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Catalytic cracking catalyst

A catalytic cracking and catalyst technology, applied in catalytic cracking, physical/chemical process catalysts, molecular sieve catalysts, etc., can solve the problems of zeolite framework destruction, zeolite product crystallinity reduction, zeolite crystallinity reduction and other problems, achieving good stability, reducing The effect of increasing coke formation rate and improving the utilization rate of heavy oil

Active Publication Date: 2014-01-15
CHINA PETROLEUM & CHEM CORP +1
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AI Technical Summary

Problems solved by technology

This treatment method uses the treatment of zeolite samples under the condition of low pH value, and does not adopt protective measures, which will easily lead to the destruction of zeolite framework and reduce the crystallinity of zeolite.
[0014] US4503023 discloses a kind of LZ~210 zeolite and its preparation method. NaY zeolite is dealuminated with fluorosilicate to increase the silicon-aluminum ratio of zeolite. When Y zeolite is dealuminated, the SiO of the zeolite product 2 / Al 2 o 3 The molar ratio usually cannot be higher than 13, otherwise, the crystallinity of zeolite products will be greatly reduced
In addition, the modified Y zeolite prepared by using fluorosilicate to dealuminate and supplement silicon has very few secondary pores, which is unfavorable for heavy oil catalytic cracking reactions

Method used

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preparation example Construction

[0032] The preparation method of the above-mentioned modified Y-type molecular sieve is obtained by using NaY molecular sieve as a raw material through the preparation process of "three-cross three-baking". The so-called "three-cross three-baking" is a general abbreviation for a molecular sieve modification process in the field. That is, the combined modification process of three times of exchange and three times of hydrothermal treatment is adopted. The rare earth and phosphorus are exchanged, and the exchange solution containing phosphorus and the exchange solution containing rare earth are added for exchange. Phosphorus can be added in any exchange process, and can be added once or several times. The rare earth can be added in any exchange process other than the first exchange, and the exchange process can also add a dealumination agent to carry out chemical dealumination to promote the removal of aluminum. The chemical dealumination process can be carried out in any exchange...

Embodiment 1

[0073] (1) Preparation of modified molecular sieves

[0074] Use NaY molecular sieve as raw material to exchange with ammonium sulfate solution. The treatment conditions are: NaY molecular sieve (dry basis): ammonium sulfate: water = 1:1.0:8 (weight ratio), adjust the pH value to 3.5 with sulfuric acid, exchange at 85°C for 1 hour, wash . Hydrothermal roasting treatment, roasting temperature 580°C, 100% steam roasting time 2h. Treat the post-baked sample with a solution containing rare earth, the treatment conditions are: a baked molecular sieve (dry basis): rare earth chloride (according to RE 2 o 3 Calculated): water = 1:0.042:8 (weight ratio), exchanged at 70°C for 1h, and washed with deionized water. Hydrothermal roasting treatment, roasting temperature 580°C, 100% steam roasting time 2h. Treat the sample after secondary baking with a solution containing phosphoric acid and oxalic acid. The treatment conditions are: secondary baking molecular sieve (dry basis): phospho...

Embodiment 2

[0084] (1) Preparation of modified molecular sieves

[0085] Use NaY molecular sieve as raw material to exchange with ammonium chloride solution. The treatment conditions are: NaY molecular sieve (dry basis): ammonium chloride: water = 1:0.8:8, adjust the pH value to 4.0 with hydrochloric acid, exchange at 90°C for 1 hour, and wash. Hydrothermal roasting treatment, roasting temperature 550°C, 80% steam roasting time 2h. Treat the post-baked sample with phosphoric acid and fluosilicic acid solution, the treatment conditions are: a baked molecular sieve (dry basis): phosphoric acid (according to P): fluosilicic acid: water = 1: 0.01: 0.03: 8, hydrochloric acid to adjust pH2. 8. Exchange at 70°C for 1 hour, filter; wash with deionized water. Hydrothermal roasting treatment, roasting temperature 550°C, 70% steam roasting time 2h. Treat the sample after secondary roasting with a solution containing rare earth, and the treatment conditions are: secondary roasting molecular sieve (...

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Abstract

The invention discloses a catalytic cracking catalyst containing 10-50wt% of modified Y-type molecular sieve, 0-30wt% of other molecular sieves, 10-70wt% of clay and 10-40wt% of inorganic oxide binder, wherein the contents of the modified Y-type molecular sieve, the other molecular sieves and the clay are measured according to dry basis, and the content of the inorganic oxide binder is measured according to oxides; the modified Y-type molecular sieve has the lattice constant of 2.420-2.440nm and the specific hydroxyl nest concentration of less than 0.35mmol / g and contains 0.05-6wt% of P, 0.03-10wt% of RE2O3 and less than 22wt% of aluminum oxide according to the weight percentage. The catalytic cracking catalyst disclosed by the invention has favorable stability in a catalytic cracking process and can be used for reducing green cokes and increasing the utilization ratio of heavy oil.

Description

technical field [0001] The present invention relates to a catalyst for catalytic cracking of hydrocarbon oil, and more specifically to a catalyst for catalytic cracking of a modified Y-type molecular sieve containing "three-cross-three-calcined" Background technique [0002] With the decreasing of petroleum resources, it has become an indisputable fact that petroleum raw materials become heavy and inferior. As the main processing method to convert heavy oil into gasoline and diesel light fuel oil, catalytic cracking inevitably needs to process more and lower quality heavy oil feedstock. The reduction of conversion rate and the increase of coke yield are one of the manifestations of the impact of the heavy and poor quality of feedstock oil on catalytic cracking. Aiming at this, people have done a lot of research on molecular sieve modification, catalyst manufacturing and process design (Liu Tao, Zhang Zhongdong, Zhang Haitao, etc. Sinoforeign Energy. 2009, 14(1): 71-77). Ho...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): B01J29/80B01J29/08C10G11/05
Inventor 龙军朱玉霞罗一斌严加松任飞杨雪田辉平庄立李明罡欧阳颖舒兴田
Owner CHINA PETROLEUM & CHEM CORP
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