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ZSM-5 mesoporous molecular sieve catalyst for preparing propylene from methanol and preparation thereof

A mesoporous molecular sieve, methanol-to-propylene technology, applied in molecular sieve catalysts, chemical instruments and methods, physical/chemical process catalysts, etc., can solve the problem of low propylene/ethylene mass ratio, low propylene selectivity, molecular sieve thermal stability and water poor thermal stability

Active Publication Date: 2008-10-08
CHINA PETROLEUM & CHEM CORP +1
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

[0005] One of the technical problems to be solved by the present invention is the problems of low propylene selectivity, low propylene / ethylene mass ratio, poor thermal stability and hydrothermal stability of molecular sieves in the prior art, and a ZSM- 5 mesoporous molecular sieve catalyst
The second technical problem to be solved by the present invention is that the preparation method of the above-mentioned modified ZSM-5 mesoporous molecular sieve catalyst is not involved in the prior art, and a new ZSM-5 mesoporous molecular sieve catalyst for methanol to propylene is provided. method

Method used

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  • ZSM-5 mesoporous molecular sieve catalyst for preparing propylene from methanol and preparation thereof

Examples

Experimental program
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Effect test

Embodiment 1～8

[0014] Molar ratio of silicon to aluminum to SiO 2 / Al 2 o 3 40 mesoporous ZSM-5 molecular sieve powder (wherein the mesopore / micropore pore volume ratio is 2.0) and 0%, 10%, 30%, 70% binder SiO in weight percentage 2 Mixed, extruded and calcined at 600°C for 8 hours. 0.1, 1.0, 3.0, 5.0 mol / L hydrochloric acid, nitric acid solution at a temperature of 20, 40, 70, 90°C with a volume liquid-solid ratio of 10 or at a temperature of 70°C with a volume liquid-solid ratio of 0.1, Exchange in 0.5, 2.0, 3.0 mol / L ammonium nitrate, ammonium sulfate or ammonium chloride solution for 1, 3, 5, 8 hours. Then at a temperature of 600°C and a space velocity of 0.2 hours -1 Treat with steam for 8 hours, soak with oxalic acid, citric acid or maleic acid solution at 70°C for 2, 3, and 5 hours at a volume liquid-solid ratio of 10, and roast at 600°C to obtain the desired modified molecular sieve catalyst.

Embodiment 9

[0016] The modified molecular sieve catalysts prepared in Examples 1 to 8 were used in the reaction of methanol conversion to propylene, using methanol as raw material, the pre-reaction temperature was 400°C, the reaction temperature was 500°C, the reaction pressure was 0.04MPa, and the space velocity of methanol was 4 Hour -1 , the reaction raw materials pass through the Al 2 o 3 The catalyst bed and the modified ZSM-5 molecular sieve bed react to generate propylene. The reaction results are listed in Table 1.

Embodiment 10～14

[0018] SiAl to SiO 2 / Al 2 o 3 40, 110, 300, ZSM-5 mesoporous molecular sieve raw powder with mesopore / micropore volume ratio of 0.2, 2.0, 5.0, 10.0, 18.0 and 30% binder SiO in weight percentage 2 Mixed, extruded and calcined at 600°C for 8 hours. Exchange in a 0.5 mol / L hydrochloric acid solution with a volume liquid-solid ratio of 10 at a temperature of 70° C. for 5 hours. Then at a temperature of 500, 600, 700°C and a space velocity of 0.2 hours -1 Under steam treatment for 4, 8, 12 hours. The desired modified molecular sieve catalyst was obtained by rinsing with oxalic acid at a volume-to-solid ratio of 10 at 90° C. for 5 hours, and roasting at 600° C.

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Abstract

The present invention relates to a ZSM-5 mesoporous molecular sieve catalyst used for manufacturing propylene by methanol and a preparation method thereof, which mainly solves the problems of low propylene selectivity, low propylene / ethylene mass ratio as well as poor thermal stability of molecular sieve and poor water thermal stability in the prior art. The present invention adopts the technical proposal of adopting ZSM-5 mesoporous molecular sieve raw powder with a silicon-aluminum mol ratio SiO2Al2O3 of 20 to 1000 and a weight percentage of 20 to 100 percent as well as at least one caking agent selected from SiO2, clay and Al2O3 to extrude, tablet or spray into shape; then treating for 1 to 8 hours by 0.1 to 3 mol / l of at least one ammonium liquor from ammonium nitrate, ammonium chloride or ammonium sulphate or 0.1 to 8.5 mol / l of at least one acid liquor from muriatic acid, nitric acid, vitriol or acetic acid under a temperature of 20 to 90 DEG C; then using steam to treat for 2 to 15 hours under the temperature condition of 400 to 700 DEG C; using a liquor of 0.1 to 3mol / l selected from at least one of oxalic acid, citric acid or maleic acid under a temperature condition of 20 to 90 DEG C to dip for 2 to 5 hours to obtain the modified molecular sieve catalyst, thus better solving the problems. The present invention can be used in the industrial production of propylene by being converted from methanol.

Description

technical field [0001] The invention relates to a ZSM-5 mesoporous molecular sieve catalyst used for producing propylene from methanol and a preparation method thereof. Background technique [0002] Propylene is an important organic chemical raw material. With the rapid growth of demand for polypropylene and other derivatives, the demand for propylene is also increasing year by year. The traditional propylene production process requires a large supply of crude oil or liquefied petroleum gas, the sharp rise in global oil prices and the depletion of future oil energy, there is an urgent need to develop new energy alternatives and new processes to solve the energy shortage caused by future oil shortages crisis. Catalytic production of light olefins (MTO) from methanol and conversion of methanol to propylene (MTP) are the most promising new technologies to replace petroleum routes. The research, development and industrialization of methanol-to-olefins technology has become a h...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): B01J29/40C07C1/20C07C11/06
CPCY02P20/52Y02P30/20Y02P30/40
Inventor 梅长松杨为民刘红星温鹏宇
Owner CHINA PETROLEUM & CHEM CORP
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