CN1145587C - 从水相中回收氟化乳化剂的方法 - Google Patents
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Abstract
本发明涉及一种可以从含有少量氟化聚合物微粒的水相中回收氟化乳化剂的方法。该方法是用少量的非离子型表面活性剂对水相进行处理。使经过调节的水相与阴离子交换树脂接触,从交换树脂中解吸出吸附的乳化剂。按本发明方法可以用絮凝剂将未处理过的水相或洗脱液中所含的含氟聚合物微粒定量沉淀。
Description
技术领域
本发明涉及废水的处理方法,主要是对含有氟化乳化剂的轻度污染废水的处理方法。由于氟化单体不具有调聚性,所以将氟化乳化剂用于氟化单体的聚合反应中。优选使用的是全氟或部分氟化的烷基羧酸或烷基磺酸的盐,较好是碱金属盐或铵盐。这些化合物是通过全氟化单体的电氟化法或调聚法来生产的,从而成本很高。因此尚缺少从废水中回收此类有价值物质的试验。
背景技术
US-A-5 442 097专利中介绍了一种从被污染的原料中以可行的方式回收氟化羧酸的方法。在该方法中,必要时可用一种足够强的酸从置于水介质中的原料中释放出氟化羧酸,然后使该氟化羧酸与一种合适的醇进行反应,并分馏出生成的酯。该方法所用的原料可以是一种聚合母液,特别是用较大量乳化剂制备含氟聚合物胶体粒子的乳液聚合反应产生的聚合母液。此处所用的“聚合母液”是指用絮凝法(没有进一步的处理步骤,如洗涤)分离含氟聚合物后产生的废水。已证明这种方法是切实可行的,但需要在原料中含有一定浓度的氟化羧酸。
在没有醇存在的条件下也可用蒸馏法回收氟化羧酸。在这个方法中,氟化羧酸以高浓度的共沸物形式被蒸馏出来。但从节能角度考虑,该方法在技术上不具备优势。此外,采用该法产生的废水处理大大难于前面已介绍的方法。
DE-A-20 44 986介绍了一种从稀溶液中回收全氟羧酸的方法。按照该方法,使含全氟羧酸的稀溶液与弱碱性阴离子交换树脂进行吸附性接触,从而将溶液中所含的全氟羧酸吸附到阴离子交换树脂内,然后用氨水溶液来洗脱阴离子交换树脂,以便使吸附的全氟羧酸转移到洗脱剂中,最后从洗脱剂中回收酸。不过对于整个洗脱过程,所需要的稀氨溶液量比较大,而且该法非常耗时的。采用US-A-4 282 162中所述的从阴离子交换剂中洗脱出被吸附的氟化乳化剂酸的方法可以克服这个缺点。在该方法中,用稀无机酸和有机溶剂的混合物将被吸附的氟化乳化剂酸从阴离子交换剂中洗脱出来。在该方法中,用酸可同时使交换树脂得到再生。
由于存在含氟聚合物胶乳粒子,故在工业上基本不采用阴离子交换树脂进行废水处理。胶乳粒子是阴离子稳定的,并因此凝结在阴离子交换树脂内,由此引起交换塔(柱)的堵塞。
发明内容
一个推荐的回收氟化乳化剂酸的方法解决了上述难题。在这个方法中用表面活性剂使分散在废水中的固体物质处于稳定状态,然后使氟化的乳化剂酸吸附到阴离子交换树脂上,最后将氟化乳化剂酸从交换树脂上洗脱出来。请见(WO-A-99/62830)。在其实施例中,采用的是浓度为100-400毫克/升的非离子型表面活性剂。
现已发现了从除乳化剂外含少量含氟聚合物微粒的水相中回收氟化乳化剂的方法,其中:
-确定非离子型表面活性剂的浓度上限值,低于该值时,结合在阴离子交换剂上乳化剂的解吸不再减少,
-将水相中非离子型表面活性剂的浓度调节到用所述方法确定的浓度上限值和仍能有效避免聚合物微粒凝结的较低浓度之间,
-将按所述方法调节的水相与阴离子交换树脂进行接触,使乳化剂被吸收到交换树脂上,
-从交换树脂释放出乳化剂。
另一方面,本发明提供一种从除乳化剂外含少量含氟聚合物微粒的水相中回收氟化乳化剂的方法。该方法将水相中非离子型表面活性剂的浓度调节到10-0.1ppm,将按所述方法调节的水相与阴离子交换树脂进行接触,使乳化剂被吸收到交换树脂上,然后用稀无机酸和有机溶剂的混合物从交换树脂释放出乳化剂。
非离子型表面活性剂的合适浓度取决于聚合物的种类,取决于表面活性剂,也取决于水相中所含的其它物质。因此,对每次需要处理的废水测定合适的非离子型表面活性剂浓度极限是有必要的。一般来说,最高浓度不超过10ppm,大多情况下其浓度在5-0.1ppm范围之内。
具体实施方式
如前所述,由于用本发明方法处理的是轻度污染的废水,所以在废水中只加入必需的少量辅助化学品,以免为下一步的废水处理增加新的污染。另一方面,如果在工业生产中有必要对各种不同废水的混合物进行综合性处理,又拟免去每次都须测定废水中的浓度极值,则一般取约3ppm这个平均值是不会有问题的。
采用少量非离子型表面活性剂的另一个优点是,除了可省去不必要的费用外,还可抑制产生工业化规模中很难处理的泡沫,在某些条件下避免废水被消泡剂进一步污染。
在生产含氟聚合物,如生产聚四氟已烯,氟化热塑性塑料和氟化弹性体时,其聚合物是用絮凝法加以分离的。这种絮凝法在高剪切比的条件下用机械方法进行,或用无机酸或无机盐通过化学沉淀法进行。凝固的含氟聚合物一般是经附聚形成块状,再用水进行洗涤,因而工艺废水量相对较大,即通常每产一吨含氟聚合物约有5-10吨废水。在这个工艺步骤中,大部份氟化乳化剂已洗涤出,并溶入废水内。其浓度通常为每立升若干个毫摩尔,相当于约1000ppm。废水中除了已列出的组分外,还含有来自聚合过程的其它化学物质,如其含量大体与乳化剂相仿的引发剂和缓冲剂以及很少量的未凝固的含氟聚合物胶乳粒子。废水中这部分胶乳粒子,通常低于0.5%重量。
现已证实,生产氟化乳化剂的成本很高,特别是因为这种产品在使用时要求很高的纯度。此外,这种乳化剂很难被生物分解,因此应尽最大可能从废水中分离出来。本发明的方法实际上可从上述的轻度污染废水中进行定量回收。
低浓度非离子型表面活性剂的另一个优点是,能从经过阴离子交换的废水中有效分离出胶乳微粒。这种微粒与少量有机絮凝剂接触后很易凝固结团。同时表明,其所需絮凝剂的用量随非离子型表面活性剂浓度的提高而增大。这种被少量表面活性剂和絮凝剂污染的含氟聚合物可用于建筑材料,并不必进行复杂加工或贮存。
合适的非离子型表面活性剂是市售有机羟基化合物的乙氧基化物和丙氧基化物,但由于环保的原因,优选的是非芳族烷氧基化物。因此,应优选使用长链醇的乙氧基化物。
有机絮凝剂例如记载在《聚合物工程与科学全书》(Encycl.Polym.Sci.Engng.),Wiley Interscience,New York 7,211(1987)中。
有机絮凝剂宜为阳离子产品,如聚氯化二烯丙基二甲基铵。
阳离子表面活性剂,如氯化二癸基二甲基铵,同样可用于沉淀非离子稳定的胶乳微粒,但其在工业规模中的用途尚成问题,原因是在操作不得法的情况下进行沉淀,微粒的电荷交换会加倍产生阳离子稳定性胶乳粒子,由此严重降低沉淀度。
现详细介绍本发明的下列实施例。
实施例
在下列实施例中,使用经机械凝结后聚合物分散体中产生的废水。该废水中含有约90%重量的聚合时所用的全氟辛酸及胶乳粒子。这些废水没有用附聚树脂的洗涤水来稀释。研究了由四氟乙烯与乙烯、全氟(正丙基-乙烯基)醚、六氟丙烯聚合反应产生的废水以及四氟乙烯、六氟丙烯和偏二氟乙烯的三元共聚物聚合时产生的废水以及这些废水的混合物。由于已证明,四氟乙烯、上述醚和乙烯的三元共聚物和共聚物的废水易于堵塞交换柱(塔),故对这种废水进行更详细的研究分析。
阴离子交换柱的尺寸如下:高为5厘米;直径为4厘米;填料量为500毫升;流速为0.5-1升/小时;运行方式:从上到下。采用市售商品名为AMPERLITE IRA 402的强碱性离子交换剂,其交换能力为1.2毫摩尔/毫升。
通过在恒定流体静压力下控制柱内流速,确定柱的填充量。这个试验进行到流出全氟辛酸时为止。一个实验室规模的典型试验,要求的量可达150升。流速可通过在开始和结束时称量给定时间内的被交换的废水来确定。在试验结束时流速降低小于20%视为可以接受的。试验开始时,阴离子交换树脂是OH型。全氟辛酸的测定极限为5ppm。
实施例1
待处理的工艺废水(聚合母液)来自四氟乙烯、六氟乙烯和偏二氟乙烯三元共聚物的聚合过程,其中聚合物胶乳粒子占0.3%重量,全氟辛酸占0.1%重量。采用市售商品名为TRITON X 100的对-辛基苯酚-乙氧基化物(Rohm &Haas,CAS-Nr.9002-93-1)。
表1
TRITON的浓度(ppm) | 50 | 10 | 3 | 0.3 |
处理废水总量(升) | 125 | 150 | 150 | 150 |
流速[升/小时]开始时结束时 | 1.00.9 | 1.00.95 | 1.01.0 | 1.01.0 |
流过下述体积后全氟辛酸浓度(ppm):50升100升125升150升 | <532>100- | <52017>100 | <5<511>100 | <5<57>100 |
临近穿透时的全氟辛酸的浓度显示在较高浓度的非离子型表面活性剂的条件下的“流出(run-out)”。在非离子型表面活性剂浓度较高时,离子交换能力趋于降低。
实施例2
重复实施例,所不同的是以市售脂肪醇聚乙二醇醚GENAPOL X 080(Hoechst AG)为非离子型表面活性剂。
表2
GENAPOL的浓度(ppm) | 300 | 30 | 3 | 0.3 |
处理废水总量(升) | 125 | 125 | 150 | 150 |
流速(升/小时)开始时结束时 | 1.00.9 | 1.00.9 | 1.00.95 | 1.00.95 |
流过下述体积后全氟辛酸浓度(ppm):50升100升125升150升 | <523>100- | <518>100- | <5<512>100 | <5<58>100 |
实施例3
重复实施例2的步骤,但处理的工艺废水(聚合母液)来自四氟乙烯与全氟(正丙基-乙基)醚的共聚物的聚合过程。这种废水含0.1%重量的全氟辛酸和0.4%重量的聚合物胶乳粒子。
表3
GENAPOL的浓度(ppm) | 30 | 3 | 0.3 |
处理废水总量(升) | 150 | 150 | 150 |
流速(升/小时)开始时结束时 | 1.00.9 | 1.01.0 | 1.00.9 |
流过下述体积后全氟辛酸浓度(ppm):50升100升125升150升 | <5<515>100 | <5<57>100 | <5<59>100 |
实施例4
重复实施例2的步骤,但处理的工艺废水(聚合母液)来自四氟乙烯和乙烯的共聚物的聚合过程,这种废水含0.2%重量的全氟辛酸和0.6%重量的聚合物胶乳粒子。
表4
GENAPOL的浓度(ppm) | 30 | 3 | 0.3 |
处理废水总量(升) | 75 | 75 | 75 |
流速(升/小时)开始时结束时 | 0.50.45 | 0.50.45 | 0.50.45 |
流过下述体积后全氟辛酸浓度(ppm):50升100升125升150升 | <5<535>100 | <5<512>100 | <5<510>100 |
实施例5
表5和表6所列的废水用市售有机絮凝剂MAGNOFLOC 1697(聚氯化二烯丙基二甲基铵,Allied Colloids Company)处理。用于定量沉淀胶乳粒子的絮凝剂最低浓度可通过滴定法测定。在缓慢搅拌下将0.1%(重量)的絮凝剂溶液滴加入到交换洗脱液中。胶乳粒子在瞬间就发生沉淀,且沉淀速度很快。如果没有发现进一步的沉淀,则就可停止滴入絮凝剂。试验结果见下表:
表5不含全氟辛酸(PFOA)的工艺废水(PFOA浓度<5ppm)
废水来源 | 实施例1 | 实施例3 | 实施例4 | ||||||
GENAPOL浓度(ppm) | 300 | 30 | 3 | 300 | 30 | 3 | 300 | 30 | 3 |
絮凝剂最低浓度(ppm) | 23 | 3.5 | 2.6 | 27 | 3.0 | 2.7 | 35 | 9 | 7.7 |
表6未作处理的废水(PFOA浓度约为1000ppm)
废水来源 | 实施例1 | 实施例3 | 实施例4 | ||||||
GENAPOL浓度(ppm) | - | 3 | 30 | - | 3 | 30 | - | 3 | 30 |
絮凝剂最低浓度(ppm) | 4.6 | 6 | 10 | 8.3 | 10 | 15 | 8.0 | 10 | 13 |
Claims (7)
1.从除乳化剂外含少量含氟聚合物微粒的水相中回收氟化乳化剂的方法,其特征在于将水相中非离子型表面活性剂的浓度调节到10-0.1ppm,将按所述方法调节的水相与阴离子交换树脂进行接触,使乳化剂被吸收到交换树脂上,然后用稀无机酸和有机溶剂的混合物从交换树脂释放出乳化剂。
2.根据权利要求1所述的方法,其特征在于所述非离子型表面活性剂的浓度为5-0.1ppm。
3.根据权利要求1所述的方法,其特征在于所述的非离子型表面活性剂是非芳族非离子型表面活性剂。
4.根据权利要求1所述的方法,其特征在于所述的非离子型表面活性剂是脂肪醇乙氧基化物。
5.根据权利要求1所述的方法,其特征在于在水相中加入有机絮凝剂,使含氟聚合物微粒得以全部沉淀。
6.根据权利要求5所述的方法,其特征在于所述的絮凝剂为有机阳离子絮凝剂。
7.根据权利要求5或6所述的方法,其特征在于将絮凝剂加入到未处理或经处理的水相中。
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PL364027A1 (en) | 2004-11-29 |
RU2248328C2 (ru) | 2005-03-20 |
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HUP0201949A3 (en) | 2003-01-28 |
DE19933696A1 (de) | 2001-01-18 |
KR100447479B1 (ko) | 2004-09-07 |
ZA200200397B (en) | 2003-06-25 |
AU6691500A (en) | 2001-02-05 |
EP1208065A1 (de) | 2002-05-29 |
SA00210609B1 (ar) | 2006-08-22 |
CZ2002128A3 (cs) | 2002-10-16 |
CN1361751A (zh) | 2002-07-31 |
JP3820369B2 (ja) | 2006-09-13 |
BR0012520A (pt) | 2002-04-02 |
TR200200135T2 (tr) | 2002-06-21 |
MXPA02000597A (es) | 2003-07-21 |
US6706193B1 (en) | 2004-03-16 |
JP2003505223A (ja) | 2003-02-12 |
CA2379931A1 (en) | 2001-01-25 |
AR024730A1 (es) | 2002-10-23 |
ES2173825T1 (es) | 2002-11-01 |
HUP0201949A2 (hu) | 2002-11-28 |
KR20020039322A (ko) | 2002-05-25 |
WO2001005710A1 (de) | 2001-01-25 |
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