CN103467242A - Recycling method of hexafluoropropylene in photooxidation reaction residue liquid - Google Patents
Recycling method of hexafluoropropylene in photooxidation reaction residue liquid Download PDFInfo
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- CN103467242A CN103467242A CN2013103998890A CN201310399889A CN103467242A CN 103467242 A CN103467242 A CN 103467242A CN 2013103998890 A CN2013103998890 A CN 2013103998890A CN 201310399889 A CN201310399889 A CN 201310399889A CN 103467242 A CN103467242 A CN 103467242A
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Abstract
The invention belongs to the field of high polymer chemistry, and provides a recycling method of hexafluoropropylene in a photooxidation reaction residue liquid. The method comprises the following steps of 1) preparing a fluorine-containing surfactant from the hexafluoropropylene in an oxidation polymerization manner and performing distillation separation on a reaction product at -40 DEG C to 100 DEG C so as to output a distilled gas phase; 2) performing alkali washing on the distilled gas phase with a sodium hydroxide solution or a potassium hydroxide solution; 3) performing water washing on the gas phase which is obtained by the step 2) and subjected to the alkali washing, and dehydrating the gas phase subjected to the water washing with a drying agent or in a refrigeration manner; and 4) performing pressurization rectification on a dehydrated gas phase compound under the pressure within 0.1MPa to 0.5MPa and under the condition that the temperature of collected materials at the top of a rectification tower is within 0 DEGC to 15 DEG C. According to the method provided by the invention, the treatment capacity of subsequent burning of the residue liquid during the preparation of the fluorine-containing surfactant is decreased; and meanwhile, the usage efficiency of the hexafluoropropylene taken as a main raw material is improved and the cost for preparing the fluorine-containing surfactant is lowered. The hexafluoropropylene is recycled by using the existing chemical equipment, so that the good economic benefit is obtained while the environment is protected.
Description
Technical field
The invention belongs to chemical field, relate in particular to the separating and purifying method of organic high fluoropolymer.
Background technology
Fluorochemical surfactant is the tensio-active agent of commercial a kind of property progressively in the last few years.With the conventional surfactants difference, fluorochemical surfactant is mainly usingd alkyl that perfluoroalkyl or perfluor or part fluoridized etc. as the hydrophobic group part in tensio-active agent, and then introduces on demand suitable connection base and hydrophilic radical.Fluorochemical surfactant can be made dispersion agent and use when the dispersion polymerization of various fluoro-resin.
Since the 1950's, Perfluorocaprylic Acid (ammonium) is (PFOA) a kind of fluorochemical surfactant be most widely used, and PFOA is widely used in hundreds of chemical industry, mechanical industry and daily perfluorination chemical product.In recent years, day by day deep along with correlative study, the same with a lot of high molecular polymers, the PFOA stabilizer pole, can not be degraded, can forever exist at occurring in nature once emit just, affect environment, experimentation on animals shows, PFOA can cause liver, reproduction, growth, heredity and the toxicity such as immune.The relevant report of SAB of American National Environmental Protection Agency is described as PFOA " possible (likely) carcinogens ", American National Environmental Protection Agency has worked out relevant plan and has impelled manufacturing enterprise initiatively to cut down PFOA material content in product, to cut down PFOA and the discharge of parent material in environment thereof.In addition, the developed countries such as America and Europe are also advancing the Study on Risk Assessment of PFOA and related substances thereof, and actively seek safer substitute products.The research of PFOA substitute becomes the current common focus of paying close attention in the world.
The method of traditional production fluorochemical surfactant is electrofluorination method and fluorine-containing alkyl iodide telomerization method.
Based on finding a kind of fluorine-containing emulsifier that can substitute Perfluorocaprylic Acid, and can overcome all drawbacks in traditional preparation method, in prior art, the preparation method of fluorine-containing emulsifier (CN101648122) adopts UV-light to cause at low temperatures, make polymerization single polymerization monomer reaction containing oxidation in fluorous solvent polymerization at certain, the photopolymerization product obtains fluorine-containing emulsifier through hydrolysis.At this, prepare in the fluorine-containing emulsifier process, after using R 1216 to carry out the photoxidation polymerization, there is a large amount of R 1216s not react, and thisly contain a large amount of R 1216 raffinates and continue on for photoxidation polyreaction efficiency and will reduce, common way is that these raffinates are carried out to burning disposal.The present invention prepares the follow-up burning disposal amount of raffinate in fluorochemical surfactant for reducing exactly, improves the service efficiency of main raw material R 1216 simultaneously, is reduced in the cost for preparing fluorochemical surfactant.
Summary of the invention
For the weak point of this area existence, the objective of the invention is to propose the recovery method of R 1216 in a kind of photooxidation reaction raffinate.
The object of the invention realizes by following technical proposals:
The recovery method of R 1216 in a kind of photooxidation reaction raffinate comprises step:
1), R 1216 under the initiation of UV-light, oxypolymerization prepares fluorochemical surfactant, reacted reaction product is-40～100 ℃ of lower fractionation by distillation, derives the gas phase distillated;
2), sodium hydroxide or potassium hydroxide solution alkali cleaning for step 1) gained gas phase;
3), step 2) gas phase after the gained alkali cleaning washes with water, desiccant dehydration or lyophilization for the gas phase after washing;
4), the dehydration after organic phase compression rectification under pressure 0.1～0.50MPa, rectifying tower top collection material temperature is 0～15 ℃.
Described photooxidation reaction, that R 1216 is under the initiation of UV-light, dioxygen oxidation R 1216 polymerization prepare fluorochemical surfactant, in reacted reaction product, there is a large amount of R 1216s not react, the process of these R 1216s and byproduct of reaction impurity detects, R 1216 content is 40%～60%, and other impurity amounts to content nearly 30～40%.These byproduct of reaction impurity mainly contain fluorine-containing low molecular alkane, fluorine-containing superoxide, fluorine-containing carbonyl compound, fluorine-containing ether.Fluorine-containing low molecule alkane comprises: tetrafluoroethylene, hexafluoroethane etc.; Fluorine-containing superoxide mainly contains CF
3oOCF
3, CF
3cF
2oOCF
3; Fluorine-containing carbonyl compound mainly contains fluorophosgene, Perfluoroacetone, and the perfluor acetylfluoride, perfluoro-propionyl fluoride, fluorine-containing ether is mainly the perfluoro-methyl ethyl ether, the perfluor dme.
Preferably, described step 1) is 30～50 ℃ of lower fractionation by distillation.
Wherein, described step 2), the mass concentration of sodium hydroxide or potassium hydroxide solution is 5～20%; Sodium hydroxide or potassium hydroxide solution from top to bottom with the gas phase counter-current absorption distillated, flux of alkaline liquor is 10m
3/ h～20m
3/ h, gas phase flow rate 5m
3/ h～20m
3/ h.
Wherein, the equipment of described alkali cleaning is that conventional material, inwall have the fluoro-containing plastic lining, or makes with Haast alloy (Hastelloy) material.Soda-wash tower is preferably used in alkali cleaning, certainly also is not limited only to this kind of mode of soda-wash tower, and the device of every applicable washing all can.Lower boiling compound enters the soda-wash tower bottom with gas phase, and alkali cleaning is contacted with the lower boiling fluorochemicals of gas phase from top to bottom with the pump Recycle design.Alkali cleaning be use soluble in the various oxyhydroxide of water, such as KOH, NaOH etc. all can, remove acidic impurities.Fluorine-containing impurities a large amount of in alkaline cleaning procedure can be got rid of, and comprising: fluorine-containing superoxide: CF
3oOCF
3, CF
3cF
2oOCF
3; Fluorine-containing carbonyl compound: fluorophosgene, Perfluoroacetone, perfluor acetylfluoride, perfluoro-propionyl fluoride, fluorine-containing ether: perfluoro-methyl ethyl ether, perfluor dme.
Wherein, the water volume of washing in described step 3) is that gaseous phase volume is than being 1:1～2:1; Water from top to bottom with the gas phase counter-current absorption.Described washing is to use deionized water, removes the alkaline matter of the trace brought by alkali cleaning.
Perhaps, in described step 3), the temperature of lyophilization is 0～10 ℃.General first freezing most of water of deviating from, and then with the vitriol oil or Silicagel dehydration.
Wherein, in described step 3), siccative is the vitriol oil or silica gel, controls gas velocity 3～10m
3.During dehydration, the vitriol oil or Silicagel dehydration agent install with container, and air-flow is through the vitriol oil or silica gel, because be to deviate from micro-moisture, so life-time service, it is not very frequent changing, until silica gel variable color or the vitriol oil are thinning, can't use.
Wherein, the tower reactor temperature of rectifying in described step 4) is controlled at 40～80 ℃, and rectifying tower top collection material temperature is 0～15 ℃, and preferably will collect the top temperature control is temperature range preferably at 8～9 ℃.
Wherein, in described step 4), the equipment of rectifying is packing tower, tetrafluoro resin class filler, for example: O type ring or Pall ring.Fluoro-containing plastic lining (tower body is the common metal material) is arranged in rectifying tower, or make with the Haast alloy material.Described fluoro-containing plastic is selected from a kind of in F46, PVDF, trifluorochloroethylene (PCTFE), fluorinated ethylene propylene (PVF), poly(vinylidene fluoride) (PVDF), voltalef (PCTFE), tetrafluoroethylene (PTFE).
Beneficial effect of the present invention:
Method of the present invention has reduced the follow-up burning disposal amount of raffinate in fluorochemical surfactant for preparing, and improves the service efficiency of main raw material R 1216 simultaneously, is reduced in the cost for preparing fluorochemical surfactant.The present invention uses existing chemical industry equipment, realizes the recovery of R 1216, has obtained fabulous economic benefit, has protected environment.
The accompanying drawing explanation
Fig. 1 is R 1216 recovery process figure of the present invention.
Embodiment
Following examples are used for the present invention is described, but are not used for limiting the scope of the invention.
Embodiment 1
Flow process is shown in Fig. 1.Reaction product after photooxidation reaction, wherein R 1216 content is 50%, reacted reaction product, in 40 ℃ of lower fractionation by distillation (hot water bath heating), derives the gas phase distillated;
Potassium hydroxide 15% solution water solution alkali cleaning for gas phase: importing the soda-wash tower that the PTFE lining is arranged, is tetrafluoro resin filler (O type ring) in tower, and potassium hydroxide 15% solution water solution is from tower top drenches, and gas phase enters at the bottom of tower, and liquid-gas ratio is the 1.5:1(volume ratio).
Gas phase after alkali cleaning washes with water: water is from the water wash column tower top drenches, and gas phase enters at the bottom of water wash column, and liquid-gas ratio is the 1.4:1(volume ratio); Gas phase after washing is first passed through the lyophilization device, under 0～5 ℃ of condition, deviates from most of moisture, then through silica-gel drier, removes a small amount of moisture, and gas velocity is 5m
3.Gas phase after dehydration is compression rectification under pressure 0.4MPa, and the tower reactor temperature is controlled at 50 ℃, and the top temperature control, at 8～9 ℃, is collected R 1216.
Cut after rectifying is through gas chromatographic analysis, and R 1216 purity is 99.9%.
Embodiment 2
Flow process is shown in Fig. 1.Reaction product after photooxidation reaction, wherein R 1216 content is 50%, reacted reaction product, in 45 ℃ of lower fractionation by distillation (hot water bath heating), derives the gas phase distillated;
Potassium hydroxide 15% solution water solution alkali cleaning for gas phase: import the soda-wash tower in PTFE is arranged, potassium hydroxide 15% solution water solution is from tower top drenches, and gas phase enters at the bottom of tower, and liquid-gas ratio is the 1.5:1(volume ratio).
Gas phase after alkali cleaning washes with water: water is from the water wash column tower top drenches, and gas phase enters at the bottom of water wash column, and liquid-gas ratio is the 1.5:1(volume ratio); Gas phase after washing is first passed through the lyophilization device, under 0～5 ℃ of condition, deviates from most of moisture, then through silica-gel drier, removes a small amount of moisture, and gas velocity is 8m
3.Gas phase after dehydration is compression rectification under pressure 0.45MPa, and the tower reactor temperature is controlled at 45 ℃, and the tower top temperature control, at 6～8 ℃, is collected R 1216.
Cut after rectifying is through gas chromatographic analysis, and R 1216 purity is 99.0%.
Above embodiment is described the preferred embodiment of the present invention; not scope of the present invention is limited; design under the prerequisite of spirit not breaking away from the present invention; various modification and improvement that the common engineering technical personnel in this area make technical scheme of the present invention, all should fall in the definite protection domain of claims of the present invention.
Claims (10)
1. the recovery method of R 1216 in a photooxidation reaction raffinate comprises step:
1), R 1216 under the initiation of UV-light, oxypolymerization prepares fluorochemical surfactant, reacted reaction product is-40～100 ℃ of lower fractionation by distillation, derives the gas phase distillated;
2), sodium hydroxide or potassium hydroxide solution alkali cleaning for step 1) gained gas phase;
3), step 2) gas phase after the gained alkali cleaning washes with water, lyophilization and/or desiccant dehydration for the gas phase after washing;
4), the dehydration after gas phase compound compression rectification under pressure 0.1～0.5MPa, rectifying tower top collection material temperature is 0～15 ℃.
2. recovery method according to claim 1, is characterized in that, described step 1) is for to go out the gas phase compound 40～50 ℃ of lower fractionation by distillation.
3. recovery method according to claim 1, is characterized in that, described step 2) in the mass concentration of sodium hydroxide or potassium hydroxide solution be 5～20%; Sodium hydroxide or potassium hydroxide solution from top to bottom with the gas phase counter-current absorption distillated, sodium hydroxide or potassium hydroxide solution flow are 10m
3/ h～20m
3/ h, gas phase flow rate 5m
3/ h～20m
3/ h.
4. according to the arbitrary described recovery method of claim 1～3, it is characterized in that, the equipment of described alkali cleaning is the fluoro-containing plastic lining, or makes with the Haast alloy material.
5. according to the arbitrary described recovery method of claim 1～3, it is characterized in that, the water volume of washing in described step 3) is 1:1～2:1 with the gaseous phase volume ratio; Water from top to bottom with the gas phase counter-current absorption.
6. according to the arbitrary described recovery method of claim 1～3, it is characterized in that, in described step 3), the temperature of lyophilization is 0～10 ℃.
7. according to the arbitrary described recovery method of claim 1～3, it is characterized in that, in described step 3), siccative is the vitriol oil or silica gel.
8. according to the arbitrary described recovery method of claim 1～3, it is characterized in that, the tower reactor temperature of rectifying in described step 4) is controlled at 40～80 ℃.
9. according to the arbitrary described recovery method of claim 1～3, it is characterized in that, in described step 4), rectifying tower top collection material temperature is 8～9 ℃.
10. according to the arbitrary described recovery method of claim 1～3, it is characterized in that, in described step 4), the equipment of rectifying is packing tower, and described filler is the tetrafluoro resin material, and described rectifying tower is provided with the fluoro-containing plastic lining or makes with the Haast alloy material at inwall.
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|---|---|---|---|
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|---|---|---|---|
| CN201310399889.0A CN103467242B (en) | 2013-09-05 | 2013-09-05 | Recycling method of hexafluoropropylene in photooxidation reaction residue liquid |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104788282A (en) * | 2015-03-17 | 2015-07-22 | 中昊晨光化工研究院有限公司 | Water removal method in perfluoropropylene production process |
| CN110023272A (en) * | 2016-11-30 | 2019-07-16 | Ａｇｃ株式会社 | The manufacturing method of the chloro- 2,3,3- trifluoro propene of 1- |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3665041A (en) * | 1967-04-04 | 1972-05-23 | Montedison Spa | Perfluorinated polyethers and process for their preparation |
| CN102516039A (en) * | 2011-11-16 | 2012-06-27 | 中昊晨光化工研究院 | Preparation method of fluorine-containing vinyl ether |
-
2013
- 2013-09-05 CN CN201310399889.0A patent/CN103467242B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3665041A (en) * | 1967-04-04 | 1972-05-23 | Montedison Spa | Perfluorinated polyethers and process for their preparation |
| CN102516039A (en) * | 2011-11-16 | 2012-06-27 | 中昊晨光化工研究院 | Preparation method of fluorine-containing vinyl ether |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104788282A (en) * | 2015-03-17 | 2015-07-22 | 中昊晨光化工研究院有限公司 | Water removal method in perfluoropropylene production process |
| CN110023272A (en) * | 2016-11-30 | 2019-07-16 | Ａｇｃ株式会社 | The manufacturing method of the chloro- 2,3,3- trifluoro propene of 1- |
| CN110023272B (en) * | 2016-11-30 | 2022-08-12 | Ａｇｃ株式会社 | Method for producing 1-chloro-2, 3, 3-trifluoropropene |
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