CN102603461A - Method for preparing 1,2-dibromotetrafluoroethane from tail gas in production of tetrafluoroethylene - Google Patents
Method for preparing 1,2-dibromotetrafluoroethane from tail gas in production of tetrafluoroethylene Download PDFInfo
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- CN102603461A CN102603461A CN201210029604XA CN201210029604A CN102603461A CN 102603461 A CN102603461 A CN 102603461A CN 201210029604X A CN201210029604X A CN 201210029604XA CN 201210029604 A CN201210029604 A CN 201210029604A CN 102603461 A CN102603461 A CN 102603461A
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- tetrafluoroethylene
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- dibromotetrafluoroethane
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Abstract
The invention relates to a method for preparing 1,2-dibromotetrafluoroethane by recycling tetrafluoroethylene from a tail gas in production of tetrafluoroethylene, which belongs to the technical field of synthesis of organic fluorine and is characterized in that: introducing the tail gas in production of tetrafluoroethylene from the bottom of a liquid bromine-containing tubular reactor in the presence of a catalyst, allowing tetrafluoroethylene in the tail gas to sufficiently react with bromine at a temperature of 0-50 DEG C under a pressure of 0-0.50MPa, and performing alkali washing, water washing and distillation purification to obtain 1,2-dibromotetrafluoroethane; and discharging other gases not reacting with bromine in the tail gas from the top of the reactor, and directly emitting the other gases after the other gases are absorbed through an alkaline liquid tank. The method provided by the invention has the following beneficial effects: tetrafluoroethylene is directly transformed and utilized with no need of separation or purification, so that the technological process is short, the investment is less, and the environmental pollution is reduced; more than 90% of tetrafluoroethylene in the tail gas is transformed to 1,2-dibromotetrafluoroethane with high chemical stability; and the method has wide market application and is suitable for industrial production.
Description
Technical field
The present invention relates to a kind ofly from tail gas generated by tetrafluoroethylene, recycle tetrafluoroethylene preparation 1, the method for 2-dibromotetrafluoroethane belongs to the organic fluorine synthesis technical field.
Background technology
Tetrafluoroethylene is one of important material in the organic fluorine compound probability, and the market of its derived product is of many uses.For example, tetrafluoroethylene reacts through the addition reaction of liquid bromine, ethene addition reaction, dehydrobromination, the synthetic 4-bromo-3,3,4,4-tetrafluoro butylene of obtaining.4-bromo-3,3,4,4-tetrafluoro butylene are the sulfuration point monomer components that can be used as multiple viton; In patent GB 1,528,342; Obtain by vinylidene, R 1216,4-bromo-3,3,4 through letex polymerization; 4-tetrafluoro butylene weight ratio is 58.9: 40.0: 1.1 fluorinated copolymers of forming, carry out peroxide vuleanization, mixing processing again after, showed the good mechanical performance.
Most of in the world company all adopts water vapor dilution cracking process to produce tetrafluoroethylene: with difluorochloromethane (CHClF
2, HCFC-22) be raw material,, make high-temperature water vapor and be preheating to difluorochloromethane near temperature of reaction and be pre-mixed and carry out cracking as thermal barrier with the superheated vapour that is higher than cracking temperature.The chemical process that scission reaction at high temperature takes place difluorochloromethane is very complicated, and split product has more than 30 component.Primary product is a tetrafluoroethylene, and by product has hydrogenchloride and R 1216, Perfluorocyclobutane, Vcon, trifluorochloroethylene, methyl chlorofluoride etc., also has carbon monoxide, hydrogen fluoride etc. in addition.
Owing to be dissolved with gases such as oxygen, nitrogen in the water vapor, so gases such as oxygen, nitrogen are along with splitting gas gets into production system together.When the oxygen level in the system reached finite concentration, because of the reactive behavior of tetrafluoroethylene is stronger, tetrafluoroethylene was prone to generate explosive substance with the oxygen reaction, and the safety that has a strong impact on tetrafluoroethylene production is carried out.Therefore, for guaranteeing the continuous operation and the production safety of total system, in the production process of tetrafluoroethylene, the lightness-removing column cat head of distillation system must discharge tail gas generated by tetrafluoroethylene continuously outside system.Because the boiling point of tetrafluoroethylene is lower, and is not easily separated with low component gas, therefore tetrafluoroethylene gas accounts for more than 75% of total discharging tail gas in tail gas generated by tetrafluoroethylene, and all the other are impurity such as carbon monoxide and trifluoromethane, methylene fluoride, C2H4F2 C2H4F2.For scale is 5000t/a tetrafluoroethylene production equipment; The exhaust emissions amount is about 70kg/h, is that 75wt% calculates with tetrafluoroethylene content in the tail gas, and the tetrafluoroethylene amount of losing along with exhaust emissions is about 52.5kg/h; Emit tetrafluoroethylene in 1 year and then be 378 tons, loss amount is very big.Tetrafluoroethylene is that present turnout is maximum, most important fluorochemical monomer, and the discharging of the not only valuable resource of waste, and a large amount of tetrafluoroethylene will pollute ambient air.
At present in the discharging tail gas recovery of tetrafluoroethylene to separate the method that generally adopts be solvent absorption: with certain solvent (being generally Freon 113 CFC-113, difluorochloromethane, chloroform etc.) as extraction agent; The method of utilizing extracting rectifying is separated fluoro-gas such as tetrafluoroethylene, methylene fluoride with carbon monoxide, oxygen etc.; Fluoro-gas returns distillation system and gets tetrafluoroethylene; But there is following distinct disadvantage in this method: extraction agent in use can get in the atmosphere with discharging tail gas; And CFC-113, chloroform etc. are progressively eliminated or forbidding by the world because of the havoc atmospheric ozone layer, and the tetrafluoroethylene recovery is lower, purity difference.The solvent absorbing process of extracting rectifying and the energy consumption of solvent resolving are high.
Summary of the invention
The objective of the invention is: provide a kind of tetrafluoroethylene recovery high, compliance with environmental protection requirements from tail gas generated by tetrafluoroethylene, recycle tetrafluoroethylene, preparation 1, the method for 2-dibromotetrafluoroethane.
For achieving the above object, the technical scheme that the present invention takes is: from tail gas generated by tetrafluoroethylene preparation 1, the method for 2-dibromotetrafluoroethane; The alkali cleaning, washing, distillation purification and the waste gas that comprise reaction product pass through the emptying after lye vat absorbs, and it is characterized in that also comprising the steps: in the presence of catalyzer; Tail gas generated by tetrafluoroethylene is fed from the tubular reactor bottom of containing the liquid bromine; Under 0~50 ℃ of temperature of reaction and pressure 0~0.50MPa condition, tetrafluoroethylene and bromine in the tail gas are fully reacted, reaction product is purified through alkali cleaning, washing, distillation again; Obtain 1, the 2-dibromotetrafluoroethane.
Do not discharge from the top of said tubular reactor in the tail gas, directly entering in the air after absorbing through lye vat again with fluoro-gas such as the methylene fluoride of bromine reaction, trifluoromethane and carbon monoxide.
The reaction of tetrafluoroethylene and bromine, available following formula is represented:
CF
2=CF
2?+?Br
2?→?BrCF
2—CF
2Br
1, the 2-dibromotetrafluoroethane has high chemical stability, can make high-efficiency fire-extinguishant, refrigerant, high-temperature gas lubricant, heat-transfer medium etc.1, the 2-dibromotetrafluoroethane also can be used as the preparation vulcanizable fluororubber and puts monomeric important organic raw material: 1, and 2-dibromotetrafluoroethane and ethene generation addition reaction generate and obtain 1,4-two bromo-1,1,2,2-tetrafluoro butane BrCF
2CF
2CH
2CH
2Br, BrCF then
2CF
2CH
2CH
2The dehydrobromination reaction takes place in Br in the alcoholic solution of NaOH, obtain 4-bromo-3,3,4,4-tetrafluoro butylene BrCF
2CF
2CH=CH
2, BrCF
2CF
2CH=CH
2It is a kind of sulfuration point monomer component that can be used as multiple viton preferably.
Said catalyzer is an inorganic acids, preferred hydrochloric acid, sulfuric acid, nitric acid, hydrofluoric acid, sulfurous acid, phosphoric acid, more preferably hydrochloric acid.In the presence of catalyzer, improved tetrafluoroethylene and the speed of reaction of liquid bromine in the tail gas, reduced the reaction times, improved the transformation efficiency of tetrafluoroethylene.Catalyst consumption is 0.05~0.1wt% of liquid bromine weight.
Said temperature of reaction is 0~50 ℃, is preferably 10~40 ℃.
Said reaction pressure is 0~0.50MPa, is preferably 0.10~0.30MPa.
Said tetrafluoroethylene tail gas can feed from the tubular reactor bottom of containing the liquid bromine continuously or off and on.
Positively effect of the present invention is: employing be with tail gas directly and the catalytic mode of liquid bromine absorb tetrafluoroethylene, do not need that Paratetrafluoroethylene separates, purifying, but, significantly reduced technical process directly with the tetrafluoroethylene trans-utilization; In reaction process, need not introduce solvent, not consume solvent, reduce pollution environment; The reaction conversion ratio of tetrafluoroethylene is high, and tetrafluoroethylene 90% above reaction conversion is 1 in the tail gas, the 2-dibromotetrafluoroethane; 1, the 2-dibromotetrafluoroethane has high chemical stability, and the market purposes is wide, and the technological process of production is short, and less investment is fit to industrialization production.
Embodiment
Describing the present invention in more detail below in conjunction with embodiment, disclose the best implementation method of the present invention, is for those of ordinary skill in the art can be understood and embodiment of the present invention.But it should be noted that the present invention never is limited to the following embodiment of announcement, based on the present invention's enlightenment, any conspicuous conversion perhaps is equal to alternative, also should be considered to fall into protection scope of the present invention.
The concentration of each material among the embodiment, except that have especially indicate, be concentration expressed in percentage by weight.
Embodiment 1
After the 20L tubular reactor is evacuated to vacuum, to wherein adding 20.10kg liquid bromine and 30ml 37% hydrochloric acid.Reactor temperature is maintained 25~30 ℃; From reactor bottom continuously with tetrafluoroethylene tail gas (consisting of of tail gas: tetrafluoroethylene 78.1%, carbon monoxide 17.7%, methylene fluoride 0.9%; Trifluoromethane 1.2%; Other is 2.1% years old) be passed in the reactor drum, and through regulating the switch of tetrafluoroethylene tail gas feed valve, making the pressure in the reactor drum is 0.20~0.25MPa.Feed tetrafluoroethylene tail gas continuously after 5 hours, stop charging, finish reaction, add tetrafluoroethylene tail gas 15.33kg altogether.Reaction product after alkali cleaning, washing, distillation are purified, is obtained 1,2-dibromotetrafluoroethane 29.70kg.Through calculating, the transformation efficiency of tetrafluoroethylene reaches 95.5% in the tail gas.
Embodiment 2
After the 20L tubular reactor is evacuated to vacuum, to wherein adding 19.80kg liquid bromine and 40ml 30% sulfuric acid.Reactor temperature is maintained 10~15 ℃; From reactor bottom continuously with tetrafluoroethylene tail gas (consisting of of tail gas: tetrafluoroethylene 78.1%; Carbon monoxide 17.7%, methylene fluoride 0.9%, trifluoromethane 1.2%; Other is 2.1% years old) be passed in the reactor drum, and to make the pressure in the reactor drum through the switch of regulating tetrafluoroethylene tail gas feed valve be 0.10~0.15MPa.Feed tetrafluoroethylene tail gas continuously after 10 hours, stop charging, finish reaction, add tetrafluoroethylene tail gas 14.30kg altogether.Reaction product after alkali cleaning, washing, distillation are purified, is obtained 1,2-dibromotetrafluoroethane 28.24kg.Through calculating, the transformation efficiency of tetrafluoroethylene reaches 97.3% in the tail gas.
Embodiment 3
After the 20L tubular reactor is evacuated to vacuum, to 30% phosphoric acid that wherein adds 20.30kg liquid bromine and 50ml.Reactor temperature is maintained 40~45 ℃, from reactor bottom with tetrafluoroethylene tail gas (consisting of of tail gas: tetrafluoroethylene 79.8%, carbon monoxide 15.1%; Methylene fluoride 1.1%; Trifluoromethane 0.7%, other is 3.3% years old) be passed in the reactor drum, making the pressure in the reactor drum is 0.40MPa.Along with the carrying out of reaction, the pressure in the reactor drum reduces gradually, when pressure is decreased to 0.10MPa, feeds tetrafluoroethylene tail gas from reactor bottom once more, and making the pressure in the reactor drum is 0.40MPa.Like this method, feed tetrafluoroethylene tail gas off and on after 3 hours repeatedly, stop charging, finish reaction, add tetrafluoroethylene tail gas 16.38kg altogether.Reaction product after alkali cleaning, washing, distillation are purified, is obtained 1,2-dibromotetrafluoroethane 31.28kg.Through calculating, the transformation efficiency of tetrafluoroethylene is 92.1% in the tail gas.
Claims (5)
1. from tail gas generated by tetrafluoroethylene preparation 1; The method of 2-dibromotetrafluoroethane comprises that alkali cleaning, washing, distillation purification and the waste gas of reaction product passes through the emptying after lye vat absorbs, and it is characterized in that also comprising the steps: in the presence of catalyzer; Tail gas generated by tetrafluoroethylene is fed from the tubular reactor bottom of containing the liquid bromine; Under 0~50 ℃ of temperature of reaction and pressure 0~0.50MPa condition, tetrafluoroethylene and bromine in the tail gas are fully reacted, reaction product is purified through alkali cleaning, washing, distillation again; Obtain 1, the 2-dibromotetrafluoroethane.
2. said from tail gas generated by tetrafluoroethylene preparation 1 according to claim 1, the method for 2-dibromotetrafluoroethane is characterized in that said catalyzer is hydrochloric acid, sulfuric acid, nitric acid, hydrofluoric acid, sulfurous acid, phosphoric acid.
3. said from tail gas generated by tetrafluoroethylene preparation 1 according to claim 1, the method for 2-dibromotetrafluoroethane is characterized in that said temperature of reaction is preferably 10~40 ℃.
4. said from tail gas generated by tetrafluoroethylene preparation 1 according to claim 1, the method for 2-dibromotetrafluoroethane is characterized in that said reaction pressure is preferably 0.10~0.30MPa.
5. said from tail gas generated by tetrafluoroethylene preparation 1 according to claim 1, the method for 2-dibromotetrafluoroethane is characterized in that said tetrafluoroethylene tail gas can feed from the tubular reactor bottom of containing the liquid bromine continuously or off and on.
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Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN112645794A (en) * | 2020-12-28 | 2021-04-13 | 山东东岳化工有限公司 | Preparation method of hexafluoro-1, 3-butadiene |
CN112876337A (en) * | 2021-03-09 | 2021-06-01 | 聊城氟尔新材料科技有限公司 | Device and process for co-production of pentafluoroethane from tetrafluoroethylene |
CN113087594A (en) * | 2021-05-11 | 2021-07-09 | 南京美茵生命科技有限公司 | Equipment and method for intermittent tandem type industrial production of 1, 2-dibromoethane |
CN115536490A (en) * | 2022-10-13 | 2022-12-30 | 中国矿业大学(北京) | Method for synthesizing tetrafluoro monobromo butene |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB1315785A (en) * | 1970-08-31 | 1973-05-02 | Kali Chemie Ag | Method of producing tetrafluorodibromoethane |
JP2000169404A (en) * | 1998-12-11 | 2000-06-20 | Tosoh Corp | Bromination of fluorine-containing olefins |
DE102005005774A1 (en) * | 2005-02-07 | 2006-08-10 | Flc Technologies Kg | Preparation of 1,2-dibromohexafluoropropane comprises reaction of hexafluorpropene-1 with elementary bromine, which is in liquid form and the initial stage reaction is initiated by the presence of 1,2-dibromohexafluoropropane |
-
2012
- 2012-02-10 CN CN201210029604XA patent/CN102603461A/en active Pending
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB1315785A (en) * | 1970-08-31 | 1973-05-02 | Kali Chemie Ag | Method of producing tetrafluorodibromoethane |
JP2000169404A (en) * | 1998-12-11 | 2000-06-20 | Tosoh Corp | Bromination of fluorine-containing olefins |
DE102005005774A1 (en) * | 2005-02-07 | 2006-08-10 | Flc Technologies Kg | Preparation of 1,2-dibromohexafluoropropane comprises reaction of hexafluorpropene-1 with elementary bromine, which is in liquid form and the initial stage reaction is initiated by the presence of 1,2-dibromohexafluoropropane |
Non-Patent Citations (1)
Title |
---|
周国华等: "四氟乙烯废气溴化制1_2_二溴四氟乙烷", 《含氟材料》 * |
Cited By (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN112645794A (en) * | 2020-12-28 | 2021-04-13 | 山东东岳化工有限公司 | Preparation method of hexafluoro-1, 3-butadiene |
CN112645794B (en) * | 2020-12-28 | 2022-12-27 | 山东东岳化工有限公司 | Preparation method of hexafluoro-1,3-butadiene |
CN112876337A (en) * | 2021-03-09 | 2021-06-01 | 聊城氟尔新材料科技有限公司 | Device and process for co-production of pentafluoroethane from tetrafluoroethylene |
CN112876337B (en) * | 2021-03-09 | 2024-07-19 | 聊城氟尔新材料科技有限公司 | Device and process for co-producing pentafluoroethane by tetrafluoroethylene |
CN113087594A (en) * | 2021-05-11 | 2021-07-09 | 南京美茵生命科技有限公司 | Equipment and method for intermittent tandem type industrial production of 1, 2-dibromoethane |
CN115536490A (en) * | 2022-10-13 | 2022-12-30 | 中国矿业大学(北京) | Method for synthesizing tetrafluoro monobromo butene |
CN115536490B (en) * | 2022-10-13 | 2024-05-17 | 中国矿业大学(北京) | Method for synthesizing tetrafluoro-bromobutene |
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Application publication date: 20120725 |