CN110563544A - Preparation method and device of 1, 2-dibromo-1, 1, 2-trifluoroethane - Google Patents
Preparation method and device of 1, 2-dibromo-1, 1, 2-trifluoroethane Download PDFInfo
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- CN110563544A CN110563544A CN201910676441.6A CN201910676441A CN110563544A CN 110563544 A CN110563544 A CN 110563544A CN 201910676441 A CN201910676441 A CN 201910676441A CN 110563544 A CN110563544 A CN 110563544A
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- dibromo
- trifluoroethane
- bromine
- trifluoroethylene
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/013—Preparation of halogenated hydrocarbons by addition of halogens
- C07C17/04—Preparation of halogenated hydrocarbons by addition of halogens to unsaturated halogenated hydrocarbons
Abstract
The invention discloses a method and a device for preparing 1, 2-dibromo-1, 1, 2-trifluoroethane. Under ultraviolet light, trifluoroethylene liquid is introduced into a bromination reaction kettle to carry out a photobromination reaction with bromine in the kettle, so that a 1, 2-dibromo-1, 1, 2-trifluoroethane crude product is obtained, and a 1, 2-dibromo-1, 1, 2-trifluoroethane product is obtained through post-treatment. Solves the problem of slow feeding caused by heat release of bromine addition reaction, and has the advantages of stable reaction, high reaction speed and the like.
Description
Technical Field
The invention relates to bromine addition reaction, in particular to a method and a device for preparing 1, 2-dibromo-1, 1, 2-trifluoroethane.
Background
The bromine addition reaction belongs to electrophilic addition, bromine molecules are polarized into polar molecules with one end carrying micro positive charges and the other end carrying micro negative charges under the influence of the outside, the positive end of the polar molecules reacts with double bonds of olefin to initially form a pi coordination compound, and then covalent bond heterolysis is carried out to obtain a sigma complex with positive charges and bromide ions.
1, 2-dibromo-1, 1, 2-trifluoroethane is an important intermediate for synthesizing hexafluorobutadiene, which is generally obtained by bromine addition reaction of trifluoroethylene with liquid bromine, and the main reaction formula is as follows:
CF2＝CFH+Br2→CF2BrCFBrH。
For example, chinese patent CN106495982B2 discloses that trifluoroethylene is washed with water and alkali, and then is introduced into liquid bromine for reaction, after the reaction is completed, the color of the liquid bromine is brown and gradually becomes lighter, and CHF ═ CF2And Br2Complete reaction conversion to CF2BrCFBrH。
However, the reaction is exothermic, so that the reaction of directly reacting trifluoroethylene with liquid bromine has obvious exothermicity, the feeding speed of the reaction is influenced, and the reaction takes longer time.
In order to overcome the defects, the invention develops the preparation method of the 1, 2-dibromo-1, 1, 2-trifluoroethane, and the method controls the reaction heat release, enables the reaction to be more stable and accelerates the reaction speed by recovering part of products to participate in bromine addition reaction and carrying out photobromination under the ultraviolet light condition.
Disclosure of Invention
The invention aims to provide a method and a device for preparing 1, 2-dibromo-1, 1, 2-trifluoroethane. The preparation method solves the problem of slow feeding caused by heat release of bromine addition reaction, and has the advantages of stable reaction, high reaction speed and the like.
In order to achieve the purpose, the invention adopts the following technical scheme:
A preparation method of 1, 2-dibromo-1, 1, 2-trifluoroethane comprises the steps of introducing trifluoroethene liquid into a bromination reaction kettle under ultraviolet light to perform a photobromination reaction with bromine in the kettle to obtain a 1, 2-dibromo-1, 1, 2-trifluoroethane crude product, and performing aftertreatment to obtain a 1, 2-dibromo-1, 1, 2-trifluoroethane product.
Further, the molar ratio of the trifluoroethylene to the bromine is 1-1.1: 1; preferably, the molar ratio of trifluoroethylene to bromine is 1.05: 1.
Further, the crude product of the 1, 2-dibromo-1, 1, 2-trifluoroethane is partially recycled to the photobromination reaction.
Further, the molar ratio of the 1, 2-dibromo-1, 1, 2-trifluoroethane crude product to bromine is 0.5-2: 1; preferably, the molar ratio of the crude 1, 2-dibromo-1, 1, 2-trifluoroethane to bromine is 1:1.
Furthermore, the wavelength range of the ultraviolet light is 190-315nm, and a straight tube type ultraviolet mercury lamp with the power of 30-100 watts is adopted.
The invention also provides a device for preparing the 1, 2-dibromo-1, 1, 2-trifluoroethane, which comprises a bromination reaction kettle, wherein the bromination reaction kettle is provided with a bromine inlet, a trifluoroethylene inlet and an ultraviolet light inlet, the ultraviolet light inlet is communicated with an illumination channel, the illumination channel is cylindrical, the side wall of the illumination channel is provided with more than two illumination ports, an ultraviolet light emitter is arranged outside the illumination ports, and the interior of the illumination channel is filled with transparent glass beads.
Further, the upper part of the illumination channel is connected with a condenser for preventing trifluoroethylene from escaping.
Furthermore, the number of the bromination reaction kettles is two, the two bromination reaction kettles are connected in series, and an outlet above a condenser of the first bromination reaction kettle is communicated with a trifluoroethylene inlet of the second bromination reaction kettle. The outlet above the condenser of the invention is part of unreacted trifluoroethylene which is introduced into the second bromination reaction kettle, thus improving the utilization rate of trifluoroethylene.
Further, a stirring device is also arranged in the bromination reaction kettle.
The invention has the following characteristics:
(1) The trifluoroethene and bromine are subjected to the photobromination reaction under the ultraviolet light condition, so that the reaction speed is increased, and the reaction time is shortened.
(2) The invention recycles part of the 1, 2-dibromo-1, 1, 2-trifluoroethane crude product, continues to participate in the photobromination reaction, is beneficial to reducing the reaction heat release, quickens the feeding speed and improves the production efficiency.
(3) The invention reasonably controls the technological parameters, and has higher yield of more than 97 percent.
Drawings
FIG. 1A schematic diagram of the apparatus for preparing 1, 2-dibromo-1, 1, 2-trifluoroethane according to the present invention.
FIG. 2 is a schematic diagram of the apparatus for preparing 1, 2-dibromo-1, 1, 2-trifluoroethane according to the present invention.
The device comprises a 1-bromination reaction kettle, a 2-bromine inlet, a 3-trifluoroethylene inlet, a 4-ultraviolet light inlet, a 5-illumination channel, a 6-illumination port, a 7-stirring device and a 8-product outlet.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions of the embodiments of the present invention will be clearly and completely described below. It is to be understood that the embodiments described are only a few embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the described embodiments of the invention without any inventive step, are within the scope of protection of the invention.
Unless defined otherwise, technical or scientific terms used herein shall have the ordinary meaning as understood by one of ordinary skill in the art to which this invention belongs.
The device for preparing 1, 2-dibromo-1, 1, 2-trifluoroethane comprises a bromination reaction kettle 1 as shown in figure 1, wherein the bromination reaction kettle is provided with a bromine inlet 2, a trifluoroethylene inlet 3 and an ultraviolet light inlet 4, the ultraviolet light inlet 4 is communicated with an illumination channel 5, the illumination channel 5 is cylindrical, the side wall of the illumination channel 5 is provided with more than two illumination ports 6, an ultraviolet light emitter is arranged outside the illumination ports 6, the illumination channel is filled with transparent glass beads, the bromination reaction kettle also comprises a stirring device 7 for fully stirring reaction raw materials, and a crude product of 1, 2-dibromo-1, 1, 2-trifluoroethane is introduced into the bottom of the bromination reaction kettle 1 through a product outlet 8 and recycled to the photobromination reaction.
In one embodiment of the invention, the upper part of the illumination channel is connected with a condenser for preventing trifluoroethylene from escaping.
The ultraviolet light of the ultraviolet light emitter has the wavelength range of 190-315nm, and adopts a straight tube type ultraviolet mercury lamp with the power of 30-100W.
The bromination reactor of the invention is an enamel kettle, and the specification can be 200L or other.
Taking a bromination reactor with the specification of 200L as an example, the process for preparing the 1, 2-dibromo-1, 1, 2-trifluoroethane comprises the following steps: firstly, conveying bromine into a bromination reaction kettle from a bromine metering tank, then introducing trifluoroethylene into the bromination reaction kettle at a feeding speed of 10-20kg/h, simultaneously opening a stirring device, stirring reaction raw materials, fully mixing the introduced trifluoroethylene with the bromine, stopping feeding when the molar ratio of the trifluoroethylene to the bromine reaches 1-1.1: 1, wherein the molar ratio of the recycling amount of a 1, 2-dibromo-1, 1, 2-trifluoroethane crude product to the bromine is 0.5-2: 1, collecting the residual 1, 2-dibromo-1, 1, 2-trifluoroethane crude product, and carrying out post-treatment to obtain a 1, 2-dibromo-1, 1, 2-trifluoroethane product.
In one embodiment of the present invention, the number of the bromination reaction kettles is two, the two bromination reaction kettles are arranged in series, and the outlet above the condenser of the first bromination reaction kettle is communicated with the trifluoroethylene inlet of the second bromination reaction kettle, as shown in fig. 2.
Example 1: influence test of crude product recycling amount and bromine ratio on system heat
Because the reaction heat release is large, in the test process, partial bromine addition product is mixed with bromine, and trifluoroethylene is introduced for reaction, and the result shows that the reaction heat release is obviously reduced, and the problem of slow feeding caused by the reaction heat release is solved. The ratio test of the recycled product and bromine was carried out in a 200L enamel kettle according to the feeding coefficient of 0.8, and the results are shown in Table 1:
TABLE 1 crude product recycle and bromine proportioning test
As can be seen from Table 1, when the ratio of the crude product recycle amount to the bromine is 2:1, the feeding can be completed within 3 hours, the feeding speed of the trifluoroethylene can reach 20.7Kg/h, but the yield is influenced by a small amount of the discharged material in a single kettle; when the ratio of the crude product to bromine is 2:3, the single kettle discharge can reach 216Kg, but the time is long. The optimal ratio of the reuse amount of the crude product to the bromine is 1:1 in comprehensive consideration.
Example 2: impact test of trifluoroethylene feeding speed on system pressure
A chlorotrifluoroethylene feeding speed test is carried out under the condition that the ratio of the crude product reuse amount to the bromine is 1:1, the influence of different feeding speeds on the system pressure is mainly considered, and the test results are shown in a table 2.
TABLE 2 trifluoroethylene feed rate vs. system pressure test
| Feed rate, kg/h | Maximum pressure of the reactor, KPa |
| 5～10 | 27.1 |
| 10～20 | 57.9 |
| 20～30 | 91.4 |
As can be seen from Table 2, when the trifluoroethylene feeding speed is 5-10Kg/h, the reaction pressure is not high, which indicates that the reaction absorption is better; when the feeding speed of the trifluoroethylene is 20-30Kg/h, the reaction pressure is higher, which indicates that the trifluoroethylene cannot be absorbed in time, and the feeding speed is too high, so that the optimal feeding speed of the trifluoroethylene in the device is 10-20 Kg/h.
Example 3: raw material ratio influence test on crude product composition
A raw material proportioning test is carried out under the conditions that the ratio of the crude product recycle amount to bromine is 1:1, and the feeding speed of trifluoroethylene is 10-20Kg/h, the influence of different raw material proportioning on the crude product composition is mainly considered, and the test results are shown in Table 3.
TABLE 3 influence of different raw material ratios on crude product composition
The data in Table 3 show that when the molar ratio of bromine to trifluoroethylene is 1:1, a small amount of bromine is not completely reacted in the crude product; when the molar ratio is 1:1.05, the bromine reaction is complete; when the feeding amount of the trifluoroethylene is continuously increased to 1:1.1, a crude product is sampled and analyzed to have higher trifluoroethylene content. Therefore, the optimal molar ratio of the trifluoroethylene to the bromine is 1: 1.05.
example 4: influence of ultraviolet light on Process and product composition
The test is carried out under the conditions that the ratio of the recycled amount of the crude product to bromine is 1:1, the feeding speed of trifluoroethylene is 10-20Kg/h, and the molar ratio of bromine to trifluoroethylene is 1:1.05, wherein batches 1-3 are carried out under the condition that an ultraviolet light device is closed, and batches 4-6 are carried out under the condition that the ultraviolet light device is opened, and the results are shown in Table 4.
TABLE 4 influence of UV light on the Process and product composition
As can be seen from Table 4, under the condition of ultraviolet light source, the reaction time is greatly shortened, and the purity of the product in the crude product composition is higher than that under the non-ultraviolet light condition, the utilization rate of the raw material is improved.
The above description of the embodiments is only intended to facilitate the understanding of the method of the invention and its core ideas. It should be noted that, for those skilled in the art, it is possible to make various improvements and modifications to the present invention without departing from the principle of the present invention, and those improvements and modifications also fall within the scope of the claims of the present invention.
Claims (10)
1. A preparation method of 1, 2-dibromo-1, 1, 2-trifluoroethane is characterized in that under ultraviolet light, trifluoroethylene liquid is introduced into a bromination reaction kettle to carry out photobromination reaction with bromine in the kettle to obtain a 1, 2-dibromo-1, 1, 2-trifluoroethane crude product, and the 1, 2-dibromo-1, 1, 2-trifluoroethane product is obtained through aftertreatment.
2. the method for preparing 1, 2-dibromo-1, 1, 2-trifluoroethane according to claim 1, wherein the molar ratio of trifluoroethylene to bromine is 1 to 1.1: 1.
3. The method for preparing 1, 2-dibromo-1, 1, 2-trifluoroethane according to claim 2, wherein the molar ratio of trifluoroethylene to bromine is 1.05: 1.
4. The method for preparing 1, 2-dibromo-1, 1, 2-trifluoroethane according to claim 1, wherein the crude 1, 2-dibromo-1, 1, 2-trifluoroethane is partially recycled to the photobromination reaction.
5. The preparation method of 1, 2-dibromo-1, 1, 2-trifluoroethane according to claim 1, wherein the molar ratio of the crude 1, 2-dibromo-1, 1, 2-trifluoroethane to bromine is 0.5 to 2: 1.
6. The method for preparing 1, 2-dibromo-1, 1, 2-trifluoroethane according to claim 1, wherein the wavelength of the ultraviolet light is in the range of 190 to 315 nm.
7. An apparatus for preparing 1, 2-dibromo-1, 1, 2-trifluoroethane according to any one of claims 1 to 6, comprising a bromination reaction kettle, wherein the bromination reaction kettle is provided with a bromine inlet, a trifluoroethylene inlet and an ultraviolet light inlet, the ultraviolet light inlet is communicated with an illumination channel, the illumination channel is cylindrical, the side wall of the illumination channel is provided with more than two illumination ports, an ultraviolet light emitter is arranged outside the illumination ports, and the interior of the illumination channel is filled with light-transmitting glass beads.
8. The apparatus of claim 7, wherein the illumination channel is connected to a condenser above the illumination channel.
9. The device according to claim 7, wherein the number of the bromination reaction kettles is two, the two bromination reaction kettles are arranged in series, and an outlet above a condenser of the first bromination reaction kettle is communicated with a trifluoroethylene inlet of the second bromination reaction kettle.
10. The apparatus of claim 7, wherein the bromination reaction kettle further comprises a stirring device.
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| CN201910676441.6A CN110563544A (en) | 2019-07-25 | 2019-07-25 | Preparation method and device of 1, 2-dibromo-1, 1, 2-trifluoroethane |
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Citations (5)
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| CH320744A (en) * | 1952-09-15 | 1957-04-15 | Neville Haszeldine Robert | Process for the preparation of halogenated organic compounds |
| CN101031529A (en) * | 2004-08-26 | 2007-09-05 | 大湖化学公司 | Chemical production processes and systems |
| CN102863313A (en) * | 2011-07-06 | 2013-01-09 | 中化蓝天集团有限公司 | Resource utilization method of tail gas from trifluoroethylene production |
| CN104591957A (en) * | 2015-02-15 | 2015-05-06 | 浙江环新氟材料股份有限公司 | Method for preparing 1,2-dibromohexafluoropropane |
| CN204865798U (en) * | 2015-08-23 | 2015-12-16 | 淮安洪阳化工有限公司 | Light chlorination reaction kettle convenient to chlorine and washing let in |
-
2019
- 2019-07-25 CN CN201910676441.6A patent/CN110563544A/en active Pending
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CH320744A (en) * | 1952-09-15 | 1957-04-15 | Neville Haszeldine Robert | Process for the preparation of halogenated organic compounds |
| GB774103A (en) * | 1952-09-15 | 1957-05-08 | Robert Neville Haszeldine | Halogenated organic compounds |
| FR1245503A (en) * | 1952-09-15 | 1960-11-10 | New halogenated organic compounds and their preparation process | |
| CN101031529A (en) * | 2004-08-26 | 2007-09-05 | 大湖化学公司 | Chemical production processes and systems |
| CN102863313A (en) * | 2011-07-06 | 2013-01-09 | 中化蓝天集团有限公司 | Resource utilization method of tail gas from trifluoroethylene production |
| CN104591957A (en) * | 2015-02-15 | 2015-05-06 | 浙江环新氟材料股份有限公司 | Method for preparing 1,2-dibromohexafluoropropane |
| CN204865798U (en) * | 2015-08-23 | 2015-12-16 | 淮安洪阳化工有限公司 | Light chlorination reaction kettle convenient to chlorine and washing let in |
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Effective date of registration: 20210107 Address after: No. 6, Gongye Road, Jiaoyang industrial concentration zone, Jiaoyang Town, Shanghang County, Longyan City, Fujian Province, 364204 Applicant after: FUJIAN DEER TECHNOLOGY Co.,Ltd. Address before: No. 6, Gongye Road, Jiaoyang industrial concentration zone, Jiaoyang Town, Shanghang County, Longyan City, Fujian Province, 364000 Applicant before: Fujian Hangfu Electronic Materials Co.,Ltd. |
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Application publication date: 20191213 |
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