CT U ^k U.S. Environmental Protection Agency Industrial Environmental Research
^B m^ f\ Office of Research and Development Laboratory
Research Triangle Park, North Carolina 27711
EPA^"600/7"77-141
December 1 977
ANALYSES OF GRAB SAMPLES
FROM FIXED-BED COAL
GASIFICATION PROCESSES
Interagency
Energy-Environment
Research and Development
Program Report
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EPA-600/7-77-141
December 1977
ANALYSES OF GRAB SAMPLES
FROM FIXED-BED COAL
GASIFICATION PROCESSES
by
Karl. J. Bombaugh
Radian Corporation
P.O. Box 9948
Austin, Texas 78766
Contract No. 68-02-2147
Exhibit A
Program Element No. EHE623A
EPA Project Officer: William J. Rhodes
Industrial Environmental Research Laboratory
Office of Energy, Minerals and Industry
Research Triangle Park, N.C: 27711
Prepared for
U.S. ENVIRONMENTAL PROTECTION AGENCY
Office of Research and Development
Washington, D.C. 20460
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ABSTRACT
This report describes the results of an analytical
screening study of selected effluent samples from operating coal
gasification units. This work was done to aid in planning for
future more comprehensive environmental test programs which will
be conducted at gasification facilities located both in this
country and abroad. A secondary objective of this work was to
evaluate EPA's phased approach to environmental testing of coal
gasification facilities.
Grab samples from five different commercial-scale
gasifiers and one pilot-scale gasifier were obtained for this
study. These samples included tar, process condensate, gasifier
ash and cyclone dust. All of the gasifiers sampled were single-
stage, fixed-bed, atmospheric pressure, air-blown units; however,
the coal feed materials consumed by those gasifiers included both
bituminous and anthracite coals. The analyses which were per-
formed were intended to identify, in a very preliminary manner,
the classes of compounds present in each sample which warrant
further attention.
A number of significant conclusions are drawn from the
results of this screening study. These conclusions relate to:
a) the classes and concentrations of components found in specific
i
samples, b) the effects of feedstock and process operating con-
dition changes upon the levels of key components detected in
those samples, and c) modifications/additions to suggested EPA
procedures which will help to insure that the maximum amount of
useful environmental information is obtained from future programs.
111
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CONTENTS
Review Notice
Abstract
Figures vi
Tables viii
Acknowledgment ix
1.0 ' INTRODUCTION 1
2.0 SAMPLE SOURCES AND PROCESS DESCRIPTIONS 3
2.1 PROCESS DESCRIPTION - SITE A 3
2.1.1 Coal Handling 3
2.1.2 Coal Gasification 5
2.1.3 Gas Purification 5
2.2 PROCESS DESCRIPTION - SITES Bl-3 6
2.3 PROCESS DESCRIPTION - SITE C 6
3.0 ANALYSES PERFORMED 9
3.1 OVERALL ANALYTICAL STRATEGY 9
3.1.1 Organic Analyses 10
3.1.2 Inorganic Analyses (Quench Liquor,
Tar and Cyclone Dust) 12
3.2 SPECIFIC SAMPLES ANALYZED AND METHODS USED... 12
3.2.1 Characterization of Quench Liquor 12
3.2.2 Characterization of Tar 14
3.2.3 Characterization of Cyclone
Bottom Dust 15
3.2.4 Characterization of Gasifier Ash 16
4.0 RESULTS 17
4.1 ANALYSIS OF SITE A QUENCH LIQUOR 17
4.1.1 Organic Analyses 17
4.1.2 Inorganic Analyses 21
iv
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CONTENTS (Continued)
4.2 ANALYSIS OF SITE A TAR 22
4.2.1 Organic Analyses 24
4.2.2 Inorganic Analyses of Tar 28
4.3 CHARACTERIZATION OF SITE A CYCLONE DUST 30
4.3.1 Organic Analyses of Site A Cyclone
Dust Extract (200g) 32
4.3.2 Inorganic Analyses 35
4.3.3 Examination by Optical Microscopy 35
4.4 CHARACTERIZATION OF SITE A GASIFIER ASH 38
4.4.1 Characterization of Organic Extract... 42
4.4.2 Inorganic Characterization of
Trace Elements 42
5. 0 DISCUSSION OF RESULTS 44
5 .1 CYCLONE DUST FROM VARIOUS SOURCES 44
5.2 TRACE ELEMENT LEVELS IN SAMPLES FROM SITE A.. 54
5.3 COMPARISON BETWEEN QUENCH LIQUOR AND WATER
QUALITY STANDARDS FOR TRACE ELEMENTS -
SITE A 54
5.4 COMPARISON OF THE ORGANIC CONSTITUENTS FOUND
IN SELECTED SAMPLES 57
5.4.1 Comparison of Site A Quench Liquor
with Site C "Wash Box" Water 57
5.4.2 Comparison of the Organic Composition
of Tar from Site A and Site C 61
5.5 CONSIDERATION OF SOME LIMITATIONS OF THE
LEVEL 1 TEST PROCEDURE 63
5.5.1 Extraction Procedure 63
5.5.2 IR Spectral Characterization 65
6.0 SUMMARY OF CONCLUSIONS AND RECOMMENDATIONS 68
REFERENCE 72
v
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FIGURES
Number Page
2-1 GASIFICATION UNIT PROCESS FLOW DIAGRAM -
SITE A 4
2-2 SCHEMATIC DIAGRAM OF THE SITE C2 PROCESS
DEVELOPMENT UNIT 8
3-1 SIMPLIFIED DIAGRAM OF ANALYSIS STRATEGY
DEFINED BY LEVEL 1 PROCEDURES 9
4-1 ANALYTICAL FLOW DIAGRAM FOR QUENCH LIQUOR
SAMPLE FROM SITE A 18
4-2 ANALYTICAL FLOW DIAGRAM FOR SITE A TAR 23
4-3 COMPARISON OF MASS DISTRIBUTIONS OF
METHYLENE CHLORIDE EXTRACTABLES IN LC
ELUENTS 26
4-4 ANALYTICAL FLOW DIAGRAM FOR SITE A
CYCLONE DUST 31
4-5 PHOTOMICROGRAPHS OF CYCLONE DUST FROM
SITE A 37
4-6 PHOTOMICROGRAPHS OF CYCLONE DUST SHOWING
SPERICAL SEGMENTS - SITE A 39
4-7 PHOTOMICROGRAPHS OF CYCLONE BOTTOM DUST -
SITE A 40
4-8 PARTICIPATE RESIDUE FROM TAR - SITE A 41
5-1 SIZE DISTRIBUTIONS OF CYCLONE DUST SAMPLES
FROM SEVERAL SITES 46
5-2 COMPARATIVE PHOTOMICROGRAPHS OF CYCLONE
DUST FROM THREE SOURCES 47
5-3 COMPARATIVE PHOTOMICROGRAPHS OF CYCLONE
DUST FROM THREE SOURCES 48
5-4 PHOTOMICROGRAPHS 'OF RESIDUE FROM SITE A
TAR 50
5-5 PHOTOMICROGRAPHS OF DUST WHICH PASSED
THROUGH THE CYCLONE - SITE B 51
5-6 PHOTOMICROGRAPHS OF DEPOSITS ON WALLS OF
PRODUCT GAS MAIN DOWNSTREAM OF THE SITE C
CYCLONE 52
5-7 PHOTOMICROGRAPHS OF PARTICIPATE RESIDUE
IN TAR - SITE C 53
vi
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FIGURES (Continued)
5-8 METHYLENE CHLORIDE EXTRACT OF QUENCH WATER 58
5-9 INFRARED SPECTRA OF ETHER EXTRACT OF
QUENCH WATER 59
5-10 ETHER EXTRACT OF ACIDIFIED QUENCH WATER 60
5-11 RELATIVE MASS DISTRIBUTIONS OF TAR EXTRACT
FRACTIONS 62
vii
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TABLES
Number Page
1-1 SAMPLES COLLECTED FOR PRELIMINARY SCREENING 2
3-1 LEVEL 1 ELUTION SEQUENCE FOR LC SEPARATION
OF EXTRACTED ORGANICS 10
3-2 ANALYSES PERFORMED ON VARIOUS SAMPLES 13
4-1 ORGANICS EXTRACTED FROM SITE A QUENCH LIQUOR 17
4-2 LC MASS DISTRIBUTION OF SITE A QUENCH LIQUOR
EXTRACT 19
4-3 SPECTRAL COMPOSITION OF SITE A QUENCH LIQUOR
EXTRACT 20
4-4 VOLATILE ORGANICS IN SITE A QUENCH LIQUOR
EXTRACT - DETERMINED BY LEVEL 1 GC ANALYSIS 21
4-5 INORGANIC ANALYSIS - TRACE ELEMENTS IN SITE A
QUENCH LIQUOR 22
4-6 ORGANIC EXTRACTABLES IN SITE A TAR 24
4-7 LC MASS DISTRIBUTION OF SITE A TAR EXTRACT 25
4-8 SPECTRAL COMPOSITION OF SITE A TAR EXTRACT 27
4-9 VOLATILE ORGANICS IN SITE A TAR BY LEVEL 1
GC ANALYSIS 28
4-10 TRACE ELEMENTS IN SITE A TAR 29
4-11 RESULTS OF DRY SCREEN TEST OF SITE A CYCLONE
DUST 30
4-12 ELEMENTAL COMPOSITION OF SITE A CYCLONE DUST 32
4-13 LC MASS DISTRIBUTION OF SITE A CYCLONE DUST
EXTRACT 33
4-14 SPECTRAL COMPOSITION OF SITE A CYCLONE DUST
EXTRACT 34
4-15 TRACE ELEMENTS IN SITE A CYCLONE DUST 36
4-16 TRACE ELEMENTS IN GASIFIER ASH 43
5-1 SOURCES OF PARTICIPATES 44
5-2 COMPARISON OF PARTICIPATE MATTER 45
5-3 TRACE ELEMENTS IN SAMPLES FROM SITE A 55
5-4 LEVELS OF TRACE ELEMENTS IN QUENCH LIQUOR FROM
SITE A VERSUS WATER QUALITY STANDARDS (yg/A) 56
5-5 COMPARISON OF EXTRACTABLES FROM QUENCH WATER 57
Vlll
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ACKNOWLEDGMENTS
The author wishes to express his thanks to the following
people for their contributions to the work which is reported here:
To Guy M. Crawford, James C. Faison, Janet M. Gon-
zales, Bonnie L. Heinrich, Clay C. Marston, Larry D. Ogle, and
Jerry L. Parr for their efforts in the analytical area,
To Gene Cavanaugh, Bill Corbett, and Gordon Page
for their helpful review comments, and finally,
• To the EPA project officer, Bill Rhodes, for his
support of this work.
IX
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SECTION 1.0
INTRODUCTION
This report describes the results of some preliminary
analyses of grab samples of selected effluents from several coal
gasification plants. This work was done as part of an EPA spon-
sored program (EPA contract No. 68-02-2147) whose overall objec-
tive is to provide a comprehensive environmental assessment of
low-Btu coal gasification and utilization processes. The purpose
of this specific study was to gain an insight into the nature
of the samples that will be encountered in an ongoing test pro-
gram and, also, to gain experience with the analytical methods
proposed for use in the program.
The work reported here includes analyses as defined by
the Environmental Protection Agency - Industrial Environmental
Research Laboratory/Research Triangle Park (EPA-IERL/RTP) Pro-
cedures Manual1 for a Level 1 environmental assessment, plus
some additional characterization of the samples. The samples
studied, which were taken from several sites, are identified in
Table 1-1. Specific sample point locations at each site are
identified in Section 2.0.
Major emphasis was placed on samples from Site A, since
that facility had already be'en selected as a priority site for
detailed testing at a later date. Work performed on samples
from other sites was done primarily to complement the work on
the Site A samples, thus providing a basis for comparing poten-
tial test sites. Another objective was to gain some concept of
the effects that might be expected from differences in plant
design and feedstock type.
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Table 1-1. SAMPLES COLLECTED FOR PRELIMINARY SCREENING
Site*
A
Bl
B2
B3
Cl
C2
Feed
coal
type
Bituminous
Anthracite
Anthracite
Anthracite
Bituminous
Bituminous
Cyclone
bottom
dust Tar
X X
X
-
X
X
X
Gasifier
bottom
ash
X
-
-
-
-
-
Process
condensate
X
-
-
-
-
X
Gas
duct
dust
_
-
X
-
X
—
* All sites utilize single-stage, fixed-bed, air-blown, atmos-
pheric pressure gasifiers
This report consists of six sections. Following the
Introduction, Section 2.0 describes the processes used and the
samples collected at each site. Section 3.0 describes the anal-
yses performed and the methods used. The analytical results are
presented in Section 4.0. A discussion of these results follows
in Section 5.0 while Section 6.0 provides a summary of the con-
clusions and recommendations which resulted from this work.
-2-.
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SECTION 2.0
SAMPLE SOURCES AND PROCESS DESCRIPTIONS
The samples examined in this study included quench
water (process condensate), tar, ash, and cyclone dust from coal
gasification plants at five different sites. All of these plants
employ fixed-bed, single-stage gasifiers operated at atmospheric
pressure. The following text provides a description of the pro-
cesses used at each site and identifies the sources of the respec-
tive samples. Since major emphasis was placed on the samples from
Site A, it is used as the descriptive model.
2.1 PROCESS DESCRIPTION - SITE A
The coal gasification unit at Site A produces low-Btu
gas from bituminous coal. The product gas is used as a combus-
tion fuel in process furnaces. The plant contains a series of
gasifiers coupled to a gas main which feeds a gas scrubbing sys-
tem. The number of gasifiers operating at any given time is
determined by process fuel needs. At the time of sampling, two
gasifiers were in operation.
A block diagram of the Site A facility is shown in
Figure 2-1. The numbers on the diagram identify the sources of
the respective grab samples.1 In the following text each of the
processing operations used at Site A is described.
2.1.1 Coal Handling
The coal handling operation at Site A consists of:
1) delivery/storage of presized bituminous coal, 2) conveying,
-3-
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COAL DUST
COAL FEEDER
VENT GASES
FUGITIVE
GASES
LIQUOR TRAP
VAPORS
LIQUOR SEPARATOR
FUGITIVE VAPORS
FUGITIVE
GASES
LIQUOR
SEPARATOR
VAPORS AND STEAM
EVAPORATOR
GASES
FEED
COAL
I
•P-
I
LOW-BTU GAS TO
PROCESS FURNACE
STEAM
AIR
COOLING WATER
STEAM
GASIFIER
ASH
(WET)
COLLECTED
PARTICULATES
(DRY)
EVAPORATOR
BY-PRODUCT
TARS AND OILS
QUENCH
LIQUOR
Figure 2-1. GASIFICATION UNIT PROCESS FLOW DIAGRAM - SITE A
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and c) storing the coal in the gasifier feed hoppers. The main
environmental problem associated with this operation is the
generation of coal dust.
2.1.2 Coal Gasification
The gas producers at Site A are atmospheric, single-
stage, fixed-bed, air-blown gasifiers. The coal feedstock enters
the top of each gasifier through a barrel valve and is spread
across the bed by a distribution arm. Steam and air are intro-
duced into the bottom of the gasifier and pass through a grate
into the gasification zone. The grate supports the bed and dis-
tributes the feed gases. Ash from the gasifier is collected in
a water sealed ash pan and removed from the unit using an ash
plow. (The ash sample for this study was taken from the ash pan
following a recent operation of the ash plow.) The raw product
gas at Site A leaves the top of the gasifier at 840-950°K (1050-
1250°F).
2.1.3 Gas Purification
Particulates are removed from the hot product gas at
Site A in a refractory-lined cyclone that operates at a temper-
ature which is slightly lower than the gasifer overhead temper-
ature. Each gasifier is equipped with its own cyclone. Trapped
particulates which collect at the bottom of each cyclone are
dumped periodically. The cyclone dust sample gathered for this
study was taken from a batch of recently dumped dust which was
allowed to cool in air.
The gas leaving the cyclones is quenched first by a
series of sprays located inside the gas collection main. It
then passes through two scrubbers in series where most of the
-5-
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residual tars, oils, and particulates are removed as the gas is
cooled to approximately 325°K (125°F). The effluent scrubbing
liquor is sent to a tar-liquor separator.
In the liquor separator, tars and oils are separated
from the aqueous condensate. The tars and oils are used as a
combustion fuel. Most of the water is recirculated to the
quenching operations. Any excess water that accumulates in the
system during the gasification process is pumped to an evapor-
ator sump. When the sump reaches a specified level, the excess
condensate is sent to an evaporator where it is evaporated and
vented to the atmosphere. The samples of Site A tar and quench
liquor used in this study were taken from the separator system.
2.2 PROCESS DESCRIPTION - SITES Bl-3
Sites Bl, B2, and B3 all use fixed-bed gasifiers which
are similar to the units used at Site A. The hot product gas at
all "B" sites is used directly as a combustion fuel after the
large particulates in the product gas are removed in a hot cy-
clone. Since anthracite coal is used as a feedstock at all "B"
sites, these systems produce essentially no tar.
Two of the "B" site particulate samples were taken
from the bottom of the cyclone and another sample from the exit
of the product gas main. These sample points correspond to
points 2 and 5, respectively, in Figure 2-1.
2.3 PROCESS DESCRIPTION - SITE C
The gasifiers at Site C are fixed-bed units which are
similar in principle to those described previously. Samples
were taken from two different systems. One system (Site Cl)
-6-
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consisted of a commercial scale gasifier and cyclone coupled to
a flare by a long run of insulated duct. One dust sample from
this unit was taken from the gas duct between the cyclone and
the flare. A cyclone dust sample from this unit was also taken
from the bottom of the cyclone (at point 2, as identified in
Figure 2-1). The other system which was sampled at Site C was
a small (two foot diameter gasifier) process development unit
that included a wash box (a single-stage scrubbing column) and
an electrostatic precipitator. A schematic diagram of this sys-
tem is shown in Figure 2-2. The process development unit tar
and wash box water samples which were studied were "old" samples
which had been previously obtained (approximately six months
prior to the time that the analyses reported here were performed)
from sample points A and B (as shown in Figure 2-2).
-7-
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COAL
HANDLING
GASIFIER
I
00
I
1
CYCLONE
^^
rt
w
PQ
a
m s
5 R
P^ t-j
0 0
w o
E£
3P
T
11AK.
rr>
PRODUCT GAS
TO TEST
BURNER
PROCESS
CONDENSATE
B
Figure 2-2. SCHEMATIC DIAGRAM OF THE SITE C2 PROCESS DEVELOPMENT UNIT
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SECTION 3.0
ANALYSES PERFORMED
This section of the report provides a description of
the analytical approach used in this screening study. Section
3.1 describes the analysis strategy defined by Level 1 procedures
and Section 3.2 spells out the analyses actually performed on
each sample.
3.1
OVERALL ANALYTICAL STRATEGY
The basic analytical strategy used for this study is
illustrated in Figure 3-1. This strategy follows the procedures
recommended for a Level 1 environmental assessment1.
SAMPLE: LIQUOR. TAR
ASH, AND
CYCLONE BOTTOM DUST
Figure 3-1.
SIMPLIFIED DIAGRAM OF ANALYSIS STRATEGY DEFINED BY
LEVEL 1 PROCEDURES
-9-
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3.1.1 Organic Analysis
Extraction and Liquid Chromatography (LC) -
A standardized scheme, as defined by the EPA Level 1
procedure, was applied to all samples. By this procedure, the
sample was extracted with methylene chloride and the mass of the
extracted material determined. Prior to concentrating the sample
extract, however, a 1 mJl portion of the solvent/extract mixture
was reserved for analysis by gas chromatography (GC). The con-
centrated extract was then separated into eight fractions by
liquid chromatography using the elution sequence shown in Table
3-1.
Table 3-1. LEVEL 1 ELUTION SEQUENCE FOR LC SEPARATION OF
EXTRACTED ORGANICS
Fraction Eluent
1 n-Pentane
2 207o methylene chloride in pentane
3 507, methylene chloride in pentane
4 methylene chloride
5 57o methanol in methylene chloride
6 207o methanol in methylene chloride
7 507o methanol in methylene chloride
8 5/70/30 concentrated HCl/methanol/
methylene chloride
Samples were evaporated onto the column packing in
order to effect a dry transfer of the sample to the column. The
carrier solvent was removed by evaporation and after the mass
-10-
-------
of the extract was determined, the respective fractions were
examined by infrared (IR) spectrometry.
Gas Chromatographic Analysis -
The gas Chromatographic determination of volatile or-
ganics in the sample extract, reported as Cy-Cia hydrocarbons,
was accomplished using a modification of Level 1 procedures. A
370 OV-101 column was used at 50°C for four minutes, followed by
a temperature program from 50°C to 150°C at 8°C per minute. The
hold time at 150°C was eight minutes. All other conditions were
those specified by Level 1.
A mixture of hydrocarbon standards was used to cali-
brate the instrument for retention times and quantitative re-
sponse. The results from each sample are reported as specified
by Level 1 procedures. For example, everything eluting in the
boiling range of 90° to 110°C is reported as Cy hydrocarbons.
Characterization of Organics by IR Spectrometry -
The infrared spectrum, between 4000-400 cm'1, was
obtained for each of the concentrated extracts and for the
respective Chromatographic fractions from each extract by using
the following procedure. An appropriate portion of each sample
was taken up in a small quantity of methylene chloride and
deposited on a KBr-plate. The plate was placed under an infra-
red lamp and purged with a gentle stream of dry nitrogen until
the solvent evaporated*. In some cases the neat sample flowed,
as a melt, over the plate. Samples which showed evidence of
strong water bands were transferred to an IrTran II window and
* Footnote. Since the Level 1 Procedures Manual1 does not
define this procedure explicitly, this commonly accepted prac-
tice was followed.
-11-
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scanned again. IR spectra were obtained on the following
matrices:
Extract of quench liquor and fractions of
quench liquor extract
• Extract of tar and fractions of tar extract
Extract of cyclone bottom dust
3.1.2 Inorganic Analyses (Quench Liquor, Tar and Cyclone Dust)
A representative portion of each sample was submitted
to Commercial Testing and Engineering Company, 228 North LaSalle
Street, Chicago, Illinois 60601, for elemental analysis by spark-
source mass spectrometry (SSMS) and, in the case of mercury,
atomic absorption spectrometry (AAS).
3.2 SPECIFIC SAMPLES ANALYZED AND METHODS USED
A summary of the samples analyzed is contained in
Table 3-2. The methods used to analyze the respective samples
are described below.
3.2.1 Characterization of Quench Liquor
Organic Analyses -
A 100-m£ portion of the quench liquor was extracted
with methylene chloride. Four equal volume extractions were
used*. As illustrated diagrammatically in Figure 3-1, a l-
portion of the combined extract was reserved for analysis by
*Footnote. The Level 1 Procedure Manual1 recommends that three
500 m£ extractions of a 10 liter sample be used. The organic
content of this sample did not justify the use of such proportions
Further, a more favorable partition ratio was sought for the com-
ponents involved - see Section 5.5.1 of this report.
-12-
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TABLE 3-2. ANALYSES PERFORMED ON VARIOUS SAMPLES
CHNS
IR of GC of LC of IR of Trace Optical Bulk Elemental Screep
Extractables Extract Extract 8 Fractions Fractions Elements Microscopy Ash Density Moisture Analyses Test
Site A Samples
Quench liquor
Tar
Cyclone dust
Ash
(Tar residue)
Site B Samples
Cyclone dust
Duct dust
Site C Samples
Quench water
Tar
Cyclone dust
Duct dust
(Tar residue)
XXXXXX------
XXXXXX------
xxxxxxxxxxxx
XX---X------
x
------xxxx-x
------XXXX--
x ~ x
xx-xx-------
-- - - - - X X X - - X
------xxx---
Level 1 Analyses 1 ArirHHonal nhararfen'zaMnn 1
-------
GC. The balance of the extract was concentrated by evaporation
and weighed. The concentrate was then transferred to a silica
gel column and separated into eight fractions using the Level 1
elution sequence shown in Table 3-1. The respective fractions
were then weighed and examined by IR spectrometry.
Following extraction by the Level 1 procedure, the
liquor was then extracted with two 40-m£ volumes of diethyl
ether. The extracted liquor was then acidified with HC1 to a
pH of 1 and extracted with two additional volumes of diethyl
ether. The respective extracts were concentrated by evaporation
and weighed. These additional extractions were done to deter-
mine whether or not the extractable organics were completely
removed by the Level 1 extraction procedure.
Inorganic Analyses -
A representative portion of each sample was submitted
to Commercial Testing and Engineering Company for elemental
analysis by SSMS and AAS.
3.2.2 Characterization of Tar
Organic Analyses -
A 0.50209 gram sample of tar was extracted for 24 hours
in a Soxhlet extractor with 200 m£ of CH2C12. A l-m& portion of
the extract was reserved for GC analysis by the method described
previously. The balance was concentrated by evaporation and
weighed, after which the extract was transferred to a silica, gel
column and separated into eight fractions by the Level 1 proced-
ure described previously. The respective fractions were then
weighed and examined by infrared spectrometry.
-14-
-------
The residue in the extraction thimble was extracted
with tetrahydrofuran (THF) to check for the presence of materials
that are insoluble in methylene chloride.
Determination of Residue Insoluble in Methylene
Chloride - A 10.12 gram sample of tar was dissolved in methylene
chloride and filtered through a medium-frit filter. The filtrate
was then filtered through Whatman No. 42 filter paper to isolate
submicron particles which may have passed through the medium-frit
filter. The weight of each residue was determined, after which
the residues were examined by optical microscopy.
Inorganic Analyses -
A representative portion of each sample was submitted
to Commercial Testing and Engineering Company for elemental
analysis by SSMS and AAS.
3.2.3 Characterization of Cyclone Bottom Dust
Organic Analyses -
A 100-gram sample of cyclone bottom dust was extracted
for 24 hours in a Soxhlet extractor with 200 m& of methylene
chloride. A l-m& portion of the extract was reserved for GC
analysis. The balance was poncentrated by evaporation and
weighed, after which it was subjected to the chromatographic
and IR procedures described previously.
Elemental Analyses for Major Elements -
Elemental analyses for C, H, N, and S were obtained
from Galbraith Laboratories, Knoxville, Tennessee.
-15-
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Inorganic Analyses -
A representative portion of each sample was submitted
to Commercial Testing and Engineering Company for elemental anal-
ysis by SSMS and AAS.
Optical Microscopy -
Cyclone bottom ash was examined by optical microscopy
at 20x and lOOx magnification. Photomicrographs were prepared
to document particle shape and relative particle size distribu-
tion. Micrographs of the cyclone dusts from the sources identi-
fied in Table 1-1 were then compared visually.
3.2.4 Characterization of Gasifier Ash
Organic Analyses -
A 50.3 gram sample of gasifier ash was extracted for
24 hours in a Soxhlet extractor with 200 m& of methylene chloride,
A l-m£ portion of the extract was reserved for GC analysis. The
balance was concentrated by evaporation and weighed. (Since the
mass of the organics extracted was less than the 8 mg minimum
specified by the Level 1 procedure, no chromatographic separation
was made.)
Inorganic Analyses -
A representative portion of each sample was submitted
to Commercial Testing and Engineering Company for elemental
analysis by SSMS and AAS.
-16-
-------
SECTION 4.0
RESULTS
The results from the analyses of the various samples
are reported in this section, along with a discussion of some
of the more significant results. Analytical flow diagrams are
provided to aid in following the presentations of data.
4.1 ANALYSIS OF SITE A QUENCH LIQUOR
The analytical flow diagram for the analysis of Site A
quench liquor is shown in Figure 4-1.
4.1.1 Organic Analyses
The results of the extraction test on Site A quench
liquor are summarized in the following table.
Table 4-1. ORGANICS EXTRACTED FROM SITE A QUENCH LIQUOR
% of total
Step mg/& extracted
1
2
3
Methylene Chloride Extractable
Ether Extractable3 at pH 7
Ether Extractable at pH 1
2231
1457
177
57.7
37.6
4.7
TOTAL EXTRACTED 3865 100
following Step 1
Following Steps 1 and 2
-------
Indicates an operation
oo
i
Figure 4-1. ANALYTICAL FLOW DIAGRAM FOR QUENCH LIQUOR SAMPLE FROM SITE A
-------
Liquid Chromatographic Separation -
The mass distribution of the methylene chloride extract,
as determined by LC, is shown in Table 4-2. Most of the extract
was eluted in Fraction 6 (solvent = 20% methanol in methylene
chloride). The IR spectrum of this fraction is very similar to
that of phenol.
Table 4-2. LC MASS DISTRIBUTION OF SITE A QUENCH LIQUOR EXTRACT
Fraction
number
1
2
3
4
5
6
7
8
Total
mg/£
0.3
1.8
5.0
17.0
163.0
1655.0
69.0
186.0
2097.1
Total Recovered
Total Loaded
7> Recovered
7o of amount
eluted
0.01
0.09
0.24
0.81
7.77
78.92
3.29
8.87
100.00%
2097 mg/fc
2231 mg/£
94.0 7o
7o of amount
loaded
0.01
0.08
0.22
0.76
7.31
74.18
3.09
8.34
93.997o
IR Spectral Characterization -
The following table contains a listing of the func-
tional group assignments on each fraction as indicated by the
IR spectra.
-19-
-------
Table 4-3. SPECTRAL COMPOSITION OF SITE A QUENCH LIQUOR EXTRACT
Fraction
Number
1
2
3
4
5
6
7
8
% of
Total
Extract
0.01
0.08
0.22
0.76
7.31
74.18
3.09
8.34
Functional Groups Present
Aliphatic hydrocarbons
Alkyl-aryl hydrocarbons
Alkyl-aryl hydrocarbons, trace
carbonyl, possible polycyclics
or multi-substituted aromatics
Alkyl-aryl hydrocarbons, possible
polycyclics, -OH present (possibly
atmospheric moisture)
Phenol + alkyl/dialkyl phenols
Principally Phenol + other phenols
Phenols
i
Alkyl-aryl CH-stretch, OH, -C=0,
Methyl Bending Vibration, '
Primary OH, possible inorganic
sulfur + other ionic compounds
GC Analyses -
The results of the GC analysis of the site A quench
liquor extract are shown in Table 4-4. The concentration values
shown are based on calibration with an external standard. The
material in the Cy range is believed to originate with the
extracting solvent since it is inconceivable that significant
levels of Cy's could be present with no detectable quantities of
either C8's or C9's.
-20-
-------
Table 4-4. VOLATILE ORGANICS IN SITE A QUENCH LIQUOR EXTRACT
-DETERMINED BY LEVEL 1 GC ANALYSIS
Range
C7
C8
C9
Cio
Cu
C 12
C 12
Projected
BP (°C)
90-110
110-140
140-160
160-180
180-200
200-220
>220
ppm wt . in
Quench Liquor
260
0
0
2544
2766
917
800
4.1.2 Inorganic Analyses
The following table contains the results of the ele-
mental analyses of site A quench water. All values except mercury
were determined by SSMS. Attention is called to the 4 yg/2, value
for selenium.
-------
Table 4-5.
INORGANIC ANALYSIS
QUENCH LIQUOR
- TRACE ELEMENTS IN SITE A
Element
Lead
Mercury*
Neodymium
Praseodymium
Cerium
Lanthanum
Barium
Cesium
Iodine
Antimony
Tin
Indium
Cadmium
Molybdenum
Zirconium
Yttrium
Strontium
Rubidium
Bromine
| Selenium
Arsenic
Germanium
yg/*
0.04
0.007
£0.01
0.005
0.01
<0.01
0.1
1
0.5
0.1
0.02
Std
£0.02
0.06
0.01
10 . 004
0.2
0.03
0.2
4
0.2
10.02
Element
Gallium
Zinc
Copper
Nickel
Cobalt
Iron
Manganese
Chromium
Vanadium
Titanium
Scandium
Calcium
Potassium
Chlorine
Sulfur
Phosphorus
Silicon
Aluminum
Magnesium
Sodium
Fluorine
Boron
Lithium
Pg/*
0.006
0.07
0.1
0.1
10.008
3
0.03
0.03
0.004
0.05
10.006
MC
MC
0.3
MC
MC
7
1
2
MC
*" 0
2
0.2
*Flameless atomic absorption
MC - major component
NOTE: Any element not listed - concentration £0.004.
Carbon, hydrogen, nitrogen and oxygen are excluded from these analyses
4.2
ANALYSIS OF SITE A TAR
The tar from site A was a black thermoplastic solid
that was converted to a viscous liquid at 100°C. Its density
was greater than water and it exhibited an odor similar to a
commercial asphalt-based pitch (xylenols). The analytical flow
diagram for this sample, which relates the procedural steps
to the data reported below, is shown in Figure 4-2.
-22-
-------
I
ro
u>
i
GRAVIMETRIC
ANALYSES
GRAVIMETRIC
ANALYSES
GRAVIMETRIC
ANALYSES
INDICATES AN OPERATION
Figure 4-2. ANALYTICAL FLOW DIAGRAM FOR SITE A TAR
-------
4.2.1 Organic Analyses
The following table contains the data obtained from
the extraction and chromatographic separation of site A tar.
Table 4-6. ORGANIC EXTRACTABLES IN SITE A TAR
Extractables In Tar grams ?0 of sample
Weight of Sample 0.50209
Weight of Extracted Organics 0.33583 66.9
Loss-on-Extraction/Evaporation 0.16625 33.1
Insoluble Residue 0.0200 4.0*
*3.97o on the medium frit + 0.1% on the filter paper
The insoluble residue microscopically was similar to
the solids taken from the bottom of the cyclone. This material
is discussed further in the sections devoted to particulate
matter (Sections 4.3.3 and 5.1).
The significant loss-on-extraction and evaporation is
not yet explained and requires further investigation. The THF
extraction of the residue remaining in the thimble after extrac-
tion with methylene chloride accounted for only a minor part of
the loss. Since the final evaporation was under an infrared
lamp, it is conceivable that part of the loss resulted from the
evaporation of some of the more volatile components. A thermom-
eter placed under the lamp read 68°C. However, the sample may
have reached a higher temperature since it probably had a lower
reflectivity.
-24-.
-------
Fractionation by Column Chromatography -
The mass distribution of the chromatographic fractions
of the Site A tar extract is shown in Table 4-7.
Table 4-7- LC MASS DISTRIBUTION OF SITE A TAR EXTRACT
Fraction
1
2
3
4
5
6
7
8
Total
Loss
mg
Eluted
0.75
5.5
48.6
23.6
20.6
147.3
14.0
20.9
281.25
54.58
mg/g
Extract
2.23
16.38
144.72
70.27
61.34
438.61
41.69
62.23
837.48
162.52
70 of
Eluent
0.27
1.96
17.28
8.39
7.32
52.37
4.98
7.43
100.00
—
Total Loaded
on Column
335.83
As with the condensate extract, the major portion of the tar
extract eluted in Fraction 6. A comparison between the normal-
ized mass distribution of the1 liquor and the tar extract is
shown in Figure 4-3. Generally, the tar contains a broader
distribution of materials, including greater amounts of less
polar materials (those eluted in Fractions 1-4).
-25-
-------
SITE A QUENCH LIQUOR
SITE A TAR
100
4-j
§
o
•H
4-1
tfl
,H
(U
pe!
50
0
CO
g
•e
td
o
o
Vi
(0
o
•H
ti
0
O
M
v\
rH
O
d
(U
(0
TJ
•rl
O
lOO
0
6 ' 7 8
Fraction
2 3 4' 5' 6% T 8'
Fraction
Figure 4-3. COMPARISON OF MASS DISTRIBUTIONS
OF METHYLENE CHLORIDE EXTRACTABLES IN LC ELUENTS
-26-
-------
IR Spectral Characterization -
The IR Spectra of the Site A tar extract and its respec-
tive fractions indicate that its composition is substantially
different from that of the quench liquor extract. Although both
spectra indicate the presence of phenolic groups, the tar spectra
also indicate the presence of N-H with considerable intermolec-
ular bonding. (This should not be a surprise since the tar is
indeed an intermolecularly bonded thermoplastic polymer.) Table
4-8 shows a summary of the spectral interpretation of the respec-
tive Site A tar extract fractions.
Table 4-8. SPECTRAL COMPOSITION OF SITE A TAR EXTRACT
Fraction Composition Relative
number (Functional groups present) percent
in extract
1 Aliphatic hydrocarbons (-CH2-) >4
some branched
2 Substituted aromatic with alkyl
and branched alkyl substituents
3 Substituted aromatic with alkyl and
branched alkyl substituents
4 Same as above plus NH stretch
5 Same as above but probably OH stretch,
trace C=0
6 Bonded OH and NH stretch
7 Primary OH, water of hydration, CO
0.27
1.96
17.28
8.39
7.32
52.37
4.98
ether, ester (acetate), split carbonyl
(possible acid)
8 Split ^C=0, (acid and ester), water of 7.43
hydration, possible ester (acetate),
aliphatic, methyl group
-27-
-------
GC Analyses -
The results from the GC analyses of Site A tar extract
are shown below. Analyses were performed on a 1 mJl aliquot of
a sample containing about 2.41 mg of tar extract/m£ of methylene
chloride. Results are reported in the form specified by Level 1
procedures.
Table 4-9. VOLATILE ORGANICS IN SITE A TAR BY LEVEL 1 GC
ANALYSIS
Range
C7
C3
C9
Ci o
Cii
Cl2
>Cl2
Projected
BP(°C)
90 to 110
110 to 140
140 to 160
160 to 180
180 to 200
200 to 220
>220
(mg/g tar)
3.0
0
0
18.2
56.7
72.5
307.5
The amount of material found in the Cy-Cia range con-
stitutes 15.0% of the total sample. The total amount of material
eluting (i.e.3 C?-Ci2 and >Cia) constitutes approximately 46% of
the original amount of the tar sample.
4.2.2 Inorganic Analyses of Tar
The following table contains the results of the trace
element analyses of the tar. All values except mercury were
determined by SSMS. Mercury was determined by flameless AAS.
-28-
-------
Any element not listed in the table, if present, was at a concen-
tration of less than 0.2 ppm by weight. Other elements not re-
ported include the major elements: carbon, hydrogen, nitrogen
and oxygen.
Table 4-10. TRACE ELEMENTS IN SITE A TAR
Element
Lead
Mercury
Neodymium
Praseodymium
Cerium
Lanthanum
Barium
Cesium
Iodine
Antimony
Tin
Molybdenum
Zirconium
Yttrium
Strontium
Rubidium
Bromine
Selenium
Arsenic
Germanium
Gallium
Zinc
ppm wt.
10
0.12
0.6
0.3
0.5
0.6
27.0
0.1
1
0.8
0.9
1
0.7
£0.2
10
0.2
2
3
4
1
8
7
Element
Copper
Nickel
Cobalt*
Iron
Manganese
Chromium
Vanadium
Titanium
Scandium
Calcium
Potassium
Chlorine
Sulfur
Phosphorus
Silicon
Aluminum
Magnesium
Sodium
Fluorine
Boron
Beryllium
Lithium
ppm wt.
3
5
5
120
0.9
3
0.8
29
0.7
630
100
6
520
17
170
25
23
71
^22
19
0.1
4
*Heterogeneous
-29-
-------
Attention is called to the concentration of selenium
in the tar which is used as a supplementary fuel in a coal-fired
power plant.
4.3 CHARACTERIZATION OF SITE A CYCLONE DUST
An analytical flow diagram for Site A cyclone dust is
shown in Figure 4-4. This diagram relates the procedural steps
followed to the data reported below. The dust from the bottom
of the cyclone was observed to be a black, granular, free-flowing
substance with a bulk density of 0.4 g/cc and a particle size
ranging between <1 and 2000 microns, as determined by a screen
test. The bulk of the material appeared to consist of particles
in the 75-400y range, as shown by the data in Table 4-11.
Table 4-11. RESULTS OF DRY SCREEN TEST OF SITE A CYCLONE DUST
Particle size
Sieve No. (dp [y]) wt % Cumulative
10
18
25
40
60
80
100
120
140
200
230
400
-400
>2000
>1000
> 710
> 425
> 250
> 177
> 149
> 125
> 106
> 74
> 63
> 37
< -37
0.3
0.2
0.1
3.1
18.9
22.3
17.9
6.9
7.6
11.6
3.8
4.6
2.7
100.0
99.7
99.5
99.4
96.3
77.4
55.1
37.2
30.3
22.7
11.1
7.3
2.7
-30-
-------
I
CO
INDICATES AN OPERATION
02-1490-8
Figure 4-4. ANALYTICAL FLOW DIAGRAM FOR SITE A CYCLONE DUST
-------
The elemental composition of the Site A cyclone dust
is shown in the following table:
Table 4-12. ELEMENTAL COMPOSITION OF SITE A CYCLONE DUST
Element Wt. Percent
Carbon 84.42
Hydrogen 1.62
Nitrogen 1.07
Sulfur* 0.67
Residue on Ignition (ROI) 10.19
Total (approximate) 98%
*Schoeniger flask method includes organic sulfur and soluble
forms of inorganic sulfur.
Since some of the sulfur contained in the ROI fraction
could also appear with the sulfur value, the total accounted for
is only an indicative value. If used as a guide, the organic
oxygen value appears to be in the vicinity of 2% as determined
by difference.
4.3.1 Organic Analyses of Site A Cyclone Dust Extract (200g)
The methylene chloride extract from 100 grams of site
A cyclone dust yielded 38.1 mg of organic residue representing
381 ppm or 0.38 mg/g. The mass distribution of the LC fractions
from that extract is shown in Table 4-13.
-32-
-------
Table 4-13. LC MASS DISTRIBUTION OF SITE A CYCLONE DUST EXTRACT
Fraction mg
1
2
3
4
5
6
7
8
Total
Mass loaded
Excess recovered
Eluted
21.84
3.53
0.21
0.57
0.62
22.69
3.76
8.87
62.09
43.97*
18.12
% of-
Eluted
35.17
5.69
0.34
0.92
1.00
36.54
6.05
14.29
100.00
ppm
in dus t
109
18
1
3
3
113
19
44
310
^Combined from two extractions
This cyclone dust sample was red hot when it was dropped
from the cyclone into an open pan. Because of heat trasfer limi-
tations, the dust cooled slowly. It is not known whether signif-
icant oxidation occurred during the cooling period, however,
there was ample time for such oxidation to occur. This sampling
procedure is not entirely faulty from an effluent characterization
point of view, however, because in the process itself, the dust
is dropped hot and allowed to cool in a deep hopper.
IR Spectral Characterization -
The organic extract from the Site A cyclone bottom dust
is significantly different from both the tar extract and the
quench liquor extract in that it is comparatively nonaromatic.
The Site A cyclone dust extract contained a major paraffinic
hydrocarbon fraction and a major ester-alcohol fraction.
-33-
-------
Table 4-14 lists the major functional groups identified in the
respective fractions.
Table 4-14.
SPECTRAL COMPOSITION OF SITE A CYCLONE DUST
EXTRACT
% of
Total
Fraction Extract
1 35.2
2 5.8
3 0.3
4 0.9
5 1.0
6 36.5
7 14.3
Assignments
Paraffinic hydrocarbons, consider-
able branching
Paraffinic functional groups ,
traces of substituted aromatics
Split carbonyls , esters (formate
or butryate) , methyl , isopropyl
and tributyl branching, primary
alcohols)
Aromatics , carbonyls , aliphatic
hydrocarbons
Split carbonyls; methyl, isopropyl
and tributyl branching; secondary
alcohols; esters; possible 5C ring
lactones ; branched cyclic alcohols
(No assignment made)
GC Analyses -
The bulk extract from the Site A cyclone dust showed
only one peak in the C? range with a concentration of 2.2 mg/g
of dust. No other components were detected in the Cy-Cia range
nor in the Ci2+ range. This result is questionable since it
would be expected that most of the organic species would be in,
the C7+ range. Further investigations of the organics in cyclone
dust extracts are suggested.
-34-
-------
4.3.2 Inorganic Analyses
The levels of trace elements measured in the Site A
cyclone dust are listed in Table 4-15. All values except mercury
were obtained by SSMS. Mercury was obtained by flameless AAS.
4.3.3 Examination by Optical Microscopy
Microscopically, the Site A cyclone dust particles
appeared to be primarily spherical in shape. They ranged in
size from 15 to 90u with many particles in the 50u size range.
Smaller particles appeared to be primarily fragments of broken
spheres. Visually, the spheres appeared to be hollow. This
observation is supported by the bulk density value of 0.4 g/cc.
Many spheres appeared to have "blow holes" in their outer shells.
These observations lead to an hypothesis that many of the parti-
cles were formed from materials which were suspended tar droplets
initially. Around each suspended droplet, a carbonized skin may
have formed from which volatile organics escaped, thus forming the
perforated hollow spheres. Such particles could be quite buoyant
in a flowing stream.
Photomicrographs -
A number of photomicrographs are included here to
illustrate the observations described above. However, it must
be recognized that a two-dimensional presentation cannot possibly
convey the information obtained subjectively by direct examina-
tion. Superior detail can also be achieved with a scanning
electron microscope, as illustrated by the two micrographs in
Figure 4-5.
-35-
-------
Table 4-15. TRACE ELEMENTS IN SITE A CYCLONE DUST
Element
Bismuth
Lead
Mercury *
Terbium
Gadolinium
Europium
Samarium
Neodymium
Praseodymium
Cerium
Lanthanum
Barium
Cesium
Iodine
Antimony
Tin
Indium
Cadmium
Silver
Molybdenum
Niobium
Zirconium
Yttrium
Strontium
Rubidium
Bromine
Selenium
ppm wt
2
60
0.01
9
2
1
9
21
5
45
45
460
1
4
8
2
Std
<2
3
14
12
80
70
340
33
20
24
Element
Arsenic
Germanium
Gallium
Zinc
Copper
Nickel
Cobalt
Iron
Manganese
Chromium
Vanadium
Titanium
Scandium
Calcium
Potassium
Chlorine
Sulfur
Phosphorus
Silicon
Aluminum
Magnesium
Sodium
Fluorine
Boron
' Beryllium
Lithium
ppm wt
27
5
130
85
130
30
16
MC
120
90
100
MC
12
MC
MC
720
MC
MC
MC
MC
MC
MC
^720
70
6
27
*Flameless atomic absorption
MC = Major Component
Note: Any element not listed concentration £0.2 ppm by wt
Carbon, hydrogen, nitrogen and oxygen are excluded from
these analyses.
-36-
-------
lOy
Figure 4-5. PHOTOMICROGRAPHS OF CYCLONE DUST FROM SITE A
Top - Optical Microscope: 100X
Bottom - Scanning Electron Microscope: 359X
-37-
-------
Figure 4-5 shows a single particle under lOOx magni-
fication. The spherical section in the lower corner of the top
photo is a typical fragment approximately 15y x 50vi. Under
three-dimensional observation, the fragment appeared to be 2-5u
thick. These particles were very fragile and could be easily
crushed. The lower photomicrograph shows a single fragment
viewed with a scanning electron microscope.
Figure 4-6 shows several other groupings of particles.
Nominal particle sizes range from 20y to 55y. Particle fragments
and hollow perforated spheres are clearly evident.
Figure 4-7 shows the particles under 20x magnification,
permitting a greater field of vision and therefore including
more particles. These photographs support the previous obser-
vations regarding particle shape and consistency.
Figure 4-8 shows the particulate residue which remained
after the Site A tar sample was extracted with methylene chlo-
ride as described in paragraph 3.2.2. This material, which
passed through the cyclone, is somewhat smaller in diameter
(dp =20y) but is very similar to the material collected by the
cyclone in that it consists of sintered fragments and hollow
spheres. A comparison will be made of these particulates with
those from three additional sources in Section 5.0 of this report,
4.4 CHARACTERIZATION OF SITE A GASIFIER ASH
The Site A gasifier ash sample was taken from the water
seal pan of the gasifier and transported as a wet aggregate.' Ex-
cess water was drained off and the ash dried prior to analysis.
-38-
-------
lOy
Figure 4-6. PHOTOMICROGRAPHS OF CYCLONE DUST SHOWING
SPHERICAL SEGMENTS - SITE A
Magnification - 100X
-39-
-------
50y
Figure 4-7. PHOTOMICROGRAPHS OF CYCLONE BOTTOM DUST - SITE A
Magnification - 20X
-40-
-------
Figure 4-8. PARTICULATE RESIDUE FROM TAR - SITE A
(This residue passed through the cyclone and was contained in the
tar sample.)
Residue = 4% by wt of tar
Magnification - 100X
-41-
-------
4.4.1 Characterization of Organic Extract
The extraction of 50.3 grams of gasifier ash yielded
0.89 mg of organics, equivalent to 18 ppm by weight. No chro-
matographic separations of this extract were made. The IR
spectrum of the extract showed the following: CH stretch and
methyl absorption bands typical of aliphatic hydrocarbons, a
split carbonyl band and a weak C-0 stretch band indicative of
an ester (possibly an acetate).
4.4.2 Inorganic Characterization of Trace Elements
The following table lists the trace elements found
in the Site A gasifier ash sample. All values except mercury
were determined by SSMS. Other elements not reported include
carbon, hydrogen, nitrogen and oxygen.
-42-
-------
TABLE 4-16. TRACE ELEMENTS IN GASIFIER ASH
Element
ppm wt
Element
ppm wt.
Uranium
Thorium
Bismuth
Lead
Thallium
Rhenium
Tungsten
Tantalum
Hafnium
Lutetium
Ytterbium
Thulium
Erbium
Holmium
Dysprosium
Terbium
Gadolinium
Europium
Samarium
Neodymium
Praseodymium
Cerium
Lanthanum
Barium
Cesium
Iodine
Antimony
Tin
Indium
Cadmium
Silver
Molybdenum
56
86
0.4
7
0.5
0.3
10
2
10
2
12
1
8
11
17
4
10
5
28
56
42
260
280
MC
10
0.3
1
4
Std
3
<0.3
22
Niobium
Zirconium
Yttrium
Strontium
Rubidium
Bromine
Selenium
Arsenic
Germanium
Gallium
Zinc
Copper
Nickel
Cobalt
Iron
Manganese
Chromium
Vanadium
Titanium
Scandium
Calcium
Potassium
Chlorine
Sulfur
Phosphorus
Silicon
Aluminum
Magnesium
Sodium
Fluorine
Boron
Beryllium
Lithium
82
430
260
MC
120
12
20
4
4
66
26
540
120
61
MC
680
510
MC
MC
29
MC
MC
230
250
MC
MC
MC
MC
MC
^56
130
22
190
MC = Major Component
Note - Any element not listed - Concentration <0.2 ppm by wt.
Carbon, hydrogen, nitrogen & oxygen are excluded from
these analyses.
-43-
-------
SECTION 5.0
DISCUSSION OF RESULTS
In this section of the report selected results from
Radian's analyses of Site A samples are compared with results of
analyses of samples from other sources. Consideration is given
to the characteristics of the particulates, trace element distri-
butions in various samples and problems found in the characteri-
zation of organics. In addition, some limitations of the Level
1 test procedures are identified.
5.1 CYCLONE DUST FROM VARIOUS SOURCES
Comparative data for particulates from Site A as well
as those from three other sources indicate properties unique to
each material. The dust sources considered are identified in
Table 5-1.
Table 5-1. SOURCES OF PARTICULATES
Site
(1) A
(2) A
(3) Bl
(4) B3
(5) Cl
(6) Cl
* Suspended
** Rp.mm/pd fi
Fuel
Bituminous
Bituminous
Anthracite
Anthracite
Bituminous
Bituminous
in tar.
rom cms duff- drvwns
Sampling
Location
Cyclone Bottom
Through Cyclone*
Cyclone Bottom
Through Cyclone**
Cyclone Bottom
Through Cyclone**
1~-rf*am of r«vr»1 one
( ) Numbers relate to columns in Table 5-2.
-44--
-------
Table 5-2 shows a comparison of the particulate matter
obtained from the six sources identified in Table 5-1. Attention
is called to the ash content and bulk density of the cyclone
bottom dust samples listed in Columns 1, 3, and 5. The large
difference between the Site B sample (3) and the others is attri-
buted to the anthracite coal used at the B Sites.
Table 5-2. COMPARISON OF PARTICULATE MATTER
Sample Location (1) (2) (3) (4) (5)
Key Site A Site A Site Bl Site B3 Site Cl
Nominal**dp , ]i 170 2-20 200.0 <1* 95.0
Moisture — — 10.5 3.3 0
Ash (Dry Bases) 10.19 — 47.28 54.73 15.4
Bulk Density 0.40 — 0.93 — 0.53
(6)
Site Cl
-20y
—
10.4
0.31
*Agglomerated **dso (See Figure 5-1.)
The photomicrographs in Figures 5-2 and 5-3 show sub-
stantial differences in the particle geometry of the cyclone dust
from the three sites. In contrast to the Site A particles which
were either hollow spheres or spherical sections, both the Site Bl
and the Site Cl particulates were irregular particles and were of
a smaller size generally. The Site Cl cyclone appeared to bring
down smaller particles using a fuel which is supposedly compar-
i
able to that used at Site A. Further, no significant amount of
sphere formation was seen at Site Cl. A few spheres having a
dp 2i20y were observed in the dust but these were in the minority.
A comparison was also made of dusts which passed
through the cyclones. This comparison is highly speculative
since the particles were not actually collected by sampling the
cyclone exit gas. Indeed, the sources were not always common to
those from which bottom dusts were obtained. However, in the
-45-
-------
2000
1000
t-i
-------
Site B (anthracite coal)
Site A (bituminous coal)
•>] lOy
Site C (bituminous coal)
Figure 5-2. COMPARATIVE PHOTOMICROGRAPHS OF CYCLONE DUST FROM THREE SOURCES
Magnification - 100X
-47-
-------
Site B (anthracite coal)
Site A (bituminous coal)
Site C (bituminous coal)
Figure 5-3. COMPARATIVE PHOTOMICROGRAPHS OF CYCLONE DUST FROM THREE SOURCES
(Same as Figure 5-2 but different view of field)
-48-
-------
absence of more valid samples, this approach does yield some
useful information.
The Site A "top" dust shown in Figure 5-4 was removed
from the tar sample by solution filtration. It resembled the
Site A bottom ash in that it consisted mainly of spherical par-
ticles and spherical sections. Particle diameters were generally
less than 20y.
The Site B3 "top" dust shown in Figure 5-5 was taken
from an accumulation of dust which was removed from the gas
transport duct. It consisted primarily of agglomerates of sub-
micron particles. It also contained translucent filaments and
colored crystals, most probably due to contamination of the dust
sample with mineral matter from the end use process.
Two types of "top" dust were obtained from Site C.
One was scraped from the walls of the gas main downstream of the
cyclone. The second was filtered from tar collected by an ESP
that was used on the small process development unit. Both types
of particles are very different from the Site A fines. The first
Site C dust sample (See Figure 5-6) consisted of ^lOy dp agglom-
erates of submicron particles. Resembling soot, it had the ap-
pearance of amorphous carbon rather than that of a sintered
\
particle, which is characteristic of cyclone bottom dust. These
particles might have been formed in the product gas duct.
The Site C tar residue shown in Figure 5-7 is truly
submicron material, with the exception of some translucent crys-
tals which appear to have grown in the tar with aging. (The
sample was taken from material which had been stored on a shelf
for some time.) Some crystals were "twinned," which suggests
that they grew in the medium. Their composition is unknown.
-49-
-------
Figure 5-4. PHOTOMICROGRAPHS OF RESIDUE FROM SITE A TAR
(Particulates which passed through the cyclone)
Magnification - 100X
-50-
-------
10y|-
Figure 5-5. PHOTOMICROGRAPHS OF DUST WHICH PASSED THROUGH THE CYCLONE - SITE B
Magnification - 100X
-51-
-------
10y|-
10y|-
10y|-
Figure 5-6.
PHOTOMICROGRAPHS OF DEPOSITS ON WALLS OF PRODUCT GAS MAIN
DOWNSTREAM OF THE SITE C CYCLONE
Magnification - 100X
-52-
-------
I0y|-
lOy
Figure 5-7. PHOTOMICROGRAPHS OF PARTICULATE RESIDUE IN TAR - SITE C
(These particles passed through the cyclone and were trapped
with the tar in the electrostatic precipitator.)
Magnification - 100X
-53-
-------
The "mud flat" pattern in the photomicrograph (Figure 5-7) is
caused by the submicron particles while the light lines are
ridges in the filter paper. The material contained no spheres
as was evident in the Site A tar residue (see Figures 4-8 and 5-4).
These preliminary data on the particulates produced by
coal gasification suggest that extreme differences in composition
and physical properties of particulates can be anticipated from
site to site. The differences may relate to the type of coal,
system design and presumably, operating conditions.
5.2 TRACE ELEMENT LEVELS IN SAMPLES FROM SITE A
Although the sampling procedures used for this study
do not justify definitive judgments regarding the transport and
fate of trace elements in the process, Table 5-3 was compiled
so that comparisons of the trace element levels in the respective
Site A samples could be made.
5.3 COMPARISON BETWEEN QUENCH LIQUOR AND WATER QUALITY
STANDARDS FOR TRACE ELEMENTS - SITE A
The levels of trace elements in the Site A quench liquor
are listed in Table 5-4 along with quality standards for several
types of water. The levels imposed by the standards are equaled
or exceeded for nearly every element listed. The largest devi-
ation is in the case of selenium. Its concentration in the Site
A quench liquor is 400 times the quality standard for surface and
public intake waters and 80 times the quality standard for irri-
gation water.
-54-
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Table 5-3. TRACE ELEMENTS IN SAMPLES FROM SITE A
Uranium
Bismuth
Lead
Mercury
Barium
Antimony
Cadmium
Molybdenum
Selenium
Arsenic
Zinc
Copper
Nickel
Chromium
Vandium
Titanium
Chlorine
Sulfur
Fluorine
Boron
Beryllium
Lithium
Ash
56
0.4
7
NR
MC
1
3
22
20
4
26
540
120
510
MC
MC
230
250
= 56
130
22
190
Cyclone Bottom
Dust
—
<2
60
0.01
460
8
<2
14
24
27
85
130
30
90
100
MC
720
MC
= 270
70
6
27
Liquor
—
--
0.
0.
0.
0.
<0.
0.
4
0.
0.
0.
o.
0.
0.
0.
0.
MC
-2
2
0.
04
007
1
1
02
06
2
07
1
07
03
004
05
3
2
Tar
—
--
10
0.12
27
0.8
--
1
3
4
7
3
5
3
0.8
29
6
520
-22
0.1
4
All values are expressed as ppm wt. except for the liquor where
values are expressed as yg/m£.
-55-
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Table 5-4. LEVELS OF TRACE ELEMENTS IN QUENCH LIQUOR FROM SITE A
VERSUS WATER QUALITY STANDARDS (yg/A)
Element
Antimony
Arsenic
Barium
Beryllium
Boron
Cadmium
Chromium
Fluorine
Mercury
Lead
Manganese
Molybdenum
Nickel
Selenium
Vanadium
Zinc
Copper
Surface
Water
—
0.05
1.0
--
1.0
0.01
0.05
--
--
0.05
0.05
--
--
0.01
--
5.0
1.0
Irrigation
Water
—
1.0
--
--
0.75
0.005
5.0
--
--
5.0
2.0
0.005
0.5
0.05
10.0
5.0
0.2
Public Water
Intake
—
0.1
--
--
1.0
0.01
0.05
--
0.002
0.05
--
--
--
0.01
--
5.0
1.0
Site A
Quench
Liquor
0.1
0.2
0.1
--
2.0
£0.02
0.03
2
0.007
0.04
0.03
0.06
0.07
4 I
0.07
0.1
-56-
-------
5.4 COMPARISON OF THE ORGANIC CONSTITUENTS FOUND IN
SELECTED SAMPLES
The organic constituents found in selected Site A
samples, when compared with those found in supposedly similar
samples from other sources, showed substantial differences in
component distribution. These differences are discussed below.
5.4.1 Comparison of Site A Quench Liquor with Site C
"Wash Box" Water
This comparison shows that the Site A quench liquor was
carrying 3.8 times the load of or^anics that was being carried by
the Site C wash box liquor. More surprisingly, the component
distribution is strikingly different. Table 5-5 shows that the
methylene chloride extraction step removed approximately 60% of
the solvent extractables from both quench liquors. However, the
composition of the respective extracts differed substantially
as shown by the IR spectra in Figures 5-8 through 5-10.
Table 5-5. COMPARISON OF EXTRACTABLES FROM QUENCH WATER
mg/£ % of Extractant
Extractant
MeCl2
Ether
Ether
(neutral)
(acidified)
TOTAL
Site A
2231
1457 .',
177
3865
Site C
411
78
146
635
Site A
57.
37.
4.
100.
7
6
6
0
Site C
64.
12.
23.
100.
6
3
1
0
The respective analyses of the methylene chloride ex-
tracts show that the Site A quench liquor contains predominantly
aromatics, particularly phenols. The ether extract of the Site C
wash box liquor seems to contain more aliphatic hydrocarbons
-57-
-------
First Extraction
25
3.0
60 MICROMETERS 1.0
2000 1600 1600 UOO WAVENUMBER (CM ) 800 600 400 200
60 MICROMETERS 8.0 10
0.4
4000
WAVENUMBER (CM')
Figure 5-8,
2000 1800 1600 UOO WAVENUMBER (CM') 800 6OO 400
METHYLENE CHLORIDE EXTRACT OF QUENCH WATER
Top: Site C Bottom: Site A
-58-
-------
Second Extraction
4000 WAVENUMBER (CM')
', 2.5 . 3.0
2000 1800 1600 UOO WAVENUMBER (CM1) 800
5.0 6.0 MICROMETERS 8.0 10
600 400
16 20 25
200
50
WAVENUMBtR (CM1)
25OO
Figure 5-9. INFRARED SPECTRA OF ETHER EXTRACT OF QUENCH WATER
Top: Site C Bottom: Site A
-59-
-------
Third Extraction
2.5
3.0
100
20
4000 WAVf NUMBER (CM1)
2500
2000 1800 1600 UOO WAVENUMBER (CM') 800 400 ^00 200
^^;^£:rr«i^.f :-^]T'rr! =ii
4000 WAVENUMBER (CM ;
2500
2000 1800 1600 UOO WAVENUMBER fc« ) ^800 600 400 200
Figure 5-10. ETHER EXTRACT OF ACIDIFIED QUENCH WATER
Top: Site C Bottom: Site A
-60-
-------
including carbonyls (1730 cm'1) and some primary alcohols
(1060 cm"1) relative to the amount of aromatics (1600 cm'1)
present. Some of these effects may have been the result of
the age differences in the two samples.
Both the ether and the acidified ether extracts of
the Site A sample show a number of sharp bands in the finger-
print region of the spectrum (1000 to 600 cm"1). These bands
have not been assigned. Assignment of these fingerprint bands
is, at best, subject to doubt with complex mixtures. Although
sharp bands like those present in these spectra are common to
substituents and polyaromatic compounds, it is difficult to be-
lieve such an assignment when it is recognized that this material
was not extractable from water with methylene chloride. Since
no carbonyl absorbance is present, the material cannot be an
organic acid. Nor can it be an aliphatic alcohol, since no
significant OH stretch is present. The absorbance is probably
due to an inorganic salt or a metal organic substance, possibly
a pyrosulfite. More work at a species specific level would be
required to characterize this substance which is present in
significant amounts. The doublet in the spectrum of the acidi-
fied ether extract of the Site C water at 950 cm"1 could well be
due to a similar type of substance. However, the Site C extract
shows a significant amount of a primary alcohol in addition to
the substances present in the Site A ether extract.
5.4.2 Comparison of the Organic Composition of Tar
from Site A and Site C
The Site A tar was a solid at room temperature whereas
the Site C tar was a moderately viscous, free-flowing liquid.
The relative mass distributions of the respective LC fractions
are shown in Figure 5-11. It is evident from these graphs that
-61-
-------
Site A
Site C
100
2345678
LC Fraction
100
50.
12 34 5 6 7 8
LC Fraction
Figure 5-11. RELATIVE MASS DISTRIBUTIONS OF TAR
EXTRACT FRACTIONS
-62-
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the paraffinic and nonpolar aromatics are more abundant in the
Site C tar. This difference in distribution may be the result
of a loss of lights in the Site A quench system. The IR spectra
of the respective fractions, for practical purposes, are compar-
able. Differences in the relative amounts of isomeric species
exist but their functional compositions are similar. The major
difference is seen in the IR spectra of Fraction 8. The Site A
sample contains a stronger /C=0 and a -C-0- vibration indicative
of acetates, suggesting that the material has been in a more
oxidative environment.
5.5 CONSIDERATION OF SOME LIMITATIONS OF THE LEVEL 1
TEST PROCEDURE
The Level 1 test procedure suffers limitations in two
areas: the extraction procedure and the IR spectral character-
ization procedure. These limitations are discussed below.
5.5.1 Extraction Procedure
A modified Level 1 extraction procedure followed by
two ether extractions, as described in section 3.2.1 of this
report, was used on the quench liquor. The recommended Level
1 extraction procedure was modified from a 20/1 sample/extractant
ratio to a 1/1 ratio in order to assure a more complete transfer
of polar organics into the organic phase. This extraction was
followed by ether extractions at pH 7 and pH 1 to determine
whether any substances remained in the condensate following the
Level 1 extraction step.
The test results, as described in section 4.1.1 indicate
that four equal volume extractions with methylene chloride did
not recover all of the organics present in the aqueous phase.
-63-
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Therefore, a methylene chloride extraction step alone does not
appear to be adequate for purposes of assessing the organics
present in quench liquors from coal gasification processes. This
is because a variety of substances produced during the thermal
degradation of coal do not partition adequately into methylene
chloride from water. The following discussion is provided to
support this conclusion.
If only the mass of the extracted organic material is
considered, then the results of the MeCl2 extraction step may
fall within the ±2 to 3 specification of the Level 1 procedure.
However, when composition is included in the consideration, this
might not be the case since the materials not extracted by the
methylene chloride are undoubtedly chemically different from
those which are. Therefore, the procedure should be modified
to include the supplementary extractions.
Attention must also be called to the specified ratio
of the sample to the extractant because the Level 1 procedure
states: "normally three 500-mH methylene chloride extractions
of 10-liter samples should be sufficient" (Reference 1, Section
8.3.1, page 97). This recommended ratio may lead to seriously
misleading results since the recommended 1:20 volume ratio could
leave many components in the water, as is demonstrated by the
following relative mass transfer equation:
F- KVe
where,
[Solute]
[Solute]
K = extractant = partition coefficient
sample
-64-
-------
F = relative mass transfer per extraction
Ve = m£ volume of extractant (MeClz) , and
/
Vg = m& volume of sample (liquor) .
To comply with Level 1 specifications of ±2 to 3, on
the order of 50% of the mass of a given component must be trans-
ferred in three extractions. In order to transfer 50% of the
dissolved mass in three extractions, about 20% per extraction
must be transferred. Using this F value in the mass transfer
equation with a volume ratio of 1:20 as specified, a K = 5.0
is obtained. This calculation shows that any substance with a
partition coefficient significantly less than 5.0 would fall out-
side the specification of the method. Because of the wide range
of polarities shown by the substances produced in coal gasifica-
tion processes, it is recommended that as a minimum, a four-step
extraction with a total volume equaling the sample volume be used
for all batchwise extractions. It is further recommended that an
extraction at pH 1 be used following extraction at pH 7 to effect
a more complete transfer of polar organics for analysis. A rea-
sonable alternative is to use a commercial continuous extractor
which can be run overnight, providing a large number of transfers
virtually unattended.
\
5.5.2 IR Spectral Characterization
The IR spectral characterizations of these grab samples
have provided information that is useful to the planning of a
more detailed sampling program. The functional groups that were
identified, indicate the types of substances that are present.
When this information is used in combination with the LC data,
it provides a profile of the substances that must be dealt with
-65-
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in a detailed sampling program as well as in a Level II analysis
to obtain species specific data. Indeed, considerable informa-
tion is contained in the spectra that is useful to the analyst.
However, taken alone, this information is inconclusive and must
be substantiated by additional analysis.
One area where the roll of IR is limited is with
materials such as tars which we know to be complex organic
materials. Spectral characterization of complex mixtures such
as tars using Level 1 procedures is of limited value to an
environmental assessment since their spectra are so diffuse and
devoid of definitive bands. The intermolecular bonding in tar
restricts molecular vibration and therefore inhibits the gen-
eration of sharp bands by which definitive assignments can be
made. As a consequence, no distinct fingerprint exists to
identify tar as an emission from a suspected source. Further;
without the use of more sophisticated separation steps, specific
hazardous species cannot be identified. The Level 1 technique
can be used only to compare tars from different sources and to
show that they are probably similar in composition. Stated
more broadly; when the spectrum of one tar is identifiably
different from that of another, it can be asserted that the
tars are different. However, when the spectra of two materials
are similar, but not identical, it can only be asserted that the
materials are probably similar on a bulk basis. Indeed, either
substance could contain harmful amounts of hazardous species not
indicated by the spectra. If such a substance were detected by
other means, the IR spectrum could not be used to establish that
the tar was the source.
f
In order to discriminate between various types of com-
pounds having similar functional groups, it is generally neces-
sary to rely on the fingerprint region of the IR spectrum
-66-
-------
(1430-800 cm"1) since absorbance in that region tends to be
molecular specific. Therefore, to discriminate between poly-
cyclic and alkylaromatic hydrocarbons, spectral bands in the
fingerprint region must be used. However, unless the sample
is in solution and relatively free of interferences from other
compounds, band assignments tend to be ambiguous. Spectral
bands can change position in the fingerprint region depending
on the physical state of the component in the sample as well as
on the nature and position of substituents in the molecule.
These uncertainties limit the utility of the fingerprint region
as a tool for functional group discrimination in complex mixtures
Assignments must therefore be based on group frequencies which
are relatively nondefinitive and indeed of limited value in
detecting polycyclic aromatic compounds. Consequently, consid-
eration of an alternative screening method is warranted.
Ultraviolet spectrometry is considerably more sensi-
tive than IR spectrometry to polycyclic aromatic hydrocarbons
and is capable of detecting traces of multiring compounds. The
UV technique should be included in the screening procedure as a
method of detecting traces of polycyclics in samples and
chromatographic fractions. Since an increase in ring number
causes the UV absorption maxima to shift to a longer wave length,
the technique can be useful in characterizing polyaromatic
materials. For example, a UV absorbance at a wavelength greater
than 330 nm can be taken as an across the board indication that
polycyclic substances are potentially present, particularly if
that absorbance is observed in LC fractions 2 or 3. Further,
the UV technique is much more sensitive than IR.
-67-
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SECTION 6.0
SUMMARY OF CONCLUSIONS AND RECOMMENDATIONS
Several judgments can be made regarding the data
obtained and the methods used in this study that will affect
the low-Btu data acquisition program. These judgments are
expressed in the conclusions and recommendations listed below:
Organic Constituents in Site A Quench Liquor:
The major organic constituent of Site A
quench liquor was phenol with lesser amounts
of di- and trisubstituted components; vola-
tile organics fell mainly in a chromatographic
boiling range of 160-200°C.
Ether Extracts;
The ether extracts of the Site A quench
liquor differed in composition from the
Site C ether extract. The Site C extract
appeared to contain more aliphatic material
than the site A extract. Active functional
groups such as C-H, ,-C=Q, and -C-0 were
not as evident in the spectra of the
Site A ether extracts as they were in
the Site C sample.
Only 57% of the extractable organics were
removed from the Site A quench liquor by
the Level 1 procedure. The remaining organics
were removed by supplemental extraction with
-68-
-------
ether from a neutral, then acidified sample.
The spectral compositions of the respective
extracts were different.
Trace Element Levels:
The levels of trace elements in the Site A
quench liquor equaled or exceeded the levels
listed in the Federal Water Quality Standards
for nearly every element. The largest deviation
was shown by selenium at 4 ppm (400 times the
quality standard for surface water).
Cyclone Dust:
The Site A cyclone bottom dust appears to
consist of hollow spheres with a nominal
particle diameter (d50) of 170y. Fines
appear to be sections of broken spheres.
The Site C dust is smaller and irregular
in shape, but of comparable bulk density.
The Site B dust (anthracite coal) has a
particle shape comparable to the Site C
dust but is more than twice as dense and
was highly agglomerated. Particulates
extracted from the Site A tar had the
same physical characteristics as the
bottom dust, though smaller in diameter.
Hypothesis:
These observations indicate that the char-
acteristics of the particles in the gasifier
-69-
-------
exit gas may depend on fuel types, system
design, and/or operating conditions. Since
those particulates may provide a mechanism
for trace element transport, particle re-
moval must be studied over a wide range of
conditions to obtain information needed for
a comprehensive and reliable assessment of
the fate of trace elements in gasification
processes.
Procedures:
The Level 1 procedures make virtually no
provisions for detecting organic sulfur
or nitrogen compounds. The IR spectral
procedure is ideal for detecting aromatic,
carbonyls and alcohols, but it is not well
suited to detecting C-S-, and C-N. Sub-
stances that contain hydrogen-bonded
hydroxl groups produce such broad bands
that discriminating spectral assignments
are virtually impossible. Conversely
an assignment that includes all possible
structures that might be represented by
a broad band is apt to be so inclusive
that it is not informative. A limited
amount of additional work, to detect the
presence of organic sulfur and/or nitrogen
would be of value to a Level 1 assessment.
At a minimum, an elemental analysis for
S and N in the eight LC fractions could
be included as a valuable "add on" to a
Level 1 test.
-70-
-------
Additional Needs - HPLC:
A moderate amount of high-pressure liquid
chromatography (HPLC) or at least thin
layer chromatography could be a valuable
adjunct to the Level 1 procedures when
used on major fractions (for example,
Fraction 6 in this study) to discriminate
between the nonvolatile component classes.
Such additional work can provide valuable
information for both the Level 1 assess-
ment and the Level II test plan. HPLC
is needed to characterize these polar
materials since they do not lend them-
selves to characterization by GCMS.
Further, since they are soluble in water,
they are of environmental concern.
Additional Needs - UV Spectrometry:
UV or Fluorescense spectrometry should be
used to detect polycyclic aromatics in the
LC fractions. These techniques are several
orders of magnitude more sensitive to poly-
cyclics than IR and they can be used in
conjunction with TLC for additional char-
acterization as required. Since sample
preparation is very simple, this work
could be done at minimal additional cost
to a basic Level 1 program.
-71-
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REFERENCE
1. Hamersma, J. W., S. L. Reynolds and R. F. Maddalone,
IERL-RTP Procedures Manual: Level 1 Environmental
Assessment.EPA-600/2-76-160a, EPA Contract No.
68-02-1412, Task 18. Redondo Beach, CA, TRW Systems
Group, June 1976.
-72-
-------
TECHNICAL REPORT DATA
(Please read Infractions on the reverse before completing)
1. REPORT NO.
EPA-800/7-77-141
3. RECIPIENT'S ACCESSION-NO.
4. TITLE AND SUBTITLE
Analyses of Grab Samples from Fixed-bed Coal
Gasification Processes
5. REPORT DATE
December 1977
6. PERFORMING ORGANIZATION CODE
7. AUTHOR(S)
8. PERFORMING ORGANIZATION REPORT NO.
Karl J. Bombaugh
9. PERFORMING ORGANIZATION NAME AND ADDRESS
Radian Corporation
P.O. Box 9948
Austin, Texas 78766
10. PROGRAM ELEMENT NO.
EHE623A
11. CONTRACT/GRANT NO.
68-02-2147, Exhibit A
12. SPONSORING AGENCY NAME AND ADDRESS
EPA, Office of Research and Development
Industrial Environmental Research Laboratory
Research Triangle Park, NC 27711
13. TYPE OF REPORT AND PERIOD COVERED
Final; 1-7/77
14. SPONSORING AGENCY CODE
EPA/600/13
is. SUPPLEMENTARY NOTES IERL-RTP project officer is William J. Rhodes, Mail Drop 61,
319/541-2851.
16. ABSTRACT
The report gives results of an analytical screening of selected effluent sam-
ples from operating coal gasification units. The work was done to aid in planning for
'uture more comprehensive environmental test programs which will be conducted at
gasification units both in the U.S. and abroad. A secondary objective was to evaluate
SPA'S phased approach to environmental testing of coal gasification units. Grab sam-
3les—including tar, process condensate, gasifier ash, and cyclone dust--from five
lifferent commercial-scale gasifiers and one pilot-scale gasifier were obtained for
the study. All were single-stage, fixed-bed, atmospheric-pressure, air-blown units:
lowever, the materials consumed by the gasifiers included both bituminous and anthra-
ite coals. The analyses were intended as a preliminary identification of the classes
f compounds in each sample which warrant further attention. The study resulted in
many significant conclusions relating to: the classes and concentrations of components
in specific samples; the effects of feedstock and process operating condition changes
the levels of key components detected in the samples; and modifications/additions
:o suggested EPA procedures which would help ensure that the maximum amount of
jseful environmental information is obtained from future programs.
7.
KEY WORDS AND DOCUMENT ANALYSIS
DESCRIPTORS
b.lDENTIFIERS/OPEN ENDED TERMS
c. COSATI Field/Group
Pollution
2oal Gasification
Sampling
Analyzing
Pars
Hondensates
Ashes
Dust
Pollution Control
Stationary Sources
13B
13H
14B
07C
07D
21B
11G
IS. DISTRIBUTION STATEMENT
Unlimited
19. SECURITY CLASS (This Report)
Unclassified
21. NO. OF PAGES
72
20. SECURITY CLASS (Thispage)
Unclassified
22. PRICE
EPA Form 2220-1 (9-73)
-73-
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