CN115417744B - Method for preparing 1-chloro-1, 1-difluoroethane - Google Patents
Method for preparing 1-chloro-1, 1-difluoroethane Download PDFInfo
- Publication number
- CN115417744B CN115417744B CN202211040372.8A CN202211040372A CN115417744B CN 115417744 B CN115417744 B CN 115417744B CN 202211040372 A CN202211040372 A CN 202211040372A CN 115417744 B CN115417744 B CN 115417744B
- Authority
- CN
- China
- Prior art keywords
- catalyst
- chloro
- difluoroethane
- dichloroethylene
- reaction
- 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
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/07—Preparation of halogenated hydrocarbons by addition of hydrogen halides
- C07C17/087—Preparation of halogenated hydrocarbons by addition of hydrogen halides to unsaturated halogenated hydrocarbons
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a preparation method of 1-chloro-1, 1-difluoroethane. The disclosed method comprises the following steps: under the action of a composite catalyst and at the reaction temperature of 60-120 ℃, 1-dichloroethylene and HF are subjected to liquid phase fluorination to prepare 1-chloro-1, 1-difluoroethane; the composite catalyst consists of a catalyst main agent and a catalyst auxiliary agent, wherein the catalyst main agent is metal halide, and the catalyst auxiliary agent is organic amine. The invention has the advantage of high selectivity.
Description
Technical Field
The invention relates to a method for preparing 1-chloro-1, 1-difluoroethane, in particular to a method for preparing 1-chloro-1, 1-difluoroethane by liquid phase fluorination by taking 1, 1-dichloroethylene as a raw material.
Background
1-chloro-1, 1-difluoroethane (HCFC-142 b), which is a high temperature refrigerant, is mainly used in refrigeration air-conditioning (high temperature air-conditioning) in high temperature environment, heat pump, mixed refrigerant and the like. HCFC-142b is progressively disabled as a transitional substitute for CFCs, but is of great interest as an organic intermediate in the preparation of polyvinylidene fluoride (PVDF) resins, i.e., HCFC-142b pyrolysis to prepare vinylidene fluoride (VDF) monomers, which in turn produce polyvinylidene fluoride (PVDF) resins. Along with the continuous expansion of the application field of the fluorine-containing polymer, the HCFC-142b used as the VDF production raw material has wide market development prospect.
2021, wang Qingsong et al were treated with SnCl 4 As a catalyst, HCFC-142b is synthesized by one-step liquid phase fluorination of VDC. The reaction is carried out in a liquid phase reaction kettle, the reaction kettle is connected with a fluorination tower and a tower top condenser, a product generated by the reaction flows back through the fluorination tower and the condenser, and the gas is discharged to a post-treatment system; the feed ratio is 1.5-1.8, the reaction temperature is 70-95 ℃, the reaction pressure is 1.1-1.3 MPa, the cold top temperature is 10-25 ℃, the VDC conversion rate is over 99.9%, and the ratio of the main reactants HFC-143a and HCFC-142b is 7:3-5:5. The reaction product of the method cannot be regulated and controlled, and the selectivity of HCFC-142b is low.
Disclosure of Invention
The invention aims to overcome the defects in the background art and provide a preparation method of 3-chloro-1, 3-tetrafluoropropane with high product selectivity.
In order to achieve the purpose of the invention, the technical scheme adopted by the invention is as follows: introducing a catalytic auxiliary agent to construct a composite catalytic system, and performing dual functions of regulating the acidity of the catalytic system and preventing the self polymerization of the 1, 1-dichloroethylene, and preparing the 1-chloro-1, 1-difluoroethane by liquid phase fluorination of the 1, 1-dichloroethylene and hydrogen fluoride with high selectivity.
For this purpose, the preparation method of the 1-chloro-1, 1-difluoroethane provided by the invention comprises the following steps: under the action of a composite catalyst and at the reaction temperature of 60-120 ℃, 1-dichloroethylene and HF are subjected to liquid phase fluorination to prepare 1-chloro-1, 1-difluoroethane; the composite catalyst consists of a catalyst main agent and a catalyst auxiliary agent, wherein the catalyst main agent is metal halide, and the catalyst auxiliary agent is organic amine.
Optionally, the metal halide is SnCl 4 、SnF 4 、TiCl 4 Or TiF 4 . Preferably TiF 4 Or TiCl 4 。
Optionally, the organic amine is one or more than two of triethylamine, n-butylamine, imidazole, isopropylamine and ethylenediamine. Preferably, one or a mixture of two of imidazole and n-butylamine.
Optionally, the molar ratio of the catalyst auxiliary agent to the catalyst main agent is 0-1: 1, a step of; the mole ratio of HF to 1, 1-dichloroethylene is 2-50: the molar quantity of the 1, 1-dichloroethylene is 10-100% of the molar quantity of the catalyst main agent.
Optionally, the molar ratio of the catalyst auxiliary agent to the catalyst main agent is 0.4-0.6:1.
Optionally, the mol ratio of HF to 1, 1-dichloroethylene is 5-10:1, and the feeding mol amount of 1, 1-dichloroethylene is 30-50% of the mol amount of the catalyst main agent.
Optionally, the reaction time is 0.5-10 h. Further alternatively, the reaction temperature is 70-90 ℃ and the reaction time is 2-5 h.
Compared with the prior art, the invention has the following beneficial effects: the catalyst activity is adjustable, and the conversion rate of the raw material VDC is basically and completely converted; the selectivity of the product is high, and the selectivity of HCFC-142b is more than 97%; the catalyst can run continuously for 200 hours and has stable activity.
Drawings
FIG. 1 is a GC-MS spectrum of 1-chloro-1, 1-difluoroethane prepared in example 1.
Detailed Description
Unless specifically stated otherwise, scientific and technical terms herein have been understood based on the knowledge of one of ordinary skill in the relevant art. It should also be understood that the temperature, concentration referred to herein are approximations for purposes of illustration. Although methods and materials similar or equivalent to those described herein can be used in the practice of the present disclosure, some suitable methods and materials are described below. Publications, patent applications, patents, and other references mentioned herein are incorporated by reference in their entirety to the extent that any conflict arises. In addition, the materials, methods, solution concentrations, and examples are illustrative only and are not intended to be limiting. In a specific scheme, a person skilled in the art can optimize the material proportion, concentration and operation parameter values involved in the method according to the disclosure of the invention by adopting a conventional experimental period so as to achieve the purpose of the invention.
In the present invention, the operating pressure of the reaction is controlled mainly by the saturated vapor pressure of the reactants at the reaction temperature, and is not generally strictly controlled, and may be conducted at a pressure lower than, equal to, or higher than the atmospheric pressure, preferably at a pressure higher than the atmospheric pressure. In addition, the reaction of the invention can be operated intermittently or continuously, and the reaction itself has no obvious requirement on the reaction form.
On one hand, the selected catalyst auxiliary agent constructs a composite catalyst system with a catalyst main agent, adjusts the acidity of the catalyst system to be equivalent to the reaction requirement, ensures the performance of the composite catalyst to reach an optimal state, and obtains better conversion rate and selectivity; on the other hand, the unique property of the catalyst auxiliary agent and the synergistic effect of the reaction system play a role in preventing or delaying the self-polymerization of the 1, 1-dichloroethylene, and effectively prolong the service life of the catalyst.
The present invention is further illustrated by the following examples, which are not intended to limit the scope of the invention. The conversion and selectivity of the reactants in the examples below were measured by GC-MS.
Example 1:
HCFC-142b is prepared by liquid phase fluorination reaction and is carried out in a 100mL stainless steel autoclave with stirring; sequentially adding TiF into a reaction kettle 4 (12.4 g,0.1 mol), imidazole (1.36 g,0.02 mol), HF (20 g,1 mol) and VDC (5.8 g,0.06 mol) were added in one portion with stirring at 90℃for 5h; after the reaction, the sample was taken and subjected to gas chromatography after washing with water to remove the acid, which showed that the conversion of VDC was 99.9% and the selectivity of HCFC-142b was 97.9%.
The GC-MS detection result of the product 1-chloro-1, 1-difluoroethane is shown in figure 1, and the mass spectrum result and the peak value thereof are as follows: the presence of m/z100 as molecular ion peak and m/z85 as CF 2 Cl ion peak, m/z65 is CF 2 ClCH 3 Ion peak after Cl removal, m/z45 is CF 2 ClCH 3 Ion peaks after Cl and F removal. This data demonstrates that the product is 1-chloro-1, 1-difluoroethane.
Examples 2 to 5:
examples 2 to 5 liquid phase fluorination reactions HCFC-142b was prepared as in example 1, except that the kinds, reaction temperatures and reaction times of the composite catalysts were changed, and the reaction results were shown in Table 1.
TABLE 1
Example 6:
to a 100mL stainless steel autoclave with stirring was added 22.5g TiCl 4 Adding 50g of HF for fluorination treatment, starting stirring, removing generated HCl through a gas phase port, and controlling the pressure within 0.20 MPa; heating to 100 ℃, keeping the temperature for 2 hours, and ending the treatment process.
Imidazole (1.36 g,0.02 mol), n-butylamine (1.8 g,0.02 mol) and VDC (5.8 g,0.06 mol) were added into the reaction vessel in this order, the reaction temperature was 70℃and the temperature was lowered after 5 hours of reaction. The samples were analyzed by gas chromatography after washing with water to remove acid, which indicated a conversion of 99.5% of VDC and a selectivity of 97.0% for HCFC-142b.
Examples 7 to 9:
examples 7 to 9 liquid phase fluorination reactions HCFC-142b was prepared as in example 6, except that the kinds of composite catalysts were changed, and the reaction results were shown in Table 2.
TABLE 2
Examples 10 to 13:
examples 10-13 liquid phase fluorination preparation of HCFC-142b same as in example 1 except for the modification of imidazole and TiF 4 The ratio, reaction temperature and reaction time, and the reaction results are shown in Table 3.
TABLE 3 Table 3
Example 14:
the continuous liquid phase fluorination was carried out in a 2L autoclave of stainless steel equipped with stirring, equipped with a distillation column and reflux condenser above, and heated at the bottom with an oil pan.
123.4g of TiF are sequentially added into the reaction kettle 4 13.6g of imidazole, 18g of n-butylamine and 400g of HF, heating to 80 ℃, and keeping the temperature for 3 hours; VDC and HF were then continuously fed into the reactor by metering pumps at a VDC feed rate of 58g/h, HF feed rate of 26g/h, a reaction temperature of 75-85deg.C, and the reaction results shown in Table 4. As shown in Table 4, the conversion of VDC was maintained at 99.5% or more and the selectivity of HCFC-142b was-97.0% in 200 hours of continuous operation.
Table 4 catalyst life evaluation
Comparative examples 1 to 3:
comparative examples 1 to 3 liquid phase fluorination reactions HCFC-142b was prepared in the same manner as in example 6, except that the catalyst was of the kind and the reaction results were shown in Table 5.
TABLE 5
As is clear from the results, HCFC-142b selectivity was low using the catalysts of comparative examples 1 to 3.
The foregoing description is only a few examples of the present invention, and is not intended to limit the present invention in any way, and any simple modification, equivalent variations and modification of the above-described examples according to the technical principles of the present invention are within the scope of the present invention.
Claims (8)
1. A process for the preparation of 1-chloro-1, 1-difluoroethane, said process comprising: under the action of a composite catalyst and at the reaction temperature of 60-120 ℃, 1-dichloroethylene and HF are subjected to liquid phase fluorination to prepare 1-chloro-1, 1-difluoroethane; the composite catalyst consists of a catalyst main agent and a catalyst auxiliary agent, wherein the catalyst main agent is metal halide, and the catalyst auxiliary agent is organic amine; the metal halide is SnCl 4 、SnF 4 、TiCl 4 Or TiF 4 ；
The organic amine is one or more than two of triethylamine, n-butylamine, imidazole, isopropylamine and ethylenediamine.
2. The method for preparing 1-chloro-1, 1-difluoroethane according to claim 1, wherein the catalyst main agent is TiF 4 Or TiCl 4 。
3. The method for producing 1-chloro-1, 1-difluoroethane according to claim 1, wherein the organic amine is a mixture of one or both of imidazole and n-butylamine.
4. The process for producing 1-chloro-1, 1-difluoroethane according to claim 1, wherein the molar ratio of the catalyst auxiliary to the catalyst main is 0 to 1:1, a step of; the mole ratio of HF to 1, 1-dichloroethylene is 2-50: the molar quantity of the 1, 1-dichloroethylene is 10-100% of the molar quantity of the catalyst main agent.
5. The process for producing 1-chloro-1, 1-difluoroethane as claimed in claim 4, wherein the molar ratio of the catalyst auxiliary to the catalyst main is 0.4 to 0.6:1.
6. The process for producing 1-chloro-1, 1-difluoroethane as claimed in claim 4, wherein the molar ratio of HF to 1, 1-dichloroethylene is 5 to 10:1, and the molar amount of 1, 1-dichloroethylene is 30 to 50% of the molar amount of the catalyst host.
7. The process for producing 1-chloro-1, 1-difluoroethane according to claim 1, wherein the reaction time is 0.5 to 10 hours.
8. The process for producing 1-chloro-1, 1-difluoroethane according to claim 1, wherein the reaction temperature is 70 to 90 ℃ and the reaction time is 2 to 5 hours.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211040372.8A CN115417744B (en) | 2022-08-29 | 2022-08-29 | Method for preparing 1-chloro-1, 1-difluoroethane |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211040372.8A CN115417744B (en) | 2022-08-29 | 2022-08-29 | Method for preparing 1-chloro-1, 1-difluoroethane |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN115417744A CN115417744A (en) | 2022-12-02 |
| CN115417744B true CN115417744B (en) | 2023-09-08 |
Family
ID=84201283
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202211040372.8A Active CN115417744B (en) | 2022-08-29 | 2022-08-29 | Method for preparing 1-chloro-1, 1-difluoroethane |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115417744B (en) |
Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2636941A1 (en) * | 1988-09-26 | 1990-03-30 | Solvay | PROCESS FOR THE MANUFACTURE OF FLUORINATED HYDROCARBON |
| AU7883591A (en) * | 1990-06-08 | 1991-12-31 | Solvay | Method for preparing 1,1-dichloro-1-fluoroethane |
| US5336816A (en) * | 1992-12-17 | 1994-08-09 | Laroche Chemicals, Inc. | Method for preparing 1,1-dichloro-1-fluoroethane |
| FR2724929A1 (en) * | 1994-09-26 | 1996-03-29 | Solvay | PROCESS FOR THE MANUFACTURE OF 1,1,1-TRIHALOETHANES |
| CN1420110A (en) * | 2001-12-12 | 2003-05-28 | 苏州联氟化学有限公司 | Composite catalyst and process for preparing fluorohydrocarbon by liquid-phase fluorination |
| CN1569784A (en) * | 2004-04-30 | 2005-01-26 | 苏州联氟化学有限公司 | Process for preparing 1,1,1-trifluoroethane and 1,1,1-difluorochloroethane |
| CN1634816A (en) * | 2004-10-26 | 2005-07-06 | 苏州联氟化学有限公司 | Process for preparing 1,1,1-trifluoroethane and 1,1,1-difluoro chloroethane |
| RU2265007C1 (en) * | 2004-05-31 | 2005-11-27 | Орлов Александр Павлович | Method for isolation of 1-fluoro-1,1-dichloroethane, 1,1-difluoro-1-chloroethane, 1,1,1-trifluoroethane and hydrogen chloride from gas synthesis |
| CN112166097A (en) * | 2018-06-15 | 2021-01-01 | 阿科玛法国公司 | Bio-based vinylidene fluoride monomers and polymers comprising the same |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0723328B2 (en) * | 1985-01-09 | 1995-03-15 | 旭化成工業株式会社 | Method for producing fluorinated hydrocarbon |
-
2022
- 2022-08-29 CN CN202211040372.8A patent/CN115417744B/en active Active
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2636941A1 (en) * | 1988-09-26 | 1990-03-30 | Solvay | PROCESS FOR THE MANUFACTURE OF FLUORINATED HYDROCARBON |
| AU7883591A (en) * | 1990-06-08 | 1991-12-31 | Solvay | Method for preparing 1,1-dichloro-1-fluoroethane |
| US5336816A (en) * | 1992-12-17 | 1994-08-09 | Laroche Chemicals, Inc. | Method for preparing 1,1-dichloro-1-fluoroethane |
| FR2724929A1 (en) * | 1994-09-26 | 1996-03-29 | Solvay | PROCESS FOR THE MANUFACTURE OF 1,1,1-TRIHALOETHANES |
| CN1420110A (en) * | 2001-12-12 | 2003-05-28 | 苏州联氟化学有限公司 | Composite catalyst and process for preparing fluorohydrocarbon by liquid-phase fluorination |
| CN1569784A (en) * | 2004-04-30 | 2005-01-26 | 苏州联氟化学有限公司 | Process for preparing 1,1,1-trifluoroethane and 1,1,1-difluorochloroethane |
| RU2265007C1 (en) * | 2004-05-31 | 2005-11-27 | Орлов Александр Павлович | Method for isolation of 1-fluoro-1,1-dichloroethane, 1,1-difluoro-1-chloroethane, 1,1,1-trifluoroethane and hydrogen chloride from gas synthesis |
| CN1634816A (en) * | 2004-10-26 | 2005-07-06 | 苏州联氟化学有限公司 | Process for preparing 1,1,1-trifluoroethane and 1,1,1-difluoro chloroethane |
| CN112166097A (en) * | 2018-06-15 | 2021-01-01 | 阿科玛法国公司 | Bio-based vinylidene fluoride monomers and polymers comprising the same |
Non-Patent Citations (1)
| Title |
|---|
| Aluminum fluoride;Hart, Amy C.;e-EROS Encyclopedia of Reagents for Organic Synthesis;1-3 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN115417744A (en) | 2022-12-02 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102405202B (en) | Process for preparing 2-chloro-3,3,3-trifluoropropene | |
| EP2826766B1 (en) | Production method for 2,3,3,3-tetra-fluoropropene | |
| CN109180420A (en) | A kind of preparation method of 1,1- difluoroethylene | |
| CN103880590A (en) | Process for preparing 1,3,3,3-tetrafluoropropene | |
| CN110467595A (en) | A kind of no sulfuric acid process metaformaldehyde synthesizer and its synthesis route | |
| WO2020029753A1 (en) | Production process of 2,2-dimethyl-1,3-propanediol | |
| US9346724B2 (en) | Method for preparing 2,3,3,3-tetrafluoropropene | |
| CN104649862A (en) | Method and equipment for producing ethanol product by taking ethyl acetate as raw material | |
| CN115417744B (en) | Method for preparing 1-chloro-1, 1-difluoroethane | |
| JP2024501820A (en) | Continuous preparation system and method for vinylidene chloride | |
| JP5511026B2 (en) | Method for producing dichloropropanol using glycerol with improved selectivity for dichloropropanol | |
| CN110283043B (en) | Method for preparing 2-chloro-1, 1,1,4,4, 4-hexafluoro-2-butene | |
| CN114516780B (en) | Preparation method of 3,4, 5-trifluoro-bromobenzene | |
| CN114262255B (en) | Method for synthesizing trans-1, 4-hexafluoro-2-butene | |
| CN114213211A (en) | Preparation method of 1, 3-dichloro-1, 1-difluoropropane | |
| JP5045124B2 (en) | Reaction control method | |
| CN104326890B (en) | A kind of Carroll reacts continuous process method | |
| CN117263764A (en) | Separation method for improving stability of fluorobenzene | |
| CN112876351B (en) | Preparation method of paraphthaloyl chloride | |
| CN116023257B (en) | Continuous production method of high-purity propionyl chloride | |
| CN112552141B (en) | Preparation method of 2-chloro-1,1,1,4,4,4-hexafluoro-2-butene | |
| CN112724013B (en) | Preparation method of isophthaloyl dichloride | |
| EP3390589B1 (en) | Gtbe compositions, methods and installations for enhanced octane boosting | |
| CN110944971B (en) | Method for producing formic acid using low boiling point formate | |
| CN101186555A (en) | Method for simultaneously preparing 1,1,1,2-tetrafluoroethane and 1,1,1-trifluoroethane |
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 |