γ-Al2O3 hydrotreating catalysts obtained using flash calcination of gibbsite and precipitation method

Journal Pre-proof Comparison of alumina supports and catalytic activity of CoMoP/␥-Al2 O3 hydrotreating catalysts obtained using flash calcination of gibbsite and precipitation method E.A. Stolyarova, V.V. Danilevich, O.V. Klimov, E. Yu. Gerasimov, V.A. Ushakov, I.A. Chetyrin, A.E. Lushchikova, A.V. Saiko, D.O. Kondrashev, A.V. Kleimenov, A.S. Noskov

PII:

S0920-5861(19)30511-5

DOI:

https://doi.org/10.1016/j.cattod.2019.09.019

Reference:

CATTOD 12471

To appear in:

Catalysis Today

Received Date:

15 April 2019

Revised Date:

30 July 2019

Accepted Date:

13 September 2019

Please cite this article as: Stolyarova EA, Danilevich VV, Klimov OV, Gerasimov EY, Ushakov VA, Chetyrin IA, Lushchikova AE, Saiko AV, Kondrashev DO, Kleimenov AV, Noskov AS, Comparison of alumina supports and catalytic activity of CoMoP/␥-Al2 O3 hydrotreating catalysts obtained using flash calcination of gibbsite and precipitation method, Catalysis Today (2019), doi: https://doi.org/10.1016/j.cattod.2019.09.019

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Comparison of alumina supports and catalytic activity of CoMoP/-Al2O3 hydrotreating catalysts obtained using flash calcination of gibbsite and precipitation method

E.A. Stolyarovaa,*, V.V. Danilevicha,*, O.V. Klimova, E.Yu. Gerasimova, V.A. Ushakova, I.A.

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Chetyrina, A.E. Lushchikovaa, A.V. Saikoa, D.O. Kondrashevb, A.V. Kleimenovb, A.S. Noskova

Boreskov Institute of Catalysis SB RAS, Pr. Lavrentieva 5, 630090, Novosibirsk, Russia PJSC «Gazprom Neft», str. Pochtamtskaya, 3-5, 190000, St Petersburg, Russia

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(*) corresponding author. Tel.: +7 (383) 326 96 69, e-mail addresses: [email protected]

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(E.A. Stolyarova); [email protected] (V.V. Danilevich)

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Graphical Abstract

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Highlights Textural properties of alumina depend on the time of hydrothermal stabilization.

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Alumina samples prepared by hydrothermal treatment have bimodal pore distribution.

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The initial alumina has an impact on the share of CoMoS phase in the catalysts.

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The hydrothermal method is more preferable to obtain CoMoP-catalysts.

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

Abstract

The influence of alumina precursors on catalytic activity CoMoP/Al2O3 hydrotreating

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catalysts has been studied. Alumina precursors were prepared by eco-friendly technology including hydrothermal treatment at different stabilization time of a flash calcined gibbsite. One

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sample was synthesized with the addition of boric acid. A reference sample of pseudoboehmite

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was obtained by precipitation from aluminum nitrate with aqueous ammonia. Alumina precursors, supports and catalysts were studied by XRD, nitrogen adsorption/desorption, XPS,

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HRTEM. CoMoP/Al2O3 catalysts were tested in hydrotreating of model feed and fuel mixture. It is shown that the samples obtained from the product of flash calcination of gibbsite,

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besides pseudoboehmite, also include the amorphous phase, while the reference sample, synthesized by precipitation, is a pure pseudoboehmite. The introduction of boron prevents the

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crystallization of pseudoboehmite. Textural properties of the catalysts depend of initial support: alumina samples prepared by hydrothermal treatment have a bimodal pore distribution with peaks at 60-70 Å and 150-200 Å, the support synthesized through reprecipitation has a unimodal distribution with a maximum at 80 Å. The initial alumina used as a catalyst support has a significant impact on the share of CoMoS phase of type II. The highest activities in the hydrotreating of model feed 3

(dibenzothiophene, quinoline and naphthalene in undecane) and fuel mixture shown catalyst prepared using hydrothermal treatment of flash calcined gibbsite without addition boric acid and with short stabilization time.

Keywords:

flash

calcination,

alumina,

pseudoboehmite,

hydrotreating,

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hydrodesulfurization, hydrodenitrogenation

1. Introduction

Due to strict environmental requirements, many scientists nowadays are engaged with

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the problem of developing high-active catalysts for hydrotreating of diesel fuel.

The properties of the resulting hydrotreating catalyst depend on a large number of

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factors. The catalytic activity depends of composition of an impregnation solution [1–6] and

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conditions of drying and calcination [7–9]. Citric acid is a very popular additive to increase a catalyst’s activity in the hydrodesulfurization (HDS) and hydrodenitrogenation (HDN)

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reactions [10–13]. Addition of acidic components such as phosphorus [14] or boron [14–16] is also widely used way to improve catalytic activity.

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One of the main ways to control properties of hydrotreating catalysts is to change the initial support. It could be done by using alumina [17–20], silica [21,22], silica-alumina [3,23],

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carbon nanotubes [24], titanium dioxide [25] , zirconia [26] or their mixture as a support of the catalysts. But currently, in industry most diesel fuel is produced using CoMo(P) catalysts supported on alumina. The most suitable and frequently used support for hydrotreating catalysts is γ-Al2O3 [14,20,27–29], which is obtained by thermal treatment of boehmite or pseudoboehmite (PBe).

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Given the number of recently published scientific papers [30–33], the interest in the synthesis of boehmite and alumina based on it, especially in transition γ-form, continues to grow. There are three main methods for producing boehmite or pseudoboehmite: 1) hydrothermal treatment of gibbsite [33–35]; 2) a reprecipitation of gibbsite or precipitation from aluminum salts [36,37]; 3) a sol-gel method [38,39]. In the first case, the value of the specific surface area does not exceed 5 m2/g. The second method involves a high consumption of reagents and the formation of large amounts of wastewater (about 300 m3/ton Al2O3). The

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third method is extremely expensive. In the Boreskov Institute of Catalysis a new eco-friendly and accessible method was developed for the synthesis of PBe by hydrothermal treatment of active aluminum

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hydroxyoxide (AAH) [40], obtained via flash calcination of gibbsite [41]. The method has important advantages, namely: the minimal consumption of reagents, the lesser amount of

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effluent, and a high degree of pseudoboehmite purity. γ-Al2O3 based on such a pseudoboehmite

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meets the requirements [42] for supports for hydrotreating catalysts. However, in the scientific literature there is no information about the effectiveness of CoMoP catalysts supported on such γ-Al2O3, compared with catalysts supported on aluminum oxides, obtained by other

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technologies, especially by precipitation.

The aim of this work is to compare alumina supports obtained through the flash

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calcination of gibbsite and the precipitation of aluminum nitrate and the catalytic activity of

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CoMoP catalysts based on them in the hydrotreating reaction of model feed and fuel mixture. 2. Experimental 2.1 Pseudoboehmite preparation Active aluminum hydroxyoxide, also known as CTA product [43], was used as a starting material for the synthesis of PBe by the hydrothermal method, described in [40]. The CTA

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product features are as follows: 100% disordered χ-like Al2O3; SBET=257 m2/g; pore volume (N2) is 0.12 cm3/g; average pore diameter is 3.1 nm; the mass loss under calcination (1000 °C) is 4.8%; the mean volumetric diameter of particles is 24 µm. The hydrothermal treatment temperature of washed active aluminum hydroxyoxide was 150 °C; the aging time was 8 h in all cases; the stabilization time at 70 °C was 4 h (samples H1 and H3) and 24 h (sample H2). Sample H3 was synthesized with the addition of boric acid (mass ratio B:Al=1:22).

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A reference sample (P1) was obtained by precipitating PBe from a solution of Al(NO3)3 by aqueous NH3 at 70 °C and aging time of 5 h under stirring. The pH of the solution was 7.0. Then the gel was filtered and washed with distilled water at 70 °C to remove impurities of

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nitrates. After that, the solid was dried at 120 °C for 24 h.

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2.2 Alumina preparation

Kneading pastes were synthesized by peptizing the powder of PBe with aqueous

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ammonium solution (0.09 mol NH3/mol Al2O3) in Z-blade mixer with continuous stirring of the formed paste for 20-30 min. The obtained plastic paste was pressed through the holes of a

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trilobular spinneret with a diameter of the circumscribed circle of 1.6 mm. Extrudates 2-4 mm long were calcined in a muffle furnace at 550 °C in air flow for 4 h.

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2.3 Catalysts preparation

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Impregnation solutions were prepared using cobalt hydroxide Co(OH)2, ammonium heptamolybdate tetrahydrate (NH4)6Mo7O24·4H2O, H3PO4 and citric acid monohydrate C6H8O7·H2O. Citric acid, cobalt hydroxide, ammonium heptamolybdate and phosphoric acid were successively dissolved in required quantity of distilled water at 50°C. In all instances, the concentrations of active metals in impregnating solutions were chosen to obtain 12.5 ± 0.2 wt.

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% of Mo and 3.5 ± 0.1 wt. % of Co and 1,5±0,1 wt.% of P in the final catalysts. The molar ratio between molybdenum and citric acid was taken as 2 : 1.1. Catalysts were prepared using vacuum impregnation method. The catalysts were dried at 120°C for 4 h in air flow after the impregnation. 2.4 Sulfiding and testing of catalysts Dried catalysts were crashed to get a fraction of 0.25-0.5 mm and were placed into a

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flow glass reactor for gas-phase sulfidation. Sulfiding occurred in H2S flow with 500 h−1 at atmospheric pressure. The process took place at two temperatures: 220°C and 400°C, for 2 h at each temperature [44]. Gas phase sulfiding samples were tested on the hydrotreating of the

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model feed.

The model feed was prepared by adding 2500 ppm S from dibenzothiophene, 200 ppm

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N from quinoline, and 5%w. naphthalene to undecane. Catalytic tests of hydrotreating of the model feed were obtained in a down-flow reactor. 0.1500 g of sulfide catalyst fraction was

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uniformly distributed in the volume of silicone carbide fraction less than 0.25 mm. The temperature of model feed hydrotreating was 280°C. The test conditions were as follows: P =

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3.5 MPa, WHSV = 80 h-1, H2/feed volume ratio = 500 Nm3/m3. Hydrotreating products were analyzed by the PerkinElmer Gas chromatograph Clarus 580.

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15 cm3 of dried catalysts extrudate was placed in the isothermal zone (300 mm long) of the down-flow reactor with the internal diameter of 16 mm [7]. A silicon carbide bed (size of

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particles 3-4 mm) was placed at the bottom of the reactor. Extrudates diluted with SiC particles with size 0.1-0.2 mm at a volumetric ratio 1:2 were located above, and the bed of silicon carbide with the particles size of 3-4 mm was placed on the top of the catalyst [45]. The temperature in the catalyst bed was monitored with a five-point mini thermocouple installed vertically in the central part of the reactor. The training and sulfidation processes occurred for 34 h. In the beginning, a gradual rise in temperature to 140°C took place, at the rate of 25 °C per hour. 7

Drying in the H2 flow for 4 h was made to remove physically sorbed water from the pores of the catalysts. After that, the pressure was gradually increased to 3.8 MPa with wetting the catalyst bed with straight-run gasoil followed by an introduction of the sulfidation feed (2% dimethyl disulfide in gasoil). Liquid-phase sulfidation occurred at two phases: 8 h at 240 oC and at 8 h at 340 °C, heating from 140 °C to 240 °C and from 240 °C to 340 °C was made at 25 °C/h. The condition of sulfidation were P = 3.8 MPa, LHSV = 2 h-1, H2/feed volume ratio = 300 Nm3/m3 [7].

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Liquid-phase sulfided catalysts were tested in the hydrotreating of straight-run gas oil and secondary fractions mixture. The properties of fuel mixture are shown in Table 1.

The condition of catalytic tests were P = 3.8 MPa, LHSV = 2.5 h-1, H2/feed volume ratio

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= 500 Nm3/m3. Tests were carried out at the process temperature of 360 °C. A 24-hour long mode consisted of stabilizing the catalyst for 14 h and sampling the liquid product each 2 h. A

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catalytic activity of the samples in the hydrodesulphurization (HDS) and hydrodenitrogenation

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(HDN) processes was characterized by a residual content of sulfur and nitrogen in the liquid product. The sulfur and nitrogen content was measured by TE Instruments XPLORER. A residual content of aromatics showed a catalytic activity of the samples in the hydrogenation

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(HYD) reactions. The determination of aromatic hydrocarbon types in middle distillates was checked as per ASTM D6591. About 1 g of sample was diluted in 10 mL heptane and next

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injected into a high performance liquid chromatograph Agilent 1260 Infinity. Standard test

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method ASTM D2887 was used for boiling range distribution of petroleum fractions by gas chromatography .

2.5 Characterization High-resolution electron microscopy (HRTEM) images were obtained by a JEM-2010

electron microscope (JEOL, Japan) with a lattice-fringe resolution of 0.14 nm at an accelerating voltage of 200 kV. The high-resolution images of the periodic structures were analyzed by the 8

Fourier method. Samples for HRTEM examination were prepared on a perforated carbon film mounted on a copper grid. The stacking number and the slab length of the sulfide active component were defined using the average data for at least 500 particles. The textural properties of the samples were determined by nitrogen physisorption using an ASAP 2400 analyzer (Micromeritics, USA). The specific surface area was measured by the BET method. The volume of mesopores was calculated by analyzing the integral curve of the pore volume distribution depending on their diameter (along the desorption branch); the

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average pore diameter in Å was calculated from equation D=4000Vp/S, where S is the surface area of a granule.

The content of cobalt, molybdenum, phosphorus, sodium and boron in the samples was

4300 DV spectrometer (PerkinElmer, United States).

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determined by atomic-emission spectroscopy with inductively coupled plasma on an Optima

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The phase analysis by X-Ray diffraction (XRD) was carried out on an HZG-4

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diffractometer (Zeiss, Germany) at a radiation wavelength of 1.54184 Å (scanning range 10°– 75°, with increment of 0.1, accumulation at a point during 10 s). The phase composition of multicomponent hydroxides and aluminum oxides was measured according to previously

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constructed calibration curves, obtained for mechanical mixtures of pure phases (for example γ- and χ-Al2O3). Calibration graphs were built in the coordinates I1/I2 = f (C1), where I1/I2 are

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the intensities of certain lines of different phases, C1 is the weight concentration of one of the

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phases. Quantitative evaluation was performed by determining the ratio of the line intensities for the corresponding phases. In analyzing the system of pseudoboehmite – “amorphous phase”, we took the ratio of the line intensities (0.0.2.) at =.2° and (1.5.2.) at =72° for pseudoboehmite and =67° for the “amorphous phase”. When analyzing the system of γ- and χ-Al2O3, the reference lines correspond to =37.2° (3.1.1.) and =45.9° (4.0.0.) for γ-Al2O3 and =42.6° (2.0.2.) for χ-Al2O3. 9

The bulk crushing strength (BCS) was measured using SMS 1471 or a similar ASTM method 7084-4 t using a bulk crushing strength instrument, VINCI Technologies, France. X-ray photoelectron spectra (XPS) were recorded using a SPECS spectrometer (Germany) with a PHOIBOS-150 hemispherical energy analyser and AlKα irradiation (hν = 1486.6 eV, 200 W). The binding energy scale was preliminarily calibrated using the peak positions of the Au4f7/2 (84.0 eV) and Cu2p3/2 (932.67 eV) core levels. The samples were supported using conductive duct tape. The internal reference method was used for the correct

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calibration of the photoelectron peaks. The C1s peak (Eb = 284.8 eV) corresponded to surface hydrocarbon-like deposits (Csingle bondC and Csingle bondH bonds) accumulated on the surface during the storage under ambient conditions. A low-energy electron gun (FG-15/40,

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SPECS) was used for the sample the charge neutralization.

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3. Results and discussion

3.1 XRD of pseudoboehmite and alumina samples

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Figure 1 shows experimental X-ray diffraction patterns of the pseudoboehmite samples H1-H3 obtained from active aluminum hydroxyoxide, and of comparative sample P1

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synthesized by precipitation, with marked positions of diffraction peaks for pseudoboehmite, which dispersion was estimated. Analysis of the diffraction patterns of aluminum hydroxides

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showed that all the powders obtained through hydrothermal treatment mainly consist of

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pseudoboehmite (Table 2, H1-H3) and a small part of the amorphous phase, while sample P1 is 100% pseudoboehmite. When the stabilization time is increased from 4 hours (sample H1) to 24 hours (sample

H2), the particle size of the sample also increases in all directions, while the phase composition does not change (Table 2). The introduction of boric acid at the stage of the pseudoboehmite synthesis prevents its

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crystallization to some extent, as evidenced by a lower height of reflections characteristic of pseudoboehmite (Figure 1). These results are consistent with the data in [46,47]. Figure 2 shows experimental X-ray diffraction patterns of the alumina samples H1-H3 and P1 obtained by thermal treatment of the corresponding aluminum hydroxides. Since the sample P1 consists only of pseudoboehmite, aluminum oxide based on it is a pure γ-Al2O3, while samples H1-H3 are a mixture of γ-Al2O3 and -Al2O3, which are formed from the pseudoboehmite and the amorphous phase.

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3.2 HRTEM data of pseudoboehmite samples

Figures 3 and 4 show HRTEM data for PBe samples H1-H3 and P1 at different magnifications. Pseudoboehmite samples H1-H3 have a needle-like morphology of particles

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with different length. Compared with sample P1, the agglomerates of particles (needles) of

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sample H2 are 2-3 times wider due to a larger crystallite size and straighter. Needle-shaped particles of samples H1-H3 are not monoliths, but consist of separate crystallites randomly

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joined in the (001) direction. The crystal structure of sample P1 is less ordered. It belongs to the needle-fibrous type and includes lamellar particles in small quantities.

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3.3 Textural characteristics and sodium content of alumina samples Figure 5 shows the curves of the integral and differential distribution of pore volume by

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the pore size according to the low-temperature nitrogen desorption for alumina samples H1-H3

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and P1. Alumina samples of H1-H3 have a wide bimodal pore distribution with peaks at 6070 Å and 150-200 Å (Fig. 5, 1-3). Unlike samples obtained through hydrothermal treatment of active aluminum hydroxyoxide, the support synthesized through precipitation has a unimodal distribution over a narrow pore size range (Fig. 5, 4) with a maximum at 80 Å. An analysis of the nitrogen adsorption-desorption isotherms of catalyst supports (Fig. 6) according to IUPAC classification [48] shows that all alumina samples belong to IV(a) type

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isotherm, which corresponds to mesoporous materials. The hysteresis loops on the adsorption isotherms are of the H1 type, which are characteristic of materials with a narrow range of uniform cylindrical mesopores. The height of the hysteresis loop decreases in the series P1 → H2 → H1 → H3. Increased stabilization time of solutions in the preparation of samples by hydrothermal method leads to an increase in the SBET (Table 3, H1 and H2) and a decrease in the average pore diameter (APD). Boron modification leads to an increase in the SBET and a further decrease in

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the average pore diameter. The specific surface area of alumina supports decreases in the series H3 → P1→ H2 → H1 (Table 3).

The sodium content in samples obtained from the product of flash calcination of gibbsite

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is lower than that obtained by precipitation of aluminum nitrate.

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3.4 Textural characteristics and chemical composition of catalysts Figure 7 shows the curves of the integral and differential distribution of pore volume by

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the pore size according to the low-temperature nitrogen desorption for catalysts H1-H3 and P1. Catalyst samples H1-H3 have the same bimodal distribution, as well as their supports, but the

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peak maxima move in a smaller area. Unlike its support, the sample of catalyst P1 is characterized by a bimodal distribution of pore volume by the pore size (Fig. 7, 4). A

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characteristic inflection point arises at 70 Å on the curve of the integral and differential distribution of pore volume by the pore size of the catalyst sample.

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The accumulated pore volume naturally decreases after the application of the

impregnating solution (Table 3). The pore volume of the catalyst relative to the support is less by 39.3-47.2% (Table 4). It is interesting that the greatest decrease in pore volume for sample P1 falls on the pores 5-10 nm in size, both in absolute values and in relative percentages, whereas for samples H1-H3, a significant decrease in pore volume occurs in a wider range from 50 to 250 Å. The maximum absolute and relative pore volume reduction among supports is 12

observed in H2 sample. The pore volume of 70-130 Å in diameter is an important characteristic for hydrotreating catalysts, since they are believed to be the most preferred for the conversion of hydrotreated molecules [49,50]. The presence of pores with a size of 150-250 Å is also an important characteristic, since the active component becomes better available for more molecules to be converted at the same time. According to the data presented in Table 3, the supports H1, H2, and H3 have a smaller pore volume of 70-130 Å than sample P1. However, after the application

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of the impregnating solution, this volume is reduced by only 0.08-0.12 cm3/g, compared with a decrease of 0.23 cm3/g in the case of sample P1. It should be noted that the P1 support and the catalyst based on it practically do not contain pores with a diameter of 150-250 Å, while the

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volume of such pores for supported on H1, H2 and H3 catalysts is significant.

The specific surface areas of the catalysts are lower than the ones of the supports by more

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than 80 m2/g (Table 3).

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Chemical compositions of catalysts are close (Table 3) and correlate with theoretically proposed values.

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3.5 Bulk crushing strength of alumina supports and catalysts Bulk crushing strength is a very important characteristic for commercial catalysts.

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Currently, industrial plants require the bulk crushing strength of hydrotreating catalysts to be at least 1.5 MPa according to the Shell SMS 1471 or ASTM 7084-4 methods [51] . The strength

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of a catalyst depends on many factors, such as the impregnation, drying [52], calcination [53], and sulfidation conditions [54]. However, the strength of initial supports has the greatest influence on the final catalyst strength (Table 3). The support H1 has the highest bulk crushing strength compared to other samples. BCS increase in the series P1
pseudoboehmite with a needle-like particle shape have the greatest BCS. This trend also exists for catalysts after impregnation of the supports. 3.6 HRTEM data of sulfided catalysts The sulfide catalysts have been investigated by HRTEM to study the influence of different ways of PBe synthesis on the morphology of active component particles. In addition, active components obtained using different methods of sulfidation were studied. According to the reference data, there is a significant difference between an active particle morphology in the

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case of gas-phase and liquid-phase sulfidation [55]. The morphology of the active component have a strong influence on the catalytic activity of the samples. Figures 8 and 9 show HRTEM images of gas-phase (marked with “-G” prefix) and liquid-phase sulfided catalysts (marked

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with “-L” prefix) respectively. Characteristics of active components of different way sulfided

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catalysts supported on alumina H1, H2, H3 and P1 are shown in Table 5. Average slab lengths are close for all catalysts and are 4.2-4.3 nm in case of gas-phase

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sulfided samples and 5.0-5.3 nm in case of liquid phase sulfided catalysts. Average stacking number and average slabs number per 1000 nm2 are close for the samples inside the group with

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different way of sulfidation. However, the active component morphologies between these groups have a significant difference. According to the reference data, average stacking number

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near 1.2±0.1 is typical for liquid-phase sulfided particles. Gas-phase sulfidation results in particles with average stacking number near 2.4±0.2 and lower average slab length (near

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4.0±0.2) then in case of liquid phase sulfidation. Sulfided particles are evenly distributed on the surface of the support; the average slabs number per 1000 nm2 is 58-67 particles for both sulfidation options. According to obtained HRTEM data, the initial alumina used as a catalyst support do not have a significant impact on the morphology of active particles of sulfided hydrotreating catalysts. Differences in the parameters of the active component are within the error limit for 14

catalysts supported on different supports. However, it is the active component morphology obtained by using liquid-phase and gas-phase ways of sulfidation that should be the reason of difference catalytic activity in the model feed hydrotreating process. 3.7 XPS data of sulfided catalysts The sulfided catalysts have been studied by XPS. Hydrotreating CoMo-catalysts have a Mo4+ state with binding energy (BE) value of 228.9 ± 0.1 eV and Co2+ state with BE = 778.9 ± 0.1 eV [56–58]. The binding energy in the S2p spectrum is 162.0 eV [59]. To confirm the

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formation of the active Co-Mo-S phase, ∆E values were calculated as ∆E1=E(Mo)-E(S) and ∆E2=E(Co)-E(S) [60], which is one of the parameters to confirm the formation of the active Co-Mo-S phase. Data obtained for sulfide catalysts are consistent with the reference data (Table

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6).

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Deconvolutions of Mo3d and Co2p spectra were made. According to the data obtained, a ratio between Mo 4+, Mo 5+ and Mo 6+ depends on the initial support and the way of the

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catalyst sulfidation. The highest part of Mo 4+ contains in the gas phase sulfided catalysts and supported on H2 (79.9%), H3 (79.3%) and P1 (80.6%). In case of gas phase sulfided catalysts

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supported on H1, the share of Mo4+ is lower (78.9%). Nevertheless, another tendency is observed in case of liquid phase sulfidation: the Mo4+ content increases in the series

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P1→H1→H3→H2. It could be explained by different mechanisms of sulfidation and different role of support in the process of CoMoS-active phase formation. A share of cobalt in the

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CoMoS-phase increase in the series H3→H2→H1→P1 for both ways of sulfidation. Thus, the gas phase sulfidation results in catalysts containing a higher share of cobalt and

molybdenum in CoMoS-phase than the liquid phase sulfidation. In case of gas phase and liquid phase sulfidation, the catalyst supported on P1 have a highest part of CoMoS-active phase. 3.8 Catalytic tests

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Gas phase catalysts were tested in the hydrotreating of model feed (2500 ppm S from dibenzothiophene, 200 ppm N from quinoline, 5%w. naphthalene in undecane). The conditions were T = 280 °C, P = 3,5 MPa, WHSV = 80 h-1, H2/feed volume ratio = 500 Nm3/m3. The results of conversion of DBT, quinoline, and naphthalene are shown in the Table 7. Conversions of the components were calculated by following formula: 𝐶𝑜𝑛𝑣 =

𝐶0 − 𝐶 ∙ 100% 𝐶0

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where C0 is the initial content of the component, and C is the content of the component after hydrotreating process. Hydrogenation of naphthalene and DBT take place in the hydrotreating process of model feed. Naphthalene transforms to tetralin under these conditions, but DBT could turn into biphenyl (BPh), phenylcyclohexane (PhCH) or bicyclohexane. The mechanism

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is shown in [61]. In this work, the presence of bicyclohexane didn’t observed in the liquid

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product; the product conversion of DBT were BPh and PhCH (Table 7). The conversion of quinoline was determined using data on residual content of nitrogen obtained by TE Instruments

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XPLORER.

The results of DBT conversion for the catalysts are close (38-40%), but the catalyst

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supported on alumina marked as H2 show the highest HDS activity and the highest activities in the processes of naphthalene HYD and conversion BPh to PhCH. This catalyst shows the lowest

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hydrodenitrogenation activity (conversion of quinoline is 44% vs 58-65% in case of other samples). The share of CoMoS-active phase in the sulfide catalyst and textural characteristics

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of the catalyst could explain it. Due to a sufficient pore volume of 70–130 Å and 150–250 Å in diameter (Table 3), as well as a sufficient specific surface area and average pore diameter, the texture characteristics of the sample are optimal for the transformation of model molecules such as naphthalene and DBT. Low activity in the HDN process is typical for high HDS activity and is explained by the competitive HDS and HDN processes. The catalyst supported on alumina with boron addition (H3) has somewhat less HDS activity, but this sample demonstrates a high 16

activity in the reaction of naphthalene HYD and conversion BPh to PhCH than sample H2. The catalyst supported on alumina prepared by precipitation of aluminum nitrate (P1) shows the lowest HDS and HYD of naphthalene activities, but this sample have the highest conversion of quinoline in the sample series. It can be assumed that the active component on the P1 surface has a greater affinity for quinoline molecules, while the active component becomes unavailable for dibenzothiophene and naphthalene molecules. Liquid phase sulfided catalysts were tested in the hydrotreating of straight-run gas oil

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and secondary fractions mixture. The condition of catalytic tests were P = 3.8 MPa, LHSV = 2.5 h-1, H2/feed volume ratio = 500 Nm3/m3. Testing were carried out at the process temperature of 360 °C. Characteristics of the liquid product are shown in Table 8.

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Residual contents of sulfur and nitrogen are important characteristics for diesel fuel. According to [62], a residual content in commercial diesel fuel has to be less than 10 ppm.

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Given 10 ppm of S in the product, the process temperature is a parameter of the catalyst

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efficiency. To demonstrate the difference between the samples, the process of fuel mixture hydrotreating was occurred at the temperature less than the temperature of 10 ppm S obtaining. The results obtained at this work show that catalysts supported on H1 provide a liquid product

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with the lowest sulfur content (13.4 ppm) compared to other samples at 360 °C. The catalysts supported on H2 show 22.0 ppm of residual sulfur and also demonstrate the lowest

ur

hydrodenitrogenation activity due to the competitive nature of HDS and HDN processes. It

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could be explained by the morphology of active component and textural properties of the samples. The catalyst deposited on H1 has a larger volume of pores with a diameter of 150250 Å than all other samples (Table 3). It also has a large pore volume of 70-130 Å than samples of the H1, H2 and H3 series. The average pore diameter of this sample is 140 Å. These factors make the active sulfide catalyst component more accessible to hydrotreated molecules of the

17

fuel mixture, which have a much more complex structure than the components of the model feed. After hydrotreating, the content of monoaromatics (MA) increases from 19.6 to 27.828.1 wt. %. It is due to hydrogenation of diaromatics (DA) and polyaromatics (PA) [63]. Also, the hydrogenation of monoaromatics takes place. A residual content of DA and PA are 5.3-5.7 wt. % and 0.6 wt. % respectively. It should be noted that hydrogenation activity of the catalyst supported on H1 is a bit higher than that of other samples, but this difference is not so noticeable

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as for hydrotreating of the model feed. Hydrotreating process lets to get a lighter product then the initial fuel mixture. In case of all catalysts, the initial boil point reduces by 24 °C, and the final boiling point becomes

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361°C. The 50% boiling temperature is 285-286 °C against 295 °C for the initial fuel mixture. Thus, hydrotreatment of straight-run gas oil and secondary fractions mixture ensures a liquid

re

product with the highest content of gas oil fraction.

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There is a good correlation between the HDN and HYD activities (Table 8), since the catalyst H1 gives the product with both the lowest N content and one of the lowest diaromatic concentrations. On the other hand, the H2 catalyst gives the product with the highest content of

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the above components.

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4. Conclusion

This paper compares alumina supports and CoMoP/-Al2O3 hydrotreating catalysts

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obtained by modern technologies of flash calcination of gibbsite and the precipitation of aluminum nitrate.

Hydrothermal treatment of the product of gibbsite flash calcination – active aluminum

hydroxyoxide – leads to the formation of pseudoboehmite with needle-like particles, while retaining a part of the amorphous phase apparently inherited from the source material. After heat treatment of such aluminum hydroxide, aluminum oxide of a mixed phase composition is 18

formed, including γ- and χ-alumina. When precipitating aluminum nitrate, 100% pseudoboehmite with a needle-fibrous particle morphology is formed. It has been established that supports obtained from a flash calcined gibbsite are characterized by a bimodal distribution of pores with a second maximum in the region of 150-250 Å, and the volume of such pores is comparable to pores of 70-130 Å. While the support obtained from aluminum nitrate has a unimodal distribution over a narrow pore size range with a maximum at 80 Å; pores of 150-250 Å in size are practically absent. The introduction of

area, but leads to a decrease in the average pore diameter.

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boron at the stage of pseudoboehmite synthesis makes it possible to increase the specific surface

Different supports investigated in this work let to obtain active CoMoS-phase with a

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close morphology, but the share of CoMoS-phase in the catalysts is different. The catalyst supported on H1 has more CoMoS-phase than samples H2 and H3. Due to the bimodal pore

re

distribution and the larger average pore diameter, which makes the active component of the

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catalyst more accessible for the simultaneous conversion of more molecules, sample H1 also shows the greatest activity in the hydrotreating of model feed and fuel mixture. Thus, the eco-friendly technology based on hydrothermal treatment of a flash calcined

na

gibbsite makes it possible to obtain hydrotreating catalysts with the highest or the same activity in the hydrodesulfurization and hydrodenitrogenation of fuel mixture compared to catalyst

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nitrate.

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supported on alumina obtained through the precipitation of pseudoboehmite from aluminum

Acknowledgements This work was conducted within the framework of budget project No. AAAA-A17117041710077-4 for Boreskov Institute of Catalysis.

19

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Figure Caption

Figure 1 – X-ray diffraction patterns (λ=1.54184 Å) of boehmite samples. 1 – P1, 2 – H1, 3 – H2, 4 – H3 Figure 2 – X-ray diffraction patterns (λ=1.54184 Å) of alumina samples. 1 – P1, 2 – H1, 3 – H2, 4 – H3 Figure 3 – HRTEM images of pseudoboehmite particles at scale = 200 nm. 1 – H1, 2 – H2, 3 –

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H3, 4 – P1 Figure 4 – HRTEM images of pseudoboehmite particles at scale = 20 nm. 1 – H1, 2 – H2, 3 – H3, 4 – P1

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Figure 5 – The curves of the integral and differential distribution of the pore volume by the pore size of alumina supports. 1 – H1, 2 – H2, 3 – H3, 4 – P1

re

Figure 6 – Nitrogen adsorption-desorption isotherms of alumina supports. 1 – H1, 2 – H2, 3 –

lP

H3, 4 – P1

Figure 7 – The curves of the integral and differential distribution of the pore volume by the pore size of the catalyst samples. 1 – H1, 2 – H2, 3 – H3, 4 – P1

– H3, 4 – P1

na

Figure 8 – HRTEM images of gas phase sulfided catalysts at scale = 20 nm. 1 – H1, 2 – H2, 3

ur

Figure 9 – HRTEM images of liquid phase sulfided catalysts at scale = 20 nm. 1 – H1, 2 – H2,

Jo

3 – H3, 4 – P1

29

ro of

-p

re

lP

na

ur

Jo Fig 1

30

ro of

-p

re

lP

na

ur

Jo Fig 2

31

ro of

-p

re

lP

na

ur

Jo Fig 3

32

ro of

-p

re

lP

na

ur

Jo Fig 4

33

ro of

-p

re

lP

na

ur

Jo Fig 5

34

ro of

-p

re

lP

na

ur

Jo Fig 6

35

ro of

-p

re

lP

na

ur

Jo Fig 7

36

ro of

-p

re

lP

na

ur

Jo Fig 8

37

ro of

-p

re

lP

na

ur

Jo Fig 9

38

Table 1 – Characteristics of fuel mixture 3740

Nitrogen, ppm

124

Density at 20°C, g/cm3

0.864

Monoaromatic hydrocarbons, wt.%

19.6

Diaromatic hydrocarbons, wt.%

14.6

Polyaromatic hydrocarbons, wt.%

1.8

ro of

Sulfur, ppm

Total aromatics, wt.%

36.0

Boiling point distribution, °C

206

-p

Initial boiling point 10%

250

re

50%

lP

90%

344 365

Jo

ur

na

Final boiling point

295

39

Table 2 – X-ray diffraction data of boehmite and alumina samples XRD Hydroxide form Sample

pseudobo

amorp


Oxide form

γ-

χa*,

ehmite, %

hous,

0>,

0>,

2>,

Al2O

Al2O

%

Å

Å

Å

3, %

3, %

Å

P1

100

–

30

62

115

ro of

7.9

100

–

38

7.9

H1

82

18

60

85

87

67

33

70

18

30

48

95

120

66

85

110

60

7.9

34 28 7.9 40 28

Jo

ur

na

* – unit cell parameter

95

re

H3

82

lP

H2

-p

25

40

Table 3 – Properties of alumina supports and catalysts Textural properties V

V

V

(70-

(150-

(N2),

130

250

cm3/g

Å),

Å),

cm3/g

cm3/g

SBET,

BCS, APD,

2

m /g

B

Na

Co

Mo

P

MPa

Å

ro of

Sample

Chemical composition, %wt.

Al2O3

192

0.67

0.22

0.17

138

-

0.009

Cat

112

0.40

0.10

0.12

140

-

0.006 3.4 12.6 1.5

1.70

Al2O3

249

0.69

0.17

0.20

109

-

0.008

0.76

Cat

144

0.37

0.08

0.09

99

Al2O3

284

0.61

0.15

0.11

87

Cat

167

0.33

0.07

0.06

78

Al2O3

261

0.75

Cat

161

0.45

-

-

-

-

-

0.005 3.5 12.7 1.6

0.72 0.008

-

-

-

0.62 0.005 3.6 12.4 1.4

0.43

0.02

112

-

0.01

-

-

-

0.20

0.01

111

-

0.008 3.5 12.6 1.7

0.82

1.69 0.64 1.65 0.53 1.34

Jo

ur

na

P1

lP

H3

-

re

H2

-p

H1

-

41

Table 4 – The change in pore volume of the samples after the application of the impregnating solution

H1

Sample / Pore size

AC1,

H2

RC2,

H3

AC,

P1

AC,

RC,

AC,

RC,

cm3/g

%

cm3/g

%

-11.1

-0.012

-23.6

range

cm3/g

%

cm3/g

30-50 Å

-0.011

-33.1

-0.009

-11.5

-0.012

50-100 Å

-0.073

-38.4

-0.110

-34.7

-0.115

100-150 Å

-0.082

-58.9

-0.064

-53.7

-0.066

150-250 Å

-0.054

-31.7

-0.104

-53.0

250-500 Å

-0.054

-51.4

-0.018

500-1000 Å

-0.008

-51.4

>1000 Å

+0.008

+46.4

-0.032

Total

-0.271

-40.9

-0.319

-0.165

-43.5

-59.4

-0.109

-40.5

-47.8

-0.007

-38.4

-0.011

-37.0

-0.000

-0.6

+0.004

+33.1

+0.005

+91.4

-127.9

-0.020

-4.3

-0.004

-35.3

-47.2

-0.273

-44.9

-0.293

-39.3

-p

-54.5

-0.053

re

lP

-40.8

+0.017 +184.3

na

ur

ro of

RC, %

Jo

1 – absolute change 2 – relative change

42

Table 5 – HRTEM data for sulfided catalysts Sulfided

Average slabs number per

Average stacking

length, nm

number

1000 nm

H1-G

4.3

2.4

67

H2-G

4.2

2.5

65

H3-G

4.2

2.5

64

P1-G

4.3

2.5

65

H1-L

5.2

1.2

H2-L

5.3

1.3

H3-L

5.0

1.4

P1-L

5.1

1.4

2

58 64

-p

62 60

Jo

ur

na

lP

re

catalyst

ro of

Average slab

43

Table 6 – XPS data of sulfided catalysts Sample Phase

H1 G

H2 L

H3

G

L

BE, Mo 3d (eV)

G

P1 L

G

L

228.8±0.1

∆E1=E(Mo)-E(S), eV

66.8±0.1

78.9

73.6

79.9

76.2

79.3

74.5

79.6

71.0

Mo5+ (%)

13.1

16.2

14.2

16.2

12.8

19.5

15.5

22.1

Mo6+ (%)

8.0

8.2

5.9

7.6

7.9

6.0

4.9

6.9

BE, Co 2p (eV)

779.1±0.1

∆E2=E(Co)-E(S), eV

617.1±0.1

79.9

77.8

77.5

75.9

75.0

71.4

Co2+ (%)

20.1

22.2

22.5

24.1

25.0

28.6

BE, S 2p (eV)

162.0±0.1

85.1

80.1

14.9

19.9

-p

CoMoS (%)

ro of

Mo4+ (%) MoS2

0.11

0.10

0.12

0.11

0.12

0.11

0.13

0.11

ICo2p/IAl2p

0.03

0.03

0.03

0.03

0.03

0.03

0.03

0.03

Jo

ur

na

lP

re

IMo3d/IAl2p

44

Table 7 – Results of the hydrotreating of the model feed Hydrotreating of the model feed DBT

Conversion to Conversion to

Quinoline

Naphthalene

conversion,

conversion,

%

%

Sample conversion,

BPh, %

PhCH, %

% 39.1

86.7

13.3

64.7

4.7

H2

40.5

84.2

15.8

43.9

5.1

H3

37.8

84.5

15.5

P1

37.8

84.9

15.1

ro of

H1

5.0

64.9

3.8

-p

58.1

Table 8 – Results of the hydrotreating of the fuel mixture

Sample N

3740

124

mixture

MA

DA

PA

TA

19.6

14.6

1.8

36.0

7.0

28.1

5.3

0.6

34.0

lP

Fuel

S

Content of aromatic hydrocarbons, wt. %

re

Residual content, ppm

13.4

H2

22.0

13.7

27.8

5.7

0.6

34.1

H3

20.4

8.9

28.0

5.6

0.6

34.2

16.2

8.2

28.0

5.6

0.6

34.2

ur

Jo

P1

na

H1

45