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Cracking catalyst containing metallic oxide modified beta zeolite

A catalyst, beta zeolite technology, applied in physical/chemical process catalysts, catalytic cracking, molecular sieve catalysts, etc., can solve problems such as low liquid yield

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

The catalyst has higher propylene yield and raw material conversion rate, but lower liquid yield

Method used

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  • Cracking catalyst containing metallic oxide modified beta zeolite
  • Cracking catalyst containing metallic oxide modified beta zeolite
  • Cracking catalyst containing metallic oxide modified beta zeolite

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0033] Take 200g sodium type β zeolite (produced by Sinopec Catalyst Qilu Branch, SiO 2 / Al 2 o 3 =25 (molar ratio), dry basis accounted for 75% by weight), mixed with 3000g deionized water and 45g ammonium chloride for beating, stirred at 80°C for 2 hours, then filtered, and repeated the above process 3 times to make the Na in the zeolite 2 The O content is less than 0.2% by weight, roasted at 600°C and 100% steam for 2 hours to obtain ammonium-exchanged zeolite beta, denoted as A-1;

[0034] 52.3g zirconium nitrate Zr (NO 3 ) 4 ·5H 2 O was dissolved in 150g ethanol (analytically pure) to obtain an impregnation solution, and then the above impregnation solution was mixed with ammonium-exchanged β zeolite A-1 evenly, left to stand for 24 hours, dried at 100°C for 24 hours, and then dried in a nitrogen atmosphere at 500°C Lower roasting for 4 hours, denoted as AC-1;

[0035] Add the above roasted β zeolite AC-1 into 2000g of inorganic acid aqueous solution (dilute hydroch...

Embodiment 2

[0038]Take 200g of sodium-type β zeolite (same as above), mix it with 2000g of deionized water and 45g of ammonium chloride, stir at 80°C for 1 hour, then filter, repeat the above process 3 times, and roast at 650°C and 100% steam for 2 Hours, the β zeolite A-2 after ammonium exchange was obtained; Na in zeolite A-2 2 The O content is less than 0.2% by weight, and the water content is 1% by weight;

[0039] Dissolve 18.9g of zirconium isopropoxide in 450g of ethanol, then mix the resulting solution with ammonium-exchanged zeolite A-2 evenly, stir for 24 hours, dry at 100°C for 24 hours, and bake at 550°C in a nitrogen atmosphere for 3 Hour, obtain the beta zeolite AC-2 after roasting;

[0040] Add the above-mentioned roasted β zeolite AC-2 into 1500 g of oxalic acid aqueous solution with an acid concentration of 2.0 mol / L, continue to stir at 90° C. for 1 hour, then filter and wash with deionized water (the amount of washing water is the dry weight of molecular sieve 15 time...

Embodiment 3

[0043] Take 200g of sodium-type β zeolite (same as above), mix it with 2000g of deionized water and 60g of ammonium chloride for slurry, stir at 90°C for 3 hours, then filter, repeat the above process twice, and Na on the zeolite 2 O content is less than 0.2% by weight, roasted at 500°C for 5 hours to obtain ammonium-exchanged β zeolite A-3;

[0044] 10.5g zirconium nitrate Zr(NO 3 ) 4 ·5H 2 O was dissolved in 200g of ethanol, and then the above solution was mixed evenly with the ammonium-exchanged β zeolite, and dried after standing for 12 hours; the dried zeolite was composed of 25.6g of tetrabutyl titanate and 200g of ethanol Mix the impregnating solution, let it stand for 12 hours, then dry it at 100°C for 24 hours, and roast it under nitrogen atmosphere at 600°C for 2 hours to obtain the roasted zeolite beta, which is denoted as AC-3;

[0045] Add the roasted beta zeolite AC-3 to 1000 g of hydrochloric acid aqueous solution with an acid concentration of 0.5 mol / L, stir...

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Abstract

The invention discloses a cracking catalyst containing metallic oxide modified beta zeolite. The cracking catalyst comprises the following ingredients by taking the weight of the cracking catalyst as a standard in percentage by weight: 10-80% of Y type zeolite, 1-50% of the metallic oxide modified beta zeolite, 5-70% of clay and 5-60% of heat-resisting inorganic oxide; based on mass of oxide, the anhydrous chemical expression of the metallic oxide modified beta zeolite is as follows: (0-0.2)Na2O.(0.5-15)ZrO2.(0-10) MxOy. (0.5-15) Al2O3.(60-97)SiO2, wherein M is one selected from Ti, Cr, Fe and Ga; x refers to atomic number of M, and y refers to a number meeting the requirement of M oxidation state. The preparation method of the catalyst comprises the steps of mixing and pulping the Y type zeolite, the metallic oxide modified beta zeolite, the clay, the heat-resisting inorganic oxide binder and water, and carrying out spray drying. The catalyst is high in heavy oil cracking capacity, and high in yield of total liquid yield and liquefied gas; the propylene concentration in the liquefied gas is obviously improved.

Description

technical field [0001] The invention relates to a catalytic cracking catalyst. Background technique [0002] With the rapid growth of the demand for derivatives such as polypropylene, the world's demand for propylene is increasing year by year. Fluid catalytic cracking is one of the important processes for the production of light olefins and propylene. In order to increase the production of low-carbon olefins and propylene, people usually add shape-selective molecular sieves to the catalyst, such as US3758403, which discloses a catalyst with ZSM-5 and large-pore zeolite (mainly Y-type zeolite) as active components, which can increase the octane number of gasoline. At the same time, it also increases the yield of C3 and C4 olefins. The large-pore zeolite cracks the raw materials to generate gasoline and diesel, and the ZSM-5 shape-selective molecular sieve further cracks them into low-carbon olefins. Although ZSM-5 is a commonly used additive at present, it can increase the...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): B01J29/80B01J35/10C10G11/05
Inventor 田辉平于善青王振波朱玉霞
Owner CHINA PETROLEUM & CHEM CORP
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