Preparation method of 1,3,3,3-tetrafluoropropene

A technology of tetrafluoropropene and tetrafluoropropane, which is applied in the field of preparation of hydrofluoroolefins, can solve the problems of harsh reaction conditions, expensive raw materials, and expensive prices, and achieve the effects of mild reaction conditions, cheap and easy-to-obtain raw materials, and easy operation

Active Publication Date: 2016-07-13
XIAN MODERN CHEM RES INST
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  • Claims
  • Application Information

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Problems solved by technology

[0004] Fluorine-chlorine exchange method is the most, Japanese patent JP10007604, US patent US6472573, European patent EP486333 reported that 1-chloro-3,3,3-trifluoropropene (HCFC-1233zd) was used as raw material to synthesize HCFC-1233zd by one-step gas phase fluorination The method of HFO-1234ze, but the reaction raw material HCFC-1233zd in the method is expensive and difficult to obtain, and the catalyst used is a chromium-containing catalyst. These chromium-containing compounds and catalysts will cause damage to the human digestive tract and kidneys, especially high-priced chromium It has a strong carcinogenic effect, is unfriendly to people and the environment during production and use, and will cause serious harm; Chinese patent CN200810000765. -240fa) as a raw material, the method for preparing HFO-1234ze by gas-phase fluorination, but the selectivity of HFO-1234ze is poor in the method, only about 50%; -1243) is the method for synthesizing HFO-1234ze as a raw material, but the raw material of this synthetic method is expensive, the route is complicated, and the addition reaction process is difficult to control
[0005] For the dehydrohalogenation method, U.S. Patent US7592494, European Patent EP2014637, European Patent EP0974571, Chinese Patent CN101265155, Chinese Patent CN101466656 and Japanese Patent JP10007605 have reported the use of 1,1,1,3,3-pentafluor

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  • Preparation method of 1,3,3,3-tetrafluoropropene

Examples

Experimental program
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Example Embodiment

[0027] Example 1:

[0028] Add trichloropropene (20.0g, 0.15mol) and 120mL chloroform to the 250mL dry three-necked flask equipped with magnetic stirring, thermometer and condenser. Under constant stirring, add anhydrous aluminum trichloride ( 2.0g, 0.015mol), and then gradually heated to 60℃, reacted for 12h, the reaction liquid was cooled to about 30℃, filtered, and the filtrate was distilled under reduced pressure. The vacuum degree was 5kPa, and the fraction at 120~125℃ was collected. 1,1,1,2,3,3-hexachloropropane (HCC-230da), the conversion rate is 85.7%, and the selectivity is 90.4%.

Example Embodiment

[0029] Example 2:

[0030] Preparation of the catalyst: a certain proportion of Zn(NO 3 ) 2 ·6H 2 O, FeCl 3 , La(NO 3 ) 3 ·6H 2 O was mixed into a 2mol / L aqueous solution, and 15% by mass ammonia was added dropwise under constant stirring at 20°C-40°C, adjusted to pH 8.0, reacted for 8h, filtered, and dried at 120°C for 2h , Then mix a certain amount of magnesia with it uniformly, and then roast at 200℃ for 1h, 5℃ / min to 320℃, roast for 2h, then 10℃ / min to 450℃, roast for 4h, and finally heat it with hydrogen fluoride at 200 The Zn-Fe-La-Mg composite catalyst was obtained by activation treatment at ℃-380℃ for about 36h.

[0031] A fixed-bed tubular reactor with an inner diameter of 38 mm was filled with 50 ml of Zn-Fe-La-Mg composite catalyst, where the molar ratio of Zn, Fe, La, and Mg was 0.5:2:0.5:7, and the catalyst Dry, and then at 250 ℃, HF and CCl 3 CHClCHCl 2 (HCC-230da, abbreviated as 230da) into the first reactor R1, control the molar ratio of the two to 10:1, the contac...

Example

[0032] Examples 3 to 5:

[0033] Examples 3 to 5 prepared HCFC-234da according to the same method in Example 2, except that the reaction temperatures of R1 and R2 in Example 2 were 250°C and 300°C, respectively, while in Examples 3 to 5, R1, The reaction temperature and reaction results of R2 and R3 are shown in Table 1.

[0034] Table 1

[0035]

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PUM

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Abstract

The invention discloses a preparation method of 1,3,3,3-tetrafluoropropene; the preparation method includes the steps: a, in the presence of a composite catalyst, carrying out a gas phase fluorination reaction of a compound represented by the general formula of CF3-xClxCHClCHF2-yCly with hydrogen fluoride through two series-connection reactors with different reaction temperatures to generate 2,3-dichloro-1,1,1,3-tetrafluoropropane, wherein in the compound general formula, x=0, 1, 2 or 3, y=1 or 2, and 2<=(x+y)<=5; and b, in the presence of a dechloridation catalyst, carrying out a gas phase dechloridation reaction of 2,3-dichloro-1,1,1,3-tetrafluoropropane with hydrogen gas to generate 1,3,3,3-tetrafluoropropene. The preparation method is mainly used for preparation of 1,3,3,3-tetrafluoropropene.

Description

technical field [0001] The invention relates to a method for preparing hydrofluoroolefins, in particular to a method for preparing 1,3,3,3-tetrafluoropropene (HFO-1234ze). Background technique [0002] Compared with chlorofluorocarbons (CFCs), hydrochlorofluorocarbons (HCFCs), and hydrofluorocarbons (HFCs), hydrofluoroolefins (HFOs) do not contain chlorine, do not pose a threat to the earth's ozone layer, and have low greenhouse effect potential. At present, it has become the focus of industrial research on fluorocarbons. 1,3,3,3-Tetrafluoropropene, namely HFO-1234ze, as a kind of hydrofluoroolefin, has an ozone depletion potential of 0 and a greenhouse effect potential of 6, and can be used as a refrigerant, blowing agent, gas Sol propellants, fire extinguishing agents, heat transfer media, propellants, gaseous dielectrics, sterilizing agent carriers, polymer monomers, and pharmaceutical and pesticide intermediates are widely used in the fields of chemical industry, fire p...

Claims

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Application Information

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IPC IPC(8): C07C21/18C07C17/23B01J27/06B01J23/83
Inventor 吕剑秦越王博白彦波张振华马辉毛伟杨志强曾纪珺李凤仙
Owner XIAN MODERN CHEM RES INST
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