The preparation method of catalyst for hydrotreatment of diesel fuel

 

(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 hydrotreatment of diesel fuel. Applying the method of preparation of the catalyst for hydrotreatment of diesel fuel by mixing alumina carrier with boric acid and molybdenum salt solution, followed by shaping, drying and calcining the granules, which, according to the invention, obtained lumbrokinase composition is impregnated with a solution of Nickel nitrate with a concentration of 110 - 175 g/l in the presence of phosphoric acid at a pH of 3.6 to-4.5 and a temperature of 40 - 60oC. 1 table.

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 hydrotreatment of diesel fuel.

There is a method of preparation of the catalyst for hydroprocessed containing aluminum oxide and boron. Prepare the gel Al2O3or Al(OH)3and B2O3hydrolysis joint aqueous solutions of organic salts or alcoholate al the ri 100 300oC in a period of time from several minutes to 48 hours, after which to increase then incubated in distilled water, again washed, filtered off, washed and dried 1 24 h at 150 250oC, is then formed (or granularit) and dried again. The prepared medium should have the following characteristics

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where 40% of the pores have a diameter of 50 nm.

The media put metals (Co, Ni, Mo) [1]

The disadvantage of this method is the complexity of technical solutions and a large number of sewage.

Known method of preparing a catalyst for hydrogenation processes, according to which 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, Xe or a mixture) atmosphere to 200 600oC. the Catalyst has the following chemical composition, wt. NiO 2 10; MoO30.2 to 20; P 0,2 10. Cataleptic raw materials 1.5 h-1. The degree of desulfurization is 92% [2]

There is also known a method of preparation of the catalyst promoted with an oxide of boron and having as macroporous regions with a pore volume of 0.1 - 0.5 cm3/g and microporous areas with high specific surface desulfurization.

The catalyst contains 0.1 to 5,0 (0,5 3,0)% of boron oxide, and 75 (65%) of boron are in tetrahedral coordination.

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 P. In the catalyst composition may include a pair of elements of Co-Mo, Ni-Mo, and in combination with phosphorus or without him. Molybdenum is present in the form of oxide in an amount of 3 to 25% Co, and Ni in the form of oxides in an amount of 0.1 to 8.0% each.

Phosphorus is contained in the elemental state in the amount of 0.5 to 3.0% as media use Al2O3in the presence of a small amount of boron. The carrier is calcined at a temperature of 760oC (539oC).

At the stage of molding of the carrier mixture of aluminum oxide and boron is produced by coprecipitation of the corresponding solutions, or impregnation of the powder of Al2O3a solution of boric krenim and fixed bed at a temperature of 260 482oC, a pressure of 70 to 210 MPa and space velocities of 0.2 to 5.0 h-1[3]

The disadvantage of this method is the low activity of the obtained catalyst that leads to the necessity of the process at a high pressure of 70 MPa.

The closest known solution of an analogous problem to the technical essence and the achieved result is a method for preparing a catalyst for Hydrotreating petroleum fractions comprising a mixture of alumina carrier with salts hydrogenating metals Nickel (cobalt and molybdenum in the presence of boric acid, drying and calcining in the optimal conditions of synthesis. The method involves the use as a carrier of aluminum borate obtained by processing technical three-hydrate of aluminum in a fluidized bed at high temperature with a speed of 50 70oC 400 600oC for 1 6 h followed by patsatsia products of thermal treatment in an acidic medium at a pH of 2.0 to 4.0, a temperature of 135 200oC, time of process 1 20 h and treatment with boric acid at pH 5 to 7 and a temperature of 80 90oC.

The catalyst prepared according to the described method has the following chemical composition, wt.

Nickel oxide (NiO) 4,0 6,0

Molybdenum oxide ="ptx2">

Index strength, kg/mm 1,7 2,0

to achieve the required depth of removal of sulfur compounds at a temperature of 360 370oC [4]

Mainegenealogy the period of operation of the catalyst is 4 to 5 months. after each regeneration 8% of the catalyst due to grinding is eliminated in the form of dust.

The present invention is directed to the development of the method of preparation of the catalyst with high gidroobesserivaniya activity, provide environmentally friendly diesel fuel with sulfur content less than 0.05%

Applying the method of preparation of the catalyst for hydrotreatment of diesel fuel by mixing alumina carrier with boric acid and molybdenum salt solution, followed by shaping, drying and calcining the granules, which, according to the invention, obtained lumbrokinase composition is impregnated with a solution of Nickel nitrate with a concentration of 110 175 g/l in the presence of phosphoric acid at a pH of 3.6 to 4.5 and a temperature of 40 60oC.

The proposed catalyst has the following chemical composition, wt.

Nickel oxide (NiO) 3,0 4,5

Molybdenum oxide (MoO3) 10,0 12,0

The sodium oxide (Na2O) 0,02 0,08

Boron oxide (B2
The difference of the proposed method against known is that lumbrokinase composition is impregnated with a solution of Nickel nitrate in the presence of phosphoric acid under certain conditions. This allows, thanks to the peculiarities of the method of preparation, to obtain a catalytic composition with a more uniform distribution of hydrogenating metals on the surface of the carrier. When this catalyst has a sufficiently high strength properties.

The proposed method for the preparation of the catalyst provides carrying out Hydrotreating process at a lower temperature.

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. After the deposition of conducting stabilization of aluminum hydroxide at a pH of 9.0 to 9.5 within 60-90 minutes, the Obtained aluminum hydroxide is filtered off and then washed chemically demineralized water for washing away impurities (Na2NO-3). The pellet was washed aluminum hydroxide in a quantity of 50 kg load in a kneading machine equipped with a steam jacket and paddle me the keys 4.0 kg H3BO4and continue mixing for 15 minutes After you obtain a homogeneous and uniform kneading machine download paramolybdate ammonium in the amount of 7.3 kg and continue stirring 20 minutes Ready weight with a dry matter content of 45% formed into pellets with a diameter of 2.5 mm Molded granules are dried at a temperature of 100oC 4 h and pierce at 450oC for 4 h at the same time preparing an impregnating solution: to 10 l of water add 83% phosphoric acid at a rate of 0.35 kg, then it dissolve 5.4 kg nitrate Nickel with continuous stirring at a temperature of 60oC. the resulting solution with a concentration of 110 g/l NiO at pH 4.5 load 50 kg of calcined lumbrokinase composition to practically complete absorption of Nickel salts. Then, the granules of the catalyst is dried at 100oC 4 h, and calcined at 500oC 2 h

Example 2

Prepare media by precipitation of the gel formed by the interaction of sodium aluminate and nitric acid. After the deposition of conducting stabilization of aluminum hydroxide at a pH of 9.0 to 9.5 within 60-90 minutes

The obtained aluminum hydroxide is filtered off and then washed chemically demineralized water for washing away impurities (Na2the machine, equipped with a steam jacket and a paddle stirrer. The mixture of aluminum hydroxide is carried out at a temperature of 80 90oC for 15 minutes Then added to the slurry of 1.2 kg H3BO4and continue mixing for 15 minutes After you obtain a homogeneous and uniform kneading machine download paramolybdate ammonium in the amount of 6 kg and continue stirring 20 minutes Ready weight with a dry matter content of 48% formed into pellets with a diameter of 2.5 mm Molded granules are dried at a temperature of 100o4 h and calcined at 450oC for 4 h

At the same time preparing an impregnating solution: to 10 l of water add 83% phosphoric acid in quantities of 1 kg, then it is dissolved 8.6 kg nitrate Nickel with continuous stirring at a temperature of 40oC.

In the resulting solution with a concentration of 175 g/l at a pH of 3.6 load 50 kg of calcined alumina-boron-molybdenum composition to practically complete absorption of Nickel salts. Then, the granules of the catalyst is dried at 100oC 4 h and calcined at 500oC 2 h

Example 3

Prepare media by precipitation of the gel formed by the interaction of sodium aluminate and nitric acid. After the deposition of conducting stabilization gitem washed chemically demineralized water for washing away impurities (Na2O NO-3).

The pellet was washed aluminum hydroxide in a quantity of 50 kg load in a kneading machine equipped with a steam jacket and a paddle stirrer. The mixture of aluminum hydroxide is carried out at a temperature of 80 90oC for 15 minutes Then added to the slurry 1.8 kg H3BO4and continue mixing for 15 minutes After you obtain a homogeneous and uniform kneading machine download paramolybdate ammonium in the amount of 11.0 kg and continue stirring 20 minutes Ready weight with a dry matter content of 45% formed into pellets with a diameter of 2.6 mm Molded granules are dried at a temperature of 400oC for 4 h

At the same time preparing an impregnating solution: to 10 l of water add 83% phosphoric acid at a rate of 0.7 kg, then it dissolve 7 kg of Nickel nitrate with continuous stirring at a temperature of 50oC.

In the resulting solution with a concentration of 145 g/l at pH 4,0 load 50 kg of calcined lumbrokinase compositions for the almost complete absorption of Nickel salt. Then, the granules of the catalyst is dried at 100oC 4 h and calcined at 500oC 2 h

Example 4

The catalysts prepared according to examples 1 to 3 were tested in the pilot the mouth of the well, space velocity of the raw material 3,0 h-1and temperatures 335oand 342oC. the Results are given in the table.

As shown, the catalysts prepared in accordance with the inventive method, have high gidroobesserivaniya activity at lower process temperatures, which will increase mainegenealogy the period of operation of the catalyst.

The use of the catalysts in the process of Hydrotreating diesel fuel provides produce clean diesel fuel with sulfur content less than 0.05% at a lower temperature process.

This will be achieved improvement of technical and economic indicators: saving energy, reducing consumption of catalyst for the hydrotreatment units.

Sources of information

1. Application France N 2561945, class B 01 J 21/02, 1985.

2. U.S. patent N 4588706, class B 01 J 27/19, 1986.

3. U.S. patent N 4724226, CL 502/204, 1988.

4. RF patent N 2008972 class. B 01 J 37/04; B 01 J 23/88, 1994, B N 5 (prototype).

The preparation method of catalyst for hydrotreatment of diesel fuel by mixing alumina carrier with boric acid and the solution Molibdenovuju composition is impregnated with a solution of Nickel nitrate with a concentration of 110 175 g/l in the presence of phosphoric acid at a pH of 3.6 to 4.5 and a temperature of 40 60oC.

 

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