WO1997030181A1 - Extraction de cobalt et/ou de nickel d'une solution d'alimentation aqueuse - Google Patents

Extraction de cobalt et/ou de nickel d'une solution d'alimentation aqueuse Download PDF

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Publication number
WO1997030181A1
WO1997030181A1 PCT/GB1997/000091 GB9700091W WO9730181A1 WO 1997030181 A1 WO1997030181 A1 WO 1997030181A1 GB 9700091 W GB9700091 W GB 9700091W WO 9730181 A1 WO9730181 A1 WO 9730181A1
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WIPO (PCT)
Prior art keywords
extractant
feed solution
optionally substituted
formula
cobalt
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Ceased
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PCT/GB1997/000091
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English (en)
Inventor
Domenico Carlo Cupertino
John Campbell
John Robert Lawson
Julie Ann Stocks
Raymond Frederick Dalton
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Syngenta Ltd
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Zeneca Ltd
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Priority claimed from GBGB9603385.7A external-priority patent/GB9603385D0/en
Priority claimed from GBGB9619251.3A external-priority patent/GB9619251D0/en
Application filed by Zeneca Ltd filed Critical Zeneca Ltd
Priority to AU13924/97A priority Critical patent/AU1392497A/en
Publication of WO1997030181A1 publication Critical patent/WO1997030181A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/06—Phosphorus compounds without P—C bonds
    • C07F9/22—Amides of acids of phosphorus
    • C07F9/24—Esteramides
    • C07F9/2454—Esteramides the amide moiety containing a substituent or a structure which is considered as characteristic
    • C07F9/2479—Compounds containing the structure P(=X)n-N-acyl, P(=X)n-N-heteroatom, P(=X)n-N-CN (X = O, S, Se; n = 0, 1)
    • C07F9/2495—Compounds containing the structure P(=X)n-N-acyl, P(=X)n-N-heteroatom, P(=X)n-N-CN (X = O, S, Se; n = 0, 1) containing the structure P(=X)n-N-P (X = O, S, Se; n = 0, 1)
    • 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
    • C22B23/00—Obtaining nickel or cobalt
    • C22B23/04—Obtaining nickel or cobalt by wet processes
    • C22B23/0476—Separation of nickel from cobalt
    • 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
    • C22B3/38—Treatment or purification of solutions, e.g. obtained by leaching by liquid-liquid extraction using organic compounds containing phosphorus
    • C22B3/385—Thiophosphoric acids, or esters thereof
    • 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

  • This specification describes a process relating to the extraction of one or more metals from an aqueous solution containing the metals, especially in the presence of other metals
  • ABTP am ⁇ do-b ⁇ s(th ⁇ o- phosphoryl) compounds
  • a process for the extraction of cobalt from an aqueous feed solution comprising cobalt which comp ⁇ ses contacting the feed solution with an extractant comprising an am ⁇ dob ⁇ s(th ⁇ ophosphoryl) compound of the formula
  • R 1 , R 2 , R 3 & R 4 each independently, represents an optionally substituted hydrocarbyl or optionally substituted hydrocarbyloxy group, or R 1 & R 2 &/or R 3 & R 4 together with the P atom, form an optionally substituted 5- to 8-membered heterocyclic ring, at a pH of greater than 2
  • the cobalt can be separated from such other metals by selective stripping, in which extractant loaded with cobalt and other metals is contacted with a weakly acidic st ⁇ pping solution, the pH of the stripping solution being chosen such that cobalt is transferred into the aqueous phase, but that the undesired 0 metals remain loaded in the extractant
  • the weakly acidic stripping solution may vary depending on the nature of the undesired metals, and their relative concentrations Commonly, the weakly acidic stripping solution is chosen to be such that the final pH of the aqueous solution after stripping is in the range of from 0 5 to 3 and preferably from 1 to 2 5 In
  • the process of the first embodiment is preferably carried out at a pH of the aqueous solution of no less than about pH 2 4 and more preferably no less than about pH 2 5, and although it has been found that Co may be extracted by certain extractants at values as low as about pH 2, the degree of extraction below pH 2 7 is relatively low and it 5 is therefore particularly preferred to operate the present process at or above pH 3 0 especially at least about pH 3 3.
  • the pH of the aqueous solution in the process of the first embodiment is commonly no more than about pH 6 5 and more especially no more than about pH 6
  • a second embodiment of the present invention there is provided a o process for the extraction of nickel from an aqueous feed solution comprising nickel, which comp ⁇ ses contacting the feed solution with an extractant comprising an am ⁇ dob ⁇ s(th ⁇ ophosphoryl) compound of the formula
  • R 1 , R 2 , R 3 & R 4 each independently, represents an optionally substituted hydrocarbyl or optionally substituted hydrocarbyloxy group, or
  • the nickel in the substantial absence of any other metals present in the feed medium which are extractable by the present extractant at a pH value 0 of greater than 4, such as bismuth, cadmium, cobalt, copper, iron, mercury, silver and zinc, these are preferably removed from the feed solution before contacting it with the extractant in the aforementioned pH range
  • the nickel can be separated from such other metals by selective stripping, in which extractant loaded with nickel and other metals is contacted with a weakly acidic stripping solution, the pH of the stripping 5 solution being chosen such that nickel is transferred into the aqueous phase, but that the undesired metals remain loaded in the extractant
  • the weakly acidic st ⁇ pping solution may vary depending on the nature of the undesired metals, and their relative concentrations Commonly, the weakly acidic stripping solution is chosen to be such that the final pH of the aqueous solution after stripping is in the range of from pH 0 5 to 4, and o preferably from 1 to 3 5,
  • R 1 , R 2 , R 3 & R 4 each independently, represents an optionally substituted hydrocarbyl or optionally substituted hydrocarbyloxy group, or
  • R 1 & R 2 &/or R 3 & R 4 together with the P atom, form an optionally substituted 5- to 8-membered heterocyclic ring, at a pH in a range from,
  • these metals may be removed from the feed medium prior to performing the present process, by any convenient method, for example, cementation in the case of copper extraction with a suitable extractant at about pH 2 or below in the case of zinc, and precipitation at pH 3 5 to pH 4 in the case of iron
  • cementation in the case of copper extraction with a suitable extractant at about pH 2 or below in the case of zinc and precipitation at pH 3 5 to pH 4 in the case of iron
  • the remaining components of a feed solution derived from a latente ore may be retained in the feed solution because they are not extracted from the feed solution by the extractant to any significant extent until above the pH at which Co and Ni can be selectively extracted by the extractant
  • the lower value (a) is preferably from about pH 2 4 to about pH 3 3 and more preferably from about pH 2 5 to about pH 3 0
  • Co may be extracted by certain extractants at values as low as about pH 2
  • the degree of extraction below pH 2 7 is relatively low and it is therefore preferred to operate the present process at or above pH 3 0
  • the upper value (b) of the pH range in which Co is selectively extracted from a feed solution containing Co and Ni is preferably from about pH 4 0 to pH 5 0, and more preferably from about 4 0 to about 4 5 although the practical upper pH value depends upon the amount of Nt which can be tolerated in the extracted Co, the specific extractant and certain other environmental factors such as temperature and the nature of other ingredients in the feed solution
  • a process for the selective extraction of cobalt from an aqueous feed solution containing cobalt and nickel and optionally other metals which comp ⁇ ses contacting the feed solution with an ABTP of Formula (1) in a range from about pH 3 to about pH 4
  • the Co, and any Ni in the loaded extractant may be subsequently stripped from the loaded ABTP by contacting the latter with an aqueous strip medium at a pH favouring transport of the Co into the strip medium
  • Ni may be removed from the Co-spent feed solution by contacting the latter solution with fresh extractant at a higher pH.
  • the pH for the extraction of Ni following removal of Co is preferably from about pH 4 up to the level at which the Ni is no longer soluble in the feed solution
  • the practical upper value (d) is about pH 6 if it is desired to extract Ni in the substantial absence of the other metals remaining in the feed solution, which are generally only extracted to a significant extent by the extractant at a pH > 6
  • the Ni, and any other metal in the loaded extractant may be subsequently stripped from the loaded extractant by contacting the latter with an aqueous strip medium at a pH favouring transport of the Ni into the strip medium
  • a process for the sequential separation of Co and Ni from a feed solution containing Co 0 and Ni (especially a feed solution derived from a latente ore from which iron, zinc and any copper have been previously removed), which comprises contacting the feed solution, (i) with an extractant comprising an ABTP of Formula (1) at a pH in a range from
  • step (a) a lower value at which Co is taken up by the extractant in order to form a loaded extractant, to 5
  • step (d) an upper value at which Ni, but substantially no other metal tn the feed solution is taken up by the extractant 5 It is preferred to repeat step (n) sufficiently often to remove substantially all the Ni from the feed solution
  • the lower value (a) in step (i) is preferably from about pH 2 7 to about pH 3 3 and more especially about pH 3 and the upper value (b) in step (i) is preferably from about pH 4 to about pH 5 and more especially from about pH 4 to about pH 4 5
  • the lower o value (c) in step (n) is preferably from about pH 4 to about pH 5 and more especially from about pH 4 5 to about pH 5
  • the upper value (d) in step (n) is preferably from about pH 5 5 to pH 6 5 and more especially about pH 6
  • the EXTRACTANT 5 The ABTPs employed in the present invention are substantially water insoluble
  • the extractant may comprise one or more different ABTPs and compositions of ABTPs in which the nature of the substituents groups represented by R 1 to R 4 differ between component ABTP, especially where the component ABTP are isomeric, are generally preferred because such isomeric compositions often have better solubility in organic solvents than a single ABTP Whilst the invention is described herein with reference to compounds of Formula (1 ), it is to be understood that the invention relates to such compounds in any possible tautome ⁇ c forms, and also to the complexes formed between ABTPs and metals
  • Optionally substituted hydrocarbyl and optionally substituted hydrocarbyloxy groups which may be represented by R 1 , R 2 , R 3 and R 4 preferably comprise optionally substituted alkyl, alkoxy, aryl and aryloxy groups including any combination of these, such as optionally substituted aralkyl and alkaryl groups
  • optionally substituted alkyl and alkoxy groups which may be represented by R 1 , R 2 , R 3 and R 4 , include groups in which the alkyl or alkoxy moieties each contain from 1 to 20, especially from 1 to 10, carbon atoms
  • optionally substituted aryl and aryloxy groups include optionally substituted phenyl and phenoxy groups
  • R 1 and R 2 and/or by R 3 and R 4 together with the P atom examples include rings wherein R 1 and R 2 together and/or R 3 and R 4 together have the following structures
  • each of X 1 and X 2 independently, represents O or S and in which one or more of the carbon atoms may be substituted by one or more substituents, particularly lower alkyl, such as C1 to C6 alkyl, substituents
  • R 1 , R 2 R 3 and R 4 are substituted hydrocarbyl or hydrocarbyloxy group or when the aforementioned heterocyclic ring is substituted
  • the subst ⁇ tuent(s) should be such as not to adversely affect the ability of the ABTP to complex with metals, especially cobalt and nickel
  • Suitable substituents include halogen, nitro, cyano, hydrocarbyl, such as C ⁇ o-alkyl, especially C 1-10 -alkyl, hydrocarbyloxy, such as C-
  • a preferred ABTP is one in which each of R 1 , R 2 , R 3 and R 4 is alkyl, especially secondary alkyl (s-alkyl) Good solubility in preferred solvents is provided when R 1 , R 2 R 3 and R 4 taken together contain at least 12 more preferably at least 16, and especially at least 20, and up to about 40, more preferably 30, saturated aliphatic, or equivalent, carbon atoms
  • R 1 , R 2 R 3 and R 4 taken together contain at least 12 more preferably at least 16, and especially at least 20, and up to about 40, more preferably 30, saturated aliphatic, or equivalent, carbon atoms
  • a phenyl or phenoxy group may be regarded as equivalent to about two or three saturated aliphatic carbon atoms
  • each of R 1 , R 2 , R 3 and R 4 is 2-pentyl
  • Another preferred ABTP is one in which at least one and especially at least two of R 1 to R 4 is optionally substituted phenoxy, preferably an alkyl substituted phenoxy group wherein the alkyl group or groups contain from 1 to 20, and especially from 1 to 10, carbon atoms
  • R 1 to R 4 is optionally substituted phenoxy, ts preferred for both ease of synthesis and because it has been found that it generally has a faster rate of extraction than some of the equivalent alkyl and aryl substituted compounds
  • R 1 is an optionally substituted 2-alkylphenoxy group
  • each of R 2 , R 3 and R 4 is a group selected from optionally substituted 2-alkylphenoxy optionally substituted phenyl, optionally substituted alkyl and optionally substituted alkoxy and at least one optionally substituted 2-atkylphenoxy group has a tertiary alkyl (t-alkyl) substituent
  • the 2-alkyl group preferably contains from 1 to 20, especially from 1 to 10, carbon atoms
  • Such an alkyl group may be primary alkyl (n-alkyl) having one or more carbon atoms, secondary alkyl (s-alkyl) having three or more carbon atoms, or tertiary alkyl (t- alkyl) having four or more carbon atoms
  • the 2-alkylphenoxy group may optionally carry one or more additional alkyl substituents, such as a 4-alkyl substituent
  • the optionally substituted 2-alkylphenoxy group contains a t-alkyl group
  • the latter may be present in addition to the 2-alkyl group and/or the 2-alkyl group may itself be a t-alkyl group
  • 2-alkylphenoxy groups include 2-t-butylphenoxy, 2-t-buty!-4-methyl- phenoxy, 2-t-butyl-5-methylphenoxy, 2,4-d ⁇ -(t-butyl)-phenoxy, 2,4-d ⁇ -(t-pentyl)-phenoxy, 2- methyl-4-t-nonylphenoxy, 2-t-butyl-4-t-nonylphenoxy, 4-octylphenoxy, 4-t-dodecyl- phenoxy, 4-t-dodecyl-2-methylphenoxy, 2-s-butylphenoxy and the like
  • At least one 2-alkylphenoxy group is 2-t-alkylphenoxy and preferably at least two 2-alkylphenoxy groups are 2-t-alkyl-phenoxy
  • Preferred 2-t- alkyl groups include 2-t-butyl
  • Optionally substituted phenyl groups which may be represented by R 2 and/or R 3 and/or R 4 in the ABTP include alkyl substituted phenyl groups, for example o-tolyl, m-tolyl, p-tolyl and xytyl groups and mixtures of such groups
  • alkyl substituted phenyl groups for example o-tolyl, m-tolyl, p-tolyl and xytyl groups and mixtures of such groups
  • a preferred optionally substituted phenyl group is phenyl itself
  • Optionally substituted alkyl and optionally substituted alkoxy groups which may be represented by R 2 and/or R 3 and/or R 4 , include alkyl and alkoxy groups preferably containing from 1 to 20, especially from 1 to 10, carbon atoms
  • Each alkyl group and the alkyl moieties of each alkoxy groups, taken independently, may be n-alkyl having one or more carbon atoms, s-alkyl containing three or more carbon atoms or t-alkyl containing four or more carbon atoms
  • optional substituents for such alkyl or alkoxy groups include halogen, nitro, cyano, hydrocarbyloxy, hydrocarbyloxycarbonyi, acyl and acyloxy groups as hereinbefore more specifically defined More than one substituent may be present in which case the substituents may be the same or different
  • R is an optionally substituted 2-alkylphenoxy group
  • each of R 2 , R 3 and R 4 is either an optionally substituted 2-alkyl
  • the ABTP in which R 1 and R 2 are both optionally substituted 2-alkylphenoxy and R 3 and R 4 are both optionally substituted phenyl are strong metal extractants
  • An example of such an ABTP is one in which R 1 and R 2 are both 2-methyl-4-t-nonylphenoxy and R 3 and R 4 are both phenyl
  • Another useful ABTP in which R 1 and R 3 are optionally substituted 2-alkylphenoxy groups and R 2 and R 4 are optionally substituted phenyl is one in which the 2-alkyl groups are t-alkyl, such as the compound in which R 1 and R 3 are both 2-t-butyl-4-methylphenoxy and R 2 and R 4 are both phenyl
  • each of R 1 , R 2 and R 3 is optionally substituted 2- alkylphenoxy and R 4 is optionally substituted phenyl
  • at least one of the 2-alkylphenoxy groups is preferably 2-t-alkylphenoxy and the others are
  • R 1 is optionally substituted 2-alkyl-phenoxy
  • at least one of R 2 , R 3 and R 4 is optionally substituted alkyl or optionally substituted alkoxy
  • any remaining group or groups from R 2 , R 3 and R 4 are selected from optionally substituted 2- alkylphenoxy and optionally substituted phenyl
  • at least one optionally substituted 2- alkylphenoxy group has a t-alkyl group
  • R 1 is optionally substituted 2-t- alkylphenoxy
  • R 2 is optionally substituted alkoxy and each of R 3 and R 4 , independently, is optionally substituted 2-alkylphenoxy or optionally substituted alkoxy, at least one of R 3 and R 4 being preferably 2-t-alkylphenoxy
  • R 1 is optionally substituted 2-t-alkylphenoxy
  • R 2 is optionally substituted alkoxy or optionally substituted phenyl
  • R 3 and R 4 are the same or different optionally substituted alkoxy groups
  • R 1 is optionally substituted 2-t- alkylphenoxy
  • R 2 is optionally substituted 2-alkylphenoxy or optionally substituted phenyl
  • R 3 and R 4 are the same of different optionally substituted alkyl groups
  • the ABTP of Formula (1) can be prepared by the methods disclosed in EP 573182A and WO 95/15329
  • the contact can be effected by attaching the extractant to a water-insoluble inert support medium and contacting the supported extractant with the feed solution, whereby the loaded-extractant may be easily separated from the feed solution after contact
  • the loaded extractant can then be separated from the feed solution by a cessation of mixing and allowing the immiscible organic and aqueous liquids to separate.
  • a typical solvent extraction process comprises a sequence of stages in which the target metal is extracted into an organic solution, stripped into an aqueous solution and recovered from the aqueous solution by any suitable means, for example by electrowinning.
  • a process for extracting a target metal from an aqueous feed solution by a sequence of stages comprising:
  • This extraction process may be applied to the extraction from aqueous solution of Co and Ni under the appropriate pH conditions, as hereinbefore described.
  • the amount of extractant compound to be used will depend to some extent upon the concentration of metal salt in the aqueous solution and also on the plant design. However, it is preferred to use from 5g to 400g of the extractant per dm 3 (litre) of organic solution. Higher concentrations may be used but tend to afford organic phases of too high viscosity for convenient handling. Lower concentrations can also be used but may involve the use of unnecessarily large volumes of solvent.
  • the volume ratio of organic solution to aqueous feed solution in stage (1) of the aforementioned process is commonly in the range of from 100:1 to 1 :100, preferably from 25:1 to 1 :25, particularly from 5:1 to 1:5, and particularly preferably from 2:1 to 1 :2.
  • aqueous solutions containing 0.1g or more, particularly 1g or more, per dm 3 of a metal such as Co or Ni it is preferred to use from 50 to 400g of the extractant per dm 3 of organic solution.
  • the extractant can be used together with an agent which modifies the behaviour thereof in the extraction process, for example an alkylphenol, alcohol or ester which may be used in an amount of from 10% to 200%, especially from 20% to 100% by weight of extractant compound
  • an agent which modifies the behaviour thereof in the extraction process for example an alkylphenol, alcohol or ester which may be used in an amount of from 10% to 200%, especially from 20% to 100% by weight of extractant compound
  • Such compounds generally weaken the extraction power of the extractant but thereby facilitate the subsequent stripping of metal therefrom In this way, a very strong extractant may be adjusted in strength to the requirements of different feed solutions and different st ⁇ pping solutions
  • Alkytphenols which may be used as modifiers in conjunction with the extractant include alkylphenols containing from 3 to 15 alkyl carbon atoms, for example 4-tert- butyiphenol, 4-heptylphenol, 5-methyl-4-pentylphenol, 2-chloro-4-nonylphenol, 2-cyano-4- nonylphenol, 4-dodecylphenol, 3-pentadecylphenol and 4-nonylphenol and mixtures thereof
  • the preferred phenols contain alkyl groups having from 4 to 12 carbon atoms, especially the mixed 4-nonylphenols obtained by condensation of phenol and propylene t ⁇ mer
  • Alcohols which may be used as modifiers in conjunction with the extractant include saturated and unsaturated hydrocarbon alcohols and polyols containing 14 to 30, preferably 15 to 25 carbon atoms
  • the alcohols are preferably highly branched with the hydroxyl group located approximately midway along the hydrocarbon backbone Especially preferred are the branched chain alcohols that may be made by condensation of short chain alcohols by the Guerbet process, such alcohols sometimes being referred to as Guerbet alcohols
  • the alcohols may contain an aromatic group or other functional group, particularly an ester group
  • Especially useful alcohols may be synthesised from highly branched precursors leading to very highly branched Guerbet alcohols containing a large number of terminal methyl groups
  • particularly efficient alcohol modifiers include highly branched isohexadecyl alcohol and iso-octadecyl alcohol, the latter being 2-(1 ,3,3- tr ⁇ methylbutyl)-5,7,7-tr ⁇ methyloctanol
  • Esters which may be used as modifiers in conjunction with the extractant include saturated and unsaturated aliphatic and aromatic-aliphatic esters containing from 10 to 30 carbon atoms
  • the esters may be mono-esters or polyesters, especially di-esters
  • the esters are preferably highly branched
  • the esters may contain other functional groups, particularly a hydroxyl group
  • Especially useful esters include 2,2,4-t ⁇ methyl-1 ,3- pentanediol isobutyrate and the benzoic acid ester thereof
  • 'highly branched' as applied to the alcohols and esters means that the ratio of the number of methyl carbon atoms to non-methyl carbon atoms is higher than 1 5 and preferably higher than 1 3
  • mixtures of alkylphenols and/or alcohols and/or esters may be employed as modifiers
  • the aforementioned modifiers may be used in the preparation of extractant compositions containing one or more extractant and one or more modifier Stages (1 ) and (2) of the aforementioned process may conveniently be carried out using well known conventional solvent extraction techniques
  • the aqueous solution containing the target metal at a pH in a defined range (as hereinbefore described) is intimately contacted, in a single stage or in multiple stages but preferably continuously, with the organic phase (for example by agitating the two phases together in a suitable vessel) for a time sufficient to allow substantial extraction of the target metal from the aqueous solution, the two phases then being separated in any conventional manner
  • the extraction is usually carried out at ambient temperature although somewhat higher temperatures, for example up to 100°C but preferably not more than 50°C, may be used if operationally convenient
  • Organic solvents which may be used for the extraction 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
  • suitable solvents include aliphatic, alicyclic and aromatic hydrocarbons and mixtures of any of these as well as chlorinated hydrocarbons such as t ⁇ chloroethylene, perchloroethylene, t ⁇ chloroethane and chloroform
  • suitable hydrocarbon solvents include low aromatic ( ⁇ 1% w/w) content hydrocarbon solvents such as ESCAID 110 commercially available from Exxon (ESCAID is a trade mark), and ORFOM SX1 1 commercially available from Phillips Petroleum (ORFOM is a trade mark)
  • Preferred solvents are hydrocarbon solvents including high flash point solvents with a high aromatic content such as SOLVESSO 150 commercially available from Exxon (SOLVESSO is a trade mark) and includes solvents which consist essentially of a mixture of t ⁇ methylbenzenes such as AROMAS
  • strip accelerating additives are generally substantially water insoluble compounds which are soluble in the organic phase and examples of strip accelerating additives which can be employed include aromatic and aliphatic amines, particularly pyndmes and azoles, such as benzimidazoles and oxazoles, quaternary ammonium compounds, hydrocarbyl, particularly alkyl and aryl, sulphonic acids, particularly alkaryl sulphonic acids including dinonylnaphthalenesulphonic acid and didodecylnaphthalene sulphonic acid, carboxyiic acids, particularly long chain alkyl and alkenyl acids comprising from 16 to 30 carbon atoms such as versatic acid, o
  • X, Y and Z each independently represent O or S, and salts thereof
  • Hydrocarbyl groups which may be represented by R 5 and R 6 independently include alkyl and aryl groups, and any combination thereof, such as aralkyl and alkaryl groups
  • Alkyl groups which may be represented by R 5 and R 6 include linear and branched alkyl groups comprising up to 20 carbon atoms, particularly from 3 to 14 carbon atoms, and preferably from 4 to 10 carbon atoms
  • tt is preferred that alkyl groups represented by R 5 and R 6 are branched, especially at the carbon atom alpha to the carbon bonded to the phosphorus atom, or in the case of R 5 -Z- moieties, alpha to the carbon bonded to Z
  • alkyi groups represented by R 5 and R 6 comprise more than one branch, with alkyl groups comprising 2 or 3 branches being especially advantageous
  • Examples of alkyl groups which may be represented by R 5 and R 6 include butyl, including sec-butyl and particularly tert-butyl, pentyl, including particularly 2-
  • Aryl groups which may be represented by R 5 and R 6 include phenyl and naphthyl groups, particularly phenyl and naphthyl groups bearing an alkyl substituent at the position ortho to the carbon bonded to the phosphorus atom, or in the case of R 5 -Z- moieties ortho to the carbon bonded to Z
  • substituents include halogen, nitro, cyano, hydrocarbyl such as C 2 o-alM, especially C ⁇ . ⁇ o-alkyl, hydrocarbyloxy, such as C ⁇ o-alkoxy, especially C 1-10 -alkoxy, hydrocarbyloxycarbonyi, such as C ⁇ o-alkoxy-carbonyl, especially C-i 10 -alkoxycarbonyl, acyl, such as C ⁇ o-alkylcarbonyl and arylcarbonyl, especially C 10 -alkylcarbonyl and phenylcarbonyl, and acyloxy, such as d. 2 o-alkylcarbonyloxy and arylcarbonyloxy especially C 10 -alkyl
  • R 5 and R 6 may represent different hydrocarbyl groups, it is often convenient for R 5 and R 6 to represent the same hydrocarbyl group
  • organothiophosphonate or organothiophosphmate compounds which may be employed in the present invention may be employed in the form of the free acid, or may be employed as a water-immiscible salt thereof, for example an alkali metal, alkaline earth metal ammonium or a zinc salt
  • Highly preferred strip accelerating additives are d ⁇ (tert- butyHthiophosphonic acid, d ⁇ (2,4,4-t ⁇ methylpentyl)th ⁇ ophosph ⁇ n ⁇ c acid and d ⁇ (2,4,4- tr ⁇ methylpentyl)phosph ⁇ n ⁇ c acid
  • One or more of the strip accelerating additives preferably compounds of
  • Formulae (4) or (5) above may be used in the preparation of extractant compositions comprising one or more am ⁇ dob ⁇ s(th ⁇ ophosphoryl) compounds and, commonly, at least one modifier
  • the strip accelerating additives can be present in an amount of up to 30%, particularly up to 15%, by weight of the ABTP, and is usually present tn an amount of at least 0.01 %, particularly from 0 1%, preferably from 0 5% to 5%, and particularly preferably from 1 to 3%, by weight of the ABTP
  • the ABTPs are often present in an amount of up to 50% by weight of the composition, commonly no more than 40%, and usually no more than 30% w/w Often, the ABTP comprises at least 5% by weight, commonly at least 10% by weight and usually at least 15% by weight of the composition
  • the balance of the composition comprises water-immiscible organic solvent(s), often in an amount of from at least 50% by weight
  • Preferred extractant compositions comprise at least 65% by weight of water-immiscible hydrocarbon solvent, an ABTP in an amount up to 30% w/w, and preferably from 5 to 25% w/w and an organ
  • the volume ratio of organic solution to aqueous stnp solution in the stage 3) of the aforementioned process is commonly in the range of from 100:1 to 1 100, preferably from 25:1 to 1 25, particularly from 5.1 to 1:5, and particularly preferably from 2.1 to 1.2
  • the processes according to the present invention are commonly carried out at a temperature of up to 75 ⁇ C, particularly a temperature in the range of from 15 to 50°C
  • EXAMPLE 1 This example serves to demonstrate the principle of sequential and selective separation of metal values but is not intended to suggest a working process in a large- scale solvent extraction ng where inter-stage neutralisation could also be employed to speed up dwell times in the extraction cell
  • Zinc sulphate heptahydrate (2.88g, PA Grade, Janssen Chemica), nickel sulphate hexahydrate (2.65g, ACS Reagent, Aldrich) and cobalt sulphate heptahydrate (2 84g, SLR Reagent, Fisons) were dissolved in distilled water and diluted to 100ml in a graduated flask ("Metal Solution A") Analysis of Metal Solution A by atomic absorption gave the following results (see Table 1)
  • CONTACT 2 The residual aqueous layer (volume 50 25 ml) from Contact 1 was stirred vigorously and contacted with a further 50ml sample of Ligand Solution B After stir ⁇ ng for 20 minutes at 25°C with no further addition of base, the pH of the aqueous layer had fallen to pH 1 75 Stirring was stopped and the layers separated Analysis of a sample of the two layers by atomic absorption gave the following results
  • CONTACT 3 The residual aqueous layer (volume 50 0 ml) from Contact 2 was stirred vigorously and contacted with a further 50 ml sample of Ligand Solution B and NaOH solution (0 6 ml, 47%) was added dropwise over 15 minutes After stirring for a further 5 minutes the pH of the aqueous layer was pH 3 8 and the aqueous and organic layers were separated Analysis of these by atomic absorption gave the following results
  • CONTACT 6 Nickel was transferred to the organic layer by contacting the residual aqueous layer from Contact 5 with a further 50ml of Ligand Solution B and raising the pH to >6 0 Control of pH was very difficult at this pH level and the final pH was 8 1
  • extractant compositions were prepared by adding, at the concentrations specified, the strip accelerating compounds given in Table 2 below, to the solution of Example 2.
  • Example 10 An organic solution having the same composition employed in Example 10 was contacted with an aqueous feed solution containing about 1240ppm zinc and 5500ppm cobalt, both as sulphates, at an organic/aqueous ratio of 1 1
  • the pH of the aqueous solution was raised to 5 0 with dilute sodium hydroxide solution, thereby effecting the transfer of all the metals from the aqueous to the organic phase
  • This loaded organic solution was separated from the aqueous feed solution, and was found by analysis to contain 1243ppm zinc and 5500ppm cobalt
  • the loaded organic solution was then stirred vigorously at an O/A ratio of 1 1 with va ⁇ ous aqueous strip solutions of sulphuric acid for 5 minutes
  • the concentrations of sulphuric acid employed were as detailed in Table 3 below
  • the two phases were separated and analysed for metal content The results of the analyses are given in Table 3 below

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Abstract

L'invention concerne la séparation sélective du cobalt et/ou du nickel d'une solution aqueuse acide et, plus particulièrement, un procédé de séparation sélective de cobalt de solutions aqueuses contenant également du nickel. Le procédé consiste à mettre la solution brute dans des conditions contrôlées de pH en contact avec un agent d'extraction contenant un composé amidobis(thiophosphoryle) de la formule (1). Dans cette formule, R?1, R2, R3 et R4¿ représentent chacun, d'une manière indépendante, un groupe hydrocarbyle éventuellement substitué ou un groupe hydrocarbyloxy éventuellement substitué ou R1 et R2 et/ou R3 et R4 forment ensemble avec l'atome de P un hétérocycle à 5 - 8 éléments, éventuellement substitué.
PCT/GB1997/000091 1996-02-17 1997-01-14 Extraction de cobalt et/ou de nickel d'une solution d'alimentation aqueuse Ceased WO1997030181A1 (fr)

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GBGB9603385.7A GB9603385D0 (en) 1996-02-17 1996-02-17 Process
GB9619251.3 1996-09-14
GBGB9619251.3A GB9619251D0 (en) 1996-09-14 1996-09-14 Metal recovery process

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Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2317385A (en) * 1996-09-14 1998-03-25 Zeneca Ltd Compositions of amidobisthiophosphoryl compound & organothiophosphinate or (thio)ester of alkyl mono/di-thiophosphonate in the extraction and recovery of zinc
AU694821B2 (en) * 1995-01-09 1998-07-30 Lionore Australia (Avalon) Pty Ltd The recovery of nickel and cobalt from lateritic ores
WO2007092994A1 (fr) * 2006-02-15 2007-08-23 Andreazza Consulting Pty Ltd Traitement de minerai de laterite
RU2378400C2 (ru) * 2007-12-19 2010-01-10 Институт химии и химической технологии СО РАН (ИХХТ СО РАН) Способ извлечения никеля из сульфатных растворов с высоким содержанием кальция и магния
CN117144140A (zh) * 2023-08-02 2023-12-01 浙江天能新材料有限公司 一种从废旧三元锂离子电池中提取镍的方法
CN117144139A (zh) * 2023-08-02 2023-12-01 浙江天能新材料有限公司 一种从废旧三元锂离子电池中提取钴的方法

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6161688A (ja) * 1984-08-31 1986-03-29 Daihachi Kagaku Kogyosho:Kk 銅および／もしくはカドミウムとコバルトおよび／もしくはニツケルとを分離する方法
EP0210387A1 (fr) * 1985-07-24 1987-02-04 American Cyanamid Company Extraction sélective de métaux hors de solutions aqueuses au moyen d'acides dithiophosphiniques
EP0400311A2 (fr) * 1989-05-31 1990-12-05 Cyanamid Canada Inc. Récupération de métaux au moyen d'acides monothiophosphiniques
EP0562709A2 (fr) * 1992-02-25 1993-09-29 Zeneca Limited Procédé de stripage de métaux à partir des phases organiques
EP0573182A1 (fr) * 1992-06-05 1993-12-08 Zeneca Limited Procédé pour l'extraction de métaux
US5378262A (en) * 1994-03-22 1995-01-03 Inco Limited Process for the extraction and separation of nickel and/or cobalt
WO1995015329A1 (fr) * 1993-12-02 1995-06-08 Zeneca Limited Amides d'acides de phosphore destines a l'extraction de metaux
US5470553A (en) * 1993-12-07 1995-11-28 Industrial Technology Research Institute Method for separating cobalt, nickel, and aluminum ions in sulfuric acid aqueous solutions and the extractant compositions used therein

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6161688A (ja) * 1984-08-31 1986-03-29 Daihachi Kagaku Kogyosho:Kk 銅および／もしくはカドミウムとコバルトおよび／もしくはニツケルとを分離する方法
EP0210387A1 (fr) * 1985-07-24 1987-02-04 American Cyanamid Company Extraction sélective de métaux hors de solutions aqueuses au moyen d'acides dithiophosphiniques
EP0400311A2 (fr) * 1989-05-31 1990-12-05 Cyanamid Canada Inc. Récupération de métaux au moyen d'acides monothiophosphiniques
EP0562709A2 (fr) * 1992-02-25 1993-09-29 Zeneca Limited Procédé de stripage de métaux à partir des phases organiques
EP0573182A1 (fr) * 1992-06-05 1993-12-08 Zeneca Limited Procédé pour l'extraction de métaux
WO1995015329A1 (fr) * 1993-12-02 1995-06-08 Zeneca Limited Amides d'acides de phosphore destines a l'extraction de metaux
US5470553A (en) * 1993-12-07 1995-11-28 Industrial Technology Research Institute Method for separating cobalt, nickel, and aluminum ions in sulfuric acid aqueous solutions and the extractant compositions used therein
US5378262A (en) * 1994-03-22 1995-01-03 Inco Limited Process for the extraction and separation of nickel and/or cobalt
US5447552A (en) * 1994-03-22 1995-09-05 Goro Nickel S.A. Process for the extraction and separation of nickel and/or cobalt

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
G. COTE & D. BAUER: "Extraction of non-ferrous metals by thiophosphorus extractants", CHEMISTRY AND INDUSTRY, no. 22, 17 November 1986 (1986-11-17), LONDOB, GB, pages 780 - 784, XP002028741 *
H. MATSUYANIA ET AL.: "Enhancement in extraction rates by addition of organic acids to aqueous phase in solvent extraction ...", JOUNAL OF CHEMICAL ENGINEERING OF JAPAN, vol. 29, no. 1, February 1996 (1996-02-01), TOKYO, JP, pages 126 - 133, XP000583012 *
PATENT ABSTRACTS OF JAPAN vol. 010, no. 226 (C - 364) 7 August 1986 (1986-08-07) *

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
AU694821B2 (en) * 1995-01-09 1998-07-30 Lionore Australia (Avalon) Pty Ltd The recovery of nickel and cobalt from lateritic ores
GB2317385A (en) * 1996-09-14 1998-03-25 Zeneca Ltd Compositions of amidobisthiophosphoryl compound & organothiophosphinate or (thio)ester of alkyl mono/di-thiophosphonate in the extraction and recovery of zinc
WO2007092994A1 (fr) * 2006-02-15 2007-08-23 Andreazza Consulting Pty Ltd Traitement de minerai de laterite
RU2378400C2 (ru) * 2007-12-19 2010-01-10 Институт химии и химической технологии СО РАН (ИХХТ СО РАН) Способ извлечения никеля из сульфатных растворов с высоким содержанием кальция и магния
CN117144140A (zh) * 2023-08-02 2023-12-01 浙江天能新材料有限公司 一种从废旧三元锂离子电池中提取镍的方法
CN117144139A (zh) * 2023-08-02 2023-12-01 浙江天能新材料有限公司 一种从废旧三元锂离子电池中提取钴的方法
CN117144140B (zh) * 2023-08-02 2025-07-01 浙江天能新材料有限公司 一种从废旧三元锂离子电池中提取镍的方法
CN117144139B (zh) * 2023-08-02 2025-07-29 浙江天能新材料有限公司 一种从废旧三元锂离子电池中提取钴的方法

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