GB2516215A - Metals recovery method and polymer for use in metals re-covery and process for making such a polymer - Google Patents
Metals recovery method and polymer for use in metals re-covery and process for making such a polymer Download PDFInfo
- Publication number
- GB2516215A GB2516215A GB1309308.3A GB201309308A GB2516215A GB 2516215 A GB2516215 A GB 2516215A GB 201309308 A GB201309308 A GB 201309308A GB 2516215 A GB2516215 A GB 2516215A
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- GB
- United Kingdom
- Prior art keywords
- metal
- polymer
- process according
- template material
- rhenium
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/20—Treatment or purification of solutions, e.g. obtained by leaching
- C22B3/22—Treatment or purification of solutions, e.g. obtained by leaching by physical processes, e.g. by filtration, by magnetic means, or by thermal decomposition
- C22B3/24—Treatment or purification of solutions, e.g. obtained by leaching by physical processes, e.g. by filtration, by magnetic means, or by thermal decomposition by adsorption on solid substances, e.g. by extraction with solid resins
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/26—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof by elimination of a solid phase from a macromolecular composition or article, e.g. leaching out
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
- C22B7/006—Wet processes
- C22B7/007—Wet processes by acid leaching
-
- 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
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/285—Treatment of water, waste water, or sewage by sorption using synthetic organic sorbents
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F6/00—Post-polymerisation treatments
- C08F6/02—Neutralisation of the polymerisation mass, e.g. killing the catalyst also removal of catalyst residues
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F6/00—Post-polymerisation treatments
- C08F6/26—Treatment of polymers prepared in bulk also solid polymers or polymer melts
- C08F6/28—Purification
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/28—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof by elimination of a liquid phase from a macromolecular composition or article, e.g. drying of coagulum
- C08J9/286—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof by elimination of a liquid phase from a macromolecular composition or article, e.g. drying of coagulum the liquid phase being a solvent for the monomers but not for the resulting macromolecular composition, i.e. macroporous or macroreticular polymers
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B61/00—Obtaining metals not elsewhere provided for in this subclass
-
- 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
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2201/00—Foams characterised by the foaming process
- C08J2201/04—Foams characterised by the foaming process characterised by the elimination of a liquid or solid component, e.g. precipitation, leaching out, evaporation
- C08J2201/05—Elimination by evaporation or heat degradation of a liquid phase
- C08J2201/0502—Elimination by evaporation or heat degradation of a liquid phase the liquid phase being organic
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2205/00—Foams characterised by their properties
- C08J2205/02—Foams characterised by their properties the finished foam itself being a gel or a gel being temporarily formed when processing the foamable composition
- C08J2205/024—Organogel, i.e. a gel containing an organic composition
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2205/00—Foams characterised by their properties
- C08J2205/02—Foams characterised by their properties the finished foam itself being a gel or a gel being temporarily formed when processing the foamable composition
- C08J2205/028—Xerogel, i.e. an air dried gel
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2339/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen; Derivatives of such polymers
- C08J2339/04—Homopolymers or copolymers of monomers containing heterocyclic rings having nitrogen as ring member
- C08J2339/08—Homopolymers or copolymers of vinyl-pyridine
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2347/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds; Derivatives of such polymers
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Manufacturing & Machinery (AREA)
- Environmental & Geological Engineering (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Mechanical Engineering (AREA)
- Polymers & Plastics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Analytical Chemistry (AREA)
- Hydrology & Water Resources (AREA)
- Water Supply & Treatment (AREA)
- Manufacture And Refinement Of Metals (AREA)
Abstract
A process of forming a porous polymer template material comprising polyÂmerising a monomer admixed with a compound of the metal to be recovered, followed by treatment of the polymer to remove the metal compound. The metal to be recovered may be rhenium and the metal compound ammonium perrhenate. The polymer may be formed by cross-linking a monomer, such as vinylpyridine, in the presence of a porogen, such as chloroform, and a metal salt. The metal can then be removed by treatment with acid to give the polymer template material. Once formed the polymer template may be comminuted. A method of selectively recovering a metal from a solution containing the metal ions comprises contacting the aforementioned porous polymer template material with the solution containing the metal ions, and recovering the metal from the polymer by treatment with hydrochloric acid.
Description
METALS RECOVERY METHOD AND POLYMER FOR USE IN METALS RE-
COVERY AND PROCESS FOR MAKING SUCH A POLYMER
Field of the Invention
This invention relates to a method of recovering high-value metals such as rhenium from superalloys, a process for making a polymer for use in a met-als recovery method, and a polymer adapted for such use.
Background to the Invention
Superalloys are metallic materials with a basic composition of nickel and cobalt or nickel and iron which, combined with other metals, form a highly re- sistant material. Use of metals such as rhenium in superalloys confers extraor-dinary properties to these alloys, such as increased resistance to corrosion and mechanical strength.
Recycling of rhenium from superalloys is an emerging market, with very little recycling actually being carried out currently using scrap super alloy or oth-is er alloys, or usually discarded production material.
Concerns and fluctuations in the mined supply of Rhenium are the main driving force behind its recycling. This is due to the fact that mining for Rhenium per se is not economically viable; it is actually a by-product of Copper and Mo-lybdenum mining. If the price of either of these metals falls to an uneconomic level, the mine is closed. The U.S. Geological Survey Mineral Commodity Summaries in January 2008 identified the World reserves of this metal to be around 10 million kilograms.
It is known that the current recycling methods employed are quite long (at 6 -9 months). The properties that the alloy is designed to offer, i.e. high strength, toughness and extraordinary wear resistance, make it a very difficult substance to work with. The preparation of super alloys for Rhenium recycling involves processes that specifically grind these materials. The actual decompo-sition in turn is carried out by wet chemistry involving heat treatment in mineral acids. This is followed by solvent extraction combined with sulphide precipita-tion and electro-deposition. Current costs for the process are in the region of $3000 per kg Rhenium recovered, with yields of around 70%. To be commer- cially attractive, an innovation to recycle rhenium requires added value by re-ducing the time constraints, reducing costs, increasing yields or a combination of the previous ones.
The present invention includes the manufacturing process of a polymeric material able to trap rhenium in order to obtain highly purified extracts of this metal in a short period of time.
Summary of the Invention
The invention provides a process for forming a porous polymer template material for use in selectively recovering a metal from a solution of the metal ions, comprising polymerising a monomer admixed with a compound of the metal to be recovered, and then treating the polymer to remove the metal com-pound therefrom.
Preferably, the template material is formed by cross-linking a monomer in the presence of a porogen and said metal compound.
The invention also provides a method of selectively recovering a metal is from a solution containing the metal ions, comprising contacting a polymer tem-plate material formed by a process according to the invention with the solution containing the metal ions, and recovering the metal from the polymer. The se-lectivity of the polymer for a specific metal enables an aqueous solution of mixed metal ions, in which the metal of interest may be a minor constituent, to be treated economically.
The invention further provides a polymeric material adapted to capture from a solution containing ions of plural metals a specific one of the metals
Detailed Description of the Invention
The general manufacturing process of the polymer used in the recycling of solutions with an important rhenium content involves the creation of a carbon lattice using a monomer, a cross-linker, initiator and a porogen and the use of a rhenium compound to create a template that is imprinted into this synthetic car-bon polymeric material. Following the key-lock principle the rhenium compound found in a concentrated solution of this metal will be trapped selectively and the rest of the solution will be eluted unaffected.
The general process of manufacturing involves the production of the template using a rhenium salt, namely ammonium perrhenate, with a rhenium concentration ranging between 1O-250mg/mL to control the trapping capacity of the polymer. These amounts can be increased to obtain higher yields.
The polymer is manufactured using the following proportions: 5-9% tem-plate (such as a rhenium salt), 2-6% monomer (such as vinylpyridine), 42-54% porogen (such as chloroform) and 35-45% of crosslinker (such as Ethylenegly-coldimethacrylate). To finalise the reaction mixture, 90-150mg of initiator (such as 1,1 -azobis(cyclohexanecarbonitrile)) is added to the container.
Once all the chemicals have been added to the reaction container the mixture is vortexed for a period of time not less than 2 minutes. After the com- plete mixture has been homogenised a flow of nitrogen is pumped into the solu-tion to eliminate all traces of oxygen that might be present for no less than 10 minutes. Once the solution has been purged with Nitrogen, the container is then sealed and then placed in an oven for not less than 48hours, at a temperature of 70°C to allow the solution to polyrnerise. As the pressure within the container is is likely to increase, the material used for the container needs to be able to withstand high pressures.
After the polymerisation is completed the solid polymer is removed from the glass vial and crushed into smaller particles mechanically with aids of mor- tar and pestle or a ball mill until the particle size is homogenous and the materi-al reaches a sand-type texture.
Once the material has been produced is placed in a column or in a con-tainer as the template has to be removed to make it functional and ready to trap rhenium. The template is dislodged by adding to the column or to the container where the material is kept, a 8M solution of hydrochloric acid (pH=-0.8) and left for 20-30 mm until all the template has been removed. The final conditioning consists of a washing process of the polymer until the pH of the eluents reach values close to 6-7. A new addition of a solution containing rhenium at pHs close to neutrality will result in rhenium being trapped.
The material can be re-used without loss of the trapping properties or damage to its structure for at least 5 cycles (number tested) but it is believed the durability goes beyond this number of cycles.
Using X-ray Fluorescence (XRF) the molecular imprinted polymer (MIP) could be analysed to determine the percentage of rhenium present within the solid MIF when samples of rhenium solution were eluted through, determining how much rhenium has been trapped by the polymer. Also Fourier transform infrared spectroscopy (FTIR) was also used to determine whether or not rheni-um is trapped in the MIP at a wavenumber of 900 cm-i.
It has also been proven that the MIP traps rhenium in a selective way. A solution containing seven different metals present in a typical alloy is proven to retain only rhenium when processed and eluted through the MIP when analysed using XRF.
Claims (15)
- CLAIMS1. A process of forming a porous polymer template material for use in selectively recovering a metal from a solution of the metal ions, comprising polymerising a monomer admixed with a compound of the metal to be recov-ered, and then treating the polymer to remove the metal compound therefrom.
- 2. A process according to Claim 1, wherein the template material is formed by cross-linking a monomer in the presence of a porogen and said metal compound.
- 3. A process according to Claim 2, wherein the metal compound is a salt.
- 4. A process according to any preceding claim, comprising commi-nuting the polymer after formation.
- 5. A process according to Claim 2 or 3, wherein the monomer is vi-nylpyridine.
- 6. A process according to Claim 5, wherein the porogen is chloro-form.
- 7. A process according to any preceding claim, wherein the polymer is treated with acid to remove the metal compound.
- 8. A process according to Claim 7, wherein the acid is concentrated hydrochloric acid.
- 9. A process according to any preceding claim, wherein the metal is rhenium.
- 10. A process according to Claim 9, wherein the metal compound is ammonium perrhenate.
- 11. A process of forming a porous polymer template material for use in selectively recovering a metal from a solution of the metal ions, substantially as described herein.
- 12. A method of selectively recovering a metal from a solution con-taining the metal ions, comprising contacting a polymer template material formed by a process according to any preceding claim with the solution contain-ing the metal ions, and recovering the metal from the polymer.
- 13. A method according to Claim 12, wherein the recovering step comprises treatment of the polymer template material with acid.
- 14. A method according to Claim 13, wherein the acid is concentrated hydrochloric acid.
- 15. A method of selectively recovering a metal from a solution con-taining the metal ions, substantially as described herein.
Priority Applications (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
GB1309308.3A GB2516215A (en) | 2013-05-23 | 2013-05-23 | Metals recovery method and polymer for use in metals re-covery and process for making such a polymer |
PCT/GB2014/051390 WO2014188158A1 (en) | 2013-05-23 | 2014-05-06 | Metals recovery method and polymer for use in metals re-covery and process for making such a polymer |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
GB1309308.3A GB2516215A (en) | 2013-05-23 | 2013-05-23 | Metals recovery method and polymer for use in metals re-covery and process for making such a polymer |
Publications (2)
Publication Number | Publication Date |
---|---|
GB201309308D0 GB201309308D0 (en) | 2013-07-10 |
GB2516215A true GB2516215A (en) | 2015-01-21 |
Family
ID=48784634
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
GB1309308.3A Withdrawn GB2516215A (en) | 2013-05-23 | 2013-05-23 | Metals recovery method and polymer for use in metals re-covery and process for making such a polymer |
Country Status (2)
Country | Link |
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GB (1) | GB2516215A (en) |
WO (1) | WO2014188158A1 (en) |
Families Citing this family (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB201500692D0 (en) | 2015-01-16 | 2015-03-04 | Fujifilm Mfg Europe Bv | Curable compositions and membranes |
CN106219658A (en) * | 2016-08-16 | 2016-12-14 | 南昌航空大学 | The classification removal of a kind of heavy metals in industrial wastewater and recovery method |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2005063382A1 (en) * | 2003-12-31 | 2005-07-14 | Council Of Scientific & Industrial Research | Synthesis of ion imprinted polymer particles |
CN101864033A (en) * | 2010-06-28 | 2010-10-20 | 济南大学 | Preparation and application of zinc ion imprinted polymer adsorbent |
WO2013063772A1 (en) * | 2011-11-02 | 2013-05-10 | Empire Technology Development Llc | Imprinted photonic polymers and methods for their preparation and use |
CN103193928A (en) * | 2013-03-19 | 2013-07-10 | 淮海工学院 | Coordination imprinted polymer and preparation method thereof |
Family Cites Families (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
AU2006312273B2 (en) * | 2005-11-14 | 2011-09-08 | The Johns Hopkins University | Molecularly imprinted polymer ion exchange resins |
US7704908B2 (en) * | 2005-12-22 | 2010-04-27 | Shell Oil Company | Method for reusing rhenium from a donor spent epoxidation catalyst |
KR101016231B1 (en) * | 2009-02-04 | 2011-02-25 | 성균관대학교산학협력단 | Method for preparing porous imprinted polymer particles for the selective separation of heavy metal ions |
CN102068968B (en) * | 2010-11-29 | 2014-07-16 | 大连海洋大学 | Lead ion imprinting integral column and preparation method thereof |
KR101206826B1 (en) * | 2010-12-13 | 2012-11-30 | 성균관대학교산학협력단 | Improved preparation of metal ion imprinted microporous polymer particles |
-
2013
- 2013-05-23 GB GB1309308.3A patent/GB2516215A/en not_active Withdrawn
-
2014
- 2014-05-06 WO PCT/GB2014/051390 patent/WO2014188158A1/en active Application Filing
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2005063382A1 (en) * | 2003-12-31 | 2005-07-14 | Council Of Scientific & Industrial Research | Synthesis of ion imprinted polymer particles |
CN101864033A (en) * | 2010-06-28 | 2010-10-20 | 济南大学 | Preparation and application of zinc ion imprinted polymer adsorbent |
WO2013063772A1 (en) * | 2011-11-02 | 2013-05-10 | Empire Technology Development Llc | Imprinted photonic polymers and methods for their preparation and use |
CN103193928A (en) * | 2013-03-19 | 2013-07-10 | 淮海工学院 | Coordination imprinted polymer and preparation method thereof |
Also Published As
Publication number | Publication date |
---|---|
WO2014188158A1 (en) | 2014-11-27 |
GB201309308D0 (en) | 2013-07-10 |
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