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Method of recycling byproduct-trifluoromethane in HCFC-22 production to prepare difluoromethane

A technology of trifluoromethane and difluoromethane is applied in the field of resource utilization of converting by-product trifluoromethane into difluoromethane, and can solve the problems of failure to convert trifluoromethane, high reaction temperature, many by-products, and the like, Achieve the effects of high catalyst selectivity, low reaction temperature, and no tail gas emissions

Active Publication Date: 2019-05-14
ZHEJIANG LANTIAN ENVIRONMENTAL PROTECTION HI TECH +1
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

[0010] In the prior art, when treating trifluoromethane with gas-phase cracking reaction, a very high reaction temperature is required to achieve a certain conversion rate, and there are many by-products and serious carbon deposition; by adding halogenated hydrocarbons, trifluoromethane is converted into HCFC- At 22 o'clock, it only converts trifluoromethane into HCFC-22, but fails to convert trifluoromethane into higher value compounds

Method used

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Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0062] Catalyst pretreatment: dichromium trioxide in N 2 Treat at 250°C for 5 hours, fluoride at 400°C for 2 hours in a mixed atmosphere of 10% hydrogen fluoride and 90% nitrogen, and finally treat at 400°C for 5 hours with hydrogen fluoride.

[0063] Reaction: Pass trifluoromethane and dichloromethane at a ratio of 1:1 (molar ratio) into a reactor containing 20ml of pretreated chromium oxide catalyst, at a temperature of 350°C, a pressure of 1bar, and a space velocity of 1000h -1 The reaction was carried out under the conditions to obtain the reaction product. During the reaction, all pipelines were kept warm to 60°C with heating tape. In the reaction product, the main product includes difluoromethane, chlorofluoromethane and chlorodifluoromethane, and its selectivity is 26.1%, 31.4% and 42.4% respectively, wherein the conversion ratios of trifluoromethane and dichloromethane are respectively 17.4% and 18.8%. The catalyst activity remained stable after 200 hours of reactio...

Embodiment 2

[0066] Catalyst pretreatment: dichromium trioxide in N 2 Treat at 200°C for 4 hours, fluoride at 350°C for 3 hours in a mixed atmosphere of 10% hydrogen fluoride and 90% nitrogen, and finally treat at 350°C for 5 hours with hydrogen fluoride.

[0067] Reaction: Pass trifluoromethane and dichloromethane at a ratio of 1:1 (molar ratio) into a reactor containing 20ml of pretreated chromium oxide catalyst, at a temperature of 450°C, a pressure of 2bar, and a space velocity of 2000h -1 The reaction was carried out under the conditions to obtain the reaction product. During the reaction, all pipelines were kept warm to 60°C with heating tape. In the reaction product, the main product includes difluoromethane, chlorofluoromethane and chlorodifluoromethane, and its selectivity is 22.5%, 25.2% and 40.5% respectively, wherein the conversion rates of trifluoromethane and dichloromethane are respectively 25.6% and 27.1%. The catalyst activity remained stable after 200 hours of reaction...

Embodiment 3

[0070] Catalyst pretreatment: dichromium trioxide in N 2 Treat at 250°C for 5 hours, fluoride at 400°C for 2 hours in a mixed atmosphere of 10% hydrogen fluoride and 90% nitrogen, and finally treat at 400°C for 5 hours with hydrogen fluoride.

[0071] Reaction: Pass trifluoromethane and dichloromethane at a ratio of 1:2 (molar ratio) into a reactor containing 20ml of pretreated chromium sesquioxide catalyst. -1 The reaction was carried out under the conditions to obtain the reaction product. During the reaction, all pipelines were kept warm to 60°C with heating tape. In the reaction product, the main product includes difluoromethane, chlorofluoromethane and chlorodifluoromethane, and its selectivity is 29.2%, 27.1% and 43.4% respectively, wherein the conversion ratios of trifluoromethane and dichloromethane are respectively 34.5% and 21.2%. The catalyst activity remained stable after 200 hours of reaction.

[0072] Rectification: The reaction product is subjected to rectif...

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PUM

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Abstract

The invention discloses a method of recycling trifluoromethane. The method includes: under action of at least one catalyst of Cr2O3, CrF3 and partially fluorinated Cr2O3, allowing trifluoromethane anddichloromethane to react to obtain a reaction product containing difluoromethane and monochlorodifluoromethane, and rectifying to obtain difluoromethane. The method can realize recycling of trifluoromethane, can convert the same into difluoromethane with high value and has great economic benefit.

Description

technical field [0001] The invention relates to a resource utilization method of by-product trifluoromethane in the production of HCFC-22, in particular to a resource utilization method of converting by-product trifluoromethane into difluoromethane. Background technique [0002] Chlorodifluoromethane (HCFC-22, R22 or CHClF 2 ) used to be the most widely used refrigerant and blowing agent, because it is an ozone-depleting substance, it will be gradually banned. However, HCFC-22 is also the main raw material for preparing plastic monomers such as tetrafluoroethylene (TFE) and hexafluoropropylene (HFP). Its mass production is inevitable, and my country's HCFC-22 production capacity has exceeded half of the global total (about 700,000 tons). CHF 3 It is an inevitable by-product produced in the process of producing R22. According to different technological processes, CHF 3 The production amount of Fluorine is about 2-5% of R22 [Journal of Fluorine Chemistry, 2012, 140:7-16]. ...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07C19/08C07C17/35C07C17/383
Inventor 韩文锋习苗王术成杨鲁腾吴志星刘武灿张建君
Owner ZHEJIANG LANTIAN ENVIRONMENTAL PROTECTION HI TECH