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Process for preparation of propylene catalysts with methanol conversion

A methanol conversion and catalyst technology, which is applied in physical/chemical process catalysts, molecular sieve catalysts, chemical instruments and methods, etc., can solve the problems of low P/E ratio, poor hydrothermal stability of catalysts, and low yield of propylene

Active Publication Date: 2008-05-07
CHINA PETROLEUM & CHEM CORP +1
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

[0005] The technical problem to be solved by the present invention is that the prior art has the problems of low propylene yield, low P / E ratio (propylene / ethylene mass ratio) and poor hydrothermal stability of the catalyst in the process of methanol conversion to propylene. Preparation method of catalyst for methanol conversion to propylene

Method used

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  • Process for preparation of propylene catalysts with methanol conversion
  • Process for preparation of propylene catalysts with methanol conversion
  • Process for preparation of propylene catalysts with methanol conversion

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1～9

[0024] Molar ratio of silicon to aluminum to SiO 2 / Al 2 o 3 40, 110, 300 ZSM-5 molecular sieve powder and 10%, 30%, 50% binder SiO in weight percentage 2 or Al 2 o 3 Mix, extrude and bake at 600°C for 8 hours. Exchange for 5 hours in 0.1, 0.5 mol / liter hydrochloric acid solution or 0.1, 1 mol / liter ammonium nitrate solution at a temperature of 70°C and a volume-liquid-solid ratio of 10:1. After washing and drying, bake at a temperature of 600°C for 8 hours. The calcined molecular sieve is at a temperature of 600°C, the partial pressure of water vapor in an inert nitrogen atmosphere is 0.04MPa, and the weight space velocity of the water liquid phase is 0.2 hours -1 Under steam treatment for 8 hours. The desired modified molecular sieve catalyst was prepared by rinsing with oxalic acid at a volume-to-liquid-solid ratio of 10:1 at a temperature of 70°C for 5 hours, and roasting at a temperature of 600°C for 8 hours. See Table 1 for details.

Embodiment 10～16

[0026] SiAl to SiO 2 / Al 2 o 3 110 ZSM-5 molecular sieve and 30% SiO by weight 2 The binders are mixed, extruded and then calcined at a temperature of 600°C for 8 hours, and exchanged in a hydrochloric acid solution with a volume-liquid-solid ratio of 10:1. The treatment conditions are: 0.1 mol / liter, and the temperature is 70°C. After washing and drying, bake at a temperature of 600°C for 8 hours. The calcined molecular sieves are subjected to temperatures of 500, 600 and 700°C, water vapor partial pressures of 0.02, 0.04 and 0.08 MPa in an inert nitrogen atmosphere, and water liquid phase weight space velocity of 0.2 hours -1 Conditioned steam treatment for 3, 8 and 12 hours. The desired modified molecular sieve catalyst was prepared by rinsing with citric acid at a volume-liquid-solid ratio of 10:1 at a temperature of 70°C for 5 hours, and roasting at a temperature of 600°C. See Table 2 for details.

Embodiment 17

[0028] The modified molecular sieve catalysts prepared in Comparative Examples 1, 3 and Examples 1 to 9 are used for the reaction of methanol conversion to propylene, with methanol as raw material, in Al 2 o 3 The bed temperature is 350°C, the modified ZSM-5 bed reaction temperature is 500°C, the reaction pressure is 0.02MPa, and the methanol liquid phase weight space velocity is 4 hours -1 , the reaction raw materials pass through the Al 2 o 3The catalyst bed and the modified ZSM-5 molecular sieve bed react to generate propylene. The reaction results are listed in Table 1.

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Abstract

The invention relates to a preparation method for converting methanol into propylene catalyst, which mainly solves the problems existing in the former art that the yield rate of the target product propylene is low, the P and E ratio (propylene / ethylene mass ratio) is low, and the hydrothermal stability is poor. The invention better solves the problems through adopting a technical proposal that ZSM-5 molecular sieve with the mol ratio SiO2Al2O3 from 20 to 1000 and adhesive are roasted after being mixed, and converted at the temperature of 20 to 100 DEG C and in 0.1 to 3 mol / L of ammonium acetate or 0.1 to 8.5 mol / L of acid solution, and steam treated for 1 to 15 hours after being roasted at the temperature of 400 to 700 DEG C and under the fluid water phase weight space velocity of 0.1 to10 hours <-1>, and then the precursor of the ZSM-5 molecular sieve is soaked with acid solution, and roasted to obtain the modified ZSM-5 molecular sieve catalyst. The invention can be used for the industrial production of converting methanol into propylene catalyst.

Description

technical field [0001] The invention relates to a method for preparing a catalyst for converting methanol into propylene. 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 the petroleum route. The research, development and industrialization of methanol-to-olefins technology has become a hot spot in the technology development of maj...

Claims

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Application Information

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IPC IPC(8): B01J29/40C07C1/20C07C11/06
CPCY02P20/52
Inventor 梅长松杨为民温鹏宇雷多陆贤钱堃
Owner CHINA PETROLEUM & CHEM CORP
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