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Preparation method and application of molecular sieve catalyst containing aluminum phosphate binder

A molecular sieve and binder technology, which is applied in the field of molecular sieve catalyst preparation, can solve problems such as research that has not yet been reported, and achieve the effects of improving conversion rate and good anti-carbon performance.

Active Publication Date: 2015-03-18
DALIAN INST OF CHEM PHYSICS CHINESE ACAD OF SCI
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

[0018] The above-mentioned aluminum phosphate binder has many advantages, but it is limited to the ZSM-5 molecular sieve system, and the research on adding aluminum phosphate binder to the ZSM-11 molecular sieve system has not yet been reported.

Method used

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  • Preparation method and application of molecular sieve catalyst containing aluminum phosphate binder

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0030] A certain amount of rare earth ZSM-11 molecular sieve with a particle size of 350nm (the rare earth content accounts for 1.2wt% of the rare earth ZSM-11 molecular sieve) was roasted at 550°C for 4h to burn off the template agent, and then used 0.8mol / L ammonium nitrate at 80°C The solution was exchanged three times, washed twice, dried at 120°C, and calcined at 540°C for 3 hours to obtain H-type molecular sieves. Zn load 5wt%; phosphoric acid solution and boehmite according to P / Al molar ratio (the molar ratio of P element in phosphoric acid solution to Al element in boehmite, the same below) is 0.8 and stirred evenly, add to the preparation in the previous step For a good molecular sieve catalyst, the weight ratio of molecular sieve dry basis to boehmite dry basis is 4, stir evenly, dry at 125°C, and then calcinate at 580°C for 6 hours. The obtained catalyst is designated as B.

Embodiment 2

[0032] A certain amount of rare earth ZSM-11 molecular sieve with a particle size of 500nm (rare earth content accounts for 2.3wt% of the rare earth ZSM-11 molecular sieve) was roasted at 500°C for 3 hours to burn off the template agent, and then used 0.6mol / L ammonium nitrate at 70°C The solution was exchanged 3 times, washed 2 times with water, dried at 120°C, calcined at 500°C for 4 hours to obtain H-type molecular sieve, and then conventionally impregnated with zinc metal, using zinc acetate solution, dried at 90°C for 1.5 hours, and calcined at 500°C for 5 hours. The Zn loading of the catalyst is 1.2wt%; the phosphoric acid solution and boehmite are stirred evenly according to the P / Al molar ratio of 0.5, and the molecular sieve catalyst prepared in the previous step is added. , After drying at 145°C, it was calcined at 500°C for 7h, and the obtained catalyst was designated as C.

Embodiment 3

[0034] A certain amount of rare earth ZSM-11 molecular sieve with a particle size of 900nm (rare earth content accounts for 2.5wt% of the rare earth ZSM-11 molecular sieve) was roasted at 550°C for 4 hours to burn off the template agent, and then heated with 0.7mol / L nitric acid at 60°C The ammonium solution was exchanged 3 times, washed 2 times with water, dried at 120°C, and calcined at 550°C for 4 hours to obtain H-type molecular sieves, and then routinely impregnated with zinc metal, using zinc nitrate solution, dried at 80°C for 3 hours, and calcined at 550°C for 6 hours. Catalyst Zn loading 4wt%; phosphoric acid solution and boehmite are stirred evenly according to the P / Al molar ratio of 0.2, and the molecular sieve catalyst prepared in the previous step is added. After drying at 150°C, it was calcined at 650°C for 6 hours, and the obtained catalyst was designated as D.

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Abstract

A preparation method and an application of a molecular sieve catalyst containing an aluminum phosphate binder particularly comprises following steps: (1) exchanging a prepared ultrafine rare earth ZSM-11 molecular sieve with an ammonium nitrate solution, drying the molecular sieve and roasting the molecular sieve to prepare an H-rare earth ZSM-11 molecular sieve; (2) supporting zinc on the H-rare earth ZSM-11 molecular sieve by a zinc salt through a conventional impregnation method, drying the molecular sieve and roasting the molecular sieve; and (3) mixing a phosphoric acid solution and boehmite to generate colloidal aluminium phosphate and uniformly mixing the colloidal aluminium phosphate with the zinc-type molecular sieve prepared in the last step according to a certain weight ratio, drying the molecular sieve and roasting the molecular sieve to obtain the molecular sieve catalyst. When the molecular sieve catalyst is used in an alkylation reaction between dimethyl ether and benzene, aromatic hydrocarbon with carbon number being 7-9 can be prepared at a high yield. The molecular sieve catalyst, compared with a molecular sieve catalyst which only contains an aluminum oxide binder, is increased in conversion rate of benzene and can promote generation of alkylation products of benzene (methyl benzene, dimethyl benzene and trimethyl benzene) and meanwhile inhibit generation of ethylation products of benzene (ethyl benzene and diethyl benzene). In addition, the molecular sieve catalyst is significantly improved in anti-carbon deposition performance.

Description

technical field [0001] The invention belongs to the production technical field of petrochemical products, and in particular relates to a preparation method and application of a molecular sieve catalyst containing an aluminum phosphate binder. Background technique [0002] Aromatics are an important basic raw material of petrochemical industry. Among the total of about 8 million known organic compounds, aromatics account for about 30%. The use of natural gas (mainly composed of methane) or petroleum refinery dry gas (mainly containing methane, ethane, ethylene) and petroleum liquefied gas or methanol (dimethyl ether) for anaerobic aromatization to prepare aromatics is currently a field in academia and industry. popular research topic. [0003] Obtaining aromatics from methanol and dimethyl ether was first seen in the MTG (Methanol to Gasoline) technology developed by Mobil Corporation of the United States. In the 1970s, Mobil Corporation developed the ZSM-5 zeolite catalyst ...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): B01J29/40C07C2/88C07C15/06C07C15/08C07C15/02
CPCY02P20/52
Inventor 徐龙伢刘惠辛文杰刘盛林谢素娟
Owner DALIAN INST OF CHEM PHYSICS CHINESE ACAD OF SCI
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