel: J. Berke and C. Hudson, State representatives in procurement

or energy departments for the various states.

Accomplishments in FY 1981

The project was completed July 1981 when reports were submitted by

the seven states. The executive summary report has been prepared and

provides a summary, conclusions, and recommendations gleaned from a series

of studies carried out in seven states on the procurement of products

containing recovered or recycled materials. The participating states were Washington, Colorado, Minnesota, Michigan, New York, New Jersey and

Florida. In addition to the seven states, the National Association of

State Purchasing Officials (NASPO) participated as project observer and

has provided a position paper reflecting the study and the future

directions of public purchasing related to the procurement of products

containing recycled or recovered materials.

The role of the National Bureau of Standards in this specific area of

public purchasing originates with the mandates of Sections 5002, 5003 and

6002 of the Resource Conservation and Recovery Act (RCRA) (P. L. 94-580)

as amended (P. L. 96-462).

In selecting the participating states the NBS endeavored to select

one state in each Federal region. However, several states that were approached could not participate at that time. It was then decided that

in addition to the states that could participate in the study to select

some states with contiguous boundaries so that the reader of the state

reports might compare the experiences of these states with regard to

products, manuf acturers, and local distributors within the same geographical region. These state pairs were Minnesoa and Michigan, and

New York and New Jersey.

The states were first approached through their respective Office of

Procurement. If the Office of Procurement could not directly take a grant

or could not carry out the tasks for any reason, they were asked to

recommend a group who could undertake the project. These recommendations

96
are reflected in the title pages of the individual state reports. The

state procurement office in each state did o^fer full cooperation with

the study teams and worked closely with them.

The task activities that NBS asked the states to perform are indicated in the following work statement:

1. Survey and report on state statutes pertaining to the

procurement of products containing recovered materials.

2. Report on past, current or future programs and other state

activities related to the procurement of products containing

recovered materials.

3. Identify and report any legal, institutional, procedural,

economic, or technical barriers to the state procurement of

products with recovered materials.

4. Identify and report on any successsful or unsuccessful

attempts to procure products with recovered materials. This

should include those initiated by state solicitation or offerings by suppliers and manufacturers.

5. Provide a listing of the State's top ten products purchased

based on volume and/or dollar value. This should include any

cooperative purchases for local governments, special districts

or agencies.

6. Provide a listing, based on the best knowledge and experience

in the State, of products that are most amenable to the

inclusion of recovered materials. If not included in listing

of ten products in item (5), then please provide volume and

dollar value of such purchases.

7. For the list of products selected for item 6, provide all

pertinent specifications, test methods, performance criteria

and other information related to the procurement of each

product.

The information was compiled from reading the individual state

reports and summarizing the results. Highlights of specific state

activities are presented following a general summary of each task. For

further details regarding any of the participating states, interested

parties are advised to read the specific state reports.

The states participating in this study indicate that purchases made

by their procurement divisions do, in fact, include many products

containing recycled materials. In some instances, the purchasing agent is unaware that the procured product contains recycled material because it is

not labelled as to content, or the vendor chooses not to disclose such

information for fear that the product may be viewed as inferior. There

has been a long-standing bias against purchasing recycled goods and a preference for goods made from virgin materials, even when the quality of

the two items is comparable.

97
Many states indicate that the lack of standards and specifications

for recycled products inhibits state procurement of products containing

recycled materials. This information is needed by procurement offices in

all states so that propr procurement decisions might be made. The

importance of the link between products containing recycled materials and

energy conservation is noted by several states. This point should be

stressed in an educational program in order that more efficient allocation

of resources might be effected.

Plans for FY 1982

1. We have asked the State of Florida to initiate work on a Public Purchasing Directory that will be national in scope.

This project will identify on a national level, producers,

manufacturers, or distributors of products containing recycled

or recovered materials. Florida will prepare a directory

based on the companies identified. The directory will

include:

a) Table of contents.

b) Inroduction and statement that inclusion does not

represent endorsement.

c) Sections for each group of materials used with companies

listed by state in alphabetical order within each section.

Listing will include company name, address, telephone

number, key contact person, recovered or recycled material

used, principal product(s) made from the recovered

materi al

d. Chart of products made from each group of recycled or recovered material.

e. List of agencies and organizations to contact for further

information, including state solid waste offices.

f. List of directories on recyclers (these directories will

include dealer/processors).

g. Bibl iography.

This directory will be of assistance to all state, local, and

national purchasing officials in their search for products containing

recycled materials. The directory is scheduled for completion December

11, 1981.

2. The State of Colorado is developing a sample purchased product

evaluation (bid modifier) for purchasing use, to compare similar

functional items with differing values of recyclables material

content. The state will:

a. Survey existing literature to determine what portions of

the work statement can use existing data. Search the

98
files of the Denver Conservation Library and other sources

for related information.

b. List the various generic items and identify the

specifications for the branded products. Prepare a list

of component parts of each branded product showing the

weight and kind of material for each component. Put this

data in tabular form for use in later phases of the work

statement.

c. Determine the average BTU required to manufacture and

deliver each of the various products. Use Table 4 from

the "Methodology for Estimating Energy Savings for State

Conservation Plans."

d. Determine the alternative methods of disposal for each

item and the relative BTU values for each method of

disposal of each item. Review trash collection and

disposal systems of representative Colorado cities seeking

to include in the sample, disposal systems that bury

trash, as well as those that burn trash. Compare these

with reports on systems elsewhere in the U.S. that

separate and collect recyclable materials from trash.

e. Determine the recyclable components of each item and the

BTU potential for each item through recycling. From the

data derived in a, above, and from tables developed by

Colorado to evaluate bids for products containing

recycled materials, estimate the BTU value of each

component of each item if it were recycled.

f. Prepare a table which develops a sum of the BTU gains and

losses attributable to each item and represent the result

as a price adjustment factor, which will weight similar

items in proportion to their recyclable value. Using the

BTU values derived, develop a formula to represent the BTU

adjustment as a factor against price. Test the factor and

the formula on various Purchase Orders, making adjustments

as necessary.

g. Prepare a report describing the methodology and

statistical approach used to develop the sample table, and

make recommendations as to the potential value of a Complete Table for general use. Supplement the report

with a workshop to present the findings and provide the

NBS with clarification and insight during those

discussions.

This project is scheduled for completion February 1, 1982.

99
B. TECHNICAL ADVISORY CENTER

IQO:
Asso ^'idtion of State and Territorial Solid

Waste Management Officials

In September 1980, the Office of Recycled Materials issued a grant to

the Association of State and Territorial Solid Waste Management Officials

(ASTSWMO). This Association is comprised of State officials responsible

for the planning and implementation of State resource recovery and

hazardous waste management programs unde-' the Resource Conservation and

Recovery Act of 1976, as amended. Forty-three States are represented by

the organization. This grant has and will assist the Department of

Commerce fulfill its responsibilities under Subtitle E, specifically the

charge to provide a forim for the exchange of technical and economic

data relating to resource recovery facilities and to provide accurate

specifications for recovered materials.

The Association has undertaken four major tasks under this grant:

Preparation of a report identifying institutional and technical

barriers to the recovery and reuse of industrial wastes; for

example, waste solvents;

A study identifying State measurement needs under Subtitle C,

hazardous waste management; Subtitle D, solid waste management;

and. Subtit. e E, resource conservation and recovery;

Evaluation of economic analysis methodologies to determine whether

or not resource conservation and recovery is a feasible option;

and.

Preparation of a report identifying resource conservation and

recovery information needs including description of State

utilization of information exchange and dissemination programs.

Activities to Date

On September 30, 1981, the Resource Recovery Committee on behalf of

the Association of State ard Territorial Solid Waste Management Officials

submitted to the Office of Recycled Materials the report States'

Measurement Needs . The report consists of the following sections

Part I: Final Report and Executive Summary: State summary

charts depicting definitions of hazardous waste,

measurement parameters, laboratory needs, and available

training programs; Conclusions and Recommendations

Part II: State Profiles (Texas, Louisiana, Oklahoma,

Pennsylvania, Mississippi, Virginia): Solid waste,

hazardous waste and resource recovery program

objectives; State agency organizational make-up; resources and manpower; selected regulations; data from

field visits on laboratory capability; other

appropriate documentation.

101
° Part III: Analytical Operations Procedure Manual Model: A

cohesive technical framework and outline of tools

necessary to augment States' hazardous waste program

based on experience and guidance of State of Louisiana.

In preparing this final report on Task II, the Association's Resource

Recovery Committee considered the following questions:

(1) Does the State have adequate laboratory support staff,

equipment, and resources or the services of a private contractor

to perform RCRA-related measurement activities?

(2) What are State laboratory equipment holdings?

(3) Are the laboratories certified? Do they have a quality

assurance program?

(4) Is there adequate laboratory and field protective equipment and

clothing?

(5) What types of technical assistance do laboratory and field

personnel need and from which entities?

(6) What are the overall prioritized needs in support of

implementing the technical requirements under RCRA?

In the first phase, the Association Committee prepared profiles of

six States' individual responses to the above cited inquiries. Those

States were Oklahoma, Texas, Louisiana, Mississippi, Virginia, and

Pennsylvania. In order to meet grant submission deadlines and present a representative cross section of States, the Committee and ASTSWMO staff

selected these States. The Committee intends to continue to prepare

selected State profiles throughout the remainder of the grant.

Findings, Task II

The Committee concluded that even though State programs vary in

stringency of regulatory requirements. State measurement needs are similar

in hazardous waste. However, Subtitle D resource recovery measurement

needs, while identified, do not exhibit the same level of priority

associated with Subtitle C program. Nevertheless, standard analytical

methods, protocols, and procedures specified in State regulations match

those methods cited in Federal criteria. Development of standard lab and

field methods for sampling and analyses as well as standard reference data

is required. The lack of availability for such measurement tools is

severely impeding national consistency on a State-to-State basis, timely

program implementation, and worker protection and safety. Consequently, a formal operating procedures manual is necessary to assure not only Stateto-State programmatic and enforcement consistency, but also in intra-State

field and functional laboratory activities. A standard laboratory

certification quality assurance prograrri does not exist and will be helpful

in attaining State-to-State consistency. Lastly, training programs and

technical assistance for laboratory and field personnel is deficient at

State level

102
Information Exchange

The Association’s goal under Task IV is assisting the TAG by

providing guidance in the establishment of a forum for the exchange of

technical and economic data relating to resource conservation and

recovery, particularly resource recovery and recycling facilities. The

effort is designed to help TAG avoid duplication of past efforts by DoG

and other Federal agencies, and maximize limited resources available to

assist governmental organization and targetted industrial sectors.

Findings to date are that available information is redundant, out-dated,

and inappropriate to current problems in the field.

According to the Association's preliminary report, data retrieval

bases and computerized information are existent but little used or limited

in scope. Since many States are unaware of existing systems, the

indications are that the user community needs guidance and assistance in

problem clarification, system awareness, and facilitation of selecting the

most feasible option for addressing individual State issues and problems.

The ASTSWMO report for this task will strive to assess the following:

(1) What are State information/data needs and their availability?

(2) What data/i nformation systems exist that are compatible or could

be easily integrated with RGRA-related activities?

(3) Have the States utilized these and other information sources and

systems in the past or present, for what type of problems, and

the ease of use?

(4) What resources are necessary or available to establish and

implement an information network?

(5) What type of information exchange or other options do the States

need and how beneficial would such an effort be to RGRA-related

activities?

Gurrently, ASTSWMO has initiated data gathering aspects of this task and

plans to conduct a seminar concerning the necessity and benefits of an information exchange forum and the identification of training and

education needs associated with this activity.

Economic Analysis

By providing governmencal officials with economic analysis

methodologies for considering the feasibility of resource recovery

projects, the Office of Recycled Materials will fulfill a charge under

Subtitle E to identify geographical location of existing or potential

markets for recovered materials, identify economic and technical barriers

to use of recovered materials, and encourage the promotion of proven

technology. To this end the Association will evaluate such models and

methodologies as requested by TAG as well as those of the Association's

interest and selection. To date, the Association has selected to study

four States active in resource conservation and recovery; Gonnecticut,

103
Florida, Minnesota, and Oregon. In addition, a survey of models

appropriate to or utilized in the field has been conducted and preliminary

evaluation commenced.

104
Edward B. Berman Associates, Inc.

Resource Recovery Planning Model

The Technical Advisory Center explored the feasibility of developing

a model design for economic evaluation of regional resource recovery

systems on a statewide basis. A study sponsored by TAC concluded that a gross design of a mathematical model to serve the following purposes was possible:

(1) Generation of a preferred regional plan for resource recovery;

(2) Evaluation of a specified plan for resource recovery; and,

(3) Prevision for the inclusion of source separation as an option.

The criteria selected for generating a preferred regional plan for

resource recovery were;

“ Minimize lifetime cost of selected plan; £r

° Minimize lifetime discounted cost; ^

Maximize net energy balance;

Optimize a composite of weighted cost and/or energy

considerations.

Based on study result', TAC concluded that the model encompassing

three primary objectives and preferred plan selection criteria was feasible. In addition, the model to be developed would include the

capacity to report for each regional plan selected or generated:

(1) c osts in total and category breakdown, annually and over lifetime of

the ^an; (2) discounted costs by total and category, annually and over lifetime of the plan; and, (^) energy balance by energy category and net

system energy balance. For generated regional plans, the model selection

would detail sites selected for processing; the recovery process selected

for each site; capacity in tons per year for each site-'process selected;

as well as, the direction and flow of the materials in the system.

The structure of the model includes a front end, an optimizer with

improved algorithm, and a back end. The front end receives all data and

data categories and determines costs. In an optimizing mode, the model

will utilize the matrix and optimizer. In an evaluation mode, the model

bypasses the optimizer and the program proceeds to the back end.

The optimizer is the Walker Fixed-Charge Linear Programming

Algorithm. This optimizer has the capability of treating costs in terms

of slopes and intercepts which are the fixed charges. With this

capability the consideration of economies of scale of centralized resource recovery processing facilities is possible and consideration of the tradeoff between economies of scale versus the transportation costs incurred in

achieving such scales.

105
The back end will receive either the specified regional plan from the

front end, or the regional plan generated from the optimizer and report

costs and energy implications. This portion will also detail the regional

plan. The report will provide all cost categories in both constant and

discounted costs and all energy categories.

Categories : Energy and Cost

The model manages a total of ten cost categories including two cost

categories for each element in the model. Cost categories can be defined

by the user. These cost categories permit the user to report separately

those costs imposed on different constituencies involved in or affected by

the regional plan.

The model encompasses ten energy categories including two separate

energy categories for each element. For example, input--No. 2 oil per

ton; output--steam per ton. In considering the maximum net energy balance

function, the weights equal to BTU equivalents will automatically be

assigned to energy categories. The user can define energy categories.

Options : Source Separation

The model will provide the user with the following source separation

opti ons

Mixed municipal solid waste (i.e., unconditionally no source

separation)

Unconditional source separation (i.e., capacity is provided for

processing only the residue); and.

Conditional source separation by price with a maximum of five

price categories (i.e., capacity is provided for processing the

residue plus the full paper tonnages).

In considering conditional source separation, paper only below the

specified cut-off price will be diverted to the processing plant. The

user must provide percentage splits for all price options offered to the

model. Under conditional source separation, capacity is provided in the

model for processing all paper since the processing plant must accept the

paper whenever offered.

Commodity Categories

The model handles a total of fifteen commodity categories. Each source separation category offered on the model requires a commodity

category. The user can also define commodity categories for intermediate

recoverable products, final recoverable products, or residues.

The model incorporates twenty transportation categories to be defined

by the user. Each category specifies a single commodity to be

transported, a distance table for packer or van haul, cost factors, and

energy balance. In the optimizing mode, each transportation activity

determination will be made on whether packer or van haul is preferred

106
based on the chosen objective function (e.g., least cost versus net energy

bal ances)

To date, the model including improved algorithm is in the process of

being entered onto the N3S computer facility and undergoing shakedown.

TAC and the firm of Edward B. Berman Associates, Inc., have entered into a cooperative agreement to develop and utilize the model in five case studies. The Louisiana Resource Recovery and Development Authority and

the City of New York have requested technical assistance in their

respective resource recovery projects and have agreed to participate in

preparation of case studies. The TAC staff has met and will continue to

work with both governmental entities in development of case studies. TAC

staff will cooperate with the Association of State and Territorial Solid

Waste Management Officials to assist that organization in its evaluation

of the model, determination of its applicability to communities seeking a resource recovery option, and awaits the recommendations on facilitating

end user manipulation of the model.

107
Opportunities for Economic Development an,cl Resource Recovery:

Hazardous, Waste Management in the Great Lakes Region

Throughout FY 81 the Great Lakes Basin Commission conducted a study

to develop methodologies for projecting the economic development effects

of hazardous waste management and to assess the potential for resource recovery of materials from selected waste streams. The three industrial

and manufacturing activities were selected as case studies: steel

manufacturing, electroplating, and paint manufacturing. This study

commenced September 1980 and was scheduled for completion by May 1982.

However, the Great Lakes Basin Commission has expired as of September

1981. Since then the Michigan Department of Commerce sought and received

from Office of Recycled Materials a new grant initiative to complete this

study and to explore implementation options. The Michigan Department of

Commerce has retained original project staff; consequently, the study

will be completed by 1982. The Michigan Department of Natural Resources

will assist as technical advisers to the project.

In the first phase of the study an assessment of the economic effects

is being conducted if economically efficient hazardous waste management

options are not available to generators. Analysis encompasses the cost of

on and off site management options, volume reduction through process

change, and resource recovery from hazardous waste streams as well as current recovery practices. A methodology for determining factors

affecting the market-ability of recovered products is under development.

Projections are being made on current market size, and impact of financial

and institutional incentives on potential market size.

Selection of Case Studies

The project staff selected industries for case studies in two steps:

1) determination of criteria for selection; 2) development and

uutilization of decision matrix. In general each candidate industry was scored for each criterion on a rank of one through three with one indicating most desirable, three least desirable. For example, a rank of one for the steel industry for the criterion "significance of industry to

the region" would indicate a high level of employment or value added in

the region. A total of twelve criteria were scored for twenty-five

candidate industries.

Criteria can be divided into three general areas: 1) industry

background; 2) waste stream characterization; and, 3) those related to

impact of the Resource Conservation and Recovery Act of 1976, as amended,

in the region. The first criteria group ensure that industries chosen are vital to the region; the second group designate industries with

significant waste management problems, and, lastly, the third group

address those industries seriously affected by implementation of RCRA in

the region.

On basis of this two step approach three selections were made:

1) steel manufacturing; 2) electroplating; and, 3) paint manufacturing.

Three other activities were considered but not selected since they are not

as signficant to the region's economy: textiles, organic chemicals, and

108
wood preserving. Other industries considered but scoring lower than

selected industries: leather tanning, pulp and paper, electric utilities,

petroleum refining, petroelum re-refining, pharmaceuticals, special

machinery manufacturing, electronic components, rubber, plastic,

pesticides, batteries, chemical wholesaling, drum reconditioning,

agricultural services, gas and service stations, soaps and detergent, and

gl ass.

In summary, steel manufacturing, electopl ating, and paint

manufacturing were chosen since all are a significant industry in the

regional economy; have a strong potential for resource recovery, and have

a high liklihood of incurring an adverse impact based on the

implementation of RCRA.

Data Acquisition

Economic analysis of hazardous waste treatment and disposal options

has progressed but encountered some difficulty in obtaining economic data

from individual firms. Or in some cases, economic data has not been

disaggregated. Nevertheless sufficient information has been obtained

directly and indirectly to proceed with information gathering tasks.

The technical identification of treatment, disposal and recovery

options have been completed.

Methodology

To date methodology for analyzing economic potential of recycling and resource recovery in the electroplating industry has been developed. A

similar analysis for solvent recovery in paint manufacturing industry has

been initiated. A preliminary report assessing the economic effect of

federal and State policies on relative costs of different treatment,

storage, and disposal options have been submitted.

Currently project staff are engaged in the development of a computer

program to select an optimal treatment, disposal or recovery option given

varying assumptions concerning landfill costs, distance to disposal site

and other parameters. When the logic for the program has been documented,

programming will begin.

109
V. Discussion

The RCRA-rel ated program continues to be responsive to the needs of

the parties concerned with resource recovery and solid waste management.

In keeping with the wishes of the new Administration, the program has

increased activities in calendar year 1981 with respect to non-hazardous

industrial wastes, e.g., the steel sludge recycling project.

The work on the components of municipal solid waste can be expected

to be completed within the next two years. Clearly, emphasis will be

placed upon reporting these results; more research involving non-hazardous

industrial waste will be undertaken as the municipal solid waste research

is completed.

The Technical Advisory Center expects to complete three major

projects in the coming fiscal year: The results obtained under the

ASTSWMO grant will serve as the foundation for NBS research in cooperation

with meeting State measurement needs in the field of resource recovery and

recycling. The model being developed cooperatively by NBS and Edward B. Berman Associates, Inc., is expected to become the basis for selection of resource recovery options by State and local governmental entities. Thus,

development of this model is responsive to Sections 5003 and 5004 of RCRA.

The Great Lakes Basin Commission/State of Michigan survey of potential

business responses to hazardous waste rules and regulations is expected to

provide insights into i ncorporating resource recovery, recycling, reuse,

and, consequently, waste reduction of discards deemed to be hazardous.

Since each ton of hazardous waste which must be disposed costs

approximately $200, the potential for savings in both dollars and

materials is very large.

The RCRA program has completed studies on the procurement of

recyclables by State and local government. In addition, the burn-orrecycle issue with respect to fiber was the subject of an extensive study,

the results of which are appended to this report. A survey of supply and

demand situation for waste fiber within 4 states (Florida, Georgia, South

Carolina and North Carolina) was completed. The report of these

investigations which were carried out by the Bureau of Industrial

Economics of the Department of Commerce is expected to be ready for public

dissemination in early December 1981.

Interagency cooperation continues to be excellent despite program

reductions in several other Federal agencies. This spirit of cooperation

is, of course, expected to continue in the coming year. Furthermore, new cooperative ventures with the Department of Defense are likely to begin.

DoD has apparently decided to implement resource recovery at many domestic

military bases. Thus, NBS research can be expected to play an important

foundation role in order that each base obtain the most appropriate resource recovery/recycl i ng methodology consistent with minimum costs.

The cooperative program on resource recovery research initiated under

the United States-Japan Scientific Treaty of May 2, 1980, has been

selected by the Japanese as one of the two most important projects in the

Non-Energy Group. The Japanese team will visit the United States in

December 1981, and a U.S. team, chaired by NBS, will visit Japan in 1982.

no
The clientele of the RCRA program includes persons at all levels of

government and industry. Program personnel serve a variety of capacities

in voluntary standards organizations such as ASTM and ASME, which

contribute to the growth of resource recovery, recycling, and reuse of

materials originally destined for waste.

In light of recent cutbacks in other Federal agencies, ORM is the

only major research center dealing with direct in-house research

concerning resource recovery in the Federal establishment. Thus, the

major responsibility for implementing resource recovery research in the

United States has devolved upon ORM. ORM accepts this challenge and

intends to meet it fully.

Ill
APPENDICES

I PROCUREMENT OF PRODUCTS CONTAINING RECOVERED MATERIAL: A SUMMARY

OF ACTIVITIES IN SEVEN STATES

II SUPPORT OF THE DEPARTMENT OF COMMERCE PROGRAMS UNDER THE RESOURCE

CONSERVATION AND RECOVERY ACT

III RECENT FEDERAL ACTIONS WHICH WILL AFFECT PRICES AND DEMANDS FOR

DISCARDED FIBERS

IV DETERMINATION OF THE CALORIFIC VALUE OF REFUSE-DERIVED-FUELS BY

LARGE-BOMB CALORIMETRY SUMMARY OF THE 1978 FISCAL YEAR RESULTS

V TEST PROCEDURES FOR THE DETERMINATION OF THE GROSS CALORIFIC VALUE

OF REFUSE AND REFUSE-DERIVED-FUEL BY CONVENTIONAL BOMB AND LARGE

BOMB CALORIMETRY

VI AN OXYGEN FLOW CALORIMETER FOR DETERMINING THE HEATING VALUE OF

KILOGRAM-SIZE SAMPLES OF MUNICIPAL SOLID WASTE

VII A LABORATORY APPROACH TO OBTAIN SUSPENSION COMBUSTION DATA FOR

REFUSE-DERIVED FUELS

VIII IPA PROGRESS REPORT No. 1

IX IPA PROGRESS REPORT No. 2

112
NBSIR 81-2316

Appendix I

Procurernsnt of Products

Containing Recovered Material:

A Summary of Activities in Seven

States

Office of Recycled Materials

U.S. Department of Commerce

National Bureau of Standards

Washington, DC 20234

July 1981

U S. DEPARTMENT OF COMMERCE

NATIONAL BUREAU OF STANDARDS

113
NBSIR 81-2316

PROCUREMENT OF PRODUCTS

CONTAINING RECOVERED MATERIAL:

A SUMMARY OF ACTIVITIES IN SEVEN

STATES

Joseph G. Berke and

Catherine H. Hudson

Office of Recycled Materials

U.S. Department of Commerce

National Bureau of Standards

Washington, DC 20234

July 1981

U.S. DEPARTMENT OF COMMERCE, Malcolm Baldrige, Secretary

NATIONAL BUREAU OF STANDARDS, Ernest Ambler, Director

114
TABLE OF CONTENTS

Page

INTRODUCTION AND BACKGROUND 1

RECOMMENDATIONS 24

State of Florida, Recommendations 25

State of Colorado, Recommendations 30

State of Michigan, Recommendations 34

State of Minnesota, Summary of Recommendations 36

State of New Jersey, Recommendations by Project Team 38

State of New York, Conclusion and Recommendations 41

State of Washington, Recommendations 43

NASPO POSITION PAPER 46

APPENDIX A 59

APPENDIX B 66

APPENDIX C 68

APPENDIX D 70

115
Appendix II

STATE MEASUREMENT NEEDS STUDY

FINAL REPORT

Contributors

Jacqueline M. Rams

Barbara Simcoe

Mary Gilroy

September 30, 1981

116
EXECUTIVE SUMMARY

The Association of State and Territorial Solid Waste Management

Officials has conducted a study for the Technical Advisory Center (TAC),

Office of Recycled Materials, Department of Commerce to determine the

State's technical capabilities and measurement needs resulting from implementation of RCRA, Subtitle C, Hazardous Waste Management regulations,

Sut title D Solid Waste Management regulations, and Subtitle E, Guidelines

for Resource Recovery and materials and energy recovery. Measurement needs

associated with RCRA will demand standard reference materials, standard

reference data, standard protocols and criteria for sampling and analysis

and possibly new analytical techniques. This ability to sample and con- duct reliable laboratory analyses becomes the enforcement tool of the act's

mandate to protect the public health and the environment. It permits es- tablishment of a baseline to which subsequent data can be legally and

quantitatively compared and evaluated for potential compliance actions;

provides extra time to develop innovative disposal, reuse, and reclamation

techniques while acting as an early warning and quality control device

for existing facilities and designs; provides the basis for setting acceptable emission levels and shaping design and performance standards for new activities; and it provides a means of acquiring a permit variance. It

therefore behooves the States, in this case the regulator, to meet RCRA's

measurement needs effectively, expeditiously, and consistently.

This report details six States' capabilities in meeting those objectives:

Louisiana, Mississippi, Oklahoma, Pennsylvania, Texas and Virginia. With

the exception of Virginia, which has entered into a cooperative agreement

with the U.S. Environmental Protection Agency (EPA), the remaining five

States have received authorization to run their own programs for Phase I program implementation. Laboratory capabilities in meeting the measurement

requirements of RCRA vary from no laboratory support and the utilization of

contractors (Louisiana) to full-service State laboratory support functions

(Oklahoma, Pennsylvania, and Texas). The ability, then, for States to comply

with RCRA's technical needs consistently on a State- to-State level has not

yet been achieved — 3r.d their capabilities of doing so in the near future

varies.

Measurement requirements associated with RCRA pertain to two general areas of waste management activities: identification of a waste to be

hazardous or non-hazardous and monitoring expectations associated with permitting of facilities, existing or new. Determination of the hazardous

characteristics for a waste (and hence its definition of being hazardous or non-hazardous) requires analytical testing for the following: ignitabili ty,

corrosivity, reactivity and EP toxicity. Monitoring requirements are asso- ciated with baseline analysis, operational analysis, and facility closure

and post-closure to assure negligible environment insult and eliminate possible enuangerment to the public health. Possible routes of entry into the

environment are via groundwater, surface water, air, soil, and leachate.

Analysis of samples from these five discharge points will specify the substrate

composition, concentration levels, the mobility of potentially threatening

hazardous constituents, and hence the level of endangerment that exists for

this activity.

117
RESULTS

1) A comparison of State and Federal testing requirements under Subtitle C

is summarized in Chart A, and for Subtitle D - Chart B. On the whole,

measurement needs cited in Federal and State criteria appear ubiquitous.

Even though some States differ in their degree of stringency (Louisiana,

Pennsylvania, Oklahoma), States (with the exception of Virginia) have adopted

the uniform and minimal requirements as specified in the Federal program.

The trend, moreover, in the other States is similar for simplicity's sake in

achieving Phase I program authorization. Subtitle D and Resource Recovery

measurement requirements, however, do not exhibit the mandatory priorities

associated with Subtitle C wastes and are therefore incomplete in such specificities.

2) Standard analytical methods, protocols and procedures specified in State

regulations match methods cited in Federal criteria. Subsequent development

of standard lab and field methods for sampling and analyses, standard refer- ence data by EPA-ORD has been detained and exascerbated by decreased funding

levels. The lack of availability for such measurement tools is severely

impeding State-to-State consistency, timely program implementation, and

worker protection and safety.

3) Few laboratory personnel had an integrated understanding of their role

in RCRA programs. Moreover, there is a serious need for a formal operating

procedures manual to insure consistency from State-to-State and within State

field and laboratory functional areas.

4) Training programs and/or technical assistance for laboratory and field

personnel and appropriate safety equipment and clothing are critically deficient at the State level. Funding to meet these needs is either inadequate

or not available.

5) A standard laboratory certification quality assurance program for RCRA

does not exist. Development of such programs will assist in attaining Stateto-State consistency.

118
Appendix III

Recent Federal Actions Which Will Affect Pri ces and Demands for Discarded Fibers

Substance of the Talk Presented October 23, 1980

by Harvey Yakowitz, Chief

Office of Recycled Materials

National Bureau of Standards

119
Good morning. As a result of recent legislation, national policies with

respect to discarded fiber have been considerably altered. The purpose

of this talk is to try to outline for you what these policies may mean

in terms of both discarded fiber supply and possible influences on

“bottom line" profits. Preliminary analysis indicates that the costs of

waste news and boxboard may be driven upward by $10 to $20 per ton (1980

dollars) above current energy value for such fiber. For example, if the

cost of energy is $4.50 per million British thermal units (MBTU), then

the energy value of a ton of "dry" (93% fiber - 7% moisture) newsprint is

about $44 per ton. New policies are likely to raise this cost to about

$65 per ton in many cases via provision of Federal funds. In addition,

demand for the fiber is likely to increase strongly in the next several years.

Lastly, there is a definite possibility that access to the fiber supply may

be curtailed or even denied as waste- to-energy facilities compete for

public and private sources of funding.

Key legislation v/hich creates the impetus for these possible changes includes:

® Interior Appropriations for FY 1980 (P.L. 96-126) - Of the

$19 billion that was appropriated, $1.5 billion is targeted for

the purchase or production of alternative fuels by way of

purchase commitments or price guarantees. Another $708 million

will support preliminary alternative fuels commercialization

activities, including $100 million for project development feasibility

studies, $100 million for cooperative agreements, and up to

$500 million for loan guarantees for the construction of alternative

fuels production facilities.

120
o Crude Oil Windfall Profit Tax (P.L. 96-223) - Industrial

Development Bonds are authorized for financing facilities

primarily used to convert solid waste into alcohol and for

equipment at facilities used primarily to convert fuel derived

from solid waste into steam. Interest on obligations used to

finance a facility may also be tax exempt under specific

circumstances. P.L. 96-223 extended the biomass fuels tax credit

from 1982 to 1985 as well.

In my opinion, the most important piece of legislation in this regard is the

Energy Security Act (P.L. 96-294) which was signed into law on June 30, 1980.

o

The Energy Security Act requires the U. S. Department of Energy (DoE) to

create an Office of Energy from Municipal Waste (EMW) within the Department.

EMW was placed by the Secretary of Energy under the Assistant Secretary

for Conservation and Solar. In addition, as required by P. L. 96-294,

DoE produced a comprehensive plan dealing with;

(1) the anticipated research, development, demonstration, and commercialization

objectives to be achieved;

(2) the management structure and approach to be adopted to carry out

such plan;

(3) the program strategies, including detailed milestone goals

to be achieved;

(4) the specific funding requirements for individual program elements

121
and activities, including the total estimated construction

costs of proposed projects; and

(S) the estimated relative financial contributions of the Federal

Government and non-Federal participants in the program.

This plan was transmitted to the Congress and the President in late

October 1980. This document will be referred to in-this presentation as "the Plan".

Plan sets forth goals for accelerating the commercialization of

waste-to-energy facilities. In accordance with the provisions of the

Energy Security Act. Federal financial incentives including construction

loans, loan guarantees for construction, price support loans, price

guarantees, demonstration projects and research and development are dealt

with as the means to achieve the following general goals which are reproduced verbatim from the Plan:

A. Achieve an estimated production or conservation of

100,000-200,000 barrels of oil equivalent per day (BOEPD) (20

to 40 percent of the 1987 synfuel goal) by 1987. This goal

can be met by encouraging viable existing systems to meet

their planned capacity and by the construction and operation

of 54,000 tons per day (TPD) to 130,000 TPD additional capacity

plus by encouraging the recycling of an additional 40,000 TPD

of materials. The additional capacity can be met by the

construction of 40-95% of the projects now in planning.

122
Additional oroduction will be encouraged through DoE outreach

activities. •

® 250,000-280,000 BOEPD (12 to 14 percent of the 1992 synfuel

goal) by 1992. This gcal can be met by having new system

capacity expanded by 160,000-180,000 TPD and materials

recovery expanded to another 70,000 TPD. It should be noted

that municipal waste will provide an early impetus to achieving

the nation's synfuel goals but larger resources of coal, oil

shale and other nonrenewables which take longer to develop,

will assume a larger portion of the goal in the future.

B. Integrate energy recovery systems and materials recovery systems.

The removal of inorganics for recycling and energy conversion will

enhance the operations and efficiency of most energy production

facilities. The recycling of certain source separated organics

such as used and overrun newsprint and cardboard boxes can displace

significant quantities of energy.

C. Develop more energy efficient waste water treatment processes for

integration into the EPA clean water program and for retrofit in

existing facilities, where it is economically feasible.

In order to achieve these goals, DoE formally created EMW on September

11, 1980. The mission statement and organizational chart are shewn

as Figure (1), also taken from the Plan.

123
FIGURE 1 5

124
6

In order to achieve the goals set forth for 1987, i.e., 100,000 to 200,000

barrels of oil per day equivalent (BPDE), total investments of $5 to $10

billion (new capital) will be required. My best estimate is about $8 billion

plus an additional $1.5 billion per year for operation and maintenance costs.

To attain the 1992 goal would require additional capital investment of between

$6 and $11 billion in the period 1987 - 1992. In other terms, the 903l is

to increase U.S. energy-from-waste capacity which currently utilizes about 9000

tons per day of municipal solid waste to about 160,000 tons per day by 1987

and to about 325,000 tons per day by 1992. Thus, a seventeen fold increase

is sought by 1987 and 36 fold increase by 1992. Achievement of the 1992

goal would mean that over 75% of the available waste be converted to

energy, and that about 200-250 new energy-from-waste facilities would be

commissioned in the next 12 years.

The Office of Energy from Municipal Waste has chosen five methods to

achieve these goals:

® Provide Financial Incentives for Accelerated Project Development;

® Maximize the Productivity of Existing Waste-to-Energy Plant Development;

° Reduce the Difficulties of Financing Pre-Construction Project

Implementation Activities;

° Demonstrate Technologies with High Commercial Potential;

® Focus Research and Development Activities on Constraints to

Improvement in Waste-to-Energy Technology and Project Success.

In order to begin the program, some $230.9 million has been allocated to

EMW For the 1981 fiscal year. Of these funds, EMW proposes to spend

125
$10.9 million on research and development for accelerating commercialization,

$20 million on demonstration of technologies deemed nearly ready for

commercialization, $15 million for cooperative agreements meant to accelerate

commercialization, $25 million for loan guarantees and $160 million for

price support loans.

The basic thinking of EMW is stated in the Plan:

"The primary strategy of EMW is to provide financial incentives sufficient

to significantly accelerate the number of new project starts in the energyfrom-waste field. Delays in new starts are primarily caused by project

costs which are not competitive with alternative methods of waste disposal.

This obstacle can be overcome by providing additional revenue during the

early years of project operation. This additional revenue would enable a project

with attractive life-cycle economics to compete more favorably with disposal

alternatives and appear more attractive to local decision makers and private

investors.

The price support loan is best suited for solving the problem of early

year cost disparities. Therefore, EMW proposes to rely primarily upon the

price support loan authority for encouraging the more rapid commerialization

of waste-to-energy projects. The loan payback provision and other features

of this mechanism accomplish a significant support mission with a minimum

federal outlay and exposure. The program is expected to trigger substantial

immediate investment of private capital for project financing.

The price support loan program available to both public and private bodies

is expected to be a major factor in helping to remove political and economic

impediments in early years of a project by utilizing the positive life-cycle

126
8

economics to reduce early-^ear disposal fees. In doing so, it will improve

the position of economically sound projects against competing waste disposal

alternatives."

Note that price support loans pfonde for a 5 year (existing facilities)

or 7 year (new facilities) period in which the Federal government provides,

in year one, about $2 per million BTU delivered by a waste- to-energy facility;

the amount of such a loan is decreased linearly for the period of the loan.

No payback is required until year eight, and the Secretary of Energy may

waive payback.

With respect to conditions foi^ Federal financial assistance of any kind,

the Energy Security Act contains what might be construed as conflicting

retuirements. Section 235 of P.L. 96-294 states that no financial assistance

can be provided unless the Secretary of Energy finds that necessary municipal

waste feedstocks are available and it is reasonable to expect they will continue

to be available for the economic life of the project. But Section 235

of P. L. 96-294 also states that the Secretary of Energy shall not provide

financial assistance unless:

"...assurances are provided that the project will not use, in any substantial

quantities, waste paper which would otherwise be recycled for a use other

than as a fuel and will not substantially compete with facilities in

existence on the date of the financial assistance which are engaged in the

separation or recovery of reuseable materials from municipal waste."

And now the potential difficulties for the fiber recycling industry become

apparent:

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9

® Major efforts will be made-utilizing Federal funds as a portion

of the necessary funding - to rapidly accelerate commercialization

of waste-to-energy facilities;

® The price of waste fiber will rapidly rise by factors of two to

three above present market values;

° Demand for waste fiber will increase rapidly;

® Access to fiber markets may be curtailed or even denied;

*

° Markets currently served by the recycling of approximately 18 million

tons of fiber annually will need to be served in large part by other

sources of fiber.

The most important factor is market access. Many potential sponsors of

energy- from-waste facilities may wish to obtain as much fiber as possible

to convert to energy in order to increase income. Hence, local flow control

ordnances may be enacted. Several such ordnances already are on the

statute books; in general, such ordnances layclaim to the entire municipal

waste stream for usage by the local governmental entity for whatever purposes

it deems best in the interest of local health, safety etc. The net effect

may be to divert fiber supplies to burning and to lock waste paper collectors

out of the local market. Indeed, in at least one case, Akron, Ohiq the

right of a municipality to take control of the municipal waste stream has

been upheld in Court.

128
10

Therefore, concern exists that access to the waste fiber supply may be

curtailed. Burning of such fiber may not be the most energy efficient use

of the fiber in any case; conflicting claims exist with respect to this

point. The Department of Energy in formulating policies regarding eligibility

for Federal financial assistance energy-from-waste facilities has not

directly dealt with the issue of market access.

Apparently, eligibility for Federal financial assistance will depend only

upon the technical and financial soundness of the proposed or existing wasteto~energy facility. Assuming that municipal solid waste can be burned to

raise energy, the question of financial soundness remains, i.e., will the

facility be able to survive economically with Federal assistance? Such

a question invites one to place oneself into the role of "Head Official"

of the waste-to-energy facility and examine the options available.

First, as any prudent business official will do, a "break even" chart

will be prepared. This chart will list supplies of waste available,

energy available from burning this material, probable operation and

maintenance costs, insurance, working capital to construct the facility

and interest on its financial obligations. Hence, there will annually be

fixed costs, e.g., principal and intevest,and variable costs, e.g., operation

and maintenance. There will be anticipated income from energy sales, tipping

fees for depositing waste at the facility, and perhaps sales of materials

such as ferrous metals. The object is to determine where income

matches or exceeds fixed plus variable costs as a function of the waste

fed to the facility. Or, in simpler terms, what is the cost per ton

needed to break even and how many tons of incinerables are required.

129
11

The results of such an analysis are easily expressed in terms of a simple

equation:

(1) = -p + M

y where

Cp is the capital cost of the project in current dollars

Ip is the interest factor to repay the capital cost on an annual

basis.

Ty is the number of tons per year of waste burned.

is the cost of operations, maintenance and other annual items expressed

in dollars per input ton, and

is the number of dollars required per input ton of waste in order

to break even.

Consider now the potential average income from burning a ton of mixed

municipal waste. If the trash contains 4500 BTU per pound or 9 MBTU per ton

and if the conversion efficiency is 67%, which is actually fairly high

for burning of such waste, then 6 MBTU per ton are recoverable for use as energy. If the price of energy is $4.50 per MBTU, then a sales income of

$26 is available per input ton of waste. In addition, tipping fees which are roughly competitive with local landfill costs can be added. In certain

areas of the United States, notably the northeast, tip fees of $15 to $20

per ton are possible. In other areas, tip fees of $5 to $10 are possible.

For illustrative purposes, let the total income our hypothetical "Head

Official" can reasonably expect be $36 per input ton of mixed waste,

i.e., $26 in energy sales and a $10 per ton tip fee. Presumably, the

130
12

Head Official will know how much waste must be disposed. Roughly,

if waste is being received from a population of 500,000 persons, 750 tons

per day will be available. Hence, a capacity of 1000 tons per day is prudent to

allow for peak loads and some expansion. Note that the municipal waste stream

does not appear to have grown significantly in the past several years.

Most waste-to-energy conversion systems cost $50,000 to $70,000 per ton

of waste to be treated daily. Assume our Head Official expects to spend

$60,000 per ton per day in capital or a total 6f $60 million for the facility

whose "shoehorn" capacity is 365,000 tons per year. If financing for 20 years

at 10% can be arranged, an annual payback of principal and interest of $7.05

million is required to deal with the current 750 tons per day (about 275,000

tons per year) of waste which can be expected to be treated at the facility.

A rough estimate for labor costs, operation and maintenance is $12 to $18

per input ton. Assume our Head Official expects costs of $15 per ton.

Solution of Equation (1) indicates that the breakeven value per input ton of

waste to deal with 275,000 tons per year is about $41 per ton. Thus, our

Head Official is looking at a shortfall of $5 per ton or nearly $1.4 million

per year.

In any case, only a few options are available to the Head Official:

(1) Get more waste.

(2) Increase conversion efficiency of the process.

(3) Utilize components having higher energy content to burn.

(4) Raise the tipping fee.

131
13

(5) Raise the energy price.

(6) Obtain funds from outside sources, e.g., the Federal government.

Note that reduction of capital costs and/or variable costs is a difficult option

to exercise. Reducing the capacity of the facility is perhaps not prudent

when a total growth margin of 25% is allowed. Insurance and labor costs are

also not likely to be easily controlled either.

Raising tipping fees or energy prices may cost the facility public support

and/or customers for the energy to be produced. Obviously, without longterm customers for the energy produced, the facility is not feasible.

Increasing conversion efficiency is not really an option for the customer;

research is needed in this area. Hence, the Head Official really is looking

at increasing the output Of saleable energy and/or obtaining outside sources

of funds.

In our example, the Head Official needs to increase output by about

1.1 MBTU per input ton or approximately 18%. Either that, or someone

needs to provide $1.4 million every year (1980 dollars) for twenty years to make

the facility economically viable.

Our Head Official, as a result of the policies espoused in the Energy

Security Act and their proposed implementation in the Plan, can solve

his problems in ways which may allow him to reduce tipping fees and perhaps

the energy price as well so as to attract customers.

132
14

Recall that price support loans will be the major Federal incentive available

to the Head Official. In the first year of operation—assuming the facility

operates precisely as hcped—a price support loan of up to $12 per ton of

waste burned is available, i.e. , $2 per MBTU by 6 MBTU per ton. But,

Federal funds cannot allow the proprietor of a waste-to-energy facility to

obtain a positive cash flow. If I were Head Official, I would want to

capture the entire $12 per ton. Hence, I need only obtain $29 per ton in

sales plus tipping fees. Furthermore, if the output of the facility can be

increased, I can further control energy and tipping fees using still more

Federal dollars to leverage the system.

Therefore, in fairly general terms, I conclude that any intelligent "Head

Official" will move to arrange matters to obtain the highest possible

output of energy per input ton of incinerable so as to maximize the possibility for increased Federal funds based upon delivered energy. For cases

of existing facilities with underutilized capacity, the impulsive force to

do so will probably be irresistible.

Accordingly, if I were "Head Official," I would take the following actions:

(1) Obtain as much source separated fiber--both boxboard and newsprint--as

possible via municipal collection from citizens onto trash collection

trucks with appropriate racks.

(2) Store this material under roof at the waste-to-energy plant for

maximum economic leverage, i.e., sale to the paper industry at prices

equivalent or higher than available from burning.

(3) Move to minimize my collection costs to obtain the fiber, e.g., flow

control laws to reduce demand competition.

133
( 4 ) Obtain waste tires, shred them at the facility, and store the chips

to burn. Brokering of tires to the recapping industry might also

occur.

( 5 ) Obtain other possible high heating value combustibles such as wood

chips or waste oil to charge to the incinerator.

(6) Apply for price support loans or other Federal aid based on total

energy expected per year after implementing the five foregoing items

insofar as possible.

Consider only the economics as applied to fiber. One ton of "dry" newsprint should yield about 10 MBTU as recoverable energy. The energy price

in our example is $45 per ton. The price support loan adds a potential $20

per ton for a total of $65 per ton value to the burn facility. Thus, the

proprietor of the burn facility may be willing to sell newsprint at some

price above $65 per ton. Boxboard would be affected similarly except that

the price would probably be in the neighborhood of $50 per ton since the

energy value is lower.

Such a scenario meets the requirement that the fiber be available for

recycling. Existing fiber collectors would not be affected directly, but

prices will rise.

As proprietor of the burn facility, I can expect to obtain about 50 tons

per day of separated fiber. I would expect a daily increase in output of

my plant of about 175 MBTU over that which would have been produced from

750 daily tons of mixed waste or an increase of about 12 percent. Rubber

and other combustibles will increase this figure.

134
16

Next, I will reduce tipping fees and/or energy prices so as to capture as

much Federal funding as possible. I will now have a viable facility and

be in fairly strong control of the waste fiber in my area. In any event,

waste fiber prices will probably treble and market access be curtailed.

Furthermore, the proprietor may well purchase a foreign-made incinerator

system.

As a further spur toward implementing waste-to-energy systems, the Department

of Housing and Urban Development (HUD) and the Department of Energy recently

formed a technical assistance team headed by Oak Ridge National Laboratory,

and assisted by the Conference of Mayors, to work with six cities in their

attempt to link resource recovery systems with economic development objectives.

Specifically, the team will offer whatever assistance desirable in the

preparation of Urban Development Action Grant applications to HUD regarding

urban waste-to-energy systems and the necessary additional information those

applications require. In addition, the use of DOE's price loan guarantees

for these projects will be explored.

The purpose in forming this team is to help cities demonstrate that with a

relatively small amount of public funds, projects that previously experienced

financing shortfalls will be able to proceed expeditiously. HUD and DOE's

intent, however, is not to subsidize waste-to-energy projects, but to assist

those projects that offer the opportunity to spur economic development in

ways that are consistent with the purposes of the Action Grant program and

urban revitalization in general.

135
1

The Technical Assistance Team will meet with City representatives to

determine what assistance would be most desirable and useful . The team

may:

® Assist in identifying financing options;

° Assist in assembling project information as it relates to the requirements of UDAG;

° Help to define and measure the urban economic development impact of

the project;

° Assess the impact of technical considerations of financing options by

determining if all technical, legal, and marketing commitments are in

order for the project to obtain the best financing possible; and

° Help to facilitate the transmission of project information to HUD/DOE

officials.

° Technical assistance to a select group of cities could expedite

their ability to use HUD funds for these projects and increase the

quality of projects submitted for HUD*s consideration .

In summary then. Federal policies are in place which are meant to increase

waste- to-energy facility capacity by a factor of 36 in the next dozen

years. Federal assistance is to be provided to accelerate commercialization

of such facilities; financial incentives are directly available from DOE

and perhaps from HUD as well. I believe that if the goals of these policies

are met, the price of waste fiber will treble and that access to supplies

may well be curtailed.

Implementation of these policies is currently underway and proposals for

obtaining Federal assistance are currently being received by the Federal

establishments. Awards are expected in early 1981.

136
Appendix

Estimating Financial Requirements for a Waste-to-Energy Facility

As shown by Equation (1):

CIp

(1) Mj where

Cp is the capital cost of the project in current dollars

Ip is the interest factor to repay the capital cost on an annual basis.

Ty is the number of tons per year of waste burned.

Mj is the cost of operations, maintenance and other annual items expressed

in dollars per input ton, and

Qy is the number of dollars required per input ton of waste in order

to break even.

Rearranging to solve for the capital cost which can be borne for a given

number of dollars income per input ton of waste.

(Qt - Hj)

(2) Cp = —j— T,

Note that

(3) = Sy + Fy + Xy where

Sy is sales income per input ton of waste to the facility. Note that

customers are assumed to be under contract to assure these sales.

Fy is the tipping fee per input ton of waste. Note that only "guaranteed"

137
2

waste, i.e., under contract can be taken into account.

Xj is any other source of income, e.g.. Federal or other assistance, per

input ton.

Now if we let Dy be the number of days per year the facility is operational.

Equation (2) becomes

(4) Cp

(Qj

-

Note that (Ty/Dy) is merely the number of tons per day of waste actually

charged to the facility - not the rated capacity - taken over the number of

days of actual operation. For example, if 1000 tons per day is charged

six days per week, then Ty becomes

(4a) Ty = (6) (52) (1000) = 312,000 TPY

while Ty/Dy is, of course, 1000 TPD

Rated capacity is nearly a meaningless term; the key to determining the

probable costs of a waste- to-energy facility is the total number of tons

of waste processed per day times the number of days per year the plant

actually operates.

Interest factors depend upon the term of the loan and the rated interest.

For a publically financed waste-to-energy plant, interest factors as a

138
3

function of rated interest may be computed from

(6) Ip = i where

(1 + i )"-

i is the interest rate and n is number of years needed to pay back

principal plus interest.

For n of 15 and 20 years respectively, equation (6) may be approximated

fairly closely as

(6A) Ip = 0.80 i + 0.052

n = 15 and i ranging from 0.05 to 0.20.

(6b) Ip = 0.85 i + 0.034

n = 20 and i ranging from 0.05 to 0.20.

Analysis of Equation (6) indicates that if the interest rate increases

by 0.0001 or, in the language of the banking community, by one basis point,

then the break even cost per input ton of waste increases by about

1.6 cents.

Energy price values per ton of waste can be expressed simply as

(7) S-j- p

= tiHPq where

Sj

p

energy sales income per input ton of waste

n is conversion efficiency of waste in to energy out.

H is the heat content of the waste, and

pQ is the delivered price of energy in $/MBTU.

139
4

Note that for mass burning, values of n range from about 0.6 to 0.71

for mixed municipal solid waste. For dry newsprint and boxboard, n values

of 0.75 to 0.80 are expected; similar values for split tires burned on a

spreader stoker can be expected.

With respect to heat content, H, mixed municipal waste averages between

7 and 10 MBTU per ton (3500 to 5000 BTU per pound). Dry newsprint has

a heat content of about 14 MBTU while boxboard has about 11 MBTU. Tires

contain about 16,000 BTU per pound of rubber or 32 MBTU per ton. Waste oil

contains about 0.14 MBTU per gallon.

Thus, to increase sales income per input ton, a high conversion efficiency

is extremely desirable. At a delivered price of $4.50 per MBTU for

energy, a reduction of 0.01 in conversion efficiency results in a loss

of $0,405 per input ton or more than $100,000 per year to a facility

treating 250,000 tons per year of waste.

Costs of operations, maintenance and other annual expenses need to be

determined on a case-by-case basis in order to insert values for My.

Thus, with Qy, My, Ty and Ip, one can estimate the total cost for a wasteto-energy facility which can be afforded. Or, if capital costs have been

decided upon, one can obtain the required income to break even or earn a

profit. By way of example, consider a situation in which the sponsor is

assured of receiving 500 TPD of municipal waste, but the sponsor knows that

an additional 500 TPD is in his "waste shed" now and wishes to capture it.

140
5

Thus, the sponsor decides that 1000 TPD may be available now and wishes to

construct a 1200 TPD plant to accommodate both the additional 500 TPD plus

anticipated growth.

At current costs, a 1200 TPD rated capacity plant is likely to cost about

$75 million. If 20 year financing at 10% is available, then Equation (6)

gives Ip = 0.118. But only 500 TPD are assured; if the plant operates 300 days

per year, then Ty = 150,000. Assume is $14 per ton; such a value is

consistent with costs in the east and midwest. Then from Equation (1);

Q-P = X 10^) (0.1181 ^ ^ $73.00 per ton.

Thus, unless the additional 500 TPD are obtained prior to proceeding, and

markets found for the energy produced, the proposed plant is probably not

feasible. But with the additional 500 TPD, Qj becomes $43.50. Sales

income plus tipping fees plus any other source of funds must equal this

figure for the plant to be financially feasible. With no sources of income

save sales plus tipping fee, a tipping fee of $14 to $18 is likely. With a

DoE sponsored price support loan of $12 per input ton in the first year

of operation, tipping fees of $1.00 to $6.00 per ton result. Note that the

key points are securing feedstocks, i.e., sufficient waste, obtaining markets

for the energy and reliable operation for 300 days per year at a conversion

efficiency of about 67%.

Suppose that obtaining the additional 500 TPD now appears to be impossible;

141
6

and, therefore, the sponsor wishes to determine whether a 600 TPD facility is

feasible. Assume that each ton of input waste results in 6 MBTU of saleable

energy and that markets for such energy have been found. (Assumes 4500 BID

per pound of waste and a conversion efficiency of 0.67) The energy price is

$4.50 per MBTU or $26 per ton. The sponsor finds that a tipping fee of

$8.50 per ton is accetable to the clientele to be served by the facility.

Hence, with no other sources of funds, income per ton of input waste is

$34.50. The value of Ty is 150,000 and again, let Ip be 0.118, i;e., a

10% note for twenty years while Mj is $14 per ton. Then by Equation (2):

C

. ($34.50 - $14.00) (I.SxI qS)

. million.

P 0.118

Thus, the sponsor can afford to build a facility costing $26.1 million having

a rated capacity of 600 TPD or $43,500 per ton per day to be treated. Such

a price may be obtainable. If coupled with providing energy for new housing

development, a hospital, school or Junior College, shopping area, etc., some

degree of positive economic growth may be achieved using waste as a

source of energy.

142
Appendix IV

NBSIR 80-1968

Determinatjon of the Calorific Value of

Refuse-Derived-Fuels by Large-Bomb

Calorimetry Summary of the 1978

Fiscal Year Results

0. R. Kirklin, E. S. Domalski and D. J. Mitche!!

Chemical Thermodynamics Division

and the

Thermal Processes Division

National Bureau of Standards

Washington. D.C. 20234

January 1980

Prepared for U.S. Department of Energy

Office of the Assistant Secretary

Conservation and Solar Applications

Division of Building and Community Systems

Urban Waste and Municipal Systems Branch

Washington, D.C. 20585

and

U.S. Environmental Protection Agency

Municipal Environmental Research Laboratory

Solid and Hazardous Waste Research Division

Cincinnati, OH 45268

143
NBSIR 80-1968

determination of the calorific value of

refuse-derived-fuels by large-bomb

CALORIMETRY SUMMARY OF THE 1978

FISCAL YEAR RESULTS

D. R. Kirkiin, E. S. Domalski and D. J. Mitchell

Chemical Thermodynamics Division

and the

Thermal Processes Division

National Bureau of Standards

Washington, D.C. 20234

January 1980

Prepared for U.S. Department of Energy

Office of the Assistant Secretary

Conservation and Solar Applications

Divison of Building and Community Systems

Urban Waste and Municipal Systems Branch

Washington, D.C. 20585

and

U.S. Environmental Protection Agency

Municipal Environmental Research Laboratory

Solid and Hazardous Waste Research Division

Cincinnati, OH 45268

U.S. DEPARTMENT OF COMMERCE, Philip M. Klutznick, Secretary

Luther H. Hodges. Jr., Deputy Secretary

Jordan J. Baruch, Assistant Secretary for Science and Technology

NATIONAL BUREAU OF STANDARDS. Ernest Ambler. Director

144
Table of Contents

Abstract v

Introduction 1

Experimental 3

Materials 3

Sample Preparation 4

Calorimetric Apparatus 5

Calorimetric Procedure 7

Discussion and Results 9

Calibration Experiments 9

RDF Combustion Experiment 12

Conclusion 17

References 21

145
- rrrfTii^

List of Tables

Table I Calibration Experiments of the Bomb Calorimeters 22

Table II

MAF Calorific Values in MJ*kg (Btu*lb~^)

of Teledyne National RDF 23

Table III

Moisture and Ash Contents of RDF Samples 24

146
Determination of the Calorific Value of Refuse-Derived-Fuels by

Large-Bomb Calorimetry

Summary of the 1978 Fiscal Year Results

Duane R. Kirklin, Eugene S. Domalski and David J. Mitchell

National Bureau of Standards

Washington, DC 2023A

ABSTRACT

An oxygen bomb calorimeter which can accommodate a 25 gram sample

of refuse or a refuse-derived-fuel (RDF) has been designed and constructed

at the National Bureau of Standards for the purpose of studying the

effects of sample processing on the measured calorific value of such

material. This large calorimeter is an enlarged and modified version of

a conventional-size calorimeter also in use at NBS. The large calorimeter

can handle samples ten times larger than the conventional-size calorimeter

and therefore can be used to investigate RDF samples with either minimal

or no processing. Calorimetric results are presented for calorific

value measurements carried out on d(densif ied)-RDF in both calorimetric

systems. Moisture- and ash-free (MAF) calorific values were obtained in

the large calorimeter from six randomly chosen unprocessed RDF samples

and had a mean value of 24.99 MJ*kg ^ (10 742 Btu*lb ^) . Another randomlychosen sample of unprocessed RDF was subjected to extensive processing

to obtain a "homogeneous” analysis sample for use in the conventionalsize calorimeter. Individual measurements in the conventional size

calorimeter on each of ten "homogeneous" sub-samples gave a mean calorific

value of 24.99 MJ*kg (10 743 Btu®lb ^) . The results of this investigation

indicate that tlie calorific value of d-RDF is unaffected by the sample

processing technique used at NBS.

147
List of Figures

Figure 1.

Pellets of benzoic acid (left), processed

RDF (middle), and unprocessed denslfied

RDF (right) 25

Figure 2.

25-gram-capacity Bomb Calorimeter 26

Figure 3.

Inner arrangement of Large Combustion Bomb 27

Figure A.

Small and large combustion bombs 28

Figure 5.

Large calorimeter system (a view from the top) 29

Figure 6.

Time-temperature curve for a bomb calorimetric

experiment. 30

148
Appendix V

NBSiR 81-2278

Test Procedures for the

Determination of the Gross

Calorific Value of Refuse and

Refuse- Derived- Fuel By

Conventional Bomb and Large

Bomb Calorimetry

SUMMARY OF THE 1979 FISCAL YEAR RESULTS

D. R. Kirklin, J. Colbert, P. Decker, 3 . Abramowitz, and E. S. Domalski

Chemical Thermodynamics Division

Center for Chemical Physics

U.S. Department of Commerce

National Bureau o^ Standards

Washington, DC 20234

June 1981

Prepared for: U.S. Department of Energy

Assistant Secretary for

Conservation and Renewable Energy

Office of Energy from Municipal Waste

Washington, DC 20585

and

U.S. Environmental Protection Agency

Municipal Environmental Research Laboratory

Solid and Hazardous Waste Research Division

Cincinnati, OH 45268

149
NBSIR 81-2278

TEST PROCEDURES FOR THE

DETERMINATION OF THE GROSS

CALORIFIC VALUE OF REFUSE AND

REFUSE-DERIVED-FUEL BY

CONVENTIONAL BOMB AND LARGE

BOMB CALORIMETRY

SUMMARY OF THE 1 979 FISCAL YEAR RESULTS

D. R. Kirklin, J. Colbert, P. Decker, S. Abramowitz, and E. S. Domalski

Chemical Thermodynamics Division

Center for Chemical Physics

U.S. Department of Commerce

National Bureau of Standards

Washington, DC 20234

June 1981

Prepared for: U.S. Department of Energy

Assistant Secretary for

Conservation and Renewable Energy

Office of Energy from Municipal Waste

Washington, DC 20585

and

U.S. Environmental Protection Agency

Municipal Environmental Research Laboratory

Solid and Hazardous Waste Research Division

Cincinnati, OH 45268

• T O*

**'*IAU 0*

U.S. DEPARTMENT OF COMMERCE, Malcolm Baldrige, Secretary

NATIONAL BUREAU OF STAtSIDARDS. Ernest Ambler. Director

150
Table of Contents

J

J

]

J

J

3

3

3

J

I

1

Abstract

I. Introduction

II. Experimental

A. Materials

1 . Benzoic Acid

2. Oxygen

3. ASTM Round Robin PDF-3 Samples

(a) First Round Robin Sample

(b) Second Round Robin Sample

(c) Third Round Robin Sample

(d) Bituminous Coal Round Robin Sample

4. Teledyne National RDF

(a) RDF Pellets

(b) RDF-3 (Fluff) Sample

5. ECO FUEL- 1 1 RDF

3

3

3

3

I

I

5. Americology RDF-3 (Fluff)

7. New Castle County, Delaware MSW

8. Steam Size Reduction RDF

9. NCRR Storage Pic RDF (Charred Storage Sample)

10.

NCRR RDF (Low Ash Sample)

B. Oxygen Bomb Calorimeters

1. 2.5 gram capacity bomb calorimeter

2. 25 gram capacity bomb calorimeter

A

151
C. Sample Preparation Apparatus

1. Steelman 450°F Electric Bake Oven

2. W. W. Grinder Corporation Hammer Mill

3. Wiley Model 4 Laboratory Mill

4. Patterson-Kel ley Company

Twin Shell Dry Blenders

5. Carver Laboratory Press, Model M

D. Sample Preparation Procedure

1. Sample Drying

2. Particle Size Reduction

3. Sample Homogenization

4. Preparation of Pelletized Analysis Samples

E. Calorimetric Procedure

III. Results and Discussion o

A. Bomb Calorimetric Measurements

1. General Discussion

2. Test Procedures

3. Sample Preparation

4. Bomb Preparation

5. Calorimeter Preparation

6. Temperature Measurements

7. Calorimeter Corrections

3. Calculation of the Calorific Value

B. Calibration of the Calorimeters

1. NBS 2,5 gram Capacity Bomb Calorimeter

2. NBS 25 gram Capacity Bomb Calorimeter

152
C. Calorimetric Measurements on RDF

1. ASTM Subcommittee E-33.01 Round Robin Testing on RDF-3

a. First Round Robin Sample

b. Second Round Robin Sample

c. Third Round Robin Sample

d. Bituminous Coal Sample

2. Americology RDF Sample

3. Large and Small Calorimeter Comparison Measurements

a. Teledyne National Sample

b. ECO FUEL- I I RDF

c. Americology RDF

4. Bureau of Mines Processing of New Castle County, Delaware MSW

5. Representative or Unique RDF's

a. Teledyne National RDF .

b. Steam Size Reduction RDF

c. NCRR Storage Pile RDF

di NCRR Low Ash RDF

IV. Summary and Conclusions

V. References

Appendix A

Evaluation of Data on Higher Heating Values Determined during ASTM Round

Robin Testing of RDF-3

Appendix B

Large Isoperibol Bomb Calorimeter
Appendix C

Emission Spectrochemical Analysis of Bomb Residues

1. Teledyne National RDF

2. ECO FUEL- I I RDF

3. Ameri oology RDF

Appendix D

Conversion Table for the Calculation of Data to Different Bases

Appendix E

Calculation of Total Moisture in an RDF Sample

Acknowledgement

154
To be presented at the Second International Symposium on Materials, ajid

Energy from Refuse; Antwerp, Belgium, October 20-22, 1981

'

- Appendix VI

AN OmfGEN FLOW CALORIMETER FOR DETERMINING THE HEATING VALUE OF KILOGRAM-SIZE SAMPLES OF MUNICIPAL SOLID WASTE^'^

K.L. Churney, M.L. Reilly , A.E. Ledford, R.V. Ryan

and E.S, Doraalskl

Chemical Thermodynamics Division, Center for Chemical Physics

Temperature Measurements and

Absolute Physical Quantities

ABSTRACT

A new calorimeter is being developed at the National Bureau of Standards to determine the enthalpies of combustion of kilogram-size samples of

municipal solid waste (MSW) in flowing oxygen near atmospheric pressure. The organic fraction of 25

gram pellets of highly processed MSW has been

burned in pure oxygen to CO2 and HjO in a small

prototype flow calorimeter. The carbon content of

the ash and the uncertainty in the amount of CO in

the combustion products contribute calorimetric errors of 0.1 percent or less to the enthalpy of

combustion. Large pellets of relatively

unprocessed MSW have been successfully burned in a prototype kilogram-size combustor at a rate of 15 minutes per kilogram with CO/CO

2 ratios not

greater than 0.1 percent. Design of the kilogramsize calorimeter has been completed and fabrication has been started.

1. INTRODUCTION

The National Bureau of Standards (NBS) has been

mandated by the O.S. Congress through Public Law

9(•)

**-580, the Resource Conservation and Recovery Act

of 1976, to develop guidelines for specifications on recoverable waste materials. NBS has made a commitment to develop a calorimeter to determine

the calorific value of kilogram-size samples of

minimally processed municipal solid waste (MSW). A large-scale calorimeter affords greater credibility because kilogram-size samples of MSW

should be more representative of the heterogeneous

bulk material than the highly processed gram-size

samples currently used in bomb calorimetric determinations.

Combustion of samples in flowing oxygen near at- mospheric pressure rather than in the high pressure oxygen of a combustion bomb was adopted for

(1) Official contribution of the National Bureau

of Standards, not subject to copyright in the

United States of America.

(2) This work is jointly sponsored by the NBS

Office of Recycled Materials and the U. S. Department of Energy, Office of Energy from

Municipal Waste.

Standards Division, Center for

safety considerations. However, the flow technique has not been used in any substantial way to determine the enthalpy of combustion of solids

since the IbSO’s. Its development was discontinued because of the simpler techniques and more

quantitative results obtained with the bomb calorimeter. Attaining complete combustion was particularly difficult with a flow system. As a consequence, the first goal of the NES project was

to demonstrate that the oxygen flow technique

could be used to obtain complete combustion of

MSW.

To calculate the calorific value of the combustible fraction of MSW, the ash produced in each

experiment must be determined quantitatively. Ash

collection is simplified by burning pellets of the

sample in such a way as to prevent ash dispersal.

Therefore the combustors were designed to burn

pellets.

The first step in tne program was to build a calorimeter for combustion of 25 gram samples of

highly processed MSW. The purpose was to establish

the equivalence of the flow results with those

obtained by bomb calorimetry (e.g. with the new

NES 25 gram capacity bomb calorimeter (1)). The

preliminary results obtained with the 25 gram flow

calorimetric system are described in Part II.

Experiments with kilogram-size samples of minimally processed MSW were undertaken as the second

step of the NBS program. The primary aim was to develop a method of burning a large heterogeneous

sample completely with the minimum scattering of

ash. Calorimetric run-tine considerations required

the combustion tine be 15 min/kg or less. Additional experiments were carried out to test the

suitability of cellulose as a combustion calibrant

for the kilogram-size calorimeter. These experiments are described in Part III.

The design of the new kilogram-size calorimeter

which is based on the results of the initial work

is summarized in the discussion in Part IV.

(•) D. R. Klrklln, E. S. Domalski, and J. Mitchell,

NB5IR b0-19b3, January I960.

155
II. 25 GRAM FLOW EXPERIMENTS

The combustor used In the 25 gram oxygen flow

experiments is shown in Fig. 1. The sample pellet

(D of Fig. 1) was placed on a quartz plate (F)

which had eight radial slots and a small central

hole which permitted circulation of oxygen

beneath the sample. The plate sat in a quartz

crucible (E) which was supported by a nichrome

stand (J). Primary oxygen (H) was supplied locally

to the sample through a three-port tubular quartz

ring which was located immediately above the

crucible. The lower edge of the Pyrex thermal

shield (C) enclosed the ring and upper edge of the

crucible. The outer boundary of the combustor

consists of the stainless steel top (N) and base

(I) plus the Pyrex wall (L) which were sealed by

rubber gaskets (B). A secondary flow of oxygen

(G) swept down between the wall of the combustor

and the thermal shield and confined the flow of

the products of combustion to the interior of the

thermal shield. Gases left the combustor through a stainless steel exit line (A) at the top. The

temperatures of the product gases near the exit

port of the thermal shield and of the midpoint of

the interior of the thermal shield were monitored

using Type K thermocouples. The thermocouples were

supported in helical Pyrex tubing (K) which stood

within the thermal shield.

The combustor was placed in a provisional calorimetric assembly similar to the final design shown

in Fig. 2. The provisional assembly consisted of an insulated bell jar filled with water which was

circulated by a stirrer (J of Fig. 2) mounted from

the bell Jar cover. The flow shield (E) caused

the water to circulate up past the combustor (L) and down along the inner wall of the jar (analogous to B). The temperature of the water was

measured with a long stem platinum resistance

thermometer (C). The product gases flowed through

the helical exit gas coil (D) into the water trap

(F) and then through a second coil before leaving

the calorimeter. The coils and trap were made

from Pyrex.

After leaving the calorimeter the product gases

were scrubbed by bubbling then through water and

then the entire gas stream was passed successively

through a variable orifice flowmeter and non- dispersive infrared detectors for measuring the

concentrations of CO and CO 2. Preliminary

analysis of the product gases by both mass spectrometry and conventional infrared spectroscopy

showed CO to be the only species present due to incomplete combustion.

Sample pellets for the 25 gram experiments were

prepared from a blended powder of minus 0.5mm

particle size. The powder was made by milling

large batches of minus 15 cm MSW from which most

of the metals, glass and entrained inorganics had

been first removed. This powder is referred to as

RDF-l<. The cylindrical pellets, which were 3.5 cm in diameter and 2.5 cm high, were prepared by

pressing the powder in a die using a force ranging

from I45 to 160 kN. The residual moisture content

of the powder was determined to be about using

Fig. 1. The 25 Gram Combustor.

Notations: A denotes the product gas exit

line, B the gasket, C the thermal

shield, D the RDF-il sample, E the

crucible, F the plate, G the secondary

oxygen, H the primary oxygen, I the

combustor base, J the crucible

support, K the thermocouple coils, L the combustor walls, M the thermocouple junctions and N the combustor

lid.

the ASTM Standard Test Method D 3173-73 (Moisture

in the Analysis Sample of Coal and Coke).

In a typical experiment, the calorimeter was

assembled and the combustor was flushed with pure

oxygen. The temperature of the calorimeter water was recorded as a function of time for approximately twenty minutes after a steady initial

drift rate was attained. Just before ignition,

the primary and secondary oxygen flow rates were

set at approximately 8 and 5 /min, respectively.

The sample was ignited by passing electrical

current through an iron fuse wire (not shown in

Fig. 1) which was in contact with the top of the

156
Fig. 2. The 25 Gram Flow Calorimeter.

Notations: A denotes the vessel lid, B the vessel can, C the thermometer, D

the exit gas coils, E the flow shield,

F the water trap, G the oxygen supply

lines, H the submarine can, I the

submarine lid, J the stirrer and L the

combustor.

pellet. A 25 gram pellet typically burned within

fourteen minutes. Upon Ignition the pellet burned

with a diffusion flame which spread over its

entire surface within the first 30 seconds. The

flame temperature was determined to be greater

than 1500°C. A small but detectable peak in

the CO concentration occurred at about 3 minutes.

The surface flame disapoeared at about the eighth

minute. The glowing sample continued to burn internally leaving a porous ash structure that had

almost the same shape as the original pellet. The

product gases contained increasing amounts of CO, which reached a peak near the eleventh minute.

However, the ratio of CO to CO

2 remained low. A typical CO - COp composition profile of the pro- duct gases is shown in Fig. 3>

ELAPSED TIME /MIN

Fig. 3* The CO - COp composition of the product

gases vs the elapsed time from ignition

for a typical experiment.

The temperature of the product gas stream at the

top of the combustor rose quickly to a peak near 600®C some 30 seconds after ignition and then

decayed exponentially as the combustion preceded.

The product gases were cooled in the exit gas

coils and approximately 85J of the water formed was collected in the trap. The gas was further

cooled in the second exit coil. Throughout the

combustion, the temperature of the product gases

leaving the calorimeter was less than 0.1°C above

the temperature of the calorimeter water.

During the first seven minutes the temperature of

the calorimeter water rose linearly at a rate near

0.25°C/min. Subsequently, the temperature of the

calorimeter water continued to rise at a progressively diminishing rate until a final steady-state

drift rate was attained about forty-five minutes

after ignition. To establish the final drift

157
rate, temperatures were recorded for at least

thirty additional minutes. The temperature rise

(from the end of the initial drift period to the

beginning of the final drift period) was typically

2.3°C.

After disassembly of the calorimeter, the ash and

the quartz crucible were weighed. The carbon content of the ash was determined from the sum of the

Bass decrease produced by heating the ash and

crucible with an oxygen-gas flame plus subsequent

analysis for total occluded carbon. The carbon in

the ash ranged from 0.015 to 0.1% of the initial

sample mass.

A small amount (<1mg) of white residue was depositeo on the thermal shield during each run. In

about one-half of the experiments, the water con- densed in the trap (see Fig. 2) was greenish blue

rather than clear. The trap also contained some

black residue. Apparently this was trapped fly

ash which had partially dissolved. Analysis

showed that no carbon was present in the residue

and that the colored solution contained Fe, Cr,

Ni, Na and K (i.e. in the range of 100 ng/ml) in

addition to the usual acidity (0.1 to 0.2 milliequivalents per milliliter).

The provisional calorimeter setup was calibrated

by burning five pellets of RDF-4 (Lot 1) whose

energy of combustion had been determined

previously with a gram-size bomb calorimeter at

KBS. The enthalpy of combustion of a different

RDF-4 (Lot 2) was measured in six experiments.

The imprecision of the flow measurements on Lots 1 and 2 were 0.9 and 1.2%, respectively, at the 95%

confidence level. (The corresponding imprecision

obtained with the bomb calorimeter for four

samples of Lot 1 was 0.fa% and for four samples of

Lot 2 was 0.5%). The ratio of the two enthalpies

measured by the' flow technique was 1.009 with an imprecision of 1.5% and an uncertainty (which

includes estimated systematic errors) of 2.7%. The

corresponding ratio for the bomb calorimeter data was 1.027 with an imprecision and uncertainty of

1.0%. The ratios agree within their combined

uncertainties. The uncertainty of the flow ratio

is greater than its imprecision because of the errors associated with the residual moisture

determination for each lot. We believe the major error in the flow measurements is in the correction for heat leak applied

to the observed temperature rise; corrections

ranged from -0.7 to 4% of the observed rise. The

corrections assume that the temperature of the

calorimeter environment is held constant and that

steady-state heat transfer between the calorimeter

water and the environment is achieved rapidly.

These conditions were not met by the provisional

setup.

Other significant corrections and their approximate magnitudes are : for CO formation (—0.6%),

for heat transport by gas flow (—0.4%), for vaporization of water (—1.6% for Lot 1 and —1.3% for

Lot 2 when inlet oxygen was saturated and— 4.3%

for dry inlet oxygen). No corrections for carbon

content of the ash or residue on the thermal

shield were made. The error Incurred is probably

less than 0.1%.

Benzoic acid was found to be unsatisfactory as a solid calibrant material for flow work. Pellets

melted and burned with a fuel rich flame that

produced large amounts of soot. Ultra-pure carbon

powder also proved to be unsatisfactory; it was

very difficult to ignite. Flame calorimetry calibrants (gaseous H 2 or CHj^) were not tested because

apparatus necessary for quantitative determination

(0.01%) of calibrants combusted was not available.

After the RDF-4 experiments, one gram pellets of pure cellulose were test burned in a similar combustor. The pellets ignited easily and burned

completely. Subsequently, bomb calorimetric meas- urements were initiated to establish the enthalpy

of combustion of this material so that it can be

used as a standard solid calibrant for the flow

calorimetry measurements.

III. TRIAL KILOGRAM COMBUSTIONS

A large combustor was designed to burn kilogramsize pellets of dried RDF-2. RDF-2 is municipal

solid waste which has been processed to reduce the

particle size so that 95 mass-percent passes

through a 15 cm square mesh screen. The burning

characteristics of the kilogram-size pellets in

oxygen were unknown and were expected to differ

from those of the 25 gram pellets. The kilogramsize pellet composition was more variable and the

physical heterogeneity measured against the sample

size was greater than the 25 gram pellet.

The goal of the trial experiments was to develop a method for completely burning 2.5 kg samples in

approximately 40 minutes or less. This time limit was estimated to be the maximum time which would

guarantee that the imprecision contributed by the

calorimetric measurements would be less than one percent.

Trial combustions of samples up to 2.2 kg of RDF-2 were carried out in a burner cooled by convective

and radiant heat losses to ambient temperature.

The burner was mounted in a large exhaust hood.

The burner design was similar to that used in the

25 gram experiments in that thermal shields were employed to keep the hot, reacting, combustion

product gases from being cooled by contact with

the outer burner walls. The combustor differed

from that used in the 25 gram experiments in that

all of the oxygen was supplied locally to the

sample; no oxygen flowed between the thermal

shield and the cool combustor walls. Oxygen was supplied in the form of high velocity Jets which

were directed either at the top of or the side of

the sample or both depending on the experiment. A diffuse, slower, flow of oxygen was directed up- ward at the bottom of the sample.

The combustor, as it appeared in the first of the

trial burns, is shown in cross section in Fig. 4. The unit consists of two chambers. The lower chamber, which was the cylindrical region enclosed by

158
)

Figr H. The 2.5 Kilogram Combustor.

Kotations; A denotes the stack, B the

upper thermal shield, C the upper

burner Jacket, D the annular plate, E the lower burner jacket, F the secondary oxygen inlets, G the support rod, H the sample support and I the primary

oxygen inlet.

the lower burner Jacket (E of Fig. *<), contained

the sample and two oxygen supply Inlets. The

sample was supported on vertical stainless steel

pins which fit into the holes of a porous stainless steel plate (H). This support system was

analogous to the quartz plate of the 25 gram

combustor. Primary oxygen was supplied to the

bottom of the sample from the inlet I. Secondary

oxygen was directed at the top of the sample by

three Jets aimed radially and horizontally by the

inlet F. The intent of the sample-oxygen supply

arrangement was to mimic as far as possible the 25 gram flow experiments while maintaining an unobstructed view of the combustion. Hence, no crucible was used.

The thermal shield (B) of the upper chamber and

upper burner jacket (C) sat on a annular steel

plate (D) which was supported by three rods (G) that projected through the lower chamber to the

concrete floor. The annular plate also supported

the lower burner jacket which was bolted to the

plate around two-thirds of its circumference.

For access to the lower chamber, one-third of the

circumference of the lower burner Jacket was a semi-cylindrical door. Two Pyrex glass viewing

ports (not shown in Fig. 4) were installed in the

door so that the course of a combustion could be

observed.

Oxygen was supplied to the primary and secondary

inlets in the lower burner Jacket by independent

sources, each consisting of three standard 6,200

liter (STP) oxygen tanks equipped with reducing

valves and connected in parallel. Flow rates were measured with variable orifice flowmeters. A product gas analysis train similar to that used in

the 25 gram experiments was used to monitor the CO

and CO2 production.

Temperatures' were monitored at as many as twelve

different locations using 18 gauge Type K thermocouples.

The RDF-2 from which the sample pellets were made

was obtained from the Teledyne National Resource

Recovery Facility in Cockeysville, Maryland where

municipal solid waste of Baltimore County is

processed. Lots were withdrawn at random from the

conveyer belt leaving the primary shredder. At MBS, the large nonconbustibles were removed and

the remainder was dried in air at 105°C for 12 to

1b hours. Sample pellets were made by compressing

the dried RDF-2 in a cylindrical die piece with a force ranging from 265 to 625 kN. A single

compression yielded a pellet with reasonably good

adhesion of the various heterogeneous horizontal

layers. This adhesion was not improved by wetting

the material with water prior to pressing. The

finished pellet had a diameter of 22 cm and a height of about 6 cra/kg sample mass. To test the

effect of increased surface area, three or seven

vertical holes were drilled in some of the pellets

using a metal drill and Jig to hold the sample.

One cellulose pellet was made by pressing pure

cellulose fluff using the same technique.

159
In all, eighteen experiments were carried out to

test the effectiveness of: (1) various arrange- ments of primary and secondary oxygen inlets, (2) preheating the oxygen, and (3) reducing heat loss- es from the sample by the use of a crucible and a radiation shield. Thirteen experiments were run with RDF-2 pellets. Five experiments were run with

pure cellulose or its substitute (a stack of un- glazed paper plates).

Changes in the apparatus made as a result of these

tests are illustrated by Fig. 5 which shows the

configuration of the lower chamber of the combustor used in the final two experiments. An RDF-2

sample with seven vertical 2.5 cm diameter holes sat on a horizontal lattice of alumina rods

which rested on a stainless steel support (see D of Fig. 5). Two tiers of secondary oxygen inlets

(B and C) were aimed radially inward and horizontally at the side of the pellet. The lower tier of

Fig. 5. The configuration of the lower chamber of

the combustor for experiments 17 and 18. Notations: A denotes the lower thermal

shield, B the upper tier of secondary

oxygen inlets, C the lower tier of

secondary oxygen inlets, D the sample

support, E the primary oxygen inlet,

F the lower tier preheat coil, C the

multiport ring oxygen inlet, K the

iron fuse, I the upper tier preheat

coil and J the crucible lid.

six inlets was supplied with oxygen that was preheated by passing it through coiled tubing (F)

which was wound on the outside of the crucible.

The upper tier of three inlets was supplied with

oxygen that was preheated by passing it through

the coll (I) which was inside of the crucible.

Oxygen was supplied to the bottom of the sample

from the primary oxygen inlet (E). Most of the

ash falls through the center of the inlet to the

bottom of the crucible. A radiation shield which

just fits the inside diameter of the annular steel

plate (D of Fig. *4) has been placed around the

crucible to reduce heat losses.

Back flow of the product gases between the crucible side and the lower thermal shield was prevented by a low upward flow of diffuse oxygen from the

multiport ring inlet (G of Fig. 5). Rectangular

openings were cut in the crucible and thermal

shield in order to observe the combustion. A Pyrex

window covered the opening in the thermal shield.

In a typical experiment, the combustor was flushed

with oxygen for ten minutes. The sample was then

ignited by passing electrical current through an iron fuse wire (H of Fig. 5) touching the top of

the sample. The flow rates were adjusted to pre- selected initial values for the experiment. Primary and secondary oxygen flows were varied to study the effectiveness of different rates and

inlet arrangements. The ratio of diffuse to directed flow was of the order of 3:1 or greater and

the total flow rate ranged between 3.5 and 11 moles per minute. At the end of the burn, the

combustor was flushed with oxygen and allowed to cool. The ash was collected and weighed. The ash

contents of RDF-2 pellets ranged from 15 to 32 % of

the initial mass and no unburned organic material was identified in the ash.

In general the most rapid burning of the sample

occurred on the areas where the secondary jets of

oxygen struck the sample. As the secondary flow

velocity was increased, these areas became white

hot and the flame became ever more turbulent.

Above a critical flow rate, the sample began to fragment vigorously with significant scattering

of burning matter and ash. As the temperature of

the preheated secondary oxygen was increased, the

flow rate at which these changes occurred was

lowered. Intense burning occurred in the vertical

holes, when present. Bright columns of flame were

observed above the holes.

No distinct glow period, analogous to that of the

25 gram samples, was observed. However, CO production tended to be larger during the combustion of

the last quarter of the sample. The fraction

combusted at any time was assumed to be the ratio

of CO^ produced up to that time divided by the

total COp production. The ratio of total CO to

CO

2 ranged from 2 to less than 0.1 molj. The time

required to burn the last quarter of all RDF-2

samples was always longer than that required to burn the first three quarters of the sample. This was due to thie presence of noncombustibles which

tended to inhibit the combustion of the last quarter of the unburned material. Peak temperatures

160
of the exhaust gases at the exit stack ranged from

365 to 500°C, depending upon the experiment, and

occurred before half of sample had been combusted.

The flame temperature above the sample was

determined to be in excess of 1*<00°C. The peak

temperature of the combustor components nearest

the sample ranged from 500 to 1200°C for the top

of the primary oxygen supply and *4^40 to 500°C for

various parts of the crucible and lower thermal

shield. Only surface corrosion of the these

components occurred and this appeared to be

minimal after one or two experiments. Actual

ignition of the combustor components only took

place when the burning sample fell from its sup- port and came into contact with the oxygen inlets.

The total burn time of RDF-2 pellets was reduced

from 77 minutes per kilogram initial mass in the

early runs with the experimental arrangement

illustrated in Fig. ^ to an acceptable 15 min/kg

using the arrangement of Fig. 5. As more than one change in sample and/or combustor configuration

was made in each trial experiment, interpretation

of the effects due to the individual changes

tends to be somewhat ambiguous. However, we draw

the following conclusions: (1) The introduction of

a crucible (having a side wall one half the height

of that shown in Fig. 5) caused a reduction in

burn times for RDF-2 pellets of 33?. (2) The

Introduction of vertical holes reduced burn times

between 10 and 50?. (3) Burn times for a single

tier of lower secondary oxygen inlets (equivalent

to C of Fig. 5) were about 50? less than those

obtained using a single tier of upper secondary

Inlets (which were directed downward at a 45°

angle toward the top edge of the pellet).

We found that cellulose pellets were easily ignited and burned smoothly leaving negligible ash.

Burn times for cellulose samples were up to 50?

shorter than those for RDF-2. Cellulose appears to

be a satisfactory potential calibrant.

IV. 2.5 KILOGRAM CAPACITY FLOW CALORIMETER

The final design adopted for the large scale calorimeter is illustrated in Fig. 6 with dimensions

of interest presented in Table 1. Stainless steel

(type 304), will be used in the fabrication of all

components except as noted.

The combustor (A of Fig. 6) will incorporate all

of the features which were evolved during the

trial burns plus additional ideas which we were

unable to’ test completely due to the various

constraints. The sample pellet is to be supported

by a ^parallel horizontal lattice of alumina rods

held by notches in the upper edge of the pan in

which the ash is to be collected. The bottom of

the ash pan will be covered by a layer of sand to prevent its Ignition if large pieces of burning

sample fall on it. Three independent tiers of up to six secondary inlets each (not shown in

drawing) will penetrate the wall of the combustor

in the region surrounding the sample. A similar

tier of six inlets will also penetrate the ash

pan to provide oxygen flow beneath the sample.

1 METER H

Fig. 6. The 2.5 Kilogram Capacity Flow Calorimeter. Notations: A denotes the combustor, B the

combustor enclosure, C the exhaust

cooling colls, D the exhaust condenser, E the flow shield, F the calorimeter vessel, G the stirrer and H the water-wall Jacket.

161
This arrangement replaces the primary inlet of the

trial combustor and overcomes the awkward ash

recovery procedure used during the trial burns. An annular disk divides the combustor into two

zones. The diameter of the combustor (41 cm) and

space betweeen the sample pellet and the annular

disk (15 cm) are comparable to the dimensions of

the crucible and lid arrangement shown in Fig. 5. An additional tier of six oxygen inlets is to be

placed in the upper zone. All oxygen can be

preheated in coils welded to the outer wall of the

combustor. Provision is made to introduce one or more interior preheat coils in the lower zone of

the combustor if desired. Initially the entire

combustor is to be made from 316 stainless steel

with welded construction and gas-tight seals at

the flanges. The various oxygen inlets will be

sealed at the combustor wall.

The combustor enclosure (B) is to be filled with

argon which will provide a clean, inert environ- ment in which all tubing and connections as well as electrical and thermocouple wiring will be

protected.

The combustor enclosure and exhaust cooling coils

(C) will be immersed in the calorimeter water held

by the calorimeter vessel (F). There will be

three complete turns of the cooling coils preceding the exhaust condenser (D) and seven turns

before the exit from the calorimeter vessel. The

exhaust cooling coils and the exhaust condenser

will be made from Incoloy 825.

The flow shield (E) and stirrer (G) are designed

to circulate the calorimeter water completely

throught the vessel about once in five minutes.

For a 2.5 kg pellet of pure cellulose, we expect a temperature rise of about 10°C.

To reduce the total mass and volume of the assembly, we plan to enclose the calorimeter vessel

with a water-wall Jacket (H). Water from a thermoatatted reservoir will be circulated through its

walls to provide the necessary constant temperature environment for the calorimeter. The Jacket

replaces the submarine vessel and lid (cf. H and I of Fig. 2) and the therraostatted, st irred-water

bath into which the conventional isoperibol calorimeter is immersed. The water bath and submarine

for a calorimeter of this size would weigh about

2800 kg.

Assembly and testing of the 2.5 kg Capacity Flow

Calorimeter is scheduled to begin in the fall of

1981.

TABLE 1.

2.5 kg CAPACITY FLCW CALORIMETER

Dimensions of Main Components

Component Height

Outside

Diameter

Wall

Thickness

Total Mass

(cm) (cm) (mm) (kg)

Combustor 155 41 3.2 74

Combustor 163 61 4.8 196 Enclosure

Flow Shield 213 79 1.6 73

Calorimeter 236 91 4.8 390

Vessel

Water-Wall 244 102 25. 454

Jacket

Additional Specifications

Calorimeter Water 983 liters

Heat Capacity 322 kJ/K (Assembly)

4111 (Water)

4433 kJ/K (Total)

162
Appendix VII

A LABORATORY APPROACH TO OBTAIN SUSPENSION

COMBUSTION DATA FOR REFUSE-DERIVED FUELS

A. Macek and S.R. Charagundla

Thermal Processes Division

U.S. National Bureau of Standards

Washington, D.C. 20234, U.S. A.

ABSTRACT

The objective of this research project is laboratoryscale measurement of burning rates of entrained RDF samples.

The resulting data are expected to be relevant for estimating

the characteristics of (a) pulverized-fuel combustion and (b)

the suspension fraction of spreader-stoker combustion. A

furnace is described allowing direct measurement of fuel-particle

burning times as functions of the parameters of the entraining

gas flow. Preliminary results on combustion of a pulverizedcoal sample in that furnace are presented. Inasmuch as RDF

samples consist of particles having a wide variety of sizes,

shapes, and densities, an ancillary study of entrainment characteristics of these samples has been made in a cold-flow elutriation apparatus constructed for that purpose. Settling

velocity data are presented (a) for particles of controlled

sizes, shapes and densities representative of RDF and (b) for

two screened fractions of an RDF sample. These results will

be used in subsequent RDF combustion studies.

I . INTRODUCTION

Over the years a large amount of information has become availablj_^n

various aspects of coal combustion in small-scale laboratory furnaces

This information forms a body of basic data which a combustion engineer can draw upon as a rough but very useful guide for prediction of coal combustion

characteristics in industrial boilers and furnaces. Among the most important data available from laboratory experiments are fuel burning rates as functions of both fuel properties and parameters of gas streams surrounding

the fuel particles. This information is required for estimation of key

boiler parameters: rate of heat release, furnace retention time, and

furnace outlet temperature.

The equivalent laboratory information does not exist for refusederived fuels (RDF). The objective of the present project is to fill some

163
of the gaps in the data base in this area, specifically for combustion of

RDF particles in suspension. The data are thus expected to be relevant to

(a) pulverized-fuel combustion and (b) the suspension fraction of spreaderstoker combustion.

This is the first progress report on the project. It includes (a) a statement of the need for and the rationale of laboratory experiments, (b)

description of the laboratory equipment, and (c) the results to date.

of particle burnout in suspension. A recent estimate based on modelling

indicates that the RDF char may not be completely burned in 2 seconds of

fuel residence time in the furnace even for very small fuel particle sizes

(about 1.5 mm diameter). Indeed, practical boiler and incinerator operations frequently indicate particulate carryover from furnaces; it must be

mentioned however, that most of these observations refer to larger initial

particle sizes. The problem is not confined to RDF. Combustion of wood

waste fuels can also lead to extensivg particulate carryover, as shown by

both practical and analytical studies *. The common problem with these

waste fuels is that they consist of irregularly shaped particles, even the

initial density of which is low compared to that of coal. The density of

the solid particles (char, ash) remaining after devolatilization is

exceedingly low, so they tend to elutriate rapidly with incomplete combustion. Thus, the entrainment of fuel particles also requires

characterization

The experimental approach to the problems of fuel particle entraiiunent

and combustion in our laboratory is being carried out in two units, a furnace and an elutriation apparatus. This equipment is described in

Section III. Here, we outline only the basic concepts of their use.

Combustion is being studied in a furnace, the basic function of which

is to supply a uniform ducted gas stream simulating the temperature and the

chemical composition of spreader-stoker or pulverized-fuel boiler gases*.

Pulverized fuel is injected into the furnace in a stream so dilute that its

combustion does not alter significantly the parameters of the hightemperature gas stream. Thus, the range of burning times of a fuel sample

is determined in each experiment as a function of a given set of gas

composition and temperature, constant throughout the experiment. The direct

objective is to obtain particle burning times as function of (a) the fuel

parameters (particle size, heating value, ash content, etc.) and (b) the

gas-stream parameters (primarily temperature, concentration of oxygen, and

particle Reynolds number). The ultimate objective is to provide a sufficient body of burning-rate data for modelling of particle combustion in

large-scale (pilot or field) furnaces where compositions and temperatures

of gases surrounding the fuel particles generally vary continuously from

ignition to burnout.

The fact that RDF consists of particles having a variety of shapes and

sizes introduces a serious problem of entrainment characterization. The

problem can be stated by comparison of RDF with coal. In view of the

reasonably uniform shapes of pulverized coal particles (all three

II. EXPERIMENTAL APPROACH

An important problem attending the combustion

164
dimensions being of the same order of magnitude) , the double-screening of

the material produces a sample of reasonably well defined average diameter

and with suitably narrow size distribution. This simple sample preparation

technique allows two a priori estimates: (a) the entrainment characteristics (e.g., the limiting settling velocity in the surrounding gas) and (b)

the burning time. In a diffusion-limited regime the latter quantity can t^en

be calculated from the particle diameter well within an order of magnitude . No such correlations can be made for RDF, because the sieving of the material produces a sample with a very wide range of entrainment characteristics. Thus even prior to any attempt at estimating particle combustion

rates one is faced with the problem of the entrainment characteristics of

RDF samples

To address the entrainment problem, we designed and constructed a coldflow elutriation apparatus . The function of the apparatus is to separate

particles of any given sample into several fractions, each characterized by

its limiting settling velocity which, in turn, is determined by a combination of three properties of particles: size, shape, and density. This

approach is useful for two reasons: (a) it defines an operational procedure

for defining RDF samples, equivalent to the customary "size cuts" which suffice for definition of samples of regularly shaped particles (ideally only

spheres of constant density, but practically also materials such as pulverized coal); (b) it allows, by means of engineering correlations, an estimate of the fraction of RDF settling in applied combustion tests which

use larger particle sizes.

III. LABORATORY EQUIPMENT

A. Combustion Apparatus

1. Furnace

A schematic representation of the laboratory furnace with its

auxiliaries is given in Fig. 1. The outer structural support is mostly

made of stainless steel. The shaded areas represent refractory lining. The

assembly consists of (a) a turbulent propane/air burner which supplies a hot (essentially adiabatic) primary stream of combustion products, (b) the

mixing /diffuser sections where the burner products are mixed with a cold

^ secondary diluent and expanded into a cavity having an area of about 130 cm , and (c) the furnace itself, which also has about the same area. Windows

made of high-temperature glass extend over almost the entire front and rear sides of the furnace. The furnace is separated from the upstream sections

either by a porous refractory plate or, interchangeably, by a perforated

stainless-steel distributor.

The temperature and the composition of the gas flowing through the

furnace are varied by use of different diluents (usually oxygen or air) and

by variation of the primary/secondary gas stream ratio. The most useful

ranges of the two key fumace-gas parameters so far have been: temperature

from 850 to HOOK and the oxygen content from 10 to 40%. Temperatures are measured as described in Section III A 2. Furnace-gas compositions are assumed to be the result of complete combustion of propane, i.e., to consist

entirely of N^, 0_, H

2

O, and CO

2

. Gas velocities in the furnace, typically, are 50 to 75 cm/sec. These flow velocities have been adequate for

165
the work done so far. Minor modifications of the furnace are planned

allowing the flow velocities to be increased to about 150 cm/sec. Under

all these conditions the gas flow will remain laminar.

Fuel particles are injected into the furnace horizontally through side

ports. In the preliminary runs with coal particles (see Section IV A) we found it convenient to locate the injection port at least half way (18 cm or more) above the bottom of the furnace, because larger particles in the

sample tend to fall initially, due to gravity, and then rise when ignited.

The requirements for injection of reasonably uniform, controllable

streams of particles without agglomeration are always demanding and had to

be addressed with care. No suitable commercial injectors appear to be available. The feeder constructed in our laboratory out of a transparent

plastic, shown in F^g.^g, is a modification of designs reported in the

research literature ’. The two functions of this instrument are (a) gengeneration of a suspended cloud of separated particles by fluidization and

(b) transportation of particles by a carrier gas, usually nitrogen. These

functions are accomplished by separate regulation of two gas streams: the

fluidizing stream and the carrier gas. It was found that agglomeration,

largely due to electrostatic charges, is minimized by vibration of the

horizontal transport tube.

The feeder has been found to operate adequately with pulverized

bituminous coal, lignite, and RDF over a range of particle sizes having

diameters around 100 Vim. Variations of the two feeder gas streams allows a wide variation of mass injection rates of the fuel. The particle size

range of this instrument is satisfactory for completion of the work with

bituminous coal and lignites. The design for a further modification for

larger RDF particles has been completed and the feeder is under

construction.

2. Temperature Instrumentation

The furnace assembly has been Instrumented for temperature measurement

at a number of stations by means of Chromel-Alumel thermocouples with t digital readout.

The highest upstream section where the temperature is measured is the

plenum just upstream of the distributor plate. The main purpose of this

measurement is to ascertain that the temperature distribution is uniform

over the cross-section. Continuous temperature monitoring at two stations

in that section, at the center and near the side-wall respectively, shows

that the requirement of uniformity is satisfied when the walls are hot.

Normal heat-up period for operation of the furnace is about 20 minutes.

Temperatures in that area are typically maintained between 1250 and 1400K;

the readings of the two thermocouples are normally within lOK or less of

each other. The farthest downstream thermocouple (not shown in Fig. 1) is

located in the stack, mainly for safety. None of these three thermocouples,

although rather large (28 gauge wires, corresponding to about 0.8 mm bead

diameters) , present problems of radiation correction. This is so for two

reasons. First, accurate values of temperatures at these three stations,

while useful for characterization of the furnace performance, are not

needed for measurement of combustion parameters. Second, the assumption

166
that the gas temperature equals the bead temperature in these sections is

good, because the two upstream stations are inside a radiating cavity and the

downstream station is in a gas stream at high velocity (> 1000 cm/sec.) and

low temperature (600K or less)

On the other hand, thermocouple measurements inside the furnace require

a significant correction because of high temperatures, low gas velocities,

and relatively low radiant surroundings at most measurement stations.

Direct estimates of radiant losses are difficult, because the effective temperature of surroundings is unknown and, furthermore, it varies with the

location in the furnace: it is relatively high near the bottom of the

furnace because of the proximity of the highly radiant distributor plate, but

it decreases toward the top of the furnace. However, since the temperature

loss due to radiation is proportional to the diameter of the radiating body, a good semi-empiral correction can be made by recording the temperature at

each measuring station with two adjacent thermocouples with spherical beads

of two different diameters, d^ and d^. The procedure for obtaining the gas

temperature from such measurements wxll now be described briefly.

The relationship between the gas temperature T and the (measured)

thermocouple bead temperature T^ in a given convectfve and radiative regime

can be written

Tg = T^ + ade^T^^(l-n)/(k Nu) (1)

where the emipirical parameter Ti can be thought of as a "view factor", i.e.

the fraction of the solid angle around the measuring station having a high

radiant temperature. Other symbols are defined in the Glossary. As ri approaches unity, the correction in Equ. 1 vanishes; as explained earlier

this is the assumption made for the cavity upstream of the distributor plate

(T = T^) . The othjj extreme assumption, n = 0, is usually made in open

no§-lumxnous flames

Inasmuch as both Nu and f) are only weak functions of the bead diameter,

we found it convenient to rewrite Equ. 1:

T = T^ + K d (1*)

g b b

where K = e^a(l-ri)/k Nu is assumed to be the same for any thermocouple at a given location in a given gas stream (varying, of course, from location to

location and for different gas-stream parameters) . Simultaneous recording

of two temperatures T^^ and T^2 thermocouples with bead diameters d^ and

d

2 respectively allows elimination of K from the set of two resulting

equations (1*). The expression for gas temperatures becomes:

T

g

+

T - T bl b2

(d2/di) (Tb2/Tbi) -1

( 2 )

r The term T^^ - T^2 usually a small difference of two large numbers,

leading to low accuracy from Equ. (2) . For example, it has been found that

for gas temperatures around lOOOK near the bottom of the furnace (large ri) ,

167
and the two bead diameters of 0.32 and 0.81 mm, is only about

25K. A refinement of the instrumentation was therefore°made, allowing

direct electronic readout of this difference, resulting in satisfactory

measurement of the gas temperature.

3. Photography

Injection of fuel particles into the furnace gases follows the

predictable visual pattern: a dark area between the point of injection and

the point of ignition corresponds to the pre-ignition heat-up time. Once

ignited, each particle gives rise to a bright trajectory from ignition to

burnout appearing as a bright streak in time-exposure photographs. Inasmuch

as, in the work to date, the particle burning times have been small fractions

of a second, each snapshot with photographic exposure times of 1 to 2 seconds

is sufficient to capture records of many burning particles. Burning times of

individual particles are obtained by means of a mechanical light-chopper

interposed between the camera and the furnace window. This technique had

been shown previo^^ly to give accurate time-resolved measurements on single

burning particles

The useful light-chopping frequency range so far has been from 200 to

1000 Hz. This range can be extended, if needed, up to 4000 Hz and down to

arbitrarily low values. In reading the photographic records care must be

taken to ascertain that the streaks modulated by the optical frequency

represent the entire burning time of the particle; i.e. they must include

both ignition and burnout, unaffected by the opening or the closing of the

camera shutte^.

B. Elutriation Apparatus

The cold-flow elutriation apparatus consists of a set of constant-area

tubes (A, C, E) and tapered transition sections (B, D, F) with appropriately small angles to prevent flow separation, arranged in the sequence

shown in Fig. 3. All sections are made of transparent plastic. Care was taken to have smooth internal surface (by buffing) and smooth transitions

between sections. :

During the operation a metered stream of air is passed through a flow

straightener and introduced at the bottom of the apparatus. A removable

particle collector is located at the top (exit) end of the apparatus.

Particles are introduced before each run, and replenished during the run

as needed, through the top by temporary removal and replacement of the

collector.

IVo modes of operation of the apparatus have been developed: one for

prepared samples consisting of particles having the same size and shape

(discs of paper or metal foil, blocks of wood, etc.); and the other for

heterogeneous samples, such as RDF.

To determine the entrainment characteristics of controlled shapes and

sizes the flow rate in the apparatus is increased until the particles

stabilize first at Station I and then at Station II. At low Reynolds

numbers this happens at two different mass flow rates, corresponding to

the same linear flow velocity. This, by definition, is the settling

168
velocity of the sample. In view of the fact, however, that the entrainment

regimes of interest to this project extend into the range of high Reynolds

numbers where vortex shedding and instability occur (see Section IV B) , such

simple determination is not always possible. Under conditions of unstable

flow the particles, having reached a height in the apparatus, tumble to

lower levels and rise again repeatedly. Under these conditions the flow is

adjusted until the particles attain their peak position at Station I or II.

Thus the minimum settling velocity of the sample is determined (which is

the important parameter in characterizing the carryover in suspension

combustion)

A modified procedure had to be developed to handle heterogeneous

samples, where the size (sieve) fraction alone is insufficient for

characterization of entrainment, because shape and density matter as well

(see Section II) . To characterize such samples the flow rate in the

apparatus is first increased until the most entrainable fraction becomes

suspended at Station I; this yields the first (lowest) settling velocity.

The flow is then further increased until a "heavier" fraction is suspended

at Station I; the lighter fraction moves to Station II or beyond to the

collector at the exit. This procedure, which can be extended to several

flow-rate increments, depending on the heterogeneity of the sample, gives

two results: (a) settling velocities for direct use in both laboratoryscale and large-scale combustors; and (b) collection of actual samples at

the exit for further use in the laboratory (examination and combustion)

IV. RESULTS TO DATE

A. Preliminary Coal Combustion

The first combustion task in this project deals with pulverized coal as the fuel. The reason for including this task is twofold. First, an important objective of the project is to determine differences in suspension

combustion of RDF relative to coal (both bituminous and lignites) , so a "baseline" study of coal is necessary. Second, inasmuch as a substantial

body of data exists with bituminous coal, obtained by different laboratory

techniques, the comparison of our results on this fuel with the previously

available information provides a good way of characterizing the performance

of our furnace.

To characterize this performance samples of bituminous coal have been

injected into furnace gases with varying compositions and at various

temperatures. At any given gas temperature the particle brightness increased and the particle burning times decreased with the oxygen content in

the furnace gas, which was thus found to be a major furnace variable

determining the burning time, as expected. In fact, at gas temperatures

around lOOOK the decrease of oxygen content below 10-12% by volume gave rise

to long, low-luminosity particle trajectories, possibly indicating the

transition from the diffusion-controlled to the slower kineticallycontrolled regimes.

In view of the facts that (a) there are indications that in our experiments at low oxygen content the observed burning times correspond to

only partial combustion of carbon (combustible matter was collected in the

cyclone) and (b) ^ priori calculations of particle burning rates in kinetic

169
regimes are highly uncertain, we make a comparison of our observed data with

the calculation for a specific case of combustion of a sample of pulverized

bituminous coal in oxygen-rich gases (obtained by use of oxygen as the

secondary diluent; see Section III A 1).

The data used for the comparison are as follows:

coal particle diameter 68 pm

gas temperature 1020K

©2 in furnace gas 38%

average burning time 14 msec

The value of the particle diameter was adopted, because the sample was sieved between 200 Mesh (74 pm) and 230 Mesh (62 pm) screens; it is only a rough approximation to the equivalent sphere diameter. The other

quantities are laboratory data determined as described in Section III A.

be^ J^e theoretical expression for the particle burning time was taken to

pD . 2

16MRTP p

(3)

This expression assumes that the combustion reaction at the surface of the

particle is C + 1/2 O

2

CO. The effective temperature in the diffusion

field was taken to be 1750K, a rough average of the measured free-stream

and estimated flame-front values. This calculation gives a theoretical

burning time of 18 msec. In view of the crudeness of assumptions this

close agreement with the experimental burning time must be considered

fortuitous

The above preliminary study shows that the laboratory combustion equipment and the experimental procedures described in this Section are suitable

for attainment of the objective of this project, i.e., the determination

of particle burning time, T = f (d , T , 0„)

P 8 ^

B. Entrainment of Particles

We are not aware of any data on RDF Particle entrainment in the form

required for determination of two numbers required for application in

combustors: the fraction of the fuel suspended by the gas stream and its

residence time in the furnace. There^^xi|^s a good data base for spherical

particles , mostly at low temperatures There are also correlations

permitting estimation of entrainment data for non-spherical particles

However, the accuracy of such estimates is questionable.

i§?"i6

We, therefore, present the entrainment information under two headings;

(a) theoretical estimates for spherical particles, which are not realistic

for RDF, but are useful as baseline comparison with coal and (b) experimental

data on non-spherical particles obtained in our laboratory.

170
1. Spherical Particles

It must first be noted that densities of RDF constitue^t^^atjgials may

vary by an order of magnitude. A few examples (in grams/cm )

’

:

wood (oven dry)

plastics

paper

glass

0.12 - 1.23

1.05 - 2.09

0.7 - 1.15

2.4 - 5.9

Entrainment velocities of such materials will now be estimated for

typical boiler conditions: T = 1370K (2000“F) and U = 750 cm/sec (30

ft/sec). The maximum sizes of (spherical) particles intrainable under these

conditions are large enough to be in the Newton’s law range: 750 < Re < 3.5 X 10 . In this regime, the drag coefficient is almost constant,

C <0.445, and the terminal velocity U (cm/sec) of a particle of diameter

d (cm) is:

= 1.73 [gd(Pp/Pg - (4)

Thus the diameter of the largest particle entrainable in a combustor stream

is

= (U/1.73)^ * (P /P„g) (5) max g p

where U is the velocity of the gas stream.

The data for coal and for several materials which may be typical

constituents of RDF, calculated by Equ. 5, are shown in Table I. It can be

seen that the estimated entrainment characteristics of RDF constituents

would not be grossly different from those of coal, if the particles were

spherical. However, the consideration of the shape factor may change these

numbers by orders of magnitude.

2. Non-Spherical Particles

Terminal velocities of a variety of particles have been measured in our cold-flow elutriation apparatus by the procedures described in Section III B.

The performance of the apparatus was checked by determination of the

suspension velocity of spherical glass beads, 1 mm in diameter. The

experimentally found velocity is 670 cm/sec. The theory (Section IV B 1)

predicts 780 cm/sec. In view of experimental uncertainties (the exact

shape and density of the spheres, etc.) the agreement is satisfactoiTr.

The experimental data for various controlled (non-spherical) shapes

and for two screened RDF samples are collected in Table II. In a few

relatively low-velocity cases the flow regime corresponded to Re < 100.

However, in many cases the particles gave a clear appearance of insta

bilities (tumbling, oscillation) as should be expected in the Newton regime

(vortex shedding, etc.)

171
regimes are highly uncertain, we make a comparison of our observed data with

the calculation for a specific case of combustion of a sample of pulverized

bituminous coal in oxygen-rich gases (obtained by use of oxygen as the

secondary diluent; see Section III A 1).

The data used for the comparison are as follows:

coal particle diameter 68 ym

gas temperature 1020K

©2 in furnace gas 38%

average burning time 14 msec

The value of the particle diameter was adopted, because the sample was sieved between 200 Mesh (74 pm) and 230 Mesh (62 pm) screens; it is only a rough approximation to the equivalent sphere diameter. The other

quantities are laboratory data determined as described in Section III A.

theoretical expression for the particle burning time was taken to

pRT 2

16MDP p

(3)

This expression assumes that the combustion reaction at the surface of the

particle is C + 1/2 0^ CO. The effective temperature in the diffusion

field was taken to be 1750K, a rough average of the measured free-stream

and estimated flame-front values. This calculation gives a theoretical

burning time of 18 msec. In view of the crudeness of assumptions this

close agreement with the experimental burning time must be considered

fortuitous

The above preliminary study shows that the laboratory combustion equipment and the experimental procedures described in this Section are suitable

for attainment of the objective of this project, i.e., the determination

of particle burning time, T = f (‘ip* 'i’g* 02^*

B. Entrainment of Particles

We are not aware of any data on RDF particle entrainment in the form

required for determination of two numbers required for application in

combustors: the fraction of the fuel suspended by the gas stream and its

residence time in the furnace. There^^xi|^s a good data base for spherical

particles, mostly at low temperatures *

. There are also correlatj^ns^^

permitting estimation of entrainment data for non-spherical particles ’ However, the accuracy of such estimates is questionable.

We, therefore, present the entrainment information under two headings:

(a) theoretical estimates for spherical particles, which are not realistic

for RDF, but are useful as baseline comparison with coal and (b) experimental

data on non-spherical particles obtained in our laboratory.

172 8
1. Spherical Particles

It must first be noted that densities of RDF constitue^t^^atjgials may

vary by an order of magnitude. A few examples (in grams/cm )

’

:

wood (oven dry)

plastics

paper

glass

0.12 - 1.23

1.05 - 2.09

0.7 - 1.15

2.4 - 5.9

Entrainment velocities of such materials will now be estimated for

typical boiler conditions: T = 1370K (2000°F) and U = 900 cm/sec (30

ft/sec). The maximum sizes of (spherical) particles intrainable under these

conditions are large enough to be in the Newton's law range; 750 < Re < 3.5 X 10 . In this regime, the drag coefficient is almost constant,

C <0.445, and the terminal velocity U (cm/sec) of a particle of diameter

d (cm) is:

1.73 [gd(Pp/Pg - l)]^''^ (4)

Thus , the diameter of the largest particle entrainable in a combustor stream

is approximately

d = (U/1.73)^ • (P„/P„g) (5) max g p

where U is the velocity of the gas stream.

The data for coal and for several materials which may be typical

constituents of RDF, calculated by Equ. 5, are shown in Table I. It can be

seen that the estimated entrainment characteristics of RDF constituents

would not be grossly different from those of coal, if the particles were

spherical. However, the consideration of the shape factor may change these

numbers by orders of magnitude.

2. Non-Spherical Particles

Terminal velocities of a variety of particles have been measured in our cold-flow elutriation apparatus by the procedures described in Section III B.

The performance of the apparatus was checked by determination of the

suspension velocity of spherical glass beads, 1 mm in diameter. The

experimentally found velocity is 670 cm/sec. The theory (Section IV B 1)

predicts 780 cm/sec. In view of experimental uncertainties (the exact

shape and density of the spheres, etc.) the agreement is satisfactory.

The experimental data for various controlled (non-spherical) shapes

and for two screened RDF samples are collected in Table II. In a few

relatively low-velocity cases the flow regime corresponded to Re < 100.

However, in many cases the particles gave a clear appearance of instabilities (tumbling, oscillation) as should be expected in the Newton regime

(vortex shedding, etc.).

173

9
Clearly, the extremely wide range of elutriation velocities for the

RDF sample cannot be ascribed to variation in size and density only:

the shape is no doubt an important factor, as expected. A direct evidence

of this is that, after elutriation and removal of the more entrainable

fraction, the residue does not consist only of large, heavy particles, but

also contains small elongated pieces.

The above results indicate the continued use of the elutriation

apparatus for two purposes: physical separation of samples according to

their entrainment characteristics for laboratory combustion studies; and

development and/or confirmation of correlations (shape factors) for nonspherical particles. It is expected that the latter activity will lead to

estimation of terminal velocities for RDF samples in applied combustion

studies

ACKNOWLEDGEMENT

Mr. C. Bulik set up the electronic instrumentation associated with

temperature measurement and the time-resolved photography for recording the

combustion of particles.

GLOSSARY

D diffusion coefficient

d diameter

g acceleration due to gravity

k thermal conductivity coefficient (gaseous)

K parameter defined by Equ. (1*)

M molecular weight of solid fuel (carbon)

Nu Nusselt number

P pressure

R gas constant

Re Reynolds number

T temperature

U velocity

e radiant emissivity

D parameter defined by Equ. (1)

p density

O Stefan-Boltzman constant

T burning time

.Scv io s c iL. pt-s

b thermocouple bead

g gas

p particle

1,2 denoting two different thermocouples

174 10
Table I

Diameter of Largest Spherical Particles Entrainable

in Hot Gas Stream Flowing at 900 cm/s at 1370K

Material 3 Density, g/cm Diameter of largest

spherical particle

entrainable, mm

Newsprint 0.C7 1.1

Wood 0.44 1.7

Plastics, Rubber 1.2 0.61

Coal 1.5 0.47

Table II

Measured Velocity for Particle Suspensxon

Particle Velocity for

Material Density,

g/cm

Shape Size Suspension,

cm/s

Newsprint 0.66 cir. disc 0.635cm dia. X 0.0076cm 90

Xerox Copy Paper 0.75 cir. disc 0 . 635cm dia. X 0.01cm 104

Aluminum foil 2.7 cir. disc 0.635cm dia. X 0.0038cm 126

Index Card 0.78 cir. disc 0.635cm dia. X 0.023cm 184

Wood 0.44 rect. plate 0.6cm X 0.62cm X 0.16cm 357

Wood 0.44 sq. block 0.7cm X 0.7cm X 0.64cm 476

RDF 7 Irregular - 20 + ;35 mesh 13/546

RDF 7 Irregular -35 + 130 mesh 6/ 446

175

11
REFERENCES

1. M.A. Field, D.W. Gill, B.B. Morgan, and P.G.W. Hawksley, Combustion

of Pulverised Coal , BCURA, Leatherhead, Surrey, England (1967).

2. R.H. Essenhigh: "Combustion and Propagation in Coal Systems",

16th Symposium (International) on Combustion , p. 389. The Combustion

Institute (1977)

3. N.M. Laurendeau: "Heterogeneous Kinetics of Coal Char Gasification

and Combustion", Prog. Energy Combust. Sci. 4, p. 221 (1978).

4. J.O.L. Wendt: "Fundamental Coal Combustion Mechanisms and Pollutant

Formation in Furnaces", ibid . 201 (1980).

5. P.M Chang and L. Carlson: "Vertical Combustor for Particulate Refuse",

Numer. Heat Trans. , j4, 101 (1981)

6. M. Liu: "Factors Affecting Hog Fuel Boiler Emissions", British

Columbia Research Council, Rep. 2376, Vancouver, Canada (1976).

7. T.N. Adams: "Combustible Carryover Predictions for a Wood-Waste

Boiler", Comb, and Flame , 34 , 47 (1979).

8. M.F.R. Mulcahy and I.W. Smith: "Kinetics of Combustion of Pulverized

Fuel", Rev. Pure Appl. Chem. 19 , 81 (1969).

9. R. Friedman and A. Macek: "Ignition and Combustion of Aluminum

Particles in Hot Ambient Gases", Comb, and Flame , 9 (1962).

10. R.J. Hamor and I.W. Smith: "Fluidizing Feeders for Providing Fine

Particles at Low, Stable Flows", Fuel , 50 , 394 (1971).

11. R.M. Fristrom and A. A. Westenberg, Flame Structure , p. 151, McGrawHill, New York (1965).

12. A. Madek and J.M. Semple: "Combustion of Boron Particles at

Atmospheric Pressure", Comb. Sci. Tech. , 1^, 181 (1969).

13. H. Schlichting, Boundary Layer Theory , McGraw-Hill (1962).

14. R. Clift, J.R. Grace, and M.E. Weber, Bubbles, Drops, and Particles , Academic Press, New York (1978).

15. H. Wadell, J. Geol. , 310 (1933).

16. H. Heywood, Symp. Interaction Fluids and Particles , Inst. Chem. Eng.,

pp. 1-8, London (1962).

17. Handbook of Chemistry & Physics , 30th ed. , Chemical Publishing Co.,

Cleveland (1948)

18. Smithsonian Physical Tables , 9th ed., Smithsonian Institution,

Washington, D.C. (1954).

176 12
Rg. 1; Laboratory furnace. TC Thermocouple

177
PARTICLE STREAM PURGE GAS

Fig. 2: Partide feeder

178
I EXHAUST

179
Appendix VIII

UNITED STATES DEPARTMENT OF COMMERCE

National Bureau of Standards

Washington. D.C. 20234

September 28, 1981

MEMORANDUM FOR The Record

From: Joseph G. Berke

Subject: Progress Report #1 on IPA

This progress report covers the period of September 8 to 11, and the

several meetings in the area, prior to officially starting at the

State Solid Waste Board on September 14.

On September 9 a meeting was held with the DoC-ITA trade specialists

in the region 9 office. They were Mr. Francis Caff rey and Mr. George

Dolan (addresses attached). The meeting was requested by Mr. Caffrey

while I was still at NBS. The purpose was to learn of the IPA

assignment and what I was to do. After reviewing the assignment the

discussion moved on to a major problem they often encounter. Many of

the companies they deal with often request standards and

specifications from the various countries to whom they wish to export

their products. To date, they have tried many ways to get foreign

product specs from various sources but with poor success. I informed

them of the NBS Spec, library and inquiry service - they never heard

about it.

Mr. Dolan in particular would like to learn about the NBS capability

to identify, locate or recommend where to find, supply or reference

various international or domestic standards. They need a point of

contact and a phone number to call for assist aTice. Mr. DoVan also

mentioned some companies come to him with ideas or products dealing

with energy conservation and asking for help with marketing, and

export. I mentioned the OERI at NBS which he had not heard about. He

thought that some of his companies could use the service. He would

like to receive several information packages and a name to contact so

he could be of more service to the companies. In the area of

recycling Mr. Dolan dealt with a company in Yuba City who has

equipment for recycling plastics. He will look up the information on them and give it to me for follow-up. DoC sponsors many seminars

around the area and we were offered the forum to talk about material

recycling, recycled product directory currently being prepared for ORM

by the State of Florida and procurement. We will discuss this more at

a later date and see how it corresponds to the duties at SWMB.

180
2

The next meeting was with Mr. Powell McDaniel, Deputy Regional

Director - MBDA. He was briefed on the IPA assignment and

specifically on the potential of Subtitle F of RCRA and how small a minority business could offer products with recoverd and recycled

material. He suggested I meet with Ms. Jennifer Stanley of the State

GSA. Ms. Staley has been supported by a continuing grant from MBDA to

help minority business get into the procurement process with state.

He would like to receive a copy of RCRA and at least the executive

summary of the ORM seven state procurement study - I will send them.

This material may be highlighted in the MBDA newsletter.

On September 10 an introductory meeting was held with several SWMB

staff. Mr. John Hagerty and I discussed my areas of interest and how

to best match them with the Board's areas. The three areas where

there is a good match are the waste-to-energy projects under Mr. Doug

Strauch - Chief of the Waste Management Division and more directly

under Mr. Armand Polansky. A second area is marketing of recovered

materials and procurement of products containing recovered materials

under Division Chief Herb Iwahiro and managers Regis Kunz and Chris

Peck. The third area is with the Dept, of Health in the area of

testing and measurement of hazardous and toxic waste under Dr. Harvey

Collins and Dr. Robert Stephens. I will be visiting both Collins and

Stephens to establish the specifics of our working relations. Dr.

Stephens is working toward a state-wide quality assurance and lab

calibration program and has expressed interest in NBS information and

SRM's. More information will be developed when we meet at the

Berkeley lab on September 22. Also met with Mr. Iwahiro and we talked

about the marketing, waste reduction and procurement projects. I will

"float" among the projects until a comfortable working system can be

developed. The three areas cited are of utmost interest to the Board

and Mr. Trumbull the Chairman. These also complement the duties of

the DOC Secretary under Subtitle E. Conversations with the area managers, Kunz and Peck, reaffirmed their interest in having NBS/DOC

help.

On September 11 - met with Ms. Jennifer Stanley of the GSA - OMBDA

office, at the suggestion of Mr. McDaniel of MBDA - DOC region 9. Ms.

Stanley was interested in the idea of developing a program for

minorities in the recycled product area. She serves on Governor's

Small Business Advisory Council and they are looking for new project

ideas to present to the Governor. I will arrange a meeting with SWMB

staff to discuss how best to structure a joint program which will then

be offered to the Governor for consideration. Should a program be

initiated Ms. Stanley will publicize it in their newsletter and offer

us a forum to present the program at various meetings. A meeting

typical of the one we may be participants in will be held October 13

in Pasadena (information enclosed) sponsored by State Senator Diane E. Watson. DOC Secretary Baldridge is listed as a keynote luncheon

181
3

speaker. Perhaps he may like to know of any program where NBS is

partcipating - if it does happen. Will call or write in with more details as they develop. As of today it is uncertain if I will

attend. Guidance from NBS would be appreciated.

Next meeting on the 11th was with Don Ekstedt - Chief of

Specifications for the State Procurement Department. He received the seven state study and would be going over it. We talked about

initiating a program with SWMB and OMBDA and he would support a program as long as it was carried out via normal procurement

processes. State is already recycling and remanufacturing office

furniture and Caltrans was evaluating recycled oils and greases.

Procurement will probably be represented at the meeting with Ms.

Stanley and SWMB. This project will be one that I may possibly carry

out myself although I suggested someone from the Board staff take a lead role with my assistance. We will see what happens!

On September 14, the IPA begins and actual onsite project involvement

will allow for the identification of needs.

A copy of the most current organizational structure is also attached.

182
Appendix IX

UNITED STATES DEPARTMENT OF COMMERCE

National Bureau of Standards

Washington, D.C. 20234

October 9, 1981

MEMORANDUM FOR The Record

From: Joseph G. Berke

Subject: IPA Progress Report No. 2 — September 14 - October 1, 1981

On September 14, 1981, the IPA assignment officially started, and the process of

getting acquainted with staff, projects, and procedures began. Opening meetings

were held with Mr. Iwahiro and Mr. Strauch to review the job I was to do for NBS

while in California and to get better acquainted with their respective program

areas. Overviews of the major board program areas are shown in the

organization chart submitted with report No. 1.

Additional general conversations were held with Dr. Robert Stevens of the Health

Department Laboratory in Berkeley. This was a followup on a previous meeting

with Dr. Stevens at NBS while he was attending a conference in May. The talks

concerned the topics of developing some sort of vol untary/mandatory laboratory

accreditation program for those labs in the State, public or private, who are doing hazardous waste analyses. A meeting was set for September 22 to discuss

the matter further. Another call was to Harry Freeman of the Governor's Office

of Appropriate Technology (OAT) to discuss their work on the disposal of

hazardous wastes by incineration. OAT is reviewing various technologies and

will select several —up to six —for possible demonstration. A report on the

study will be issued soon, and we will get a copy. I informed him of the NBS

work and interest in the subject, and we will meet in about two weeks to discuss

details.

On this first day I also attended a meeting of the staff of the Office of Market

Research and Development. Here I reviewed the IPA task and offered the services

of NBS in appropriate areas. Projects in this area include a study of the

export market for fibers collected in California. Specifically, the interest

involves (1) export market and in-state mill capacity for waste paper in all

categories, (2) influential factors governing the export of waste paper from

California, (3) what products made from waste paper can be exported or sold in

California, (4) information on future mill capacity, new construction, etc.,

and (5) a model or methods for projecting the supply and demand for waste paper.

A call was placed to Jim Owens and Diana Friedman of BIE/DoC to see if the

information was available on a state-specific basis. It was not. I also

requested a copy of the ORM-funded study of waste paper markets in four southeastern states. The report cannot be released yet because it is still being

reviewed at DoC. This report may be of help in the study here. A second area

of interest of this Office is the procurement of products containing recovered

material. The seven-state study is very helpful in showing what is happening

around the country. The Florida projects on a directory of suppliers and the

Colorado project on developing bid evaluation criteria for recycled products are going to be very helpful in California. I will continue to work with Cathy

Hudson on these. I also prepared an outline for a joint project between SWMB

183
2

and GSA on such procurements in California. We will be presenting the outline

to the State purchasing director as soon as SWMB staffing of the project is

settled. A draft copy of the procurement project is attached. This procurement

project has the strong interest and support of the chairman, Mr. Trumbull, and

the Board members themselves. Mr. Trumbull mentioned the support and interest

during a brief meeting with him. He also suggested that I attend, in his

behalf, the meetings of the Toxic Substances Coordinating Council. I am trying

to get in touch with proper people, but so far, no one representing the Council

has returned the calls —I will keep trying.

Also attended the staff meeting of the Program Development Group and once again

reviewed my IPA assignment. This group contains the oil recycling program. The

people in this program are aware of the NBS work and are interested in meeting

with Don Becker when he visits the Board on October 7. The meetings have been

arranged.

Another series of meetings were held with staff members of the Waste Management

Section--under the direction of Mr. Strauch. Several ongoing projects in this

group are similar to several ongoing at NBS. The first of these involves the

leaching of MSW, as received, ashing the MSW by ASTM methods, and leaching again

by both the California method and the EPA extraction method. A different MSW

sample from the same batch is used for the two leachings. EAL laboratories is

under contract to perform the tests and report the results. Conversations with

the EAL project director indicate that they are aware of NBS, the SRM materials,

and that they are one of the commercial labs participating in the DoE/LETC Waste

Characterization Program that NBS also participates in. They are interested in

the NBS work in waste and would like to hear more about the IPA project and be

made aware of waste related SRM's, data, research, etc. A further meeting was agreed to, but a time has not yet been set. It will probably be after their

work on the state project is complete--about a month or two.

Another project, by Brown-Vence and Associates, is looking at the uses for fly

ash. A meeting is scheduled for October 6 to discuss the project and inform

them of the NBS work on the subject in CBT, CAC, and the literature search

already performed. The Waste Management Section of the SWMB also monitors the

ix major waste-to-energy projects being carried out around the state. It

ppears that the actual technical needs reside with the cities and counties

carrying out the work. More effort will be made to interact directly with the

project directors to determine their technical needs. A new project that is in

the planning stage addresses the problem of testing and monitoring the migration

of landfill gas as well as to look at maximum recovery of the gas. Once the

project gets going, the NBS participating role will be better defined. Attached

is an article describing the problem and the project.

The first in-person meeting with the Health Department Lab in Berkeley took

place September 22. Dr. Stevens was called out of town so the meeting was with

Ms. Janice Nakao, a health chemist. We talked about my IPA and what programs

NBS had that may be of help. One need was inorganics in water covering the

elements and compounds cited in the Federal Register, Part III,

December 3, 1979, and on page 64 of the August California Assessment Manual.

184
3

Basically, SRM's are needed for various waste stream constituents in various

matrices found in the environment. A copy of the manual is available in CAC,

and the specific pages referred to are attached. The next major topic and area

of measurement need revolve around a laboratory QA and Certification Program for

public and private state laboratories. There is no legislation to establish a program, but it is being worked on. The program would be for labs doing

hazardous waste analysis for cleanups after spills, for transporters, for

enforcement and monitoring, and for the benefit of all interested parties.

Currently, lab selection is done by "people knowing the good ones," by word of

mouth, and from experience. In the absence of formal legislation, the thought

ran to a voluntary accreditation program. This would include onsite

inspections, reference sample analysis, equipment calibration, procedure review,

and staff capability. NBS could be a participant in many of these areas. One

thought was to hold a statewide conference on the subject of measurement needs

and voluntary accreditation. This will have to be developed in more detail in

subsequent meetings, but it is a thought.

Another major area of need involves training, information, and methods for use

by county officials, who are generally first on the scene of a spill or other

accident, to quickly determine what the material or mixtures of materials are

and the treatment. Most labs are not well equipped, some even have activation

analysis units--but not all. Most are one- to two-person operations, and yet

they are the ones closest to the problem and who arrive at the scene first.

Thus, rapid simple onsite screening tests are necessary along with proper data

and training. The test, as a minimum, quickly identifies if a material is

explosive, flammable, corrosive, etc., and how to treat the problem. One area

of information and training is the effects of the surrounding matrix--dust

,

asphalt, concrete, etc. --on the material spilled and how the natural matrix can

be quickly "subtracted out" of an analysis to isolate the material in question.

A brief conversation with a lab chemist indicated the need for SRM's of pure

malathion and maloxion. The material they buy from standard suppliers is

commercial grade, and they need pure certified material. They also need stock

solutions of organo-leads in a solvent that can be diluted to various

concentrations. There was great interest in our synthetic leachates and the PCB

in Oil SRM. It would be useful to prepare a brochure or a list of SRM's that

have application to hazardous waste testing, even those older ones that when

leached provide an interesting leachate--a new use for an old product. I have

requested, through Steve Carpenter, samples of the leachates for Berkeley .

Another project at the Board involves a study to determine the feasibility of a "waste research institute." The firm of Gibbs ard Hill are do'’’'c the study.

Possible options include a oilot plans t: verify ;nt -‘ec:'': i''.z3r ?. basic research laboratory, owner/operator training facility, technical

evaluating and reporting center, economic research on MSW, or a combination of some of the above. The study is just getting started, and I will be following

it closely. I provided the project person with contacts at NBS to discuss basic

research in MSW as well as other information about ASTM, ASME, and other items

of initial value to the study. The results should be useful to the NBS mission

of technical assistance to the States.

185
4

A meeting with Dr. Harvey Collins, Chief of the Environmental Health Branch--

Department of Health Services, identified the need for critically analyzed

compiled technical data on such items as treatment, disposal, analyses, sampling

of hazardous and toxic wastes--whether from a fresh spill or an old abandoned

site. There is a lot of new information coming out, some good but mostly poor,

and someone needs to look at the material. Perhaps a focused program within

SRD, monitored by ORM, could be established. Dr. Collins also suggested visits

to Dr. Storm in Hazardous Materials Management and to Dr. Heslep, Director of

the Berkeley Lab, to brief them on the NBS program and my role in California. A

copy of Dr. Collins' branch organization chart is attached.

This concludes report No. 2. It would be very helpful to me to hear from

various NBS staff about the format and contents of this report, areas of

interest that they want me to specifically pursue, and current NBS "products" or expertise that can be applied to the above subjects.

Attachments

cc

C. Reimann

C. C. Gravatt

D. Johnson

ORM Staff

186
Conferences Sponsored

November 20-21, 1980 -- Workshop on the Procurement of Products Containing

Recovered Materials. Held at NBS.

May 18 - 20, 1981

September 28 - October 1, 1981

DoE/NBS Workshop on Environmental Speciation and

Monitoring Needs for Trace Metal -Containing

Substances from Energy-Related Processes. Held

at NBS.

4th International Conference on Used Oil Recovery

and Reuse Co-sponsored by U.S.D.O.E. and

U.S.N.B.S. Held at Caesars Palace, Las Vegas.

Technical and Professional Committees

Becker, Donald A. Voting Member, ASTM Committee D-2

Member, Technical Divisions

B, C, L, N, P Member, ASTM Test Monitoring Board

Berke, Joseph B. Member, ASTM Committee D-38

ASTM E-38, Vice-Chairman, Awards

Member, ASTM Committee D-34

Matthews, R. T. Member, ASTM D-34

Member, ASTM D-19

Yakowitz, H. Vice Chairman, ASTM Committee

D-34.02

187
Publ ications

1. Berke, J. G. and Hudson, C. H., NBSIR 81-2316, "Procurement of

Products Containing Recovered Material: A Summary of Activities in

Seven States", (July 1981).

2. Becker, D. A., "Re-refined Lube Oil Consistency and Quality: The

Ultimate Question," Proceedings, Second European Congress on the Recycling of Used Oils, Syndicat National des Fabri cants

Raffineurs, Paris (October 1980). In Press.

3. Becker, D. A. and Hsu, S. H., "Status Report on the Characteri zati on of Re-refined Lubricating Base Oils," SAE Paper No. 801382, Society of

Automotive Engineers, Warrendale, PA (October 1980).

4. Becker, D. A., "Research Methodology in Used Oil Recycling,"

Proceedings, Conference on Atomic and Nuclear Methods in Fossil Energy

Research, American Nuclear Society (December 1980). In Press.

5. Becker, D. A., Rook, H. L., and LaFleur, P. D., "High Purity

Materials, Standards, and Reference Materials," Chapter 5, Section 4

in Nondestructive Activation Analysis, edited by S. Amiel, Elsevier

Scientific Publ. Co., NYC (1961).

6. Becker, D. A., "Recycling-Oil", Encyclopedia of Chemical Technology,

John Wiley and Sons, Inc., NYC. "( In "Preparation)

7. Domalski, E. S., Kirklin, D. R., and Mitchell, D. J., "Determination

of the Calorific Value of Refuse and Refuse-Derived-Fuels by Large

Bomb Calorimetry. Summary of the 1978 Fiscal Year Results," NBSIR 80-

1968, January 1980.

8. Domalski, E. S., Kirklin, D. R., Colbert, J., Decker, P. Abramowitz, S., "Test Procedures for the Determination of Gross

Calorific Value of Refuse and Refuse-Derived-Fuel by Conventional and

Large Bomb Calorimetry. Summary of 1979 FY Results," NBSIR 81-2278,

June 1981.

9. "Chemical Waste Incinerator Ships - The Interagency Program to Develop

a Capacity in the United States," to the Society of Naval Architests

and Marine Engineers, Washington, DC, September 23, 1981. Coauthors:Gerald 0. Chapmen, U.S.E.P.A., Daniel Leubecker, Maritime

Administration, Lissa Martinez, Maritime Administration, Rosalie,

Matthews, U.S.D.O.C., Donald A. Oberacher, U.S.E.P.A., and Frits

Wybenga, U. S. Coast Guard.

188
Invited Talks

Becker, D. A., "Alternative Utilization: Recycled Oil Used As Fuel,"

Fourth International Conference on Used Oil Recovery and Reuse, Las Vegas

(September 1981).

Becker, D. A., "NBS Research on Re-refined Engine Oil Tests," Fourth

International Conference on Used Oil Recovery and Reuse, Las Vegas

(September 1981).

Becker, D. A., "Re-refined Lube Oil Consistency and Quality: The Ultimate

Question," Second European Congress on the Recycling of Used Oils, Paris

(October 1980).

Becker, D. A., "Current Status of the NBS Recycled Oil Program," Third

Annual Conference, National Association of Oil Recovery Coordinators,

Raleigh, N.C. (April 1981).

Becker, D. A., "Recycled Oil Burned for Fuel: Positive or Negative?",

American Boiler Manufacturers Association Meeting, Chicago (April 1981).

Becker, D. A., "Activities in Recycled Oil and Product Quality," Used Oil

Recycling Seminar Series for State Programs; Orlando, FL (July 1981);

Philadelphia (September 1981).

Berke, J. 6., "Prepared 5 minute tape on Resource Recovery for the

Department ofCommerce Radio Feature Service.

Domalski, E. S., "Design Characteristics of the 2.5 Kilogram Capacity Flow

Calorimeter," Subcommittee E38.01 on Energy, Philadelphia, PA, Apr. 1981.

Domalski, E. S., "Recent Developments in the Design and Construction of

the 2.5 Kilogram Capacity Flow Calorimeter," ASME Research Committee on Industrial and Municipal Wastes, New York, NY, June 1981.

Matthews, R. .T., "National Conference of State Legislators' Annual

Meeting, Atlanta, Georgia, July 3, 1981: Panel on "Garbage - The Resource

of the 80' s."

Yakowitz, H., Address to Chief Executive Officers of member companies of

the American Paper Industry (Phoenix, Arizona), October 1980.

Yakowitz, H., Presentation to the Eastern Regional Conference, National

Association of Recycling Industries (New York, New York), December 1980.

Yakowitz, H., Presentation to the California State Solid Waste Management

Board (Sacramento, California), "Federal Plans for Resource Recovery from

Municipal Waste," January 1981.

189
Yakowitz, H., Presentation as member of U.S. delegation at Waste

Management Policy Group meeting. Organization for Economic Cooperation and

Development (Paris, France), "National Bureau of Standards Activities in

Recycled Materials," April 1981.

Yakowitz, H., Presentation to the Executive Board of the Association of

State and Territorial Solid Waste Management Officials (Washington, DC),

"Department of Commerce Program in Resource Recovery," 1981.

Yakowitz, H., Presentation to American Iron and Steel Institute Task Group

(Pittsburgh, Pennsylvania), "Possibilities for the Recycling of Steel Mill

Sludges," July 1981.
NBS-114A (REV. 2-80

U.S. DEPT. OF COMM.

BIBLIOGRAPHIC DATA

SHEET (See instructions)

1. PUBLICATION OR

REPORT NO.

NBSIR 81-2417

2. Performing Organ. Report No. 3. Publication Date

November 1981

4. TITLE AND SUBTITLE

Technical Activities of the Office of Recycled Materials

5. AUTHOR(S)

Donald A. Becker, Joseph G. Berke. Eugene $. Domalski. Rosalie

6. PERFORMING ORGANIZATION (If joint or other than MBS. see instructions) 7.

Harvey

T. Matthews & Yakowit?

Contract/Grant No.

national bureau of standards

DEPARTMENT OF COMMERCE

WASHINGTON, D.C. 20234

8.

Type of Report & Period Covered

9.

SPONSORING ORGANIZATION NAME AND COMPLETE ADDRESS (Street, City, State, ZIP)

10.

SUPPLEMENTARY NOTES

I I Document describes a computer program; SF-185, FlPS Software Summary, is attached.

11.

ABSTRACT (A 200~word or less factual summary of most significant information. If document includes a significant

bibliography or literature survey, mention it here)

A review of recycled materials programs at NBS, for FY 198T is presented

in this annual report.

1

I;:

12.

KEY WORDS (Six to twelve entries; alphabetical order; capitalize only proper names; and separate key words by semicolons)

i

13.

Energy-from-waste; materials market; oil

refused-deri ved-fuel ; re-refined oil.

AVAILABILITY

I I Unlimited

rX1 For Official Distribution. Do Not Release to NTIS

analysis; recycled materials;

14. NO. OF

PRINTED PAGES

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