A method of obtaining a catalyst of liquid-phase oligomerization of olefins

 

(57) Abstract:

The invention relates to the field of organic chemistry and catalysis, in particular to a method for preparing catalysts for the oligomerization of olefins, C3-C4in various types of gas that can be used in the petrochemical industry, for example in the processing of propane-propylene and butane-butylene fraction of cracking. Describes the method of preparation of the catalyst of liquid-phase oligomerization of olefins, C3-C4providing for receiving dikelilingi or nicolelovesbritney composition by contacting aqueous solutions of salts of Nickel with the carrier-silicate or aluminum silicate, drying and calcination, wherein the composition is produced by coprecipitation of salts of Nickel with silica gel or aluminum silicate in an aqueous solution of ammonia at pH 8-10, followed by filtration of the suspension, forming masses pressing or extrusion of aluminum hydroxide. The method allows to obtain a highly efficient, selective and stable catalyst for liquid-phase oligomerization of propylene and butylenes, operating at moderate temperatures (up to 100C) for extended periods (>100 h) time. 1 C.p. f-crystals, 1 table.

IRow oligomerization of olefins, C3-C4in various types of gas that can be used in the petrochemical industry, for example in processing papandropoulos and butane-butylene fraction of cracking. Currently oligomers C3C4-olefins is obtained using a solid phosphoric acid catalyst having a number of drawbacks due to the entrainment of acid and sintering of the catalyst in the reaction. Zeolite catalysts are devoid of these shortcomings, however, the reaction of oligomerization on them is not selectively, in addition, the process is carried out mainly in the gas phase at elevated temperatures (170-450oC) that leads to rapid deactivation of the catalysts.

The most selective di - and trimerization of olefins proceeds in the presence of a Nickel complex catalysts in organic solvents or solid carriers. So, for example, (U.S. Pat. USA N3755490) process is carried out in the presence of a black amorphous complex of Nickel on a substrate of aluminosilicate. The catalyst prepared by deposition of Nickel acetylacetonate and hexachloride aluminum in organic solvents on silica-alumina substrate in the absence of oxygen. The reaction is carried out at 68-71oC and a pressure of 11 to 14 ATM. However, the idea is implemented technologies.

A method of obtaining catalysts for the oligomerization of olefins involving the modification of porous media salts of Nickel in aqueous solutions, followed by drying and calcination. The catalysts are inorganic compounds of Nickel on a substrate of SiO2, Al2O3or silicate (U.S. Pat. USA N 3658935 and 3649710). Nickel may be present on the catalyst surface in the form of NiO, NiO2, NiO6, Ni2O2or a mixture of oxides in an amount of 0.1-35 weight. %, mostly 15-30%. The reaction is carried out at a temperature 79,4 121, 1millionoC and a pressure of 30-50 bar. Conversion of propylene at 87,8oC and W = 4.1 h-133%.

Closest to the present invention is a method for preparing a catalyst for the oligomerization of propylene (U.S. Pat. USA N4608450). The catalyst is prepared by impregnation of a silica-alumina gel 40/60 SiO2-Al2O3an aqueous solution of Nickel acetate, dried at 148oC and calcined in air at 450oC for 8 hours. The reaction of oligomerization of propylene is carried out at 55oC, the pressure of 11.25 MPa and a flow rate of 0.5 h-1. Conversion in C6-+ over 40 hours is 54% with a selectivity to dimers 40 wt.%.

The disadvantage ukazi little time stable operation of the catalyst.

The purpose of technical solution is the method of obtaining a highly efficient, selective and stable catalyst for liquid-phase oligomerization of propylene and butylenes, operating at moderate temperatures (up to 100oC) for a long (over 100 hours) time versus 80 hours for the catalyst prepared by the method of the prototype.

To achieve the technical result in the production method of the catalyst for the oligomerization of olefins, involving contacting SiO2or aluminosilicate with an aqueous solution of salts of Nickel, evaporation, drying and calcination, which differ according to the invention that the catalyst is prepared by coprecipitation of salts of Nickel from various sources SiO2(including silicates) in aqueous solutions of ammonia at pH 8-10. The resulting suspension is stirred at a temperature of 20-100oC for 0.5-10 hours, then filtered and washed with distilled water and molded with aluminum hydroxide, followed by drying and calcination of the pellets.

According to the invention as a carrier uses different silicates or silicate, and silicate containing Al2O3only as impurities.

According to the invention the addition of aluminum oxide can be added to the catalyst at the stage of precipitation of silicate (silicate) Nickel by adding to the suspension an aqueous solution of salt (nitrate) aluminum.

The amorphous silicate or aluminosilicate) Nickel has the following composition, wt.%:

The predominant within

NiO - 20-85; 30-70

Al2O3-- 0,1-20; 5-10

SiO2-- 10-70; 20-50

Na2O*-0,01-1,0; 0,05 - 0,5

*-In the deposition of Nickel on liquid glass is an excess of Na2O removed by ion exchange of the obtained silicate of Nickel and ammonium salts.

Obtained in this way silicate (silicate) Nickel can be used as a catalyst for the oligomerization of olefins after surgery molding with aluminum hydroxide pressing or extrusion. Before carrying out the reaction, the catalysts were dried at 120oC for 3 hours and was progulivali in air at 350oC for 2 hours and at 550oC for 3 hours.

The invention is illustrated in the following examples.

Example 1. 718 g of aluminosilicate gel (the content of SiO2to 18.6 wt.%, Al2O3-- 1.4 wt.%, the rest is water) was placed in a flask with stirrer and rushed 670 ml of distilled water. Under stirring was added 240 g of Nickel nitrate dissolved in 320 ml of distilled water. To the mixture was added concentrated ammonia solution to pH 9. The suspension is heated water. Carefully blended 230 g of the obtained Nickel-silicate and 38 g of aluminum hydroxide (pseudoboehmite: loss of mass on ignition - 70 wt. %) was evaporated to formemost, sformovat into pellets, dried at 120oC for 3 hours, probalily at a temperature of 350oC - 2 hours and at 550oC - 3 hours.

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

NiO - 40,0

Al2O3- 23,2

SiO2- 36,8

Example 2. 430 g of aluminosilicate gel (the gel, see example 1) was placed in a flask with stirrer and added to 400 ml of distilled water. Under stirring was added 340 g of Nickel nitrate dissolved in 450 ml of distilled water. To the mixture was added to 55 g of aluminum nitrate dissolved in 150 ml of distilled water. Then added concentrated ammonia solution to pH 9. The suspension was heated to 90oC and kept for 3 hours with continuous stirring, then filtered, washed with distilled water, was evaporated to formemost, sformovat into pellets, dried at 120oC for 3 hours, probalily at a temperature of 350oC - 2 hours and at 550oC - 3 hours.

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

NiO - 56,0

Al is with a stirrer and is added with stirring a solution of 480 g of Nickel nitrate in 640 ml of distilled water. Then brought the pH of the suspension to 9.0 Prilepa 25% ammonia solution (0.5 liters), was heated to 90oC and kept under stirring for 3 hours. Next was filtered and washed precipitate with distilled water. The precipitate (Nickel-silicate) are thoroughly mixed with the calculated quantity of aluminum hydroxide (pseudoboehmite: loss of mass on ignition - 70 wt. %) adding 100 ml of water for better mixing, brought the pH of the suspension to 5.0, Prilepa concentrated nitric acid and evaporated to formulate. He sformovat into granules, dried in air at 120oC for 3 hours, probalily at a temperature of 350oC - 2 hours and at 550oC - 3 hours. The resulting catalyst has the following composition, wt.%:

NiO - 40,0

Al2O3- 20,4

SiO2- 39,6

Example 4. The catalyst was prepared according to the method of the prototype - 140 g dried amorphous aluminosilicate composition 40/60 - SiO2/Al2O3was soaked with a solution of 340 g of Nickel acetate in 200 ml of distilled water, dried at 148oC, was mixed with 38 g of aluminum hydroxide (pseudoboehmite: loss of mass on ignition - 70 wt. % sformovat into granules, probalily at a temperature of 450oC - 8 hours. The resulting catalyst has followed is alization example 1 were loaded into the flow reactor was heated to 55oC in a stream of inert gas (N2) and was passed through it to layer under a pressure of 40 ATM. propane-propylene fraction (PPF) fraction of cracking composition:

Composition, wt.%

C1- 2,3

C2- 1,0

C3H8- 27,2

C3H6- 57,4

and-C4H10- 10,0

n-C4H10- 0,2

the amount of C4H8- 1,8

C5- 0,1

The volumetric feed rate was 2 h-1. After 16 hours the yield of liquid products (C5+) missed propylene was 67.8 wt.%, and the performance of 10.7 g of oligomer/g-CT including Fractional composition of the products of the oligomerization below:

Composition, wt.%

C3-4(dissolved) - 13,0-13,6

C5- -

C6- 44,4 - 46,7

C7- 2,8 - 2,9

C8- to 2.1 - 2.5

C9- 24,1 - 25,4

C10+to 11.2 to 11.3

Example 6. Through 10 cm3(7 g) of the catalyst from example 2 under the conditions of example 5 at temperatures of 55 and 75oC missed the propane-propylene fraction. The test results presented in the table.

Example 7. Through 10 cm3catalyst from example 3 missed in the conditions of example 5 propane-propylene fraction. After 16 hours the yield of liquid products on a missed propylene composition of the example 4, prepared according to the method of the prototype, missed in the conditions of example 5 propane-propylene fraction. After 16 hours the yield of liquid products on a missed propylene was a 51.2 wt.%, and performance - 8,0 g oligomer/g-CT h

From examples 5, 6 and 7 shows that the Nickel(alumino)silicate catalysts for the proposed method provides higher (65,2-67,8%) degree of conversion of propylene than the catalyst obtained by the method of the prototype impregnated aluminosilicate gel with an aqueous solution of Nickel acetate (example 8). The selectivity of the formation of liquid reaction products (oligomers) in all examples 5-7 is 95-97%.

Furthermore, the preparation of the catalysts according to the specified method allows a wider range to vary the chemical composition (primarily the content of NiO - up to 60% against 40% on prototype). Obtained by the proposed method, the catalysts can be used for processing not only olefins in pure form, but gas with low content of olefinic u/C.

1. A method of obtaining a catalyst of liquid-phase oligomerization of olefins WITH3- C4providing for receiving dikelilingi or nicolelovestitanic and calcination, characterized in that the composition is produced by coprecipitation of salts of Nickel with silica gel or aluminum silicate in an aqueous solution of ammonia at pH 8 to 10, followed by filtration of the suspension, forming masses pressing or extrusion of aluminum hydroxide.

2. The method according to p. 1, characterized in that the addition of aluminum hydroxide is introduced into the catalyst at the stage of precipitation of silicate or aluminosilicate Nickel by adding to the suspension an aqueous solution of aluminium nitrate.

 

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