WO2017054057A1 - Procédé de récupération de zinc à partir d'une solution - Google Patents

Procédé de récupération de zinc à partir d'une solution Download PDF

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Publication number
WO2017054057A1
WO2017054057A1 PCT/AU2016/050926 AU2016050926W WO2017054057A1 WO 2017054057 A1 WO2017054057 A1 WO 2017054057A1 AU 2016050926 W AU2016050926 W AU 2016050926W WO 2017054057 A1 WO2017054057 A1 WO 2017054057A1
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WO
WIPO (PCT)
Prior art keywords
zinc
solution
ammonium carbonate
aqueous
extractant
Prior art date
Application number
PCT/AU2016/050926
Other languages
English (en)
Inventor
Nicholas James Welham
Original Assignee
Metaleach Limited
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from AU2015903957A external-priority patent/AU2015903957A0/en
Application filed by Metaleach Limited filed Critical Metaleach Limited
Priority to CA3000543A priority Critical patent/CA3000543A1/fr
Priority to AU2016333158A priority patent/AU2016333158A1/en
Priority to TR2018/04416T priority patent/TR201804416T1/tr
Priority to MX2018004024A priority patent/MX2018004024A/es
Priority to US15/764,059 priority patent/US20180237886A1/en
Publication of WO2017054057A1 publication Critical patent/WO2017054057A1/fr
Priority to ZA2018/02641A priority patent/ZA201802641B/en
Priority to AU2022203277A priority patent/AU2022203277A1/en

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B19/00—Obtaining zinc or zinc oxide
    • C22B19/20—Obtaining zinc otherwise than by distilling
    • C22B19/24—Obtaining zinc otherwise than by distilling with leaching with alkaline solutions, e.g. ammonia
    • 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
    • C22B3/04—Extraction of metal compounds from ores or concentrates by wet processes by leaching
    • C22B3/12—Extraction of metal compounds from ores or concentrates by wet processes by leaching in inorganic alkaline solutions
    • C22B3/14—Extraction of metal compounds from ores or concentrates by wet processes by leaching in inorganic alkaline solutions containing ammonia or ammonium salts
    • 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
    • C22B3/384—Pentavalent phosphorus oxyacids, esters thereof
    • C22B3/3846—Phosphoric acid, e.g. (O)P(OH)3
    • 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
    • C22B3/30—Oximes
    • 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 relates to a method for recovering zinc from an ammoniacal ammonium carbonate solution. More particularly, the present invention relates to a method for recovering zinc from an ammoniacal ammonium carbonate solution by way of solvent extraction.
  • Zinc is typically derived from the sulphide mineral sphalerite by roasting the ore to form zinc oxide, leaching the zinc oxide in sulphuric acid, purifying the solution by adding zinc dust and then electrowinning the zinc. Purification of the pregnant leach solution can also be undertaken through the use of a solvent extraction process.
  • a method for recovering zinc from an aqueous ammoniacal ammonium carbonate zinc solution comprising the steps of: i. Contacting the aqueous ammoniacal ammonium carbonate zinc solution with an organic solution of a zinc extractant, such that a portion of the zinc is transferred from the aqueous ammoniacal ammonium carbonate zinc solution, producing a zinc-depleted aqueous ammoniacal ammonium carbonate solution and a zinc-enriched organic solution of a zinc extractant; ii. Separating the zinc-enriched organic solution of a zinc extractant from the zinc-depleted aqueous ammoniacal ammonium carbonate solution; iii.
  • ammoniacal solutions are chemically distinct from acid solutions.
  • an acid leach solution the level of carbonate will be very low due to the low solubility of CO 2 under the acid conditions necessary for leaching.
  • the addition of carbonates to such a solution therefore results in the evolution of C0 2 .
  • the ammoniacal solutions there is a much higher solubility of bicarbonate/carbonate ions and so C0 2 does not evolve.
  • step ii) more specifically comprises:
  • step iii) more specifically comprises:
  • step iv) more specifically comprises:
  • the method further comprises the step of:
  • Leaching a zinc-containing ore with an ammoniacal solution to produce the aqueous ammoniacal ammonium carbonate zinc solution more specifically comprises the step of:
  • the zinc-containing ore contains carbonate minerals.
  • the zinc-containing ore is a zinc carbonate (smithsonite, ZnC0 3 , or hydrozincite Zn 5 (C03)2(OH) 6 ) containing ore. With such ores, a portion of the carbonate present in the ore will be dissolved concomitantly with the zinc during leaching in an ammoniacal solution, which may initially contain no carbonate ions, to produce the aqueous ammoniacal ammonium carbonate zinc solution.
  • the method further comprises the step of:
  • the carbon dioxide evolved during step (iii) is absorbed into an aqueous solution containing ammonia. Still preferably, the carbon dioxide evolved during step (iii) is absorbed into the zinc- and carbonate-depleted aqueous ammoniacal ammonium carbonate solution produced during step (i).
  • step (iii) Contacting the aqueous zinc ammoniacal ammonium carbonate solution with an organic solution of a zinc extractant, such that a portion of the zinc and the carbonate is transferred from the aqueous ammoniacal ammonium carbonate zinc solution, producing a zinc-depleted carbonate-depleted aqueous ammoniacal ammonium carbonate solution and a zinc-and carbonate-enriched organic solution of a zinc extractant; and the carbon dioxide evolved during step (iii) is absorbed into an aqueous solution, the aqueous solution of carbon dioxide is used in the ammoniacal leaching of a zinc- containing ore to produce the aqueous ammoniacal ammonium carbonate zinc solution which is the feed to step (i).
  • step (i) In one form of the method of the present invention is performed in a continuous manner, and at least a portion of the organic solution of a zinc extractant of step (i) is provided by the zinc-depleted organic solution of a zinc extractant provided by subsequent method steps.
  • the method more specifically comprises a method for recovering zinc from an aqueous ammoniacal ammonium carbonate zinc solution containing free ammonia, the method comprising the steps of: a) Contacting the aqueous ammoniacal ammonium carbonate zinc solution containing free ammonia with an organic solution of a zinc extractant, such that a portion of the zinc and ammonia is transferred from the aqueous ammoniacal ammonium carbonate zinc solution containing free ammonia, producing a zinc- and ammonia-depleted aqueous ammoniacal ammonium carbonate solution and a zinc- and ammonia-enriched organic solution of a zinc extractant; b) Separating the zinc-enriched ammonia-enriched organic solution of a zinc extractant and zinc-depleted ammonia-depleted aqueous solution; c) Contacting the zinc-enriched ammonia-enriched organic solution with an ammonia scrub solution to reduce ammonia thereby producing a zinc-rich
  • the ammonia scrub solution preferably has a pH less than 2. More preferably, the ammonia scrub solution has a pH less than 3. Still preferably, the ammonia scrub solution has a pH less than 4. Still preferably, the ammonia scrub solution has a pH less than 5. Still preferably, the ammonia scrub solution has a pH less than 6. Still preferably, the ammonia scrub solution has a pH less than 7.
  • the ammonia scrub solution preferably has a pH in the range 2-8. Still preferably, the ammonia scrub solution has a pH in the range 3-8. Still preferably, the ammonia scrub solution has a pH in the range 4-8. Still preferably, the ammonia scrub solution has a pH in the range 5-8. Still preferably, the ammonia scrub solution has a pH in the range 6-8. Still preferably, the ammonia scrub solution has a pH in the range 7-8.
  • ammonia present in the zinc-enriched ammonia-enriched organic solution is present as weakly-held ammonium NH 4 + ions. In the presence of protons, the weakly-held ammonium ions are displaced by the more strongly-held protons of the ammonia scrub solution.
  • the ammonia scrub solution is produced by dilution of the zinc-enriched aqueous acid solution produced in the process. More preferably, the ammonia scrub solution is composed of a dilute solution of a mineral acid, selected from the group: sulphuric acid, hydrochloric acid, nitric acid. In a highly preferred form the ammonia scrub solution is dilute sulphuric acid.
  • the ammonia scrub solution is carbonic acid, a solution of carbon dioxide in water. More preferably, the concentration of carbonic acid in solution is maintained by constant replenishment of carbon dioxide.
  • the method more specifically comprises a method for recovering zinc from an aqueous impurity-containing ammoniacal ammonium carbonate zinc solution, the method comprising the steps of: a) Contacting the aqueous impurity-containing zinc ammoniacal ammonium carbonate solution with an organic solution of a zinc extractant, such that a portion of the zinc and the impurities from the aqueous impurity-containing ammoniacal ammonium carbonate zinc solution producing an impurity-depleted zinc-depleted aqueous ammoniacal ammonium carbonate solution and an impurity-enriched zinc-enriched organic solution of a zinc extractant; b) Separating the impurity-enriched zinc-enriched organic solution of a zinc
  • the impurity scrub solution preferably has a pH less than 0. More preferably, the impurity scrub solution has a pH less than 1 . Still preferably, the impurity scrub solution has a pH less than 2. Still preferably, the impurity scrub solution has a pH less than 3. Still preferably, the impurity scrub solution has a pH less than 4. Still preferably, the impurity scrub solution has a pH less than 5. Still preferably, the impurity scrub solution has a pH less than 6. Still preferably, the impurity scrub solution has a pH less than 7.
  • the impurities present in the impurity-enriched zinc-enriched organic solution are present in weakly-held forms. In the presence of protons, the weakly-held impurity ions are displaced from the impurity-enriched zinc-enriched organic solution by the more strongly held protons of the impurity scrub solution. As would be recognised by those skilled in the art, different impurities will be held with differing strength and some impurities will require a lower pH impurity scrub solution than other.
  • the impurity scrub solution preferably contains zinc ions
  • the concentration of zinc in the impurity scrub solution is preferably less than 1 g/L. More preferably, the concentration of zinc in the impurity scrub solution is less than 2 g/L. Still preferably, the concentration of zinc in the impurity scrub solution is less than 3 g/L. Still preferably, the concentration of zinc in the impurity scrub solution is less than 4 g/L. Still preferably, the concentration of zinc in the impurity scrub solution is less than 5 g/L.
  • the concentration of zinc in the impurity scrub solution is less than 7 g/L. Still preferably, the concentration of zinc in the impurity scrub solution is less than 10 g/L. Still preferably, the concentration of zinc in the impurity scrub solution is less than 15 g/L. Still preferably, the concentration of zinc in the impurity scrub solution is less than 20 g/L. Still preferably, the concentration of zinc in the impurity scrub solution is less than 30 g/L. Still preferably, the concentration of zinc in the impurity scrub solution is less than 50 g/L. Still preferably, the concentration of zinc in the impurity scrub solution is less than 60 g/L. Still preferably, the concentration of zinc in the impurity scrub solution is less than 75 g/L. Still preferably, the concentration of zinc in the impurity scrub solution is less than 1 00 g/L. Still preferably, the concentration of zinc in the impurity scrub solution is less than 1 50 g/L.
  • the impurities present in the impurity-enriched zinc-enriched organic solution are present in weakly-held forms. In the presence of zinc ions, the weakly-held impurity ions are displaced from the impurity-enriched zinc-enriched organic solution by the more strongly held zinc ions. As would be recognised by those skilled in the art, different impurities will be held with differing strength and some impurities will require a higher zinc concentration in the impurity scrub solution than others.
  • the method of the present invention may more specifically comprise both of: a method for recovering zinc from an aqueous ammoniacal ammonium carbonate zinc solution containing free ammonia; and a method for recovering zinc from an aqueous impurity-containing ammoniacal ammonium carbonate zinc solution, such that the method of the present invention comprises both the steps of:
  • the method of the present invention may more specifically comprise both of: a method for recovering zinc from an aqueous ammoniacal ammonium carbonate zinc solution containing free ammonia; and a method for recovering zinc from an aqueous impurity-containing ammoniacal ammonium carbonate zinc solution, the steps of : Contacting the zinc-enriched ammonia-enriched organic solution with an ammonia scrub solution to remove ammonia thereby producing a zinc-enriched ammonia-depleted organic solution of a zinc extractant and an ammonia- enriched solution; and
  • the method of the present invention is performed at elevated temperature.
  • the method of the present invention is performed at 1 5-80°C. Still preferably the method of the present invention is performed at 15-70°C. Still preferably, the method of the present invention is performed at 15-60°C. Still preferably, the method of the present invention is performed at 15-50°C. Still preferably, the method of the present invention is performed at 15-40°C. Still preferably, the method of the present invention is performed at 15-30°C. Still preferably, the method of the present invention is performed at 15-25°C. Still preferably, the method of the present invention is performed at ambient temperature. As would be understood by a person skilled in the art, the performance of the method of the present invention at ambient temperature is advantageous as no additional operations costs are incurred by increasing the temperature of the method.
  • the method of the present invention is performed at 20-80°C. Still preferably the method of the present invention is performed at 20-70°C. Still preferably the method of the present invention is performed at 20-60°C. Still preferably the method of the present invention is performed at 20-50°C. Still preferably the method of the present invention is performed at 20-40°C. Still preferably the method of the present invention is at 20-30°C.
  • the method of the present invention is performed at 25-80°C. Still preferably the method of the present invention is performed at 25-70°C. Still preferably the method of the present invention is performed at 25-60°C. Still preferably the method of the present invention is performed at 25-50°C. Still preferably the method of the present invention is performed at 25-40°C. Still preferably the method of the present invention is performed at 25-30°C.
  • the method of the present invention is performed at 30-80°C. Still preferably the method of the present invention is performed at 30-70°C. Still preferably the method of the present invention is performed at 30-60°C. Still preferably the method of the present invention is performed at 30-50°C. Still preferably the method of the present invention is performed at 30-40°C.
  • the concentration of zinc in the ammoniacal ammonium carbonate solution is less than 0.1 g/L. Still preferably, the concentration of zinc in the ammoniacal ammonium carbonate solution is less than 1 g/L. Still preferably, the concentration of zinc in the ammoniacal ammonium carbonate solution is less than 2 g/L. Still preferably, the concentration of zinc in the ammoniacal ammonium carbonate solution is less than 3 g/L. Still preferably, the concentration of zinc in the ammoniacal ammonium carbonate solution is less than 4 g/L. Still preferably, the concentration of zinc in the ammoniacal ammonium carbonate solution is less than 5 g/L.
  • the concentration of zinc in the ammoniacal ammonium carbonate solution is less than 7 g/L. Still preferably, the concentration of zinc in the ammoniacal ammonium carbonate solution is less than 10 g/L. Still preferably, the concentration of zinc in the ammoniacal ammonium carbonate solution is less than 15 g/L. Still preferably, the concentration of zinc in the ammoniacal ammonium carbonate solution is less than 20 g/L. Still preferably, the concentration of zinc in the ammoniacal ammonium carbonate solution is less than 30 g/L. Still preferably, the concentration of zinc in the ammoniacal ammonium carbonate solution is less than 50 g/L.
  • the concentration of zinc in the ammoniacal ammonium carbonate solution is less than 60g/L. Still preferably, the concentration of zinc in the ammoniacal ammonium carbonate solution is less than 75 g/L. Still preferably, the concentration of zinc in the ammoniacal ammonium carbonate solution is less than 1 00 g/L. Still preferably, the concentration of zinc in the ammoniacal ammonium carbonate solution is less than 150 g/L. Still preferably, the concentration of zinc in the ammoniacal ammonium carbonate solution is less than 250 g/L. Still preferably, the concentration of zinc in the ammoniacal ammonium carbonate solution is less than 500 g/L.
  • the concentration of zinc in the ammoniacal ammonium carbonate solution is between 0.1 and 1 g/L.
  • the concentration of zinc in the ammoniacal ammonium carbonate solution is between 0.1 and 2 g/L.
  • the concentration of zinc in the ammoniacal ammonium carbonate solution is between 0.1 and 3 g/L.
  • the concentration of zinc in the ammoniacal ammonium carbonate solution is between 0.1 and 4 g/L.
  • the concentration of zinc in the ammoniacal ammonium carbonate solution is between 0.1 and 5 g/L.
  • the concentration of zinc in the ammoniacal ammonium carbonate solution is between 0.1 and 7 g/L. Still preferably, the concentration of zinc in the ammoniacal ammonium carbonate solution is between 0.1 and 10 g/L. Still preferably, the concentration of zinc in the ammoniacal ammonium carbonate solution is between 0.1 and 15 g/L. Still preferably, the concentration of zinc in the ammoniacal ammonium carbonate solution is between 0.1 and 20 g/L. Still preferably, the concentration of zinc in the ammoniacal ammonium carbonate solution is between 0.1 and 30 g/L. Still preferably, the concentration of zinc in the ammoniacal ammonium carbonate solution is between 0.1 and 50 g/L.
  • the concentration of zinc in the ammoniacal ammonium carbonate solution is between 0.1 and 60 g/L. Still preferably, the concentration of zinc in the ammoniacal ammonium carbonate solution is between 0.1 and 75 g/L. Still preferably, the concentration of zinc in the ammoniacal ammonium carbonate solution is between 0.1 and 1 00 g/L. Still preferably, the concentration of zinc in the ammoniacal ammonium carbonate solution is between 0.1 and 150 g/L. Still preferably, the concentration of zinc in the ammoniacal ammonium carbonate solution is between 0.1 and 200 g/L. Still preferably, the concentration of zinc in the ammoniacal ammonium carbonate solution is between 0.1 and 250 g/L. Still preferably, the concentration of zinc in the ammoniacal ammonium carbonate solution is between 0.1 and 350 g/L. Still preferably, the concentration of zinc in the ammoniacal ammonium carbonate solution is between 0.1 and 500 g/L.
  • the concentration of free ammonia in the ammoniacal ammonium carbonate solution is less than 0.1 g/L.
  • the concentration of free ammonia in the ammoniacal ammonium carbonate solution is less than 1 g/L.
  • the concentration of free ammonia in the ammoniacal ammonium carbonate solution is less than 2 g/L.
  • the concentration of free ammonia in the ammoniacal ammonium carbonate solution is less than 3 g/L.
  • the concentration of free ammonia in the ammoniacal ammonium carbonate solution is less than 4 g/L.
  • the concentration of free ammonia in the ammoniacal ammonium carbonate solution is less than 5 g/L. Still preferably, the concentration of free ammonia in the ammoniacal ammonium carbonate solution is less than 7 g/L. Still preferably, the concentration of free ammonia in the ammoniacal ammonium carbonate solution is less than 10 g/L. Still preferably, the concentration of free ammonia in the ammoniacal ammonium carbonate solution is less than 15 g/L. Still preferably, the concentration of free ammonia in the ammoniacal ammonium carbonate solution is less than 20 g/L. Still preferably, the concentration of free ammonia in the ammoniacal ammonium carbonate solution is less than 30 g/L.
  • the concentration of free ammonia in the ammoniacal ammonium carbonate solution is less than 50 g/L. Still preferably, the concentration of free ammonia in the ammoniacal ammonium carbonate solution is less than 60 g/L. Still preferably, the concentration of free ammonia in the ammoniacal ammonium carbonate solution is less than 75 g/L. Still preferably, the concentration of free ammonia in the ammoniacal ammonium carbonate solution is less than 100 g/L. Still preferably, the concentration of free ammonia in the ammoniacal ammonium carbonate solution is less than 150 g/L. Still preferably, the concentration of free ammonia in the ammoniacal ammonium carbonate solution is less than 200 g/L.
  • the concentration of free ammonia in the ammoniacal ammonium carbonate solution is less than 250 g/L. Still preferably, the concentration of free ammonia in the ammoniacal ammonium carbonate solution is less than 300 g/L.
  • the concentration of free ammonia in the ammoniacal ammonium carbonate solution is between 0.1 and 1 g/L.
  • the concentration of free ammonia in the ammoniacal ammonium carbonate solution is between 0.1 and 2 g/L.
  • the concentration of free ammonia in the ammoniacal ammonium carbonate solution is between 0.1 and 3 g/L.
  • the concentration of free ammonia in the ammoniacal ammonium carbonate solution is between 0.1 and 4 g/L.
  • the concentration of free ammonia in the ammoniacal ammonium carbonate solution is between 0.1 and 5 g/L.
  • the concentration of free ammonia in the ammoniacal ammonium carbonate solution is between 0.1 and 7 g/L. Still preferably, the concentration of free ammonia in the ammoniacal ammonium carbonate solution is between 0.1 and 10 g/L. Still preferably, the concentration of free ammonia in the ammoniacal ammonium carbonate solution is between 0.1 and 15 g/L. Still preferably, the concentration of free ammonia in the ammoniacal ammonium carbonate solution is between 0.1 and 20 g/L. Still preferably, the concentration of free ammonia in the ammoniacal ammonium carbonate solution is between 0.1 and 30 g/L.
  • the concentration of free ammonia in the ammoniacal ammonium carbonate solution is between 0.1 and 50 g/L. Still preferably, the concentration of free ammonia in the ammoniacal ammonium carbonate solution is between 0.1 and 60 g/L. Still preferably, the concentration of free ammonia in the ammoniacal ammonium carbonate solution is between 0.1 and 75 g/L. Still preferably, the concentration of free ammonia in the ammoniacal ammonium carbonate solution is between 0.1 and 1 00 g/L. Still preferably, the concentration of free ammonia in the ammoniacal ammonium carbonate solution is between 0.1 and 150 g/L.
  • the concentration of free ammonia in the ammoniacal ammonium carbonate solution is between 0.1 and 200 g/L. Still preferably, the concentration of free ammonia in the ammoniacal ammonium carbonate solution is between 0.1 and 250 g/L. Still preferably, the concentration of free ammonia in the ammoniacal ammonium carbonate solution is between 0.1 and 300 g/L.
  • the concentration of ammonium carbonate in the ammoniacal ammonium carbonate solution is less than 0.1 g/L.
  • the concentration of ammonium carbonate in the ammoniacal ammonium carbonate solution is less than 1 g/L.
  • the concentration of ammonium carbonate in the ammoniacal ammonium carbonate solution is less than 2 g/L.
  • the concentration of ammonium carbonate in the ammoniacal ammonium carbonate solution is less than 3 g/L.
  • the concentration of ammonium carbonate in the ammoniacal ammonium carbonate solution is less than 4 g/L.
  • the concentration of ammonium carbonate in the ammoniacal ammonium carbonate solution is less than 5 g/L. Still preferably, the concentration of ammonium carbonate in the ammoniacal ammonium carbonate solution is less than 7 g/L. Still preferably, the concentration of ammonium carbonate in the ammoniacal ammonium carbonate solution is less than 10 g/L. Still preferably, the concentration of ammonium carbonate in the ammoniacal ammonium carbonate solution is less than 15 g/L. Still preferably, the concentration of ammonium carbonate in the ammoniacal ammonium carbonate solution is less than 20 g/L.
  • the concentration of ammonium carbonate in the ammoniacal ammonium carbonate solution is less than 30 g/L. Still preferably, the concentration of ammonium carbonate in the ammoniacal ammonium carbonate solution is less than 50 g/L. Still preferably, the concentration of ammonium carbonate in the ammoniacal ammonium carbonate solution is less than 60 g/L. Still preferably, the concentration of ammonium carbonate in the ammoniacal ammonium carbonate solution is less than 75 g/L. Still preferably, the concentration of ammonium carbonate in the ammoniacal ammonium carbonate solution is less than 100 g/L.
  • the concentration of ammonium carbonate in the ammoniacal ammonium carbonate solution is less than 150 g/L. Still preferably, the concentration of ammonium carbonate in the ammoniacal ammonium carbonate solution is less than 200 g/L. Still preferably, the concentration of ammonium carbonate in the ammoniacal ammonium carbonate solution is less than 300 g/L. Still preferably, the concentration of ammonium carbonate in the ammoniacal ammonium carbonate solution is less than 500 g/L.
  • the concentration of ammonium carbonate in the ammoniacal ammonium carbonate solution is between 0.5 and 1 g/L.
  • the concentration of ammonium carbonate in the ammoniacal ammonium carbonate solution is between 0.5 and 2 g/L.
  • the concentration of ammonium carbonate in the ammoniacal ammonium carbonate solution is between 0.5 and 3 g/L.
  • the concentration of ammonium carbonate in the ammoniacal ammonium carbonate solution is between 0.5 and 4 g/L.
  • the concentration of ammonium carbonate in the ammoniacal ammonium carbonate solution is between 0.5 and 5 g/L.
  • the concentration of ammonium carbonate in the ammoniacal ammonium carbonate solution is between 0.5 and 7 g/L. Still preferably, the concentration of ammonium carbonate in the ammoniacal ammonium carbonate solution is between 0.5 and 10 g/L. Still preferably, the concentration of ammonium carbonate in the ammoniacal ammonium carbonate solution is between 0.5 and 15 g/L. Still preferably, the concentration of ammonium carbonate in the ammoniacal ammonium carbonate solution is between 0.5 and 20 g/L. Still preferably, the concentration of ammonium carbonate in the ammoniacal ammonium carbonate solution is between 0.5 and 30 g/L.
  • the concentration of ammonium carbonate in the ammoniacal ammonium carbonate solution is between 0.5 and 50 g/L. Still preferably, the concentration of ammonium carbonate in the ammoniacal ammonium carbonate solution is between 0.5 and 60 g/L. Still preferably, the concentration of ammonium carbonate in the ammoniacal ammonium carbonate solution is between 0.5 and 75 g/L. Still preferably, the concentration of ammonium carbonate in the ammoniacal ammonium carbonate solution is between 0.5 and 100 g/L. Still preferably, the concentration of ammonium carbonate in the ammoniacal ammonium carbonate solution is between 0.5 and 150 g/L.
  • the concentration of ammonium carbonate in the ammoniacal ammonium carbonate solution is between 0.5 and 200 g/L. Still preferably, the concentration of ammonium carbonate in the ammoniacal ammonium carbonate solution is between 0.5 and 300 g/L. Still preferably, the concentration of ammonium carbonate in the ammoniacal ammonium carbonate solution is between 0.5 and 500 g/L.
  • the concentration of carbonate in the ammoniacal ammonium carbonate solution is less than 0.1 g/L.
  • the concentration of carbonate in the ammoniacal ammonium carbonate solution is less than 1 g/L.
  • the concentration of carbonate in the ammoniacal ammonium carbonate solution is less than 2 g/L.
  • the concentration of carbonate in the ammoniacal ammonium carbonate solution is less than 3 g/L.
  • the concentration of carbonate in the ammoniacal ammonium carbonate solution is less than 4 g/L.
  • the concentration of carbonate in the ammoniacal ammonium carbonate solution is less than 5 g/L.
  • the concentration of carbonate in the ammoniacal ammonium carbonate solution is less than 7 g/L. Still preferably, the concentration of carbonate in the ammoniacal ammonium carbonate solution is less than 10 g/L. Still preferably, the concentration of carbonate in the ammoniacal ammonium carbonate solution is less than 1 5 g/L. Still preferably, the concentration of carbonate in the ammoniacal ammonium carbonate solution is less than 20 g/L. Still preferably, the concentration of carbonate in the ammoniacal ammonium carbonate solution is less than 30 g/L. Still preferably, the concentration of carbonate in the ammoniacal ammonium carbonate solution is less than 50 g/L.
  • the concentration of carbonate in the ammoniacal ammonium carbonate solution is less than 60 g/L. Still preferably, the concentration of carbonate in the ammoniacal ammonium carbonate solution is less than 75 g/L. Still preferably, the concentration of carbonate in the ammoniacal ammonium carbonate solution is less than 1 00 g/L. Still preferably, the concentration of carbonate in the ammoniacal ammonium carbonate solution is less than 150 g/L. Still preferably, the concentration of carbonate in the ammoniacal ammonium carbonate solution is less than 200 g/L. Still preferably, the concentration of carbonate in the ammoniacal ammonium carbonate solution is less than 250 g/L. Still preferably, the concentration of carbonate in the ammoniacal ammonium carbonate solution is less than 350 g/L. Still preferably, the concentration of carbonate in the ammoniacal ammonium carbonate solution is less than 500 g/L.
  • the concentration of carbonate in the ammoniacal ammonium carbonate solution is between 0.5 and 1 g/L.
  • the concentration of carbonate in the ammoniacal ammonium carbonate solution is between 0.5 and 2 g/L.
  • the concentration of carbonate in the ammoniacal ammonium carbonate solution is between 0.5 and 3 g/L.
  • the concentration of carbonate in the ammoniacal ammonium carbonate solution is between 0.5 and 4 g/L.
  • the concentration of carbonate in the ammoniacal ammonium carbonate solution is between 0.5 and 5 g/L.
  • the concentration of carbonate in the ammoniacal ammonium carbonate solution is between 0.5 and 7 g/L. Still preferably, the concentration of carbonate in the ammoniacal ammonium carbonate solution is between 0.5 and 10 g/L. Still preferably, the concentration of carbonate in the ammoniacal ammonium carbonate solution is between 0.5 and 15 g/L. Still preferably, the concentration of carbonate in the ammoniacal ammonium carbonate solution is between 0.5 and 20 g/L. Still preferably, the concentration of carbonate in the ammoniacal ammonium carbonate solution is between 0.5 and 30 g/L. Still preferably, the concentration of carbonate in the ammoniacal ammonium carbonate solution is between 0.5 and 50 g/L.
  • the concentration of carbonate in the ammoniacal ammonium carbonate solution is between 0.5 and 60 g/L. Still preferably, the concentration of carbonate in the ammoniacal ammonium carbonate solution is between 0.5 and 75 g/L. Still preferably, the concentration of carbonate in the ammoniacal ammonium carbonate solution is between 0.5 and 100 g/L. Still preferably, the concentration of carbonate in the ammoniacal ammonium carbonate solution is between 0.5 and 150 g/L. Still preferably, the concentration of carbonate in the ammoniacal ammonium carbonate solution is between 0.5 and 200 g/L. Still preferably, the concentration of carbonate in the ammoniacal ammonium carbonate solution is between 0.5 and 250 g/L.
  • the concentration of carbonate in the ammoniacal ammonium carbonate solution is between 0.5 and 350 g/L. Still preferably, the concentration of carbonate in the ammoniacal ammonium carbonate solution is between 0.5 and 500 g/L.
  • controlling will be understood to include any steps that could be taken to ensure that the molar ratio of carbonate to zinc in the aqueous ammoniacal ammonium carbonate zinc solution is within the required range.
  • methods of controlling the molar ratio of carbonate to zinc in the aqueous ammoniacal ammonium carbonate zinc solution include, but are not limited to: adding a soluble carbonate salt, such as those of sodium, potassium or ammonium; and passing gaseous carbon dioxide through the solution.
  • the molar ratio of carbonate to zinc in the aqueous solution is less than 0.1 .
  • the molar ratio of carbonate to zinc in the aqueous solution is less than 0.25. Still preferably, the molar ratio of carbonate to zinc in the aqueous solution is less than 0.50. Still preferably, the molar ratio of carbonate to zinc in the aqueous solution is less than 0.75. Still preferably, the molar ratio of carbonate to zinc in the aqueous solution is less than 0.9. Still preferably, the molar ratio of carbonate to zinc in the aqueous solution is less than 1 .0. Still preferably, the molar ratio of carbonate to zinc in the aqueous solution is less than 1 .1 .
  • the molar ratio of carbonate to zinc in the aqueous solution is less than 1 .25. Still preferably, the molar ratio of carbonate to zinc in the aqueous solution is less than 1 .5. Still preferably, the molar ratio of carbonate to zinc in the aqueous solution is less than 2.0.
  • the molar ratio of carbonate to zinc in the aqueous solution is between 0.05 and 0.1 .
  • the molar ratio of carbonate to zinc in the aqueous solution is between 0.05 and 0.25.
  • the molar ratio of carbonate to zinc in the aqueous solution is between 0.05 and 0.50.
  • the molar ratio of carbonate to zinc in the aqueous solution is between 0.05 and 0.75.
  • the molar ratio of carbonate to zinc in the aqueous solution is between 0.05 and 0.9.
  • the molar ratio of carbonate to zinc in the aqueous solution is between 0.05 and 1 .0.
  • the molar ratio of carbonate to zinc in the aqueous solution is between 0.05 and 1 .1 . Still preferably, the molar ratio of carbonate to zinc in the aqueous solution is between 0.05 and 1 .1 . Still preferably, the molar ratio of carbonate to zinc in the aqueous solution is between 0.05 and 1 .25. Still preferably, the molar ratio of carbonate to zinc in the aqueous solution is between 0.05 and 1 .5. Still preferably, the molar ratio of carbonate to zinc in the aqueous solution is between 0.05 and 2.0.
  • the molar ratio of carbonate to zinc in the aqueous solution is between 0.1 and 1 .0.
  • the molar ratio of carbonate to zinc in the aqueous solution is between 0.25 and 1 .0. More preferably, the molar ratio of carbonate to zinc in the aqueous solution is between 0.5 and 1 .0. Still preferably, the molar ratio of carbonate to zinc in the aqueous solution is between 0.75 and 1 .0. Still preferably, the molar ratio of carbonate to zinc in the aqueous solution is between 0.9 and 1 .0. Still preferably, the molar ratio of carbonate to zinc in the aqueous solution is between 0.95 and 1 .0.
  • the molar ratio of carbonate to zinc in the aqueous solution is between 0.1 and 1 .1 .
  • the molar ratio of carbonate to zinc in the aqueous solution is between 0.25 and 1 .1 . More preferably, the molar ratio of carbonate to zinc in the aqueous solution is between 0.5 and 1 .1 . Still preferably, the molar ratio of carbonate to zinc in the aqueous solution is between 0.75 and 1 .1 . Still preferably, the molar ratio of carbonate to zinc in the aqueous solution is between 0.9 and 1 .1 . Still preferably, the molar ratio of carbonate to zinc in the aqueous solution is between 0.95 and 1 .1 .
  • the molar ratio of carbonate to zinc in the aqueous solution is between 0.1 and 1 .5.
  • the molar ratio of carbonate to zinc in the aqueous solution is between 0.25 and 1 .5. More preferably, the molar ratio of carbonate to zinc in the aqueous solution is between 0.5 and 1 .5. Still preferably, the molar ratio of carbonate to zinc in the aqueous solution is between 0.75 and 1 .5. Still preferably, the molar ratio of carbonate to zinc in the aqueous solution is between 0.9 and 1 .5. Still preferably, the molar ratio of carbonate to zinc in the aqueous solution is between 0.95 and 1 .5.
  • the molar ratio of carbonate to zinc in the aqueous solution is between 0.1 and 2.0.
  • the molar ratio of carbonate to zinc in the aqueous solution is between 0.25 and 2.0. More preferably, the molar ratio of carbonate to zinc in the aqueous solution is between 0.5 and 2.0. Still preferably, the molar ratio of carbonate to zinc in the aqueous solution is between 0.75 and 2.0. Still preferably, the molar ratio of carbonate to zinc in the aqueous solution is between 0.9 and 2.0. Still preferably, the molar ratio of carbonate to zinc in the aqueous solution is between 0.95 and 2.0.
  • the molar ratio of carbonate to zinc in the aqueous solution can be determined using any method available to those skilled in the art.
  • the content of zinc and carbonate in the aqueous phase can be determined by taking an aliquot of the solution and measuring the zinc concentration using, for example, an atomic absorption spectrometer.
  • Carbonate can be measured gravi metrically by precipitation using barium ions or by a pH titration.
  • the molar ratio of ammonia to zinc in the aqueous solution is less than
  • the molar ratio of ammonia to zinc in the aqueous solution is less than
  • the molar ratio of ammonia to zinc in the aqueous solution is less than
  • the molar ratio of ammonia to zinc in the aqueous solution is less than
  • the molar ratio of ammonia to zinc in the aqueous solution is less than
  • the molar ratio of ammonia to zinc in the aqueous solution is less than
  • the molar ratio of ammonia to zinc in the aqueous solution is less than
  • the molar ratio of ammonia to zinc in the aqueous solution is less than
  • the molar ratio of ammonia to zinc in the aqueous solution is less than
  • the molar ratio of ammonia to zinc in the aqueous solution is less than
  • the molar ratio of ammonia to zinc in the aqueous solution is less than
  • the molar ratio of ammonia to zinc in the aqueous solution is less than
  • the molar ratio of ammonia to zinc in the aqueous solution is less than
  • the molar ratio of ammonia to zinc in the aqueous solution is less than
  • the molar ratio of ammonia to zinc in the aqueous solution is less than
  • the molar ratio of ammonia to zinc in the aqueous solution is less than
  • the molar ratio of ammonia to zinc in the aqueous solution is between 0.05 and 0.1 .
  • the molar ratio of ammonia to zinc in the aqueous solution is between 0.05 and 0.25.
  • the molar ratio of ammonia to zinc in the aqueous solution is between 0.05 and 0.50.
  • the molar ratio of ammonia to zinc in the aqueous solution is between 0.05 and 0.75.
  • the molar ratio of ammonia to zinc in the aqueous solution is between 0.05 and 0.9.
  • the molar ratio of ammonia to zinc in the aqueous solution is between 0.05 and 1 .0.
  • the molar ratio of ammonia to zinc in the aqueous solution is between 0.05 and 1 .1 .
  • the molar ratio of ammonia to zinc in the aqueous solution is between 0.05 and 1 .25.
  • the molar ratio of ammonia to zinc in the aqueous solution is between 0.05 and 1 .5.
  • the molar ratio of ammonia to zinc in the aqueous solution is between 0.05 and 2.0.
  • the molar ratio of ammonia to zinc in the aqueous solution is between 0.05 and 3.0.
  • the molar ratio of ammonia to zinc in the aqueous solution is between 0.05 and 5.0.
  • the molar ratio of ammonia to zinc in the aqueous solution is between 0.05 and 1 0.0.
  • the molar ratio of ammonia to zinc in the aqueous solution is between 0.05 and 20.0.
  • the molar ratio of ammonia to zinc in the aqueous solution is between 0.05 and 50.0.
  • the molar ratio of ammonia to zinc in the aqueous solution is between 0.05 and 100.0.
  • the zinc extractant is selected from the group: liquid organophosphorus extractant, liquid oxime extractant, carboxylic acid extractant and combinations thereof.
  • the molecular formula of the carboxylic acid extractant contains 6-14 carbon atoms. In a preferred form of the invention, the molecular formula of the carboxylic acid extractant contains 8-12 carbon atoms.
  • the oxime extractant is selected from an aldoxime, a ketoxime or a mixture of both.
  • the organophosphorus extractant is a derivative of phosphoric, phosphonic, phosphinic or dithiophosphinic acid.
  • the organophosphorus extractant is Bis(2-ethylhexyl) hydrogen phosphate (also known as, Bis(2-ethylhexyl) phosphoric acid, Bis(2-ethylhexyl) phosphate, Bis(2- ethylhexyl) hydrophosphoric acid, BEHPA, BEHP, BEHHPA, BEHHP, Di-(2-ethylhexyl) phosphoric acid, D2EHPA, D2EHPA, (C 8 H 7 0) 2 P0 2 H and has the CAS Number 298- 07-7).
  • Bis(2-ethylhexyl) hydrogen phosphate also known as, Bis(2-ethylhexyl) phosphoric acid, Bis(2-ethylhexyl) phosphate, Bis(2- ethylhexyl) hydrophosphoric acid, BEHPA, BEHP, BEHHPA, BEHHP, Di-(2-ethylhexyl) phosphoric
  • the species extracted from other aqueous media has two molecules of the organic extractant per divalent metal ion
  • the species extracted from ammoniacal ammonium carbonate solution is understood to extract with only one molecule of the extractant, with the charge being balanced by another monovalent anion in the system, such as hydrogen carbonate (bicarbonate),
  • the molar ratio of ammonia to zinc in the aqueous ammoniacal ammonium carbonate zinc solution is four, or greater.
  • the molar ratio of ammonia to zinc in the aqueous ammoniacal ammonium carbonate zinc solution is four, or greater, the zinc in the aqueous ammoniacal ammonium carbonate zinc solution will be present as the tetraamine complex ion Zn(NH3) 4 2+ .
  • the molar ratio of carbonate to zinc in the aqueous ammoniacal ammonium carbonate zinc solution is one, or greater.
  • At least 1 0% of the zinc species present in the organic solution is in the form of ZnRHC0 3 . More preferably, at least 20% of the zinc species present in the organic solution is in the form of ZnRHCOs. Still preferably, at least 30% of the zinc species present in the organic solution is in the form of ZnRHC0 3 . Still preferably, at least 40% of the zinc species present in the organic solution is in the form of ZnRHC0 3 . Still preferably, at least 50% of the zinc species present in the organic solution is in the form of ZnRHC0 3 . Still preferably, at least 60% of the zinc species present in the organic solution is in the form of ZnRHC0 3 .
  • At least 70% of the zinc species present in the organic solution is in the form of ZnRHC0 3 .
  • at least 80% of the zinc species present in the organic solution is in the form of ZnRHC0 3 .
  • at least 90% of the zinc species present in the organic solution is in the form of ZnRHC0 3 .
  • at least 95% of the zinc species present in the organic solution is in the form of ZnRHC0 3 .
  • at least 99% of the zinc species present in the organic solution is in the form of ZnRHC0 3 .
  • 100% of the zinc species present in the organic solution is in the form of ZnRHC0 3 .
  • the molar ratio of ammonia to zinc to carbonate in the aqueous ammoniacal ammonium carbonate zinc solution is about 4:1 :1 .
  • the concentration of zinc extractant in the organic solution is less than 0.1 vol%.
  • the concentration of zinc extractant in the organic solution is less than 1 vol%.
  • the concentration of zinc extractant in the organic solution is less than 2vol%.
  • the concentration of zinc extractant in the organic solution is less than 3vol%.
  • the concentration of zinc extractant in the organic solution is less than 4vol%.
  • the concentration of zinc extractant in the organic solution is less than 5vol%.
  • the concentration of zinc extractant in the organic solution is less than 7vol%.
  • the concentration of zinc extractant in the organic solution is less than 10vol%.
  • the concentration of zinc extractant in the organic solution is less than 15vol%. Still preferably, the concentration of zinc extractant in the organic solution is less than 20vol%. Still preferably, the concentration of zinc extractant in the organic solution is less than 30vol%. Still preferably, the concentration of zinc extractant in the organic solution is less than 40vol%. Still preferably, the concentration of zinc extractant in the organic solution is less than 50vol%. Still preferably, the concentration of zinc extractant in the organic solution is less than 60vol%. Still preferably, the concentration of zinc extractant in the organic solution is less than 70vol%. Still preferably, the concentration of zinc extractant in the organic solution is less than 80vol%.
  • the concentration of zinc extractant in the organic solution is between 0.5 and 1 vol%.
  • the concentration of zinc extractant in the organic solution is between 0.5 and 2vol%.
  • the concentration of zinc extractant in the organic solution is between 0.5 and 3vol%.
  • the concentration of zinc extractant in the organic solution is between 0.5 and 4vol%.
  • the concentration of zinc extractant in the organic solution is between 0.5 and 5vol%.
  • the concentration of zinc extractant in the organic solution is between 0.5 and 7vol%.
  • the concentration of zinc extractant in the organic solution is between 0.5 and 10vol%.
  • the concentration of zinc extractant in the organic solution is between 0.5 and 15vol%.
  • the concentration of zinc extractant in the organic solution is between 0.5 and 20vol%. Still preferably, the concentration of zinc extractant in the organic solution is between 0.5 and 30vol%. Still preferably, the concentration of zinc extractant in the organic solution is between 0.5 and 40vol%. Still preferably, the concentration of zinc extractant in the organic solution is between 0.5 and 50vol%. Still preferably, the concentration of zinc extractant in the organic solution is between 0.5 and 60vol%. Still preferably, the concentration of zinc extractant in the organic solution is between 0.5 and 70vol%. Still preferably, the concentration of zinc extractant in the organic solution is between 0.5 and 80vol%.
  • the method further comprises the step of: adding a phase modifier to the organic solution of a zinc extractant prior to the step of:
  • the concentration of the phase modifier is less than 0.1 vol%.
  • the concentration of the phase modifier is less than 1 vol%.
  • the concentration of the phase modifier is less than 2.5vol%.
  • the concentration of the phase modifier is less than 5vol%.
  • the concentration of the phase modifier is less than 7.5vol%.
  • the concentration of the phase modifier is less than 10vol%.
  • the concentration of the phase modifier is less than 15vol%.
  • the concentration of the phase modifier is less than 20vol%.
  • the concentration of the phase modifier is 0.1 1 -50vol%. Still preferably, the concentration of the phase modifier is 1 -50vol%. Still preferably, the concentration of the phase modifier is 2.5- 50vol%. Still preferably, the concentration of the phase modifier is 5-50vol%. Still preferably, the concentration of the phase modifier is 7.5-50vol%. Still preferably, the concentration of the phase modifier is 10-50vol%. Still preferably, the concentration of the phase modifier is 15-50vol%.
  • the phase modifier is an organic alcohol.
  • the organic alcohol is selected from the group: 1 -decanol, 2-ethyl hexanol, and p-nonyl phenol.
  • the phase modifier is isodecanol (1 -decanol, decan-1 -ol, CAS 1 12-30-1 , C10H22O).
  • the phase modifier is trioctyl phosphine oxide (TOPO).
  • the phase modifier is tributyl phosphate (TBP, CAS 1 26-73-8, C12H27O4P).
  • the organic solution of a zinc extractant comprises a zinc extractant and a diluent.
  • the diluent is >50% aliphatic.
  • the diluent is >60% aliphatic.
  • the diluent is >70% aliphatic.
  • the diluent is >80% aliphatic.
  • the diluent is >90% aliphatic Still, preferably, the diluent is >95% aliphatic.
  • the diluent is 50-100% aliphatic. Still preferably, the diluent is 60-100% aliphatic. Still preferably, the diluent is 70-100% aliphatic. Still preferably, the diluent is 80-1 00% aliphatic. Still preferably, the diluent is 90-1 00% aliphatic. Still preferably, the diluent is 95-1 00% aliphatic.
  • the diluent is kerosene.
  • the molar ratio of carbonate to zinc in the organic solution is less than 0.1 .
  • the molar ratio of carbonate to zinc in the organic solution is less than 0.25.
  • the molar ratio of carbonate to zinc in the organic solution is less than 0.50.
  • the molar ratio of carbonate to zinc in the organic solution is less than 0.75.
  • the molar ratio of carbonate to zinc in the organic solution is less than 0.9.
  • the molar ratio of carbonate to zinc in the organic solution is less than 1 .0.
  • the molar ratio of carbonate to zinc in the organic solution is less than 1 .1 .
  • the molar ratio of carbonate to zinc in the organic solution is less than 1 .25. Still preferably, the molar ratio of carbonate to zinc in the organic solution is less than 1 .5. Still preferably, the molar ratio of carbonate to zinc in the organic solution is less than 2.0. Still preferably, the molar ratio of carbonate to zinc in the organic solution is less than 3.0. Still preferably, the molar ratio of carbonate to zinc in the organic solution is less than 5.0. Still preferably, the molar ratio of carbonate to zinc in the organic solution is less than 10.0. Still preferably, the molar ratio of carbonate to zinc in the organic solution is less than 20.0.
  • the molar ratio of carbonate to zinc in the organic solution is between 0.05 and 0.1 .
  • the molar ratio of carbonate to zinc in the organic solution is between 0.05 and 0.25.
  • the molar ratio of carbonate to zinc in the organic solution is between 0.05 and 0.50.
  • the molar ratio of carbonate to zinc in the organic solution is between 0.05 and 0.75.
  • the molar ratio of carbonate to zinc in the organic solution is between 0.05 and 0.9.
  • the molar ratio of carbonate to zinc in the organic solution is between 0.05 and 1 .0.
  • the molar ratio of carbonate to zinc in the organic solution is between 0.05 and 1 .1 . Still preferably, the molar ratio of carbonate to zinc in the organic solution is between 0.05 and 1 .25. Still preferably, the molar ratio of carbonate to zinc in the organic solution is between 0.05 and 1 .5. Still preferably, the molar ratio of carbonate to zinc in the organic solution is between 0.05 and 2.0. Still preferably, the molar ratio of carbonate to zinc in the organic solution is between 0.05 and 3.0. Still preferably, the molar ratio of carbonate to zinc in the organic solution is between 0.05 and 5.0. Still preferably, the molar ratio of carbonate to zinc in the organic solution is between 0.05 and 10.0. Still preferably, the molar ratio of carbonate to zinc in the organic solution is between 0.05 and 20.0.
  • the molar ratio of carbonate to zinc in the organic solution is between 0.05 and 2.0. Still preferably, the molar ratio of carbonate to zinc in the organic solution is between 0.25 and 2.0. Still preferably, the molar ratio of carbonate to zinc in the organic solution is between 0.5 and 2.0. Still preferably, the molar ratio of carbonate to zinc in the organic solution is between 0.5 and 1 .5. Still preferably, the molar ratio of carbonate to zinc in the organic solution is between 0.75 and 1 .25. Still preferably, the molar ratio of carbonate to zinc in the organic solution is between 0.9 and 1 .1 . Still preferably, the molar ratio of carbonate to zinc in the organic solution is between 0.95 and 1 .05.
  • the molar ratio of carbonate to zinc in the organic solution can be determined using any method available to those skilled in the art.
  • the content of zinc and carbonate in the organic phase can be determined by taking an aliquot of the organic solution and mixing it thoroughly with a larger volume of 150 g/L sulphuric acid, ensuring that any gaseous carbon dioxide evolved is captured.
  • the phases should then be allowed to separate and an analysis of the aqueous phase for zinc and carbonate ions using standard methods may be performed. To ensure that all of the zinc and carbonate have been stripped, further contacts with fresh 150 g/L sulphuric acid may be required. This method gives the zinc and carbonate concentrations in the organic directly and this data can be used to determine the molar ratio of Zn:C0 3 in the organic.
  • the molar ratio of ammonia to zinc in the organic solution is less than
  • the molar ratio of ammonia to zinc in the organic solution is less than
  • the molar ratio of ammonia to zinc in the organic solution is less than
  • the molar ratio of ammonia to zinc in the organic solution is less than
  • the molar ratio of ammonia to zinc in the organic solution is less than
  • the molar ratio of ammonia to zinc in the organic solution is less than
  • the molar ratio of ammonia to zinc in the organic solution is less than
  • the molar ratio of ammonia to zinc in the organic solution is less than
  • the molar ratio of ammonia to zinc in the organic solution is less than
  • the molar ratio of ammonia to zinc in the organic solution is less than
  • the molar ratio of ammonia to zinc in the organic solution is less than
  • the molar ratio of ammonia to zinc in the organic solution is less than
  • the molar ratio of ammonia to zinc in the organic solution is less than
  • the molar ratio of ammonia to zinc in the organic solution is less than
  • the molar ratio of ammonia to zinc in the organic solution is less than
  • the molar ratio of ammonia to zinc in the organic solution is less than
  • the molar ratio of ammonia to zinc in the organic solution is less than
  • the molar ratio of ammonia to zinc in the organic solution is less than
  • the molar ratio of ammonia to zinc in the organic solution is between 0.001 and 0.1 .
  • the molar ratio of ammonia to zinc in the organic solution is between 0.001 and 0.25.
  • the molar ratio of ammonia to zinc in the organic solution is between 0.001 and 0.50.
  • the molar ratio of ammonia to zinc in the organic solution is between 0.001 and 0.75.
  • the molar ratio of ammonia to zinc in the organic solution is between 0.001 and 0.9.
  • the molar ratio of ammonia to zinc in the organic solution is between 0.001 and 1 .0.
  • the molar ratio of ammonia to zinc in the organic solution is between 0.001 and 1 .1 .
  • the molar ratio of ammonia to zinc in the organic solution is between 0.001 and 1 .25.
  • the molar ratio of ammonia to zinc in the organic solution is between 0.001 and 1 .5.
  • the molar ratio of ammonia to zinc in the organic solution is between 0.001 and 2.0.
  • the molar ratio of ammonia to zinc in the organic solution is between 0.001 and 3.0.
  • the molar ratio of ammonia to zinc in the organic solution is between 0.001 and 5.0.
  • the molar ratio of ammonia to zinc in the organic solution is between 0.001 and 1 0.0.
  • the molar ratio of ammonia to zinc in the organic solution is between 0.001 and 20.0.
  • the molar ratio of zinc to the zinc extractant in the organic solution is less than 0.1 .
  • the molar ratio of zinc to the zinc extractant in the organic solution is less than 0.25.
  • the molar ratio of zinc to the zinc extractant in the organic solution is less than 0.50.
  • the molar ratio of zinc to the zinc extractant in the organic solution is less than 0.75.
  • the molar ratio of zinc to the zinc extractant in the organic solution is less than 0.9.
  • the molar ratio of zinc to the zinc extractant in the organic solution is less than 1 .0.
  • the molar ratio of zinc to the zinc extractant in the organic solution is less than 1 .1 . Still preferably, the molar ratio of zinc to the zinc extractant in the organic solution is less than 1 .25. Still preferably, the molar ratio of zinc to the zinc extractant in the organic solution is less than 1 .5. Still preferably, the molar ratio of zinc to the zinc extractant in the organic solution is less than 2.0. Still preferably, the molar ratio of zinc to the zinc extractant in the organic solution is less than 3.0. Still preferably, the molar ratio of zinc to the zinc extractant in the organic solution is less than 5.0. Still preferably, the molar ratio of zinc to the zinc extractant in the organic solution is less than 10.0. Still preferably, the molar ratio of zinc to the zinc extractant in the organic solution is less than 20.0.
  • the molar ratio of zinc to the zinc extractant in the organic solution is between 0.05 and 0.1 .
  • the molar ratio of zinc to the zinc extractant in the organic solution is between 0.05 and 0.25.
  • the molar ratio of zinc to the zinc extractant in the organic solution is between 0.05 and 0.50.
  • the molar ratio of zinc to the zinc extractant in the organic solution is between 0.05 and 0.75.
  • the molar ratio of zinc to the zinc extractant in the organic solution is between 0.05 and 0.9.
  • the molar ratio of zinc to the zinc extractant in the organic solution is between 0.05 and 1 .0.
  • the molar ratio of zinc to the zinc extractant in the organic solution is between 0.05 and 1 .1 . Still preferably, the molar ratio of zinc to the zinc extractant in the organic solution is between 0.05 and 1 .25. Still preferably, the molar ratio of zinc to the zinc extractant in the organic solution is between 0.05 and 1 .5. Still preferably, the molar ratio of zinc to the zinc extractant in the organic solution is between 0.05 and 2.0.
  • the molar ratio of zinc to the zinc extractant in the organic solution is between 0.1 and 1 .1 .
  • the molar ratio of zinc to the zinc extractant in the organic solution is between 0.25 and 1 .1 .
  • the molar ratio of zinc to the zinc extractant in the organic solution is between 0.5 and 1 .1 .
  • the molar ratio of zinc to the zinc extractant in the organic solution is between 0.75 and 1 .1 .
  • the molar ratio of zinc to the zinc extractant in the organic solution is between 0.9 and 1 .1 .
  • the molar ratio of zinc to the zinc extractant in the organic solution is between 0.95 and 1 .05.
  • the concentration of zinc in the aqueous ammoniacal ammonium carbonate zinc solution is preferably 20-25 g/L; the concentration of ammonia in the aqueous ammoniacal ammonium carbonate zinc solution is preferably 21 -26 g/L; the concentration of carbonate in the aqueous ammoniacal ammonium carbonate zinc solution is preferably 18-23 g/L; the concentration of the organic solution of a zinc extractant is 30-40vol%; the concentration of the phase modifier is 5-10vol%; the diluent used is greater than 98% aliphatic; the molar ratio of zinc extractant to zinc in the organic solution is 0.95 to1 .05; and the molar ratio of carbonate to zinc in the organic solution is 0.95 to 1 .05, the zinc species present in the
  • Figure 1 is a flow diagram representing the method of the embodiment, in the context of an aqueous ammoniacal zinc solution produced by the ammoniacal leaching of a zinc carbonate ore;
  • Figure 2 is a graphical representation of the loading isotherms for Zn and CO3 ions from the high carbonate solution of Example 1 ;
  • Figure 3 is a graphical representation of the loading isotherms for Zn and C0 3 ions from the low carbonate solution of Example 2;
  • Figure 5 is a graphical representation of the Zn/D2EHPA ratios for isotherms of Figure 4; and Figure 6 is a graphical representation of the zinc extraction as a function of equilibrium pH after 1 , 2 and 3 contacts in the trials of Example 4.
  • a zinc ore 20 is leached 10 in an ammoniacal ammonium carbonate solution 62 to produce a slurry 27 comprising an aqueous zinc ammoniacal ammonium carbonate solution containing impurities and a zinc-depleted solid, the slurry is subjected to solid- liquid separation 1 1 , to produce a solid waste 41 , which is disposed of, and an impurity- containing zinc ammoniacal ammonium carbonate solution 30.
  • the aqueous impurity- containing zinc ammoniacal ammonium carbonate solution 30 is then introduced into a solvent extraction loading stage 1 2, in which the aqueous impurity-containing zinc ammoniacal ammonium carbonate solution 30 is contacted with an organic solution of a zinc extractant, in the form of D2EHPA, dissolved in an aliphatic 43.
  • a zinc extractant in the form of D2EHPA, dissolved in an aliphatic 43.
  • the zinc, some impurities and some ammonia are transferred into the organic phase, thereby producing a zinc-depleted impurity-depleted ammonia-depleted aqueous ammoniacal ammonium carbonate solution 60 and a zinc-enriched impurity-enriched ammonia-enriched organic solution of a zinc extractant 33 which are then separated.
  • the zinc-depleted impurity- depleted ammonia-depleted aqueous ammoniacal ammonium carbonate solution 60 is largely recycled back to the leach with a small volume 31 used to absorb the carbon dioxide 59 evolved during the zinc strip 15 forming a carbonic acid solution 32.
  • the impurity-enriched ammonia-enriched zinc-enriched organic solution of a zinc extractant 22 proceeds to an ammonia scrub extraction 13.
  • the impurity-enriched ammonia-enriched zinc-enriched organic solution of a zinc extractant 33 is contacted with an acidic solution of carbonic acid 32, thereby producing an impurity-enriched ammonia-depleted zinc-enriched organic solution 47 and an ammoniacal ammonium carbonate solution 61 , which is combined with the raffinate 60 from the SX loading stage 12 to form an ammoniacal ammonium carbonate solution 62 which is recycled back to the leach stage 1 0.
  • the impurity-enriched ammonia-depleted zinc-enriched organic solution 47 is then contacted with an acidic aqueous solution containing zinc 56 in an impurity scrub stage 14 forming an acidic aqueous solution containing zinc and impurities 58, which can be disposed of and an impurity-depleted ammonia-depleted zinc-enriched organic solution of a zinc extractant 49.
  • the impurity- depleted ammonia-depleted zinc-enriched organic solution of a zinc extractant 49 proceeds to a zinc strip stage 1 5 where it is contacted with a strongly acidic solution 51 producing a zinc-enriched acid aqueous phase 52, an impurity-depleted ammonia- depleted zinc-depleted organic solution of a zinc extractant 43 and carbon dioxide 59.
  • the zinc-enriched acid aqueous phase 52 proceeds to zinc electrowinning 1 6 where zinc cathodes 53 are produced.
  • the impurity-depleted ammonia-depleted zinc-depleted organic solution of a zinc extractant 43 is recycled back to the SX loading stage 12.
  • the carbon dioxide 59 is absorbed into an aqueous solution 31 and the resultant solution 32 used in the ammonia scrub 13.
  • a zinc silicate ore was leached with an ammoniacal ammonium carbonate solution consisting of -25 g/L free ammonia and ⁇ 8 g/L of ammonium carbonate. After 24h of leaching, the solution was separated by filtration, the zinc tenor of this solution was 4.67 g/L.
  • An organic phase comprising 1 00mL of D2EHPA diluted to 1 .00L with aliphatic kerosene (Recosol V80), giving a solution containing 0.303M D2EHPA, was made up.
  • Example 1 The leaching run in Example 1 was repeated using -1 g/L of ammonium carbonate, this being the only difference between the two runs.
  • the solution tenor for zinc of 4.60 g/L is very close to that from Example 1 , evidently, the level of carbonate ions in the leach solution has little effect on the extent of leaching from this ore.
  • the extraction process and analyses were also repeated to give the isotherms shown in Figure 3.
  • a zinc bearing ammoniacal ammonium carbonate solution was made by leaching a dolomite ((Ca,Mg)C0 3 ) hosted smithsonite (ZnC0 3 ) ore in an ammoniacal solution for 24h. After this time the solution was filtered to eliminate solids. The resultant solution contained 1 9 g/L of zinc, 30 g/L of total ammonia (i.e. ammonia + ammonium) and ⁇ 29g of carbonate ions. This gives a carbonate to zinc molar ratio of 1 .04.
  • Two organic solutions were prepared with either 40 or 60vol% D2EHPA in addition to 5vol% TBP, the balance being kerosene. The aqueous and organic solutions were shaken together at different volume ratios, allowed to settle and the aqueous solution analysed for zinc. The zinc concentration in the organic solution was calculated by difference.
  • Figure 4 show the extraction isotherms for 40 and 60vol% D2EHPA along with the isotherm for 10vol% in high carbonate solution from Example 1 .
  • the experimental data are shown as points, the lines show a Langmuir isotherm calculated from the data.
  • the composition of the species present in the organic solution at saturation can be determined from the maxima of the Langmuir isotherms.
  • the molar ratio of zinc to D2EHPA in the organic phase can be calculated. 40vol% D2EHPA is -1 .21 M, 83 g/L Zn is 1 .27M, thus the molar ratio Zn/D2EHPA is 1 .05. Similarly, in the 60vol% D2EHPA run, the ratio is 1 .02. Accordingly, it appears that the zinc species extracted from ammoniacal ammonium carbonate can be summarised as ZnR, which is significantly different to the ZnR 2 species extracted from other aqueous media.
  • the Langmuir isotherm can also be used to determine the Zn/D2EHPA ratio for any level of loading of the organic. This data is shown in Figure 5 for all three isotherms from Figure 3.
  • the D2EHPA molecules attach to opposite sides of a square plane surrounding the zinc effectively forming a much longer chain, which a structural formula of R-Zn-R.
  • the longer chains more readily become entangled raising the viscosity to the point where it is too high for industrial use.

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Abstract

La présente invention concerne un procédé de récupération de zinc à partir d'une solution ammoniacale aqueuse de zinc et de carbonate d'ammonium. Le procédé comprend les étapes consistant à : mettre la solution ammoniacale aqueuse de zinc et de carbonate d'ammonium en contact avec une solution organique d'un agent d'extraction de zinc de telle sorte qu'une partie du zinc est transférée à partir de la solution ammoniacale aqueuse de zinc et de carbonate d'ammonium, ce qui produit une solution ammoniacale aqueuse de carbonate d'ammonium appauvrie en zinc et une solution organique enrichie en zinc d'un agent d'extraction de zinc ; séparer la solution organique enrichie en zinc d'un agent d'extraction de zinc de la solution ammoniacale aqueuse de carbonate d'ammonium appauvrie en zinc ; mettre la solution organique enrichie en zinc en contact avec une solution acide aqueuse, ce qui produit une solution acide aqueuse enrichie en zinc et une solution organique appauvrie en zinc d'un agent d'extraction de zinc ; et récupérer du zinc à partir de la solution acide aqueuse enrichie en zinc.
PCT/AU2016/050926 2015-09-29 2016-09-29 Procédé de récupération de zinc à partir d'une solution WO2017054057A1 (fr)

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CA3000543A CA3000543A1 (fr) 2015-09-29 2016-09-29 Procede de recuperation de zinc a partir d'une solution
AU2016333158A AU2016333158A1 (en) 2015-09-29 2016-09-29 Method for recovering zinc from solution
TR2018/04416T TR201804416T1 (tr) 2015-09-29 2016-09-29 Çözelti̇den çi̇nkonun elde edi̇lmesi̇ne yöneli̇k yöntem
MX2018004024A MX2018004024A (es) 2015-09-29 2016-09-29 Metodo para recuperar zinc de una solucion.
US15/764,059 US20180237886A1 (en) 2015-09-29 2016-09-29 Method for recovering zinc from solution
ZA2018/02641A ZA201802641B (en) 2015-09-29 2018-04-20 Method for recovering zinc from solution
AU2022203277A AU2022203277A1 (en) 2015-09-29 2022-05-16 Method for Recovering Zinc from Solution

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Cited By (1)

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Publication number Priority date Publication date Assignee Title
CN112079509A (zh) * 2020-09-17 2020-12-15 河北威远生物化工有限公司 一种含醇、碳酸铵和氨废水的回收利用方法

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CN110817930A (zh) * 2019-07-25 2020-02-21 重庆东群科技有限公司 一种生产碳酸锌铵的方法

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1453859A (en) * 1972-12-20 1976-10-27 Kennecott Copper Corp Process for removing ammonia from solutions of oxime-metall chelate
US4105743A (en) * 1976-06-15 1978-08-08 Mx-Processer Reinhardt & Co. Ab Selectively extracting copper, zinc, nickel from a mixture of metal hydroxides
WO2010071932A1 (fr) * 2008-12-24 2010-07-01 Metaleach Limited Procédé d'extraction de zinc à partir de solutions ammoniacales aqueuses
AU2010228105B2 (en) * 2009-03-24 2012-05-17 Metaleach Limited Method for leaching zinc from a zinc ore
US8388729B2 (en) * 2007-07-13 2013-03-05 Metaleach Limited Method for ammoniacal leaching

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1453859A (en) * 1972-12-20 1976-10-27 Kennecott Copper Corp Process for removing ammonia from solutions of oxime-metall chelate
US4105743A (en) * 1976-06-15 1978-08-08 Mx-Processer Reinhardt & Co. Ab Selectively extracting copper, zinc, nickel from a mixture of metal hydroxides
US8388729B2 (en) * 2007-07-13 2013-03-05 Metaleach Limited Method for ammoniacal leaching
WO2010071932A1 (fr) * 2008-12-24 2010-07-01 Metaleach Limited Procédé d'extraction de zinc à partir de solutions ammoniacales aqueuses
AU2010228105B2 (en) * 2009-03-24 2012-05-17 Metaleach Limited Method for leaching zinc from a zinc ore

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112079509A (zh) * 2020-09-17 2020-12-15 河北威远生物化工有限公司 一种含醇、碳酸铵和氨废水的回收利用方法

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CA3000543A1 (fr) 2017-04-06
MX2018004024A (es) 2018-11-09
PE20181209A1 (es) 2018-07-24
US20180237886A1 (en) 2018-08-23
TR201804416T1 (tr) 2018-05-21
AU2022203277A1 (en) 2022-06-02
AU2016333158A1 (en) 2018-04-19

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