CN106831406B - A kind of method and device of two fluoracyl fluorides of nonmetal catalyzed preparation - Google Patents
A kind of method and device of two fluoracyl fluorides of nonmetal catalyzed preparation Download PDFInfo
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- CN106831406B CN106831406B CN201710078031.2A CN201710078031A CN106831406B CN 106831406 B CN106831406 B CN 106831406B CN 201710078031 A CN201710078031 A CN 201710078031A CN 106831406 B CN106831406 B CN 106831406B
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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
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/14—Preparation of carboxylic acid esters from carboxylic acid halides
Abstract
The present invention provides a kind of method and devices of two fluoracyl fluorides of nonmetal catalyzed preparation.This method utilizes N doping catalyst, with 1,1,2,2- tetrafluoro ethyl etherate for raw material；Under 160~240 DEG C of gas phases of reaction temperature, reaction velocity be 50~200h‑1Under the conditions of reacted, generate two fluoracyl fluorides.Two fluoracyl fluorides of the generation can further be converted into ethyl difluoro with ethanol synthesis by importing in ethanol solution.The present invention avoids proposing environmentally protective non-metallic catalyst using catalyst such as traditional solid acids, good reaction selectivity, and raw material availability is high, and product purity is high, easy to industrialized production.
Description
Technical field
The invention belongs to Organic fluoride chemical technology fields, and in particular to a kind of side of two fluoracyl fluorides of nonmetal catalyzed preparation
Method and device.
Background technique
Ethyl difluoro can be prepared using two fluoracyl fluorides, ethyl difluoro is very important industrial chemicals,
Medicine preparation, pesticide synthesis etc. extensive application.US005710317A discloses a kind of preparation side of two fluoracyl fluorides
Method, by 1- alkoxy -1,1,2,2- tetrafluoroethane are reacted through metal oxide oxidation catalyst to be made, but its stability is to be improved.
US8299300 discloses a kind of preparation method of two fluoracyl fluorides, utilizes hydrofluoric acid displacement dichloroacetyl using chromium-based catalysts
Chlorine.The raw material and product of this reaction have stronger corrosivity, it is difficult to industrialize.CN105523915 discloses a kind of two acetyl fluorides
The preparation method of fluorine, this method are supported on γ-Al with two kinds or more of rare earth perfluor hydrochlorate2O3It, can be or on zeolite molecular sieve
Tetra- fluoro ethyl alkyl ether of 1,1,2,2- is cracked under lower temperature.
Currently, the preparation process of two fluoracyl fluorides is there is process flow length, raw material or by-product corrosivity are strong, react steady
The problems such as qualitative poor, activity is low, catalyst is at high cost, it is difficult to realize industrialization.
Summary of the invention
It is an object of the present invention to provide the methods of a kind of two fluoracyl fluorides of nonmetal catalyzed preparation and ethyl difluoro.
The two fluoracyl fluoride preparation methods that new corrosivity is weak, product purity is high, catalyst toxicity is small, reaction stability is good are had developed,
Suitable for industrialized production.
Present invention technical solution used for the above purpose is as follows:
The method of two fluoracyl fluorides of nonmetal catalyzed preparation provided by the invention are as follows: be with 1,1,2,2- tetrafluoro ethyl etherate
Raw material, it is pre- it is thermal evaporation after, in the presence of nitrogen-dopped activated carbon catalyst, in 160~240 DEG C of gas phase reactions of temperature, reaction pressure
For normal pressure, reaction velocity is 50~200h-1, carry out reaction under the conditions of nitrogen protection and generate two fluoracyl fluorides.
Preferably, the preheating temperature is 160~200 DEG C.
Preferably, the nitrogen-dopped activated carbon catalyst is immersed on absorbent charcoal carrier for nitrogen compound and is made, the nitrogen
Compound is ammonium chloride, urea, imidazoles, polyvinylpyrrolidone, one or more of in melamine.
Preferably, nitrogen compound doping is preferably 5~20wt% in the nitrogen-dopped activated carbon catalyst.
Preferably, the nitrogen-dopped activated carbon catalyst makes as follows:
Using active carbon as carrier；Nitrogen compound is dissolved in solvent, nitrogen compound solution is obtained；By absorbent charcoal carrier
Be placed in nitrogen compound solution, be sufficiently impregnated under vacuum, rotate out excess of solvent, 80~120 DEG C dry 2~6 hours, then
Obtain the nitrogen-dopped activated carbon catalyst within charing 4~8 hours for 500~900 DEG C under nitrogen protection.
Preferably, the solvent be water, ethyl alcohol, ethylene glycol or propylene glycol, vacuum impregnation 1~8 hour.
Preferably, reaction temperature is 160~240 DEG C, and reaction velocity is 80~140h-1。
The present invention also provides a kind of nonmetal catalyzed methods for preparing ethyl difluoro, and this method comprises the following steps:
Step 1, with 1,1,2,2- tetrafluoro ethyl etherate for raw material, it is pre- it is thermal evaporation after, using nitrogen-dopped activated carbon catalyst,
Under normal pressure, temperature is 160~240 DEG C, and reaction velocity is 50~200h-1Catalysis reaction is carried out under the conditions of nitrogen protection generates two
Fluoracyl fluoride gas；
Step 2, two fluoracyl fluoride gases of aforementioned generation are passed through in ethanol solution and carry out reaction generation difluoroacetic acid second
Ester.
In technical solution of the present invention, a kind of method of two fluoracyl fluorides of nonmetal catalyzed cracking preparation is loaded into nitrogen and mixes
The fixed bed reactors of miscellaneous catalyst are passed through nitrogen and are heated to 160~240 DEG C, 1,1,2,2- tetrafluoro after being then introduced into preheating
Ethyl etherate carries out catalysis reaction under the conditions of 160~240 DEG C of reaction temperature and reaction velocity are 80~140h-1, generates two
Fluoracyl fluoride, two fluoracyl fluorides import ethanol solution and ethanol synthesis generates ethyl difluoro.
The present invention also provides a kind of device of two fluoracyl fluorides of nonmetal catalyzed preparation, the device include: gas purifier,
Piston pump, head tank, preheating chamber, check valve, fixed bed reactors, double sections of temperature control thermocouples, crystal reaction tube, refrigerated separation dress
It sets, collection of products device；
The gas purifier is connect with fixed bed reactors, and gas purifier is for purifying nitrogen, after purification
Nitrogen by pipeline to fixed bed reactors；
The head tank is connected with piston pump intake, and piston pump discharge is connected with preheating chamber, and 1,1,2,2- in head tank
Tetrafluoro ethyl etherate raw material enters preheating chamber by piston pump；
The preheating chamber is connected with check valve, and the check valve other end is connected to fixed bed reactors；After preheating chamber preheating
1,1,2,2- tetrafluoro ethyl etherate raw material fixed bed reactors are entered by check valve；
Double section temperature control thermocouples and crystal reaction tube are set in fixed bed reactors, and the crystal reaction tube is built-in
Nitrogen-dopped activated carbon catalyst is carried, double section temperature control thermocouples are used for heating in reactor；
The outlet of the fixed bed reactors is connected to refrigerated separation device, and the other end of refrigerated separation device is connected to production
Object collection device；Reaction product in the fixed bed reactors be delivered to refrigerated separation device carry out condensation be directly entered product
Collection device.
Compared with prior art, beneficial effects of the present invention are as follows:
1, the nitrogen-dopped activated carbon catalyst that the present invention uses is non-metallic catalyst, and carrier selects activity cheap and easy to get
Charcoal, there is no Heavy metals cause poison pollute the problem of, and under optimum condition catalytic activity be able to maintain stablize it is longer when
Between.Reaction raw materials and catalyst involved in reaction are using prior art preparation or commercially available, easily realization industrialization.
2, the process corrosivity that the present invention prepares two fluoracyl fluorides is weak, product purity is high, catalyst toxicity is small, reaction
Two good fluoracyl fluoride preparation methods of stability are suitable for industrialized production.
Detailed description of the invention
Fig. 1 is the structural schematic diagram of two fluoracyl fluoride devices of nonmetal catalyzed preparation in the present invention.
Specific embodiment
Technical solution of the present invention is described in detail below with reference to embodiment.The reagent and raw material used below be not as
It illustrates, is commercially produced product.
Referring to Fig. 1, which is the structural schematic diagram that catalyst of the present invention prepares two fluoracyl fluoride devices, is implemented below
Catalytic cracking reaction involved in example is all made of the device.As shown in Figure 1, the device include: gas purifier 1, piston pump 2,
Head tank 3, preheating chamber 4, check valve 5, fixed bed reactors 6, double sections of temperature control thermocouples 7, crystal reaction tube 8, refrigerated separation dress
Set 9 and collection of products device 10.The piston pump 2 is used with hop controller, accurate to control feedstock amount.Fixed bed reactors
6 adjust reaction temperature, 8 loading catalyst of inner quartz reaction tube by double sections of temperature control thermocouples 7.Refrigerated separation device 9 will react
The high-temperature gas of device output is cooled to -10~20 DEG C, and unreacted raw material and two fluoracyl fluorides are collected in collection of products device 10.
Gas purifier 1 is connect with fixed bed reactors 6, and for purifying to nitrogen, purified nitrogen passes through gas purifier 1
Pipeline is to fixed bed reactors 6.The head tank 3 is connected with 2 entrance of piston pump, the outlet of piston pump 2 and 4 phase of preheating chamber
Even, 1,1,2,2- tetrafluoro ethyl etherate raw material in head tank 3 enters preheating chamber 4 by piston pump 2.Preheating chamber 4 and check valve 5
It is connected, 5 other end of check valve is connected to fixed bed reactors 6；1,1,2,2- tetrafluoro ethyl etherate after the preheating of preheating chamber 4 is former
Material enters fixed bed reactors 6 by check valve 5.Double sections of temperature control thermocouples 7 and crystal reaction tube 8 are set to fixed bed reactors
In 6, nitrogen-dopped activated carbon catalyst is loaded in crystal reaction tube 8, double sections of temperature control thermocouples 7 are used for adding in reactor
Heat；The outlet of fixed bed reactors 6 is connected to refrigerated separation device 9, and the other end of refrigerated separation device 9 is connected to collection of products
Device 10；Reaction product in fixed bed reactors 6 be delivered to refrigerated separation device 9 carry out condensation be directly entered collection of products dress
Set 10.
Embodiment 1
The preparation of nitrogen-dopped activated carbon catalyst.
It takes 8.82g urea to be dissolved in 100mL deionized water and is made into certain density solution, be placed in 500mL eggplant type flask,
Then 100g active carbon is added, is impregnated 3 hours at vacuum degree 0.1MPa, excludes excess of solvent using Rotary Evaporators, is placed in
Dried in 120 DEG C of baking ovens, after in tube furnace, nitrogen atmosphere it is lower 700 DEG C carbonize 5 hours, obtain N doping catalyst U-AC.
Embodiment 2
The preparation of nitrogen-dopped activated carbon catalyst.
It takes 5.68g imidazoles to be dissolved in 70mL ethyl alcohol and is made into certain density solution, be placed in 250mL eggplant type flask, then
60g active carbon is added, is impregnated 4 hours at vacuum degree 0.1MPa, excludes excess of solvent using Rotary Evaporators, is placed in 120 DEG C
Dried in baking oven, after in tube furnace, nitrogen atmosphere it is lower 800 DEG C carbonize 6 hours, obtain N doping catalyst IM-AC.
Embodiment 3
The preparation of nitrogen-dopped activated carbon catalyst.
It takes 3.17g melamine to be dissolved in 50mL ethylene glycol and is made into certain density solution, be placed in 250mL eggplant type flask
In, 50g active carbon is then added, is impregnated 2 hours at vacuum degree 0.1MPa, excludes excess of solvent using Rotary Evaporators, sets
Dried in 120 DEG C of baking ovens, after in tube furnace, nitrogen atmosphere it is lower 600 DEG C carbonize 7 hours, obtain N doping catalyst Mel-AC.
Embodiment 4
The preparation of nitrogen-dopped activated carbon catalyst.
It takes 15.61g polyvinylpyrrolidone to be dissolved in 100mL propylene glycol and is made into certain density solution, be placed in 500mL eggplant
In type flask, 90g active carbon is then added, is impregnated 3 hours at vacuum degree 0.1MPa, is excluded using Rotary Evaporators extra molten
Agent is placed in 120 DEG C of baking ovens and dries, after in tube furnace, nitrogen atmosphere it is lower 900 DEG C carbonize 4 hours, obtain N doping catalyst
PVP-AC。
Embodiment 5
Catalytic pyrolysis 1,1,2,2- tetrafluoro ethyl etherate prepares two fluoracyl fluorides
28mL N doping catalyst U-AC, fixed bed reactors are filled in crystal reaction tube (17mm Φ × 750mm L)
Electric furnace is arranged under the nitrogen for being passed through 50mL/min to be heated to 180 DEG C with the rate of 5 DEG C/min and maintain 60min.Stop afterwards logical
Enter nitrogen, imports preheated 1,1,2,2- tetrafluoro ethyl etherate of raw material, it is 100h that control raw material flow, which keeps reaction velocity,-1,
Start to collect when there is condensate liquid and utilizes chromatogram ration analysis.The result shows that the reaction conversion ratio is 28.2%, choosing
Selecting property is 97.6%.Reaction condition is kept, sustained response is analyzed again after for 24 hours, reaction conversion ratio 28.8%, selectivity
It is 97.7%
Embodiment 6
Catalytic pyrolysis 1,1,2,2- tetrafluoro ethyl etherate prepares two fluoracyl fluorides
32mL doping type catalyst IM-AC, fixed bed reactors are filled in crystal reaction tube (17mm Φ × 750mm L)
Electric furnace is arranged under the nitrogen for being passed through 80mL/min to be heated to 220 DEG C with the rate of 5 DEG C/min and maintain 60min.Stop afterwards logical
Enter nitrogen, imports preheated 1,1,2,2- tetrafluoro ethyl etherate of raw material, it is 130h that control raw material flow, which keeps reaction velocity,-1,
Start to collect when there is condensate liquid and utilizes chromatogram ration analysis.The result shows that the reaction conversion ratio is 35.3%, choosing
Selecting property is 98.5%.Reaction condition is kept, is analyzed again after sustained response 48h, reaction conversion ratio 36.1%, selectivity
It is 98.7%
Embodiment 7
A kind of method that catalytic pyrolysis 1,1,2,2- tetrafluoro ethyl etherate prepares two fluoracyl fluorides.
30mL doping type catalyst Mel-AC, fixed bed reaction are filled in crystal reaction tube (17mm Φ × 750mm L)
Electric furnace is arranged under the nitrogen for being passed through 70mL/min and is heated to 200 DEG C with the rate of 5 DEG C/min and maintains 60min for device.After stop
It is passed through nitrogen, imports preheated 1,1,2,2- tetrafluoro ethyl etherate of raw material, it is 80h that control raw material flow, which keeps reaction velocity,-1,
Start to collect when there is condensate liquid and utilizes chromatogram ration analysis.The result shows that the reaction conversion ratio is 32.8%, choosing
Selecting property is 99.1%.Reaction condition is kept, is analyzed again after sustained response 48h, reaction conversion ratio 32.3%, selectivity
It is 98.5%
Embodiment 8
A kind of method that catalytic pyrolysis 1,1,2,2- tetrafluoro ethyl etherate prepares two fluoracyl fluorides.
30mL doping type catalyst PVP-AC, fixed bed reaction are filled in crystal reaction tube (17mm Φ × 750mm L)
Electric furnace is arranged under the nitrogen for being passed through 100mL/min and is heated to 210 DEG C with the rate of 5 DEG C/min and maintains 60min for device.After stop
It is passed through nitrogen, imports preheated 1,1,2,2- tetrafluoro ethyl etherate of raw material, it is 150h that control raw material flow, which keeps reaction velocity,-1, start to collect when there is condensate liquid and utilize chromatogram ration analysis.The result shows that the reaction conversion ratio is 29.4%,
Selectivity is 98.7%.Reaction condition is kept, is analyzed again after sustained response 36h, reaction conversion ratio 27.1%, selection
Property is 97.3%
It above are only part preferred embodiment of the invention, the present invention is not limited in the content of embodiment.For ability
For technical staff in domain, can there are various change and change in the conception range of technical solution of the present invention, made
What changes and change, within that scope of the present invention.
Claims (5)
1. a kind of method of two fluoracyl fluorides of nonmetal catalyzed preparation, this method are as follows: with 1,1,2,2- tetrafluoro ethyl etherate be original
Material, it is pre- it is thermal evaporation after, using nitrogen-dopped activated carbon catalyst, under normal pressure, temperature be 160~240 DEG C, reaction velocity be 50~
200h-1Catalysis is carried out under the conditions of nitrogen protection reacts obtained two fluoracyl fluorides；The nitrogen-dopped activated carbon catalyst is nitrification
Object is immersed on absorbent charcoal carrier and is made, and the nitrogen compound is ammonium chloride, urea, imidazoles, polyvinylpyrrolidone, melamine
It is one or more of in amine；Nitrogen compound doping is 5~20wt% in the nitrogen-dopped activated carbon catalyst.
2. a kind of method of two fluoracyl fluorides of nonmetal catalyzed preparation as described in claim 1, it is characterised in that: described 1,1,
The temperature of 2,2- tetrafluoro ethyl etherate raw material preheating is 120~200 DEG C.
3. a kind of method of two fluoracyl fluorides of nonmetal catalyzed preparation as described in claim 1, which is characterized in that the nitrogen is mixed
The specific of miscellaneous activated-carbon catalyst obtains nitrogen compound solution the preparation method comprises the following steps: nitrogen compound solution is dissolved in solvent, institute
Stating solvent is water, ethyl alcohol, ethylene glycol or propylene glycol；Absorbent charcoal carrier is placed in the nitrogen compound solution, vacuum impregnation 1~
8 hours, excess of solvent is rotated out, is dried at 80~120 DEG C 2~6 hours, then 500~900 DEG C of charings 4 under nitrogen protection
Obtain the nitrogen-dopped activated carbon catalyst within~8 hours.
4. a kind of method of two fluoracyl fluorides of nonmetal catalyzed preparation as described in claim 1, it is characterised in that: will fill in advance
The reactor of good nitrogen-dopped activated carbon catalyst is passed through nitrogen and is heated to 160~240 DEG C, is then introduced into pre- thermal evaporation 1,1,
2,2- tetrafluoro ethyl etherate carries out catalysis reaction.
5. a kind of nonmetal catalyzed method for preparing ethyl difluoro, this method comprises the following steps:
Step 1, with 1,1,2,2- tetrafluoro ethyl etherate be raw material, it is pre- it is thermal evaporation after, using nitrogen-dopped activated carbon catalyst, normal
Pressure, temperature are 160~240 DEG C, and reaction velocity is 50~200h-1Catalysis reaction is carried out under the conditions of nitrogen protection generates difluoro second
Acyl fluorides gas；The nitrogen-dopped activated carbon catalyst is immersed on absorbent charcoal carrier for nitrogen compound and is made, the nitrogen compound
It is one or more of in ammonium chloride, urea, imidazoles, polyvinylpyrrolidone, melamine；The nitrogen-dopped activated carbon catalyst
Middle nitrogen compound doping is 5~20wt%；
Step 2, two fluoracyl fluoride gases of aforementioned generation are passed through in ethanol solution and carry out reaction generation ethyl difluoro.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2010064999A (en) * | 2008-09-12 | 2010-03-25 | Central Glass Co Ltd | Method for producing difluoroacetic acid fluoride |
| CN102762525A (en) * | 2010-02-17 | 2012-10-31 | 中央硝子株式会社 | Method for producing semiconductor gas |
| CN104289246A (en) * | 2014-10-11 | 2015-01-21 | 中国科学院上海高等研究院 | Novel mercury-free catalyst and application of mercury-free catalyst in synthesis of vinyl chloride |
| CN105461560A (en) * | 2015-12-31 | 2016-04-06 | 天津市长芦化工新材料有限公司 | Synthesizing method for ethyl difluoroacetate |
| CN105523915A (en) * | 2015-12-21 | 2016-04-27 | 山东东岳高分子材料有限公司 | Method for high-yield gas-phase catalytic cracking preparation of difluoroacetyl fluoride |
-
2017
- 2017-02-14 CN CN201710078031.2A patent/CN106831406B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2010064999A (en) * | 2008-09-12 | 2010-03-25 | Central Glass Co Ltd | Method for producing difluoroacetic acid fluoride |
| CN102762525A (en) * | 2010-02-17 | 2012-10-31 | 中央硝子株式会社 | Method for producing semiconductor gas |
| CN104289246A (en) * | 2014-10-11 | 2015-01-21 | 中国科学院上海高等研究院 | Novel mercury-free catalyst and application of mercury-free catalyst in synthesis of vinyl chloride |
| CN105523915A (en) * | 2015-12-21 | 2016-04-27 | 山东东岳高分子材料有限公司 | Method for high-yield gas-phase catalytic cracking preparation of difluoroacetyl fluoride |
| CN105461560A (en) * | 2015-12-31 | 2016-04-06 | 天津市长芦化工新材料有限公司 | Synthesizing method for ethyl difluoroacetate |
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