CN107739298A - The preparation method and device of a kind of difluoroethanol - Google Patents
The preparation method and device of a kind of difluoroethanol Download PDFInfo
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- CN107739298A CN107739298A CN201710968662.1A CN201710968662A CN107739298A CN 107739298 A CN107739298 A CN 107739298A CN 201710968662 A CN201710968662 A CN 201710968662A CN 107739298 A CN107739298 A CN 107739298A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/09—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrolysis
- C07C29/12—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrolysis of esters of mineral acids
- C07C29/124—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrolysis of esters of mineral acids of halides
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Abstract
The present invention relates to a kind of preparation method of difluoroethanol and device.The preparation method and device of the difluoroethanol, solvent and potassium hydroxide reaction generation intermediate product in closed reactor, then 2 excessive chlorine 1 are slowly introducing into reactor, 1 Difluoroethane, it is 2,2 difluoroethanols that can obtain high-purity by product progress separating-purifying after reacting a period of time.The present invention is using the Difluoroethane of 2 chlorine 1,1 production difluoroethanol, and raw material is the accessory substance of the Difluoroethane of 1 chlorine 1,1, and raw material is easy to get, cost is low；Reaction condition is gentle, accessory substance is few, environmentally safe.
Description
Technical field
The present invention relates to a kind of preparation method of difluoroethanol and device.
Background technology
Difluoroethanol is mainly used in the fields such as synthesis fluorine-containing medicines, agricultural chemicals and dyestuff.2,2- difluoroethanols are a kind of weights
The aliphatic fluoro-containing intermediate wanted, it is the colourless liquid with alcohol smell under normal temperature, its property is stable, can be with water and various organic
Solvent arbitrarily dissolves each other.Due to its unique physicochemical properties and molecular structure, the property different from other alcohols is made it have
Can, a variety of organic chemical reactionses can be participated in, so exploitation prospect is wide.
Have the technology that many patents and document report are used to prepare the difluoroethanol, such as Chinese patent application at present
Number technology disclosed in 2012800356104, technology disclosed in the patent comprise the steps of：Step (i)：The chloro- 2,2- difluoros of 1-
Ethane reacts in a suitable solvent with the alkali metal salt of formic acid or acetic acid generates corresponding 2,2- difluoros ethyl ester or 2,
2- difluoro ethylhexoates, it is characterised in that be added slowly to be heated to desired reaction temperature by chloro- 2, the 2- Difluoroethanes of 1-
In the mixture of the solvent and formic acid of degree or the alkali metal salt of acetic acid；Step (ii)：The fluoro ethyl first of 2,2- bis- derived from step (i)
Acid esters or 2,2- difluoros ethylhexoate carry out ester exchange in the presence of alcohol and optional alkali.Technology disclosed in the patent has one
The defects of individual obvious：Caused solid waste is more and is difficult to handle, therefore industrial production cost is higher.
Technology disclosed in number of patent application 2012102863533, using self-control catalyst, 180~250 DEG C, 5~
Under the conditions of 10MPa, difluoroethanol is generated using hydrogen reducing difluoro acetate.In patent using ester and hydrogen at high temperature under high pressure
There is security risk in reaction, caused hydrochloric acid has corrosion security risk to equipment in reaction, and patent does not refer to catalyst in addition
Service life and treatment technology.
Other such as using difluoroacetic acid carboxylate as raw material reduction prepare the technology path of difluoroethanol due to process route is long,
Cost of material is high, is economically worthless.
The content of the invention
The present invention is in order to make up the deficiencies in the prior art, there is provided a kind of cost is low, reaction condition is gentle, accessory substance is few,
The preparation method and device of environmentally safe difluoroethanol, solve problems of the prior art.
The present invention is achieved through the following technical solutions：
A kind of preparation method of difluoroethanol, comprises the following steps：
(1) add a certain amount of solvent and potassium hydroxide in a kettle to be reacted under agitation, reaction temperature 110
DEG C~200 DEG C, 0.5~12 hour reaction time；
(2) after the completion of step (1) reaction, 2- chlorine-1,1-difluoroethanes, reaction temperature 170 are slowly added into reactor
DEG C~250 DEG C, in 6~24 hours reaction time, 2,2- difluoroethanols are then separated and collected from reaction product.
It is kept stirring in step (1) and step (2) course of reaction, 50~600 revs/min of mixing speed.
Step (1) reaction temperature is 130 DEG C~160 DEG C, and the reaction time is 2~6 hours.
Step (2) reaction temperature is 190 DEG C~230 DEG C, and the reaction time is 6~12 hours.
The chloro- 1,1- Difluoroethanes addition speed of 2- was added by 2~6 hours in step (2) is defined.
Step (1) and step (2) reaction are carried out in inert nitrogen gas.
Step (1) and step (2) during the course of the reaction or reaction start before add 5%~10% potassium hydroxide weight
Water.
The solvent is gamma-butyrolacton, and the mol ratio of solvent and potassium hydroxide is 2~10:1,2- chlorine-1,1-difluoroethane
Mol ratio with potassium hydroxide is 1~3:1.
A kind of preparation facilities of difluoroethanol, including 2- chlorine-1,1-difluoroethanes storage tank, solvent tank, reactor, thick steaming
The chloro- 1,1- Difluoroethanes storage tank of kettle, bottom storage tank, surge tank, rectifying column, high-boiling components storage tank, overhead condenser, 2- and difluoro second
Alcohol storage tank, the bottom of the 2- chlorine-1,1-difluoroethanes storage tank and solvent tank pass through the top phase of pipeline and reactor respectively
Even, the top of the reactor is also connected by pipeline with the top of crude steam kettle, the top of the crude steam kettle also by pipeline with
The top of surge tank is connected, and the bottom of crude steam kettle is connected by pipeline with bottom storage tank, and the bottom of surge tank passes through pipeline and essence
The top for evaporating tower is connected, and the bottom of rectifying column is connected by pipeline with the top of high-boiling components storage tank, passes through pipe at the top of rectifying column
The top of the condenser of road one chloro- with 2- 1,1- Difluoroethanes storage tank and difluoroethanol storage tank respectively is connected.
The beneficial effects of the invention are as follows：The preparation method and device of the difluoroethanol, solvent and hydrogen in closed reactor
Nak response generation intermediate product is aoxidized, then excessive 2- chlorine-1,1-difluoroethanes are slowly introducing into reactor, when reacting one section
Between after, it is that can obtain 2, the 2- difluoroethanols of high-purity that product is carried out into separating-purifying.The present invention uses the chloro- 1,1- difluoros second of 2-
Alkane produces difluoroethanol, and raw material is the accessory substance of 1- chlorine-1,1-difluoroethanes, and raw material is easy to get, cost is low；Reaction condition is gentle,
Accessory substance is few, environmentally safe.
Brief description of the drawings
The present invention is further illustrated below in conjunction with the accompanying drawings.
Fig. 1 is the structural representation of the present invention.
In figure, 1,2- chlorine-1,1-difluoroethane storage tanks, 2, solvent tank, 3, reactor, 4, crude steam kettle, 5, bottom storage tank,
6th, surge tank, 7, rectifying column, 8, high-boiling components storage tank, 9, condenser, 10,2- chlorine-1,1-difluoroethane storage tanks, 11, difluoroethanol
Storage tank.
Embodiment
For the technical characterstic for illustrating this programme can be understood, below by embodiment, and its accompanying drawing is combined, to this hair
It is bright to be described in detail.
As shown in figure 1, a kind of preparation facilities of difluoroethanol, including 2- chlorine-1,1-difluoroethanes storage tank 1, solvent tank
2nd, the chloro- 1,1- difluoros of reactor 3, crude steam kettle 4, bottom storage tank 5, surge tank 6, rectifying column 7, high-boiling components storage tank 8, condenser 9,2-
Ethane storage tank 10 and difluoroethanol storage tank 11, the bottom of the 2- chlorine-1,1-difluoroethanes storage tank 1 and solvent tank 2 lead to respectively
Piping is connected with the top of reactor 3, and the top of the reactor 3 is also connected by pipeline with the top of crude steam kettle 4, described
The top of crude steam kettle 4 is also connected by pipeline with the top of surge tank 6, and the bottom of crude steam kettle 4 passes through pipeline and the phase of bottom storage tank 5
Even, the bottom of surge tank 6 is connected by pipeline with the top of rectifying column 7, and the bottom of rectifying column 7 passes through pipeline and high-boiling components storage tank
8 top is connected, the top of rectifying column 7 by pipeline through a condenser 9 respectively with 2- chlorine-1,1-difluoroethanes storage tank 10 and two
The top of fluoroethanol storage tank 11 is connected.Embodiment 1：
The preparation method of the difluoroethanol, comprises the following steps：
(1) 600g solvents are added in 1.5L reactors and 100g potassium hydroxide is reacted under agitation, reaction temperature
For 140 DEG C, 0.5 hour reaction time；
(2) after the completion of step (1) reaction, chloro- 1, the 1- difluoros second of 2- is slowly added to 100mL/h flow into reactor
Alkane 300g, 200 DEG C of reaction temperature, in 10 hours reaction time, crude steam kettle 4 then is sequentially sent to from by product, rectifying column 7, is carried out
Separation, obtains 2,2- difluoroethanols.
Step (1) and step (2) reaction are carried out in inert nitrogen gas, control 600 revs/min of mixing speed.
In step (1) and step (2) course of reaction or reaction starts the preceding water for adding 5%~10% potassium hydroxide weight.
The solvent is gamma-butyrolacton.
The chloro- 1,1- Difluoroethanes storage tanks 1 of 2- and solvent tank 2 are respectively used to store the chloro- 1,1- Difluoroethanes of 2- and γ-fourth
Lactone.
The specific method for separating and collecting 2,2- difluoroethanols in step (2) from reaction product is：
The product discharged at the top of reactor is sent into crude steam kettle, at 120-150 DEG C of temperature and 0.2-0.4MPa pressure,
2, the 2- difluoroethanols in product are made to be separated with solvent and potassium chloride, solvent and potassium chloride are sent into bottom storage tank, 2,2- difluoro second
Alcohol is sent into surge tank and stored.
Crude product 2 in surge tank, 2- difluoroethanols are sent into rectifying column from rectifier and carry out rectifying, the high-boiling components of bottom of towe
High-boiling components storage tank is sent into discharge, and the gaseous substance of tower top is sent into condenser condensation, obtains 2- chlorine-1,1-difluoroethanes, difluoro second
Alcohol.
Embodiment 2：
The present embodiment and the difference of embodiment 1 are：600g solvents and 100g hydrogen-oxygens are added in 1.5L reactors
Change potassium, control mixing speed 600r/min, 160 DEG C of temperature, react 1.5h；Again with the 100mL/h chloro- 1,1- bis- of flow input 2-
Fluoroethane 300g, 250 DEG C of temperature control, 10h is reacted, difluoroethanol is separated and collected after the completion of reaction.
Embodiment 3：
The present embodiment and the difference of embodiment 1 are：1000g solvents, 100g hydrogen-oxygens are added in 1.5L reactors
Change potassium and 10g water, control mixing speed 400r/min, 130 DEG C of temperature, react 1h；It is chloro- with 100mL/h flow input 2- again
1,1- Difluoroethane 300g, 190 DEG C of temperature control, 8h is reacted, difluoroethanol is separated and collected after the completion of reaction.
Embodiment 4：
The present embodiment and the difference of embodiment 1 are：1600g solvents and 100g hydrogen-oxygens are added in 1.5L reactors
Change potassium, the oxygen that nitrogen displacement goes out in reactor, control mixing speed 300r/min, 150 DEG C of temperature, react 2.5h；Again with
60mL/h flow input 2- chlorine-1,1-difluoroethane 200g, 195 DEG C of temperature control, react 6h, difluoro are separated and collected after the completion of reaction
Ethanol.
Embodiment 5：
The present embodiment and the difference of embodiment 1 are：600g solvents and 100g hydrogen-oxygens are added in 1.5L reactors
Change potassium, control mixing speed 600r/min, 110 DEG C of temperature, react 0.5h；Again with the 100mL/h chloro- 1,1- bis- of flow input 2-
Fluoroethane 300g, 180 DEG C of temperature control, 10h is reacted, difluoroethanol is separated and collected after the completion of reaction.
Embodiment 6：
The present embodiment and the difference of embodiment 1 are：600g solvents, 100g hydroxides are added in 1.5L reactors
Potassium and 6g water, control mixing speed 600r/min, 140 DEG C of temperature, react 0.5h；2- chloro- 1 is put into 100mL/h flow again,
1- Difluoroethane 300g, 190 DEG C of temperature control, 10h is reacted, difluoroethanol is separated and collected after the completion of reaction.
The experimental result of table 1
Experimental result can be seen that when reaction temperature is too high from table 1, and by-product height boiling is more, and temperature is too low, and reaction is again
Not exclusively, optimum temperature is about (1) 130~160 DEG C of step, (2) 190~210 DEG C of step；Adding suitable quantity of water into reaction can be with
Make reaction more steady, solution colour is preferable after reaction；Reaction conversion ratio is higher under inert gas shielding, and by-product height boiling compared with
It is few；The other process route reaction temperature, pressure are gentleer compared to conventional art.
Part is not described in detail by the present invention, is the known technology of those skilled in the art of the present technique.Finally illustrate, the above is real
Example is applied to be merely illustrative of the technical solution of the present invention and unrestricted, although having been carried out specifically to the present invention with reference to preferred embodiment
It is bright, it will be understood by those within the art that, technical scheme can be modified or equivalent substitution, and
The objective and scope of technical solution of the present invention are not departed from, it all should cover among scope of the presently claimed invention.
Claims (9)
1. a kind of preparation method of difluoroethanol, it is characterized in that：Comprise the following steps：
(1) a certain amount of solvent and potassium hydroxide is added in a kettle to be reacted under agitation, reaction temperature be 110 DEG C~
200 DEG C, 0.5~12 hour reaction time；
(2) 2- chlorine-1,1-difluoroethanes are slowly added to after the completion of step (1) reaction, into reactor, 170 DEG C of reaction temperature~
250 DEG C, in 6~24 hours reaction time, 2,2- difluoroethanols are then separated and collected from reaction product.
2. the preparation method of difluoroethanol according to claim 1, it is characterized in that：Step (1) and step (2) course of reaction
In be kept stirring for, 50~600 revs/min of mixing speed.
3. the preparation method of difluoroethanol according to claim 1, it is characterized in that：Step (1) reaction temperature be 130 DEG C~
160 DEG C, the reaction time is 2~6 hours.
4. the preparation method of difluoroethanol according to claim 1, it is characterized in that：Step (2) reaction temperature be 190 DEG C~
230 DEG C, the reaction time is 6~12 hours.
5. the preparation method of difluoroethanol according to claim 1, it is characterized in that：The chloro- 1,1- difluoros second of 2- in step (2)
Alkane addition speed was added by 2~6 hours to be defined.
6. the preparation method of difluoroethanol according to claim 1, it is characterized in that：Step (1) and step (2) reaction are lazy
Carried out in property gas nitrogen.
7. the preparation method of difluoroethanol according to claim 1, it is characterized in that：Step (1) and step (2) were being reacted
In journey or reaction starts the preceding water for adding 5%~10% potassium hydroxide weight.
8. the preparation method of difluoroethanol according to claim 1, it is characterized in that：The solvent is gamma-butyrolacton, solvent
Mol ratio with potassium hydroxide is 2~10:The mol ratio of 1,2- chlorine-1,1-difluoroethane and potassium hydroxide is 1~3:1.
9. a kind of device for the preparation method for realizing any described difluoroethanols of claim 1-8, it is characterized in that：Including 2-
Chloro- 1,1- Difluoroethanes storage tank, solvent tank, reactor, crude steam kettle, bottom storage tank, surge tank, rectifying column, high-boiling components storage tank,
Overhead condenser, 2- chlorine-1,1-difluoroethanes storage tank and difluoroethanol storage tank, the 2- chlorine-1,1-difluoroethanes storage tank and molten
The bottom of agent storage tank is connected by pipeline with the top of reactor respectively, and the top of the reactor also passes through pipeline and crude steam kettle
Top be connected, the top of the crude steam kettle is also connected by pipeline with the top of surge tank, and the bottom of crude steam kettle passes through pipeline
Be connected with bottom storage tank, the bottom of surge tank is connected by pipeline with the top of rectifying column, the bottom of rectifying column by pipeline with
The top of high-boiling components storage tank is connected, and the top of rectifying column is stored up with 2- chlorine-1,1-difluoroethanes respectively by pipeline through a condenser
Tank is connected with the top of difluoroethanol storage tank.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201710968662.1A CN107739298A (en) | 2017-10-18 | 2017-10-18 | The preparation method and device of a kind of difluoroethanol |
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| CN201710968662.1A CN107739298A (en) | 2017-10-18 | 2017-10-18 | The preparation method and device of a kind of difluoroethanol |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS62273925A (en) * | 1986-05-23 | 1987-11-28 | Asahi Chem Ind Co Ltd | Production of 2,2-difluoroethanol |
| US20040152926A1 (en) * | 2001-07-02 | 2004-08-05 | Hideyuki Mimura | Process for producing fluorinated alcohol |
| CN1736973A (en) * | 2001-09-14 | 2006-02-22 | 东曹氟技术株式会社 | Method for producing 2,2,2-trifluoroethanol |
-
2017
- 2017-10-18 CN CN201710968662.1A patent/CN107739298A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS62273925A (en) * | 1986-05-23 | 1987-11-28 | Asahi Chem Ind Co Ltd | Production of 2,2-difluoroethanol |
| US20040152926A1 (en) * | 2001-07-02 | 2004-08-05 | Hideyuki Mimura | Process for producing fluorinated alcohol |
| CN1736973A (en) * | 2001-09-14 | 2006-02-22 | 东曹氟技术株式会社 | Method for producing 2,2,2-trifluoroethanol |
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Application publication date: 20180227 |
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