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 rat

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

Example

[0023] [Examples 1-9]

[0024] The molar ratio of silicon and aluminum to SiO 2 / Al 2 O 3 ZSM-5 molecular sieve powder of 40, 110, 300 and 10%, 30%, 50% of binder SiO in weight percentage 2 Or Al 2 O 3 Mix and calcinate at 600°C for 8 hours after extruding. Exchange in a 0.1, 0.5 mol / L hydrochloric acid solution or 0.1, 1 mol / L ammonium nitrate solution with a volume of liquid-to-solid ratio of 10:1 at a temperature of 70°C for 5 hours. After washing and drying, it is calcined at 600°C for 8 hours. Put the calcined molecular sieve at a temperature of 600°C, a partial pressure of 0.04 MPa of water vapor in an inert nitrogen atmosphere, and a weight space velocity of water liquid phase of 0.2 hours. -1 Steam treatment for 8 hours. The required modified molecular sieve catalyst was prepared by immersing oxalic acid with a volume liquid-solid ratio of 10:1 at a temperature of 70°C for 5 hours, and calcining at a temperature of 600°C for 8 hours. The details are shown in Table 1.

Example

[0025] [Examples 10-16]

[0026] Compare silicon aluminum to SiO 2 / Al 2 O 3 110 ZSM-5 molecular sieve and 30% by weight SiO 2 The binder is mixed, extruded and calcined at a temperature of 600° C. for 8 hours, and exchanged in a hydrochloric acid solution with a volume-to-solid ratio of 10:1. The treatment conditions are: 0.1 mol / liter, and the temperature is 70°C. After washing and drying, it is calcined at 600°C for 8 hours. Put the calcined molecular sieve at the temperature of 500, 600 and 700℃, the partial pressure of water vapor in an inert nitrogen atmosphere is 0.02, 0.04 and 0.08MPa, and the weight space velocity of the water liquid phase is 0.2 hours. -1 Under the conditions, steam treatment for 3, 8 and 12 hours. The required modified molecular sieve catalyst was prepared by leaching with citric acid at a volume liquid-solid ratio of 10:1 at a temperature of 70°C for 5 hours, and calcining at a temperature of 600°C. See Table 2 for details.

Example Embodiment

[0027] [Example 17]

[0028] The modified molecular sieve catalysts prepared in Comparative Examples 1, 3 and Examples 1-9 were used for the conversion of methanol to propylene. 2 O 3 The bed temperature is 350°C, the reaction temperature of the modified ZSM-5 bed is 500°C, the reaction pressure is 0.02MPa, and the methanol liquid phase weight space velocity is 4 hours -1 , Under the condition of water / methanol molar ratio of 2:1, the reaction raw materials pass through Al 2 O 3The catalyst bed and the modified ZSM-5 molecular sieve bed react to generate propylene. The results of the reaction are shown 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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