Synthesis of Ni–W aromatic hydrocarbon hydrogenation catalysts by the ex situ and in situ decomposition of a precursor based on a dendrimer network

Article abstract of DOI:10.1134/S0965544116120112

A Ni–W precursor supported on a dendrimer-containing crosslinked polymer (42 wt % of a third-generation polypropylenimine dendrimer) has been first synthesized. The precursor has been subjected to the ex situ and in situ decomposition in a hydrocarbon feedstock to prepare an unsupported Ni–W sulfide catalyst. The activity of the resulting catalyst in the hydrogenation of aromatic hydrocarbons has been studied using the example of naphthalene. The process has been conducted in an autoclave-type reactor in a temperature range of 350–400°C at a hydrogen pressure of 5.0 MPa. It has been shown that the in situ synthesis of a Ni–W catalyst leads to the formation of particles exhibiting higher activity in the hydrogenation of naphthalene. The in situ synthesized Ni–W particles have been characterized by TEM and XPS.

Full text of DOI:10.1134/S0965544116120112

ISSN 0965-5441, Petroleum Chemistry, 2016, Vol. 56, No. 12, pp. 1107–1113. © Pleiades Publishing, Ltd., 2016.
Original Russian Text © I.A. Sizova, A.B. Kulikov, A.V. Zolotukhina, S.I. Serdyukov, A.L. Maksimov, E.A. Karakhanov, 2016, published in Nanogeterogennyi Kataliz,
2016, Vol. 1, No. 2, pp. 100–106.
Synthesis of Ni–W Aromatic Hydrocarbon Hydrogenation Catalysts
by the Ex Situ and In Situ Decomposition of a Precursor
Based on a Dendrimer Network
I. A. Sizovaa, *, A. B. Kulikova, A. V. Zolotukhinab, S. I. Serdyukova, b,
A. L. Maksimova, b, and E. A. Karakhanovb
aTopchiev Institute of Petrochemical Synthesis, Russian Academy of Sciences, Moscow, Russia
bFaculty of Chemistry, Moscow State University, Moscow, Russia
*e-mail: isizova@mail.ru
Received June 12, 2016
Abstract⎯A Ni–W precursor supported on a dendrimer-containing crosslinked polymer (42 wt % of a third-
generation polypropylenimine dendrimer) has been first synthesized. The precursor has been subjected to the
ex situ and in situ decomposition in a hydrocarbon feedstock to prepare an unsupported Ni–W sulfide cata-
lyst. The activity of the resulting catalyst in the hydrogenation of aromatic hydrocarbons has been studied
using the example of naphthalene. The process has been conducted in an autoclave-type reactor in a tempera-
ture range of 350–400°C at a hydrogen pressure of 5.0 MPa. It has been shown that the in situ synthesis of a
Ni–W catalyst leads to the formation of particles exhibiting higher activity in the hydrogenation of naphtha-
lene. The in situ synthesized Ni–W particles have been characterized by TEM and XPS.
Keywords: nickel–tungsten sulfide catalysts, polypropylenimine dendrimer networks, hydrogenation of aro-
matic hydrocarbons, in situ synthesis of catalysts
DOI: 10.1134/S0965544116120112
Hydrocracking and hydrotreating play an import- respective sulfides can be prepared in situ in the reac-
ant role in the petroleum refining industry as major tion medium [10, 11] or ex situ [10, 12]. It was shown
processes for producing diesel fuels and lubricants [1, that the incorporation of a second metal into the
2], especially in recent years in view of tightening envi- structure of a nanosized sulfide from water-containing
ronmental requirements [2, 3]. In this context, the precursors is typically accompanied by the polymer-
development of effective catalysts for the hydrogena- ization of hydrated ions of transition metals (cobalt,
tion and hydrocracking of heavy hydrocarbons, par- nickel) to form complex oxides and hydroxides [11].
ticularly those containing fused aromatic moieties, This process leads to a decrease in the degree of pro-
under conditions similar to the industrial conditions is motion of the resulting nanosized sulfides, an increase
becoming of primary importance [4]. Sulfide catalysts in the fraction of transition-metal sulfide particles,
based on some metals, such as molybdenum and tung- and a decrease in the total activity of the system. A
sten, have proved to be highly efficient in these pro- method to suppress the hydrolysis process is the use of
cesses [1, 4–6]; the use of a second metal, such as Fe, nitrogen-containing chelating ligands, in particular,
Co, or Ni, provides a significant increase in the cata- ethylenediamine [1, 4, 9, 13]. In this case, an alterna-
lyst efficiency owing to the synergistic effect [1, 7, 8].
tive to ethylenediamine can be nitrogen-containing
polymers, namely, polypropylenimine dendrimers,
whose three-dimensional globular macromolecules
have a branched regular structure and comprise a large
number of donor-chelating groups [14, 15].
Previously, an approach has been proposed to bind
these molecules into “megamers” to prepare catalyst
systems with a high content of metal nanoparticles
with a size of 0.5–3.0 nm dispersed in the polymer [16,
Previously, it has been shown that the activity of
these bimetallic sulfide catalysts substantially depends
on the synthesis method and the nature of feed mate-
rials [4, 6]. For example, it was found that the use of
thiotungstates and thiomolybdates as a metal source
provides the formation of significantly more effective
hydrogenation catalysts than commercial sulfided
CoMo/Al2O3 and NiMo/Al2O3 [7, 9]. In the case of
hydroconversion and hydrodearomatization reactions 17]. This study is focused on the preparation of
conducted in slurry systems using hydrogen-soluble nickel–tungsten sulfide catalysts supported on net-
precursors, catalytically active nanosuspensions of works of crosslinked polypropylenimine dendrimers
1107

1108
SIZOVA et al.
XPS: 284.9 (C 1s, 69.2%); 398.3 (N 1s, 4.6%);
and on the examination of catalyst activity in the
hydrogenation of a model substrate (naphthalene) 531.5 (O 1s, 26.2%) eV.
under various conditions.
Ammonium thiotungstate (NH4)2WS4 was pre-
pared as described in [18].
The synthesis of the nickel–tungsten precursor
supported on a dendrimer network was conducted in
two stages. At the first stage, 340 mg (0.99 mmol)
of (NH4)2WS4 (the amount corresponding to a tung-
sten : dendrimer end-group ratio of 1 : 2) was
added under stirring to a dendrimer network suspen-
sion (500 mg) in 5 mL of THF, which was placed in a
50-mL single-neck round-bottom flask equipped with
a reflux condenser and a magnetic stirrer. The salt res-
idues were washed off with another 10-mL portion of
THF. Reaction was run at the boiling temperature of
the solvent under stirring for 12 h; in about 30 min
after the beginning of the reaction, the mixture
became yellow-orange. Upon completion of the reac-
tion, the suspension was evaporated to dryness on a
rotor at 40°C. The resulting intermediate product was
an ochreous powder and had a weight of 850 mg.
At the second stage, a solution of 144 mg
(0.495 mmol) of Ni(NO3)2 ⋅ 6 H2O in 5 mL of water
was added dropwise to the resulting precursor
(850 mg) suspended in 5 mL of water at room tem-
perature under stirring. In this case, the Ni/W ratio
was 1/2. After that, reaction was run at room tempera-
ture under stirring for 12 h; before the entire Ni(NO3)2
solution was added, the reaction mixture became red-
brown. After the reaction, the resulting red-brown
precipitate was separated from the solution containing
the reaction by-products by centrifugation, washed
with water and ethanol, and air-dried. The weight of
the resulting product was 763 mg (66%).
EXPERIMENTAL
Synthesis Procedures
Reagents used as precursors without further purifi-
cation were as follows: polymer Pluronic 123
(Aldrich), dimethylformamide (DMF; Komponent-
Reaktiv, reagent grade), iodomethane (Chemical
Line, 99.5%), tetrahydrofuran (THF; Komponent-
Reaktiv, analytical grade), 3,3'[prim]-dimethoxy-
4,4'[prim]-biphenyldiisocyanate (Aldrich, 85%), and
Ni(NO3)2 ⋅ 6 H2O (Reakhim, analytical grade).
A dendrimer network containing 42 wt % of the
third-generation polypropylenimine dendrimer with
16 amino end groups (DAB(NH2)16) was synthesized
as described in [16, 17] using 3,3'[prim]-dimethoxy-
4,4'[prim]-biphenyldiisocyanate as a crosslinking
agent in the presence of methylated polymer Pluronic
123 to increase the size of cavities in the network. The
NCO/NH2 ratio was 1 : 1.
One gram (~0.17 mmol) of polymer Pluronic 123
and 5 mL of DMF were placed in a 10-mL round-bot-
tom flask. After that, 360 mg of K2CO3 was added to
the resulting solution under stirring. Reaction was run
at a temperature of 150°C under stirring for 1 h. Next,
100 μL (1.6 mmol) of iodomethane was added; the
reaction was further run at the above temperature for
12 h. After that, DMF was stripped off on a rotor. The
methylated polymer was dissolved in 15 mL of chloro-
form and separated from K2CO3 by decantation. One
gram (0.6 mmol) of DAB(NH2)16 was added to the
solution; the resulting mixture was homogenized at
room temperature for 12 h. Upon the completion of
stirring, chloroform was stripped off on a rotor to form
a brown oil. The weight of the resulting associate was
1.92 g (a yield of 96%). The DAB(NH2)16–Pluronic
123 associate was suspended in 50 mL of THF. Next,
The catalyst was prepared by the decomposition of
the Ni–W precursor supported on the dendrimer net-
work. The catalyst was formed by two methods:
—ex situ: in this case, the catalyst precursor was
further sulfided at a temperature of 350°C and a
hydrogen pressure of 2.0 MPa under stirring for 6 h.
Reaction was run in a benzene medium in the pres-
ence of elemental sulfur used as a sulfiding agent. The
resulting catalyst was separated from the solution by
centrifugation and air dried.
1.4
g
(4.75 mmol) of 3,3'[prim]-dimethoxy-
4,4'[prim]-biphenyldiisocyanate was added to the
resulting suspension under stirring. Reaction was run
at 70°C for 12 h. Upon the completion of the reaction,
the mixture was evaporated on a rotor. The resulting
ochreous-yellow material was washed with water and
ethanol to remove the polymer and air-dried. The
weight of the product was 1.86 g (74%).
—in situ: directly during the catalytic reaction
under the process conditions.
Catalytic Testing Procedure
IR spectroscopy and X-ray photoelectron spec-
troscopy (XPS) data for the resulting sample are as fol-
lows:
IR: 3321 (N–Hst in NH–C(=O)); 2990 (C–Hst in
aromatics); 2940 (C–Hst); 2869 (C–Hst, CH2–Nst);
1685, 1587, 1509 (C=Ost in NH–C(=O)); 1465 (N–
Hδ, CH2δ, X–N–Hδ); 1396 (CH2δ); 1245, 1201, 1171,
1127, 1094, 1027 (C–Nst in NH–C(=O)); 927 (C–Hδ
ArH); 813 (C=Cδ in aromatics); 780 (N–Hδ) cm–1;
Ten milligrams of the precursor/catalyst and 2 mL
of a 10% solution of naphthalene in n-hexadecane
were placed in a steel autoclave equipped with a glass
cartridge test tube. If necessary, an additional sulfid-
ing agent was added. After that, the autoclave was
sealed and filled with hydrogen to a pressure of
5.0 MPa. Reaction was run at a temperature of 350–
400°C under vigorous stirring for 5 h. The hydro-
gen/substrate and naphthalene/tungsten molar ratios
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SYNTHESIS OF Ni–W AROMATIC HYDROCARBON HYDROGENATION CATALYSTS
1109
Conversion, %
Conversion, %
100
30
25
20
15
10
5
without sulfur
S (2.5 wt %)
80
60
40
20
0
350
360
380
400
0
Temperature, °С
without S
2.5% S
DMDS
Sulfiding agent
Fig. 2. Dependence of naphthalene conversion on
the reaction temperature in the presence of the ex situ
synthesized catalyst (reaction conditions: 350°C, 5.0 MPa
Fig. 1. Dependence of naphthalene conversion on the sul-
fiding agent in the presence of the ex situ synthesized cat-
H , 5 h).
2
alyst (reaction conditions: 350°C, 5.0 MPa H , 5 h).
2
RESULTS AND DISCUSSION
were 60/1 and 105/1, respectively. After the reaction,
the autoclave was cooled to room temperature and
depressurized. The reaction products were analyzed by
gas–liquid chromatography.
Naphthalene Hydrogenation in the Presence
of Ni–W–S Nanocatalysts
The Ni–W catalyst synthesized by ex situ decom-
position was tested in the hydrogenation of naphtha-
lene. The effect of both the process temperature and
the nature of the sulfiding agent on the catalyst activity
was studied (Figs. 1, 2). The addition of the sulfiding
agent in an amount of 2.5 wt % of the total weight of
the feedstock in the system led to an abrupt (about
threefold) decrease in naphthalene conversion. How-
ever, even in the absence of the sulfiding agent, naph-
thalene conversion at 350°C was as low as 24%. In all
the three cases, the only reaction product was tetralin.
An increase in temperature led to a significant
increase in naphthalene conversion using both the sul-
fided and nonsulfided feedstocks (Fig. 2); the best
results were obtained at 380°C. In this case, the naph-
thalene conversion was 91–96%. For both feedstock
types, the main reaction product was tetralin with a
selectivity of 65–75%; the fraction of this product
increased in the case of the sulfided feedstock. Other
reaction products were cis- and trans-decalins; their
average ratio was 1 : 3.
Catalyst and Reaction Product Investigation Procedures
The structure and morphology of the in situ syn-
thesized catalyst samples were studied on a JEOL
JEM-2100 analytical electron microscope. XPS stud-
ies of the resulting samples were conducted using a
Physical Electronics PHI-5500 ESCA XPS instru-
ment as described in [19].
Analysis of the naphthalene hydrogenation prod-
ucts was conducted on a Kristallyuks 4000 M chro-
matograph equipped with a flame-ionization detector
and a SPB-1 capillary column coated with the
polydimethylsiloxane stationary liquid phase (dimen-
sions, 30 m × 0.25 mm; carrier gas, helium; split ratio,
1 : 90). Chromatograms were processed using the
NetChromWin software program according to
changes in the relative areas (in %) of the peaks of the
substrate and reaction products.
Naphthalene conversion (conv, %) was calculated
as the degree of conversion of the feed aromatic com-
pound to tetralin and decalins using the following for-
mula:
It should also be noted that, in the presence of sul-
fur, naphthalene conversion significantly increases
even at 360°С (81% against 31% in the nonsulfided
feedstock). Apparently, this fact may be attributed to
the additional sulfiding of the sulfide catalyst surface
and, as a consequence, to the formation of a larger
number of active sites on this surface. In the absence of
additional amounts of sulfur, the formation of WS2
particles is hindered; it begins at higher temperatures
mproduct
mproduct + munreacted
(1)
conv =
× 100%,
where mproduct is the total mass of reaction products
(rel. %) and munreacted is the mass of the unreacted
naphthalene (rel. %).
Reaction product selectivity (Si, %) was calculated
as the ratio of the mass of the ith product to the total (380°C) [17]. In contrast, at 350°C or lower tempera-
mass of the products formed.
tures, sulfur apparently acts as a catalyst poison; this
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1110
SIZOVA et al.
(а)
(b)
Tetralin
Decalins
Conversion, %
100
Selectivity, %
100
80
60
40
20
0
80
60
40
20
0
350
360
380
400
350
360
380
400
Temperature, °С
Temperature, °С
Fig. 3. Dependences of (a) naphthalene conversion and (b) reaction product selectivity on the reaction temperature in the pres-
ence of the in situ synthesized Ni–W catalyst (reaction conditions: 5.0 MPa H , 5 h).
2
feature is responsible for low naphthalene conversions neous hydrogenation catalysts [23]. This feature may
in the presence of sulfur under these conditions.
be primarily explained by the thermodynamic charac-
teristics of naphthalene hydrogenation, namely, a
higher amount of heat released during the hydrogena-
tion of tetralin compared with that of naphthalene
[23]. In the case under study, the further hydrogena-
tion of tetralin is suppressed apparently by the pres-
ence of nitrogen-containing ligands in the system.
A further increase in temperature to 400°C led to a
decrease in naphthalene conversion in both the sul-
fided and nonsulfided feedstocks; this finding is
apparently associated with thermodynamic con-
straints in the hydrogenation of aromatic hydrocar-
bons, which is an equilibrium process [18].
Using the example of the ex situ synthesized cata-
lyst, it was shown that the catalyst activity increases in
the presence of sulfiding agents with the increasing
temperature (Fig. 2). A similar tendency was exhibited
by the in situ synthesized Ni–W catalyst at 350°C
(Fig. 5). As in the previous case, additional sulfiding
was implemented by the introduction of 2.5 wt % of
elemental sulfur in a 10% solution of naphthalene in
hexadecane. The sulfiding agents were dimethyl disul-
fide (DMDS), dimethyl sulfoxide (DMSO), and ele-
mental sulfur.
It was found that the addition of 2.5 wt % of ele-
mental sulfur to the feedstock leads to a significant
increase in the activity of the in situ synthesized cata-
lyst. In this case, the naphthalene conversion
increased from 68 to 97%, while the total selectivity for
decalins increased from 2 to 37%. The use of DMDS
did not lead to considerable changes in conversion
compared with the reaction without sulfur. In con-
trast, in the case of addition of DMSO, the reaction
hardly occurred at all: the naphthalene conversion did
not exceed 3%.
Simultaneously, the possibility of synthesizing the
Ni–W catalyst by the decomposition of the precursor
supported on the dendrimer network directly during
naphthalene hydrogenation in a slurry mode, i.e.,
in situ, was explored. Figure 3 shows the dependence
of naphthalene conversion on process temperature. As
in the case of the ex situ synthesized catalyst, the opti-
mum process temperature was 380°C: the naphtha-
lene conversion achieved 98%. There was a direct cor-
relation between the total fraction of decalins and the
catalyst activity (Fig. 3b). Thus, it was as low as 2% at
350°C and as high as 55% at 380°C. In this case, as
before, the ratio of cis- and trans-decalins was 1 : 3;
this value is apparently typical for catalysts based on
tungsten and nickel.
Further comparison of the behavior of the two cat-
alysts in the hydrogenation of naphthalene was con-
ducted at 380°C. Note that, at comparable naphtha-
lene conversions (91 and 98% for the ex situ and in situ
synthesized catalysts, respectively), the in situ synthe-
sized catalysts exhibit higher selectivity for decalins
(55% against 44%). Thus, it may be assumed that the
in situ synthesis of the Ni–W catalyst provides the for-
mation of more active species that contribute to fur-
ther hydrogenation of tetralin to decalin. These data
are in agreement with the previous results obtained for
the Ni–W catalyst in the hydrogenation of diben-
zothiophene [22].
The results may be interpreted using the TEM and
XPS data (Fig. 6). The survey images of both catalysts
show characteristic layered structures composed of
WS2 nanosheets united into agglomerates (500–
1000 nm). It is clearly seen that the use of elemental
sulfur as a sulfiding agent leads to the formation of
At the same time, it should be noted that the dom- long yet narrow “bands” composed, on average, of
inant formation of tetralin is not typical for heteroge- two or three layers. In addition, the formation of
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SYNTHESIS OF Ni–W AROMATIC HYDROCARBON HYDROGENATION CATALYSTS
1111
Selectivity, %
Conversion, %
100
100
80
60
40
20
0
tetralin
decalins
80
60
40
20
0
without S (2.5 wt %) DMDS
sulfur
DMSO
Sulfiding agent
ex situ
in situ
Fig. 5. Dependence of naphthalene conversion on the sul-
fiding agent in the presence of the in situ synthesized cata-
Fig. 4. Dependence of reaction product selectivity on the
lyst (reaction conditions: 350°C, 5.0 MPa H , 5 h).
2
synthesis method used for the Ni–W catalyst (reaction
conditions: 350°C, 5.0 MPa H , 5 h).
2
100 nm
100 nm
(а)
(b)
5 nm
5 nm
(c)
(d)
Fig. 6. Micrographs of the Ni–W–S catalysts synthesized in situ using (a, c) elemental sulfur and (b, d) DMSO as a sulfiding
agent.
agglomerates with a considerably larger number of lay- is this feature that is responsible for a decrease in the
catalyst activity in the hydrogenation of naphthalene.
ers (seven to ten) is observed (Fig. 6c).
The XPS data on the elemental composition of the
catalyst surface are shown in Table 1. The sample sur-
face contains W, Ni, C, S, and O elements. A high car-
bon content in the active phase on the catalyst surface
is consistent with the literature data [24] and may be
associated with the use of dendrimer networks as a
support. The absence of nitrogen in the composition
of the two catalysts may be attributed not only to the
A different situation is observed for the catalyst
synthesized using DMSO as a sulfiding agent. In this
case, large ordered crystallites composed of up to
400–500 layers are formed (Fig. 6d). The result is that
the number of sites active in hydrogenation, which are
located at the corners and edges of tungsten disulphide
crystallites [6], is significantly lower for the catalyst
synthesized in situ using DMSO as a sulfiding agent; it decomposition of the dendrimer networks and the
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1112
SIZOVA et al.
Table 1. Elemental composition of the surface of the cata-
sulfur in the oxidation state +6 (a binding energy of
169 eV [26]) is absent on the surface of the two cata-
lysts.
lysts synthesized in situ using different sulfiding agents
Atomic concentration, %
Sulfiding agent
Thus, it may be stated that the use of DMSO as a
sulfiding agent leads to formation of the catalyst with
an insufficient degree of sulfiding of the surface,
which, in turn, may be attributed to the replacement of
sulfur atoms present on the catalyst surface by oxygen
atoms contained in DMSO molecules. The derived
data correlate with the assumption made in [27] that,
for the in situ synthesis of the catalyst in the presence
of DMSO, it is necessary to introduce an additional
sulfiding agent.
С
W
Ni
S
O
S (2.5 wt %)
DMSO
69.6
67.6
2.8
6.3
0.3
0.3
6.8
10.6
20.5
15.2
removal of a portion of amine moieties but also to the
fact that the rest of the moieties is mostly located
inside the support.
Note that the W/S atomic ratio is higher for the cat-
alyst synthesized in the presence of DMSO as a sulfid-
ing agent; this finding suggests that, in this case, sulfur
atoms are removed from the sample surface. In con-
trast, a lower Ni/W ratio for the same catalyst may be
explained by the fact that nickel atoms are mostly
located between tungsten disulfide layers rather than
on catalyst surface.
The valence states of tungsten and sulfur on the
sample surface are listed in Table 2. The determined
binding energy values are consistent with the literature
data [22, 23].
In this study, the Ni–W precursor supported on the
dendrimer network has been first synthesized. This
precursor has been subjected to decomposition by two
methods, namely, ex situ and in situ, to prepare the
Ni–W catalyst; it has been shown that the catalyst syn-
thesis in situ in the hydrocarbon feedstock leads to the
formation of Ni–W particles exhibiting a higher activ-
ity in the hydrogenation of naphthalene. To increase
the naphthalene conversion in the presence of this cat-
alyst, the hydrocarbon feedstock should be subjected
to additional sulfiding. It has been found that the
activity of the Ni–W catalysts synthesized by the
decomposition of respective precursors supported on
dendrimer networks significantly depends on both the
process temperature and the nature of the sulfiding
agent. Thus, the optimum reaction conditions are a
temperature of 380°C and the use of sulfur as a sulfid-
ing agent, whereas the reaction in DMSO, conversely,
requires additional sulfiding.
It is evident that the surface of the catalyst synthe-
sized in situ in the presence of elemental sulfur con-
tains tungsten mostly in two forms: sulfide and oxide.
Their ratio is 87/13; it is also responsible for the high
activity of the catalyst. Conversely, in the case of the
catalyst synthesized in the presence of DMSO, oxy-
gen-containing forms of tungsten (WOxSy, WO3) are
dominant; their total fraction is more than 75%. A
comparatively low degree of sulfiding of the surface of
the catalyst synthesized in the presence of DMSO is
also confirmed by data on the valence states of sulfur,
among which the fraction of oxysulfide significantly
ACKNOWLEDGMENTS
This work was supported by the Russian Science
increases. On the other hand, it should be noted that Foundation (agreement no. 15-13-00123).
Table 2. XPS data for the W 4f and S 2p levels of the Ni–W catalysts synthesized in situ using DMSO and elemental sulfur
as sulfiding agents
Sulfiding agent
Element
S (2.5 wt %)
DMSO
State
binding energy, eV concentration, at % binding energy, eV concentration, at %
WS2
32.5
–
87.0
–
32.4
33.1
24.1
27.0
48.9
53.9
46.1
W 4 f7/2
WOxSy
WO3
36.4
162.2
163.4
13.0
61.6
38.4
36.1
S2–
162.2
163.4
S 2p3/2
(O2S)6–
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SYNTHESIS OF Ni–W AROMATIC HYDROCARBON HYDROGENATION CATALYSTS
1113
A.L.,
16. Karakhanov,
E.A.,
Maksimov,
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PETROLEUM CHEMISTRY Vol. 56 No. 12 2016