CN113527040A - Preparation method of halogenated propylene - Google Patents

Preparation method of halogenated propylene Download PDF

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CN113527040A
CN113527040A CN202010320787.5A CN202010320787A CN113527040A CN 113527040 A CN113527040 A CN 113527040A CN 202010320787 A CN202010320787 A CN 202010320787A CN 113527040 A CN113527040 A CN 113527040A
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halogenopropene
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CN113527040B (en
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刘敏洋
于万金
林胜达
刘武灿
张建君
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Zhejiang Chemical Industry Research Institute Co Ltd
Sinochem Lantian Co Ltd
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Sinochem Lantian Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C17/00—Preparation of halogenated hydrocarbons
    • C07C17/25—Preparation of halogenated hydrocarbons by splitting-off hydrogen halides from halogenated hydrocarbons
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/06—Halogens; Compounds thereof
    • B01J27/125—Halogens; Compounds thereof with scandium, yttrium, aluminium, gallium, indium or thallium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/06—Halogens; Compounds thereof
    • B01J27/135—Halogens; Compounds thereof with titanium, zirconium, hafnium, germanium, tin or lead
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/0231—Halogen-containing compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/19—Catalysts containing parts with different compositions
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C17/00—Preparation of halogenated hydrocarbons
    • C07C17/26—Preparation of halogenated hydrocarbons by reactions involving an increase in the number of carbon atoms in the skeleton
    • C07C17/272—Preparation of halogenated hydrocarbons by reactions involving an increase in the number of carbon atoms in the skeleton by addition reactions
    • C07C17/278—Preparation of halogenated hydrocarbons by reactions involving an increase in the number of carbon atoms in the skeleton by addition reactions of only halogenated hydrocarbons

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Abstract

A method for preparing a halopropene, comprising: the halopropene shown in the structural formula III is prepared by dehydrochlorination of the chlorofluoropropane shown in the structural formula II under the action of a metal base catalyst and a phase transfer catalyst, and the reaction formula is as follows:

Description

Preparation method of halogenated propylene
Technical Field
The invention relates to preparation of halogenated propylene, in particular to a method for preparing 2,3,3, 3-tetrafluoropropene or chloro-2, 3,3, 3-tetrafluoropropene by dehydrochlorination of telomeric products of chlorofluoromethane and trifluoroethylene.
Background
2,3,3, 3-tetrafluoropropene (HFO-1234yf), 1-chloro-2, 3,3, 3-tetrafluoropropene (HCFO-1224yd) and 1, 1-dichloro-2, 3,3, 3-tetrafluoropropene (CFO-1214ya) are 3 common halopropenes, especially HFO-1234yf and HCFO-1224yd, which have potential applications to replace existing refrigerants due to their excellent environmental properties, while CFO-1214ya is a raw material for synthesizing HFO-1234yf and HCFO-1224yd, and also has high research value.
2,3,3, 3-tetrafluoropropene has zero ODP, 4 GWP, life-time climate performance (LCCP) lower than that of the traditional refrigerant HFC-134a, system refrigeration performance better than HFC-134a, and atmospheric decomposition products same as HFC-134a, so the refrigerant is considered as the most potential automobile refrigerant substitute at present and is accepted by a plurality of mainstream automobile manufacturers. The Asahi glass-de-Nitro patent WO2011162341A discloses a method for preparing 2,3,3, 3-tetrafluoropropene by using 1, 1-dichloro-2, 3,3, 3-tetrafluoropropene (CFO-1214ya) as a raw material and performing hydrogenation reduction under the action of a palladium catalyst. However, the degree of hydrogenation reduction reaction is difficult to control, intermediates or over-reduction products such as 1-chloro-2, 3,3, 3-tetrafluoropropene (HCFO-1224yd), 1-chloro-2, 3,3, 3-tetrafluoropropane (HCFC-244eb) and 2,3,3, 3-tetrafluoropropane (HFC-254eb) are easy to generate, the product selectivity is low, the post-treatment operation is complicated, the byproduct HFC-254eb is easy to generate further dehydrofluorination reaction in the alkali washing treatment process to generate 3,3, 3-trifluoropropene (HFO-1243zf) with the boiling point close to that of HFO-1234yf, and the impurity separation difficulty is further increased. Although the problems can be improved by controlling the reaction temperature of the catalyst bed and the alkali washing absorption temperature, the improvement degree is not obvious, and the control difficulty of the process conditions is large, so that the method is not suitable for industrial amplification.
1-chloro-2, 3,3, 3-tetrafluoropropene (HCFO-1224yd) has an ODP of zero, a GWP of less than 1, good chemical stability and excellent refrigeration performance, and can be used for air conditioning,Refrigerators and the like. Asahi glass Pat. No. WO2017146189A also discloses a method for preparing HCFO-1224yd by CFO-1214ya hydrogenation reduction, which can inhibit the formation of by-products (HFO-1234yf, HFC-254eb and other over-reduction products) by changing the formula of the catalyst, reducing the amount of hydrogen and controlling the temperature of the catalyst bed, thereby obtaining the target product HCFO-1224yd with high selectivity. Specifically, the molar ratio (H) of hydrogen to CFO-1214ya is set21214ya) below 1.4, and even below 1.0, but considering the yield of product 1224yd, H2The/1214 ya needs to be higher than 0.4; controlling the temperature of a catalyst bed layer below 130 ℃; the specific surface area is less than 40m2The palladium catalyst (loaded on the surface of active carbon) shows better catalytic activity, stability and product selectivity. The reaction is industrially easy to carry out and can be stably produced, but the selectivity of the main product HCFO-1224yd is less than 20%. The Asahi nitroxide patent WO2018030408A discloses that the catalytic activity, stability and product selectivity are promoted by adding appropriate amounts of chloride ions to the palladium catalyst during the CFO-1214ya hydrogenation reduction process, but the HCFO-1224yd selectivity is still below 30%.
The method for preparing the halogenated propylene by hydrogenation reduction generally has the problem of low product selectivity, and a plurality of fluorine-containing byproducts such as 1-chloro-1, 2,2,3,3, 3-hexafluoropropane, 1-chloro-1, 1,2,2,3, 3-hexafluoropropane, 1-chloro-1, 3,3, 3-tetrafluoropropene, 2-chloro-1, 3,3, 3-tetrafluoropropene and the like exist in reaction products, so that the impurities are difficult to effectively remove by adopting common rectification due to similar properties of the fluorine-containing byproducts, and the difficulty in post-treatment is increased.
Japanese patent JP3778298A discloses a process for producing CFO-1214ya by dehydrofluorination using 1, 1-dichloro-2, 2,3,3, 3-pentafluoropropane (HCFC-225ca) as a raw material under the action of an alkali catalyst. However, HCFC-225ca used as a raw material in this production method is produced by telomerization of tetrafluoroethylene and monofluorodichloromethane, and usually contains a large amount of the isomer 1, 3-dichloro-1, 2,2,3, 3-pentafluoropropane (HCFC-225cb) and is separated and purified to be used as a raw material for the above reaction. However, HCFC-225ca and HCFC-225cb have similar boiling points, are difficult to purify by common rectification, and can obtain high-purity HCFC-225ca for reaction by means of multi-stage rectification and the like, and the separation difficulty is large.
Disclosure of Invention
In order to solve the technical problems, the invention provides a preparation method of halogenated propylene, which has the advantages of simple process, mild reaction conditions and high product selectivity.
The purpose of the invention is realized by the following technical scheme:
the invention provides a preparation method of halogenated propylene, wherein the preparation method of the halogenated propylene adopts chlorofluoropropane shown in the following structural formula II as a raw material, and the halogenated propylene shown in the structural formula III is prepared by dehydrochlorination reaction under the action of a metal base catalyst and a phase transfer catalyst, and the reaction formula is as follows:
Figure BDA0002461294930000031
compared with other structural formulas of the chlorofluoromethane, such as 1, 2-dichloro-2, 3,3, 3-tetrafluoropropane, the chlorofluoromethane with the structure of the invention can be prepared by liquid phase telomerization reaction, and the liquid phase telomerization product has high selectivity, does not have byproducts with boiling points close to those of difficult separation, and can obtain a high-purity target product only by simple rectification.
The invention also provides a preparation method of the halogenated propylene, wherein the preparation method of the halogenated propylene adopts the chlorofluoromethane as a raw material, and comprises the following steps:
a telomerization process: carrying out telomerization on raw materials of chlorofluoromethane shown in a structural formula I and trifluoroethylene under the action of a liquid-phase catalyst to prepare chlorofluoropropane shown in a structural formula II; the liquid phase catalyst comprises a first catalyst and a second catalyst, wherein the first catalyst is a Lewis acid catalyst, and the second catalyst is CHxFy-1Clz+1(ii) a Wherein y is more than or equal to 1, z is more than or equal to 1, and x + y + z is 4;
dehydrochlorination step: the chloropropane is subjected to dehydrochlorination reaction under the action of a metal base catalyst and a phase transfer catalyst to prepare the halopropene shown in the structural formula III;
the reaction formula is as follows:
Figure BDA0002461294930000041
in the telomerization step:
the first catalyst is at least one halide selected from Al, Sb, Ti, Zr and Hf. Preferably, the first catalyst is selected from ZrCl4、HfCl4、TiCl4、AlF3、SbF5At least one of them. More preferably, the first catalyst is ZrCl4Or HfCl4。
The second catalyst is selected from at least one of chloroform, trifluoromethane, dichloromethane, tetrafluoromethane and carbon tetrachloride, and is selected according to the raw material of the fluorochloromethane.
In the dehydrochlorination step:
the metal base catalyst is selected from at least one of metal hydroxide, metal carbonate or metal bicarbonate. Preferably, the metal base catalyst is potassium hydroxide. Further, the concentration of the metal base catalyst is 5-60 wt%; preferably, the concentration of the metal base catalyst is 10-40 wt%.
The phase transfer catalyst is quaternary ammonium salt. Preferably, the phase transfer catalyst is at least one selected from tetrabutylammonium bromide, tetramethylammonium hydroxide and tetramethylammonium chloride. Further preferably, the phase transfer catalyst is tetramethylammonium hydroxide.
In chemical reactions, the ratio of raw materials to catalyst, reaction temperature, reaction time, etc. all affect the reaction result, and especially the combination of multiple variables can greatly affect the reaction result.
In the telomerization process for preparing the halogenated propylene, the molar ratio of the raw materials of the chlorofluoromethane to the trifluoroethylene is 1: 0.1-1: 10; more preferably, the molar ratio of the raw material of the fluorochloromethane to the trifluoroethylene is 1:1 to 1:5. The dosage of the first catalyst is 0.01-50 wt% of the mass of the raw material of the chlorofluoromethane; more preferably, the amount of the first catalyst is 0.1-10 wt% of the mass of the raw material of the fluorochloromethane. The molar ratio of the second catalyst to the raw material of the chlorofluoromethane is 1: 0.01-1: 10; more preferably, the molar ratio of the second catalyst to the raw material of the fluorochloromethane is 1: 0.1-1: 5.
The liquid phase telomerization process is carried out at the temperature of-30-100 ℃ and the pressure of 0.5-2.0 MPa, and the reaction time is 1-50 h. More preferably, the reaction temperature is 0 to 50 ℃, the pressure is 0.8 to 1.5MPa, and the reaction time is 5 to 10 hours.
In the dehydrochlorination process for preparing the halogenated propylene, the molar ratio of the chlorofluoropropane to the metal base catalyst is as follows: 1: 0.1-1: 5.0, and the reaction temperature is 10-100 ℃. Preferably, the molar ratio of the chlorofluoropropane to the metal base catalyst is as follows: 1: 1.0-1: 2.0, and the reaction temperature is 30-60 ℃.
The invention adopts the first catalyst and the second catalyst to carry out liquid phase telomerization reaction under the catalysis of the first catalyst and the second catalyst, and the first catalyst and the second catalyst supplement each other and are not enough. First catalyst dissociation activation raw material fluorochloromethane CHxFyClzForm F-、CHxFy-1Clz +、Cl-、CHxFyClz-1 +Plasma; the second catalyst inhibits F formed by dissociation-、CHxFy-1Clz +、Cl-、CHxFyClz-1 +Plasma recombination, thereby ensuring F-And CHxFy-1Clz +Ions and trifluoroethylene generate directional telomerization reaction, and telomerization product CF is obtained with high selectivity3CHFCHxFy-1Clz。
Meanwhile, the raw material of the chlorofluoromethane, the second catalyst, the telomerization product and the target product of the halogenated propylene have one-to-one correspondence, and the raw material of the chlorofluoromethane CHxFyClzA second catalyst CHxFy-1Clz+1Telomeric product CF3CHFCHxFy-1ClzAnd the target halopropene CF3CF＝CHxFy-1Clz-1Structural watch ofThe expression can be known. If the raw material is monofluoro dichloromethane, the second catalyst is trichloromethane, the corresponding telomerization product is 3, 3-dichloro-1, 1,1, 2-tetrafluoropropane, and the target product is 1-chloro-2, 3,3, 3-tetrafluoropropene. When the raw material is monochloromethane fluoride, the second catalyst is dichloromethane, the corresponding telomerization product is 3-chloro-1, 1,1, 2-tetrafluoropropane, and the target product is 2,3,3, 3-tetrafluoropropene. When the raw material is trichlorofluoromethane, the second catalyst is carbon tetrachloride, the corresponding telomerization product is 3,3, 3-trichloro-1, 1,1, 2-tetrafluoropropane, and the target product is 1, 1-dichloro-2, 3,3, 3-tetrafluoropropene.
The preparation method of the halogenated propylene specifically comprises the following steps:
A1. carrying out liquid phase telomerization reaction on raw materials of the chlorofluoromethane and trifluoroethylene in a first reaction kettle under the combined action of a first catalyst and a second catalyst; specifically, adding a first catalyst and a second catalyst into a first reaction kettle for mixing, introducing nitrogen to replace air in the kettle, and then adding raw materials of chlorofluoromethane and trifluoroethylene for reaction;
A2. after the reaction is finished, collecting unreacted gas-phase raw materials of trifluoroethylene and/or chlorofluoromethane, a small amount of entrained products and a second catalyst;
A3. carrying out solid-liquid separation treatment such as filtration, rectification or flash evaporation on the materials in the reaction kettle, wherein the solid part is the first catalyst, and the liquid part is further rectified and separated to obtain a second catalyst and a telomerization product;
the unreacted gas-phase raw material and the first and second catalysts can be returned to the step A1 for reuse;
A4. adding the telomerization product, a metal base catalyst and a phase transfer catalyst into a second reaction kettle, and introducing nitrogen to replace air in the kettle;
A5. setting the dehydrochlorination reaction temperature to start reaction;
A6. and after the reaction is finished, carrying out liquid separation and rectification treatment on the reaction product to obtain a target product.
Compared with the prior art, the invention has the beneficial effects that:
the invention provides a method for preparing a Lewis acid and CHxFy-1Clz+1The method for obtaining telomeric product fluoropropylene by jointly catalyzing the reaction of the fluorochloromethane and the trifluoroethylene and obtaining the corresponding halogenated propylene after dehydrochlorination treatment of the fluorochloropropane has the advantages of easily obtained raw materials, simple process, mild reaction conditions, high selectivity of the telomeric product and the target product, suitability for industrial amplification and the like.
Detailed Description
The present invention is further illustrated by the following examples, which are not intended to limit the invention to these embodiments. It will be appreciated by those skilled in the art that the present invention encompasses all alternatives, modifications and equivalents as may be included within the scope of the claims.
Example 1
This example presents a process for the preparation of 1-chloro-2, 3,3, 3-tetrafluoropropene (HCFO-1224yd) comprising a telomerization step and a dehydrochlorination step, in particular:
a telomerization process:
A1. an autoclave made of Inconel alloy with the volume of 250mL is used as a reactor, and 3.0g of first catalyst ZrCl is added4Respectively adding 20.0g of second catalyst trichloromethane into the reaction kettle, sealing the reaction kettle, introducing 1.0MPa of nitrogen to replace the air in the reaction kettle, and repeating the steps for three times;
A2. after the air in the reaction kettle is completely replaced, 29.87g (0.29mol) of monofluoro dichloromethane and 23.78g (0.29mol) of trifluoroethylene are introduced in sequence;
A3. setting the reaction temperature to be 30 ℃, the stirring speed to be 300rpm, the initial reaction pressure to be 0.9MPa, gradually reducing the pressure along with the reaction, and the reaction time to be 10 h;
A4. after the reaction is finished, collecting unreacted gas-phase raw materials of trifluoroethylene and/or chlorofluoromethane, a small amount of entrained products and a second catalyst; carrying out solid-liquid separation treatment such as filtration, rectification or flash evaporation on the materials in the reaction kettle, wherein the solid part is the first catalyst, and the liquid part is further rectified and separated to obtain a second catalyst and a telomerization product;
the unreacted gas-phase raw material and the first and second catalysts can be returned to the step A1 for reuse.
The telomeric product was analyzed by gas chromatography, which revealed that: the conversion of monofluorodichloromethane was 85.0%, the selectivity for 3, 3-dichloro-1, 1,1, 2-tetrafluoropropane was 72.9%, the by-products included 1, 3-dichloro-1, 2,2, 3-tetrafluoropropane and 1, 3-dichloro-1, 2,3, 3-tetrafluoropropane, the selectivities were 14.8% and 11.1%, respectively, and a small amount of other by-products.
Dehydrochlorination step:
B1. an Inconel alloy high-pressure autoclave with the volume of 250mL is adopted as a reactor, 20g of telomerization product, 40g of 25 wt% KOH solution and 1g of tetramethylammonium hydroxide are respectively added into a reaction kettle, the reaction kettle is sealed, 1.0MPa nitrogen is introduced to replace the air in the reaction kettle, and the steps are repeated for three times;
B2. setting the reaction temperature to be 50 ℃, the stirring speed to be 300rpm and the reaction time to be 5 hours after the air in the reaction kettle is completely replaced;
B3. after the reaction is finished, the reaction product is subjected to liquid separation and rectification treatment to obtain the target product 1-chloro-2, 3,3, 3-tetrafluoropropene.
The reaction product was analyzed by gas chromatography, and it was found that: the conversion of 3, 3-dichloro-1, 1,1, 2-tetrafluoropropane (HCFC-234ea) was 90.8% and the selectivity to HCFO-1224yd, the main product, was 91.2%.
Example 2
This example presents a process for the preparation of 2,3,3, 3-tetrafluoropropene (HFO-1234yf) comprising a telomerization step and a dehydrochlorination step, the telomerization step being as described in example 1, differing from example 1 by: the first catalyst adopts HfCl4The amount of addition was 3.0g, methylene chloride was used as the second catalyst in an amount of 20.0g, and 19.87g (0.29mol) of monochloromethane as the raw material fluorochloromethane was used as the raw material, while the amount of addition was 24.6g (0.30mol) of trifluoroethylene as the raw material, the reaction temperature was 10 ℃ and the other conditions were kept constant.
The telomeric product was analyzed by gas chromatography, which revealed that: the conversion of monochloromethane monofluoride was 76.5%, the selectivity for 3-chloro-1, 1,1, 2-tetrafluoropropane was 81.2%, the main by-product was 1-chloro-1, 1,2, 3-tetrafluoropropane, the selectivity was 15.3%, and a small amount of other by-products were also present.
The dehydrochlorination procedure was as described in example 1.
The reaction product was analyzed by gas chromatography, and it was found that: the conversion rate of 3-chloro-1, 1,1, 2-tetrafluoropropane is 92.1%, and the selectivity of the main product HFO-1234yf is 93.5%.
Example 3
This example presents a process for the preparation of 1, 1-dichloro-2, 3,3, 3-tetrafluoropropene (CFO-1214ya) comprising a telomerization step and a dehydrochlorination step, the telomerization step being as described in example 1, except that in example 1: the first catalyst adopts TiCl4The amount of carbon tetrachloride was used as the second catalyst in an amount of 3.0g, the amount of carbon tetrachloride was used as the second catalyst in an amount of 15.0g, the amount of fluorotrichloromethane as the raw material in an amount of 27.50g (0.20mol) was used as the fluorochloromethane, the amount of trifluoroethylene as the raw material was kept constant, the amount of carbon tetrachloride was used as the second catalyst in an amount of 24.6g (0.30mol), and the other conditions were kept constant.
The telomeric product was analyzed by gas chromatography, which revealed that: the conversion of monofluorotrichloromethane was 65.8%, the selectivity for 3,3, 3-trichloro-1, 2,2, 2-tetrafluoropropane was 78.3%, the major by-product was 1,3, 3-trichloro-1, 1,2, 3-tetrafluoropropane, the selectivity was 20.3%, and a small amount of other by-products were also present.
The dehydrochlorination procedure was as described in example 1.
The reaction product was analyzed by gas chromatography, and it was found that: the conversion of 3,3, 3-trichloro-1, 2,2, 2-tetrafluoropropane was 88.9%, and the selectivity to the main product, CFO-1214ya, was 85.6%.
Example 4
This example presents a process for the preparation of 1-chloro-2, 3,3, 3-tetrafluoropropene (HCFO-1224yd) as described in example 1, with the only difference that: in the dehydrochlorination step, a 25 wt% NaOH solution (40g) was used instead of the 25 wt% KOH solution.
The reaction product was analyzed by gas chromatography, and it was found that: the conversion of 3, 3-dichloro-1, 1,1, 2-tetrafluoropropane (HCFC-234ea) was 70.6% and the selectivity to HCFO-1224yd, the main product, was 81.6%.
Example 5
This example presents a process for the preparation of 1-chloro-2, 3,3, 3-tetrafluoropropene (HCFO-1224yd) comprising a telomerization step and a dehydrochlorination step, the telomerization step being as described in example 1, and the same as in example 11 different from that: the first catalyst adopts AlF3The amount used was 3g, and the other conditions were kept constant.
The telomeric product was analyzed by gas chromatography, which revealed that: the conversion of monofluorodichloromethane was 66.6%, the selectivity for 3, 3-dichloro-1, 1,1, 2-tetrafluoropropane was 51.2%, the main by-products were 1, 3-dichloro-1, 2,2, 3-tetrafluoropropane and 1, 3-dichloro-1, 2,3, 3-tetrafluoropropane, the selectivities were 20.1% and 15.2%, respectively, and a small amount of other by-products was also present.
The dehydrochlorination procedure was as described in example 1.
The reaction product was analyzed by gas chromatography, and it was found that: the conversion of 3, 3-dichloro-1, 1,1, 2-tetrafluoropropane (HCFC-234ea) was 80.6% and the selectivity to HCFO-1224yd, the main product, was 89.8%.
Example 6
This example presents a process for the preparation of 1-chloro-2, 3,3, 3-tetrafluoropropene (HCFO-1224yd) comprising a telomerization step and a dehydrochlorination step, the telomerization step being as described in example 1, except that in example 1: the mass of the reaction raw materials, namely, the monofluorodichloromethane and the trifluoroethylene, is respectively 30g and 72g, and other conditions are kept unchanged.
The telomeric product was analyzed by gas chromatography, which revealed that: the conversion of monofluorodichloromethane was 77.3%, the selectivity for 3, 3-dichloro-1, 1,1, 2-tetrafluoropropane was 76.9%, the main by-products were 1, 3-dichloro-1, 2,2, 3-tetrafluoropropane and 1, 3-dichloro-1, 2,3, 3-tetrafluoropropane, the selectivities were 16.4% and 12.1%, respectively, and a small amount of other by-products was also present.
The dehydrochlorination procedure was as described in example 1, except that in example 1: the phase transfer catalyst adopts tetrabutyl ammonium bromide, and other conditions are kept unchanged.
The reaction product was analyzed by gas chromatography, and it was found that: the conversion of 3, 3-dichloro-1, 1,1, 2-tetrafluoropropane (HCFC-234ea) was 85.9%, and the selectivity to HCFO-1224yd, the major product, was 90.6%.
Example 7
This example presents a process for the preparation of 1-chloro-2, 3,3, 3-tetrafluoropropene (HCFO-1224yd) comprising a telomerization step and a dehydrochlorination step, the telomerization step being as described in example 1, except that in example 1: the reaction temperature is 50 ℃, the initial reaction pressure is 1.2MPa, and other conditions are kept unchanged.
The telomeric product was analyzed by gas chromatography, which revealed that: the conversion of monofluorodichloromethane was 92.7%, the selectivity for 3, 3-dichloro-1, 1,1, 2-tetrafluoropropane was 55.7%, the main by-products were 1, 3-dichloro-1, 2,2, 3-tetrafluoropropane and 1, 3-dichloro-1, 2,3, 3-tetrafluoropropane, the selectivities were 24.9% and 18.4%, respectively, and a small amount of other by-products was also present.
The dehydrochlorination procedure was as described in example 1, except that in example 1: the reaction temperature was 80 ℃ and the other conditions were kept constant.
The reaction product was analyzed by gas chromatography, and it was found that: the conversion of 3, 3-dichloro-1, 1,1, 2-tetrafluoropropane (HCFC-234ea) was 95.1% and the selectivity to HCFO-1224yd, the main product, was 80.8%.
Comparative example 1
This comparative example presents a process for the preparation of 1-chloro-2, 3,3, 3-tetrafluoropropene (HCFO-1224yd) comprising a telomerization step as described in example 1, with the exception of example 1: the first catalyst adopts ZnCl2The amount used was 3g, and the other conditions were kept constant.
The telomeric product was analyzed by gas chromatography, which revealed that: the conversion of monofluorodichloromethane was 13.8%, and no 3, 3-dichloro-1, 1,1, 2-tetrafluoropropane was produced.
Comparative example 2
This comparative example presents a process for the preparation of 1-chloro-2, 3,3, 3-tetrafluoropropene (HCFO-1224yd) comprising a telomerization step as described in example 1, with the exception of example 1: the reaction is directly carried out by only the first catalyst without adding the second catalyst, and other conditions are kept unchanged.
The telomeric product was analyzed by gas chromatography, which revealed that: the conversion rate of monofluorodichloromethane is 66.1 percent, the products are mainly difluorochloromethane and trichloromethane, and no 3, 3-dichloro-1, 1,1, 2-tetrafluoropropane is generated.
Comparative example 3
This comparative example presents a process for the preparation of 1-chloro-2, 3,3, 3-tetrafluoropropene (HCFO-1224yd) comprising a telomerization step as described in example 1, with the exception of example 1: the reaction is directly carried out by only the second catalyst without adding the first catalyst, and other conditions are kept unchanged.
The telomeric product was analyzed by gas chromatography, which revealed that: only a small amount of trifluoroethylene is generated from the polymerization product, and no 3, 3-dichloro-1, 1,1, 2-tetrafluoropropane is generated.
Comparative example 4
This comparative example presents a process for the preparation of 1-chloro-2, 3,3, 3-tetrafluoropropene (HCFO-1224yd) comprising a telomerization step as described in example 1, with the exception of example 1: the second catalyst mass was reduced to 3.0g (0.025mol) and the other conditions were kept constant.
The telomeric product was analyzed by gas chromatography, which revealed that: the conversion of monofluorodichloromethane was 78.5%, the products were mainly difluoromonochloromethane and trichloromethane, the selectivity for 3, 3-dichloro-1, 1,1, 2-tetrafluoropropane was only 3.8%, and a small amount of trifluoroethylene was also polymerized.
Comparative example 5
This comparative example presents a process for the preparation of 1-chloro-2, 3,3, 3-tetrafluoropropene (HCFO-1224yd) comprising a telomerization step as described in example 1, with the exception of example 1: the amount of the first catalyst added was reduced to 0.01g, the amount of the raw material monofluorodichloromethane added was increased to 103g (1.0mol), the amount of the raw material trifluoroethylene added was increased to 82g (1.0mol), and the other conditions were kept constant.
The telomeric product was analyzed by gas chromatography, which revealed that: the conversion rate of monofluoro-dichloromethane is 5.9%, no 3, 3-dichloro-1, 1,1, 2-tetrafluoropropane is generated, and a small amount of trifluoroethylene is polymerized.
Comparative example 6
This comparative example presents a process for the preparation of 1-chloro-2, 3,3, 3-tetrafluoropropene (HCFO-1224yd) comprising a telomerization step as described in example 1, with the exception of example 1: the second catalyst was changed to dichloromethane in an amount of 20g, and the other conditions were kept unchanged.
The telomeric product was analyzed by gas chromatography, which revealed that: the conversion rate of monofluorodichloromethane is 56.9%, the products are mainly difluorochloromethane and trichloromethane, no 3, 3-dichloro-1, 1,1, 2-tetrafluoropropane is generated, and a small amount of trifluoroethylene is polymerized.

Claims (12)

1. A method for preparing halogenated propylene, which is characterized in that: the preparation method of the halogenated propylene comprises the following steps:
the halopropene shown in the structural formula III is prepared by dehydrochlorination of the chlorofluoropropane shown in the structural formula II under the action of a metal base catalyst and a phase transfer catalyst, and the reaction formula is as follows:
Figure FDA0002461294920000011
wherein y is more than or equal to 1, z is more than or equal to 1, and x + y + z is 4.
2. The process for producing a halogenopropene according to claim 1, characterized in that: the chlorofluoropropane shown was prepared by the following steps:
the raw material of the fluorochloromethane shown in the structural formula I and trifluoroethylene are subjected to telomerization under the action of a liquid-phase catalyst to prepare the fluorochloropropane shown in the structural formula II, wherein the reaction formula is as follows:
Figure FDA0002461294920000012
the liquid phase catalyst comprises a first catalyst and a second catalyst, wherein the first catalyst is a Lewis acid catalyst, and the second catalyst is CHxFy-1Clz+1。
3. The process for producing a halogenopropene according to claim 1, characterized in that: the metal base catalyst is selected from at least one of metal hydroxide, metal carbonate or metal bicarbonate; the phase transfer catalyst is quaternary ammonium salt, and is selected from at least one of tetrabutylammonium bromide, tetramethylammonium hydroxide and tetramethylammonium chloride.
4. The process for producing a halogenopropene according to claim 2, characterized in that: the first catalyst is at least one halide selected from Al, Sb, Ti, Zr and Hf.
5. The process for producing a halogenopropene according to claim 3, characterized in that: the first catalyst is selected from ZrCl4、HfCl4、TiCl4、AlF3、SbF5At least one of them.
6. The process for producing a halogenopropene according to claim 3, characterized in that: the molar ratio of the raw materials of the chlorofluoromethane to the trifluoroethylene is 1: 0.1-1: 10.
7. The process for producing a halogenopropene according to claim 3, characterized in that: the dosage of the first catalyst is 0.01-50 wt% of the mass of the raw material of the chlorofluoromethane.
8. The process for producing a halogenopropene according to claim 3, characterized in that: the molar ratio of the second catalyst to the raw material of the chlorofluoromethane is as follows: 1: 0.01-1: 10.
9. The process for producing a halogenopropene according to claim 3, characterized in that: the molar ratio of the chlorofluoropropane to the metal base catalyst is as follows: 1: 0.1-1: 5.0.
10. The process for producing a halogenopropene according to claim 3, characterized in that: the second catalyst is at least one of trichloromethane, trifluoromethane, dichloromethane, tetrafluoromethane and carbon tetrachloride.
11. The process for producing a halogenopropene according to claim 3, characterized in that: the telomerization reaction is carried out at the temperature of minus 30-100 ℃ and the pressure of 0.5-2.0 MPa, and the reaction time is 1-50 h.
12. The process for producing a halogenopropene according to claim 1, characterized in that: the dehydrochlorination reaction temperature is 10-100 ℃.
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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2022218204A1 (en) * 2021-04-15 2022-10-20 浙江省化工研究院有限公司 Method for preparing 2,3,3,3-tetrafluoropropene
CN115557827A (en) * 2022-08-29 2023-01-03 西安近代化学研究所 Preparation method of 3-chloro-3,3-difluoropropylene
CN116037117A (en) * 2023-03-31 2023-05-02 北京宇极科技发展有限公司 Initiator, fluorination catalyst and preparation method of E-1, 3-tetrafluoropropene and Z-1, 3-tetrafluoropropene

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1589248A (en) * 2001-09-25 2005-03-02 霍尼韦尔国际公司 Process for producing fluoroolefins
CN102947257A (en) * 2010-06-23 2013-02-27 旭硝子株式会社 Production method for 1,1-dichloro-2,3,3,3-tetra-fluoropropene and 2,3,3,3-tetrafluoropropene
CN106458800A (en) * 2014-06-06 2017-02-22 旭硝子株式会社 Method for producing 1,1-dichloro-3,3,3-trifluoropropane
WO2019003896A1 (en) * 2017-06-27 2019-01-03 Ａｇｃ株式会社 Production method for 2-chloro-1,1,1,2-tetrafluoropropane and/or 3-chloro-1,1,1,2-tetrafluoropropane, and production method for 2,3,3,3-tetrafluoropropene
CN109438170A (en) * 2018-11-27 2019-03-08 浙江三美化工股份有限公司 A kind of preparation method of 2,3,3,3- tetrafluoropropenes

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1589248A (en) * 2001-09-25 2005-03-02 霍尼韦尔国际公司 Process for producing fluoroolefins
CN102947257A (en) * 2010-06-23 2013-02-27 旭硝子株式会社 Production method for 1,1-dichloro-2,3,3,3-tetra-fluoropropene and 2,3,3,3-tetrafluoropropene
CN106458800A (en) * 2014-06-06 2017-02-22 旭硝子株式会社 Method for producing 1,1-dichloro-3,3,3-trifluoropropane
WO2019003896A1 (en) * 2017-06-27 2019-01-03 Ａｇｃ株式会社 Production method for 2-chloro-1,1,1,2-tetrafluoropropane and/or 3-chloro-1,1,1,2-tetrafluoropropane, and production method for 2,3,3,3-tetrafluoropropene
CN109438170A (en) * 2018-11-27 2019-03-08 浙江三美化工股份有限公司 A kind of preparation method of 2,3,3,3- tetrafluoropropenes

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2022218204A1 (en) * 2021-04-15 2022-10-20 浙江省化工研究院有限公司 Method for preparing 2,3,3,3-tetrafluoropropene
CN115557827A (en) * 2022-08-29 2023-01-03 西安近代化学研究所 Preparation method of 3-chloro-3,3-difluoropropylene
CN116037117A (en) * 2023-03-31 2023-05-02 北京宇极科技发展有限公司 Initiator, fluorination catalyst and preparation method of E-1, 3-tetrafluoropropene and Z-1, 3-tetrafluoropropene

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