A catalyst for hydrotreating petroleum fractions and the method of its preparation

 

(57) Abstract:

The invention relates to catalytic chemistry, in particular to the preparation of catalysts for Hydrotreating petroleum fractions, and can be used in the refining industry. Describes a new catalyst for Hydrotreating petroleum fractions containing oxides of molybdenum, Nickel and/or cobalt and aluminum, molded in the form of hollow cylindrical granules with a certain ratio of the outer diameter to the inner diameter. The catalyst additionally contains silicon oxide in the following ratio, wt. percent: molybdenum oxide, 4 to 8, the oxide of Nickel and/or cobalt oxide 1 - 3, the silicon oxide 4 - 8, aluminum oxide - the rest is up to 100, and is the ratio of the outer diameter to the inner diameter of 2.7 to 6.0. The technical result is an increase in the strength of the catalyst of the protective layer for Hydrotreating petroleum fractions. 2 S. p. f-crystals, 1 table.

The invention relates to catalytic chemistry, in particular to the preparation of the catalyst for Hydrotreating of crude oil, and can be used in the oil industry.

The aim of the invention is to increase the mechanical strength of the catalyst protective is the technical essence and the achieved effect is the catalyst of the protective layer for Hydrotreating petroleum fractions [SU 1815993 A1, 10.03.96] containing wt.%: Nickel oxide 2-2; molybdenum oxide 3-4; alumina rest to 100, formed as hollow cylindrical granules with an external diameter of 10-15 mm and an inner diameter of 3-5 mm, the Use of such a catalyst as the catalyst of the upper confining layer in the Hydrotreating reactors instead of porcelain balls helped to reduce the pressure drop in the reactor to reduce the amount of catalyst dust and crumbs, to increase the service life of the main Hydrotreating catalyst prior to regeneration to 24-28 months, increase the degree of removal of sulfur soedinenii up to 98% for diesel fractions for P= 4-6 MPa, Vc=3-5 h-1temperature 340-360oC. the Disadvantage of this catalyst is not sufficiently high mechanical strength.

The closest known solution for the method of producing catalyst for Hydrotreating of crude oil in the form of hollow cylinders, allowing to reduce the hydraulic resistance layer alumnirelations and aluminoborosilicate catalysts in the process of Hydrotreating of crude oil is the way [SU 1297899 A1, 23.03.87]. The known method is to obtain a carrier in the form of new cylinders with a certain ratio of the outer poverhnosti. Introduction active components carry out the impregnation of the finished carrier with an aqueous solution of paramolybdate ammonium nitrate Nickel or cobalt in the presence of the stabilizer - tartaric acid taken in the quantity of 1-4 wt.%. Obtaining catalyst includes precipitation, peptization, forming aluminum hydroxide, drying, calcination and impregnation received media these solutions paramolybdate ammonium nitrate Nickel or cobalt, and reptitiously aluminum hydroxide to impose an additional 4-6 wt.% an aqueous solution of ammonia and 4-8 wt.% triethylene glycol, dried up 60-65% humidity and formed into hollow cylinders of specified sizes. The disadvantage of this catalyst is a complex way of its preparation and low strength.

The invention consists in the following.

The invention is directed to solving the problem of obtaining high catalyst protective layer for Hydrotreating petroleum fractions to improve the dispersion of the raw material flow, reduce the hydraulic resistance by preventing clogging of the catalyst layer of the corrosion products, to protect the core layer catalyst from coking due to the increased acaat to solve the problem. This technical result is achieved by obtaining the catalyst, the composition of which enter 10-40 wt.% kaolin with the following chemical composition of the catalyst, wt. percent: molybdenum oxide 4-8, oxide of Nickel and/or cobalt 1-3, the silicon oxide 4-18, alumina rest to 100 and the catalyst is molded in the form of hollow cylindrical granules with the ratio of the outer diameter to the inner 2,7-6,0; method of preparation of the catalyst, including the precipitation of aluminium hydroxide, peptization, heating to a certain temperature, holding at that temperature with continuous stirring for 1-4 hours, the introduction of fractions of 0.01-0.2 mm-alumina containing from 11 to 14 wt.% molybdenum oxide and 3-5 wt.% oxide of Nickel and/or cobalt, and the introduction of 10-40 wt.% kaolin, mixing, molding in the form of hollow cylindrical granules with a certain ratio of external diameter to the internal diameter of 2.7 to 6.0, drying, calcining at 650-850oC.

Essential features of the invention are present in the catalyst composition of kaolin, the ratio of its components, the ratio of the outer diameter to the inner diameter and the method of preparation of the catalyst.

Distinctive features of this invention are nelidina 4-8, oxide of Nickel and/or cobalt 1-3, the silicon oxide 4-18, alumina rest to 100, a certain ratio of external diameter to the internal diameter of 2.7 to 6.0, and the method of preparation of the catalyst, namely, that with the purpose of increasing the mechanical strength of the catalyst is aluminum hydroxide after peptization is heated to 70-80oC and kept at this temperature for 1-4 hours, then injected 50-70 wt.% -aluminum oxide containing oxides of molybdenum, Nickel and/or cobalt with a particle size of 0.01 to 0.2 mm, and 10-40 wt.% kaolin.

The novelty of the present invention is to obtain a catalyst of the protective layer for Hydrotreating petroleum fractions in the form of a hollow cylinder with a ratio of the outer to the inner diameter of 2.7 to 6.0, containing 10-40 wt.% kaolin to improve the mechanical strength, and method of its production, including the introduction of pre-warmed to 70-80oC and aged at this temperature for 1-4 hours aluminum hydroxide fraction of aluminum oxide of 0.01-0.2 mm, containing oxides of molybdenum, Nickel and/or cobalt and subsequent introduction of 10-40 wt.% kaolin, drying and calcining at a temperature of 650-850oC.

This solution allows you get auktsionnyi cycle of operation of the installation.

The invention is illustrated by the following examples.

Example 1. 500 g of aluminum hydroxide, sulfate obtained by the method, with a humidity of 80 wt.% peptizer with continuous mixing 45 ml of 56% nitric acid to pH 3-4 and add 500 ml of water, heated to 70oC with constant stirring withstand a weight of 2 hours at this temperature.

Simultaneously prepare active-alumina containing oxides of molybdenum, Nickel and/or cobalt in the following way. Take 3500 g pellet of aluminum hydroxide, sulfate obtained by the method, with a humidity of 80 wt.%, stirred at 50oC to obtain a homogeneous mass. Then, with continuous stirring and heating in a lot make salt paramolybdate ammonium [(NH4)6Mo7O246H2O] mass of 84.0 g, continue to mix until obtaining a mass with a moisture content of 68 wt.% and gradually add in the weight of concentrated nitric acid until the pH of the medium 4, continue to stir and maintain the temperature of the mass 50oC for 30 minutes the Mass is formed into extrudates, provalivajut, dried at 190oC for 10 hours and calcined at 550oC 4 hours. Cooked-alumina containing oxides of molybdenum and Nickel , has the following hi,0. Then keep grinding pellets in a ball mill, filtering the fraction of 0.01 to 0.2 mm

Later in the prepared aluminum hydroxide is injected 737 g fraction of 0.01-0.2 mm-alumina containing oxides of molybdenum and Nickel, with a moisture content of 5 wt. % and 291 g of kaolin with a moisture content of 14 wt.% and the content of SiO245 wt.%. The mass is thoroughly mixed, formed into cylindrical pellets with a ratio of outer diameter to inner diameter of 4 by extrusion, dried at 190oC for 10 hours and calcined at 650oC 4 hours.

The catalyst has the following chemical composition, wt.%: NiO - 2,0; MoO3- 7,3; SiO2to 10.7; Al2O3- the rest is up to 100.

The strength of the catalyst - 135% compared to the prototype (example 7).

Example 2. The catalyst prepared according to example 1, except that the heat treatment of the finished catalyst are as follows: dried at 190oC 10 h and calcined at 850oC 4 h

The catalyst has the following chemical composition, wt.%: NiO - 2,0; MoO3- 7,3; SiO2to 10.7; Al2O3- the rest is up to 100.

The strength of the catalyst - 145% compared to the prototype (example 7).

Example 3. The catalyst prepared according to example 1, only prepared according to example 1 hydrox is.% Nickel oxide (NiO), with moisture content of 5 wt.% and 465 g of kaolin with a moisture content of 14 wt.% and the content of SiO245 wt.%. Next, the catalyst is prepared analogously to example 1.

The catalyst has the following chemical composition, wt.%: NiO - 1,7; MoO3- 6,4; SiO2- 15,0; Al2O3- the rest is up to 100.

The strength of the catalyst 140% compared to the prototype (example 7).

Example 4. The catalyst prepared according to example 1, except that in the preparation of aluminum hydroxide containing metal oxides, instead of 84 g of Nickel nitrate [Ni(NO3)26H2O] take 84 g of cobalt nitrate [Co(NO3)26H2O] and granules prepared catalyst molded in the form of hollow cylindrical pellets with a ratio of outside diameter to the inside of 2.7. The heat treatment is carried out analogously to example 1.

The catalyst has the following chemical composition, wt.%: CoO - 2,0; MoO3- 7,3; SiO2to 10.7; Al2O3- the rest is up to 100.

The strength of the catalyst 140% compared to the prototype (example 7).

Example 5. Prepare the catalyst of example 1, but the catalyst has the following chemical composition, wt.%: NiO -2,0; MoO3is 7.3; SiO2- 4,0; Al2O3- the rest is up to 100.

The strength of the catalyst - 120% with EBUSY chemical composition, wt.%: NiO - 1,0; MoO3- 4,0; SiO2- 18,0; Al2O3- the rest is up to 100.

The strength of the catalyst is 150% compared to the prototype (example 7).

Physico-chemical properties of catalysts and heat treatment conditions shown in the table. The table shows that the introduction of the catalyst of silica from kaolin helps to increase the durability of the catalyst (120-150% vs. 100% in the prototype). Also the method of preparation of this catalyst compared to the prototype, more economical as excluded stage impregnation of the carrier, and the above sequence of operations and the introduction of kaolin allow to obtain high strength catalyst.

1. The catalyst of the protective layer for Hydrotreating petroleum fractions containing oxides of molybdenum, Nickel and/or cobalt and aluminum, molded in the form of hollow cylindrical granules with a certain ratio of the outer diameter to the inner diameter, wherein the catalyst further comprises an oxide of silicon in the following ratio, wt.%:

Molybdenum oxide - 4 - 8

Oxide of Nickel and/or cobalt - 1 - 3

The silicon oxide - 4 - 18

Aluminum oxide - the Rest is up to 100

and is the ratio of the outer diameter is rootcandy oil fractions, including deposition of aluminum hydroxide, peptization, the introduction of active components, the molding in the form of hollow cylindrical granules, drying, annealing, characterized in that the aluminum hydroxide after peptization is heated to 70 - 80oC and maintained at this temperature with stirring for 1 to 4 hours, enter 50 to 70 wt.% fraction of 0.01 - 0.2 mm-alumina containing from 11 to 14 wt.% molybdenum and 3 to 5 wt.% oxide of Nickel and/or cobalt, then enter 10 to 40 wt.% kaolin, dried and calcined at a temperature of 650 - 850oC.

 

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FIELD: production of hydrorefining catalyst.

SUBSTANCE: the invention presents a method of production of hydrorefining catalysts, that provides for preparation of non-calcined catalyst for hydrorefining of hydrocarbonaceous raw materials polluted with low-purity heteroatoms. The method includes: combining of a porous carrying agent with one or several catalytically active metals chosen from group VI and group III of the Periodic table of elements by impregnation, joint molding or joint sedimentation with formation of a predecessor of the catalyst containing volatile compounds, decrease of the share of the volatile compounds in the predecessor of the catalyst during one or several stages, where at least one stage of decrease of the shares of the volatile compounds is carried out in presence of at least one compound containing sulfur; where before the indicated at least one integrated stage of decrease of the share of volatile compounds - sulfurization the indicated predecessor of the catalyst is not brought up to the temperatures of calcination and the share of the volatile compounds in it makes more than 0.5 %. Also is offered a not-calcined catalyst and a method of catalytic hydrorefining. The invention ensures production of a catalyst of excellent activity and stability at hydrorefining using lower temperatures, less number of stages and without calcination.

EFFECT: the invention ensures production of a catalyst of excellent activity and stability at hydrorefining using lower temperatures, less number of stages and without calcination.

10 cl, 8 ex, 4 dwg

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