Binder-free zsm-5/β co-crystallized molecular sieve catalyst and its preparation method and use

A co-crystallized molecular sieve and binder-free 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 poor catalyst stability and low propylene selectivity, and overcome poor stability and cost. Economical and easy-to-obtain raw materials

Active Publication Date: 2018-04-06
CHINA PETROLEUM & CHEM CORP +1
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

[0007] One of the technical problems to be solved by the present invention is the problem of poor catalyst stability and low propylene selectivity in the existing methanol conversion to propylene reaction, and a binder-free ZSM-5 / β co-crystal molecular sieve catalyst is provided

Method used

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  • Binder-free zsm-5/β co-crystallized molecular sieve catalyst and its preparation method and use
  • Binder-free zsm-5/β co-crystallized molecular sieve catalyst and its preparation method and use

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0031] Weigh 30 grams of white carbon black and 4.8 grams of alumina, add 60 grams of silica sol (SiO 2 The mass percentage is 40%) for kneading and molding, and the shaped catalyst is baked at 100°C for 3 hours.

[0032] Add 20 grams of triethylamine, 10 grams of tetrapropylammonium hydroxide and 3 grams of distilled water in advance in the reactor, and place 60 grams of the above-mentioned cylindrical product in the reactor after sealing the porous stainless steel mesh top, and then heat it under hydrothermal conditions. Under the condition of controlling the growth direction of molecular sieve crystals, the gas-solid phase treatment was carried out at 120°C for 8 days. After the product was taken out, it was washed with distilled water, dried in the air and then calcined at 550°C in an air atmosphere. It was exchanged three times with 5% ammonium nitrate solution at 80°C, dried and calcined in a muffle furnace at 550°C for 8 hours to obtain a binderless ZSM-5 / β cocrystal z...

Embodiment 2

[0034] Take by weighing 40 grams of diatomaceous earth and 6.5 grams of aluminum sulfate, add 45.5 grams of silica sol (SiO 2 The mass percentage is 40%) for kneading and molding, and the shaped catalyst is baked at 100°C for 3 hours.

[0035] Add 10 grams of ethylenediamine, 20 grams of tetraethylammonium hydroxide and 10 grams of distilled water in advance in the reactor, place 50 grams of the above-mentioned cylindrical product in the reactor and seal it above the porous stainless steel mesh, and heat it under hydrothermal conditions. Under the condition of controlling the growth direction of molecular sieve crystals, the gas-solid phase treatment was carried out at 150° C. for 5 days. After the product was taken out, it was washed with distilled water, dried in the air and then calcined at 550°C in an air atmosphere. It was exchanged three times in 5% ammonium chloride solution at 90°C, dried and calcined in a muffle furnace at 600°C for 4 hours to obtain a binder-free ZS...

Embodiment 3

[0038] Take by weighing 30 grams of rice husk ash and 4.8 grams of alumina, add 42.2 grams of silica sol (SiO 2 The mass percentage is 40%) for kneading and molding, and the shaped catalyst is baked at 100°C for 3 hours.

[0039] Add 10 grams of ethanolamine, 20 grams of tetrapropylammonium hydroxide and 20 grams of distilled water in advance in the reactor, place 30 grams of the above-mentioned cylindrical product in the reactor and seal it above the porous stainless steel mesh, under hydrothermal conditions, The growth direction of molecular sieve crystals is controlled, and gas-solid phase treatment is carried out at 160° C. for 3 days. After the product was taken out, it was washed with distilled water, dried in the air and then calcined at 550°C in an air atmosphere. It was exchanged three times in 5% ammonium nitrate solution at 90°C, dried and calcined in a muffle furnace at 500°C for 4 hours to obtain a binderless ZSM-5 / β co-crystal molecular sieve catalyst with a sha...

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Abstract

The invention relates to a binder-free ZSM-5 / β co-crystallized zeolite molecular sieve catalyst and its preparation method and application, which mainly solves the problem that the ZSM-5 / β-co-crystallized zeolite molecular sieve prepared by the prior art has relatively low activity when a binder is contained. The problem of poor strength when low and no binder. In the present invention, the catalyst comprises the following components in terms of weight percentage: a) 87-99.25% ZSM-5 / β co-crystallized molecular sieve with a shape index of 3-100; b) 0.5-5% Mg, Ca, Sr , Ba at least one element; c) 0.2~5% of at least one element in V, Cr, Mn, Fe, Co, Ni; d) 0.05~3% of La, Ce, Pr, Nd at least The technical scheme of an element solves the problem well, and the prepared catalyst can be used in the industrial production of methanol to propylene.

Description

technical field [0001] The invention relates to a binder-free ZSM-5 / β co-crystal molecular sieve catalyst, a preparation method and application thereof. Background technique [0002] Zeolite molecular sieves are widely used in the field of catalysis because of their uniform and ordered microporous structure, large specific surface area, and high hydrothermal stability. Due to the small particle size, zeolite powder is very inconvenient in practical application, and has weaknesses such as difficult recovery, easy deactivation and aggregation, so it needs to be shaped in advance. Generally, a binder needs to be added during the molding process, but after adding the binder, on the one hand, the binder has a certain pore blocking effect on the molecular sieve, which affects the diffusion performance; on the other hand, the addition of the binder also substantially affects the molecular sieve. The active center has a "dilution" effect, making the actual reaction space velocity l...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): B01J29/80C07C11/06C07C1/20
CPCY02P20/52
Inventor 任丽萍滕加伟赵国良李斌
Owner CHINA PETROLEUM & CHEM CORP
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