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High stability molecular sieve catalyst for preparing propylene transformed from methanol and preparation thereof

A methanol conversion and catalyst technology, which is applied in the direction of molecular sieve catalysts, physical/chemical process catalysts, chemical instruments and methods, etc., can solve the problems of molecular sieve catalysts such as poor thermal stability and hydrothermal stability, easy coking and deactivation, and achieve good resistance Coking performance, improved anti-coking performance, good hydrothermal stability effect

Active Publication Date: 2011-07-13
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 problem of poor thermal stability and hydrothermal stability of molecular sieve catalysts in the prior art, and the problem of easy coking and deactivation. A new high-stable molecular sieve catalyst for methanol conversion to propylene is provided

Method used

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  • High stability molecular sieve catalyst for preparing propylene transformed from methanol and preparation thereof
  • High stability molecular sieve catalyst for preparing propylene transformed from methanol and preparation thereof
  • High stability molecular sieve catalyst for preparing propylene transformed from methanol and preparation thereof

Examples

Experimental program
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Effect test

Embodiment 1～6

[0018] SiAl to SiO 2 / Al 2 o 3 40, 110, 300 ZSM-5 molecular sieve raw powder and 0%, 10%, 30%, 60% 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 use at least one solution selected from lanthanum, cerium, praseodymium or neodymium nitrate or chloride at a temperature of 20 to 90°C for 4 to 8 hours, and exchange the modified molecular sieve precursor at a temperature of 500, 600, 700 ℃, space velocity 0.2 hours -1 Under steam treatment for 8 hours. The desired modified molecular sieve catalyst was prepared by rinsing with oxalic acid at 70°C for 5 hours at a volume-liquid-solid ratio of 10, and roasting at 600°C.

Embodiment 7

[0020] The modified molecular sieve catalysts prepared in Examples 1 to 6 and the molecular sieve precursors I and II prepared in Comparative Examples 1 and 2 were used in the methanol conversion reaction to produce propylene, using methanol as a raw material at a pre-reaction temperature of 400°C , the reaction temperature is 470°C, the reaction pressure is 0.04MPa, and the space velocity of methanol is 12 hours -1 , under the condition of water / methanol molar ratio 3, the reaction raw materials pass through 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 and Table 4.

Embodiment 8～15

[0022] Molar ratio of silicon to aluminum to SiO 2 / Al 2 o 3 110 ZSM-5 molecular sieve powder and 30% binder SiO in weight percent 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 20, 40, 70, 90°C with a volume liquid-solid ratio of 10 or 0.1, 0.5 at a temperature of 70°C with a volume liquid-solid ratio of 10 , 2.0, 3.0 mol / L ammonium nitrate, ammonium sulfate, and ammonium chloride solutions for 1, 3, 5, and 8 hours. Then treat it with cerium nitrate solution at a temperature of 70°C for 6 hours, and place the exchanged modified molecular sieve precursor at a temperature of 600°C and a space velocity of 0.2 hours -1 Under steam treatment for 8 hours. Use oxalic acid, citric acid, and maleic acid solutions to wash at 70°C for 2, 3, and 5 hours at a volume-to-solid ratio of 10, and roast at 600°C to obtain the desired modified molecular sieve catalyst.

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Abstract

The present invention relates to a high stability molecular sieve catalyst for preparing propylene by being converted from methanol and a preparation method thereof which mainly solve the problems of poor molecular sieve stability and water thermal stability as well as easy coking and deactivation in the prior art. The present invention adopts the technical proposal of adopting the molecular sieve raw powder with a silicon-aluminum mol ratio SiO2 / Al2O3 of 20 to 40 and a weight percentage of 25 to 99.9 percent as well as at least one caking agent from SiO2, clay and Al2O3 to extrude, tablet or spray ball to 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, phosphoric acid or acetic acid under a temperature of 20 to 90 DEG C; then using 0.1 to 5 percent of at least one liquor selected from lanthanum, cerium nitrate or chloride calculated by weight percentage to treat for 4 to 8 hours 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, phosphoric acid and 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 high-stable molecular sieve catalyst for producing propylene by converting 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 the petroleum route. The research, development and industrialization of methanol-to-olefins technology has become a...

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 梅长松谢在库温鹏宇刘红星陆贤钱堃
Owner CHINA PETROLEUM & CHEM CORP
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