NATL INST OF STAND S TECH

AlllOb T7fl cIS0

IMBSIR 78-1453

Recycled Oil Program:

Phase I - Test Procedures for

Recycled Oil Used as Burner

Fuel

D. A. Becker

J. J. Comeford

Recycled Oil Program

Office of Recycled Materials

National Measurement Laboratory

National Bureau of Standards

Washington, DC 20234

October 1978

Issued February 1979

Report to the

Federal Trade Commission

Washington, DC 20234

QC

100

U56

78-1453

’>.5iO!tal Bureau of Standards APR 1 7 1971

I

NBSIR 78-1453 IT"

RECYCLED OIL PROGRAM:

PHASE I - TEST PROCEDURES FOR

RECYCLED OIL USED AS BURNER

FUEL

D. A. Becker

J. J. Comeford

Recycled Oil Program

Office of Recycled Materials

National Measurement Laboratory

National Bureau of Standards

Washington, DC 20234

October 1978

Issued February 1979

Report to the

Federal Trade Commission

Washington, DC 20234

U.S. DEPARTMENT OF COMMERCE, Juanita M. Kreps, Secretary

Jordan J. Baruch, Assistant Secretary for Science and Technology

NATIONAL BUREAU OF STANDARDS, Ernest Ambler, Director

Abstract

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.

i

Table of Contents

Page

Abstract . . ..... . . i

List of Tables ........... iv

Li'st of Figures ^

1. Introduction .* 1

2. Burner Fuel Oil Specifications ...... 4

3. Characteristics of Recycled Oils Used as

Burner Fuel 10

4. Evaluation of Test Procedures ......... 14

5. Test Procedures for Operational Performance 21

5.1 Sampling Test Procedure 22

5.1.1 Sampling ......... 23

5.2 Test Procedures for Bulk Properties 30-

5.2.1 Flash Point 31

5.2.2 Pour Point 36

5.2.3 Distillation Temperature . .• 40

5.2.4 Viscosity ..... 44

5.2.5 Density .......... 52

5.2.6 Copper Corrosion ...... 58

5.2.7 Aniline Point 64

5.2.8 Heating Value 68

5.3 Test Procedures for Impurities 81

5.3.1 Water and Sediment 82

5.3.2 Carbon Residue 103

5.3.3 Ash 110

5.3.4 Total Sulfur ..... 120

5.3.5 Acidity 130

6. Test Procedures for Impurities of Potential Environmental

Concern .................

6.1.1 Lead ...............

6.1.2 Polynuclear Aromatic Hydrocarbons

6.1.3 Halogens (Chlorine and Bromine)

7 © Re ferences . . . © • © . © © . © © © . . © © . . © . . .

8. Appendix A. Energy Policy and Conservation Act,

Section 383 ..............

* ii

Table of Contents (cont’d.)

Page

9. Appendix B. Fuel Oil Specifications ........

B.l ASTM D396-76, Standard Specification

for Fuel Oils ........

B.2 Federal Specification W-F-815C,

Fuel Oil, Burner

B.3 Military Specification MIL-F-859E,

Fuel Oil, Burner . . . . B.4 Military Specification MIL- F- 168S4F

Fuel Oil, Diesel, Marine . . . .

m

List of Tables

Page

1. Summary of Specifications Contained in D 396 and

W-F-815 C 6

2. Lubricating Oil Additives and Contaminants Likely

to be Found in Used Oils 11

3. Summary of Reported Used Oil Analyses 12

4. NBS Test Procedure Evaluation Process ....... 17

5. Summary of Sampling Requirements ......... 24

6. Precision of Flash Point Test Procedures for Virgin

Fuel Oils ............... 33

7. Repeatability of the Flash Point Test Procedure . . 34

8. Precision of the Pour Point Test on Fuel Oils and

Fuel Oil Blends (D 97) 38

9. Repeatability of Distillation Temperatures for

Distillate Fuel Oils (D 86) 42

10. Repeatability of the Kinematic Viscosity (ASTM D445)

for Recycled Oils, Used Oils, and Used Oil/

Virgin Fuel Oil Blends 48

11. Effect of Volatiles Removal on the Kinematic

Viscosity Test Procedure (D 445) ......... 49

12. Effect of Particulates on the Kinematic Viscosity

of Used Oils (D 445) 50

;3. ASTM Precision for D 1298 and D 2 8 7 ] 2 ]..... . 55

14. Measurement of the API Gravity for Recycled Oils,

Used Oils, and Fuel Oil/Used Oil Blends (D1298) . . 56

15. Copper Corrosion Test on Fuel Oils at 50 °C

for 3 Hours (D 130) 60

16. Copper Corrosion Test on Fuel Oils and Used Oils

at 100 °C for 3 Hours. ................ 61

17. Repeatability of the Aniline Point Test Procedure

for Distillate Fuel Oils (D 611, Method A) . . . . . 66

iv

Page

18. Experimental Heat of Combustion Data 71

19. Uncorrected Gross Heat of Combustion for Fuel Oils

as Estimated from Their Gravity 75

20. Comparison of Estimated and Experimental Gross Heats

of Combustion ..... 77

21 . Results from the Centrifuge Methods for Water

and Sediment ................... 87

22. Repeatability of the Water by Distillation Test

Procedure (D 95) ........... 91

23. Repeatability of Test for Sediment by Extraction . 92

24. Sequential Sediment Determinations Using Single

Thimble ................... 95

25. Precision Criteria for Procedure B of D 893 [26] 99

26. Repeatability of the Coagulated Insolubles Test

Procedure (D 893) ........ 100

27. Precision of Carbon Residue Test Procedure for

Virgin Fuel Oils . 106

28. Repeatability of the Carbon Residue Test Procedure

on Distillate Fuel/Used Oil Blends (on 10 - Percent

Distillation Residue) - D 524 (% wt)...... 107

29. Repeatability of the Carbon Residue Test Procedure

for Recycled Oil and Virgin Oil/Used Oil Blends - D 524 ' 108

30. Repeatability of the D 482 and D 874 Ash Test

Procedure .......... .... qi 5

31. Elemental Recovery in Sulfated Ash (D 874) for the

Major Constituents in Recycled Fuel Oils 119

32. Sulfur Data for Fuel Oils and Recycled Oils . . . 125

33. Precision of D 1552 Test Procedure for Sulfur. . . 126

34. Comparability of the D 1093 and Modified D 1093 Test

Procedures .................... 136

35. Repeatability of the Acidity Test Procedure for

Petroleum Oils Using the Modified ASTM D 1093 . . 133

v

List of Figures

Page

1. NBS test procedure evaluation process . . . * . . . 18

2. Electron photomicrograph of particles in used

automotive oil extract at 2500X magnification ... 93

3. Electron photomicrograph of 'particles in used

automotive oil extract at 25,000X magnification.. . 93

4. Electron photomicrograph of particles in used

automotive oil extract at 100,000X magnification. . 93

5. Potent iome trie Titration of Recycled Oil Sample. . 140

vi

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

purpose of this report is to provide a se

procedures which may be applied to a recy

its substantial equivalency to a new oil

use as a burner fuel. For the purposes o term "substantially equivalent" (as used

taken to mean equal performance of the oi

important operational parameters concerne

end use.

NBS program, and the

t of evaluated test

cled oil to establish

for the specific end

f this report , the

in the EPCA) has been

1 with respect to the

d with this particular

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, consistent with obtaining the

required results.

F.uel 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 installs t ions

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 of a burner fuel oil are controlled

through the use of specifications of which two, the American

Vll

1

1

Society for Testing and Materials (ASTM) Specifications D 396-76

and the Federal Specification VV-F-815C, are the primary specifications in current use. These specifications are discussed

further in the body of this report, and include test procedures

which are designed to evaluate the significant and important

properties of the 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.

t 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 356 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 • pr inciples by a scientist knowledgeable in the technical area which

the 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 performab il ity 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 performabil ity of the test where

these effects were significant.

• • « Vlll

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 procedures 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 described 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

IX

TEST PROCEDURES FOR RECYCLED OIL USED AS BURNER FUEL

1. Introduction

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 (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 prescribed under subsection (d) (1) (A) (i) , is substantially

equivalent to new oil for a particular end use.
I
2

(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. 1 (4) The term 'manufacturer' means any person who re-rcfines 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, and (d) to

reduce the environmental 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 concentrations in used oil and by the

basic hydrocarbons themselves.

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 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 NB3 program plan has been (a) to review existing burner fuel oil

specifications and test procedures and, utilizing available information

1 In this report, the term "new oil" is used interchangeably with the

term "virgin oil."

3

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, consistent with obtaining the required results.

4

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:

ASTM 3 D 396-76, Standard Specification for Fuel Oils

B

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

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

MIL-F-16884G, Military Specification, Fuel Oil, Diesel, Marine

2 Numbers in brackets indicate the literature references at the end of

this report.

3 American Society for Testing and Materials.

5

These specifications are included in this report as Appendix B. The

first two, ASTM D 396 and W-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 W-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 petroleum-derived 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 fractions and are classified on the basis of distillation

temperature (10-percent point and 90-percent 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 described 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 ensure that evaporation proceeds with a minimum of residue.

Table

1.

Summary

of

Specifications

Contained

inD

396

and

W-F-815C 6

ino

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"Legal"

refers

to

applicable

laws

or

regulations

setting

maximum

sulfur

levels

and

minimum

flash

point

levels.

Table

1.

Summary

of

Specifications

Contained

inD

396

and

W-F-815C

(Continued) 7

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A

"Legal"

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regulations

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maximum

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minimum

flash

point

levels.

8

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 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 climates for

handling.

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

than Grade 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, ' 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

r
.
9

such tests is to assure that the "...consumer receives a product of

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

10

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 performance-related 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 through

15 and are summarized in table 3. Very little information is available

in the literature on the direct effect of these contaminants on recycled

m 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

Table

2.

Lubricating

Oil

Additives

and

Contaminants

Likely

to

be

Found

in

Used

Oils

[4,

5,

7]

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>• c CD

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CO

C i—!

44 0 a 4H CO E 03 e £ £ 0 3H Ci 0 r- 44 a 0 (3 o 03 0 O O 3 X 0 3 0 0

X3

u < 0 U

u 3 0 > au £ 0c

a) iH

>1 a 0 03

44 3 CO

H 0 •H 03 3

•• Sh 3 t1 « CO 03 0 3 •H

Cc 3 C rH 0 aa 0 rH 0 a a 0

44

a o £ a 0 0 Sh 0 0 i—i S 0 3 •» 0 E •H > a CO a 0 rH 03 03 0 • • a 3 c 0 •• a

CO 0 CO 3 a

C

O

rX

O 0 o > 0 0 a c • •H 0 rC •• E H CO a • i—1 44 CO O Sh rH 0 CO .. 0 0 0 •H C 0 0

44 144 > rH o *H

a

a c 1—1 0 •H Sh a £ 0 £ 0 0 44 3 0 > 0 •H 0 i—1 0 >1 •*H a a a a > 0 3 03 rH 03 a c Sh a 0 rH 0 03 3 c 0 O 0 O u O'* £ < CO 0 a U a CO 0 0 c — 0 0 •H 0 3 i 0 0 •- a P - 0 0 H •H 0 - 0 0 p a a a a a l 0 a p 0 rH > 0 0 0 0 a 0 a 'H 3 >1 a 0 r- 1 E 3 • 0 0 0 0 0 0 3 3 P a 0 0 0 0 0 3 > o 0 a a 0 a a 3 •H a CP p O 0

•iH

a

a • 0 i—i a • 0 0 >! r3 0 a •H 3 a • 0 a a 0 0 0 3 rH 0 0 E 0 a 0 a •H i—i 0 a

•H o • c 0 0 0 a *H >i •H

—

O E 3 a

O

03 •H 0 0 a 0 • a • - 03 0 a 0 0 0 3

03

a 03

a •H .. 0 •«.

p 0 0 0 l a 0 ••

p 0 0 0 a 3 a a 0 3 0 • • a a 0 O O 0 0 o • - •- 0 p

•H 3 3 a

a •H 0 ,—! 0 0 3 3 c a 0 1 0 0 a

a 03 0 0 0 3 x

a 0 a £ 0 0 0 0 > o 03

a 03 0 1 a 0 0 0 a 0 >, •• • 0 CP ,3 3 • • •H 3 3 3 •H . - 0 £ p 0 03 3 > »—i 0 0 •H a a 0 0 a 0 3 0 o 0 0 c 0 •• a a 3 0 0 0 0 a 0 a 0

r* 3 H CP

O

a 0 ,—t

03 0 0 0 0 0 r~

a

a 3 03 •H 03a i—!

03

a

a 0 . 0 C CP a 0 a O-l rH a 0 •H 0 o 0 a 03 0 E 0 >, 4C . •H a 0 o •H 0 - 3h E 0 0 £ 3 a 03 0 0 a a 0 0

AC 0 3 a c •H P 03

a •rH

a 0 0 •H 0 0 0 « - U

a

a o 03

a

H 0 03 3 3 0 0 0 a ••

N 03X > 0 0 3 0 f—1 p

a 0 o a Co •H 0 0 X rHa >, 0 3 •H 0 a 03 03 0 a 0 3 0 c a •H a 03 a 0 >, a a a * •H a 42 3 3 0 0 O •H a a 0 3 0 - 03 a 0 u r" • • a 3 0 0 3 0 . - a

•H

N 0 c 0 a 0 0 3 0 03 0 0 0 a 0 0 a • • 0 • • £ a 0 *H *- 0 0 •H 0 >, CP a •«. i

i 0 0 a 0 0 0 0 £ a 0 0 V a 03 a ,—i 0 3 0 3 . p a E . - a a 0 O

•«

a

C 0 a £ 0 •H >•

— 3 0 • 0 0 0 a

a o 0 0 0 H

a o a 3 3 3 E a 0 •H

a E 0 03

a 0 03 •H 3 a 0 0 0 H 0 0 •H 0 •H -H a 0 0 a -h 0 • - a 0 3 a 0 a 3 0 *H 0 r- cn 0 a 3 0 0 a •* 0 0 X 43 0 0 E a 0 *H 4C 0 •H 2 c 0 a a 0 a •H 0 E i 0 a E 0 a 0 0 3 0 0 a 0 a

*H 0 a 0 0 3 0 0 0 >1a 0 *H la - H 0 3 >,a

a

a

a r— •H 0 a Cn a 0 a CP 0 0 0 rH 3 a a a a 0 •H 3 a rH c 3 a a rH c a o a 0 0 a 3 *H 0 0 0 3 0 3

r- E 0 X 3 0 £ 0 c r~* < 0 u a Q E a 0 > a a i—i < a < a 0 £ « 0 0 W 3 < C4 0

rH 03 -H 3 0

(0 rH O 0

•H *H

rH

a 3 a

(0 CO a 3

03 03 >1 3 a -h

Table

3.

Summary

of

Reported

Used

Oil

Analyses

[4-15]

12

U

<44 CO CO

CM VO ON CO o 40 • • • • •

Cft vO AT in o in o o rH

pH

O CMm ON vO

•H CO co ON O CO p

a) rpH • • • i—l • CO <3 <3 <3 <3

•H 1 1 1 • • • l 1 l • 1 1 i Z z Z Z 4Jw r-. tH CM pH in P • • . • • d CO m o in o CO o o o a at CM pH m V M pH CO CM

<3 < C < <£ <; 2: z 2: z 2 2; z d m n eo m e'- en m

at <r

r- co at o

in pH

rApHmcMonONr'-OvOAr n n n <

co

cm o

at coON oMOuOs I I I I I I 1 I I I z VO CO CM H N H in O O CO t-'-ONOOocMm.Ho.-i

oo >H r- r-. pH in

O pH l-» 00ia I I I pa rrH i—I d o o

VO

CM

pH vO

O

on o m

cm on

m Ov <*w «=• CM CO pH I I I

pH ON ON

pH pH

CM CO

lO CO pH

[-»

m o

vO r-- at

•v *n i—I CM CMI I I m m o

co

v ON

CO

pH < 4-1 A43 ft) 60 E

*pt P /

ft) rH /A 4-1 £ o 4-1 43 o > 43 00

4-1

A Pa CO /—V

cn o 43 Pa •H ft) 4J a 43 ft) 43 /A

4J o s^ 43 5 00 4J O N-/ S'? pH Pa pH 43 /A

Ll AT '

' Pa 43 ft) oo 4-1 o PL 0) cn P 43 2 H 43

4-1 E a) o a 44 S'? ft) 00

Pa cO o P E pH o /~N P3 SM v-^ PA 2 •pi Pv

4-1

O i—i 3 43 pH 43 ft) E U CO vO o pH P 44 0 - ft) Pa CL /PA

ft) 33 A-' > O pH 3 ft) 03

p SM 43 /A CL E a CO > o pH P ft) d '—/

Pa E /A 'p CL o A4 >N Pa cn •H U pH 4-1 •H S'? 4300 a. E CL u 4-1 40 Pa C d a d d in in /A CL, CL in vp

P-, PA *p-< 43 -H •H > M—1

ft) rH S'? E '—/ CL

p E s

4-1 > SM ft) o pH Li •H ft) cl '—/ u CL s CL •H d A4 ft) C Oh 00 P O d Cl. E o CL p CL

cn >-t N-'

C •H c in (3 •H JH v-/ P E 43 •—- d

O oO Ll a) rH pC iH

O Pa )-4 P •H

p CL •pH o ft) Z M o cn 4-1 A 43 4-1 o IH o U •H in E d

cn

h 4-1d cn 03d 43

M 4—1 pH pH

C ,—i

Ll o d P o

•pi Pj

d CO ft)

d rH cu indd 43 P ;Hdd 43 0) pH 14 > <3 P3 P3 O tu Pd < u Ph U CO CM o P3 CU pJ < M

4-1 c

ft) 4-1 cn •H

cncood

•pi

ft) 43

Pa r—o « d AT >4 E . ( ft) •H d in • i—1

4-1 pH /-s 4-1 d •pi 41 P

03 o Li o O A m Cl d

a; ft)

d

Li Pa Li O pH

d <44 d cn ft)

ft) o •pi Li

V4 43 ft) ft) d 4-1 d

43 o •H

4-1

p in

p PA

d • M in 4-1 o

03 pH •H CJ

ft) •pi in

4-1 o o cn

in

a •iH •H pH in pH d •H 44 •H > P

in J-4 43

4-1 4-J in cn *

ft) P • 44

4-1 •p CM

d

C • a) pH •pi m o

pH Li d •d • ft) ft) u CL a in a) o d in m d M <i) vO

4-1

O ft) AT

d <44 cn d w <44 •

ft) o

a) pH in d 43 d 44 vH d d d > pH o d o tH o 44

Ll

d ft)d . CL > CO o ft) • d o .—l

4-1 in pH 43 o 4-1 0) d Li d d cn u in ft) pH

ft) ft) Li 44 tH

d 4-1 2 ft)

d

d

•H > > d 4-» d •H d d 4-1 d d

cn ft)

d Co 44

ft)U T3

d o o a) 4-1 d d d <4-1 d pH 43

a) <4-4 ft) o d

i-i •pi 4-1 43 ft) 44

a)

d •H Pa pH

d

>44 E d CL

d

ft)

d •pi co E

Li ft) pH

d II ft) II in

4-J i> Pa • in 4-1 Li CO a) < o ft) ft) CO c •

V-H 43 > CO o Z

CO 43

Od a) 00 43

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).

13

recycled used oil as a burner fuel and, when completed, should provide

additional information and data on these questions [ 16 ].

0

14

4. 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 procedures 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 developed

by this same organization as required when new concerns or problems are

identif ied.

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 impurities and contaminants

may make the oils unfit for further use in certain applications. Any
V
15

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 performance 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
I
16

contaminants in recycled oils interfere v/ith the measurement 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 procedures for these impurities must be

evaluated for their ability to reliably measure the component 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 procedures for three impurities

in recycled oil which may be significant because of environmental

considerations. These impurities are lead, polynuclear aromatic hydro-

, carbons, 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
'

i I '%
17

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.

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 encompases.

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 perf ormability of the test procedure 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

perf ormability 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.
.
18

Figure 1. NBS test procedure evaluation process.

19

automotive 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.

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 'reproducibility' multilaboratory-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-operatorlaboratory] single results as would be exceeded in the long run
I H '
20

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), nitrosamin.es,

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 beyond the scope of this report and their

effect on these test procedures was not evaluated.

r

21

5. 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 properties 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 adequate

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 aeid, 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 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."

Specific test procedures are discussed below.

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).
.


23

5.1.1 Sampling

Proper sampling of fuel oils is important because the commercial

value of a petroleum product 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 statistical 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].

^ 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).

&

24

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. ,

Table 5.

Specif ication

Summary of Sampling Requirements

Requirement

D 396-76

W-F-815C

No requirement.

Take one sample in accordance with D 270

(physical methods)

.

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

to D 270; composite the samples if their APIgravities do not vary from the average by more

than 0.3° (0.0012 density units).

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

1. ASTH 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 suggestion for sampling. Under

section 2.1, the grades of fuel oil are required to be "homogeneous

® American Petroleum Institute; see also Section 5.2.5, Density of this

report.

Pi

25

hydrocarbon oils," but criteria for the determination of homogeneity are

not included.

2 . W-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 W-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.

26

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

n 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] (see Section 5.2.5, Density).

MIL-F-859E is presently not used by the U.S. Navy, which now uses

MIL-F-16884G [22].

27

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

This specification contains essentially the same sampling requirements as W-F-815C, which calls for samples to be taken in accordance

with ASTM D 270.

For recycled oils, an adequate sampling procedure is especially

important in order to provide 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 wich virgin

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

Stratification of several recycled used oils was noted in the

literature for used oil/virgin distillate oil blends [5,14]. This

stratification apparently occurred largely due to the difficulty of

adequately mixing dissimilar oil types in large tanks. The problems

with reprocessed used oils and virgin residual oils are less well documented; however, an API Task Force recognized the homogeneity problems

28

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 0 percent up to 15 percent by volume, v/v)

.

The recommended sampling requirements for recycled 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 inhomcgeneity 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. 7 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.

7 See Section 5.2.5, Density of this report.

29

Samples may be composited to a single sample if the lot is homogeneous. If the lot is not homogeneous, specification tests will

be performed separately 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 recommended to obtain samples

for the various tests used to characterize bulk lots of recycled oil to

be used as fuel.
1 ' I
30

5.2 Te.' _ 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 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 performance (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

performance of the test.

The individual test procedures are discussed below.
Hj |f
31

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 contamination 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.

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
.
32

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. 3

The Pensky-Martens test procedure was evaluated for recycled oil

used as burner fuel. As part of this evaluation the D 93-77 test

3 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.

33

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 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.

Table 6. Precision of Flash Point Test Procedures

for Virgin Fuel Oils

Flash

range

point

Repeatabil ity DCReproducibility

104° C and 2° C ( 4° F) 3.5° C ( 6° F)

under

Above 104° C 5.5° C (10° F) 8.5° C (15° F)

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

e be consulted for additional details.

”D Duplicate results by the same operator should be considered suspect

if they differ by more than these amounts.

c 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)

34

/N /-N /-N /—

rs /-s r- <r NO in rH o <r cn in un in m CM m CO cn on

U* r—1

rH rH rH CM CNI «H

H 0 v-/ 'w' eM 00 ON n- 0- 00 f" <r ON

pH

u « 4-1 3 o ON CO rH rH r>4 NO ON cn 3 u nO NO NO m CM cn in oo CM O C pH pH J3

OJ 4-1 4-1 G c • <*. • CN • M • • #* • Pi •H

*H /—

N

/~N /*N /-N 5

S-i o m

m

m <r rH rH co r- cn 3 a m m m CM m CO m on r>4 3 a r—1

rH rH rH CM CM i—1 rH

U

X xz '—

v—

v-x 'w' s-/ Vw'w 'w' V-/ 3 w cn 4-1 3 cn cn cn rH cn rH r- 00 3

rH • H

44 00 00 CO pH i—1CO 00 rH CN 3

NO NO NO

m CM cnm on CM • Cu rH rH cn S

rH 3

-H 4-1 O E 3 O

cn o 3 M 3

4-1

C 3 3

Jh 33 3 3

XZ 3 cn > 3

-rH rH

4-1 <4H OE 3

cn o rH cn cn 4-1 cu

r-l r-l 3 E

P-. ft, 3 3

CO CM v-/ cn CM CM "0

CM o rH rH 3 • A o 52 •H •H m /*N CO 4-1 :s /"“N O O > 3 c

rH SM CM XZ rH cn m cn iH pH 4H > 3 O

rHm rH rH 3 0) •H )-i cu 3 Ph Ch 3 3 3

pH V-/ 4* + 4-1 MH

a

a 33 XZ

a /P-N /^N /^N 3 <r cn E r—1

rH rH rH 33 33 <r cm CM 3) CM 3 3 •H iH •H 3 3 CM CM CM TO O rH

CO o o o o rH rH o o O 3 3 44 o o Dc 3= rH r-l rH rH >N >N VwP >wP 3 -3 4-1 • a) 3 0) a) o 3 C C c 00 3 3 3 3 0) 3 rH pH pH *H 3 3 C

<4-1

H 14-1

u •H *H «H rH 3-4 •H O O o o CM 3 4-1 CM CM CM «H m m cn CM CU 3

no 33 no 3 O CU 3 • • « • • • 3 QJ <3 00 3 < J3 O O o o o o cn cn cn 53 52 53 52 52 7^ 53 53 53 3 ^3 I ri

35

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

procedure, 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.

36

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)

for flow characteristics. The lowest temperature at which movement of

the oil is observed is the experimentally determined pour point. This

test is generally applied to grade Nos. 1, 2, and 4 fuel oil [2]. It is

usually not specified for Nos. 5 and 6 since preheating may be
I
37

required for handling, transfer, and use of these oils, depending on

climate and equipment; however, a "low pour" fuel oil may be specified

j for grade No. 6 [2]

.

The precision of method D 97 for virgin fuel oils is stated to be

as follows [2].

i

"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 Reproducibility —The results submitted by each of two

laboratories should be considered suspect only if the two results

differ by more than 10 F (or 6 C)

.

7.3 For oils tested by the procedure described in 5.9, reproducibility of this order cannot be expected, as these oils show

anomalous pour points depending on their thermal history. 5 " [These special-case oils include black oil, cylinder stock, and

nondistillate fuel oil.]

" 5 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 evaluated for use with recycled oils.

As part of this evaluation the test was applied to a number of virgin

and recycled distillate fuel oils, distillate fuel oil/used oil blends,

and heavier recycled fuel oils. These data are shown in table 8, and

33

CSI 1—a

iH in 3 LO CM

/~N “N

O 1 1 p* pM 3 4/

C\ 0 33 M3 CM Q 3 •<r CO O a l 1 e o 3

03c 3

0)

d 1—1

“H

paO tH /"V /*—N / - , /P*N

a 1—1 o o m

m

H 3 m 1—11—1 CM CO

•H 3 O l 1 1 1 1 O 3 3 s-/ v—

4M o c0 «—1

Pm 3 vO co <n CM e'- 3 3 <T CM CM CO en 3 a 1 1 1 | l Pm o

03C

cO

CO r—1

•HO

03

r— 3

0> rHtf 3 3 3 3 tH1 1 1 /-s Pm >> *H 1 1 rH

m 3 O 1 1 4/ 4/

d 3 1 o oi 3 5-5 33H3c

•H0

P-i 3 3 *4

rH 3 CM i—1 I—1T—I 3 CU -D CO CO CO CO 3 B B pH rH rH 1—1 O co 3 a Pm Pm Pm

Pm cod -—i 3

jdw

4-1 rH i—( l—l T—I O 3 3 3 3 3 3 3 3 d 4-1 i~a 4M /—s 44 4m o d d

•H 3 3 *h 3 -H 3 3

CO i—f 3 so 3 00 3 03 4J •H a 3 3 3 3 3 d 3 O e iH *H pH *H i—1 3 i—l 0) 3 I-1 r* rH i—l pH T—I 3 CO *H w •H 'w' •h jo •H

Pm 4-1 4-1 4-1 3

CO pH

43d

co .—I CO •H -H •H -H •H 0 Q O o o Q O Q co3i—1 rQ

cO H

rH

•HO 3

*0 tH CO 3 (M 3 OQ

(H

i—1

cst CM CM 3

«P-N 3 m 3 m rH l rH 41 •H3

co CO MT •H i 03d

•H • 00 3 5m oo •tH

—

.P-S ^4 ^-v r-\ /—4 3 >

in

m r4 r— C3\ O'

r— )M \D 43 4j- <r cn ^r O 3 1 1 + + 1 l l 4-1 rC 4 ' 4 41 -—i

4-1 4-i v-/ 3 3

<r <r -o- <r

m <r rH <T 03 3 <r

m in rH rH mt nr <r <r

dO 1 1 1 1 1 1 l l 3 4M 03C d 3 3 o 3

*H -a CM

4_) 6 3 3 • 3 d CO rH o

rH 3 s o rH 3 a 3 e 03 3 "3 3 3 d CO 3 O • o o o o 00

t-M o o o 3

4-p iH T—I rH 3 .c

C

p3 3 33

'd CO 2: 3 3 3 W 3 3 m 3 -a 3 3 3 •H 3 o •H

5m

d

a •H 03

i—. 3

T—I '3‘ CO <T 3 CO 3

CO CM CO CO o *3 3

T—I rJ 1—1 rH

d

d rM

Pm P4 Pm 3 a 4-1 a tH

rH -a rH

•H *H O 3 O o 1 3 4H W

1—1 T—I > •H 3 •H •H 3 3 4-1 rH T—I tH 3 3 3

4M CO -H 3 <v

O

W

•H

O 3 3 S 3 1M 3 03 4m ww o pC o

4-1 03 iH 3 3 3 d 03 3 T3 3 d 3

pH 3 3 3 3 0) 3 3 3

pH iH r-l 4M i—I

rH 3 c

•H -a 3 CJ CJ 03 3 3

•U 3 Do 3 a

B

CO tH 3 4J CJ i—1

CJ rH

W 3

•H •H 3 3 3 *H <D -H 3 d 3 a O Dm rH Pi O Dh o •H a 3 CO 3 3 3

•H 3 3

CO pd e O 6 a 3 • S d d 3 o o •H 3 3 -H 3

rH 3 O

O CMa 3 3 1 CM 6 d 3

CM 1 m

m o 3 3 •H 1 U1 4M >

CO Xi o

39

the repeatability and reproducibility of the pour point test for these

samples are consistent with those for virgin fuel oils as discussed

above. Host used automotive crankcase oils will lower the pour point of

virgin fuel oils, both distillate and residual. This effect is shown in

table 8 for the distillate fuel oil/used oil blends, and is most likely

due to the presence of pour point depressants in these high additive

oils. The results of our evaluation indicate that the pour point test

procedure, D 97, can be effectively used with a recycled fuel oil.

CONCLUSION

The pour point of a fuel oil is a useful indicator of the lowtemperature flow characteristics of fuel oil. ASTM method D 97—66,

"Pour Point of Petroleum Oils," has been evaluated with recycled 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.
,
40

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 batch to batch to avoid frequent resetting

of burner controls and to maintain maximum performance 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.

I
-
41

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 example, in our evaluation cf 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 including 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 No. 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 temperature 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].]

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

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43

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 foe 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 chatacteristics of distillate recycled oils to be

used for fuel.
<•
44

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, 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
,
45

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.

-2

Frequently, the centistokes (cSt) is used (1 cSt = 10 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."

r

46

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

D 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 recycled 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 ]im 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)

Nos. 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.
~1
47

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.

abl-

_y„

.._t

,eat

-it}

th^

*..:neir. _

V_^_„

sit.,V

.»STK~•

*5)

Re^r.ed

Used

Oils,

and

Used

Oil/Virgin

Fuel

Oil

Blends

48330oy

CO 3 3 0 C 30

Cl

U

H

U To 3

Jh 0 O 0 ai

0-i l-i

rH

d 3 0

rt o •3

to 3

Jh rH iH 3 0 to > 3

mh0 Jh 3 0 a 30 s e

CO cdo3o3

JhV00Q

CM CTv r-1 CO CM \0 \f O O' CO

in vo co o i-»

rl

N 1/1 CO

N

MO >J

O CO

O0 m mo oo o

rtHH

M CM

O 3 mO

O

i-l CM

CM I CO I I 3 I I PH I II I I I I I I 0 0 3 3 3 d0

rH CN JO CMO

12 CM w co

d

O 3 rH

60 3 -H

In 0 O 3 CO > P O CTv CTv MO CO

CM 00 CO in CTv H rO MO CO 00

CN CN CN CN CO

in Ol CM vO CM

cm co

mm 0

rH CO vO O'' 00 CM (N CM CM CO o r-H m O O

rH CN

CN

rH I 1 I CO I I I rH I I | PH I I I 0 CO 3 3 3 d0

rH ^ rH H CM 3 O CMO r-s rH £2 rH 0^0 3 rH 3 rH Ph

•H 3/

d o 3 rH 003 "H

Jh 0 O

•H CO > ^

CM rH CM <r o 0 O o 00 CM CTv 0

<r • • • • • 5 • <3- r-. o C" lO m ro. m MO vO vO -Cy A 3 • ' <r A jct • * e* A cm o, m • 0 r-> o m co CO MO CM #v <r in CTv r-~ VO O rH 1 • • • • • •H vO m <- VO o A ('. O CTv r-~ in MO r- MO CO

CTv 0 • • 0 IE in 0 H 0

MO

y to 3 .X < 0 d • Jh 0 d HT 00

Jh •H y 3 . 0 3 d 3 0 0 0 3 30 rH 3 X 3 3 0 CN 0 o j0 3 3 JH o o o O o O o 3 0 o o o o O rH e 0 0 3 i—t

rH rH rH V-/ o 0 3 0

M- 3 0 0 CO 3 Jh ''— t

0 0 60 1 Jh 0 M0 3 3 C 0 CT' 0 3 0 3 CO 0 0 0 •H 3 )H > 3 3 . 0 3 0 C-H 0 Cu 0 3 CO E JO o < u 1 3 0 > i 1 1 o H 1—i C l m in | 1 vO • v—

•H 3 •H l 1 0 0 O O 0 60 3

60 0 • i—1 0 0 0 >H 3 0 0 3 3 O 0 3 o 0 d 3 3 3 3 •H 0 0 O 3 y d 0 o

JH 3 3 3 0 0 d 0 30 0

CU 0 0 3 0 3 3 3 0

<r co <r CN rH

O 0 d ts 0 3 f—t CM co co CN rH CO 3 o Jh y

rJ rH rH

O o rH 0 3 0 0 To

u

Ph pH ET pH

y 3 30 rH 3 3 y 3 a. 3 3 0 O rH 0 d 3 0 •H C3 3 3 0 y 30 rx O 0 •rt 0 53 0 y 0 3 3 E-h 3 3 0 0 0 3 d •H 0 1 1 0 d 3 Jh 3. a: 33 o 0 0 . 0 d d 3 To CJ 3 Jh CJ 3 0 0 d 0 U o 0 rH 1—i

}H

u 0 -O o 0 s rH 3 3 y y Jh O Jh H o

rH

OO rH 0 3 NT 0 co

m 3 3 3 3 Or 0 30 < 3 rH T—t 0 0 O 0 3 U 3

CO 0 /—v 0 /-V 0 0 d 0 0 c 0 3 3 < 3 P3 3 3 rH 3 0 To •H 03 rH 3 MH rH rH 0 U 3 3 3 3 0 0 0 rH 0 3 3 0 o 0 •rt u 0

•3

O 3 O 3 o 3 O 3 O Mh Pi IHC 0 •rH

d 0 0 In 0 Jh iH 3 0 a •H O 3

rH rH rH 3 rH 3 0 0 0 0 d JO 0 U 0 o 0 u o y o O 0 O 0 3 E 3 3 0 3 3

To 3 >. CO To co a. 0 O. 0 to 3 o 30 3 o 30 a MH y 3« y w E u S u iH 2 d O > 2 O 0 0 0 o o 3

Pi OS PCj cj cj > 0 30y 3 0 r
I
Table

11.

Effect

of

Volatiles

Removal

on

the

Kinematic

Viscosity

Test

Procedure

(D

445)

49 • a)p0rO

QJ

n

U

0) 0 a o 04 m uo r- p

Oi tO in tO to 04

•H • • • • • • p CO co CO co co CO Cd

-p r~ rO

O to tO e

to «—1

rH a,

04

•Hpp

in i—i o

id co r- r" CO CM 0

r~ CO 04 CM CM 04 o x:

-P • • • • • • p

•H o o in to r- to r~ c to to tO to to in in M XI

<D rH

04 • E ^

V XI cd p

in

X • ID r—1

IDp 0 04 o x: P > iH rH to p ID

ID • • • <D P >1 o o o E in

*0

Xi 0 —

3 p

4H >1 ' p

no •H

<D

r—1 > •<H O X! • E cd CD P

(0 • P cd W rH a)

<u 0 O

a r—\ > in a) •H CM o CG to to to i—i p p >1 to m CM co id cd • • • • • • s «—i

co CO •^r CM CM in Eh

O o\° •H to > —

< P

ID <0 P x:

cd

p S r—1 c

•H P •H o cd x:

X3

p

<u

p •H

r—I

to s

•rH cd • <D o u P p X r* O o p c i C c c 0 id r- 0 p p o S in •H 0 o rH to UO •H p E •H CO 04 a a) o in •H T> > Q Q p p a) •H iH rH o in P a> S S

in 0 0 0 Eh Eh in

<v E tp to to CD a ID O < < p p P0 id Cn Cd <p W <d iH C c o o O •H •H

04 'O >i in in in E a> o 0 O ID O in ID •H U o c TJ P o ID ID c C in •H H

<Dp cd cd in iH 0) CM rH v p p •H

cu P CM r—1

CO X3 XI x: E £ O o rH o o Eh

(0 3 s 3 b w c • cd XI

O

r

50

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. Consequently, 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.

Table 12. Effect of Particulates on the Kinematic Viscosity

of Used Oils (D 445)

Viscosity (cSt at 40° C)

Sample After

* number Description Initial centrifugation

W022 Composite used motor oil 78.60, 78.59 78.42, 78. 44

W004 Used automotive crankcase oil 66.61, 66.40 65.60, 65. 55

won Used automotive crankcase oil 103.65, 103.65 103.35, 103 .37

Initial viscosity measurement made after stripping with D 3607-77

(see text)

.

51

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 Transparent 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.

52

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 reported 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

141 5 API gravity, in degrees = — — ° r n0 ^ 0 t: - J 6 specific gravity at 60 F/60 F

131.5.

53

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

Nos. 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 Hydr'oraeter 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,
1 II r I
54

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 repeatability of the

API gravity for these samples is consistent with the ASTM repeatability

as shown in table 13.

One problem encountered during the NBS evaluation 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 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

procedure that the formation of air bubbles in the sample is to be

avoided, and if formed, sufficient time must be allowed for all such
I
Table

13.

ASTM

Precision

for D

1298

and D

287

[2]

55 ICJ Sn 3 4-» CM CM tn tn 3 *H tH iH tH tH O tH O O O O H *H o o cn o o m

m

CX fa • • • • • • • 0) tH pd o o o o o o o 1 >>

4-1 4-1 to

m tO tO

to *H o o o O

41 tH o o o o

£X -H o o rH o o CM CM

a) fa • • • • • • • cd to o o o o o o O

*'» fa fa o e / N /—\ o fa O fa fa tO o to o o O O O

fa vO fa to to o o O 4-1 o 4-1 4-1 tO cO /^N to c0 to

c_> o e 4-1 CO o 4-1 CO CO

co to CO 3 m to 4) 4)

4-1 >H >—

4) tH 01 3

•H

H

H >-i

C 4-1 >> 00 4-1 >t co oo

£3 CO

u 41 3 4-1 4) 41 •H 3 •H 3 3

fa > v

—

fa > '—

^—** eO CO 00 l-i OO H >t On

fa oo 4-1 fa oo 4-1 44 '—

•H >—

•H •H

a > o > >

Sn •H c0 •H CO cO

4-1 iw

H 4-1 y-i

uU

•H •H 00 •H •H 00 OO

CO CJ CO CJ c 3 M G ai IH

M

a) CX fa 41 cx fa fa Q 00 Q 00 < < O CJ

V 0 0 fa M in fa fa m fa fa 3 • o o • o a 0

4J 4) <r to 00 <r tO 00 CO

to 00 H c

CM r>» CM

m n41 to o O O O o o O a h 4-1 4-1 4-1 4-1 4-1 44 44 § CM CTv CM CM Ot CM CM H 1

0k

CM -O’ t CM sr <3-

4-1 6 c CO CO

m 3 a 41 3 3 o ai o H o o

<H

a cOu * o

01

O 3 ex CO ai CO CX.HO to •H 3 •H

4-1

H

G > cr > H 4) a CO C CO c tH

ex

U o ex. o tH H c o G <

4)H CO 00

4-> 3 at cr>

to -a CM CM 00

ai a) H V

tH f—1

CM o Q a a Ha

56

ll* 3

0)M2

>1 XX>

03PJ

(0 XPX PX

in r- • 0) 0) •01 3

ID > CD »~N

cn pH CN CN CN CN rH CN CN CN rH CN 3c rH rH rH rH rH rH * rH pH pH

CD CN 03 03 ^r 03 03 03 03 O' 03 03 05 —1 •H •H • •HO) •H •H •H • •H •H •pH CQ P p P ID P p p p co p p P • * 0 X X CN X cn rH X X X CN X X X cn H cn r—. X ’ % —

— '—

*

•H 01 03 «* rH rH *• pH o 01 u P o m rH PO 00 iD r~ 03 03 ^r CO -cr X X r- 03 01 p 01 • • • • • • • •H •H • • • • • • • •H p 3 Cn o a cn rH rH «cr •T m ID in p p X X X X X cn cn p 05

01 01 o •or on

m CN CN CN

X

X CN CN CN CN CN CN CN

X

cn 3 • —

—

cn

D

m *» * «* *> «*. * 0) \ rH (3 r- CN o lO o rH ro CO ID CO X X ^r X X X X X X CN pH

rH

a

•H

X CN pH rH in •T rr an ID

mm

X

XXXX

X cn cn cn r~ rH £ o •H Em 3* m m cn m ro CN CN CN N CN CN CN CN CN CN CN CN CN rH rH 03 > in X 03 c

01 P o 0) 3 cn o cn Em 01 H X rH 00 A 3 cd 03 • X C < •— p ID

03 0 CN X

05 cn

cn P m <7> i O r- pH i CO 00

X i CNX o rH

rH 01 • • i • • • i • • • • i • • • X a •CN rH i in e’ nr i ID ID X X i cn r- X 01 O o •or i cn m m i CN CN CN CN i CN rH rH rH 3 O O U O

cnX 3

iH c X

bbX XI o 0 0 H 3 a rH - ^—* O03 CJ >• •H O ln o o in O o o o o o o P o 0 '—' rH 

1 rH o o o o o o 3 X 3 3 X X rH X X H

a>

x 2 P —

>

1 X CN O X >0 Q 3 p v x-x

0)

X 3 CN CN CN rH pH *H -cr

XX

X ro 2 cd n cn cn cn m cn PO CN X ro CN X ro

"p rH rH rH rH rH rH 2 X pH o o O

p § 3 Cm Cm Cm Cm Cm Cm r~ Em Cm S s 0 w c '—

inc: i—1 Xo

0)

X -O

0)

X f0 3 X P

Em 0 ON

CN in in i i i i i i O CN m cn X O

Em Em s

>1 X

•H

XI

•pHo33op

a,3p3g

(0

>1 X

•H

XI

03 -P

H 0 0 X

HH

H 03 cu 3 •H •H *H 3 < t t—t X 3 o 0 o CD • 3 3 X 3 - 3 3 3 X X X P cn G c X X 3 3 3 3 3 X 0 X H H H 3 3 3 «r 0 • •H 3 3 03 H H •H •H •H X X X E-! a H

<4-1

XX

X

X •H •H 0 0 0 C/3 cn •H 0 CD 05 03 X 0 0 X X X < *H 0 X X X X 3 3 3 03 05 03 > X P X X X i—i X 3 3 3 3 3 3 3 i 3 c o X •H cn 3 3 cn cn cn 3 3 3 2 c 3 3 cn X X X 3 3 3 3 3 X X X X 0 cn g 3 U) cn 3 X X cn cn cn _c 3 3 D X X 3 3 3 3 3 3 X P 3 3 3 3 3 X X X p P P 0 3 3 3 3 3 X •H X 3 X

«n c C

XXX cn cn cn c C

G cn 21

X

03

X 3 3 •H 3 3 o o 3 0 O 0 X

X

X 3 3 3 cn C G Cn G C >, >. >i CD CD CD cn cn cn cn 0 0 S p 3 3 p 3 3 o o O E E E p p p 0 X CD X X X X H H 3 3 3 0 0 0 X X X CD E « > CO CQ > CQ CQ a 2 2 U U CJ > > > P 3 0

inv

D ID 3

a,po

Em 3 o i CN W CN W O

o3 3

CDCn

05POX

cn 3c

<3CoXXo

0)oo3co

>1

CD X3

0)cn

cn

a)oop

CD Xo2 3C

03 CN

cnO2

<D 3

ccP

Cnc3

ai5x

0) X

aio

03 H

a.

cn •HxXXO

cno

•HX

cn •Hp

0) Xo

03P

05 Xo

Ep X

•H

cnOu

cn •H> po

Em

these

trials,

efforts

were

made

to

minimize

bubble

formation

(see

text).

57

bubbles 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 charac-

.teristic for the evaluation and monitoring of fuel oils. The ASTM test

procedures 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 evaluated 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.
^1
58

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

"corrosive" 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 tendencies of the fuel oil to corrode copper and

copper alloys are made using specially prepared copper strips. The

effects due to corrosive species in the oil are indicated by discoloration and blackening of the strip [3]. Fuel oil specifications usually

place limits on the degree 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.

59

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

numerical 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 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 W-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.

Table

i5.

Copper

Corrosion

Test

on

Fuel

Oils

at

50° C

for 3

Hours

(D

130)

60

to >4 So tH

4) 4) CO CO CO CO <U <U 43 43 5 >

to 00 CO CO CO CO to to ai a) o o c c c d Cd CO CO CO d d d d rH rH

cO CO •H •H 1-4

d 14 1-t cd CO o O r4 rH

udd a. CU 43 43 43 43

d

d i—1 r4

D <U o o o -

—

**

—. O

O o o >4 So .H 4-t 4-1 5

*> o CJ o AJ 4-1 0) <U o o o O 44 44 •H 4*1 -H 4^ 44 44 o 43 43 rH rH r4 rH i-4 rH 4CC 44 O 44 a 43 43

00 to o o »—4 rH t—1

rH to to r4 cd r-4 CO to to •H •H •H tH <U a) ai a) •H •H J3 rH J3 rH t4 •H

•J .J > > >4 >4

J rJ 44 43 2! 43 rJ rJ

43 43

CO CO 43 43 43 43 43 43

43

X •H •H 43 43 CO CO CO CO CO CO CO CO d d CO CO -r4 •H -H *H 43 43 •H H

d •H •H

d (-1 •H

d

d

d

d CO CO

dd o d C CO ca d d d (4 d d iH •H d d

•H

d

d 4-t 4-t 1-1 14 CO cd cd COd

d

dd cO cO AJ CO CO CO CO 44 44 44 44 d o d o 44 44 •

CO 4-1 4-1 CU CU 4-1 44 cd •H cO •H d 4-1 4-t 44 44 44 44 44 CO 44 CO 44 44 to 4J 4-t cd cd 44 44 r- H 43 o o 43 43

•H 43 43

d 1-t 43 43 'So 'So to to

d 44d to To

d

CO to to <v at to to •H •H •H •H

d

dd

d •H •H cO

0) *H •H TO 43 •H •H rH rH rH rH cd

O COO rH rH o # rH t-l O o i—1

r-4 to to to CO « a

Q

O to CO CM

CO to :r S CO to i

COo

'Z

do (U •H 43

44

d

43 CO CO

CO CJ . to H •H CO d 43 43 co aj cO cO cO CO CO CO CO CO d 44 r4 rH CM CM rH tH rH rH rH tH < vT rH rH d d •H at

CO CO <u H CO

CO 4J

i—1at

CJ E 43 Od 44 rH 44 •H

<U •H

44

O rH <U aJ •H a

rH 0)

O CO rH tH 44 d rH

d •H •H 43 iH CO 43 o Or o O 44 43 43 4) •H ca ai •H

•H CO tH rH CO

O co AJ iH

44 i—1•H •H •H

dd CO

H

a 0) 43O •r

O CU rH /-N 44

O

•H 3 CM CM 4) > CO P3 a) CO d 44 •3 rH 43 43 44 •H •H 44 CO O <U *H • <u . ai •H 44 d (U •H <U •H

CO

d >HO o co o co CO

O 44 CJ CO CJ 43

a) *Ha 2: 3 Z 3 O s CO

d o •H 44

a to So rH C4 o 3) 3J Or > d o cu S'? S'? 6-S 5^5 E 44 43 O E d

d

•H a) 3 o o O

O

O 3 d CO o <U o > pi 44 CTt r4 in m u CO M a CO n

4-1 c

<U

0)

d

r-\ 0) O. 43 e e

cO 3

CO c

rH -T CM r^. CO

CO CM CM CO CO

rH rJ

O o o Ch

d3

COCO

<US O 0) •3 »H CO 4) d 3 t£<

tt,

CM III III

4-t H

cooo

CO >

CO JO

Used

oil

was

W022;

virgin

distillate

fuel

oil

was

F131.

Table

1&

Copper

Corrosion

Test

on

Fuel

Oils

and

Used

Oils

at

100° C

for 3

Hours

(D

130)

61

0) 03 03 a)

a) 1) CO CO co co 03 03 0) 03 03 03 •o ”3

to to

d

d £ d 13 03 03 03 CO 00 00 00 00 00 0) 03 c c 03 03 03 d CO CO CO CO d d d d d d 34 34

ca 03 34 34 34 34

dddd 03 03 03 03 03 03

OO

u

u 3-i

O

O

O

O 03 03 03 03 34 34 34 34 34 34 i-4 i-4 o o O \ \ -

34 34 34 34

OO

O

OO

OO

O

i-4 3 3 O o O

O o a

O 44 4-) o o OO 44 44 44 44 44 44 *r4 •H

U Jd jd rH i—i i—1 rH J<5 JJ JJ jd Jdxx jd jd 44 44 ao ao rH i-4 i—i i-H 34 34 34 34 CO CO CO to co co 1-4 r4

•H •H cu oi a) 03 03 03 03 03 •H •H t4 •H •H *H 3 3

>* >4 >4

QQ

CQ -3

J 4 .J kJ 44 IS

Jd Jd

co CO Jd jd jd Jd -d r- Jd Jd jd Jd jd Jd Jd Jd Jd Jd •H •H

d CO CO CO CO co co CO CO CO co co CO CO co CO CO

C

d o •H •H •H •H -H •H •H •H •H •H i4 i4 34 34 l4 d d d d d d d d d d d d d d d d 03 03 u 3-1 34 34 34 34 34 34 34 34 34 34 34 34 34 34 34 44 44 d 03 03 03 03 03 03 03 03 03 <d 03 03 d o3 03 03 c 44 44 4-1 44 44 44 44 44 44 44 44 44 44 44 44 44 03 03 tC 44 44 •H 4-1 4-1 44 44 44 44 44 44 44 44 44 44 44 44 44 44 03 03

CO jd rC -3

X

X r—

X jd

X Jd

X jd x.

x

— i— 34 34

03 ao co co CO CO 00 CO to CO co CO co 00 co "co "cb 03 03 O • *i4 •H •H -H *H •H •H •H •H •H •H •H •H i4 •H t4 od rO

iH r-4 f-4 t-4 t-4 i-4 i-4 t-4 i-4 rH i-4 f-4 i-4 i-4 i-4 i-4 o JD CO CO CO CO CO CO CO CO CO co CO CO CO CO CO CO IS co

•H

4-1

ttf u - •H 03 03 -d -d 4d 4d jd Jd a jd 03 03 03 03 03 03

aV

4-1 1-4 r4 i-4 r4 i-4 i-4 i-4 r-4 i-4 i-4 i-4 t-4 i-4 i-4 i-4 i-4 CM CM

•H

CO

CO03 ^4O

1“4

i-4 i—1

r4 i-4 i-4 e •H 8^ i4 •H •H •H •H *3 i-4 o O o o o O O o O /-s 03 •H

•H

r4

in 34 CO

O

44 iH i-4 t-4 i-4 i-4 i-4 3 a a) • #3 03 03 0) 03 , 0) >4-1 03 •H 3 CM i-4 CM 3 3 3 3 3 i-4 03 >

54 4-1

H t-4 <44 >44 >44 44 >44 3 44 -H o • O • •H CO •H 44

CO c o o O

d

d

d

dd CO

O o •H 2: T3 s •H •H •H t4 H X o E a ao <13 'O co CO to CO co oo a O

34 CO S'? a) 34 34 34 34 34 i4 E 44 H o 3 o co •H H 44 i4 t4 Jd O 3 > Os m 3 > > > > > ^ a < u

03 i-4 SO Os in

O CM CM

rO CO CM CM CM CO CM CM e i-H i-4 i-4 i-4 1-4 O O 3e

3*4 C*4 P* &4 t>4 5

a) •3 •a

03 CM

d

d

m sO sO | 14 Cl 03 1 ac i-4 -4 I W PQ 1 r

W033

Composite

used

3b

Dark

tarnish

Magenta/

automotive

oil

3b

Dark

tarnish

multicolored

from

service

Magenta/

station A

multicolored

Table

16.

Copper

Corrosion

Test

on

Fuel

Oils

and

Used

Oils

at

100° C

for 3

Hours

(D

130)

(continued)

62 3 3 a)

<u 3 oo n J-i c o o 3 3 cO

u AJ AJ rH rH HI HI J-i A! o 3 o O O o 3 c o O

rH 3 CO 3 a CJ a) GJ CO o Pi rH rH •H •H to 00 HI rH

CJ eo P3 HI HI 3 3 J= «

rH rH In 2 00 3 3 •H S X

X .3 r3

X

CO CO 3 3 J3

•H •H

x •H •H 3 c 3 3 3 3 3 •H o M 3 3 H •H H i-i 3 3

•H 3 O

O 3 3 3 3 O • HI HI •H •H HI J-i HI HI 3 -H vr

CO CO CO 3 HI 3 3 3 O O 3 HI 3 3 O 3

00 HIU J-i HI HI HI HI

U 3

•H 3 3 AJ . 3 3 .3 1-4 3

CO

H o o J-i

U

UM 00O

CD 3 CJ CJ 3 3 3 3'

H CJ CM

O 3 *3

Q •3 3 rH

O

O

O

O CO • In s IS S 3

r\

O 3

•H 3

HI * • J-i

X 3 rH 00 3 3 cd CO

•HH CM 3 X 3 3 .o

X cd 3 rH 3 3 <H CM CO CM CM rH pH 3

J-I

H 3 3 3 3 £ H 3 3 HI 3 2 3

rH

X 3 rH

•Ho

rH "03

rH 3 3 U-l 3

•H HI HI rH 3 3 rH Hi 3 3 a) Or O 3 H 3 rH rH <3 rH PQ cO < 3 m 4-J H 3 O 3 •H *H 3 3 ? cd rH

HI 3 3 3 O 3 3 3 0) 3 3 rH •H a 3 •H 4-1 3 4-1 3 iH 3 iH 3 rH o

•H 3 > > C3 rH

MU cO J-l 3 J-i •H

u HI •H

H 3 3 3 3 3 3 -H 3 -H 3 U 3 3 H HI 3 3 3 3 3 O 3 O )-( O J-I O cn •H 3 3 O 3 O rH CM rH 3 rH 3 HI 3 HI 3 r— 3 O E •H 3 3 ^ 3 ' 3 v-r 3 '—

HI

Q cx, o s HI >> 3 Ph 3 3 E HI o 3 3 HI 3 iH 3 rH 3 1—1 3 rH c c o 3 M HI 3 3 3 -H 3 *H C -H C •H •H o

CJ 3 4-1 3 PS iH Pi

O Pi

O

M

O

H o 00 3 U

rH 3 o

a.

x 'T E E o 3 3 13 W C • A CM E3

rS1 CO 'O- \C> r» CM CM CO CO CO co O 3 X rH rH o o 3 3

Eh Eh 33 33E

rH *-» rHHO 33 r—1 3 3 J-i 3 0C

Eh

X II m

m I III IiI o3

a)co E3

COoo

CO •H> 3 X

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.

64

5.2.7 Aniline Point

The aniline point is defined as the minimum equilibrium solution

temperature for equal volumes 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 differences, the aniline point is often used to provide an

estimate of the aromatic hydrocarbon content of petroleum mixtures.

Oils with high aromatic content have swelling and deteriorating effects

on natural and synthetic 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 n-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 temperature 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
'

I

\

I

I

a
65

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 evaluated in this study but is

a thin-film version 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.

The D 611 test procedure (method A) was evaluated for use with

recycled oils. As part of this evaluation the aniline point was determined 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 consistent 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.
-
Table

1?.

Repeatability

of

the

Aniline

Point

Test

Procedure

for

Distillate

Fuel

Oils

(D

611,

Method

A)

66 o<

4J CM > c —s

P~k /*\

r P—s 1-4 •H r—* o O o m vO o • 3 O • • • • • • 3 3

CU Ui r~ CO vO 00 co MO o JO o <3- co CO HT 2: o 3 v> i—1

rH *i i—4 r—4 r—4 p V-/ >-/ •—p

V/ ' '—p 3 o

•H o 3 4-1 r—1 o O o O CN CM O 3

•H <— • • • • • • 3 p—

p st CT> o CTV CM o l-i 3

<5; MO

m 00

m vO 00

O 3

4-1

— « Pk - * n 3 3 O o o CM o o 3 l-i • • • • • . • 3 3

'3- CTv o CTv CM o 3 a. VO m 00 in vO 00 4-1 cu 3 3

X3

4J

4-1 P

•rl •HO 3 a- > O • 5 o c 3 3 cn 3 o rH 3 5 "3 rH 3 3

rH rH o o 3 3 Op 3 •H

r—4 3 H

H 3 J>S o • rH

J-l 4) >v XI JO

O

H pH a. 3 •H o >v 1 l-i 3 •H i-i O c

r—4 B

B -a 3 o 3 -H 3 o 4J 3 o 3 o- 4J o J3 •H i—4 •H Xi ?o rH o 3

00 3 i—4 3 H )-i 3 3 3 3

•H 3 3 3 3 3 3 B l-i •H

t-3 S >4 s a > <4-1

O <4-1 p- cn *3 3 3 JO

4-1 i-i 4-1 3 o 3 4-1 rH U-l rH J3

r—l pH 00 pH •H cn •H •H 3 4J rH 4-1 i—t 3 3 3 3

U-i •H 3 •H 3 U-4 3 3 3 O s 4-1 3 3 P •H o 3 3 4-1 •H 4J •H i—1

P—N

rH 3 oo 3

4-1 rH pH i—4 /—s

pn CM

a i—4

1-1

C

a •H •H •H CM CM CM >.

r—1

•H •H

•H o o 4-1 CM CM o 3 •H > B

V4 CO o o D£ 3 4-1 3 o rH r—4 •H 3 :s l-i cn 3 pH 3 4J 3 •3 S'? H -3 rH

a) 3 3 S'? 5s? o 3 3 4J •H Q <4-4 U-i 3 rH m pH J3 3 -—p '—p

v-P 4J 3 u i—4 3 3 rH 3 o 3

•H •H

O 3 3 3 <4-1 l-i <4-4 •H

00 oo >v 3

p- 3 o 3 O

1-1 3 pH 3 3 3 3 3 3

•H •H 3 *H 1—4 t—i

r—1 3 •H •H cu > > fa O 03 03 03 u cn 3

•H c 3

4-1

O 3 3 3 o 4-1 3

41 V4

H 3 1-4

OOO

W 4-1U •H rH 3 04 rH >0- pH t—4 rH 3 o •H 3 • CU JO CO CO CN CO CO co 4-1 c 3 cr 4J B B »—4

i—4 XI rH rH rH

O P 3 3

CO 3 fa fa 4^. Eh fa fa 3 3 -H 1-1 •H CO c l-i l-i O 3 3 1-1 3 a. JO 3 3 a cn jo rH 3 3 B cx 3

to P 3 e •H

4-1 3 3 3 rH

•H i—l 3 •H

H 0) • -O 3 3

•H o <r pH 3 3 o a) 3 JO HO pQ <J .3 a. 3 3 1 P—N P—. 3 3 O B 3 3

f-4 (0 i—1

CM 1 CM CM CM •H

C 3 3 j= -3

4)

M 3 0C I N_P ^-p •^-p > 3 CO CO

H 4-1 3 pQ 3 3

67

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 Solvents," has been evaluated and may be used to obtain

the aniline point of recycled distillate oils to be used for fuel.

t

68

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 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 combustion. The results are usually expressed as

"megajoules per kilogram" (MJ/kg) or, more conventionally, "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 value within a particular virgin fuel oil

grade is small, and it is often stated that the value can normally be

calculated with sufficient accuracy from other known data [19]. The

heating value is often not quoted in virgin fuel oil specifications as

it is not directly controllable in the manufacture of the fuel [3, 19].

The specific gravity or the related quantity API gravity, normally

included in fuel oil specifications, is often used to estimate the

heating value of virgin fuel oils [19], and this will be discussed later

in this section.

69

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 procedure, ASTM D 2382-76, "Heat of Combustion of

Hydrocarbon Fuels by Bomb Calorimeter (High-Precision Method) ," is

similar to D 240, but modified to provide increased measurement precision for special applications such as weight-limited vehicles. D 2382

is based on procedures developed at NBS [23]. This high-precision test

procedure is not required for routine measurements on burner fuel oils.

70

The results of D 240 can be expressed in two ways, as the "Gross

Heat of Combustion" [H or (^(gross)], or as the "Net Heat of Combustion" [H^ or

<3^ (nec) ] . The gross heat of combustion is defined as

"...the heat released by the combustion of a unit mass of fuel in a

constant volume bomb with substantially all of the water condensed to

the liquid state" [2]. The net heat of combustion is "...the heat

released by the combustion 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 measured

directly when using conventional bomb calorimetry, and is the quantity

preferred by the ASTM for reporting the heating value of fuel oils [2],

net heat of combustion, H , is stated to be the most significant value

n for estimation of heat system efficiencies. However, the accurate

determination of H^ requires knowledge 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

The

Experimental

gross

heat

of

combustion

[MJ/kg

(Btu/lb) ]

71

/> s s •n on o> r». 00 CO M0 CO o

CQ MO oo CO i—1

i—1OO r- r-- r-1

ON cr*

O CM f'. UO o CM

CO > A

A

a

a

AA 0k

A

•H Ui co co ON CO 00 00 on o o r—1

rH i—l f—1

1-1 rH rH r—1 U 4-1 3 CO '— V-/ M/ v s hi CM CO CO CO CO v£> CM E O i—l rH CM CO uo CM m CO O X> • • • . • « • # CJ CO <r <r <r CM CO CO <r vj- s—1

'3- < <r <r >3- <r MJ —s

r—« N /—V

-Q co CO o CO <J“ o o < MO CO on m M0 CM in uo H CO rH on o M0 CO o CO

CO

MaA

A

A

•H

H CO CTn CO CO CO CO CTv ON

OO rH rH rH i—i rH rH rH rH

l-i nl 3 to v-/

w v_x M/ v-/ MC E H CO o 00 CO CM CM rH 1—1 S O . CO uo rH on < o m o O -Q « • • . • • • • CJ CO oo <r <r rH CO <r <r UO

i—1MT 'T

X"S yrs /TO /T, /N yr-s /T-S /TS /—N X-S 3 CO CO M0 CN UO O o CM nO rH CO ON CM <04 00 o co <r vO r^. CO <r CM rH O'. o NO M0 <r <r co co c CO ON or <r CO CN rH rH M0 I-- r-~ o c CO CO

<unj

i-i TJ CO CO CO 00 CO CO CO 00 CO CO CO CO ON ON ON ON

0) o rH rH rH rH rH rH rH rH rH rH rH rH rH rH rH rH

44

H V-/ 'w' '•w*' v-/ v»/ . 'W

(0 n> Pi 0) UO

m r*- <r UO uO

m ON o UO MO ON ON CO CO

DS o o ON ON o O rH rH <r UO MO nO CM CM ON ON

<r <r CM CM or CM CM cn co CO CO <r <r <r <r <r <r <T <r < MT 'S’ <r MT >3 vT 5u3 o

c. i—l i—i X •H •rH w i—I O O i—l i—1 3 tH T-f -H TJ i—l 1 TJ 1—1 TJ o o i—l i—l o O ai in | TJ /—v 3 •H 3 • •H 3 <u co o 3 3 T! CO o 3 •H CO HI rH 3 3 1—1 rH 3 l-i OJ 3 3 CJ Hi & 0) 44 4-1 3 3 3 44 •H <u tH TJ iH 3 3 3 <y > 3 14 3 > > '—r o u 44 TJ TJ 4-1 4-1 4-1 -H 4-1 CO 03 4-1 •H Hi

t—l CJ <0 3 •H 4J iH Hi iH HI 3 3

x> tn 3 i—1 i—1 3 3 CO

O CO 0) CO o CO

O 3 0) •H O O •H iH O E O 3 -X O S •H H Q 60 >N >N 60 60 Cu O CU •H CJ CU o U n o O 1-1 E hi e 4-4 o E HI O 3

•H 3 3 H •H

O 3 o 0) HI o 3 Hi 4-1 > Pi Pi > > CJ 3 CJ Hi CO CJ 3 44 3 3 Hi rH 3 UO m 'S- CM O CM CO CO

CU JO CM CO CO CM CO CM CM • CO B E i—1

rH 1—1 o i—1 O

O o 3 3

CO 3

Eh pH Eh Eh Eh :s E:

rHHO 3

TJ i 1 rH 3 3 Hi 3 6C Eh

U0

m uo vO M0 ii 11 j1

as ja o

Reference

method

was

similar

to

ASTM D

2386,

which

isa

more

precise

method

than D

240

[23]

Test

procedure

used

was

ASTM D

240.

72

is described in reference 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 recycled oils provided a precise baseline against which a

comparison of the heating value of recycled 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 constituents, 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
!
73

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 recycled 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 combustion 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 percent of the measured heating value.

The equation upon which these tables are based is given in reference

24 :

(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 following factors:
I

I

I

I

I
74

(gross) = 1 . 8 [ (12,400 - 2100 d

2

) x ( 1 )

Equation (1) can also be written in terms of API gravity, using the

relationship between specific gravity and API gravity given in Section

5.2.5 of this report:

<4 <sross) 22 > 300 - (Btu/lb)

iT (2)

Qy (gross) = 51.869 -

( i 3X~

5

~5 +

8

' ° ^Tfyz

- (MJ/kg) (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:

- 0.01 (% H2 0 + % ash + % S) + X* (% S) (4)

where = corrected heat of combustion. 7

= uncorrected heat of combustion (from eq. (2) or

(3) in the text). 8

The symbols Q and Q are those used in reference 24; Q corresponds

to H as H is defined in D 240.

g g

With slightly less. accuracy , table 19 may be used.

8
r
75

Table 19. Uncorrccted Gross Heat of Combustion for Fuel Oils

as Estimated from Their Gravity [24]

Uncorrected gross heat of corabusGravity Density tion at constant volume (Q ) Degrees

API at

60° F

Specif ic

at

60°/ 60° F

Pounds

per

gallon

MJ/kga Btu/lb

10 1.0000 8.337 43.08 18,520

11 .9930 8.279 43.21 18,580

12 .9861 8.221 43.33 18,630

13 .9792 8.164 43.45 18,680

14 .9725 8.108 43.56 18,730

15 .9659 8.053 43.67 18,780

16 .9593 7.998 43.78 18,820

17 .9529 7.944 43.89 18,870

18 .9465 7.891 44.00 18,920

19 .9402. 7.839 44.10 18,960

20 .9340 7.787 44.21 19,000

• 21 .9279 7.736 44.31 19,050

22 .9218 7.686 44.40 19,090

23 .9159 7.636 44.50 19,130

24 .9100 7.587 44.60 19,170

25 .9042 7.538 44.69 19,210

26 .8984 7.490 44.78 19,250

27 .8927 7.443 44.87 19,290

28 .8871 7.396 44.96 19,330

29 .8816 7.350 45.04 19,360

30 .8762 7.305 45.13 19,400

31 .8708 7.260 45.21 19,440

32 .8654 7.215 45.29 19,470

33 .8602 7.171 45.37 • 19,510

34 .8550 7.128 45.45 19,540

35 .8498 7.085 45.52 19,570

36 .8448 7.043 45.60 19,600

37 .8398 7.001 45.67 19,640

38 .8348 6.960 45.75 19,670

39 .8299 6.920 45.82 19,700

40 .8251 6.879 45.89 19,730

41 .8203 6.839 45.96 19,760

42 .8155 6.799 46.03 19,790

43 .8109 6.760 46.09 19,820

44 .8063 6.722 46.16 19,840

45 .8017 6.684 46.22 19,870

46 .7972 6.646 46.29 19,900

47 .7927 6.609 46.35 19,930

48 .7883 6.572 46.41 19,950

49 .7839 6.536 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)

.

76

X = 0.09A1 = 22.5 x 4.183 x 10 ^ for units of MJ/kg;

** 40.5 = 22.5 x ogQ x 1*8 for units of Btu/lb.

4 . ioOO

% H2O = 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 composite

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 recycled oils) . Using equations (2) and (3)

,

the uncorrected

gross heats of combustion were then obtained (Q^) . These values were

corrected for the water, ash, and sulfur contents of the samples using

equation (4)

,

and the corrected gross heats of combustion calculated

(Qy) . 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 30.

The test procedures used to obtain the various corrections in table

20 were ASTM D 95-70, "Water in Petroleum Products and Bituminous
'
Table

20.

Comparison

of

Estimated

and

Experimental

Gross

Heats

of

Combustion

[MJ/kg

(Btu/lb)]

77

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78

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 appropriate test method for ash required additional

evaluation since equation (4)

,

an empirical equation 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 calculation 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 compared 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 exception

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.
-
79

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 evaluated 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.
1
80

In addition, our limited results indicate that the indirect method

for estimating heating value, as described above and with the appropriate

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.

e

81

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 procedures 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.

82

5.3.1 Water and Sediment

Water and insoluble impurities (sediment) are present in most crude

oils and in some semi-refined 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. Sediment

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 equipment (excluding

copper and copper-containing alloys) , and the corrosive deterioration of

storage 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 sediment 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 commonly used for the determination of water and sediment in petroleum products are the following:
v
83

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 generally used for virgin

fuel oils and is the method cited in the ASTM specification (D 396-76)

and the Federal specification (W-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 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

84

solvents or solvent-demulsifier 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 Materials 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,

demulsifiers, 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
.
85

obtained in accordance with the latest edition of Method D 95 - API 2560

[note: water by distillation] and Method D 473 - API 2561 [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 Petroleum 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; condensed solvent and water are continuously separated 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 Standard 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 constant weight.

86

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 recommended

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 procedures constituting

the D 96 Base Method Ci.e., D 95 for water and D 473 for sediment).

The precision of D 95 (water by distillation) is stated to be as as

Table

21.

Results

from

Centrifugation

Methods

for

Water

and

Sediment

87

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88

as follows (on samples of equal volume, using 10 mL or 25 mL traps) [2]:

>, RepeatabilityM - Duplicate determinations of water by the same operator

should be considered suspect if they differ by more than the following amounts

Water Collected

mL

0 to 1.0 0.1 mL

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:

i

Water Collected

mL

0 to 1.0 0.2 mL

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

is greater.”

It should be noted that D 95 does not require reporting of the sample

volume taken nor the water volume actually collected, leading to possible

' 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 the^e tests are found in table 22, and indicate

acceptable repeatabilities for these samples. These results tend to
I fI
89

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 recycled 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

90

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 performed on sample W022, and the toluene solvent containing the

dissolved used oil plus any particles passing through the thimble was

collected for examination with an electron microscope. To 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
1
91

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<u <l) <u

3m1 P1 OO

Dr 3

co o > tu d>

r—1

dJ TO

+1

pp •H

p P •H P O

-H 3 3 4J o P

tH 3 O o o 0 ^ o .—. d) Dr •H 0 tn tn e p < 4-> fa t—1 X d> •H -— — o d) P

<d jj 4J

X TO TO 3 0

4»

a t—

H 3 CO 0 o O 4M 41 TO

(0 •H •H

H fd 0 -H 0 *H 3

a) P 0 0 -P P -p P H to <d Dr o •3 tn <u tn 0) (d <u

aj tn rH

H 0) TO Di TO Dr 3 p >i

fa a> d) a) to dJ <D TO -H 4J D 3 3 3 <u tn dJ tn •H 3 -H

4-1 4-1 4M 3 4m 3 tn

D1 H • d) •H ‘H d) d) -H

CM TO to 4>

HH

HH

p P X

CM ai

v •H

H Qr •H Dm td rH H tn 0 c 4) 4>

a) CO

O o 0 ^ § •H o <d

r—!

>1 >i Dr to tn TO tn tn 3 dJ

A

a o E a) ^ d) * P Dr

(0 a) d) 0 tn tn -H d) <U Eh fa fa U D D > i ^ h x: o tn > *HH

«H d) XI *H h id 0 o Dr 4J TO 1 i 1 E tn rH (d in in 1 i 1 10 id d)

a)p 1 i ! w 3 O'

fa 0

fll

Table

23.

Repeatability

of

Test

for

Sediment

by

Extraction

(D

473)

92

co

CO

A vO

4J 03 o rH a> * X 0J • fH • CM

6C rH o • o CO

•H -0 <r • 03 6 0k •k o £ •H O CTi CM 0k cd X 1 CO rH o in vO 0k > u 1 o o o «<r oo in rH CNI X 1 • • • • r^. • <r

•r> 1 o o o <r • v£> • . S'S a» co rH iH

03 0% 0k #» #» *> 3 CO rH vj- cd * <d •k •* 03 03 CO O O 00 o m <r <T d c*s O rH O CN Cn iH nt cni UO o . • • • • • • • . •H o o o HT CO vO o o CM

4Jdd 0k -u r^- d m co

a) • • o o rH d 03 rH kO C\ o CO o a) iH rH rH •k •k r- vO o rH O o o iH co < o O • • • 43 <r co • .

4-1 • £ o o O • • « o o d •H O «H iH

03 -C

n 0k * 0k •> £ 4-1 CO cr. CO X •> •k #k UO

•H rH co <r rH uo iH ON VO rH CO

03 2 O o o o o O CO

O

O o

0) 03 • • • • • • • • • • cn IS o o o o rH *H rH o o o

0) S-i rH 03 rH o CM CO <r CM co a H3 CO CO CM CO co CM CM 6 £ rH iH o rH iH o O

co 3

co

d

Ch Ch P-* Ch 12

4-1 Xo

4-J o

<D ^ 03 1 < O o 0 4-1 0) d o CJ o A 0k 4-1 \£ d' •H

d 1—1

rH 3 o 3 4-J o 0k •H •H d o O CJ •H rH rH rH O O 4-J 03 d

4J •H

H •H 03 03 '

* d

cOO

O rH rH 03 03 4-1

n

n 03 ^ 0) 03 03

d

X

d rH iH <J iH

a 3 < 3 pa 3 03 03 0) CJ 0) 0) 03 44 4-1 rH 4h d

cn 3 3 03 3 03 03 0) 0) -H •H 60

03 4H uh

a 4h

a 03a 03

O 4->

O rH 4-1

d

Qd

d 03d 03d •H •H 03 •H

d

d 3 d 3 rH 3 >H 3 03 03 o d

d

•H •H

O •H

O

a o O

O

O > 1 3

60 60 03 60 03 03 03 Cu *H 03 03 03 d d ^ u s_r CJ CJ ' E hi 3 d

•H •H •H 03 03

O 03 03 > > > Pd PS CJ 33 0360

603

eu

•HO 03 03 rH d

03

d 3 et

(<4

v£>

mm l t i I I l

(U i—i x9xH

«]

93

- • *> *v7 V XV. *, s».

. -> '

.

’ '« -• ftPi- r'.'S e./T

• . **•' « • ;

*•' £-<•* •'

• .* '* '• • ’ . ft. . • ^ • .

• - • . .-* ? *• */ . * •#» * * !' • *- ; ‘ v>rr.- . '*

• v*

• 6 f «i' r. ^ :

•: <i v. • f

' * ''..vv:n t 9

: -L*

: te

4*r*u * />.

6* .

7*

: •«& .-,**•

* L..^V

*6* • , V'/' - • V

*.«*

i •* s' Wf .

\** ^

•

<s

ft %

'

% t &

’

*

. - "A

%

• «

-

--ft '** * • % \

*

ft #

fti ^

*£ O •or

Gk v, * *

5 pm

. On.^4

ft

»

* © f * *V

ft..- *Q

*

' <3. l

0-5 pm

Figure 2.

Electron Photomicrograph of

Particles in Used Automotive

Oil Extract at 2500 X

Magnification.

Figure 3.

Electron Photomicrograph of

Particles in Used Automotive

Oil Extract at 25,000 X

Magnification,

a

<&•

L-. 0-1 pm

Figure A,

Electron Photomicrograph of

Particles in Used Automotive

Oil Extract at 100,000 X

Magnification, (Note apparent

agglomeration of particles)
nm
94

observed have a size range of 20 nanometers (nm) to 0.3 micrometer

(ym) , 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.

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 sediment 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

r

Table

24.

Sequential

Sediment

Determinations

Using

Single

Thimble

(D

473)

95

pi X

•H3X

8^3o

•H

PI3

COuuX3

fol X

HU

O ON CM cd NO

M 3 co r—( o 1 ND iH ON

•H cn o o o l m r— X 3 • • • i • • H o o o 1 NO rH o

•3 CO rH <r CO aj 00 ON 3 co o o CO m CO ON O 3 O rH o CM rH >3- NO O CO • • • • • • • CU CO 3 o o o *<r vO o o

»H ON CO ON r~-m

X CO -O’ tH

m tH tH ON

Pi o o o o o o r-

*HX4-i o o o rH tH o o 3 P<

i-i a) CU X G E

CO 3

CO 3 o o CN cn 'cr CN

cn CO CN cn cn CN CO

tH rH o rH rH o o

pH Pu Cn :s m «3o

Pi 3 3 3 3 o o > O

Pi Pi iH CO • 3 3 pi '

/ 3 3 O O O O o CD CO 6 rH •H •H V-/ N-> o •H XJ

PI 4->

Oa

a rH rH 3 3

tH •rl •H 3 3 pi

Pi rH rH

O

O PI pi

O •H •H TJ CD

X

CO

O

O rH rH 3 3 3

ai 3 a) CO « rH rH 3 3 3 60

<U 3 4-1 ipi rH 3 3 3 3 3 •H IH 4H *3 •3 PI •H U

01 3 •H Pi 3 3 3 rH rH m j-i 'O

•H •H

O 3 o 3

t>0 60 >N >N a, 3 "0 M Pi 3 O G •3 3

•H -H 0) 3 o C 60 > > P3 Pd u M 60

rH

•HO 3

-3 rH 3 3 Pi 3 60 pH

vO NO

m

m

a) rHX3XH

96

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.

The solids content of an oil may be determined using ASTM D 893-69

(amended in 1978), "Insolubles in Used Lubricating Oils." 15 This method

is identical to Method 3121 - Federal Test Method Standard 791S. It

covers the determination of substances which are insoluble in pentane

and/or toluene (Procedure A—Pentane Insolubles and/or Toluene Insolubles)

,

and substances 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

10

The 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].
1
97

useful for the determination of "insolubles in used lubricating oils," and

for the coagulated insolubles," ...additional finely divided materials that

may have been held in suspension because of the detergent character of

the oil" [2], 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 summarized as follows [26]:

"A sample of used lubricating oil is mixed with pentane-coagulant solution

and centrifuged. The precipitate is washed twice with pentane, dried,

and weighed to give coagulated pentane insolubles. For coagulated

toluene insolubles a separate sample of the oil is mixed with pentanecoagulant solution and centrifuged. The precipitate is washed twice

with pentane, once with toluene-alcohol solution, 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 evaluated 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 results of these tests are
,
98

found in table 26, and the experimental repeatability is consistent 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

product [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 593 (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 procedure for coagulated

toluene insolubles, D 893, appears to provide a useful indication of the

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.

Table 2

5..

Precision

Criteria

for

99

VO

COON

00o

44OM333

to

0)oo

a, 3 3

•H3 3

•H CD O 3

a)3

cu3 3 3 CO •H rH 3 3 a) 3 o E 00 E DO O CO r~- vO <r o O

O 40 o 3 O 4-1 o rH rH t-H 4-C ro vO 00 o d •H • o . • • • O • • • • O o o o o o O o o rH

•H 3

CO c o m a) CD rH

DO33

<Dd3>

rHO

CO 3 o o . CQ

0) • o • o a »H • rH • M

rH rH »3- CO rH rH CO rH *• • • 1 • i • • • • d d 3 3 O O o Hi o o o rH o o c O 3 o 3 •H vO •H

CD • > • > HI rH HI

DJ o o o O 3 CM 3 c 3 • 3 o cr O O* o 3

II 3 3 « 3

Dd >s CO DO

HJ HJ 3 HI •H rH E rH DO E o •H 3 o

Hi DO rH Hi 44 3 O 41

HJ CO *3 3 d TO 3 3 •H 3 > a. >

4) 3 4) 3 •H 3 3 •H *3 d d d d 3 PS d Hi

0) cO 4) CO 3 3 3 3

CO 3 3 Hi 3 -3 3 -3 3 d rH d rH rH

(U o 41

O 3 O 3

Pi

H PH

H Hi HJ Hi 3 3 > •3 3 3 3 HJ 3

HI 3 HJ 3 T—1 3

*3 3 *3

00

d 3 d o O o

>N >N

H

a •H

HI Hi CO 3

>N >v •H •H

a iH

HI Hi rH rH

O 3

•H •H •rl

H 3 CO 3 O rH rH DO DO Hi Hi cu •H •H •H H 0, w a.

>> DO DO

OO

H CO CO 3 3 3 3 3

4-1 HI •3 *3 3 Hi 3

to CO

O

O 3 3 3

0) 4) 3 Hi DO DO DO

a. a. cu cu , H £ H 4) 4) 4) 3

PS PS pci PS 3 DO o o HJ

HJ

do 3

T3 •H 3 •H 3 HJ TO QJ •3 Hi 3

•H

O DO 3 i_j 3 CU HJ w •H 3 > H

TD 3 Hi Os o iH O Q HJ *4_j 3 DO 44 Q iH 3 HJ 2 r—1 c/1 S 3 •H rH 41 rH r. JO *H

HJ o DO CM •H

O

•H 3 1 3

r—N HJ

a 3 T)

Cs -H TO GJ

H HJ 3 3 O CO CO •H 3 3 Hi D C rH d HJ CU

•H 3 HJ 3 u-» 00 DO rH Hi O

•H 3 P

ON 3 •H

g Hi to rH 3 o O e

TO

r CJ

O •H 3 O 3 CU rH d Hi 3 cu 3 Cl* r—1 H 3 p

*3 3 DO CO •H 3

Hi 3 < DO 3 3 >-/ rH HJ Dd O 4i 3

HI

d 3 o Hi rH o d 3 DO

HJ •H •H 3 ^0 3 3 3 3 HJ •H

PQ •H 3 HJ 3 rH M •> 3 C 3 JO 3 d 3 3 d 3 Hi o Hi 3 •rl •H CU rH HJ 44

('» HJ

O

r~*

O

m •H >, HJ 3

ON TO Hi 3 3 • TO O TO 3 3 c o 3 HJ 3 HJ Hi 3 3 HJ rH CU rH

iid Hi 3 3 DO M O rH 3 HJ O

Os DO 3 3 3 Hi HI 3 00 Hi CU •H • rH 3 Hi rH 3 Hi O >% 3 rH

•rl 3 3 o Hi 3 3

DO rH HI

O rH -4 •H D3 d «s HJ 3 3 3 3 -H CO 3 d d 3 rH Hi 3 3

TO o Hi 3 O 3 O 3 O Hi DO 3 3

Hi

d

O 3 3 •H DO

Cu •H CU TO rH 3 3 3 Hi HJ 3

PS 3 3 3 3 1—1 d DO O HJ 3 3 H Hi £ DO 3 Pi •H • 3

rHr—

O HJ 44 CO o

HI • • 3 O 3 3 DO ON

TO HJ HJd r-H 3 3 O o O

HJ

d jd 3 r» 3 o ‘rl o 3

r-l 60 3 u CM 3 £ 3 d 3 3 3 CJ 60 iH CU >. TO 3 3 3 E rH 3 £ O o •H o 3 3 o 3 rH a ’“0 O o rH HJ 3

II o 3 44

r CU CO

U-l 3 o PO

D « HJ 3 M 3 3 d 3 n

DO 3 3 o 3 3 HJ DO O *H 3 ,—|

Hi HJa 3 o 3 TO Hi 3 3 CO DO T3 41 3 3 DO c 3 3 o CU CO 3 •H

100

033

d>duod

XiH

hi »3

6C r- P * •H rH r>» r» 00 O' cn tO CO to to d CO O tO CM CO vO oo CM cn 00 O'

CO

dd • • • • • • • • • • #

CT\ c rH

O o o 'O' o o CM o o o /—v CO d p w P 3 3 • P X Q rM i—1

CM

M * ft ft ft «t ft •k 0k

d

v»

O

O o rH Cn CN tO

O COO to COm hi

H CO o o m rH CO r-' on CO cn 00 O'

d 3 • • • • • • • • • • • d • u w •H o o o o '0- o o CM o o o d CO 3 d to cn

•3

T—1

00

a>

p o 3 03 P o i—i

CO P o -d

d

u o o rH o CO co <r CO cn CO

m 3 3

PM CO o O CO f'' CM on CO •<r co r-' MT fH •H 3 CO • • • • • • • • • • • CO u •H d o o CO O' to O rH CO to to CM > d)

COd tH rH

d

a) •d 3 P /r~\ •H H d cO 3 0k -Pft

ft 0k * CO tH

•u hi rH #» rH

A 0k •t * O »d O' •H

CO CO 3 o o f"

m cn <T CO rH CO CO

m <r

O

a>-

T—1 d co o O CM CM ON CO CN cn 00 ON

d

tH 3 P-c 3 • • • • • • • • • • • Q P P 60 fH o o CO to O rH CO m to CO t-/ co 3 C0 rH

i—1 OU 3 O CJ 3 o

?H

•HO

d

d> rH CO d H 3 6C Em

CM v£> vO

m

m

d

*d

a)CDdSo

tH

HI

CO

P< hi3d

CO tH

d Pi .h d CM 1 1 o CM CO 'T <r CM CO <r CO 3

cd

O3 3 P p CO CO CO CM CO co co CM CM CM CO P O

60

B

B .H rH iH

O rH iH rH o o o o H

O

COO

CO 3

CO 3

Eh Ph Eh Eh Ph Eh Eh :s & Pi HIc

cd iH3

60

y-N

d to »H < P d Pi o O > CO CJ d d •H Sn So o o HI T—i d t—f H» Pi Pi o o 0* o 0k O •H J3 Pi H 3 3 B HI < HI C HI P O HI d

rH

O

O o Q

•H 3 CO CO cO HI Jd

d Jd

d Jd

d 03 X!O

rQ

O Nff tH rH 3 d

a < o CJ P a o •H CM

H

d •H •H

H cd o u o Pi o Pi P HI HI rH rH f—1

rH

OO HI 3 d HI 3 'd HI 3 HI 60

cd

a

H •H •H

H •d 03 o o 03

O o 03O 3 >N

d •H

O

OOO rH iH

d 'd 03 •H 'd 03 •H H3 03

H •H

H

P< Pi

d

d 03d '—Pi a)

H a) '—

O 03 •d

d

O

r—1

rH rH rH 3 3 3 d

d

d

d

d tH 3

Pd 03

dd

dd tH /"S tH /—vtH

H P •H Pi P <H Pi HI

d 3 3 3 3 < P d

d

d a) 03 03 o P tH tH tH tH d) no HI tH 3 60 ?H 3 CO fH 3 d d 3 « d d d d •H •H •H 3 •H •H 3 •H H iH rH

v£> 3 3 3 3 rH

O fH CJ 03 o tH •H o IH •H o tH XX XX dJ

CM *H •H •H •H

O Pi

O PiO

d rHd rH

d 3 3 fH

60 00 60 60 En 3 >n 3 P •d

Hp •d Pi P •d Pi rH tH 3 d Pi Pi Pi pi O O O O B fH d 1 B d 1 B a 1 o O O

rH •H •H •H •H

dw

d co

O *H 03

d to 03

d CO 03

d 03 03

p

co > > > > Pd Pd N-^ CJ o P pi CO P Pi 03 P u 5 3

•H • 0\

•a

a)

cO

r-l3

60

COoo

•d

0) U

cO fH3

60

COO

CJ

a)60 T33

rH

03

CJ3

dJ

•H

CO

a)

>-i EnH

J-l cO iJ HdO

CO rHP

«J x>

a d>

101

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 Oil's 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 relative density

value of 2.0, close to- that of sand, was selected. We suspect that the

102

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 separately, the third way, is also satisfactory

103

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 coke-forming propensity of a

fuel oil. The carbon residue test is generally applicable to relatively

nonvolatile petroleum products which partially decompose on distillation

at atmospheric 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

reducing the efficiency of vaporizing pot-type and sleeve-type burners

or fouling nozzles in small residential- type burners.

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 samples that are mobile below

104

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 requires, "The sample, after

being weighed into a special glass bulb having a capillary opening, is

placed in a metal furnace maintained at approximately 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 Dossibility 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 percentage of the original sample, and reported as Ramsbottom carbon

residue" [2].

For virgin oils, the carbon residue is normally 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 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

105

not separately determined for existing specifications. However, if ashforming 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 content

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 procedure for virgin oils

• is given graphically in the ASTM test method, and examples taken from

this figure are given in table 27. These precision data are applicable

to both distillate and residual petroleum oils.

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

106

Table 27. Precision of Carbon Residue Test Procedure

for Virgin Fuel Oils

Ramsbottom Difference, percent carbon residue

carbon residue

average percent Repeatability Reproducibility

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

a Data taken from ASTM D 524-76, "Ramsbottom Carbon Residue of

Petroleum Products," figure 4.

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 contaminants normally found in used lubricating

oils would increase the carbon residue test results 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

Table

28.

Repeatability

of

the

Carbon

Residue

Test

Procedure

on

Distillate

Fuel/Used

Oil

Blends

(on

10-Percent

Distillation

Residue) - D5

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Table

29.

Repeatability

of

the

Carbon

Residue

Test

Procedure

for

Recycled

Oil

and

-Virgin

Fuel

Oil/Used

Oil

Blends

- D

524

108

T3c

<u

T3

0)

cn3

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o 03 O 3 3

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t-i

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II

II

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03 <

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•H 'O O

a) r—( r—

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'Ou

cn

•T3

4-1 00

O

CN

CNo

^25s

rso

CN

CNo

ts

5-S p-

• sO

*o

4-1 oo

5-5

03 •H 3 H *3

> -a

3-i 03U

o •H 1 CN CO CN rH <r cn rH cn Os cn m o o cn l r- CO Os Os CO rH m cn SO m rH 3 03 1 -H 3-i 1 NT NT <r <r <r o m m m m m o

OO 1 rH rH rH rH rH rH

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-H o ii ii n II

oo >

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-a

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o

cn

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fj-i

033 « O

ss

SO

•o

5S

SO

o

SS SJ o o

Measurement

by

operator

a.

Measurement

by

operator

b.

W022

carbon

residue

is

3.77

percent

(standard

deviation

of

the

mean

is

0.02%,

n=3)

.

109

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 determine the carbon

residue of these products.

110

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 deposits 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].

Ill

Since the ash forming constituents of crude oil generally have lowvolatility, 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 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 No. 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 specif ications 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 recycled oils used as fuel often

contain both lubricating 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.

112

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 "sulfated 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 containing 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 usable for the determination of residues from calcium,

zinc, magnesium (probably), barium, potassium, sodium, and tin [2]; and

• (2) a preliminary 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 caii reliably indicate the maximum level of ash-forming constituents

which may be found in a recycled oil used for burner fuel.

113

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

0 - 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 lor 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

0 - 85

where: X = average of the two test results in units of percent sulfated

ash" [2], This reproducibility works out to 0.027 weight percent sulfated

ash, or 27 percent at the 0.1-p’ercent sulfated ash level, and 0.189

weight percent sulfated ash, or 18.9 percent at the 1.0-percent sulfated

ash level.
.

4ft .
114

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 recycled 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 automotive oils (W022 and W011) indicated

lead recoveries 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 confirmed, and it was

further reported that the phosphorus would most likely be found in the

final ash as the phosphate (P0^“ 3

) or pyrophosphate (P^-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 averaged 880 pg/g (range = 716 to 1035 pg/g.
.m

—
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fj'i II

115

to e

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116

n=6) . These results are consistent with the phosphorus concentrations

reported for 30 used lubricating oils obtained throughout the country

(average = 901 yg/g, range = 81 to 1393 yg/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

1

1

slightly larger than the ASTM repeatability. 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 fact retained in the sulfated ash, and

11

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 yg/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 . .ightly

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)

.

117

this question was evaluated through analysis of the sulfated ash residue

as described below. 1

2

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 _in situ (in their original crucibles) . These

"dissolution recovery", values were higher than the average recovery values

Ti

" There is some evidence to suggest that the compounds of lead retained in

the sulfated ash, while apparently reproducible, are not stochiometrically

lead sulfate.

118

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 that 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]

.

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 sulfated 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.

119

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

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%

Uncertainty values are the standard deviation of the mean, s//n.

Sample U022 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.

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.

120

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],

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]. Lowtemperature 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
'
121

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 unnecessary 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-P.ay Spectrographic 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 recycled 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],

122

This standardization factor is obtained "using an oil sample of similar

type to the unknown 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 proceeds, the sulfur oxides

bleach the blue color, and more iodate is added. The amount of standard

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 interfering elements include iron, aluminum,

calcium, silicon, and lead which are sometimes present 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.

123

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 recycled oils used as fuel.

In method D 1551, "Sulfur in Petroleum Oils (Ouartz-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 evaluated

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 organometallic compounds, both of which are often present in

used oils, and because the method was discontinued by the ASTM in 1976.

124

Method D 2622, "Sulfur in Petroleum Products (X-Ray Spectrographic

Method)," covers the determination of total sulfur in liquid petroleum

products. In this method, the sample is placed in the x-ray beam, and

O 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 previously 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 percent S and the ASTM reproducibility is 0.16 x percent S. This

method is a possible alternative for D 1552; however, it was not the

primary method evaluated for recycled oils because it requires expensive

and highly specialized instrumentation, and because the method may

require 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 repeatabilities 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 Reference

Material (SRM 1623) having a certified sulfur 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
*
Table

32.

Sulfur

Data

for

Fuel

Oils

and

Recycled

Oils

125

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126

this fuel oil was calculated. The standard deviation of these 12

values was 0.042-percent sulfur. The values obtained did not vary from

the average by more than 0.038-percent sulfur, indicating acceptable

repeatability of the D 1552 method for virgin fuel oil.

Table 33. Precision of D 1552 Test Procedure for Sulfur [2]

Sulfur, (wt. % range) Repeatability Reproducibility

0.0 to 0.5

0.5 to 1.0

1.0 to 2.0

2.0 to 3.0

3.0 to 4.0

4.0 to 5,0

0.05 0.08

0.07 0.11

0.10 0.17

0.16 0.26

0.22 0.40

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 instrumentation, 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 show in table

32 and are discussed further, below.

Contaminants normally found in recycled oils do not significantly

interfere in this test procedure. The test procedure states that alkali
,
127

and alkaline earth metals, zinc, phosphorus, and lead do not Interfere,

and chlorine in concentrations less than 1 weight percent does not

interfere [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 automobile 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 indicates that the nitrogen interference will

be very small at low concentrations of nitrogen. For example, for a

sulfur concentration of approximately 2 wt.%, the presence of one-half wt.

percent nitrogen caused an error of 0.06 wt.% sulfur on the low side, or

about 3% relative. Our experimental 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.

128

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 results of these analyses indicated that, except for

one sample (F 133) , the XRF values for sulfur agreed with the hightemperature method (D 1552) in view of the latter's stated reproducibility.

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 discrepancy had been noted, centrifuging did not appreciably

129

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-perceht 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.

r

130

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

+

(H20)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 concentrations 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 (effective concentration) of hydronium ion which it

contains, or

131

1

pH = log ( 1 ) [H+

]

= -log [H ]

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

_ 3 hydronium ion concentration may be 1 x 10 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, say 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 contain 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

132

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 recycled 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 second 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 constituents into groups

133

having weak-acid, strong-acid, 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 inflections 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 quantitation 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: reference 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

134

the petroleum product and the sample is considered to fail the test [2].

There is no precision 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 automotive 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 sufficient amounts of free

water could not be separated 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 a sufficient

quantity of free water (even with high additive motor oils) so that

the test procedure 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.

135

Data are shown in table 34 for the several petroleum oils for which

15 rnL 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 (KOH) on sample F134 using ASTM method D 664 verified the

presence of this buffering effect, and required an average of 4.34 mg

KOH per gram of F 134 for neutralization. ] Recycled distillate fuel oil

sample 7L24 had a much smaller buffering 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.

Table

34.

Comparability

of

the D

1093

and

Modified D

1093

Test

Procedures

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137

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 addition, 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 (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, KOH) used to titrate the acidic components

of the oil sample, and the resulting electrode potential plotted against

volume of titrant (Figure 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 details; for examples used in

D 664, values of approximately - 200 millivolts were used) .
villi
138

Table 35. Repeatability of the Acidity Test Procedure for Petroleum

Oils Using the Modified ASTM D 1093

a

Acidity

Fuel oil

grade Description

Sample

number

Methyl orange

indicator pH

b

2 Virgin distillate fuel oil F131 Neutral « 6.48

Neutral 6.58

4 Virgin residual fuel oil F126 Neutral 6.42

Neutral 6.35

5 Virgin residual fuel oil F125 Neutral 6.48

Neutral 6.33

6 Virgin residual fuel oil F022 Neutral 7.03

(source A) Neutral 7.01

6 Virgin residual fuel oil F130 Neutral 5.93

(source B) Neutral 6.04

c Recycled distillate fuel oil 7L24 Acid 3.60

Acid 3.52

5 Recycled residual fuel oil F134 Acid

d

4.30

Acid 4.22

, .Q Acid 4.24

— Composite used automotive oil W022 Neutral 5.80

• Neutral 5.92

——— Used oil feedstock to re-refiner W023 Neutral 6.32

Neutral 6.42

Used oil from service station W033 Neutral 5.64

Neutral 5.62

*— Used industrial oil W037 Neutral 5.20

Neutral 5.18

3

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 pK = 7.00.

c 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.
1 '
139

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 sulfuric 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 recommended 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 appears to be essentially equivalent to the

methyl orange indicator (including the effect of dilution with the

larger volume of water) would be a pH of 4.5. 12 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).

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 ].
t
Electrode

Potential

(millivolts)

140

Figure 5. Potentiometric Titration of Recycled Distillate

Fuel Oil Sample 7L24

Volume titrant (mL of 0.1898 N KOH)

141

CONCLUSION

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.

142

Acknowledgments

The authors wish to thank Mr. Robert Pedall, Industrial

Research Associate of the Association of Petroleum Re-refiners,

for his excellent technical 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.

We also wish to thank Drs. Ian Bartky and Curt Reimann

of the National Measurement Laboratory Director’s Office for

their advice and suggestions, 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 for her untiring efforts in the preparation of this report and for her diligent endeavors as program

secretary which have significantly contributed to making the

Recycled Oil Program more efficient and effective.
t
References

[ 1] Fuel Oils, Commercial Standard CS 12-48, Sixth Edition

(Sept. 25, 1948).

[ 2] 1977 Annual Book of ASTM Standards, Part 23, ASTM

Philadelphia, PA, 1977.

['3] Criteria for Quality of Petroleum Products, Ed. J. P. Allinson

(Applied Science Publishers, LTD., Essex, England, 1975).

[ 4] Swain, J. W. , Recycled Oils for Fuel Uses (unpublished report

to the National Bureau of Standards - Jan. 1978).

[ 5] Chansky, S. et al., Waste Automotive Lubricating Oil Reuse

as a Fuel, Report No. EPA - 600/5-74-032, Environmental

Protection Agency, Washington, D.C., (Sept. 1974).

[ 6] Swain, J. W. , Assessment of Industrial Hazardous Waste

Management Practices: Petroleum Re-refining Industry,

Environmental Protection Agency, Washington, D.C., (in press).

[ 7] Report to the Congress: Waste Oil Study, Environmental

Protection Agency, Washington, D.C. (April 1974).

[ 8] Anon., Waste Lube Oils Pose Disposal Dilemma, Environmental

Science and Technology 6_, 25 (January 1972) .

[ 9] Berry, E. E., et al, 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. Pet. Inst., Washington,

D.C. (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 Management Program,

(March 1976).

[12] Sahagian, J., et al., Waste Oil Recovery and Reuse Program - Residue Management, GCA/Technology Report No. GCA-TR - 7 5 - 3 - G

,

prepared for Maryland Environmental Services (April 1975).

[13] Cotton, F. 0., et al., Waste Lubricating Oil Research, series

of research reports by the Bartlesville Energy Research Center,

Department of Energy, Bartlesville, Oklahoma (1975 - 1977).

[14] Becker, D.A. , editor, Measurements and Standards for Recycled

Oil - I, NBS Special Publication 488, National Bureau of

Standards, Washington, D.C. (Aug. 1977).

[15] Becker, D. A., editor, Measurements and Standards for

Recycled Oil - II, NBS Special Publication XXX, National

Bureau of Standards, Washington, D.C. (in press).

[16] Kaufman, H. B., (EPA) Private Communication.

[17] ASTM Standards on Precision and Accuracy For Various

Applications (ASTM, Philadelphia, Pa., 1977).

[18] Significance of ASTM Tests for Petroleum Products, Special

Publication No. 7-B (ASTM, Philadelphia, Pa., 1955).

[19] Boldt, K. , and Hall, B. R. , eds., Significance of tests for

Petroleum products, Book, ASTM Special Technical Publication

7C (ASTM, Philadelphia, PA, Jan. 1977).

[20] 1976 Annual Book of ASTM Standards, Part 30 (ASTM, Philadelphi

Pa, 1977).

[21] Minutes, Subcommittee on Statistical Methods, ANSI Committee

Z-l on Quality Assurance (Sept. 10, 1975).

[22] Davis, E. C., Private communication, Naval Ship Engineering

Center (Oct. 13, 1977).

[23] Precise Measurement of Heat of Combustion with a Bomb

Calorimeter (NBS Monograph 7, 1960, out of print).

[24] Thermal Properties • of Petroleum Products (NBS Miscel laneous

Publication 97, Nov. 9, 1929).

[25] Guthrie, V. B. , Ed., Petroleum Products Handbook, (McGrawHill 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.).

[27] Burke, R. , (NBS) private communication.

[28] Whisman, M. S., et al . , Waste lubricating oil research:

part 4, BEF.C . RI - 76/4 (Oct. 1976).

[29] Gorsuch, T. T., The Destruction of Organic Matter, Volume

39 of the International Series of Monographs in Analytical

Chemistry, Pergamon Press, New York (1970).

[30] Bremorris, E., et al., Materials Research and Standards 7,

459 (1967).

[31] Kolthoff, I. M. , and Sandell, E. B. , Textbook of Quantitative

Inorganic Analysis, Macmillan Company, NYC (1948).

[32] Handbook of Chemistry, 8th edition, edited by M. A. Lange

(Handbook Publishers, Inc., Sandusky, Ohio, 1952).

[33] Laitinen, H. A., Chemical Analysis, McGraw-Hill Co. Inc.,

NYC (1960).

[34] Kruger, J., (NBS) Private Communication.

APPENDIX A

Energy Policy and Conservation Act

Section 383

Report to Congress.

Energy impact

Statement.

42 USC 6363.

Defmltiboi.

Rules.

Pub. Law 94- 163 - 70 - December 22, 1975

the agency determines lias the effect of requiring, permitting, or

inducing the inefficient use of petroleum products, coal, natural "as,

electricity, and other forms of energy, together with a statement of the

need, purpose, or justification of any such requirement or such action. Each such report shall be submitted to the Congress within one year

after the date of enactment of tiiis Act.

(6) Except as provided in subsection (c), each of the agencies

specified in subsection (a) (1) shall, where practicable and consistent

with the exercise of their authority under oilier law, include in any

major regulatory action (as defined by rule by each such agency)

taken by each such agency, a statement of the probable impact of such

major regulatory action on energy efficiency and energy conservation.

(c) Subsection (b) shall not apply to any authority exercised under

any provision of law designed to protect the public health or safety.

FEDERAL ACTIONS WITH RESPECT TO RECYCLED On,

Sec. SS3. (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 consumotion 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. (b) As used in this section r (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 “recvcled oil'

1 means

(A) used oil from which physical and chemical contami- nants 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 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 whicli 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.(-D 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 otherwise^ 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.

(d) (1) (A) T\ ithin 90 days after the date on which the Commission receives the report under subsection (c), the Commission shall,

by rule, prescribe

89 STAT. 940
1 If
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 00-day period, the Admin- Rules,

jstrator of the Environmental Protection Agency shall, by ride, 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 pursuant 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 ]awr 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 standards prescribed under subsection (d) (1) (A) (ii) ; and

(2) no rule or order of the Commission may require any con-_ tainer 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) revi sing 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 governments 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.

TITLE IV—PETROLEUM PRICING POLICY AND OTHER

AMENDMENTS TO THE ALLOCATION ACT

Part A—Pricing Poi.ict

OIL TRICING FOLIC

Sec. 401. (a) The Emergency Petroleum Allocation Act of 1073 is 15 USC 751 amended by adding at the end thereof the following new sections : note.

89 STAT, 941

APPENDIX B

Fuel Oil Specifications

i

.H RICAN NAflON

standard

3naT)

zsmJ AN SI /ASTM D 396 - 76*

Standard Specification for

FUEL OILS 1

This Standard is issued under the fined designation D 396: the number immediately following the designation indicates the sear of original adoption or. in the case of revision, the year of last revision. A number in parentheses indicates the year of

last reapproval.

• 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-buming 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.

\2 This specification is for the use of purchasing 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 1. 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

Tester 3 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.S

cSt (45 SUS) at 3SC C (100’FMnis 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 Oilsd 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. 1, 2. 4. and 5 snail 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 ProJucts 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 " -\n Evaluation of Methods for Determination of Sulfur in Fuel Oils" bs A R. Crawford.

Esso Mathematics & Systems Ir.c. jnd G. V. Dyroff. 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

D 396

Oils by Centrifuge: 3 and Grade No. 6 by

Method D 95. Test for Water in Petroleum

and Other Bituminous Materials. 3 and

Method D 473. Test for Sediment in Crude

and Fuel Oils by Extraction. 3 4.1.4 Carbon Residue—Method D 524. Test for Ramsbottom Carbon Residue of Pe- troleum Products. 3

4.1.5 Ash—Method D 432. Test for Ash

from Petroleum Oils. 3 4.1.6 Distillation —Distillation of Grade

No. 1 and No. 2 oils shall be determined in accordance with the Method D 36. Test for Distillation of Petroleum Products. 3

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 3 and of Grades Nos. 4, 5, and 6 in accordance with

Method D 38. Test for Saybolt Viscosity 3

4.1.8 Gravity—Method D 237, Test for API Gravity of Crude Petroleum and Petro- leum Products (Hydrometer Method). 3

4.1.9 Corrosion —Method D 130, Test for Copper Corrosion by Petroleum Products,

Copper Strip Test,'1 3 h test at 50’C (I22°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,2-3 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- In addition, the sulfur of Grade No. 1 may be

determined by Method D 1265 , Sulfur in Petroleum Products (Lamp Method).2-3

‘ Annual Book ofASTM Standards. Par( 24.

214

TADLE

1

Detailed

Requirement*

for

Fuel

Oil*

D 396

x

n

0.5 or

legal 0

5. *

or

legal legal legal legal

L

Ly.S-i %

Civ, G 3

X

n2

r-> m

6 6

* • • z z

0 c ri c

C' 3 0 • . *r = r-' c . . =°.«n «0

O r~\ O *"*»

Kinematic

Viscosity,

cSl°

cj r7

»

• -

O •(N <=-

Xn2

. . • • oc

2

• • • • r4

•

* )

• rf

CT0u•COr%<

X2

^ . ft. r<

r>4 m

^

«n« ->o 522

_c2

_ b

3 0 ®p 'O — ra <n A A

Saybolt

Viscosity,

s"

O

b ^

a ^

— ^

O ~

3

u.

x

n

12

• • • • o' • • |

* *T

cI

•

• •

• •

•

• m • r>4

CJbn-§

0 —

>eD

X2

°\ o' o'

• r* r* 0 0 * m — . m O'

c 0

>0 ^ rv«

•

• <nm

^ TA TA

• £n *j 3 3 Q u

CL£H

v5O

O

2

M O . tO O

atw-» m t

rd ^ m ^

• •

2 ^ = : : : S c.

• : 1 §! X2

-S' " ^

CM T • • •

<| e' X2

O O O

0 b b

Car- bon Resi- due

on

10 % Hottoms, X i VO «r» . « 3 1 —• f> 2 j 0 O

O --3 - ~ x ! V“> wn O 0 O

3 ! O O *") 0 O Sib 0 b —^ b

w *r _ c-|pr t- w

1 —. —- oO >oO

2 j 1 = 1 ci 1 ci : :

S •= u <— M

in

3H

or

legal (100) 38

or

legal (100) 55

or

legal (

130 )

55

or

legal (

130 )

55

or

legal (

130 )

Orade

of

Fuel

Oil

No. 1

A

distillate

oil

intended

for

vaporizing

pot-type

burners

and

other

burners

requiring

this

grade

of

fuel

No. 2

A

distillate

oil

for

general

purpose

heating

for

use

in

burners

not

requiring

No. 1

fuel

oil

No.

4 Preheating

not

usually

required

for

handling

or

burning No. 5

(Light)

Preheating

may

be

required

depending

on

climate

and

equipment

No. 5

(Heavy)

Preheating

may

be

required

for

burning

and,

in

cold

climates,

may

be

required

for

handling

215

D 396

i

216

fill* D 396

APPENDIX

XI. SIGNIFICANCE OF AST.M SPECIFICATION FOR FUEL OILS

XI.1 Scope XI. 1. 1 AST.M 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. 1 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. X13 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 ensure that evaporation proceeds with

a minimum of residue. Xl.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 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 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.

Xl.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. 3 (light) and is in- tended for use in similar service. Preheating may be necessary in some types of equipment for burning and in colder climates for handling.

Xl.3.6 Grade No. <5, sometimes referred to as "Bunker C." is a high-viscostiy oil used mostly in commercial and industrial heating. It tequires pre- heating in the storage lank 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: XI.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.Xl .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 VI 1, Shell-Amsterdam 214S-I, Method D 3245-IP 230/69,

Test for Pumpability of Industrial Fuel Oils. 5 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 fue! 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 burn-

* Annual Book ofASTM Standards. Part 15.

217
-
<sn>

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 06 . Test for Distillation of Petroleum Products.’ and then determine the carbon residue concentrated in the remaining 10 percent bottoms. XI.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 v-ear 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. I 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 installations. 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. I and

2—The viscosity of an oil is a measure of its resistD 396

ance to flow. In fuel oil it is highls significant since

it indicates both the relative case with which the oil will flow or may be pumped, and the case of atomization. Viscosity limits for No. I and No 2 grades arc

specified to help maintain uniform fuel flow m appliances with gravity flow, and to provide satisfac- tory atomization and constant Row 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 weightvolume 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 comoonents of the fuel system. This property is specified

only for No. 1 distillate fuel. X 1 .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 takes no position respecting the validity of anv patent rights asserted

in connection with any item mentioned in this standard. Users of this standard are expressly advised that determination 0/ the

validity of any such patent rights, and the risk of infringement of such rights, is entirely their own responsibility.

218

VV-F-81 5C

July 30, 197?

SUPERSEDING

VV-F-81 5B

16 December 1 3^*9

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 o i 1 -burn i ng

,

heat-generating equipment (see 6.1).

1.2 Cl ass i f? cat 1 on . Burner fuel oil covered by this specification shall

be of the following grades as specified (see '6.2):

Grade Mo. 1 Grade No. 2

Grade No. 4

Grade No. 5 (Light)

Grade No. 5 (Heavy)

Grade No. 6

Distillate

Distillate

Light residual or heavy distillate

Res i dual

Res i dua

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
iM
v v**r ~o i pu

(Single copies of this specification and other product specificati ons re- quired by activities outside the Federal Government for tidding purposes are

available without charge at the General Services Adm i n i s t ra t i on Regional

Off ices in Boston, New York, Wash i ng ton , D. C., Atlanta, Chicago, Kansas

City, Mo., Fort V/orth, 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.)

Mi litary Standards :

M1L-STD-105 * Sampling Procedures and Tables for Inspection by Attributes

M1L-STD-230 - Packaging, Packing and Marking of Petroleum and Related

Products

(Cop ies 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

D 86

D 88

D 93

D 95

D 97

D 129

D 130

D 270

D 287

D kb$

0 bll

D b§2

D 52 b

D 61

- Flash Point by Tag Closed Tester

- Distillation of Petroleum Products

- Saybol t V i scos i ty

- Flash Point by Pensky-Martens Closed Tester

- Water in Petroleum and Other Bituminous Materials

- Pour Point

- Sulfur in Petroleum Products by the Bomb Method

- Detection of Copper Corrosion from Petroleum Products by the

Copper Strip Tarnish Test

- Sampling Petroleum and Petroleum Products

- API Gravity of Crude Petroleum and Petroleum Products

(Hydrometer Method)

- Viscosity of Transparent and Opaque Liquids (Kinematic and

Dynamic Viscosities)

- Sediment In Crude and Fuel Oils by Extraction

- Ash from Petroleum Products

- Ramsbottom Carbon Residue of Petroleum Products

- Test for Aniline Point in Petroleum Products

2
,
VV-F-8I5C

0 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 Viscosi ty

D 2622 - Sulfur in Petroleum Product (X-Ray Spect rog raph i c 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 petrol eum- derived products.

In the procurement of new fuel oils, suppliers are prohibited from adulteratin

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 requi rements . 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,

qr 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 maximum 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 Workmansh i

p

. The fuel oil shall be homogeneous in appearance, free

from visible foreign matter such as grit or fiber.

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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.

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.

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 wi th 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 24 hours),

through the same processing equipment, 'with no change in the ingredient

mate r i a 1 s .

4 . 3 Samp ling .

4.3-

1 Sampling for examination of packed containers . Take a randon sample

of packed containers from each packaged lot in accordance v/i th MI L— STD— 105

at inspection level I! and acceptable quality level (AOL) = 2.5 percent

defect i ve

4.3-

2 Samp ling for tests . Take samples for tests in accordance with ASTM

method D 270.

4.4 Inspection . Perform inspection in accordance with method S 60 1 of

Fed. Test Method Std. No. 791.

4.4.1 Examination of packed containers . Examine samples taken in accordance with 4.3.1 for compliance with M1L-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 Ml L-STD— 105 , reject the lot represented by the

sample

VV-F-8I5C

b.S Classification of tests . ‘All tests are quality conformance tests.

b. 6 Test methods . Perform tests in accordance with the applicable methods

1 is ted i n Tab le I 1 .

TABLE 11. Test methods

Tes t AS1H test method

number

Flash point-!/

• D 93 or D 56

Pour point

No. 1 , 2 , and b)

0 97

Water and sediment (grades D 1796

V/ater (grades No. 5 and 6) D 95

Sediment (grades No. 5 and 6) D ^73

Carbon residue, Ramsbottom D 52b

Ash D bS2

Distillation temperature D 86

Viscosity, Kinematic D bb 5

Viscosity, Sayboltf/ D 2161 or D 83

Gravity, API D 287

Copper strip corrosion// D 130

Sul fur// D 1552, 0129,

D 1551 or D 2622

Aniline point D 611

i/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.

2/The test shall be run for 3 hours at 212°F. (100°C.).

//ASTM method D 1552 is the preferred method. D 129, D 1551 and D 2o22 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:

7

VV-J--0 IpL

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 wi th a heated surface or by radiation.

6.1.2 Grade No. 2 . A heavier distillate than grade flo. 1. It is intended

for use in a tom i z i ng- type burners which spray the oil into a combustion

chamber where the tiny droplets burn wh i 1 e in suspension. The grade of oil

is used in most domestic burners and in many medium-capacity commercialindustrial burners where its ease of handling and ready availability sometimes justify its higher cost over the residual grades.

6.1.3 Grade Mo. b . Usually a light residual but sometimes a heavy distillate. It is intended for use in burners equipped v/i th 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. b Grade Mo. 5 (light) . A residual fuel of intermediate viscosity for

burners capable of handling fuel more viscous than grade No. A without preheating. Preheating may be necessary in some types of equipment for burning

and in colder climates for handling.

6.1.5 Grade No . 5 f 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 Grade No. 6 . A h i ah- v i sees i ty 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 ).

r

8

VV-F-815C

6.3 Sulfur content fscc 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 requ i rements in this specification. Sulfur limits should

be specified in all contracts or purchase orders, in compliance with the

current legal requ i reran ts 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 wi th Executive Order

11282, Control of Air Pollution Originating from

Federal Installations.

MILITARY CUSTODIANS:

Army - MR

Navy - YD

Ai r Force - 68

Revi ew activities:

Army - WC

Navy - YD, SA

Air Force - 68

DSA - PS

User activities:

Navy - MC, SH

Prepari ng act i v i ty

Army - MR

(Project No. 91^0-00^0)

CIVIL AGENCY INTEREST:

GSA

s. savspjrsK? office: : 1972 c - fLV-i <69 ( 3? )

Orders for this publication ore to be placed with Genera] Services Admini-

.-.tj a tier:, a c ~inq as on a pent for the Superintendent of Documents. See

.section 2 el this specification to obtain extro copies and other documents

referenced herein. Price 19 cents each.

9

'/ " t } /

MIL-F-359E

27 SEPTEMBER 13«5 SUPERSEDING

MII/-F—859D

21 DECEMBER ItU

(SEE 6.5)

MILITARY SPECIFICATION

FUEL O'L BURNER

/ Au $yfr\*c in -i man f-ilo ry /or iu<> Ay a// b*poir(- m*a(i irui .1 "i^l * f*»# Uipartmint of luff***.

L SCOPE

1.1 Scope. This specific?.' ion covers burr; er fuel oil for sb am power- 1 ves.seo of th Navy and. for other steam powered vessels of the Government service.

L2 Classification. Burner fuel oil shall be the following grade (see G.2) :

Burner fuel oil- -Navy special

(NATO symbol K-77 ).

Z 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 —

Military

MIL-STD-290

Lubricants, LiquidFuels, and Related

Products; Methods

of Testing.

Packaging, Packing and Marking

of Petroleum and

Related Products.

'

' -> j»i e-s of tpocificutioru, riaedards, drs'srinprg, bh-d

p Uca..jns ,-eqeired by tuppliers la comse-ctioa with

specific procurement functions should ba obtsjn-ed

from the procuring activity or its directed by tba

contracting officer.)

2L2 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 sha n •*oply.

American Society for Testing and

Materials (ASTM)

ASTM Part 17 — Petroleum ProductsFuols, Solvents,

Engine Tests, Lubricating Oils,

Cutting Oils,

Greasa.

D-88

D-92

D-93

D-96

— Viscosity, Ssybolt — Flash and Fire

Points by Clsvoland Cup Open. — Flash Point by Penshy - Martens

Closed Tester, — Water in Petroleum

Products and Othrsc ®ue

/>;

0/10

MIL-F—&59E

er Bituminous Materials. D-97 — Cloud and Pour

Points.

D-129 — Test for Sulfur in Petroleum Products by the Bomb

Method.

Maximum Fluidity

Tompcraturo of

Residual Fuel Oil

(Tentative).

D-1796 —- Test for Water end

Sediment In Fuel

Olio by Centrifuge.

D-189 — Test for Conradson

Carbon Residue of

Petroleum Products.

(Application for *np!cs should b« addrwaod to tb* American Society for Testing and Materials, 11)19 Race Street, Philadelphia, Pa. 19103.)

INTERSTATE COMMENCE COMMISSION

D-270

D-287

D-473

D-482

D-1659

— Method of Sampling

Petroleum and Pe- troleum Products

(Tentative)

— Test for API Gravity of Crude Pe- troleum and Petro- leum Products

(Hydrometer

Method )

Code of Federal Regulations

(Application for copies should be addressed to Lb* Superintendent of Documents, Government Printing

Office, Washington, D.C, 20402).

(Technical society and technical eussoefotkya spsari- fications and standards ara frcncmlly available for reference from libraries. They tro also distributed among technical groups and using Federal ageteriefc.)

3. REQUIREMF.NTS — Test for Sediment I-i Crude Petroleum

and Fuel Oil By

Extraction. — Test for Ash From

Petroleum Products. — Method of Test for

3.1 Material.

3.1.1 The burner fuel oil shall consist of

a hydrocarbon oil. Additives aro not permitted.

3-2 Chemical and physical requireEvents. The fuel oil shall conform to the chemical

and physical requirements of table I.

Tail* ]. Citmirel amd pAy

Lisles

T**t

1

ASTT3 t»iM

Flash point, closed cup (min.) *F. 160 1102 D-23

Fira point (min.) *F. ' £00 nos D-OS

Viscosity, et 122*F. (mix.) 8SF £04 D-4J3

1 w7U

MIL—F—

Tails I. CiimUal and pkytUal f«quiretntn(s—Conilntxtl

Utntta

T««*

BBttsfc-er 1

AKTV

f wrxAh>s4 »UJHt>rT

Viscosity, at 122*F. (ma.) SSU 225 304 D-88

Viscosity, at 85*F. (min.) SSU •225 304 D-88

Ash (max.) percent 0.10 5421 D—<82

Water, by distillation (max.) percent 0.5 £001 D-05

A-PJ. gravity (min.) 11.5 401 D-237

Pour point, upper (max.) * *F. 15 * 201 D-07

Fluidity at 32*F. * Pass D-1559

* Appendix

Carbon residue (max.) percent 15 ’5001 D-18S

Sediment by extraction (max.) percent 0.12 3002 D—473

Water and sediment (max.) percent * 0.5 3000 D-1736

Thermal stability (NBTL heater) * •Pass “3451 —

Explosiveness

Sulphur (max.)

(max.) percent 50

3.50 5202

1161 —D-129

« FTD-STD-m. «&« I.J.

‘ tquivaJrot l© • p*>roxim»Ul7 M S3U at 1I3*F. If rUeosity at Itt* F. k &&& 1$$ kaea SSTJ tbs rUcoilly at W‘F. md cot b4 mc^rarrd.

• If Lh* poor po4«t k Um Lb* a 14*F. tK« fi»Wlty *«*d eM W*

*6e* 44-1.1.

• frrc 4. 4.1.1 Pour teat aoi required ^fe<ra fi® 1 d i ty 1st b p4rtorw#^ »nd p*a»es. 'Sea 4X1.1.

• Applicable only on tamp Sea Ukaa at tup?* «r*i refinery. Unk farm, or plpu Una.

( 8«c 14 »o4 U.

• H D-J<41 U an option*] method and ruf ta vm4 In lUm of K BT L aealar.

3.3 Fire point. When the flash point of

the fuel is ]75“F. or higher, the fire point

need not be determined. If the water content of the fuel prevents accurate determination of the fire point, the fuel oil will bo

acceptable if the foaming duo to water

starts below the fire point, and at a temperature not lower than 195*F.

3.4 Thermal stability. When subjected

to the thermal stability test specified in ta- ble I fuel oil Navy special shall show a No.

I tube or better.

fLS 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 II and I. CompatiUf 12

3
-
I

MIL—F—859

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 requirements as specified herein. Except as otherwise specified, the supplier may utilize his own facilities or any commercial laboratory

acceptable to the Government. The Government reserves the right to perform any of the inspections set forth in the specification where such inspections are deemed to assure supplies and services conform to pre- scribed requirements.

4.2 Sampling.

4.2.1 Bulk lot. An indefinite quantit of

material from one storage tank oiTered 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 53-gallon drums or smaller containers

of identical size and type filled from one

storage tank. Acceptance tests (shall be per- formed upon a composite of samples taken

In the number and as specified In ASTM

D-270.

44

4.3.1 Tests 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 bo In accordance with the specified method

tsee table I).

4.3.1.2 Pour point. In determining the

pour point three consecutive tests of' the

'•ame sample, using the same test jar, shall

l>e conducted. The value to be reported,

provided the results of the three tests check

within 5*F.; shall be the average of the

three results to the nearest multiple of 5. All other details of the test shall be La ac- cordance with the specified method (see ta- ble I).

4-i.l.S Fluidity test. The object of the

fluidity test is to ascertain if the oil will flow through a 1/2 inch pips under slight

pressure (such ns it would ba subjected to by a pump or by its own head 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 separata testa of Navy

special fuel and reference fuel H snd Navy

special fuel and reference fuel I at a ratio

of 1:1.

5. PREPARATION FOR DELIVERY

3.1 Packaging, packing, and marking.

Packaging, packing, and marking shall be

In accordance with MII^-STB-230.

5.2 Marking of shipments. Shipping containers shall be marked in accordance with

MIL-STD-290. The nomenclature shall be

as follows: Fuel Oil, Burner, Navy special

(NATO symbol F-77), MIL-F-359. In

addition, the Information required by Coda

of Federal Regulations 49CFR 71-78 shall appear on each Individual container and on

all Ehlpplnar containers.

i 0713

MIL--F-C59E

6, NOTES

6.1 Intended us«. Fuel oil Navy special

la intended for use in all steam vessels of

the Navy, and other Government vessels as required.

&2 Ordering data. Procurement documents should specify tho following:

(a) Title, number, and date of Oils specification.

(b) Quantity required (see 42. 2.).

(c) Packaging, packing and marking required (see 5.1 and 5.2).

6.3 Certain provisions of this specification aro tho subject of an International

standardization agreement (NATO). YThen

amendment revision, or cancellation of this

specification is proposed, the departmental

custodians will inform their respective Departmental Standardization Ofiics so that

appropriate action may be taken respecting

the international agreement concerned.

(L4 Information relative to obtaining H

and I reference fuels may ha obtained from

the cognizant klUIt&ry inspector.

<L5 Changes from previous issue. The

extent of changes (deletions, additions,

etc.) preclude the annotation of the individual changea from the previous Issue of

this document.

Ceatodiins: Arai-—ME

y«TT—sh

Air Fore©—68

Rerirw eetiritira:

Array—MR

N»ry—SIX

Air Fore©—58

UWr ftrtiritlee: Array—CE, CL, MU

Nery—YD

InJerusticnal tee(loea 6)

Prrts-sFiajf fectMty:

Nery—SH

(Preject SHC-GSIS)

U714 % V. «. ©*«KS«4S®R7 rCUMTiS* CWK9I tSItSi—IfSi— ( V-81V

-^7

C

M1L-F-8S9E

AMENDMENT

4 August 1967

SUPERSED i,cl/

Aeendaent

24 August 1966

MILITARY SPECIFICATION

FUEL OIL, BURNER

This aaendaent foros a part of Military Specification KIL-F-8S9E, dated 22 Septeal

1966 and is nandatory for use by all Dcpartsents and Agencies of the Departaent i Defense

Page 2. paragraph 2.2, under AMERICAN SOCIETY F08 TESTING AND MATERIALS (ASTJf) : J D-1661 - Thera al Stability of U. S. Navy Special Fuel Oil."

Page 3, Table I: Delete and substitute:

"Table I • Chemical and physical requirements (Continued)

Viscos i ty , at 1 2

2 ' F . (aax .

)

Viscosity, at 8S*F. (sin.)

Ash (aa-£.) Water, by distillation (six.) A.P.I. gravity (ain.) Pour point, upper (aax.)-5/

Fluidity at 32*F.— ^

Carbon residue (Rax.)

Sediaent by extraction (oax.) Water and sediaent (nil.)

Thenasl stability

Explosiveness (nix.)

•Sulphur (six , )

Llcits

i cs t eethod, . r.’xnberA/2310!

I sotiod

1 nva be r

S3TD 123 j \j 4 D- bi ssa ^22S 3 04 D- 83

percent 0.10 S4 2

D-4S2 • percent O.S 3001 D-9S

11.401 D- 237

IS •5/201 D-97

^Ps£8 £-1659

2/sooi

Appesa

percent IS

‘ 3-109

percent 0.12 3002 D-473

percent —7

0 . s —7 Pa j *

3000 D- 1 796

D-1661

percent SO 11 SI 3. SO S 2 C 2 D-l 29 See footnotes to table I on next page.

CHANGES FROM PREVIOUS ISSUE. THE OUTSIDE MARGINS OP THIS DOCUMENT HVVE SEEN HfJ

,T I" TC3 ITTuTCA TH VCiZ^Z C'/DCNCES (DELETIONS, ADDITIONS, ETC.) FROM TH~ DEVIOUS 1 HAVE BEEN HADE. THIS HAS BEEN DOME AS A CONVENIENCE ONLY AND THE GOVERNMENT

ASSUMES NO LIA3IL1TY WHATSOEVER FOR ANY 1 NACCURAC I ES IN THESE NOTATIONS . 3ID! AND CONTRACTORS ARE CAUTIONED TO EVALUATE THE REQUIREMENTS OP THIS DOCUMENT SJ ON THE ENTIRE CONTENT AS WRITTEN IRRESPECTIVE OF THE MARGINAL NOTATIONS AND

RELATIONSHIP TO THE LAST PREVIOUS ISSUE.

nc ouo

U7U8

i Klls-FSW

u&sxtair - i 24 Auguat I9C6

MILITARY SPECIFICATION

FUEL OIL, BURNER

This aj^endsont fon^* a part, of Military Spocif ieation iCiy-F-^j^E*

dated 22 September 19t>5 nrd is Banda Lory for use by oil Depart&onta m

Agencies of the Deportment of Defense.

Pago 2, paragraph 2.2, undor AMERICAN SOCIETY FOR 7ES7II«>j A.ID MAtnRIALo

(AETM)j Add "D-1661 - Tnerxal Stability of U.S. Navy Special Fuel Oil.”

Pago 3* Table I: Delete and substitute:

Table I - Chemical ard physical requircconta (Continued)

liza&a

fvKir>^

fcOE&l-^ 1

A.TTH

***^•*3

Vl»e*slty, et 122*P. (hbajl) ssu 225 sot D-88

Ybecslty, at G5’F. (mia.) ssu •225 204 D-68

Asb (es au) jx. ree.it 0.10 (421 D-4S2

Water, by dUtilUUon (eisl) p«re«&t OS SO01 D-96 AJM. gTETily (ns la.) 1U 401 D-2S7

Pocr poiat, upper <t&&s.) • •?. 16 •201 D-07

FluUJty et S2*F.* • Pus D-lf>5» Appendix

C&rbea rajidao (bull) psrecat 16 •6001 D-189

Sedisiast by cxU-cctiae (m&s.) percent 0.12 2002 D—(73 Web«r sad fc&dlmvet (max.) p*re*nt •os 1000 D-17W

ThsmcJ rtsbCity * Pas* D-1661

Erptestrenese

Selpber (zees.)

(kai.) percent 60

110 6202

1161 —D-129

(4 U

• WoM to M-*w=snto»to*r ts CSV to 1 err. U Ttonoity .1 iu*r. L) emu lUo IM BSV m4 tea tx* CSV tto

Vfc«G»iSr U H'P. Knsd to omitoi

•H Vto y-'TT (Mat to kaa Ils» U*P. lb* fiato®? *mA eto to parUmaA.

4l 3l 1 1 Si Pour test rot required when fluidity test is performed and passes,

• 6s» 4. 3» 1 • 1

* eejy tr<t •teu MiUt"

teAaa «d (/wsr, car

FSC 9U0

Pago 1 of 2 page*

/ >L

#••• • t'A
,j

I
KLL-r -?, r/)Z

AKEttttL.YT - 1

C«S4ed>cee: Ats; —MB

N»tT—

Ah ferr<c—48

Rrttre trllTitira! Army—MR

S.,r_g|t

Air Fwc*~C8

Urer ertintU-s: Array—CK. GL, HU

Nrry—YD

Preparing Mlirllyt

Jserf—S II

(Prejret il< 8-0024 )

I

of 2 p*£es

7b9

MTI.-F - 16 3R4C

7_ ’larch 197 3 SUPERSEDING

MIL-F-163S4F

3 November 106 5 (£ee 6.4)

MILITARY SPEC I F I CAT I Or

FUEL OIL, DIESEL, MARI. IE

This sped f ication is approved for use by all Departments and Agencies of the Deoartment of Defense.

1. SCOPE

1.1 This specification covers one grade of marine Diesel fuel (EA70 symbol f F - 7 6 ).

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, Liquid Fuels, and Related Products; Method of

Testing.

MILITARY

MIL-STD-290 - Packaging, Packing and Marking of Petroleum, and Related

Products

(Copies of specifications, standards, drav/ings, and publications required by suppliers

in connection with soecific procurement functions should be obtained from, the procuring

activity or as directed by the contracting officer.)

2.2

Other publica tions . The following documents form a part of this specification to the extent specified herein. Unless otherwise indicated, the issue- in effect cn date of

invitation for bids or request for proposal shall apply.

AMERICA

DD

D

DD

D

D

D

D

D

DD

D

D

D

D

D

D

D

DE

N SOCIETY FOR TESTING AND MATERIALS (ASTM)

86 - Distillation of Petroleum Products.

93 - Flash Point by Pensky-Mar tens Closed Tester.

97 - Pour Point.

129 - Sulfur in Petroleum Products by the Bomb Method.

130 - Copper Corrosion by Petroleum Products.

287 - API Gravity of Crude Petroleum and Petroleum Products

(Hydrometer Method) . 445 - Viscosity of Transparent and Opaque Liquids (Kinematic ar.d Dynamic Vicosities).

482 - Ash from Petroleum. Products.

524 - Ramsbottom Carbon Residue of Petroleum Products.

611 - Aniline Point and Mixed Aniline Point of Petroleum Produces

and Hydrocarbon Solvents.

613 - Ignition Quality of Diesel Fuels by the Cetane Method.

665 - Rust-Preventing Characteristics of Steam-Turbine Oil in

the Presence of Water.

974 - Neutralisation Number by Color-Indicator Titration.

976 - Calculated Cetane Index of Distillate Fuels.

1500 - ASTM Color of Petroleum Products (ASTM Color Scale)

1552 - Sulfur in Petroleum Products (High-Temperature Method),

* Test for.

2274 - Test for Stability of Distillate Fuel Oil (Accelerated Method).

2500 - Test for Cloud Point of Petroleum Oils.

2622 - Test for Sulfur in Petroleum Products (X-Ray Spectrographic

Method)

2709 - Water and Sediment in Distillate Fuels by Centrifuge, Test for.

29 - Recommended Practice for Indicating Which Places of Figures Are to

Be Considered Significant in Specified Limiting Values.

FSC 9140
f ~f ..r
MIL-F-1C884G

(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 grouos

and using Federal agencies.)

3. REQUIREMENTS

3 . 1 Req

test methods,

results will

those cases,

repeatability

provided an i falling outsi

requirement,

unit" in the

accordance wi

uirements contained herein are not subject to corrections for tolerance of

If multiple determinations are made by the inspecting laboratory, average

be used except for those test methods where repeatability data are given. In

the average value derived from the individual results that agree within the

limits given may be used at the discretion of the inspection authority,

ndication is given of the total number or results obtained and the number

de the repeatability limits. For purposes of determining conformance with each

and observed value or calculated value shall be rounded off "to the nearest

last right-hand place of figures used in expressing the limiting value, in

th 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 requTrements specified m table I. Table I - Chemical and physical requirements.

Characteristics Requirements

FED-STD-79

test method

ASTM

test method

Ignition quality, cetane number

(min) (see 4.3.1) 45 D 613

Appearance—

Distillation

50 percent point, °F

90 percent point, °F (max)

Clear, bright, and

free from visible

particulate matter.

Record

675°F (357. 2°C) D 86

2 / End point, °F (max)—

Residue plus loss, percent (max)

Flash point °F (min)

7 2 5 ° F (385 °C)

3.0

140°F (60°C) D 93

Pour point, ®F (max) 20 °F (-6 . 7°C) D 97

Cloud Doint, °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 12 9 —

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 ml (max) 2. 5i/ D 2274

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.

*[y ASTM D 1552 and ASTM D 2622 may be used as alternate methods. ~ Average of three determinations is acceDtable.

2 /

3/

2

MIL-F-16834C

3.4 Additive s . 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)/10Q gallons (gal)

(U.S.), 24 milligrams (mq)/liter or 109 mg/gal (U.K.)) in order to prevent the formation

of gum:

(a) N, N

' - diisopropyl -para-pheny lcnediamine

(b) N, i: ' - diseconda ry butyl-para-phenylenedi amine

(c) 2, 6 - ditertiary butyl-4- me thylphenol

(d) 2, 4 - dimethyl -6 -tertiary butylphenol

(e) 2, 6 - ditertiary buty lphe.nol

(f) 75 percent min. 2 , 6-ditertiary butylphenol

25 percent min. tertiary and tritertiary butylphenols

3.4.2 Me tal deactivator . A metal deactivator, N, N ' - disalicyclidene-1 , 2 propanediarniine 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.)).

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 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 Government

rnment reserves tne right to pe T

" f ^^ such inspections are deemed necessar

orn any of the inspections set forth in the specification where

o assure supplies and services conform to prescribed

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.

f 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.

f 4.3 Sampling .

t 4.3.1 Sampling for examination of. the preparation for de livery .

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.

I 4.3.2 Sampling for tests . Take samples for tests in accordance with AST'4 D 270.

Test the samples in accordance with table I and 4.6.

j 4.4 Inspection . Perform inspection in accordance with method 9601 of FED-STD-791.

f 4.4.1 Examina tion of the p reparation for del ivery. Samples taken in accordance

•with 4.3.1 shall be examined 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, the lot

represented by the sample shall be rejected.

f 4.5 Classification of tests . All tests are quality conformance tests.

3
I
!.IL-F- I ^84C

i . v Tost methods . 4.6.1 Ignition guali tv . When the apparatus specified in AST'I 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 nrocess or processes and the same specific crude source. In all instances the product subnitt^'4 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 AST.'I 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 Demul sif i cat ion . The test for demulsi f ication shall be conducted in accordance

with method 3201 of FLD-STD-791 with the following exceptions:

(a) Synthetic sea water prepared in accordance with AST.'I D 665 shall be

used as the emulsifying fluid.

(b) The test temperature shall be 77° + 2°F (25° + 1.1°C).

(c) The demulsif ication 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 specif ication

5. PREPARATION! FOR DELIVERY

I 5.1 Packaging , packing , accordance with !lIL-STD-290 . be as specified (see 6.2).

6 . NOTES

i 6.1 Intended use. This grade of marine Diesel fuel is intended for use in

engines in submarines and for such other uses as may be specified at Lemoera ture

30 °F <-l.l°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 NATO STANAG-1135 . When amendment, revision, or cancellation of this spec;

fication 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 "2" TO INDICATE WHERE CHANGES

(ADDITIONS, MODIFICATIONS, CORRECTIONS, DELETIONS) FROM TEE PREVIOUS ISSUE HAVE BEEN MADE.

THIS WAS DOME AS A CONVENIENCE ONLY AND THE GOVERNMENT ASSUMES NO LIABILITY WHATSOEVER FOR

ANY INACCURACIES IN THESE NOTATIONS. BIDDERS AND CONTRACTORS ARE CAUTIONED TO EVALUATE TEE

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

International interest (see section 6)

,, *U.S. GOVERNMENT PRINTING OFFICE :1973-714-M1

Preparing activity:

Navy - SH

(Project 9140-0039)

Diesel

above

and marking. Packaging, packing, and marking shall be in

The level of packaging, level of packing, type, and size shall