WO2019125207A1 - Protective layer catalyst - Google Patents

Abstract

The invention relates to protective layer catalysts located before the main catalyst for hydrotreating hydrocarbonaceous feedstocks. A catalyst is described which comprises a bimetallic complex compound [Ni(H₂O)₂]₂[Mo₄O₁₁(C₆H₅O₇)₂] at a concentration of 5.3 to 7.9 wt %; a carrier, γ-Al₂O₃, is the remainder; which catalyst has a specific surface area of 265 to 285 m²/g, pore volume of 0.70 to 0.72 cm³/g, an average pore diameter of 100 to 105, and which is in the form of granules with the cross section in the form of a circle with a diameter of 3±0.1 mm and a length of up to 20 mm. After the sulfidation according to generally known methods, the catalyst comprises, wt %: Mo - 1.99-2.98; Ni - 0.61-0.91; S - 1.66-2.48; the carrier is the remainder.

Description

 The catalyst of the protective layer The invention relates to catalysts of a protective layer located in front of the catalysts of the main layer in the process of hydrotreatment of hydrocarbons with a high content of silicon.

At present, Russian refineries have switched to the production of diesel fuels, which, according to the residual sulfur content, meet the new Russian and European standards. At the same time, a mixture of straight-run diesel fractions with light gas oils of secondary processes - catalytic cracking and coking is used as a feedstock for commercial diesel fuel. These secondary distillates contain significant amounts of dissolved organosilicon compounds. When hydrotreating, organosilicon compounds decompose with the formation of silicon dioxide, which, deposited on the surface of hydrotreating catalysts, leads to their accelerated deactivation. To minimize deactivation, a protective layer of a catalyst is available in front of the main Hydrotreating catalysts that can extract most of the silicon compounds from the feedstock and thereby protect the main Hydrotreating catalyst from deactivation. The active metals contained in the catalyst of the protective layer, ensure the conversion of soluble organosilicon compounds into insoluble compounds, and also prevent the formation of carbonaceous deposits on the catalyst surface. The porous structure of the catalyst protective layer allows you to accumulate in the catalyst significant amounts of silicon dioxide with minimal deactivation. Since the volume of hydrotreating reactors is fixed, and the protective layer catalyst is not highly active in targeted hydrotreating reactions — desulfurization, hydrogenation, and diazotization reactions, the amount of protective layer catalyst in the reactor should be minimal. Usually, the amount The catalyst of the protective layer loaded into the hydrotreating reactor is selected so that its silica capacity is sufficient to ensure the planned life of the main catalyst. Accordingly, the silicon capacitance is the most important characteristic of the protective layer catalyst.

 In recent years, due to an increase in the depth of oil refining, the share of secondary distillates in the feedstock to produce diesel fuels monotonously increases, the proportion of silicon compounds in proportion to the feedstock increases. In this regard, it is necessary to develop new catalysts for the protective layer, which have an increased capacity for silicon dioxide.

 There are many variants of hydrotreating processes, including the use of various catalysts for the protective layer, and the process is carried out under conditions typical for hydrotreating petroleum distillates with different ratios between the catalysts of the protective and base layers.

So, the known method of Hydrotreating petroleum fractions [US Pat. RF N ° 2353644], according to which the Hydrotreating is carried out at elevated temperature and pressure and circulation of hydrogen-containing gas in two stages in the presence of a package of alumina catalysts at a temperature of 330-390 ° C, pressure of 40-50 MPa, circulation of hydrogen-containing gas 250-400 nm ³ / m ^{3 of} raw material, the space velocity of the raw material supply is 0.8–1.3 h ¹ in the presence of a catalyst pack, which includes, in the first stage, the catalyst of the protective layer as the upper retaining layer and AHM as the lower layer, in the following ratio, wt.% : ride protective layer isolator 3,0 - 10,0; alum nickel molybdenum catalyst - the rest. In the second stage, the catalytic package includes AKM or AHM as the upper layer and AKM as the lower layer, in the following ratio of components, wt.%: Alumino-cobalt-molybdenum catalyst 20.0-30.0; alum nickel molybdenum catalyst - the rest.

There is also known a method of obtaining low-sulfur oil fractions [US Pat. RF N ° 2140964], according to which high-sulfur medium-distillate fractions are hydrotreated in the presence of an alumina-catalyst package, including a protective layer pre-activated with a sulfur-containing agent, provided that the catalytic package contains 2-10 wt.% of the catalyst of the protective layer obtained by impregnation of the carrier - alumina, calcined at a temperature not lower than 800 ° C and containing 2-5 wt.% a-alumina, 73-85 wt.% d-alumina and 25-10 May. % g-alumina, formed in the form of geometric bodies having a size of 8-20 mm and the ratio of volume to surface area of 1-0-2.5 mm / mm, aqueous solutions of salts of active ingredients, followed by drying and calcining.

 A known process for the catalytic hydroprocessing of silicon-containing naphtha [US Pat. USA N2 6576121, C 10G 45/04], according to which silicon-containing raw materials, to which is added from 0.01 to 10 vol. % of water is contacted at a temperature of 350 or 400 ° C, a pressure of 20-50 bar in the presence of hydrogen with a commercial hydrotreating catalyst having a specific surface of 380 m / g and a pore volume of 0.6 cm / g.

 Also known catalyst for hydrotreating the upper layer and the method of its preparation [US Pat. RF N ° 2235588], according to which the method of preparation of the catalyst is that aluminum hydroxide with a moisture content of 50-80 wt.% Is mixed with a ceramic mixture with a fractional composition of 0.01-0, 1 mm, containing 65-76 wt.% Silicon dioxide and 24-35 wt.% Alumina, successively add a salt of molybdenum, a salt of cobalt or nickel, in the mixture is added a solution of nitric acid in an amount sufficient to create the acidity of the pH of the mass equal to 3-4, formed into hollow cylindrical granules, dried and calcined. The catalyst contains 19-50 wt.% Silicon dioxide, aluminum oxide, oxides of molybdenum, cobalt or nickel - the rest.

 A common disadvantage for the above-listed hydrotreating options and catalysts for the protective layer is that with their use it is not possible to achieve a high extraction of silicon from the raw materials due to the low capacity of the used catalysts for silica.

Closest to the proposed technical solution for the achieved result is the process of removing silicon from hydrocarbons in the presence of an adsorbent catalyst described in [Pat. USA No 81062503, С07С7 / 12, July 28, 2009]. The adsorbent catalyst contains 5% MoO ₃ and 1% NiO deposited on a hydrotalcite of the general formula [Mg _0.75 A1 _{0 5} (OH) ₂ ] 0.125 C0 ₃ 0.5 H ₂ 0, where the molar ratio Mg / Al = 3. The process of removing silicon from hydrocarbon feedstock is carried out in the presence of an adsorbent catalyst at a temperature in the range of 80-360 ° C, a pressure in the range of 0.5-5.0 MPa, a hydrogen / feedstock ratio of 10-1000 nm ³ H ₂ / m ^{3 of} raw materials, volume flow of raw materials 1-20 h ^'1 . Before using in the process of removing silicon from hydrocarbon feedstock, the catalyst-adsorbent is sulphidized with a solution of dimethyl disulfide in gasoline having a sulfur concentration of 10,000 ppm at 2.0 MPa, consumption of the sulfiding mixture 3 hours ¹ , hydrogen / sulfiding mixture ratio 200 nm ³ / m ³ 2 hours at 230 ° C and 2 hours at 320 ° C. This adsorbent catalyst has a silicon capacity of 10.68% (22.85% of Si0 ₂ ) and is completely deactivated in 95.75 hours when converting raw materials containing 1200 ppm of silicon.

The main disadvantage of the known catalyst is that it has a non-optimal chemical composition, which causes its low capacity for silicon dioxide. In particular, hydrotalcite being a carrier is a material from the class of layered double hydroxides, while for hydrotalcite with a molar ratio Mg / Al = 3, the specific surface does not exceed 200 m ² / g with a pore volume in the range of 0.32-0.81 cm ³ / g. Such textural characteristics do not allow high capacity for silica. As compounds of active metals, the known catalyst contains 5% MoO ₃ and 1% NiO. It is known that during the sulfidation of catalysts containing oxides of molybdenum and nickel, a significant part of the metals forms the Type I NiMoS phase, which has low activity in the target hydrotreating reactions — the desulfurization, hydrogenation and diazotization reactions. Accordingly, the catalyst, initially containing oxides of molybdenum and nickel, will have less resistance to blocking the surface with carbonaceous deposits, as compared with catalysts containing compounds, which during sulfidation selectively turn into Type II phase highly reactive in NiMoS hydrotreating reactions. This explains the low resistance of a known catalyst to deactivation, which manifests itself in the form of its complete deactivation. less than 100 hours of work. Accordingly, the known catalyst has a low silica capacity and low deactivation resistance.

 The invention solves the problem of creating an improved catalyst of a protective layer located in front of the catalysts of the main layer in the process of hydrotreating hydrocarbon raw materials with a high content of silicon.

 The proposed catalyst is characterized by:

1. The optimal chemical composition of the catalyst, which contains nickel and molybdenum in the form of a bimetallic complex compound [Ni (H ₂ 0) ₂ ] ₂ [Mo ₄ 0 _ll (C ₆ H ₅ 0 ₇ ) ₂ ], which selectively turns into NiMoS during sulfidation phase, which has an increased activity in the reactions of desulfurization, hydrogenation and diazotization.

 2. Optimal concentrations of bimetallic compounds, which, on the one hand, are sufficient to prevent the formation of deactivating carbon deposits on the catalyst surface, and, on the other hand, are not so large as to impair the texture characteristics of the catalyst.

 3. Optimum textural characteristics - specific surface, volume and pore diameter, providing an increased catalyst capacity for silicon dioxide.

 4. Increased content in the sulfided NiMoS catalyst of the phase, which protects the catalyst from carbonization.

 5. The presence in the composition of the catalyst Y-A ^ Oz, on the one hand, acts as a carrier for the sulfide active component, and on the other hand, contains various surface OH-groups that catalyze the decomposition of organosilicon compounds with the formation of silicon dioxide.

 EFFECT: catalyst has an increased capacity for silicon dioxide and increased resistance to deactivation by carbonaceous deposits in the conditions of hydrotreating silicon-containing hydrocarbons.

The problem is solved by the composition of the catalyst protective layer, which contains nickel and molybdenum in the form of a bimetallic complex compound [Ni (H ₂ 0) ₂ ] ₂ [Mo ₄ On (C ₆ H ₅ 0 ₇ ) ₂ ] with a concentration of 5, 3-7, 9 May. %; the carrier is -Alhos - the rest.

The catalyst has a specific surface area of 265-285 m ² / g, a pore volume of 0.70-0.72 cm3 / g, an average pore diameter of 100-105 A, and presents granules with a cross section in the form of a circle with a diameter of 3 ± 0.1 mm and a length of 20 mm.

 After sulfidation by known methods, it contains, May. %: Mo - 1.99-2.98; Ni - 0.61-0.91; S - 1.66-2.48; the carrier is the rest, while the sulfided catalyst contains 75-85% nickel in the NiMoS phase, determined according to XPS data by decomposition of the Ni2p line.

A distinctive feature of the proposed catalyst in comparison with the prototype is its chemical composition, namely that the inventive catalyst contains nickel and molybdenum in the form of a bimetallic complex compound [Ni (H ₂ 0) ₂ ] ₂ [Mo ₄ On (C ₆ H ₅ 0 ₇ ) ₂ ] with a concentration of 5, 3-7, 9 May. %; the carrier of a-oz is the rest. The decrease in the content of the bimetallic complex compounds below the claimed limits leads to a decrease in the lifetime of the catalyst, an increase in the content of the bimetallic compounds leads to a decrease in the capacity of the catalyst for silica.

The second distinguishing feature of the proposed catalyst in comparison with the prototype is that it has a specific surface of 265-285 m ² / g, a pore volume of 0.70-0.72 cm3 / g, an average pore diameter of 100-105 A, is granules with a cross section in the form of a circle with a diameter of 3 ± 0.1 mm and a length of up to 20 mm.

 The third distinguishing feature of the proposed catalyst in comparison with the prototype is that after sulphidation by known methods, the catalyst contains, May. %: Mo - 1.99-2.98; Ni - 0.61-0.91; S = 1, 66-2.48; the carrier is the rest, while the sulfided catalyst contains 75-85% nickel in the NiMoS phase, determined according to XPS data by decomposition of the Ni2p line.

 The technical result consists of the following components:

1. The inventive chemical composition of the catalyst provides further production of a sulfided catalyst containing supported metals mainly in the form of the NiMoS phase, which has an increased activity in the hydrogenation, desulfurization and diazotization reactions and, thus, protects the catalyst from accelerated deactivation by carbon deposits in the conditions of the hydrotreating process.

 2. The declared textural characteristics of the catalyst (specific surface area, pore volume and diameter) in combination with a low concentration of supported metals - Ni and Mo provide the maximum catalyst capacity for silica.

3. The use of g-A1 ₂ 0 ₃ as a carrier with a high specific surface contributes to the preparation of a highly dispersed sulphide active component, with various surface OH groups g-A1 ₂ 0 ₃ catalyzing the decomposition of organosilicon compounds with the formation of silicon dioxide.

 Description of the proposed technical solution.

First, prepare the carrier - g-A1 ₂ 0 ₃ with a high specific surface, high pore volume and pore diameter, ensuring good diffusion of organosilicon compounds along the granule.

The original aluminum monohydroxide powder AYuON with the pseudoboehmite structure is mixed in a Z-shaped mixer for 1 h with a peptizing agent, which is used as a 25% aqueous solution of ammonia (with a molar ratio of NH ₃ / A1 ₂ 0 ₃ = 0.09). Carrier granules are produced by extrusion using a fluoroplastic die (diameter of the filler 3.9 mm) with a cylindrical hole at a molding pressure = 5.0-7.0 MPa with a plunger displacement speed of 2.0 mm / s. The finished extrudates are dried in air at a temperature of 1 to 10 ° C for 4 hours. The dried granules are heated in air to 550 ° C at a heating rate of 275 ° C / hour, then calcined at a temperature of 550 ° C for 4 hours. As a result, g-A1 ₂ 0 ₃ in the form of cylindrical granules with a cross-sectional diameter of 3 ± 0.1 mm.

Using this carrier, a supported catalyst of the protective layer is prepared. First, prepare the impregnating solution containing bimetallic complex compound [Ni (H ₂ 0) ₂ ] ₂ [Mo ₄ On (C ₆ H ₅ 0 ₇ ) ₂ ]. For this purpose, given amounts of ammonium paramolybdate (NH ₄ ) ₆ Mo ₇ 0 ₂₄ · 4H ₂ 0, nickel (II) basic carbonate NiC0 ₃ ^" mNi (0H) ₂ ^" nH ₂ 0, citric monohydrate are weighed. Measured cylinder measure preset amount of distilled water. A measured amount of water is poured into the flask and an anchor of the magnetic stirrer is placed. The flask is placed on the heating surface of a heated magnetic stirrer. Set the rotation speed of the stirrer 300 rpm and the temperature of the solution 60 ° C. A measured amount of citric acid is loaded into the flask and stirred under visual inspection.

Then, a portion of ammonium paramolybdate is added to the flask to a solution of citric acid with constant stirring and maintaining the solution temperature (60 ± 5) ° C. The solution is stirred until a homogeneous transparent solution is obtained containing the complex compound molybdenum (VI) citrate (NH ₄ ) ₄ [Mo ₄ (C ₆ H ₅ 0 ₇ ) ₂ 0 _l] ]. A portion of nickel (II) basic carbonate is added to the previously obtained aqueous solution of molybdenum citrate (VI). In this case, the liquid foams, and its temperature rises to 70 ° C. Stirring is continued at (65-70) ° C until a homogeneous transparent solution of green color, not containing turbidity, bubbles and foam, is obtained. The solution contains nickel and molybdenum in the form of a bimetallic complex compound [Ni (H ₂ 0) ₂ ] ₂ [Mo ₄ O _l (C ₆ H ₅ 0 ₇ ) ₂ ].

 The prepared solution is poured into a calibrated measuring cylinder, after which the volume of the solution is adjusted to the specified amount by adding distilled water. To confirm the presence in the solution of a bimetallic complex compound, it is studied by the method of IR-spectroscopy.

The resulting solution is impregnated with a carrier on the basis of g-A1 ₂ 0 ₃ , while using the impregnation of the carrier on the capacity. After impregnation, the catalyst is dried in air at a temperature of 110-150 ° C.

 The result is a catalyst containing Nickel and molybdenum in the form of a bimetallic complex compounds

[Ni (H ₂ 0) ₂ ] ₂ [Mo ₄ 0 _li (C ₆ H ₅ 0 ₇ ) ₂ ] with a concentration of 5, 3-7, 9 May. %; g-A1 ₂ 0 ₃ carrier - the rest.

After sulphidation by known methods, the catalyst contains, in May. %: Mo - 1.99-2.98; Ni - 0.61-0.91; S - 1.66-2.48; the carrier is the rest, while the catalyst contains 75-85% nickel in the NiMoS phase, determined according to XPS data by decomposing the Ni2p line. The invention is illustrated by the following examples and tables:

 Example 1

 First prepare the carrier. Mixing is carried out in a laboratory mixer with Z-shaped blades. Measured 137 g of aluminum hydroxide AYuN with the structure of pseudo-boehmite, having a loss on ignition at 550 ° C of 27%, is loaded into the capacity of the mixer. Measured 155 ml of distilled water, 6.04 ml of 25% aqueous ammonia solution are poured into a chemically resistant glass beaker, then stirred with a glass rod. The prepared solution is poured to aluminum hydroxide and stirred until a plastic molding material is obtained. Mixing time averages 30 minutes.

 The finished mass is transferred from the mixer to the molding cylinder of the laboratory extruder and is forced through the die hole, which provides cylindrical granules with a cross section in the form of a circle with a diameter of 3 ± 0.1 mm.

Then, heat treatment is carried out, including drying and calcining. The extrudates are dried in a drying oven at 110 ° C for 2 hours. At the end of the drying process, the extrudates are broken into particles up to 20 mm long. The dried granules are heated in air to 550 ° C at a heating rate of 275 ° C / hour, then calcined at 550 ° C for 4 hours. The result is g-A1 ₂ 0 ₃ in the form of cylindrical granules with a cross-section diameter of 3 ± 0.1 mm up to 20 mm. The output of the carrier is 100 g. The moisture capacity is 0.85-0.89.

Next, a solution of the bimetallic complex compound [Nϊ (H2q) 2] 2 [Mq4qp (P ₆ H5q7) 2] is prepared, for which 4.7 g of citric acid C ₆ H ₈ 0 _{7 are} successively dissolved in 100 ml of distilled water with stirring; 8.6 g of ammonium paramolybdate (NH ₄ ) ₆ Mo ₇ q _24c 4H ₂ q and 1.5 g of nickel (II) carbonate basic aqueous NiC0 ₃ · mNi (OH) 2 * pNgO. After complete dissolution of all components, the solution is made up to 200 ml by adding distilled water.

The infrared spectra of the solution are recorded, which were recorded on a Shimadzu FTIR-8300 spectrometer in the spectral range 700-6000 cm ¹ s 4 cm ¹ resolution. The IR spectroscopic data for the impregnating solution coincide with the data for the bimetallic complex compound shown in Table 1.

100 g of the obtained carrier is impregnated with a capacity of 89 ml of a solution containing 5.6 g of the bimetallic complex compound [Ni (H ₂ 0) ₂ ] ₂ [Mo ₄ On (C ₆ H ₅ 0 ₇ ) ₂ ] at 20 ° C for 60 min Then the catalyst is dried in air at 110 ° C.

The catalyst contains, may. %: [Ni (H ₂ 0) ₂ ] ₂ [Mo ₄ On (C ₆ H ₅ 0 ₇ ) ₂ ] - 5.3; the carrier is -Alhos - the rest.

The catalyst has a specific surface area of 285 m ² / g, a pore volume of 0.72 cm ³ / g, an average pore diameter of 100 A, and is a cylindrical particle with a cross-sectional diameter of 3 ± 0.1 mm and a length of up to 20 mm.

Next, the catalyst is sulfided with a straight-run diesel fraction, which additionally contains 1.5 May. % sulfidizing agent - dimethyl disulfide (DMDS), with a volumetric feed rate of sulfiding mixture 2 h ¹ and the ratio of hydrogen / raw materials = 300 according to the following program:

 - drying the catalyst in the Hydrotreating reactor in a stream of hydrogen at 140 ° C for 2 h;

 - wetting of the catalyst with a straight-run diesel fraction for 2 h;

 - supply of sulfiding mixture and increase in temperature up to 240 ° С with a temperature rise rate of 25 ° С / h;

 - sulfidization at a temperature of 240 ° C for 8 h (low-temperature stage);

 - an increase in the temperature of the reactor to 340 C with a rate of rise of temperature of 25 ° C / h;

 sulphidation at 340 ° С for 8 h.

 The result is a catalyst that contains, may. %: Mo - 1.99; Ni — 0.61; S — 1.66; g-Ao-OE carrier - the rest.

Next, the catalyst is characterized by the method of x-ray photoelectron spectroscopy (XPS). XPS spectra were recorded using a SPECS spectrometer (Germany) using a PHOIBOS-150 and A1 K hemispherical energy analyzer (hv = 1486.6 eV, 200 watts). Data on the content in the catalyst NiMoS phase are shown in table 2.

Next, determine the catalyst capacity for silicon dioxide and its resistance to decontamination under hydrotreating conditions. As raw material is used straight-old diesel fraction containing 0.2475% sulfur, nitrogen rrsh 64 having a density of 0.845 g / cm ^3, a boiling range 210- 360 ° C, T ₉₅ - 356 ° C, to which is added the amount of hexamethyldisiloxane corresponding silicon concentration in raw materials 800 pps

The process is carried out under conditions typical for Russian industrial hydrotreating units: the volumetric feed rate is 4 hours, the ratio of H ₂ / raw materials = 550 nm H ₂ / m of raw materials, pressure 3.8 MPa, temperature 360 ° С. The continuous test time is 160 hours. The test results of the catalyst are shown in Table 3.

 Example 2

 Prepare the media, similarly to example 1.

Next, prepare a solution of the bimetallic complex compound [Ni (H ₂ 0) ₂ ] ₂ [Mo ₄ O _li (C ₆ H ₅ 0 ₇ ) ₂ ], for which 6.35 g of citric acid C are successively dissolved in 100 ml of distilled water with stirring ₆ H ₈ 0 ₇ ; 11.61 g of ammonium paramolybdate (NH ₄ ) ₆ Mo ₇ 0 ₂₄ x4H ₂ 0 and 2.02 g of nickel (II) carbonate basic water N1CO ₃ · mNi (OH) ₂ · pN ₂ 0. After complete dissolution of all components, adding distilled water volume of the solution is adjusted to 200 ml.

The IR spectra of the solution are recorded, which were recorded on a Shimadzu FTIR-8300 spectrometer in the spectral range 700-6000 cm ¹ with a resolution of 4 cm ¹ . The IR spectroscopic data for the impregnating solution coincide with the data for the bimetallic complex compound shown in Table 1.

100 g of the obtained carrier is impregnated with a capacity of 89 ml of a solution containing 7.56 g of the bimetallic complex compound [Ni (H ₂ 0) ₂ ] ₂ [Mo ₄ On (C ₆ H ₅ 0 ₇ ) ₂ ] at 50 ° C for 30 min Then the catalyst is dried in air at 130 ° C.

The catalyst contains, may. %: [Ni (H ₂ 0) ₂ ] ₂ [Mo ₄ Ou (C ₆ H ₅ 0 ₇ ) ₂ ] - 7.0; g-A1 ₂ 0 ₃ carrier - the rest. The catalyst has a specific surface area of 273 m ² / g, a pore volume of 0.71 cm ³ / g, an average pore diameter of 102 A, and is a cylindrical particle with a cross-sectional diameter of 3 ± 0.1 mm and a length of up to 20 mm.

 The catalyst is sulfide as in Example 1.

The result is a catalyst that contains, may. %: Mo - 2.66; Ni — 0.8; S is 1.99; g-A1 ₂ 0 ₃ carrier - the rest.

 Next, the catalyst is characterized by the method of x-ray photoelectron spectroscopy (XPS). XPS spectra were recorded using a SPECS spectrometer (Germany) using a hemispherical energy analyzer PHOIBOS-150 and A1 K and irradiation (hv = 1486.6 eV, 200 W). Data on the content in the catalyst NiMoS phase are shown in table 2.

 Next, determine the capacity of the catalyst for silicon dioxide and its resistance to decontamination under hydrotreating conditions as in example 1. The results of the testing of the catalyst are shown in table 3.

 Example 3

 Prepare the media, similarly to example 1.

Next, prepare a solution of the bimetallic complex compound [Ni (H ₂ 0) ₂ ] ₂ [Mo ₄ On (C ₆ H ₅ 0 ₇ ) ₂ ], for which, 7.03 g of citric acid C _{6 are} successively dissolved in 100 ml of distilled water with stirring H ₈ 0 ₇ ; 12.86 g of ammonium paramolybdate (NH ₄ ) ₆ Mo ₇ q _24c 4H ₂ q and 2.24 g of nickel (II) carbonate basic water N1CO ₃ · mNi (OH) ₂ · pN ₂ 0. After complete dissolution of all components, adding distilled water volume of the solution is adjusted to 200 ml.

The IR spectra of the solution are recorded, which were recorded on a Shimadzu FTIR-8300 spectrometer in the spectral range 700-6000 cm ¹ with a resolution of 4 cm ¹ . The IR spectroscopic data for the impregnating solution coincide with the data for the bimetallic complex compound shown in Table 1.

100 g of the obtained carrier is impregnated with a capacity of 89 ml of a solution containing 8.37 g of the bimetallic complex compound [Ni (H ₂ 0) ₂ ] ₂ [Mo ₄ Oi _l (C ₆ H ₅ 0 ₇ ) ₂ ] at 80 ° C for 120 min Then the catalyst is dried in air at 150 ° C. The catalyst contains, may. %: [Ni (H ₂ 0) ₂ ] ₂ [Mo ₄ On (C ₆ H ₅ 0 ₇ ) ₂ ] -7.9; g-A1 ₂ 0 ₃ carrier - the rest.

The catalyst has a specific surface of 265 m ² / g, a pore volume of 0.70 cm ³ / g, an average pore diameter of 105 A, and is a cylindrical particle with a cross-sectional diameter of 3 ± 0.1 mm and a length of up to 20 mm.

 The catalyst is sulfide as in Example 1.

The result is a catalyst that contains, may. %: Mo - 2.98; Ni — 0.91; S — 2.48; g-A1 ₂ 0 ₃ carrier - the rest.

 Next, the catalyst is characterized by the method of x-ray photoelectron spectroscopy (XPS). XPS spectra were recorded using a SPECS spectrometer (Germany) using a hemispherical energy analyzer PHOIBOS-150 and A1 K and irradiation (hv = 1486.6 eV, 200 W). Data on the content in the catalyst NiMoS phase are shown in table 2.

 Next, determine the capacity of the catalyst for silicon dioxide and its resistance to decontamination under hydrotreating conditions as in example 1. The results of the testing of the catalyst are shown in table 3.

Table 1.

IR spectra of bimetallic complex compounds in solution.

The position of the absorption bands in cm ¹ .

Таблица 2.

Table 2.

XPS data for sulfided catalysts

Table 3.

The results of testing catalysts in the conversion of diesel fuel containing 800 ppm of silicon.

The catalyst prototype described in [US Pat. USA N ° 8l06250, С07С7 / 12, July 28, 2009] has a maximum silicon capacity of 10.68% (22.85% of Si0 ₂ ) and is completely deactivated in 95.75 hours.

 Thus, as can be seen from the above examples, the proposed catalyst, due to its chemical composition and texture, has a high silicon capacity and resistance to deactivation, significantly exceeding the analogous parameters of the prototype catalyst.

Claims

Claim 1. The catalyst of the protective layer comprising nickel, molybdenum and a carrier, characterized in that it contains nickel and molybdenum in the form of a bimetallic complex compound [Ni (H ₂ 0) ₂ ] ₂ [Mo ₄ On (C ₆ H ₅ 0 ₇ ) ₂ ] with a concentration of 5, 3-7, 9 May. %; g-A1 carrier ₂ 0 ₃ - the rest.  2. The catalyst according to claim 1, characterized in that it has a specific surface area of 265-285 m / g, a pore volume of 0.70-0.72 cm / g, an average pore diameter of 100-1 105 A, is cylindrical granules with a cross section of a circle with a diameter of 3 ± 0.1 mm and a length of up to 20 mm. 3. The catalyst according to claim 1, characterized in that it contains, after sulfidization, in May. %: Mo - 1.99-2.98; Ni - 0.61-0.91; S - 1.66-2.48; g-A1 carrier ₂ 0 ₃ - the rest.  4. Catalyst according to claim 1, characterized in that after sulfiding it contains 75-85 wt.% Nickel in the NiMoS phase, determined according to XPS data by decomposing the Ni2p line.