CN100334048C - Device for treating perfluoroisobutylene methanol absorption liquid - Google Patents
Device for treating perfluoroisobutylene methanol absorption liquid Download PDFInfo
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- CN100334048C CN100334048C CNB2006100679713A CN200610067971A CN100334048C CN 100334048 C CN100334048 C CN 100334048C CN B2006100679713 A CNB2006100679713 A CN B2006100679713A CN 200610067971 A CN200610067971 A CN 200610067971A CN 100334048 C CN100334048 C CN 100334048C
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- Prior art keywords
- perfluoroisobutylene
- methyl alcohol
- absorption liquid
- methyl
- methyl ether
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- 239000007788 liquid Substances 0.000 title claims abstract description 83
- 238000010521 absorption reaction Methods 0.000 title claims abstract description 70
- NOUSFPXUYQICRZ-UHFFFAOYSA-N methanol 1,1,3,3,3-pentafluoro-2-(trifluoromethyl)prop-1-ene Chemical compound OC.FC(F)=C(C(F)(F)F)C(F)(F)F NOUSFPXUYQICRZ-UHFFFAOYSA-N 0.000 title abstract 3
- AQHKYFLVHBIQMS-UHFFFAOYSA-N 2-[difluoro(methoxy)methyl]-1,1,1,3,3,3-hexafluoropropane Chemical compound COC(F)(F)C(C(F)(F)F)C(F)(F)F AQHKYFLVHBIQMS-UHFFFAOYSA-N 0.000 claims abstract description 70
- 238000009835 boiling Methods 0.000 claims abstract description 18
- 239000006228 supernatant Substances 0.000 claims abstract description 15
- OKKJLVBELUTLKV-UHFFFAOYSA-N methanol Natural products OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 209
- -1 perfluoroisobutylene methyl alcohol Chemical compound 0.000 claims description 88
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 40
- 230000008676 import Effects 0.000 claims description 16
- 238000003756 stirring Methods 0.000 claims description 12
- 238000012545 processing Methods 0.000 abstract description 4
- 239000012530 fluid Substances 0.000 abstract description 2
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 50
- 238000000034 method Methods 0.000 description 47
- 239000003513 alkali Substances 0.000 description 42
- 229910052731 fluorine Inorganic materials 0.000 description 40
- 239000011737 fluorine Substances 0.000 description 40
- 239000012043 crude product Substances 0.000 description 36
- 238000006243 chemical reaction Methods 0.000 description 29
- 238000000926 separation method Methods 0.000 description 26
- 239000007864 aqueous solution Substances 0.000 description 25
- 239000007789 gas Substances 0.000 description 23
- 230000003068 static effect Effects 0.000 description 21
- DAFIBNSJXIGBQB-UHFFFAOYSA-N perfluoroisobutene Chemical group FC(F)=C(C(F)(F)F)C(F)(F)F DAFIBNSJXIGBQB-UHFFFAOYSA-N 0.000 description 16
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 15
- 230000008569 process Effects 0.000 description 13
- 239000000243 solution Substances 0.000 description 12
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 11
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 11
- 239000000463 material Substances 0.000 description 10
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 9
- 239000012670 alkaline solution Substances 0.000 description 9
- NROKBHXJSPEDAR-UHFFFAOYSA-M potassium fluoride Chemical compound [F-].[K+] NROKBHXJSPEDAR-UHFFFAOYSA-M 0.000 description 9
- 239000002351 wastewater Substances 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 8
- 238000001816 cooling Methods 0.000 description 8
- 229910000040 hydrogen fluoride Inorganic materials 0.000 description 8
- 238000002203 pretreatment Methods 0.000 description 8
- 238000004821 distillation Methods 0.000 description 7
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 7
- 238000007781 pre-processing Methods 0.000 description 7
- 238000003860 storage Methods 0.000 description 7
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 7
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 6
- 239000002253 acid Substances 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 238000005406 washing Methods 0.000 description 6
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 5
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical group CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 5
- 238000004458 analytical method Methods 0.000 description 5
- 230000007797 corrosion Effects 0.000 description 5
- 238000005260 corrosion Methods 0.000 description 5
- 238000012856 packing Methods 0.000 description 5
- 239000012071 phase Substances 0.000 description 5
- 238000000197 pyrolysis Methods 0.000 description 5
- 235000011121 sodium hydroxide Nutrition 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- 230000008021 deposition Effects 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 239000012074 organic phase Substances 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000009833 condensation Methods 0.000 description 3
- 230000005494 condensation Effects 0.000 description 3
- 238000005796 dehydrofluorination reaction Methods 0.000 description 3
- 238000004090 dissolution Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 235000015320 potassium carbonate Nutrition 0.000 description 3
- 238000011084 recovery Methods 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 229910001220 stainless steel Inorganic materials 0.000 description 3
- 239000010935 stainless steel Substances 0.000 description 3
- 239000002699 waste material Substances 0.000 description 3
- HIXDQWDOVZUNNA-UHFFFAOYSA-N 2-(3,4-dimethoxyphenyl)-5-hydroxy-7-methoxychromen-4-one Chemical compound C=1C(OC)=CC(O)=C(C(C=2)=O)C=1OC=2C1=CC=C(OC)C(OC)=C1 HIXDQWDOVZUNNA-UHFFFAOYSA-N 0.000 description 2
- SZNYYWIUQFZLLT-UHFFFAOYSA-N 2-methyl-1-(2-methylpropoxy)propane Chemical compound CC(C)COCC(C)C SZNYYWIUQFZLLT-UHFFFAOYSA-N 0.000 description 2
- 241000196324 Embryophyta Species 0.000 description 2
- 239000008346 aqueous phase Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 231100001010 corrosive Toxicity 0.000 description 2
- 230000002950 deficient Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 239000012467 final product Substances 0.000 description 2
- 238000005194 fractionation Methods 0.000 description 2
- 231100000086 high toxicity Toxicity 0.000 description 2
- 229910001512 metal fluoride Inorganic materials 0.000 description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 description 2
- 235000011181 potassium carbonates Nutrition 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 231100000004 severe toxicity Toxicity 0.000 description 2
- 235000017550 sodium carbonate Nutrition 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- 230000007480 spreading Effects 0.000 description 2
- 238000003892 spreading Methods 0.000 description 2
- 238000011179 visual inspection Methods 0.000 description 2
- 239000003039 volatile agent Substances 0.000 description 2
- LGPPATCNSOSOQH-UHFFFAOYSA-N 1,1,2,3,4,4-hexafluorobuta-1,3-diene Chemical compound FC(F)=C(F)C(F)=C(F)F LGPPATCNSOSOQH-UHFFFAOYSA-N 0.000 description 1
- QMIWYOZFFSLIAK-UHFFFAOYSA-N 3,3,3-trifluoro-2-(trifluoromethyl)prop-1-ene Chemical compound FC(F)(F)C(=C)C(F)(F)F QMIWYOZFFSLIAK-UHFFFAOYSA-N 0.000 description 1
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 1
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical compound ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 206010069351 acute lung injury Diseases 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 239000003518 caustics Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 239000002826 coolant Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000284 extract Substances 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 150000004673 fluoride salts Chemical class 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 230000035876 healing Effects 0.000 description 1
- VBZWSGALLODQNC-UHFFFAOYSA-N hexafluoroacetone Chemical compound FC(F)(F)C(=O)C(F)(F)F VBZWSGALLODQNC-UHFFFAOYSA-N 0.000 description 1
- 239000003317 industrial substance Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- GBMDVOWEEQVZKZ-UHFFFAOYSA-N methanol;hydrate Chemical compound O.OC GBMDVOWEEQVZKZ-UHFFFAOYSA-N 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 231100001228 moderately toxic Toxicity 0.000 description 1
- BCCOBQSFUDVTJQ-UHFFFAOYSA-N octafluorocyclobutane Chemical compound FC1(F)C(F)(F)C(F)(F)C1(F)F BCCOBQSFUDVTJQ-UHFFFAOYSA-N 0.000 description 1
- 235000019407 octafluorocyclobutane Nutrition 0.000 description 1
- 239000011698 potassium fluoride Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
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- 230000002441 reversible effect Effects 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- DFEYYRMXOJXZRJ-UHFFFAOYSA-N sevoflurane Chemical compound FCOC(C(F)(F)F)C(F)(F)F DFEYYRMXOJXZRJ-UHFFFAOYSA-N 0.000 description 1
- 230000002269 spontaneous effect Effects 0.000 description 1
- 230000002459 sustained effect Effects 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The present invention discloses a tubular processor used for processing absorption liquid of perfluoroisobutylene methanol, which comprises a barrel body and a lower weak lye inlet (2), a middle inlet (3) of the absorption liquid of the perfluoroisobutylene methanol, a lower outlet (10) of octafluoro isobutyl methylether, an upper overflow port (6) of supernatant fluid and an upper boiling gas outlet (8) which are arranged on the barrel body.
Description
Patent application of the present invention is that the application number submitted on June 4th, 2004 is 200410024921.8, denomination of invention is divided an application for the Chinese patent application of " treatment process and the equipment of perfluoroisobutylene methyl alcohol absorption liquid ".
Technical field
The present invention relates to the treatment process of perfluoroisobutylene methyl alcohol absorption liquid, also relate to the equipment that is used to handle perfluoroisobutylene methyl alcohol absorption liquid.
Background technology
Pyrolysis method production tetrafluoroethylene and R 1216 are (for example, tetrafluoroethylene pyrolysis method production R 1216) can produce perfluoroisobutylene (PFIB) in the process, perfluoroisobutylene is valuable industrial chemicals, and therefore how fully utilizing perfluoroisobutylene effectively is the common concerned issue in global fluorine chemical field.
β position CF in the perfluoroisobutylene molecule
3Strong sucting electronic effect cause the Electron Affinities of the two keys of its C=C to substantially exceed two keys of C=C in perfluorobuttene-1, perfluorobuttene-2, R 1216, the tetrafluoroethylene molecule, so perfluoroisobutylene (its Lct that shows that chemically reactive is big, toxicity is high
50Be 0.87mgmin/L, than big ten times in phosgene), and volatile (boiling point is 6.4 ℃), do not have and to smell tastelessly, be difficult in the air being found in case leak into.Perfluoroisobutylene belongs to pneumotropism severe toxicity gas, and human body sucks perfluoroisobutylene gas can cause acute lung injury.
The high toxicity of perfluoroisobutylene, be difficult to precaution and be difficult to healing property, limited the direct utilization of perfluoroisobutylene.Produce the security of R 1216 process in order to improve the tetrafluoroethylene pyrolysis method, the method that adopts the methyl alcohol selectivity to absorb perfluoroisobutylene is in the prior art eliminated the perfluoroisobutylene of severe toxicity and is produced in the R 1216 production process at the tetrafluoroethylene pyrolysis method.Therefore it is comprehensive utilization perfluoroisobutylene methyl alcohol absorption liquid technology that present comprehensive utilization perfluoroisobutylene technology has been developed.
The tetrafluoroethylene pyrolysis method is produced the splitting gas that contains perfluoroisobutylene that R 1216 produces or is contained the high boiling material of perfluoroisobutylene splitting gas and excessive methyl alcohol contact reacts, can produce the methanol mixed solution that mainly contains (also containing perfluoroisobutylene sometimes) such as octafluoro isobutyl-methyl ether, seven fluorine iso-butylene methyl ethers (on a small quantity), perfluoroolefine compounds, hydrogen fluoride (below be referred to as perfluoroisobutylene methyl alcohol absorption liquid).This perfluoroisobutylene methyl alcohol liquid absorption element complexity along with the variation of component and ambient conditions, can be destroyed original absorption-dissolution equilibrium, thereby discharge the toxic gas that is dissolved in wherein when it is handled.Therefore perfluoroisobutylene methyl alcohol absorption liquid comprehensive utilization difficulty is big, and treatment process commonly used at present remains burning.
Secondly but existing burning disposal has very big defective, at first wastes useful resource, burns that the waste gas that produces also needs to handle again, its tail gas and waste residue still pollute the environment.Therefore, the integrated conduct method that needs a kind of perfluoroisobutylene methyl alcohol absorption liquid.
Seven fluorine iso-butylene methyl ethers are a kind of important chemical material, and for example, it can be used for producing Perfluoroacetone, Ultane, hexafluoro-isobutene etc.In addition, seven fluorine iso-butylene methyl ether stability in storagies are better than octafluoro isobutyl-methyl ether.
Susumu Misaki deposits
The fluorine chemistry magazine(Journal of Fluorine Chemistry, 29 (1985) 471-474) disclose a kind of in the presence of alkali (as the potassium hydroxide of 25-50%) on, octafluoro isobutyl-methyl ether dehydrofluorination is degraded into the method for seven fluorine iso-butylene methyl ethers and 2-trifluoromethyl-3-methoxyl group-1-perfluoro propylene, and its chemical equation is as follows:
(CF
3)
2CHCF
2OCH
3→(CF
3)
2C＝CFOCH
3+CF
2＝C(CF
3)CF
2OCH
3
The use liquid caustic soda is sloughed hydrofluoric reaction conditions and the result in the compound
| The kind of alkali | The consumption of alkali (with respect to 1 mole of octafluoro isobutyl-methyl ether) | Temperature of reaction (℃) | Reaction times (hour) | The transformation efficiency of octafluoro isobutyl-methyl ether | The productive rate of seven fluorine iso-butylene methyl ethers | The yield of 2-trifluoromethyl-3-methoxyl group-1- |
| KOH | ||||||
| 2 | 65-85 | 1.5 | 100 | 80.3 | 4.2 | |
| KOH | 1.1 | 65-85 | 1.5 | 97.4 | 83.3 | 7.1 |
| NaOH | 1.1 | 65-85 | 1.8 | 86.1 | 77.7 | 3.2 |
| Ca(OH) 2 +KOH | 0.5 1.1 | 65-85 | 1.5 | 100 | 79.5 | 0.9 |
Annotate: the concentration of alkali is 50%
In view of Susumu Misaki discloses in the presence of alkali (as the potassium hydroxide of 25-50%), octafluoro isobutyl-methyl ether dehydrofluorination is degraded into the method for seven fluorine iso-butylene methyl ethers and 2-trifluoromethyl-3-methoxyl group-1-perfluoro propylene, this area has proposed the treatment process of following several perfluoroisobutylene methyl alcohol absorption liquids, to obtain important chemical material-seven fluorine iso-butylene methyl ether:
1) directly alkalize perfluoroisobutylene methyl alcohol absorption liquid, fractionation by distillation then;
2) straight run distillation perfluoroisobutylene methyl alcohol absorption liquid, the high cut of intercepting octafluoro isobutyl-methyl ether content are used for alkalization preparation seven fluorine iso-butylene methyl ethers;
3) perfluoroisobutylene methyl alcohol absorption liquid is directly washed, and removes a large amount of methyl alcohol and other water solubles and fluoride gas, again with the centinormal 1 alkaline solution reaction of 25-50%.
But all there is defective in these methods.For example,
Therefore the needs exploitation is a kind of can carry out method and apparatus continuous, simple and direct processing to the perfluoroisobutylene methyl alcohol absorption liquid of heterogeneity and the coexistence of different phase.
Summary of the invention
The purpose of this invention is to provide and a kind ofly can carry out method and apparatus continuous, simple and direct processing the perfluoroisobutylene methyl alcohol absorption liquid of heterogeneity and the coexistence of different phase.
Therefore, the invention provides a kind of treatment process of perfluoroisobutylene methyl alcohol absorption liquid, it comprises the steps:
1) with the centinormal 1 alkali aqueous solution pre-treatment of 1-25% perfluoroisobutylene methyl alcohol absorption liquid;
2) separate remove be dissolved with fluorochemical, methyl alcohol and other water solubles that reaction forms on the liquid that disappears;
3) make step 2) separate the lower floor's solution obtain and react with the centinormal 1 alkali aqueous solution of 25-50%.
The present invention also provides a kind of equipment that is used to handle perfluoroisobutylene methyl alcohol absorption liquid, it comprises that with equivalent concentration be 1-25% alkali aqueous solution pre-treatment perfluoroisobutylene methyl alcohol absorption liquid, obtain the equipment (pre-processing device) of octafluoro isobutyl-methyl ether crude product and be the equipment that the alkaline solution of 25-50% is handled described crude product with equivalent concentration, it is characterized in that described is 1-25% alkali aqueous solution pre-treatment perfluoroisobutylene methyl alcohol absorption liquid with equivalent concentration, and the equipment (pre-processing device) that obtains octafluoro isobutyl-methyl ether crude product comprising:
Tubular type treater, this tubular type treater have bottom sig water import, middle part perfluoroisobutylene methyl alcohol absorption liquid import, the outlet of bottom octafluoro isobutyl-methyl ether crude product, top supernatant liquor spillway, upper gas escape orifice.
Pre-processing device of the present invention also can comprise one second static separation device, and its top links to each other with the bottom octafluoro isobutyl-methyl ether outlet of tubular type treater, and its underpart links to each other with the crude product storage tank by the crude product pipeline.
Description of drawings
Below, further specify the present invention in conjunction with the accompanying drawings.In the accompanying drawing:
Fig. 1 is a process flow sheet of handling perfluoroisobutylene methyl alcohol absorption liquid;
Fig. 2 is the synoptic diagram that is used as the plate washer stirring tower of tubular type treater in the better example of the present invention.
Embodiment
In this article, except as otherwise noted, otherwise the concentration of alkali aqueous solution is equivalent concentration.
The present invention handles perfluoroisobutylene methyl alcohol absorption liquid and mainly comprises three steps with the method that reclaims purpose product seven fluorine iso-butylene methyl ethers:
1. with the centinormal 1 alkali aqueous solution pre-treatment of 1-25% perfluoroisobutylene methyl alcohol absorption liquid
Purpose with the centinormal 1 alkali aqueous solution pre-treatment of 1-25% perfluoroisobutylene methyl alcohol absorption liquid is to remove the impurity except that octafluoro isobutyl-methyl ether and seven fluorine iso-butylene methyl ethers in the perfluoroisobutylene methyl alcohol absorption liquid as much as possible.After adding alkali aqueous solution, be dissolved in that hydrogen fluoride can react with alkali in the perfluoroisobutylene methyl alcohol absorption liquid, form soluble fluoride.Because the alkali aqueous solution that adds is a kind of dilute alkaline soln that contains big water gaging, therefore, the soluble fluoride of formation can be dissolved in aqueous phase with methyl alcohol again.This shows that the concentration of the alkali aqueous solution that adds should be too not high in this step, otherwise the fluoride dissolution that the water-content in the system is not enough to form is at aqueous phase, the fluorochemical precipitation of generation can have a negative impact to the reactions steps of back.
The concentration of the alkaline solution of Jia Ruing is the highest in this step is no more than 25%, better the highlyest is no more than 20%, better the highlyest is no more than 15%.
In addition, under the effect of alkali, part alkene contained in the perfluoroisobutylene methyl alcohol absorption liquid can decompose, and forms metal fluoride and enters water, thereby further reduce the content of impurity fluorine cpd.In addition, during alkali also plays a part and perfluoroisobutylene methyl alcohol absorption liquid in acid ion, in order to avoid it produces corrosive nature to equipment.Therefore, the concentration of the alkali aqueous solution of adding can not be too low.The concentration of the alkaline solution of Jia Ruing is minimum in this step is not less than 1%, better is not less than 3%, better is not less than 5%.
The alkali that is applicable to the inventive method is without particular limitation, as long as it is water miscible and can have a negative impact to the subsequent reaction step.In a better example of the present invention, described alkali can be selected from the alkali or the strong base-weak acid salt of the solubility of periodictable IA family or the element formation of IIA family, for example lithium hydroxide, potassium hydroxide, sodium hydroxide, hydrated barta, yellow soda ash, salt of wormwood or the like.Because final product Potassium monofluoride solubleness in water is big, therefore preferred potassium hydroxide and the salt of wormwood of using.
Be not wishing to be bound by theory, the inventor thinks, with the centinormal 1 alkali aqueous solution pre-treatment of 1-25% perfluoroisobutylene methyl alcohol absorption liquid the time, following physics one chemical transformation has taken place mainly:
1) hydrogen fluoride and alkali (as potassium hydroxide) carry out thermopositive reaction, generate Potassium monofluoride;
2) a part of octafluoro isobutyl-methyl ether and alkali (as potassium hydroxide) carry out thermopositive reaction, generate seven fluorine iso-butylene methyl ether and Potassium monofluorides;
3) be partly dissolved in lower boiling fluoride gas in the perfluoroisobutylene methyl alcohol absorption liquid, desorb discharges with gas form because balance is destroyed for perfluorobuttene-1, perfluorobuttene-2, perfluorobutadiene, perfluorocyclobutane (if absorption technique also is dissolved with R 1216, tetrafluoroethylene before the methyl alcohol);
4) methyl alcohol is extracted by water, metal fluoride salt (as Potassium monofluoride) is dissolved in water, the derivative of a spot of octafluoro isobutyl-methyl ether, seven fluorine iso-butylene methyl ethers and degree of depth defluorinate thereof is dissolved in water, forms the waste water that contains octafluoro isobutyl-methyl ether and organic fluoride, Potassium monofluoride, methyl alcohol etc. such as seven fluorine iso-butylene methyl ethers and derivative thereof.
In the present invention, described alkali aqueous solution depends on the concentration of the impurity except that octafluoro isobutyl-methyl ether and seven fluorine iso-butylene methyl ethers in the methyl alcohol absorption liquid with respect to the consumption of perfluoroisobutylene methyl alcohol absorption liquid.Those of ordinary skill in the art can easily determine the add-on of alkali aqueous solution according to concrete perfluoroisobutylene methyl alcohol absorption liquid.In a better example of the present invention, the weight feed molar ratio of described perfluoroisobutylene methyl alcohol absorption liquid and alkali aqueous solution is 1: 0.5-12 is preferably 1: 0.5-5, more preferably 1: 0.5-3.
In addition, as mentioned above, after adding equivalent concentration was the dilute alkaline soln of 1-25%, a part of octafluoro isobutyl-methyl ether can carry out thermopositive reaction with alkali (as potassium hydroxide), generates seven fluorine iso-butylene methyl ether and Potassium monofluorides.If reacting weight is too high, then can make the temperature fast rise of reaction system.Therefore, in a better example of the present invention, adopt refrigerative method for example that the temperature of reaction system is controlled at below 100 ℃, be preferably below 56 ℃, more preferably below 30 ℃.Described method of cooling is without particular limitation, and those of ordinary skill in the art can easily determine suitable method of cooling, example according to its expertise. as, water-cooled, air cooling etc.
In addition, allow in alkali aqueous solution, to add some materials relevant, as Potassium monofluoride, organofluorine compound etc. with system.Allow the existence of these materials, help process water and recycle.
2. separate the supernatant liquor of removing fluoride gas, dissolving Potassium monofluoride and the methyl alcohol etc. that are dissolved in the methyl alcohol absorption liquid
Because the proportion of the crude product of octafluoro isobutyl-methyl ether (containing a small amount of seven fluorine iso-butylene methyl ethers) is about 1.5, greater than the proportion of supernatant liquor.The crude product and the supernatant liquor of octafluoro isobutyl-methyl ether (containing a small amount of seven fluorine iso-butylene methyl ethers) almost can not dissolve each other simultaneously.Therefore, another feature of the present invention is to utilize the impure supernatant liquor and the solution that contains octafluoro isobutyl-methyl ether crude product of differential liberation of solution proportion.Separating step of the present invention is without particular limitation, can be any separating step known in the art.For example, can adopt separating funnel to separate described two kinds of solution.Whether in the present invention, term " supernatant liquor " is meant the liquid on the crude product top of octafluoro isobutyl-methyl ether (containing a small amount of seven fluorine iso-butylene methyl ethers), and as clear as crystal irrelevant with it.
The octafluoro isobutyl-methyl ether crude product that obtains can randomly further be purified to obtain the elaboration of octafluoro isobutyl-methyl ether.Described method of purification can be a method well-known in the art, for example, can adopt distillating method.
3 organic phase and the centinormal 1 alkali aqueous solution reactions of 25-50% that separation is obtained
Exist as Susumu Misaki
The fluorine chemistry magazine(Journal of Fluorine Chemistry, 29 (1985) 471-474) described, in the presence of the centinormal 1 alkali aqueous solution of 25-50%, octafluoro isobutyl-methyl ether dehydrofluorination is degraded into the method for seven fluorine iso-butylene methyl ethers and 2-trifluoromethyl-3-methoxyl group-1-perfluoro propylene, and its chemical equation is as follows:
(CF
3)
2CHCF
2OCH
3→(CF
3)
2C＝CFOCH
3+CF
2＝C(CF
3)CF
2OCH
3
The alkali that uses in this step can be selected from the alkali or the strong base-weak acid salt of the solubility of periodictable IA family or the element formation of IIA family, for example lithium hydroxide, potassium hydroxide, sodium hydroxide, hydrated barta, yellow soda ash, salt of wormwood or the like.Described alkali can be identical or inequality with the alkali that uses in the step 1).
The reaction that octafluoro isobutyl-methyl ether is degraded into seven fluorine iso-butylene methyl ethers is a kind of thermopositive reaction, therefore, need for example control speed of reaction or use the cooling system to control the temperature of reaction system.Those of ordinary skill in the art can easily take the temperature of adequate measures control reaction system in conjunction with its expertise after having read content disclosed by the invention.
The present invention also provides a kind of equipment that is used for perfluoroisobutylene methyl alcohol absorption liquid treatment process of the present invention, it comprises that with equivalent concentration be 1-25% alkali aqueous solution pre-treatment perfluoroisobutylene methyl alcohol absorption liquid, obtains the equipment (following abbreviation pre-processing device) of octafluoro isobutyl-methyl ether crude product and is the equipment that the alkaline solution of 25-50% is handled described crude product with equivalent concentration.As shown in Figure 1, described is 1-25% alkali aqueous solution pre-treatment perfluoroisobutylene methyl alcohol absorption liquid with equivalent concentration, and the equipment that obtains octafluoro isobutyl-methyl ether crude product comprises:
In a better example of the present invention, described equipment comprises one second static separation device 4, and its top links to each other with the bottom octafluoro isobutyl-methyl ether outlet 10 of tubular type treater 1, and its underpart links to each other with crude product storage tank 5 by crude product pipeline 19.
In a better example of the present invention, described tubular type treater 1 also comprises middle part backflow import 20; And described pre-processing device also comprises the first static separation device 9, its top links to each other with the top supernatant liquor spillway 6 of tubular type treater 1, the middle part links to each other with waste water storage tank 11 by waste pipe 18, and the bottom links to each other with the middle part backflow import 20 of tubular type treater 1 through valve 17.The purpose that adopts the first static separation device 9 is that further Separation and Recovery is entrained in the octafluoro isobutyl-methyl ether crude product in the supernatant liquor of desiring to abandon, to improve the organic efficiency of producing.
In another better example of the present invention, described tubular type treater 1 also has a top boiling pneumatic outlet 8, and described pre-processing device also comprises condenser 7, and its import links to each other with the top boiling pneumatic outlet 8 of tubular type treater 1, the tail gas outlet pipe 15 of waste water storage tank 11, the tail gas outlet of crude product storage tank 5 by pipeline 16; Outlet links to each other with next procedure equipment by pipe 14.The purpose that adopts condenser 7 is that the high temperature fraction that is entrained in the boiling gas is reclaimed in condensation, to improve the rate of recovery of product.
During operation, enter this tubular reactor by pipeline 13 from the bottom sig water import 2 of tubular reactor 1 through the sig water of metering; Perfluoroisobutylene methyl alcohol absorption liquid through metering enters this tubular reactor by pipeline 12 from the middle part perfluoroisobutylene methyl alcohol absorption liquid import 3 of tubular reactor 1.Following process takes place in the perfluoroisobutylene methyl alcohol absorption liquid that enters tubular reactor under the effect of diluted alkaline water:
1) since the compatibility of water and methyl alcohol greater than the compatibility of octafluoro isobutyl-methyl ether (containing a small amount of seven fluorine iso-butylene methyl ethers) and methyl alcohol, therefore under the powerful dissemination of for example agitator etc., make the mixing liquid miniaturization of octafluoro isobutyl-methyl ether (containing a small amount of seven fluorine iso-butylene methyl ethers)-methyl alcohol, the methyl alcohol that is dissolved in the octafluoro isobutyl-methyl ether (containing a small amount of seven fluorine iso-butylene methyl ethers) can be extracted by water.Octafluoro isobutyl-methyl ether crude product (containing a small amount of seven fluorine iso-butylene methyl ethers) proportion (being 1.5) is greater than the proportion of methanol-water solution, spontaneous generation sedimentation; Enter the second static separation device 4 via bottom octafluoro isobutyl-methyl ether outlet 10.Along with the increase that enters the crude product amount in the second static separation device 4, the octafluoro isobutyl-methyl ether crude product that accumulates in this static separation device enters octafluoro isobutyl-methyl ether crude product intercepting basin (thick ether storage tank) 5 automatically through pipeline 18 under the effect of static pressure;
2) fluorochemical (except that hydrogen fluoride) that is dissolved in the lower boiling (boiling point is below normal temperature) in the octafluoro isobutyl-methyl ether (containing a small amount of seven fluorine iso-butylene methyl ethers) will discharge with gas form, forms bubble.These fluorochemicals and octafluoro isobutyl-methyl ether compatibility are good, will carry out than the octafluoro isobutyl-methyl ether of lower boiling (56 ℃ of bp) easily.Therefore under the powerful dissemination of for example agitator etc., make the bubble miniaturization, the octafluoro isobutyl-methyl ether of gas-entrained in the bubble is contacted with water.Because the proportion effect, the octafluoro isobutyl-methyl ether in water precipitates, and separates with other fluoride gas.In a better example of the present invention, make fluoride gas remaining lower boiling (boiling point is below normal temperature), that be insoluble in water enter condenser 7 from the top boiling pneumatic outlet 8 of tubular type treater 1, through condenser remove a part of boiling point than higher material after, leave the system that handles perfluoroisobutylene methyl alcohol absorption liquid through pipeline 14.The gas that leaves can further fully utilize;
3) buck of 1-25% and hydrogen fluoride and part octafluoro isobutyl-methyl ether carry out thermopositive reaction, cause that system temperature rises, cause low-boiling octafluoro isobutyl-methyl ether (56 ℃ of bp) volatilization, therefore in a better example of the present invention, system need be cooled off and the fractional condensation expellant gas;
4) in order to improve the rate of recovery of octafluoro isobutyl-methyl ether crude product, in a better example of the present invention, make the waste water that contains methyl alcohol-potassium fluoride aqueous solution and a small amount of octafluoro isobutyl-methyl ether crude product etc. overflow to the first static separation device 9, go into waste water storage tank 11 by pipeline 18 overflows after further isolating octafluoro isobutyl-methyl ether crude product from the top supernatant liquor spillway 6 of tubular reactor 1; Open the valve 17 of the first static separation device, 9 bottoms when the octafluoro isobutyl-methyl ether crude product in the first static separation device 9 runs up to when a certain amount of, allow thick ether return tubular type treater 1.
Fig. 2 is the synoptic diagram of a better example of tubular type treater 1 of the present invention, and this is that a kind of plate washer stirs tower, it comprise a plurality of paddles 30 of rotating around central shaft that are parallel to each other and a plurality of be parallel to each other be positioned at the longitudinal baffle 31 that Ta Bishang radially extends.As shown in Figure 2, the methyl alcohol absorption liquid by inlet 3 enter stir tower, dilute alkaline soln enters the stirring tower by inlet 2, both mix mutually under the stirring action of paddle 30.Longitudinal baffle 31 can reinforcing mass transfer and prolongation fluid path.
In a better example of the present invention, the length-to-diameter ratio of described tubular type treater is greater than 1, better greater than 5, more preferably greater than 10.Utilizing the tubular type treater of big L/D ratio to help perfluoroisobutylene methyl alcohol absorption liquid and diluted alkaline water fully to contact with octafluoro isobutyl-methyl ether crude product fully separates with supernatant liquor;
Tubular type treater of the present invention can vertically be installed, but its also tiltable install, only otherwise influence its reaction and separating effect gets final product.In a better example of the present invention, the length direction of described tubular type treater and horizontal direction have for example 30-150 °, are preferably 60-120 ° angle.But the vertical length increase that increases the tubular type treater helps octafluoro isobutyl-methyl ether crude product and fully separates with supernatant liquor.
Advantage of the present invention
The present invention serially, side by side the perfluoroisobutylene methyl alcohol absorption liquid to heterogeneity and different phase coexistences reacts, extracts gas phase, extraction liquid phase, gas-liquid separation, liquid liquid isolation integral, has simplified treating processes and equipment;
The present invention can continuously, sealing handle highly toxic perfluoroisobutylene methyl alcohol absorption liquid, high toxicity, lower boiling Fluoride Separation in the perfluoroisobutylene methyl alcohol absorption liquid are come out to become tail gas, make that the moderately toxic octafluoro isobutyl-methyl ether crude product that is separated simultaneously can further be fully utilized;
The present invention uses Principles of Chemical Engineering to carry out separation, the conveying of material automatically, saves the manpower and the energy, realizes the automatic production process of less energy-consumption;
The present invention uses two kinds of reverse continuously abundant contact process of liquid, has significantly reduced the usage quantity of water and the eliminating amount of waste water, has saved the expense of wastewater treatment;
The present invention uses the sig water long-time continuous fully to contact perfluoroisobutylene methyl alcohol absorption liquid, removed the corrosives hydrogen fluoride in the perfluoroisobutylene methyl alcohol absorption liquid effectively, prevented the corrosion of hydrogen fluoride to the condenser of materials such as metal or lass lining, pipeline, reactor etc., widen the scope of equipment materials used, greatly reduced practical matter purpose expense.
Further specify the present invention below in conjunction with embodiment.
Use pre-processing device as shown in Figure 1.The tubular type treater that adopts is long 2 meters, and the 316L Stainless Steel Helices tower that internal diameter is 60 millimeters loads 3 * 3 316L stainless steel winding filler (the filler loading level is 2.0 kilograms).The upper end of described Stainless Steel Helices tower has top boiling pneumatic outlet 8 and top supernatant liquor spillway 6.0.5 meter of spillway spreading, the stainless first static separation device 9 of 80 millimeters 316L of internal diameter has an opening for feed 19 that links to each other with the discharge port of the described first static separation device 9 by valve in described packing tower middle and lower part; There are bottom sig water import 2 and bottom octafluoro isobutyl-methyl ether outlet 10 in the lower end of described packing tower; Bottom octafluoro isobutyl-methyl ether exports 0.5 meter of 10 spreading, the stainless second static separation device of 80 millimeters 316L of internal diameter; At packing tower pipe range 1/2 place methyl alcohol absorption liquid import 3 is arranged.
Feed the solution of potassium carbonate of equivalent concentration 10% in the bottom of described packing tower sig water import 2; Feed perfluoroisobutylene methyl alcohol absorption liquid at methyl alcohol absorption liquid import 3 places at 1/2 place of pipe range.Feed 0-5 ℃ cold water in the condenser.When the potassium hydroxide solution that feeds equivalent concentration 10% is 1.2: 1 with the weight that feeds perfluoroisobutylene methyl alcohol absorption liquid, the crude product of the octafluoro isobutyl-methyl ether that the second static separation device is discharged automatically, octafluoro isobutyl-methyl ether content in crude product analysis situation is octafluoro isobutyl-methyl ether 68%, seven fluorine iso-butylene methyl ethers 10%, methyl alcohol 0.9%.
When in the visual inspection first static separation device the liquid demixing phenomenon is arranged the time, open the bottom valve of the first static separation device, lower liquid is returned the tubular type treater.
After operation after a while, open the tubular type treater, not finding has the deposition of sending out fluorochemical on the tube wall, also find no the obvious corrosion phenomenon.
The flap that packing tower among the embodiment 1 is changed into as Fig. 2 structure stirs tower.Use the oar formula to stir 300 rev/mins of the long 17mm of blade, wide 10mm, rotating speeds.The crude product of the octafluoro isobutyl-methyl ether that the second static separation device is discharged automatically, octafluoro isobutyl-methyl ether content in crude product analysis situation is octafluoro isobutyl-methyl ether 66%, seven fluorine iso-butylene methyl ethers 12%, methyl alcohol 0.3%.
When in the visual inspection first static separation device the liquid demixing phenomenon is arranged the time open the bottom valve of the first static separation device, lower liquid is returned the tubular type treater.
After operation after a while, open the tubular type treater, not finding has the deposition of sending out fluorochemical on the tube wall, also find no the obvious corrosion phenomenon.
Adopt the method identical with embodiment 1, but the alkaline solution that adds is that equivalent concentration is 1% potassium hydroxide solution, its amount is 10 times of embodiment 1, the crude product of the octafluoro isobutyl-methyl ether that the second static separation device is discharged automatically, octafluoro isobutyl-methyl ether content in crude product analysis situation is octafluoro isobutyl-methyl ether 70%, seven fluorine iso-butylene methyl ethers 8%, methyl alcohol 0.7%.
After operation after a while, open the tubular type treater, not finding has the deposition of sending out fluorochemical on the tube wall, also find no the obvious corrosion phenomenon.
Adopt the method identical with embodiment 2, but the alkaline solution of adding is that equivalent concentration is 25% solution of potassium carbonate, the weight feed molar ratio of alkali aqueous solution and methyl alcohol absorption liquid is 3: 1.
After operation after a while, open the tubular type treater, not finding has the deposition of sending out fluorochemical on the tube wall, also find no the obvious corrosion phenomenon.
Comparative example 1
1050 gram perfluoroisobutylene methyl alcohol absorption liquids are fed in the three-necked flask of the 2000ml that has stirring and condenser, with 0～3 ℃ water cooling prolong.The solid KOH of 200 grams 85% is dropped in the three-necked flask in batches 20～25 ℃ of control reaction temperature, sustained reaction 5 hours, gas phase loss 330 grams.
Reaction solution poured in the 2000ml matrass distill, obtain purity (stratographic analysis) and be 91% seven fluorine iso-butylene methyl ethers, 150 grams, front-end volatiles 450 grams are adhering to white-yellowish solid on the matrass wall, need big water gaging to dash and remove, therefore produce the methanol waste water that contains F-in a large number.
Comparative example 2
Repeat above-mentioned experiment, with three washing reaction liquid of moisture of 6 times of amounts, isolate subnatant at every turn and wash, upper strata liquid is the methanol waste water that contains F-.Again with subnatant with anhydrous magnesium sulfate drying after to going in the matrass to distill, obtain purity and be 91.5% seven fluorine iso-butylene methyl ethers, 190 grams, front-end volatiles are 350 grams, almost do not have solids in the matrass, but raffinate is arranged.
Comparative example 3
1000 gram perfluoroisobutylene methyl alcohol absorption liquids are fed straight run distillation in 2000 milliliters of matrasss, as water coolant, distill, obtain with 0～3 ℃ water:
20～50 ℃ of cut 150 grams
5 1～65 ℃ of cut 520 grams
66～80 ℃ of cut 100 grams
Raffinate 20 grams
Loss 210 grams
Find that material is to the distillation plant seriously corroded.
In adding 300 gram 50%KOH solution in 1000 three-necked flasks that have stirring and condenser that 520 grams (51～65 ℃ of cuts) are housed, with 0～3 ℃ water cooling prolong.54 ℃ were reacted 2 hours down, reaction solution can't separate, need to add the water more than 2 times, just can tell organic phase, use 4 times moisture secondary washing organic phase again, obtain 350 grams, seven fluorine iso-butylene methyl ether crude products, stratographic analysis shows that seven fluorine iso-butylene methyl ethers are 64%, and octafluoro isobutyl-methyl ether is 14%.
Comparative example 4
Repeat the step of above-mentioned comparative example 3, but change KOH into NaOH, the reaction back generates the little NaF of solubleness, causes the NaF particulate to mix with subnatant, needs to add water dissolution NaF more than ten times difficult each other the separation, therefore produces the methanol waste water that contains F-in a large number.
Comparative example 5
1000 gram perfluoroisobutylene methyl alcohol absorption liquids are added to (existing loss of material) in the 2000ml three-necked bottle, add 600 gram 50%KOH solution again, 54 ℃ were reacted 3 hours, and reaction finishes the water that the back adds 3 times of amounts, just can tell lower floor's organic phase 420 and restrain.But octafluoro isobutyl-methyl ether that 14% end of still having an appointment in the subnatant transforms and 1% methyl alcohol.
Comparative example 6
In 2 hours 1000 gram perfluoroisobutylene methyl alcohol absorption liquids are fed in the three-necked flask of the 2000ml that has stirring and condenser that 2 times of water have been housed, with 0-3 ℃ water cooling prolong, the control mixing temperature is below 15～20 ℃.Tell subnatant 510 grams, wherein contain octafluoro isobutyl-methyl ether 70%, seven fluorine iso-butylene methyl ethers 5%, methyl alcohol 1.9% and other fluorochemicalss.But find that two kinds of liquid all show acid, glass flask is corroded.
Comparative example 7
1000 gram perfluoroisobutylene methyl alcohol absorption liquids are fed in the 2000ml three-necked flask of the KOH solution that 1000 gram 20%wt are housed, and 0-3 ℃ water cooling equilibrium condensation pipe is collected escaping gas with-78 ℃ of cold wells.The control mixing temperature added perfluoroisobutylene methyl alcohol absorption liquid in 2 hours below 15 ℃.Restir 2 hours left standstill 2 hours, told subnatant.The water washing secondary that adds 3 times of amounts again obtains subnatant 513 grams.Wherein contain octafluoro isobutyl ether 48.8%, seven fluorine iso-butylene methyl ethers 37.9%, methyl alcohol 1.3%.Cold well is collected 279 gram volatile matter.
Claims (5)
1. tubular type treater that is used to handle perfluoroisobutylene methyl alcohol absorption liquid, it comprises:
Bottom sig water import (2);
Middle part perfluoroisobutylene methyl alcohol absorption liquid import (3);
Bottom octafluoro isobutyl-methyl ether outlet (10);
Top supernatant liquor spillway (6); With
Top boiling pneumatic outlet (8).
2. tubular type treater as claimed in claim 1 is characterized in that it also comprises middle part backflow import (20).
3. tubular type treater as claimed in claim 1, it is characterized in that described tubular type treater comprises that plate washer stirs tower, described stirring tower comprise a plurality of paddles (30) of rotating around central shaft that are parallel to each other and a plurality of be parallel to each other be positioned at the longitudinal baffle (31) that Ta Bishang radially extends.
4. as each described tubular type treater among the claim 1-3, it is characterized in that its length-to-diameter ratio is greater than 1.
5. tubular type treater as claimed in claim 4 is characterized in that length-to-diameter ratio is greater than 10.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4960947A (en) * | 1987-07-21 | 1990-10-02 | Nippon Mektron Limited | Process for producing hexafluoroacetone or its hydrate |
| CN1073424A (en) * | 1991-12-20 | 1993-06-23 | 埃勒夫阿托化学有限公司 | Synthesizing of N-perfluorooctyl bromide |
| US6217765B1 (en) * | 1998-08-10 | 2001-04-17 | Sharp Kabushiki Kaisha | Waste water treatment method and waste water treatment equipment capable of treating fluorine waste water containing organic matter, phosphor and hydrogen peroxide |
| US6413417B1 (en) * | 1999-01-28 | 2002-07-02 | Sharp Kabushiki Kaisha | Waste water treatment apparatus |
-
2004
- 2004-06-04 CN CNB2006100679713A patent/CN100334048C/en not_active Expired - Lifetime
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4960947A (en) * | 1987-07-21 | 1990-10-02 | Nippon Mektron Limited | Process for producing hexafluoroacetone or its hydrate |
| CN1073424A (en) * | 1991-12-20 | 1993-06-23 | 埃勒夫阿托化学有限公司 | Synthesizing of N-perfluorooctyl bromide |
| US6217765B1 (en) * | 1998-08-10 | 2001-04-17 | Sharp Kabushiki Kaisha | Waste water treatment method and waste water treatment equipment capable of treating fluorine waste water containing organic matter, phosphor and hydrogen peroxide |
| US6413417B1 (en) * | 1999-01-28 | 2002-07-02 | Sharp Kabushiki Kaisha | Waste water treatment apparatus |
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Assignee: CHANGSHU 3F ZHONGHAO NEW CHEMICAL MATERIALS Co.,Ltd. Assignor: Shanghai 3F New Material Co.,Ltd. Contract fulfillment period: 2007.9.14 to 2013.9.14 Contract record no.: 2008320000038 Denomination of invention: Device for treating perfluoroisobutylene methanol absorption liquid Granted publication date: 20070829 License type: Exclusive license Record date: 20080808 |
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Address after: Room 801, 560 Xujiahui Road, Huangpu District, Shanghai 200025 Patentee after: Shanghai Huayi sanaifu New Material Co.,Ltd. Address before: 200025 Xujiahui Road, Shanghai, room 560, No. 1301, room Patentee before: SHANGHAI 3F NEW MATERIAL TECHNOLOGY Co.,Ltd. |
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