Ind. Eng. Chem. Process Des. Dev.

1901, 20, 349-358 949

Kinetics of Donor-Solvent Liquefaction of Bituminous Coals in

Nonisothermal Experiments
Govlndan Mohan and Harry Sllla
Department of Chemistry and Chemical Englmrhg, Stevens Institute of Technobgy, Hoboken, New Jersey 07030

An Illinois No. 6 coal was liquefied in a batch reactor under nonisothermal conditions from 330 to 450 O C using
tetralin as a hydrogendonor solvent at total pressures up to 70 atm and reaction times from 5 to 60 min. A
separation scheme was developed using liquid-solid chromatography on alumina to separate the Ilquefled products
into classes of compounds consisting of mixtures of aromatics, ethers, nltrogens, hydroxyls, and multifunctionals.
Using these classes of compounds several kinetic models were tested by flttlng experimental nonlsothermal
concentration-time profiies using a nonlinear parameter estimation technique. The multifunctional compounds were
considered as reaction intermediates which then decomposed reversibly Into aromatics, ethers, nitrogens, and
hydroxyls. It was found that this kinetic model predicts concentration-time profiles satisfactorily. This work has
also established the use of preparative liquld-solkl chromatography as a reliable and useful method for separating
coal liquids for kinetic studles.

Introduction
In view of the need to develop commercially viable
processes for deriving liquid fuels from coal a description
of coal liquefaction kinetics is necessary for reactor design
and scaleup. Most coal liquefaction processes involve
dissolution of the coal by using a hydrogen-donor solvent
with added gaseous hydrogen, but among the various
solvents employed in laboratory studies tetralin has been
found to be the most common hydrogen donor. Fur-
thermore, synthetic solvents designed to simulate a typical
process solvent invariably contain significant amounts of
tetralin. The addition of gaseous hydrogen in donor-sol-
vent liquefaction in several laboratory investigations has
been shown to yield higher conversions (Han et al., 1978).
Recently, Maddocks and Huffman (1978) proposed that
no hydrogen gas be added in the first dissolution stage of
a two-stage coal liquefaction process. Also, in recent lab-
oratory studies Mitchell and Whitehurst (1978) and Lon-
ganbach et al. (1979) liquefied coal at short contact times
in the absence of gaseous hydrogen. In our studies tetralin
was used as the donor solvent without added gaseous hy-
drogen.
The kinetics of coal liquefaction are very complex
leading to the formation of numerous compounds. The
approach in kinetic studies has been to attempt to separate
these compounds into kinetically similar classes based
on some separation technique. Most studies used methods
of separation that depend on solubility in various solvents
to separate coal liquids. These studies are summarized in
Table I. Recently, Brunson (1979) used distillation to
measure the kinetics of formation of gaseous and liquid
products using a coal-derived hydrogen-donor solvent.
Prather et al. (1977) indicated the feasibility of using
analytical liquid-liquid chromatography (LLC) to char-
acterize coal liquefaction solvents for studying kinetics, but
they did not attempt to use this approach to obtain
product compositions for estimating kinetic parameters.
Whitehurst et al. (1977) separated coal liquid products by
liquid-solid chromatography (LSC) on silica using various
eluting solvents in sequence. They concluded that the coal
liquefaction products contained a large number of com-
pounds with very similar hydrocarbon skeletons differing
only by the various functional groups, and they also did
not propose any kinetic model based on the separated
products.
A summary of kinetic models and rate constants based
on product compositions obtained by solubility in various
0196-4305/81/1 120-0349$01.25/0
solvents with the definition for the various solubility classea
is given in Table I. These experiments were carried out
with and without catalysts and donor solventa using mostly
bituminous coals. The proposed kinetic models for li-
quefaction with or without donor solvents are in many
cases similar. In many of the studies a hydrogen-donor
solvent with an added catalyst was used.
In the earlier proposed kinetic models the reaction
products, oils and asphaltenes, were combined or treated
separately to determine reaction rate constants. Pelipetz
et al. (1955) and Hill et al. (1966) assumed that only a
single thermal decomposition process occurs. Falkum and
Glenn (1952) found that the hydrogenolysis of Spitsbergen
coal occurred in two distinct stages and suggested that two
constituents are present in coal, one of which degraded
much faster than the other. Such a model, involving two
reactive constituents, was investigated by Curran et al.
(1967) and Struck et al. (1969) and was found to fit their
experimental conversion data on coal extraction and
coal-extract hydrocracking processes. Weller et al. (1951)
proposed that the conversion of coal to oils involves two
consecutive first-order reactions with asphaltenes as an
intermediate product. They determined the rate constants
for both steps as shown in Table I. On the other hand,
Liebenberg and Potgieter (1973) proposed two simulta-
neous reactions for the formation of oils and asphaltenes
in order to explain their experimental data. Yoshida et
al. (1976) expanded this model to allow for oils formation
by two paths. Recently, Chiba and Sanada (1978) assessed
the previous models consisting of oils and asphaltenes and
suggested using the formation of oils from two active coal
components to explain the experiments in the literature.
Recently, a third class of compounds, the preasphalt-
enes, was isolated from coal liquefaction products and was
shown to be a key reaction intermediate by Sternberg et
al. (1975). Thus a more complex model was proposed by
Schweighardt and Sharkey (1976) using preasphaltenes in
addition to oils and asphaltenes. Subsequently, simplified
versions of this model have been satisfactorily tested in
a batch reactor (Shalabi et al., 1979) as well as in a con-
tinuous reactor (Cronauer et al., 1978; Traeger, 1979).
Squires (1978) proposed a more comprehensive working
model for donor-solvent coal liquefaction, but the model
has not been tested to date because the isolation procedure
for the product oil and semi-coke has not been es-
tablished.
In this study LSC was employed to separate the coal
0 1981 American Chemical Society
350 Ind. Eng. Chem. Process Des. Dev., Vol. 20, No. 2, 1981

Table I. Summary of Coal Liquefaction Mechanisms Baeed on Solubility Separations

hydrogen donor rate constant at
investigators kinetic schemea coal solvent added catalyst 400 OC, min-I
Pelipetz et al. (1955) Wyoming none none k , = 0.0030
Hill et al. (1966) Utah tetralin none k , = 0.0372
Falkum and Glenn Spitsbergen none Ca-Cu-Cr k , = 0.0068
(1952)

Curran et al. (1967) Pittsburgh tetralin none k , = 3.0200

k , = 0.1160
Struck et al. (1969) Pittsburgh none ZnO/ZnCI, k , = 0.2400
extract k , = 0.0062
Weller et al. (1951) Pittsburgh none SnS, NH,CI k , = 0.0270
Anthraxylon k , = 0.0011

Liebenberg and bituminous tetralin none k , t k , = 0.0039

Potgieter (1973)
Yoshida et al. (1976) Japan decrystallized red-mud k , = 0.0037
anthracene oil and sulfur k , = 0.0049
k , = 0.0170

Cronauer et al. (1978) Belle Ayr hydrogenated none k , = 0.1492

phenanthrene k , = 0.1979
k , = 0.0855
k , = 0.0240
k , = 0.1546
k , = 0.0735

Shalabi et al. (1979) Kentucky tetralin none k , = 0.00043

k , = 0.00007
k , = 0.00075
k , = 0.00005
k , = 0.00120
k , = 0.00005
G, gases; 0, oils (hexane solubles); A, asphaltenes (hexane insolubles, benzene solubles); P, preasphaltenes (benzene in-
solubles; tetrahydrofuran solubles).

liquids into classes of compounds for kinetic analysis.
Chromatographic separation promises to be a more effi-
cient and perhaps more fundamental method.
Experimental Section
System Design. Since Storch et al. (1940) reported the
use of batch reactors for kinetic studies, many investigators
have employed these massive reactors of various capacities.
These reactors require long heat-up and cool-down times,
during which significant reactions can occur. The ap-
proaches used to minimize these nonisothermal heat-up
times have been to use small reactors constructed from
tubing (Neavel, 1976) or to first heat up the solvent to the
reaction temperature and inject the coal slurry with a
pump (Shalabi et al., 1979). If isothermal conditions
cannot be obtained experimentally, then a calculation
procedure is required to correct for the nonisothermal
conditions, which is the approach adopted here. Earlier,
Yergey et al. (1974) applied the nonisothermal analysis to
estimate the kinetic rate parameters for the hydro-
desulfurization of coal. Recently, Morita et al. (1979) used
a nonisothermal analysis for estimating the reaction rate
parameters in studying the effect of hydrogen pressure on
the rate of direct liquefaction of some Japanese coals.
The experiments discussed here were conducted in 1-L
stirred reactor (Autoclave Engineers, Model AFP-1005,
Magnedrive), shown in Figure 1, where all materials in
contact with the coal slurry are 316 stainless steel. A coal
slurry injection system was designed and added to the
reactor to minimize reactant heat-up times. This system
included a double-pipe heat exchanger to prevent over-
heating of the Teflon seat of the ball valve caused by heat
conduction from the reactor. Nevertheless, the Teflon
seats still had to be cleaned or replaced after a few in-
jections because of coal deposits or erosion. The holdup
of the slurry in the injector, which was washed and mixed
with the reactor wash at the end of a run, was found to
be less than 0.5% of the slurry injected. This method of
slurry injection caused a temperature drop of 30 "C of the
reaction mixture upon injection, thus requiring a method
to correct for the nonisothermal reaction conditions.
The furnace temperature was controlled by a propor-
tional action temperature controller using a chromel-alu-
me1 thermocouple and solid-state switching (Barber-Col-
man, Series 530). The reaction temperature was measured
manually (*l OC) with another chromel-alumel thermo-
couple inserted into the thermowell of the reactor using
a cold-junction compensator and a potentiometer. The
temperature was also recorded with a Leeds & Northup
Speedomax X/L 680 recorder with a full scale response
of 1 8.
All the components of the Magnedrive impeller were
disassembled and cleaned thoroughly after each run.
Neither the graphite bearings of the Magnedrive impeller
nor the stainless steel gasket needed replacement during
the course of this work, because of the care and cleaning
procedure adopted. The reaction mixture was stirred at
1500 rpm since the mass transfer resistance has been re-
 Ind. Eng. Chem. hocess Des. Dev., Vol. 20, No. 2, 1981 351

NITROGEN
REACTION
CHECK VALVE
SOLVENT PREHEATING WENCH

530

400
0
STATOR FOR
TACHOMETER u'
BALL VALVE
28 300
ir DOUBLEPIPE
HEAT EXCHANGER
200

IO0

I I I I

0 I 2 3 4
TIME, h

Figure 2. Typical temperature-time profile.

- W E N C H WATER
INLET Experimental Procedure. In a typical experiment, the
reactor is assembled and leak tested with nitrogen. Then
264 g of tetralin is introduced into the reactor at ambient
pressure, flushed with nitrogen, and heated to a steady-
COOLING COIL-
-FURNACE state temperature while stirring at 1500 rpm. A slurry
consisting of 30 g of coal in 36 g of tetralin is injected from
THERMOWELL- INJECTION TUBE the feed reservoir using nitrogen at a pressure of 30 atm
IMPELLER as shown in Figure 1. The coal will settle from more
concentrated slurries in the feed reservoir whereas less
concentrated slurries cool the reaction mixture appreciably.
The final solvent/coal ratio in the reactor was 10 in all
Figure 1. Coal liquefaction reactor system. experiments to keep the tetralin concentration relatively
constant during reaction (Hill et al., 1966; Shalabi et al.,
Table 11. Ultimate and Proximate Analyses of 1979). After injection of the cold slurry, the reaction
Illinois No. 6 Coalo mixture is cooled by approximately 30 O C after which the
ultimate proximate temperature rises steadily during the experiment as can
be seen in a typical temperature-time profile shown in
mass % mass % Figure 2. The pressure rise during reaction was about 25
(moisture (moisture
component free basis) component free basis) atm. After the desired reaction time, the reaction is rapidly
quenched by passing cold water through the cooling coils
hydrogen 4.8 volatile matter 42.3 and by blowing cold air over the reactor after dropping the
carbon 68.9 fixed carbon 45.2 furance with the aid of laboratory jacks.
nitrogen 1.2 ash 12.5
sulfur 3.1
The experiments were carried out at temperatures from
(total) 330 to 450 OC and pressures under 70 atm. Temperatures
oxygen 8.9 below 330 O C are ineffective for coal dissolution, resulting
ash 12.5 in low conversions (Guin et al., 1979) and temperatures
* Coal source, River King Mine, Ill. Donated by U.S. greater than 450 "C lead to excessive coke formation
Department of Energy, Pittsburgh, PA. Dried prior to (Storch et al., 1940). Reaction times of 5, 10, 15, 20, 30,
use. 40, and 60 min were selected for all the experiments.
Because injection of the coal slurry required 1 min and
ported to be insignificant at this speed (Hill et al., 1966). quenching 2 min, reaction times less than 5 min were not
Also, when the impeller speed was reduced to 1300 rpm considered. After 60 min a limiting conversion was
in this investigation, there were no significant changes in achieved.
the product concentrations. Product Separation Procedure. The separation
Materials. The coal used in all experiments was a procedure for the reaction products is shown in Figure 3.
high-sulfur and a high-ash Illinois No. 6 coal from the River After the reactor is cooled down to room temperature, the
King mine. The analyses of the coal are given in Table gaseous products are bubbled through 0.4 M lead acetate
11. The coal was dried, ball-milled and sieved through a solution to remove the H a and thus determine the amount
200 U.S.standard mesh screen and stored in a desiccator of sulfur in the gas phase. The black precipitate of PbS
under nitrogen atmosphere prior to its use. formed is filtered, washed with 0.1 M HN03 and then with
Technical grade tetralin was used as received from City distilled water before drying at 110 "C to constant weight.
Chemicals Corp., New York, and was analyzed by LC and Overall mass balances made for each experiment showed
found to contain 25 mol % of decalin and less than 1% better than 96% recovery of the total charge to the reactor.
of naphthalene. The reagent grade solvents used for The unwashed material sticking to the walls of the reactor,
washing the reactor and for the chromatographic separa- estimated to be 1%of the total charge, and the product
tions, and the alumina packing (Fisher No. A-540), used gaws constituted the losses. In early experiments methane,
to separate the liquid reactions products, were obtained ethane, propane, butane, and hydrogen were found from
from Fisher Scientific Co. a GC-MS analysis of the product gases, but no attempt was
352 Ind. Eng. Chem. Process Des. Dev., Vol. 20, No. 2, 1981
THFWIB*OFREACTDR
4-4
REACTOR
GASES
p-/-'T' SLURP"
'
i '
TETRALIN
NiTRDGlNS
HIOROXYLS
*SH
Figure 3. Separation scheme for coal liquefaction reaction products.
made to account for the gaseous products in subsequent
runs.
The slurry products were collected in two stainless steel
flasks and centrifuged to separate the sediment (heavy
liquids plus solids) from the liquids. After the reactor
surfaces were washed with tetrahydrofuran (THF), the
wash was combined with the sediment. The total wash
was then extracted with THF in a Soxhlet extractor to
recover THF solubles. Subsequently, the THF in the
extract was evaporated in a Rotavap and the undissolved
material dried to constant weight and its ash content de-
termined. Any water produced during the liquefaction
would be evaporated in this step.
The Soxhlet extract was combined with the centrifuged
liquids and the mixture was then distilled at 125 "C and
8 cmHg to remove most of the unreacted tetralin and its
decomposition products, naphthalene and dihydro-
naphthalene. Volatile coal liquids could also be removed
at this point but these losses are small because the total
loss for the whole experiment is only 2%. The bottoms
product, referred to as Solvent Refined Coal (SRC), was
stratified. In order to obtain a uniform sample for liq-
uid-solid chromatography (LSC) the SRC was dissolved
in T H F to produce a homogeneous solution. Approxi-
mately 5 mL of this solution was evaporated in a Rotavap
at 25 OC and 2 mmHg to eliminate THF in order to obtain
an accurate sample (1.5 f 0.001 g) for LSC separations.
Then the sample for the chromatographic column was
redissolved in THF and mixed with 10 g of alumina in a
gas washing bottle to produce a material resembling wet
sand. The alumina was then dried at 25 "C and 2 mmHg
in the wash bottle where the evaporating THF vapors
smoothly fluidized the alumina with no visible solids en-
trainment. The dry alumina with the adsorbed sample was
then loaded onto the top of a 25 mm i.d. X 600 mm
preparative chromatographic column, which had been
slurry-packed with 60 g of alumina in hexanes and
equilibrated overnight. The adsorbed SRC was then eluted
0.25 r
t L E A 0 ACETATE
SCRUBBER
I
A 800 1200 I IO
VOLUME ELUTED, mi
Figure 4. A typical preparative liquid-solid chromatogram for
I "*C""U I solvent refined coal.
PACKING: BONDAPAK CI8/PORASIL B PEAKS 1. DECALIN
SOLVENT: METHANOLIWATER (77:23) 2. TOLUENE (Internal Standard1
FLOWRATE. 2.5 mllmin 3. NAPHTHALENE
4. DIHYDRONAPHTHALENE
5. TETRALIN
UULTlFUNCTlONilLI
DISTILLATE SATURATES
Figure 5. Comparison of analytical liquid chromatograms of the
distillate and the saturates fractions.
with the sequence of solvents used by Schiller and Mat-
hiason (1977). Each eluted sample was concentrated in
a Rotavap and the solutions transferred to tared vials
where the solvents were evaporated at 25 "C and 2 mmHg
and the residues weighed. The uneluted material, which
was obtained by difference, is the irreversibly adsorbed,
multifunctional and highly polar components of the SRC.
Six fractions were produced, five eluted and one adsorbed,
as shown in Figure 4. Reproducibility of the separations
in duplicate determinations ranges from 2% for the small
fractions and up to 5% for the large fractions.
The coal products are divided into six classes of com-
pounds, namely, aromatics, ethers, nitrogens, hydroxyls,
multifundionals, and unreaded coal. The volatile portions
of similar chromatographic fractions were analyzed by
Schiller and Mathiason (1977) using high resolution mass
spectrometry and it was found that the aromatics fraction
contained polyaromatic hydrocarbons and some aromatic
ethers; the ethers fraction, benzofurans and naphthofurans;
the nitrogens fraction, carbazoles, quinolines, and aza-
pyrenes; and the hydroxyls fraction, phenols, hydroxy
aromatics, and hydroxy ethers.
The distillate and the saturates fraction from the SRC
were analyzed by analytical liquid-liquid chromatography
(LLC) using a methanol-water mobile phase, and the
chromatograms are compared in Figure 5. It is clear that
both these fractions contain only decalin, naphthalene,

3800I
I / I IO 20 30 40 50 60
TIME, mln
Figure 6. Chebyshev fit to the measured reaction temperature-time
profile.
dihydronaphthalene, and tetralin. Furthermore, it was
found that in the blank runs, using tetralin without coal
under similar reaction conditions, the same product con-
centrations were produced within experimental error.
Hence no significant amounts of naphthalene and di-
hydronaphthalene are derived from the coal under the
reaction conditions used, and the saturates fraction con-
tains the unrecovered tetralin and its reaction products
from the distillation step. Therefore, the saturates fraction
from the SRC was combined with the distillate and was
not considered in the kinetic schemes. The aromatics
fraction was partially soluble in the mobile phase and when
analyzed showed the absence of decalin, naphthalene,
dihydronaphthalene, and tetralin. The other fractions
obtained from the preparative chromatographic separa-
tions are insoluble in the mobile phase.
Kinetic Modelling and Parameter Estimation
The kinetic models are obtained by performing a dif-
ferential mass balance for each class of compounds present
in reactor a t any instant. Thus, the general set of dif-
ferential equations representing a proposed reaction
scheme and the initial conditions are written as
Xi(0) = XIJi
The rate, Rj, depends on the component concentrations,
X i , and temperature. The kinetic models developed here
are restricted to systems of fmt-order reactions, where the
temperature dependence for the rate constant is given by
the classical Arrhenius expression
k j = Aj exp(-Ej/(RT)) (2)
The objective then is to estimate the rate parameters,
Aj and E,, for proposed kinetic models by using nonlinear
regression techniques (Bard, 1974). The estimation pro-
cedure consists of fitting the solutions of eq 1to the con-
centration measurements made at different reaction times
and temperatures since the experiments are nonisothermal.
The temperature variation during an experiment (Figure
6) is fitted by a 10-term series expansion in Chebyshev
polynomials (Esch, 1974) with the Chebyshev coefficients
determined by unweighted least-squares fitting to the
reaction temperature-time profile. Hammings modified
predictor-corrector method is used to numerically integrate
the set of simultaneous linear differential equations given
by eq 1. The nonlinear estimation algorithm (Meeter,
1965) is based on Marquardts method (1963), which
combines the best features of the Gauss-Newton and
steepest descent methods.
Ind. Eng. Chem. Process Des. Dev., Vol. 20, No. 2, 1981 353
s
1 0.16 i-
REACTION TIME, min
Figure 7. Desulfurization of Illinois No. 6 coal.
The starting values for the rate parameters, Aj and Ej,
were obtained by executing the isothermal version of the
program using values for the rate constants that are con-
sistent with those in Table I. The optimal parameter
estimates of this program were the maximum likelihood
estimates and they are neither unique nor global. Ob-
taining a satisfactory fit of a kinetic model to the exper-
imental concentration-time profiles by this method does
not verify the correctness of a kinetic scheme because good
fits can always be obtained if the kinetic scheme is made
sufficiently complex so as to introduce additional param-
eters. The method, however, does allow one to reduce the
number of possibilities because some kinetic schemes may
be eliminated because of poor fits. Once a satisfactory fit
has been obtained additional experimental information is
required before the kinetic scheme can be accepted. Also,
parameter estimation is useful in planning experiments.
Desulfurization. The coal used in this work is a very
reactive Illinois coal with 3.7 mass % sulfur and 12.5% ash
content. In order to estimate the extent of desulfurization,
the mass fraction of sulfur removed as H2Swas calculated
on the basis of total sulfur in the coal. With such high ash
content any iron oxides in the coal might be converted to
sulfides, and the pyrites into pyrrhotite and hydrogen
sulfide. Some sulfur may be present as organic compounds
in the THF solubles, but this was not determined. It was
found that up to 18% of the total sulfur is removed as H a
during the experiment with large desulfurization occurring
at higher temperatures and extended times as shown in
Figure 7. These results are consistent with those reported
by Longanbach et al. (1979) for the liquefaction of a West
Kentucky 9/14 coal using Wilsonville recycle solvent under
similar conditions of temperatures and pressures except
that the reaction times were less than 5 min and sol-
vent/coal ratios less than 3.
Coal Conversion Kinetics. Coal conversion is based
on the fraction of liquefied coal that is insoluble in tet-
rahydrofuran. The coal converted on the dry and ash-free
basis, defined as
WC - WR
x = (3)
WC
was reproducible within 4% absolute error. A first-order
irreversible reaction scheme for coal dissolution is assumed
in accordance with earlier investigations (Han et al., 1978)
and the kinetic model is represented as
dx
- = -k(X, - X ) (4)
dt
x(0) = 0
354 Ind. Eng. Chem. Process Des. Dev., Vol. 20, No. 2, 1981

hydroxyls ( H )
nitrogens (N)
ti." y
coal (c) 2 multifunctionals ( M ) (5)
1.. A ethers (E 1
aromatics (A )

-
d
dt

I/
REACTION TIME, min

Figure 8. Conversion of Illinois No. 6 coal during liquefaction.

Table 111. Kinetic Parameters for Conversion of

Illinois No. 6 Coal
~~

limiting activation frequency

temp conversion, energy, factor,
range,"C Xe kcal/g-mol min-*
330-390 0.75 18.2 1.86 x 105
390-450 0.88 19.1 3.53 x 105

where the limiting conversion of a given coal, xe, obtained

at long reaction times, is a function of temperature as well
as the donor-solvent type (Cronauer et al., 1978). The
numerical solution of the above model is compared with
the experimental data in Figure 8. The best-fit rate pa-
rameters, determined by the estimation program, are given
in Table 111. The value of activation energy for coal
'MAlI'AM

aromatics (A)
e ethers (E)
dissolution agrees very well with that of 18.7 kcal/g-mol
for bituminous coals liquefied in a well-mixed batch reactor all the reactions shown in eq 5 are made reversible with
(Hanet al., 1978). the exception of the formation of the multifunctional
Coal Liquefaction Kinetics. To obtain kinetic models compounds from coal. The kinetic model corresponding
for coal liquefaction, the liquefied coal products were to the kinetic scheme in eq 10 is given by the set of
equations in matrix form in eq 11 and eq 12, 13, and 14.
separated into classes of compounds according to their
chemical functionalities, namely, aromatics (A), ethers (E), 0 0 0
nitrogen compounds (N), hydroxyl compounds (HI, large
multifunctional compounds (M), and unreacted coal (C). 0
Because significant qualitative differences in concentra- kMN 0 -kNM 0 0
tion-time profiles for the multifunctional compounds were ME 0 0 EM 0
observed at high and low temperatures, the entire exper-
imental range was divided into a high temperature range MA 0 0 0
(390-450 "C) and a low-temperature range (330-390 "C).
Several models were tested in order to obtain the best-fit
to the experimental concentration-time profiles.
A. High-Temperature Liquefaction. The experi-
mental concentration-time profile for the multifunctional
compounds in the high-temperature range (390-450 " C )
suggests that they me reaction intermediates. Perhaps this
is due to the initial thermal breakup of the "coal [XC, XM, XH, XN, XE, XAlO = [I,0, 0, 0, 0, 01 (12)
molecules'' to produce large free radicals, which are then P2 = ( ~ M H+ ~ M +N ME + MA) (13)
stabilized by abstraction of hydrogen from tetralin. Sub-
sequent bond breaking of these stabilized-multifunction- x , = 0.88 (Table 111) (14)
al-large molecules, which are highly polar, produce several The concentration-time profiles for the proposed mod-
smaller and less polar compounds. Accordingly, kinetic els, calculated according to the procedure outlined earlier,
models 1 and 2 were tested. are compared with the experimental concentration-time
Kinetic Model 1. Model 1 consists of a series-parallel profiles in the high temperature range in Figures 9 and 10.
reaction scheme of first-order irreversible reactions with Undoubtedly, model 2 with all but one reaction reversible
the large multifunctional compounds as reaction inter- fits the data best, which is further confirmed by the lower
mediates (eq 5). The kinetic model corresponding to the value of the minimum sum of squares of the residuals
kinetic scheme in eq 5 is given by the set of equations in shown in Table IV. Numerical values of the kinetic pa-
matrix form in eq 6 and eq 7, 8, and 9. rameters for model 2 are given in Table V. Reversible type
 Ind. Eng. Chem. Process Des. Dev., Vol. 20, No. 2, 1981 355

I.",

1I Q 6 1 hMULTIFUNCTIONALS

NREACTEDCOAL

REACTION TIME, min

REACTION TIME, min
Figure 9. Comparison of kinetic model 1with experimental product Figure 10. Comparison of kinetic model 2 with experimental
concentrations in the high-temperature range. product concentrations in the high-temperature range.
Table IV. Kinetic Model Discrimination Using
Regression Analysis
sum of squares of residuals
kinetic model high temp low temp
Based on Chromatography
H f 0.61 \
1. C -M 4N 0.3378 0.1817
7;

a 0.0346

REACTION TIME, min

Based on Solubility
Figure 11. Comparison of kinetic model 1 with experimental
/O product concentrations-in the low-temperature range.
4. c - 0 0.0696 0.0256
\ P 1.01 r

5. c - A 0.0359 b
\)

0.0336 b i 0.61 \

Model does not apply. Estimation converges to neg-

ative rate constants.

Table V. Rate Parameters for Kinetic Model 2

high temperature low temperature REACTION TIME, mm

E, E, Figure 12. Comparison of kinetic model 2 with experimental

rate para- kcal/ kcall product concentrations in the low-temperature range.
meter A, min-' g-mol A, min-' gmol
CM 8.21 x 105 19.1 2.11 x lo6 19.5 will not fit the experimental data because it will not pro-
k MH 2.21 X lo8 29.1 7.34 x 105 19.4 duce the peak shown in Figure 10, which is characteristic
~ H M 2.57 X lo5 19.3 2.31 X lo6 19.5 of consecutive reactions. The activation energies for all
~ M N 6.41 X 10' 29.2 1.87 x 105 19.1 the reaction steps range from 17 to 29 kcal/g-mol. I t is
~ N M 1.54 X lo8 28.8 2.33 X lo6 19.2 found that all the reverse reactions are kinetically faster
ME 1.52 X lo8 28.1 1.16 X lo6 19.6 than the corresponding forward reactions, which agrees
EM 4.32 X lo5 17.2 1.25 x 107 20.1
with the high concentration for the large multifunctional
MA 1.18 X lo8 29.3 3.92 x 105 19.6
AM 4.74 x 105 20.0 1.94 x lo6 19.0 compounds obtained experimentally. It is also found that
the hydroxyl compounds dominate the other functional
reactions to describe coal liquefaction kinetics have been compounds, which is consistent with the abundance of
suggested by Squires (1978). Model 3 shown in Table IV hydroxyl groups found in the bituminous coal structure
356 Ind. Eng. Chem. Process Des. Dev., Vol. 20, No. 2, 1981

Table VI. Combination of Coal-Derived Products Obtained from Chromatographic Separations t o Oils,
Asphaltenes, and Preasphaltenes
chromatographic fraction elution solvent combination rule solubility description classical definition
saturates hexanes
aromatics ( A ) toluene A + 0.5E oils (0) hexane solubles
ethers (E) chloroform
nitrogens (N) chloroform 0.5E + N + 0.5H asphaltenes (, A,) hexane insolubles
benzene solubles
hydroxyls (H) 90% THF/10% ethanol 0.5H + M preasphaltenes (P) benzene insolubles
THF solubles
large multifunctionals (M) uneluted

(Whitehurst el al., 1977; Wiser, 1978). 1.01

B. Low-Temperature Liquefaction. In the low-tem-
perature range (330-390 "C)it is again found that not
model 1 but model 2 (Table IV) fits the experimental
concentration-time profiles as shown in Figures 11 and 12.
It can also be seen in Figure 12 that the multifunctional 0.6-
compounds do not peak as was found in the high-tem-
perature range because in the low-temperature range the E
i
net rate of formation of the multifunctional compounds E 0.4-
is slower. Thus model 3, where the reaction products were 2
L
assumed to form directly from the coal, was tested. Y
Kinetic Model 3. In this kinetic scheme all reaction 8 0.2-
HYDROXYLS-,
steps are assumed to be first order and irreversible. The
multifunctional (MI
hvdroxvls ( H) I
10 20 30 40 50 60 70
REACTION TIME, mm

Figure 13. Comparison of kinetic model 3 with experimental

product concentrations in the low-temperature range.

1.01
aromatics (A) ethers (E)

kinetic model corresponding to the above kinetic scheme Cl.1 -

is given by the set of equations in matrix form in eq 16 and QUI
0 0 0 0 0
PREAWHALTENES 7
0 0
0 0

E].[ti.]
kCN 0 0 0 0 0
kCE 0 0 0 0 0
UNREACTEDCOAL
kCA 0 0 0 0 0

-kCN (l-xe) (16)

OA Ib io 3b 40 510 60 7
REACTION TIME, mm
-k C E
Figure 14. Comparison of kinetic model 4 with experimental
XA -kCA
product concentration in the high-temperature range.
eq 17, 18, and 19.
of SRC fractions based on their solubilities in various
[XC, X M , X H , X N , XE, X A l O = (17)
0, 0, 0, 0, 01 solvents are preasphaltenes, asphaltenes, and oils. Since
6 3 = ( k C M + k C H -t- k C N + ~ C +
E kCA) (18) LSC separations produced five fractions, some way of
combining these fractions is required to obtain the frac-
x, = 0.75 (Table 111) (19) tions based on solubility. Whitehurst el al. (1977) sug-
In Figure 13 model 3 is fitted to the experimental con- gested a formula for combining the nine chromatographic
centration-time data. A slightly better fit of the data, fractions obtained in their work into oils, asphaltenes, and
however, is obtained with model 2 as can be seen by the asphaltols (pyridine solubles, benzene insolubles) on the
lower value of the s u m of squares of the residuals, possibly basis of chemical functionality, C-H skeletal structures,
due to the greater number of parameters in model 2 as and molecular weight rangea that might be common among
compared to model 3. The fact that model 2 fits both the the two different product classifications. A similar com-
experimental concentration-time data for both the high bination rule, as given in Table VI, is used in this inves-
and low temperature range, whereas none of the other tigation.
kinetic models tested do, may be significant. The acti- Three simplified versions of the kinetic model recently
vation energy for the various steps in model 2 has been proposed by Cronauer et al. (1978) shown in Table I were
found to be approximately 19 kcal/g-mol. fitted to the concentration-time profdes obtained by these
Comparison of Kinetic Models Based on Solubility. rules of combining the LSC fractions. The tested models
As it has been discussed earlier, the classical definitions are given in Table IV. Model 4 fits the data reasonably
 Ind. Eng. Chem. Process Des. Dev., Vol. 20, No. 2, 1981 357

Table VII. Comparison of Kinetic Parameters for the Formation of Oils, Asphaltenes, and Preasphaltenes
reactor batch CSTRa batch batchb
technique nonisothermal isothermal nonisothermal isothermal
(390-450"C) (400-470"C) (330-390 "C) (350-400"C)
coal Illinois No. 6 Belle Ayr Illinois No. 6 Kentucky No. 9
(bituminous) (subbituminous) (bituminous) (bituminous)
solvent tetralin hydrogenated hydrogenated tetralin tetralin
anthracene oil phenanthrene
reaction E A E A E A E A E A
coal + oils 19.8 1.71 X lo5 14.1 3.11 X lo3 28.9 2.10 X l o 8 19.1 1.58 X lo5 40.0 1.21 X 1 O ' O
coal ---f asphaltenes 18.9 1.44 X lo5 15.6 1.12 X 10" 8.6 9.63 X 10 19.4 3.61 X lo5 30.0 8.34 X lo6
coal ---f preasphaltenes 29.3 1.49 X l o 9 13.8 2.81 X lo3 4.3 4.94 19.2 1.20 X lo6 29.0 2.25 X lo6
preasphaltenes + as- 29.2 2.05 X 10' 12.8 9.66 X 10' 33.9 2.48 X lo9
phaltenes
asphaltenes + oils 29.0 1.14 X lo7 16.0 1.42 X l o 3 25.6 1.53 X lo7
a Cronauer et al. (1978). Shalabi et al. (1979). E , activation energy, kcal/g-mol;A, frequency factor, min-I.

1
0
PREMPHALTENES 7 0

0.2 L:ASQH~EST

'0 IO
0

20
UNREACTED COAL

OILS

30
7
40
,

50
9
60 70
UNREACTEDCOAL

REACTION TIME, mm REACTION TIME, mm

Figure 15. Comparison of kinetic model 4 with experimental Figure 16. Comparison of kinetic model 7 with experimental
product concentrations in the low-temperature range. product concentrations in the high-temperature range.

well in the low-temperature range but not as well in the

high temperature range as shown in Figures 14 and 15.
Models 5 and 6 were found to fit the data in the high-
temperature range but yielded negative values for some
of the rate constants. By analogy to model 2, model 7 with
reversible steps is proposed and is found to fit the data
very well in both high- and low-temperature ranges as
shown in Figures 16 and 17.
Unfortunately, no kinetic data exist in the literature for
Illinois No. 6 coal based on solubility measurements to
make a strictly valid comparison. It is of interest, however,
to make the best comparison that can be made at this time.
Thus, the kinetic parameters obtained by Cronauer et al.
(1978) and Shalabi et al. (1979) are compared in Table VI1
using other bituminous coals. Model 6 (Table IV) is es-
sentially identical with the kinetic model proposed by
Shalabi et al. (1979) shown in Table I with the exception
of the reaction where oils are formed from the preas-
phaltenes. Most of the kinetic parameters differ sub-
stantially from the values calculated here. This dis-
agreement may be caused by the differences in the coal-
solvent systems or the method of combining the LSC
fractions to obtain the oils, asphaltenes and preasphaltenes.
Conclusions
It has been found that nonisothermal experiments with
Illinois No. 6 coal liquefied in tetralin as the donor solvent
will yield reliable kinetic data for evaluation of kinetic
models. Liquid-solid chromatography has also been es-
tablished as an adequate separation method to model
donor-solvent coal liquefaction kinetics. The fact that the
rate data, and in particular, that of the multifunctional
<
R
/
cr1.- el01
1
P
: I\
I
REACTION TIME. mh
Figure 17. Comparison of kinetic model 7 with experimental
product concentrations in the low-temperature range.
compounds, fall into two temperature regions is of par-
ticular interest, but the reason for this effect is not known.
Model 3, with fewer parameters, fits the concentration-
time profiles in the low-temperature range almost as well
as model 2, but model 2 has been found to fit both tem-
perature ranges. A tentative method for combining the
five chromatographic fractions is proposed to obtain the
classical grouping of the compounds, preasphaltenes, as-
phaltenes, and oils, based on solubilities. In the high-
temperature region model 7 (Table IV) was found to be
the best, but all models gave reasonably good fits. Model
7 also fitted the data well in the low-temperature region.
358 Ind. Eng. Chem. Process Des. Dev. 1981, 20,358-360

Although the fit for model 7 is good, the calculated kinetic
parameters differ considerably from literature values. This
may be due to the difference in coal-solvent systems or the
method of combining chromatographic fractions to obtain
the solubility fractions. Whether kinetic models using LSC
separations are better than kinetic models using separa-
tions based on solvent solubility remains to be answered,
but LSC is probably more suitable for on-line analysis in
coal liquefaction plants.
Acknowledgment
The computational assistance of Ms. Joann Gherardi,
Mr. David German, and Mr. Jay Fleishman, supported by
Stevens Work Study Program, is appreciated.
Nomenclature
A = frequency factor, min-
Aii = stoichiometriccoefficients (positive if reaction j generates
class i, negative if it consumes class i, and zero if it does
not involve class i)
E = activation energy, kcal/g-mol
kj = first-order rate constant for reaction j
km = first-order constant for reaction step; A B
R = gas constant, 1.987 cal/g-mol K
- Shalabi, M. A.; Baldwln, R. M.; Baln, R. L.; Gary, J. H.; Golden, J. 0. Ind.
R, = rate of reaction step j , min-
t = time, min
T = absolute temperature, K
Wc = mass of dry, ash-free feed coal
W , = mass of dry, ash-free residue as THF insolubles
x = coal conversion defined by eq 3
x , = limiting coal conversion
Xi = mass fraction of class i, based on dry, ash-free feed coal
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Accepted November 12, 1980

Use of Solvent Extraction in the Production of the Ammonium Salt

of 3,5-Dinitro-l,2,4-triazole
Klen Y. Lee, Donald G. Ott, and Mary M. Stlneclpher
Los Alamos Scientific Laboratory, Los Alams, New Mexico, 87545

A process for the production of the ammonium salt of 3,5dinitro-l,2,4-triazole (ADNT) has been developed. The
process includes solvent extraction of 3,5dinitro-l,2,4-triazole (DNT) with water-insoluble, high-molecular-weight
amines and the preparation of the ammonium salt with anhydrous ammonia. The extraction of DNT is based on
the reaction of the free-base form of the amine with the organic acid to form the water-insoluble DNT-amine salt.
The production of ADNT is achiived by regeneration of the amine to its free-base form with a basic stripping agent
in a suitable diluent. The complete process requires 6 to 7 h on a laboratory bench scale and appears to be feasible
for large-scale production. The process could be applied to the production of any ammonium salt with properties
similar to those of ADNT.

Introduction Type 12/12B dropweight impact sensitivitiesof 59/80 cm,

The ammonium salt of 3,5-dinitro-1,2,4-triazoie(ADNT) and has a critical temperature of 222 C in 0.8 mm thick
is an explosive with several interesting properties. It is slab geometry.
soluble in water (28 g/100 mL), has a calculated PCJof 262 The parent compound, 3,5-dinitro-l,2,4-triazole (DNT),
kbar at its crystal density of 1.632 g/cm3, melts with loss was first prepared by U.S. Navy researchers (Burchfield
of ammonia at 170 O C , has ERL (Fedoroff et al., 1975) et al., 1963; Wiley et al., 1964), but a better method was
0196-4305/81/1120-0358$01.25/00 1981 American Chemical Society