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WO2008030179A1 - Polymères de métal imprimé destinés à prélever sélectivement le cobalt - Google Patents

Polymères de métal imprimé destinés à prélever sélectivement le cobalt Download PDF

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Publication number
WO2008030179A1
WO2008030179A1 PCT/SE2007/050633 SE2007050633W WO2008030179A1 WO 2008030179 A1 WO2008030179 A1 WO 2008030179A1 SE 2007050633 W SE2007050633 W SE 2007050633W WO 2008030179 A1 WO2008030179 A1 WO 2008030179A1
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Prior art keywords
cobalt
imprinted polymer
ions
polymer according
ligand
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Ceased
Application number
PCT/SE2007/050633
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English (en)
Inventor
Börje SELLERGREN
S.V. Narasimhan
Anupkumar Bhaskarapillai
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Publication of WO2008030179A1 publication Critical patent/WO2008030179A1/fr
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Classifications

    • 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
    • C02F1/68—Treatment of water, waste water, or sewage by addition of specified substances, e.g. trace elements, for ameliorating potable water
    • C02F1/683—Treatment of water, waste water, or sewage by addition of specified substances, e.g. trace elements, for ameliorating potable water by addition of complex-forming 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
    • B01J20/268—Polymers created by use of a template, e.g. molecularly imprinted polymers
    • 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
    • C02F2101/006—Radioactive 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

Definitions

  • the present invention relates to an imprinted polymer selective for cobalt ions in the presence of iron ions, a process for preparation of said imprinted polymer, and use of said imprinted polymer.
  • a variety of structural materials such as carbon steel, monel, Incoloy, stainless steel and stellite are employed in the cooling water systems of power plants. These materials interact with the coolant at high temperature and form deposits of metal oxides. This problem becomes severe in case of nuclear power plants as the metal oxide deposits may have trapped radioactive metal ions in the oxide lattice which leads to the build up of radioactivity, thereby necessitating regular clean up campaigns.
  • the clean up operation which is generally done by continuous circulation of complexing chemical formulations, the metal ions are brought out into the solution and trapped by the ion-exchange resin beds that form a part of the clean up circuit.
  • the resin bed traps all the metal ions.
  • R1 , R2 nuclear reactor decontaminations
  • large quantity of ferrous ion which is non-radioactive is released along with small quantity of radioactive cobaltous ions.
  • the ion exchange resins currently used do not have high selectivity towards the radioactive cobaltous ions, they are coabsorbed with other ions, resulting in the generation of large amounts of radioactive waste which require costly and elaborate disposal procedures..
  • the amount of radioactive waste can be substantially reduced if a resin, which is highly selective towards cobaltous ions in presence of ferrous ions can be developed.
  • This kind of highly selective resins can also be of great use during the decommissioning of existing nuclear power plants in selectively concentrating many radioactive metal ions present in small amount.
  • a material which can specifically pick up the particular metal ion of concern can reduce the amount of toxic waste.
  • the present invention deals with providing such a material wherein the metal of interest which has to be trapped is cobaltous ions in presence of ferrous ions from a solution containing complexing agents as well. Achieving this kind of selectivity for a particular metal ion against a close competitor through conventional ion-exchange resins may not be feasible unless there are highly specific ligands available for the particular metal ion.
  • the technique of molecular imprinting (R3) has been widely accepted to be a convenient and powerful technique for preparing polymeric materials with pre-determined selectivity for various substances. The method as described in
  • R3 has been demonstrated to be effective for metal ions, saccharides, amino acid derivatives and other organic compounds of low molecular weight.
  • the method usually involves pre-organisation of functional hosts around a "template” molecule in an organic solution containing a large excess of cross-linking monomers, followed by polymerization to form a cavity and stabilize the three-dimensional distribution of binding functionalities in the polymer matrix that is complementary to the template.
  • the resulting polymer exhibits high selectivity for rebinding of the template molecule or ion which was used to prepare the polymer.
  • metal ions as templates and suitable ligand groups as functional hosts, ion- selective imprinted polymers can be synthesized. Hence this approach is chosen for the synthesis of the material of interest.
  • this method has another advantage.
  • the radioactive cobaltous ion which is picked up by the MIP can be easily stripped by change of the pH of the medium to extract the radioactive Cobalt in a smaller volume to process the liquid waste.
  • the MIP can be reused. There is no need to handle the radioactive organic polymer waste.
  • US 7,001 ,963 discloses a process for removal of cobalt.
  • the removal of cobalt disclosed in the application is not specific.
  • As disclosed in the examples of US 7,001 ,963 iron is also bound to the imprinted polymer. Thus materials according to the aforementioned invention would not be useful for the above mentioned industrial application.
  • the present invention relates to an improved imprinted polymer for specific removal of cobalt ions in presence of iron ions.
  • the present invention relates to an imprinted polymer capable of specific binding to cobalt ions in the presence of iron ions, thus solving the problems relating to additional binding of iron and/or iron ions.
  • the selective removal of cobalt ions in the presence of iron ions is achieved by an imprinted polymer having the general Formula I;
  • D is a crosslinker bearing at least one vinylgroup
  • A is a cobalt complex having the following general Formula II:
  • Co is cobalt in +2 oxidation state
  • M is any alkali or alkaline earth metal ion or a cation derived from organic bases, such as triethylamine, diisopropylamine or quartemary ammonium salts such as tetrabutyl ammonium hydroxide
  • L is a polymerizable ligand.
  • the polymerizable ligand is N-(R)-iminodiacetic acid, where R preferably is 4-vinylbenzyl.
  • polymerizable ligands (L) are any imino acid bearing at least one vinyl group; a Schiff base of the type 2, 6- pyridinedicarboxaldehydebis(p-vinylphenylimine) or other polymerizable Schiff bases derived from 2,6-pyridinedicarboxaldehyde; a Schiffs base prepared from a salicylaldehyde bearing at least one vinyl group; and a cyclohexane bearing at least one amino group.
  • the present invention also relates to a process for preparation of an imprinted polymer wherein an imprinted polymer having the general Formula I;
  • D is a crosslinker bearing at least one vinylgroup;
  • A is a cobalt complex having the following general Formula II:
  • M is any alkali or alkaline earth metal ion or a cation derived from organic bases, such as tri
  • L polymerizable ligands
  • Other possible polymerizable ligands (L) are any imino acid bearing at least one vinyl group; a Schiff base of the type 2, 6-pyridinedicarboxaldehydebis(p-vinylphenylimine) or other polymerizable Schiff bases derived from 2,6-pyridinedicarboxaldehyde; a Schiffs base prepared from a salicylaldehyde bearing at least one vinyl group and a cyclohexane bearing at least one amino group;.
  • the porogen may be any solvent but is preferably a lower aliphatic alcohol such as methanol, ethanol or propanol.
  • the invention provides an imprinted polymeric material which picks up only cobaltous ions and not ferrous ions from a solution containing both.
  • the invention also provides a method for the preparation of the above polymeric composition.
  • the present invention also relates to the use of the polymer according to the invention for specific removal of cobaltous ions and radioactive cobaltous ions from a complexing or a non-complexing solution containing cobaltous and ferrous ions.
  • the present invention also relates to the use of the polymer according to the invention for specific removal of cobaltous ions and radioactive cobaltous ions from a complexing or a non-complexing solution containing cobaltous and ferrous ions.
  • the present invention as described above relates to an imprinted polymer having total selectivity for cobalt ions in the presence of iron ions.
  • the above mentioned patent disclose a process for preparation of a composition which contains three different types of ligands, whereas the present invention provides a composition comprising at least one imprinted polymer which has only one type of ligand. Furthermore, the present invention provides a process wherein, the metal complex is prepared, separated and then incorporated into the polymeric network.
  • One embodiment of the present invention relates to a process for preparation of an imprinted polymer, wherein said imprinted polymer is prepared in-situ in presence of an organic base.
  • organic lipophilic cations such as quartemary ammonium ions, as the counterions M, will result in an enhanced solubility of complex Il in organic solvents of lower polarity. This in turn will stabilize the complex which thus will be incorporated into the polymer with all Lewis basic sites of the ligands coordinated to the metal ion.
  • the polymeric composition provided in the present invention surprisingly exhibits total selectivity (specificity) towards cobalt ions in the presence of ferrous ions, as shown in Example 2.
  • the enhanced performance is due to a much improved material (imprinted polymer) compared to the material disclosed in prior art (US 7,001 ,963).
  • the present invention retains the same specificity even in presence of a strong complexing agent selected from the group consisting of Nitrilotriacetic acid,
  • Ethylenedimaine tetraacetic acid Ethyleneglycol-O, O'-bis(2-aminoethyl)-N, N, N', N'- tetraacetic acid and N-(2-Hydroxyethyl)ethylenediamine-N, N', N'-triacetic acid, as disclosed in Example 3.
  • one of the examples shows a selective pick up of cobalt (7.2mg/g) over iron (1.55mg/g) and the rest indicate a higher capacity for iron over cobalt.
  • the present invention provides a polymeric composition which shows total specificity towards cobaltous ions over iron (ferrous) ions.
  • the wording 'template' means the cobaltous ion around which the crosslinked polymeric matrix is formed;
  • MIP means a molecularly imprinted polymer synthesized in presence of the template ion, and the term “NIP” means non- imprinted polymer which is synthesized in the absence of the template ion according to the definitions found in reference R3.
  • the wording and terms "MIP”, “imprinted polymer”, and “molecularly imprinted polymer” are used interchangeably. Furthermore the terms “selectivity”, “specificity” and “specific” are used interchangeably.
  • an interval is present it is intended to mean each individual number within the interval, as well as each possible subinterval within the interval, for example the interval from 0 to 50 comprises the subintervals from 2 to 10, from 25.1 to 25.5 and from 5 to 40 etc.
  • Alkaline metals may be any of the monovalent metals of group I of the periodic table (lithium or sodium or potassium or rubidium or cesium or francium).
  • Alkaline earth metals may be any of a group of metallic elements, especially calcium, strontium, magnesium, and barium, also including beryllium and radium.
  • the present invention relates to the preparation of resins with predetermined selectivity through the process of metal imprinting.
  • the present invention provides an imprinted polymer (MIP) which is highly specific for cobalt against ferrous ions. Imprinting process had long been used for inducing/enhancing selectivity for a particular metal or molecule.
  • MIP imprinted polymer
  • Molecular/metal imprinting involves pre-organisation of functional hosts around a template molecule/metal ion in a solvent containing a large excess of cross-linking monomers, followed by polymerization to provide a three-dimensional distribution of binding functionalities in the polymer matrix that is complementary to the template. After removal of the template, the resulting polymer exhibits high selectivity for rebinding of the template molecule or ion which was used to prepare the polymer.
  • the present invention relates to metal imprinting with an objective to generate specificity towards cobalt ions.
  • One embodiment of the present invention relates to metal imprinting with an objective to generate a MIP (molecularly imprinted polymer) being selective towards cobalt ions.
  • MIP molecularly imprinted polymer
  • the MIP has a selectivity of between 90-100%, more preferably between 95- 100%, more preferably between 98-100 %, and most preferred selectivity between 99-100%.
  • One embodiment of the present invention relates to metal imprinting with an objective to generate a MIP (molecularly imprinted polymer) being selective towards cobalt ions in the presence of iron ions, has a selectivity of between 90-100%, more preferably between 95- 100%, more preferably between 98-100 %, and most preferred a selectivity between 99- 100%.
  • MIP molecularly imprinted polymer
  • selective (specific) binding of cobalt ions is achieved by incorporating a cobalt complex within a crosslinked polymeric network followed by removal of the metal ions from the synthesized polymer. This results in a polymer having sites which are designed to take up cobalt ions preferentially over its close competitor ferrous ions from a solution containing both.
  • the selectivity of a metal imprinted polymer depends on many factors such as disclosed in R4: a) the specificity of the interaction of the ligand with the cation b) the coordination geometry and coordination number of the cations c) the charge on the cation and d) to some extent, the size of the cation.
  • a (polymerisable) vinyl derivative of iminodiacetic acid namely, [N-(4-vinylbenzyl)imino]diacetic acid was synthesised and used as complexing monomer in the synthesis of cobalt imprinted polymer.
  • Example 1 A procedure for the synthesis of Imprinted and non-imprinted polymers: a) Synthesis of Cobalt Complex:
  • the polymers synthesised were first stirred in methanol to remove un-reacted reactants. NIP was washed with alkaline solution to remove any unreacted free ligands, washed with water and dried. The MIP was subjected to extraction of the metal template (Cobalt) by treatment with 1 :1 MeOH/HCI (0.1 N) mixture for 24 hrs, followed by repeated extractions with 0.1 N HCI till there was no more cobalt coming out of the polymer. The polymer was then washed water and methanol dried and used for evaluation. The extracted solutions were analysed by Atomic Absorption Spectroscopy (AAS) for the amount of cobalt. The analysis showed that 41 % of the cobalt used in making the MIP was removed and the theoretical capacity was calculated to be 94.6 ⁇ mols/g.
  • AAS Atomic Absorption Spectroscopy
  • Example 2 Evaluation of the MIP and NIP in a complexinq buffer
  • Example 3 Evaluation of MIP and NIP in presence of strong complexinq agent: To check the ability of the polymers to pickup metal ions in presence of strong complexing agents, the tests were carried out in presence of Nitrilotriacetic acid. The tests were carried out the same way as explained in example 2, but the solution contained nitrilotriacetic acid along with metal ions and citrate buffer. Table 2:
  • Example 4 In-situ synthesis of Cobalt imprinted polymer using an organic base: 0.32 mols of the ligand N-(4-vinylbenzyliminodiacetic acid), and 0.58 mmol of tetrabutylammonium hydroxide were taken in 2.5 ml of dry methanol or dry toluene. To this solution, 0.16 mmol of Co(NO 3 ) 2 x 6 H2O were added slowly and dissolved. To this 6.1 mmol of crosslinking agent Ethylene Glycol dimethacrylate and 1 wt% of initiator AIBN were added and the solution polymerised at 62 0 C for 24 hrs followed by curing at 75 0 C for 24 hrs. The polymer was crushed, washed with methanol and the cobalt ions removed by extraction with dilute HCI.
  • Example 5 A typical use of the polymer in a nuclear plant clean up process: The imprinted polymer is packed into a column and put before the normal ion exchange column during the clean up operation. This ensures that all the radioactive cobalt is picked up by the imprinted polymer and the other normal ion exchange resin would pick up only the other ions such as ferrous ions which are in excess. This results in concentration of radioactive waste within a small volume thereby reducing the amount of radioactive waste.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Hydrology & Water Resources (AREA)
  • Engineering & Computer Science (AREA)
  • Environmental & Geological Engineering (AREA)
  • Water Supply & Treatment (AREA)
  • Analytical Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

La présente invention concerne un polymère imprimé sélectif pour les ions cobalt en présence de 5 ions fer. Les polymères imprimés peuvent être représentés par la formule générale I; AXDy (I), 10 où x et y sont des fractions molaires telles que 0 < x, y < 1 et x + y = 1; D est un agent de réticulation qui contient au moins un groupe vinyle; A est un complexe de cobalt représenté par la formule générale II suivante : 15 MnCoa(L)b c H2O (II), où a est 1; b est compris entre 1 et 6; c est compris entre 0 et 8; n est compris entre 0 et 2; 20 Co est du cobalt à l'état d'oxydation +2; M est n'importe quel ion métallique alcalino-terreux ou alcalin et L est un ligand polymérisable. L'invention concerne également un processus de préparation dudit polymère imprimé, et l'utilisation dudit 25 polymère imprimé. 15
PCT/SE2007/050633 2006-09-07 2007-09-07 Polymères de métal imprimé destinés à prélever sélectivement le cobalt Ceased WO2008030179A1 (fr)

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SE0601899 2006-09-07

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106979930A (zh) * 2017-05-23 2017-07-25 中国科学院地质与地球物理研究所 一种定量分析土壤沉积物样品中游离铁含量的方法
CN113061215A (zh) * 2021-05-20 2021-07-02 重庆科技学院 一种基于MOFs的钴离子印迹聚合物及其制备方法和应用
WO2022247694A1 (fr) * 2021-05-24 2022-12-01 江苏铭丰电子材料科技有限公司 Matériau de remplissage et son procédé de préparation, et procédé de préparation de feuille de cuivre électrolytique pour transmission de signal haute fréquence
CN119192505A (zh) * 2024-10-17 2024-12-27 西南科技大学 一种用于核医疗废液净化的多孔离子印迹亚胺吸附材料及其制备方法

Citations (1)

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Publication number Priority date Publication date Assignee Title
US7001963B2 (en) * 2003-09-29 2006-02-21 Council Of Scientific And Industrial Research Cobalt imprinted polymer composition for selective removal of cobalt, process for preparation thereof, and process for removal of cobalt

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7001963B2 (en) * 2003-09-29 2006-02-21 Council Of Scientific And Industrial Research Cobalt imprinted polymer composition for selective removal of cobalt, process for preparation thereof, and process for removal of cobalt

Non-Patent Citations (2)

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Title
BRUENING R.L. ET AL.: "The application of molecular recognition technology (MRT) for the removal of impurities and the recovery of metals in copper electrorefining and electrowinning", SYMPOSIUM SERIES - SOUTH AMERICAN INSTITUTE OF MINING AND METALLURGY, S16 (HIDDEN WEALTH), 1996, pages 45 - 54, XP003018685 *
WULFF G.: "Molecular Imprinting in Cross-linked Materials with the Aid of Molecular Templates - A Way towards Artificial Antibodies", ANGEWANDTE CHEMIE INTERNATIONAL EDITION IN ENGLISH, vol. 34, no. 17, 1995, pages 1812 - 1832, XP000524863 *

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106979930A (zh) * 2017-05-23 2017-07-25 中国科学院地质与地球物理研究所 一种定量分析土壤沉积物样品中游离铁含量的方法
CN106979930B (zh) * 2017-05-23 2018-04-24 中国科学院地质与地球物理研究所 一种定量分析土壤沉积物样品中游离铁含量的方法
CN113061215A (zh) * 2021-05-20 2021-07-02 重庆科技学院 一种基于MOFs的钴离子印迹聚合物及其制备方法和应用
WO2022247694A1 (fr) * 2021-05-24 2022-12-01 江苏铭丰电子材料科技有限公司 Matériau de remplissage et son procédé de préparation, et procédé de préparation de feuille de cuivre électrolytique pour transmission de signal haute fréquence
JP2023534885A (ja) * 2021-05-24 2023-08-15 江蘇銘豊電子材料科技有限公司 フィラー及びその生成方法、高周波信号伝送用電解銅箔の製造方法
JP7436997B2 (ja) 2021-05-24 2024-02-22 江蘇銘豊電子材料科技有限公司 フィラー及びその生成方法、高周波信号伝送用電解銅箔の製造方法
US12491491B2 (en) 2021-05-24 2025-12-09 Jiangsu Mingfeng Electronic Materials Co., Ltd Filling material, method for preparing same and method for preparing electrolytic copper foil for high-frequency signal transmission
CN119192505A (zh) * 2024-10-17 2024-12-27 西南科技大学 一种用于核医疗废液净化的多孔离子印迹亚胺吸附材料及其制备方法
CN119192505B (zh) * 2024-10-17 2025-05-16 西南科技大学 一种用于核医疗废液净化的多孔离子印迹亚胺吸附材料及其制备方法

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