EPA-650/2-73-042
December 1973
Environmental Protection Technology Series
.;>::>•>
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EPA-650/2-73-042
GASIFICATION OF FOSSIL FUELS
UNDER OXIDATIVE, REDUCTIVE,
AND PYROLYTIC CONDITIONS
by
A. L. Yergey, F.W. Lampe,
M. L. Vestal, E. J . Gilbert, and G. J . Fergusson
Scientific Research Instruments Corporation
6707 Whitestone Road
Baltimore, Maryland 21207
Contract No. 68-02-0206
Program Element No. IABOI3
ROAP No. 2IADD04
EPA Project Officer: L. Stankus
Control Systems Laboratory
National Environmental Research Center
Research Triangle Park, North Carolina 27711
Prepared for
OFFICE OF RESEARCH AND DEVELOPMENT
U.S. ENVIRONMENTAL PROTECTION AGENCY
WASHINGTON, D. C. 20460
December 1973
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This report has been reviewed by the Environmental Protection Agency and
approved for publication. Approval does not signify that the contents
necessarily reflect the views and policies of the Agency, nor does
mention of trade names or commercial products constitute endorsement
or recommendation for use.
11
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TABLE OF CONTENTS
PAGE
INTRODUCTION 1
EXPERIMENTAL 3
INSTRUMENTATION AND THEORY 3
IMPROVEMENTS IN EXPERIMENTAL TECHNIQUE 8
ARGON AS DILUENT GAS 8
SAMPLE HOMOGENEITY EXPERIMENTS 9
ON-LINE COMPUTER SYSTEM 10
COMPUTERIZATION OF THE NON-ISOTHERMAL KINETICS
LABORATORY 10
SYSTEM HARDWARE 10
SYSTEM SOFTWARE 14
EXPERIMENTAL DATA 17
EVOLUTION CURVES IN OXIDIZING ATMOSPHERES 19
EVOLUTION CURVES IN PYROLYTIC ATMOSPHERES 21
GAS EVOLUTION CURVES IN REDUCING
ATMOSPHERES 22
SPECIAL EXPERIMENTS 24
CO2 + CO REACTIONS 24
AIR OXIDATIONS 25
DISCUSSION 26
KINETIC PARAMETERS 26
OXIDATION REACTIONS 29
HYDROGASIFICATIONS 31
CARBON DIOXIDE - CARBON REACTION 32
SUMM AR Y 34
APPENDIX A - Gaseous Evolution Data For Oxidative Reactions 35
APPENDIX B - Gaseous Evolution Data For Pyrolysis Experiments 84
APPENDIX C - Gaseous Evolution Data For Reducing Reactions 141
APPENDIX D - Gaseous Evolution Data For 13C Reactions 169
APPENDIX E - Gaseous Evolution Data For Air Reactions 174
BIBLIOGRAPHY 177
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LIST OF FIGURES
Pages
Figure 1
Figure 2
Figure 3
Figures 4-47
Figures 48 - 102
Figures 103 - 128
Figures 129 - 132
Figures 132 - 133
Block Diagram of the Coal Research
Facility
Schematic of Computer and Peripheral
Interconnections
Kinetic Parameters for CO Evolution -
Oxidizing Atmosphere, SRI Coal No, 5
Oxidation Experiments - Appendix A
Pyrolysis Experiments - Appendix B
Reduction Experiments - Appendix C
13C Experiments - Appendix D
Air Experiments - Appendix E
13
28
40 - 83
86 - 140
143 - 168
170 - 173
175 - 176
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LIST OF TABLES
TABLE I.
TABLE II.
TABLE III.
TABLE IV.
TABLE V.
TABLE VI.
TABLE VII.
TABLE VIII.
TABLE IX.
TABLE X.
TABLE XI.
Pages
Run Conditions , Representative Sample 9
Hardware Components of On-Line Computer 11
System
SystemSoft-ware 15
Proximate and Ultimate Analysis Summaries 18
Kinetic Parameters (Oxidation and Reduction
Reactions) 27
Kinetic Parameters ( CO2 - Coke Reactions) 33
Peak Temperatures in Oxidative Gasification
of Coal - Appendix A 36
Effect of Water Vapor on Oxidative Gasification
of Coal - Appendix A 33
Peak Temperatures in Treatment of Coke
(SRI-7) with CO2 in Ar - Appendix A 39
Peak Temperatures for Pyrolysis of Coals
and Cokes Heated at 30°/min in Argon -
Appendix B 85
Peak Temperatures in Reducing Atmospheres
of Hydrogen at 10 atm Pressure - Appendix C 142
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INTRODUC TION
This final report describes our studies on the gasification of coals and
related fossil fuels performed under Contract 68-02-0206 with the
Environmental Protection Agency.
Contract efforts in the past have resulted in the development of the com-
puterized non-isothermal kinetics laboratory1, and in the demonstration of
the value of the non-isothermal kinetics treatment for the study of chemical
reactions related to coal desulfurization1'2. The work described in this report
clearly demonstrates the ability of the non-isothermal kinetics laboratory to
generate large amounts of phenomenological data concerning complex reaction
systems. The relatively short times required for data production, the number
of different materials which have been used or obviously could be used, and
the quality of the data produced indicate the power of the non-isothermal kinetics
technique. Possible future importance of the non-isothermal kinetics method
can perhaps be fully appreciated for the first time through the results pre-
sented in this report. The apparent practical applications of the method to
studies of desulfurization, combustion and gasification given here and in past
reports could be extended to studies of the practical basis of the chemical
industry, heterogeneous reaction kinetics.
Gasification studies have been performed on a variety of bituminous coals,
anthracite , lignite , and some chars under a large variety of reaction condi-
tions. Oxidative gasifications have been performed in a range of oxygen con-
centrations from 0.1% to 20% O2 by volume at pressures up to 10 atm. Re-
ductive gasifications in pure hydrogen have been carried out routinely at
hydrogen pressures of up to 20 atm.
-1-
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Several experiments which utilize the unique capabilities of the non-
isothermal kinetics technique have also been performed. First are a number
of fuel pyrolysis studies carried out in an argon atmosphere, and intended
to determine the thermal evolutionary behavior of some materials present in
these fuels. Second, the non-isothermal kinetics technique permits the study
of particular reactions of importance in gasification under conditions where inter-
fering reactions are limited in extent or totally absent. In this fashion, the
CO shift reaction with coal chars and coals was studied.
A great deal of progress was made toward the goal of operational on-
line data acquisition and storage system using a mini-computer. The com-
puter and its peripherals have all functioned as a system. The interfacing
hardware as well as the data acquisition software are in near-final form.
The actual operation of the computer/mass spectrometer in an on-line,
real-time situation will be deferred until a future date.
-2-
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EXPERIMENTA L
INSTRUMENTATION AND THEORY
The experimental apparatus and the mathematical treatment of results
used in the non-isothermal kinetics method have been fully described in earlier
publications1"5. During the performance of the research described in this
report, the apparatus was used in virtually an unaltered form from that given
in the descriptions cited, but important changes hi the apparatus are given in a
following section. For the sake of completeness, a brief description of the
apparatus and a brief theoretical summary are given below.
A block diagram of the non-isothermal kinetics apparatus is shown in
Figure 1. Hydrogen or helium, at flow rates selected for an experiment, is.
passed over a finely ground ( 100-200 mesh) sample of coal placed into a
quartz tube inside the furnace. Temperatures within the furnace are increased
linearly with time, and are maintained to within a few degrees of a preselected
heating rate by differential controls within the temperature programmer.
The heating rates possible within this apparatus can vary from about l°C/min
to 100°C/min.
The sweep gases used in this work also serve as chemical ionization
reagent gases since their concentrations are much greater than the gaseous
reaction products. Source pressures in the mass spectrometer are maintained
atabout one Torr so that ions formed originally by electron impact undergo
mutiple ion-neutral collisions. In the case of hydrogen, this results in H3
being the most abundant ion in the source, as shown in Equations ( 1) and (2).
Ions derived from the desulfurization reaction product gases are formed by a
proton transfer from H3 as shown in Equation ( 3) .
-3-
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GAS
IN
YE
/
FURNACE
REACTOR
/
\
FURNACE
CONTROLLER
/
\
LINEAR
TEMPERATURE
PROGRAMMER
\
NT
...
TEMPERATURE
1 "' MEASUREMENT ' "
CHEMICAL
IONI7.ATION
^s_ ni i A n*?! IPMI p ^^
MASS
SPECTROMETER
A
f
^>v
DIGITIZER
k AND
' MASS SELECTOR
\/
K
j
T2M,...
PAP;:.!* TAPE
FL::CH
COMPUTERIZED
DATA
HANDLING
SYSTEM
Figure 1 Block Diagram of the Coal Research Facility
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H2 + e -» 2e + Hz+
H2+ + H2 -^H3+ + H (2)
H3+ + H2S — H3S+ + H2 (3)
Because the proton affinities of the product gases are higher then that of H2,
the product gases are preferentially protonated, an effect which results in a
great sensitivity increase compared with normal electron impact ionization.
An analogous situation involving charge transfer occurs when He is used as
the reagent gas.
Ions leaving the source region are mass-analyzed in a quadrupole mass
filter and their intensities are amplified by an electron multiplier. Signals
from both the multiplier and a thermocouple are input to the digitizer and mass
spectrometer controller. This device allows the monitoring of the intensities
of up to nine peaks in the mass spectrum by stepping the mass filter to
appropriate focussing voltages. The rate at which the controller steps through
the mass settings and temperature is selected to be comparable to the furnace
heating rate, so that intensity versus temperature plots result.
The mathematical treatment of reaction product intensity versus tempera-
ture profiles obtained by linear heating of a bed of material can be summarized
using a general reaction considered to proceed in the furnace. Consider
Equation (4), the reaction of a particular solid species, P , with gas H2 passing
over it. For the purpose of this brief summary, it will be assumed that the reaction
is first order in P and zeroth order inH2 and that gaseous products are swept from
the chamber without further reaction.
P 4- H2 -» PH2 ( 4)
-5-
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The differential expression of the reaction rate is:
- 3£= ^fr1 • k[p) (5>
where the reaction rate constant, k, is given by the Arrhenius equation:
(6)
where ko is the temperature-independent Arrhenius pre-exponential factor,
E is the activation energy, and R and T have their usual meaning. Equation (5)
can be integrated to yield:
[PJ_
l-^=-(]
" [P] r
o o (7)
where [P] is the concentration of the reactant at a time, t, and f P] 0 is the
initial concentration of the reactant. Consider now a reaction where the tempera-
ture may be varied linearly with time as :
dT , ,
m= — (8)
j «-p
where T , and t are as above and m is the heating rate. When — r— =m=0 then
at
k in ( 7) does not vary with time, and the integration of the right-hand side
of ( 7) becomes trivial. In cases where m^ 0, (6) and ( 8) are substituted
into (7) , and the integration limits become those temperatures between which
reaction is observed;
o fo-
F5Y - - — \ Q. d
[P\ /m J
T; (9)
-6-
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The integration of ( 9) can be completed by use of an approximation for the
exponential integral. Making use of an expression for [P] and fP] 0 in terms
of the volumes of gaseous products, viz:
[P] = *(V0 -V) (10)
where V is the volume of gas evolved up to temperature T, V0 is the total
gas volume evolved and a is a proportionality factor, and then differentiating
this expression with respect to T, yields the expression:
d\' 7o
, L " ' RTJ
(11)
Equation ( 11) defines the shape of the intensity versus temperature peaks
obtained as data in non-isothermal kinetics experiments. Analysis of these peaks
for the kinetic parameters E and k'K** «+
where Tm is the absolute temperature of a peak maximum. Plots of ( 12) using
data from experiments conducted at a variety of heating rates, result in deter-
minations of the kinetic parameters desired. A more complete discussion of
data analysis, involving reaction orders other than first as well as back reactions,
is given in the previously cited references.
-7-
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IMPROVEMENTS IN EXPERIMENTAL TECHNIQUE
ARGON AS DILUENT GAS
The non-isothermal kinetics laboratory performed quite reliably during
the course of the contract in a form virtually unaltered from previous descrip-
tions1'3. Several improvements to the experimental techniques have,
however, been made.
Previous work in oxidizing atmospheres was done using helium as the
carrier gas. Helium, although desirable because of its inertness, has an
ionization potential of 24.6 eV, which is sufficient energy to cause extensive
fragmentation of sample gases in charge exchange chemical ionization.
Argon, with an ionization potential of 15.8 eV, has been used in place of
helium as the diluent in oxidizing atmosphere studies because the inertness
is attained with considerably reduced fragmentation. Nitrogen, with an ioni-
zation potential near argon, and much less expensive than argon, is not useable
because the N2 ion has the same mass as CO , a crucial product gas in
oxidizing experiments, and thus CO production could not be followed. Some
fragmentation of CO2 to yield CO , a process which occurs at energies
higher than 20 . 5 eV , is seen with the use of argon. This fragmentation is
undoubtedly due to the presence of the small amounts of Ar ion observed
in the chemical ionization mass spectrometer. Although at first it would be
anticipated that any Ar formed by electron impact would be quickly eliminated
by the large numbers of collisions occurring between the ions and neutrals
present in the source at typical operating conditions, nevertheless, this species
is observed at high source pressures. Apparently, the mechanisms which exist
++
for the decomposition of the Ar - Ar collision complex into two argon
singly charged ions are very inefficient and sufficient quantities of the doubly
charged ion are present to effect some fragmentation in the source.
-8-
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SAMPLE HOMOGENEITY EXPERIMENTS
Ant area of continuing concern for experiments performed in the non-
isothermal kinetics laboratory has been the reliability of data interpretation
when sample sizes of the order of 10-15 mg are used. The well known inhomo-
geneity of coal, coupled with small samples, could result in interpretations
which are based not on the average properties of the coals, but on the properties
of a totally unrepresentative portion of the material. On the other hand, the use
of small samples in the bed - is imperative to the non-isothermal kinetics
method, if adequate resolution is to be obtained from sequential evolution of a
particular gaseous product.
A series of experiments has been performed to investigate the repro-
ducibility of H2S evolutions from small samples. Scientific Research Instruments
Corporation Coal # 10 .(Kentucky 4% Sulfur, USBM #110 from bed 14 of the
Shamrock mine^was used. The entire quantity of this coal in hand was subjected
to a four-fold rifle sampling, resulting in sixteen final samples. Non-isothermal
kinetic runs were performed on a portion of each of the eight odd-numbered
samples. The standard run conditions are shown in Table I.
TABLE I RUN CONDITIONS, REPRESENTATIVE SAMPLE
Material - SRI Coal #10, Kentucky 4% Sulfur
Weight - 15 mg Initial Temperature -80CC
Particle Size _ 100-200 mesh Carrier Gas - H2
Heating Rate - 14°/min Flow Rate - 100 scc/min
The eight H2S intensity-temperature profiles resulting from these experiments
although not given here, are sufficiently alike in all respects for seven of the
eight experiments, that recognition of the material used in the experiments would
be readily accomplished. It appears that the use of small carefully chosen samples
can reflect with some confidence, the average behavior of the material chosen
for a non-isothermal kinetics experiment.
-9-
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ON LINE COMPUTER SYSTEM
COMPUTERIZATION OF THE NON-ISOTHERMAL KINETICS LABORATORY
The non-isothermal kinetics laboratory has been computerized to some
extent in past years1. The results of this computerization are demonstrated
by the bulk of this report, in that substantial quantities of data have been pro-
duced. The computerization of the past has been an off-line raw data
reduction system with additional programming necessary for data analysis.
The computerization, as it is presently structured, however, has several drawbacks.
There is an upper limit for a data acquisition rate, a lower limit on data reduction
time, and a high long-term cost. The first computerization of the non-isothermal
kinetics laboratory involved data recording on punched paper tape. Because
the paper tape is limited in speed, data acquisition rates for non-isothermal
kinetics experiments are limited to speeds corresponding to heating rates of
about 100°/min. Recent incremental improvements in data reduction software
on the time-shared computer being used have permitted data reduction for a
given experiment to be done in thirty minutes, but at the cost of an operator1 s
time and useage charges for the time sharing service.
The use of an on-line, real-time mini-computer data acquisition system is
seen as solving all three of the problems described above. Data acquisition can
be done easily at heating rates that conservatively are on order of magnitude
faster than are currently feasible, raw data reduction can be completed simul-
taneously with the completion of an experiment, and only a single operator will be
required for the entire process of experiment supervision and raw data reduction.
SYSTEM HARDWARE
An evaluation of cost, programming ease, and quality resulted in the choice
of a Varian 620/L computer with 12K, 16 bit core, a paper tape reader, and
1.17M, 16 bit word disc for the task of interfacing with the non-isothermal
kinetics laboratory. The hardware components of this system are listed in Table II,
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TABLE II. HARDWARE COMPONENTS OF ON-LINE COMPUTER SYSTEM
Varian Components
6ZQ/L Central Processor with 12, 288 words of 16-bit core, 1. 8|j. sec
cycle time, 130 member instruction set, 4 operational and
5 buffer registers.
Buffered Interlace Controller (BIG) allows programmable block data
transfers
Real Time Clock (RTC) at 400 Hz
Power Fail/Restart ( PF/RS) interrupts programs at power failure
and automatically restarts upon power recovery
Priority Interrupt Module ( PIM) allows branching and return to programs
based on the status of external signals such as real-time data
ready or internal function complete signals.
Mpveable Head Disc with capacity for 1. 17 M 16-bit words formatted
into 8 sectors and 203 tracks on two sides of a magnetic oxide
medium, 10 operations with interrupt capability, and a 92K
16-bit word transfer rate.
Buffered I/O Controller allows interfacing to SRIC Digitizer and Mass
Spectrometer Controller
Universal Asynchronous Series Controller allows use of Typagraph
plotting teletype in place of standard teletype
300 cps Paper tape Reader
Other Components
{used previously in non-isothermal kinetics laboratory)
Tally 60 cps Paper Tape Perforator
Typagraph Model 3 Plotting Teletype Terminal ( TTY)
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The first seven items listed along with the controllers for the last four items
are located in two CPU console chassis, while the remaining items, two being
peripheral devices, are contained in separate chassis.
Figure 2 shows a schematic representation of the functional connections
between various components in the system. The CPU is the main control device
and supervisor for the entire system. Information transfer between the CPU
and various peripherals is carried out along the I/O lines, although block word
transfers for the paper tape system and the disc can be effected through the BIC .
The PIM is a very necessary and a very useful device for the optimum ionization
of other kinds of programming. In data acquisition for example, such as a raw
data reduction/analysis program, the PIM interrupts a program whenever the
SRIC digitizer has data to transfer. When the transfer is complete, the program
execution continues from the point of interruption. A similar operation can be
used in the copying of information from one peripheral to another or between a
peripheral and core. The latter case is important because of the wide disparity
in rates which exist between core and any peripheral. If interrupt signals are
received by the PIM from two devices simultaneously, they are dealt with in a
hierarchical fashion with number 1 on Figure 2 having the highest priority. The
PF/RS acts as the PIM does, but only for the specific case of power failures and
restarts. In addition, it has a priority higher than any of those in the PIM. The
RTC is used in establishing a time-base for the acquisition of data in a real-
time experiment, or for the execution of particular operations at predetermined
real-time points.
Considerable difficulty was encountered in bringing the hardware to a
functioning state. The principle components of the system were delivered one
month after the date agreed upon with the manufacturer, but in addition, final
delivery of the correct system components was not accomplished until five
months after the original delivery date. A fully functioning system is virtually
accomplished but due to delays incurred principally by disc hardware malfunctions,
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UJ
i
CPU
TRAP REQUEST
INTERRUPT/TRAP ACKNOWLEDGE
INTERRUPT REQUEST
PF/RS
Q
<
W
os
w
H
U
tf
Q
<
U
WRITE
REG.
READ
REG
USAC
1
TTY
RTC
w
a;
READY
PAPER
TAPE
CCNIROITFR
300 CPS
READER
BIG
60 CPS
PUNCH
O
Ut
CO
O
<5
c
DISC
CCNTROLLER
1
DISC
PIM
•+
BUFFERED
I/O
CCNTROLLER
SRIC
DIGITIZER
FIGURE 2. Schematic of Computer and Peripheral Interconnections
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software development allowing full system integration was slowed considerably
from initial projections. Use of the buffered I/O controller in the interrupt
mode will be deferred until a future date .
SYSTEM SOFTWARE
Software intended for use for the on-line computer connection to the non-
isothermal kinetics laboratory is grouped in two large sections . One section
is that supplied by the computer manufacturer, and the other section is that
developed by Scientific Research Instruments Corporation. Table III lists
the software in each of these catagories.
The Varian software is a necessary tool that was used in developing the
software for executing the real task assigned to the computer. The existance
of MOS and the disc hardware, in addition to being required for data acquisition
should have eased the entire job of applications software development. To a
large extent, this was true, especially in the later development stages where
program modules were assembled and then stacked together for execution. The
difficulties involving hardware, that were described above, limited the use-
fulness of MOS. In addition, there was an acutely felt lack in the MOS software
package for an easy-to-use line editor. The editor present in MOS was found
to be slow, difficult to operate, and inconvenient. Aside from this lack, however,
the remaining utility software, the assembler, compiler, loader, and executive,
was found to be adequate. The other Varian software listed in Table III was
found to be satisfactory for its intended purposes, and thus very valuable at
particular times .
Although development of the SRIC software package was hampered by the
hardware failures encountered and by the lack of a useable MOS editor, the pro-
grams listed in Table III have all been written, and have been tested to some
extent with the exception of VEZGRAF. This particular program requires
some experimentation to detemine the optimum size of pieces which can be
handled by 1ZK of core storage.
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TABLE III. SYSTEM SOFTWARE
Varian Software
Name
MOS
MAINTAIN
AID
BLD
SRIC Software
Purposes
Operating System for Disc useage. Includes
an assembler, compiler for FORTRAN,
loader, disc executive, and the ability to
manipulate peripherals.
Family of diagnostic programs used for
locating failures in the CPU or any peri-
pherals . Also used in checking for correct
functioning of apparatus after completion of
interfacing .
Stand-alone debugging program, permanently
resident in high core locations .
Stand-alone load and dump program for use
with binary information only. Permanently
located in high core.
ACQI
LINED
FLIM
VEZGRAF
MTM, etc.
Data acquisition and raw data reduction
program
Source code editor for any language in any
format.
Disc file management program which converts
disc to a random access device.
Modified form of Typagraph program
EZGRAF, which enables a computer of
limited core size to drive the plotting
teletype
Translated forms of previously written
SRIC data analysis programs to permit data
analysis with on-line systems.
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The protocol of software development was to use the excellent editor
available to us in a time-shared computer service to develop the LINED pro-
gram. LINED is an extremely versatile line and source code editor which
can then be used to develop the other programs in the SRIC package. Future
plans call for the elimination of the MOS editor from the disc system file and
replacing it with the LINED programming.
The FLIM program is intended to alter the formatting of the disc so that it
can be considered a random access device. This is very necessary for the
efficient storing of data files on the disc. It utilizes the concept of a disc table
of contents permitting the addition and subtraction of files without the
necessity of operator bookkeeping required by MOS. FLIM is the beginning
of a random access MOS package also slated for future development.
ACQI is the real time data acquisition programming for the on-line com-
puterized non-isothermal kinetics laboratory. As such.it takes data from the
SRIC digitizer and mass spectrometer controller at any time in an experiment
when such digital information is ready, by using the PIM described above. In the
long intervals, by computer time standards, between sequential data presentations,
ACQI creates separated intensity versus temperature profiles for each species
monitored in the experiment, corrects for heating ramp linearity and temperature
skewing, and stores the data files via block data transfers through the BIC, on
the disc. At the end of an experiment, ACQI writes an end-of-file after the
stored data and updates the indexing of FLIM. The use of ACQI replaces MULT,
MOD FILE, CAFILE and PIP used with the time shared computer1 to read-in
data from punched paper tapes , and then separate it into individual data files.
The programs such as MTM, LSTS and CURVE1 are retained in the on-line
configuration of the computerized non-isothermal laboratory because trans-
lation between two Fortran dialects permits these valuable data analysis pro-
grams to be used.
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EXPERIMENTAL DATA
A major objective of the experimental program during the past year
has been to utilize the computerized non-isothermal kinetic laboratory1 to
obtain as much kinetic data as possible pertinent to the oxidative gasification,
pyrolysis, hydrogenation , and desulfurization of representative coals
and cokes. With this objective in mind, we have studied the evolution of a
variety of gases from three typical coals, from cokes derived from these
coals, from an anthracite and from a lignite, as these solid materials are
heated at various rates from room temperature to 1400°K under oxidative
conditions, under reducing conditions and under purely pyrolytic conditions.
Proximate and Ultimate analysis summaries of these materials appear in Table IV
In this section we present the results of our non-isothermal experiments
in terms of computer-drawn evolution curves of the most significant gases
evolved from the various coals and cokes under the various conditions of
treatment. The evolution curves are presented as plots of the mass spectro-
metric ion-currents of ions derived from chemical ionization of the pertinent
gases as functions of the absolute temperature of the bed of coal or coke.
The currents of the various ions are presented in the plots in terms of arbitrary
units whose magnitude is proportional to the instantaneous concentration of
evolved gas in the gas stream leaving the solid bed of coal or coke. For example,
under oxidative conditions in which the treatment gas consists of 99% argon
and 1% oxygen, the H2O ion-intensity is proportional to the concentration of
water in the gas stream. On the other hand, under reducing condition in which
the treatment gas is pure hydrogen, the H3O ion-intensity is proportional to
the concentration of water in the gas stream leaving the bed of solid coal
or coke.
It is useful to point out here at the outset that blank runs, in which
only the quartz wool plugs are present in the reactor, show evolution peaks
of CO+, H2O+, and CH3+ at low temperatures (/•~520°K) . Therefore, little
-17-
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TABLE IV
PROXIMATE AND ULTIMATE ANALYSIS SUMMARIES
Proximate
Ultimate
oo
Material Mine Bed
SRI Coal 5 Little Dog Seam 6
Illinois
ISGS: 32-
11.60F
SRI Coal 7 Royal Franklin
Maryland
USBM: 106
SRI Coal 10 Shamrock No. 14
Kentucky
USBM: 110
Anthracite
Lignite North Beulah
%Nominal % foFixed
S Volatile s C %C
4.5 40.8 44.1 69.35
3 20.5 62.8 75.64
4 31.3 46.5 65.30
.67 9.0 76.0 84.23
.55 30.1 33.0 60.47
( dry basis)
%H %N %S
5.67 1.24 4.23
4.73 1.47 3.13
4.67 1.39 3.20
2.64 1.20 0.75
7.04 0.93 0.54
%Ash %O*
9.73 9.78
13.67 1.36
17.31 8.13
7.10 4.08
8.83 22.19
* by difference
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if any, significance should be attached to the appearance of these peaks in
the non-isothermal treatments of the coals and cokes .
EVOLUTION CURVES IN OXIDIZING ATMOSPHERES
The evolution of gases from the coal designated as SRI-5, when this
coal is heated from 300-1400°K at a heating rate of 30 °/min gas stream
containing 99% argon and 1% oxygen, may be seen by reference to
Figures 4-9. These are typical evolution curves that show the concentration
of H2O, CO, NO, CO2, SO2, and O2, respectively, as a function of temperature.
The oxygen is a reactant gas in these studies and the inverted peaks shown
in Figure 9 indicate a decrease in intensity of O2 in the ion source of the
mass spectrometer detection system. As will be discussed in the next
section, this may mean that the O2 concentration in the gas leaving the solid
reactant bed has been lowered; however, this conclusion may be made only
with caution, since it is possible that the experimental artifact of O2 reaction
in the ion-source with a product gas may be responsible for the apparent
decrease in O2 concentration in the gas stream. The flow rate of gas through
the coal sample in the experiments shown in Figures 4-9 was 200 cc/min .
It is clear from Figures 4-9 that ( l) the evolution of H2O exhibits
peaks at 605°, 715° and 869°; (2) peaks in the concentration of CO are found
at 766° and 840°; ( 3) a single peak at 828° is found for the concentration of
NO; (4) two peaks at 566° and 888° are observed for CO2; ( 5) a single peak
at 829°K is observed for the evolution of SO2. As mentioned earlier, the
studies depicted in Figures 4-9 were carried out at a heating rate of 30° /min
When the reactions are studied at different heating rates similar peaks are
observed but at different temperatures. In fact, as shown in an earlier report1
it is this shift in location with heating rate that permits the determination of
activation energy for the process involved in production of the peak. Rather
than show the individual curves such as in Figures 4-9 for all heating rates
studied, these data will be shown when appropriate in an equivalent but more
refined form in activation energy plots.
-19-
-------
In Figures 10-15, the concentrations of H2O, CO, NO, CO2, SO2, and O2,
respectively, from an identical treatment ( 1% O2 in Ar, 30°/min heating
rate) of the coal designated as SRI-7 are shown as functions of the absolute
temperature.
The concentrations of H2O, CO, NO, CO2, SO2, and O2 in the gas
stream leaving a solid reactant bed of the coal designated as SRI-10,
respectively, as functions of the temperature are shown in Figures 16-21.
Similar plots for the concentrations of the same gases observed when
anthracite and lignite are treated under the same conditions, are shown in
Figures 22-27 and 28-33 respectively.
The concentrations as functions of temperature of H2O, CO, CO2,
and O2 in the gas stream leaving a solid bed of a coke prepared from SRI-5
when this solid is treated identically ( 1% O2 in Ar, 30°/min) are shown in
Figures 34-37, respectively. Figures 38-43 show the concentrations of H2,
H2O, CO, NO, CO2, and O2 respectively, observed when a coke prepared
from SRI-7 is treated with 1% O2 in Ar but at a slightly lower heating rate
of 20" /min.
Finally, we show in Figures 44-47, the concentrations of H2O, CO, CO2,
and O2, respectively, as a function of temperature observed from the oxidation
treatment of a coke prepared from the coal designated as SRI-10. In this set
of experiments, the conditions of 1% O2 in Ar and a heating rate of 30° /min were
employed.
While Figures 4-47 present a rather complete experimental picture of
the non-isothermal oxidative treatment of coals SRI-5, SRI-7, SRI-10 for a
particular heating rate, the most pertinent information, namely the location
of peaks as functions of heating rates is shown in Table VII , Appendix A.
-20-
-------
The effect of adding water (at its vapor pressure at room temperature)
to the stream of 1% oxygen in argon may be seen in Table VIII. Each coal was
examined at only two heating rates, namely 15 and 40°/min and analyses were
made only for CO, CO2> and O2.
Since the oxidative gasification of coal or coke required oxygen in
some form to be delivered to the solid reactant, a number of experiments
were conducted in which a coke prepared from SRI-7 coal was treated non-
isothermally with a gas stream of 0.1% CO2 in Ar. The results, in terms
of peak temperatures for H2> H2O, CO, NO, "CH3" and CO2 are given in
Table IX. The "CH3" refers to the appearance of—15 and represents a
fragment ion from a hydrocarbon. Thi s probably comes from quartz wool as
it was also observed in blank experiments.
EVOLUTION CURVES IN PYROLYTIC EXPERIMENTS
In order to differentiate between actual oxidative processes and those
due to pyrolysis in the experiments described in which the oxygen and carbon
dioxide reactants are contained in a great excess of argon, experiments
were conducted in which the gas evolution from a pure argon stream was
examined. These were studied at only one heating rate, namely 30°/min.
The results for coals SRI-5, SRI-7, and SRI-10 are given in
Figures 48-54, 55-61 , and 6Z-68, respectively; those for anthracite and
lignite are shown in Figures 69-75 and 76-82 respectively; and those for cokes
prepared from coals SRI-5, SRI-7, and SRI-10 are shown in Figures 83-89,
90-95, and 96-102, respectively.
The peak temperatures for the various evolved gases are tabulated for
convenience in Table IX.
-21-
-------
GAS EVOLUTION CURVES IN REDUCING ATMOSPHERE
Studies have also been conducted on the evolution of CH4, H2O, C2H6,
and H2S from the same solid reactants when these are heated from 300°-1400°
in a stream of hydrogen. The studies have been carried out with hydrogen
pressures of 1, 10, and 20 atmospheres. Under such conditions the predominant
ion in the ion source of the detecting mass spectrometer is H3 and the ions
derived from the gases being evolved from the solids in the reactor are
produced via reaction of these gases with H3 . We believe that the most
reliable analytical results will be obtained when H3 is sufficiently abundant
that no depletion of H3 will be observed when other gases evolved by the coal
are present to react with it. With the size of the coal samples used ( 15 mg)
very significant depletion of H3 is observed when H2 at 1 atmosphere and
200 cc/min is employed. However, at 10 atm of H2 and 2000 cc/min and
above>as will be seen, the intensity of H3 remains constant throughout the ri
and is taken as being indicative of satisfactory and reliable analyses.
As an example of the above consider the dependence of H3 intensity on
temperature shown in Figures 103 and 104.. The curve in Figure 103 refers
to H2 reactant at 1 atm and the scatter of points indicates most probably,
consumption of H3 via reaction with evolved gases. On the other hand, as
shown in Figure 104 the H3 intensity remains constant throughout when H2
at 10 atm and 2000 cc/min are employed. We take the behavior of reagent gas
ion,H3^ shown in Figure 10 4 to indicate more reliable data and, have presented
the evolution curves for the conditions embodied therein.
The evolution curves of CH4 ( CH5+) , H2O (H3O+) , and C2H6( C2H5+)
from the coal designated as SRI-5 are shown in Figures 105-107. The
variation of H3 intensity with temperatures in the experiments with Coal
SRI-7 is shown in Figure 108 and the evolution curves for CH4, H2O, C2H6,
and H2S are given in Figures 109-112. The corresponding curves for
CoalSRI-10, Anthracite and Lignite are given in Figures 113-116, 117-119
and 120-123, respectively. The corresponding curves for a coke prepared
from SRI-7 are given in Figures 124-128 although these refer to a heating rate
of 15°/min rather than the 40c/min pertaining to the other solid samples.
-22-
-------
It is to be noted in Figure 127, that .even at 10 atm very significant
depletions of H3 occur when the coke sample is treated with hydrogen.
This signifies the presence of much more evolved gas from the coke samples
then from the non- pretreated coal samples.
-23-
-------
SPECIAL EXPERIMENTS
CO2 + C REACTIONS
In the oxidative gasification of coal or coke in O2-containing atmospheres
there is, of course, no question that the carbon in the evolved CO originates
in the solid reactant. However, in the oxidative gasification experiments in
which the solid reactant is treated with CO2 it is by no means certain that the CO
observed as a product contains any carbon derived from the solid.
To investigate this question in an unambiguous fashion we have treated
a carbon sample containing 13C with a gas mixture consisting of 1% 12CO2 in
argon and have observed the temperature dependence of the concentrations of
12CO+(— 28) and 13CO+ (— 29) .
e e
Figure 129 and 130 show the use of the non-isothermal method in analyzing
the isotopic content of the carbon sample. These figures show, respectively,
the production of 13CO2 and 12CO2 in an experiment in which the carbon sample was
treated with a gas mixture consisting of 1% O2 in Ar. The intensities of the peaks
indicate that the carbon sample is 57% 13C; an identical conclusion is reached by
examination of the 1ECO and 13CO evolved.
Figures 131 and 132 show the temperature dependence of the 13CO and
12CO concentrations, respectively, when the carbon sample is treated with a gas
mixture consisting of 1% 12CO2 in argon. It is clear from these figures that the
ratio of the amounts of 13CO to 12CO evolved is unity and reflects the isotopic
abundance in the solid as given by Figure 129 and 130.
-24-
-------
AIR OXIDATIONS
A number of experiments were performed using air at one atmosphere
passing over the coal beds. The results from all of these experiments were
similar in nature, and Figures 133 and 134are presented as examples. The
CO2 evolution shown in Figure 133 shows an extremely sharp spike in CO2 pro-
duction during which time the CO2 concentration swamps the signal amplifier.
Somewhat similar behavior is exhibited by the water evolution shown in
Figure 134 although this plot shows a preliminary dehydration before the spike.
It is apparent that as a particular temperature is reached, a very rapid
oxidation, quite probably an explosive oxidation, occurs . The stoichiometry
of the experimental arrangement is such that an excess of oxygen is present, a
2 to 1 molar excess of oxygen per minute compared to a 10 to 1 deficit present
in the previously presented oxidative studies. Commercial gasification
stoichiometry is much closer to the conditions present when 1% O2 in Ar is the
reactant gas. During this rapid oxidation, the temperature of the coal sample
in the furnace is undoubtedly not that shown on the temperature axis of
Figures 133 and 134.. The usual experimental conditions utilize low stoichiometric
amounts of oxygen coupled with gas flow rates to maintain average sample tempera-
tures near the furnace temperature, even though surface temperatures of the
sample may be quite different from the average. The rapidity of the air oxidation
will not permit these controlling conditions to be obtained thereby resulting in the
average temperatures and surface temperatures being unknown.
-25-
-------
DIS CUSSION
The large number of experiments performed during this contract research
by using the computerized non-isothermal kinetics laboratory has resulted in an
extremely large data output. Careful cataloging of the detailed behavior of a
variety of fossil fuels under a number of reaction conditions, was performed
in the previous section of this report. A cursory study of that data is sufficient
to demonstrate the complexity of the reactions resulting in gasification. The
interpretation of non-isothermal kinetics data offered in the remainder of this
report will be only the beginnings of understanding of this material.
KINETIC PARAMETERS
Table V presents the kinetic parameters of activation energy and frequency
factor for a number of important carbon gasification reactions occurring in coals
and cokes. These parameters are the result of analysis of the temperature
maxima of the various gas evolutions according to the procedure outlined in the
discussion of equation 12, and presented in detail elsewhere1. It includes para-
meters for gasifications from both oxidation and reduction studies. An example
of a typical plot is presented as Figure 3.
The occurence of several evolution maxima for a particular product gas are
a routinely observed phenomenon, as seen by inspection of the data in the previous
section. The complexity of the gasification kinetics, however, often makes it
difficult to identify a particular reaction by a progressive increase in Tm when
experiments are performed at several heating rates. This difficulty in identifying
reactions can be seen quite well by inspection of Table VII, VIII, and IX, Appendix A
Nevertheless, thirteen reactions have been identified in the studies of coal with
oxygen, oxygen/water, and hydrogen. These reactions, six producing CO, three
yielding CO2, two each producing methane and ethane, are summarized in Table V.
Reactions, although involving identical reactanta and products, are classified as
separate based on differences in temperature and maxima occurrance.
-26-
-------
TABLE V
KINETIC PARAMETERS
Oxidizing Atmosphere
SRI Coal No. 5
SRI Coal No. 7
SRI Coal No. 10
SRI Coke No. 7
Reducing Atmosphere
Three bituminous coals
(SRI Nos. 5, 7, 10
Tm
(30°/min)
835°K
752
900
1180
752
1000
Tm
(40°/min)
850°K
1031
CO Evolution
1/2 O2 + C — » CO
E
( kcal/mole)
14.0
21.2
27.0
30.0
21.2
10.0
CH4 Evolution
2H2 + C -» CH4
E
( kcal/mole)
11.7
21.5
log ko
3.0
5.8
6.1
5.0
5.8
1.1
log ko
2.2
4.0
Tm
( 30°/min)
883°K
1075
1075
Tm
(40°/min)
774°K
880
CO2 Evolution
O2 + C -» CO2
E
( kcal/mole)
14.8
10.0
10.0
C2H$ Evolution
3H2 + 2C -» C2H6
E
( kcal/mole)
11.3
20.5
log ko
3.1
1.0
1.0
log kg
2.7
4.5
-------
-4 -Of
i.
o
G
T
v
*
*
-16.
(.
?.CC
*icf 6
1.4C
1.6C
I/IV
SYMBOL KO.PTS- T.TOKKI)
ra 4 KINETIC PAHAVKTEKb FOh CO RVOLuiIOl,-0\I UI/.I NG AlM--COAI. ft b
* ICC
Figure 3
-28-
-------
OXIDATION REACTIONS
Nine reactions were observed for the evolution of CO and CO2 from three
bituminous coals and coke. The kinetic parameters shown in Table V for
these reactions are based on data taken from Table VII. and VIII. Kinetic parameter
for multiple evolutions are presented for the case of CO from SRI coal no. 7
because it was the only material for which it was possible to clearly identify several
trends of Tm increasing as a function of heating rate, although the identity of the
third reaction ( Tm - at 1180°K) may be doubtful. Confidence in the values
reported for these kinetic parameters is increased by the fact that in several
cases, evolutions occur at the same temperature in both the oxygen and oxygen
water experiments.
An important feature of the kinetic parameters present in Table V is the
general lack of coincidence in the occurrence of reactions. With the exception
of a single CO evolution from Coals No. 7 and 10, and the evolution of CO2
from Coal and Coke No. 7, no two reactions coincide. This is quite a remarkable
difference in a comparison of these carbon gasification reactions and the desul-
furization reactions previously reported1'2'4. In the sulfur reactions, five or
six desulfurization reactions were common to a total of twelve different fossil
fuels.
At the present time, observation of the general lack of coincidence for
Tm of oxidation reactions is attributed to differences in the carbon matrices
of the coals used for the experiments. Differing reactivity of coal macerals
is a well known phenomenon7 and the predominance of particular maceral
types in a given coal sample seems quite reasonable. The fact that several
different sets of experimental conditions yield similar Tm values for CO and
CO2 evolutions in particular coals tends to confirm the existence of such macro-
scopic differences in the coal materials used. The coincidence of one reaction
-29-
-------
producing CO in Coal No. 7 with the single identifiable reaction for CO pro-
duction in Coal No. 10 may indicate that some carbon matrix elements occur
in common for these two materials. Also of interest is that although the
identified reaction producing CO from Coke No. 7 shows no counterpart in
Coal No. 7, the only CO2 evolution identified in either of these materials yields
Trn values which indicate that they are the closely similar processes. At
present, no reason can be given for the coking process altering the carbon
matrix for one type of reaction and not for the other.
No detailed models are offered for the differing reaction kinetics
parameters because of a lack of physical information on the carbon matrices
present. An important area of future work would be the development of such
models with the use of pore size distributions and petrographic data on these
coal materials .
Some comparisons are possible between the data in Table V and activation
energies which appear in the literature. Van Krevelen8 in reviewing Oreshko1 s
work for which a thermo-balance technique was used, presents activation
energies for four different stages of oxidation. In two of the four stages,
decomposition reaction products yield CO and CO2. The first of these is alow
temperature decomposition occurring below 425°K and has an activation energy
of about 6 kcal/mole, and the second is a higher temperature decomposition with
activation energies 25-35 kcal/mole at temperatures higher then 525°K.
Three of the seven different reactions observed for oxidative gasifications
appear to be in agreement with Oreshko1 s activation energies for the combustion
stage of oxidation. The reamining four reactions occur with lower activation
energies than those discussed by van Krevelen. It is interesting that the higher
activation energy reactions occur for CO evolutions only, and then in only
two of the four materials shown in Table V. The presence of the low activation
energy, higher temperature reactions appears to indicate in another way that
several different kinds of carbon sites participate in the oxidative gasification
reactions .
-30-
-------
HYDROGASIFICATIONS
Two reactions each for methane and ethane evolution yielded kinetic
parameters as shown in Table V . The data used to calculate these values
came exclusively from hydrogasification studies conducted at 1 atm. Despite
the fact that H2 concentrations may vary under these conditions, the progressions
of Tm values with heating rate are more apparent for the 1 atm experiments. The
The Tm values at a particular heating rate, consistently separate into four
different temperature ranges for each of the three bituminous coals used. Kinetic
parameters for these hydrogasification reactions in the three coals must all
be nearly equal, and the calculations done were based on this assumption.
A quite remarkable, and we feel quite significant, coincidence of values
is noted in the kinetic parameter values for hydrogasification. Nearly identical
values of activation energy and frequency factor are obtained for the evolution
of methane and ethane for both the high and low activation energy processes
yielding these gases. More remarkable, however, is that methane is evolved
at much higher temperatures than ethane in both cases. A similar kind of
coincidence is observed in the evolution of COand CO2 from SRI Coal No. 5
and from the coke of SRI Coal No. 7.
These kinetic parameter data for oxidative and hydro-gasification seem
to indicate fundamental differences in the mechanisms of hydrogen and oxygen
interactions with coals. These differences are no doubt significant to com-
mercial gasification processes, and without a doubt these differences re-
emphasize the complexity of gasification reactions . It is hoped that work will be
done in the future toward the understanding of these mechanisms.
-31-
-------
THE CARBON D I O X I D E - C A R B O N REACTION
In the oxidative treatment of coke with carbon dioxide, carbon monoxide
is observed as a product as may be seen by reference to Table IX. In such
a process it is not immediately clear as to whether the carbon in the carbon
monoxide product is that originally contained in the carbon dioxide reactant
(in which case the carbon monoxide would not be a gasification product) or
whether it is derived from the solid coke. Thus if the reactions were
COE( g) + coke —» CO(g)+ oxygenated coke (13)
the CO would obviously not be a coke gasification product. On the basis of
previous studies9 using 14CO2 as a radioactive tracer it would appear that ( 13)
is a rapid process at temperatures of 1000°K and above. The conclusions of the
study of Bonner and Turkevich9 may not be directly appliable to the observation
here that carbon monoxide is a low temperature product of the oxidation of coke
by carbon monoxide ( of Table X) .
As shown in Figures 131 and 132 when a carbon sample containing 57%
13C is treated with 1ZCO2 in a non-isothermal experiment the CO evolved in the
range 520-840°K is 51% 13CO and 49% 12CO. If the process producing CO were
CO2( g) + carbon —» CO( g) + oxygenated carbon
Oxygenated carbon —* CO( g)
the observed 12CO could not be less than the 13CO. Hence, the result shows
that we may safely conclude CO to be a gasification product.
-32-
-------
While coke and coal are of course different solid reactants than the
carbon sample upon which this conclusion is based, we see no reason why this
conclusion concerning the low temperature gasification may not be safely
applied to coke and coal.
The kinetic parameters for two carbon gasification reactions resulting
from CO2 reactions with coke from SRI Coal No. 7 are given in Table VI,
TABLE VI Kinetic Parameters (CO2 - Coke Reactions)
Tm ( 30°/min) E Log kp
kcal/mole
700°K ( estimate) 17.5 5.0
991 25 4.9
-33-
-------
SUMMARY
During the past year, gasification studies in a variety of oxidizing and
reducing atmospheres were performed on a variety of fossil fuels. In all,
a total of 245 non-isothermal kinetics experiments were performed on eight
different coals and coal chars.
Representative data illustrating the qualitative differences between each
of the coals in each of the gasification conditions is presented in this report.
A total of thirteen different carbon gasification reactions were identified
in the course of this work. Included in these reactions is a previously unreported
low temperature gasification of carbon by carbon dioxide, itself a gasification
product. The kinetic parameters of activation energy and frequency factor for
these reactions were calculated.
-34-
-------
APPENDIX A: Gaseous Evolution Data for Oxidative Reactions
Table VII : Peak Temperatures in Oxidative Gasification of Coal
Table VIII : Effect of Water Vapor on Oxidative Gasification of Coal
Table IX : Peak Temperatures in Treatment of Coke with CO2 in Ar
Figures : 4-47
,35-
-------
TABLE VII
Peak Temperatures in Oxidative Gasification of Coal
Reactant Gas = 1% O2 in Ar
Solid Heating Temperatures at which
Reactant Rate H2O
Coal °/min
SRI-5 15 553
681
798
30 605
715
869
40 704
884
992
SRI-7 15 553
73Z
872
950
30 597
718
786
913
1008
40 609
755
810
1025
SRI-10 15 550
702
853
30 597
726
900
960
40 710
955
1062
CO NO
773
766 828
840
770
888
1277**
743 940
894
575 924
766 997
905
1185
588 820
790 950
942 1040
1210**
733 870
860
575 938
751
916
1066**
768 935
882
1011
1295**
Peaks Observed - °K
CO2
551
764
820
566
888
898
1240
547
863
977
608
697
1100
615
745
1103
540
868
568
987
580
1160
1248
SO2
746
829
680
860
730
718
763
1068
740
790
1088
762
775
02*
576
847
567
768
996
577
932
-36-
-------
TABLE VII (continued)
Solid Heating
Reactant Rate
Coal °/min
Anthracite 15
30
40
Lignite 15
30
40
Temperatures at which Peaks Observed - °K
HEO
552
916
586
1040***
598
817
998
583
674
619
685
726
419
625
742
CO
542
862
962
572
927
577
917
1248
663
576
716
1013**
595
716
1025**
NO
897
566
938
995
578
972
652
742
575
775
586
815
CO2
545
930
565
1048
576
938
1137
687
553
808
586
828
S02 02*
542
900
1048 575
1007
935 578
1050 980
1180
575
708
588
730
* Negative Peaks
** Peak is actually a shoulder on the high-temperature side of another peak
*** Uncertain
-37-
-------
TABLE VIII
EFFECT OF WATER VAPOR ON OXIDATIVE GASIFICATION OF COAL
Reactant Gas: 1%O, in Ar, saturated at 300°K with H,O
Solid Reactant Heating Rate
Peak Temperatures in °K
H2O CO
Coal
SRI-5
SRI-7
SRI-10
Anthracite
Lignite
0 /min
15
40
15
40
15
40
15
40
15
40
862 803
1153
863
884
973
867
781
946
911
961
1158
817
875
1022
872
976
1100
870
955
1042
917
1009
1132
690
784
745
840
1070
797
608
960
1081
879
949
971
1080
690
740
*Negative Peaks
-38-
-------
TABLE IX
Peak Temperatures in Treatment of Coke (SRI-7) with CO2 in Ar
(Gas Flow Rate = 150 cc/min)
Heating Rate
0 /min
5
15
20
30
40
60
Peak Temperatures in °K
H,
500
560
1098
585
1100
595
1080
604
1108
H2O
927
520
868
580
1035
614
1046
630
1093
639
1133
CO
509
564
1014
586
998
594
737
1048
605
745
1066
NO
500
562
580
590
600
"CH3"
CO2*
500
554
1015
575
1023
588
1070
598
1077
Negative Peaks
-39-
-------
R164B.DAT
32CC
1
8
I
I
T
E
N
S
I
1600
8CC-
I I I
740 96C
TEMPERATUREt *K
52C
118C
14C
SYMBOL MO.PTS-
1 113
LEGEND
H20* TROM SRI COAL #5» AR+1*02 AT 2CC CC/MIli. 3C»/MI»
Figure 4
-40-
-------
R164C.DAT
8
I
N
T
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N
S
I
T
4 <•»/».
w
3CC-
2CO
ICC-
•I-
52C
74C 96C
TEMPERATURE» *K
118C
SYMBOL NO.PTS.
69
LEGEND
CO* PROM SRI COAL #5t AR+1*OE AT 2CC CC/MINt 3C»/MIN
Figure 5
-41-
-------
R164D-DAT
100
8r
v
H
/
Z
I
I
T
t.
I
S
I
T
I
60
•4-
+
300
520
740
TENPEBATUBE,
960
1180
14C
SYMBOL IO.PTS. LEGEND
18 HO* FROM SRI COAL #5» AH+1*02 AT 200 CC/MIHt 3C«/MIH
Figure 6
-42-
-------
H164P-DAT
8(
4 6CCC
I
K
T
E
H
S
I
* Af\f\/\,
v %v\
_H 1 \
740 960
TENPERATUHB* »K
520
14C
SYMBOL BO.PTS. LEGEND
126 C02+ FROM SRI COAL #5, AR+1*02 AT 200 CC/MIN» 30*/MID
Figure 7
-43-
-------
E164G.DAT
15C
120
E
6
4
I
V
T
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M
S
I
T
T
90
60-
30-
I
*iAr
Ox/id
520
740 96C
TEMPEBATUBEt *K
1180
14CC
SYMBOL MO.PTS. LEGEND
35 S02+ FROM SRI COAL #5» AB+W02 AT 200 CC/MItU 3C*/MIH
Figure 8
-44-
-------
R164E-DAT
8C
64C
48
I
N
T
E
H
S
I
T
32CO
.•"•V
•*"
\
745 96C
TEMPERATURE. *K
530
118C
14C
SYMBOL
NO.PTS*
125
LEGEND
02f
SRI COAL
AR-H*02 AT 2CC CC/MINf 30-/HIH
Figure 9
-45-
-------
R163B.DAT
5AA/\
v/v/«J
4CC
N
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E
8 3C*
I
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T
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T
Inn
\f\j\
(H
30C
•
•
I 1 I
740 960
TEMPERATUREt «K
520
1130
14CC
SYMBOL HO.PTS. LEOEHD
121 H2CH- FROM SRI COAL #7, AH+K02 AT 200 CC/MIR, 30«/MIH
Figure 10
-46-
-------
R163C-DAT
2
8
I
H
T
I
N
S
I
T
r
3001
2C£
• I < t
740 960
TEMPERATORE* •(.
300
520
14C
SYMBOL NO.PTS* LEGBID
112 CO* FROM SRI COAL #7. AR+1*02 AT 2CC CC/MIII*
Figure 11
-47-
-------
R163D.DAT
15!
120
3
0
I
I
T
E
II
S
I
T
T
9(
60
r.
v .
300
sac
740 9
TEMPEBATUJiE* «K
SYMBOL NO.PTS.
LEGEND
HO* FROM SRI COAL
AR-MX02 AT 200 CC/KINt 30«/«H
Figure 12
-48-
-------
H163F.DAT
I
N
T
E
N
S
I
T
4/\/\A-
W\y\/
2000-
520
740 960
TEMPERATURE* *K
1400
SYMBOL NO*PTS
121
LEGEND
C02* FROM SRI COAL #?» AR+1W2 AT 200 CC/MIH* 3C»/MIK
Figure 13
-49-
-------
R163&.DAT
6
4
I
V
T
E
fi
S
I
T
T
360
240
ISO
300
520
740 96G
TEMPERATURE* *K
118C
14C
SYMBOL NO.PTS. LEGEND
36 S02* FROM SRI COAL #7t Afi+l*03 AT 2CO CC/MIS, 3C»/MIN
Figure 14
-50-
-------
R163E.DAT
8C
64(
48 CO
I
N
T
E
N
S
I
T
32Ow'
160
30C
520
74C 960
TEMPERATURE, *K
SYMBOL NO.PTS- LEGEND
121 02+ FROM SRI COAL #7t AR+1*02 AT 200 CC/MIH* 30»/MIN
Figure 15
-51-
-------
K
/
E
1
8
I
H
T
B
F
S
I
T
1000-
500^
R165B.DAT
3CC
520
96C
118C
14C
TEMPERATURE. •£
SYMBOL HO.PTS. LECEKD
129 H20+ TBOH SRI COAL #1C» AR+1*02 AT 2CC CC/MIMt 3C»/MIN
Figure 16
-52-
-------
R165C.DAT
2
8
I
N
T
E
N
S
I
-t-
52C
74C 96C
TEMPERATURE* »K
nac
SYMBOL RO.PTS- LEGEKD
94 C(H FROM SRI COAL #1C» AR+1*02 AT 2CC CC/HIN» 3C»/HIN
Figure 17
-53-
-------
R165D.DAT
IOC
8C
M
E
3
I
N
T
E
R
S
I
T
Y
60
40-
2C-
520
74C
960
118C
14C
TEMPERATURE.
SYMBOL HO-PTS. LEGEHD
34 H04- ?HOM SRI COAL # 1C. AR+K02 AT 2CC CC/MIK. 3C«/«IN
Figure 18
-54-
-------
R165F.DAT
4
4 6CCC1
I
N
T
E
N
S
I
•f-
520
74C 96C
TEMPERATURE* *K
118C
SYMBOL NO.PTS. LEGEHC
129 C0?f FROM SHI COA1 #10t AR-»-l*02 AT 2CC CC/MIHt 3O/MIN
Figure 19
-55-
-------
H165C.DAT
4CC4
320
B
6
4
240
T
E
H
S
I
T
T
160-
80-
+
•+•
+
•irtrt
Oi/v
52C
743 96C
TEMPERATURE* *K
14C
SYMBOL HO.PTS. LEGEKD
11 S02+ FBOM SRI COAL #1C* AH+1*02 AT 2CC CC/HIN* 3C«/MIN
Figure 20
-56-
-------
R165E.DAT
64CC
3
2
I
H
T
E
N
S
I
T
T
16CC-
-f-
-*•
52C
740 960
TEMPERATURE, *K
SYMBOL NCNPTS-
129
LKEND
02+ FROM SRI COAL #10t Aftfl<02 AT 2CC CC/«IK» 3C»/MIH
Figure 21
-57-
-------
1
8
R166B-DAT
6C
4500
I
R
T
E
H
S 3CCO
T
y
•4-
52C
740 96C
TEMPERATURE* «K
14C
SYMBOL HO.PTS- LEGEND
106 R20+ FROM AHTHHACITE* AR+1*02 AT 20C CC/MIH* 3C»/MIN
Figure 22
-58-
-------
R166C»DAT
75C
2
8
I
N
T
E
N
S
I
T
Y
450'
SCO-
ISO
w\/v
52C
740 96G
TEMPERATURE, -K
1180
SYMBOL NO.PTS* LEGEND
8C CO+ FROM /1KTHRAC1TE, AB+1*02 AT 2CC CC/MINt 3C»/MIN
Figure Z3
-59-
-------
K166D.DAT
I
II
T
B
N
S
I
T
T
1CC+
8/Y
V
6(
40
2C
•f-
300
52C
74C 96C
TEMPERATURE, «K
118!
SYMBOL NO-PTS- LEGEMD
39 HO+ PROM ANTHRACITEt AR+K02 AT 2CC CC/MIHt 3O/HIN
Figure 24
-60-
-------
3
2
I
N
T
E
N
S
I
T
y
R166E.DAT
75CC
15C
•f-
-I-
52G
74C 960
TEMPERATURE* *K
iiac
140C
SYMBOL NO.PTS. LEGEND
106 02* FROM ANTHRACITEj AB+1*02 AT 20G CC/MIUf 3C»/MIK
Figure 25
-61-
-------
R166F.DAT
COCO
8000
M
E
4
I
V
T
E
•
S
I
J 400CM
2000
•*•
-I-
300
520
740 960
TEMPERATOEE, •!
1180
1400
SYMBOL IO.PTS.
106
LEGEND
C02f FBOH ANTHRACITEr AR-»-l*02 AT 200 CC/MIUt 3C-/MIB
Figure 26
-62-
-------
R166G-DAT
5*^±
w
40'
6
4
I
N
T
E
H
S
I
T
Y
30-
2C'
1C-
-t-
-H
74C
TEMPERATURE,
52C
118C
14 C
SYMBOL HO.PTS. IEGB1ID
11 S02f FROM ANTORACITEt AR+1*02 AT 2CC CC/MIKt 3O/MIH
Figure 2.1
-63-
-------
M
I
1
8
I
N
T
E
R
S
I
T
T
R167B»DAT
6t
4800-
3600-
24CO
. .
3CC
52C
118G
UC
TEMPERATURE.
SYMBOL HO.PTS-
128
LEGEND
H20+ PROM LIGNITE* AB+1*02 AT 300 CC/MIN, 3C«/KIN
Figure 28
-64-
-------
R167C«DAT
32C
2
8
I
N
T
E
N
S
I
T
Y
24C
16O
80-
3CC
520
740 960
TEMPEfiATORE. »K
1180
14C
SYMBOL HO.PTS- LEGEND
81 CO+ FHOH LIGNITEt AR+1*02 AT 2CC CC/HIHt 3C-/HIH
Figure 29
-65-
-------
R167D.DAT
I
N
T
E
N
S
I
T
Y
50-
4/%
\j
30
20
It,
«
520
740 960
TEMPERATURE* *K
1180
14C
SYMBOL BO.PTS. LEGEND
17 NO* FROK LIGNITEf AR+1X02 AT 200 CC/MIBf 30»/HIN
Figure 30
-66-
-------
R167F.DAT
4
4
I
N
T
E
N
S
I
T
Y
2f\f\f\,
\s\j\s
52C
74C
96C
1190
14CC
TEMPERATURE* «K
SYMBOl NO.PTS. LEGEND
130 C02; FROM LIGNITE. AR-H*02 AT 2CC CC/WIN, 3C»/MIN
Figure 31
-67-
-------
H167C.DAT
8*v
\j'
H
/
E
6
4
I
H
T
E
H
S
I
T
T
40
2O
I I I
740 960
TEMPERATURE, *K
300
520
1180
14C
SYMBOL NO.PTS. LEGEHD
6 S024- FROM LIGHITE, AH;i%02 AT 200 CC/MI1* 30-/MIN
Figure 32
-68-
-------
I
N
T
E
N
S
I
T
Y
45CO-
15C
R167E«DAT
520
740
96C
1180
TEMPERATURE, *K
SYMBOL NO-PTS. LEGEND
02+ FROM LIGNITEt AR+1%02 AT 200 CC/MIS* 3G«/MIN
Figure 33
-69-
-------
PR71A-DAT
1
8
I
N
T
E
N
S
I
T
Y
36
12-
1f\r\r
\j\j\.
12CC
140C
TEMPEBATOFEi
SYMBOL NO-PTS. LEGEND
47 H20+ PROM SRI COKE #5t AR+K02 AT ICC CC/MIN, 15MG SAMPLEt 3C»/MI1I
Figure 34
-70-
-------
PP71B-DAT
64-
48-
i
N
T
E
N
S
T
T
Y
3?-
16'
H
v
TEMPERATURE, -K
SYMBOL NO-PTS. LEGEND
53 CO+ FROM SFI COKE #5» AR+1%02 AT 1CCCC/MIN, 15MG SAMPLE, 3O/MIN
Figure 35
-71-
-------
PK71D.DAT
I
N
T
E
N
S
I
T
Y
8rt^
w
TEMPER/I TUREi
12C
Ur
SYMBOL NO.PTS. LEGEND
137 C02+ FROM SRI COKE #5» AP+1*02 AT 1CCCC/KIN» 15MG SAMPLE* 3C-/MIN
Figure 36
-72-
-------
PR71C-DAT
V
/
E
3
T
N
T
•R
N
S
I
T
Y
1504
90-
60-
•V-
wv./
•» •f
5?0
74 C
TKMPERATURE,
96 C
118C
1400
SYMBOL NO.PTS. LTOEND
1RC 0?+ FROM SPI COKE #5, AP+17.02 AT 10CCC/MIN, 15MG SAMPLE. 3O/MIN
Figure 37
-73-
-------
R1G5A-DAT
BC
K
2
I
N
T
E
N
S
I
T
Y
40-
+
+
-H =
Oww Iwwv
TEMPERATUREt -K
SYMBOL NO-PTS.
LKCEND
H?+ FPOK SRI COKE #7» AR+iy.02 AT 1CCCC/WIN» 15WG SAMPLE* 2C-/VIN
Figure 38
-74-
-------
1?5C
i
8
I
N
T
E
N
S
I
T
•"•
y
75C
25C
R1C5B.DAT
..-'•
o r»/
" w
I'!.'
TEMPERATURE.
SYMBOL NO-PTS«
2CP
LEGEND
H?0+ 7POM SRI COKE #7, AR+17-02 AT 100CC/VTN, 15MG S^'pTP, 20»/Mlli
Figure 39
-75-
-------
R1C5C-DAT
16C
2
8
I
N
T
E
N
S
I
T
Y
12C-
4O
8r\f\
w
TEMPERATURE,
1400
SYMBOL NO.PTS. LEGEND
107 CO+ FHOM SRI COKE #7,
AT 1CCCC/MIN, 15"G SAVPTK»
Figure 40
-76-
-------
R1C5D.D/T
1 or*'
M
/
K
80-
I
N
T
V
N
S
I
T
Y
60-
4C-
rtn •* r>
ww 1 v*
TEMPERATURE, -K
1+00
SYMBOL NO-PTS. LEGEND
4C NO+ FROM SRT COKE #7, AR+1202 AT 1GGCC/MIN. 15MG SAVPLF, 20»/MIN
Figure 41
-77-
-------
R1C5F.DAT
4
4
I
N
T
E
N
S
I
T
y
jr
occ
TEMPERATURE.
1r*/>/%
WWW
12CC
149
SYMBOL NO-PTS.
181
LEGEND
C0?+ FROM SRI COKE #7, AR+1*02 AT 1CCCC/MIN, 15MG SAMPLE* 2C-/MIH
Figure 42
-78-
-------
I
N
T
E
N
S
I
T
*
v
2<">r\.l
vwT
R1C5E-DAT
...X"
'<•.
•x.
52C
74 C
96C
TEMPERATURE. «K
118!
SYMBOL NO-PTS.
2C2
LEGEND
02+ FROM SRI COKE #7. AR+1%0? AT ICCCC/MINt 15HG SAVPLE.
Figure 43
-79-
-------
PR69A-DAT
15Ct
120
1
8
I
N
T
E
K
S
I
T
Y
9/v
w
.*
1400
TEMPERATUREt »K
SYMBOL NO-PTS. LEGEND
88 H20+ FROM SPI COKE #10. AE+17.02 AT 1CCCC/MI Ntl5 MG SAWPLE»30-/MTN
CHANGES FOR NEXT FUN ? ALL
Figure 44
-80-
-------
T
N
T
F,
N
S
T
T
Y
1?-
ROC 1
TFMPrPATURK,-K
1400
SYMPOT, NO
PTS-
50
CO+ FHOM SPT COKF #1C» AR+17.0?, 1COCC/MIK, 15VG SAMPLE, 3C-/MIN
Figure 45
-81-
-------
PB68D.DAT
640
4
4
I
N
T
E
N
S
I
T
Y
48(
32C
16C
12C
——I
1400
TEMPERATURE.
SYMBOL NO.PTS- LEGEND
114 C02+ FROM SRI
CHANGES FOR NEXT RUN ?
COKE #10. AR+1*02 AT ICCCC/H'H, 15MG SAMPLE.
Figure 46
-82-
-------
PP.6nc.PJT
M
/
F
T
N
1
F
N
S
T
T
Y
40-
7-4
1400
SYMBOL NO-PTS. T.FGFND
17R 0?+ FP
SPT COKF
AT
15W SflVPLF, 3P-/MIK
Figure 47
-83-
-------
APPENDIX B: Gaseous Evolution Data for Pyrolysis Experiments
Table X: Peak Temperatures for Pyrolysis of Coals and Cokes
Heated at 30°/min in Argon
Figures: 48 - 102
-84-
-------
TABLE X
Peak Temperatures for Pyrolysis of Coals and Cokes Heated
at 30°/min in Argon
Solid
Reactant
SRI-5
SRI-7
SRI-10
Anthracite
Lignite
Coke-
SRI-5
Coke-
SRI-7
Coke-
SRI-10
H2
608
714
600
827
1213
608
947
1082
635
701
597
608
840
608
1092
Peak T(
"CH3"
608
817
860
600
829
874
856
940
608
927
628
704
823
598
991
600
850
607
992
imperatun
H2O
629
726
828
632
741
860
751
1265
641
873
675
719
817
618
1053
630
850
641
1062
es in °K
CO
605
744
605
807
625
729
927
1254
603
625
696
1010
606
608
806
602
NO
608
677
608
800
640
730
994
1258
600
634
690
603
608
806
613
CO2
610
700
607
810
674
733
941
607
760
918
646
597
970
608
806
610
S02
616
704
805
588
806
606
718
817
839
932
599
828
630
599
597
806
1222
608
-85-
-------
H224A-DAT
I
N
T
E
N
S
I
T
Y
?f*.
\J
-f-
-f-
52C
74C 96C
TEMPERATURE. «K
119C
SYMBOL NO.PTS-
141
LEGEND
H?+ FROM SRI COAT. #5t AH AT 200 CC/MIN, 3C«/MIN
Figure 48
-86-
-------
I
N
T
F
N
S
T
T
1
y
?^^i.
w
»^ • •«•••• ••*
52C
74 C
TEMPEhATUREf
96 C
SYVBOL NO-PTS. LTOEND
141 CH3+ FROM SRTCOAL #b, AR AT 2CG CC/MIN, 3C»/MIN
Figure 49
-87-
-------
I
N
T
E
N
S
I
T
16C
1?CC
9A/V
W*y»
4rt/>.
^v
*..••«.
5?C
740
TEMPERATURE,
96C
11SC
SYMBOL NO.PTS. LEGEND
141 H20+ FRCW Shi COAL #5, AR AT ?CC CC/MIN, 3C-/MIN
Figure 50
-88-
-------
RP24D-DAT
V.
K
?
R
I
N
T
E
N
S
I
T
Y
9nr\.
w^
6/•!/->.
\/*^
_| (
74 G
TEMPERATURE.
52C
96C
1180
14C
SYVPOL KO.PTS- LKGEND
141 CO+ FROf-' SKT COAL A'5. AR AT
?GG CC/VIK. 3C7./MIK
Figure 51
-89-
-------
40
V
/
E
T
E
N
S
I
T
Y
PC'
520
74 C
96C
113C
TEMPERATURE.
SYMBOL NO.PTS- LEGEND
141 NO+ FROM SRI COAL #5t Aft AT
CC/MIN. 3C-/HIN
Figure 52
-90-
-------
K224f.DAT
4
4
I
K
T
E
K
S
I
T
Y
90'•
52C
74C 96G
TEMPERATURE. «K
11QC
SYMBOL NO.PTS. LEGEND
141 C0?+ FIVOH SPI COAL #5, AR AT 2CC CC/MIN. 3G«/KIN
Figure 53
-91-
-------
1
-------
h??o/I.DAT
1r\r\
\>\j
T
N
T
V,
N
S
I
T
Y
40-
52C
74C
9GC
118C
TEMPShATUltK. »K
SY^POL NO.
PTS«
1.3?
LEGEND
!!?+ FROf
SRT COAT, #7. Afi AT 2CC CC/MU. 3C«/MU«
Figure 55
-93-
-------
KP25B.DAT
1
5
I
N
T
E
N
S
I
T
Y
52C
740 96C
TEMPERATURE, «K
SYMBOL NO«PTS«
130
LEGEND
CH3+ FftOM SHI COAL #7, Afi AT 200 CC/MIN, 3C«/MIN
Figure 56
-94-
-------
1 COG'
soc
h22bC.DAT
1
n
I
N
T
N
S
T
T
••*.
•+•
-H
+
52C
740 9bC
TEN'PRHATUREt «K
118C
14C
SYMBOL
131
LEGKND
H?0+ FROM SHI COAL #7, AH Vf POO CC/MIN,
Figure 57
-95-
-------
2
8
T
N
T
E
N
S
I
T
Y
9/\/v
wv>
6rtA.
vw
-H
119C
52C
740 96C
TEMPERATURE. «K
14C
SYMBOL NO-PTS. LEGEND
131 CO+ FROM SRI COAL #7, AR AT ?CC CC/MIN» 3C»/MIN
Figure 58
-96-
-------
M
/
V,
I
N
T
E
N
S
I
T
Y
H225E-DAT
52G
74C
96C
118C
TEMPERATURE* »K
SYKPOT.
LEGEND
NO+ FHOt-' SRI COAL ',17, AR AT ?CC CC/MIN* 3C-/MIN
Figure 59
-97-
-------
4
4
r
N
T
F
N
S
I
T
Y
40
30'
!*••*»« •
» •**• *•
520
74C
TEKPERATUREt
96C
SYMBOL NO.PTS-
131
LEGEND
C02+ FHOH SKI COAL #?, AH AT 200 CC/MINi 30VMIN
Figure 60
-98-
-------
6
4
I
K
T
S
I
T
Y
5?C
740 96C
TEMPERATURE, -K
119C
14C
SYVPOL KO-PTS.
107
LEGEND
S0?+ FROM SM COAL H7, AR AT 2GC CC/I-'IN, 5C-/MIN
Figure 61
-99-
-------
h?26A«DAT
F
2
I
N
T
R
N
S
I
T
Y
3f\f\.
\j\t
-t-
520
740 96C
TEMPERATURE* «K
14CC
SYMBOL NO-PTS.
136
I.EttBND
H?+ FROM SKI COAL
AH AT 200 CC/MIM, 3C«/MIN
Figure 62
-100-
-------
T
N
T
E
N
S
r
T
Y
Rr>r\f\,
\'\.t\'
£>2C
74C
96C
118C
TEMPERATURE, -K
SYVBOT, HO.PTS-
1CS6
LEGEND
CH3+ TKOV Shi COAT A'lC, AH AT 2CC CC/N'IN 3O/MIN
Figure 63
-101-
-------
lf226C.DAT
/
R
1
0
I
N
T
K
M
S
I
6A/-XA
VV/W
4-
•+•
52C
740 96C
TEMPERATURE. 'K
119C
14C
SYMBOL NO.PTS- LEGEND
136 H20+ FHOM SRI COAL^IC. AR AT 2CG CC/KIN. 30"/MIN
Figure 64
-102-
-------
M
/
K
T
N
T
E
N
S
I
T
Y
52C
740
TES'PEKATUKEf
96C
SYVPOT. KO-PTS. LEG FIND
135 MO+ FROM SRI COAL #1C. Ah AT 2CC CC/MIN*
Figure 65
-103-
-------
R226G.DAT
6
4
I
N
T
E
N
S
I
T
Y
16C
8f\
\j
r-v
H
•»..«»•
520
74C 960
TEMPERATURE. «K
SYMBOL NO.PTS. LEGEND
134 S02+ FROM SRI COAL #10. AK AT 200 CC/MIN. 306/MIN
Figure 66
-104-
-------
K226D.DA1
4CCCH
?
8
r
N
T
E
N
S
I
T
If
5?C
1
\
1 1
74 C
TEMPEKATUHE.
t
96C
•K
1 ii i
1 1Q ^ 1 A^
iiOv I'tu
SYMBOL KO.PTS-
135
LKGEKD
CO+ FliOM SHI COAT, #10» Ah AT 2CC CC/MIN, 3G6/KIK
Figure 67
-105-
-------
R2P6F-DAT
4
4
I
N
T
F,
N
S
T
T
Y
6nr\L
wwT
.«"'
.•««•*'••«
+
-H 1
740 96C
TEMPERATURE, «K
5?C
113C
SYMBOL NO.PTS- LEGEND
135 C0?+ FROM SHI COAL #1C» AR AT 2CC CC/KIN* 3O/MIN
Figure 68
-106-
-------
K22ftA'DAT
I
N
T
K
N
S
I
T
Y
52C
740 96C
TEMPERATURE* «K
nac
SYMBOL NO-
PTS-
119
LEGEND
H2+ FROt-1
SI(I AtlTRHACITE. AR AT
CC/MIN, 3C"/MIN
Figure 69
-107-
-------
I
N
T
E
K
S
I
6f\f\,
\t\'
400'
^....•'
52C
74 (
96C
113C
TWPERATUHK, «K
SYt'POT, NO.PTS. I.EGFKD
11H C"3+ Ff'OM Shi A K'i'H
H AT ?CC CC/MI!-;, 30-
Figure 70
-108-
-------
1
R
I
M
T
F
N
S
I
T
y
6n/\
^j\j
• •
-t-
52C
740 96C
TEMPEHATUhE, »K
11BC
14C(
SYMBOL IIO.PTS- I.RGFKD
118 !!20+ FhOM SRI ANTFFRACITE> Ah AT 2CC CC/1'IN, 3C-/KIN
Figure 71
-109-
-------
: ?'?-•'P-:,'A I
?
q
T
N
T
F
S
I
4CC
?r*f\,
V/*y
52G
74C 060
TFVFFFtATufiEi »K
SY'-'POT, NO-FTS.
co-f- ^por SH Mi'iiHRAcm:i AI- AT ^cc cc/mi.
Figure 72
-110-
-------
i<223K«DAT
I
lM
T
E
N
S
I
T
Y
• •••*! •« »w • *
* • •••• ••••••*
• * * • •• •
52C
740 96C
TEKPKHATUHE. «K
use
14C
SYMBOL KO-PTS.
LEGEHD
KO+ FKOK SRI AKTHRAOTTE. Ah AT 20C CC/MIN. 3C=>/MIN
Figure 73
-111-
-------
4
4
I
I!
T
E
K
5
I
T
y
40' •
?<-.
o
74
960
113C
140C
SYMBOL NO.PTS. LEOEHD
119 f:02+ FKOf Shi ANTfifiACITE. Ah AT 2CC CC/l'It-ii 30-/MN
Figure 74
-112-
-------
1 n±
i o
f
/
r
6
4
T
N
T
E
r;
s
i
T
Y
4
-f-
52C
74C
TEMPERATUHK,
96(
HOC
SYftpOT. N'O-PTS.
LEGEND
S0?+
SHI ANTHRACITE, AH AT ?CC CC/MIN, 3C«/MIN
Figure 75
-113-
-------
I'
E
?
T
t;
T
v,
K
s
I
T
y
40-
520
74
960
(•
14CC
SY!'BOr, I.O.PTS.
1.'51
^+ KK)'-' SKI UGMTK, AH *1 ^00 CC/KH.,
Figure 76
-114-
-------
K227B.DAT
I
N
T
V,
K
S
I
T
?4CO
1 O
JM ,.
1 ^>^rt
1 .C ww
52C
740 96C
TEMPKRATUREi »K
11SC
14C
SYMBOL NO.PTS. LKGKKD
131 CH3+ FROM SRI MGMITEt AH AT 2CC CC/KIN* 3C-/MIN
Figure 77
-H5-
-------
I-1
/
F
1
T
K
f;
S
I
T
Y
—I 1 1-
74C 9(3C
TEf-'PERATUUE. -K
113C
Mrw
w».
SYMBOL tiO-PTS. T,^H!I!)
f/ SHI
F.t Ali AT ?CC CC/t-'It., ^
Figure 78
-116-
-------
?r\r\r\ i
v >\/\' T
T
R
M
S
T
T
Y
52C
74C 96C
TEMPERATURE. -K
110J
SYf-"ROI, MO.PTS.
CO+ b'HOr SHI LIGMTF., AH AT i'CC CC/l'.Ilit 3C«
Figure 79
-117-
-------
•i
V
\.
S
T
T
Y
t-.f', '••( ->!)•if
x*—»•
•t-
IVJC
SYf'l'OT, l.O.hTS- r,KGKt.])
7? KO+ FS-OI-1
Figure 80
-118-
-------
600C1'
I
M
T
E
N
S
I
T
Y
KP27F.DAT
.*'
740 96C
TEMPERATURE, «K
SYVPOT, JiO.PTS. LEGEND
115 C02+ FROM SKI I.IGMTE. Ah AT 2CC CC/KIht 3C6/KIN
Figure 81
-119-
-------
6
4
I
N
T
E
t-1
S
I
T
Y
In.
\j
52C
74 C
TEVPEKATURE,
96 C
14C
SYMBOL NO.PTS- LEGKKD
46 S0?+ FROM SPI L
AT ?CC CC/MIN. 3C-/MIW
Figure 8Z
-120-
-------
HPP9A-DAT
I
N
T
E
N
S
T
T
Y
60-
3/>/^
ww
74C
TRMP^RATURR,
96C
SYMBOL KO.PTS. LKGRND
13R H2+ FFOM SHI COKE
AH AT 20C CC/MIN, 3C»/MIN
Figure 83
-121-
-------
h229P.DAT
V
/
F
I
K
T
E
N
S
I
T
Y
ISO?
9r\r
\j\
inn I
w v-»T
-=¥
H ^ \-
740 96C
TEMPERATURE. «K
**•••• *••»
52C
SYMBOL NO.PTS- T.EGENU
13R CH3+- FKOf-' SRI COKE #5t Aft AT ?CC CC/KINi SC'/F/IH
Figure 84
-122-
-------
1 0^/"«.
I c >./w
1
q
I
N
T
S
I
•-...••
*••..
74!
96C
14CC
SYMBOT. NO.PTS- LKGKKD
138 H?0+ KHO^ SRI COKF fib, AH M'
3O/KIN
Figure 85
-123-
-------
V.
/
T.
I
M
T
F
H
S
I
T
y
r
-H
74G 96C
TEh'PEHATUHEt -K
5?C
SYMBOL NO.PTS-
130
LBRFND
CO+ FftOM Shi CORK #
AR AT ?OC CC/MTN, 3C-/MIN
Figure 86
-124-
-------
K2Z-JK-DAT
I
N
T
S
T
T
Y
74 C 96C
TEMPEHATUKE, »K
118C
SYMPOT. NO.PTS. LKGKND
NO+ Ff.Of-' SHI COKE #
Ah AT 2CO CC/f'INi 30-/MTN
Figure 87
-125-
-------
4
4
I
N
T
E
S
T
T
Y
15C+
9«.
w
60-
3«.
V
h229F-DAT
52C
74(
96C
1400
SYWBOL NO.PTS- LEGEND
138 C02+ FhOM SIiI COKE #5, AK AT PCC CC/MIK, .'iC'/MIU
Figure 88
-126-
-------
6
4
I
N
T
F.
N
S
I
T
Y
15-
5-
74C
96C
TEMPFliATUhEt
SYMPOT. NO
. PTS«
].'35
LR;FHD
S0?+
Sid COKE #5, M AT ?OC CC/MN. 3C«/f-'IN
Figure 89
-127-
-------
R162A.DAT
200
160
120
I
I
T
B
I
S
I
T
T
8/x
«7
40
/ V
•*•
•*•
300
520
740 960
TEMPERATURE, »K
1180
Mn/1
l/v.
SYMBOL
IO«PTS
145
H2+ rKOM SRI COKE f?» AR GABBIER GAS AT 200 CC/HIB. 30* /MI I
Figure 90
-128-
-------
4CCC
1
8
I
If
T
K
I
S
I
T
3000
2000
1000
R152B.DAT
300
520
740 960
TEMPERATURE* •!
1180
14C
SYMBOL HO.PTS.
145
LEGEHD
H20+ FROM SRI COKE *7. AR CARRIER CAS AT 200 CC/MII* 30*/MIH
Figure 91
-129-
-------
R152ODAT
500f
4CO
N
I
2
3
Ovtj
200
100
yt
i
V
300
520
740 960
TINPERAT0BS* •!
11SC
1400
SYMBOL HO.PTS. LKEHD
145 C(H FROM SRI COO *7, AR CARRIER GAS AT 200 CC/KIIt 50*/HII
Figure 92
-130-
-------
R152E.DAT
8i
V
600-
4
4
T
I
H
S
T
1
4«*\
\J\S
•
•
\
3CC
520
74C
TEMPERATURE i
960
118C
14CC
SYMBOL
145
LEGEND
C02f FROM SRI COO *7« AR CARRIER GAS AT 2CC CC/MIlt 3C*/HI
Figure 93
-131-
-------
R152F.DAT
160
6
4
I
N
T
I
R
S
I
T
T
1ZO
80
300
520
740 960
TEMPERATOBS* *E
118!
14;
SYMBOL IO.PTS. LECEHD
145 S02f FROM SRI COKE f7t AI CARRIER CAS AT 200 CC/MIN* 30*/MIH
Figure 94
-132-
-------
R152D.DAT
25C
2C01
15CH
I
I
T
I
I
S
I
I
T
Irt/Y
\M/
52C
740 960
TEMPERATURE, «K
118C
14C
SYMBOL NO.PTS* LKEHD
145 NCH- FROM SRI COKE «7t AR CARRIER GAS AT 2CC CC/MIN» 3O/MIH
Figure 95
-133-
-------
h23CA-PA'r
40
3"Y
w
I
N
T
E
N
S
I
T
Y
2«.
w
I".
V
•4-
520
•74C
TEMPERATURE*
960
118C
SYMBOL NO'PTS- LEGEND
12n H?+ FROV SRI COKE #lCt AH AT 200 CC/MIN, 30-/KIN
Figure 96
-134-
-------
K23CR-JJAT
1
5
T
K
S
I
T
Y
600-
?rx/^i.
v^
5HC
74C 96C
TEMPKRATUKE. »K
118G
SYMPOI, NO.PTS. LEGEND
1C? CH3+ FROM SKI COKB #10, AH A T 200 CC/HIN. 3C-/HIN
Figure 97
-135-
-------
1
3
I
N
T
E
N
S
I
T
Y
6r\r\
ww
•'
52C
74C
14 (
TEMPERATURE. «K
SYMBOL NO-PTS' LEGEND
1?7 R?0+ FT-OM SHI COKE #lCt AH AT 2CC CC/MIK. 3G«/MIN
Figure 98
-136-
-------
Ft?3CT).r>AT
l?OCi
I-'
V,
?
R
1
N
T
E
t!
S
I
T
Y
9
6nir
v/v
52C
74C 96C
TEMPERATURR, «K
SYMBOL NO.PTS- LEGEKD
1P7 C(H FROM SPI COKE #
C» AH AT 2GC CC/KIN, 30»/MIN
Figure 99
-137-
-------
K23CE-DAT
3
I
N
T
E
N
S
I
T
Y
5*V
w
40
30
2^«
V
-f-
520
740 96C
TEMPERATURE. »K
11SC
SYMBOL NO.PTS- LEGEND
53 NO+ FROM SRI COKE #10. AH AT 200 CC/MIh, 3C«/MIN
Figure 100
-138-
-------
K?3CF«DAT
4
4
I
M
T
F
11
S
T
T
Y
3^.
w
52C
74C 9GC
TEMPERATURE, »K
1190
SYMBOL NO.PTS« LEGEND
52 C0?+ FROM SRI COKE #1C» AH AT 2CC CC/t-'IHi 3O/MIN
Figure 101
-139-
-------
R23Cr,.n Al-
6
4
I
N
T
E
»
S
I
T
Y
6-
4-
5?G
74C
TEMPERATURE,
96C
118C
145
SYMBOL NO-PTS. LEGEND
9 S02+ FROM SRI COKE #10. AR AT 2CC CC/MIh*
Figure 102
-140-
-------
APPENDIX C: Gaseous Evolution Data for Reducing Reactions
Table XI: Peak Temperatures for Reducing Atmospheres of
Hydrogen at 10 atm.
Figures: 103 - 128
-141-
-------
TABLE XI
Peak Temperatures in. Reducing Atmospheres of Hydrogen at 10 atm Pressure
Temperature of Observed Peaks, °K
Solid Reactant Heating Rate CH,
H,0
C,H
2" 6
H2S
Coal °/min
SRI-5 15 1148
40 1200
132Z
SRI-7 15 1068
1193
40 814*
866
1120
SRI-10 15
40
Anthracite 15
40 1169
Lignite 15 972
40 1064
571
685
718
827
630 619
749 772
796
888
597
773
640 614 776
817 800
585
742
872
632 608
780 761
877
581
784
635
826
577
803
641 610
893
* Uncertain
-142-
-------
R182A»DAT
I
N
T
E
N
S
I
T
Y
6f\**tf\
wwv
2f\f\f
wwv
« .
•N
52C
740 96C
TEMPERATUREt »K
118C
SYWBOL NO.PTS.
238
LEGEND
H3f FROM SRI COAL #5t H2 CARRIER GAS AT 2CC CC/HIN, 4C»/MIN
Figure 103
-143-
-------
R193A.DAT
232C
174C
I
N
T
E
N
S
I 116C
T
Y
52C
740
96C
118C
TEHPERATURE. «K
SYMBOL NO.PTS. LEGEND
?34 H3-«- FROM SRI COAL #5. H2 CARRIER GAS AT 2CCC CC/MIN* 4C»/MINt 1C ATM
Figure 104
-144-
-------
R193B«DAT
1
7
I
N
T
E
N
S
I
T
Y
??4C-
168C-
4-
-t-
Ox/v.
52C
74 C
TEMPEflATUREt
96C
118!
SYMBOL NO-PTS. LEGEND
79 CH5+ TfiOM SRI CO/L
H2 CARRIER GAS AT 2CCC CC/MIN» 4C-/MIN, 1C ATM
Figure 105
-145-
-------
K 193C-DAT
1
9
I
N
T
E
N
S
4nne
wwv
520
74C 960
TEMPERATUREf «K
118C
14C
SYMBOL KO-PTS. LEGEND
234 H30+ FROM SRI COAL #5t H2 CARRIER GAS AT 2000 CC/MIN, 4C»/MIN, 1C ATM
Figure 106
-146-
-------
R193D.DAT
960'
2
9
I
N
T
E
N
S
I
T
Y
72C
480
24 C
52C
740 96C
TEMPER/TUHEi »K
use
NO.PTS* LEGEND
63 C2H5+ FROM SRI COAL #5, H2 CARRIER GAS AT 2CCC CC/MIN, 4C«/MIN, 10 AW
Figure 107
-147-
-------
R194A.DAT
I
N
T
E
N
S
I
T
Y
6CC-
520
740 960
TEHPERATUREt »K
H/\rv
vv>
SYMBOL NO.PTS. LEGEND
235 H3f FROM SRI COAL #7. H2 CARRIER &AS AT 2000 CC/MIN. 40«/MINi 10 ATM
Figure 108
-148-
-------
H194B.DAT
1
7
I
N
T
E
N
S
I
T
Y
96;
720'
480
24C-
• *v ••,
52C
74 C
TEMPERATURE,
96C
118C
14C
SYMBOL NO.PTS. LEGEND
134 CH5+ FROM SRI COAL #7, H2 CAHHIEft GAS AT 2CCC CC/MIN, 4C»/MIN» 1C ATM
Figure 109
-149-
-------
R194C-DAT
776C
5820
I
N
T
E
K
S
I
T
3880
194C
v*xr.
52C
74C 96C
TEMPERATURBt »K
118C
SYMBOL NO.PTS. LEGEND
234 H30+ FROM SRI CO/L #7i R2 CARRIER CAS AT 2000 CC/MINi 4C«/MINt 1C ATM
Figure 110
-150-
-------
K194D-DAT
H
/
K
I
N
T
E
N
S
I
T
r
184C
138C
9?C
46C
52C
74C
TEMPERATURE,
96C
118C
SYMBOL NO.PTS* LEGEND
77 C2H5+ FROM SHI COAL #7, H2 CARRIER GAS AT 2CCG CC/MIJU 4C-/MIN, 1C ATM
Figure 111
-151-
-------
R194F-DAT
24C
3
5
I
N
T
E
N
S
I
T
Y
19C
12C
6C
52C
740 96C
TEMPERATURE. »K
118C
Wr\r
\j\.
SYMBOL
NO-PTS.
19
LEGKNL
H3S+ FROM
SRI COAL #7, H2 CARRIER GAS AT 2CCC CC/MIN. 4O/MIN. 1C AWf
Figure 112
-152-
-------
R193A.DAT
I
N
T
E
N
S
I
T
Y
6/x/V
v>w
—I 1 1—
74C 96C
TEMPERATUREt «K
520
iiac
SYMBOL NO-PTS. LEGEND
231 H5f FROM SRI COAL #lCt H2 CARRIER GAS AT 2CCC CC/MINt 4C»/MIN» 1C ATK
Figure 113
-153-
-------
R198B.DAT
36C
1
7
I
N
T
E
N
S
I
T
y
12CC
.->*
3CC
52C
74C 96C
TEMPERATUREt »K
118C
Ur\f\
wv
SYMBOL RO.PTS. LEGEND
70 CH5+ FROM SRI COAL #10. H2 CARRIER GAS AT 2CCO CC/MIN. 4C»/MIN.10 ATM
Figure 114
-154-
-------
R198C-PAT
1
9
I
N
T
V.
N
S
I
T
y
3rtr*/\,
w w
52C
74C 96C
TEMPERATUREt »K
iiac
SYMBOL NO.PTS-
231
LEGEND
H3CH- FROM SRI COAL #10 t H2 CARRIER GAS AT 2CCC
CC/MIN.4O/MIN, 1C AW
Figure 115
-155-
-------
R198D.DJT
8(
I
N
T
E
N
S
I
4/\/\
W
2CC
52C
74C
TEMPERATUBE»
96C
SYMBOL NO«PTS«
35
LEGEND
C2H5+ FROM SRI COAL #1C» H2 CARRIER GAS AT 2CCC CC/MIN. 4C»/NIN, 1C ATM
Figure 116
-156-
-------
H199A-DAT
I
H
T
E
N
S
I
T
Y
7/^rt.
\j\j
3CC
52C
74
96C
1180
TEMPERATURE. -K
SYMBOL NO.PTS.
23C
LEGEND
H3+ FROM SRI ANTHR» H2 CARRIER &AS AT 2C
CC/MIN. 4C»/NIN, 1C ATM
Figure 117
-157-
-------
R199B-DAT
M
/
E
1
7
I
N
T
E
N
S
I
T
Y
.v
-t-
520
740
TEMPEHATUREi
96C
118C
SYMBOL NO.PTS. LEGEND
70 CH5+ FROM SRI ANTHR. H2 CARRIER GAS AT 2000 CC/MINf 4G»/MIN, 10 ATM
Figure 118
-158-
-------
H199C-DAT
4400-
1
9
I
N
T
E
N
S
I
T
Y
. •.
-f-
•4-
52C
740
TEMPERATURE,
96C
1180
SYMBOL
NO.PTS-
230
LEGEND
H30+ FROM
Sfil ANTHRi H2 CARRIER GAS AT 2000 CC/MIN, 4C-/MIN. 1C ATM
Figure 119
-159-
-------
H2C1A.DAT
32C
24 CO
I
N
T
E
N
S
I 16CC
T
Y
Rn/V
V*_«
52C
74C
96C
118C
TEMPERATURE. «K
SYMBOL NO-PTS.
216
LEGEND
H5+- FROM SRI UG-> H2 CARRIER GAS AT 2CCC CC/MIN» 4C»/MIN» 1C ATM
Figure 120
-160-
-------
1
7
I
N
T
E
N
S
I
T
Y
Brnr\,
w
4CO
520
74
96C
118C
TEMPERATURE, «K
SYMBOL NO.PTS- LEGEND
44 CH5-t- FROM SRI LIG , H2 CARRIER GAS AT 2CCC CC/MINi 4G«/HIN» 1C ATM
Figure 121
-161-
-------
R2C1C-DAT
1
9
I
N
T
E
N
S
I
T
Y
1200
V*
4-
•f-
520
740
TEMPERATURE*
96C
SYMBOL NO.PTS. LEGEND
216 H30+ FROM SRI LIG» H2 CARRIER GAS AT 2CCC CC/MIN. 40»/MIN, 1C ATM
Figure 122
-162-
-------
K2C1D.DAT
25Ct
2
9
I
N
T
E
N
S
I
T
Y
150
S'V
\J
520
740 960
TEMPERATUREf «K
118C
SYMBOL NO.PTS-
1C
LEGEND
C2H5+ FROM SRI LIG, H2 CARRIER GAS AT 20CC CC/MIN, 40-/MIN, 1C ATM
Figure 123
-------
R148A-DAT
OC/C/C
6000
I
I
T
E
I
S
I 40CO
t
I
2009*
I I <
740 960
TEWPERATOREt •!
300
520
118C
SYMBOL IO«PTS* LKKID
112 H9f FBOM SBI COEB *7» H2 CARRIER GAS AT 2000 CC/NIIt 15•/«!!, 10 ATM
Figure 124
-164-
-------
B148B.DAT
AQft/V
iiO\s\s
M
/
8
3600
9400
1200
300
520
740 960
TEMPERATURE* •!
1180
1400
SYMBOL 10.PTS. LEOEH)
64 CBS* ?ROM SRI COKE »7. R2 CARRIER GAS AT 2000 CC/NII* 15*/MIIt 1C ATM
Figure 125
-165-
-------
B148COAT
3000
3400
1
9
I
I
T
I
I
I
T
Y
in*
lo\
•v
300
520
740 §60
TEMPRHATDRI* •£
1180
1400
SYMBOL IO.PTS. LEOHD
112 E304- TBOM SH COCI *7» H2 CAHRIEB GAS AT 2000 CC/MIH» 15«/NII> 1C ATM
Figure 126
-166-
-------
H143D.DAT
M
/
E
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200-
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740 960
TIMPIIATUBIt *I
I I
1400
52C
1180
STMBOL MO*PTS* LKEID
113 C2H&4- rBON SRI COKB *7t HZ CARBIEE GAS AT 2CCC CC/MIlt 16*/HIIt 10 AIM
Figure 127
-167-
-------
R148F.DAT
125+
100
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5
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S
I
T
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> I I
740 960
TEMPERATURE* •!
300
520
1180
14C
SYMBOL IO.PTS. LKIID
78 H3S+ FBOM SRI COKE «7« B2 CARBIER GAS AT 2COO CC/MIH, 15«/NIH» 10 ATM
Figure 128
-168-
-------
APPENDIX D: Gaseous Evolution Data for 13C Reactions
Figures: 129 - 132
-169-
-------
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96 C
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SYMBOL
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Figure 129
-170-
-------
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SYN'ROL NO-PTS. T.KGKKD
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Figure 130
-171-
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60 nO."^)+ FHO'-' ShT C13, Af< + 17.C02 AT 2CC CC/KIN.
Figure 131
-172-
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•i r\r\r\ L
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SYMBOL NO-PTS. f.FXJEND
179 C0^)+ FROM SHI 013. Ah -H 1X-CO? A'l ?CC CC/MN. 3C»/MIN
Figure 132
-173-
-------
APPENDIX E: Gaseous Evolution Data for Air Reactions
Figures: 133 - 134
-174-
-------
4000-1
f-'
/
F
4
4
T
E
r;
s
T
T
Y
?400-
52C
740
TEMFEhATUKE,
9GC
118G
SYMBOL NO-PTS- LEGEND
39 C0?-f FPOK Sfil COAL #1C» AT h AT 2CC CC/MIN
Figure 133
-175-
-------
I>?33C.DA1
I
N
T
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N
S
I
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Y
4rtrt
v/w
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96C
113C
TEHPEhATUhEt «K
SYMBOL NO-PTS. LEGEND
35 H20+ FROM SRI COAL #10t AI f» AT 2CC CC/MIN. 3C«/MIN
Figure 134
-176-
-------
BIBLIOGRAPHY
1. Scientific Research Instruments Corporation Report No. SRIC 71-15
( 1971) . NTIS No. PB 211481
2. Scientific Research Instruments Corporation Report No. SRIC 70-14
( 1969) . NTIS No. PB 211338
3. Operators Manual for Non-Isothermal Kinetics Laboratory, Scientific
Research Instruments Corporation ( 1972) .
4. A. L. Yergey, et al. , (1972), Non-Isothermal Kinetic Studies of the
Hydrodesulfurization of Coal, submitted for publication.
5. K. H. von Heek, H. Juntgen and W. Peters, Ber. BunsenPhys. 71,
113(1967).
6. F. H. Field, Ace. Chem. Research JL, 42(1968).
7. For example see C. Y. Wen, Optimization of Coal Gasification Processes
Vol. 1, U.S. Department of the Interior, Office of Coal Research,
Chapter IV.
8. D. W. van Krevelen, Coal, Elsevier ( 196!) Chapters XII and XIII.
9. F. Bonner and John Turkevich, J. Am. Chem. Soc. 73, 56l(i95l).
-177-
-------
BIBLIOGRAPHIC DATA
SHEET
1. Report No.
EPA-650/2-73-042
3. Recipient's Accession No.
4. Title and Subtitle
Gasification of Fossil Fuels Under Oxidative, Reductive,
and Pyrolytic Conditions
5- Report Date
December 1973
6.
7. Author^) G. J. Fergusson
A.L.Yergey, F.W.Lampe. M. L. Vestal, E.J.Gilbert, and
8. Performing Organization Rept.
N°- SRI 72
9. Performing Organization Name and Address
Scientific Research Instruments Corporation
6707 Whites tone Road
Baltimore, Maryland 21207
10. Project/Task/Work Unit No.
ROAP 21ADDQ4
11. Contract/Gram No.
68-02-0206
12. Sponsoring Organization Name and Address
EPA, Office of Research and Development
NERC-RTP, Control Systems Laboratory
Research Triangle Park, NC 27711
13- Type of Report & Period
Covered
Final
14.
15. Supplementary Notes
16. Abstracts The report contains kinetic reaction data produced in a non-isothermal
kinetics laboratory while gasifying selected types of coal under oxidative, reductive,
and pyrolytic conditions. Types of coal cover the range, including lignite and anth-
racite. Evolution of thermal decomposition products under study conditions were
investigated at different fuel heating rates and gasification pressures. Gaseous prod-
uct evolution rates , as the function of temperature, were graphed Tor different coals
exposed to indicated gasification regimes. The evolution of such gaseous species as
H2O, CO, CO2, O2, SO2, NO, H2, CH4, H2S, and C2H2 was followed up in conjunc-
tion with 13 different coal gasification reactions as identified previously and in the
course of this work. The kinetic reaction parameters, such as activation energy and
frequency factors for these reactions, were calculated and presented earlier and in
this report.
17. Key Words and Document Analysis, 17o. Hcscriptors
A • T^ t * If
Air Pollution
Coal Gasification
Fossil Fuels
Oxidation
Reduction (Chemistry)
Pyrolysis
Kinetics
17b. Identificrs/Open-Ended Terms
Air Pollution Control
17c. COSATI Field/Group 4Q£) Q7D
18. Availability Statement
Unlimited
19. Security Class (This
Report)
UNCLASSIFIED
20. Security Class (This
Page
UNCLASSIFIED
21. No. of Pages
178
22. Price
FORM NTIS-35 (REV. 3-721
USCOMM-OC M9S2-P72
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