United States      Industrial Environmental Research  EPA-600/7-79-200
Environmental Protection  Laboratory          August 1979
Agency        Research Triangle Park NC 27711
Pollutants from Synthetic
Fuels Production:
Coal  Gasification
Screening  Test Results

Interagency
Energy/Environment
R&D  Program  Report

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                                              EPA-600/7-79-200

                                                     August 1979
Pollutants from  Synthetic Fuels Production
    Coal Gasification  Screening Test  Results
                                 by

                   J. G. Cleland, S. K. Gangwal, C. M. Sparacino,
                   R. M. Zweidinger, D. G. Nichols, and F. O. Mixon

                          Research Triangle Institute
                             P. 0. Box 12194
                    Research Triangle Park, North Carolina 27709
                            Grant No. R804979
                        Program Element No. EHE623A
                       EPA Project Officer: N. Dean Smith

                    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

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                    POLLUTANTS FROM SYNTHETIC FUELS PRODUCTION:
                     COAL GASIFICATION SCREENING TEST RESULTS

                                     ABSTRACT

     Coal gasification test runs have been conducted in a semi batch, fixed-bed
laboratory gasifier in order to evaluate various coals and operating conditions
for pollutant generation.  Thirty-eight tests have been completed using char,
coal, lignite, and peat.  Reactor temperatures ranged from 790°C to 1035°C
with high carbon and sulfur conversions in the bed.
     Extensive analyses were performed for organic and inorganic compounds and
trace elements in the tars and hydrocarbon oils, aqueous condensates, and
reactor residues resulting from the gasification tests.  Over 300 compounds
were identified from the various gasifier streams, and more than 100 of these
compounds were quantified for several of the test  runs.
     Statistical analyses have been performed on the data.  The quantity and
composition of the various effluents have been examined  in relation to coal
type and operating variables.  Results are reported for  sulfur species in the
product gas stream, for  consent decree pollutants  contained as volatile organic
compounds in  the product gas, for  phenol  and  related compounds in the aqueous
condensate and  tar/oil  sample,  and for polynuclear aromatic  hydrocarbons  (PNA)
species  in the  tar/oil.
                                        m

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                              TABLE OF CONTENTS
Section                                                                   Page

Abstract	    iii
List of Figures	      v
List of Tables	     vi
Acknowledgments  	   viii

     1.0  Introduction 	      1

     2.0  Screening Test Conditions  	      4

          2,1  Fossil Fuels Gasified 	      4
          2.2  Reactor Operating Conditions  	      4
          2.3  Effluent Sampling and Chemical Analysis 	      6

     3.0  Experimental Results  	   10

          3.1  Reactor System Behavior  	   10
          3.2  Chemical Analysis Results   	   13

     4.0  Material Balance Results   	   34

          4.1  Computation Procedure   	   34
          4.2  Material Balance Adjustments  	   42
          4.3  Trace  Element Balances  	   43

     5.0  Statistical Analysis  	   48

          5.1  Linear Regression Technique   	   48
          5.2  Statistical Analysis  Results:  Phase  I  	   51
          5.3  Statistical Analysis  Results:  Phase  II   	   54

     6.0  Conclusions	   69

 References	   73

 Appendices
           I.   Signal  Processing System  	   76

          II.   Pollutant  Production  Factors  	   82
                                        iv

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                              LIST OF FIGURES

Number                                                                     Page
  1    Gasifier and sampling train 	    2
  2    Tar partitions	22
  3    Production factors for major pollutants from run no.16 with
       Illinois No.6 coal  	23
  4    Production factors for major pollutants from run no.21 with
       Illinois No.6 coal	24
  5    Production factors for major pollutants from run no.23 with
       Illinois No.6 coal  	25
  6    Production factors for major pollutants from run no.41 with
       Western Kentucky No.9 coal	26
  7    Production factors for major pollutants from run no.25 with
       Montana Rosebud coal  	27
  8    Production factors for major pollutants from run no.33 with
       Wyoming subbituminous coal  	  28
  9    Production factors for major pollutants from run no.35 with
       Wyoming subbitumino'us coal  	29
 10    Production factors for major pollutants from run no.36 with  North
       Dakota Zap lignite coal	30
 11    Production factors for major pollutants from run no.43 with  North
       Dakota Zap  lignite coal	31
 12    Comparison of the observed  and  predicted  tar organic  base  yields
       for  the RTI gasifier  screening  tests	63
 13    Comparison  of the observed  and  predicted  tar organic  acid  yields
       for  the RTI gasifier  screening  tests	64
 14    Comparison  of the observed  and  predicted  tar yields for  the  RTI
       gasifier  screening tests  	  65
 15    Comparison  of the observed  and  predicted  H2S yields for  the  RTI
       gasifier  screening  tests  	  .  	  66
 16    Comparison  of the observed  and  predicted  COS yields for  the  RTI
       gasifier  screening  tests  	  67
 17    Signal  processing hardware  configuration   	   77
 18    Signal  processor function relative to gasification tests  	   78
 19    Signal  processor function relative to GC  analyses  	   79
 20    Signal  processing software system   	   81

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                              LIST OF TABLES

Number                                                                   Page
  1     Analysis of Fuels Gasified  	    5
  2     Experimental  Test Parameters  and  Commercial Gasifier Operating
        Conditions 	    7
  3     Operating Conditions—Screening Tests	    8
  4     Residue (Bottom Ash)  Analyses   	   12
  5     Compounds Identified  in Gasifier  Effluents  	   14
  6     Pollutant Production  	   16
  7     Reactor Gas Streams  	   19
  8     Tar Pollutants	   20
  9     Weight Percent of Individual  Fractions Obtained from Crude  Tar
        Partitioning	:	   21
 10     Primary Elements of Tars 	   33
 11     Elemental Balances for RTI  Screening Runs  	   35
 12     Material Balance Results for Run  No.16 (Illinois No.6
        Bituminous Coal) 	   36
 13     Material Balance Results for Run  No.*25 (Montana Subbituminous
        Coal)	   37
 14     Material Balance Results for Run  No.33 (Wyoming Subbituminous
        Coal)   	    38
 15     Material Balance Results for Run  No.36 (North Dakota Lignite
        Coal)   	    39
 16     Material Balance Results for Run  No.41 (Western Kentucky
        Bituminous Coal)  	    40
 17     Trace Metal Analyses  (Tar and Condensate)  	    44
 18     Trace Metal Analyses—Residue  (Bottom Ash)	    45
 19     Comparison of  Trace Element Analysis Results 	    47
 20     Important Gasifier Operating Parameters  	    49
 21     Important Pollution Production Parameters and Gasifier
        Performance Variables   	    50
 22     Summary of  the Statistical Analysis of the RTI Gasifier Screening
        Runs Using All  Independent Variables  in  Table  20  	    52

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LIST OF TABLES (continued).

Number                                                                  Page
  23    Ranking of Operating Parameters in the Order of Importance in

24

25

26

II-l

II-2

II-3

II-4

II-5

II-6

II-7

II-8

II-9

Influencing Pollutant Production 	
Ranking of the Most Important, Independent Operating
Influencing Pollutant Production 	

Parameters

55

56
-Summary of the Statistical Analyses of the RTI Gasifier Using
the Most Important, Independent Operating Variables
Summary of Linear Models for Pollution Production and
Performance 	
Pollutant Production in Coal Gasification—Run No. 16:
No. 6 Coal 	
Pollutant Production in Coal Gasification— Run No. 21:
No. 6 Coal 	
Pollutant Production in Coal Gasification—Run No. 23:
No. 6 Coal 	
Pollutant Production in Coal Gasification— Run No. 41:
Kentucky No. 9 	
Pollutant Production in Coal Gasification— Run Mo. 25:
Rosebud Coal 	
Pollutant Production in Coal Gasification— Run No. 33:
Subbituminous Coal 	
Pollutant Production in Coal Gasification— Run No. 35:
Subbituminous Coal 	
Pollutant Production in Coal Gasification— Run No. 36:
Dakota Zap Lignite 	
Pollutant Production in Coal Gasification — Run No. 43:
Dakota Zap Lignite 	

Gasifier

Illinois

Illinois

Illinois

Western

Montana

Wyoming

Wyoming

North

North

58

60

83

84

85

86

87

88

89

90

91
                                     VII

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                               ACKNOWLEDGMENTS

     The project "Pollutants from Synthetic Fuels  Production,"  has  been
sponsored by the U.S. Environmental  Protection  Agency (EPA)  through the  Fuel
Process Branch, Industrial  Environmental  Research  Laboratory,  at Research
Triangle Park, North Carolina.   The  guidance of Dr.  N.  Dean  Smith,  Project
Officer, Mr. William J. Rhodes, Program Manager, and Mr.  T.  Kelly Janes,
Branch Chief, are gratefully acknowledged.
     Substantial contributions  and collaboration have been provided by a
number of personnel at the Research  Triangle Institute (RTI).   These persons
include David Green, John Pierce, William McMichael, Robert Truesdale, Edward
Bean, and Tina Webb of the Process Engineering Department.  From the Environ-
mental Measurements Department, major inputs were provided by Peter Grohse and
Denny Wagoner, as well as Douglas Minick, Jesse McDam'el, Steven Frazier,  and
Kenneth Tomer of the Chemistry and Life Sciences Division.  Deborah Whitehurst
and Ty Hartwell participated in the statistical analysis of data.  William
Drake assisted in signal processor software development.
     Mr. Fred Schwarz of the Process Engineering Department manufactured and
fabricated  essentially the complete gasification facility in the RTI machine
shop.  His  insights  and handiwork gave rise to  functional and productive
hardware.
                                     vm

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                             1.0  INTRODUCTION

     This project is being conducted by the Research Triangle Institute in
order to develop an understanding of the nature and extent of the production
of environmental pollutants in synthetic fuels processes.   Screening test runs
have been conducted in a laboratory scale nonisothermal  reactor.   Eight distinct
coals or related materials have been gasified under various operating con-
ditions so as to screen the pollutants produced by a variety of feed materials
considered to be candidates for coal gasification within the United States.
     A report on the facility construction and preliminary tests was pre-
viously prepared.   That report described the design and construction of the
gasification facility including the reactor and associated feed devices, the
sampling and analysis system development, and the on- and off-line data
collection and evaluation capability.  (See Figure 1).
     Some 38 gasification tests were conducted in order to (1) establish the
range of operating conditions over which the laboratory reactor can be success-
fully operated,  (2) establish the operating characteristics of the gasifier
and ascertain the extent to which its  results match those of large scale
units,  (3) conduct extensive chemical  analysis work aimed at the  identification
of the chemical  species in the  various effluents from the gasifier,  (4) com-
plete approximate quantitative  analyses on the gasifier effluents which are
present  in sufficient quantities to be environmentally significant, and  (5)
establish operating conditions  for  parametric studies.  The fossil fuel
sources which have been gasified include FMC char,  Illinois No.6  coal, Western
Kentucky No.9 coal, Pittsburgh  No.8 coal, Montana Rosebud coal, Wyoming sub-
bituminous (Smith-Roland)  coal, North  Dakota Zap lignite, and North Carolina
humus peat.  These tests  have been  conducted both with externally supplied
heat as  well as  with  heat  derived from partial combustion  taking  place as  a
part of the overall gasification process.

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          STEAM GENERATION SYSTEM
ro
                                             SCRUBBER
                                                    STEAM FURNACES
                        WATER SUPPLY
                                                                                                    SAMPLE PORTS
                                                                                                         RESIN
                                                                                                         CARTRIDGES
                                                                                                   CONTINUOUS
                                                                                                   ANALYZER
|J7J>_' HEACTOR_  _  _  _ _  	|

       REACTOR SYSTEM
       AND NONVOLATILE       J
       SAMPLING
                                                                                                                         ~]
                                                                                                  I	I
                                                                                                    PRODUCT GAS SAMPLING
                                                                                                    ANALYSIS. METERING
       |	j«2

       REACTANT GAS SUPPLY AND CONTROL
                                                   Figure 1.  Casifier  and sampling train.

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     Operating conditions have been chosen in many cases to approximate those
of large scale gasifier operations producing low heating value fuel  gas or
synthesis gas.  However, coal  addition has been by way of batch addition to
the reactor from a pressurized lockhopper.  Thus, the coal  feed has  been a
batch process while the addition of air and/or steam to the reactor  has
involved continuous flow throughout a gasification test run.   Hence, operation
of the reactor during the screening tests is referred to as being in the
semi batch fixed-bed mode.
     If the effluent concentrations for a semibatch run are averaged by integra-
tion  over the time of the run  to simulate the steady-state concentrations of a
continuous process, then the semibatch reactor produces effluent concentrations
which appear to provide a reasonably good simulation of gas product  compositions
from full scale process gasifiers.  Where comparative results are available,
the results obtained in this study have shown good agreement for such major
pollutants as sulfur compounds, phenols, total organics, benzene derivatives,
and total tar.
     Companion reports are simultaneously being prepared and issued on (1) the
sampling and analysis methodology which has been developed for use in this
project and (2) the health and environmental significance of the results which
                                            2 3
have been obtained from the screening tests.     Separate reports are also
planned on related topics.  One is intended on the transient behavior of the
gasification test runs relative to both reactor operation and the concentration
of effluents.  Another is to be a comparison of the results of this study with
the available comparative data on pilot plant and commercial gasification
operations.
     Future reports will  also  present  information relative to parametric
studies, which examine the  generation  and control of  potential pollutants  in
coal gasification  under  various operating conditions.   The parameters  under
consideration are  coal type, coal  particle size,  reactant  flow rates,  chemical
additives, and other  factors.   Information being  generated in this-project  is
intended to provide a  basis for the  assessment  of the potential  health and
environmental  significance  of  the effluents from coal  gasification  processes.
The  project results should  also lead to process  modifications  and/or  control
technology developments  which  permit substantial  reductions  in  potential
emissions.

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                     2.0  SCREENING TEST CONDITIONS

     Screening tests have been completed using selected coals,  lignite,  peat,
and a coal-derived char.  Semibatch fixed-bed gasification was  conducted to
generate, collect, process, analyze, characterize, and evaluate the pollutants
from the gasification of each feed material.   Flow rates of steam and/or air
were predetermined for each run so as to achieve desired reaction temperatures.
Additionally, external furnaces were utilized to control the temperatures and
heating rates involved.  An on-line signal processing system was utilized to
collect process data, to collect and analyze gas chromatograph output signals,
and to perform overall data processing functions.  This POP 11/34 system and
associated equipment and software are described in an appendix.
2.1  FOSSIL FUELS GASIFIED
     The eight distinct fossil fuel sources which have been studied during the
screening tests are presented in Table 1.  These coals and related materials
have been subjected to determinations of free swelling index, heating value,
ultimate analysis, proximate analysis, sulfur species, and ash fusion temper-
ature.  These values are typical or representative of the various coal seams
from which the samples were obtained.  (It is known that the moisture content
as well as other  possible  parameters for a particular coal type can vary from
one sample to another.  Representative analyses,  as shown in Table 1, were
used for the screening  test studies.  However,  individual analyses for the
particular feed material utilized  for each gasifier test run are being
performed for the feed  materials  in the  parametric test runs of this research
program).
2.2  REACTOR OPERATING  CONDITIONS
     The air-to-coal  ratio, steam-to-coal  ratio,  reactor  pressure  and tempera-
ture were selected  for  many of  the screening  tests in  order  to  obtain con-
ditions  comparable  to those used  in pilot  plant or commercial  coal  gasification

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                                                    TABLE  1.  ANALYSIS OF  FUELS  GASIFIED
en
Fuel
U. Kentucky
FHC Char
Illinois
No. 6
Bituminous
Montana
Rosebud
Subbi luminous
N.C. Humus
Peat
Pittsburgh
No. 8
Wyoming
Subbi luminous
N. Dakota
Lignite
M. Kentucky
No. 9
Bituminous
Btu/lb (inc. Volatile Fixed
moisture & Moisture Ash Hatter Carbon
ash) XXX X
11,090 1.90 19.70 7.80 71.50
11,331 6.85 13.52 32.58 47.05
9,004 21.19 8.86 31.56 38.39
4,975 45.98 3.67 31.81 16.54
12,288 3.08 11.09 29.16 56.67
7,880 15.56 6.31 38.30 39. 30
7,880 29.63 6.39 28.57 35.41
12,130 7.03 7.83 38.78 46.36
Sulfur:
Sulfate
Organic
Pyritic Carbon Hydrogen Oxygen Nitrogen FSI
Total X X X X X
1.80 74.02 1.48 1.70 1.3 <1 .0
0.15
1.16
1.71
3.02 63.26 5.37 13.46 1.35 3.5
0.17
0.21
0.21
0.59 53.95 6.87 . 28.53 1.20 0.0
0.05
0.06
0.01
0.12 30.22 5.34 59.84 0.81 0.0
<0.01
1.28
1.24
2.53 72.29 3.45 8.62 1.95 7
0.07
0.08
0.40
0.55 56.80 5.94 30.02 0.38 0
0.01
0.54
<0.01
0.56 46.82 9.85 35.63 0.73
0.05
2.90
1.83
4.78 67.36 5.58 13.68 1.08 4
Ash
Fusion
Temp.
°F
2600*
2350°F**
(2030-
2730°F)
2280*
(2150-
2240°F)

2270°F**
(2060-
2780°F)
2280°F*
(2110-
2460°F)
2340°F**
2090°F**
(1970-
2400°F)
        *As received--*!) and XO include that portion in moisture
        "Mean temperature

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reactors.  Table 2 presents various experimental  test conditions for the RTI
tests in relation to selected gasifier operating  conditions.   While the air-
to-coal ratio is generally lower for the RTI tests, most of the conditions
which have been examined have shown a quite close correspondence to those for
pilot scale and commercial fixed-bed gasification processes.
     Actual quantities of coal, steam, air, and tar involved in various
screening tests are presented in Table 3.  Steam-to-carbon ratios have been
investigated over the range from 0.4 to 18 g/g and air-to-carbon ratios from
0 to about 4 g/g.  Although the air-to-coal ratio has varied depending upon
the intended method of supplying heat to the reactor, the steam-to-coal ratio
has been predominantly in the range of 0.5 to 3.0 g/g.  (Excessive steam
simply passes through the reactor and results in additional aqueous condensate
formation in the reactor condenser system).  Maximum bed temperatures  have
been in  the range of 900 to 1000°C.  Carbon conversions have ranged from  52
to near  100 percent, oxygen-to-coal ratios from 0.0 to 0.9 g/g, and steam-to-
oxygen ratios from  0.9 to infinite.  Both  internal and external heat has  been
supplied to the  reactor system.
2.3  EFFLUENT SAMPLING AND CHEMICAL ANALYSIS
     The effluent gas stream  from  the fixed-bed  reactor passes  through a
particulate trap which  is  insulated  to  maintain  hot  gas conditions.  This is
immediately followed  by a  refrigerated  condenser unit  which  remov.es aqueous
condensate and  low  volatile  organic  material  at  the  system pressure.   The
condenser  unit  is followed by a backpressure  regulator.
     A glass  sampling system has  been  installed  on the low pressure side  of
the  backpressure regulator.   This  system includes  ports for  grab  samples  and
a  valving  system for  direct  adsorbent cartridges.  A port  also  exists  for
removal  of a  continuous gas  stream for  infra-red analysis.   Further,  the
primary  gas  stream  passes through  a  continuous dry gas meter to measure the
total  volumetric flow of  the effluent stream.
      Raw gas  samples  were collected  periodically during the  gasification  test.
These  samples were  contained in special glass sample bulbs  and maintained
under controlled conditions  in a specially designed sample storage chest.

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TABLE 2.  EXPERIMENTAL TEST PARAMETERS AND COMMERCIAL GASIFIER OPERATING CONDITIONS

Air/Coal g/g
Steam/Coal g/g
Carbon Conversion %
Coal Residence Tine (mln.
Tar Produced g/g
Gas Produced SCF/lb
HHV Btu/SCF
Throughput Ib/hr ft2
Coal Type
Pressure psia
Mesh Size
Maximum Temperature °C
Heatup Time to 800°C
(mln.)
Gas Composition
CO
C02
CH4
H2
N2
H2S
HHV Btu/SCF
RTI Tests
21
1.1
3.1
97
340
0.035
48
106
16
Illinois
No. 6
200
8 x 16
1015
20

16
18
5.4
30
30
0.4
200
23
2.2
1.2
96
300
0.033
56
96
19
Illinois
No. 6
200
8 x 16
1050
11

10
18
3.1
13
55
O.fi
100
25
1.7
0.50
99.7
180
0.018
41
142
30
(•ion tana
Subbit.
200
8 x 16
1060
3

24
9.1
2.4
13
52
0.06
140
32
1.5
0.37
99.5
110
0.011
32
183
44
Wyoming
Subbit.
200
8 x 16
1050
5

29
9.1
5.7
20
36
0.07
210
33
1.5
0.36
98.9
110
0.012
35
201
45
Wyoming
Subbit.
200
8 x 16
1040
8

32
4.9
5.7
20
37
0.07
210
35
1.7
0.37
97
110
0.029
40
128
46
Hy owing
Subbit.
200
8 x 16
910
23

16
12
3.7
14
54
0.08
130
METC*
2.3
0.31
98.7
120-540
0.022
47
153
107
Illinois
No. 6
315
2" x 0
—
__

21.8
6.9
2.0
17.8
51.5
156
5,6
Lurgi
3.0
1.5
95
60
NA
52
195
248
Subbl luminous C
New Mexico
300
1.75" x 0.08"
--
„

17.4
14.8
5.1
23.3
38.5
NA
200
Wellman
Galusha5
3.5
0.4
99+
120-540
0.06
NA
168
899
Bituminous
ATM
2" x 1.25"
1300
__

28.6
3.4
2.7
15.0
50.3
NA
170
Uoodal 1
Duckham5
2.3
0.25
99
NA
0.075
NA
175
70
HVCB
ATM
1.5" x 0.25"
1200
--

28.3
4.5
2.7
17.0
47.2
0.3
170

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                                          TABLE 3.   OPERATING  CONDITIONS—SCREENING TESTS
oo
^""-•^Test
Coal ^v^
Steam (g)
Air (g)
Coal (g)
Air/Coal
Steam/Coal
Air/Steam
T * °C
max
Carbon Conversion (%)
Sulfur Conversion (X)
Tar Yield (g/g Coal)
RTI Test Number
16
Illinois No. 6
3704
1350
1569
0.86
2.4
0.35
941
89
93
0.036
21
Illinois No. 6
4713
1720
1543
1.1
3.1
0.35
984
97
98
0.033
23
Illinois No. 6
1952
3288
1594
2.1
1.2
1.8
1020
96
95
0.033
41
Western Kentucky
1390
3060
1250
2.5
1.1
2.2
1034
99.8
98
0.030
25
Montana
748
2482
1491
1.7
0.50
3.4
1006
99.7
85
0.018
33
Wyoming
500 '
2097
1396
1.5
0.36
4.2
1010
98.9
91
0.012
35
Wyoming
527
2461
1420
1.7
0.37
4.6
790
97
85
0.029
36
North Dakota
639
1939
1444
1.3
0.44
3.1
916
99.7
91
0.013
43
North Dakota
422
2022
1458
1.4
Kl.29
4.8
914
99.4
80
0.0072
           Mime averaged maximum bed temperature.

-------
These  samples were systematically subjected to gas chromatographic analysis
for a  range of specific compounds including ethane, ethylene, and acetylene;
benzene, toluenes, and xylenes; hydrogen sulfide, carbonyl sulfide, and other
sulfur species.  Moreover, a continuous gas monitor was utilized in all
screening tests in order to obtain a continuous analysis for methane, carbon
monoxide, carbon dioxide,  and  hydrogen.
     The adsorbent cartridges have utilized XAD-2 resins for the volatile
organic constituents.  A single cartridge was used throughout the initial
portion of the run, the so-called surge period.  A valving arrangement
permitted switching of the cartridge to a fresh resin for utilization during
the so-called steady-state period, which presumably represents primarily the
char gasification process.  These XAD-2 resins were extracted with, methylene
chloride; the extracts were subjected to GC/mass spectrometer analysis.
     The condensate collection container was drained periodically throughout
a run with the content being accumulated for a complete gasification test.
This mix of aqueous condensate and low volatile organic material was sub-
jected to phase separation followed by a detailed chemical partitioning
process.  The aqueous phase was extracted with methylene chloride to remove
residual organic constituents.  The low volatile organic phase was extracted
so as to obtain tar acids, tar bases, polar neutrals, nonpolar neutrals, PNA,
                                           2
and hexane insoluble chemical  constituents.
     The effluents from screening test runs have been subjected to a wide
variety of chemical and bioassay tests in order to characterize and evaluate
                3
these materials.    Individual  reports have been prepared on the sampling and
analysis scheme as well as the environmental/health aspects of the results
                         2 "5
which have been obtained.      Additional reports are under preparation to
describe the results of parametric runs using the fixed-bed coal gasification
unit.

-------
                         3.0  EXPERIMENTAL RESULTS

     Chemical analysis results have been obtained for the raw gas  bulb samples,
the XAD-2 adsorbent resin samples, the low volatile organic material  (tar),
the aqueous condensate, and bottom ash, which remained within the  reactor.
The results include continuous monitor values for four primary gases,  GC
analyses for a variety of hydrocarbon and sulfur species gases, GC/MS  analyses
for volatile and low volatile organic compounds, plus a variety of elemental
determinations by atomic absorption and other techniques.
3.1  REACTOR SYSTEM BEHAVIOR
     A detailed examination of the temperature profiles throughout various
screening test runs was completed.  These results indicate that (1) the
initial temperature distribution undergoes considerable modification early in
a run  (surge period) but maintains a common character throughout the steady-
state  period in most cases, and (2) severe temperature gradients occur at or
near the top of the fixed-bed of solids throughout a run.  The surge period
is generally of relatively  short duration, e.g., 20 minutes,  and is indicated
by that period over which the methane  concentration  in  the  raw effluent gas
is 2 percent, by volume, or greater.   Thus,  reasonably  uniform temperature
control was  obtained over the duration of the char gasification process
(steady-state period).
     Results that  have been obtained with various  coals  in  the RTI gasification
tests  indicate that the degree of  desulfurization  during  partial gasification
is always  higher than  the carbon  conversion.  Sulfur  in  the resulting  gas is
present mainly in  the  form  of hydrogen sulfide.  Recent  research7 conducted
in Germany has also indicated that during the gasification  of coal at  tempera-
tures  about  950°C,  rapid degassing takes  place  which  involves desulfurization
of the coal, with  up  to 55  percent of  the sulfur being  removed  in the  first
four seconds.  The resulting material  is  a coke or char which reacts  with
oxygen and/or steam to produce carbon  monoxide,  carbon  dioxide, and hydrogen.
     Raw gas analyses  indicate a  decrease in hydrogen  sulfide concentration
with time  followed typically  by a  period  of  level  (constant) concentration,
or in  some cases, an increase.  Carbonyl  sulfide concentrations were found
                                     10

-------
generally to initially decrease and then level off or follow the hLS pattern.
These concentrations of carbonyl sulfide generally were found to be between
one to two orders of magnitude lower than those for the hydrogen sulfide,
Methanethiol and thiophene concentrations for all  tests were found to undergo
an early decrease from an initial maximum value to levels below the detection
limits of the gas chromatograph being utilized, i.e., below 1 ppm by volume.
     Additional work is, of course, needed in elucidating the mechanisms for
the formation of sulfur species.  It is generally believed that pyritic
compounds give rise to hydrogen sulfide under the reducing conditions typical
in coal gasification processes.  Other sulfur compounds such as methanethiol,
ethanethiol, thiophene, etc., may well  result from the decomposition of
organically bound sulfur in the coal material.  An additional consideration is
that elemental sulfur may well exist in the gas phase.
     Considering the behavior of the lower sulfur coals tested, the surge
phase levels of volatile organic sulfur compounds, e.g., methanethiol and
thiophene, are found to be much lower than those for the high sulfur Illinois
No.6 coal.  For reactive coals, e.g., Wyoming subbituminous and Montana
Rosebud, the levels of devolatilized organic sulfur compounds were reduced to
lower than minimum detectable levels as measured with an FPD detector on the
GC within less than 15 minutes from the introduction of the coal into the
reactor.  Ninety percent or more of the Cg-Cg aromatics also evolved during
the first 15 minutes of these tests.
     Concentration of the inorganic sulfur compounds HLS and COS were generally
found to follow the C0« concentration.   These concentrations reached a minimum
about midway during the tests carried out over 1000°C, but decreased mono-
tonically for tests carried out at lower temperatures (900°C).  In some cases
the concentrations of H^S and COS were found to increase near the end of a
run, indicating that relatively inactive sulfur-containing compounds in the
reactor were being converted after almost all of the carbon content had been
converted.
     The residue (bottom ash) analyses for various screening test runs are
presented in Table 4.  These values indicate that substantial carbon conversions
were obtained in almost all of the screening test runs.  Sulfur conversions
generally were not as high, indicating that while there may be char species
                                    11

-------
                                  TABLE 4.  RESIDUE (BOTTOM ASH) ANALYSES

Volatile Matter
Fixed Carbon
Moisture
Ash
C
H
N
S
Cl
0 (difference)
Organic Sulfur
Pyritic Sulfur
Sulfate Sulfur
X
I
%
X
I
X
X
%
X
X
X
X
X
Heating Value (Btu/lb.)
F.S.I..


16
2.04
34.46
0.15
63.35
35.90
0.29
0.32
1.06
HA
-
NA
NA
NA
3890
0

21
4.80
11.14
0.46
83.60
14.51
0.'43
0.53
0.43
< 0.01
0.04
0.24
0.09
0.10
. 1990
0

23
6.58
10.37
0.68
82.37
15.57
0.52
0.57
0.92
NA
-
0.40
0.25
0.27
2263
0

25
5.88
-
0.66
96.50
1.77
0.20
0.06
1.16
NA
-
0.07
0.04
1.05
< 50
0
RTI Test
33
9.94
9.76
2.58
77.72
15.28
1.19
0.14
1.20
0.05
1.84
1.04
0.15
0.01
2700
1/2
Number
35
2.00
26.76
2.53
68.71
24'. 81
0.71
0.31
1.28
0.03
1.62
0.86
<.01
0.42
3933
NA

36
1.59
2.66
3.76
91.99
2.52
0.15
0.06
1.03
0.08
0.41
0.15
0.80
0.08
309
1/2

41
2.76
0.10
o.n
97.03
1.64
0.02
0.08
0.88
0.04
0.20
0.83
0.03
0.02
340
1/2

43
14.38
_
4.69
88.51
5.24
1.63
0.00
2.21
0.09
_
0.44
0.06
1.71
544
NA
NOTE:  NA = Not Analyzed.
       C and H are exclusive of moisture.

-------
possessing relatively low reactivity carbon, the residual sulfur compounds are
quite resistant to gasification.  This is particularly true for sulfur which
has been oxidized to, or originally was, sulfate sulfur.  It is of interest to
note, that in almost every case the organic sulfur content also exceeded the
sulfate sulfur level within the reactor residue.  The two exceptions are for
runs 25 and 43 which involved Montana Rosebud and North Dakota lignite feed
materials, respectively.  (The individual carbon conversion and sulfur conver-
sion values for each of the runs shown in Table 4 can be found in Table 3).
3.2  CHEMICAL ANALYSIS RESULTS
     The gas chromatograph/mass spectrometer analysis of the various samples
and extracts (partitions) obtained from the sampling and analysis programs
associated with the gasification tests have resulted in the identification of
more than 300 organic species.  Additional compounds have been quantitated by
direct gas chromatographic analysis.  Atomic absorption measurements have been
performed on the various effluents to determine trace element compositions.
     Special attention has been given to compounds which were judged to have
environmental significance with less attention being paid to organic species
which currently available information indicates as being harmless.  Criteria
utilized for the analysis of screening test samples for this selectivity were
twofold:  first, compounds were specifically selected for study if they
possessed moderately toxic to severe health hazard potentials as evidenced by
a toxic threshold value less than 17 mg/m  and were suspected to occur in the
gasifier effluents; and secondly, any compound present in the effluents at
                        3
concentrations of 5 mg/m  or greater was given consideration.  The list of
compounds which have been detected throughout the screening test sequence is
provided in Table 5.  (It should be noted that some of the compounds listed
were detected only in the aqueous condensate which was collected from the
condenser unit on the effluent stream.   The compounds thus identified may have
been formed as a result of reaction of precursors in the condenser system.)
     The quantity of selected compounds produced in various of the screening
test runs per unit mass of carbon converted in the gasifier is presented in
Table 6.  It may be noted that the sulfur species and phenolic type compounds
                                      13

-------
             TABLE  5.    COMPOUNDS  IDENTIFIED  IN  GASIFIER  EFFLUENTS
                            (Arranged  by  MEG  Category)
MEG Category    Name
     Category
                                                        Name
                                                                               MEG Category
                                                                                               Name
1.   Aliphatic  Hydrocarbons
        methane
        ethane
        propane
        n-butane
        (sobutane
        n-pentane
        Isopentane
        n-hexane
        2-methylpentane
        3-methylpentane
        n-heptane
        n-octane
        n-nonane
        n-decane
        n-undecane
        n-dodecane
        n-tHdecane
        n-tetradecane
        n-pentadecane
        n-hexadecane
        methylcyclobutane
        cyclopentane
        cyclohexane
        d1methyleye1ohexane
        trlmethy1cyclohexane
        cyclooctane
        dimethyIdecahydronaphthalene
        ethene
        propene
        butene
        Isobutene
        hexene
        1-pentene
        2-methy1-1-butene
        1,3-butadiene
        pentadlene
        cyclopentene
        cyclohexene
        cyclopentadlene
        ethyne
        propyne

2.   Alkyl Hal ides
        d1ch1oromethane(artifact)
        trlchloromethane(artifact)
        carbon  tetrachlorfde
           (artifact)

3.   Ethers
        dlethylether
        pheny1-2-propynyIether
        1-methoxynaphtha1ene
        2-(iiethoxynaph tha 1 ene
        3,6-d1mthoxyphenanthrene
        2-methoxyf1uorene

5.   Alcohols
        3,5,5-trlmethyl-l-hexano!

7.  Aldehydes,  Ketones
        acetaldehyde
        butanal
        pentana 1
        p-hexanal
        n-heptanal
        n-octanal
        n-nonanal
        undecanal
	dodecanal
 1.    (Continued)
         benzaldehyde
         dlmethylbenzaldehyde
         acetone
         methylIsopropyl ketone
         butanone
         1-pheny1-1-propanone
         2-pentanone
         acetophenone
         o-hydroxyacetophenone
         m-hydroxyace tophenone
         benzophenone
         9-fluorenone
         benzofluorenone
         d1hydroxyanthraqui none
         tetrahydroanthraqui none
         phenanthrfdone

 8.    Carboxylic Acids  and Derivatives
         acetic add
         benzole add
         benzamlde
         ethyl  acetate
         a thy 1 benzyl acetate
         methyl  benzoate
         isobutyl  cinnamate
         dibutyl phthalate(artifact)
         d1isobutyl phthalate
            (artifact)
         dlcyclohexyl  phthalate
            (artifact)

 9.    NUHles
         acetonltrile
         cyanobutadiene
         benzonitrile
         2.2'-dicyanobiphenyl

10.    Amines
         aniline
         diphenylamine
         benzidlne
         1-aminonapnthaiene
         N-methyl-o-toluidine

13.   Thiols, Sulfides, and  Bisulfides
         methanethiol
         ethanethiol
         2,3,4-trithiapentane
         dimethyl  sulfide
         dimethyl  disulfide
         trlthiahexane
         d1pheny1  disulfide

15.   Benzene,  Substituted Benzene
              Hydrocarbons
         benzene
         toluene
         o-xylene
         m-xylene
         p-xylene
         ethyl benzene
         styrene
         methylstyrene
         ethylstyrene
         n-propyibenzene
         Isopropylbenzene
         1,2-dimethylbenzene
         t-butylbenzene
	n-oentvlbenzene	
IS.    (Continued)

         3,5-d1methyl-l-fsopropyl-
            benzene
         triethyl benzene
         o-ethyltoluene
         m-ethyltoluene
         trlmethylbenzene
         1,2,4-trimethyl-
            benzene
         1,3,5-trlmethylbenzene
         o-d1ethylbenzene
         m-d1ethylbenzene
         p-d1ethylbenzene
         methyltetrahydro-
            naphthaiene
         dimethyltetra-
            hydronaphthalene
         trimethyltetra-
            hydronaph tha1ene
         1,2,3,4-tetrahydro-
            naphthaiene
         5,8-d1methyl-l-n-octyl-
            1,2,3,4-tetrahydronaph-
            thalene
         1-methyl-4-n-hepty1-
            1.2,3,4-tetra-
            hydronaphthaiene
         bipheny1
         nmthylbiphenyl
         3-methylbipheny1
         diphenylroethane
         d1pheny1 ethane
         di (ethylPheny1)
            ethane
         stllbeneO.2
            dlphenylethene)
         me thy1pheny1ethyne
         d1pheny1ethyne
         1,2-diphenylpropane
         dlxylylethane
         o-terphenyl
         m-terphenyl
         p-terphenyl
         indan
         methylindan
         dimethylindan
         pentamethy 1 indan
         indene
         methylindene
         methy-l-2,3-dihydro-
            indene
         dlmethylindene
         trimethylindene

 18.   Phenols
         phenol
         o-cresol
         m-cresol
         p-cresol
         o-ethylphenol
         in-ethyl phenol
         p-ethy1 phenol
         Isopropylphenol
         o-allylpnenol
         m-phenylphenol
         2,3-xylenol
         2,4-xylenol
         2,5-xylenol
         2.6-xylenol
                                                      14

-------
TABLE  5   (continued).
   ME6 Category
Name
MEG Category
                                        Name
MEG Category
                                                                                Name
    18.    (Continued)

            3,4-xylenol
            3,5-xylenol
            3-methy1-6-ethylphenol
            2-methy!-4-ethylphenol
            4-tert-butyl-o-cresol
            di-t-butyl-4-
              ethy1 phenol
            trtmethyl phenol
            2-hydroxynaphthalene
            methy1hydroxynaphthalene
           hydroxyfluorene

    21.    Fused Polycycllc Hydrocarbons
            naphthalene
            cyclobutadlbenzene
            1-methyl naphthalene
            methyld1hydronaphtha1ene
            2-methy1naphtha1ene
           ethylnaphthalsne
            1sopropy1 naphtha 1ene
            1-methyl-7-isopropy1-
              naphthaiene
            l,2-d1hydro-3,5,3-
              trimethylnaphthaiene
            2-benzy1 naphtha1ene
           dimethyl naphtha 1ene
            l,4-d1nethylnaphthalene
           2,3-d1methyInaphthalene
           2.6-d1methy1 naphtha 1ene
           trimsthyInaphthalene
           acenaphthene
           acenaphthylane
           methylacenaphthy1ene
           3-methy1acenaphthy1ene
           anthracene
           9-methy1 anthracene
           ethyl anthracene
           phenanthrene
           methylphenanthrene
           1-methylphenanthrene
           3-methylphenanthrene
           4,5-methylenephenanthrene
           propenylphenanthrene
           trans-9-propenylphen-
              anthrene
           8-n-bu ty1phenanthrene
           2,/-dimethylphenanthrene
           pyrene
           methylpyrene
           1,2-benzanthracene
           hexahydro-l,2-benz-
              anthracene
           methyl-1,2-benzanthracene
           2.3-benzanthracene
              (naphthacene)
           3,4-benzophenanthrene
           methylbenzophenanthrene
           5,8-dlmethy1- 3,4-benzo-
              phenanthrene
           9,10-benzophenanthrene
              (triphenylene)
           1,2.3,4-tetrahydro-9,10-
              benzophenanthrene
           2-methyl-9,10-benzophen-
              anthrens
           chrysene
           methylchrysene
           benzo(a)pyrene
           benzo(e)pyr«ne
   	perylene	
                      21.    (Continued)
                               2-n-hexylperylene
                               benzo(g.h,1)perylene
                               dibenzo(a,h)anthracene

                      22.    Fused Non-Alternant Polycycllc
                                      Hydrocarbons
                               f1uorene
                               nwthylfluorene
                               1-me thylfl uorene
                               dime thy If] uorene
                               fluoranthene
                               1,2,3,4-tetrahydro-
                                 fluoranthene
                               benzo(a)fluorene
                               benzo(b)fl uorene
                               benzo(b)f1uoranthene
                               benzo(k) fluoranthene
                               1ndeno(l,2,3 cd)
                                 pyrene

                      23.    Heterocycllc Nitrogen Compounds
                               pyrrole
                               methyl pyrrole
                               pyrfdlne
                               methyl  pyridlne
                               4-acetylpyHdlne
                               d1methylpyr1d1ne
                               tr1methylpyr1d1ne
                               2,4-d1methyl-6-ethy1-
                                 pyrtdlne
                               2-hydroxy-4-pheny1pyri d1ne
                               2-hydroxy-6-phenylpyridine
                               3,4-d1phenylpyr1d1ne
                               benzopyrldlne
                               2,2'-d1methyl-4,4--
                                 dlpyrldyl
                               indole
                               methylIndole
                               methyl-3-allylhydroindole
                               3-methyl-3-allyd1hydro-
                                 indole
                               phenylIndole
                               3-methyl-2-phenylIndole
                               3,3'-biindolyl
                               quinoline
                               isoquinoline
                               methylquinpline
                               3-methyIguinoline
                               6-methylqu1noline
                               sthylquinollne
                               3-n-propylqulnol1ne
                               4-n-propylqu1noline
                               8-n-propylqu1nol1ne
                               <31methylqu1nol1ne
                               2,6-d1methylquino11ne
                               methylphenylquinoxalIne
                               4-styrylqu1nol1ne
                               7,8-benzoqu1noline
                               3-methylbenzoquinol1ne
                               benzimldazole
                               methylbenzlnrldazole
                               2-ethylbenzimidazole
                               benzylbenzimldazole
                               benzothlazole
                               2-m«thy1 -5-pheny1te trazo1e
                               dlphenyloxazole
                               acHdine
                               d1n«thy1acr1d1ne
                               acridone
                               carbazole
                               9-methylcarbazole
                                          23.    (Continued)
                                                   1,2,3,4-tetrahydrocarbazole
                                                   3-am1no-9-ethylcarbazole
                                                   vlnylphenylcarbazole
                                                   1,4-dihydro-2,3-benzo(b)
                                                      carbazole
                                                   2-am1no-4-phenyl-6-methyl-
                                                      pyr1m1d1ne*
                                                   2-am1no-5-ch1oro-4,6-
                                                      dlmethy 1 pyrlmidi ne*
                                                   4-(l,2.3,4-tetrahydro-2-
                                                      naphthyl)-morphol1ne
                                                   3-benzyHndene  phthallmlde*

                                          24.    Heterocycllc Oxygen  Compounds
                                                   furan
                                                   benzofuran
                                                   2-methylbenzofuran
                                                   3-methy1benzofuran
                                                   5-methy1benzofuran
                                                   7-methy1benzofuran
                                                   3,3-d1hydro-2-methylbenzofuran
                                                   dimethylbenzofuran
                                                   3,6-d1methylbenzofuran
                                                   di hydromethy1pheny1benzofuran
                                                   d1benzofuran
                                                   xanthene

                                          25.    Heterocycllc Sulfur Compounds
                                                   thiophene
                                                   2-methylthiophene
                                                   3-methylthiophene
                                                   2,3-d1methy!thiophene
                                                   2,4-dimethy1thiophene
                                                   2,5-dimethy1thi ophene
                                                   3,4-d1methy1thiophene
                                                   trimethylthiophene
                                                   i sopropy1thiophene
                                                   ethylthiophene
                                                   2-n-propyl-5-
                                                      isobutylthiophene
                                                   benzothiophene
                                                   methylbenzothlophene
                                                   dimethylbenzothiophene
                                                   trimethylbenzo-
                                                      thiophene
                                                   benzodithiophene.
                                                   me thyIbenzodithiophene
                                                   dibenzotniophene
                                                   methyldibenzothiophene
                                                   di hydrodi methy1thi eno-
                                                      thiophene
                                                   dimethylthiaindene
                                                   thiaxanthene

                                          42.    Carbon Compounds
                                                   carbon  monoxide
                                                   carbon  dioxide

                                          47.    Nitrogen  Compounds
                                                   ammonia
                                                   hydrogen cyanide

                                          52.    Sulfur Compounds
                                                   sulfur
                                                   sulfur dioxide
                                                   hydrogen sulflde
                                                   carbonyl sulfide
                                                   carbon dlsulfide

                                          99.    Hydrogen
                                                   hydrogen
                                                          15

-------
                                    TABLE 6.  POLLUTANT PRODUCTION
                                             produced in all streams)


g carbon
converted

Compound
hydrogen sulfide
carbonyl sulfide
niethanethlol
e thane thiol
carbon disulflde
thiopliene
methyl thiophene
hydrogen cyanide
auinon 1 a
an i 1 1 ne
qulnoline
acridine
Indole
phenol
cresols
xylenols
t rime thy 1 phenol
o-isopropyl phenol

16 21
3.8E3 3.8E3
4.0E2 2.0E2
3.9E1 8.3E1
-
7.8E1 4.9E1
1.8E3 5.9E2
3.2E2 .OE3
.3E2
.5E4
.5E1
.7E2
9.1E1
3.1EO
4.3E2 4.7E2
7.2E2 1.3E3
7.4E2
6.5E1
*" ""

23
9.8E4
5.6E2
5.2E1
2. 1EO
2.5E2
3.8E3
1.1E3
-
-
1.0E1
1.3E2
8.1E1
-
7.8E2
1.7E3
7.6E2
1.3E2
1.3E2
RTI
25
4.6E3
~'l.5E2
4.1EO
-
-
5.2E1
1.1E1
1.2E2
8.7E3
1.3EO
9.5E1
2.5EO
1.3EO
8.3E2
1.0E3
1.9E2
2.3E1
"
Test
33
3.4E3
2.0E2
2.5E1
-
-
1.6E1
1.8E2
-
-
1.6EO
I.8E1
4.3EO
-
2.7E3
8.9E2
3.1E3
5.8E1
2.0E1
Number
35
5.9E2
3.1E2
4.6E1
-
-
5.5E1
5.5E1
-
-
2.5EO
6.3EO
1.8EO
1.3EO
2.9E3
2.6E3
2.3E3
7.4E1
3.3E1

36
4.9E2
3.7E2
1.7E2
1.4E2
-
1.1E3
2.9E1
1.4E2
6.0E3
-
2.5E1
1.8E1
-
1.4E3
1.0E3
I.1E3
3.0E1
8.9EO

41
4.0E4
8.5E2
5.8E1
-
1.1EO
4.0E2
4.9E2
-
-
-
4.9E1
2.1E1
-
1.2E3
1.3E3
2.9E2
7.6E1
3.2E1

43
3.1E3
5.8E2
2.4E1
-
1.4E1
1.9E1
7.6E1
-
-
-
3.9EO
-
-
2.7E3
2.0E3
4.1E3
3.8E2
4.5E1
Note:  Ammonia was not measured in these runs.

-------
TABLE 6 (continued).
Compound
benzene
toluene
xytenes
ethylbenzene
indan
in dene
dibenzofuran
fluoranthene
fluorene
naphthalene
anthracene
phenanthrene
chrysene
pyrene
perylene


16
5.0E3
3.5E4
8.9E1
3.7E1
5.9E1
4.1E2
-
4.0E2
4.8EO
1.2E3
7.1E2
2.2E2
-
1.2E2
-

21
-
-
4.4E2
4.4E2
2.4E1
9.3EO
3.5E2
7.1E2
4.3E2
4.0E3
7.7EO
1.2E3
4.3E2
4.8E2
-

23
1.4E4
5.2E3
6.3E2
4.9E2
3.4EO
3.6E2
4.5E2
7.1E2
2.5E1
4.8E3
4.1E2
1.2E3
4.6E2
5.9E2
2.0E2
RTI
25
6.6E3
1.0E3
8.9E2
5.6E2
7.1EO
1.6E2
3.5E2
3.6E2
2.4E2
5.9E2
2.0E2
5.9E2
2.4E2
3.3E2
8.9E2
Test Number
33
8.1E3
3.3E3
8.1E2
2.0E2
1.4E2
9.8E2
1.1E2
5.8E1
1.0E2
6.3E2
1.5E2
7.2E1
3.7E1
4.5E1
2.4E1
35
6.8E3
4.0E3
1.5E3
6.2E2
3.6E1
2.6E2
8.7E1
2.2E1
8.9E1
2.5E2
1.4E2
8.5E1
3.6E1
6.3E1
1.3E1
36
1.1E4
3.1E3
8.3E2
3.8E2
1.4E1
1.7E2
6.6E1
1.4E2
8.5E1
5.2E2
2.1E2
1.3E2
4.7E1
8.5E1
1.5E1
41
1.9E4
3.0E3
4.1E2
7.4E2
7.4E1
7.4E2
3.6E2
1.5E3
3.4E2
3.5E3
1.0E3
9.8E2
-
1.1E3
-
43
3.4E3
2.1E3
6.2E2
1.9E2
3.7E1
4.8E2
7.6E1
2.3E1
6.3E1
1.7E2
1.1E2
3.6E1
9.1E1
2.0E2
1.3EO

   Note:  Ammonia was not measured in these runs.

-------
generally dominated in terms of quantity produced.   Additionally,  ammonia,'
benzene, toluene, naphthalene,  and phenanthrene were present at substantial
levels.
     A list of selected compounds of intermediate volatility, which may easily
condense from a gasifier effluent gas stream, is presented in Table 7.   The
quantity of each produced during gasification per unit of coal loaded into the
gasifier is presented for six different tests.  This table also identifies
which of these compounds have been detected in products from the Morgantown
fixed-bed gas producer, as well as a Chapman-Wilputte gasification unit. *
Similar information for chemical compounds contained in the crude tar from
various screening test runs is presented in Table 8.
     Additionally, the mass of the individual fractions obtained via crude tar
partitioning for the screening test runs are shown  in Table 9.  These values
have been averaged for the various coal types utilized in order to obtain the
relative amounts of individual partitions shown  in  Figure 2.  As can be seen  in
this figure, the total quantity of tar  generated per unit mass of  coal  loaded
or coal converted was highest  for bituminous  coals,  i.e., Western  Kentucky No.9
and Illinois No.6, and was  least  for the North  Dakota  lignite.  The Wyoming and
Montana Rosebud  coals were  at  intermediate levels relative  to tar  production.
The PNA fraction was  the  predominant individual  fraction  in every  case.  While
the total tar  produced  is very nearly  the  same  from the  gasification of Wyoming
subbituminous  coal and Montana Rosebud  coal,  the Wyoming  coal  resulted  in
larger percentage of  organic acids and  less  PNA compounds than  from  the Montana
coal.
     The quantities of  pollutants produced per  unit mass  of carbon converted
during the  coal  gasification process are shown  graphically  in Figures  3 through
11.  Numerical  values are also provided representing  the  total  amount  of
compound measured  per unit  of  coal  loaded  into  the  gasifier.   These  bar graphs
and numbers represent total  pollutant  quantities generated  for all  the various
effluents  collected.  The compounds  have been ranked so  that the  mass  per  unit
of carbon  converted of  each of the  various compounds shown  may be observed.
These  figures  represent a span of over 4 orders of  magnitude in the specific
pollutant  mass production quantity,  as expressed in units of yg pollutant per
gram  of carbon converted.   Thus,  it  was necessary  to represent these output
values in  logarithmic form  in  order  that the specific mass  values resulting
could  be displayed in such  a comparative fashion on a single diagram.
                                      18

-------
                                TABLE 7.   REACTOR GAS  STREAMS4*8
Compounds
9 produced/g coa)
Methyl thiophenes
Cy- thiophenes
C.-benzenes
Benzofuran
Indan
Indene
Phenol
Cresols
Xylenols
Naphthalene
Biphenyl
Olphenyline thane
Oibenzofuran
Anthracene
Phenanthrene
C, -benzenes
Acenaphthene

5
2
2
5
1
1
7
1

4
5
8
2
4
1

21
.1E-4
.OE-4
.3E-4
.4E-5
.3E-5
.2E-4
.4E-5
.8E-4*
*
.5E-4
.OE-6
.1E-7
.6E-5
.1E-6
.8E-6
NA
NA
23
4.8E-4
2.4E-4
2.2E-4
1.4E-4
1.5E-6
1.6E-4
9.9E-5
2.3E-4*
*
1.5E-3
7. OE-6
7. OE-6
3. OE-5
3.0E-10
2.0E-10
NA
NA
RTI Test
25
5.6E-6
2.5E-6
1.4E-4
2.5E-5
3.7E-6 •
7.9E-5
7.4E-5
2.5E-5
5.2E-5
9.6E-5
1.5E-6
7.4E-7
2.2E-6
1.5E-6
NA
NA
NA
No.
32
l.OE-5
3.3E-6
l.OE-4
1.6E-5
4.1E-6
4.9E-5
1.3E-4
7.1E-5
1 . 3E-4
2.6E-4
2.5E-6
l.OE-6
2.6E-6
8.1E-7
NA
3.9E-5
NA
33
l.OE-4
2.7E-6
al.lE-4
NA
7.6E-5
5.4E-4
1.2E-3
3.2E-4
1.4E-3
2.5E-4
6.3E-6
2.8E-6
1.8E-5
2.3E-6
0
2.3E-5
NA

3
2
1
2
1
5
2
7
8
3
1
7
1

1
5
35
.OE-5
.3E-5
.3E-5
.1E-4
.OE-5
.4E-4
.9E-4
.7E-4
.OE-4
.5E-5
.OE-6
.5E"-6
.3E-6
.2E-6
0
.2E-4
.OE-7
Found In
METC
Cond.
X
X
X
X
X
X
X

X

X


X
X
Found In
METC
Tar

X
X
X
X
X
X

X
X
X


X
X
Found In Found In Found In
C-W C-W C-W
Vent Gas Cond. Tar

X

X XX
X XX
X
X
X XX


X X

X
X X
C-W - Chapman-Wllputte

-------
                                                     TABLE 8.  TAR POLLUTANTS4'8
(V)
o
Compounds
g produced/g coal
Quinoline
Acridine
Naphthalene
Fluorene
Dibenzofuran
Fluoranthene
Chrysene
Perylene
Anthracene
Phenol
Cresols

1
5
1
2
2
4
2


9
3
21
.OE-4
.7E-5
.9E-3
.7E-4
.5E-4
.1E-4
.7E-4
NA
NA
.7E-5
.7E-4
23
8.2E-5
5.0E-5
8.5E-4
1.5E-4
1.7E-4
4.3E-4
2.8E-4
1.2E-4
2.4E-4
1.5E-4
4.6E-4
RTI
Test
25
5.0E-5
1
2
1
9
1
1
4
1
7
1
.3E-5
.1E-4
.3E-4
.4E-5
.9E-4
.3E-4
.7E-5
.1E-4
.5E-5
.3E-4
Number
32
1
3
1
4
3
1
9
7
1
3
1
.1E-5
.8E-6
.3E-4
.6E-5
.8E-5
.4E-4
.7E-5
.4E-5
.5E-4
.8E-5
.2E-4
33
l.OE-5
2.4E-6
8.9E-5
5.7E-5
4.1E-5
3.2E-5
2.1E-5
1.3E-5
8.2E-5
1.6E-4
3.5E-4
35
1.2E-5
1.1E-5
4.6E-5
4.8E-5
4.2E-5
1.2E-5
7.0E-6
7.5E-5
7.5E-5
3.3E-4
7.7E-4
METC
NA
NA
7.2E-4
1.6E-5
1.5E-4
NA
NA
NA
NA
1.4E-5
6. OE-4
Chapman
Wilputte
1.9E-3
9.0E-5
2.1E-4
2.4E-4
NA
1.4E-4
2.9E-4
8.0E-5
6.E3-4
1.8E-4
NA
            *Maximum of  three  samples  assumed  0.034  g  tar/g  coal.

-------
TABLE 9.  WEIGHT PERCENT OF INDIVIDUAL FACTIONS OBTAINED FROM CRUDE TAR PARTITIONING


Tar Mass (grams)
X Organic Acids
% Organic Bases
X Insoubles
% Nonpolar Neutrals
& PNA's
% Polar Neutrals
1 Tar/Coal

6
15.9
30.3
12.5
13.9
13.0
16.5
13.8
1.54

16
56.5
13.2
6.0
9.5
29.8
33.3
8.1
3.59

20
54.3
13.96
5.52
16.70
12.56
44.49
6.76
3.44
Test Number
21
5.11
10.05
7.49
10.15
13.95
53.13
5.23
3.30

23
52.33
12.9
7.2
11.3
11.1
53.6
4.0
3.26

25
26.42
11.1
4.8
2.8
7.4
68.7
5.2
1.77

26
26.46
13.3
6.6
5.4
17.2
51.4
6.0
1.78

32
14.7
14.6
5.3
6.2
16.5
51.9
5.5
1.081

Test Number

Tar Mass (grains)
X Organic Ads
X Organic Bases
X Insolubles
X Nonpolar Neutrals
X DNA's
X Polar Neutrals
X Tar/Coal
33
16.823
26.9
3.3
1.7
20.4
39.8
7.8
1.20
35
41.2
29.6
3.4
4.)
18.3
35.4
9.2
2.90
36
12.0
—
--
—
--
—
—
--
38P
1.194
9.93
1.04
1.82
- 49.68
29.94
7.59
0.159
38G
12.93
20.37
3.73
0.33
23.75
35.57
11.45
1.72
41
37.56
5.22
7.06
8.05
12.50
61.75
5.42
3.00
43
10.49
25.28
5.42
5.66
20.70
33.21
9.73
0.719
44
30
6.47
6.49
4.80
11.22
67.38
3.64
2.40

-------
              TAR PARTITIONS (Averaged)

                   (Tar as percent of coal)
y\
 iORACID
 I I I I I I T
 ORBASE
 \\ \ \ \ n
—NPNEU-
            2.78%
            yu^gougcc
            ooooooooc
            OOOoOCOOC
            S92SS939S
                        1.82%     1.78%
                                                0.78%
W.Ky. #9
Wyoming     Montana
N.D. Lig.
                 Figure 2.  Tar partitions.
                           22

-------
   Compound
                           Log ug  pollutant/g  carbon converted
 Toluene
 Benzene
 Hydrogen Sulflde
 Thiophene
 Naphthalene
 CresoIs
 Anthracene
 Phenol
 Indene
 FTuoranthene
 Carbonyl Sulfide
 Methyl thlophene
 Phenanthrene
 Pyrene
 Xylenes
 Carbon 01su1f1de
 Indan
 Methanethlol
 Ethyl benzene
 Fluorene
           1           2
2.0E-2  g/g coal loaded
2.8E-3
2.1E-2
l.OE-3
6.9E-4
4.1E-4
4.0E-4
2.4E-4
2.3E-4
2.3E-4
2.3E-4
1.8E-4
T.3E-4
6.8E-5
5.1E-5
4.3E-5
2.3E-5
2.2E-5
2.1E-5
2.7E-6
Figure  3.   Production  factors  for  major pollutants  from run  no.  16
             with  Illinois  No.6  coal.    NOTE:   Ammonia was not  measured
             in this run.
                                        23

-------
                                Log _g pollutant/g carbon converted
Hydrogen Sulfide
Ammonia
Naphthalene
Cresols
Phenanthrene
Methylthiophene
Xylenols
Huoranthene
Thiophene
Pyrene
Phenol
Dibenzofuran
Xy1enes
Ethyl benzene
Chrysene
Fluorene
Carbonyl Sulfide
Ouinoline
Hydrogen Cyanide
Acridine
Methanethiol
Trimethy 1 phenol
Carbon Disulfide
Indan
Aniline
[ndene
Anthracene
Indole
 2.1E-2
 8.8E-3
 2.2E-3
 7.3E-4
 6.8E-4
 5.6E-4
 4.0E-4
 3.8E-4
 3.3E-4
 2.7E-4
 2.6E-4
 2.5E-4
 2.4E-4
 2.4E-4
 2.4E-4
 2.4E-4
 1.1E-4
J9.2E-5
•8.0E-5
,5.1E-5
;4.6E-5
'3.6E-5
 2.7E-5
I1.3E-5
 4.4E-6
 8.0E-6
 4.4E-6
g/g coal  loaded
      1.7E-6
Figure  4.   Production factors for major pollutants from  run  no.  21
              with  Illinois  No.6 coal.
                                            24

-------
Compound
Hydrogen Sulfide
Benzene
Toluene
Naphthalene
Thiophene
Cresols
Phenanthrene
Methyl thiophene
Phenol
Xylenols
Fluoranthene
Xylenes
Pyrene
Carbonyl Sulfide
Ethyl benzene
Chrysene
Dibenzofuran
Anthracene
Indene
Carbon Oisulfide
Perylene
Trimethyl phenol
Quinoline
Acridine
Methanethiol
Fluorene
Aniline
Indan
Ethanethiol
Log ug pollutant/g carbon converted
V 1 t t
1 £ J T
g/g coal loaded 6.0E-2
3.5E-3
3.2E-3
3.0E-3
2.3E-3
l.OE-3
7.7E-4
6.7E-4









-











4.7E-4
4.6E-4
4.2E-4
3.8E-4
3.6E-4
3.4E-4
2.9E-4
2.SE-4
2.1E-4
2.4E-4
2.2E-4
1.5E-4
1.2E-4
8.1E-5
8.1E-5
4.9E-5
3.2E-5
1.5E-5
6.1E-6
2.0E-6
1.3E-6
Figure 5.  Production factors for major pollutants from run no.  23
           with Illinois No.6 coal.   NOTE:   Ammonia was not measured
           in this run.
                                 25

-------

Hydrogen Sulfide
Benzene"
Naphthalene
Toluene
Fluoranthene
Cresols
Phenol
Pyrene
Anthracene
Phenanthrene
Carbonyl Sulfide
Indene
Ethyl benzene
Methyl thiophene
Xylenes
Thiophene
Oibenzofuran
Fluorene
Xylenols
Ethanethiol
Trimethyl phenol
Indan
Methanethiol
Quinol ine
o-isopropylphenol
Ac r1 dine
Carbon Disulfide
Log ug pollutant/g carbon
i i i
2.7E-2 g/g coal loaded
1.3E-2 |
2.5E-3
2.0E-3
l.OE-3
8.8E-4
8.2E-4
7.4E-4
6.7E-4
5.6E-4
5.7E-4
5.0E-4
4.2E-4 '
3.3E-4
3.2E-4
2.7E-4
2.4E-4
2.3E-4
1.9E-4
1.1E-4
5.1E-5
5.0E-5
3.8E-5
3.3E-5
2.2E-5
1.4E-5
J 7.4E-7
Figure 6.  Production factors in major pollutants from run no.41 with
           Western Kentucky No.9 coal.  NOTE:  Ammonia was not
           measured in this run.

                                 26

-------
                                     Log ug  poHutants/g carbon  converted
                                    	i	i	
  Ammonia
  Benzene
  Hydrogen  Sulfide
  Toluene
  Perylena
  Xylenes
  Phenol
  Phenanthrene
  Naphthalene
  Cresols
  Fluorantnene
  Pyrene
  Ethylbenzene
  Fluorene
  Chrysene
  Anthracene
  Dibenzofuran
  Inderte
  Carbonyl  Sulfide
  Quinoline
  Thiophene
  Acridine
  Trimethylphenol
  Hydrogen  Cyanide
  Methylthiophene
  Indan
  Methanethiol
  Indole
  Aniline
4.8E-3
3.6E-3
2.5E-3
5.4E-4
4.3E-4
4.8E-4
4.2E-4
3.2E-4
3.2E-4
2.3E-4
2.0E-4
1.8E-4
1.5E-4
1.3E-4
1.3E-4
1.1E-4
9.3E-5
3.3E-5
8.0E-5
5.1E-5
2.8E-5
1.4E-5
1.2E-5
6.3E-6
5.9E-6
3.8E-6
2.2E-6
   6.8E-7
   S.3E-7
g/g coal  loaded
Figure  7.   Production  factors for major  pollutants  from  run  no.25 with
              Montana Rosebud coal.
                                             27

-------
     Compound
  Benzene
  Hydrogen Sulfide
  Toluene
  Xylenols
  Phenol
  Indene
  Cresols
  Xylenes
  Naphthalene
  Ethylbenzene
  Carbonyl Sulfide
  Methylthlophene
  Anthracene
  Indan
  Dlbenzofuran
  Fl uorene
  Phenanthrene
  Trimethylphenol
  Fluoranthene
  Pyrene
  Chrysene
  Methanethiol
  Perylene
  o-isopropylphenol
   quincline
   Thiopnene
   Acridlne
   Aniline
                                  Log ug pollutant/g carbon converted
A.6E-3   q/q coal loaded
 1.9E-3
 1.8E-3
 1.7E-3
 1.5E-3
 5.5E-4
 5.1E-4
 4.6E-4
 3.5E-4
 1.1E-4
 1.1E-4
 l.OE-4
 8.5E-5
 7.6E-5
 5.9E-5
 5.7E-5
 4.1E-5
 3.4E-5
 3.2E-5
 2.1E-5
 2.5E-5
 1.4E-5
 1.3E-5
 1.2E-5
 l.OE-5
 9.0E-6
        2.4E-6
        8.7E-7
Figure  8.   Production factors for major  pollutants from  run  no.33 with
              Wyoming  subbituminous  coal.   NOTE:   Ammonia was not measured
              in this  run.
                                                28

-------
                                    Log jQ  pollutant/g carbon converted
        Hydrogen Sulfide
        Benzene
        Toluene
        Phenol
        Cresols
        Xylenes
        Xylenols
        Ethyl benzene
                 3.5E-3
                3.5E-3
                2.0E-3
                1.2E-3
                1.1E-3
                7.4E-4
                5.4E-4
                1.9E-4
        Carbonyl Sulfide  1.6E-4
        Indene
        Naphtnalene
        Anthracene
        Fluorene
        Oibenzofuran
        Phenanthrene
        Trimethylphenol
        Pyrene
        Thiophene
                1.3E-4
                7.9E-5
                7.2E-S
                4.6E-S
                4.5E-5
                4.4E-5
                3.8E-5
                3.2E-5
                2.8E-5
Methylthiophene  j 2.8E-5
Chrysene
Indan
                       .  1.9E-S
                         I.3E-5
        o-isopropy!phenolj  1.7E-5
        Fluoranthene
        Perylene
        Quinoline
        Aniline
        Acridine
        Indole
1           Z
 g/g  coal loaded
Figure  9.   Production  factors  for  major pollutants  from  run  no.  35
             with Wyoming subbituminous  coal.   NOTE:   Ammonia  was  not
             measured  in this run.
                                          29

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Benzene
Ammonia
Hydrogen Sulfide
Toluene
Phenol
Thiophene
Xylenes
Naohthalene
Carbon Sulfide
Ethyl Benzene
Anthracene
Indene
Methanethiol
Xylenols
Fluoranthene
Phenanthrene
Pyrene
Fluorene
Dibenzofuran
Ethanethiol
Chrysene
Trimethyl Phenol
Methyl Thiophene
Ouinol ine
Acridine
Perylene
Indan
o-Isopropylphenc
Log ug pollutant/g carbon converted
5.4E-3 g/g coal loaded
2.5E-3 1
2.3E-3
1.4E-3
l.GE-3
5.1E-4
3.9E-4
2.4E-4
1.7E-4
1.6E-4
l.OE-4
7.9E-5
7.9E-5
6.9E-5
6.3E-5
6.2E-5
4.0E-5
4.0E-5
3.1E-5 J
2.2E-5
2.2E-5
1.4E-5
1.3E-5
1.2E-5
8.3E-5
6.9E-6
•6.4E-6
)l)4.2E-6
Figure 10.   Production factors for major pollutants from run no.  36
            with North Dakota Zap lignite coal.
                                  30

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                                  Log i,g pollutant/g carbon  converted
     Benzene
     Hydrogen Sulfide
     Toluene
     Xylenols
     Cresols
     Phenol
     Xylenes
     Carbonyl Sulfide
     Indene
     Trimethyl Phenol
     Naphthalene
     Ethylbenzene
     Anthracene
     Chrysene
     Methylthiophene
     Dibenzofuran
     Fluorene
     o-Isoprophylphenol
     Indan
     Phenanthrene
     Ethanethiol
     Methanethiol
     Fluoranthene
     Pyrene
     Thiophene
     Carbon Disulfide
     Quinoline
     Perylene
 I.6E-3
 1.4E-3
 9.1E-4
 3.7E-4
 4.9E-4
 3.5E-4
 2.9E-4
 2.7E-4
 2.2E-4
•1. 7E-4
 7.7E-5
 6.0E-5
 5.2E-5
U.3E-5
 3.5E-5
 3.5E-5
 2.9E-5
 2.1E-5
 1.7E-5
 I.7E-5
 I.3E-5
I1.1E-5
9.5E-6
 1.1E-5
8.9E-6
6.7E-6
 1.8E-6
  6.3E-7
g/g coal loaded
Figure  11.   Production factors for major  pollutants  from  run  no.  43
               with North Dakota Zap lignite coal.   NOTE:  Ammonia  was
               not  measured  in  this  run.
                                          31

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     Figures 3 through 11 indicate that no consistent hierarchy of compounds
exists regardless of whether one considers compounds produced from an  in-
dividual coal or from coals of equal rank gasified under alternative operating
conditions.  Ammonia was not measured in all of these tests; yet, it is known
that ammonia occurs at high levels in the effluent of gasifiers operating on
fuels containing nitrogen.  It is important to note that benzene, toluene,
and xylene as well as sulfur species^ phenolic compounds, and two-ring PNAs
were important in every case.
     The composition of the major elements in selected tars (low volatile
organic condensate) is shown in Table 10.  While the sulfur and nitrogen
content of these materials is relatively high, the higher oxygen content
indicates that phenolic, carboxylic, and other hetero-oxygen compounds are
present in relatively significant quantities.
     In order to effectively analyze the extensive data obtained during the
screening test sequence, material balance computations and  statistical
correlation  analyses were performed.  Data values were entered  into a com-
puter memory for the statistical analysis.  Stepwise multiple  linear regression
techniques were utilized in order to effectively evaluate the  influence of
the independent variables present during these experiments.  The material
balance results, as well as the statistical analysis technique  and  results,
are discussed in the following sections.
                                       32

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TABLE 10.  PRIMARY ELEMENTS OF  TARS
                                   1,4,9
Run
No.
6
15
16
21
23
25
33
35
36
41
43
METC
METC
METC
Coal Type
Illinois No. 6
Illinois No. 6
Illinois No. 6
Illinois No. 6
Illinois No. 6
Montana Rosebud
Wyoming Subbituminous
Wyoming Subbituminous
North Dakota Lignite
Western Kentucky No. 9
North Dakota Lignite
Montana Rosebud
Western Kentucky No. 9
New Mexico Subbituminous
















Weight Percent of Element in Tar
% Carbon
78.7
87.5
87.6
87.7
86.0
88.6
86.5
83.0
86.1
86.3
82.3
78.0
80.0
84.4
% Hydrogen
6.3
6.1
6.2
6.1
5.8
6.0
6.0
7.7
7.0
6.1
7.5
6.6
8.7
7.2
% Nitrogen
1.3
1.3
2.1
1.4
1.6
0.8
0.8
1.5
1.3
1.6
1.8
1.1
1.9
1.7
% Sulfur
2.9
1.9
1.6
1.8
2.5
0.7
2.4
0.5
0.7
2.7
0.9
2.4
2.7
1.4
% Oxygen
10.9
3.2
2.4
3.1
3.8
4.0
4.3
7.4
4.9
2.8
7.0
11.0
NA
NA
                 33

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                        4.0  MATERIAL BALANCE RESULTS

     A variety of screening tests have been performed in the RTI  fixed-bed
gasifier.  One purpose of these tests was to develop operating procedures  and
sampling techniques for the gasifier.  Nine runs representing five coal  types
were chosen as candidates for complete material  balances- on ash and the major
elements:  hydrogen, oxygen, carbon, nitrogen and sulfur.  The material
balances were taken over the length of the gasification run which was con-
sidered to be the time from the coal drop to oxygen breakthrough.
     Results of the material balances are summarized in Table 11.  It can  be
seen that the average of the overall material balance for each of the runs
gives a 100 percent closure but with a standard deviation of 13 percent.  The
other component balances except sulfur are within 11 percent of closure but
they also have a large standard deviation indicating considerable scattering
of the closures.  Sulfur is the component in the material balances which
appears in the smallest amounts.  The deficiency in the closure of the sulfur
balances is probably due to the sampling procedure used in these preliminary
screening runs.  This point as well as experimental deviations in other
balances are discussed in more detail below.  Also discussed is the possible
improvement of the balances obtained by making judicious and reasonable changes
in experimental values that could perhaps be in error.
4.1  COMPUTATION PROCEDURE
     Detailed material balances were performed  for various runs on each of the
five coals considered.  The amount  of each of the major components in the
various  inlet or outlet streams was  computed.   Sample results are shown in
Tables 12 through  16.
     The coal charge for each  experiment was measured within ± 1  gram using a
scale; however, it was found that 4 to 5 grams  of coal  usually retained in the
coal feeder giving an error of up to 0.5 percent in  the  coal  feed  reported in
Tables 12 through  16.  An  ultimate  analysis  of  the coal  charges  for  each
individual run was not made and this could  be a source  of  considerable  error
due  to changes  in  moisture  content.  The amount of  each  major element  in  the
                                      34

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co
en
                                 TABLE 11. ELEMENTAL BALANCES FOR RTI SCREENING RUNS

                                                % Closure (outlet wt./inlet wt.)
RUM 1
16
21
23
25
33
35
36
41
43
Standard
Deviation
OVERALL
74
(96)
91
(97)
117
(100)
97
98
107
(100)
99
(101)
106
(100)
111
(101)
13
(2)
HYDROGEN
64
(99)
86
(95)
114
(100)
82
100
80
(98)
80
(112)
118
(109)
95
(115)
17
(10)
OXYGEN
64
(100)
91
(100)
119
(100)
101
104
92
(99)
90
(100)
109
(100)
105
(100)
16
(1)
CARBON
81
86
97
86
84
91
(100)
37
(100)
106
87
(100)
8
(9)
NITROGEN
94
96
121
(99)
100
100
126
(100)
115
(104)
105
.(100)
128
(101)
13
(3)
SULFUR
75
63
114
72
53
12
48
81
73
28[20]*
ASH
114
123
118
85
65
107
74
72
123
24
     [  ]  Excludes Run #35

     NOTE:  By adjusting selected  experimental  values,  results shown In parentheses  are  obtained.

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                        TABLE 12.  MATERIAL BALANCE RESULTS  FOR  RUN NO.16  (ILLINOIS NO.6 BITUMINOUS COAL)
co

Component
Coal
Steam
Air
Total Input
Gas
Condensate
Tar
Residue
Total Output
Balance, %
Total *
Amount
1572.8
4110.0
2021.4
7704.2
3569.2
1734.0
(3461.6)
59.6
325.7
5688.5
(7416.1)
74
(96)
Hydrogen
Amount
83.36
456.67
540.03
147.78
192.67
(384.62)
3.69
0.94
345.08
(537.03)
64
(99)
Oxygen
Amount
191.88
3653.33
380.76
4225.97
1147.59
1541.33
(3076.95)
1.43
0.00
2690.35
(4225.97)
64
(100)
Carbon
Amount
1046.54
1046.54
680.32
52.25
115.85
848.42
81 .:
Nitrogen
Amount
23.91
1640.60
1664.51
1561.53
1.24
1.04
1563.61
94
Sulfur
Amount
48.44
48.44
31.97
0.95
3.42
36.34
75
Ash
Amount
178.67
178.67
204.44
204.44
114
     *•
      Amounts in Grams

     NOTE:  By adjusting selected experimental values, results shown in parentheses are obtained.

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                      TABLE 13. MATERIAL BALANCE  RESULTS  FOR RUN  MO.25  (MONTANA  SUBBITUMINOUS COAL)
co

Component
Coal
Steam
Air
Total Input
Gas
Con den sate
Tar
Residue
Total Output
Total *
Amount
1495.0
704.0
2901.1
5100.1
4020.9
783.0
24.4
114.3
4942.6
Hydrogen
Amount
102.71
78.22
180.93
60.82
87.00
0.23
148.05
Oxygen
Amount
426.52
625.78
676.00
1728.30
1051.49
696.00
0.12
1747.61
Carbon
Amount
806.55
806.55
673.04
22.78
0.46
696.28
Nitrogen
Amount
17.94
2225.13
2243.07
2232.23
0.11
2232.34
Sulfur
Amount
8.82
8.82
3.30
1.64
1.37
6.31
Ash
Amount
132.46
132.46
112.0
112.0
     Balance,  %
97
82
101
86
100
72
85
      Amounts  in  Grams

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                   TABLE  14.  MATERIAL  BALANCE RESULTS FOR RUN NO.33 (WYOMING SUBBITUMINOUS COAL)

Component
Coal
Steam
Air
Total Input
Gas
Condensate
Tar
Residue
Total Output
Total ^
Amount
1399.6
504.0
2027.7
3931 . 3
3219.2
545.0
16.8
71.4
3852.4
Hydrogen
Amount
83.14
56.00
139.14
75.43
60.56
1.86
0.87
138.72
Oxygen
Amount
420.16
448.00
472.45
1340.61
905.30
484.44
5.37
1.36
1396.47
Carbon
Amount
793.57
793.57
651.49
7.61
11.20
670.30
Ni trogen
Amount
5.32
1555.25
1560.57
1584.27
0.73
0.10
1585.10
Sulfur
Amount
9.10
9.10
2.72
1.25
0.88
4.85
Ash
Amount
88.31
88.31
57.0
57.0
Balance, %                   98           100         104             84            100              53          65
*
 Amounts in Grams

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                       TABLE 15. MATERIAL BALANCE RESULTS FOR RUN NO.36 (NORTH DAKOTA LIGNITE COAL)
GO
IO


Component
Coal
Steam
Air
Total Input
Gas

Condensate

Tar
Residue Particulates
Total Output

Balance, %

Total *
Amount
1446.7
629.8
2414.4
4490.9
3681 . 2
(3590.6)
676.0
(871.1)
14.9
71.6
4443.7
(4548.2)
99
(101)
Hydrogen
Amount
94.90
69.98
-
164.88
56.23
(86.44)
75.11
(96.79)
1.15
0.11
132.60
(184.49)
80
(112)
Oxygen
Amount
563.63
559.82
562.57
1686.02
910.16
-
600.89
(774.30)
1.25
0.31
1512.61
(1686.02)
90
(100)
Carbon
Amount
677.04
_
-
677.04
572.65
(663.29)
-
-
12.17
1.88
586.70
(677.34)
87
(100)
Nitrogen
Amount
10.56
_
1851.79
1862.35
2139.23
(1927.74)
-
-
0.13
0.04
2139.40
(1927.91)
115
(104)
Sulfur
Amount
8.10
_
-
8.10
2.94
-
-
-
0.16
0.77
3.87
-
48
-
Ash
Amount
92.44
_
-
92.44

_
_
_
_
68.44
68.44
-
74
-
       Amounts  in Grams

      NOTE:   By adjusting selected experimental values, results shown in parentheses are obtained.

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               TABLE 16. MATERIAL  BALANCE  RESULTS  FOR  RUN  NO.41  (WESTERN KENTUCKY BITUMINOUS COAL)


Component
Coal
Steam
Air

Total Input

Gas
Condensate

Tar
Residue Particulates
Total Output

Balance, %

Total *
Amount
1250.0
1388.0
3764.2
(3956.2)
6402.0
(6594.2)
5316.4
1360.0
(1183.3)
35.0
84.0
6795.4
(6618.7)
106
(100)
Hydrogen
Amount
62.37
154.22
_
_
216.59

101.48
•151.09
(131.46)
3.27
0.01
255.85
(236.22)
118
(109)
Oxygen
Amount
230.54
1233.78
877.06
(921.80)
2341 . 38
(2386.12)
1334.36
1208.75
(1051.67)
-
0.09
2543.20
(2386.12)
109
(100)
Carbon
Amount
786.59
-
-
-
786.59

800.56
-
-
30.05
0.04
830.65

106

Nitrogen
Amount
17.39
-
2887.16
(3034.44)
2904.55
(3051.83)
3050.96
0.16
-
0.71
-
3051.83

105
(100)
Sulfur
Amount
37.14
-
-
-
37.14

28.99
-
-
1.01
0.02
30.02

81

Ash
Amount
115.63
-
-
-
115.63

—
-
-
-
83.80
83.80

72

*
 Amounts in Grams

NOTE:  By adjusting selected experimental values, results shown in parentheses are obtained.

-------
coal feed was obtained by multiplying the coal charge by the as-received
ultimate analysis.
     Steam was fed to the gasifier at a constant rate using a positive dis-
placement metering pump.  The accuracy of the steam input is thought to be
fairly high, i.e., ± 5 percent, since the pump was calibrated prior to use.
     The flow of air to the gasifier was not constant since it was used to
maintain the maximum temperature in the gasifier below a specified limit.  The
flow rate measurement was based on the heat capacity of the gas and could have
been in error by 10 percent.  The total flow of air was obtained by integrating
the flow measurements taken at least every two minutes over the length of the
run.
     The flow of product gas was estimated by differentiating the dry test
meter data; from a consideration of system leakage, flow rate was estimated
to be accurate to within ± 20 percent.  The composition of the gases were
determined by two independent measurements. The gas composition was monitored
every two minutes for CO, COo. CH», and Hp.  The accuracy of these measure-
ments of CO, C02, and CH. was considered to be within ± 1 percent of the
measured percentage but the H~ measurement could be in error by as much as ± 3
percent.  Bulb samples were taken throughout the runs.  These were analyzed
for the major components as well as minor components such as benzene, toluene,
xylene, and sulfur compounds.  Major gases were detected within a 2 percent
accuracy, and BTX and sulfur compound measurements were estimated to be accu-
rate within 10 percent.  In order to perform material balances on the gasifi-
cation runs shown in Tables 12 through 16, the discrete concentration values
were multiplied by the flow rate and summed (integrated) over the duration of
the run.   The integrated data showed that up to 8 percent of the product gas
was unaccounted for in these data.  Sources of error in the integration could
be due to inaccurate flow rates and/or inaccurate measurement of the time
intervals between samples.  In coal gasification the devolatilization of coal
takes place rapidly; thus, if only a few sample bulbs are taken during the
initial stage of a batch run, considerable amounts of devolatilization pro-
ducts may leave the system undetected.  This could explain the nonclosure of
the sulfur balances shown in Table 11.
     The condensate is measured volumetrically and this measure is converted
to weight.   The accuracy in the measurement is estimated to be normally within
                                       41

-------
± 5 percent.  In cases where the condensate was analyzed for contaminants,  the
contaminants were considered in the elemental  breakdown of the condensate.
Otherwise, the condensate was considered to be essentially water.
     The amounts of tar reported in Tables 12  through 16 consist of the actual
tar phase plus organics extracted from the condensate.   The ultimate analysis
of the tar was determined by standard techniques.   In several  runs  the tar
analyses were not available and the composition of the tar was estimated from
the analysis of tars from runs using the same  coal.   This procedure could
introduce little error into the elemental balances because of the small amounts
involved.
     The residue is weighed accurately; however, there are inadvertent losses
in removing the residue from the gasifier.  The ultimate analysis was obtained
by standard procedures.  The weight of particulates retained in the filter  in
most cases was not taken.  Several of the runs showed a net loss of ash.  The
missing ash could be contained in the unmeasured particulates.
4.2  MATERIAL BALANCE ADJUSTMENTS
     Better closures of the material balances  can be obtained by the reasonable
adjustment of selected experimental measures.   For example, in Table 12 it can
be seen that 4110 g of steam was fed to the gasifier but that only 1734 g of
condensate is reported to be collected.  This  represents a steam conversion of
58 percent which is not typical for Illinois No. 6 coal.  By increasing the
condensate mass so that the oxygen closure is  assured, the hydrogen and over-
all balances approach 100 percent closure for the run, as can be seen  in Table
12.  In Table 16 both the air flow and condensate measurements were adjusted
to ensure closure of nitrogen and oxygen.  This resulted in improvements to
both the overall balance and the hydrogen balance.
     Table 15 shows a case where both the condensate and gas analysis  were
adjusted to give closure of carbon and oxygen resulting  in improved closures
of the hydrogen and nitrogen balances.  The corrected amount of condensate
shown in Table 15 appears too large, in that it exceeds  the steam  input;
however, taking into account the moisture in the  lignite coal,  the corrected
condensate corresponds to almost 20 percent steam decomposition.
     Adjustments similar to those discussed above were made  in  several  other
runs.  Table  11 summarizes these  results.   It  can  be  seen  that  the average  of
                                       42

-------
the closures for each of the major components is improved and that the scatter
within the closures is reduced.  Some of the arbitrariness involved in the
adjustments could be removed from the material balance analyses using a well-
known procedure which minimizes the sum of the weighted squares of the
differences between an experimental measurement and a computed measurement,
where the computed composition analysis must sum to 1.0.  There is sufficient
redundancy of measurements in the RTI gasifier system that this procedure
could be used.  Such may be justified for the parametric test runs, for which
more precise control is being exercised over the reaction process.
     The adjusted material balances for the nine gasifier runs as summarized
in Table 11 demonstrate that the major elements can, in principle, be accounted
for in semi batch experiments.  RTI is presently attempting to further reduce
the errors in the material balances by performing gas bulb sampling more
frequently in the initial stage of the runs, and using improved operating
procedures and calibration techniques.
4.3  TRACE ELEMENT BALANCES
     Samples of aqueous condensate, tars, and reactor residues were subjected
to atomic absorption measurement so as to determine the levels of various
trace elements present.  Table 17 presents the results of tar and condensate
analysis for antimony, arsenic, cadmium, and lead.   Arsenic, beryllium,
cadmium, lead, mercury, and selenium analyses were determined in the reactor
residue samples as shown in Table 18.  These tables present trace element
concentrations in yg/g for the gasifier effluents as well as the percentage of
the element originally present in the feed which was recovered in the tar,
condensate and gasifier ash.  The operating conditions for each run shown are
presented in Table 3,
     The trace element behavior is seen in these tables to be quite variable.
Two important factors may be primarily responsible.  First the feed coals
varied greatly in their inherent trace element contents.  Then, individual
coal  charges were not always analyzed seoarately, allowing possible error due
to non-homogeneity within a given coal type.  Further, the metallic elements
present in the reactor system, viz.,  iron, nickel,  cadmium, and manganese, may
have entered various of the samples as a result of corrosion phenomena.
                                      43

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                             TABLE 17.   TRACE  METAL  ANALYSES  (TAR  AND  CONDENSATE)
                                                  M9/9  (%  Recovered)

TEST

Antimony
Arsenic
Cadmium
Lead

Antimony
Arsenic
Cadmi urn
Lead
16

NA
1.3(1.4)
NA
NA

0.014(26)
0.0063(2.3)
NA
NA
21

NA
4.2(4.3)
.035(1.7)
1.1(1.5)

0.0035(13)
0.23(16)
0.0038(12)
0.030(2.8)
23
Tar yg/g (%
NA
4.6(4.7)
.027(0.8)
.31(0.4)
Condensate ug/ml
0.0096(23)
0.44(20)
0.00013(0.2)
0.012(0.7)
25
Recovered)
NA
NA
NA
NA
(% Recovered)
<.003
0.11(4.6)
0.0044(3.4)
0.0085(0.7)
33

0.14(0.3)
.20(0.3)
NA
NA

<.003
0.036(2.0)
NA
NA
35

.095(5.4)
.48(1.9)
.017(1.9)
.73(21)

<.003
0.013(0.7)
0.015(22)
0.021(7.8)
36

.42(2.6)
.66(0.2)
.042(0.6)
2.1(6.8)

<.003
0.029(0.6)
0.00013(0.1)
0.044(9.0)

NA = Not Analyzed
No Tar or Condensate Analyses Available for Tests  41  or 43

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                                TABLE  18.   TRACE  METAL ANALYSES - RESIDUE (BOTTOM ASH)
                                                          yg/g (% Recovered)
en
TEST
Arsenic
Beryl 1ium
Cadmium
Lead
Mercury
Selenium
                    16

                  13(84)
                   NA
                   NA
                   NA
    21

  12(51)
6.5(99)
0.88(177)
9.0(54)
  23
41
25
33
35
36
                  3.0(41)   1.4(13)
9.1(46)     7.2(20)
4.5(82)    11(100)
0.41(108)   1.8(188)
4.9(34)      NA
 <1          NA
1.7(18)     9.9(30)
          4.8(29)      16(90)
          4.9(95)       NA
          0.028(3.1)    NA
          2.1(27)       NA
           <1           NA
          1.8(18)       NA
                      8.3(77)      41(84)
                      3.4(67)    3.7(52)
                      0.22(57)   0.51(43)
                      2.3(154)   1.4(28)
                       <1          NA
                      5.9(37)      NA
     43

  54(112)
3.2(46)
1.0(87)
0.53(11)
  NA
  15(104)
     NA = Not Analyzed

-------
     Beryllium was presented at low levels in the coals and was  retained
principally in the reactor residue.  Beryllium retention was most pronounced
for the higher rank coals.  Arsenic retention was higher for the lower rank
coals.  Cadmium levels indicate that contamination from the metallic reactor
system may have taken place.  The unusually low recovery for cadmium in Run
25 (Montana Rosebud) as compared with the other coals studied (3.1 percent
versus 43 percent or higher) may be due to the use of a nonrepresentative
coal sample for the original trace element determination.  (Trace element
determinations for parametric runs are being performed by selecting samples
for analysis from small aliquots which have been specifically prepared for
each run.)
     A comparison of selected trace element distribution results of the RTI
screening tests with those available from various research gasifiers are
presented in Table 19.  The RTI gasifier was found to accumulate arsenic in
the reactor residue when gasifying Pittsburgh No.8 seam coal, as shown  in
Table 19.  This may be an error or artifact, rather than an actual condition.
The Synthane PDU gasifier of the Pittsburgh Energy Technology Center was
found to accumulate arsenic, cadmium and lead when operating with an Illinois
No.6 coal.  This may be associated with the fact that the Synthane gasification
process does not achieve a high carbon conversion as a result of limited
fluidized bed residence time.   (The resulting char material is  assumed  to  be
useful in'alternative conversion steps in order  to fully utilize  the carbon
content of the material.)
     Overall, the comparative data indicate that trace element  behavior is
quite variable in gasification  processes.  Low elemental recovery rates
indicate  that significant percentages of the elements escape to one or  more
effluents.  Arsenic, cadmium, lead, and mercury must then all be  regarded  as
potentially volatile elements in coal gasification reactors.
                                     46

-------
Table  19.   COMPARISON  OF  TRACE  ELEMENT  ANALYSIS  RESULTS  10'1]'12
               Mass Fraction  	^Sen1c	    Cadm1um        Lead          Mercury
                   (ug/g)
                                        01              u             «)               01
  Feed                                   •§•§•§              p
  Process                        ~v      "*       "S      '£      "S      ~       «5      '£
  Research Group                 ££££££££


  Pittsburgh No. 8 Coal
  RTI Gasifler
  Research Triangle Institute     8.71   20.6     0.16   0.01    6.50    2.62.   0.13   <0.03

  Pittsburgh No. 8 Coal
  Hygas PDU Gasifler
  Institute of Gas Technology     9.6     3.4     0.78   0.30    5.9     2.2     0.27    0.01

  Illinois No. 6 Coal
  RTI Gasifler
  Research Triangle Institute     3.26    2.39    0.34   0.13   16.8     0.30   0.12   <0.03

  Illinois No. 6 Coal
  Hygas PDU Gasifler
  Institute of Gas Technology     24      16       0.89   0.21   11       5.8    0.12   <0.01

  Illinois No. 6 Coal
  Synthane POU Gasifler  •
  Pittsburgh Energy Research
  Center                         1.3     3.3     0.01   0.77    1.1   21       0.14    NO
               f          _       _         		.^_____^_

  Montana Rosebud Coal
  RTI Gasifler
  Research Triangle Institute     0.71   <0.02    0.14   0.04   20.5     1.98    0.10   <0.03

  Montana Rosebud Coal
  GEGAS Gaslfier
  Peabody Coal Company            2.6     1.2     1.0    6.1     1     51       0.09    0.12



NO = Not detected.
                                           47

-------
                     5.0  STATISTICAL ANALYSIS OF DATA

     A statistical analysis of the RTI gasifier screening runs  was  carried  out
to identify the most important operating parameters affecting the production
of selected potential pollutants.   A stepwise linear regression analysis  was
used to determine the correlation  between the operating and production para-
meters .
     A list of the important gasifier operating parameters is shown in Table
20.  These were used as the independent variables in correlating the pollutant
production parameters which were considered to be the dependent variables in
the analysis.  The operating parameters were chosen from a more extensive set
using engineering judgment and past experience in analyzing gasifier data.   Of
the 20 variables, 14 characterize the coal used in the tests and the remainder
describe the operation of the gasifier.  The heating rate during pyrolysis
(HTRT), air-to-coal  (AC) and steam-to-coal (SC) ratios,  and bed  temperature
(TMAXAVG) are  known  to affect both the quantity and distribution of products
from gasifiers.   The amount of coal charged  (CLCHRG) and the average gas flow
into the gasifier (TGAS) were chosen  as  independent variables  because  they are
indicative of  gas-solid contacting and bed height.
5.1  LINEAR REGRESSION TECHNIQUE13
     Selected  pollutant production variables  along with  several  other  indicators
of gasifier performance, which make  up the dependent  variable  set, are shown
in Table 21.   In  general,  the pollutant  production  parameters  are yields for
a  specific compound  per unit of carbon gasified,  or coal  loaded.  They were
chosen because the  raw  product gas concentration  of these  compounds typically
exceeded published  thresholds for adverse health  effects.
     The stepwise linear  regression  analysis was  carried out using a  standard
statistical  program. Briefly, the stepwise  computer  program finds  the single-
                                            2                   2
variable model which produces  the largest R   statistic (where  R  is the  square
of the multiple correlation  coefficient).   After entering the  variable with
              2
the  largest  R , the program  uses  the partial correlation coefficients to
select the next variable  to  enter the regression.  That is,  the program  enters
the  variable with the highest partial correlation coefficient (given  that  the
                            n
variable with the largest R   is  already in  the model.)  An F test is  performed
                                      48

-------
         Table  20.   IMPORTANT  GASIFIER  OPERATING  PARAMETERS
         (Independent  Variables  in  the  Regression Analysis)
 PCTVOLMT
 PCTASH
 SULFUR
 HTRT


 AC
 AS
 PCTMOIST
 FBTULB
 CLCHRG
 TGAS
 TMAXAVG

 ORG
 SULFATE
 SC
 FXDCAR
 PYR
 CARBON
 HYDRO
OXY
NITRO
 Percent  volatile matter  in coal.
 Percent  ash  in coal.
 Total percent sulfur  in  coal.
 Heating  rate of the coal during pyrolysis phase
 taken as the slope of the time temperature curve
 as the coal  is heated from 300°C to 700°C.
 Air-to-coal ratio (g/g).
 Air-to-steam ratio (g/g).
 Percent moisture in coal.
 Higher heating value of  coal.
 Coal charged to the gasifier (g).
 Average gas flow rate into gasifier (slpm).
 Mean of the maximum bed  temperature averaged over
 the entire test, °C.
 Percent organic sul.fur in coal.
 Percent sulfur as sulfate in coal.
 Steam-to-coal ratio (g/g).
 Percent fixed carbon in coal.
 Percent sulfur as pyrites in coal.
 Percent carbon in coal.
Percent hydrogen in coal.
Percent oxygen in coal.
 Percent nitrogen in coal.
                              49

-------
  Table 21.   IMPORTANT POLLUTION  PRODUCTION  PARAMETERS  AND
  GASIFIER PERFORMANCE VARIABLES  (Dependent  Variables  In  The
                     Regression Analysis)
SCFLB
BTUSCF
ORACL
ORBCL
NPNCL
PNACL
PCTTARCL
AR4
SU2
BEN10
BTX
PHET
CRET
HS10
CS10
SRAT10
MTH10
NAPT
PTHT
INE8
BFU8
FTH4
FLU4
Total gas produced (scf/lb coal)
Higher heating value of gas produced (Btu/scf)
Tar organic acid yield (g x 100/g coal)
Tar organic base yield (g x 100/g coal)
Tar nonpolar neutral yield (g x 100/g coal)
Tar polynuclear aromatic yield (g x 100/g coal)
Percent tar yield from coal
Tar arsenic yield (ug/g carbon converted)
Ash sulfur yield (yg/g carbon converted)
Benzene production (ug in bulb/g carbon converted)
BTX production (yg/g carbon converted)
Total phenol production (yg/g carbon converted)
Total cresol production (yg/g carbon converted)
HgS yield in gas (yg/g carbon converted)
COS yield in gas (yg/g carbon converted)
Ratio H2S to COS in gas (g/g)
CH3SH yield in gas (yg/g carbon converted)
Total naphthalene yield (yg/g carbon converted)
Total phenanthrene yield (yg/g  carbon  converted)
Indene yield in gas (g/g  carbon converted)
Benzofuran yield in gas (yg/g carbon converted)
Fluoranthene yield  in  tar  (yg/g carbon converted)
Fluorene yield  in tar  (yg/g carbon  converted)
                             50

-------
to determine if the variable to be entered has a probability greater than the
specified significance level for entry into the analysis.  (For the analysis
presented here this level was 50 percent.)  After a variable is added, the
program searches all the variables already included in the model and computes
a partial F-statistic to determine if these variables should remain in the
model.  Any variable not producing a partial F significant at the specified
significance level for retention, i.e., 0.10, is then deleted from the model.
The process then continues by determining if any other variables should be
added to the regression.  The process terminates when no variable meets the
conditions for inclusion or when the next variable to be added to the model is
the one previously deleted from it.
5.2  STATISTICAL ANALYSIS RESULTS:  PHASE I
     The results of the analysis using the independent variables from Table 20
and the dependent variables in Table 21 are summarized in Table 22.  Entrees
in this table correspond to the order of importance of each independent vari-
able in accounting for the variation in each dependent variable.  For example,
in the row labeled "SCFLB" (total scf of product gas per Ib coal) a value of 1
                                                              •
was entered in column "AC" (air-to-coal ratio.)  This means that the air-to-
coal ratio was the most important parameter in correlattng the total product
gas.  Also from the same row it can be seen that the steam-to-coal ratio was
the second most important variable in correlating the total product gas with a
linear model.
     The positive or negative sign following each numerical entree in Table 22
is the sign of the coefficient of the corresponding independent variable in
the linear model.   For example, examination of the first two dependent variables
shows that the volume of product gas increases and the heating value of the
gas decreases with increase in air-to-coal ratio.  This is to be expected due
to increased nitrogen concentration in the product gas.
     In order to identify the most important variables affecting pollutant
production, the most important independent variables in determining each of
                                                      2
the dependent variables (dependent variables with an R  less than 0.500 were
not considered) shown in Table 22 were assigned the value of V equal to seven
minus its ranking in any specific correlation giving an overall ranking index
W which gives a measure of the overall  importance of that variable in affecting
pollutant production.
                                   51

-------
TABLE 22.  SUMMARY OF THE STATISTICAL ANALYSIS OF THE RTI GASIFIER
          SCREENING RUN USING ALL INDEPENDENT VARIABLES IN TABLE 20
Dependent
Variables
gas produced
(SCFLB)
gas HHV
(BTUSFC)
organic acids
(ORACL)
organic bases
(ORBCL)
nonpolar neutrals
(NPNCL)
PNAs
(PNACL)
tar yield
(PCTTARCL)
arsenic in tar
(AR4)
sulfur in ash
(SU2)
benzene yield
(BEN10)
BTX yield
(BTX)
phenol yield
(PHET)
cresols yield
(CRET)
hydrogen sulfide
(HS10)

ifE
• c
.— >
0 t—
a.



n-
2+
2+

2+







Independent Variables
^— «
to >-
ta o
Q.






5+








i— u_
rs _i
CO 3





1 +

2+

1 +

1 +




01
(O
c — «
•r- 1—

X— *•
0) <
r- C3
C 1—



2+


3-




2-



>ed temperature
TMAXAVG)



3-
6-






4+


2-
to
0
•1—
c
ItJ
o». — •.
J- CD
0 QL
Oj
°














 UJ
•0 1—
«*- 
S- O
-o cc
6^








3+





Q>
CD
X >-
0 X
o
&«














c:
o>
i- o
E »-•
z
&s



4+






5-
1-


CM
o:
0.965
0.766
0.662
0.981
0.338
0.876
0.850
0.768
0.688
0.838
0.958
0.346
0.456
0.715
No.
Observations
34
25
19
19
19
18
19
8
18
17
15
14
14
21
                                                                               (continued)

-------
     Table 22 (continued).
Dependent
Variables
carbonyl sulfide
(CS10)
H2S/COS
JSRAT10)
methanethiol
(MTH10)
naphthalene
(NAPT)
phenanthrene
(PTHT)
indene
(INE8)
benzofuran
(BFU8)
fluoranthene
(FTH4)
fluorene
(FLU4)
Independent Variables
£ vol . matter
[PCTVOLMT)








4+

co
V) 1 —
tO CJ
a.










3 C£
«*- rs
i— U_
•3 —i
10 ID
CO





1 +




Ol
10
t-
Cn
*-> cc.
to t—
Ol n:











r-  CO
01 
r- Q
4- X
U_

4-








co
0
0-










o ~zz.
XJ 0
S- CQ
03 CC.
o >Q
x: >-










c
O)
en
x >-
0 X
o










c
Ol
en
i. 0
4-> 
-------
     The independent variable(s)  of greatest importance  were  different  de-
pending upon the specific dependent variable of interest.   Table  22  shows that
the sulfur level was of primary importance in the yield  of organic tar  bases
and benzene, both of which are known to have a high level  of  potential  for
carcinogenic and/or mutagenic activity.  Gasifier operating parameters  CLCHRG
(coal charged) and TGAS (inlet gas flow rate) were found to be  of importance
in the production of several  pollutants.   As discussed previously, these
parameters represent the reactor bed height and the conditions  of gas-solid
contacting.  The mechanism(s) through which the parameters identified in Table
23 influence pollutant production is not explicitly known at  present.  It is
possible that mechanisms of pollutant production may not directly involve the
identified parameters but that these parameters may be indicative of inter-
mediate processes or parameters not considered in the analysis  but which are
highly correlated with the identified parameters.  A more basic phenomeno-
logical study of gasification process would help reveal  the relationship
between the identified independent parameters and pollutant production rates;
such work is planned as a part of this project.
5.3  STATISTICAL ANALYSIS RESULTS:  PHASE II
     Statistical analyses were performed to determine if the independent para-
meters shown in Table 23 are significantly correlated with each other.  In the
case where two variables have a high degree of correlation one can be eliminated
from the analysis.  A reduction in variables  is beneficial in that the linear
models for predicting pollutant product yields would involve fewer independent
variables.  A strategy was developed for reducing redundant variables:
     1.   Starting with the most  important variable as listed in Table 23,
          variables of lesser importance were eliminated from consideration as
          a primary parameter if  they  had a high degree of correlation with
          the most important variable.
     2.   Step 1 was repeated throughout Table 23 until no variables were
          remaining for consideration.
Applying this procedure to Table  23 resulted  in the set of primary independent
variables listed in Table 24.  The stepwise  linear regression procedure
described above was applied  in correlating the pollutant production yields and
gasifier performance variables listed  in Table 21 with the primary dependent
variables in Table 24.  The  results of this  analysis are summarized  in Table
                                   54

-------
         TABLE 23.  RANKING OF OPERATING PARAMETERS IN THE ORDER OF
                    IMPORTANCE IN INFLUENCING POLLUTANT PRODUCTION

Independent
Variable
% sulfur
(SULFUR)
coal charged
(CLCHRG)
inlet gas flow
JTGAS)
% vol . matter
(PCTVOLMT)
bed temperature
(TMAXAVG)
steam/coal
CSC)
% sulfate S
(SULFATE)
air/ steam
(AS)
heating rate
(HTRT)
% pyritic S
(PYR)
air/coal
(AC)
% organic S
(ORG)
heating value
(FBTULB
% nitrogen
(NITRO)
% hydrogen
(HYDRO)
% fixed coal
(FXDCAR)
% ash
(PCTASH)
% moisture
(PCTMOIST)
% carbon
(CARBON)
% oxygen
(OXY)
Ranking
Index*
W
29
25
22
19
18
17
16
15
13
12
11
6
5
5
4
3
2
0
0
0
Overall Importance
in Pollutant Formation
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20

*The overall  ranking index, W, is the sum of the V values from the individual
 correlations, where V is seven minus the ranking of the independent variable
 under consideration.
                                     55

-------
      TABLE 24.   RANKING OF THE  MOST IMPORTANT,  INDEPENDENT OPERATING
                     PARAMETERS  INFLUENCING  POLLUTANT  PRODUCTION

Independent
Variable
% sulfur
(SULFUR)
% sulfate S
(SULFATE)
% vol . matter
(PCTVOLMT)
steam/coal
(SO
coal charged
(CLCHRG)
inlet gas flow
(TGAS)
bed temperature
(TMAXAVG)
air/ steam
(AS)
air/ coal
(AC)
heating rate
(HTRT)
Ranking
Index*
W
40
24
22
21
20
18
16
15
12
8
Overall Importance
in Pollutant Production
1
2
3
4
5
6
7
8
9
10

*The overall  ranking index, W, is the sum of the V values from the individual
 correlations, where V is seven minus the ranking of the independent variable
 under consideration.
                                      56

-------
 25.   (The entries  in this  table have the same significance  as  described for
 Table 22.)   An  overall  ranking  of importance  of  the  dependent  variables in
 affecting pollutant  production  was again performed.   The  results of this
 ranking are shown  in Table 24.
      The linear models  for pollutant yields and  gasifier  performance using the
 dependent variable listed  in  Table 24 are shown  in Table  26.   The entries in
 the  columns of  this  table  are coefficients of the corresponding independent
 variables in the linear model of the dependent variable.  For  example, the
 product gas yield  is given by
      SCFLB  = -12.23  + 3.928*SC  + 0.01611*CLCHRG  + 19.12*AC-0.1472*HTRT.
      Relative to the yields of  potential  pollutants  considered in this analysis,
 the  coal  characterization  parameters of  total  sulfur, sulfate  and volatile
 content were the most important parameters.   The importance of the volatile
 matter  content  of  the raw  coals  undoubtedly reflects  the  fact  that the coal-
 derived volatiles  contain  many  of  the  potential  pollutants under study here.
 The  three sulfur variables of total  sulfur, pyritic  sulfur, and organic sulfur
 were found  to exhibit generally  the  same  behavior in  the  regression analyses.
 This is  explained  by  the fact that the pyritic sulfur and organic sulfur
 levels  were highly correlated with the total  sulfur  level, the correlation
 coefficients  being 0.90 and 0.85 respectively.
      The  importance  of sulfur indicated  in Tables 24  and  26 may to some extent
 be the  result of statistical bias which  lacks physical meaning.  However,  an
 attempt  to  further evaluate the  possible  existence of causative factors has
 been  initiated.   The  sulfur species, viz., pyritic,  organic, and/or total
 sulfur content,  were  intercorrelated as  independent variables relative to
dependent variables as hydrogen sulfide yield, etc.   Moreover,  the iron con-
tent of the coal is highly correlated with the pyritic sulfur.   Iron is
capable of substituting for sulfur in thiophene structures;  thus,  a higher
iron pyrite content for coal can result in a greater potential  for the modi-
fication of organically bonded sulfur.
     Also, sulfur is  known to form thia- and dithiaether linkages  in hydro-
carbon media.  This can be a form of "vulcanization"  in  which the  presence of
the sulfur promotes the formation and/or maintenance of  larger  molecular
                                     57

-------
TABLE 25.  SUMMARY OF THE STATISTICAL ANALYSES OF THE RTI GASIFIER
         USING THE MOST IMPORTANT, INDEPENDENT OPERATING VARIABLES

Dependent
Variables
gas produced
(SCFLB)
gas HHV
(BTUSFC)
organic acids
(ORACL)
organic bases
(ORBCL)
nonpolar neutrals
(NPNCL)
PNAs
(PNACL)
tar yield
(PCTTARCL)
arsenic in tar
IAR4)
sulfur in ash
(SU2)
benzene yield '
(BEN10)
BTX yield
(BTX)
phenol yield
(PHET)
cresols yield
(CRET)
hydrogen sulfide
(HS10)
carbonyl sulfide
(CS10)
H2S/COS
(SRAT10)
methanethiol
(MTH10)
Independent Variables
t vol . matter
(PCTVOLMT)



1 +
1 +
1 +

1 +


3+







3^
*3 _l
00




2+

1 +
2+
1 +





1 +



O)
tj
01
O) X

4-
3+



2+



4+







10
o
u
i. O
r- ^

1 +
1-

6-




2+





1 +


E
V
1/1
i- oo
r-eC




3-
2-










2-

•o
 00
(U <
•— o
C 1—



2+


3-



2-





3-

aed temperature
(TMAXAVG)



3-
5-









2-



if
^ —i
10 oo







4+

1 +

2-



3-
1 +
2-
steam/coal
(SO
2+
2+







1 +
u
1 +


2+

H
CM
o:
0.965
0.766
0.662
0.955
0.313
0.777
0.860
0.768
0.608
0.878
0.710
0.251
0.456
0.701
0.801
0.731
0.334
No.
Observations
34
25
19
19
19
17
19
8
18
17
15
14
14
21
21
21
19
                                 58

-------
TABLE 25 (continued).
Dependent
Variables
naphthalene
(NAPT)
phenanthrene
(PTHT)
indene
(INE8)
benzofuran
(BFU8)
fluoranthene
(FTH4)
fluorene
(FLU4)
Independent Variables







steam/coal
JSC)

3-




C\J
o;
0.323
0.990
0.091
0.513
0.555
0.261
No.
Observations
15
7
16
14
16
16
                                     59

-------
TABLE 26.  SUMMARY OF LINEAR MODELS FOR POLLUTION
            PRODUCTION AND GASIFIER PERFORMANCE

INTERCEPT
INDEPENDENT
VARIABLES
SULFUR
SULFATE
PCTVOLMT
SC
CLCHRG
TGAS
TMAXAVG
AS
AC
HTRT
R2
No. Observations

INTERCEPT
INDEPENDENT
VARIABLES
SULFUR
SULFATE
PCTVOLMT
SC
CLCHRG
TGAS
TMAXAVG
AS
AC
HTRT
R2
No. Observations
ORACL
9.623E-1


_-
--
1.815E-2
--
--
7.733E-3
- 1.456E-3
--
--
--
0.662
19
AR4
- 1.159E-3


2.378E-4
--
--
—
7.500E-7
_-
--
--
--
--
0.768
8
ORBCL
3.155E-2


3.372E-2
--
4.950E-3
--
1.123E-4
—
- 2.682E-4
- 2.319E-2
1.510E-2
—
0.955
19
SU2
- 1.791E+1


--
1.399E+2
--
--
—
--
--
--
5.632
—
0,608
18
PNACL
- 9.817E-1


3.474E-1
--
—
--
7.792E-4
- 1.516E-2
--
--
9.913E-3
--
0.777
18
BEN10
-5.372E+3


--
2.585E+2
--
7.195E+3
—
- 2.172E+2
__
—
1.184E+2
—
0.878
17
PCTTARCL
- 5.916


4.694E-1
5.447
1.014E-1
--
2.315E-3
--
--
--
--
—
0.860
19
BTX
8.350E+3


—
- 2.420E+4
—
1.084E+4
--
—
--
—
—
—
0.710
15
                                               continued
                           60

-------
TABLE  26  (continued).


INTERCEPT
INDEPENDENT
VARIABLES


SULFUR
SULFATE
PCTVOLMT
SC
CLCHRG
TGAS
TMAXAVG
AS
AC
HTRT
R2
No. Observations

INTERCEPT
INDEPENDENT
VARIABLES
SULFUR
SULFATE
PCTVOLMT
SC
CLCHRG
TGAS
TMAXAVG
AS
AC
HTRT
R2
No. Observations
HS10

1.148E+5




1 . 502E+4
--
--
--
--
--
- 1.242E+2
--
--
--
0.701
21
















CS10

- 8.406E+2
i
t
i
i
i
—
- 4.962E+3
—
3.639E+2
!
	
--
--
9.352E+2
--
0.801
21
FTH4
- 1.482E-5


1.490E-4
—
--
--
1.611E-2
--
—
--
--

0.555
16
PTHT
.) 	
- 1.462E+1




1.388
--
—
- 4.332E-1
9.725E-3
--
—
--
--
--
0.990
7
SCFLB
- 1.223E+1


— _
--
--
3.928
--
—
--
--
1.912E+1
- 1.472E-1
0.965
34
BFU8

1.459E+3




__
-_
__
__
__
-_
- 1.120
- 7.813E+1
__
—
0.513
14
BTUSCF
1 . 990E+2


_ _
__
._
2.143E+1
-_
--
--
__
- 5.963E+1
9.628E-1
0.766
25
                                    61

-------
weight hydrocarbons» i.e., tars.   Clearly,  the sulfur,  nitrogen,  and  oxygen
content of gasifier tar precursors influences its  chemical  properties.
     The most important gasifier operating  variable affecting  pollutant
production was the steam-to-coal  ratio.   This variable  had  a  significant
influence on benzene and total BTX production.  (The steam  may have functioned
to reduce the oxygen partial pressure in the reactor during the devolatilization,
i.e., unsteady-state, period.  This phenomenon should not occur in a  continuous
fixed-bed gasifier).  The other operating variables except  the heating  rate
listed in Table 24 also had about the same  order of significance in influencing
pollutant production as did the steam-to-coal ratio.  Heating rate was  only
found to be influential in the yield of tar PNA.
     The height of the coal bed in the RTI  laboratory gasifier was also found
to have some statistical influence on various of the output (dependent)
variables, as measured by the coal charge quantity (CLCHRG).   This is pro-
bably a result of the fact that a greater bed height reduces the zone above
the bed where residence time and thermal conditions are favorable to the
cracking or gasification of tars and oils,  for example.  Hence, as the coal
charge quantity increases the yield of tar, for example, may increase,  as was
found in this study.
     In Figures 12 through 16, the predicted yields for several pollutants are
compared to the experimental values obtained  from  the RTI gasifier.  It can
be seen that the agreement is reasonable even though the gasifier runs include
a variety of coals and operation conditions.
     The predicted yield of organic bases (ORBCL)  in crude gasifier tar is
shown in Figure 12 versus the actual yield.   A correlation coefficient of
0.955 was obtained.  Six independent variables appear in the correlation, as
shown in the second  column of Table 26.  The  amount of scatter in the data is
seen to be quite low and uniform over the range of the correlation for the 19
values available.
     The predicted polynuclear aromatics (PNACL) yield in crude gasifier tar
is shown in Figure 13  versus  the actual yield.  The noticeable degree of
scatter seen in this figure  is reflected by  a correlation coefficient of
0.777.  As seen in Table 26,  the three  independent variables which most
successfully represent  the yield of polynuclear aromatics are  coal sulfur
content (SULFUR),  coal  charge amount  (CLCHRG),  the gas flow rate  (TGAS) to
                                     62

-------
CO
                      0.27 '
                      0.24
                        .21
                  S   °*18
                 o
                 o
                  X

                  C7I
                      0.1S
                  
                  o
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                  Q.
0.09
0.06
0.01
                       0.00  »
                            !
                                3.00    0.0?    0.06    0.09    0.12    0.15    0.18    0.21     0.24    0.27    0.30

                                            Observed Tar  Organic Base Yield (g  x 100/g coal)

          Figure 12.   Comparison of the observed and  predicted tar organic  base yields for the  RTI  gasifier screening
                       tests.

-------
                o
                u
               O
               o
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                    2.1   »
                    1.8
                    1.5
                    1.2
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                                     0.3
                                               0.6
                                     0.9
1.2
                                                                              1.5
1.8
                                                                              2.1
                                                                                                            2.4
                                      Observed Polynuclear Aromatlcs Yield (g x  100/g  coal)

         Figure  13.   Comparison of the observed  and predicted tar  organic acid yields for the RTI  gasifier screening
                      tests.

-------
01
                  3.6
                  3.0
                  2.4
              o
              o
              o
              o
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               O)
               OJ
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                          0.0
                                        0.6
S.2
1*8
                                                                                                 J..C
                                                                                                            A   A
                                                                                                               3.6
                                              Observed Percent Tar  Yield (g x IGO/g coal)

            Figure  14.   Comparison of observed and predicted tar  yields for the RTI gasifier screening tests.

-------
cr>
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                    64 COO *
                    56000
                    48000
                    40000
                    32000
                    24000
                    16000
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                                   10000
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30000
                                                                40000
                                                           50000
                                                                                   60000
                                                                                             70000
                                                                                        80000
                                                                                                                90000
                                                                                                          100000
                                       Observed H2S Yield in the  Product 6as(yg/g  carbon gasified)


              Figure 15.   Comparison  of observed and  predicted  hUS yields for  the RTI gasifier screening  tests.

-------
cr>
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                 5000
                 1500
             
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-------
the gasifier, and the air/coal  feed  ratio  (A/C).   (One  of  the  observations  is
not shown on Figure 13 as it was  off-the-scal.e used.)
     Figure 14 displays the predicted versus observed yield  of crude  gasifier
tar (PCTTARCL), expressed as percent of the raw coal feed  which appears  as
tar, i.e., grams tar x 100/grams  coal.   A  good correlation was obtained;  the
correlation coefficient was 0.860 based on four significant  independent  vari-
ables.  These were the total sulfur  (SULFUR), sulfate  sulfur (SULFATE),  percent
volatile matter (PCTVOLMT), and quantity of coal  used  (CLCHRG).
     The yield of hydrogen sulfide is displayed in Figure  15 where the pre-
dicted values are plotted versus the measured values.   Some  20 of the 21
observations are shown, one being off-scale.  The degree of  scatter is reason-
ably low  (correlation coefficient = 0.701); one point is seen to be at an
extreme value and could be considered an "outlier."  The hydrogen sulfide
yield was found to be higher when the total sulfur level of the raw coal was
higher and lower when the reactor bed temperature was lower.
     The  carbonyl sulfide yields were always secondary to those for hydrogen
sulfide by about two orders of magnitude.   A reasonably good correlation
              2
coefficient  (R  = 0.801) resulted for the carbonyl sulfide yield in terms of
the sulfate, steam/coal ratio and air/coal ratio, as shown in Table 26.
However,  it  is seen  in Figure 16 that the data are heavily grouped near the
low end of the range of yield values.  Probably the most  significant  aspects
are that  (a) the carbonyl sulfide yield did  not vary substantially, even with
wide variations  in the total sulfur  content  of the feed coal,  and  (b) the
yield level  was well-correlated by three  variables each of which provide
measures  of  oxygen input to  the gasifier.   (This  latter condition may indicate
that carbonyl  sulfide  is formed primarily via  secondary reactions, for example
from hydrogen  sulfide  interactions with oxygen and oxides of  carbon.  It is
generally known  that the reaction of hLS  and  CO to form COS and H~ tends to be
near an equilibrium  condition  in  the raw  product  gas from a coal gasifier.
This  latter  condition  is consistent  with  the  general concentration levels
observed, i.e.,  the  H2S/COS  ratio was  in  the  range of  20  to 200 typically.)
                                      68

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                             6.0  CONCLUSIONS

     The objective of this project is to develop a  fundamental  understanding
of those factors which influence the production of  potential  environmental
pollutants in synfuel processes.  This information  is needed  to provide guid-
ance for the control of potentially harmful  pollutants from future synfuels
plants.
     A series of screening tests have been completed using a  laboratory scale
gasification reactor.  The purpose of these screening tests was to compare
pollutants, qualitatively and quantitatively, from  a variety  of coals under
similar gasification conditions.  Coals tested were Montana Rosebud, Wyoming
subbituminous, North Dakota Lignite, Pittsburgh No.8, Illinois No.6, Western
Kentucky No.9, and FMC char.  Chemical analyses of  the coals, particulate
residues, tars, aqueous condensates, primary gaseous products, and volatile
organics have been performed.  Emphasis has been upon determination of the
organic constituents in the effluent streams.
     The laboratory reactor has been operated primarily as a nonisothermal
pollutant generation facility.  Steam furnaces have been utilized to provide a
primary reactant to the bottom of the vertical reaction chamber.  Also, pres-
surized air and/or oxygen have been supplied for reaction.  The air-to-steam
ratios have been controlled so as to achieve operating conditions representa-
tive of practical gasifier operation.  Further, both the steam and air rates
have been controlled so that the coal bed temperature is maintained at desir-
able levels.  In this way, successful operation of the reactor has been achieved
while operating with simultaneous temperature control; this is provided through
use of a three-zone electric furnace which surrounds the reactor.  Data collec-
tion has been possible as a result of the utilization of a POP 11/34 signal
processing  system operated on-line with the  reactor facility.
     High carbon conversions have been achieved as desired.  Higher rank coals
showed slightly less carbon conversion; they possess a somewhat lower reactivity.
Also, the conversion of the sulfur species in the  feed coal have  been generally
above 80 percent during gasification  runs to approximately 1000°C.   It has
been concluded  that  the level of  sulfur conversion can be  increased  if the
overall residence time for reaction  exceeds  that required  for  carbon conver-
sion alone.   However, the screening  test  runs were terminated  once  oxygen  was
detected in the gas  exit  stream.

                                      69

-------
     Two distinct  time phases  for  reaction were observed in the screening test.
 runs.  These  have  been characterized as surge and steady-state periods.  The
 surge period  involves devolatilization of the coal and represents the conditions
 under which effluent concentrations vary substantially with time.  After the
 methane concentration in the effluent gas has dropped below approximately two
 volume percent,  it has been observed that the temperature and concentration of
 the effluent  stream is generally well behaved, i.e., steady-state.  It is
 believed that this phase involves  primarily the gasification of char via the
 carbon/steam  reaction, the partial oxidation of carbonaceous material, and the
 carbon/carbon dioxide reaction.  The supporting evidence for the understanding
 of reactor behavior and characterization of pollutant production has been
 obtained as a result of using  sampling and analysis techniques which have been
 specifically  developed for these studies.'
     Application of these testing  methods have provided concentrations and
 amounts for the  reactor residue, aqueous condensate, oils and tar, as well as
 the primary gas  product stream.  This stream has been subjected to routine gas
 chromatographic  analysis as well as infra-red measurements so as to success-
 fully maintain known and desirable operating conditions within the facility.
 Relative quantities of organic pollutants have resulted from these tests.  For
 convenience,  these results have been expressed as mass of compound produced
 from each effluent per unit of feed carbon converted within the reactor.  The
 dominant compounds which have been identified in the effluent streams are
 hydrogen sulfide,-carbonyl sulfide, phenol, cresols, benzene, toluene, naphtha-
 lene, anthracene,  and phenanthrene.  Additional studies are currently underway
 to characterize  the tar fractions  relative to the wide distribution of compounds
which are contained therein.
     The Western Kentucky No.9 and Illinois No.6 coals were found to generate
 larger tar yields, while subbituminous and lignite coals resulted in somewhat
 less tar production.  The smallest yield of PNA and organic base materials
were obtained from North Dakota lignite, while the largest yields resulted
from Western  Kentucky No.9 coal.  Generally, the tar yields were found to be
substantial during these runs.   This is in agreement with the tar yields of
commercial  fixed bed coal  gasifiers operating with medium and high volatile
                    14 15
coal feed materials.
                                   70

-------
     Trace element studies have indicated that arsenic,  cadmium,  lead  and
mercury may also generally be volatilized during gasification.   (Additional
results on trace element analyses have recently been obtained via neutron
activation analysis techniques.  While the results are generally  in agreement
with those of atomic absorption, both sets have revealed that measurements  of
the trace elements being carried by the primary gas stream may be necessary
to fully account for the fate of these elements within the gasification
process.
     Material balance calculations have been completed for many of the screening
test runs.  It was generally difficult to achieve a high degree of closure on
material balances for the semibatch tests as they were conducted over extended
time periods.  However, overall closure was obtained for these runs at a
level well within a standard deviation of only 13 percent.  Closure was
•obtained least well for sulfur, ash, and hydrogen.  (It has been demonstrated
that the percentage closure for the individual elements can be substantially
improved by adjusting the material balances so as to force closure on a
selected element, e.g., oxygen.  This condition indicates that some experi-
mental  error is present in the results which  is due, perhaps, to inaccuracies
in the  overall determination of gas flow rates.)
     A  statistical analysis of the RTI gasifier screening runs was carried
out  to  identify the most  important operating  parameters affecting  the produc-
tion of selected  pollutants.   Specifically, a  stepwise  linear regression
analysis was used to determine  the correlation  between  the operating,  and
production parameters.  Some 20 operating variables were  chosen  for analysis.
In the  production of potential  pollutants,  the  coal characterization  parameters
of total sulfur,  sulfate  and volatile content were  the  most  important quantities
in determining yields.  Total  sulfur was  indicated  to significantly affect
the  production of both  sulfur  and  nonsulfur compounds.  The  most important
gasifier operating variable affecting pollutant production was the steam-to-
coal ratio.  This variable had a  significant  influence  on benzene  and  total
BTX  production.   A number of other operating  variables  were  also of significance
in  influencing pollutant  production.  Heating rate  was  found  to  be influential
in  the  yield of  the  PNA fraction  of  the  tar.
     The  statistical analysis  also showed that increases  in  both the  air-to-
steam  ratio  and  the  bed temperature  decreased the yield of  several of the
major  pollutants.  However,  no significant correlation  existed  between the
                                      71

-------
selected independent variables and the yields of phenol and naphthalene.
Since phenol is the primary pollutant in the gasifier condensate, a mechanis-
tic approach to explaining the production of phenol rather than the statis-
tical approach is warranted.
     The screening test runs have been extremely useful in providing operating
experience with a unique experimental facility.  The simultaneous function of
the reactor facility, signal processing system, and sampling system has required
check-out procedures and numerous troubleshooting tasks.  The successful
operation of a gasification process in which feed materials and operating
variables are intentionally being changed for experimental purposes gives rise
to complexities in chemical process control.  However, a versatile system has
been established and prepared for parametric test runs.
     Parameters for gasification tests are pressure, temperature, coal  particle
size, reactant flow rates, and coal additives.   Hence, operation of the test
facility under carefully controlled conditions  in which specifically determined
variables are set at preselected values will be performed and analyzed.  This
is intended to provide basic data for the understanding of pollutant formation
during coal gasification.
                                     72

-------
                               REFERENCES


1.  Cleland, J. G., F. 0. Mixon, D. G. Nichols, C.  f1.  Sparacino,  and D.  E.
    Wagoner, "Pollutants from Synthetic Fuels Production:   Facility Con-
    struction and Preliminary Tests," U.S. Environmental  Protection Agency,
    EPA-600/7-78-171, August 1978.

2.  Gangwal, S. K., P. M. Grohse, D. E. Wagoner, D. J. Mi nick, C. M. Sparacino,
    and R. A. Zweidinger, "Pollutants from Synthetic Fuels Production:
    Sampling and Analysis Methods for Coal Gasification,"  U.S. Environmental
    Protection Agency, EPA-600/7-79-201, August 1979.

3.  Nichols, D. G., J. G. Cleland, D. A. Green, F.  0.  Mixon, T. J. Hughes,
    and A. W. Kolber, "Pollutants from Synthetic Fuels Production:  Environ-
    mental Evaluation of Coal Gasification Screening Tests," U.S. Environ-
    mental Protection Agency, EPA-600/7-79-202, August 1979.

4.  Gillmore, D. W., and A. J. liberators, "Pressurized, Stirred, Fixed-Bed
    Gasification," in;  Symposium Proceedings:  Environmental Aspects of
    Fuel Conversion Technology, II (December 1975,  Hollywood, Florida), U.S.
    Environmental Protection Agency, EPA-600/2-76-149, pp. 125-132, June
    1979.

5.  Cavanaugh, E. C., W. E. Corbett, and G. C. Page,  "Environmental Assessment
    Data Base for Low/Medium-Btu Gasification Technology:  Vol.  I, Technical
    Discussion," U.S. Environmental Protection Agency, EPA-600/7-77-125a,
    November 1977.

6.  Cavanaugh, E. C., W. E. Corbett, and G. C. Page,  "Environmental Assessment
    Data Base for Low/Medium-Btu Gasification Technology:  Vol.  II, Appendices
    A-F,"  U.S. Environmental  Protection Agency, EPA-600/7-77-125b,  November
    1977.  .

7.  Hauk,  R., et al., "Gas-Wasserfach, Gas-Erdgas," 118:  No.10,  427-340,
    October  1977.

8.  Page,  C. C., "Application of  Environmental Assessment Methodology,"
    Working  Paper, Radian  Corporation,  1978.   (See EPA-600/7-78-022, October
    1978).

9.  Lewis, P.  S.,  "A Study of Stirred,  Fixed-Bed Gas  Producer Behavior  with
    Caking Coals," in:   Proceedings  of Fourth  National Conference on Energy
    and the  Environment, AIChE/APCA,  pp.  43-49, October 1976.

10.  Attari,  A.,  J. Pau,  and M.  Mensinger,  "Fate of Trace  and Minor Constituents
    of Coal  During Gasification,"  U.S.  Environmental  Protection  Agency, EPA-
    600/2-76-258,  September 1976.

11.  Somerville,  M. H.,  and J. L.  Elder,  "A Comparison of  Trace Element  Analyses
    of North Dakota  Lignite Laboratory Ash with Lurgi Gasifier Ash and  Their
     Use in Environmental Analyses,"  jn_:   Symposium Proceedings:   Environmental
    Aspects  of Fuel  Conversion  Technology, III,  (September 1977, Hollywood,
     Florida),  U.S.  Environmental  Protection Agency, EPA-600/7-78-063,  pp.  292-
     315,  April  1978.

                                     73

-------
12.  Forney, A. J., W. P. Haynes, S.  J.  Gasior,  R.  M.  Kornosky,  C.  E.  Schmidt,
     and A. G. Sharkey, "Trace Elements  and Major Component  Balances Around
     the Synthane PDU Gasifier," in:   Symposium  Proceedings:   Environmental
     Aspects of Fuel Conversion Technology, II  (December 1975, Hollywood,
     Flordia), U.S. Environmental Protection Agency,  EPA-600/2-76-149,  pp.67-
     81, June 1976.

13.  Statistical  Analysis System Users Guide. 1979  Edition,  SAS  Institute,
     P. 0. Box 10066, Raleigh, NC  27605.

14.  Handbook of  Gasifiers and Gas Treatment Systems,  FE-1772-11, Dravo
     Corporation, Pittsburgh,  PA, February 1976.

15.  Ad Hoc Panel on Low-Btu Gasification  of Coal,  National  Research Council,
     "Assessment  of Low-and Intermediate-Btu Gasification  of Coal," National
     Academy of Sciences, Washington,  DC,  1977.
                                    74

-------
          APPENDICES





 I.   Signal  Processing System-



II.   Pollutant Production Factors
              75

-------
                                APPENDIX  I
                         SIGNAL PROCESSING  SYSTEM

     The laboratory reactor facility which  has  been  used  to  study  coal  gasi-
fication and pollutant generation is equipped with  versatile signal  processing
and data handling capabilities.  The hardware includes  an on-line  digital
processor, i.e., the central  processing unit, as well as  quick-response
accessories.  Detectors for temperatures, pressures, flow rates, and chemical
compositions are connected directly to the  experimental  facility,  as shown in
Figure 17.  Signals from these detectors or monitors move directly to the
industrial control (remote),  i.e., ICR, where signal conversion and con-
ditioning occurs.  The ICR is connected directly to the CPU, which is a POP
11/34.  Operator access to the CPU may be achieved via  a console at the CPU
or a terminal near the experimental system.
     Generally, four modes of system operation are in use.  The first mode
represents "system generation" activities,  i.e., software introduction and/or
modification.  The second operational mode is that of real-time signal
processing, i.e., the activity which involves experimental runs on the
laboratory gasifier and/or real-time chemical analysis operations using gas
chromatographs.  Next, the post-experimental data processing activity  is
conducted.  The fourth mode" of system function  is that of batch processing,
i.e., the execution of user prepared programs in source  (FORTRAN) language.
     The functional states of  the signal processing system which are active
for the performance of experimental gasification tests are shown in Figure
18.  Before the tests, scan condition and display inputs are provided  along
with test parameters, and load and start instructions.    During the gasifi-
cation tests, data are stored, print and store  alarms are activated; and,
other user overrides are  instituted.  Subsequent to each gasification  test, a
run log is  produced and data accumulated during the run  are processed  to
determine average  temperatures,  flow rates,  compositions and other  relevant
data values.  Carbon conversion  and steam conversion values are also computed.
     Signal processor  function 1n  support of gas chromatograph  (GC) analyses
is also an  important component of  system use.   As shown  in  Figure  19,  various
system operations  take place before, during, and after the  GC  analyses.
Before GC runs,  the operator introduces  input  parameters and calibration
                                     76

-------
                                                       Mass
    Console
                          C.P.U.
                                                       Storage
Room Divider
   Experimental
     System
                          I.C.R.
 GC
GC
GC
Terminal
                                  1.   Decwriter (LA-36)
                                  2.   Central  Processing Unit
                                      (POP 11/34)
                                  3.   Dual Disk Drives (RK05)
                                  4.   Coal Gasification  Process
                                  5.   Industrial Control, Remote
                                  6.   Gas Chromatograph  Units
                                  7.   Video Terminal  (VT-52)
           Figure  17.  Signal processing hardware configuration.
                                      77

-------
                     Hardware
                    Diagnostics
    Before Gasification Test
                         Define &
                         Store Test
                        Parameters
 Scan, Condition,
& Display Inputs
  Load Test
Parameters &
Start the Test
    During Gasification Test
    After Gasification Test
                                           Stop
                                           Scan
                                                              Store Test
                                                                 Data
                                                                 Stop
                                                                 Test
                     Log and/or Analyze
                         Test Data
                                              Print &
                                            Store Alarms
Figure 18.   Signal  processor  function  relative  to  gasification  tests,
                                             78

-------
                    Hardware
                   Diagnostics
    Before GC Run
  Scan,
Condition,
& Display
  Inputs
    Prepare,
   Modify, or
   Recalibrate
Analysis Method
                                                                    Call  Method
                                                                      & Start
                                                                      Extract
                                                                      & Store
                                                                    Peak Data
    During GC  Run
                                                                     Stop GC
                                                                       Run
    After GC Run
                                             Stop
                                             Scan
                       Identify Peak*
                         & Compute
                       Concentrations
                                                                   Print Report
                                                                    of GC Run
                                                                    Call New
                                                                  Analysis Method
                                                                    if Wanted
                                                                   Load Stored
                                                                     Data &
                                                                  Analyze Again
Figure 19.   Signal processor  function  relative to GC analyses,
                                         79

-------
instructions.  During operation of the gas chromatographs,  the signal  pro-
cessor is receiving input data through an analog/digital  converter interface.
After the GC run, the signal  processing system is activated to determine
residence times for compound identification as well  as the  integration and
correction of peak areas for an accurate determination of the concentration of
each species being analyzed.  Next, a report is printed of the results of the
GC runs.
     The various software packages which have been prepared in this project in
support of gasification test run monitoring, gas chromatograph operation and
data analysis are shown in Figure 20.  This figure displays the functional
interrelations among the software packages and the signal processing system
hardware.  It may be noted that most of the software serves a supervisory
function.  As such, these software packages provide the capability for on-line
data collection, system monitoring, and process variable manipulation.  Thus,
accurate and comprehensive data collection can be achieved.  Further the
continuous monitoring of specific process variables permits control over the
range of these variables and immediate response should the level  of a critical
variable, e.g.,  reactor temperature or pressure, exceed its safety threshold.
     The software packages which have been implemented in  support of GC data
collection and analysis include programs  to achieve input/output, perform  peak
integration  including baseline correction, compute test parameters, list
parameters,  assemble and store data,  generate  summary  reports,  etc.  A  cap-
ability  for  achieving simultaneous use of two  or more  GC systems  is being
developed.
                                      80

-------
                                         DIALOG
                                        COMMAND
                                       INTERPRETER
VIDEO AND
HARD-COPY
TERMINALS
oo
                                             Figure 20.   Signal  processing  software system.

-------
         APPENDIX II
POLLUTANT PRODUCTION FACTORS
 (g produced/g coal loaded)
              82

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TABLE I1-1.
POLLUTANT PRODUCTION IN COAL GASIFICATION—RUN N0.16:
              ILLINOIS NO.6 COAL
         g produced/g coal loaded

H2S
COS
cs2
methanethiol
e thane thiol
thiophene
methyl thiophene
ammoni a
benzene
tol uene
xyl enes
phenol
cresols
xylenols
chrysene
perylene
pyrene
fluorene
anthracene
naphthalene
biphenyl
Indene
benzofuran
di benzofuran
aniline
GAS
2.1E-2
2.2E-4
4.2E-5
2'.2E-5

l.OE-3
1.8E-4
N/A
2.8E-3
2.0E-2
4.9E-5
1.3E-5
1.1E-5



2.5E-7
1.8E-8
1.4E-6
7.0E-5
l.OE-6
2.3E-4
3.3E-4


CONDENSATE











2.2E-4
3.8E-4












TAR





,





7.8E-6
1.9E-5



6.4E-5
2.7E-6
3.9E-4
6.1E-4



3.2E-7

TOTAL
2.1E-2
2.2E-4
4.2E-5
2.2E-5
N/A
l.OE-3
1.8E-4
N/A
2.8E-3
2.0E-2
4.9E-5
2.4E-4
4.1E-4
N/A
N/A
N/A
6.4E-5
2.7E-6
3.QE-4
6.8E-4
l.OE-6
2.3E-4
3.3E-4
3.2E-7
N/A
                                83

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TABLE II-2.
POLLUTANT PRODUCTION IN COAL GASIFICATION—RUN NO.21
               ILLINOIS NO.6 COAL
           g produced/g coal loaded

H2S
COS
cs2
methanethiol
ethanethiol
thiophene
methylthiophene
ammonia
benzene
toluene
xylenes
phenol
cresols
xylenols
chrysene
perylene
pyrene
fluorene
anthracene
naphthalene
blphenyl
indene
benzofuran
di benzofuran
aniline
GAS
2.2E-2
1.2E-4
3.0E-5
5.0E-5

3.6E-4
6.0E-4
7.8E-4.


2.6E-4
8.3E-5
2.0E-4
2.0 E-4




4.8E-6
5.0 E-4
5.6E-6
5.6E-6
6.3 E-5
3.0E-5

CONDENSATE







8.7E-3



l.OE-4
2.4E-4
1.5E-4











TAR











9.4E-5
3.6E-4
8.7E-5
2.6E-4

2.9E-4
2.6E-4

1.9E-3



2.4E-4
8.7E-6
TOTAL
2.2E-2
1.2E-4
3.0E-5
5.0E-5
N/A
3.6E-4
6.0E-4
9.5E-3
N/A
N/A
2.6E-4
2.8E-4
8.0E-4
4.4E-4
2.6E-4
N/A
2.9E-4
2.6E-4
4.8E-6
2.4E-3
5.6E-6
5.6E-6
6.3E-5
2.7E-4
8.7E-6
                            84

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       TABLE II-3.
POLLUTANT PRODUCTION IN COAL GASIFICATION—RUN NO.23
              ILLINOIS NO.6 COAL
          g produced/g coal loaded

H2S
COS
cs2
methanethiol
ethanethiol
thiophene
methylthiophene
ammonia
benzene
tol uene
xyl enes
phenol
cresols
xyl enol s
chrysene
perylene
pyrene
fluorene
anthracene
naphthalene
biphenyl
indene
benzofuran
dibenzofuran
aniline
GAS
5.9E-2
3.4E-4
1.5E-4
3.1E-5
1.3E-6*
2.3E-3
6.6E-4

8.7E-3
3.1E-3
3.8E-4
1.3E-4
3.1E-4





4.1E-6
2.0E-3
9.3E-6
2.2E-4
1.9E-4
4.1E-5

CON DENS ATE











1.9E-4
2.4E-4
9.3E-5











TAR











1.5E-4
4.5E-4
3.5E-4
2.8E-4
1.2E-4
3.5E-4
1.5E-5
2.4E-4
8.5E-4



1.7E-4
6.1E-6
TOTAL
5.9E-2
3.4E-4
1.5E-4
3.1E-5
1.3E-6
2.3E-3
6.6E-4
N/A
8.7E-3
3.1E-3
3.8E-3
4.7E-4
l.OE-3 .
4.4E-4
2.8E-4
1.2E-4
3.5E-4
1.5E-5
2.4E-4
2.9E-3
9.3E-6
2.2E-4
1.9E-4
2.1E-4

*Includes dimethyl sulfide.
                                     85

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       TABLE II-4.
POLLUTANT PRODUCTION IN COAL GASIFICATION—RUN NO.41
            WESTERN KENTUCKY NO.9
          g produced/g coal loaded

H2S
. COS
cs2
methanethiol
ethanethiol
thiophene
methyl thiophene
ammonia
benzene
to! uene
xylenes
phenol
cresols
xylenols
chrysene
perylene
pyrene
fluorene
anthracene
naphthalene
blphenyl
Indene
benzofuran
dlbenzofuran
aniline
GAS
2.7E-2
5.7E-4
7.5E-7
3.8E-5
1 . 1 E-4*
2.7E-4
3.3E-4

1.3E-2
1.7E-3
2.8E-4
3.6E-4
2.4E-4





6.9E-6
2.1E-3
5.7E-6
5.0E-4
1.2E-4
3.5E-6

CONDENSATE











4.2E-4
3.8E-4
5.3E-5











TAR











3.6E-5
2.6E-4
1.4E-4


7.2E-4
2.3E-4
6.8E-4
2.6E-4



2.4E-4
6.3E-7
TOTAL
2.7E-2
5.7E-4
7.5E-7
3.8E-5
1.1E-4
2.7E-4
3.3E-4
N/A
1.3E-2
1.7E-3
2.8E-4
8.2E-4
8.8E-4
1.9E-4
N/A
N/A
7.2E-4
2.3E-4
6.8E-4
2.7E-3
5.7E-6
5.0E-4
1.2E-4
2.4E-4
6.3E-7
*Includes dimethyl sulfide.
                                       86

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TABLE II-5.
POLLUTANT PRODUCTION IN COAL  GASIFICATION—RUN NO.25
            MONTANA ROSEBUD COAL
         g produced/g coal  loaded

H2S
COS
cs2
methanethiol
ethanethiol
thiophene
methylthlophene
ammonia
benzene
tol uene
xylenes
phenol
cresols
xylenols
chrysene
perylene
pyrene
fluorene
anthracene
naphthalene
biphenyl
Indene
benzofuran
dibenzofuran
aniline
GAS
2.5E-3
8.0E-5

2.2E-6

2.8E-5
5.9E.-6
5.9E-4
3.6E-4
5.4E-4
4.8E-4
8.0E-5
2.8E-5
5.6E-5




1.6E-6
l.OE-4
1.6E-6
8.3E-5
2.6E-5
2.3E-6

CONDENSATE







4.2E-3



2.6E-4
1.1E-4
9.6E-6











TAR











7.6E-5
1.4E-4
4.1E-5
1.3E-4
4.8E-4
1.8E-4
1.3E-4
1.1E-4
2.1E-4



9.6E-5
6.8E-7
TOTAL
2.5E-3
8.0E-5
N/A
2.2E-6
N/A
2.8E-5
5.9E-6
4.8E-3
3.6E-3
5.4E-4
4.8E-4
4.2E-4
2.8E-4
1.1E-4
1.3E-4
4.8E-4
1.8E-4
1.3E-4
1.1 E-4
3.1E-4
1.6E-6
8.3E-5
2.6E-5
9.8E-5
6.8E-7
                                87

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TABLE II-6.
POLLUTANT PRODUCTION IN COAL GASIFICATION-RUN MO.33
        WYOMING SUBBITUMINOUS COAL
         g produced/g coal loaded

H2S
COS
cs2
methanethiol j
ethanethiol
thiophene
; methylthiophene
ammonia
benzene
to! uene
xylenes
phenol
cresols
xylenols
chrysene
perylene
pyrene
fluorene
anthracene
naphthalene
biphenyl
indene
benzofuran
dibenzofuran
aniline
GAS
1.9E-3
'1.1E-4

1.4E-5

9.1E-6
l.OE-4

4.6E-3
1.8E-3
4.6E-4
1.2E-3
3.3E-4
1.4E-3




2.4E-6
2.6E-4
6.3E-6
5.5E-4

1.8E-5

CONDENSATE









.

1.3E-4
1.4E-4
5.1E-5











TAR

-









1.6E-4
3.5E-5
2.7E-4
2.0E-5
1.3E-5
2.6E-5
5.7E-5
8.3E-5
8.9E-5



4.1E-5
8.7E-7
TOTAL
1.9E-3
1.1E-4
N/A
1.4E-5
N/A
9.1E-6
l.OE-4
N/A
4.6E-3
1.8E-3
4.6E-4
1.5E-3
5.1E-4
1.7E-3
2.0E-5
1.3E-5
2.6E-5
5.7E-5
8.5E-5
3.5E-4
6.3E-6
5.5E-4
N/A
5.9E-5
8.7E-7

-------
TABLE II-7.
POLLUTANT PRODUCTION IN COAL GASIFICATION—RUN NO.35
        WYOMING SUBBITUMINOUS COAL
         g produced/g coal loaded

H2S
COS
cs2
methanethiol
ethanethiol
thiophene
methyl thiophene
ammonia
benzene
tol uene
xylenes
phenol
cresols
xylenols
chrvsene
perylene
pyrene
fluorene
anthracene
naphthalene
biphenyl
Indene
benzofuran
dibenzofuran
aniline
GAS
3.8E-3
2.0E-4

2.5E-5

3.0E-5
3.0E-5

3.8E-3
2.2E-3
8.0E-4
6.0E-4
2.8E-4
7.1E-4




1.2E-6
8.5E-5
3.0E-6
1.4E-4
l.OE-4
7.3E-6

CON DENS ATE











6.8E-4
4.1E-4
8.5E-5











TAR











3.2E-4
7.8E-4
4.9E-4
2.0E-5
6.9E-6
3.5E-5
4.9E-5
7.6E-5
4.7E-5



4.1E-5
1.4E-6
TOTAL
3.8E-3
2.0E-4
N/A
2.3E-5
N/A
3.0E-5
3.0E-5
N/A
3.8E-3
2.2E-3
8.0E-4
1.6E-3
1.5E-3
1.3E-3
2.0E-5
6.9E-6
3.5E-5
4.9E-5
7.7E-5
1.3E-4
3.0E-6
1.4E-4
l.OE-4
4.8E-5
1.4E-6
                                 89

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        TABLE II-8.
POLLUTANT PRODUCTION IN COAL GASIFICATION-RUN NO.36
         NORTH DAKOTA ZAP LIGNITE
         g produced/g coal loaded

H2S
COS
cs2
methanethlol
ethanethiol .
thiophene
methyl thiophene
ammonia
benzene
toluene
xyl enes
phenol
cresols
xylenols
chrysene
perylene
pyrene
fluorene
anthracene
naphthalene
biphenyl
indene
benzofuran
dibenzofuran
aniline
GAS
2.3E-3
1.7E-4

7.9E-5
2.2E-5*
5.1E-4
1.3E-5

5.1C-3
1.4E-3
3.9E-4
1.6E-4
1.4E-4
4.9E-4




9.3E-7
2.3E-4
3.2E-6
7.9E-5
1.4E-5


CON DENS ATE

•



.





4.7E-4
2.5E-4
6.2E-5











TAR











4.7E-5
9.1E-5
7.1E-6
2.2E-5
6.9E-6
4.0E-5
4.0E-5
l.OE-4
1.8E-5



3.1E-5

TOTAL
2.8E-3
1.7E-4
N/A
7.9E-5
2.2E-5
5.1E-4
1.3E-5
N/A
5.4E-3
1.4E-3
3.9E-4
6.8E-4
4.8E-4
5.6E-4
2.2E-5
6.9E-6
4.0E-5
4.0E-5
l.OE-4
2.5E-4
3.2E-6
7.9E-5
1.4E-5
3.1E-5
N/A
'Includes dimethyl  sulfide.
                                      90

-------
TABLE I1-9.
POLLUTANT PRODUCTION IN COAL GASIFICATION—RUN NO.43
         NORTH DAKOTA ZAP LIGNITE
         g produced/g coal loaded

H2S
COS
cs2
methanethiol
ethanethiol
tniophene
methylthiophene
ammonia
benzene
to! uene
xylenes
phenol
cresols
xylenols
chrysene
perylene
pyrene
fluorene
anthracene
naphthalene
biphenyl
indene
benzofuran
dibenzofuran
aniline
GAS
1.4E-3
2.7E-4
6.7E-6
1.1E-5
1 . 3E-5*
8.9E-6
3.5E-5

1.6E-3
9.1E-4
2.9E-4
1.9E-5
1.1E-4
8.1E-7




4.0E-6
.5.1E-5
2.1E-6
2.2E-4
6.3E-5
7.7E-7

CONDENSATE











1.2E-3
6.9E-4
1.4E-4











TAR











3.7E-5
1.2E-4
8.7E-4
4.2E-5
6.3E-7
9.5E-6.
2.9E-5
4.9E-5
2.6E-5



3.4E-5
2.7E-8
TOTAL
1.4E-3
2.7E-4
6.7E-6
1.1E-5
1.3E-5
8.9E-6
3.5E-5
N/A
1.6E-3
9.1E-4
2.9E-4
1.3E-3
9.2E-4
l.OE-3
4.2E-5
6.3E-7
9.5E-6
2.9E-5
5.3E-5
7.7E-5
2.1E-6
2.2E-4
6.3E-5
3.4E-5
2.7E-8
                               91

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                                 TECHNICAL REPORT DATA
                           (Pleas* read Instructions on the reverse before completing}
 1. REPORT NO.         ~~
  EPA-600/7-79-200
         2.
                                    3. RECIPIENT'S ACCESSION NO.
 4-TITL5ANOSU8T'TI-6 Pollutants from Synthetic Fuels Pro-
 auction: Coal Gasification Screening Test Results
                                    3. REPORT DATE
                                     August 1979
                                                       6. PERFORMING ORGANIZATION CODE
     HOR(S) J.G.Cleland, S.K.Gangwal, C. M.Sparacino,
 R.M. Zweidinger, D.G.Nichols, andF.O.Mixon
 7. AUTI
                                    8. PERFORMING ORGANIZATION REPORT NO
 9. PERFORMING OROANIZATION NAME AND ADDRESS
 Research Triangle Institute
 P.O. Box 12194
 Research Triangle Park, North Carolina 27709
                                    10. PROGRAM ELEMENT NO.
                                    EHE623A
                                    11. CONTRACT/GRANT NO.

                                    Grant R804979
 12. SPONSORING AGENCY NAME AND ADDRESS
 EPA, Office of Research and Development
 Industrial Environmental Research Laboratory
 Research Triangle Park, NC  27711
                                                  NO PERIOD COVERED
                                    13. TYPE OF REPORT AND PERIOD CC
                                    Task Final; 8/78 - 7/79
                                    14. SPONSORING AGENCY CODE
                                     EPA/600/13
 is.SUPPLEMENTARY NOTES ffiRL-RTP project officer is N. Dean Smith, Mail Drop 61,  919/
 541-2708. Grant-related reports include EPA-600/7-78-171, EPA-600/7-79-201, and
 EPA-600/7-79-202.
  O. ABSTRACT
           The report gives screening results of 38 coal gasification tests in a semi-
 batch, fixed-bed laboratory gasifier to evaluate various coals and operating condi-
 tions for pollutant generation. The tests involved char, coal, lignite, and peat.  Reac-
 tor temperatures ranged from 790 C to 1035 C with high carbon and sulfur conversions
 in the bed. Extensive analyses were performed for organic and inorganic compounds
 and trace elements in the tars and hydrocarbon oils, aqueous condensates, and reac-
 tor residues resulting from the gasification tests. Over 450 compounds were identi-
 fied from the various gasifier streams: more than 100 of the compounds were quanti-
 fied for several of the test runs.  Statistical analyses have been performed on the
 data.  The quantity and composition of the various samples have been examined in
 relation to coal type and operating variables. Results are reported for sulfur species
 in the product gas  stream, for consent decree pollutants  contained as volatile  orga-
 nic compounds in the product gas, for phenol and related compounds in the aqueous
 condensate and tar/oil sample, and for PNA species  in the tar /oil.
17.
                             KEY WORDS AND DOCUMENT ANALYSIS
                 DESCRIPTORS
 Pollution
 Coal Gasification
 Charcoal
 Coal
 Lignite
 Peat
Sulfur
Phenol
Polycyclic Compounds
Aromatic Compounds
                                          b.lOENTIFIERS/OPEN ENDED TERMS
Pollution Control
Stationary Sources
Synthetic Fuels
Char
Consent Decree Pollu-
 tants
 Polvnuclear Aromatics
                                                c.  COSATI Field/Group
13 B
13H
21D
07B
07C
13. DISTRIBUTION STATEMENT
 Release to Public
                                          19. SECURITY CLASS (ThisReport)
                                          Unclassified
                                                21. NO. OF PAGES

                                                    100

                       20. SECURITY CLASS /Thispage)
                       Unclassified
                        22. PRICE
EPA Form 2220-1 (9>73)
                                           92

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