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MCM-22/ZSM-5 in-situ intergrowth methanol aromatization catalyst and preparation method of catalyst

A technology of MCM-22 and ZSM-5, applied in the field of methanol-to-aromatic catalysts, can solve problems such as low aromatization yield, and achieve the effects of increasing relative content, improving activity and reducing clogging.

Active Publication Date: 2015-04-29
CHINA PETROLEUM & CHEM CORP +1
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

[0010] One of the technical problems to be solved by the present invention is the technical problem of low aromatization yield in the methanol aromatization fluidized bed catalyst composition prepared by the prior art

Method used

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  • MCM-22/ZSM-5 in-situ intergrowth methanol aromatization catalyst and preparation method of catalyst

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0030] 140 grams of kaolin (55.3% SiO 2 , 42.5%Al 2 o 3 , 2.2% other oxides), 40 grams of ZSM-5 molecular sieve (the molar ratio of silica to alumina is 400), 50 grams of silica sol (40% SiO 2 ) and 370 grams of water were mixed evenly, and sprayed to obtain 20-200 μm pellets, which were roasted at 900°C for 4 hours to obtain spray microspheres ZQ1 with a particle size of 10-200 μm.

[0031] Get 100 grams of spray microspheres ZQ1, 0.65 grams of sodium hydroxide, 0.63 grams of aluminum nitrate, 1.7 grams of hexamethyleneimine and 500 grams of water and mix evenly (in the composition of this mixture, silicon oxide in kaolin is removed, and the remaining raw materials The ratio of silica to alumina is 200), and transferred to a closed reactor for crystallization at 120°C for 120 hours. After crystallization, the product was washed, dried at 120°C for 4 hours, and calcined at 550°C for 8 hours to obtain sodium molecular sieve microspheres MZQ1. Sodium-type microspheres were e...

Embodiment 2

[0036] 60 grams of kaolin, 120 grams of ZSM-5 molecular sieve (the molar ratio of silicon oxide to aluminum oxide is 75), 20 grams of white carbon black (99.0% SiO 2 ) and 500 grams of water were mixed evenly, and sprayed to obtain 10-200 μm pellets, which were roasted at 1000°C for 4 hours to obtain spray microspheres ZQ2 with a particle size of 10-200 μm.

[0037] Get 100 grams of spray microspheres ZQ2, 2.2 grams of sodium hydroxide, 2.96 grams of aluminum sulfate, 20 grams of hexamethyleneimine and 500 grams of water and mix well (in the composition of this mixture, silicon oxide in kaolin is removed, and the remaining raw materials The ratio of silicon dioxide to aluminum oxide is 75), and transferred to a closed reactor for crystallization at 120°C for 120 hours. After crystallization, the product was washed, dried at 120°C for 4 hours, and calcined at 550°C for 8 hours to obtain sodium molecular sieve microspheres MZQ1. Sodium-type microspheres were exchanged with 1 mo...

Embodiment 3

[0041] Mix 40 grams of kaolin, 350 grams of silica sol, 20 grams of ZSM-5 molecular sieve (the molar ratio of silicon oxide to aluminum oxide is 20), and 300 grams of water, spray molding to obtain 10-200 μm pellets, and roast at 950 ° C After 4 hours, spray microspheres ZQ3 with a particle size of 10-200 μm were obtained.

[0042] Get 100 grams of spray microspheres ZQ3, 51.6 grams of sodium hydroxide, 28.2 grams of aluminum chloride, 200 grams of hexamethyleneimine and 5000 grams of water and mix them evenly (in this mixture, remove the silicon oxide in kaolin, and the rest of the raw materials The ratio of silica to alumina is 20), and transferred to a closed reactor for crystallization at 120°C for 120 hours. After crystallization, the product was washed, dried at 120°C for 4 hours, and calcined at 550°C for 8 hours to obtain sodium molecular sieve microspheres MZQ1. Sodium-type microspheres were exchanged with 1 mol / L ammonium nitrate solution, washed, dried at 120°C for...

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Abstract

The invention relates to an MCM-22 / ZSM-5 in-situ intergrowth methanol aromatization catalyst and a preparation method of the MCM-22 / ZSM-5 in-situ intergrowth methanol aromatization catalyst, aiming at solving the technical problems that the existing fluidized bed catalyst has low aromatic hydrocarbon yield when used for methanol aromatization. The MCM-22 / ZSM-5 in-situ intergrowth methanol aromatization catalyst is prepared from the following components: (a) 0.5-10.0 parts of at least one of ZnO or Ga2O3; (b) 0.5-10.0 parts of oxides of at least one of P, Fe or Mn; (c) 80.0-99.0 parts of 10-200mum microspheres for in-situ synthesis of MCM-22 / ZSM-5 in-situ intergrowth molecular sieve. The MCM-22 / ZSM-5 in-situ intergrowth methyl alcohol aromatization catalyst can solve the problem and can be used for industrial production of aromatics prepared by methanol.

Description

technical field [0001] The invention relates to a methanol-to-aromatics catalyst synthesized by in-situ technology, in particular to an MCM-22 / ZSM-5 in-situ symbiotic molecular sieve-based methanol-to-aromatics fluidized bed catalyst. Background technique [0002] Aromatics (in which benzene, toluene and xylene are respectively called B, T and X, and the three are collectively called BTX) are important basic organic chemical raw materials. Aromatics mainly come from catalytic reforming and steam cracking by-product pyrolysis gasoline (nearly 90%)-petroleum route, and only about 10% from coal route. From the perspective of energy distribution, my country lacks oil and gas but is rich in coal, and its dependence on foreign crude oil has exceeded 50%, which has threatened national energy security. Moreover, the depletion of petroleum resources and the long-term high volatility of petroleum prices have brought unprecedented severe challenges to energy and chemical industries ba...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): B01J29/00C07C1/20C07C15/02
CPCY02P20/52
Inventor 汪哲明周伟张铁柱
Owner CHINA PETROLEUM & CHEM CORP
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