Fluorine-containing weak coordination anion modified copper-based catalyst for acetylene hydrochlorination reaction as well as preparation method and application thereof

A technology of acetylene hydrochlorination and anion modification, which is applied in the direction of physical/chemical process catalysts, chemical instruments and methods, hydrogen halide addition preparation, etc., can solve the problems of poor stability and low activity of copper-based catalysts, and achieve improved stability properties, improving the activity of copper-based catalysts, and enhancing the acidity of Lewis acids

Active Publication Date: 2021-06-04
NANKAI UNIV +1
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

[0007] Aiming at the current ubiquitous copper-based catalysts with low activity and poor stability

Method used

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  • Fluorine-containing weak coordination anion modified copper-based catalyst for acetylene hydrochlorination reaction as well as preparation method and application thereof

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0043] (1) 10.06 g of tetrahydrate trifluoroacetate is dissolved in 19.00 g of anhydrous ethanol to obtain a bronze ion and trifluoroacetate anion of the impregnation liquid;

[0044](2) Immerse the above impregnation liquid onto 20.00 g of activated carbon by an equal volume impregnation method, and the room temperature is sealed for 1 hour;

[0045] (3) The impregnated activated carbon first was dried in a vacuum oven (vacuum degree less than -0.09 MPa) at 50 ° C for 1 hour, and then dried in a vacuum oven (vacuum degree less than -0.09 MPa) for 4 hours, A1.

[0046] A1 at 180 ° C in reaction conditions, acetylene air speed 80h -1 At the end of the hydrochloride volume ratio of 1.2: 1, the acetylene conversion is 85.0%, and the reaction selectivity was 99.8%.

Embodiment 2

[0048] (1) 14.66 g of a copper boricrate (45% aqueous solution) was taken, and 7.00 g of deionized water was added to the impregnation fluid of copper-containing ion and tetrafluoroborate.

[0049] (2) Immerse the above impregnation liquid onto 20.00 g of activated carbon by an equal volume impregnation method, and the room temperature is sealed for 1 hour;

[0050] (3) The impregnated activated carbon first was dried in a vacuum oven at 50 ° C for 1 hour, followed by drying at a vacuum oven (vacuum degree less than -0.09 MPa) at a vacuum oven at a vacuum oven at a vacuum oven at a vacuum oven at a vacuum oven at a 90 ° C. Catalyst. A2.

[0051] A2 is 180 ° C in the reaction conditions, acetylene air is 40h -1 At a substantial ratio of hydrogen chloride ratio 1.2: 1, the acetylene conversion is 90.1%, and the reactive selectivity is 99.8%.

Embodiment 3

[0053] (1) 10.06 g of tetrahydrate trifluoroacetate is dissolved in 19.00 g of anhydrous ethanol to obtain a bronze ion and trifluoroacetate anion of the impregnation liquid;

[0054] (2) Immerse the above impregnation liquid onto 20.00 g of activated carbon by an equal volume impregnation method, and the room temperature is sealed for 1 hour;

[0055] (3) The impregnated activated carbon first was dried in a vacuum oven (vacuum degree less than -0.09 MPa) at 50 ° C for 1 hour, and then dried in a vacuum oven (vacuum degree less than -0.09 MPa) for 4 hours, A3.

[0056] A3 in the reaction conditions 180 ° C, acetylene air speed 60h -1 At a substantial ratio of hydrogen chloride ratio 1.2: 1, the acetylene conversion was 91.0%, and the reactive selectivity was 99.9%.

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Abstract

The invention relates to a fluorine-containing weak coordination anion modified copper-based catalyst for acetylene hydrochlorination reaction and a preparation method and application thereof, wherein a carrier of the catalyst is activated carbon, a main active component is copper ions, and fluorine-containing weak coordination anions are introduced on the basis. Fluorine, as an element with the maximum electronegativity, is very high in the electron withdrawing capacity, so that negative charges in molecules can be highly delocalized; therefore, fluorine-containing anions are stable, have weak coordination and are commonly used for activity research of electrophilic reagents. Fluorine-containing weak coordination anions are introduced into the copper-based catalyst, so that the Lewis acid acidity of metal ions is enhanced, an active center electronic structure is adjusted, on one hand, acetylene is conveniently activated by copper to generate a vinyl copper intermediate, and on the other hand, the adsorption and desorption capability of the catalyst on raw material gas and product gas is adjusted, and the activity and the stability of the copper-based catalyst are effectively improved.

Description

Technical field [0001] The invention belongs to the field of chemical catalysis, and more particularly to a fluorine-containing cohesive anion modified copper-based catalyst for acetylene hydrochlorination reaction and a preparation method thereof. Background technique [0002] PVC (PVC) is one of the five general resins in the world, and is widely used in various industries such as chemical, building materials, agriculture and medical devices. In 2018, China's total PVC capacity exceeded 24 million tons, accounting for more than 40% of total PVC production capacity. It is estimated that by 2026, the total demand in global PVC is expected to reach 56.2 million tons. Polyvinyl chloride (PVC) production requires a vinyl chloride monomer (VCM), in view of the special energy structure of "rich coal, reidarable oil, less gas", my country's choice of technical maturity, less water consumption, low production cost, and coal The basic acetylene method production route, but the core link ...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): B01J27/06C07C21/06C07C17/08
CPCB01J27/06C07C17/08C07C21/06
Inventor 李伟张鲜明韩冲
Owner NANKAI UNIV
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