CN103073385B - A kind of method absorbing degrading perfluorinated iso-butylene - Google Patents
A kind of method absorbing degrading perfluorinated iso-butylene Download PDFInfo
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- CN103073385B CN103073385B CN201210583643.4A CN201210583643A CN103073385B CN 103073385 B CN103073385 B CN 103073385B CN 201210583643 A CN201210583643 A CN 201210583643A CN 103073385 B CN103073385 B CN 103073385B
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Abstract
The invention discloses a kind of method absorbing degrading perfluorinated iso-butylene, first-selection carries out Pintsch process to fluorinated olefin monomers, in Pintsch process production process, from pyrolyzer, splitting gas is out through the circulated sprinkling absorption tower containing the certain temperature alcohols material aqueous solution, highly toxic substance perfluoroisobutylene in splitting gas is absorbed by the alcohols material of circulated sprinkling absorption tower internal recycle spray, perfluoroisobutylene and alcohols material react and generate perfluor isobutyl-alkyl oxide, perfluor isobutyl-alkyl oxide in the tower reactor of absorption tower with the layering of the alcohols material aqueous solution, the alcohols material aqueous solution on tower reactor upper strata through recycle pump at absorption tower internal recycle, the perfluor isobutyl-alkyl oxide of lower floor delivers to residual liquid processing apparatus through transferpump.<b />
Description
Technical field
The present invention relates to a kind of method absorbing degrading perfluorinated iso-butylene.
Background technology
Perfluoroisobutylene is a kind of by product having toxicity produced in Fluorine containing olefine product Pintsch process is produced, the aerial objectionable impurities maximum allowable concentration of perfluoroisobutylene is 0.1mg/m3, its toxic action band is narrow, dangerous large, suck excessive perfluoroisobutylene and can cause pulmonary edema, make expiratory dyspnea and dead.Therefore need in process of production to deal carefully with it.At present, the most frequently used treatment process is the perfluoroisobutylene absorbed with lower alcohol in splitting gas, and alcohol and perfluoroisobutylene addition reaction can occur at normal temperatures, generate " fluorine ether "---α-perfluor isobutyl-alkyl oxide that toxicity is less.A kind of method of lower alcohol absorbing and removing perfluoroisobutylene is disclosed as far back as the European patent document EP0002098 eighties in last century (A1), the method be by a certain amount of splitting gas containing perfluoroisobutylene in cylinder with lower alcohol and hydrogen halide mixture reaction, entered to analyze and find, the perfluoroisobutylene content in splitting gas reduces along with the growth in reaction times.The method is intermittent reaction, is not suitable for the continuous production technology of Fluorine containing olefine product.Within 2007, patent documentation CN200510044481.7 discloses a kind of perfluoroisobutylene minimizing technology being applied to R 1216 and producing, the method removes perfluoroisobutylene by absorbing from pyrolyzer splitting gas out through alcohols material, then with aqueous sodium carbonate or calcium chloride water, a small amount of alcohol taken out of in splitting gas is absorbed, finally with the vitriol oil or silica gel, drying is carried out to splitting gas again.The method only considers splitting gas can take a certain amount of alcohol out of through alcohols material absorption, and the measure taken with aqueous sodium carbonate or calcium chloride water absorption alcohol, but find (the treatment process containing high density octafluoroisobutene raffinate according to the study, Shen Jianmin, organic fluorine industry, 3 phases in 2006, P37 ~ 38), perfluoroisobutylene and alcohols material react " the fluorine ether " that generates---perfluor isobutyl-alkyl oxide and the volatility of seven fluorine isobutenyl alkyl oxides produced after decomposing all stronger, more than about 20 DEG C can major part volatilize, therefore the cleaved band of gas goes out in the reaction, because " fluorine ether " is oil-soluble substance, can not be absorbed by aqueous sodium carbonate or calcium chloride water, so distillation system can be entered by the cleaved band of gas, affect the quality of R 1216.
Summary of the invention
The invention provides a kind of method absorbing degrading perfluorinated iso-butylene, it can absorb the perfluoroisobutylene removed in Fluorine containing olefine splitting gas, and the by product " fluorine ether " produced can be separated simultaneously, not bring distillation system into, ensure that the quality of Fluorine containing olefine product.
Present invention employs following technical scheme: a kind of method absorbing degrading perfluorinated iso-butylene, it comprises the following steps: first-selection carries out Pintsch process to fluorinated olefin monomers, in Pintsch process production process, from pyrolyzer, splitting gas is out through the circulated sprinkling absorption tower containing the certain temperature alcohols material aqueous solution, highly toxic substance perfluoroisobutylene in splitting gas is absorbed by the alcohols material of circulated sprinkling absorption tower internal recycle spray, perfluoroisobutylene and alcohols material react and generate perfluor isobutyl-alkyl oxide, perfluor isobutyl-alkyl oxide in the tower reactor of absorption tower with the layering of the alcohols material aqueous solution, the alcohols material aqueous solution on tower reactor upper strata through recycle pump at absorption tower internal recycle, the perfluor isobutyl-alkyl oxide of lower floor delivers to residual liquid processing apparatus through transferpump.
Described fluorinated olefin monomers is tetrafluoroethylene monomer or R 1216 monomer.Described alcohols material is methyl alcohol, ethanol, ethylene glycol, propyl alcohol or propylene glycol, and the mass percentage of the alcohols material aqueous solution is 30% ~ 65%.In described circulated sprinkling absorption tower, the volume of the alcohols material aqueous solution is 60% ~ 90% of tower reactor volume.The circulated sprinkling absorption tower of the described alcohols material aqueous solution is set to secondary or three grades of circulated sprinkling absorption towers.In described circulated sprinkling absorption tower, the temperature of the alcohols material aqueous solution is-5 ~ 20 DEG C.
The present invention has following beneficial effect: the mode that the present invention uses circulating absorption tower to spray the alcohols material aqueous solution absorbs the perfluoroisobutylene in splitting gas, absorption reaction produce by product perfluor isobutyl-alkyl oxide in tower reactor with the layering of the alcohols material aqueous solution, and the lower floor in tower reactor is divided because density is large, because the loop exit of tower reactor is on the upper strata at interface, so just can ensure in the alcohols material aqueous solution of circulated sprinkling without perfluor isobutyl-alkyl oxide, and, because this ether is positioned at lower floor in tower reactor, upper strata has the aqueous solution of alcohols material to close, so the stronger perfluor isobutyl-alkyl oxide of volatility also can not evaporate into the upper strata of tower, the rectification working process that the cleaved band of gas enters below.Meanwhile, because perfluor isobutyl-alkyl oxide is a kind of added value very high " fluorine ether ", can be used for producing the expensive chemical materials such as Perfluoroacetone, Ultane.Perfluoroisobutylene is absorbed compared to using pure alcohols material, in above-mentioned processing method, perfluor isobutyl-alkyl oxide directly can be separated with the alcohols material aqueous solution on upper strata, only be dissolved with a small amount of alcohols material, this is that the postorder purification processes of " fluorine ether " alleviates burden.
Accompanying drawing explanation
Fig. 1 is process flow sheet of the present invention.
Embodiment
In FIG, the invention provides a kind of method absorbing degrading perfluorinated iso-butylene, it comprises the following steps: first-selection carries out Pintsch process to fluorinated olefin monomers, fluorinated olefin monomers is tetrafluoroethylene monomer or R 1216 monomer, in Pintsch process production process, from pyrolyzer, splitting gas is out through the circulated sprinkling absorption tower containing the certain temperature alcohols material aqueous solution, alcohols material is methyl alcohol, ethanol, ethylene glycol, propyl alcohol or propylene glycol, the mass percentage of the alcohols material aqueous solution is 30% ~ 65%, in circulated sprinkling absorption tower, the volume of the alcohols material aqueous solution is 60% ~ 90% of tower reactor volume, in described circulated sprinkling absorption tower, the temperature of the alcohols material aqueous solution is-5 ~ 20 DEG C, the circulated sprinkling absorption tower of the alcohols material aqueous solution is set to secondary or three grades of circulated sprinkling absorption towers, highly toxic substance perfluoroisobutylene in splitting gas is absorbed by the alcohols material of circulated sprinkling absorption tower internal recycle spray, perfluoroisobutylene and alcohols material react and generate perfluor isobutyl-alkyl oxide, perfluor isobutyl-alkyl oxide in the tower reactor of absorption tower with the layering of the alcohols material aqueous solution, the alcohols material aqueous solution on tower reactor upper strata through recycle pump at absorption tower internal recycle, the perfluor isobutyl-alkyl oxide of lower floor delivers to residual liquid processing apparatus through transferpump.
Below in conjunction with embodiment, the present invention is described in more detail.
Embodiment 1:
Export at the pyrolyzer of tetrafluoroethylene, CFC-22 splitting gas enters the circulating absorption tower of the alcohols material aqueous solution with the speed of 160kg/h, perfluoroisobutylene content in splitting gas is about 1.5%, recycle column adopts two-stage absorption tower, the alcohols material aqueous solution uses methanol aqueous solution, concentration is 40%, spray flux is at 10m3/h, pressure in tower reactor is pressure-fired, temperature controls at about-5 ~ 10 DEG C, after the absorption of methanol aqueous solution, peak is not gone out with perfluoroisobutylene in gas chromatographic analysis splitting gas and perfluor isobutyl-methyl ether, the content of the perfluor isobutyl-methyl ether of tower reactor lower floor methyl alcohol is by analysis less than 10%.
Embodiment 2:
Export at the pyrolyzer of R 1216, TFE splitting gas enters the circulating absorption tower of the alcohols material aqueous solution with the speed of 80kg/h, perfluoroisobutylene content in splitting gas is about 7.0%, recycle column adopts two-stage absorption tower, the alcohols material aqueous solution uses methanol aqueous solution, concentration is 60%, spray flux is at 10m3/h, pressure in tower reactor is pressure-fired, temperature controls at about-5 ~ 0 DEG C, after the absorption of methanol aqueous solution, peak is not gone out with perfluoroisobutylene in gas chromatographic analysis splitting gas and perfluor isobutyl-methyl ether, the content of the perfluor isobutyl-methyl ether of tower reactor lower floor methyl alcohol is by analysis less than 15%.
Embodiment 3:
According to embodiment 1, the alcohols material aqueous solution adopts aqueous ethanolic solution.Splitting gas, after absorbing process, is analyzed perfluoroisobutylene and perfluor isobutyl-methyl ether and is not gone out peak, and the content of the perfluor isobutyl-methyl ether of tower reactor lower floor methyl alcohol is by analysis less than 15%.
Embodiment 4:
According to embodiment 2, the alcohols material aqueous solution adopts aqueous ethanolic solution.Splitting gas, after absorbing process, is analyzed perfluoroisobutylene and perfluor isobutyl-methyl ether and is not gone out peak, and the content of the perfluor isobutyl-methyl ether of tower reactor lower floor methyl alcohol is by analysis less than 20%.
Claims (1)
1. one kind absorbs the method for degrading perfluorinated iso-butylene, it comprises the following steps: first-selection carries out Pintsch process to fluorinated olefin monomers, in Pintsch process production process, from pyrolyzer, splitting gas is out through the circulated sprinkling absorption tower containing the certain temperature alcohols material aqueous solution, highly toxic substance perfluoroisobutylene in splitting gas is absorbed by the alcohols material of circulated sprinkling absorption tower internal recycle spray, perfluoroisobutylene and alcohols material react and generate perfluor isobutyl-alkyl oxide, perfluor isobutyl-alkyl oxide in the tower reactor of absorption tower with the layering of the alcohols material aqueous solution, the alcohols material aqueous solution on tower reactor upper strata through recycle pump at absorption tower internal recycle, the perfluor isobutyl-alkyl oxide of lower floor delivers to residual liquid processing apparatus through transferpump, described fluorinated olefin monomers is tetrafluoroethylene monomer or R 1216 monomer, described alcohols material is methyl alcohol, ethanol, ethylene glycol, propyl alcohol or propylene glycol, the mass percentage of the alcohols material aqueous solution is 30% ~ 65%, in described circulated sprinkling absorption tower, the volume of the alcohols material aqueous solution is 60% ~ 90% of tower reactor volume, the circulated sprinkling absorption tower of the described alcohols material aqueous solution is set to secondary or three grades of circulated sprinkling absorption towers, in described circulated sprinkling absorption tower, the temperature of the alcohols material aqueous solution is-5 ~ 20 DEG C.
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| CN109999716B (en) * | 2019-03-29 | 2021-04-27 | 三明学院 | Nonionic fluorine-containing surfactant and preparation method and application thereof |
| CN113616973B (en) * | 2021-08-19 | 2022-05-13 | 四川大学 | Catalytic cracking method of waste perfluoropolyether lubricating oil |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0002098A1 (en) * | 1977-11-10 | 1979-05-30 | E.I. Du Pont De Nemours And Company | Removal of perfluoroisobutylene |
| US5705719A (en) * | 1996-08-01 | 1998-01-06 | E. I. Du Pont De Nemours And Company | Selective removal of perfluoroisobutylene from streams of halogenated hydrocarbons |
| CN1483679A (en) * | 2003-07-23 | 2004-03-24 | 上海三爱富新材料股份有限公司 | Degradation method for fluorine-containing ether and method for treating fluofine-containing ether sewage |
| CN1583693A (en) * | 2004-06-04 | 2005-02-23 | 上海三爱富新材料股份有限公司 | Treating method and apparatus for perfluoro-isobutene methanol absorbing liquid |
| CN1923775A (en) * | 2005-08-29 | 2007-03-07 | 山东东岳高分子材料有限公司 | Removed method for poisonous component of cleaved product in hexafluoropropylene manufacturing technique |
-
2012
- 2012-12-30 CN CN201210583643.4A patent/CN103073385B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0002098A1 (en) * | 1977-11-10 | 1979-05-30 | E.I. Du Pont De Nemours And Company | Removal of perfluoroisobutylene |
| US5705719A (en) * | 1996-08-01 | 1998-01-06 | E. I. Du Pont De Nemours And Company | Selective removal of perfluoroisobutylene from streams of halogenated hydrocarbons |
| CN1483679A (en) * | 2003-07-23 | 2004-03-24 | 上海三爱富新材料股份有限公司 | Degradation method for fluorine-containing ether and method for treating fluofine-containing ether sewage |
| CN1583693A (en) * | 2004-06-04 | 2005-02-23 | 上海三爱富新材料股份有限公司 | Treating method and apparatus for perfluoro-isobutene methanol absorbing liquid |
| CN1923775A (en) * | 2005-08-29 | 2007-03-07 | 山东东岳高分子材料有限公司 | Removed method for poisonous component of cleaved product in hexafluoropropylene manufacturing technique |
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