EPA-600/2-76-258
September 1976
Environmental Protection Technology Series
FATE OF TRACE AND MINOR CONSTITUENTS
OF COAL DURING GASIFICATION
Industrial Environmental Research Laboratory
Office of Research and Development
U.S. Environmental Protection Agency
Research Triangle Park, North Carolina 27711
-------
RESEARCH REPORTING SERIES
Resnarch reports of the Office of Research and Development, U.S. Environmental
Protl~ction Agency, have been grouped into five series. These five broad
categories were established to facilitate further development and application of
en vi 'onmental technology. Elimination of traditional grouping was consciously
planned to foster technology transfer and a maximum interface in related fields.
The five series are:
1.
2.
3.
4.
5.
Environmental Health Effects Research
Environmental Protection Technology
Ecological Research
Environmental Monitoring
Socioeconomic Environmental Studies
This report has been assigned to the ENVIRONMENTAL PROTECTION
TECHNOLOGY series. This series describes research performed to develop and
dem)nstrate instrumentation, equipment. and methodology to repair or prevent
environmental degradation from point and non-point sources of pollution. This
work provides the new or improved technology required for the control and
treat'nent of pOllution sources to meet environmental quality standards.
EPA REVIEW NOTICE
Thin report has been reviewed by the U. S. Environmental
Protection Agency, and approved for publication. Approval
doen not signify that the contents necessarily reflect the
views and policy of the Agency, nor does mention of trade
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This document is available to the public through the National Technicallnforma-.
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EPA-600/2-76-258
September 1976
FATE OF TRACE AND MINOR
CONSTITUENTS OF COAL
DURING GASIFICATION
by
A. Attari, J. Pau, and M. Mensinger
Institute of Gas Technology
3424 South State Street
Chicago, niinois 60616
Contract No. 68-02-1307
ROAPNo. 21ADD-024
Program Element No. 1AB013
EPA Project Officer: William J. Rhodes
Industrial Environmental Research Laboratory
Office of Energy, Minerals, and Industry
Research Triangle Park, NC 27711
Prepared for
U.S. ENVIRONMENTAL PROTECTION AGENCY
Office of Research and Development
Washington, DC 20460
-------
ABSTRACT
This report covers the continuation of a study initiated
by the Environmental Protection Agency to investigate the fate
of trace constituents of coal during the coal gasification pro-
cess for the production of pipeline-quality gas.
The present work concentrates on the fate of 39 minor
and trace elements of Montana lignite and Illinois No" 6 bi-
tuminous coal during gasification in a 0.1 m (4-inch) reactor
of an IGT process development unit (PDU) as well as a Montana
lignite gasification run conducted at HYGAS pilot plant. The
samples available for this study were limited to coal feed and
. .
coal residue samples of the pretreatment (in case of bituminous
coal) and hydrogasification stages o.f the above units.
Examination of the data, obtained in this stud~ indicate
that significant loss of volatile trace elements from coal
occurs during coal gasification, regardless of the feed type
or the size of the gasification unit.
The elements so removed,
will likely concentrate in the quench water and acid-gas scrub-
ber, thus requiring a systematic recovery and disposal of the
accumulated elements.
. ii, .
-------
TABLE OF CONTENTS
INTRODUCTION
Page
1
CHAPTER I.
EXPERIMENTAL
2
2
A.
B.
THE HYGAS PROCESS-
SAMPLE SELECTION
E.
CONCLUSION
4
4
15
16
C.
D.
ANALYTICAL RESULTS
DISCUSSION OF THE RESULTS
CHAPTER II.
ANALYTICAL METHODS
17
17
17
17
IDENTIFICATION OF INSTRUMENTATION
SAMPLE PREPARATION
A. SIZE REDUCTION
B. ORGANIC MATTER REMOVAL
C. SAMPLE DISSOLUTION AND ANALYSIS
1. CATEGORY I ELEMENTS
2. CATEGORY II ELEMENTS
3. CATEGORY III ELEMENTS
4. CATEGORY IV ELEMENTS
REFERENCES CITED
17
18
18
29
32
33
38
iii
-------
Table ,No.
1
2
3
4 1
5
6
7
8
9
10
11
12
13
14
15
LIST OF TABLES
List of Selected Coal Gasification Samples
From 0.1 m Reactor IGT Process Development Unit
Lignite Samples Selected From a 3-Day
Steady-State Period of HYGAS Run No. 21
.' 7" ";"
Proximate and Ultimate Analyses of Hontana ,
Lignite Samples From IGT 0.1 m PDU Gas if ica t,iqn~uns
Proximate and Ultimate Ana1yses:.of Illinois 'NQ. ,6", !,
Bituminous Coal Samples, From IGT 0.1 m PDU
Gasification Runs
Proximate and Ultimate Analyses of'M6n't:ana' '
Lignite Samples From HYGAS Run No. 27
Concentration of
Feed and Residue
Runs of Illinois
Feed Basis
'Minor and Trace Elements" in:
Samples of PDU Gasificat:ion' :
No.6, Calculated on th~
, ,
Concentration of Minor and Trace Elements in
Feed and Residue Samples ofPDU Gasification'
Runs of Montana Lignite, Calculated on .,the
Feed Basis
Concentration of Minor and Trace Elements.-in
Feed and Residue Samples of HYGAS Run No. 27,
Calculated on the Feed Basis
: : '
, '
Concentration of Trace and Minor Elements in
Feed and Residue Samples and Their Percent Change
During Gasification
Methods For Sample Preparation
Analytical Methods For Chemical Analysis of
Solid Samples'
Operational Parameters For The Determination
of Category I Elements
Operational Parameters For The Determination
of Category I Elements
, 10
Boiling Points of As, Se, Te, Sb, and Sn Fluorides
Operational Parameters For the Determination
of As, Se, Te, Sb, and Sn
'iv
Page
.,'. 5
, .
6
7
I.
8
9-10
:,':1
11
12
13'
14
19
20-24
26
28
30
31
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Table No.
16
17
Figure 1
LIST OF TABLES CONT'D.
Page
Analytical Line Pairs For Group III Elements
32
Operational Parameters For TQeDetermination
of Ag
37
LIST OF FIGURES
The IGT HYGAS Process
3
v
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INTRODUCTION
This study is the continuation of a program initiated by
the Environmental. Protection Agency in May of 1972 to investi-
,
gate the fate of 11 trace elements, contained in a Pittsburgh
.f. . 4
No.8 bituminous coa~, during gas1 1cat10n.
The scope of the program was subsequently expanded (under
Contract No. 68-02-1307) to cover the investigation of a total
of 39 trace and minor elements in two series each, of Montana
lignite and Illinois No.6 bituminous coal samples and residues
obtained from the past hydrogasification runs conducted in an
IGT 0.1 m process development unit (PDU) - also referred to
as 4-inch (reactor) bench-scale unit. The expanded program
(commencing in January, 1973) also included the analysis of
a series of feed and solid residue samples from a HYGAS coal
gasification run, using Montana lignite.
An amendment to the contract required the preparation of
a comprehensive test plan which consisted of the preparation
of a preliminary plan for the eventual execution of an orderly
test program involving all the streams of a HYGAS~based
commercial plant-- but included no actual sampling or analysis.
The above test plan has been completed and reported under a
30
separate cover.
The contents of this report are concerned only with the
analysis of solid samples and include no sampling or analysis
of the gaseous and liquid streams of either PDU or HYGAS
pilot plant.
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CHAPTER I.
EXPERIMENTAL
A.
The HYGAS Process
The HYGAS Process shown in Figure 1, was developed by the Institute of '
Gas Technology (Chicago) for the T,1,.;3., Department of the Interior's Office
of Coal Research (now ERDA) and the American Gas Association, and has reach-
,ed the pilot plant stage. The pilot plant is designed to process 68 me,tric
tons of coal and produce 42,500 cobic meters of "pipeline' quality gas daily.
This proce~s can' operate with any rank or' type of coal and ~s, tailored
... ''''. '. ,,' ' , "i . \' , . .'.
for the :naximumthermal e~ficiency by optimizing 'the direct form~ti~I?- of
" . " " J."
methane in the reactor. High temperature (650 to 760°C in the first stage,
and 870 ~O' 980°C' in' the second stage) guaranteereasonab1~ reaction rates,
It. ;
arid high pressure (about 75 atm iri both stages) increases equilibrium
methane :rie1d.
,
,
I ,: " ", I '
Th.~ most active fraction. C!f co~l is hydrogasified to fOi,Iii. methane,
'I , ...
while th4~ less active fraction is used to generate hydrogen in, support ~f
. . '. " ;. . ~) : .' ..; . I - '
the reactions. ' The raw gas from the hydrogasifier contains substantial
", '
. I ~ t I
. , ,
amounts of carbon monoxide and hydrogen. These,are converted ~ndirect1y to
. "..' . .'.'):.',.: ' , ,
methane during catalytic clea?,-up methanation, b0C!sting the heating value
. f., .
of the gHS, and reducing carbon monoxide content to below 0.,1%.
In the HYGAS pilot plant op~rations,c~~l is ground to -8 mesh size
. .' - . -
and fed into a pretreater if th~, :feed is,, an agg1ome~ating coa~; otherwise
it is fee. dinictly to the slurry preparation sectiop if coal is non...,agg1om-
. . . . " " " ~ i . .'. . : '.' I '. . . ~." .
erating. The caking t~nde'~~Y'~f coa~ is destroyed in the pr~t~~a~~r ?y
mild surface oxidat"1.on Of the' 1 't' . 1 ".'" -'. th' '.d t
coa par .1C es, us~;ng a1r a.s, . ,e OX1 an .
All types of ,coal, ,w:~th, or 'iitho,ut, pretreatment" .are slurried with
a by-product aromatic oil and then pumped to a pressure of 83 atm and moved
to the reactor.
and recycled.
The oil is evaporated in a sl11rry d~ier~ a~d,later condensed
..', . ,I, .
The dried coal is moved ~o, the bottom of the first hydrogasi-
fication stage.
! "
In the first stage of reactor, coal enters a high-velocity rising
stream of hot gases that originate in the lower, second stage. As the solids/
gas mixture rises, the coal is rapidly heated by dilute-phase contact with hot
2
-------
IIYIIIUII;h~1I1I1I
COAL t
SLURRY SHIFT
650 - 7600 C CONVERSION
FIRST STAGE L 75 Atm
SECOND STAGE .. GAS SULFUR
SLURRY RAW HYDROGEN -RICH PURIFICATION RECOVERY
FUEl GAS
PREPARATION GAS AND STEAM FROM
\.IV ANY OF THREE HYDROGEN ElEMENTAL
COAL COAL. COAL PRODUCTION SCHEMES METHANATION SULFUR
PREPARATION I PRETREATMENT UNDER EVALUATION AT IGT .
I I
I AIR I
I I DE HYDRA TlON
L___~__..J
4300 C ;, 1 Atm PUMP 870 - .9800- c CHAR ..
. . 75 Atm PIPELINE GAS
D-24-Z78
GAS: HIGH MHHANl CUNllNI
QUENCH
Figure 1. The IGT HYGAS process.
-------
reactioIJ gases.
At tpe top of this riser-reactor, gas velocity is reduced,
solids drop. out, and gas continues upward, drying incoming coal in the
slurry drier.
Hot char is channeled downward to a dense-phase fluidized
bed in the second, high-temperature reactor stage.
the fluidized bed contacting char with good mixing.
Hot gases pass ~hrough
Organic carbon remain-
ing in char after this stage can be used at other process points to produce
both hydrogen and heat required in the HYGAS conversion process.
Subsequent process steps include quench, shift to a 3:1 ratio of
hydrogen to carbon monoxide, gas purification, methanation, and drying
be'fore tfle final product. emerges as high-Btu SNG.
B.
Sample Selection
After the examination of data from a large number of gasification
runs conducted in 1GT process development unit (PDU) on Montana lignite
and 111i:1ois No.6 bituminous coal, four series of coal feed and residue
samples '"ere selected.
The samples were collected from two similar
hydrogas:lfication runs on each of the above two coal types and consisted
of feed, intermediate residue, and the final residue samples.
These
samples and their gasification sequences are outlined in Table 1.
An additional series of feed and residue samples were also obtained
from the steady-state periods of HYGAS run No. 27 on Montana lignite, as
listed in Table 2.
The scope of this work was limited to the analysis of coal feed and
solid re~;idue samples only and did not include any liquid or gaseous samples.
c.
Analytical Results
Prclximate and ultimate analyses for the above 28 samples are reported
in Tab1e~; 3, 4, and 5.
in Tab1e~ 6, 7, and 8.
Trace and minor element concentrations are reported
The reported values for the trace and minor elements,
are calct1ated on the coal-feed basis.
The average values of each element, in feed and final residue samples
(from siuilar gasification runs conducted on the same type of coal) are
reported in Table 9 along with percent change (loss or gain) of each element
during gasification. The percent change values are calculated from the
'4
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Table 1.
LIST OF SELECTED COAL GASIFICA TION SAMPLES FROM( O. 1 M REACTOR)
IGT PROCESS DEVELOPMENT UNIT
1.
*
Illinois No.6 Bituminous Coal
A.
Fi;rst Series:
F-FP-99
Fed to Pretreater
Fed to Hvd:ro-
~ or
F-HT-156. gasifier
R -FP-99
> R -HT -156
B.
Second Series:
R-FP-105
F-FP-105 Fed to Pretreater >. or Fed to Hydro-
F-HT-155 gasifier
)- R-HT-155
U1
II.
L" . t
Montana IgnIte
A.
First Series:
F-HT-254 Fed to ls~?tage
Hydrogasifler
R:-HT-254 Fed to 2nd Stage
) F-~;'-256-1Hydroga:sifier
R-HT -2 56-1
B. Second Series:
F-HT-255 .Fed to 1s~?tage :>
Hydrogasifier
R-HT-255
or ~e~ to 2n?f"Stage ~ R-HT-256-2
F-HT-256-2. Y rogasl Ier
*
Each sample in these two series is prefixed by a letter F or R (designating feed or residue,
respectively) followed by letters FP or HT (denoting a pretreatment or hydrogasification run,
respectively) and is, finally, suffixed by the correspol.ldin~ serial run number.
. .
t This feedstock does not agglomerate in the hydrogasifier, therefore, it has not been pretreated,
but it has been hydrogasified in two stages. of increasing severity.
-------
Table 2. LIGNITE SAMPLES SELECTED FROM A 3-DAY'
. STEADY-STATE PERIOD OF HYGAS RUN NO. 27
.'
*
Sampll~ De_~ignation Date
. F..2 7 -300 3-3-74
R..2 7 -329 3-3-74
R.;27'-330 3-3-74
R ..2 7 - 3 31 3-3-74
R..2 7 -332 3-3'-74
F,'..2 7 -342 ' 3 -4 - 74
R ..2 7 -366 3 -4 - 74
" . . .
F ..27 - 3 79 3-5-74
..
R - 27 - 381 ..1: 3 -5 - 74
R -2 7 ,..406 3-5-74
R - 2 7 .,.408 3-6-74
F-27,..410 .3-6-74
R-2 7 -411 3-6-74
R-2 7 -412 3 -6 - 74
F-27-428 3 -6 -74
R,..2 7.439 3 -6 - 74
',- .
Tinie
.
I '-,
05:40
04:00
12 : 05'
16:00
20:00
09:30 .
12:15
08:00
08:50
12:20
00:20,
02.:20
04: 0 5
. 08:05
08 :45
12:12
,.
,-
. I' '. . .
.' . .
it".' ','. '\' - . .,' "
. Letter prefixesF and R designate feed or residue samples I respectively.
. ,.
"
6
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Table 3. PROXIMATE AND ULTIMATE ANALYSES OF MONTANA LIGNITE SA1V1PLES
FROM IGT 0.1 m PDU GASIFICAT1.QN RUNS.
Proximate, As Received F-HT-254 F-HT-256-1 R-HT-256-1 F-HT-255 F-HT-256-2 R-HT-256-2
Moisture 12. 1 2.0 0.8 11. 6 1.3 0.8
Volatile Matter 36.0 9. 1 7. 6 '36.3 9.4 7. 1
Ash 9.2 18.9 23.4 8.3 18.8 25.3
Fixed Carbon 42.7 70.0 68.2 43.8 70.5 66~8
(by difference)
Total 100.0 100.0 100.0 100.0 100.0 100.0
Ultimate, Dry Basis
Ash (corrected for S03) 10. 41. 19.30 23. 61 9.38 19.09 25. 52
---J Carbon 62.3 73.6 70.3 62. 7 73.4 69.1
Hydrogen 4.10 1. 76 1.0.9 4.09 1. 81 0.95
Sulfur 1. 18 0.80 0.82 0.80 1. 13 0.80
Nitrogen 0.88 0.57 0.39 0.96 0.68 0.36
Oxygen ( by difference) 21. 12 3.97 3.79 22.07 3.89 3.27
Total 100.00 100.00 100.00 100.00 100.00 100.00
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Table 4. PROXIMATE AND. ULTIMATE ANALYSES OF ILLINOIS NO.6
BITUMINOUS.COAL SAMPLES, FROM IGT 0.1 m PDU GASIFICATION RUNS.
Proximate, As Received F-FP-99 F-HT-156 R-HT-156 F-FP-105 F-HT-155 R-HT-155
Moisture 13. 3 1.4 0.3 9.4 1.1 0.5
Volatile Matter 33.0 22.7 1.0 33. 7 23.0 4. 1
Ash 8.8 11. 3 22.1 9.6 12.9 20.5
Fixed Carbon 44.9 64.6 76.6 47.3 63.0 74.9
(by difference)
Total 100.0 100.0 100.0 100.0 100.0 100.0
(X) Ultimate,D ry Basis
Ash (corrected for S03) 10. 10 11 . 48 22.20 10.58 13.08 20.63
Carbon 70. 1 70.3 74.7 71.1 68. 6 77.0
Hydrogen 4.88 3.58 0.59 4.61 3.25 ' 1. 17
Sulfur 3.74 ,3.33 1. 78 3.'90 3.63 1. 44
Nitrogen 1.07 1. 20 0.41 1. 01 1. 34 O. 56
Oxygen (by difference) 10.11 10.11 0.32 8.80 10. 10
Total 100.00 100.00 100.00 100.00 100.00 100.80
-------
Table. 5. PROXIMATE AND ULTIMATE ANALYSES OF
MONTANA LIGNITE SAMPLES FROM HYGAS RUN NO.2 7
Spent Char
Feed Samples (Residue) Samples
Proximate (as received) F-300 F - 342 F-379 F-410 F-428 R - 32 9 R-330 R-331
Moisture 10.8 10.6 11.5 9. 1 9.4 2. 1 2. 7 2.2
Volatile Matter 34.2 33.8 34.6 35.2 36.5 16.1 17.4 11.9
Ash' 9.2 10. 3 10. 7 10. 7 9.9 27. 7 29.4 39. 1
Fixed Carbon
(by difference) 45.8 45.3 43.2 45.0 44.2 54.1 50.5 46.8
Total 100. 0 100. 0 100.0 100. 0 100.0 100.0 100. 0 100.0
Ultimate (dry basis)
Ash (corrected for S03) 10. 33 11. 49 12. 11 11.77 10. 92 28.26 30.24 39.94
'" Carbon 63.4 61.8 62.3 61.9 62.6 61.6 59.5 54.2
Hydrogen 4.23 4.08 3.87 4.09 4.18 2.41. 2.57 1. 64
Sulfur 0.67 1.03 1. 14 O. 78 0.80 0.64 0.67 0.41
Nitrogen 0.92 0.91 0.91 0.92 0.93 0.65 0.69 0.17
Oxygen (by difference) 2 O. 45 20~ 69 19.67 20.54 2 O. 57 6.44 6.33 3.64
Total 100.00 100. 00 100. 00 100. 00 100.00 100.00 ' 100.00 100.00.
-------
Table,S. Cont. PROXIMATE AND ULTIMATE ANALYSIS OF
MONTANA LIGNITE SAMPLES FROM HYGAS' RUN NO. 27
Spent Char (Residue) Samples
Proximate (as received) R - 3 32 R -366 R -381 R -406 R-408 R -411 R..412 R -439
Moisture 2.4 4. 1 7.2 't.O 1. 7 2.2 3.2 1.7
Volatile Matter 19. 7 25.5 22.6 23.1 12.6 10. 1 18. 0 15.5
Ash 25. 7 21. 1 23.5 23.4 32.9 36.2 28.0 33.2
Fixed Carbon . ,-,"
(by difference) 52.2 49.3 46.7 49.5 52.8 51.5 50.8' 49.6
Total 100. 0 100. 0 1 ~O~ 0 ]:OO~O 100.0 100.0 100. 0' 100. 0
Ultimate (dry basis)
.... Ash (corrected for S03) '26. 35 '22. 03 2 5-. 3 5 24.37 ~3.50 '37. 02 ,,28. 97 33.- 76
o Carbon 63. 1 62.8 66.5 63.'9 58~8 57.3 ,60.0 57. 5
Hydrogen 2.75 3.32 2.50 2.85 2.02 1. 57 2.61 1.98
Sulfur 0.66 0.85 O. 77 0.96 0.59 O. 31 O. 78 0.49
Nitrogen' O. 77 0.95 0.73 0.84 "0.49 0.24 ,'0.63 0.47
Oxygen (by difference) . 6.37 10.05 '4: 15 7.08 ' 4.60 3.56 7.01 5.80
Total 100. 00 100.00 100. 00 100.00 100.00 100.00 100.00 '100.00
-------
Table 6 . CONCENTRATION . OF MINOR AND TRACE ELEMENTS
IN FEED AND RESIDUE SAMPLES OF PDU GASIFICATION
RUNS OF MONTANA LIGNITE, CALCULATED ON THE FEED BASIS.
Feed Samples Pretreatment Residues HydroRasified Residues
Elements , ppm F- FP-99 F-FP-I05 F-IIT-156 F-HT-155 R-IIT-156 R-IIT-155
Antimony 0.79 1.3 0.58 0.98 0.57 0.87
Arsenic 28 20 . 26 17 20 12
Barium 28 33 28 33 28 33
Beryllium 0.94 1.1 0.81 0.89 0.69 0.82
Bismuth 1.0 1.1 0.98 0.89 0.50 0.57
Boron 200 200 190 200 170 200
Cadmium 0.96 0.81 0.51 0.60 0.24. 0.17
Calcium 4,500 2,500 3,300 2,200 2.500 2,100
Chlorine 2.300 2,300 (a) 1,500 . 550 620
Chromium 14 16 14 16 14. 16
Cobalt 3.6 3.7 3.6 3.7 3.6 3.7
Copper 18 20 18 20 18 20
Fluorine 58 65 56 62 41 49
Germanium 4.0 4.5 . 4.1 4.0 3.8 4.0
Iron 14,000 14,000 14,000 13,000 13,000 13,000
Lead 6.3 15 3.5 8.1 3.7 7.9
Lithium 32 35 31 35 31 34
Magnesium 530 610 570 640 550 620
Manganese 57 39 52 36 41 36
Mercury 0.17 0.072 0.034 0.016 0.005 0.004
Molybdenum 6.5 . 7.5 6.2 7.5 6.2 7.4
Nickel 16 14 15 13 14 14
Nitrogen 10,000 10,000 11,000 11,000 1,900 2,900
Potassium 1,100 1,100 1,100 1,100 1,100 1,100
Samarium 0.78 . 0.70 0.70 0.72 0.75 0.72
Selenium 15 12 13 9.2 9.4 5.5
Silicon 20,000 .21,000 19,000 22,000 19,000 21,000
Silver 0.11 0.10 0.080 0.057 0.041 0.030
'Sodium 1,4:>0 1,500 1,500 1,500 1,500 1,500
Strontium 36 39 37 39 36 38
Sulfur 37,000 39,000 29,000 29,000 8,100 7,400
Tellurium 8.5 7.7 6.3 6.2 5.1 4.4
Thorium <1 <1 <1 <1 . <1 <1
Tin 2.1 1.8 1.6 1.3 1.2 0.91
Titanium 720 820 720 820 730 770
Vanadl'um 14 21 12 19 11 18
Ytterbium . 0.53 0.58 0.50 0.60 0.47 0.55
Zinc 51 47 48 35 40 32
Zirconium 34 35 34 32 33 36
a.
Insufficient samples
11
-------
Table 7. CONCENTRATION OF MINOR AND TRACE ELEMENTS
IN FEED AND RESIDUE SAMPLES OF PDU GASIFICATION
RUNS OF MONTANA LIGNITE, CALCULATED ON THE FEED BASIS.
'Feed Samples First StaRe Residues Second StaRe Residues
l:lements, ppm F-HT-254 F-IIT-255 F-HT-256-1 F-IIT-256-2 R-IIT-256-1 R-IIT-256-2
J n timony 1.3 1.1 1.1 1.0 0.95 0.91
J .rsenic 19 18 12 10 8.6 8.5
I arium 1,300 1,400 1,200 1,400 1,200 1,400
lery11ium 0.98 0.99 0.99 1.0 0.78 0.75
I ismuth 0.69 0.74 0.56 0.64 0.43 0.38
I or on 82 88 69 62 64 58
(admium' 0.74 0.70 0.63 0.57 0.34 0.31
( alcium 17 , 000 16,000 18,000 17,000 18,000 17,000
( h10rine 210 150 230 150 110 79
(hromium 14 14 12 12 11 11
(oba1 t 4.2 4.5 4.2 4.5 4.3 4.6
(opper 8.2 9.4 8.2 7.0 .6.7 5.6".
Fluorine 73 69 51 50 43 47
Germanium 2.5 2.8 2.0 2.1 2.0 2.1
Iron 9,000 5,6.00 9,700 9,000 9,000 9,700
Lend 1.9 1.9 1.6 1.0 1.2 0.90
Lithium 5.9 5.9 5.9 5.8 5.6 5.9
Magnesium 5,800 5,900 5,700 5,700 5,800 5,600
Manganese 8.9 8.9 9.0 9.0 . 8.6 '8.5
Mercury 0.21 (1. 3)" 0.090 0.014 0.012 0.003
M)lybdenum 2.0 2.1 2.1 2.1 1.9 1.8
N lcke1 22 24 21 21 21 21
N ltrogen 8,800 9,600 3,100 3,300 1,700 1,300
P.)tassium 340 350 320 350 330 340
5 marium 0.51 0.50 0.50 0.50 0.50 0.50
S .~lenium 1.8 1.6 1.2 1.1 0.63 0.53
5 LJ.icon 13,000 . 12,000 12,000 12,000 12,000 11,000
SLIver 0.25 0.23 0.22 0.25 0.25 0.22
S.,dium '180 190 180 180 170 180
S.:rontium 350 370 310 300 230 230
S'llfur 12,000 8,000 4,300 5,600 3,600 2,900
T.!llurium 0.42 0.43 0.35 0.37 0.25 0.23
Thorium <1 <1 <1 <1 <1 <1
Tln 1.9 1.9 1.8 1.8 1.8 1.8
T.ltanium 310 330 350 330 350 330
Vanadium 63 72 55 58 51 58.
y~,: terbium 0.35 0.38 0.37 0.32 0.32 0.32
Z:~DC 13 12 12 11 9;6 9.4
Z:.rconlum 25 25 23 22 23 21
" this' result was Dot used
Due to possible contamination,
12
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Table 8. CONCENTRATION OF MINOR AND TRACE ELEMENTS
IN FEED AND RESIDUE SAMPLES OF HYGAS RUN NO. 27
CALCULATED ON THE FEED BASIS.
Feed SamDles Final Sta2e Hydro2asified Residue Samples
E1ements,ppm F-300 F-342 F-379 F-410 F-428 R-329 R-330 R-331 - R- 332 R-366 R-381 R-406 R-408 R-411 R-412 R-439
Antimony 0.13 0.10 0.11 0.11 0.11 0.075 0.043 0.048 0.049 0.066 0.064 0.063 0.050 0.041 0.016 0.066
Arsenic 11 12 14 12 10 10 9.5 8.8 9.1 13 11 10 8.7 8.2 10 8.2
Barium 1,200 1,100 1,300 1,100 1,300 1,300 1,100 1,200 1,300 1,300 1,200 1,200 1,000 1,000 1,100 1,000
Beryllium 0.51 0.43 0.53 0.45 0.42 0.44 0.45 0.54 0.43 0.46 0.49 0.56 0.66 0.68 0.50 0.54
Bismuth 0.95 0.91 0.93 0.90 1.0 0.49 0.69 0.60 0.56 0.51 0.47 0.44 0.68 0.41 0.56 0.56
Boron 72 75 69 78 79 34 34 54 39 42 47 31 46 46 36 60
Cadmium 5.1 3.8 5.7 4.2 4.3 2.9 1.2 2.5 1.9 3.7 2.4 3.4 2.0 2.8 1.2 1.1
Chlorine 230 - 190 200 310 260 (a) 430 1,200 380 810 580 910 900 710 480 870
Chromium 5.3 5.7 6.9 7.7 7.6 5.8 7.1 6.5 5.7 5.4 6.4 6.8 4.8 4.2 7.0 4.1
Copper 7.0 7.2 9.9 9.1 9.1 9.8 9.5 7.8 10 12 7.6 7.2 6.5 6.2 9.2 5.7
..... Fluorine 82 75 75 68 70 56 47 46 55 52 60 48 56 59 51 52
I.,..) Lead 9.1 8.5 9.5 8.4 8.9 5.2 4.6 5.0 5.4 7.5 5.8 4.8 5.3 5.5 5.9 6.5
Lithium 6.3 6.1 6.6 7.1 6.5 6.9 6.5 6.2 6.7 7.2 5.7 5.7 6.5 6.3 7.6 6.0
Msnganese 85 97 97 93 88 82 76 94 84 87 94 (a) 88 91 87 88
Mercury 0.11 0.14 0.11 0.10 0.092 0.018 0.014 0.013 0.018 0.027 0.020 - 0.021 0.018 0.008 0.011 0.015
Molybdenum 2.7 3.0 2.9 2.9 2.8 3.0 3.0 2.7 3.0 3.2 2.8 2.9 2.9 2.8 3.2 2.8
Nickel 3.4 3.6 5.2 3.6 3.5 3.7 3.8 3.7 3.7 4.3 3.3 3.7 4.5 3.4 4.1 3.5
Nitrogen 9,200 9,100 9,100 9,200 9,300 2,600 2,600 500 3,300 4,900 3,300 3,900 1,700 700 2,500 1,600
Selenium 1.7 1.4 1.2 1.2 1.3 0.81 L5 0.62 1.6 1.7 1.3 1.3 0.61 0.51 1.5 0.60
Sl1 ver 2.9 2.3 2.2 2.1 2.5 2.3 2.5 2.3 2.2 2.2 2.3 2.1 2.3 2.3 2.4 1.9
Sodium 250 280 290 270 250 270 260 270 230 250 250 240 230 250 280 220
Strontium 380 -360 390 380 370 290~ 280 410 310 300 410 (a) 380 380 330 370
Sulfur 6,700 10,300 11,400 7,800 8,000 2,600 2,500 1,200 2,800 4,400 3,400 4,500 2,000 900 3;000 1,600
Tellurium 0.43 0.32 0.40 0.47 0.51 0.35 0.25 0.36 0.39 0.41 0.37 0.17 0.31 0.27 0.17 0.32
Tin 2.1 2.3 2.5 1.9 1.9 1.7 1.9 1.7 1.8 1.5 1.4 1.7 2.6 1.6 1.8 1.4
Vanadium 12 10 13 12 11 8.4 6.5 11 6.9 9.0 9.8 9.6 7.7 8.1 10 7.1
Zinc 4.6 5.8 7.6 14 5.5 5.4 7.2 6.6 5.9 5.6 6.4 7.4 6.9 6.4 5.8 5.8
a. Insufficient Samples.
-------
'!'a~!~ 9. tV'1\1 f" '1:""1'1'1> " '" T 1'\ 'U I'\T.'O ",,~14_..... ..- L'u.L'IUK E;i.uiliNl:;
--"'._"""""'.L""~'" .LV"''' V.L: .1.L'-t1..\J.c. fiJ. 'I U
IN FEED AND RESIDUE SAMPLES AND THEIR PERCENT CHANGE
DURING GASIFICATION
Process Develooment Unit Runs HYGAS Run
Illinois No. 6 Coal I Montana Lignite 2 Montana Lignite 3
Elements, ppm Feed Final Residue % Change 4 ~ Final Residue % Change 4 Feed Final Residue % Change 4
Antimony 1.0 0.72 -28 1.2 0.93 -23 0.11 0.053 -52
."'.:n:;~~::.: .LU -jj HI 8.6 -52 ] 2 9.7 -19
Ba ri um 31 31 0 1,300 1,300 0 1,200 1,200 0
Beryllium 1.0 0.76 -24 0.98 0.77 -21 0.47 0.52 +11
Bismuth 1.1 ' 0.54 -51 0.72 0.41 -43 0.94 0.54 -42
Boron 200 180 -10 85 61 -28 75 43 -43
Cadmium 0.89 0.21 -76 0.72 0.33 -54 4.6 2.3 -50
Calcium 3,500 2,300 -34 17 ,000 17 ,000 0 ND ND
Chlorine 2,300 590 -74 180 95 -47 240 730 +204
Ch romium 15 1) 0 14 11 -21 6.6 5.8 -12
Cobalt 3.6 3.6 0 4.4 4.4 0 ND ND
Copper 19 19 0 8.8 6.2 -30 8.5 8.3 - 2
Fluorine 61 45 -26 71 45 -37 74 53 -28
Germanium 4.3 3.9 - 9 2.7 2.1 -22 ND ND
Iron 14,000 13,000 - 8 9,200 9,300 + 1 ND ND
Lead 11 5.8 -1,7 1.9 1.0 -47 8.9 5.6 -37
Lithium 33 33 0 5.9 5.8 - 2 6.5 6.5 0
Magnesium 570 580 + 2 5,900 5,700 - 3 ND ND
Manganese 48 39 -19 .8.9 8.5 - 4 92 87 - 5
Mercury 0.12 0.005 -96 0.21 0.008 -96 0.11 0.017 -85
.....
.s:-- Molybdenum 7.0 6.8 - 3 2.1 1.9 -10 2.9 2.9 0
Nickel 15 14 - 7 23 21 - 9 3.9 3.8 - 3
Nitrogen 10,000 2,400 -76 9,200 1,500 -84 9,200 2,500 -73
Potassium 1,700 1,700 0 340 330 - 3 ND ND
Samarium 0.74 0.74 0 0.51 0.50 - 2 ND ND
Selenium 13 7.5 -42 1.7 0.58 -66 1.4 1.1 -21
Silicon 20,000 20,000 0 13,000 12,000 - 7 ND ND
Silver 0.11 0.036 -67 0.24 0.24 0 2.4 2.3 - 4
Sodium 1,400 1,500 + 7 180 170 - 6 270 250 - 7
Strontium 37 37 0 360 230 -36 380 350 - 8
Sulfur 38,000 7,800 -79 9,900 3,300 -67 8.800 2,600 -70
Tellurium 8.1 4.8 -41 ,0.42 0.24 -43 0.43 0.31 -28
Thorium <1 <1 <1 <1 ND ND
.Tin 2.0 1.1 -45 1.9 1.8 - 5 2.1 1..7 -19
Titanium 770 750 - 3 320 340 + 6 ND ND
Vanadium 17 14 -18. 67 54 -19 12 8.6 -28
Ytterbium 0.56 0.51 - 9 0.37 0.32 -14 ND ND
.Zinc 49 36 -27 13 9.5 -27 7.5 6.3 -16
Zi rconium 34 34 0 25 22 -12 ND ND
NOTES:
1. Average values of analytical results from two a1m~lar gasification rUns shown in Table 6.
2. Average values of analytical results from two similar gasification runs listed in Table 7.
3. Average values of analytical results from 5 feed and 11 residue samples shown in Table 8.
4. Minus sign indicates loss and plus sign indicates gain of sny given element. The percent losses shown
for PDU runs are good to t6 percent (i.e.. losses below 10-12% are not signif~cant).
-------
listed average elemental concentrations.
Extensive information, regarding the detailed analytical procedures
developed for this project, appear in Chapter II of this report.
D.
Discussion of the Results
In general, the samples obtained from the PDU hydrogasification runs
were more suitable for this type of study than the HYGAS samples. The PDU
hydrogasification uses a dry-fed and dry-discharged process causing no sig-
nificant cross contamination from one run to the next.
Whereas, the HYGAS
plant uses a coal-toluene slurry to feed the coal and a coal-water slurry
to discharge the residue, causing contamination of discharged samples by
the accumulated soluble salts in the recycled process water. This is par-
ticularly evident in a two-fold increase in chloride concentration for HYGAS'
samples (se~ Table 9).
In addition to errors from contamination, the HYGAS residue samples
showed a great variation in ash content from a low of 22.03 percent to a
high of 39.94 percent, whereas the spread for the ash in feed samples was
10.33 percent to 12.11 percent (see Table 5).
The spread in the ash (and
consequently the trace element) content of the HYGAS residues are caused by
periodic process up-sets.
Because of the above mentioned difficulties in obtaining representative
samples from HYGAS operation, we do not consider the reported data for HYGAS
as reliable as the PDU data.
Nevertheless, all reported data show the same
general trend in removal of volatile elements during gasification, with a few
exceptions.
Deviating from this trend are the elements Ca, Cu, Ag, Sr, and.
Sn, which exhibit substantially different behavior during the gasification
of the two feedstocks under discussion.
Considering the data presented in Table 9 for the PDU samples only,
it is apparent that the elements Ca, Ag, and Sn, show significant loss
during the gasification of Illinois No.6 bituminous coal, but show 100%
retention in the residue samples of Montana lignite.
The order is completely
reversed, however, with Cu and Sr.
This behavior can not be assigned to
experimental errors, since the results for the elements involved showed good
15
-------
repeatability for PDU samples from one similar sample to the next and also.
among th~ replicates of the same sample (of the order of I5). In other words,
the diff,~rential losses of these elements from the two feed types seem to be
quite re.ll and may be due to the differences in chemical forms (in which they
occur) h.iving different resistance to the reducing. atmosphere of the hydro-
gasifier for hYQride formation, or simply, this is the case of differential
volati1i;:y of their compounds in the two coals.
.It is also conceivable that.
the mild oxidation prevailing during pretreatment (of Illinois No.6 only)
may additionally playa role in their behavior.
E.
Conclusion
. Thts study along with many other recent investigations into the beha-
vior and distribution of trace elements in the production of synthetic fuels,
constitute only a beginning.
There is enough reliable information generated,
as a rest.It of this study, to indicate the need for an expanded program in
this aree.. Much more comprehensive programs than the present effort are
needed in order to compile adequate information for the proper design of the
critically needed supplemental fuel plants.
16
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CHAPTER II. ANALYTICAL METHODS
Identification of Instrumentation
The following instruments were used in this work:
Plasma Machine, Model IPC 1l05B by International Plasma Corporation.
Atomic Absorption Spectrophotometer Model 303 with a background
compensator installed internally by Perkin-Elmer Corporation.
Atomic Absorption Spectrophotometer Model 305B by Perkin-Elmer
Corporation.
Graphite Furnace,-Model HGA-2000 by Perkin-Elmer Corporation.
Three-Meter, Grating Emission Spectrograph by Baird-Atomic
Corporation
Spectrophotometer, Model DB by Beckmari, Inc.
Research pH Meter, Model 12 by Corning Corporation.
Fluoride Specific Ion Electrode by Corning Corporation.
Calomel Fiber-Junction Reference Electrode by Corning Corporation.
Digital Volt-Ohm-Milliampere Meter, Model 460 by Simpson, Inc.
Sample Preparation
A. Size Reduction
All coal and residue samples were air dried and were crushed to pass
an 80 - mesh sieve.
B. Organic Matter Removal
Several methods are available to prepare coal samples for trace elements
analysis.
The first step in each technique usually involves the destruction
of the organic material in the coal.
One method of organic material destruc-
tion is the high temperature ashing (HTA) process, by which, the sample is
ashed in a muffle furnace at 400 to 800°C, resulting in the rapid oxidation
of the organic material.
Significant losses of volatile trace elements such
as arsenic, selenium, cadmium, and antimony during HTA, make this process
unacceptable for the analysis of these elements.
The wet oxidation method,
on the other hand, will introduce additional contaminants because of the
large quantities of mineral acids used in the sample digestion.
17
-------
The low temperature ashing (LTA) process removes the organic matter
by plasma oxidation, at 1 rom oxygen pressure, and low temperature (~l100C).
This methc,d is the most effective way to achieve the oxidation of organic
matter without introducing additional contaminants or undue loss of volatile
trace elen.ents. Some trace elements will be lost even during LTA, such as
mercury, sulfur, nitrogen, and chlorine, which must be analyze~ in whole
coal samples by other suitable methods.
The details of the low temperature ashing technique have been described
in several publications 1,2,3,4. For this study, we have followed the LTA
procedure that was developed for our earlier work4 on bituminous coal samples,
except that the power input had to be increased from 15 watts/cell (used on
bituminous samples) to 20 watts/cell for lignite samples, in order to
maintain b.e LTA temperature at or below 115°C for the oxidation of organic
matter.
C.
Sample Dissolution and Analysis
Since there were nearly 40 elements to be analyzed, no single
dissolution procedure was found to be suitable for the entire list of
elements.
In fact, certain refractory elements were analyzed directly in the
LTA ash sIDlples by emission spectroscopy. The bulk of the elements, however,
were divided into four convenient categories or groups according to their
particular analytical requirements as outlined in Tables 10 and 11.
1.
Cc.tegory I Elements
Care ~~s taken to insure that better than 95% of initial organic matter
in the coal samples were driven off by the LTA ashing before the addition
of concentrated HCl04 to the samples to prevent explosion.
A 0.5 g sample of LTA ash was weighed into a 100 ml Teflon beaker
followed by the addition of 20ml conc. HN03 and 5 ml cone. HCl04. The
beaker was heated gently until the initial reactions had subsided and the
solution had become clear, indicating the complete oxidation of any residual
organic matter. The beaker was removed and allowed to cool, rinsing the
cover with a few ml of deionized water followed by the addition of 10 ml
49% HF.Th~ heating was applied again until nearly all of HCl04 was driven
off. The bo~aker was, next removed from the hot plate and allowed to cool
18
-------
Table 10.
METHODS FOR SAMPLE PREPARATION
Cate20ries
Methods of Sample Dissolution
I
Dissolution by HCl04 - HF treatment,
then put in HCl matrix.
II
Dissolution by HZS04 - HNO) treatment,
then put in HZS04 matrix.
III
Analyzed by Emission Spectrography
without a sample dissolution step.
......
\0
IV
Individual methods required for
sample dissolution.
Elements
Li, Na, K, Be, Mg, Ca, Ti,
V, .Cr, Mo, Mn, Fe, Co, Ni,
Cu, Zn, Cd, Pb, and Bi
As, Se, Te, Sb, and Sn
Zr, Sm, Yb, and Ge
Ag, B, Ba, F, Hg, Cl, N,
S, Si, and Th
-------
Tal,Ie 11.' ANALYTICAL METHODS FOR CHEMICAL ANALYSIS
OF SOLID SA MPLES
Detect~on Precision,
Constituent Method Range c .%d
Limi t
Antimony 1. L T A -acid dis solution a 0.001 ppm 0.04-2 ppm 5
Iodid e - benz.en e ext r action
Flameles s AAS
2. LTA-acid dissolutiona O. 00 1 ppm 3
Hydride formation
Heated-quartz- cell AAS
Arsenic 1. L T A -acid di s solution a O. 01 ppm 3.0 -30 ppm 7
Flameless AAS
2. LTA-acid dissolution a 0.05 ppm 5
Ion- exchange column
separation
APCD-MIBK extraction
Air-CzHz flame AAS
3. LTA-acid dissolution a 0.001 ppm 7
Ion-exchange column
separation
APCD- MIBK extraction
Flamele s s AAS '
4. LTA-acid dissolution a 0.001 ppm .3
Hydride formation
Heated-quartz- cell AAS
Barium 1. HTA-acid dissolution a 0 . 0 1 ppm 20 ppm - 5
NzO-CzHz FES 2%
2. HT A - acid di s solution a 0.001 ppm 4
HZS04 ppt
NH40H-EDTA redissolution
NzO-CzHz FES
3. HTA-NaZCOJ fusion 65 0.001 ppm 4
Hot-water leaching
HCl dissolution
NzO-CzHz FES
Beryllium 1. LTA-acid dissolution a 0.002 ppm 0.2-2 ppm . 7
NzO-CzHz AAS
2. LTA-acid dissolution a 0.0001 ppm 5
Flameless AAS
Bismuth LTA-acid dissolution a 0.02 ppm 0.2-2 ppm 5
APCD-MIBK extraction
Flameless AAS
20
-------
Table 11, Cont'd. ANALYTICAL METHOD~ FOR CHEMICAL ANALYSIS
OF SOLID SAMPLES
Detection Precision,
Constituent Method Limitb Range c %d
Boron LTA-NazC03 fusion a o. 05ppm 30 - 500 ppm .s
Diol-CHC13 extraction
NzO-CzHz FES
Cadmium 1. LTA -acid dissolution a 0.005 ppm O. 1 -10 ppm 4
APCD-MIBK extraction
Air -CzHz flame AAS
2. LTA-acid dissolution a 0,.0001 ppm 1-50 ppm I 5
APCD-MIBK extraction
Flameles s AAS
Calcium LTA-acid dissolution a 0 . 002 ppm 0.1%-2% 3
Air-CzHz flame AAS
Chlorine Eschka-HN03 extraction65 1 ppm 0.01% '" 8
Amperonietric titration 0.5%
Chromium LTA-acid dissolution a o. 01 ppm 10-500 ppm 4
Air-CzHz flame AAS
Cobalt 1. LTA-acid dissolution a 0.001 ppm 1-50 ppm 5
Flameless AAS
2. LTA-acid dissolution a 0.0001 ppm 6
APCD-MIBK extraction
Flameless AAS
Copper LTA-acid dissolution a O. 0 1 ppm 5-50 ppm 3
Air-CzHz flame AAS
Fluorine a O. 1 ppm 30 - 300 ppm 9
Oxygen Bomb - SIE
Germanium LTA-emission spectro- 1 ppm 1-40 ppm 10
graphy
Iron LTA -acid dissolution a 0.005 ppm 0.2%-5% 2
Air-CzHz flame AAS
Lead 1. LTA-acid dissolution a 0.0 Ippm 2-50 ppm 4
APCD-MIBK extraction
Air-CzHz flame AAS
2. LTA-acid dissolution a 0.001 ppm 6
APCD-MIBK extraction
Flameles s AAS
Lithium LTA-acid dissolution a 0.001 ppm 2-50 ppm 3
NzO-CzHz FES
21
-------
Table 11. Cont'd. ANALYTICAL METHODS FOR CHEMICAL ANALYSIS
. OF SOLID SAMPLES
Detectbon Precision,
Constituent Method Limit Range c . %d
Magne.siur.:1 LTA-acid dissolution a 0~001 ppm 0.02%---1% 2
Air-CzHzf1ame AAS
Manganes€: LTA -acid dis solution a 0 . 0 1 ppm 5 - 100 ppm 3
Air-CzHz flame AAS
:.Mer cu ry Total combustion - O. 1 ppb O. 0 1- 5 ppm 10
KMn04a
Cold vapor flameless AAS
Molybdenum LTA-acid dissolution a 0.005 ppm 1- 10 ppm 6
Flameless AAS
Nickel' LTA -acid dis solution a O. 01ppm 10-50 ppm 4
Air-CzHz flame AAS
Nitrogen KJe1dahl digestion -
titrationl
Potas sium L TA -acid'"dis solutiona 0.001 ppm 0.02%-0.2% 3
Air-CzHz FES
Samarium LTA-emission 0 . 5 ppm 0.2-2 ppm 10
a
spectrography.-
Selenium 1. L T A -acid di s solution a 0.01 ppm O. 1-50 ppm 6
Flameless AAS
2. LTA -acid dis solution a 0.00 I ppm 5
Ion- exchange column
separation
APCD-MIBK extraction
Flameless AAS
Silicon 1. LTA-gravimetric O. 1 mg 1 %-5 % 2
methoda
2. LT A -acid digestion O. I ppm 3
bomba . .
NzO-CzHz flame AAS
Silver LTA-acid dissolutiona 0.001 ppm O. 1 - 5 ppm 6
Flameless AAS
Sodium LTA-acid dissolution a 0.005 ppm 0.01 - 3
Air-CzHz FES O. 2 ppm
22
-------
Table 11, Cont'd. ANALYTICAL METHODS FOR CHEMICAL ANALYSIS
OF SOLID SAMPLES
Detection Precision,
Constituent Method Limitb Range c %d
Strontium L T A -acid dis solutiona 0.001 ppm 10-500 ppm 3
NzO-CzHz FES
Sulfu r Es chka - gravimetric O. 1 mg 0.1% '" 5% 2
method!
Tellurium .1. LTA-acid dissolution a O. 0 1 ppm O. 1 ...;, 10 ppm 6
F1ame1es s AAS
2. LTA-acid dissolution a . O. 001 ppm. 5
Ion-exchange column
separation
APCD-MIBK extraction
Flameles s AAS
Thorium LtA-acid dis solution a 0.02 ppm 0.1 '" 5ppm 6
Ion-exchange column
separation
Colorimetric method
Tin 1. L T A -acid dis solution a O. 01 ppm . O. 1 '" 5 ppm 6
Iodide-isopropy1/ ether
extraction
F1ameless AAS
2. L T A -acid dis solution a O. 0 1 ppm 5
Hydride formation
Heated-quartz-cell AAS
Titanium LTA-acid dissolution a O. 1 ppm 0.01% '" 4
NzO-CzHz flame AAS O. 1 %
Vanadium 1. LTA-acid dissolution a O. 2 ppm 10 -100 ppm 10
NzO-CzHz flame AAS
2. L TA -acid dis solution a O. 0 1 ppm 5
Ion- exchange column
separation'
APCD-MIBK extraction
NzO-CzHz flame AAS
Ytterbium LTA-emission O. 1 ppm O. 1 -1 ppm 10
a
spectrography
23
-------
" .
Table 11, Cantld. . ANALYTICAL METHODS FOR CHEMICAL ANALYSIS
OF SOLID SAMPLES
"-
Constituent
Method
Detection Presicion,
Limitb Range c %d
O. 0 1 ppm 5-100 ppm 6
1 ppm 10 -100 ppm 10
Zinc
LTA-acid disso1utiona
Air-CzHz flame AAS
Zirconium
LTA-emission
a
spectrography
Abbreviations:
AAS - Atomic absorption spectrophotometer
APCD - Ammonium pyrrolidine carbodithioate
. Dio1 - 2 ..ethy1-1, 3 -hexanediol
EDTA - Ethylenediamine tetraacetic acid
FES - Flame emission spectrophotometer
HTA- High-temperature ashing
L T A - Low-temperature ashing
MIBK - Methylisobuty1 ketone
SIE - Selective ion electrode.
Notes:
a
Methods currently in use at IGT.
b
.," .
Detection limits are estimated as the concentratioZt of the constituent in
the sample solution or mixture that would produce a signal twice as large
as the background noise level. In gravimetric methods, detection limits
are expr,:!s sed as the minimum weight the balance can accurately weigh
(0. 1 mg :In IGT' s Analytical Laboratory).
c
The range refers to the estimation of the constituent concentration in tbe
sample.
d
Precisio;1s are estimated by applying the specified analytical method to
the sample in the estimated range.
24
-------
before adding 5 ml of 6N HCl plus 30 ml of water and gently reheating the con-
tent until the solution became clear. After cooling the solution the contents
were quantitatively transferred to a 50 ml volumetric flask and brought up to
mark with deionized water for analysis by one of several atomic absorption
(or emission)methodst depending on the particular element ,being sought.
The Category I elements were further divided into three sub-groups At
Bt and Ct according to differences in the methods for their determinations.
Sub-group A included those elements which could be determined by
direct aspiration into a flame, namely Lit Na, K, Mg, Ca, Cr, Mn, Fe, Ni,
Cu,
Znt Tit and V.
In this group, Li, Na, and K were determined
by
air-CZHZ emission flame photometry, since they have higher sensitivity by
the flame emission method than flame atomic absorption methodS. In order
to suppress the ionization effect, 1000 ppm of Cs was added to all the
standard and sample solutions.
are given in Table 12.
Operational parameters for these elements
Mg, Ca, Cr, Mn, Fe, Ni, Cu, and Zn were determined by air-CZHZ flame
atomic absorption spectrophotometry (AAS). One thousand ppm of lanthanum
was added to all the standard and sample solutions, in order to eliminate the
possible chemical interferences from the sample matrix with the determination
of Ca and Mg.
Ti and V were determined by NZO - CZHZ flame AAS.
meters are given in Table lZ.
The operational para-
Sub-group B, consists of Be, Co, and Mo, which were determined by direct
introduction of the sample solution (or its dilution) into the graphite fur-
n~ce, and quantified by flameless atomic absorption.
The detection limits for Be and Co, using a graphite furnacet are about
O.OOOZ mg/ml and 0.006 mg/ml, respectively.
Therefore, these two elements
were measured in a very dilute sample solution with no significant matrix
effect.
On the other hand, Mo not having a very high sensitivity, even with
NOTE:
The maximum temperature which the teflon beaker can withstand is
-350°C, therefore, the hot plate should not be set higher than that.
Z5
-------
laDle .L-'. 0:i?ERAlIONAL :i?ARAMETER~ ~'0K "Hili lJ.lH' ~J:<.M.J.l'IAT.LV l'I Vl<'
CATEGORY I ELEl1ENTS
Spectral Opera tional Detection Relative Standard
Elements Flame type Mode Wa ve Length Band Width Range Limit k Deviation (RSD)
nm ~/ml
670.8 *
Li Air-CzHz Emission' 0.13 0-2 0.001 3 - 5%
Na Air-CzHz Emission 580.0 0.13 0 -10 0.0005 ... 3 "/.
K Air-CzHz Emission 766.5 0.13 0 -10 0.0005 - 3,,/.
Mg Air-C1Hz Absorption 285.2 0.6 0-1.0 0.0003 ... 2 "/.
Ca Air-CzHz Abso.rption 422.7 0.6 0 -10 0.002 ...2%
Ti NzO- CzHz Absorption 364.3 0.6 0 - 50 0.1 ... 5 '1.
V NzO-CzHz Absorption 318.4 0.6 0 - 5.0 0.02 -8%
r-..> Cr Air-CzHz Absorption 357.9 0.6 0 - 5.0 0.005 - 5%
0'\ Mn Air-CzHz Absorption 7.79.5 0.6 0 -10 0.002 -3%
Fe Air-CzHz Absorption 7.48.3 0.2 0 -10 0.005 ... 2 "/.
Ni Air-CzHz Absorption 7.3Z.0 0.2 0-5 0.005 - 5"/.
Cu Air-CzHz . Absorption 324.8 0.6 0-1:> 0..005 -2%
Zn Air-CzHz Absorption 7.13.9 0.6 0 - 2. 0 0.002 - 3,,/.
* '
In lignite samples lithium content is much lower than in the bitwninous samples and the RSD is higher
for lignite samples.
Vocal Length
Dispersion
400 mm
UV -- 0.65 run/mzn
0.03 to 10 mrn
Visible -- 1.3 nrn/rnrn
Slit upening
-------
the graphite furnace, had to be measured. in the original sample solution
without further dilution. The standard addition method was used to offset
the matrix effect. Furthermore, because of the memory effect, the graphite
cell was cleaned between runs (especially following a high conc. Mo solution)
at the maximum temperature of the furnace until the baseline returned to the
proper place. The background corrector was used for all the measurements,
using the graphite furnace in order to compensate for any unspecific mole~ .
cular absorption.
in Table 13.
The operational parameters for Be, Co, and Mo are given
Sub-group C, consist of Bi, Cd, and Pb which may be determined following
solvent extraction by aspirating the organic phase into a flame, or by intro-
ducing the organic phase into the graphite furnace.
In most cases, the use
of the graphite furnace required the use of the standard addition method,
which was not only tedious but less precise.
Using extraction as a separation
method, it was possible to eliminate the matrix effect in the graphite furnace
and also to pre-concentrate the sub-group C elements.
'Bi, Cd, and Pb were separated from the major constituents in the sample
I . 7,8
solution by a simple so vent extract10n , using sodium diethyldithiocarba-
mate or the ammonium pyrrolidinecarbodithioate as the chelating agents.
These ions were quantitatively extracted into methylisobutylketone (MIBK) in
a single pass extraction. With approximately 20 ml of the original sample
solution extracted into 5 ml MIBK, Pb and Cd were determined by direct aspir-
ation into an air-C2H2 flame. However, since the sample solution was not
available in sufficient quantity, the graphite furnace was used for their
determinations.
One ml of acid solution was extracted into 5 ml or MIBK to
recover Pb and Cd, and 5 ml of sample solution was extracted into 5 ml of
MIBK for Bi determinations.
are present in Table 13.
The operational parameters of the instrument
27
-------
Table 13. OPERATIONAL PARAMETERS FOR THE DETERMINATION OF
CATEGORY I ELEMENTS
Sample
Solution Spectral Operation Drying Ashing Atomizing *
Elements Matrix Wave Length, Band Width Ral'1ge Cycle Cycle Cycle RSD
om -1.@/r04-
Bi MIBK .223.0 0.2 0 - 0.1 120 .C-30 See 150 .C-30 See 2300 .C-5 See - 5'1.
Be Hcl 234.9 0.6 0 - 0.001 150 .C-50 See 450 .C- 50 See 2400 .C-5 See -3'1.
Cd MIBK 228.8 0.6 0 - 0.01 120 .C-30 See 150 .C-30 See 2000 .C-5 See - 5'1.
Co He! 240.7 0.2 0 - 0.1 150 .C- 50 See 450 .C-50 See 2300 .C-5 See -3%
N Mo Hcl 313.3 0.2 0 - 0.1 150 .C-60 See 450 .C-60 See 2700 .C-lO See -10'1.
"(XI
Pb MIBK 283.3 0.2 0 - 0.01 120 .C-30 See 150 .C-30 See 2000 .C-5. See -3'1.
* Relative standard deviation
-------
2.
Category II Elements
As shown in Table 14 the fluorides
of arsenic,
selenium, and
..-
tellurium have moderate to high volatilities. Therefore, instead of HF-HCl04
acids a mixture of HN03 - H2S04 acids was used to prevent the loss of these
elements during sample decomposition and dissolution.
Sample dissolution ~as accomplished by , weighing a 0.5g of LTA
sample into a glass beaker and adding 29 ml of cone. HN03 and 5 Ml selenium-
free sulfuric acid.* The beaker was covered and heated gently for about one
hour, followed by a second period at higher heating until the sulfuric acid
fumes had appeared and the solution had turned clear. Next, 5 ml of
deionized water were added and the solution was heated to white fumes
again.
Then 30 ml of deionized water were added, the solution boiled,
filtered into a 50 ml v~lumetric flask and brought up to 50 ml mark.
Arsenic, selenium and tellurium were determined by introducing the
sample solution or its dilution directly into a graphite furnace and making
the measurements.
given in Table 15.
The operational parameters for these elements are
. d. d 11 12
Antimony was extracted as its 10 1 e , , using benzene. 'An aliquot
of the sample solution containing approximately 0.1 ~g of antimony was
placed in a centrifuge tube. The sulfuric acid concentration was adjusted
to 5~, and sufficient KI was added so that the final volume had a concen-
tration of 0.01 M in KI.
The final volume of the sample solution was
adjusted to 5 ml, then 0.5 ml of benzene
was added by a micropipet.
The
solution was then shaken vigorously for one minute and centrifuged,
retaining the benzene phase for the determination of antimony by graphite
furnace.
Tin was extracted from acid solutions with 1.5 M KI and 1.5 M H2S04
into an isoproplyl ether solution12, thus extracting the tin in ether layer
for determination in the graphite furnace.
for these elements are given in Table 15.
The operational parameters
*NOTE: Selenium-free sulfuric acid is prepared by diluting 150 ml concen-
trated H2S04 with 150 ml deionized water, adding 15 ml HBr and
boiling until the volume is reduced to less than 200 mI.
29
-------
TABLE 14. BOILING POINTS OF 10
As, Se, Te, Sb and Sn FLUORIDES
Compound Boiling Point, °c
As F3 -80
As F5 -8.5
Se F6 -34.5
Se F4 >100
Te F6 3S.S
Te F4 >97
Sb F3 319.., Sub1.
Sb FS 147.S
Sn F2
Sn F4 705 Sub1
30
-------
Table 15. OPERATIONAL PARAMETERS FOR THE DETERMINATION OF
As, Se, Te, Sb, and Sn.
Solution Spectral Operatio~ Drying Ashing Atomizing *
Elements Matrix Wave Length Band Width Range Cycle Cycle Cycle RSD
nm -lJg/m1-
As H2S04 193.7 0.2 0 - 0.1 120 °C-60 See 400 °C-60 See 2000 °C":'5 See 5%
Se H2S04 196.0 0.6 0 - 0.1 120 °C-60 See 400 °C-60 See 2000 °C-5 See 5%
Te H2S04 214.3 0.2 0 - 0.1 120 °C-60 See 400 °C-60 See 2400 °C-5 See 6%
w 2000 0C-8 See
""" Sb Benzene 217.6 0.2 0 - 0.05 100 °C-30 See 150 °C-30 See 7%
Sn Isopropyl 224.6 0.2 0 - 0.2 100 °C-30 See 150 °C-30 See 2400 °C-5 See 7%
Ether
*
Relative Standard deviation
-------
3.
Category III Elements
The compounds of the elements belonging to this group were either diffi-
cult to b:~ing into solution, or were present at such low concentrations that
the dissolution step wouid have diluted them beyond the sensitivity of the.
instrument used for their measurement.
Group III elements include Ge, Sm, Yb,
and Zr.
Arc..emission spectrography was used for their determinations.
This
method had the following advantages:
1)
Acid dissolution was not necessary,
2) The setlsitivity was high enough for the determination of these elements,
3) It offered speed of operation. Usually, any emission spectrographic
method fo]' a particular kind of sample requires a certain amount of time for
method.development and set-up.
Since a relatively small number of samples
required this analysis, the standard addition method was used to offset the
interferences from sample matrix.
The analytical line pairs are given in
Table
Table 16. ANALYTICAL LINE PAIRS
FOR GROUP III ELEMENTS
Ge 303.9lnm I Fe 303.79 nm
Sm 442.43 nml Fe 441.51 nm
Yb 398.80 nml Fe 400.53 nm
Zr 360.12 nml Fe 365.15 nm
One part of the LTA ash sample was mixed with two parts of spectro-
chemically pure graphite powder, containing known amounts of each element
sought. The-electrodes were National Spectrographic Laboratory L400 cratered
electrode and L3951 round top counter electrode. The mixture was loaded into
a cratered electrode with a spatula, and made into a cone shape with a sharp-
ened graphite rod. The 3 mm wide analytical gap was surrounded by an 80%
argon and 20% oxygen atmosphere from a Stallwood jet in order to eliminate
CN band emission.
The conditions for arcing were 10 see pre-arcing at 5 amp,
50 sec arcing at 10 amp, and then 60 see arcing at 15 amp.
The pre-arcing
step was important because the LTA sample still contained some residual car-
bonaceous natter, which would have volatilized first, resulting in a high
back~round reading.
32
-------
The photographic Plate was developed in Eastman D-19 Developer for 3 min
and fixed for another 3 min in Eastman Fixer with a cold'tapwater rinse in
between.
The temperature of the developer and the fixer was kept constant
with a water bath.
4.
Category IV Elements
The procedures for the sample preparation and determination of elements
in this group have been developed for each element individually.
this group are, Hg, F, B, Ba, Si, Ag, Cl, and Th.
Elements in
Many methods are available for the determination of mercury13-l9, how-
ever, the flameless atomic absorption method (with minor modifications) was'
adopted for this study. A one-g sample of whole coal was burned in an ASTM
carbon-hydrogen train with CuO as the only packing material. Mercury vapors
were collected from the combustion effluents in an absorbing solution contain-
ing 1% KMn04 in 0.1 N H2S04' which was then reduced by a solution made up by
dissolving 4 g SnC12 and 2 g NH20H in concentrated HCl and then diluted to
100 mI.
The absorbing solution and other reagents were checked prior to use to
make certain that ,there was no detectable amount of mercury present as contam-
inant. Before the operation, the carbon-hydrogen train was purged overnight
with mercury-free oxygen ata flow rate of 20 ml/min at the operating temper-
ature.
Blank runs were made to make sure that combustion train was free from
contamination.
Following the combustion, an aliquot of the absorbing solution, contain-
ing less than 20 nanograms of mercury was drawn into a 50 ml plastic syringe.
Water was added to bring the total volume to 10 ml, followed by the addition
of 5 ml of the reducing solution. Clean air was drawn in to give a total gas
volume of 30 ml in the syringe.
The syringe was capped and shaken vigorously
for 30 seconds, then the vapor contents were injected into the cell, taking
care not to inject any solution.
After tracing the signal for 5-10 seconds,
the air was drawn back into the syringe from the cell and the cell was purged
with air so that recorder pen returned to the baseline.
33
-------
F1u)rine was determined in whole coal by an oxygen-bomb combustion and
selective ion electrode method19,20. A 19 sample of -80 mesh coal was weighed
in a stai':lless steel container, and then fired in an oxygen bomb, cbarged with
30 atm of oxygen and 10 ml 0.05 N NaOH.
After firing, the bomb was cooled,
depressur:lzed, and sample solution was transferred to a 50 ml glass beaker.
The bomb '~as rinsed thoroughly with three 5 ml portions of 0.05 N NaOH, add-
ing the r:lnsings to the sample solution.
The total solution was heated gently
on a hot plate to expel1 dissolved C02 and 02' then transferred to 25 ml vol-
umetric flask and diluted to volume.
Ten m1 of sample solution was mixed with 10 ml of a buffer solution,
made by m:Lxing 57 ml of acetic acid and 58 grams sodium chloride with 4 grams
of cyclohl!xanediamine-tetra-acetic acid.
final vol'~e brought to 1 liter.
The pH was adjusted to 5.3 and the
The measurements were made using a fluoride-ion electrode against a
reference electrode.
A research pH meter on mV mode was used as the readout.
The standard addition method was used by adding 20 and then 40 mg of fluoride
to the sO:.ution after the initial measurement was made.
The concentrations
were read from a standard curve and the percent recovery calculated from the
concentrations.
In earlier work, boron in coal was determined by emission spectrographic
method.
llowever, since then, the extraction of boron by 2-ethyl-l, 3-hexane-
diol into an organic solvent and subsequent determination by N20 - H2 flame,
22 23 24 .
emission s:pectrophotometry , , was found, to be a simpler procedure. It
was also comparable to colorimetric methods in its precision and sensitivity,
but easie]' to follow.
The LTA sample was used for boron determination, because there are many
contradictory statements in the literature concerning the gains and losses of
boron during the high temperature ashing process. However, a few samples
ashed at 500 °c in this. laboratory and analyzed for boron, showed comparable
results with LTA ash samples.
'34
-------
A mixture of 0.2 grams LTA sample and 3 grams of Na2CO) was 'fused on a
blast burner for 5 to 10 minutes, and dissolved in the proper amount of HCl.
The total sample solution was adjusted to 20 ml in a plastic separatory funnel.
Ten ml of a 1:9 solution of 2-ethyl-l, 3-hexanediol in chloroform was added
to the separatory funnel. After the extraction of boron by the organic phase,
the chloroform was drained from the bottom of the funnel and aspirated into a
N20 - H2 flame, with a flow rate of 12 l/min for both gases. Using a 5cm
slot burner head the emission of B02 was ,measured at 518.2 nm. The slit
width was set at 4 on the Perkin-Elmer 305B Atomic Absorption Spectrophoto-
meter corresponding to 0.6 nm of the spectral band width. A blank solution
was also aspirated between the sample solutions, using zero suppression to
adjust the baseline.
The determination of the Ba in solution, using an emission NiO - C2H2
flame was relatively easy26,27. The sample dissolution for.the determination
of barium in coal samples, however, presented a unique problem due to the
wide range of the barium contents in coal samples and very low solubility of
the barium sulfate in acid solution.
The direct acid dissolution of LTA samples of lignite by HCl04 - HF
treatment was not satisfactory and gave low results. Because of the low con-
centration of barium in bituminous samples, the HTA sample could be dissolved
by HCl04 - HF acid treatment provided that the sample size was kept smaller
than O.lg and the final volume was at least 100 mI.
The lignite samples were dissolved in sulfuric acid and recovering the
barium as barium sulfate.. The barium sulfate was redissolved either by ethyl-
d' , "d25
ene 1am1ne tetra acet1c aC1 or by fusion with sodium carbonate followed by
aqueous leachings to separate the sulfate from the barium and dissolution of
the barium carbonate in hydrochloric acid.26 These methods were found to be
adequate for the determination of barium by N20 - CZHZ flame emission. The
background emission, however, caused by the large amounts of Ca in'the solu-
tion as CaOH was corrected by measuring both sides of the barium 553.5 nm
emission line.
The average of the measurements was then used to correct the
measurement made at the 553.5 nm Ba emission line.
35
-------
SiH,con was determined either by the classical gravimetric method
using HF c.evolatilization method, or by 'NZO - CZHZ flame atomic absorption
spectrophctometry following the Parr acid-::digestion bomb treatment. These
two methoc,s gave comparable results, but the atomic absorption method was
preferred because it was less time consuming.
In the acid-digestion bomb method for Si, 0.1 g of LTA sample was put
in a 25 ml Parr acid-digestion bomb with 3 ml HN03 (conc.) and 0.5 ml HF (48%).-
The bomb ~'as tightly closed by hand and placed in an oven at 150 °c for 1-2
hours.
Tt.e bomb was then, removed from the oven and cooled to room tempera-
ture and cpened carefully.
A 10 ml volume of a saturated boric acid solution
was next ~,dded to the contents to react with excess HF acid.
The sample solu-
tion was tr~nserred to a 100 ml pl~sti~ volumetric flask and'brought to volume
with deior.ized water.
A series of standard solutions were also prepared in
the same ~.cid matrix, and their absorption signals were measured at 251. 8 run.
The determination of Ag was accomplished by the graphite furnace/atomic
absorptior, method. The LTA sample was dissolved by HCl04 - HF treatment,
followed ty HN03 instead of HCl, to prevent precipitation of Agel. All glass-
ware were carefully rinsed with 3 N HN03 and deionized water to remove traces
of chloric.e ion. The sample solution was then introduced directly into a
graphite furnace.
The operational parameters are listed in Table 17.
Chlorine was measured by Eschka/amperometric titration method. The
sample prE!paration steps followed the ASTM method. The filterate from Eschka
procedure: was titrated amperometrically against 0.005 N AgN03 solution, using
20 ml of Hample solution, 5 ml acetone, and 5 ml 1% gelatin solution. .Nitrogen
was passed through the solution for at least 5 minutes before the titration
had begun.
Tho]:ium was determined by a colorimetric method after the separation
of thoriwl by extraction with trifluorothenoyl acetone (TTA), and back-extrac-
tion.29 rhe iron (III) whi~h interferred with the extraction of Th in TTA was
first removed by extraction with isopropyl ether from a 6 N HCl solution.
The thorium so separated was then reacted with thorin, and its absorbance
was measured in spectrophotometer at 545 nm with a 5 cm cell.
was used .as reference blank..
A zero standard
36
-------
Ag
Wave
LenJ;th (run)
328.1
Table 17. OPERATIONAL PARAMETERS FOR THE
DETERMINATION OF Ag.
Spectral Operation
Band Range
Width (run) ~g/ml)
0.6 0-0.1
* Relative standard deviation
Drying
Cycle
150 .C-60 See
37
Ashing
Cycle
500 .C-60 See
Atomizing
Cycle
2400 .C-5 See
*
RSD
50/.
-------
References Cited
1.
F. W. Frazer, andC. B. Belcher, "Quantitative Determination of the
Mineral-Matter Content of Coal by a Radiofrequency-Oxidation
Tec::lnique". Fuel~,41-46 (1973).
2.
H. J .::lluskoter, "Electronic Low-Temperature Ashing of Bituminous
Coa.l". Fuel 44, 285-291 (1965). .
3 .
R. R. Ruch, H. J. Gluskoter, and N. F. Shimp, IIOccurrence and
Distribution of Potentially Volatile Trace Elements ip. Coaill.
Env:~ronmentalGeologyNotes, No. 72,1974, 96pp. ill. Geological
Survey.
4.
A. Attari, "Fate of Trace Constituents of Coal During Gasification".
EPA Technology Series, EPA-650/2-73-004, 31 pp (1973).
5.
E. E. Pickett, and S. R. Koirtyohann, J1Emission Flame Photometry -
A N,~w Look at an Old Method". Anal. Chem. i!.., 28A-42A (1969).
6.
J. W. Robinson, and P. J. Slevin, "Recent Advances in Instrumentation
in Atomic Absorption". American Laboratory, Aug. 10-18, 1972.
7.
H. Bq>,de, "Systematishe Untersuchungen tiber die Anwendbarkeit der
Diathyldithio-carbaminate in der Analyse". Z. Analyt. Chem.
142, 414-423 (1954).
8.
1/
H. Bode, "Systematishe Untersuchungen uber die Anwendba'rkeit der
"
Diathyldithiocarbamate in der Analyse". Z. Analyt. Chem. 143,
182..195 (1954).' -
9.
H. Ma:.issa, und E. Sch8ffmann, "Uber die Verwendung von Substituie'rten
Dithiocarbamaten in der Microana1yse Ill". Microchim. Acta 42,
18 7 -;~ 0 2 (1 955). -
10. Handbook of Chemistry and Physics, p. B63 - p. B156, 51st Edition,
197(-1971, The Chemical Rubber Company.
11. R. W. Ramette, "Benzene Extraction of Antimony Iodide".
30, H58-1159 (1958).
Anal. Chem.
12. G. Mo:~rison, and H. Freiser, "Solvent Extraction in Analytical
Chelnistry. John Wiley & Sons, lnc. 1957.
13. B. C. Southworth, J. H. Hodecker, and K. D. Fleischer, "Determination
of Mercury in Organic Compounds". Anal. Chem.1.Q, 1152-1153 (1958).
14. B. W. Bailey, and F. C. Lo, "Cold Vapor Atomic Absorption De.termination
of Mercury in Coal". JAOAC 54,1147-1149 (1971).
15. 0.1. Joensuu, "Mercury Vapor Detector". Appl. Spec. ~, 526-528 (1971).
16. J. V. O'Grouman, N. H. Suhr, and P. L. Walker, Jr.; I'The Determination
of M.ercury in Some American Coa1sl/. Appl. Spec. 26,44-47 (1972). .
38
-------
.. .
17. J. Marinenko, 1. May, andJ. 1. Dinnin, IIDeterminationofMercury
in Geological Materials by Flameless Atomic Absorption Spectrometry".
USGS Prof. Paper 800B, B 151-B155, (1972).
18. H. J. Isaq, and W. L. Zielinski, Jr., "Hot Atomic Absorption
. Spectometry Method for the Determination of Mercury at the
Nanogram and Subnanogram Levelil. Anal. Chern.. 46,1436-1438
(1974).
19. M. P. Stainton, "Syringe Procedure for Transfer of Nanogram Quantities
of Mercury Vapor for Flameless Atomic Absorption Spectrophotometry".
Anal. Chern. 43, 625-627 (1971).
20. J. Thomas, Jr., andH. J. Gluskoter, "Determination of Fluoride
in Coal with the Fluoride Ion-Selective Electrode". Anal. Chern.
46,1321-1323 (1974).
21. D. A. Levaggi, W. Dyung, and M. Feldstein, IIMicrodetermination of
Fluoride in Vegetation by Oxygen Bomb Combustion and Fluoride
Ion Electrode ~nalysis". JAPCA~, 277-279 (1971).
22. E. E. Pickett, J. C. Pau, andS. R. Koirtyohann, "Determination of
Boron in Fertilizers by Emission Flalne Photometry in the Air-
Hydrogen Flame". JAOAC 54,796-800 (1971).
23. J. C. Pau, E. E. Pickett, and S. R. Koirtyohann~ "Determination of
Boron in Plants by Emission Spectroscopy with the Nitrous Oxide-
Hydrogen Flame". Analyst 97,860-865 (1972).
24. E. E. Pickett, and J. C. Pau, "Emission Photometric Determination
of Boron in Unboronated Fertilizers Using Nitrous Oxide-Hydrogen
Flamel'. JAOAC~, 151-153 (1973). .
25. F. J. Welcher, "The Analytical Uses of Ethylene-Diamine-Tetra
acetic Acid". p. 147-148, D. Van Nostrand Co. Inc. 1958.
26. W. F. Hillebrand, and G. E. F. Lundell, "Applied Inorganic Analysis".
p. 630-631, John Wiley &Sons, Inc. 1961. .
27. E. E. Pickett, and S. R. Koirtyohann, liThe Nitrous Oxide-Acetylene
Flame in Emission Analysis - I". Spectrochim. Acta. 23B, 235-244
(1968). -
28. S. R. Koirtyohann, and E. E. Pickett, lIThe Nitrous Oxide-Acetylene
Flame in Emission Analysis -1111. Spectrochim. Acta. 23B,
673-685 (1968). -
29. 1. M. Kolthoff, Editor, IITreaties on Analytical Chemistry".
Vol. 5, 13 9-216 (1961) Interscience Publishers, Inc.
Part II,
30. A. Attari, M. Mensinger, J. Pau, IIInitial Environmental Test Plan
for Source Assessment of Coal Gasification, II EPA Technology
Series, EPA-600/2-76-259, 145 pp (1976).
39
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TECHNICAL REPORT DATA
(Please read /us1ructions all the rel'erse before completing)
1. REPORT NO. 12. 3. RECIPIENT'S ACCESSION' NO.
EPA-600/2-76-258
4. TITLE A"iD SUBTITLE FATE OF TRACE AND MINOR 5. REPORT DATE
September 1976
CONSTITUENTS OF COAL DURING GASIFICATION 6. PERFORMING ORGANIZATION CODE
7. AUTHOR(S) 8. PERFORMING ORGANIZATION REPORT NO.
A. Attari, J. Pau, and M. Mensinger
9. PERFORMING ORGANIZATION NAME AND ADDRESS 10. PROGRAM ELEMENT NO.
Institute of Gas Technology lAB013; ROAP 2lADD-024
3424 South State Street 11. CONTRACT/GRANT NO.,
Chicago, Illinois 60616 68-02-1307
12. SPONSORING AGENCY NAME AND ADDRESS 13. TYPE OF REPO?{ AN/PERIOD COVERED
EPA, Office of Research and Development Task Final; -12 74
14. SPONSORING AGENCY CODE --
Industrial Environmental Research Laboratory
Research Triangle Park, NC 27711 EPA-ORD
15. SUPPLEMENTARY I\IOTES IERL-RTP project officer for this report is W. J. Rhodes, Mail
Drop 61, 919/549-8411, Ext 2851. . . .
16. ABSTRACT The report gives results of a study of the fate of selected minor and trace
elements of Montana lignite and Illinois No.6 bituminous coals during development of
the FrrGAS process. Solid residue. samples from various development stages were
analyzed. The data indicate that certain volatile trace elements are removed from
the coal during gasification. Removed from the solids during processing were such
elements as antimony, arsenic, bismuth, cadmium, chlorine, fluorine, mercury '
lead, selenium, and tellurium. It is estimatedthat, in a full scale operation, these
will appear in the quench water system.
17. KEY WORDS AND DOCUMENT ANALYSIS
a. DESCRIPTORS' b.IDENTIFIERS/OPEN ENDED TERMS C. COSATI Field/Group
Air Pollution Air Pollution Control l3B
Coal Gasification Stationary Souroes l3H
Chemical Analysis Trace Elements 07D
Lignite HYGAS Process 21D
Bituminous Coal Minor Constituents
18. DISTRIBUTION STATEMENT 19. SECURITY CLASS (This Report) 21. NO. OF PAGES
Unclass Hied 45
Unlimited 20. SECURITv CLASS (This page) 122. PRICE
Unclassified
EPA Form 2::20-1 (9.73)
40
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