Cracking assistant for improving low-carbon olefin concentration

A technology for low-carbon olefins and catalytic cracking aids, which is applied in the fields of hydrocarbon cracking to hydrocarbon production, cracking, catalytic cracking, etc., can solve the problem of insufficient propylene and butene concentrations, achieve good coke and dry gas selectivity, and improve octane value, the effect of increasing the ethylene concentration

Active Publication Date: 2014-05-14
CHINA PETROLEUM & CHEM CORP +1
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

[0009] The existing additives using β zeolite still have the problem that the concentration of propylene and butene in the liquefied gas is not high enough

Method used

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  • Cracking assistant for improving low-carbon olefin concentration
  • Cracking assistant for improving low-carbon olefin concentration
  • Cracking assistant for improving low-carbon olefin concentration

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preparation example Construction

[0027] In the preparation method of the catalytic cracking aid provided by the present invention, the phosphorus-aluminum inorganic binder containing the first clay, based on its dry weight, contains Al 2 o 3 15 to 40% by weight of aluminum components, based on P 2 o 5 45-80% by weight of the phosphorus component and 1-40% by weight of the first clay on a dry basis, the P / Al weight ratio is 1.0-6.0, the pH is 1.0-3.5, and the solid content of the binder is 15 ~60% by weight. The preparation method of the first clay-containing phosphorus-aluminum compound inorganic binder comprises:

[0028] (1) Dispersing the alumina source, the first clay and water into a slurry with a solid content of 8 to 45% by weight; the alumina source is aluminum hydroxide and / or alumina that can be peptized by acid, and The dry basis of the first clay and Al 2 o 3 The weight ratio of the alumina source is 1~40:15~40;

[0029] (2) under stirring, add concentrated phosphoric acid to the slurry obt...

Embodiment 1

[0065] Beta zeolite (Naβ, produced by Qilu Catalyst Factory, SiO 2 / Al 2 o 3 =25, sodium oxide content 4.5% by weight, the same below) with NH 4 Cl solution exchange wash to Na 2 The O content is lower than 0.2% by weight, and the filter cake is obtained by filtration; dried, and the obtained sample is roasted at 350°C for 2 hours, and then heated to 550°C for 4 hours to remove the template agent; take 100g (dry basis) of the above-mentioned molecular sieve and add water Prepare a molecular sieve slurry with a solid content of 10% by weight, add 20g of oxalic acid during stirring, heat up to 80°C and stir for 1h, filter and wash until the filtrate is neutral; add water to the filter cake and beat to obtain a molecular sieve slurry with a solid content of 40% by weight, and mix 6.8gH 3 PO 4 (Concentration 85%) and 3.2gCu(NO 3 ) 2 ·3H 2O was dissolved in 30 g of water, mixed with the molecular sieve slurry, impregnated and dried; the obtained sample was calcined at 550° C...

Embodiment 2

[0068] beta zeolite with NH 4 Cl solution exchange wash to Na 2 The O content is lower than 0.2% by weight, and the filter cake is obtained by filtration; dried, and the obtained sample is roasted at 150°C for 2 hours, then heated to 350°C for 2 hours for 30 minutes, and then heated to 500°C for 4 hours for 30 minutes. Template removal agent: Take 100g of the above-mentioned molecular sieve (dry basis) and add water to prepare a molecular sieve slurry with a solid content of 10% by weight, add 10g of fluosilicic acid during stirring, heat up to 60°C and stir for 1h, filter and wash until the filtrate is neutral; add water to the filter cake Beating to obtain a solid content of 40% by weight molecular sieve slurry, 11.8gH 3 PO 4 (concentration 85%) with 6.3gCuCl 2 Dissolved in 90g of water, mixed with filter cake, soaked and dried; the obtained sample was roasted at 550°C for 2 hours, namely the modified β molecular sieve provided by the present invention.

[0069] Elementa...

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Abstract

The invention discloses a cracking assistant for improving the low-carbon olefin concentration. The cracking assistant comprises a phosphorus and transition metal-containing beta molecular sieve, a first-clay-containing phosphorus aluminum inorganic binder, other inorganic binder and second clay; the first-clay-containing phosphorus aluminum inorganic binder comprises 15-40 wt% by Al2O3 of an aluminum component, 45-80 wt % by P2O5 of a phosphorus component and 1-40 wt % by dry basis of first clay, the weight ratio of P to Al is 1-6; the phosphorus and transition metal-containing beta molecular sieve comprises 1-10wt% by P2O5 of phosphorus and 0.5-10 wt % by metallic oxide of a metal; and in the 27Al MAS NMR (Magic Angle Spinning Nuclear Magnetic Resonance) of the phosphorus and transition metal-containing beta molecular sieve, the ratio of resonance signal peak area at the chemical shift of 40+-3ppm to resonance signal peak area at the chemical shift of 54+-3ppm is greater than 1, and the percentage of the sun of the resonance signal peak area at the chemical shift of 0+-3ppm and the resonance signal peak area at the chemical shift of-12+-3ppm to the total peak area is less than 10%. The cracking assistant is used for catalytic cracking, and can improve ethylene concentrations in a catalytic cracking dry gas, and improve propylene and isobutylene concentration in a liquefied gas.

Description

technical field [0001] The invention relates to a cracking aid for catalytic cracking to produce light olefins. Background technique [0002] Low-carbon olefins Olefin is an important organic chemical raw material, and the world's demand for low-carbon olefins is increasing year by year. Fluid catalytic cracking is one of the important processes for producing low-carbon olefins. For most catalytic cracking units, adding additives is an effective technical way to increase the production of low-carbon olefins. However, the prior art has no obvious effect on increasing the concentration of isobutene in liquefied gas. From the perspective of isobutene formation and reaction chemistry in the FCC process, β molecular sieve is an effective active component. The main problem of β molecular sieve in use is that on the one hand, its structure is easily damaged during the process of removing its template agent, and on the other hand, it is easy to dealuminate during the reaction proc...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): B01J29/76B01J29/78B01J29/70C10G11/05C07C4/06C07C11/02
Inventor 陈蓓艳沈宁元朱玉霞罗一斌欧阳颖任飞蒋文斌黄志青宋海涛邓景辉
Owner CHINA PETROLEUM & CHEM CORP
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