CN101735264B - 一种螯合剂及其应用 - Google Patents
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Abstract
本发明公开了一种螯合剂以及该螯合剂在超临界CO2螯合萃取金属离子中的应用。该螯合剂具有低聚乙二醇桥链，两端以磷酸酯化形成的中性多齿配位结构，侧链含有直链或含有支链脂肪烃基、含单个硅原子或Si-O-Si键的脂肪烃基、含有全乙酰化β-葡萄糖基的烷基等。本发明的螯合剂对金属离子具有强螯合作用，适用于被金属离子污染的固体基质如电子垃圾、固体核废料等的无害洁净化处理，以及高精密集成电路或晶片的清洗，特别适用于与超临界CO2螯合萃取金属离子。
Description
技术领域
本发明属于绿色化学技术领域，具体涉及一种螯合剂及其应用。
背景技术
重金属对自然环境的污染破坏相当严重，工业中产生的大量废液、废渣等包含有较多的重金属离子，如果处理不当，不但消除不了重金属离子对环境的污染，反而会给环境带来二次污染。此外，对核工业产生高放射性金属离子的废液废渣，科学家们一直在探索一种行之有效的绿色净化处理技术。
除了工业废液废渣污染外，当今另一种重金属污染源-大量的电子垃圾，在我国和世界其它主要电子产品消费国造成的重金属环境污染也愈加严重。目前含有重金属的电子垃圾，要么经过简单掩埋法处理，要么经过普通的化学沉淀法处理，虽然能暂时消除地面污染源，但对地下水源或地下微生物环境的破坏却是非可逆的。电子垃圾中多含有金、银、钯等贵金属，如能找到行之有效的净化处理方法，不但可以解决环境污染问题，而且还可以回收大量贵金属。为了避免重金属离子对环境的危害，世界各国均制定了严格的标准及规范，并在净化技术研发方面投入了巨大的人力、物力和财力，以期变害为利，变废为宝。
超临界CO2萃取技术，已经发展了近三十年，作为绿色化学化工技术，正逐步推广到工业、农业、环保等领域。超临界CO2，兼有气体和液体的双重优点和特性，具有低粘度，传质快，操作条件温和，后续处理简单，低成本、惰性、对环境友好等诸多优点。带电荷的金属离子本身不溶于超临界CO2，但在超临界CO2中加入适当的螯合剂，金属离子往往可被有效地萃取出来。因此，超临界CO2螯合萃取技术将在重金属污染物的处理方面发挥作用。该技术可以应用到环境重金属污染的净化、食品和药品中重金属离子的脱除、核废料放射性金属的有效回收处理、电子垃圾中贵金属(如金、铂、银等)和贱金属(如铜、镍、锌、铁等)的有效回收利用、高精密仪器或微小尺寸集成电路晶片的无害清洗等诸多领域。
超临界螯合萃取金属离子技术发展到现在已经近二十年了。传统的螯合剂种类很多，如有机单磷配体类：磷酸三丁酯(TBP)、Cyanex272、Cyanex301、Cyanex302类(例如美国CYTEC Industries，Inc.公司生产试剂)DDC类，β-二酮类，冠醚类和有机胺类等。传统螯合剂分子在超临界CO2流体中溶解度有限，通常需要借助氟化作用提高溶解度和萃取效率。但是，氟化反应所需的原料成本很高，限制了该技术的应用和推广；虽然添加改性剂(常见如甲醇、乙醇等)可以在一定程度上提高超临界CO2螯合萃取金属离子的效率，但是改性剂会对环境造成二次污染。
所以，开发新型和实惠的螯合剂来增强超临界CO2螯合萃取金属离子技术的“高效、绿色”特性是此领域研究的热点问题。
Novomestska等将三甘醇作为桥链，合成了具有两个“P(O)-OH”结构基团的酸性螯合剂，侧链为直链C12脂肪烃基，常规的液液萃取表明，其具有高萃取效率和对某些金属离子的萃取选择性。(Collect.Czech.Chem.Commun.2006，71(10)，1427-1444)。
发明内容
本发明提供了一种螯合剂，解决了传统螯合剂在CO2超临界萃取金属离子中溶解度低，萃取效率不高的问题。
一种螯合剂，具有如通式(I)所示的结构式：
其中，X为-(CH2CH2O)n-CH2CH2-，其中n为1～6的整数；
R1为甲基、乙基、丙基或异丙基；
R2为碳原子数在6到8之间的脂肪烃基，或为具有通式-(A)3-Z的基团，A为亚甲基；
Z为-Si[(CH2)yCH3]3，其中y为0、1、2或3；或
Z为-Si(CH3)α[-(O-Si(CH3)2)β-O-Si((CH2)γCH3)3]δ，其中β为0、1、2或3，γ为0、1、2或3，α为1或2，δ为1或2，且α+δ＝3；或
Z为如式(II)所示，其中-Ac为乙酰基，m为0、1、2或3
低聚乙二醇(乙撑氧基数目低于七)是具有多个金属配位位点而具有较强金属螯合作用的功能体。其来源广泛，可作为一种较为理想的螯合剂结构单元的选择。但是，低聚乙二醇在超临界二氧化碳中的溶解度有限，尤其在与金属离子形成螯合物后，溶解度更低，导致金属离子的萃取效率非常低，甚至不能萃取。为了增强低聚乙二醇在超临界CO2中的溶解度及金属离子的萃取效率，将其磷酸酯功能化是一种优异的选择。一方面，由于P＝O基具有优秀的亲CO2的特性，比C＝O基对CO2的亲和能力高近两倍，能够突出“CO2-philic”即亲二氧化碳特性；另一方面，P＝O基比C＝O基碱性更强，更易于与金属离子结合，将大大提高低聚乙二醇的螯合能力。同时，选用含带有支链脂肪烃基、硅烷烃基或乙酰化的糖基作为侧链也能够增强整个分子的亲二氧化碳的能力，从而从整体上增强了超临界二氧化碳螯合萃取金属离子的效率。
所述螯合剂的合成原料为三氯氧磷、低聚乙二醇以及通式(I)结构中侧链R1和R2所分别对应的带有羟基的醇或乙酰化的糖。通常的合成方法为溶剂法，溶剂选用甲苯或二氯甲烷，以吡啶作为缚酸剂，在0～5℃下反应完成。第一步反应三氯氧磷和低聚乙二醇按摩尔比2∶1反应，然后滴加与三氯氧磷等摩尔量的带有R2基团的醇或全乙酰化的糖，反应后，滴加与三氯氧磷等摩尔量的带有R1基团的短链脂肪醇，待整个反应结束后，萃取分离出粗产品，最后经硅胶柱层析提纯分离(详见实施例1)，反应工艺的目标物收率超过40％。
本发明还提供了所述螯合剂在超临界CO2螯合萃取金属离子中的应用。
本发明的螯合剂可用于螯合萃取金属离子，尤其适用于与超临界CO2流体相结合，从含有金属离子的固体基质中螯合萃取金属离子。
结合超临界CO2流体螯合萃取金属离子时的条件优选压力为12～25MPa，温度为45～60℃。
所述金属离子包括镧系金属离子、锕系金属离子、铁离子、钴离子、镍离子、铜离子、锌离子、铅离子、铬离子、汞离子、银离子、金离子等金属离子。
本发明螯合剂中的低聚乙二醇桥链上的多个氧原子具有孤对电子，与金属离子能够形成多个配位键，同时，P＝O基团上的氧原子比桥链上的氧原子具有更强的碱性，能形成更稳定的金属螯合物。本发明螯合剂利用侧链亲CO2的作用，金属螯合物在超临界CO2中具有较高的溶解度，这样提高了萃取效率。在相同的超临界CO2萃取条件下，本发明的对称中性有机磷酸酯螯合剂较传统的金属螯合剂萃取效率更高。
具体实施方式
实施例1
首先将0.1mol的三氯氧磷放入盛有100ml无水甲苯的250ml三口烧瓶中，然后在0℃条件下将含有0.05mol四甘醇和0.11mol吡啶的30ml无水甲苯溶液逐滴加入到烧瓶中，边滴加边搅拌，反应约10h后，接着滴加含有0.1mol异辛醇和0.1mol吡啶的30ml无水甲苯溶液，搅拌反应15h，接着滴加30ml甲醇(含吡啶0.1mol)滴加到溶液中，搅拌反应3h，待整个反应结束后，用200ml pH＝1的去离子水将混合溶液中的有机吡啶盐酸盐溶解，再加入300ml甲苯萃取分离出粗产品，水层分别用200ml甲苯洗涤两次，合并有机相，加入无水硫酸镁，过滤，蒸馏除去有机溶剂，粗产品最后经硅胶柱(300～400目)层析提纯分离，制得如通式(I)所示的螯合剂，该螯合剂中R1为甲基，R2为异辛基，中间桥链为四甘醇，产品性状为透明浅黄色粘性液体，收率超过40％(ESI MS检测，分子离子峰606.7)。
在313K～333K和12MPa～25MPa条件下，用静态法测定了上述螯合剂在超临界CO2中的溶解度，结果表明在60℃，20MPa条件下，其溶解度超过7％(质量分数)。
萃取金属离子：首先制备固体样品，取一块Whatman 42#滤纸(1×2cm2)，滴加含有La3+、Eu3+离子的硝酸盐溶液10μl(溶液离子浓度均为1000ppm)，然后在室温(25℃)过夜晾干。
将萃取釜顶部用玻璃棉填充，向上述晾干的滤纸上首先滴加10μl去离子水，再向滤纸上涂覆约60mg的螯合剂，塞入萃取釜内，密封。然后将萃取釜升温至60℃，通入超临界CO2加压至20MPa，静态萃取20min，接着动态萃取20min，流速为1ml/min。萃取结束后，缓慢减压至大气压。用ICP-MS检测分析(PQ3型电感耦合等离子体质谱仪，美国热电公司)。检测结果表明三种金属离子萃取率均高于90％。
实施例2
制备R1为甲基、R2基团为3-三甲基硅基-丙基、中间桥链为二甘醇的如通式(I)所示的螯合剂，其制备方法与实施例1反应条件相同，每一步骤反应物替换为相应的反应底物即可(即二甘醇替代四甘醇，3-三甲基硅基-丙基-醇替代异辛醇，其他保持不变)产物为透明浅黄色粘稠液体，产率约45％，ESI MS分子离子峰为522.6。
在313K～333K和12MPa～25MPa条件下，用静态法测定了该螯合剂在超临界CO2中的溶解度，结果表明在60℃，20MPa条件下，其溶解度超过14％(质量分率)。
制备固体样品：取一块Whatman 42#滤纸(1×2cm2)，滴加含有La3+、Eu3+离子的硝酸盐溶液10μl(溶液离子浓度均为1000ppm)，然后在室温(25℃)过夜晾干。
将萃取釜顶部用玻璃棉填充，向上述晾干的滤纸上首先滴加10μl去离子水，再向滤纸上涂覆约60mg的螯合剂，塞入萃取釜内，密封。然后将萃取釜升温至60℃，通入超临界CO2加压至20MPa，静态萃取20min，接着动态萃取20min，流速为1ml/min。萃取结束后，缓慢减压至大气压。用ICP-MS检测分析(PQ3型电感耦合等离子体质谱仪，美国热电公司)。检测结果表明三种金属离子萃取率均高于93％。
另外，条件与上述相同，当采用甲醇作为萃取改性剂(5％V/V，甲醇与超临界二氧化碳的体积比)时，萃取结果表明三种金属离子几乎可定量萃取。
实施例3
制备R1为甲基、R2基团为糖基[(2R，3R，4S，5R，6R)-2-(乙酰氧基甲基)-6-(3-溴丙基)四氢-2H-吡喃-3，4，5-三乙酸酯]、中间桥链为二甘醇的如通式(I)所示的螯合剂，其制备过程与实施例1反应条件相同，每一步骤反应物替换为相应的反应底物，(即二甘醇替代四甘醇，R2糖基醇替代异辛醇，其他保持不变)产物为透明黄色粘稠液体。
条件除与实施实例1相同外，当采用甲醇作为萃取改性剂(5％V/V，甲醇与超临界二氧化碳的体积比)时，结果表明三种金属离子的萃取率高于98％。
实施例4
合成方法与实施例1条件相同，R1为甲基、R2基团为3-三甲基硅基-丙基、中间桥链为四甘醇的如通式(I)所示的螯合剂，反应过程同实施例2，其中第一步将反应底物二甘醇替换为四甘醇，产品性状为透明黄色粘性液体。
首先制备固体样品：首先将定量的金属离子(Fe3+、Ni2+、Cs+离子)和螯合剂按照摩尔比1∶10的比例在四氯甲烷中反应，待反应完全后，将一定量的硅胶放入反应溶液中(按每300mg硅胶嵌入金属离子共100mg)，振荡摇匀，挥发完全四氯甲烷。
将萃取釜顶部用玻璃棉填充，向上述晾干的硅胶置入萃取釜内，再用少量玻璃棉填充并密封。然后将萃取釜升温至60℃，缓慢通入超临界CO2加压至20MPa，静态萃取30min，接着动态萃取30min，流速为0.8ml/min。萃取结束后，缓慢减压至大气压。用ICP-OES检测分析(PQ3型电感耦合等离子体质谱仪，美国热电公司)。检测结果表明Fe3+和Cs+金属离子萃取率均高于92％，而Ni2+低于30％。
实施例5
采用实施例3含糖基的中性磷酸酯作为螯合剂，条件除与实施实例4相同外，当采用甲醇作为萃取改性剂(5％V/V，甲醇与超临界二氧化碳的体积比)时，结果表明Fe3+和Cs+金属离子的萃取率高于95％，Ni2+低于50％。
Claims (2)
1.一种螯合剂，其特征在于，如通式(I)所示：
其中，X为-(CH2CH2O)n-CH2CH2-，其中n为1～6的整数；
R1为甲基；
R2为碳原子数在6到8之间的脂肪烃基，或为具有通式-(A)3-Z的基团，A为亚甲基，Z为-Si(CH3)3。
2.如权利要求1所述的螯合剂在超临界CO2螯合萃取金属离子中的应用，其特征在于，所述金属离子为镧系金属离子或铁离子。
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