CN1102865C - 用键合到膜上的能束缚离子的配位体分离和浓缩某些离子的方法 - Google Patents
用键合到膜上的能束缚离子的配位体分离和浓缩某些离子的方法 Download PDFInfo
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Abstract
一种从含有高浓度的其它离子的源溶液中除去、分离和浓缩某些选择离子的方法,包括使源溶液与由能束缚离子的共价地键合到具有亲水表面性质的膜上的配位体接触。组合体上的配位体部分具有对选择离子的亲合力并能与之形成络合物,从而,从源溶液中除去它们。然后,通过与其量少得多的接收液接触,从组合体中除去选择离子,选择离子在接收溶液中是可溶的,或所述接收溶液与组合体上的配位体部分相比具有对这些选择离子的较大的亲合力,从而定量地从配位体中解吸出这些络合的离子,并在所述接收溶液中以浓缩的形式回收它们。如此除去的浓缩离子可用已知的方法进一步分离和回收。该方法可以用来从各种源溶液中除去包括贵金属和其它过渡金属在内的选择离子。可以用在半导体、核废料的净化、金属冶炼、环境净化、提供超高纯流体、电力和其它工业领域中。此外,本发明还提供了一种配位体-膜的组合体。
Description
本发明的领域
本发明涉及与膜以共价键键合的能束缚离子的(ion-binding)配位体,以及用配位体-膜组合体从溶液中除去和浓缩某些选择离子的方法,其中这些离子可与其它以高浓度存在的离子混合。特别是,本发明涉及一种配位体-膜组合体,并涉及一种从源溶液中与其它离子的混合物中除去这些离子的方法,该方法是这样实现的:使这种溶液流过含有配位体-膜组合体接触设备,形成选择离子与配位体组合物的络合物,然后,使其量比源溶液的量少得多的接收液流过接触设备,从离子已固定在其上的组合体中打破选择离子的络合物,从而除去并浓缩接受溶液中的选择离子。如此除去的这些浓缩离子可再用已知的方法来回收。
背景技术
具体应用在本发明实施方案中这种类型的复合膜,以前就已在Steuck的US 4 618 533公开了。所公开的这种类型的一些能束缚离子的配位体也是已知的。例如,Bradshaw等人在US 4 952 321中公开了一种结合到固体无机载体,如氧化硅或硅胶上的含胺烃,其中配位体是通过一个含有三烷氧基硅烷基团的烃间隔基被键合到固体无机载体上的。Tarbet等人在US5 071 819和5 084 430中公开了含硫和氮的烃作为能束缚离子的配位体。Bradshaw等人在US 4 959 153和5 039 419公开了一种含硫的烃配位体。Bradshaw等人在US4 943 375和5 179 213上公开一种能束缚离子的冠状配位体(Crown)和穴状配位体(Cryptands)配位体。Bruening等人在US 5 182 251上公开了一种含氨基烷基膦酸的烃的配位体。Bradshaw在US 4 960 882上公开了一种可质子-离子化的大环配位体。Tarbet等人在US 5 078 978上公开了一种含吡啶的烃的配位体。Bruening等人在US 5 244 856上公开了一种含聚四烷基铵和聚三烷基胺的烃配位体。Bruening等人在US 5 173 470上公开了一种含氮的硫醇和/或硫醚-芳烷基烃的配位体。Bruening等人在US 5 190 661上公开了一种含硫的烃配位体同时也含有吸电子基团。1993年5月7日的待审申请08/058 437公开了一种氧给体的大环,例如含大环聚醚穴状配位体(cryptands)、杯状配位体(calixarenes)和球状配位体(spherands),多臂状配位体(multiarmed)醚和其混合物的配位体。所有这些现有技术都涉及将配位体经含硅烷的间隔基键合到固体无机载体上。然而,研究人员以前并未提出将络合物、强烈相互作用和高选择性的能束缚离子的配位体引入到膜中,然而这是非常必要的,这是因为这些膜具有高的表面对面积的比率(surface-to-area ratios)、便利的物理形式、易于生产、易于使用、成本低廉。本发明成功地实现了这一伟绩。
本发明概述
本发明的组合体包括通过酰胺、酯、硫醚、羰基或其它合适的键共价地键合到膜上的能束缚离子的配位体。本身是亲水性的、或部分亲水的,并含有适合于产生这些键的膜是优选的。这些膜包括聚酰胺,如尼龙、纤维素材料,如纤维素、再生纤维素,乙酸纤维素、和硝化纤维素。如果所用的膜不含活性基团,则可以进行适当的改性和衍生。复合膜也有用的。复合膜包括多孔聚合物膜基材和沉积在其上的不溶于水的交联涂层。适合于形成膜的基材的富代表性的聚合物包括氟化聚合物,包括聚(四氟乙烯)(“TEFLON”),聚偏氟乙烯(PVDF)等;聚烯烃,如聚乙烯、超高分子量聚乙烯(UPE)、聚丙烯、聚甲基戊烯等;聚苯乙烯或取代聚苯乙烯;聚砜,如聚砜、聚醚砜等;包括聚对苯二甲酸乙二醇酯、聚对苯二甲酸丁二醇酯等的聚酯;聚丙烯酸酯和聚碳酸酯;乙烯基聚合物,如聚氯乙烯、聚丙烯腈。共聚物也可以来用形成聚合物膜基材,如丁二烯和苯乙烯的共聚物、氟化乙烯-丙烯共聚物、乙烯-一氯三氟乙烯共聚物等。
对于复合膜,并不认为基材膜材料会影响所得到的膜的性能,它在组合体中的限制仅在于它的被涂布能力,或者不溶于水的含有适当活性基团的聚合物层在其表面的沉积能力。这样提供了一种能与水或其它水溶液起良好作用的亲水层。其最终结果是,当有机配位体固定到具有亲水表面的亲水膜或复合膜上时,任何给定的配位体分子的基本特征都不会由于固定到表面的过程或表面本身的性质而有改变。
复合膜的涂层包括聚合的交联单体。合适的富有代表性的可聚合单体包括羟烷基丙烯酸酯或甲基丙烯酸酯,如1-羟基丙-2-基-丙烯酸酯、和2-羟基丙-1-基-丙烯酸酯、羟基丙基甲基丙烯酸酯、2,3-二羟基丙基丙烯酸酯、羟基乙基丙烯酸酯、羟基乙基甲基丙烯酸酯等和其混合物。可用的其它可聚合单体包括丙烯酸,2-N,N-二甲基氨基乙基甲基丙烯酸酯、硫乙基甲基丙烯酸酯等,丙烯酰胺、甲基丙烯酰胺、乙基丙烯酰胺等。本发明范围内可用的其它种类的亲水涂层包括如缩水甘油基丙烯酸酯和甲基丙烯酸酯环氧官能团,如氨基乙基甲基丙烯酸酯的伯胺,和如乙烯基苄氯、乙烯基苄胺和p-羟基乙烯基苯的苄基衍生物。
复合膜的涂层还含有一个沉积晶体系统,如涉及到以”NAFION”为商标名的材料。”NAFION”是一种磺酸或全氟聚醚的磺酸钠。
在选择一个复合膜时的基本考虑是位于膜基材上的涂层是决定用来共价地固定配位体的化学性质的决定因素。例如,显示羧酸官能团的复合膜可与来自配位体的胺侧基形成酰胺键,这是配位体定位的最稳定方法之一。以上提到的这种复合聚合物可以用羧酸活性基团制备,这种羧酸活性基团可以容易地与配位体上的胺基团反应,转变成酰胺。然而任何对于酸性氯化物是有活性的其它有机基团可被用来把配位体固定到表面。这种基团的其它例子可以是酯、硫酯、格利雅(Grignard)试剂等。
如果在表面上的活性基团是磺酸,那么用磺酰氯化物将会产生与用羧酸官能团得到的相类似的结果。含有磺酸反应基团的这种聚合物可以从上述的Dupont以”NAFION”为商品名而得到。
这种配位体是从包括含胺烃、含硫和氮烃、含硫烃、冠状配位体和穴状配位体、含氨基烷基膦酸烃、含聚亚烷基-聚胺-聚羧酸的烃、含可质子-离子化的大环、含吡啶的烃、含聚四烷基铵和聚三烷基胺的烃、含硫醇和/或硫醚-芳烷基氮的烃、含硫的也含有吸电子基团的烃、和大环的聚醚穴状配位体当与混有其它离子的溶液接触时,其中的配位体能够选择地络合某些,如碱金属、碱土金属、贵金属、其它过渡金属和过渡后跟金属的离子。
用配位体膜组合体来除去和浓缩某些选择离子的方法可以以任何能使要除去的离子与固定在膜上的配位体接触的方式来进行。该方法总的来说包括从一多离子溶液中选择地除去和浓缩一种或多种选择的离子,从而使之与其它多种离子分开,在该溶液中,其它离子可以高得多的浓度存在。可以使多离子溶液或源溶液与本发明的组合体接触,在这里公开的一个优选方案中,包括使大量的多离子溶液与本发明的组合体材料接触。接触优选在一个包括一柱体的接触装置内进行,该柱体具有本发明的组合体,通过使多离子溶液流过柱体,从而与本发明的组合体接触。然而,可以使用各种接触设备以代替柱体。选择的一种或多种离子与本发明的组合体络合。在络合步骤之后,用少量的接收液体(receiving liquid)或洗脱液与吸附了的组合体接触,通过化学或热的方法来打破络合,并溶解选择的种离子,从组合体中把它们带走。选择的离子可以通过已知的方法从接收液中回收。
更具体地说,该方法包括将上面提及的那种配位体共价地键合到例如前面提及的那些复合膜的一种复合膜上,从而形成一种络合剂。然后将络合剂引入到如柱体的接触装置内。含有多种离子的溶液流过柱体与络合剂接触,因此选择的离子与络合剂发生络合。这样,选择的离子与流出柱体的离子混合物中的其它离子分离开来。然后,少量的接收液体或洗脱剂穿过柱体打破络合,溶解并带走选择的一种或多种离子。之后,通过已知的方法从接受相中回收选择的离子。
本发明的详细描述 配位体-膜组合体的制备
本发明的组合体可以通过任何合适的方法来制备,其中配位体应能共价地键合到具有活性官能团的膜上。
选择的膜提供了选择的堆积性能和选择的表面性能。对天然亲水膜,其选择的堆积和表面性能由含有该膜的任何聚合物提供。对于复合膜,选择的堆积性能由膜的基材来提供,选择的表面性能由涂层提供。复合膜是通过将单体直接沉积到包括孔的内表面在内的基材的表面,通过交联单体的就地沉积来形成的。交联单体在多孔基材上的必要沉积作为一种直接涂布来进行,不需要或不利用中间键合化学基团。可以使用任何涂布聚合物单体,只要它能通过自由基聚合并能交联就行。对聚合单体的唯一要求是应能在多孔膜的整个表面上涂布,这样能提供具有配位体活性的官能团的表面,这些官能团具有足够的亲水性,能有效地使用要固定的配位体。通常,多孔基材的平均孔径为0.001-10μm,通常优选约0.1-5.0μm。复合膜通过适当的方法来形成,如美国专利US4 618 533中所描述的方法,该文献在这里引入作为参考。简单地说,这一方法包括用一种能润湿基材整个表面的适当溶剂清洗多孔膜基材,然后,在能引起单体自由基聚合的条件下,将基材浸泡到可通过自由基聚合的单体、聚合引发剂和交联剂的溶剂混合物中,并用交联剂聚合物涂布多孔基材。涂布的聚合物膜表面含有能活化的亲水或极性取代基,并把配位体共价地键合到膜的表面。
按美国专利US 4 618 533制备的复合膜在其表面含有羧酸基团。其它合适的基团包括羟基、磺酸基、环氧基、伯胺基、和衍生的苄基,正如上面提及的聚合物一样。
简单地说,利用沉积晶体技术制备复合膜的方法包括用适当的能润湿基材整个表面的溶剂洗涤多孔膜基材。然后,将基材浸泡到含有要沉积的晶体的溶液中。再除去溶液,用将晶体沉积并固定到基材上的化合物处理基材。在使用之前洗涤并干燥膜。
在本发明中,羧酸基团的活化是例如通过使羧酸基团与亚硫酰氯反应,形成酸性氯化物基团,其反应式如下:
含有活性胺、醇、硫醇、格利雅试剂等的配位体(L)可以通过-C(O)Cl基团共价地键合到膜上,如:(1) (2) (3) (4)
在类似的方式中,磺酸基团的活化是,例如,通过磺酸基与亚硫酰氯按如下反应式反应形成磺酰氯基:
磺酰氯基也可以通过磺酸基与五氯化磷或三氯化磷的反应来获得。
含有活性胺、醇等的配位体(L)可以通过-S(O)2Cl基团按下述共价地键合到膜上:(1) (2)
与由羧酸形成的酸性氯化物的反应相比,该反应难于进行。然而,只要能在配位体与膜之间形成稳定的共价键的任何反应就可以使用。对于本发明,已发现酰胺键是最稳定的,而且易于形成。
对于配位体,可以采用含有-NH2、-OH、-SH、-MgX基团的那些,这些基团具有反应活性,能与固定官能团的膜形成共价键,这些配位体描述在下述专利中,这些专利在这里引入作为参考:含有胺基的烃(US 4 952 321),含有硫和氮的烃配位体(US 5 071 819和5084 430),含硫的烃配位体(US 4 959 153和5 039 419)、冠状配位体和穴状配位体(US 4 943375和5 179 213),含有氨基烷基膦酸的烃配位体(US 5 182 251),可质子-离子化的(proton-ionizable)的大环配位体(US 4 960 882),含有吡啶的烃配位体(US 5 078 978),含有聚四烷基铵和聚三烷基胺的烃配位体(US 5 244 856),含有硫醇和/或硫醚芳烷基氮的烃配位体(US 5 173 470),含有硫和吸电子基团的烃配位体(US 5 190 661)。
一种氧给体大环配位体,如在93年5月7日申请的共同待审的申请08/058 437中所公开的,具有反应活性基团固定能力的配位体,可以通过许多反应方式来制备,这里描述两种方式。第一种包括顺式二羟基冠醚与聚醚二醇(polyether diol)反应,在这里二醇基已通过与“离去(leaving)”基团,如甲苯磺酰基氯的反应被活化了。如下反应方程式(反应A)显示了通过顺式二羟基冠醚(通式3)与苯甲磺酰化的(tosylated)聚醚二元醇(通式4)反应,形成了氧给体大环配位体(通式2),其中Ts表示甲苯磺酰基,R3、R4、R5和R6单独是选自由下列基团组成的组:H、烯丙氧基甲基、烷基硫代(alkylthio)、烷基氨基、羧基、羧基烷基和环氧烷基(epoxyalkyl)。R7是选自由H和烷基组成的组,Z是选自由O-亚苯基、O-亚萘基或烷基组成的组,R1和R2各自是选自由H、烯丙基、链烯基、羧基、羧烷基、烯丙氧基、氨基烷基、羟基、硫代和烷基硫代组成的组。不直接与膜表面上的相应的基团反应的官能团必须进一步反应以产生共价键。例如,羧烷基官能团能转化为一个酸性氯化物,再与乙二胺(大量过量)反应以提供一个具有自由胺的单酰胺。然后与膜反应。此外,n是一个2-4的整数,a是0或1的整数,b是0-3的整数,其前提条件是当a是0时,b至少为1,而m是一个0-5的整数。为提供具有活性的反应基团与活性膜反应,应遵循这样的原则:基团R1-R6中有一个或两个,优选仅一个,不是H。剩余的基团R1-R6是H。
当Ts或甲苯磺酰基是如上所描述的时,也可以使用其它离去基团,如甲磺酰盐(mesylates)、氯化物、溴化物等。甲苯磺酰基是优选的,这是因为它是结晶,并且具有较好的反应性能。
第二个反应方程式包括顺式二溴甲基冠醚与聚醚二醇反应。如下反应方程式(反应B)显示了通过顺式二溴甲基冠醚(通式5)与聚醚二醇(通式6)反应,形成了氧给体大环配位体(通式2),其中的符号与上述通式2中符号的意义相同:
具有反应活性基团的相应于通式2的化合物再与用亲水官能团衍生得到的膜反应。
含有多亚烷基-多胺-多羧酸的烃配位体可以通过各种方法制备。例如,在其中一种方法中,多亚烷基-多胺-多羧酸配位体是键合到膜上的。在第二种方法中,多亚烷基多胺是与膜反应,再与多羧酸反应。
上描述的配位体被固定到如硅胶、氧化硅、玻璃、玻璃纤维、氧化镍、氧化锆、氧化铝、氧化钛等固体载体上。将配位体固定到固体载体上是通过硅烷间隔基来实现的。使用这些固体载体存在某些缺点。例如,它们经常不得不盛放在塔或类似结构中,不具备膜的其它外形的适应性。而且,硅烷的化学性质是复杂的,对某些反应或应用有限制。最后,无机载体在某些溶液介质中的不稳定性或甚至部分溶解性使它们在某些分离应用中性能不好或不可接受。然而,固定到上述无机固体载体上的这些配位体以前并未被固定到膜上。
本发明的新颖之处在于膜配位体的结合和使用这种结合在除去必要离子的方法。以前使用过的任何膜都可以通过改性用于本发明。由于配位体本身不是新的,它们可用配位体(“L”)表示,可以进一步分类,即:含胺烃配位体;含硫和氮的烃配位体;含硫烃配位体;冠状配位体和穴状配位体;含氨基烷基膦酸的烃配位体;可质子-离子化的大环配位体;含吡啶的烃配位体;含聚四烷基铵和聚烷甲基胺的烃配位体;含硫醇和/或硫醚芳烷基氮的烃配位体;含硫和吸电子基团的烃配位体;氧给体大环配位体。这里所列出的配位体仅作为例子,并不是全部。也可以使用其它已知的或将被开发的配位体,其限制只在于它们应能共价地固定到膜上,并能从要处理的溶液中选择地吸引和键合选择的要除去的离子。
本发明的膜配位体组合体可用如下通式表示:
M-B-L其中,M是任何衍生具有亲水表面的膜或复合膜,并含有极性官能团;L是上面定义的含有能与膜上的活化了的极性基团反应的官能团的配位体,B是活化了的极性基团与配位体上的官能团之间形成的共价键。富有代表性的B键是选自由酰胺(NHCO)、酯(COO)、硫酯(COS)、羰基(CO)、醚(O)、硫醚(S)和磺酰胺(SO2NH)组成的组。
对于本领域内的技术人员来说,通过如下的实施例,能用于分离选择离子的本发明的膜/配位体组合体将变得更加明显,其中每一个实施例都利用了按美国专利US 4 618 533制备的复合膜,含有羧酸基团或磺酸基团。
实施例1
在本实施例中,按下列步骤制备含氮配位体的衍生膜。将一块3×3英寸的,用含有(固定在其表面上的)羧酸官能团的交联丙烯酸,按美国专利US 4 618 533的方法涂布的聚四氟乙烯(PTFE)(“TEFLON”)膜,浸泡在足够多的亚硫酰氯中,完全覆盖膜的表面。用这种溶液覆盖此膜保持8-14小时,使得亚硫酰氯反应并把羧酸基团转变成酸性氯化物。然后,移出这一活化了的膜,并用己烷进行彻底清洗。其它有机溶剂,如甲苯,也能同样地起作用。此后,这一活化膜放在含有由3g五亚乙基六胺配位体和足够多的甲苯的烧瓶中,使得该膜完全被这种混合物所覆盖。使这一混合物反应8-14小时,在配位体的胺基团中的一个胺基与膜上的酸性氯化物基团之间形成一酰胺键。再用有机溶剂洗涤该膜,以除去未键合的配位体,并在一个通风很好的通风橱中进行空气干燥。在干燥后,检测膜以确定其离子键合性质。检测结果见实施例14。
实施例2
在本实施例中,将一块3×3英寸的,用含有羧酸官能团的交联丙烯酸,按美国专利US 4 618 533的方法涂布的聚偏氟乙烯(PVDF)膜转化为酸性氯化物形式,然后用五亚乙基六胺按实施例1的方法衍生。
在下面的实施例3-12中,将用实施例1的羧酸衍生的PTFE复合膜用于配位体固定。然而,实施例2的PVDF复合膜也已使用,结果类似。当测定固定到实施例1和2中的复合膜上的配位体的分离性能时,发现其结果基本相同。
实施例3
在本实施例中,按下列步骤制备含氮和硫配位体的衍生膜。按实施例1的方法制备一块3×3平方英寸的含有羧酸官能团的PTFE复合膜,并用亚硫酰氯处理。然后,作为第一步,这一材料与五亚乙基六胺反应,经酰胺键把胺键合到膜上。洗涤这一中间产品,并浸泡在含甲苯和1g乙烯硫化物(ethylene sulfide)的第二溶液中,以提供具有-NHCH2CH2SH基团的配位体。当然,也要保证溶液在所有的时间内都能将膜覆盖住。每一步的反应时间都是8-14小时。在膜被干燥后,按实施例15所示测定其离子络合性能。
实施例4
在本实施例中,按下列步骤制备含氮和硫配位体的衍生膜。按实施例1的方法用亚硫酰氯处理一块3×3平方英寸的含有羧酸官能团的PTFE复合膜。然后,这一材料用亚乙基二胺处理,代替实施例3中的五亚乙基六胺。这一反应的结果是得到了经酰胺键键合到膜上的这样一种材料,该材料含有一个自由氨基,然后,按实施例3与含甲苯和乙烯硫化物的溶液进一步反应。在膜被干燥后,按实施例16所示测定其离子络合性能。
实施例5
在本实施例中,按下列步骤制备含硫配位体的衍生膜。含有羧酸基的PTEF复合膜按实施例4制备,使羧酸基转化成酸性氯化物的形式。然后,将膜浸泡在含有甲苯和乙烷二硫醇(ethanedithiol)与一个当量的2-甲基氮丙啶的反应产物的溶液中,以将-CONHCH2CH(CH3)SCH2CH2SH配位体固定在膜上。自由的SH基团用含有甲基碘和碳酸钠的甲醇溶液封闭。在膜被干燥后,按实施例17所示测定其离子络合性能。
实施例6
在这一实施例中,制备含有冠醚的配位体,并按如下方法固定到膜上。含有羧酸基团的酸性氯化物形式的PTFE复合膜按实施例1的方法制备。用于固定的冠是通过将2g烯丙氧基甲基-18-冠-6溶解在二氯甲烷或苯中制备的。通过向搅拌的混合物中添加过氧化氢(1-2小滴30%的溶液),烯丙基中的双键被转化为环氧化物。然后,向环氧化的冠中添加氢氧化铵(0.2g),并将温度升高到30℃-60℃之间。反应进行6-14小时,以形成包括18-冠-6的配位体,该冠中含有-CH2OCH2CH(OH)CH2NH2基团。这一含配位体的反应混合物被添加到含有膜的甲苯溶液中。这一方法使得18-冠-6经一酰胺键而被固定,这一方法也可以用来固定各种其它的大环化合物,或含双键的起始材料。在膜被干燥后,按实施例18所示测定其离子络合性能。
实施例7
在这一实施例中,按下列步骤制备含氨基膦酸配位体的衍生膜。按实施例4的方法用亚硫酰氯和乙二胺处理一块3×3平方英寸的含有羧酸基团的PTFE复合膜,通过将膜放到盛有83ml浓盐酸、83ml水和70g磷酸的三颈圆底烧瓶中,使所得到的氨基-酰胺基被进一步反应。混合物加热回流,在1小时内慢慢地添加270ml甲醛。混合物再回流1-4小时,使配位体经含有-CONHCH2CH2N(CH2PO(OH)2)2基的酰胺键而被固定。用水洗涤这一产品并干燥。该产品按实施例19所示测定其离子络合性能。
实施例8
这一实施例中,除用五亚乙基六胺代替乙二胺,并按这一替换调节反应试剂的量外,按实施例7的方法进行。得到了含-CONH(CH2CH2NH)5CH2PO(OH)2基的配位体。该产品按实施例20所示测定其离子络合性能。
实施例9
在这一实施例中,按如下方法制备含有氮配位体的衍生膜。把一块3×3英寸的,在其表面含有羧酸基团的实施例1的PTFE膜转化为酸性氯化物的形式,并与甲苯中的四杂氮(tetraaza)-12-冠-4反应,在一个环氮原子与酸性氯化物之间形成一个酰胺键。所得膜用甲苯洗涤四次,再按实施例7用浓盐酸、磷酸和甲醛处理,生成具有大环氨基烷基膦酸侧基的膜。这一材料按实施例21所示测定其离子络合性能。
实施例10
在这一实施例中,按如下方法制备含有氨基羧酸膜。这一材料的制备一直到将乙二胺经酰胺键固定到表面都按照实施例7进行。然后,通过将膜放入盛有200ml二甲基甲酰胺(DMF)、0.1g二甲基氨基吡啶(DMAP)、25ml吡啶和1g二亚乙基三胺五乙酸(DTPA)二酐(dianhydride)的烧瓶中,该材料进一步反应。混合物在80℃下反应24-72小时。用水洗涤最终产品,并干燥,按实施例22所示测定其束缚离子的性能。
实施例11
在这一实施例中,按如下方法将含氮穴状配位体固定到含有羧酸基团的PTFE复合膜上。生产固定有穴状配位体2.2.2的膜方法同样按实施例6进行,例外的是用烯丙氧基甲基-穴配位体-2.2.2代替18-冠-6。在膜被干燥后,按实施例23所示测定其离子络合性能。
实施例12
在这一实施例中,按如下方法将含氮冠固定到膜上。按实施例1的方法制备含有羧酸基的酸性氯化物形式的PTFE复合膜。按实施例9,使溶解在甲苯中的六氮杂(hexaza)-18-冠-6与膜反应8-14小时。在按实施例24测定离子除去性能之前,用甲苯洗涤并干燥膜。
实施例13
在一实施例中,通过沉积晶体技术用“NAFION”涂布超高分子量的聚乙烯(UPE)膜,以生成在其表面具有磺酸活性基团的膜,然后制备含氮配位体衍生的膜。
UPE膜片(2×12英寸、3×13英寸或直径为2.75cm的盘),每一块都用150ML HPLC级的异丙醇漂洗三次,再用150ml HPLC级的甲醇漂洗三次。然后膜用空气干燥直到重量恒定。此后,将膜用甲醇预先润湿,并将其浸润在50ml“NAFION”Solution(溶液)(全氟聚醚离子交换粉末的磺酸或磺酸钠盐在低级脂肪醇和10%水中5%wt的溶液,AldrichChemical Co.)中约5分钟。然后,将“NAFION”溶液滗析出来,将膜浸泡到二氯甲烷中。再用150ml二氯甲烷将每一块膜漂洗三次,空气干燥2小时,再在真空下干燥过夜(15小时)。
通过与五氯化磷反应将膜上的磺酸基转化为磺酰氯的形式,得到活化膜,这类似于实施例1中从羧酸形成酸性氯化物的形式。这样,2×12英寸、3×3英寸或直径为2.75cm的盘形,用“NAFION”涂布的UPE膜浸渍在足够多的五氯化磷溶液中,完全覆盖膜的表面。将膜浸泡8-14小时,以使五氯化磷将磺酸基团转化为磺酰氯基团。将这一含有磺酰氯基团的活化膜从五氯化磷溶液中移出并用己烷或甲苯充分洗涤。然后将活化膜放入盛有3g五亚乙基六胺配位体和足够多的甲苯的溶液的烧瓶中,保证完全覆盖该膜。混合物反应8-14小时,在配位体的氨基中的一个和活化膜的磺酰氯基之间形成磺酰胺键。再用有机溶剂洗涤膜以除去未键合的配位体,并空气干燥。
也可以根据上述指导制备其它配位体衍生的膜。还可以用上面描述的方式通过形成磺酰胺键或磺酸酯键将配位体固定到磺酸衍生的膜上。
金属离子的回收和浓缩
本发明的金属离子回收和浓缩涉及使用本发明的上面限定的组合体从金属离子混合物中选择回收所选择的离子。从营养水供应线、高纯度流体、废液、沉积物和工业液体中回收和/或分离金属离子以及从废液,如从照相和X射线胶片的悬浮液中回收金属的有效方法在现代技术中是真正需要的。这些离子通常是以低浓度存在于含有其它离子的溶液中,而其它离子是以高得多的浓度存在。因此确实需要一种方法以选择性地回收和浓缩这些不希望的有害的和/或所希望的离子。本发明通过使用本发明的键合到膜上的配位体有效地实现了这一分离。
从混合离子溶液中选择地回收和浓缩金属离子的方法大概包括用本发明的组合体络合源溶液中的选择离子,然后,打破络合释放出络合离子,将释放出来的离子溶解在其量比源溶液少得多的接收溶液中。这里所用的“源溶液”“载液”等是指含有一种或多种选择要浓缩、分离、和/或回收的离子与其它离子以及未被选择要除去的络合或化学试剂的混合物,其它离子或试剂在溶液中是以高得多的浓度存在于溶液中。这里所用的“接收溶液”、“解吸液”、“洗脱液”“洗脱剂”是指对要浓缩、分离、和/或回收的离子具有较大亲合力的水溶液,或这些离子在其中是可溶的溶液。在每一种情况下,选择的离子都在接收溶液中从浓缩形式的配位体上定量地解吸下来,因为在通常情况下接收溶液具有比源溶液少得多的量。
通过考察下面的实施例,使用本发明的膜/配位体组合体来从溶液中分离选择离子的方法对本领域内的技术人员来说是很明显的。
实施例14
将一片0.2g的实施例1的膜放到盛有25ml5×10-4M的CuCl2、1M乙酸钠和0.1M乙酸(Ph=5.5)的烧杯中。膜与源溶液接触120分钟。然后,从源溶液中移出膜,在水中漂洗,放到1M HCl组成的5ml接收溶液中。
在与膜接触前和后用火焰原子吸收(AA)光谱分析源溶液和接收溶液中的铜和钠。起初源溶液中含有23g/l的钠和31ppm的铜,但在与膜接触后,含有23g/l的钠和约1ppm的铜。
起初接收溶液中的铜和钠含量低于可检测量,但在与膜接触后,含有其量检测不出来的钠和154ppm的铜。这一实施例显示膜-配位体分离相对钠来说,对铜是高度选择的,通过与膜接触铜容易从源溶液中除去,铜离子可以回收到少量的接收溶液中。可以预见,当使用更大量的源溶液和更大的膜时,接收溶液中的铜离子的浓度将会更高。
实施例15
将一片0.2g的实施例3的膜放到盛有25ml5×10-4M的Hg(NO3)2、0.1M Ca(NO3)2和0.5M NaNO3的烧杯中。膜与源溶液接触120分钟。然后,从源溶液中移出膜,在水中漂洗,放到由0.5M硫脲和0.1M HNO3组成的5ml接收溶液中。
在与膜接触前和后分析源溶液和接收溶液,用感应偶合等离子体(ICP)光谱分析汞的存在,用火焰原子吸收(AA)光谱分析钙和钠的存在。起初源溶液中含有4g/l的钙和12.5g/l的钠和101ppm的汞,但在与膜接触后,源溶液中含有4g/l的钙和12.5g/l的钠和<1ppm的汞。
起初接收溶液中的钙、钠和汞的含量低于可检测量,但在与膜接触后,溶液含有其量检测不出来的钙和钠以及505ppm的汞。因此,汞从还含有钙和钠的源溶液中高度选择地分离出来了。汞容易从含有离子混合物的源溶液中除去,通过洗脱在简单的接收溶液中,汞被回收并浓缩。与实施例14一样,可以预见,使用一个更大规模的分离系统,特别是使用柱状形式的工程膜,可以改进浓缩因子。
实施例16
将一片0.2g的实施例4的膜放到盛有25ml5×10-4M的AgNO3、0.1M Fe(NO3)3和0.1M NaNO3的烧杯中。膜与源溶液接触120分钟。然后,从源溶液中移出膜,在水中漂洗,放到由6M HCl组成的5ml接收溶液中。
在与膜接触前和后分析源溶液和接收溶液,用火焰原子吸收(AA)光谱分析银、铁和钠的存在。起初源溶液中含有5.6g/l的铁和12.5g/l的钠以及54ppm的银,但在与膜接触后,源溶液中含有5.6g/l的铁和12.5g/l的钠以及<1ppm的银。
起初接收溶液中的铁、钠和银的含量低于可检测量,但在与膜接触后,接收溶液含有其量检测不出来的铁和钠以及265ppm的银。膜-配位体这种结合能高度选择地从混合离子源溶液中除去银离子。银离子可以以纯净的形式回收并浓缩。
实施例17
将一片0.2g的实施例5的膜放到盛有25ml5×10-4M的PdCl2、6M HCl、0.1MNiCl2和0.1M FeCl3和0.1M ZnCl2的烧杯中。膜与源溶液接触120分钟。然后,从源溶液中移出膜,在水中漂洗,放到由2M NH3和1M HCl组成的5ml接收溶液中。
在与膜接触前和后分析源溶液和接收溶液,用ICP光谱分析钯、镍、和锌的存在。起初源溶液中含有5.9g/l的镍、和5.6g/l的铁和6.5g/l的锌以及52ppm的钯,但在与膜接触后,源溶液中含有5.9g/l的镍、5.6g/l的铁和6.5g/l的锌以及<1ppm的钯。
起初接收溶液中的镍、铁、锌和钯的含量低于可检测量,但在与膜接触后,接收溶液含有其量检测不出来的镍、铁和锌以及262ppm的钯。膜-配位体这种结合能高度选择地从混合离子源溶液中键合钯离子,并除去、纯化和回收钯离子。
实施例18
将一片0.2g的实施例6的膜放到盛有25ml5×10-4M的Pb(NO3)2、1M HNO3、0.1M Mg(NO3)2和0.1M Ca(NO3)2的烧杯中。膜与源溶液接触120分钟。然后,从源溶液中移出膜,在水中漂洗,放到由0.03M EDTA的四钠盐组成的5ml接收溶液中。
在与膜接触前和后分析源溶液和接收溶液,用火焰AA光谱分析铅、镁和钙的存在。起初源溶液中含有2.4g/l的镁、和4.0g/l的钙和102ppm的铅,但在与膜接触后,源溶液中含有2.4g/l的镁、和4.0g/l的钙和约2ppm的铅。
起初接收溶液中的镁、钙、和铅的含量低于可检测量,但在与膜接触后,接收溶液含有其量检测不出来的镁、和钙以及495ppm的铅。膜-配位体这种结合能高度选择地从混合离子源溶液中除去铅离子,并回收和浓缩相对纯的铅。
实施例19
将一片0.2g的实施例7的膜放到盛有25ml5×10-4M的Sb和2M H2SO4、0.3MCuSO4、和0.1M NiSO4的烧杯中。膜与源溶液接触120分钟。然后,从源溶液中移出膜,在水中漂洗,放到由6M HCl组成的5ml接收溶液中。
在与膜接触前和后分析源溶液和接收溶液,用火焰AA光谱分析铜、镍、和锑的存在。起初源溶液中含有5.9g/l的镍、和19g/l的铜和56ppm的锑,但在与膜接触后,源溶液中含有5.9g/l的镍、和19g/l的铜和<5ppm的锑。
起初接收溶液中的镍、铜、锌和锑的含量低于可检测量,但在与膜接触后,接收溶液含有其量检测不出来的镍、铜以及285ppm的锑。由此,膜-配位体这种结合能选择地从混合离子源溶液中键合锑离子,并除去、纯化和回收锑。
实施例20
将一片0.2g的实施例8的膜放到盛有25ml的含有5ppm的铁、5ppm的铅、5ppm的铜、5ppm的镍和5ppm的锌的自来水的烧杯中。自来水中含有相对高浓度的钠、钾、钙和镁离子。膜与源溶液接触240分钟。然后,从源溶液中移出膜,在水中漂洗,放到由6M HCl组成的5ml接收溶液中。
在与膜接触前和后分析源溶液和接收溶液,用ICP光谱分析铁、镍和锌,用火焰AA光谱分析铜和铅。起初源溶液中每一种金属含量如上所述。但在与膜接触后,源溶液中每一种金属的含量都<1ppm。
起初接收溶液中的铁、铅、镍、铜和锌的含量低于可检测量,但在与膜接触后,接收溶液含有25ppm的镍、25ppm的铜、24ppm的铁、26ppm的铅、和26ppm的锌。因此,尽管源溶液中存在钠、钾、钙和镁离子,但是膜-配位体这种结合能容易地从含离子混合物的源溶液中除去铁、铅、铜、镍和锌。
实施例21
将一片0.2g的实施例9的膜放到盛有25ml的含有200ppb的铁和1%HF的烧杯中。膜与源溶液接触480分钟。然后,从源溶液中移出膜,在水中漂洗,放到由37%的HCl组成的5ml接收溶液中。
在与膜接触前和后分析源溶液和接收溶液,用石墨炉AA光谱分析铁。起初源溶液中含有200ppb的铁。但在与膜接触后,源溶液中含有10ppb的铁。
起初接收溶液中的铁的含量低于可检测量,但在与膜接触后,接收溶液含有910ppb的铁。因此,尽管源溶液中铁的量非常低,并存在酸和能与铁强烈螯合的氟,但是膜-配位体这种结合能容易地从源溶液中除去铁。
实施例22
将一片0.2g的实施例10的膜放到盛有25ml的含有10ppm的铁、10ppm的铜、10ppm的镍、0.5M HF和0.5M NaF的烧杯中。膜与源溶液接触240分钟。然后,从源溶液中移出膜,在水中漂洗,放到由3M HCl组成的5ml接收溶液中。
在与膜接触前和后分析源溶液和接收溶液,用ICP光谱分析铁和镍,用火焰AA光谱分析铜。起初源溶液中铁、铜和镍的每一种金属含量为10ppm。但在与膜接触后,源溶液中每一种金属的含量都<1ppm。
起初接收溶液中的铁、铜、镍和钠的含量低于可检测量,但在与膜接触后,接收溶液含有的钠低于检测水平及分别为50ppm的铁、镍的铜。因此,膜-配位体这种结合能容易地从源溶液中移去铁、铜和镍,并且这三种金属可以从源溶液中分离和回收。
实施例23
将一片0.2g的实施例11的膜放到盛有25ml的含有5ppm的钾,Ph=8的去离子蒸馏水的烧杯中。膜与源溶液接触120分钟。然后,从源溶液中移出膜,在水中漂洗,放到由0.1M HCl组成的5ml接收溶液中。
在与膜接触前和后分析源溶液和接收溶液,用火焰AA光谱分析钾。起初源溶液中含有15ppm的钾,但在与膜接触后,源溶液中的钾含量<1ppm。
起初接收溶液中的钾含量低于可检测量,但在与膜接触后,接收溶液含有75ppm的钾。因此,通过与膜键合的方法,能容易地从源溶液中移去钾,并通过在接收液中洗脱而得到回收。
实施例24
将一片0.2g的实施例12的膜放到盛有25ml的含有均为5ppm的铅、镉、汞、铜和镍的自来水的烧杯中。膜与源溶液接触480分钟。然后,从源溶液中移出膜,在水中漂洗,放到由6M HCl组成的5ml接收溶液中。
在与膜接触前和后分析源溶液和接收溶液,用ICP光谱分析汞、镉和镍,用火焰AA光谱分析铅、铜和汞。起初源溶液中铅、镉、汞、铜和镍每一种金属含量为5ppm,但在与膜接触后,源溶液中每一种金属的含量都<1ppm。
起初接收溶液中的铅、镉、汞、铜和镍的含量低于可检测量,但在与膜接触后,接收溶液含有均为25ppm的每一种金属。因此,尽管源溶液中存在也含有钠、钾、钙和镁离子,铅、镉、汞、铜和镍能容易地从源溶液中移去。进而通过吸附到膜的方法,所有从溶液中被移出的元素,被接收液回收和浓缩。
实施例25
将一片(直径为2.75cm的盘)0.04g的实施例13的膜放到一膜夹(一O形环和一夹子)中。这一装置允许盘的一个直径为1.83cm的部分与流过该膜的溶液接触。通过使用真空泵真空抽吸,5ml的含有6ppm的Cu的1M Zn(NO3)2、0.01M乙酸钠和0.1M乙酸的源溶液以1ml/min的速度流过该膜。然后用2ml 1M NH4Cl以1ml/min的速度流过该膜进行洗涤。之后,用3ml由0.5MHCl组成的接收液以2ml/min的速度流过该膜。
在其流过膜之前和之后分析源溶液和接收溶液,用火焰原子吸收光谱分析铜、锌、钠。起初源溶液含有6ppm的铜、65g/l的Zn和2.3g/l的Na。在与膜接触后,源溶液中Zn和Na的含量都未改变,而Cu的含量是2ppm。
起初接收溶液中的Cu、Zn和Na的含量低于可检测量,但在流过膜后,接收溶液含有检测不出来的Zn和Na,但含有10ppm的Cu。因此,膜-配位体这种结合对高浓度的Zn和Na的源溶液中的低浓度Cu具有高的选择性。
根据上面的描述,应当理解本发明的配位体-膜组合体提供了一种可用于从选择离子和其它离子的混合物中分离、回收和浓缩这些金属离子的材料,甚至是当所述其它离子是以高得多的浓度存在时也可以使用。然后,可以使用这些材料技术中已知的标准技术,从接收溶液中分析或进一步浓缩回收的金属。
虽然在本发明中,已通过某些具体的膜-键合配位体描述了用于分离和浓缩某些金属离子的方法,但是使用这些配位体的类似方法也在下面的权利要求书中所限定的本发明的方法的范围之内。
Claims (54)
1.一种适于从溶液中除去选择离子的组合体,包括一种能束缚离子的配位体,该配位体具有对选择离子的亲合力,所选择的离子是共价地键合到聚合物膜上的,所述聚合物膜一配位体可用如下通式表示:
M-B-L其中,M是具有亲水表面特性和含有极性官能团的任何聚合物膜,L是任何对选择离子具有亲合力的、含有对聚合物膜上的活化的极性基团有活性的官能团,B是聚合物膜上的活化了的极性基团与配位体上的官能团反应形成的共价键。
2.根据权利要求1的组合体,其中L是选自由含胺烃;含硫和氮的烃;含硫的烃;冠状配位体和穴状配位体;含氨基烷基膦酸的烃;可质子-离子化的大环;含吡啶的烃;含聚四烷基铵和聚三烷基胺的烃;含硫醇和/或硫醚芳烷基氮的烃;含硫和吸电子基团的烃;氧给体大环组成的组中的一种配位体。
3.根据权利要求2的组合体,其中B是选自由酰胺(NHCO)、酯(COO)、硫酯(COS)、羰基(CO)、醚(O)、硫醚(S)、磺酸酯(SO3)和磺酰胺(SO2NH)键组成的组中的一种共价键。
4.根据权利要求3的组合体,其中M是选自由聚酰胺和纤维素组成的组中的一种膜。
5.根据权利要求4的组合体,其中所述膜是含有尼龙的聚酰胺。
6.根据权利要求3的组合体,其中所述的膜是选自由纤维素、再生纤维素、纤维素乙酸酯和硝化纤维素组成的组中的一种纤维素。
7.根据权利要求3的组合体,其中M是一种复合膜,包括由第一聚合物形成的膜基材,所述基材的整个表面被通过晶体沉积技术用第二聚合物直接涂布,并具有亲水表面。
8.根据权利要求7的组合体,其中所述第一聚合物是选自由氟化聚合物、聚烯烃、聚苯乙烯、聚砜、聚酯、聚丙烯酸酯、聚碳酸酯、乙烯基聚合物和聚丙烯腈组成的组中的一种聚合物或共聚物。
9.根据权利要求8的组合体,其中所说的第二个聚合物是全氟化聚醚。
10.根据权利要求3的组合体,其中M是一种复合膜,包括由第一聚合物形成的膜基材,所述基材的整个表面由单体在该基材上就地聚合并就地交联所形成的交联的第二聚合物直接涂布,并具有亲水表面。
11.根据权利要求10的组合体,其中第一聚合物是选自由氟化聚合物、聚烯烃、聚苯乙烯、聚砜、聚酯、聚丙烯酸酯、聚碳酸酯、乙烯基聚合物和聚丙烯腈组成的组中的一种聚合物或共聚物。
12.根据权利要求11的组合体,其中所述的第二聚合物是由选自由丙烯酸酯、甲基丙烯酸酯、乙基丙烯酸酯、丙烯酸、丙烯酰胺、甲基丙烯酰胺、乙基丙烯酰胺以及其混合物组成的组中的一种可聚合单体所形成的。
13.根据权利要求12的组合体,其中L是含胺烃配位体。
14.根据权利要求12的组合体,其中L是含硫和氮的烃配位体。
15.根据权利要求12的组合体,其中L是含硫烃配位体。
16.根据权利要求12的组合体,其中L是冠状配位体。
17.根据权利要求12的组合体,其中L是穴状配位体。
18.根据权利要求12的组合体,其中L是含氨基烷基膦酸的烃配位体。
19.根据权利要求12的组合体,其中L是可质子-离子化的大环配位体。
20.根据权利要求12的组合体,其中L是含吡啶的烃配位体。
21.根据权利要求12的组合体,其中L是含聚四烷基铵和聚三烷基胺的烃配位体。
22.根据权利要求12的组合体,其中L是选自由含硫醇-芳烷基氮的烃配位体和硫醚-芳烷基氮的烃配位体组成的组中的一种。
23.根据权利要求12的组合体,其中L是含硫和吸电子基团的烃配位体。
24.根据权利要求12的组合体,其中L是氧给体大环配位体。
25.根据权利要求12的组合体,其中B是酰胺键。
26.根据权利要求3的组合体,其中B是磺酰胺键。
27.一种从源溶液中浓缩、除去和分离选择离子的方法,包括如下步骤:
(a)使具有第一体积的所述源溶液与一种组合体接触,所述组合体包括一种能束缚离子的配位体,该配位体具有对选择离子的亲合力,该离子共价地键合到聚合物膜上的,所述聚合物膜配位体组合体可用如下通式表示:
M-B-L其中,M是具有亲水表面性质和含有极性官能团的任何聚合物膜,L是对选择离子具有亲合力的、含有对聚合物膜上的活化的极性基团有活性的官能团,B是聚合物膜上的活化了的极性基团与配位体上的官能团反应形成的共价键,其中组合体的所述配位体部分具有对选择离子的亲合力,如在所述选择离子与所述组合体中的所述配位体部分之间形成络合物;
(b)从与所述组合体的接触中移出源溶液,这时选择离子已络合到所述组合体上;和
(c)使具有络合到其上的选择离子的组合体与较少量的接收水溶液接触,所述的选择离子在所述接收溶液中是可溶的,或所述接收溶液与组合体上的配位体部分相比具有对这些选择离子的有较大的亲合力,从而定量地从配位体中解吸出这些选择离子,并在所述接收溶液中以浓缩的形式回收所述选择离子。
28.根据权利要求27的方法,其中L是选自由含胺烃;含硫和氮的烃;含硫的烃;冠状配位体和穴状配位体;含氨基烷基膦酸的烃;可质子-离子化的大环;含吡啶的烃;含聚四烷基铵和聚三烷基胺的烃;含硫醇和/或硫醚芳烷基氮的烃;含硫和吸电子基团的烃;氧给体大环组成的组中一种的配位体。
29.根据权利要求28的方法,其中B是选自由酰胺(NHCO)、酯(COO)、硫酯(COS)、羰基(CO)、醚(O)、硫醚(S)、磺酸酯(SO3)和磺酰胺(SO2NH)键组成的组中的一种共价键。
30.根据权利要求29的方法,其中M是选自由聚酰胺和纤维素组成的组中的膜。
31.根据权利要求30的方法,其中所述膜是含有尼龙的聚酰胺。
32根据权利要求30的方法,其中所述的膜是选自由纤维素、再生纤维素、纤维素乙酸酯和硝化纤维素组成的组中的一种纤维素。
33.根据权利要求29的方法,其中M是一种复合膜,包括由第一聚合物形成的膜基材,所述基材的整个表面被通过晶体沉积技术用第二聚合物直接涂布,并具有亲水表面。
34.根据权利要求33的方法,其中第一聚合物是选自由氟化聚合物、聚烯烃、聚苯乙烯、聚砜、聚酯、聚丙烯酸酯、聚碳酸酯、乙烯基聚合物和聚丙烯腈组成的组中的一种聚合物或共聚物。
35.根据权利要求34的方法,其中所说的第二聚合物是全氟聚醚。
36.根据权利要求29的方法,其中M是一种复合膜,包括由第一聚合物形成的膜基材,所述基材的整个表面由单体在所述的基材上就地聚合并就地交联所形成的交联的第二聚合物直接涂布,并具有亲水表面。
37.根据权利要求36的方法,其中第一聚合物是选自由氟化聚合物、聚烯烃、聚苯乙烯、聚砜、聚酯、聚丙烯酸酯、聚碳酸酯、乙烯基聚合物和聚丙烯腈组成的组中的一种聚合物或共聚物。
38.根据权利要求37的方法,其中第二聚合物是由选自由丙烯酸酯、甲基丙烯酸酯、乙基丙烯酸酯、丙烯酸、丙烯酰胺、甲基丙烯酰胺、乙基丙烯酰胺以及其混合物组成的组中的一种可聚合单体所形成的。
39.根据权利要求38的方法,其中L是含胺烃配位体。
40.根据权利要求38的方法,其中L是含硫和氮的烃配位体。
41.根据权利要求38的方法,其中L是含硫烃配位体。
42.根据权利要求38的方法,其中L是冠状配位体。
43.根据权利要求38的方法,其中L是穴状配位体。
44.根据权利要求38的方法,其中L是含氨基烷基膦酸的烃配位体。
45.根据权利要求38的方法,其中L是可质子-离子化的大环配位体。
46.根据权利要求38的方法,其中L是含吡啶的烃配位体。
47.根据权利要求38的方法,其中L是含聚四烷基铵和聚三烷基胺的烃配位体。
48.根据权利要求38的方法,其中L是选自由含硫醇-芳烷基氮的烃配位体和含硫醚-芳烷基氮的烃配位体组成的组中的一种。
49.根据权利要求38的方法,其中L是含硫和吸电子基团的烃配位体。
50.根据权利要求38的方法,其中L是氧给体大环配位体。
51.根据权利要求38的方法,其中B是酰胺键。
52.根据权利要求29的方法,其中B是磺酰胺键。
53.根据权利要求27的方法,其中所述组合体是被放在用于支撑所述组合体的接触装置中,其中,所述的接触装置包括使源溶液和接收液流过所述组合体的元件。
54.根据权利要求53的方法,其中所述接触装置包括一柱状元件。
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- 1995-04-25 DE DE69530384T patent/DE69530384D1/de not_active Expired - Lifetime
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- 1995-04-25 CZ CZ963097A patent/CZ309796A3/cs unknown
- 1995-04-25 BR BR9507546A patent/BR9507546A/pt not_active Application Discontinuation
- 1995-04-25 WO PCT/US1995/004833 patent/WO1995029008A1/en active IP Right Grant
- 1995-04-25 EP EP95916458A patent/EP0757589B1/en not_active Expired - Lifetime
- 1995-04-25 AU AU22952/95A patent/AU686796B2/en not_active Ceased
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- 1996-10-25 NO NO964536A patent/NO964536L/no unknown
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Also Published As
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DE69530384D1 (de) | 2003-05-22 |
LV11791A (lv) | 1997-06-20 |
JPH09511948A (ja) | 1997-12-02 |
KR100406507B1 (ko) | 2004-05-31 |
AU686796B2 (en) | 1998-02-12 |
PL317023A1 (en) | 1997-03-03 |
EP0757589A1 (en) | 1997-02-12 |
BR9507546A (pt) | 1997-08-05 |
US5980987A (en) | 1999-11-09 |
AU2295295A (en) | 1995-11-16 |
LT96152A (en) | 1997-05-26 |
CA2188649A1 (en) | 1995-11-02 |
HUT75287A (en) | 1997-05-28 |
FI964305A (fi) | 1996-12-23 |
EP0757589A4 (en) | 1997-11-19 |
CZ309796A3 (en) | 1997-09-17 |
FI964305A0 (fi) | 1996-10-25 |
US20010021413A1 (en) | 2001-09-13 |
WO1995029008A1 (en) | 1995-11-02 |
US6544422B2 (en) | 2003-04-08 |
LT4226B (en) | 1997-10-27 |
US5618433A (en) | 1997-04-08 |
NO964536D0 (no) | 1996-10-25 |
NO964536L (no) | 1996-10-25 |
ATE237398T1 (de) | 2003-05-15 |
NZ284360A (en) | 1998-01-26 |
HU9602915D0 (en) | 1996-12-30 |
JP3100638B2 (ja) | 2000-10-16 |
US5547760A (en) | 1996-08-20 |
CN1151128A (zh) | 1997-06-04 |
EP0757589B1 (en) | 2003-04-16 |
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