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Application of a Supported Catalyst in Trifluoromethane Cracking

A supported catalyst, trifluoromethane technology, applied in physical/chemical process catalysts, metal/metal oxide/metal hydroxide catalysts, organic chemistry, etc., can solve the problem of high conversion rate, few target products and low cracking efficiency and other problems, to achieve the effect of high temperature resistance and strong acid corrosion resistance, improving corrosion resistance and improving use stability

Active Publication Date: 2020-07-07
SHANGHAI INST OF ORGANIC CHEM CHINESE ACAD OF SCI
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

Thermal cracking was first proposed, that is, direct cracking of empty tubes. However, due to the relatively stable fluoroform, the cracking temperature of empty tubes is high. Generally, a high temperature above 850°C is required to achieve cracking of fluoroform, and the cracking efficiency is low; not only that, thermal cracking High energy consumption, easy to produce strong carcinogens at high temperature, perfluoroisobutylene
In 2001, William R.Dolbier, Jr. [J.Am.Chem.Soc.2001, 123, 6767-6772] of the University of Florida explored empty tube pyrolysis, and the conversion rate was only 10% at 800 °C, and the by-product More, less target product, this method cannot be applied industrially
Catalytic cracking can be expected to reduce reaction temperature, improve conversion rate and productive rate, but can realize the catalyzer of fluoroform catalytic conversion, only in 2010, Australia Eric M.Kennedy reported activated carbon supported potassium catalyst [Journal of FluorineChemistry 131 (2010) 698 –703] Catalytic cracking of fluoroform can be realized, and a conversion rate of about 30% can be realized at 800 °C, but the space velocity used is low, the selectivity is poor, and the target product is few, and it is still difficult to realize industrial application
In view of the lack of effective catalysts for fluoroform cracking, this patent has invented a high-efficiency fluoroform cracking catalyst through catalyst design, preparation, screening and optimization, which can significantly reduce the catalytic cracking temperature to an industrially usable temperature (below 600°C) And the conversion rate is high, the selectivity is high, and the yield of high value-added products tetrafluoroethylene and hexafluoropropylene is high

Method used

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  • Application of a Supported Catalyst in Trifluoromethane Cracking
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  • Application of a Supported Catalyst in Trifluoromethane Cracking

Examples

Experimental program
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Effect test

Embodiment 1

[0027] Manganese chloride is used as the precursor, and the manganese catalyst supported on activated carbon is prepared by acid treatment:

[0028] The activated carbon is treated with 30% nitric acid by mass concentration at 90°C for 5h, filtered and washed with water to neutrality, and the filter cake is baked at 120°C for 12h to obtain acid-treated activated carbon;

[0029] Impregnation method or immersion fluorination method: Put 9.82g of manganese chloride into 10mL of deionized water, heat and stir to dissolve evenly, add 10g of acid-treated activated carbon carrier, stir well, stand for 12h, then dry at 80℃ for 12h, put Put it into a quartz boat, roast with 100mL / min nitrogen at 500℃ for 4h to obtain activated carbon-supported manganese solid, then soak the solid with a mass concentration of 10% HF aqueous solution for 1h, filter, wash with water, and dry at 80℃ to obtain activated carbon-supported fluoride Manganese catalyst, the manganese mass loading is 30%.

[0030] Pre...

Embodiment 2

[0035] The catalyst obtained in Example 1 was used to test the catalytic activity of trifluoromethane cracking at different temperatures: 3g of the acid-treated activated carbon-supported manganese catalyst obtained in Example 1 was filled into the reaction tube, and trifluoromethane was introduced at a flow rate of 50 mL / min. Then the reaction tube is heated from 300°C to 900°C by program, and after every 50°C temperature rise, the temperature is kept constant for half an hour, and then sampled by gas chromatography for analysis. According to the change of the peak area of ​​trifluoromethane before and after the reaction, the conversion rate from 300°C to 900°C was calculated; the selectivity was obtained by comparing the peak area of ​​tetrafluoroethylene and hexafluoropropylene standard products. The result is shown in the figure.

Embodiment 3

[0037] The catalyst obtained in Example 1 was used to test the catalytic activity of trifluoromethane cracking at different space velocities: 3 mL of the acid-treated activated carbon-supported manganese catalyst obtained in Example 1 was filled into the reaction tube, and trifluoromethane was introduced, the flow rate was adjusted, and the space velocity was controlled. It is 100 / h-9000 / h, and then the temperature of the reaction tube is raised to 600°C for half an hour, and then sampled by gas chromatography for analysis. According to the changes in the peak area of ​​trifluoromethane before and after the reaction, the conversion rate at different space velocities was calculated; the selectivity was obtained by comparing the peak areas of tetrafluoroethylene and hexafluoropropylene standard products. The result is shown in the figure.

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PUM

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Abstract

The invention relates to a catalyst used in cracking of trifluoromethane and preparation thereof. The catalyst is characterized by adopting zirconium oxide, magnesium oxide, activated carbon, acid treated activated carbon, alumina and the like as carriers, auxiliaries contain alkali metals K, Na and Cs, carrying capability of active components is 1-50% (mass percent), and molar content of metal auxiliaries is not higher than 50% of the total molar content of the active components and the metal auxiliaries. The catalyst provided by the invention has the characteristics that trifluoromethane catalytic cracking reaction temperature is low and is lower than 600 DEG C, catalyst dosage is low, conversion rate and yield are high, selectivity is high, high temperature resistance and strong acid resistance are good and high value-added products can be obtained; the catalyst is not only effectively improved in thermal stability resistant to high temperature agglomeration but also effectively improved in corrosion resistance through fluorination treatment, so that use stability of the catalyst is improved; and raw materials are available, technology is simple, and industrialization application can be realized.

Description

Technical field [0001] The invention relates to a catalyst for the cracking of trifluoromethane in the field of fluorine chemicals and a preparation method thereof, in particular to the application of a supported catalyst in cracking of trifluoromethane. Background technique [0002] Trifluoromethane is abbreviated as fluoroform, which is a very strong greenhouse gas (GWP value is about 14800, equivalent to CO 2 14800 times) and has a longer lifespan in the atmosphere. It is currently known as the second-highest greenhouse gas with greenhouse effect. Fluoroform has been listed as a restricted emission gas in the Kyoto Agreement. In the process of producing R22 by fluorine chemical enterprises, the annual production of fluoroform as the main by-product reaches more than 10,000 tons. Judging from the figure of 3 billion tons of China's carbon emissions trading, fluoroform emissions account for about 1% of China's carbon emissions, and it is an industrial waste that seriously pollu...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): B01J23/04B01J23/06B01J23/34B01J23/44B01J23/46B01J23/50B01J23/58B01J23/656B01J23/66C07C17/269C07C21/185C07C21/18
Inventor 杨军刘爽汪绘枢
Owner SHANGHAI INST OF ORGANIC CHEM CHINESE ACAD OF SCI
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