xvEPA
Pollutants from
Synthetic Fuels
Production:
Facility Construction
and Preliminary
Tests
Interagency
Energy/Environment
R&D Program Report
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RESEARCH REPORTING SERIES
Research reports of the Office of Research and Development, U.S. Environmental
Protection Agency, have been grouped into nine series. These nine broad cate-
gories were established to facilitate further development and application of en-
vironmental technology. Elimination of traditional grouping was consciously
planned to foster technology transfer and a maximum interface in related fields.
The nine series are:
1. Environmental Health Effects Research
2. Environmental Protection Technology
3. Ecological Research
4. Environmental Monitoring
5. Socioeconomic Environmental Studies
6. Scientific and Technical Assessment Reports (STAR)
7. Interagency Energy-Environment Research and Development
8. "Special" Reports
9. Miscellaneous Reports
This report has been assigned to the INTERAGENCY ENERGY-ENVIRONMENT
RESEARCH AND DEVELOPMENT series. Reports in this series result from the
effort funded under the 17-agency Federal Energy/Environment Research and
Development Program. These studies relate to EPA's mission to protect the public
health and welfare from adverse effects of pollutants associated with energy sys-
tems. The goal of the Program is to assure the rapid development of domestic
energy supplies in an environmentally-compatible manner by providing the nec-
essary environmental data and control technology. Investigations include analy-
ses of the transport of energy-related pollutants and their health and ecological
effects; assessments of, and development of, control technologies for energy
systems; and integrated assessments of a wide range of energy-related environ-
mental issues.
REVIEW NOTICE
This report has been reviewed by the participating Federal Agencies, and approved
for publication. Approval does not signify that the contents necessarily reflect the
views and policies of the Government, nor does mention of trade names or commercial
products constitute endorsement or recommendation for use.
This document is available to the public through the National Technical Informa-
tion Service, Springfield, Virginia 22161.
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EPA-600/7-78-171
August 1978
Pollutants from Synthetic
Fuels Production:
Facility Construction
and Preliminary Tests
by
J. G. Cleland, F. O. Mixon, D. G. Nichols,
C. M. Sparacino, and D. E. Wagoner
Research Triangle Institute
P.O. Box 12194
Research Triangle Park, North Carolina 27709
Grant R804979
Program Element No. EHE623A
EPA Project Officer: Thomas W. Petrie
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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ABSTRACT
This project seeks to develop a fundamental understanding of those
factors and conditions that cause the production of environmental
pollutants in processes oriented to the production of synthetic fuels.
The information so generated is to aid in the control of the potentially
hazardous material which may be produced in the fossil fuels conversion
plants utilized in coming years. The project involves the operation of
a laboratory coal gasification system, the collection and chemical analysis
of effluent stream samples, the compilation and analysis of the resulting
data, and the evaluation and comparison of these data.
The experimental work has included the design, fabrication, and
preliminary operation of the laboratory gasifier to represent conditions
which may be utilized in commercial plants for coal conversion to synthetic
fuel gas. An experimental program has also been developed for the chemical
analysis of organic compounds produced in the reaction process. Sampling
procedures as well as specific chemical analysis techniques have been
studied, developed, and implemented for utilization in this work. The
research has focused on three major product categories:
1. major gas products (permanent gases);
2. volatile organic compounds (low-level gas components);
3. low volatile organic compounds (tar components).
Screening tests are underway to establish acceptable operating con-
ditions for the system, to identify the various organic compounds of
interest to the study, and to determine coal types for further study.
These will be followed by parametric tests to characterize the compounds
contained in the synthesis reactor effluent stream as a function of the
reactor operating parameters. Kinetic tests are also planned to determine
the rates of formation of various pollutants of significance and the
possible application of this information to the reduction of pollutant
ii
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formation in operating systems. The engineering studies involve the
planning of the various test runs included in this experimental project
and the interpretation of the results thus far obtained from the various
experimental tests. The data are utilized to assess the nature and
extent of various environmental hazards resulting from specific com-
pounds produced during synthetic fuels operations.
An operating experimental system has been achieved which functions
both successfully and reliably. Analytical chemical methods have been
developed which promise to achieve the levels of sensitivity and the
extent of compound identification and quantisation required to meet the
objectives of this project. This facility has the capability for solid
fuel gasification at temperatures ranging up to about 1370°K (2000°F),
pressures to about 1.2 MPa (300 psia), and product gas generation rates
of the order of 20 standard liters/min. Glass sample bulbs are used to
collect gases for subsequent gas chromatographic analysis. In addition,
Tenax and XAD-2 resin cartridges are used to adsorb volatile organic
compounds for subsequent analysis on a gas-liquid chromatography/mass
spectrometer/computer analysis system. The organic compounds of low
volatility, which constitute the tars and organic materials contained
within the aqueous condensate, represent an important class of materials
for identification and quantisation. These samples are partitioned into
organic acids, organic bases, and PNA hydrocarbons for subsequent analysis.
The gas chromatography/mass spectroscopic analysis of the organic
samples collected from coal tests typically reveal the presence of more
than 200 compounds. Equally large numbers of compounds appear to be
present in the less volatile samples collected from the tar and water
condensate trap. A specific list of organic compounds for identification
and quantisation has been developed to reduce the task of organic compound
characterization to one of practical proportions. These compounds include
benzene, naphthalene, acenaphthene, pyrene, fluorene, fluoranthene, phenol,
cresol, pyridine, and dibenzofuran.
iii
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Future work in this project will be concerned with parametric
studies which examine the generation and control of potential pollutants
in coal gasification under various operating conditions. The parameters
to be considered for investigation include coal type, grind size, steam
and air (oxygen) flow rates, coal pretreatment, bed depth, temperature,
pressure, and reactant residence times. It is also anticipated that the
reactor can be operated in both the fixed bed and fluidized bed con-
figurations. Thermodynamic and reaction kinetic studies are intended to
describe the pollutant generation process as well as to attempt to
determine (1) the mechanism of the formation of various pollutant
materials, (2) the rate of production of each of the pollutant materials,
and (3) the influence of various operating conditions upon the level of
each pollutant in the effluent stream. The information being generated
provides the basis for the assessment of the hazard potential of the
effluents from coal gasification processes and is intended for use to
determine the extent to which these hazards may be reduced.
This report is submitted to describe facility construction and pre-
liminary tests performed in partial fulfillment of Research Grant R804979
by the Research Triangle Institute under sponsorship of the U.S. Environ-
mental Protection Agency. This report covers a period from November
1976 through April 1978.
IV
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CONTENTS
Abstract ii
Figures vi
Tables vii-viii
List of Abbreviations ix-x
Acknowledgments xi
Section
1 Introduction 1
2 Conclusions, Problem Areas and Plans 4
2.1 Conclusions 4
2.2 Problem Areas 6
2.3 Future Plans 7
3 Reactor and Accessories 8
3.1 Experimental Equipment 8
3.2 Data Acquisition and Control System 11
4 Sampling Systems 14
4.1 Equipment Items 14
4.2 Sampling Procedures 16
5 Analytical Chemical Methods 20
5.1 Gas Analysis 20
5.2 Volatiles Analysis 22
5.3 Semivolatiles Analysis 23
6 Experimental Results 28
6.1 Reactor Performance 28
6.1.1 Overall Feed Conversion and Reactor Temperature
Profiles 28
6.1.2 Low Level Gas Constituents 39
6.1.3 Comparative Gasification Data 43
6.2 Chemical Analysis Results 46
6.2.1 Primary Gas Products 46
6.2.2 Volatile Organic Products 47
6.2.3 Semivolatile Organic Products 69
7 Discussion of Results 85
7.1 Feed Conversion 85
7.2 Primary Gaseous Products 87
7.3 Volatile Organic Products 88
7.4 Semivolatile Organic Products 89
7.5 Evaluation of Results 91
References 100-102
Appendix I — The Kinetics of Char Gasification 1-1
Appendix II — Multimedia Environmental Goals: MATE and EPC Con-
cepts II-l
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FIGURES
Number Page
1 Plan-view sketch of laboratory 9
2 Gasification system 10
3 Gasifier and sampling train 15
4 Vapor collection and analytical systems for organic
vapors 18
5 Schematic of gas chromatograph 21
6 Solvent partition scheme for tars 25
7 Major product gas concentrations (char run 4) 36
8 Major product gas concentrations (coal run 6) 37
9 Major product gas concentrations (coal run 16) 38
10 Sulfur-containing gas compositions (char runs 2 and 4) . . 40
11 Sulfur-containing gas compositions (coal run 6) 41
12 Sulfur-containing gas compositions (coal run 16) 42
13 Total ion current chromatogram of GC/MS analysis of
upstream Tenax sample for char run 2 48-49
14 Total ion current chromatogram of GC/MS analysis of
upstream Tenax sample for char run 4 51-52
15 Total ion current chromatogram of GC/MS analysis of
upstream Tenax sample for coal run 6 55-56
16 Total ion current chromatogram of GC/MS analysis of
steady-state XAD-2 sample for coal run 6 59-60
17 Total ion current chromatogram of GC/MS analysis of
Tenax sample 2 for coal run 16 63-64
18 Total ion current chromatogram of GC/MS analysis of
steady-state XAD-2 sample for coal run 6 66-67
19 Gas product/contaminants during run 6 72
20 Modified partition scheme for semivolatiles 75
21 Total ion current plot. Semivolatile organic acid fraction
from run 6 76
22 Total ion current plot. Semivolatile organic base fraction
from run 6 78
23 Total ion current plot. Semivolatile PNA fraction from
run 6 80
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TABLES
Number Page
1 Operating Parameters for GLC-MS Comp System 27
2 Coal, Char and Residue Analyses 29
3 Data on RTI Preliminary Gasification Tests 30
4 Sample Analyses for Gasification Run 4 32
5 Sample Analyses for Gasification Run 6 33
6 Sample Analyses for Gasification Run 16 34-35
7 Coal Gasification: Operating Conditions and Primary
Products 44
8 Typical Coal Gasifier Operating Characteristics 45
9 Compounds Identified from Tenax Sample Upstream of XAD-2
Char Run 2 50
10 Compounds Identified from Tenax Sample Upstream of XAD-2
Char Run 4 53-54
11 Compounds Identified from the Upstream Tenax Sample from
Coal Run 6 57-58
12 Compounds Identified from the Steady-State XAD Sample from
Coal Run 6 61-62
13 Compounds Identified from Tenax Cartridge No.2 from Coal
Run 16 65
14 Compounds Identified in the Extract of Steady-State XAD
Trap from Coal Run 16 68
15 Organic Compounds Adsorbed from Product Gas Stream,
Gas Stream Concentration (yg/1) 70-71
16 Weight Percent of Various Tar Fractions Via Partition
Procedure 73
17 Weight Percent Recovery Via Modified Partition Procedure
with Model Compounds 73
18 , Compounds Identified in the Organic Base Fraction
from Run 6 77
19 Compounds Identified in the Semivolatile PNA Fraction
from Run 6 79
20 Compounds Identified in the Semi volatile PNA Fraction
from Run 6 81-82
vii
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TABLES (continued)
Number Page
21 Quantitation for Semivolatile Organic Compounds in Coal
Gasifier Tar Product 84
22 List of Specific Hazardous Compounds for Identification
in this Study 93
23 Gasifier Pollutants Compared to Minimum Acute Toxicity
Effluent Limits and Estimated Permissible Concentrations . 98
II-l Multimedia Environmental Goals II-4
II-2 Derivation of Health Based EPC's II-7
11-3 Derivation of Ecology Based EPC's 11-8
viii
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LIST OF ABBREVIATIONS AND SYMBOLS
AQ — frequency (pre-exponential) factor
amu — atomic mass units
BKG — background compound
AEa — activation energy for reaction
EPC — estimated permissible concentration
e5 — standard (reference) compound
e.v. — electron volts
FID -- flame ionization detector
FPD — flame photometric detector
GC -- gas chromatographic column
GLC ~ gas-liquid chromatographic column
k — reaction rate constant
K — reaction equilibrium constant
M — mesh (screen size)
MATE — minimum acute toxic effluent
MERC — Morgantown Energy Research Center
MS — mass spectrometer
p -- partial pressure
PERC — Pittsburgh Energy Research Center
PNA — polynuclear aromatic hydrocarbon
ppm ~ parts per million, by volume
R — ideal-gas law constant
RTI — Research Triangle Institute
S ~ surface area for reaction
SCOT ~ support coated open-tube column
STP — standard temperature and pressure
ix
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T — temperature, °K
TC — thermal conductivity detector
Tenax ~ polymer adsorbent
tent — tentative
TIC — total ion current
X — fractional chemical conversion
XAD-2 — Amberlite resin adsorbent
NOTE: Standard metric units and abbreviations are provided throughout this
report.
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ACKNOWLEDGMENTS
The work reported herein has been conducted at RTI under the
direction of Forest 0. Mixon, Manager, Process Engineering Department.
The design, construction and operation of the reactor facility and its
accessories has been the responsibility of John Cleland, David Green and
Fred Schwarz. Duane Nichols has assisted in experiment planning as well
as data analysis and interpretation. Signal processing and data storage
aspects have been handled by William Drake, John Pierce, Kenneth Lei and
and Sherry Wheelock.
Denny Wagoner, Santosh Gangwal, Peter Groshe and Robert Denyszyn
developed and implemented the gas sampling system as well as the
associated chemical analysis procedures. The adsorbent cartridge
sampling procedures, the tar partitioning scheme and the associated
chemical analysis data interpretation work were all performed by Charles
Sparacino, Ruth Zweidinger, Sarah Willis, Jesse McDaniel and Douglas
Minick. Significant mass spectrometric support activities were con-
tributed by Kenneth Tomer, William Hargrove and David Rosenthal.
Thanks are due to Mr. Albert J. Forney (retired), formerly of the
Pittsburgh Energy Research Center and Dr. Richard M. Felder of North
Carolina State University for providing background information relative
to the physical and chemical aspects of the coal gasification process.
This research-grant project has received its support as a part of
the program on the environmental assessment of synthetic fuels through
the Fuel Process Branch, Energy Assessment and Control Division,
Industrial Environmental Research Laboratory, U.S. Environmental Pro-
tection Agency, Research Triangle Park, N.C. Substantial contributions
have been made by Dr. Thomas W. Petrie, Project Officer, Mr. William J.
Rhodes, Program Manager and Mr. T. Kelly Janes, Branch Chief, Fuel
Process Branch of IERL-RTP.
XI
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1.0 INTRODUCTION
The Research Triangle Institute has undertaken a project directed
toward understanding the nature and extent of the production of environ-
mental pollutants in synthetic fuels processes. This project sponsored
by the Industrial Environmental Research Laboratory/Research Triangle
Park of the U.S. Environmental Protection Agency is in its second year
of a five-year project period.
The overall purpose of this program is twofold: (1) to develop a
fundamental understanding of those factors and conditions that cause the
production of environmental pollutants in synthetic fuels processes; and
(2) to provide information needed for the control of potentially hazardous
material from plants which may be used to produce synthetic fuels in the
coming years.
The work to date includes equipment construction, installation, and
preliminary experimental testing. '"'-I In addition, initial work has
been performed relative to the interpretation of experimental data
T291
obtained from a variety of analytical chemical test procedures. J
After completion of the preliminary testing of the reactor and sampling
system and the satisfactory development of analytical chemical tests and
methods, the laboratory gasifier system is to be utilized to screen the
pollutants from a variety of coals considered to be candidates for coal
gasification within the United States. These screening tests will be
concerned with the characterization of the chemical constituents of the
reactor effluent stream as a function of the input coal utilized and the
reactor operating conditions. An additional aspect of the experimental
program involves the study of the fate, rate of conversion and mechanism
of formation of the pollutants of significance that are generated via
the coal gasification process. It is hoped that the results of this
study will permit the reduction of pollutant formation in operating
reactor systems.
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Additional analytical work which is to be a part of the overall
project effort involves the utilization of results of the screening
tests to (1) project human exposure to discharges from alternative coal
gasification plants and (2) establish priority ratings for the various
pollutants based on the extent to which projected exposures are hazardous.
During the first year of this project, a coal gasification laboratory
was designed and made operational. Tests have been completed for a low
volatile, noncaking char to check out the operating system. In addition,
a series of preliminary experiments utilizing FMC char and Illinois No.6
coal has been performed.
A sampling system made of stainless steel was first used. This
sampling system has since been replaced by a glass system which offers
greater versatility for use in the sampling process. Gas samples are
collected using glas.s sample bulbs, Tenax adsorbent cartridges and XAD-2
adsorbent cartridges. Samples from the glass bulbs are introduced
directly to the inlet system of the gas chromatograph to quantitatively
determine the amounts of permanent gases, sulfur species gases and C-,-Cg
hydrocarbons.
Thermal desorption recovers volatile organics from the Tenax car-
tridges and methylene chloride is used to extract organic compounds from
the XAD-2 adsorbents. The samples thus obtained are analyzed using the
technique of gas-liquid chromatography/mass spectrometry/computer analysis.
A substantial effort is required to achieve an appropriate instrument
calibration for these analyses in order to permit the accurate quali-
tative and quantitative determination of the organic compounds present.
Tars that are collected in a condensate trap are subjected to a
solvent partition scheme in order to isolate the compound categories of
organic acids, organic bases, polar neutral compounds, nonpolar neutral
compounds, PNA hydrocarbons and cyclohexane insoluble material. Various
techniques have been studied for the analysis of the organic acids,
organic bases and PNA hydrocarbons. These include exclusion chroma-
tography, reverse-phase chromatography, nuclear magnetic resonance
analysis and direct probe mass spectrometry. The greatest success has
been achieved utilizing capillary chromatography, temperature programming
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and GC/MS detection for these low volatile compounds. The direct probe
technique of sample introduction to a mass spectrometer operating at low
voltage levels has also shown some promise as a chemical analysis technique
of value in this study. A working list of specific hazardous compounds
has been developed based upon (1) the EPA Effluent Guidelines Division's
list of priority pollutants of BAT revision studies (consent decree
compounds), (2) minimum acute toxic effluents (MATE) values and (3)
known pollutant compounds occurring in relatively high concentrations in
the effluent streams. Therefore, the organic compounds that are being
identified and quantitatively determined include those which are known
hazardous materials or possess potential as environmental hazards in
relation to releases to the air, water streams or solid waste depositories.
A number of previous research projects have concerned the chemical
analysis of effluents from commercial and/or developmental gasification
processes. These include studies on fixed bed, fluidized bed, and
entrained bed gasification reactor systems. Uniquely, this study has
its focus on a complete evaluation of the chemical and toxic nature of
the effluent streams as well as a fundamental understanding of the
influence of the reactor operating conditions upon the results achieved.
The parametric values of operating conditions for this study, therefore,
are selected to characterize the various coal gasification processes
rip ig"|
currently under development.1- ' J
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2.0 CONCLUSIONS, PROBLEM AREAS AND PLANS
An experimental bench-scale investigation has begun which includes
the generation, collection, processing, analysis, characterization and
evaluation of the pollutants from the gasification of coal. Coal and
coal char have been gasified in a fixed bed reactor under selected
operating conditions. Particulates, condensates, organic volatile
compounds and effluent gases have been collected and processed for
characterization and chemical analysis. Analytical chemical measure-
ments include: the ultimate and proximate analyses of the coals, chars
and residues; the gas chromatographic analysis of the primary gaseous
products; the adsorption and analysis with GLC/MS/computer interpretation
of the volatile organic compounds; and the collection, partition, and
GLC/MS analysis of the semivolatile (tars and other low volatile organic)
compounds.
Primary progress to date includes the equipment assembly and pre-
liminary testing which have led to a number of conclusions. Additional
results and recommendations are anticipated after the analysis and
evaluation of the data from experiments in this program.
2.1 CONCLUSIONS
The laboratory coal gasification reactor system, which has been
constructed, assembled, and operated as a part of this project, can be
operated to simulate the primary operating conditions, the gas yield and
composition and the tar yield of commercial and developmental coal
gasifiers,so as to provide a means to study the processes and conditions
under which both major and minor pollutants are formed. Data records
can be assembled, compiled and stored, representing the operating
conditions with such a gasifier as a function of the reaction time and
the reactor configuration. To date, the reactor has been operated in
the semibatch fixed bed mode. However, it is anticipated that a fluidized
bed mode of operation will also be feasible.
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Sample collection equipment and procedures have been developed for
particulates, semivolatile organic compounds (tars and other low volatile
organics), aqueous condensates, volatile organic compounds and primary
gaseous effluents. This sampling procedure has been specifically
developed to permit a careful analytical determination of the types and
quantities of the various compounds present in each of the samples which
are collected.
Reliable gas chromatographic techniques have been identified and
used on the primary gaseous effluent stream. GLC/MS/computer analysis
techniques are being employed for both the volatile organics and the
semivolatile organic constituents. The qualitative and quantitative
determination of polynuclear aromatic hydrocarbons has been successful
up to compounds having five condensed aromatic rings. A partitioning
scheme has been perfected for use with the tars collected during the
experiments. The major components of the tar acids and tar bases have
molecular weights up to 350. The polar and nonpolar neutral compounds
have been present in significant quantities up to molecular weights of
approximately 450. The PNA fraction has been found to contain a series
of compounds resulting in prominent peaks at atomic mass unit intervals
of 24 or 26 from 178 to 380. These results correspond to condensed
aromatic structures with from 3 to 9 rings. The highest intensity peaks
occurred at the atomic mass unit values of 202, 252, and higher, in-
dicating that lesser amounts of the lower molecular weight PNA compounds
were present in the sample.
Over nine classes of organic compounds were identified in the
gasification reactor effluents that were judged to be potentially
hazardous. These include benzene and some of its derivatives, phenol,
other phenol-type compounds, and polynuclear aromatic hydrocarbons.
Also included were compounds containing the hetero-atoms of sulfur,
nitrogen, and oxygen.
A list of 102 specific hazardous compounds has been prepared for
use in this study. This includes 42 of the 131 compounds on the EPA
Effluent Guidelines Division list of priority pollutants for BAT revision
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studies (consent decree compounds). Some 25 hazardous compounds from
the list of 102 have been identified in the effluent stream from the
coal gasifier. These 25 include 14 of the consent decree compounds.
Of the 102 specific hazardous compounds under study, 21 have pre-
viously been identified in effluents from the fixed bed gas producer at
the Morgantown Energy Research Center, 39 in the products of various
coal liquefaction operations, and 52 in the products of coal coking
operations.
2.2 PROBLEM AREAS
Some difficulty was encountered in operating equipment at low flow
rates for the steam feed to the reactor. This problem has been
effectively alleviated by the proper selection of operating conditions,
including the heat rates selected for the three steam generating furnaces.
Further, heating rates are needed for the reactor coal bed such that
conversion temperatures are at desired levels for both noncaking and
moderately caking (agglomerating) coals. This has required that specific
attention be paid to the operating temperatures achieved when the external
reactor furnace is operating.
Development of chemical analytical techniques for high molecular
weight organic compounds occurring at trace levels has been particularly
challenging. These methods have been under continual improvement through-
out the effort to date. It appears that direct probe techniques utilizing
low voltage mass spectrometer operation will permit a characterization
of these compounds and that a substantial effort is required for the
analysis of each sample on the GLC/MS/computer analysis system. Some
consideration has been given to automating the process of compound
identification being utilized with this approach.
It has been quite difficult to compile complete information on the
potential hazardous effects associated with all of the various compounds
that may be associated with the conversion of coal to gaseous products.
However, the utilization of toxic information expressed in lethal dose
statistics, as well as the literature data on carcinogenic effects of
various compounds, are being used. This information has been used in
the form of minimum acute toxic effluent (MATE) values.
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2.3 FUTURE PLANS
It is anticipated that future experiments to be conducted with the
equipment described herein will be divided into three test types:
screening tests on various solid fuels representative of those materials
having potential for synthetic gas production; parametric tests in which
temperatures, pressures, air-to-steam ratios and other operating conditions
will be varied to simulate commercial and/or developmental gasification
reactors; and kinetic tests aimed at measuring rates of pollutant con-
version. The specific operating conditions will be carefully selected
based upon the laboratory system operability as defined by equipment
design, laboratory experience and the aim to simulate practical gasifi-
cation conditions. As in commercial and/or developmental gasification
reactors, it may be necessary to pretreat some high-volatile coal types
in order to successfully operate the gasification reactor with the high
caking (agglomerating) coals.
Continuing effort is planned to further develop techniques appro-
priate to the sampling and chemical analysis of the PNA organic compounds
and other trace constituents of the gasification reactor effluent stream.
Sample partitioning, high pressure liquid chromatographic techniques and
possible sample derivatization methods may be necessary. It is anti-
cipated that chromatographic and mass spectrometric methods will be
employed. The automation of the compound identification process would
permit a substantial increase in the productivity of this effort.
The automatic collection of operating data, the processing of gas
chromatographic data and data storage and retrieval capabilities are
being implemented. The data and signal processing system may make it
possible to perform data reduction and correlation studies in a routine
fashion for at least some of the results to be achieved with the
laboratory gasification system.
Correlations of the results of this study are being sought with
respect to such parameters as feed type, operating conditions, classes
of compounds emitted, characteristic functional groups possessed by the
effluents and hetero-atoms present with these compounds. This effort is
expected to become more meaningful as more types of solid feed are
studied.
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3.0 REACTOR AND ACCESSORIES
3.1 EXPERIMENTAL EQUIPMENT
A plan-view sketch of the reactor laboratory in use for this project
is shown in Figure 1. Solid fuel feed material is prepared and stored
in the laboratory in preparation for each of the gasification tests.
Runs to date have included both char and coal feed material with a size
of 8 X 16 mesh. A coal charge is placed in the reactor feed hopper
which is inside the enclosed high pressure area. The gas storage
cylinders provide nitrogen or other permanent gases to the reactor.
Deionized water is metered to steam generation furnaces in order to
provide a steady flow rate of steam to the reactor. The metering pumps
have the capacity to supply from 0.5 to 5.0 kg of water/hour to the
reactor.
The reactor system is shown in Figure 2. The reactor is constructed
from a nominal 3-inch diameter (7.6 cm), schedule 160, type 310 stainless
steel pipe and is approximately 1.2 m in length. Above it is located
the coal hopper and coal feed system. This consists of a nominal 2-inch
(5 cm) diameter, schedule 40 steel pipe, which is approximately 0.5 m in
length. The sight glass joints are connected to the coal feed system
with flanges at each end. The sight glass permits the operator to view
the descent of solid feed as it is added to the reactor. A pneumatically
actuated Jamesbury stainless steel ball valve is located between the
feed hopper and the reactor. Once the coal solids have been admitted
into the reactor space, a bed of solids exists within the reactor which
is supported by an aluminum flow distributor.
Steam and other gases are introduced into the bottom of the gasifi-
cation reactor below the distributor plate. The steam is generated in a
series of three furnaces, which are shown in the lower left-hand portion
of Figure 2 and are located within the high-pressure area. The steam
supply tubing has been insulated to prevent heat losses. Strip heaters
are also utilized in order to ensure that superheated steam is fed to
the reactor under closely controlled conditions.
8
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The product gases that emerge from the reactor immediately enter
the particulate trap. This trap contains a stainless steel braided cup
which functions as a flow impinger. Further, the particulate trap is
packed with glass wool as a medium to facilitate removal of solid
particles from the hot gas stream. This trap is heated and insulated to
prevent a substantial tar accumulation in the trap.
The gas stream then passes to the tar trap where a volume of
approximately 8 liters is available for the accumulation of tar and
aqueous condensate. This trap may be tapped periodically for removal of
the accumulated material. This trap is water-cooled in order to remove
the latent heat of condensation from the accumulated material. The
product gases then pass from the tar trap and through the high-pressure
enclosure, shown at the firewall on the right side of Figure 2.
3.2 DATA ACQUISITION AND CONTROL SYSTEM
A number of pressure and temperature values are continuously
monitored, periodically recorded and available for digital display.
Locations of these monitors are shown in Figure 2. Pressure transducers
are used to continuously monitor the pressure of the nitrogen or air,
the steam feed and the product gas stream. Thermocouple indicators have
been installed to measure the various temperatures which may be of
significance in this work. Thermocouples are located at the outlet of
each of the three steam furnaces, at the steam inlet to the reactor and
in the bottom and top of the coal hopper. In addition, the reactor
furnace contains thermocouple detectors in each of its three zones. The
reactor thermowell contains six distinct thermocouple locations over the
length of the reactor. Further, thermocouples are located at the product
gas outlet within the tar-condensate trap.
The three steam generating furnaces are controlled by a single
Lindberg control system. Over long periods of time, temperatures may be
controlled at steady-state levels representing the desired saturation
and/or superheat steam condition. The on/off control mode of this
system has made operation at low steam rates somewhat more erratic than
11
-------
desired. This problem has been brought under control by the addition of
insulation to the system and the use of strip heaters on the inlet steam
line.
The vertical furnace that surrounds most of the reactor during
operation is controlled in essentially the same manner as the three
steam generating furnaces. This furnace does, however, contain three
independently operated heated zones, each of which can demand a maximum
of 2.6 kW. The furnace controller allows the selection of temperatures
in the range of 200 to 1200°C for each zone. The three-zone electric
furnace controller contains a datatrack programmer which will permit the
introduction of any preselected temperature sequence for the three
zones.
The measurement and control points for the gasification system are
also shown in Figure 2. A Beckman continuous oxygen analyzer is used to
monitor the oxygen level in the inlet gas flow or the product offgas
stream when such is deemed desirable. The monitoring of the oxygen
level can be regarded as a safety precaution as well. The presence of
oxygen in an otherwise reducing gas system represents a potential com-
bustion excursion or an explosive condition.
A backpressure regulator is used to maintain the gasification
reactor pressure. By sensing fluctuations in the upstream pressure and
varying the flow accordingly, the backpressure regulator is capable of
maintaining the upstream pressure within ± 1 psi when operating at 1000
psi, i.e., ± 0.007 MPa at 7.0 MPa. After passing through the backpressure
regulator, the gas stream flows through the wall of the high pressure
area to the gas sampling system.
Pressure, temperature, and flow rate signals from the reactor
control system are provided to the signal processor for collection,
reduction, analysis, storage and reporting. The data acquisition
system includes a signal processor (DEC PDP-11/34) with 64K words of
memory, dual disk drive, an alpha-numeric CRT and a 30 cps DECwriter.
(This signal processor and its accessories are being programmed for data
processing in support of the gas chromatographic units which are used to
analyze gaseous effluent samples.)
12
-------
The CRT terminal and the hard copy printer (DECwriter) have a full
keyboard, which permits dialog between the system and its users. These
terminals are used for entry of operator's commands, display of process
conditions and the generation of messages and data lists.
13
-------
4.0 SAMPLING SYSTEMS
4.1 EQUIPMENT ITEMS
A versatile sampling system has been designed, assembled and inter-
faced with the coal gasification reactor. This system is intended to
remove particulate solids, tars, aqueous condensates and other semi-
volatile organic material, volatile organic compounds and fixed gases.
Figure 3 shows the sampling train in relation to the coal gasifier. -"
A particulate filter, which was described in the previous section,
is intended to operate at or near the gas exit temperatures so as to
remove only those solid particles which are entrained in the gas stream.
During the preliminary runs, low volatile materials (tars) have been
collected along with aqueous condensate in the water-cooled tar trap
which follows the particulate trap. The tar trap is equipped with a
valve at the bottom so that samples may be collected periodically during
a reactor run. The traps have Varian high-vacuum flanges to ensure that
gas releases do not occur. These traps are maintained at the system
pressure, which was 1.2 MPa during the preliminary runs.
The gaseous effluent stream leaving the tar trap expands to nearly
ambient pressure through the backpressure regulator. It enters the
sampling manifold which is housed inside a fume hood maintained at or
below 50°C. A three-way valve allows flow diversion to an XAD-2 car-
tridge during the surge period accompanying initial introduction of a
coal sample into the reactor. Check valves are located downstream of
the XAD-2 cartridges to facilitate proper gas routing. These cartridges
are also maintained at or below 50°C by means of water circulation in
their outer jackets. Tenax cartridges are located so that they may be
used to sample the gas stream both before and after the XAD-2 cartridges.
The total volume of gas pulled through the cartridges is kept within the
limits of the breakthrough volume, which has been predetermined for the
amount of Tenax resin employed.
14
-------
en
COAL
IT*
L
PARTICULATE TRAP
REACTOR
CAS
IN
BACK PRESSURE REGULATOR
TENAX TRAP
TAR/HiO
' TRAP
TO DRY
TEST METER
& CONTINUOUS
GAS ANALYZER
TENAX TRAP
TO CRYOGENIC
TRAP
Figure 3. Gaslfier and sampling train.
-------
Tenax-GC resin is a porous polymer material that is based on 2,6-
diphenyl-p-phenylene oxide. It was developed by AKZO Research Laboratories
and is marketed by Enka, NV of the Netherlands.
The Amberlite XAD-2, a product of the Rohm and Haas Corporation, is
a polystyrene-divinyl-benzene copolymer and has a crosslinked open lattice
structure with a porosity between 0.4 and 0.5. This material, when pre-
pared in the 20- to 50-mesh size used in this study, has a surface area
o
of approximately 300 cm /gm. The Tenax cartridges have provided valuable
information in the preliminary tests. The results from the use of Tenax
cartridges have validated the efficacy of the XAD-2 cartridges for
adsorbing organic compounds having a range of volatility values.
The total gas flow through the sampling system is measured downstream
of the sampling devices by means of a Rockwell dry test meter. Gas
volumes that have passed through the adsorbent trap are either monitored
for their volumetric flow rate or redirected to the dry test meter so as
to provide an accumulated total volume of gases generated by the gasifi-
cation reactor.
Grab sample ports are used to collect individual sample volumes
that are analyzed for permanent gases, sulfur-containing gases and C-j-Cg
hydrocarbons via gas chromatograph. The glass sample bulbs used for
this sampling procedure are employed periodically for sample collection
and then stored in a specially designed constant-temperature chest in
order to preserve the samples until the end of the run, i.e., approximately
four hours, for subsequent gas chromatographic analysis. The glass-to-
metal fittings are ultratorr vacuum fittings, providing for leakproof
operation from high vacuum to 0.30 MPa (25 psig). All metal fittings
are of stainless steel and are of the flangeless, ferruled type.
4.2 SAMPLING PROCEDURES
At the conclusion of each run, the particulate trap is removed from
the system. The collected materials are removed from the trap by a
methylene chloride wash sequence. The wash solution is filtered to
16
-------
determine the residue of insoluble material. The solution and residue
are retained for analysis.
The contents of the tar trap are removed periodically during the
reactor operation. These samples consist of tar materials and aqueous
condensates. The samples are marked, weighed and delivered to the
analytical chemical laboratory for analysis.
The sampling strategy for the collection of individual glass bulb
samples, as well as the Tenax and XAD-2 samples, is planned before each
run is conducted. This includes planning the time intervals between
various bulb samples, the times for collection of the individual Tenax
cartridge samples and the time at which the switchover will be made from
the surge XAD-2 to the steady-state XAD-2 cartridge sample. A run is
initiated with nitrogen flow passing to the surge XAD-2 cartridge and
with continuous purging of the first sampling bulb with nitrogen.
Typically the surge XAD-2 sample is taken during the first 40
minutes of the run at which point the valving is used to switch the
stream flow to the steady-state XAD-2 cartridge. The XAD-2 resins in
both the surge and the steady-state cartridges are contained within a
cylindrical packed section which is 64 mm in diameter and 330 mm in
length. When feasible, six additional XAD-2 samples are obtained
utilizing the grab sample ports of the sampling system. Three liters/min
of product gas are passed for five minutes through each of these cartridges,
for example.
The Tenax samples are obtained about two hours after the start of
each run. The Tenax resin is contained within the cylindrical packed
section, 12 mm in diameter, 65 mm in length; some 200 ml of gas is
passed through the Tenax cartridges in 30 sees. The upstream Tenax
cartridge is utilized on the gas stream prior to its passsage through
the steady-state XAD-2 cartridge. The downstream Tenax cartridge is
utilized for sampling the gas stream downstream of the steady-state XAD-2
cartridge. A diagram of the sampling technique for Tenax cartridges
is displayed in Figure 4. This figure also indicates the equipment
17
-------
FLOW
METER
-0-
PUMP
CARTRIDGE
GAS
METER
\
GLASS
FIBER
FILTER
NEEDLE
VALVE
VAPOR COLLECTION SYSTEM
PURGE
GAS
ION
CURRENT
RECORDER
GLASS
JET
SEPARATOR
TWO
POSITION
VALVE
THERMAL
DESORPTION
CHAMBER
MASS
SPECTROM-
ETER
CAPILLARY
GAS
CHROMATOGRAPH
CARRIER
GAS
COMPUTER
I
HEATED
BLOCKS
CARRIER
GAS
EXHAUST
CAPILLARY
TRAP
PLOTTER
ANALYTICAL SYSTEM
Figure 4. Vapor collection and analytical systems for organic vapors.
18
-------
involved in thermal desorption of the Tenax samples which precedes
introduction of desorbed vapors to gas chromatographic analysis.
The grab sample ports are used to divert a portion of the main gas
flow through 500-ml gas sample bulbs as one part of the sampling pro-
cedure. These bulbs are removed periodically by closing stopcock
valves at either end and disengaging the end connectors. These sample
bulbs are then placed in a constant temperature storage box and retained
until the end of the run at which time they are analyzed using a gas
chromatograph.
19
-------
5.0 ANALYTICAL CHEMICAL METHODS
The analytical chemical methods being employed in this study have
been selected from previous efforts directed toward the chemical analysis
of synthetic fuel materials or developed specifically for this study
based on experience with the types of organic compounds of particular
interest to the study. The pollutants from synthetic fuels generally
include polynuclear aromatic hydrocarbons, organic acids typically
containing oxygen atoms, organic bases which typically contain nitrogen
atoms and other more volatile organic compounds. These latter compounds
include sulfur-containing species, e.g., methyl mercaptan and thiophene.
Specific analysis techniques are being utilized for each type and/or
category of organic compounds involved.
5.1 GAS ANALYSIS
The 500-ml gas bulb samples are analyzed by GC without removal of
the bulbs from the constant temperature container in which they are
temporarily retained. A vacuum inlet system is used to transfer sample
gas from the bulbs to the sample inlet equipment. A Heise vacuum gauge
with 1-ml graduations is used for the introduction of precise quantities
of this sample gas into the gas chromatographic units.
A Carle AGC 111-H gas chromatograph is being used for primary gases
and hydrocarbon constituents. Figure 5 shows this instrument, which
contains three columns. Columns 1 and 2 are used directly for the gas
analysis; column 3 is employed as a part of the helium referenced gas
system. The valves VI and V2 are utilized to control the sample flow
through columns 1 and 2. The hydrogen analysis is conducted using these
two columns in series. Then column 1 (Porapak N) is used to determine
the levels of carbon dioxide, ethane, ethylene, acetylene and hydrogen
sulfide. Oxygen, nitrogen, methane and carbon monoxide are determined
using column 2 (molecular sieve 13X). Column 3 simply serves as a flow
20
-------
COL 2
SAMPLE VENT
LEFT
INLET
HELIUM
| EXHAUST
I
I
CONTROLLED | AMB|ENT HYDROGEN
TEMPERATURE | TRANSFER
* 1 * TUBE
RIGHT
INLET
COL 1
COL 2
COL 3
6' - 60/80 PORAPAK N
7' • 80/100 MOLECULAR SIEVE 13X
61 - 8X OV-101 ON 80/100 CHROMOSORB W AWDMCS
-NITROGEN
-HELIUM
RESTRICTOR
Figure 5. Schematic of gas chromatograph.
-------
restrictor for the reference side of the thermal conductivity cell that
is used with this gas chromatograph.
The vacuum inlet system is also utilized for the introduction of
sample bulb gases to a Perkin-Elmer 3920B gas chromatograph. This in-
strument is equipped with a thermal conductivity (TC), flame ionization
detector (FID) and a flame photometric detector (FPD) for the analysis
of C-|-Cg hydrocarbons as well as sulfur-containing gases. A Durapak
phenyl isocyanate column in combination with the TC or FID is used for
the analysis of the hydrocarbon gases. The sulfur-containing gases,
HpS, COS, CSp* mercaptans and thiophene are being successfully analyzed
using a Carbopak B/l.5% XE60/1% HgPO, column and the FPD. Calibration
gases have been obtained from the National Bureau of Standards and Scott
Environmental Technology, Inc. The FPD is known to have a six-fold
linear dynamic range and only relative standards are needed for its
calibration. The nonlinearity of the FPD has been overcome by trans-
forming the analog signal obtained from it to a logarithmic one.
Accurate calibration has been performed using compounds of interest at
varying concentrations.
5.2 VOLATILES ANALYSIS
As was seen in Figure 4, Tenax cartridges are placed into a
desorption chamber and heated to desorb the volatile organic compounds
that are collected in the sampling system. A purge gas transports these
volatiles to a capillary trap where they are condensed for subsequent
analysis. The inlet manifolds for introducing the sample into the
analytical instrument consists of four main components:
1. Desorption chamber.
2. Two-position high pressure (low volume) valve.
3. Gold-plated capillary trap.
4. Temperature controller.
The adsorbed organic material on a sample of Tenax resin is vaporized
by rapid heating to 175°C. The vapor is transferred into a high resolution
22
-------
capillary GC column. This column is interfaced to a double-focusing
mass spectrometer (Varian CH7). During the analysis of each sample, the
mass spectrometer repeatedly scans the column effluent approximately
every 7 seconds. The scans range from 28 to 400 atomic mass units. The
information from these scans is accumulated by an on-line computer onto
a magnetic tape. The data include peak intensities, total ion current
(TIC) values and Hall probe signals (instrument calibration indicators).
XAD-2 samples are prepared for analysis by removing a 20-gram
portion of the resin sample which contains adsorbed material. Extraction
with methyl ene chloride follows for up to 24 hours. The extract is then
concentrated by evaporation under reduced pressure. The final volume of
extract is 1-ml.
The volatile organic samples thus obtained from the Tenax and XAD-2
cartridges are utilized in a combined gas/liquid chromatography column/
mass spectrometer/computer. Further details on this analytical chemical
technique are presented by Sparacino"- B'^y-l and Pellizzari. *
The processing of mass spectrometer data involves extraction of the
TIC data and the preparation of a plot of TIC vs. the spectral number.
A computer then generates mass spectral plots of the compound(s) repre-
sented by individual peaks on the TIC plots. Mass spectral plots display
ion mass vs. ion intensity and represent the characteristic mass spectra
of the compound(s). The components of the sample are then identified by
comparing the mass cracking pattern of the unknown mass spectra to an
eight-major peak index of mass spectra. The identification can be
confirmed by comparing the cracking pattern and elution temperature on
two different GC columns with authenticated compounds. This technique
T231
has been used by Pellizzari, et a!.L J to identify some 200 components
in coal gasification samples. Successful identification has been
achieved with approximately 200 ng of individual components transferred
onto the capillary column.
5.3 SEMIVOLATILES ANALYSIS
The semi volatile materials, sometimes called nonvolatile materials,
represent the organic material collected in the tar/water condensate
23
-------
trap. This is an exceedingly complex sample for which a complete analysis
methodology has not been fully developed. The methodology used herein
involves extraction with methylene chloride followed by GLC/MS/computer
analysis. The methylene chloride extracts organic material from the
aqueous phase. This extract is then concentrated and subjected to
chemical analysis. A sample is provided to the inlet system of a high
resolution glass capillary chromatography column which functions on the
inlet system of a gas chromatograph. The chromatography column was
specifically prepared in the laboratory at RTI for use in these studies.
With it, severe tailing of phenol-type compounds, characteristic of
commercially available columns, has been avoided.
The tar fraction from the tar trap is partitioned using a technique
modified from that of Novotny, et a!.*- •* The partitioning scheme is
depicted in Figure 6. The tars are thus partitioned into six fractions,
namely, acidic compounds, basic compounds, nonpolar neutral, polar
neutrals, PNA and insoluble materials. The procedure has been validated
through the testing of standard mixtures and by the use of radionuclide-
labelled materials.
The acid, base and PNA fractions are analyzed using gas chroma-
tography/mass spectrometer/computer analysis techniques. The use of
peak areas from the GC trace is not feasible due to the complexity of
the sample. The two mass spectrometers which have been used for this
purpose are a Finnigan 3300 and 1KB 2091. Compound identification is
performed as described above in Section 5.2.
Quantisation of specific compounds has also been performed for some
selected samples. The quantitation process involves monitoring specific
ions and comparing their ion intensities with those of carefully chosen
internal standards. Primary standard samples are prepared containing
known quantities of primary standard compounds. In addition, internal
standard compounds are added to both primary standard samples and the
unknown samples. The internal standards that have been used include
pentadeutero-phenol, heptadeutero-quinoline and decadeutero-anthracene.
These compounds represent acidic, basic and PNA materials, respectively.
24
-------
TAR
I INSOLUBLE
I NON-POLAR!
Figure 6. Solvent partition scheme for tars,
25
-------
The primary standard samples are analyzed to generate relative
molar response values for the specific ions resulting from the primary
standard compounds. Quantitation is then achieved by using three pieces
of information: quantity of internal standards added to each unknown
sample; the measured peak area obtained for the primary ion of the
internal standards; and the measured peak area for the selected ion of
each unknown sample. This technique has recently been validated for
both the quadrupole and the magnetic sector mass spectrometer instruments
used in this work. Both instruments have employed high resolution glass
capillary chromatography columns containing OV-101 or SE-30 stationary
phases. Table 1 provides operating parameters which have been utilized
with this system.
26
-------
TABLE 1. OPERATING PARAMETERS FOR 6LC-MS COMP SYSTEM
Parameter
Setting
Inlet-manifold
desorption chamber
valve
capillary trap - minimum
maximum
thermal desorption time
GLC - (Gas/Liquid Chromatograph)
SCOT capillary columns
carrier (He) flow
transfer line to ms
MS - (Mass Spectrometer)
scan range
scan rate, automatic-cyclic
filament current
multiplier
ion source vacuum
260°C
180°C
-195°C
+175°C
10 min.
20°C, 4 C°/nrin.
<3 ml/min.
210°C
m/e 20 ->• 300
1 sec/decade
300 yA
6-0 _6
-\4 x 10 torr
27
-------
6.0 EXPERIMENTAL RESULTS
The most significant experimental results obtained in this study to
date deal with the reactor performance and the analysis of chemical
substances generated by the reactor. Reactor performance testing has
focused on coal gasification under carefully controlled (preselected)
conditions for a sustained time period. The chemical analyses that have
been obtained include data for the primary gas products, the volatile
organic species, and the semivolatile organic materials which have been
collected in the tar trap.
6.1 REACTOR PERFORMANCE
Reactor performance testing has involved the running of three or
more test runs per month. Four runs have been selected from the initial
16 experimental test runs for description in this report. These runs,
designated as numbers 2, 4, 6 and 16, are runs for which sufficiently
complete information is available to provide a meaningful description
and to allow comparisons. The other runs have been useful for overall
system characterization and debugging purposes.
6.1.1 Overall Feed Conversion and Reactor Temperature Profiles
As seen in Tables 2 and 3, the initial runs were conducted utilizing
a char that had previously been generated from Western Kentucky coal in the
COED process.'- -• The elemental and proximate analyses for the feed charge
and the reactor residue subsequent to reaction are shown in Table 2. Data
on the gasification tests are provided in Table 3. As was anticipated,
the percentage of carbon conversion was a direct function of the total
residence time; however, it was observed that the degree of sulfur
conversion during the reactor test was substantially higher than that of
the carbon conversion. This was found to be the case not only for the
char material used in Runs 2 and 4 but also for the Illinois No.6 coal
used in Runs 6 and 16. Generally, this reflects that the sulfur species
28
-------
TABLE 2. COAL, CHAR AND RESIDUE ANALYSES
ro
10
Quantity
Carbon, X
Hydrogen, X
Oxygen, %
Nitrogen, %
Sulfur, %
Ash, %
Moisture, X
Volatile Matter, X
Fixed Carbon, X
Higher Heating Value.
Btu/lb
Free Swelling Index,
FSI
FMC Char
(Runs 1,2,3,4)
74.02
1.48
1.7
1.3
1.8
19.7
1.0
7.8
71.5
11.090
<1.0
Residue
(Run 1)
13.82
0.82
<0.1
0.3
0.2
85.0
0.9
6.3
7.8
570
0.0
Residue
(Run 2)
69.81
1.11
1.0
0.9
1.0
26.2
1.5
4.3
68.0
10,315
0.0
Residue
(Run 3)
52.16
9.73
—
0.39
1.16
43.9
2.38
2.83
50.8
7,615
0.0
Residue
(Run 4)
55.72
0.54
0.43
0.29
0.31
42.0
0.70
2.17
55.1
8,218
0.0
Raw Coal
(Runs 5,6)
63.26
4.61
7.37
1.38
3.01
13.52
6.85
32.58
47.05
11,331
3.5
Residue
(Run 5)
68.54
0.63
0.59
0.70
1.08
26.41
2.05
3.87
67.67
9,882
0.0
Residue
(Run 6)
57.78
0.60
1.35
0.48
0.51
34.64
4.64
2.13
58.59
8,540
0.0
-------
TABLE 3. DATA ON RTI PRELIMINARY GASIFICATION TESTS
CO
o
Run
No.
2
FMC
Char
4
FMC
Char
6
Illinois
No. 6 Coal
16
Illinois
No. 6 Coal
Average
Maximum
Temp.
(°K)
1,018'
1,054
1,079
1,208
' Total
Reactor
Pressure
(MPa)
1.5
1.5
1.5
1.5
Total
Reaction
Time
(hr.)
1.45
4.63
4.50
4.28
Feed
Amount (kg)
Heating
Value
{kcal/kg)
0.175
6,302
0.597
6,302
1.034
6,757
1.494
6,536
Carbon (X)
Sulfur (X)
74.8
1.82
74.0
1.82
67.9
3.23
65.0
2.85
Residue
Amount (kg)
Heating
Value
(kcal/kg)
0.118
5,817
0.303
4,597
0.372
4,975
0.325
2,160
Carbon (%)
Sulfur (%)
70.9
1.01
56.11
0.31
60.6
0.53
35.9
1.06
Conversion
Carbon (%}
36.1
58.0
67.9
88.6
Sulfur (X)
62.6
93.8
94.1
92.3
-------
present are more volatile and more reactive than some of the carbonaceous
materials present. This is not surprising in that the conditions of
reaction which were imposed are those for pyrolysis and partial gasifi-
cation (the carbon/steam reaction).
Tables 4, 5 and 6 present sample analysis information on the
primary gas stream generated by the reactor. These data are also dis-
played graphically in Figures 7 through 9. It is seen in Figure 7,
which represents a char material gasified in Run 4, that the methane
level experiences only a small variation over the entire duration of the
run. This is to be contrasted with the behavior shown in Figures 8 and
9, which represents the gasification of Illinois No.6 coal, in which the
methane content displays its largest value quite early in the reaction
process. This indicates that methane is being produced primarily by the
pyrolytic decomposition of volatile matter from the coal. Alternatively,
the hydrogen content of the product gas was found to increase to a
relatively high value on a nitrogen-free basis and retained an essentially
constant value over the remainder of the run. The carbon monoxide and
carbon dioxide levels of product gas were found to increase over the
initial transient period to essentially steady values intermediate to
those for the methane and hydrogen.
The test runs that have been performed using the RTI laboratory
coal gasification reactor can be divided into two general categories:
external heat tests and combustion heat tests. In the case of external
heat test runs, the reactor is operated without air (or oxygen) supplied
to the inlet. The thermal energy required to maintain the reactor at
the desired operating temperature for external heat tests is supplied by
the vertical furnace which surrounds the reactor. Those runs for which
air represents one of the inlet flow streams are referred to as combustion
heat tests since a certain amount of thermal energy for maintaining the
bed temperature results from the partial combustion reactions which
occur within the bed. For these runs, the external vertical furnace may
also be used to provide additional thermal energy required to achieve a
predetermined operating temperature level.
31
-------
GO
TABLE 4. SAMPLE ANALYSES FOR GASIFICATION RUN 4
(Char dropped after 23 minutes from blank sample collection)
On Stream •»•
Time From
System Blank
(Minutes)
Gas
N2
H2
CO
co2
CH
L
C2H4
C2H6
H2S
COS
Unit
%
%
%
%
%
ppm
ppm
%
ppm
0
>98
<0.01
<0.01
0.02
0.08
<11
<1
<0.01
0
62
74.5
11
0.9
8.6
4.9
16
160
0.58
8.4
123
27.7
38.8
3.1
20.0
8.9
47
380
0.61
10.5
183
8.8
46.7
10.8
22.5
9.6
8.6
48
0.62
147
204
6.7
48.0
15.9
20.8
10.2
6.8
32
0.59
95
264
14.5
43.3
18.4
14.8
7.0
2.1
12
0.11
69.3
Gasifier Conditions
Initial char weight:
Nitrogen Flow:
Steam Flow:
Temperature:
Pressure:
600 grams
500 mfc/minute (STP)
8 gms/minute
Programmed profile: Ramp increase 700-950°C, ramp decrease 950-775°C.
1.5 MPa (200 psig)
-------
TABLE 5. SAMPLE ANALYSES FOR GASIFICATION RUN 6
CO
CO
On Stream
Time (Min) •*
Gases
H2
co2
CO
CH4
C2H6
C2H,
C3H6
C3H8
H2S
COS
CH3SH
Thiophene
Unit
%
%
%
%
ppm
ppm
ppm
ppm
ppm
ppm
ppm
ppm
5
2.69
1.47
1.49
6.56
11100
2900
2800
3300
13600
53
51
68
18
8.62
3.34
2.76
15.42
25100
5000
5600
7900
29400
100
45
151
45
16.18
5.62
2.87
25.36
38500
8300
8800
9600
34500
45
100
184
73
28.55
9.83
3.93
17.69
4800
1000
1000
1100
12000
83
34
96
112
46.81
17.88
6.96
7.59
270
96
52
120
5900
44
10
<5
139
49.32
19.3
12.75
4.62
92
31
26
23
6500
66
10
<5
152
51.35
18.68
16.96
3.78
•
63
22
20
17
5300
48
3
<5
227
50.11
20.09
17.34
2.96
22
8
7
5
5100
24
3
<5
Gasifler Conditions;
Illinois No.6 Coal Weight: 1034 gms.
Nitrogen Flow: 1 liter/min (STP)
Steam Flow: 20.7 gms/rain.
Temperature: Programmed Profile: Ramp increase 600-925°C.
Pressure: 1.5 MPa (200 psig).
-------
TABLE 6. SAMPLE ANALYSES FOR GASIFICATION RUN 16
CO
On Steam
Time (Mln) +
Gases
H2
co2
CO
CH4
C2H6
C2H4
C3H6
C3H8
H2S
COS
CH3SH
Thlophene
Unit
%
%
%
X
ppm
ppm
ppm
ppm
ppm
ppm
ppm
ppm
9
23.46
4.17
6.78
28.40
13.345
11,005
1,894
1,525
18,986
48
27
858
20
32.56
4.99
8.61
22.73
8.736
4,836
1,036
780
18,667
45
9
576
30
39.60
8.53
13.43
6.66
1,465
660
154
136
7,278
33
<5
48
43
37.74
11.01
14.48
2.98
153
56
16
15
5,129
29
28
60
37.28
15.79
17.15
2.57
48
10
1
1.3
5,068
32
6
78
36.58
16.87
16.98
2.47
37
8
4,072
33
<5
90
35.98
17.14
16.37
2.42
28
5
3,979
30
105
35.82
17.42
16.22
2.43
25
4
4,024
27
120
34.30
17.54
15.65
2.38
29
6
3,947
33
Gaslfler Conditions:
Illinois No. 6 Coal Weight: 1573 gms.
Nitrogen Flow: 5 llter/mln (STP)
Steam Flow: 13.7 gms/mln
Temperature: Programmed Profile: Ramp Increase 255-973°C
Pressure: 1.5 MPa (200 pslg).
(continued)
-------
TABLE 6. SAMPLE ANALYSES FOR GASIFICATION RUN 16 (continued)
CO
en
On Steam
Time (Hln) >
Gases •
H2
co2
CO
CH4
^6
C2H4
C3H6
C3H8
H2S
COS
CH3SH
Thlophene
Unit
%
X
%
%
ppm
ppm
ppm
ppm
ppm
PPm
PPm
ppm
135
35.07
18.15
15.06
2.36
23
4
3,908
27
151
33.87
18.05
14.53
2.29
24
6
3,351
26
165
34.29
18.48
14.15
2.32
20
3
3,800
27
180
33.38
18.80
13.61
2.28
24
5
4,042
26
195
33.45
18.72
13.13
2.22
22
5
4,033
27
210
32.35
18.66
12.76
2.14
17
3
4,120
25
225
31.43
18.70
12.23
2.03
17
4
3,736
25
240
29.45
19.08
11.67
1.93
16
3
3,149
24
255
29.76
19.24
11.34
1.85
13
3
3,436
23
270
27.62
19.20
11.76
1.66
12
3
3,265
22
Gaslfler Conditions:
Illinois No.6 Coal Weight: 1573 gms.
Nitrogen Flow: 5 I1ter/m1n (STP)
Steam Flow: 13.7 gms/mln
Temperature: Programmed Profile: Ramp Increase 255-973°C.
Pressure: 1.5 MPa (200 pslg).
-------
50
Run 4
loc:
40
to
•a:
CO
Ul
to
o
30
20
to
o
D_
.
900
,' AVG. BED TEMPERATURE
80C
700 §
600
TIME (MINUTES FROM COAL DROP)
Figure 7. Major product gas concentrations (char run 4)
36
-------
Run 6
CO
•vl
60
u
oc
111
a.
UJ
S
_j
O
> UJ
— in
OUL
111
£g
!S
O
CO
O
40
20
O
O
oc
o.
/
. H,
TEMPERATURE
.O--O--O O- O
V
\,'
p-'
_
-o co2
a co
a
-O C»A
i
40
80 120 160 200
TIME (MINUTES FROM COAL DROP)
240
280
Figure 8. Major product gas concentrations (coal run 6)
1000
900
(O
oc
M
OC
OC
D
<
OC
800 iu
d.
5
m
t-
Q
UJ
m
UJ
700 0
<
oc
UJ
<
600
500
-------
Run 16
CO
CD
60
50
ul
S
s
$
40
F 30
ui
u
il 20 •
2
10
'AVO
" --zg-t^S^-.^.
^_-o o—
.o-
.D-O-
• D-
CO,
CO
1200
1000
800
600
400
200
O
o
CH,
i.o
2.0 3.0
t. HOURS (FROM COAL DROP)
4.0
5.0
Figure 9. Major product gas concentrations (coal run 16).
-------
Run 2 which utilized coal char as a feed material has been
designated as a combustion heat test since air, in addition to steam,
was used in the reactor. Runs 4 and 6 employed a coal char and Illinois
No.6 coal, respectively. Both Runs 4 and 6 are designated as external
heat runs since no air or oxygen was fed to the reactor throughout the
test run period. Run 16 is designated a combustion heat run since air
was supplied, resulting in some heat of combustion within the reactor to
help support the bed temperature level. Figures 7 through 9 also display
the average bed temperature as a function of time for Runs 4, 6, and 16,
respectively. For Run 4, the average bed temperature increases to a
maximum value and decreases, in linear fashion, as a result of the
introduction of a ramp increase followed by a ramp decrease in the
programmed temperature input. For Run 6, a ramp increase followed by a
constant temperature is introduced via the external heater furnace. The
response closely and linearly follows the input profile. For Run 16,
the temperature was found to remain steady after the initial devolatili-
zation period for the coal had been completed. As can be seen in this
figure, the average bed temperature reaches steady-state at about the
same time at which the methane and hydrogen concentrations seem to
achieve steady values.
6.1.2 Low Level Gas Constituents
Tables 4, 5, and 6 as well as Figures 10, 11, and 12 (sulfur
gases only) display data on the concentrations of the minor gaseous
components of the primary gas product stream. The tables show that
ethane and hydrogen sulfide are the two low level constituents that
occur in largest concentrations. These components generally display
their largest concentrations within the initial few minutes of the
reaction process. A similar statement can be made regarding the other
low level gas constituents which are shown. The maximum ethane concen-
tration of 3.8 percent was observed in Run 6. This value decreased to
22 ppm at the conclusion of the run. The maximum ^S concentration
occurred for Run 6 at the same sampling time at a value of 3.5 percent.
This value had decreased to 0.5 percent when the run was concluded.
Measurable quantities of ethylene, propane, propylene, carbonyl sulfide,
39
-------
100,00 _
10,00'
g
ca
§
_ 1,000-
t
o.
o
s
100
10
• Run 2, H2S
ORun 4, H2S
A Run 2, COS
A Run 4, COS
40
280
80 120 160 200
TIME (MINUTES FROM COAL DROP)
Figure 10. Sulfur-containing gas compositions (char runs 2 and 4).
40
-------
Run 6
100,000
10,000
—
tn
Ul
Ul
c
u.
Ul
(9
O
oc
z
?
O
H
OC
ui
U
O
U
1,000
100
10
ocos
40
80 120 160 200
TIME (MINUTES FROM COAL DROP)
240
280
Figure 11. Sulfur-containing gas compositions (coal run 6).
41
-------
Run 16
100,000
10,000
01
at
£1,000
o
cc
z
1
I
cc
100
2
ai
•
• • HjS
• •—.. . « • COS
*
\
\
\
\
\
\
\
\
\
\
\
\
,\
40
\THIUPH
B
»
\
\
\
»
\
t
\
\
\
\
R
80
120 160 200
TIME (MINUTES) FROM COAL DROP
240
280
Figure 12. Sulfur-containing gas compositions (coal run 16)
42
-------
methyl mercaptan and thiophene were detected. As seen in Figures 11 and
12, the methyl mercaptan and thiophene concentrations were found to
decrease quite rapidly to levels below the detection limit of the gas
chromatograph with the FPD detector employed in this work.
6.1.3 Comparative Gasification Data
Data from representative sampling periods were selected from both
char and coal gasification tests for comparison with literature values
for both fixed bed and fluidized bed gasifiers. As can be seen in Table
7, the overall results that have been achieved with the laboratory
gasifier in this study are quite comparable to those reported for the
fixed bed gasifier of the Morgantown Energy Research Center (MERC) and
the fluidized bed gasifier of the Synthane process under development at
the Pittsburgh Energy Research Center (PERC). The concentrations of
hydrogen sulfide, carbonyl sulfide, ethane and ethylene are of the same
order of magnitude from the RTI test runs as they are from the MERC and
PERC results. It can also be noted that the amount of tar produced,
0.022 kg/kg of coal converted, is the same value for Run 6 at RTI and
the MERC reactor. Finally, the amount of fuel gas product was 2.7 to
o
2.9 Mm /kg of coal converted in Runs 6 and 16 and in the MERC reactor.
It can be noted in Table 7 that the hydrogen-to-carbon monoxide
ratio is generally higher from the RTI laboratory reactor than those
ratios in the other two processes presented. This is directly attribut-
able to the fact that the RTI experiments to date have employed lower
air-to-steam feed ratios than those typical of commercial or proposed
fixed bed coal gasification reactors. Higher air-to-steam ratios, in
the range of the candidate processes, are to be utilized in ongoing
parametric studies in this project.
Typical coal gasifier operating characteristics are presented in
Table 8 for seven candidate coal gasification processes of major current
interest. The results of this study are anticipated to be relevant to
these processes. The RTI reactor has been operated at 1.5 MPa pressure
throughout the initial tests, however. While representative results
have been obtained at this pressure, it is anticipated that various
pressure levels will be selected for experimentation during the para-
metric phase of the current research project.
43
-------
TABLE 7. COAL GASIFICATION: OPERATING CONDITIONS
AND PRIMARY PRODUCTS
Test Run No.
Feed Material
Feed Amount, Kg
Pressure, MPa
Temperature (exit)°C
Temperature (max.)°C
Time @ Sample, min
Component (HF)
o2 (x)
N2 + Ar (5)
CO (X)
co2 (%)
H2 (X)
CH4 (X)
H2S (X)
COS (ppm)
C2H4 (ppm)
C2H6 (ppm)
Tar (kg/kg coal)
Gas Product, Mm /kg
Gas Product, scf/lb
Mo. 2
FMC Char
Air
0.175
1.5
285
735
77
3.0
56.9
2.0
17.4
9.0
4.9
1.3
63
23
157
—
12.8
220
No. 4
:MC Char
External
heat
only
0.600
1.5
353
833
123
—
27.7
3.1
20.0
38.8
8.9
0.6
11
47
380
—
3.5
56
No. 6
111. £6
Coal
External
heat only
1.034
1.5
367
726- -
73
~
35.1
4.0
10.1
29.4
18.2
1.2
83
1000
4800
0.022
2.8
44.6
No. 16
111. =6
'Air
1.573
1.5
454
955
78
~
26.6
17.0
16.9
36.6
2.5
0.5
33
8
37
0.035
2.7
43.8
MERC
(Air
Blown)
111. 26
Coal
0.22
650
1350
~
~
51.5
21.8
6.9
17.8
2.0
0.2*
315
NA
2000
0.022
2.9
47
Synthane
(Air
Blown)
111.56
Coal
*.
1.9
MA
987
—
—
43.4
10.1
17.9
21.5
5.6
0.7*
NA
NA
7000
0.047
1.3
20.7
Synthane
(Oxygen
Blown)
111.16
Coal
*
4.2
760
932
—
--
—
13.2
36.2
32.3
15.0
1.6*
150
NA
16000
0.047
0.81
13.8
MF~Moisture Free
*Elemental composition of feed coal varies somewhat from that used in the RTI tests.
44
-------
TABLE 8. TYPICAL COAL GASIFIER OPERATING CHARACTERISTICS
en
Air/Coal Ratio,
kg/kg (Ib/lb)
Steam/Coal Ratio,
kg/kg (Ib/lb)
Nominal Pressure,
MPa (psla)
Exit Gas Temperature,
°K (UF)
Maximum Temperature,
ov /or\
^ \ * 1
Oil and Tar Product,
kg/kg coal (lb/ton)
Paniculate Product,
kg/kg coal (lb/ton)
Gas Product,
Nm3/kg coal (scf/lb coal)
Higher Heating Value,
J/Nm3 (Btu/scf)
Cold Gas Efficiency, %
Gas Composition,
Cold & moisture free
CO
C02
"2
CH4
N^ + Ar
H2S + COS
Wellman-Galusha
Fixed-Bed
3.5 (3.5)
0.4 (0.4)
0.10(14.7+)
922 (1200)
1633 (2400)
0.06 (120)
0.03 (60)
3.8 (64)
6.0 x 106
060)
75
28.6
3.4
15.0
2.7
50.3
MERC Stirred Bed
Fixed-Bad
3.0 (3.0)
0.5 (0.5)
2.1(285)
922 (1200)
1633 (2400)
0.04 (70)
0.03 (60)
3.0 (50)
5.2 x 106
(140)
79
20.4
8.7
15.5
2.4
52.5
0.5
Woodall-Duckham
Fixed-Bed
2.3 (2.3)
0.25(0.25)
0.1+04.7+
394 (250)
1477 (2200)
0.08 (150)
Low
2.9 (49.7)
6.5 x 106
075)
77
28.3
4.5
17.0
2.7
47.2
0.3
U-Gas
Fluldlzed-Bed
3.0 (3.0)
0.5 (0.5)
2.5(350)
1116 (1550)
1311 (1900)
Small
Recycled
3.7 (63)
5.7 x 106
0*4)
79
19.6
9.9
17.5
3.4
48.9
0.7
OCR
Low-Btu Gasifler
Three Stage
Fluldized-Bed
3.2 (3.2)
0.7 (0.7)
1.75(235)
1255 (1800)
1422 (2100)
None
Fine Ash
4.9 (83.3)
6.0 x 106
060)
88
25.7
5.2
23.4
--
45.5
0.2
Synthane*
Fluldlzed-Bed
0.35*(0.35)
1.25 (1.25)
7.0 (1000)
1033 (1400)
1255 (1800)
0.05 (104)
0.3 (600)
0.81 (13.8)
1.3 x 107
(355)
NA
13.2[10.1]**
36.2[17.9]
32.3[21.5]
15.0[5.6]
- [43.5]
1.6[0.7]
Combustion Engr.
Entrained Flow
3.5 (3.5)
NA
0.1+(14.7i)
1144 (1COO)
2255 (3600)
Negligible
Small
3.9 (66.7)
4.7 x 106
(127)
69
22.1
7.0
17.0
0.03
53.3
0.6
*0xygen blown operation typical for Synthane process.
**Gas composition for airblown operation for Synthane process.
NA-not available.
-------
6.2 CHEMICAL ANALYSIS RESULTS
The chemical analysis results which are reported herein should be
regarded as preliminary findings. This is because the experimental
laboratory reactor and its accessories, the sampling system and the
chemical analysis procedures have all been under development during the
tests reported to date. Nonetheless, it seems desirable that these
results be presented since they have demonstrated: (1) the feasibility
of operating the reactor for sufficient time periods at pressure to
collect meaningful samples for further chemical analysis; (2) the ability
to achieve operating conditions that simulate conditions in commercial
or prototype reactor processes; and (3) the efficacy of procedures for
systematic analysis of permanent gases and volatile organic compounds,
as well as the high molecular weight semivolatile organic compounds
contained within the tar products from the reactor. A substantial
effort has been required to achieve these results. The operation of
reactors at elevated temperatures and pressures is difficult. The
large number and high level of complexity of the organic compounds
resulting from coal conversion present a particularly challenging
analytical task.
6.2.1 Primary Gas Products
The data presented in Figures 7 through 9 showed that the com-
position of the primary gas stream from the reactor for the runs focused
upon herein is well behaved. The results from the gas chromatography
analysis of the primary gas product stream account for all of the major
components. Figures 10 through 12 showed concentration profiles for the
primary sulfur species which were present in the product gas stream for
these runs. Generally, the hydrogen sulfide and carbonyl sulfide levels
were found to decrease slightly to a steady value after the initial 40
minutes of the reactor operation. However, the methyl mercaptan and
thiophene levels were found to decrease quite dramatically during the
initial operating time periods.
46
-------
6.2.2 Volatile Organic Products
Chemical analysis results have been obtained for the volatile
organic compounds removed using Tenax or XAD-2 resin cartridges. The
samples have been subjected to both qualitative and quantitative
evaluation for their primary peaks. Total ion current plots were
generated by gas chromatography/mass spectrometry/computer analysis. In
spite of their preliminary nature, the following graphs and tables show
that the resolution of individual components has been achieved quite
successfully by the chemical analysis procedures utilized.
For Run 2, which is a combustion heat run with a coal char, the
results are displayed in Figure 13 and Table 9 for a Tenax cartridge
collected upstream of an XAD-2 adsorbent. Run 4 is an external heat run
using char feed. Figure 14 and Table 10 display the results obtained
for this run using ah XAD-2 cartridge operating on the raw reactor gas
stream. Run 6 is an external heat run using coal. An XAD-2 cartridge
result obtained for Run 6 is shown in Figure 15 and Table 11 and can be
compared to Figure 14 and Table 10. Over 80 distinct compounds were
detected in the effluent from the char feed material as compared with
over twice that number from the Illinois No.6 coal.
Also, for Run 6, results of a steady-state XAD-2 cartridge are shown
in Figure 16 and Table 12. This sample, which was collected during the
char gasification stage of the conversion process, i.e., after the
devolatilization stage, shows some 20 prominent organic constituents as
compared with some 60 found during the devolatilization stage.
Run 16 also utilized Illinois No.6 coal. This run employed an air-
to-steam rate of approximately 0.5 on a weight-to-weight basis. The
analytical chemical results for volatile organic compounds obtained for
this run are presented in Figures 17 and 18 and Tables 13 and 14 for a
Tenax and a steady-state XAD-2 cartridge, respectively. It was found
that a somewhat greater amount of volatile organic material resulted
from Run 6 than from Run 16. It is believed that this is due to the
fact that in Run 16 the oxidative process associated with the air feed
was responsible for reducing volatile organic material loading of the
effluent gas stream.
47
-------
12
20
00
30000-
•
E 0 0 (i 0 -
10000-
-
0-
300
1
2"
J 11
l 10
1 Jl .
L . J
0 3050 31
1
00
u
16
U*-
3150 33
18
•
2
21
V *
3
24
1 27 30 32
00 3850 3300 3350 3400 34!
SPEC!', 3000 - 3S"50 III 13V(/CHflR TX 1 . BEFOKF '£rSEPl 7r/"35ri5E30GSC STEP SPECS"! I«T=- 1000
1
20 i 40
0 ' 5
Temperature (°C)
i 60 i 80 i 100 i 120 il40
1 10 ' 15 '20 !25 F30
Time (min.)
Figure 13^ Total ion current chromatogram of GC/MS analysis of upstream Tenax
sample for char run 2.
-------
37
<£>
jj
14C
30
5
49
48 I
1 |i J
\ 38 41 «3 45 I | \/' '
' ' ?.9 4£ ytj^!£-*~*~5U
^^w^^r^,,,,^,.
I ,160 , 180
' 35 '40
2
59
/
^•5*5556 5758J ^^5!_-'v 63 164 65 ,.A^,-.68 6r9
3ii?0 3700 3?t'U 'JJiiO 3!jO
Temperature (°C)
, 200 , 220 , 240
1 45 'SO '55
390(1
Time (min.)
Figure 13 (cont'd)
-------
TABLE 9. COMPOUNDS IDENTIFIED
XAD-2 CHAR RUN 2
FROM TENAX SAMPLE UPSTREAM OF
Chromato-
graphic
Peak No.
1
4
5
7
8
9A
10
11
12
12A
13
14
15
ISA
16
17
17A
18
19
19A
20
20A
21A
21B
21C
22
23
24
24A
25
26
26A
27
29
30
31
32
32A
33
33A
35
36
36A
37
37A
37B
Elution
Temp .
co
47
49
50
52
55
58
59
61
63
65
67
69
71
73
74
77
78
80
82
83
84-7
87
92
94
95
100
107
109
110
113
115
116
117
127
129
132 „
133
136
136
139
145
147
148
149
150
151
Compound
co2
carbonyl sulfide
sulfur dioxide
butene isoner
acetaldehyde
acetonitrile
acetone
diethyl ether
dichloronethane (BKC)
carbon disulfide (tent)
C.HgO isoner (tent)
2-nethylpentane
3-nethylpentane
hexafluorobenzene (ef)
n-hexane
ethyl acetate
C7H16 l80Der
methylcyclopentane
perfluorotoluene (ef)
CjH^O isoner (tent)
benzene
thiophene
trichloroethylene (BKG)
C7H16 isoner (tent)
C7H16 lsoner
acetic acid
toluene
nethylthiophene isomer (tent)
methylthiophene isoner
C-H-.0 isoner
ii-octane (tent)
C8H16 i80ner
tetrachloroethylene (BKC)
ethylbenzene
xylene isoner
styrene
£-xylene
CjHjg isoner
n-nonane
isopropylbenzene (tent)
benzaldehyde
C.-alkyl benzene isoner
Cj-alkyl benzene isoner
benzonitrile
phenol
methylstyrene laoner (tent)
Chronato-
graphic
Peak No.
37C
37D
38
-
39
39A
39B
40
41
41A
42
43
43A
43B
45
46
47
-
48
49
50
51
52
52A
53
54
55
57
58
59
61
65
Elution
Temp.
(°C)
151
152
153
-
155
155
156
159
160
161
163
165
166
167
170
172
176
-
178
181
183
186
187
188
190
192
195
204
206
209
218
231
Compound
C,-alkyl benzene isomer (tent)
methylstyrene isomer
benzofuran + C,-alkyl benzene
isoner
ii-decane
C,-alkyl benzene isomer (tent)
dichlorobenzene isoner (BKG)
C.-alkyl benzene isoner
sat. hydrocarbon
indan
indene
acetophenone
cresol isoner
C^-alkyl benzene isoner
n-nonanal
n-undecane
C2-alkyl phenol + C^-alkyl
benzene (tent) isoners
dinethylphenol isoner
C.-alkyl phenol isoner
C.-alkyl phenol isomer
benzoic acid + 2- (p-tert-bu-
tylphenoxy)ethanol (tent)
naphthalene
2 , 3-benzothiophene
C.-alkyl phenol isoner
C.-alkyl phenol isoner
C,-alkyl phenol isomer
g-nethylnaphthalene
a-nethylnaphthalene
benzanide
C14H30 iaoner
sat. hydrocarbon
50
-------
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Time (min.)
Figure 14. Total ion current chromatogram of GC/MS analysis of upstream Tenax sample for
char run 4.
-------
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41
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Temperature (°C)
100 i 2nn
2f.
2/.0 inorlinrm.,1
35
50
50
Time (min.)
Figure 14 (cont'd).
-------
TABLE 10. COMPOUNDS IDENTIFIED FROM TENAX SAMPLE UPSTREAM OF XAD-2,
CHAR RUN 4
Chromato-
graphic
Peak No.
1
1A
IB
2
3
3A
3B
3C
3D
3E
4A
4B
5
5A
5B
6
7
7A
7B
7C
7D
8
8A
9
9A
10
IDA
10B
IOC
11
11A
11B
12
12A
13
13A
13B
13C
14
15
16
16A
16B
17
18
ISA
Elucion
Temp.
49
50
5i:
55
57
57
58
58
59
62
63
63
64
65
65
66
68
69
69
70
72
73
74
76
78
79
80
82
83
84
85
88
89
92
96
98
101
104
106
111
112
112
114
116
118
119
Compound
co2
hydrogen sulfide
carbonyl sulfide
sulfur dioxide
C.Hg isomer
n-bucane
me thane thiol
C_H,S, isomer (tent)
t, O f.
acetaldehyde
isopentane
furaa
C5H10 isomer
ii-penCane
acetonitrile
dichloroethylene isomer (BKG)
dichloromethane (BKG)
carbon disulfide
C.HgO aldehyde isomer (tent)
C-&. , isomer
acetone
butanal + C7Hifi isomer (tent)
2-methylpentane
C,H0 isomer (tent)
o o
3-methylpentane
hexafluorobenzene (el)
n-hexane
chloroform (tent) (BKG)
methyl ethyl ketone (tent)
C^ELg isomer
methylcylopentane
- C7H16 isomer
perfluorotoluene (el)
benzene
thiophene
trichloroethylene (BKG)
C-H. , isomer
CgH^g isomer
CgH-, isomer
acetic acid
toluene
methylthiophene
CgHj^O isomer (tent)
CgH^g isomer (tent)
hexanal
n-octane
tetrachloroethylene (tent) (BKG)
Chroma to-
graphic
Peak No.
20
21
22
22A
23
24
24A
24B
24C
25
25A
26
27
27A
27B
-
28
28A
-
29
29A
30
30A
30B
30C
30D
31
31A
32
32A
33
33A
34
-
35
35A
36
36A
37
37A
37B
38
39
40
41
41A
Elucion
Temp.
129
131
135
135
136
138
138
142
146
147
147
148
150
151
152
-
152
154
-
154
155
156
159
160
160
161
162
163
164 '
165
166
167
170
-
171
173
173
176
178
178
179
181
183
186
188
189
Compound
ethylbenzene
xylene isomer
styrene
n-hep canal
o-xylene
C.H.g isomer
CqH20 isomer
isopropylbenzene
C10H22 l30mer
benzaldehyde
n-propylbenzene
ethyltoluene isomer
benzonitrile
phenol
mechylstyrene + cigH22 (tent)
isomer s
2-octanone
methylstyrene isomer +
n_-octanal
benzofuran
C.-alkyl benzene isomer
nj-decane
C^-alkyl benzene isomer
C.-alkyl benzene isomer
C,-alkyl benzene isomer
C11H24 isomer
indan
indene
C^-alkyl benzene isomer
C^-alkyl benzene isomer
acetophenone
cresol isomer
methyllndan or C,H--benzene
isomer
n-nonanal
Cj-alkyl benzene isomer
11— undecane
C2~alkyl phenol isomer
dimethylphenol isomer
C13H26 lsomer (tent)
dimethylphenol isomer
Cj-alkyl phenol isomer
C2-alkyl phenol isomer
Cj-alkyl phenol isomer
naphthalene
2 , 3-benzo thiophene
53
-------
Table
Chromato-
graphic
Peak No.
42
43
43A
44
44A
44B
45
45A
46
47
47A
48
48A
49
10 (cont'd)
Elution
Temp.
(°C)
190
192
193
195
197
201
204
206
211
215
216
222
227
230
Chromaco- Elucion
Compound graphic Temp. Compound
Peak No. (°C)
ri-dodecane
C.-alkyl phenol isomer
C.-alkyl phenol isomer
C.-alkyl phenol isomer
propiophenone
undecanal (tent)
S-methylnaphchalene
a- methyl naphthalene
dodecanal (tent)
biphenyl
n-tridecane (tent)
C14H28 1SOmer
C_-alkyl naphthalene isomer
unsat. hydrocarbon
54
-------
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Temp (C°)
20 40 60 P8d 100
II II
1 1 1 1
m • / _f \ «V/
1^0 140
1 1
30
Figure 15. Total ion current chromatogram of GC/MS analysis of upstream Tenax sample for
coal run 6.
-------
en
en
1 3 56T8 4 Si 4
run
8 B
n
n
I
3 'I 0 0
160
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7
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180
200
40
220
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50
Figure 15 (cont'd)
-------
TABLE 11. COMPOUNDS IDENTIFIED FROM THE UPSTREAM
TENAX SAMPLE FROM COAL RUN 6
Chromatographic
Peak No.
2
3
4
5
5a
5b
6
7
8
9
9a
10
11
lla
12
13
13a
15
15a
15b
16
17
17a
18
19
20
21
22
22a
23
24
24a
25
25a
26
26a
27
27a
28
28a
29
29a
30
30a
30b
Compound
Ug/i
carbon dioxide
carbonyl sulfide
sulfur dioxide
butene isomer
butene isoaer
CjEj^ isomer
C^ isoaer
unsaturated hydrocarbon
acetone
CeH._ isomer
carbon disulfide - mathylene
chloride (BKC)
CCH, isomer
3 U
C.H, isoner
C-Hg isomer
C.Hyj isomer
methyl ethyl kecone
C6*12 iaomer
n— hexsne
CgHj, isomer
C,H-_ - C_F- isomers (el)
O 12 / o
C6H12 isoaer
CgHg isomer
C6*W 1"OBer
benzene 7.7
thlopheae 1.3
methyl isopropyl ketone
2-pentsnone
trichloroethylene (BKG)
CyHj^ Isomer
n-heptane
C_B_, + 71 — isomers
C-E-. isomer
C-H. , isomer
acetic acid
C7H10 1*°*er
C7BU isoaer
toluou 5.7
methylthiophene Isomer 10.1
methyl chlophene Isoaer 0.9
CgH. , isomer
C8H16 l80"er
CgH.g isomer
n-octane
CgEL, isomer
CfPl6 iB01*r
Chromatographic
Peak No.
30c
30d
30e
30f
30g
30h
301
30J
31
32
32a
32b
33
34
34a
35
35a
36
37
38
38a
39
39a
40
41
41a
42
42a
43
43a
44
44a
44b
45
46
47
47a
47b
48
48a
48b
49
50
50a
Compound
C8H14 isolner
CgH-. isoner
CgH14 isomer
CgH22 Isoaer
CgH., Isoaer
C|*H^ .. isomer
CgH. g isomer
CgH^j isomer
ethylbenzene
xylene isomer
dimethylthiophene isomer
dinethylthiophene isomer
styrene
o- xylene
Cj-thiopheae
CgH... isomer
C9H18 Uoffler
Isopropylbenzene
CgHlg isomer
S^S * C10H22 iaoaers
C10H22 isotaer
n-propylbenzene
C ,-thiophene
C.-benzene
phenol
Cj-thiophene + C^-benzene
isomers
Cj-benzene + C.H,-benzene
isomers
Cj-chiophene isoner
benzofuran + C.-benzene isoner
n-decane
2 , 3 ,4-trlmathy Ithlophene
C^-thiophene isoaer
C^-benzene isomer
C -benzene Isoaer
cresol + C^Hj -benzene Isomers
ludene
C^-benzene isoner
C4-benzene isomer (tent)
C^-benzene isomer
cresol + C4-thlophene isomers
C^-benzene isomer
C^-thiophene Isomer
C^-benzene isomer
C^Hy-benzene
va/i
0.8
6.2
1.8
11
2.9
3.7
2.3
1.9
6.5
19.5
57
-------
Table 11 (cont'd)
Chromatographic
Peak No.
51
51a
52
52a
53
53a
54
54a
55
56
57
58
58a
59
59a
59b
59b
59c
60
60a
60b
60c
61
62
62a
63
63a
64
64a
64b
64c
65
66
67
68
69
70
71
72
72a
73
73a
74
Compound /£
C, -benzene isomer
C4H?-benzne
C11H22 isoner
C.-phenol
methyl benzofuran isomer 0.4
C11H24 isonBr
methyl benzofuran isomer 4.1
C.-benzene
C.-benzene + ciiH22 iBomers
C.-benzene isomer
C,H_-benzene isomer
C.-phenol isomer
C -benzene isomer
C,R--benzene isomer
C.-benzene isomer
C,-thiophene iaomer
C,-thiophene- isomer
ethylphenol isomer
methyl indene isomer
C fl-benzene isomer 5.6
C.-benzene isomer
4
methyl indene isomer 6.1
C.-benzene isomer
C.-phenol isomer
C,H--benzene isomer
benzole acid
C.H--benzene isomer
naphthalene 35
C.Hg -benzene isomer
2,3-benzothiopbene + n- 3.7
dodecane + C.-benzene isomer
C-Hq-benzene isomer
dimethylbenzofuran Isomer 1.2
C13H28 iaoner
dimethylbenzofuran isomer
C.-benzene isomer
o
C.Hg-benzene isomer
methyl dihydronaphthalane
isomer
C.Hg-benzene isomer
methyl dlhydronaphthalene
isomar
C.H_-benzene Isomer
C14H30 i800Br
C12H16 iaOIBer
C H + C B —benzene isomers
13 26 5 9
Chromatograohic
Peak No'.
74a
75
76
76a
76b
77
77a
78
79
80
80a
81
81b
82
83
84
85
85a
86
86a
87
87a
87b
Compound
C. ,H__ +• methylbenzo-
thiophene isomers
tridecane
S-methylnaphthalena 4.9
C,H_ -benzene isomer
methylbenzothiopbene isomer
a-methylnaphthalene
CgH.-benzene isomer (tent)
Cg^^-benzene isomer
C14H30 isOTer
C13H32 iBOOCr
hydrocarbons
n-tetradecane
ethyl-naphthalene isomer
dlmathylnaphthalene isomer
dimathylnaphthalene isomer
dime thy Inaphthalene isomer
C.,H36 isomer + biphenylene
C, -naphthalene iaomer
n-pentadecane + acenapbthene
C. -naphthalene isomer
dibenzofuran + ^R^L5~ 0-0?
benzene isomers
C.-naphthalene isomer
C.-naphthalene isomer
58
-------
Ul
VO
in B>
z vo
2.
s
5
S3
in
de
a —
P 5
c
-------
en
o
O»O
140°
-+—
15
160C
180
200
220
20
25
Figure 16 (cont'd).
-------
TABLE 12. COMPOUNDS IDENTIFIED FROM THE STEADY-STATE
XAD SAMPLE FROM COAL RUN 6
Chromatographic
Peak No.
1
2
2a
3
4
5
6
7
8
8a
9
10
lOa
11
lla
lib
lie
lid
lie
12
12a
12b
13
13a
14
148
15
ISa
16
16a
17
17a
18
19
19a
20
20a
21
22
23
Z3a
24
24a
Compound ^
toluene
CgHjg isomer
C.Hj, + dichloromethane (blcg)
C8H16 I80ner
C9H18 ison'r
ethylbenzene + > 30
ethylthiophene
diaethylthiophene +
xylene isoners > 30
Etyrene
zyleoe Isoner > 30
dinethylthiophene isomer > 30
C9H18 is°Der
n-nonane
unsaturated hydrocarbons
C.-benzene Isoner
C,!^,. isomer
C9H16 1SOIller
CgHjg iaomer
C.H.-benzene Isooer
C10H22 ia°a'r
C.-benzene isomer 18
unsaturated hydrocarbons
C.-chiophene Isoaer
C.-benzene isomer 19
C.-thiophene isomer
C.-benzene isomer 7.4
C_-thiophene
C.-benzene + 5.8
trinethylthiophene
unknown
benzofuran
oetbylstyrene isomer
C.-benzene isomer 27
phenol 40
C10H20 1»OT"r
crinethylthlophene Isoaer
C10H22 isoner
C3-benrene isomer 6.8
diechylbenzene
indan 7.4
indene 110
c4-beozene isoner 7.1
C.-benzene isomer
C^-benzene isomer 7.4
cresol isomer 45
Chromatographic
Peak No.
25
25a
25b
25c
25d
25e
25f
26
26a
26b
27
28
29
29a
29b
29c
29d
30
30a
30b
31
31a
31b
31c
31d
32
32a
33
33a
33b
33c
33d
33e
33f
33g
33b
34
34a
35
35a
35b
35c
Compound
C.-benzene isooer
4
C.-thiophene +
cresol isooer
C.-benzene Isomer
C,-thiophene isomer
C.H.-benzene Isomer
C,-thiophene •*• aethylindene
isoners
1,2-diaethyl etbylbenzene isoner
C B.-benzene isomer
4 7
C.-benzene isomer
cresol isomer
C,E--benzene isomer
methylbenzofuran isomer
mechylbenzofuran isomers
C.-thiophene isomer
C.-benzene isomer
4
C.-benzene + C.-phenol isomer
C11H22 iaoaer
mechylindene isomer
C,B--benzene isomer
C.-benzene isomer
4
C11H24 tsoner
C^B.-benzene Isomer
C,Bg-benzene isomer
C11322 + C4H7*benz"ne isomers
C11H24 l8OTer
nechyl-2,3-dlhydroindene isomer
C.-benzene isomer
mecbylindene isoner
C.B^-benzene + C.-benzene
isomers
C^-benzene
mechylindene isomer
C.-phenol isomer
n-pentylbenzene
C.-thiophene isoner
C.-benzene isomer
C.Hg-benzene isomer
naphthalene
C.-phenol + unknown
dimethylindan isoner
cg-benzene isooer
CjHj-benzene + Cj-phenol
isomers
C^-phenol + dioethylbenzofuran
mg
10
45
38
70
15
20
57
40
270
84
230
61
-------
Table 12 (cont'd)
Chromatographic
Peak No.
36
36a
37
37a
37b
38
38a
39
39a
39b
40
40a
40b
41
4 la
Alb
Ale
Aid
42
42a
42b
42c
42d
43
43a
43b
44
44a
AAb
44c
AAd
AAe
AAf
45
45a
46
46a
Compound
mg
Cj-benzene + dimethylbenzo-
furan isomers
Cj-phenol isomer
dimethyl benzofuran isomer
(tent)
CjHj-benzene isomer (tent)
alkyl benzene isomer
C12H26 i'omer
Cg-benzene + C^-phenol
isomers
CjHj-benzene isomer
Cj-phenol isomer
C13H28 l80ner
Cj-phenol isomer
dimethyllndan isomer
C11H12 i80IIler
C.H.-benzene isomer
C,-phenol isomer
C,-phenol isomer
methylbenzothiophene isomer
.(tent)
C,Hq-benzene isomer
B-methylnaphthalene 0.6
methyl benzothiophene
isomer (tent)
C.H. .-benzene isomer
methyl benzothiophene isomer
(tent)
CgB,-benzene isomer
o-methylnaphthalene tr
saturated hydrocarbon
CgHjj-benzene or unknown
n-tridecane
CE. .-benzene or unknown
saturated hydrocarbon
C14H26 *"»**
C1AH28 lsooer
biphenyl 0.6
dlmethyl-1-thiaindene isomer
(tent)
ethylnaphthalene isomer
dimethyl thiaindene isomer
(tent)
dimethyl naphthalene isomer
saturated hydrocarbon
Chromatographic
Peak No.
A6b
A7
48
48a
49
49a
49b
49c
49d
50
50a
51
51a
51b
51c
51d
51e
Slf
51g
51h
511
52
53
53a
53b
54
54a
54b
Compound
mg
trimethyl tetrahydro-
phthalene isomer
dimethyl naphthalene isomer
n-tetradecane
dimethyl naphthalene
acenaphthtlene
dimethyl naphthalene isomer
hydrocarbons
acenaphthene 0.6
C13ai2 ^soner
C14H14 lsomer
C13H12 i80ner
n-hezadecane
C^-naphthalene isomer
dibenzofuran (tent) 2.7
saturated hydrocarbon
C.-naphthalene isomer
C.-naphthalene isomer
fluorene
C13H12 isomer
hydrocarbon
C. .H..O isomer
13 10
i fi i fi Isomer
C16H18 i
-------
0>
(A)
30000-1
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30000-
10000-
I? Is
81
V
\*
8 9 8
o-
f 0 CO
SPFCS 4000
[»T|nmi^mi>'i>T^«niipr^>|tTnim«|inyMpliiliii»|i.iiHpriMj"il^.|»iyMim
-------
(7)
N34
"U
o
(0
i!4-;u
MS mi
160
H-
180
4-
40
MI. oo
•«., so
Temperature (°C)
200 220
1 h
240
ISOTHERMAL
Time (min)
50
Figure 17 (cont'd).
-------
TABLE 13. COMPOUNDS IDENTIFIED FROM TENAX CARTRIDGE NO.2
FROM COAL RUN 16.
Chronacographlc
Peak So.
18a
18b
24a
24b
27
28
30
37
42
43
44
44b
54
57
Compound
benzene
thlophene
toluene
oechylthlophene
ethylbenzene
zylene, a,p-
xylene, o-
isopropylbenzene (cumeoe)
Indan
indene
crasol isooer
C.-alkylbenzcne Isooer
naphthalene
2 , 3-benzothlophene
Pg/i
1100
150
125
110
12
.» 40
12
52
8
125
43
2
81
1
Chromatographic Compound
Peak No. pg/&
65
-------
cr>
er>
50 Temperature (°C) 10°
150
4-
6 Time (min)
18
Figure 18. Total ion current chromatogram of GC/MS analysis of steady-state XAD-2
sample for coal run 16.
-------
a*
o
o
in
Temperature (°C)
200 2^0
26
Time (rain)
31
Figure 18 (cont'd).
-------
TABLE 14. COMPOUNDS IDENTIFIED IN THE EXTRACT OF
STEADY STATE XAD TRAP FROM COAL RUN 16.
Chronato^raphic
Peak No.
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
Coaoound
ethylbenzene
a.p-xylene
di=echylthiophene isocer
o-xylene +
scyrene
BKC +
dloechylchlophene isomer
C9H22
isopropylthiophene
isop ropy Ibenzene
C,-beazene
C_-thiophene isoners
benzofuran
C,-benzene
C,-benzene
indan
Indene +
phenol
diechy Ibeazene
C^-benzene
C, -benzene
C,H_-benzene +
o-cresol
C^Hj-benzene
oechyl-benzofuroa
=S
2.0
6.3
0.6
1.6
0.9
O.i
0.3
0.5
0.2
1.6
24
3.S
1.8
1.9
cr
1.4
Chroracc-jraphlc
Pejx. :.'o.
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
- or.pour.a
eechyl-benzofuran (cent)
hydrocarbon +
n.p-cresol
oechyl Indene
naphthalene
benzochlophene +
dloechylphenol
dieechylphenol •*•
3 , 6-dlcechy Ibenzof uran
nechyl-dlhydronaphchalene
S-oechylr.aphthalene
ci-oechylnapbchalene
biphenyl
dioechylnaphchalene
blphenylene
acenaphthalene
dibenzofuran
fluorene
C,H.Se or unknown
245
BKG
BKG
anthracene -
d.. anthracene
hydrocarbon
fluoranchene
pyrene
=g
3.4
8.1
41.6
9.7
8.0
(tent)
1.9
1.0
0.9
0-7
1.4
0.2
0.1
< 0.1
< 0.1
68
-------
A summary of quantitative chemical analysis results obtained by
utilizing Tenax and XAD-2 resin adsorbers is presented in Table 15.
This table indicates that the Tenax cartridges are more effective than
XAD-2 resins for the removal of compounds having a higher volatility,
e.g., benzene, thiophene, and toluene. Alternatively, the XAD-2 resins
function quite effectively in the capture of high molecular weight
organic materials, e.g., naphthalene, biphenyl and anthracene. The
results for Run 16 which are shown in Table 15 have been plotted for
visualization and comparison. These are shown in Figure 19. Generally,
it was found that these concentrations decreased monotonically from the
high value detected in the initial Tenax sample. Hydrogen sulfide,
carbonyl sulfide and naphthalene appear to be generated at effectively
a constant level after the initial transient. The relatively constant
values for hydrogen sulfide and carbonyl sulfide shown in Figure 19
probably result from the gasification of sulfur retained with the char
after the devolatilization process is effectively complete. It is
believed that the behavior shown by naphthalene results from its being
held up in its passsage through the tar trap and sampling system much
like retention on a chromatographic column. This belief is supported by
the fact that naphthalene is less volatile than the other components
shown in Figure 19.
It should be emphasized that the concentration scale (ordinate-
axis) on Figure 19 displays logarithms of the concentration values.
Thus, the concentrations of these volatile organic constituents were
found to undergo extreme variations over the duration of the gasifi-
cation tests, i.e., up to three orders of magnitude in most cases.
6.2.3 Semivolatile Organic Products
Table 16 presents results obtained by solvent partitioning of
various tar products resulting from RTI operations and other coal con-
version operations. Samples H-l, B-l, and B-2 were obtained to use in
this study for the initial testing of the efficacy of the partitioning
procedure. The procedure in its present form eliminates losses due to
69
-------
TABLE 15. ORGANIC COMPOUNDS ADSORBED FROM PRODUCT GAS STREAM
GAS STREAM CONCENTRATION (yg/1)
Run
Compound
Cenzene
Thiophene
Toluene
Xylene*
Phenol
Dimethyl Phenol
C_-Alkyl Phenol
Naphthalene
Uphenyl
Anthracene
ndane
2
Upstream
Tenax
5.4
2.0
7.6
0.13
0.3
1.1
0.5
9.8
2
Steady-
State
XAD
160
14
1.3
4
Upstream
Tenax
50
6
0.3
0.2
1.3
52
0.075
TR
4
Steady-
State
XAD
1.7
0.4
0.07
6
Upstream
Tenax
7.7
1.3
5.7
9.9
1.9
35
6
Steady-
State
XAD
•
17.8
23.7
49.7
0 4
0.06
4.4
16
Surge
XAD
78
16
TR
61
0.7
3.2
16
Steady-
State
XAD
2.6
1.4
15.8
0.3
0.61
16
Tenax
NO. 2
1,100
150
125
>52
81
8
16
Tenax
No. 4
60
2.2
872
4.2
16
Tenax
No. 6
12.6
0.8
6.9
1.0
13.0
1.8
83
1.2
-------
TABLE 15 (cont'd)
Run
Compound
fethanethiol
[Methyl Mercaptan)
Oesols*
Xbenzofuran
:luorene
Fluoranthene
'yrene
enzothlophene
* Dimethyl phenol)
Acenaphthene
2
Upstream
Tenax
2.3
2
Steady-
State
XAD
4
Upstream
Tenax
0.1
0.2
4
Steady-
State
XAD
6
Upstream
Tenax
(0.07)
6
Steady-
State
XAD
68.1
(1.6)
0.4
16
Surge
XAD
12
TR
2.7
0.4
16
Steady-
State
XAD
0.53
0.1
TR
TR
3.7
16
Tenax
NO. 2
43
16
Fenax
No. 4
16
Tenax
No. 6
6.3
1.3
TR - Trace Quantity
NQ -Not Quant Hated
* - Includes Isomers
( ) = Tentative Identification
-------
(RUN 16)
10.000
o
o
1,000
100
10
O= BENZENE
A« THIOPHENE
O= TOLUENE
O= XYLENES
• = NAPTHALENE
^7= INOANE
*= CRESOLS
100
200
260,
Time, Min.
Figure 19. Gas product/contaminants during run 16.
72
-------
TABLE 16. WEIGHT PERCENT OF VARIOUS TAR FRACTIONS
VIA PARTITION PROCEDURE
Sample No.
(Source)
H-l
B-l
B-2
Run 6*
(RTI)
Run 16*
(RTI)
Total Tar
(9)
—
—
--
15.9
48.7
Nonpolar
Neutrals
(X)
3.2
7.5
20.1
13.0
29.8
Polar
Neutrals
(X)
12.1
5.6
8.6
13.8
8.1
Organic
Acids
(X)
14.2
3.4
2.7
30.3
13.2
Organic
Bases
(X)
1.3
41.9
1.5
12.5
6.0
PNA
(%)
18.3
22.8
38.9
16.5
33.3
Insolubles
(X)
13.6
13.5
4.4
13.9
9.6
*Partition procedure used with samples of Runs 6 and 16 was a modification of
that used with sample H-l, B-l, and B-2; the modification eliminated losses
due to the existence of emulsions.
TABLE 17. WEIGHT PERCENT RECOVERY VIA MODIFIED PARTITION
PROCEDURE WITH MODEL COMPOUNDS
Sample No.
(Source)
Sample
Mass
(g)
Nonpolar | Polar | Organic] Organic] |
Neutrals .Neutrals, Acids , Bases , PNA Insolubles
(X) ' (X) I (X) I (X) I (X) I (X)
CLS-1
(RTI)
CLS-2
(RTI)
0.258 | 22.2 | 97.3 | 92.3 | 94.8 I 75.8
0.031 | 80.2 | 72.0 | 97.2 | 96.4 |lOO
73
-------
the existence of emulsions by use of a particular wash sequence. This
procedure is displayed in Figure 20 with underlines denoting the modifi-
cations (updated steps) that have been introduced to the procedure.
Table 17 displays information on the validation of the modified
partitioning procedure. Validation was conducted using model organic
compounds. It employed benzoic acid and phenol (organic acids), quinoline
(organic base), hexadecane (nonpolar neutral), ethylene glyocol (polar
neutral) and phenanthrene (PNA). These results are regarded as quite
acceptable with one exception. The 22.2 percent recovery for the hexa-
decane in Sample No. CLS-1 is regarded as a spurious result. About 97
percent recovery has been achieved for nonpolar substances in subsequent
tests.
Three fractions from the partitioning of the tars collected during
Run 6 have been analyzed using high resolution capillary column gas
chromatography analyses/mass spectrometer detection/computer data pro-
cessing. Figure 21 and Table 18 present these results for the organic
acid fractions. Thirty-one compounds were identified in the organic
acid fractions, 17 of which were phenol-type compounds. Section 7.5 of
this report discusses the hazard potential of the various organic com-
pounds which have been detected in this study.
Figure 22 and Table 19 present the results of the organic base
fractions from the tar material of Run 6. Some 40 compounds have been
identified in this fraction, most of which are nitrogen-containing
organic compounds representing substituted pyridines, quinolines and
carbazoles. The phthalate esters detected in the organic acid and the
organic base fractions may well represent artifacts resulting from
plasticizers that have been utilized in the manufacture of plastic
components of the gas sampling system.
Figure 23 and Table 20 show the output achieved for the polynuclear
aromatic (PNA) fraction from the tar collected during Run 6. These com-
pounds range from two to five condensed aromatic ring structures. The
74
-------
Particulace Extract
Wash 3X with LM NaOH
CH2C12 layer
Wash 2X wlch
I
-- NaOH layers
CH.C1- layer H20 layer
* * (pH-10)
Wash 2X with
Wash with
Wash with CH2C12
CH-
layer
\
NaOH layer
1
10Z
and
ch
20Z H,SO,
Adjust to pH 2 with 6N HC1
Extract with CHC1
| Organic Acids]
AQ
Cyclohexane layer
(1) Evaporate to
dryness.
(2) Dissolve in
H.,0 layer
CHjCl. layer •
Wash 2X with
H20
layer
Wash 2X wlch
Adjust to pH 2 with IN HC1
Extract 3X with CHC1
I Organic Acids]
AQ
laver
I
H2SOA layer
Adjust to pH 12 wlch 10Z NaOH
Extract 3X with CHCl
CH.C1. layer- H20 layer
(pH-5)
Evaporace to
1
dryness
[Organic Bases|
I
AQ
Wash SX with
Cyclohexane
Insolubles
1- Extract CH2C12
(1) Added
cyclohexane
(2) Wash 3X with
4:1 CH3OH/H20
R20 layer
Adjust to pH 12 with 1M NaOH
Extract 3X with CHCl
±
[Organic Bases]
AQ
Cyclohexane layer
at.
(1) Concentrate
(2) Wash 6X with CHjNOj
CH2OH/H20 layer
Wash 4X with cyclohexane
r
Cyclohexane layer
jS02 layer
|
Evaporate to
dryness
Cyclohexane layer
Evaporate to dryness
CH,OH/H,0 layer
•* I *
Freeze dry
j-
1 Polar Neutralaj
|Son-Polar Neutrals|
Figure 20. Modified partition scheme for semivolatiles,
75
-------
500 600
Mass Number (a.m.u.)
800
100
200
300
400
Figure 21. Total ion current plot.
500 600
Mass Number (a.m.u.)
Semi volatile organic acid fraction from run 6.
700
-------
Chroma to-
graphic
Peak No.
1
2
3
3
4
5
6
7
7
8
8
9
10
11
11
11
12
TABLE
Elution
Temp.
CO
74
87
90
91
94-102
106-109
110
115
115
121-122
122
129
129
132
133
134
137
18. COMPOUNDS IDENTIFIED IN THE SEMIVOLATILE ORGANIC ACID
FRACTION FROM RUN 6
Compound
phenol
o-cresol
p-cresol
m-cresol
zylenols
ethylphenols
C.-pnenol
methylethylphenol
o- and m-hydroxyacetophenone
methylethylphcnols
crime thy Iphenol
o-allyl phenol
cerephthal aldehyde
7-methylbenzo (b) fur an
2-methyl-5-phenyltetrazole
vinylphenylcarbazole
phenyl-2-propynyl ether
Chromato-
graphic
Peak No.
13
14
15
16
16
17
18
19
20
21
22
22
23
23
23
24
Elution
Temp.
CO
144
151
160
162
163
167
173
178
189
198
201
202
235
235
236
265
Compound
p-ethylacetophenone
i-butyl cinnamate
dl-t-butyl-4-ethylphenol
B-naphthol
o-nitroso-8— naphthol
d-naphthol and phthalates (plasticizers)
a-methoxynaphthalene
B— methoxynaphthalene
1, 2-dlhdro-3, 5 , 8-trimethylnaphthalene
phthalates (plasticizer)
dl-butyl phthalates (plasticizer)
dicyclohexylphthalate (plasticizer)
2-n— propyl-5— i-butylthiophene
4— t-butyl phenoxymethylacetate
4 , 9-dimethy 1 naphthol ( 2 , 3-b ) thiophene
butyl phthalyl butyl glycolate
77
-------
oo
~l I—I—I—I—I—I—I—I—1—I—I—I—I—I—I—I—I—I—I—I—I—1—1—I—I—I—I—I—I—I
TEMPERATURE
Figure 22. Total ion current plot. Semivolatile organic base fraction from run 6.
-------
TABLE 19. COMPOUNDS IDENTIFIED IN THE ORGANIC BASE
FRACTION FROM RUN 6
Chromato-
graphic
Peak No.
1
2
3
4
5
6
7
8
9
10
11
11
12
13
14
14
15
16
16
17
18
18
19
20
20
21
22
22
Elucion
Temp.
Co
103
114
117
122
126
140
140
141
144
145
154
154
154
156
157
157
160
162
162
164
166
166
168
170
170
173
175
175
Compound
pyridine
N-methyl-o-toluidine?
4-acecyl pyridine
quinoline butiodide
2,6-
-------
00
o
ts>
1 1 1 1 \ 1 1
TEMPERATURE
Figure 23. Total 1on current plot. Semivolatile PNA fraction from run 6.
-------
TABLE 20. COMPOUNDS IDENTIFIED IN THE SEMIVOLATILE PNA
FRACTION FROM RUN 6
Chronato-
graphic
Peak No.
1
2
3
4
4
5
5
6
7
8
9
9
10
11
12
13
14
14
15
15
16
17
18
19
20
20
21
22
23
24
24
25
26
27
28
29
30
31
31
Elucion
Temp.
CO
117
124
130
134
134
137
137
139
150
152
165
165
166
169
172
174
178
178
181
181
182
184
186
187
190
190
192
193
194
198
198
198
199
202
210
213
215
218
219
Compound
methyl phenyl acetylene?
7-methylbenzo(b)furan
methyl indenes
naphthalene
2.3-dihydro-2-methylbenzofuran
l-hydroxy-2-methyl-4-ethyl-
benzene
hydroxyacetophenone?
1-methy 1-4-nor-hexy 1-1 ,2,3,4-
tetrahydronaphthalene
2-methylnaphthalene
1-methylnaphthalene
ethylnaphthalene
2 , 6-dime thy Ibenzo (b) thiophene
1,5-2,6-2,7-, and 1,6-di-
methylnaphthalene
1,5- and 2,3-dlmethyl-
napb.thaJ.ene
1 , 3-dimethy Inaphthalene
1 , 2-dlmethy Inaphthalene
acenaphthene or biphenyl
methylbiphenyl
2-ethyl-5(or 7)-oethylbenzo(b)
thiophene
2-i-propylnaphthalene
dlbenzofuran
propylnaphthalene
propylnaphthalene
propylnaphthalene
fluorene
propylnaphthalene
fluorene
l,3-dihydro-4,6-dlmethyltnieno
(3 ,4-c) thiophene
2-methylbiphenyl or fluorene
2-hydrozyfluorene
fluorene
2-tert-butylnaphthmlen«
2-hydroxyfluorene
l-methyl-7-lso-propyl-
naphthalene?
1-oethylfluorene
methozyfluorenes
methozyfluorenes or ortho- and
para-phenylanl«ole
phenanthrene
anthracene
Chromato-
graphic
Peak No.
32
33
34
34
35
35
36
36
37
38
39
40
40
41
42
43
44
45
46
47
48
49
49
50
50
50
51
51
52
52
52
52
53
53
53
54
54
54
55
55
56
57
58
Elution
Temp.
CO
224
230
231
231
234
236
239
239
240
242
244
252
252
253
255
256
258
261
263
264
265
265
265
265
265
265
265
265
265
265
265
265
265
265
265
265
265
265
265
265
265
265
265
Compound
dimethylfluorene
3-methyldibenzo thiophene
phenyl X-xylyl ketone?
me thy Idibenzo thiophene
me thy Id ibenzo thiophene
methylphenanthrene
N-metbylcarbazole
methylcarbazole isomer
methylcarbazole isomer
tetrahydroanthraquinone?
4,5-dimethyl-9,10-dlhydro-phenanthrene?
dime thy Iphenanthrenes
pyrene
pyrene
8-nor-butyl-phenanthrene?
ethylanthracene
pyrene
1-methy Ibenzo (1, 2-b : 4 , 3-b)-dithiophene
hexadecapyr ene ?
trimethylphenanthrene?
1-methylpyrene
crlmethylphrenanthrene
methylpyrene
methylpyrene
trimethylphenanthrene
1 , 4-dimethylanthracene
1,2,3, 4-tetrahydrotriphenylene
1, 4-dihydro-2, 3-benzcarbazole
tetr ahydro tr ipheny lene
dihydrobenzcarbazole
methylpyrene
4.4' -dichloroblpheny 1?
tetrahydrotriphenylene
methylpyrene
dihydrozyanthraquinone
butyl phthalyl butyl phthalate
(plasticizer)
3-nor-hezylperylene?
3 , 6-dimethozyphenanthrene
3,3'-Bi-indolyl
4,4' -dichlorobiphenyl
1 , 2-diphenybenzene
1, 4-diphenylbenzene
1 , 3-diphenylbenzene
81
-------
Table 20 (cont'd)
Chromato-
graphic
Peak No.
59
60
61
62
62
63
EluCion
Temp.
CO
265
265
265
265
265
265
Compound
hexahydrobenzo (a) anthracene
diphenybenzene
criphenylene
di-nor-octylphthalate (plasticizer)
di-2-echylhexylphchalate
(plastlcizer)
mechy Ibenzo (a) anthracene or
3-methylchrysene or
2-methylcriphenylene
Chromato-
graphic
Peak No.
64
65
66
67
67
68
Elution
Temp.
CO
265
265
265
265
265
265
Compound
5-methy Ibenzo (a) anthracene?
9-, 10-, or ll-methylbenz(a)-
anthracene
perylene? or benzpyrene?
5 , 8-difflethy Ibenzo ( c ) phenanthrene ?
benzpyrene or perylene
3-methylacenaphthylene
82
-------
two-ring compounds are represented by benzofuran, methyl indene or
naphthalene. Five-ring structures are benzopyrene or perylene.
The tar product from Illinois No.6 coal obtained in Run 16 has been
analyzed to yield results shown in Table 21. These compositions expressed
in percent by weight are compared to those obtained with tar from the
Morgantown Energy Research Center (MERC) fixed-bed coal gasification
unit. These results indicate that a wide variety of complex organic
compounds is present in the coal gasifier tar product. This same con-
clusion is supported by results that were obtained utilizing low ionizing
voltages with a direct probe mass spectrometer with these tar products
from Illinois No.6 coal. The direct probe mass spectrometer results are
summarized as follows:
1. Tar acids — about 50 significant peaks at 300 to 500 amu, 50
minor peaks at 350 to 400 amu, and few peaks beyond about 420
amu (190°C).
2. Tar bases -- major components at 200 to 350 amu, about 70
minor components at 400 to 470 amu, and few peaks beyond 470
amu (235°C).
3. Nonpolar neutrals -- significant peaks up to 450 amu (230°C).
4. Polar neutrals — major components at 200 to 400 amu, about 60
minor components from 540 to 620 amu, and few peaks beyond
about 630 amu (230°C).
5. Polynuclear aromatics -- major peaks at 178 to 350 amu in
increments of 24 to 26 amu, and few peaks beyond 380 amu.
83
-------
TABLE 21. QUANTITATION FOR SEMIVOLATILE ORGANIC COMPOUNDS
IN COAL GASIFIER TAR PRODUCT
Compound
RTI
Illinois No.6 Coal
Pittsburgh Coal
Naphthalene
Anthracene
Fluoranthene
Phenanthrene
Benzidine
Pyrene
m-Cresol
Phenol
o-Cresol
Fluorene
Dibenzofuran
1.97
1.31
0.71
0.41
0.36
0.21
0.04
0.03
0.02
0.01
0.001
3.00
NA
0.01
0.55
NA
NA
1.20
0.62
0.57
1.19
1.14
84
-------
7.0 DISCUSSION OF RESULTS
The results which have been obtained in preliminary tests deal with
the performance of the coal gasification reactor process, the degree of
conversion of coal and coal char feed material and the initial charac-
terization and quantitation of the chemical constituents of the primary
gaseous product stream, the volatile organic products and the semivolatile
organic materials. The gasification reactor system, the signal processing
and control system, the product sampling system and the chemical analysis
procedures have all been developed, tested and implemented. A full
program of testing and study of pollutant formation has started on a
variety of solid feed material using various selected operating con-
ditions.
7.1 FEED CONVERSION
The gasification studies that have been conducted to date utilized
either a char from Western Kentucky coal or raw Illinois No.6 coal. These
runs were conducted at a pressure of 1.5 MPa (200 psig). Steam was fed
to the conversion reactor in all the runs whereas only runs designated
as combustion heat runs used an air feed stream. The external vertical
furnace on the reactor was operated during each run so as to achieve a
predetermined temperature vs. time history for the reaction process.
The operability of the reactor system was thus demonstrated for achieving
desired operating conditions.
As the bed temperature increased, the relative proportion of
hydrogen in the effluent gas from char gasification was found to dramat-
ically increase. This indicates that as the bed temperature increases,
hydrogen is produced by the reaction of steam with the char material.
Both the char/steam and the char/oxygen reactions are known to have a
substantial temperature dependence. These reactions are discussed in
Appendix I of this report. Reaction rates, in general, increase with
temperature. For the conditions experienced to date, the rates of feed
85
-------
conversion have been more than twice as great in the combustion heat
runs compared to the runs in which no air or oxygen was fed to the
reactor.
Gasification of Illinois No.6 coal in the RTI reactor initially
involves the devolatilization of the coal. Dramatic changes are seen
during the early periods of these runs regarding the volatile matter
content of the coal as well as the sulfur content (cf., Tables 2-6).
Primary gas stream compositions similarly indicate that initial
devolatilization takes place and results in a high level of methane
formation in the reactor (cf., Figures 7-9).
Sufficiently complete information is available on Runs 2, 4, 6 and
16 of the runs completed to date to provide insight as to the influence
of the steam and air rates on the gasification process. The air-to-
steam mass ratios were 1.0 and 0.5 for Runs 2 and 16, respectively. No
air was used for Runs 4 and 6. Hence, Runs 2 and 16 are designated as
combustion heat test runs and Runs 4 and 6 are regarded as external heat
test runs. A comparison of Runs 6 and 16 indicates that the level of
sulfur conversion was effectively the same for these two runs, i.e.,
about 90 percent. Yet, more feed material and a higher carbon content
of that material was consumed in Run 16 over essentially the same time
period. In particular, the gasification rate for Run 16 was approximately
2 2
42 kg/hr m as compared with 20 kg/hr m for Run 6.
Generally, the coal gasification reactor and its accessories have
been demonstrated to be able to simulate operating conditions character-
istic of those prevailing in commercial and/or developmental gasification
reactors. Operating conditions and primary gas stream compositions
have been tabulated for use in the selection of operating conditions for
the test runs (cf., Tables 7 and 8). Reactor operating parameters for
future test runs will be varied in order to study the influence of the
reaction operating conditions upon the nature and concentration of the
various pollutants which result from the process. Parameters will
include air-to-steam mass ratios up to about 10.0, pressures to 2.3 MPa
(300 psig) and various operating temperatures in order to encompass the
range of operating conditions of practical significance.
86
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The tests conducted to date have been in the fixed bed reactor con-
figuration. Lurgi coal gasifiers^26'27'30^ in commercial use are of
this type. Fixed bed reactors for use with U.S. coals have been under
development for a number of years.t2*7'14*31] Hence, it is clear that
the fixed bed configuration is an important one for investigation. In
addition, it is anticipated that experimental studies in a fluidized bed
configuration will be feasible as a part of the current project. Fluidized
bed coal gasifiers and combustion units are also under active development
in this country. A leading example is the Synthane process system'-9'16'25-'
at the Pittsburgh Energy Research Center.
7.2 PRIMARY GASEOUS PRODUCTS
There are six primary gas products with concentrations generally in
the 1 percent by volume level or greater. These are nitrogen, hydrogen,
carbon monoxide, carbon dioxide, methane and hydrogen sulfide. Steam is
also present in the product gas stream. However, condensation occurs
within the tar trap and the gases are dried prior to chemical analysis.
Gas composition values are expressed on a moisture-free basis.
As was anticipated, the composition of the effluent gas stream
varies appreciably with changes in the type of feed material as well as
changes in the feed rates of steam and air. In addition, the operating
temperature has been found to influence the composition of the product
gas stream (cf., Tables 4-6 and Figures 7-12). Generally, it is known
that steam is consumed by both the carbon/steam reaction and the water-
gas shift reaction. These reactions produce hydrogen, carbon monoxide
and carbon dioxide. Based on the methane levels obtained in the runs
reported herein, it is clear that some of the hydrogen reacts with the
carbon to produce methane. The carbon-hydrogen reaction may in fact be
the predominant mode of methane formation after the initial devolatil-
ization period.
The amount of gas product resulting from the gasification of a unit
weight of feed material was found to be 2.7 to 2.9 Nm3/kg for each of
the coal runs. With char feed material, however, the measured rates of
effluent gas per unit weight of char converted were higher since more
87
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reactant gas passed through the reactor per unit of feed material con-
verted (cf., Table 7).
7.3 VOLATILE ORGANIC PRODUCTS
High levels of ethane, ethylene, carbonyl sulfide, methyl mercaptan
and thiophene were measured during the devolatilization process for the
runs involving Illinois No.6 coal (cf., Tables 4-6 and Figures 10-12).
Ethane and hydrogen sulfide concentrations as high as 3.85 and 3.45
percent, respectively, were detected after 45 minutes of reactor
operation in Run 6. These values dropped off to steady-state levels of
approximately 5000 ppm and 20 ppm for the hydrogen sulfide and ethane,
respectively. Propane and propylene were also detected in the ppm con-
centration range as products of the devolatilization process. The
behavior of those constituents associated with devolatilization was
found to be quite distinct from those associated with the char gasifi-
cation process. The devolatilization products were found to reach
maximum values quite rapidly or to be at high levels initially and then
decay quite rapidly to very low levels. This was characteristic of
ethane, ethylene, propane, propylene, methyl mercaptan and thiophene.
Alternatively, hydrogen sulfide and carbonyl sulfide reached effectively
level values for extended periods of time, i.e., four hours and beyond.
In addition to the volatile organic constituents of the primary gas
streams that were analyzed via direct gas chromatographic techniques,
other volatile organic compounds were present at low levels and/or
possessed somewhat higher boiling points. They were removed from the
gas stream using either Tenax or XAD-2 adsorbent cartridges. The Tenax
was found to be most effective for adsorbing polar compounds such as
alcohols, glycols, diols, phenols, amines, amides, aldehydes and ketpnes.
Further, it was effectively desorbed upon heating. The XAD-2 adsorbent
was found to be particularly effective for aromatic hydrocarbons, which
can form pirpi bond complexes with its structure. Organic compounds
were removed from the XAD-2 material via Soxlet extraction using
methylene chloride. The procedure for sample collection and sample
retrieval from these adsorbents has been validated for use in this
project.
-------
Numerous compounds were found in the products of the gasification
tests at concentrations at the microgram/liter level (cf., Figures 13-
18). The Tenax cartridge samples collected from the gasification of
char showed prominent peaks that have been interpreted as benzene,
toluene, thiophene, phenol and naphthalene. The gasification tests with
Illinois No.6 coal yielded additional prominent peaks from the sample
collected via the Tenax adsorbent material. These peaks represented
primarily benzene, thiophene, methyl thiophene, phenol, cresols, alkyl-
substituted benzenes, benzofuran, methyl-substituted benzofuran and
naphthalene.
The XAD-2 resin was more effective for removing compounds having
boiling points just above benzene, i.e., toluene, phenol, thiophene,
derivatives, indene, cresols, naphthalene, etc. This resin therefore,
is particularly effective in accumulating the organic compounds that are
present in lower concentrations and are less volatile (cf., Figures 16
and 18).
A quantitative determination of concentrations of compounds of
interest used both internal and primary standard samples with the mass
spectrometer system. For the Illinois No.6 coal used in Run 6, the
prominent peaks resulting from the XAD-2 resin were xylenes, phenol,
indan, indene, cresols, methyl indene and naphthalene. The concen-
trations of the phenol, indan and naphthalene were 23.7, 4.4, and 49.7
mg/m3, respectively. Additional PNA compounds identified in the sample
at 0.1 mg/m3 or greater were e-methyl naphthalene, biphenyl, acenaphthalene
and anthracene. Section 7.5 of this report deals with the potential
hazard associated with these compounds.
7.4 SEMIVOLATILE ORGANIC PRODUCTS
The organic compounds that were collected in the tar trap are
referred to as semi volatile organic compounds since these materials have
very high boiling temperatures. Water also condenses in this trap. Thus,
organic compounds in the effluent stream possessing a relatively high
water solubility accumulate to some degree in this trap. They include
89
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phenol and cresols. The partitioning scheme developed for use in this
project has been validated relative to its capability for separating the
tar produced into the categories of organic acids, organic bases, polar
neutral compounds, nonpolar neutral compounds, PNA hydrocarbons and
cyclohexane insoluble material.
Various analytical methods have been studied for use in the
analysis of the fractions resulting from partitioning of the tars. The
methods include exclusion chromatography, reverse phase chromatography,
nuclear magnetic resonance analysis and direct probe mass spectrometry.
The greatest success has been achieved utilizing capillary chromatography
columns with temperature programming and GC/MS detection for these
semivolatile compounds. The use of low ionizing voltages with a direct
probe mass spectrometer has made it possible to detect the parent com-
pounds for these semivolatile organic materials.
The primary results obtained to date for the chemical analysis of
the organic .acids, organic bases and PNA compounds have been achieved
using high resolution capillary column gas chromatographic analysis/mass
spectrometer detection/computer data processes (cf., Figures 21-23 and
Tables 18-20). Almost without exception, the organic acids were found
to be oxygen-containing compounds. These include phenols, furans,
ethers, etc. The organic bases were primarily nitrogen-containing
compounds including derivatives of pyridine, quinoline, carbazole,
diphenyl amine and other compounds. The PNA fractions showed condensed
ring aromatic structures from two to five rings as the predominant
material. These include naphthalene, fluorene, phenanthrene, anthra-
cene, pyrene, methyl pyrene, triphenylene, and benzpyrene. A few
compounds containing hetero-atoms were also detected in the PNA
fractions. Some of these were derivatives of benzofuran, hydroxy-
fluorene, methyl carbazole, etc. The following section of this report
discusses the potential hazards associated with many of these compounds.
90
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7.5 EVALUATION OF RESULTS
This report on pollutant production from synthetic fuels has in-
volved equipment construction, installation and preliminary testing.
The results that have been obtained to date on the gasification of char
and coal are for a relatively narrow range of operating conditions. The
initial emphasis has been placed upon achieving the successful operation
of the reactor and sampling system as well as the reliable chemical
analysis of the various compounds generated in the gasification process.
The gasification tests have been conducted at high steam partial pressures
and low or zero air flow rates. In all cases, external heat has been
applied to the reactor utilizing the vertical reactor furnace. Carbon
conversions have been carried to about 88 percent for some 2 kg of coal
during the most exhaustive tests to date.
Preliminary evaluation has been made of the chemical analysis
results obtained for the gasification of char and raw coal. The results
show that very high levels of volatile and semivolatile organic compounds
are produced during the initial period of the gasification run from the
volatile matter content of the raw coal. This material is made up of
many compounds and probably possesses a high hazard potential.^ ' ^
The tests which have been conducted with and without air flow indicate
that the presence of air generally tends to result in more internal heat
generation within the coal bed and subsequently higher local temperatures
within the bed. Higher levels of carbon monoxide on a nitrogen-free
basis were measured for those runs for which air was provided as one of
the feed streams, whether the primary reactant was char or raw coal.
The amount of tar material produced in the runs with raw coal was
quite substantial, i.e., of the order of 0.022 kg of tar/kg of coal
converted (40 Ibs of tar/ton of coal converted). The amount of gas
products formed/unit of coal converted was also substantial, some 2.8
Nm3/kg (45 scf/lb). These results for the tar and gas produced during
the RTI laboratory gasification tests with Illinois No.6 coal have been
found to be in very close agreement with results which have been obtained
91
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with this same coal on the fixed bed gasifier at the Morgantown Energy
hieved wit
'- » » » J
Research Center.*- ' '' Comparable values have been achieved with
other commercial and/or developmental gasification processes
(cf., Tables 7 and 8).
A list of 102 specific hazardous compounds that have been selected
for identification in this work is presented in Table 22. The compounds
listed in this table are either on the EPA Effluent Guidelines Division's
list of primary pollutants for BAT revision studies (consent decree
compounds), possess minimum acute toxic effluents (MATE) values which
are <_ 17 mg/m or are known to be associated with coal conversion pro-
cesses in relatively high concentrations. The MATE value of 17 mg/m or
less has been established in order that only compounds having a high
hazard potential will be included, yet the list of compounds so selected
would be of manageable proportion. This criterion also represents a
concentration level at which measurements can successfully be made
utilizing the chemical analysis techniques which have been selected for
use in this study. See Appendix II for a presentation of background
concepts on the use of MATE and EPC values as "multimedia environmental
goals."
Indication is provided in Table 22 as to which of the listed com-
pounds are on the consent decree list, which have been identified in the
effluents from the laboratory gasifier runs conducted to date and which
have been identified in effluents from other coal conversion operations.
In the latter category are those compounds which have been found in the
effluent stream from the fixed bed pilot gasifier at the Morgantown
Energy Research Center*- ^ and those which have been reported in the
effluent from coal liquefaction operations'- '-' as well as those from
coal coking operations. •*
Of the 102 specific hazardous compounds listed, 42 are consent
decree compounds. A total of 25 hazardous compounds have been
identified in the effluent stream from the RTI gasifier, 21 have been
identified in effluents from the MERC gasifier, 39 in the products of
various coal liquefaction operations and 52 in the products of coal
coking operations. Some 33 of the 102 compounds on the list are PNA
materials. Of these 33, 14 have been detected in the effluents from the
RTI laboratory gasifier to date.
92
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TABLE 22. LIST OF SPECIFIC HAZARDOUS COMPOUNDS FOR
MEG's
No.
02A020
02A040
02A080
02A250
02B020
03B060
04A020
05B100
07A020
07A060
07B080
08A160
08B060
08B100
08D280
09A040
09A060
10A040
10A060
10A140
10C040
10C080
10C100
10C120
10C140
10C200
10C220
11A020
11B020
11B080
Consent
Decree
Compounds Name
* Methyl Bromide
* Methyl Chloride
* Methyl ene Chloride
* Chloroethane
* Vinyl Chloride
1,4-Dioxane
Chloromethyl Methyl Ether
1-Phenyl Ethanol
Formaldehyde
* Acrolein
* Isophorone
Phthalic Acid
3-Hydroxypropanic Acid
B-Propiolactone
* Phthalate Esters
* Acrylonitrile
1-Cyanoethane
Ethyleneimine
Ethanol ami ne
Butyl amines
Aminotoluenes
Anisidines
1,4-Diaminobenzene
4-Aminobiphenyl
* Benzidine
1-Aminonaphthalene
2-Aminonaphthalene
Diazomethane
Monomethylhydrazine
* 1 ,2-Diphenylhydrazine
J 1 UU 1
I II III IV
Coal Coal
Type RTI MERC Liq. Coking
PN
PN
PN
PN
PN
NN
PN
PN
PN XX
PN
PN
TA
TA
PN
PN X
TB
PN
TB
TB
TB
TB X
TB
TB
TB
TB
TB X
TB X
TB
TB
TB
continued
93
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TABLE 22. LIST OF SPECIFIC HAZARDOUS COMPOUNDS FOR
IDENTIFICATION IN THIS STUDY (continued)
Consent
MEG's Decree
No. Compounds
12B020
13A020
13A040
1 3A080
13A100
14B020
1 5A020 *
1 5A040 *
1 5A060 *
15A160
15B020
1 5B080
1 6A020 *
1 6A202 *
1 6B020
17A020 *
17A060
18A020 *
18A041
18A042
18A140
18A142 *
18A144
18B060
1 9A020 *
1 9A040 *
20A020 *
20A040
20A060 *
20A100 *
Name
N-Methyl -N-Ni troso-Ani 1 ine
Methyl me rcaptan
Ethanethiol
n-Butanethiol
Benzenethiol
Dimethyl Su If oxide
Benzene
Toluene
Ethyl Benzene
Biphenyl
Indane
Xylene
Chlorobenzene
2-Chloronaphthalene
a-Chloro toluene
Ni trobenzene
4-Nitrobiphenyl
Phenol
Cresol
m-Cresol
Xylenols
2,4-Xylenol
2,6-Xylenol
1 ,4-Dihydroxybenzene
2-Chlorophenol
2,4-Dichlorophenol
2-Nitrophenol
3-Nitrophenol
4-Nitrophenol
2 ,4-Dini trophenol
Type
TB
PN
PN
PN
PN
PN
PNA
PNA
PNA
PNA
PNA
PNA
PN
PNA
PNA
PN
PN
TA
TA
TA
TA
TA
TA
TA
TA
TA
TA
TA
TA
TA
I
RTI
X
X
X
X
X
X
X
X
X
X
X
X
II III
Coal
MERC Liq.
X
X X
X X
X X
X X
X X
X X
X X
X X
X X
X X
X
IV
Coal
Coking
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
continued
94
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TABLE 22. LIST OF SPECIFIC HAZARDOUS COMPOUNDS FOR
MEG's
No.
21A020
21A100
21A120
21A140
21A180
21B040
21B060
21B080
21B101
21B120
21B180
21C080
21C100
21C160
21D020
21D040
21D080
22A020
22B040
22C020
22C040
22C080
23A020
23B020
23B220
23B240
23C020
23C160
23C180
23D020
24B020
25A020
Consent
Decree
Compounds Name
* Naphthalene
* Acenaphthene
* Acenaphthvlene
* Anthracene
* Phenanthrene
* Benz(a)anthracene
7 , 1 2-Dimethyl benz ( a ) anthracene
3-Methyl chol anthrene
Benzo(c) phenanthrene
* Chrysene
* Pyrene
* Dibenz(a,h)anthracene
* Benzo(a)pyrene
Picene
Dibenzo(a,h)pyrene
Dibenzo(a,i)pyrene
* Benzo(ghi)perylene
* FT uorene
* Fluoranthene
* Benzo(k)fluoranthene
Benzo(j)fluoranthene
* Benzo(b)fluoranthene
Pyridine
Quinoline
Dibenz(a,j)acridine
Dibenz(a,h)acridine
Pyrrole
Dibenzo(c,g)carbazole
Dibenzo(a,g)carbazole
Benzothiazole
Dibenzofuran
Thiophene
v V-UII 11111
Type
PNA
PNA
PNA
PNA
PNA
PNA
PNA
PNA
PNA
PNA
PNA
PNA
PNA
PNA
PNA
PNA
PNA
PNA
PNA
PNA
PNA
PNA
TB
TB
TB
TB
TB
TB
TB
TB
PNA
PNA
jcu ;
I II III
Coal
RTI MERC Liq.
XXX
XXX
x
XXX
X X
X
X
X
X X
X
XXX
XXX
X
X
X X
X
X
X
X
X
XXX
XXX
continued
IV
Coal
Coking
x
x
x
X
X
X
X
X
X
X
X.
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
95
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TABLE 22. LIST OF SPECIFIC HAZARDOUS COMPOUNDS FOR
IDENTIFICATION IN THIS STUDY (continued)
MEG's
No.
25B080
42B100
45B100
46B900
46B920
47A360
47B160
76B900
78B900
83B900
Consent
Decree
Compounds Name
Benzonaphthothiophene
* Carbon Monoxide
Organotin
Tetramethyllead
Tetraethyllead
* Cyanides
* Ammonia
Nickel ocene
Copper-8-Hydroxy-
quinoline
Alkyl Mercury
I
Type RTI
PNA
PN X
Organometals
Organometals
Organometals
PN X
NN X
Organometals
Organometals
Organometals
II
MERC
X
X
X
III
Coal
Liq.
X
X
X
X
IV
Coal
Coking
X
X
X
X
NN
PN
TA
TB
PNA =
I
II
III =
IV
Nonpolar neutral compounds.
Polar-neutral compounds.
Organic acidic compounds.
Organic basic compounds.
Polynuclear aromatic compounds.
Compound(s) identified in products of coal gasification in this study.
Compound(s) identified in products of MERC fixed-bed coal gasifier.
Compound(s) identified in products of coal liquefaction experiments.
Compounds identified in products of coal carbonization (coking-
operations).
96
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The chemical nature of essentially all of the compounds which have
been detected in coal conversion operations is judged to be consistent
with the basic chemical nature of the starting material. There are two
exceptions to this in Table 22. First, phthalate esters were detected
in the RTI laboratory gasifier. This material may be an artifact, i.e.,
a result of plasticizer which was present in the plastic components of
the fittings utilized in the gas sampling system. Second, 3-methyl
cholanthrene is reported to have been detected in coal liquefaction
operations. This compound typically occurs environmentally via the
pyrolysis of cholesterol.
Since the operating temperatures, pressures, and feed materials for
coal gasification processes encompass the range of variables typical for
many coal liquefaction and/or coal coking processes, it is likely that
any of the compounds which have previously been identifed in coal lique-
faction or coal coking operations may at some time be identified in a
product of a coal gasification process. The work plan for this project
should allow clear delineation of those operating conditions under which
various compounds are formed as well as the concentrations of these com-
pounds in the effluent stream. Such information is essential to a full
and complete evaluation of the occupational health and safety as well as
the environmental hazard potential of coal gasification processes.
An initial effort to identify and analyze the environmental hazard
represented by the effluent stream of RTI's coal gasification reactor
has been performed utilizing the preliminary data resulting from the
runs which have been conducted on Illinois No.6 coal. These results are
presented in Table 23. The maximum concentration measured for various
hazardous compounds is tabulated. Values detected for the gas stream as
well as concentrations measured in the aqueous condensate are presented.
Those concentration values which exceed their corresponding MATE values
are identified with an asterisk. The table also contains the MATE
values and Estimated Permissible Concentrations (EPC) for comparison. A
MATE value is the estimated concentration of a contaminant in air (or
water) which will not result in adverse effects to human health provided
97
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TABLE 23. GASIFIER POLLUTANTS COMPARED TO MINIMUM ACUTE TQXICITY EFFLUENT
LIMITS AND ESTIMATED PERMISSIBLE CONCENTRATIONSL5]
Compound
Naphthalene
Biphenyl
Anthracene
Benzene
Thiophene
Carbonyl Sulfide
Hydrogen Sulfide
Methyl Mercaptan
Toluene
Xylenes
Phenol
Cresols
Fl uorene
Fluoranthene
Pyrene
Phenanthrene
Benzidene
Dibenzofuran
Benzothiophene
Acenaphthene
Maximum Concentration
Recorded
gas water
yg/m yg/A
3.9E5*
1.4E4*
2.1E3*
1.1E6
3.8E3
4.5E2
1.3E8*
9.0E5*
1.4E7*
6.8E5*
2.4E4*
2.5E5*
1.0E2
2.7E3
4.0E2
1.6E3
8.E3
4.8E2
5.5E5
3.7E5
2.0E5*
3.4E5*
3.1E3
2.0E5
5.8E3
1.1E5*
1.0E5
3.1E2
MATE
air water
yg/m yg/A
5.0E4
1.0E3
5.7E4
3.0E3
4.5E3
4.5E5
1.5E4
1.1E3
3.7E5
4.35E5
1.9E4
2.2E4
9.0E4
2.3E5
1.6E3
1.4E4
2.3E4
7.5E5
8.4E5
4.5E4
6.7E4
5.0EO
5.0EO
1.4E6
0.45E6
2.4E4
2.1E5
air
yg/m3
119
2.4
133
71.4
8
800
364
2.1
893
1040
45
52
162
556
57
25
41
EPC
water
ygA
690
2000
414
40
260
304
800
8333
280
124
*value listed exceeds corresponding MATE value.
MATE = minimum acute toxicity effluent limit value.
EPC= estimated permissible concentration value.
98
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exposure is of limited duration. Such a value may represent the upper
limit to the acceptable concentration of that substance for an individual
pollutant source. The EPC is the estimated concentration of a substance
that will not result in toxic effects to humans or to the ecology for
continuous exposure. Such values are appropriate for use for ambient
air (or water) into which one or many pollution sources have been
dispersed. (See also Appendix II.)
As can be seen in Table 23, nine organic compounds were present in
the gasifier effluent stream in sufficiently high concentration to
exceed the appropriate MATE values for air contamination and three
compounds were present in sufficiently high concentrations in the
aqueous condensate collected during the run to exceed the appropriate
MATE value for water contamination. Hydrogen sulfide, methyl mercaptan,
benzene and toluene were the most prominent compounds exceeding their
MATE values in the gas phase. Phenol, cresols and phenanthrene were the
three compounds exceeding their MATE values for water.
It may "be noted that the presence of compounds in the reactor
effluent stream at concentrations which exceed the corresponding MATE
values does not imply the release of these compounds at the same concen-
trations. Once the various hazardous materials have been identified and
characterized, it should then be possible to design suitable control
systems for the removal of these materials. This provides justification
for this comprehensive study which aims to identify and characterize the
potentially hazardous compounds associated with synthetic fuels pro-
duction from solid materials.
99
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Fixed Bed Gas Producer," Proceedings Symposium on Coal Processing
and Conversion, West Virginia Geological and Economic Survey,
Morgantown, W. Va., March 1976.
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formation Overview," Oak Ridge National Laboratory, ORNL/EIS-94 &
95, Vols. 1 & 2, April 1977.
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Proceedings 1977 Lignite Symposium, Grand Forks, N.D., 1977.
8. Field, M. A., "Combustion and Flame," 1_4> 237 (1970).
9. Forney, A. J., et al., "Analyses of Tars, Chars, Gases, and Water
Found in Effluents from the Synthane Process," Pittsburgh Energy
Research Center, PERC/TPR-75/2, November 1975.
10. Gammage, R. B., "Proceedings of the Second ORNL Workshop on Exposure
to Polynuclear Aromatic Hydrocarbons in Coal Conversion Processes,"
Oak Ridge National Laboratory, CONF-770361, December 1977.
11. Gillmore, D., and A. J. Liberatore, "Pressurized, Stirred, Fixed-
Bed Gasification," Proceedings of Symposium on Environmental Aspects
of Fuel Conversion Technology—II, EPA-600/2-76-149, June 1976.
12. Johnson, J. L., "Coal Gasification," Advances in Chemistry Series,
American Chemical Society, 131, 145 (1974).
100
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13. Kingsbury, 6. L., "Development of Multimedia Environmental Goals
for Pollutants from Fuel Conversion Processes," Symposium Pro-
ceedings: Environmental Aspects of Fuel Conversion Technology, III
(September 1977, Hollywood, Florida), EPA-600/7-78-063, April 1978.
14. Lewis, P. S., et al., "Stongly Caking Coal Gasified in a Stirred-
Bed Producer," U.S. Bureau of Mines, RI-7644, 1972.
15. Lewis, P. S., "A Study of Stirred, Fixed-Bed Gas Producer Behavior
with Caking Coals," Proceedings of Fourth National Conference on
Energy and Environment, AIChE, October 1976.
16. McMichael, W. J., et al., "Synthane Gasifier Effluent Streams,"
Pittsburgh Energy Research Center, PERC/RI-77/4, March 1977.
17. Mixon, F. 0., "Pollutants from Synthetic Fuels Production," Annual
Report for EPA Grant No. R804979010, IERL-RTP, Research Triangle
Park, N. C., October 1977.
18. National Research Council, "Evaluation of Coal-Gasification Technology:
Part 11-Low and. Intermediate Btu Fuel Gases," National Academy of
Sciences, Washington, D. C., 1973.
19. National Research Council, "Assessment of Low- and Intermediate-Btu
Gasification of Coal," National Academy of Sciences, Washington, D.
C., 1977.
20. Novotny, M., et al., "The Methods for Fractionation, Analytical
Separation and Identification of Polynuclear Aromatic Hydrocarbons
in Complex Mixtures," J. Chrom. Sci. 12, 606 (1974).
21. Page, G. C., "Fate of Pollutants in Industrial Gasifiers," Symposium
Proceedings: Environmental Aspects of Fuel Conversion Technology,
III (September 1977, Hollywood, Florida), EPA-600/7-78-063, April
1978.
22. Pellizzari, E. D., et al., "Collection and Analysis of Trace Organic
Vapor Pollutants in Ambient Atmospheres," Env. Sci. Tech. 9^, 556-
560 (1975). See also: J. T. Bursey, et al., "Application of
Capillary GC/MS/Computer Techniques," American Lab., pp. 35-41,
December 1977.
23. Pellizzari, E. D., "Identification of Components of Energy-Related
Wastes and Effluents," EPA-600/7-78-004, January 1978.
24. Petersen, M. R., et al., "Characterization of Substances in Products,
Effluents, and Wastes from Synthetic Fuels Production Test," Battelle
Pacific Northwest Laboratory, BNWL-2131, September 1976.
101
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25. Sharkey, A. G., Jr., et al., "Mass Spectrometric Analysis of Streams
from Coal Gasification and Liquefaction Processes," Pittsburgh
Energy Research Center, PERC/RI-75/5, November 1975.
26. Shaw, H., and E. Magee, "Evaluation of Pollution in Fossil Fuel
Conversion Processes-Lurgi Process," Exxon Research and Engineering
Co., EPA-650/2-74-009-C, July 1974.
27. Si nor, J. E., "Evaluation of Background Data Relating to New Source
Performance Standards for Lurgi Gasification," EPA-600/7-77-057,
June 1977.
28. Sparacino, C. M., "Analytical Techniques and Analysis of Coals,
Tars, Waters and Gases," Symposium Proceedings: Environmental
Aspects of Fuel Conversion Technology, III (September 1977, Hollywood,
Florida), EPA600/7-78-063, April 1978.
29. Sparacino, C. M., "Analytical Methodology for Characterization of
Coal Tars," Symposium on Process Measurements for Environmental
Assessment, (Atlanta, Georgia, February 1978).
30. Woodall-Duckham, Ltd., "Trials of American Coals in a Lurgi Gasifier
at Westfield, Scotland," FE-105, 1974.
31. Woodmansee, D. E., and P. M. Palmer, "Gasification of a Highly
Caking Coal in the GeGAS Pressurized Gas Producer," 173rd National
Meeting, American Chemical Society, March 1977.
102
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APPENDIX I
The Kinetics of Char Gasification
1-1
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APPENDIX I
THE KINETICS OF CHAR GASIFICATION
The gasification of coal char with steam, or with steam and air, is
a much slower process than that of coal devolatilization. Hence, the
char conversion rates are of primary importance in determining the
overall rate of gasification processes which aim to achieve high levels
of carbon conversion. Generally, the char-steam reaction is slower than
the char-oxygen reaction, although the activation energy (temperature
dependence) is of the order of 35 kilocalories per gram-mole (146 kJ/mol)
for both.
The theoretical order of these reactions is not firmly established
since the mechanisms for them are not fully understood. It appears that
the physical state of the char and the presence of foreign matter can
influence the reaction process. In fact, a catalytic effect due to
alkali metal compounds is well known. At high steam partial pressures,
the char-steam reaction tends toward a zero-order reaction with respect
to the steam partial pressure according to experimental evidence.
Otherwise, both the char-steam and the char-oxygen reactions, for most
practical purposes, can be regarded as first-order with respect to the
gas reactant concentration or partial pressure.
The char-steam reaction has been represented with some success by
the expression
0-x)
This rate equation accounts for both the forward reaction of char with
steam and the reverse tendency of hydrogen and carbon monoxide combination
to generate the original reactants. The initial (maximum) rate is
dx
dt
kv
RT
PH,OPCO
n RT
PH20 K KTJ
1-2
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obtained when the second term is deleted, i.e., by the following relation
dT = n*f pH2o(1"x)-
An examination of rate data published on the char-steam reaction
indicates a decided variation of rates with the type of char and the
F121
operating pressure. An interpolation of these dataL J for the con-
ditions of this study, viz., high volatile coal char and a pressure of
1.5 MPa (200 psig), give rise to the following rate values:
= A0exp(-AEa/RT)
where: AE. =37.2 kcal/mol
a
AQ = 5.54 x 103 sec"1MPa"1.
For the char-oxygen reaction, the reacting region is confined to a
thin layer starting at the external particle interface if the reaction
rate is chemical reaction controlled.'- •" Based upon the external surface
area of the char particles,
BT = ksssp02-
Here Sg is the specific external surface area of the particles and k is
the chemical reaction rate constant based upon the external surface area
of the reacting particles.
1-3
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The reaction rate constant kg has been developed for char by Field,
et al.,^ to be
ks = A0exp{-AEa/RTs}
where: AE, =35.7 kcal/mol
d
AQ = 8.71 x 105kg/m2-s.(MN/m2) .
When the reaction rate is limited by the diffusion of gases through
the ash layer and/or the gas film on the particles, then the rate constant
can be replaced by the factor [(l/(l/kdiff + 1/k )].
Experimental evidence from previous investigators indicates that
the reactivity of chars with oxygen in the chemical reaction control
regime depends strongly upon the degree of gasification of the char. As
the carbonaceous matter in a char particle is consumed by reaction with
oxygen, a dramatic modification of the pore structure of the particle
takes place. This pore structure phenomenon may well be the primary
factor that determines the char reactivity with oxygen, thus masking
major influences associated with the parent coal or the conditions of
devolatilization under which the char was generated.
1-4
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APPENDIX II
Multimedia Environmental Goals: MATE and EPC Concepts
II-l
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APPENDIX II
MULTIMEDIA ENVIRONMENTAL GOALS: MATE AND EPC CONCEPTS
The achievement and maintenance of an acceptable (or quality)
environment must from a practical viewpoint involve the establishment of
maximum allowable concentrations of chemical contaminants in the air,
water, and solid materials which constitute the natural environment.
Such concentrations may be referred to as Multimedia Environmental Goals
(MEG) values. Ambient level MEG values thus represent the concentrations
of contaminants or degradation products in the ambient air, water, or
solid materials below which unacceptable negative effects to the surrounding
populations or ecosystems do not occur. Emission level MEG values are
concentrations of contaminants or degradation products in emissions,
effluents, or disposals representative of the control limits achievable
through technology.
A Multimedia Environmental Goals project, which is an integral part
of the environmental assessment methodology program currently being
developed under the guidance of the Fuel Process Branch of IERL-RTP at
the Research Triangle Park in North Carolina, has been concerned with
the definition and quantisation of MEG values. A master list of chemical
compounds has been compiled for study. More than 600 chemical substances
and physical agents are included representing individual compounds,
complex effluents/mixtures and nonchemical degradants (such as visual
effects, subsidence, heat, and noise). Primary emphasis has been placed
on contaminants from fossil fuels processes (particularly coal gasifi-
cation and coal liquefaction). The primary selection criterion was that
the substance be associated with fossil fuels processes. Secondary
emphasis has been placed on substances for which federal standards or
criteria exist or have been proposed, substances for which threshold
limit values or lethal dose values have been reported, substances which
have been identified as suspected carcinogens or substances which appear
II-2
-------
on the EPA consent decree list. Additionally, substances may be in-
cluded which are present in the environment as pollutants and/or have
been identified as being highly toxic.
To organize the more than 600 master list entries, substances have
been arranged into categories based on chemical functional groups for
organic compounds and on the most important chemical element present for
inorganic compounds. This categorization scheme emphasizes logical
relationships between groups of substances so that each category is
characterized by toxicologically and chemically similar substances. A
total of 85 categories (26 organic and 50 inorganic compounds) have
resulted. A MEG number was assigned to each of the compounds addressed,
the first two digits of which represent the category.
Methods of detection for some of the compounds within a specific
category are known to be similar. Analysis of such groups as a whole is
in some cases practical for broad screening applications. Phenolic
compounds are thus addressed collectively by water quality recommen-
dations; hence, phenols are grouped as a category in the master list.
Emission level MATE values pertain to gaseous emissions to the
land, aqueous effluents to water, and solid waste to be disposed to
land. These goals may have as their bases technological factors or
ambient factors. Technological factors refer to the limitations placed
on the control levels by technology, either existing or developing.
Since there is a relationship between contaminant concentrations and
emissions and the presence of these contaminants in ambient media, it is
imperative to consider ambient factors when establishing emission level
goals. Ambient factors included in the project are minimum acute
toxicity effluents (MATE) values, ambient level concentration (ALC)
values and elimination of discharge (EOD) values. This categorization
is shown in Table II-l. MATE values are concentrations of pollutants in
undiluted emission streams that would not adversely affect those persons
or ecological systems exposed for short periods of time. ALC values are
permissible concentrations of pollutants in emission streams which,
after dispersion, will not cause the level of contaminant in the ambient
II-3
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TABLE I1-1. MULTIMEDIA ENVIRONMENTAL GOALS
Emission Level MEG Values
I. Based on Best Technology
A. Existing Standards
a. New Source Performance Standards
b. Best Available Technology
B. Developing Technology
Engineering Estimates (R&D goals)
II. Based on Ambient Factors
A. Minimum Acute Toxicity Effluent Values
a. Based on Health Effects
b. Based on Ecological Effects
B. Ambient Level Goals
a. Based on Health Effects
b. Based on Ecological Effects
C. Elimination of Discharge Values
Natural Background
Ambient Level MEG Values
I. Current or Proposed Ambient Standard or Criteria
A. Based on Health Effects
B. Based on Ecological Effects
II. Toxicity Based Estimated Permissible Concentration (EPC) Values
A. Based on Health Effects
B. Based on Ecological Effects
III. Zero Threshold Pollutants (EPC) Values
Based on Health Effects
(Individual MEG values for each subcategory may be defined for air, water,
and land (solid material) concentrations.)
II-4
-------
receiving medium to exceed a safe continuous exposure concentration.
EOD values are concentrations of pollutants in emission streams which
after dilution will not cause the level of contaminant to exceed levels
measured as "natural background."
Ambient level MATE values incorporate three categories of information
to describe estimated permissible concentrations for continuous exposure.
The three categories are: (1) current or proposed federal ambient standards
or criteria; (2) toxicity values including both acute and chronic effects;
and (3) carcinogenicity or teratogenicity values. The existence of
thresholds for carcinogens, teratogens and mutagens has been widely
debated and is still unresolved. Estimated permissible concentrations
must still be defined, however, if goals representing acceptable environ-
mental quality are to be achieved.
A methodology for evaluating and ranking pollutants for the purpose
of environmental assessment has been developed that can be used to
establish MEG values for a large number of compounds. The system
requires certain empirical data which are extrapolated through simple
models to yield estimated permissible concentration (EPC) values or
minimum acute toxicity effluent (MATE) values. The methodology relates
to ambient level goals and emission levels goals (hazard to human health
or to ecology induced by short term exposure to emissions). It is
recognized that there are several other criteria pertinent to the develop-
ment of MEG values that have not been incorporated into the methodology
thus far developed. Additional work, however, is ongoing. New research
is needed before refined models of estimation can be developed to allow
inclusion of such criteria as synergisms, antagonisms and other possible
secondary pollutant associations.
Two types of estimated permissible concentration values are integrated
through selected models. Empirical data concerning the effects of chemical
substances for human health and the ecology are translated into a set of
toxicity-based EPC values. Another set of EPC values is supplied by a
system relating carcinogenic or teratogenic potential to medium concen-
trations considered to pose acceptable risks. Overall, the methodology
II-5
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defines a total of 22 different kinds of EPC values, many of which are
interrelated. The EPC values have been coded by subscript for easy
identification as shown in Tables II-2 and II-3.
MATE values as emission level goals are analogous to EPC values as
ambient level goals. The basic difference is that MATE values represent
concentration limits in effluents, emissions, and discharges for short-
term exposure whereas EPC values could be considered as lifetime con-
tinuous exposure values for the ambient environment. Fourteen different
MATE values have been defined in the methodology. MATE values carry
three subscripts: the first defines whether the value refers to air (a),
water (w), or land (1); the second, whether the value refers to human
health (h) or the ecological environment (e); and the third, which model
was used to derive the value (numerical index). The MATE values that
have been used in this study were obtained from the report "Multimedia
Environmental Goals for Environmental Assessment," Volume 2, MEG Charts
and Background Information (EPA-600/7-77-136b).
II-6
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TABLE I1-2. DERIVATION OF HEALTH BASED EPC'S
Data
TLV or NIOSH Recommendation
(occupational exposure)
LD50' LDU
Bioassay data (carcinogen
testing)
Bioassay data (teratogen
testing)
LD50
Interrelationship
TLV «
EPCWH
EPCWC
EPCWT
EPCLH
EPCLC
EPCLT
LD50*
' EPCAH**
a cpr **
tKLAC
a ppr **
hKLAT
a FPP
tKLWH
a EPCwc
- EPCWT
Specific EPC Derived
EPCAH1, EPCAC1
EPCAH2
EPCAC2
EPCAT
EPCWH1
EPCWH2
EPCWC
EPCWT
EPCLH
EPCLC
EPCLT
*Handy, R., and A. Schindler, "Estimation of Permissible Concentration of
Pollutants for Continuous Exposure," Environmental Protection Agency, Research
Triangle Park, N.C. EPA-600/2-76-155, June 1976.
**Stokinger, E.H., and R. L. Woodward, "Toxicologic Methods for Establishing
Drinking Water Standards," J. Am. Water Works Assn., 50, 515-529 (1958).
II-7
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TABLE I1-3. DERIVATION OF ECOLOGY BASED EPC'S
Data
Interrelationship
Specific EPC Derived
Air concentration causing an
effect in vegetation
LC50 or TLm
Tainting Level
Cumulative Potential
Application Factor*
Hazard Level*
EPC
L£
EPC
WE
EPC
AE
EPC
EPC
EPC
EPC
EPC,
WEI
WE2
WE3
WE4
WE4
EPC
LE
*Value supplied in Water Quality Criteria.
Subscript Key: A (air); W (water); L (land); E (ecological effects); numbers
refer to specific models.
II-8
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TECHNICAL REPORT DATA
(Please read instructions on the reverse before completing)
REPORT NO.
EPA-600/7-78-171
2.
3. RECIPIENT'S ACCESSION-NO.
.TITLE AND SUBT,TLEpollutants from Synthetic
Production: Facility Construction and Preliminary
Tests
5. REPORT DATE
August 1978
6. PERFORMING ORGANIZATION CODE
. AUTHOR(S)
J.G.Cleland, F.O.Mixon, D.G.Nichols,
C. M. Sparacino. and D. E. Wagoner
8. PERFORMING ORGANIZATION REPORT NO.
i. PERFORMING ORGANIZATION 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
2. SPONSORING AGENCY NAME AND ADDRESS
EPA, Office of Research and Development
Industrial Environmental Research Laboratory
Research Triangle Park, NC 27711
13. TYPE OF REPORT AND PERIOD COVERED
Phase; 11/76-4/78
14. SPONSORING AGENCY CODE
EPA/600/13
5. SUPPLEMENTARY NOTES T£RL-RTP project officer is Thomas W. Petrie, Mail Drop 61,
is. ABSTRACT Tne j^po^ describes the facility construction and gives results of prelim-
inary tests for a project that seeks a fundamental understanding of the factors and
conditions that cause the production of environmental pollutants in synthetic fuels pro-
cesses. Tasks include: operation of a laboratory-scale coal gasification facility; col-
lection and chemical analysis of effluent stream samples; compilation and analysis of
resulting data; and evaluation of these data. The experimental system operates suc-
cessfully and reliably at gasification temperatures up to 1370 K, pressures up to
1.2 MPa, and gas generation rates of about 20 standard liters/mm. Analytical chemi-
cal methods, developed for analysis of effluents from these coal gasification tests,
promise to achieve the required levels of sensitivity and extent of compound identifi-
cation and quantitation. For example, liquid chromatography/mass spectrometer/
computer analysis is used to quantitate organic compounds. The major pollutant
classes are benzene and its substituents, thiols and sulfides, phenols, fused poly-
cyclics, sulfur heterocyclics, and inorganic sulfur compounds.
7.
KEY WORDS AND DOCUMENT ANALYSIS
DESCRIPTORS
b.lDENTIFIERS/OPEN ENDED TERMS
c. COSATI Field/Group
Pollution
Fuels
Coal Gasification
hemical Analysis
Benzene
Thiols
Phenols
Polycyclic Com-
pounds
Sulfur Heterocyclic
Compounds
Pollution Control
Stationary Sources
Synthetic Fuels
Fuel Production
Sulfides
Fused Poly eye lies
13B
21D
13H
07D
07C
18. DISTRIBUTION STATEMENT
Unlimited
19. SECURITY CLASS (This Report I
Unclassified
21. NO. OF PAGES
125
20. SECURITY CLASS (This page)
Unclassified
22. PRICE
EPA Form 2220-1 (9-73)
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