The preparation method of catalyst for hydrotreating petroleum fractions

 

(57) Abstract:

Usage: petrochemistry. The inventive catalyst for Hydrotreating petroleum fractions obtained by the introduction of aluminum hydroxide in the amount of 5-15% by weight of the crushed aluminoborosilicate catalyst in the presence of phosphoric and boric acids, followed by shaping, drying and calcining the granules media. Salts of Nickel and molybdenum is introduced into the carrier by impregnation its granules with a solution of these salts, repeated drying and calcining. The technical result is a simplification of the process and ensuring high gidroobesserivaniya activity of the obtained catalyst.

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

Known method of preparing the catalyst promoted with boron oxide in an amount of 0.1 to 5.0%.

In the composition of the catalyst comprises a metal selected from the elements V, VI, VIII and VA groups.

It is preferable to use Co, Mo, Ni or a mixture thereof, and R. Molybdenum is present in the form of oxide in an amount of 3-25%, Co or Ni in the form of oxides in an amount of 0.1 to 8.0 is luminia and boron is produced by precipitation from appropriate solutions, or impregnation of the powder of Al2ABOUT3a solution of boric acid or other suitable boron compounds. The catalyst used in the Hydrotreating of petroleum fractions at a temperature 260-482oWith the pressure 70-210 MPa and space velocity of the raw material of 0.2 to 5.0 h-1(U.S. patent 4724226, 1988).

The disadvantage of this method is the low activity of the obtained catalyst, which leads to the need for a process at a high pressure of 70 MPa.

Known methods of preparation of the catalyst Hydrotreating petroleum fractions using the techniques of putting in hydrooxide media salts of Nickel and molybdenum, forming, drying and calcining the obtained granules carried out in various ways, including the use of phosphoric and nitric acids (RF patents 2098181, 1997, 2008972, 1994). These methods allow to obtain catalysts with high efficiency.

At the present time remains a challenge finding new, better ways of preparation of the catalyst Hydrotreating petroleum fractions with controlled porous structure.

Closer to the proposed invention is a method you need a kitchen is as aluminum and aluminoborosilicate crumbs with a particle size of 10-100 μm, pre-treated with a solution of nitric acid at pH 1.5 to 3.0 and a temperature of 80-95oWith assumed mass ratio (4-9): 1. Crushed allocability catalyst - aluminoborosilicate crumb, pre-treated as above described, is introduced into the aluminum hydroxide with subsequent shaping, drying and calcining the granules media. Granules of the carrier is impregnated with a solution of salts of hydrogenating metals - Nickel and molybdenum, followed by drying and calcining (RF patent 2084285, 1997).

The disadvantage of this method lies in the complexity of the technology of preparation of the catalyst, as indicated crumbs before putting in the media is necessary to treat with nitric acid.

Object of the invention is the simplification of the preparation of the catalyst, while maintaining its high activity.

The task is achieved by the described method of preparation of catalyst for Hydrotreating petroleum fractions by introducing the aluminum hydroxide crushed aluminoborosilicate catalyst with subsequent shaping, drying and calcining the pellets carrier, impregnating the latter with a solution of salts of Nickel and molybdenum, re-drying and is carried out in the presence of phosphoric and boric acids and crushed allocability the catalyst is used in amounts of 5-15% by weight of aluminum hydroxide.

The proposed catalyst has the following chemical composition, wt.%:

Nickel oxide (NiO) - 2,5-4,0

Molybdenum oxide (Moo3) - 10,0-12,0

The sodium oxide (Na2O) - 0,03-0,1

Boron oxide (2O5) - 0,3-0,9

The oxide of phosphorus (P2O5) - 3,2-5,0

Aluminum oxide (Al2O3) - Rest

Index strength, kg/mm - 2,2-3,0

The average radius of the pores,- - 120-200

Add chopped aluminoborosilicate catalyst provides a carrier, the average radius of the pores is 120-200< / BR>
As crushed aluminoborosilicate catalyst may be used aluminoborosilicate crumb, which is a waste product of aluminoborosilicate catalyst, exhaust and fresh allocability catalyst, preferably crushed to a size less than 0.05 mm as specified catalyst may be used, in particular, aluminoborosilicate catalysts for Hydrotreating, hydrocracking, hydroisomerization oil fractions.

The media prior to impregnation is dried at a temperature of 120-180

This method of preparation of the catalyst provides the structure of the catalyst, which is optimal in the processing of petroleum fractions, in particular vacuum gasoil.

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

Example 1.

Prepare media by precipitation of the gel formed by the interaction of sodium aluminate and nitric acid at a temperature of 50oC. After the deposition conduct stabilization of aluminum hydroxide at pH of 9.0, temperature 90oC for 60 min, the Obtained aluminum hydroxide is filtered off and then washed with demineralized water for washing from ions of Na+and NO3-. The pellet was washed aluminum hydroxide in the amount of 100 kg load in a kneading machine, then add 2.0 kg N3IN4and 8.0 kg N3RHO4and continue stirring for 5 minutes Then the resulting slurry add 5 kg (5 wt.%) crushed to a size less than 0.05 mm aluminoborosilicate catalyst (MEO - 4 wt.%, Moo3- 12 wt.%, Na2O - 0.07 wt.%, Al2ABOUT3- else) and continue stirring for 20 minutes Prepared a lot fo granules impregnated with the solution, which is prepared as follows: into the container pour 200 DM3ammonia water and 200 DM3water until the ammonia content of 14%, add 5,0 kg ammonium molybdate under stirring. After the complete dissolution of ammonium molybdate add 7,4 kg of Nickel nitrate and stirred for 60 minutes

The resulting solution was fed into propitiating, where to download the calcined granules. Impregnation lead for 20 min, after which the granules of the catalyst is dried at 180oWith and calcined.

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

Nickel oxide (NiO) - 2,5

Molybdenum oxide (Moo3) to 12.0

The sodium oxide (Na2O) - 0,03

Boron oxide (2O5) - 0,9

The oxide of phosphorus (P2O5) - 3,2

Aluminum oxide (Al2O3) - Rest

Index strength, kg/mm - 2,7

The average radius of the pores,- 120

In the process of Hydrotreating of vacuum gas oil at a temperature of 360oC, a pressure of 40 MPa, the space velocity of the feedstock 1.5 h-1the degree of desulfurization is 95,0%.

Example 2.

The method is carried out analogously to example 1, except that, if"ptx2">

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

Nickel oxide (NiO) - 4,0

Molybdenum oxide (Moo3) - 10,0

The sodium oxide (Na2O) - 0,1

Boron oxide (2O5) - 0,3

The oxide of phosphorus (P2O5) - 5,0

Aluminum oxide (Al2O5) - Rest

Index strength, kg/mm - 3,0

The average radius of the pores,- 200

In the process of Hydrotreating of vacuum gas oil at a temperature of 360oC, a pressure of 40 MPa, the space velocity of the feedstock 1.5 h-1the degree of desulfurization is 97%.

Thus, the proposed method for the preparation of the catalyst simplifies the process and provides a high gidroobesserivaniya activity of the obtained catalyst.

The preparation method of catalyst for Hydrotreating petroleum fractions by introducing the aluminum hydroxide crushed aluminoborosilicate catalyst with subsequent forming, drying, and calcining the pellets carrier, impregnating the latter with a solution of salts of Nickel and molybdenum, again drying and calcining, characterized in that the introduction of aluminum hydroxide crushed aluminoborosilicate catalyst is p used in the amount of 5-15% by weight of aluminum hydroxide.

 

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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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