Method for preparing fluorine-containing olefin by selective dehydrohalogenation with halogenated hydrocarbon

A technology for dehydrohalogenation and fluorine-containing olefins, which is applied in the fields of dehydrohalogenation preparation, chemical instruments and methods, metal/metal oxide/metal hydroxide catalysts, etc. There are many by-products in the process, and the effect of high dehydrohalogenation selectivity and high conversion rate

Active Publication Date: 2012-12-26
山东华安近代环保科技有限公司
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  • Abstract
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  • Application Information

AI Technical Summary

Problems solved by technology

The gas phase method has many by-products and short catalyst life, which limits the preparation of fluorine-containing olefins as an industrial production method

Method used

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  • Method for preparing fluorine-containing olefin by selective dehydrohalogenation with halogenated hydrocarbon
  • Method for preparing fluorine-containing olefin by selective dehydrohalogenation with halogenated hydrocarbon
  • Method for preparing fluorine-containing olefin by selective dehydrohalogenation with halogenated hydrocarbon

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Experimental program
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preparation example Construction

[0023] 1. Preparation of composite catalyst

[0024] The composite catalyst is prepared by the co-precipitation-impregnation method. The sulfate, nitrate or chloride salt of alkaline earth metal is dissolved in water, and then the precipitant ammonia water, sodium hydroxide or sodium carbonate aqueous solution is added dropwise to the above solution, and the slurry is filtered out After drying, the doping ion solution is impregnated in the catalyst matrix, and then dried and calcined to obtain a composite catalyst for dehydrohalogenation.

[0025] For example: 11.0g magnesium chloride (MgCl 2 ), 24.0g barium nitrate (Ba(NO 3 ) 2 ) was dissolved in 200ml distilled water to make a solution, and then 5mol / l sodium carbonate (Na 2 CO 3 ) aqueous solution was added dropwise to the above solution to pH = 11, the slurry was filtered out, dried overnight at 150°C, and then the solid was immersed in 50ml of KCl aqueous solution for 5 hours, and evaporated to dryness on a rotary eva...

Embodiment 1

[0027] A series of composite alkaline earth metal oxides were used as dehydrohalogenation catalysts. In a typical test, 60ml of composite catalyst (BaO / MgO) is loaded into a fixed-bed tubular reactor with a diameter of Φ38mm, and at a reaction temperature ranging from 200°C to 850°C, 90wt.% of 2- A mixture of chloro-1,1,1,2-tetrafluoropropane (HCFC-244bb), 5wt.% of 2-chloro-3,3,3-trifluoropropene and 5wt.% of HF was passed through the catalyst bed. The reaction product was washed with water and alkali to remove HCl and HF, and then analyzed by gas chromatography. The analysis method was the area normalization method. The reaction results are shown in Table 1.

[0028] Table 1

[0029]

Embodiment 2

[0031] The same operating conditions as in Example 1, the difference is that the reaction raw material 2-chloro-1,1,1,2-tetrafluoropropane is replaced by 2,3-dichloro-1,1,1-trifluoropropane ( HCFC-243db), the reaction results are shown in Table 2.

[0032] Table 2

[0033]

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Abstract

The invention discloses a method for preparing fluorine-containing olefin by selective dehydrohalogenation with halogenated hydrocarbon. Halogenated fluorocarbon containing three or more carbon atoms of which at least one hydrogen atom and at least one halogen atom are on the adjacent carbon atoms is used as a raw material. In the presence of a catalyst, a fluorine-containing olefin product is obtained through high temperature gas phase dehydrohalogenation reaction, wherein the reaction temperature is between 150 DEG C and 850 DEG C, the reaction pressure is 0-10atm of absolute pressure, and the contacting time of the reacting raw material and the compound catalyst is 0.3s-14s. The method for preparing fluorine-containing olefin by selective dehydrohalogenation which enables halogenated fluorocarbon to be highly selected has the advantages of high activity of compound catalyst, good stability, less by-product, and being capable of avoiding the complex product separation process and realizing higher economic production of fluorine-containing olefin.

Description

technical field [0001] The present invention relates to the preparation method of compound, more specifically, relate to a kind of method of selective dehydrohalogenation of halogenated hydrocarbon to prepare fluorine-containing olefin, this method uses at least one hydrogen atom and at least one halogen atom on the adjacent carbon atom Halofluoroalkanes containing three or more carbon atoms are used as raw materials, and in the presence of composite catalysts, undergo high-temperature gas-phase dehydrohalogenation to form fluorine-containing olefin products. Background technique [0002] Hydrofluorocarbons (HFCs) have been widely used as refrigerants, blowing agents, cleaning agents, organic solvents and heat transfer media. Although HFCs do not contain chlorine and do not damage the ozone layer, most HFCs have high global warming potential (GWP), which can cause global warming and have been listed as greenhouse gases by the Kyoto Protocol. For the above reasons, there is ...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07C17/25C07C21/18B01J23/04B01J23/78B01J23/02B01J23/10
Inventor 吕剑毛伟
Owner 山东华安近代环保科技有限公司
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