WO1995018159A1 - Resines echangeuses d'ions - Google Patents

Resines echangeuses d'ions Download PDF

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Publication number
WO1995018159A1
WO1995018159A1 PCT/AU1994/000793 AU9400793W WO9518159A1 WO 1995018159 A1 WO1995018159 A1 WO 1995018159A1 AU 9400793 W AU9400793 W AU 9400793W WO 9518159 A1 WO9518159 A1 WO 9518159A1
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WO
WIPO (PCT)
Prior art keywords
ion exchange
exchange resin
resin according
polymer
acid
Prior art date
Application number
PCT/AU1994/000793
Other languages
English (en)
Inventor
Frank Lawson
William Harold Jay
Original Assignee
Montech Pty. Ltd.
Linfox Technology Pty. Ltd.
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Montech Pty. Ltd., Linfox Technology Pty. Ltd. filed Critical Montech Pty. Ltd.
Priority to AU13757/95A priority Critical patent/AU694159B2/en
Publication of WO1995018159A1 publication Critical patent/WO1995018159A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
    • C08L75/04—Polyurethanes
    • 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
    • B01J39/00—Cation exchange; Use of material as cation exchangers; Treatment of material for improving the cation exchange properties
    • B01J39/08—Use of material as cation exchangers; Treatment of material for improving the cation exchange properties
    • B01J39/16—Organic material
    • B01J39/18—Macromolecular compounds
    • 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
    • C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
    • C08F283/006—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polymers provided for in C08G18/00
    • C08F283/008—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polymers provided for in C08G18/00 on to unsaturated polymers
    • 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
    • C08F8/00—Chemical modification by after-treatment
    • C08F8/30—Introducing nitrogen atoms or nitrogen-containing groups
    • C08F8/32—Introducing nitrogen atoms or nitrogen-containing groups by reaction with amines
    • 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
    • C08F8/00—Chemical modification by after-treatment
    • C08F8/42—Introducing metal atoms or metal-containing groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/4009—Two or more macromolecular compounds not provided for in one single group of groups C08G18/42 - C08G18/64
    • C08G18/4072—Mixtures of compounds of group C08G18/63 with other macromolecular compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/63—Block or graft polymers obtained by polymerising compounds having carbon-to-carbon double bonds on to polymers
    • C08G18/632—Block or graft polymers obtained by polymerising compounds having carbon-to-carbon double bonds on to polymers onto polyethers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/63—Block or graft polymers obtained by polymerising compounds having carbon-to-carbon double bonds on to polymers
    • C08G18/638—Block or graft polymers obtained by polymerising compounds having carbon-to-carbon double bonds on to polymers characterised by the use of compounds having carbon-to-carbon double bonds other than styrene and/or olefinic nitriles
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/67—Unsaturated compounds having active hydrogen
    • C08G18/69—Polymers of conjugated dienes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/83—Chemically modified polymers
    • C08G18/833—Chemically modified polymers by nitrogen containing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2110/00—Foam properties
    • C08G2110/0008—Foam properties flexible
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2270/00—Compositions for creating interpenetrating networks

Definitions

  • the present invention relates to a process for recovery of gold and/or silver from solutions and ion exchange resins for the recovery of gold and/or silver from solution.
  • anion exchange resins are superior to currently available activated carbon with respect to both the kinetics of loading and the equilibrium loading of gold cyanide
  • resins may be eluted at room temperature, whereas activated carbon must be eluted at temperatures approaching 100 ⁇ C,
  • resins may be used to recover free cyanide ions or metal cyanide complexes from tailings streams.
  • Resins are not poisoned by organic species such as flotation reagents, machine oils and lubricants, solvents, etc. to the same extent as observed for activated carbon. It has also been observed that species such as hematite, shales, clays, alumina, etc. decrease the loading of gold on activated carbon and also act as "preg robbers"; the same decrease in loading is not reported for resins.
  • organic species such as flotation reagents, machine oils and lubricants, solvents, etc.
  • ion exchange resins are manufactured in bead form generally from polystyrene-divinyl benzene, acrylic, or phenol-formaldehyde resins. It has been proposed that ion exchange fibres can be produced from either polyacrylonitrile onto which active ligands can be attached, or polypropylene fibres on to which polystyrene-divinyl benzene can be grafted. Ligands can then be attached to the surface of the ion exchange resins or fibres by conducting one or more suitable chemical reactions.
  • a problem associated with proposed RIP processes is one of resin loss.
  • the following potential sources of resin loss in an RIP plant have been identified: (a) abrasion of the resin beads by physical contact with the ore pulp,
  • Japanese Patent 78 06,296 suggests the use of guanidine-based ion exchange resins for the recovery and separation of gold from silver and platinum group metals.
  • UK Patent Application GB 2186563 A also suggests solvent extractants and ion exchange resins based on the guanidine ligand.
  • Patent Application 2,005,259 also suggest the use of guanidine-based resins.
  • PCT/AU93/00312 the disclosure of which is incorporated herein by reference, relates to ion exchange resins comprising a polymer containing ion exchanging sites dispersed or distributed throughout a polyurethane matrix wherein the ion exchanging sites are introduced subsequent to the formation of the polyurethane matrix. It has surprisingly been found that when the ion exchange resins of PCT/AU93/00312 are provided with an amine functionality that superior gold and/or silver extraction results are achieved. The particularly superior results as illustrated in the examples were not expected from a review of the prior art.
  • the resins of the present application are not restricted to the type described in PCT/AU93/00312 but include any polyurethane resin which has been provided with an amine functionality.
  • a gold complex and/or silver complex selective ion exchange resin comprising a polyurethane matrix having an amine functionality.
  • amine functionality includes all nitrogen- containing compounds including primary, secondary and tertiary amines, quaternary amine salts, aromatic or heterocyclic amines, guanidine-based complexes and imides.
  • the polyurethane matrix may be a polyurethane foam or resin or an interpenetrated polyurethane foam or resin.
  • a second polymer having the amine functionality may be dispersed or distributed throughout the polyurethane matrix or the matrix may be provided with an amine functionality.
  • dispersed or distributed when used herein includes a dispersion of discrete particles as well as networks of polymers which are intimately mixed throughout or incorporated within the polyurethane matrix such as in interpenetrating polymer systems.
  • the present invention also provides a process for the extraction of gold and/or silver from solutions including the steps of:
  • the above resin and process are particularly useful to extract cyanide complexes from solution.
  • Polyurethane resins are noted for their abrasion and chemical resistance. These resins can be produced as beads, sheets or as fibres, but in particular, they may be expanded to form foams with the cellular properties varying from a microcellular expanded product to highly expanded foams with a density of 10 kg/m 3 . By the correct selection of polyols, blowing agents and cell control agents these cells may be closed or open. In an open celled product, most of the cell windows are removed during production to leave only the struts behind. If a more open cellular product is desired, then the polyurethane foam can be further improved by "reticulation", a mechanism well-known to those skilled in the production of polyurethane foams.
  • particles including metal powders, metal alloy particles, inorganic materials (such as barytes) , metal oxides (such as magnetite or ferrosilicon) may be added to the polyurethane to modify its final density and thereby match the density of the pulp solution and if required, to assist in recovery of the resin from the aqueous solutions or pulps by magnetic means.
  • the ion exchange resin of the present invention comprises a urethane polymer as a matrix or continuous phase. Ways in which an amine functionality may be provided to the matrix are described in PCT/AU93/00312 as follows.
  • a second polymer may be dispersed or distributed throughout a polyurethane matrix, the second polymer being provided with an amine functionality.
  • the amine functionality may be provided in a number of different ways. For example a polymer having no amine functionality may be introduced into urethane raw materials, a polyurethane polymerisation reaction may then be conducted to form a polyurethane matrix having the polymer dispersed or distributed therein. The introduced polymer may then be chemically modified in one or more steps to provide the amine functionality.
  • a polyurethane resin may be interpenetrated with one or more monomers, at least one of which has one or more ligands attached. The one or more monomers may then be polymerised to provide a polymer containing said ligands. The ligands may either have an amine functionality or be subsequently modified to provide an amine functionality.
  • a polyurethane matrix may be provided, the matrix may be interpenetrated with one or more monomers. The monomers may be polymerised to provide a polymer and the polymer may then be chemically modified to provide an amine functionality.
  • polyurethane foams or resins can be interpenetrated with a second polymer prior to, during, or subsequent to production.
  • Such an interpenetration may be by any suitable polymer such as those described in PCT/AU93/00312.
  • the dispersed or distributed phase polymer typically may be a polymer formed from monomers of styrene, acrylonitrile, vinyl chloride, vinylidene chloride, divinyl benzene, butadiene, epichlorohydrin, caprolactone, thi odig1yco1 , thiodi ani 1 ine , di a11y1 amine , methylacrylonitrile, hydrazides, dicyclopentadiene, vinyl butyral, succinic anhydride, allyl halides, allyl malonic acid, acryloyl chloride, polyacetal, vinyl alcohol, aminosalicylic acid, dimethylolpropionic acid, ⁇ -methyl styrene,
  • Such chemical modification may be, for example, chlorination, chloromethylation, hydroxylation, nitration, amination and the like.
  • Examples are styrene monomer reacted with divinylbenzene, subsequently chloromethylated and then aminated; chloromethylstyrene polymerised and then aminated; acrylonitrile monomer polymerised and then aminated; 1-vinylimidazole copolymerised with methylbisacrylamide; acrylonitrile polymerised with styrene monomer or divinylbenzene and then aminated.
  • Typical polymers which may form the dispersed phase include polystyrene, styrene-divinyl benzene, styrene- acrylonitrile, styrene-acrylonitrile-methylmethacrylate, acrylonitrile-methylmethacrylate, polyacrylonitrile, polyacrylates, acrylic or methacrylic esters, acrylonitrile- unsaturated dicarboxylic acid-styrene, vinylidene chloride- acrylonitrile, epoxy(glycidyl methacrylate)-acrylonitrile, poly p-methylstyrene, polyureas, aniline-phenol-formaldehyde, phenol-formaldehyde, styrene-butadiene, styrene-acrylonitrile- butadiene, acrylonitrile-polyethylene glycol, polyamides, polyacrylamides, polyimidazoles, allylglycidyl
  • polystyrene-divinyl benzene Particularly suitable in the context of the present invention have been found to be polymers formed from a polystyrene-divinyl benzene, polyacrylonitrile and polyacrylates.
  • the polymers may then undergo a further chemical reaction such as chloromethylation or amination.
  • This second polymer may then be further reacted by suitable chemical modifications to include ligands.
  • suitable chemical modifications to include ligands.
  • ligands can be introduced into a polyurethane matrix are discussed in PCT/AU93/00312 but are by no means limiting. For example, by chloromethylation, chlorination, carboxylation, amination, phosphorylation, thioureation, diazotisation, amidoximation, oximation, etc. or other processes to attach specific ligands to the second polymer. Preferred in the context of the present invention is chloromethylation.
  • the chemical modification may also modify the polyurethane matrix.
  • ligands may be attached to the amide groups, hydroxyl groups, reactive methyl groups, or to the aromatic ring of the isocyanate component of the polyurethane matrix if an aromatic isocyanate is used in the production of the polyurethane resin.
  • reactive sites may be incorporated into the polyurethane by modifying an isocyanate with a material containing reactive sites (such as a dihydroxy compound) to form a prepolymer and further reacting the prepolymer with additional materials to produce the desired polyurethane.
  • the polyurethane resin containing ligands such as chloromethylated sites may then undergo a further chemical modification such as amination.
  • chloromethy1styrene may be substituted for polystyrene and therefore, an interpenetrated polyurethane resin containing chloromethylated polystyrene, crosslinked with divinyl benzene or other suitable monomer may be produced. This resin may then undergo further chemical modification such as amination.
  • the monomer(s) or blend of monomer(s) and comonomer(s) is interpenetrated into a polyurethane matrix which has been provided with unsaturated sites during its manufacture.
  • monomers particularly reactive monomers, such as hydroxy ethyl methacrylate, octene diol, hexene 1,2 diol, polybutadiene diol may be incorporated into the polyurethane during its manufacture to provide reactive unsaturated sites in the cured polyurethane.
  • One or more different unsaturated monomers may then be interpenetrated into the cured polyurethane and polymerised. The resultant polymer is thus chemically bound into the polyurethane matrix.
  • Vinylpyridine, 1-vinylimidazole, diallyldimethylammonium chloride, [3- (methacryloylamino)propyl . trimethylammonium chloride, styryl guanidine and/or its complexes, styrylimidazole and/or its complexes, are examples of such monomers containing an unsaturated functional group. Whilst it is preferred that the monomer(s) or blend of monomer(s) and comonomer(s) be interpenetrated into a polyurethane matrix containing an unsaturated group it is not a requirement of the invention that such reactive sites should be present in the polyurethane matrix.
  • a hydroxyl-containing compound may be reacted with a diisocyanate to produce an isocyanate- terminated prepolymer.
  • This prepolymer may then be included as one of the raw materials in the polyurethane resin manufacture.
  • the reactive compound are octene diol, hexene 1,2 diol, polybutadiene diol.
  • the diisocyanate include toluene diisocyanate (TDI) and various grades of diphenylmethane-4,4'-diisocyanate (MDI).
  • TDI toluene diisocyanate
  • MDI diphenylmethane-4,4'-diisocyanate
  • An interpenetrated polyurethane which contains a suitable ligand may be induced to undergo a further chemical reaction such as alkylation.
  • a polyurethane may be interpenetrated with a second polymer such as vinylpyridine and then the pyridine site may be methylated by reaction with a methyl halide or ethylated by reaction with an ethyl halide.
  • the interpenetration may be conducted in the presence of a comonomer such as divinylbenzene.
  • a polyurethane resin containing an acrylonitrile polymer was reacted with an amine to form an imidazoline functional group and then further reacted with a methyl or ethyl halide.
  • copolymer polyols may be produced by the grafting polymerisation of unsaturated monomers on to poly(ethylene oxide) (EO) or poly (propylene oxide) (PO) or mixed EO-PO containing polyols.
  • Typical monomers include styrene, divinylbenzene, acrylonitrile, acrylates, vinyl acetate, styryl guanidines, styryl imidazoles, vinylpyridine, 1-vinylimidazole and [3-(methacryloylamino)propyl]- trimethylammonium chloride and mixtures thereof.
  • This polymer polyol may then be incorporated as a raw material in the manufacture of a polyurethane.
  • Suitable isocyanate monomers include toluene diisocyanate (TDI), PAPI (a polyaryl polymethylenepolyisocyanate as defined in U.S. Patent No.
  • Desired ligands can then be reacted with the unreacted isocyanate groups.
  • TDI, MDI or HDI may be reacted at elevated temperature in the presence of a urethane reaction catalyst such as triethylamine with hydroxyl groups and/or amide groups present in the polyurethane resin such that one of the isocyanate groups remains unreacted.
  • This unreacted isocyanate group may then undergo a further reaction such as by amination by alkyl amines.
  • the unreacted isocyanate group may then be reacted with water to form an amine. This amine site may then be induced to undergo a further chemical reaction if so desired.
  • amine functionality includes all nitrogen containing compounds including primary, secondary and tertiary amines, quaternary amine salts, aromatic or heterocyclic amines, guanidine-based complexes and imides.
  • Preferred amination includes alkyl amines wherein the alkyl chain is preferably between 1 and 6 carbons long, or which can be reacted to form an imidazoline ligand, or guanidine, pyridine, quinoline, pyrrolidine, diallylamine, dibenzylamine, or other suitable amine as are more fully discussed below.
  • polyurethane foams incorporate polystyrene-divinyl benzene.
  • the benzene ring is preferably then chloromethylated.
  • a further reaction may desirably be conducted in which amine functional groups are incorporated into the polyurethane foam or resin. Varying lengths of alkyl chain have been incorporated. Dimethylamine, diethylamine, diethanolamine, hexamethylenetetramine, ethylenediamine, 2- ethyleneiminoimidazoline, trimethylamine, triethylamine, tributylamine, dimethylethanolamine, are typical of such alkylamines.
  • guanidine functional groups have also been introduced into the polyurethane foam or resin.
  • guanidine, 2-ethylhexylguanidine, di-o-tolyl guanidine, di-n-alkyl guanidine, dioctylguanidine, N-(6- aminohexyl)-N'-butyl guanidine complexes, styrylimidazoline complexes are examples of such ligands.
  • amine functionality introduced includes pyridine, quinoline, benzylamine, dibenzylamine, pyrrolidine, diallylamine, aminodiacetate, amino phosphonic acids, benzyldimethylamine, benzylimidazoline, 2-methylimidazoline (lysidine), benzyllysidine.
  • organic amines may also be incorporated into the polyurethane foam or polyurethane resin.
  • Patent ZA 89/2733 and having the formula:- R 1
  • R 4 ⁇ . in which each of R 1 , R 2 , R 3 , and R 4 independently of each other, represent hydrogen, alkyl, alkenyl or aryl (including substituted aryl) with the further possibility that the functional group may be protonated and have a counter ion associated therewith; and British Patent Application GB 2186563A containing the functional group:-
  • R x through R 5 is selected from the group consisting of H, a resin, aromatic and aliphatic groups containing from 2-25 carbon atoms.
  • ZA 89/2733 and GB 2186563A are herein incorporated by reference and the term "guanidine complexes" when used herein includes those compounds disclosed in ZA 89/2733 and GB 2186563A.
  • polyacrylonitrile or polyacrylonitrile copolymers such as with styrene or styrenedivinylbenzene is incorporated into the polyurethane foam.
  • Amine functionality is then preferably introduced into the polymer. For example, diethylenetriamine and ethylenediamine have been reacted with the nitrile group introduced into the polyurethane resin. By the selection of reaction conditions, so imidazoline groups may be formed.
  • Organic extractants including tributylphosphate, dibutyl butyl phosphate, trioctylamine, tri-(C 8 -C 10 ) alkyl methyl ammonium chloride, guanidine functionality, imidazoline functionality such as laurolimidazoline, may also be included into the polyurethane foam or polyurethane resin.
  • the resins of the present invention are also capable of impregnation with organic extractants which are capable of removing desired metal ions from solution.
  • Any suitable amine extractant may be incorporated into the resin of the invention.
  • Such amine extractants include trioctylamine, guanidine functionality, tri-(C 8 -C 10 ) alkyl methyl ammonium chloride, or other extractant, including tributylphosphate and dibutyl butyl phosphate.
  • An example of such an extractant is Aliquat 336 (TM) [tri-(C 8 -C 10 ) alkyl methyl ammonium chloride] a quaternary-based organic extractant manufactured by Henkel Corporation.
  • the incorporation of these extractants can be modified by either pre- or post-incorporation of a diisocyanate or a diisocyanate prepolymer onto the polyurethane foam and curing it such as by passing steam through the isocyanate-impregnated polyurethane foam containing the organic extractant.
  • the organic extractant may be blended with the diisocyanate component (providing that the organic reactant does not react with the diisocyanate to form a solid product prior to its incorporation onto the polyurethane foam or resin).
  • Resins of the invention may include an amine functionality and also contain an organic extractant.
  • the resins of the present invention offer exceptional abrasion resistance, and resistance to osmotic shock. These resins can be formed into particles of a size such that they can be readily recovered from gold and/or silver circuits. This particle size may be significantly larger than for conventional ion exchange resins. As previously noted, conventional ion exchange resins require a small particle size to enable them to have sufficient exchange capacity. Conventional resins are also generally made macroreticular to increase their capacity and has been reported leads to osmotic shock which can degrade the resin. It has been reported that this process may lead to pores being generated in the ion exchange resin which can block and reduce its capacity to remove metal ions from solution.
  • the resins of the present invention are particularly suitable for the extraction of gold and/or silver complexes, for example cyanide complexes from solutions. They may be used to extract gold cyanide from a gold cyanide containing solution which is part of a pulp or slurry.
  • the application of the polyurethane foams of the invention is not restricted to the recovery of gold cyanide only. Extraction of other gold complexes such as the gold halides, particularly chloride and bromide, gold thiourea, gold thiosulphate, gold thiocyanate can also be achieved by the application of interpenetrated and modified polyurethane foams or impregnated polyurethane foams.
  • Silver cyanide and other silver complexes, particularly thiosulphates, which may occur in solution, or in the recovery of silver from silver ores, or silver which may occur in association with gold in gold ores may also be recovered by the process of the invention.
  • Resins which are selective for different precious metals such as gold, silver and the platinum group metals may be produced and used to separate mixtures of precious metals.
  • the solutions may be clarified, such as is normally obtained in gold heap leaching operations. Or it may be from pulps, such as occur in carbon-in-pulp or carbon-in-leach processes.
  • Stripping of the polyurethane resin of the invention may be accomplished by a suitable solvent such as sodium or ammonium thiosulphate, acidified thiourea, zinc cyanide, or in some instances, pH control by stripping at a pH in excess of 12.
  • a suitable solvent such as sodium or ammonium thiosulphate, acidified thiourea, zinc cyanide, or in some instances, pH control by stripping at a pH in excess of 12.
  • a further advantage of the present invention is that polyurethane foams do not suffer from hypochlorite degradation and will not reduce the gold to gold metal during the period that they are in the plant providing the solution conditions are correctly established. If reduction occurs, it is within the polymer, and therefore is not lost by abrasion as is the case with activated carbon.
  • Polyurethane foams were interpenetrated with a mixture of styrene monomer, divinyl benzene, and 2,2'- azobisisobutryro-nitrile (AIBN). The interpenetration and curing was conducted at 70°C in a nitrogen atmosphere. This foam was then chloromethylated by reacting 1 gram of the interpenetrated polyurethane foam at room temperature for 2 hours with 5 grams of octyl chloromethyl ether together with stannic tetrachloride catalyst in a suitable solvent.
  • AIBN 2,2'- azobisisobutryro-nitrile
  • This chloromethylated polyurethane foam was then further reacted with the amines as listed in Table 1 and under the conditions as given.
  • TOA toluene > 10,000 70-80°C, 24h
  • the resin from the Example was then methylated by reacting this resin with a 2 mole excess of methyl halide dispersed in a suitable solvent for 16 hours at room temperature.
  • a polyurethane foam was produced as follows:
  • a polyurethane foam was produced as follows:
  • a polyurethane foam was produced as follows:
  • the polymer loaded with gold cyanide from Example 7 was contacted with 20 millilitres of a 1 molar solution of sodium hydroxide at room temperature for 18 hours, The gold cyanide was eluted from the polymer.
  • the guanidine-based polymer loaded with gold cyanide from Example 3 was contacted with 20 millilitres of a 1 molar solution of sodium hydroxide at room temperature for 18 hours. The gold cyanide was eluted from the polymer.
  • Example 7 The resin in Example 7 was contacted at room temperature with a solution containing 160 ppm of free cyanide ions together with the following metal cyanide complexes at a pH of 10.5 for 1 hour and 3 hours to give the sorption results below:
  • Example 3 The dimethylamine-based resin in Example 3 was contacted at room temperature with a solution containing 160 ppm of free cyanide ions together with the following metal cyanide complexes at a pH of 10.5 for 1 hour, 3 hours and 24 hours to give the sorption results below:
  • Styryl guanidine monomer was synthesised. 1.5 grams of a polyurethane foam in which 10 % by weight of polybutadiene diol was included as a raw material during its manufacture was interpenetrated with a mixture of 4 grams of this monomer, 0.1 gram of divinylbenzene and 18 milligrams of AIBN and then cured for 24 hours at 70°C under a nitrogen atmosphere.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • General Chemical & Material Sciences (AREA)
  • Solid-Sorbent Or Filter-Aiding Compositions (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Processes Of Treating Macromolecular Substances (AREA)
  • Polyurethanes Or Polyureas (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

L'invention concerne une résine échangeuse d'ions sélective d'un complexe d'or et/ou d'argent, comprenant une matrice polyuréthanne possédant une fonctionnalité amine, ainsi que des procédés servant à récupérer l'or et/ou l'argent dans des solutions en utilisant cette résine échangeuse d'ions.
PCT/AU1994/000793 1993-12-24 1994-12-23 Resines echangeuses d'ions WO1995018159A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU13757/95A AU694159B2 (en) 1993-12-24 1994-12-23 Ion exchange resins

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
AUPM3112 1993-12-24
AUPM3112A AUPM311293A0 (en) 1993-12-24 1993-12-24 Ion exchange resins

Publications (1)

Publication Number Publication Date
WO1995018159A1 true WO1995018159A1 (fr) 1995-07-06

Family

ID=3777736

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/AU1994/000793 WO1995018159A1 (fr) 1993-12-24 1994-12-23 Resines echangeuses d'ions

Country Status (5)

Country Link
AU (1) AUPM311293A0 (fr)
CA (1) CA2178803A1 (fr)
NZ (1) NZ278304A (fr)
WO (1) WO1995018159A1 (fr)
ZA (1) ZA9410325B (fr)

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1999013116A1 (fr) * 1997-09-05 1999-03-18 Arton (No. 001) Pty. Ltd. Procede servant a recuperer de l'or ou de l'argent
WO1999015273A1 (fr) * 1997-09-25 1999-04-01 Holbray Pty. Ltd. Echange d'ions
WO2002028529A2 (fr) * 2000-10-04 2002-04-11 Yeda Research And Development Co. Ltd. Resines echangeuses d'ions pour extraction de cyanure d'or
CN113231048A (zh) * 2021-06-23 2021-08-10 东华理工大学 一种铀吸附剂及其制备方法和应用
CN114057950A (zh) * 2020-07-30 2022-02-18 湖北远大生命科学与技术有限责任公司 球形聚氨酯接枝改性的聚丙烯酸酯大孔阴离子树脂及其制备方法和在牛磺酸生产中的应用
CN116354365A (zh) * 2023-03-14 2023-06-30 衢州诺尔化工科技有限公司 一种氟硅酸法制氟化钾精制的方法

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
SCIENCE, Volume 258, issued 23 October 1992, S. NAKANISHI, "Molecular Diversity of Glutamate Receptors and Implications for Brain Function", pages 597-603. *
THE JOURNAL OF BIOLOGICAL CHEMISTRY, Volume 269, Number 2, issued 14 January 1994, N. OKAMOTO et al., "Molecular Characterization of a New Metabotropic Glutamate Receptor mGluR7 Coupled to Inhibitory Cyclic AMP Signal Transduction", pages 1231-1236. *

Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1999013116A1 (fr) * 1997-09-05 1999-03-18 Arton (No. 001) Pty. Ltd. Procede servant a recuperer de l'or ou de l'argent
WO1999015273A1 (fr) * 1997-09-25 1999-04-01 Holbray Pty. Ltd. Echange d'ions
EP1027158A1 (fr) * 1997-09-25 2000-08-16 Holbray Pty. Ltd. Echange d'ions
EP1027158A4 (fr) * 1997-09-25 2002-08-28 Holbray Pty Ltd Echange d'ions
US7001523B1 (en) 1997-09-25 2006-02-21 Oretek Limited Ion exchange
WO2002028529A2 (fr) * 2000-10-04 2002-04-11 Yeda Research And Development Co. Ltd. Resines echangeuses d'ions pour extraction de cyanure d'or
WO2002028529A3 (fr) * 2000-10-04 2002-07-04 Yeda Res & Dev Resines echangeuses d'ions pour extraction de cyanure d'or
CN114057950A (zh) * 2020-07-30 2022-02-18 湖北远大生命科学与技术有限责任公司 球形聚氨酯接枝改性的聚丙烯酸酯大孔阴离子树脂及其制备方法和在牛磺酸生产中的应用
CN114057950B (zh) * 2020-07-30 2024-03-22 湖北远大生命科学与技术有限责任公司 球形聚氨酯接枝改性的聚丙烯酸酯大孔阴离子树脂及其制备方法和在牛磺酸生产中的应用
CN113231048A (zh) * 2021-06-23 2021-08-10 东华理工大学 一种铀吸附剂及其制备方法和应用
CN116354365A (zh) * 2023-03-14 2023-06-30 衢州诺尔化工科技有限公司 一种氟硅酸法制氟化钾精制的方法
CN116354365B (zh) * 2023-03-14 2023-10-24 衢州诺尔化工科技有限公司 一种氟硅酸法制氟化钾精制的方法

Also Published As

Publication number Publication date
ZA9410325B (en) 1995-12-14
NZ278304A (en) 1997-02-24
CA2178803A1 (fr) 1995-07-06
AUPM311293A0 (en) 1994-01-20

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