CN101659718B - Method for removing perfluoro caprylic acid from dispersing liquid of perfluoro polymer by using two-section method - Google Patents
Method for removing perfluoro caprylic acid from dispersing liquid of perfluoro polymer by using two-section method Download PDFInfo
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- CN101659718B CN101659718B CN 200910018957 CN200910018957A CN101659718B CN 101659718 B CN101659718 B CN 101659718B CN 200910018957 CN200910018957 CN 200910018957 CN 200910018957 A CN200910018957 A CN 200910018957A CN 101659718 B CN101659718 B CN 101659718B
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- dispersion liquid
- perfluorocaprylic acid
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Abstract
The invention relates to a method for removing a perfluoro caprylic acid from a dispersing liquid of perfluoro polymer by using a two-section method, comprising the steps: carrying out a first section of absorption on the dispersing liquid of the perfluoro polymer by using anion exchange resins with alkalescence; and carrying out a second section of absorption through ion exchange resins with strong alkaline to completely remove the caprylic acid from the dispersing liquid of the perfluoro polymer. The perfluoro caprylic acid of the produced dispersing liquid of the perfluoro polymer can not be detected according to a certificate organization, and the produced dispersing liquid completely conforms to various indexes, therefore, the method is suitable for scale and continuous production.
Description
Technical field
The invention belongs to the fluoro-containing macromolecule material technical field, remove the method for Perfluorocaprylic Acid behind the particularly fluorine-containing dispersion liquid, especially remove the method for Perfluorocaprylic Acid in the (per) fluoropolymer dispersion liquid.
Technical background
Perfluorocaprylic Acid (PFOA) plays important effect as auxiliary agent in (per) fluoropolymer (especially tetrafluoroethylene) is produced, but its potential carinogenicity, and the use that makes Perfluorocaprylic Acid and contain the product of Perfluorocaprylic Acid has been subjected to bigger restriction.European Union's " about the instruction of sale of restriction Perfluorooctane sulfonates and use " (PFOS instruction) is in formal enforcement on June 27th, 2008.According to instruction regulation: 1) in the product composition prescription,, must not on European Union market, sell if contain PFOS greater than gross weight 0.005% (50ppm).2) contain the part of PFOS in work in-process or the part, if PFOS concentration is greater than this 0.1% (1000ppm) of gross weight partly; Or the PFOS concentration on textiles or the coated material then can not be sold on European Union market greater than 1ug/m2.This PFOS instruction flag European Union and is formally completely forbidden the use of PFOS in commodity.PFOS is widely used in civilian and the industrial production field, and the enforcement of this instruction will directly influence the outlet of products such as China's textiles, leather, papermaking, packing, dyeing and printing auxiliary, makeup.
Equally, European Parliament has also proposed European Union's requirement for restriction to Perfluorocaprylic Acid (PFOA), and they are also under a cloud to have the danger identical with PFOS.The application of Perfluorocaprylic Acid (PFOA) and derived product thereof comprises household product surface treatment (as the non-stick pan cooker), convenience food packages etc., require European Commission to examine dangerous incident again, sought safer alternative method, and define dangerous minimizing measure, genotoxic potential, extensive incidence and the persistence of Perfluorocaprylic Acid (PFOA) in all age level crowds caused the great attention of American public and surveillance authority.According to the file record, Perfluorocaprylic Acid (PFOA) can cause animal to suffer from the carcinoma of testis of liver, pancreas, and Perfluorocaprylic Acid (PFOA) is put into California 65 motion carcinogenic substances.
Perfluorocaprylic Acid (PFOA) content is commonly 1500-3500ppm in the polytetrafluoroethyldispersion dispersion product at present, and content is higher than European Union's required standard far away.Therefore it is extremely urgent to carry out removing of Perfluorocaprylic Acid (PFOA) in the poly-tetrafluoro emulsion.
Anionite-exchange resin can exchange absorption to negatively charged ion in the liquid, and this is known.This resinoid can be with the OH of self
-Or Cl
-Deng group the negatively charged ion in the liquid is exchanged, remove original anionic effect in the liquid thereby reach exchange, Perfluorocaprylic Acid (PFOA) is with C in fluorine-containing dispersion liquid
7F
15COO
-Form exist, so anionite-exchange resin has the function of exchange absorption to it.
Anionite-exchange resin is divided into strongly basic anion exchange resin and weak base anion-exchange resin substantially, its characteristics are: strongly basic anion exchange resin to remove ability strong, can reach the effect that removes fully, and the higher liquid of pH value is less to the influence that it removes ability; But its exchange capacity is less, and carries after saturated and wash comparatively difficulty, puies forward the washing lotion large usage quantity.The ability that removes of weak base type anionite-exchange resin a little less than, still have the part survivor ion in the liquid of absorption back, and more relatively poor than higher liquid removal effect to pH; But its loading capacity is bigger, carries easily and washing, and it is less to carry the washing lotion consumption.
Prior art is only to utilize weak-base ion-exchange resin to carry out ionic adsorption (per) fluoropolymer (especially tetrafluoroethylene) dispersion liquid, initial Perfluorocaprylic Acid (PFOA) content of the dispersion liquid after this method removes is about 10-30ppm, reduce through the weak-base ion-exchange resin exchange capacity after the long-term exchange use, Perfluorocaprylic Acid (PFOA) content inevitably occurs and increase, even can reach the situation that is higher than 50ppm.
Summary of the invention
At the deficiencies in the prior art, the present invention proposes a kind of two-section method and removes Perfluorocaprylic Acid method in the (per) fluoropolymer dispersion liquid.
Summary of the invention
The present invention utilize strong basic ion exchange resin and weak-base ion-exchange resin separately characteristics the (per) fluoropolymer dispersion liquid is handled, realize removing fully the purpose of Perfluorocaprylic Acid in the (per) fluoropolymer dispersion liquid (PFOA), the technical problem that solves is to make Perfluorocaprylic Acid in the (per) fluoropolymer dispersion liquid (PFOA) content meet European Union's " PFOS instruction " required standard, and ion exchange resin is regenerated under the less situation of carrying the washing lotion consumption.
Detailed Description Of The Invention
A kind of two-section method removes Perfluorocaprylic Acid method in the (per) fluoropolymer dispersion liquid, adopt weak base anion-exchange resin to carry out first section absorption earlier the (per) fluoropolymer dispersion liquid, it is 11-30ppm that wherein Perfluorocaprylic Acid is removed to concentration, carry out second section absorption by strong basic ion exchange resin again, making in the product (per) fluoropolymer dispersion liquid Perfluorocaprylic Acid be removed to concentration is below the 10ppm.
(per) fluoropolymer comprises tetrafluoroethylene, perfluoroethylene-propylene (F46).
Wherein, preferred D301 of described weak-base ion-exchange resin or D301SC type anionite-exchange resin, the preferred D201 type of described strong basic ion exchange resin anionite-exchange resin, 201 * 4 type anionite-exchange resin or 201 * 7 type anionite-exchange resin.The ion exchange resin of described each model is known products, but market is buied.
Further preferred, weak-base ion-exchange resin is a D301 type weak base anion-exchange resin, and strong basic ion exchange resin is a D201 type strongly basic anion exchange resin.
Described weak-base ion-exchange resin and strong basic ion exchange resin are filled into respectively in two ion exchange columns, and weak-base ion-exchange resin and strong basic ion exchange resin packed height are the 1/3-2/3 of ion exchange column height.Two ion exchange column series connection.
Preferably, above-mentioned ion exchange column is of a size of
300mm highly is 2000mm.
Preferably, the speed of (per) fluoropolymer dispersion liquid by weak-base ion-exchange resin and strong basic ion exchange resin is 2-4 times of resin volume/per hour.
Use the inventive method, polytetrafluoroethyldispersion dispersion at first carries out first section absorption by weak base type ion exchange resin, the Perfluorocaprylic Acid more than 95% (PFOA) can be removed, and contain Perfluorocaprylic Acid (PFOA) in the dispersion liquid this moment is 11-30ppm.Absorption by second section strong basic ion exchange resin, Perfluorocaprylic Acid residual in the dispersion liquid (PFOA) can be approached all to remove, can reach below the 10ppm through deviating from back Perfluorocaprylic Acid (PFOA) content, need to prove that 10ppm is the logical mark company of a SGS examination criteria ultimate value, Perfluorocaprylic Acid (PFOA) content reach 10ppm when following certification authority's detection less than Perfluorocaprylic Acid.
It is big both to have brought into play the weak-base ion-exchange resin adsorptive capacity by the inventive method, carries easily and advantage such as washes, and has brought into play strong basic ion exchange resin again to remove fully, is subjected to the pH value to influence little advantage.Because 95% Perfluorocaprylic Acid is all by first section weak-base ion-exchange resin absorption, so carrying of weak-base ion-exchange resin washed frequency and is greater than strong basic ion exchange resin.Can only carry during regeneration and washing, wash and can carry during the strong basic ion exchange resin unsaturation to saturated weak-base ion-exchange resin.After weak-base ion-exchange resin is saturated, carries and washing exchanging saturated weak-base ion-exchange resin with the 2wt% ammoniacal liquor of 4 times of weak-base ion-exchange resin volumes; After strong basic ion exchange resin is saturated, carries and washing exchanging saturated strong basic ion exchange resin with the 4wt% sodium hydroxide solution of 4 times of resin strong basic ion exchange resin volumes.Carry the flow velocity of washing lotion by ion exchange resin and be 3 times of resin volumes/per hour.The ion exchange resin of carrying after washing can come into operation to neutrality with pure water rinsing.If selecting for use strong base ion exchange resin that dispersion liquid is carried out Perfluorocaprylic Acid separately removes, the consumption of putting forward washing lotion during regeneration is the washing lotion of carrying of 10 times of ion exchange resin, in addition because the exchange capacity of strong basic ion exchange resin only is 1/2 of a weak-base ion-exchange resin, therefore separately use strong basic ion exchange resin to remove Perfluorocaprylic Acid, it is put forward the frequency of washing is 2 times of weak-base ion-exchange resin.Therefore this method can only use 1/5 situation of putting forward washing lotion to be issued to the effect that removes Perfluorocaprylic Acid with strong basic ion exchange resin fully.
Embodiment
Following examples are to further specify of the present invention, but the present invention is not limited thereto.
Used ion exchange column is of a size of among the embodiment if no special instructions
300mm, highly be 2000mm, and be furnished with relevant temperature meter, pH value meter, carry the washing lotion recycle pump, carry the washing lotion storage tank, tensimeter, flow take into account respective line, the ion exchange resin of employed each model is the big chemical industry company limited in east, Zibo product, the macroreticular ion exchange resin that is that the D prefix is arranged in the ion exchange resin type number does not have the gel-type ion-exchange resin that is of D prefix.Ion exchange resin all activates processing by prior art before being filled into ion exchange column.Among the embodiment in the raw materials used (per) fluoropolymer dispersion liquid content of Perfluorocaprylic Acid at 1000-3500ppm.
Ion exchange resin after the use carries out manipulation of regeneration by the following method:
After weak-base ion-exchange resin is saturated, carries and washing exchanging saturated weak-base ion-exchange resin with the 2wt% ammoniacal liquor of 4 times of weak-base ion-exchange resin volumes; After strong basic ion exchange resin is saturated, carries and washing exchanging saturated strong basic ion exchange resin with the 4wt% sodium hydroxide solution of 4 times of resin strong basic ion exchange resin volumes.Carry the flow velocity of washing lotion by ion exchange resin and be 3 times of resin volumes/per hour.The ion exchange resin of carrying after washing can come into operation to neutrality with pure water rinsing.
Embodiment 1: adopt D301 type anionite-exchange resin and D201 type anionite-exchange resin
Raw material: 2000 kilograms of polytetrafluoroethyldispersion dispersions (content of Perfluorocaprylic Acid is 2500ppm).
D301 type and two kinds of ion exchange resin of D201 type are filled into two ion exchange columns respectively, and packed height is at ion exchange column 2/3.With 3 times of resin volumes/hour flow velocity make polytetrafluoroethyldispersion dispersion successively by D301 resin ion exchange column and D201 resin ion exchange column, polytetrafluoroethyldispersion dispersion temperature before entering ion exchange column is lower than 50 ℃, pH value 9.After carrying out first section absorption with the D301 weak base anion-exchange resin earlier, Perfluorocaprylic Acid concentration wherein is 15ppm, after carrying out second section absorption by the D201 strong basic ion exchange resin again, polytetrafluoroethyldispersion dispersion Perfluorocaprylic Acid (PFOA) content wherein is below the 10ppm, is lower than its test pole limit value 10ppm.After the polytetrafluoroethyldispersion dispersion product of producing carried out total analysis, every index was all within normal range.
Embodiment 2: adopt D301 type anionite-exchange resin and 201 * 7 type anionite-exchange resin
Raw material: 2000 kilograms of polytetrafluoroethyldispersion dispersions (content of Perfluorocaprylic Acid is 3000ppm).
D301 type and two kinds of ion exchange resin of 201 * 7 types are filled into two ion exchange columns respectively, and packed height is at ion exchange column 1/3.With 2 times of resin volumes/hour flow velocity make the raw material polytetrafluoroethyldispersion dispersion successively by D301 resin ion exchange column and D201 * 7 resin ion exchange columns, polytetrafluoroethyldispersion dispersion temperature before entering ion exchange column is lower than 50 ℃, pH value 8.5.After carrying out first section absorption with the D301 weak base anion-exchange resin earlier, Perfluorocaprylic Acid concentration wherein is 14ppm, carry out second section absorption by 201 * 7 strong basic ion exchange resins again, dispersion liquid after two sections absorption Perfluorocaprylic Acid (PFOA) content wherein is below the 10ppm, is lower than its test pole limit value 10ppm.After the polytetrafluoroethyldispersion dispersion product of producing carried out total analysis, every index was all within normal range.Ion exchange resin after the use carries out manipulation of regeneration by the method for embodiment 1.
Embodiment 3: adopt D301SC type anionite-exchange resin and 201 * 7 type anionite-exchange resin
Raw material: 2000 kilograms of polytetrafluoroethyldispersion dispersions (content of Perfluorocaprylic Acid is 1500ppm).
D301SC type and two kinds of ion exchange resin of 201 * 7 types are filled into two ion exchange columns respectively, and packed height is at ion exchange column 2/3.With 4 times of resin volumes/hour flow velocity make the raw material polytetrafluoroethyldispersion dispersion successively by D301 resin ion exchange column and 201 * 7 resin ion exchange columns, polytetrafluoroethyldispersion dispersion temperature before entering ion exchange column is lower than 50 ℃, pH value 7.5.Earlier the Perfluorocaprylic Acid concentration of carrying out after first section absorption wherein with the D301SC weak base anion-exchange resin is 18ppm, carry out second section absorption by 201 * 7 strong basic ion exchange resins again, dispersion liquid after two sections absorption Perfluorocaprylic Acid (PFOA) content wherein is below the 10ppm, is lower than its test pole limit value 10ppm.After the polytetrafluoroethyldispersion dispersion product of producing carried out total analysis, every index was all within normal range.Ion exchange resin after the use carries out manipulation of regeneration by the method for embodiment 1.
Embodiment 4: adopt D301 type anionite-exchange resin and D201 type anionite-exchange resin
Raw material: 2000 kilograms of perfluoroethylene-propylene dispersion liquids (content of Perfluorocaprylic Acid is 3500ppm).
D301 type and two kinds of ion exchange resin of D201 type are filled into two ion exchange columns respectively, and packed height is at 2/3 ion exchange column height.With 3 times of resin volumes/hour flow velocity make perfluoroethylene-propylene (F46) dispersion liquid respectively by two ion exchange columns, guarantee that dispersion liquid temperature before entering ion exchange column is lower than 50 ℃, the pH value is 7.After carrying out first section absorption with the D301 weak base anion-exchange resin earlier, Perfluorocaprylic Acid concentration wherein is 13ppm, carry out second section absorption by the D201 strong basic ion exchange resin again, F46 dispersion liquid after two sections absorption Perfluorocaprylic Acid (PFOA) content wherein is below the 10ppm, is lower than its test pole limit value 10ppm.After the F46 dispersion liquid product of producing carried out total analysis, every index was all within normal range.Ion exchange resin after the use carries out manipulation of regeneration by the method for embodiment 1.
Claims (4)
1. a two-part removes Perfluorocaprylic Acid method in the (per) fluoropolymer dispersion liquid, it is characterized in that adopting weak base anion-exchange resin to carry out first section absorption earlier the (per) fluoropolymer dispersion liquid, it is 11-30ppm that wherein Perfluorocaprylic Acid is removed to concentration, carry out second section absorption by strong basic ion exchange resin again, making in the product (per) fluoropolymer dispersion liquid Perfluorocaprylic Acid be removed to concentration is below the 10ppm;
(per) fluoropolymer in the described (per) fluoropolymer dispersion liquid is tetrafluoroethylene or perfluoroethylene-propylene;
Described weak base anion-exchange resin is D301 type or D301SC type anionite-exchange resin;
Described strong basic ion exchange resin is selected from D201 type anionite-exchange resin, 201 * 4 type anionite-exchange resin or 201 * 7 type anionite-exchange resin.
2. two-part as claimed in claim 1 removes Perfluorocaprylic Acid method in the (per) fluoropolymer dispersion liquid, it is characterized in that, described weak base anion-exchange resin and strong basic ion exchange resin are filled into respectively in ion exchange column, and weak-base ion-exchange resin and strong basic ion exchange resin packed height are the 1/3-2/3 of ion exchange column height.
3. two-part as claimed in claim 2 removes Perfluorocaprylic Acid method in the (per) fluoropolymer dispersion liquid, it is characterized in that, described ion exchange column is of a size of
300mm highly is 2000mm.
4. two-part as claimed in claim 1 removes Perfluorocaprylic Acid method in the (per) fluoropolymer dispersion liquid, it is characterized in that the speed of (per) fluoropolymer dispersion liquid by weak base anion-exchange resin and strong basic ion exchange resin is 2-4 times of resin volume/per hour.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200910018957 CN101659718B (en) | 2009-09-22 | 2009-09-22 | Method for removing perfluoro caprylic acid from dispersing liquid of perfluoro polymer by using two-section method |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200910018957 CN101659718B (en) | 2009-09-22 | 2009-09-22 | Method for removing perfluoro caprylic acid from dispersing liquid of perfluoro polymer by using two-section method |
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| CN101659718A CN101659718A (en) | 2010-03-03 |
| CN101659718B true CN101659718B (en) | 2011-05-04 |
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| US11014999B2 (en) * | 2018-04-24 | 2021-05-25 | Inhance Technologies, LLC | Systems and methods for processing fluoropolymer materials and related workpieces |
| CN111085278A (en) * | 2018-10-18 | 2020-05-01 | 中国石油化工股份有限公司 | Method for removing boron trifluoride |
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