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Cu-SSZ-13/M-AlPO composite molecular sieve catalyst, preparation method and applications thereof

A composite molecular sieve, cu-ssz-13 technology, applied in molecular sieve catalysts, physical/chemical process catalysts, chemical instruments and methods, etc., can solve the problems of low stability, low yield and selectivity, complex channel structure distribution, etc. problems, to achieve the effect of improving thermal stability and hydrothermal stability

Active Publication Date: 2018-05-11
CHINA PETROLEUM & CHEM CORP +1
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  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

[0012] One of the technical problems to be solved by the present invention is the problem that the stability of methanol-to-olefins catalyst used in the prior art is not high, and the yield and selectivity of ethylene, propylene and butene in light olefins are low, and a new Cu -SSZ-13 / M-AlPO composite molecular sieve catalyst, the composite molecular sieve in the catalyst has complex pore structure distribution, high catalytic activity and good stability, and is used in the preparation of ethylene, propylene and butene in light olefins from methanol The advantages of higher yield and selectivity

Method used

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  • Cu-SSZ-13/M-AlPO composite molecular sieve catalyst, preparation method and applications thereof
  • Cu-SSZ-13/M-AlPO composite molecular sieve catalyst, preparation method and applications thereof
  • Cu-SSZ-13/M-AlPO composite molecular sieve catalyst, preparation method and applications thereof

Examples

Experimental program
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Effect test

Embodiment 1

[0040] Synthesis of Cu-SSZ-13 / M-AlPO Composite Molecular Sieve

[0041] Weigh 375.25g of sodium aluminate [NaAlO 2 , purity ≥98%wt., 4.57mol] was dissolved in 1214.73mL deionized water, and after stirring evenly, the solution was divided into two parts by mass, 26% and 74%, respectively, and recorded as solution S S and solution S P , 939.31g of acidic silica sol [SiO 2 ,40wt.%, 6.26mol], 212.95g of Cu-DETA chelate [made from copper salt and diethylenetriamine, 1.31mol, n(Cu:DETA=1:1)] into the Ss solution, fully stirred Finally, add 171.25g of sodium hydroxide [NaOH, 4.28mol] into the above solution to adjust the pH value of the solution between 9 and 10, and continue stirring for 1.2h to obtain solution S S '; 199.37g of orthophosphoric acid [H 3 PO 4 , 85%wt, 1.72mol], 66.16g of zinc nitrate [Zn(NO 3 ) 3 ·6H 2 O, 0.22mol] and 126.23g of triethylamine [TEA, 1.24mol] into S P , stirred for 0.6h to obtain solution S P ’, the solution S S ’ with solution S P ’ were ...

Embodiment 2

[0043] Synthesis of Cu-SSZ-13 / M-AlPO Composite Molecular Sieve

[0044] Weigh 579.41g of aluminum sulfate [Al 2 (SO 4 ) 3 18H 2 O, purity ≥98wt.%, 0.87mol] was dissolved in 11713.22mL deionized water, and after stirring evenly, the solution was divided into two parts by mass, 60% and 40%, respectively, and recorded as solution S S and solution S P , 166.69g of silica [SiO 2 , 99%wt., 2.78mol], 217.18g of copper nitrate [Cu(NO 3 ) 2 ·3H 2 O, 99%wt., 0.92mol] and 174.16g of tetraethylenepentamine [TEPA, 0.92mo] were put into the Ss solution, and after fully stirring, 229.71g of lithium hydroxide [LiOH, 9.57mol] was added to the above solution to adjust the pH of the solution The value is between 8 and 9, and the solution S is obtained after continuing to stir for 1.1h S '; 91.75g ​​of ammonium dihydrogen phosphate [NH 4 h 2 PO 4 ,0.80mol], 33.54g of gallium nitrate [Ga(NO 3 ) 3 9H 2 O, 0.13mol] and 21.87g of ethylamine [EA, 0.49mol] into S P , stirred for 2.2h to...

Embodiment 3

[0046] Synthesis of Cu-SSZ-13 / M-AlPO Composite Molecular Sieve

[0047] Weigh 5325.26g of aluminum nitrate [Al(NO 3 ) 3 9H 2O, purity ≥98%wt., 14.19mol] was dissolved in 28886.86mL deionized water, and after stirring evenly, the solution was divided into two parts by mass, 50% and 50%, respectively, and recorded as solution S S and solution S P , 8537.85g of silica sol [SiO 2 , 40wt%, 56.92mol], copper acetate [Cu(OAc) of 258.41g 2 ·H 2 O, purity ≥98%wt., 1.29mol] and 188.60g of triethylenetetramine [TETA, 1.29mol], after fully stirring, 1329.99g of potassium hydroxide [KOH, 22.71mol] was added to the above solution to adjust the pH value of the solution Between 10 and 11, continue stirring for 1 hour to obtain solution S S ’; 1555.38g of orthophosphoric acid [H 3 PO 4 , 85%wt, 13.49mol], 823.96g of manganese nitrate [Mn(NO 3 ) 2 4H 2 O, 3.28mol] and 2327.21g of di-n-propylamine [DPA, 22.99mol], stirred for 2.1h to obtain solution S P ’; the solution S S ’ with s...

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Abstract

The invention relates to a Cu-SSZ-13 / M-AlPO composite molecular sieve catalyst, a preparation method and applications thereof. In the prior art, the stability of the methanol-to-olefin catalyst is nothigh, the selectivity of ethylene, propylene and butylene in low-carbon olefins is low, and the yield is low. A purpose of the present invention is mainly to solve the problems in the prior art. According to the technical scheme of the present invention, the Cu-SSZ-13 / M-AlPO composite molecular sieve catalyst is used, and comprises, by weight, a) 10-100% of a Cu-SSZ-13 / M-AlPO composite molecularsieve, and b) 0-90% of a binder. With the technical scheme, the problems in the prior art are well solved. The obtained catalyst of the present invention can be used in the industrial production of methanol-to-olefin.

Description

technical field [0001] The invention relates to a Cu-SSZ-13 / M-AlPO composite molecular sieve catalyst, a preparation method and an application thereof. Background technique [0002] Due to the wide range of internal pore size distribution and the rich diversity of topological structures, zeolite molecular sieve materials are widely used in the fields of adsorption, heterogeneous catalysis, carriers of various guest molecules, and ion exchange. They are mainly characterized by selective adsorption, and their unique pore system enables them to sieve molecules of different sizes, which is why this type of material is called "molecular sieve". In theory, only materials with adsorption capacity (guest molecule water or template can be removed) can be called microporous materials or molecular sieves. According to the definition of the International Union of Pure and Applied Chemistry (IUPAC), porous materials can be divided into the following three categories according to their p...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): B01J29/83B01J29/76B01J29/84C07C1/20C07C11/04C07C11/06C07C11/08
CPCB01J29/763B01J29/83B01J29/84B01J2229/18C07C1/20C07C11/04C07C11/06C07C11/08Y02P20/52Y02P30/20Y02P30/40
Inventor 乔健滕加伟袁志庆张铁柱
Owner CHINA PETROLEUM & CHEM CORP
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