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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 solvents with the definition for the various solubility classea
In view of the need to develop commercially viable is given in Table I. These experiments were carried out
processes for deriving liquid fuels from coal a description with and without catalysts and donor solventa using mostly
of coal liquefaction kinetics is necessary for reactor design bituminous coals. The proposed kinetic models for li-
and scaleup. Most coal liquefaction processes involve quefaction with or without donor solvents are in many
dissolution of the coal by using a hydrogen-donor solvent cases similar. In many of the studies a hydrogen-donor
with added gaseous hydrogen, but among the various solvent with an added catalyst was used.
solvents employed in laboratory studies tetralin has been In the earlier proposed kinetic models the reaction
found to be the most common hydrogen donor. Fur- products, oils and asphaltenes, were combined or treated
thermore, synthetic solvents designed to simulate a typical separately to determine reaction rate constants. Pelipetz
process solvent invariably contain significant amounts of et al. (1955) and Hill et al. (1966) assumed that only a
tetralin. The addition of gaseous hydrogen in donor-sol- single thermal decomposition process occurs. Falkum and
vent liquefaction in several laboratory investigations has Glenn (1952) found that the hydrogenolysis of Spitsbergen
been shown to yield higher conversions (Han et al., 1978). coal occurred in two distinct stages and suggested that two
Recently, Maddocks and Huffman (1978) proposed that constituents are present in coal, one of which degraded
no hydrogen gas be added in the first dissolution stage of much faster than the other. Such a model, involving two
a two-stage coal liquefaction process. Also, in recent lab- reactive constituents, was investigated by Curran et al.
oratory studies Mitchell and Whitehurst (1978) and Lon- (1967) and Struck et al. (1969) and was found to fit their
ganbach et al. (1979) liquefied coal at short contact times experimental conversion data on coal extraction and
in the absence of gaseous hydrogen. In our studies tetralin coal-extract hydrocracking processes. Weller et al. (1951)
was used as the donor solvent without added gaseous hy- proposed that the conversion of coal to oils involves two
drogen. consecutive first-order reactions with asphaltenes as an
The kinetics of coal liquefaction are very complex intermediate product. They determined the rate constants
leading to the formation of numerous compounds. The for both steps as shown in Table I. On the other hand,
approach in kinetic studies has been to attempt to separate Liebenberg and Potgieter (1973) proposed two simulta-
these compounds into kinetically similar classes based neous reactions for the formation of oils and asphaltenes
on some separation technique. Most studies used methods in order to explain their experimental data. Yoshida et
of separation that depend on solubility in various solvents al. (1976) expanded this model to allow for oils formation
to separate coal liquids. These studies are summarized in by two paths. Recently, Chiba and Sanada (1978) assessed
Table I. Recently, Brunson (1979) used distillation to the previous models consisting of oils and asphaltenes and
measure the kinetics of formation of gaseous and liquid suggested using the formation of oils from two active coal
products using a coal-derived hydrogen-donor solvent. components to explain the experiments in the literature.
Prather et al. (1977) indicated the feasibility of using Recently, a third class of compounds, the preasphalt-
analytical liquid-liquid chromatography (LLC) to char- enes, was isolated from coal liquefaction products and was
acterize coal liquefaction solvents for studying kinetics, but shown to be a key reaction intermediate by Sternberg et
they did not attempt to use this approach to obtain al. (1975). Thus a more complex model was proposed by
product compositions for estimating kinetic parameters. Schweighardt and Sharkey (1976) using preasphaltenes in
Whitehurst et al. (1977) separated coal liquid products by addition to oils and asphaltenes. Subsequently, simplified
liquid-solid chromatography (LSC) on silica using various versions of this model have been satisfactorily tested in
eluting solvents in sequence. They concluded that the coal a batch reactor (Shalabi et al., 1979) as well as in a con-
liquefaction products contained a large number of com- tinuous reactor (Cronauer et al., 1978; Traeger, 1979).
pounds with very similar hydrocarbon skeletons differing Squires (1978) proposed a more comprehensive working
only by the various functional groups, and they also did model for donor-solvent coal liquefaction, but the model
not propose any kinetic model based on the separated has not been tested to date because the isolation procedure
products. for the product oil and semi-coke has not been es-
A summary of kinetic models and rate constants based tablished.
on product compositions obtained by solubility in various In this study LSC was employed to separate the coal
0196-4305/81/1 120-0349$01.25/0 0 1981 American Chemical Society
350 Ind. Eng. Chem. Process Des. Dev., Vol. 20, No. 2, 1981
liquids into classes of compounds for kinetic analysis. reactor to minimize reactant heat-up times. This system
Chromatographic separation promises to be a more effi- included a double-pipe heat exchanger to prevent over-
cient and perhaps more fundamental method. heating of the Teflon seat of the ball valve caused by heat
conduction from the reactor. Nevertheless, the Teflon
Experimental Section seats still had to be cleaned or replaced after a few in-
System Design. Since Storch et al. (1940) reported the jections because of coal deposits or erosion. The holdup
use of batch reactors for kinetic studies, many investigators of the slurry in the injector, which was washed and mixed
have employed these massive reactors of various capacities. with the reactor wash at the end of a run, was found to
These reactors require long heat-up and cool-down times, be less than 0.5% of the slurry injected. This method of
during which significant reactions can occur. The ap- slurry injection caused a temperature drop of 30 "C of the
proaches used to minimize these nonisothermal heat-up reaction mixture upon injection, thus requiring a method
times have been to use small reactors constructed from to correct for the nonisothermal reaction conditions.
tubing (Neavel, 1976) or to first heat up the solvent to the The furnace temperature was controlled by a propor-
reaction temperature and inject the coal slurry with a tional action temperature controller using a chromel-alu-
pump (Shalabi et al., 1979). If isothermal conditions me1 thermocouple and solid-state switching (Barber-Col-
cannot be obtained experimentally, then a calculation man, Series 530). The reaction temperature was measured
procedure is required to correct for the nonisothermal manually (*l OC) with another chromel-alumel thermo-
conditions, which is the approach adopted here. Earlier, couple inserted into the thermowell of the reactor using
Yergey et al. (1974) applied the nonisothermal analysis to a cold-junction compensator and a potentiometer. The
estimate the kinetic rate parameters for the hydro- temperature was also recorded with a Leeds & Northup
desulfurization of coal. Recently, Morita et al. (1979) used Speedomax X/L 680 recorder with a full scale response
a nonisothermal analysis for estimating the reaction rate of 1 8.
parameters in studying the effect of hydrogen pressure on All the components of the Magnedrive impeller were
the rate of direct liquefaction of some Japanese coals. disassembled and cleaned thoroughly after each run.
The experiments discussed here were conducted in 1-L Neither the graphite bearings of the Magnedrive impeller
stirred reactor (Autoclave Engineers, Model AFP-1005, nor the stainless steel gasket needed replacement during
Magnedrive), shown in Figure 1, where all materials in the course of this work, because of the care and cleaning
contact with the coal slurry are 316 stainless steel. A coal procedure adopted. The reaction mixture was stirred at
slurry injection system was designed and added to the 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
0.25 r
THFWIB*OFREACTDR
4-4
REACTOR
GASES
t L E A 0 ACETATE
SCRUBBER
p-/-'T' SLURP"
'
i ' I
A 800 1200 I IO
VOLUME ELUTED, mi
NiTRDGlNS
HIOROXYLS
*SH UULTlFUNCTlONilLI
s
1 0.16 i-
3800I
I / I IO 20 30 40 50 60
TIME, mln
REACTION TIME, min
Figure 6. Chebyshev fit to the measured reaction temperature-time Figure 7. Desulfurization of Illinois No. 6 coal.
profile.
dihydronaphthalene, and tetralin. Furthermore, it was The starting values for the rate parameters, Aj and Ej,
found that in the blank runs, using tetralin without coal were obtained by executing the isothermal version of the
under similar reaction conditions, the same product con- program using values for the rate constants that are con-
centrations were produced within experimental error. sistent with those in Table I. The optimal parameter
Hence no significant amounts of naphthalene and di- estimates of this program were the maximum likelihood
hydronaphthalene are derived from the coal under the estimates and they are neither unique nor global. Ob-
reaction conditions used, and the saturates fraction con- taining a satisfactory fit of a kinetic model to the exper-
tains the unrecovered tetralin and its reaction products imental concentration-time profiles by this method does
from the distillation step. Therefore, the saturates fraction not verify the correctness of a kinetic scheme because good
from the SRC was combined with the distillate and was fits can always be obtained if the kinetic scheme is made
not considered in the kinetic schemes. The aromatics sufficiently complex so as to introduce additional param-
fraction was partially soluble in the mobile phase and when eters. The method, however, does allow one to reduce the
analyzed showed the absence of decalin, naphthalene, number of possibilities because some kinetic schemes may
dihydronaphthalene, and tetralin. The other fractions be eliminated because of poor fits. Once a satisfactory fit
obtained from the preparative chromatographic separa- has been obtained additional experimental information is
tions are insoluble in the mobile phase. required before the kinetic scheme can be accepted. Also,
parameter estimation is useful in planning experiments.
Kinetic Modelling and Parameter Estimation Desulfurization. The coal used in this work is a very
The kinetic models are obtained by performing a dif- reactive Illinois coal with 3.7 mass % sulfur and 12.5% ash
ferential mass balance for each class of compounds present content. In order to estimate the extent of desulfurization,
in reactor a t any instant. Thus, the general set of dif- the mass fraction of sulfur removed as H2Swas calculated
ferential equations representing a proposed reaction on the basis of total sulfur in the coal. With such high ash
scheme and the initial conditions are written as 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
Xi(0) = XIJi found that up to 18% of the total sulfur is removed as H a
The rate, Rj, depends on the component concentrations, during the experiment with large desulfurization occurring
X i , and temperature. The kinetic models developed here at higher temperatures and extended times as shown in
are restricted to systems of fmt-order reactions, where the Figure 7. These results are consistent with those reported
temperature dependence for the rate constant is given by by Longanbach et al. (1979) for the liquefaction of a West
the classical Arrhenius expression Kentucky 9/14 coal using Wilsonville recycle solvent under
similar conditions of temperatures and pressures except
k j = Aj exp(-Ej/(RT)) (2) that the reaction times were less than 5 min and sol-
The objective then is to estimate the rate parameters, vent/coal ratios less than 3.
Aj and E,, for proposed kinetic models by using nonlinear Coal Conversion Kinetics. Coal conversion is based
regression techniques (Bard, 1974). The estimation pro- on the fraction of liquefied coal that is insoluble in tet-
cedure consists of fitting the solutions of eq 1to the con- rahydrofuran. The coal converted on the dry and ash-free
centration measurements made at different reaction times basis, defined as
and temperatures since the experiments are nonisothermal.
The temperature variation during an experiment (Figure WC - WR
x = (3)
6) is fitted by a 10-term series expansion in Chebyshev WC
polynomials (Esch, 1974) with the Chebyshev coefficients
determined by unweighted least-squares fitting to the was reproducible within 4% absolute error. A first-order
reaction temperature-time profile. Hammings modified irreversible reaction scheme for coal dissolution is assumed
predictor-corrector method is used to numerically integrate in accordance with earlier investigations (Han et al., 1978)
the set of simultaneous linear differential equations given and the kinetic model is represented as
by eq 1. The nonlinear estimation algorithm (Meeter, dx
1965) is based on Marquardts method (1963), which - = -k(X, - X ) (4)
dt
combines the best features of the Gauss-Newton and
steepest descent methods. 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
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
a 0.0346
5. c - A 0.0359 b
\)
0.0336 b i 0.61 \
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
1.01
aromatics (A) ethers (E)
E].[ti.]
kCN 0 0 0 0 0
kCE 0 0 0 0 0
UNREACTEDCOAL
kCA 0 0 0 0 0
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
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.
Although the fit for model 7 is good, the calculated kinetic Falkum, E.; Glenn, R. A. F d I 9 5 2 , 31, 133.
parameters differ considerably from literature values. This Guh, J.; Tarrer, A.; Taybr, L., Jr.; Rather, J.; Green, S., Jr. Ind. ng. Chem.
Rocess Des. Dev. 1976, 75, 490.
may be due to the difference in coal-solvent systems or the Han, K. W.; Dixit, V. B.; Wen, C. Y. Ind. Eng. Chem. Process Des. Dev.
method of combining chromatographic fractions to obtain 1978, 17, 16.
Hili, 0. R.; Harlri, H.; Redd, R. 1.; Anderson, L. L. A&. Chem. Ser. 1966, No.
the solubility fractions. Whether kinetic models using LSC 55, 427.
separations are better than kinetic models using separa- Llebenberg, B. J.; Potgieter, H. G. J. Fuel1973, 52(4), 130.
tions based on solvent solubility remains to be answered, Longanbach, J. R.; Droege, J. W.; Chauhan, S. P. Repr. Div. Fuel Chem.,
Am. Chem. Soc. 1979, 24(2). 52.
but LSC is probably more suitable for on-line analysis in Maddocks, R. R.; Huffman, E. L. Prepr. Div. Pet. Chem., Am. # e m . Soc.
coal liquefaction plants. 1978, 23(4), 1296.
Marquardt, D.W. J . Soc. Ind. Appl. Meth. 1963, 17(2), 431.
Acknowledgment Meeter, D. A. Nonlinear Least Squares (&ushaus), Program No. COO17-00/
SOO17-00, Unhrerslty of Wisconsin Computing Center, Madison, WI, 1965.
The computational assistance of Ms. Joann Gherardi, Mitchell, T. 0.; Whltehurst, D. D. Paper No. 116, 71st Annual Meeting of the
AIChE, American InstlMe of Chemical Engineers, New York, Nov 1978.
Mr. David German, and Mr. Jay Fleishman, supported by Morlta, M.; Sato, S.; Hashlmoto, T. Repr. Dlv. Fuel Chem., Am. Chem.
Stevens Work Study Program, is appreciated. Soc. 1979, 24(2). 270.
Neavel, R. C. Fuel 1978, 55(7), 237.
Nomenclature Pelipetz, M. G.; Salmon, J. R.; Bayer, J.; Clark, E. L. Ind. Eng. Chem. 1955,
47(10), 2101.
A = frequency factor, min- Rather, J. W.; Tarrer, A. R.; Guh, J. A.; Johnson, D. R.; Neely, W. C. Llquid
Aii = stoichiometriccoefficients (positive if reaction j generates Fuels from Coal, Elllngton, R. T., Ed.; Academic Press: New York, 1977;
p 245.
class i, negative if it consumes class i, and zero if it does Schiller, J. E.;Mathiason, D. R. Anal. Chem. 1977, 49, 1225.
not involve class i) Schwelghardt, F. K.; Sharkey. A. 0. Prepr. 1976 Coal Chemistry Workshop,
E = activation energy, kcal/g-mol pp 72-85, Stanford Research Instltute, Menio Park, CA, Aug 1976.
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.
Eng. Chem. Process Des. Dev. 1979, 18, 474.
Squires, A. M. Appl. Energy 1978. 4. 161.
Sternberg. H.; Raymond, R.; Schwelghardt, F. K. Pfepr. Div. Fuel Chem.,
Am. Chem. Soc. 1975, 20(4), 198.
R, = rate of reaction step j , min- Storch, H. H.; Fisher, C. H.; Eisner, A.; Clarke, L. Ind. Eng. Chem. 1940,
t = time, min 32(3), 346.
T = absolute temperature, K Struck, R. T.; Clark, W. E.; Dudt, P. J.; Rosenhoover, W. A.; Zlelke, C. W.;
Wc = mass of dry, ash-free feed coal &in, E. Ind. Eng. Chem. Process Des. Dev. 1989, 8 , 546.
W , = mass of dry, ash-free residue as THF insolubles Traeger, R. K. Paper No. 19% 86th National Meeting of the AIChE, American
Institute of Chemical Engineers, New York, Apr 1979,
x = coal conversion defined by eq 3 Weller. S.; Pelipetz, M. G.; Friedman, S. Ind. Eng. Chem. 1951, 43(7), 1575.
x , = limiting coal conversion Whitehurst, D. D.; Farcaslu, M.; Mitchell, T. 0.; Dickert, J. J., Jr. The Nature
Xi = mass fraction of class i, based on dry, ash-free feed coal and Orlgin of Asphakenes in Processed Coals. EPRI Final Report, AF-
460, Electric Power Research Institute, Palo Alto, CA, July 1977.
L i t e r a t u r e Cited Wiser, W. H. Chemisw of Coal Liquefaction: Status and Requirements.
Scientific Problems of Coal Utlllzation, Cooper, B. R., Ed.; p 232, DOE
Bard, Y. Nonllnear Parameter Estimation, Academic Press, New York, Symposium Series 46, CONF-770509, National Technlcal Information
1974. Services, Springfield. VA. 1978.
Brunson, R. J. Fuel 1979, 58(3), 203. Yergey. A. L.; Lampe. F. W.; Vestal, M. L.; Day, A. G.; Ferguseon, G. J.;
Chiba, T.; Sanada. Y. Nenryo Kyokai Sbi 1978, 57(612), 259. Johnson, W. H.; Snyderman, J. S.; Essenhigh, R. H.; Hudson, J. E. Id.
Cronauer. D. C.; Shah, Y. T.; Ruberto, R. G. Ind. Eng. Chem. Process Des. Eng. Chem. Process Des. Dev. 1974, 13, 233.
Dev. 1978, 17, 281. Yoshida, R.; Maekawa, Y.; Ishii, T.; Takeya, G. Fuel 1976, 55(10), 337.
Curran, G. P.; Struck, R. T.; Gorln, E. Ind. Eng. &em. Process Des. Dev.
1967, 6, 166.
Esch, R. Handbook of Applied Mathematics, Pearson, C. E., Ed.; Van Receioed for reuiew December 31, 1979
Norstrand-Reinhold: New York, 1974; p 964. Accepted November 12, 1980
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.