Application of supported catalyst in cracking of trifluoromethane

A supported catalyst, trifluoromethane technology, applied in physical/chemical process catalysts, metal/metal oxide/metal hydroxide catalysts, organic chemistry, etc., can solve high conversion rate, low cracking efficiency, and many by-products and other problems, to achieve the effects of high temperature resistance, strong acid corrosion resistance, improved use stability, high conversion rate and high yield

Active Publication Date: 2018-01-26
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 supported catalyst in cracking of trifluoromethane
  • Application of supported catalyst in cracking of trifluoromethane
  • Application of supported catalyst in cracking of trifluoromethane

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0027] Manganese chloride was used as a precursor, and acid-treated activated carbon supported manganese catalyst was prepared:

[0028] Activated carbon was treated with nitric acid with a mass concentration of 30% at 90°C for 5 hours, filtered, washed with water to neutrality, and the filter cake was baked at 120°C for 12 hours to obtain acid-treated activated carbon;

[0029] Impregnation method or impregnation 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 evenly, let stand for 12h, then dry at 80°C for 12h, put into a quartz boat, 100mL / min nitrogen, roasted at 500°C for 4 hours to obtain activated carbon-loaded manganese solids, and then soak the solids in 10% HF aqueous solution for 1 hour, filter, wash with water, and dry at 80°C to obtain activated carbon-loaded manganese solids. Manganese catalyst, manganese mass loading is 30%.

[0030]Precip...

Embodiment 2

[0035] The trifluoromethane cracking catalytic activity under the catalyst test different temperature that adopts embodiment 1 to obtain: the 3g acid treatment activated carbon supported manganese catalyst that embodiment 1 obtains is packed into reaction tube, feeds trifluoromethane, and flow rate is 50mL / min, Then, the temperature of the reaction tube was raised from 300° C. to 900° C., and the temperature was kept constant for half an hour every time the temperature was increased by 50° C., and then analyzed by gas chromatography sampling. According to the change of trifluoromethane peak area before and after the reaction, the conversion rate from 300°C to 900°C was calculated; the selectivity was obtained by comparing the peak areas of tetrafluoroethylene and hexafluoropropylene standard products. The results are shown in Fig.

Embodiment 3

[0037] Using the catalyst obtained in Example 1 to test the trifluoromethane cracking catalytic activity under different space velocities: the 3mL acid-treated activated carbon-loaded manganese catalyst obtained in Example 1 is packed into the reaction tube, feeds trifluoromethane, adjusts the flow rate, and controls the space velocity The temperature is 100 / h-9000 / h, and then the temperature of the reaction tube is raised to 600°C for half an hour, and then analyzed by gas chromatography sampling. According to the change of trifluoromethane peak area 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 results are shown in Fig.

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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 trifluoromethane cracking in the field of fluorine chemical industry and a preparation method thereof, in particular to the application of a supported catalyst in trifluoromethane cracking. Background technique [0002] Trifluoromethane, referred to as fluoroform, is a very strong greenhouse gas (GWP value is about 14800, equivalent to CO 2 14,800 times of that) and has a long lifespan in the atmosphere, and is currently known as the greenhouse gas with the second highest greenhouse effect. Fluoroform has been listed as a restricted emission gas in the Kyoto Protocol. In the production of R22 in 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 a serious industrial waste that pollutes...

Claims

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Application Information

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Patent Type & Authority Applications(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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