CN101024205B - 从镀膜操作除去金属的方法 - Google Patents

从镀膜操作除去金属的方法 Download PDF

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CN101024205B
CN101024205B CN2006100647958A CN200610064795A CN101024205B CN 101024205 B CN101024205 B CN 101024205B CN 2006100647958 A CN2006100647958 A CN 2006100647958A CN 200610064795 A CN200610064795 A CN 200610064795A CN 101024205 B CN101024205 B CN 101024205B
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S·R·瓦斯康切洛斯
N·R·布兰福德
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    • C—CHEMISTRY; METALLURGY
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
    • B01J20/26—Synthetic macromolecular compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
    • B01J20/26—Synthetic macromolecular compounds
    • B01J20/265—Synthetic macromolecular compounds modified or post-treated polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • B01J20/28002—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their physical properties
    • B01J20/28004—Sorbent size or size distribution, e.g. particle size
    • C—CHEMISTRY; METALLURGY
    • 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
    • C02F2001/425—Treatment of water, waste water, or sewage by ion-exchange using cation exchangers
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/10—Inorganic compounds
    • C02F2101/20—Heavy metals or heavy metal compounds
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/10—Inorganic compounds
    • C02F2101/20—Heavy metals or heavy metal compounds
    • C02F2101/203—Iron or iron compound
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/10—Inorganic compounds
    • C02F2101/20—Heavy metals or heavy metal compounds
    • C02F2101/206—Manganese or manganese compounds
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/10—Inorganic compounds
    • C02F2101/20—Heavy metals or heavy metal compounds
    • C02F2101/22—Chromium or chromium compounds, e.g. chromates
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
    • C02F2103/16—Nature of the water, waste water, sewage or sludge to be treated from metallurgical processes, i.e. from the production, refining or treatment of metals, e.g. galvanic wastes

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  • Environmental & Geological Engineering (AREA)
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  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Hydrology & Water Resources (AREA)
  • Chemically Coating (AREA)
  • Treatment Of Water By Ion Exchange (AREA)
  • Water Treatment By Electricity Or Magnetism (AREA)
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Abstract

本发明涉及用于除去金属的化合物和方法，例如，从无电镀膜操作中除去离子钴，优选除去后的水平小于5ppm。接着，金属可以被填埋或为电解提取和再利用而再生。本发明使用一种离子交换介质，该介质含有硅石骨架并被膦酸盐基团官能化。

Description

从镀膜操作除去金属的方法
技术领域
本发明涉及除去金属的方法，例如从无电镀膜操作(electroless platingoperation)中除去离子钴，优选除去后水平小于5ppm。接着，所述金属可以被填埋或为电解提取和再利用而再生。
背景技术
在化学和生物化学工业中使用酸催化剂进行大量化学转换。大量均相和多相催化剂被使用，其中的一些需要在高温下生效并产生相当大量的副产品和废物。这些不希望得到的产品和废物必须被处理和销毁。对更环保的方法—“绿色化学”—的需求突出了可再利用、更有效和更有选择性的催化剂的必要性。这种必要性已经引起对能够催化多种化学转换的新材料设计的研究。这样的新催化剂的关键要求是非常好的热稳定性，对化学侵蚀的高度不敏感性，高官能团负载量，固定的并且刚性的结构，最佳的官能团以避免重排和副产品，有限的溶胀性，在有机溶剂中的不可溶性，易于净化和高复用性，高的抗老化性和易于接近进行化学转变的官能团。另外，制造这些催化剂体系的方法必须是灵活的以使得能够生产出适合特定反应的最佳结构和形状。这将包括在大孔到微孔结构之间调节多孔性，载有不同的官能团，易于生成不同的金属衍生物和选择性的pH范围。
已经有多种金属和催化剂被嵌入或吸附在硅石和其它材料的表面。这些体系面临的问题之一是，由于活性官能团与硅石的连接通常很微弱，而使活性官能团丧失。新的有机硅石材料要求拥有上述性能的同时，还具有牢固附着于和连接于多种金属和催化剂上的官能团。因为更严格的环境规则，对从各种被金属污染的溶剂和水基废物以及污水中除去和回收金属更有效的体系的需求日益增长。例如，工业如核工业和电镀工业产生巨大数量的水基排出物，该排出物被不希望的金属离子严重污染。已经使用阳离子交换剂从溶液中除去金属离子。所使用的阳离子交换剂的种类主要是有机的、带有连接到部分苯环上的磺酸盐基的部分交联的聚苯乙烯骨架。这些聚苯乙烯磺酸基阳离子交换剂的物理和化学性质受到聚合体骨架的有机本质的强烈影响，因此有一些缺点影响它们应用的技术领域。这些局限包括较低的耐温性(100—130℃)，对化学侵蚀的敏感性而这能导致聚合物母体的完全破裂，大的溶胀性，在某些有机溶剂中的不可用性和需要溶胀以使官能团可接近。有机膦酸阳离子交换剂也在例如美国专利No.5,281,631中进行了报道。这些体系是基于亚乙烯基二膦酸和苯乙烯、丙烯腈和二乙烯基苯的共聚产物。然而，这些有机膦酸树脂的物理和化学性质与基于聚苯乙烯磺酸的体系非常相似，因此它们的应用领域也是有限的。
无机聚合物体系如硅石、氧化铝和氧化钛，它们没有这些缺点，已经作为离子交换剂被进行研究。活性官能团或金属通过不同方式连接到这些体系。然而，这些体系面临只有低含量的官能团能与这些表面连接的事实。这些体系面临的其它问题之一是官能团可在使用中或静置时被除去。这是由于在官能团和载体的表面原子之间的连接相当地微弱。美国专利No.4,552,700和5,354,831已经描述了基于磺酸基团连接到有机聚硅氧烷骨架上的强酸性阳离子交换剂。所报导的材料具有通式(O3/2Si-R1-SO3)xMx，其中R1是烷基或环烷基片断，M是氢或一价到四价的金属离子，氧原子的自由价被通式中其它基团的硅原子和/或被例如SiO4/2，R1SiO3/2，TiC4/2，AlO3/2等的交联桥成员饱和。当这些材料作为阳离子交换剂时，普遍认为与其它官能团相比，磺酸基团与一定范围的金属络合的有效性是有限的。另外，由于磺酸盐基团是一价阴离子因而也受到限制，因此同其它官能团比较，需要更多这些官能团以与金属键合。
发明内容
本发明涉及除去金属的方法，例如从无电镀膜操作中除去离子钴，优选除去后水平小于5ppm。接着，金属可以被填埋或为电解提取(回收(reclamation))和再利用而再生。本发明使用了包含硅石骨架并被膦酸盐基用官能化的离子交换介质。
具体实施方式
本发明使用的化合物如下所述：
式1：
其中R和R1分别独立地为氢，直链或支链的C1-40烷基，C2-40链烯基或C2-40炔基，芳基或C1-40烷芳基或任选的络合金属离子Mn+/n，其中n是从1到8的整数；硅酸盐(silicate)氧原子的自由价被下列的一种或多种饱和：式1中其它基团的硅原子，氢，直链或支链的C1-12烷基或交联桥成员R3 qM1(OR2)mOk/2或Al(OR2)3-pOp/2或R3Al(OR2)2-rOr/2；其中M1是Si或Ti；R2是直链或支链的C1-12烷基；R3是直链或支链的C1-6烷基；k是从1到4的整数，q和m是从0到2的整数；m+k+q＝4；p是从1到3的整数；r是从1到2的整数；或其它已知的氧金属桥键体系(oxo metal bridging systems)；x，y和z是整数以使对于片断R3 qM1(OR2)mOk/2 or AI(OR2)3-pOp/2或R3AI(OR2)2-rOr/2始终存在的情况x:y+z的比值为从0.00001到100000变化，同时整数z为从0到200y。式1可以缩写为XxYyZz，其中X代表[O3/2SiCH(CH2PO(OR)(O R1))CH2CH2Si O3/2]，Y代表[O3/2SiCH2CH2PO(OR)(O R1)]和Z代表[O3/2SiCH2CH2CH2PO(OR)(O R1)]。
关于本发明所用的化合物的更多细节，它们的制备和使用参见公开号No.U.S.2004/0077889的文献，在此作为参考引用。
本发明所用的上述化合物的效率可为大约0.5-5mmol/g。如下表I所示，所述介质能够将钴降低到远低于检测极限。
表I
金属离子种类 初始金属离子浓度(ppm) 在接触w/介质后金属离子浓度(ppm)
Cr+3 100 0
Mn+2 100 0.05
Fe+3 100 0.16
Co+2 100 0
Ni+2 100 0.12
Pb+2 100 0.08
Cu+2 100 0.08
Zn+2 100 0.07
Cd+2 100 0.06
本发明所用的上述化合物的粒径优选是大约5—500μm，更优选是20—100μm。这些材料也可以与纳米过滤器(nanofilter)联合使用以浓缩金属，然后将浓缩物通过改性硅石以除去钴。处理的pH范围优选是大约6—10，更优选是大约7.5-9。所述改性硅石材料可以从Phosphonics Ltd.商购。本发明的方法在微电子工业应用上特别有用。
本发明已经通过特定实施方式进行描述，很明显本发明的很多其它形式和改变对本领域的熟练技术人员来说是显而易见的。所附的权利要求和本发明一般来说应当解释为覆盖落在本发明真正的精神和范围内的所有这些显而易见的形式和改变。

Claims (10)

1.一种从无电镀膜操作中除去金属的方法，包括向所述操作添加包括以下式1化合物的组合物：
Figure FSB00000173001500011
其中R和R1分别独立地为氢，直链或支链C1-40烷基，C2-40链烯基或C2-40炔基，芳基或C1-40烷芳基或任选的络合金属离子Mn+/n，其中n是从1到8的整数；硅酸盐氧原子的自由价被下列一种或多种饱和：式1中其它基团的硅原子，氢，直链或支链C1-12烷基或交联桥成员R3 qM1(OR2)mOk/2或Al(OR2)3-pOp/2或R3Al(OR2)2-rOr/2；其中M1是Si或Ti；R2是直链或支链C1-12烷基；R3是直链或支链C1-6烷基；k是从1到4的整数，q和m是从0到2的整数；以使得m+k+q＝4；p是从1到3的整数；r是从1到2的整数；或者其它已知的氧金属桥键体系；x，y和z是整数以使对于片断[O3/2SiCH(CH2PO(OR)(OR1))CH2CH2SiO3/2]x和[O3/2SiCH2CH2PO(OR)(OR1)]y始终存在的情况x∶y+z的比值为从0.00001到100000变化，同时整数z是从0到200y。
2.如权利要求1中所述的方法，其中所述化合物的数量是0.5-5mmol/g。
3.如权利要求1中所述的方法，其中从无电镀膜操作中除去金属到小于5ppm的水平。
4.如权利要求1中所述的方法，其中所述的金属包括钴。
5.如权利要求4中所述的方法，其中钴能为回收而再生。
6.如权利要求1中所述的方法，其中使用的所述化合物的粒径是5-500μm。
7.如权利要求6中所述的方法，其中使用的所述化合物的粒径是20-100μm。
8.如权利要求1中所述的方法，其中所述化合物与纳米过滤器联合使用。
9.如权利要求1中所述的方法，其中处理的pH是6-10。
10.如权利要求9中所述的方法，其中处理的pH是7.5-9。
CN2006100647958A 2005-12-12 2006-12-12 从镀膜操作除去金属的方法 Expired - Fee Related CN101024205B (zh)

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US5281631A (en) 1991-12-20 1994-01-25 Arch Development Corp. Phosphonic acid based ion exchange resins
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