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. Applying the method of preparing a catalyst for Hydrotreating petroleum fractions, according to which the aluminum hydroxide containing 20-30% solids, mixed with solutions of boric and phosphoric acids at pH 2.0 to 3.5, the resulting suspension is stirred at a temperature of 50-70oC for 5-15 min, give it consistently paramolybdate ammonium and Nickel nitrate, dried at a temperature of 110-150oC and calcined at a temperature of 500-550oC. 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 Hydrotreating petroleum fractions.

There is a method of preparation of the catalyst for hydrogenation processes containing oxides of aluminum and boron. Prepare the gel Al2O3or Al(OH)3and B2O3hydrolysis of the joint solutions of organic salts or alcohol is th and dried at 100-300oC in a period of time from several minutes to 48 hours, after which to increase the size of the pores is kept 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: Sbeats=180-400 m2/g; Vthen=0.5-1 cm3/g; dcf7,5 nm, 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.

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, d>600 A, 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 R. In the catalyst composition may include a pair of elements of Co-Mo, Ni-Mo, and in combination with phosphorus and is 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 acid or other suitable boron compounds. The catalyst used in the processes in fluidized and fixed bed at a temperature 260-482oC, the pressure 70-210 and at space velocities of 0.2 to 5.0 h-1[2]

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 more than 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 by mixing alumina carrier with salts hydrogenating metals Nickel (cobalt and molybdenum in the presence of boric acid, followed by drying and calcining the granules, where as alumina but the rise of temperature at a speed of 50-70oC to 400-600oC for 1-6 h, followed by patsatsia product heat treatment in an acidic medium at pH of a suspension of 2.0 to 4.0, the temperature 135-200oC, time of process 1-20 h and treatment with boric acid at pH 5-7, a temperature of 80-90oC.

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

Nickel oxide (NiO) 4,0-6,0

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

Boron oxide (2O3) 6,0-10,0

-aluminium oxide (Al2O3) Else

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

to achieve the required depth of removal of sulfur compounds (less than 0.05%) at a temperature of 360-370oC [3]

Mainegenealogy period of the catalyst is 4-5 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, which has a higher strength and a higher activity. This reduces the consumption of the catalyst and increases mainegenealogy between 4-5 months until 10-11 months

Applying the method of preparing a catalyst for Hydrotreating petroleum fractions, whereby the hydroxide and the obtained suspension is stirred at a temperature of 50-70oC for 5-15 min, give it consistently paramolybdate ammonium and Nickel nitrate, dried at a temperature of 110-150oC and calcined at 500-550oC.

The proposed catalyst has the following chemical composition, wt.

Molybdenum oxide (MoO3) 9,0-10,5

Nickel oxide (NiO) 2,8-3,8

Boron oxide (2O3) 1,0-2,0

The oxide of phosphorus (P2O5) 1,5-3,0

The sodium oxide (Na2O3) 0,02-0,09

Aluminum oxide (Al2O3) Else

Index strength, kg/mm, not less than 2.2

The difference of the proposed method against known is that the aluminum hydroxide containing 20-30% solids, is mixed simultaneously with a solution of boric and phosphoric acids, as well as other sequence of introduction of the hydrogenating metals.

This allows a more uniform distribution of the active metal on the carrier surface and to reduce the temperature of the process.

Example 1. 950 kg hydroxide luminia received by presidenial technical alumina, in the form of g-Al2O3after filtering operations and leaching of cations of sodium, loaded into a kneading machine and at a temperature of 50oC mix to obtain the od of the SUB>2BO3) and phosphoric (3.2 kg H3PO4) acids. The resulting suspension is stirred at a pH of 2.0 and a temperature of 50oC for 5 min and then mixed with salts hydrogenating metals. Under stirring and heated under a suspension imposed consistently salt paramolybdate ammonium and process for 10 minutes, then injected nitrate Nickel and are stirring for another 20 min at a temperature of 95oC. Consumption of salt is 11,0 kg paramolybdate ammonium and 9.6 kg of Nickel nitrate.

The catalyst was formed into pellets, dried at 110oC 6 h and calcined at 500oC.

The finished catalyst has the following chemical composition, wt.

Molybdenum oxide (MoO3) 9,0

Nickel oxide (NiO) 2,8

Boron oxide (B2O3) 1,5

The oxide of phosphorus (P2O5) 1,5

The sodium oxide (Na2O) 0,02

Aluminum oxide (Al2O3) The rest is up to 100

Index strength, kg/mm 2,4

Example 2. 950 kg of aluminum hydroxide obtained by presidenial technical alumina, in the form of g-Al2O3after filtering operations and leaching of cations of sodium, loaded into a kneading machine and at a temperature of 50oC is stirred until a homogeneous man3BO3) and phosphoric (3.7 kg H3PO4) acids.

The resulting suspension is stirred at a pH of 3.0 and a temperature of 60oC for 10 min and then mixed with salts hydrogenating metals. Under stirring and heated under a suspension imposed consistently salt paramolybdate ammonium and process for 10 minutes, then injected nitrate Nickel and are stirring for another 20 min at a temperature of 95oC.

The consumption of salt is 12.0 kg of paramolybdate ammonium and 10.2 kg of Nickel nitrate.

The catalyst was formed into pellets, dried at 150oC 6 h and calcined at 535oC.

The finished catalyst has the following chemical composition, wt.

Molybdenum oxide (MoO3) 10,5

Nickel oxide (NiO) 3,8

Boron oxide (2O3) 2,0

The oxide of phosphorus (P2O5) 2,0

The sodium oxide (Na2O) 0,06

Aluminum oxide (Al2O3) Else

Index strength, kg/mm 2,3

Example 3. 600 kg of aluminum hydroxide obtained by presidenial technical alumina, in the form of g-Al2O3after filtering operations and leaching of cations of sodium, loaded into a kneading machine and at a temperature of 50oC mix to potworami boric (3.1 kg H3BO3) and phosphoric (3.5 kg H3PO4) acids.

The resulting suspension is stirred at a pH of 3.5 and a temperature of 70oC for 15 min and then mixed with salts hydrogenating metals. Under stirring and heated under a suspension imposed consistently salt paramolybdate ammonium and process for 10 minutes, then injected nitrate Nickel and are stirring for another 20 min at a temperature of 95oC.

The salt consumption is 11.5 kg paramolybdate ammonium and 10.0 kg of Nickel nitrate.

The catalyst was formed into pellets, dried at 130oC 6 h and calcined at 550oC.

The finished catalyst has the following chemical composition, wt.

Molybdenum oxide (MoO3) 9,5

Nickel oxide (NiO) 3,4

Boron oxide (B2O3) 1,6

The oxide of phosphorus (P2O5) 3,0

The sodium oxide (Na2O) 0,09

Aluminum oxide (Al2O3) Else

Index strength, kg/mm 2.5

The catalysts obtained according to the claimed method, were tested in the process of Hydrotreating diesel fuel (sulfur content of 0.9% ) at a temperature of 345oC, a pressure of 4.0 MPa and space velocity of the raw material 3,0 h-1.

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From the above examples (1-3) shows that the use of the proposed method of preparation of the catalyst Hydrotreating allows to obtain a catalyst with high strength properties with a higher gidroobesserivaniya activity at low initial temperature (residual content of sulfur compounds in the hydrogenation product was 0.025-0,047%).

The proposed method for the preparation of the catalyst compared with the existing technology allows to increase the strength of the catalyst, to reduce losses during operation and to improve technical and economic parameters of the process for hydrotreatment of diesel fuel. Lowering the process temperature to 345oC allowed to increase mainegenealogy the period up to 10-11 months.

The preparation method of catalyst for Hydrotreating petroleum fractions comprising a mixture of aluminum hydroxide with boric acid and salts of hydrogenating metals, followed by drying and calcining, wherein the aluminum hydroxide containing 20 to 30% solids, mixed with solutions of boric and phosphoric acids at pH 2.0 to 3.5, the resulting suspension is stirred at 50 70oC for 5 to 15 minutes and give it consistently paramolybdate the shumilkin)

 

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FIELD: chemistry.

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