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Mercury-free catalyst for preparation of VCM (vinyl chloride monomer) through acetylene hydrochlorination and using method

A technology for chlorination of vinyl chloride and non-mercury catalysts, which is applied in the direction of organic compound/hydride/coordination complex catalysts, physical/chemical process catalysts, molecular sieve catalysts, etc. Provide stability data and other issues to achieve the effect of avoiding frequent replacement, avoiding insufficient activity, and excellent stability

Inactive Publication Date: 2015-04-29
阳永荣
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

The catalyst has a certain activity, but the selectivity is much lower than that of industrial mercuric chloride catalysts, and the key performance of catalyst stability is not mentioned
[0005] Chinese patent CN102357366A discloses a catalyst for acetylene hydrochlorination with palladium as the active component and molecular sieve as the carrier, but according to the data in the examples, its activity is still much lower than that of industrial mercuric chloride catalysts, and no stability data is given
[0007] In summary, the non-mercury catalysts that have been reported now often cannot take into account all aspects of performance, and it is difficult to meet the requirements of industrial applications. Therefore, there are no examples of industrial applications so far.

Method used

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Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0022] Weigh 0.0135g of chloroplatinic acid hexahydrate and 0.1g of copper chloride dihydrate, dissolve them in 3mL of 1% polyvinyl alcohol aqueous solution, mix them well, and slowly add them dropwise to 5g of coconut shell charcoal, and keep stirring. After the dropwise addition was completed, the obtained sample was left to stand at room temperature for 1 hour, then dried at 180°C for 18 hours and taken out for use. The platinum metal content of the active component in the catalyst is 0.1%, the additive content is 1.57%, and the polyvinyl alcohol content is less than 0.6%.

[0023] Get 1g of the above-mentioned catalyst and fill it in a fixed-bed reactor with an inner diameter of 10mm, with a space velocity of 25 / h, HCl:C 2 h 2 =1.05, reacted at 180°C for 48h. The initial conversion rate of acetylene was 99.3%, and the absolute deactivation rate was 0.105% / h.

Embodiment 2

[0025] Weigh 0.0083g of chloroplatinic acid hexahydrate and 0.15g of magnesium nitrate, dissolve in 3mL of 2% polyvinylpyrrolidone aqueous solution, mix well and slowly add it dropwise to 5g of coconut shell charcoal, and keep stirring. After the dropwise addition was completed, the obtained sample was left to stand at room temperature for 1 hour, then dried at 180°C for 18 hours and taken out for use. The platinum content in the catalyst is 0.06%, the additive content is 3%, and the polyvinylpyrrolidone content is less than 1.2%.

[0026] Get 1g of the above-mentioned catalyst, and fill it in a fixed-bed reactor with an inner diameter of 10mm, with a space velocity of 100 / h, HCl:C 2 h 2 =1.05, reacted at 180°C for 48h. The initial conversion rate of acetylene was 82.2%, and the absolute deactivation rate was 0.12% / h.

Embodiment 3

[0028] Get the catalyst of 1g embodiment 2, space velocity is constant, HCl: C 2 h 2 =1.3, reacted at 180°C for 48h. The initial conversion rate of acetylene was 88.1%, and the absolute deactivation rate was 0.085% / h.

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Abstract

The invention discloses a mercury-free catalyst for preparation of a VCM (vinyl chloride monomer) through acetylene hydrochlorination and a using method. The mercury-free catalyst comprises chemical components in percentage by mass as follows: not higher than 0.1% of an active component, 0.1-20% of an additive, not higher than 10% of a stabilizer and the balance of a carrier, wherein the active component is a precious metal. Compared with the prior art, the mercury-free catalyst has the obvious advantages as follows: the high-activity precious metal is used as the active component, insufficient activity of base metals is avoided, and the basic requirement of industrial application is met; the content of the precious metal is not higher than 0.1%, the cost is substantially reduced, and the possibility of large-scale investment application is provided; the catalyst is excellent in stability, frequent replacement can be avoided, and the operability of industrial application is realized.

Description

technical field [0001] The invention relates to the field of catalysts used in the production of vinyl chloride by the calcium carbide method, in particular to a non-mercury catalyst used in the production of vinyl chloride by hydrochlorination of acetylene and a use method thereof. Background technique [0002] Vinyl chloride (VCM) is an important chemical basic raw material, and its industrial production routes mainly include ethylene method and acetylene method. The acetylene method is simple, but uses highly toxic and volatile HgCl loaded on activated carbon 2 As a catalyst, industrial production often requires a lot of energy and resources to prevent and control pollution. In practical applications, the volatilization of mercuric chloride will lead to a decrease in activity, and the catalyst needs to be overturned after a period of time, which is extremely harmful to the health of workers. According to statistics, in 2012, my country's acetylene process PVC production...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): B01J31/30B01J31/26B01J27/18B01J29/03C07C17/08C07C21/06
Inventor 阳永荣田晓晖蒋斌波王靖岱黄正梁廖祖维
Owner 阳永荣
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