CN1191997C - 从废水中回收氟化链烷酸的方法 - Google Patents
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Abstract
本发明涉及一种从废水中回收氟化的链烷酸的方法，其特征在于，用非离子型或阳离子型表面活性剂或有类似作用的表面活性物质使废水中细分散的固体稳定，随后将氟化的链烷酸结合到阴离子交换树脂上，再从阴离子交换树脂上洗脱氟化的链烷酸。
Description
发明领域
氟化的单体在含水分散液中的聚合中，因为氟化链烷酸没有调聚性质，所以使用它们作为乳化剂。具体地说，使用全氟化的或部分氟化的链烷羧酸或链烷磺酸的盐、优选碱金属盐或铵盐。这些化合物通过电氟化或通过氟化单体的调聚来制备。这些化合物是昂贵的。所以，已作了许多努力来从废水中回收这些有价值的材料。
背景技术
US-A-5442097公开了一种从污染的原料中以可用的形式来回收氟化羧酸的方法。在这一方法中，如果需要，在含水介质中，用足够强的酸将氟化羧酸从这些材料中释放出来，然后将氟化羧酸与适合的醇反应，再将生成的酯蒸出。在这里，原料可为聚合母液，特别是从乳液聚合得到的聚合母液，其中借助相对大量的乳化剂，以胶体颗粒的形式制得氟化聚合物。已证明这一方法是很有用的，但它要求氟化羧酸在原料中有一定浓度。
DE-A-2044986公开了一种从稀溶液中回收全氟羧酸的方法，在该法中，将全氟羧酸的稀溶液与弱碱性阴离子交换树脂进行吸附接触，因此溶液中存在的全氟羧酸吸附在阴离子交换树脂上，用氨水溶液洗脱阴离子交换树脂，从而将吸附的全氟羧酸转移到洗脱液中，最后从洗脱液中分离全氟羧酸。但是，完成洗脱需要相对大量的稀氨水溶液，而且这一方法也是很耗时的。这些缺点被从US-A-4282162已知的用于吸附在碱性阴离子交换剂上的氟化的乳化剂酸洗脱的方法克服，在这一方法中，用稀无机酸和有机溶剂的混合物进行吸附的氟化的乳化剂酸从阴离子交换剂中的洗脱。在这一方法中，同时用这种酸再生离子交换树脂。
已经发现，最后提到的这一方法在工业实施中有一些问题，特别是当处理的废水含有很细的固体时，过去这样的固体不认为或至少不认为是一个问题。在这种情况下，装有阴离子交换树脂的设备被这些固体不同程度地迅速堵塞，由于流动阻力增加和性能下降，这一问题变得十分显著。在这里，通常使用的上游过滤器或玻璃料是无效的。
还发现，这些困难是由于乳化剂酸使细固体保持在相对稳定的胶体悬浮液中引起的。当这些酸随后通过阴离子交换树脂从体系中除去时，这一相对稳定的分散液被破坏，使固体沉积，并堵塞离子交换树脂。因此还发现，如果在废水与阴离子交换剂接触以前，通过加入非离子型或阳离子型表面活性添加剂(表面活性剂)使固体在废水中的分散液稳定，那么由US-A-4282162已知的方法的性能可得到相当大的改进。
发明内容
因此，本发明提供了一种从废水中回收氟化的链烷酸的方法，该法包括通过非离子型或阳离子型表面活性剂或有类似作用的表面活性物质使细分散在废水中的固体稳定，随后使氟化的链烷酸结合到阴离子交换树脂上，再从阴离子交换树脂中洗脱氟化的链烷酸。
适合处理的废水是其中存在表面活性的氟化链烷酸的工艺废水。本发明方法特别适合于氟化单体用乳液聚合方法聚合产生的废水。在乳液聚合工艺中，在用作乳化剂的相对高浓度的氟化链烷酸存在下和缓和搅拌下，氟化单体转化成极细地分散的胶体形式的聚合物，在达到所需的固体浓度以后，例如通过剧烈的搅拌使制得的胶乳凝结，这样聚合物作为细粉末沉积出来。
已发现，在已知的处理中，相对低分子量的聚合物材料会引起各种困难；当聚合过程得到宽分子量分布时，这些低分子量聚合物的不良影响就变得特别显著。在这样的“困难”废水的情况下，本发明的方法显示出它的能力。
在废水与离子交换树脂接触以前，除去固体也是已知的(1998年6月2日的德国专利申请书19824614.5，题目为“由废水中回收氟化的烷酸的方法”)。但是，它的缺点是，就除去固体的设备和加入的辅助化学品的数量来说(例如石灰乳液、铝盐、絮凝剂)，费用高。特别是在低的固体浓度下，完全除去胶体材料需要相对大量的化学品，在固体除去中这些化学品仅被有限程度除去。
在本发明的方法中，因为加入少量易于优先生物降解的表面活性剂就足以使胶体稳定并确保离子交换剂无故障的操作，所以大幅度地降低了设备和化学品的费用。
氟化链烷酸在离子交换树脂上的吸附可用本身已知的方法进行。适合的树脂特别是强碱性阴离子交换树脂，例如以商品名AMBERLITE IRA-402、AMBERJET 4200(两者都由Rohm &Haas提供)、PUROLITE A845(Purolite GmbH提供)或LEWATITMP-500(Bayer AG提供)购得的。
可按本身已知的方法，使用装在常规设备例如管或柱中的离子交换树脂(废水流过这些设备)来进行吸附。
结合的氟化链烷酸的洗脱同样按本身已知的方法进行，优选US-A-4282162中公开的方法。例如，使用稀无机酸和有机溶剂的混合物进行洗脱。
适合以聚合应用中所要求的高纯度分离链烷酸的方法例如是上述US-A-5442097中公开的或US-A-5312935中公开的那些方法，其中首先使洗脱液基本上不含水，然后再用氧化剂处理。
氟化链烷酸吸附后剩下的废水按已知的方法处理，这一处理取决于其他材料的含量。
具体实施方式
用以下实施例来说明本发明。
实施例1-4和对比例
使用的原料为四氟乙烯和全氟(正丙基乙烯基醚)共聚产生的废水，其中全氟正辛酸和全氟异辛酸(PFOA)的铵盐用作乳化剂。PFOA的浓度为750毫克/升。
在一搅拌容器中，将1000克这种母液与0.1克非离子型表面活性剂TRITON X-100(Rohm & Haas，对辛基苯酚乙氧化物，CASNo.9002-93-1)或GENAPOL UD088(Hoechs+AG，脂肪醇聚乙二醇醚)混合并搅拌。
将大约50毫升商业强碱性离子交换树脂(AMBERLITE IRA-402，Rohm & Haas；苯乙烯-二乙烯基苯型，阴离子：氯离子，凝胶，总容量：1.3克当量/升，堆积密度：710克/升)放在圆柱形玻璃柱中(长度：25厘米，直径16毫米)，装有玻璃料并用水清洗过。为了给离子交换剂进料，用泵将溶液送入向上通过床层。收集离开柱子的水作为多次样品，并测定PFOA的浓度。用压力表测量离子交换剂床层上的压降。收集离开柱子的水作为多次样品，并测定PFOA的浓度。
在不加表面活性剂(对比例)的条件下，因为聚合物沉积和树脂明显成块使压降增加到1巴/米以上，进料实验不得不停止。
| 实施例1 | 实施例2 | 实施例3 | 实施例4 | 对比例 | |||||
| 表面活性剂 | GENAPOL | TRITON | TRITON | TRITON | 无 | ||||
| 废水量[毫升] | 浓度 | 100毫克/升 | 100毫克/升 | 200毫克/升 | 400毫克/升 | ||||
| 离子交换剂床层压降(巴/米] | |||||||||
| 02003004005006001000 | 0.120.160.120.120.120.120.12 | 0.240.200.240.240.240.24 | 0.240.240.240.24 | 0.160.160.240.240.24 | 0.200.401.60(停止) | ||||
| 废水中PFOA[毫克/升] | 2.5 | 5.1 | 4.2 | 4.2 | 3.3 | ||||
实施例5
将150毫升洗脱溶液由甲醇、浓硫酸(96％)和水(质量比：89％、7％、4％)混合制得。进料以后，首先用100毫升水清洗离子交换剂柱，以便从柱中除去残留的废水。然后以0.5米/小时的线速将洗脱溶液通过柱子，并收集洗脱溶液。最后用另外50毫升水清洗柱子。洗脱溶液含有约95％所用废水中的作为乳化剂的酸。
Claims (6)
1.一种从废水中回收氟化的链烷酸的方法，该方法包括：
1)用非离子型或阳离子型表面活性剂或表面活性物质稳定极细地分散在废水中的固体；
2)通过离子交换反应，将所述氟化的链烷酸结合到阴离子交换树脂上。
2.根据权利要求1的方法，其中所述废水是氟化单体聚合产生的废水。
3.根据权利要求1或2的方法，还包括使废水中的可转变成固体的材料沉积的步骤。
4.根据权利要求1或2的方法，还包括从阴离子交换树脂上洗脱所述氟化的链烷酸的步骤。
5.根据权利要求4的方法，其中所述洗脱步骤是使用稀无机酸和有机溶剂的混合物进行的。
6.根据权利要求1或2的方法，其中所述氟化的链烷酸选自氟化的链烷羧酸和氟化的链烷磺酸，并且用作氟化单体聚合的乳化剂。
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19824615A DE19824615A1 (de) | 1998-06-02 | 1998-06-02 | Verfahren zur Rückgewinnung von fluorierten Alkansäuren aus Abwässern |
| DE19824615.3 | 1998-06-02 |
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| Publication Number | Publication Date |
|---|---|
| CN1303356A CN1303356A (zh) | 2001-07-11 |
| CN1191997C true CN1191997C (zh) | 2005-03-09 |
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| CNB998068977A Expired - Lifetime CN1191997C (zh) | 1998-06-02 | 1999-05-27 | 从废水中回收氟化链烷酸的方法 |
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| US (1) | US6518442B1 (zh) |
| EP (2) | EP1209125B2 (zh) |
| JP (1) | JP3678650B2 (zh) |
| KR (1) | KR100499439B1 (zh) |
| CN (1) | CN1191997C (zh) |
| AT (2) | ATE301103T1 (zh) |
| AU (1) | AU4370299A (zh) |
| CA (1) | CA2334023C (zh) |
| CZ (1) | CZ20004380A3 (zh) |
| DE (3) | DE19824615A1 (zh) |
| ES (1) | ES2176138T3 (zh) |
| HU (1) | HUP0102254A3 (zh) |
| PL (1) | PL194343B1 (zh) |
| RU (1) | RU2224721C2 (zh) |
| TR (1) | TR200003531T2 (zh) |
| WO (1) | WO1999062830A1 (zh) |
| ZA (1) | ZA200006906B (zh) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106132525A (zh) * | 2014-03-31 | 2016-11-16 | 旭硝子株式会社 | 阴离子型含氟乳化剂的回收方法 |
Families Citing this family (56)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE19857111A1 (de) * | 1998-12-11 | 2000-06-15 | Dyneon Gmbh | Wäßrige Dispersionen von Fluorpolymeren |
| DE19932771A1 (de) | 1999-07-14 | 2001-01-18 | Dyneon Gmbh | Verfahren zur Eluierung fluorierter Emulgatoren |
| DE19933696A1 (de) | 1999-07-17 | 2001-01-18 | Dyneon Gmbh | Verfahren zur Rückgewinnung fluorierter Emulgatoren aus wässrigen Phasen |
| DE19953285A1 (de) | 1999-11-05 | 2001-05-10 | Dyneon Gmbh | Verfahren zur Rückgewinnung fluorierter Emulgatoren |
| US6593416B2 (en) | 2000-02-01 | 2003-07-15 | 3M Innovative Properties Company | Fluoropolymers |
| US6720360B1 (en) * | 2000-02-01 | 2004-04-13 | 3M Innovative Properties Company | Ultra-clean fluoropolymers |
| US6794550B2 (en) | 2000-04-14 | 2004-09-21 | 3M Innovative Properties Company | Method of making an aqueous dispersion of fluoropolymers |
| US7125941B2 (en) * | 2001-03-26 | 2006-10-24 | 3M Innovative Properties Company | Aqueous emulsion polymerization process for producing fluoropolymers |
| US7045571B2 (en) | 2001-05-21 | 2006-05-16 | 3M Innovative Properties Company | Emulsion polymerization of fluorinated monomers |
| US6737489B2 (en) | 2001-05-21 | 2004-05-18 | 3M Innovative Properties Company | Polymers containing perfluorovinyl ethers and applications for such polymers |
| US20030125421A1 (en) * | 2001-08-03 | 2003-07-03 | Hermann Bladel | Aqueous dispersions of fluoropolymers |
| US7279522B2 (en) * | 2001-09-05 | 2007-10-09 | 3M Innovative Properties Company | Fluoropolymer dispersions containing no or little low molecular weight fluorinated surfactant |
| JP2003285076A (ja) * | 2002-01-25 | 2003-10-07 | Jiemuko:Kk | 含フッ素乳化剤の回収法 |
| JP2003285075A (ja) * | 2002-01-25 | 2003-10-07 | Jiemuko:Kk | フッ素含有乳化剤回収方法 |
| US6833418B2 (en) | 2002-04-05 | 2004-12-21 | 3M Innovative Properties Company | Dispersions containing perfluorovinyl ether homopolymers and use thereof |
| US6822059B2 (en) | 2002-04-05 | 2004-11-23 | 3M Innovative Properties Company | Dispersions containing bicomponent fluoropolymer particles and use thereof |
| EP1514848B1 (en) * | 2002-06-19 | 2006-04-05 | Sasakura Engineering Co. Ltd. | Process for the recovery of fluorine-containing emulsifiers |
| EP1441014A1 (en) * | 2003-01-22 | 2004-07-28 | 3M Innovative Properties Company | Aqueous fluoropolymer dispersion comprising a melt processible fluoropolymer and having a reduced amount of fluorinated surfactant |
| US6991732B2 (en) | 2003-07-02 | 2006-01-31 | Arkema | Process for the recovery of fluorosurfactants by active charcoal |
| ATE529451T1 (de) * | 2003-11-17 | 2011-11-15 | 3M Innovative Properties Co | Wässrige ptfe-dispersionen mit einem niedrigen gehalt an fluorierten emulgatoren |
| EP1561729A1 (en) * | 2004-02-05 | 2005-08-10 | 3M Innovative Properties Company | Removal of fluorinated surfactants from waste water |
| EP1561742B1 (en) * | 2004-02-05 | 2012-11-21 | 3M Innovative Properties Company | Method of recovering fluorinated acid surfactants from adsorbent particles loaded therewith |
| DE602004021467D1 (de) * | 2004-03-01 | 2009-07-23 | 3M Innovative Properties Co | Verfahren zum Beschichten eines Gegenstands mit einer fluorhaltigen Kunststoffsdispersion |
| US7304101B2 (en) * | 2004-07-19 | 2007-12-04 | 3M Innovative Properties Company | Method of purifying a dispersion of ionic fluoropolymer |
| US20060135681A1 (en) * | 2004-12-22 | 2006-06-22 | Cavanaugh Robert J | Viscosity control for reduced fluorosurfactant aqueous fluoropolymer dispersions by the addition of cationic surfactant |
| EP1700869A1 (en) | 2005-03-11 | 2006-09-13 | 3M Innovative Properties Company | Recovery of fluorinated surfactants from a basic anion exchange resin having quaternary ammonium groups |
| GB2427170A (en) * | 2005-06-17 | 2006-12-20 | 3M Innovative Properties Co | Fluoropolymer film having glass microspheres |
| GB0514398D0 (en) * | 2005-07-15 | 2005-08-17 | 3M Innovative Properties Co | Aqueous emulsion polymerization of fluorinated monomers using a fluorinated surfactant |
| US20080015304A1 (en) | 2006-07-13 | 2008-01-17 | Klaus Hintzer | Aqueous emulsion polymerization process for producing fluoropolymers |
| GB0523853D0 (en) | 2005-11-24 | 2006-01-04 | 3M Innovative Properties Co | Fluorinated surfactants for use in making a fluoropolymer |
| GB0525978D0 (en) * | 2005-12-21 | 2006-02-01 | 3M Innovative Properties Co | Fluorinated Surfactants For Making Fluoropolymers |
| GB0514387D0 (en) * | 2005-07-15 | 2005-08-17 | 3M Innovative Properties Co | Aqueous emulsion polymerization of fluorinated monomers using a perfluoropolyether surfactant |
| US20070025902A1 (en) * | 2005-07-15 | 2007-02-01 | 3M Innovative Properties Company | Recovery of fluorinated carboxylic acid from adsorbent particles |
| GB2430437A (en) * | 2005-09-27 | 2007-03-28 | 3M Innovative Properties Co | Method of making a fluoropolymer |
| RU2388537C2 (ru) * | 2005-10-14 | 2010-05-10 | Асахи Гласс Компани, Лимитед | Способ регенерации основной анионообменной смолы |
| US7728087B2 (en) | 2005-12-23 | 2010-06-01 | 3M Innovative Properties Company | Fluoropolymer dispersion and method for making the same |
| US20070276103A1 (en) * | 2006-05-25 | 2007-11-29 | 3M Innovative Properties Company | Fluorinated Surfactants |
| US7754795B2 (en) * | 2006-05-25 | 2010-07-13 | 3M Innovative Properties Company | Coating composition |
| US7666928B2 (en) | 2006-05-31 | 2010-02-23 | E.I. Du Pont De Nemours And Company | Staged addition of non-fluorinated anionic surfactant to reduced fluorosurfactant fluoropolymer dispersion |
| US8119750B2 (en) * | 2006-07-13 | 2012-02-21 | 3M Innovative Properties Company | Explosion taming surfactants for the production of perfluoropolymers |
| BRPI0807109A2 (pt) * | 2007-02-16 | 2014-05-06 | 3M Innovative Properties Co | Sistema e processo para a remoção de fluoroquiímicos da água |
| US20100072134A1 (en) * | 2007-03-06 | 2010-03-25 | Mader Brian T | Ultrasonically induced cavitation of fluorochemicals |
| US20080264864A1 (en) * | 2007-04-27 | 2008-10-30 | 3M Innovative Properties Company | PROCESS FOR REMOVING FLUORINATED EMULSIFIER FROM FLUOROPOLMER DISPERSIONS USING AN ANION-EXCHANGE RESIN AND A pH-DEPENDENT SURFACTANT AND FLUOROPOLYMER DISPERSIONS CONTAINING A pH-DEPENDENT SURFACTANT |
| GB0712191D0 (en) * | 2007-06-25 | 2007-08-01 | 3M Innovative Properties Co | Process for removing fluorinated compounds for an aqueous phase originating from the preparation of fluoropolymers |
| JP5256002B2 (ja) * | 2008-11-25 | 2013-08-07 | オルガノ株式会社 | フォトレジスト現像排水の排水処理システム |
| CN103796759B (zh) * | 2011-09-13 | 2016-10-26 | 旭硝子株式会社 | 阴离子性含氟乳化剂的回收方法 |
| WO2015053235A1 (ja) | 2013-10-10 | 2015-04-16 | 旭硝子株式会社 | 含フッ素乳化剤の回収方法 |
| DE102014100694A1 (de) | 2014-01-22 | 2015-07-23 | Friedrich-Alexander-Universität Erlangen-Nürnberg | Verfahren und Vorrichtung zur Abtrennung von fluorierten Kohlenwasserstoffen aus einer wässrigen Phase |
| KR102468123B1 (ko) | 2016-11-15 | 2022-11-24 | 도요 고한 가부시키가이샤 | 폴리에스테르계 열가소성 필름의 제조방법, 폴리에스테르계 열가소성 필름 |
| US11548800B2 (en) | 2019-04-26 | 2023-01-10 | Geyser Remediation LLC | Water purification apparatus and method |
| JP7236004B2 (ja) * | 2019-04-26 | 2023-03-09 | ダイキン工業株式会社 | フルオロポリマー水性分散液の製造方法及びフルオロポリマー水性分散液 |
| US11452987B2 (en) | 2019-06-19 | 2022-09-27 | The Johns Hopkins University | Contaminate sequestering coatings and methods of using the same |
| WO2020260702A1 (en) | 2019-06-28 | 2020-12-30 | Katholieke Universiteit Leuven | Adsorptive removal of perfluorinated or partially fluorinated surfactants |
| TWI727723B (zh) * | 2020-03-26 | 2021-05-11 | 臺北醫學大學 | 含氟廢液的處理及回收方法 |
| US11840471B1 (en) | 2021-12-20 | 2023-12-12 | Republic Services, Inc. | Method for removing per- and polyfluoroalkyl substances (PFAS) from waste water |
| WO2023208919A1 (en) | 2022-04-28 | 2023-11-02 | Röhm Gmbh | Poly(meth)acrylat impact modifier with reduced metal ion content and method for its production |
Family Cites Families (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3536643A (en) † | 1967-09-01 | 1970-10-27 | Cosden Oil & Chem Co | Polyethylene emulsion process |
| US3882153A (en) | 1969-09-12 | 1975-05-06 | Kureha Chemical Ind Co Ltd | Method for recovering fluorinated carboxylic acid |
| GB1314607A (en) | 1969-09-12 | 1973-04-26 | Kureha Chemical Ind Co Ltd | Method for recovering perfluorinated emulsifiers |
| DE2903981A1 (de) * | 1979-02-02 | 1980-08-07 | Hoechst Ag | Rueckgewinnung fluorierter emulgatorsaeuren aus basischen anionenaustauschern |
| DE2908001C2 (de) * | 1979-03-01 | 1981-02-19 | Hoechst Ag, 6000 Frankfurt | Verfahren zur Herstellung konzentrierter Dispersionen von Fluorpolymeren |
| DE4213154C1 (zh) | 1992-04-22 | 1993-06-17 | Hoechst Ag, 6230 Frankfurt, De | |
| DE4402694A1 (de) | 1993-06-02 | 1995-08-03 | Hoechst Ag | Verfahren zur Rückgewinnung von fluorierten Carbonsäuren |
-
1998
- 1998-06-02 DE DE19824615A patent/DE19824615A1/de not_active Withdrawn
-
1999
- 1999-05-27 CN CNB998068977A patent/CN1191997C/zh not_active Expired - Lifetime
- 1999-05-27 US US09/700,639 patent/US6518442B1/en not_active Expired - Lifetime
- 1999-05-27 PL PL99344575A patent/PL194343B1/pl not_active IP Right Cessation
- 1999-05-27 ES ES99926443T patent/ES2176138T3/es not_active Expired - Lifetime
- 1999-05-27 EP EP02075014.7A patent/EP1209125B2/de not_active Expired - Lifetime
- 1999-05-27 DE DE59903664T patent/DE59903664D1/de not_active Expired - Lifetime
- 1999-05-27 EP EP99926443A patent/EP1093441B1/de not_active Expired - Lifetime
- 1999-05-27 AT AT02075014T patent/ATE301103T1/de not_active IP Right Cessation
- 1999-05-27 JP JP2000552048A patent/JP3678650B2/ja not_active Expired - Fee Related
- 1999-05-27 DE DE59912370T patent/DE59912370D1/de not_active Expired - Lifetime
- 1999-05-27 KR KR10-2000-7013595A patent/KR100499439B1/ko not_active IP Right Cessation
- 1999-05-27 CA CA002334023A patent/CA2334023C/en not_active Expired - Fee Related
- 1999-05-27 HU HU0102254A patent/HUP0102254A3/hu unknown
- 1999-05-27 CZ CZ20004380A patent/CZ20004380A3/cs unknown
- 1999-05-27 AT AT99926443T patent/ATE228972T1/de not_active IP Right Cessation
- 1999-05-27 AU AU43702/99A patent/AU4370299A/en not_active Abandoned
- 1999-05-27 RU RU2000133334/15A patent/RU2224721C2/ru not_active IP Right Cessation
- 1999-05-27 TR TR2000/03531T patent/TR200003531T2/xx unknown
- 1999-05-27 WO PCT/EP1999/003673 patent/WO1999062830A1/de active IP Right Grant
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106132525A (zh) * | 2014-03-31 | 2016-11-16 | 旭硝子株式会社 | 阴离子型含氟乳化剂的回收方法 |
| CN106132525B (zh) * | 2014-03-31 | 2018-02-06 | 旭硝子株式会社 | 阴离子型含氟乳化剂的回收方法 |
Also Published As
| Publication number | Publication date |
|---|---|
| DE59912370D1 (de) | 2005-09-08 |
| EP1209125B2 (de) | 2014-07-23 |
| ES2176138T1 (es) | 2002-12-01 |
| CA2334023C (en) | 2007-12-04 |
| WO1999062830A1 (de) | 1999-12-09 |
| PL194343B1 (pl) | 2007-05-31 |
| EP1093441A1 (de) | 2001-04-25 |
| CZ20004380A3 (cs) | 2001-09-12 |
| ATE228972T1 (de) | 2002-12-15 |
| EP1093441B1 (de) | 2002-12-04 |
| DE19824615A1 (de) | 1999-12-09 |
| KR100499439B1 (ko) | 2005-07-07 |
| ZA200006906B (en) | 2001-09-26 |
| CN1303356A (zh) | 2001-07-11 |
| US6518442B1 (en) | 2003-02-11 |
| PL344575A1 (en) | 2001-11-05 |
| ATE301103T1 (de) | 2005-08-15 |
| KR20010071370A (ko) | 2001-07-28 |
| CA2334023A1 (en) | 1999-12-09 |
| AU4370299A (en) | 1999-12-20 |
| HUP0102254A2 (hu) | 2001-10-28 |
| JP3678650B2 (ja) | 2005-08-03 |
| JP2002516885A (ja) | 2002-06-11 |
| RU2224721C2 (ru) | 2004-02-27 |
| TR200003531T2 (tr) | 2001-04-20 |
| ES2176138T3 (es) | 2003-07-01 |
| DE59903664D1 (de) | 2003-01-16 |
| HUP0102254A3 (en) | 2002-06-28 |
| EP1209125A2 (de) | 2002-05-29 |
| EP1209125B1 (de) | 2005-08-03 |
| EP1209125A3 (de) | 2003-10-22 |
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