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Cracking auxiliary agent for increasing low-carbon olefin concentration

A technology of low-carbon olefins and catalytic cracking additives, applied in the direction of hydrocarbon cracking, cracking, catalytic cracking, etc., can solve the problem of low-carbon olefin concentration, achieve good wear resistance, improve heavy oil conversion capacity, and increase production rate effect

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] However, the concentration of low-carbon olefins in the liquefied gas of the above additives is not high

Method used

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  • Cracking auxiliary agent for increasing low-carbon olefin concentration
  • Cracking auxiliary agent for increasing low-carbon olefin concentration
  • Cracking auxiliary agent for increasing low-carbon olefin concentration

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preparation example Construction

[0028] 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 15-40% by weight aluminum component, with 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, and does not contain chlorine, its P / Al weight ratio is 1.0-6.0, its pH is 1.0-3.5, and its solid content is 15-60% by weight. The preparation method of the phosphorus-aluminum inorganic binder containing the first clay comprises:

[0029] (1) Dispersing the alumina source, the first clay and water into a slurry with a solid content of 8-45% 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 of meter is 1-40:15-40;

[0030] (2) under stirring, add concentrated phosphoric acid to the slur...

Embodiment 1

[0071] 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 2 O was dissolved in 30 g of water, mixed with the molecular sieve slurry, impregnated and dried; the obtained sample was calcined at 550° ...

Embodiment 2

[0074] 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.

[0075] Elementa...

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Abstract

The invention relates to a cracking auxiliary agent for increasing low-carbon olefin concentration. The cracking auxiliary agent contains a modified beta molecular sieve, a first clay-containing phosphorus-aluminum inorganic binder, and other inorganic binders and VIII group metal additives, and contains or does not contain second clay, wherein the first clay-containing phosphorus-aluminum inorganic binder comprises an aluminum component, a phosphorus component and first clay, the modified beta molecular sieve containing the phosphorus and the transition metal comprises 1-10 wt% (calculated as P2O5) of the phosphorus and 0.5-10 wt% (calculated as metal oxide) of the metal, and in the 27Al MAS NMR of the molecular sieve, a ratio of the resonance signal peak area at the chemical shift of 40+ / -3 ppm to the resonance signal peak area at the chemical shift of 54+ / -3 ppm is more than or equal to 1, and the sum of the resonance signal peak areas at the chemical shifts of 0+ / -3 ppm and -12+ / -3 ppm accounts for less than or equal to 10% of the total peak area. According to the present invention, the cracking catalyst composition is used for catalytic cracking of petroleum hydrocarbons, and can be provided for increasing the catalytic cracking liquefied gas yield, increasing the concentration of the low-carbon olefin in the liquefied gas, especially the concentration of isobutene, increasing the ratio of ethylene to dry gas, and increasing the gasoline octane number, and the heavy oil conversion capacity of the main catalyst is not affected when the auxiliary agent is blended in the large proportion manner.

Description

technical field [0001] The invention relates to a cracking aid for increasing the concentration of low-carbon olefins in catalytic cracking. 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 dealumi...

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 陈蓓艳欧阳颖朱玉霞罗一斌蒋文斌任飞沈宁元黄志青宋海涛邓景辉
Owner CHINA PETROLEUM & CHEM CORP
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