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Method for preparing propylene by catalytic cracking olefin with four carbon or above

A technology of catalytic cracking and olefins, which is applied in the production of bulk chemicals, hydrocarbon cracking to produce hydrocarbons, organic chemistry, etc. It can solve the problems of poor catalyst stability and achieve the effect of improving stability, good carbon deposition resistance and stability

Active Publication Date: 2009-02-11
CHINA PETROLEUM & CHEM CORP +1
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

[0010] The technical problem to be solved by the present invention is to overcome the problem of poor catalyst stability in previous literatures, and provide a new method for producing propylene by catalytic cracking of olefins with carbon four and above

Method used

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  • Method for preparing propylene by catalytic cracking olefin with four carbon or above
  • Method for preparing propylene by catalytic cracking olefin with four carbon or above
  • Method for preparing propylene by catalytic cracking olefin with four carbon or above

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Experimental program
Comparison scheme
Effect test

Embodiment 1～3

[0023] Molecular sieve silicon aluminum ratio has a significant impact on the stability of the catalyst. ZSM-5 molecular sieves with three silicon-aluminum ratios of A, B, and C were synthesized according to the ratio and crystallization conditions in Table 1.

[0024] Table 1

[0025] Molecular sieve Proportion Crystallization conditions SiO 2 / Al 2 o 3 The molar ratio of A 40SiO 2 :Al 2 o 3 :30TPABr:26OH -1 : 7600H 2 o 140℃，24h 40 B 80SiO 2 : Al 2 o 3 : 30TPABr : 80NaCl : 26OH -1 : 7600H 2 o 140℃，48h 80 C 160SiO 2 : Al 2 o 3 : 30TPABr : 80NaCl : 26OH -1 : 7600H 2 o 140℃，60h 160

[0026] 5 grams of ZSM-5 molecular sieve A was calcined at 600° C. for 10 hours in an air atmosphere. Then placed in 200 ml, 5% wt NH 4 NO 3 In the solution, exchange at a temperature of 85-90°C for 2 hours, and repeat 3 times. After the exchange, the hydrogen-type ZSM-5 molecular sieve w...

Embodiment 4～5

[0028] C used in the experiment 4 The raw material comes from the raffinate mixed carbon four in the ethylene plant. The raw material composition is shown in Table 2.

[0029] Table 2 Composition of mixed carbon four in ethylene plant raffinate

[0030] project Raw material composition (weight%) Isobutane 1.81 n-butane 5.05 Propylene 0.12 Acetylene 0.08 Anti-butene 11.25 Butene-1 32.07 Isobutylene 43.39 Butene 6.20 C 4 above 0.04

[0031] Take 2 grams of catalyst A-1, activate the catalyst at 500°C under a nitrogen atmosphere for 2 hours before the reaction, and then use the raffinate mixed carbon four as raw material, at 500°C, the weight space velocity is 3 hours -1 The reaction is carried out under certain conditions. During the reaction, water is added to the raw material as a diluent gas, and the water / olefin weight ratio is 1.5. Take another 2 grams of A-1 catalyst, pre-reaction at 500 ° C, space v...

Embodiment 7～9

[0035] Take 2 grams of A-1, B-1, and C-1 catalysts respectively, and pre-react at 500°C with a space velocity of 3.0 hours before the reaction -1 Under the water vapor atmosphere, after processing for 24 hours, A-2, B-2, and C-2 catalysts were prepared. Before the reaction, the catalyst was activated at 500°C under a nitrogen atmosphere for 2 hours, and then the residual mixed carbon four was used as raw material at 500°C with a weight space velocity of 3 hours -1 The reaction is carried out under certain conditions. During the reaction, water is added to the raw material as a diluent gas, and the water / olefin weight ratio is 1.5. The initial butene conversions of A-2, B-2, and C-2 after steam treatment were all greater than 75%. After a reaction time of 500 hours, the performance of the catalysts was compared.

[0036] Table 2 Effect of silicon-aluminum ratio on catalyst stability

[0037]

[0038]It can be clearly seen from Table 2 that after the same t...

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Abstract

The present invention relates to the process of catalytically cracking C4-C8 olefin to produce propylene, and the process is superior to available technology, which has the problems of poor high temperature hydrothermal stability of catalyst with dealumination and deactivation. The technological scheme of the present invention is that C4-C8 olefin material is catalytically cracked to produce propylene at the reaction temperature of 400-600 deg.c, reaction pressure of 0-0.2MPa and weight space velocity of 1-10 / hr under the action of catalyst with ZSM-5 molecular sieve in the SiO2 / Al2O3 ratio of 10-180 as the main active component. The process may be used in industrial production of propylene through cracking olefin.

Description

technical field [0001] The invention relates to a method for producing propylene by catalytic cracking of olefins with carbon four and above, in particular to a method for producing propylene by catalytic cracking of carbon four to carbon eight olefins. Background technique [0002] Mixed C4 olefins are by-products of FCC units in ethylene plants and refineries, and can only be used as low value-added products such as liquefied gas fuels. It is economically and technically feasible to further process it into propylene and ethylene and make full use of this considerable amount of precious olefin resources. [0003] The active components of catalysts usually used for olefin cracking are molecular sieves such as hydrogen ZSM-5, ZSM-11 or SAPO-34. A large amount of inert gas as a heat carrier and diluent is extremely beneficial to the performance of this reaction, and the most ideal dilution The agent is water. However, the presence of water in the reaction process is extremel...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): C07C4/06C07C11/06
CPCY02P20/52
Inventor 谢在库许宁滕加伟赵国良
Owner CHINA PETROLEUM & CHEM CORP
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