U.S. Environmental Protection Agency Industrial Environmental Research
Office of Research and Development Laboratory
Research Triangle Park, North Carolina 27711
EPA-600/7-77-143
December 1977
TECHNICAL MANUAL FOR THE
ANALYSIS OF FUELS
Interagency
Energy-Environment
Research and Development
Program Report
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RESEARCH REPORTING SERIES
Research reports of the Office of Research and Development, U.S. Environmental
Protection Agency, have been grouped into seven series. These seven broad categories
were established to facilitate further development and application of environmental
technology. Elimination of traditional grouping was consciously planned to foster
technology transfer and a maximum interface in related fields. The seven series
are:
1. Environmental Health Effects Research
2. Environmental Protection Technology
3. Ecological Research
4. Environmental Monitoring
5. Socioeconomic Environmental Studies
6. Scientific and Technical Assessment Reports (STAR)
7. Interagency Energy-Environment Research and Development
This report has been assigned to the INTERAGENCY ENERGY-ENVIRONMENT
RESEARCH AND DEVELOPMENT series. Reports in this series result from the effort
funded under the 17-agency Federal Energy/Environment Research and Development
Program. These studies relate to EPA's mission to protect the public health and welfare
from adverse effects of pollutants associated with energy systems. The goal of the
Program is to assure the rapid development of domestic energy supplies in an environ-
mentally-compatible manner by providing the necessary environmental data and
control technology. Investigations include analyses of the transport of energy-related
pollutants and their health and ecological effects; assessments of, and development
of, control technologies for energy systems; and integrated assessments of a wide
range of energy-related environmental issues.
REVIEW NOTICE
This report has been reviewed by the participating Federal Agencies, and approved
for publication. Approval does not signify that the contents necessarily reflect the
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products constitute endorsement or recommendation for use.
This document is available to the public through the National Technical Information
Service, Springfield, Virginia 22161.
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EPA-600/7^77-143
December 1977
TECHNICAL MANUAL
FOR THE ANALYSIS OF FUELS
by
L.N. Davidson, W.J. Lyman,
D. Shooter, and J.R. Valentine
Arthur D. Little, Inc.
Acorn Park
Cambridge, Massachusetts 02140
Contract No. 68-02-2150, T.D. 20602
Program Element No. EHB529
EPA Project Officer: Larry D. Johnson
Industrial Environmental Research Laboratory
Office of Energy, Minerals, and Industry
Research Triangle Park, N.C. 27711
Prepared for
U.S. ENVIRONMENTAL PROTECTION AGENCY
Office of Research and Development
Washington, D.C. 20460
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TABLE OF CONTENTS
Page
LIST OF TABLES v
CHAPTER I - INTRODUCTION 1
1. Objectives 1
2. General Recommendations 2
3. Contents of the Manual 3
4. Criteria for Methods Selection 4
CHAPTER II - GASEOUS FUELS 7
1. Introduction 7
2. Sampling 8
3. Analysis Methods 9
4. References 10
CHAPTER III - LIQUID PETROLEUM FUELS 17
1. Introduction/Summary 17
2. Sampling 18
3. Analyses 19
4. References 19
CHAPTER IV - SHALE OIL AND COAL LIQUIDS 33
1. Introduction/Summary 33
A. Shale Oil 33
B. Coal Liquids 35
2. Sampling 37
3. Analyses 38
4. References 39
CHAPTER V - METHYL FUEL 51
1. Introduction/Summary 51
2. Sampling 52
3. Analyses 53
4. References 54
iii
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TABLE OF CONTENTS
(continued)
Page
CHAPTER VI - COAL AND COKE ' 63
1. Introduction/Summary 63
A. Coal 63
B. Coke 64
2. Sampling 65
A. Coal 65
B. Coke 66
3. Analyses 67
A. Coal 67
B. Coke 67
4. References 68
CHAPTER VII - REFUSE-DERIVED SOLID
FUELS (RDSF) AND PEAT 75
1. Introduction/Summary 75
A. Refuse-Derived Solid Fuels 75
B. Peat 76
2. Sampling 77
A. Refuse-Derived Solid Fuels 77
B. Peat 79
3. Analyses 79
A. Refuse-Derived Solid Fuels 79
B. Peat 80
4. References 81
APPENDIX A - AVAILABLE STANDARD REFERENCE MATERIALS 93
APPENDIX B - LABORATORY DIRECTORIES 103
APPENDIX C - TYPICAL VALUES (RANGES) OF PARAMETERS 107
SPECIFIED FOR EACH FUEL
APPENDIX D - RESULTS OF FUEL ANALYSIS TESTS 127
iv
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CHAPTER I
INTRODUCTION
1. OBJECTIVES
This manual is intended for use as a guide to fuel sampling and analysis
in IERL/RTP projects concerned with fossil fuel utilization. The infor-
mation given is basically a description and discussion of established
methods of sampling analysis for a variety of hydrocarbon fuels. The
analyses covered are those that are of prime concern to the engineer, or
project director, involved in a pollution related research project.
The coverage of non-standard methods and of additional parameters that
may be required in environmental assessments will be included in a forth-
coming Level 2 sampling and analysis manual. The non-standard methods
will include, for example, those that are state-of-the-art or that use
rapid instrumental techniques. The parameters added will be those
yielding information on the chemical nature of the fuel (e.g., classes
of organic chemicals), trace element composition, or certain additional
physical properties.
This manual indicates what fuel analyses are normally required in
connection with fuel-utilization research, and what established methods
are applicable for the analysis. If this manual serves only to point
out the importance of methods specification in fuel analysis, it will
have been of value. Too frequently, analyses of samples - including
fuels - result in inaccurate or meaningless results because an inappro-
priate method was used. It should not be assumed by the researcher or
project director that the analytical laboratories (Government or private)
will use the method that is both appropriate and standard. It is,
unfortunately, easy to make this assumption, in part because methods
published by one organization, the American Society for Testing and
-------
Materials (ASTM), are so widely recognized and used. There are, however,
a large number of ASTM methods available for various fuels, including two
or more alternative methods for many parameters, and the choice of the
most applicable method is important. In addition, many standard methods,
including some ASTM methods, leave certain options to the parties con-
cerned - e.g., the temperature or pressure at which a test is to be made.
If the researcher or project director does not specify the options to be
used, the laboratories may run the test in an inappropriate manner.
2. GENERAL RECOMMENDATIONS
Upon questioning, analytical laboratories conducting fuel analyses are
likely to give statements such as: "We follow ASTM methods or the equi-
valent"; "Generally use ASTM or a closely related method"; "Follow ASTM
almost entirely". It is recommended that, such statements aside, the
exact method of analysis be specified for every parameter by the re-
searcher or project director. In many cases, the method chosen will be
one that is routinely carried out by the laboratory, and this is a de-
sirable feature. If the laboratory indicates that it normally uses a
different method for one or more of the parameters, then a determination
must be made on the applicability of the method and the desirability of
its use. One area where such determinations may be frequently required
is that of instrumental methods for carbon, hydrogen, and nitrogen anal-
yses. If the method normally used with the instrument is applicable for
the fuel in question, then it may be desirable to use that instrumental
method since it may result in time and cost savings. If a large number
of samples are to be analyzed by any such non-standard method, then steps
should be taken to check both the accuracy and precision of the method.
Five additional recommendations are: (1) that the laboratory be required
to specify the exact method of analysis (and any modification) used on
samples for a given report; (2) that the laboratory be required to state
the detection limits of the method (or instrument) used for any result
that is near or below the detection limit; (3) that the precision of the
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results be included in all reporting; (4) that the parties concerned
agree, in advance, on the basis for reported results (e.g., "as-received"
versus "moisture-free" for fuel containing water) if it is not specified
by the chosen method; and, (5) for any large sampling and analysis pro-
gram that the laboratory be required to submit information on its qual-
ity control procedures, including the results of any tests carried out
(e.g., blanks, standards, duplicate results) during the course of the
program.
3. CONTENTS OF THE MANUAL
For each fuel covered, the manual indicates what analyses are likely to
be required, and what method(s) and analysis and sampling procedures are
available. For each method of analysis listed - preferred plus alter-
nates in many cases - the manual gives a summary of the method, a dis-
cussion of its applicability, and information on the accuracy and preci-
sion of the method, if known. The main emphasis is on methods of anal-
ysis; sampling methods are, in general, only discussed briefly.*
The listing in this manual of an analytical method as "preferred" method
does not mean that it is the only acceptable method, or even that it is
the best from an analytical standpoint. What is implied is a recommenda-
tion over the other available methods based on considerations of appli-
t
cability, precision and accuracy, availability of detailed instructions,
and current or expected usage. The criteria for the selection of methods
to be included in this manual, and for the selection of "preferred" meth-
i
ods, are given in the following subsection.
*For additional guidance in sampling, the reader should refer to "Techni-
cal Manual for Process Sampling Strategies for Organic Materials," U.S.
Environmental Protection Agency, Research Triangle Park, Durham, North
Carolina; April, 1976. (EPA-600/2-76-122, NTIS Report PB 256-696/AS.)
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The analyses listed for each fuel may not meet the information needs of
all research projects, nor is the listing intended to be a maximum or
minimum set of analyses. For a given research project, the parties con-
cerned should use the given list as a starting point and then add or sub-
tract parameters as the program's informational needs dictate.
The fuels covered in this manual are: gaseous fuels, coal and coke, coal
liquids, shale oil, liquid petroleum fuels (broken into several cate-
gories), waste lubricating oil, methyl fuel, refuse-derived solid fuel
(from municipal refuse), and peat. Not all of the fuels covered are in
commercial use, at present. These unconventional fuels were included,
however, because of their likely use in the future and the need, there-
fore, for research programs to be carried out on them.
Each subsequent chapter of this manual covers a fuel or fuel grouping.
The introduction to each chapter defines the fuels being discussed, in-
dicates the analyses covered (and the preferred method of analysis), and
gives other supplemental information about the fuel that may be of in-
terest in any environmental assessment of processes using the fuel. A
section on sampling is given and is followed by the main section describ-
ing the methods of analysis. References for each chapter are given at
the end of the text portion of that chapter.
Appendices give (1) information of the availability of Standard Reference
Materials for fuel-related analyses; (2) a listing of laboratory direc-
tories; (3) typical values (ranges) for the parameters specified for each
fuel; and, (4) the results of fuel analysis tests conducted by the con-
tractor and three analytical service laboratories.
4. CRITERIA FOR METHODS SELECTION
The criteria used in the selection of the preferred and alternate methods
of analysis involved the following considerations:
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1. Applicability of the method to the fuel in question;
2. The accuracy and/or precision of the method;
3. The availability of the publication containing the method and the
extent to which the method is currently used in laboratories con-
ducting fuel analyses.
The considerations listed in #1 and #2 were dominant in most instances.
No attempt was made - in the preparation of this manual - to review all
available methods because of limitations on time and funds. If a parti-
cular method was deemed applicable and "available", then it was consi-
dered. No method was considered for inclusion in this manual unless it
had been reported in sufficient detail in the open literature. Addi-
tionally, no attempt was made to resolve, by laboratory tests, the nu-
merous uncertainties concerning the applicability of specified methods
to fuels other than those the method was originally intended for. Some
laboratory tests on unconventional fuels were carried out as part of this
program (see Appendix D), but the scope of these tests was insufficient
to make a defensible decision on the applicability of the method used.
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CHAPTER II
GASEOUS FUELS
1. INTRODUCTION/SUMMARY
Gaseous fuels are mixtures of vapor-phase species including low molecular
weight hydrocarbons (up to and including small amounts of Cj compounds),
carbon oxides, nitrogen, hydrogen, helium, sulfur compounds (hydrogen sul-
fide and/or mercaptans), and oxygen. Fuels from different sources have
rather different compositions as, for example:
Natural Gas - methane is major component with lesser amounts of saturated
hydrocarbons, trace amounts of sulfur compounds and air com-
ponents, no carbon monoxide^.
Industrial Gas (coal gasification) - carbon monoxide and dioxide, some
hydrocarbons (but little methane), nitrogen, minor amounts
of sulfur compounds2'^.
The relatively small number of compounds possible in gaseous fuels has re-
sulted in the development of methods for the identification and measure-
ment of individual major and minor components using either gas chromato-
graphy or mass spectrometry. While standardized procedures for such mea-
surements have been established, continuing improvements in instrumentation
and chromatographic column technology have resulted in modified procedures
which allow the analyses to be carried out more quickly and conveniently
with no loss in precision or accuracy. Laboratories which are very active
in the area of gas analyses often develop and utilize procedures and equip-
ment based upon these modifications and improvements before such improve-
ments have been incorporated into standards such as the ASTM methods.
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Table II-l presents a summary of analyses for gaseous fuels along with
the preferred methods. Section 3 of this chapter provides additional in-
formation on analytical procedures, as well as alternate methods. The
preferred methods have all been selected from the American Society for
Testing and Materials (ASTM) methods for gaseous fuels1. A more complete
listing and description of methods applicable to the various composition
and physical property parameters is given in Table II-2.
2. SAMPLING
Methods for sampling gaseous fuel streams will vary according to the pres-
sure, temperature, and content of reactive gases (such as H2S) of the par-
ticle stream. Pressure in natural gas streams, for example, may vary from
several thousands of pounds at the well-head and some transmission lines
down to a few inches of water in service feed lines. In some industrial
applications where the gasification process equipment is close to the end
use, gases may be at temperatures above ambient.
General directions for sampling natural and manufactured1gases at low
temperature and low pressure are covered in ASTM D 1145, "Standard Method
of Sampling Natural Gas"1, and ASTM D 1247, "Standard Method of Sampling
Manufactured Gas"1, respectively.
Grab samples representative of the gas stream at one point in time are
generally taken, although continuous, integrated samples can be obtained
by use of a slow, regulated flow into a large sample container.
In sampling from a pipe, or other vessel, it is generally good practice to
use a sampling probe, or tip, which protrudes some distance into the vessel
and away from the wall, in order to avoid any effects of condensation,or
reaction at the wall which might alter the composition of the sample being
taken.
-------
A more general approach to sampling gaseous products from coal gasification
processes has been described by TRW2. In some cases, the product fuels may
be hot and may still contain some amounts of sulfur compounds, higher hydro-
carbons, and ammonia which have not been removed.
3. ANALYSIS METHODS
Table II-2 gives a more complete description of methods applicable to each
parameter. When more than one method is available, the preferred method is
listed first. The parameters are listed in that same order as in Table II-l.
The principal methods for measurement of major constituents in gaseous fuels
are gas chromatography and mass spectrometry. Gas chromatography is a very
powerful technique for separation and measurement of complex mixtures. How-
ever, this technique is dependent upon the availability and use of reference
standard gas mixtures for empirical calibration of quantitative and qualita-
tive (i.e., chromatographic retention time) response. For best results,
these calibration mixtures should be reasonably close in composition to the
sample(s) of interest.
Mass spectrometry affords qualitative identification of major components.
With the use of suitable reference standards, it can give more quantita-
tive information as well as provide further identification.
Because of the varying need for standards, initial analysis of a completely
unknown gaseous fuel should probably be done using mass spectrometry. Once
an approximate composition is known, then gas chromatography, with appro-
priate standards, can be used for subsequent analyses.
The estimates of precision given in Table II-2 are drawn largely from ASTM
studies. The accuracy of these measurements is, for the most part, a func-
tion of the accuracy with which the calibration standards have been made.
In addition, for the methods which involve consumption or reaction of
large volumes of sample, the accuracy of the measurement will also be a
-------
function of the state of the volume measurement apparatus.
Measurement of the calorific value and density of isolated (i.e., small
volume) samples of gaseous fuels is not often done. Instrumentation for
such measurements is really designed for continuous operation, and requires
relatively large volumes of sample to reach stable operation. Calculations
of both calorific value and density, based upon the composition data from
gas chromatography and mass spectrometry, is now done frequently as part
of the gas analysis5'6.
4. REFERENCES
1. "Annual Book of ASTM Standards (1974) - Part 26: Gaseous Fuels; Coal
and Coke; Atmospheric Analysis," American Society for Testing and Mate-
rials, Philadelphia, Pennsylvania.
2. Hamersma, J. W. and Reynolds, S. L., "Tentative Procedures for Sam-
pling and Analysis of Coal Gasification Processes," TRW Systems, U. S.
Environmental Protection Agency Contract No. 68-02-1412, Task Order
No. 3, March, 1975.
3. Tillman, D. A., "Status of Coal Gasification," Environmental Science
Technology, Volume 10, pages 34-38, 1976.
4. Purcell, J. E., Gilson, C. P., "Improved Analysis of Natural Gas,"
Chromatrography Newsletter, Volume 1, pages 45-50, 1972.
5. Private communication with Mr. James Baratta, Washington Gas Light Com-
pany, Arlington, Virginia, April, 1977.
6. Private communication with Mr. Louis Molinini, Gcllob Analytical Ser-
vice Corporation, Berkeley Heights, New Jersey, April, 1977.
7. "Annual Book of ASTM Standards (1974) - Part 24: Petroleum Products
and Lubricants (II)," American Society for Testing and Materials, Phila-
delphia, Pennsylvania.
10
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Table II-l
ANALYSES FOR GASEOUS FUELS
SUMMARY LISTING
PARAMETER
Natural Gas
Components
Gasification
Process,
Components
1.
2.
3.
4. Total Sulfur
Compounds
5. Calorific Value
PREFERRED METHOD3
ASTM D 1137
ASTM D 1946
(or modification
thereof)
ASTM D 2725
ASTM D 1072
By calculation from
components in ASTM
D 1137 and ASTM
D 1946 above; or
ASTM D 1826 (con-
tinuous gas calori-
meter)
APPROXIMATE
AMOUNT OF
SAMPLE NEEDED
FOR ANALYSIS13
tt)
^ 0.3
* 0.3
3e
30 e
100
COST OF SRM
ANALYSIS0 AVAILABLEd
($)
100
150 - 250
30
50
Not known
G-l
G-2
special
G-2
special
G-2
special
G-3
a. All ASTM methods are given in References #1 and #7.
b. These are the sample requirements for a single analysis. Approximate
Amount of Sample Needed for Analysis = Volume (STP) of Sample Required
for Analysis.
c. Estimated based on prices charged by analytical service laboratories in
early 1977.
d. See Appendix A, Table A-l for Standard Reference Materials available.
e. There is some question regarding the stability of such samples in sam-
pling containers. Where possible, the samples should be taken and
treated at the source. If this is not possible, the appropriate inert
(e.g., glass) sample containers should be used.
11
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Table II-2
METHODS OF ANALYSIS FOR GASEOUS FUELS
PARAMETER
SUGGESTED METHOD(S)
No./Title Ref.
1.
Natural Gas:
Components
A.
ASTM
D 1137
B.
ASTM
D 1945
SUMMARY OF METHODS
A portion of the gas sample is
subjected to mass spectroscopic
analysis. The mass spectrum of
the mixture is analyzed by com-
parison with the spectra of in-
dividual, pure components of
the mixture.
Individual constituents are
separated by gas chromato-
graphy on a column suitable
for the required separation,
and are measured by means of
a thermal conductivity detec-
tor. Constituent identifica-
tion and quantitative calibra-
tion are accomplished by ana-
lyzing reference standard gas
mixtures under same conditions.
APPLICABILITY
Natural gases, including
saturated hydrocarbons to
Cg, carbon oxides, in hy-
drogen sulfide, Ci~C2,
mercaptans; minimum level
for measurement is 0.1% in
mixture.
02, N2, CHj, - uses molecu-
lar sieve column. C02,
Cj-Cg hydrocarbons uses
partition column of sill-
cone oil or other absor-
bants. Can also be used
for separation of some
synthesis gases.
ACCURACY (A) AND PRECISION (P)*
(P) The expected precision (95%
confidence) for the analysis
of natural and synthetic gases
over a range of concentrations
is:
0% - 1%
1% - 5%
5% - 25%
> 25%
Individual
Analyst
0.1
0.1
0.1 - 0.3
0.2
Between
Labs
0.1 - 0.2
0.2 - 0.4
0.3 - 0.9
0.5 - 2.
The variations in precision
result from different studies;
in general analyses of natural
gas give better precision than
those of synthetic gases.
(P) Reproducibillty: The expected_
precision (95Z confidence) over
the rahge of concentrations is:
0% - 1%
1% - 5%
5% - 25%
> 25%
Heavy (C6)
fractions
Individual
Analyst
0.03
0.05
0.15
0.30
5% of
amount
Between
Labs
0.06
0.1
0.2
0.6
10% of
amount
All notes appear on the last page of this table.
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Table II-2
METHODS OF ANALYSIS FOR GASEOUS FUELS
(continued)
PARAMETERS
SUGGESTED METHOD(S)
No./Title Ref.
1.
Natural Gas:
Components
(continued)
C.
ASTM
D 1945
(Variations of)
2.
Synthetic Gas:
Components
A.
ASTM
D 1946
B.
ASTM
D 2650
3a. Hydrogen Sulfide ASTM D 2725
SUMMARY OF METHODS
Variations of D 1945 include
the following modifications:
a. Use of smaller columns
with different liquid
substrates
b. Use of porous polymer
column packing*)
c. Use of temperature pro-
gramming
Method similar to that for
natural gas (D 1945) except
that different chromotographic
columns used to afford separa-
tion of large amounts of car-
bon monoxide, nitrogen, and
unsaturated hydrocarbons often
found in synthesis gases.
Method basically the same as
for natural gas. See #1 (Na-
tural Gas), Part A.
Hydrogen sulflde is scrubbed
from the gas stream with zinc
acetate solution. The sulflde
is treated with acidified solu-
tion of an aromatic amlne and
ferric chloride catalyst to
form methylene blue due which
is measured by colorimetry.
APPLICABILITY
Each of the variations has
been applied to analysis
of natural gas.
Column packing and length
modified as necessary for
particular mixture.
Applicable to mixtures of
saturated and unsaturated
hydrocarbons, and carbon
monoxide.
Applicable to gases con-
taining up to 23 mg HaS/
cu meter. Limit of method
is .023 mg HaS. Should be
applicable for all synthe-
sis gases.
ACCURACY (A) AND PRECISION (P)
(P) Relative standard deviations
range from 0.1Z to 4Z for
major to trace (0.05Z) hydro-
carbons .
(P) See information given in
#1 (Natural Gas), Part C.
(P) See information given in
II (Natural Gas), Part A.
(P) The repeatability (individual
analyst - 95Z confidence) over
the range of applicability (in
ng/cu meter) is:
Sulfide
Cone.
Range
< II
1Z - 5Z
5Z - 23Z
Repeatability
0.2
0.4
10Z of amount
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Table II-2
METHODS OF ANALYSIS FOR GASEOUS FUELS
(continued)
PARAMETER
3b. Hydrogen Sulfide
and Hercaptan
Sulfur
SUGGESTED METHOD(S)
No./Title Ref.
ASTM D 2385
SUMMARY OF METHOD
Hydrogen sulfide is scrubbed
from the gas stream with neu-
tral cadmium sulfate solution,
and mercaptans with alkaline
cadmium sulfate solutions.
Sulfide and mercaptana are
measured by iodometric titra-
tion.
APPLICABILITY
Applicable to gases con-
taining up to 100 mg H2S/
cu meter and 22 mg mercap-
tan S/cu meter. Limit of
method is 20 mg. Method
should be applicable for
any synthesis or reformer
gas. Sample should be
collected at the source.
ACCURACY (A) AND PRECISION (P)*
(P) The precision (95Z confidence)
over the range of applicability
(in mg/cu m) is:
Sulfide Expected Precision (mg/cu m)
Cone. Individual Labs
2.3
23
115
0.7
2.5
8.2
0.9
3.4
11.A
4. Total Sulfur
A.
ASTM
D 1072
B.
ASTM
D 3031
5. Calorific Value ASTM D 1826
Sample is burned in closed
system and sulfur oxides are
absorbed (as sulfate) into
sodium carbonate solution.
Sulfate is titrated with bar-
ium chloride solution to a
color indicator endpoint.
Sample is combusted in hydro-
gen to hydrogen sulfide and
measured by the methylene
blue method.
A known flow of gas is burned
and the heat transferred to a
known air flow. The tempera-
ture of the air is then related
to the calorific value.
Applicable to gases con-
taining 23 mg S/cu meter
to 700 mg S/cu meter.
Applicable to gases con-
taining up to 23 mg S/cu
meter, and not more than
0.5Z of Cs and heavier
hydrocarbons.
Applicable to gases in
the 8,000 K cal to
11,000 K cal/cu meter
(900 Btu to 1,200 Btu/
cu foot); apparatus can
be adjusted for gases
of lower calorific value.
(A) Accuracy expected to be from
2 mg S/cu m to 16 mg S/cu m.
(P) No precision data.
(P) The expected precision (95Z
confidence) over the range of
applicability (in mg S/cu m)
is:
Repeatability
0.2
0.4
10Z of amount
< 1Z
1Z - 5Z
5Z - 23Z
(P) With weekly standardization
precision (95Z confidence) ex-
pected to be 0.3Z or better.
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Notes for Table II-2;
*Precision, when known, is usually given as either repeatability and/or reproducibility. The number
given for repeatability is the acceptable difference for duplicate results by the same laboratory;
that for reproducibility is the acceptable difference of duplicate results submitted by two or more
laboratories. The original reference should be checked if precision is critical since the wording
may imply special conditions for the applicability of the precision numbers given.
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CHAPTER III
LIQUID PETROLEUM FUELS
1. INTRODUCTION/SUMMARY
Liquid petroleum fuels include all the fractions commonly isolated from
the distillation of crude oil and are listed below in order of decreasing
volatility.
1. Liquefied petroleum gas
2. Gasoline (motor and aviation)
3. Gas turbine fuels
4. Diesel fuels
5. Heating oils
The discussion also deals with waste lubricating oils which are sometimes
combusted. Table III-l gives a summary listing of the fuel analyses that
are important for liquid petroleum fuels combustion, along with an identi-
fication of the preferred method of analysis. Quantities of the sample
required, costs, and standard reference materials (where available) are
given in Table III-2. Additional information on the methods of analysis
is tabulated in Section 3"of this chapter. All of the methods discussed
are taken from the American Society for Testing and Materials' (ASTM)
standards for petroleum products and lubricants1.
i
A complete environmental assessment of processes using certain liquid
petroleum fuels will require analyses beyond those covered by this manual;
for example, analysis of trace metals in heating oils and waste lubricat-
ing oils, analysis of hydrocarbon components such as polunuclear aromatics
in heavy heating oils, and stability to oxidation.
Petroleum fuels consist mainly of hydrocarbons which increase in molecular
weight and structural complexity from liquefied petroleum gas to heating
17
-------
oils. The fuels are specified according to physical and use-related para-
meters and, therefore, may differ in chemical composition from sample to
sample.
Nitrogen, sulfur, and trace metals are only present in trace quantities
f\
in the lighter fuels, i.e., up to gas turbine fuels or light heating oils .
The heavier heating oils contain higher amounts of nitrogen, sulfur, and
trace metals because processing of the crude oil concentrates these mate-
rials in the heavier fractions. Performance specifications for gasoline,
diesel oil, and gas turbine fuels strictly limit the amounts of these im-
purities which may be present. However, some of the fuels may contain
additives, e.g., lead alkyl compounds are added to gasoline to improve its
anti-knock properties. Waste lubricating oils may contain a variety of
added components such as phosphorus, zinc, calcium, and barium.
Petroleum fuels may be subjected to long periods of storage, and additives
(e.g., sulphonates, amines, metal phenolates) are used to inhibit oxida-
tion.
Sulfur is present as mercaptans, sulfides, and thiophenes. Nitrogen is
found as derivatives of pyridine and pyrole. Oxygen compounds are quinones,
phenols, and acids.
2. SAMPLING
Procedures for sampling liquid petroleum fuels are given in ASTM D 270,
"Standard Method of Sampling Petroleum and Petroleum Products"1. This
standard describes the various types of sampling procedures and sampling
containers to be used for different liquid petroleum fuels. Liquefied
petroleum gas (LPG) must be sampled in a different manner because of its
high volatility at room temperature. ASTM D 1265 describes the '."Standard
Method of Sampling Liquefied Petroleum Gases"1.
18
-------
3. ANALYSES
Table III-3 gives, for each parameter of interest, additional information
on the method(s) of analysis deemed suitable. When more than one method
is listed, the preferred method is listed first. The parameters are list-
ed in the order given in Table III-l.
Most of the methods described are already widely accepted for the analysis
of petroleum fuels1. Because the different petroleum fractions cover such
a wide range of properties, more than one method is necessary to provide
analysis for certain parameters. This is particularly true for liquefied
petroleum gases which have a high volatility2.
Compositional analysis of the heavier petroleum fractions (e.g., heating
oils) becomes very complex. Methods for separation and identification of
classes of compounds and individual components have been developed by
EPA3 and by the U. S. Bureau of Mines (American Petroleum Institute)4.
A detailed discussion of these techniques which involve liquid chromato-
graphy separation and infra-red or gas chromatography/mass spectrometry
identification techniques is beyond the scope of this study.
The ASTM Annual Book of Standards 5 contains many alternative analyses for
some of the parameters listed; our choice has been made from those which
appeared to offer the widest applicability.
1 4. REFERENCES
1. "Annual Book of ASTM Standards (1974) - Parts 23, 24, and 25: Petro-
leum Products and Lubricants," American Society for Testing and Mate-
r ials, Philad elphia, Pennsylvania.
2. "Liquefied Petroleum Gas, Specifications and Test Methods," Gas Pro-
cessors Association, Publication No. 2140-75.
3. "IERL-RTP Procedures Manual: Level 1 - Environmental Assessment,"
EPA 600/2-76-160a, June, 1976.
19
-------
4. Haine, W. E. and Thompson, C. J., "Separating and Charactizing High
Boiling Distilates - The USBM-API Procedure," U. S. ERDA, LERC/RI-75/5,
July, 1975.
5. "Annual Book of ASTM Standards (1974) - Part 26: Gaseous Fuels; Coal
and Coke; Atmospheric Analysis," American Society for Testing and Mate-
rials, Philadelphia, Pennsylvania.
6. "Annual Book of ASTM Standards (1974) - Part 30: Standard Method of
Test for Total Nitrogen in Organic Materials by Modified Kjeldahl
Method," American Society for Testing and Materials, Philadelphia,
Pennsylvania.
20
-------
Table III-l
ANALYSES FOR LIQUID PETROLEUM
PARAMETER
1. Carbon (Total)
and Hydrogen
2. Nitrogen
3. Sulfur
4. Oxygen
5. Chlorine
6. Water and
Sediment
7. Ash
8. Calorific Value'
9. Carbon Residue
10. Distillation
11. Vapor Pressure
12. Flash Point
13. Pour Point
14. Viscosity
15. Density
16. Corrosion
NA - Not Applicable
LIQUIFIED
PETROLEUM GAS
NA
NA
ASTM D 2784
a
NA
NA
NA
NA
ASTM D 2158b
NA
ASTM D 1267
NA
NA
NA
ASTM D 1657
ASTM D 1838
a. Obtained by difference.
b. Residue of higher boiling hyd
GASOLINE
ASTM D 3178
NA
ASTM D 1266
___a
NA
ASTM D 1094
NA
ASTM D 240
NA
ASTM D 86
ASTM D 323
ASTM D 93
ASTM D 97
NA
ASTM D 1298
ASTM D 130
rocarbons, not
FUELS
PREFERRED METHODS
GAS TURBINE
FUELS
ASTM D 3178
ASTM E 258
ASTM D 129
___ a
NA
ASTM D 2709
ASTM D 482
ASTM D 240
ASTM D 524
ASTM D 86
ASTM D 323
ASTM D 93
ASTM D 97
ASTM D 445
ASTM D 1298
ASTM D 130
carbon residue
DIESEL FUEL
ASTM D 3178
ASTM E 258
ASTM D 129
a
NA
ASTM D 2709
ASTM D 482
ASTM D 240
ASTM D 524
ASTM D 86
NA
ASTM D 93
ASTM D 97
ASTM D 445
ASTM D 1298
ASTM D 130
•
HEATING OIL
ASTM D 3178
ASTM E 258
ASTM D 129
a
ASTM D 808
ASTM D 1796
ASTM D 482
ASTM D 240
ASTM D 524
ASTM D 86
NA
ASTM D 93
ASTM D 97
ASTM D 445/
ASTM D 88
ASTM D 1298
ASTM D 130
WASTE
LUBRICATING OILS
ASTM D 3178
ASTM E 258
ASTM D 129
a
ASTM D 808
ASTM D 1796
ASTM D 482
' ASTM D 240
ASTM D 524
ASTM D 86
NA
ASTM D 93
ASTM D 97
ASTM D 445/
ASTM D 88
ASTM D 1298
ASTM D 130
-------
Table III-2
ANALYSES FOR
LIQUID PETROLEUM
FUELS
SUMMARY LISTING
PARAMETER
APPROXIMATE
AMOUNT OF
SAMPLE NEEDED COST OF
PREFERRED METHODa FOR ANALYSIS15 ANALYSIS0
SRM
AVAILABLE*1
(g)e ($)
1.
2.
3.
4.
5.
6.
7.
8.
9.
10.
11.
12.
13.
14.
15.
16.
Carbon (Total)
and Hydrogen
Nitrogen
Sulfur
Oxygen
Chlorine
Water and
Sediment
Ash
Calorific Value
Carbon Residue
Distillation
Vapor Pressure
Flash Point
Pour Point
Viscosity
Density
Corrosion
ASTM
ASTM
ASTM
ASTM
ASTM
—
ASTM
ASTM
ASTM
ASTM
ASTM
ASTM
ASTM
ASTM
ASTM
ASTM
ASTM
ASTM
ASTM
ASTM
ASTM
ASTM
ASTM
ASTM
D
E
D
D
D
D
D
D
D
D
D
D
D
D
D
D
D
D
D
D
D
D
D
3178
258
2784
1266
129
808
2709
1796
482
240
2158
52.4
86
1267
323
93
97
445
88
1657
1298
1838
130
0
'b 2
24 -
2 -
0.6 -
—
0
100
50 -
100
0.6 -
100
50
100
1,200
1 -
75 -
45 -
.2 (30 - 70)
15 - 25
40
15 20
1.0 25
.8 20
ml 5
60 6.5 - 20
0.7 24 - 40
ml
ml 15
ml 25
ml
7 liters 10 - 20
90 16 - 25
55 12 - 20
LF-1
LF-2
LF-2
LF-5
f 8-15
100
600
—
30 -
30 -
ml 13.5 - 25
ml
-f 5
90
90 6.5 - 20
Notes appear on following page.
22
-------
Notes to Table III-2;
a. All methods given are by the American Society for Testing and Mate-
rials. Specific references are cited in Table III-3 for each para-
meter.
b. These are the sample requirements for a single analysis.
c. Estimates based on prices charged by analytical services laboratories
for petroleum fuels in early 1977.
d. See Appendix A for details.
e. Note that many values are in ml.
f. The amount needed varies with the type of equipment used and, for
viscosity, with the value of the viscosity.
23
-------
Table III-3
METHODS OF ANALYSIS FOR LIQUID PETROLEUM FUELS
PARAMETER
1. Carbon (Total)
and Hydrogen
SUGGESTED METHOD(S)
No./Title Ref.
ASTM D 3178
2. Nitrogen
ASTM E 258
Modified
Kjeldahl
(See Note #
to
-C-
SUMMARY OF METHODS
A weighed sample Is burned In a
closed system and the products
of combustion fixed In an ab-
sorption train. CC>2 absorber
may contain NaOH, KOH, or soda
lime. Moisture absorber is
anhydrous magnesium perchlorate
(Mg(C10,,)2).
A sample is digested in a mix-
ture of sulfuric acid, potas-
sium sulfate and mercuric ox-
ide converting nitrogen to
ammonium sulfate. After mer-
cury Is precipitated with so-
dium sulfide, the solution is
made alkaline with sodium hy-
droxide and the liberated
ammonia distilled Into an acid
solution. The amount of acid
neutralized is determined by
titration with sodium hydrox-
ide.
APPLICABILITY
Method developed for coal
and coke. Sample boats
may have to be modified to
hold liquid sample. Not
applicable to LPG.
Method developed for nitro-
gen containing organic com-
pounds. Not applicable for
materials containing N-0,
N-N linkages. Should be
applicable for petroleum
liquids, except LPG.
ACCURACY (A) AND PRECISION (P)*
(P) Not specified for petroleum
liquids. For coal and coke:
Repeatability:
Carbon - 0.3%
Hyrdogen - 0.07%
(P) Not specified for petroleum
liquids, for organic com-
pounds in general:
Repeatabilityi 0.1% abso-
lute for two results, each
the average of duplicate de-
terminations. See Reference
96 for additional information.
ReproducIbllity; 0.22 abso-
lute for two results, each
the average of duplicate de-
terminations. See Reference
#6 for additional information.
3. Sulfur
A.
ASTM
D 129
General Bomb
(See Note #2)
A sample is oxidized In a bomb
containing oxygen under pres-
sure. The sulfur, as sulfate
in the bomb washings, is deter-
mined gravimetrically as
barium sulfate.
Generally applicable for
petroleum products that
are not highly volatile
and that contain at least
0.1% sulfur. Not appli-
cable to LPG, gasoline,
or lubricating oils con-
taining additives.
(P) Repeatability; 0.4% to 0.6%
when S is between 0.1% and 1.0%.
Reproduclblllty; 0.05% to 0.09%
When S is between 0.1% and 1.0%.
See Reference #1 for additional
information.
All notes appear on the last page of this table,
-------
Table III-3
PARAMETER
3. Sulfur
continued
to
in
4. Oxygen
METHODS OF ANALYSIS FOR LIQUID PETROLEUM FUELS
(continued)
SUGGESTED METHOD(S)
No./Title Ref.
B.
ASTM
D 1266
Lamp
Method
C.
ASTM
D 2784
Oxy-hydrogen
Burner
D. ASTM 1
D 1552
High-Temperature
Method
ASTM D 271
SUMMARY OF METHODS
A sample Is burned in a closed
system using a suitable wick
lamp with an atmosphere of 70%
COa, 30% 02- The oxides of
sulfur are oxidized to sulfuric
acid with hydrogen peroxide.
Sulfate in the absorbant is
determined by titration with
NaOH or by precipitation as
BaSOif.
A sample is burned in an oxy-
hydrogen burner in CO /O atmos-
phere. Oxides in sulfur are ab-
sorbed in hydrogen peroxide and
oxidized to sulfuric acid. Sul-
fate ion is determined by titra-
tion with barium perchlorate or
by precipitation of barium sul-
fate followed by trubidometry.
A sample is burned in a stream
of oxygen at high temperature
to convert about 97% of the
sulfur to S02. The combustion
products are absorbed in acid
solution of Kl/atarch indicator.
Potassium lodate is added as
the combustion proceeds and
the amount of standard iodate
consumed is a measure of the
sulfur content of the sample.
Oxygen is determined indirectly
by subtracting from 100 the per-
centages of hydrogen, carbon,
sulfur, nitrogen, and ash.
APPLICABILITY
Applicable to volatile pet-
roleum products that con-
tain more than 0.002% sul-
fur and can be completely
burned in a wick lamp.
Applicable to LPG contain-
ing more than 1 ppm of sul-
fur, not more that 100 ppm
halogen.
Applicable to petroleum
fractions boiling above
350°F, particularly lubri-
cating oils containing addi-
tives. Chlorine interferes
above 1%, nitrogen may in-
terfere above 0.1%.
Method developed for coal
and coke.
ACCURACY (A) AND PRECISION (P)*
(P) Repeatability: 5 ppm -
80 ppm: 0.116 * ppm S
80 ppm: (0.01 x ppm s).+ 8.5
Reproduclbillty; 5 ppm -
125 ppm: 0.145 x ppm S
125 ppm - 280 ppm: (0.508 x
ppm S) - 45.4
Not stated
(P) Repeatability:
0 - 0.5 wt. % S: 0.05
0.5 - 1.0 wt. % S: 0.07
1.0 - 2.0 wt. % S: 0.10
Reproduciblllty;
0 - 0.5 wt. Z S: 0.08
0.5 - 1.0 wt. % S: 0.11
1.0 - 2.0 wt. % S: 0.17
Not known
-------
Table III-3
METHODS OF ANALYSIS FOR LIQUID PETROLEUM FUELS
(continued)
PARAMETER
5. Chlorine
6.. Water and
Sediment
to
ON
SUGGESTED METHOD(S)
No./Title Ref.
ASTM D 808
Bomb Method
(See Note ff3)
A.
ASTM
D 1796
Centrifuge
(See Note #4)
B.
ASTM
D 95
Water by
Distillation
SUMMARY OF METHODS
Sample Is oxidized by combus-
tion In a bomb containing oxy-
gen under pressure. The chlor-
rine compounds liberated are
absorbed in a sodium carbonate
solution and the amount of
chlorine present determined
gravlmetrically by precipita-
tation as silver chloride.
The combined volume of water
and sediment is measured volu-
metrically at the bottom of a
centrifuge tube after a 50:50
solvent/sample mixture is cen-
trifuged in a specified manner
and at a specific temperature
(49°C, or 60eC, If wax contri-
butes to volume of water and
sediment).
The sample is heated under re-
flex with a water immiscible
solvent which co-distills with
the water in the sample. Con-
densed solvent and water are
continuously separated In a
trap, the water settling in
the graduated section of the
trap and measured volumetri-
cally.
APPLICABILITY
Method developed for lub-
ricating oils and greases.
Assumes other halogens are
not present; lower limit of
applicability is 0.1% chlor-
rine.
Applicable to crude oils
and fuel oils (based on
petroleum). Not applicable
if water content is less
than 0.05%.
Applicable to crude petro-
leum, tars, and products
derived from these mater-
ials.
ACCURACY (A) AND PRECISION (?)*
'(P) For lubricating oils and
greases:
Repeatability: 0.07 % for
chlorine content in range
of 0.1% to 2%.
Reproduclbllity: 0.10%
for chlorine content in
range of 0.1Z to 2Z.
(P) Repeatability: Ranges
from 0.01% to 0.07% when
value is 0.1% to 1.0%,
respectively.
Reproduclbllity: Ranges
0.11% to 0.20% when value
is 0.1% and 1.0%, respec-
tively.
(P) Repeatability; 0.1 ml if
if water collected Is
< 1.0 ml.
Reproduoibllity: 0.2 ml
if water collected is
< 1.0 ml.
-------
Table III-3
METHODS OF ANALYSIS FOR LIQUID PETROLEUM FUELS
(continued)
PARAMETER
SUGGESTED METHOD(S)
No./Title Ref.
7. Ash
ASTM D 482
(See Note 93)
a.
Calorific
Value
ASTM D 240 - 1
(See Notes «3
and #5)
9. Carbon Residue A. ASTM
D524
Rams-bottom
(See Note #6)
SUMMARY OP METHODS
A sample is ignited in a cru-
cible or evaporating dish and
allowed to burn until only ash
and carbon remain. The carbon-
aceous residue is reduced to an
ash by heating in a muffle fur-
nace at 775°C, cooled and weigh-
ed.
A weighed sample is burned in
an oxygen bomb calorimeter
under controlled conditions.
The heat of combustion is com-
puted from temperature obser-
vations before, during, and
after combustion. Allowance
is made for thermochemical
and heat transfer corrections.
Either isothermal or adia-
batic calorimeter jackets may
be used.
A sample is placed in a special
glass bulb having a capillary
opening and then placed in a
metal furnace maintained at i,
550°C. Heating is for 20 min-
utes. The bulb is then cool-
ed in a dessicator and weigh-
ed. A modification is given
for light distllate oils; the
method, as given above, is
used on a 10Z distillation
residue of the sample.
APPLICABILITY
Applicable to most types
of petroleum oils, in-
cluding crude, residual
fuels, distilates, and
lubricating oils (con-
taining no additives).
Applicable to a wide vari-
ety of substances, but par-
ticularly to liquid hydro-
carbon fuels of both low
and high volatility.
Applicable to relatively
non-volatile petroleum
products which oartially
decompose on distillation
at atmospheric pressure.
High ash content may give
erroneously high values.
ACCURACY (A) AND PRECISION (P)*
(P) Repeatability: 0.002%
when ash is in range of
0.002% to 0.15%.
Reproducibiity: 0.004%
when ash is in range of
0.002% to 0.15%. See Re-
ference #1 for additional
information.
(P) Repeatability:
30.6 cal/g (55 Btu/lb)
Reproducibility;
97.2 cal/g (175 But/lb)
(P) Repeatability: 0.25Z for
average carbon residue of
0.1Z. See Reference fl
for other points.
Reproducibility: 0.035%
for average carbon resi-
due of 0.1%. See Refer-
ence fl for other points.
-------
Table III-3
METHODS OF ANALYSIS FOR LIQUID PETROLEUM FUELS
(continued)
PARAMETER
9.
Carbon Residue
continued
Si
00
10. Distillation
SUGGESTED HETHOD(S)
No./Title Ref.
B.
ASTM
D 189
Conradson
(See Note #6)
C.
ASTM
D2158
Residues
(See Note 06)
ASTM D 86
Petroleum
Products
SUMMARY OF METHODS
A sample is placed in a covered
crucible and subjected to des-
tructive distillation. At the
end of a 30 minute heating per-
iod the crucible is cooled and
weighed. Modifications are
prescribed for high residue
materials.
A 100 ml sample of LPG is
weathered in a 100 ml centri-
fuge tube. The volume of resi-
due remaining at 100°F is
measured.
A 100 ml sample is distilled
under prescribed conditions
which depend on the vapor
pressure and initial and final
distillation points. Syste-
matic observations of temper-
ature and condensate volume
are made, and the reported
results calculated from their
data.
APPLICABILITY
Applicable to relatively
non-volatile petroleum
products which partially
decompose at atmospheric
pressure. High ash con-
tent may give erroneously
high values.
Applicable to sample of
LPG such as propane, bu-
tane, or mixtures.
These residues are higher
boiling hydrocarbons not
carbon residue.
Applicable to motor and
aviation gasolines, avia-
tion turbine fuels, dis-
tilate fuel oils, and
similar petroleum pro-
ducts.
ACCURACY (A) AND PRECISION (P)*
(P) Repeatability; 0.022* for
average carbon residue of
0.0%. See Reference til
for other points.
Reproduclbilty: 0.058% for
average carbon residue of
0.1%. See Reference 01
for other points.
(P) Repeatability:
Residue number 0-20: 5
20 - 40: 10
40 - 60: 20
Reproductbllity;
Residue number 0-20: 10
20 - 40: 10
40 - 60: _30
(P) Varies with the initial
boiling point and 'end
point of the material
and with, the rate of
change of thermometer
readings. See Refer-
ence tl for data.
-------
Table III-3
METHODS OF ANALYSIS FOR LIQUID PETROLEUM FUELS
(continued)
PARAMETER
11. Vapor Pressure
SUGGESTED METHOD(S)
Ho./Title Ref.
A. ASTM
D 323
Reid
Method
SUMMARY OF METHODS
One chamber of the apparatus is
filled with a chilled sample,
and connected to an air chamber
at 37.8°C (100"F) or other 'tem-
perature. The apparatus is im-
mersed in a. constant-temperature'
bath at 37.8°C (100°F) and shaken
until equilibrium is reached.
The vapor pressure is then ob-
tained from manometer readings,
suitably 'corrected if the air
chamber was not initially at
37.8eC (100'F).
APPLICABILITY
.Applicable to crude (pet-
roleum) oil and volatile
non-viscous petroleum pro-
ducts, except liquid petro-
leum gases.
ACCURACY (A) ACT PRECISION (P)*
(P) Repeatability: VarJ.es
with vapor pressure; is
0.2% pressures in range
of .35 to 1.1 kg/cm2
(5 to 16 Ibs).
ro
B.
ASTM
D 1267
LPG Method
Similar to the Reid Method, the
test apparatus consists of two
interconnected chambers and is
equipped with a pressure guage.
It is purged with sample then
completely filled. 402 is sub-
sequently withdrawn to provide
free space for product expan-
sion. The apparatus is equili-
brated at 100°F and the guage
pressure observed.
Applicable to LPG con-
taining less than 52
hydrocarbons boiling
above 32°F and with
vapor pressure not ex-
ceeding 225 psi.
(P) Repeatability; 0.5 Ib
0.52 of mean value.
Reproducibility;
1.01 Ib + 0.52 of nean
value.
12. Flash Point
ASTM D 93
Penaky-
Marteus
Closed Cup
A sample is heated in a covered
cup at a slow, constant rate
with continual stirring. A small
flame is directed into the cup-
through opening in the cover -
at regular intervals with simul-
taneous Interruption of the stir-
ring. The flash point is the
lowest temperature at which the
vapor above the sample is ignited
by the test flame.
Applicable to fuel oils,
lube oils, and other petro-
leum liquids.
(P) Repeatability: 2°C for
flash points under 104.4"C,
5.5"C for flash.
Reproducibility; 3.5°C
for flash points under
104.4°C. 8.5"C for flash
points above 104.4°C. See
Reference fl for addition-
al data on precision for
viscous materials.
-------
Table III-3
PARAMETERS
14. Viscosity
LO
O
METHODS OF ANALYSIS FOR LIQUID PETROLEUM FUELS
(continued)
13. Pour Point
SUGGESTED METHOD (S)
No./Title Ref.
ASTM D 97
A.
ASTM
D 445
Kinematic
and Dynamic
(See Note 07)
B. ASTM
D 88
Saybolt
(See Notes #7
and #8)
SUMMARY OF METHODS
After preliminary heating, a
sample is cooled at a speci-
fied rate and examined at inter-
vals of 3°C (5°F) for flow
characteristics. The lowest
temperature at which movement
of the oil is observed is the
pour point. A modification
for determining the lower (min-
imum) pour point of black oil,
cylinder stock and non-dlsti-
late fuel oil is given.
The time (in seconds) it takes
a fixed volume of sample to
flow through a capillary Is
measured. The capillary is
calibrated and used with a
reproducable driving head and
with a closely controlled temp-
erature. The kinematic vis-
cosity is the product of the
measured flow time and the
calibration constant of the
viscosity is calculated from
the kinematic viscosity. Test
temperature must be specified
by the parties concerned.
The time required for a 60 ml
sample to flow through a cal-
ibrated orifice is measured
under carefully controlled
conditions. This time is cor-
rected by an orifice factor
and reported as the viscosity
of the sample at that temper-
ature. Test temperature must
be specified by the parties
concerned.
APPLICABILITY
Applicable to any petro-
leum oil.
ACCURACY (A) AND PRECISION (P)*
(P) Repeatability: 3°C (5°F)
Reproduclbllity; 6°C.
(10°F) - above not appli-
cable when modified pro-
cedure is used.
Applicable to liquid
petroleum products.
Not LPG.
(P) Repeatability: 0.35% of mean
Reprodueibility; 0.7Z of mean
Applicable to petroleum
products at test temper-
atures between 21.1°C and
and 98.9°C (70°F and
210°F).
Not given
-------
Table III-3
METHODS OF ANALYSIS FOR LIQUID PETROLEUM FUELS
(continued)
PARAMETER
IS. Density
CO
16. Corrosion
SUGGESTED METHOD(S)
Ho./Title Kef.
A. ASTM
D 1298
Density,
Specific
Gravity, or
API Gravity
B.
ASTM
D 1657
S.G. of
light hydro-
carbons by
hydrometer
A.
ASTM
D 130
Copper
Strip
SUMMARY OF METHODS
A sample is brought to the pre-
scribed temperature and trans-
ferred to a cylinder at approx-
imately the same temperature.
An appropriate hydrometer is
lowered into the sample and
allowed to settle. The density
is then read from the hydro-
meter scale where it breaks the
liquid surface. Test temper-
ature preferred near 15°C (60°F)
but may be between (18°C and
90°C [0°F and 195°F). Test
temperature should be speci-
fied by parties concerned.
All readings are reduced to
15"C (60°F) for reporting.
The pressurized cylinder is
purged with the sample and
then filled to a level at
which the hydrometer floats
freely. The density is read
from the hydrometer scale
where it breaks the liquid
surface.
A polished copper strip is Im-
mersed in a sample at a certain
temperature for a time char-
acteristic of the sample being
tested. The copper strip is
then removed, washed and com-
pared with the ASTM Copper
Strip Corrosion Standards Mod-
ifications are given for dif-
ferent types of petroleum pro-
ducts; in some cases the parties
concerned must specify the temp-
erature and time for the test.
APPLICABILITY
1 Applicable to crude petro-
leum and petroleum pro-
ducts normally handled as
liquids and having a Reid
vapor pressure of 1.8 kg/
cm* (26 Ibs/in2) or less.
Applicable" to LPG and
other light hydrocar-
bons with Reid vapor
pressure above 26 lb/
in2.
Applicable to petroleum
fuel oils, gasolines, lu-
bricating oils, and certain
other petroleum products.
ACCURACY (A) AND PRECISION (P)*
(P) Repeatability:
0.0005 to 0.0006 for specific
gravity and density, and 0.1
to 0.2 for API gravity, depend-
ing on type of oil. See Refer-
ence ill for details.
Reproducability:
0.0012 to 0.0015 for specific
gravity and density, and 0.3
tp 0.5 for API gravity, de-
pending on type of oil. See
Reference 11 for details.
(P) Repeatability: 0.001
Reproducibility: 0.003
Not given
-------
Table III-3
METHODS OF ANALYSIS FOR LIQUID PETROLEUM FUELS
(continued)
SUGGESTED METHOD(S)
PARAMETER No./Title Ref. SUMMARY OF METHODS APPLICABILITY ACCURACY (A) AND PRECISION (P)*
16. Corrosion B. ASTM 1 This test is similar to ASTM Applicable to LPG and simi- Not given
continued D 1838 D 130 above except that the lar low boiling petroleum
Copper container is a closed cylinder liquids.
Strip LPG which can be pressurized. A
temperature of 100°F for one
hour is normally specified.
^Precision, when known, is usually given as either repeatability and/or reproducibility. The number given for repeatability is the acceptable
difference for duplicate results by the same laboratory; that for reproducibility is the acceptable difference for duplicate results submitted
by two or more laboratories. The original reference should be 'checked if precision is critical since the wording may imply special conditions
for the applicability for the precision numbers given. Accuracy is given when listed in the original reference.
1. Data from analyses of two petroleum fuels for nitrogen by another method, ASTM 32281, are given in Appendix D. This is also a modified
Kjeldahl method, but in only Intended for use when nitrogen is present from 0.03 wt. 7. to 0.10 wt. Z.
2. Data from analyses of two petroleum fuels for sulfur by another method, ASTM's "High Temperature Method" (ASTM D 1552)1 are given, in Appen-
dix D. A warning is given .the nitrogen, when present in excess of 0.1%, may interfere with this method. Both shale oil and coal liquids.
contain nitrogen above this level.
3. Data from analyses of two petroleum fuels by this method are given in Appendix D.
4. An essentially similar method is given in ASTM D96, "Standard Method of Test for Water and Sediment in Crude Oils"1.
5. Another acceptable method is given in ASTM D 2382, "Standard Method of Test for Heat of Combustion of Hydrocarbon fuels by Bomb Calorimeter
(High Precision Method)"1. It is designed specifically for use with aviation turbine fuels when the permissible difference between duplicate
determinations: is of the order of 0.1%. The method can be used for a wide range of volatile and non-volatile materials where slightly greater
differences in precision can be tolerated1.
6. While no exact correlation exists between the Conradson (D 189) and Ramsbottom (D 524) methods for carbon residue, an approximate correlation
for petroleum products has been found and is shown graphically in Reference #1. The correlation may not be valid for unusual petroleum products
and ASTM urges caution in the application of this correlation at low carbon residues.
7. Tables are given in ASTM D 2161 for conversion of kinematic viscosity (in centistrokes) to Saybolt viscosity (in seconds) and the reverse.
8. This frequently used method was, until recently, included in Part 23 of ASTMvs Book of Standards and was under the jurisdiction of ASTM Commit-
tee D-2 on petroleum products and lubricants. The method has recently transferred to the jurisdiction of ASTM Committee D-8 on asphalt and,
accordingly, is now found in Part IS of ASTM's Book of Standards. This transfer was in accordance with ASTM's plans to phase-out non-metric
methods of test for petroleum products.
-------
CHAPTER IV
SHALE OIL AND COAL LIQUIDS
1. INTRODUCTION/SUMMARY
A. Shale Oil
Shale oil is taken here to include any liquid organic material recovered
from oil shale that is suitable for combustion. This includes both crude
and refined shale oil. Shale oil is usually recovered from oil shale by
a process called retorting, which subjects the shale to high temperatures
(500°C to 550°C) at which the bonds linking the organic compounds to the
remainder of the rock matrix are broken. The liberated compounds in the
gaseous state are collected, condensed, and upgraded into a liquid pro-
duct that is the rough equivalent of a crude oil. Other processes for the
recovery of shale oil are being investigated, but are not as far advanced
as retorting. While detailed development plans have been prepared for
major shale oil production facilities, no shale oil is being commercially
produced at this time (mid-1977).
Table IV-1 gives a summary listing of the fuel analyses that are important
for shale oil (and coal liquids) combustion, along with an identification
of the preferred method of analysis and other information relating to the
analyses. Additional information on the methods of analysis, including
alternate methods for some parameters, is given in Section 3 of this chap-
ter. All of the methods discussed are given by the American Society for
Testing and Materials (ASTM), primarily in their standards for petroleum
products and lubricants1- None of the methods discussed were developed
specifically to include applicability to shale oils and coal liquids, but
they are, nevertheless, expected to be adequate.
A set of standard methods for the analysis (specification testing) of shale
oils and coal liquids do not exist, at present, though a laboratory method
for the examination of crude shale oil was published by the Bureau of Mines
33
-------
in 195210. The publication discusses several shale oil analyses including
water, distillation, nitrogen, sulfur, specific gravity, pour point, and
viscosity. The methods discussed are based on Bureau of Mines methods for
petroleum11 with modifications included to take into account the apparent
poor heat stability of shale oil and the presence of large quantities of
olefins and nitrogen compounds. Because the methods are not sufficiently
detailed for use as a standard method, they have not been listed in this
manual. Comments have, however, been included in Table IV-3 of this chap-
ter, where appropriate.
Environmental assessments of processes using shale oil and coal liquids
will need to include additional fuel analysis beyond those covered in this
manual. Those likely to be required include trace elements in the fuel
and in the ash, characterization of organic compounds present, and possi-
bly, fuel-stability tests.
Shale oils differ from petroleum oils in composition and this may be an im-
portant aspect in an environmental assessment*. The organic material in
oil shale is composed of a soluble bitumen fraction consisting of about 20%
of the available organic matter, while the remainder exists as insoluble
kerogen. The organic fraction of the shale may be around 15% of the oil
shale. While oil shales are found in many areas of the U. S., the most im-
portant are found in the Green River formations in Colorado, Wyoming, and
Utah. The kerogen of these shales consists of polycylic subunits intercon-
nected by long chain alkanes and isoprenoids. The matrix also contains sub-
stantial amounts of entrapped, uncondensed alkanes, and fatty acids. The
shale oil made from this material contains substantially higher amounts of
nitrogen, oxygen, olefins, and ring compounds than does petroleum oil. Sul-
fur contents are generally lower than in petroleum oils. For some of the
crude shale oils, over half of the material consists of compounds of sulfur,,
nitrogen, and oxygen, and less than half consists of pure hydrocarbons. The
*Much of the information below is from Reference #2. Additional informa-
tion is given in Reference #3.
34
-------
nitrogen compounds tend to concentrate in the higher boiling portions of
shale oil.
Nitrogen in shale oil (naphtha fraction) is present as pyridines, pyrroles,
and nitriles. Sulfur is primarily in the form of thiophenes, with some
sulfides and small amounts of disulfides and thiols present. Oxygen com-
pounds found include phenols and carboxylic acids. A majority of the ni-
trogen and sulfur compounds are heterocyclic - that is, with the hetero-
atoms contained in the rings. A significant amount of work has been done
to determine the hydrocarbon types (including N- and S- compounds) in shale
oils and procedures for shale oil characterization have been worked out.
A bibliography, listing publications on this and other subjects, is given
in Reference #4.
Of all the possible variables which affect the characteristics of shale
oil, the method of production is, by far, the most significant. A vari-
ety of in situ and ex situ retorting processes have been proposed and
each may lead to a different quality of oil. The composition of the
shale oil will also vary from location to location and with the depth
(of the original oil shale) at a given location.
B. Coal Liquids
The processing of coal to clean fuels - liquid, gaseous, or solid - is of
considerable interest. There are two principal processes for accomplish-
ing the conversion to liquid:!
1. Pyrolysis - coal is heated to induce carbonization and thermal crack-
ing.
2. Dissolution - coal is liquefied by an extractive process, usually
through the agency of a solvent.
35
-------
Both of these processes present a large number of alternative schemes for
producing coal-derived liquids. For example, in dissolution of coal, pro-
cesses might involve hydrogenation, catalysis, thermal liquefaction, and
a host of other variables, singly or in combination.
The diversity of process conditions, as well as the many possible start-
ing materials (including both coals and solvents), can lead to a multitude
of product liquids. In addition, the final upgrading or refining of the
coal liquid, e.g., to desulfurize, further increases the complexity of
classifying the resulting oil. The precise chemical nature of most coal
liquids is unknown. Frequently, the composition is described in terms of
solubility in various solvents, such as hexane, pentane, pyridine, and
benzene. Large fractions of coal liquids are often found to be aspha-
tenes - a general term usually referring to high molecular weight com-
pounds, boiling above 650°F and soluble in benzene (but insoluble in
light parafins such as pentane)12.
There are several apparent differences between petroleum products and coal
liquids, such as13:
• The oils from coal contain large concentrations of oxygen and other
heteroatoms.
• Branching of components is very different.
• High levels of polynuclear aromatics and rings substituted with one
to three alkyl groups are present in the coal-derived materials.
The distinctions between the two types of oil are related to structure of
the chemical compounds. Although the range of values for parameters will
differ, the analytical procedures are essentially the same. Since sepa-
rate methods for coal liquids have not, as yet, been proposed, those cur-
rently accepted for petroleum products are considered most appropriate.
However, one must exercise caution in the analysis of coal liquids due to
36
-------
the possible inclusion of unreacted coal in the liquid. This problem is
a result of the difficulty of solid/liquid separation in certain conver-
sion processes.
2. SAMPLING
Procedures for collecting representative samples of shale oil or coal liq-
uids will have to be tailored to (1) the nature of the material being sam-
pled; (2) the nature of the fuel processing, handling, or storage equip-
ment; and, (3) the precision and accuracy requirements of the analyses to
be carried out. Since neither material is currently in commercial produc-
tion, most sampling in the near term will be connected with bench or pilot
scale research facilities.
Standard sampling methods for shale oil and coal liquids have not been
developed, but the procedures given in ASTM D 270, "Standard Method of
Sampling Petroleum and Petroleum Products"1, will give a significant amount
of guidance. This "method" actually includes numerous methods for sam-
pling from a wide variety of containers for a wide variety of sample types,
as shown by the examples below.
General Methods: bottle or grab, tap, continuous, dipper, tube, thief,
boring, grab, and others;
Sample Containers; stationary tanks, ship or barge tanks, tank cars, and
packaged lots (e.g., cans, drums, barrels);
Sample Types; average, all-levels, running, spot, top, upper, middle,
lower, clearance, bottom, drain, water and sediment, composite, and
several others.
The parties concerned should agree on a sampling procedure for each pro-
ject. It should be noted that several ASTM methods of analysis require
37
-------
a specific sampling procedure to be used, including D 323 - Reid Vapor
Pressure - which is included in this manual.
ASTM D 270 also covers specifications for sample containers, sample han-
dling, labeling, and shipping. Because shale oil and coal liquids may
contain carcinogens, laboratory coats and gloves should be work whenever
there is the chance of spillage. The gloves should be made of butyl
rubber, rather than neoprene or any other material, since they have
been found to have the slowest permeation rate for a similar material,
coal tar creosote7.
3. ANALYSES
Table IV-2 gives, for each parameter of interest, additional information
on the method(s) of analysis deemed suitable. When more than one method
is listed, the preferred method is given first. The parameters are list-
ed in the order given in Table IV-1.
It should be noted that none of the listed methods were developed for
specific applicability to shale oil and coal liquids. Most methods were
developed for petroleum and petroleum products. While it is expected
that the listed methods will be generally applicable to shale oil and
coal liquids, this has yet to be proven by laboratory tests. It is pos-
sible that unanticipated problems will require some methods modifications.
Caution should be used in the comparison of any precision inforamtion
given in Table IV-2. Sample homogeneity may not be comparable and the
absolute value of the parameters being measured may differ significantly
in some cases.
38
-------
Specific Comments on Shale Oil
Many crude shale oils contain a substantial quantity of water, often in
the form of a stable emulsion. This water may be removed by distillation.
The Bureau of Mines has recommended drying samples of crude shale oil,
prior to subsequent analyses, with any equipment (e.g., drying oven, flask,
tubing, condenser, and receiver) that provides for the removal of water
from the sample without overheating or loss of oil1". The water content
may be measured, by weight difference, by this method, but may not be as
accurate as the method specified in this manual - ASTM D 95.
The Bureau of Mines report states that the specific gravity, sulfur con-
tent, nitrogen content, pour point, and viscosity are to be obtained on
the dried sample. This may not always be desirable for combustion studies
and the parties concerned should agree on the basis of the reporting.
4. REFERENCES
1. "Annual Book of ASTM Standards (1974) - Parts 23, 24, and 25: Petro-
leum Products and Lubricants," American Society for Testing and Mate-
rials, Philadelphia, Pennsylvania.
2. "Report of the Conference-Workshop entitled Analytical Chemistry Per-
taining to Oil Shale and Shale Oil," held June 24-25, 1974, at the
National Science Foundation, Washington, D. C.
3. "Fuel Contaminants - Volume 1: Chemistry," U. S. Environmental Pro-
tection Agency, Office of Research and Development, Washington, D. C.,
1976.
4. "A Bibliography of Oil Shale and Shale Oil," U. S. Energy Research
and Development Administration, Laramie Energy Research Center,
Laramie, Wyoming, 1974 - plus addendums for 1975 and 1976.
5. "Annual Book of ASTM Standard (1974) - Part 26: Gaseous Fuels; Coal
and Coke; Atmospheric Analysis," American Society for Testing and
Materials, Philadelphia, Pennsylvania.
6. "Annual Book of ASTM Methods (1974) - Part 30: Standard Method of
Test for Total Nitrogen in Organic Materials by Modified Kjeldahl
Method," American Society for Testing and Materials, Philadelphia,
Pennsylvania.
39
-------
7. Personal communication from Mr. Gerard C. Colletta, Arthur D. Little,
Inc., April, 1977. Selection of butyl rubber is based on preliminary
results of laboratory tests carried out by Arthur D. Little, Inc., for
the National Institutes of Occupational Safety and Health in a program
entitled, "Development of Performance Criteria for Protective Clothing
Used Against Carcinogenic Liquids."
8. Lake, G. R., McCutchan, P., Van Meter, R., and Neel, J. C., "(Deter-
mination of Nitrogen in Shale Oil and Petroleum) Effects of Digestion
Temperature on Kjeldahl Analysis," Analytical Chemistry, Volume 23,
No. 11, pages 1634-1638 (1954).
9. Ball, J. S. and Van Meter, R., "Determination of Nitrogen in Shale
Oil and Petroleum - Application of Established Methods," Analytical
Chemistry, Volume 23, No. 11, pages 1632-1634 (1954).
10. Stevens, R. F., Dinneen, G. V., and Ball, J. S., "Analysis of Crude
Shale Oil," U. S. Department of the Interior, Bureau of Mines Report
of Investigations No. 4898, 1952.
11. Smith, N. A. C., Smith, H. M., Blade, 0. C., and Carton, E. L., "The
Bureau of Mines Routine Method for the Analysis of Crude Petroleum:
I - The Analytical Method," Bureau of Mines Bulletin 490, 1951.
12. Whitehurst, D. D., Farcasiu, M., and Mitchell, T. 0., "The Nature and
Origin of Asphaltenes in Processed Coals," Mobil Research and Develop-
ment Corporation, Princeton, New Jersey.
13. Sharkey, A. G., Jr., "Mass Spectrometric Analysis of Process Streams
for Coal-Derived Fuels," Energy Research and Development Administra-
tion, Pittsburgh Energy Research Center, Pittsburgh, Pennsylvania.
40
-------
Table IV-1
ANALYSES FOR SHALE OIL AND COAL LIQUIDS
SUMMARY LISTING
APPROXIMATE
AMOUNT OF
SAMPLE NEEDED COST OF SRM
PARAMETER PREFERRED METHOD3 FOR ANALYSIS13 ANALYSIS0 AVAILABLE*1
1.
2.
3.
4.
5.
6.
7.
8.
9.
10.
11.
12.
13.
14.
15.
16.
Carbon (Total)
and Hydrogen
Nitrogen
Sulfur
Oxygen
Chlorine
Water and
Sediment
Ash
Calorific Value
Carbon Residue
a. Distillation
(distilates)
b. Distillation
(crudes)
Vapor Pressure
Flash Point
Pour Point
Viscosity
Density
Corrosion
ASTM D 3178
ASTM E 258
ASTM D 129
ASTM D 271
ASTM D 808
ASTM D 1796
ASTM D 482
ASTM D 240
ASTM D 189
ASTM D 86
ASTM D 285
ASTM D 323
ASTM D 93
ASTM D 97
ASTM D 445
ASTM D 1298
ASTM D 130
(g)
0.2 15
£ 2.e 15
0.6 - 1.0e 8
NP
0.8e *
50. - 60. 5
100. e 10
0.6 - 0.7e 10
10. 10
*
100. - 120. 10
300 + 10
1. - 7. liters 15
* 75. - 90. 7
•v, 45. - 55. 7
f 7
f 4
* 30. - 90. 6
($)
- 30
- 20
- 25 LF-2
20
- 15
- 15
- 30 LF-5
- 15
- 30
- 30
- 20
- 15
- 20
- 20
- 10
- 20
Notes on following page.
41
-------
Notes for Table IV-1;
NP - Not Pertinent
a. All methods given are by the American Society for Testing and Mate-
rials. Specific references are cited in Table IV-2 for each para-
meter.
b. These are the sample requirements for a single analysis.
c. Estimates based on prices charged by analytical services laboratories
for petroleum fuels in early-1977.
d. See Appendix A for details.
e. The amount needed varies with the value of the parameter being mea-
sured.
f. The amount needed varies with the type of equipment used and, for
viscosity, with the value of the viscosity.
42
-------
Table IV-2
METHODS OF ANALYSIS FOR SHALE OIL (SO) AND COAL LIQUIDS (CL)
PARAMETER
1. Carbon (Total)
and Hydrogen
SUGGESTED METHOD(S)
No./Title Ref.
ASTM D 3178
2. Nitrogen
ASTM E 258
Modified
Kjeldahl
(See Note #1)
OJ
SUMMARY OF METHODS
A weighed sample is burned in
a closed system and the pro-
ducts of combustion fixed in
an absorption train. C02 ab-
sorber may contain NaOH, KOH,
or soda lime. Moisture absor-
ber is anhydrous magnesium per-
chlorate (Mg(C10it)2).
A sample is digested in a mix-
ture of sulfuric acid, potas-
sium sulfate and mercuric ox-
ide converting nitrogen to
ammonium sulfate. After mer-
cury is precipitated with so-
dium sulfide, the solution is
made alkaline with sodium hy-
droxide and the liberated
ammonia distilled into an acid
solution. The amount of acid
neutralized is determined by
titration with sodium hydrox-
ide.
APPLICABILITY
Method developed for coal
and coke. Sample boats
may have to be modified
to hold liquid samples.
Method developed for
nitrogen-containing organic
compounds. Not applicable
for materials containing
N-0, N-N linkages. Should
be applicable to SO and CL.
ACCURACY (A) AND PRECISION (P)*
(P) Unknown for SO and CL. For
coal and coke:
Repeatability:
Carbon - 0.3%
Hydrogen - 0.07%
(P) Unknown for SO and CL. For
organic compounds in general
expect:
Repeatability: 0.1Z absolute
for two results, each the aver-
age of duplicate determinations.
See Reference 06 for additional
information.
Reproducibllity: 0.2% absolute
for two results, each the aver-
age of duplicate deterinations.
See References it6 and 99 for
additional information.
3. Sulfur
ASTM D 129
General Bomb
(See Note #2)
A sample is oxidized in a bomb
containing oxygen under pres-
sure. The sulfur, as sulfate
in the bomb washings, is deter-
mined gravimetrially as barium
sulfate.
Generally applicable to
petroleum products that
are not highly volatile
and that contain at least
0.1% sulfur. Should be
applicable to SO and CL.
i(P) Unknown for SO and CL.
petroleum oils:
For
Repeatability: 0.04% to 0.06%
when S is between 0.1% and 1.0%.
Reproducibility: 0.05% to
0.09% when S is between 0.1%
and 1.0%. See Reference tl
for additional Information.
4. Oxygen
ASTM D 271
Oxygen is determined indirectly
by subtracting from 100 the per-
centages of hydrogen, carbon,
sulfur, nitrogen, and ash.
Method developed for coal
coke.
Not known
All notes appear on the last page of this table.
-------
Table IV-2
METHODS OF ANALYSIS FOR SHALE OIL (SO) AND COAL LIQUIDS (CL)
(continued)
PARAMETER
5. Chlorine
6.
Water and
Sediment
SUGGESTED METHOD(S)
No./Title Ref.
ASTM D 808
Bomb Method
(See Note #3)
A.
ASTM
D 1796
Centrifuge
(See Note (M)
SUMMARY OF METHODS
Sample is oxidized by combus-
tion in a bomb containing oxy-
gen under pressure. The chlo-
rine compounds liberated are
absorbed in a sodium carbonate
solution and the amount of
chlorine present determined
gravimetrlcally by precipita-
tion as silver chloride.
The combined volume of water
and sediment is measured volu-
metrically at the bottom of a
centrifuge tube after a 50:50
solvent/sample mixture is cen-
trifuged in a specified manner
and at a specific temperature
(49°C, or 60"C if wax contri-
butes to volume of water and
sediment).
APPLICABILITY
Method developed for lub-
ricating oils and greases.
Assumes other halogens are
not present. Lower limit
of applicability is 0.1%
chlorine which may be high-
er than values found in
most SO and CL.
Applicable to crude oils
and fuel oils (based on
petroleum). Should be ap-
plicable to SO and CL.
Not applicable if value
is less than 0.05%.
ACCURACY (A) AMD PRECISION (P)*
(P) Unknown for SO and CL. For
lubricating oils and greases;
Repeatability; 0.07Z for
chlorine content in range
of O.U to 2Z
Reproduclbility: 0.10Z for
chlorine content In range of
0.1Z to 2%.
(P) Unknown for SO and CL. For
petroleum crude and fuel oils:
Repeatability; Ranges from
0.1% to 0.07% when value is
0.1% and 1.0%, respectively.
Reproducibillty^ Ranges from
0.11% to 0.20% when value is
0.1% and 1.0%, respectively,
B.
ASTM
D 95
Water by
Distillation
The sample is heated under re-
flux with a water Immiscible
solvent which co-distills with
the water in the sample. Con-
densed solvent and water are
continuously separated in a
trap, the water settling in
the graduated section of the
trap and measured volumetri-
cally.
Applicable to crude petro-
leum, tars, and products
derived from these mater-
ials. Should be applicable
to SO and CL.
(P) Unknown for SO and CL.
petroleum oils:
For
Repeatability: 0.1 ml if
water collected is < 1.0 ml.
Reproduclbility; 0.2 ml if
water collected is < 1.0 ml.
-------
PARAMETER
Table IV-2
METHODS OF ANALYSIS FOR SHALE OIL (SO) AND COAL LIQUIDS (CL)
(continued)
6. Water and
Sediment
continued
SUGGESTED METHOD(S)
No./Title Ref.
C.
ASTM
D 473
Sediment by
Extraction
SUMMARY OF METHODS
A sample is placed in a refrac-
tory thimble and extracted with
hot toluene until the residue
reaches constant weight.
APPLICABILITY
Applicable for crude petro-
leum and fuel oils. Should
be applicable to SO and CL.
ACCURACY (A) AMD PRECISION (P)*
(P) Unknown for SO and CL. For
petroleum oils with O.OZ to
0.4% sediment:
Repeatability: 0.017 S Z +
0.255 S Z where S is average
weight result in weight Z.
Reprodueibility: 0.033 SZ
+ 0.255 S Z where S is the
average result in weight Z.
7. Ash
•P-
l/i
ASTM D 482
(See Note #3)
A sample is ignited in a cru-
cible or evaporating dish and
allowed to burn until only ash
and carbon remain. The car-
bonaceous residue is reduced
to an ash by heating in a muf-
fle furnace at 775°C, cooled
and weighed.
Applicable to most types of
petroleum oils, including
crude, residual fuels, dis-
tillates, and lubricating
oils (containing no addi-
tives). Should be appli-
cable to SO and CL.
(P) Unknown for SO and CL. For
petroleum oils:
Repeatability; 0.002Z when
ash is in range of 0.002Z
to 0.15Z.
Reprodueibility: 0.004Z when
ash is in range of 0.002Z to
0.15Z. See Reference 11 for
additional information.
8. Calorific
Value
ASTM D 240
(See Notes 93
and 05)
A weighed sample is burned in
an oxygen bomb calorimeter
under controlled conditions.
The heat of combustion is com-
puted from temperature obser-
vations before, during, and
after combustion. Allowance
is made for thermochemical
and heat transfer corrections.
Either isothermal or adia-
batic calorimeter jackets may
be used.
Applicable to a wide vari-
ety of substances, but par-
ticularly to liquid hydro-
carbon fuels of both low
and high volatility. Should
be applicable to SO -and CL.
(P) Unknown for SO and CL. For
others:
Repeatability;
30.6 cal/g (55 Btu/lb.)
Reprodueibility;
97.2 cal./g (175 Btu/lb.)
-------
Table IV-2
METHODS OF ANALYSIS FOR SHALE OIL (SO) AND COAL LIQUIDS (CL)
(continued)
PARAMETER
9. Carbon Residue
SUGGESTED METHOD(S)
Ho./Title Ref.
A.
ASTM
D 189
Conradson
(See Note 1)
B.
ASTM
D 524
Ramsbottom
(See Note #6)
SUMMARY OF METHODS
APPLICABILITY
A sample is placed in a covered
crucible and subjected to des-
tructive distillation. At the
end of a 30 minute heating per-
iod, the crucible is cooled and
weighed. Modifications are pre-
scribed for high residue mate-
rials .
A sample is placed in a special
glass bulb having a capillary
opening and then placed in a
metal furnace maintained at
*> 550°C. Heating is for 20 min-
utes. The bulb is then cooled
in a dessicator and weighed. A
modification is given for light
distilate oils; the method, as
given above, is used on a 10%
distillation residue of the sam-
ple.
Generally applicable to
nonvolatile petroleum pro-
ducts which particularly
decompose at atmospheric
pressure. High ash con-
tent may give erroneously
high values. Should be
applicable for crude SO
and CL.
Generally -applicable to
relatively nonvolatile
petroleum products which
partially decompose on
distillation at atmos-
pheric pressure. High ash
content may give errone-
ously high values. Method
should be applicable for
SO and Cl.
ACCURACY (A) AND PRECISION (P)*
(P) Unknown for SO and CL. For
other:
Repeatability; 0.022Z for
average carbon residue of
0.1%. See Reference fl for
other points.
Reprbducibility; 0.058% for
average carbon residue of
0.1%. See Reference #1 for
other points.
(P) Unknown for SO and CL. For
others:.
Repeatability; 0.025% for
average carbon residue of
0.1%. See Reference fl for
other points.
Reproducihdlity; 0.035% for
average carbon residue of
0.1%. See Reference Si for
other points.
10. Distillation
A.
ASTM
D 86
Petroleum
Products
A 100-ml sample is distilled un-
der prescribed conditions which
depend on the vapor pressure and
initial and final distillation
points. Systematic observations
of temperature and condensate
volume are made, and the report-
ed results calculated from these
data.
Applicable to motor and
aviation gasolines, avia-
tion turbine fuels, dis-
tilate fuel oils, and
similar petroleum products.
Should be applicable for
low boiling or distilate
SO and CL.
(P) Varies with the initial boil-
ing point and end point of
the material and with the
rate of change of thermometer
readings. See Reference #1
for data.
-------
Table IV-2
METHODS OF ANALYSIS FOR SHALE OIL (SO) AM) COAL LIQUIDS (CL)
(continued)
PARAMETER
10. Distillation
continued
SUGGESTED METHOD(S
Ho./Title Ref.
B. ASTM
D 285
11. Vapor Pressure
ASTM D 323
Reid Method
12. Flash Point
A.
ASTM
D 93
Pensky-
Martens
Closed Cup
SUMMARY OF METHODS
One or more 300-ml portions are
distilled from a flask equipped
with a fractionating column at
a rate of 4 ml to 5 ml per min-
ute to a predetermined thermo-
meter reading. A 100-ml por-
tion of the total distilate
is distilled in accordance with
ASTM D 86. The predetermined
temperature for the initial
crude distillation is specified
by the parties concerned in the
evaluation; it is not specified
in the method.
One chamber of the apparatus is
filled with a chilled sample,
and connected to an air chamber
at 37.8°C (100'F) or other tem-
perature, The apparatus is im-
mersed in a constant-temperature
bath at 37.8"C (100°F) and shaken
until equilibrium is reached.
The vapor pressure is then ob-
tained from manometer readings,
suitably corrected if the air
chamber was not initially at
37.8"C (100-F).
A sample is heated, in a cover-
ed cup, at a slow, constant rate
with continual stirring. A small
flame is directed into the cup-
through opening in the cover -
at regular intervals with simul-
taneous interruption of the stir-
ring. The flash point is the
lowest temperature at which the
vapor above the sample is ignited
by the test flame.
APPLICABILITY
Applicable for any crude
petroleum of the class
known commercially as
refinable crude oils.
Should be applicable for
crude SO and CL.
ACCURACY (A) AND PRECISION (P)*
Not given
Applicable to crude (petro-
leum) oil and volatile non-
viscous petroleum products,
except liquified petroleum
gases. Should be applicable
for SO and CL.
(P) Unknown for SO and CL. For
petroleum products:
Repeatability: Varies with
vapor pressure; is 0.2Z for
pressures in range of .35 kg/
cm2 to 1.1 kg/cm2 (5 Ibs to
6 Ibs).
Applicable for fuel oils,
lube oils, and other liq-
uids. Should be applicable
for SO and CL.
(P) Unknown for SO and CL. For
others (excluding suspensions):
Repeatability; 2°C for flash
points under 104.4°C. 5.5"C
for flash points above 104.4°C.
Reproducibility; 3.5°C for
flash points under 104.4°C.
8.5°C for flash points above
104.4°C. See Reference *1
for additional information.
-------
Table IV-2
METHODS OF ANALYSIS FOR SHALE OIL (SO) AND COAL LIQUIDS (CL)
(continued)
PARAMETER
12. Flash Point
continued
SUGGESTED METHOD(S)
No./Title Ref.
B.
ASTM
D 92
Cleveland
Open Cup
13. Pour Point
ASTM D 97
-P-
00
14. Viscosity
A. ASTM
D 445
Kinematic
and Dynamic
(See Note 91)
SUMMARY OF METHODS
A sample is placed in an open
cup and its temperature in-
creased rapidly at first and
then at a slow, constant rate
as the flash point is approach-
ed. At specified intervals, a
test flame is passed across the
cup. The lowest temperature at
which the vapors ignite is the
flash point.
After preliminary heating, a
sample is cooled at a specified
rate and examined at Intervals
of 3°C (5°F) for flow charac-
teristics. The lowest tempera-
ture at which movement of the
oil is observed is the pour
point. A modification for de-
terminating the lower (minimum)
pour point of black oil, cylin-
der stock, and non-distilate
fuel oil is given.
The time (in seconds) it takes
a fixed volume of sample to
flow through a capillary is
measured. The capillary is
calibrated and used with a re-
producible driving head and
with a closely controlled tem-
perature. The kinematic vis-
cosity is the product of the
measured flow time and the
calibration constant of the
viscometer. The dynamic vis-
cosity is calculated from the
kinematic viscosity. Test tem-
perature must be specified by
the parties concerned.
APPLICABILITY
Applicable to all petro-
leum products, except
fuel oils and those hav-
ing an open cup flash
point below 79°C. Should
be applicable for SO and
CL.
Applicable to any petro-
leum oil. Should be appli-
cable for SO and CL.
Generally applicable to
liquid petroleum products.
Should be applicable for SO
and CL.
ACCURACY (A) AND PRECISION (P)*
(P) Unknown for SO and CL. For
others:
Repeatability; 8°C
Reproducibility: 17°C
(P) Unknown for SO and CL. For
others:
Repeatability: 3°C (5"F)
Reproducibility: 6°C (10°F)
(Above not applicable when
modified procedure is used.)
(P) Unknown for SO and CL. For
others:
Repeatability: 0.35% of mean
Reproducibility; 0.7% of mean
-------
Table IV-2
METHODS OF ANALYSIS FOR SHALE OIL (SO) AND COAL LIQUIDS (CL)
(continued)
PARAMETER
14. Viscosity
continued
SUGGESTED METHOD(S)
No./Title Ref.
B. ASTtf
D 88
Saybolt
(See Motes #7
and #8)
15. Density
ASTH D 1298
Density, Speci-
fic Gravity, or
API Gravity
vo
16. Corrosion
ASTM D 130
Copper Strip
SUMMARY OF METHODS
The time required for a 60-ml
sample to flow through a cali-
brated orifice is measured un-
der carefully controlled condi-
tions. This time is corrected
by an orifice factor and re-
ported as the viscosity of the
sample at that temperature.
Test temperature must be speci-
fied by the parties concerned.
A sample is brought to the pre-
scribed temperature and trans-
ferred to a cylinder at appro-
ximately the same temperature.
An appropraite hydrometer is
lowered into the sample and
allowed to settle. The density
is then read from the hydro-
meter scale where it breaks the
liquid surface. Test tempera-
ture preferred near 15°C (60°F),
but may be between -18°C and
90°C (0°F and 195°F). Test tem-
perature should be specified by
parties concerned. All readings
are reduced to 15°C (60°F) for
reporting.
A polished copper strip in im-
mersed in a sample at a certain
temperature for a time charac-
teristic of the sample being
tested. The copper strip is
then removed, washed, and com-
pared with the ASTM Copper
strip Corrosion Standards.
Modifications are given for
different types of petroleum
products; in some cases, the
parties concerned must specify
the temperature and time for
the test.
APPLICABILITY
Generally applicable to
petroleum products at test
temperatures between 21.1°C
and 98.9°C (70°F and 210°F).
Should be applicable for SO
and CL.
Generally applicable to
crude petroleum and petro-
leum products normally
handled as liquids and
having a Reid vapor pres-
sure of 1.8 kg/cm2 (26 Ibs/
in2) or less. Should be
applicable for SO and CL
Generally applicable to
petroleum fuel oils, gaso-
lines, lubricating oils,
and certain other petro-
leum products. Should be
applicable for SO and CL.
The temperature and time
best suited for SO and CL
corrosion tests are un-
known and should be deter-
mined by the parties con-
cerned.
ACCURACY (A> AND PRECISION (P)*
Not given
(P) Unknown for SO and CL.
others:
For
Repeatability: 0,0005 to
0.0006 for specific gravity
and density, .and 0.1 to 0.2
for API gravity, depending
on type of oil. See Refer-
ence 01 for details.
Reproducibility; 0.0012 to
0.0015 for specific gravity
and density, and 0.3 to 0.5
for API gravity, depending
on type of oil. See Refer-
ence 01 for details.
Not given
-------
Notes for Table IV-2;
^Precision, when known, is usually given as either repeatability and/or reproducibility. The number given for repeatability
is the acceptable difference for duplicate results by the same laboratory; that for reproducibility is the acceptable differ-
ence for duplicate results submitted by two or more laboratories. The original reference should be checked if precision is
critical since the wording may imply special conditions for the applicability of the precision numbers given. Accuracy is
given when listed in the original reference.
1. Data from analyses of shale oil and coal liquids for nitrogen by another method, ASTM 322B1, are given in Appendix D. This
is also a modified Kjeldahl method, but is only intended for use when nitrogen is present from 0.03 wt. Z to 0.10 wt. Z.
2. Data from analyses of shale oil and coal liquids for sulfur by another method, ASTM's "High Temperature Method" (ASTM D 1552)1,
are given in Appendix D. A warning is given that nitrogen, when present in excess of 0.1%, may interfere with this method.
Both shale oil and coal liquids contain nitrogen above this level.
3. Data from analyses of shale oil and coal liquids by this method are given in Appendix D.
4. An essentially similar method is given in ASTM D 96, "Standard Method of Test for Water and Sediment in Crude Oils"1.
5. Another acceptable method is given in ASTM D 2382, "Standard Method of Test for Heat of Combustion of Hydrocarbon Fuels by
Bomb Calorimeter (High Precision Method)"1. It is designed specifically for use with aviation turbine fuels when the per-
missible difference between duplicate determinations is of the order of 0.1Z. The method can be used for a wide range of
volatile and non-volatile materials where slightly greater differences in precision can be tolerated1.
6. While no exact correlation exists between the Conradson (D 189) and Ramsbottom (D 524) methods for carbon residue, an appro-
ximate correlation for petroleum products has been found and is shown graphically in Reference #1. The correlation may not
be valid for unusual petroleum products (and, thus-, SO and CL), and ASTM urges caution in the application of this correlation
at low carbon residues.
7. Tables are given in ASTM D 2161 for conversion of kinematic viscosity (in centistokes) to Saybolt viscosity (in seconds) and
the reverse.
8. This frequently used method was, until recently, included in Part 23 of ASTM's Book of Standards and was under the jurisdic-
tion of ASTM Committee D-2 on petroleum products and lubricants. The method has recently transferred to the jurisdlcation of
ASTM Committee D-8 on asphalt and, accordingly, is now found in Part 15 of ASTM's Book of Standards. This transfer was in
accordance with ASTM's plans to phase-out non-metric methods of test for petroleum products.
-------
CHAPTER V
METHYL FUEL
1. INTRODUCTION/SUMMARY
Methyl fuel is taken here to include material produced in a methanol-
synthesis type of operation where the higher alcohol impurities are not
removed, but most of the water is removed. The fuel composition will vary
depending on the feed stock used and the process involved, but, typically,
it will be around 90% to 95% methanol, 0.1% to 10% higher alcohols, and
0.5%> /to 5% water.
Proposed raw materials for methyl fuel include: (1) middle-east flare 1;;
gas (converted to methyl fuel at the well site); (2) domestic coal; and,
(3) wastes, both domestic and agricultural. At present, methyl fuel is
not being made commercially. Possible uses for the methyl fuel include:
use as a fuel for boilers and gas turbines; use as a fuel - complete or
as an additive to gasoline - for automobiles; or, regasification to Syn-
thetic Natural Gas (SNG).
Table IV-1 gives a summary of the fuel analyses that are important for
methyl fuel, along with an identification of the preferred method of anal-
ysis and other information relating to the analyses. Additional informa-
tion on the methods of analyses, including alternate methods for some
parameters, is given in Section 3 of this chapter. All of the methods
discussed, except those for chloride and higher alcohols, are given by
the American Society for Testing and Materials (ASTM). Many of these
ASTM methods are specified as standard methods of analysis to be used
for methanol. They have beeji identified in Table IV-1. The chloride
and higher alcohol analyses prescribed are given by the Association of
Official Analytical Chemists (AOAC).
No analyses for carbon, hydrogen, and oxygen have been prescribed, as their
concentration may be calculated with sufficient accuracy one the concen-
51
-------
trations of methanol, water, and higher alcohols are known. The methanol
content may be derived from the specific gravity, viscosity, boiling point,
or vapor pressure, if the content of higher alcohols is small. All of
these properties vary with water content, and.tables of values (at differ-
ent water contents) are available in the literature or in the manufac-
turer's data sheets. When the content of higher alcohols is large, the
methanol content may be roughly estimated by subtracting the percentages
of higher alcohols plus water from 100.
An analysis for sulfur has been included, even though the concentration
is expected to be quite low. The catalysts used in making methyl fuel
are quite sensitive to contamination by sulfur, and its concentration is
accordingly reduced to low levels, often 0.1 ppm, in the feed material.
Nitrogen will be present only to the extent that it is present in the feed
material. Nitrogen compounds are likely to be present as amines in methyl
fuel. Chlorides are likely to be present when methyl fuel is shipped by
ocean-going tankers. Salt water contamination in the tanks is the source
of the chlorides. The higher alcohols found in methyl fuel consist.pri- „
marily of ethanol, n-propanol, and iso-butanol. They are desirable com-
ponents of methyl fuel in one respect as they will increase the calorific
value. Small amounts of other organics, such as methyl ether, acetone,
and resins, may also be present. It is not clear, at this time, if cer-
tain additives would have to be added to methyl fuel to make it suitable
for various uses and/or unsuitable for other uses.
If methyl fuel was to be investigated as a automotive fuel, then certain
other analyses may need to be included. This may include, for example,
research octane number, motor octane number, and corrosion tests other
than the copper strip method.
2. SAMPLING
Procedures for collecting representative samples of methyl fuel will have
to be tailored to (1) the nature of the material being samples; (2) the
52
-------
nature of the fuel processing, handling, or storage equipment; and, (3)
the precision and accuracy requirements of the analyses to be carried out.
Since methyl fuel is not currently in commercial production, most sampling
in the near term will be connected with bench, or pilot, scale research
facilities.
Methods for sample collection may be taken either from ASTM E 300, "Stan-
dard Recommended Practice for Sampling Industrial Chemicals"5, or ASTM
D 270, "Standard Method of Sampling Petroleum and Petroleum Products"2-
The ASTM E 300 methods are specified in ASTM D 1152s for the collection
of a representative sample of methyl alcohol. Method ASTM E 300 covers
statistical considerations. The sample collection methods are based on
those given in D 270, so the differences are minimal. Both methods in-
clude variations for sampling from a wide variety of containers for a wide
variety of sample types, as shown by the examples below.
General Methods: bottle or grab, tap, continuous, dipper, tube, thief,
boring, grab, and others;
Sample Containers; stationary tanks, ship or barge tanks, tank cars, and
packaged lots (e.g., cans, drums, barrels);
Sample Types; average, all-levels, running, spot, top, upper, middle,
lower, clearance, bottom, drain, water and sediment, composite, and
several others.
The parties concerned should agree on a sampling procedure for each pro-
ject.
3. ANALYSES
Table V-2 gives, for each parameter of interest, additional information
on the methods of analysis deemed suitable. When more than one method is
listed, the preferred method is given first. The parameters are listed
in the order given in Table V*l,
53
-------
It should be noted that none of the listed methods were developed for
specific applicability to methyl fuel, though some are specifically appli-
cable to methanol. While it is expected that the listed methods will be
generally applicable to methyl fuel, this has yet to be proven by labora-
tory tests. It is possible that unanticipated problems will require some
methods modifications.
Caution should be used in the comparison of any precision information given
in Table V-2. Sample homogeneity may not be comparable and the absolute
value of the parameters being measured may differ significantly in some
cases.
4. REFERENCES
1. "Annual Book of ASTM Standards (1974) - Part 30: Soap, Engine Cool-
ants; Polishes; Halogenated Organic Solvents; Activated Carbon, In-
dustrial Chemicals," American Society for Testing and Materials,
Philadelphia, Pennsylvania.
2. "Annual Book of ASTM Standards (1974) - Part 23: Petroleum and -
Petroleum Products," American Society for Testing and Materials,
Philadelphia, Pennsylvania.
3. "Annual Book of ASTM Standards (1974) - Part 31: Water," American
Society for Testing and Materials, Philadelphia, Pennsylvania.
4. "Official Methods of Analysis of the Association of Official Analyti-
cal Chemist," William Horwitz (ed.), Twelfth Edition, 1975. Pub-
lished by the Association of Official Analytical Chemists (AOAC),
Washington, D. C.
5. "Annual Book of ASTM Standards (1974) - Part 29: Paint - Fatty Oils
and Acids, Solvents, Miscellaneous; Aromatic Hydrocarbons; Naval
Stores," American Society for Testing and Materials, Philadelphia,
Pennsylvania.
6. See, for example, article by C. Carr and J.A. Riddick, "Physical
Properties of Methanol-Water Systemsj" Ind. Eng. Chem. 43. 692-696,
1951.
54
-------
Table V-l
ANALYSES OF METHYL FUEL
SUMMARY LISTING
1.
2.
3.
4.
5.
6.
7.
8.
9.
10.
11.
12.
13.
14.
PARAMETER
Nitrogen..
Sulfur
Chloride
Water
Higher Alcohols
Nonvolatile Matter
Calorific Value
Specific Gravity
Viscosity
Distillation
Flash Point
Vapor Pressure
Corrosion Rate
Acidity
PREFERRED METHOD a
ASTM E 258
ASTM D 1266 and
ASTM D 516
AOAC
ASTM E 346/E 203e
AOAC
ASTM D 1353^
ASTM D 240
ASTM E346/D 891e
(Method C)
ASTM D 445
ASTM D 1078® 'f
ASTM D 93
ASTM D 323
ASTM D 1616
ASTM D 1613e'f
APPROXIMATE
AMOUNT OF
SAMPLE NEEDED
FOR ANALYSIS -
(g)
2.
20
10-50
100
1-10
100
100
1
25
100
80
1-7 liters
10
60
COST OF SRM
ANALYS I S c AVAILABLE
($)
15 - 20
* 20 , LF-2
* 10 *
^ 15
* 15
30 - 50
•b 10
10 - 30
4-10
7-20
10 - 20
7-15
15 - 20
6-20
7-15
All notes appear on the following page.
55
-------
Notes for Table VI-1;
a. Specific references to methods listed are given in Table V-2. All
method numbers beginning with 'DT or 'E' are from ASTM. AOAC refers
to methods given by the Association of Official Analytical Chemists.
b. These are the approximate sample requirements for a single analysis
of a material for which the method is directly applicable. Somewhat
different amounts may be required for methyl fuel. The amounts re-
quired by a laboratory may be larger for a variety of reasons, in-
cluding those connected with sample preparation.
c. Estimates based on prices charged by analytical service laboratories
for petroleum products or water in early-1977.
d. See Appendix A for details.
e. These test methods are specified by ASTM for methanol in E 346, "Stan-
dard Methods for Analysis of Methanol"5.
f. These test methods are specified by ASTM for methyl alcohol in D 1125,
"Standard Specification for Methyl Alcohol"5.
g« The amount needed varies with the type of equipment used and the vis-
cosity of the sample.
56
-------
Table V-2
METHODS OF ANALYSIS FOR METHYL FUEL
PARAMETER
SUGGESTED HETHOD(S)
Ho./Title Ref.
1. Nitrogen
ASTH E 258
Modified
KJeldahl
2. Sulfur
A.
Cn
Asm
D 1266
Lamp Method
B.
ASM
D 516
Sulfate in
Water
SUMMARY OF METHODS
A sample is digested in a mix-
ture of sulfurlc acid, potas-
sium sulfate, and mercuric
oxide converting nitrogen to
ammonium sulfate. After mer-
cury is precipitated with so-
dium sulflde, the solution is
made alkaline with sodium hy-
droxide and the liberated am-
monia distilled-into an acid
solution. The amount of acid
neutralized is determined by
titration with sodium hydrox-
ide.
A sample is burned In a closed
system using a lamp and an ar-
tificial atmosphere (70% C02,
30Z 02). Sulfur oxides are ad-
sorbed and oxidized to sulfuric
acid with H2°2> and solution
flushed with air to remove COj.
Sulfur, as sulfate, in the ad-
sorbent is determined acidi-
metrically by titration, or
gravimetrically, by precipita-
tion as BaSOi,.
Sulfate ion may be either (a)
precipitated and weighed as
BaSOit after removal of silica
and other Insoluble matter,
(b) converted to BaSOi, in a
controlled manner and the tur-
bidity measured, or (c) titrat-
ed in an alcoholic solution
under acid conditions with
solution.
APPLICABILITY
Method developed for ni-
trogen containing organic
compounds. Not applicable
for materials containing
N-0, N-N linkages. May be
applicable to MF.
Applicable to light petro-
leum products with sulfur •
contents above 0.002 wt Z.
Modification of procedure
(Appendix Al of Method)
allows detection of 5 ppm
sulfur. May be applicable
to MF if sulfur is primar-
ily connected with volatile
compounds.
Applicable to water and
wastewater. First method
(a) directly applicable for
samples containing "<• 20 ppm
sulfate Ion; others are par-
ticularly useful below 20
ppm. May be applicable to
MF if sulfur is primarily
in form of sulfate ions.
ACCURACY (A) ASP PRECISION (P)*
(P) Unknown for MF. For organic
compounds in general expect:
Repeatability:
0.1Z absolute for two results,
each the average of duplicate
determinations. See Reference
fi for additional Information.
Reproducibility:
0.2Z absolute for two results,
each the average of duplicate
determinations. See Reference
#1 for additional information.
(P) Unknown for MF. For others
with 0.01% to O.'04% sulfur:
Repeatability:
0.005Z
Reproducibility:
0.010 + 0.025 S where S = total
wt % sulfur in the sample.
(P) Unknown for MF. For -other
applicable samples:
Method a: l.OZ
Method b; 51 or 2 mg/1, which-
ever Is greater.
Method c; 0.7 mg/1 for samples
up to 100 mg/1. See
Reference 13 for addi-
tional information.
All notes appear on the last page of this table.
-------
Table V-2
METHODS OF ANALYSIS FOR METHYL FUEL
(continued)
PARAMETER
3. Chloride
4. Water
Ui
00
5. Higher Alcohols
SUGGESTED METHOD(S)
No./Title Ref.
AOAC 9.043-
9.045
Chloride (10)
ASTM
E 346/E203
Karl Fisher
Reagent
AOAC 9.075-
9.080
Gas Chroma-
tographic
Method (16)
and Alterna-
tive Method
(17)
SUMMARY OF METHODS
Sample is titrated in an acid
medium with AgNOs solution.
End point is determined with
pH meter and specified glass
electrodes. Equivalence volt-
age predetermined with stan-
dard solution of chloride in
ethanol.
A sample is dissolved in a
suitable liquid and titrated
with Karl Fisher reagent,
which is a mixture of iodine,
sulfur dioxide, pyridine, and
methanol or glycol ether.
End point may be determined
either visually or electro-
metrically.
Quantitative determination of
higher alcohols made by mea-
surement of peak height after
passing sample through gas
chromatograph having a flame
ionization detector. Column
for Method 16 is 23Z Carbowax
1500 on Chromosorb W; column
for Method 17 is 2Z glycerol
and 2% 1,2,6-hexanetriol on
Gas-Chrom R.
APPLICABILITY
Method developed for dis-
tilled liquors (spirits).
Should be applicable to
MF.
Applicable for determina-
tion of free water and
water of hydration in liq-
uid organic compounds (plus
other types of compounds)
over a wide concentration
range. Specifically appli-
cable to determination of
water in the presence of
alcohols. Method specified
by ASTM for testing of
methanol.
Method developed for dis-
tilled liquors (spirits),
specifically to look for
n-propyl alcohol, iso-
butyl alcohol, isoamyl
alcohol and ethyl acetate
in spirits. May be appli-
cable to MF.
ACCURACY (A) AND PRECISION (P)*
Not given
(P) Unknown for MF. For others,
varies with several factors;
see Reference #1 for discus-
sion. Sensitivity is i> 0.1 mg
water for visual tltrations;
less than 0.02 mg for electro-
metric titrations.
Not given
-------
Table V-2
METHODS OF ANALYSIS FOR METHYL FUEL
(continued)
PARAMETER
6. Nonvolatile
Matter
SUGGESTED METHOD(S)
No./Title Kef.
ASTM D 1353
7. Calorific
Value
ASTM D 240
Ui
vo
8. Specific
Gravity
ASTM
E 346/D 891
(Method C)
Pycnoneter
SUMMARY OF METHODS
A sample is evaporated to dry-
ness in a platinum evaporating
dish over a steam bath. After
further drying for •«• 1 hour in
an oven at 105°C, the nonvola-
tile matter is determined from
the wieght of the residue in
the dish.
A weighed sample is burned in
an oxygen bomb calorimeter
under controlled conditions.
The heat of combustion is com-
puted from temperature obser-
vations taken before, during,
and after combustion. Allow-
ance is made for themochemi-
cal and heat transfer correc-
tions. Either isothermal or
adiabatic calorimeter jackets
may be used.
A calibrated pycnoraeter is
filled with the sample and put
in a water bath at 20°C for at
least 30 minutes. At the end
of this period, the liquid
'level in the pycometer is ad-
justed to the calibration
mark, removed from the bath
and weighed. The specific
gravity is calculated as the
ratio of the sample weight to
an equal volume of water at
20°C.
APPLICABILITY
Applicable to volatile
solvents used in paint,
varnish, lacquer and re-
lated products. Method
specified by ASTM for
testing of methyl alcohol.
Applicable to a wide vari-
ety of substances, but par-
ticularly to liquid hydro-
carbon fuels of both low
and high volatility.
Should be applicable to MF.
Generally applicable to in-
dustrial aromatic hydrocar-
bons and related materials.
Method specified by ASTM
for testing of methanol.
ACCURACY (A) AND PRECISION (P)*
(P) Unknown for MF. For others:
Repeatability:
0.0009 g/100 ml for two re-
sults, each the average of
duplicate determinations.
Repr oducibili try;
0.0024 g/100 ml for two re-
sults, each the average of
duplicate determinations.
(P) Unknown for MF. For others:
Repeatability;
30.6 cal/g (55 Btu/lb.)
Reproducibility:
97.2 cal/g (175 Btu/lb.)
(P) Unknown for MF. For methanol:
Repeatability;
0.00008 units for difference
in two values
Reproduclbility:
0.00055 units for difference
in two values
-------
Table V-2
METHODS OF ANALYSIS FOR METHYL FUEL
(continued)
PARAMETER
9. Viscosity
SUGGESTED METHOD(S)
No./Title Ref.
ASTM D 445
Kinematic
and
Dynamic
10. Distillation
ASTM D 1078
SUMMARY OF METHODS
The time (in seconds) it takes
a fixed volume of sample to
flow through a capillary is
measured. The capillary is
calibrated and used with a re-
producible driving head and
with a closely controlled tem-
perature. The kinematic vis-
cosity is the product of the
measured flow tine and the
calibration constant of the
viscometer. The dynamic vis-
cosity is calculated from the
kinematic viscosity. Test
temperature must be specified
by the parties concerned.
A sample is distilled under
conditions equivalent to a
simple batch differential dis-
tillation. Distillation Is at
a rate of 4 to 5 ml/minute.
Readings of the distillation
thermometer are recorded after
collecting 5, 10, 20, 30, 40,
50, 60, 70, 80, 90, and 95 ml
of distillate. Distillation
is continued to the dry point
and the temperature recorded.
APPLICABILITY
Generally applicable to
liquid petroleum products.
Should be applicable to MF.
ACCURACY (A) AND PRECISION (P)*
(P) Unknown for MF. For others:
Repeatability!
0.35% of mean
Reproduclbillty:
0.7% of mean
Generally applicable to or-
ganic liquids boiling be-
tween 30°C and 300°C. Speci-
fically applicable to oxy-
genated compounds (e.g., al-
cohols). Method specified
by ASTM for testing of meth-
anol.
(P) Unknown for MF. For acetone:
Repeatability;
Ranges from 0.09°C to 0.24°C
from initial boiling to dry
point. 0.26-C for distilla-
tion range.
Reproduclbility:
Ranges from 0.32°C to 0.51 °C
at various points/ It is
0.66°C for distillation range.
See Reference.#5 for addition-
al data.
-------
Table V-2
METHODS OF ANALYSIS FOR METHYL FUEL
(continued)
PARAMETER
11. Flash Point
SUGGESTED METHOD(S)
Ho./Title Ref.
A.
ASTM
D 93
Peusky-
Martens
Closed Cup
B.
ASTM
D 92
Cleveland
Open Cup
12. Vapor Pressure
ASTM D 323
Reid Method
SUMMARY OF METHODS
A sample is heated, in a cov-
ered cup, at a slow, constant
rate with continual stirring.
A small flame is directed into
the cup - through an opening-
in the cover - at regular in-
tervals with simultaneous in-
terruprion of the stirring.
The flash point is the lowest
temperature at which the vapor
above the sample is ignited by
the test flame.
A sample is placed an in open
cup and its temperature in-
creased rapidly, at first, and
then at a slow, constant rate
as the flash point is approach-
ed. At specified intervals, a
test flame is passed over the
cup. The lowest temperature
at which the vapors ignite is
the flash point.
A chamber of the apparatus is
filled with a chilled sample
and connected to an air cham-
ber at 37.8'C (100°F) or
other temperature. The appa-
ratus is immersed in a constant
temperature bath at 37.8°C
100°F) and shaken until equili-
brium is reached. The vapor
pressure is then obtained from
manometer readings, suitably
corrected if the air chamber
was not initially at 37.8°C
(100"F).
APPLICABILITY
Applicable to fuel oils,
lube oils, and other liq-
uids. Should be appli-
cable to MF.
Applicable to all petro-
leum products except fuel
oils and those having an
open cup flash point below
79°C. Should be applicable
to MF.
Applicable to crude (petro-
leum)oil and volatile non-
viscous petroleum gases.
Should be applicable to MF.
ACCURACY (A) AND PRECISION (P)*
(P) Unknown for MF. For others
(excluding suspensions):
Repeatability:
2°C for flash points under
104.4°C. 5.5"C for flash
points above 104.4"C.
Reproducibility;
3.5°C for flash points under
104.4*C. 8.5-C for flash
points above 104.4°C. See
Reference #2 for additional
data on precision for vis-
cous materials.
(P) Unknown for MF. For others:
Repeatability; 8°C
Reproducibility; 17°C
(P) Unknown for MF.
leum products:
For petro-
Repeatability:
Varies with vapor pressure;
is 0.2Z for pressures in
range of .35 to 1.1 kg/o»2
(5 to 6 Ibs.)
-------
Table V-2
METHODS OF ANALYSIS FOR METHYL FUEL
(continued)
PARAMETER
SUGGESTED METHOD(S)
No./Title Ref.
13. Corrosion
ASTM D 1616
Copper Strip
14. Acidity
ASTM D 1613
ON
ro
SUMMARY OF METHODS
A polished copper strip is im-
mersed in a test tube filled
with the.sample and heated at
reflux temperature for 30 min-
utes. At the end of this per-
iod, the copper strip is re-
moved, washed, and compared
with copper strip corrosion
standards.
The sample is mixed with either
an equal volume of water or an
equal volume of alcohol, and
titrated with aqueous sodium
hydroxide solution to the
phenolphthalein and end point.
Acidity is reported as acetic
acid.
APPLICABILITY
Generally applicable to
mineral spirits and cer-
tain other products used
in the paint industry.
Should be applicable to
MF.
Generally applicable to or-
ganic compounds and hydro-
carbon mixtures used In
paint, varnish, and lacquer
solvents and diluents where
acidity as acetic acid is
below 0.05%. Method speci-
fied by ASTM for testing of
methanol.
ACCURACY (A) AND PRECISION (P)*
Not given
(P) Unknown for MF. For others:
Repeatability;
0.0008% absolute for two re-
sults each the average of
duplicate, determinations.
Reproduciblllty;
0.0014% absolute for two re-
sults each the average of
duplicate determinations
*Precision, when known, is usually given as either repeatability and/or reproducibllity. The number given for repeatability
is the acceptable difference for duplicate results by the same laboratory; that for reproducibility is the acceptable differ-
ence for duplicate results submitted by two or more laboratories. The original reference should be checked if precision is
critical, since the wording may imply special conditions for the applicability of the precision numbers given. Accuracy is
given when listed in the original reference.
-------
CHAPTER VI
COAL AND COKE
1. INTRODUCTION/SUMMARY
A. Coal
Coal is the term applied to those rocks in the earth's crust which are fos-
silized plants from prehistoric times. Coals are comprised of five major
elements: carbon, hydrogen, oxygen, nitrogen, and sulfur. The material
is non-homogeneous with respect to physical and chemical characteristics,
and typically consists of alternating bands of bright and dull material.
Classification by rank, according to ASTM D 388, divides coal into four
major classes with regard to rank or age - anthracitic, bituminous, sub-
bituminous, and lignitic. These classes are further broken down into
sub-groups based on the limits of fixed carbon, volatile matter, and cal-
orific value.
With two exceptions, the methods of analysis discussed herein, may be
placed into two categories: proximate analysis and ultimate analysis.
A proximate analysis includes moisture, volatile matter, ash, and
fixed carbon (determined by difference) for a coal sample. An ultimate
analysis includes moisture, carbon, hydrogen, nitrogen, sulfur, ash,
and oxygen (by difference). Several components are common to both sets
of analyses reducing the total number of determinations necessary to
completely identify a particular coal sample. The two exceptions to
proximate and ultimate analyses are chlorine content and the coal heating
value which are important in evaluating the properties of a sample.
Table VI-1 presents a summary of the analyses for coal with the preferred
methods. Section 3 of this chapter provides additional information on
analytical procedures, as well as alternate methods. The preferred meth-
ods have all been selected from the American Society for Testing and Mate-
rials (ASTM) methods for coal and coke1. These procedures are approved
63
-------
by the American National Standards Institute and are generally accepted
throughout the United States. They are essentially the same as those
methods recommended by the Bureau of Mines for analyzing coal and coke2
and the procedures accepted by the American Society of Mechanical Engi-
neers in the Power Test Codes for Solid Fuels3.
B. Coke
The principal use of coke in the United States is as a fuel in the iron
blast furnace, foundry, cupola, and for other industrial uses. Coke is
produced during the heating of coal in the absence of air ; the process
is called carbonization. Undergoing thermal decomposition, the light
constituents of the coal are volatilized, and the heavier components
crack, releasing hydrogen. The ash of the coal, as well as part of the
sulfur, is contained in the carbonaceous residue, coke. The nature
of the coke formed depends upon the original coal and the carbonization
process employed. Coke may also be produced from other sources such as
the delayed coking process which utilizes petroleum heavy residuals.
Although coke may vary greatly in physical form and chemical composition,
a standard set of analyses is applicable to most samples. The analytical
techniques for coke are almost identical to those for coal which are
listed in Table VI-1. Differences which may occur in sample size and pre-
paration are described in Section 3, dealing with actual methods. As an
added note, although the analysis for chlorine in coal and coke is essen-
tially the same, the chlorine content of coke is usually negligible and
not required.
64
-------
2. SAMPLING
A. Coal
It is of prime importance that coal samples be representative with res-
pect to the bulk material. Obtaining a uniform sample is a difficult
task due to the heterogeneous nature of coal. Detailed procedures for
every situation are not available. However, several general objectives
in sampling may be stated. Intended as guidelines in the planning of a
sampling operation, they include:
1. The sample should be collected in a manner appropriate to the condi-
tion of the coal, e.g., sampling from a conveyor vis-a-vis from a
rail car.
2. A gross sample from a lot of coal should be a composite of small in-
crements.
3. The size and number of increments will depend upon the desired pre-
cision, as well as the nature of the coal itself.
4. The increments must be distributed throughout the lot to be sampled.
5. The number of gross samples depends upon the size of the lot.
6. The samples collected should be protected from loss of moisture, as
well as contamination.
After collection of the gross sample, the material is air*-dried under con-
trolled conditions, i.e., humidity and temperature, if possible. (The
loss of weight of the sample is also determined.) The air dried sample
is then crushed to pass a No. 60 sieve (250 micron). A riffle - which is
a sample divider - is then used to reduce the sample to about 50 g. After
thorough mixing of the material, portions for the various analytical de-
terminations are weighed and placed in appropriate containers. The above
65
-------
procedures are described in detail in ASTM D 2234, "Collection of a Gross
Sample of Coal"1, and ASTM D 2013, "Preparing Coal Samples for Analysis"1.
A procedure for laboratory handling of samples is presented in the Bureau
of Mines report, "Methods of Analyzing and Testing Coal and Coke"2.
B. Coke
As with coal, bulk supplies of coke are nonhomogeneous, and require care-
ful sampling procedures. The objective is to first obtain a gross sample
representative of the bulk material, and then progressively reduce the
weight for a laboratory sample. To carry out this procedure, the follow-
ing general steps1 should be followed:
1. Gross samples should be taken directly from the coke-conveying equip-
ment, e.g., railroad car, supply bin. Samples generally should not
be taken from the surface of the coke.
2. Increments for the gross sample should be taken systematically.
3. The gross sample is crushed and mixed, and the total weight is re-
duced to about 13.6 kg (30 Ibs.) - .64 cm (1/4 inch) in size - for
the laboratory sample.
4. A special moisture sample should be taken before crushing.
Coke samples are dried in the laboratory only if the samples are
wet. The .64 cm (1/4 inch) size sample is mixed, reduced, and crushed to
produce 50 grams of a sample passing a No. 60 sieve (250 micron). After
mixing thoroughly, portions for the various analytical procedures are
weighed. The described procedures are presented in detail in ASTM D 346,
"Sampling Coke for Analysis"1, ASTM D 271, "Laboratory Sampling and Anal-
ysis of Coal and Coke"1, and in the Bureau of Mines report, "Methods of
Analyzing and Testing Coal and Coke"2.
66
-------
3. ANALYSES
A. Coal
Due to the oxidation of coal, it is important that analyses be conducted
as soon as possible after sample collection.
Table VI-2 provides a brief summary of pertinent methods and their appli-
cability. In cases where more than one method may be suitable, the pre-
ferred method is listed first. The primary sources for these analyses
are the ASTM procedures1 and "Methods for the Analysis and Testing of
Coal and Coke," set forth by the British Standards Institution (BSI)1*.
As mentioned previously, the former techniques are widely accepted in
the United States and are, thus, listed as preferred methods. The BSI
methods are generally the same as those proposed by the International
Organization for Standardization. They are similar in the analytical
approach to ASTM, although the actual techiques are somewhat different.
Descriptions of ultimate and proximate analyses are given in ASTM D 3172,
"Proximate Analysis of Coal and Coke"1, ASTM D 3176, "Ultimate Analysis
of Coal arid Coke"1, and ASTM D 271, "Laboratory Sampling and Analysis of
Coal and Coke"1. It is important that all analyses be reported on a con-
sistent basis, with respect to sample moisture. Results are usually re-
ported on an "as received" basis or on a "dry" basis. From a knowledge
of the moisture, the calculation of one basis from the other is simple.
However, it should be stressed that the basis upon which an analysis is
reported must be specified.
B. Coke
The methods for analyzing coke are essentially the same as for coal (des-
cribed in Table VI-2). Differences in technique may occur as the result
of the coke's physical form or chemical composition and are noted. De-
terioration of the sample is not usually considered a problem.
67
-------
4. REFERENCES
1. "Annual Book of ASTM Standards (1974) - Part 26: Gaseous Fuels; Coal
and Coke; Atmospheric Analysis," American Society for Testing and
Materials, Philadelphia, Pennsylvania.
2. "Methods of Analyzing and Testing Coal and Coke," U. S. Department
of the Interior, Bureau of Mines, Washington, D. C., 1967.
3. "Solid Fuels - Power Test Codes," American Society of Mechanical
Engineers, New York, New York, 154.
4. "Methods for the Analysis and Testing of Coal and Coke," British
Standards Institution, London, England; BS 1016, Parts 3, 5, 6, and
8.
68
-------
Table VI-1
ANALYSES FOR COAL AND COKE
SUMMARY LISTING
1.
2.
3.
4.
5.
6.
7.
8.
9.
10.
PARAMETER
Sulfur
Carbon (Total)
and Hydrogen
Nitrogen
Ash
Volatile Matter
Moisture
Chlorine
Gross Calorific
Value
Oxygen
Fixed Carbon
PREFERRED METHOD a
ASTM D 3177
ASTM D 3178
ASTM D 3179
ASTM D 3174
ASTM D 3175
ASTM D 3173
ASTM D 2361
ASTM D 2015
ASTM D 3176
ASTM D 3172
APPROXIMATE
AMOUNT OF
SAMPLE NEEDED
FOR ANALYSIS b
(8)
0.1 - 1.0
0.2
1.0
1.0
1.0
1.0
1.0
1.0
NPe
NPf
COST OF SRM
ANALYSIS c AVAILABLE d
($)
5-15 SF-1
20 - 30
15 - 25
5-15 SF-1
5-15
4-15
NA
10 - 20 SF-5
NP - Not Pertinent; NA - Not Available
a. Specific references to methods listed are given in Table VI-2.
b. These are the sample requirements for a single analysis.
c. Estimated range based on prices charged by analytical service labora-
tories in early-1977. Prices for proximate and ultimate analyses are
always quoted - they range from $20 to $40 and $40 to $100, respec-
tively - but the analyses are not always the same as those listed in
the test.
d. See Appendix A for details.
e. Determined by difference from ultimate analysis.
f. Determined by difference from proximate analysis.
69
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Table VI-2
METHODS OF ANALYSIS FOR COAL AND COKE
PARAMETER
1. Sulfur
-vl
O
2. Carbon (Total)
and Hydrogen
SUGGESTED METHOD(S)_
No./Title Ref.
A.
ASTH
D 3177
(See Note #1)
B.
BS 1016
Part 6
(See Note #2)
A. ASTM
D 3178
(See Notes #
#4, and #5)
B. BS 1016
Part 6
(See Note #6)
SUMMARY OF METHODS
Eschka Method: Sample is ig-
nited with Eschka mixture in
air at 800°C for 1.5 hours.
Ingitlon of coke may require
additional time. After extrac-
tion with hot water, BaCl2 is
used to precipitate BaSOi,.
Sulfur is determined gravl-
metrically after filtration.
Bomb-Washing Method: Washings
from bomb calorimeter are
treated in manner similar to
Eschka Method. References:
ASTM D 2015/D 3286, Gross Cal-
orific Value of Solid Fuel.
High Temperature Method: Sam-
ple is burned at 1350°C in
. oxygen current for four min-
utes. Sulfur is converted to
oxides and absorbed in H202
to form R2SOit (which is ti-
trated with sodium borate).
Acidity due to HC1 is deducted.
Combustion of sample occurs
under oxygen flow, at 850°C
to 900°C, for up to 30 min-
utes. HaO and C0£ are trap-
ped in sampling train with
appropriate absorbents.
This method is similar to the
ASTM procedure, but combustion
is controlled at 1350°C.
APPLICABILITY
Coal and coke.
ACCURACY (A) AND PRECISION (P)*
(P) Repeatability:
Coal (< 2Z S) - 0.05%
Coal (> 2Z S) - 0.102
Coke - 0.03Z
Reproducibility:
Coal (< 2% S) - 0.10Z
Coal (> 2Z S) - 0.20Z
Coke - 0.05Z
Coal and coke.
Coal and coke.
(P) Repeatability; 0.05Z
Reproducibility; 0.10Z
Coal and coke.
Coal and coke.
(P) Repeatability:
Carbon - 0.3Z
Hydrogen - 0.07Z
(P) Repeatability:
Carbon - 0.25Z
Hydrogen - 0.12Z
Reproducibility;
Carbon - 0.50Z
Hydrogen - 0.25Z
All notes appear at the end of this table.
-------
Table VI-2
METHODS OF ANALYSIS FOR COAL AND COKE
(continued)
PARAMETER
3. Nitrogen
4. Ash
5. Volatile Matter
SUGGESTED METHOD(S)
No./Title Ref.
A.
ASTM
D 3179
B. BS 1016 2
Part 6 -
(See Note #7)
A. ASTM
D 3174
(See Notes 98,
t9, and 010)
B. BS 1016
Part 3
A.
B.
ASTM
D 3175
BS 1016
Part 3
_ SUMMARY OF METHODS
Kjeldahl-Gunnlng Method: Ig
sample is digested in l^SOt,
for three to six hours with
heating. Coke nay require
12 to 16 hours. Ammonia is
distilled into H2S04 solution
and titrated. An alternate
approach uses boric acid in
place of
Semi-micro Kjeldahl: 0.1 g
sample is treated in a simi-
lar manner to the previous
method (with boric acid).
Sample is ignited in an open
crucible at 700«C to 750°C
until constant weight is
attained. Coke is ignited
at 950°C.
Sample is ignited at 815 °C.
Sample is heated in a cov-
ered crucible at 950°C for
seven minutes. A modified
method Is employed for
sparking coals as well as
some cokes.
Sample is heated at 900°C for
seven minutes.
APPLICABILITY
Coal and coke. (Coke is
ground to smaller particle
size.)
Coal and coke.
Coal and coke.
Coal and coke.
Coal and coke.
Coal and coke.
ACCURACY (A) AND PRECISION (P)*
(P) Repeatability: 0.05Z
(P) Repeatability; 0.05Z
Reproduclbillty; 0.10Z
(P) Repeatability: 0.2Z to 0.5Z
Reproduciblllty; 0.3Z to l.OZ
(P) Repeatability: 0.15Z to 0.25Z
Reproduclbllity: 0.3Z to 0.5Z
(P) Repeatability:
Coal - 0.3Z to l.OZ
Coke - 0.2Z to 0.5Z
Reproduciblllty;
Coal - 0.6Z to 2.0Z
Coke - 0.4Z to l.OZ
(P) Repeatability; 0.2Z to 0.3Z
Reproduciblllty: 0.5Z to l.OZ
-------
Table VI-2
METHODS OF ANALYSIS FOR COAL AND COKE
(continued)
PARAMETER
SUGGESTED METHOD(S)
No./Title Ref.
6. Moisture
A. ASTM
D 3173
B. BS 1016
Part 3
(See Note
to
7. Chlorine
A.
ASTM
D 2361
B.
BS 1016
Part 8
SUMMARY OF METHODS
Sample is dried in oven at
104°C to 110°C for one hour,
under a stream of dry air.
This is an indirect method,
dependent upon the weight
loss of the sample.
Sample is dried in oven at
104°C to 110eC for one hour,
under a stream of nitrogen.
The determination may be in-
direct (as described above),
or direct by measuring the
moisture contained in an ab-
sorption tube.
Oxygen Bomb Method: Sample is
burned with Eschka mixture in
a bomb with oxygen.
Eschka Method: Sample is heat-
ed with Eschka mixture in oxi-
dizing atmosphere at 675°C for
1.5 hours.
In both methods, chloride is
determined by titration, either
colorimetrically or potentio-
metrically.
The same procedure is followed
as in the sulfur determination
of BS 1016, Part 6. HC1 is de-
termined by titration.
APPLICABILITY
Coal and coke.
Coal and coke.
Coal and coke.
Coal and coke.
ACCURACY (A) AND PRECISION (P)*
(P) Repeatability; 0.22 to 0.37.
Reproducibtlity: 0.3% to 0.5%
(P) Repeatability: 0.10% to 0.15Z
(P) Repeatability; 0.03Z
Reproducibility; 0.06%
(P) Repeatability:
(< 4%) - 0,02%
(> 4%) - 0.05%
Reproducibility:
(< 4%) - 0.02%
(> 4%) - 0.05%
-------
Table VI-2
PARAMETER
8. Gross Calorific
Value
METHODS OF ANALYSIS FOR COAL AND COKE
(continued)
SUGGESTED METEOP(S)
No./Title Ref.
A. ASTM
D 2015
(See Note #12)
B. ASTM
D 3286
(See Note 012)
C. BS 1016
Part 5
(See Notes #12
and #13)
SUMMARY OF METHODS
Adiabatlc Bomb Calorimeter
Method: Sample is burned in
oxygen and calorific value de-
termined from temperature rise.
Isothermal-Jacket Bomb Calori-
meter Method: Sample is burned
in oxygen and calorific value
is determined from temperature
readings and other heat sources.
Method is similar to ASTM pro-
cedures, using adiabatic, iso-
thermal, or static calorimeter.
APPLICABILITY
ACCURACY (A) AND PRECISION (P)*
Solid fuels.
Solid fuels.
Coal and coke.
(P) Repeatability: 29 cal/g
Reproducibility; 72 cal/g
U)
*Precision, when known, is usually given as either repeatability and/or reproducibility. The number
given for repeatability is the acceptable difference for duplicate results by the same laboratory;
that for reproducibility is the acceptable difference of duplicate results submitted by two or more
laboratories. The original reference should be checked if precision is critical since the wording
may imply special conditions for the applicability of the precision numbers given.
-------
Notes for Table VI-2;
1. There Is a titrimetric alternative to the gravimetric method, involving precipitation with barium chromate and subsequent iodometric
determination of remaining chrornate. Reference: International Standard 334, Coal and Coke - Determination of Sulphur - Eschka Method.
2. This method is useful for rapid results, or for a large number of determinations. The chlorine content of the sample is determined
at the same time as sulfur.
3. This is sometimes called the Liebig Method.
4. Nitrogen dioxide is produced, introducing an error in the carbon determination.
5. It is necessary to correct for hydrogen originally present as moisture in the sample.
6. Nitrogen dioxide is not produced at this high temperature.
7. The macro-method requiring 1 g of sample is necessary where bands of varying nitrogen composition occur in coal seams.
8. For low ash coke, a large sample size of 5 g may be necessary.
9. There is a modified ASTM procedure for samples high in calcite and/or pyrite.
10. The ash content must be corrected for sample moisture, if a pre-dried sample is not used.
11. The use of nitrogen in place of air prevents oxidation of the sample.
12. Corrections must be applied for-, heats of formation of H2S04 and HN03.
13. In the case of certain cokes, a correction for.unburned carbon may be required.
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CHAPTER VII
REFUSE-DERIVED SOLID FUELS (RDSF) AND PEAT
1. INTRODUCTION/SUMMARY
A. Refuse-Derived Solid Fuels
Refuse-derived solid fuels (RDSF) are taken here to primarily include pro-
cessed municipal refuse; the processing may include magnetic separation,
shredding, air classification, chemical treatment, milling or other such
processes. It is not the intent of this chapter to cover methods appli-
cable to raw (unprocessed) municipal refuse. Also the methods covered
here for RDSF are not intended to be applicable to refuse-derived liq-
uid fuels, industrial refuse-derived fuels, or agricultural and forestry
wastes.
RDSF may be used as the sole fuel in a heat-generating process, or it may
be used as a supplementary fuel. Several systems are currently operational
and several publicly and privatelyr^ponsored research projects are ongoing.
The use of RDSF is likely to grow signficantly in the years to come.
Table VII-1 gives a summary listing of the fuel analyses that are impor-
tant for RDSF combustion, along with an identification of the preferred
method of analysis and other information relating to the analyses. Addi-
tional information on the methods of analysis, including alternate methods
for most parameters, is given in Section 3 of this chapter. All of the
methods discussed are either fromjthe American Society for Testing and
Materials (ASTM) methods for coal and coke1, ASTM methods for peat5, Bu-
reau of Mines methods for coal and coke3, or U. S. Environmental Protec-
tion Agency (EPA) methods for solid waste2. While Only the EPA methods
were developed for specific application to RDSF (and other solid wastes),
both the ASTM and the Bureau of Mines methods for the more common para-
meters have been successfully used to characterize RDSF.
75
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It should be recognized that there is currently no generally accepted set
of standard analytical methods for the characterization of RDSF. The EPA
has, however, recently contracted with the ASTM (E38.01 Energy Subcommit-
tee) to develop such a set of standard methods for the sampling and anal-
ysis of RDSF. Tentative standard methods may be available in about two
years. Final approval by ASTM may require additional time.
It is expected that a significant number of methods will be modifications
of the existing ASTM methods for coal and coke. Because of this expecta-
tion, and because the ASTM methods for coal and coke seem to be generally
applicable to RDSF, they have been listed as the preferred method for all
methods covered in their manual. Their principal weakness may be that
test sample sizes may be too small for RDSF (that is not sufficiently homo-
geneous) resulting in erratic results on replicate samples. In such cases,
sample sizes should be increased (when possible) to allow the use of a re-
presentative portion.
Environmental assessments of processes using RDSF will need to include
additional fuel analyses beyond those covered in this manual. Those like-
ly to be required include: microbiological tests (including tests for
pathogenic organisms); trace elements in the fuel and in the ash; soluble
portions of the fuel (especially chloride and alkalies) and the ash; trace
organics in fuel leachate; odor; and, possibly, tests to determine the bio-
logical stability of the stored fuel.
B. Peat
According to the ASTM definition given in D 26075:
"The term peat refers only to organic matter of geologic
origin, excluding coal, formed from dead plant remains
in water and in the absence of air. It occurs in a bog,
swampland,, or marsh, and it has an ash content not ex-
ceeding 25% by dry weight."
Peat may appear to consist solely of fibrous material, even after it has
been shredded and milled. Minimum fiber contents (based on oven-dried
weights) are given for various classifications of peat in ASTM D 26075.
76
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Currently, peat is not used commercially as a fuel in the United States,
though significant deposits do occur in several of the north-central
states. It is used widely as a fuel in Ireland and Russia.
Table VII-2 gives a summary listing of the fuel analyses that are important
for peat combustion, along with an identification of the preferred method
of analysis and other information relating to the analyses. Additional
information on the methods of analysis, including alternate methods for
most parameters is given in Section 3 of this chapter. All of the meth-
ods discussed are either from ASTM methods for coal and coke1, ASTM meth-
ods for peat5, Bureau of Mines methods for coal and coke3, or EPA methods
for solid waste2. Only the methods (preferred methods in Table VII-2) for
nitrogen, moisture, ash, organic matter, and sieve analysis were specifi-
cally developed for peat. With regard to the other methods, no data were
available indicating the preferred methods were applicable. But, again,
the choice seems reasonable. As with RDSF, the chief weakness of the meth-
ods that are not intended for peat analyses may be inadequate sample size.
When working with peat that is not sufficiently homogeneous, the sample
sizes for these analyses should be increased, if possible.
Environmental assessments of processes using peat will heed to include
additional fuel analyses beyond those covered in this manual. Those
likely to be required include: trace elements in the fuel and in the
ash; soluble portions of the fuel and the ash (especially chloride and
alkalies); and, possibly, 'tests' to determine the biological stability of
the stored fuel.
2. SAMPLING
A. Refuse-Derived Solid Fuels
Sample collection and preparation must be given careful attention for
RDSF. The objectives of any sampling program should include:
77
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1. The collection of representative (bulk) samples;
2. Statistical sub-sampling to convenient working weights;
3. Preparation of a dry, uniform-textured material; and,
4. Disease control.
RDSF (taken here to be a processed municipal refuse) in its as-fired form
may lack any real homogeneity,and its composition may vary on both a daily
and seasonal basis.
Procedures for collecting gross samples of RDSF will have to be tailored
to (1) the nature of the material being sampled; (2) the nature of the
fuel-processing/handling equipment; and, (3) the precision and accuracy
requirements of the analyses to be carried out. Relatively simple grab
samplings may suffice for some purposes; the total sample should be the
composite of several grab samples spread out, both in space (e.g., differ-
ent portions of a stroage pile) and time. One description of such meth-
ods is given in the Bureau of Mines report, "Characterizing Combustible
Portions of Urban Refuse for Potential Use as Fuel"1*. When more preci-
sion is required in the gross sample, the methods described in ASTM
D 2334, "Standard Methods for Collection of a Gross Sample of Coal"1, may
be applicable with only slight modification; Section 8 and Appendices A-l
and A-2 of this method are especially pertinent.
The preparation of a laboratory sample from a gross sample .usually in-
volves three basic operations: (1) drying; (2) grinding or pulverizing;
and, (3) mixing. Procedures adequate for the preparation of a laboratory
sample of RDSF are given in several sources. The procedures of ASTM
D 2013, "Standard Method for Preparing Coal Samples for Analysis"1, and
ASTM D 271, "Standard Methods of Laboratory Sampling and Analysis of Coal
and Coke"1, are considered acceptable. In addition, the procedures given
for the preparation of a laboratory sample of coal by the Bureau of Mines3
and for the preparation of a laboratory sample of solid waster-related
materials by the EPA2 are suitable. Of all these methods, only those
given by the EPA are specifically intended for use with RDSF. It should
be noted that most of the ASTM analytical methods specify the type of
73
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sample to be used, including reference to a specific sample preparation
procedure.
None of the above mentioned methods give any detailed consideration to
disease control, though suggestions are given2'4 that the outside of the
sample collection bags be sprayed with Lysor&'and that the collectors and
analysts wear gloves (e.g., neoprene-coated canvas), and, possibly, face
masks. .Face masks, such as surgical masks, are recommended when working
with RDSF in the finely divided form2- The health risks associated with
handling municipal refuse are not well documented and there appear to be
no regulations for worker protection. Tetanus inoculation is one addi-
tional precaution that could be taken. Additionally, special care should
be taken in handling material known to contain hospital wastes; this ma-
terial could, in addition, be sterilized by various procedures.
B, Peat
Sampling methods for peat are given in ASTM D 2944, "Standard Method of
Sampling Peat Materials"5. This method covers procedures for obtaining
samples for use in the determination of moisture, ash, organic matter,
nitrogren, particle size range, and other parameters not covered in this
manual. For parameters other than the above, it may be necessary to use
the ASTM, Bureau of Mines, or EPA methods for the preparation on a labora-
tory sample* since they will yield a more homogeneous sample better suited
for those analyses where only small quantities are used.
3. ANALYSES
A. Refuse-Derived Solid Fuels
Table VII-3 gives, for each parameter of interest, additional information
on the method(s) of analysis deemed suitable. When more than one method
is listed, the preferred method is given first. The parameters are list-
ed in the order given in Table VII-1.
*See Section 2-A above for titles of and references to these methods.
79
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Three generally applicable comments should be considered. First, where
ASTM methods for coal and coke have been listed, the sample requirements
are generally small (see Table VII-1). These sample sizes may be inade-
quate for RDSF that is not as homogeneous as a similarly processed sample
of coal. Thus, sample sizes may need to be increased in some cases and
appropriate adjustments made in the analytical procedure. Additionally,
larger sample sizes would be preferable for the determination of the cal-
orific value of RDSF because their values are roughly half of those of the
more common fuels (e.g., coal, fuel oil). This can lead to additional
difficulty in the precise determination of temperature changes required
in the method. In this particular case, care should be taken not to in-
crease the sample size beyond the safe capacity of the bomb being used.
Second, caution should be used in the comparison of any precision informa-
tion given in Table VII-3 that derives from tests on coal and coke. The
homogeneity of the sample may not be comparable, and even if it was, the
values given in Table VII-3 may not apply where the absolute values of the
parameter being measured in RDSF are significantly different from those in
coal and coke. Such is the case, for example, with the calorific value.
Third, because the moisture content of RDSF may be highly variable - and
high on an absolute scale as well - it is suggested that analytical results
be reported on a "moisture-free" basis. The moisture-free sample is one
that has been dried at elevated temperatures (approximately 105°C) in a
manner such as is specified in either ASTM D 3173 or D 2974.
B. Peat
Information on all except two of the preferred methods of analysis for
peat (as listed in Table VII-2) is given in Table VII-3. Thus, Table VII-3
should be used for all of the peat analyses except nitrogen and size dis-
tribution. Equivalent information for these two parameters is given in
Table VII-4.
80
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The cautionary statements given above in Section 3-A for RDSF are also
applicable to peat. This holds especially for the variability (and high
values) of the moisture content and the resulting need to report all other
analyses on a moisture-free basis.
4. REFERENCES
1. "Annual Book of ASTM Standards (1974) - Part 26: Gaseous Fuels;
Coal and Coke; Atmospheric Analysis," American Society for Testing
and Materials, Philadelphia, Pennsylvania.
2. Bender, D. F., Peterson, M. L., and Stierli, J. (eds.), "Physical,
Chemical and Microbiological Methods of Solid Waste Testing," U. S.
Environmental Protection Agency, Cincinnati, Ohio; May, 1973.
3. "Methods of Analyzing and Testing Coal and Coke," U, S. Department
of the Interior, Bureau of Mines, Washington, D. C., 1967.
4. Schultz, H., Sullivan, P. M., and Walker, F. E., "Characterizing
Combustible Portions of Urban Refuse for Potential Use as Fuel,"
U. S. Department of the Interior, Bureau of Mines Report of Inves-
tigations, RI 8044, 1975.
5. "Annual Book of ASTM Standards (1974): Part 19: Natural Building
Stones; Soil and Rock; Peats, Mosses and Humus," American Society
for Testing and Materials, Philadephia, Pennsylvania.
81
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Table VII-1
1.
2.
3.
4.
5.
6.
7.
8.
9.
10.
11.
12.
13.
NP
a.
b.
c.
d.
ANALYSES FOR REFUSE-DERIVED SOLID FUELS
SUMMARY LISTING
APPROXIMATE
AMOUNT OF
SAMPLE NEEDED
PARAMETER PREFERRED METHOD3 FOR ANALYSISb
(g)
Carbon (Total)
and Hydrogen ASTM D 3178 0.2
Nitrogen ASTM D 3179 1.0
Sulfur ASTM D 3177 1.0
Oxygen ASTM D 271 NP
Chlorine ASTM D 2361 1.0
Moisture ASTM D 3173 1.0
Volatile Matter ASTM D 3175 1.0
Ash ASTM D 3174 1.0
Ash Fusibility ASTM D 1857 3-5 (of ash)
Apparent Density ASTM D 291 ^ 35 kg
(Procedure A)
Sieve Analysis ASTM D 410 min. 45 kg
Calorific Value ASTM D 2015 1.0
Carbonate Carbon ASTM D 1756 5.0
- Not Pertinent; NA - Not Available.
COST OF SRM
ANALYSIS0 AVAILABLEd
($)
20 - 30
15 - 25 SF-4
5-15
NA
4-15
5-15
5-15
15 - 25
5-10
4-12
10 - 20 SF-5
NA
All ASTM methods are given in Reference #1.
These are the sample requirements for a single analysis of coal or coke and
may be significantly different from the amount of RDSF needed. Greater
amounts of RDSF may be required for samples with little homogeneity. The
amounts required by a laboratory may also be larger for a variety of reasons,
including those connected with sample preparation.
Estimated ranged based on prices charged by one or more service laboratories
for coal analyses in early-1977.
See Appendix A for details.
82
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Table VII-2
ANALYSES FOR PEAT
SUMMARY LISTING
APPROXIMATE
AMOUNT OF
1.
2.
3.
4.
5.
6.
7.
8.
9.
10.
11.
12.
13.
NP -
a.
b.
PARAMETER
Carbon (Total)
and Hydrogen
Nitrogen
Sulfur
Oxygen
Chlorine
Moisture
Organic Matter
Ash
Ash Fusibility
Apparent Density
Sieve Analysis
Calorific Value
Carbonate Carbon
• Not Pertinent; NA -
All ASTM methods are
These are the sample
PREFERRED METHOD3
ASTM D 3178
ASTM D 2973
ASTM D 3177
ASTM D 271
ASTM D 2361
ASTM D 2974
(Method II)
ASTM D 2974
ASTM D 2974
ASTM D 1857
ASTM 291
(Procedure A)
ASTM D 2977
ASTM D 2015
ASTM D 1756
Not Available
given in Reference
requirements for a
SAMPLE NEEDED
FOR ANALYSIS
(g)
0.2
1.0
1.0
NP
1.0
100-300
10.
10.
3-5 (of ash)
*> 35 kg
100-300
1.0
5.0
#1.
single analysis
COST OF SRM
ANALYS is c AVAILABLE'
($)
20 -
15 -
5 -
—
NA
4 -
5 -
5 -
15 -
5 -
4 -
10 -
NA
of coal
30
25 SF-4
15
15
15
15
25
10
12
20 SF-5
or coke and
d.
may be significantly different from the amount of peat needed. Greater
amounts of peat may be required for samples with little homogeneity. The
amounts required by a laboratory may also be larger for a variety of reasons,
including those connected with sample preparation.
Estimated range based on prices charged by one or more service laboratories
for coal analyses in early-1977.
See Appendix A for details.
83
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Table VII-3
METHODS OF ANALYSIS FOR REFUSE-DERIVED SOLID FUELS (RDSF)
PARAMETER
1. Carbon (Total)
SUGGESTED METHOD(S)
Title/No. Ref.
A. ASTM
D 3178
(See Notes #1
and 112)
B. EPA
00
2. Nitrogen
A.
ASTM
D 3179
(See Notes #1,
#2, «3, and #4)
B. EPA-
Kjeldahl
SUMMARY OF METHODS
A weighed sample is burned in
a closed system and the pro-
ducts of combustion fixed in
an adsorption train. C02 ad-
sorber may contain NaOH, KOH
or soda lime. Moisture adsor-
ber is anhydrous magnesium per-
chlorate (Mg (ClOi,) 2 ) .
Essentially similary to ASTM
D 3178, but with additional
components in the combustion
train to insure complete com-
bustion of certain chemicals
and to remove undesirable pro-
ducts of combustion.
Analysis is by either the
Kjeldahl-Gunning or an alter-
native method. In both, ni-
trogen is converted to ammo-
nium salts which are subse-
quently decomposed; ammonia
is recovered by distillation
and finally determined by al-
kalimetric or acidlmetric
titration.
Kjeldahl method is similar to
that in ASTM D 3179.
APPLICABILITY
Method developed for coal
and coke. Should be ade-
quate for RDSF.
Generally applicable to
dry solid waste samples
containing 0.5% to 83.0%
carbon and 0.01% to 7.8%
hydrogen. Modifications
required for samples with
high values of As, Sb, Bi,
or Hg.
Method developed for coal
and coke. Should be ade-
quate for RDSF.
Applicable to RDSF if ni-
trogen content is primarily
organic and/or ammoniacal.
ACCURACY (A) AND PRECISION (P)*
(P) Unknown for RDSF. For coal
and coke:
Repeatability;
Carbon - 0.3%
Hydrogen - 0.07%
(A) Carbon determined within 1%
of true value; hydrogen with-
in 2% to 4%.
(P) See data given in Reference 12.
Tests showed standard deviations
for duplicate samples to be in
the following ranges:
Carbon - 0.04% to 0.22%
Hydrogen - 0.04% to 0.22%
(P) Unknown for RDSF. For coal
and coke:
Repeatability: 0.05%
(A) Tests on SRM's** always
yielded > 98.5% recovery.
(P) See data given in Reference 92.
Tests showed standard deviations
on replicate samples to range
from 0.01% to 0.12%.
All notes appear on the last page of this table.
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Table VII-3
METHODS OF ANALYSIS FOR REFUSE-DERVIED SOLID FUELS (RDSF)
(continued)
PARAMETER
2. Nitrogen
(continued)
SUGGESTED METHOD(S)
Title/No. Ref.
C. EPA 2
Comprehensive
D. EPA
00
3. Sulfur
A. ASTM
D 3177
(See Notes 01,
92, and 04)
B. ASTM
D 3177
(See Notes 01,
92, and f4)
SUMMARY OF METHODS
This is a modified Kjeldahl
procedure where nitrates are
first reduced wtih metallic
chromium in an acid medium.
An instrumental method in which
the sample is decomposed 'at high
temperatures in the absence of
air and with the aid of oxidiz-
ing agents. All nitrogen re-
duced to N2 and, after removal
of COz, is measured volumetri-
cally. (Analysis time * 15
minutes.)
Bomb Washing Method: Sulfur is
determined in the washings from
the oxygen-bomb calorimeter
following the calorimetric de-
termination (ASTM D 2015).
Eschka Method: Sulfur is deter-
mined as BaSO,, after sample is
heated (with the Eschka mixture)
in a controlled manner and sul-
fur containing residue extracted
with hot water. BaCla is used
to precipitate the sulfur. (The
method is more time consuming
than the bomb washing method.)
APPLICABILITY
Applicable to RDSF, espe-
cially for those with high
chloride-nitrate ratios.
Applicable to RDFS, in-
cluding samples with high
nitrate contents.
Method developed for coal
and coke. Should be ade-
quate for RDSF.
Method developed for coal
and coke. Should be ade-
quate for RDSF. Bureau of
Mines Eschka method (see
Reference #3) has been used
successfully on RDSF (see
Reference 04).
ACCURACY (A) AND PRECISION (P)*
(A) Tests on SRM's always yielded
> 98.2% recovery.
(P) See data given in Reference 1/2.
Tests showed standard deviations
on replicate samples to range
from 0.01% to O.UZ.
(A) Tests on SRM's always yielded
> 99% recovery.
(P) See data given in Reference #2.
Tests showed standard deviations
on replicate samples to be in
the range of O.OOZ to 0.10Z.
(P) Unknown for RDSF. For coal
and coke:
Repeatability r
Coal (< 2Z S) - 0.05Z
Coal (> 2Z S) - 0.10Z
Reproducibility:
Coal (< 2Z S) - 0.10Z
Coal (> 2Z S) - 0.20Z
(P) Same as for bomb washing
method.
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Table VII-3
METHODS OF ANALYSIS FOR REFUSE-DERIVED SOLID FUELS (RDSF)
(continued)
PARAMETER
SUGGESTED METHOD(S)
Title/No. Ref.
SUMMARY OF METHODS
It. Oxygen
5. Chlorine
00
ON
6. Moisture
A. ASTM
D 271
(See Note #2)
B. EPA
A. ASTM
D 2361
(See Notes 92
and #4)
B. EPA
A. ASTM
D 3173
(See Notes #1
and #2)
Determined indirectly by sub-
tracting from 100 the percent-
ages of hydrogen, carbon, sul-
fur, nitrogen, moisture, and
ash.
Determined indirectly from
known values for total carbon,
carbonate carbon in sample,
carbonate carbon in ash, hydro-
gen, nitrogen, sulfur, chlo-
rine, and volatiles (or ash).
Sample oxidized either in an
Eschka combustion apparatus or
a bomb containing oxygen under
pressure. Combustion residue
is collected in acid solution
and chlorine determined by
potentiometric titration or
by modified Volhard procedure.
Sample is oxidized in a bomb
containing oxygen under pres-
sure. Combustion products ad-
sorbed in a carbonate solution
are acidified and titrated with
mercuric nitrate.
Moisture is determined by mea-
suring the weight loss in a
sample after heating in an
oven, through which dry air is
circulated, for one hour.
APPLICABILITY
Method developed for coal
and coke. Should be appli-
cable for RDSF.
Applicable for RDSF.
Method developed for coal.
Should be applicable for
RDSF. Bureau of Mines (see
Reference #3) has been used
successfully on RDSF (see
Reference #4).
Applicable to RDSF. Io-
dine and bromine, if pre-
sent, will add to chlorine
result. Chromate and sul-
fate interfere when present
in excess of 10 mg/1, as
will ferric ions in excess
of 20 mg/1.
Method developed for coal
and coke. Should be appli-
cable for RDSF. (1 g test
specimen used.) Bureau of
Mines method (see Reference
#3) has been used success-
fully on RDSF (see Refer-
ence #4).
ACCURACY (A) AND PRECISION (P)*
Not known
(P) Inspection of past data, by
EPA, Indicates precision
should be within VI to 21.
(P) Unknown for RDSF. For coal:
Repeatability: 0.03%
Reprodueibillty; 0.06%
(A) EPA tests with SRM's had
mean recoveries of about
98%.
(P) See data give in Reference 92.
Tests showed standard deviations
on replicate sample to range,
with one exception, from 0.01%
to 0.04%.
(P) Unknown for RDSF. For coal
and coke:
Repeatability;
Coals (< 5% moisture) - 0.2%
Coals (> 5% moisture) - 0.3%
Reprodueibillty;
Coals (< 5% moisture) - 0.3%
Coals (> 5% moisture) - 0.5%
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Table VII-3
METHODS OF ANALYSIS FOR REFUSE-DERIVED SOLID FUELS (RDSF)
(continued)
PARAMETER
6. Moisture
^continued)
7. Volatile Hatter
00
SUGGESTED METHOD(S)
Title/No. Ref.
B. ASTM
D 2974
(See Note 04)
A. ASTM
D 3175
(See Notes 91
and #2)
B. EPA
C. ASTM
D 2794
SUMMARY OF METHODS
An as-received or air-dried
sample is heated in the open
air at 105°C for 16 hours.
Volatile matter is determined
from the weight loss after sam-
ple is heated in an oven at
950° ± 20°C for seven minutes.
A modification for sparking
samples is prescribed. Cruci-
ble with sample is kept cover-
ed to keep air out.
Volatile matter is determined
from the weight loss after the
sample is heated in an oven at
600°C (achieved gradually) for
two hours. Crucible are left
open (lids are tilted) to allow
air circulation over samples.
"Organic Matter" determined
from weight loss of sample
heated at S50°C (in an un-
covered dish) in an oven.
APPLICABILITY
Method developed for peat.
Should be applicable for
less homogeneous samples
of RDSF where larger sam-
ples must be used. (10 g
test specimen used.)
Method developed for coal
and coke. Should be appli-
cable for RDSF. Only vola-
tile hydrocarbons are mea-
sured .
Applicable for RDSF.
Method allows the oxi-
dation of elemental car-
bon.
Method developed for peat.
Should be applicable for
RDSF.
ACCURACY (A) AND PRECISIOH (P)*
Not given
(P) Unknown for RDSF. For other
materials:
Repeatability: Ranges from
0.2Z for coke up to 0.7Z for
low grade coal and 1Z for
lignite and peat.
Reproducibility; Ranges from
0.4Z for coke up to 1.4Z for
low grade coal and 2Z for
lignite and peat.
(A) EPA tests with SRM's showed
yields between 99.92Z and
100.45Z.
(P) See data given in Reference 12.
Tests showed standard deviations
on replicate combustible refuse
sample to range from 0.2Z to
2.2Z.
Not given
-------
Table VII-3
METHODS OF ANALYSIS FOR REFUSE-DERIVED SOLID FUELS (RDSF)
(continued)
PARAMETER
SUGGESTED HETHOD(S)
Title/Mo. Ref.
6. Moisture
{continued)
7. Volatile Matter
B. ASTM
D 2974
(See Note #4)
A. ASTM
D 3175
(See Notes 01
and #2)
00
00
B. EPA
C.
ASTM
D 2794
SUMMARY OF METHODS
An as-received or air-dried
sample is heated in the open
air at 105°C for 16 hours.
Volatile matter is determined
from the weight loss after sam-
ple is heated in an oven at
950° ± 20°C for seven minutes.
A modification for sparking
samples is prescribed. Cruci-
ble with sample is kept cover-
ed to keep air out.
Volatile matter is determined
from the weight loss after the
sample is heated in an oven at
600"C (achieved gradually) for
two hours. Crucible are left
open (lids are tilted) to allow
air circulation over samples.
"Organic Matter" determined
from weight loss of sample
heated at 550°C (in an un-
covered dish) in an oven.
APPLICABILITY
Method developed for peat.
Should be applicable for
less homogeneous samples
of RDSF where larger sam-
ples must be used. (10 g
test specimen used.)
Method developed for coal
and coke. Should be appli-
cable for RDSF. Only vola-
tile hydrocarbons are mea-
sured.
Applicable for RDSF.
Method allows the oxi-
dation of elemental car-
bon.
Method developed for peat.
Should be applicable for
RDSF.
ACCURACY (A) AND PRECISION (P)*
Not given
(P) Unknown for RDSF. For other
materials:
Repeatability; Ranges from
0.2Z for coke up to 0.7Z for
low grade coal and 1Z for
lignite and peat.
Reproducibility; Ranges from
0.4Z for coke up to 1.4Z for
low grade coal and 2Z for
lignite and peat.
(A) EPA tests with SRM's showed
yields between 99.92Z and
100.45Z.
(P) See data given in Reference *2.
Tests showed standard deviations
on replicate combustible refuse
sample to range from 0.2Z to
2.2Z.
Not given
-------
Table VII-3
PARAMETER
11. Sieve Analysis
12. Calorific Value
00
VO
METHODS OF ANALYSIS FOR REFUSE-DERIVED SOLID FUELS (RDSF)
(continued)
SUGGESTED METHOD(S)
Title/No. Ref.
A. ASTM
D 410
B. ASTM
A. ASTM
D 2015
(See Notes 9k
and #6)
B. ASTM
D 271
(See Notes #2
and 16)
C. EPA
Total Beat
of Combustion
(See Note 16)
SUMMARY OF METHODS
Sample is passed through a
series of sieves, largest
first, and the amount retained
on each sieve weighed.
Samples are sieved succes-
sively with a series of
sieves, smallest first, and
the amount retained on each
sieve weight.
A weighed sample is burned in
an adiabatic bomb calorimeter
and the calorific value deter-
mined from temperature obser-
vations made before and after
combustion.• Thermometer and
thermochemical corrections
are required.
A weighed sample is burned in
a bomb calorimeter and the
calorific value determined
from temperature and time
observations made before,
during, and after combustion.
Thermometer and thermochemi-
cal corrections are required.
Method uses Parr adiabatic
calorimeter in a manner simi-
lar to that given in ASTM
D 2015.
APPLICABILITY
Method developed for bulk
samples of coal. Should be
applicable for bulk samples
of RDSF that have not been
finely shredded.
Method developed for pul-
verized coal. Should be
applicable for finely shred-
ded RDSF having no particle
>. 0.32 cm (1/8").
Method developed for solid
fuels and should be appli-
cable to RDSF.
Method developed for coal
and coke. Should be appli-
cable to RDSF. Bureau of
Mines method (see Reference
93) has been used success-
fully on RDSF (see Reference
#4).
Applicable to RDSF with
particle size less than
2 mm.
ACCURACY (A) AMD PRECISION (P)*
(F) Unknown for RDSF. For coal,
sum of weights should be with-
in 21 of initial sample weight.
(P) Unknown for RDSF. For coal:
Repeatability: 1Z on all
sizes
Reproducibility: 3Z on No. 200
sieve
(P) Unknown for RDSF. For 60-
mesh pulps (see D 2015 in
Reference fl).
Repeatability; : 27.8 cal/g
(50 Btu), dry basis
Reproducibility: 55.6 cal/g
(100 Btu), dry basis
(P) Unknown for RDSF. For coal
and coke:
Repeatability: 27.8 cal/g
(50 Btu), dry basis
Reproducibility; 55.6 cal/g
(100 Btu), dry basis
(A) EPA tests with SRM's gave
average value 1.2Z from
true value.
(P) See data given in Reference 12.
Tests showed standard deviations
of duplicate (combustible) re-
fuse samples were 42 cal/g (76
Btu/lb).
-------
Table VII-3
METHODS OF ANALYSIS FOR REFUSE-DERIVED SOLID FUELS (RDSF)
(continued)
PARAMETER
13. Carbonate Carbon
SUGGESTED METHOD(S)
Title/No. Ref.
A. ASTH
D 1756
B. EPA
vo
O
SUMMARY OF METHODS
Carbonate carbon is determined
as carbon dioxide by decompos-
ing, with hydrochloric acid, a
weighed sample in a closed sys-
tem. The evolved carbon diox-
ide is absorbed in an absorbent
(NaOH or KOH on an inert car-
rier). The increase in weight
of the absorbent is measured,
and the carbon dioxide content
of the sample determined from
this figure.
Carbonate carbon is determined
• gravlmetrically after reacting
the sample with hydrochloric
acid and fixing the evolved
gases in an adsorption train.
C<>2 from the carbonate carbon
is adsorbed in Nesbitt bulbs
(containing Indicard and acti-
cated alumina).
APPLICABILITY
Method developed for coal.
Should be applicable to
RDSF.
Applicable for RDSF. Good
results achieved on samples
with carbonate contents from
0.05Z to 8.0Z.
ACCURACY (A) AND PRECISION (P)
(P) Unknown for RDSF. For coal:
Repeatability;
0.05Z for C02 < 1Z
0.10Z for C02 > 1Z
Reproducibility;
0.10Z for C02 < 1Z
0.20Z for C02 > 1Z
(A) EPA tests with SWA'a had
average yield of 99.7Z.
(P) See data given In Reference 92.
Tests showed standard deviation
for duplicate analyses on por-
tions of refuse ranged from
0.01Z to 0.18Z.
*Precision, when known, is usually given as either repeatability and/or reproducibility. The number
given for repeatability is the acceptable difference for duplicate results by the same laboratory;
that for reproducibility is the acceptable difference for duplicate results submitted by two or more
laboratories. The original references should be checked if precision is critical since the wording
may imply special conditions for the applicability of the precision numbers given.
**SSM: Standard Reference Materials.
-------
Notes for Table VII-3;
1. Method also given in ASTM D 271. (See Reference #1.)
2. A similar method is specified in the Bureau of Mines publication, "Methods of Analyzing and Testing
Coal and Coke". (See Reference #3.)
3. An additional alternative method for the analysis of nitrogen in RDSF is given in ASTM D 2973,
"Standard Method of Test for Total Nitrogen in Peat Materials"5. The method is similar to the
ASTM D 3179 ("alternative") method with the major difference being that D 2973 requires a 10 g
tests sample versus a 1 g test sample for D 3179. Data from duplicate analyses of RDSF by this
method (D 2973) are given in Appendix D.
4. Data from analyses of a RDSF by this method are given in Appendix D.
5. A compact apparent density may also be determined by applying a 9.07 kg (20 pound) plunger,
30.48 cm x 30.48 cm (12" x 12") to the top of the box containing the sample. When this is done,
the vertical dimensions of the compacted sample must be measured to determine the volume.
6. These methods determine the gross calorific value which is obtained under conditions of constant
volume. It is often desired to have the net calorific value which is the value corresponding to
combustion at atmospheric pressure, under conditions such that all water in the products remains
in the form of vapor. The net calorific value may be calculated from the gross calorific value,
as described in ASTM D 407l.
-------
Table VII-4
METHODS OF ANALYSIS FOR PEAT - SUPPLEMENTARY LISTING
(See Table VII-3 for information on other specified analyses for peat.)
PARAMETER
SUGGESTED METHOD(S)
No./Title Ref.
1. Nitrogen
ASTM D 2973
2. Size Distribution ASTH D 2977
SUMMARY OF METHODS
Nitrogen is converted into
ammonium salts by destructive
digestion and., subsequently,
decomposed in a hot alkaline
solution from which the ammo-
nia is recovered by distilla-
tion and finally determined
by acidlmetric titration.
An air-dried sample is sepa-
rated into four designated
fractions by means of an 8-
mesh and a 20-mesh sieve.
One fraction consists of for-
eign matter removed manually
from the 8-raesh sieve.
APPLICABILITY
ACCURACY (A) AND PRECISION (P)
Method developed for peat. Not given
Method developed for peat.
Will not be adequate for
finely milled peat.
Not given
N>
-------
APPENDIX A
AVAILABLE STANDARD REFERENCE MATERIALS
93
-------
TABLE OF CONTENTS
Page
1. Introduction 97
2. Types of Reference Materials 97
3. Reference Materials of Various Fuel Categories 98
A. Gaseous Fuels 98
B. Liquid Fuels 98
C. Solid Fuels 98
4. Sources of Reference Materials 99
LIST OF TABLES
Page
Table A-l - Standard Reference Mateirals for
Gaseous Fuels 100
Table A-2 - Standard Reference Materials for
Liquid Fuels 101
Table A-3 - Standard Reference Materials for
Solid Fuels 102
95
-------
1. INTRODUCTION
Reference materials are mixtures or pure substances which have been pre-
pared or analyzed in such a way that the concentrations of particular
elements in these materials, or particular physical properties, are known
accurately. Such materials of known composition are often used in commerce
and other fields to establish the accuracy of new chemical and physical
analysis methods. In addition, analysis of those materials allows assess-
ment of the performance of the analysts carrying out the tests. Submission
of portions of appropriate reference materials as part of a sample set can
also constitute a type of quality assurance program on analyses being per-
formed. This can be of particular use when the analytical laboratory is
remote from the group originating the samples.
2. TYPES OF REFERENCE MATERIALS
There are various types or classes of reference materials which can be
used to check on the accuracy and precision of analyses.
Those substances which are most accurately characterized, either by pre-
paration or by analysis, are generally termed "certified" reference mate-
rials. The U.S. Bureau of Standards refers to their known substances as
Standard Reference Materials (SRM). Such materials are prepared, tested,
and certified by experts in their fields. Thus, these reference materials
are suitable for validating both the absolute accuracy and the precision
of analytical methods.
Other homogeneous materials can be used to provide data on inter- and intra-
laboratory precision and relative accuracy. Frequently, a large portion
of a single sample, deemed to be representative of the materials being
analyzed, will be thoroughly homogenized and split into two or more
samples submitted to the laboratories involved.
In addition, if suitable laborabory facilities and expertise are available,
portions of a sample can be treated ("spiked") with known amounts of one
97
-------
or more elements or compounds. The "spiked" samples, together with a por-
tion of the original "unspiked" material, are submitted for analysis. The
recovery of the added elements or compounds is indicative of the accur-
acy being achieved.
3. REFERENCE MATERIALS FOR VARIOUS FUEL CATEGORIES
A. Gaseous Fuels
Virtually all gaseous reference mixtures are prepared by blending pure com-
ponents, both by weight and by volume, rather than analyzing a "real" sam-
ple. This approach is practical since the number of possible components
in any gaseous fuel is relatively limited, while the range of concentration
varies widely according to the source of the gas,
Gaseous fuel standards are available from commercial suppliers in "certi-
fied" and "analyzed" grades. A listing of the sources is given in Table
A-l.
B. Liquid Fuels
A listing of reference' materials available for liquid fuels is given in
Table A-2. As can be seen, only a limited number of parameters are cover-
ed by available materials. This lack of materials for other parameters
has been attributed, for the most part, to the lack of demand. Standards
suitable for other parameters, such as nitrogen, can be prepared by "spik-
ing" a low nitrogen oil with one or more appropriate (heterocyclic, ali-
phatic, etc.) nitrogen compounds. Metals can be added as organometalic
complexes. Suitable materials of this nature are available from the
National Bureau of Standards (SRM 1051-1080) or from Continental Oil Company,
Ponca City, Oklahoma (additives marketed as CONOSTANS^).
C. Solid Fuels
A listing of the reference materials available for solid fuels is given in
Table A-3. The principal matrix available is coal, and the number of para-
meters covered is quite limited. A frequently stated reason for the limit-
98
-------
ed number of coal materials available is that they tend to be unstable due
to oxidation. As shown in the listing, a botanical standard for trace ele-
ments and nitrogen should be a reasonably close match for the cellulosic
fuels, peat and RDSF, in lieu of materials specific to those fuels. "Spik-
ing" solid fuels with additives is more difficult than with liquid fuels
since achieving homogeneous distribution takes considerably more time and
care. Spiking should only be attempted if the fuel is very finely divided
and is easily mixed in a ball or roller mill.
A. SOURCES OF REFERENCE MATERIALS
Sources of the various reference materials are listed on Tables A-l to A-3.
In addition to the National Bureau of Standards, contacts were made with
U. S. marketing representatives of European and Japanese standards organi-
zations. Unfortunately, no fuel-related reference materials are available
at this time, from any source.
Compounds for "spiking" purposes (nitrogen-containing organics, for example)
are available from a number of reliable reagent chemical supply firms, such
as Eastman Kodak Company. As noted under Liquid Fuels, organometallic addi-
tives are available from Continental Oil Company.
99
-------
Table A-l
STANDARD REFERENCE MATERIALS FOR GASEOUS FUELS
NUMBER
STANDARD FOR:
DESCRIPTION
GF-1 Natural gas components
GF-2 Gaseous fuel components
Prepared mixture simulating
natural gas
Custom-blended mixtures of
components can be made up
to correspond to any gaseous
fuel composition. Mixtures
generally available in "pri-
mary standard" (highest ac-
curacy) and "working" or
"certified standard" grades.
SOURCE
PC
MGP
SET
Sources; PC - Philips Chemical Company, Borger, Texas
MGP - Matheson Gas Products, East Rutherford, New Jersey
SET - Scott Environmental Technology, Inc., Plumsteadville,
Pennsylvania
100
-------
Table A-2
STANDARD REFERENCE MATERIALS FOR LIQUID FUELS
NUMBER
STANDARD FOR:
DESCRIPTION
LF-1 S in residual oil
LF-2 S in distilate oil
LF-3 Trace elements (Ni, Pb,
V, Zn, Fe, S) in resi-
dual oil
LF-4 Trace Ni and V in resi-
dual oil
LF-5 Calorific value
SRM 1621, 1622, 1623 (1.1%,
2.1%, and 0.3% S)
SRM 1624 (0.2% S)
SRM 1634
GM-5 (certified by Western
Gas and Oil Association and
American Petroleum Institute)
SRM 217b (2,2,4-trimethyIpen-
tane, heat of combustion stan-
dard) [Also see Table A-3:
S-5.]
SOURCE
NBS
NBS
NBS
NBS
NBS
Source; NBS - National Bureau of Standards, Office of Standard Reference
Materials, Washington, D. C.
101
-------
Table A-3
STANDARD REFERENCE MATERIALS FOR SOLID FUELS
NUMBER
SF-1
SF-2
SF-3
SF-4
SF-5
STANDARD FOR:
DESCRIPTION
Ash and S in coal
Trace elements (14)
in coal
Trace Hg in coal
N and trace elements (14)
in RDSF and peat
Calorific value
SRM 1631 (set of 3)
SRM 1632
STM 1630
SRM 1571 (prepared from
leaves)
SRM 39i (benzoic acid, heat
of combustion standard)
SOURCE
NBS
NBS
NBS
NBS
NBS
Source; NBS - National Bureau of Standards, Office of Standard Reference
Materials, Washington, D. C.
102
-------
APPENDIX B
LABORATORY DIRECTORIES
103
-------
LABORATORY DIRECTORIES
Given below is a list of laboratory directories which may be of use in ob-
taining the services of an analytical laboratory for fuel analyses. For
listings that cover a specific geographical area, it is suggested that
State directories be consulted. The Department of Commerce or its equi-
valent in most states publishes directories of research organizations
and laboratories within the State.
1. The American Council of Independent Laboratories, Inc., Directory,
1976.
Published by: ACIL
1725 'K1 Street, N. W.
Washington, D. C.
(The Directory is revised every two years. The 1978 Directory will
be available in early 1978.)
2. Industrial Research Laboratories of the United States, Fourteenth
Edition, 1975.
Published by: R. R. Bowker Company
1180 Avenue of the Americas
New York, New York 10036
(Directory is revised approximately every five years.)
3. Directory of Testing Laboratories, STP 333 C, January, 1973.
Compiled and published by: American Society for Testing and Materials
1916 Race Street
Philadelphia, Pennsylvania 19103
4. Directory of Testing Laboratories, Commerical and Institutional,
STP 333 A, November, 1969.
Compiled and published by: American Society for Testing and Materials
1916 Race Street
Philadelphia, Pennsylvania 19103
105
-------
5. LABGUIDE 1975-1976, August, 1975. ACS Laboratory Guide to Instruments,
Equipment and Chemicals.
Published by: American Chemical Society
115 Sixteenth Street, N. W.
Washington, D. C. 20036
(Pubished annually in August by the ACS.)
6. Union Internationale des Laboratoires Independants, Register of Mem-
bers. 1975.
Published by: Ashbourne House
Alberon Gardens
London NW11 OBN
England
(Listing covers laboratories in North and South America, Europe,
Australia, and other localities.)
106
-------
APPENDIX C
TYPICAL VALUES (RANGES) OF PARAMETERS
SPECIFIED FOR EACH FUEL
107
-------
TABLE OF CONTENTS
Page
Introduction
LIST OF TABLES
Page
Table C-l - Typical Values (Ranges) of Parameters
Specified for Gaseous Fuels 112
Table C-2 - Typical Values (Ranges) of Parameters
Specified for Liquid Petroleum Fuels 114
Table C-3 - Typical Values (Ranges) of Parameters
Specified for Shale Oil 116
Table C-4 - Typical Values (Ranges) of Parameters
Specified for Coal Liquids 119
Table C-5 - Typical Values (Ranges) Expected from
Methyl Fuel Analyses 121
Table C-6 - Typical Values (Ranges) of Parameters
Specified for Coal and Coke 122
Table C-7 - Typical Values (Ranges) of Paramters
Specified for Refuse-Derived Solid
Fuels (RDSF) 123
Table C-8 - Typical Values (Ranges) of Parameters
Specified for Pear 125
109
-------
INTRODUCTION
The following tables give typical values, or ranges, of the parameters
specified for each of the fuels covered in this manual. The values asso-
ciated with any range are not necessarily the maximum and minimum values
that could be found, but generally delineate a range that most values will
be found in.
The sources used in the preparation of a table are listed with each table.
Ill
-------
Table C-l
TYPICAL VALUES
(RANGES) OF PARAMETERS SPECIFIED FOR GASEOUS FUELS
PETROLEUM GASES
PARAMETER NATURAL GAS
Hydrocarbons - mol %
nil _ QO
dntf yj
C2H6/C2H4 3.9/0
C3H6/C3H6 0.7/0
f* TT /ft T¥ A 1 /A
^ifH-1 0' ^^"8 -"•'
> Cij 0.2
H
10 Others - mol %
CO
H2
C02 1
N2 0.6
02
H2S (in mg/cu m) *v 1
Total S (in ^ 1
mg/cu m)
Calorific Value 1,000 (9,000)
Btu/scf (K cal/cu m)
COAL GASES , ,,
Lurgi (02)a Koppers-Totzel£ No. 4 Fuel Oil
10-14 24-28
2-3/18-21
0.3-0.7/2-3
0/0.7-1.5
3-4 (some
aromatics)
25-30 55
50-60 35 12-14
7
> 0.5 1 30 (inert
carrier gas)
Sulfide content .dependent upon sulfur in feed -
may be up to 7,000 mg/cu m for high sulfur (3%)
400 (3,600) 300 (2,700) 1,200 (10,700)
Hydrogasification
of Heavy Naphtha
34
12/9
0.4/2
0.1/0.5
< 0.1/2-3
40
trace
990 (8,800)
All notes and sources of information on following page.
-------
Notes for Table C-l;
a. For bituminous coal.
b. For 62, bituminous coal.
Sources:
1. Kirk-Othmer, Encyclopedia of Chemical Technology, Volume 10: "Gas,
Manufactured", Second Edition, Interscience, New York, 1966.
2. Tillman, D. A., "Status of Coal Gasification," Environmental Science
Technology, Volume 10, pages 34-38, 1976.
113
-------
Table C-2
AVERAGE VALUES OF PARAMETERS SPECIFIED FOR PETROLEUM FUELS
LPG GASOLINE (BY GRADE) TURBINE FUELS (BY GRADE)
la.
Ib.
2.
3.
4.
5.
6.
7.
8.
9.
10.
11.
12.
13.
14.
15.
16.
PARAMETERS
Carbon, wt. Z
Hydrogen, wt. Z
Nitrogen, wt. Z
Sulfur, wt. Z
Oxygen, wt. Z
Chlorine, wt. Z
Water and Sediment
Ash, wt. Z
Calorific Value, Btu/lb.
Carbon Residue, wt. Z
Distillation Temperature
Volute Evaporated:
10Z, *F
50Z, "F
90Z, °F
End Point
Vapor Pressure, Ib.
Flash Point, "F
Pour Point, °F
Viscosity, Kinematic CS
Density, g/cm3
Corrosion, t
PROPANE BUTANE A B C D E AVIATION GASOLINE TYPE A
— —
_ _
__
0.1 M 0.1 M 0.1 M 0.1 H 0.1 M 0.05 M 0.055
_ __
— —
none 0.2
_ —
21560 21180 18720-18800 18600
_
•
158 149 140 131 122 158 369
170-250 170-245 170-240 170-235 170-230 221 410
374 374 365 365 365 212-257 464
437 437 437 437 437 338 500
124 (70°F) 31 (70°F) 9 10 11.5 13.5 15 7.0 —
— — 110
— — -72 FP -40
— — 8.85
0.509 0.509 39-51 (API)
1111111 1 1
TYPE B
0.044
0.1
18700
222
315
'423
480
3 M
—
-60
2.94
45-57 (API)
1
All notes appear on the last page of this table.
-------
Table C-2
la.
Ib.
2.
3.
4.
5.
6.
7.
8.
9.
10.
11.
12.
13.
14.
15.
16.
PARAMETER
Carbon, vt. Z
Hydrogen, vt. Z
Nitrogen, wt. Z
Sulfur, wt. Z
Oxygen, wt. Z
Chlorine, wt. Z
Water and Sediment
Ash, wt. Z
Calorific Value, Btu/lb.
Carbon Residue, wt. Z
Distillation Temperature
Volume Evaporated:
10Z, T
50Z, *P
90Z, *F
End Point
Vapor Pressure, Ib.
Plash Point, °F
Pour Point, *P
Viscosity, Kinematic CS
Density, g/cm3
Corrosion, I
/
AVERAGE VALUES OF PARAMETERS SPECIFIED FOR PETROLEUM FUELS
(continued)
DIESEL FUEL (BY GRADE) HEATIUG OILS (BY GRADE)
l(C-B) 2(T-T) 3(R-R) 4 (S-M) *1 #2 *4 t5 16 HASTE OIL
0.14 0.22 0.29 0.54 0.07 0.25 0.77 1.07 1.33 0.3
0.03 M 0.1 M 0.1 M 0.5 M T 0.1 M 0.5 M 0.16 M 0.15 4.4
0.0005 0.0009 0.001 0.0023 0.1 M 0.035 0.41 1.3-1.8
0.057 0.088 0.117 0.163 0.052 0.116 3.3 6.7 10.7 2.2
393 430 440 448 390 432 496
440 490 502 509 437 499 674
501 557 574 582 550 M 640 M
542 600 618 622 533 629 754
100 Ml 125 Ml 130 Ml 130 Ml 100 Ml 100 Ml 130 Ml 130 Ml 150 Ml 215
OH 20 M 20 M
1.84 2.54 2.74 2.79 1.79 2.61 15.4 60.2 —
42 (API) 37 (API) 35 (API) 34 (API) 43 (API) 35 (API) 21 (API) 17 (API) 12 (API) 25 (API)
233 — 3
LPG: Liquefied Petroleum Gas
T: Trace
M: Maximum Specified Value ML: mn-limipi Specified Value
API: API units - (141.2/sp. gr.) - 131.5
-------
Table C-3
TYPICAL VALUES (RANGES) OF PARAMETERS SPECIFIED FOR SHALE OIL
TYPICAL RANGE OF VALUES^
la
Ib
2.
3.
4.
5.
6.
7.
8.
9.
10.
11.
12.
13.
14.
15.
16.
NA -
a.
b.
PARAMETERS
. Carbon, wt. %
. Hydrogen, wt. %
Nitrogen, wt. %
Sulfur, wt. %
Oxygen, wt. %
Chlorine, wt. %
Water and Sediment
Ash, wt. %
Calorific Value, Btu/lb. (cal/g)
Carbon Residue, wt. %
Distillation, Volume %
(Typical Values)
IBP to 400 °F
400°F to 600°F
600 °F to 900 °F
900 °F + higher
Vapor Pressure
Flash Point
Pour Point, °C (°F)
Viscosity, SUS at 100°F
Density, g/cm3
Corrosion
• Not Available
CRUDE
80 - 85
10 - 12
1.2 - 2.4
0.5 - 1.0
1.5 - 6
< 0.1
NAb
* 0.06 (?)
NA
1.5 - 5
18%
24%
34%
24%
NA
NA
4.4 - 32 (40 - 90)
50 - 350
0.88 - 0.94
NA
Sources used are listed on the following pages.
Typical quantities of "bound water" in crude shale oil
REFINED
80 - 85
10 - 12
1.0 - 1.6
0.5 - 1.0
1-2
< 0.1
NA
< 0.01
* 20,000 (11,000)
NA
NA
NA
NA
NA
NA
.75 - .9
for distillates
NA
produced above1-
ground retorts may be only a few percent. Crude shale oil from in situ
retorting may contain from a few percent to 50 percent distillable water.
(See Source #3 on the following page.)
116
-------
Sources for Table C-3;
1. Van Nostrand's Scientific Encyclopedia. Fifth Edition, 1976,
Douglas M. Considine, Editor, Van Nostrand Rinehold Company.
2. Ruberto, R. G., Jewell, D. M., Jensen, R. K., and Cronauer, D. C.,
"Characterization of Synthetic Liquid Fuels," Shale Oil, Tar Sands.
and Related Fuel Sources, Chapter 3. Teh Fu Yen, Editor, Advances
in Chemistry Series 151, American Chemical Society, Washington, D. C.,
1976.
3. Jackson, L. P., Poulson, R. E. Spedding, T. J. , Phillips, T. E., and
Jensen, H. B., "Characteristics and Possible Roles of Various Waters
Significant to In Situ Oil-Shale Processing," Colorado School of Mines
Quarterly, Volume 70, October, 1975, pages 105-134.
4. Jackson, L. P., Morandi, J. R., and Poulson, R. E., "Compositional
Variation of Retorted Shale Oils with Stratigraphy: Wyoming Core,
Northern Green River Basin," paper presented at the Fuel Chemistry
Division Symposium on "Oil Sand and Oil Shale," American Chemical
Society Meeting, May 29-June 2, 1977, Montreal, Canada.
5. Poulson, R. E., Smith, J. W., Young, N. B., Robb, W. A., and Spedding,
T. J., "Minor Elements in Oil Shale and Oil Shale Products," U. S.
Energy Research and Development Administration, Laramie Energy Re-
search Center, Laramie, Wyoming, January, 1977. (Report No. LERC/RI-
77/1.)
6. Poulson, R. E., "Nitrogen and Sulfur in Raw and Refined Shale Oils,"
Division of Fuel Chemistry, American Chemical Society. Preprints
Volume 20, No. 2, April 6-11, 1975, pages 183-197.
7. Frost, C. M. and Poulson, R. E., "Nitrogen Types in Syncrudes from In
Situ Crude Shale Oil," Division of Fuel Chemistry, American Chemical
Society. Preprints Volume 20, No. 2, April 6-11, 1975, pages 176-182.
8. Jensen, H. B., Poulson, R. E., and Cook, G. L., "Characterization of
a Shale Oil Produced by In Situ Retorting," Division of Fuel Chemistry,
American Chemical Society. Preprints Volume 15, No. 1, March 29-
April 2, 1971, pages 133-121.
9. Dinneen, G. V., Ball, J. S., and Thome, H. M., "Composition of Crude
Shale Oils," Industrial and Engineering Chemistry, Volume 44, No. 11,
1952, pages 2362-2365.
10. "Report of the Conference-Workshop entitled 'Analytical Chemistry Per-
taining to Oil Shale and Shale Oil'," sponsored by and held at the
National Science Foundation, Washington, D. C., June 24-25, 1974.
117
-------
Sources for Table C-3 (continued);
11. Poulson, R. E., Frost, C. M., and Jensen, H..B., "Characteristics of
Synthetic Crude from Crude Shale Oil Produced by In Situ Combustion
Retorting," Division of Fuel Chemisty, American Chemical Society. Pre-
prints, Volume 19, No. 2, 1975, pages 175-182.
12. Robinson, W. E. and Cook, G. L., "Compositional Variations of the Or-
ganic Matter of Green River Oil Shale - Colorado No. 1 Core," U. S.
Department of the Interior, Bureau of Mines Report of Investigations
No. 7492, 1971.
13. Robinson, W. E. and Cook, G. L., "Compositional Variations of the Or-
ganic Material from Green River Oil Shale - Wyoming No. 1 Core," U. S.
Department of the Interior, Bureau of Mines Report of Investigations
No. 7280, 1973.
14. Ruark, J. R., Sohns, H. W., and Carpenter, H. C., "Gas Combustion Re-
torting of Oil Shale Under Anvil Points Lease Agreement: Stage II,"
U. S. Department of the Interior, Bureau of Mines Report of Investi-
gations No. 7540, 1971.
15. "Fuel Contaminants - Volume 1: Chemistry," U. S. Environmental Pro-
tection Agency, Research Triangle Park, Durham, North Carolina, 1976.
(Report No. EPA-600/2-76-177a.)
118
-------
Table C-4
TYPICAL VALUES (RANGES) OF PARAMETERS
SPECIFIED FOR COAL LIQUIDS
PARAMETER TYPICAL RANGE OF VALUES a
la. Carbon (Total), wt. % 80-90
Ib. Hydrogen, wt. % 5-10
2. Nitrogen, wt. % 0.1-2.5
3. Sulfur, wt.% < ,.1-3.0
4. Oxygen, wt. % 0.1-12
5. Chlorine, wt. % < 0.1
6. Water and Sediment, wt. % < 5
7. Ash, wt. % 0.1 - 1.0
8. Calorific Value, Btu/lb. (cal/g) 15,000 - 20,000
(8,330 - 11,100)
9. Carbon Residue, wt. % NA
10. Distillation, Volume %
(Typical Values)
IBP to 400°F 10% - 20%
400°F to 600°F 20% - 50%
600°F to 900°F 20% - 50%
900°F + higher 10% - 20%
11. Vapor Pressure NA
12. Flash Point NA
13. Pour Point, °C (°F) < 38 (< 100)
14. Viscosity, SUS at 100°F NA
15. Density ' °-85 ~ 1-2
16. Corrosion NA
NA - Not Available
a. Sources used are listed on the following page.
119
-------
Sources for Table C-4;
1. Cusumano, J. A., DallaBetta, E. A., and Levy, R. B., "Scientific Re-
sources Relevant to the Catalytic Problems in the Conversion of Coal,"
ERDA FE-2017-1, October, 1976.
2. Whitehurst, D. D., Farcasiu, M., and Mitchell, T. 0., "The Nature and
Origin of Asphaltenes in Processed Coals," Mobil Research and Develop-
ment Corporation, Princeton, New Jersey.
3. Yen, T. F., Shale Oil, Tar Sands, and Related Fuel Sources, American
Chemical Society, Washington, D. C., 1976.
4. Work in progress at Arthur D. Little, Inc., under ERDA contract no.
EX-76-C-01-1754, "Experimental Study of an Extracting Coking Process
to Produce Low-Sulfur Liquid Fuels from Bituminous Coal."
120
-------
Table C-5
TYPICAL VALUES OF PARAMETERS SPECIFIED FOR METHYL FUEL ANALYSIS
PARAMETER
Methanol Content, wt. %
1. Nitrogen
2. Sulfur
3. Chloride
4. Water, wt. %
5. Higher Alcohols, wt. %
6. Nonvolatile Matter, wt. %
7. Calorific Value, Btu/.lb. (cal/g)
8. Specific Gravity (20°C/20°C)
9. Viscosity, cp (25°C)
10. Boiling Point, °C (1 atm.)
11. Flash Point, °C
12. Vapor Pressure, mm Hg (20°C)
13. Corrosion Rate
14. Acidity, wt. % as acetic acid
APPROXIMATE OR ESTIMATED VALUE
90 - 95
?, probably small
?, probably very
small (< 1 ppm)
?, present only if
shipped by ocean
tanker
0.5 - 5
0.1 - 10
*> 0.01
10,000 (5,550)
0.80 - 0.82
0.67 - 0.79
65 - 67
11 - 13 (closed cup)
18 - 21 (open cup)
75 - 90
?
* 0.015
Sources;
1. Personal communications with Stanley Dale and Douglas Shooter,
Arthur D. Little, Inc.
2. Manufacturer's data sheets for methanol.
3. Carr, C., and Riddick, J. A., "Physical Properties of Methanol-
Water Systems," Industrial Engineering Chemistry, 43. pages 692-
696, 1951.
121
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Table C-6
TYPICAL VALUES (RANGES) OF PARAMETERS
SPECIFIED FOR COAL AND COKE
TYPICAL RANGE OF VALUES (MAF BASIS)
la.
Ib.
2.
3.
4.
5.
6.
7.
8.
9.
PARAMETER
Carbon (Total), wt. %
Hydrogen, wt. %
Nitrogen, wt. %
Sulfur, wt. %
Oxygen, wt. %
Chlorine, wt. %
Moisture, wt. %
Volatile Matter, wt. %
Ash, wt. %
Calorific Value, Btu/lb.
(cal/g)
COAL
60. -
2.9 -
0.5 -
0.25 -
2.0 -
< 0.5
1.0 -
3.5 -
5.0 -
8,000 -
(4,440 -
95.
5.6
2.1
5.0
35.0
50.0
60.
20.0
16,000
8,880)
COKE
90 -
1 -
NA
0 -
NA
Trace
0.5 -
0.5 -
0.5 -
12,000 -
(6,660 -
95 a
2 a
10
5.0
6.0
20
16,000
8,880)
NA - Not Available
a. Rough estimate only.
Sources:
1. Steam, Its Generation and Use, The Babcock and Wilcox Company, New
York, New York, 1963.
2. Kirk-Othmer, Encyclopedia of Chemical Technology, Second Edition,
Volume 5, 1967, page 627.
3. Mezey, E. J., Singh, S., and Hissong, D. W., "Fuel Contaminants:
Volume 1 - Chemistry," EPA-600/2-76-177a, July, 1976.
122
-------
Table C-7
TYPICAL VALUES (RANGES) OF PARAMETERS SPECIFIED FOR
REFUSE-DERIVED SOLID FUELS (RDSF)
(Values applicable to municipal RDSF)
PARAMETER
la. Carbon (Total), wt. %
Ib. Hydrogen, wt. %
2. Nitrogen, wt. %
3. Sulfur, wt. %
4. Oxygen, wt, %
5. Chlorine, wt, %
6. Moisture, wt. %
7.
8.
9.
Volatile Matter, wt.
Ash, wt. %
Ash Fusibility, C°
Initial deformation
Softening (H = W)
Softening (H = 1/2W)
Fluid
TYPICAL RANGE OF VALUES
(DRY BASIS)a
35 - 50
5-7
0.3 - 1.5
0.1 - 0.7
30 - 40
0.1 - 1.0
1-5 (as fired basis)
for some highly
processed RDSF
25 - 55 (as fired basis)
for RDSF that has
not been dried or
chemically treated
35 - 90
5-35
Reducing
Atmosphere
1030 - 1130
1200 - 1290
1210 - 1310
1320 - 1400
10. Apparent Density, lbs./ft.3 (g/cm3)
11. Sieve Analysis
12. Calorific Value, Btu/lb. (cal/g)
13. Carbonate Carbon
Oxidizing
Atmosphere-
1110 - 1150
1240 - 1300
1250 - 1340
1360 - 1480
10 - 40 (0.24 - 0.56)
(Average particle size may range
from 0.01 cm for highly processed
RDSF up to 2 cm for others.)
4,000 - 8,500 (2,200 - 4,700)
NA
NA- Not Available
a. Sources used are listed on the following page.
b. From Source #4; data are from three samples of St. Louis Refuse, with
magnetic metals removed.
123
-------
Sources for Table C-7;
1. Schultz, J., Sullivan, P. M., and Walker, F. E., "Characterizing Com-
bustible Portions of Urban Refuse for Potential Use as Fuel," U. S.
Department of the Interior, Bureau of Mines Report of Investigations,
RI 8044, 1975.
2. Solid Wastes; Origin, Collection, Processing, and Disposal, C. L. Man-
tell, Editor, John Wiley and Sons, New York, 1975.
3. "Report of Analyses for Union Electric Company," St. Louis Missouri,
by Research 900, Division of Ralston-Purina Company, St. Louis, Mis-
souri. Unpublished data from December, 1973, through June, 1974.
4. Handbook of Solid Waste Disposal, Materials and Energy Recovery,
Pavoni, J. L., Heer, J. E., Jr., and Hagerty, D. S., Van Nostrand
Reinhold Company, New York, 1975.
5. "Power Boilers: The Ultimate Solution for Solid Waste?", Spaite, P.
and Miller, C., Power Engineering, Volume 76 (No. 3), pages 54-55,
March, 1972.
6. "Specifications for Materials Recovered from Municipal Refuse,"
Alter, H. and Reeves, W. R.; Report to the U. S. Environmental Pro-
tection Agency, Cincinnati, Ohio, May, 1975. (EPA-670/2-75-034.)
7. Personal communication from Thomas Lamb, Arthur D. Little, Inc., March,
1977.
124
-------
Table C-8
TYPICAL VALUES (RANGES) OF PARAMETERS SPECIFIED FOR PEAT
TYPICAL RANGE OF VALUES
PARAMETER (DRY BASIS)
la. Carbon (Total), wt. % 45-60
Ib. Hydrogen, wt% 3.5 - 6.8
2. Nitrogen, wt. % 0.75 - 3.0
3. Sulfur, wt. % ^0.3
4. Oxygen, wt. % 20-40
5. Chlorine, wt. % £ 0.1
6. Moisture, wt. % 70-90 (as found)
30 - 50 (air dried)
7. Organic Matter, wt. % 45-75
8. Ash, wt. % -v 10
9. Ash Fusibility NA
10. Apparent Density NA
11. Sieve Analysis NA
12. Calorific Value, Btu/lb. (cal/g) 7,500 - 9,600 (4,200 - 5,300)
13. Carbonate Carbon NA
NA - Not Available
Sources;
1. Kirk-Othmer, Encyclopedia of Chemical Technology, Second Edition,
1967. (See article on "Coal," Volume 5, page 627.)
2. Van Nostrand's Scientific Encyclopedia, Fifth Edition, 1976,
Douglas M. Considine, Editor, Van Nostrand Rinehold Company.
3. Analyses of peat by Arthur D. Little, Inc. See Appendix D.
125
-------
APPENDIX D
RESULTS OF FUEL ANALYSIS TESTS
127
-------
TABLE OF CONTENTS
Page
1. Introduction
2. Analyses Conducted
3. Description of Fuels 132
A. No. 4 Fuel Oil !32
B. Coal Liquids 132
C. Shale Fuel Oil 132
D. Waste Lubricating Oil 132
E. Milled Peat 133
F. Processed Municipal Refuse 133
4. Discussion of Results 133
5. Results for N, S, Cl, Ash, Heat of Combustion,
Moisture, and Organic Matter 134
LIST OF TABLES
Page
Table D-l - ASTM Methods Suggested by Contractor
to be Used for Indicated Analyses 135
Table D-2 - Analyses of Coal Liquid 136
Table D-3 - Analyses of Shale Fuel Oil 137
Table D-4 - Analyses of No. 4 Fuel Oil 138
Table D-5 - Analyses of Waste Lubricating Oil 139
Table D-6 - Analyses of Processed Municipal Refuse 140
Table D-7 - Analyses of Milled Peat 142
129
-------
1. INTRODUCTION
The Contractor (Arthur D. Little, Inc.), in conjunction with four analyti-
cal service laboratories, undertook a number of fuel analyses - primarily
on uncommon fuel materials - for a variety of reasons. It was expected
that the analyses conducted on the uncommon fuels would, if successful,
lend some support to a statement of applicability for the method chosen
and used, and it was expected that a comparison of the inter- and intra-
laboratory precision would yield some insight - if not valid data - on
the precision of the method, as applied to the fuel in question. Finally,
the results of the analyses were of general interest (1) to confirm liter-
ature data on the range of values to be expected, or (2) to give values
not obtained from the literature.
2. ANALYSES CONDUCTED
Samples of shale oil, coal liquid, No. 4 fuel oil, waste lubricating oil,
processed municipal refuse, and peat were sent to three laboratories who
were asked to analyze - in duplicate - for sulfur, nitrogen, chlorine,
ash, heat of combustion, and (for the two solid fuels) moisture and or-
ganic matter. The methods specified are shown in Table D-l. Some vari-
ability of the methods used for the nitrogen and sulfur analyses had to
be accepted because one or more of the laboratories did not perform
the specified methods. The methods in Table D-l were selected very
early in the course of this project in order to allow sufficient time for
completion of the analyses and, in some cases, are not the preferred
method given in this report.
131
-------
The analyses were conducted in the period between March 1977, and May
1977.
3. DESCRIPTION OF FUELS
A. No. 4 Fuel Oil
A sample of this commercial grade oil was obtained from the Contractor's
facilities on March 16, 1977, at a point just prior to the inlet to a
boiler. The tanks in which the fuel was stored.had been recently cleaned.
B. Coal Liquids.
A sample of coal liquid (7.0% hydrogen) was obtained from a commercial
source. The material is derived from a solvent-refined coal process.
This is an extractive process in which a petroleum-based donor liquid is
placed in contact with coal under hydrogen pressure resulting in an ex-
tracted coal oil.
C. Shale Fuel Oil
A sample of a shale oil distillate was obtained from a private source. The
grade of the 'distillate was intended to be suitable for use as a turbine
fuel for aircraft. The shale fuel oil was produced in a special run and
•should not be considered typical of all shale oil distillate.
D. Waste Lubricating Oil
A sample of waste lubricating oil (from automobile crank cases) was ob-
tained from a service garage in Cambridge, Massachusetts, on March 8, 1977.
132
-------
E. Milled Peat
A sample of garden-grade peat was obtained from a commercial source in
March, 1977. The peat container specified the contents to be "pure"
Canadian Sphagnum Peat Moss. Because of the excessively fibrous and in-
homogeneous nature of the peat, it was milled (in a ball mill) prior to
shipment to the analytical laboratories.
F. Processed Municipal Refuse
A sample of processed municipal refuse was obtained from a private source
on March 7, 1977. The material is produced by subjecting raw municipal
refuse to the following series of operations: size reduction, magnetic
separation, screening, chemical treatment, milling, and, final screening.
This is a more highly processed fuel than is prepared at many locations
and may, therefore, not be representative of refuse-derived solid fuels.
4. DISCUSSION OF RESULTS
The results of the analyses are given in the following section. The
results from two laboratories agreed, in most cases, within the reproduci-
bility limits for the method. These two laboratories also had generally
good precision on the duplicate analyses carried out for each parameter.
Laboratory #3 was "off" in some data, did not carry out many of the required
solid fuel analyses, and did not perform duplicate analyses. The problems
associated with this laboratory, though significant, could not be corrected
within the timeframe of this study; their results are included here, in
part, to demonstrate the variability of results that may be obtained from
different laboratories.
Significant discrepancies can be seen in the results for peat and, to a
much lesser extent, for the processed municipal refuse. It is thought
that differences in drying techniques (leading, possibly, to insufficient
drying) may be the root cause of the differences in the peat analyses by
133
-------
laboratories #1 and #2. The outer (cardboard) peat container was received
by laboratory #2 in a damaged condition, though the inner plastic bag con-
taining the sample was not broken. Still, some loss of moisture may have
occurred in shipping. These results clearly indicate the importance of
sealed sample containers where moisture determinations are required, and
the importance of thorough drying for samples containing significant amounts
of water (e.g., peat, refuse-derived solid fuels, crude shale oils, etc.).
5. RESULTS FOR N, S. Cl. ASH, HEAT OF COMBUSTION
MOISTURE. AND ORGANIC MATTER
The results for N, S, Cl, ash, heat of combustion, moisture, and organic
matter for the six fuels are given in Tables D-2 through D-7.
134
-------
Table D-l
u>
Ul
ASTM METHODS SUGGESTED BY CONTRACTOR TO BE USED FOR INDICATED ANALYSES
SAMPLE NITROGEN
Liquid Coal D 3228-73
Shale Oil D 3228-73
No. 4 D 3228-73
Fuel Oil
Waste Lubri- D 3228-73
eating Oil
Processed D 2973-71
Municipal
Waste
Peat D 2973-71
SULFUR CHLORINE
D 1266-70 D 808-63
with 10:1
dilution
with sul-
fur free
solvent
D 1266-60 D 808-63
with 10:1
dilution
with sul-
fur free
solvent
D 1552-64 D 808-63
D 1552-64 D 808-63
D 3177-73 D 2361-66
Bombwashing
Method
D 3177-73 D 2361-66
Bombwashing
Method
ASH MOISTURE
D 482-74
and
D 874-72
D 482-74
or
D 874-72
D 482-74
and
D 874-72
D 482-74
and
D 874-72
D 2974-71 D 2974-71'
(Method II)
D 2974-71 D 2974-71
(Method II)
HEAT OF
ORGANIC COMBUSTION
MATTER (BTU)
D 240-76
D 240-76
D 240-76
D 240-76
D 2974-71 D 2015-66
or
D 3286-73
D 2974-71 D 2015-66
or
D 3286-73
-------
Table D-2
ANALYSES OF COAL LIQUID
r AJ\AL1£j J. UJX.
(METHOD USED)
Nitrogen, wt. %
(D 3228-73)
LAO
NUMBER
1
2
3
DUPLICATES
0.85, 0.82,
0.81, 0.83
0.31
AVERAGE
0.84
0.82
(0.31)
NOTES
Sulfur, wt. %
(D 1552-64)
Chlorine, wt.
(D 808-63)
Ash, wt. %
(D 482-74, dry)
Ash, wt. %
(D 874-72,
sulfated)
Heat of Combustion,
Btu/lb (D 240-76)
Average
2
3
Average
2
3
Average
1
2
3
Average
0.83
1
2
3
Average
1
2
3
Average
0.60, 0.54
0.50, 0.51
0.53
0.01, 0.04
< 0.1, < 0.1
"trace"
0.57
0.51
0.53
0.54
0.03
< 0.1
—
—
< .001,
< .001
< .01, < .01
0.003
< .001,
< .001
< .01, < .01
NA
16,914; 16,926
16,920; 16,882
20,895
< .001
< .01
0.003
< .001
< .01
16,920
16,901
(20,895)
16,910
Lab #3 used Perkin-
Elmer 240
Average excludes
results from Lab #3
Average excludes
results from Lab
#3
136
-------
Table D-3
ANALYSES OF SHALE FUEL OIL
PARAMETER
(METHOD USED)
Nitrogen, wt. %
(D 3228-73)
"AS-RECEIVED" BASIS
Sulfur, wt. !
(D 1552-64)
Chlorine, wt. %
(D 808-63
Ash, wt. %
(D 482-74, dry)
Ash, wt. %
(D 874-72
sulfated)
Heat of Combustion,
Btu/lb (D 240-76)
NUMBER
1
2
3
Average
2
3
Average
2
3
Average
1
2
3
Average
DUPLICATES
0.29, 0.27
0.25, 0.25
0.52
AVERAGE
0.28
0.25
(0.52)
0.26
1
2
3
Average
1
2
3
Average
0.54, 0.53
0.47, 0.48
0.54
0.05, 0.04
< 0.1, < 0.1
"none"
0.54
0.48
0.54
0.52
0.05
< 0.1
—
—
< .001,
< .001
< .01, < .01
0.001
< .005,
< .002
< .01, < .01
NA
19,323; 19,292
19,298; 19,315
19,269
< .001
< .01
0.001
< .004
< .01
19,308
19,307
19,269
19,295
NOTES
Lab #3 used Perkin-
Elmer 240
Average excludes
results from Lab #3
137
-------
Table D-4
PARAMETER
(METHOD USED)
Nitrogen, wt. %
(D 3228-73)
Sulfur, wt. %
(D 1552-64)
Chlorine, wt. %
(D 808-63)
Ash, wt. %
(D 482-74, dry)
Ash, wt. %
(D 874-72,
sulfated)
Heat of Combustion,
Btu/lb (D 240-76)
ANALYSES
LAB
NUMBER
1
2
3
Average
1
2
3
Average
1
2
3
Average
1
2
3
Average
1
2
3
Average
1
2
3
Average
OF NO. 4 FUEL
"AS-RECEIVED"
DUPLICATES
"none detected"
0.12, 0.12
0.10
0.42, 0.45
0.43, 0.45
0.44
0.00, 0.04
< 0.1, < 0.1
"trace"
< .001,
< .001
0.02, 0.02
0.01
< .001
< .001
0.02, 0.03
NA
19,162; 19,165
19,233; 19,207
19,197
OIL
BASIS
AVERAGE
0.12
0.10
0.11
0.44
0.44
0.44
0.44
0.02
< 0.1
—
—
< .001
0.02
0.01
* 0.01
< .001
0.03
—
—
19,164
19,220
19,197
19,194
NOTES
Lab #3 used Perkin-
Elmer 240
138
-------
Table D-5
ANALYSES OF WASTE LUBRICATING OIL
PARAMETER
(METHOD USED)
Nitrogen, wt. %
(D 3228-73)
Sulfur, wt. %
(D 1552-64)
Chlorine, wt.
(D 808-63)
Ash, wt. %
(D 482-74, dry)
Ash, wt. %
(D 874-72,
sulfated)
Heat of Combustion,
Btu/lb (D 240-76)
LAB
NUMBER
1
2
3
Average
"AS-RECEIVED" BASIS
DUPLICATES AVERAGE
"none detected"
0.06, 0.06
0.28
0.06
0.28
1
2
3
Average
1
2
3
Average
1
2
3
Average
1
2
3
Average
1
2
3
Average
0.41, 0.38
0.37, 0.36
0.38
0.19, 0.20
0.23, 0.22
0.22
1.35, 1.34
1.35, 1.33
1.27
1.24, 1.49
1.60, 1.51
NA
18,917; 18,963
19,077; 19,052
18,911
0.40
0.37
0.38
0.38
0.20
0.23
0.22
0.22
1.35
1.34
1.27
1.32
1.37
1.56
—
1.47
18,940
19,065
18,911
18,972
NOTES
Lab #3 used Perkin-
Elmer 240
139
-------
Table D-6
ANALYSES OF PROCESSED
PARAMETER
(METHOD USED")
Nitrogen, wt. %
(D 3179-73)
(D 2973-71)
(D 2973-71)
Sulfur, wt. %
(D 3177-73,
Bombwashing)
Sulfur, wt. %
(D 3177-73,
Eschka Fusion)
Chlorine, wt %
(D 2361-66)
Ash, wt. %
(D 2974-71)
Moisture, wt. %
(D 2974-71,
Method II)
T All
')" ft
NUMBER
1
2
3
Average
1
2
3
Average
1
2
3
Average
1
2
3
Average
1
2
3
Average
1
2
3
Average
"AS-RECEIVED"
DUPLICATES
0.40, 0.42
< 0.01
0.60, 0.51
NA
0.60, 0.55
NA
NA
0.48, 0.48
NA
14.02, 14.04
13.98
2.89, 2.90
3.39. 3.42
NA
BASIS
AVERAGE
0.41
—
•— —
—
0.56
—
—
—
0.58
—
—
— —
0.48
—
—
—
14.03
—
—
—
2.90
3.41
—
3.2
MUNICIPAL REFUSE
"DRY" BASIS
DUPLICATES AVERAGE
0.43, 0.41 0.42
0.34, 0.34 0.34
__
0.38
0.62, 0.53 0.58
0.58, 0.55 0.57
—
0.58
0.62, 0.57 0.60
NA
—
—
0.49, 0.49 0.49
0.22, 0.25 0.24
—
—
14.44, 14.46 14.45
14.0, 13.9 14.0
—
14.2
—
—
—
—
NOTES
Lab #3 used Perkin-
Elmer 240
Mr dried moisture
0.00%
-------
Table D-6
ANALYSES OF PROCESSED MUNICIPAL REFUSE (continued)
PARAMETER
(METHOD USED)
Organic Matter, wt. /
(D 2974-71)
Heat of Cumbustion,
Btu/lb (D 2015-66)
LAB
NUMBER
I 1
2
3
Average
1
2
3
Average
"AS-RECEIVED" BASIS "DRY" BASIS
DUPLICATES AVERAGE DUPLICATES AVERAGE NOTES
83.08, 83.06 83.07
82.6, 82.7 82.7
NA
82.9
8,149; 8,098 8,124 8,393; 8,340 8,367
8,365; 8,344 8,355
NA
8,361
NA - Analysis not done
-------
Table D-7
PARAMETER
(METHOD USED)
Nitrogen, wt. %
(D 3179-73)
(D 2973-71)
(D 2973-71)
Sulfur, wt. %
(D 3177-73,
Bomb wash ing)
Sulfur, wt. %
(D 3177-73,
Eschka Fusion)
Chlorine, wt. %
(D 2361-66)
Ash, wt. %
(D 2974-71)
Moisture, wt. %
(D 2974-71,
LAB
NUMBER
1
2
3
Average
1
2
3
Average
1
2
3
Average
1
2
3
Average
1
2
3
Average
1
2
3
Average
ANALYSES
"AS-RECEIVED"
DUPLICATES
0.56, 0.55
0.05
0.10, 0.08
NA
0.06, 0.08
NA
0.02, 0.02
NA
2.76, 2.51
2.72
53.15, 53.03
(12.7, 12.6)*
NA
OF MILLED
BASIS
AVERAGE
0.56
—
—
—
0.09
—
—
—
0.07
—
—
— —
0.02
—
—
—
2.64
—
2.72
2.68
53.09
(12.7)
—
—
PEAT
"DRY" BASIS
DUPLICATES AVERAGE NOTES
2.05, 2.00 2.03
0.92, 0.92 0.92
Lab #3 used Perkin-
Elmer 240
1.5
0.36, 0.30 0.33
0.32, 0.27 0.30
—
0.32
0.23, 0.28 0.26
NA
—
— —
0.09, 0.09 0.09
< 0.1, <0.1 < 0.1
—
—
10.10, 9.21 9.66
5.12, 5.68 5.40
—
7.5
— Air dried moisture =
41.8% (Lab #1)
—
—
—
All notes on following page.
-------
CO
Table D-7
ANALYSIS OF MILLED PEAT (continued)
rAJCUinCilJiR.
(METHOD USED)
Organic Matter, wt.
(D 2974-71)
Heat of Combustion,
Btu/lb (D 2015-66)
jjlVU
NUMBER DUPLICATES AVERAGE DUPLICATES AVERAGE NOTES
% 1 44.15, 44.40 44.28
2 82.2, 81.8 82.0
3 NA
Average — —
1 3,837; 3,939 3,888 14,055; 14,428 14,242
2 — 8,052; 8,083 8,068
3 NA
Average — —
NA - Analyses not done
*Sample possibly air dried before analysis due to tear in container during shipment to lab.
-------
TECHNICAL REPORT DATA
(Please read Instructions on the reverse before completing)
1. REPORT NO.
EPA-600/7-77-143
2.
3. RECIPIENT'S ACCESSION NO.
4. TITLE AND SUBTITLE
Technical Manual for the Analysis of Fuels
5. REPORT DATE
December 1977
6. PERFORMING ORGANIZATION CODE
7. AUTHOR(S)
L.N.Davidson, W.J.Lyman, D.Shooter, and
J.R.Valentine
8. PERFORMING ORGANIZATION REPORT NO.
9. PERFORMING ORGANIZATION NAME AND ADDRESS
Arthur D. Little, Inc.
Acorn Park
Cambridge, Massachusetts 02140
10. PROGRAM ELEMENT NO.
EHB529
11. CONTRACT/GRANT NO.
68-02-2150, T.D. 20602
12. SPONSORING AGENCY NAME AND ADDRESS
EPA, Office of Research and Development
Industrial Environmental Research Laboratory
Research Triangle Park, NC 27711
13. TYPE OF REPORT AND PERIOD COVERED
Final: 12/76-12/77
14. SPONSORING AGENCY CODE
EPA/600/13
is. SUPPLEMENTARY NOTES IERL-RTP project officer is Larry D. Johnson, Mail Drop 62,
919/541-2557.
16. ABSTRACT
manua^ jg for ^QQ QQ a guide in research projects concerned with fuel
combustion. Basically, it describes and discusses standard methods of sampling and
analysis for a variety of hydrocarbon fuels. The analyses covered are those of prime
concern to the combustion engineer; no attempt is. made to cover all analyses that may
be required in a complete environmental assessment of any fuel combustion process.
For each fuel covered, the manual indicates the analyses that are likely to be required
the preferred method of analysis , and available sampling procedures. For each me-
thod of analysis listed (preferred plus alternates, in many cases), the manual sum-
marizes the method, discusses its applicability, and describes its precision. The
manual covers gaseous fuels, liquid petroleum fuels, waste lubricating oil, shale oil,
coal liquids, methyl fuel, coal, coke, refuse -derived solid fuels, and peat. The
appendices give: the availability of Standard Reference Materials for fuel-related
analyses; laboratory directories; typical values (or ranges) of parameters specified
for each fuel; and results of fuel analyses conducted by the contractor.
17.
KEY WORDS AND DOCUMENT ANALYSIS
DESCRIPTORS
b.lDENTIFIERS/OPEN ENDED TERMS
COS AT I Field/Group
Pollution
Hydrocarbons
Fuels
Combustion
Analyzing
Sampling
Coke. Coal
Methodology
Petroleum Products
Fuel Oil
Shale Oil
Wastes
Carbinols
Refuse
Pollution Control
Stationary Sources
Gaseous Fuels
Waste Lubricating Oil
Refuse-Derived Solid
Fuel
13B
07C
21D
21B
14B
11G
11H
08G
18. DISTRIBUTION STATEMENT
Unlimited
19. SECURITY CLASS (This Report/
Unclassified
21. NO. OF PAGES
143
20. SECURITY CLASS (Thispage)
Unclassified
22. PRICE
EPA Form 2220-1 (9-73)
144
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