A modification method of in-situ crystallization type catalytic cracking catalyst

A catalytic cracking and in-situ crystallization technology, applied in physical/chemical process catalysts, molecular sieve catalysts, chemical instruments and methods, etc. The effect of improving catalyst performance, reducing ammonia nitrogen pollution and low sodium oxide content

Active Publication Date: 2016-07-06
PETROCHINA CO LTD
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

The raw material processed in the method disclosed in this patent application is NaY molecular sieve synthesized by sol-gel, and in this method, NaY molecular sieve needs beating treatment before alkali washing, and the process is relatively cumbersome, and this method will increase the difficulty of NaY filtration and water washing. Therefore, it is not easy to realize in industrial production
[0009] U.S. Patent No. 3,326,797 also proposes a method for alkali treatment of molecular sieves: the equivalent molar concentration of hydroxide is 0.1 to 15 mol / L, the temperature is 0 to 100°C, and the time is 5 minutes to 5 hours. The alkali treatment in the method is mainly to extract Skeleton silicon in molecular sieves, this method only deals with molecular sieves with a silicon-aluminum ratio of 6-12, and is not applicable to molecular sieves with a ratio of less than 6
For in-situ crystallization products, when the concentration of sodium hydroxide in the solution exceeds 3mol / L and the time exceeds 3 hours, it is easy to cause the microsphere strength of the crystallization product to decrease, and the crystallinity of the molecular sieve will decrease more. When the temperature is 0 ~60°C or when the concentration of sodium hydroxide is less than 0.2mol / L, it has little effect on the matrix of the in-situ crystallization product and cannot achieve the desired effect
[0010] According to the existing technology, the ammonium salt used in the modification of the in-situ crystallization type catalytic cracking catalyst is too large, and the activity and selectivity of the catalyst cannot be significantly improved.

Method used

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  • A modification method of in-situ crystallization type catalytic cracking catalyst
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  • A modification method of in-situ crystallization type catalytic cracking catalyst

Examples

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Embodiment 1

[0052] Put 500g of crystallization product 1, sodium hydroxide and deionized water into a stainless steel kettle under stirring, sodium hydroxide / crystallization product = 0.15, exchange at 95°C for 1 hour, remove the filtrate by filtration, and deionize the filter cake with deionized water Wash until the pH value is less than 10 to obtain the alkali-treated product; the alkali-treated product, ammonium sulfate and deionized water, ammonium sulfate / alkali-treated product=0.05, exchange at pH=3.0~3.5, 90°C for 1.5 hours, and filter to remove the filtrate , the filter cake was washed with deionized water and dried to obtain an exchange material; the first exchange material was exchanged with rare earth chloride once more, and the exchange conditions were: rare earth / an exchange material=0.05, pH=3.5-4.2, and the temperature was 90°C. The time is 1 hour, and the exchanged material is filtered, washed, and dried to obtain the second batch; the second batch is roasted at 550 ° C and...

Embodiment 2

[0054] Put 500g of crystallization product 2, potassium hydroxide and deionized water into a stainless steel kettle under stirring, potassium hydroxide / crystallization product=0.08, exchange at 85°C for 1 hour, remove the filtrate by filtration, and use deionized water for the filter cake Wash until the pH value is less than 10 to obtain the alkali-treated product; the alkali-treated product, ammonium sulfate and deionized water, ammonium chloride / alkali-treated product=0.09, exchange at pH=3.0~3.5, 90°C for 2 hours, and filter to remove The filtrate and the filter cake were washed with deionized water and dried to obtain an exchange material; the first exchange material was exchanged with rare earth nitrate once again, and the exchange conditions were: rare earth / one exchange material=0.045, pH=3.5-4.2, and the temperature was 90°C. The time is 1 hour, and the exchanged material is filtered, washed, and dried to obtain the second batch; the second batch is roasted at 600°C and...

Embodiment 3

[0056] Put 500g of crystallization product 3, sodium hydroxide and deionized water into a stainless steel kettle under stirring, sodium hydroxide / crystallization product=0.01, exchange at 75°C for 3 hours, filter to remove the filtrate, and deionize the filter cake with deionized water Wash until the pH value is less than 10 to obtain the alkali-treated product; the alkali-treated product, ammonium nitrate and deionized water, ammonium nitrate / alkali-treated product=0.15, exchange at pH=3.0-3.5, 90°C for 2 hours, and filter to remove the filtrate , the filter cake was washed with deionized water and dried to obtain an exchange material; the first exchange material was exchanged with rare earth nitrate once again, the exchange conditions were: rare earth / an exchange material=0.06, pH=3.5~4.2, temperature was 90°C, time For 1 hour, the exchanged material was filtered, washed, and dried to obtain the second batch; the second batch was roasted at 620°C and the water vapor intake wa...

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Abstract

A method for modifying an in-situ crystallization type catalytic cracking catalyst. The method is to firstly treat the crystallized product of the in-situ crystallization type FCC catalyst with alkali under hydrothermal conditions, then exchange four times with ammonium ions and rare earth ions, and roast twice to obtain the desired catalyst product. . In the alkali treatment, the amount of alkali added is such that the weight ratio of alkali / crystallized product is 0.01-0.15, the reaction temperature is 70-100° C., and the treatment time is 0.1-3 hours. The method does not increase the modification cost of the catalyst, and greatly reduces the amount of ammonium salt used, thereby reducing the burden and investment in the treatment process of ammonia-nitrogen-polluted primary ammonia-nitrogen wastewater. It is an environmental protection technology in catalyst production; the prepared catalyst has relatively high With low sodium oxide content, the pore volume increases, and the catalyst performance remains basically unchanged or improved.

Description

technical field [0001] The invention relates to a modification method of a catalytic cracking catalyst, in particular to a modification method of an in-situ crystallization type catalytic cracking catalyst. Background technique [0002] In FCC catalysts, sodium oxide will seriously affect the activity, selectivity and stability of the catalyst, so the content of sodium oxide in the catalyst is strictly limited. At present, FCC catalysts include all clay catalytic cracking catalysts (in situ crystallization catalysts), semi-synthetic catalysts and fully synthetic catalysts. The in-situ crystallization catalyst uses a one-step method to prepare the molecular sieve and the matrix, which is convenient and quick, but the sodium oxide is distributed in the matrix and the molecular sieve at the same time, which greatly increases the difficulty of reducing the sodium oxide. For this reason, people use ion exchange to reduce the content of sodium oxide in the catalyst, thereby prepa...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): B01J29/08
Inventor 赵晓争王宝杰高雄厚刘宏海张莉黄世英胡清勋张忠东赵红娟李晓艳曹庚振刘明霞杨一青滕秋霞陈淑琨朱夔
Owner PETROCHINA CO LTD
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