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Preparation method for MFI/MOR composite zeolite molecular sieve catalyst without binder

A composite zeolite, binder-free technology, applied in molecular sieve catalysts, physical/chemical process catalysts, chemical instruments and methods, etc., can solve the problems of low activity and poor strength, achieve high mechanical strength, avoid mechanical mixing, structure regular effect

Active Publication Date: 2012-10-10
CHINA PETROLEUM & CHEM CORP +1
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

[0008] The technical problem to be solved by the present invention is that the MFI / MOR composite zeolite molecular sieve catalyst prepared by the prior art has low activity when containing a binder, poor strength when not containing a binder, and MFI or MOR single zeolite molecular sieves in catalysis, adsorption The problem of diffusion and adsorption limitation of compounds outside the pore size range of molecular sieves in other fields, providing a new method for the preparation of binder-free MFI / MOR composite zeolite molecular sieves

Method used

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  • Preparation method for MFI/MOR composite zeolite molecular sieve catalyst without binder
  • Preparation method for MFI/MOR composite zeolite molecular sieve catalyst without binder
  • Preparation method for MFI/MOR composite zeolite molecular sieve catalyst without binder

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0023] Weigh 20 grams of MOR zeolite (SiO 2 / Al 2 o 3 The molar ratio is 30) and 6.2 grams of alumina, adding 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.

[0024] Add 20 grams of ethylenediamine and 10 grams of distilled water to a 200 ml autoclave in advance, place the cylindrical shaped sample prepared above in the reaction kettle, the catalyst sample is not in contact with the solution in the kettle, seal the autoclave and put it into an oven at 150°C Take it out after crystallization for 80 hours, wash it with water until it is colorless, bake it in an oven at 120°C for 2 hours, then put it in a muffle furnace and heat it up to 400°C for 10 hours to prepare a binder-free MFI / MOR composite zeolite molecular sieve.

[0025] The XRD pattern shows that the product contains the characteristic diffraction peaks of MFI zeolite molecular sieve and MOR zeolite molecular sieve, and th...

Embodiment 2

[0027] Weigh 5 grams of MOR zeolite (SiO 2 / Al 2 o 3 Molar ratio is 20) and 2.8 grams of sodium metaaluminate, add 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.

[0028]Add 5 grams of ethylenediamine, 5 grams of triethylamine and 10 grams of distilled water in advance in a 200 ml autoclave, place the cylindrical shaped sample prepared above in the reaction kettle, the catalyst sample is not in contact with the solution in the kettle, and after the autoclave is sealed Put it in an oven, crystallize at 130°C for 200 hours, take it out, wash it until colorless, put it in an oven at 120°C for 2 hours, then put it in a muffle furnace and heat it up to 450°C for 8 hours to prepare a binder-free MFI / MOR composite zeolite molecular sieve.

[0029] The XRD pattern shows that the product contains the characteristic diffraction peaks of MFI zeolite molecular sieve and MOR zeolite molecular...

Embodiment 3~6

[0031] According to the method of embodiment 1, select SiO respectively 2 / Al 2 o 3 For MOR zeolites with molar ratios of 40, 60, 80 and 100, the preparation process remains unchanged, the raw material composition and preparation conditions are shown in Table 1, and the results of the binder-free MFI / MOR composite zeolite molecular sieves prepared are listed in Table 2.

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Abstract

The invention relates to a preparation method for an MFI / MOR composite zeolite molecular sieve catalyst without a binder, which mainly solves the problem that an MFI / MOR composite zeolite molecular sieve prepared by the prior art has low activity if a binder is contained and has poor strength if no binder is contained. In the invention, an MFI / MOR composite zeolite molecular sieve without any binder is obtained through the following scheme: 20 to 80% of an MOR zeolite molecular sieve, 5 to 20% of aluminum compound and 10 to 80% of silicon oxide are mixed, molded and dried so as to obtain a preformed catalyst precursor mixture I, wherein the weight of aluminum compound is less than that of the silicon oxide; the mixture I is put in template steam and crystallized at a temperature of between 130 to 200 DEG C for 20 to 200 hours so as to obtain an MFI / MOR composite zeolite molecular sieve precursor without any binder; the catalyst precursor is dried and baked at a temperature of between 400 to 600 DEG C for 2 to 10 hours. The MFI / MOR composite zeolite molecular sieve obtained through the scheme can solve the above-mentioned problem and can be used as a catalyst to convert C4 hydrocarbon to alkene and aromatic hydrocarbons.

Description

technical field [0001] The invention relates to a preparation method of a binder-free MFI / MOR composite zeolite molecular sieve catalyst. 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. 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 larger, leading to faster d...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): B01J29/80C07C4/06C07C11/04C07C11/06C07C2/00C07C15/02
CPCY02P20/52
Inventor 任丽萍滕加伟徐建军
Owner CHINA PETROLEUM & CHEM CORP
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