The preparation method of catalyst for hydrotreating petroleum fractions

 

(57) Abstract:

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

The catalyst was prepared by impregnation of the support with a solution of salts of Nickel and molybdenum in the presence of phosphoric acid at pH = 2,5 - 3,5, followed by drying and calcination.

As a carrier, a mixture of aluminum hydroxide and aluminoborosilicate crumbs with a particle size of 10 to 100 microns, pre-treated with a solution of nitric acid at pH = 1.5 to 3.0 and a temperature of 80 - 95oC, taken in the mass ratio (4 - 9):1. table 1.

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

Known method of preparing a catalyst for Hydrotreating, which used the main bearer of soosazhdenie of silicates and alumets. In the preparation of the basic carrier and alumosilicates original mix aluminol and silicasol in this ratio is>. Alumosilicate mixed with 5 to 50% wt. (20 to 40% wt.) inorganic oxide (ZrO2, IhO2or B2O3). The obtained dry mixture is impregnated with a solution of boron compounds and phosphates so that the phosphate content of boron was 13 35% Then the carrier is dried and impregnated with a solution of salts of Nickel and molybdenum. Then again dried and calcined at 700 1200oC. the Method can be illustrated as follows. Water glass diluted with water, acidified with hydrochloric acid, diluted with water and mixed with an aqueous solution of Al2(SO4)3. Then to the mixture was added a concentrated solution of NH4OH, diluted with water and at a pH of 9.4 precipitated hydrogel. It is filtered off and washed with water to remove ions of Na+SO-4and NH+4. The hydrogel repulping in an aqueous solution of phosphoric and boric acid. Reformirovanie carried out at 70oC, then the precipitate is dried at 120oC, crushed and passed through a sieve of 10 to 30 mesh. The resulting powder was impregnated with a solution containing molybdenum acid and Nickel nitrate in an aqueous solution of ammonia.

The impregnated particles are dried and calcined for 1 h at 600oC. Obtain a catalyst containing 2.0% by weight. NiO and 16% wt. MoO

A known method of preparation of Hydrotreating catalyst, whereby the catalyst is prepared by impregnation of the pre-calcined alumina with a solution of salts of hydrogenating metals VIB and VIII groups (including salts of Mo and Ni) in the presence of P-containing acids, including H3PO3H3PO4or mixtures thereof, followed by drying and calcination. This can be used any Al2O3with a specific surface area of 20 to 350 m2/, the Catalyst is dried at 25 200oC, then heated in an inert (N2, He, Ar, Kr, or a mixture) atmosphere to 200 600oC. the Catalyst has the following chemical composition, wt. Ni 0,2 10; Mo 0,2 20; P 0,2 10.

The catalysts were tested in the Hydrotreating of gas oil at a temperature of 315 - 343oC, a pressure of 56 MPa, the space velocity of the feedstock 1.5 h-1. The degree of desulfurization is 92%

The disadvantage of this method is that the resulting catalyst has nedostatecnou essence and the achieved result is a method for preparing a catalyst for Hydrotreating petroleum fractions by pre-impregnation of the calcined alumina with a solution of salts of Nickel and molybdenum in the presence of phosphoric acid, followed by drying and calcining the resulting catalyst mass, where as aluminium oxide using the oxide obtained by heat treatment of three-hydrate of aluminum with a particle size of 0.04 to 0.10 mm drum in a rotating oven at 350 500oC for 15 to 180 min with subsequent hydration of the amorphous product at pH 5.0 to 5.5 and 75 of the 90oC, plasticization in an autoclave at 140 300oC for 3 to 6 h, molding, drying and calcination and impregnation is carried out at a pH of 1.5 to 3.5. The resulting catalyst has a strength factor of 2.4 to 2.5 kg/mm and an average pore size of 12 nm.

The disadvantage of this method is that the catalyst obtained in this way has a low strength, which leads to increased consumption during operation in an industrial environment, as well as lack of stable activity in the process of Hydrotreating petroleum fractions.

The present invention is directed to providing a method of preparing a catalyst for Hydrotreating petroleum fractions having high strength and high stable activity.

The problem is solved in that in the method of preparing a catalyst for Hydrotreating petroleum fractions by impregnation of the carrier with a solution of salts of Nickel and molybdenum in the presence of FOS the invention, as a carrier, a mixture of aluminum hydroxide and aluminoborosilicate crumbs with a particle size of 10 to 100 microns, pre-treated with a solution of nitric acid at a pH of 1.5 to 3.0 and a temperature of 80 95oC, taken in the mass ratio (4 9) 1.

Aljumokalievye crumb used in the present method, is a waste in the production aluminoborosilicate catalyst or exhaust allocability catalyst, which is then ground in a ball mill to a size of 10 to 100 μm.

The composition aluminoborosilicate crumbs, wt.

CoO 2,5 4,0

MoO310 14,0

Na2O less than 0.1

Al2O3the rest of it.

Received aluminoborosilicate powder is treated with a solution of nitric acid at a pH of 1.5 to 3.0 and a temperature of 80 95oC and mixed with aluminum hydroxide in a predetermined ratio. The resulting carrier has a specific surface of 190 210 m2/g, a bulk density of 0.55 to 0.68 cm3/g, average pore 22 is 28 nm. A feature of this carrier are increased strength properties, the strength factor is 2.7 3.2 kg/mm

Prepared the above SP is pH of 2.5 to 3.5. The obtained catalyst mass is dried at a temperature of 100 - 120oC for 1 to 2 h and calcined at a temperature of 400 500oC for 2 to 4 h

The finished catalyst has the following main indicators:

bulk density of 0.60 to 0.72 cm3/g;

the strength factor of 2.7 to 3.2 kg/mm;

chemical composition, wt.

NiO 3,0 3,6

CoO 0,3 0,6

MoO39,0 11,0

Na2O less than 0.1

Al2O3else

The inventive method differs from the known fact that as a carrier, a mixture of aluminum hydroxide and aluminoborosilicate crumbs with a particle size of 10 to 100 microns, pre-treated with a solution of nitric acid at a pH of 1.5 to 3.0 and a temperature of 80 95oC, taken in the mass ratio (4 9) 1.

Thus, the inventive method of preparing a catalyst for Hydrotreating petroleum fractions meets the criteria of the invention of "novelty."

Below are specific examples of the implementation of the proposed method.

Example 1.

Ball mill load 500 g exhaust aluminoborosilicate catalyst. Grinding should be performed within 60 min before the formation of crumbs with a particle size of 10 to 30 μm. Obtained the notes in the amount of 80 ml.

At a temperature of 95oC and a pH of 1.5, the suspension is stirred for 30 min to obtain a homogeneous mass. 10 g of the resulting mass is mixed with 90 g of pellets of aluminum hydroxide (calculated on dry substance) at a temperature of 85oC. Then the mass is evaporated to dryness at 50% of the Finished mass is formed into pellets, dried at 110oC for 10 h and calcined at 520oC for 4 hours. Ready media has the following physicochemical properties:

bulk density of 0.68 cm3/g

the specific surface of 210 m2/g

a safety factor of 2.7 kg/mm

the average radius of the pores 25 nm.

100 g of the obtained carrier is loaded into the apparatus, in which the impregnation. To do this, prepare separately nikelsoderzhashchij solution.

90 g of ammonium molybdate dissolved in water at a temperature of 92oC, there is added 60 g of Nickel nitrate and then poured in 32 ml of phosphoric acid to achieve a pH of 2.5.

The prepared solution is poured granules media and incubated at 80

90oC for 15 minutes Then the catalyst pellet is discharged, dried at 120oC for 1 h and calcined at 400oC for 4 h

Gotesti 2.7 kg/mm

Chemical composition, wt.

NiO 3,0

CoO 0,3

MoO39,0

Na2O 0,06

Al2O3the rest of it.

Example 2.

Ball mill load 500 g exhaust aluminoborosilicate catalyst. Grinding is carried out for 50 min before the formation of crumbs with a particle size of 30 to 65 μm.

Received aluminoborosilicate chips are loaded into the apparatus with stirrer and heated, poured a solution of nitric acid in the amount of 75 ml.

At a temperature of 90oC and a pH of 2.0, the suspension is stirred for 40 min to obtain a homogeneous mass.

20 g of the resulting mass is mixed with 80 g of pellets of aluminum hydroxide (calculated on dry substance) at a temperature of 85oC. Then the mass is evaporated to dryness 52%

The finished mass is formed into pellets, dried at 110oC for 10 h and calcined at 520oC for 4 h

Ready media has the following physicochemical properties:

bulk density of 0.61 cm3/g

specific surface area of 200 m2/g

a safety factor of 3.0 kg/mm

the average radius of the pores 23 nm

100 g of the obtained carrier is loaded into the apparatus, in which oudestraat ammonium dissolved in water at a temperature of 92oC, there is added 60 g of Nickel nitrate and then poured in 35 ml of phosphoric acid to achieve a pH of 3.0.

The prepared solution is poured granules media and incubated at 80

90oC for 15 minutes Then the granules of the catalyst is dried at 100oC for 2 h and calcined at 450oC for 3 h

The finished catalyst has the following characteristics:

bulk density of 0.65 cm3/g

the strength factor of 2.9 kg/mm

Chemical composition, wt.

NiO 3,6

CoO 0,6

MoO311,0

Na2O 0,09

Al2O3else

Example 3.

Ball mill load 500 g of waste from production aluminoborosilicate catalyst. Grinding is carried out for 40 min before the formation of crumbs with a particle size of 65 to 100 μm.

Received aluminoborosilicate chips are loaded into the apparatus with stirrer and heated, poured a solution of nitric acid in 70 ml.

At a temperature of 80oC and pH 3.0, the suspension is stirred for 50 min to obtain a homogeneous mass.

14 g of the obtained mass is mixed with 86 g of pellets of aluminum hydroxide (calculated on dry substance) in temp>C for 10 h and calcined at 520oC for 4 h

Ready media has the following physico-chemical characteristics:

bulk density of 0.55 cm3/g

the specific surface of 190 m2/g

a safety factor of 3.2 kg/mm

the average radius of the pores 28 nm.

100 g of the obtained carrier is loaded into the apparatus, in which the impregnation. To do this, prepare separately nikelsoderzhashchij solution. 90 g of ammonium molybdate dissolved in water at a temperature of 92oC, there is added 60 g of Nickel nitrate and then poured in 35 ml of phosphoric acid to achieve a pH of 3.5.

The prepared solution is poured granules media and incubated at 80

90oC for 15 minutes

Then, the granules of the catalyst is unloaded, dried at 110oC for 1.5 h and calcined at 500oC for 2 h

The finished catalyst has the following characteristics:

bulk density of 0.60 cm3/g

a safety factor of 3.2 kg/mm

Chemical composition, wt.

NiO 3,4

CoO 0,5

MoO310,0

Na2O 0,07

Al2O3else

From the above examples (1 3) shows that the use of ASS="ptx2">

The catalysts prepared by the proposed method were tested in the process of Hydrotreating diesel fuel containing 0,83% wt. sulfur compounds. The tests were carried out at a temperature of 345oC, a pressure of 4.5 MPa and space velocity of the raw material 4,0 h-1.

The test results presented in the table.

Thus it is seen that the catalysts prepared by the proposed method are more stable activity in comparison with the known method. In addition, the inventive method for preparation of the catalyst Hydrotreating reduces consumption of raw materials and thereby reduce the amount of harmful emissions into the atmosphere as nitrous gases and ammonia.

The preparation method of catalyst for Hydrotreating petroleum fractions by impregnation of the carrier with a solution of salts of Nickel and molybdenum in the presence of phosphoric acid at a pH of 2.5 to 3.5, followed by drying and calcining the resulting catalyst mass, characterized in that as a carrier, a mixture of aluminum hydroxide and aluminoborosilicate crumbs with a particle size of 10 to 100 microns, pre-treated with a solution of nitric acid at a pH of 1.5 to 3.0 and a temperature of 80 95

 

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