Cracking auxiliary agent for improving catalytic cracking low-carbon olefin concentration

A technology of additives and concentration, applied in catalytic cracking, hydrocarbon cracking to hydrocarbon production, molecular sieve catalyst, etc., can solve the problems of low propylene concentration, low propylene selectivity, high dry gas and coke yield, and improve octane number. , the effect of improving the conversion rate of heavy oil and improving the selectivity

Active Publication Date: 2013-04-03
CHINA PETROLEUM & CHEM CORP +1
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

The zeolite materials and catalysts disclosed in the prior art are used as additives in the catalytic cracking process. The selectivity of propylene is not high, and the concentration of propylene in the liquefied gas is low. The existing molecular sieves with MFI structure modified by phosphorus and transition metals are used in catalytic cracking. Production of propylene with high dry gas and coke yields

Method used

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  • Cracking auxiliary agent for improving catalytic cracking low-carbon olefin concentration
  • Cracking auxiliary agent for improving catalytic cracking low-carbon olefin concentration
  • Cracking auxiliary agent for improving catalytic cracking low-carbon olefin concentration

Examples

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preparation example Construction

[0030] The preparation method of the modified MFI molecular sieve of the present invention is to modify the MFI molecular sieve containing phosphorus and transition metals with a silicon-containing compound, including mixing the roasted molecular sieve with MFI structure containing phosphorus and transition metals with a silicon source , and then keep the resulting mixture at 145-190° C. for 2-80 hours to carry out reaction crystallization (also called crystallization). SiO 2 The weight ratio of silicon source in terms of silicon source to the MFI molecular sieve containing phosphorus and transition metals in dry basis is 0.03~0.3:1, preferably 0.05~0.15:1; the reaction crystallization temperature is preferably 150-190°C, more preferably 170-190°C; reaction crystallization time is preferably 5-50 hours, more preferably 12-24 hours.

[0031] Mix the calcined molecular sieve with MFI structure containing phosphorus and transition metals with the silicon source, preferably add a...

specific Embodiment approach

[0036] A specific embodiment of the preparation method provided by the invention includes:

[0037] (1) According to molecular sieve: ammonium salt: H 2 O=1: (0.1 ~ 1): (5 ~ 10) weight ratio Sodium type molecular sieve with MFI structure is exchanged at room temperature to 100 ° C for 0.3 ~ 1 hour and then filtered and dried;

[0038] (2) Impregnating and modifying the ammonium-exchanged molecular sieve with a phosphorus-containing compound solution and a solution containing a transition metal compound, then drying and roasting; the roasting temperature is 400-800° C.; The metal compound solution impregnates the ammonium-exchanged molecular sieve, which may be impregnated with a solution containing both a phosphorus compound and a transition metal compound, or may be impregnated separately with a solution containing a phosphorus compound and a solution containing a transition metal compound; the impregnation Can be carried out one or more times, preferably, impregnation with ...

Embodiment 1

[0045] 5kg NH 4 Cl was dissolved in 100kg of water, and 10kg (dry basis) of crystallization product ZSM-5 molecular sieve (produced by Sinopec Catalyst Qilu Branch Company, produced by amine method, SiO 2 / Al 2 o 3 =50), after exchanging at 90°C for 0.5h, filtered to obtain a filter cake; 0.9kg H 3 PO 4 (concentration 85% by weight) and 0.81kgFe(NO 3 ) 3 9H 2 O was dissolved in 9kg of water, and the impregnating solution and filter cake were mixed and impregnated, dried, and roasted at 550°C for 2 hours; take 1kg of the above-mentioned roasted molecular sieve, and mix it with 0.536kg of tetraethyl orthosilicate (Beijing Chemical Reagent Company, Analytical grade, SiO 2 content 28% by weight), 0.333kg tetrapropylammonium bromide (Guangzhou Dayou fine chemical factory production, analytical purity, 99%) and the mixture of 1.2L water are mixed, are placed in the crystallization kettle that contains polytetrafluoroethylene liner, After static crystallization at 150°C for 2...

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Abstract

The invention provides a cracking auxiliary agent used for improving propylene concentration. The auxiliary agent comprises 10-75wt% of phosphorus and transition metal-modified MFI molecular sieve, 0-60wt% of clay, 15-60wt% of an inorganic oxide binder, 0.5-15wt% of a VIII-family metal additive, and 2-25wt% of a phosphorus additive. The phosphorus and transition metal-modified MFI-structured molecular sieve has no absorption peak at 1633cm<-1> on an infrared spectrum obtained with trimethylpyridine as probe molecules, and has a phosphorus distribution of 0-0.8. D is a ratio of the phosphorus content from the edge to a 1 / 5 position of the center of molecular sieve crystal to the phosphorus content at the center of molecular sieve crystal, which is characterized by using a TEM-EDX method. The transition metal is one or more selected from Fe, Co, Ni, Cu, Mn, Zn, Sn and Bi. The auxiliary agent is used in catalytic cracking, and assists in improving catalytic cracking liquefied gas yield, and improving yields of low-carbon olefins such as ethylene, propylene, isobutylene, and the like. With the catalyst, low-carbon olefin concentration in catalytic cracking liquefied gas is improved, heavy oil conversion capacity of catalyst combination is improved, dry gas and coke selectivity is improved, and gasoline octane number is improved.

Description

technical field [0001] The invention relates to a cracking aid for increasing the concentration of low-carbon olefins in catalytic cracking liquefied gas. Background technique [0002] Low-carbon olefins are important organic chemical raw materials. With the rapid growth of demand for their derivatives, the world's demand for low-carbon olefins is also increasing year by year. Fluid catalytic cracking is one of the important production processes for the production of low-carbon olefins. In order to increase the production of low-carbon olefins, the use of catalysts or additives with MFI structure zeolites containing phosphorus and transition metals is an effective technical approach. [0003] CN 1465527A discloses a zeolite with MFI structure containing phosphorus and transition metals. The anhydrous chemical expression of the zeolite is (0-0.3) Na 2 O·(0.5~5)Al 2 o 3 ·(1.3~10)P 2 o 5 ·(0.7~15)M 2 o 3 ·(70~97)SiO2 2 , wherein M is selected from one of the transition ...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): B01J29/46B01J29/40B01J29/48C10G11/05C07C4/06C07C11/06C07C11/09C07C11/04
CPCY02P20/52
Inventor 陈蓓艳蒋文斌朱玉霞罗一斌欧阳颖田辉平沈宁元黄志青宋海涛邓景辉
Owner CHINA PETROLEUM & CHEM CORP
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