Catalyst and method of oligomerization of lower olefins

 

(57) Abstract:

The invention relates to catalysts and to methods of producing oligomers of lower olefins in the gas or liquid phase oligomerization of olefins from ethylene, propane, propylene and butane-butylene gas fractions or mixtures thereof. Describes a catalyst for the oligomerization of lower olefins, containing in its composition nicolelovesrice, zeolite and alumina in the following ratio, wt.%: NiO 10-80, Al2O31-50, SiO210-60, zeolite 1-40. As zeolite supplements you can use the zeolite group of pentelow, ZSM-4, the mordenite. Also describes a method of oligomerization of lower olefins using the catalyst of the above catalyst. The use of the catalysts of the proposed structure can significantly reduce the temperature of the process and increase the yield of liquid oligomer (polymer-gasoline) missed olefins. 2 C. p. F.-ly, 7 PL.

The invention relates to the field of organic chemistry and catalysis, in particular to catalysts and methods of producing di-, tri - and tetramers of lower olefins that can be used in the refining and petrochemical industry for the processing of olefinic and gases in processes of refining urgent task is to find new ways of their utilization, especially for registergui gases. So along with the traditional methods of processing processes of alkylation, polymerization) is considered and a different approach - oligomerization of light olefins C2-C4receiving high-octane components of motor fuels, or intermediates for various chemical industries.

The present invention using combined zeolite-Nickel(alumino)silicate catalyst allows you to recycle ethylene, propylene and butylene (both separately and together) to obtain the mainly di - and trimers of n-olefins.

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, they are relatively quickly deactivated due to coke deposits, because the process is conducted mainly in the gas phase at elevated temperatures (170-450oC). For processes of oligomerization of olefins often use high zeolites groups of pentelow (ZSM-5, ZSM-11, etc) and their modifications, Russian Academy of Sciences is Gomersal them flows selectivity with the formation of a wide range of products, wikipaedia at the level of the gasoline fractions (U.S. Pat. USA N 4456781). The introduction of Nickel in such zeolites improves the selectivity of the process.

Known oligomerization of olefins using Nickel-containing crystalline aluminosilicates (HZSM-5, HZSM-11) or mixtures thereof (U.S. Pat. USA N 4542251), aimed at processing individual olefins C3-C6.

Closest to the present invention is a catalyst for oligomerization, which is prepared by impregnating silica gel with an aqueous solution of Nickel acetate, dried at 148oC and calcined in air at 450oC for 8 hours, and the method of obtaining (PCT Int. Appl. WO 91 09.826 CI C 07 C 11/02-Exxon) octanol liquid-phase dimerization bocenago raw material with the use of this catalyst. The method consists in the oligomerization of a mixture of butenes at a temperature of 185oC, a pressure of 70 ATM with a bulk velocity 0,99 h-1.

The disadvantage of these catalysts and the method is the low degree of conversion of olefins at temperatures below 80oC, short time stable operation of the catalyst.

The technical problem solved by the invention is the development of highly efficient and selective catalyst for the indigenous temperatures (up to 100oC) for a long time with high selectivity.

The catalyst according to the invention is prepared as follows: amorphous silicate or aluminosilicate) Nickel is prepared by coprecipitation of salts of Nickel and various sources SiO2(including aluminosilicate) aqueous solution of ammonia at a pH of 8-10. The resulting suspension was stirred at a temperature of 20-100oC for 0.5-10 hours, then was filtered and washed with distilled water. The estimated amount of the thus obtained amorphous silicate or aluminosilicate) Nickel was then mixed with the calculated quantity of zeolite type pentasil and aluminum hydroxide pseudoboehmite patterns. The mass was thoroughly mixed, evaporated (if necessary) to the desired moulding consistency and was molded by extrusion into pellets with a length of 5-7 mm and a diameter of 2-3 mm Granules were pravalivai in air, dried at 120oC for 5 hours and was progulivali at 350 for 2 hours and at 550oC for 3 hours.

According to the invention, the zeolite and alumina may be added to the catalyst during mechanical mixing, and at the stage of precipitation of silicate (silicate) Nickel, and at the stage of deposition instead gidroksimetil as zeolite supplements instead of group zeolite to use zeolites of type ZSM-4, the mordenite.

The observed technical effects - an increase in the degree of transformation of raw materials, reduction of the process temperature is due to the fact that the addition of zeolite and alumina provide the required porous structure and the acidity of the catalyst and improve its technological and operational characteristics.

The proposed method of producing di-, tri - and tetramers of olefins, C2-C4is contacting the feedstock at low temperature and elevated pressure with a catalyst of the following composition, wt.%: NiO - 10-80, Al2O3- 1-50, SiO2- 10-60, zeolite - 1-40.

The process is carried out at a temperature of 30-100oC, a pressure of 1-10 MPa and space velocity of the liquid raw material is 0.5 - 6 h-1(in the case of the gas - 250-2200 h-1).

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 a concentrated solution of ammonia to dug with distilled water. Carefully blended 230 g of the obtained Nickel-silicate, 38 g of aluminum hydroxide (pseudoboehmite: loss of mass on ignition - 70%) and 7 g of zeolite DCM (domestic analogue of ZSM-5). The mass was evaporated to formemost, sformovat into pellets, dried at 120oC for 5 hours, probalily at a temperature of 350oC - 2 hours and at 500oC - 3 hours. The resulting catalyst had the following composition, wt.%: NiO - 36,0, Al2O3- 20,9, SiO2- 33,1, zeolite - DCM - 10,0 (K-p N 1).

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 55 g of aluminum nitrate dissolved in 150 ml of distilled water, and added 7 g of zeolite computers. 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 7 hours, probalily at a temperature of 350oC - 2 hours and at 500oC - 3 hours. Polucen the P CLASS="ptx2">

Example 3. 297 g of ground silica gel (grain size 0.5 mm) were placed in a flask with stirrer and 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 calculated amounts of zeolite type CVM and aluminum hydroxide by 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 pellets, dried at 120oC for 3 hours, probalily at a temperature of 350oC - 2 hours and at 500oC - 3 hours. The resulting catalyst has the following composition, wt.%: NiO - 36,0, Al2O3- 18,4, SiO2- 35,6, zeolite - DCM - 10,0 (K-p N 3).

Example 4. The catalyst was prepared according to example 1, by changing the ratio of components and the type of zeolite, so that the final product had the following composition, wt.%: NiO - 42,0, Al2O3is 21.8, SiO2- 16,2, zeolite - DCM - 20,0 (K-p N 4).

Example 5. The catalyst gotovolume composition, wt.%: NiO - 36,0, Al2O3- 20,9, SiO2- 33,1, zeolite ZSM-4 - 10,0 (K-p N 5).

Example 6. The catalyst was prepared according to example 1, with the difference that instead of zeolite computers used type zeolite of the mordenite. The resulting catalyst had the following composition, wt.%: NiO - 36,0, Al2O3- 20,9, SiO2- 33,1, mordenite - 10,0 (K-p N 6).

Examples 7-11. The catalyst was prepared according to example 1, by changing the ratio of components and the type of zeolite, so that the final product had the following composition (see table. 1 - catalysts N 7-11).

Examples 12-30. The catalysts obtained in examples 1-11, experience in the way of oligomerization of olefins, C2-C4. The process is carried out by running the install with catalyst loading of 12 cm3. The composition of the raw materials used are shown in table 2.

Table 3 presents data on the conversion of various feedstocks containing olefins, C2-C4- ethane-ethylene (EEF), propane-propylene fraction (PPF) and butane-butylene (BBF) fractions. Liquid products obtained during the transformation of the gas fractions accumulate within 6 hours, and then chromatographic determine their composition, analysis of process gases is carried out every hour. Table 4 shows the faction is the procedure oligomerization of lower olefins. The process is carried out under the conditions of examples N 12-30, changing the temperature, pressure and volumetric feed rate. The results are given in table 5.

Example 38. The catalyst was prepared according to the method of the prototype - 430 g of aluminosilicate gel composition 40/60 SiO2/Al2O3was placed in a flask with stirrer. Under stirring was added 340 g of Nickel acetate dissolved in 450 ml of distilled water was heated to 90oC and kept for 3 hours with continuous stirring, dried at 148oC, was mixed with 38 g of aluminum hydroxide (pseudoboehmite: loss of mass on ignition - 70%), sformovat into pellets, dried at 120oC for 5 hours, probalily at a temperature of 450oC - 8 hours.

The resulting catalyst has the following composition, wt.%: NiO - 36,0, Al2O3- 45,8, SiO2- 18,2.

Examples 39, 40. The catalysts were prepared as described in example 38, by changing the ratio of components so that the catalyst had the following composition, respectively, wt.%:

NiO - 10,0, Al2O3- 64,5, SiO2- 25,5.

NiO - 80,0, Al2O3- 14,3, SiO2- 5,7.

Examples 41-48. Catalyst N 38-40 experience in the way of oligomerization of lower olefins, C2

The results are given in table 6.

Examples 49-55. Catalyst N 38 are experiencing in the way of oligomerization of lower olefins, C2-C4. The process is carried out in the examples 41-48 N, changing the temperature, pressure and volumetric feed rate. The results are given in table 7.

Comparison of transformation of the same species of the gas on the catalyst for the proposed method (examples 12-37) and the prototype (examples 41-55), indicates a higher performance (output and eat liquid oligomers) of the first group of catalysts.

Example N 12-37 shows that the maximum yield is observed for samples of catalyst No. 1 and 2, containing 5-10% zeolite supplements. The selectivity of the formation of liquid reaction products (oligomers) in all examples 12-37 is 92-97%.

1. The catalyst for the oligomerization of lower olefins, containing in its composition amorphous silicate or aluminosilicate of Nickel, characterized in that it further contains an additive in the form of a zeolite from the following group: computers, ZSM-4, mordenite and alumina with the following content of components in the calculation of the oxides, wt.%:

NiO - 10 - 80

Al2O3- 1 - 50

NiO - 10 - 80

Al2O3- 1 - 50

SiO2- 10 - 60

Zeolite - 1 - 40

and the process is carried out at a temperature of 30 - 100oC, a pressure of 1 to 10 MPa and space velocity of the liquid raw material is 0.5 to 6 h-1in the case of gaseous raw materials 250 - 2200 h-1.

 

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