ISSN 0361-5219, Solid Fuel Chemistry, 2009, Vol. 43, No. 3 , pp. 165–176. © Allerton Press, Inc., 2009.

Original Russian Text © A.S. Maloletnev, 2009, published in Khimiya Tverdogo Topliva, 2009, No. 3 , pp. 44–57.

Current Status of the Hydrogenation of Coals

A. S. Maloletnev
Institute for Fossil Fuels, Leninskii pr. 29, Moscow, 119991 Russia
e-mail: anatoly-maloletnev@rambler.ru
Received November 26, 2008

Abstract—The theoretical and experimental studies carried out at the Institute for Fossil Fuels during recent
years in the modernization of hydrogenation technologies for coal conversion into a liquid fuel under low
hydrogen pressure (10 MPa for bituminous coals and 6 MPa for a number of brown coals) are surveyed. These
studies are based on the advances of catalysis science and on the current concepts of the hydrogenation of
organic compounds and coal multimer. The capacity and cost efficiency of a coal chemical enterprise in the
commercialization of the technology are substantiated.
DOI: 10.3103/S0361521909030082

At present, in connection with possible reduction of
resources, high costs for the exploration of new depos-
its, and long-distance environmentally insecure trans-
port of oil to Europe, North America, and Japan
research and development continues to be carried out
intensively in many countries of the world (Australia,
Great Britain, Germany, Spain, Indonesia, Colombia,
People’s Republic of China, Pakistan, Poland, the
United States, South Africa, Japan, etc.). It is directed
toward the production of motor fuels from alternative
sources of raw materials (coal, shale, peat, biomass,
polymer and rubber containing wastes, etc.) with the
application of the processes of gasification, direct
hydrogenation, pyrolysis, hydropyrolysis, coking, ther-
mal dissolution, etc. [1, 2].
The most effective method to obtain the liquid fuel
from coals is the destructive hydrogenation. In Russia,
the studies on hydrogenation of solid fuels into motor
fuel and chemical feedstock began to develop in the
1920s based on fundamental studies [3] in the area of
hydrogenation reactions of organic compounds under
hydrogen pressure in connection with a shortage of
motor oil fuels and advances in the development of
commercial production in Germany [4].
Experimental work was performed at the Institute
for High Pressure Physics (GIVD), Fossil Fuels Insti-
tute of the USSR Academy of Sciences (IGI), the All-
Union Scientific-Research Institute of Synthetic Liquid
Fuel and Gas (VNIGI), the Ukrainian Scientific-
Research Coal-Chemical Institute (UKhIN) and other
organizations. At the end of the thirties in Russia, two
pilot plants operated in Kemerovo and Kharkov, where
hydrogenation technology of coals under a hydrogen
pressure of 30 MPa and above was perfected. In the fif-
ties in the USSR was created a commercial production
of liquid fuel by the coal hydrogenation in Angarsk.
In connection with the appearance of inexpensive
West-Siberian oil, this production was stopped in 1957.
Thereafter, research work in the area of coal hydroge-
nation was aimed at the creation of technologies for
processing of coal under lower pressure instead the
pressure was used at the plants of Germany, England,
USSR, and other countries (30–70 MPa) to improve
economic indices of production and to make the pro-
duction of liquid fuel from coal competitive to the pro-
duction of motor fuel from oil.
Scientific principles of chemistry and the technol-
ogy of production of liquid products from coals under
low pressure of hydrogen were developed by Soviet
researchers [5–9]. Scientific principles of domestic
technology of production of liquid fuel by hydrogena-
tion of coal under low pressure of hydrogen (10 MPa
for bituminous coals and 6 MPa for a number of brown
coals; 425–435°C; response time at the coal liquefac-
tion stage was 60 min; fine-grained, so-called pseudo-
homogeneous, Mo-containing catalyst) were devel-
oped. The technology was applied at the Pilot Plant ST-
5 (Tula oblast, productivity up to 10 tons of coal per
day) [10].
A possibility of using so low pressure for drastic
processing of coals became feasible due to the creation
of new methods of drying and preparation of coals for
hydrogenation, use of high-performance microcatalytic
system on the base of water-soluble Mo salts, donors of
hydrogen, stabilizers at the coal liquefaction stage, and
new catalysts for hydrorefining of liquid coal products.
Note that one of the ways to improve environmental
safety of motor fuels from the products of coal liquefac-
tion is an organization of methanol production by gas-
ification of coal and synthesis of high-antiknock oxy-
gen-containing additives on the base of accompanying
gases C4 of coal liquefaction in particular, methyl-tert-
butyl ether (MTBE), addition of which to motor gaso-
line produced from coal distillates makes it possible to
obtain pollution-free gasoline meeting Euro-2 standard.

165
166 MALOLETNEV
Brown coal
Air,
steam Coal and catalyst
preparation
HYDROGENATION
Gasification 6 MPa, 425 °C
Slag,
CO2 HYDROFINING
Energy 6 MPa, 400 °C
gas
CATALYTIC REFORMING
2.5 MPa, 500 °C
Diesel
fuel
Gasoline
Fig. 1. Flow diagram of production of motor fuels using IGI technology [32].
The processing of coal using IGI technology supports it
(Fig. 1).
As a result of coal hydrogenation, some amount of
water is formed (3–5% of coal), which is partially used
to prepare solution of a catalyst, while the bulk is added
to residues of the process such as sludge, containing
unconverted coal (5–10%), mineral components, and
catalyst. Thereupon they are dispersed and combusted
as a fuel-dispersed suspension to reactivate catalyst and
utilize wastewater.
Physicochemical principles of the method. A new
concept of structure and reactivity of low-metamor-
phism coals as a self-associated multimer, together with
the modern achievements of science in the area of catal-
ysis and the novel concepts of regularities of hydroge-
nation of organic compounds were assumed as a basis
of upgrading the process of hydrogenation liquefaction
of coal [11–13].
Multimeric structure of low-metamorphic coals is
governed mainly by electron donor–acceptor (EDA)
interaction involving the following functional groups:
−OH, –COOH, –COOM, –C=O, and others. EDA
interactions with the participation of aromatic frag-
ments make the main contribution into multimer struc-
ture. This happens both at the expense of dispersive
contribution during increase of polarizability of con-
densed nuclei and decrease of a distance between their
planes, as well as the formation of complexes with
charge transfer when ionization potential reduces and
Oxygen,
steam
Hydrogen
Gasification
Slag,
CO2
Gas
C1 – C4
H2 + CO
Methanol
synthesis
METHYL Methanol
TERT-BUTYL ETHER
(MTBE) SYNTHESIS
electron affinity grows during enlargement of aromatic
fragments. Minimum of general intermolecular interac-
tion falls on the coals with the carbon content of 85–
86% (vitrinite reflection index Rr is ~1.0%) that stems
from the structural peculiarities of such coals, the
organic matter of which is characterized by low oxygen
content and initial stage of clusterization involving aro-
matic blocks of the structure. It is worthwhile to use
low-ash coals of low-grade metamorphism, i.e., brown
ones, together with low- and medium-grade metamor-
phic bituminous coals.
A specific character of the structure of coal organic
mass (COM) governs mechanism of degradation reac-
tions and peculiarities of their behavior during liquefac-
tion. Initial phase of structure disintegration includes
breaking of EDA bonds with transfer of the certain
blocks and their associates into liquid soluble state.
Kinetic description of these transformations provides
feasibility of several simultaneously occurring stages,
which take into account in the generalized view the pro-
cesses of multimer dissociation. Value of the apparent
activation energies falls into the range of representative
values of EDA interactions [14], while formation of
quasicomponents (preasphaltenes, asphaltenes, and
oils) occurs according to parallel scheme with prevail-
ing accumulation of oils (molecular weight is in the
range from 200 to 300 amu). These processes progress
in the range from 350 to 380°C in a short period of time
(5–20 min) and they are not accompanied by consump-
SOLID FUEL CHEMISTRY Vol. 43 No. 3 2009
 CURRENT STATUS OF THE HYDROGENATION OF COALS
tion of gaseous hydrogen, i.e. its pressure in the system
does not affect the process at a conversion of COM up
to 50–70%.
At temperatures beyond 380–400°C, the activation
energy of formation of liquid products grows substan-
tially, consumption of gaseous hydrogen increases,
since a considerable disintegration of the COM struc-
ture and primary liquefaction products occurs at the
expense of cleavage of valence bond in the components
of associates and due to their saturation with hydrogen.
Catalytic thermal processes capture heterogeneous
areas of COM as witnessed by the formation of NH3,
H2S, H2O, ëO2, and low-molecular phenols. At this
stage, a role of hydrogen concentration in the reaction
mass increases significantly. The concentration is deter-
mined by hydrogen pressure in the process, the coal
structure, the paste-forming agent properties, and
above all, it depends on the mechanism of action of cat-
alysts applied and the character of their distribution in
the reaction mixture coal with paste-forming agent.
Thermodynamics of the process. One of the pivotal
questions of the problem of coal liquefaction is an opti-
mization of hydrogen transfer reaction from the paste-
forming agents, containing donors of hydrogen to the
macromolecular blocks of COM. The use of H-donors
is caused by relevance to elevate the hydrogen content
in the obtained liquid products in comparison with its
content in coal, which can be estimated by the values of
H/C atomic ratio, which is ≈0.85 for brown coals of the
Kansk-Achinsk Basin and ≈0.8 for gas coals from the
Kuznetsk Basin, while H/C ratio in motor fuels reaches
the values >1.8. Using H-donors facilitates coal multi-
mer dissociation, stabilizes degradation products,
which are transferred into liquid phase of COM macro-
molecules, and promotes reactions of removal of het-
eroatoms from them [15].
To forecast reactivity on hydrogenation of potential
hydrogen donors a cycle of thermodynamic calcula-
tions was used for typical reactions, occurring during
coal liquefaction.
As H-donors the most active compounds (hydro
derivatives of aromatic compounds and molecular
hydrogen), and as acceptor aromatic hydrocarbons with
ring number from 2 to 4, compounds having Ph–M–Ph
valence bridge bonds (where M is methylene or meth-
ylene–oxygen bonds), together with compounds having
heteroatoms in chain of π-electron conjugation (pyr-
role, furan, thiophene, their benzo and dibenzo deriva-
tives, phenol, etc.) were chosen for thermodynamic cal-
culations.
Hydrogen transfer reaction in general view is pre-
sented as:
a 1 A + a 2 D → a 3 A ( +H ) + a 4 D ( –H ),
where A is hydrogen acceptor; D is hydrogen donor;
A(+H) is partially (or completely) hydrogenated accep-
tor; D(-H) is partially (or completely) dehydrogenated
donor; a1, a2, a3, and a4 are stichiometric coefficients.
SOLID FUEL CHEMISTRY Vol. 43 No. 3 2009
167
Table 1. Characteristic of typical donors of hydrogen carriers
[15]
Hydrogen content, %
Compound
Htotal Har
Naphthalene 6.29 6.29
4,5-Dihydropyrene 5.92 4.98
9,10-Dihydroanthracene 6.71 4.47
1,4-Dihydronaphthalene 7.74 4.65
Tetralin 9.15 3.05
Decahydronaphthalene 13.12 0
For the hydrogen transfer reaction ∆Gr isobaric poten-
tial (Gibbs energy) of the reaction and reaction equilib-
rium constant were calculated:
K r = exp ( – ∆G r /RT ),
where R is the universal gas constant, and T is absolute
temperature, K.
The calculations were made basically for standard
thermodynamic conditions (temperature is 25°C, pres-
sure is 101.325 kPa) in the ideal gas approximation. A
criterion of optimal structure of hydrogen donor was
determined as a result of thermodynamic calculations
[16].
In the works [17, 18], it is shown that evaluation of
energy of C–H bond can be also made using correlation
between rate constants and change of enthalpy of reac-
tions with the participation of different donors and def-
inite acceptor. As a reactivity index of H-donor, the rate
constant was used (Table 1 and Fig. 2). It is seen in
Fig. 2 that the index is determined by the hydrogen con-
tent of the donor molecule. When passing from aro-
matic compound to the corresponding hydro derivative
optimal value of hydrogen content is ≈1.5%.
Content of aromatic hydrogen (Har) can also serve
as an additional criterion of optimal structure of H-
donor (Table 1). Really, when Har is ~4.0–4.5% effi-
ciency of H-donor properties of paste-forming agent
during liquefaction of coal decreases drastically.
The basic regularities, established on thermody-
namic analysis of model compounds and reactions are
also valid for total process of coal hydrogenation in
spite of a multitude of reaction centers of coals and
accordingly greater number of chemical reactions
occurring during liquefaction. This stems presumably
from the symbatic action of H-donors in reactions of
different types (hydrogenation of aromatic hydrocar-
bons, elimination of heteroatoms, destructive hydroge-
nation) and correlations of kinetic and thermodynamic
factors for reactions of every type.
The data on the influence of substituents in the mol-
ecules of donors on the equilibrium constant point to
the possibility to increase activity of hydroaromatic H
donors by matching of suitable substituents. For exam-
168 MALOLETNEV

Reactivity index of H-donors p, mol

7 log k 6.83 1.2
6 Row 1
Row 2
5 4.13
0.8 C
4 3.48
2.86
3 2.51
1.89
2 1.45 0.4
1.05 1.16 D
0.95 DH
1 0 0
CH
0
1 2 3 4 5 6 δH
Hydrogen content in H-donors, % 0 5 10 15 20
Time, min
Fig. 2. Effect of increasing hydrogen content in H-donors Fig. 3. Kinetics of conversion of hydrogen acceptor (A) in
on their reactivity index. the presence of hydrogen donor (D) and carrier (C) [20].
Row 1 shows an increase in the hydrogen content with
respect to corresponding aromatic hydrocarbons, and row 2
shows the logarithm of the rate constant of hydrogen trans- respectively (Figs. 3 and 4; Table 2). From Fig. 4, it fol-
fer to the diphenylmethyl radical at 275°C: (1) naphthalene, lows that consumption of hydrogen donor grows lin-
(2) 4,5-dihydropyrene, (3) 9,10-dihydroanthracene, (4) 1,4-
dihydronaphthalene, (5) tetralin, and (6) decahydronaph- early with increase in conversion of acceptor. As this
thalene. takes place, the greater is the value of k2, the greater is
the consumption of hydrogen donor.
As a result of calculations, it was found that depend-
ple, in [19] it is noted that introduction of hydroxyl ing on response time mole concentration of acceptor
group into position 5 of 1.2.3.4-tetrahydronaphthalene and donor exponentially decreases, while mole concen-
molecule increases yield of liquid products up to 85% tration of carrier decreases negligible and at τ = 6 min
during bituminous coal hydrogenation. it remains virtually constant.
Note that, from thermodynamic positions, hydrogen When studying kinetics of hydrogenation of brown
transfer reactions in the process of hydrogenation could coal from the Kansk-Achinsk Basin in the presence of
progress efficiently at comparatively low temperatures emulsified Mo-containing catalyst (0.05% by coal) and
[20]. In this connection, in further investigations and oil paste-forming agent under hydrogen pressure of
development work search of technological ways to per- 10 MPa results were obtained presented in Table 3 [24].
form the process of coal liquefaction in low-tempera-
ture region is of certain interest. Currently advertising
articles about such investigations performed by foreign D, %
companies have already appeared in the literature. 100

Kinetics of coal hydrogenation. Kinetic aspects of

coal hydrogenation under low pressure are examined in
detail in works [21–23]. As noted above, in the process
of coal hydrogenation under low hydrogen pressure a 80
participation of effective donors and carriers of hydro-
gen in the paste-forming agent composition is one of
a
the basic factors contributing to conversion level of b
COM. The role of donors as well as carriers of hydro- 60 c
gen in liquefaction of coals is studied extensively; how- d
ever, published works are free of data for interaction e
between donors and carriers on their simultaneous par-
ticipation in these processes. The study of kinetics of
such interactions clarified the mechanism of hydrogen 40
20 40 60 80
transfer that is necessary for effective performance of A, %
the process [23]. This problem was considered using as
an example the following reactions. Pyrene, 1,2-dihy- Fig. 4. Acceptor conversion dependence of the hydrogen
dronaphthalene, and anthracene were taken as hydro- donor conversion [20]: explicit data is given in line with
gen acceptor (A), hydrogen donor (D), and carrier (C), conventional signs (a–e) in Table 2.

SOLID FUEL CHEMISTRY Vol. 43 No. 3 2009

 CURRENT STATUS OF THE HYDROGENATION OF COALS 169

Table 2. Rate constants (min–1) become an additional solvent for unconverted COM
and inhibit of its precipitation on walls of apparatus.
Conventional
signs for data k1 k2 k3 Molecular weights of asphaltenes and preasphaltenes
in Fig. 4 in the liquid products obtained using IGI technology are
similar to each other and comprise 320–400 amu for
a 0.018 0.12 0.18 asphaltenes and 350–600 amu for preasphaltenes.
b 0.036 0.12 0.18 These values are significantly lower than the quantities
c 0.060 0.12 0.18 of the values of molecular weights for the products,
d 0.036 0.06 0.18 given in literature on foreign processes of hydrogena-
tion of coals. Formation of asphaltenes and preasphalt-
e 0.036 0.024 0.18 enes having lowered molecular weights are due to both
the nature of initial coal and conditions of carrying out
destructive hydrogenation under low hydrogen pres-
Developed mathematical-statistical model was used to sure, namely, using an active pseudohomogeneous Mo
optimize certain stages of the hydrogenation process, catalyst, applying elemental sulfur and paste-forming
for example at the stage of heating of coal paste in the agent (hydrogen donor) [21].
preheater at the Pilot Plant ST-5. As a result of carried
out development work at the Pilot Plant ST-5, it was Maximum conversion of coal and yield of liquid
found that at the stage of heating of coal–oil paste up to products under a pressure of 10 MPa is achieved in the
the temperature of 400–450°C a formation of mass of temperature range of 420–440°C and response time of
malthenes occurs directly from COM and further on the 15–20 min. However, for complete conversion of
hydrogenation process (influence of response time and asphaltenes this time in real-life environment needs to
be increased many times over. Owing to analysis of
temperature) it occurs from asphaltenes and preasphalt- multiple results of hydrogenation of brown coals under
enes, that slows down the process and requires expo- autoclave conditions and in environment of IGI stand
sure of reaction mass in the reactor over a long period flow installation (temperature of 350–450°C, pressure
of time. of 6–20 MPa, Mo catalyst) kinetic model of COM
This formation mechanism of desired products was transformations (Fig. 5) [23]. According to the model,
corroborated in the work [25]. It was found that at ini- effective rate constant KΣ = K1 + K2 + K3 + K4 … as the
tial stages of coal liquefaction (up to 15 min) total con- sum of constants of separate directions of transforma-
version of COM is described satisfactorily by a first- tions of COM and products obtained from it was taken
order equation. Amount of apparent energy of activa- as a generalized kinetic performance of coal reactivity.
tion of coal total conversion is 84 ± 8 kJ/mol and for Catalysts for coal hydrogenation. When coals are
reactions of formation of oils, gases, asphaltenes, and hydrogenated the concept of catalyst has uncertain and
preasphaltenes it amounts to 63 ± 6, 109 ± 10, 113 ± 8, relative meaning by the virtue of multitude of occurring
and 122 ± 9 kJ/mol, i.e., oils formed at the initial stages chemical reactions (destruction of coal multimer, acti-
of coal conversion (molecular weight is 200–250 amu) vation of molecular hydrogen, and others), while the

Table 3. Data on the hydrogenation of coal from the Borodinskoe deposit of the Kansk-Achinsk Basin [24]

Time of Yield of products

Conver-
Tempe- isothermal hydrogen % per initial COM % per converted COM
sion level gas,
rature, soaking of consump-
of COM,
°C autoclave, % per
tion, % per preas- asphal- oils + gas preas- asphal- oils + gas
% COM
min COM phaltenes tenes + water phaltenes tenes + water
400 0* 44.9 3.4 0.4 8.2 7.3 29.4 18.3 16.3 65.4
425 0 59.6 5.7 0.7 14.1 11.2 34.3 23.7 18.8 57.5
450 0 72.6 8.2 1.0 17.9 14.9 39.8 24.7 20.5 54.8
400 10 57.6 4.9 0.6 11.9 9.7 36.0 20.7 16.8 62.5
425 10 77.3 8.4 1.1 20.6 16.3 40.4 26.6 21.1 52.3
450 10 87.5 12.5 1.6 17.2 19.5 50.8 19.7 22.3 58.0
400 20 64.8 5.7 0.8 14.3 11.3 39.2 22.1 17.4 60.5
425 20 90.2 9.7 1.3 17.1 20.4 52.7 19.0 22.6 58.4
450 20 91.2 13.3 1.7 14.6 18.6 58.0 16.0 20.4 63.6
* Heating and cooling of autoclave without isothermal soaking.

SOLID FUEL CHEMISTRY Vol. 43 No. 3 2009

170 MALOLETNEV
K4
K1
COM Gas
K3
K2 K5
K7
K6
Preasphaltenes Asphaltenes Oils
K8
K10 K9
Carboides
Fig. 5. Diagram of organic matter conversion of brown
coals [23].
substances and mixtures used as a catalyst endure irre-
versible changes. It is agreed that the catalysts for coal
hydrogenation are the substances increasing the con-
version of coal into liquid (benzene-soluble) products.
The oxides and sulfides of transition metals (Mo, W,
Co, Sn, Ni, Fe, etc.) together with natural formations
and waste products containing these metals in amounts
from tenths of a percent to 5–10% per metal are added
to such compounds. Compounds of Mo (Germany,
1927) and Sn (England, 1936) were used in industrial
practice; however, owing to the lack of methods of their
reactivation a transition was made to iron-containing
catalysts (1.2% iron sulfate and 1.8% red mud, which
are waste products of alumina, and 0.2% sodium sul-
fide). The problem of reactivation of Mo catalyst in the
processes developed in the United States (H-Coal,
EDS, Dow Chemical Liquefaction) is not solved, con-
sequently as before the preference is given for search-
ing iron-containing systems, which are unpromising in
the case of realizing the process under low hydrogen
pressure (10 MPa and lower). Creation of scientific
principles and technology for preparation of composi-
tions activating the process and which have dimensions
comparable to the size of associates of coal multimers
is a major task in the area of catalysis on coal hydroge-
nation and not a traditional matching active additives or
their combinations. Support of transport of highly
active microcompositions with the paste-forming agent
to the surface of coal particles at the start of the process
and into microcracks appearing as solid coal substances
are conversed, together with the transport into space
between associates formed from coal multimer is an
important task of the catalysis as well. Inner action of
catalyst microadditives makes so beneficial effect that
offers a great challenge for efficient implementation of
the process under low hydrogen pressure. For this goal
as starting compounds soluble in raw material molyb-
denum naphthenates [26], molybdenum alkylphos-
phate and sulfonate [27], emulsion of ammonium par-
amolybdate aqueous solution [28], etc., are used.
Forming and using aqueous solutions of Mo-con-
taining catalysts as emulsions with paste-forming agent
turned out the most efficient way to add the catalysts
when coals are hydrogenated using IGI technology.
In this case on heating reaction mixture (coal–paste-
forming agent–catalyst aqueous solution) an uniform
distribution of the catalyst in the volume of coal–oil
paste, its transformation into sulfide derivatives (MoS2)
occurs and efficiency of using in the hydrogenation
process increases sharply due to the fact that the
formed cluster structures are substantially smaller in
size (5–7 nm) than the coal associates, which are being
repeatedly covered with the catalyst, activating molec-
ular hydrogen dissolved in the volume.
For process activation (achievement of more than
90% conversion of COM), it is sufficient to use Mo
additive in amount less than 0.1% per coal. However,
the catalyst containing so little amount of Mo needs to
be reactivated using capital-intensive technology. Intro-
duction of nickel sulfate into water-soluble Mo-con-
taining catalytic system showed that 30% substitution
of Ni for Mo in high-speed hydrogenation environment
(heating time is 1–2 min, 425°C, 10 MPa, 4.0% addi-
tion of S, oil paste-forming agent) and relatively short
response time (3–15 min) facilitates the improvement
of fractional composition of obtained liquid products
(yield of low-molecular distillate products increases)
when the conversion of COM is 82.0–87.8 [29].
Hereafter, experimental studies were directed at the
use of new fine-grained catalytic systems having low-
ered content of Mo or excluding its reactivation. Find-
ings of the study are given in the review article. Exper-
iments for study of catalytic activity of the Ni–Mo cat-
alytic systems prepared as 5% aqueous solutions in the
alkaline and acid medium (Mo : Ni mass ratio is in the
range from 30 to 70) and used as 3% solution per the
organic mass of paste (OMP) under 6 and 10 MPa at the
stage of liquefaction of brown coal from the Borodin-
skoe deposit of the Kansk-Achinsk Basin were carried
out in a 0.5-l rotary autoclave at 380, 400, and 425°C
for 0, 30, 60, and 120 min. Using more diluted aqueous
solutions of catalysts is less efficient since introduction
of additional amount of water into reaction mixture
reduces hydrogen partial pressure in the system as well
as it requires additional heat expenditure to heat water
to the process temperature that drops economic indica-
tors of production. Before applying catalysts coal was
predried at 80°C under vacuum (residual moisture con-
tent is 0.8–1.0%). To prepare paste, coal was mixed
with technical grade tetralin in a 1 : 3 mass ratio. Tetra-
lin had the following composition: 91.4 wt % base
material, 1.4 wt % naphthalene, 2.3 wt % decaline, and
4.9 wt % methylindan. As an additive, elemental sulfur
(2.0 wt %) was introduced into the paste. Activity of
catalysts was evaluated using conversion of COM,
overall yield of benzene-soluble liquid products, and
gas, together with solid products (unconverted COM
together with ash). Hydrogenation data are given in
Tables 4 and 5.
SOLID FUEL CHEMISTRY Vol. 43 No. 3 2009
 CURRENT STATUS OF THE HYDROGENATION OF COALS 171

Table 4. Data on the hydrogenation of brown coal from the Borodinskoe deposit in the presence of ammonium paramolyb-
date and aqueous solutions of Ni–Mo-catalysts (425°C, τ is 2 h, 2.0% of S, coal/tetralin ratio is 1 : 3, autoclave)
Catalyst
(NH4)6Mo7O24 (NH4)6Mo7O24
(NH4)6Mo7O24
Characteristic + Ni(NO3)2 + Ni(OH)2
Pressure, MPa
6.0 10.0 6.0 10.0 6.0 10.0
1. Input, wt %: 100.0 100.0 100.0 100.0 100.0 100.0
1.1. Raw materials, including: 23.8 23.7 24.0 23.9 24.0 23.8
coal 71.3 71.5 71.2 71.5 71.2 71.3
tetralin 1.9 1.9 1.9 1.8 1.9 1.9
sulfur 3.0 2.9 2.9 2.8 2.9 3.0
5% catalyst solution, including
Mo 0.05 0.05 0.044 0.042 0.044 0.045
Ni – – 0.101 0.098 0.101 0.105
1.2. Consumption of molecular hydrogen for reactions 1.0 2.0 1.5 2.1 1.9 2.4
Total 101.0 102.0 101.5 102.1 101.9 102.4
2. Output, wt %:
2.1. Liquid products* 84.9 85.9 87.5 88.3 88.0 88.4
2.2. Solid products** 5.2 4.1 5.9 5.0 3.8 3.2
2.3. Gas, including: 8.0 10.0 5.7 6.7 7.5 8.6
C1–C4 2.4 3.3 1.8 2.1 2.4 2.6
CO 0.5 1.1 0.2 0.3 0.2 0.3
CO2 3.0 3.3 2.2 2.5 2.9 3.0
H2S 2.1 2.3 1.5 1.8 2.0 2.7
2.4. Water 2.9 2.0 2.4 2.1 2.6 2.2
Total 101.0 102.0 101.5 102.1 101.9 102.4
COM conversion, wt % 92.3 93.5 92.6 95.7 94.0 95.5
Fractional composition of liquid products, wt %
boiling point below 180°C 11.3 15.2 9.4 11.5 15.4 15.8
180–230°C 73.2 68.9 66.6 64.3 69.3 67.3
above 230°C 15.2 15.3 23.5 24.2 15.3 16.1
loss 0.3 0.6 0.5 – – 0.8
Notes: * Benzene-soluble.
** Unconverted COM + ash.

From Table 4, it follows that at 425°C increase in
conversion of COM into liquid products in the presence
of Ni–Mo catalysts containing 0.042–0.045% Mo in
comparison with ammonium paramolybdate (0.05% of
Mo) comprises 0.8–3.1% under pressure of 6 MPa and
it is 2.4–2.5% under pressure of 10 MPa. Is seems that
in their presence formation of NiS along with MoS2
hastens the process of hydrogenation with formation of
HS• and H• radicals that makes it possible to achieve
deeper conversion of coal compared to the use of only
Mo. As hydrogen pressure changes from 6 to 10 MPa
Ni–Mo catalyst used in a form of aqueous solution of a
mixture of (NH4)6Mo7O24 + Ni(OH)2 demonstrated
higher catalytic activity virtually by all basic indicators
of hydrogenation. In its presence a lower residual con-
tent of solids (3.2–3.8%) in hydrogenation products,
higher yield of fractions having end boiling point of
180°C (15.4–15.8%), and moderate gassing (7.5–
8.6%) in comparison with aqueous solution of ammo-
nium paramolybdate and Ni–Mo catalyst used as a
(NH4)6Mo7O24 + Ni(NO3)2 were noted.
The obtained data make it possible to appraise the
above Ni–Mo-catalyst as a sufficiently effective cata-
lytic system to hydrogenate coal into liquid fuel under

SOLID FUEL CHEMISTRY Vol. 43 No. 3 2009

172 MALOLETNEV

Table 5. Data on the hydrogenation of brown coal from the Borodinskoe deposit in the presence of (NH4)6Mo7O24 + Ni(OH)2
catalyst (6.0 MPa, 2.0% of S, coal/tetralin ratio is 1 : 3; Mo/Ni ratio in the catalyst is 30 : 70; autoclave)
Yield of products, wt %
COM
Time of
conver- per initial COM per converted COM
reaction,
sion,
min oils asphalt- preas- solid oils asphalt- preas-
wt % gas gas
+ water enes phaltenes products + water enes phaltenes
Temperature, 380°C
0* 54.4 23.6 4.7 5.2 20.9 45.6 43.4 8.6 9.6 38.4
30 69.6 20.6 9.0 10.5 29.5 30.4 29.6 13.0 15.0 42.4
60 70.2 20.4 9.1 10.8 29.9 29.8 29.0 13.0 15.4 42.6
Temperature, 400°C
0 75.7 37.7 7.3 9.3 21.4 24.3 49.8 9.7 12.3 28.2
30 77.7 33.9 10.0 11.0 22.8 22.3 43.6 12.9 14.2 29.4
60 81.5 33.7 10.2 11.2 26.4 18.5 41.4 12.5 13.7 32.4
Temperature, 425°C
0 77.5 32.1 14.5 9.8 21.1 22.5 41.4 18.7 12.7 27.2
30 89.3 30.3 22.0 11.4 25.6 10.7 33.9 24.6 12.8 28.7
60 89.7 29.1 22.3 12.5 25.8 10.3 32.4 24.9 13.9 28.8
120 94.0 32.8 22.8 12.6 25.8 6.0 34.9 24.2 13.4 27.5
* Heating and cooling of autoclave without isothermal soaking.

low pressure of hydrogen. In its presence under pressure
of 6 MPa as response time increased from 0 to 60 min
(Table 5) conversion of COM increased from 54.4 to
70.2% at 380°C, from 75.7 to 81.5% at 400°C, and it
was 77.5–89.7% at 425°C. The conversion of coal had
the highest value of 94.0% after 120 min of hydrogena-
tion of coal. Over the whole investigated temperature
interval increase in response time was accompanied by
the growth of gassing, therewith CO2 + H2S comprised
more than 65.0% in the composition of the formed gas.
From the experimental data, it follows that distribu-
tion character of hydrogenation products depending on
temperature, response time is identical, and oils and gas
are dominant products. Yield of oils per COM
decreases as the hydrogenation time increases, while
yield of remaining products grows (Table 5). With com-
mon time of experiment, temperature elevation causes
considerable increase in conversion of COM and yield
of asphaltenes. Yield of preasphaltenes therewith first
remains practically at same level and then declines
apparently at the expense of continuation of reactions
for their conversion into low-molecular products.
Obtained data can be taken as a basis for formation
of recommendations to carry out further research and
they can be considered as one of the ways to enhance
efficiency of liquid fuel production by hydrogenation of
coals using IGI technology commercially.
Hydrogenation of coal distillates. Liquid products
(40–45%) produced from coal generally consist of frac-
tions having end boiling point of 360°C and they serve
as potential raw materials for production of motor fuels
by the methods of hydrofining, hydrocracking, and cat-
alytic reforming used in petroleum refineries.
Research on hydrorefining of initial coal distillates
having different fractional composition was carried out
using domestic and foreign stationary catalysts by
example of liquefaction products from the coals of the
Kansk-Achinsk Basin. To this effect industrial domes-
tic catalysts (Al–Co–Mo and Al–Ni–Mo, TU [Russian
Technical Specifications] 38-101194-77), test samples
of macroporous catalysts prepared at the Boreskov
Institute of Catalysis, Siberian Branch, Russian Acad-
emy of Sciences, catalysts of the Institute VNIINP
(Russia), and Haldor Topsoe (Denmark) catalysts were
used [30, 31].
Liquid products of coal hydrogenation include both
heterocyclic compounds and considerable amount of
aromatic hydrocarbons. Removal of heterocyclic com-
pounds and obtaining of hydrocarbon fuels with
improved environmental characteristics in the presence
of industrial hydrofining catalysts existing in oil pro-
cessing does not lead to problems [32]. For reduction of
content of aromatic hydrocarbons from 45–50% to
20% and under in the composition of diesel fuels to suit
requirements of Euro standards for environmentally
safe motor fuels accepted in many European countries
it is necessary to use new catalytic systems at the stage
of hydrorefining of coal distillates. Nickel–tungsten
sulfide catalyst (NVS-30) prepared at VNIINP is one of
such systems. It makes possible under low pressure to
achieve 92% desulfurization of coal distillates and 75%
hydrogenation of aromatic hydrocarbons [33] in com-

SOLID FUEL CHEMISTRY Vol. 43 No. 3 2009

 CURRENT STATUS OF THE HYDROGENATION OF COALS 173

Table 6. Characteristic of components of motor gasoline produced from coal distillates

Standard value for motor
Component of motor
Characteristic gasoline according to
gasoline
GOST R 51105-97
Octane number, no less than:
motor method 82.5 84.6
research method 91.0 92.9
Content of lead, mg/dm3, no more than 0.01 Unavailable
Content of manganese, mg/dm3, no more than 18 The same
Content of soluble gums, mg per 100 ml of fuel, no more than 5.0 0.2
Breakdown time, min, no less than 360 415
Weight fraction of sulfur, %, no more than 0.05 0.003
Volume fraction of benzene, %, no more than 5 0.25
Corrosion test of copperplate Stands, I class Stands
Appearance Transparent Transparent
Density at 15°C, kg/m3 725–780 749

Table 7. Characteristic of diesel fuel from coal liquefaction products

Standard value for diesel fuel
Component of diesel
Characteristic of Euro, I class according to
fuel
GOST R 52368-2005
Cetane number, no less than 51 51
Cetane index 〈1〉, no less than 46 46
Density at 15°C, kg/m3 820–845 839
Fractional composition, °C
distillated at temperature under 250°C, vol % no less than 65 68
distillated at temperature under 350°C, vol % no less than 85 87
95 vol % distillated at temperature no higher than, °C 360 358
Cloud point temperature, °C no higher than –16 –18
Limiting filterability temperature, °C no higher than –26 –26
Flash point determined in the closed crucible, °C, no higher than 55 40
Content of sulfur, wt % no more than 0.05 0.03
Content of water, mg/kg no more than 200 no
Corrosion test of copperplate (for 3 h at 50°C) Stands, I class Stands

parison with 75% and 35% for existing industrial cata-
lysts, respectively (Tables 6 and 7). After hydrofining in
the presence of the catalyst coal distillates having the
boiling point range of 180–360°C in their physico-
chemical properties and running ability suit require-
ments of Euro-3 standard for low-sulfur diesel fuel, and
hydrofined gasoline can be used as a component of
motor gasoline conforming to Euro-2 standard.
Hydrogen production. In connection with extensive
use of hydrogenation processes in the processing of
coals and their distillates satisfaction of need in high-
quality hydrogen is a major task during commercial
realization of the mentioned processes. At present gas-
ification of coal is a sole technical industrial method to
produce hydrogen necessary for coal hydrogenation
and hydrorefining of obtained liquid products. The gas-
ification of coal using oxygen–steam blast in fluidized
bed under pressure of 2–3 MPa with hot gas cleaning is
one of such processes. This process is significantly
more efficient than the processes previously used at
domestic and foreign gas works (in the early 1960s in
Russia, gas was produced from coal, shale, and peat in
amount up to 35 billion cubic meters per annum), since
makes it possible to enhance gasification coefficient of
efficiency from 60–70 to 85% and to reduce capital
expenditure by 20% compared to well-known indus-
trial methods (LURGI, KOPPERS–TOTZEK, and
WINKLER).

SOLID FUEL CHEMISTRY Vol. 43 No. 3 2009

174 MALOLETNEV

Table 8. Commodity balance of a unit for the hydrogenation of coal from the Kansk-Achinsk Basin
Item wt % on a wet coal basis t/year
Taken:
(1) as-received coal, including: 100.0 3600000
dry coal 61.6 2217600
consumption for hydrogenation 58.9 2120234
(2) Mo-containing catalyst – 74
Total 100.0 3600000
Obtained:
(1) AI-93 unleaded motor gasoline 6.9 246600
(2) Low-sulfur diesel fuel (S ≤ 0.03%) 15.1 543000
(3) Elemental sulfur 0.05 1300
(4) Ammonia 0.2 6500
(5) Slag after the combustion of hydrogenation sludge 22.15 797400
Total commercial products 44.4 1594800
(6) Unit auxiliaries
fuel gas 12.9 463000
ammonia 0.3 900
(7) Gaseous, liquid, and solid wastes 42.0 1526900
(8) Losses 0.4 14400
Total 100.0 3600000

Table 9. Cost effectiveness of the manufacture of motor fuels by the hydrogenation of coals from the Kansk-Achinsk Basin
Value in the manufacture of
Item Dimensionality
gasoline diesel fuel
Total output of motor fuels t 246600 543000
Producer price ruble/t 8734 7900
Liquidation value thousands of rubles 2148564 4289700
Operating costs thousands of rubles 1093508 2030802
Profit:
gross profit thousands of rubles 1055056 2558898
after-tax profit (minus 20%) thousands of rubles 844045 1807118
Capital expenditure for the manufacture of products thousands of rubles 3271000 6075000
Payback period of capital expenditure with respect to profit:
gross profit year 3.1 2.4
after-tax profit year 3.9 3.7
Level of the profitability of manufacture with respect to profit:
gross profit % 32 42
after-tax profit % 25 29

Using a method of short-cycle adsorption to remove [34]. Development and industrial production of a great
impurities of hydrocarbons, carbon oxides, ammonia, number of new adsorbents (silica–alumina and carbon
and hydrogen sulfide is an important factor of hydrogen molecular sieves, silica gels, and others having specific
saving on industrial production of liquid fuel from coal surface areas of several hundred square meters per

SOLID FUEL CHEMISTRY Vol. 43 No. 3 2009

 CURRENT STATUS OF THE HYDROGENATION OF COALS
gram of adsorbent) facilitated widespread adoption of
the method. Separation of gas mixtures using short-
cycle adsorption is based on different interaction force
of adsorbent with various gases and on different
adsorption rates of various gases.
Hydrogen cleaning is performed in two stages. First
easily adsorbable heavy components and subsequently
methane, carbon monoxide, and nitrogen are removed.
Hydrogen content in the cleaned gas is 96.0–96.5 vol %,
but it is 99.999 vol % when needed. Traditionally, reac-
tivation through depressurization is used in short-cycle
adsorption. Short duration of adsorption and reactiva-
tion, usually within several minutes is the next distin-
guishing feature of short-cycle adsorption, causing this
process received the name short-cycle adsorption
(SCA). From the above, it follows that cheap hydrogen
purified from undesirable impurities can be produced
from circulating hydrogenous gas using the SCA
method. This gas can be efficiently utilized to improve
quality and quantum of output at the stage of coal
hydrogenation and hydrorefining of coal distillates.
Ways to implement the technology of coal hydroge-
nation on industrial scale. At present, a construction of
parent enterprise (module) having capacity sufficient
for development of non-model-based and difficult-to-
model technology elements is the only possible way to
implement the technology of coal hydrogenation on
industrial scale. On the other hand, the enterprise has to
be cost-beneficial and ensure a profit at the market.
According to a number of features, the module with
capacity of 500 thousand tons of liquid products per
annum (3.6 million tons of brown coal and 1.6 million
tons of bituminous coal per annum) is the most agree-
able to these conditions. On evidence of OAO Tulain-
zhneftegaz, this capacity can be provided with one pro-
cessing line. Using low pressure on hydrogenation of
coal and coal distillates makes it possible both to reduce
substantially amount of cost per unit for creation and
operation of industrial enterprise and to use in full for
this purpose equipment produced by enterprises of
Russia that is substantial, since it does not require addi-
tional investment of capital for creation of machine
building resources. It was corroborated by practice of
designing, equipment manufacture for experimental
industrial installations (ST-5 and ST-75), sketch elabo-
ration of equipment for industrial modular installations.
Modules are constructed at the territories adjacent to
enterprises of coal industry (coal open pits, mines,
coal–preparation plants), having reserves of low-ash
(Ad is 10–12% for brown colas and 5–8% for bitumi-
nous ones) fine grade coals (fineness under 13 mm)
with no limitation for moisture content, trace elements,
and other impurities detrimental for the common use in
power engineering, coking, communal-general service,
and agriculture. Availability of natural gas and coke
oven gas substantially (by 25–40%) reduces outputs for
the production of motor fuels owing to the possible har-
nessing of them for technological purposes.
SOLID FUEL CHEMISTRY Vol. 43 No. 3 2009
175
Module consists of the following basic units (grind-
ing, powdering, and deep drying); preparation of the
mixture (1 : 1 ratio) of coal and inherent liquid product
(paste-forming agent) with catalyst; transport of a mix-
ture into reaction system in a flow of hydrogenous gas;
conversion of coal into liquid products in tubular reac-
tors; separation of liquid products from ash; processing
of coal distillates into motor fuels with improved envi-
ronmental properties; production of fuel gas and hydro-
gen using coal gasification; heat and power supply of
module with standard thermal power plant; auxiliary
productions including gas and water cleaning from det-
rimental impurities preceding discharge into atmo-
sphere and open reservoirs; packaging and shipment of
finished products to consumers (liquefied gases, motor
gasoline, diesel oil and jet engine fuel, furnace oil, fuel
oils, and other items of production). Production capac-
ity of the module can supply a region with population
size of 0.8–1.0 million of people with liquefied gas,
motor fuel and associated products.
As an example, in Tables 8 and 9 summarize the
cost-effectiveness and commodity balance of produc-
tion of motor fuels using hydrogenation of coals from
the Kansk-Achinsk Basin composed of industrial enter-
prise with capacity of 500 000 tons of motor fuels per
annum.
In summary, note that, in spite of oil abundance and
underload of refineries with processing, practically all
scientific and technical together with economic prereq-
uisites exist for the creation of industrial module instal-
lations in coal-mining regions of the country with the
annual capacity of 500 000 tons of liquid fuel at the
price of coal oil not over US $150 per ton.
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