A bifunctional catalyst of a sodium-free silica-alumina molecular sieve encapsulating metal nanoparticles and a preparation method thereof

A technology of metal nanoparticles and bifunctional catalysts, which is applied in the direction of molecular sieve catalysts, catalyst activation/preparation, chemical instruments and methods, etc., can solve the problems that molecular sieves do not have acid catalytic function, do not involve molecular sieve acid catalytic function, and process complexity, etc. Achieve the effects of adjustable molecular sieve acid properties and pore structure, uniform distribution of metal nanoparticles, and uniform distribution of metal particles

Active Publication Date: 2021-05-25
INST OF PROCESS ENG CHINESE ACAD OF SCI
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

[0006] CN 107020147A (2017) discloses a MFI structure sheet molecular sieve catalyst, preparation method and application of encapsulating metal oxides or metal nanoparticles. First, a sheet MFI structure molecular sieve is synthesized, and then a silicon support column is used to support a sheet MFI structure molecular sieve And the metal oxide or metal nanoparticles are encapsulated between the sheets, which is equivalent to the method of post-treatment modification to realize the MFI structure molecular sieve encapsulation of metal oxide or metal nanoparticles, and the content of metal oxide in the entire catalyst is 0.1 ~5wt%; in addition, the method requires many steps and long crystallization time
[0007] However, the above work on encapsulating metals with molecular sieves only uses the structural characteristics of molecular sieves to achieve encapsulation of metals, and does not involve the acid catalytic function of molecular sieves. The synthesized molecular sieves do not have acid catalytic functions and cannot be realized.
Moreover, the currently reported patents and documents are more focused on molecular sieve encapsulation of noble metal catalysts, the process is complicated and there are many steps
As future industrial catalysts, non-noble metals such as Ni, Co, and Fe will have more competitive advantages, but there are still limited reports on encapsulating non-noble metal catalysts, especially the dispersion of metal Ni particles is a very difficult challenge

Method used

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  • A bifunctional catalyst of a sodium-free silica-alumina molecular sieve encapsulating metal nanoparticles and a preparation method thereof
  • A bifunctional catalyst of a sodium-free silica-alumina molecular sieve encapsulating metal nanoparticles and a preparation method thereof
  • A bifunctional catalyst of a sodium-free silica-alumina molecular sieve encapsulating metal nanoparticles and a preparation method thereof

Examples

Experimental program
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Effect test

Embodiment 1

[0078] This embodiment illustrates the H-ZSM-5 (SiO 2 / Al 2 o 3 =100) bifunctional catalyst and preparation method of molecular sieve:

[0079] (1) Mix SB powder, tetrapropylammonium hydroxide (TPAOH) and deionized water, and conduct hydrothermal treatment at 150°C for 4 hours to obtain a colorless, clear and transparent solution A; wherein, the molar composition of A is: TPAOH / Al 2 o 3 =15,H 2 O / Al 2 o 3 =50.

[0080] (2) Slowly drop the complexed transparent solution of nickel and ethylenediamine into the solution A of step (1), without obvious precipitation; then add solid silica gel, tetrapropylammonium hydroxide (TPAOH) and deionized water, Stir for 6h to obtain a mixture B; wherein, the molar composition of B is: SiO 2 / Al 2 o 3 =100, TPAOH / SiO 2 =0.2,H 2 O / SiO 2 =10, Ni / SiO 2 = 0.02.

[0081] (3) Transfer mixture B into a crystallization kettle, crystallize at 100°C for 24h, then adjust to 120°C for 24h, take it out, filter, dry, roast, and reduce to obta...

Embodiment 2

[0084] This embodiment illustrates the H-ZSM-5 (SiO 2 / Al 2 o 3 =100) bifunctional catalyst and preparation method of molecular sieve:

[0085] (1) Mix SB powder, tetrapropylammonium hydroxide (TPAOH) and deionized water, and perform hydrothermal treatment at a temperature of 150°C for 4 hours to obtain a colorless, clear and transparent solution A; wherein, the molar composition of A is: TPAOH / Al 2 o 3 =15,H 2 O / Al 2 o 3 =50.

[0086] (2) Nickel nitrate and ethylenediamine complex aqueous solution are slowly added dropwise in the solution A of step (1), no obvious precipitation is generated; then add solid silica gel, tetrapropyl ammonium hydroxide (TPAOH) and deionized water, stir Treat for 6h to obtain mixture B; wherein, the molar composition of B is: SiO 2 / Al 2 o 3 =100, TPAOH / SiO 2 =0.2,H 2 O / SiO 2 =10, Ni / SiO 2 = 0.02.

[0087] (3) Transfer the mixture B into a crystallization kettle, crystallize at a temperature of 170° C. for 14 hours, take it out, f...

Embodiment 3

[0098] This embodiment illustrates the H-ZSM-5 (SiO 2 / Al 2 o 3 =200) Molecular sieve bifunctional catalyst and preparation method:

[0099] (1) Using SB powder as the aluminum source, add tetrapropylammonium hydroxide (TPAOH) and deionized water, and conduct hydrothermal treatment at 140°C for 2 hours to obtain a clear and transparent solution A; wherein, the molar ratio of A is: TPAOH / Al 2 o 3 =15,H 2 O / Al 2 o 3 =50.

[0100] (2) Slowly add nickel and ethylenediamine complexed transparent solution into solution A of step (1), without obvious precipitation; then add solid silica gel, tetrapropylammonium hydroxide (TPAOH) and deionized water, and stir Treat for 6h to obtain mixture B; wherein, the molar composition of B is: SiO 2 / Al2 o 3 =200, TPAOH / SiO 2 =0.15,H 2 O / SiO 2 =10, Ni / SiO 2 = 0.04.

[0101] (3) Transfer the mixture B into a crystallization kettle, crystallize at 170°C for 12 hours, take it out, filter, dry, roast, and reduce to obtain a dual-funct...

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Abstract

The present invention relates to a bifunctional catalyst of a sodium-free aluminosilicate acidic molecular sieve encapsulating metal nanoparticles and a preparation method thereof. The bifunctional catalyst is added with a metal precursor during the in-situ synthesis process of a sodium-free aluminosilicate acidic molecular sieve. Utilize the "one-step method" to realize the encapsulation of metal nanoparticles by sodium-free silica-alumina acidic molecular sieve, and obtain a dual-functional catalyst with both metal hydrogenation/dehydrogenation function and molecular sieve acid catalytic function; the metal content in the dual-functional catalyst is 0.1-10wt %, the distribution of metal nanoparticles is uniform, the particle size is uniform, and the size is 1-10nm.

Description

technical field [0001] The present invention relates to the field of catalysts, in particular to a dual-functional catalyst and a preparation method of a sodium-free silico-alumino acidic molecular sieve encapsulating metal nanoparticles, to be precise, to an encapsulating non-precious metal Ni, Co, Cu, Fe, Mo , Zn, Mn, Cr, etc. at least one kind of nano-particle sodium-free aluminosilicate acidic molecular sieve dual-function catalyst and preparation method, and a dual-function catalyst with metal hydrogenation / dehydrogenation function and molecular sieve acid catalysis function. Background technique [0002] Catalysis is the core technology in the chemical and chemical production process, and catalyst is the soul of the entire catalytic technology. Metal particles are generally the key active components in reactions such as hydrogenation, oxidation, and dehydrogenation; molecular sieves, as a type of inorganic porous material, are the most widely used catalytic materials i...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): B01J29/70B01J29/76B01J29/78B01J29/46B01J29/40B01J29/48B01J37/10B01J37/18B01J37/08
Inventor 曹宏斌石艳春谢勇冰
Owner INST OF PROCESS ENG CHINESE ACAD OF SCI
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