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Core-shell microsphere catalyst

A catalyst, core-shell type technology, applied in the field of small ball catalysts, can solve problems such as easy coking, low P/E ratio, small pore size of molecular sieve catalysts, etc.

Active Publication Date: 2014-09-24
CHINA PETROLEUM & CHEM CORP +1
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

SAPO series molecular sieve catalysts have small pore size, easy to coke, and low P / E ratio in product components, so they are not suitable for MTP process

Method used

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Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0052] 7.8 kg dry rubber powder (containing 74% by weight Al 2 o 3 , produced by Sinopec Catalyst Changling Branch, the same below) was dissolved in 1694 kg of tetrapropyl ammonium hydroxide aqueous solution (containing 20% ​​by weight of tetrapropyl ammonium hydroxide), and then 577 kg of solid silica gel (Qingdao Ocean Chemical Co., Ltd. Company production, the same below), stirring and mixing for 2 hours. The molar composition of the resulting reaction mixture is: TPAOH / SiO 2 =0.2, SiO 2 / Al 2 o 3 =140,H 2 O / SiO 2 =9.5. The reaction mixture was charged into a stainless steel crystallization kettle, and crystallized at 130°C for 90 hours under continuous stirring and autogenous pressure. Then the crystallized product was filtered, washed, and dried at 120°C for 16 hours to obtain the molecular sieve raw powder product A1.

[0053] Put the above-mentioned dried raw powder A1 in a muffle furnace and calcined at 550° C. for 6 hours to obtain calcined molecular sieve po...

Embodiment 2

[0058] Put 4.5 kg of dry rubber powder and 1271 kg of tetrapropyl ammonium hydroxide aqueous solution (containing 20% ​​by weight tetrapropyl ammonium hydroxide, produced by Sinopec Catalyst Jianchang Branch) into a stainless steel crystallization kettle for dissolution, and then add 260 kg Deionized water and 577 kg of solid silica gel were stirred and mixed for 2 hours. The molar composition of the resulting reaction mixture is: TPAOH / SiO 2 =0.15, SiO 2 / Al 2 o 3 =180,H 2 O / SiO 2 =9. The reaction mixture was crystallized at 140°C for 75 hours under continuous stirring and autogenous pressure. Then the crystallized product was filtered, washed, and dried at 120°C for 16 hours to obtain the molecular sieve powder product B1.

[0059] Put the above dried raw powder B1 in a muffle furnace and calcined at 550°C for 4 hours to obtain calcined molecular sieve powder B2.

[0060] Take 200 kg of the above-mentioned roasted molecular sieve powder B2 on a dry basis and add it t...

Embodiment 3

[0064] Add 0.8 kg of aluminum hydroxide to 330 kg of tetrapropylammonium hydroxide aqueous solution to dissolve, then add 150 g of deionized water and 150 kg of white carbon black (manufactured by Guangdong Haihua Chemical Co., Ltd.), and stir and mix for 2 hours. The molar composition of the resulting reaction mixture is: TPAOH / SiO2 =0.17, SiO 2 / Al 2 o 3 =300,H 2 O / SiO 2 =12. The reaction mixture was charged into a stainless steel crystallization kettle, and crystallized at 120°C for 100 hours under continuous stirring and autogenous pressure. Then the crystallized product was filtered, washed, and dried at 120°C for 16 hours to obtain the molecular sieve powder product C1.

[0065] Put the above dried raw powder C1 in a muffle furnace and calcined at 600°C for 2 hours to obtain calcined molecular sieve powder C2.

[0066] Take 100 kg of the above-mentioned roasted molecular sieve powder C2 on a dry basis and add it to 1000 kg of deionized water for stirring and beatin...

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Abstract

A core-shell microsphere catalyst is characterized by comprising a core component and a shell component. The core component comprises 30-95 wt% of a ZSM-5 molecular sieve composition and 5-70 wt% of an inorganic oxide; the diameter of the core component accounts for at least 50% of the diameter of the microsphere; the shell component comprises 30-95 wt% of a ZSM-11 molecular sieve composition and 5-70 wt% of an inorganic oxide; the ZSM-5 molecular sieve composition comprises 0.1-10 wt% of phosphorus on a basis of P2O5, and 0-10 wt% of rare earth on a basis of oxide; in the ZSM-5 molecular sieve, the content of alkali metal is less than 0.2 wt% on a basis of oxide, the mole ratio of SiO2 to Al2O3 is 100-1000, the BET-method specific surface area determined by a nitrogen adsorption method is 300-600 m2 / g, the total pore volume is 0.2-0.6 mL / g, and the pore volume of mesopores with a pore diameter more than 2 nm accounts for 30-70% of the total pore volume. The catalyst of the invention can be used in reaction for preparing propylene by methanol catalytic dehydration, and has the characteristics of high activity, good propylene selectivity, and long reaction life.

Description

technical field [0001] The present invention relates to a pellet catalyst containing molecular sieves, more specifically the present invention relates to a pellet catalyst containing ZSM-5 and ZSM-11. 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. Among the traditional sources of propylene production, about 70% comes from petroleum hydrocarbon steam cracking process, and another 28% comes from heavy oil catalytic cracking process, all rely on petroleum resources. Declining oil production capacity and sharply rising global oil prices are forcing researchers to develop new alternative energy sources and new processes to produce bulk chemicals. The conversion technology from coal, natural gas, biomass, etc. to methanol through synthesis gas has matured and realized large-scale industrial production. Catalytic...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): B01J29/40B01J35/08C07C11/06C07C1/24
CPCY02P20/52
Inventor 李明罡张巍王萍王殿中罗一斌慕旭宏舒兴田汪燮卿刘建强
Owner CHINA PETROLEUM & CHEM CORP
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