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Mercury-free catalyst for acetylene hydrochlorination

A non-mercury catalyst, acetylene hydrochlorination technology, applied in physical/chemical process catalysts, metal/metal oxide/metal hydroxide catalysts, organic chemistry, etc., can solve the problem of easy pulverization, high catalyst cost, and activated carbon strength It can improve the anti-wear strength, reduce the catalyst cost, and reduce the amount of gold.

Active Publication Date: 2014-08-27
DALIAN RES & DESIGN INST OF CHEM IND
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

At present, activated carbon loaded with mercuric chloride is still used as a catalyst in the industry. This catalyst has three major disadvantages: first, the activated carbon has low strength, poor wear resistance, and is easy to pulverize, and the catalyst cannot be regenerated after deactivation; secondly, mercuric chloride is a It is a highly toxic substance that is easily sublimated and lost, and enters the environment, causing ecological deterioration and environmental pollution; finally, my country's mercury resources have been basically exhausted, and catalysts rely on imported raw material mercury to maintain production
[0016] The above-mentioned gold-containing non-mercury catalysts directly load the active component Au on the surface of activated carbon in the form of compounds, complexes or nanoparticles, resulting in poor thermal stability and easy sintering of the active component gold.
Moreover, the high content of precious metal gold leads to high catalyst cost, thus, it is difficult to realize industrialization

Method used

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  • Mercury-free catalyst for acetylene hydrochlorination

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0033] Weigh 1.9199g of SnCl 2 ·2H 2 O was dissolved in 40mL of absolute ethanol, and after mixing well, reflux and stir in a reflux stirring device at 78°C for 3h, and then stand and age in a 30°C constant temperature water bath for 8h to obtain a metal sol. The sol was sprayed onto 20g coconut shell activated carbon, and then dried at 80°C for 12 hours and 300°C for 4 hours to obtain coconut shell activated carbon with metal oxide film;

[0034] Weigh 0.4642g of Bi(NO 3 ) 3 ·5H 2 O and 2.2830g of Cu(NO 3 ) 2 ·3H 2 Dissolve O in 40mL of dilute nitric acid solution, then take 1.2mL of 16.7mg / mL HAuCl 4 ·4H 2 The aqueous solution of O was added to it, sprayed twice on the coconut shell activated carbon with oxide film, and then dried at 80°C for 12 hours and calcined at 200°C for 4 hours to obtain a non-mercury catalyst.

Embodiment 2

[0036] Weigh 1.9199g of SnCl 2 ·2H 2 O was dissolved in 40mL of absolute ethanol, and after mixing well, reflux and stir in a reflux stirring device at 78°C for 3h, and then stand and age in a 30°C constant temperature water bath for 8h to obtain a metal sol. The sol was sprayed on 20g coconut shell activated carbon, dried at 80°C for 12 hours, and baked at 300°C for 4 hours to obtain coconut shell activated carbon with metal oxide film;

[0037] Weigh 0.6200g Ce(NO 3 ) 3 ·6H 2 O and 2.2830g of Cu(NO 3 ) 2 ·3H 2 Dissolve O in 40mL of dilute nitric acid solution, then take 1.2mL of 16.7mg / mL HAuCl 4 ·4H 2 The aqueous solution of O was added to it, sprayed twice on the coconut shell activated carbon with oxide film, and then dried at 80°C for 12 hours and calcined at 200°C for 4 hours to obtain a non-mercury catalyst.

Embodiment 3

[0039] Weigh 3.8398g of SnCl 2 ·2H 2 O was dissolved in 40mL of absolute ethanol, and after mixing well, reflux and stir in a reflux stirring device at 78°C for 3h, and then stand and age in a 30°C constant temperature water bath for 8h to obtain a metal sol. The sol was sprayed onto 20g coconut shell activated carbon, and then dried at 80°C for 12 hours and 300°C for 4 hours to obtain coconut shell activated carbon with metal oxide film;

[0040] Weigh 0.4642g of Bi(NO 3 ) 3 ·5H 2 O and 2.2830g of Cu(NO 3 ) 2 ·3H 2 Dissolve O in 40mL of dilute nitric acid solution, then take 1.2mL of 16.7mg / mL HAuCl 4 ·4H 2 The aqueous solution of O was added to it, sprayed twice on the coconut shell activated carbon with oxide film, and then dried at 80°C for 12 hours and calcined at 200°C for 4 hours to obtain a non-mercury catalyst.

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Abstract

The invention provides a mercury-free catalyst for acetylene hydrochlorination and a preparation method thereof. The mercury-free catalyst comprises a carrier, a metal oxide film and catalyst active components, wherein the catalyst active components are distributed on the metal oxide film, and the catalyst active components include a main catalyst of gold and promoters including copper, bismuth and at least one rare earth element; the metal oxide film is applied to the surface of the carrier and the inner wall of a large hole channel, the thickness of the metal oxide film is 1 to 100 nm, and the specific surface area of the metal oxide film is 1 to 50 m<2> / g; the weight percent of the main catalyst of gold and the carrier is 0.01 to 0.2%. The mercury-free catalyst provided by the invention has the advantages of high activity and good selectivity and is suitable for the production process of a vinyl alcohol monomer with a calcium carbide acetylene method.

Description

technical field [0001] The invention relates to a non-mercury catalyst for acetylene hydrochlorination and a preparation method thereof. More specifically, the present invention relates to a gold-containing non-mercury catalyst with a metal oxide thin film and a method for its preparation. Background technique [0002] In the production of vinyl chloride in my country, the proportion of vinyl chloride monomer produced by calcium carbide acetylene process is as high as 70%. At present, activated carbon loaded with mercuric chloride is still used as a catalyst in the industry. This catalyst has three major disadvantages: first, the activated carbon has low strength, poor wear resistance, and is easy to pulverize, and the catalyst cannot be regenerated after deactivation; secondly, mercuric chloride is a A highly toxic substance, which is easily sublimated and lost, enters the environment, causing ecological deterioration and environmental pollution; finally, my country's mercu...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): B01J23/89B01J23/68C07C17/08C07C21/06
Inventor 孟纪文邵玉昌林春迎
Owner DALIAN RES & DESIGN INST OF CHEM IND
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