Propylene all-silicon molecular sieve based catalyst prepared through methanol conversion and preparation method thereof

A technology for all-silicon molecular sieve and methanol conversion, which is applied in molecular sieve catalysts, physical/chemical process catalysts, chemical instruments and methods, etc. It can solve the problems of poor hydrothermal stability of catalysts, increased content of methane and coke, and low P/E ratio of catalysts, etc. problem, achieve high methanol conversion activity, improve propylene selectivity, and good hydrothermal stability

Inactive Publication Date: 2016-11-23
CHINA UNIV OF PETROLEUM (EAST CHINA)
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

Chinese patent applications CN 200710039068.0, CN 200710043956.X and CN 200610117872.1 are treated with ammonium solution or acid solution, and then treated with steam and acid solution to prepare methanol conversion to propylene catalyst, which solves the problem of low catalyst P / E ratio and catalyst hydrothermal stability The problem of poor performance, but the process steps are many, which is not conducive to industrial promotion
However, the presence of alumina can cause an increase in methane and coke content, shortening catalyst life

Method used

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  • Propylene all-silicon molecular sieve based catalyst prepared through methanol conversion and preparation method thereof
  • Propylene all-silicon molecular sieve based catalyst prepared through methanol conversion and preparation method thereof
  • Propylene all-silicon molecular sieve based catalyst prepared through methanol conversion and preparation method thereof

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0063] 15 g of all-silicon microporous ZSM-5 molecular sieves were calcined at 550° C. for 4 h. Add 12g of ammonium nitrate and 150g of water to it, treat the above solution in a water bath at 80°C and strong stirring for 2h, suction filter until neutral, dry at 110°C for 2h, then repeat the above operation twice, each time the amount of ammonium nitrate Both are 0.8 times the amount of molecular sieves, and the amount of water is 10 times the mass of molecular sieves. Finally, it is roasted at 550 ° C for 3 hours to become a hydrogen-type all-silicon molecular sieve. After the molecular sieve was pressed into tablets, 1.2 g was taken for micro-reaction evaluation. Infrared detection ( figure 1 a), its 3200-3600cm -1 The peak area at 3740cm -1 The ratio of the peak areas at is 10:21. Evaluation results show that the conversion rate of methanol is 100wt%, and the carbon-based yield of propylene is 45.6%.

[0064] In the following examples, unless otherwise specified, the r...

Embodiment 2

[0066] Mix 1.2g of sodium hydroxide and 300g of water into a solution with a concentration of 0.1mol / L, add 10g of all-silicon microporous ZSM-5 molecular sieve to the solution, stir in a water bath at 60°C for 4 hours, and filter until neutral. Dry at 110°C for 3h, then bake at 550°C for 4h. Take 5g of molecular sieve after the above operation, add 4g of ammonium nitrate and 50g of water to it, place the above solution in a water bath at 80°C for 2 hours, repeat the above operation twice, and finally roast at 550°C for 3 hours to obtain the desired hydrogen form All silica molecular sieve. Infrared detection ( figure 1 b), the molecular sieve 3200-3600cm -1 The peak area at 3740cm -1 The peak area ratio at 17:5. The evaluation results show that the conversion rate of methanol is 100wt%, and the carbon-based yield of propylene is 51.7C%.

Embodiment 3

[0068] Mix 35g all-silicon microporous H-ZSM-5 molecular sieve and 22.0g pseudo-boehmite evenly, add 15g nitric acid solution (4wt%) to it and knead, extrude with a mold with a diameter of 1.5mm, dry in the air, place Dry at 110°C for 4h, then bake at 600°C for 4h. Dissolve 2.0g of ammonium dihydrogen phosphate in 40g of water, impregnate the solution on the above catalyst by multiple impregnation, dry at 120°C for 1 hour after each impregnation, and finally roast at 600°C for 3 hours to obtain the final product The all-silicon molecular sieve catalyst, the evaluation result of the catalyst shows that the conversion rate of methanol is 100wt%, and the carbon-based yield of propylene is 50.6%.

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Abstract

A preparation method of a propylene catalyst prepared through methanol conversion comprises the following steps that 1, an all-silicon molecular sieve is treated in alkali liquor, the concentration of the alkali liquor ranges from 0.005 mol / L to 0.5 mol / L, the mass ratio of the molecular sieve to the solution is 1:1 to 1:50, and preferably, the concentration of the alkali liquor ranges from 0.01 mol / L to 0.2 mol / L, and the mass ratio of the molecular sieve to the solution is 1:5 to 1:30; 2, the all-silicon molecular sieve after alkali treatment in the step 1 is directly dried, or filtering and drying are carried out after ion exchange; 3, the all-silicon molecular sieve in the step 2 is dried and calcined and then pressed into particles, and the propylene catalyst prepared through methanol conversion is obtained; or the all-silicon molecular sieve after calcination in the step 2 is mixed and kneaded with an adhesive, then extrusion moulding, drying and calcination are carried out, and the propylene catalyst prepared through methanol conversion is obtained. The prepared catalyst is high in methanol conversion activity, good in propylene selectivity and high in stability.

Description

technical field [0001] The invention relates to the field of petrochemical industry, in particular to an all-silicon molecular sieve catalyst for converting methanol into propylene. Background technique [0002] Propylene is the most demanded and widely used basic organic chemical raw material in the petrochemical industry. At present, the production of propylene mainly comes from light hydrocarbon cracking and catalytic cracking processes. Due to the increasing shortage of global oil resources and the uncertainty of the market, the traditional propylene production route will inevitably be adjusted to the direction of diversification of raw materials. Among them, methanol to propylene from natural gas or coal is the most promising process route to replace the petroleum route. Natural gas or coal to methanol technology has reached maturity, the key to the feasibility of this process is the development of methanol or dimethyl ether to propylene process and catalyst. [0003...

Claims

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Application Information

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IPC IPC(8): B01J29/40C07C1/20C07C11/06
CPCY02P20/52
Inventor 李春义孟晓静孟哲陈晨黄慧文张强
Owner CHINA UNIV OF PETROLEUM (EAST CHINA)
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