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Method for improving catalytic selectivity of supported catalyst and application thereof

A supported catalyst and selectivity technology, applied in catalytic reactions, molecular sieve catalysts, chemical instruments and methods, etc., can solve problems such as incompatibility between conversion rate and selectivity, difficulty in ensuring active components, and decline in catalyst selectivity , to achieve the effect of improving molecular size selectivity and chemical reaction site selectivity

Active Publication Date: 2017-06-13
NANJING UNIV OF TECH
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

In order to further improve the catalytic efficiency of shape-selective catalysts and expand the scope of application of shape-selective catalysis, researchers often combine nano-metal active components with them, and use the high catalytic activity of nano-metals to further improve the conversion rate of selective catalysis and develop new selective catalysts. However, due to the confinement effect of the nanopores of shape-selective catalysts (molecular sieves, metal-organic framework materials), it is often difficult for nano-metal components to fully enter the pores of shape-selective catalysts, resulting in a significant drop in catalyst selectivity.
In response to this problem, researchers have continuously improved the means of loading and recombination techniques, and developed composite methods such as dual-solvent method, vapor deposition method, and plasma sputtering method, which solved the problem of incompatibility between conversion rate and selectivity to a certain extent, but still It is difficult to ensure that all active components enter the pores, thereby reducing the influence of active components on selectivity. At the same time, these methods are often complicated and difficult to be used for large-scale preparation of high-efficiency shape-selective catalysts

Method used

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  • Method for improving catalytic selectivity of supported catalyst and application thereof
  • Method for improving catalytic selectivity of supported catalyst and application thereof
  • Method for improving catalytic selectivity of supported catalyst and application thereof

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0018] Example 1: Selective Catalytic Hydrogenation of Alkenes over Molecular Sieve Catalysts

[0019] Choose an aperture of A-type molecular sieves, Pt / molecular sieve supported catalysts were prepared by the traditional impregnation method. Before the reaction, the prepared catalyst was dried in a vacuum oven at 120° C. for 10 h. Weigh 20 mg of processed The molecular sieve catalyst was placed in a 12ml glass bottle, 3ml of ethyl acetate, 62.5 μL of n-hexene and 65 μL of cis-cyclooctene were added, and sealed with a silica gel stopper. Then use a vacuum pump to pump out the gas in the bottle, and inject pure hydrogen at the same time, and repeat the operation 5 times. After the mixture was ultrasonically dispersed for 10 min, the reaction was stirred at room temperature for 24 h.

Embodiment 2

[0020] Example 2: Selective Catalytic Hydrogenation of Alkenes with Poisoned Pt / Molecular Catalyst

[0021] Take by weighing 20mg of processed in embodiment 1 The molecular sieve catalyst was placed in a 12ml glass bottle, 2ml of ethyl acetate and 100μL of poisoning agent quinoline were added, sealed with a silica gel stopper, the mixture was ultrasonically dispersed for 10min, and stirred at room temperature for 2h. Centrifuge, wash 3 times with ethyl acetate, dry, and place in a 12ml glass bottle. Add 3 mL of ethyl acetate, 62.5 μL of n-hexene, and 65 μL of cis-cyclooctene, and seal with a silicone stopper. Then use a vacuum pump to pump out the gas in the bottle, and inject pure hydrogen at the same time, and repeat the operation 5 times. After the mixture was ultrasonically dispersed for 10 min, the reaction was stirred at room temperature for 24 h. The reaction product yield and selectivity of comparative examples 1 and 2 are as shown in table 1.

[0022] Table 1 T...

Embodiment 3

[0024] Example 3: Selective catalytic hydrogenation of olefins before and after Pt / C catalyst poisoning

[0025] According to the process of Examples 1 and 2, the catalyst carrier was replaced by activated carbon to carry out the Pt / C catalyst catalytic hydrogenation reaction, and the results are shown in Table 2.

[0026] Table 2Pt / C catalyst is used for the catalytic hydrogenation reaction result of n-hexene and cis-cyclooctene

[0027]

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Abstract

The invention relates to a method for improving the catalytic selectivity of a supported catalyst and application thereof. When a catalyst support is a porous one, a poisoning agent of which the kinetic diameter is greater than the dimension of a support pore and a previously prepared supported catalyst are sufficiently stirred to react; and when the catalyst support is a non-porous one, a poisoning agent of which the kinetic diameter is greater than that of a target selective reactant and the previously prepared supported catalyst are sufficiently stirred to react, thereby obtaining the poisoned supported catalyst. According to the method, the catalytic activity of internal metal nanoparticles is retained by reducing the catalytic activity of metal nanoparticles on the external surface of the support; or the effect of improving the catalytic selectivity of the supported catalyst is achieved by screening the target reactant by means of the poisoning agent. The method can effectively improve molecular dimension selectivity or chemical reaction site selectivity in catalytic hydrogenation reaction of olefin.

Description

technical field [0001] The invention relates to the technical field of selective catalysts, in particular to a method for improving the catalytic selectivity of a supported catalyst and its application. Background technique [0002] Shape-selective catalysis has a history of nearly 60 years since it was proposed by Weisz and Frilette in 1960. With the wide use of ZSM-5 and other series of molecular sieve materials in fine chemical industry and petrochemical industry, shape-selective catalysis has been widely used by more and more people. It is well known and has aroused extensive interest of researchers. The selectivity mechanism of shape-selective catalysis is mainly to use the confinement effect of nanopores to select reactants, products or intermediate products through diffusion restriction and steric hindrance effect, so as to achieve selective hydrogenation, selective oxidation, etc. catalytic effect. In recent years, with the rapid development of nanocatalyst prepara...

Claims

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Application Information

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IPC IPC(8): B01J31/02B01J31/26B01J31/38B01J29/74B01J23/42B01J23/44C07C5/03C07C9/15C07C5/05C07C11/107C07C13/26
CPCC07C5/03C07C5/05B01J23/42B01J23/44B01J29/7407B01J31/0217B01J31/0244B01J31/26B01J31/38B01J2231/645B01J2229/34C07C9/15C07C11/107C07C13/26
Inventor 霍峰蔚张所瀛房传真张伟娜孟凡辰张文垒李红峰
Owner NANJING UNIV OF TECH
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