WO2004108973A1 - Solvent extraction composition comprising sulphonic acid with a 4-(alpha branched) acyl-(3h)-pyrazol-3-ones and processes of metal extraction - Google Patents

Solvent extraction composition comprising sulphonic acid with a 4-(alpha branched) acyl-(3h)-pyrazol-3-ones and processes of metal extraction Download PDF

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Publication number
WO2004108973A1
WO2004108973A1 PCT/GB2004/001855 GB2004001855W WO2004108973A1 WO 2004108973 A1 WO2004108973 A1 WO 2004108973A1 GB 2004001855 W GB2004001855 W GB 2004001855W WO 2004108973 A1 WO2004108973 A1 WO 2004108973A1
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optionally substituted
metal
formula
solvent
alkyl group
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PCT/GB2004/001855
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French (fr)
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John Campbell
Alan David Sugarman
Ronald Matthys Swart
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Cytec Technology Corp.
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    • 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
    • C22B15/00—Obtaining copper
    • C22B15/0063—Hydrometallurgy
    • 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
    • C22B3/26—Treatment or purification of solutions, e.g. obtained by leaching by liquid-liquid extraction using organic compounds
    • C22B3/40—Mixtures
    • C22B3/406—Mixtures at least one compound thereof being a heterocyclic compound
    • 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
    • C22B15/00—Obtaining copper
    • C22B15/0063—Hydrometallurgy
    • C22B15/0084—Treating solutions
    • 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
    • C22B3/26—Treatment or purification of solutions, e.g. obtained by leaching by liquid-liquid extraction using organic compounds
    • 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
    • C22B3/26—Treatment or purification of solutions, e.g. obtained by leaching by liquid-liquid extraction using organic compounds
    • C22B3/36—Heterocyclic compounds
    • C22B3/362—Heterocyclic compounds of a single type
    • 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

Definitions

  • the present invention concerns processes using 4-acyl-(3H)-pyrazol-3-ones for the solvent extraction of metals, particularly copper, from aqueous solutions, especially acidic solutions obtained by leaching ores.
  • compositions comprising sulphonic acid kinetics boosters and 4-(alpha branched)acyl-(3H)-pyrazol-3-ones show advantage in metal extraction processes.
  • a solvent extraction composition comprising a sulphonic acid and a solvent extractant of formula
  • R 1 is an aryl group optionally substituted with one or more groups selected from C M2 alkyl or halo
  • R 2 is C 1-12 alkyl group or a phenyl optionally substituted with one or more groups selected from C 1-12 alkyl or halo
  • R 3 is an alpha branched alkyl group containing at least eight carbon atoms, and tautomers or salts thereof.
  • Aryl groups which may be represented by R 1 may contain 1 ring or 2 or more fused rings.
  • Aryl groups include aromatic and heteroaromatic groups.
  • the fused rings may include cycloalkyl, aryl or heterocyclic rings.
  • Examples of aryl groups include optionally substituted phenyl, naphthyl, thienyl and pyridyl groups.
  • R 1 is a phenyl optionally substituted with one or more groups selected from C 1-12 alkyl or halo.
  • Phenyl groups optionally substituted with one or more groups selected from C 1-12 alkyl or halo which may be represented by R 1 or R 2 include those of formula:
  • R" to R 8 each independently represent H, halo, or a C 1-12 alkyl group.
  • R 4 to R 8 are halo, preferably the halo is CI or F.
  • the C 1-12 alkyl group can be linear or branched, and preferably is methyl, ethyl or isopropyl.
  • R s represents a halo group or a C 1-12 alkyl group, with R 4 , R 5 , R 7 and R 8 representing H.
  • R 4 to R 8 are all hydrogen.
  • a preferred 4-(alpha branched)acyl-(3H)-pyrazol-3-one is one in which R is a phenyl optionally substituted with one or more groups selected from C 1-12 alkyl or halo, preferably R 1 is an unsubstituted phenyl group; R 2 is C 1-12 alkyl group or a phenyl optionally substituted with one or more groups selected from C 1-12 alkyl or halo, preferably R 2 is a methyl group; and R 3 is an alpha branched alkyl group containing at least eight carbon atoms, preferably a tertiary alpha branched alkyl with at least eight carbon atoms, most preferably a secondary alpha branched alkyl with at least eleven carbon atoms.
  • 4-(alpha branched)acyl-(3H)-pyrazol-3-ones wherein R 3 is an isomeric mixture of tertiary alpha branched alkyl groups.
  • the isomeric mixture of tertiary alpha branched alkyl groups is preferably derived from a Versatic acid.
  • Versatic acids are isomeric mixtures of acids with a fixed number of carbons.
  • Preferred Versatic acids are C10 and C13 Versatic acids which result in 4-(alpha branched)acyl-(3H)-pyrazol-3-ones where R 3 is a C9 or C12 alkyl group.
  • Preferred 4-(alpha branched)acyl-(3H)-pyrazol-3- ones are those where R 3 is an isomeric mixture of tertiary alpha branched alky groups comprising 9 or more carbon atoms of formula:
  • R 9 and R 10 are independently linear or branched alkyl groups.
  • the isomeric variation results from variations in the number of carbons atoms in the R 9 and R 10 groups.
  • Sulphonic acids which are suitable for use in compositions of the present invention typically are soluble in the solvents used in metal extraction and show reduced solubility in aqueous acid solution.
  • Sulphonic acids which are suitable for use in compositions of the present invention, generally are organic sulphonic acids, typically optionally substituted hydrocarbyl sulphonic acids.
  • R 11 is an optionally substituted hydrocarbyl group.
  • Optionally substituted hydrocarbyl groups which may be represented by R 11 preferably comprise optionally substituted alkyl and aryl groups including combinations of these, such as optionally substituted aralkyl and alkaryl groups.
  • Optionally substituted alkyl groups which may be represented by R 11 include groups which contain a total number of alkyl carbons of from 7 to 50, especially from 8 to 40 carbon atoms.
  • a preferred optionally substituted alkyl sulphonic acid is one in which R 11 is alkyl, preferably containing more than 8, and especially more than 10, and more preferably more than 15 saturated aliphatic carbon atoms.
  • Optionally substituted aryl groups which may be represented by R 11 include optionally substituted phenyl groups and naphthy! groups. When R 11 is an any! group, it is preferably a substituted naphthyl group.
  • the optionally substituted hydrocarbyl sulphonic acid is an optionally substituted naphthyl sulphonic acid
  • the optionally substituted naphthyl sulphonic acid is preferably a compound of formula (4):
  • R 12 and R 13 are each independently an optionally substituted alkyl group. It should be understood that as drawn, each ring of compound of formula (4) may independently be substituted with one or more groups represented by R 12 and R 13 respectively.
  • Optionally substituted alkyl groups which may be represented by R 12 and R 13 include groups which contain a total number of alkyl carbons of from 5 to 30, especially from 7 to 20 carbon atoms.
  • R 12 and R 13 may be the same or different.
  • R 2 and R 13 are the same.
  • R 12 and R 13 are unsubstituted alkyl groups. Most preferably C9 unsubstituted alkyl groups. Examples of optionally substituted naphthyi suiphonic acids inciude dinonylnaphthalenesulphonic acids.
  • Optional substituents which may substitute the hydrocarbyl group of R 11 , include halogen, nitro, cyano, hydrocarbyl, such as C ⁇ -alky!, especially C ⁇ -alky!; hydrocarbyloxy, such as C ⁇ o-alkoxy, especially C 1-10 -alkoxy; hydrocarbyloxycarbonyl, such as acyl, such as
  • compositions of the present invention comprising optionally substituted hydrocarbyl sulphonic acids are advantageous in that they show increased extraction kinetics. However, with certain highly preferred compositions the increase in kinetics can also be achieved while ameliorating iron transfer.
  • a solvent extraction composition comprising a sulphonic acid of formula (5):
  • R 13 and R 4 each independently is an optionally substituted alkyl group
  • R 15 and R 16 each independently is hydrogen or an optionally substituted alky! group
  • X is an integer, and a solvent extractant of formula (1 ):
  • R is an aryl group optionally substituted with one or more groups selected from C 1-12 alkyl or halo;
  • R 2 is C 1-12 alkyl group or a phenyl optionally substituted with one or more groups selected from C 1-12 alkyl or halo;
  • R 3 is an alpha branched alkyl group containing at least eight carbon atoms, and tautomers or salts thereof. Preferences for the solvent extractant of formula (1 ) are described as herein before in connection with the first aspect the present invention.
  • R 13 and R 14 may be the same or different. Preferably, R 13 and R 14 are the same.
  • Optionally substituted alkyl groups which may be represented by R 13 and R 14 include groups which contain a total number of alkyl carbons of from 5 to 40, especially from 7 to 30 carbon atoms.
  • Examples of optionally substituted alkyl groups which may be represented by R 13 and R 14 include amyl, hexyl, octyi, nonyl, decyl, dodecyl, tridecyl and nonadecyl.
  • R 13 and R 14 are selected to be optionally substituted alkyl groups each containing eight or more alkyl carbons, for example octyl, nonyl, decyl, dodecyl, tridecyl and nonadecyl groups. More preferably, R 13 and R 14 are selected to be tridecyl groups.
  • Optionally substituted alkyl groups which may be represented by R 15 and R 16 include groups which contain a total number of alkyl carbons of from 1 to 20.
  • R 15 and R 16 may be the same or different. Preferably, R 15 and R 15 are the same. More preferably R 15 and R 16 are both hydrogen. X is preferably 1 , 2 or 3. Most preferably, X is 1.
  • compositions of the present invention have been found to be most suited to use in solvent extraction systems where the solvent used has a low aromatic hydrocarbon content.
  • a solvent extraction composition comprising a water immiscible organic solvent, preferably with a low aromatic hydrocarbon content, a sulphonic acid and a solvent extractant of formula (1 ):
  • R 1 is an aryl group optionally substituted with one or more groups selected from C 1-12 alkyl or halo;
  • R 2 is C 1-12 alkyl group or a phenyl optionally substituted with one or more groups selected from C 1-12 alkyl or halo;
  • R 3 is an alpha branched alkyl group containing at least eight carbon atoms, and tautomers or salts thereof. Preferences for the solvent extractant of formula (1 ) and the sulphonic acid are described as herein before in connection with the first and second aspects the present invention.
  • the composition may comprise one or more different 4-(alpha branched)acyl- (3H)-pyrazol-3-ones, especially where the component 4-(alpha branched)acyl-(3H)- pyrazol-3-ones are isomeric.
  • Such isomeric mixtures may have better solubility in organic solvents than a single 4-acyl-(3H)-pyrazol-3-one and are preferred.
  • the 4-(alpha branched)acyl-(3H)-pyrazol-3-one are often present in an amount of up to 60% by weight of the composition, commonly no more than 50%, and usually no more than 40 % w/w. Often, the 4-(alpha branched)acyl-(3H)-pyrazol-3-one comprises at least 1%o by weight, commonly at least 2.5% by weight and usually at least 5% by weight of composition, and preferably comprises from 7.5 to 20%, such as about 10%, by weight of the composition.
  • the composition may comprise one or more different sulphonic acids.
  • the sulphonic acids are often present in an amount of up to 2% by weight based on the total weight of 4-(alpha branched)acyl-(3H)-pyrazo!-3-one present, commonly no more than
  • the sulphonic acids comprise at least 0.01% by weight, commonly at least 0.05% by weight and usually at least 0.1 % by weight based on the total weight of 4-(alpha branched)acyl-(3H)-pyrazol-3-one present, and preferably comprises from 0.05 to 1% such as about 0.2% by weight based on the total weight of 4-(aipha branched)acyl-(3H)-pyrazoi-3-one present.
  • Organic solvents which may be present in the composition include any mobile organic solvent, or mixture of solvents, which is immiscible with water and is inert under the extraction conditions to the other materials present.
  • the organic solvent has a low aromatic hydrocarbon content.
  • Preferred organic solvents are hydrocarbon solvents which include aliphatic, alicyclic and aromatic hydrocarbons and mixtures thereof as well as chlorinated hydrocarbons such as trichloroethylene, perchloroethylene, trichloroethane and chloroform.
  • Highly preferred organic solvents having a low aromatics content include solvents and solvent mixtures where the amount of aromatic hydrocarbons present in the organic solvent is less than 30%, usually around 23% or less, often less than 5%, and frequently less than 1%.
  • Suitable hydrocarbon solvents include ESCAID 110, ESCAID 115, ESCAiD 120, ESCAiD 200, and ESCAiD 300 commerciaiiy available from Exxon
  • Suitable solvents are hydrocarbon solvents include high flash point solvents and solvents with a high aromatic content such as SOLVESSO 150 commercially available from Exxon (SOLVESSO is a trade mark).
  • solvents with a low aromatic content More preferred are solvents with a low aromatic content.
  • Certain suitable solvents with a low aromatic content have aromatic contents of ⁇ 1 % w/w, for example, hydrocarbon solvents such as ESCAID 110 commercially available from Exxon (ESCAID is a trade mark), and ORFOM SX 10 and ORFOM SX11 commercially available from Phillips Petroleum (ORFOM is a trade mark).
  • hydrocarbon solvents of relatively low aromatic content such as kerosene, for example ESCAID 100 which is a petroleum distillate with a total aromatic content of 23% commercially available from Exxon (ESCAID is a trade mark), or ORFOM SX7, commercially available from Phillips Petroleum (ORFOM is a trade mark).
  • ESCAID 100 which is a petroleum distillate with a total aromatic content of 23% commercially available from Exxon (ESCAID is a trade mark)
  • ORFOM SX7 commercially available from Phillips Petroleum
  • the composition comprises at least 30%, often at least 45% by weight, preferably from 50 to 95% w/w of water-immiscible hydrocarbon solvent.
  • the composition in the form of a . concentrate.
  • the concentrate may then be diluted by the addition of organic solvents as described herein above to produce compositions in the ranges as described herein above.
  • the concentrate contains a solvent, it is preferred that the same solvent is used to dilute the concentrate to the "in use" concentration range.
  • the concentrate composition comprises up to 30%, often up to 20% by weight, preferably up to 10% w/w of water-immiscible hydrocarbon solvent. Often the concentrate composition comprises greater than 5% w/w of water-immiscible hydrocarbon solvent.
  • the viscosity of the acylpyrazolones of the present invention means that concentrates do not display appreciably higher viscosity than extractant compositions at "in use” concentrations. In certain high strength concentrates it may be necessary to employ a higher than normal aromatic hydrocarbon content. In such cases where a high aromatic hydrocarbon containing solvent is used in the concentrate, solvent of very low aromatic hydrocarbon content may be used to dilute the concentrate to the "in use" concentration range.
  • compounds or mixtures of compounds selected from the group consisting of alcohols, esters, ethers, polyethers, carbonates, ketones, nitriles, amides, carbamates, sulphoxides, acids of sulphur and phosphorous compounds, for example sulphonic acids, and salts of amines and quaternary ammonium compounds may also be employed as additional modifiers or kinetics boosters in the composition of the invention.
  • mixtures comprising a first compound selected from the group consisting of alcohols, esters, ethers, polyethers, carbonates, ketones, nitriles, amides, carbamates, sulphoxides, acids of sulphur and phosphorous compounds, for example sulphonic acids, and salts of amines and quaternary ammonium compounds and a second compound selected from the group consisting of alkanols having from 6 to 18 carbon atoms, an alkyl esters having from 7 to 30 carbon atoms, and tributylphosphate.
  • a first compound selected from the group consisting of alcohols, esters, ethers, polyethers, carbonates, ketones, nitriles, amides, carbamates, sulphoxides, acids of sulphur and phosphorous compounds, for example sulphonic acids, and salts of amines and quaternary ammonium compounds
  • a second compound selected from the group consisting of alkanols having from
  • a process for the extraction of a metal from solution in which an acidic solution containing a dissolved metal is contacted with a solvent extraction composition comprising a water immiscible organic solvent and a solvent extractant, whereby at least a fraction of the metal is extracted into the organic solution, characterised in that the solvent extraction composition comprises a water immiscible organic solvent, preferably with a low aromatic hydrocarbon content, a sulphonic acid and a solvent extractant of formula (1 ):
  • R 1 is an aryl group optionally substituted with one or more groups selected from C 1-12 alkyl or halo;
  • R 2 is C 1-12 alkyl group or a phenyl optionally substituted with one or more groups selected from C 1-12 alkyl or halo;
  • R 3 is an alpha branched alkyl group containing at least eight carbon atoms, and tautomers or salts thereof.
  • Metals that may be extracted in the process according to the third aspect of the present invention include copper, cobalt, nickel, manganese and zinc, most preferably copper.
  • the extractant of formula (1 ), the sulphonic acid and the water immiscible organic solvent are as herein described before.
  • the aqueous acidic solution from which metals are extracted by the process of the third aspect of the present invention often has a pH in the range of from -1 to 7, preferably from 0 to 5, and most preferably from 0.25 to 3.5.
  • the metal to be extracted is copper pH values of less than 3 chosen so that the copper is extracted essentially free of iron, cobalt or nickel.
  • the solution can be derived from the leaching of ores or may be obtained from other sources, for example metal containing waste streams such as from copper etching baths.
  • the concentration of metal, particularly copper, in the aqueous acidic solution will vary widely depending for example on the source of the solution. Where the solution is derived from the leaching of ores, the metai concentration is often up to 75g/l and most often from 1 to 40g/l. Where the solution is a waste stream, the metal concentrations can vary from 0.5 to 2g/l for a waste water stream, to somewhat higher for those from other waste streams, for example Printed Circuit Board waste streams, and can be up to 150g/l, usually from 75 to 130g/l.
  • Preferred solvent extraction compositions are those where the organic solvent solutions may contain the acyl pyrazolone in an amount approaching 100% ligand, but typically the acyl pyrazolone will be employed at about 10 to 40% by weight.
  • Highly preferred solvent extraction compositions are those comprising an organic solvent with a total aromatic content of around 23% or less, one or more acyl pyrazolones selected from 2-Phenyl-5-methyl-4-(2-hexyIdecan-1-oyl)-3-pyrazolone or 2-Phenyl-5-methyl-4-(2- butyloctan-1-oyI)-3-pyrazolone in a total amount of between 5 to 40% by weight and one or more sulphonic acids selected from dioctylsulphosuccinate or ditridecylsulphosuccinate in a total amount of between 0.01 to 2% by weight based on the total weight of 4-(alpha branched)acyl-(3H)-pyrazol-3-one present.
  • acyl pyrazolones selected from 2-Phenyl-5-methyl-4-(2-hexyIdecan-1-oyl)-3-pyrazolone or 2-Phenyl-5-methyl-4-(2- butyloctan
  • the process of the fourth aspect of the present invention can be carried out by contacting the solvent extractant composition with the aqueous acidic solution containing a dissolved metal.
  • Ambient or elevated temperatures such as up to 75°C can be employed if desired. Often a temperature in the range of from 5 to 60°C, and preferably from 15 to 40°C, is employed.
  • the aqueous solution and the solvent extractant are usually agitated together to maximise the interfacial areas between the two solutions.
  • the volume ratio of solvent extractant to aqueous solution are commonly in the range of from 20:1 to 1 :20, and preferably in the range of from 5:1 to 1 :5.
  • organic to aqueous volume ratios close to 1 :1 are maintained by recycle of one of the streams.
  • the metal can be recovered from the solvent extractant by contact with an aqueous acidic strip solution.
  • the aqueous strip solution employed in the process according to the third aspect of the present invention is usually acidic, commonly having a pH of 2 or less, and preferably a pH of 1 or less, for example, a pH in the range of from -1 to 0.5.
  • the strip solution commonly comprises a mineral acid, particularly sulphuric acid, nitric acid or hydrochloric acid.
  • acid concentrations, particularly for sulphuric acid in the range of from 130 to 200g/l and preferably from 150 to 180g/l are employed.
  • preferred strip solutions comprise stripped or spent electrolyte from a copper electro-winning cell, typically comprising up to 80g/l copper, often greater than 20g/l copper and preferably from 30 to 70g/l copper, and up to 220g/l sulphuric acid, often greater than 120g/l sulphuric acid, and preferably from 150 to 180g/l sulphuric acid.
  • the volume ratio of organic solution to aqueous strip solution in the process of the fourth aspect of the present invention is commonly selected to be such so as to achieve transfer, per litre of strip solution, of up to 50g/l of metal, especially copper into the strip solution from the organic solution.
  • transfer is often from 10g/I to 35g/l, and preferably from 15 to 20g/l of copper per litre of strip solution is transferred from the organic solution.
  • Volume ratios of organic solution to aqueous solution of from 1 :2 to 15:1 and preferably from 1 :1 to 10:1 , especially less than
  • Both the separation and stripping process can be carried out by a conventional batch extraction technique or column contactors or by a continuous mixer settler technique.
  • the latter technique is generally preferred as it recycles the stripped organic phase in a continuous manner, thus allowing the one volume of organic reagent to be repeatedly used for metal recovery.
  • a preferred embodiment of the fourth aspect of the present invention comprises a process for the extraction of a metal from aqueous acidic solution in which: in step 1 , the solvent extraction composition comprising an extractant of formula (1 ) is first contacted with the aqueous acidic solution containing metal, in step 2, separating the solvent extraction composition containing metal-solvent extractant complex from the aqueous acidic solution; in step 3, contacting the solvent extraction composition containing metal-solvent extractant complex with an aqueous acidic strip solution to effect the stripping of the metal from the water immiscible phase; in step 4, separating the metal-depleted solvent extraction composition from the loaded aqueous strip solution.
  • metals are present and are solvent extracted, it may be desirable that said metals are stripped by first changing the oxidation state of the metal in the metal- solvent extractant complex.
  • a process for the stripping of a metal from an organic solution in which a solvent extractant composition containing a complexed metal is contacted with a medium capable of changing the oxidation state of the metal, whereby at least a fraction of the metal is released from the organic solution, characterised in that the solvent extraction composition comprises a water immiscible organic solvent, preferably with a low aromatic hydrocarbon content, a sulphonic acid and a solvent extractant of formula (1):
  • R 1 is an aryl group optionally substituted with one or more groups selected from C ⁇ - 12 alkyl or halo
  • R 2 is C 1-12 alkyl group or a phenyl optionally substituted with one or more groups selected from C 1-12 alkyl or halo
  • R 3 is an alpha branched alkyl group containing at least eight carbon atoms, and tautomers or salts thereof.
  • R 1 is an aryl group optionally substituted with one or more groups selected from
  • R 2 is C 1-12 alkyl group or a phenyl optionally substituted with one or more groups selected from C 1-12 alkyl or halo;
  • R 3 is an alpha branched alkyl group containing at least eight carbon atoms, and tautomers or salts thereof.
  • the medium capable of changing the oxidation state of the metal may be an oxidising or a reducing medium.
  • the medium is a reducing medium.
  • the reducing medium is typically selected according to the reduction potential which is matched to the complexed metal.
  • the complexed metal is preferably iron in oxidation state III.
  • Reducing mediums include metals and alloys of metals which are capable of reducing cations of the metal to a lower oxidation state, sulphur dioxide, hydrogen sulphide.
  • metals or alloys of metals are employed as a reducing medium, preferably these metals or alloys of metals are used in the presence of an acid.
  • Preferred reducing mediums include zinc, aluminium, cadmium, manganese, magnesium, a zinc/acid mixture and a copper/acid mixture.
  • 60.80 triplet, 2xCH3), 61.30 (multiplet, alkyl 1 1H), 51.50 (multiplet, CH 2 ), 61.80 (multiplet, CH 2 ), 62.45 (singlet, CH 3 ), 52.90 (multiplet, CH), 57.30 - 7.9(multiplets,aryl 5H), 512 -14 (broad singlet, OH).
  • Organic extractant solution (A) : Acyl pyrazolone (0.2M) in Orfom SX7 (+ booster)
  • Aqueous feedstock (B) : Mixed metal solution containing 3 g/l copper and 3g/l iron(lll) at pH2.0
  • Example 2 Test to show the effects sulphonic acids of formula (5) on extraction characteristics of acyl pyrazolones.
  • Iron extracted by acyl pyrazolone extractants may be difficult to remove from the organic phase under normal strip conditions (ie contacting organic phase with strongly acidic aqueous solution).
  • the following examples show comparison test of various potential reductive strip mediums when applied to Fe(lll) loaded acyl pyrazolones.
  • Copper/Acid mixture is highly effective as a reductive medium for the stripping of iron.
  • the reductive mediums of Zn/H 2 S0 4 and SO 2 /HCI are more effective in removing iron than the standard acid stripping conditions not employing reductive mediums.

Abstract

A solvent extraction composition comprising a sulphonic acid and a solvent extractant of formula (1): wherein R1 is an aryl group optionally substituted with one or more groups selected from C1-12 alkyl or halo; R2 is C1-12 alkyl group or a phenyl optionally substituted with one or more groups selected from C1-12 alkyl or halo; R3 is an alpha branched alkyl group containing at least eight carbon atoms, and tautomers or salts thereof.

Description

SOLVENT EXTRACTION COMPOSITION COMPRISING SULPHONIC ACID ITH A 4- (ALPHA
BRANCHED) ACYL- (3H) -PYRAZOL-3-ONES AND PROCESSES OF METAL EXTRACTION
The present invention concerns processes using 4-acyl-(3H)-pyrazol-3-ones for the solvent extraction of metals, particularly copper, from aqueous solutions, especially acidic solutions obtained by leaching ores.
Recently, in GB the use of 4-(alpha branched)acyl-(3H)-pyrazol-3-ones, and compositions thereof, in processes for the solvent extraction of metal, particularly copper, is described.
In certain applications, it can be desirable to alter the kinetics of the metal extraction process, particularly to increase the rate of metal transfer in the extraction stages of the process. Surprisingly, it has been found that compositions comprising sulphonic acid kinetics boosters and 4-(alpha branched)acyl-(3H)-pyrazol-3-ones show advantage in metal extraction processes.
According to a first aspect of the present invention, there is provided a solvent extraction composition comprising a sulphonic acid and a solvent extractant of formula
Figure imgf000002_0001
Formula (1) wherein
R1 is an aryl group optionally substituted with one or more groups selected from CM2 alkyl or halo; R2 is C1-12 alkyl group or a phenyl optionally substituted with one or more groups selected from C1-12 alkyl or halo;
R3 is an alpha branched alkyl group containing at least eight carbon atoms, and tautomers or salts thereof.
Whilst the invention is described herein with reference to a compound of Formula (1 ), it is understood that it relates to said compound in any possible tautomeric forms, and also the complexes formed between 4-(alpha branched)acyl-(3H)-pyrazol-3-ones and metals, particularly copper. An example of one tautomeric form of the compound of formula (1) is the tautomeric compound of formula (2):
Figure imgf000002_0002
Formula (2) wherein R1, R2 and R3 are as defined above for the compound of Formula (1).
Aryl groups which may be represented by R1 may contain 1 ring or 2 or more fused rings. Aryl groups include aromatic and heteroaromatic groups. When the aryl group comprises fused rings, the fused rings may include cycloalkyl, aryl or heterocyclic rings. Examples of aryl groups include optionally substituted phenyl, naphthyl, thienyl and pyridyl groups.
Preferably, R1 is a phenyl optionally substituted with one or more groups selected from C1-12 alkyl or halo.
Phenyl groups optionally substituted with one or more groups selected from C1-12 alkyl or halo which may be represented by R1 or R2 include those of formula:
Figure imgf000003_0001
wherein R" to R8 each independently represent H, halo, or a C1-12 alkyl group. When any of R4 to R8 are halo, preferably the halo is CI or F. When any of R4 to R8 are a C,.^ alkyl group, the C1-12 alkyl group can be linear or branched, and preferably is methyl, ethyl or isopropyl.
Preferably only Rs represents a halo group or a C1-12 alkyl group, with R4, R5, R7 and R8 representing H.
When any of R1 or R2 is an optionally substituted phenyl group, it is most preferred that R4 to R8 are all hydrogen.
A preferred 4-(alpha branched)acyl-(3H)-pyrazol-3-one is one in which R is a phenyl optionally substituted with one or more groups selected from C1-12 alkyl or halo, preferably R1 is an unsubstituted phenyl group; R2 is C1-12 alkyl group or a phenyl optionally substituted with one or more groups selected from C1-12 alkyl or halo, preferably R2 is a methyl group; and R3 is an alpha branched alkyl group containing at least eight carbon atoms, preferably a tertiary alpha branched alkyl with at least eight carbon atoms, most preferably a secondary alpha branched alkyl with at least eleven carbon atoms.
Highly preferred 4-(alpha branched)acyl-(3H)-pyrazol-3-ones where R3 is a secondary alpha branched alkyl are 2-Phenyl-5-methyl-4-(2-hexyldecan-1-oyl)-3- pyrazolone and 2-Phenyl-5-methyl-4-(2-butyloctan-1-oyl)-3-pyrazolone.
Highly preferred are 4-(alpha branched)acyl-(3H)-pyrazol-3-ones wherein R3 is an isomeric mixture of tertiary alpha branched alkyl groups. The isomeric mixture of tertiary alpha branched alkyl groups is preferably derived from a Versatic acid. Versatic acids are isomeric mixtures of acids with a fixed number of carbons. Preferred Versatic acids are C10 and C13 Versatic acids which result in 4-(alpha branched)acyl-(3H)-pyrazol-3-ones where R3 is a C9 or C12 alkyl group. Preferred 4-(alpha branched)acyl-(3H)-pyrazol-3- ones are those where R3 is an isomeric mixture of tertiary alpha branched alky groups comprising 9 or more carbon atoms of formula:
Figure imgf000004_0001
where R9 and R10 are independently linear or branched alkyl groups. The isomeric variation results from variations in the number of carbons atoms in the R9 and R10 groups. Sulphonic acids which are suitable for use in compositions of the present invention typically are soluble in the solvents used in metal extraction and show reduced solubility in aqueous acid solution.
Sulphonic acids which are suitable for use in compositions of the present invention, generally are organic sulphonic acids, typically optionally substituted hydrocarbyl sulphonic acids.
Preferred are optionally substituted hydrocarbyl sulphonic acids of Formula (3):
R^SOaH (3) wherein:
R11 is an optionally substituted hydrocarbyl group.
Optionally substituted hydrocarbyl groups which may be represented by R11 preferably comprise optionally substituted alkyl and aryl groups including combinations of these, such as optionally substituted aralkyl and alkaryl groups.
Optionally substituted alkyl groups which may be represented by R11 include groups which contain a total number of alkyl carbons of from 7 to 50, especially from 8 to 40 carbon atoms. A preferred optionally substituted alkyl sulphonic acid is one in which R11 is alkyl, preferably containing more than 8, and especially more than 10, and more preferably more than 15 saturated aliphatic carbon atoms.
Optionally substituted aryl groups which may be represented by R11 include optionally substituted phenyl groups and naphthy! groups. When R11 is an any! group, it is preferably a substituted naphthyl group.
When the optionally substituted hydrocarbyl sulphonic acid is an optionally substituted naphthyl sulphonic acid, the optionally substituted naphthyl sulphonic acid is preferably a compound of formula (4):
Figure imgf000004_0002
(4) wherein: R12 and R13 are each independently an optionally substituted alkyl group. It should be understood that as drawn, each ring of compound of formula (4) may independently be substituted with one or more groups represented by R12 and R13 respectively.
Optionally substituted alkyl groups which may be represented by R12 and R13 include groups which contain a total number of alkyl carbons of from 5 to 30, especially from 7 to 20 carbon atoms.
R12 and R13 may be the same or different. Preferably R 2 and R13 are the same. Preferably, R12 and R13 are unsubstituted alkyl groups. Most preferably C9 unsubstituted alkyl groups. Examples of optionally substituted naphthyi suiphonic acids inciude dinonylnaphthalenesulphonic acids.
Optional substituents, which may substitute the hydrocarbyl group of R11, include halogen, nitro, cyano, hydrocarbyl, such as C^-alky!, especially C^-alky!; hydrocarbyloxy, such as C^o-alkoxy, especially C1-10-alkoxy; hydrocarbyloxycarbonyl, such as
Figure imgf000005_0001
acyl, such as
C1.20-alkylcarbonyl and arylcarbonyl, especially C1-10-alkylcarbonyl and phenylcarbonyl; and acyloxy, such as C1-20-alkylcarbonyloxy and arylcarbonyloxy, especially C^o-alkylcarbonyloxy and phenylcarbonyloxy. There may be more than one substituent in which case the substituents may be the same or different. The compositions of the present invention comprising optionally substituted hydrocarbyl sulphonic acids are advantageous in that they show increased extraction kinetics. However, with certain highly preferred compositions the increase in kinetics can also be achieved while ameliorating iron transfer.
According to a second aspect of the present invention there is provided a solvent extraction composition comprising a sulphonic acid of formula (5):
Figure imgf000005_0002
(5) wherein:
R13 and R 4 each independently is an optionally substituted alkyl group; R15 and R16 each independently is hydrogen or an optionally substituted alky! group; and X is an integer, and a solvent extractant of formula (1 ):
Figure imgf000006_0001
Formula (1) wherein
R is an aryl group optionally substituted with one or more groups selected from C1-12 alkyl or halo;
R2 is C1-12 alkyl group or a phenyl optionally substituted with one or more groups selected from C1-12 alkyl or halo;
R3 is an alpha branched alkyl group containing at least eight carbon atoms, and tautomers or salts thereof. Preferences for the solvent extractant of formula (1 ) are described as herein before in connection with the first aspect the present invention.
R13 and R14 may be the same or different. Preferably, R13 and R14 are the same.
Optionally substituted alkyl groups which may be represented by R13 and R14 include groups which contain a total number of alkyl carbons of from 5 to 40, especially from 7 to 30 carbon atoms. Examples of optionally substituted alkyl groups which may be represented by R13 and R14 include amyl, hexyl, octyi, nonyl, decyl, dodecyl, tridecyl and nonadecyl.
Preferably, R13 and R14 are selected to be optionally substituted alkyl groups each containing eight or more alkyl carbons, for example octyl, nonyl, decyl, dodecyl, tridecyl and nonadecyl groups. More preferably, R13 and R14 are selected to be tridecyl groups.
Optionally substituted alkyl groups which may be represented by R15 and R16 include groups which contain a total number of alkyl carbons of from 1 to 20.
R15 and R16 may be the same or different. Preferably, R15 and R15 are the same. More preferably R15 and R16 are both hydrogen. X is preferably 1 , 2 or 3. Most preferably, X is 1.
The compositions of the present invention have been found to be most suited to use in solvent extraction systems where the solvent used has a low aromatic hydrocarbon content.
According to a third aspect of the present invention there is provided a solvent extraction composition comprising a water immiscible organic solvent, preferably with a low aromatic hydrocarbon content, a sulphonic acid and a solvent extractant of formula (1 ):
Figure imgf000007_0001
Formula (1) wherein
R1 is an aryl group optionally substituted with one or more groups selected from C1-12 alkyl or halo;
R2 is C1-12 alkyl group or a phenyl optionally substituted with one or more groups selected from C1-12 alkyl or halo;
R3 is an alpha branched alkyl group containing at least eight carbon atoms, and tautomers or salts thereof. Preferences for the solvent extractant of formula (1 ) and the sulphonic acid are described as herein before in connection with the first and second aspects the present invention.
The composition may comprise one or more different 4-(alpha branched)acyl- (3H)-pyrazol-3-ones, especially where the component 4-(alpha branched)acyl-(3H)- pyrazol-3-ones are isomeric. Such isomeric mixtures may have better solubility in organic solvents than a single 4-acyl-(3H)-pyrazol-3-one and are preferred.
The 4-(alpha branched)acyl-(3H)-pyrazol-3-one are often present in an amount of up to 60% by weight of the composition, commonly no more than 50%, and usually no more than 40 % w/w. Often, the 4-(alpha branched)acyl-(3H)-pyrazol-3-one comprises at least 1%o by weight, commonly at least 2.5% by weight and usually at least 5% by weight of composition, and preferably comprises from 7.5 to 20%, such as about 10%, by weight of the composition.
The composition may comprise one or more different sulphonic acids. The sulphonic acids are often present in an amount of up to 2% by weight based on the total weight of 4-(alpha branched)acyl-(3H)-pyrazo!-3-one present, commonly no more than
1.5%, and usually no more than 1 % by weight based on the total weight of 4-(alpha branched)acyl-(3H)-pyrazol-3-one present. Often, the sulphonic acids comprise at least 0.01% by weight, commonly at least 0.05% by weight and usually at least 0.1 % by weight based on the total weight of 4-(alpha branched)acyl-(3H)-pyrazol-3-one present, and preferably comprises from 0.05 to 1% such as about 0.2% by weight based on the total weight of 4-(aipha branched)acyl-(3H)-pyrazoi-3-one present..
Organic solvents which may be present in the composition include any mobile organic solvent, or mixture of solvents, which is immiscible with water and is inert under the extraction conditions to the other materials present. Preferably the organic solvent has a low aromatic hydrocarbon content. Preferred organic solvents are hydrocarbon solvents which include aliphatic, alicyclic and aromatic hydrocarbons and mixtures thereof as well as chlorinated hydrocarbons such as trichloroethylene, perchloroethylene, trichloroethane and chloroform. Highly preferred organic solvents having a low aromatics content include solvents and solvent mixtures where the amount of aromatic hydrocarbons present in the organic solvent is less than 30%, usually around 23% or less, often less than 5%, and frequently less than 1%.
Examples of suitable hydrocarbon solvents include ESCAID 110, ESCAID 115, ESCAiD 120, ESCAiD 200, and ESCAiD 300 commerciaiiy available from Exxon
(ESCAID is a trade mark), SHELLSOL D70 and D80 300 commercially available from Shell (SHELLSOL is a trade mark), and CONOCO 170 commercially available from Conoco (CONOCO is a trade mark). Suitable solvents are hydrocarbon solvents include high flash point solvents and solvents with a high aromatic content such as SOLVESSO 150 commercially available from Exxon (SOLVESSO is a trade mark).
More preferred are solvents with a low aromatic content. Certain suitable solvents with a low aromatic content, have aromatic contents of <1 % w/w, for example, hydrocarbon solvents such as ESCAID 110 commercially available from Exxon (ESCAID is a trade mark), and ORFOM SX 10 and ORFOM SX11 commercially available from Phillips Petroleum (ORFOM is a trade mark). Especially preferred, however on grounds of low toxicity and wide availability, are hydrocarbon solvents of relatively low aromatic content such as kerosene, for example ESCAID 100 which is a petroleum distillate with a total aromatic content of 23% commercially available from Exxon (ESCAID is a trade mark), or ORFOM SX7, commercially available from Phillips Petroleum (ORFOM is a trade mark).
In many embodiments, the composition comprises at least 30%, often at least 45% by weight, preferably from 50 to 95% w/w of water-immiscible hydrocarbon solvent.
Advantageously, it may be preferred to make and supply the composition in the form of a . concentrate. The concentrate may then be diluted by the addition of organic solvents as described herein above to produce compositions in the ranges as described herein above. Where the concentrate contains a solvent, it is preferred that the same solvent is used to dilute the concentrate to the "in use" concentration range. In many embodiments, the concentrate composition comprises up to 30%, often up to 20% by weight, preferably up to 10% w/w of water-immiscible hydrocarbon solvent. Often the concentrate composition comprises greater than 5% w/w of water-immiscible hydrocarbon solvent. The viscosity of the acylpyrazolones of the present invention means that concentrates do not display appreciably higher viscosity than extractant compositions at "in use" concentrations. In certain high strength concentrates it may be necessary to employ a higher than normal aromatic hydrocarbon content. In such cases where a high aromatic hydrocarbon containing solvent is used in the concentrate, solvent of very low aromatic hydrocarbon content may be used to dilute the concentrate to the "in use" concentration range.
If desired, compounds or mixtures of compounds selected from the group consisting of alcohols, esters, ethers, polyethers, carbonates, ketones, nitriles, amides, carbamates, sulphoxides, acids of sulphur and phosphorous compounds, for example sulphonic acids, and salts of amines and quaternary ammonium compounds may also be employed as additional modifiers or kinetics boosters in the composition of the invention. Particularly preferred are mixtures comprising a first compound selected from the group consisting of alcohols, esters, ethers, polyethers, carbonates, ketones, nitriles, amides, carbamates, sulphoxides, acids of sulphur and phosphorous compounds, for example sulphonic acids, and salts of amines and quaternary ammonium compounds and a second compound selected from the group consisting of alkanols having from 6 to 18 carbon atoms, an alkyl esters having from 7 to 30 carbon atoms, and tributylphosphate. According to a fourth aspect of the present invention, there is provided a process for the extraction of a metal from solution in which an acidic solution containing a dissolved metal is contacted with a solvent extraction composition comprising a water immiscible organic solvent and a solvent extractant, whereby at least a fraction of the metal is extracted into the organic solution, characterised in that the solvent extraction composition comprises a water immiscible organic solvent, preferably with a low aromatic hydrocarbon content, a sulphonic acid and a solvent extractant of formula (1 ):
Figure imgf000009_0001
Formula (1 ) wherein
R1 is an aryl group optionally substituted with one or more groups selected from C1-12 alkyl or halo;
R2 is C1-12 alkyl group or a phenyl optionally substituted with one or more groups selected from C1-12 alkyl or halo; R3 is an alpha branched alkyl group containing at least eight carbon atoms, and tautomers or salts thereof.
Metals that may be extracted in the process according to the third aspect of the present invention include copper, cobalt, nickel, manganese and zinc, most preferably copper. The extractant of formula (1 ), the sulphonic acid and the water immiscible organic solvent are as herein described before. The aqueous acidic solution from which metals are extracted by the process of the third aspect of the present invention often has a pH in the range of from -1 to 7, preferably from 0 to 5, and most preferably from 0.25 to 3.5. Preferably, when the metal to be extracted is copper pH values of less than 3 chosen so that the copper is extracted essentially free of iron, cobalt or nickel. The solution can be derived from the leaching of ores or may be obtained from other sources, for example metal containing waste streams such as from copper etching baths.
The concentration of metal, particularly copper, in the aqueous acidic solution will vary widely depending for example on the source of the solution. Where the solution is derived from the leaching of ores, the metai concentration is often up to 75g/l and most often from 1 to 40g/l. Where the solution is a waste stream, the metal concentrations can vary from 0.5 to 2g/l for a waste water stream, to somewhat higher for those from other waste streams, for example Printed Circuit Board waste streams, and can be up to 150g/l, usually from 75 to 130g/l. Preferred solvent extraction compositions are those where the organic solvent solutions may contain the acyl pyrazolone in an amount approaching 100% ligand, but typically the acyl pyrazolone will be employed at about 10 to 40% by weight. Highly preferred solvent extraction compositions are those comprising an organic solvent with a total aromatic content of around 23% or less, one or more acyl pyrazolones selected from 2-Phenyl-5-methyl-4-(2-hexyIdecan-1-oyl)-3-pyrazolone or 2-Phenyl-5-methyl-4-(2- butyloctan-1-oyI)-3-pyrazolone in a total amount of between 5 to 40% by weight and one or more sulphonic acids selected from dioctylsulphosuccinate or ditridecylsulphosuccinate in a total amount of between 0.01 to 2% by weight based on the total weight of 4-(alpha branched)acyl-(3H)-pyrazol-3-one present. The process of the fourth aspect of the present invention can be carried out by contacting the solvent extractant composition with the aqueous acidic solution containing a dissolved metal. Ambient or elevated temperatures, such as up to 75°C can be employed if desired. Often a temperature in the range of from 5 to 60°C, and preferably from 15 to 40°C, is employed. The aqueous solution and the solvent extractant are usually agitated together to maximise the interfacial areas between the two solutions.
The volume ratio of solvent extractant to aqueous solution are commonly in the range of from 20:1 to 1 :20, and preferably in the range of from 5:1 to 1 :5. In many embodiments, to reduce plant size and to maximise the use of solvent extractant, organic to aqueous volume ratios close to 1 :1 are maintained by recycle of one of the streams. After contact with the aqueous acidic solution, the metal can be recovered from the solvent extractant by contact with an aqueous acidic strip solution.
The aqueous strip solution employed in the process according to the third aspect of the present invention is usually acidic, commonly having a pH of 2 or less, and preferably a pH of 1 or less, for example, a pH in the range of from -1 to 0.5. The strip solution commonly comprises a mineral acid, particularly sulphuric acid, nitric acid or hydrochloric acid. In many embodiments, acid concentrations, particularly for sulphuric acid, in the range of from 130 to 200g/l and preferably from 150 to 180g/l are employed. When the extracted metal is copper, preferred strip solutions comprise stripped or spent electrolyte from a copper electro-winning cell, typically comprising up to 80g/l copper, often greater than 20g/l copper and preferably from 30 to 70g/l copper, and up to 220g/l sulphuric acid, often greater than 120g/l sulphuric acid, and preferably from 150 to 180g/l sulphuric acid.
The volume ratio of organic solution to aqueous strip solution in the process of the fourth aspect of the present invention is commonly selected to be such so as to achieve transfer, per litre of strip solution, of up to 50g/l of metal, especially copper into the strip solution from the organic solution. In many industrial copper electrowinning processes transfer is often from 10g/I to 35g/l, and preferably from 15 to 20g/l of copper per litre of strip solution is transferred from the organic solution. Volume ratios of organic solution to aqueous solution of from 1 :2 to 15:1 and preferably from 1 :1 to 10:1 , especially less than
6:1 are commonly employed.
Both the separation and stripping process can be carried out by a conventional batch extraction technique or column contactors or by a continuous mixer settler technique. The latter technique is generally preferred as it recycles the stripped organic phase in a continuous manner, thus allowing the one volume of organic reagent to be repeatedly used for metal recovery.
A preferred embodiment of the fourth aspect of the present invention comprises a process for the extraction of a metal from aqueous acidic solution in which: in step 1 , the solvent extraction composition comprising an extractant of formula (1 ) is first contacted with the aqueous acidic solution containing metal, in step 2, separating the solvent extraction composition containing metal-solvent extractant complex from the aqueous acidic solution; in step 3, contacting the solvent extraction composition containing metal-solvent extractant complex with an aqueous acidic strip solution to effect the stripping of the metal from the water immiscible phase; in step 4, separating the metal-depleted solvent extraction composition from the loaded aqueous strip solution.
Where certain metals are present and are solvent extracted, it may be desirable that said metals are stripped by first changing the oxidation state of the metal in the metal- solvent extractant complex.
According to a fifth aspect of the present invention, there is provided a process for the stripping of a metal from an organic solution in which a solvent extractant composition containing a complexed metal is contacted with a medium capable of changing the oxidation state of the metal, whereby at least a fraction of the metal is released from the organic solution, characterised in that the solvent extraction composition comprises a water immiscible organic solvent, preferably with a low aromatic hydrocarbon content, a sulphonic acid and a solvent extractant of formula (1):
Figure imgf000012_0001
Formula (1 ) wherein
R1 is an aryl group optionally substituted with one or more groups selected from Cι-12 alkyl or halo; R2 is C1-12 alkyl group or a phenyl optionally substituted with one or more groups selected from C1-12 alkyl or halo;
R3 is an alpha branched alkyl group containing at least eight carbon atoms, and tautomers or salts thereof.
In a further aspect of the present invention, there is provided a process for the stripping of a metal in the presence of one or more other metals from an organic solution in which a solvent extractant composition containing a complexed first metal and a complexed second metal is contacted with a medium capable of changing the oxidation state of the second metal, whereby at least a fraction of the second metal is released from the organic solution, characterised in that the solvent extraction composition comprises a water immiscible organic solvent, preferably with a low aromatic hydrocarbon content, a sulphonic acid and a solvent extractant of formula (1 ):
Figure imgf000012_0002
Formula (1 ) wherein
R1 is an aryl group optionally substituted with one or more groups selected from
C,.12 alkyl or halo;
R2 is C1-12 alkyl group or a phenyl optionally substituted with one or more groups selected from C1-12 alkyl or halo; R3 is an alpha branched alkyl group containing at least eight carbon atoms, and tautomers or salts thereof.
The medium capable of changing the oxidation state of the metal may be an oxidising or a reducing medium. Preferably, the medium is a reducing medium. The reducing medium is typically selected according to the reduction potential which is matched to the complexed metal.
When the medium is a reducing medium, the complexed metal is preferably iron in oxidation state III. Reducing mediums include metals and alloys of metals which are capable of reducing cations of the metal to a lower oxidation state, sulphur dioxide, hydrogen sulphide.
When metals or alloys of metals are employed as a reducing medium, preferably these metals or alloys of metals are used in the presence of an acid. Preferred reducing mediums include zinc, aluminium, cadmium, manganese, magnesium, a zinc/acid mixture and a copper/acid mixture.
The invention is further illustrated, but not limited, by the following examples.
Examples
Preparation of 2-phenyl-4-(2-hexyldecan-1-oyl)-5-methyl -(3H)-pyrazol-3-one
A mixture of 2-phenyl-5-methyl-(3H)-pyrazol-3-one (164g, 1 M) and dioxane (700ml) were heated to 60°C until complete solution obtained. Calcium hydroxide (148g, 2M) was added and mixture stirred for 30 minutes, 2-hexyldecanoyl chloride (274.5g, 1 M) added drop wise over 30 minutes. The temperature is raised to 95-100°C and held at this temperature, with stirring, overnight. Cooled to RT and reaction mixture drowned out into 2N hydrochloric acid solution (3litres). The brown oil was extracted into hexane and washed with methanol/water, the organic phase was separated off and dried over magnesium sulphate and solvent removed under reduced pressure. Yield 85% (strength 91.4%, calculated by copper uptake). The product can be further purified by high vacuum distillation.
Mass Spec : Mol wt 412, found 411 (M-H)", 413 (M-H)+ . H1NMR (CDCI3, 300Hz) δθ.85 (triplet, 2xCH3), 51.25 (multiplet, alkyl 20H), 61.50 (multiplet, CH2), 61.80 (multiplet, CH2), 52.50 (singlet, CH3), 62.95 (multiplet, CH), 67.30 (triplet, aryl H), 67.50 (triplet, aryl
2H), 67.90 (doublet, aryl 2H).
Preparation of 2-phenyl-4-(2-butyloctan-1-oyl)-5-methyl -(3H)-pyrazol-3-one
A mixture of 2-phenyl-5-methyl-(3H)-pyrazol-3-one (82g, 0.5M) and dioxane (400ml) were heated to 60°C until complete solution obtained. Calcium hydroxide (74g, 1 M) Was added and mixture stirred for 30 minutes, 2-buyloctanoyl chloride (109g, 0.5M) added drop wise over 30 minutes. The temperature is raised to 95-100°C and held at this temperature, with stirring, overnight. Cooled to RT and reaction mixture drowned out into 2N hydrochloric acid solution (1.5litres). The brown oil was extracted into hexane and washed with water, the organic phase was separated off and dried over magnesium sulphate and solvent removed under reduced pressure. Product high vacuum distilled to yield a straw coloured oil. Wt 116g, Strength 96.4% (by copper uptake), Yield 56%. Mass Spec : Mol wt 356, found 355 (M-H)", 357 (M-H)+ . H1NMR (CDCI3, 300Hz)
60.80 (triplet, 2xCH3), 61.30 (multiplet, alkyl 1 1H), 51.50 (multiplet, CH2), 61.80 (multiplet, CH2), 62.45 (singlet, CH3), 52.90 (multiplet, CH), 57.30 - 7.9(multiplets,aryl 5H), 512 -14 (broad singlet, OH).
An extraction kinetics test was carried out to measure the time taken to achieve equilibrium distribution of copper under standard stirring conditions.
Reagents:
Organic extractant solution (A) : Acyl pyrazolone (0.2M) in Orfom SX7 (+ booster) Aqueous feedstock (B) : Mixed metal solution containing 3 g/l copper and 3g/l iron(lll) at pH2.0
Method:
• Transfer 400 ml of the sample solution (A) to the vessel and allow to equilibrate to the water bath temperature (25 ± 1 °C).
• Separately equilibrate 400 ml of aqueous feedstock (B) to the water bath temperature.
• When both solutions are at 25°C start the stirrer, pre-set to give 1270 rpm when stirring an aqueous/organic mixture, and add the aqueous feedstock solution to the vessel rapidly via a wide neck funnel, starting a stop clock halfway through the addition.
• After 29 seconds, transfer about 20 ml of the mixture into a separating funnel. This should take about 2 seconds and gives a sample representative of the condition after 30 seconds of stirring. As the sample disengages in the separating funnel, run the aqueous layer off to prevent further copper transfer. Identify the remaining organic phase sample Org.0.5.
• Similarly, draw another sample off after 1 min and identify this as Org.1.
• Continue stirring for a total of 15 minutes taking samples at regular intervals (2,3,4,5,10,15 mins).
• Separate the phases and analyse copper extracted into the organic phase
Calculate the % copper extracted at the various time intervals using the following formula: % Cu extracted. (0.5 min) = Cu in Org. at t=0.5 X 100
Cu in Org . at equilibrium Comparitive Examples - Test to show the effects of additives without sulphonic acid groups on the extraction characteristics of acyl pyrazolones.
Figure imgf000015_0001
* %ATE = Percent approach to equilibrium
Example 1 - Test to show the effects sulphonic acids of formula (4) on extraction characteristics of acyl pyrazolones
Figure imgf000015_0002
Figure imgf000016_0001
Example 2 - Test to show the effects sulphonic acids of formula (5) on extraction characteristics of acyl pyrazolones.
Figure imgf000016_0002
Conclusion
When conventional kinetics boosters are employed, there is little or no improvement in the time taken to achieve the 100% Cu ATE level. By comparison, when a sulphonic acid is employed, the time taken to achieve the 100% Cu ATE level is significantly reduced. Further, when the sulphonic acid is a compound of formula (5) kinetics are improved and also less iron transfer is achieved. Reductive Strip
Iron extracted by acyl pyrazolone extractants may be difficult to remove from the organic phase under normal strip conditions (ie contacting organic phase with strongly acidic aqueous solution). The following examples show comparison test of various potential reductive strip mediums when applied to Fe(lll) loaded acyl pyrazolones.
Example 3
Acyl pyrazolone (0.2M) in Orfom SX7 stirred with an aqueous solution containing Cu2" (3g/l) and Fe3" (3g/i) overnight. Iron extracted into organic phase analysed at
1278ppm. Portions of the iron loaded organic solution (10ml) were stirred for 1 hour with: -
(a) Copper powder (10g)
(b) Hydrochloric acid solution (10ml at 8M) (c) Copper powder (10g) and Hydrochloric acid solution (10ml at 8M)
The organic phase was then analysed for Fe3+ content
Figure imgf000017_0001
Conclusion, Copper/Acid mixture is highly effective as a reductive medium for the stripping of iron.
Example 4
Acyl pyrazolone (0.2M) in Orfom SX7 stirred with an aqueous solution containing Cu2+ (3g/l) and Fe3+ (3g/l) for 1 hour. Iron extracted into organic phase analysed at 417pprn. Portions of the iron loaded organic solution (10ml) were stirred with: -
(d) Sulphuric acid (10ml at 4M) overnight
(e) Activated zinc granules (10g) and sulphuric acid (10 ml at 1 M) for 1 hour
(f) Water (10ml) and a stream of sulphur dioxide / hydrochloric acid gases for 5 minutes The organic phase was then analysed for Fe3+ content
Figure imgf000018_0001
Conclusion, the reductive mediums of Zn/H2S04 and SO2/HCI are more effective in removing iron than the standard acid stripping conditions not employing reductive mediums.

Claims

1. A solvent extraction composition comprising a sulphonic acid and a solvent extractant of formula (1 ):
Figure imgf000019_0001
Formula (1) wherein
R( is an aryl group optionally substituted with one or more groups selected from C1-12 alkyl or halo;
R2 is C1-12 alkyl group or a phenyl optionally substituted with one or more groups selected from C1-12 alkyl or halo;
R3 is an alpha branched alkyl group containing at least eight carbon atoms, and tautomers or salts thereof.
2. A solvent extraction composition comprising a water immiscible organic solvent, preferably with a low aromatic hydrocarbon content, a sulphonic acid and a solvent extractant of formula (1):
Figure imgf000019_0002
Formula (1 ) wherein
R1 is an aryl group optionally substituted with one or more groups selected from C1-12 alkyl or halo; R2 is C1-12 alkyl group or a phenyl optionally substituted with one or more groups selected from C.,.12 alkyl or halo;
R3 is an alpha branched alkyl group containing at least eight carbon atoms, and tautomers or salts thereof.
3. A solvent extraction composition according to Claim 1 or Claim 2 wherein the sulphonic acid is an optionally substituted naphthyl sulphonic acid of formula (4):
Figure imgf000020_0001
(4) wherein R12 and R13 are each independently an optionally substituted alkyl group.
4. A solvent extraction composition according to Claim 1 or Claim 2 wherein the sulphonic acid is a compound of formula (5):
Figure imgf000020_0002
(5) wherein: R13 and R14 each independently is an optionally substituted alkyl group;
R15 and R16 each independently is hydrogen or an optionally substituted alkyl group, preferably with both R15 and R16 being hydrogen; and X is an integer, preferably with X equals 1.
5. A process for the extraction of a metal from solution in which an acidic solution containing a dissolved metal is contacted with a solvent extraction composition comprising a water immiscible organic solvent and a solvent extractant, whereby at least a fraction of the metal is extracted into the organic solution, characterised in that the solvent extraction composition comprises a water immiscible organic solvent, preferably with a low aromatic hydrocarbon content, a sulphonic acid and a solvent extractant of formula (1 ):
Figure imgf000020_0003
Formula (1) wherein
R1 is an aryl group optionally substituted with one or more groups selected from
C1-12 alkyl or halo;
R2 is C1-12 alkyl group or a phenyl optionally substituted with one or more groups selected from C1-12 alkyl or halo; R3 is an alpha branched alkyl group containing at least eight carbon atoms, and tautomers or salts thereof.
6. A process for the stripping of a metal from an organic solution in which a solvent extractant composition containing a complexed metal is contacted with a medium capable of changing the oxidation state of the metal, whereby at least a fraction of the metal is released from the organic solution, characterised in that the solvent extraction composition comprises a water immiscible organic solvent, preferably with a low aromatic hydrocarbon content, a sulphonic acid and a solvent extractant of formula (1):
Figure imgf000021_0001
Formula (1) wherein
R is an aryl group optionally substituted with one or more groups selected from C- 2 alkyl or halo;
R2 is C,.12 alkyl group or a phenyl optionally substituted with one or more groups selected from C1-12 alkyl or halo; R3 is an alpha branched alkyl group containing at least eight carbon atoms, and tautomers or salts thereof.
7. A process for the stripping of a metal in the presence of one or more other metals from an organic solution in which a solvent extractant composition containing a complexed first metal and a complexed second metal is contacted with a medium capable of changing the oxidation state of the second metal, whereby at least a fraction of the second metal is released from the organic solution, characterised in that the solvent extraction composition comprises a water immiscible organic solvent, preferably with a low aromatic hydrocarbon content, a sulphonic acid and a solvent extractant of formula (1):
Figure imgf000021_0002
Formula (1) wherein R1 is an aryl group optionally substituted with one or more groups selected from
C1-12 alkyl or halo;
R2 is C1-12 alkyl group or a phenyl optionally substituted with one or more groups selected from C1-12 alkyl or halo; R3 is an alpha branched alkyl group containing at least eight carbon atoms, and tautomers or salts thereof.
8. A process according to Claim 6 or 7 wherein the medium capable of changing the oxidation state of the metal is a reducing medium.
9. A process according to Claim 8 wherein the reducing medium is sulphur dioxide, zinc, manganese, magnesium, a zinc/acid mixture and a copper/acid mixture.
10. A process according to any one of Claims 5 to 9 wherein the sulphonic acid is an optionally substituted naphthyl sulphonic acid of formula (4):
Figure imgf000022_0001
(4) wherein R12 and R13 are each independently an optionally substituted alkyl group.
11. A process according to any one of Claims 5 to 9 wherein the sulphonic acid is a compound of formula (5):
Figure imgf000022_0002
(5) wherein:
R13 and R14 each independently is an optionally substituted alkyl group; R 5 and R16 each independently is hydrogen or an optionally substituted alkyl group, preferably with both R15 and R16 being hydrogen; and X is an integer, preferably with X equals 1.
PCT/GB2004/001855 2003-06-06 2004-04-29 Solvent extraction composition comprising sulphonic acid with a 4-(alpha branched) acyl-(3h)-pyrazol-3-ones and processes of metal extraction WO2004108973A1 (en)

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WO2007040817A1 (en) * 2005-09-14 2007-04-12 Cytec Technology Corp. Phenoxypyrazole composition and process for the solvent extraction of metals
CN105861827A (en) * 2016-04-08 2016-08-17 中南大学 Acid-alkaline coupling extraction system used for extraction and separation of multi-metal solutions and application thereof
CN106893874A (en) * 2017-02-21 2017-06-27 中南大学 A kind of method that nickel is reclaimed in the nickel-containing waste water from ammonia

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EP0129448A1 (en) * 1983-04-19 1984-12-27 Societe Nationale Des Poudres Et Explosifs Process for selectively extracting copper using 4-acyl(3H)-pyrazol-3-ones
WO2003054237A1 (en) * 2001-12-20 2003-07-03 Cytec Technology Corp. 4-(alpha branched)acyl- (3h)-pyrazol-3-ones for use in the extraction of metals, especially copper, from solution

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EP0129448A1 (en) * 1983-04-19 1984-12-27 Societe Nationale Des Poudres Et Explosifs Process for selectively extracting copper using 4-acyl(3H)-pyrazol-3-ones
WO2003054237A1 (en) * 2001-12-20 2003-07-03 Cytec Technology Corp. 4-(alpha branched)acyl- (3h)-pyrazol-3-ones for use in the extraction of metals, especially copper, from solution

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Publication number Priority date Publication date Assignee Title
WO2007040817A1 (en) * 2005-09-14 2007-04-12 Cytec Technology Corp. Phenoxypyrazole composition and process for the solvent extraction of metals
US8088810B2 (en) 2005-09-14 2012-01-03 Cytec Technology Corp. Phenoxypyrazole composition and process for the solvent extraction of metals
US8470052B2 (en) 2005-09-14 2013-06-25 Cytec Technology Corp. Phenoxypyrazole composition and process for the solvent extraction of metals
CN105861827A (en) * 2016-04-08 2016-08-17 中南大学 Acid-alkaline coupling extraction system used for extraction and separation of multi-metal solutions and application thereof
CN105861827B (en) * 2016-04-08 2017-09-12 中南大学 A kind of soda acid coupling extraction system separated for many metal solution extractions and its application
CN106893874A (en) * 2017-02-21 2017-06-27 中南大学 A kind of method that nickel is reclaimed in the nickel-containing waste water from ammonia
CN106893874B (en) * 2017-02-21 2018-01-05 中南大学 A kind of method that nickel is reclaimed in the nickel-containing waste water from ammonia

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