^T °" ** \

to NBS TECHNICAL NOTE 1130

U.S. DEPARTMENT OF COMMERCE/ National Bureau of Standards

Recycled Oil Program:

Phase I - Test Procedures for

Recycled Oil Used as Burner Fuel

QC

100

U5753

no. 1130

1980

c.2
NATIONAL BUREAU OF STANDARDS

The National Bureau of Standards' was established by an act of Congress on March 3, 1901. The Bureau's overall goal is to strengthen and advance the Nation's science and technology

and facilitate their effective application for public benefit. To this end, the Bureau conducts

research and provides: (1) a basis for the Nation's physical measurement system, (2) scientific and technological services for industry and government, (3) a technical basis for equity in trade, and (4) technical services to promote public safety. The Bureau's technical work is per- formed by the National Measurement Laboratory, the National Engineering Laboratory, and

the Institute for Computer Sciences and Technology.

THE NATIONAL MEASUREMENT LABORATORY provides the national system of

physical and chemical and materials measurement; coordinates the system with measurement

systems of other nations and furnishes essential services leading to accurate and uniform

physical and chemical measurement throughout the Nation's scientific community, industry,

and commerce; conducts materials research leading to improved methods of measurement,

standards, and data on the properties of materials needed by industry, commerce, educational

institutions, and Government; provides advisory and research services to other Government

agencies; develops, produces, and distributes Standard Reference Materials; and provides

calibration services. The Laboratory consists of the following centers:

Absolute Physical Quantities2 — Radiation Research — Thermodynamics and

Molecular Science — Analytical Chemistry — Materials Science. THE NATIONAL ENGINEERING LABORATORY provides technology and technical ser- vices to the public and private sectors to address national needs and to solve national problems; conducts research in engineering and applied science in support of these efforts; builds and maintains competence in the necessary disciplines required to carry out this research and technical service; develops engineering data and measurement capabilities;

provides engineering measurement traceability services; develops test methods and proposes

engineering standards and code changes; develops and proposes new engineering practices;

and develops and improves mechanisms to transfer results of its research to the ultimate user. The Laboratory consists of the following centers:

Applied Mathematics — Electronics and Electrical Engineering2 — Mechanical

Engineering and Process Technology 2 — Building Technology — Fire Research —

Consumer Product Technology — Field Methods.

THE INSTITUTE FOR COMPUTER SCIENCES AND TECHNOLOGY conducts

research and provides scientific and technical services to aid Federal agencies in the selection, acquisition, application, and use of computer technology to improve effectiveness and

economy in Government operations in accordance with Public Law 89-306 (40 U.S.C. 759), relevant Executive Orders, and other directives; carries out this mission by managing the Federal Information Processing Standards Program, developing Federal ADP standards

guidelines, and managing Federal participation in ADP voluntary standardization activities; provides scientific and technological advisory services and assistance to Federal agencies; and

provides the technical foundation for computer-related policies of the Federal Government.

The Institute consists of the following centers:

Programming Science and Technology — Computer Systems Engineering.

'Headquarters and Laboratories at Gaithersburg, MD, unless otherwise noted; mailing address Washington, DC 20234.

2 Some divisions within the center are located at Boulder, CO 80303.
Recycled Oil Program: Phase I - Test Procedures

for Recycled Oil Used as Burner Fuel

National Bureau of Stift&rfe

Library, E-01 Admin, Bide. D. A. Becker 1QDn

J. J. Comeford AUG 2 7 1980

Dot ace - Cure,

Recycled Oil Program

Office of Recycled Materials

National Measurement Laboratory

National Bureau of Standards

Washington, DC 20234

"*e*u of W~,

U.S. DEPARTMENT OF COMMERCE, Philip M. Klutznick, Secretary

Luther H. Hodges, Jr., Deputy Secretary

Jordan J. Baruch, Assistant Secretary for Productivity, Technology and Innovation

(I. C NATIONAL BUREAU OF STANDARDS, Ernest Ambler, Director

Issued August 1980
National Bureau of Standards Technical Note 1130

Nat. Bur. Stand.(U.S.),Tech. Note 1 130, 93 pages (Aug. 1980) CODEN: NBTNAE

Supersedes NBSIR 78-1453

U.S. GOVERNMENT PRINTING OFFICE

WASHINGTON: 1980

For sale by the Superintendent of Documents, U.S. Government Printing Office, Washington, D.C. 20402

Price. $4.25

(Add 25 percent for other than U.S. mailing)
The Energy Policy and Conservation Act requires the National Bureau

of Standards (NBS) to develop test procedures which can be used to establish the "substantial equivalence" of recycled oils with new oils. This report covers the first phase of the NBS program, and contains test procedures which may be used for establishing the substantial equivalency

of recycled petroleum oils (including blends of recycled oils with new oils) to new oils for use as a burner fuel. Test procedures were selected

and evaluated for their ability to reliably measure the property under

test.

Key words: Fuel oil; petroleum standards; petroleum test methods;

recycled burner fuel oil; substantial equivalency; used oil; waste oil.

m
Table of Contents

Page

Abstract iii

Executive Summary v

1. Introduction 1

2. Burner Fuel Oil Specifications 1

3. Characteristics of Recycled Oils Used as Burner Fuel 2

4. Evaluation of Test Procedures 4

5. Test Procedures for Operational Performance 7

5.1 Test Procedure for Sampling 7

5.1 Sampling 7

5.2 Test Procedures for Bulk Properties 9

5.2.1 Flash Point 9 5.2.2 Pour Point 11 5.2.3 Distillation Temperature 11 5.2.4 Viscosity 13 5.2.5 Density 16 5.2.6 Copper Corrosion 17 5.2.7 Aniline Point 19 5.2.8 Heating Value 21

5.3 Test Procedures for Impurities '. 26

5.3.1 Water and Sediment 26 5.3.2 Carbon Residue 32 5.3.3 Ash 34 5.3.4 Total Sulfur 38 5.3.5 Acidity 41

6. Test Procedures for Impurities of Potential Environmental Concern 45

6.1 Test Procedures for Three Recycled Fuel Oil Impurities 45

6.1.1 Lead 45 6.1.2 Polynuclear Aromatic Hydrocarbons 47 6.1.3 Halogens (Chlorine and Bromine) 51

7. References 54

8. Appendix A. Energy Policy and Conservations Act, Section 383 57

9. Appendix B. Fuel Oil Specifications 61

B.l ASTM D 396-76, Standard Specification for Fuel Oils 62 B.2 Federal Specification VV-F-815C, Fuel Oil, Burner 69 B.3 Military Specifications MIL-F-859E, Fuel Oil, Burner 79 B.4 Military Specification MIL-F-16884F, Fuel Oil, Diesel, Marine 87

IV
TEST PROCEDURES FOR RECYCLED OIL

USED AS BURNER FUEL

Executive Summary

This report was prepared in response to the Energy Policy and Conservation Act (EPCA, Public

Law 94-163; 42 U.S.C. 6201 et seq.). Section

383(c) of this law requires the National Bureau

of Standards (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." It also requires that after development

of these test procedures they be reported to the Federal Trade Commission.

This report covers the first phase of the NBS program, and the purpose of this report is to provide a set of evaluated test procedures which

may be applied to a recycled oil to establish

its substantial equivalency to a new oil for the specific end use use as a burner fuel. For the purposes of this report, the term "substantially

equivalent" (as used in the EPCA) has been taken

to mean equal performance of the oil with respect

to the important operational parameters concerned

with this particular end use.

The NBS program plan ha existing burner fuel oil s procedures and, utilizing

and data on used and recyc properties of recycled oil the important operational

evaluate the existing test

properties; and (c) to de test procedures where requ extent possible, existing

utilized and the simplest

consistent with obtaining

s been (a) to review

pecifi cations and test available information

led oils, identify the

s which are related to parameters; (b) to procedures for these

velop new or modified

ired. To the maximum

test methods are method employed,

the required results.

Fuel oils found in commerce exhibit a range of values for each specified property, as do the recycled oils which may be used separately or blended with them. Used petroleum oils recycled

for use as burner fuel oils are obtained from a variety of sources. Examples of such sources

include automobile garages and service stations,

truck and taxi fleets, military installations,

industrial plants and manufacturing facilities

of all types, and waste water treatment plants.

Indications are that at the present time much of the used oil recycled as fuel receives minimal

processing to remove contaminants. These contaminants may be of concern for either operational

or environmental considerations.

The important properties

are controlled through the u of which two, the American S and Materials (ASTM) Specif

the Federal Specification VV primary specifications in cu specifications are discussed

of this report, and include

are designed to evaluate the important properties of the

of a burner fuel oil se of specifications

ociety for Testing

cations D 396-76 and -F-815C, are the rrent use. These

further in the body test procedures which

significant and

fuel as these properties are related to operational performance.

The primary objective of these tests is to assure that the consumer receives a product of consistent and satisfactory quality for the purpose intended.

The test procedures called for in specifications for new burner fuel oils have been developed over a considerable period of time, in response to the specific problems and needs of various industries and users. Because the test procedures which are contained in the ASTM D 396 Specification were those believed by ASTM to be of greatest significance in determining the performance characteristics of the oils for the types of burners in which they are most commonly

used, this group of test procedures served as a starting point for the NBS investigation. The

NBS evaluation of specific test procedures was made using the following evaluation process:

1. Determination of those properties for which recycled oils used for fuel should

be tested.

a. Based on virgin fuel oil specifications

(ASTM and Federal).

b. Based on information and data from

external publications and sources.

2. Preliminary review of the test procedures

on the basis of established physical and chemical principles by a scientist knowl- edgeable in the technical area which this test encompassed.

3. Preliminary selection of most appropriate

test procedure from those tests available.

4. Experimental evaluation of the test to establish whether it was capable of reliably measuring the property under

test. This evaluation included one or more of the following:

a. Verification of the performability of the test by evaluating the repeatability with a variety of recycled and used oils, and where appropriate, blends

of used oils with virgin fuel oils.

b. Examination of the effects of known recycled oil impurities on the performability of the test where these effects were significant.

c. Establishing the ability of the test procedure to provide the correct or "true" concentrations for those tests which measure impurity levels.

5. Development of new test procedures or modification of existing tests where

necessary to provide an acceptable test procedure to measure the desired property.

6. Final selection of the evaluated test

procedure.
The test procedures contained in this report

have been separated into four general groups:

sampling, bulk properties, impurities, and

impurities of potential environmental concern. The section on sampling contains a procedure for

providing a representative sample needed for

each of the ensuing test procedures, and a recommendation for the evaluation of homogeneity

of the bulk lot. The second section contains

test procedures for the bulk properties of flash

point, pour point, distillation temperature,

viscosity, density, copper corrosion, aniline

point, and heating values. The third section

contains test procedures for determining various

impurities in a recycled oil: water and sediment, carbon residue, ash, total sulfur, and

acidity. The final section contains test pro- cedures for impurities having potential environmental concern. It includes lead, polynuclear

aromatic hydrocarbons, and two of the halogens

(chlorine and bromine).

The test procedures listed above are de- scribed in the report, with citation of the most

recent publication of the complete procedure,

and include a detailed description of any necessary modifications. They have been

evaluated for recycled oil which is to be used

as burner fuel oil. These tests are capable of establishing the "substantial equivalence" of such recycled oils to virgin burner fuel oils

for purposes of operational performance.

VI
TEST PROCEDURES FOR RECYCLED OIL USED AS BURNER FUEL

1. Introduction

hazards from disposal of used oil. It is well known that there are serious environmental

problems associated with improper disposal

practices for used oil, including widespread

contamination by the high heavy-metal concen- trations in used oil and by the basic hydrocarbons themselves.

This report was prepared in response to the Energy Policy and Conservation Act (EPCA, Public

Law 94-163; 42 U.S.C. 6201 et seg. ). Section

383(c) of this law requires the National Bureau

of Standards (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." It also requires that

after development of these test procedures they

be reported to the Federal Trade Commission

(FTC). A copy of this section of the EPCA is included as Appendix A. This report covers the first phase of the NBS program and contains test procedures which may be used for establishing

the substantial equivalency of recycled petroleum oils (including blends of recycled oils

with new oils) to new oils for use as a burner

fuel.

The following definitions are taken from the

EPCA and are adopted for this report:

"(1) the term 'used oil' means any oil which has been refined from crude oil, has been used, and as a result of such use has been contaminated by physical or chemical

impurities.

(2) The term 'recycled oil' means

(A) used oil from which physical and chemical contaminants acquired through

use have been removed by re-refining or other processing, or

(B) any blend of oil, consisting of such re-refined or otherwise processed

used oil and new oil or additives, with

respect to which the manufacturer has determined, pursuant to the rule pre- scribed under subsection (d)(l)(A)(i)

,

is substantially equivalent to new oil for a particular end use. (3) The term 'new oil' means any oil which

has been refined from crude oil and has not been used, and which may or may not contain

additives. Such term does not include used

oil or recycled oil

.

(4) The term 'manufacturer' means any person who re-refines or otherwise processes

used oil to remove physical or chemical

impurities acquired through use or who blends

such re-refined or otherwise processed used

oil with new oil or additives.

(5) The term 'Commission' means the Federal Trade Commission."

In the EPCA, the purposes of the section on recycled oil were stated as (a) to encourage

recycling of used oil, (b) to promote the use

of recycled oil, (c) to reduce the consumption

of new oil 1

, and (d) to reduce the environmental

The purpose of this report is to provide a set of evaluated test procedures which may be applied to a recycled oil to establish its sub- stantial equivalency to a new oil for the specific end use as a burner fuel. For the purposes

of this report, the term "substantially equivalent" as used in the EPCA has been taken to mean equal performance of the oil with respect

to the important operational parameters con- cerned with this particular end use.

The NBS program plan has been (a) to review

existing burner fuel oil specifications and test procedures and, utilizing available information

and data on used and recycled oils, identify the properties of recycled oils which are related to the important operational parameters; (b) to evaluate the existing test procedures for these

properties; and (c) to develop new or modified

test procedures where required. To the maximum

extent possible, existing test methods are utilized and the simplest method employed, consis- tent with obtaining the required results.

2. Burner Fuel Oil Specifications

Fuel oils found in commerce exhibit a range

of values for each specified property, as do the recycled oils which may be used separately or blended with them. The first general set of

fuel oil classifications in the U.S. was issued

by the National Bureau of Standards in 1929

[l] 2

. They were the first industrywide attempt

to classify fuels according to significant

properties. These standards, based on a joint

conference of consumers, burner manufacturers,

and general interest groups held on January 9, 1929, were issued as Commercial Standard (CS) 12-29. This standard was revised in 1933, 1934,

1938, and 1940, with the final revision issued

in 1948 as CS 12-48 [1], and remained in effect

until 1966, at which time it was withdrawn.

These first standards established the presently

used fuel oil grades.

At the present time, the following sets of specifications are, or in the recent past have

been, used for burner fuel oils:

ASTM3 D 396-76, Standard Specification for

Fuel Oils

VV-F-815C, Federal Specification, Fuel Oil, Burner

MIL-F-859E, Military Specification, Fuel Oil, Burner

*In this report, the term "new oil" is used

interchangeably with the term "virgin oil."

^Number in brackets indicate the literature

references at the end of this report.

3 American Society for Testing and Materials.
MIL-F-16884G, Military Specification, Fuel Oil , Diesel , Marine

These specifications are included in this report

as Appendix B. The first two, ASTM D 396 and

VV-F-815C, are the primary specifications in current use and are summarized in table 1. These two widely used specifications are virtually identical, except as noted in table 1. Also, the VV-F-815C specification contains the statement "...suppliers are prohibited from

adulterating either Grade No. 5 or Grade No. 6 fuel oil with waste crankcase lubricants or similar products" (section 3.1).

The general requirements of these specifications are that the fuel oil consist of petroleumderived products, with two broad general classifications employed—distillates and residuals.

The approximate atmospheric boiling point ranges

for distillate fuel oils are, for No. 1 (kerosine),

149 °C (300 °F) to 302 °C (576 °F) and, for No. 2, 160 °C (320 °F) to 343 °C (649 °F). Distillate

fuel oils consist of overhead or distilled frac- tions and are classified on the basis of distillation temperature (10 percent point and 90 per- cent point) and viscosity. Residual fuel oils

are bottoms remaining after distillation or blends of these bottoms with distillates and are classified on the basis of viscosity.

The fuel oil grades in general use are de- scribed in the ASTM fuel oil specification

(D 396) as follows [2]:.

"XI. 3 Grades

"XI. 3.1 Grade No. 1 is a light distillate

intended for use in burners of the vaporizing

type in which the oil is converted to a vapor

by contact with a heated surface or by radiation. High volatility is necessary to en- sure that evaporation proceeds with a minimum

of residue.

XI. 3. 2 Grade No. 2 is a heavier distillate

than grade No. 1. It is intended for use in atomizing type burners which spray the oil into a combustion chamber where the tiny

droplets burn while in suspension. This

grade of oil is used in most domestic burners

and in many medium capacity commercial

industrial burners where its ease of handling

and ready availability sometimes justify its higher cost over the residual fuels.

XI. 3. 3 Grade No. 4 is usually a light

residual, but it sometimes is a heavy distillate. It is intended for use in burners

equipped with devices that atomize oils of

higher viscosity than domestic burners can

handle. Its permissible viscosity range

allows it to be pumped and atomized at rel- atively low storage temperatures. Thus, in all but extremely cold weather it requires

no preheating for handling.

XI. 3. 4 Grade No. 5 (Light) is residual

fuel of intermediate viscosity for burners

capable of handling fuel more viscous than

grade No. 4 without preheating. Preheating

may be necessary in some types of equipment

for burning and in colder climates for

handl ing.

XI. 3. 5 Grade No. 5 (Heavy) is a residual

fuel more viscous than Gjcade No. 5 (light)

and is intended for use in similar service.

Preheating may be necessary in some types of equipment for burning and in colder climates

for handling.

XI. 3. 6 Grade No. 6, sometimes referred to

as 'Bunker C,

1 is a high-viscosity oil used

mostly in commercial and industrial heating.

It requires preheating in the storage tank to permit pumping, and additional preheating at the burner to permit atomizing. The extra equipment and maintenance required to handle

this fuel usually preclude its use in small installations.

XI. 3. 7 Residual fuel oil supplied to meet

regulations requiring low sulfur content may differ from the grade previously supplied.

It may be lower in viscosity (and fall into a different grade number). If it must be fluid

at a given temperature, Method D 97 may not accurately reflect the pour point which can

be expected after a period of storage. It is suggested that the purchaser and supplier

discuss the proper handling and operating

techniques for a given low-sulfur residual

fuel oil in the installation where it is to be used."

Fuel oil specifications include "...control

tests which aim at evaluating significant and

important properties of the fuel.... The tests may be physical or chemical in character and in very many cases, are empirical procedures, and

as such, are designed to provide an indication

of certain characteristics of the fuel" [3].

The primary objective of such tests is to assure

that the "...consumer receives a product of

consistent and satisfactory quality for the purpose intended" [3].

3. Characteristics of Recycled Oils Used as Burner Fuel

Used petroleum oils recycled for use as burner fuel oils are obtained from a variety of sources. These sources include automotive

garages and service stations, truck and taxi

fleets, military installations, industrial

plants and manufacturing facilities of all types, and waste-water treatment plants. The

major types of used petroleum oils which are recycled into burner fuel oils are listed in table 2. Also listed are some of the additives

and contaminants which are typical of these oils.

These impurities can cause both performancerelated and environment- related problems [4,5].

A recent Environmental Protection Agency (EPA)

estimate (1976) indicates that as much as 90 percent of the easily recoverable used oil was being used as fuel with little or no processing

to remove contaminants [6].

In addition to the additives and contaminants

listed in table 2, there have been many analyses

of used oils and waste oils, primarily for inorganic constituents. These analyses are found in references [4-15] and are summarized in table 3.
Table 1. Summary of specifications contained in D 396 and VV-F-815C.

Fuel oil grades (number)

Test procedures

Flash point, °F (°C)

Pour point, °F (°C)

Water and sediment,

volume %

1 2 4

(lijjht)

130 (55)

or legal

(heavy)

130 (55) or legal

(BunRer C)

100 (38) or legal 100 (38) or legal 130 (55) or legal 140 (60) or legal

(-18) 20 (-7) 20 (-7) — — —

0.05 0.05 0.50 1.00 1.00 2.00

Carbon residue on 10% bottoms,

weight %

0.15 0.35

Ash, weight % — —

Distillation temp. °F (°C)

10% point (max) 420 (215) —

90% point (min)

(max) 550 (288)

540 (282) 640 (338)

Kinematic viscosity, cSt

At 100 °F (38 °C)

Minimum 1.4 2.0

- Maximum 2.2 3.6

At 122 °F (50 °C)

Minimum

Maximum —

—

API gravity, degrees

(min) 35 30

Copper strip corrosion (max) (ASTM

specifications at

50 °C; Federal specifications at 100 °C)

No. 3 No. 3

Sulfur, weight % (max) 0.5 or legal 0.5

or legal

Aniline point,

°F (°C) [Federal

specifications only]

report report

0.10

5.8

26.4

legal

0.10

>26.4

65

legal

0.10

>65

194

(42)

1 (81)

legal

>92 638

legal

"Legal" refers to applicable laws or regulations setting maximum sulfur levels and minumum flash

point levels. Viscosity values in parentheses are for information only and not necessarily limiting.
Very little information is available in the literature on the direct effect of these con- taminants on recycled oil used as burner fuel.

A 1974 report by the EPA discussed some environmental impacts of the combustion of untreated

waste oil and was particularly concerned with

the lead emissions from burning used automobile

crankcase oil [5]. A current EPA research

effort is focused on the experimental evaluation

of the environmental effects of combusting

recycled used oil as a burner fuel and, when

completed, should provide additional information

and data on these questions [16].

Evaluation of Test Procedures

The test procedures called for in specifications for new burner fuel oils have been

developed over a considerable period of time in response to specific problems and needs of the

various industries and users. These test proce- dures have essentially all been developed by

ASTM Committee D-2 (Petroleum Products and

Lubricants), with continuous review and revision,

as necessary. New or modified tests are de- veloped by this same organization as required

when new concerns or problems are identified.

The properties selected for inclusion in the ASTM D 396 specification are "...those that are believed to be of the greatest significance in determining the performance characteristics of the oils in the types of burners in which they

are most commonly used" [2]. Because the purpose

of this study is to enable the ultimate determination of substantially equivalent performance

between new fuel oils and recycled fuel oils,

this group of test procedures served as a starting point for the NBS investigation.

As described in section 3 of this report, a recycled oil may be derived from a variety of

used oils including automotive oils, industrial

oils, hydraulic oils, or any combination of

these. For these recycled used petroleum oils,

the base hydrocarbons do not significantly

change as a result of use [13]. Rather, the

Table 2. Lubricating oil additives and contaminants likely to be found

in used oils [4,5,7].

Used oil type

Motor oils

Typical kinds of additives

Antiwear : zinc organo-dithiophosphates;

organic phosphorus compounds.

Corrosion inhibitors : sulfonates; amine

phosphates; organic phosphites.

Detergents and dispersants : calcium,

magnesium, barium, and zinc sulfonates,

phosphonates, and phenates; alkenyl

succinimides; acrylic polymers.

Viscosity index improvers : isobutylene

polymers; acrylate polymers.

Pour-point depressants : lates; polyacryl amides.

polymethacryPrimary source and type

of typical contaminants

Gasoline : lead and lead

compounds; halogens.

Additives : zinc and zinc

compounds; phosphorus

compounds, etc.

Combustion products : polynuclear aromatics; water; oxygenated compounds; sludge;

varnish.

Fuel : volatile liquid.

Contamination : dirt; wear

metals.

Hydraulic and

industrial oils

Antifoam agents : silicones; synthetic

polymers.

Antioxidants : zinc organo-dithiophosphates; hindered phenols; aromatic

amines; sulfurized phenols.

Many of the above plus:

Extreme pressure additives : organo- sulfur compounds; organo-chlorine

compounds; lead compounds; amines.

Emulsifiers : surfactants; sulfonates;

naphthenates; fatty acid soaps.

Antiseptics : alcohols; phenols;

chlorine compounds.

Coolant leaks : water, ethylene

Many of the above plus:

Additives : sulfur and

sulfur compounds; chlorine

and chlorinated compounds;

fatty oils.

Contamination : metal particles.

Solvents : volatile liquid.
Property or test

Viscosity (SUS at 40 °C)

L API gravity (60 °F) Water (% by volume) BS&W (% by volume) h Benzene insolubles (% by weight)

Gasoline dilution (% by volume)

Flash point (°F)

Heating value, Btu/lb

Ash, sulfated (% by weight)

Carbon residue (% by weight)

Fatty oils (% by weight)

Chlorine (% by weight)

Sulfur (% by weight)

Zinc (ppm)^

Calcium (ppm)

Barium (ppm)

Phosphorus (ppm) Lead (ppm)

Aluminum (ppm) Iron (ppm)

Table 3. Summary of reported used oil analyses [4-15]'

Motor oils Industrial oils

87 to 837

19.1 to 31.3. 0.2 to 33.8°

0.1 to 42

0.56 to 3.33

2.0 to 9.7

175 to 427 13,571 to 19,300

0.03 to 6.43

1.82 to 4.43

NA 0.17 to 0.47 0.17 to 1.09 260 to 1,787

211 to 2,291

9 to 3,906

319 to 1,550

85 to 21,676

< 0.5 to 758

97 to 2,401

143 to 330 25.7 to 26.2

0.1 toNA

C NA

NA

4.6

i

315 to 355 17,250 to 17,990

3.2 toNA5.9

f

to 60 <0.1 to 0.83

0.54 toNA

NA

NA

NA

NA

NA

NA

1.03

Most references did not provide data on all tests listed; therefore, data may be inconsistent

between different tests. Very limited data were available for used industrial oils, on only 5 oils [4]. SUS = Saybolt Universal Seconds (see sec. 5.2.4, Viscosity, this report). One sample had a water content of 46.5 percent, but is considered an outlier.

NA = data not available.

Values for the industrial oils were stated to be for the regular ash, not sulfated. ppm (as the element) = 0.0001 weight percent or 10 4 ppm = 1 weight percent. BS&W = Bottom Settlings and Water (see sec. 5.3.1, Water and Sediment, this report).

impurities and contaminants may make the oils

unfit for further use in certain applications.

Any determination of "substantial equivalence"

requires that for each test procedure, the necessary properties of a recycled fuel oil be evaluated with respect to the impurities and contaminants which could reasonably be expected

to affect that test. Where it has been found

that a property or impurity is important to the performance of a recycled oil and an acceptable

virgin fuel oil test procedure is not available,

a new or modified test procedure has been

developed.

The evaluation of specific test procedures in the following section is separated into four

parts. The first part (section 5.1) covers a procedure to provide a representative sample

needed for each of the test procedures, and a recommendation for the evaluation of homogeneity

of the bulk lot. A procedure for sampling is especially important because of the differing

densities of oils obtained from a variety of sources, which may result in an inhomogeneous

recycled oil [8]. Section 5.2 covers the tests recommended for the bulk properties of a recycled fuel oil. Section 5.3 contains the test procedures recommended for measuring the impurities and contaminants which may be found in a recycled fuel oil and which may affect the per- formance of that recycled fuel oil. Section 6 contains additional test procedures which may be needed as a result of environmental concerns

about recycled oil used as a burner fuel.

The bulk properties of a fuel oil, as discussed in section 5.2, include characteristics such

as flash point, pour point, and density. The

evaluation of test procedures for these kinds of properties with recycled oils involves a determination of whether or not impurities or contaminants in recycled oils interfere with the mea- surement of that property. It further requires

that acceptable precision be obtained with the test procedure when using recycled oils.

Section 5.3 contains test procedures for measuring impurities in a recycled fuel oil. The impurities which are normally found in such

a recycled oil include water, sediment, ash,

sulfur, and carbon residue. These same impurities are also found in new fuel oils,
although usually at much lower levels. Test pro- cedures for these impurities must be evaluated

for their ability to reliably measure the compo- nent under test when used with recycled oils and

to provide an accurate and precise result. Since

recycled oils often contain different types and/or

amounts of impurities, care must be taken during

the evaluation to consider the potential effects

of these on the test procedure.

Section 6 of this report includes test pro- cedures for three impurities in recycled oil which may be significant because of environmental considerations. These impurities are

lead, polynuclear aromatic hydrocarbons, and the halogens (chlorine and bromine). While it is recognized that environmental regulation is the responsibility of the EPA and that these effluents

are not now regulated in fuel oils (new or recycled), test procedures for measuring the

impurity levels have been developed for them and

are included in this report.

The test procedure evaluation process is described in detail in table 4 and schematically

in figure 1. In these evaluations, used auto- motive oils were often taken as' samples because

of their generally high levels of contaminants.

The contaminants contained in these composite

oils include water, volatiles (e.g., gasoline),

polymeric additives, ethylene glycol, lead,

halogens, and both wear metals and dirt. As described in table 4, the effects of such impurities and contaminants on a test procedure were evaluated in part by examining the analytical

precision (i.e., repeatability and/or reproducibility) of the test with oils containing such

contaminants. Other types of samples, e.g., recycled oils and virgin fuel oils, were also

used in the evaluation process. Where possible,

independent determinations were made using other

methods to verify the accuracy of the procedure

and the effects of other impurities on the test

under examination.

Table 4. NBS test procedure evaluation process

1. Determination of those properties for which

recycled oils used for fuel should be tested.

a. Based on virgin fuel oil specifications

(ASTM and Federal).

b. Based on information and data from external

publications and sources. PROGRAM PLAN

Identify important

properties

I

Preliminary review of

test procedure

i -\

' Virgin oil specifications i

i j 1 External publications

1 and information I

I J

i 1 ^

I Existing testj

, procedures |

Preliminary selection

of test procedure

Experimental evaluation

• Establish scientific basis

• Verify performability

• Determine effects of impurities,

contaminants or changes

• Substantiate accuracy

Acceptable

Not Acceptable

Final selection of evaluated test procedure

Test procedure development

Modify existing test Develop new test Experimental evaluation

T

2. Preliminary review of the test procedures on the basis of established physical and chemical

principles by a scientist knowledgeable in the

technical area which the test encompasses.

3. Preliminary selection of most appropriate test procedure from those tests available.

4. Experimental evaluation of the test to establish whether it is capable of reliably measuring the property under test. This evaluation

may include one or more of the following:

a. Verify the performability of the test pro- cedure by evaluating the repeatability with

a variety of recycled and used oils and,

where appropriate, blends of used oils

with virgin fuel oils.

b. Examine the effects of known recycled oil impurities on the performability of the test where these effects are significant.

c. Establish the ability of the test procedure

to provide the correct or "true" concentrations for those tests which measure impurity

levels.

5. Development of new test procedures or modification of existing tests where necessary to provide an acceptable test procedure to measure

the desired property.

6. Final selection of the evaluated test procedure.

To Federal Trade Commission

Figure 1. NBS Test Procedure Evaluation Process.

With regard to establishing the precision of

a petroleum oil test procedure, a detailed discussion of concepts and terms is found in ASTM

E 177-71, "Standard Recommended Practice for Use
of the Terms Precision and Accuracy as Applied

to Measurement of a Property of a Material." In

E 177, note 7 states that, "Some ASTM standards

contain the terms 'repeatability' and 'reproducibility'.... Usually 'repeatability' has meant single-laboratory-operator precision and

' reproducibil ity' multi laboratory-- operator

precision " ASTM D 3244-74T, "Tentative

Recommended Practice for Defining a Basis for Petroleum Product Quality Disputes," defines

"repeatability" and "reproducibility" as the

terms are used by ASTM Committee D-2 on Petroleum Products and Lubricants: Repeatability

"...is defined as that difference between two such [single-operator-laboratory] single results

as would be exceeded in the long run in only one case in twenty in the normal and correct operation

of the test method" [17]. Reproducibility is defined in exactly the same way referring to the difference between two results obtained by

"...operators working in different laboratories,

each obtaining single results on identical test

material when applying the same method" [17].

D 3244, in turn, cites ASTM Research Report

D-2-1007, "Manual on Determining Precision Data

for ASTM Methods on Petroleum Products and Lubricants," published in 1972, which provides

detailed guidance for experimental evaluation of precision.

Wherever appropriate, special impurities or problems found in other likely types of recycled

oils besides used automotive oils have also been

considered in the individual tests (e.g., copper corrosion for used industrial oils). Occasionally,

the presence of an unusual contaminant in a used

oil may make the oil unsuitable for use as a fuel. Examples of such unusual contaminants may include chlorinated solvents, certain transformer

fluids such as polychlorinated biphenyls (PCB's),

nitrosamines, and other toxic chemicals. (Listings of hazardous and toxic chemicals may be obtained from the Occupational Safety and Health

Administration (OSHA) and/or the EPA.) Although

the presence of such unusual contaminants has occasionally been noted in the literature or in various reports, they were considered to be be- yond the scope of this report and their effect

on these test procedures was not evaluated.

Test Procedures

This section contains test procedures which

have been evaluated for use with recycled oil for use as a burner fuel. These tests aim at evaluating important performance-related prop- erties of the fuel oil. In addition to specific

requirements for the various test procedures

and limiting values, fuel oil specifications

also contain general requirements. Since these

general requirements are also required for ade- quate performance of a recycled oil, they are included here as stated in ASTM D 396-76.

"2. General Requirements

"2.1 The grades of fuel oil specified

herein shall be homogeneous hydrocarbon oils,

free from inorganic acid, 4 and free from

excessive amounts of solid or fibrous foreign matter likely to make frequent cleaning of suitable strainers necessary.

"2.2 All grades containing residual compo- nents shall remain uniform in normal storage

and not separate by gravity into light and heavy oil components outside the viscosity

limits for the grade."

Specific test procedures are discussed below.

5.1 Sampling

Proper sampling of fuel oils is important

because the commercial value of a petroleum pro- duct is judged by the characteristics of the sample as determined by laboratory tests [18].

The sample obtained for evaluation in the laboratory must be representative of the lot or a wrong evaluation will be made, regardless of the accuracy of subsequent tests.

Physical sampling methods used to obtain

representative samples from bulk lots of fuel

oil are described in the ASTM method D 270-65 5 (reapproved in 1975), "Sampling Petroleum and Petroleum Products" [19]. Method D 270 describes

and specifies many different procedures, depending on the type of container (ship, barge tank,

tank car, etc.) and the vapor pressure of the product.

Another sampling procedure applicable to fuel oils is given by ASTM E 300-73, "Sampling Industrial Chemicals." In addition to a procedure

for physical sampling of simple liquids (based

on D 270), it includes several sections on sta- tistical considerations. In the discussion

of simple liquids, E 300 notes that, "Although

single-phase liquids are homogeneous by definition, it may be desirable to check for this

condition by sampling from various sections of the container" [20]. The statistical sections

of E 300 are currently undergoing revision [21].

Fuel oil specifications and standards vary considerably in their requirements for sampling,

ranging from none to fairly detailed requirements. The sampling requirements of existing

fuel oil specifications are summarized in table

5, followed by a more detailed discussion of the requirements of each specification.

4 A qualitative determination of the acidity of a hydrocarbon liquid may be made using ASTM D 1093-65, "Acidity of Distillation Residues or Hydrocarbon Liquids" [2] (see sec. 5.3.5, Acidity,

this report).

5 The first number, i.e., D 270, is the ASTM test

method, while the second number, i.e.; -65, is the year of last revision (1965).
Table 5. Summary of sampling requirements.

Specification Requirement

D 396-76 No requirement.

VV-F-815C Take one sample in accordance

with D 270 (physical methods).

MIL-F-859E Take upper, middle, and lower

samples according to D 270; com- posite the samples if their API gravities do not vary from the average by more than 0.3° (0.0012

density units).

MIL-F-16884G Same as W-F-815C

American Petroleum Institute; see also Section

5.2.5, Density of this report.

1. ASTM D 396-76, Standard Specification for

Fuel Oils

The D 396-76 specification provides minimum

criteria for fuel oils and is widely used in the marketplace for procurement purposes. This

specification contains no requirement or sugges- tion for sampling. Under section 2.1, the grades of fuel oil are required to be "homo- geneous hydrocarbon oils," but criteria for the determination of homogeneity are not included.

2. VV-F-815C, Federal Specification, Fuel Oil, Burner

This specification is identical to ASTM D 396-76 in most respects. One major difference

exists, however, in the sampling requirements.

In VV-F-815C, a bulk lot is defined in section 4.2 as follows:

"4.2 Lot

"4.2.1 Bulk lot . An indefinite quantity of

a homogeneous mixture of one grade of fuel

oil offered for acceptance in a single, isolated container; or manufactured in a single

plant run (not exceeding 24 hours), through

the same processing equipment, with no change

in the ingredient materials."

For the details of sample collection, ASTM

method D 270 is cited. Several methods are specified in D 270 for bulk sampling, depending

on the type of container. For example, storage

tanks, ships, and barges require bottle sampling;

storage tanks with taps, tap sampling; open discharge streams, dipper sampling; and tank

cars and storage tanks, thief sampling. Thief

samplers may be used for bottom sampling, while

bottle sampling may be used to obtain an all- levels sample, upper-, middle-, and lower-tank

samples, multiple composite tank samples, etc. The sampling details must be recorded for each

specific sample.

3. MIL-F-859E, Military Specification, Fuel Oil, Burner (Navy Special)

This military specification provides very specific directives for sampling. Section 4.2.1

specifies the sampling method and criteria for determining homogeneity of the sampled lot.

"4.2 Sampling

"4.2.1 Bulk lot. An indefinite quantity of

material from one storage tank offered for

acceptance. To establish homogeneity, upper, middle, and lower samples as prescribed in ASTM D-270 shall be taken from each lot and subjected to API gravity determinations in accordance with method 401 of FED-STD-791.

To be considered homogeneous, those gravities

shall not vary from the average more than

0.3°. If the lot is homogeneous, samples

shall be composited for acceptance testing.

If the lot is not homogeneous, acceptance

tests shall be performed separately upon the upper, middle, and lower samples."

Federal Test Method Standard No. 791B-Method

401, referred to above, is actually the ASTM method D 287-67, "API Gravity of Crude Petroleum

and Petroleum Products (Hydrometer Method)." An identical and preferred method is the international version, ASTM D 1298-67, "Density, Specific Gravity or API Gravity of Crude Petroleum

and Liquid Petroleum Products by Hydrometer

Method" [2].

MIL-F-859E is presently not used by the U.S. Navy, which now uses MIL-F-16884G [22].

4. MIL-F-16884G, Military Specification, Fuel Oil,

Diesel , Marine

This specification contains essentially the same sampling requirements as VV-F-815C, which

calls for samples to be taken in accordance with

ASTM D 270.

For recycled oils, an adequate sampling pro- cedure is especially important in order to pro- vide acceptable evaluation of the product by

testing. This is so because of the high levels

of impurities often found in used oils collected

for recycling (see section 3 of this report).

These impurities include water, sediment (including fine particulates), volatile solvents,

lead, and the like. Processing of used oil for

use as a fuel by low-level techniques such as settling and/or centrifugation is not likely to remove all or even most of these impurities.

Stratification resulting from differing densities

may occur due to settling of particulates or water, lack of adequate homogenization of used

oils from different sources, improper blending

with virgin fuel oil in a large tank, or for other reasons [5].

Stratification of was noted in the lite

distillate oil blends

tion apparently occur

ficulty of adequately

in large tanks. The

used oils and virgin

documented; however,

the homogeneity probl

several recycled used oils rature for used oil/virgin

[5,14]. This stratificared largely due to the difmixing dissimilar oil types

problems with reprocessed

residual oils are less well

an API Task Force recognized

ems of used oil and used
the following method to assure homogeneity [9].

First, a special pump was installed to allow the

used oil in storage tanks to be recirculated.

Second, the tank supplying the used oil/virgin

residual fuel oil to the combustion system was equipped with a large stirrer. Finally, the density of the waste oil in the supply tank was measured every half-hour during operation of the test system to monitor homogeneity (note:

used oil/virgin residual oil blends ranged

from percent up to 15 percent by volume, v/v).

The recommended sampling requirements for re- cycled used oils used for fuel are the physical

sampling procedures as given in ASTM D 270, which

are applicable to recycled oils, with a modification to check homogeneity. This modification

utilizes variations in density, or API gravity,

to indicate an inhomogeneity of the material in the sampled lot. To check for this a sampling

procedure based on MIL-F-859E is suggested for evaluating bulk lots. An evaluation of the test procedure is given in this report. 6 Possible

language for specifying the examination of a bulk lot for homogeneity is as follows:

For bulk lots where a bulk lot is defined

as an indefinite quantity of hydrocarbon oil of one grade in a single isolated container,

upper, middle, and lower samples will be taken

using thief or bottle samples as described

in ASTM D 270, section 14. Samples may be composited to a single sample if the lot is homogeneous. If the lot is not homogeneous,

specification tests will be performed sepa- rately on the upper, middle, and lower samples.

Homogeneity will be determined on the basis of density ASTM D 1298 or ASTM D 287. Lots will be considered homogeneous if the gravity determinations for the upper, middle,

and lower samples do not vary from the average

by more than 0.0012 density units or 0.3° API gravity.

Conclusion

The ASTM D 270-65 sampling procedures are applicable to recycled oil for use as burner

fuel with the modification described above to check homogeneity. These procedures are recom- mended to obtain samples for the various tests

used to characterize bulk lots of recycled oil to be used as fuel.

modifications as described in the individual test procedures. Two additional tests, aniline point

and heating value, are recommended for use with

recycled oils. A test for the heating value is particularly important since the combustion energy

is the primary commodity of trade for a fuel oil.

These test procedures were evaluated for use with recycled oils using the evaluation process described in section 4 of this report. In general, for this category of test procedures, the test itself attempts to simulate actual perfor- mance (e.g., flash point is the lowest temperature at which the petroleum product "flashes").

Therefore, the test procedure itself defines the correct or "true" value for the measurement. The evaluation of this type of test procedure is thus concerned primarily with whether or not contaminants and impurities interfere with the perfor- mance of the test.

The individual test procedures are discussed

below.

5.2.1 Flash Point

Flash point is the temperature to which a fuel must be heated to produce a vapor/air

mixture capable of being ignited with an open

flame. It is also an indication of maximum safe handling temperature of a burner fuel oil - both

important aspects of performance. The flash

point of recycled oils may be lowered by contam- ination of the specified fuel oil grade by a more volatile component. Therefore, a major

concern for the flash point test is its ability

to detect contamination of a recycled oil with a more volatile material such as a solvent or gasoline dilution from a used crankcase oil.

The usual test procedure for determining

flash point of virgin fuel oils is the ASTM method D 93-77, "Flash Point by Pensky-Martens

Closed Tester." This test procedure is identical to the British Institute of Petroleum Test Method 34/71 and the Federal Test Method 1102 - Federal Standard Number 791B. This test is stated to be applicable to virgin petroleum

products such as all burner fuel oils, lubricating oils, and other petroleum liquids. D 93

is the ASTM referee method for flash point in cases of dispute for both the ASTM fuel oil specification and the Federal specification for burner fuel oils.

5.2 Test Procedures for Bulk Properties

This section contains test procedures for

the bulk properties of a recycled used oil to

be used as a burner fuel. The bulk properties

which are tested and specified for virgin burner

fuel oils are flash point, pour point, distillation temperature, viscosity, density, and copper

corrosion. Test procedures for these properties

are also recommended for recycled oils, some with

B See Section 5.2.5, Density of this report.

Two additional flash point test procedures

are available but were not evaluated in this

program. In the Cleveland Open Cup test method

(ASTM D 92-72) the procedure states it is inappropriate for use with fuel oils or for the detection of the presence of small concentrations of

a lower flash point material [2]. The other

method is ASTM D 56-77, "Test for Flash Point by

Tag Closed Tester." Since D 56 can only be used with the distillate fuel oils (grade numbers 1 and 2), it is therefore of limited applicability

to recycled fuel oils.

In the Pensky-Martens test method (D 93-77),

the sample is contained in a cup that has a
cover containing a shutter, which is normally

closed during heating and opened only briefly at intervals for the test. "The sample is heated

at a slow, constant rate with continual stirring.

A small flame is directed into the cup at regular

intervals with simultaneous interruption of

stirring. The flash point is the lowest temperature at which application of the test flame causes the vapor above the sample to ignite"

[2]. D 93-77 includes a basic procedure, method

A, and also a method B, "Determination of Flash

Point of Suspensions of Solids and Highly Viscous

Materials" [2]. Method B is the same as method

A except for requiring a higher stirring speed

and a slower heating rate. The precision, as developed with virgin fuel oils and as stated in

D 93-77, is shown in table 6 for both methods. 7

The Pensky-Martens test procedure was evaluated for recycled oil used as burner fuel. As part of this evaluation the D 93-77 test procedure was applied to a number of used oils,

recycled oils, virgin distillate fuel oils,

virgin distillate fuel oil/used oil blends, and

used oil mixed with gasoline. These data are shown in table 7 and indicate that the repeatability of the flash point test for these samples

7 In D 93-77, the repeatability and reproducibility table for method B is for viscous

materials "...which tend to form a surface

film" [2]. The samples tested which required

method B do not form such films; therefore, we compared against the method A table.

Table 6. Precision of flash point test procedures for virgin fuel oils

b Flash point

range

104 °C and

under

Above 104 °C

Repeatability

2 °C (4 °F)

5.5 °C (10 °F)

Reproducibility

3.5 °C (6 °F)

8.5 °C (15 °F)

Table and footnotes are from ASTM method D 93-77. The method should be consulted

for additional details.

''Duplicate results by the same operator should be considered suspect if they differ

by more than these amounts.

'Results submitted by each of two different laboratories should be considered suspect

if they differ by more than these amounts.

Table 7. Repeatability of the flash point test procedure (D 93-77).

Sample

No. 2 fuel oil (F131)

No. 2 fuel oil + 5% W022a No. 2 fuel oil + 15% W022

No. 1 fuel oil (F132)

No. 5 recycled fuel oil (F134)

No. 5 recycled fuel oil (F133)

Used oil (W024)

a Used oil (W022) a

Used oil (W022) with 5%

gasoline added (v/v)

Experimental

flash point, °C (°F)

68.3 (155)

68.3 (155)

68.3 (155)

69.2 (157)

67.8 (154)

68.9 (156)

51.1 (124); 51.7 (125)

121.7 (251); 121.7 (251)

138.3 (281); 137.8 (280)

58.1 (138); 56.7 (134)

91.7 (197); 89.4 (193)

22.8 ( 73); 23.9 ( 75)

c

W022 and W024 are used automotive crankcase oils.

Apparent flash point; sample flashed at room temperature without heating.

10
is consistent with that of virgin fuel oils, as shown in table 6. The D 93 test method states

in note 2 that this method may be employed for

the detection of contamination of lubricating

oils by minor amounts of volatile materials,

which indicates that this test procedure should

be effective in measuring this type of contamination.

Conclusion

The flash point test is used to indicate both

the safety and the adequate performance of the burner fuel [19]. The Pensky-Martens test pro- cedure, ASTM D 93-77, has been evaluated with

recycled fuel oils, blends of virgin fuel oil with recycled oil, and oils containing volatile

contaminants. This test may be used to establish

that a product meets the specified minimum value

of flash point.

5.2.2 Pour Point

Fuel oils are often stored in outside tankage,

and a knowledge of the lowest temperature at which the fuel can be transferred from tank to burner is necessary. The pour point describes

the flow characteristics of an oil and the lowest temperature at which the oil will flow

under standard test conditions [2,19]. An indication of this temperature is given by the pour point, which is the temperature at which

wax crystals crystallize out of the hydrocarbon

fuel and the wax structures build up sufficiently

to prevent the flow of the oil under low forces

[3]. This temperature can also be used as an indication of the low temperature pumpability of the oil. Additives are sometimes used to lower

the pour point.

The test procedure used for virgin fuel oils

is ASTM D 97-66 (reapproved in 1971), "Pour

Point of Petroleum Oils." This test is identical to IP 15/67, to Method 201 - Federal Test Method Standard No. 791B, and to British

Standard 4452, and is intended for use on any petroleum oil [2].

To determine the pour point using D 97, the

sample is heated and then cooled at a specified

rate and examined at intervals of 5 °F (3 °C)

is generally applied to grade numbers 1, 2, and

4 fuel oil [2]. It is usually not specified for numbers 5 and 6 since preheating may be required

for handling, transfer, and use of these oils,

depending on climate and equipment; however, a "low pour" fuel oil may be specified for grade

number 6 [2].

The precision of method D 97 for virgin fuel oils is stated to be as follows [2].

"7. Precision

"7.1 Repeatability-Duplicate results by the same operator should be considered

suspect if they differ by more than 5 °F (or

3 °C).

7.2 Reproduc

by each of two ered suspect on

by more than 10

7.For oi Is described in 5. order cannot be anomalous pour

thermal history

include black o distillate fuel

ibility—The results submitted

laboratories should be considly if the two results differ

°F (or 6 °C).

tested by the procedure

9, reproducibility of this

expected, as these oils show

points depending on their

. 5 " [These special-case oils

il, cylinder stock, and non- oil.]

" b It is a recognized property of these oils

that the temperature to which they have been

subjected before testing influences their

pour points. Although the lower pour points

as determined by the special procedure will show approximately the reproducibility given, the upper pour points will show greater

variations depending on the previous thermal

history of the oils. Further information on this subject is contained in Proceedings,

ASTEA, Am. Soc. Testing Mats., Vol 31, Part

I, 1931, pp. 468-470, and Vol 32, Part I, 1932, pp. 402-405."

The D 97 test procedure was eva with recycled oils. As part of th the test was applied to a number o recycled distillate fuel oils, dis oil/used oil blends, and heavier r oils. These data are shown in tab repeatability and reproducibility

point test for these samples are c those for virgin fuel oils as disc Most used automotive crankcase oil the pour point of virgin fuel oils

late and residual. This effect is table 8 for the distillate fuel oi blends, and is most likely due to of pour point depressants in these

oils. The results of our evaluati

that the pour point test procedure

effectively used with a recycled f

Conclusion

luated for use

is evaluation

f virgin and filiate fuel ecycled fuel

le 8, and the

of the pour

onsi stent with

ussed above,

s wi 1 1 lower

, both distilshown in 1/used oil the presence

high additive

on indicate

, D 97, can be

uel oil.

The pour point of a fuel oil is a useful indi- cator of the low- temperature flow characteristics

of fuel oil. ASTM method D 97-66, "Pour Point

of Petroleum Oils," has been evaluated with re- cycled fuel oils and with blends of virgin fuel oils and used oils, and may be used to measure

the pour point of recycled petroleum oils to be used as fuel.

5.2.3 Distillation Temperature

Distillation (volatility) characteristics of distillate fuel oils are important indicators of performance. Heating installations which use vaporizing or atomizing burners operated with

distillate fuel oils require fuels that contain

sufficient volatile components to ensure ready

ignition and a stable flame [19]. In addition,

the volatility of the fuel must be uniform from

11
Table 8. Precision of the pour point test on fuel oils and fuel oil blends (D 97).

Pour point, °C (°F)

Fuel oil grade

1

2

2

2

2

Sample

Sample

number

Distillate fuel

oil (virgin)

F132

Distillate fuel

oil (virgin)

F131

Distillate fuel

oil blend

(F131)

b

Distillate fuel oil blend(F131)

Distillate fuel

oil blend

(F131)

Recycled distillate fuel oil 7L24

Recycled fuel

oil F133

Recycled fuel

oil F134

% recycled

oil*

(ir

(5) a

(10)

£

100

100

100

Operator 1

-46 (-51)

23 (-10)

23 (-10)

32 (-25)

-37 (-35) -37 (-35)

-54 (-65)

-54 (-65)

-14 (+ 7) -14 (+ 7)

-45 (-49) -44 (-47)

-41 (-42) -44 (-47)

Operator 2

-46 (-51)

32 (-25)

-48 (-55)

W022 composite used automotive oil; not processed beyond collection and storage.

Sample number in parentheses for blends indicates the sample number for the virgin distillate

fraction.

Viscosity measurements on this oil placed it between grade numbers 2 and 4.

batch to batch to avoid frequent resetting of burner controls and to maintain maximum perfor- mance and efficiency of the heating system [19].

The distillation temperature test is generally

not applied to residual fuel oils [19].

There are five different ASTM distillation

test procedures, but only one of them is normally used for fuel oils [19]. This test is D 86-77,

"Distillation of Petroleum Products," and is identical to Method 1001 - Federal Test Method

Standard No. 791B, Institute of Petroleum

designation 123/68, British Standard 4349, and

Deutsche Norm DIN 51751. The D 86 test procedure provides that "A 100-ml sample is distilled

under prescribed conditions which are appropriate

to its nature.... Systematic observations of

thermometer readings and volumes of condensate

are made, and from these data, the results of the test are calculated and reported" [2]. For

the distillate fuel oils the temperatures at which 10 percent and 90 percent of the total volume have distilled are the values usually

used in specifications. In addition, the

initial boiling point and the 50-percent volume

point are also often recorded.

The precision of this test procedure is dependent upon the rate of change of the thermometer reading at each stage at which a result

is obtained. There are two nomographs given

with the test procedure which provide estimates

of repeatability and reproducibility based on information taken during the test [2]. For ex- ample, in our evaluation of this test procedure

using virgin distillate fuel oils, the repeatability according to the ASTM nomographs ranged

from 1 to 3 °C. The ASTM reproducibility was higher by a variable factor.

The distillation temperature test procedure

(D 86) was evaluated for use with recycled oils. As a part of this evaluation, D 86 was applied

to a series of distillate fuel oil samples in- cluding virgin oils, recycled oil, and blends

of virgin distillate fuel oils with 10-percent

used automotive crankcase oil. The results of these tests are found in table 9. Two of the test samples examined, a 10 percent blend of

used automotive oil with a grade number 1 virgin

fuel oil and the distillate fuel oil product

from a recycler, failed to distill to the 90 percent point within the temperature range limitations of the test apparatus. [This tem- perature limitation is also due to the fact that

if oils are heated above 370 °C (700 °F) they

tend to decompose ("crack") and provide unreliable results [19].]

12
Table 9. Repeatability of distillation temperatures for distillate fuel oils (D 86).

Fuel ASTM

oil Sample % Recycled % Sample [listillation repeatabil ity

grade Sample of method, °C

Virgin

number

F132

oil recovered

BP

temperatu res, °C

1 181.1 179.6, 179 6 1.6

fuel oil 10 194.6 195.7, 194 7 1.3

50 219.7 220.7, 220 2 1.3

90 257.8 258.8, 256 8 1.8

2 Virgin F131 — BP 191.3 194.3, 186 6, 190 7 2.5

fuel oil 10 214.3 213.3, 216 7, 217 7 1.7

50 258.3 257.3, 258 8, 259 8 1.5 (D b 90 318.4 312.4, 318 9, 316 9 2.2 Virgin F132 10

c BP 178.3 178.3 1.9 oil/used 10 194.3 196.3 1.6

oil blend 50,

90

d 223.3 223.3 1.4

(2)

b — —

Virgin F131 10

C BP 188.4 196.5 2.2 oil/used 10 215.0 , 217.5 1.7

oil blend 50

e 90 264.5

352.6

266.5

, 357.6

1.6 2.6 ___f Recycled

fuel oil 7L24 100 BP

10 n 50g

138.7

207.7

349.0

, 128.6

, 211.2

, 354.0

Off scale

2.9

1.5

a The D 86-77 test procedure states in a footnote that "Precision for this method is under review.

Indications are that precision for initial boiling point... may be indeterminate" [2]. Indicated grade is for the distillate virgin oil fraction; the blended fuel oil sample is not considered a distillate fuel for some uses. Used oil sample blended with the distillate fuel is W022, a composite used automotive crankcase

oil which was not processed beyond collection and storage.

Unable to distill 90 percent of sample within temperature range of test apparatus; 80 percent

distilled at 338.4 °C, leaving a black, gummy residue.

Sample near end of distillate fraction and had rapid temperature rise. The viscosity characteristics of this recycled distillate fuel oil placed it between fuel oil grade numbers 2 and 4. 9 Due to excessive temperature rise, unable to go above the 50 percent point.

This evaluation indicates that the D 86 test procedure for distillation temperature is a useful test for the volatility characteristics

for recycled fuel oils. While the test results

for both the recycled oils and the virgin oils

often fell somewhat outside the indicated ASTM repeatability, this is not considered to be a serious problem. In fact, footnote 8 in the test procedure indicates that the precision of

this test is under review, especially for the

initial boiling point measurement [2]. However,

this test procedure will provide appropriate

information on the volatility characteristics of distillate recycled fuel oil samples.

Conclusion

The distillation (volatility) characteristics

are important indicators of performance for distillate fuel oils. The D 86-77 test procedure,

"Distillation of Petroleum Products," has been

evaluated with recycled distillate fuel oil and

blends of virgin distillate fuel oils with used

automotive oil. This test procedure may be used

to obtain the appropriate volatility characteristics of distillate recycled oils to be used

for fuel

5.2.4 Viscosity

Viscosity, or the internal resistance exhibited as one portion or layer of a liquid is moved in relation to another portion, is an important characteristic of fuel oil. It is indicative of the rate at which the oil will flow in fuel systems and the ease with which it can be atomized in a given type of burner. Overly viscous oils can produce problems throughout the heating oil system, including pumping

difficulties, burner ignition problems, and

flashback or erratic operation of the burner

[19]. An unsuitable viscosity also affects the output or delivery of a spray nozzle and the angle of spray, with subsequent poor atomization

and possible carbonization of the burner tip,

13
carbon deposition on the walls of the firebox,

or other problems caused by poor combustion

[19].

The test procedure generally used for determining

the viscosity of virgin fuel oils is ASTM method

D 445-74, "Kinematic Viscosity of Transparent

and Opaque Liquids (and the Calculation of Dynamic Viscosity)" [2]. This test procedure is identical to Method 305.6 - Federal Test Method

Standard No. 791B, the Institute of Petroleum

Designation IP 71/66, the British Standard 4708,

and the Deutsche Norm DIN 51550. This test procedure is applicable to liquid petroleum

products, both transparent and opaque, and covers all grades of fuel oil.

Another test procedure for the viscosity of

fuel oils is ASTM D 88, "Saybolt Viscosity," but

this method has now been withdrawn by ASTM Committee D-2, and the D 445 test for kinematic

viscosity is the method now preferred by this ASTM committee [19]. If desired, the Saybolt

viscosities can be calculated from the kinematic

viscosity using ASTM method D 2161-74, "Conversion

of Kinematic Viscosity to Saybolt Universal

Viscosity or to Saybolt Furol Viscosity" [2].

In the kinematic viscosity method, D 445, "The time is measured in seconds for a fixed

volume of liquid to flow under gravity through

the capillary of a calibrated viscometer under a reproducible driving head and at a closely

controlled temperature. The kinematic viscosity

is the product of the measured flow time and the calibration constant of the viscometer" [2].

The cgs unit of kinematic viscosity is one centimeter squared per second and is called one stokes (St). The SI unit of kinematic viscosity

is one meter squared per second and is equivalent

to 10 4 St. Frequently, the centistokes (cSt) is used (1 cSt = 10- 2 St).

The precision of the D 445 test procedure for "...clean, transparent oils tested between 15 and 100 °C (60 and 212 °F)" is stated as follows

[2]:

"Repeatability-Duplicate results by the same operator, using the same viscometer,

should be considered suspect if their difference is greater than 0.35 percent of their

mean.

"Reproducibility--The results submitted by

each of two laboratories should not be considered suspect unless their difference is greater than 0.7 percent of their mean."

No statement of precision is given for oils

which are not clean and transparent.

The D 445 kinematic viscosity test procedure

was evaluated for use with recycled oils to be used as fuel. As part of this evaluation, the

445 test procedure was applied to recycled

oils, used oils, virgin fuel oils, and used

oil/virgin fuel oil blends. The results of

these tests are found in table 10. With the

exception discussed below, the results are consistent with the ASTM repeatabilities for

transparent oils even though many of the re- cycled oils and oil blends are opaque.

During this evaluation, two potential problems

were examined. One potential problem is the presence of volatile components in the recycled,

used or waste oils. A second potential problem

is the effect of particulates which are suspended

in many used lubricating oils, and which pass through the 75 urn sieve recommended in D445 for

solids removal.

Since viscosities are measured at 40 °C or

50 °C, evaporation of volatile contaminants may occur during the measurement process. This, in fact, does occur with some used oils and is evidenced by increased viscosity with time

leading to a lack of repeatability (e.g., table

10, sample W011). However, the less viscous

(presumably higher volatility) numbers 1 and 2 virgin fuel oils did not show such changes with

time, leading to the tentative conclusion that

used oil sample W011 (and perhaps W022) contains

quite volatile components -- likely to be due to gasoline contamination.

It is possible to strip volatile components

by using ASTM method D3607-77, "Removing Volatile

Contaminants from Used Engine Oils by Stripping".

The procedure involves passing a stream of

nitrogen for 4.5 hours through a weighed 25-mL

sample maintained at 90 °C (194 °F) and determining the weight loss. Viscosity measurements

made before and after this procedure on samples

of used oil and a sample of recycled oil are listed in table 11. The percentage of volatiles

stripped from the various samples is also given,

as well as the percentage of water in the samples,

since the water contributes to the total volatiles removed at this temperature. (Water was determined by distillation, D95; see Section

5.3.1, Water and Sediment.) It can be seen that

repeatable values are obtained by this procedure,

yet the change in viscosity after stripping is large and strongly correlated with the volatiles

concentration in these particular samples. It

is concluded that this stripping procedure, in removing volatile contaminants of the oil, also removes components which contribute to its viscosity (and undoubtedly higher heating value,

an attribute of great importance for use as a fuel). A lower stripping temperature would

appear not to be a satisfactory solution to this

problem. Consequently, for those oils where the presence of highly volatile contaminants is suspected, as evidenced by changes in viscosity measurements with time leading to values outside

the ASTM repeatability limit, and as evidenced

by low flash point values (see Section 5.2.1,

Flash Point), it is recommended that the test report indicate lack of repeatability for ASTM

D445. This will allow purchasers to learn the value of the viscosity of the "as-is" material,

while at the same time, alerting them to possible

contamination by highly volatile compounds.

14
Table 10. Repeatability of the kinematic viscosity, (ASTM D445) of recycled fuels,

used oils, and used oil/virgin fuel oil blends.

Kinematic viscosity (cSt)

Virgin Percent Sample fuel oil recycled

Description number oil*

F132

grade

Virgin fuel oil 1 Used oil (W022)/fuel ( 1) oil (F132) blends ( 5) (10)

(20)

Virgin fuel oil F131 2 Used oil (W022)/fuel ( 1) oil (F131) blends ( 5)

(10)

(20)

1.561, 1.562

1.647, 1.649

1.805, 1.801

2.086, 2.093

2.782, 2.782

2.125, 2.120

2.389, 2.389

2.652, 2.639

2.956, 2.956

3.892, 3.898

Recycled distillate 7L24 — 100 5.405, 5.402

fuel oil

Recycled fuel oil F133 5 100 74.55 , 74.41

(source A)

Recycled fuel oil F134 5 100 56.98 , 57.02

(source B)

5 100

5 100 — (100) — (100)

6

Composite used crank- W022 (100) 60.73 , 60.84

case oil

Composite used crank- W011 (100) 65.97, 66.24, 67.27

case oil

Virgin fuel oil F130 6 67.02e

, 66.90

8

Numbers in parenthesis indicate percentages of a used automobile crankcase oil, which was

not processed beyond collection and storage.

Obtained at 40 °C unless otherwise noted. (Temperature as listed in ASTM 396-77).

Viscosity characteristics place this fuel oil between grades 2 and 4. Not within ASTM repeatability due to loss of volatiles (See text).

e Obtained at 50 °C. (Temperature as listed in ASTM 396-77 for this grade).

Table 11. Effect of volatiles removal on the kinematic viscosity test procedure (D 445).

Volatiles Water , (% by vol.

)

(% by vol.) Initial Stripped

3.42 0.19 60.73 78.60

3.70 60.84 78.59

4.68 0.10 65.97

C 103.65 4.56 66.24

67.27 103.65

2.26 0.64 56.98 63.47

2.36 57.02 63.44

Sample

number Description

W022 Composite used motor oil

W011 Used automotive crankcase oil

F134 Recycled fuel oil

3 Obtained using ASTM D 3607-77. Obtained using ASTM D 95; note that water is also removed from the sample by the stripping procedure.

This series of results is not within the ASTM repeatability (see text).

15
To evaluate the effect of small particulates,

samples of used oils were centrifuged at high

speed (15. 5K revolutions per minute) for 20 minutes. Preliminary experiments had shown that

centriguation caused significant temperature

increases in the samples, undoubtedly leading to viscosity increases due to volatiles loss. Con- sequently, the stripping method described above

(ASTM D 3607-77) was used to remove volatile

components before the samples were measured.

Viscosities of the samples before and after

centrifugation are given in table 12. The

results are consistent with the presence of colloidal particles suspended in a liquid (viscosity of the suspension greater than the fluid).

The magnitude of the effect is very small: within the repeatability of the test procedure

itself. For the used oils examined then, the presence of these small particles will not affect viscosity measurements to any great

extent.

Conclusion

The viscosity characteristics of a fuel oil are important for assuring acceptable flow and

pumpability performance in service. ASTM test method D 445-74, "Kinematic Viscosity of Trans- parent and Opaque Liquids (and the Calculation

of Dynamic Viscosity)," is an appropriate test procedure for the measurement of this characteristic for recycled fuel oils, with one modification for oils which give evidence (increased

viscosity with time outside repeatability limits,

low flash point) of contamination by volatiles:

a notation in the test report that repeatability

was not obtained, and the viscosity values listed

in sequence.

5.2.5 Density

The density, or mass per unit volume, of a fuel oil enters into most pricing structures and

is used by refiners in the control of refinery

operations [19]. The determination of the density

serves at least three purposes: (1) it provides

a check on uniformity for bulk quantities of

fuel oils (see also Section 5.1.1, Sampling);

(2) it permits the calculation of weight per gallon; and (3) it provides information for

estimation of the heating value of a fuel oil (see also Section 5.2.8, Heating Value).

Values for the mass unit volume may be re- ported in three ways for petroleum products: as density, as specific gravity, or as API gravity.

The density of a fuel oil is the mass of a unit

volume at a specified temperature (15 °C and

60 °F are the usual temperatures for petroleum

product measurements [2]). The specific gravity

(or relative density) of a fuel oil is the ratio

of the mass of a given volume of the product at some temperature to the mass of an equal volume

of distilled water at the same temperature, both masses being corrected for buoyancy in air. The

API gravity of petroleum products is based on an arbitrary hydrometer scale which is related to the specific gravity in accordance with the formula

API gravity, in degrees =

141.5

specific gravity at 60 °F/60 °F

- 131.5.

The API gravity is generally used for most

commercial transactions in the United States as well as in refinery practice, while the specific

gravity is in general use in some foreign countries. The value for API gravity is required in existing fuel oil specifications only for grade

numbers 1 and 2.

Two procedures are available for measuring

this characteristic. The first one is ASTM D 1298-67 (reapproved in 1977), "Density, Specific

Gravity or API Gravity of Crude Petroleum and Liquid Petroleum Products by Hydrometer Method"

[2]. D 1298 is identical to API Standard 2547, to the Institute of Petroleum Designation IP 160/68, to the British Standard 4714, and to the

Deutsche Norm DIN 51757. The second procedure

is ASTM D 287-67 (reapproved in 1977), "API Gravity of Crude Petroleum and Petroleum Products

(Hydrometer Method)," which is identical to API Standard 2544 and to Method 401 - Federal Test Method Standard No. 791B [2]. D1298, used internationally, is the preferred one since it provides

means for converting values determined in any one of the three systems of measurement to equivalent values in either of the other two. For

the measurement of API gravity, the two test procedures are essentially equivalent, so an evaluation of D1298 will serve to evaluate D287

at the same time.

Both of the above procedures are based on the

principle that the depth of immersion of body

floating in a liquid is inversely proportional

to the density of the liquid. The floating body,

with appropriate graduations, is called a hydrometer. The sample is brought to the prescribed

temperature, transferred to a cylinder, and the appropriate hydrometer is lowered into the sample

and allowed to float. After temperature equilibrium is reached, the hydrometer scale is read

and the temperature noted [2].

The ASTM repeatabilities and reproducibilities

of D 1298 and D 287 are shown in table 13. For very viscous products, the D 1298 test procedure

states that "...no specific variations can be given" [2].

The hydrometer test procedure for determining

the density of fuel oils (D 1298) was evaluated

for use with recycled oils. As part of this

evaluation the test procedure was applied to a number of used oils, recycled oils, virgin oils,

and virgin fuel oil/used oil blends. These data

are shown in table 14 and indicate that the re- peatability of the API gravity for these samples

is consistent with the ASTM repeatability as shown in table 13.

One problem encountered during the NBS eval- uation was the entrapment and slow release of small bubbles in some samples of recycled oil after very vigorous agitation (e.g., use of a mechanical shaker). These air bubbles could

result in an apparent increase of one degree or

16
Table 12. Effect of particulates on the kinematic viscosity of used oils (D 445).

Sample

number

W022

W004

won

Description

Composite used motor oil

Used automotive crankcase oil

Used automotive crankcase oil

Viscosity (cSt at 40 °C)

Initial"

78.60, 78.59

66.61, 66.40

103.65, 103.65

Initial viscosity measurement made after stripping with D 3607-77 (see text).

After

centrifugation

78.42, 78.44

65.60, 65.55

103.35, 103.37

Table 13. ASTM precision for D 1298 and D 287 [20]

Test procedure

D 1298

Type of

petroleum

product

Transparent,

nonviscous

Temperature

range

-2 to 24.5 °C

29 to 76 °F

42 to 78 °F

Units

Density (kg/L at 15 °C)

Specific gravity (at 60 °F/60 °F)

API gravity (degrees at 60 °F)

RepeatabilityReproducibility

0.000^ 0.0012

0.0005 0.0012

0.1 0.3

D 1298 Opaque,

nonviscous

-2 to 24.5 °C Density (kg/L at 15 °C)

29 to 76 °F Specific gravity (at 60 °F/60 °F)

42 to 78 °F API gravity (degrees at 60 °F)

0.0006 0.0015

0.0006 0.0015

0.2 0.5

D 287 All 42 to 78 °F API gravity (degrees at 60 °F) 0.2 0.5

more for the API gravity. This problem is eliminated by the use of gentle agitation for the sample container, or any method which does not introduce air bubbles. The D1298 procedure

indicates in Sections 7.2 and 7.5 of the pro- cedure that the formation of air bubbles in the sample is to be avoided, and if formed, suf- ficient time must be allowed for all such bub- bles to come to the surface and be removed from

the cylinder. The data in table 14 demonstrate

this problem, and the API gravity values for

several heavier residual oils were generally

lower in later trials after more gentle agitation was employed.

Conclusion

The density, specific gravity, or API gravity

is a useful characteristic for the evaluation

and monitoring of fuel oils. The ASTM test pro- cedures D 1298-67, "Density, Specific Gravity or

API Gravity of Crude Petroleum and Liquid Petroleum Products by Hydrometer Method," and D 287-67,

"API Gravity of Crude Petroleum and Petroleum

Products (Hydrometer Method)," have been eval- uated for use with recycled fuel oils, used oils,

and blends of virgin fuel oils with used oils. These tests may be used to establish that a fuel

oil product meets the appropriate requirements

for density, specific gravity, or API gravity.

5.2.6 Copper Corrosion

Tests for corrosion are of a qualitative type

and are made to ascertain whether fuel oils are

free of a tendency to corrode copper fuel lines and brass or bronze parts used in the burner

assemblies [19]. The copper corrosion test is considered to be a test for "active" or "cor- rosive" sulfur in petroleum products and, as such, complements the test for total sulfur,

which is discussed in Section 5.3.4, Total Sulfur, of this report.

Organic sulfur compounds (e.g., mercaptans,

sulfides, polysulfides, thiophenes, etc.) are present in most petroleum products in variable

amounts, depending on the crude oil origin and

the refining processes [3]. Tests of the ten- dencies of the fuel oil to corrode copper and copper alloys are made using specially prepared

copper strips. The effects due to corrosive

17
Table 14. Measurement of the API gravity for recycled oils, used oils,

and fuel oil/used oil blends (D 1298)

a

.

Fuel

oil Description

Virgin distillate fuel oil Blend

Blend

Sample

number

F132 (F132)

(F132)

Percent recycled

oil

API

[at

gravity, degrees

60 °F (15.6 °C)]

grade Operator 1

42.3

41.9

Operator 2

1 (°) b K

C (10) D,C

42.9, 43.0

41.7, 41.7

41.2, 41.3

2 Virgin distillate fuel oil Blend

Blend

F131

(F131)

(F131)

u

< 5

> b'c

(10)

D,C

35.0

34.7 34.1

35.0

34.6 34.0

___d Recycled distillate fuel oil 7L24 100 34.1 34.1 (trial 1)

34.3, 34.3 (trial 2)

5

5 Recycled fuel oil Recycled fuel oil F133 F134

100

100 26.4

26.8, 26.8

25 8 25 8

26. 6^ 26.6, 26.4, 26.5 (trial 1 25.8, 25.7 (trial 2)

25.6 (trial 3)

Composite used oil

Composite used oil

Composite used oil

Virgin residual fuel oil

Virgin residual fuel oil Virgin residual fuel oil

W023

W022

W033

F125

F130

F022

(100)

(100)

(

(100)'

26.8

26.6

23.2

17.9

11.0

26.6 (trial 1)

26.4, 26.4 (trial 2)

e 26.8, 26.8 (trial 1)

26.4, 26.4 (trial 2)

e 28.6, 28.6, 28.7, 28.7 (trial 1 28.8, 28.8 (trial 2)

e

23.8, 23.9 (trial 1)

23.7, 23.7 (trial 2)

e 23.5 (trial 3)

e

17.9

11.2

For purposes of the ASTM repeatability and reproducibility (table 13), these samples are assumed to

be "non-viscous".

W022 composite used oil.

Not processed beyond collection and storage.

Viscosity characteristics of this oil place it between grade numbers 2 and 4.

For these trials, efforts were made to minimize bubble formation (see text).

species in the oil are indicated by discoloration and blackening of the strip [3]. Fuel oil specifications usually place limits on the de- gree of staining permitted by distillate fuel oils.

The test procedure commonly used to measure

copper corrosion is ASTM D 130-75, "Detection of Copper Corrosion from Petroleum Products by the Copper Strip Tarnish Test" [2]. This method is identical to Method 5325 - Federal Test Method

Standard No. 791B, Institute of Petroleum designation IP 154/69, British Standard 4351, and

Deutsche Norm DIN 51756. The D 130 procedure is conducted as follows: "A polished copper strip

is immersed in a given quantity of sample and

heated at a temperature and for a time characteristic of the material being tested. At the end of this period the copper strip is removed,

washed, and compared with the ASTM Copper Strip

Corrosion Standards" [2]. It is assigned a nu- merical rating from la (slight tarnish) to 4c (corrosion). Thus, the corrosiveness of the sample is interpreted "...accordingly as the appearance of the test strip agrees with one of the strips of the ASTM Copper Strip Corrosion

Standards" [2]. Consequently, the ASTM D 130 test procedure is a qualitative one, and no statements are included in the test regarding

repeatability and reproducibility [2].

The D 130 copper corrosion test was evaluated

for use with recycled oils. As a part of this

evaluation, the test was applied to virgin fuel oils, used oils, and recycled oils. The results

are summarized in tables 15 and 16. Table 15 contains the results of the D 130 test with the

18
Table 15. Copper corrosion test on fuel oils at 50 °C for 3 hours (D 130).

Fuel oil grade

Sample

number

F131

Description

Tarnish

classification

la

la

Designation Color

2 Virgin fuel oil Slight tarnish

Slight tarnish

Light orange

Light orange

7L24 Recycled distillate

fuel oil

2b

2b Moderate tarnishModerate tarnish

Violet pink

Violet pink

Blend 90% number 2; la Slight tarnish Yellow/brassy

10% used oil

b la Slight tarnish Yellow/brassy

Blend 50% number 2; la Slight tarnish Yellow/brassy

50% used oil

b la SI ight tarnish Yellow/brassy — W022 Composite used

automotive oil la

la Slight tarnish

SI ight tarnish

Light orange

Light orange

W037 Industrial waste oil (Source B) 4a

4a

Dark tarnish/

corrosion

Dark tarnish/

corrosion

Multicolored/

black

Multicolored/

black — W033 Composite used oil from

service station

la

la Slight tarnishSlight tarnish

Light yel low Light yellow

Viscosity measurements on this oil place it between grade numbers 2 and 4. Used oil was W022; virgin distillate fuel oil was F131.

conditions called for in the ASTM D 396 fuel oil specification, 3 hours at 50 °C. Increasing the test temperature to 100 °C, as called for in the

Federal specification VV-F-815C, resulted in a moderate increase in the severity of the test

(i.e., increased corrosion of the copper strip)

as indicated by the test results shown in table

16. Note that one of the recycled oils, the distillate oil (7L24), caused copper corrosion

as defined by the ASTM standard strips (i.e.,

number 4 rating) at the 100 °C temperature but did not at 50 °C.

Conclusion

The corrosive properties of a recycled fuel

oil are measured in order to assure long burner

life and adequate performance in the field. ASTM test procedure D 130-75 has been evaluated

for recycled oils and can be used to indicate

the relative corrosiveness of the fuel oil for copper and copper-alloy components.

5.2.7 Aniline Point

The aniline point is defined as the minimum

equilibrium solution temperature for equal vol- umes of aniline and sample [2]. The aniline

point is useful as an aid in the characterization of pure hydrocarbons and in the analysis

of hydrocarbon mixtures. Aromatic hydrocarbons

exhibit the lowest and paraffins the highest

aniline point values [2]. Because of these

19

differences, the aniline point is often used

to provide an estimate of the aromatic

hydro-carbon content of petroleum mixtures.

Oils with high aromatic content have swelling

and deteriorating effects on natural and syn- thetic rubbers [18]. The aniline point may therefore be of interest for distillate fuel oil products that come in contact with rubber gaskets

or seals.

The test procedure for aniline point is ASTM

D 611-77, "Aniline Point and Mixed Aniline Point

of Petroleum Products and Hydrocarbon Solvents."

In this method, "Specified volumes of aniline

and sample, or aniline and sample plus v-heptane,

are placed in a tube and mixed mechanically.

The mixture is heated at a controlled rate until the two phases become miscible. The mixture is then cooled at a controlled rate and the temper- ature at which two phases separate is recorded

as the aniline point or mixed aniline point" [2].

Test procedure ASTM D 611-77 is called for in the Federal and military specifications for distillate fuel oils, although limits are not specified. It is not included in the ASTM fuel oil specifications. The repeatability for the D 611 test for virgin fuel oils is given as 0.16 °C (0.3 °F) for clear or light-colored samples, and

0.3 °C (0.6 °F) for moderately dark to very dark

samples [2]. Alternative variations of this

method (methods A through E) are given in the ASTM test procedure. Method A was used in this

study and is used with transparent distillate

fuel oils. Method B was not specifically eval- uated in this study but is a thin-film version
Table 16. Copper corrosion test on fuel oils and used oils at 100 °C for 3 hours (D 130).

Fuel oil grade

Sample

number

F131

Description

Tarnish

classification

lala

Designation Color

2 Virgin fuel oil Slight

Slight

tarnish

tarnish

Light orange

Light orange

Blend 90% number 2; 10%

used oil lblb SlightSlight

tarnish

tarnish

Yellow/orange

Yellow/orange

Blend 50% No. 2; 50%

used oil

lblb Slight

Slight

tarnish

tarnish

Yellow/orange

Yellow/orange

4 F126 Virgin fuel oil lb

lb SlightSlight

tarnish

tarnish

Dark orange Dark orange

4 F129 Virgin fuel oil lc

lb SlightSlight

tarnish

tarnish

Dark orange Dark orange

5 F125 Virgin fuel oil la

la SlightSlight

tarnish

tarnish

Light orange

Light orange

6 F130 Virgin fuel oil la

la SlightSlight

tarnish

tarnish

Light orange

Light orange

6 F022 Virgin fuel oil (high sulfur)

la

la SlightSlight

tarnish

tarnish

Light orange

Light orange — W022 Composite Used

Automotive oil 2c2c Moderate tarnishModerate tarnish

Multicolored

Multicolored

W033 Composite used

automotive oil from service

station A

3b

3b Dark tarnishDark tarnish

Magenta/

multicolored

Magenta/

multicolored

W040 Composite used

automotive oil from service

station B

2a Moderate tarnish Red

.. _b 7L24 Recycled distillate fuel oil 4a

4b

Corrosion

Corrosion

Black

Black

5 F133 Recycled fuel

oil (source A) 2c3a Moderate tarnish

Dark tarnish

Multicolored

Multicolored

5 F134 Recycled fuel

oil (source B) 2b

2b Moderate tarnish

Moderate tarnish

Magenta

Magenta — W036 Industrial waste

oil (source A)

la Slight tarnish Light orange — W037 Industrial waste

oil (source B) 4c Corrosion Black

Used oil was W022; virgin distillate fuel oil was F131. Viscosity measurements on this oil placed it between grade numbers 2 and 4.

20
of method A (based on the same chemical principle) for use with highly colored samples.

Methods C and D are not appropriate for burner

fuel oils, and method E is used only with a specific automatic aniline point apparatus.

The aniline points of several virgin distillate

fuel oils were determined, and the repeatability

of the results, as shown in table 17, is consistent with the stated ASTM repeatabilities.

5.2.8 Heating Value

Since the primary function of a fuel oil is to produce heat, the combustion energy, often

referred to as heating value or calorific value,

is an important fuel property. A knowledge of

the heating value (i.e., heat of combustion) is necessary to determine the combustion efficiency

Table 17. Repeatability of the aniline point test procedure for distillate fuel oils (D 611, Method A).

Aniline point

(°C (°F))

Fuel oil grade

Sample

number

F132

Description Color

1 Virgin fuel oil Light yellow

2 F131 Virgin fuel oil Medium yellow

a 7L24 Recycled distillate fuel

oil Yellow-brown

(2)

b F131c Blend 0% W022) Medium brown

(2)

b F131C Blend (5% W022) Dark brown

(2)

b F131C Blend (10% W022) Very dark

64.0, 64.0 (147.0)

59.0, 59.0 (138.0)

80.0, 80.0 (176.0)

59.2, 59.2 (138.5)

62.0, 62.2 (143.6, 144.0)

80.0, 80.0 (176.0)

Viscosity characteristics of the recycled distillate fuel oil place it between Grades numbers 2 and 4. Such blends are not considered distillate fuels for some purposes. Sample number indicated is for the virgin distillate fraction.

These samples required special illumination (light behind aniline point apparatus) to observe the aniline point.

The D 611 test procedure (method A) was eval- uated for use with recycled oils. As part of

this evaluation the aniline point was deter

mined for several virgin distillate fuel oil/

used oil blends and a recycled distillate fuel

oil. These data are also shown in table 17 and indicate that the repeatability of the aniline point test for these samples is con- sistent with the stated ASTM repeatability.

The aniline point could be determined for several blends of virgin distillate fuel oil with up to 10-percent used automotive crankcase oil using supplementary lighting behind

the sample. If even darker samples are to

be measured, the thin-film variation of D 611,

method B, may need to be used.

Conclusion

The aniline point may be of interest to obtain

a relative indication of the aromatic content of

a distillate fuel oil. Method A of ASTM method

D 611 "Aniline Point and Mixed Aniline Point of Petroleum Products and Hydrocarbon Sol vents, "has been evaluated and may be used to obtain the aniline point of recycled distillate oils to be used for fuel

and performance of all types of oil-burning equipment, as well as to assure equity in commerce

[3].

The heating value of a fuel is the amount of heat given off as a result of its complete com- bustion. The results are usually expressed as "megajoules per kilogram" (MJ/kg) or, more con- ventionally, "British thermal units per pound"

(Btu/lb) [19]. (Note: One Btu/lb is equivalent

to 2.326 kJ/kg; 1000 kJ/kg = 1 MJ/kg. The Btu used throughout this section is the International

Table Btu.)

The variation in heating va ticular virgin fuel oil grade

is often stated that the value

calculated with sufficient ace known data [19]. The heating

quoted in virgin fuel oil spec

is not directly controllable i of the fuel [3,19]. The speci

related quantity API gravity,

in fuel oil specifications, is estimate the heating value of

[19], and this will be discuss

section.

lue within a paris smal 1

, and it can normal ly be uracy from other

value is often not ifications as it

n the manufacture

fie gravity or the normally included

often used to virgin fuel oils

ed later in this

21
The direct determination of the heating value

is made in an oxygen bomb calorimeter under specified conditions involving careful standardization

of equipment and rigid adherence to prescribed

details of operation. When properly run, the

bomb calorimeter test can yield highly accurate

results, but is time consuming and costly to perform on a routine basis [19].

The test procedure used to experimentally

determine the heating value of virgin fuel oils

is ASTM D 240-76, "Heat of Combustion of Liquid

Hydrocarbon Fuels by Bomb Calorimeter" [2]. This

test is identical to Method 2502 - Federal Test Method Standard No. 791B, and is similar to the Institute of Petroleum test IP 12/73 and British

Standard BS 4379:1969. The D 240 test procedure

states that the "Heat of combustion is determined

in this method by burning a weighed sample in an oxygen bomb calorimeter under controlled conditions. The heat of combustion is computed from

temperature observations before, during and after

combustion, with proper allowance for thermochemical and heat transfer corrections" [2].

A second test procedu

of Combustion of Hydroca

rimeter (High-Precision

D 240, but modified to p ment precision for speci

weight-limited vehicles,

procedures developed at precision test procedure

routine measurements on

re, ASTM D 2382-76, "Heat

rbon Fuels by Bomb CaloMethod)," is similar to rovide increased measureal applications such as

D 2382 is based on NBS [23]. This highis not required for burner fuel oils.

The results of D 240 can be expressed in two

ways, as the "Gross Heat of Combustion" (Hg or QyCgross)), or as the "Net Heat of Combustion"

[H

n or Q„ (net)]. The gross heat of combustion

is defined as "...the heat released by the com- bustion of a unit mass of fuel in a constant volume bomb with substantially all of the water con- densed to the liquid state" [2]. The net heat of

combustion is "...the heat released by the com- bustion of a unit mass of fuel at a constant

pressure of 1 atm [atmosphere] (0.1 MPa) with

the water remaining in the vapor state. .. "[2].

The gross heat of combustion is the value mea- sured directly when using conventional bomb

calorimetry, and is the quantity preferred by the ASTM for reporting the heating value of fuel oils [2]. The net heat of combustion, H n

, is stated to be the most significant value for

estimation of heat system efficiencies. However,

the accurate determination of H n requires know- ledge of the hydrogen content of the fuel [2,24].

Since the emphasis of this report is on more

routine test methods, only the gross heat of combustion was considered.

The precision of the D 240 test procedure is stated to provide a repeatability of 0.13 MJ/kg

(55 Btu/lb) and a reproducibility of 0.40 MJ/kg

(175 Btu/lb) [2].

The D 240 test procedure was evaluated for

use in determining the heating value of recycled

oils to be used for fuel. As a part of this

evaluation, the D 240 test procedure was applied

to a number of virgin fuel oils, recycled used

oils, and composite used automotive oils. The

data are shown in table 18. The NBS Reference

Method given in the table is described in refer- ence 23, from which test procedure D 2382 is derived, and is more accurate than D 240. The

use of this reference method on used and re- cycled oils provided a precise baseline against

which a comparison of the heating value of re- cycled oils, as measured by two commercial

testing laboratories using D 240, could be made.

With one exception, the results from both

commercial laboratories were in good agreement

with the NBS values. Sample F133 results were considerably higher than the NBS results (3.6

percent and 2.8 percent), even though they

agreed with each other well within the stated D 240 reproducibility. This sample contains an unusually high ash content (4.7 percent sulfated

ash, D 874) and was identified during analyses

of other impurities as having a high rate of particulate settling. These characteristics of F133 are consistent with the possibility that

the commercial laboratories did not obtain a representative portion of the ash-forming con- stituents, which would result in a high heating

value. The NBS analyst was aware of the high

particle content of most used and recycled oils,

and employed very vigorous agitation immediately

prior to removing the analytical sample. It therefore is reasonable to suggest that the higher results of the commercial laboratories

compared to the NBS results for sample F133 may

well represent the difficulties in representative

sampling of an inhomogeneous material. (See

also discussion on this sample later in this

section.

)

The results from the two commercial testing

laboratories also agreed well with each other. Laboratory A obtained heating values which fell within 1 percent of the heating values obtained

by laboratory B for 7 of the 8 oil samples. Our conclusion is that the D 240 test procedure is effective in measuring the heating value of re- cycled oils used for fuel when a representative

sample is taken for analysis.

In addition to the direct determination of

fuel oil heating value for fuel oils, indirect

methods for estimating the heating value are often used in practice [19]. These indirect

methods have gained wide popularity due to their

simplicity and low cost. These indirect methods

are based on the correlation of the heat of com- bustion with the specific gravity or API gravity,

and empirical tables have been prepared for virgin

oils [24,25]. Values in these tables can be corrected for the amounts of water, sulfur and

ash found in fuel oils to obtain a more accurate

heating value [24]. Reference 24 states that

this procedure gives estimates of the heating

value of virgin fuel oils good to within 1 per- cent of the measured heating value.

The equation upon which these tables are based

is given in reference 24:

22
Table 18. Experimental heat of combustion data.

Experimental gross heat of combustion (MJ/jg (Btu/lb))

Fuel oil grade

Sample

number

5 F125

5 F133

5 F134

6 F022

F130

W022

W023

W033

Description

Virgin fuel oil

Recycled fuel oil

Recycled fuel oil

Virgin fuel oil

Virgin fuel oil

Composite used

automotive oil

Composite re- refiners feed- stock (dried)

Composite used

automotive oil from service

station (dried)

NBS Reference

method

44.05 (18,939)

44.07 (18,948)

42.95 (18,466)

42.97(18,472)

44.04 (18,935)

44.05 (18,940)

42.15(18,120)

42.13 (18,112)

43.49 (18,696)

43.50 (18,701)

43.65 (18,768)

43.66 (18,769)

44.29 (19,042)

44.29 (19,042)

44.98 (19,338)

44.98 (19,337)

Commercial,

laboratory A

43.88 (18,867)

44.50 (19,133)

44.18 (18,993)

41.98(18,050)

43.42 (18,668)

44.02(18,924)

44.31 (19,050)

45.01 (19,350)

Commercial,

laboratory B

44.12 (18,969)

44.17 (18,989)

44.28 (19,037)

42.38 (18,218)

43.53 (18,713)

43.23 (18,586)

44.36 (19,073)

44.82 (19,270)

a Reference method was similar to ASTM 2382, which is a more precise method than D 240 [23].

b Test procedure used was ASTM D 240. Note discussion of this sample in text.

Q (gross) = 12,400 - 2100 d

2 in calories/g where

d = specific gravity at 60°/60° F

To convert this equation to International

Table Btu/lb, it must be multipled by the fol- lowing factors:

Q

v (gross) =

1.8[(12,400 - 2100 d

2

) x f^ffg] (1)

Equation (1) can also be written in terms of API gravity, using the relationship between spe- cific gravity and API gravity given in Section

5.2.5 of this report:

Q

v (gross) =

22,300 - pjfffigjjjjp, (Btu/lb) n

(2)

Q

v (gross)

51 - 869 " (mT^APi)2 (MJ/k9 } (3)

Table 19 gives the gross heat of combustion

for mixed hydrocarbon fuels having no water,

sulfur, or ash, calculated from the API gravities.

The Btu/lb values in the table are calculated

from equation (2) and rounded to the nearest 10. The MJ/kg values are calculated from equation

(3), and rounded to the nearest 0.01.

Reference 24 gives an equation to correct the gross heating value for the amounts of water,

sulfur, and ash found in fuels:

Q

v =

Q

- 0.01 Q •{% H 2 + % ash + % S) + X-(% S) (4)

where 5 = corrected heat of combustion. 8 ^v

Q = uncorrected heat of combustion (from eq.

v (2) or (3) in the text). 9

8 The symbols Q v and Q v are those used in ref- erence 24; Q v corresponds to H a as Hg is defined in D 240.

9With slightly less accuracy, table 19 may

be used.

23
Table 19. Uncorrected gross heat of combustion for fuel oils as

as estimated from their gravity [24].

Gravity

Degrees Specific

API at at

60 °F 60°/60° F

10 1.0000

11 .9930

12 .9861

13 .9792

14 .9725

15 .9659

16 .9593

17 .9529

18 .9465

19 .9402

20 .9340

21 .9279

22 .9218

23 .9159

24 .9100

25 .9042

26 .8984

27 .8927

28 .8871

29 .8816

30 .8762

31 .8708

32 .8654

33 .8602

34 .8550

35 .8498

36 .8448

37 .8398

38 .8348

39 .8299

40 .8251

41 .8203

42 .8155

43 .8109 44 .8063

45 .8017

46 .7972

47 .7927 48 .7883

49 .7839

Density

Pounds

per gallon

8.337

8.279

8.221

8.164

8.108

8.053

7.998

7.944

7.891

7.839

7.787

7.736

7.686

7.636

7.587

7.538

7.490

7.443

7.396

7.350

7.305

7.260

7.215

7.171

7.128

7.085

7.043

7.001

6.960

6.920

6.879

6.839

6.799

6.760

6.722

684

646

609

572 6.536

Uncorrected gross heat of combus- tion at constant volume (Q )

MJ/kga Btu/lbb

43.08 18,520

43.21 18,580

43.33 18,630

43.45 18,680

43.56 18,730

43.67 18,780

43.78 18,820

43.89 18,870

44.00 18,920

44.10 18,960

44.21 19,000

44.31 19,050

44.40 19,090

44.50 19,130

44.60 19,170

44.69 19,210

44.78 19,250

44.87 19,290

44.96 19,330

45.04 19,360

45.13 19,400

45.21 19,440

45.29 19,470

45.37 19,510

45.45 19,540

45.52 19,570

45.60 19,600

45.67 19,640

45.75 19,670

45.82 19,700

45.89 19,730

45.96 19,760

46.03 19,790

46.09 19,820

46.16 19,840

46.22 19,870

46.29 19,900

46.35 19,930

46.41 19,950

46.47 19,980

The column in MJ/kg does not appear in the original reference but was added for the purposes of this report (calculated from the basic equation).

The values were calculated from the basic equation in terms of International Table Btu/lb (see text).

24
X = 0.0941 =

22.5 x 4.183 x 10

J for units of MJ/kg;

= 40.5 = 22.5 x f^ffl x 1-8 for un1ts of Btu/1b -

% H

? = water content of fuel oil in percent by weight.

% ash = noncombustible content of fuel oil in percent by weight.

% S = sulfur content of fuel oil in percent by weight.

In order to examine the indirect method for

estimating the heating value of recycled fuel oils, a number of recycled fuel oils and com- posite used automotive oils were investigated.

The density (API gravity) of these oil samples

was measured using ASTM test procedure D 1298

(see also this report, Section 5.2.5, Density,

for a discussion of density measurements on re- cycled oils). Using equations (2) and (3), the uncorrected gross heats of combustion were then

obtained (Q ). These values were corrected for

the water, «(sh, and sulfur contents of the samples

using equation (4), and the corrected gross heats of combustion calculated (Q ). It- should be noted that these corrections can be substantial —

up to 5.5 percent of the heat of combustion—for even this relatively small sample group. Final

values were rounded to the nearest 0.01 MJ/kg

(10 Btu/lb) and are given in table 20.

The test procedures used to obtain the various

corrections in table 20 were ASTM D 95-70, "Water

in Petroleum Products and Bituminous Materials

by Distillation," for the water content (see

also Section 5.3.1, this report), and ASTM D 1552-64, "Sulfur in Petroleum Products (HighTemperature Method)," for the sulfur content

(see also Section 5.3.4, this report). The ap- propriate test method for ash required additional

evaluation since equation (4), an empirical equa- tion developed through analyses of many samples

of virgin fuels, was apparently based on results

obtained using the ASTM D 482 (regular) ash method,

or equivalent. However, as discussed in detail

in Section 5.3.3 of this report, the sulfated

ash (ASTM D 874) is required to retain all the ash-forming constituents in a recycled or used

oil. Since the sulfated ash value was always

greater than the regular ash value for the used

and recycled oils examined, the substitution of the sulfated ash value in the heating value cal- culation may produce a systematic shift. Therefore, corrected estimated heating values were calculated for both ash methods (see table 20), and the results are discussed below.

These estimated heating values can be com- pared with the experimental results from the

NBS Reference Method of high-precision oxygen

bomb calorimetry, also given in table 20. It can

be seen that the estimates agree well with the experimental values for the oils; with one ex- ception— recycled fuel oil (F133) —all of the estimated heating values fall within 1 percent

of the NBS values, regardless of the ash test procedure used. The F133 value was overcorrected

by somewhat more than 1 percent for both cases.

Table 20. Comparison of estimated gross heats of combustion (MJ/kg (Btu/lb))

Fuel Q (corrected)

oil gradeSample

number

F133

Description

Spec if ic gravity,

°API

5 Recycled fuel

oil 25.8

5 F134 Recycled fuel

oil 25.7 — W022 Composite used

automotive oil 26.4 — W023 Composite re- refiner's feed- stock (dried)

26.4

W033 Composite used

automotive oil from service

station (dried)

28.7

Experimental

heat of . Using D 482 ash Using D 874 ash combustion m

42.46 (18,260)

43.87 (18,600)

43.78 (18,820)

44.11 (18,960)

42.41 (18,230) 42.96 (18,469)

43.74 (18,800) 44.05 (18,938)

43.39 (18,650) 43.66 (18,768)

44.03 (18,930) 44.29 (19,042)

44.62 (19,180) 44.61 (19,180) 44.98 (19,338)

Q (corrected) = estimated gross heat of combustion corrected for water, ash, and sulfur contents

(see text).

Average experimental gross heat of combustion value using high-precision oxygen bomb calorimetry

(NBS Reference Method) [23].

25
There is a small systematic difference in the

results: the estimated heating values based on the regular (D 482) ash correction more closely

approximate the NBS experimentally determined

values than the estimates based on the sulfated

(D 874) ash correction by about 0.3 percent, a negligible amount. Thus, for this group of oils

the sulfated ash (D 874) correction is adequate.

These results suggest that the gross heat of combustion may be obtained for recycled oils

through use of density measurements and corrections (the indirect method). Given the limited

specific gravity range examined (25.7 - 28.7°

API), further investigation would appear necessary

before the indirect method could be recommended.

Conclusion

The heating value or combustion energy is an important characteristic of fuel oils. ASTM

test D 240-76, "Heat of Combustion of Hydrocarbon Fuels by Bomb Calorimeter," has been eval- uated for use with recycled fuel oils, and used

oils. This test procedure may be used to establish the heating value of a recycled oil to be used as fuel, with the modification that the recycled oil sample be vigorously agitated immediately prior to taking the test sample so that

all particulate material be in complete suspension.

In addition, our limited results indicate

that the indirect method for estimating heating

value, as described above and with the appro- priate corrections, may be able to be used to obtain the heating value of recycled oils. It

is suggested, however, that at the present time

primary reliance be placed on the D 240 method

as standard.

5.3 Test Procedures for Impurities

This section contains evaluated test procedures for the determination of impurities which

are deleterious to the performance of a recycled

oil to be used as a burner fuel. The impurities

which are currently included in virgin fuel oil specifications are water and sediment, carbon

residue, ash, total sulfur, and acid. Test pro- cedures for measuring these impurities are also

recommended for use with recycled oils, with the modifications as described in the individual test procedures.

These test procedures were evaluated for use with recycled oils using the evaluation process described in section 4 of this report. In general, test procedures for these impurities must

be evaluated for their ability to reliably measure the constituent under test.

The individual test procedures are discussed

below.

5.3.1 Water and Sediment

Water and insoluble impurities (sediment) are present in most crude oils and in some semirefined products such as fuel oils [18]. Appreciable amounts of water and sediment in a fuel

oil tend to cause fouling of handling facilities

and to give trouble in burner mechanisms. Sedi- ment may accumulate in storage tanks and on filter

screens or burner parts, resulting in obstruction

to free passage of oil from the tank to the burner. Significant amounts of water can lead to the production of emulsions which are removable only

with difficulty [3]. Water is considered an important cause of corrosion in tanks and equip- ment (excluding copper and copper-containing

alloys), and the corrosive deterioration of stor- age tanks is often associated with the water

bottoms which accumulate from atmospheric condensation and contamination [3].

The amounts of water and sediment in petroleum products are determined by three general

techniques: centrifugation, distillation, and extraction. In centrifugation, water and sedi- ment are separated from the petroleum product

and measured volumetrically; in distillation, water is separated from the petroleum product

and measured volumetrically; and in extraction,

the solid insoluble components above a certain

size are separated from the petroleum product

and measured by weight.

The specific test procedures which are com- monly used for the determination of water and

sediment in petroleum products are the following: ASTM D 1796-68 (reapproved in 1973), "Water and

Sediment in Crude Oils and Fuel Oils by Centrifuge"

[27]; ASTM D 96-73 (reapproved in 1977), "Water

and Sediment in Crude Oils" [2]; ASTM D 95-70

(reapproved in 1975), "Water in Petroleum Products

and Bituminous Materials by Distillation" [2];

and ASTM D 473-69 (reapproved in 1974), "Sediment

in Crude and Fuel Oils by Extraction" [2]. The

D 1796 and D 96 Methods are actually multiple

test procedures and reference the D 95 test for water and the D 473 test for sediment, calling

them "Base Methods" (D 96) or for "difficult

types of oils" (D 1796).

ASTM method D 1796 is the test procedure gener- ally used for virgin fuel oils and is the method

cited in the ASTM specification (D 396-76) and

the Federal specification (VV-F-815C) for burner

fuel oil grades 1 through 5. (Note: For grade

6 fuel oil, these specifications cite methods D 95 for water and D 473 for sediment.) D 1796 is identical to Method 3000 - Federal Test Method

Standard No. 791B, to the API Standard 2548, to the Institute of Petroleum Designation 75/69, to the British Standard 2882, and to the Deutsche

Norm DIN 51793. This method (D 1796) covers the determination of water and sediment in crude

oils and fuel oils by diluting with an equal

volume of toluene saturated with water, thorough,

mixing, heating to a prescribed temperature, and

then spinning at a specified centrifugal force

and time period. Centrifuging is repeated until two consecutive readings of the combined water

26
and sediment agree. For domestic usage in the United States, the D 1796 method refers the user

to ASTM method D 96 and notes that (1) some oils may require other solvents or solvent-demulsif ier combinations for adequate separation of the water

and sediment, and (2) "...with some types of oils it is difficult to obtain water and sediment

contents with this method. When this situation

is encountered, ASTM Method D 95- API 2560, Test

for Water in Petroleum and Other Bituminous Ma- terials or IP 74 and ASTM Method D 473-API

2561-IP 53, Test for Sediment in Crude and Fuel Oils by Extraction may be used" [27].

A second test procedure is ASTM D 96-73, "Water

and Sediment in Crude Oils" [2]. This procedure

is identical to Method 3003 - Federal Test Method

Standard No. 791B, to the API Standard 2542, and

to the Deutsche Norm DIN 51793. The D 96 test procedure defines a primary centrifuge method

and two alternative centrifuge methods for determining the volume of combined water and sediment

in crude oil. It further specifies Base Methods

for water (by distillation, using ASTM D 95) and sediment (by extraction, using D 473), determined

separately. [Note: Although the D 96 procedures

are described as being for crude oil, the D 1796 centrifuge test for water and sediment in fuel oils refers the user to the D 96 method for unusual or difficult samples.] The D 96 Primary Method

(and Alternative Method A) describes various

possible solvents, demulsif iers, and temperatures

to consider for difficult to analyze oil samples.

Alternative Method B describes a simplified test

procedure. In cases of dispute as to which water

and sediment test value is the "true" value, the

D 96 Base Method states that "The sum of the results obtained in accordance with the latest

edition of Method D 95 - API 2560 [note: water

by distillation [and Method D 473 - API 256]

[note: sediment by extraction], shall be the correct value for water and sediment. These

methods shall be considered as the Base Method

and shall be used when agreement cannot be reached

between the purchaser and seller when using any

of the other methods described" [2].

The distillation test procedure for water is ASTM D 95-70 (reapproved in 1975), "Water in Petroleum Products and Bituminous Materials by

Distillation" [2]. This procedure is identical

to the API Standard 2650, the Institute of Petro- leum Designation 74/70, and the British Standard

4385. This method is stated to be applicable to crude petroleum, fuel oil, road oil, lubricating

oil, and petroleum sulfonates (e.g., dispersants,

detergents) [2]. In this method, the sample is refluxed with a water immiscible solvent which

co-distills with the water in the sample; con- densed solvent and water are continuously sep- arated in a trap, the water settling in the graduated section of the trap and the solvent

returning to the still [2].

The sediment by extraction test procedure is ASTM D 473-69 (reapproved in 1974), "Sediment in Crude and Fuel Oils by Extraction" [2]. This

procedure is identical to Method 3002 - Federal Test Method Standard No. 791B, to the API Stan- dard 2561, the Institute of Petroleum Designation

53/66, the British Standard 4382, and the Deutsche

Norm DIN 51789. In this method, the sample is placed in a refractory thimble and extracted

with hot toluene until the residue reaches con- stant weight.

Test procedures based on centrifugation are more rapid and less costly than the others available for water and sediment determinations. In addition, the specifications for virgin fuel oils place limits on the combined contaminants

for all grades except grade 6. Thus, initial

evaluation studies were directed towards this

particular measurement technique. A number of recycled fuel oils and used automotive crankcase

oils were analyzed for water and sediment using

both D 1796 and D 96 (with 1 percent by volume

of a demulsifier, n-butyl diethanolamine). The

results from these two test procedures were then

compared to results obtained by the D 96 Base Method (D 95 plus D 473). [Note: As recom- mended in D 96 for converting the D 473 results

to a volume basis before combining with the D 95 results, the sediment value (obtained on a weight

basis) was arbitrarily assigned a specific gravity

of 2.0 for conversion to a volume basis.] These

results are shown in table 21, and indicate that

both these centrifuge methods, D 1796 and D 96 with demulsifier, give results very different

from those obtained by the Base Method. These

results can be explained by the high concentrations of contaminants such as dispersants, detergents, and finely divided particulates found in many recycled and used oils. These types of contaminants are known to cause difficulties

with centrifugation methods [2]. Consequently,

the D 96 and D 1796 test procedures utilizing

centrifugation were not considered further, and the evaluation directed towards the test proce- dures constituting the D 96 Base Method (i.e., D 95 for water and D 473 for sediment).

The precision of D 95 (water by distillation)

is stated to be as as follows (on samples of

equal volume, using 10-mL or 25 mL traps) [2]:

"Repeatability" - Duplicate determinations of water by the same operator should be considered

suspect if they differ by more than the following amounts:

Water collected, mL

to 1.0 0.1

1.1 to 25 0.1 mL or 2 percent of the mean, whichever is greater.

"Reproducibility - The results submitted by each

of two laboratories should be considered suspect

if they differ by more than the following amounts:

Water collected, mL

to 1.0 0.2 mL

1.1 to 25 0.2 mL or 10 percent of the mean, whichever

is greater."

27
Table 21. Results from centrifugation methods for water and sediment.

Water and sediment concentrations, percent by volume

Fuel

oil grade Description

Sample

number

F133

Centrifuge

only (D 1796)

4.8, 4.7

Centrifuge

demulsifier

4.8,

with

(D 96)

a

4.6

Base Method.

(D 95 & 473D,C

5 Recycled fuel oil (source A)

0.53

5 Recycled fuel oil (source B)

F134 6.4

d

, 4.0

d 0.6e

, 0.5e 6.0

d

, 6.6e

, 5.8

d 6.0

e 1.29 — Composite used automo- motive oil W022 0.2, 0.1 6.0 0.22

— Used oil feedstock to re-refiner (sampling

period A)

W023 3.0 14.0, 13.4 5.73

Demulsifier used was n-butyl diethanolamine at 1 percent by volume. The sediment concentrations used to calculate these values were those obtained with new extraction

thimbles (see text). Percent by volume; sediment as determined by method D 473 assigned a specific gravity of 2.0 as recommended in D 96 (see text).

Operator 1. Operator 2.

It should be noted that D 95 does not require

reporting of the sample volume taken nor the water volume actually collected, leading to pos- sible problems in comparing the precision of results. It is therefore recommended that the test procedure for water by distillation (ASTM

method D 95) be modified to include reporting

the sample volume taken for analysis.

The ASTM D 95 test procedure for water by

distillation was evaluated for use with recycled

oils. As a part of this evaluation, the repeatability of the D 95 test procedure was determined

for recycled fuel oils and used oils. The results

of these tests are found in table 22, and indicate

acceptable repeatabil ities for these samples.

These results tend to confirm that the determination of water by distillation (D 95) is an acceptable test procedure for use with recycled

oils to be used for fuel.

The ASTM D 473 test procedure for sediment by

extraction was investigated next. The precision

of the D 473 method is stated by ASTM as follows

(for 0.0 to 0.4 percent sediment) [2]:

"Repeatability - Duplicate results by the same operator should be considered suspect if they

differ by more than 0.017 + 0.255 S, where S is the average result in weight percent.

"Reproducibility - The results submitted by each

of two laboratories should be considered suspect

if the two results differ by more than 0.33 + 0.255 S, where S is the average result in weight

percent." The ASTM procedure does not provide

precision criteria for sediment levels above 0.4 percent by weight.

The ASTM D 473 test procedure for sediment by

extraction was then evaluated for use with recy- cled oils. As a part of this evaluation, the

repeatability of the D 473 test procedure was determined for recycled oils, used oils and

virgin fuel oils. The results of these tests

are found in table 23.

As can readily be seen from table 23, test

results for sediment which include tests made

with both new and reused thimbles vary widely.

During this test evaluation, two details were detected which required further investigation.

First, from visual observation of the extract it was apparent that fine particulates were passing

through the refractory thimbles for the recycled

oils and used oils. Second, it was noticed that

the sediment values for recycled or used oils were lower for new thimbles, in spite of using

the appropriate methods as specified in the

D 473 procedure for reuse of the thimble. In some cases, as noted in table 23, reuse resulted

in plugging of the thimbles, and therefore caused

solvent and sample retention in the thimble

throughout the remainder of the test procedure.

To investigate whether particulates were in fact passing through the refractory thimble during

the extraction procedure, an extraction was per- formed on sample W022, and the toluene solvent

containing the dissolved used oil plus any par- ticles passing through the thimble was collected

for examination with an electron microscope. To

28
Table 22. Repeatability of the water by distillation test procedure (D 95).

Fuel oil Sample Test sample Water by distillation,

grade Description number volume (mL) D 95 (% by volume)

5 Recycled fuel oil (source A) F133 100 0.13, 0.20

5 Recycled fuel oil (source B) F134 100 0.60, 0.70, 0.63

Composite used automotive oil W022 100 0.20, 0.19, 0.20, 0.18

Sample

number Test samplevolume (mL)

F133 100

F134 100

W022 100

W023 50

W024 50

F022 50

Used oil feedstock to re-refiner W023 50 5.78, 5.60 (sampling period A)

Used oil feedstock to re-refiner W024 50 3.60, 3.50 (sampling period B)

Virgin residual fuel oil F022 50 0.04, 0.04

Sample volume not required to be reported by ASTM D 95 method, but necessary in order to establish

repeatability and reproducibility.

Table 23. Repeatability of test for sediment by extraction (D 473).

Sediment concentrations (% by weight)

Fuel oil grade Description

Sample

number

F131

New thimbles

0.018, 0.011

Reused thimbles

2 Virgin fuel oil

6 Virgin fuel oil

,

(source A) F130 0.039, 0.016,

0.043

0.033, 0.030, 0.038,

0.101, 0.019

6 Virgin fuel oil

,

(source B) F022 0.016, 0.019 0.004, 0.002

5 Recycled fuel oil , (source A) F133 1.05, 0.61, 0. 57 4.28

a

, 4.45, 4.11,

3.90, 3.78

5 Recycled fuel oil

,

(source B) F134 1.01, 1.43, 1. 1.39, 1.34

37, 6.15

a

, 6.56

a

, 0.96 — Composite used automotive oil W022 0.067, 0.070,

0.017

0.44, 1.71, 0.32,

0.24 — Used oil feedstock to W023 0.085, 0.062 2.54, 1.42

re-refiner (source A)

Thimble plugged during extraction (see text).

29
prepare the sample for this examination, a thin

carbon-film grid was dipped into the thoroughly

mixed solvent and oil, air dried, and coated

with a thin layer of carbon. The samples were examined by scanning electron transmission microscopy, and a random collection of images taken. Three of these images are shown in figures 2, 3 and 4, with different magnifications as noted in the scale. It is apparent that large numbers of very small particles are present in this sample

extract, and these particles have apparently

readily passed through the refractory thimble.

The particles observed have a size range of 20 nanometers (nm) to 0.3 micrometer (pm), with the

majority of particles having dimensions of about

100 nm. Particle aggregation is observed, and many of the larger particles may be aggregates. Most of the particles have smooth, nearly spherical shapes.

../*•

' »-V;;- %:*

** IP**

--; I

•'*%-•<

m

a >* *

.;"

' '«&*>*>. '£''5** 4>' "-/^W:>~. \ *: •*

*-: 5 urn

Figure 2. Electron Photomicrograph of Particles

in Used Automative Oil Extract at 2500 X Magnification.

Figure 3. Electron Photomicrograph of Particles

in Used Automotive Oil Extract at 25.000 X Magnification.

Figure 4. Electron Photomicrograph of Particles

in Used Automotive Oil Extract at 100,000 X Magnification. (Note Apparent Agglomeration of Particles.

)

The second detail noticed, the lower values

obtained using only new thimbles, was investigated further. A series of experiments was made on six oils (two virgin fuel oils, two recycled fuel oils, and two used oils) using

a single thimble for three consecutive runs on each oil. The results of this series of experiments, shown in table 24, clearly show cases of increasing sediment values.

The data shown in table 23 indicate that the

D 473 test procedure for sediment by extraction

can capture and measure the larger particles in

a recycled fuel oil, when a new extraction thimble is used for each run. Note, however, that

for the recycled or used oils, in two cases out

of four (F133, W022) some of the differences

between duplicate measurements exceed the ASTM

repeatability (assuming the ASTM repeatability

can be extrapolated above the 0.4 percent sedi- ment level as stated in the procedure). While

it is known that there are large numbers of very

small particles present in a used automotive

crankcase oil, some of which readily pass through

the refractory thimbles specified for use with

the test procedure, there is no information

available to indicate that these fine particles

cause problems in the operational performance of the fuel oil. Therefore, for the purposes of

this test procedure, sediment can be defined as those particles retained in the extraction thimbles at the completion of the tests. While the test procedure for sediment by extraction (D

473) determines the quantity of larger particles

in a recycled fuel oil (those particles which

could reasonably be expected to cause operational performance problems in service), there may

also be a need at some later date to measure the

total solids content of a recycled fuel oil. Therefore, an additional test procedure which

was available for determining the substances

insoluble in pentane and/or toluene was investigated.

30
Table 24. Sequential sediment determinations using single thimble (D 473).

Sediment by extraction (% by weight)

Fuel oil grade Description

Virgin fuel oil

Virgin fuel oil

Recycled fuel oil (source A)

Recycled fuel oil (source B)

Composite used automotive oil

Industrial waste oil (source B)

Sample New Second Third

number thimble use use

F130 0.039 0.033 0.030 F130 0.043 0.101 0.019

F022 0.019 0.004 0.002

F133 1.05 4.28

a

F134 1.01 6.15

a 6.56

a

W022 0.017 0.438 1.71

W037 0.795 0.699 0.796

Thimble plugged during extraction.

The solids content of an oil may be determined using ASTM D 893-69 (amended in 1978),

"Insolubles in Used Lubricating Oils." 10 This

method is identical to Method 3121 - Federal Test Method Standard 791B. It covers the determination of substances which are insoluble in pentane and/or toluene (Procedure A--Pentane

Insolubles and/or Toluene Insolubles), and sub- stances which are insoluble in pentane and/or

toluene with the use of a coagulant (Procedure

B—Coagulated Pentane Insolubles, and/or Coagulated Toluene Insolubles). The test procedure

is. stated to be useful for the determination

of "insolubles in used lubricating oils." In addition, for the coagulated insolubles, the coagulant (Procedure B) will collect". . .additional finely divided materials that may have

been held in suspension because of the detergent

character of the oil" [20]. Since these finely

divided materials were of particular interest

for this study, only the test for coagulated

insolubles (Procedure B) was investigated.

The D 893 test method (Procedure B) is sum- marized as follows [26]: "A sample of used lubricating oil is mixed with pentane-coagulant so- lution and centrifuged. The precipitate is washed twice with pentane, dried, and weighed to give coagulated pentane insolubles. For coag- ulated toluene insolubles a separate sample of the oil is mixed with pentane-coagulant solution

and centrifuged. The precipitate is washed twice

with pentane, once with toluene-alcohol solution,

i0The original D 893-69 test procedure included

benzene as the second solvent; however, this

was amended in 1978 to conform to health and safety regulations, and toluene was substituted

for benzene. The amended test procedure is essentially the same as the older method, with

substitution of the toluene solvent for benzene,

plus a revision of the precision portion of the procedure [26].

and once with toluene. The insoluble material

is then dried and weighed to give coagulated

toluene insolubles." The revised section on precision for reference [26] gives the repeatabilities and reproducibilities for Procedure B as shown in table 25.

The D 893 test method (Procedure B) was eval- uated for use with recycled oils used for fuel and with used automotive crankcase oils. As part of this evaluation, the coagulated pentane

and coagulated toluene insolubles were determined for a number of virgin fuel oils, recycled

fuel oils, and used lubricating oils. The re- sults of these tests are found in table 26, and

the experimental repeatability with the stated ASTM repeatabilities. In two cases, samples

W023 and W038, the coagulated pentane insolubles

would not dry properly and resulted in a semisolid material, (even after drying as described

in the test procedure), apparently due to a resinous component of the used oil. The difference between the coagulated pentane insolubles

and the coagulated toluene insolubles is defined

as the "insoluble resins" contained in the pro- duct [26]. The latter value, coagulated toluene

insolubles, always resulted in a dry product and was always equal to, or less than, the coagulated

pentane insolubles.

In addition, one of the samples (F 134) had a coagulated toluene insolubles result which was

less than the sediment by extraction. In an attempt to resolve this inconsistency, a second

set of tests was run using D 893 (Procedure B) with a higher level of coagulant. The results were approximately 30 percent higher than those

using the coagulant concentration prescribed in the D 893 method.

The above results indicate that the test pro- cedure for coagulated toluene insolubles, D 893, appears to provide a useful indication of the

31
Table 25. Precision criteria for procedure B of D 893 [26].

Type

Repeatability

Repeatability

Reproducibility

Reproducibility

Solvent

used

Pentane

Toluene

Pentane

Toluene

Average insolubles Precision criteria content (percent) iE!srcent insolubles)

0.0 to 1.0 0.07 Over 1.0 10% of mean

0.1 0.068

a 0.4 0.14

0.8 0.19

0.0 to 1.0 0.10 Over 1.0 15% of mean

0.1 0.30

b 0.4 0.60

0.8 0.86

1.1 1.00

Repeatability = 0.21 -/TI where I„ = coagulated

Reproducibility = 0.957 -/TI where I R =

These precision data were derived from the equation:

toluene insolubles.

These precision data were derived from the equation:

coagulated toluene insolubles. In addition, at the June 1978 ASTM it was decided to add the following

note: "The poor interlaboratory precision (reproducibility) of this portion of the test is such that

Procedure B, coagulated toluene insolubles, is unsuitable for the purpose of comparison of interlaboratory results" (Minutes of ASTM Committee D-2, RDD VI Section B, July 20, 1978). It is unclear at present

whether this poor reproducibility is due to the test procedure or to the substantial problems of reliable

sampling of used oils for their insolubles content.

insoluble solids content of a recycled fuel oil. However, this test should be used with caution

since for some recycled fuel oils the recommended

coagulant level may not allow separation of all of the fine particulates in the oil sample.

Conclusion

The water and sediment concentrations are important considerations for adequate fuel oil performance in service. Recycled oils used for

fuel may contain substantial amounts of these

impurities. ASTM method D 95-70, "Water in Petroleum Products and Bituminous Materials

by Distillation," has been evaluated with

recycled fuel oils and used lubricating oils,

and is a satisfactory method for determination

of the water content in recycled oils used as

fuel, with the modification that the sample

volume taken for analysis be reported. Also, ASTM method D 473-69 (reapproved in 1974),

"Sediment in Crude and Fuel Oils by Extraction,"

has been evaluated with recycled oils, used oils,

and virgin fuel oils. This test is recommended

as a satisfactory test procedure for the determination of larger particles in a recycled fuel oil, with the modification that a new refractory

thimble be used for each determination.

It has also been shown that centrifugation

techniques which determine water and sediment

simultaneously are not satisfactory for all types

of used and recycled oils. This means that water

must be measured (by volume) separate from sediment, which is measured by weight. Thus, there

are three ways to report the values: together

by volume, together by weight, or separately.

The first one requires the density of the sediment. In the ASTM procedure (see page 86, this

report), an arbitrary density value of 2.0, close

to that of sand, was selected. We suspect that

the sediment in used and recycled oils is much

more dense than sand. Consequently, a combined

value based upon volume is not recommended.

Since the density of water is well established,

it would be satisfactory to report a combined

value for water and sediment on a weight basis . Reporting the water and sediment values sepa- rately, the third way, is also satisfactory.

5.3.2 Carbon Residue

The carbon residue of a petroleum product is the amount of carbonaceous residue formed during

evaporation and pyrolysis of that product. It provides an indication of the relative cokeforming propensity of a fuel oil. The carbon

residue test is generally applicable to rela- tively nonvolatile petroleum products which

partially decompose on distillation at atmo- spheric pressure, and it is used primarily to predict the performance of distillate fuels,

grade numbers 1 and 2 [25]. A high carbon

residue value for a distillate fuel oil would

indicate a tendency to form excessive carbon

and/or deposits on burning, thereby greatly re- ducing the efficiency of vaporizing pot-type and

sleeve-type burners or fouling nozzles in small residential-type burners.

32
Table 26. Repeatability of the coagulated insolubles test procedure (D 893).

Coagulated insolubles (% by weight)

Fuel oil grade Description

Sample

number

F132

Pentane insolubles

0.00, 0.00

Toll insoli

0.00

ene bles

1 Virgin fuel oil

2 Virgin fuel oil F131 0.021, 0.013 0.012, 0.017

6 Virgin fuel oil (source A) F130 3.27, 3.30 0.59, 0.67

6 Virgin fuel oil (source B) F022 7.75, 7.73 0.12, 0.27

5 Recycled fuel oil (source A) F133 5.29, 5.27 4.56, 4.88

5 Recycled fuel oil F134 0.94, 0.93 0.70, 0.67 (Source B) F134 1.33 b 1.34

b 0.93b 0.89b — Composite used automotive

oil W022 3.21, 3.43 2.30, 2.26 — Used oil feedstock to W023 15.98

C

, 15.89

C 0.96, 0.93 re-refiner (source A, sampling period A)

Used oil feedstock to re-refiner (source A, sampling period B)

Used oil feedstock to re-refiner (source B)

W024

W038

5.83

3.95

5.78

2.45

0.88, 0.86

0.75, 0.76

Coagulated insolubles for this oil are lower than sediment (D 473) values (see text).

Coagulated insolubles using 2X the coagulant concentration specified in D 893. Oily sludge; would not dry properly.

Black tarry residue.

The available virgin oil test procedures for carbon residue are ASTM D 524-76, "Ramsbottom

Carbon Residue of Petroleum Products," and ASTM

D 189-76, "Conradson Carbon Residue of Petroleum

Products" [2]. The usual test procedure for determining carbon residue of virgin fuel oils

is the Ramsbottom carbon residue test, which is identical to Method 5002 - Federal Test Method

Standard 791B and to the British Institute of Petroleum test method IP 14/65 (British standard

4451). The method D 189 (Conradson carbon residue) was not evaluated for this report since

existing fuel oil specifications do not call for this method and because in note 2 of method D 189 it is stated that, "In general, Ramsbottom

Carbon Residue is the preferred method for sam- ples that are mobile below 90 °C. The Conradson

Carbon Residue is finding use to characterize

heavy residue fuel coker feed stocks, etc., which

cannot readily be loaded into a Ramsbottom coker

bulb, and when it is desirable to examine or further test the residue." It should be noted

that all grades of fuel oil are mobile at 90 °C or below.

The Ramsbottom D 524-76 test procedure re- quires, "The sample, after being weighed into a special glass bulb having a capillary opening,

is placed in a metal furnace maintained at ap- proximately 1020 °F (550 °C). The sample is thus quickly heated to the point at which all volatile matter is evaporated out of the bulb

with or without decomposition while the heavier

residue remaining in the bulb undergoes cracking

and coking reactions. In the latter portion of the heating period, the coke or carbon residue

is subject to further slow decomposition or slight oxidation due to the possibility of breathing air into the bulb. After a specified

heating period, the bulb is removed from the

bath, cooled in a desiccator, and again weighed.

The residue remaining is calculated as a per- centage of the original sample, and reported as Ramsbottom carbon residue" [2].

For virgin oils, the carbon residue is nor- mally specified only for distillate fuel oil,

grade numbers 1 and 2, and is measured on the 10-percent residue after distillation (see

section 7 of ASTM D 524-76). Petroleum products

33
containing ash-forming constituents will provide

a value which includes both the carbonaceous

residue and the ash. Normally, the ash content

of a distillate fuel oil would be very low and

is not separately determined for existing specifications. However, if ash-forming constituents

are present in a distillate fuel oil, they would

be expected to contribute to the carbon residue

value. If desired, or if large amounts of ash- forming constituents are suspected, the ash con- tent of the fuel oil may be determined separately

using ASTM method D 482-74 or, for a recycled

fuel oil, method D 874-77 (see Section 5.3.3,

Ash, this report). (Note: The ash included in the carbon residue test should not be assumed to

be similar in composition to other ashing tests.)

The Ramsbottom carbon residue test can also

be applied to residual fuel oils and lubricating

base oils, although not normally used as part of specifications. With these heavier oils, the test procedure is applied to 100-percent samples

as received, rather than on the 10-percent residuum specified for distillate fuel oils. For such oils, the carbon residues usually range

from a few percent up to approximately 15 percent.

The precision of the carbon residue test pro- cedure for virgin oils is given graphically in the ASTM test method, and examples taken from

this figure are given in table 27. These pre- cision. data are applicable to both distillate

and residual petroleum oils.

Table 27. Precision of carbon residue test procedure for virgin fuel oils.

Ramsbottom Diffe rence, percent

carbon residue carbon residue

average percent Rep eatabiity Reproducibi 1 ity

0.10 0.026 0.036

0.30 0.040 0.061

1.0 0.082 0.15

3.0 0.22 0.38

10 0.80 1.4

Data taken from ASTM D 524-76, "Ramsbottom

Carbon Residue of Petroleum Products," figure 4.

The Ramsbottom carbon residue test procedure

(D 524-76) was evaluated for recycled oil used

as burner fuel. As part of this evaluation the

D 524 test procedure was applied to a number of recycled and used oils, virgin distillate fuel oils, virgin distillate fuel oil /used oil blends,

and virgin residual oil/used oil blends. Typical

data are shown in tables 28 and 29. All of our results indicated that the repeatability of the

carbon residue test for recycled oils and virgin

oil/ recycled oil blends falls within that of virgin fuel oils, as shown in table 27.

As a result of the test procedure evaluation,

it became apparent that some additives and con- taminants normally found in used lubricating

oils would increase the carbon residue test re- sults as determined by D 524. These additives

and contaminants include both organics such as long-chain polymeric molecules (e.g., viscosity

index improvers, pour point depressants), and

inorganics (e.g., ash-forming constituents such

as zinc, lead and calcium compounds, wear metals). Our results indicate that the carbon residue

test procedure is a useful indicator of the total residue-forming potential of a recycled distillate fuel oil.

Conclusion

The carbon residue test is a useful indicator

of performance for distillate fuel oils. The

Ramsbottom carbon residue test procedure, ASTM

D 524-76, has been evaluated with recycled fuel oils and blends of virgin fuel oil with used

oil. This test may be used to establish that a product meets the specified values of carbon

residue, limited to distillate fuels on the 10- percent residuum. Method D 524 can also be used

with the heavier residual oils in order to deter- mine the carbon residue of these products.

5.3.3 Ash

The ash content of a fuel oil is defined as that residue, free from carbonaceous matter,

remaining after ignition in air at a specified

high temperature [3,19]. The ash in virgin fuel oils results from a variety of inorganic and

metal -containing compounds present in the crude

oil, from contaminants acquired during transportation and storage, and from additives which are used to improve particular fuel properties [3].

The ash in recycled fuel oils results primarily

from the additives and contaminants found in used lubricating oils. Particular ash-forming

constituents may include lead (from leaded gasoline); wear metals; silica from dust and dirt;

and calcium, zinc, and magnesium additives.

Depending on the use of the fuel, the amount

of ash has a considerable bearing on whether or not detrimental effects will occur. Ash in virgin heavy fuel oils can cause clogging or de- posits and high-temperature corrosion in boilers;

it may attack refractory materials (e.g. bricks)

used in the construction of high-temperature

furnaces, kilns, etc.; and it may affect the finished product in certain industrial processes

such as ceramic and glass manufacture [3]. There

are also certain environmental restrictions on the emission of ash particulates from stacks. For a recycled fuel oil, the ash content can reasonably be expected to have effects similar

to those described above for virgin fuel oils.

It is also known that many residual recycled

fuel oils and used lubricating oils have ash levels considerably higher than virgin fuel oils [5,7].

Since the ash forming constituents of crude

oil generally have low-volatility , they ultimately concentrate in the residue from distillation and therefore, distillate fuel oils tend

to contain only negligible amounts of ash-forming

constituents [3]. However, both distillate and

residual fuels may pick up ash contributors during

34
Table 28. Repeatability of the carbon residue test procedure on distillate fuel/used oil blends (on 10-percent distillation residue) - D 524 (% Wt.).

Added automotive used oil (% v/v)

a

Fuel oil grade Sample 0.0 0.1 0.2 0.5 1.0 5.0

1 F132 0.11 0.18 0.26 2.21

0.14 0.16 0.28 2.20

2 F131 0.20 0.23 0.36 0.47 1.78

0.20 0.24 0.37 0.51 1.73

For used oil W022 with carbon residue of 3.81, 3.78, 3.73, the average equals 3.77 percent (not

distilled; standard deviation of the mean is 0.02%, n = 3).

Table 29. Repeatability of the carbon residue test procedure for recycled oil and virgin fuel oil /used oil blends - D 524.

Fuel oil/used oil blend

Fuel oil gradeSample

number

8-2-273

Virgin oil carbon residue (%)

Used oil concentration (w/w)

100% (recycled distillate fuel oil)

Carbon

residue (%)

4 1.26?

1.30°

Avg.

SD

= 1.27

= 0.03

6 F022 14.72

14.88

14.92

14.71

14.94

16.7% W022C

Avg.

SD

12.67 12.86

12.97

= 12.83

= 0.15

Avg. SD 14.83

0.11

F130

Avg.

SD

53

39

6345

5.50 0.10

16.7% W022 5.50 5.35

5.66

5.09

Avg. = 5.40

SD = 0.24

Measurement by operator a. Measurement by operator b. c W022 carbon residue is 3.77 percent (standard deviation of the mean is 0.02%, n = 3).

35
transportation from the refinery. Fuel oil specifications usually include ash content for residual

fuels only, with the ash content of distillate

fuels included in the carbon residue specification (see also Section 5.3.2, Carbon Residue,

this report). Specifications for grade number 6 residual fuel oil do not have a limiting value

for ash.

Two test procedures are available for the

determination of ash in petroleum products. The

first method is ASTM D 482-74, "Ash from Petroleum Products" [2]. This method is also found

as Method 5421 -Federal Test Method Standard No. 791B, Institute of Petroleum Designation 4/65,

British Standard 4450, and Deutsche Norm DIN

51575. This test procedure is usually called

for in specifications for virgin residual fuel oils. However, method D 482, in note 2, states

that, "This method is not intended for the analysis of unused lubricating oils containing additives; for such samples use ASTM Method D 874-IP

163, Test for Sulfated Ash from Lubricating Oils

and Additives,... neither is it intended for the analysis of lubricating oils containing lead nor

for used engine crankcase oils" [2]. Since re- cycled oils used as fuel often contain both lub- ricating oil additives and lead and are often

made from used engine crankcase oils, the "regular

ash" method (D 482) was considered to be less promising and a second ash method was considered.

This second method is ASTM D 874-77, "Sulfated

Ash from Lubricating Oils and Additives" [2].

This test procedure is also found as Method 5422 - Federal Test Method Standard No. 791B, Institute

of Petroleum Designation 163/65, British Standard

4716, and Deutsche Norm DIN 51575. The term "sul- fated ash" is defined as "...the residue remaining

after the sample has been carbonized, and the residue subsequently treated with sulfuric acid

and heated to constant weight" [2]. A summary of the D 874 test procedure is as follows: "The sample is ignited and burned until only ash and

carbon remain. After cooling, the residue is treated with sulfuric acid and heated at 775 °C until oxidation of carbon is complete. The ash

is then cooled, re-treated with sulfuric acid, and heated at 775 °C to constant weight" [2].

This test procedure also has a precautionary

note stating that it was "...not intended for

the analysis of used engine oils or oils con- taining lead" and a cautionary statement regarding possible problems with magnesium and phosphorus [2]. However, the D 874 test procedure

was examined further because (1) it is stated

to be usuable for the determination of residues

from calcium, zinc, magnesium (probably), barium,

potassium, sodium, and tin [2]; and (2) a pre- liminary examination suggested that the test may

also retain lead from used lubricating oils.

While it is recognized that the sulfated ash test procedure will provide test results which

are somewhat higher than the regular ash procedure, due in part to the incorporation of sulfate into the ash residue, it is necessary to provide a test procedure which can reliably

indicate the maximum level of ash-forming con- stitutents which may be found in a recycled oil used for burner fuel.

The repeatability of the D 874 test procedure

for virgin petroleum oils is stated as follows: "The difference between successive test results,

obtained by the same apparatus under constant operating conditions on identical test material

would, in the long run, in the normal and correct operation of the test method, exceed the following values only in 1 case in 20:

0.047 X

' 85

where: X = average of the two test results in units of percent sulfated ash" [2]. For example,

with an oil having a 0.1 percent sulfated ash

(by weight), the repeatability is given as 0.006

weight percent sulfated ash, or 6 percent; for a 1.0 percent sulfated ash, the repeatability is 0.047 weight percent sulfated ash, or 4.7 percent.

The reproducibility of the D 874 test procedure

for virgin petroleum oils is stated as follows: "The difference between two, single and independent results, obtained by different operators

working in different laboratories on identical test material would, in the long run, in the

normal and correct operation of the test method,

exceed the following values only in 1 case in

20: 0.189 X

' 85

where: X = average of the two test results in units of percent sulfated ash" [2]. This repro- ducibility works out to 0.027 weight percent

sulfated ash, or 27 percent at the 0.1 percent

sulfated ash level, and 0.189 weight percent

sulfated ash, or 18.9 percent at the 1.0 per- cent sulfated ash level.

The D 874-77 sulfated ash test procedure was evaluated for use with recycled oils to be used

as burner fuel. As a part of the evaluation, the

D 874 test was applied to a number of used oils,

recycled oils, virgin fuel oils, and a blend of virgin residual fuel oil with used oil. The

results of these analyses are shown in table 30. In general, the results indicate that the repeatabilities obtained for D 874 with used and re- cycled oils are consistent with the ASTM criteria.

This table also includes some results for the

D 482 (regular ash) procedure, and it may be seen that the standard deviations obtained for that

method are similar to those for the D 874 method.

(Note: D 482 precision statement does not cover

ash values above 0.15 percent). However, chemical analyses of the D 482 ash from two used auto- motive oils (W022 and W011) indicated lead re- coveries of only 59.9 percent and 62.2 percent,

respectively.

In order to establish that the D 874 sulfated

ash test procedure can reliably indicate the primary ash-forming constituents in a recycled

fuel oil, it was necessary to further evaluate

the three possible problems mentioned in the test procedure; phosphorus, lead and magnesium.

For phosphorus, the D 874 test procedure states that "when phosphorus is present with metals, it remains partially or wholly in the sulfated ash

as metal phosphates" [2]. This statement was

36
Fuel oil grade

Table 30. Repeatability of the D 482 and D 874 ash test procedures.

Sample

description

Virgin fuel oil

Virgin fuel oil

Virgin fuel oil

Virgin formulated motor oil

Used automotive crankcase oil

Used automotive crankcase oil

Composite used automotive

crankcase oil

Above sample centrifuged to remove large to moderate

particulates

Sample Ash, wei qht percent

number D 482 D 874

Average SO nf Average SD

a

n

F126 0.0203 .0003 ( 3) 0.0215 ( 1)

F125 0.0294 .0006 ( 3) 0.0268 ( 1)

F022 0.0487 .0006 ( 3) 0.0507 ( 1)

M011 0.840 .005 ( 3) 1.09 .03 ( 6) won 1.42 .05 (16) 1.84 .04 (ID

W004 2.16 .04 ( 3) 3.06 .06 ( 3)

W022 1.81 .03 ( 6) 2.68 .07 (ID

W022

Re-refiner's feedstock used oil W023

Service station used oil

Recycled fuel oil (source A)

Recycled fuel oil (source B)

Fuel oil/used oil blend

(20% W022)

1.25 .03 ( 3) 1.43

Numbers in parentheses are n (= number of determinations).

Centrifuged for 20 minutes at 20,000 x gravity.

.02 ( 6)

W023 1.27 .01 ( 2) 1.423 .003 ( 2)

W033 0.64 .02 ( 2) 0.66 .03 ( 2)

F133 4.58 .02 ( 2) 4.70 ( 1)

F134 0.95 .01 (2) 1.25 .02 ( 2)

(F022) 0.581 .005 ( 2)

confirmed, and it was further reported that the phosphorus would most likely be found in the

final ash as the phosphate (P0 4 3

) or pyrophosphate

(P2 7 ~ 4

) [27]. In order to establish the magnitude

of the problem, phosphorus concentrations were determined in two recycled fuel oils and four

used automotive lubricating oils, and these av- eraged 880 ug/g (range = 716 to 1035 ug/g, n = 6). These results are consistent with the phosphorus

concentrations reported for 30 used lubricating

oils obtained throughout the country (average = 901 ug/g, range = 81 to 1393 ug/g, n = 30) [28]. The potential gravimetric effect (i.e., substitution of phosphate or pyrophosphate for oxide

and/or sulfate) of a phosphorus impurity at the above concentrations on the sulfated ash result

was calculated. These calculations indicate that

for the six used and recycled fuel oils described

earlier, the maximum potential gravimetric effect

on the sulfated ash values is only slightly larger

than the ASTM repeatability. 11 Therefore, for the purposes of this report, i.e., indicating the maximum level of ash-forming constituents in a recycled fuel oil, the phosphorus problem should

not be considered important.

For lead, the D 874 test procedure states

that it is "...not intended for the analysis of used engine oils or oils containing lead" [2]. Although the above statement may be interpreted

to mean that lead is lost during the test procedure,

discussions with persons originally involved

with the test procedure suggest that the statement

was included to eliminate errors in estimation

of the additive levels for used motor oils, based

on the sulfated ash result. Regardless, it was

felt important to establish whether lead is in

lx For example, the worst case is F 134 which has

a sulfated ash value of 1.25% (table 30) and a phosphorus concentration of 823 ug/g. If this

phosphorus is assumed to quantitatively remain

in the ash as the phosphate, and to substitute

only for the oxide (no sulfate substitution),

this maximum gravimetric effect is calculated

to be 6.0 percent, only slightly higher than

the ASTM repeatability of 5.6 percent for that

ash level. If substitution of phosphorus for sulfate occurs, the gravimetric effect will

be affected in the opposite direction, but never more than the ASTM repeatability (at

these phosphorus concentrations).

37
fact retained in the sulfated ash, and this ques- tion was evaluated through analysis of the sul- fated ash residue as described below. 12 .

For magnesium, the D 874 test procedure states

that it may not react the same as other alkali

metals, and the magnesium data "...should be interpreted with caution" [2]. For this element

also, an investigation was made of the amount

recovered in the sulfated ash (compared to the amount in the original oil sample), and is described below. In addition to lead and magnesium,

an elemental balance was obtained for calcium and

zinc. These four elements are the major inorganic

constituents in many recycled fuel oils and used

oils.

For this investigation, samples of two used

automotive lubricating oils (W022 and W011) were

ashed using D 874, and the sulfated ash residues

removed from the crucibles and analyzed by atomic

absorption spectroscopy. The amounts of the four

elements found in the ash were then compared to the amounts expected from analyses of the starting

materials, i.e., the used oils, and the percentages of the elements recovered in the ash are shown in table 31. No assumptions were made as to the chemical form of the element in the ash.

The data in table 31 show average recoveries

for all four elements of greater than 85 percent.

In order to evaluate whether some of the elements

were retained on the walls of the silica crucible,

one set of ash samples was dissolved i_n situ (in

their original crucibles). These "dissolution

recovery" values were higher than the average

recovery values in every case except for calcium,

which remained the same. For lead, the average dissolution recovery (one value for each oil sample) was 97.1 percent, and for zinc the the average dissolution recovery was 94.0 percent.

Reference 29 also indicates that both lead and

zinc can form stable, insoluble silicates on the

surface of silica crucibles, which may not be completely removed even with acid dissolution.

[It should be noted that formation of silicates

or an insoluble residue in the crucible is not a problem for the sulfated ash procedure since the

final weight of the ash is determined in the

crucible, but only for the evaluation of that

procedure.] The results indicate that these

four elements, lead, calcium, zinc and magnesium, are substantially retained in the sulfated

ash procedure, and confirm that this test is a useful indicator of the maximum level of ash- forming constituents in recycled oils used as fuel.

One additional concern in this test procedure

involves the crucible material. The D 874 method

specifies that porcelain, fused silica, or platinum crucibles may be used, "...except for samples

containing elements injurious to platinum" [2].

Table 31. Elemental recovery in sulfated ash

(D 874) for the major constituents in recycled

fuel oils.

Average percent recovery of specified

element in the sulfated ash

Element Used Oil W022b %

Used Oil W011

c %

Lead 85.6 ± 5.8 94.2 ±1.6

Calcium 99.4 ± 1.6 96.5 ±1.7

Zinc 88.1 ±3.7 90.2 ± 6.8

Magnesium 105 ± 3 90.8 ± 7.3

lz There is some evidence to suggest that the compounds of lead retained in the sulfated

ash, while apparently reproducible, are not stochiometrically lead sulfate.

Uncertainty values are the standard deviation

of the mean, sA/n~

Sample W022 is a composite used automotive oil;

number of determinations for each element

(n) = 4. Sample W011 is a used automotive crankcase

oil; number of determinations for each element

(n) = 3.

It further states that phosphorus may attack the platinum under the conditions of the test

procedure. Also, reference 29 indicates that

lead can form an alloy with platinum. Both of these elements are present in many recycled fuel oils. Therefore, it is recommended that the sul- fated ash test procedure be modified to indicate

that platinum dishes or crucibles should not be used with recycled fuel oils or used automotive

lubricating oils.

Conclusion

The ash content of a fuel oil is an important

indicator of performance for residual fuel oils,

including recycled oils used as fuel. ASTM method

D 874-77, "Sulfated Ash from Lubricating Oils

and Additives," has been evaluated with recycled

fuel oils, a virgin fuel oil/used oil blend, and

used automotive oils and is a satisfactory method

for indicating the maximum level of ash-forming

constituents in these petroleum products, with

the modification that platinum vessels should

not be used.

5.3.4 Total Sulfur

The sulfur content of a fuel oil is of concern

for the control of corrosion in combustion and

exhaust systems and for the reduction of environmentally important emissions. In both industrial

and Federal fuel oil specifications, the sulfur

is covered under two categories, total sulfur

and corrosive sulfur. This section discusses

test procedures for total sulfur, while Section

5.2.6, Copper Corrosion, discusses a test procedure for corrosive sulfur. It should be noted

that the test for total sulfur is important for both corrosion (especially of exhaust systems)

and for emissions, while the test for corrosive

sulfur considers only copper corrosion [18].

38
It is important that petroleum products be noncorrosive and remain so during service [19].

Crude petroleum usually contains a variety of sulfur compounds, most of which are removed

during refining to reduce the corrosive tendencies of the refined product. Particular attention is given to the control of sulfur content

in distillate fuel oils used in various household and industrial heating systems. In addition, the products of fuel oil combustion may contain sulfur compounds that are corrosive or become corrosive in the presence of moisture

[19]. Low-temperature corrosion can become

significant due to condensation of sulfuric acid

if the temperature of the stack gas is below the

"dew point" of the gas. Stack gas temperatures

can be considerably lowered when more efficient

energy-saving equipment is used, possibly causing severe corrosion problems [25]. A test for

total sulfur is also important to assure that

the fuel meets legal requirements (if any) for sulfur content, as well as applicable sulfur

oxide emission standards. Any test procedure

should be accurate in order to minimize unnec- essary cost in reducing the sulfur levels of the

fuel oils to meet these legal requirements.

A number of test procedures for total sulfur

are used with virgin fuel oils. These are ASTM

D 129-64, "Sulfur in Petroleum Products (General Bomb Method)"; D 1266-70, "Sulfur in Petroleum

Products (Lamp Method)"; D 1551-68 (reapproved

in 1973), "Sulfur in Petroleum Oils (Quartz-Tube

Method)"; D 1552-64 (reapproved in 1973), "Sulfur

in Petroleum Products (High-Temperature Method)";

and D 2622-77, "Sulfur in Petroleum Products

(X-Ray Spectrographs Method)." Except for the x-ray method, these test procedures involve the combustion of the sample and determination of the resulting oxides of sulfur by an appropriate

chemical method.

Method D 1552, the high-temperature method,

was selected for further evaluation with recy- cled oils because it is currently in common use and appears to be least affected by the contaminants usually found in used oils recycled for

use as fuel. In the D 1552 method, "The sample

is burned in a stream of oxygen at a sufficiently

high temperature to convert about 97 percent of the sulfur to sulfur dioxide. A standardization

factor is employed to obtain accurate results"

[2]. This standardization factor is obtained

"using an oil sample of similar type to the un- known sample and of accurately known sulfur content . . . ." [2]. The combustion products

are passed into an absorber containing an acid

solution of potassium iodide and starch indicator. A slight blue color is developed in the absorber solution by the addition of standard

potassium iodate solution. As combustion pro- ceeds, the sulfur oxides bleach the blue color, and more iodate is added. The amount of stan- dard iodate consumed during the combustion is a measure of the sulfur content of the sample [2].

In D 129, "The sample is oxidized by combustion in a bomb containing oxygen under pressure.

The sulfur, as sulfate in the bomb washings, is determined gravimetrically as barium sulfate"

[2]. This test procedure was not evaluated for

use with recycled oils because, as stated in note 1 of the test, "This method is not applicable to samples containing elements that give

residues, other than barium sulfate, which are insoluble in dilute hydrochloric acid and would

interfere in the precipitation step. These in- terfering elements include iron, aluminum, cal- cium, silicon, and lead which are sometimes pre- sent in greases, lube oil additives, or additive

oils. Other acid insoluble materials that interfere are silica, molybdenum disulfide, asbestos,

mica, etc. The method is not applicable to used

oils containing wear metals, and lead or silicates

from contamination. Samples that are excluded

can be analyzed by ASTM Method D 1552, Test for Sulfur in Petroleum Products (High-Temperature

Method)" [2]. Recycled oils for use as fuel almost always contain one or more of these interfering elements or materials.

In method D 1266, "Sulfur in Petroleum Products

(Lamp Method)," the fuel oil sample is burned in a prescribed lamp placed in a closed system having

an artificial atmosphere; the sulfur oxides formed

during combustion are absorbed in a hydrogen

peroxide solution; and, finally, the sulfuric

acid formed is titrated with a standard sodium

hydroxide solution and the amount of sulfur in the original sample is calculated [2]. This

method is not often used for determination of sulfur in fuel oils, and, in addition, reference

18 states that "Method D 1266 is not applicable

to samples that contain halogens, phosphorus,

nitrogen, or other acid-forming compounds."

Since many recycled oils often contain halogens,

phosphorus, and other acid-forming contaminants,

this method was not evaluated for use with re- cycled oils used as fuel.

In method D 1551, "Sulfur in Petroleum Oils

(Quartz-Tube Method)," "The sample is vaporized

and burned in a stream of air, and the oxidation

completed by passing over quartz particles maintained at a temperature of 950 to 1000 °C. The combustion products are passed through hydrogen

peroxide which absorbs the sulfur as sulfuric

acid and the chlorine as hydrochloric acid. The

absorbent is then analyzed for total acidity and

for chloride ion" [2]. This method was not eval- uated for use with recycled oil because it is stated in the method that it gives erroneous

results when applied to materials containing

phosphorus and many organometall ic compounds,

both of which are often present in used oils, and because the method was discontinued by the ASTM in 1976.

Method D 2622, "Sulfur in Petroleum Products

(X-ray Spectrographic Method)," covers the deter- mination of total suflur in liquid petroleum products. In this method, the sample is placed in the x-ray beam, and the intensity of the sulfur

Ka line at 5.373 a is measured. The intensity of

a corrected background is subtracted, and the resultant net counting rate is compared to pre- viously prepared calibration curves to obtain

the concentration of sulfur in weight percent.

For sulfur concentrations between 0.015 to 5.0 percent, the ASTM repeatability is 0.05 x per- cent S and the ASTM reproducibility is 0.16 x percent S. This method is a possible alternative

39
Table 32. Sulfur data for fuel oils and recycled oils.

% Sulfur, D 1552 % Sulfur, D 2622

c Sample % Recycled Original Centrifuged

number Grade/source oil Operator 1

1.19

Operator 2

1.24

sample

ND

C

sample

F125 5/virgin fuel oil ND 1.17 1.12

F022 6/virgin fuel oil 3.06

3.22 3.17

3.06

3.17

3.14

2.96

2.92

2.91

ND

F134 5/recycled fuel 100 0.51 0.50 0.44 0.48

oil (source A) 0.45

0.45

0.52 0.49

F133 5/recycled fuel 100 0.49 0.55 0.42

oil (source B) 0.47 0.54 0.35

0.43

F133 Above sample,

centrifuged

100 ND 0.48 0.47

(100)

d 0.51 0.49 W022 Composite used auto- 0.38 0.38 0.36 0.38

motive crankcase 0.38 0.44 0.40

oil (20)

d 0.43

Fuel oil/used oil 2.36 ND 2.52 ND blend (80% grade 6, 2.58 2.59

F022; 20% used 2.63 2.57

oil, W022)

X-ray fluorescence method; see text for discussion of results between methods.

Centrifuged for 20 minutes at 20,000 x gravity.

ND = not determined.

Used oil not processed beyond collection and storage.

for D 1552; however, it was not the primary

method evaluated for recycled oils because it requires expensive and highly specialized in- strumentation, and because the method may re- quire corrections for elements commonly found in recycled oils (phosphorus, zinc, barium, lead,

calcium, and chlorine) [2]. However, since both

the instrumentation and operators with appropriate

experience and expertise were available to us, this method was used to analyze for sulfur in selected oil samples in an attempt to estimate

the accuracy of the ASTM D 1552 method, the one selected for extensive evaluation in this report.

These data are found in table 32, and the results

are discussed below.

For ASTM method D 1552, the repeatabil ities and

reproducibilities for judging the acceptability of results as stated in the ASTM method are shown in table 33. An NBS virgin fuel oil Standard Refer- ence Material (SRM 1623) having a certified sul- fur concentration of 0.268 percent was analyzed

12 times using D 1552 during 2 different days

and using 3 different operators, and the repeatability of the method for this fuel oil was calculated. The standard deviation of these 12 values was 0.042 percent sulfur. The values ob- tained did not vary from the average by more

than 0.038 percent sulfure, indicating acceptable repeatability of the D 1552 method for

virgin fuel oil

Table 33. Precision of D 1552 test procedure

for sulfur [20].

Sulfur,

(wt. % range) Repeatabil ity Reproducibility

0.0 to 0.5 0.05 0.08

0.5 to 1.0 0.07 0.11

1.0 to 2.0 0.10 0.17

2.0 to 3.0 0.16 0.26

3.0 to 4.0 0.22 0.40

4.0 to 5.0 0.24 0.54

Method D 1552, the high-temperature method,

was evaluated for use with recycled oils. Since

this is a comparative analytical technique, it requires fuel oils with known sulfur contents

for calibration and standardization of the in- strumentation, and two NBS SRM's having certified sulfur concentrations were routinely used

for calibration. The usual procedure was to establish the standardization factor each day. As a part of the evaluation of D 1552, a number

of virgin fuel oils, recycled oils, and a virgin

fuel oil /recycled oil blend were analyzed for sulfur content. The results of these analyses

are shown in table 32 and are discussed further,

below.

40
Contaminants normally found in recycled oils

do not significantly interfere in this test procedure. The test procedure states that alkali

and alkaline earth metals, zinc, phosphorus, and

lead do not interfere, and chlorine in concentrations less than 1 weight percent does not inter- fere [2]. In the D 1552 procedure, it is stated

that nitrogen present in excess of 0.1 weight

percent may interfere, depending upon the type

of nitrogen compound present in the oil and the combustion conditions of the test [2]. It is known from published surveys that most used auto- mobile crankcase oils contain nitrogen compounds

around the 0.1 weight percent (1000 ppm) level: analyses of 30 composite used oils averaged 814

ppm nitrogen, with a range of 530 to 1770 ppm

(w/w) [28]. A potential nitrogen interference

may be eliminated by the addition of about 250 mg of dry sodium azide to the iodometric titration vessel before initiation of the combustion

process. The sodium azide reacts rapidly and preferentially with the oxides of nitrogen, but

does not participate in or interfere with the sulfur determination [30]. (Reference 30 should

also be consulted regarding hazards in the use of sodium azide. This chemical can react to form

explosive compounds unless neutralized in a suitable manner.) However, reference 30 also indi- cates that the nitrogen interference will be very small at low concentrations of nitrogen.

For example, for a sulfur concentration of ap- proximately 2 wt.%, the presence of one-half wt. % nitrogen caused an error of 0.06 wt.% sulfur

on the low side, or about 3% relative. Our ex- perimental data comparing the D 1552 results

with an independent analytical method which does

not suffer from nitrogen interference (x-ray

fluorescence, D 2622) indicates that an error,

if present, is small and within the expected

ASTM repeatability and reproducibility (table

32). Consequently, we do not recommend any test modification such as sodium azide addition to the titration vessel.

The results of analyses for sulfur using this test (table 32) exhibit the repeatability of

D 1552 for determining the sulfur content for

virgin fuel oils, recycled and used oils, and

blends of virgin fuel oils with used oils.

As described above, X-ray fluorescence (XRF)

analyses (D 2622) were carried out on many of the fuel oil samples shown in table 32 in order

to obtain an independent verification of the

actual sulfur content of these oils. The re- sults of these analyses indicated that, except

for one sample (F 133), the XRF values for sul- fur agreed with the high-temperature method

(D 1552) in view of the latter' s stated repro- ducibility.

It was noted that during the D 2622 measurements some of the recycled oil and used oil samples showed a decrease in sulfur signal with

time, possibly due to settling of lead and perhaps other types of particles to the bottom of the sample cell. (This "settling" decreased the sulfur signal by 10 percent in 100 seconds for the worst case, sample F133.) In an attempt

to understand this behavior and explain the

F 133 result, three oils were centrifuged

for 20 minutes at 20,000 x gravity to remove

larger particles, and were then reanalyzed.

The results of these analyses, also shown in table 32, demonstrate that for sample F133 the removal of larger particles by centrifuging led

to analytical results by D 2622 which agreed

very well with the D 1552 values, while the

D 1552 results did not change after this treatment. For the other two oils for which no dis- crepancy had been noted, centrifuging did not appreciably change the D 2622 sulfur results.

As a final check for the D 1552 test procedure, a sulfur balance was calculated for the virgin fuel oil /used oil blend shown in table

32. The D 1552 analytical results for the fuel oil, F022 (80 percent), and the used automotive

crankcase oil, W022 (20 percent), provided a calculated blend concentration of 2.59 percent

sulfur. This value is consistent with the

D 1552 results for the blended sample as shown

in table 32.

Conclusion

The sulfur content of fuel oil is an important

characteristic that is controlled by law in most

areas. ASTM method D 1552, "Sulfur in Petroleum

Products (High-Temperature Method)," has been

evaluated with recycled fuel oils, used oils, and

a blend of virgin fuel oil with used oil and is

a satisfactory, rapid method for the determination of sulfur in these petroleum products.

5.3.5 Acidity

Some petroleum products are routinely treated

with mineral acid as part of a refining procedure.

Any residual mineral acid in a petroleum product

is stated to be "obviously. .. undesirable" [2]. The general requirements of a burner fuel oil as described in the ASTM D 396-76 specification

include the statement, "The grades of fuel oil specified herein shall be... free from inorganic

acid...." [2] (see also page 21 of section 5, Test Procedures, this report).

The word "acid" is a chemical term, and can

be defined as a substance that in water solution

ionizes with the formation of hydronium as one

of its ions (Arrhenius definition of an acid).

[Note:

+ hydronium ions are hydrated hydrogen

ions, H (H2 0)x]. One acid is characterized as being stronger or weaker than another, depending

on its degree of ionization, i.e., whether a larger or smaller concentration of hydronium

ions are present in a solution at a specific

total concentration of acid. The concentration

of hydronium ions in a solution is usually determined by use of a color indicator dye (which

changes color over a certain specific concentration range of hydronium ions, e.g., methyl orange).

by electrical measurements (potentiometry) , or by titrating the acid with a base to neutrality

as determined using a suitable indicator. The common practice is to express hydronium ion con- centrations in terms of a system known as the

pH scale. The pH value of a solution is the logarithm of the reciprocal of the activity

41
(effective concentration) of hydronium ion

which it contains, or

pH = log

[H+

]

! - "log [H+

] (1)

For pure water or a neutral solution, the hydronium ion concentration is 1 x 10 -7 moles per

liter, and the pH = 7. For a strong acid, the

hydronium ion concentration may be 1 x 10 -3 moles per liter, and then the pH = 3. (Note:

where the activity coefficient of the acid is less than 1.0, the actual pH value will vary

between, for example 3.0 and 3.5).

While a test procedure for acidity is not likely to be needed for virgin fuel oils because

of the many check tests made during various stages

of refinery operations [18], there is a possibility of acid contamination of a recycled fuel oil due to improper disposal practices, or due to use of mineral acid in the reprocessing procedure

during recycling into the fuel oil. Any mineral

acid present in significant amounts in a fuel

oil could result in serious corrosion problems,

especially for storage, transfer and burner systems.

In practice, the statement "...fuel oil...

shall be... free from inorganic acid..." [2] is impossible to confirm and only an upper bound

can be determined from any test method. Also,

both recycled and virgin fuel oils usually con- tain weak organic acids. and other components

which may be involved in chemical reactions

and/or buffering effects which neutralize or mask the presence of small amounts of an inorganic acid. (Note: Solutions of weak acids and

their salts or of weak bases and their salts are called "buffers" since they resist a change in hydronium ion activity upon addition of small amounts of strong acids or bases [31]). Further,

with regard to acidity, the important characteristic of a recycled fuel oil is the hydronium

ion activity, not the source of the ions. Therefore, the overall hydronium ion activity, or pH, appears to be the appropriate measurement rather

than the inorganic acid content.

There are two test procedures which can be used for the determination of acidity in recy- cled petroleum oils. The first procedure is ASTM method D 1093-65 (reapproved in 1975),

"Acidity of Distillation Residues or Hydrocarbon

Liquids." This test is similar to Method 5101.6 - Federal Test Method Standard No. 791B. The sec- ond test procedure is ASTM D 664-58 (reapproved

in 1975), "Neutralization Number by Potentiometric

Titration." This test is identical to Method

5106 -Federal Test Method Standard No. 791B, to the Institute of Petroleum Designation 177/64,

and to the British Standard 4457. A third test procedure, ASTM method D 974-64 (reapproved in 1977), "Neutralization Number by Color-Indicator

Titration," cannot be used with most recycled

fuel oils due to their dark coloration.

The D 1093 test procedure is a very simple

qualitative test, in which "The sample of... hydrocarbon liquid is shaken with water and the aqueous

layer tested for acidity to methyl orange" [2].

Preliminary review of this method indicated it

should be adequate for testing of fuel oil acidity, and therefore D 1093 was selected for further evaluation.

Test procedure D 664, neutralization number

by potentiometry, covers procedures for determination of acidic and/or basic constituents in petroleum products, and resolves these consti- tuents into groups having weak-acid, strongacid, weak-base, and strong-base ionization

properties [2]. This procedure involves dissolving the sample in a mixture of toluene and

isopropyl alcohol containing a small amount of water, and titrating it potentiometrically with

alcoholic potassium hydroxide or hydrochloric

acid solution. The meter readings are plotted

against the respective volumes of titrating

solution, and the end points taken at the in- flections in the resulting curve [2]. Since the

D 664 method can differentiate between strong

and weak acids, it can indicate whether a petroleum product contains a mineral (inorganic) acid

contaminant (strong acid), or an organic acidic

constituent (weak acid), or both. However, if a very small amount of strong acid is present in the sample in addition to weak acid(s), the quan- titation of that strong acid may be somewhat

obscured by the weak acid titration curve.

Method D 1093 can be used to test for acidity

directly in a hydrocarbon liquid, or in the distillation residue from a gasoline or petroleum

solvent. For a recycled fuel oil, the sample of hydrocarbon liquid can be used without distillation. The D 1093 method uses 50 mL of the petroleum sample, which is placed in a clean

centrifuge tube along with 15 mL of water and

three drops of methyl orange indicator solution.

(Note: Methyl orange indicator is a 0.1 percent water solution, and changes to a red color at approximately pH = 3.1 to 4.4 [32]). The stoppered tube is thoroughly shaken (caution: refer- ence 2 should be consulted for appropriate

venting procedures), and then centrifuged for

a specified period of time in order to separate

the water layer. A red or pink color in the aqueous layer indicates the presence of "acidity"

in the petroleum product and the sample is con- sidered to fail the test [2]. There is no pre- cision indicated for this test procedure.

The D 1093 test procedure for acidity was evaluated for recycled oils used as burner fuel. As part of this evaluation, the D 1093 test was applied to a number of recycled oils, used auto- motive lubricating oils, and virgin fuel oils. Two problems identified with this test procedure

were: 1) inadequate separation of the water

layer, and 2) use of the methyl orange indicator. These problems are discussed further

below.

During the evaluation, it was found that suf- ficient amounts of free water could not be sepa- rated under the conditions of the D 1093 test

for some of the recycled and used oils samples

which contained high levels of detergents and

dispersants. After additional investigation,

the test procedure was modified to use 50 mL of water (instead of 15 mL) with the 50 mL sample

of oil. This modification assures separation of

42
a sufficient quantity of free water (even with

high additive motor oils) so that the test pro- cedure can be completed. The effect of this

modification on the pH (hydronium ion concentration) would be to make the solution to be tested

more dilute, thus somewhat diluting any acid

which may be present from the oil sample. This

dilution effect can be calculated from equation

(1) above, and a pH = 3.00 would result in pH = 3.52 for the modified procedure, and a pH = 4.00

would result in a pH = 4.52 for the modified

procedure. This dilution effect would be reduced

by any buffering which might take place in the system due to the presence of one or more weak

acids, approaching zero dilution effect for a strongly buffered system.

Data are shown in table 34 for the several petroleum oils for which 15 mL of water could be separated, compared with results from the modified D 1093 procedure on the same oils. The results using methyl orange indicator as specified in the test agree for both of the procedures. The pH measurements shown in the table were made on the separated water sample after

removal from the centrifuge tube using a capillary syringe, and were made using a pH meter. These pH results are similar for two of the samples, the paraffin oil and sample number

F134, due to buffering effects of water (for the paraffin oil), and residual additives and/or

organic acids (for F134). (Note: Potentiometric titration with potassium hydroxide (K0H)

on sample F134 using ASTM method D 664 verified

the presence of this buffering effect, and required an average of 4.34 mg K0H per gram of

F 134 for neutralization.) Recycled distillate

fuel oil sample 7L24 had a much smaller buf- fering effect, and the modified D 1093 test procedure results showed an average pH change of 3.13 to 3.56, which is close to the calculated

effect due to dilution.

The second problem identified was use of methyl orange indicator as the detector for establishing the hydronium ion activity. In addition to the rather wide range of pH covered

by most indicators (e.g. methyl orange range is 3.1 to 4.4 [32]), the pH range of indicators

also may be affected by factors such as temperature, electrolyte concentration, the presence

of organic solvents, and the presence of colloidal particulates [33]. These effects can cause a shift in the color range of one or more

pH units [33]. The use of a potentiometric determination of the hydronium ion activity, such as

a pH meter, would eliminate this problem.

The modified D 1093 test procedure was then

applied to a variety of recycled fuel oils, used

oils, and virgin fuel oil samples, and the results

are shown in table 35. This table contains both

the colorimetric results as obtained from the methyl orange indicator, as well as pH measurements made on the separated water layer using

a potentiometric determination (pH meter). The data in table 35 indicate that, while most of the oil samples tested neutral to methyl orange,

the two recycled oil samples discussed earlier

(7L24 and F134) were the only samples tested

which gave positive tests for acidity. In ad- dition, the pH measurements on these two oils

indicated that the hydronium ion activities were definitely higher than the other samples. (Note:

Separate tests demonstrated that the presence of the methyl orange indicator has no detectable

influence on the resulting pH measurement.)

In order to investigate the nature of the acidity for the oil which tested strongly

positive to the modified D 1093 test procedure,

sample 7L24 (recycled distillate fuel oil) was evaluated further using potentiometric titration

Table 34. Comparability of the D 1093 and modified D 1093 test procedures.

Fuel oil grade DescriptionSample

number

50 mL oil + 15 Methyl orange indicatormL water

pjj 6.89

6.82

50 mL oil + Methyl oranc indicator

Neutral

Neutral

50

e mL water —

Paraffin oil Paraffin oil Neutral

Neutral 6.78

6.80

c

c Recycled distillate fuel oil Recycled distillate fuel oil 7L24

7L24 Acid

Acid

3.14

3.12 AcidAcid

3.60

3.52

5

55

Recycled fuel oil Recycled fuel oil Recycled fuel oil

F134

F134

F134

Acidd

e ND

f

4.28

ND

Acid^j

Acid°

Acida

4.30

4.22

4.24

Conditions for D 1093 test procedure.

Conditions for modified D 1093 test procedure (see text).

Viscosity measurements on this oil place the fuel oil grade between 2 and 4. Water after centrifugation was only slightly pink.

Insufficient water separated for color observation or pH measurement.

ND = Not determined.

43
Table 35. Repeatability of the acidity test procedure for petroleum

oils using the modified ASTM D 1093 .

Acidity

Fuel oil grade

2

4

5

6

6

Description

Virgin distillate fuel oil

Virgin residual fuel oil

Virgin residual fuel oil

Virgin residual fuel oil (source A)

Virgin residual fuel oil (source B)

Recycled distillate fuel oil

Recycled residual fuel oil

Composite used automotive oil

Used oil feedstock to re-refiner

Used oil from service station

. Q Used industrial oil

Sample

number

Methyl orange indicator P

H

b

F131 Neutral

Neutral

6.48

6.58

F126 Neutral

Neutral

6.42

6.35

F125 Neutral

Neutral

6.48

6.33

F022 Neutral

Neutral

7.03

7.01

F130 Neutral

Neutral

5.93

6.04

7L24 Acid

Acid

3.60

3.52

F134 AcidJ Acid°

Acida

4.30

4.22

4.24

W022 Neutral

Neutral

5.80

5.92

W023 Neutral

Neutral

6.32

6.42

W033 Neutral

Neutral

5.64

5.62

W037 Neutral

Neutral

5.20

5.18

In order to obtain adequate separation of the water layer, the ASTM D 1093 test procedure was modified

to add 50 mL of water to the 50 mL oil sample, instead of the normal 15 mL of water (see text). Water added to fuel oil had a pH = 7.00. Viscosity measurements on this oil place the fuel oil grade between 2 and 4. Water after centrifugation only slightly pink.

Used oil from an industrial wastewater treatment plant.

(ASTM method D 664) to determine whether a detectable amount of a strong acid (i.e., inorganic

acid) was present. In this experiment, a strong

base (potassium hydroxide, K0H) used to titrate

the acidic components of the oil sample, and the

resulting electrode potential plotted against

volume of titrant (fig. 5). In D 664, the strong

acid is calculated from the volume of titrant

required to take the sample to the appropriate

electrode potential (see D 664 for specific de- tails; for examples used in D 664, values of

approximately - 200 millivolts were used). The

results of this potentiometric evaluation, are found in figure 5. The titration curve of sample

7L24 did not indicate the presence of a strong

acid, only weak acids. The presence of the sul- furic acid in the second sample was easily detected.

The above results suggest that the ASTM D 1093 test procedure may be used with modifications to indicate the hydronium ion activity

(acidity) of recycled fuel oils. The recom- mended modifications to this procedure are: 1)

increasing the volume of water used from 15 mL

to 50 mL, and 2) removal of the separated water

layer from the centrifuge tube and determination

of the hydronium ion activity with a pH meter. An appropriate hydronium ion activity which ap- pears to be essentially equivalent to the methyl

44
Conclusion

+ 200

+ 100

Sample j*

Sample No. 7L24

g) plus 0.301

meq H2S04

8 -200

HI

-300

-400 - Strong acid component

_L

1 2 3 4 5 6:

Volume Titrant

(mL of 0.1898 N KOH)

Figure 5. Potentiometric Titration of Recycled

Distillate Fuel Oil Sample 7L24.

orange indicator (including the effect of dilution with the larger volume of water) would

be a pH of 4.5. 13 Thus, a pH value less acid

than pH = 4.5 would indicate a "neutral" result

(e.g., pH = 5.0), while a pH value more acid

than 4.5 would provide a "positive" indication

of acidity (e.g., pH = 4.0).

l3 The selection of a pH = 4.5 for the determination of a "positive" vs. "neutral" result appears appropriate due to comparability with the methyl orange results. However, there is some evidence

to indicate that, in the absence of other influences,

the corrosion of ferrous materials is possible

at hydronium ion activities of 10~5 (pH = 5) or higher [34].

The presence of high hydronium ion activity

(acidity) in a recycled oil to be used for fuel would be expected to have a deleterious effect

upon the storage-transfer-burner system. The ASTM method D 1093-65 (reapproved in 1975),

"Acidity of Distillation Residues or Hydrocarbon

Liquids," may be used to indicate the hydronium

ion activity (acidity) of recycled fuel oils,

with the modifications that the amount of water

initially added to the oil sample be increased

to 50 ml_, and that potentiometric detection be used to determine the hydronium ion activity

(acidity) of the separated water. A pH = 4.5 would be approximately equivalent to the methyl orange indicator color change as specified in the original ASTM test procedure.

6. Test Procedures and Data for Impurities of Environmental Concern

During the process of evaluating test pro- cedures for recycled oil used as fuel we be- came aware of three impurities which may be of special concern for environmental reasons. These impurities are lead, polynuclear aromatic

hydrocarbons (PAH), and the two halogens, chlorine

and bromine. They are often found in used and recycled oils, sometimes at relatively high concentrations, and were therefore investigated further.

It is recognized that environmental considerations with regard to recycled oil are the respon- sibility of the EPA. It is also recognized that

the EPA has not at present set limits for the three

impurities mentioned above in either new or recycled

fuel oils, even though they have indicated strong

interest in two of these, lead and PAH's [7, 35]. We have therefore developed and/or evaluated test procedures for these three impurities should they

be needed.

The individual test procedures are discussed

below.

6.1 Test Procedures for Three Recycled Fuel

Oil Impurities

6.1.1 Lead

The lead content of a recycled fuel oil is important both in relation to the control of ash

and deposits in burner systems, and to the re- duction of environmentally important emissions.

While the lead content is negligible in virgin

fuel oils, ( < 0.01 weight percent), it is found

in concentrations of up to 1.5 percent by weight

in crankcase drain oils. Lead and lead compounds

found as impurities in recycled oil used as fuel result primarily from the use of leaded gasolines.

At the present levels of consumption of leaded

gasoline, significant concentrations of lead in used automotive crankcase oils (and therefore in oil recycling feed stocks) may be anticipated

for some time.

45
Lead is not included in either industrial or

Federal fuel oil specifications. However, test procedures for carbon residue and/or ash are in- cluded in these specifications and lead and lead

compounds in fuel oil are partially included in these tests. For example, data included in this

report in part 5.5.3, Ash, demonstrate that the

ash test currently included in fuel oil specifications (ASTM D 482) measures approximately 60 percent of the lead content actually present in the oil.

The Environmental Protection Agency (EPA) has indicated that lead emission from the burning of used automotive crankcase oil is a significant

environmental problem [5,7]. There have been

several studies on the environmental impact of burning fuels containing lead, and the feasibility of lead removal where emission controls

are not available [36,37]. Additional work on this subject is currently in progress at the

EPA [16].

While there are no standardized test procedures available for lead in lubricating oils,

there are several test procedures for the determination of lead in other types of petroleum

products. These include ASTM method D 2788-72

(Reapproved 1977), "Trace Metals in Gas Turbine

Fuels (Atomic Absorption Method)" [2]; and

D 2787-12 (Reapproved 1977), "Lead and Vanadium

in Gas Turbine Fuels." There is also a method

for lead in grease, ASTM D 1262-55 (Reapproved

1976), "Lead in New and Used Greases" [2].

Method D 2788-72, the atomic absorption

analysis method, was selected for further evaluation with recycled oils because (1) the

instrumentation is widely available in petroleum testing laboratories, (2) this analytical

technique is the one usually used for lead analyses in lubricating oils, and (3) the method

appeared to be capable of acceptable accuracy and

precision on recycled and used oils.

In the D 2788-72 atomic absorption method,

"the oil sample, after appropriate dilution

with organic solvents, is burned in the flame

of an atomic absorption spectrometer. Light energy from a hollow cathode lamp is passed

through the flame where a part of this energy

is absorbed. The concentration of the element

in the diluted sample is directly related to the absorption measured. The addition of the appropriate internal standard furnishes the calibration needed to calculate the concentration of the element in the undiluted oil sample"

[2]. The method is capable of allowing analysis

for a number of elements in addition to lead with

additional runs on a single sample, but contains

no statement of precision.

In order to eval

D 2788-72 method, s analyzed by isotope

(IDMS). This IDMS

at NBS as a highly

the determination o sample materials, i [38], although too

uate the accuracy of the

everal oil samples were also

dilution-mass spectrometry

method has been established

precise absolute method for

f lead in a wide variety of

ncluding petroleum products

costly and impractical for

routine use. This IDMS method is referred to

as the "Reference Method."

The accurate determination of lead in recy- cled oils is particularly difficult, due in part

to the tendency of particulates containing lead

to settle to the bottom of the container. To assure homogeneous distribution of the various

types of lead species present, a 20 minute shaking of the sample container on a very vigorous

mechanical shaker (i.e., a paint shaker or equivalent) was employed prior to sub-sampling for analysis. In addition, it was found that during

the atomic absorption analyses, the diluted oil samples had to be agitated immediately prior to analysis (e.g., 30 inversions of a 100 ml volume

of 1 percent oil in methyl isobutyl ketone was sufficient to provide a homogeneous solution

for 2 minutes).

As part of the evaluation, this D 2788-72

method was used to determine the lead content

of several oils, and the results were compared

to results using the Reference Method. The data

indicated that while the D 2788-72 test procedure has reasonably good precision, it appears

to have a significant positive bias (table 36).

Because of the observed discrepancies of the method even with the above modifications, the

D 2788-72 method was evaluated further to reduce

this uncertainty. Additional investigation into

the method established that (1) the lead calibration curve developed as part of the test pro- cedure is apparently non- linear over the to 30 ppm (by weight) range indicated as acceptable in the test procedure, and (2) the presence of zinc

and calcium compounds in the oil samples (present

as additive components) along with the particulate

nature of the lead appeared to enhance the lead

signal for certain oils, even using the method

of additions as described in D 2788-72.

The problems described above appear to be due

primarily to the particulate nature of the lead

and lead compounds found in used automotive

crankcase oils. Additional evaluation of the test procedure indicated the problems could be substantially improved by the introduction of

a dispersant along with ultrasonic agitation of the diluted sample just prior to final dilution

and analysis. The modified D2788-72 procedure

is described below.

Modified D 2788-72 Test Procedure

Prepare lead metal lo-organic standard as de- scribed on NBS-SRM 1059b Certificate of Analysis;

however, methyl isobutyl ketone (MIBK) is substituted for the light oil in the dissolution procedure. Prepare concentrations of working solu- tion fresh daily using MIBK.

Place sample in a virgorous paint shaker, and

agitate for 20 minutes. Transfer 1 g test por- tions to a tared 50 mL beaker. Reweigh beaker

and transfer test portion to 100 mL volumetric

flask using methyl isobutyl ketone (MIBK). Add

5 mL of a 1 percent succinimide dispersing agent

and dilute to calibrated volume with MIBK. Just

46
Table 36. Initial comparison of lead values from the D 2788-72 method and the reference method.

a '

Sample

Jy££ Number

Composite used W022

automotive oils

Composite used W022

automotive oils

Used automotive won

crankcase oil

Used automotive won

crankcase oil

Standard

Method n Mean deviation

Reference 8 1.311 0.009

D 2788 12 1.438 0.062

Reference 3 0.657 0.006

D 2788 4 0.745 0.034

Results are in percent by weight

The Reference Method used was isotope dilution-mass spectrometry (see text).

prior to the sampling of the test portion for the standard addition, place the volumetric flask in an ultrasonic bath and agitate the sample for

10 minutes. Then transfer immediately four aliquots of the test portion to volumetric flasks.

(Note: The optimum concentration of lead for flame AAS is 5 to 10 ug/mL. If the final lead concentration including the standard addition

exceeds 20 ug/mL a non- linear curve is obtained

which has a tendency to produce high analytical

values.) With a volumetric pipet transfer known

concentrations of the lead metallo-organic stan- dard solution to three of the volumetric flasks

and dilute to calibrated volume with MIBK.

Turn on the AAS instrument and insert a lead hollow cathode lamp. Adjust the lamp current to the recommended value and set the wavelength to 283.3 nm using a spectral bandpass of 0.7 nm. Allow the hollow cathode lamp to warm up for 15 minutes. Insert a 10 cm single slot burner head

on the burner. Turn on the air-acetylene flame

and adjust the nebulizer to a flow rate of 2 to

3 mL/min. Then while nebulizing MIBK, adjust the acetylene flow rate to obtain a lean flame. Neb- ulize the unknown solutions and obtain a net ab- sorbance for each solution. Always nebulize MIBK

before and after taking a measurement. Repeat the measurements three times and then determine the concentration in the unknown sample by extrapolation.

Additional analyses using the above modified

D 2788-72 method on four used recycled oils pro- vided the data shown in table 37. These data

indicate that the precision of the test procedure

is good (although a full-scale precision study

has not been made), and results from the modified D 2788-72 procedure agreed reasonably well with the Reference Method for three of the four

oils analyzed. The results from the fourth oil (W023) agreed reasonably well with the value

found by the Reference Method when the relatively large sampling variability (as indicated by

the large relative standard deviation of the Reference Method for that sample) is considered.

Conclusion

Should it be deemed necessary to measure the

lead content of recycled fuel oil for either

performance (ash and deposits) or environmental

concerns, ASTM Method D 2788-72 (Reapproved

1977), "Trace Metals in Gas Turbine Fuels (Atomic

Absorption Method)" has been evaluated with re- cycled fuel oil and used oils. The method will

give acceptable results with a precision of ap- proximately ± 10 percent if the D 2788-72 test

is used along with the modifications as described

in the report.

Because of the fine particulate nature of the lead (and other metals) contaminants, particular

attention must be paid to obtaining and preserving a representative sample.

6.1.2 Polynuclear Aromatic Hydrocarbons

Polynuclear aromatic hydrocarbons (PAH's,

PNA's), or polycyclic organic matter (POM), have been of scientific interest due to the proven mutagenicity and/or carcinogenicity of a number

of these compounds. PAH's are known to concen- trate in used automotive lubricating oils, appar- ently coming from the gasoline or diesel fuel and their combustion products [39]. A recent publication has also suggested that used auto- motive crankcase oils, containing PAH's, may be

a major mutagenic burden in the aquatic environ- ment [40]. In light of this information, test procedures for PAH's have been investigated and

a method has been developed and is provided which

can be used to indicate the PAH content of recy- cled oils intended for use as fuel, should such

47
Table 37. Comparison of lead values from the modified D 2788-72 method

and the reference method.

Reference Method

1 Modified D 2788-72L

Type Number Percent

lead

c Standard

deviation

Relative

SD (%) n

8

Percent

lead

c Standard

Deviation

Relative

SD (%) n

Composite used

crankcase oil (Source A)

W022 1.311 0.009 0.7 1.33 0.054 4.1 12

Composite used

crankcase oil W011

(Source B)

Re-refiners feed- stock used oil W023

Recycled fuel

oil F134

0.657 0.006 0.9

0.477 0.030 6.3

0.533 0.001 0.3

0.662 0.013 2.0

0.526 0.027 5.2 12

0.491

u 0.042 8.5

The Reference Method used was isotope dilution-mass spectrometry (see text). See text for modification of the D 2788-72 procedure.

Results are in percent by weight.

The sampling sequence for these three samples was 0.534, 0.488, and 0.451 percent lead, indicating

rapid settling of lead-containing particulates in the original oil sample. Additional evidence

for the particulate problem with sample F 134 can be found in Section 5.3.1 of this report (sediment

test procedure).

a test be found necessary. Due to the difficulties involved in the accurate analysis of PAH's

in complex matrices such as petroleum oils, this test is a nonroutine, research laboratory method.

No routine test procedure for PAH is currently

available.

PAH's are multiple-ring structures consisting

of two or more fused aromatic rings, and typically have four or more rings. The relative carcinogenicity of a number of these compounds has been indicated [39]. Benzo(a)pyrene (B(a)P), a five-ring polynuclear aromatic hydrocarbon, has been often used by the EPA and others as an in- dicator compound for total PAH [35,41]. This

compound has been indicated as having a high

carcinogenic activity [39].

One of the reasons EPA has used B(a)P as an indicator for total PAH is the difficulty in individually determining the carcinogenic PAH compounds which may be present in each sample

of interest. Justification for selecting B(a)P

as an indicator compound for total PAH was de- veloped in an EPA study in which an air pollution data indicated a correlation between the

B(a)P concentration and the concentration of

10 other PAH's [41]. For the purposes of this

report, a test procedure for the determination

of B(a)P in oil was developed and is included

here.

A number of methods are available for the

separation and/or quantitation of B(a)P, including gas chromatography, gas chromatography/mass

spectrometry, high-performance liquid chromatography (HPLC), and thin-layer chromatography cou- pled to fluorescence spectroscopy. Each of these analytical techniques generally involves

a preliminary extraction, a separation by one

of the above chromatographic techniques, fol- lowed by qualitative and quantitative determination of B(a)P. A major problem with all of these techniques is the petroleum lubricating

oil matrix, which is composed of thousands of organic compounds including paraffinic, naphthenic, and aromatic molecules with sidechains,

cross-linking, various degrees of unsaturation,

etc.

Previous NBS research in trace organic analysis indicated that a HPLC method, using a two- column separation system, would provide an ac- ceptable test procedure for B(a)P. Several ad- vantages of this method include:

1) capability for utilizing relatively

large samples, enhancing B(a)P detectability and reducing problems from con- tamination, absorption and adsorption;

2) each of the two columns can be optimized

for different characteristics, providing

a highly selective separation; and

48
3) fluorescence emission spectroscopy can

be used as the detection technique, pro- viding high sensitivity and specificity.

It should be noted that all of the analytical

techniques, including the HPLC test procedure

discussed below, are research methods requiring

sophisticated instrumentation and highly skilled

analysts.

The HPLC method described here was especially

developed for the quantitative determination of B(a)P in petroleum oils, and is described in greater detail in reference 42. In general,

following appropriate sample preparation in- cluding a 20 minute shaking in a vigorous,

double action paint shaker before sampling, the five-condensed-ring PAH fraction is isolated

from the other components of the petroleum oil on the first chromatographic column, and this

fraction (containing the B(a)P) is collected.

Separation of the B(a)P from other five-ring

PAHs is made on the second chromatographic column,

with further selectivity obtained by fluorimetrically monitoring the effluent for identification and determination of the B(a)P. The specific test procedure is described in more detail

below.

Experimental

Instrumentation: The liquid chromatographic

unit used in this work consisted of two high pressure pumps and a solvent programmer; a sample

injector; an ultraviolet (254 nm) photometric

detector; and a spectrofluorometer equipped with

a 10 uL flow cell. The columns used were uBondapack-NH2 and uBondapak-C 18 . 14 Data were obtained

from the resultant chromatograms on a strip chart

recorder.

Methodology: This HPLC method utilizes two chromatographic columns for the isolation and separation of individual PAH compounds. The

first chromatographic column (uBondpak-NH2 ) provides a separation of PAH based on ring size. The degree of alkylation of the PAH compound has little effect on retention volumes. The second

column (uBondapak-C 18 ) provides a separation re- lated to the aqueous solubilities of the respec- tive PAH compounds. Parent PAHs can be sepa- rated from both their alkylated homologs and

their structural isomers on the latter column. Efficient isolation of individual PAH from

complex mixtures of hydrocarbon (i.e., petroleum) was ahieved by using both of these

columns in an integrated procedure.

The concentration of B(a)P in some re- cycled fuel oils, used oils, and virgin

fuel oil samples was measured using the following procedure:

1) The density of each sample was determined by accurately weighing 10 mL of

oil on an analytical balance, and by

measuring its volume in a class "A" volumetric flask.

2) Dilution and filtration of the samples were accomplished by filling a 1.33 mL stainless

steel sample loop with the oil to be measured, followed by pumping the contents of the loop through a 2 urn filter into a 10.0

mL volumetric flask. The sample was then

diluted to 10.0 mL with methylene chloride.

3) Isolation of the five-ring PAH fraction

was effected by injecting 200 uL of the diluted filtrate onto a 300 x 12 mm uBondapak-NH column. The B(a)P fraction was collected in a volume of ^20 mL (see

fig. 6).

4) This 20 mL was reduced to a volume of be- tween 200 and 500 uL using a N2 purge at room temperature. The volume measurement

was made by means of a micro syringe, calibrated to 5 uL.

5) Separation of B(a)P from other five-ring

PAH isomers and quantification was accom- plished by injecting 23 uL of the frac- tionated oil on a 300 x 4 mm uBondapak C 18 column. Further selectivity was obtained

by monitoring the chromatographic effluent

fluorimetrically, with the excitation wave- length (295 nm) and emission wavelength

(403 nm) optimized for the detection of B(a)P. B(a)P was identified in each oil on the basis of both the chromatographic reten- tion volume and its fluorescence emission

spectrum (fig. 7).

Results: The concentration of B(a)P in each

sample was calculated using the following equation:

Concentration of B(a)P in oil =

(Peak height) (K X )(K2 ) (K3 ) (K4 ) (V)(p)

14 In order to describe work in this field ade- quately, it has been necessary to identify com- mercial materials and equipment. In no case does

such identification imply recommendation or en- dorsement by the National Bureau of Standards, nor does it imply that the material or equipment is necessarily the best available for the purpose.

The terms in this equation are defined as:

Peak

height = Height of B(a)P chromatographic

peak in mm.

V = 1.33 mL, volume of oil analyzed.

p = Density of oil in g/mL.

K 1 = Unfractionated dilution factor; the ratio of the volume to which the fil- tered oil was diluted to the volume

which was injected for fractionation

(10/0.2).

49
ft

10 20 30 40 50

mL

Figure 6. Prefractionation of an Oil on uBondapak-NH2

. Mobile Phase: 5 Percent Methylene Chloride in Hexane.

K„ = Fractionated dilution factor; the ratio of the volume to which the filtering PAH fraction was concen- trated to the volume of the sample

injected for analysis (x/0.023, where

x = original sample size in mL).

K. = Fluorescence response factor for B(a)P

in mm/ug.

K. = Attenuation factor; correction for

the difference in detector attenu- ation used when calculating K_ and

that used for the analysis.

Data on the repeatability of this HPLC test procedure for B(a)P in a number of petroleum oils

is found in table 38. The oils which were ana- lyzed include recycled oils, used automotive oils, and virgin residual fuel oils. The relative stan403

Figure 7. The Analysis of a Prefractionated Oil on (jBondapak-C 18 . A = Ultraviolet Elution Profile

at 254 nm; B = Fluorescence Elution Profile With

Excitation at 295 nm and Emission Monitored at 403 nm; C = Fluorescence Emission Spectrum of Benzo(a)Pyrene. Mobile Phase: 30 Percent Water in Acetonitrile.

dard deviations of these results ranged from 4 to 22 percent. A solution of known concentrations

of five pure PAH compounds (B(a)P, 2-methyl naphthalene, phenanthrene, f luoranthene, and chrysene)

in hexane was used to verify the retention volume

of B(a)P and to confirm the detector calibration.

The average result from four determinations of B(a)P

in this solution was 51 ug/g with an uncertainty

of ± 6 (jg/g (twice the standard deviation of the

mean). This result agrees well with the prepared

B(a)P concentration of 53.8 ug/g in this standard

solution.

Conclusion

The polynuclear aromatic hydrocarbon content

of recycled oils used for fuel may be of interest

from environmental considerations. A test proce- dure for the detection and determination of benzo(a)pyrene (B(a)P), a PAH which may be useful as an indicator of total PAH content, was developed

and is included here, should such a test be found

necessary. Only research analytical test procedures such as that reported herein are available

for the determination of B(a)P in petroleum

samples.

50
Table 38. Repeatability of the HPLC test procedure for B(a)P in petroleum oils.

B(a)P Concentration (ug/g)

Fuel oil grade Description

Sample

number — PAH solution3

5 Virgin fuel oil F125

6 Virgin fuel oil F130

__.b Recycled distillate

fuel oil 7L24

5 Recycled fuel oil (Source A) F133

5 Recycled fuel oil (Source B)

F134 — Composite used

automotive oil W022 — Used oil feedstock

to re-refiner

W023 — Used tractor diesel 8B3

Individual values

58, 50, 43, 52

2.7, 2.9, 2.9, 3.7

33, 36, 35, 33

9.3, 8.2, 7.3, 6.1

3.4, 4.0

9.0, 7.8

10, 8, 11, 10, 11, 14, 14, 16, 12, 14, 17

16, 10, 14, 13, 10, 14, 12, 11

motor oil 1.5, 1.3, 1.7, 1.3

Relative

standard

Mean deviation (%)

51 12

3.0 15

34 24

7.7 18

3.7 111

8.4 10

12 22

12 17

1.4 13

PAH solution was made from five pure PAH compounds, dissolved in hexane; B(a)P concentration was 53.8 ug/g (see text).

Viscosity measurements on this oil placed it between grade numbers 2 and 4.

6.1.3 Halogens: Chlorine and Bromine

While chlorine and bromi

found at significant levels

burner fuel oils, they are trations in many recycled f used automobile crankcase o oils from vehicles utilizin

been analyzed and found to cent by weight of both chlo

primarily to the industries

hydrocarbons as "scavengers

levels of chlorine are foun

industrial cutting oils, wh

into fuel oil. While there

specific studies on the env halogens in burner fuel oil some halogenated hydrocarbo

ne are not normally

nor measured in found at high concenuel oils derived from

il . For example, used

g leaded gasolines have contain 0.1 to 0.3 per- rine and bromine, owing

use of halogenated

" for lead. Also, high

d in certain types of ich may be recycled appear to be no ironmental effects of

s, the toxicity of

ns is well established.

For the purposes of this report, analytical

methods for the analysis of chlorine and bromine

in petroleum oils have been evaluated, and a test procedure for these elements is included here,

should such a test be found necessary.

Analytical methods which were considered for the determination of chlorine and/or bromine

include ASTM 808-63 (reapproved in 1976),

"Chlorine in New and Used Petroleum Products

(Bomb Method)"; D 1317-64 (reapproved 1973),

"Chlorine in New and Used Lubricants (Sodium

Alcoholate Method)"; x-ray fluorescence; and neutron activation analysis.

In the D 808-63 method, "The samples are oxidized by combustion in a bomb containing

oxygen under pressure. The chlorine compounds

thus liberated are absorbed in a sodium carbonate solution and the amount of chlorine present

is determined gravimetrically by precipitation

as silver chloride" [2]. This test procedure

was originally developed for chlorine-containing

industrial oils, and assumes that compounds con- taining halogens other than chlorine will not be present [2]. For used automotive crankcase oil,

samples usually contain high levels of both

chlorine and bromine. They also usually con- tain foreign materials which would be expected

to interfere in a gravimetric determination using

silver ions (e.g., silica, lead). Therefore, the

D 808-63 test procedure would provide only a single value, which would include all silver

halogens, plus all other insoluble materials present.

The D 1317-64 method consists of dissolving

the samples in a low boiling hydrocarbon mixture,

and further boiling "under reflux with metallic

sodium and n-butyl alcohol. Under these conditions the chlorine is converted to sodium chloride

which is then extracted with water. The chlorine

51
in the extract is determined volumetrical ly by

titration with silver in the presence of thiocyanate" [2]. This method was originally developed for chlorine-containing industrial oils,

and assumes that compounds containing halogens

other than chlorine are not present [2]. In order to circumvent this difficulty, the pro- cedure was modified by utilizing an ion chromatographic determination instead of the silver

titration method described in D 1317-64. The

modified sodium alcoholate method provides for the quantitative determination of both chlorine

and bromine in an oil sample, and improves the sensitivity down to approximately 1 pg/g for

chlorine and 10 pg/g for bromine.

X-ray fluorescence analysis (XRF) is a wellknown analytical method which can be used to determine both chlorine and bromine in petroleum products. In this method, the sample is placed in the x-ray beam, and the intensity

of the appropriate fluorescence x-ray is measured. The intensity of a corrected background,

appropriate to the element of interest, is sub- tracted from this intensity. The resultant net counting rate is then compared to previously pre- pared calibration curves to obtain the concentration of the element. This method was used in the

U.S. Army/EPA study on re-refined lubricating

oils, for the determination of chlorine [43].

The method suffers from several problems, including a lack of sensitivity for both chlorine and

bromine at low levels (i.e., less then 100 pg/g),

a sensitivity to the geometrical location of the halogens within the sample (a problem with samples

having high particulate loadings), and x-ray self- shielding effects due to the high lead content

of some samples.

In the neutron activation analysis (NAA)

method, the sample is irradiated in a neutron source (usually a nuclear reactor, in order to obtain the required sensitivity) for a period

of time, and, after withdrawing the sample,

the resulting induced radioactivity is measured.

This radioactivity is detected and quantitated

using a high resolution germanium semiconductor

detector. Each element of interest may be uniquely identified through observation of its gamma- ray energy, half-life and peak ratios if multiple gamma-rays are produced. The NAA method measures total chlorine and total bromine in a fuel oil sample, regardless of chemical

form or location, and does not suffer from significant problems with contaminants expected to be

in used crankcase oils or recycled fuel oils.

The sensitivity of NAA for both chlorine and

bromine is below 5 ug/g using conventional analysis methods. With more specialized methods,

this sensitivity can be lowered to well below

i ug/gIn table 39, analytical results are shown for halogen analyses by the four methods described

above. Method D 808-63 gave poor agreement with

the other methods, even if the chlorine and bro- mine concentrations together are considered. The

modified D 1317-64 method provided reasonably

good results, except for sample B 033, and shows

potential for providing a good method for both

chlorine and bromine in petroleum products,

including recycled burner fuel oil. At the pre- sent time, however, it is felt that this method

requires additional development in order to assure both consistant accuracy and reliability.

The XRF method has been evaluated in detail

in Section 5.3.4 of this report, for use with

sulfur, and this method when used for the halo- gens suffers from some of the same problems de- scribed in detail in that section. However, if the instrumentation is available, the XRF method

can be used to obtain very approximate chlorine

and bromine values quickly.

The NAA method has been found to be both

repeatable and consistent with results from

other analytical methods, including the values

shown in table 39. Although not considered a routine analytical technique, the NAA method is straightforward and analyses can be obtained

commercially. Analyses were completed for all of the samples described in table 39 using the

procedure described below. Although this proce- dure is not in ASTM format or highly detailed,

it provides sufficient information for an experienced individual to duplicate these analysis.

General Description of the Neutron Activation

Analysis Procedure: Oil samples were vigorously

shaken in a paint shaker for 20 minutes immediately

before subsampling for analysis. Approximately

0.100 g samples were taken in duplicate, and trans- ferred into small preweighed polyethylene vials

which had previously been cleaned with nitric acid

and distilled water. After reweighing to determine sample weight, the vials were heat-sealed

and irradiated for 5.0 minutes in the RT-4 pneu- matic tube facility of the NBS nuclear reactor. The thermal neutron flux at that position is 1.3 x 10 13 n-cm~2 *s -1

. Standards, in the form

of aqueous solutions of NaCl and KBr, were pre- pared from reagent grade chemicals and handled

identically to the samples.

After irradiation, the induced radioactivities were allowed to decay for approximately 30 minutes (chlorine) or 1 day (bromine) before

collecting the gamma-ray spectra on a Ge(Li) de- tector system and pulse height analyzer. Counting periods were approximately 5 minutes for chlorine ( 38 C1 isotope; 37.18 m half-life) and

15 minutes for bromine ( 82 Br isotope; 35.34 h half-life). After counting, the spectra were

analyzed, peak areas calculated, and concen- trations determined after comparison with the appropriate standards. Photopeaks used for analysis were 1642 keV and 2168 keV (chlorine),

and 554 keV, 776 keV, and 1317 keV (bromine).

Comparisons of peak ratios and concentrations

from the various gamma-ray photopeaks confirmed

the isotopic purity and lack of interferences

for these determinations.

Blank levels were determined in the polyethylene vials for both chlorine and bromine, and were found to be 14 ± 2 ug/g for chlorine,

and negligible (< 1 pg/g) for bromine. These

blank levels were substracted from the total (sample and vial) value to give the appropriate

concentration in the oil sample.

52
Table 39. Analytical results for halogen analyses by various methods ug/g.'

Description

Re-refined lube basestock

(Re-refiner A)

Sample

Number

848'

Chlorine analysis

Re-refined lube basestock B049

(Re-refiner B)

Re-refined lube basestock 879

(Re-refiner C)

Re-refiner lube basestock 849 (Re-refiner D)

Re-refined lube basestock B033 (Re-refiner E)

Used crankcase oil W004

(Source A)

Used crankcase oil W011

(Source B)

Composite used crankcase W022

oil

Used oil feedstock to W023

re- refiner

D 808

u

75, 70

ND

630, 690

910, 760

145, 244

5160, 5180

D 1317

L

ND9

6

ND

ND

87, 84

ND

2800, 2960 ND

4360,4350 2960

2040, 1940 1085

XRF

U

< 100

ND

1010

1250

ND

ND

ND

ND

ND

NAA

C

27

3, 1

920, 940

1110, 1150

200, 190

160, 180

3300, 3200

1740, 1850

2850, 2900

1370, 1350

1300, 1140

Bromine analysis

D 1317c

ND

< 12

ND

ND

12

ND

ND

2970

1093

< 2, < 5

15, 12

13, 10

< 2, < 2

2800, 2950

1620

2700, 2700

1100, 1050

1130, 1125

It should be noted that the re-refined lube basestocks shown in this table were specially selected

for inclusion because of their relatively high halogen contents, and were not representative of the halogen concentrations found in most re-refined lube basestocks.

The D 808 method does not differentiate between chlorine and bromine; therefore the values shown

in the chlorine column includes both halogens and should be interpreted as "apparent chlorine"

content, using this method. The D 1317 method was modified to utilize ion chromatography as a selective detection technique,

and therefore was able to provide both chlorine and bromine values (see text).

The x-ray fluorescence (XRF) analytical values were taken from the U.S. Army/EPA study on re-refined oils (AFLRL Report No. 98, May 1978) [43].

e NAA = neutron activation analysis (see text). (Note: All NAA results have blank values subtracted.)

These re-refined lube oil basestocks were obtained by the U.S. Army as part of their study on re-refined oils, and were included with additional analyses.

9 ND = Not determined.

Precision for this method is estimated to be approximately ± 10 percent (relative standard

deviation) for samples containing 100 ug/g or more of the halogens, based on results found in table 39 as well as extensive experience with

the technique. At lower concentrations, this

uncertainty may be somewhat larger.

we have included a test procedure in this report

in case it should be found to be necessary. The neutron activation analysis (NAA) test procedure

has been evaluated for use with recycled fuel oils

and used oils, and may be used to establish the

total chlorine and/or total bromine concentrations

of such products.

Conclusion

Some recycled fuel oils and used motor oils

contain high concentrations of chlorine and bro- mine, with combined totals possibly in the 2,000

to 6,000 ug/g range. While we are not aware of specific restrictions or deleterious effects of these halogens in a recycled fuel oil at such levels on either performance or the environment,

Acknowledgments

The authors wish to thank Mr. Robert Pedal!

,

Industrial Research Associate of the Association

of Petroleum Re-refiners, for his excellent tech- nical assistance and laboratory work. Without

access to his 20-years experience in petroleum

testing and oil recycling, our efforts would

have been considerably more difficult.

53
We also wish to thank Drs. Ian Bartky and Curt Reimann of the National Measurement Laboratory Director's Office of their advice and sug- gestions; Messrs. Richard Doitteau and Steven

Serkiz and Miss Gayle Sillery for their help in the laboratory work; and the many scientists

throughout the NBS who contributed greatly to the efforts reported here.

Finally, the authors especially wish to thank

Mrs. Helen Anne Hurd and Mrs. Virginia Davis for their untiring efforts in the preparation of this report and for their diligent endeavors

which have significantly contributed to making

the Recycled Oil Program more efficient and

effective.

References

[1] Fuel Oils, Commercial Standard CS 12-48,

Sixth Edition (September 25, 1948).

[2] 1977 Annual Book of ASTM Standards, Parts

23 and 24 (ASTM Philadelphia, PA, 1977).

[3] Criteria for Quality of Petroleum Products,

J. P. Allinson, ed. (Applied Science Pub- lishers, LTD., Essex, England, 1973).

[4] Swain, J. W. , Jr., Recycled Oils for Fuel Uses (unpublished report to the National Bureau of Standards, January 1978).

[5] Chansky, S. , McCoy, B. , and Surprenant, N.

,

Waste Automotive Lubricating Oil Reuse as

a Fuel , Report No. EPA - 600/5-74-032

(Environmental Protection Agency, Washington, D.C., September 1974).

[6] Swain, J. W. , Jr. , Assessment of Industrial

Hazardous Waste Management Practices in Petroleum Re-refining Industry Report No. EPAISW-144c (Environmental Protection

Agency, Washington, DC, June 1977).

[7] Report to the Congress: Waste Oil Study,

(Environmental Protection Agency, Washington, DC, April 1974).

[8] Anon., Waste Lube Oils Pose Disposal

Dilemma, Environmental Science and

Technology 6, 25 (January 1972).

[9] Berry, E. E. , MacDonald, L. P., and

Skinner, D. J., Experimental Burning of Waste Oil as a Fuel in Cement Manufacture,

Environment/Canada Report No. EPS 4-WP-75-1

(June 1975).

[10] American Petroleum Institute: Energy From

Used Lubricating Oils, API Publication No. 1588 (Am. Petroleum Institute, Washington,

DC, October 1975) (including errata sheets).

[11] Cukor, P., Technical, Economic and Environmental Assessment of Used Oil Recovery and

Disposal for Ontario, Report by Teknekron,

under contract to the Ontario Energy Man- agement Program, (March 1976).

[12] Suprenant, N. , Sahagian, J., and Hall, R. , Waste Oil Recovery and Refuse Program - Residue Management, GCA/Technology Report

No. GCA-TR-75-3-G, prepared for Maryland

Environmental Services (April 1975).

[13] Whismann, M. L. , Goetzinger, J. W. , and Cotton, F. 0. , Waste Lubricating Oil Re- search, series of research reports by the Bartlesville Energy Research Center, (Department of Energy, Bartlesville, OK,

1974 - 1977).

[14] Becker, D. A. , ed. , Measurements and Standards for Recycled Oil - I, NBS Special

Publication 488 (National Bureau of Standards, Washington, DC, August 1977).

[15]

[16]

[17]

[18]

[19]

[20]

[21]

[22]

[23]

[24]

Becker, D. A. , ed. , Measurements and Standards for Recycled Oil - II, NBS Special Publication 556, (National Bureau

of Standards, Washington, DC, September

1979).

Kaufman, H. B. tion (1978).(EPA) Private CommunicaASTM Standards on Precision and Accuracy

for Various Applications (ASTM, Phi 1 del

phia, PA, 1977).

Significance of ASTM Tests for Petroleum

Products, Special Publication No. 7-B

(ASTM, Philadelphia, PA, 1955).

Boldt, K. and Hall, B. R. , eds. , Significance of Tests for Petroleum Products, ASTM Special Technical Publication 7C (ASTM, Philadelphia, PA, January 1977).

1976 Annual Book of ASTM Standards, Part 30 (ASTM, Philadelphia, PA, 1977).

Minutes, Subcommittee on Statistical

Methods, ANSI Committee Z-l on Quality Assurance (Sept. 10, 1975).

Davis, E. C. , Private communication, Naval Ship Engineering Center (Oct. 13, 1977).

Precise Measurement of Heat of Combustion

with a Bomb Calorimeter (NBS Monograph 7, 1960, out of print).

Thermal Properties of Petroleum Products

(NBS Miscellaneous Publication 97, Nov. 9, 1929).

[25] Guthrie, V. B. , ed. , Petroleum Products

Handbook , (McGraw-Hill Book Co., New York,

1960).

[26] ASTM Committee D-2, Preprint for Letter Ballot 1978 (to be published in 1978 Annual Book of Standards, Part 23, (ASTM, Philadelphia, PA, in press).

[27] Burke, R. , (NBS) private communication

(1978).

54
[28] Whisman, M. S. , Cotton, F. 0., Gletzinger,

J. W. , and Reynolds, J. W. , Waste lubricating oil research: Part 4, A Summary of Composition Variations Among Thirty Used

Lubricating Oils Selected for Seasonal

and Geographical Significance, BERC.RI- 76/4 (Oct. 1976).

[29] Gorsuch, T. T. , The Destruction of Organic Matter , Vol. 39, International Series of Monographs in Analytical Chemistry (Per- gamon Press, New York, NY (1970).

[30] Bremorris, E. , Deering, J. R. , Meade, C. F. , and Keyworth, D. A., Materials Research and Standards 7, 459 (1967).

[31] Kolthoff, I. M. and Sandell, E. B. , Text- book of Quantitative Inorganic Analysis

pp. 43-46 (Macmillan Company, New York,

NY, 1948).

[37] Skinner, D. J., Preliminary review of used

lubricating oils in Canada, EPA 3-WP-74-4

(Environmental Protection Service, Environ- ment Canada, June 1974; revised January

1976).

[38] Barnes, I. L. , Murphy, T. J., Gramlich,

J. W. , and Shields, J. R. , Lead separation

by anodic deposition and isotope ratio mass spectrometry of microgram and smaller

samples, Anal. Chem. 45, 1881-1884 (1973).

[39] Dipple, A. , Polynuclear Aromatic Carcinogens , ACS Monograph 173, C. E. Searle,

Editor, Chap. 5 (American Chemical Society,

Washington, DC, 1976).

[40] Payne, J. F. , Martins, I., and Rahimtula, A., Crankcase Oils: Are They a Major Mutogenic

Burden in the Aquatic Environment?, Science , 200, 329-330 (1978).

[32] Lange, M. A. , ed. , Handbook of Chemistry , 8th edition, (Handbook Publishers, Inc.,

Sandusky, OH, 1952).

[33] Laitinen, H. A. , Chemical Analysis (McGrawHill Co. Inc., New York, NY, 1960).

[34] Kruger, J. , (NBS) Private Communication

(1978).

[35] Atmospheric Polycyclic Organic Matter

(POM): Sources and Population Exposure

(Draft EPA Report, by Energy and Environmental Analysis, Inc., Arlington, VA).

[36] Air Quality Criteria for Lead, EPA-600/8-

77-017 (December 1977).

[41] Preferred Standards Path Report for Polycyclic Organic Matter (U.S. Environmental

Protection Agency, Durham NC, October 1974).

[42] May, W. and Brown, J. , in Proceedings , Second NBS Conference on Measurements

and Standards for Recycled Oil , NBS Special

Publication 556, (National Bureau of Stan- dards, Washington, DC, 1978).

[43] Frame, E. A. and Bowen, T. C. , Jr., U.S. Army/Environmental Protection Agency Re- refined Engine Oil Program, AFLRL Report

No. 98, U.S. Army Mobility Equipment

Research and Development Command (May,

1978).

55

APPENDIX A

Energy Policy and Conservation Act

Section 383

57
Pub. Law 94-163 - 70 - December 22, 1975

FEDERAL ACTIONS WITH RESPECT TO RECYCLED OIL

42 USC 6363. Sec. 383. (a) The purposes of this section are

( 1 ) to encourage the recycling of used oil

;

(2) to promote the use of recycled oil

;

(3) to reduce consumption of new oil by promoting increased

utilization of recycled oil; and

(4) to reduce environmental hazards and wasteful practices associated with the disposal of used oil. Definitions. (b) As used in this section

:

(1) the term "used oil"' means any oil which has been refined from crude oil, has been used, and as a result of such use has been contaminated by physical or chemical impurities.

(2) The term "recycled oil'' means

(A) used oil from which physical and chemical contami- nants acqiured through use have been removed by re-refining or other processing, or (B) any blend of oil, consisting of such re-refined or otherwise processed used oil and new oil or additives, with respect to which the manufacturer has determined, pursuant

to the rule prescribed under subsection (d) (1) (A) (i), is substantially equivalent to new oil for a particular end use. (3) The term "new oil" means any oil which has been refined from crude oil and has not been used, and which may or may not

contain additives. Such term does not include used oil or recycled

oil.(4) The term "manufacturer" means any person who re-refines or otherwise processes used oil to remove physical or chemical

impurities acquired through use or who blends such re-refined or otherwise processed used oil with new oil or additives.

(5) The term "Commission" means the Federal Trade Commission.

(c) As soon as practicable after the date of enactment of this Act, the National Bureau of Standards shall develop test procedures for the determination of substantial equivalency of re-refined or otherwise

processed used oil or blend of oil, consisting of such re-refined or other- wise processed used oil and new oil or additives, with new oil for a particular end use. As soon as practicable after development of such

test procedures, the National Bureau of Standards shall report such

procedures to the Commission.

Rules. (d)(1)(A) Within 90 days after the date on which the Commission receives the report under subsection (c), the Commission shall, by rule, prescribe

89 STAT. 940

58
December 22, 1975 - 71 - Pub. Law 94-163

(i) test procedures for the determination of substantial equivalency of re-refined or otherwise processed used oil or blend of

oil, consisting of such re-refined or otherwise processed used oil and new oil or additives, with new oil distributed for a particular end use ; and

(ii) labeling standards applicable to containers of recycled oil in order to carry out the purposes of this section. (B) Such labeling standards shall permit any container of recycled

oil to bear a label indicating any particular end use for which a deter- mination of substantial equivalency has been made pursuant to sub- paragraph (A) (i). (2) Not later than the expiration of such 90-day period, the Admin- Rules, istrator of the Environmental Protection Agency shall, by rule, prescribe labeling standards applicable to containers of new oil, used oil, and recycled oil relating to the proper disposal of such oils after use. Such standards shall be designed to reduce, to the maximum extent

practicable, environmental hazards and wasteful practices associated with the disposal of such oils after use. (e) Beginning on the effective date of the standards prescribed pur- suant to subsection (d) (1) (A) —

(1) no rule or order of the Commission, other than the rules required to be prescribed pursuant to subsection (d) (1) (A), and

no law, regulation, or order of any State or political subdivision thereof may apply, or remain applicable, to any container of

recycled oil, if such law, regulation, rule, or order requires any

container of recycled oil, which container bears a label in accord- ance with the terms of the rules prescribed under subsection (d)(1)(A), to bear any label with respect to the comparative

characteristics of such recycled oil with new oil which is not

identical to that permitted by the rule respecting labeling stand- ards prescribed under subsection (d) (1) (A) (ii) ; and

(2) no rule or order of the Commission may require any container of recycled oil to also bear a label containing any term,

phrase, or description which connotes less than substantial equivalency of such recycled oil with new oil. (f) After the effective date of the rules required to be prescribed under subsection (d)(1)(A), all Federal officials shall act within

their authority to carry out the purposes of this section, including

(1) revising procurement policies to encourage procurement of

recycled oil for military and nonmilitary Federal uses whenever

such recycled oil is available at prices competitive with new oil procured for the same end use; and

(2) educating persons employed by Federal and State govern- ments and private sectors of the economy of the merits of

recycled oil, the need for its use in order to reduce the drain on

the Nation's oil reserves, and proper disposal of used oil to avoid waste of such oil and to minimize environmental hazards asso- ciated with improper disposal.

59

APPENDIX B

Fuel Oil Specifications

61
IS

(AMERICAN NATIONAL] ISTANOABD! ANSI/ASTM D396-76*

Standard Specification for FUEL OILS 1

This Standard is issued under the fixed designation D 396: the number immediately following the designation indicates the \ear of original adoption or. in the case of revision, the year of last revision. A number in parentheses indicates the year of

iasl reapprovat.

• Note — The Fahrenheit equivalent in Column 7 of Table 1 was corrected editorially in January 1977.

1. Scope

1.1 This specification (Note) covers grades

of fuel oil intended for use in various types of

fuel-oil-burning equipment under various cli- matic and operating conditions. Note—For information on the significance of

the terminology and test methods used in this specification, see the Appendix.

1.2 This specification is for the use of pur- chasing agencies in formulating specifications

to be included in contracts for purchases of

fuel oils and for the guidance of consumers of

fuel oils in the selection of the grades most

suitable for their needs.

2. General Requirements

2.1 The grades of fuel oil specified herein

shall be homogeneous hydrocarbon oils, free from inorganic acid, and free from excessive amounts of solid or fibrous foreign matter

likely to make frequent cleaning of suitable

strainers necessary.

2.2 All grades containing residual components shall remain uniform in normal storage and not separate by gravity into light and

heavy oil components outside the viscosity

limits for the grade.

3. Detailed Requirements

3.1 The various grades of fuel oil shall con- form to the limiting requirements shown in Table I. 3.2 Modifications of limiting requirements

to meet special operating conditions agreed upon between the purchaser, the seller, and

the supplier shall fall within limits specified

for each grade, except as stated in supplementary footnotes for Table 1.

4. Test Methods

4.1 The requirements enumerated in this specification shall be determined in accord- ance with the following ASTM Methods,2 except as may be required under 4.1.1. 4.1.1 Flash Point—Method D 93, Test for Flash Point by Pensky-Martens Closed Tester, 3 except where other methods are prescribed by

law for the determination of minimum flash point. For Grades No. 1 and No. 2, Method D 56, Test for Flash Point by Tag Closed

Tester3 may be used as an alternative with the same limits, provided the flash point is below 79.4°C (175°F) and the viscosity is below 5.8

cSt (45 SUS) at 3S°C (TOOT). This method

will give slightly lower values. In cases of dis- pute, Method D 93 shall be used as the ref- eree method.

4.1.2 Pour Point—Method D 97, Test for Pour Point of Petroleum Oils.3 Alternative

test methods that indicate flow point properties may be used for low sulfur residual fuels by agreement between purchaser and supplier. 4.1.3 Water and Sediment—The water and

sediment in Grades Nos. I, 2, 4, and 5 shall be determined in accordance with Method D

1796, Test for Water and Sediment in Fuel

•This specification is under the jurisdiction of ASTM

Committee D-2 on Petroleum Products and Lubricants. Current edition approved Aug. 27, 1976. Published October 1976. Originally published as D 396 - 34 T. Last previous edition D 396 - 75.

' For information on the precision of the ASTM methods

of test for fuel oils refer to "An Evaluation of Methods for Determination of Sulfur in Fuel Oils" by A. R. Crawford.

Fsso Mathematics & Systems Inc. and G. V. Dvroff. Esso

Research and Engineering Co.. 1969. This document is available from the* Publications Section. American Petro- leum Institute, 2101 L. St., N.W., Washington. D.C.

20037. 'Annual Book ofASTM Standards. Part 23.

213

62
iSfe D 396

Oils by Centrifuge; 3 and Grade No. 6 by Method D 95, Test for Water in Petroleum and Other Bituminous Materials.' and Method D 473. Test for Sediment in Crude

and Fuel Oils by Extraction.' 4.1.4 Carbon Residue—Method D 524, Test for Ramsbottom Carbon Residue of Pe- troleum Products.'

4.1.5 Ash—Method D 482. Test for Ash

from Petroleum Oils.' 4.1.6 Distillation —Distillation of Grade

No. 1 and No. 2 oils shall be determined in accordance with the Method D 86. Test for

Distillation of Petroleum Products.'

4.1.7 Viscosity—Viscosity of Grade No. 1 and 2 shall be determined in accordance with Method D 445. Test for Kinematic Viscosity of Transparent and Opaque Liquids and the Calculation of Dynamic Viscosity' and of Grades Nos. 4, 5, and 6 in accordance with

Method D 88. Test for Saybolt Viscosity.'

4.1.8 Gravity—Method D 287, Test for API Gravity of Crude Petroleum and Petro- leum Products (Hydrometer Method).'

4.1.9 Corrosion— Method D 130, Test for Copper Corrosion by Petroleum Products, Copper Strip Test,3 3 h test at 50'C (122°F).

4.1.10 Sulfur—The sulfur content of any

grade may be determined by any of the fol- lowing methods: Method D 129, Sulfur in Petroleum Products by the Bomb Method,2 -' Method D 1552, Sulfur in Petroleum Products, High-Temperature Method,2,3 or Method D 2622, Sulfur in Petroleum Products (X-Ray Spectrographic Method).2,4 In addition, the sulfur of Grade No. 1 may be determined by Method D 1266, Sulfur in Petroleum Products (Lamp Method).2,3

'Annual Book ofASTM Standards, Part 24.

214

63
D 396

T E * E it> V) I*

00 o CI ^T

si: SI:

eu£' — s Ta i Ci

sJPS

So

11

•5 8. i o 5 3 — £

_ H

"°

3 |= 2-s Ji°-S 3 3

o .5 el

.E = = ^ S M M 2 U = u ° •»« =

Z < k>J= .0 .5 Z 0. 3 .2 J

wi Isl

? E L. ° X .S -o -. E

O ffwH. d Ji °" M fl Zo. „ O J" >* WJ Ti -1 - S Zo. g.S E o-^

215

64
D 396

ii* 7°

Copper

SiripCor- rosion s

Speci-fic Grav- ity (dog AIM)

c:

a

« -

.E o>

5

\

COo

5 A

bO

U

00<

1

C5

Q

>

u.

5

o

o

cs A U

ri

'cD

5 oo

o

E s

§

A

= ?

Q u

exE

'c

ft.

o o 5

2

Car- bon Resi- due

on

IU

Bottoms, 2

2 o

a

cs o

O w

to•o —

E

.c ,0 -o •111

i C a

- rt

c o

o c

E «

o ^

2 w - • o •- w^

SSIT8 »»E5

-5 5 S-E

E g

.S *

c E S u

O -O

"S'i

E =

c —

o .E

"^ c

g"2* o-2#§? g "8

<« t. 3 ^ 6E": U < "^ Eo

c o

g I Z => 1 S--0 -g E°E ,"

llll^|l|f|E£

» to% c.2 K* 2 — " -°

> (S I

* -

g > : a « a - Sso • S|SA,

216

65
D 396

APPENDIX

XI. SIGNIFICANCE OF ASTM SPECIFICATION FOR FUEL OILS

Xl.l Scope XI. 1.1 ASTM Specification D 396, for Fuel

Oils, divides fuel oils into grades based upon the

types of burners for which they are suitable. It places limiting values on several of the properties of

the oils in each grade. The properties selected for limitation are those that are believed to be of the

greatest significance in determining the performance characteristics of the oils in the types of burners in which they are most commonly used. X1.2 Classes XI.2.1 Because of the methods employed in their production, fuel oils fall into two broad classifications: distillates and residuals. The distillates consist of overhead or distilled fractions. The residuals are bottoms remaining from the distillation, or blends

of these bottoms with distillates. In Specification D

396, Grades No. I and No. 2 are distillates and the grades from No. 4 to No. 6 are usually residual, although some heavy distillates may be sold as Grade No. 4. XI.3 Grades XI.3.1 Grade No. 1 is a light distillate intended

for use in burners of the vaporizing type in which

the oil is converted to a vapor by contact with a healed surface or by radiation. High volatility is necessary to ensure that evaporation proceeds with

a minimum of residue. XI.3. 2 Grade No. 2 is a heavier distillate than

grade No. 1. It is intended for use in atomizing type

burners which spray the oil into a combustion chamber where the tiny droplets burn while in sus- pension. This grade of oil is used in most domestic

burners and in many medium capacity commercialindustrial burners where its ease oT handling and

ready availability sometimes justify its higher cost over the residual fuels. XI.3. 3 Grade No. 4 is usually a light residual,

but it sometimes is a heavy distillate. It is intended

for use in burners equipped with devices that at- omize oils of higher viscosity than domestic burners

can handle. Its permissible viscosity range allows it to be pumped and atomized at relatively low

storage temperatures. Thus, in all but extremely

cold weather it requires no preheating for handling. XI.3.4 Grade No. 5 (Light) is residual fuel of

intermediate viscosity for burners capable of handling fuel more viscous than grade No. 4 without

preheating. Preheating may be necessary in some

types of equipment for burning and in colder cli- mates for handling. XI.3. 5 Grade No. 5 (Heavy) is a residual fuel more viscous than Grade No. 5 (light) and is in- tended for use in similar service. Preheating may be

necessary in some types of equipment for burning und in colder climates for handling. XI. 3. 6 Grade No. 6, sometimes referred to as "'Bunker C." is a high-viscosity oil used mostly in commercial and industrial heating. It requires pre- heating in the storage tank to permit pumping, and

additional preheating at the burner to permit atomizing. The extra equipment and maintenance re- quired to handle this fuel usually preclude its use in small installations. XI.3. 7 Residual fuel oil supplied to meet regulations requiring low sulfur content may differ from

the grade previously supplied. It may be lower in viscosity (and fall into a different grade number). If

it must be fluid at a given temperature. Method D

97 may not accurately reflect the pour point which

can be expected after a period of storage. It is sug- gested that the purchaser and supplier discuss the proper handling and operating techniques for a

given low-sulfur residual fuel oil in the installation where it is to be used.

X1.4 Significance of Test Methods XI .4.1 The significance of the properties of fuel

oil on which limitations are placed by the specifica- tion is as follows: Xl.4.1.1 Flash Point-The flash point of a fuel

oil is an indication of the maximum temperature at which it can be stored and handled without serious

fire hazard. The minimum permissible flash point is usually regulated by federal, state, or municipal laws and is based on accepted practice in handling and

use.XI.4. 1.2 Pour Point— The pour point is an indi- cation of the lowest temperature at which a fuel oil can be stored and still be capable of flowing under

very low forces. The pour point is prescribed in accordance with the conditions of storage and use. Higher pour point fuels are permissible where

heated storage and adequate piping facilities are provided. An increase in pour point may occur when

residual fuel oils arc subjected to cyclic temperature variations that may occur in the course of stor- age or when the fuel is preheated and returned to storage tanks. To predict these properties, test methods such as British Admiralty Method VII, Shell-Amsterdam 2148-1, Method D 3245-IP 230/69,

Test for Pumpability of Industrial Fuel Oils, 1 or Method D 1659, Test for Maximum Fluidity Temperature of Residual Fuel Oil.' may be required. XI.4. 1.3 Water and Sediment — Appreciable amounts of water and sediment in a fuel oil tend to cause fouling of facilities for handling it, and to

give trouble in burner mechanisms. Sediment may

accumulate in storage tanks and on filter screens or burner parts, resulting in obstruction to flow of oil from the tank to the burner. Water in distillate fuels may cause corrosion of tanks and equipment

and it may cause emulsions in residual fuels. XI.4. 1.4 Carbon Residue— The carbon residue of a fuel is a measure of the carbonaceous material

left after all the volatile components are vaporized

in the absence of air. It is a rough approximation of

the tendency of a fuel to form deposits in vaporizing burners, such as pot -type and sleeve-type burn1 Annual Book ofASTM Standard*. Part 25.

217

66
#

ers, where the fuel is vaporized in an air-deficient atmosphere. To obtain measurable values of carbon residue in the lighter distillate fuel oils, it is necessary to distill the oil to remove 90 percent of it in accordance

with ASTM Method D 86, Test for Distillation of Petroleum Products,' and then determine the carbon residue concentrated in the remaining 10 percent bottoms. Xl.4.1.5 Ash—The amount of ash is the quantity of noncombustible material in an oil. Excessive amounts may indicate the presence of materials

that cause high wear of burner pumps and valves, and contribute to deposits on boiler heating surfaces. XI.4. 1.6 Distillation —The distillation test shows

the volatility of a fuel and the ease with which it can be vaporized. The test is of greater significance for oils that are to be burned in vaporizing type burners than for the atomizing type. For example,

the maximum 10 percent and 90 percent distilled temperatures are specified for grade No. 1 fuel. The

limiting 10 percent value assures easy starting in vaporizing type burners and the 90 percent limit excludes heavier fractions that would be difficult to vaporize. The limits specified for grade No. 2 heating oil define a product that is acceptable for burners of the atomizing type in household heating installa- tions. Distillation limits are not specified for fuel

oils of grades Nos. 4, 5, and 6. XI .4.1 .7 Viscosity Limits for Grades S'os. 1 and

2—The viscosity of an oil is a measure of its resistD 395

ance to flow. In fuel oil it is highly significant since

it indicates both the relative ease with which the oil will flow or may be pumped, and the ease of atomization. Viscosity limits for No. I and No. 2 grades are

specified to help maintain uniform fuel flow in appliances with gravity flow, and to provide satisfac- tory atomization and constant flow rate through the small nozzles of household burners. For the heavier grades of industrial and bunker fuel oils, viscosity is of major importance, so that adequate preheating

facilities can be provided to permit them to be pumped to the burner and to provide good atomization. However, it is equally important that the max- imum viscosity under the existing conditions be

such that the oil can be pumped satisfactorily from

the storage tank to the preheater. XI.4. 1.8 Gravity— Gravity alone is of little sig- nificance as an indication of the burning characteristics of fuel oil. However, when used in conjunction

with other properties, it is of value in weight- volume relationships and in calculating the heating

value of an oil. XI .4.1 .9 Corrosion —The corrosion test serves to indicate the presence or absence of materials that might corrode copper, brass, and bronze components of the fuel system. This property is specified only for No. I distillate fuel. Xl.4.1.10 Limited sulfur content of fuel oil may

be required for special uses in connection with heat treatment, nonferrous metal, glass, and ceramic

furnaces or to meet federal, state or local legislation or regulations.

The American Society for Testing and Materials lakes no position respecting the validity of any patent rights asserted

in connection with any item mentioned in this standard. Users of this standard are expressly advised that determination of the

validity of any such patent rights, and the risk of infringement of such rights, is entirely their own responsibility.

218

67

VV-F-815C

July 10, 1972

SUPERSEDING

VV-F-815B

16 December 1 969

FEDERAL SPECIFICATION

FUEL OIL, BURNER

This specification was approved by the Commissioner, Federal Supply

Service, General Services Administration, for the use of all Federal

agencies.

1. SCOPE AND CLASSIFICATION

1.1 Scope . This specification covers fuel oil for stationary oi 1 -burn i ng, heat-generating equipment (see 6.1).

1.2 Class i f icat ion . Burner fuel oil covered by this specification shall

be of the following grades as specified (see 6.2):

Grade No. 1 - Distillate

Grade No. 2

- Disti 1 late

Grade No. k

- Light residual or heavy distillate

Grade No. 5 (Light) - Residual

Grade No. 5 (Heavy) - Residual

Grade No. 6

- Residual (Bunker C)

2. APPLICABLE DOCUMENTS

2.1 Specifications and standards . The following specifications and standards of the issue in effect on date of invitation for bids or request for

proposal, form a part of the specification to the extent specified herein.

Federal Standards:

Fed. Test Method Std. No. 791 - Lubricants, Liquid Fuels and Related

Products; Methods of Testing

(Activities outside the Federal Government may obtain copies of Federal

Specifications and Standards and Handbooks as outlined under General Information in the Index of Federal Specifications and Standards, and at the

prices indicated in the Index. The Index, which includes cumulative monthly

supplements as issued, is for sale on a subscription basis by the Superintendent of Documents, U. S. Government Printing Office, Washington, D. C. 20402

FSC 9140

69
VV-F-8I5C

(Single copies of this specification and other product specifications re- quired by activities outside the Federal Government for bidding purposes are available without charge at the General Services Administration Regional

Offices in Boston, New York, Washington, D. C., Atlanta, Chicago, Kansas

City, Mo., Fort Worth, Denver, San Francisco, Los Angeles, and Auburn,

Washington.

(Federal Government activities may obtain copies of Federal Specifications

and Standards and the Index of Federal Specifications and Standards from

established distribution points in their agencies.)

Military Standards :

MIL-STD-105 " Sampling Procedures and Tables for Inspection by Attributes

Mll-STD-290 - Packaging, Packing and Marking of Petroleum and Related

Products

(Copies of Military Specifications and Standards required by suppliers in

connection with specific procurement functions should be obtained from the

procuring activity or as directed by the contracting officer.)

2.2 Other publications . The following documents form a part of this specification to the extent specified herein. Unless otherwise indicated, the

issue in effect on date of invitation for bids or request for proposals shall

apply.

American Society for Testing and Materials- (ASTM)

Standards :

D 56 - Flash Point by Tag Closed Tester

D 86 - Distillation of Petroleum Products

D 88 - Saybolt Viscosity

D 93 - Flash Point by Pensky-Martens Closed Tester

D 95 - Water in Petroleum and Other Bituminous Materials

D 97 - Pour Point

D 129 - Sulfur in Petroleum Products by the Bomb Method

D 130 - Detection of Copper Corrosion from Petroleum Products by the

Copper Strip Tarnish Test

D 270 - Sampling Petroleum and Petroleum Products

D 287 - API Gravity of Crude Petroleum and Petroleum Products

(Hydrometer Method)

D kh5 - Viscosity of Transparent and Opaque Liquids (Kinematic and

Dynamic Viscosities)

D *»73 - Sediment in Crude and Fuel Oils by Extraction

D 482 - Ash from Petroleum Products

D 524 - Ramsbottom Carbon Residue of Petroleum Products

D 611 - Test for Aniline Point in Petroleum Products

70
VV-F-8I5C

D 1551 - Sulfur in Petroleum Products (Quartz Tube Method)

D 1552^- Sulfur in Petroleum Products (High Temperature Method)

D 1796 - Water and Sediment in Crude Oils and Fuel Oils by Centrifuge

D 2161 - Conversion of Kinematic Viscosity to Saybolt Universal or to Saybolt Furol Viscosity

D 2622 - Sulfur in Petroleum Product (X-Ray Spectrographs Method)

(The ASTM methods listed above are included in Part 17 or Part 18 of the

Annual Book of ASTM Standards and are available individually. Application

for copies should be addressed to the American Society for Testing and

Materials, 1916 Race Street, Philadelphia, Pennsylvania 19103.)

(Technical Society specifications and standards are generally available

for reference from libraries. They are also distributed among using Federal

agencies.)

3. REQUIREMENTS

3.1 Material . Burner fuel oil shall consist of petroleum-derived products.

In the procurement of new fuel oils, suppliers are prohibited from adulterating

either Grade No. 5 or Grade No. 6 fuel oil with waste crankcase lubricants or with similar products. Blending of various compatible grades of the material

to produce an intermediate grade is permitted; however, such blending shall be

accomplished by mechanical mixing or agitation in a tank, or by in-line blending prior to loading the product into transport equipment. The product formed

by such blending shall comply with all the requirements of the grade produced.

3.2 Physical and chemical requirements . Burner fuel oil shall conform to the physical and chemical requirements given in Table I and in 3-2.1, 3-2.2,

and 3.2.3.

3-2.1 Sulfur -content .

3.2.1.1 In the U.S.A. For all grades of fuel, sulfur limits shall be as specified by the applicable contract, the Environmental Protection Agency,

or the state or community where the fuel is to be used, whichever is more

restrictive.

3.2.1.2 Outside the U.S.A . For procurement outside the U.S.A., the maxi- mum sulfur content shall be 0.5 percent for No. 1 fuel and 1.0 percent for

No. 2 fuel or as may be imposed by a foreign country or local community where

the fuel is to be used, whichever is more restrictive.

3.2.2 Copper strip corrosion . For grades 1 and 2 fuel oil, the copper

strip corrosion shall be a maximum of No. 3 per ASTM D 130.

3.2.3 Workmanship . The fuel oil shall be homogeneous in appearance, free

from visible foreign matter such as grit or fiber.

71
VV-F-815C

TOO

cn>- .e

co • — u.

4-1 O

TO— tu — V. — 3

4-» 4-> CO (0 I— i_ o toD.E

0)

c

>? —

o o

<T\ QtX> C o —

LA O

o.

xin dv1 <

o —

— O

D

x:

>- cn X —

(X) 3

<*? B O 3 —

-o c —

O in

a)

_) jC *-> o

rn W C o < ro ' 1- — o

Ll o_ •

«- E

TO .-

+-• -o 3 co

to >- E

X) 3

ck> o

>

cm| — I 4-> O 3 —

o o • Cl.Cl.UCO CO o oc o ca 1 LA CM -3- CA i LA vO *—

•>%, ^_^

1 CM CM 1 1 o oo i -3" CM LA **—

o o

CL Q. 1 <!> TO 1 Oi

LA

OC

o •

1 CM CM^, 1 -3- <~wr|

I o I —O O I

LA LA — CO

o LA o

TO o LA o

o

o o

o o — — CM

CO ^-^ .^-^

.

r-~ r-» i i o 1 o i o i i i *w_^ CM «—

C-' ^—*

TO t TO TO ^_^ TO TO „ . CO en co OILA cn LA cn LA cn la

pa TO pa to la TO LA TO LA TO vO o u o L. o i_ o L. o L- o

o O o o pa O PA O CA o LA

TO3

to

0) 0) —

4-> 4-< W

TO TO 0) •— »— V.

jC

in o

L. T3 TO TO TO L- O 3 3 3 TO >."0 -O "TO .* > — — — C

TO l/l </> C/> 3

o) to a) to co X a: oc oc —

*j >• x: >

cn re 4JA .— LA 41 vO

-J X

V H

co 3

3 O

"O to c

TO >>

t-i TO i-l 60 TO 2 E

o o

4J c

03

4-1 M-) C O 1-1O

<n o. eo v.- i-l 3

4-1 O

»i a • •o <u C "O >- O <1) 3 O i-t

<4-l TO >i -H U

a) a.

"O o. e

TO co <U Vi *J •H TO 3 x: *J v u c

TO V

Id « -H

TO XI M co E

TO 3 TO >

to u -a c C) TO to x: -u x: -u o

5 TO TO

TO DTO

TOO

4J

CO

TO

*J >,

TO

u

TO

M TO C co -i 3 U

E O

E

>» 3

-| E.

TO

•-I -O «M i-( 4J •H O <fl O O TO

TO >

o. »-i o

CO O i-t

TO TO XI X.

• 4-1 ^ W ^

TO TO S

E i-t O

•-I "O

(0 TO o >

CO TO >

TO E Xi 3

E -<

^-t i-i

•H X. E co

TO 4-1 X c

4J -^O

•o a.

TO ^t s~S

U-l O

•i-t ON u

TO E

a. 3

cn E

•p-i co c

C TO TO . oX TJ ^>

co C • TO O

CO l-l VO O TO • X CO IA

4J TO >-' X

C O • TO 1-, Ci, X 3 o

4-1 D- O

r-t

TO X C X n) 4J C X

O O 4J

O ^^ o • TO O

C ovO

4-1 CM O CM c ^

-c • C Cn

TO oO

r-4 <T cO 4J

TO c

o -v

•-t TO 4J ••-* TO cm E -H U O

O TO in a. C CO

1-1 TO U X

O

cm >^

TO

TO E

Lj

TO 4JC

CO -i-t TO O

CO D.

TO X c c

u

1-«

CL .-<a

co 3 TO

4.1 U

C -o O

r^ TO £

O TO

CL- Ij TO GOX

w TO 3 *-• O cm O

CL, -W c

.-< OX 4J >> c a

•r-t CO o

Du (0

•TO M C

C 4J •M CO

CO "U

TO3 4J

r-t C

TO TO

u

CICO c

0> CM X c-> 5 ^

inw

TOcw

3

CJ X

M

>> TO 60

4-i a. c

•M -r^ CO O N O i-l —I o E

CO TO O

1-1 X M > H TO CM| CO|^-|

72
>- XZ

a.

wOO in

in <u - J* > o

4-1

O in H>- u

inoo

in

w - "a > cO

+->

u

— <u O in J>

>•

CO CO

0)C •!-> — c * r— — U- — o o c a. <

>- i/i c

4-> <u •— — CD s: > V.

TO <ZT)

—

V. 0) a.

C3 XI <. • *—

X

Li. • to 5 O 2:

CM

O

CM

O i— la V—--

4-1 c

TO •—

2:X

TO LL ^-, 2: O <-> o — CO • rA c

+J

N

•—

ro z: • X

CJ TO s: OLA

O

1- . 3 LL.

LL. CM

CM

C

+J •—

ro 2:

^.^ # • X

CJ TO •— o SI

TO oo

in oa

l_ - 0)> • — u_ C o => oo C

4-1 - —

ro z:c

«— J-> O CL , 1-

<u

O 3 W

4- flj Q

4-O

a) o

ro

i_ o OZ O

O I O- CL I CD CD

LA

O ) rA rA I I I I I I I I I I I I I

CNJ cAvO

CM 4000

CM LA

CA-3"

^1 ^ OO rA

vO

-3- cn

*l \ VOvO| C-J I LA vO I MO —

vO| vo|

CM LA

rA r~- I1 -3- —

rA

rA

CM LA-a- 000 O LA O rA l~-^ *—' »—' CA OOO LA LA O — rA CA

-O .—

<u 0)

4-> 4-» 4-1 in w

ro TO CD •— »—

w— .!_ i_

a ro r— .

3 • — •— 4-> >-X> M 4J .c

(/> (/) en TO in

0) CJ

TO It

L 3 3 CD x> x> .*

._

— c

in I/) 3

a) a;

m qq_i 3- az o: ce-

4J >.

jc >

Cn ro LA — LA CD vO

-I I

a> •O

0)

O I ^4 in

H) 4-» u> E 44 in .c — O •H CD h- C2 > L. 4-

IDCO c O <U 0) CO 3 • 0 xz out .-i

4-»

M

C TOO X) c CD •— E CD <D -O - cn CD in TO L. C O J3 3 u u <D TO 4-»

fl> cn

— ^: i-l CD Q.

-a

—

CL

l_ ^-1«8 X)

O a> a. c in x: XI O 3 0)

i/> ^: 3 'jO 3

CNJ x> s CD t-l

O E -0 -C •rH -C "O 3 c -0 4-1 O in

<DC ro 0)

CD i_ 4-> 1-1 ~—

1_ > . 

<U

M

X a) 4J 3 E 3 O 2O — tr > <U CD «W ^.

4-> »—

— «_ Q. ^O CD

O 4-1 3 C ro O CL) ro O O

4J 4- .

4- •— ^ 4-> •

O cn 4-> CD C

ro c E cu .—

XZ a> •— c •— XIO

1/1 c >

.- CO

4-> c4 CL c TO CD O 4-> LL> c C 3

.— CD TO QJ

M

O

4-> >. L. > . 

X) CL

O 4-1 TJO CD

TO 4J • — CD TO .— L. 2

L. c i/l -C <4- •—

O

4-» <L>

O 4-> XI 4- 3 _i

XOU c 3 cr

a) L. in

C TO

m CD

0) .— CD L. • >- Q. > CD XI c ^-^ J3 3 <D *— (A • O 0) 4-1 .— — X

4-> LA JZ CD <+- 0) TO C 4J J3 — J3 .—

E

a; 4J en E c 4J C ^~ in

O

•— TD ••—

C CD .CDC

TD d) CD "O TO •

»—

D <D 1E — _C

inO .— CD in !_ *J X <D CD O c

a) a> L. J3 CD •—

szCD « 4-) 4-> a> ro — — X CL O 3 •— 4-1 ro m C M- >- TO E l_ a CO J^ c 3

^~ ^^

M l/l 4->

O

CL ^-» "O in

C D.

TO H) • 4-1 *— CD c -C L. T3 C XZ O XZ

in .— CD CD t- L. cn

— 3 — E CD •—

4J c cr

— Q. CLXZ

ro

O 0) a.— • • »— — i_ CL XZ 1. i_ XI ^— *-> 3 in <D • O CD — in in XZ 

4J

4-1 TO •^ ^~ 4-1 N-^ s~-^ TO

(rt l_ cd ro • CD •— 4-> •— _Q — c ^— X XZ •a X — 4-1 TO •^ TO D O >

E CD >• ro c O • L. -a >- .

E — 4-> in 1

• TO J3 a) 4-1 <D Ix, i_ 3 * <u <D c 3 e in 0) 4J M- * j: cn CD 4- O CD

J-> c . 4-> c E ^O

C

TO a) L.

O TO AJ 1_

—

•— 3 E 3 ^ "*" l_ m 3 

MO 3 4- 4-> u- 13 

cn >- •

c XI

O <L) 3 C CD i~i -a 3 •^ c m 1/1 — cn • 

TO in ro

4-» X) c in CL c i+- s 3 TO O >- 2 in 3 O 1— 1_ O L. O V- _* O O in TO — 3 c E 4-> c >- •— in O ro

TO c <u

— 4-> > m <D a. 4-1 3 1_ * — CD i_ 4) O a) x> in CD O CD 2 •—

-C E -C c O c CD _c

O

1- TO 3: ro

O cz 3:

— ro

VV-F-815C

la| vo| r-l

73
VV-F-815C

4. QUALITY ASSURANCE PROVISIONS

4.1 Responsibility for inspection . Unless otherwise specified in the contract or purchase order, the supplier is responsible for the performance of

all inspection requirements as specified herein. Except as otherwise specified in the contract or order, the supplier may use his own or any other

facilities suitable for the performance of the inspection requirements specified herein, unless disapproved by the Government. The Government reserves

the right to perform any of the inspections set forth in the specification

where such inspections are deemed necessary to assure supplies and services

conform to prescribed requirements.

k.2 Lot .

k. 2.1 Bulk lot . An indefinite quantity of a homogeneous mixture of one

grade of fuel oil offered for acceptance in a single, isolated container;

or manufactured in a single plant run (not exceeding 2k hours), through the same processing equipment, with no change in the ingredient materials.

4.2.2 Packaged lot . An indefinite number of 55~gallon drums or smaller

unit containers of identical size and type, offered for acceptance, and

filled with a homogeneous mixture of one grade of fuel oil from a single,

isolated container; or filled with a homogeneous mixture of one grade of

fuel oil, manufactured in a single plant run (not exceeding 2k hours),

through the same processing equipment, with no change in the ingredient

materials .

k. 3 Sampl i ng .

4.3.1 Sampling for examination of packed containers . Take a randon sample

of packed containers from each packaged lot in accordance with MIL-STD-105

at inspection level II and acceptable quality level (AQL) = 2.5 percent

defect i ve

.

4.3.2 Sampl ing for tests . Take samples for tests in accordance with ASTM

method D 270.

4.4 Inspect ion . Perform inspection in accordance with method 9601 of

Fed. Test Method Std. No. 791.

A.A.I Examination of packed containers . Examine samples taken in accordance with k. 3.1 for compliance with MIL-STD-290 with regard to fill, closure,

sealing, leakage, packaging, packing, and marking requirements. Reject any

container having one or more defects or under the required fill. If the

number of defective or underfilled containers exceeds the acceptance number

for the appropriate plan of MIL-STD-105, reject the lot represented by the

sample

.

74
VV-F-8I5C

h.S Classification of tests . 'All tests are quality conformance tests.

k.(> Test methods . Perform tests in accordance with the applicable methods

1 isted in Table I I .

TABLE I I . Test methods

ASTH test method

Test number

Flash pointl/ D 93 or D 56

Pour point D 97

Water and sediment (grades No. 1, 2, and h) D 1 796

Water (grades No. 5 and 6) D 95

Sediment (grades No. 5 and 6) D ^73

Carbon residue, Ramsbottom D 52*1 Ash *j82

Distillation temperature D 86

Viscosity, Kinematic D hk$

Viscosity, Sayboltl/ D 2l6l or D 88

Gravity, API D 287

Copper strip corrosion 3/ D 130

SulfurV D 1552, 0129,

D 1551 or D 2622

Ani 1 ine point D 61

1

Jl/ASTM D 93 is the preferred method. D 56 may be used as an alternate for

grade No. 1 with the same limits. In case of dispute, D 93 shall be used

as the referee method.

1/ASTM D 2161 is the preferred method.

3/The test shall be run for 3 hours at 212°F. (100°C).

VASTM method D 1552 is the preferred method. D 129, D 1551 and D 2622 may

be used as alternate methods.

5. PREPARATION FOR DELIVERY

5.1 Packaging, packing, and marking . Unless otherwise specified in the

contract or purchase order (see 6.2), packaging, packing, and marking shall

be performed in accordance with MIL-STD-290.

6. NOTES

6.1 Intended use . Burner fuel oils covered by this specification fall

into two broad classes, distillates and residuals. The oils are intended

for use in various types of fuel-burning equipment under various climatic

and operating conditions, for the generation of heat in furnaces for heating

buildings, for the generation of steam, or for other purposes. The grades

covered by this specification are intended for specific applications as indicated below:

75
VV-F-815C

6.1.1 Grade No. 1 . A light distillate oil intended for use in burners of

the vaporizing type in which the oil is converted to a vapor by contact with

a heated surface or by radiation.

6.1.2 Grade Mo. 2 . A heavier distillate than grade No. 1. It is intended

for use in atomizi ng-type burners which spray the oil into a combustion

chamber where the tiny droplets burn while in suspension. The grade of oil

is used in most domestic burners and in many medium-capacity commercialindustrial burners v/here its ease of handling and ready availability sometimes justify its higher cost over the residual grades.

6.1-3 Grade No. h . Usually a light residual but sometimes a heavy distillate. It is intended for use in burners equipped with devices that

atomize oils of higher viscosity than domestic burners can handle. Its permissible viscosity range allows it to be pumped and atomized at relatively

low storage temperatures. Thus, except in extremely cold weather, it requires

no preheating for handling.

6.1. A Grade No. 5 (1 ight) . A residual fuel of intermediate viscosity for

burners capable of handling fuel more viscous than grade No. h v/ithout preheating. Preheating may be necessary in some types of equipment for burning

and in colder climates for handling.

6.1.5 Grade No. 5 (heavy) . A residual fuel more viscous than grade No. 5 (light). It is intended for similar service. Preheating may be necessary

in some types of equipment for burning and in colder climates for handling.

6.1.6 G rade No. 6 . A high-viscosity oil, sometimes referred to as "Bunker

C", and used mostly in commercial and industrial heating. It requires preheating in the storage tank to permit pumping and additional preheating at the burner to permit atomizing. The extra equipment and maintenance required

to handle this fuel usually preclude its use in small installations.

6.2 Ordering data . Procurement documents should specify the following:

(a) Title, number, and date of this specification.

(b) Grade of oil required (see 1.2).

(c) Quantity of oil required. The fuel oil should be purchased by

volume, the unit being one U.S. gallon of 231 cubic inches at 60°F. (15.6°C).

Outside the U.S.A., oil may be purchased in SI (metric) units if agreeable to purchaser and supplier.

(d) Whether bulk or packaged delivery is required.

(e) Type and size of containers if packaged delivery is required

(see 5-1).

(f) Maximum permissible sulfur content (see 3-2.1 and 6.3).

76
VV-F-815C

6.3 Sulfur content (see 3-2.1) . Sulfur content of burner fuel oils is being increasingly restricted because of air-pollution problems. Maximum

limits for sulfur vary from one region or metropolitan area to another, and

are likely to be reduced even further. Accordingly, it is not possible to set out specific requirements in this specification. Sulfur limits should

be specified in all contracts or purchase orders, in compliance with the

current legal requirements in the particular state or community, or with the

standards of the Environmental Protection Agency.

NOTE: The provisions for sulfur limits in this paragraph

and in 3-2.1 are in consonance with Executive Order

11282, Control of Air Pollution Originating from

Federal Installations.

MILITARY CUSTODIANS: Preparing activity:

Army - MR Army - MR

Navy - YD

Air Force - 68 (Project No. 91 40-00^0)

Review activities : CIVIL AGENCY INTEREST:

Army - WC GSA

Navy - YD, SA

Ai r Force - 68

DSA - PS

User activities :

Navy - MC, SH

*U. S. SOTi'Si^'SET FIEETING OFFICE : 197? C - ?lh-lc9 ( 3? )

Orders for this pubiic-itlcn «re to be placed with Genera] Servicer. Arlmlnlstraticn, acting s:s on apent for the Superintendent of Documents. See

section P of this specification to obtain extra copies ^nd other documents

referenced herein. Price 1^ ennts each.

77

M1L~F-#59E

ajaaraan urn

MIL-T-SMD

tl DECEMBEB IMS

(SEX «J)

MILITARY SPECIFICATION

FUEL OIL, BURNER

nH aad Aa*»rir$ of Ik* Ittfartwuml »f ittftmM.

L SCOPE

LI Scope. This specification covers burn- er fuel oil for steam powered vessels of the Navy and for other steam powered vessel* of the Government service. L2 Classification. Burner fuel oil shall be the following grade (see 6.2) :

Burner fuel oi! —Navy special

(NATO symbol F-77

2. APPLICABLE DOCUMENTS

2.1 The following documents of the issue in effect on date of invitation for bids or request for proposal, form a part of the

specification to the extent specified herein. STANDARDS

Federal

FED-STD-791 — Lubricants, LiquidFuels, and Related Products; Methods

of Testing.

MlUTABY

MIL-STD-290

0/10

Packaging, Packing and Marking

of Petroleum and

Related Products.

( Copies of •pedSca.tiona, ataaakfak, < publication* required by nppUan ta i •peeifte procurement lanrtfai anaaM a* from the procuring aettrity «r as

contracting oAcer.) kv <••

22 Other publications. The following

documents form s part of this T*a4*T*l

im

to the extent specified herein. Unless other- wise indicated, the issue in effect on dais

of invitation for mas or request far proposal shs'l "pply.

Amkucan Soamr ron Tbttno and

Mateuals (ASTM)

ASTM Put 17— Petroleum Paols. Sortontt, Bngino Testa, Lev

bricstiof Oils.

Cutting OilSo

Gross*.

D-88 — Viscosity. Snytelt,

D-92 — Flaab and Fire

Points by Ores,

knd Cop Opsm.

D-S3 — Flash Point by Penalty - Martens

Dosed Tutor. D-M — Water la Fotrolenm

Product*, and OthncttM

ni

79
MTL-F-859E

er Bituminous Materials. D-97

D-129

D-189

D-270

D-287

Cloud

Points. and Pour

D-473

D-482

D-1659

— Test for Sulfur in Petroleum Products by the Bomb

Method. — Test for Conradson

Carbon Residue of Petroleum Products. — Method of Sampling

Petroleum and Pe- troleum Products

(Tentative). — Test for API Gravity of Crude Pe- troleum and Petro- leum Products

(Hydrometer

Method). — Test for Sediment In Crude Petroleum and Fuel Oil By

Extraction. — Test for Ash From

Petroleum Products. — Method of Test for

Maximum Fluidity

Temperature of

Residual Fuel Oil (Tentative).

D-1796 — Test for Water and

Sediment in Fuel Oils by Centrifuge.

(Application for ~»p»ee should he iJdwui to the American Society for Testing- sad Materials, UK

Race Street, Philadelphia, Pa. 1910S.)

Interstate Commerce Commission

Code of Federal Regulations

( Application for copies should be addressed to the • Superintendent of Document*, Government Pristine

Office, Washington. D.C 20401).

(Technical society and technical aaeseJatioa specifications and standards are generally available for

reference from libraries. They are also distribated tmonic technical (roups and using Federal agoadea.) r REQUIREMENTS

3.1 Material.

3.1.1 The burner fuel oil shall consist of

a hydrocarbon oil. Additives are not permitted.

X2 Chemical and physical reejalremeata,

The fuel oil shall conform to the chemical and physical requirements of table I.

Tim I. Ck»mieml aad pkytlfml r*f*ii >(•!•

Umim

Tat

•Matter •

ASTN

SN%a«4

Flash point, closed cup (mln.) •F. ISO not D-M

Fire point (mln.) *F. •200 uoa D-M

Viscosity, at 122* P. (mas.) SSF 304 D-tt

2 o/H

80
MD>-F-*r'9E

Tails I. Comical and phyrlsal rtqvlrtimnU—Ccnlinord

U«Jte

Test SMtaei AJTM

Vbeoeity. at 122'F. (max.) SSU 225 304 d-m

Viseo-ity. »t 86'F. (min.) SSU •228 304 D-n

Aah (mix.) percent 0.10 8421 IV-tS*

Water, by distillation (max.) percent 04 3001 D-M

AJJ. gravity (mln.) ItJ 401 D-W7

Pour point, upper (max.) * *F. IS •201 D-VI

Fluidity at 32*F.« Pass D-ISS3

Carbon residue (max.) percent 15 •6001 D-Ut

Sediment by extraction (max.) percent 0.12 3002 D-473

Water and sediment (max.) percent •0.6 3000 D-1TM

Thermal stability (KBTL beater) 'Paaa •3441 —

Explosirenesa (max.)

Sulphur (max.)

percent 50 1181

340 6203 IM2S

• rTD-rnvrti.

•Saa IX •Eni»u« u s»pre<iB.ulT H SSU at lrJT. If rtKo.itr »t in*r. a> n »tir

ri^o.n r at 1ST. asa4 a« ka «»mil

• If Uw aoar aolat a Ua llu ll"F. IX* BaMIt* Md M W mNiiil. •Saa 4.4.1X •Saa UU Poar uat aot fxr.!rW obft SaMltr tart b p.rfarav-i aa<

' Saa 14X1.

• AaalWaala sal/ <m umpUa l»k«» CI • »»»' ** ulaa rr. task r»ra>. *r alaa Uaa. tall aa4 IX

" D-1WI U aa oalloaal autaoa aa4 air W aasa la Uaa a( MBTL aaalar.

13 Fire point. When the flash point of the fuel is 175*F. or higher, the fire point need not be determined. If the water content of the fuel prevents accurate determination of the Are point, t"ho fuel oil will be

acceptable if the foaming due to water

starts below the Are point, and at a temperature not lower than 19S"F.

3.4 Thermal stability. When subjected

to the thermal stability test specified ia Ublo I fuel oil Navy special shall show a No.

1 tube or better. X5 Compatibility. Burner fuel oil Navy

special, when tested In accordance with

4.4.2 shall show a No. 2 tube or better with

each of Reference Fuels H and I. Compatlul 12

81
MIL-F-859E

bility need not be run on each blend of fuel unless the composition is altered to the ex- tent that a total component change of 10 percent relative to the blend that passed

the compatibility test has been made.

4. QUALITY ASSURANCE

PROVISIONS

4.1 Responsibility for inspection. Unless

otherwise specified in the contract or pur- chase order, the supplier is responsible for the performance of all inspection require- ments as specified herein. Except as other- wise specified, the supplier may utilize his own facilities or any commercial laboratory

acceptable to the Government. The Govern- ment reserves the right to perform any of the inspections set forth in the specifica- tion where such inspections are deemed to assure supplies and services conform to pre- scribed requirements.

42 Sampling.

4.2.1 Bulk lot. An indefinite quantitv of material from one storage tank offered for acceptance. To establish homogeneity, upper,

middle, and lower samples as prescribed in ASTM D-270 shall be taken from each lot and subjected to API gravity determinations in accordance with method 401 of FED-STD-791. To be considered homogeneous, those gravities shall not vary from the average more than 0.3*. If the lot is homogeneous, samples shall be composited for ac- ceptance testing. If the lot is not homogeneous, acceptance tests shall be performed

separately upon the upper, middle, and

lower samples.

4.2.2 Packaged lot. An indefinite number of 55-gaIlon drums or smaller containers

of identical size and type filled from one

storage tank. Acceptance testa shall be per- formed upon a composite of samples taken

in the number and as ipecifled in ASTM

D-270.

«4 TMt*.

4.3.1 Testa shall be conducted in accord- ance with the applicable methods of FEDSTD-791 as specified in table I and the fol- lowing :

4.3.1.1 Carbon residue. A 5-gm. sample

shall be used. Other details of the teat shall be in accordance with the specified method

(see table I).

4.3.1.2 Pour point. In determining the pour point three consecutive testa of the same sample, using the same teat jar, shall be conducted. The value to be reported,

provided the results of the three testa check

within 5'F4 shall be the average of the

three result* to the nearest multiple of &

All other details of the test shall be in ac- cordance with the specified method (see ta- ble I).

4.3.1.3 Fluidity Utt. The object of the

fluidity test is to ascertain If the oil wiB

flow through a 1/2 inch pipe onder alight pressure (such aa it would be subjected te by a pump or by its own bend from an

overhead tank) at the specified temperature.

4.3.2 Compatibility test The compatibility test shall consist of subjecting to the thermal stability test separate testa of Navy

special fuel and reference fuel H and Navy

special fuel and reference fuel I at a ratio of 1:1.

5. PREPARATION FOR DELIVERY

5.1 Packaging, pecking, and marking.

Packaging, packing, and marking shall be

in accordance with MIL-STD-S90.

SJ Marking of ahlnaseata. Shipping containers shall be marked la accordance with

MIL-STD-290, The nomenclature shall be

as follows: Fuel Oil. Burner, Nary special

(NATO symbol F-7T), M1L-F-459. In

addition, the Information required by Code

of Federal Regulations 49CFR Tl-78 shall appear on each individual container and on

nil shipping containers. 0713

82
ML-F-459E

«. NOTES tion are the subject of an International standardisation agreement (NATO). Who

6.1 Intended us*. Fuel oil Navy special amendment revision, or esncenatton of this U intended for um in all steam vessels of specification is proposed, the departmental

the Navy, and other Government vessels as <tirf/w»«M will inform their respective Derequired, partmental Standardisation Office so that

appropriate action may be taken respecting

&2 Ordering data. Procurement doco- the international agreement concerned. menu should specify the following:

i*\ t:m. .n~K>- „_j j » .* *vi •* Information relative to obtaining H

£!1%JT

»~» I «*•"*• fuel, may be obtained from

Spe<afte*t,on- the cognizant Military inspector. (b) Quantity required (see 4^2).

15 Change* frssa preview lassie. The

(c) Packaging, packing and mark- extent of changes (deletions, additions,

ing required (see 5.1 and 5.2). etc) preclude the annotation of the indi- ridual changes from the previous issue of

<L3 Certain provisions of this specific*- this docnment.

CwtodiaM: rvfrisg aetMtr: Armj—MR Hawy—8B

Xmrj—SH (Ti»)»t •Me-SSlS)

Air

Bnlnr actiTlUn: Armj—MR

Navy—8R

Air Uwr artWillm: Amy—CE. CL. MC

N»»r—TD

latrraatioaal (•*• arttlo* •)

U/i4

83
MIL-F-BS9E

AMENDMENT2

4 Autust 1967 SUPERSEDING*/ Amendse*C-l

24 August 19** MILITARY SPECIFICATION

FUEL OIL, BURNER

This amendment forms a part of Military Specification MIL-F-IS9E, dated 22 S«pteal

1966 and is mandatory for use by all Departatents and Agencies of the Department i Defense.

Page 2. paragraph 2.2, under AMERICAN SOCIETY FOR TESTING AND MATERIALS (ASTM) : J '0-1661 - Thermal Stability of U. S. Navy Special Fuel Oil."

Page 3, Table I: Delete and substitute: "Table I • Chemical and physical requirements (Continued)

Limits

1 Test

number*' ARM

method

number

Viscosity, at 122*7. (max.) S50 225 1 S04 D-J«

Viscosity, at «S*F. (min.) Ash (max.)

later, by distillation (max.) A.F.I, gravity (min.)

ssa

percent

percent

1/22S

0.10 o.s

11.

s

304

S421 3001

! 401

0-4g2 • D-9S B-2S7

Four point, upper (max.)!/

Fluidity at Zl'V.!/ ^

IS 1/201 D-97 „»»•• _ £-l»S9

AW**

Carbon residue (max.) Sediment by extraction (max.)percent

percent

IS

0.12 ysoot 3002 D-100D-473

Mater and sediment (max.) percent IVs 3000 0-1790

Thermal stability I'p... D-1661 Explosiveness (max.)

Sulphur (max.)

percent SOs.so

11 SI S201 0-129

See footnotes to table I on next page.

IfCHANGES FROM PREVIOUS ISSUE . THE OUTSIDE MARGINS OF THIS DOCUMENT HAVE REEM MAI "f" TO INDICATE WHEW OUNCES (DELETIONS. ADDITIONS. ETC.) FROM TMR PREVIOUS I HAVE BEEN MADE. THIS HAS BEEN DONE AS A CONVENIENCE ONLY AND THE GOVERNMENT

ASSUMES NO LIABILITY NHATSOBVIR FOB ANY INACCURACIES IN THESE NOTATIONS. BIH

AND CONTRACTORS ARE CAUTIONED TO EVALUATE THE REQUIREMENTS OF THIS BOCWENT Mi ON THE ENTIRE CONTENT AS WRITTEN IRRESPECTIVE OF THE MARGINAL NOTATIONS AND

RELATIONSHIP TO THE LAST PREVIOUS ISSUE.

fYl

FSC B14B

84
XIL-F-859S

awhmot - 1 24 August 1966

KIUTARI SPECIFICATKW

FUEL OIL, BUKKER

This amendment forms a part of Military Specification MIL-F-859E,

dated 22 September 1965 aid is mandatory for use by all Department* and

Agencies of the Department of Defense.

Page 2, paragraph 2.2, under AMERICAN SOCIETT FOR TESTIBG AND MATERIALS

(ASTM)i Add -D-1661 - Thermal Stability of U.S. Ury Special Fuel Oil."

Page 3, Table It Delete and substitute: "Table I - Chemical and physical requirements (Continued)

vhwfcy. at mrr. <«»»*.> Thcnlty. at H*y. (ak)

Aeaiawm.)

Water, fcr JtrtHUtt— (au.) AJP1 cravitjr (rala.)

8SU ssu

•r.

(mas.)

Baflawt ky atncdaa (au.)

Water aad t«dl»«al (au.)

IttaWlty

(mac)

04» OJ

u

Pat*

li

0.U

•OJ •Pan W

•421 D-Of •Ml D-»6

401 0-»7

•Ml D~n

D-l«»

M01 D-18» mm D-4T1 MM D-17M

D-1661

1111 •Ml D-1M

>laU

tui im * tr m Bta — ia*F. M *»

k « rr. •—< m m> i i i

• « *» »~> *•** h »«. *• u*r. m* wu> «—i m

•e- 4.3.1.2.

•t ttrr. b «

la-Aj'.ll!: Pour test not required when fluidity test is performed and passes, a- 4.3.1.1

f FSC 9U0 I •atMalu

Page 1 of 2 pages

7ee

85
mL-r-ey>E

MCtnCCT - t

Frtpwlaa activity!

*arv-«H <riw|c«t tt4»=0024)

**fav MtWHJrai Amv—MB

j»«t»—ra

Air r« Vw* arttvillM! Aray-C* 01* MB

P*f* 2 of 2 pme*»

?««

86
MIL-F-16384G

7 March 197 3 svPLAsr.oir.n MIL-F-16384F

3 November 1965

(See .6.4)

MILITARY SPECIFICATION

FUEL OIL, DIESEL, MARINE

This specification is approved for use by all Departments and Agencies of the Department of Defense.

1

.

SCOPE

1.1 This specification covers one grade of marine Diesel fuel (IIATO symbol |F-76|).

2. APPLICABLE DOCUMENTS

2.1 The following documents, of the issue in effect on date of invitation for bids or request for proposal, form a part of the specification to the extent specified herein. STANDARDS

AMERICAN SOC

D 86 - D 93 - D 97 - D 129 - D 130 - D 287 -

FEDERAL

FED-STD-791 - Lubricants, Liquid Fuels, and Related Products; Method of Testing. MILITARY

MIL-STD-290 - Packaging, Packing and Marking of Petroleur, and Related

Products

.

(Copies of specifications, standards, drawings, and publications required by suppliers

in connection with specific procurement functions should be obtained fron the procuring

activity or as directed by the contracting officer.)

2.2 Other publications . The following documents form a part of this specification to the extent specified herein. Unless otherwise indicated, the issue in effect on date of invitation for bids or request for proposal shall apply.

IETY FOR TESTING AND MATERIALS (ASTM)

Distillation of Petroleum Products.

Flash Point by Pensky-Martens Closed Tester.

Pour Point. Sulfur in Petroleum Products by the Eomb Method. Copper Corrosion by Petroleum Products.

API Gravity of Crude Petroleum and Petroleum Products

(Hydrometer Method)

.

Viscosity of Transparent and Opaque Liquids (Kinematic and Dynamic Vicosities).

Ash from Petroleum Products.

Ramsbottom Carbon Residue of Petroleum Products. Aniline Point and Mixed Aniline Point of Petroleum Products

and Hydrocarbon Solvents.

Ignition Quality of Diesel Fuels by the Cetane Method. Rust-Preventing Characteristics of Steam-Turbine Oil in the Presence of Water. Neutralization Number by Color-Indicator Titration.

Calculated Cetane Index of Distillate Fuels.

- ASTM Color of Petroleum Products (ASTM Color Scale)

.

- Sulfur in Petroleum Products (High-Temperature Method)

,

Test for.

- Test for Stability of Distillate Fuel Oil (Accelerated Method).

- Test for Cloud Point of Petroleum Oils.

- Test for Sulfur in Petroleum Products (X-Ray Spectrographs

Method)

.

- Water and Sediment in Distillate Fuels by Centrifuge, Test for. Recommended Practice for Indicating Which Places of Figures Are to

Be Considered Significant in Specified Limiting Values. FSC 9140

D 445 -

D 482

D 524 D 611

D 613

D 665

D 974

D 976

D 1500

D 1552

D 2274

D 2500

D 2622

D 2709

E 29 -

87
MIL-F-16884G

(Application for copies should be addressed to the American Society For Testing and

Materials, 1916 Race Street, Philadelphia, Pennsylvania 19103.)

(Technical society and technical association specifications and standards are generally

available for reference from libraries. They are also distributed among technical grouDs

and using Federal agencies.)

3. REQUIREMENTS

3.1 Requirements contained herein are not subject to corrections for tolerance of test methods. If multiple determinations are made by the inspecting laboratory, average results will be used except for those test methods where repeatability data are given. In those cases, the average value derived from the individual results that agree within the repeatability limits given may be used at the discretion of the inspection authority,

provided an indication is given of the total number or results obtained and the number

falling outside the repeatability limits. For purposes of determining conformance with each

requirement, and observed value or calculated value shall be rounded off "to the nearest

unit" in the last right-hand place of figures used in expressing the limiting value, in accordance with the rounding-off procedure given in ASTM E 29.

3.2 Material . The fuel supplied under this specification shall be distillate fuel and may contain only those additives specified in 3.4.

3.3 Chemical and physical requirements . The diesel fuel shall conform to the physical

and chemical requirements specified in table I. Table I - Chemical and physical requirements.

FED-STD-791 ASTM

Characteristics Requirements test method test method

Ignition quality, cetane number

(min) (see 4.3.1) 45 D 613 AppearanceDistillation: Clear, bright, and

free from visible

particulate matter.

50 percent point, °F Record

90 percent point, °F (max) 675°F (357. 2°C) D 86 End point, °F (max)-' 725°F (385°C)

Residue plus loss, percent (max) 3.0 Flash point °F (min) 140°F (60°C) D 93 Pour point, *F (max) 20°F (-6.7°C) D 97 Cloud point, °F (max) 30°F (-1.1°C) D 2500 Viscosity at 100°F (37.8°C)

Kinematic, centistokes 1.8 - 4.5 D 445 Carbon residue, on 10 percent

bottoms, percent (max) (see 4.6.2) 0.20 D 524,

Sulfur, percent (max) 1.00 D 129-' Corrosion (max) at 212°F (100°C) No. 1 ASTM D 130 Color (max) 5 D 1500

Ash, percent (max) 0.005 D 482 Gravity (hydrometer) Record D 287 Demulsif ication, minutes (max) (see 4.6.3) 10 3201 Acid number (max) 0.30 D 974 Neutrality Neutral 5101 Aniline point, °F Record D 611 Accelerated stability, total

insolubles mg/100 2. 5i/ ml (max) D 2274 T7

2/

3/

47

A slight haze is acceptable providing a maximum water and sediment of 0.01 percent is obtained using procedure ASTM D 2709. As the end point of the distillation is approached, if either a thermometer reading

725°F (385°C) or a decomposition point is observed, discontinue the heating and resume

the procedure as directed in ASTM D 86. ASTM D 1552 and ASTM D 2622 may be used as alternate methods.

Average of three determinations is acceptable.

88
MIL-F-16884G

3.4 Additives . The additives listed herein may be used singly or in combination in amounts not to exceed those specified.

3.4.1 Antioxidants . The following active inhibitors may be blended separately or in combination into the fuel in total concentration not in excess of 0.4 pounds of inhibitor (not including weight of solvent) per 1,000 barrels of fuel (9.1 grams (g)/100 gallons (gal) (U.S.), 24 milligrams (mg) /liter or 109 mg/gal (U.K.)) in order to prevent the formation of gum

:

(a) N,N' - diisopropyl-para-phenylenediamine

(b) N,N" - disecondary butyl-para-phenylenediamine

(c) 2,6 - ditertiary butyl-4-methylphenol

(d) 2,4 - dimethyl-6-tertiary butylphenol

(e) 2,6 - ditertiary butylphenol

(f) 75 percent min. 2 ,6-ditertiary butylphenol

25 percent min. tertiary and tritertiary butylphenols

3.4.2 Metal deactivator . A metal deactivator, M, N' - disalicyclidene-1 , 2 propanedi- amine may be blended into the fuel in an amount not to exceed 2 pounds of active ingredient

per 1,000 barrels of fuel (2.2g/100 gal (U.S.), 5.8 mg/liter or 25 mg/gal (U.K.)).

t 3.4.3 Ignition improver . The following additives, to raise the ignition quality of

the fuel, may be used as required to conform to this specification:

Amyl nitrate (mixed primary nitrates)

.

Hexyl nitrate (N-hexyl nitrate).

Cyclohexyl nitrate.

4. QUALITY ASSURANCE PROVISIONS

4.1 Responsibility for inspection . Unless otherwise specified in the contract or purchase order, the supplier is responsible for the performance of all inspection require- ments as specified herein. Except as otherwise specified in the contract or order, the supplier may use his own or any other facilities suitable for the performance of the inspection requirements specified herein, unless disapproved by the Government. The Government

reserves the right to perform any of the inspections set forth in the specification where

such inspections are deemed necessary to assure supplies and services conform to prescribed

requirements.

# 4.2 Lot .

£ 4.2.1 Bulk lot . Bulk lot shall be considered an indefinite quantity of a homogenous

mixture of material offered for acceptance in a single isolated container.

# 4.2.2 Packaged lot. Packaged lot shall be considered an indefinite number of 55- gallon drums or smaller unit containers of identical size and type, offered for acceptance,

and filled with a homogenous mixture of material from one isolated container; or filled

with a homogenous mixture of material manufactured in a single plant run (not exceeding 24 hours) through the same processing equipment, with no change in ingredient material.

J 4.3 Sampling .

} 4.3.1 Sampling for examination of the preparation for delivery .

j 4.3.1.1 Packaged lot. A random sample of packed containers shall be taken from each

lot in accordance with MIL-STD-105, at inspection level II, and acceptable quality level

(AQL) equals 2.5 percent defective. Examine the sample in accordance with 4.4.1.

{ 4.3.2 Sampling for tests. Take samples for tests in accordance with ASTM D 270. Test the samples in accordance with table I and 4.6.

f 4.4 Inspection. Perform inspection in accordance with method 9601 of FED-STD-791.

f 4.4.1 Examination of the preparation for del ivery . Samples taken in accordance

with 4.3.1 shall be examlried for compliance with MIL-STD-290 with regard to fill, closure,

sealing, leakage, packaging, packing, and marking requirements. Reject any container having

one or more defects, or under the required fill. If the number of defective or underfilled

containers exceeds the acceptance number for the appropriate plan of MIL-STD-10 5, the lot represented by the sample shall be rejected.

f 4.5 Classification of tests . All tests are quality conformance tests.

89
MIL-F-16884G

4.6 Test methods.

4.6.1 Ignition quality . When the apparatus specified in ASTM D 613 is not available

for product inspection purposes, the cetane index may be authorized in lieu of the cetane

number, provided that sufficient data are available to establish the cetane index number

correlation for a finished product or a blend of products from the same manufacturing proc- ess or processes and the same specific crude source. In all instances the product submitted shall be of sufficiently high cetane index to assure a cetane number at least as high as that shown in table I. In no case shall the cetane index be less than 45. The calculated

cetane index shall not be used in determining the ignition quality of fuel containing

ignition improvers. The cetane index shall be determined by ASTM D 976. 4.6.2 Carbon residue . When the finished fuel contains a cetane improver the carbon

residue requirement specified in table I shall apply to the base fuel without the cetane

improver.

4-6.3 Demulsification . The test for demulsification shall be conducted in accordance

with method 3201 of FED-STD-791 with the following exceptions:

(a) Synthetic sea water prepared in accordance with ASTM D 665 shall be used as the emulsifying fluid,

(b) The test temperature shall be 77° + 2°F (25° + 1.1°C).

(c) The demulsification time shall be that required for separation into two layers with no cuff at the interface. A lacy emulsion which does not

form a band or cuff on the wall of the cylinder shall be disregarded.

# 4.7 Inspection of preparation for delivery . The packaging, packing, and marking shall be inspected for compliance with section 5 of this specification.

5. PREPARATION FOR DELIVERY

s 5.1 Packaging , packing , and marking . Packaging, packing, and marking shall be in accordance with MIL-STD-290. The level of packaging, level of packing, type, and size shall

be as specified (see 6.2).

6

.

NOTES

6.1 Intended use. Phis grade of marine Diesel fuel is intended for use in Diesel

engines in submarines and for such other uses as may be specified at temperature above

30°F (-1.1°C).

6.2 Ordering data . Procurement documents should specify the following:

(a) Title, number, and date of this specification.

(b) Applicable level of packaging and packing required (see 5.1).

(c) Unit container quantity (see 5.1).

6.3 Certain provisions of this specification are the subject of international standard- ization agreement IJATO STANAG-1135. When amendment, revision, or cancellation of this specification is proposed which will affect or violate the international agreement concerned, the preparation activity will take appropriate reconciliation action through international

standardization channels including departmental standardization offices, if required.

6.4 THE MARGINS OF THIS SPECIFICATION ARE MARKED " #

" TO INDICATE WHERE CHANGES

(ADDITIONS, MODIFICATIONS, CORRECTIONS, DELETIONS) FROM THE PREVIOUS ISSUE HAVE BEEN HADE. THIS WAS DONE AS A CONVENIENCE "ONLY AND THE GOVERNMENT ASSUMES NO LIABILITY WHATSOEVER FOR ANY INACCURACIES IN THESE NOTATIONS. BIDDERS AND CONTRACTORS ARE CAUTIONED TO EVALUATE THE REQUIREMENTS OF THIS DOCUMENT BASED ON THE ENTIRE CONTENT IRRESPECTIVE OF THE MARGINAL NOTATIONS AND RELATIONSHIP TO THE LAST PREVIOUS ISSUE. Custodians

:

Army - MR

Navy - SH Air Force - 68 Review activities:

Army - MR , ME

Navy - SH Air Force - 68 DSA - PS, GS

Preparing activity:

Navy - SH (Project 9140-0039)

International interest (see section 6)

4

90
NBS-114A (rev. »-76)

U.S. DEPT. OF COMM. 2,Gov*t AccessJoR NoJ 3. feftigten!'* Accession: Ho. BIBLIOGRAPHIC DATA

SHEET

1. PUBLICATION OR REPORT NO.

TN 1130

4. TITLE AND SUBTITLE

Recycled Program: Phase I - Test Procedures for

Recycled Oil Used as Burner Fuel

5. Publication Date August 1980

i. PerfeosJBjl Organization Code

7. AUTHOR(S)

D.A. Becker and J.J. Comeford

8. Performing Organ. Report No.

9. PERFORMING ORGANIZATION NAME AND ADDRESS

NATIONAL BUREAU OF STANDARDS

DEPARTMENT OF COMMERCE

WASHINGTON, DC 20234

19, P^iecl/fask/Wo* Unit No.

11. Contract/Grant No.

12. SPONSORING ORGANIZATION NAME AND COMPLETE ADDRESS (Street. City, State, ZIP)

Same as above.

13. Type of Report & Period Covered

Final

14. Sponsoring Agency Code

15. SUPPLEMENTARY NOTES

Supersedes NBSIR78-1453

|

| Document describes a computer program; SF-185, FIPS Software Summary, is attached.

16. ABSTRACT (A 200-word or leas factual summary ol moat significant information. If document includes a significant bibliography or

literature survey, mention it here,)

The Energy Policy and Conservation Act requires the National Bureau of

Standards (NBS) to develop test procedures which can be used to establish the

"substantial equivalence" of recycled oils with new oils. This report covers

the first phase of the NBS program, and contains test procedures which may be

used for establishing the substantial equivalency of recycled petroleum oils

(including blends of recycled oils with new oils) to new oils for use as a burner fuel. Test procedures were selected and evaluated for their ability to

reliably measure the property under test.

17. KEY WORDS (six to twelve entries; alphabetical order; capitalize only the first letter of the first key word unless a proper name;

separated by semicolons) Fuel oil; petroleum standards; petroleum test methods; recycled burner fuel oil;

substantial equivalency; used oil; waste oil

18. AVAILABILITY [S} Unlimited

I I For Official Distribution. Do Not Release to NTIS

fcl Order From Sup. of Doc, U.S. Government Printing Office, Washington, DC

20402

I I Order From National Technical Information Service (NTIS), Springfield, VA. 22161

19. SECURITY CLASS

(THIS REPORT)

UNCLASSIFIED

20. SECURITY CLASS

(THIS PAGE)

UNCLASSIFIED

21. NO. OF

PRINTED PAGES

93

22. Price

$4.25 — ^

__———iM^ USCOMM-DC

There's

anew

look

J

er

... the monthly

/ >^k ^^v 1 / magazine of the Nationj^ ^\^^^^r / al Bureau of Standards.

/ ^^^, / Still featured are special ar- ^^^^^k^r/ tides of general interest on ^-^^^ ^j / current topics such as consum- js>^-S /

er product safety and building ^^ technology. In addition, new sections are designed to . . . PROVIDE

SCIENTISTS with illustrated discussions

of recent technical developments and

work in progress . . . INFORM INDUSTRIAL

MANAGERS of technology transfer activities in Federal and private labs. . . DESCRIBE TO MANUFACTURERS advances in the field of voluntary and

mandatory standards. The new DIMENSIONS/NBS also

carries complete listings of upcoming conferences to be

held at NBS and reports on all the latest NBS publications,

with information on how to order. Finally, each issue carries a page of News Briefs, aimed at keeping scientist and consumalike up to date on major developments at the Nation's physical sciences and measurement laboratory.

(please detach here) SUBSCRIPTION ORDER FORM

Enter my Subscription To DIMENSIONS/NBS at S11.00. Add $2.75 for foreign mailing. No additional postage is required for mailing within the United States or its possessions. Domestic remittances should be made either by postal money order, express money order, or check. Foreign remittances should be made either by international money order, draft on an American bank, or by UNESCO

coupons. Send Subscription to:

I

NAME-FIRST, LAST

I I I I I I I I I I I I I I I I I I I I I I I I

Remittance Enclosed (Make checks payable

to Superintendent of Documents)

Charge to my Deposit Account No.

COMPANY NAME OR ADDITIONAL ADDRESS LINE

I I I Ill I I I I I I I

STREET ADDRESS

I I I I I I I I I I I I I I I I I I I I I I I I I I I l I

I I I I I I I I I I I I I I I

STATE

I I I I

MAIL ORDER FORM TO:

Superintendent of Documents

Government Printing Office Washington, D.C. 20402

PLEASE PRINT

NBS TECHNICAL PUBLICATIONS

PERIODICALS

JOURNAL OF RESEARCH—The Journal of Research of the National Bureau of Standards reports NBS research and develop- ment in those disciplines of the physical and engineering sciences in which the Bureau is active. These include physics, chemistry,

engineering, mathematics, and computer sciences. Papers cover a broad range of subjects, with major emphasis on measurement

methodology and the basic technology underlying standardization. Also included from lime to time are survey articles on topics

closely related to the Bureau's technical and scientific programs. As a special service to subscribers each issue contains complete

citations to all recent Bureau publications in both NBS and non- NBS media. Issued six times a year. Annual subscription: domestic

$13: foreign SI 6.25. Single copy, $3 domestic: $3.75 foreign. NOTE: The Journal was formerly published in two sections: Section A "Physics and Chemistry" and Section B "Mathematical

Sciences." DIMENSIONS/NBS—This monthly magazine is published to in- form scientists, engineers, business and industry leaders, teachers, students, and consumers of the latest advances in science and

technology, with primary emphasis on work at NBS. The magazine

highlights and reviews such issues as energy research, fire protection, building technology, metric conversion, pollution abatement,

health and safety, and consumer product performance. In addition, it reports the results of Bureau programs in measurement

standards and techniques, properties of matter and materials, engineering standards and services, instrumentation, and

automatic data processing. Annual subscription: domestic $11;

foreign $13.75. NONPERIODICALS

Monographs—Major contributions to the technical literature on

various subjects related to the Bureau's scientific and technical activities. Handbooks—Recommended codes of engineering and industrial practice (including safety codes) developed in cooperation with in- terested industries, professional organizations, and regulatory

bodies. Special Publications—Include proceedings of conferences sponsored by NBS, NBS annual reports, and other special publications

appropriate to this grouping such as wall charts, pocket cards, and

bibliographies. Applied Mathematics Series—Mathematical tables, manuals, and

studies of special interest to physicists, engineers, chemists,

biologists, mathematicians, computer programmers, and others engaged in scientific and technical work.

National Standard Reference Data Series—Provides quantitative data on the physical and chemical properties of materials, compiled from the world's literature and critically evaluated. Developed under a worldwide program coordinated by NBS under

the authority of the National Standard Data Act (Public Law

90-396).

NOTE: The principal publication outlet for the foregoing data is the Journal of Physical and Chemical Reference Data (JPCRD)

published quarterly for NBS by the American Chemical Society

(ACS) and the American Institute of Physics (AIP). Subscriptions,

reprints, and supplements available from ACS, 1 155 Sixteenth St., NW, Washington, DC 20056.

Building Science Series—Disseminates technical information developed at the Bureau on building materials, components,

systems, and whole structures. The series presents research results,

test methods, and performance criteria related to the structural and

environmental functions and the durability and safety characteristics of building elements and systems.

Technical Notes—Studies or reports which are complete in themselves but restrictive in their treatment of a subject. Analogous to monographs but not so comprehensive in scope or definitive in treatment of the subject area. Often serve as a vehicle for final reports of work performed at NBS under the sponsorship of other government agencies.

Voluntary Product Standards—Developed under procedures

published by the Department of Commerce in Part 10, Title 15, of

the Code of Federal Regulations. The standards establish nationally recognized requirements for products, and provide all concerned interests with a basis for common understanding of the

characteristics of the products. NBS administers this program as a supplement to the activities of the private sector standardizing

organizations. Consumer Information Series—Practical information, based on N BS research and experience, covering areas of interest to the con- sumer. Easily understandable language and illustrations provide

useful background knowledge for shopping in today's technological marketplace. Order the above NBS publications from: Superintendent of Documents, Government Printing Office, Washington, DC 20402. Order the following NBS publications—FIPS and NBSlR's—from

the National Technical Information Services, Springfield, VA 22161

.

Federal Information Processing Standards Publications (FIPS

PUB)—Publications in this series collectively constitute the Federal Information Processing Standards Register. The Register

serves as the official source of information in the Federal Govern- ment regarding standards issued by NBS pursuant to the Federal Property and Administrative Services Act of 1949 as amended,

Public Law 89-306 (79 Stat. 1127), and as implemented by Executive Order 11717(38 FR 12315, dated May 11, 1973) and Part 6 of Title 15 CFR (Code of Federal Regulations).

NBS Interagency Reports (NBSIR)—A special series of interim or

final reports on work performed by NBS for outside sponsors

(both government and non-government). In general, initial dis- tribution is handled by the sponsor; public distribution is by the National Technical Information Services, Springfield, VA 22161,

in paper copy or microfiche form.

BIBLIOGRAPHIC SUBSCRIPTION SERVICES

The following current-awareness and literature-survey bibliographies are issued periodically by the Bureau:

Cryogenic Data Center Current Awareness Service. A literature sur- vey issued biweekly. Annual subscription: domestic $35; foreign $45. Liquefied Natural Gas. A literature survey issued quarterly. Annual

subscription: $30.

Superconducting Devices and Materials. A literature survey issued quarterly. Annual subscription: $45. Please send subscription or- ders and remittances for the preceding bibliographic services to the National Bureau of Standards, Cryogenic Data Center (736) Boulder, CO 80303.
U.8. DEPARTMENT OF COMMERCE

National Buraau of Standards

Washington. O.C. 20834

OFFICIAL BUSINESS

Penalty for Private Use. $300

POSTAGE AND FEES PAID

U.S. DEPARTMENT OF COMMERCE COM-215

SPECIAL FOURTH-CLASS RATE

BOOK

.