Methanol conversion to propylene all-silicon molecular sieve catalyst and preparation method thereof

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

Inactive Publication Date: 2019-01-29
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, CN200710043956.X and CN 200610117872.1 are treated with ammonium solution or acid solution, and then treated with steam and acid solution to prepare the catalyst for methanol conversion to propylene, which solves the problem of low catalyst P / E ratio and poor hydrothermal stability of the catalyst problems, but the process steps are numerous, 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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  • Methanol conversion to propylene all-silicon molecular sieve catalyst and preparation method thereof
  • Methanol conversion to propylene all-silicon molecular sieve catalyst and preparation method thereof
  • Methanol conversion to propylene all-silicon molecular sieve catalyst 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 hours. 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, t...

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

The preparation method of the catalyst for the conversion of methanol to propylene comprises the following steps: (1) treating the all-silicon molecular sieve in lye, the concentration of the lye is 0.005-0.5mol / L, and the mass ratio of the molecular sieve to the solution is 1:1- 1:50; preferably, the concentration of the lye is 0.01-0.2mol / L, and the mass ratio of the molecular sieve to the solution is 1:5-1:30; (2) The all-silicon molecular sieve after the alkali treatment in step (1) is directly dried or after ion exchange, then filter and dry; (3) the all-silicon molecular sieve in step (2) is compressed into particles after being dried and roasted to obtain a catalyst for methanol conversion to propylene; or the all-silicon molecular sieve after step (2) is roasted and The binder is mixed and kneaded, extruded, dried and calcined to obtain a catalyst for methanol conversion to propylene. The prepared catalyst has high methanol conversion activity, good propylene selectivity and high 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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Patent Type & Authority Patents(China)
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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