CN105254470A - Method for removing impurities 1,1,2,2,3,3,4,5-octafluorocyclopentane - Google Patents
Method for removing impurities 1,1,2,2,3,3,4,5-octafluorocyclopentane Download PDFInfo
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- CN105254470A CN105254470A CN201510795812.4A CN201510795812A CN105254470A CN 105254470 A CN105254470 A CN 105254470A CN 201510795812 A CN201510795812 A CN 201510795812A CN 105254470 A CN105254470 A CN 105254470A
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- octafluorocyclopentane
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Abstract
The invention relates to a method for removing impurities 1,1,2,2,3,3,4,5-octafluorocyclopentane, and belongs to the field of fluorine-containing fine electronic chemicals. According to the removing method, alkaline solutions with different concentrations are adopted to be fully and evenly mixed with a sample to be treated according to a certain proportion, and after reacting is performed for a period of time in a specific environment, the purpose that the octafluorocyclopentane is removed due to the fact that an elimination reaction takes place is finally achieved. The removing method is convenient to control, handy in raw material source, safe in process, capable of repeatedly utilizing aqueous phase liquid, good in environmental protection property and low in cost, is successfully verified in actual production and is more suitable for industrial scale production.
Description
Technical field
The present invention relates to fluorine-containing fine electronic field of chemicals, particularly relate to a kind of method of impurity 1,1,2,2,3,3,4, the 5-Octafluorocyclopentane removed in 1,1,2,2,3,3,4-seven fluorine pentamethylene.
Background technology
Along with the reinforcement of environmental consciousness, progressively eliminating the promise of ODS substitute for cashing Montreal protocol, constantly weeds out the old and bring forth the new in clean-out system industry in countries in the world, releases environmental-protecting performance successively, electronic product clean-out system that cleaning performance progressively improves.
According to its environmental protection parameter, products characteristics, development course, at present ODS substitute technology was generally divided into for four generations.First-generation cleaning technique is withdrawn from the market comprehensively, the domestic HCFC-141b mainly used in s-generation cleaning technique, and developed country then mainly uses hydrocarbon class clean-out system in third generation cleaning technique and HFE-449s1 etc.According to the resolution of Montreal protocol, entered the superseded stage of HCFCs in the world, Japan AGC stopped HCFC-225ca/cb producing in 2013, domesticly also will eliminate HCFC-141b before the year two thousand twenty comprehensively.So far, also there is not a kind of replacement scheme and technology of clear and definite, feasible HCFCs class clean-out system in China.
1,1,2,2,3,3,4-seven fluorine pentamethylene (C
5f
7h
3) there is very high industrial value, boiling point: 82.5 DEG C, its ODP value is 0, GWP100 value lower (195), low toxicity, not fire, be mainly used in advanced semiconductor cleaning field, there is supereminent clean ability, be considered to one of representative products in forth generation clean-out system.
Patent WO9851650A1 reports with 1, and 1,2,2,3,3,4,5-octafluoro cyclopentenes is raw material Liquid preparation methods 1,1,2, the method of 2,3,3,4-seven fluorine pentamethylene, experiment finds that the solvent of opposed polarity has a significant impact reaction preference, at generation target product 1,1,2,2,3, while 3,4-seven fluorine pentamethylene, also can obtain by product 1,1,2,2,3,3,4,5-Octafluorocyclopentane.
Patent GB1046095 reports the technology that 1,1,2,2,3,3,4,5-octafluoro cyclopentenes shortening prepares 1,1,2,2,3,3,4,5-Octafluorocyclopentane, finds in preparation process, can generate 1,1,2,2,3,3,4-seven a small amount of fluorine pentamethylene.But due to 1,1,2,2,3,3,4-seven fluorine pentamethylene and 1,1,2,2,3,3,4,5-Octafluorocyclopentane boiling point closely, be difficult to by distillation, both are separated.
1,1,2,2,3,3, the boiling point of 4.5-Octafluorocyclopentane is 79 DEG C, with 1, and 1,2,2,3, relatively, and both molecular structures are also more similar for 3,4-seven fluorine pentamethylene (boiling point 82.5 DEG C), be difficult to realization by technology such as extraction, rectifying, molecular sieve adsorption and be isolated removal, cause quality product can not reach the requirement of high-quality product, such as, in rectifying separation test, under the condition of total reflux, 1,1 of tower top and tower reactor, 2,2,3,3, the content of 4,5-Octafluorocyclopentane does not have obvious difference, shows that this by product component can not be separated by the way of rectifying.
Summary of the invention
The object of the invention is the defect in order to overcome the more difficult removal of difficult separating impurity in target product in existing production technology, studying that a kind of raw material sources are convenient, process safety is convenient to controls, energy-conserving and environment-protective, lower-cost effective ways, applicable suitability for industrialized production.
A kind of a small amount of impurity 1 removed in raw material 1,1,2,2,3,3,4-seven fluorine pentamethylene, the method of 1,2,2,3,3,4,5-Octafluorocyclopentane, it is characterized in that: add basic solution in the feed, mix, make 1,1,2,2,3,3,4,5-Octafluorocyclopentane generation eliminative reaction sloughs a hydrogen fluoride, generates 1,1,2,2,3,3,4-seven fluorine cyclopentenes, then remove 1 by rectifying, 1,2,2,3,3,4-seven fluorine cyclopentenes.
Described basic solution is at least one in potassium hydroxide, sodium hydroxide, sodium carbonate, solution of potassium carbonate, and described alkali lye weight percent concentration is 0.01% ~ 20%.
Preferred potassium hydroxide or sodium hydroxide solution, described alkali lye weight percent concentration is 0.05% ~ 5%.
The mass content of described impurity 1,1,2,2,3,3,4,5-Octafluorocyclopentane is 0.2 ~ 2.8%, and described raw material and basic solution volume ratio are 1:1 ~ 10.
Preferred 1:1 ~ 5.
The described eliminative reaction time is 5min ~ 120min.
Preferred 10min ~ 60min.
Described hybrid mode is mixing in pump chamber, Venturi mixes, outer circulation type mixes or is uniformly mixed.
Described rectifying condition is pressure 0.2 ~ 0.3MPa, tower top temperature 105 ~ 120 DEG C.
The present invention is liquid phase reaction, by 1, and 1,2,2,3, there is eliminative reaction in the basic conditions and slough a hydrogen fluoride in 3,4,5-Octafluorocyclopentane, generate 1,1,2,2,3,3,4-seven fluorine cyclopentenes, this by product is by rectifying 0.2 ~ 0.3MPa, the rectifying condition of tower top temperature 105 ~ 120 DEG C and rectifiable removing.Due to principal product in raw material 1,1,2,2,3,3,4-seven fluorine pentamethylene and impurity 1,1,2,2,3,3, the structure comparison of 4,5-Octafluorocyclopentane is similar, in the basic conditions, can slough a hydrofluoric eliminative reaction equally, generate 1,1,2,2,3,3-hexafluoro cyclopentenes, this by product is by rectifying pressure 0.2 ~ 0.3MPa, the rectifying condition of tower top temperature 100 ~ 125 DEG C and rectifiable removing.Experimental study through us proves, the classification of alkali lye is different, concentration is different, the difference of two-phase mixtures intensity, all directly can have influence on the speed of reaction when reaction efficiency of two kinds of reactions.Preferred method in the present invention, can make 1,1,2,2,3,3,4,5-Octafluorocyclopentane while high-level efficiency is eliminated, and reduces the decomposition loss of 1,1,2,2,3,3,4-seven fluorine pentamethylene.
Process of the present invention is summarized as follows:
The certain density alkali lye preparing some amounts is placed in container, adds pending organic phase liquid according to a certain percentage, starts mixed reactor, makes organic phase and aqueous phase fully mix and react.After for some time, stop stirring, leave standstill, get levels fluid analysis respectively and detect.
Production amplification process is summarized as follows:
First in reactor, squeeze into pure water, then squeeze into pending organic phase liquid, according to concentration of lye computed in advance, the concentrated base prepared is added in still, start mixed reactor, make organic phase and aqueous phase fully mix and react.At interval of for some time, organic phase and alkali lye sampling analysis are detected in process.
The inventive method good stability, be convenient to control, raw material sources facility, process safety, aqueous phase liquid can reuse, the feature of environmental protection is good, cost is lower, and the checking of succeeding in actual production, be relatively applicable to industrial scale and produce.
Embodiment
Patent CN103570490A reports a kind of vapor-phase synthesis 1,2-bis-chloro-3,3,4,4,5, the method of 5-hexafluoro cyclopentenes, the method take hexachlorocyclopentadiene as starting raw material, under the effect of certain catalyzer, by the exchange chloride for fluoride with HF, obtain 1,2-bis-chloro-3,3,4,4,5,5-hexafluoro cyclopentenes.
Patent CN103570491A reports the method for chloro-3,3,4,4,5, the 5-seven fluorine cyclopentenes of a kind of gas phase catalytic synthesis 1-, and the method obtains chloro-3,3,4,4,5, the 5-seven fluorine cyclopentenes of 1-to fluoridizing further of chloro-3,3,4,4,5, the 5-hexafluoro cyclopentenes of 1,2-bis-.
Our unit adopts three step vapor phase processs, and the first step adopts the method described in patent CN103570490A, and second step adopts the method described in patent CN103570491A, take hexachlorocyclopentadiene as raw material, go through two steps to fluoridize and obtain 1-chloro-3,3,4,4,5,5-seven fluorine cyclopentenes; 3rd step adopts conventional method for hydrogenation, and with chloro-3,3,4,4,5, the 5-seven fluorine cyclopentenes of 1-for raw material, shortening obtains target product 1,1,2,2,3,3,4-seven fluorine pentamethylene.In production process, by-product impurities 1,1,2,2,3,3,4,5-Octafluorocyclopentane can be produced.
Below in conjunction with embodiment, the present invention is further described.
The raw materials used organic phase sample of removing of the present invention belongs to outside the middle product of impure 1,1,2,2,3,3,4, the 5-Octafluorocyclopentane that our unit produces, and all the other are commercially available.
The present invention is according to 1,1,2,2,3,3,4-seven fluorine pentamethylene and 1,1,2,2,3,3,4,5-Octafluorocyclopentane structural similitude and the equal feature of rate of decomposition, and adopt and in the basic conditions eliminative reaction occurs, process and method comprises the steps:
Embodiment 1
By organic phase sample one (1,1,2 pending for 50ml, 2,3,3, containing impurity 1,1,2 in 4-seven fluorine pentamethylene, 2,3,3,4,5-Octafluorocyclopentane) being 0.10% with 20ml concentration, sodium hydroxide solution mixes, and be placed in container and stir, start reaction, stop after 30min, get organic phase and enter chromatographic instrument detection.
Embodiment 2
By organic phase sample one (1,1,2 pending for 50ml, 2,3,3, containing impurity 1,1,2 in 4-seven fluorine pentamethylene, 2,3,3,4,5-Octafluorocyclopentane) being 0.10% with 20ml concentration, potassium hydroxide solution mixes, and be placed in container and stir, start reaction, stop after 30min, get organic phase and enter chromatographic instrument detection.
Embodiment 3
By organic phase sample one (1,1,2 pending for 70ml, 2,3,3, containing impurity 1,1,2 in 4-seven fluorine pentamethylene, 2,3,3,4,5-Octafluorocyclopentane) being 0.10% with 20ml concentration, sodium hydroxide solution mixes, and be placed in container and stir, start reaction, stop after 30min, get organic phase and enter chromatographic instrument detection.
Embodiment 4
By organic phase sample one (1,1,2 pending for 70ml, 2,3,3, containing impurity 1,1,2 in 4-seven fluorine pentamethylene, 2,3,3,4,5-Octafluorocyclopentane) being 0.10% with 20ml concentration, sodium carbonate solution mixes, and be placed in container and stir, start reaction, stop after 30min, get organic phase and enter chromatographic instrument detection.
Embodiment 5
By organic phase sample two (1,1,2 pending for 70ml, 2,3,3, containing impurity 1,1,2 in 4-seven fluorine pentamethylene, 2,3,3,4,5-Octafluorocyclopentane) being 0.10% with 20ml concentration, potassium hydroxide solution mixes, and be placed in container and stir, start reaction, stop after 15min, get organic phase and enter chromatographic instrument detection.
Embodiment 6
By organic phase sample two (1,1,2 pending for 70ml, 2,3,3, containing impurity 1,1,2 in 4-seven fluorine pentamethylene, 2,3,3,4,5-Octafluorocyclopentane) being 0.10% with 20ml concentration, potassium hydroxide solution mixes, and be placed in container and stir, start reaction, stop after 30min, get organic phase and enter chromatographic instrument detection.
Embodiment 7
By organic phase sample two (1,1,2 pending for 70ml, 2,3,3, containing impurity 1,1,2 in 4-seven fluorine pentamethylene, 2,3,3,4,5-Octafluorocyclopentane) being 0.20% with 20ml concentration, potassium hydroxide solution mixes, and be placed in container and stir, start reaction, stop after 30min, get organic phase and enter chromatographic instrument detection.
Embodiment 8
By organic phase sample two (1,1,2 pending for 70ml, 2,3,3, containing impurity 1,1,2 in 4-seven fluorine pentamethylene, 2,3,3,4,5-Octafluorocyclopentane) being 0.10% with 20ml concentration, solution of potassium carbonate mixes, and be placed in container and stir, start reaction, stop after 30min, get organic phase and enter chromatographic instrument detection.
Embodiment 9
By organic phase sample two (1,1,2 pending for 70ml, 2,3,3, containing impurity 1,1,2 in 4-seven fluorine pentamethylene, 2,3,3,4,5-Octafluorocyclopentane) be the potassium hydroxide of 0.10% with 20ml concentration, the potassium fluoride solution of 0.05% mixes, be placed in container and stir, start reaction, stop after 30min, get organic phase and enter chromatographic instrument detection.
Embodiment 10
By 1 ton of pending Industrial products one (containing impurity 1,1,2,2,3,3,4,5-Octafluorocyclopentane in 1,1,2,2,3,3,4-seven fluorine pentamethylene) and 2.2m
3concentration is the potassium hydroxide solution mixing of 0.10%, is placed in 3m
3container in stir, start reaction, stop after 30min, get organic phase enter chromatographic instrument detect.
Embodiment 11
By 1 ton of pending Industrial products two (containing impurity 1,1,2,2,3,3,4,5-Octafluorocyclopentane in 1,1,2,2,3,3,4-seven fluorine pentamethylene) and 2.2m
3concentration is the potassium hydroxide solution mixing of 0.10%, is placed in 3m
3container in stir, start reaction, stop after 30min, get organic phase enter chromatographic instrument detect.
Embodiment 12
By 1 ton of pending Industrial products three (containing impurity 1,1,2,2,3,3,4,5-Octafluorocyclopentane in 1,1,2,2,3,3,4-seven fluorine pentamethylene) and 2.2m
3concentration is the potassium hydroxide solution mixing of 0.10%, is placed in 3m
3container in stir, start reaction, stop after 30min, get organic phase enter chromatographic instrument detect.
Embodiment 13
By 1 ton of pending Industrial products four (containing impurity 1,1,2,2,3,3,4,5-Octafluorocyclopentane in 1,1,2,2,3,3,4-seven fluorine pentamethylene) and 2.2m
3concentration is the potassium hydroxide solution mixing of 0.10%, is placed in 3m
3container in stir, start reaction, stop after 30min, get organic phase enter chromatographic instrument detect.
Experimental result
Claims (9)
1. remove a small amount of impurity 1 in raw material 1,1,2,2,3,3,4-seven fluorine pentamethylene for one kind, the method of 1,2,2,3,3,4,5-Octafluorocyclopentane, it is characterized in that: add basic solution in the feed, mix, make 1,1,2,2,3,3,4,5-Octafluorocyclopentane generation eliminative reaction sloughs a hydrogen fluoride, generates 1,1,2,2,3,3,4-seven fluorine cyclopentenes, then remove 1 by rectifying, 1,2,2,3,3,4-seven fluorine cyclopentenes.
2. method according to claim 1, described basic solution is at least one in potassium hydroxide, sodium hydroxide, sodium carbonate, solution of potassium carbonate, and described alkali lye weight percent concentration is 0.01% ~ 20%.
3. method according to claim 2, described basic solution is potassium hydroxide or sodium hydroxide solution, and described alkali lye weight percent concentration is 0.05% ~ 5%.
4. method according to claim 3, the mass content of described impurity 1,1,2,2,3,3,4,5-Octafluorocyclopentane is 0.2 ~ 2.8%, and described raw material and basic solution volume ratio are 1:1 ~ 10.
5. method according to claim 4, described raw material and basic solution material are than being 1:1 ~ 5.
6. method according to claim 5, the described eliminative reaction time is 5min ~ 120min.
7. method according to claim 6, preferred 10min ~ 60min.
8. method according to claim 1, described hybrid mode is mixing in pump chamber, Venturi mixes, outer circulation type mixes or is uniformly mixed.
9. method according to claim 1, described rectifying condition is pressure 0.2 ~ 0.3MPa, tower top temperature 105 ~ 120 DEG C.
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| CN201510795812.4A CN105254470A (en) | 2015-11-18 | 2015-11-18 | Method for removing impurities 1,1,2,2,3,3,4,5-octafluorocyclopentane |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2002055457A2 (en) * | 2001-01-15 | 2002-07-18 | Showa Denko K.K. | Process for purifying octafluoropropane, process for preparing the same, and use thereof |
| CN1847205A (en) * | 2005-03-31 | 2006-10-18 | 沈阳化工学院 | Method of separating 1,2-dichloropropane with DD mixture |
| CN103328423A (en) * | 2010-11-16 | 2013-09-25 | 霍尼韦尔国际公司 | Process for producing 2,3,3,3-tetrafluoropropene |
-
2015
- 2015-11-18 CN CN201510795812.4A patent/CN105254470A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2002055457A2 (en) * | 2001-01-15 | 2002-07-18 | Showa Denko K.K. | Process for purifying octafluoropropane, process for preparing the same, and use thereof |
| CN1847205A (en) * | 2005-03-31 | 2006-10-18 | 沈阳化工学院 | Method of separating 1,2-dichloropropane with DD mixture |
| CN103328423A (en) * | 2010-11-16 | 2013-09-25 | 霍尼韦尔国际公司 | Process for producing 2,3,3,3-tetrafluoropropene |
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Application publication date: 20160120 |