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High-mesoporous H-ZSM-5 molecular sieve with uniformly distributed bulk-phase mesopores as well as preparation method and application

A uniformly distributed and molecular sieve technology, applied in the direction of molecular sieve catalysts, molecular sieve characteristic polycrystalline silicon, chemical instruments and methods, etc., can solve the problems of skeleton aluminum removal, reduce the acidity of molecular sieves, etc., to inhibit carbon deposition and improve diffusion performance Effect

Active Publication Date: 2018-12-21
TAIYUAN UNIV OF TECH
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

Steam dealumination and acid dealumination may cause the removal of part of the skeleton aluminum, reducing the acidity of molecular sieves

Method used

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  • High-mesoporous H-ZSM-5 molecular sieve with uniformly distributed bulk-phase mesopores as well as preparation method and application
  • High-mesoporous H-ZSM-5 molecular sieve with uniformly distributed bulk-phase mesopores as well as preparation method and application

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0031] (1) Synthesis of pure silicon molecular sieve silicalite-1

[0032] Ethyl orthosilicate is used as silicon source, tetrapropylammonium hydroxide is used as template, ethanol and deionized water are used as solvent, and ethyl orthosilicate is used as SiO2 In terms of tetrapropyl ammonium hydroxide in terms of TPAOH, the molar composition of each raw material is 1SiO 2 : 0.27TPAOH: 4EtOH:10H 2 O, the above solution was aged at 35°C for 5 hours and then transferred to a crystallization kettle for crystallization at 170°C for 3 days. After the product was centrifugally washed and dried, the powder was roasted in a muffle furnace at 550°C for 6 hours to obtain a 0.2 μm Pure silicon molecular sieve silicalite-1.

[0033] (2) Preparation of bulk homogeneous mesoporous Na-ZSM-5

[0034] The pure silicon molecular sieve silicalite-1 prepared in step (1) is used as the silicon source, sodium metaaluminate is used as the aluminum source, and SiO is formed according to the molar ...

Embodiment 2

[0042] (1) Synthesis of pure silicon molecular sieve silicalite-1

[0043] The raw material molar composition of embodiment 1 is adjusted 1SiO 2 : 0.2TPAOH: 4EtOH: 46H 2 O, aging at 25°C for 6 hours, crystallization at 150°C for 4 days, the obtained product was centrifugally washed and dried, and the powder was calcined in a muffle furnace at 400°C for 7 hours to obtain a 0.6 μm pure silicon molecular sieve silicalite-1.

[0044] (2) Preparation of bulk homogeneous mesoporous Na-ZSM-5

[0045] The pure silicon molecular sieve silicalite-1 prepared in step (1) is used as the silicon source, sodium metaaluminate is used as the aluminum source, and SiO is formed according to the molar composition 2 : Al 2 o 3 =1: 0.0056 dissolved in a TPAOH solution with a concentration of 0.1mol / L, where TPAOH : silicalite-1=10ml: 1g, fully stirred at room temperature, crystallized in a crystallization kettle at 150°C for 5 days, and the obtained product was centrifugally washed and dried A...

Embodiment 3

[0050] (1) Synthesis of pure silicon molecular sieve silicalite-1

[0051] The raw material molar composition of embodiment 1 is adjusted 1SiO 2 : 0.17TPAOH: 3EtOH: 46H 2 O, aged at 40°C for 4 hours, crystallized at 130°C for 9 days, the product obtained was centrifugally washed and dried, and the powder was calcined in a muffle furnace at 450°C for 7 hours to obtain a 1 μm pure silicon molecular sieve silicalite-1.

[0052] (2) Preparation of bulk homogeneous mesoporous Na-ZSM-5

[0053] The pure silicon molecular sieve silicalite-1 prepared in step (1) is used as the silicon source, sodium metaaluminate is used as the aluminum source, and SiO is formed according to the molar composition 2 : Al 2 o 3 =1: 0.0033 dissolved in a TPAOH solution with a concentration of 0.2mol / L, where TPAOH: silicalite-1=10ml: 1g, fully stirred at room temperature, crystallized in a crystallization kettle at 200°C for 2 days, and the obtained product was washed and dried by centrifugation Aft...

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Abstract

The invention relates to a high-mesoporous H-ZSM-5 molecular sieve with uniformly distributed bulk-phase mesopores. A particle size of the high-mesoporous H-ZSM-5 molecular sieve is 0.2 to 5 micrometers, a silicon / aluminum molar ratio is 30 to 300, and an average pore size of the bulk-phase uniform mesopores is 6 to 30 nm. The high-mesoporous H-ZSM-5 molecular sieve has the advantages that the cost is low, the methanol conversion rate of methanol catalyzed hydrocarbon production is 100 percent, the liquid hydrocarbon yield is 21 to 28.9 percent, and the reaction time is 160 to 254 hours.

Description

technical field [0001] The invention relates to a method for preparing a molecular sieve catalyst, in particular to a method for preparing a high mesopority H-ZSM-5 molecular sieve with uniform bulk mesopore distribution for methanol-to-hydrocarbon production. Background technique [0002] China is short of oil resources, and its dependence on foreign crude oil reached 68.4% in 2017, which is not conducive to energy security and social and economic development. Compared with the increasingly tight oil resources, my country's coal resources are relatively rich, and the conversion of coal into synthetic gas for the production of methanol has achieved industrialization. Methanol is further catalyzed by acidic catalysts such as ZSM-5 and SAPO-34 to produce olefins, aromatics, gasoline and other chemical products. [0003] ZSM-5 is a zeolite molecular sieve with MFI topology, which has high hydrothermal stability, large specific surface area and rich and adjustable surface prope...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C01B39/40C01B37/02B01J29/40B01J35/10C07C1/20C07C11/02C07C15/02
CPCC01B37/02C01B39/40C07C1/20B01J29/40B01J37/0018C01P2002/72C01P2004/04C01P2006/16C01P2004/61C01P2004/62B01J35/647C07C11/02C07C15/02Y02P20/52
Inventor 李忠付廷俊崔丽萍马倩
Owner TAIYUAN UNIV OF TECH