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Binder-free ZSM-5 molecular sieve catalyst, and preparation method and use thereof

A ZSM-5, binder-free technology, applied in molecular sieve catalysts, physical/chemical process catalysts, hydrocarbon cracking and hydrocarbon production, etc., can solve the problems of poor catalyst stability and low propylene selectivity

Inactive Publication Date: 2014-10-22
CHINA PETROLEUM & CHEM CORP +1
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

[0004] 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 molecular sieve catalyst is provided

Method used

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  • Binder-free ZSM-5 molecular sieve catalyst, and preparation method and use thereof
  • Binder-free ZSM-5 molecular sieve catalyst, and preparation method and use thereof

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0045] With tetrapropylammonium bromide as the template, aluminum nitrate as the aluminum source, and silica sol as the silicon source, the raw materials are first molarally mixed with SiO 2 / Al 2 o 3 =200;OH － / SiO 2 =0.3; R / SiO 2 =0.5;H 2 O / SiO 2 = 40 mixed in a ratio of 40, hydrolyzed completely at room temperature, put into a stainless steel reactor, controlled the growth direction of molecular sieve crystals under hydrothermal conditions, and crystallized at 100°C for 60 hours to obtain the molar ratio of silicon to aluminum SiO 2 / Al 2 o 3 NaZSM-5 molecular sieve with a shape index of 200 and a shape index of 50.

[0046] Weigh 70 grams of the above silicon-aluminum molar ratio SiO 2 / Al 2 o 3 200, NaZSM-5 molecular sieve with a shape index of 50, 5 grams of white carbon black, 6.5 grams of alumina, and 62.5 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. 15 grams of trie...

Embodiment 2

[0050] Tetrapropylammonium hydroxide is used as a template, aluminum sulfate is used as an aluminum source, water glass is used as a silicon source, and raw materials are molar ratios of SiO 2 / Al 2 o 3 =500;OH － / SiO 2 =0.05; R / SiO 2 =1.5;H 2 O / SiO 2 = 10, using the method described in Example 1, crystallized at 80°C for 100 hours to obtain the molar ratio of silicon to aluminum SiO 2 / Al 2 o 3 NaZSM-5 molecular sieve with a shape index of 500 and 3.

[0051] Weigh 50 grams of the above silicon-aluminum molar ratio SiO 2 / Al 2 o 3 NaZSM-5 molecular sieve with a shape index of 500 and 3, 2.8 grams of sodium metaaluminate, and 90 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. 50 grams of triethylamine and 10 grams of distilled water were pre-added in the reaction kettle, and 60 grams of the above-prepared cylindrical product was placed in the reaction kettle above the porous st...

Embodiment 3

[0056] Tetrapropylammonium hydroxide and ammonia water are used as templates, sodium aluminate is used as aluminum source, silica sol is used as silicon source, and the raw materials are molar ratio SiO 2 / Al 2 o 3 =300;OH － / SiO 2 =0.08; R / SiO 2 =0.5;H 2 O / SiO 2 = 20, using the method described in Example 1, crystallized at 180°C for 40 hours to obtain the molar ratio of silicon to aluminum SiO 2 / Al 2 o 3 NaZSM-5 molecular sieve with a shape index of 300 and a shape index of 60.

[0057] Weigh 10 g of the above SiO 2 / Al 2 o 3 300, NaZSM-5 molecular sieve with a shape index of 60, 120 grams of white carbon black, 4.2 grams of aluminum sulfate, adding 175 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. A mixture of 30 grams of ethylamine and 3 grams of distilled water was added in advance to the reaction kettle, and 20 grams of the cylindrical product prepared above was placed...

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Abstract

The invention relates to a binder-free ZSM-5 molecular sieve catalyst, and a preparation method and a use thereof. The problems of low activity of a binder-containing ZSM-5 molecular sieve in the prior art and low intensity of a binder-free ZSM-5 molecular sieve in the prior art are mainly solved. The binder-free ZSM-5 molecular sieve catalyst comprises 90-100wt% of a ZSM-5 molecular sieve with the shape index of 3-100 (the shape index is defined as a length ratio of a longest edge to a shortest edge of a molecular sieve crystal in a three dimensional direction), 0-5wt% of a P element or oxide thereof, and 0-5wt% of at least one of V, Cr, Mn, Fe, Co and Ni, or oxide thereof. The preparation method well solves the problems, and the binder-free ZSM-5 molecular sieve catalyst prepared in the invention can be used in the industrial production for preparing propylene by using methanol.

Description

technical field [0001] The invention relates to a binder-free ZSM-5 molecular sieve catalyst and its preparation and application. Background technique [0002] Zeolite molecular sieves are widely used in the field of catalysis because of their uniform and ordered micropores, 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. In the molding process, it is generally necessary to add a binder. The binder content generally accounts for 30~40% of the total weight of the catalyst, or even higher, so that the catalyst has a specific shape and a certain mechanical strength. From this point of view, the adhesive Binder is necessary. However, the binder is generally an inert component, and the addition of the binder essentially has a "dilute" effect on the active...

Claims

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Application Information

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IPC IPC(8): B01J29/40B01J29/42B01J29/46B01J29/48C07C11/06C07C1/20C07C4/06
CPCY02P20/52
Inventor 任丽萍滕加伟李斌徐建军
Owner CHINA PETROLEUM & CHEM CORP
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