Catalysis Today 305 (2018) 117–125

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Catalysis Today
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Hydrocracking of vacuum gas oil over NiMo/Y-Al2O3: Effect of mesoporosity T

introduced by zeolite Y recrystallization
⁎
M.O. Kazakova, , K.A. Nadeinaa, I.G. Danilovaa, P.P. Dika, O.V. Klimova, V.Yu. Pereymaa,
E.Yu. Gerasimova, I.V. Dobryakovab, E.E. Knyazevab,c, I.I. Ivanovab,c, A.S. Noskova
a
Boreskov Institute of Catalysis SB RAS, Pr. Lavrentieva 5, 630090 Novosibirsk, Russia
b
Department of Chemistry, Moscow State University, Lenin Hills 1/3, 119991 Moscow, Russia
c
A.V. Topchiev Institute of Petrochemical Synthesis RAS, Leninskiy Prospect 29, 119991 Moscow, Russia

A R T I C L E I N F O A B S T R A C T

Keywords: Hydrocracking of vacuum gas oil was studied over micro-mesoporous zeolite based catalysts, obtained by zeolite
Hydrocracking Y recrystallization. The contribution of mesoporosity in recrystallized materials was varied by adjusting the
Vacuum gas oil content of alkali and the temperature of hydrothermal treatment. The increase of recrystallization degree results
Stacked bed in the increase of mesopore to micropore volume of zeolite Y as well as to the decrease of the contribution of
Catalyst
strong Brønsted acid sites in faujasite cages and the increase of the contribution of Brønsted acid sites in me-
Zeolite recrystallization
Micro-mesoporous zeolite Y
sopores. The highest hydrocracking activity and middle distillates yield is achieved over NiMo catalyst obtained
with micro-mesoporous material with low degree of recrystallization. This effect is due to the improved ac-
cessibility of active sites and easier transport of bulky molecules provided by mesopores, on the one hand, and
optimal zeolitic acidity, on the other hand. The highest selectivity to middle distillates is achieved over catalyst
with the highest degree of zeolite recrystallization. This observation can be explained by the decrease of the
contribution of strong BAS (bridging Si-O(H)-Al groups) accompanied by the increase of concentration of BAS in
mesopores.

1. Introduction preferred. NiMo catalysts are used when a supplementary hydro-

denitrogenation (HDN) activity is required, while NiW catalysts are
Hydrocracking is one of the main processes in oil refinery for the used when hydrogenation activity is a priority [12].
conversion of a wide range of low-value heavy feedstocks into high- Depending on the support composition, hydrocracking catalysts are
quality products, mainly transportation fuels [1,2]. This technology is classified into non zeolite catalysts, based on amorphous silica-alumina
extremely versatile and provides the production of middle distillates of (ASA), and zeolite catalysts, which can be grouped into low zeolite and
superior quality: diesel fuel with high cetane number, low aromatics high zeolite content catalysts [1,13]. Amorphous catalysts are less ac-
and sulfur content, good cold flow properties and jet fuel with high tive for hydrocracking than zeolite catalysts, however they provide
smoke point and low freeze point. Hydrocracking catalysts are bifunc- higher selectivity to middle distillates [14]. Zeolite catalysts are sub-
tional catalysts, comprising both hydrogenation and acid functions. stantially more active due to higher acidity. Higher activity allows
Cracking as well as isomerization activity is provided by the acidic operating the process at lower temperatures and provides middle dis-
component, while the supported metals provide hydrogenation activity tillates of higher quality. At present, zeolite commercial hydrocracking
[3]. Typically, mixed transition metal sulfides (NiMo or NiW) [4–8] or catalysts are based on ultrastable Y zeolites (USY) [12,13]. The activity
noble metals (Pt or Pd) [9–11] are used in hydrocracking catalysts. and selectivity of a catalyst and products distribution (gases, naphtha,
Noble metals possess much higher hydrogenation activity, however, kerosene, diesel) are determined by the balance between acid function
they can be used only in a low-sulfur or sulfur-free environment, i.e. in and hydrogenation function [1,15,16]. Catalysts with high acidity but
hydrocracking units with a separate recycle system for the second-stage weak hydrogenation function produce light products such as naphtha
operation. In the presence of hydrogen sulfide and organic sulfur and gases, whereas catalysts with lower acidity and enhanced hydro-
compounds as well as ammonia and nitrogen compounds, i.e. single- genation activity produce middle distillates. At the same time, the ac-
stage hydrocracker or first-stage operation, mixed metal sulfides are cessibility of zeolite acid sites should be taken into account, since

⁎
Corresponding author.
E-mail address: [email protected] (M.O. Kazakov).

http://dx.doi.org/10.1016/j.cattod.2017.08.048
Received 19 May 2017; Received in revised form 15 August 2017; Accepted 22 August 2017
Available online 26 August 2017
0920-5861/ © 2017 Elsevier B.V. All rights reserved.
M.O. Kazakov et al. Catalysis Today 305 (2018) 117–125

diffusion limitation may play a major role in the conversion of large 2.1.2. Preparation of the supports and catalysts
molecules due to zeolite microporous structure. As has been shown by AlOOH boehmite produced by ISCZC (Russia) and RFAU zeolites
hydrocracking of model compounds of different molecular sizes and were used for the preparation of supports.
atmospheric residue [17,18], enhanced mesoporosity of zeolite Y is Four supports denoted as FAU-Al2O3 and RFAUx-Al2O3 (where x –
favorable for hydrocracking of heavy feeds. RFAU sample number) with zeolite content of 30 wt% were prepared by
The most generally applied approach to increase the accessibility of mixing of zeolite and AlOOH followed by peptization with HNO3 and
active sites and minimize diffusion limitation is the creation of meso- extrusion of obtained paste using plunger extruder. The obtained trilobe
pores inside the microporous zeolite crystals [19–21]. A wide variety of extrudates were dried at 120 °C and calcined at 550 °C.
methods have been developed for generating mesopores in zeolites, NiMo/FAU-Al2O3 and NiMo/RFAUx-Al2O3 catalysts were prepared
however the most common approach is based on the removal of fra- by impregnation of the corresponding supports with aqueous solution
mework aluminium (dealumination) or silicon (desilication) atoms prepared from nickel carbonate, ammonium heptamolybdate and citric
[22]. One of the promising strategy for the preparation of zeolites with acid with mass ratio of the components 1: 2.9: 2.5. Impregnated cata-
a secondary mesoporosity, which are referred to as micro-mesoporous lysts were dried at 120 °C and calcined at 550 °C. Ni and Mo content in
zeolite materials, is zeolite recrystallization with surfactants [23–29]. the catalysts was 3.0 ± 0.1 and 9.8 ± 0.5 wt% respectively.
The procedure involves zeolite dissolution leading to partial destruction Also, two catalysts NiMo/Al2O3 and NiW/ASA-Al2O3 were pre-
of a zeolite and extraction of zeolitic fragments and the following re- pared. NiMo/Al2O3 catalyst and NiW/ASA-Al2O3 were used as the first
assembling of the dispersed species into mesoporous phase. Depending and second layers in a stacked bed to approximate conditions in la-
on the degree of zeolite recrystallization, micro-mesoporous materials boratory unit to industrial ones. NiMo/Al2O3 was prepared using si-
can be obtained as mesoporous zeolite crystals, coated with thin films of milar impregnation solution but without calcination after drying at
mesoporous materials, composite materials consisting of two co-crys- 120 °C [41]. Ni and Mo content in NiMo/Al2O3 catalyst was 3.7 and
tallized zeolitic and mesoporous phases or mesoporous materials with 12.5 wt% respectively. NiW/ASA-Al2O3 catalyst was prepared by im-
zeolitic fragments in the walls [28]. Recrystallization significantly in- pregnation with the aqueous solution prepared from nickel carbonate,
creases the volume of mesopores and the accessibility of acid sites. With ammonium paratungstate and citric acid followed by subsequent drying
increasing the degree of recrystallization the number and strength of at 120 °C and calcination at 550 °C [42]. Ni and W content in NiW/ASA-
the acid sites decreases, while the accessibility of the sites is improved. Al2O3 catalyst was 3.1 and 17.4 wt% respectively.
Superior performance of recrystallized materials with respect to parent
zeolites have been confirmed in a wide range of reactions including 2.2. Characterization
alkylation of aromatics on recrystallized mordenite [30], methanol
dehydration on recrystallized ZSM-5 [31], skeletal isomerization of 1- Elemental analysis of the catalysts was carried out using the method
butene on recrystallized ferrierite [32,33], hydroisomerization of oc- of atomic emission spectroscopy with inductively coupled plasma (ICP-
tane and hexadecane on Pt-containing recrystallized mordenite [34], AES) on Optima 4300 DV.
hydrodealkylation, transalkylation and disproportionation of alkylaro- Low temperature adsorption-desorption of N2 for zeolites was
matics on recrystallized mordenite [24,35,36], cracking of vacuum gas measured at 77 K using an automated porosimeter (ASAP 2000
oil (VGO) on recrystallized faujasite [27,37]. NiW-modified micro- Micromeritics). The BET method was applied to calculate the total
mesoporous zeolite material obtained by recrystallization of BEA surface area, which was used for comparative purposes. The t-plot
showed higher activity and selectivity for middle distillates in hydro- method was used for determination of microporosity. The total sorbed
cracking of Daqing vacuum residue than parent BEA, MCM-41 and the volumes, including adsorption in the micropores and mesopores, were
mechanical mixture of BEA and MCM-41 [38]. calculated from the amount of nitrogen adsorbed at a relative pressure
The advantages of the strategy for the preparation of micro-meso- P/P0 of 0.95, before the onset of interparticle condensation. Pore size
porous zeolite materials by zeolites recrystallization can be used to distribution was calculated by BJH method using the adsorption branch
increase the selectivity to middle distillates of USY-based hydrocracking of the isotherm.
catalysts. In this work we present the results on the effect of meso- Textural properties of the catalysts and supports were determined
porosity introduced by zeolite Y recrystallization on the performance of by nitrogen physisorption using an ASAP 2400 Micrometrics instru-
NiMo/Y-Al2O3 catalyst in hydrocracking of vacuum gas oil. ment.
Hydrocracking was performed with non-pretreated feed and stacked HRTEM images were obtained on a JEM-2010 electron microscope
catalyst beds [39]: the top layer – hydrotreating catalyst, the interlayer (JEOL) with a lattice-fringe resolution of 0.14 nm and operated at an
– ASA-based hydrocracking catalyst and the bottom layer – hydro- accelerating voltage of 200 kV. The high-resolution images of periodic
cracking catalyst based on micro-mesoporous zeolite Y. This approach structures were analyzed by the Fourier method. Samples to be ex-
allows simulating commercial process conditions for single-stage hy- amined by HRTEM were prepared on a perforated carbon film mounted
drocracker or first-stage operation, when zeolite catalyst operates in the on a copper grid.
presence of NH3, H2S and small amounts of unconverted organic hetero Temperature programmed desorption of ammonia (TPD-NH3) was
compounds. performed on chemisorption analyzer USGA-101 (production of UNISIT
Ltd., Russia) equipped with TC detector.
Surface acid sites of the zeolites were characterized by IR spectro-
2. Experimental scopy of adsorbed carbon monooxide. IR spectra were recorded on a
Shimadzu FTIR-8300 spectrometer within the spectral range of
2.1. Preparation 700–6000 cm−1 with a resolution of 4 cm−1 and 500 scans for signal
accumulation. The powder samples were pressed into thin self-sup-
2.1.1. Preparation of micro-mesoporous zeolites Y porting wafers (0.004-0.006 g/cm2) and activated in the special IR cell
Micro-mesoporous zeolites Y were obtained by hydrothermal at 773 K for 2 h in dynamic vacuum of 10−3 mbar. CO was introduced
treatment of dealuminated zeolite Y denoted as FAU (CBV-720, Zeolyst) at liquid nitrogen temperature by doses up to an equilibrium pressure of
in a mixture of ammonia and hexadecyltrimethylammonia bromide 13 mbar. The strength of Brønsted acid sites (BAS) was estimated by the
aqueous solutions according [40]. Contribution of micro- and meso- method of hydrogen bonds based on the change in the stretching vi-
porosity in micro-mesoporous zeolites Y was varied by altering the bration frequency of the OH groups that occurred under CO absorption.
concentration of ammonia solution and the temperature of hydro- The higher the shift of IR band of OH stretching vibration of the hy-
thermal treatment. The recrystallized materials were denoted as RFAU. droxyls groups (ΔnOHOH⋯CO), the stronger is the acidity of OH group.

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M.O. Kazakov et al. Catalysis Today 305 (2018) 117–125

The concentration of BAS (method-I) was determined from the integral D7213 standard test method. Product yields were defined by summing
intensity of the band attributed to corresponding OH–group in the H- up an amount of fractions, determined by SIMDIS-GC, and an amount of
complexes with the CO molecules using the following coefficients fractions from the gas effluent from the separator. According to ASTM
(А0 = 54 cm/μmol for the complexes with νOHOH⋯CO 3190–3300 cm−1 D86, liquid samples were fractioned by distillation at atmospheric
and А0 = 27 cm/μmol for complexes with νOHOH⋯CO pressure into naphta (< 130 °C), middle distillates (130–360 °C) and
−1
3385–3500 cm ). Good correlation between the concentration of acid unconverted oil (> 360 °C). Sulfur content in middle distillates was
sites determined by ammonia and by CO was shown in ref. [43]. The measured by ultraviolet fluorescence on Xplorer-NS, TE Instruments.
shift of IR band of the acidic hydroxyls groups (ΔνOHOH⋯CO) were re- VGO conversion was referred to the fraction 360 °C+ in the feedstock.
calculated into the value of proton affinity (PA): PA [kJ/mol] The content of this fraction was 86.6 wt%. The net conversion of VGO
= 1390−442.5*log10(ΔνOHOH⋯CO) /(ΔνOHSiOH⋯CO), where 1390 kJ/ (XVGO) and selectivity to middle distillates (SMD) were calculated using
mol corresponds to the PA of surface OH-groups of Aerosil [44]. The the following equations:
concentration of BAS (method-II) was evaluated from the integral in-
360°C+in feed(wt%) − 360°C+in product(wt%)
tensity (A) of CO band in the range of 2170–2180 cm−1 using the XVGO (%) = × 100%
360°C+in feed(wt%)
equation C = A/A0 with the molar integral absorption coefficients va-
lues А0 = 2.7 cm/μmol [45]. The concentration of Lewis acid sites 130-360°C in product(wt%) − 130-360°C in feed(wt%)
(LAS) was evaluated from the integral intensity of CO band in the range SMD (%) = × 100%
360°C+ in feed(wt%) − 360°C+ in product(wt%)
of 2180–2233 cm−1. The following molar integral absorption coeffi-
cients values (A0, cm/μmol) were used: 1.23 (2233–2225 cm−1), 1.1 The results of catalyst testing are reported as the average value of
(2216–2206 cm−1), 0.9 (2198–2190 cm−1) [46]. The concentration of gas and liquid product samples taken for each 6 h from 144 to 192 h on
OH groups was assessed from the integral intensities of absorption stream (Supporting Information, Fig.S1).
bands in the hydroxyls stretching region using following coefficients
(А0 = 7.5 and 4.7 cm/μmol for strongly acidic bridged hydroxyl groups 3. Results and discussion
in the faujasite supercages and sodalite cages, correspondingly [45]). In
the presented spectra, the absorbance was normalized to sample wafer 3.1. Morphology and textural properties of zeolite materials
density.
In the present study, a series of recrystallized Y zeolites with dif-
ferent degree of recrystallization (RFAU1 < RFAU2 < RFAU3) were
2.3. Catalytic testing and product analysis synthesized from commercially available USY. The chemical composi-
tion of the parent zeolite and the samples RFAU1-3 shown in Table 2
Testing in hydrocracking of vacuum gas oil was carried out in a points to slight decrease of Si/Al ratio with recrystallization, which
high-pressure trickle-bed unit. Catalysts in the form of trilobe granules could be due to partial desilication in basic solution. XRD data pre-
with a length of 3–6 mm and without defects were used for the loading sented in Fig. S2 indicate that the crystal structure is preserved during
the reactor. The total volume of catalysts in the reactor was 60 cm3: first recrystallization, whereas the crystallinity is slightly reduced.
layer – NiMo/Al2O3 20 cm3; second layer – NiW/ASA-Al2O3 20 cm3; Typical fragments of HRTEM images of the studied zeolites are
third layer – NiMo/RFAUx-Al2O3 20 cm3. To minimize a breakthrough shown in Fig. 1. Parent zeolite has well-crystallized particles with mi-
of the feed through a catalyst bed, catalyst granules were mixed with croporous structure as well as mesopores formed by framework deal-
SiC. A mixed feed comprising straight-run VGO (69 wt%), heavy coker umination. HRTEM data for the sample RFAU1 show the presence of
gas oil (22 wt%) and fractions from solvent extraction unit (aromatic dissimilar mesopores piercing zeolite crystals, while the surface of
extract − 7 wt%) and solvent dewaxing unit (petrolatum − 2 wt%), zeolite crystals of RFAU2 is observed to be covered by a film of worm
was used as a feed. The properties of the feedstock used are shown in like mesoporous solid (Fig. S3). At the same time, the zeolite micro-
Table 1. Catalysts were sulfided in situ at a pressure of 3.5 MPa using porous structure is mainly maintained. HRTEM data for RFAU3 (Figs. 1
the mixture of straight run diesel fraction, dimethyl disulfide and ani- and S4) point to the formation of micro/mesoporous nanocomposites,
line. The catalyst loading and sulfidation procedures are thoroughly in which zeolite crystals are co-crystallized with the fragments having
described in [39]. Hydrocracking tests were carried out at a pressure of hexagonal mesoporous structure similar to those of MCM-41 materials.
16.0 MPa, a liquid hourly space velocity (LHSV) of 0.71 h−1 and H2 to Textural properties of the parent and recrystallized zeolites are
oil ratio of 1500 (v/v). The temperature in the reactor was 360 °C given in Table 2. The parent FAU sample already has substantial vo-
during the first 12 h, and then the temperature was increased up to lume of mesopores generated by ultrastabilization. The formation of
390 °C and higher. Each experimental temperature (390 and 410 °C) additional intracrystalline mesoporosity in recrystallized zeolite mate-
was maintained for 192 h. Gas effluent from the separator was analyzed rials is confirmed by the low temperature nitrogen adsorption data
by gas chromatography using FID and capillary column. Liquid pro- (Fig. 2). Parent zeolite has type IV nitrogen adsorption-desorption iso-
ducts were analyzed by SIMDIS-GC in accordance with the ASTM therm with a distinct H4 hysteresis loop, which is typical for micro-
mesoporous materials obtained by dealumination. The secondary me-
Table 1 sopore system is characterized by a broad pore size distribution, the
Properties of feedstock.
mesopores being accessible mostly through micropores. The re-
Characteristic Value crystallized samples show the appearance of marked step at P/
a
Boiling range , °C Table 2
5–10 wt% 306–342 Characteristics of parent (FAU) and recrystallized (RFAU) zeolites.
20–30 wt% 393–434
40–50 wt% 460–476 Sample Si/Al SBET, m2/g Pore volume, cm3/g Mesopore diameter, Ǻ
60–70 wt% 489–502
80–90 wt% 515–533 Vmicro Vmeso Vtotal
95 wt% 549
Sulfur content, wt% 0.966 FAU 16.5 709 0.26 0.19 0.45 –
Nitrogen content, wt% 0.109 RFAU1 16.0 761 0.20 0.32 0.52 30
Density (20 °C), g/cm3 0.927 RFAU2 15.3 772 0.17 0.39 0.56 28
RFAU3 15.0 842 0.12 0.51 0.63 27
a
According to ASTM D7213.

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M.O. Kazakov et al. Catalysis Today 305 (2018) 117–125

Fig. 1. HRTEM images for parent (FAU) and

recrystallized (RFAU) zeolites.

the same time, the volume of micropores decreases by a factor of

1.3–2.2, while the volume of mesopores increases by 1.7–2.7 times with
respect to the parent zeolite. This effect is more pronounced for the
sample with higher degree of recrystallization. On the base of HRTEM
and low temperature nitrogen adsorption data and according to the
classification proposed in [28], RFAU1 and RFAU2 samples can be re-
ferred to mesoporous zeolites, while RFAU3 sample – to micro-meso-
porous nanocomposites.

3.2. Nature and concentration of acid sites of zeolites

The nature of OH-groups over parent and recrystallized zeolites was

studied by FTIR spectroscopy. The IR spectrum of OH groups of FAU
sample reveals eleven bands (Fig. 3, sp. 1). The most intense signals at
3746, 3630 and 3570 cm−1 are typical for IR spectra of USY zeolites
[45,48–50], and assigned to terminal Si-OH groups, bridging Si-O(H)-Al
groups in the supercages (HF, high frequency) and bridging OH in so-
dalite cages (LF, low frequency), respectively. The band at ca.
3630 cm−1 is asymmetric and contains two shoulders at 3620 and
3646 cm−1. The shoulder at 3738 cm−1 corresponds to internal or
defect silanol OH groups typical for zeolites and MCM-41 aluminosili-
cates, which are located in the close vicinity to the lattice imperfection
or Lewis acid site (e.g., tricoordinated Al atom) [51,52]. The less in-
Fig. 2. Nitrogen adsorption-desorption isotherms and pore size distributions of parent tense bands at 3550 and 3600 cm−1 are mostly attributed to LF and HF
(FAU) and recrystallized (RFAU) zeolites. groups polarized by Lewis acidic extraframework Al species [48,50].
Other low intense bands at 3670, 3695 and 3725 cm−1 can possibly be
P0 = 0.3–0.4, which is characteristic of capillary condensation within assigned to the acid OH groups, while signals and 3775 and 3790 cm−1
uniform mesopores [47]. This step becomes sharper with increasing the can be attributed to basic hydroxyl groups attached to tricoordinated Al
recrystallization degree. Plots of pore size distribution (Fig. 2) show the atoms, which are partially connected to the framework.
formation of mesopores of ca. 3 nm in diameter. At the same time, the The nature of the OH-groups in recrystallized samples is similar to
type of hysteresis is changing from H4 type to H2 and H1 pointing to that of the parent fajausite. Recrystallization of parent FAU zeolite into
formation of more open mesoporous network, accessible from the outer RFAU(1–3) samples leads to a moderate decrease in the signals of
surface of the crystal. The comparison of the textural properties of the bridging OH-groups in the IR spectra (Fig. 3, sp. 2–4), to the increase in
parent and recrystallized Y zeolites shows that recrystallization results the peaks of Al-OH species and to the significant increase in the in-
in the increase of a specific surface area and pore volume (Table 2). At tensity of the bands corresponded to Si-OH groups. Varying the con-
centration of different types of OH-groups in the investigated samples is

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M.O. Kazakov et al. Catalysis Today 305 (2018) 117–125

3738 cm−1), indicating a lateral interaction with electron-pair acceptor

sites (Si-O(H)⋯Al3+ groups) (Fig. 4A). Coordinatively unsaturated
species forms typically at the external surface of zeolite micro-
crystallites or in the mouths of micropores under extraction of alumi-
nium species from the zeolite framework. We propose that these defect
silanol groups can be located both at the external surface of zeolite
crystallites and in the intracrystalline mesopores. Formation of
Brønsted acid sites primarily located inside the channels of mesoporous
MCM-41 aluminosilicates with Si:Al < 50 has been observed in [51].
Since the concentration of the groups with band at 3715 cm−1 in-
creased with the concentration of Al, authors concluded that these
groups are partially located at local defects caused by incorporation of
Al. In this work, it is shown that the concentration of Si-OH groups
increases proportionally to the increase of mesopore volume with the
increase of parent FAU zeolite recrystallization degree. At the same
time, the concentration of Si-O(H)⋯Al3+ groups with the band at
3738 cm−1 also increases but not proportionally to the increase in the
volume of mesopores. Fig. 4A shows that the formation of mesopores by
recrystallization leads to the small increase in the concentration of
terminal Al-OH groups, which are characteristic for amorphous phase
Fig. 3. IR spectra of zeolite samples in the OH region: 1–FAU; 2–RFAU1; 3–RFAU2; of alumina.
4–RFAU3. (Dash lines – decomposition of the spectrum of FAU sample). Progressive CO adsorption was carried out on all four zeolites.
During low temperature CO adsorption on FAU sample, the HF band
fully disappeared, and a new band at 3280 cm−1 appeared, but LF band
Table 3
Type and concentration of some OH-groups and acid sites of zeolites.
was only partially perturbed and shifted down to 3190 cm−1 (Fig. 5, sp.
1). This corresponds to a shift ΔνO-H⋯CO]350 cm−1 for HF band, a ty-
Type of sites Absorbance Micro-mesoporous zeolite Y pical value for USY zeolites [45,48], and to a shift ΔνO-H⋯CO]380 cm−1
bands, cm−1 for LF band [45], located possibly in destroyed sodalite cages. The
FAU RFAU1 RFAU2 RFAU3
appearance of small negative peaks at ca. 3550 and 3600 cm−1 in
Concentration of some OH-groups, μmol/g difference spectra after CO adsorption can be due to perturbation of a
Si-O(H)-Al in supercages νOH 89 63 62 55 few bridging Si-O(H)-Al groups polarized by LAS species. It should be
3620–3645 noted that the strength of BAS does not change at the increase of zeo-
(HF)
lites recrystallization degree. The appearance of positive bands at
Si-O(H)-Al in sodalite cages νOH 3570 (LF) 38 30 24 22
3190–3280 cm−1 is accompanied by two broad bands near at 3385*
BAS concentration (by FTIR of adsorbed CO), μmol/g
and 3420* cm−1. However, corresponded negative peaks are not
Strong BAS in faujasite cages, by method I 66 44 38 32
νO-H = 3570–3630 cm−1 νO-H⋯CO
identified. It can be assumed that the appearance of the latter peak is
3190–3280 caused by the perturbation of the acid OH groups attached to tri-
ΔνO-H⋯CO = 350–380 cm−1 by method II 97 72 65 62 coordinated Al atom (bands at 3670 cm−1) [52]. The band at
PA 1140–1125 kJ/mol νCO 2180 3738 cm−1, which is observed as a shoulder to the band at 3746 cm−1
BAS at external surface of by method I 19 26 25 38
in initial spectrum, exhibits also a large shift (ΔνO-H⋯CO]265 cm−1) at
microcrystallites or in νO-H⋯CO 3475
mesopores, higher CO pressure. It demonstrates that these Si-O(H)⋯Al3+ groups
νO-H = 3738 cm−1 are less acidic than bridging Si-O(H)-Al groups in faujasite cages ac-
ΔνO-H⋯CO = 265 cm−1 cording to the value of the low frequency shift of OH vibrations with
PA 1190 kJ/mol adsorbed CO. Besides, the highest pressure of CO close to equilibrium
BAS with PA 1190–1200 kJ/ by method II 50 61 60 79
mol νCO 2170
results in the shift in the intensity of the silanol bands from 3746 cm−1
to ca. 3660 cm−1: a shift of ∼ 90 cm−1 is typical for weak acidic
LAS concentration (by FTIR of adsorbed CO), μmol/g
terminal Si-OH groups [45].
Strong LAS νCO 18 28 33 24
2225–2233 The concentration of BAS (method I) for the zeolite samples is given
Total LAS νCO 47 75 84 71 in Table 3 and Fig. 4B. It can be seen that the concentration of strong
2192–2233 BAS in the faujasite cages (PA 1140–1125 kJ/mol) decreases in the
Total acidity, μmol/g following order: FAU > RFAU1 > RFAU2 > RFAU3, but the con-
Total acid sites by IR CO, 194 208 209 212 centration of BAS on crystallites external surface (PA 1190 kJ/mol)
method II increases in the following order: FAU < RFAU2 ≈ RFAU1 < RFAU3.
by TPD NH3 382 378 349 340
It is shown that the concentration of strong BAS in the faujasite cages
(method I) decreases proportionally to the decrease of micropore vo-
shown in Table 3 and Fig. 4A. The observed alterations are due to the lume, caused by the increase of the degree of parent FAU zeolite re-
partial withdrawal of siliceous and aluminium species from the zeolite crystallization. The concentration of BAS dealing with defect Si-O(H)
framework, the formation of mesopores and the destruction of the local ⋯Al3+ groups increases with the increase of mesopore volume si-
surrounding of the part of Si and Al atoms that leads to the formation of multaneously to the increase of the degree of parent FAU zeolite re-
additional Al-OH and Si-OH groups. crystallization, but not proportionally. We assume that these BAS are
Formation of extraframework Al species under the destruction of located at the external surface of zeolite microcrystallites and in the
framework bridging Si-O(H)-Al groups deals with the increase in the intracrystalline mesopores or in the channels of MCM-41-like material.
concentration of Al-OH groups partially attached to the framework According to IR spectra of adsorbed CO in carbonyl region, surface
(band at 3670–3725 cm−1) and the increase in the concentration of groups in all the samples can be attributed to three types of LAS and
other silanol hydroxyl groups shifted to lower wavenumbers (band at two types of BAS. As shown by way of example for FAU, the adsorption
of CO (Fig. 6) on all the samples leads to the appearance of the

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Fig. 4. Integrated intensity of absorbance

bands of some OH-groups (A), and con-
centration of strong BAS in faujasite cages,
BAS in mesopores and total LAS (by IR data
of CO adsorption) (B) vs. Vmicro/Vtotal of the
zeolites. A: 1) Si-OH terminal groups with
band at 3746 cm−1; 2) Si-O(H)-Al groups in
faujasite cages with band at
3550–3648 cm−1; 3) Si-O(H)⋯Al3+ groups
−1
with band at 3738 cm ; 4) Al-OH groups
with band at 3670–3725 cm−1; 5) Al-OH
terminal groups with band at
3775–3790 cm−1.

Fig. 6. IR difference spectra of CO adsorbed at pressure of 3 mbar and liquid nitrogen

Fig. 5. IR difference spectra in the OH-region between the initial zeolites and those with temperature on 1–FAU; 2–RFAU1; 3–RFAU2; 4–RFAU3. IR difference spectra for zeolite
3.0 mbar of adsorbed CO at liquid nitrogen temperature: 1–FAU; 2–RFAU1; 3–RFAU2; FAU between the initial one and those with increased dosage of adsorbed CO: (a)
4–RFAU3. PCO = 0.2 mbar; (b) PCO = 0.4 mbar, (c) PCO = 0.7 mbar, (d) PCO = 1.0 mbar, (e)
PCO = 2.0 mbar, (f) PCO = 3.0 mbar.

following absorbance bands: (1) 2235–2225 cm−1 relating to CO

complexes with Al3+ ions in pentahedron environment being specific the following order: FAU < RFAU3 < RFAU1 < RFAU2. The con-
structure defects of zeolites (strong LAS), (2) 2216–2210 cm−1 corre- centration of strong BAS determined by method II correlates with the
sponding to LAS of medium strength, (3) 2198–2192 cm−1 relating to ones estimated by method I and the concentration of bridging Si-O(H)-
CO complex with Al3+ ions of alumina clusters (weak LAS) [46], (4) Al groups in the faujasites cages.
2180 cm−1 corresponding to CO complex with strong BAS (PA TPD NH3 profiles of parent (FAU) and recrystallized (RFAU) zeolites
1140–1125 kJ/mol), (5) 2170 cm−1 relating to CO complex with BAS, are shown in Supporting Information, Fig. S5. The TPD NH3 profiles of
characterized by PA 1190–1200 kJ/mol (due to the content of the samples exhibit the shape typical for USY [53]. Recrystallization of
Na2O < 0.02 wt%) and (6) 2157 cm−1 corresponding to CO complex parent FAU zeolite into RFAU(1–3) samples is accompanied by the
with Si-OH groups [45]. Concentrations of LAS and BAS estimated by decrease of the peak centered at 380–390 °C. It can be seen from TPD
method II are given in Table 3. It can be seen, that the concentration of NH3 profiles (Fig. S5) that the intensity of this peak decreases in the
strong and total LAS is minimal for parent FAU zeolite and increases in following order: FAU > RFAU1 > RFAU2 > RFAU3. This result is in

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Fig. 7. HRTEM images for FAU-Al2O3 and

RFAU3-Al2O3 supports.

good agreement with the decrease of the concentration of strong BAS in size distribution of recrystallized zeolites, used for supports preparation
the faujasite cages with PA 1140–1125 kJ/mol, determined by IR (Fig. 2). Besides, mesopores with diameter up to 12 nm are also ob-
spectroscopy of adsorbed carbon monoxide (Table 3), as well as with served.
the decrease of the intensity of the bands in the region of ca. The surface area and pore volume of the obtained supports, con-
3500–3630 cm−1 (Fig. 3) assigned to bridging Si-O(H)-Al groups taining 30 wt% of zeolite and 70 wt% of alumina, are in the range of
(Brønsted acid sites, which are connected with the zeolite framework). 358–409 m2/g and 0.55-0.68 cm3/g respectively (Table 4). The in-
It should be noted that the total concentration of acid sites estimated by corporation of 3.0 ± 0.1 wt% of Ni and 9.8 ± 0.5 wt% of Mo (cor-
IR data of CO adsorption is slightly lower, than the concentration of responds to 18–19 wt% of NiO and MoO3 content) in the supports in-
acid sites determined by TPD NH3 (Table 3). Possibly, this is due to duces a decrease of a specific surface area and pore volume. After
smaller kinetic diameter of ammonia molecule compared to carbon metals incorporation surface area decreases by 17–32%, while total
monoxide molecule. The total concentration of acid sites determined by pore volume decreases by 24–31%. Changes in pore size distribution
TPD NH3 slightly decreases with zeolite recrystallization. after metals incorporation (Fig. S7) show that active metals in NiMo/
RFAU-Al2O3 samples are localized in mesopores generated by zeolite
3.3. Properties of supports and catalysts recrystallization (pores with diameter from 2.3 to 4.5 nm) as well as in
mesopores with higher diameter.
The morphology of the obtained supports containing 30 wt% of
zeolite was studied by HRTEM (Fig. 7). HRTEM images for FAU-Al2O3 3.4. Hydrocracking activity and selectivity
and RFAU3-Al2O3 show the presence of the areas related to alumina,
zeolitic microporous structure of the parent FAU zeolite and meso- Hydrocracking catalysts prepared by loading the similar amount of
porous fragments of recrystallized zeolite. The surface of zeolite crys- Ni and Mo on the FAU-Al2O3 and RFAU-Al2O3 supports were sulfided
tallites is decorated with alumina particles, which have needle-shaped and evaluated for catalytic performance in VGO hydrocracking.
morphology. At the same time, the morphology of the both parent and Catalytic tests were carried out with non-pretreated feedstock (Table 1)
recrystallized zeolites is maintained. Thus, it can be assumed that the and the studied catalysts were loaded in stacked beds containing NiMo/
method for the support preparation used in this work preserves the Al2O3 as the top layer, NiW/ASA-Al2O3 as the interlayer and NiMo/
structure of micro-mesoporous zeolite materials. FAU-Al2O3 or NiMo/RFAU-Al2O3 as the bottom layer. The top layer and
Textural properties of the supports and catalysts as well as the the interlayer catalysts were used for the transformation of sulfur- and
content of Ni and Mo in the catalysts are given in Table 4. The corre- nitrogen-containing compounds in order to prevent zeolite catalyst
sponding nitrogen adsorption-desorption isotherms and pore size dis- from poisoning. In this case, NiMo/FAU-Al2O3 and NiMo/RFAU-Al2O3
tributions are shown in Figs. S6 and S7 . FAU-Al2O3 and RFAU-Al2O3 catalysts were tested in the presence of NH3, H2S and small amounts of
supports show type IV isotherms according to the widely known clas- unconverted organic hetero compounds. Table 5 summarizes the results
sifications [54,55]. The nitrogen adsorption-desorption isotherms of the of NiMo/FAU-Al2O3 and NiMo/RFAU-Al2O3 testing in VGO hydro-
NiMo-containing catalysts are quite similar to that of the corresponding cracking. The net conversion of VGO at 390 °C is between 15.5 and
supports (Supporting Information, Fig. S6). The metals incorporation in 20.8% for all catalysts and middle distillates yield is in the range of
the supports does not change the shape of hysteresis loop. The differ- 25.4-28.5 wt%. Thus, the difference between the studied catalysts in
ence is in the lower amount of adsorbed nitrogen in comparison with hydrocracking activity is not significant at 390 °C process temperature.
the corresponding support. Plots of pore size distribution (Supporting Increase of the process temperature to 410 °C leads to the significant
Information, Fig. S7) show that FAU-Al2O3 have mesopores mainly with increase of VGO conversion and middle distillates yield. For NiMo/
2–12 nm in diameter. It can be assumed that these mesopores are FAU-Al2O3 catalyst, VGO net conversion is 62.1% and middle distillates
contributed mostly by alumina. RFAU-Al2O3 supports are characterized yield is 46.5 wt% at the selectivity of 61.5%. NiMo/RFAU1-Al2O3 and
by the presence of mesopores with a very narrow pore size distribution NiMo/RFAU2-Al2O3 catalysts have similar selectivity to middle dis-
and a maximum at about 3 nm. This is in good agreement with the pore tillates but this selectivity is achieved at much higher VGO net

Table 4
Characteristics of the supports and catalysts.

Support SBET, m2/g Pore volume, cm3/g Catalyst Ni, wt% Mo, wt% SBET, m2/g Pore volume, cm3/g

FAU-Al2O3 403 0.62 NiMo/FAU-Al2O3 3.0 9.3 274 0.44

RFAU1-Al2O3 409 0.68 NiMo/RFAU1-Al2O3 2.9 9.8 341 0.51
RFAU2-Al2O3 358 0.55 NiMo/RFAU2-Al2O3 3.1 10.1 298 0.42
RFAU3-Al2O3 386 0.61 NiMo/RFAU3-Al2O3 3.1 10.3 277 0.42

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Table 5
The results of VGO hydrocracking: VGO net conversion, products yield and selectivity to middle distillates.

Catalyst NiMo/FAU-Al2O3 NiMo/RFAU1- Al2O3 NiMo/RFAU2- Al2O3 NiMo/RFAU3- Al2O3

Temperature, °C 390 410 390 410 390 410 390 410

VGO net conversion, % 19.5 62.1 17.0 75.5 20.8 69.2 15.5 60.2
Products yield, wt%
Gas 0.6 3.3 0.3 5.5 0.4 4.0 0.1 2.8
Naphta < 130 °C 2.4 17.0 1.3 20.0 1.6 19.1 0.4 12.6
MDa 130–360 °C 26.4 46.5 25.6 53.0 28.5 49.9 25.4 49.7
Residue > 360 °C 70.5 33.2 72.8 21.5 69.4 27.0 74.1 34.9
MD selectivity, % 76.9 61.5 83.0 60.6 83.9 60.9 89.6 69.7

a
Middle distillates.

conversion of 75.5 and 69.2% respectively. As a result, these catalysts

provide significantly higher middle distillates yield in comparison with
NiMo/FAU-Al2O3. The ratio between the yield of middle distillates to
the yield of naphtha is 2.6–2.7 for three aforementioned catalysts.
Another situation is observed for the NiMo/RFAU3-Al2O3 catalyst,
which was prepared with the zeolite Y with the higher degree of re-
crystallization (RFAU3). NiMo/RFAU3-Al2O3 has similar to NiMo/FAU-
Al2O3 VGO net conversion. At the same time, NiMo/RFAU3-Al2O3
provides substantially higher middle distillates yield due to higher se-
lectivity. The ratio between the yield of middle distillates to the yield of
naphtha is 3.9 for this catalyst. For all studied catalysts sulfur and ni-
trogen content in the obtained middle distillates is lower than 10 ppm
and 5 ppm respectively.
The hydrocracking performance of the catalysts strongly depends on
the acidity and the accessibility of acid sites of zeolite component. Fig. 8. Selectivity to middle distillates at 50% VGO net conversion vs. ratio of con-
Brønsted acidity of the support is generally known to be mainly re- centration of BAS in mesopores to concentration of strong BAS in faujasite cages (by IR
sponsible for the acid catalyzed reactions during hydrocracking data of CO adsorption).
[14,56]. The accessibility of acid sites is determined by zeolite textural
properties and has considerable effect on hydrocracking, since diffusion surface of microcrystallites or in mesopores, which represent defect
limitations in the pores of zeolite can decrease the activity, by limiting silanol OH groups located in the close vicinity of the Lewis acid site (Si-
access to the active sites, and/or the selectivity, by causing products to O(H)⋯Al3+). It is clearly seen from Fig. 8 that the increase of the ratio
be retained in the pores, leading to overcracking [10]. In general, the of BAS in mesopores to strong BAS in faujasite cages results in sig-
increase of mesopore volume of the zeolite component is beneficial for nificant increase of the selectivity to middle distillates. Obviously, re-
hydrocracking [19–21] as the presence of mesopores facilitates trans- acting molecules would rather undergo secondary cracking reactions in
port of bulky hydrocarbon molecules in the zeolite catalyst due to zeolite micropores than in mesopores due to diffusional limitations that
higher diffusion rates in larger pores. will lead to the formation of side products.
Despite the fact that the parent FAU zeolite already contains sub-
stantial contribution of mesopores, which are beneficial for the middle
4. Conclusions
distillate selectivity, the microporous part of zeolite still responsible for
the decreased activity and selectivity due to limited accessibility of
A series of micro-mesoporous zeolites Y of similar chemical com-
active sites and secondary cracking reactions in micropores. This effect
position with varying mesoporosity was obtained by recrystallization of
is clearly seen in Table 5, which shows that the activity of the hydro-
dealuminated zeolite Y. The contribution of mesoporosity in re-
cracking catalyst increases with the increase of mesoporosity of parent
crystallized materials was varied by adjusting the content of alkali and
FAU generated by mild recrystallization (RFAU1 and RFAU2), re-
the temperature of hydrothermal treatment. The increase of re-
flecting the greater accessibility of zeolite active sites for bulky mole-
crystallization degree resulted in the increase of mesopore to micropore
cules of the heavy feedstock. At the same time, the selectivity to middle
volume of zeolite Y due to the formation of additional intracrystalline
distillates also increases. The reason for this can be due to better
mesoporosity. According to FTIR spectroscopy, the nature of the OH-
transport of bulky molecules in the pore system of recrystallized zeoi-
groups in recrystallized zeolites was similar to that of the parent fa-
lites, which results in the decrease of residence time of products and
jausite. FTIR spectroscopy of adsorbed CO revealed, that the increase of
therefore minimization of secondary cracking reactions. Deeper re-
mesopore to micropore volume by recrystallization is accompanied by
crystallization (RFAU3) leads to the increase of hydrocracking catalyst
the decrease of the contribution of strong Brønsted acid sites in faujasite
selectivity to middle distillates, however the activity decreases, most
cages and the increase of contribution of Brønsted acid sites at the
probably due to the decrease of the concentration of strong BAS in
external surface of microcrystallites or in mesopores, which represent
faujasite cages (Table 3).
defect silanol OH groups located in the close vicinity of the Lewis acid
The comparison of the catalytic properties of a series of Y zeolites
site (Si-O(H)⋯Al3+). NiMo based hydrocracking catalysts were pre-
with similar chemical composition but varying mesoporosity in-
pared using parent and recrystallized micro-mesoporous zeolites and
troduced by recrystallization reveals the correlation between the se-
evaluated in the hydrocracking of a VGO. The highest VGO net con-
lectivity of NiMo/Y-Al2O3 hydrocracking catalysts and the concentra-
version of 75.5% and middle distillates yield of 53.0 wt% were
tion of different types of acid sites of zeolites (Fig. 8). The increase of
achieved over NiMo/RFAU1-Al2O3 catalyst obtained with micro-me-
mesopore to micropore volume of zeolite Y by recrystallization is ac-
soporous material with low degree of recrystallization. This effect is due
companied by the decrease of the contribution of strong BAS in fauja-
to the improved accessibility of active sites, easier transport of bulky
site cages with the increase of contribution of BAS at the external
molecules provided by mesopores, on the one hand, and optimal

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zeolitic acidity, on the other hand. The highest selectivity to middle 10272–10276.
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