Catalyst for preparing propylene transformed from methanol

A methanol conversion and catalyst technology, applied in physical/chemical process catalysts, molecular sieve catalysts, hydrocarbon production from oxygen-containing organic compounds, etc., can solve problems such as low P/E ratio, poor hydrothermal stability of catalysts, and low propylene yield

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

AI Technical Summary

Problems solved by technology

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

Method used

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  • Catalyst for preparing propylene transformed from methanol
  • Catalyst for preparing propylene transformed from methanol
  • Catalyst for preparing propylene transformed from methanol

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1～9

[0023] 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

[0025] 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

[0027] 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 3 The 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 present invention relates to a catalyst for manufacturing propylene by being converted from methanol which mainly solves the problems of low yield of the target product propylene, low P / E( the mass ratio of propylene to ethane) and poor water thermal stability of catalyst in the prior art. The present invention adopts the technical proposal for adopting 30 to 100 percent of molecular sieve raw powder with a silicon-aluminum mol ratio SiO2Al2O3 of 20 to 1000 ZSM-5 calculated by weight percentage and at least one caking agent from SiO2, clay and Al2O3 to compose a catalyst; then treating the catalyst for 1 to 5 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 before in use; then using steam to treat for 1 to 15 hours under the conditions that the temperature is 400 to 700 DEG C, the partial pressure of the steam in inertia atmosphere is 0.01 to 0.1MPa and the empty speed of the water liquid phase weight is 0.1 to 10hour<-1> and selecting at least one of oxalic acid, citric acid, phosphoric acid and ortartaric acid under a temperature condition of 20 to 90 DEG C 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 catalyst for converting methanol to 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 major international oil comp...

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 谢在库梅长松杨为民刘红星温鹏宇方敬东张玉贤
Owner CHINA PETROLEUM & CHEM CORP
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