Catal. Sustain. Energy 2015; 2: 4356

Original paper

Open Access

M.P. Yunusov , Sh.M. Saidaxmedov, Sh.B. Djallova, Kh.A. Nasullaev, Sh.T. Gulyamov, N.F.Isaeva,
E.I.Mirzaeva

Synthesis and Study of Ni-Mo-Co Catalysts for

Hydroprocessing of Oil Fractions
Abstract: The problems of synthesis of Ni-Mo, Ni-Mo
Co and Co-Mo oxide catalysts for hydrodesulfurization
and hydrogenation of aromatic hydrocarbons in the
composition of kerosene, diesel and oil fractions are
discussed. The influence of spent adsorbent and kaolin
as the additives on the physical-chemical and catalytic
properties of bimetallic and trimetallic catalysts is
established.
Keywords: hydrogenation, desulfurization, polyaromatic
compounds, Ni-Mo, Ni-Mo Co, Co-Mo oxide catalysts,
phase composition, electronic spectra
DOI 10.1515/cse-2015-0003
Received December 18, 2014; accepted April 2, 2015

Currently, petroleum hydrocarbons and natural gas are

the major source of energy. The processing of hydrocarbon
raw materials into various types of commodity fuel and
oils envisages generally, ecological, economic and quality
questions aspects. Insufficient cleaning of fuel from sulfur
and aromatic hydrocarbons is a cause of environmental
pollution. The existence of mercaptan sulfur in the
composition of natural gas causes intense corrosion of
pipelines and equipment and causing enormous economic
damage .
To solve this problem, conditions of an increase in
production of oil, with the high content of sulfurous
compounds and resin-asphaltene substances in
thecatalytic processes, with hydrotreating are used.

*Corresponding author: M.P. Yunusov: Uzbek Research ChemicalPharmaceutical Institute named A Sultanov, 100125, Republic of
Uzbekistan, Tashkent, st. Durmon Yuli 40,
E-mail: myunusov_uz@rambler.ru
Sh.M. Saidaxmedov, Sh.B. Djallova, Kh.A. Nasullaev, Sh.T.
Gulyamov, N.F.Isaeva, E.I.Mirzaeva: Uzbek Research ChemicalPharmaceutical Institute named A Sultanov, 100125, Republic of
Uzbekistan, Tashkent, st. Durmon Yuli 40

Mainly the supported MoO3/ -Al2O3 catalysts promoted

with cobalt or nickel ions are used [1-3]. Most researchers
attribut high activity of Co-Mo and Ni-Mo catalysts to
formation of CoMoS type phase during the sulfiding of
the oxidic form. It is believed that a single co-impregnation
with the solutions, by using the complexing agents and
introduction of a nickel or cobalt into molybdenum
heteropoly composition, is occurring [4]. It is noteworthy
the unusual combination of nickel and cobalt in the
composition of Co-Mo / -Al2O3 hydrotreating catalysts.
Nickel as the (co) promoter promotes a retention of
cobalt cations in phase CoMoS. Herewith, a synergistic
increase in the activity of the catalysts in hydrogenation
and hydrodesulfurization reactions is observed [5].
Properties of active phase depend on set of factors and are
defined by the way of obtaining of oxide precursors, the
carrier nature, structure and ratio of active components,
and also their distribution on a granule.
This paper studies the influence of spent adsorbent
and local kaolin used as additives on the process of
synthesis, physical-chemical and catalytic properties of
Co-Mo, Ni-Mo and Co-Ni-Mo catalysts for hydroprocessing
of petroleum fractions. To identify commonality of
phenomena, we synthesized a series of catalysts and
model systems of different composition. Particular
attention has been paid to the effect of impurities on the
texture, the coordination state of transition metal ions on
the distribution of active components on the granules and
catalytic activity.
Research is directed on the quality improvement of
fuel and oils at the expense of decrease in the content of
sulfuric and polyaromatic compounds in hydrocarbon
raw materials at moderate temperature and pressure of
hydrogen. The received results will allow expanding a rawmaterial base for manufacture of catalysts and rationally
to use a waste of the gas-processing industry.

2015 M.P. Yunusov et al., licensee De Gruyter Open.

This work is licensed under the Creative Commons Attribution-NonCommercial-NoDerivs 3.0 License.

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M.P. Yunusov et al.

Experimental

f(R)=

For the catalysts synthesis, the kaolin (K) from

Angren Kaolin Ltd., industrial alumina hydroxide
(GOA) Hemel Ltd, Dnepropetrovsk; spent adsorbent
(AO) Shurtan Gas Chemical Complex; N3 JSC
Electrochimprom, Chirchik
and carriers on their
basis have been used. For impregnation, water solutions
(NH4)4Mo7O24 4H2O Uzbek Refractory and heat-resistant
metals, Chirchik; 34 JSC Ammophos, Almalyk
and two salts (NO3)26H2O and Ni(NO3)26H2O JSC,
Uralsky plant chemicals have been prepared.
Diffraction patterns of samples are obtained on
diffractometer Dron-3 using
the filtered radiation
CuK, tube voltage - 30 kV, current strength - 20 mA . The
size of crystallites were calculated from the broadening
of the corresponding diffraction peaks. Assignment of
the lines in the diffraction patterns was carried out using
JCPDS card file. Electronic spectra were registered in
area using spectrometer Hitachi-330. Analyzer JHA
8800R Super probe (Jeol, Japan) with diameter of a
microprobe 2.5 microns was used for study of distribution
of elements on carriers grain. Porous characteristics
and the specific surface area of catalysts and carriers
were determined using a porosimeter Carlo Erba
based on mercury penetration at a pressure from 0 to
200 MPa. The content of active elements Co, Ni, Mo in
catalysts was determined by absorption spectroscopy
using SP 9 atomic adsorption spectrophotometer PYE
UNICAM. To determine the strength and concentration
of the acid-base sites, the following set of indicators
with specific absorption bands in the visible region of
the electronic spectra were used (the values of pKa are
in brackets): anthraquinone (- 8.2), benzalatsetofenon
(-5.6), ditsintalatseton (-3.3), benzolazodifenilamin (+1.5),
bromfenolblau (+3.8), bromkrezolpurpur (+6.1), neytralrot
(+6.8),
phenolphthalein
(+9.3),
Thymolphthalein
(+10.3). The spectrophotometer Hitachi -330 is used
for registration the spectra of adsorbed indicators. Two
spectra were analyzedto determine the concentration of
surface sites with a given pKa. The first belongs to sample
after thermal vacuum treatment or after calcination in
air, the second, to adsorbed indicator on the surface,
pre-poisoned with the determined amount of butylamine
(for determining acid site), or benzoic acid (to define of
basic centers). The values of Kubelka-Munk function f
(R) were determined from the maxima of the bands of
indicator in the electronic spectra before and after the
poisoning of the surface according to [6]:

acid =

(1 - R)2
2 R
f(R) poison

f(R) - f(R)poison
Here R - coefficient of diffuse reflectance, Cacid - the
concentration of acid sites, Cpoison is the concentration of
poisoned with n-butylamine sites, f (R) and f (R) poison Kubelka-Munk functions at the maximum for the band of
acid form of the corresponding indicator before and after
the poisoning of surface acid sites.
To evaluate the catalytic properties of samples,
the hydrocarbon feedstock of Fergana refinery is
used: kerosene fraction (boiling point 398-513 K), the
diesel fraction (boiling temperature - 433-633 K) and a
deasphalted oil fraction (the boiling point - > 773 K). The
amount of sulfur in the hydrocarbon feedstock before and
after hydrogenation was determined by combustion of
samples,with the capture of produced SO2, its oxidation to
SO3 followed by titration. Quantitative determination of
the polyaromatic compounds (PAC) in the feed oil and the
hydrogenation was carried out by adsorption separation
on silica gel, followed by weighing the separated fraction
with a refractive index nD 20 more than 1.55. Activity in
hydrodesulfurization and hydrogenation of polyaromatic
substances in thecomposition of asphalt-free residue and
kerosene fraction is studied on continuous-flow setting
at pressure 4 P and temperature 573 -593 K, of diesel
fraction at pressure 5 P and temperature 633 K. Activity
of the prepared catalysts is estimated on relative decrease
in the content of sulfur and concentration of polycyclic
aromatic hydrocarbons in hydrogenation, obtained after
process on continuous- flow setting, in comparison with
raw materials.
Calculated
componential
composition
of
hydrodesulfurization catalysts: I 1% Ni, 3% CoO, 12%
MoO3; II 4% Ni, 12% MoO3; III 4% , 12% MoO3. Next
catalysts were used for hydrogenation of polyaromatic
compounds: IV 1.7% Ni, 4.2% CoO, 17.8% MoO3; V
6% Ni, 18% MoO3 and VI 6% , 18% MoO3.
Catalysts were prepared by two methods using
solutions of active ingredients stabilized with H3PO4.
Method 1. Dry mixes of composition: GOA+K (12%),
+ (25%) and G+ (35%) + K (12%) are peptized with
the diluted solution N3, then the necessary quantity of
one of the solutions of active components is added. Catalytic
mass is carefully mixed, molded in the form of extruded
cylinders of about 4 mm in diameter and 5-6 mm in length
and trilobes of the same dimensions. The obtained granules
were dried and calcined at 673 and 823 K.

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Synthesis and Study of Ni-Mo-Co Catalysts for Hydroprocessing of Oil Fractions

Method 2. At first, an extrusion molded aluminakaolin carriers (similar to catalysts of the method 1) from
the peptized with nitric acid mixes of the composition:
carrier AK-1 GOA+K (12%) carrier AK-1, GOA+ (35%) +
(12%) carrier AK-2 and + (25%) carrier AK-3. The
formed carriers are calcined at 823 K, after cooling they
are impregnated with one of joint solutions. To obtain the
catalysts of hydrogenation of the composition IV VI, the
procedure of impregnation is repeated after intermediate
calcinations at 473 K. Final calcinations temperature of
all catalysts was either 673 or 823 K. In tables 1 and 2 the
physical-chemical characteristics of carriers and catalysts
are given. According to results of chemical analysis, the
fluctuations from sample to sample is 7-12%.

Results and their discussion

Industrial GOA (fraction less than 0,063 mm) represented
a mix of pseudo-boehmite with crystallite size of 3-6
nanometers and gibbsite with crystallite sizes of 20-250
nanometers. The surface of non-calcined sample has a
weak acidic properties and the calcined alumina has a
set of strong and moderate aprotic acid centers (able1).
Spent adsorbent (fraction of 0.15 0.10 mm)
had the following phase composition: -Al2O3, -Al2O3
and boehmite with the sizes of crystallits from 10 to 100
nanometers. The content
of impurity was ranged : Na2O (1.17-1.71%), Cl (0.81.4%), CaO (0.01-0.09%), and also TiO2 (0.3-0.5%) and
V2O5 (0.2-0.4%). Spent adsorbent of AO differed with
broad-porous structure and low specific surface [7].
After calcination at 823 K and burning-out of organic
components specific surface increased to 170 m2/g and the
volume of wide pores reached 0.5 m3/g. On a surface of
the initial sample, the basic sites = + 9.3 - +10.3, along
with the weak acid sites with = +3.8 - +6.1, prevailed.
After calcination, the set of moderate aproton and the
proton acid sites, and also the basic sites with = +10
are identified. Initial kaolin (fraction less than 0.063 mm)
had differently porous structure and a low specific surface.
Mineral composition of kaolin: Al2O3 (23.5-24.5%), SiO2
(48.3-48.9%), P2O5 (0.59-0.69%), SO3 (0.32-0.44%), K2O
(0.97-1.09%), CaO (0.35-0.67%), FeO (0.17-2.73) and BaO
(0.15-0.43%). The sample of initial kaolin has weak acid
properties (able 1). For kaolin composition the kaolinite
mineral (lines of average intensity from interplanar spacing
with d = 0.714-0.718; 0.446; 0.357 and 0.22-0.26 nm) and
quartz crystals (intensive lines from interplanar spacing
with d = 0.426; 0.334; 0.245-0.246; 0.181- 0.182; 0.154- 0.155
and 0.137-0.138 nm) are identified [8].

45

Calcination of dry mixes GOA+, GOA++, as well

as at synthesis of carriers AK-1, -2 and -3, leads to
transformation of alumina hydroxide into oxide form. In
XRD, wide lines of -Al2O3 (0.198 and 0.139 nm) and narrow
lines of quartz (d = 0.427; 0.334- 0.335 nm) were detected.
Kaolin almost completely destroyed the alumina-kaolinborate carrier [9].
Not-sufficient water absorption of carriers AK-2 and
-3 required the use of concentrated solutions for the
design of hydrotreating catalysts of calculated structure.
Steady combined solutions have been obtained at value
= 1.3-1.5. Under these conditions, the contact of
polymer molybdenum ions with the Co2+ or Ni2+ ions is
able to form a heteropoly anions sixth row(structure of
the Anderson) [4]. As a result in combined solutions the
hydrated molybdate of type 4 and heteropolyanions
[NiH6Mo6O24] 4 , [CoH6Mo6O24] 4 co-existed, together with
cations 2 +, Ni2 +, NH 4 + and anions N3 and 43 .
XRD studies have revealed a number of amorphous
and crystal phases in compositions of steamed and dried
at 473 K combined solutions. Position of diffraction lines,
their relative intensity and the identified compounds
are given in Table 3. Unlike bimetallic systems, the
dehydratedNi-- system did not contain crystal
phases. When the samples are calcined at the temperature
of catalysts preparation, the phase composition is changed
and essentially differed from the composition of products
of thermal treatment of the combined solutions obtained
in [10]. In XRD, the intensity of lines has decreased by
20-30% from crystal phases of hydrated molybdates
NiMoO4. x H2O, x. NiMoO4. y H2O and MoO4. x H2O.
Instead, intensity of the lines belong to heteropolyacids
increased and the lines belong to cobalt nitrate crystallites
with different content of crystallization water are appeared.
Removal of the crystallization water of from hydrated
nickel and cobalt molybdate, as well as decomposition
of (NH4)4[NiH6Mo6O24].5H2O advantageously proceeded
in a temperature range 623-673 K. Crystal phases of Ni
and were not found. Disappearance of lines from
(NH4)4[CoH6Mo6O24].5H2O and occurrence of base lines
from phase 3 after calcination of cobalt containing
systems at 623 K coincided with literary data on thermal
instability heteropolymolybdate of cobalt [11].
XDR analysis indicates the presence of anhydrous
cobalt molybdate after the calcination of sample at 823 K.
In the nickel-cobalt-molybdate system lines from CoMoO4
are absent and the lines of NiMoO4 were more intense than
for nickel-molybdenum system. We explain this fact with
the insertion of 2+ ions into a crystal lattice of hydrated
nickel molybdates at the hydrothermal stage of synthesis
above 473 K [10].

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M.P. Yunusov et al.

Preparation of catalysts by mixing

method (Method 1).
The texture of the catalysts obtained by the Method 1,
strongly enough differed from a texture of initial
components (able 1, 2). Low-percentage catalysts I-1, II-1
and III-1 and V-1 on GOA+ contained a combination of
rather small pores and had good mechanical durability.
With concentration increase (samples of a series of 1
structure IV-VI), the smallest pores disappeared. Diameter
of larger pores was simultaneously narrowed and the
specific surface decreased. The chosen combination of
large particles AO with small particles of GOA and K has
provided prevalence of wide pores on samples GOA +
(40%) + K(10%) and + (30%). Formation of smaller
pores, in comparison with the calcined initial components
has been noted. All catalysts on the basis of + (30%)
have differing small pore volumes, and samples with the
smaller content of kaolin do not satisfy strength criterion.
Agitation of combined solution of active metals and
powders of carriers provided close contact and deep
interaction of reagents. As a result of the acid consumption
for superficial hydrolysis of particles hydroxides and
alumina oxides, incoming into catalyst mass, increased
up to 3.5-3.9. As consequence, hydrated molybdates of
nickel (cobalt) and ammonium salts of heteropoly acids
dropped out in a ground with the formation of amorphous
products. In XRD of all calcined catalysts of the first
series against lines - alumina oxide and quartz, very
wide halo is marked in area d = 0.64-0.23 nm. This area

is characteristic for a number of molybdenum structures,

including hydrated molybdates of nickel and cobalt.
Occurrence of the halo is specified in formation of range
of compounds of transitive metals and their high enough
dispersion. But the absence of accurate lines in XRD has
not allowed receiving the information on phase structure
of active components.
Electronic spectra of systems with ions of nickel,
cobalt and molybdenum are well studied and widely
applied to research of catalysts. Reference of peaks of
absorption is made on literary data on research of various
catalysts and model systems [12-19]. In spectra of calcined
kaolin and carriers on its basis absorption peaks are
found out at 18200 and 19600 cm1 (Fig. 1, curves 1, 2).
They corresponded to the formation of structures Fe3+O-Fe2+ from impurity-ions Fe2+, described in E.A. Aripov
s monography [19]. The initial AO was characterized by
unstructured high level of continuous absorption (Fig. 1,
curve 3). We have explained it by presence of impurity
V3+ and products of consolidation of an organic origin
(deactivated catalysts of polymerization and the rest of
polymers) [7]. In spectra of the calcined AO and carriers
on its basis (Fig. 1, curve 4), it shows a V25- (weak peaks
45500; 36400; 35700; 20000 and 10000 cm1) impurity. For
reduction of distortion of electronic spectra of compounds
of nickel, cobalt and molybdenum because of imposing of
peaks of absorption of carriers survey is carried out in a
mode Auto zero.
Spectral researches testified to a variety of structures
of active components in model systems (Fig. 1, curves 5-10)

Table 1: Physical-chemical characteristics of the initial components and synthesized carriers

Sample

Durability;
kg/mm2

Sspec.;
m2/g

Radius of pores; nm.

( volume of pores; cm3/g)

Concentration of the superficial centers

with various values of ; (mg-eqv/g)
Thermoevacuated t 723 K

Non thermoevacuated

205

3.7-9(0.39);
50-170(0.008)

- 5.6(0.07); -3.3(0.24);
+1.5(0.48)

+3.8(0.23); +6.8(0.28)

2.5

54.6

8-10(0.27); 30-200(0.08);
>500(0.003)

-3.3(0.001); +1.5(0.05);
+3.8(0.31); +6.1(0.11);
+9.3(0.012)

+3.8(0.08); +6.1(0.09);
+9.3(0.22); +10.3(0.07)

52.5

<3.7(0.09); 10-20(0.05);
100-1000(0.012)

-3.3(0.002); -1(0.02);
1.5(0.05); +3.8(0.12);
+9.3(0.02)

+1.5(0.02); +3.8(0.11)

-1

4.3

265

4-5(0.41); 5-15 (0.08);

>100 (0.03)

-8.2(0.008); -5.6(0.08);
-3.3(0.23);+1.5(0.34);
+9.3(0.01)

+3.8(0.42); +6.1(0.15)

-2

2.4

111.3

7-10(0.37); 50-100(0.30);
>100(0.1)

-1(0.01; 1.5(0.20);
+3.8(0.33); +9.3(0.005)

+1.5(0.01); +3.8(0.11);
+6.1(0.37); +9.3(0.014)

-3

2.8

91.4

4-8(0.17); 60-90(0.25);
>100(0.007)

+1.5(0.13); +3.8(0.23);
+6.1(0.25); +9.3(0.01)

+3.8(0.15); +6.1(0.17);
+9.3(0.08)

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Synthesis and Study of Ni-Mo-Co Catalysts for Hydroprocessing of Oil Fractions

47

Table 2: Physical- chemical and catalytic characteristics of the synthesized catalysts (calcined at 673 K)
Estimated content;
%

Ni

0.88
1.68
5.93

3.02
4.22
0

12.2
17.9
17.8

4.03
1.65

0
4.08

3.97
1.73

Impregnation Radius of pores; nm.

object
( volume of pores; g/cm3)
( method)

S;
2/

The content in hydrogenation of various fractions;%

Kerosene
(4 MP, 593 K)

Diesel
(5MP; 633 K)

Asphalt-free
(4 MPa; 573 K)

Sulfur

PC

Sulfur

PC

Sulfur

4-8(0.32); 45-160(0.012)
5-7(0.36); 40-160(0.01)
5-7(0.34); 40-160(0.01);

117.0
107.8
101.4

15.8
13.4
12.9

0.095
0.083
0.090

13.9
13.4
13.5

0.0964
0.0960 31.9
0.0990 31.2

0.450
0.440
0.525

12.1 G++
17.3 (1)

<3.7(0.15); 7-12(0.28); 30 -180(0.03)

<3.7(0.15);7-12(0.23); 30 -170(0.02)

132,3
135,2

14.3
13.1

0.081
0.078

13.4
12.5

0.0083
0.0075 29.3

0.446
0.448

0
4.18

12.4 +;
17.2 (1)

3.7-5(0.12); 7-12(0.20); 60 -300(0.04) 59,4

< 4(0.14); 6-11(0.23); 60 -300(0.02) 63.3

14.7
13.6

0.133
0.124

14.3
14.1

0.1730
0.1350 30.5

0.760
0.720

1.05
1.73
0

3.06
4.20
3.98

12.3 -1
17.9 (2)
12.1

3.7-5(0.43); 5-15(0.065);>100(0.02)
3.7-5(0.45); 5-15(0.060); >90(0.02)
3.7-5(0.42); 5-15(0.063);>100(0.01)

287.3
295.5
290.0

14.0
9.9
14.9

0.063
0.054
0.073

13.3
12.7
13.7

0.0021
0.0019 31.0
0.0026

0.372
0.365
0.485

1.04
1.70
6.03

3.12
4.19
0

12.5
17.6
18.1

-2
( 2)

7-10(0.13); 45-170(0.31)
<3.7(0.12); 5-7(0.10); 45-160 (0.32)
<3.7(0.10); 5-7(0.09); 45-160 (0.36)

99,4
109.5
105.8

14.2
9.5
7.8

0.066
0.057
0.054

13.8
11.7
11.3

0.0023
0.0015 28.8
0.0011 25.2

0.374
0.368
0.360

4.32

12.7

Industrial

3.-5(0.40); 5-20(0.05); >100(0.04)

235,2

14.5

0.092

13.8

0.0036 32.2

0.480

16.85

0.25

14.5

0.97

1.32

G+
(1)

The content of sulfur and polyaromatic compounds (PC) in initial raw materials;%

32.4

Fig. 1. Electronic spectra of diffuse reflection of carriers components (1-4) and steamed combined solutions (5-10) for impregnation of Ni-
(5-7), - (8) and -Ni- (9-10) catalysts. 1 kaolin calcined at 823 K; 2 carrier AK-3; initial spent adsorbent ; 4 spent adsorbent
calcined at 823 K; 1.5 (5-6, 8-10), 6 (7); thermal treatment at 473 K (5, 7-9) and 673 K (6, 10).

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M.P. Yunusov et al.

and catalysts prepared by the method 1 (Fig. 2). According

to Table 3 data, the basic part of nickel and cobalt in
investigated combined solutions was in the compound of
hydrated molybdates. Ammonium salts of heteropoly acid
were formed much less, and cobalt and nickel nitrates
were present in trace quantities. At mixture of components
of catalysts, competitive interaction of compounds of
combined solutions with superficial hydroxyl groups
of alumina as a part of carriers was observed. About the
depth of interaction of the carrier with cobalt ions we
judged by occurrence and intensity of a triplet of peakss
18000; 16600 and 15000 cm1 from ions Td2 +. Occurrence
of diffuse reflection in electronic spectra 16800 and
15800 cm1 from ions NiTd2 + after calcinations at 823 K
unequivocally specified reflexions of a characteristic
doublet in formation nickel - alumina spinls (Fig. 2, a
curve 3). The intensity of peakss from spinl structures
NiTd2 + and Td2 + was maximum in a catalyst spectrum to
GOA, without addition of kaolin (Fig. 2, curves 3-4, 7-8).
We explain this by the high reactionary ability of pseudoboehmite as a part of mix GOA+, in comparison with
spent adsorbents (Fig. 2, curves 5, 9).
Macro crystalline boehmite and alumina oxides as a
part of AO, reacted with cations Ni 2+ and other components

of impregnating solution more slowly. Besides, access

of active components to a surface of particles AO at
impregnation and drying stages has been complicated
by a film of consolidation products. Organic impurities
completely burnt out at 823 K. Therefore, cations Ni 2+ and
2+ in the course of heat treatment did not havetime to
enter tetrahedral emptiness -Al2O3 and formed superficial
oxide film. About formation of Ni1+, 1+ or their mixes,
we judged by obvious increase in level of continuous
absorption in electronic spectra of catalysts on + (Fig.
2, curves 2, 5).
In spectra of bimetallic and trimetallic catalysts
on mix + (calcined at 823 K) distinct peakss of
corresponding molybdates have been observed (Fig. 2,
curves 5, 9) [12]. The wide peak of charge transfer in
oxygen containing complexes of 6+ into electronic
spectra with edge nearby 35000 cm1 indicated on the
presence of polymerized molybdate-ions. At the transition
to a high-percentage catalysts, the peak edge moved to
32000 cm1, due to increase in degree of polymerization.
The wide peak of absorption is related to ions h2+ in
the compound of cobalt molybdate at 19600 cm1with
shoulder nearby 21300 cm1. Cobalt-molybdenum and
nickel-molybdenum associates have been identified on

Fig. 2. Electronic spectra of diffuse reflection of catalysts hydrodesulfurization (1-2, 5-7, 9-10) and hydrogenation of the polyaromatic hydrocarbons (3-4, 8) prepared by the method 1 to GOA (4), mixtures GOA+ (1-3, 6-8) and + (5,9-10). Ni- (1-5) and -Ni- (6-10) catalysts.
Thermal treatment at 473 K (1,6), 673 K (2,7) and 823 K (3-5, 8-10). -Ni-/+ after water and water-ammonia extraction.

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49

Table 3: The detected phases and observed lines in diffractograms of the samples obtained by evaporation and impregnation of solutions.
Sample

Phase composition

Inter-planar spacing (d-spacing); nm (intensity of a spectral line;%)

Ni
(473 K)

NiMoO4xH2O
xNiOMoO3yH2O
(NH4)4[Ni(OH)6Mo6O18]5H2O
4 H2O
(NH4)4[(OH)6Mo6O18]5H2O
(N3H2O

0.820 (60); 0.431(25); 0.401(20); 0.325 (100); 0.300(90); 0.280(15); 0.245(12); 0.20
(25); 0.190(25)
0.670 (40);0.62(11); 0.379(37); 0.349(34); 0.334 (63); 0.337(25); 0.326(40);
0.311(32); 0.277(20); 0.265(9.0)
1.11(8); 0.803(6); 0.58(7); 0.510 (12); 0.375(3); 0.312(3); 0.303( 6); 0.271(3)
0.628(10); 0.341(30); 0.337(80); 0.335(100); 0.312 (20); 0.306 (70); 0.8000.223(10-15)
1.087(4); 1.102 (3); 0.572(7); 0.512(9); 0.373(2)
0.493(5); 0.491(4); 0.478-0.480(4); 0.443(3); 0.297 (3)

-
( 473 K)
- Ni -
(473 K)

Ni (623 K )

- (623 K )

- Ni -
(623 K )

Amorphous phase

Halo 0.80- 0.26 (5-8)

NiMoO4xH2O
NiMoO4
xNiOMoO3yH2O
(NH4)4[Ni(OH)6Mo6O18]5H2O
3
4 H2O
4
3
xNiOMoO3yH2O
NiMoO4xH2O
NiMoO4

Ni (823 K )
NiMoO4
- (823 K )
4
- Ni - (823 K ) 3
Ni ()MoO4
3

0.820 (23); 0.431(7); 0.401(3); 0.325 (100); 0.300(90); 0.280(5); 0.20 (12); 0.190(10)
0.611(23); 0.368(11); 0.341(22); 0.308(34);0.273(27); 0.232(5); 0.190(6); 0.1707(5);
0.147(4)
0.672(20); 0.379(18); 0.335(23); 0.326 (17)
1.10(3); 0.511(5); 0.303( 2)
0.692(12); 0.325(21)
0.633 (15); 0.383(33); 0.350 (23); 0.338 (100); 0.338(43); 0.314 (26)
0.623(13); 0.354(22); 0.313 (26)
0.697 (55); 0.325 (100)
0.697 (55); 0.620 (10); 0.498 (8); 0.379(32); 0.350(45); 0.325 (100); 0.315(31);
0.278(28); 0.265 (23)
0.823 (15); 0.697 (55); 0.433(17); 0.411(9); 0.380(65) ; 0.325 (100) ; 0.300 (20);
0.247(5)
0.615 (5); 0.37(3); 0.34 (20); 0.307(50); 0.272(30); 0.206(10); 0.191(4)
0.61(23); 0.37(5); 0.341(28); 0.308 (100); 0.273 (50); 0.22(10); 0.206(55); 0.190(13);
0.171 (13)
0.625(45); 0.374(8); 0.354(38); 0.313 (100); 0.278(30); 0.273(10)
0.692(12); 0.325(21)
0.615(15); 0.37(7); 0.341(23); 0.308 (100); 0.273 (44); 0.22(7); 0.206(36); 0.190(5);
0.171 (8)
0.325(18)

the presence of a peak of absorption in the area of 3200029000 cm1 [12]. The ions of nickel Nih2 + in structure close
to Ni4 peaks 24000-23000 nearby 13600-13200 cm1
[14-16] corresponded. At transition from + to carrier
GOA+AO+K and further to GOA+ relative intensity of
peaks of absorption of molybdates decreased. Structures
with parameters of electronic spectra close to massive
phases of Ni4 and 4 appeared during the
calcinations of hydrated molybdates not entered into
reaction with the carrier (able 3, Fig. 1, curves 6- 7, 9-10).
Weak inflections nearby 14000 and 13000 cm1
indicate a presence of insignificant quantity of superficial
structures of nickel-alumina-molybdates and nickelmolybdates. In the spectrum of catalyst IV-1/GOA+K
(Fig.1, curve 3) the wide absorption peak was observed
at 14200 cm1 from partially hydroxylated ions Nih2+ which
are bonded simultaneously with a surface of alumina
hydroxide and anions 42 [12, 14, 16]. Shoulder

occurrence at about 12700 cm1 confirms the distortion

of octahedral symmetry of ion Ni 2+ at introduction in
its coordination sphere of anions 42. Intensity of
absorption peak of about 12700 cm1 increased at obtaining
nickel-molybdenum catalysts on a mix GOA+ + and
the more so on + (Fig. 2, curves 3, 5).
Further spectral display of interaction of heteropoly
compounds, formed in compound solutions, and with
a surface of carrier components has been considered.
The central atoms of nickel and cobalt in heteropoly
compounds are located inside coordination sphere
of heteropoly molibdate-anions. Their spectral
characteristics differ from h2+ of external coordination
sphere in hexa-aqua complexes (2)62+, (N3)2
and 4 a little. Really, spectra of dehydrated Ni-,
- and Ni-- catalysts were characterized by low
level of absorption in the area of 15000-13000 cm1. With
an increase in temperature up to 673 K in spectra, Ni-

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M.P. Yunusov et al.

of catalysts insignificant displacement of peaks to 14500

and 13400 cm1, characteristic for the process of water
removal of their coordination sphere Nih2+ (Fig. 2, curves
1,2) was observed only. The intensity of the peaks at 21000,
19200 and 16000 cm1 considerably increased in similar
conditions in spectra - and Ni-- catalysts
from ions h2 + (Fig. 2, curves 6, 7). This could be due
to replacement of double-charged cations, in particular
cobalt, from position of the central atom in heteropoly
anion [H6Mo6O24] 4 by alumina triple-charged
cations on the surface of alumina hydroxide [11]. A new
heteropoly anion [AlH6Mo6O24] 3 has been strongly bound
with the carrier. It was possible to judge this indirectly
by occurrence of additional weak peaks of absorption at
945 and 665 cm1 in IR spectra about behavior of similar
chemical interaction. The given peaks were shown in IR
spectra of bimetallic and trimetallic catalysts and are
characteristic for interaction of heteropoly compounds in
row 6 with the double-charged central atom and triplecharged cation Al3 + of surfaces of oxides and alumina
hydroxide [4, 11]. Cations h2+, together with NH4+ outside
of coordination sphere, became salt-forming. Obvious
growth of the peaks at 18300-16600 cm1, after ignition
Ni-- and - catalysts at temperature 823 K, we
connect with introduction of salt-forming cobalt cations in
tetrahedral emptiness in carrier volume. This temperature
coincided with phase transition of alumina hydroxides
as a part of the carrier in oxide, when the last is most
reactive. Spectra of trimetallic catalysts on all studied
carriers were notable for abundance of absorption peaks
and bend points (Fig. 2, curves 6-9). A series of peaks
at 27000-23000, 21000, 19200 and a bend point about
13000 cm1 in electronic spectra indicated on formation
of molybdates of cobalt and nickel. High extinction of
triplet of peaks Td2+ at 15000, 16600 and 18000 cm1,
overlapping absorption peaks, characteristic for ions
NiTd2+ (16800 and 15800 cm1), h2+ (19000 cm1) and Nih2+
(15000 m1), not allowed to estimate unequivocally ratio
of octahedral and tetrahedral coordinated ions. Presence
of bends in areas 27000- 23000 and 17000- 13000 cm1 is
not in contradiction, but also did not prove formation of
associates Al NiMo and Al CoMo.
The method of selective extraction has been used for
the estimation of bridging durability of active components
structures within the carrier. Theprocessing by water units
of metals of molybdates and poly-molybdates, contained
inside the volume of pores (weak interaction) were
removed. With a water solution of ammonia, associates of
various structures chemically connected with the pores
surface, thecarriers (strong tie) were extracted. Spinel
structures were not removed during selective extraction.

According to selective removal, active components are

most strongly contacted with carrier GOA+K (able
4). About 8% of active components of low-percentage
catalysts of hydrodesulfurization (samples of structure
I-III) have been aggregated in the form of volume metals of
molybdates and removed during processing using water.
The degree of extractionof cobalt from trimetallic catalysts
was always considerably greater than nickel. At alkaline
hydrolysis in the solution of ammonia nickel and cobalt
have been extracted in small quantities.
The quantity of extracted by water volume of
compounds of molybdenum increased in catalysts of
structure IV-VI by 14-16%. Thesynthesis of all catalysts
through method 1, in that ionic degree, there was an
irreversible introduction of ions of cobalt, nickel and
molybdenum in a lattice of alumina oxide. During the
impregnation of + after consecutive extraction by
water and water solution of ammonia, the minimum
quantity of the inserted metals testified that this was
indeed a process to suppress spinel formation. All
received extracts have been enriched by molybdenum,
in comparison with the stoichiometrical molybdates of
type 4 (3 / = 1.93). The ratio of 3 /
as a part of the dehydrated water extracts increased
from 2.25 from catalysts on GOA+ to 8.01 on GOA++
and again decreased to 1.98 on +. It was testified that
there was not a proportional dependence of composition
and solubility of structures with ions of molybdenum on
content. The maximum quantity of poly compounds
of molybdenum is shown in catalysts on the basis of
GOA++. The content of Al2O3 and SiO2 in the water
extracts of catalysts on 1-2% exceeded their concentration
in control extracts of their calcined mechanical mixes
GOA+, GOA++ and +.
The determined differences have been caused by
surface screening of hydroxide and alumina oxides as a part
of AO by-products of consolidation of organic substances.
Large particles of AO have been poorly resolved by the
diluted acids and interaction of components of combined
solutions with a surface of carriers at mixing and drying
stages has been complicated. Possibly, structures with the
formulation of[AlMo6O24H6]/Al2O3 have been potentially
formed. The compounds formed in combined solutions
at a stage of preparations (able 3), were aggregated in
volume of pores. At the heat treatment, decomposition
processes of heteropoly molybdates to molybdates and
molybdenum oxide, extraction of water from hydrated
molybdates, transition of boehmite in -Al2O3 and burning
out of organic substances simultaneously proceeded. As a
result, about 77% of molybdates units of nickel and cobalt
were removed during water extraction, and absorption

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51

Table 4: Composition of catalysts with the various carriers after processing by water and water solution of ammonia depending on the
preparation method.
Oxides

Content;%
G+

Al23
Si2
P25
Co
Ni
Mo3
Al23
Si2
P25
Co
Ni
Mo3

G+

G++

II-1

NH4OH

I-1

NH4OH

IV-1

NH4OH

IV-1

NH4OH

76.1
3.90
3.31
4.11
11.9
-1
IV-2
66.1
4.15
4.69
4.20
1.73
17.9

75.7
3.88
3.30
3.71
11.0

75.1
3.85
2.97
3.69
9.90

64.7
4.22
4.66
3.31
1.54
15.1

64.1
4.20
4.11
3.28
1.50
12.5

64.8
4.31
4.12
3.17
1.47
8.13

61.7
8.28
4.26
0.73
0.50
7.35

2
66.2
3.85
4.66
1.33
0.64
10.04

NH4OH
65.6
3.81
4.65
1.28
0.42
7.83

2
76.0
3.53
3.25
1.81
7.6

NH4OH
77.2
3.50
3.22
1.80
3.30

62.9
8.44
4.35
4.18
1.73
17.2
-3
V-2
61.7
8.56
4.17
4.8
13.2

62.4
8.35
4.26
0.90
0.54
8.32

NH4OH
64.5
3.87
4.60
3.06
1.52
12.4

65.5
4.35
4.63
4.08
1.65
17.3
-2
II-2
75.8
3.87
3.31
4.24
12.3

65.3
4.32
4.55
3.22
1.53
9.45

2
65.2
3.95
4.63
3.10
1.52
14.5

65.8
4.24
4.71
4.22
1.68
17.9
-2
IV-2
66.8
4.14
4.71
4.19
1.70
17.6

2
63,0
7.23
3.11
1.44
6.73

NH4OH
62.2
7.12
3.07
1.40
5.05

Non-standard designations
GOA - industrial alumina hydroxide; AO - spent adsorbent ; K- kaolin; R - coefficient of diffuse reflectance; Cacid - the concentration of acid
sites; Cpoison - the concentration of n-butylamine poisoned sites; f (R) and f (R) poison - Kubelka-Munk function for the band maximum of acid
form of the corresponding indicator before and after the poisoning of surface acid sites; PAC- polyaromatic compounds; GOA+K (12%)
carrier AK-1; GOA+ (35%) + (12%) carrier AK-2 ; + (25%) carrier AK-3 ; Hydrodesulfurization catalysts: I 1 % Ni, 3% CoO,
12% MoO3; II 4% Ni, 12% MoO3; III 4% , 12% MoO3; Hydrogenation of polyaromatic compounds: IV 1.7% Ni, 4.2% CoO,
17.8% MoO3; V 6% Ni, 18% MoO3 and VI 6% , 18% MoO3.

peaks in the vicinity of 32000-29000 cm1 disappeared.

The lowered specific surface of samples (able 2) also
has been testified to formation of massive low- dispersed
molybdates. As a part of water extracts from catalysts on
, the ratio of MoO3/NiO, MoO3/CoO and MoO3/NiO+CoO
was close to stoichiometry corresponding to molybdates.
At the increase of temperature of the catalysts up to 673
K,molybdenum ions, cobalt and nickel have not been fully
diffused in to the volume of the carrier, and were easily
removed using water (able 4). After calcining the sample
to a up to 823 K, content of Ni2+Td and Co2+Td (or their sums)
in catalysts after water and aqua-ammoniac extraction
has increased from 4.5% to 8.3%.
Research of a profile of change of concentration Co,
Ni, on carrier grain has revealed uniform distribution
of active metals for all catalysts prepared in the method1
(Fig. 3, photos 1-3). It is caused by good agitation of
catalyst mass and small migration of sparingly soluble
compounds in the drying and catalysts calcination
processes.

Preparation of catalysts by impregnation

method (Method 2).
Narrow-porous carrier AK-1, at the moment of
impregnation, had on a surface weak acid sites with =
+3.8. mediums at the first impregnation, by combined
solutions, changed from 1.5 to 2.8 (Table 1). Repeated
impregnation at synthesis of high-percentage catalysts was
accompanied by change of from 1.5 to 2.0. In process of
growth of active components, concentration mechanical
durability of granules of carrier AK-1 increased, and
the maximum on a curve of distribution of pores in the
sizes moved towards reduction of their radii (able 1, 2).
On the basis of these data the conclusion is drawn, that
active components are adsorbed mainly insmall pores,
with radii less than 5 nanometers. Degree of extraction by
water of structures of active components has increased, in
comparison with similar catalysts on GOA+ (able 4). In
particular, the content of water-soluble cobalt in catalysts
on -1 (calcined at 673 K) reached 26-30%, and nickel
about 12% from the initial. After calcination at 823 K,
the degree of removal was 7%. Solubility of structures
of molybdenum during the calcinations has changed
minimally.

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Fig. 3. Distribution of elements on a cut of granules of various catalysts

Electronic spectra of diffuse reflections of the catalysts

obtained on carrier AK-1 by method 2, differed from method
1 only by lower level of absorption in the area of 16800 and
15800 cm1 (Fig. 4). The analysis of intensity of absorption
characteristic for NiAl2O4 has revealed concentration
decrease of spinel structures in the following number of

catalysts II-2/AK-1> I-2/-1> IV-2/-1> V-2/-1. These

data coincide with results of selective extraction of cobalt
and nickel (able 2).
Research of profile of concentration non-uniformity
of elements distribution on a cut of granules of the
catalysts prepared by unitary impregnation on -1 is

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Synthesis and Study of Ni-Mo-Co Catalysts for Hydroprocessing of Oil Fractions

determined to be (Fig. 3, photos 4-6) similar to [20]. For

Ni- catalysts, formation of a superficial ring in width
smaller than 1300 microns with the raised concentration
of molybdenum (13.0-13.2% 3) and phosphorus (2.53.5% 25) was characteristic. Further concentration
gradually decreased to 3.0-3.5% 3 and 0.5-0.6%
25 in the central part of a granule. In the case of -
and Ni-- catalysts, contours of a ring in width 600
microns with high concentration (about 20% 3, 3- 5%
25) have been accurately outlined. Moving to the center
the content of the 3 decreased to 3.2%. The zone of
high concentration of molybdenum did not coincide with
a profile of distribution of cobalt: a ring in width about
1000 microns (4.5% ) and 1.9% in the central
part of a granule. Concentration of Ni in bimetallic and
trimetal catalysts in the centre and on periphery was
practically identical (Photos not shown).
At double impregnation, the zone in width of
1300 microns from the maximum concentration of
molybdenum (21-23% 3) and phosphorus (4.7- 6.2%
25) displaced on 100-120 microns deep into granules. On
periphery and in the central part, there is 16.8 and 14.2%
of 3 , respectively. The tendency of the molybdenum
to alignis caused, in our opinion, by weak interaction of
heteropoly compounds with the carrier at the first stage
of synthesis and high acidity of a semi-product of the

53

catalyst at the second impregnation. Poorly connected

heteropoly anions [NiH6Mo6O24]4 with a high content of
molybdenum, were partially transferred together with new
portion of combined impregnated solution into deeper
layers of a granule. Heteropoly anions [H6Mo6O24]4
already at the first impregnation strongly contacted
with the carrier due to formation of new connection
[AlMo6O24H6]4. At repeated impregnations, there was
no cobalt redistribution; border smoothing between zones
was observed only. Thus, the width of zone with the raised
concentration of elements of molybdenum, cobalt and
phosphorus reached 1000 microns (Photos not shown).
The impregnation of macro porous carrier AK-2 with
combined solutions of active metals for preparation of lowpercentage catalysts shows an insignificant increase in
the concentration ofof small pores. The volume and radius
of larger pores has decreased by nearly 200% (Tables 1, 2).
We have explained this fact by the following processes. At
contact with the basic surface of carrier AK-2, first of all
heteropoly compounds with a strong acidity ( < +1.5)
were chemisorbed. Acidity of medium in pore space, as
a result of removal of the most acidic components from
impregnation solution at chemical adsorption, rose to
2.7-3.0. Solutions of hydrated molybdates of nickel and
cobalt are steady in the given interval , therefore on
transport channels pores in radius of 7-10 nanometers in

Fig.4. Electronic spectra of diffuse reflection of catalysts for hydrodesulfurization (1-2, 6) and hydrogenation of the polyaromatic hydrocarbons (3-5) prepared by the method 2 with impregnation of carriers AK-1 (1, 3, 5), -2 (2, 4) and -3 (6). Ni- (1-2,5) and -Ni- (3-4,6)
catalysts. Thermal treatment at 673 K (5) and 823 K (1-4, 6).

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M.P. Yunusov et al.

volume of granules arrived. In the process of impregnation

solution, moving from a surface into deep layers, the
value continued to rise. At 3.5 the solubility of hydrated
molybdates of nickel and cobalt sharply decreased and
they fell out in pores. In the process of calcination there
was no migration of the rest of the 4 2. At
thermal decomposition, the remainder of the localized
volume of large pores, new pores with radiuses less
than 3 nm were formed. The smallest pores of the carrier
were filled with impregnated solution containing a high
deficiency of molybdenum. Therefore, during drying
and calcination on internal surface of small pores, the
monolayer of molybdates of metals were generated and
the sizes changed less. Insignificant decrease in a specific
surface indicated on high enough dispersion of units of
the large pores located in cavities.
The width of a ring with high concentration of
molybdenum (12.2% 3) and phosphorus on a cut of
granules of low-percentage Ni-Mo catalysts on -2 has
increased to 1500 microns per (compared with AK-1),
with a concentration of of 7% 3 in the central part
of a granule (Photos not shown). In case of Ni--Mo and
-, catalysts a superficial ring with 3 14.2% and
P2O5 2.7-3.8% was considerably narrow 1000 microns,
but the width of a ring with high concentration of cobalt
(4.0 - 4.6%) has increased to 1700-2000 microns per
(Fig. 3, photos 7-9).
The estimation of superficial properties of lowpercentage catalysts of thermo processed at 473- 823 K
has revealed the presence only of the proton acid sites
in an interval from +1.5 to 8.2. Concentration of the
acid sites changed among Ni-Mo> Ni-Co-Mo> Co-Mo.
The force of the acid sites on all catalysts considerably
decreased with increase in content of AO and temperature
of calcination. We explain these facts with destruction
of heteropoly compounds of molybdenum. On a surface
of ready catalysts calcined at 673 K concentration of the
acid centers with = 6.3 - 5.6 was within 0.18-0.15
mg-ekv/g, and with = 5.6 - 3.3 was about 0.22
mg-ekv/g . At catalysts ignited at 823 K these sizes were
equal to 0.07-0.05 and 0.27-0.34 mg-ekv/g, accordingly.
At storage on air all catalysts as after intermediate at 473
K, and final heating at 673 or 823 K, possessed properties
of proton acid, including the sites with negative values
of . The concentration maximum fell to the sites with
+1.5 and made 0.34-0.45, 0.30-0.37 and 0.17-0.28
mg-ekv/g, accordingly.
Thus, repeated impregnation occurred at contact
of acidic solution of active metals with acid surface of
a semi product of the catalyst. Thanks to a wide pores,
impregnated solution quickly, and without appreciable

change of structure, were distributed on volume of

granules in regular intervals. On a cut of granules of
catalysts, the molybdenum content moving from the
periphery to the centre decreased from 18.5-19.8% to 16.917.7% That is, it was close to uniform, similar to method 1
(Fig.3, photos 1-3).
Too small of water absorption in carrier AK-3 did
not allowa high-percentage catalysts, even at repeated
impregnation (able 4). Catalysts on -3 differed with
small specific surface (57 m2/g) and low dispersion of
active components. It followed from occurrence of lowintensity lines with d = 0.820; 0.671; 0.432; 0.403; 0.335;
0.325; 0.300; 0.280; 0.203; 0.190 nm from crystal hydrated
molybdates of nickel in sample NiO (4.8%) - 3
(13.2%)/AK-3, obtained by double impregnation and
dehydrated at 473 K. During impregnation, an impurity of
the basic character, as a part of the carrier has dissolved
with formation of sodium, calcium and potassium
molybdates and raised of combined solution till 3.54.2. In these conditions, heteropoly compounds were
quickly destroyed, and hydrated molybdates of nickel
were precipitated, mainly in surface layer of granules.
Macro distribution of active elements on -3, after the
first impregnation was typical to crust with a narrow
zone 40-70 microns of high concentration of molybdenum,
cobalt and nickel for binary and trimetal catalysts. As a
result of repeated impregnation following distribution of
metals in volume of granules is received: 3 (12.2%),
(2.1%) and NiO (0.6%). The width of a superficial
ring with concentration 3 (18 - 19%), (8%) and
NiO (3%) has increased to 50-100 microns (Fig. 3, photos
10-12).
For all catalysts of series 2, an increase in quantity
of molybdate structures extracted by water (able 4), in
comparison with mechanical mix GOA+ and -1 was
marked. It has provendurability, attenuation of tie of
molybdenum with a surface of carriers AK-2 and -3. The
quantity of molybdenum extracted by water from structure
of catalysts was above, than by aqua-ammoniac solution.
Relation of 3 / NiO, 3/oO and 3 /NiO+
in dry water extracts was about 1.928 and corresponded
to stoichiometry of mono molybdates of type 4.
The analysis of dry extracts from catalysts on -3 has
revealed increase of concentration Na2O, K2O and in
comparison with mix + 5-7 times. We connect it with
extraction of molybdates of alkaline metals, well soluble
in water.
Prevalence of volume molybdates, not co-operating
with carriers components containing adsorbent AO, is
confirmed by electronic spectra of diffused reflections.
Intensity of peaks absorbing in the field of 19000-25000

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Synthesis and Study of Ni-Mo-Co Catalysts for Hydroprocessing of Oil Fractions

and 13300-12200 cm 1 (Fig. 4, curves 1-4), corresponding to

phases NiMoO4 and MoO4 increased, in comparison with
catalysts on -1. The kind of spectra of high-percentage
catalysts IV-2/AK-2, V/AK-2 (Fig. 4, curves 4, 5) and VI/
-2 was close to spectra of the model systems obtained
by evaporation and calcination at 673 K of corresponding
impregnation solutions (Fig. 1, curves 6,10). Ions of NiTd2 +
were not shown in spectra.
An obvious increase of the level of continuous
absorption at drawing of active components on carrier
AK-3, along with displacement of edge of a strip of
transfer of charge 6 + from 30000 to 38000 cm1 verifies
depolymerization of molybdate-ions and interaction with
impurities (Fig. 4, curves 1, 2, 6). The part of ions of nickel
and cobalt was not included into structure of molybdates
and after heat treatment was in a kind of radio amorphous
oxide formations. Thus, the considerable quantity of
as a part of the carrier destabilized impregnation solution
and was accompanied by formation low active compounds
concentrated on a surface of granules.
Analyzing the received results, we have come to
conclusion that the mechanism of influence of AO on
formation of oxide precursors of active phases depends on
quantity and the way of introduction of the additive. It is
confirmed with data of activity of catalysts calcined at 673
K in a number of processes (able 2). Activity of catalysts
of similar structure after glowing at 823 K was lower on
5-6%, than thermo processed at 673 K. Introduction of
35% of the additive of AO and 10% kaolin does not render
negative influence on the activity of catalysts irrespective
of a way of preparation in reactions hydrogenolysis of
sulfurous compounds and hydrogenation of polyaromatic
compounds. At synthesis by a method of mixture, surface
screening by organic adjournment leads to the additional
formation of associates of hydrogenating elements
and to the increase of hydrodesulfurization function.
Degree of elimination of the general and mercaptan
sulfur from various fractions of oil was comparable to
activity of impregnation catalysts on -1, -2 and pure
-Al2O3 with similar structure of active components. The
increase of hydrodesulfurization activity on trimetallic
catalysts in comparison with the bimetallic was observed.
Application of -Ni- and - catalysts with the
studied parity of elements and AO addition it is expedient
only at synthesis by the mixture method. In impregnation
catalysts, the considerable part of cobalt is in a kind of
individual oxide phase no connected with molybdenum
and settles down on granule periphery. Activity of
Ni- impregnation catalysts on -2 in reactions of
hydrogenolysis and hydrogenation of polyaromatic
compounds was considerably above, than on -1 and

55

synthesis by method 1. We explain this by simultaneous

increase of poorly and moderately connected structures
of molybdenum, reduction of content of NiAl2O4 and
improvement of porous structure. Thanks to maximum
quantity of disperse nickel molybdates, not included in
structure of the carrier, distributed evenly along the cut
at double impregnation -2, bimetallic Ni- catalysts
show high activity in hydrogenation of polyaromatic
hydrocarbons.

Conclusion
Based on these results we can conclude that:
1. A new approach to the preparation of hydroprocessing
catalysts, which is based on the use of kaolin, and
the spent adsorbent in the carrier as components
of catalysts for the synthesis of structures
targeted oxide precursors, which are active in the
hydrodesulfurization and hydrogenation reactions.
2. The effect of additives - spent adsorbent and kaolin
on the formation of porous structure, acid-base
properties of the carriers and the coordination state
of the active components is established. Introduction
of the spent adsorbent is the best way to increase the
share of wide pores, lowered acidity of carrier and
allowed us to obtain a uniform distribution of Co, Ni
and Mo on the catalyst granule.
3. Comparison
of
hydrodesulfurization
and
hydrogenation activity of series catalysts allows a
positive effect to be established with introduction of
the additives - kaolin and spent adsorbent into the
composition of catalyst, and combining the promoters
Co and Ni. Optimal effect is achieved when the spent
adsorbent content of 30-35% and a synthesis method
based on impregnation.
4. Within this approach can be prepared catalysts for
deep processing of oil fractions for the production
of environmentally friendly products, including
fuels that meet high quality standards for sulfur
content and aromatics. Catalysts containing the
spent adsorbent as additives can also be used for
purification of natural gas from mercaptans, as well
as methane conversion.

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