RU2492922C1 - Composition and method of synthesising catalyst of hydroxygenation of oxygen-containing hydrocarbon raw material - Google Patents

Abstract

FIELD: chemistry.

SUBSTANCE: invention relates to catalysts and their obtaining. Catalyst of hydroxygenation of oxygen-containing carbon raw material or combined hydrofining of oil fractions and oxygen-containing compounds, obtained from vegetable (renewable) raw material, which contains compounds of molybdenum (15-25 wt % MoO₃) and nickel (4.0-6.0 wt %. NiO), dispersed on the surface of alumooxide carrier modified with hydrocarbon coating (content of carbon is 1-3 wt %, specific surface area not less than 200 m²/g, specific volume of pours 0.8-1.1 cm³/g, average diameter of pours not less than 100 Ǻ). Method of said catalyst synthesis is described.

EFFECT: increased activity and stability of catalyst.

3 cl, 2 tbl, 9 ex

Description

The invention relates to the field of chemistry, in particular to catalysts designed for hydrodeoxygenation of oxygen-containing hydrocarbon feedstocks, and can be used in the refining and petrochemical industries.

Limited reserves and rising prices for petroleum raw materials stimulate the need for the development of catalysts and technologies for processing renewable organic raw materials for the production of environmentally friendly motor fuels. Currently, biofuels are considered a real alternative to traditional petroleum fuels, as they have several advantages: they reduce dependence on fossil oil; characterized by the optimal ratio of received and invested energy; reduce greenhouse gas emissions and harmful substances (particulate matter, unburned hydrocarbons, sulfur oxides); are biodegradable, non-toxic and renewable; contribute to the diversification of the agricultural economy.

As raw materials for the production of motor fuels from renewable resources, Pancake week crops (soy, rape, sunflower, etc.), animal fats, algae and wood are used.

Known single-stage and two-stage technology for the production of biodiesel, which is a monoalkyl esters of fatty acids obtained from plant or animal raw materials by transesterification (US 5972057, US 5525126, C07C 67/03, 2008114559/04). The resulting carboxylic esters have high cetane characteristics and low viscosity. However, there are a number of disadvantages: low miscibility with petroleum fuel, insufficiently good temperature characteristics, the formation of a by-product glycerol (content of about 10 wt.%), Low thermo-oxidative stability, increased formation of coke deposits in the engine, emissions of nitrogen oxides during fuel combustion.

The above disadvantages can be eliminated by the deoxygenation reaction of an oxygen-containing hydrocarbon feed. As a result of the deoxygenation reaction, n-paraffin hydrocarbons are formed, which are subsequently isomerized in order to increase their low-temperature properties.

There is also known a method (US 4992605) for a one-stage process for processing vegetable oils (rapeseed, sunflower, soybean, palm oil) and wood pyrolysis products (bio-oil) by deep hydrocracking. In the process, sulfide catalyst compositions of NiMo and CoMo were used. The process was carried out at a hydrogen pressure of about 15 MPa and a temperature of 350-450 ° C. The ultimate goal is to obtain a diesel component with a high cetane number and pour point.

A commercially attractive area in the development of the production of high-quality petroleum products is the creation of catalytic technologies for their production from renewable raw materials together with oil fractions at oil refineries. The essence of the process lies in the fact that in hydrotreating or hydrocracking plants, in addition to hydrodesulfurization of petroleum feedstock, there is a chemical transformation of the components of renewable feedstock into hydrocarbons, identical in composition to the components of the oil fractions.

For example, US 2008/017357 A1 proposes a method for hydrotreating oils (of vegetable or animal origin) and petroleum feeds. The technology uses a two-reactor scheme with various catalytic compositions. The first catalyst is required to remove sulfur-containing compounds from oil fractions up to 50 ppm. Part of the products from the first reactor is sent to the second hydrotreatment reactor, where it is mixed with plant (animal) raw materials. The processing of plant materials in combination with petroleum fractions is mentioned in US Pat. No. 2,163,563. The processing is carried out in the presence of hydrogen under high pressure (from 50 to 500 atm) using a Ni (S) / Al ₂ O ₃ catalyst. Combined hydrotreating of renewable and petroleum feedstocks is also disclosed in US Pat. No. 1,016,020 A1.

All of the above technologies are based on the hydrodeoxygenation reaction of renewable raw materials (wood pyrolysis products, vegetable and animal fats). In the literature for the hydroprocessing of renewable raw materials, various catalytic compositions are used.

Known hydrodeoxygenation catalysts based on Pd, Pt, Ni, Co supported on Al ₂ O ₃ and / or SiO ₂ (EP 1741767, C10G 3/00 and 2004/0230085 A1). Hydrodeoxygenation is carried out at a pressure of up to 15 MPa and a temperature of 200-400 ° C. It is noted that the removal of oxygen from the feedstock occurs both on the route of the hydrodeoxygenation reaction and on the decarboxylation reaction. The direction of the deoxygenation route depends on the sulfur content of the process feed. With an increase in sulfur content, the reaction mainly proceeds along the decarboxylation route.

A method of preparing a catalyst (RU 376062 C1) for producing diesel fuel from natural raw materials based on crystalline silicoaluminophosphates with a zeolite-like structure of the SAPO-31 type is described. EFFECT: high activity of the catalyst both in the hydrogenation of unsaturated hydrocarbons and ether bonds, as well as in decarboxylation (and / or decarbonylation) and in isomerization of the resulting normal structure paraffins with high selectivity for isomeric products. The process of producing diesel fuel is carried out in one stage.

A known catalyst (RU 2356629 C1) for hydrodeoxygenation of oxygen-containing aliphatic compounds such as carboxylic acids, their esters and triglycerides, which is a composite composite containing noble metal (in an amount of not more than 5.0 wt.%) Or contains nickel, or copper, or iron, or their combination in reduced form in an amount of not more than 54.7 wt.% and, at least, transition metals that differ from those listed above, in oxide form in an amount of not more than 40 wt.%, the carrier is the rest. Three variants of a catalyst preparation method are described. The hydrodeoxygenation process is carried out using the catalyst described above at a hydrogen pressure of less than 3.0 MPa, a temperature of 250-340 ° C. EFFECT: high activity of catalysts and mild process conditions. The use of a catalyst based on a noble metal (Pd) for processing biocomponents is also proposed in patent US 007956224 B2.

The use of the above catalyst compositions in the processing of mixed raw materials containing a significant amount of heteroatomic and unsaturated compounds is impractical due to the rapid deactivation of the catalysts. Therefore, the basis for creating catalysts for processing mixtures of renewable and petroleum feedstocks are sulfide catalysts, which should have high activity in the reactions of hydrogenolysis of heteroatomic compounds, hydrogenation of unsaturated components, resistance to coke formation on the catalyst surface, high tolerance to water and carbon oxides, and resistance to catalytic I will give.

The preparation of n-paraffin hydrocarbons by the hydrodeoxygenation of fatty acid triglycerides in the presence of sulfidized hydrocracking catalysts — Co (Ni) Mo / Al ₂ O ₃ and at a temperature of 350-450 ° C and a pressure of H ₂ 4.8-15.2 MPa (US 4992605, C10L 1/04) is described. ; US 5705722, C07C 1/00). It has been shown that during the processing of palm oil at a temperature of 360 ° C, a pressure of 5.5 MPa and a space velocity of 1.18 h ^-1 , 8.7 wt.% Water and 82 wt.% Organic fraction (hydrocarbons C ₁₅ -C ₁₈ ) are formed.

Mo-catalysts are known (US 20110166396 A1) for hydrodeoxygenation for the processing of petroleum and renewable raw materials (vegetable oils, animal fats, fatty acids, methyl esters of fatty acids). The patent proposes a method for reducing the rate of catalyst deactivation and reducing the hydraulic resistance in the reactor. A distinctive feature of the proposed Mo / Al ₂ O ₃ catalyst is the use of a carrier with a bimodal pore distribution (the pore volume with a size of more than 50 nm should be at least 10-15 wt.%). The catalyst carrier are oxides of aluminum, silicon and titanium (or their composition). Mo concentration from 0.1 to 20 wt.%. The hydrodeoxygenation reaction is carried out at a hydrogen pressure of 20-100 bar, a temperature of 200-350 ° C, a space velocity of 0.1-10 h ^-1 , the hydrogen circulation rate of 200-300 nm ³ / m ^{3 of} raw materials.

US 0186020 A1 describes hydroconversion catalysts for a mixture of a vegetable (concentration from 1% to 75% by weight) and petroleum feed. The process was carried out on Co (Ni) sulfide catalysts with the following parameters: pressure 4 MPa to 10 MPa, temperature in the reactor 320-400 ° C, space velocity 0.5-2 h ^-1 , circulation rate 200-1000 nm ³ / m ³ raw materials. Comparison of the obtained product with mineral diesel fuel showed a higher cetane number and oxidative stability, and lower density.

The patents (WO 2012/018520 A2 and WO 2011/099686 A1) provide catalysts for the processing of vegetable oils and bio-oil obtained by wood pyrolysis. The following catalyst compositions have been proposed Mo / ZrO ₂ , NiMo / ZrO ₂ , CoMo / TiO ₂ , NiW / TiO ₂ , NiMo / C, NiW / AlPO ₄ and NiMo / Nb ₂ O ₅ . Comparative tests showed a higher activity of the catalysts using ZrO ₂ and TiO ₂ as a carrier. Among them, the highest diesel component yield and stability are observed for NiMo / ZrO ₂ and NiW / TiO ₂ systems.

A method for the synthesis of catalysts for producing hydrocarbons C ₁₀ -C ₃₀ from plant materials (US 0019763 A1) is described. The process is carried out under hydrotreating conditions using Co (Mo) (S) / Al ₂ O ₃ and Co (Mo) (S) / ZSM-5 catalysts. The patent indicates the possibility of joint processing of plant materials and oil fractions.

A known catalyst and method for the joint processing of petroleum and vegetable oil (US 20110239532 A1). For hydrodeoxygenation, a commercial catalyst UOP UF 210 based on NiMo / Al ₂ O _{3 was used} . Vegetable oil is fed into the reactor in the presence of DMDS (0.025). The temperature in the reactor is 340-350 ° C, the volumetric feed rate of 1 h ^-1 , the pressure is 3.5 MPa, the circulation rate of the VSG is 1500 nm ³ / m ^{3 of} raw material.

The processing of lignin into motor fuels using CoMo / Al ₂ O ₃ and CoMo / Al ₂ O ₃ -SiO ₂ sulfide catalysts is described in US 2011/0237838 A1. The tests of the catalysts were carried out in a mixing autoclave at a hydrogen pressure and a temperature of 350-375 ° C. Analysis of the reaction products showed that the hydrogenated product mainly consists of alkyl derivatives of mono-, bi- and tricyclic naphthenes.

Closest to the composition of the claimed catalyst for the hydrodeoxygenation of an oxygen-containing hydrocarbon feed (the presence of an active component, promoter) is the catalyst described in patent US 2010/0043278 A1.

The prototype catalyst is prepared by impregnation of a high-purity alumina support having pore sizes from 5 to 40 nm and containing phosphorus oxide or silicon oxide in an amount of 0.001-1.0 wt.%. an aqueous solution containing a molybdenum salt (ammonium heptamolybdate, ammonium dimolybdate) and nickel nitrate, and orthophosphoric (citric) acid to stabilize. Next, the impregnated sample is dried at temperatures of 25-200 ° C and calcined for 2 hours at temperatures of 350-750 ° C.

After calcination, the catalyst contains (wt.%): 2.0-5.0 NiO, 10-18 MoO ₃ , 0.001-1.0 P ₂ O ₅ , 0.001-1.0 SiO ₂ , has a high specific surface area of 195-245 m ² / g.

The catalyst is highly capable of hydrodeoxygenation of an oxygen-containing hydrocarbon feed consisting of triglycerides of various origins, in the presence of sulfur-containing compounds or in H ₂ S / H ₂ medium to maintain the sulfide state of the active phase.

The main disadvantages of this catalyst are:

- the need for a stage of high-temperature calcination of the catalyst, which leads to the migration of promoter atoms into the carrier with the formation of spinels of the type NiAl ₂ O ₄ inactive in catalytic reactions;

- the use as a carrier of alumina containing acidic centers of the Lewis type, as well as phosphorus and silicon oxides, which leads to a fairly rapid deactivation of the catalyst due to coking with hydrocarbon components.

The present invention is directed to the development of a composition and method for the synthesis of a catalyst for hydrodeoxygenation of an oxygen-containing hydrocarbon feed containing molybdenum and nickel compounds dispersed on the surface of an alumina carrier modified with a carbon coating (coke) and intended for carrying out hydrodeoxygenation processes of an oxygen-containing hydrocarbon feed or joint hydrotreating of oil fractions and oxygen-containing compounds obtained from vegetable (renewable) cheese i.

A catalyst for the hydrodeoxygenation of an oxygen-containing hydrocarbon feedstock is disclosed, including nickel and molybdenum, aluminum and carbon oxides, which, according to the invention, has the following composition, wt.%: NiO 4.0-6.0, MoO ₃ 15-25, C 1.0-3.0, the rest Al ₂ O ₃ .

A distinctive feature of the invention is the totality of the proposed solutions, including:

- the absence of phosphorus and silicon oxides in the composition of the catalysts, which allows to increase the resistance of the catalyst to coking;

- the initial precursors of the oxide phase of the catalysts are nickel salts of molybdone-nickel heteropoly acids Ni ₂ [Ni (OH) ₆ Mo ₆ O ₁₈ ] or Ni _3.5 H ₂ [NiMo ₉ O ₃₂ ] formed by the reaction of nickel hydroxocarbonate NiCO ₃ · nNi (OH) ₂ · mH ₂ O with H ₄ [Ni (OH) ₆ Mo ₆ O ₁₈ ] or H ₉ [NiMo ₉ O ₃₂ ] stabilized with dibasic or tribasic organic acids (oxalic, malonic, maleic, lactic, tartaric, succinic, citric). The high solubility of the precursors provides the formation of a stable impregnating solution with a pH of 2-4;

- γ-Al ₂ O ₃ carbonized by the method of pyrolysis of organic compounds is used as a carrier, which contains a carbon coating in an amount of 1-3 wt.% (in terms of carbon) and has a reduced concentration of Lewis-type acid centers, which also improves the stability of the catalyst to coking. The textural characteristics of the support, and the nominal high specific surface area (not less than 200 m ² / g), pore volume (0.8-1.1 cm ³ / g), and average pore diameter (not less than 100 Ǻ), ensure high dispersion of the active phase of the catalyst;

- thermal stages of preparation of the catalysts include only the stage of drying at temperatures of 25-130 ° C. The absence of the stage of calcination of the catalysts makes it possible to exclude the interaction of nickel atoms with the surface of the carrier, and, therefore, prevents the formation of spinels inactive in catalysis.

A comparative analysis of the composition of the prototype and the present invention shows that the common features are the composition of the catalysts, which includes the oxides of molybdenum, nickel and aluminum. The differences of the claimed catalyst from the known one lie in the quantitative content of molybdenum and nickel oxides and the method of synthesis of the catalyst, namely, the presence of carbon on the surface of the support and catalyst, in the composition of the initial precursors of molybdenum and nickel oxides, and the thermal treatment of the catalyst.

The above-described synthesis method of the proposed catalyst allows to increase the activity of the Ni-Mo catalyst for hydrodeoxygenation of oxygen-containing raw materials at temperatures of 270-340 ° C, a pressure of 3.0-5.0 MPa and a hydrogen circulation rate of 300-600 nl / l and the catalyst resistance to deactivation.

The invention is illustrated by the following examples.

Example 1

To prepare a joint impregnating solution of salts of the active components, 18.0 g of 6-molybdone-nickel heteropoly acid H ₄ [Ni (OH) ₆ Mo ₆ O ₁₈ ] and 4.3 g of nickel hydroxocarbonate NiCO ₃ · nNi (OH) ₂ · mH ₂ O are dissolved in 45 cm ^{3 of} hot distilled water with stirring. After the completion of the CO ₂ extraction, 5.0 g of citric acid monohydrate CH ₂ C (OH) CH ₂ (COOH) ₃ · H ₂ O are added to the resulting solution and the volume is adjusted to 72 cm ³ with water. The pH of the impregnation solution is 2.0-3.0. Carbonized alumina (with carbon content = 2.0 wt.%) Weighing 80 g is kept in vacuum for 30 minutes, then filled with a joint impregnating solution having a temperature of 40 ° C. The carrier is kept in an impregnating solution for 15 minutes. The resulting catalyst was dried at room temperature in an air stream and at temperatures of 80, 100, 130 ° C for 2 hours at each temperature.

The composition of the catalyst after calcination in air for 2 h at 550 ° C, wt.%: MoO ₃ 15.0, NiO 4.0 (table 1).

Example 2

To prepare a joint impregnating solution of salts of the active components, 21.1 g of 6-molybdon-nickel heteropoly acid H ₄ [Ni (OH) ₆ Mo ₆ O ₁₈ ] and 5.0 g of nickel hydroxocarbonate NiCO ₃ · nNi (OH) ₂ · mH ₂ O are dissolved in 45 cm ^{3 of} hot distilled water with stirring. After the completion of the CO ₂ evolution, 5.9 g of citric acid monohydrate CH ₂ C (OH) CH ₂ (COOH) ₃ H ₂ O are added to the resulting solution, and the volume is adjusted to 68 cm ³ with water. The pH of the impregnation solution is 2.0-3.0. Carbonized alumina (with carbon content = 2.0 wt.%) Weighing 75 g was kept in vacuum for 30 minutes, then filled with a joint impregnating solution having a temperature of 40 ° C. The carrier is kept in an impregnating solution for 15 minutes. The resulting catalyst was dried at room temperature in an air stream and at temperatures of 80, 100, 130 ° C for 2 hours at each temperature.

The composition of the catalyst after calcination in air for 2 h at 550 ° C, wt.%: MoO ₃ 17.8, NiO 4.7.

Example 3

To prepare a joint impregnating solution of salts of the active components, 21.1 g of 6-molybdon-nickel heteropoly acid H ₄ (Ni (OH) ₆ Mo ₆ O ₁₈ ] and 5.0 g of nickel hydroxocarbonate NiCO ₃ · nNi (OH) ₂ · mH ₂ O are dissolved in 45 cm ^{3 of} hot distilled water with stirring.After the completion of the CO ₂ evolution, 6.5 g of tartaric acid HOOC-CH (OH) -CH (OH) -COOH are added to the resulting solution and the volume is adjusted with water to 68 cm ³ , the pH of the impregnation solution is 2.0-3.0. Carbon oxide aluminum (with carbon content = 2.0 wt.%) weighing 75 g is kept in vacuum for 30 minutes, then pour with a joint feedstock solution having a temperature of 40 ° C. The carrier is kept in the impregnation solution for 15 minutes, the resulting catalyst is dried at room temperature in a stream of air and at temperatures of 80, 100, 130 ° C for 2 hours at each temperature.

The composition of the catalyst after calcination in air for 2 h at 550 ° C, wt.%: MoO ₃ 17.6, NiO 4.8.

Example 4

To prepare a joint impregnating solution of salts of the active components, 21.1 g of 6-molybdon-nickel heteropoly acid H ₄ [Ni (OH) ₆ Mo ₆ O ₁₈ ] and 5.0 g of nickel hydroxocarbonate NiCO ₃ · nNi (OH) ₂ · mH ₂ O are dissolved in 45 cm ^{3 of} hot distilled water with stirring. After the completion of the CO ₂ extraction, 5.0 g of succinic acid HOOC-CH ₂ -CH ₂ -COOH was added to the resulting solution, and the volume was adjusted with water to 68 cm ³ . The pH of the impregnation solution is 2.0-3.0. Carbonized alumina (with carbon content = 2.0 wt.%) Weighing 75 g was kept in vacuum for 30 minutes, then filled with a joint impregnating solution having a temperature of 40 ° C. The carrier is kept in an impregnating solution for 15 minutes. The resulting catalyst was dried at room temperature in an air stream and at temperatures of 80, 100, 130 ° C for 2 hours at each temperature.

The composition of the catalyst after calcination in air for 2 h at 550 ° C, wt.%: MoO ₃ 17.7, NiO 4.7.

Example 5

To prepare a joint impregnating solution of salts of the active components, 19.7 g of 9-molybdon-nickel heteropoly acid H ₉ [NiMo ₉ O ₃₂ ] and 5.8 g of nickel hydroxocarbonate NiCO ₃ · nNi (OH) ₂ · mH ₂ O are dissolved in 45 cm ^{3 of} hot distilled water with stirring. After the completion of the CO ₂ evolution, 7.4 g of tartaric acid HOOC-CH (OH) -CH (OH) -COOH was added to the resulting solution, and the volume was adjusted with water to 68 cm ³ . The pH of the impregnation solution is 2.0-3.0. Carbonized alumina (with carbon content = 2.0 wt.%) Weighing 75 g was kept in vacuum for 30 minutes, then filled with a joint impregnating solution having a temperature of 40 ° C. The carrier is kept in an impregnating solution for 15 minutes. The resulting catalyst was dried at room temperature in an air stream and at temperatures of 80, 100, 130 ° C for 2 hours at each temperature.

The composition of the catalyst after calcination in air for 2 h at 550 ° C, wt.%: MoO ₃ 17.7, NiO 4.7.

Example 6

To prepare a joint impregnating solution of salts of active components, 24.0 g of 6-molybdon-nickel heteropoly acid H ₄ [Ni (OH) ₆ Mo ₆ O ₁₈ ] and 5.5 g of nickel hydroxocarbonate NiCO ₃ · nNi (OH) ₂ · mH ₂ O are dissolved in 48 cm ³ hot distilled water with stirring. After the completion of the CO ₂ evolution, 6.5 g of citric acid monohydrate CH ₂ C (OH) CH ₂ (COOH) ₃ H ₂ O are added to the resulting solution and the volume is adjusted to 66 cm ³ with water. The pH of the impregnation solution is 2.0-3.0. Carbonized alumina (with carbon content = 2.0 wt.%) Weighing 73 g was kept in vacuum for 30 minutes, then filled with a joint impregnating solution having a temperature of 40 ° C. The carrier is kept in an impregnating solution for 15 minutes. The resulting catalyst was dried at room temperature in an air stream and at temperatures of 80, 100, 130 ° C for 2 hours at each temperature.

The composition of the catalyst after calcination in air for 2 h at 550 ° C, wt.%: MoO ₃ 20.0, NiO 5.2.

Example 7

To prepare a joint impregnating solution of salts of the active components, 27.6 g of 6-molybdon-nickel heteropoly acid H ₄ [Ni (OH) ₆ Mo ₆ O ₁₈ ] and 6.0 g of nickel hydroxocarbonate NiCO ₃ · nNi (OH) ₂ · mH ₂ O are dissolved in 48 cm ³ hot distilled water with stirring. After the completion of the CO ₂ evolution, 7.1 g of citric acid monohydrate CH ₂ C (OH) CH ₂ (COOH) ₃ H ₂ O are added to the resulting solution, and the volume is adjusted with water to 63 cm ³ . The pH of the impregnation solution is 2.0-3.0. Carbonized alumina (with carbon content = 2.0 wt.%) Weighing 70 g was kept in vacuum for 30 minutes, then filled with a joint impregnating solution having a temperature of 40 ° C. The carrier is kept in an impregnating solution for 15 minutes. The resulting catalyst was dried at room temperature in an air stream and at temperatures of 80, 100, 130 ° C for 2 hours at each temperature.

The composition of the catalyst after calcination in air for 2 h at 550 ° C, wt.%: MoO ₃ 23.0, NiO 5.8.

Example 8 (prototype)

To prepare a joint impregnating solution of salts of the active components, 19.4 g of ammonium heptamolybdate (NH ₄ ) ₆ Mo ₇ O ₂₄ · 4H ₂ O are dissolved in 45 cm ^{3 of} hot distilled water. Then, 15.4 g of nickel nitrate Ni (NO ₃ ) ₂ · 6H ₂ O and 11.2 g of citric acid monohydrate CH ₂ C (OH) CH ₂ (COOH) ₃ · H ₂ O are added to the solution with stirring. After the evolution of CO _{2, the} resulting solution adjusted with water to 72 cm ³ . The pH of the impregnating solution is 3.0-4.0. Alumina (with a content of SiO ₂ 0.6 wt.%, P ₂ O ₅ 0.6 wt.%) Weighing 80 g is kept in vacuum for 30 minutes, then it is poured with a joint impregnating solution having a temperature of 40 ° C. The carrier is kept in an impregnating solution for 15 minutes. The resulting catalyst is dried at room temperature in an air stream and at temperatures of 80, 100, 120 ° C for 2 hours at each temperature, then the temperature is raised at a rate of 1 ° C / min to 550 ° C and incubated for 2 hours

The composition of the catalyst after calcination in air for 2 h at 550 ° C, wt.%: MoO ₃ 15.1, NiO 4.0.

Example 9 (prototype)

To prepare a joint impregnating solution of salts of the active components, 23.1 g of ammonium heptamolybdate (NH ₄ ) ₆ Mo ₇ O ₂₄ · 4H ₂ O are dissolved in 45 cm ^{3 of} hot distilled water. Then, 18.8 g of nickel nitrate Ni (NO ₃ ) ₂ · 6H ₂ O and 13.8 g of citric acid monohydrate CH ₂ C (OH) CH ₂ (COOH) ₃ · H ₂ O are added to the solution with stirring. After the evolution of CO _{2, the} resulting solution adjusted with water to 68 cm. The pH of the impregnation solution is 3.0-4.0. Alumina (with a content of SiO ₂ - 0.6 wt.%, P ₂ O ₅ - 0.6 wt.%) Weighing 76 g was kept in vacuum for 30 min, then filled with a joint impregnating solution having a temperature of 40 ° C. The carrier is kept in an impregnating solution for 15 minutes. The resulting catalyst is dried at room temperature in an air stream and at temperatures of 80, 100, 120 ° C for 2 hours at each temperature, then the temperature is raised at a rate of 1 ° C / min to 550 ° C and incubated for 2 hours

The composition of the catalyst after calcination in air for 2 h at 550 ° C, wt.%: MoO ₃ 18.0, NiO 4.9.

The proposed synthesis method allows to obtain catalysts with the following texture characteristics (table 2): specific surface area of 150-180 m ² / g, specific pore volume of 0.38-0.46 cm ³ / g and average pore diameter of 112-120 Ǻ. Since the oxide form of the proposed catalysts contains a significant amount of water and organic compounds, the values of texture characteristics are slightly less than that of prototypes calcined at 550 ° C (samples 8 and 9). In the process of sulfidation of catalysts, organic precursors decompose and water is removed from the surface of the granules, while the specific surface area and pore volume increase 1.2-1.4 times.

The activity of the catalysts in the hydrodexigenation of an oxygen-containing hydrocarbon feed was determined by the ability to remove oxygen from oxygen-containing compounds: guaiacol and its hydrogenation products (pyrocatechol, cresols, phenol and cyclohexanol). As shown in [E. Laurent, B. Delmon, Appl. Catal. A: Gen. 109 (1994) 77-96], guaiacol in comparison with other oxygen-containing compounds is the most stable in deoxygenation reactions and the most prone to coke formation. Therefore, the use of raw materials based on it is justified for modeling oxygen-containing bio-oil compounds.

The catalysts prepared according to the proposed method (according to examples 1-7) and the catalysts according to prototype 8 and 9 were tested in the process of hydrodeoxygenation of a raw material containing guaiacol 3.0 wt.%, Dimethyl disulfide (DMDS) 0.3 wt.% In a toluene solvent, in a flow unit with the following conditions: temperature 280 ° C, bulk feed rate of 8.0 h ^-1 , pressure 3.0 MPa, hydrogen / feed circulation rate of 500 nl / l (table 2). Before testing, the catalysts were sulfidized with a mixture of DMDS in n-heptane (sulfur content 1.5 wt%) with gradual heating of the catalyst at a rate of 25 ° C / h and holding at 240 ° C for 8 h and 340 ° C for 6 h.

; $$n_D^{20}=\mathrm{1,479}$$

; содержание серы 1.130 мас.%, содержание кислорода 0.5 мас.%; температура начала кипения 180°C; температура выкипания 96% объема 360°C. В трубчатый реактор загружали 15 см³ катализатора, разбавленного SiC до общего объема 30 см³. Сульфидирование проводили смесью диметилдисульфида и керосиновой фракции при 240°C в течение 10 ч и при 340°C в течение 8 ч. Условия испытания: давление водорода 4.0 МПа, кратность циркуляции водорода 600 нл/л сырья, объемная скорость подачи сырья 1.5 ч^-1, температура в реакторе 340°C.The catalysts were also tested in the process of joint hydrotreating of oil fractions and oxygen-containing compounds obtained from plant (renewable) raw materials. For this, we used a mixture consisting of a straight-run diesel fraction (98 wt.) And guaiacol (2 wt.%), With the following characteristics: $$p_{\mathrm{four}}^{\mathrm{twenty}}=0.848$$

; $$n_D^{\mathrm{twenty}}=\mathrm{1,479}$$

; sulfur content 1.130 wt.%, oxygen content 0.5 wt.%; boiling point 180 ° C; boiling point 96% of the volume 360 ° C. 15 cm ^{3 of} catalyst diluted with SiC were charged into a tubular reactor to a total volume of 30 cm ³ . Sulfidation was carried out with a mixture of dimethyl disulfide and a kerosene fraction at 240 ° C for 10 hours and at 340 ° C for 8 hours. Test conditions: hydrogen pressure 4.0 MPa, hydrogen circulation rate of 600 nl / l of feed, bulk feed rate of 1.5 h ^-1 , the temperature in the reactor is 340 ° C.

The activity of the catalysts in hydrodesulfurization (GDS) was evaluated by the formula

, $$GD\mathrm{FROM}=\frac{S\mathrm{from}-S_{gg}}{S_{\mathrm{from}}}\cdot \mathrm{one\; hundred}\%$$

,

where GDS is the degree of hydrodesulfurization,%;

S _with - sulfur content in raw materials, wt.%;

S _g - sulfur content in the hydrogenate, wt.%.

The activity of the catalysts in hydrodeoxygenation (GDO) was evaluated by the formula:

, $$GD\mathrm{ABOUT}=\frac{O_{\mathrm{from}}-O_{gg}}{O_{\mathrm{from}}}\cdot \mathrm{one\; hundred}\%$$

,

where GDO - the degree of hydrodeoxygenation,%;

O _with the oxygen content in the feed, wt.%;

O _g - oxygen content in the hydrogenate, wt.%.

During tests in the hydrodeoxygenation of guaiacol, the catalysts reached stationary activity for 5-7 hours of continuous operation. The specific catalytic activity (UCA), measured in g O / (g (Mo + Ni) · h), was calculated after 10 hours of continuous operation. The stability of the catalysts was evaluated by changing the value of the UCA after 50 hours of continuous testing. The catalytic activity of the proposed catalysts is 2.0-2.3 times higher than that of the prototypes (table 2). The stability of the proposed catalysts was 95-97%, which is 13-15% higher than that of the prototypes.

In the process of joint hydrotreating of the diesel fraction and guaiacol, the catalysts reached stationary activity for 15–20 h of continuous operation. Table 2 presents the test results of the catalysts. The catalysts of the claimed composition and synthesis method have a higher catalytic activity in hydrodeoxygenation (99.8-100%) and hydrodesulfurization (99.0-99.6%) than prototypes. In the presence of the proposed catalysts in the process of joint hydrotreating of the diesel fraction and guaiacol, complete removal of oxygen (GDO is 100%) and the production of hydrogenate with a sulfur content of less than 50 ppm (GDS is 99.8%) are achieved.

Thus, the inventive catalysts show high efficiency in the processes of hydrodeoxygenation of oxygen-containing hydrocarbon feedstocks or joint hydrotreating of oil fractions and oxygen-containing compounds obtained from plant (renewable) feedstocks.

table 2 Textural Characteristics and Catalytic Properties of Catalysts No. Texture Features ¹ The sulfur content in the catalyst, wt.% Catalytic properties in the hydrodeoxygenation of guaiacol ² Catalytic properties in the joint hydrotreatment of diesel fraction and guaiacol ³ S _BET , m ² / g V _p cm ³ / g D _Wed , Ǻ before testing after testing

UKA, $$\frac{gO}{g(Mo+Ni)\cdot h}$$

Stability% GDO,% GDS,% Example 1 182 0.46 119 8.0 7.3 0.37 96 99.8 99.0 Example 2 175 0.45 118 9.4 8.6 0.40 97 99.9 99.3 Example 3 174 0.45 118 9.5 8.6 0.41 97 99.9 99.5 Example 4 175 0.43 119 9.4 8.5 0.41 96 99.9 99.4 Example 5 177 0.45 119 9.5 8.6 0.42 97 99.9 99.6 Example 6 161 0.42 117 10.2 9.1 0.41 96 one hundred 99.6 Example 7 152 0.38 112 11.2 9.9 0.40 95 one hundred 99.6 Example 8 (prototype) 196 0.60 119 8.7 6.5 0.17 83 99.5 98.3 Example 9 (prototype) 182 0.53 118 9.6 6.7 0.18 82 99.4 98.5 ¹ - Textural characteristics measured by nitrogen adsorption at 77K of prepared catalyst samples: S _BET , m ² / g — specific surface area calculated by BET from nitrogen adsorption isotherms; V _p , cm ³ / g - specific pore volume measured from isotherms of nitrogen desorption; D _cf , Ǻ is the average pore diameter calculated by the BJH method from nitrogen desorption isotherms; ² - Catalytic properties of the catalysts: UCA, g O / (g (Mo + Ni) · h) - specific catalytic activity, measured after 10 hours of continuous operation. Stability,% - the stability of the catalyst, calculated as the ratio of UCA after 50 hours of continuous operation, to UCA after 10 hours ³ - Catalytic properties of catalysts: GDS,% - catalytic activity in hydrodesulfurization, GDO,% - catalytic activity in hydrodeoxygenation, measured after 30 hours of continuous operation.

Claims (3)

1. The composition of the catalyst for the hydrodeoxygenation of an oxygen-containing hydrocarbon feed containing molybdenum compounds (15-25 wt.% MoO ₃ ) and nickel (4.0-6.0 wt.% NiO) dispersed on the surface of a carbon-modified alumina carrier (carbon content 1 -3 wt.%, Specific surface area of at least 200 m ² / g, specific pore volume of 0.8-1.1 cm ³ / g, average pore diameter of at least 100 Ǻ) and intended for carrying out hydrodeoxygenation processes of oxygen-containing hydrocarbon feedstocks or joint hydrotreating oil fra ktsiy and oxygen-containing compounds obtained from plant (renewable) raw materials. 2. A method of synthesizing a catalyst for hydrodeoxygenation of an oxygen-containing hydrocarbon feedstock according to claim 1, comprising impregnating a carbon-modified alumina support with an aqueous solution of Mo and Ni compounds, characterized in that a joint impregnating solution is prepared containing nickel salts of molybdenum-nickel heteropoly acids stabilized with dibasic or tribasic organic acids (oxalic, malonic, maleic, dairy, wine, amber, lemon), at a pH of 2.0-3.0, and a single impregnation is performed akuumirovannogo carrier at a temperature of 40 ° C with subsequent heat treatment at temperatures not exceeding 130 ° C. 3. The method according to claim 2, characterized in that Ni ₂ [Ni (OH) ₆ Mo ₆ O ₁₈ ] or Ni _3.5 H ₂ [NiMo ₉ O ₃₂ ] are used as molybdenum and nickel compounds.