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Method for improving stability of catalyst during resource utilization of HFC-23

A technology of HFC-23 and HCFC-22, which is applied in the field of suppressing the selectivity of by-product CFC-12, can solve the problems of low product selectivity and increased selectivity, and achieve the goal of improving selectivity, improving stability and reducing carbon deposition Effect

Active Publication Date: 2021-06-18
ZHEJIANG RES INST OF CHEM IND CO LTD +2
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

However, in this method, the selectivity of by-product CFC-12 is significantly increased, reaching 2% to 8%, and the product selectivity is low

Method used

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Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0033] Catalyst preparation: mix dichromium trioxide and dicobalt trioxide powders by grinding, control the Co mass content to 1.0%, and obtain 1.0% Co / Cr 2 o 3 catalyst precursor. For the 1.0% Co / Cr2 o 3 The catalyst precursor is subjected to two-stage fluorination treatment: 1) fluorination treatment at 250°C for 2 hours in a mixed atmosphere of 10% hydrogen fluoride and 90% nitrogen; 2) fluorination treatment at 300°C for 5 hours in a hydrogen fluoride atmosphere. The catalyst obtained after fluorination treatment is designated as catalyst 1.

[0034] Recycling of HFC-23: Chlorofluoromethane and chloroform are passed into a reactor equipped with 50ml of catalyst 1 at a ratio of 1:1.5 (molar ratio), and the reaction is carried out at a reaction temperature of 310°C, a pressure of 1 bar, and a residence time of 5s. The conversion rate of trifluoromethane is 26.6%, the selectivity of HCFC-22 is 44.8%, the selectivity of HCFC-21 is 54.7%, the selectivity of by-product CFC-12...

Embodiment 2

[0036] Preparation of the catalyst: the powders of chromium sesquioxide and ferric oxide are mixed by grinding, and the mass content of Fe is controlled to be 1.0%, so as to obtain 1.0% Fe / Cr 2 o 3 catalyst precursor. For the 1.0% Fe / Cr 2 o 3 The catalyst precursor is subjected to two-stage fluorination treatment: 1) fluorination treatment at 250°C for 2 hours in a mixed atmosphere of 10% hydrogen fluoride and 90% nitrogen; 2) fluorination treatment at 300°C for 5 hours in a hydrogen fluoride atmosphere. The catalyst obtained after fluorination treatment is designated as catalyst 2.

[0037] Recycling of HFC-23: Chlorofluoromethane and chloroform are passed into a reactor equipped with 50ml of catalyst 2 at a ratio of 1:1.5 (molar ratio), and the reaction is carried out at a reaction temperature of 310°C, a pressure of 1 bar, and a residence time of 5s. The conversion rate of trifluoromethane was 26.3%, the selectivity of HCFC-22 was 44.9%, the selectivity of HCFC-21 was 5...

Embodiment 3

[0039] Preparation of the catalyst: the powders of chromium trioxide and nickel trioxide are mixed by grinding, and the mass content of Ni is controlled to be 1.0%, so as to obtain 1.0% Ni / Cr 2 o 3 catalyst precursor. For the 1.0% Ni / Cr 2 o 3 The catalyst precursor is subjected to two-stage fluorination treatment: 1) fluorination treatment at 250°C for 2 hours in a mixed atmosphere of 10% hydrogen fluoride and 90% nitrogen; 2) fluorination treatment at 300°C for 5 hours in a hydrogen fluoride atmosphere. The catalyst obtained after fluorination treatment is designated as catalyst 3.

[0040] Recycling of HFC-23: Chlorofluoromethane and chloroform are passed into a reactor equipped with 50ml of catalyst 3 at a ratio of 1:1.5 (molar ratio), and the reaction is carried out at a reaction temperature of 310°C, a pressure of 1 bar, and a residence time of 5s. The conversion rate of trifluoromethane is 25.3%, the selectivity of HCFC-22 is 43.8%, the selectivity of HCFC-21 is 55.5...

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PUM

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Abstract

The invention discloses a method for improving the stability of a catalyst during resource utilization of HFC-23. The resource utilization is realized by a fluorine-chlorine exchange reaction of HFC-23 and halogenated hydrocarbon; the catalyst for the fluorine-chlorine exchange reaction comprises a main catalyst and a metal oxide; and the metal oxide is at least one selected from K, Na, Fe, Co, Cu, Ni, Zn and Ti, and the addition amount of the metal oxide is 0.1-5 wt%. The catalyst has the advantages of good stability, long service life, low content of the by-product CFC-12 and the like.

Description

technical field [0001] The invention relates to resource utilization of HFC-23, in particular to a method for improving catalyst stability and simultaneously suppressing the selectivity of by-product CFC-12 in the resource utilization of HFC-23. Background technique [0002] HFC-23 (CHF 3 , trifluoromethane, R23) is the industrial production of HFC-22 (HCFC-22, difluorochloromethane, R22 or CHClF 2 ) is an inevitable by-product, has a strong greenhouse effect, and its global warming potential (GWP, Global Warming Potential) is CO 2 14800 times. According to statistics, my country's HFC-23 emissions accounted for 68% of the world's emissions in 2013, with an output of more than 20,000 tons, equivalent to CO 2 Annual emissions reached 296 million tons. Therefore, the resource utilization of HFC-23 is an important topic in realizing energy saving and emission reduction. [0003] At present, in the industry, the by-product HFC-23 produced in the production process of HCFC-2...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07C17/20C07C19/10B01J23/86B01J37/26B01J38/14
CPCC07C17/202B01J23/864B01J23/862B01J23/866B01J37/26B01J38/14C07C19/10B01J27/132B01J37/0018B01J37/0036B01J37/04Y02P20/584B01J23/94B01J38/04
Inventor 韩文锋王术成周飞翔刘武灿张建君李西良
Owner ZHEJIANG RES INST OF CHEM IND CO LTD
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