CN1134403C - 从废水中回收氟化链烷酸的方法 - Google Patents
从废水中回收氟化链烷酸的方法 Download PDFInfo
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/42—Treatment of water, waste water, or sewage by ion-exchange
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- B—PERFORMING OPERATIONS; TRANSPORTING
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Abstract
可用以下步骤从废水中分离氟化的乳化剂酸：首先优选用沉积法从废水中除去细固体和/或可转变成细固体的材料，随后使废水与阴离子交换树脂接触，再从阴离子交换树脂中洗脱吸附的乳化剂酸。
Description
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。
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废料中有一定浓度。
US-A-4369266公开了一种氟代聚合物分散体的超滤中得到的渗透物，它是氟化的且含有具有稳定化能力的乳化剂，使它经过碱性交换树脂，其中回收氟化的乳化剂并得到随后的流出物。
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，这一问题变得十分引人注意。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树脂接触以前将这些固体从废水中除去，那么由US-A-4282162已知的方法的性能可得到相当大的改进，从而使它也适用于含细固体的废水。
本发明的另一方面是，本发明有可能不仅除去所存在的固体，而且也除去其他可转变成固体的干扰组分。这样的干扰组分可为与离子交换树脂也能结合的其他酸或其盐，因此它们不仅占有离子交换容量，而且还可能需要在乳化剂酸的洗脱过程中和/或洗脱过程后有特殊的预防措施。
这样的干扰酸的一个例子是草酸，它常常用作缓冲剂。例如，以化学计量或以过量或不足量，作为氯化物或氢氧化物加入的钙离子能使所有的或一部分草酸作为微溶的草酸盐沉积，优选与存在的任何其他细分散的干扰固体一起沉积。
因此，本发明提供一种从废水中回收氟化的乳化剂酸的方法，该法包括首先从废水中除去细固体和/或可转变成细固体的材料，随后将氟化的乳化剂酸结合在阴离子交换树脂上，并从阴离子交换树脂上洗脱氟化的乳化剂酸。本发明的另一些方面及其优选的实施方案将在下面详述。
适用于处理的废水是这样的工艺废水，在这样的废水中存在表面活性的氟化链烷酸。该法特别适用于氟化的单体乳液法聚合产生的废水，在乳液法中，在相对高浓度的氟化的乳化剂酸存在下和在缓和搅拌下，氟化的单体转化成细分散的聚合物，该聚合物呈细分散的胶体形式，以及在乳液法中，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，以致聚合物作为细粉末沉积。
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”废液的情况下，本发明的方法显示出它的能力。
除去细固体的方法取决于这些特殊的情况：
在酸性废水的情况下，可用适合的碱例如氢氧化钙充分地(可能部分地)进行中和，使胶体和任何可沉积的物质例如存在的草酸盐离子沉积，同时使乳化剂酸或其盐仍留在溶液中。
使干扰胶体沉积的另一可能方法是加入适合的金属盐，例如铝盐(例如氟化铝和硫酸铝)、钙盐(例如氯化钙)、镁盐(例如氯化镁和硫酸镁)、铁盐(例如氯化铁(II)或氯化铁(III)和硫酸铁)。在酸性废水的情况下，也可能加入相应的金属，例如铝、铁或镁。为了改进絮凝，还可加入少量的絮凝剂。
使干扰的胶体沉积的另一可能的方法是电凝结。在这里，给废水施加一电场使胶体颗粒凝结。在惰性电极(例如钛)的情况下，颗粒沉积在表面上。在可溶性电极(例如铁和/或铝)的情况下，有高电荷：直径比的金属阳离子进入溶液，它们象在加入金属盐的情况中那样引起凝结。电凝结的优点是，它不需要另外加入阴离子，例如氯离子或硫酸根离子。为了改进凝结，可加入少量的凝结剂。
除去细固体的适合机械方法是交叉流过滤(例如使用薄膜、离心分离)、深床层过滤(例如砂层过滤器)或加入助滤剂的涂层过滤(例如纤维素、珍珠岩、硅藻土)。
沉积的固体可用本身已知的方法分出，例如用过滤法(如果需要，还使用助滤剂)、倾析法、浮选法或沉积法。
乳化剂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AMBERLITEIRA-402、AMBERJET 4200(两者都由R0hm & 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。
结合的乳化剂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。USA-4282162的方法公开了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乳化剂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。
吸附乳化剂酸以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或是否返回该工艺。如果需要，还可用常规的吸附剂例如活性炭除去残留的氟化的乳化剂酸。
按照本发明的一个实施方案，为了回收有很低草酸含量的纯的氟化乳化剂酸，用铝盐溶液处理废水，同时缓慢混合；随后用石灰乳液将pH值调节到6-7.5；过滤出生成的沉积物；用硫酸将溶液的pH值调节到7以下后，让溶液通过离子交换剂。
用以下实施例说明本发明。
实施例1
使用的原料为四氟乙烯(TFE)和全氟(正丙基乙烯基醚)(PPVE)共聚产生的废水，其中摩尔比为9∶1的全氟正辛酸和全氟异辛酸的铵盐(PFOA)用作乳化剂。在母液中PFOA的浓度为1200毫克/升以及草酸浓度为1600毫克/升。
在一搅拌容器中，将14升母液与1.5克/升浓度10％(重量)的氯化铝溶液混合，并剧烈搅拌。过滤出生成的沉积物。
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)装入一圆柱形玻璃柱中(长度：25厘米，直径：16毫米)，玻璃柱装有玻璃料并用水清洗过。为了给离子交换剂进料，用泵将预处理过的母液以线速1米/小时泵入。向上通过该柱，收集离开柱子的水，由质量平衡测定PFOA的浓度。进料以后，用100毫升水清洗柱子。
为了再生离子交换剂，将150毫升89％(重量)甲醇、7％(重量)浓硫酸和4％(重量)水的混合物以0.5米/小时的线速通过该柱，并收集洗脱液。随后用100毫升水清洗柱子。
洗脱液含有85％废水中存在的乳化剂酸和3900毫克/升草酸。
实施例2
在一搅拌容器中，将14升实施例1的母液与1.5克/升浓度10％(重量)的氯化铝溶液混合，并剧烈搅拌。随后用浓度10％(重量)的石灰乳液将pH值调节到7.5。过滤出生成的沉积物，然后用稀硫酸将溶液的pH值调节到4。
离子交换剂的进料和再生的方案和步骤与实施例1类似。
在这里，洗脱液含有95％的废水中存在的乳化剂酸和1毫克/升草酸。
实施例3
将16升由处理氟化的聚合物得到的废水放入一搅拌容器中。聚合使用PFOA的铵盐作为乳化剂，PFOA的浓度为1200毫克/升。将2克浓度10％(重量)的氯化铝浓度加到该溶液中，并将混合物剧烈搅拌。随后加入浓度10％(重量)的石灰乳液使pH值达到7.5，再加入3毫克/升絮凝剂(PRAESTOL A 3015L，Slockhausen GmbH & Co.KG；聚丙烯酰胺)。过滤出生成的沉积物，然后用硫酸将pH值调节到4。
离子交换剂的进料和再生按实施例1进行。
在这里，洗脱液含有91％的废水中存在的乳化剂酸。
对比例
使用的原料为TFE和PPVE共聚产生的母液，其中PFOA的铵盐用作乳化剂。PFOA的浓度为1200毫克/升。
将大约50毫升实施例1规定的强碱性离子交换剂装入一圆柱形玻璃柱(长度：25厘米，直径16毫米)，装有玻璃料和用水清洗过。为了给离子交换剂进料，用泵将未处理的母液泵送向上通过床层。用压力表测量离子交换剂床层的压降。在400毫升母液通过后必需停止进料实验，因为沉积的聚合物使树脂结块。
Claims (9)
1.一种从废水中回收氟化的乳化剂酸的方法，该方法包括，首先从氟化的单体聚合产生的废水中除去细的固体和/或可转变成细的固体的材料，随后将氟化的乳化剂酸结合在阴离子交换树脂上，再从阴离子交换树脂上洗脱氟化的乳化剂酸。
2.根据权利要求1的方法，其中将细的固体沉积。
3.根据权利要求1的方法，其中用机械方法除去细的固体。
4.根据权利要求1的方法，其中将可转变成固体的材料沉积。
5.根据权利要求1、2或4中任一项的方法，其中用沉积法分离出已沉积的材料。
6.根据权利要求1、2或4中任一项的方法，其中用浮选法分离出已沉积的材料。
7.根据前述权利要求中任一项的方法，其中为了回收有很低草酸含量的纯的氟化乳化剂酸，用铝盐溶液处理废水，同时缓慢混合；随后用石灰乳液将pH值调节到6-7.5；过滤出生成的沉积物；用硫酸将溶液的pH值调节到7以下后，让溶液通过离子交换剂。
8.根据上述权利要求中任一项的方法，其中使用的阴离子交换树脂为强碱性阴离子交换树脂。
9.根据上述权利要求中任一项的方法，其中用稀无机酸和有机溶剂的混合物从阴离子交换树脂上洗脱所述氟化的乳化剂酸。
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| Publication number | Priority date | Publication date | Assignee | Title |
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| 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 |
| US5017480A (en) | 1987-08-10 | 1991-05-21 | Ajimomoto Co., Inc. | Process for recovering L-amino acid from fermentation liquors |
| 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 DE19824614A patent/DE19824614A1/de not_active Withdrawn
-
1999
- 1999-05-27 AT AT99926442T patent/ATE222229T1/de not_active IP Right Cessation
- 1999-05-27 AT AT02075150T patent/ATE307793T1/de not_active IP Right Cessation
- 1999-05-27 RU RU2000133332/04A patent/RU2226186C2/ru not_active IP Right Cessation
- 1999-05-27 CN CNB998068985A patent/CN1134403C/zh not_active Expired - Lifetime
- 1999-05-27 EP EP99926442A patent/EP1084097B1/de not_active Expired - Lifetime
- 1999-05-27 JP JP2000552073A patent/JP3678651B2/ja not_active Expired - Fee Related
- 1999-05-27 DE DE59902354T patent/DE59902354D1/de not_active Expired - Lifetime
- 1999-05-27 PL PL344576A patent/PL193358B1/pl not_active IP Right Cessation
- 1999-05-27 AU AU43701/99A patent/AU4370199A/en not_active Abandoned
- 1999-05-27 HU HU0102469A patent/HUP0102469A2/hu unknown
- 1999-05-27 ES ES99926442T patent/ES2176137T3/es not_active Expired - Lifetime
- 1999-05-27 DE DE59912723T patent/DE59912723D1/de not_active Expired - Lifetime
- 1999-05-27 EP EP02075150A patent/EP1193242B1/de not_active Expired - Lifetime
- 1999-05-27 CA CA002334105A patent/CA2334105A1/en not_active Abandoned
- 1999-05-27 US US09/700,636 patent/US6613941B1/en not_active Expired - Fee Related
- 1999-05-27 TR TR2000/03530T patent/TR200003530T2/xx unknown
- 1999-05-27 KR KR10-2000-7013634A patent/KR100518480B1/ko not_active IP Right Cessation
- 1999-05-27 WO PCT/EP1999/003672 patent/WO1999062858A1/de active IP Right Grant
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Also Published As
| Publication number | Publication date |
|---|---|
| DE59902354D1 (de) | 2002-09-19 |
| EP1084097B1 (de) | 2002-08-14 |
| ZA200006907B (en) | 2001-08-07 |
| EP1084097A1 (de) | 2001-03-21 |
| DE19824614A1 (de) | 1999-12-09 |
| DE59912723D1 (de) | 2005-12-01 |
| RU2226186C2 (ru) | 2004-03-27 |
| TR200003530T2 (tr) | 2001-03-21 |
| HUP0102469A2 (hu) | 2001-10-28 |
| ES2176137T1 (es) | 2002-12-01 |
| PL344576A1 (en) | 2001-11-05 |
| ATE222229T1 (de) | 2002-08-15 |
| EP1193242B1 (de) | 2005-10-26 |
| AU4370199A (en) | 1999-12-20 |
| KR20010071377A (ko) | 2001-07-28 |
| ES2176137T3 (es) | 2003-03-01 |
| CA2334105A1 (en) | 1999-12-09 |
| PL193358B1 (pl) | 2007-02-28 |
| EP1193242A1 (de) | 2002-04-03 |
| KR100518480B1 (ko) | 2005-10-05 |
| ATE307793T1 (de) | 2005-11-15 |
| WO1999062858A1 (de) | 1999-12-09 |
| CN1303363A (zh) | 2001-07-11 |
| US6613941B1 (en) | 2003-09-02 |
| JP2002516892A (ja) | 2002-06-11 |
| JP3678651B2 (ja) | 2005-08-03 |
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