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Mesopore and micropore compound ZSM-5 zeolite material

A technology of ZSM-5 and zeolite materials, which is applied in the direction of crystalline aluminosilicate zeolite, borocarbane silicone crystalline aluminosilicate zeolite, etc., can solve the problem that ZSM-5 zeolite materials cannot be contained at the same time, the deactivation speed is fast, and the pores Issues such as low utilization

Active Publication Date: 2010-06-09
CHINA PETROLEUM & CHEM CORP +1
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  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

[0004] The technical problem to be solved by the present invention is that the ZSM-5 zeolite material currently used in industry cannot contain mesopores and micropores at the same time, the channel utilization rate is low, and the ZSM-5 zeolite material is used for reactions such as toluene disproportionation. Problem, to provide a new mesoporous and microporous hierarchical porous ZSM-5 zeolite material

Method used

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  • Mesopore and micropore compound ZSM-5 zeolite material
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  • Mesopore and micropore compound ZSM-5 zeolite material

Examples

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Embodiment 1

[0013] Sodium hydroxide, tetraethyl orthosilicate, pseudobombalite, tetrapropylamine hydroxide (TPAOH) aqueous solution, water, etc. are used as raw materials, and the molar ratio is 3Na 2 O: 100SiO 2 : 2Al 2 o 3 : 30TPA 2 O: 40H 2 Prepare the ZSM-5 crystallization precursor solution with the ratio of O, then add potato starch template, crystallize at 180°C for 8 days, filter, wash, dry, and roast to obtain mesoporous and microporous composite ZSM-5. 5 molecular sieves A. attached figure 1 The XRD spectrum of the material shows typical ZSM-5 crystal phase characteristics. The material SiO 2 / Al 2 o 3 The molar ratio is 52, and the micropore volume is 0.12cm 3 / g, the mesopore volume is 0.36cm 3 / g, the mesopore volume is three times that of the micropore volume. Among them, the size distribution of mesopores is 5-40 nanometers, see attached figure 2 , the pore size distribution of micropores is 0.5-0.6 nanometers.

Embodiment 2

[0015] Sodium hydroxide, silica sol, sodium aluminate, TPAOH aqueous solution, water, etc. are used as raw materials, and the molar ratio is 2Na 2 O: 100SiO 2 : 1Al 2 o 3 : 20TPA 2 O: 50H 2 Prepare the ZSM-5 crystallization precursor solution according to the ratio of O, and then add wheat starch as template agent to obtain microporous-mesoporous composite ZSM-5 molecular sieve B according to the preparation method in Example 1. The material SiO 2 / Al 2 o 3 The molar ratio is 102, and the micropore volume is 0.12cm 3 / g, the mesopore volume is 0.44cm 3 / g, the pore volume of mesopores is 3.7 times that of micropores, wherein the size distribution of mesopores is 5-50 nanometers, and the size distribution of micropores is 0.5-0.6 nanometers.

Embodiment 3

[0017] Using sodium hydroxide, ethyl orthosilicate, aluminum isopropoxide, tetrapropylammonium bromide, water, etc. as raw materials, the molar ratio of 2Na 2 O: 100SiO 2 : 1Al 2 o 3 : 20TPA 2 O: 50H 2 Prepare the ZSM-5 crystallization precursor solution according to the ratio of O, and then add soluble starch as a template and follow the preparation method in Example 1 to obtain a microporous-mesoporous composite ZSM-5 molecular sieve C. The material SiO 2 / Al 2 o 3 The molar ratio is 104, and the micropore volume is 0.12cm 3 / g, the mesopore volume is 0.6cm 3 / g, the pore volume of mesopores is 5 times that of micropores, in which the size distribution of mesopores is 6-45 nanometers, and the size distribution of micropores is 0.5-0.6 nanometers.

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Abstract

The invention relates to a mesopore and micropore compound ZSM-5 zeolite material and mainly aims to solve the problem that the ZSM-5 zeolite material cannot contain mesopores and micropores at the same time, the problem that inactivation speed is high when the ZSM-5 zeolite material is used in the reactions such as toluene disproportionation and the like in the prior art. To solve the problems existing in the prior art, the invention adopts a technical scheme that: in the mesopore and micropore compound ZSM-5 zeolite material, the molar ratio of SiO2 to Al2O3 is 15 to 500, and the material has 0.5 to 0.6 nanometer micropores and 5 to 100 nanometer mesopores, and the pore volume of the mesopores is 1 to 10 times that of the micropores. The mesopore and micropore compound ZSM-5 zeolite material can be applied to the industrial production of conversion and treatment of aromatic hydrocarbons, such as toluene disproportionation.

Description

technical field [0001] The invention relates to a ZSM-5 zeolite material composed of mesoporous and microporous hierarchical pores. Background technique [0002] At present, the conventional ZSM-5 zeolite molecular sieve used in oil refining and petrochemical industry is a microporous crystal molecular sieve, and its crystal contains micropores with a size of about 0.5-0.6 nanometers. Due to their small pore size, the diffusion of gas reactant molecules in the pores is limited, resulting in low effective utilization of micropores. On the other hand, for some small molecule high-temperature catalytic reactions, smaller pores are also likely to cause catalyst coking and loss. Live, affecting the service life of the catalyst. Moreover, they are not suitable for catalytic reactions of macromolecules. Since the 1990s, mesoporous molecular sieve materials such as M41 series and SBA series have been discovered. Although they have large pore diameters (2-50 nanometers), their stab...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C01B39/38
Inventor 刘志成谢在库孔德金王仰东
Owner CHINA PETROLEUM & CHEM CORP
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