SU1505573A1 - Catalyst for alkylation of toluene by ethylene - Google Patents

Abstract

This invention relates to catalytic chemistry, in particular, catalysts for the alkylation of toluene with ethylene. To increase the activity and selectivity of the catalyst, a composition containing, in wt.%, Is used: lanthanum 0.1-1.0

decationized ultrahigh-silica zeolite NTsVM 64.7-99.8

alumina rest. The catalyst allows to increase the degree of toluene conversion from 38.4 to 52%, the degree of ethylene conversion from 70.3 to 98%, and the selectivity from 61.7 to 77%, and also has a high stability over time during multi-cycle operation due to its content the composition of lanthanum. In addition, the use of a catalyst allows the process to be carried out at 400-420 ° C (versus 450 ° C in the known case). 1 tab.

Description

The invention relates to the field of catalysts for petrochemistry, in particular catalysts for the alkylation of toluene with ethylene.

The purpose of the invention is to increase the activity and selectivity of the catalyst due to the additional content of lanthanum in its composition and a new ratio of components.

Example. Air-dry powdered ultrahigh-silica zeolite of the type CMV - composition, wt.%:, 3.65; SiO 90.4; 3.32; KjO 2.6; with a ratio of SiO: 42, 1 is subjected to ion exchange in a solution of 1 n. ammonium chloride containing 50 sp of 25% NH OH at the rate of 6 ml of solution per 1 g of zeolite is carried out

triple treatment at room temperature for 6 hours with intermediate washing of the zeolite with distilled iodine and subsequent treatment with a new portion of the solution. The degree of substitution of Na for the NH ion is 95–98%, the Na content is 0.01–0.02 mg-eq / g.

The resulting MN-form composition, wt.%: NajO 0.01; , 3.64; Sio

90.4; n SiO,

A1,0z

42.2 placed in a Buchner funnel and washed with distillate until a negative reaction to chlorine ion in the filtrate, dried in air for a day, then in a drying cabinet at 110–120 ° C for 3 h and calcined in a muffle furnace at 520 ° C leaked

about SP

SP

00

4-5 hours. The decationized form of the NCWM is obtained.

To a 10% aqueous solution of aluminum sulfate (6.5 g A1 (504), in 26.5 g NO) an aqueous solution of ammonia (1: 1) is added with vigorous stirring and aluminum hydroxide gel is precipitated at pH 8- 8.5. After sedimentation, the gel is left to mature for 2-3 hours, then the distillate is washed from the anions with bidistille with the addition of a few drops of ammonia. The washed gel is activated twice with 0.3 and a solution, placed in a Buchner funnel and washed to a negative reaction to the chlorine anion on the filter. Filtered and slightly dried in air, the mass of aluminum hydroxide is divided by weight into ten equal parts (3 g each).

To 3 g of the obtained aluminum hydroxide gel are added with vigorous stirring 99.9 g of NCVM prepared in this way. The mass is pressed between sheets of filter paper and molded by pressing at a pressure of 150 kg / cm in granules of 1 to 2-3 mm in size, which are then dried at room temperature for 20 hours at 3 hours and calcined at 500 ° C for 4 hours.

9.99 g of the obtained mass is impregnated with a solution of lanthanum nitrate, containing 0.031 g of la (Koz) in 10 ml of water, during the day. Then the catalyst is dried in a drying cabinet at 100-110 ° C for 2 hours and calcined for 4 hours at 500 ° C in a muffle furnace, and then pressed.

The resulting catalyst has a composition, wt.%: NCVM 99.8; 0.1; ,one.

10 cm of catalyst is loaded into the reactor and activated with dry air for 2 hours at, the temperature is reduced to the temperature of the experiment and activated with nitrogen for 0.5 hours. Toluene is fed into the reactor at a mass rate

3.5

and ethylene at a rate of 70 ml / min.

at atmospheric pressure and molar ratio of toluene: ethylene 0.9: 1. The content of ethyltoluenes in liquid products at 420 С is 39.5 wt.%, The conversion depth

toluene sera 52.3%, ethylene 98.0%, ethyl toluene formation selectivity 75.5%.

The reaction products are analyzed by gas chromatography using a column filled with inert AW with 10% apiezon L applied under the following conditions; column temperature 110 ° C, evaporator 200 ° C,

helium carrier gas.

Catalysts of other formulations are prepared analogously to the example. Data on the testing of catalytic activity in the reaction of alkylation of toluene with ethylene are given in taftitz.

The additional content of lanthanum in the catalyst composition allows to increase the degree of toluene conversion from 38.4 to 52%, the degree of ethylene conversion from 70.3 to 98%, and the selectivity from 61.7 to 77%.

The catalyst according to the invention has a high stability in time and high-cycle operation, which is due to the introduction of lanthanum into its composition, which stabilizes the work towards the formation of alkyl products.

Increasing the catalyst activity allows the process of alkylation of toluene with ethylene at 400-420 ° C (versus 450 ° C on a known catalyst) with a higher yield of the target products and a low yield of cracking by-products. The proposed catalyst cokes to a lesser extent and is easily regenerated in a stream of air at 550 C.

Claims (1)

Invention Formula A catalyst for the alkylation of toluene with ethylene, including a decationized ultrahigh silica zeolite NTsVM and alumina, o, t l and h a - y y and with the fact that, in order to increase the activity and selectivity of the catalyst, it additionally contains lanthanum at the following content of components, wt,% 0.1-1.0 64.7-99.8 Else