RU2286847C1 - Method of preparing petroleum fraction hydrofining catalyst - Google Patents

Abstract

FIELD: petroleum processing catalysts.

SUBSTANCE: catalyst designed for using in petroleum fraction hydrofining, which contains oxides of cobalt, molybdenum, phosphorus, lanthanum, boron, and aluminum, is prepared by mixing aluminum hydroxide with boric acid solution and nitric acid solution of lanthanum carbonate followed by drying, calcination, impregnation of resulting carrier with cobalt nitrate and ammonium paramolybdate solution in nitric acid at pH 2.0-3.5 and 40-80°C in presence of phosphoric acid followed by drying and calcination at elevated temperature.

EFFECT: enabled production of hydrogenate with reduced content of sulfur compounds.

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Description

The invention relates to the field of oil refining, in particular to a method for the preparation of catalysts intended for use in the hydrotreatment of petroleum fractions.

From patent No. 2102146 (RU, IPC ⁷ 01 J 37/04, publ. 20.01.98, bull. No. 2) there is known a method for preparing a catalyst for hydrotreating oil fractions, which involves mixing an alumina carrier with boric acid and a molybdenum salt solution. The resulting aluminobormolybdenum composition is impregnated with a solution of nickel nitrate in the presence of phosphoric acid at a pH of 3.6-4.5 and a temperature of 40-60 ° C.

The resulting catalyst has a strength index of 2.2-2.5 kg / mm of the diameter of the granule and provides a degree of desulfurization at a temperature of 335 ° C at the level of 91.9%. During hydrotreating of the benzene-toluene-xylene fraction, the degree of desulfurization at a temperature of 250 ° C is 75.0%, while hydrogenation is necessary 3-4 times a year due to coking of the catalyst in order to restore the activity of the catalyst.

The closest (prototype) in technical essence and the achieved result solution, known from patent No. 2197323 (RU, В 01 J 23/88, publ. 27.01.03.), Is a solution that describes a method for preparing a catalyst for hydrotreating oil fractions containing oxides of cobalt, molybdenum, phosphorus, lanthanum, boron and aluminum oxide. The known method includes extrusion molding aluminum hydroxide containing modifying compounds, drying, calcining, impregnating with a solution of the compounds of the active components of nickel and / or cobalt, molybdenum, followed by drying and calcination. As the aluminum hydroxide, the rehydration product of the X-ray amorphous layered aluminum compound of the formula Al ₂ O ₃ · nH ₂ O, where n = 0.3-1.5, which contains partially or fully modifying metal compounds selected from the group: sodium, iron, is used , lanthanum, cerium, zinc, copper, tungsten, in an amount of 0.01-5 wt.% and / or at least one non-metal compound selected from the group: phosphorus, fluorine, boron, in an amount of 0.5-10 wt. %

The catalyst manufactured by a known method has a sufficiently high strength and activity.

The disadvantage of this method of preparation of the catalyst is the complexity of the technical solution.

The present invention is directed to the development of a method for preparing a catalyst with increased hydrodesulfurization activity in the processing of petroleum feed containing large amounts of unsaturated hydrocarbons.

The inventive method of preparing a catalyst for hydrotreating oil fractions containing oxides of cobalt, molybdenum, phosphorus, lanthanum, boron and alumina, comprising impregnating the carrier with compounds of the active components — a solution of cobalt nitrate and ammonium paramolybdate, followed by drying and calcination at elevated temperatures, in which according the invention, aluminum hydroxide is mixed with a solution of boric acid and nitric acid solution of lanthanum carbonate, followed by drying and calcination, and the impregnation of the obtained ator cobalt nitrate solution and ammonium paramolybdate is carried out at pH 2.0-3.5 and temperature of 40-80 ° C in the presence of phosphoric acid.

The resulting catalyst has the following component composition, wt.%:

Soo 2.5-4.0 MoO ₃ 8.0-12.0 Na ₂ O 0.01-0.08 La ₂ o ₃ 1.5-4.0 P ₂ O ₅ 2.0-5.0 B ₂ O ₃ 0.5-3.0 Al ₂ About ₃ rest.

A comparative analysis of the prototype and the present invention shows that common features are the composition of the catalysts, which includes cobalt, molybdenum, phosphorus, lanthanum, boron and aluminum oxide oxides, as well as impregnation of the carrier with compounds of the active components — a solution of cobalt nitrate and ammonium paramolybdate, followed by drying and calcination at elevated temperature.

The difference of the proposed method from the known one is that aluminum hydroxide is mixed with a solution of boric acid and a nitric acid solution of lanthanum carbonate, followed by drying and calcination, and the carrier is impregnated with a solution of cobalt nitrate and ammonium paramolybdate at pH 2.0-3.5 and temperature 40-80 ° C in the presence of phosphoric acid.

Prepared by the proposed method, the catalyst provides a more efficient hydrotreating of raw materials containing an increased amount of unsaturated hydrocarbons.

The following are specific examples of the implementation of the proposed method.

Example 1

The carrier is prepared by mixing aluminum hydroxide (a cake of pseudoboehmite and boehmite structure, consisting of 60-40 wt.% Pseudoboehmite and 40-60 wt.% Boehmite. The composition includes up to 0.10 wt.% Na ₂ O) in an amount of 40 kg from 0 , 7 kg of boric acid and nitric acid solution of lanthanum carbonate. The resulting mass is stirred at a temperature of 30 ° C for 15 minutes. After obtaining a homogeneous mass, add 1.5 DM ³ 25% aqueous ammonia and the mass is stirred at 80 ° C for 20 minutes. The finished mass with a dry matter content of 50% is molded into granules with a diameter of 1.7 mm The formed granules are dried for 5 hours at a temperature of 120-200 ° C, and then calcined at a temperature of 450 ° C for 5 hours.

At the same time, an impregnating solution is prepared: 400 dm ^{3 of} water is poured into the solvent, 40 dm ^{3 of} phosphoric acid are added and 170 kg of cobalt nitrate are charged with continuous stirring at a temperature of 40 ° C. The resultant solution with a concentration of 50 g / dm ³ at pH 3.5 CoO charged 120 kg of ammonium paramolybdate to prepare a solution with a concentration of 200 g / dm ³ MoO _3.

Next, the carrier is impregnated with compounds of the active components, which is carried out as follows. The calculated amount of the carrier obtained by the above-described method is loaded into the container, after which the calculated amount of the impregnating solution (40 ° C, pH 3.5) containing cobalt nitrate, ammonium paramolybdate and phosphoric acid is added from the measuring device.

The carrier impregnated with compounds of active components is dried at a temperature of 150 ° C and calcined at a temperature of 450 ° C.

The finished catalyst contains the following ratio of components, wt.%:

Soo 4.0 MoO ₃ 12.0 Na ₂ O 0.08 La ₂ o ₃ 4.0 P ₂ O ₅ 2.0 B ₂ O ₃ 3.0 Al ₂ About ₃ rest.

The catalyst has a strength index of 2.3 kg / mm of pellet diameter. Testing it during hydrotreatment of diesel fuel at a temperature of 335 ° C provides a 92.5% removal depth of sulfur compounds. Using it in the process of hydrofining the benzene-toluene-xylene fraction at 230 ° C provides a reduction in sulfur compounds by 82 wt.%. At the same time, the inter-regeneration period is 11 months; after 2 years of operation, hydrogen treatment of the catalyst is required after 6 months.

Example 2

The carrier is prepared by mixing aluminum hydroxide (a cake of pseudoboehmite and boehmite structure, consisting of 60-40 wt.% Pseudoboehmite and 40-60 wt.% Boehmite. The composition includes up to 0.10 wt.% Na ₂ O) in an amount of 40 kg from 0 , 6 kg of boric acid and nitric acid solution of lanthanum carbonate. The resulting mass is stirred at a temperature of 30 ° C for 15 minutes. After obtaining a homogeneous mass, add 1.5 DM ³ 25% aqueous ammonia and the mass is stirred at 80 ° C for 20 minutes. The finished mass with a dry matter content of 50% is molded into granules with a diameter of 1.7 mm The formed granules are dried for 5 hours at a temperature of 120-200 ° C, and then calcined at a temperature of 450 ° C for 5 hours.

At the same time, an impregnating solution is prepared: 400 dm ^{3 of} water is poured into the solvent, 50 dm ^{3 of} phosphoric acid are added and 160 kg of cobalt nitrate are charged with continuous stirring at a temperature of 80 ° C. The resultant solution with a concentration of 50 g / dm ³ at pH 2.0 CoO charged 110 kg of ammonium paramolybdate to prepare a solution with a concentration of 190 g / dm ³ MoO _3.

Next, the carrier is impregnated with compounds of the active components, which is carried out as follows. The calculated amount of the carrier obtained by the above-described method is loaded into the container, after which the calculated amount of an impregnating solution (80 ° C, pH 2.0) containing cobalt nitrate, ammonium paramolybdate and phosphoric acid is added from the measuring device.

The carrier impregnated with compounds of active components is dried at a temperature of 150 ° C and calcined at a temperature of 450 ° C.

The finished catalyst contains the following ratio of components, wt.%:

Soo 2,5 MoO ₃ 8.0 Na ₂ O 0.01 La ₂ About ₃ 1,5 P ₂ O ₅ 5,0 B ₂ O ₃ 0.5 Al ₂ About ₃ rest.

The catalyst has a strength index of 2.3 kg / mm of pellet diameter. Testing it during hydrotreatment of diesel fuel at a temperature of 335 ° C provides a 93.0% depth of removal of sulfur compounds. Using it in the process of hydrofining the benzene-toluene-xylene fraction at 230 ° C provides a reduction in sulfur compounds by 83 wt.%. At the same time, the inter-regeneration period is 11 months; after 2 years of operation, hydrogen treatment of the catalyst is required after 6 months.

The study of the proposed catalysts in the hydrotreatment process provides hydrogenated with a low content of sulfur compounds. At the same time, the improvement of technical and economic indicators will be achieved: saving energy costs and material resources.

Claims (1)

A method of preparing a catalyst for hydrotreating oil fractions containing oxides of cobalt, molybdenum, phosphorus, lanthanum, boron and alumina, comprising impregnating the carrier with compounds of the active components — a solution of cobalt nitrate and ammonium paramolybdate, followed by drying and calcination at elevated temperatures, characterized in that aluminum hydroxide is mixed with a solution of boric acid and a nitric acid solution of lanthanum carbonate, followed by drying, calcination and impregnation of the resulting carrier with a solution of nitrogen islogo cobalt ammonium paramolybdate and pH equal to 2.0-3.5, temperature 40-80 ° C in the presence of phosphoric acid.