CN102766017A - Preparation method of tetrachloro-1,2-difluoroethane - Google Patents
Preparation method of tetrachloro-1,2-difluoroethane Download PDFInfo
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- CN102766017A CN102766017A CN2012102697478A CN201210269747A CN102766017A CN 102766017 A CN102766017 A CN 102766017A CN 2012102697478 A CN2012102697478 A CN 2012102697478A CN 201210269747 A CN201210269747 A CN 201210269747A CN 102766017 A CN102766017 A CN 102766017A
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Abstract
The invention belongs to the technical field of fluoride industry, in particular relates to a preparation method of tetrachloro-1,2-difluoroethane. According to the preparation method of tetrachloro-1,2-difluoroethane, raw materials, namely by-products generated during the production process of 1,1-difluoro-1-chloroethane, have a photo-chlorination reaction with chlorine under the action of light to produce tetrachloro-1,2-difluoroethane, wherein the by-products are high-boiling residues comprising 1,2 dichloro-1,1- chloroethane, 1,1-difluoro-1,2,2- trichloroethane and 1,1-difluoro-1-chloroethane. The preparation method has the advantages that the consumption of raw materials of the product is reduced, the by-products generated during the production process are effectively recycled and used, the loss of fluorine resources is effectively reduced, the energy is saved and the product quality is guaranteed.
Description
Technical field
The invention belongs to the fluorine chemical technical field, be specifically related to a kind of preparation method of C2Cl4F2.
Background technology
C2Cl4F2 (R112) is a kind of very important fluorine chemical material, and existing production technology generally adopts Sesquichloratum and hydrogen fluoride as raw material, in the presence of the catalyzer antimony pentachloride, react to make, but this technical transform rate is low, and product yield is low.
In recent years, along with production-scale continuous expansion of difluoro monochlorethane and development, the high boiling material that produces in its production process (comprising difluoro ethylene dichloride, two trifluorotrichloroethanes and a small amount of difluoro monochlorethane) is more and more.If this part material is used as a kind of solvent; Not only cost is high; And can produce contamination to environment after the solvent evaporates, and therefore most important to the recycling of this partial material, thus promoted each enterprise and R&D institution to this Study on Technology and exploitation.
In the epoch that the fluorine ore resource lacks day by day; Reduce the waste of fluorine resource, the recovery utilization rate of raising fluorine resource; Reduce it simultaneously as solvent a large amount of volatilizations cause in atmosphere environmental disruption and pollution; Improve the yield of product, cut down the consumption of raw materials and production cost, there is crucial meaning in society.
In difluoro monochlorethane production process, owing to the fluctuation of light application time and reaction conditions, can be attended by the generation of side reaction, how the by product that produces being carried out efficient recovery is the basic assurance that reduces the wasting of resources, reduction environmental pollution with utilizing.To the characteristic that produces by product in the production of difluoro monochlorethane, in conjunction with the rich experiences that my company accumulates in the refrigeration agent production industry, my company has developed a kind of preparation method of C2Cl4F2 through technology upgrading and innovation independent development.
Summary of the invention
The preparation method who the purpose of this invention is to provide a kind of C2Cl4F2, this method has carried out reclaiming effectively and utilizing to producing the by product that produces in the difluoro monochlorethane process, has reduced the loss of fluorine resource, has practiced thrift the energy.
The preparation method of C2Cl4F2 of the present invention is to be raw material to produce the by product that produces in the difluoro monochlorethane process, under the effect of illumination and chlorine carry out optical chlorinating reaction and make C2Cl4F2; Said by product is the high boiling material that comprises difluoro ethylene dichloride, two trifluorotrichloroethanes, difluoro monochlorethane;
Its reaction equation is following:
C
2H
3F
2Cl+3Cl
2→C
2F
2Cl
4+3HCl↑
C
2H
2F
2Cl
2+2Cl
2→C
2F
2Cl
4+2HCl↑
C
2HF
2Cl
3+Cl
2→C
2F
2Cl
4+HCl↑。
Described optical chlorinating reaction temperature is 150 ~ 250 ℃, and reaction pressure is 0.02 ~ 0.05MPa, and the reaction times is 30 ~ 300 seconds.
The mol ratio of described by product and chlorine is 1:3 ~ 4.
The present invention will produce the high boiling material that produces in the difluoro monochlorethane process and collect; Under the effect of illumination, make high boiling material and chlorine carry out chlorination reaction and make the C2Cl4F2 bullion, then bullion is carried out rectification and purification and make purity at the C2Cl4F2 finished product more than 99.9%.Can the hydrogenchloride water that reaction process generates be absorbed in addition become hydrochloric acid soln, the hydrochloric acid of when obtaining the high purity C2Cl4F2, having gone back by-product.
The R112 that the present invention makes is mainly used in the liver fluke wormer of producing cooling agent, narcotic, aerosol, propelling agent, the clear agent of precision instrument, treatment ox, as resin intermediate etc.
Technological process is following:
The high boiling material that produces in the difluoro monochlorethane production process and chlorine are carried out chlorination reaction make C2Cl4F2 bullion gas under the illumination effect; The hydrogen chloride gas that reaction generates absorbs through the absorption tower and makes hydrochloric acid, and then through alkali lye neutralize, compress, slightly heat up in a steamer, rectifying, drying makes the C2Cl4F2 highly finished product.Hydrochloric acid is used for selling as sub product, and the waste liquid that produces in the alkaline cleaning procedure is discharged to the WWT operation and handles.
The present invention's technology is simple, and product yield is high, and lab scale is achieved success.It is few that this technology has a three-waste pollution, easy control of reaction system, and low power consumption and other advantages is easy to realize large-scale industrial production.Can obtain highly purified C2Cl4F2 through the present invention; Method of the present invention can be handled the by product that produces in the dichloro one fluoroethane production process timely and effectively; Thereby improve the recovery utilization rate of fluorine resource, avoid causing environmental pollution, obvious social benefit.In process of production, produce the by product that 1 ton of difluoro monochlorethane obtains and can make about 0.06 ton C2Cl4F2 with it, calculate by producing 10000 tons of difluoro monochlorethanes per year, can make about 600 tons of C2Cl4F2 every year, economic benefit very significantly.
Beneficial effect of the present invention is following:
The present invention has reduced the raw material consumption of product; And the by product in its production process carried out effective recovery and utilization, and effectively reduced the loss of fluorine resource, practiced thrift the energy, guaranteed the quality of product.
Description of drawings
Fig. 1 is a process flow sheet of the present invention.
Embodiment
Below in conjunction with embodiment the present invention is done and to further describe.
Embodiment 1
The preparation method of C2Cl4F2 of the present invention; Be to be raw material to produce the by product that produces in the difluoro monochlorethane process; Under the effect of illumination, carry out optical chlorinating reaction with chlorine and make C2Cl4F2, said by product mainly comprises difluoro ethylene dichloride and two trifluorotrichloroethanes and a spot of difluoro monochlorethane;
Its reaction equation is:
C
2H
3F
2Cl+3Cl
2→C
2F
2Cl
4+3HCl↑
C
2H
2F
2Cl
2+2Cl
2→C
2F
2Cl
4+2HCl↑
C
2HF
2Cl
3+Cl
2→C
2F
2Cl
4+HCl↑
Described temperature of reaction is 150 ℃.
Described reaction pressure is 0.05MPa.
280 seconds described reaction times.
The mol ratio of described by product and chlorine is 1:3.
Each substances content is a difluoro monochlorethane 8.46% before the experiment, difluoro ethylene dichloride 61.73%, two trifluorotrichloroethane 29.81%.
Each substances content of experiment back is a difluoro monochlorethane 1.25%, difluoro ethylene dichloride 31.55%, two trifluorotrichloroethane 12.46%, and C2Cl4F2 54.74%, C2Cl4F2 purity is 99.92%.
Embodiment 2
The preparation method of C2Cl4F2 of the present invention; Be to be raw material to produce the by product that produces in the difluoro monochlorethane process; Under the effect of illumination, carry out optical chlorinating reaction with chlorine and make C2Cl4F2, said by product mainly comprises difluoro ethylene dichloride and two trifluorotrichloroethanes and a spot of difluoro monochlorethane;
Its reaction equation such as embodiment 1.
Described temperature of reaction is 180 ℃.
Described reaction pressure is 0.03MPa.
200 seconds described reaction times.
The mol ratio of described by product and chlorine is 1:3.
Each substances content is a difluoro monochlorethane 8.46% before the experiment, difluoro ethylene dichloride 61.73%, two trifluorotrichloroethane 29.81%.
Each substances content of experiment back is a difluoro monochlorethane 1.82%, difluoro ethylene dichloride 29.47%, two trifluorotrichloroethane 10.41%, and C2Cl4F2 58.30%, C2Cl4F2 purity is 99.91%.
Embodiment 3
The preparation method of C2Cl4F2 of the present invention; Be to be raw material to produce the by product that produces in the difluoro monochlorethane process; Under the effect of illumination, carry out optical chlorinating reaction with chlorine and make C2Cl4F2, said by product mainly comprises difluoro ethylene dichloride and two trifluorotrichloroethanes and a spot of difluoro monochlorethane;
Its reaction equation such as embodiment 1.
Described temperature of reaction is 200 ℃.
Described reaction pressure is 0.04MPa.
150 seconds described reaction times.
The mol ratio of described by product and chlorine is 1:3.
Each substances content is a difluoro monochlorethane 8.46% before the experiment, difluoro ethylene dichloride 61.73%, two trifluorotrichloroethane 29.81%.
Each substances content of experiment back is a difluoro monochlorethane 2.52%, difluoro ethylene dichloride 26.36%, two trifluorotrichloroethane 12.74%, and C2Cl4F2 58.38%, C2Cl4F2 purity is 99.93%.
Embodiment 4
The preparation method of C2Cl4F2 of the present invention; Be to be raw material to produce the by product that produces in the difluoro monochlorethane process; Under the effect of illumination, carry out optical chlorinating reaction with chlorine and make C2Cl4F2, said by product mainly comprises difluoro ethylene dichloride and two trifluorotrichloroethanes and a spot of difluoro monochlorethane;
Its reaction equation such as embodiment 1.
Described temperature of reaction is 230 ℃.
Described reaction pressure is 0.02MPa.
100 seconds described reaction times.
The mol ratio of described by product and chlorine is 1:4.
Each substances content is a difluoro monochlorethane 8.46% before the experiment, difluoro ethylene dichloride 61.73%, two trifluorotrichloroethane 29.81%.
Each substances content of experiment back is a difluoro monochlorethane 2.27%, difluoro ethylene dichloride 23.73%, two trifluorotrichloroethane 12.34%, and C2Cl4F2 61.66%, C2Cl4F2 purity is 99.92%.
Embodiment 5
The preparation method of C2Cl4F2 of the present invention; Be to be raw material to produce the by product that produces in the difluoro monochlorethane process; Under the effect of illumination, carry out optical chlorinating reaction with chlorine and make C2Cl4F2, said by product mainly comprises difluoro ethylene dichloride and two trifluorotrichloroethanes and a spot of difluoro monochlorethane;
Its reaction equation such as embodiment 1.
Described temperature of reaction is 250 ℃.
Described reaction pressure is 0.03MPa.
50 seconds described reaction times.
The mol ratio of described by product and chlorine is 1:4.
Each substances content is a difluoro monochlorethane 8.46% before the experiment, difluoro ethylene dichloride 61.73%, two trifluorotrichloroethane 29.81%.
Each substances content of experiment back is a difluoro monochlorethane 1.65%, difluoro ethylene dichloride 22.42%, two trifluorotrichloroethane 14.48%, and C2Cl4F2 61.45%, C2Cl4F2 purity is 99.93%.
Embodiment 6
The preparation method of C2Cl4F2 of the present invention; Be to be raw material to produce the by product that produces in the difluoro monochlorethane process; Under the effect of illumination, carry out optical chlorinating reaction with chlorine and make C2Cl4F2, said by product mainly comprises difluoro ethylene dichloride and two trifluorotrichloroethanes and a spot of difluoro monochlorethane;
Its reaction equation such as embodiment 1.
Described temperature of reaction is 225 ℃.
Described reaction pressure is 0.02MPa.
80 seconds described reaction times.
The mol ratio of described by product and chlorine is 1:3.
Each substances content is a difluoro monochlorethane 8.46% before the experiment, difluoro ethylene dichloride 61.73%, two trifluorotrichloroethane 29.81%.
Each substances content of experiment back is a difluoro monochlorethane 3.14%, difluoro ethylene dichloride 26.93%, two trifluorotrichloroethane 12.75%, and C2Cl4F2 57.18%, C2Cl4F2 purity is 99.90%.
Claims (7)
1. the preparation method of a C2Cl4F2 is characterized in that: to produce the by product that produces in the difluoro monochlorethane process is raw material, under the effect of illumination and chlorine carry out optical chlorinating reaction and make C2Cl4F2;
Said by product is the high boiling material that comprises difluoro ethylene dichloride, two trifluorotrichloroethanes, difluoro monochlorethane;
Its reaction equation is following:
C
2H
3F
2Cl+3Cl
2→C
2F
2Cl
4+3HCl↑
C
2H
2F
2Cl
2+2Cl
2→C
2F
2Cl
4+2HCl↑
C
2HF
2Cl
3+Cl
2→C
2F
2Cl
4+HCl↑。
2. the preparation method of C2Cl4F2 according to claim 1 is characterized in that described optical chlorinating reaction temperature is 150 ~ 250 ℃.
3. the preparation method of C2Cl4F2 according to claim 1 is characterized in that described optical chlorinating reaction pressure is 0.02 ~ 0.05MPa.
4. the preparation method of C2Cl4F2 according to claim 1 is characterized in that the described optical chlorinating reaction time is 30 ~ 300 seconds.
5. the preparation method of C2Cl4F2 according to claim 1, the mol ratio that it is characterized in that described by product and chlorine is 1:3 ~ 4.
6. according to the preparation method of the arbitrary described C2Cl4F2 of claim 1 ~ 5, it is characterized in that the C2Cl4F2 bullion that described optical chlorinating reaction obtains, make purity at the C2Cl4F2 more than 99.9% through rectification and purification.
7. the preparation method of C2Cl4F2 according to claim 6 is characterized in that hydrogenchloride water absorption the becoming hydrochloric acid soln that reaction process is generated.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106977362A (en) * | 2016-11-07 | 2017-07-25 | 浙江埃克盛化工有限公司 | 1.1.1 the recoverying and utilizing method of the high-boiling components produced in chlorodifluoroethane production process |
| CN107056581A (en) * | 2017-05-22 | 2017-08-18 | 山东东岳化工有限公司 | The separation method of the high-boiling components of the Difluoroethane production technology of 1 chlorine 1,1 |
| CN113264810A (en) * | 2021-06-03 | 2021-08-17 | 常熟三爱富振氟新材料有限公司 | Preparation process of F112 |
| CN113372214A (en) * | 2021-06-03 | 2021-09-10 | 常熟三爱富振氟新材料有限公司 | Continuous rectification process of F112 |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101948367A (en) * | 2010-09-06 | 2011-01-19 | 浙江巍华化工有限公司 | Preparation method taking 1,1,1-trifluoroethane as raw material |
-
2012
- 2012-07-31 CN CN2012102697478A patent/CN102766017A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101948367A (en) * | 2010-09-06 | 2011-01-19 | 浙江巍华化工有限公司 | Preparation method taking 1,1,1-trifluoroethane as raw material |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106977362A (en) * | 2016-11-07 | 2017-07-25 | 浙江埃克盛化工有限公司 | 1.1.1 the recoverying and utilizing method of the high-boiling components produced in chlorodifluoroethane production process |
| CN107056581A (en) * | 2017-05-22 | 2017-08-18 | 山东东岳化工有限公司 | The separation method of the high-boiling components of the Difluoroethane production technology of 1 chlorine 1,1 |
| CN107056581B (en) * | 2017-05-22 | 2020-03-27 | 山东东岳化工有限公司 | Method for separating high-boiling residues in 1-chloro-1, 1-difluoroethane production process |
| CN113264810A (en) * | 2021-06-03 | 2021-08-17 | 常熟三爱富振氟新材料有限公司 | Preparation process of F112 |
| CN113372214A (en) * | 2021-06-03 | 2021-09-10 | 常熟三爱富振氟新材料有限公司 | Continuous rectification process of F112 |
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Application publication date: 20121107 |