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In-situ synthesized ZSM-5/Beta symbiotic molecular sieve based catalyst and preparation method thereof

A symbiotic molecular sieve, ZSM-5 technology, applied in the direction of molecular sieve catalysts, physical/chemical process catalysts, chemical instruments and methods, etc., can solve the problems of low propylene yield and low catalytic cracking activity, so as to improve the relative content and yield Improve, enhance the effect of selectivity

Active Publication Date: 2015-04-29
CHINA PETROLEUM & CHEM CORP +1
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

[0009] One of the technical problems to be solved by the present invention is that the fluidized bed catalyst prepared by the prior art for catalytic cracking to produce ethylene and propylene has the technical problems of low catalytic cracking activity and low yield of ethylene and propylene

Method used

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  • In-situ synthesized ZSM-5/Beta symbiotic molecular sieve based catalyst and preparation method thereof
  • In-situ synthesized ZSM-5/Beta symbiotic molecular sieve based catalyst and preparation method thereof
  • In-situ synthesized ZSM-5/Beta symbiotic molecular sieve based catalyst and preparation method thereof

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0031] 60 grams of dry base kaolin (55.3% SiO 2 , 42.5%Al 2 o 3 , 2.2% other oxides), 60 grams of Beta molecular sieve (SiO 2 with Al 2 o 3 The molar ratio is 50), 200 grams of silica sol (40wt% SiO 2 ) and 520 grams of water were evenly mixed, and sprayed to obtain 10-200 μm pellets, which were roasted at 900°C for 4 hours to obtain sprayed microspheres WQ1.

[0032] Get 100 grams of spray microspheres a, 10.8 grams of sodium hydroxide, 10 grams of aluminum nitrate, 12.4 grams of ethylenediamine and 600 grams of water and mix well (in this mixture, kaolin is not included, and the silicon-aluminum molar ratio of the remaining raw materials is 50 ), transferred to a closed reactor for crystallization at 120°C for 120 hours. After crystallization, the product was washed, dried at 120°C for 4 hours, and calcined at 550°C for 8 hours to obtain sodium molecular sieve microspheres GWQ1. GWQ1 was exchanged with 1 mole of ammonium nitrate solution, washed, dried at 120°C for 8 ...

Embodiment 2

[0037] Mix 40 grams of kaolin on a dry basis, 100 grams of Beta molecular sieve (silicon-aluminum molar ratio of 120), 150 grams of silica sol and 310 grams of water, spray molding to obtain 10-200 μm pellets, and roast at 1000 ° C for 4 hours to obtain spray microspheres. Ball WQ2.

[0038] Get 50 grams of spray microspheres a, 16.0 grams of sodium hydroxide, 5.6 grams of aluminum sulfate, 6.2 grams of triethylamine and 300 grams of water and mix well (in this mixture, kaolin is not included, and the silicon-aluminum molar ratio of the remaining raw materials is 120 ), transferred to a closed reactor for crystallization at 160°C for 72 hours. After crystallization, the product was washed, dried at 120°C for 4 hours, and calcined at 550°C for 8 hours to obtain sodium molecular sieve microspheres GWQ2. GWQ2 was exchanged with 1 mole of ammonium nitrate solution, washed, dried at 120°C for 8 hours, and calcined at 600°C for 3 hours to obtain hydrogen microspheres HGWQ2. The rel...

Embodiment 3

[0042] 140 grams of dry base kaolin, 40 grams of Beta molecular sieve (mole ratio of silicon to aluminum is 75.0), 20.2 grams of white carbon black (99.0% SiO 2 ) and 640 grams of water were evenly mixed, and sprayed to obtain 10-200 μm pellets, which were roasted at 900°C for 4 hours to obtain sprayed microspheres WQ3.

[0043] Get 100 grams of spray microspheres a, 4.0 grams of sodium hydroxide, 1.1 grams of aluminum chloride, 12.4 grams of hexamethylenediamine and 600 grams of water and mix well (in this mixture, kaolin is not included, and the silicon-aluminum molar ratio of the remaining raw materials is 75.0 ), transferred to a closed reactor for crystallization at 180°C for 12 hours. After crystallization, the product was washed, dried at 120°C for 4 hours, and calcined at 550°C for 8 hours to obtain sodium molecular sieve microspheres GWQ3. GWQ3 was exchanged with 1 mole of ammonium nitrate solution, washed, dried at 120°C for 8 hours, and calcined at 600°C for 3 hour...

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Abstract

The invention relates to an in-situ synthesized ZSM-5 / Beta symbiotic molecular sieve based catalyst and a preparation method thereof and mainly aims at solving the technical problems that the cracking activity of an existing fluidized bed catalyst is low and the yield of ethylene and propylene is low when the existing fluidized bed catalyst is used in a process of preparing the ethylene and the propylene from petroleum hydrocarbon through the catalytic cracking. The in-situ synthesized ZSM-5 / Beta symbiotic molecular sieve based catalyst comprises the following components in percentage by weight: (a) 1.0-10.0% of at least one of oxides of P, La and Mn, and (b) 90.0-99.0% of an in-situ synthesized ZSM-5 / Beta symbiotic molecular sieve microsphere catalyst with the particle size of 10-200 microns. By adopting the technical scheme, the problems are relatively well solved, and the in-situ synthesized ZSM-5 / Beta symbiotic molecular sieve based catalyst can be applied to industrial production of preparing the ethylene and the propylene from the petroleum hydrocarbon through the catalytic cracking.

Description

technical field [0001] The invention relates to a ZSM-5 / Beta in-situ symbiotic catalytic cracking fluidized bed catalyst, in particular to a fluidized bed catalyst prepared by in-situ crystallization technology for catalytic cracking to produce ethylene propylene. Background technique [0002] Ethylene and propylene are two very important petrochemical raw materials. At present, ethylene and propylene are mainly produced by steam cracking process in the world. Because the traditional steam cracking reaction temperature is as high as 820-1000°C, the process energy consumption is very high, accounting for about 50% of the energy consumption of the entire ethylene industry. This process is a non-catalytic free radical thermal cracking mechanism, and the ethylene / propylene ratio in the product is low (0.5~0.7). At present, the traditional steam cracking process is facing a severe test in the face of the country's requirements for energy saving and consumption reduction of 20% d...

Claims

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Application Information

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IPC IPC(8): B01J29/80C07C4/06C07C11/04C07C11/06
CPCY02P20/52
Inventor 汪哲明肖景娴许烽
Owner CHINA PETROLEUM & CHEM CORP
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