CN113527040B - Preparation method of halogenated propylene - Google Patents

Preparation method of halogenated propylene Download PDF

Info

Publication number
CN113527040B
CN113527040B CN202010320787.5A CN202010320787A CN113527040B CN 113527040 B CN113527040 B CN 113527040B CN 202010320787 A CN202010320787 A CN 202010320787A CN 113527040 B CN113527040 B CN 113527040B
Authority
CN
China
Prior art keywords
catalyst
halopropene
reaction
structural formula
raw material
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN202010320787.5A
Other languages
Chinese (zh)
Other versions
CN113527040A (en
Inventor
刘敏洋
于万金
林胜达
刘武灿
张建君
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Zhejiang Chemical Industry Research Institute Co Ltd
Sinochem Lantian Co Ltd
Original Assignee
Zhejiang Chemical Industry Research Institute Co Ltd
Sinochem Lantian Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Zhejiang Chemical Industry Research Institute Co Ltd, Sinochem Lantian Co Ltd filed Critical Zhejiang Chemical Industry Research Institute Co Ltd
Priority to CN202010320787.5A priority Critical patent/CN113527040B/en
Publication of CN113527040A publication Critical patent/CN113527040A/en
Application granted granted Critical
Publication of CN113527040B publication Critical patent/CN113527040B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • 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

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)

Abstract

A process for the preparation of a halopropene comprising: the fluorophlorpropane shown in the structural formula II 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, wherein 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-tetrafluoropropene or chloro-2, 3-tetrafluoropropene by dehydrochlorination of a telomerization product of chlorofluoromethane and trifluoroethylene.
Background
2, 3-tetrafluoropropene (HFO-1234 yf) 1-chloro-2, 3-tetrafluoropropene (HCFO-1224 yd) and 1, 1-dichloro-2, 3-tetrafluoropropene (CFO-1214 ya) are 3 common halopropenes, in particular HFO-1234yf and HCFO-1224yd, the CFO-1214ya is a raw material for synthesizing HFO-1234yf and HCFO-1224yd, and has high research value because of the excellent environmental performance of the refrigerant.
The ODP of 2, 3-tetrafluoropropene is zero, the GWP value is 4, the Life Cycle Climate Performance (LCCP) is lower than that of the traditional refrigerant HFC-134a, the system refrigeration performance is better than that of HFC-134a, and the atmospheric decomposition products are the same as that of HFC-134a, so that the system is considered to be the most potential automobile refrigerant substitute at present and has been accepted by a plurality of mainstream automobile manufacturers. The Xudizi patent WO2011162341A discloses a process for preparing 2, 3-tetrafluoropropene by hydrogenation reduction of 1, 1-dichloro-2, 3-tetrafluoropropene (CFO-1214 ya) as a starting material in the presence of a palladium catalyst. But the hydrogenation reduction reaction degree of the method is difficult to control, is easy to generate 1-chloro-2, 3-tetrafluoropropene (HCFO-1224 yd) intermediate or over-reduced products of 1-chloro-2, 3-tetrafluoropropane (HCFC-244 eb) and 2, 3-tetrafluoropropane (HFC-254 eb), the product selectivity is low, the post-treatment operation is complicated, and the byproduct HFC-254eb is easy to undergo further dehydrofluorination reaction in the alkaline washing treatment process to generate 3, 3-trifluoropropene (HFO-1243 zf) with the boiling point close to that of HFO-1234yf, so that the impurity separation difficulty is further increased. Although the problems can be improved by controlling the reaction temperature of the catalyst bed and the alkaline washing absorption temperature, the improvement degree is not obvious, the control difficulty of the process condition is high, and the method is not suitable for industrial scale-up.
The ODP of the 1-chloro-2, 3-tetrafluoropropene (HCFO-1224 yd) is zero, the GWP value is less than 1, the chemical stability is good, the refrigeration performance is excellent, and the catalyst can be used for refrigeration systems of air conditioners, refrigerators and the like. The Xudi patent WO2017146189A also discloses a method for preparing HCFO-1224yd by hydrogenation reduction of CFO-1214ya, wherein the formation of byproducts (HFO-1234 yf, HFC-254eb and other over-reduced products) is inhibited by changing the catalyst formulation, reducing the hydrogen consumption, controlling the catalyst bed temperature and the like, so that the target product HCFO-1224yd is obtained with high selectivity. Specifically, the molar ratio of hydrogen to CFO-1214ya (H 2 /1214 ya) is controlled below 1.4, even below 1.0, but H is considered in view of the yield of product 1224yd 2 Higher than 0.4 is needed for/1214 ya; the temperature of the catalyst bed is controlled below 130 ℃; adopting the specific surface area of less than 40m 2 The palladium catalyst (loaded on the surface of the active carbon) per gram shows better catalytic activity, stability and product selectivity. The reaction is easy to implement industrially and can be stably produced, but the selectivity of the main product HCFO-1224yd is lower than 20 percent. Xu (Chinese character)The nitrate patent WO2018030408A discloses that during the CFO-1214ya hydrogenation reduction, the catalytic activity, stability and product selectivity are promoted by adding an appropriate amount of chloride ions to the palladium catalyst, but the selectivity of HCFO-1224yd is still below 30%.
The above-mentioned method for preparing halopropene by hydrogenation reduction has the general problem of low product selectivity, and the reaction product contains more 1-chloro-1,2,2,3,3,3-hexafluoropropane, 1-chloro-1, 2, 3-hexafluoropropane a plurality of fluorine-containing byproducts such as 1-chloro-1, 3-tetrafluoropropene, 2-chloro-1, 3-tetrafluoropropene and the like, because the fluorine-containing byproducts have similar properties, the impurities are difficult to effectively remove by adopting common rectification, and the post-treatment difficulty is increased.
Japanese patent JP3778298A discloses a process for preparing CFO-1214ya by dehydrofluorination under the action of a base catalyst using 1, 1-dichloro-2, 3-pentafluoropropane (HCFC-225 ca) as a starting material. However, the HCFC-225ca used in the preparation method is prepared by telomerization of tetrafluoroethylene and monofluorodichloromethane, and usually contains a large amount of isomer 1, 3-dichloro-1, 2, 3-pentafluoropropane (HCFC-225 cb), and the HCFC-225ca can be used as the raw material for the reaction after separation and purification. 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 multistage rectification and the like, thereby having higher separation difficulty.
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 invention aims at realizing the following technical scheme:
the invention provides a preparation method of halogenated propylene, which adopts fluorine chloropropane shown in the following structural formula II as a raw material, and prepares the halogenated propylene shown in the structural formula III through dehydrochlorination reaction under the action of a metal base catalyst and a phase transfer catalyst, wherein the reaction formula is as follows:
compared with other structural formulas of the fluoro-chloromethane, such as 1, 2-dichloro-2, 3-tetrafluoropropane, the fluoro-chloromethane with the structure can be prepared by liquid phase telomerization, the liquid phase telomerization product has high selectivity, no by-product with the boiling point close to that of difficult separation exists, and the target product with high purity can be obtained by simple rectification.
The invention also provides a preparation method of the halogenated propylene, which adopts the fluoro-chloromethane as the raw material, and comprises the following steps:
and (3) a telomerization process: the raw material of the fluoro-chloro-methane and the trifluoroethylene shown in the structural formula I are subjected to telomerization reaction under the action of a liquid phase catalyst to prepare fluoro-chloro-propane shown in the 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 CH x F y-1 Cl z+1 The method comprises the steps of carrying out a first treatment on the surface of the Wherein y is greater than or equal to 1, z is greater than or equal to 1, and x+y+z=4;
dehydrochlorination process: the fluorophlorpropane is subjected to dehydrochlorination reaction under the action of a metal base catalyst and a phase transfer catalyst to prepare halogenated propylene shown in a structural formula III;
the reaction formula is as follows:
in the telomerization process:
the first catalyst is selected from at least one halide in Al, sb, ti, zr, hf. Preferably, the first catalyst is selected from ZrCl 4 、HfCl 4 、TiCl 4 、AlF 3 、SbF 5 At least one of them. More preferably, the first catalyst is ZrCl 4 Or HfCl 4 。
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 chlorofluoromethane.
In the dehydrochlorination process:
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 metal base catalyst concentration is 10 to 40wt%.
The phase transfer catalyst is a 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 reaction results are affected by the ratio of raw materials, the ratio of raw materials to catalyst, the reaction temperature, the reaction time, and the like, and particularly, the combination of multiple variables can have a great influence on the reaction results.
In the telomerization process for preparing the halopropene, the molar ratio of the raw material fluorochloromethane to the trifluoroethylene is 1:0.1-1:10; more preferably, the molar ratio of the raw material fluorochloromethane to the trifluoroethylene is 1:1-1:5. The dosage of the first catalyst is 0.01-50wt% of the mass of the raw material chlorofluoromethane; more preferably, the first catalyst is used in an amount of 0.1 to 10wt% based on the mass of the raw material chlorofluoromethane. The molar ratio of the second catalyst to the raw material chlorofluoromethane is 1:0.01-1:10; more preferably, the molar ratio of the second catalyst to the raw material chlorofluoromethane is 1:0.1-1:5.
The liquid phase telomerization process is carried out at the temperature of minus 30 ℃ to 100 ℃ and the pressure of 0.5 MPa to 2.0MPa, and the reaction time is 1 h to 50h. 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 halopropene, the molar ratio of the fluorophlorperazine 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 fluorine chloropropane 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 catalyze the liquidPhase telomerization, the two complement each other, which is indispensable. First catalyst dissociation activation raw material fluorine chloromethane CH x F y Cl z Form F - 、CH x F y-1 Cl z + 、Cl - 、CH x F y Cl z-1 + A plasma; the second catalyst inhibits F formed by dissociation - 、CH x F y-1 Cl z + 、Cl - 、CH x F y Cl z-1 + Plasma recombination to ensure F - And CH (CH) x F y-1 Cl z + The ions and trifluoroethylene are subjected to directional telomerization reaction to obtain a telomerization product CF with high selectivity 3 CHFCH x F y-1 Cl z 。
Meanwhile, the raw material of the invention, namely the fluoro-chloromethane, the second catalyst, the telogen and the target product of the halopropene have one-to-one correspondence, which is obtained from the raw material of the fluoro-chloromethane CH x F y Cl z Second catalyst CH x F y-1 Cl z+1 Telomerization product CF 3 CHFCH x F y-1 Cl z And the target product halopropene CF 3 CF＝CH x F y-1 Cl z-1 The structural expression of (2) can be known. If the raw material is monofluorodichloromethane, the second catalyst is trichloromethane, the corresponding telogen product is 3, 3-dichloro-1, 2-tetrafluoropropane, and the target product is 1-chloro-2, 3-tetrafluoropropene. When the raw material is monofluoro-chloromethane, the second catalyst is methylene dichloride, the corresponding telogen product is 3-chloro-1, 2-tetrafluoropropane, and the target product is 2, 3-tetrafluoropropene. When the raw material is monofluorotrichloromethane, the second catalyst is carbon tetrachloride, the corresponding telogenic product is 3, 3-trichloro-1, 2-tetrafluoropropane, and the target product is 1, 1-dichloro-2, 3-tetrafluoropropene.
The preparation method of the halopropene comprises the following steps:
A1. under the combined action of a first catalyst and a second catalyst, raw materials of chlorofluoromethane and trifluoroethylene undergo liquid phase telomerization in a first reaction kettle; specifically, adding a first catalyst and a second catalyst into a first reaction kettle, mixing, introducing nitrogen to replace air in the kettle, and then adding raw material chlorofluoromethane and trifluoroethylene to react;
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. filtering, rectifying or flash evaporating the materials in the reaction kettle to obtain a solid-liquid separation treatment, wherein the solid part is a first catalyst, and the liquid part is further rectified and separated to obtain a second catalyst and a telogen;
the unreacted gas-phase raw material and the first and second catalysts can be returned to the step A1 for reuse;
A4. adding a 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 dehydrochlorination reaction temperature to start reaction;
A6. after the reaction is finished, the reaction product is subjected to liquid separation and rectification treatment to obtain the target product.
Compared with the prior art, the invention has the following beneficial effects:
the invention proposes the use of Lewis acid and CH x F y-1 Cl z+1 The method for preparing the telomerization product of the fluorophlogopropane by jointly catalyzing the reaction of the fluorochloromethane and the trifluoroethylene and obtaining the corresponding halogenated propylene after dehydrochlorination treatment of the fluorophlogopropane has the advantages of easily obtained raw materials, simple process, mild reaction conditions, high selectivity of the telomerization product and the target product, suitability for industrialized amplification and the like.
Detailed Description
The invention will be further illustrated with reference to the following specific examples, without limiting the invention to these specific embodiments. It will be appreciated by those skilled in the art that the invention encompasses all alternatives, modifications and equivalents as may be included within the scope of the claims.
Example 1
The present example proposes a process for the preparation of 1-chloro-2, 3-tetrafluoropropene (HCFO-1224 yd) comprising a telogenic process and a dehydrochlorination process, in particular:
and (3) a telomerization process:
A1. an autoclave made of Inconel alloy and having a volume of 250mL was used as a reactor, and 3.0g of ZrCl as a first catalyst was used 4 And 20.0g of trichloromethane serving as a second catalyst are respectively added into the reaction kettle, 1.0MPa of nitrogen is introduced into the reaction kettle after the reaction kettle is sealed to replace air in the reaction kettle, and the process is repeated for three times;
A2. 29.87g (0.29 mol) of fluorodichloromethane and 23.78g (0.29 mol) of trifluoroethylene are sequentially introduced after the air in the reaction kettle is completely replaced;
A3. setting the reaction temperature to be 30 ℃, stirring the mixture at 300rpm, setting the initial reaction pressure to be 0.9MPa, gradually reducing the reaction pressure along with the reaction, and setting the reaction time to be 10 hours;
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; filtering, rectifying or flash evaporating the materials in the reaction kettle to obtain a solid-liquid separation treatment, wherein the solid part is a first catalyst, and the liquid part is further rectified and separated to obtain a second catalyst and a telogen;
unreacted gas phase feed and the first and second catalysts may be returned to step A1 for reuse.
The telomerization product was analyzed by gas chromatography, as follows: the conversion of monofluorodichloromethane was 85.0%, the selectivity of 3, 3-dichloro-1, 2-tetrafluoropropane was 72.9%, and the byproducts including 1, 3-dichloro-1, 2, 3-tetrafluoropropane and 1, 3-dichloro-1, 2, 3-tetrafluoropropane were 14.8% and 11.1%, respectively, with a small amount of other byproducts.
Dehydrochlorination process:
B1. adopting an autoclave made of Inconel alloy with the volume of 250mL as a reactor, respectively adding 20g of telomerization product, 40g of 25wt% KOH solution and 1g of tetramethylammonium hydroxide into the reactor, sealing the reactor, and then introducing 1.0MPa nitrogen to replace air in the reactor, and repeating the steps for three times;
B2. setting the reaction temperature to 50 ℃ after the air in the reaction kettle is completely replaced, stirring the reaction kettle at 300rpm, and reacting the reaction kettle for 5 hours;
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-tetrafluoropropene.
The reaction product was analyzed by gas chromatography, as follows: the conversion of 3, 3-dichloro-1, 2-tetrafluoropropane (HCFC-234 ea) was 90.8% and the selectivity of the main product HCFO-1224yd was 91.2%.
Example 2
This example proposes a process for the preparation of 2, 3-tetrafluoropropene (HFO-1234 yf) comprising a telomerization process and a dehydrochlorination process, the telomerization process steps being as described in example 1, differing from example 1 in that: the first catalyst adopts HfCl 4 The addition amount is 3.0g, the addition amount is 20.0g, the addition amount of the second catalyst is 19.87g (0.29 mol) of the raw material of the fluorochloromethane, the addition amount of the raw material of the trifluoroethylene is 24.6g (0.30 mol), the reaction temperature is 10 ℃, and other conditions are kept unchanged.
The telomerization product was analyzed by gas chromatography, as follows: the conversion of monofluoromethane was 76.5%, the selectivity of 3-chloro-1, 2-tetrafluoropropane was 81.2%, the major by-product was 1-chloro-1, 2, 3-tetrafluoropropane, the selectivity was 15.3%, and there were small amounts of other by-products.
Dehydrochlorination procedure was as described in example 1.
The reaction product was analyzed by gas chromatography, as follows: the conversion of 3-chloro-1, 2-tetrafluoropropane was 92.1%, and the selectivity of the main product HFO-1234yf was 93.5%.
Example 3
This example proposes a process for the preparation of 1, 1-dichloro-2, 3-tetrafluoropropene (CFO-1214 ya) comprising a telomerization procedure and a dehydrochlorination procedure, the telomerization procedure being as described in example 1, the difference from example 1 being that: tiCl is used as the first catalyst 4 The addition amount is 3.0g, the addition amount is 15.0g, the addition amount of the second catalyst is 27.50g (0.20 mol) of the raw material fluorochloromethane and the addition amount of the monofluorotrichloromethane, the addition amount of the raw material trifluoroethylene is 24.6g (0.30 mol), and other conditions are kept unchanged.
The telomerization product was analyzed by gas chromatography, as follows: the conversion of monofluorotrichloromethane is 65.8%, the selectivity of 3, 3-trichloro-1, 2-tetrafluoropropane is 78.3%, the main byproduct is 1, 3-trichloro-1, 2, 3-tetrafluoropropane, the selectivity is 20.3%, and other byproducts are small.
Dehydrochlorination procedure was as described in example 1.
The reaction product was analyzed by gas chromatography, as follows: the conversion of 3, 3-trichloro-1, 2-tetrafluoropropane was 88.9% and the selectivity of the main product CFO-1214ya was 85.6%.
Example 4
This example presents a process for the preparation of 1-chloro-2, 3-tetrafluoropropene (HCFO-1224 yd) with the following steps as in example 1, the only difference being: in the dehydrochlorination step, 25wt% NaOH solution (40 g) was used instead of 25wt% KOH solution.
The reaction product was analyzed by gas chromatography, as follows: the conversion of 3, 3-dichloro-1, 2-tetrafluoropropane (HCFC-234 ea) was 70.6% and the selectivity of the main product HCFO-1224yd was 81.6%.
Example 5
This example proposes a process for the preparation of 1-chloro-2, 3-tetrafluoropropene (HCFO-1224 yd) comprising a telomerization process and a dehydrochlorination process, the telomerization process steps being as described in example 1, differing from example 1 in that: the first catalyst adopts AlF 3 The amount was 3g, and the other conditions remained unchanged.
The telomerization product was analyzed by gas chromatography, as follows: the conversion of monofluorodichloromethane was 66.6%, the selectivity of 3, 3-dichloro-1, 2-tetrafluoropropane was 51.2%, the major by-products were 1, 3-dichloro-1, 2, 3-tetrafluoropropane and 1, 3-dichloro-1, 2, 3-tetrafluoropropane, the selectivities were 20.1% and 15.2%, respectively, and small amounts of other by-products were found.
Dehydrochlorination procedure was as described in example 1.
The reaction product was analyzed by gas chromatography, as follows: the conversion of 3, 3-dichloro-1, 2-tetrafluoropropane (HCFC-234 ea) was 80.6% and the selectivity of the main product HCFO-1224yd was 89.8%.
Example 6
This example proposes a process for the preparation of 1-chloro-2, 3-tetrafluoropropene (HCFO-1224 yd) comprising a telomerization process and a dehydrochlorination process, the telomerization process steps being as described in example 1, differing from example 1 in that: the mass of the reaction raw materials of monofluorodichloromethane and trifluoroethylene is 30g and 72g respectively, and other conditions are kept unchanged.
The telomerization product was analyzed by gas chromatography, as follows: the conversion of monofluorodichloromethane was 77.3%, the selectivity of 3, 3-dichloro-1, 2-tetrafluoropropane was 76.9%, the major by-products were 1, 3-dichloro-1, 2, 3-tetrafluoropropane and 1, 3-dichloro-1, 2, 3-tetrafluoropropane, the selectivities were 16.4% and 12.1%, respectively, and there were small amounts of other by-products.
Dehydrochlorination procedure the procedure is as described in example 1, except that: the phase transfer catalyst adopts tetrabutylammonium bromide, and other conditions are kept unchanged.
The reaction product was analyzed by gas chromatography, as follows: the conversion of 3, 3-dichloro-1, 2-tetrafluoropropane (HCFC-234 ea) was 85.9% and the selectivity of the main product HCFO-1224yd was 90.6%.
Example 7
This example proposes a process for the preparation of 1-chloro-2, 3-tetrafluoropropene (HCFO-1224 yd) comprising a telomerization process and a dehydrochlorination process, the telomerization process steps being as described in example 1, differing from example 1 in that: the reaction temperature was 50℃and the initial reaction pressure was 1.2MPa, with other conditions remaining unchanged.
The telomerization product was analyzed by gas chromatography, as follows: the conversion of monofluorodichloromethane was 92.7%, the selectivity of 3, 3-dichloro-1, 2-tetrafluoropropane was 55.7%, the main byproducts were 1, 3-dichloro-1, 2, 3-tetrafluoropropane and 1, 3-dichloro-1, 2, 3-tetrafluoropropane, the selectivities were 24.9% and 18.4%, respectively, and small amounts of other byproducts were also present.
Dehydrochlorination procedure the procedure is as described in example 1, except that: the reaction temperature was 80℃and the other conditions remained unchanged.
The reaction product was analyzed by gas chromatography, as follows: the conversion of 3, 3-dichloro-1, 2-tetrafluoropropane (HCFC-234 ea) was 95.1% and the selectivity of the main product HCFO-1224yd was 80.8%.
Comparative example 1
This comparative example proposes a process for the preparation of 1-chloro-2, 3-tetrafluoropropene (HCFO-1224 yd) comprising a telogenic procedure, the telogenic procedure being as described in example 1, differing from example 1 in that: the first catalyst adopts ZnCl 2 The amount was 3g, and the other conditions remained unchanged.
The telomerization product was analyzed by gas chromatography, as follows: the conversion of monofluorodichloromethane is 13.8%, and 3, 3-dichloro-1, 2-tetrafluoropropane is not generated.
Comparative example 2
This comparative example proposes a process for the preparation of 1-chloro-2, 3-tetrafluoropropene (HCFO-1224 yd) comprising a telogenic procedure, the telogenic procedure being as described in example 1, differing from example 1 in that: the reaction is directly carried out by the first catalyst without adding the second catalyst, and other conditions are kept unchanged.
The telomerization product was analyzed by gas chromatography, as follows: the conversion rate of the monofluorodichloromethane is 66.1%, the products are mainly difluoro chloromethane and trichloromethane, and 3, 3-dichloro-1, 2-tetrafluoropropane is not generated.
Comparative example 3
This comparative example proposes a process for the preparation of 1-chloro-2, 3-tetrafluoropropene (HCFO-1224 yd) comprising a telogenic procedure, the telogenic procedure being as described in example 1, differing from example 1 in that: the reaction is directly carried out by only the second catalyst without adding the first catalyst, and other conditions are kept unchanged.
The telomerization product was analyzed by gas chromatography, as follows: only a small amount of trifluoroethylene is produced from the polymerization product, and 3, 3-dichloro-1, 2-tetrafluoropropane is not produced.
Comparative example 4
This comparative example proposes a process for the preparation of 1-chloro-2, 3-tetrafluoropropene (HCFO-1224 yd) comprising a telogenic procedure, the telogenic procedure being as described in example 1, differing from example 1 in that: the mass of the second catalyst was reduced to 3.0g (0.025 mol) and the other conditions remained unchanged.
The telomerization product was analyzed by gas chromatography, as follows: the conversion of monofluorodichloromethane is 78.5%, the products are mainly difluoro chloromethane and trichloromethane, the selectivity of 3, 3-dichloro-1, 2-tetrafluoropropane is only 3.8%, and the products are also a small amount of trifluoroethylene self-polymerization products.
Comparative example 5
This comparative example proposes a process for the preparation of 1-chloro-2, 3-tetrafluoropropene (HCFO-1224 yd) comprising a telogenic procedure, the telogenic procedure being as described in example 1, differing from example 1 in that: the amount of the first catalyst added was reduced to 0.01g, the amount of the raw material monofluorodichloromethane added was increased to 103g (1.0 mol), the amount of the raw material trifluoroethylene added was increased to 82g (1.0 mol), and the other conditions were kept unchanged.
The telomerization product was analyzed by gas chromatography, as follows: the conversion of monofluorodichloromethane was 5.9%, no 3, 3-dichloro-1, 2-tetrafluoropropane was produced, and a small amount of trifluoroethylene was also self-polymerized.
Comparative example 6
This comparative example proposes a process for the preparation of 1-chloro-2, 3-tetrafluoropropene (HCFO-1224 yd) comprising a telogenic procedure, the telogenic procedure being as described in example 1, differing from example 1 in that: the second catalyst was replaced by dichloromethane in an amount of 20g, the other conditions remaining unchanged.
The telomerization product was analyzed by gas chromatography, as follows: the conversion of monofluorodichloromethane is 56.9%, the products are mainly difluoro chloromethane and trichloromethane, 3-dichloro-1, 2-tetrafluoropropane is not generated, and a small amount of trifluoroethylene self-polymerization product is also generated.

Claims (8)

1. A preparation method of halogenated propylene is characterized in that: the preparation method of the halogenated propylene comprises 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:
the liquid phase catalyst comprises a first catalyst and a second catalyst, wherein the first catalyst is a Lewis acid catalyst and is selected from ZrCl 4 、HfCl 4 、TiCl 4 、AlF 3 At least one of (a) and (b); the second catalyst is CH x F y-1 Cl z+1 Selected from chloroform, dichloromethane or carbon tetrachloride;
the fluorophlorpropane shown in the structural formula II 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, wherein the reaction formula is as follows:
wherein y is greater than or equal to 1, z is greater than or equal to 1, and x+y+z=4;
when the raw material fluorochloromethane is monofluorodichloromethane, the second catalyst is trichloromethane, the fluorochloropropane shown in the structural formula II is 3, 3-dichloro-1, 2-tetrafluoropropane, and the halopropene shown in the structural formula III is 1-chloro-2, 3-tetrafluoropropene;
when the raw material fluorochloromethane is monofluorochloromethane, the second catalyst is methylene dichloride, the fluorochloropropane shown in the structural formula II is 3-chloro-1, 2-tetrafluoropropane, and the halopropene shown in the structural formula III is 2, 3-tetrafluoropropene;
when the raw material fluorochloromethane is monofluorotrichloromethane, the second catalyst is carbon tetrachloride, the fluorochloropropane shown in the structural formula II is 3, 3-trichloro-1, 2-tetrafluoropropane, and the halopropene shown in the structural formula III is 1, 1-dichloro-2, 3-tetrafluoropropene.
2. The method for producing halopropene as claimed in claim 1, wherein: 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 at least one selected from tetrabutylammonium bromide, tetramethylammonium hydroxide and tetramethylammonium chloride.
3. The method for producing halopropene as claimed in claim 1, wherein: the molar ratio of the raw material of the chlorofluoromethane to the trifluoroethylene is 1:0.1-1:10.
4. The method for producing halopropene as claimed in claim 1, wherein: the dosage of the first catalyst is 0.01-50wt% of the mass of the raw material chlorofluoromethane.
5. The method for producing halopropene as claimed in claim 1, wherein: the molar ratio of the second catalyst to the raw material of the chlorofluoromethane is as follows: 1:0.01-1:10.
6. The method for producing halopropene as claimed in claim 1, wherein: the molar ratio of the fluorophlorperazine to the metal base catalyst is as follows: 1:0.1-1:5.0.
7. The method for producing halopropene as claimed in claim 1, wherein: the telomerization reaction is carried out at the temperature of minus 30 ℃ to 100 ℃ and the pressure of 0.5 MPa to 2.0MPa, and the reaction time is 1 h to 50h.
8. The method for producing halopropene as claimed in claim 1, wherein: the dehydrochlorination reaction temperature is 10-100 ℃.
CN202010320787.5A 2020-04-22 2020-04-22 Preparation method of halogenated propylene Active CN113527040B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202010320787.5A CN113527040B (en) 2020-04-22 2020-04-22 Preparation method of halogenated propylene

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202010320787.5A CN113527040B (en) 2020-04-22 2020-04-22 Preparation method of halogenated propylene

Publications (2)

Publication Number Publication Date
CN113527040A CN113527040A (en) 2021-10-22
CN113527040B true CN113527040B (en) 2023-09-01

Family

ID=78094092

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202010320787.5A Active CN113527040B (en) 2020-04-22 2020-04-22 Preparation method of halogenated propylene

Country Status (1)

Country Link
CN (1) CN113527040B (en)

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20240208887A1 (en) * 2021-04-15 2024-06-27 Zhejiang Research Institute Of Chemical Industry Co., Ltd Method for preparing 2,3,3,3-tetrafluoropropene
CN116041138A (en) * 2022-08-19 2023-05-02 江西中欣埃克盛新材料有限公司 Method for co-producing R244bb and R1234yf by taking R134a and methylene dichloride as raw materials
CN115557827B (en) * 2022-08-29 2024-10-15 西安近代化学研究所 Preparation method of 3-chloro-3, 3-difluoropropene
CN116037117B (en) * 2023-03-31 2023-07-25 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

Also Published As

Publication number Publication date
CN113527040A (en) 2021-10-22

Similar Documents

Publication Publication Date Title
CN113527040B (en) Preparation method of halogenated propylene
EP1658252B1 (en) Process for the manufacture of 1,3,3,3- tetrafluoropropene
EP1678106B1 (en) Process for producing fluoropropenes
EP2585423B1 (en) Method for prolonging a catalyst's life during hydrofluorination
CA2598382C (en) Integrated hfc trans-1234ze manufacture process
US7829747B2 (en) Process for dehydrofluorination of 3-chloro-1,1,1,3-tetrafluoropropane to 1-chloro-3,3,3-trifluoropropene
US9180433B2 (en) Catalysts for 2-chloro-1,1,1,2-tetrafluoropropane dehydrochlorination
US7091388B2 (en) Method of making 1,1,3,3,3-pentafluoropropene
US8710282B2 (en) Integrated process for the manufacture of fluorinated olefins
JP5805812B2 (en) Integrated HFC Transformer-1234ZE Manufacturing Method
JP5653833B2 (en) Process for producing polychloropropane
CN115215722B (en) Co-production preparation method of 2, 3-tetrafluoropropene and 1-chloro-3, 3-trifluoropropene
CN113527045B (en) Preparation method of fluorophlorpropane
CN115215724B (en) Method for preparing 2, 3-tetrafluoropropene by two-step method
CN115215723B (en) Co-production preparation method of 2, 3-tetrafluoropropene and 1-chloro-2, 3-tetrafluoropropene
CN114436764B (en) Preparation method of 1-chloro-2, 3-tetrafluoropropene and intermediate thereof
CN118063282A (en) Preparation method of 2-chloro-1, 2-tetrafluoropropane
US20190300459A1 (en) Method for improving the production of a chlorinated alkane by chlorination of a chloroalkene using a diluent
CN117567236A (en) Method for co-producing 3, 3-trifluoropropene and 2, 3-tetrafluoropropene
JP2024515341A (en) Method for Producing 2,3,3,3-Tetrafluoropropene

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant