Accepted Manuscript

Title: Guard Bed Catalysts for Silicon Removal During

Hydrotreating of Middle Distillates

Authors: K.A. Nadeina, M.O. Kazakov, A.A. Kovalskaya, V.I.

Danilevich, O.V. Klimov, I.G. Danilova, D.F. Khabibulin,
E.Yu. Gerasimov, I.P. Prosvirin, V.A. Ushakov, K.V. Fedotov,
D.O. Kondrashev, A.V. Kleimenov, A.S. Noskov

PII: S0920-5861(18)31184-2
DOI: https://doi.org/10.1016/j.cattod.2018.11.075
Reference: CATTOD 11811

To appear in: Catalysis Today

Received date: 20 July 2018

Revised date: 29 October 2018
Accepted date: 30 November 2018

Please cite this article as: Nadeina KA, Kazakov MO, Kovalskaya AA, Danilevich VI,
Klimov OV, Danilova IG, Khabibulin DF, Gerasimov EYu, Prosvirin IP, Ushakov VA,
Fedotov KV, Kondrashev DO, Kleimenov AV, Noskov AS, Guard Bed Catalysts for
Silicon Removal During Hydrotreating of Middle Distillates, Catalysis Today (2018),
https://doi.org/10.1016/j.cattod.2018.11.075

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Guard Bed Catalysts for Silicon Removal During Hydrotreating of Middle
Distillates

K.A. Nadeinaa,*, M.O. Kazakova,*, A.A. Kovalskayaa, V.I. Danilevicha, O.V. Klimova, I.G.

Danilovaa, D.F. Khabibulina, E.Yu. Gerasimova, I.P.Prosvirina, V.A. Ushakova, K.V.

Fedotovb, D.O. Kondrashevb, A.V. Kleimenovb, A.S. Noskova

a
Boreskov Institute of Catalysis SB RAS, Pr. Lavrentieva 5, 630090 Novosibirsk, Russia

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b
PJSC «Gazprom Neft», str. Pochtamtskaya, 3-5, 190000, St Petersburg, Russia

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*Corresponding authors.

E-mail addresses: lakmallow@catalysis.ru (K.A. Nadeina), kazakov@catalysis.ru (M.O.

Kazakov). U
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Graphic abstract
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Highlights:

 NiMo/Al2O3 catalysts with different texture were studied in Si removal.

 Increase in the surface area of Al2O3 leads to the increase in OH groups amount.
 Catalyst with the highest surface area has the highest Si capacity.
 The higher silicon capacity, the lower hydrodesulfurization activity.
Abstract

The influence of textural characteristics of NiMo/Al2O3 on silicon capacity and hydrotreating

activity has been investigated so as to develop guard-bed catalyst for silicon removal from middle
distillates. Series of NiMo/Al2O3 catalysts with a specific surface area from 150 to 210 m2/g and
an average pore diameter from 21.1 to 10.5 nm have been synthesized. The difference in textural
characteristics has been achieved by variation of aging time and temperature of hydrothermal
treatment of boehmites. The boehmites, supports and catalysts were studied by various physico-

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chemical methods: XRD, nitrogen adsorption-desorption, IR spectroscopy, UV-Vis, 1H NMR,

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Al NMR, XPS, SEM, HRTEM. Catalysts were tested in hydrotreating of diesel fuel

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contaminated with decamethylcyclopentasiloxane as a model silicon compound. It is shown that
the increase in aging time and temperature of hydrothermal treatment of initial boehmites results

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in the decrease of OH groups concentration per 1 g of an alumina support. The increase of the OH
groups content leads to higher silicon capacity, while HDS activity of catalysts decreases. The

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study of catalysts surface after reaction showed that Si located on a support surface and did not
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cover directly active component particles. However, its location on the support near edges of active
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component particles could result in the decrease of HDS activity due to limited accessibility of the
active sites.
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Keywords: Hydrotreating, Demetallization, Silicon removal, Alumina, Textural Characteristics

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1 Introduction

In modern oil refinery, hydrotreating (HDT) is one of the key technologies to produce clean
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fuels. It includes wide range of units with diverse operating conditions. Despite of the fact that
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hydrotreating processes exist for more than 70 years, they are still being changed. In recent years,
the HDT technologies are developing to the conversion of heavy oils, which are characterized by
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a large number of different contaminants and require severe conditions to achieve high conversion.
Therefore, new HDT catalysts are becoming necessary. Such catalysts are the systems based on
Ni, Co, Mo and W sulfides. Deactivation of such catalysts are still a critical problem due to
continuous tendency in worsening of oil quality at necessity to maintain maximal activity of
existing catalysts.
One of the reasons for deactivation of hydrotreating catalysts is the poisoning by silicon
compounds. The presence of silicon in petroleum fractions is caused by polydimethylsiloxanes
(PDMS), which are added to increase the recovery of crude oil from the reservoir and as defoamers
to avoid foaming in various processes, such as coking, visbreaking, steam cracking or distillation
[1,2]. Total concentration of silicon can vary from a few hundred μg/kg to several mg/kg [3,4]. As
it was shown in [5], thermal decomposition of PDMS results in the formation of cyclic siloxanes
as the major products. The same situation was observed for PDMS degradation under thermal
cracking of hydrocarbons [6,7]. The formed silicon species distillate from light to heavy petroleum
cuts depending on their boiling points: the higher the boiling point, the greater molecular weight

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of cyclic siloxanes [8].

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NiMo/Al2O3 are commonly used as the guard-bed catalysts from silicon poisoning [9]. In
numerous works, silicon species are shown to adsorb strongly on a catalyst support and, after long

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time on stream, these species can reduce the accessibility of Ni-Mo-S sites for feed molecules

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resulting in the decrease in HDS activity. Silicon contamination has a strong negative impact
especially on HDN activity and a negative impact on HDS activity [10,11]. Usually, a
concentration below 15 wt% of SiO2 in a catalyst can be tolerated during the cycle of a commercial
catalyst [12]. U
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In catalysts with Al2O3 support, deposition of silicon species is an activated and
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diffusionally controlled reaction between silicon species and alumina OH groups. Silicon is
adsorbed on the entire catalyst surface, resulting in surface, pore volume and active site losses.
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Only few studies discussing the problems of HDT catalysts poisoning by silicon species
are available [10,11,13,14]. For example, Kellberg et al. studied spent Ni-Mo/Al2O3 HDT catalysts
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from coker naphtha by the combination of 29Si MAS, 29Si CP/MAS and 13C CP/MAS [10]. It was
shown that silica species on catalyst surface consisted mainly of bulk SiO 2 carrying the surface
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species SiOH, Si(OH)2, ≡SiCH3, =SiOHCH3 and =Si(CH3)2. All of these species interact with Al-
O and AlOH groups of the support.
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In the work of Perez-Romo et al. [11], commercial Ni-Mo/Al2O3 HDS catalyst was tested
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in silicon removal from coker naphtha. It was shown that the amount of the silicon adsorbed on
the catalyst increased over the first few days. However, after 30 days on stream, an increasing
difference between the content of measured silicon and the calculated values (in the case of
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complete removal of Si from the feed) was observed. This finding suggested that the reaction
kinetics is diffusion limited. In addition, the authors observed leakage effect of Si from catalyst
due to the decreased amount of available active sites. Moreover, the authors experimentally
established that sorption of up to 10 wt% of Si from the feed resulted in the decrease of the catalyst
surface area from 292 m2/g to 140 m2/g after 700 days on stream.
Unfortunately, the literature data mostly refer to the removal of silicon from coker naphtha,
whereas this problem also concerns heavier fractions, in particularly diesel fractions, which can
also comprise light gas oils from coker and visbreaker. However, information on catalysts for
silicon removal from diesel fractions is very scarce. One of the most important differences in diesel
fractions from coker naphtha is the greater size of molecules involved in the reaction. In this case,
there is a possibility that diffusional limitations will significantly influence silicon capacity of a
catalyst. Therefore, it is necessary to find the compromise between a high surface area, a pore
diameter and a pore volume to provide maximal silicon capacity. In addition, it is known that
silicon pick-up depends on unit operating temperature, i.e. the amount of deposited silicon

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increases with the increase of the process temperature [8,15]. Concerning diesel fractions, it is

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necessary to take into account that the HDT process temperature for diesel fractions is higher
comparing to HDT of coker naphtha and, consequently, it may lead to the need to increase the pore

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volume to avoid pore plugging or to increase surface area to increase silicon capacity of a catalyst.

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In both cases, a reduce of the breakthrough of silicon to the underlying catalyst layers will be
achieved.
In addition to silicon removal, guard bed catalysts should have medium HDS and HDN
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activity. Thus, there is a trade-off for the guard bed catalyst between Si pick-up capacity and HDS
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activity. Activity of catalysts in hydrodesulfurization also depends on textural characteristics of
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catalysts due to a change in the morphology of active metals, as well as, the interaction of silica
compounds with its surface groups.
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Obviously, in this case, it is necessary to study the influence of textural characteristics of

guard-bed catalysts on Si removal from diesel fractions. Therefore, in this study the series of
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NiMo/Al2O3 catalysts with different textural characteristics have been synthesized and studied.
The main parameters, which effect silicon capacity and HDS activity, have been defined.
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2. Experimental
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2.1 Preparation of supports and catalysts

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Alumina supports were prepared from aluminum hydroxides, which were synthesized by
hydration of thermoactivated gibbsite in different conditions. The method of synthesis is described
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in [16].
Aluminum hydroxides were prepared by the following way:
1) Hydration of centrifugal thermal activation (CTA) product in a solution of nitric
acid with an acid module of 0.04 (mol HNO3/mol Al2O3), T = 50°C, solid to liquid ratio 1:5 and
duration 2 hours;
2) Washing the hydrated product of CTA with distilled water;
 3) Separation of the liquid and solid phases by filtration;
4) Hydrothermal treatment of the filter cake in a solution of nitric acid in a Parr 4520
autoclave with a volume of 2 liters (USA, Parr Instrument Company);
5) Spray drying of the colloidal solution containing alumina monohydrate in YC-015
dryer (China, Pilotech) at an air outlet temperature of 130-150°C.
Conditions of hydrothermal treatment of CTA product are given in Table 1.
The supports were prepared by extrusion of a kneading paste. The preparation of kneading
pastes was carried out by peptizing the powder of alumina monohydrate with aqueous ammonium

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solution (0.09 mol NH3/mol Al2O3) in Z-blade mixer with continuous stirring of the formed paste

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for 30 minutes. The obtained paste was extruded using a fluoroplastic spinneret with trilobe holes
by VINCI extruder at P = 3.5–4.0 MPa and plunger moving at 1.2 mm/s. Supports with a cross-

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section diameter of granule 2.5±0.2 mm were prepared in the present work. Then, granules were

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dried at 120ºС in air flow for 4 h and calcined at 550ºC in air flow for 4 h.
Catalysts were prepared by similar preparation technique. The supports were impregnated
by an aqueous solution prepared from nickel carbonate NiCO3·mNi(OH)2·nH2O (48 wt% of Ni),
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ammonium heptamolybdate (NH4)6Mo7O24·4H2O and citric acid with mass ratio of the
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components 1:2.9:2.5. Then catalysts were dried at 120°C for 4 h and calcined at 550ºC for 4 h.
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Metals contents in catalysts were 6.0±0.1 wt% of Mo and 2.0±0.1 wt% of Ni. Designation of
supports and catalysts is given in Table 1.
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2.2 Sulfiding and HDS testing of catalysts

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All of the catalysts were sulfided and subsequently tested in hydrotreating of model feed
in a fixed bed reactor. In all cases, catalysts were in the form of fraction with a particle size of
0.25-0.5 mm. A sample portion equivalent to 2 cm3 of a catalyst was placed in the isothermal zone
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of the reactor. Sulfiding was performed with a dimethyl disulfide solution (20 g/L) in a straight-
run diesel fraction with 0.25 wt% of sulfur in the following conditions: a pressure of 3.8 MPa, a
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volumetric hydrogen/sulfiding mixture ratio of 300 and a stepwise elevated temperature (140, 240,
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340°C). This method of sulfiding is optimized version of the one described in [17]. This method
is similar to the sulfiding techniques used at refineries.
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Diesel fraction (0.25 wt% of S) with addition of decamethylcyclopentasiloxane as a model

silicon compound was used as a feedstock. The content of Si in the feedstock was 166 ppm. Testing
was carried out in the following conditions: LHSV of 10 h-1, a volumetric H2/feed ratio of 550,
P=3.8 MPa, T=360°C. After start up, during first 24 h time on stream catalysts were tested in HDS
of diesel fraction (without silicon addition) to measure initial HDS activity. Then the feedstock
was switched to diesel fraction containing model silicon compound. Testing was carried out until
the silicon content at the inlet and outlet of the reactor became the same. Silicon content in the
feedstock and in the liquid products was determined by the mass spectroscopy with inductively
coupled plasma using Agilent 7700 ICP-MS (Agilent Technologies). HORIBA SLFA-2100 was
used to measure residual sulfur content in liquid products. Difference in a residual sulfur contents
for each HDS point was in precision of measurement for Horiba equipment. Uncertainty of
measurements for our sulfur content is ±5 ppm. General uncertainty for testing was ±10 ppm. A
silicon capacity of the catalysts was determined by chemical analysis of spent catalysts.

2.3 Investigation techniques

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2.3.1 XRD

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X-ray diffraction (XRD) studies were carried out using a HZG-4 diffractometer (Freiberger

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Präzisionsmechanik, Germany) equipped with a copper anode (Cu Kα) with a wavelength of
1.54184 Å.

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2.3.2 SEM
Scanning electron microscopy (SEM) were carried out using a scanning electron

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microscope JSM-6460 LV (JEOL), whose primary electron energy was 15-20 keV. The local
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chemical composition was determined using an accessory for elemental analysis of Oxford
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Instruments.
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2.3.3 HRTEM

HRTEM images were obtained on a JEM-2010 electron microscope (JEOL, Japan) with a
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lattice-fringe resolution of 0.14 nm and points 0.194 nm at an accelerating voltage of 200 kV. The
high-resolution images of the periodic structures were analyzed by the Fourier method. Samples
for HRTEM examination were prepared on a perforated carbon film mounted on a copper grid.
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The particle size of the initial AlOOH powders and the slab length of the sulphided active
components were defined using the average data for at least 500 particles.
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2.3.4 27Al MAS NMR and 1H MAS NMR

1
Н and 27
Al NMR were performed using a Bruker Avance 400 NMR spectrometer
operating at 9.4 T with frequencies 400 and 104.3 MHz, respectively. All spectra were recorded
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for samples spinning under magic angle (MAS) at 14 kHz using a Bruker 4 mm MAS H/X probe.
The spectra were obtained by the Fourier transform of the free induction decay (FID). In the case
of 27Al, FID excitation was performed using a single-pulse sequence, the width of the excitative
π/12 pulse was 1 μs. The delay between pulses was 1 s. The number of accumulations was 2048
scans. In the case of 1H, FID excitation was carried out using the echo of the sequence 90 τr 180
τr, the duration of the π/2 pulse was 5 μs. The time τr was one rotation of the rotor. Relaxation
time was 2 s. The number of accumulations was 1024 scans. The experiments were carried out at
room temperature. As external standards of the scale of chemical shifts, TMS for 1H and 0.3 M
Al(NO3)3 aqueous solution for 27Al were used.
Prior to the 1H NMR spectroscopy, the samples were dehydrated under a vacuum of 10-3
bar at 450°C for 6 hours, then sealed in glass ampoules. The ampoules were opened immediately
before the NMR spectra were recorded in a dry box purged with Ar.
2.3.5 Nitrogen adsorption-desorption.

The textural properties of the catalysts and supports were determined by nitrogen

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physisorption at 77ºK using an ASAP 2400 (USA) instrument. Prior to analysis, samples were

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subjected to a N2 flow at 150ºC and 30 atm for 2 h. The BET surface areas were calculated from
the nitrogen uptakes at relative pressures ranging from 0.05 to 0.30. The total pore volume was

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derived from the amount of nitrogen adsorbed at a relative pressure close to unity (in practice, P/P0

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= 0.995) by assuming that all accessible pores had been filled with condensed nitrogen in the
normal liquid state. The pore size distribution was calculated using the BJH method for the

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desorption branch of the isotherm. The obtained results have measurement error 5%.
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2.3.6 IR spectroscopy
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IR spectra were recorded by Shimadzu FTIR-8300 spectrometer within the spectral range
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of 700–6000 cm-1 with a resolution of 4 cm-1 and 300 scans for signal accumulation. The powders
of alumina supports were pressed into thin self-supporting wafers (0.007-0.010 g/cm2) and
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activated in the special IR cell at 500ºC for 1 h in air and further at 550ºC for 2 h in dynamic
vacuum of 10-3 mbar. In the presented spectra, the absorbance was normalized to sample wafer
density.
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2.3.7 UV–Vis DRS

UV-Vis diffuse reflectance spectra (UV-Vis DRS) of the oxide NiMo catalysts (calcined
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in air at 550°C) were recorded using a UV-2501 PC Shimadzu spectrometer with an IRS-250A
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diffusion reflection attachment in the 11000-54000 cm-1 range. The measurements were performed
in a 2 mm quartz cell in air at room temperature using the BaSO4 as a reference.
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2.3.8 XPS

Photoelectron spectra were recorded using SPECS spectrometer with PHOIBOS-150-

MCD-9 hemispherical energy analyzer (Al Kα, irradiation, hν = 1486.6 eV, 200 W). The samples
were supported onto double-sided conducting copper scotch tape. Binding energy (BE) scale was
preliminarily calibrated by the position of the peaks of Au4f7/2 (BE = 84.0 eV) and Cu2p3/2 (BE =
932.67 eV) core levels. The binding energies of peaks were calibrated by the position of the C1s
peak (BE = 284.8 eV) corresponding to the surface hydrocarbon-like deposits (C-C and C-H
bonds) [18]. The survey spectra were recorded at pass energy of the analyzer of 50 eV, while that
for the narrow spectral regions was 20 eV. The atomic ratio of elements was calculated from the
integral intensities of photoelectron peaks corrected by corresponding atomic sensitivity factors
[19].
2.3.9 CHNS

The total carbon, hydrogen, nitrogen and sulfur content in the catalysts were determined with
a CHNS elemental analyzer Vario EL Cube (Elementar Analysensysteme GmbH). HCNS analysis

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data are expressed in reference to fresh catalysts.

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3. Results and discussion

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3.1. Alumina monohydrate powders

Investigation of aluminum hydroxides (Fig. 1) showed that all powders had phase

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composition similar to pseudoboehmites. The X-ray particle size was determined by the Selyakov-
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Scherrer formula. It is shown that the change in the temperature and time of hydrothermal
treatment results in changing of the average particle size, namely, there is an increase in the size
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of coherent scattering region (Dcsr) from 6.5 to 14.0 nm for the samples from B1 to B5. Considering
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the accuracy of the method ±0.5 nm at a particle size up to 50 nm, it can be argued that there is a
linear dependence of the particle size on the time and temperature of hydrothermal treatment in
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the series of B1-B5 samples. The longer time and higher temperature of hydrothermal treatment,
the larger the average particle size of primary crystals.
Scanning electron microscopy was used to investigate the surface of the patterns. The
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images of various surfaces obtained under different hydrothermal conditions are shown in Fig. 2.
At a sufficiently high resolution, it was found that the particles were agglomerates of needles of
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different lengths. Moreover, the longer the time and higher temperature of hydrothermal treatment,
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the higher crystallization degree of the needles.

According to HRTEM (Fig. 2), B1 and B2 samples contain particles with needle shape
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with the size ~20 nm, whereas B3, B4 and B5 samples contain the mixture of fine-crystalline
particles and long needles. The size of fine-crystalline particles increases from 2-3 nm to 200-300
nm, while the size of needles increases from 10-20 nm to 10 µm at the increase of the aging time
from 8 to 24 h. The correlation of the HRTEM, SEM and XRD data allows us to see the correlation
between the average sizes of the primary particles and the agglomerates of these particles, namely,
an increase in the size of the primary particles resulted in the enlargement of the agglomerates.
 As a result, it can be concluded that the change in temperature and time of hydrothermal
treatment during synthesis of alumina monohydrate powders provides a preparation of poorly
crystallized boehmites or pseudoboehmites. These pseudoboehmites have different size of primary
crystallites and large agglomerates. The higher temperature and the longer time of hydrothermal
treatment, the larger size of pseudoboehmite particles. It can be expected that the change in particle
size will result in the change in the number of contact points between the particles at the stage of
the supports kneading and, as a result, in the change in the texture characteristics of the supports.

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3.2 Supports and catalysts

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According to XRD, all supports are γ-Al2O3 (Fig. S1). The surface areas and pore structure

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were determined by nitrogen adsorption analysis. The study of the supports showed that the
increase of the temperature and time of hydrothermal treatment of alumina monohydrates resulted

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in the decrease of the specific surface area of the supports from 241 to 156 m2/g and in the increase
of the average pore diameter from 10.2 to 21.6 nm (Table 2). In addition, there is a significant

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increase in the pore volume from 0.61 to 0.85 cm3/g. Thus, the series of the supports with different
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specific surface areas and the average pore diameters was prepared by variation of the preparation
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conditions of alumina monohydrates powders.
Due to the fact that the initial powders of alumina monohydrates differ in particle size, one
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could expect a change at the coordination level of aluminum atoms. Therefore, all the prepared
samples were studied by the 27Al NMR method to determine the coordination state of aluminum
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atoms.
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The Al NMR spectra of the samples (Fig. 3) are a superposition of two non-Gaussian
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lines, which is caused by the influence of the second order of the quadrupole interaction and is
broadened due to the statistical distribution of interaction parameters. To provide correct analysis
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of the spectra, modeling of the shape of the lines using the Czjzek model was used [20]. The
following parameters of the spectra were calculated: the parameters of quadrupole interaction CQ,
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distributions of these parameters, isotropic chemical shifts δISO, and relative intensities of the lines.
The shape of the lines (the broadening due to the second order of the quadrupole interaction (QI))
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for different samples is almost the same, which is due to the same parameters of the QI for all
samples. The modeling showed that the parameters varied insignificantly. The greatest change
between the samples was observed in the line intensities. All calculated parameters are presented
in Table 3.
Table 3 shows that chemical shifts as well as QI parameters are almost the same for
different samples. There is a monotonic decrease in line intensities and, consequently, in
AlO6/AlO4 ratios from the sample Al1 to Al5. Thus, AlO6/AlO4 ratio changes in the range of 1.36-
1.67. The values of this ratio for γ-Al2O3 in the literature [21,22] varies from 1.7 to 2.0 that slightly
overcome the values determined in present work according to Czjzek model. It should be noted
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that Czjzek model has been used to calculate the parameters of Al NMR spectra of aluminas
quite recently. The resulting parameters using this model are more correct in comparison with
earlier models data, since aluminum oxides are amorphous systems. Recently, there are reported
simulation of 27Al MAS NMR spectra for γ-Al2O3 using the Czjzek model that has been effective
in resolving Al sites in the disordered oxides [23].

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In the range of 17-40 ppm, there is the line with a low intensity for all samples. This area

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is characteristic for 5-coordinated aluminum, which local surrounding is significantly distorted. It
results in the high values of QI parameters in comparison with AlO4 and AlO6 and, therefore, larger

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line width. The low intensity of the line, combined with its large width, leads to the fact that it is

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not possible to model correctly the line shape in the 17-40 ppm region. Nevertheless, it is obvious
that the intensity of the line corresponding to AlO5 increases monotonically in the Al1-Al5 series.
To determine the possible composition of the OH groups, 1H NMR spectra were recorded.
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The spectra are superposition of several lines, the decomposition of which is a mathematically
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incorrect problem and requires additional information about the possible number of lines and their
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position. The decomposition of the spectra and the assignment of the lines of 1H NMR spectra for
γ-Al2O3 based on the two-dimensional heteronuclear 27
Al-1H NMR spectroscopy D-HMQC are
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given in [24]. The spectra in [24] were obtained in a high field (18T) and at a high rotation speed
(20 kHz), which makes it possible to select data on the number of lines and their shifts as a starting
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point for the deconvolution of the spectra obtained in this work.

In [24], the authors decomposed 1H NMR spectra of γ-Al2O3 into 5 main groups:
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- terminal ОН groups OH-µ1-AlIV in the range of 0-0.2 ppm;

- bridged ОН groups OH-µ2-(AlVI,Aln) in the range of 0.8-2.3 ppm;
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- bridged ОН groups OH-µ2-(AlV,Aln) in the range of 1.5-2.2 ppm;

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- bridged ОН groups OH-µ2-(AlIV,Aln) in the range of 1.9-2.5 ppm;

- bridged ОН groups OH-µ3-(Aln)3 in the range of 2.5-4.0 ppm.
To determine the exact number of observable lines and their chemical shifts, the additional
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experiments on T2 relaxation (spin echo sequence) are employed by varying the interpulse delay
τr in the spin echo sequence. The interpulse delays τr synchronized with sample rotation
frequencies (14 kHz) are varied 1, 5, 10 and 40 rotational periods. This approach facilitates to
discriminate the 1H NMR lines of different spin-spin relaxation time T2 providing a basic
knowledge on their number and positions (see Fig. S2). Several fitting parameters as chemical
shifts and line widths can be fixed. The line intensity is derived from spin echo experiment with
τr = 1 corrected according T2 values for each lines.
The spectra (Fig. 4) contain clearly visible four lines of one terminal and three bridged OH
groups (Table S1). In general, one can assert that there is a step-by-step decrease of concentrations
of all OH groups. Total concentration of OH groups normalized per unit weight decreases in the
series of the samples Al-1 (Σ = 1), Al-2 (Σ = 0.95), Al-3 (Σ = 0.87), Al-4 (Σ = 0.75), Al-5 (Σ =
0.71). However, there are no tendencies referring to definite type of groups.
The IR spectra of Al2O3 supports in the region of the OH groups stretching vibrations

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recorded after outgassing at 823 K are reported in Fig. 5. The spectra of the surface hydroxyl

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groups of all studied alumina supports contain the main vibration bands at ca. 3790, 3775, 3728,
3685 and 3590 cm-1, which are typical for -Al2O3 [25,26].

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In the series Al1Al3Al5, there is a proportional decrease in intensities of almost all

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absorption bands of isolated hydroxyl OH groups. The exceptions are bands at 3775 and 3790 cm-
1
, whose integrated intensity decreases more significantly. These bands are assigned to terminal

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OH groups over one tetrahedrally coordinated Al ion (3790 cm-1) and over one octahedrally or
tetrahedrally coordinated Al ion in a nonvacant environment (3775 cm-1) [25–27]. The decrease in
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the number of OH groups observed by IR is well correlated with the decrease in the AlO 6/AlO4
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ratios. These data are in good accordance with the data in [9], where it is shown that such changes
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are caused by the increase in the amount of OH groups coordinated to tetrahedral aluminum. It
was noted that there is a relative increase in the integral intensity of the band at 3590 cm-1, which
corresponds to multicoordinated [25] or H-bonded [27] OH groups in the series Al1  Al3  Al5
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that is caused by changes in Al coordination.

To define correlation of OH groups on specific surface areas of the supports, total
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concentrations of isolated hydroxyl groups was calculated from integrated intensity of bands at
3830 - 3610 cm-1 using molar integral absorption coefficients Ao = 1.5 cm/-mol for unassociated
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hydroxyls [28]. The total concentration of the isolated surface hydroxyl groups decreases in the
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line Al1(1366 -mol/g)  Al3(1274 -mol/g)  Al5(1088 -mol/g). The total concentration of the
isolated OH groups on a specific surface area basis increases in the line Al1(5.7 -mol/m2) 
Al3(6.5 -mol/m2)  Al5(7.0 -mol/m2). Surface OH-density of alumina supports varies in the
A

line Al1(3.4 OH`s/nm2)  Al3(3.9 OH`s/nm2)  Al5(4.2 OH`s/nm2) and corresponds to hydroxyls
cover of various aluminas at ca. 2.3÷5.5 OH`s/nm2 [27] when dexydroxylation temperatures are
similar. It can be asserted that the increase in the density of OH groups per unit of the surface at
the increase of pore diameters results in a relative decrease of concentration of some isolated ОН
groups and in an increase of concentrations of H-bonded ОН groups describe above.
 The IR and NMR data correlate well with each other and textural characteristics of the
supports and catalysts. The data show direct dependence of the composition of the hydroxyl cover
of the supports on the specific surface area values. The main conclusion is that a decrease of the
support surface area results in the decrease of OH groups concentration per 1 g of the support; at
the same time, concentration of OH groups per 1 m2 increases. On the one hand, an increase in the
amount of OH groups (for high surface area supports and catalysts) should increase the number of
sites, which are involved in the sorption of silicon compounds. On the other hand, when diffusion
limitations being present, it would be better to use the supports and catalysts with higher pore

T
diameters and pore volumes. In this case, an increase in the number of OH groups per unit of the

IP
support surface (for the samples with lower surface areas) can also positively affect silicon
capacity. However, higher surface OH-density presumably may increase the probability of

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interaction of one Si atom with two Al atoms resulting in blockage of higher amount of OH groups

SC
by one molecule of silicon compound.
Figures 6 and 7 show the nitrogen adsorption-desorption isotherms and pore size
distribution obtained through the Barrett–Joyner–Halenda method for supports and catalysts.
U
Presence of the hysteresis loop at P/P0 between 0.7 and 1.0 indicates the existence of mesopores
N
[29]. The main difference between the samples is the height of the isotherms. It is interesting that
A
the higher temperature and aging time of boehmites, the greater height of an isotherm, i.e. the
greater the pore volume. Also, it is noted that there is a rapid increase in nitrogen adsorption
M

capacity at P/P0 above 0.8 that allowed us to propose the presence of macropores [30]. The change
in the shape of isotherms is caused by the change of pores shapes. Thus, it is known that isotherms
ED

of Al1-Al3 samples are characteristic for the systems with cylindrical type of pores, while
isotherms of Al4 and Al5 samples correspond to slot-like pores or wedge-shaped pores narrowed
PT

on the one side [31,32]. Therefore, changes in sizes of primary particles and agglomerates leads to
the change in the shape of pores.
E

Supporting of active metals results in the decrease of the height of isotherms that correlates
CC

with the decrease of the textural parameters (Table 2). However, supporting of metals do not
change the shapes of isotherms that indicates uniform distribution of active metals in the pores of
the supports without changing of pores shapes.
A

The synthesized supports significantly differ in pore size distributions. Al1 support, which
is characterized by lower hydrothermal treament temperature of the boehmite, has bimodal pore
size distribution with the maximums at 6.3 and 15.1 nm. The increase in the temperature and the
decrease in the time of hydrothermal treatment results in redistributions of pore diameters, namely,
the amount of pores in the range of 10-20 nm increased, while the peak at 4-10 nm decreased.
Further increase of the aging time led to the formation of larger amount of mesopores in the range
of 10-50 nm. In general, it can be stated that an increase of time and temperature of hydrothermal
treatment of alumina monohydrate powders results in the formation of wider pore size distribution
with preferential formation of mesopores with the diameters of 10-60 nm. Supporting of active
metals leads to the decrease in the volume of all pores that is characterised by the decrease of the
distribution curve in the whole range of pores presence. Such tendency indicates uniform
distribution of active metals in pores of the supports.
The diffuse reflectance UV–Vis spectra of the NiMo/Al2O3 catalysts in the oxide state are
reported in Fig. 8. The intense adsorption band at about 220–320 nm could be assigned to the

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ligand-metal charge transfer (LMCT) O2−→ Mo6+. The CT band centered at ca. 225 nm and 250-

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300 nm for all samples can indicate the presence of isolated tetrahedral coordinated Mo sites and
polymolybdate-like structure containing MoOh ions, correspondingly [33]. Ni2+ (O2−→ Ni2+ LMCT

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transitions) can also give a contribution to absorption in this UV region (250-320 nm) [34].

SC
The edge energies of the LMCT transitions slightly decrease in the series of the catalysts
GB-Si-1 (Eg = 3.67 eV)  GB-Si-2 (3.61 eV)  GB-Si-3 (3.58 eV)  GB-Si-4 (3.57 eV)  GB-Si-

U
5 (3.45 eV). The red shifts of the absorption edge of molybdenum polyhedra in the spectra of
NiMo/Al2O3 catalysts with the increase of their pore diameters can be explained by low increase
N
of the average particle size of molybdenum oxide species (MoxOy domain) in these catalysts [35].
A
In [9], it is shown that hydrothermal treatment of alumina monohydrates, which results in the
crystallite growth of the corresponding -Al2O3 supports, is accompanied by evident increase in
M

the average slab length and stacking number of (Ni)MoS2 phases.

In addition to the CT bands due to overlapping of Mo and Ni species, which appear in the
ED

UV region, the visible spectra of these catalysts exhibit bands in the 500–900 nm region. These
bands are associated only with d→d transitions of Ni2+ species. For all samples, there is a doublet
PT

at 600 and 635 nm with a shoulder at 550 nm, which can be assigned to 3T1 → 3T1 (P), 3T1 → 1E
and 3T1 → 1T2 transitions of tetrahedral Ni (II) ions in the Al2O3 lattice, and adsorption band at
E

710 nm can be ascribed to the 3A2g → 3T1g(P) transitions of octahedrally coordinated Ni (II) ions
CC

[36–38]. These bands are characteristic of nickel aluminate (NiAl2O4) that can be described as a
partial inverse spinel. It indicates that Ni(II) ions occupy both octahedral and tetrahedral sites of
the oxygen lattice. The intensity of the bands (600 and 635 nm), which are assigned to the
A

interaction between Ni ions and a support, decreases in the line GB-Si-2  GB-Si-3  GB-Si-4 
GB-Si-1  GB-Si-5. On the other hand, the bands at 380-410 nm and 710-720 nm can be ascribed
to the 3A2g → 3T1g(P) and 3A2g → 3T1g (F) transitions of octahedrally coordinated Ni (II) ions and
are fingerprints for NiO [38,39]. A slight increase in the intensity of these bands, especially the
380-410 nm band, which characterizes dispersed NiO, is observed for the samples with increasing
pore size, i.e. from GB-Si-1 to GB-Si-5.
 In addition, the spectra of all samples contain absorption maximum at 773 nm, which is
together with the band at 710-720 nm, can be ascribed to the d-d transitions of octahedrally
coordinated Ni (II) ions in NiMoO4 [40]. Intensities of these bands slightly increases with
increasing pore size, i.e. from GB-Si-1 до GB-Si-5.
Therefore, UV–Vis data suggest the existence of three types of Ni species in our catalysts:
highly dispersed and isolated Ni2+ interacting with alumina (NiAl2O4 spinel-like phases), well-
dispersed supported NiO phases, as well as NiMoO4 nanoparticles. The concentration of NiMoO4
increases for the samples with increasing pore diameters, i.e. from GB-Si-1 to GB-Si-5. The

T
increase in the amount of NiMoO4 phase indicates the reduction of the interaction between nickel

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and the support as in [41]. It is possible that such increase in the amount of NiMoO4 phase and the
decrease of the interaction is caused by a decrease in a surface area of a support and decrease of a

R
dispersion of the active component particles. Obviously, the formation of NiMoO4 phase should

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result in selective synthesis of NiMoS phase, while Ni2+ and NiO species would result in the
formation of low active individual components.
HRTEM data of sulfide catalysts are given in Table 4. Comparison of HRTEM images of
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alumina monohydrates and γ-Al2O3 supports on their base shows that particle morphologies did
N
not change during preparation of the supports. Sulfide active component particles seen on
A
microphotographs of all catalysts have the morphology similar to the Co-Mo-S phase in high active
hydrotreating catalysts [42,43]. Average stacking numbers are similar for GB-Si-1-GB-Si-4
M

samples and slightly increases for GB-Si-5 sample. On the contrary, average slab length values
significantly change. There is a parabolic dependence of a slab length in the series with the highest
ED

values for GB-S-1 and GB-Si-5 samples and the lowest value for GB-Si-3 sample. It is not obvious,
why there is such dependence of the active component particle morphology on the conditions of
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their preparation. However, the parabolic dependence of a slab length correlates with the change
in the interaction of nickel particles with a support. There is the lowest slab length for the samples
E

with the strongest interaction between active component and a support, while the samples with
CC

lower interaction between active component and a support have the largest slab length. It should
be noted that active component particles may adsorb on OH groups of alumina supports. Therefore,
there could be an influence on silicon capacity due to the difference of NiMo morphology.
A

Moreover, catalysts for silicon removal are also catalysts with a mild HDT activity and the
morphology of active component particles could significantly influence their HDT activity. In this
case, adsorption of silicon on definite OH groups of alumina support could result in the decrease
of accessibility of more or less Ni-Mo-S active sites due to proximity to active component particles
and decrease the activity of catalysts.
 3.3 Catalytic activity

Catalysts have been tested in hydrotreating of diesel fraction contaminated with a model
silicon compound. As it is mentioned in the Introduction section, PDMS is used in oil refining to
avoid foaming during different processes. However, PDMS decomposes to series of cyclic
siloxanes under thermal exposures. In this work, decamethylcyclopentasiloxane (boiling point -
210°C) was used as a model silicon compound in order to reproduce the silicon species present in
diesel fractions. The higher Si content in comparison with industrial streams was taken in order to
ensure rather fast (about 10 days on-stream) attainment of ultimate silicon capacity of the catalyst.

T
During testing of catalysts, silicon capacity (g of Si/g of a fresh catalyst) and

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desulfurization degree (Fig. 9а) have been determined. Obviously, the silicon capacity increases
with increasing specific surface area of the catalysts. However, it is noted that the highest rise in

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silicon capacity occurs at transition from 120 to 170 m2/g. The catalysts with the specific surface

SC
area of 170-200 m2/g have rather similar silicon capacities. The further increase in the surface area
results in the considerable increase of the silicon content in a spent catalyst.

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Comparison of NMR and IR data allow us to conclude that silicon capacity directly
N
depends on the amount of OH groups on the alumina surface (Fig. 9b). Notably, the concentration
of OH groups per 1 g of a support increases, while the concentration of OH groups per 1 m2
A
decreases.
M

Desulfurization activity was measured at the start of the run for all catalysts to obtain
information on the real HDS activity. Initial HDS activity was measured during the first 24 hours
ED

of the tests, when only diesel fraction without silicon compound was fed to the reactor, before the
switch to diesel fraction contaminated with model silicon compound. It should be noted that
several independent tests of HDS activity for some of the studied catalysts showed that steady state
PT

conditions were reached (Fig. 9a, red). It is interesting that the measured conversions are rather
similar. However, there is a tendency that they correlate well with silicon capacities of the samples.
E

The higher specific surface areas, the higher HDS activity. Considering sulfide catalysts prior to
CC

the reaction, a parabolic dependence of the slab length on the specific surface area of the catalysts
is observed. However, there is no dependence of the HDS activity on the morphology of the active
A

component particles. Moreover, according to UV-Vis data, concentration of NiMoO4 decreases

with increasing specific surface area and increasing amount of Ni, which interacts with an alumina
support and does not included into NiMo phase composition. Therefore, the only explanation of
the difference in the starting HDS activity could be better dispersity of the active component
particles on the support surface.
After starting of the tests with the feed contaminated by Si, HDS activity of all catalysts
decreases day-by-day. The first 3-4 days, a significant decrease was observed. Then, decrease of
the activity is much slower and achieves steady state at about 2 weeks after tests start.
Desulfurization degrees at the end of the test after saturation by silicon are significantly lower than
the initial ones. The dependence curve of HDS activities at the end of the run is inversely
proportional to the specific surface area of the catalysts (Fig. 9a, blue). It should be noted that the
residual sulfur content grew rapidly enough from the beginning to the end of testing to reach a
steady state. At the same time, the silicon content in the feed and in the product was the same when
catalytic tests ended. Regarding the state of active metals in spent catalysts, it can be noted that,
according to XPS data (Table 5), Ni and Mo particles are mainly in the NiMoS phase - 60-70%

T
Mo in the form of Mo4+ and 40-60% Ni as Ni2+. Examples of decomposition of Mo3d XPS spectra

IP
of the spent catalysts are shown in Fig. S3. Such values are characteristic for hydrotreating
catalysts in which a predominant fraction of the active component is present as a NiMoS phase.

R
CHNS data of the sulfide catalysts after testing show that active metals are in the form of sulfides,

SC
however, the amount of sulfur is slightly lower than expected that can be caused by the washing
of the samples. An interesting fact is that, according to CHNS and XPS data, the active metals are
in the form of a NiMoS phase even at high silicon contents. It is noted that the ratios of Mo/Si,
U
Ni/Si and Al/Si increase with a decrease in the surface areas of the samples, which is associated
N
with a decrease in the dispersion of active metals and, as a consequence, an increase in the number
A
of metals per unit surface with a decrease in the number of OH groups occupied by Si.
Investigation of the spent catalysts by HRTEM and EDX methods showed that silicon present on
M

catalysts surface as globular amorphous SiO2 particles. Microphotograph (Fig. 10) shows the
fragment of GB-Si-5 catalyst. SiO2 particles determined by EDX are highlighted by red color. It
ED

can be seen that SiO2 particles do not overlap the sulfide particles of the active component (they
are shown by black arrows). Thus, there is no direct blocking of active metals. It is in agreement
PT

with the results obtained in [10,11,13]. In these studies it was shown that silicon containing species
interacted with OH groups of an alumina support. However, there were no evidence that Si species
E

cover active component particles. Moreover, the authors in [11] showed that there was no decrease
CC

of HDS and HDN activities due to a long period of time. But when the content of Si becomes high,
HDN activity decreases at first due to the decreased access of the promoter atom. Therefore, there
is no or probably small covering of active component particles. In our case, the decrease in HDS
A

activity can be explained by high coverage of catalysts surface by Si atoms and greater surrounding
of active metals by large silicon containing species. On the other hand, there could be some
influence of coke present in the catalysts. According to CHNS data (Table 6), the amount of coke
in catalysts increases with increasing surface area and increasing content of silicon in catalysts. It
can be assumed that coke in catalysts can block the active component particles. In this case, it
should cause higher decrease of HDS activity of the catalysts with smaller surface area. However,
there is a controversy situation for the series GB-Si-1-GB-Si-5. It can be assumed that coke
somehow interacts with Si and accumulate it. It is known that in HDS process catalysts accumulate
most coke amount during first hours on stream [44]. Then, the amount of coke increases slightly.
Therefore, the coke could form the layer on the support surface at first covering part of OH groups
of an alumina. Then Si species can deposit on free OH groups of a support as well as on the coke
layer.
Then, the difference in the HDS activity of the catalysts can be explained as follows (Fig.
11). In catalysts with a high specific surface area, active component particles locate relatively far

T
from each other as compared to catalysts with a low surface area. Therefore, upon catalysts

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poisoning by silicon compounds, SiO2 particles surround active component particles, thereby
making it difficult for the feed molecules to access the active sites (Fig. 11, top). With a decrease

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in the surface area, an access to the OH groups of a support is limited by the sorption of NiMo

SC
particles on them. The particles of the active component are closer to each other, consequently,
their blocking by SiO2 particles is reduced (Fig. 11, bottom part). Therefore, the decrease in the
activity of catalysts in HDS reactions is less pronounced for catalysts with a low surface area in
comparison with catalysts with a larger surface area. U
N
A
4 Conclusion
The series of NiMo/Al2O3 catalysts with different texture characteristics for removal of Si
M

during hydrotreating of middle distillates was studied. It was found that an increase in the specific
surface area of supports led to an increase in the number of OH groups and tetrahedral Al in an
ED

alumina per 1 g of a support and a decrease in the density of OH groups per 1 m 2 of the surface.
At the same time, an increase in the number of OH groups resulted in an increase in the silicon
PT

capacity of the catalysts, while reducing their HDS activities. Investigation of the spent catalysts
made it possible to find out that silicon was deposited on the surface of the catalysts in the form of
E

globular particles of amorphous silicon oxide, which did not block directly active component
CC

particles, but made it difficult for feed molecules to access active sites. At the same time, the active
metals remained in the NiMoS phase in all catalysts. In general, it can be concluded that, upon
hydrotreating of middle distillates, catalysts with a higher surface area have higher silicon capacity,
A

but the activity of these catalysts in HDS reactions falls in proportion to the silicon content.
Therefore, to achieve a high capacity for silicon during hydrotreating of middle distillates, it is
necessary to use guard bed catalysts with high surface area. On the other hand, the decrease in
HDS activity is less pronounced for the catalysts with a low surface area, which can be more
tolerant for silicon poisoning in comparison with catalysts with a larger surface area.
 Acknowledgements
The work was supported by Ministry of Education and Science of the Russian Federation:
Project No. 14.604.21.0155, identification number of the project RFMEFI60417X0155.
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Figure 1 – XRD patterns of alumina monohydrate samples
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Figure 2 – SEM (on the left) and HRTEM (on the right) images of alumina monohydrate
samples
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Figure 3 - 27Al MAS NMR spectra of the supports
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Figure 4 – The spectra of 1H NMR of the supports

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Figure 5 - IR spectra of Al2O3 supports in the OH region: (1) Al1, (2) Al3, (3) Al5. In the
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presented spectra, the absorbance was normalized to a sample wafer density

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Figure 6 – Nitrogen adsorption-desorption isotherms

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Figure 7 – Pore size distribution for a) supports, b) catalysts

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Figure 8 - UV–Vis DR spectra of NiMo/Al2O3 catalysts with different supports: (1) GB-Si-1, (2)
GB-Si-2, (3) GB-Si-3, (4) GB-Si-4, (5) GB-Si-5
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Figure 9 – а) Silicon capacity and desulfurization degree for the catalysts, b) dependence of

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silicon capacity on concentration of OH groups of the support
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Figure 10 – The fragment of the HRTEM image of GB-Si-5 catalyst after testing: black arrows
point sulfide active component, red area points SiO2

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Figure 11 – Possible scheme of active component blockage by SiOx particles

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Table 1 – Conditions of alumina monohydrate preparation, designation of supports and catalysts

Alumina monohydrates
Sample B1 B2 B3 B4 B5
T, °С 150 160 160 160 160
Aging time, h 8 6 8 12 24
Supports
Sample Al1 Al2 Al3 Al4 Al5
Catalysts
Sample GB-Si-1 GB-Si-2 GB-Si-3 GB-Si-4 GB-Si-5

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Table 2 – Textural characteristics of the supports and catalysts

Supports Catalysts
SSA, Vpore, Dpore, SSA, Vpore, Dpore,
Sample Sample
m2/g cm3/g nm m2/g cm3/g nm
Al1 241 0.61 10.2 GB-Si-1 209 0.55 10.5
Al2 215 0.69 12.9 GB-Si-2 203 0.63 12.3
Al3 195 0.75 15.4 GB-Si-3 186 0.69 14.9
Al4 167 0.85 20.3 GB-Si-4 171 0.80 18.7
Al5 156 0.84 21.6 GB-Si-5 151 0.81 21.3

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Table 3 – Parameters for the spectra modeling
Sample δISO, ppm CQ, MHz ΔCQ, MHz IntY, % AlO6/AlO4
13.34 4.90 3.16 62.57
Al1 1.67
71.0 6.25 6.59 37.43
13.68 4.90 3.16 59.12
Al2 1.45
71.38 6.25 6.59 40.88
13.29 4.90 3.16 59.53
Al3 1.47
71.38 6.25 6.59 40.47
13.34 4.90 3.16 58.57
Al4 1.41
71.0 6.25 6.59 41.43
13.42 4.90 3.16 57.61
Al5 1.36

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Table 4 – Morphology of active component particles

Catalyst Average slab length, nm Average stacking number

GB-Si-1 5.3 2.2
GB-Si-2 4.4 2.1
GB-Si-3 3.6 2.2
GB-Si-4 4.4 2.3
GB-Si-5 5.7 2.6

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Table 5 – Surface concentrations of Ni and Mo and ratios of Mo/Si, Ni/Si , Al/Si in catalysts after
reaction
Catalysts Mo4+,% Mo5+,% Mo6+,% Ni0,% Ni2+,% Mo/Si Ni/Si Al/Si
GB-Si-1 68 19 13 58 42 0.12 0.04 2.2
GB-Si-2 68 19 12 48 52 0.15 0.06 3.4
GB-Si-3 63 20 17 43 57 0.14 0.05 3.1
GB-Si-4 61 20 19 39 61 0.15 0.06 3.2
GB-Si-5 70 17 13 41 59 0.22 0.08 4.1

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Table 6 – CHNS data for the sulfide catalysts after reaction
Catalysts С, wt% Н, wt% N, wt% S, wt%
GB-Si-1
4.9 1.8 0.2 4.3
GB-Si-2
4.6 1.9 0.1 3.4
GB-Si-3
3.7 2.3 0.2 3.9
GB-Si-4
3.2 2.1 0.2 3.9
GB-Si-5
3.3 2.4 0.3 5.1

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