CN108516932A - The method that trichloro ethylene prepares trifluoro-acetyl chloride - Google Patents
The method that trichloro ethylene prepares trifluoro-acetyl chloride Download PDFInfo
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- CN108516932A CN108516932A CN201810532942.2A CN201810532942A CN108516932A CN 108516932 A CN108516932 A CN 108516932A CN 201810532942 A CN201810532942 A CN 201810532942A CN 108516932 A CN108516932 A CN 108516932A
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- acetyl chloride
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/58—Preparation of carboxylic acid halides
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
Abstract
The present invention relates to the preparation method of compound, method that especially a kind of trichloro ethylene prepares trifluoro-acetyl chloride；It the described method comprises the following steps：（1）The preparation of 1,1,1 trifluoro, 2,2 dichloroethanes：Trichloro ethylene is perfluorinated, mixed gas is obtained after thermal chlorination, and mixed gas, which enters, carries out catalytic chlorination reaction in the retort equipped with activated carbon, reaction temperature is 180 240 DEG C, and the speed ratio that chlorine and mixed gas are controlled during catalytic reaction is 1:10‑80；Gas is washed through scale after reaction, and fractionation obtains product；（2）The preparation of trifluoro-acetyl chloride；The preparation method of the present invention, it is simple for process, it is at low cost, reaction conversion ratio is high, and environmental pollution is small, and the present invention claims reactor, there are gas-phase spaces, and gas liquid film is to have light obstructing member, mercury lamp is completely immersed in light obstructing member hereinafter, the TFAC generated can be effectively prevent, by mercury lamp RADIATION DECOMPOSITION, to also avoid etching problem of the decomposition product to glass reactor and fluorescent tube in gas-phase space.
Description
Technical field
The present invention relates to the preparation method of compound, method that especially a kind of trichloro ethylene prepares trifluoro-acetyl chloride.
Background technology
Acid chloride group in TFAC can easily react with amine and alcohols material, generate amides and ester respectively
Class compound is a kind of important source material of synthetic pesticide and medicine.
Several methods that can be used for preparing TFAC have been disclosed.US3883407 is described and is radiated gas phase by ultraviolet lamp
Aoxidize 1,1,1- tri- fluoro- 2,2- dichloroethanes of the water content less than 0.1% and prepare TFAC, this reaction need in certain temperature and
It could be carried out under pressure, and think that this reaction is not suitable for carrying out in the liquid phase, since the hydrofluoric acid that side reaction generates can be rotten
Lose ultraviolet lamp tube.US5241113 is described and is made by using 1,1,1- tri- fluoro- 2,2- dichloroethanes of activated carbon catalysis oxidation
Standby TFAC, higher reaction temperature cause the carbon-to-carbon rupture in part material, poor selectivity.US5041647 is described logical
Peroxidating 1,1, tri- fluoro- 2,2- dichloroethanes of 1- prepare TFAC, but must make catalyst using water, to prevent office in reactor
Requirement of portion's overheat to stirring is also quite harsh, can be with trifluoroacetic acid (TFAA) while generating TFAC due to the presence of water
It generates, there is also difficulties for the separation between TFAC, TFAA and water three.US5259938 is described through liquid phase oxidation 1,1,1-
Three fluoro- 2,2- dichloroethanes prepare TFAC, and the part of 280nm is less than by filtering out light source medium wavelength, improves the choosing of reaction
Selecting property, while the etching problem of glass reactor is can avoid, require liquid phase material to be full of entire reactor in reaction, in reactor
There is no the buffering of gas-phase space, this is unsafe in the industrial production.
Invention content
The technical problem to be solved by the present invention is to：Overcome insufficient in the prior art, a kind of trichloro ethylene is provided and prepares trifluoro
The method of chloroacetic chloride.
To achieve the above object, the technical solution adopted by the present invention is as follows：
A kind of method that trichloro ethylene prepares trifluoro-acetyl chloride, the described method comprises the following steps：
（1）The preparation of 1,1,1- tri- fluoro- 2,2- dichloroethanes：Trichloro ethylene is perfluorinated, obtains mixed gas after thermal chlorination, mixes
Gas, which enters, carries out catalytic chlorination reaction in the retort equipped with activated carbon, reaction temperature is 180-240 DEG C, catalytic reaction process
The speed ratio of middle control chlorine and mixed gas is 1:10-80；Gas is washed through scale after reaction, and fractionation obtains product；
（2）The preparation of trifluoro-acetyl chloride：Step（1）In 1,1,1- tri- fluoro- 2,2- dichloroethanes obtained be transferred in retort,
It is continuously passed through oxygen and chlorine under stirring, is radiated by mercury lamp and carries out photochemical oxidation reaction, 1 vaporized in reaction, 1,1- tri-
Fluoro- 2,2- dichloroethanes is produced by continuing to participate in reaction in the condenser condensing reflux to reactor above reactor
Product trifluoro-acetyl chloride is discharged from condenser overhead, and by-product hydrogen chloride is absorbed by water absorption, unreacted chlorine by alkali cleaning
It is handled；The liquid level constant of tri- fluoro- 2,2- dichloroethanes of 1,1,1- in retort is maintained simultaneously.
Preferably, the activated carbon is Alveolate activated carbon, and the shaped activated carbon uses hydrofluoric acid solution in room temperature in advance
Lower immersion treatment 24-48h, is then cleaned with distilled water, dry in drying box after cleaning, is removed moisture, is then used nitrogen
Gas further removes moisture removal or ashes, then activates 24-36h with chlorine.
Preferably, there is light obstructing member in the retort below gas liquid film, the light obstructing member is using corrosion resistant
Black-out cloth, the black-out cloth are located at the outside of retort.
Preferably, the mercury lamp is inserted into from the top of retort.
Preferably, the reflux temperature in the retort is 120-130 DEG C, reflux ratio 2.5-3.
Preferably, the step（2）The liquid level constant of tri- fluoro- 2,2- dichloroethanes of 1,1,1- uses in middle maintenance retort
Catheter imports.
The advantageous effect of technical solution using the present invention is：
1, preparation method of the invention, simple process and low cost, reaction conversion ratio is high, and environmental pollution is small；
2, the present invention claims reactor, there are gas-phase spaces, and gas liquid film, to have light obstructing member, mercury lamp is completely immersed in
Light obstructing member is hereinafter, can effectively prevent the TFAC generated, by mercury lamp RADIATION DECOMPOSITION, to also avoid decomposition product pair in gas-phase space
The etching problem of glass reactor and fluorescent tube.
Specific implementation mode
The following examples can make those skilled in the art that the present invention be more fully understood, but these embodiments are not
Limiting the scope of the invention." one embodiment " or " embodiment " referred to herein refers to that may be included in the present invention at least
A particular feature, structure, or characteristic in one realization method.In the present specification different places occur " in one embodiment
In " the same embodiment not is referred both to, nor the individual or selective embodiment mutually exclusive with other embodiment.
Embodiment 1
A kind of method that trichloro ethylene prepares trifluoro-acetyl chloride, includes the following steps：
（1）The preparation of 1,1,1- tri- fluoro- 2,2- dichloroethanes：Trichloro ethylene is perfluorinated, obtains mixed gas after thermal chlorination, mixes
Gas, which enters, carries out catalytic chlorination reaction in the retort equipped with activated carbon, reaction temperature is 180-240 DEG C, catalytic reaction process
The speed ratio of middle control chlorine and mixed gas is 1:10-80；Gas is washed through scale after reaction, and fractionation obtains product；Activity
Charcoal is Alveolate activated carbon, and shaped activated carbon uses hydrofluoric acid solution immersion treatment 24-48h at room temperature in advance, then with distillation
Water is cleaned, dry in drying box after cleaning, is removed moisture, moisture removal or ashes is then further removed with nitrogen, then use
Chlorine activates 24-36h；
（2）The preparation of trifluoro-acetyl chloride：Step（1）In 1,1,1- tri- fluoro- 2,2- dichloroethanes obtained be transferred in retort,
It is continuously passed through oxygen and chlorine under stirring, is radiated by mercury lamp and carries out photochemical oxidation reaction, mercury lamp 500w is vaporized in reaction
Tri- fluoro- 2,2- dichloroethanes of 1,1,1- by continuing to join in the condenser condensing reflux to reactor above reactor
With react, product trifluoro-acetyl chloride is discharged from condenser overhead, and by-product hydrogen chloride passed through by water absorption, unreacted chlorine
Alkali cleaning absorption is handled；The liquid level constant of tri- fluoro- 2,2- dichloroethanes of 1,1,1- in retort is maintained simultaneously.Gas in retort
There are light obstructing member, the light obstructing member that corrosion resistant black-out cloth, the black-out cloth is used to be located at retort below liquid interface
Outside；Mercury lamp is inserted into from the top of retort；Reflux temperature in retort is 120-130 DEG C, reflux ratio 2.5-3.It maintains
The liquid level constant of tri- fluoro- 2,2- dichloroethanes of 1,1,1- is imported using catheter in retort.
Reaction closes mercury lamp after 5 hours, and reaction terminates.Experimental analysis instrument is given birth to for Zhejiang Fu Li Analytical Instrument Co., Ltd
The GC9790J type gas chromatographs with thermal conductivity detector (TCD) of production, chromatographic column are produced using Lanzhou Chemical Physics research institute of the Chinese Academy of Sciences
SP1000 type chromatographic columns, raw material purity >=99.9% after gas chromatographic analysis, in addition to raw material, oxygen, chlorine in gas-phase product
Gas and the external TFAC of hydrogen chloride gas account for 97.3%, and symbiosis is at 0.97molTFAC.Tri- fluoro- 2,2- dichloroethanes of 1,1,1- in the liquid of bottom
Content 95.14%, by-product CFC-113a4.94%.The glass such as several post-reactors of successive reaction, reflux condensing tube are found no
Corrosion phenomenon.
Embodiment 2
Embodiment 2 is reacted with experiment 1 the difference is that be not added with barn door below 2 gas liquid film of embodiment, other conditions with
Test it is 1 identical, in addition to raw material, oxygen, chlorine and the external TFAC of hydrogen chloride gas account for 90% in gas-phase product, symbiosis at
0.95molTFAC.1,1,1- tri- fluoro- 2,2- dichloroethane contents 94.14%, by-product CFC-113a6.78% in the liquid of bottom.Reaction
Find there is glass corrosion phenomenon at device gas liquid film and gas phase position, condensing reflux pipe.
Embodiment 3
In embodiment 3 reaction with experiment 1 the difference is that mercury lamp power in embodiment 3 is 200w, other conditions and experiment 1
Identical, in addition to raw material, oxygen, chlorine and the external TFAC of hydrogen chloride gas account for 96% in gas-phase product, symbiosis is at 0.92molTFAC.
1,1,1- tri- fluoro- 2,2- dichloroethane contents 94.32%, by-product CFC-113a5.65% in the liquid of bottom.The glass such as reactor, condenser pipe
Glass finds no corrosion phenomenon.
It is enlightenment with above-mentioned desirable embodiment according to the present invention, through the above description, relevant staff is complete
Various changes and amendments can be carried out without departing from the scope of the technological thought of the present invention' entirely.All essences in the present invention
With within principle, any modification, equivalent substitution, improvement and etc. done should all be included in the protection scope of the present invention god.This
The technical scope of item invention is not limited to the contents of the specification, it is necessary to determine its technology according to right
Property range.
Claims (6)
1. a kind of method that trichloro ethylene prepares trifluoro-acetyl chloride, it is characterised in that：It the described method comprises the following steps：
（1）The preparation of 1,1,1- tri- fluoro- 2,2- dichloroethanes：Trichloro ethylene is perfluorinated, obtains mixed gas after thermal chlorination, mixes
Gas, which enters, carries out catalytic chlorination reaction in the retort equipped with activated carbon, reaction temperature is 180-240 DEG C, catalytic reaction process
The speed ratio of middle control chlorine and mixed gas is 1:10-80；Gas is washed through scale after reaction, and fractionation obtains product；
（2）The preparation of trifluoro-acetyl chloride：Step（1）In 1,1,1- tri- fluoro- 2,2- dichloroethanes obtained be transferred in retort,
It is continuously passed through oxygen and chlorine under stirring, is radiated by mercury lamp and carries out photochemical oxidation reaction, 1 vaporized in reaction, 1,1- tri-
Fluoro- 2,2- dichloroethanes is produced by continuing to participate in reaction in the condenser condensing reflux to reactor above reactor
Product trifluoro-acetyl chloride is discharged from condenser overhead, and by-product hydrogen chloride is absorbed by water absorption, unreacted chlorine by alkali cleaning
It is handled；The liquid level constant of tri- fluoro- 2,2- dichloroethanes of 1,1,1- in retort is maintained simultaneously.
2. the method that trichloro ethylene according to claim 1 prepares trifluoro-acetyl chloride, it is characterised in that：The activated carbon is
Alveolate activated carbon, the shaped activated carbon use hydrofluoric acid solution immersion treatment 24-48h at room temperature in advance, then with distillation
Water is cleaned, dry in drying box after cleaning, is removed moisture, moisture removal or ashes is then further removed with nitrogen, then use
Chlorine activates 24-36h.
3. the method that trichloro ethylene according to claim 1 prepares trifluoro-acetyl chloride, it is characterised in that：In the retort
There are light obstructing member, the light obstructing member that corrosion resistant black-out cloth, the black-out cloth is used to be located at retort below gas liquid film
Outside.
4. the method that trichloro ethylene according to claim 1 prepares trifluoro-acetyl chloride, it is characterised in that：The mercury lamp is from anti-
The top of tank is answered to be inserted into.
5. the method that trichloro ethylene according to claim 1 prepares trifluoro-acetyl chloride, it is characterised in that：In the retort
Reflux temperature be 120-130 DEG C, reflux ratio 2.5-3.
6. the method that trichloro ethylene according to claim 1 prepares trifluoro-acetyl chloride, it is characterised in that：The step（2）
The liquid level constant of tri- fluoro- 2,2- dichloroethanes of 1,1,1- is imported using catheter in middle maintenance retort.
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| CN201810532942.2A CN108516932A (en) | 2018-05-29 | 2018-05-29 | The method that trichloro ethylene prepares trifluoro-acetyl chloride |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2020057013A1 (en) * | 2018-09-20 | 2020-03-26 | 浙江衢化氟化学有限公司 | Photooxidation preparation method for halo acetyl chloride |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0659729A1 (en) * | 1993-12-23 | 1995-06-28 | Solvay Fluor und Derivate GmbH | Process for preparing chlorides of polyfluorochloro- and perfluoro carboxylic acids in the presence of chlorine |
| CN1312241A (en) * | 2000-02-29 | 2001-09-12 | 阿托菲纳公司 | preparation for 1,1,1,-trifluoro-2,2-dichloroethane |
| CN1644575A (en) * | 2004-09-01 | 2005-07-27 | 浙江蓝天环保高科技股份有限公司 | Preparation of high purity, 1,1,1-trifluoro-2,2,-dichloroethane |
| CN101735034A (en) * | 2009-12-18 | 2010-06-16 | 杭州原正化学工程技术装备有限公司 | Method for preparing trifluoroacetyl chloride |
| CN101735033A (en) * | 2009-12-18 | 2010-06-16 | 杭州原正化学工程技术装备有限公司 | Method for preparing trifluoroacetyl chloride from 2,2-dichloro-1,1,1-trifluoroethane |
| CN106892813A (en) * | 2015-12-17 | 2017-06-27 | 浙江蓝天环保高科技股份有限公司 | A kind of method that difluoro chloracetyl chloride is prepared by gas phase photooxidation reaction |
-
2018
- 2018-05-29 CN CN201810532942.2A patent/CN108516932A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0659729A1 (en) * | 1993-12-23 | 1995-06-28 | Solvay Fluor und Derivate GmbH | Process for preparing chlorides of polyfluorochloro- and perfluoro carboxylic acids in the presence of chlorine |
| CN1312241A (en) * | 2000-02-29 | 2001-09-12 | 阿托菲纳公司 | preparation for 1,1,1,-trifluoro-2,2-dichloroethane |
| CN1644575A (en) * | 2004-09-01 | 2005-07-27 | 浙江蓝天环保高科技股份有限公司 | Preparation of high purity, 1,1,1-trifluoro-2,2,-dichloroethane |
| CN101735034A (en) * | 2009-12-18 | 2010-06-16 | 杭州原正化学工程技术装备有限公司 | Method for preparing trifluoroacetyl chloride |
| CN101735033A (en) * | 2009-12-18 | 2010-06-16 | 杭州原正化学工程技术装备有限公司 | Method for preparing trifluoroacetyl chloride from 2,2-dichloro-1,1,1-trifluoroethane |
| CN106892813A (en) * | 2015-12-17 | 2017-06-27 | 浙江蓝天环保高科技股份有限公司 | A kind of method that difluoro chloracetyl chloride is prepared by gas phase photooxidation reaction |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2020057013A1 (en) * | 2018-09-20 | 2020-03-26 | 浙江衢化氟化学有限公司 | Photooxidation preparation method for halo acetyl chloride |
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Application publication date: 20180911 |