EPA-650/2-74-025
April 1974
Environmental Protection Technology Series
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EPA-650/2-74-025
APPLICABILITY OF THE MEYERS
PROCESS FOR CHEMICAL
DESULFURIZATION OF COAL:
INITIAL SURVEY OF FIFTEEN COALS
by
J. W. Hamersma, M. L. Kraft,
C. A. Flegal, A. A. Lee, and R. A. Meyers
Systems Group of TRW, Inc.
One Space Park
Redondo Beach, California 90278
Contract No. 68-02-0647
ROAP No. 21AFJ-32
Program Element No. 1AB013
EPA Project Officer: L. Lorenzi, Jr.
Control Systems Laboratory
National Environmental Research Center
Research Triangle Park, North Carolina 27711
Prepared for
OFFICE OF RESEARCH AND DEVELOPMENT
U.S. ENVIRONMENTAL PROTECTION AGENCY
WASHINGTON, D.C. 20460
April 1974
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This report has been reviewed by the Environmental Protection Agency
and approved for publication. Approval does not signify that the
contents necessarily reflect the views and policies of the Agency,
nor does mention of trade names or commercial products constitute
endorsement or recommendation for use.
11
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ABSTRACT
Run-of-the-mine coal samples were collected from each of 15 US mines
located in 11 states from New Mexico and Montana to West Virginia and
Pennsylvania. Each coal was treated separately by the Meyers Process
(ferric sulfate extraction) and float-sink fractionation (physical
cleaning). The Meyers Process removed 83-99% of the pyritic sulfur
(40-64% of the total sulfur) from all of the coals which contained
sufficient pyritic sulfur for accurate sulfur determination (i.e.,
greater than 0.3% w/w). Four of the coals were reduced to less than
1% total sulfur by the Meyers Process while one of the coals was reduced
to less than 1% total sulfur by physical cleaning (1.90 float material,
14 mesh x 0). With the exception of one mine, the Meyers Process
removed significant to very large increments of sulfur over that
separable by physical cleaning. Significant amounts of As, Be, Cr,
Mn, Hit Se and Zn were removed along with the pyrite by the Meyers
Process.
This report was submitted in fulfillment of Contract 68-02-0647 under
the sponsorship of the Office of Research and Development, Environmental
Protection Agency.
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TABLE OF CONTENTS
Section Page
1.0 CONCLUSIONS 1
2.0 RECOMMENDATIONS 3
3.0 INTRODUCTION 4
4.0 PROGRAM RESULTS 9
4.1 Summary 9
4.2 Selection, Sampling and Preparation of Coals 13
4.2.1 Selection of Coals 13
4.2.1.1 Rationale 13
4.2.1.2 Coal Sample Selection 17
4.2.2 Sampling of Coals 24
4.2.3 Coal and Sample Preparation at TRW 28
4.3 Chemical Removal of Pyritic Sulfur 30
4.3.1 Experimental Method ' 30
4.3.1.1 Extraction Procedure 31
4.3.1.2 Sulfur Forms Analysis 32
4.3.2 Pyritic Sulfur Removal Results 35
4.3.3 Heat Content Changes and Ferric Ion Consumption. . 38
4.3.4 Removal of Residual Sulfate 40
4.3.5 Ash Changes 45
4.3.6 Organic Sulfur Changes 45
4.3.7 Miscellaneous Data 50
4.4 Float-Sink Testing 53
4.4.1 Procedures 53
4.4.2 Results and Discussions 53
4.5 Organic Sulfur Extraction Experimentation 57
4.5:1 Baseline Conditions 57
4.5.2 Experimental Procedure ' 58
4.5.3 Organic Sulfur Extraction Results 58
4.6 Trace Elements in Coal 63
4.6.1 Coal Composition 63
4.6.2 Methods for Trace Element Analysis 65
4.6.3 Discussion of Trace Element Analysis Results ... 69
IV
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TABLE OF CONTENTS - Continued
Section Page
5.0 ACKNOWLEDGEMENTS 75
6.0 REFERENCES 76
7.0 GLOSSARY OF ABBREVIATIONS AND SYMBOLS 77
8.0 UNIT CONVERSION TABLE 79
9.0 APPENDICES 80
Table of Contents 81
Figures 82
Tables 83
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TABLES
Page
1. Summary of Pyrite Removal Results 10
2. Coal Selection 14
3. Coal Analysis Summary 15
4. Average Sulfur Content of U.S. Coal 17
5. Average Sulfur Content of Coals by State 17
6. Sieve Analysis of Coals Ground to 100 Mesh x 0 29
7. Sulfur Forms Analyses - ASTM Standards for Duplicate Analyses. 34
8. Summary of Pyritic Sulfur Removal Data 36
9. Summary of Heat Content Changes and Excess Ferric Ion
Consumption ... 39
10. Sulfate Retention as a Function of Wash Procedure and Reaction
Conditions. . 41
11. Special Sulfate Removal Experiments - Camp Nos.l&2 Coal. ... 42
12. Special Sulfate Removal Experiments - Orient No.6 Coal .... 43
13. Summary of Ash Changes 46
14. Summary of Organic Sulfur Data 48
15. Miscellaneous Data 51
16. Summary of Float-Sink Tests, 14 Mesh x 0 Coal, Comparison
to Meyers Process. . . 54
17. Extraction of Organic Sulfur - Dry Basis Sulfur Forms Analysis 59
18. Extraction of Organic Sulfur - Dry Basis Proximate Analysis. . 60
19. Organic Sulfur Removal Calculations 62
20. Reported Trace Elements Distribution in Two Coals. ....... 64
21. Trace Analysis Sensitivities 66
22. Trace Element Retention 68
23. Trace Element Composition of Untreated Coals 71
24. Pooled Standard Deviations 72
25. Trace Element Removal 74
VI
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FIGURES
Page
1. Pyritic Sulfur Removal Process Chemistry 4
2. Sulfur Product from Pyrite Removal Process 5
3. Percentage Distribution of Cumulative Coal Production of the
United States to 1 January, 1967. . 16
4. Coal Fields of the Conterminous United States 16
5. Coal Resources of the United States 18
6. U.S. Bureau of Mines Sampling, Handling System 25
7. Sulfur Forms Analysis Scheme 33
vii
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1.0 CONCLUSIONS
1. Only one of the fifteen run-of-mine (ROM) coals investigated in
this survey met the Clean Air Act sulfur oxide emission standard of 0.6 Ibs*
of sulfur/106 btu for new stationary combusion sources.
2. The process for chemical removal of pyritic sulfur from coal
(Meyers Process) was demonstrated to be capable of removing:
a) 89 to 95% of the pyritic sulfur (44 to 59% of the total .
sulfur) from the six Appalachian Basin coals experimentally
investigated in the survey program. An additional coal -
from the Walker Mine - contained insufficient pyritic sulfur,
0.07% w/w, for measurable evaluation in this program.
b) 96 to 99% of the pyritic sulfur (44 to 57% of the total
sulfur) from the three Eastern Interior Basin coals investi-
gated.
c) 98% of the pyritic sulfur (64% of the total sulfur) from
the single Western Interior Basin coal investigated.
d) 57 to 82% of the pyritic sulfur from the four Western coals
investigated. Of these four samples only coal from the
Colstrip Mine contained sufficient pyritic sulfur, 0.34%,
of which 82% was removed, to give reasonatily accurate results.
e) significant amounts of As, Be, Cr, Mn, Ni, Se and Zn.
3. Seven potentially hazardous trace elements - Ag, Be, Cd, Hg, Sb,
Sn and Se - were generally present in the coals studied in amounts that
may be of minimal environmental significance (<3 ppm) from coal combustion
facilities. .
4. The Meyers Process reduced the total sulfur content of four
coals under investigation to below 1.0% (three of these were reduced to
0.7% or less).
*EPA policy is to express all data in Agency Documents in metric
units. Because implementing this practice will result in undue cost,
NERC/RTP is providing conversion factors for the particular non-metric
units used in this document. These factors are located on page 79.
1
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5. Most coals showed an increase in heat content after Meyers Process
treatment. For the Appalachian and some of the Eastern Interior Basin coals,
this heat content rise amounted to 6-9% of the initial heating value. When
calculated on a dry mineral matter free basis,a heat content loss of 2.8-8.3%
was found for Western coals, a heat content change of +.4 to -5.1% was
found for Interior Basin coals, and a heat content change of +2.6 to -4.6%
was found for Appalachian coals.
6. Ash removal, in addition to that accounted for by the pyrite
decrease, was observed in varying degrees for all coals.
7. Sulfate retention on some of the treated coal samples required
additional washing to reduce the sulfate levels to values equal to or
lower than the starting sulfate contents.
8. Float-sink testing showed that conventional coal cleaning could
reduce only one of the coals tested to a sulfur content value as low as
that obtainable by the Meyers Process (Jane Mine - but with 15% btu loss).
9. The extraction of seven coals was studied with p-cresol, with
the results showing no significant organic sulfur removal.
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2.0 RECOMMENDATIONS
1. The Meyers Process should continue to be tested on additional
coals from all parts of the U.S. in order to further define the applicability
of the process for meeting legislated sulfur oxide pollution control standards,
2. Future studies should include removal of pyritic sulfur from various
coal size and density fractions typical of the output of coal preparation units
for the purpose of establishing optimum combinations of the Meyers Process
with current coal handling and treatment practice.
3. Process parameters necessary to effect optimum residual elemental
sulfur and sulfate removal as well as the fate of major acid soluble ash
constituents such as calcium, magnesium and non-pyritic iron should be
studied.
4. Near-term emphasis should be placed on Eastern coal since the process
applicability as defined by the first coals extracted appears to be greatest
for this region of the country, and since 60% of current coal production in
the U.S. is mined in this region.
5. Further studies on the utilization of p-cresol to selectively leach
organic sulfur from U.S. coals should not be performed.
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3.0 INTRODUCTION
The Meyers Process is a new and economically attractive method for
the desulfurization of coal for control of sulfur oxide emissions from
stationary combustion sources. The process utilizes a regenerable
aqueous ferric sulfate leaching unit to chemically convert and remove the
pyritic sulfur content of coal as elemental sulfur and iron' sulfate. In
addition, the ash content of the coal is decreased by 10 to 40% and the
heat content per unit weight increased by as much as 8%. The process
chemistry for both leaching and regeneration is outlined in Figure 1.
CRUSHED COAL IS TREATED WITH FERRIC SULFATE SOLUTION
FeS + 4.6 Fe(S0) + 4.8HO -10.2 FeSO + 4.8 H
0.8S
GENERATED SULFUR IS REMOVED BY VAPORIZATION OR SOLVENT EXTRACTION
FERRIC SULFATE SOLUTION IS REGENERATED WITH OXYGEN AND EXCESS
FERRIC AND FERROUS SULFATES ARE REMOVED
9.6 FeSO
2.4
IRON
SULFATES
4.8
RECYCLE
SOLUTION
Figure 1. Pyritic Sulfur Removal Process Chemistry
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The detailed chemistry, reaction kinetics, and engineering and
economic viability of the process were established under an Environmental
Protection Agency sponsored bench-scale program (Contract No. EHSD 71-7)
for evaluation of the Meyers Process (1). Because of the success of the
bench-scale program and the national need for sulfur oxide control technol-
ogy, the process is now in a pilot plant design phase.
Other major methods which offer promise for the control of sulfur
oxides from coal burning stationary sources include: flue gas scrubbing,
coal liquefaction and physical cleaning. These alternative methods are
compared to the Meyers process in the following discussions.
Chemical desulfurization has some inherent advantages over flue gas
scrubbing for sulfur oxide control in that, a) application of this process
requires no major modification of existing or new power plant facilities
or of power plant operation, b) sulfur is removed from coal directly as
elemental sulfur (Figure 2) and iron sulfate, and in relatively small
Figure 2. Sulfur Product from Pyrite Removal Process (IX)
amounts (e.g., approximately 200,000 tons/yr for reducing 3.2 x 106 tons/yr
of a 4% sulfur coal to 0.8% sulfur vs 1,000,000 tons/yr of a gypsum sludge
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throwaway material for comparable sulfur oxide removal using non-regener-
able limestone scrubbing). This second advantage does not apply, of
course, when comparing the Meyers Process to the regenerable flue gas
scrubbing processes now under investigation. The iron sulfates from the
Meyers Process may be converted to an insoluble basic iron sul fate form
by calcining, may be used to start up additional process plants, or may
possibly be sold as a chemical product in some locations.
This process has advantages over coal liquefaction in that (a) oper-
ation under conditions of 100°C to 130°C, ambient to 100 psig is possible,
while coal liquefaction requires temperatures of 400-500°C and pressures
in excess of 1,000 psi; (b) a thermal efficiency of greater than 90% is
obtained compared with a thermal efficiency for coal liquefaction of
approximately 70-80% (this is an important factor in the conservation of
the overall U. S. energy base); and (c) only air or oxygen is required
as a consumable chemical, while liquefaction requires at least 1 to 2%
by weight hydrogen or synthesis gas and for catalytic liquefaction a
significant amount of catalyst is found to be unrecoverable. However,
coal liquefaction is capable of reducing a broader range of coals to
meet the Clean Air Act standards.
The Meyers Process has advantages over physical cleaning (or separa-
tion by physical methods of coal into rock rich and rock lean portions)
in that (a) large quantities of waste products are not generated (e.g.,
for typical physical cleaning of coal, which is basically practiced to
remove non-combustible rock, 5-10% of the carbon content of the coal is
discarded along with the rock rich fraction giving rise to a secondary
pollution problem of acid drainage from tailings, while for deep cleaning
of coal, whose purpose would be to remove a large quantity of the pyritic
sulfur, up to 30% or 40% by weight of the coal may be discarded giving
rise not only to an acid drainage problem but to physical and combustion
hazards due to the mass of reject; (b) pollutants are converted into
small amounts of potentially useful chemicals - elemental sulfur and iron
sulfate; and (c) consistent and greater reductions in overall pyritic
sulfur content can be achieved.
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Because of the widespread application of physical cleaning techniques
for removal of non-combustible rock from coal (which includes some pyrite),
this process deserves to be compared directly to the Meyers Process for
applicability in meeting the standards of the Clean Air Act. Indeed, in
actual practice simple coal washing may well be used prior to the Meyers
Process to provide an improved coal product containing both minimum ash
and minimum sulfur and optimum heating value.
Therefore, the present program for a "Survey of the Applicability of
the Meyers Process for Chemical Desulfurization of U. S. Coals" (Contract
No. 68-02-0647) was established to determine the potential of the Meyers
Process to desulfurize United States coals and to establish a comparison
with physical cleaning of coal. Significantly, both processes are amenable
to simple laboratory testing - the Meyers Process through a chemical leach
with ferric sulfate solution as described in Figure 1, and physical clean-
ing through utilization of float-sink testing in dense media. In addition,
it was a further objective of the program to determine the fate during
chemical leaching of 18 minor elements commonly found in domestic coals.
The potential of this process to provide a means to meet Federal
standards of performance for new stationary sources is high. The Appalach-
ian Coal Basin is an illustrative example. This coal region has particular
importance as it provides 60% of current United States coal production,
with 22 billion tons of identified and recoverable reserves, and is also
the major single area of U. S. sulfur oxide air pollution. Presently,
approximately 90% of the coal mined for utility use in the Appalachian
Basin exceeds the sulfur content required to meet the sulfur dioxide
emission standard of no greater than 1.2 Ibs of SO emitted per million
/^
btu's of input energy. However, on the basis of sulfur forms data, appli-
cation of the .chemical removal process can increase the quantity of
Appalachian coal capable of meeting the performance standard by a factor
of four, to nearly 40%, at 95% pyritic sulfur removal (this amount of
removal was achieved for all four coals tested in the previous bench-scale
program and for most coals tested under this applicability study). In
addition, many of the Appalachian coals could meet state standards for
existing sources using the Meyers Process.
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There are 23 major coal mining districts in the United States with
several hundred identifiable coals, all of which vary significantly in
composition, i.e., ash content, carbon content, sulfur content, pyrite
distribution, etc. Thus, in order to establish the applicability of
chemical removal of pyritic sulfur from coal process technology for sul-
fur oxide pollution control in the United States, the amount of sulfur
which may be removed from representatives of the widest possible variety
of coals must be determined. The present survey program evaluated 15
U.S. coals from mines in the Appalachian, Eastern Interior, Western
Interior and Western areas of the United States.
This report of the survey program contains data on over 70 coal
extractions and 180 coal float-sink determinations, necessitating more
than 2500 separate chemical and spectroscopic analyses. Therefore, the
following guide is provided for the readers who wish to focus their at-
tention in a specific area. Program results are presented in five major
areas:
Selection, sampling and preparation of coals
t Chemical removal of pyritic sulfur
Float-sink studies
Organic sulfur extraction
Evaluation of trace element changes
These sections are followed by references, a glossary, and appendices.
Those readers desiring to review the experimental data obtained for removal
of pyritic sulfur from coal are directed to Sections 4.1, 4.3 and 4.4
(pp.9, 30 and 53, respectively), as well as the appendix tables cited in
these sections. Those readers desiring the selection criteria of coals
for the survey are directed to Section 4.2, while those readers interested
in experimental' methods and sample techniques and preparation are direc-
ted to Sections 4.2 and 4.3 (pp.13 and 30, respectively). Float-sink
(washability) studies are reported in Section 4.4 (pp.53). Extraction of
organic sulfur is presented in Section 4.5 (pp.57)> and the trace element
studies are presented in Section 4.6 (pp.63).
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4.0 PROGRAM RESULTS
The program results are presented in the six sections to follow:
Summary, Selection and Sampling, Chemical Removal of Pyritic Sulfur, Float-
Sink Testing, Extraction of Organic Sulfur, and Trace Elements in Coal.
4.1 SUMMARY
The Meyers Process is operable over a wide range of conditions
(e.g.,100°C-130°C, coal top sizes of 1/4" to 200 mesh x 0, pressures from
ambient to 100 psig, and both with and without concurrent regeneration
of leach solution). Detailed discussion of the data obtained utilizing
these variations is presented in the final report for the bench-scale
program (1).
A set of reaction conditions amenable to laboratory testing which
is within the above range of variables was selected for this survey
program. More specifically, testing was conducted at approximately 100°C and
ambient pressure, and the leach solution was ppriodically changed in order to
maintain reasonable reaction rates. Each coal was found to require specific
conditions for maximum pyrite removal and total sulfur content reduction
relative to one or more of the following factors: reaction time, coal
particle size, degree and type of washing for sulfate removal and excess
utilization of ferric ion. More than one reaction trial was often necessary
for identification of the conditions for high removal.
A summary of the best results to date for chemical removal of
pyritic sulfur and the optimum results for conventional coal washing
(float-sink evaluation) are shown in Table 1. The table describes the re-
sults from the coals which contained sufficient pyritic sulfur for
accurate sulfur removal determination (i.e. > 0.3% w/w). Actual total sulfur
values before and after chemical removal are shown in columns 2 and 3.
These may be compared with the column 4 total sulfur values which could be
obtained for full process optimization (at 95% pyrite removal with no
increase in starting sulfate or measured organic sulfur content). Thus for
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example, although 99% pyrite conversion was obtained for the Camp Nos.l&2
mines,the total sulfur was reduced to 2.1%, not the theoretical 1.8%, due
to a slight increase in other sulfur forms.
However, it can be seen that for approximately one-half of the
coals near optimum results have already been obtained (Mines 1, 3, 5,
6, 8 and 9 are reduced to within 0.3% sulfur of optimum results), but
for the remaining mines, additional processing improvements are necessary
to reach near optimum values for total sulfur removal. These improvements
could include higher temperature operation, more efficient sulfate re-
moval, etc. However, in each case the Meyers Process reduced the total
sulfur content of the coals to values lower than that obtainable by con-
ventional coal cleaning (compare columns 3 and 7). In most cases, sub-
stantial differences were found.
Four of the coals treated by the Meyers Process were reduced to
total sulfur values below 1% (Mines 1-4), and Mines 1-3 were reduced to
sulfur levels near the Clean Air Act standard for New Stationary Sources
of .6-.8% sulfur. The total sulfur removed after Meyers Process treat-
ment varied from 40-64% removal with an average of approximately 50%
(column 6) , and pyrite conversions (Column 5) averaged 93% for the
coals shown in the Table. Trace element analyses were performed (for
18 trace elements) in triplicate on the starting coal and on each of three
treated coal samples on eacr. of three treated coal samples for ten of
the coals surveyed. The results showed that arsenic, beryllium, chromium,
lithium, manganese, nickel, lead, selenium and zinc could be substantially
removed from many of the coals during the Meyers Process treatment.
Arsenic, beryllium, manganese, nickel, lead and zinc were particularly
noteworthy as having a high degree of removal for most coals where they
were present 'in measurable quantities.
Studies were also performed on the use of p-cresol extraction
for removal of an organic sulfur rich portion of the coal. This method
had been studied in the bench-scale program (1) and found to show some
promise, but the results were not clear. Extraction of seven of the
11
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fifteen survey coals indicated no measureable partitioning of organic
sulfur by p-cresol.
The results are presented in detail in the following five sections
and in the cited Appendix divisions.
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4.2 SELECTION, SAMPLING AND PREPARATION OF COALS
TRW, in consultation with the Environmental Protection Agency Project
Officer,selected fifteen coal mines which were sampled on the basis of the
following criteria:
(a) widest possible variety of coal beds, coal regions and coal
rank,
(b) high production and reserves,
(c) sulfur content in coal sufficiently high to require control
of sulfur oxide emissions from combustion.
The selected coal mines, the annual production of each mine in 1972, and the
analysis summary of each coal sample are given in Tables 2 and 3. The fol-
lowing sections of this report present the rationale for selection, a dis-
cussion of the coals and mines selected, a description of the sampling of
the coals, and a review of the sample preparation for testing at TRW.
4.2.1 Selection of Coals
4.2.1.1 Rationale
For the original program (EPA Contract EHSD 71-7)^ two coals were
selected from the Appalachian basin and two from the Eastern Interior basin.
In the Appalachian basin the coals were from the Pittsburgh and Lower Kit-
tanning seams while in the Eastern Interior coal basin the coals were from
the No.5 and No.6 seams.
Some of the background information which was utilized to aid in the
selection of the fifteen coals for this study is presented below in three
paragraphs: Previous Production by State, Distribution of Coal Reserves
and Distribution of Sulfur Content.
Previous Production by State - Figure 3 shows the percentage
distribution of the cumulative production of coal in the United
States up to January 1, 1967. In descending order of production,
the six most productive states were: Pennsylvania, West Virginia,
Illinois, Kentucky, Ohio and Indiana. These states have pro-
duced slightly over 84% of the coal consumed to date.
Distribution of Coal Reserves in the United States - the distri-
bution of the coal reserves in the United States is shown by
Figure 4, which gives aereal distribution and Figure 5, which
quantitatively describes the total resources remaining. From an
examination of Figure 5, it is apparent that coal from the fol-
lowing seven states would represent the vast majority of the
remaining resources of bituminous coal in the United States:
Illinois, W.Virginia, Colorado, Pennsylvania, Kentucky, Ohio
and Indiana.
13
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PRODUCTION AND RESERVES
STATES WEST
OF THE
MISSISSIPPI
RIVER
WESTERN INTERIOR BASIN 3.6
ROCKY MOUNTAIN STATES 4.4
WEST COAST AND ALASKA 0.5
ALABAMA 2.7
TENNESSEE 1.1
VIRGINIA 2.6
OTHER STATES 0.9
INDIANA 3.3
Figure 3.
Percentage Distribution of Cumulative Coal
Production of the United States to 1 January 1967
COAL FIELDS OF THE UNITED STATES
Figure 4.
Coal Fields of the Conterminous United States
16
-------
Distribution of Sulfur Content in Coal - Table 4 shows the
general distribution and average sulfur content of U.S. coals,
This distribution shows that the major areas containing high
sulfur coal are east of the Mississippi River.
TABLE 4
AVERAGE SULFUR CONTENT OF U.S. COAL*
Coal Resources Determined
by Mapping and Exploration
Total bituminous coal, subbituminous
coal , and lignite
Bituminous coal east of the
Mississippi River
Low Sulfur
(1.0% or
Less)
65%
20%
Med i urn
Sulfur
(1.1-3.0%) '
15%
37%
High
Sulfur
( +3%)
20%
43%
*Dry basis.
A review of the average sulfur content of the states previously
demonstrated to be of interest from a reserve or production point of view
are listed below in Table 5.
TABLE 5
AVERAGE SULFUR CONTENT OF COALS BY STATE*
State
Colorado
West Virginia
Illinois
Kentucky
Ohio
Indiana
Pennsylvania
%S
0.56
1.40
2.95
2.22
3.52
3.00
1.96
*Dry basis.
4.2.1.2 Coal Sample Selection
APPALACHIAN COALS
Coals sampled, as noted in the following sections, are given in their
descending stratigraphic order in the Monongahela, Conemaugh, and Allegheny
stratigraphic groups, as defined in Pennsylvania and correlated with other
beds of the Appalachian Region.
Sewickley Seam - the Sewickley seam, most recent in geologic age
of the coal beds investigated, is present in Pennsylvania (Greene,
Butler, Clarion, Armstrong, Washington, Feyette, Westmoreland and
Allegheny Counties), West Virginia (Marion, Monongalia, Wetzel,
17
-------
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18
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Marshall and Ohio Counties, where an estimated 2 billion tons
remain), and Ohio, where the Sewickley correlates with the
Meiggs Creek (or No. 9) seam which is found in Monroe, Belmont,
Harrison and Jefferson Counties. The Meiggs Creek seam ranks
third in production in Ohio. This program initiated the exam-
ination of this coal with a sample from the Warwick mine of
the Duquesne Light Company in Greene County, Pennsylvania.
This mine produces 2 million tons of coal per year. State maps
showing the extent of this bed and location of the single
sample taken to date are shown in Appendix A as Figures A-l,
A-2 and A-3.
Pittsburgh Seam - the Pittsburgh bed has been described as the
most valuable individual mineral deposit in the United States.
It is of minable thickness over an area of about 6,000 square
miles in Pennsylvania (Washington, Greene, Indiana, Somerset,
Allegheny, Armstrong, Westmoreland and Fayette Counties where
approximately 7 billion tons remain), West Virginia (parts of
Brooke, Ohio, Marshall, Wetzel, Monongalia, Marion, Doddridge,
Harrison, Taylor, Preston, Mineral, Barbour, Upshur, Lewis,
Gilmer, Braxton, Calhoun, Clay, Roane, Kanawha, Putnam, Mason,
Cabell and Wayne Counties with approximately 10 billion tons
of minable reserves), and eastern Ohio (primarily Belmont,
Harrison, Jefferson, Carroll, Columbiana and Mahoning Counties
which contain some 10 billion tons of reserve). Pittsburgh
coal is also found in the Georgis Creek basin (Garrett and
Allegheny Counties, Maryland) where only about 2 million tons
remain. A Pittsburgh coal from Greene County,.Pennsylvania was
examined in the previous bench-scale program^). This program
expands the coverage of the Pittsburgh bed by sampling coals
from the Egypt Valley No.21 mine of t^ Hanna Coal Co., Division
of Consolidation Coal Co., in Belmont County, Ohio, which pro-
duces five million tons of coal a year from this strip mine,
and the Humphrey No.7 mine, also of the Consolidation Coal Co.,
in Monongalia County, W. Virginia which produces more than
three million tons per year from this deep mine. State maps
showing the counties containing minable Pittsburgh coal and
the locations of the mines sampled to date are shown in Figures
A-4, A-5 and A-6. In this case, where the remaining reserves
are rather clearly defined, the yearly production of the mines
sampled represent approximately one-three thousandths of the
seam reserve.
Lower Freeport Seam - the Lower Freeport seam is also present in Penn-
sylvania, West Virginia, Ohio and Maryland, where it is sometimes
called the No.SA coal. In Pennsylvania it is present in Lawrence,
Beaver, Washington, Greene, Butler, Allegheny, Fayette, West-
moreland, Armstrong, Indiana, Somerset, Cambria, Bedford and
Fulton Counties. In West Virginia, it is minable in parts of
Nicholas, Roane, Braxton, Preston, Ohio, Brooke and Hancock
Counties. Of the original 700 million tons minable in West
Virginia, comparatively little has been removed. In Ohio the
Lower Freeport is present and of importance in Jefferson, Athens,
and Perry Counties where some 3 billion tons remain. In Maryland
19
-------
the Lower Freeport is mined in Garrett and Allegany Counties in
the northwest corner of the state bordering on West Virginia and
Pennsylvania. For this program, a sample was taken from the Jane
Mine of the Rochester and Pittsburgh Coal Co., in Armstrong County,
Pennsylvania, which produces 2 million tons per year from two
deep mines. State maps showing the counties with minable Lower
Freeport coal as well as the location of the mine sampled are
shown in Figures A-7, A-8 and A-9. Since only two counties in
Maryland are of concern, they are not mapped.
Upper Kittanning Seam - the Upper Kittanning coal is strati-
graphically the uppermost of the three Kittanning coals originally
named at Kittanning, Pennsylvania. In Pennsylvania (Lawrence,
Beaver, Washington, Greene, Fayette, Westmoreland, Armstrong,
Clarion, Jefferson, Indiana, Somerset, Cambria and Clearfield
Counties) the seam is thin and thus infrequently deep-mined. In
West Virginia, the coal is of sufficient thickness for mining
in parts of Kanawha, Nicholas, Clay, Braxton, Webster, Upshur,
Lewis, Randoph, Barbour, Harrison, Taylor, Marion, Monongalia and
Preston Counties over an area of some 1400 square miles. The
original reserves in West Virginia were estimated at 4 billion
tons and since this bed has not been a major producer for the
state, the majority of the coal remains.
The Upper Kittanning seam is not a major coal bed in Ohio but geo-
logically it follows the Lower Kittanning in its persistence from
northeast to southwest in the Ohio coal fields. In Maryland, the
Upper Kittanning seam is mined in both Garrett and Allegany
Counties where it forms parts of the 1 billion tons of remaining
coal reserves.
One sample for this program was taken from the Walker Mine of the
Buffalo Coal Co., in Garrett County, Maryland, where two
hundred thousand tons a year are taken by auger and strip mining.
State maps showing the extent of this bed are shown in Figures
A-10, A-ll and A-12. (Maryland, where the sample was taken, is
again not shown because of the two county representations.)
Lower Kittanning - the Lower Kittanning bed is most pervasive
throughout the northern part of the Appalachian basin throughout
portions of Pennsylvania, West Virginia, Ohio and Maryland. In
Pennsylvania (Lawrence, Beaver, Washington, Greene, Fayette,
Westmoreland, Butler, Clarion, Armstrong, Somerset, Indiana,
Jefferson, Clearfield, Cambria, Bedford and Fulton Counties) it
is widely strip mined. In West Virginia the Lower Kittanning
(also called the No.5 Block) is minable in parts of Mingo, Logan,
Boone, Wayne, Lincoln, Kanawha, Nicholas, Fayette, Clay, Roane,
Braxton, Webster, Randolph, Upshur, Lewis, Barbour, Taylor, Marion,
Monongalia, Preston and Mineral Counties. It covers an area
greater than 2600 square miles and is estimated to have originally
contained over 10 billion tons. Though one of the most mined beds
of West Virginia much of this reserve remains. This coal is present
in most of the counties comprising the coal fields of eastern Ohio,
extending from Mahoning County in the northeast through Lawrence
20
-------
and Scioto Counties in the southeast. In Ohio, the estimated
minable reserves total three billion tons. The coal is also
present in the two coal counties of Maryland (unmapped) though
not of major commercial importance.
The previous program examined a Lower Kittanning coal from
Indiana County, Pennsylvania. During the present program, a
sample was also obtained from the Fox mine of the C&K Coal Co.,
in Clarion County, Pennsylvania which produces two million tons
per year from this strip mine. State maps showing the extent
of this bed and the location of the two samples are shown
as Figures A-13, A-14 and A-15.
Mason Seam - to provide an example of an Eastern Kentucky coal,
a sample was taken from the Dixie Fuel Company's No.l mine in
Harlan County, Kentucky which mines three hundred thousand tons
a year from this seam. A state map showing the location of
the sampling point in the Upper Cumberland reserve district is
shown in Figure A-16.
21
-------
EASTERN INTERIOR REGION
No.5 Bed (Seam) - the No.5 Bed is the most widespread and com-
mercially valuable coal bed in the Eastern Interior coal basin.
It is known in Illinois as the No.5, Harrisburg or Springfield
beds; in Indiana as the Springfield or No.V bed;and in western
Kentucky as the No.9 bed. It is of minable thickness over an
area of about 20,000 square miles in the three states and it is
recognizable as a lithologic unit over an area of about 30,000
square miles. In southeastern Illinois, it is 4-5 feet thick
over large areas; in Indiana it has an average thickness of
5 feet and locally is as much as 11 feet thick throughout its
area of occurrence. From the standpoint of resources, it is
the most important bed in Indiana and western Kentucky, and it
is second only to the Herrin No.6 bed in Illinois.
In Illinois the No.5 Bed is present in strippable quantities in
some fifty counties having more than forty-one billion tons of
reserves. In Indiana the Springfield (No.V) Bed is present in
Sullivan, Vigo, Knox, Greene, Daviess, Pike, Gibson, Posey,
Vanderburgh and Warrick Counties, which contain twenty six
billion tons of reserve.
The correlating coal seam in western Kentucky (the No.9 Bed) is
commonly found throughout the entire reserve district and pre-
sently may be mined in Butler, Daviess, Henderson, Hopkins,
Muhlenberg, Ohio, Union,or Webster Counties.
The original program utilized a No.5 coal from Fulton County,
Illinois, and the present program gathered samples from two
Peabody Coal Company mines: the Eagle No.2 deep mine in Gallatin
County, Illinois, and the Camp Nos.l and 2 deep mines in Union
County, Kentucky. These mines presently produce a total of
three million tons per year. State maps showing the extent of
these correlated beds are shown as Figures A-17, A-18 and A-19.
Herrin No.6 Bed (Seam) - the Herrin No.6 bed is recognizable
over an area of about 15,000 square miles in the Eastern Inte-
rior coal basin, where it is second in commercial importance
only to the No.5 bed. It is known in western Kentucky as the
No.ll bed and in Indiana as the Hymera or VI bed. This coal
attains maximum thickness in southern Illinois, where it is
locally as much as 14 feet thick. In central Illinois and in
western Kentucky, the Herrin (No.6) bed is 5-7 feet thick over
large areas. It thins eastward and is relatively unimportant in
Indiana. It also thins toward the northwest edge of the basin.
From the standpoint of resources and production, it is the most
important coal in Illinois. In Illinois the No.6 bed has re-
serves in fifty-six counties, totalling approximately sixty-six
billion tons. In Kentucky the No.ll bed is presently being
mined in Hopkins, Ohio and Muhlenberg Counties. Indiana's
equivalent Hymera (No.VI) bed is of lesser importance but it
occurs in minable thickness in Sullivan, Knox, Pike, Gibson,
Warrick, Vanderburgh and Posey Counties.
22
-------
The previous bench-scale program^' utilized a No.6 coal from
Randolph County, Illinois and the present program examined a
sample of No.6 coal from the Orient No.6 mine of the Freeman
Coal Mining Company in Jefferson County, Illinois. State maps
showing the extent of the minable beds and the location of the
mine samples are shown in Figures A-20, A-21 and A-22.
WESTERN INTERIOR REGION
Des Moines No.1 - to provide a sample of coal from the Western
Interior Region, an Iowa coal from Marion County (the Des Moines
No.l) seam was selected. Some one hundred thousand tons per
year of this coal are mined by the Wei don Coal Company
at their Wei don strip mine which is one of the largest in the
state. Iowa's total reserves are an estimated 7 billion tons.
WESTERN COAL REGION
Wadge Seam - the Wadge seam of the Yampa field in the Green
River region is an example of coals from the northwestern part
of Colorado. The Edna mine of of the Pittsburg and Midway Coal
Mining Company in Routt County was sampled; it produces nine
hundred thousand tons per year and is one of the larger mines
in Colorado. The Wadge seam in Colorado correlates with other
coals of the Green River Region mined in the Rock Springs area
in southwestern Wyoming. In Colorado, the reserves are esti-
mated at some one and one-half billion tons.
No.6, 7 and 8 Seams (Fruitland Formation) - the No.6, 7 and 8
seams of the Fruitland Formation are presently being mined by
one of the largest stripping operations in the nation at the
Navajo mine in San Juan County, New Mexico. This mine is ope-
rated by the Utah International Company and produces over six mil-
lion tons of coal per year. The coal resources of New Mexico
are estimated at 62 billion tons, 80% of which are sub-bituminous
coals which include the coal mined at the Navajo mine.
Roland-Smith Seam - the Roland-Smith seam of the Powder River
Region represents one of the largest strippable reserve areas
of sub-bituminous coal in the U.S. For this program a sample
of the seam was taken from the Belle Ayr mine in Campbell
County (center of the Powder River Region) operated by the Amax
Corporation.
Rosebud Seam - the Rosebud seam of sub-bituminous coal is repre-
sentative of the vast reserves (20 billion tons) of strippable
coal available in the Fort Union Region of Eastern Montana. This
region is represented in northeastern Wyoming by the coals of.
the Powder River Region and translates into the lignites of
eastern Montana and western North Dakota. For the survey program,
a sample was taken from a large mine in the area, the Col strip
23
-------
mine in Rosebud County, operated by the Western Energy Corpora-
tion. This mine produces five million, five hundred thousand
tons of coal per year.
4.2.2 Sampling of Coals
One-ton samples of raw run-of-mine (ROM) coal were collected from
each mine. The samples taken in increments that represent at least a day's
production. Stopped belt samples were utilized as a first preference
and falling stream intercepts as an alternative. Auger sampling of unit
trains containing western coals was also utilized in cases where it could
be shown that the train contained only ROM coal from a single seam and mine.
The samples were sealed in plastic-lined drums (six per mine) for
shipment to Commercial Testing and Engineering Laboratory (CT&E) where
each 2,000 pound gross sample was crushed to IV' x 0 by a jaw crusher,
divided into four parts and treated as follows:
a IV' x 0 fraction for float-sink fractionation,
t a second part was crushed to 3/8" x 0 for float-sink fractionation,
a third part was crushed to 14 mesh x 0 for float-sink fractiona-
tion. A 25-lb sample of this material was also sent to TRW for
chemical processing to remove pyritic and organic sulfur,
the remaining part was held in reserve.
Float-sink fractionation of portions 1, 2 and 3 above was performed
with organic liquids at 1.30, 1.40, 1.60 and 1.90 specific gravities. The
resulting fractions were analyzed for ash, total sulfur, and pyritic sul-
fur on a dry basis. These results were then used to calculate washability
tables to determine cumulative recoveries and rejects at the various
specific gravities.
Since four coal mine samples (Edna, Navajo, Belle Ayr, and Colstrip)
had such low pyritic sulfur content that float-sink fractionation for its
removal appeared impractical, these samples were omitted from float-sink
studies.
Figure 6 illustrates the sequence of sampling and testing.
The procedures used to collect each of the 15 1-ton samples are
described below:
24
-------
FIGURE 6. U.S. BUREAU OF MINES
SAMPLING, HANDLING SYSTEM
AMENDED
R.O.M
Sample - 2000 Ibs
1
Lined 55gal Drums
I
Shipped to C.T.&E. Lab.
Crushed to 1-1/2" Top Size
Jaw Crusher
1 J
1/4 of Sample V4 of
uversize Screen
Over;
3/8"
1
Fines i
I Crushed to
1 Impact
>ize screen 1
I
Sample
,
1/4 of
J
1/4 of Sample
(Reserve)
Sample
3/8" Top Size Crushed to -14 Mesh
Crusner Hammer Mi 11
' "14 Mesh . i \
1 Overs 1/p Screen - , . _ -14
Fines
1
I
Oversize Screen
100 Mesh
Mesh
14 Mesh T*RW ,
1 Sample *
* Float-Sink Anal .
Fines Sp.Gr. 1.3
1 1 4
<
;
| Oversize Screen
Fines
1
Chem.Anal .
T.S.,Py.S.,Ash
J
C 1 /\ a + C ! L. fl ., 1
100
I
l fi
1 U
l.Q
Mesh - .. -
6 Ibs. Used
Fines
1
i
Chem.Anal .
T.S.,Py.S.,Ash
Sp.Gr. 1.3
1.4
1.6
1.9
300 Ibs. Used
1
Float-Sink Anal.
Sp.Gr. 1.3
1.4
1.6
1.9
150 Ibs. Used
25
-------
* Edna Mine. Wadge Seam, Routt County. Colorado. Pittsburg and
Midway Coal Mining Co. The raw run-of-the-mine coal crushed to
3" x 0 was collected on April 10, 1973,at 10-minute intervals
by cutting a stream at the discharge chute throughout a three
and a half hour period.
Navajo Mine, Blended Seams 6.7,8, San Juan County, New Mexico,
Utah International Co. The raw run-of-the-mine coal was collec-
ted by taking stopped belt increments at 10-minute intervals
throughout a 3-1/2 hour period on April 12, 1973, from the No.7
blend pile. The raw coal had been blended in the pile to rep-
resent proportional portions of Seams 6, 7 and 8 as produced by
this mine.
Belle Ayr Mine, Roland-Smith Seam, Campbell County, Wyoming,
Amax Corporation. The raw run-of-the-mine sample crushed to
2 x 0" was collected throughout a 24-hour period on February 13,
1973, as 10,000 tons of Belle Ayr coal was transferred to barges
at East St.Louis, Illinois. Stopped belt increments were taken
at 10-minute intervals throughout the entire transfer operation.
Col strip Mine, Rosebud Seam, Rosebud County, Montana, Western
Energy Cor p o r a tion. The raw run-of-the-mine sample crushed to
IV x 0 was collected on March 31, 1973, at the Commonwealth
Edison State Line Plant, Hammond, Indiana, from 10,000 ton
unit train No.CS-3. Thirty pound increments were taken from
1 each car of the 100-car unit train by means of a truck mounted
coal auger driven to a depth of 8 feet.
Weldon Mine^ Des Moines Seam No.1. Marion County, Iowa, Weldon
Coal Company. The raw run-of-the-mine sample crushed to 2" x 0
was taken on April 4, 1973, by removing fifteen 16-lbs increments
form each of 9 cars (135 increments total) as loaded by the
Weldon Coal Company.
Eagle Mine No.2, Illinois No.5 Seam, Gallatin County, Illinois,
Peabody Coal Company. The raw run-of-the-mine sample was col-
lected over a 5-hour period on January 29, 1973, at Eagle No.2
mine in Gallatin County, Illinois. Sixty increments of approxi-
mately 35 Ibs each were taken from the stopped belt leading from
the raw coal silo.
t Orient No.6 Mine, Herrin No.6 Seam, Jefferson County, Illinois,
Freeman Coal Mining Corp. The raw run-of-the-mine sample was
collected on January 31, 1973, at the Orient No.6 mine in
Jefferson County, Illinois. A 1-ton gross sample was collected
in 55-lbs increments taken every 10 minutes over a 6-hour period
from the automatic sampler on the raw coal belt.
t Camp Mine 1 & 2, No.9 Seam, Union County, Kentucky, Peabody Coal
Company. The raw run-of-the-mine coal was collected throughout
a 4-hour period on January 30, 1973. The raw coal from the two
Camp mines is blended in a silo prior to the automatic sampler.
Forty-eight increments were collected by the secondary cutter of
the automatic sampler at 5-minute intervals.
26
-------
* Walker Mine, Upper Kittanning Seam, Garrett County, Maryland,
Buffalo Coal Co. . The raw run-of-the-mine sample was collected
over a 4-hour period on March 7, 1973. Sixty increments were
collected from 15 locations in the raw coal pit.
Egypt Valley No.21 Mine, Pittsburgh No.8 Seam, Belmont County,
Ohio, Hanna Coal Co. On March 5, 1973,a raw run-of-the-mine
sample was obtained over a 4-1/2-hour period. This sample was
taken in four 35-40 Ib increments at each of fifteen locations
in the raw coal.
No.1 Mine, Mason Seam, Marian County. Kentucky, Dixie Fuel Co.
The" raw run-of-the-mine sample was collected over a 5-hour
period on March 28, 1973. Increments of approximately
150 Ibs each were collected at 8-minute intervals. The gross
6000 Ib sample was then reduced in size by the cone and
quartering method to 2276 Ibs.
Jane Mine, Lower Freeport Seam, Armstrong County, Pennsylvania,
Rochester & Pittsburgh Coal Co. The raw run-of-the-mine sample
crushed to 1-1/2" was collected throughout a 4-hour period on
March 8, 1973. One hundred and eighty increments were taken from
the raw coal belt leading from the crusher. Stop-belt sampling
was employed throughout the sampling period.
Fox Mine, Lower Kittanning Seam. Clarion County, Pennsylvania,
C&K Coal Co. The raw run-of-the-mine sample was collected
over a 4-1/2 hour period on March 8, 1973. From 15 locations
in the raw coal pit, 4 increments of 40 Ibs each were taken
from each location.
Harwick Mine, Sewickley Seam, Greene County, Pennsylvania,
Duquesne Light Company. The raw run-of-the-mine sample was
collected throughout four, 3-1/2 hour periods on March 5, 1973.
Increments were taken from the No.l stopped belt at 5
minute intervals. A tct-1 of forty increments, each weighing
about 50 Ibs, was taken.
Humphrey No.7 Mine, Pittsburgh No.8 Seam, Monongalia County,
West Virginia, Consolidation Coal Company. The raw run-of-the-
mine coal was collected over a 3 hour and 20 minute period on
March 6, 1973. The Pittsburgh No.8 Seam was sampled at the
automatic sampler on No.l belt going from the mine to the
cleaning plant. Forty increments of approximately 55 Ibs
each were collected after the primary sampler by stopping the
feed belt to the secondary sampler crusher and cleaning the
belt.
27
-------
4.2.3 Coal and Sample Preparation at TRW
A 25-lb (11.4 kg) sample of coal ground to 14 mesh x 0 was shipped
from CT&E to TRW in a sealed polyethylene bag inside a 5-gallon can. If
any surface moisture was observed, the coal was spread on a polyethylene
sheet in a fume hood and allowed to air dry from 4 to 6 hours. This gross
sample was then reduced by riffling into two 1600-2000g portions. One sample was
stored under nitrogen or argon in a glass container as a reserve, and the
other was ground in a disintegrator with a 0.58 mm screen. After several
passes, the entire lot was sieved using a 100-mesh screen. All oversize
material was then passed through the grinder several more times and re-
sieved; this process was repeated until more than 99% of the material
passed through a 100-mesh screen. The remaining 1% or less, which was
slate and other rock-like material, was discarded.
The entire lot of 100 mesh x 0 coal was then thoroughly mixed by
conventional cone and quartering techniques on a polyethylene sheet. The
coal was then bottled as 100.Og samples in containers that had been
flushed with nitrogen or argon. In order to guarantee relatively uniform
samples, the coal was periodically mixed during this process.
The sieve analysis is summarized in Table 6 while complete data is
presented in Appendix G. Note that while the coal is 100% 100 x 0 mesh,
in most cases 91% will pass a 150 mesh screen and 70% will pass a 200 mesh
screen.
28
-------
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4.3 CHEMICAL REMOVAL OF PYRITIC SULFUR
This section presents descriptions of the experimental methods and
summarizes results from the studies involving chemical removal of
pyritic sulfur from the surveyed coals. The removal of trace elements from
coals as a result of the Meyers Process is described in Section 4.6
together with a discussion of the experimental methods used to determine
the trace element composition. One coal of the fifteen sampled, the Walker,
contained too little pyritic sulfur to be included in the chemical removal
studies ( <0.1% w/w). Because of this and the need to relate current pro-
gram results to previous experimentation, the Lower Kittanning seam coal
utilized in the bench scale programMwas substituted for the Walker coal.
Also included in this section are discussions of (a) pyritic sulfur removal,
(b) ferric ion consumption and its relationship to the final heat content of
coal, (c) ash changes, (d) sulfate retention, (e) changes in the organic sul-
fur content and (f) miscellaneous findings.
4.3.1 Experimental Method
The general conditions for pyritic sulfur removal have been adapted
from the previous bench scale studies (EHSD 71-7)^with the objective of
obtaining maximum pyritic sulfur removal and of simulating process de-
sign as nearly as possible. A check-out run with Lower Kittanning coal
was performed to establish baseline extraction values.
Mesh Size - Coal ground to 100 mesh x 0 or finer has been found to
give the maximum extraction rates and to be most satisfactory for labora-
tory scale sampling.
Ferric Ion Concentration - Ferric sulfate solution IN^ in ferric ion
appears to be optimum, although differences due to concentration change do
not appear to be great.
Reaction Temperature - The reaction temperature was held at the reflux
of a IN^ ferric sulfate solution which is approximately 102°C. This allows
a reasonably high reaction rate and yet does not require pressure equipment.
A trial experiment was run for each coal (due to the high variance in
the behavior of individual coals) in order to select the reaction time,
leach solution to coal weight ratio, and number of leach solution changes
needed for maximum removal.
30
-------
Reaction Time - Each coal was leached a total of ten or more hours
depending on the characteristics of the individual coal treated.
Ferric Ion to Total Iron Ratio - Since the rate of pyrite removal is
slowed substantially by ferrous ion accumulation, each coal was treated
under conditions designed to keep this ratio >0.80 by one of the following
means:
t Increasing the leach solution to coal ratio(v/w)from a nominal
10 to a maximum of 40
Changing the leach solution after 3-6 hours of reaction
or more often if required
A combination of the above.
Post Sample Treatment - After treatment the samples were thoroughly
washed to remove any residual leach solution and then dried. All sample
calculations were done on a dry basis in order to eliminate variables due
to wetness of the coal. Sulfur forms and proximate analysis have been ob-
tained for each treated coal sample.
4.3.1.1 Extraction Procedure - The exact procedure used in this sur-
vey is described below:
One hundred grams of 100 mesh x 0 coal are added to 2 £
refluxing 1N_ ferric sulfate solution contained in a 4-neck,
3 a glass cylindrical reaction vessel equipped with a mechan-
ical stirrer, reflux condenser,and a thermocouple attached to
a recorder. Each vessel also has a stopcock at the bottom
for taking samples and is heated by a specially constructed
heating mantle. After the coal addition, an additional 0.5 £ of
l]i ferric sulfate solution is used to wash down the sides of
the vessel. At this point, the initial solution sample is taken
and the leaching process is considered started. Then, the re-
action mixture, which is at 88+4°C, is rapidly brought
to reflux, a process that takes 8-12 minutes. Leacn solution
samples for each analysis are taken by drawing a 200 ml aliquot
of the reaction mixture from which a 20 ml sample is taken and
cooled immediately to 0°C. Unused material is returned to the
reaction flask. After cooling, a 14 ml aliquot is centrifuged
to removal all suspended solids and 10 ml of this is used for
iron analysis. Any remaining coal or leach solution is re-
turned to the reaction flask.
31
-------
After 4-6 hours, the heating is stopped and the reaction
mixture is drained from the flask and vacuum filtered as dry
as possible to produce a dewatered product. The final reaction
volume and approximate solution retention on the coal are then
determined. The unwashed coal is then slurried with 200 ml
fresh ferric sulfate solution at 30 C and added to 2 £ fresh
]\± ferric sulfate solution at reflux. Another 300 ml ferric
sulfate is then used to wash any residual coal into the flask.
An initial leach solution sample is then taken and the entire
reaction mixture is brought to reflux in 8-12 minutes. Leach
solution samples are taken at regular intervals and, after a
total elapsed reaction time of 10 to 24 hours, the reaction
mixture is drained from the reaction flask, filtered, and
washed with 0.5-1.0 £ water.
The extracted coal is then slurried with 2 a of 1N_ sulfuric
acid at ^80° C for 2 hours, filtered, and stirred with another
2 a ~\H_ sulfuric acid at ^80°C for an additional two hours. After
filtration, this procedure is repeated with 2 £ water at ^80°C.
If scheduling does not permit coal to be extracted with toluene
immediately, it is stirred at ^50°C for an extended period until
it can be filtered and extracted with toluene for removal of free
sulfur formed during the leaching operation.
After the extraction of residual sulfate and iron by
the above washing procedure, the wet coal is transferred
into a 1 £ round bottom flask equipped with a mechanical
stirrer and Dean-Stark trap. A 400 ml volume of toluene is
added and the mixture is brought to reflux. This is con-
tinued for 15 minutes beyond the point when all the water
has been removed by azeotropic distillation (approximately
0.75-1.25 hr and 50-75 ml). The hot coal slurry is then
filtered, washed with 50-75 ml toluene and dried in a
vacuum oven at 100-120 C. The coal is then weighed and
analyzed.
4.3.1.2 Sulfur Forms Analysis - The procedure for sulfur forms analysis
is described in ASTM Standard D2492 and consists of extraction of sulfate
sulfur along with non-pyritic iron with 51V HC1. Sulfate is determined by
precipitation of BaSO, with Bad- after removal of iron from the solution.
This is followed by a 2N_ nitric acid extraction to remove pyritic sulfur.
The nitric acid extraction is performed on either the extracted sample or
a fresh sample. Pyritic sulfur is always determined by the titration of
the iron associated with the pyritic sulfur because nitric acid usually
removes a small amount of organic sulfur. If a fresh sample of coal is
used for nitric acid extraction, a blank iron determination must be made
on the HC1 extraction solution because all iron is extracted by nitric
acid. Even though the two sample method involves more work, it is used
most often because it allows simultaneous determination of sulfate and
pyritic sulfur, and, in general, the sample size necessary for the sulfate
32
-------
sulfur determination creates problems for oyritic sulfur determination and
v-lae versa.. The schematic of the analysis is given in Figure 7.
Coal, 5g 5v ur'n * a) sulfate as BaSOi,.> % w/w sulfate sulfur
reflux
30 min. 5) non-pyritic iron as mg/g.
Coal, Ig 2ft UMQ> a) total iron as mg/g
reflux b) mg pyritic iron/g = mg total Fe/g -
30 mm. mg non..pyritic Fe/g.
c) calculation of % w/w pyritic sulfur.
or
Coal, 5g r-M ur'i> sulfate as BaSOu 9MUMn > pyritic iron * % w/w
reflux refte3
30 min. 30 min.
Figure 7. Sulfur Forms Analysis Scheme
In the pyritic sulfur iron determination which is performed by
converting all the iron to the ferrous form and then oxidizing it back
to the ferric form with potassium dichromate, there are several possible
sources of error. These are listed below:
Color extracted by the nitric acid is often similar to
the ferric ion in color and if not removed completely, inter-
feres in the step where all the iron is reduced to the
ferrous form. Addition of excess reducing agent at this
point causes a poor final end point.
Organic matter extracted by nitric acid, if not removed,
is attacked by potassium dichromate, causing a diffuse
and fading end point.
Even under the best conditions, the indicator that is
used has an end point that has a tendency to fade.
The ASTM standards for precision are listed in Table 7 and show that
while the same operator can be expected to attain the same repeatability
as the standard Eschka (total) sulfur analysis, the matter of judgment in-
volved results in a much lower reproducibility between laboratories. In
practice, the standards for the Eschka analysis can be met by almost any
33
-------
analyst, while those for pyritic sulfur can only be met w'th difficulty
by an experienced analyst. Note that in this context the organic sulfur
value is the sum of all these errors and, thus, is a very sensitive error
indicator.
TABLE 7
SULFUR FORMS ANALYSIS - ASTM STANDARDS FOR DUPLICATE ANALYSES
MAXIMUM PERMISSIBLE SPREAD3
Total Sulfur
Laboratory
Sameb Different
Below 2%
.05 .10
Over 2%
.10 .20
Pyritic Sulfur
Laboratory
Same Different
.05 .30
.10 .40
Sulfate Sulfur
Laboratory
Same Different
.02 .04
na
Organic1" Sulfur
Laboratory
Same Different
.12 .44
.22 .64
All values are % w/w sulfur.
Same operator using the same equipment on the same day.
Sum of all errors, not an ASTM standard.
Coal samples from the same mine analyzed before and after treatment
fall into a special category. The subjective conditions under which these
analyses are run can be quite different and probably would be inter-
mediate between those assumed for replicate analyses on the same sample
done in the same or different laboratories. In addition, two sets of
samples are being analyzed and the maximum permissible A % for any form
could be double that for a single set of samples. Although this is not a
rigorous statistical analysis, it should be noted that the ASTM procedures
as set up allow for considerable variation for A % organic sulfur values
and, when this does occur, caution should be used in interpreting the
results.
A further difficulty occurs when very low (0.00-0.15% w/w) pyritic
sulfur values are encountered. In these cases, the blanks and other cor-
rections may even exceed the actual titration volume, and the presence of
only slight amounts of organic matter introduces substantial relative
error into the determination.
34
-------
4.3.2 Pyritic Sulfur Removal Results
Table 8 summarizes the results of the pyritic sulfur removal experi-
ments. The percentage removal may be calculated by dividing the difference
between the initial and final weight percent pyritic sulfur by the initial
weight percent pyritic sulfur. However, because of the ash (both pyritic
and excess) that is removed, the remaining pyritic sulfur in the treated
coal is slightly concentrated and analysis on a weight basis to calculate
percent removal results in a value lower than is actually the case. For
this reason, a corrected value was also calculated which compares the
weight of the pyrite in the treated coal to the weight of pyrite in the
untreated coal. The latter value, though harder to calculate because it
requires a material balance, is more nearly accurate than the former;
consequently, this value will be used in the following discussions.
The results of the pyritic sulfur removal are very encouraging in that
with the exception of the very low pyrite western coals, 89-99% w/w pyritic
sulfur removal was achieved for all the coals treated. The low initial
pyritic sulfur content of the western coals limited pyritic sulfur analysis
accuracy to an extent which obscured the percentage removal calculations.
For this reason calculated removals of only 59-89% were obtained even
though the pyritic sulfur levels in the treated coals were reduced to a
measured 0.03-0.06% w/w.
The standard set of reaction conditions utilized a reaction time of
23 hours, one change of leach solution during the 4 to 6 hour time period,
and 100 mesh x 0 coal. Although high removal was achieved with the Belle
Ayr and Colstrip coals using a reaction time of only 13 hours, these condi-
tions were not sufficient for high removal from the Weldon, Orient No.6,
Camp Nos.l&2 and Egypt Valley No.21 coals. Samples of these coals were ground
to 200 mesh x 0 to expose more finely divided pyrite encapsulated in the coal
and at the same time allow faster extraction, since the particles would be
ground to smaller size and thus present a greater surface area for reaction.
The 200 mesh x 0 Camp Nos. 1 & 2 coal was run for 23 hours (Run No.5)
which resulted in 99% pyrite removal compared to 80-89% removal (Run Nos.
1-4) for 100 mesh x 0 coal. The remaining pyrite was reduced from 0.62%
to 0.02% w/w. Since Run No.5 indicated a much increased rate of removal
35
-------
TABLE 8
SUMMARY OF PYRITIC SULFUR REMOVAL DATAa
Mine
Edna
Navajo
Belle Ayr
Col strip
yeldon
Eagle No. 2
Orient No. 6
Camp Nos 1 and 2
Egypt Valley No. 21
No. 1 (Dixie Fuel)
Jane
Fox
Warwick
Humphrey No 7
(Greene Co.)f
Seam
Uadge
Nos. 6, 7, 8
Roland-Smith
Rosebud
Des Moines No. 1
Illinois No. 5
Herrin No. 6
No. 9
Pittsburgh No. 8
Mason
Lower Freeport
Lower Kittanning
Sewickley
Pittsburgh
Lower Kittanning
Rank
hvCb
hvCb
subA
subA
hvCb
hvAb
hv^b
hvAb
hvAb
hvAb
hvAb
hvAb
hvAb
hvAb
mvb
Run
Number
1-3
1-3
1-3
1-3
1-3
4
1
2
3
4
1-3
4
5
1-3
4
5
6
1-3
4
1-3
1-2
3
1-3
4
1-3
4
1-3
1-3
Total
Rxn Time
23
23
6-10e
12-13e
23
13
13
14
14
23
23
23
13
13
23
23
13
13-225
13
23
u-z-f
23
23
13
23
13
23
12
Leach
Changes
1
2
1
1-2
2
1
2
1
1
1
1
1
1
1
1
2
1
1
1
1
1
1
1
1
1
1
1
1
Meshb
100
100
100
100
100
200
100
100
100
100
100
200
200
100
100
200
200
100
200
100
100
100
100
200
100
100
100
100
Initial
0.14 + .015
0.28 + 044
0.22 + .017
0.34 + .015
5.24 i .038
2.64 + .154
1.30 + .084
2 80 t .120
5.07 + 025
1.98 + 062
1 44 + .098
3 09 + .017
1 09 + .086
1.59 + .114
3.58 + .080
Fi nal
0 06 +_ .020
0.04 + .040
0.03 + .012
0.06 + 006
0.47 + .099
0.15
0.36
0 11
0.33
0.19
0.32 + .076
0.12
0.06
0 62 + .210
0.33
0 02
0.14
0 62 + .178
0 38
0 21 < .045
0.14 + .007
0.63
0.37 +_ 163
0.47
0 09 + .043
0.06
014^ .055
0.38 + .089
Removed
0.08 + .025
0.24 + 059
0.19 + .021
0.28 + .016
4.77 i .106
5.19
2.28
2 53
2.31
2.45
0.98 + .113
1.18
1 24
218+ 242
2.47
2.78
2.66
4 45 + 180
4.69
1.77 + .077
1.30 + .098
0.81
2.72 + .164
2.62
1 00 + .096
1 03
1.45 t_ .127
3.20 + .120
Pyri te
Nominal c
57
86
86
82
91
97
86
96
88
93
75
91
95
78
88
99
95
88
93
89
90
56
88
85
92
94
91
89
Removal , I w/w
Corrected"1
59
87
89
83
92
98
94
98
91
94
76
92
96
BO
89
99
96
89
93
90
91
60
89
85
92
95
91
90
Dev.
15
14
5.6
1 9
1 9
-
-
-
6 1
-
-
J 6
-
3 5
2 3
0 8
-
5 3
-
4 0
,
3 5
2.5
aWalker mine omitted due to low pyntic sulfur content (0.07%).
b!00 mesh x 0 and 200 mesh x 0 coal is symbolized as 100 and 200, respectively
cTh1s value is calculated by dividing the pyntic sulfur loss in % w/w by the initial
% w/w pyntic sulfur.
^This value is calculated by dividing the number of mill) mules of sulfur loss by the
initial number of milli moles of pyntic sulfur.
Indicates different reaction times with no significant difference in results.
Lower Kittanning coal from previous bench-scale program!1).
36
-------
an additional experiment (Run No. 6) was performed with a total reaction
time of 13 hours. This run resulted in 96% pyrite removal with a final
pyrite content of 0.14% w/w. Another set of experiments, using 200 mesh
x 0 Orient No. 6 (Run Nos. 4-5) coal, gave much better removals than
obtained with -100 mesh coal. In the 23-hour run, the removal was in-
creased from 76% to 92%, and the final pyrite content was reduced from
0.32% to 0.12% w/w. Reducing the reaction time to 13 hours gave an
apparent increase in removal to 96% with a final pyrite content of 0.06%
w/w. Because the above results are from single experiments, the detailed
results should be used with caution, although the general observations
provide valid trends.
A series of 13-hour runs using 200 mesh x 0 coal was also conducted
on the Egypt Valley No. 21, Fox, Warwick, and Weldon coals. This resulted
in increased pyrite removal from 89 to 93% for the Egypt Valley coal; 92
to 95% for the Warwick coal; 92 to 98% for the Weldon coal; and a reduction
from 89 to 85% for the Fox coal. The corresponding final pyrite changes
were 0.62% to 0.38%, 0.09% to 0.06%, 0.47% to 0.15%, and 0.37% to 0.47%,
respectively. Thus, grinding the coals to 200 mesh x 0 allows a much
faster rate of reaction and equal or increased pyrite removal is observed
in all but one case. Further work is necessary in order to determine
whether this is general for all coals.
Although the precision of the results of this survey has been excel-
lent, Run No. 2 on the Eagle No. 2 coal and Run No. 3 on the Jane coal
are anomalous as the former shows lower than expected final pyrite and
the latter shows higher than expected final pyrite. The data and cir-
cumstances surrounding these experiments have been examined and checked
and no systematic reasons can be found for these discrepancies. Similarly,
the high standard deviation for Runs 1 to 3 on the Camp Nos. 1 and 2 coal
led to the discovery that the temperature controllers were maintaining
all the leach solutions 2-6°C below reflux and that the spread in removals
appeared to parallel these differences. Run No. 4, carefully held at
reflux, resulted in much higher removal. A close examination of the
results in Appendices C and D also shows that the spread between tripli-
cate pyritic sulfur value is often of the order of 0.2-0.3% w/w. Thus
duplicate or triplicate runs or determinations are necessary in order to
37
-------
get results that can be treated with a relatively high degree of con-
fidence .
4.3.3 Heat Content Changes and Ferric Ion Consumption
Table 9 summarizes the effect of chemical extraction of pyritic sulfur
from coals with ferric sulfate solutions on the heat content of the coals
and how this effect is related to excess ferric ion consumption over that
needed for pyrite removal. Because pyrite removal is in effect the
removal of low btu "ash" (2995 btu/lb), its removal in most cases has
more than compensated for any oxidation of the coal matrix. Thus, with
the exception of the Western coals and one Interior Basin coal, heat
content increases of 1.5-8.9% were observed. The Western coals,with low
initial pyrite (0.14-0.34% w/w) and a high order of reactivity with ferric
ion, had heat content decreases of 0.1-4.3%.
Although dry btu determinations are useful for those interested in
shipping and using coal, a true picture of the effect of ferric ion oxida-
tion of the organic coal matrix and its relationship to excess ferric ion
consumption can only be obtained by examining the dry mineral matter free
heat contents that have been corrected to eliminate any contributions to
the heat content by pyrite. These values (also listed in Table 9) show a
heat content loss of 2.9-8.3% for the Western coals, a +0.4 to -5.1% change
for the Eastern and Western Interior Basin coals, and a +2.6 to -4.6% change
for the Appalachian Basin coals. Since, theoretically, heat content gains
are not possible, any gains must be attributed to inaccuracies in experi-
mental determinations and assumptions inherent in the equation used to cal-
culate these values. Thus, close examination of these differences, in view
of experimental uncertainties and calculation assumptions, indicates that
with the exception of the Orient No. 6 mine, the No. 1 mine (Dixie Fuel)
and the Western coals, the reaction of ferric ion with the organic matrix
has such a small effect on the heat content of the coal that the differ-
ences may not be statistically significant.
The extent of reaction of the ferric ion with the organic coal matrix
is illustrated by examining excess ferric ion consumption. This value was
calculated by subtracting from the total ferrous ion produced the amount
of ferrous ion that should have been produced by pyrite removal, assuming
the reaction chemistry of Figure 1 and dividing by the dry mineral matter
38
-------
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39
-------
free organic material. These calculations show that the coals fall into
three distinct classes, with the Appalachian Coal Basin coal consuming
0.62-1.69mM/g excess ferric ion, the Interior Coal Basin coal 1.20-4.77mM/g
excess ferric ion and the Western coals 5.33-19.09mM/g excess ferric ion.
(Use of 200 mesh x 0 coal seems to increase ferric ion consumption.) In
general, these results follow the degree of metamorphism of these coals.
The Western coals have low rank and an open pore structure which provides
an abundance of active sites for reaction. The Eastern Interior Basin
coals have a higher rank but still have an open pore structure that allows
substantial reaction, while the Appalachian Basin coals, through of similar
rank, have the most closed pore structure and as a result show very little
reaction with the ferric ion.
4.3.4 Removal of Residual Sulfate
After extraction of pyritic sulfur substantial sulfate was retained
on some coals when a minimal coal wash procedure was used. This wash
consisted of three 500 ml hot water rinses of the coal on the filter
funnel after filtration of the reaction mixture. This procedure, which
was used on all trial runs and the final triplicate runs for Camp Nos.l&2
and Orient No.6 coals, resulted in sulfate values (sulfur as sulfate, but
referred to only as sulfate in the following discussion) ranging from a
very acceptable 0.06% w/w (Colstrip and Jane) to a very high 0.45-0.85%
w/w (Edna, Belle Ayr, Orient No.6 and Eagle No.2) with the majority of
coals falling in the range of 0.2-0.4% w/w (see Table 10).
It- is currently believed that sulfate retained on the treated coals can
be reduced or eliminated by one or more of the following methods: (a) con-
trol of acidity and iron concentration or form during extraction, (b) selec-
tion of optimum filtration temperature, (c) equilibration of the leach
solution with the coal as in the thickener section of a process plant, or
(d) selection of the appropriate washing parameters. Because detailed
evaluation of these processing techniques was not practical during this
program, only approaches involving washing techniques were investigated.
These methods, once determined, could then be easily incorporated into
the laboratory procedure.
40
-------
TABLE 10
SULFATE RETENTION AS A FUNCTION CF WASH PROCEDURE AND REACTION CONDITIONS
Coal Mine
Edna
Navajo
Belle Ayr
Colstrip
Heldon
Eagle No. 2
Orient No. 6
Camp NOS. 1 & 2
Egypt Valley No. 21
No. 1 (Dixie Fuel)
Jane
Fox
(Green Co.)
Warwick
Humphrey No. 7
Seam
Madge
Nos. 6, 7, 8
Roland-Smith
Rosebud
Des Moines No. 1
Illinois No. 5
Herri n No. 6
No. 9 (U. Ky.)
Pittsburgh No. 8
Mason
Lower Freeport
Lower Kittanning
Lower Kittanning
Sewickley
Pittsburgh
Run
Number
Trial
1-3
Trial
1-3
Trial
1
2-3
Trial
Trial
1-3
Trial
1-3
4
Trial
1-3
4
Trial
1-3
4
5
1-3
4
5
6
Trial
1-3
4
Trial
1-3
Trial
1-3
Trial
1-3
4
1-3
Trial
1-3
4
Trial
1-3
Reaction
Time
(Hrs)
12
23
12
23
21
6.5
10.5
23
13
12-13
14
23
13
23
13-14
23 ,
21
23
23
13
13
23
23
13
13
13-22
13
12
23
13
12-23
13
23
13
13
13
23
13
14
23
Mesh
100 x 0
100 x 0
100 x 0
100 x 0
100 x 0
100 x 0
100 x 0
mo x n
100 x 0
100 x 0
100 x 0
100 x 0
200 x 0
100 x 0
100 x 0
100 x 0
100 x 0
100 x 0
200 x 0
200 x 0
100 x 0
100 x 0
200 x 0
200 x 0
100 x 0
100 x 0
200 x 0
100 x 0
100 x 0
100 x 0
100 x 0
100 x 0
100 x 0
200 x 0
100 x 0
100 x 0
100 x 0
100 x 0
100 x 0
100 x 0
Wash
Procedure3
Minimal
Standard
Mi nimal
Standard
Minimal
Standard
Standard
Minimal
Minimal
Standard
Minimal
Standard
Standard
Minimal
Standard
Standard
Minimal
Minimal
Standard
Standard
Minimal
Standard
Standard
Standard
Minimal
Standard
Standard
Minimal
Standard
Minimal
Standard
Minimal
Standard
Standard
Minimal
Minimal
Standard
Standard
Minimal
Standard
Sulfate
Retention
" w/w
0.68
0.49
0.54
0.15
0.64
0.14
0.14
0.23
0.06
0.06
0.31
0.18
0.12
0.85
0.18
0.23
0.45
0.62
0.35
0.17
0.42
0.28
0.25
0.16
0.25
0.11
0.13
0.26
0.09
0.06
0.06
0.31
0.09
0.09
0.30
0.35
0.14
0.07
0.10
0.10
Initial
Sulfate
/' w/w
0.00
0.03
0.00
0.00
0.15
0.04
0.01
0.06
0.14
0.08
0.00
0.05
0.10
0.01
0.01
See text for explanatiorrof procedures
41
-------
Table 11 summarizes sulfate extraction experiments performed on the
treated Camp Nos. 1 and 2 coal. Note that both methanol and aqueous methanol
are much less effective than water in reducing the sulfate content of the
coal, but that the addition of 1% v/v sulfuric acid to aqueous methanol
reduced the sulfate to 0.24% w/w. Because methanol is detrimental to sul-
fate removal, the use of 1% aqueous sulfuric acid could be even more
effective. In addition, basic solutions such as 5% w/v sodium carbonate
and 10% v/v concentrated ammonium hydroxide in aqueous methanol and
chelating agents such as 3% w/w ethylenediamine tetracetic acid and 10% w/w
tetraethvlene tetramine are apparently slightly more effective than water
in reducing the sulfate level.
TABLE 11
SPECIAL SULFATE REMOVAL EXPERIMENTS
CAMP NOS. 1 AND 2 COALa'b
Experiment
1
2
3
4
5
6
7
8
Reagent
H20
CH3OH
aq.CH3OHC
1% H2S04 in aq. CH3OHC
5% Na2C03 in aq.CH3OHc
10% NH4OH in aq.CH3OHc
3% EDTA in aq. CH3OHC
10% Tetraethylene
tetramine in aq. CH3OH
Temp., °C
Reflux
Reflux
Reflux
Reflux
Reflux
Reflux
Reflux
Reflux
Final % S04, w/w
0.19
0.33
0.49
0.24
0.13
0.20
0.13
0.11
alnitial sulfate retention 0.42% w/w, the ratio of coal to extraction
solution was 1:60 w/v
Extraction time of four hours followed by thorough water wash
GMethano1: water ratio of 7:3
Table 12 summarizes a second set of sulfate extraction experiments per-
formed on treated Orient No. 6 coal. With this coal, an additional wash
with either water, 0.1-3N. sulfuric acid or 1N_ oxalic acid for one hour at
elevated temperature was effective in reducing the sulfate level from 0.62
to 0.25% w/w or less.
42
-------
TABLE 12
TE REMOVAL
ORIENT NO. 6 COAL'
SPECIAL SULFATE REMOVAL EXPERIMENTS
a,b
Experiment
1
2
3
4
5
6
7
Reagent
H20
0.1N hLSO.
2 4
0.5N H,SO.
2 4
l.ON H9SO,
2 4
3. ON H-SO,
2 4
l.ON H2S04
IN Oxalic Acid
Temp.,°C
^90
^80
^80
^80
^80
^30
^60
Final % S04> w/w
0.25
0.21
0.23
0.19
0.23
0.36
0.16
alnitial sulfate retention 0.62% w/w, the ratio of coal to extraction
solution was 1:20 w/v
Extraction time of one hour followed by thorough hot water wash
Washing with 1!N sulfuric acid at 30°C (Expt. 6) was not nearly as effective
giving a final sulfate value of 0.36% w/w and indicating that elevated
temperature is necessary for more effective sulfate removal. However, since
these results are from single experiments and the grouping of these values
with the exception of Experiment 6 is so close, the remaining six methods
in Table 12 should be considered equally effective at this point.
Based on the above experimentation, water washing as well as washing
with dilute sulfuric acid is capable of removing residual sulfate. Dilute
sulfuric acid should be also an advantage in those cases where basic iron
sulfates are present. Basic solutions or chelating agents, though effective,
will introduce unnecessary process expense and should not be considered if
the above are effective. Therefore, the following standard procedure was
adopted for the survey studies in order to ensure, without optimization,
a low level of sulfate in the treated coals.
43
-------
The extracted coal is slurried with 2 st, of IN sulfuric acid at
^80°C for 2 hours, filtered and stirred with another 2 a IN.
sulfuric acid at ^80°C for an additional two hours. After
filtration, this procedure is repeated with 2 £ water at ^80°C.
If scheduling does not permit the coal to be extracted with
toluene immediately, stirring is continued at ^50°C for an ex-
tended period until filtration and extraction can be performed.
The results listed in Table 10 show that the final sulfate can be re-
duced to 0.06-0.14% w/w for Appalachian Basin coals, 0.16-0.35% w/w for the
Eastern Interior Basin coals, 0.12-0.18% w/w for the Western Interior Basin
coal (Weldon),and 0.06-0.49% w/w for the Western coals using this method.
Thus, while not necessarily the best procedure, this standard method
achieved an acceptable final sulfate level.
In order to determine how additional washing would affect sulfate
levels, samples of the Egypt Valley No. 21, Fox, Warwick, and Humphrey No. 7
coals that had already been washed and extracted with toluene to remove
elemental sulfur were refluxed in 1:20 w/v ratio of coal to both IN^ and O.lj\[ sul-
furic acid for four hours. After filtration and rinsing, the samples were
refluxed in 1:20 w/v ratio of coal to water to remove residual acid and
sulfate. This resulted, in all cases, in a sulfate level of <0.01% w/w.
In regard to sulfate retention, the following observations should also
be considered:
o After minimal washing the Appalachian coals have a much
lower sulfate retention than the other survey coals
o The final sulfate after washing seems to increase with
increasing ferric sulfate leaching time
o - The mesh size does not seem to affect the final sulfate
retention
Thus, while the problem of sulfate retention has been reduced in
importance, the amount of sulfate retained appears to depend somewhat
on the individual characteristics of the coal. Also, the washing
procedure used here, while fitting into the general constraints of the
Meyers Process, has not been optimized. In particular, the use of a
continuous counter current wash or multiple washes may be as effective
as the prolonged washes used above. In addition, a sulfuric acid wash may
not be necessary. Thus, for a complete understanding of the problem, several
44
-------
coals should be investigated in detail in order to determine the minimum
conditions necessary for sulfate removal.
4.3.5 Ash Changes
Table 13 summarizes ash changes that occurred upon extraction of the
coal with ferric sulfate. The calculated change was obtained by multiplying
the absolute percent pyritic sulfur removed by 1.25 for upon ashing pyrite,
FeS?, is converted to iron oxide, Pe^Oo, as follows:
FeS2 + 2.75 QZ > 0.5 Fe203 + 2 S02
In all cases, more ash was removed than can be accounted for by pyrite
removal alone. In general, excess removal was greatest for the Western
and the Eastern Interior Basin coals. The only Appalachian coal with a
high excess removal is the Warwick coal, which probably is the result of
its very high 40.47% initial ash.
Since the aqueous extraction solution is both acidic and oxidizing,
inorganic materials in the ash could be brought into solution by either
an acidic or oxidizing attack. However, the most likely mechanism of
solution probably is dissolution of basic inorganic compounds by the
sulfuric acid that is present in solution. Since acid soluble compounds
of sodium, potassium, magnesium and iron, such as oxides and carbonates,
can be major constituents of coal ash, they could easily account for the
excess ash removal. However, since research has thus far not accurately
defined this situation, additional experimentation should be performed in
order to establish purification requirements for recycled ferric sulfate
streams. Operation of a continuous large-scale (pilot) facility may be
required to completely clarify potential problems in this area.
4.3.6 Organic Sulfur Changes
After several coals had been extracted, the results seemed to indi-
cate that the treated coal apparently had a higher organic sulfur content
than the starting coal. Although organic sulfur increases of 0.01-0.12%
w/w were attributable to ash removal, these did not account for all of
the apparent increases. In addition, the organic sulfur value is the
least accurate of all sulfur analyses because it is not determined directly
45
-------
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but by subtracting the amount of pyritic and sulfate sulfur from the total
sulfur. For this reason the organic sulfur value contains resultant errors
from all three analyses. Thus, according to ASTM Standards, duplicate or-
ganic sulfur values with spreads of up to 0.4-0.6% w/w can be considered ac-
ceptable for analyses done by different operators in different laboratories.
The problem is made even more ambiguous due to the possibility that treat-
ing the coal with ferric sulfate solution can introduce a systematic error
in the results. Therefore, a thorough statistical analysis was made in order
to assess the validity of the indicated results.
The statistical analysis of the organic sulfur data is tabulated in
Table 14. Note that the actual percent w/w differences were corrected for
any expected increase due to actual ash removal (see Table 13). Single runs
are included for informational purposes even though only limited statistical
information can be obtained from them. In the fourteen cases where multiple
runs were performed, six show an increase of more than +0.1%, and one shows
a difference of -0.14%. Of the remaining seven cases, four show an increase
of less than 0.1% and three a decrease of less than 0.1%.
All the data were then tested for significance by applying the t test
in which the value of t was calculated according to the equation:
, (f - A") /"n"
t = -* *
where A = average starting organic sulfur,
B = the average final organic sulfur,
n = the number of values in each set, and
Oj = the standard deviation of the difference B" - A"
d
The value of t is then used to determine the level of significance by
consulting a standard table of values used for the t distribution (2).
From an analytical point of view a systematic error of 0.1% is easily
possible and from a practical perspective differences less than 0.1% are
not important; therefore, the data were tested for statistical significance
for a difference >0.1% w/w. Using this criterion, the Weldon, Egypt Valley
No. 21, Fox, and Warwick coals had >0.1% w/w organic sulfur increase with
a significance of 90 or more percent. The No. 1 (Dixie Fuel) and the
Humphrey No. 7 mines were significant at the 80% and 70% levels, respec-
47
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48
-------
tively. When tests were made for significance for differences >0.4% w/w,
the Weldon and Egypt Valley No. 21 coals still had 80% significance, while
the Fox and Warwick coals began losing significance at the 0.2% difference
level.
The data were further examined for geographic correlations. The
Eastern Interior Basin coals showed no statistical differences between
the starting and final coal analyses, while the coals from the Western
U. S. showed no gain at the 0.1% level. The Western Interior Basin coal
and six out of the seven Appalachian coals showed significant increases
at the 0.1% level. The reader should note, however, from the single runs
which are listed that individual final organic sulfur values can vary
considerably. Also, the Orient No. 6, Camp Nos. 1 and 2, and Weldon
samples ground to 200 mesh x 0 showed greater final organic sulfur content
while the Fox sample shows less.
The selection of coals was not extensive enough to make comparison
between seams. However, both the Egypt Valley No. 21 and Humphrey No. 7
coals were from the Pittsburgh seam, and while the former showed a sub-
stantial increase, the latter showed only a slight increase, indicating
that perhaps local rather than general factors determine the amount of
increase.
These organic sulfur increases could result from three possible sources:
(a) actual organic sulfur increases caused by either sulfonation or sul-
fation reactions, or (b) apparent organic sulfur increases caused by
formation of unextractable inorganic sulfur species during coal leaching,
and (c), incomplete removal of elemental sulfur in the toluene extraction
step. Partially oxidized coals, coals with many phenolic groups of other
active sites, or highly porous coals with a large internal surface area
should be prime candidates for sulfonation or sulfation. Coals of this
type included in the survey are the Western and the Western and Eastern
Interior Basin coals. In fact, these two groups of coals in general had
a higher ferric ion consumption (see Table 9) than the Appalachian coals.
Ferric ion oxidation of coal should typically produce phenols, alcohols
and other reactive sites which could easily react with the sulfuric acid
present in any extraction. Since both of these groups of coals did not
show a significant organic sulfur increase, the possibility of sulfonation
or sulfation reactions is presently considered unlikely.
49
-------
Apparent organic sulfur increase could result from insoluble inor-
ganic compounds such as CaSO^ or Fe(OH)S04 precipitating in the pores of
tightly structured coal such as is the case for most Appalachian coals.
Coals with high pyritic sulfur contents such as Egypt Valley No. 21,
Weldon, and Fox could produce significant amounts of sulfate internally
which could precipitate as CaSCty in the coal pores by reactiong with CaO or
CaC03 present in all coal ash or could form insoluble Fe(OH)S04 under appropriate
conditions. Even though the analytical procedure for hydrochloric acid ex-
traction of sulfate sulfur was designed specifically to remove sulfate formed
by oxidation or weathering and thus could very well miss deeply imbedded in-
organic material, it seems unlikely that more than 0.1? sulfate sulfur could
be missed in the analysis even in the Appalachian coals.
The third possibility is the incomplete removal of the elemental sulfur
in the toluene extraction step. This sulfur would raise the total sulfur
value but not result in erroneously high pyritic or sulfate sulfur values. Because
organic sulfur is calculated by difference, this additional sulfur would then
result in a higher organic sulfur value. Since the extraction step has not
been optimized and is presently performed only once, this source should be
considered an excellent possibility. In addition, this residual elemental
sulfur would be expected to be the greatest in the highly structured and
small-pored Appalachian coals, and less in the more porous Internal Basin and
Western coals. Because actual results follow these trends, it is felt that
this is the probable source of the organic sulfur increase. Additional
experimentation is required to confirm this possibility and to establish
tentative solutions.
4.3.7 Miscellaneous Data
Table 15 contains miscellaneous data which was accumulated during
this survey and which is treated briefly in the paragraphs below:
The Free Swelling Index (FSI) is an indication of the caking
qualities of a coal and thus has some importance in evaluation
of a coal for coking and for use in certain types of steam
boilers. The data shows that, with coals that have high
excess reactivity with ferric ion (such as the Eastern
Interior Basin coals), the FSI is reduced substantially.
Coals that have little excess reactivity with ferric sulfate
(such as the Appalachian 3asin coals) had little or no
change upon treatment. This is consistent with the gen-
erally accepted idea that slight oxidation of a coal
reduces its FSI.
50
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Nitrogen Content - The nitrogen content of the treated and
untreated coals was monitored on the same 10 group samples
that were analyzed for trace element changes. Since it can
be safely assumed that the nitrogen is primarily organic
in nature, the nitrogen values of the treated coals were
corrected for ash loss upon extraction. When these values
are compared to the original values, there are no significant
differences,indicating that the nitrogen content of the
coals is not affected by the leaching process.
The Fi1tration Rates of the various coals are qualitatively
shown in the last column of Table 15. These observations
are based on the amount of time required to obtain a dewatered
filter cake from 100 g of 100 mesh x 0 coal in 2.5 £ of
leach solution. A label of fast(F) indicates no problem in
filtration with the rate proceeding near the maximum rate
of the funnel; medium (M) indicates a slower, but still accept-
able rate; and slow (S) indicates that unacceptably long times
were required for filtration. Coals ground to 200 mesh x 0
always filtered slower.
Rank - The rank of the treated and untreated coals is the
same in all instances except for the Orient No. 6, Belle Ayr and Navajo
coals. Because rank is determined only heat content for hvAb
and lower ranked coals, only minor differences in rank should be
expected because rank is quite insensitive to small btu changes.
52
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4.4 FLOAT-SINK TESTING
Float-sink testing (washability studies) were run on eleven of the
fifteen coals by Commercial Testing and Engineering Company in order to
determine how conventional float-sink procedures compare to the Meyers
Process in efficiency of pyrite removal, heat content change, and ash loss.
In addition, information was obtained that can be used to evaluate a com-
bined two-step process involving coal washing followed by the Meyers Pro-
cess that would produce coal containing minimum amounts of pyrite and
ash and a maximum of heating value.
4.4.1 Procedures
The mine samples, representing fifteen mines and coal seams, were se-
lected, sampled and prepared according to the procedures described in
Section 4.2 of this report. No tests were run on the four samples from
the Edna, Navajo, Belle Ayr and Col strip mines since they contained less
than 0.3% w/w pyritic sulfur and 1.0% total sulfur and were judged econo-
mically unfeasible for washing in order to remove pyritic sulfur.
Five hundred pounds each of the 1-1/2" x 100 mesh, 3/8" x 100 mesh
and 14 mesh x 0 portions obtained from the initial sampling of the coals
were fractionated according to standard float-sink procedures using organic
liquids of 1.30, 1.40, 1.60 and 1.90 specific gravities. Head samples for
each size (or grind), each gravity portion and the two 100 mesh x 0 samples
were analyzed on a dry basis for % w/w ash, total sulfur and pyritic sulfur.
The raw data were then used to calculate washability data showing cumu-
lative recovery and cumulative reject at the various specific gravities for
each of the size portions. A complete set of tables showing all the data
is included in Appendix E.
4.4.2 Results and Discussions
Table 16 shows the summary of the results for the 14 mesh x 0 portions
at 1.90 and 1.60 specific gravities and how they compare to the Meyers Pro-
cess for total sulfur and pyritic sulfur reductions and ash removal. The
14 mesh x 0 portions, even though it may be too fine a grind to be used in a
commercial installation, was chosen because in most instances this size
generates the best results that can be obtained by float-sink procedures.
53
-------
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13
-------
The IV x 100 mesh portions from the Eagle No.2 and Humphrey No.7 mines
gave results similar to that of the 14 mesh x 0 portions and in the case
of the Weldon coal, better results were observed. With all other coals,
coal cleaning potential decreased when washing coarser material.
In Table 16 the % float-sink btu/lb loss was calculated from the % w/w and ash
content of the cumulative material rejected at the specific gravity of interest.
This value was assumed to represent the total heat content loss and was
subtracted from 100% to give the btu recovery. For the Meyers Process complete
organic material recovery was assumed because no evidence has been found to
date that indicates material other than ash is dissolved in the leaching
process. The percent heat content recovery was then calculated using the
before and after dry, mineral matter free, pyrite btu free, heat content
of the coal.
The analysis of the 1.90 float material shows that 0.1-1.9% w/w more
total sulfur is removed from the coal by the Meyers Process when compared
to the float-sink method. For the 1.60 float material the corresponding
figure is 0.0-1.5% w/w with the majority of the values for both specific
gravities being between 0.4 and 1.0%. It should be noted that commercial
methods using 3/8" x 100 mesh or 1-1/2" x 100 mesh coal are not as efficient
as the laboratory procedure using 14 mesh x 0 coal. On the other hand,
larger chemical processes are often more efficient than laboratory scale, thus
the Meyers Process may be more advantageous than is apparent from the present data.
The advantages of the chemical leaching is even more apparent from the
final pyrite values. For all but three coals, the final pyrite values are
between 0.06 and 0.15% w/w when the coals were treated by the Meyers Pro-
cess; however, even when using the 1.60 float material, physical washing
only gave final pyritic sulfur values between 0.8 and 3.0% w/w. The 1.60
float material of the washed Jane and Warwick coals had final pyritic sul-
fur of 0.3 and 0.4% w/w, respectively, making them possibly competitive
with the Meyers Process. The two high values for chemical leaching of 0.4%
for the Egypt Valley and Fox coals are still much better than 1.60 float
material values of 3.0 and 1.2% for the washed coals. Note, however, that
90% pyrite removal is not always reflected in the total sulfur values due
to slight increases in other sulfur forms. Although for approximately one-
55
-------
half of the coals the results are already near optimum (see Table 1),
additional processing improvements will be necessary to reach near optimum
values for the others. However, in each case the Meyers Process reduced
the total sulfur content of the coals lower than that obtainable by con-
ventional coal cleaning. In most cases, substantital differences were
found.
The btu or heat content recovery for the 1.90 float material is 93-99%
and for the 1.60 float material, it varies from 89-97% with a median value of
95%. In contrast, chemical leaching results in 98-100% btu recovery. Only
the No.l (Dixie Fuel)and the Orient No.6 coals reacted with the ferric sul-
fate leach solution sufficiently to cause heat content reductions as high
as 5%. Thus, for almost every coal the Meyers Process is more efficient
than physical separations with respect to btu recovery.
Table 16 also summarizes ash changes as the result of both processes.
Note that in most cases, especially the Warwick, Jane, Egypt Valley No.21,
Eagle No.2, Camp Nos.l&2 and Orient No.6 coals, substantially more ash is removed
by physical cleaning compared to the Meyers Process (in which only ash corres-
ponding to pyrite is removed). Only in low ash cases such as the Fox and
Humphrey No.7 coals are both processes comparable. With the Walker coal
which had essentially zero pyritic sulfur, only ash reduction was achieved.
However, ash reduction in itself is valuable in that reduced shipping costs,
reduced load on electrostatic precipitators and enhanced heating values are
realized. In addition, a certain part of the ash is soluble in the leach
solution of the Meyers Process and any initial ash reduction should reduce
purification requirements on this solution, and depending upon pyrite re-
x
duction, operating costs of the Meyers Process. Thus, depending on the
situation, a simple washing procedure on coals containing >20% w/w ash may
be advantageous prior to treatment with the Meyers Process.
56
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4.5 ORGANIC SULFUR EXTRACTION EXPERIMENTATION
From the previous bench-scale program (Ref.l) studies for the re-
moval of organic sulfur from coal p-cresol appeared to offer promise for
partitioning coal into organic sulfur rich and organic sulfur lean frac-
tions according to data obtained by analysis of the extracted and unextrac-
ted coal. However, analysis of the extracted portion did not confirm
these results. It was the objective of this survey program to assess the
effect of p-cresol on various types of coals in order to obtain additional
information regarding the possibility of organic sulfur partition. The
results are presented below.
4.5.1 Baseline Conditions
The baseline conditions for organic sulfur removal were determined
from the work performed under Contract EHSD 71-7 (Ref.l). A discussion of the
various test parameters is presented below:
Mesh Size - coal that has been ground to 100 mesh x 0
gives the highest apparent organic sulfur removal and
is easily handled in the laboratory.
Reaction Time - extraction for 1.25 hours was used
since this allows adequate time for extraction without
excessive dissolution or degradation of the coal,
Solvent Ratio - p-cresol was identified as the most
effective solvent for experimentation on removal of
organic sulfur from coal. A ratio of 1:4 w/v was effec-
tive and desirable from a laboratory standpoint,
Reaction Temperature - a reaction temperature of 180-200°C
was used for sulfur removal. Since water in the coal can
drastically lower the reflux temperature of p-cresol, the
coal was dried under vacuum at 120°C before use.
t Post Sample Treatment - after extraction, the samples were
filtered, washed with fresh p-cresol, and then dried. All
calculations were performed on a dry basis in order to
eliminate variables from wetness of coal. Sulfur forms
and proximate analyses were obtained on each treated coal
sample.
ft Material Balance - a coal and sulfur material balance was
obtained by weighing the coal before and after treatment
and recovering the dissolved solids from solution by dis-
tilling the cresol. The residue was analyzed to complete
the sulfur balance.
57
-------
4.5.2 Experimental Procedure
Seven survey program coals have been extracted in triplicate according
to the following procedure:
One hundred grams of coal were dried in a vacuum oven for 8 hours
at 120°C. The dried coal was then added to 400 ml p-cresol at 195°C.
The mixture was refluxed for 1.25 hours. The reflux temperature was
185-202°C depending on the relative dryness of the coal, with most of
the runs being performed at >195°C. The mixture was filtered, washed
with 200 ml cold p-cresol and dried in a vacuum oven at ^1600C for
at least 36 hours. The extracts and all trap materials were then
combined for each set of triplicate runs. This solution, containing
dissolved coal and sulfur compounds, was then reduced to dryness by
vacuum distillation at 120°C. The extracts were then further dried
at ^160°C for at least 36 hours in a vacuum oven.
In order to insure that no sulfur compounds escape into the atmos-
phere, the exit gases from the reaction, vacuum distillation and filtration
flasks as well as the oven were passed through a dry ice-acetone (78°C) trap.
These traps were all checked for weight loss and evolution of volatile sul-
fur compounds. The results were negative in all cases. The material from
the traps used for the vacuum distillation and final oven drying of the
extracts is being saved for further analysis if warranted.
4.5.3 Organic Sulfur Extraction Results
The average starting and final sulfur forms and proximate analyses are
given in Tables 17 and 18. Because dissolving the organic matrix of the
coal has the effect of raising the ash content of the undissolved coal (as
well as pyritic sulfur content) with the resulting dilution of the remaining
organic,sulfur, the organic sulfur values of the initial, final and extracted
coal were converted to dry mineral matter free values using the Parr
Formulae (ASTM Standard D388) and are listed in Table 19. These data show
the problems attendant with obtaining the organic sulfur content by the
difference between the total sulfur content and the sum of pyrite and sul-
fate contents. The inherent errors of the individual determinations and
errors introduced during handling operations, together with those arising
from calculations involving differences, tend to obscure the validity of the
data. For these reasons, more meaningful data would be obtained if a
direct organic sulfur content analysis method were available.
58
-------
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60
-------
The results presented in Table 19 show that there is little or no
statistically significant organic sulfur removal, and in one case (Orient
No.6 coal) there is an organic sulfur gain. The conclusion that little
organic sulfur is extracted is substantiated from the measurement of the
sulfur content of the p-cresol extract and its relationship to the weight
of coal in the extract. As shown in Table 19 the sulfur content of the
extract is nearly identical to the initial coal sulfur content, which
indicates that no selective extraction of sulfur was obtained. As a con-
sequence of this finding, further studies of selective organic sulfur
removal with p-cresol should be discontinued.
61
-------
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4.6 TRACE ELEMENTS IN COAL
The primary objective of the trace element analysis portion of this
program was to assess the effects that the Meyers Process for chemical
desulfurization of coal would have on the levels of trace elements in
various U.S. coals. The process for removing pyritic sulfur may well re-
move some of the trace elements which are present in many coals and which may
be emitted as air pollutants upon combustion.
Trace element distributions have only recently been determined for
a few coals. Table 20 shows trace element distributions on two coals
analyzed by the Illinois Geological Survey and indicates the approximate
levels and ranges of elements to be expected in coals. Since little work
had been reported on trace element analysis in coal, no well established
analytical methods were available at the start of this program,and, con-
sequently, new procedures had to be developed to meet the objectives of this
program.
4.6.1 Coal Composition
The following sections describe coal composition analysis methods
and procedure assessments.
The broadest classifications which can be applied to the overall
coal composition are mineral matter, organic matter, and moisture. The
mineral matter normally comprises 5-40% of the coal composition. By far
the majority of the mineral matter in coal belongs to shale, kaolin, and
and sulfide groups which, when ashed, produce metal oxides of Si, Al, Fe, and
Ti, as well as oxides of the alkali and alkaline earth metals. These major
species, as well as Pp05> are economically determined for coal and coke ash
using ASTK 2795 procedures. Trace elements that were of interest in this
removal study included >Ag, As, B, Be, Cd, Cr, Cu, F, Li, Hg, Pb, Mn, Ni,Sb,
Se, Sn, V, and Zn.
-63-
-------
TABLE 20
REPORTED TRACE ELEMENTS DISTRIBUTION IN TWO COALS
Element
Hg
Sb
Mn
Ga
Se
As
Br
P
V
Be
Cu
Ni
Zn
Pb
Ge
Cr
Co
Cd
B
F
Sn
Mo
Ag
(Parts
IGS C-155668
0.49
8.9
90
7.5
1.2
93
10
29
15
2.9
25
60
213
183
35
4
23
0.9
115
(93) 46
<1.8
6.2
Per Million - PPM) h
NBS Coal
0.17
38
2.8
5.7
54
1.8
28
26
24
1.9
22
8.6
<0.4
43
80
9.6
<4
Illinois Geological Survey reference coal number C-15566.
National Bureau of Standards "standard" coal (see Appendix H).
-64-
-------
4.6.2 Methods for Trace Element Analysis
Several criteria are involved in the selection of appropriate trace
element analytical procedures. Of these, sensitivity, accuracy, precision
and selectivity are of primary importance. Scope, sampling and standards
requirements, cost of equipment and time for analysis are considerations
of great practical significance.
Sensitivity in analytical chemistry reflects the ability to discern
the difference between very small amounts of a substance. Detectability
refers to the smallest quantity of a substance which can be determined with
a specified degree of confidence. For the purposes of this program, the
required sensitivity of a trace determination is recommended to be around
a few ppm. In practical terms, this would represent an emission from a
100 ton/hr power plant of <0.5 Ib/hr.
In describing the analysis result, accuracy and precision are fre-
quently used rather loosely. Accuracy as normally refers to deviation of
the determined value from the true value. Precision refers to deviation
among determined values regardless of accuracy. Since the purpose of this
program was primarily to determine the effectiveness of the extraction
processes, an analytical precision of ±10% relative (a) was recommended
for the trace element determination. Since no standard methods were avail-
able for analyzing coal samples for trace elements, no level of accuracy
could be set. If there were a problem with the accuracy of the analytical
method used, the trouble or error would, hopefully, be systematic and have
no effect on the conclusions reached about the removal of the trace elements
from coal.
Of the several methods generally used for trace element analyses,
three fit the overall requirements of the proposed study. These were spect-
rophotometry and fluorometry, atomic emission and absorption spectroscopy
and instrumental neutron activation analysis. A comparison of these
methods is presented in Table 21, based upon the criteria established above.
In this table, a method was judged not applicable if it could not achieve
the stated precision, sensitivity and assumptions about accuracy or if the
analysis represented too high a cost. The information in Table 21 shows
that instrumental neutron activation analysis was applicable only to two
-65-
-------
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to
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66
-------
thirds of the elements of interest. In addition, the cost of this method was
judged higher than the other two methods. For these reasons, INAA was not
used.
In considering atomic emission or absorption spectroscopy and
spectrophotometric and fluorometric techniques, a careful approach to
sample preparation must be established. In both of these cases, the
element is actually determined in an aqueous solution. This necessitates
ashing or digesting the coal prior to analysis. The data presented in
Table22 clearly show the undesirability of high temperature ashing proce-
dures for sample preparation. The low temperature plasma ashing technique
was preferred by TRW for trace element analyses over chemical digestion;
however, both were studied in this program. In addition to the ashing
requirement, spectrophotometric and fluorometric techniques frequently
require liquid-liquid extractions of metal complexes to isolate the species
in question or to remove interferences. Since atomic absorption and
emission spectroscopy do not require such extractions, they were greatly
preferred for the analyses of aqueous solutions. Only for the analyses of
F, As, and B were the spectrophotometric and fluorometric techniques
considered competitive or technically required.
In the course of this program, ten group samples (including raw
coal, and the pyrite extraction product) were analyzed for the follow-
ing trace elements: Ag, As, B, Be, Cd, Cr, Cu, F, Hg, Li, Mn, Ni, Pb,
Sb, Se, Sn, V and Zn. The specific group samples analyzed were selected
by the EPA Project Officer. The criteria for selection of the analysis
procedures were:
1. a sensitivity of 1 ppm on a whole coal, dry weight basis
2. precision of +10% relative (a)
3. lowest cost among equivalent methods
Based upon these criteria, all the trace analyses except these for As, B
and F were performed using atomic absorption spectroscopy. The elements
As, B and F were determined spectrophotometrically. Details of the pro-
cedures development and the methods finally adapted are presented in
Appendix H.
-67-
-------
TABLE 22
Trace Element Retention*
Element
Pb
Sn
Cu
Cd
Sb
Ba
Mn
Ni
Mo
Zn
Ti
Co
Cr
Low Temperature
Ashing
(100-120°C)
101%
95
98
92
99
97
99
97
98
96
95
96
112
Muffle Furnace
Ashing
(550°C)
46%
87
92
53
46
99
107
99
116
39
92
97
100
Wet
Ashing
97%
112
96
100
97
96
103
99
100
99
93
98
101
*Data from International Plasma Corporation.
-68-
-------
4.6.3 Discussion of Trace Element Analysis Results
The results of trace element analyses for 18 elements in ten coals
before and after treatment by the Meyers Process are presented in Appendix H,
Tables H-4 through H-13. A summary of the trace element levels in the un-
treated coals appears in Table 23. All analyses were run in triplicate on
both untreated and treated coals in order to get a good estimate of precision
of the results and a reliable estimate of the trace element removal. These
analyses were run on three separate samples of untreated coal in order that
all sources of error such as sampling, ashing, dissolution, handling and
final analysis would be included in the final precision estimate. In a
similar manner, three separately extracted coal samples were each analyzed
once for the composition of the treated coal.
Up to eleven sets of calculated standard deviations (a) for each ele-
ment in the untreated coal (a total of 18 groups) were used to calculate a
pooled standard deviation (s) for each element. The same was done for the
treated coal. The pooled standard deviation is calculated as follows:
c -
a = standard deviation for a given set of analyses
4> = number of analyses in a given set
The results of these calculations are given in Table 24 and show that on
both an individual and an average basis, the results for the treated coal
are only slightly less precise and in some cases much more precise than
those on the untreated coal. Thus, the manipulation required in coal leaching
apparently either did not introduce significant contamination or was intro-
ducing contamination in a fairly uniform way. Since both sets of data were
similar, they were used to calculate a pooled standard deviation for the
analysis of each element. These values are probably a more reliable
estimate of the error associated with each analysis.
The final column in Table 24 lists the average of all values used in the
error analysis. Because these values are a combination of results of extrac-
ted and unextracted coals and because values below the detection limits were
not used, these numbers do not represent average levels of trace element in
the coals studied.
69
-------
Examination of the data in Table 23 shows that 7 of the 18 elements in
this study occurred in the coals at levels which may be of minimal environ-
mental significance from coal combustion facilities. The elements which oc-
curred at levels less than 3 ppm are: Ag, Be, Cd, Hg, Sb, Se and Sn. In
keeping with the low levels at which these elements were present, the % rel-
ative deviations of these analyses were generally high: Ag ±68%, Be ±27%,
Cd ±44%, Hg ±27%, Sb ±91%, Se ±67%. For Sn no coal showed any value above the
2.5 ppm detection limit. Although no general conclusion can be made as to
the removal of these elements by the Meyers Process, several showed some
promise in cases where they were present in significant amounts. Particularly
noteworthy is Se which was found in four coals at levels of 17, 5, 5 and
4 ppm and in each case was removed to less than the analysis limit of 2.5 ppm.
Evidence also shows that when Be is present at levels greater than 1 ppm
significant reductions could be obtained through application of the Meyers
Process.
Five of the remaining elements - As, B, Cu, Li and Pb - were generally
present in the range of 3-30 ppm while the remaining six - Cr, F, Mn, Ni, V
and Zn - were generally above 30 ppm. The analytical precision of these
eleven elements, while not as good as had been hoped, was generally acceptable:
As ±15%, B ±12%, Cr ±5%, Cu ±11%, F ±14%, Li ± 10%, Mn ±9%, Ni ±13%, Pb ±44%,
V ±25%, Zn ±8%. Notable exception are V and Pb for which unaccebtably high
scatter was obtained. For these two elements several coals (5 for V and
4 for Pb) showed apparent increases after extraction, further indicating
unidentified difficulties in the analyses. The problem with V is believed
to be interelement interferences. The problem with Pb analysis is not now
known.
A summary of trace element removals is presented in Table 25. Examina-
tion of the removal efficiency data indicates that As, Mn and Zn are effec-
tively removed in all or nearly all of the coals studied. On the other hand,
B, Cu and F showed insignificant levels of removal except for specific coals.
The maximum removals for these three elements are: F-44%, B-87% and Cu-100%.
Whether the occasional high values for B and Cu represent real differences
in the mineral form present or simply anomalous data cannot be determined
from the present study. The elements Cr and Ni generally showed good re-
moval efficiencies with some unaccountable data. The data for Li showed
70
-------
TABLE 23
TRACE ELEMENT COMPOSITION OF UNTREATED COALS
(PARTS PER MILLION, PPM)
Element
Ag
As
B
Be
Cd
Cr
Cu
F
Hg
Li
Mn
Ni
Pb
Sb
Se
Sn
V
Zn
WESTERN COALS
J, 0-
* t.
<0.1 <0.1
0.4 <0.01
11 35
<0.5 0.5
0.6 <0.5
<0.5 <0.5
27.3 8
47.9 29
0.22 0.20
<0.3 4
48 87
61 31
3 3
2 1
5 ' <2.5
<2.5 <2.5
1 103
49 9
EASTERN INTERIOR COAL BASIN
~ ^ 3
o 5
Z Z 01
£ i
"5> " i-
- £ 5
<0.1 <0.1 8.
6.6 15.2 5.7
30 43 272
0.5 6 1.5
0.5 0.7 0.8
126 74 122
18 36 17
151 105 215
0.16 0.12 0.16
4 23 10.5
86 57 98
136 53 27
29 0.5 25
1 <1 <1
4 5 <2.5
<2.5 <2.5 <2.5
64 69 105
215 25 97
APPALACHIAN COAL BASIN
"-> a?1- "o W
0. * !- £ r-
$S* 1 8 1 |S
-3 U. 3 ;£
4. 2. <0.1 4. 0.5
22.2 28.9 23.5 12.9 9.1
34 27 16 20 26
0.7 0.8 2.0 1 0.4
<0.5 <0.5 <0.5 <0.5 <0.5
55 55 94 81 26
26 35 25 24 16
68 122 93.5 251 78.5
0.31 0.11 0.07 0.14 0.06
26 38 4 76 13
41 46 24 31 31
41 33 147 44 17
15 25 5 16 7
<1 <1 <1 <1 <1
<2.5 <2.5 17 <2.5 <2.5
<2.5 <2.5 <2.5 <2.5 <2.5
02 147 94 78 77
31 34 105 55 18
71
-------
TABLE 24
POOLED STANDARD DEVIATIONS
(PARTS PER MILLIOM, PPM)
Element
Ag
As
B
Be
Cd
Cr
Cu
F
Hg
Li
Mn
Ni
Pb
Sb
Se
Sn
V
Zn
s Untreateda(n)b
2.01 (5)
2.29 (11)
7.65 (12)
0.49 (9)
0.36 (11)
3.03 (10)
2.52 (12)
12.15 (11)
0.036 (12)
2.73 (11)
5.56 (12)
7.96 (12)
4.05 (11)
1.18 (3)
5.91 (5)
-
19.80 (12)
5.26 (12)
s Treated9 (n)
2.50 (6)
1.01 (8)
1.69 (9)
0.19 (6)
0.30 (2)
4.10 (9)
2.76 (9)
23.94 (9)
0.054 (9)
1.37 (10)
3.04 (10)
5.48 (9)
6.53 (9)
-
1.15 (2)
-
20.47 (9)
6.06 (10)
s Total9
2.30
1.88
5.89
0.40
0.35
3.58
2.62
18.41
0.045
2.19
4.58
7.01
5.31
1.18
5.03
-
20.10
5.64
Average0
3.4
12.8
48.7
1.5
0.8
74.2
23.1
128.1
0.17
22.7
53.4
55.9
12.1
1.3
7.5
-
79.4
72.7
Untreated = raw coal; treated = extracted coal; total = all sets of data
from treated and untreated coal .
Number of sets of data included, includes data from NBS coal analysis.
Average of all numbers used for calculation; "less than" values were
not used.
72
-------
TABLE 25
TRACE ELEMENT REMOVAL
(* W/W)
Element
Ag
As
B
Be
Cd
Cr
Cu
F
Hg
Li
Mn
Ni
Pb
Sb
Se
Sn
V
Zn
WESTERN
COALS
&.
>> Q-
a: -r-
i-
(U +J
t/i
'o! "o
CD O
Inda Ind
N.D.b Ind
N.D. 86+2
Ind Ind
Ind Ind
Gain Gain
19+7 Gain
44+9 N.D.
41+7 N.D.
Gain Gain
92+25 93+3
89+6 58+5'
Gain 93+11
Ind Ind
N.D. Ind
Ind Ind
Gain 93+11
95+1 N.D.
EASTERN INTERIOR
COAL BASIN
us
CM
O
O 2: ul
Z OOJ
u -z.
0) C t3
r- 0) O. C
Ol T- E (C
10 l_ «
UJ O O .
Gain Ind 50+33
90+17 88+3 82+9
N.D. 30+8 87+1
Ind 92+48 67+27
Ind 71+45 N.D.
71+5 23+6 45+30
Gain 100+11 N.D.
N.D. 14+2 N.D.
N.D. N.D. N.D.
Gain 78+3 90+7
77+7 89+1 0 96+3
65+10 Gain Gain
98+J Gain N.D.
Gain Ind Ind
N.D. N.D. Ind
Ind Ind Ind
N.D. N.D. N.D.
84+1 82+4 55+J8
APPALACHIAN COAL BASIN
1"
1o >>
y -* c\j -r- ^: r-
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CT> O *O O
-------
widely mixed results which are unexplained on the basis of either analysis
error or likely sources of contamination.
In summary, the trace element studies to date have shown that the
analysis procedures are generally acceptable with the exception of pro-
cedures for V and Pb. The studies also indicate that As, Be, Cr, Mn, Ni,
Se and Zn are amenable to removal by the Meyers Process in at least some
American coals. Seven elements - Ag, Be, Cd, Hg, Sb, Se and Sn - were not
generally present in the coals at levels exceeding 3 ppm. Three elements,
B, Cu and F, do not appear to be removed in significant amounts by the
Meyers Process.
74
-------
5.0 ACKNOWLEDGMENTS
The following TRW personnel deserve acknowledgment: W.P. Kendrick
and D. Kilday for experimental assistance; E.A. Burns and R.J. Ottinger
for technical assistance; J.I. Blumenthal and B. Dubrow for managerial
assistance;and C.M. Yarden for report coordination.
The Program Manager for this study at the Systems Group of TRW Inc.,
was Robert A. Meyers and the monitoring Project Officer for this Environ-
mental Protection Agency contract was Lloyd Lorenzi, Jr. Appreciation is
expressed to Mr. Lorenzi for his guidance and encouragement. Messrs. I.
Foster and R. Kaplan of the Commercial Testing and Engineering Company
(Chicago, Illinois) deserve special recognition for their cooperation in
expediting coal sampling and analyses for TRW at CT&E.
75
-------
6.0 REFERENCES
1. Hamersma, J. W.,E. P. Koutsoukos, M. L. Kraft, R. A. Meyers,
G. J. Ogle, and L. J. Van Nice, "Chemical Desulfurization of
Coal: Report of Bench-Scale Developments", EPA R2-73-173, pre-
pared for the Office of Research and Monitoring of the
Environmental Protection Agency, Research Triangle Park, N. C.,
February, 1973.
2a. Youden, W. J., "Statistical Methods for Chemists," John Wiley &
Sons, New York, 1951, p. 119.
2b. Bauer, E. L., "A Statistical Manual for Chemists," Academic Press,
New York, 1971, p. 61.
3. Personal Communication and Technical Literature, International
Plasma Corporation.
4. Furman, N. H.,Ed., "Scotts Standard Methods of Analysis," 6th ed.,
Vol. 1, D. Van Nostrand Co., Princeton, New Jersey, 1962.
5. Slaving, W.,"Chemical Analysis," Vol. 25, Interscience Publishers,
New York, 1968.
6. Anzino, E. E.and G. K. Billings, "Atomic Absorption in Geology,"
Elseiver Publishing Co., New York, 1967.
7. Ruch, R. R., H. J. Gluskoter, and N. F. Shimp, "Occurrence and
Distribution of Potentially Volative Trace Elements in Coal."
Illinois Geological Survey, EPA Contract 68-02-0246, Personal
Communication with H. J. Gluskoter.
8. Medlin.J. H., N. H. Suki, J. B. Bodkin, "Atomic Absorption
Newsletter," Vol. 8, No. 2, 1972.
9. U. S. Bureau of Mines Report No. 7184, "Colorimetric Method for
Arsenic in Coal," October, 1968.
10. Fisher Technical Paper TD142, "Reagant of Choice for Arsenic,"
November, 1960.
11. Main, J. M., Anal. Chem., Vol. 44, 2015, 1972.
76
-------
7.0 GLOSSARY OF ABBREVIATIONS AND SYMBOLS
Abbreviations
Abs
ASTM
btu
cal
eq
Exp.
Kcal
ml
ppm
Rxn.
wt
Symbols
C
A
P
H
mM
N_
P
R
Sl
S
absolute
American Society for Testing and Materials
British Thermal Unit
calories
equation
experiment
kilocalories
mil liliter
parts per million
reaction
weight
concentration.
difference in quantity following delta.
micron.
molarity.
millimole.
normality.
total pressure, atmospheres.
gas constant, cal/mole, °K.
sulfur.
elemental sulfur.
organic sulfur.
pyritic sulfur.
total sulfur.
sulfate.
77
-------
Symbols (cont'd)
a standard deviation.
T absolute temperature, °K.
t time, hours (leaching)-minutes (regeneration)
V volume.
W pyrite concentration in coal, wt%.
Y ferric ion to total iron ratio.
78
-------
8.0 UNIT CONVERSION TABLE
To Convert From
btu
feet
gallons
inches
ounces
pounds
pounds
temp (°F -32
tons
calories
meters
liters
centimeters
grams
grams
kilograms
temp (°C)
kilograms
Multiply By
252.0
0.3048
3.785
2.540
28.35
453.6
0.4536
0.5556
907.2
79
-------
9.0 APPENDICES
80
-------
APPENDICES
TABLE OF CONTENTS
APPENDIX A Seam Extent and Sample Location
APPENDIX B Ranking of Treated and Untreated Coals . . . .
APPENDIX C Untreated Coal Analysis Data
APPENDIX D Pyritic Sulfur Removal Data
APPENDIX E Washability Tables
APPENDIX F Organic Sulfur Removal Data
APPENDIX G Sieve Analysis Data
APPENDIX H Methods Development and Trace Element Analysis
Data. . . .
Page
85
108
122
127
132
166
169
171
81
-------
APPENDICES
FIGURES
Page
Maps - Seam Extent and Sample Location
A-l Pennsylvania - Sewickley Seam 86
A-2 West Virginia - Sewickley Seam 87
A-3 Ohio - Sewickley Seam 88
A-4 Pennsylvania - Pittsburgh Seam 89
A-5 West Virginia - Pittsburgh Seam 90
A-6 Phio - Pittsburgh Seam 91
A-7 Pennsylvania - Lower Freeport Seam 92
A-8 West Virginia - Lower Freeport Seam 93
A-9 Ohio - Lower Freeport Seam 94
A-10 Pennsylvania - Upper Kittanning Seam 95
A-ll West Virginia - Upper Kittanning Seam 96
A-12 Ohio - Upper Kittanning Seam 97
A-13 Pennsylvania - Lower Kittanning Seam 98
A-14 West Virginia - Lower Kittanning Seam 99
A-15 Ohio - Lower Kittanning Seam 100
A-16 Eastern Kentucky - Mason Seam 101
A-17 Illinois - No.5 - Harrisburg-Springfield Seam 102
A-18 Indiana - Springfield - No.V Seam 103
A-19 Western Kentucky - No.9 Seam 104
A-20 Illinois - Herrin No.6 Seam 105
A-21 Western Kentucky - No. 11 Seam 106
A-22 Indiana - Hymera No.VI Seam 107
82
-------
APPENDICES
TABLES Page
B-l to B-3 Coal Ranking Data
B--1 Untreated Coal 109
B-2 Pyritic Sulfur Extractions 113
B-3 Organic Sulfur Extractions 117
B-4 Computer Program for Determining the Rank of
Coal. . 119
C-l to C-4 Untreated Coal Analyses
C-l Edna, Navajo, Belle Ayr and Colstrip Mines 123
C-2 Weldon, Eagle No.2, Orient No.6 and Camp
Nos.l&2 Mines 124
C-3 Walker, Egypt Valley Mo.21, No.l and
Jane No.l&2 Mines 125
C-4 Fox, Warwick and Humphrey No.7 Mines. . . 126
D-l to D-4 Pyritic Sulfur Removal Data
D-l Edna, Navajo, Belle Ayr and Colstrip Mines 128
D-2 Weldon, Eagle No.2, Orient No.6 and Camp
Nos.l&2 Mines 129
D-3 Egypt Valley No.21, No.l, Jane
and Fox Mines 130
D-4 Warwick and Humphrey No.7 Mines and
Lower Kittanning Coal 131
E-l to E-33 Washability Tables
E-l Eagle No.2 Mine - IV x 100 Mesh 133
E-2 Eagle No.2 Mine - 3/8" x 100 Mesh .... 134
E-3 Eagle No.2 Mine - 14 Mesh x 0 135
E-4 Orient No.6 Mine - IV x 100 Mesh .... 136
E-5 Orient No.6 Mine - 3/8" x 100 Mesh. ... 137
E-6 Orient No.6 Mine - 14 Mesh x 0 138
E-7 Camp Nos.l&2 Mines - IV x 100 Mesh ... 139
E-8 Camp Nos.l&2 Mines - 3/8" x 100 Mesh. . . 140
E-9 Camp Nos.l&2 Mines - 14 Mesh x 0 141
E-10 Weldon Mine - IV x 100 Mesh 142
E-ll Weldon Mine - 3/8" x 100 Mesh 143
E-12 Weldon Mine - 14 Mesh x 0 144
E-13 Walker Mine - IV x 100 Mesh 145
E-14 Walker Mine - 3/8" x 100 Mesh 146
E-15 Walker Mine - 14 Mesh x 0 147
E-16 Egypt Valley No.21 Mine - IV x 100 Mesh. 148
E-17 Egypt Valley No.21 Mine - 3/8" x 100 Mesh 149
E-18 Egypt Valley No.21 Mine - 14 Mesh x 0 . . 150
E-19 No.l Mine (Dixie Fuel Co.) - IV x 100 Mesh 151
E-20 No.l Mine (Dixie Fuel Co.)-3/8" x 100 Mesh 152
E-21 No.l Mine (Dixie Fuel Co.) - 14 Mesh x 0. 153
83
-------
APPENDICES
TABLES - continued
Page
E-22 Jane Mine - 1%" x TOO Mesh 154
E-23 Jane Mine - 3/8" x 100 Mesh 155
E-24 Jane Mine - 14 Mesh x 0 156
E-25 Fox Mine - 1%" x 100 Mesh 157
E-26 Fox Mine - 3/8" x 100 Mesh 158
E-27 Fox Mine - 14 Mesh x 0 159
E-28 Warwick Mine - IV x 100 Mesh 160
E-29 Warwick Mine - 3/8" x 100 Mesh 161
E-30 Warwick Mine - 14 Mesh x 0 162
E-31 Humphrey No.7 Mine - 1%" x 100 Mesh 163
E-32 Humphrey No.7 Mine - 3/8" x 100 Mesh 164
E-33 Humphrey No.7 Mine - 14 Mesh x 0 165
F-l to F-2 Organic Sulfur Removal Data
F-l Eagle No.2, Camp Nos.l&2 and Orient No.6 Mines. . 167
F-2 Belle Ayr, Colstrip and Jane 168
G-l Sieve Analyses Data 170
H-l Atomic Absorption Background for Trace
Elemental Analysis 174
H-2 Atomic Absorption Analytical Parameters 176
H-3 to H-l3 Trace Element Analyses Data
H-3 NBS Standard Coal 182
H-4 Colstnp Mine 183
H-5 Eagle No.2 Mine 184
H-6 Orient No.6 Mine 185
H-7 Camp Nos.l&2 Mines 186
H-8 Egypt Valley No.21 Mine 187
H-9 Jane Mine 188
H-10 Fox Mine 189
H-ll Warwick Mine 190
H-12 Humphrey No.7 Mine 191
H-13 Belle Ayr Mine 192
84
-------
Appendix A
Seam Extent and Sample Location
85
-------
>- ^
GO <->
Q_ OO U_
86
-------
*<
LJJ
ZOO
o:
o
87
-------
OHIO
SEWICKLEYSEAM
FIGURE A-3
-------
«=r
-------
90
-------
\J
OHIO
PITTSBURGH SEAM
FIGURE A-6
-------
is g
uj O
Q I u_
92
-------
Lu oo
oi o; *
u_
> QL S-
<>"> ^ rS
93
-------
OHIO
LOWER FREEPORT SEAM
FIGURE A-9
94
-------
LLJ
1/1
:i!
i ^
LU
!£ i
jd- g
95
-------
00
O
pi o;
'1.4
96
-------
OHIO
UPPER KinANNING SEAM
FIGURE A-12
97
-------
;« 2
-
>- LU
oo &: Q:
z: w n
2 S o
LU O
Q. _J U.
98
-------
XD03NVH
oo
o
iS «
99
-------
OHIO
LOWER KITTANNIIMGSEAM
FIGURE A-15
100
-------
a; z LU
£03=
101
-------
ILLINOIS
N0.5- HARRISBURG - SPRINGFIELD SEAM
FIGURE A-17
102
-------
INDIANA
SPRINGFIELD - NO.I SEAM
FIGURE A-18
103
-------
; UJ
; OO UJ
O- ^
L- 5
104
-------
ILLINOIS
HERRINNO 6 SEAM
FIGURE A-20
105
-------
CM
<
106
-------
INDIANA
HYMERA - NO.YE SEAM
FIGURE NO. A-22>
107
-------
Appendix B
Ranking of Treated and Untreated Coals
108
-------
Table B-l
Coal Ranking Data-Untreated Coal
EDNO-UNTREOTED
MDISTUPE= 8.41*. MDISTBTU= 11£16
.:.ULFUP= .75--:!. RSH= 9.13'., ETU= 12246
FIXED I:RPBDN= 50.22*. VDLRTILE MRTTEP= 40.65:-;
DRY MINEPRL HOTTER FPEE FIXED CRPBON= 55.84*
DRY MIMERRL MRTTER FPEE VDLRTILE MRTTER= 44.16'
DRY MINEPRL MRTTEP FPEE BTU= 13602
MDIST MINERRL MRTTER FPEE BTU= 12458
EPR STRNDRRD-* :iULFUP= .73*
PflNK =
CLRSS 11-5.' BITUMINDUS-HIGH VDLRTILE C
HRVRJD-UNTPERTED
MDISTUPE=11 . 07*? MDISTBTU= 8937
ruLFUP= .si'.< R-:H= 25.2?** BTU= 10050
FIXED CflRBDh= 39.20*. VDLRTILE MRTTEP= 35.51*
DRY MINEPRL HOTTER FPEE FIXED CRPBDM= 54.09*
DPY MINERfiL HOTTER FPEE VDLRTILE MRTTER= 45.91'
DRY MINEROL MRTTEP FPEE ETU= 13849
MOIST MINEROL MRTTEP FPEE BTU= 12316
EFR STRNDRPD-* SULFUP= .60*
RONK=
CLOSG 11-51. BITUMINDUS-HIGH VDLRTILE C
BELLE RYP-UNTPERTED
MDISTURE=19.14*. MDISTBTU= 9731
3ULFUR= .76*. OSH= 7.55*- BTU= 12034
FIXED CRPBDN= 45.34*. VDLRTILE MRTTEP= 47.11*
DPY MINEPOL MRTTEP FPEE FIXED CRPBDN= 49.47*
DPY MINERflL MRTTEP FPEE VDLRTILE HOTTER* 50.53*
DPY MINEROL MRTTEP FPEE BTU= 13111
MDIST MINEROL MRTTEP FPEE BTU= 10601
EPR STRNDRPD-* SULFUR* .72*
PRNK =
CLR::S 11-5- BITUMINDUS-HIGH VDLRTILE C-OGGLDMEROTING
CLRSS III-l'SUBEITUHINDUS R.NDhflGGLDHEROTING
109
-------
COLSTPIP-UNTRERTED
MDIiTURE=20.41'-;, MOISTBTU= 9225
SULFUP= l.Gi:;, RSH= 10.38:-., BTU= 11591
FIXED CRPBDN= 46.53';. VDLRTILE MRTTER= 43.09'.
DRY MINEPflL MRTTEP FREE FIXED CRPEDN= 52.56M
DRY MINERflL MRTTER FREE VDLflTILE MRTTER= 47.44:
DRY MINEPflL MRTTEP FREE BTU= 13065
MOIST MIHEPRL MRTTER FREE BTU= 10398
EFR STRNDRPD-': SULFUP= .70'.
PflMK =
CLflSS- 111-2, SUBBITUMIMOUS E
WELDDN-UNTREfiTED
MDI::TURE=13.29';, MOISTBTU= 10197
:ULFUR= 6.39':. RCH= 15.74.'-.. ETU= 11760
FIXED CflPBDM= 43.64'., VDLflTILE MRTTEP= 40.6£\
DRY MIMERRL MfiTTEP FREE FIXED CflPBDM= 53.70V.
DRY MIHEPflL MRTTER FREE VDLRTILE MRTTER= 46.30'i
DRY MINEPflL MRTTER FREE ETU= 14331
MDIST MINERRL MRTTEP FREE BTU= 12427
EPR STflhDRRD-'. 'SULFUP= .71?.
PflNK =
CLflSS II-5> BITUMINDUS-HIGH VDLRTILE C
ERGLE ND.d-UNTPERTED
MDISTURE= 3.31';- MDISTBTU= 10216
SULFUR= 4.29;.» flSH= 26.53'., BTU= 10566
FIXED CflRBDN= 39.17'-;, VDLRTILE MRTTER= 34.30V.
DRY MINERRL MRTTER FREE FIXED CRPBDN= 55.85V.
DRY MINEPflL MfiTTER FREE VDLRTILE MRTTEP= 44. IS
DRV MINERRL MRTTEP FREE BTU= 14994
MOIST MINEPRL MRTTEP FREE BTU= 14498
EPR STflNDflPD-V. CULFUP= .63'.
PflNK =
CLRSC I 1-3, BITUMINDUS-HIGH VDLRTILE R
DP IENT NO.6-UNTPERTED
MDISTUPE= 3.51'., MOISTBTU= 10771
SULFUR= 1.66'., fl.I'H= 22.51:;. BTU= 11163
FIXED CRPBDN= 45.82'., VDLRTILE MRTTEP= 31.67'.
DRY MINERRL MRTTEP FREE FIXED CRRBDN= 60.94';
DRY MINEPRL MRTTEP FREE VDLRTILE MRTTEP= 39.06'
DRY MINEPRL MRTTEP FREE BTU= 14814
MDIST MINEPRL MRTTER FREE ETU= 14294
EPR STRNDflPD-'; SULFUP= .67:.
PRNK=
CLflSS 11-3. BITUMINOUS-HIGH VDLflTILE R
110
-------
CRMP NOS.1&.2-UNTPERTED
MDISTURE= 3.99;;, MQISTBTU= 10662
:::ULFUR= 4.51V., flSH= £1.13?: > BTU= 11105
FIXED C.flRBON= 43.01V.» VDLRTILE MRTTER= 35.86';
DRY MINEPflL MflTTER FREE FIXED CflRBOM= 56.67?;
DRY MINERflL MflTTEP FREE VOLATILE MflTTER= 43.33:
DRY MINERflL MflTTEP FREE BTU= 14552
MOIST MINERflL MfiTTEP FREE BTU= 13971
EPfl STflNDflRB-?; SULFLIR= -67V.
PflNK=
CLflSS 11-4, ElTUMINOUS-HIGH VOLRTILE E
l.lflLKER-UNTRERTED
MDISTURE= £.07V., MOISTBTU= 12341
SULFLIR= .71?;, RSH= 16.67V., ETU= 12602
FIXED C:fiRBON= 64.44V., VOLRTILE MRTTER= 18.89';
DRY MINERflL MRTTER FREE FIXED CflPBDN= 78.83';
DRY MIMERflL MflTTER FREE VDLflTILE MRTTER= £1.171
DRY MIMERflL MflTTER FREE BTU= 15398
MOIST MINEPRL MflTTEP FREE BTU= 15079
EPR STflhDRRD-'; SULFUP= .76V.
RflhK=
CLflSS ll-l- EITLIMIMOUS-LOW VOLRTILE
EGYPT VfiLLEY HO.21-UMTPEftTED
MDISTURE= 2.07:-;. MQISTBTU= 10375
SULFUR= 6.55;'.' RSH= 25.29:-;» BTU= 10594
FIXED CflRBDM= 38.59'-.« VOLRTILE MflTTEP= 36.12?:
DRY MIMERflL MflTTER FREE FIXED CflPEOM= 54.44:-;
DRY MINERflL MflTTEP FREE VOLRTILE MflTTER= 45.56?;
DRY MIMEPflL MflTTEP FREE BTU= 14851
MOIST MINEPflL MflTTEP FREE BTU= 14543
EPfl STflMDflRD-V. SULFUR= .64>.
PflHK =
CLflSS 11-3, BITUMINOUS-HIGH VDLflTILE fl
HO.1 -DIXIE FUEL >-UNTPEflTED
MOISTURE= 2.22?;? MOISTBTU= 12764
SULFUP= 3.12V., RSH= 11.39'., ETU= 13054
FIXED CflRBDh= 49.70?;, VOLRTILE MflTTEP= 38.91?;
DRY MINEPflL MftTTEP FREE FIXED CflPBOM= 57.26?.
DRY MINEPflL MflTTEP FREE VOLflTILE MflTTER= 42.74-'
DRY MINERflL MflTTEP FREE BTU= 14997
MOIST MINERflL MflTTER FREE BTU= 14664
EPfl STRNDflRB-?; SULFUP= .78?;
RflMK=
CLflSS 11-3, ElTUMINOUS-HIGH VDLflTILE fl
111
-------
JRNE-UNTRERTED
MDISTURE= 1.17*. MOISTBTU= 11792
SULFUR= 1.35*. RSH= 21.75*. BTLI= 11932
FIXED CRPBDN= 48.18':* VDLRTILE MRTTER= 30.07*
DRY MIMERRL MRTTEP FREE FIXED CRRBDM- 63.45*
DRY MINEPflL MflTTER FREE VDLRTILE MRTTER= 36.55*
DRY MINERflL MRTTER FREE BTU= 15682
MDIS.T MINEPflL HOTTER FREE ETU= 15498
EPR STRNDRRD-* SULFUR= .72'.
RRNK =
CLflSS 11-3. BITUMINOUS-HIGH VDLRTILE R
FDX-UNTRERTED
MDISTURE= l.S3':i. MDISTBTU= 12736
.:ULFUP= 3.83\» RiH= 13.55'x.P BTU= 12973
FIXED CRRBDM= 48.1SV., VDLRTILE MRTTEP= 38.33*
DRY MINERRL MRTTEP FREE FIXED CRRED«= 57.11*
DRY MlhERRL MRTTER FREE VDLflTILE MRTTER= 42.8'i
DRY MINEPflL MRTTER FREE BTU= 15347
MDIST MIMERRL MRTTER FREE BTU= 15066
EPR STfiMDflRD-* SULFUP= .78*
PflMK=
CLflGS II-3i BITUMIhDUS-HIGH VDLRTILE R
UflPHICK-UNTREflTED
MDISTURE= 1.50*> MDISTBTU= 8483
SULFUR= 1.37*;. RiH= 40.47*» ETU= S612
FIXED CHRBDM= 31.76** VDLRTILE MRTTER= 27.77*
DPY MIMERRL MRTTEP FREE FIXED CRREDh= 56.82*
DRY MlhEPRL MRTTEP FREE VDLRTILE MRTTER= 43.18:
DRY MIMERRL MRTTER FREE BTU* 15381
MDIST MINERflL MRTTER FREE BTU= 15150
EPR STRNDRRD-* SULFUR= .52'-.
PRNK=
CLflSS I I-3« BITUMINDUS-HIGH VDLRTILE R
HUMPHREY NC .7-UMTPERTED
MOISTURE* 1.63** MDISTBTU= 13409
SULFUR= £.58*» RSH= 9.88*1. BTU= 13631
FIXED CRPBON= 52.46*. VDLRTILE MRTTER= 37.66*
DPY MINEPflL MRTTEP FREE FIXED LRPBON= 59.23*
DRY MINERflL MflTTEP FREE VOLRTILE MRTTER= 40.77'
DPY MINEPRL MRTTER FREE ETU= 15356
MDIST MINERRL MRTTER FREE ETU= 15106
EPR STRNDflRD-* SULFUR= .82*
PflNK=
CLflSS 11-35 BITUMINDUS-HIGH VDLRTILE fl
112
-------
Table B-2
Coal Ranking Data-Pyritic Sulfur Extractions
EDNfi-TFEfiTED
MOISTUPE= 8.41'-. - MOISTBTU= 11175
SULFUP= 1.14':^ RSH= 6.77*. BTU= 12201
FIXED CflRBDN= 50.88?;. VDLRTILE MRTTEP= 42.35';
DRY MINEPRL MRTTER FREE FIXED CRRBON= 55.08:-;
DRY MINEPRL MRTTER FREE VDLRTILE MRTTER= 44.92:-;
DRY MINEPRL MflTTER FREE BTU<= 13136
MOIST MINERRL MRTTER FREE BTU= IE077
EF'R STRNDRPD---: SULFUR= .73';
RRNK=
CLflSS 11-5 i El TUMINOUS-HIGH VDLRTILE C
MRVR.JD-TPERTED
MDISTUPE=11 .f\7':< MDISTBTU= 89£4
G:IJLFUR= .76^» RSH= 20.53'.» ETU= 10035
FIXED CRPBOM= 43.65'^ VDLRTILE MRTTEP= 35.8£':
DRY MIMEPRL MRTTER FREE FIXED CRPBDM= 56.E4X
DRY MINERRL MRTTER FREE VDLfiTILE MRTTEP= 43.76'.
DRY MIMEPRL MRTTER FREE BTU= 1,2908
MOIST MINERRL MRTTER FREE ETU= 11479
EPR STRNDRRH-'; SULFUR* .60'.
PRNK=
CLflSS 11-5. BITUMINOUS-HIGH VDLRTILE C i-RGGLDMERRTING
CLRSS III-l vi.UBBITUMINDUS R i-NONRGGLDMERRTING
BELLE RYR-TPERTED
MDISTUPE=19.14Ji» MDISTBTU= 9315
SULFUR= .8£V., RSH= 3.37?., BTU= 11520
FIXED CRRBDN= 49.61';- VDLRTILE MRTTER= 47 . 0£\
DRY MINERRL MRTTER FREE FIXED CRRBDN= 51.60?:
DRY MINEPRL MRTTEP FREE VOLRTILE MRTTER= 48.40:-;
DRY MINEPRL MRTTEP FREE BTU* 11958
MOIST MINEPRL MRTTEP FREE BTU= 9670
EPR STRNDRRD-x. SULFUP= .69?;
RRNK=
CLflSS III-£» SUBBITUMINDUS B
113
-------
COLSTPIF-TRERTED
MDISTURE=£0.41*. MDISTBTU= 9010
SULFUR= .69*> RSH= 5.17*. BTU= 113E1
FIXED CflRBDN* 52.38*. VDLflTILE MRTTER= 42.45*
DRY MIHERRL MflTTEP FREE FIXED CRPEGM= 55.59V.
DRY MIMERflL MRTTER FREE VGLflTILE MflTTER= 44.41';
DRY MINEPflL MRTTER FREE BTU= 11993
MDIST MIMERRL MRTTEP FREE BTU= 9545
EPR STRMDRRD-* SULFUR= .68'.
PRMK.=
CLflSS 111-2. SUBBITUMINDUS B
I..IELDDM-TRERTED
MDI STURE= 13 . £91: MO I STETU= 1 0833
TULFUR= £.34:.'* RSH= 6.43'^ BTU= 12493
FIXED CRREGM= 54.96V.* VDLRTILE MRTTER= 38.61.'.
DRY MIMEPRL MRTTER FREE FIXED CflRBDN= 59.51V.
DRY MIMERRL MRTTER FREE VDLflTILE MRTTER= 40.49*
DRY MIMERRL MRTTEP FREE BTU= 13467
MDIST MIMERRL MflTTEP. FREE BTU= 11677
EPR STRMDRRD-'i SULFUR= .75?.
RRMK=
CLflSS 11-5' BITUMINDUS-HIGH VDLRTILE C
ERGLE MD.£-TREflTED
MDISTURE= 3.31'.» MQISTBTU= 11 0£4
SULFUR= £.!£*» RSH= 19.80*» BTU= 11401
FIXED CRRBDM= 45.70V., VDLRTILE MRTTER= 34.50*
DRY MIMEPRL MflTTER FREE FIXED CRRBnN= 58.60*
DRY MINEPRL MRTTER FREE VDLflTILE MRTTER= 41.40*
DRY MINEPRL MRTTER FREE ETU= 14579
MDIST MIMERRL MRTTEP FREE BTU= 14096
EPR STflMDflRD-* SULFUR* .68'.
PRMK=
CLflSS II-3» BITUMIMCUS-HIGH VDLRTILE R
DRIEMT ND.6-TPEflTED
MDISTURE= 3.51*> MDISTBTU= 10647
:i:ULFUR= 1.40*. RSH= 18.85*-. BTU= 11034
FIXED CflRBDM= 49.£3*» VDLRTILE MRTTEP= 31.93*
DRY MIMERRL MflTTEP FREE FIXED CRREDM= 62.15*
DRY MIMERRL MRTTER FREE VDLflTILE MflTTEP= 37.35*
DRY MIMEPRL MflTTEP FREE ETU= 13898
MDIST MIMERRL MflTTEP FREE BTU= 13410
EPfl STflMDRRD-* SULFUR* .66*
RRMK=
CLflSS II-4> BITUMIMDUS-HIGH VDLRTILE B
114
-------
CflMP MDS.l;i:2-TPEflTED
MQISTUPE= 3.99'. - MQISTBTU= 11£7£
:.IJLFUP= 2.77%:. R.:H= 15.77-.- ETU= 11740
FIXED CRPBDh= 47.78%. VDLfiTILE MRTTER= 36.45%
DRV MINERRL HOTTER FREE FIXED CRRBON= 58.16':
DRY MINERflL MflTTER FREE VDLflTILE MflTTEP= 41 .84'-;
DRV MIHERRL MRTTER FREE BTU= 14238
MOIST MIMERflL MflTTER FREE BTU= 13669
EPR STRNDRRD-% SULFUR= .70'.
PflNK=
CLRSG 11-4' BITUMINOUS-HIGH VDLRTILE B
EGYPT VOLLEY HO.21-TPEflTED
MDISTURE= £.07-;. MOISTBTU= 11268
SULFUR= 2.89'.- RSH= 18.86%. BTU= 11506
FIXED CRPBDN= 43.06V., VDLRTILE MflTTER= 38.08%
DRY MINEPRL MOTTER FREE FIXED CRRBOM= 54.62%
DRY MIMERflL MflTTER FREE VDLOTILE MOTTER= 45.38V.
DRY MIMERflL MflTTEP FREE BTU= 14554
MOIST MINEPRL MOTTEP FREE BTU= 14253
EPR STflMDflRD-% SULFUP= .6?V.
RRMK=
CLflSS 11-3? BITUMIMDUS-HIGH VOLATILE fl
ND . 1 ( DIXIE FUEL !: -TPEOTED
MOISTURE= 2.22%j MDISTBTU= 13045
SULFUR= 1.62%. RSH= 8.50%» BTU= 13341
FIXED CRPBDM= 53.87%. VOLRTILE MflTTER= 37.63%
DRY MINEPRL MflTTEP FREE FIXED CflPBON= 59.63%
DRY MIHERRL MflTTER FREE VOLRTILE MflTTER= 40.37%
DRY MIMERflL MflTTEP FREE BTU* 14743
MOIST MIMERflL MflTTER FREE BTU= 14416
EFfl STflhDRRD-% SULFUP= .80%
PflMK=
CLflSS 11-3' BITUMINDUS-HIGH VDLflTILE fl
JflME-TPEflTED
MDISTURE= 1.17%. MOISTBTU= 12272
SULFUP= .67%. RSH= 17.99%. BTU= 12417
FIXED CRPBON= 51.65%. VOLRTILE MflTTEP= 30.36%
DRY MIMEPRL MflTTER FREE FIXED CflRBDM= 64.27%
DRY MIMEPRL MflTTEP FREE VDLflTILE MflTTEP= 35.73:
DRY MIMEPflL MflTTER FREE BTU= 15440
MOIST MIMERflL MflTTER FREE BTU= 15259
EPfl STflMDflPD-% SULFUP= .75%
RflNK=
CLflSS 11-3. BITUMINOUS-HIGH VOLRTILE fl
1T5
-------
FDX-TRERTED
MOISTURE* 1.83V., MOISTBTU* 12933
SULFUR* 1.645i» flSH*
FIXED CflPBDN= 51.97%, VDLRTILE MRTTER= 38.31";
DRY MINERflL MftTTER FREE FIXED CflPBDN= 58.38*
DRY MINEPflL MftTTER FREE VDLflTILE MflTTER= 41 .62';
DRY MINERRL MftTTER FREE BTU= 14775
MDIST MINERflL MftTTER FREE BTU= 14504
EPft STRNDftRD-'/. SULFUR* .795:
RflMK*
CLflSS II-3» BITUMIMDUS-HI6H VDLRTILE R
I..IRRWICK-TRERTED
MOISTURE* 1.5Q5J» MOISTBTU* 9225
SULFUR* .82^.» flSH* 35.325:» BTU* 9365
FIXED CRPBDN= 38.07V., VDLRTILE MRTTER= 126.61'.
DRY MINERflL MRTTER FREE FIXED CflRBOH* 61 .80';
DRY MIMERftL MRTTEP FREE VDLRTILE MRTTER= 38.20V.
DRY MINERflL MflTTER FREE BTU* 15184
MDIST MINERflL MflTTER FREE BTU= 14956
EPfl STflNDflRD--; SULFUR* .565-.
RflMK*
CLflSS II-3J EITUMINDUS-HIGH VDLRTILE R
HUMPHREY ND.7-TRERTED
MOISTURE* 1.635;, MOISTBTU* 13722
SULFUR* 1.495S, flSH* 6.97V., BTU* 13949
FIXED CflPBDM* 55.995s, VOLflTJLE MRTTEP= 37.04'.
DRY MINERflL MflTTER FREE FIXED CflRBDM* 60.85'i
DRY MINERflL MflTTER FREE VDLflTILE MftTTER= 39.155i
DRY MINERflL MflTTER FREE BTU* 15137
MDIST MINERflL MflTTER FREE BTU* 14890
EPfl STflNDflRD-* SULFUR* .84:.
RflMK*
CLflSS I 1-3, BITUMINOUS-HIGH VDLflTILE fl
116
-------
Table B-3
Coal Ranking Data-Organic Sulfur Extractions
ERGLE ND.2-TPEflTEB
MOISTURE= 3.31'; i. MDISTBTU= 9464
SULFUR= 4.165;, RSH= 30.585i» BTU= 9738
FIXED CflRBOh= 39.62** VDLRTILE MflTTER= 29.80:;
DRV MINEPflL MflTTER FREE FIXED CflRBDM- 60.29?;
DRY MINEPflL MflTTER FREE VDLflTILE MflTTER= 39.71";
DRY MINERflL MflTTER FREE BTU= 14799
MOIST MIMERRL MflTTER FREE ETU= 14309
EPfl STflNDflRD-5s SULFUR= .59Ji
PfiNK=
CLflSS II-3» BITUMIMDUS-HIGH VDLRTILE R
CRMP NOS.1k£-TREflTED
MDISTURE= 3.99.'-.. MDISTBTU= 10078
SULFUR= 5.185i» RSH= E5.665SP BTU= 10497
FIXED CflRBOh= 41.115i» VDLftTILE MflTTER= 33.£3Ji
DRY MINERflL MflTTER FREE FIXED CftRBDH- 58.085S
DRY MIMERflL MflTTER FREE VOLflTILE MflTTER= 41.92'.
DRY MIMEPflL MflTTER FREE BTU= 14729
MDIST MIMERflL MflTTER FREE BT(J= 14141
EPfl STflNDflRD-*". SULFUR* .63*
RflMK=
CLflSS II-3» BITUMINOUS-HIGH VOLflTILE fl
ORIENT N0.6-TRERTED
MDISTURE= 3.515i» MOISTBTU= 10287
SULFUR= 1.83''., RSH= 24.55:-., BTU= 10661
FIXED CRRBON= 45.25'ij VDLflTILE MfiTTEP= 30.£05j
DRY MINERflL MflTTER FREE FIXED CflRBDN*= 62.05';
DRY MINEPflL MflTTER FREE VDLfiTILE MflTTER= 37.95>.
DRY MINERflL MflTTER FREE BTU= 14578
MOIST MINERflL MflTTER FREE BTU= 14066
EPfl STflNDflRD-'-. SULFUR= .64'.
RflNK=
CLflSS 11-3!. BITUMINOUS-HIGH VOLflTILE fl
lt7
-------
BELLE flYR-TRERTEB
MDISTURE=19.14*> MDISTBTU= 9667
SULFUR= .79*!- flSH= 7.78*» BTU= 11955
FIXED CflRBDM= 45.48*!- VDLflTILE MflTTER= 46.74V.
DRY MINERflL MflTTER FREE FIXED CflRBDN= 49.76*
DRY MINERflL MflTTEP FREE VDLRTILE MflTTER= 50.24*
DRY MINEPflL MRTTER FREE BTU= 13060
(ID 1ST MINERflL MRTTER FREE BTU= 10561
EPfl STflNDflRD-* SULFUP= .72*
RflNK=
CLflSS 11-5, BITUMINOUS-HIGH VOLRTILE CjflGGLDMERflTING
CLflSS III-lvSUBBITUMINDUS fl>NDNflGGLDMERflTIN6
FDX-TPERTED
MDISTUPE= 1.83*. MDISTBTU= 12025
SULFUR= 4.13*!- flSH= 16.49V., ETU= 1
FIXED CflRBDM* 48.62V., VDLflTILE MRTTER= 34. 89*
DRY MINERflL MflTTER FREE FIXED CRRBG«= 60.06V.
DRY MIMEP.RL MRTTER FREE VDLflTILE MRTTER= 39.94V.
DRY MIMERRL MflTTEP FREE BTU= 15064
MDIST MINERflL MflTTER FREE BTU= 14788
EPR STflMDRPD-V. SULFUR= .73;-;
CLflSS 1 1-3 i BITUMIMOUS-HIGH VDLflTILE fl
CDLSTRIP-TREflTED
MDISTIJPE=£0.4r". i. MDISTBTU= 9053
SULFUR= .90'.' RSH= 10.28*. BTU= 11374
FIXED CRPBDM= 49.09*, VDLRTILE MRTTER= 40.63*
DRY MINERflL MflTTER FREE FIXED CflREDN= 55.33*
DRY MIMERflL MflTTER FREE VDLflTILE MflTTER* 44.62*
DRY MINERflL MflTTEP FREE BTU= 12802
MDIST MINERflL MflTTEP FREE BTU= 10189
EPfl STRNDflPD-* SULFUP= .68*
RflNK=
CLflSS Ill-d. SUBBITUMINDUS B
JflNE-TPEflTED
MDISTURE= 1 .17* * MDISTBTU= 1098 0
SULFUR= £.08*» flSH= £5.48*. BTU= 11110
FIXED CflPBDN= 46.81*!. VDLflTILE MRTTEP= £7.71*
DRY MINERflL MflTTER FREE FIXED CflRBDN= 65.18*
DRY MINERflL MflTTER FREE VDLflTILE MflTTER= 34.82*
DRY MINERflL MflTTEP FREE BTU= 154£6
MDIST MINEPRL MflTTEP FREE BTU= 15£46
EPfl STflNDflRD-* SULFUR= .67*
RflNK=
CLflSS 11-3 - BITUMINDUS-HIGH VDLflTILE fl
118
-------
Table B-4
Computer Program for Determining
the Rank of Coal
VOLflTILE MRTTERi. flND MOISTURE*)
, 08*fiSH*0 .55+SULFUR) )
08+RSH+ 0 .55*SULFUP ) ) > » 1 0 0
PROGPRM RflNK < I NPUT .- OUTPUT ,TRPE6 )
C CLfiSSIFICRTIDN OF CDRLS EY RflNK
REWIND 6
PRINT 67
67 FDRMRT OPRINTOUT IS SRVED ON TRPE 6
1 PRINT 9
9 FDRMRT OINPUT CORL NRME DR NUMBER*)
RERD SjQjO'P'M
8 FORMRT CR8*R8»fi8.fi8>
PRINT £
2 FDRMRT f*INPUT SULFUR* RSHi- BTU.
RCCEPT SULFUR .RSH-.BTUD >VM .RMOIST
FC=IOO-'.:RSH+VM)
ETU=ETUD* <(100.-HMDIST)x100.)
DPVFC=< RMDIST^BTU
'.- 6 »3 > SULFUR ,RSH . BTUD»FC VM
f 6 H 4 ': DRYFC . DRYVM . DRYBTU > WETBTU
EPRSUL
00 ,
PR I NT
PRINT
WRITE
WRI TE
WRITE
WR I TE
WRITE
WRITE
WR I TE
FDRMRT
FORMRT
1* C
PRINT 4*
'.' 6
(6
<>
*>F5.2 «*:;. MOISTBTU=*»F6.0)
ULFUR=* >F5 .£»*>. > RSH=* >F6 .£ -.*. > BTU=* «F6 . 0 jx+FIXED*
o.F6.£»^.p VDLRTILE MRTTEP=* .F6 .£ :
DRYFC DRYVM - DRYBTU ' WETBTU
4 FORMRT ODRY MINERRL MRTTER FREE FIXED CRRBON=*»F6 .£
1*DRY MINERRL MRTTER FREE VOLRTILE MRTTEP.=* ,F6 .£
£*DPY MINERRL MRTTER FREE BTU=**F6.0x
3*MDIST MINERRL MRTTER FREE BTU=*>F6.0>
-------
PRINT 7, EPRSUL
7 FDPMFIT -r+EPfi STflNDflRD-* SULFUR=* ..F4 .£,+:-.*:
PRINT 5
5 FDRMFlT f*RflNK=*>
RfiNK SORT IMG
IF (DRYFC-98.> 11,10,10
11 IF 13,30,30
13 IF (DRYFC-78.> 14,40,40
14 IF ':BRYFC-69.> 15 ,50 »50
15 IF aiETETU-14000.::- 16,60>60
16 IF 17,70.70
17 IF 18»80?80
IS IF 19.90,90
19 IF '.:WETBTU-9500.> £00,100,100
£00 IF ££ »11 0 »11 0
££ IF '.:U1ETETU-6300.> £3 »120,120
£3 IF 13 0 »10 «10
10 PRINT 1111
WRITE <6»llin
GD TD 1000
£0 PRINT £1
WRITE <"6p£l>
GD TD 1000
30 PRINT 31
WRITE C6»31)
GD TD 1000
40 PRINT 41
WRITE f6«41>
GD TD 1000
50 PRINT 51
WRITE <6f51>
GD TD 1000
60 PRINT 61
WRITE
GD TD 1000
80 PRINT 81
WRITE <6»8n
GD TD 1000
90 PRINT 91
WRITE <6,91>
GD TD 1000
100 PRINT 101
WRITE f6P!01>
GD TD 1000
120
-------
110
PRINT
WRITE
GD TD
PRIMT
WRITE
GD TD
111
<6»111>
1000
121
<6»1£1>
1000
130
1111
21
31
41
51
61
71
81
91
101
111
121
131
1 0 0 0
700
68
PRINT 131
WRITE <6»131)
FDRMflT OCLflSS
FDRMflT
FDPMflT
FDRMflT
FDRMflT
FDRMflT
FDRMflT
FDPMflT
1-1.. METfl-flNTHRflCITE*::-
!-£> flNTHRflCITE*)
I-3» SEMIflNTHRflCITE*)
II-l? BITUMINDUS-LDW VDLflTILE*>
II-2> BITUMIMDUS-MEDIUM VDLflTILE*)
11-3. BITUMIMDUS-HIGH VDLflTILE flO
II-4> BITUMINDUS-HIGH VOLATILE B*>
II-5. BITUMIMDUS-HIGH VDLflTILE C*>
FDRMflT OCLflSS II-5» BITUMIMDUS-HIGH VDLflTILE C»*
l*flGGLDMERflTING*x*CLfl.SS III-l vSUBBITUMIMDUS RjMDNflSGLDMERflTIMe*-)
FDRMflT OCLflSS 111-2.- -SUBBITUMINDUS B*>
111-3» SUBBITUMIMDUS C*>
IV-1 , LIGNITE fl*^'
IV-2> LIGNITE B*>
OCLflSS
OCLflSS
OCLflSS
OCLflSS
OCLflSS
f. *CLflSS
OCLflSS
OCLflSS
OCLflSS
OCLflSS
OCLflSS
'00
69
FDPMflT
FDRMflT
FDRMflT
PRINT i
FDRMflT O
PRINT 68
FDPMflT
flCCEPT GD
IF '.'GD.:' 69 »69*1
PRINT 700
END
121
-------
Appendix C
Untreated Coal Analyses Data
122
-------
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Appendix D
Pyritic Sulfur Removal Data
Notes: The complete general procedure used to
treat the coals is contained in Section 4.3 of
this report. Variables such as mesh, reaction
time, and leach numbers and times are listed in
the tables. Numbers in parenthesis are not
considered valid for various reasons and are
included for completeness. Averages are included
only where appropriate.
127
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Pennsylvania
T31
-------
Appendix E
Washability Tables
NOTE: Coal was liability results have been
performed through standard float
and sink testing, discussed in
Section 4.4.
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165
-------
Appendix F
Organic Sulfur Removal Data
Note: The complete procedure used to treat these
coals is contained in Section 4.5 of the report.
166
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167
-------
TABLE F-2
ORGANIC SULFUR REMOVAL DATA
BELLE AYR, FOX, COLSTRIP.AND JANE MINES
Mine, Seam, and
Location
Belle Ayr Mine,
Roland-Smith Seam,
Campl '11 County,
Wyom i
Fox Mine,
Lower Kittanning
Seam,
Clarion County,
Pennsylvania
Colstrip Mine,
Rosebud Seam,
Rosebud County,
Montana
Jane Mine
Lower Freeport Seam,
Armstrong County,
Pennsylvania
Run
Number
1
2
3
Average
Treated _
Average
Untreated
1
2
3
Average
Treated
Averaqe
Untreated
1
2
3
Averaqe
Treated
Average
Untreated
1
2
3
Average
Treated
Average
Untreated
Dry Forms of Sulfur, % w/w
Total
0.86
0.80
0.71
0.79
_t075
0.76
+ .029
4.12
4.07
4.19
4.13
+ .060
3.83
+ .038
0.85
0.97
0.88
0.90
t.062
1.01
+ .006
2.00
2.17
2.08
2.08
+.085
1.85
+ .015
Pyri tic
0.37
0.24
0.33
0.31
+ .066
0.22
+ .017
3.83
3.74
3.85
3.79
+ .064
3.09
+ .017
0.31
0.37
0.32
0.33
+..C32
0.34
+ .015
1.73
1.75
1.69
1.72
+.031
1.44
+ .048
Sulfate
0.00
0.00
0.00
0.00
+ .01
0.00
+ .01
0.01
0.00
0.03 ,
0.01
+ .015
0.05
+ .015
0.02
0.02
0.00
0.01
+ .012
0.00
+ .00
0.00
0.00
0.00
0.00
±.01
0.002
+ .004
Organic
0.49
0.56
0.38
0.48
±.100
0.54
+ .035
0.28
0.33
0.31
0.33
+ .089
0.69
+ .044
0.52
0.58
0.56
0.5f
±.071
0.67
±.019
0.27
0.42
0.39
0.36
±.079
0.41
+ .051
Dry Proximate Analysis, % w/w
Ash
7.77
7.76
7.81
7.78
± .026
7.55
± .058
16.45
16.30
16.72
16.49
+ .212
13.55
+ .031
9.99
11 .01
9.86
10.28
± .630
10.38
± .075
25.64
25.54
25.25
25.48
+86.6
21.75
+ .081
Volatile
Matter
47.51
45.40
47.32
46.74
± .167
47.11
±1.55
34.04
35.66
34.98
34.89
+ .813
38.33
+_ .580
41.78
38.72
41.39
40.63
±1.67
43.09
± .733
28.41
27.90
26.84
27.71
± .800
30.07
+ .289
Fixed
Carbon
44.72
46.84
44.87
45.47
+ .191
45.35
±1.50
49.51
48.04
48.30
48.02
+ .784
48.12
+ .560
48.23
50.27
48.75
49.08
±1.06
46.53
± .801
45.95
46.56
47.91
46.81
±1.00
48.18
+ .250
Heat
Content
btu/lb
11797
11993
12074
11955
±142
12034
±74.5
12186
12275
12285
12249
+51.5
12973
+ 17.6
11653
10839
11631
11374
±463
11591
±67
11013
11179
11139
11110
±86.6
11932
+38.2
168
-------
Appendix G
Sieve Analysis Data
169
-------
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170
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Appendix H
Methods Development and
Trace Element Analysis Data
171
-------
The purpose of the methods development phase of the program was to
evaluate and set up the analytical methods to be used for coal trace ele-
mental analysis for the elements Ag, As, B, Be, Cd, Cr.Cu, F, Hg, Li, Mn, Ni,
Pb, Sb, Se, Sn, V, and Zn and to identify obvious and/or possible problem
areas. Methods development involved the assessment of various dissolution
methods for coal and coal ash, and the effect these procedures had on the
subsequent analysis . Based on the results of this study, a scheme was
devised and tested for the analysis of all elements using a combination
of plasma ashing in conjunction with conventional atomic absorption,
micro thermal analysis and colorimetric techniques.
Sample dissolution can conceivably be accomplished by decomposing
and dissolving the coal and ash simultaneously with an oxidizing acid
attack, such as the H2$04 -HN03-HC104 method used by the National Bureau of
Standards for their atomic absorption mercury analysis in coal (6), or by
first oxidizing the coal matrix by ashing either at low or high temperature,
and then dissolving the residue by some appropriate technique. This study
utilized low temperature oxygen plasma ashing since high temperature
ashing (e.g. 500°C in a muffle furnace) has been reported to be unusable
since many of the more volatile elements such as As, Cd, Hg, Pb, Sb, Se,
and Zn, are lost(3,7). The ash remaining after decomposition of the coal
matrix is then dissolved and the analysis performed. Since quantitative
dissolution techniques vary with differing elemental and molecular composi-
tion, a search for a common dissolution procedure for the elements of
interest was made utilizing readily available 1iterature(4-8). Because the
majority of the compounds normally associated with coal ash are oxides,
silicates or sulfides, conventional dissolution methods for these classes
of compounds, such as HF attack in conjunction with either HUSO*, HCIO*
or HN03 for silicates (6,7) and LiBCLfusion for oxides (8), were given first
consideration. The final evaluation was performed using 100 mesh x 0 Lower
Kittanning coal and the five dissolution methods discussed below. One
procedure was a chemical digestion using hLSO^-HNOg-HClO^S) while the
remaining four methods involved the dissolution of the low temperature
ashing residue and included: (1) Na^CO., fusion followed by HNOo
172
-------
dissolution of the melt,(2) direct HN03 attack, (3) LiB02 fusion followed
by HN03 dissolution of the melt, and (4) HN03-HF digestion. All residues from
the above digestions were filtered, washed, and dry ashed. These residues
were then weighed and analyzed qualitatively by either X-ray fluorescence
or electron beam microprobe. The results of these qualitative analyses
showed that of the five methods used only two, HNCL-HF and LiBO~ fusion
followed by HNCL dissolution of the melt, were effective in dissolving all
of the elements of interest. Of these two methods the HNCL-HF method was
chosen as the preferred method.
The elemental analysis of the dissolved coal and coal ash samples
was done by atomic absorption spectrophotometry (AA), using either flame
or fTameless techniques with some auxiliary methods being employed for As,
B, and F. Atomic absorption as a general analytical tool is normally con-
sidered free of interelement interferences and, because of the large dilu-
tions normally employed, is usually unresponsive to matrix changes. Trace
elemental analysis in coal does not follow general rules since the elements
of interest are present in a very dilute form in a relatively concentrated
matrix, consisting of the major inorganic components of the coal ash as
well as the relatively high concentrations of fluxes and acids needed for
the dissolution. In preparation for the analysis a search was made of
readily available literature for known interferents for each element and
the techniques employed for their removal. This data is compiled in Table
H-l along with the expected detection limit for each element based on a 2g
sample dissolved in 100 ml of solution.
Since the predominant type of interference for the majority of the
elements reported in the literature is molecular absorption, the sample
background absorption was monitored for each element using a hydrogen
continuum lamp with a wavelength close to the analytical wavelength
(Table H-2). An evaluation of the analytical and background absorption
data generated by the analysis of the five solutions encompassing different
dissolution procedures showed significant background signals to be present
for the majority of the elements using the L1B02-HNO ,HN03-H2S04-HC104,and the
173
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0 flame Slight 1000 pom Cu
0 flameless
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1 flame Sr at 50 mg/ml
5 f]ame H?SO., H..PO,., 5000 ppm Na
0 flameless H
1 Colorimetric method - none
reported
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0-c aliquot) '
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NO,-, F-
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175
-------
TABLE H-2
ATOMIC ABSORPTION ANALYTICAL PARAMETERS
(A) Flame Methods
Element An»lyt1cil(Jl} Sl1t(A) Background (A*) Slit (A) Flame Conditions
Mn
Cu
Cr
N1
Sn
Ag
Sb
V
Pb
Cd
Zn
LI
Be
Hg
Sb
2795
3247
3579
2320
2246
3281
2176
4408
2833
2288
2139
6708
2349
2537
2176
4
10
4
2
4
10
4
2
10
4
10
10
10
B)
10
10
2882
3171
3563
2316
2186
3257
2241
-
2850
2297
2197
6698
2312
f Tameless AA methods
2241
4
10
4
2
4
10
4
-
10
4
10
10
10
10
Air-Ace tylenp
Air-Acetylene
NgO-Acetylene
NO- Acetylene
hydrogen-Air
Ai r-Acatylene-lean
Air-Acetylene-lean
lt>0 Acetylene-
emission mode
Air-Acetylene-lean
Air-Acetylene-lean
Air-Acetylene-lean
Air-Acetylene-lean
N-0-Acetylene
Ar flow, 2 SCFH, use
10cm cell heated to
200*C
pry at instrument . .
Se
Sn
1960
2863
*« h 1. I M*f VI -J\J I VI £. Ill
atomize at sattlng of
10
1879
2840
10 Same settings as for Sb,
except for addition of
H? whose flow Is
regulated at 10 psig
4 Same setting as for Sb
176
-------
Na2C03-HN03 dissolution procedures. The HN03-HF procedure was found to
be virtually free of background absorption, with the exception of Cd for
which a small background signal was found.
H.I. Atomic Absorption Analysis Procedures
Analyses of Ag, Be, Cd, Cr, Cu, Li, Mn, Ni, Pb, Sb, Se, Sn, V,
and Zn were all performed by atomic absorption methods on a single sample
of coal ash. A 2g sample of coal in a Petri dish was placed in an Inter-
national Plasma Corporation Model 1001B plasma asher and ashing begun.
Approximately once every 4 hours the console was opened and the coal
stirred to expose fresh surfaces. Ashing was continued 2-3 days until no
black particles remained.
The ash was then transferred into a Parr Instrument Co. Model 4745
24 ml Teflon acid digestion bomb using repeated deionized water washings. After
the volume was adjusted to approximately 10 ml, 2 ml of cone. HN03 (70% w/w
Ultrex high purity) were added, and the solution was heated on a low-heat hot
plate for 2 hours. An additional 2 ml cone. HNO, and 2.5 ml cone. HF
(52% w/w, Ultrex high purity) were then added and the bomb was assembled. The
bomb was then placed in an oven at 130° + 5°C for 4 hours. After cooling,
the solution was filtered (if necessary) into a 100 ml volumetric flask.
After adjusting the volume to 100 ml the solution was transferred to a
polyethylene bottle for storage.
In all cases the glassware used was carefully cleaned with dilute
HN03 followed by repeated rinsings with deionized water and a final rinsing
with acetone. All glassware was then stored in a specially covered area
until needed. Transfer to polyethylene containers was accomplished as
soon as possible to minimize absorption on the walls of the glass containers.
If storage was required at any time the solutions were refrigerated.
The solutions prepared in the above fashion were analyzed directly
for 14 trace elements on a Fisher Scientific Co. Model 810 atomic absorp-
tion spectrophotometer (AA) using the operating conditions listed in
Table H-2. The background wavelengths listed in Table H-2 were used to
'177
-------
monitor for possible interfering molecular absorptions. Since the dual
channel feature of the instrument allows simultaneous readings at the
analytical and background wavelengths for these purposes, appropriate
selection of flame conditions was used to eliminate possible interelement
effects. It was necessary to apply corrections only in the case of Cd and
on occasion for Be and Mn. Analysis for V was somewhat unsatisfactory by
either atomic absorption or flame emission methods. Flame emission was used
throughout the study for V and potential problems with this analysis are
discussed below.
Analyses for Sb, Se, and Sn were performed using a Fisher Scientific
Company Model 2 micro thermal analyzer attachment to the AA since flame
analysis methods were felt to be too insensitive to this study.
The detection limit for Se and Sn was still 2.5 ppm as opposed to
the desired 1 ppm; however, the cost of achieving a lower analysis limit
for these two elements was judged to be unwarranted in view of the
probable additional costs involved. For all of the analyses using the
micro thermal atomizer, background corrections were applied and standard
additions of the element of interest were used for quantitative work.
In most cases these three elements were not found in the samples studied.
H.2. Analysis Procedures for As. B. F and Hg
Separate analytical procedures had to be utilized for As, B, F and
Hg due to the facts that AA is too Insensitive for As and B, Hg is
reported to be lost during plasma ashing (6), and AA techniques are not
applicable to F.
The procedure chosen for As is a modified U.S. Bureau of Mines
procedure (1,9,10). A 1 g sample of coal 1s mixed with 1 g of MgO 1n a
porcelain crucible. The crucible is then heated slowly to 650°C and held for
1-1/2 hrs. The residue is transferred to a 125 ml Erlenmeyer flask using
acidified water. To this solution is added 5 ml cone. HC1, 2 ml KI
solution,and 1 ml of SnCl2 solution and the mixture is allowed to stand
for 15 min. This flask is connected to a receiving flask via a tube
containing glass wool to which a few drops of lead acetate solution has
been added. Ten ml of a solution of 5g silver diethyldithiocarbamate in
1000 ml pyridine is added to the receiver and 3g zinc to the reaction
flask. After allowing 30 min for complete arsine gas evolution the
178
-------
absorbing solution is transferred to a 1 cm cell where its absorbance is
measured at 540 my against the neat reagent using a Beckman DKII spectro-
photometer. The arsenic concentration is calculated after referral to a
calibration curve generated using a standard arsenic solution.
A colorimetric procedure is also used for B'(ll). A 1 g sample of coal in
a platinum crucible is ashed in a muffle furnace at 550°C for 1 hr. The
ash is fused with 1 g Na2C03 and then taken into solution with 1 N HC1 and
diluted to 100 ml. Then 2 ml of this solution in a 10 ml Nalgene centri-
fuge tube is extracted with 2 ml of 10% chloroform solution of 2-ethyl-l,
3-hexandiol. The organic phase is then separated and added to a 50 ml
Nalgene volumetric flask with 1 ml of a 0.375% (w/v) solution of curcumin
in glacial acetic acid and 0.3 ml of cone. I^SO*. After allowing 15 min
for color development the sample is diluted to 50 ml with Q5% ethanol and
the absorbance read at 550p against 95% ethanol on a Beckman Model DKII
spectrophotometer. A reagent blank is also run and subtracted from the
sample reading. The B concentration is then determined using a calibra-
tion curve.
The analysis procedure for Hg is one currently in use by the U.S.
Bureau of Mines (4). A 0.5g coal sample in a ceramic crucible
is placed in a Leco Instrument Co. tube furnace at 450°C fitted to
maintain an 0^ flow rate of 0.5 A/min. The combustion gases are swept
through an unheated quartz tube packed with lOg of gold foil for amal-
gamating the Hg vapor. After the initial combustion is complete (about
7 min) the temperature is increased to 650°C for 3 min. The gold foil
trap is then fitted with an Ar purge at 1 £/min and heated to 850°C for
15 sec. The Hg vapor released from the foil is swept into a 10 cm quartz
cell positioned in the atomic absorption spectrophotometer and Hg is
determined using the conditions in Table H-l. Calibration is accomplished
using known volumes of Hg saturated air in the analysis procedure.
Fluorine in coal was determined using an automated complexone
method. In preparation for the analysis an 0.5 g sample of coal is
mixed with 1 g CaO in a nickel crucible and ashed at 600°C for 2 hours.
The sintered cake is then fused with 2 G NaOH, dissolved in water and
diluted to 250 ml. This solution is then ready for analysis by the
179
-------
standard procedure in which fluoride reacts with the red cerous che-
late of alizarin complexion to produce a color which is measured spectro-
photometrically at 624 my.
H.3. Procedure Assessment
In order to determine the adequacy of the analysis procedures,
arrangements were made for TRW to participate in a round-robin concerned
with trace elements in coal. This was conducted by the National Bureau
of Standards under EPA contract. The National Bureau of Standards
prepared a standard coal for mercury and submitted samples of this coal
to a number of laboratories around the country for trace element
determinations. A sample of this coal was sent to TRW and analyzed
for the various trace elements using the procedures described above.
Table H-3 contains the TRW results obtained on the NBS coal.
Included in the table are the analysis values reported by the Illinois
Geological Survey using INAA. In general the TRW analyses are in fair
agreement with those reported by IGS except in the cases of F, Ni, Pb,
and Sn. For Ni, Pb, and Sn there are possible matrix effects
that may have been responsible for the poor agreement. The lack of
agreement in the F determinations could not be resolved.
H.4. Analysis Results
The results of trace element analyses for 18 elements in ten coals
before and after treatment by the Meyers process are presented in
Tables H-4 to H13. All analyses were run in triplicate on both untreated and
treated coals in order to get a good estimate of precision of the results
and a reliable estimate of the trace element removal. These analyses
were run on three separate samples of untreated coal in order that all
sources of error such as sampling, ashing, dissolution, handling, and final
analysis would be included in the final precision estimate. In a similar
manner, three separately extracted coal samples were each analyzed once
for the three values on the treated coal.
A standard deviation was then calculated for each set of results and
this was used to determine which results should be discarded. A value
falling outside 2a of the mean was not used. Discarded values are in
parentheses in the data tables. The differences between the initial
180
-------
average value and the final average value are also presented in the tables
The deviations on the differences were calculated using Equation 1:
Vb
Also reported are the calculated % removals. The standard deviation for the
amount removed was calculated using Equation 2:
2 . 1 2 (2)
r(a-b)/a V 74 ' 0a + ' ab
In cases where o/ ^\, is larger or the same as the value of the % different
N.D. is entered in the % change column to indicate that any apparent differtjrvt
in the initial and final values is not statistically valid. In all cases
where the element was not detected in the starting coal "Ind" appears in the
ppm change and % change column.
181
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TECHNICAL REPORT DATA
(Please read iHitniclittm on the reverse before completing)
\. REPORT NO.
EPA-650/2-74-025
3. RECIPIENT'S ACCESSION-NO.
4 TITLE AND SUBTITLE Applicabmty of fly, MeyerS PrOCeSS
for Chemical Desulfurization of Coal: Initial Survey
of Fifteen Coals
5. REPORT DATE
April 1974
6. PERFORMING ORGANIZATION CODE
w Hamersma) M.L.Kraft, C.A. Flegal,
A. A. Lee, and R. A. Meyers
8. PERFORMING ORGANIZATION REPORT NO
9 PERFORMING ORGANIZATION NAME AND ADDRESS
Systems Group of TRW, Inc.
One Space Park
Redondo Beach, California 90278
1O. PROGRAM ELEMENT NO.
1AB013; ROAP 21AFJ-32
11. CONTRACT/GRANT NO.
68-02-0647
12. SPONSORING AGENCY NAME AND ADDRESS
EPA, Office of Research and Development
NERC-RTP, Control Systems Laboratory
Research Triangle Park, North Carolina 27711
13. TYPE OF REPORT AND PERIOD COVERED
Final
14. SPONSORING AGENCY CODE
15. SUPPLEMENTARY NOTES
16. ABSTRACT
The report gives detailed experimental results of applying chemical
desulfurization technology to a variety of U. S. coals. Run-of-mine coal samples
were collected from 15 U.S. coal mines in 11 states. Each coal was treated
separately by the Meyers Process (ferric sulfate extraction) and float-sink
fractionation (physical coal cleaning). The Meyers Process removed 83-99% of the
pyritic sulfur (40-64% of the total sulfur) from all the coals that contained sufficient
pyritic sulfur for accurate sulfur determination. Four coals were reduced to less
than 1. 0% total sulfur by the Meyers Process , and one coal was reduced to less than
~ total sulfur by physical cleaning. Except for one mine, the Meyers Process
removed significant increments of sulfur over that removed by physical cleaning. The
Meyers Process also removed significant amounts of selected trace elements along
with the pyrite.
KEY WORDS AND DOCUMENT ANALYSIS
DESCRIPTORS
b.lDENTIFIERS/OPEN ENDED TERMS
c. COSATI field/Group
Air Pollution
'oal
oal Preparation
Desulfurization
Sulfur
Pyrite
Air Pollution Control
Stationary Sources
Meyers Process
Ferric Sulfate Extraction
Float-Sink Fractionation
13B
8G, 21D
81
7A
7B
Trace Elements
3 DISTRIBUTION STATEMENT
Unlimited
19. SECURITY CLASS (Tills Report)
Unclassified
21. NO OF PAGES
200
20 SECURITY CLASS /Thispage)
Unclassified
22. PRICE
EPA Form 2220-1 (9-73)
193
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