US20070253878A1 - Preparation of Zinc Chemicals from the Minor Flow of a Process - Google Patents

Preparation of Zinc Chemicals from the Minor Flow of a Process Download PDF

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Publication number
US20070253878A1
US20070253878A1 US11/662,061 US66206105A US2007253878A1 US 20070253878 A1 US20070253878 A1 US 20070253878A1 US 66206105 A US66206105 A US 66206105A US 2007253878 A1 US2007253878 A1 US 2007253878A1
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United States
Prior art keywords
zinc
solution
preparation
extraction
acid
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Abandoned
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US11/662,061
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English (en)
Inventor
Mikko Ruonala
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Outokumpu Technology Oyj
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Outokumpu Technology Oyj
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Assigned to OUTOKUMPU TECHNOLOGY OYJ reassignment OUTOKUMPU TECHNOLOGY OYJ ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: RUONALA, MIKKO
Publication of US20070253878A1 publication Critical patent/US20070253878A1/en
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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B19/00—Obtaining zinc or zinc oxide
    • C22B19/20—Obtaining zinc otherwise than by distilling
    • C22B19/26—Refining solutions containing zinc values, e.g. obtained by leaching zinc ores
    • 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
    • C22B19/22—Obtaining zinc otherwise than by distilling with leaching with acids
    • 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
    • C22B3/06—Extraction of metal compounds from ores or concentrates by wet processes by leaching in inorganic acid solutions, e.g. with acids generated in situ; in inorganic salt solutions other than ammonium salt solutions
    • C22B3/08—Sulfuric acid, other sulfurated acids or salts thereof
    • 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
    • C22B3/38—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

  • the invention relates to the preparation processes of zinc and zinc chemicals. To be more precise, the invention relates to a process arrangement and circuit for preparing zinc chemicals in connection with a hydrometallurgical purification and preparation process of zinc.
  • the primary production refers to various dissolutions of zinc ores, zinc concentrates and calcines and the treatment of solutions obtained therefrom by means of various hydrometallurgical methods, including liquid-liquid extraction.
  • the secondary production refers to the use of various raw materials of lesser volumes, such as particulates of electric furnaces, Waeltz oxides and galvanizing cinders, as raw material.
  • a method for the preparation of zinc, a method is widely used, wherein zinc concentrate is calcined to form zinc oxide, the zinc oxide is dissolved in a diluted sulphuric-acid solution in a so-called neutral dissolution, the zinciferous solution is purified, and zinc is separated from the purified solution by electrolytic separation.
  • the zinc dissolves and the major part of the iron contained by the zinc calcine can be separated as zinc ferrite that does not dissolve in the diluted acid.
  • the solution obtained from the neutral dissolution contains bivalent iron, cadmium, copper, cobalt, nickel, calcium, manganese and chlorides.
  • the solution obtained from the neutral dissolution is purified by a multi-stage solution purification process. Normally, the solution purification comprises three stages, wherein copper, cobalt, nickel, and finally, cadmium are removed.
  • the zinciferous sulphate solution obtained from the neutral dissolution is also suitable for a feed material in the leaching method of zinc.
  • the liquid-liquid extraction has been used for zinc preparation mainly in small-scale processes that employ secondary raw materials.
  • the U.S. Pat. No. 5,135,652 describes a solvent extraction that can be used to selectively separate zinc from the zinc sulphate solution, which may contain zinc sulphate up to its saturation concentration, and one or more of a group containing the following: bivalent iron, trivalent iron, calcium, magnesium, manganese, sodium, potassium, arsenic, antimony, copper, cadmium, germanium, and indium.
  • the purpose of this invention is to provide a new kind of a process arrangement for producing pure zinc chemicals from the minor flow of a zinc preparation process of a calcining-dissolving-electrolysis type.
  • the invention is based on the fact that part of the production of the zinc sulphate-containing solution obtained from the dissolving of the calcining-dissolving-electrolysis plant is directed to the preparation of zinc chemicals. As only part of the production of the zinc sulphate solution is directed to the preparation of zinc chemicals, the actual recovery process of zinc that is based on the electrolysis is not disturbed.
  • the preparation process of zinc chemicals is based on a selective separation of zinc by extraction with known extraction techniques.
  • the known extraction process is based on the use of any organically substituted phosphoric acid or organically substituted thiophosphinic acid. According to the invention, the extraction process is connected to the calcining-dissolving-electrolysis process described above.
  • the invention provides considerable advantages.
  • the bottleneck of the production lies in the electrolysis process.
  • the solution according to the invention for taking the minor flow to the preparation line of zinc chemicals adds value to the actual production process of zinc.
  • the invention provides an advantageous process solution for the preparation of zinc chemicals of a lesser demand.
  • a strong acid solution is generated as a by-product, which can simply be recycled to be exploited in the preparation process of zinc. In that case, no separate investments for the final treatment of the acid solution are needed.
  • the invention comprises a process circuit and arrangement for preparing pure zinc chemicals from a zinc sulphate-containing solution by an extraction method, whereby the raw material flow of the extraction is separated as a minor flow from the calcining-dissolving-electrolysis type process line of zinc primary production after the neutral dissolving stage.
  • FIG. 1 shows a simplified process chart of the calcining-dissolving-electrolysis type preparation process of zinc and the preparation stage of zinc chemicals connected thereto.
  • a calcine 10 containing zinc oxide is dissolved in a sulphuric-acid solution in a neutral dissolution.
  • the neutral dissolution is typically carried out in several stages.
  • a solution residue 12 which is not soluble in the dissolution and contains iron, among others, is directed to a strong acid dissolution.
  • a zinc sulphate-containing solution 11 is directed to a multi-stage solution purification, wherein a zinc powder 14 is used to precipitate copper, cobalt, nickel and cadmium.
  • the solution-purified zinc sulphate solution 15 is directed to an electrolysis plant, wherein the zinc is recovered at cathodes 16 by means of electrolysis.
  • the electrolyte, from which the zinc was recovered 17 contains a considerable amount of sulphuric acid, which is reintroduced by directing it to the strong acid dissolution, among others.
  • the strong acid dissolution the acid is used up in reactions. Accordingly, in addition to the recycled acid, a certain amount of pure acid is added into the process.
  • the neutral dissolution the pH of the solution should not be raised too high. It is reasonable to adjust the pH of the neutral dissolution with fresh acid and, in addition, with an acid 18 that is obtained from the strong acid dissolution.
  • a minor flow 13 is separated from the main flow 11 of the zinc sulphate-containing solution obtained from the neutral dissolution, and directed to the extraction of zinc.
  • DEHPA diethylhexylphosphoric acid
  • D2EHPA di-2-ethylhexylphosphoric acid
  • Zinc is separated from the organic phase by stripping it with an acid-containing solution 21 .
  • the raffinate 19 which is generated in the extraction, contains sulphuric acid, among others, and is directed to the strong acid stage to be reused.
  • the pure zinc can be recovered in a sulphuric-acid solution, wherein the content of zinc can be up to 150 g/l.
  • Various pure zinc products can be prepared from this solution 20 by any known methods, such as by chemical precipitation or evaporation.
  • the invention relates to the preparation processes of zinc and zinc chemicals. To be more precise, the invention relates to a process arrangement and circuit for preparing zinc chemicals in connection with a hydrometallurgical purification and preparation process of zinc.
  • the primary production refers to various dissolutions of zinc ores, zinc concentrates and calcines and the treatment of solutions obtained therefrom by means of various hydrometallurgical methods, including liquid-liquid extraction.
  • the secondary production refers to the use of various raw materials of lesser volumes, such as particulates of electric furnaces, Waeltz oxides and galvanizing cinders, as raw material.
  • a method for the preparation of zinc, a method is widely used, wherein zinc concentrate is calcined to form zinc oxide, the zinc oxide is dissolved in a diluted sulphuric-acid solution in a so-called neutral dissolution, the zinciferous solution is purified, and zinc is separated from the purified solution by electrolytic separation.
  • the zinc dissolves and the major part of the iron contained by the zinc calcine can be separated as zinc ferrite that does not dissolve in the diluted acid.
  • the solution obtained from the neutral dissolution contains bivalent iron, cadmium, copper, cobalt, nickel, calcium, manganese and chlorides.
  • the solution obtained from the neutral dissolution is purified by a multi-stage solution purification process. Normally, the solution purification comprises three stages, wherein copper, cobalt, nickel, and finally, cadmium are removed.
  • the zinciferous sulphate solution obtained from the neutral dissolution is also suitable for a feed material in the leaching method of zinc.
  • the liquid-liquid extraction has been used for zinc preparation mainly in small-scale processes that employ secondary raw materials.
  • the U.S. Pat. No. 5,135,652 describes a solvent extraction that can be used to selectively separate zinc from the zinc sulphate solution, which may contain zinc sulphate up to its saturation concentration, and one or more of a group containing the following: bivalent iron, trivalent iron, calcium, magnesium, manganese, sodium, potassium, arsenic, antimony, copper, cadmium, germanium, and indium.
  • the purpose of this invention is to provide a new kind of a process arrangement for producing pure zinc chemicals from the minor flow of a zinc preparation process of a calcining-dissolving-electrolysis type.
  • the invention is based on the fact that part of the production of the zinc sulphate-containing solution obtained from the dissolving of the calcining-dissolving-electrolysis plant is directed to the preparation of zinc chemicals. As only part of the production of the zinc sulphate solution is directed to the preparation of zinc chemicals, the actual recovery process of zinc that is based on the electrolysis is not disturbed.
  • the preparation process of zinc chemicals is based on a selective separation of zinc by extraction with known extraction techniques.
  • the known extraction process is based on the use of any organically substituted phosphoric acid or organically substituted thiophosphinic acid. According to the invention, the extraction process is connected to the calcining-dissolving-electrolysis process described above.
  • the invention provides considerable advantages.
  • the bottleneck of the production lies in the electrolysis process.
  • the solution according to the invention for taking the minor flow to the preparation line of zinc chemicals adds value to the actual production process of zinc.
  • the invention provides an advantageous process solution for the preparation of zinc chemicals of a lesser demand.
  • a strong acid solution is generated as a by-product, which can simply be recycled to be exploited in the preparation process of zinc. In that case, no separate investments for the final treatment of the acid solution are needed.
  • the invention comprises a process circuit and arrangement for preparing pure zinc chemicals from a zinc sulphate-containing solution by an extraction method, whereby the raw material flow of the extraction is separated as a minor flow from the calcining-dissolving-electrolysis type process line of zinc primary production after the neutral dissolving stage.
  • FIG. 1 shows a simplified process chart of the calcining-dissolving-electrolysis type preparation process of zinc and the preparation stage of zinc chemicals connected thereto.
  • a calcine 10 containing zinc oxide is dissolved in a sulphuric-acid solution in a neutral dissolution.
  • the neutral dissolution is typically carried out in several stages.
  • a solution residue 12 which is not soluble in the dissolution and contains iron, among others, is directed to a strong acid dissolution.
  • a zinc sulphate-containing solution 11 is directed to a multi-stage solution purification, wherein a zinc powder 14 is used to precipitate copper, cobalt, nickel and cadmium.
  • the solution-purified zinc sulphate solution 15 is directed to an electrolysis plant, wherein the zinc is recovered at cathodes 16 by means of electrolysis.
  • the electrolyte, from which the zinc was recovered 17 contains a considerable amount of sulphuric acid, which is reintroduced by directing it to the strong acid dissolution, among others.
  • the strong acid dissolution the acid is used up in reactions. Accordingly, in addition to the recycled acid, a certain amount of pure acid is added into the process.
  • the neutral dissolution the pH of the solution should not be raised too high. It is reasonable to adjust the pH of the neutral dissolution with fresh acid and, in addition, with an acid 18 that is obtained from the strong acid dissolution.
  • a minor flow 13 is separated from the main flow 11 of the zinc sulphate-containing solution obtained from the neutral dissolution, and directed to the extraction of zinc.
  • DEHPA diethylhexylphosphoric acid
  • D2EHPA di-2-ethylhexylphosphoric acid
  • Zinc is separated from the organic phase by stripping it with an acid-containing solution 21 .
  • the raffinate 19 which is generated in the extraction, contains sulphuric acid, among others, and is directed to the strong acid stage to be reused.
  • the pure zinc can be recovered in a sulphuric-acid solution, wherein the content of zinc can be up to 150 g/l.
  • Various pure zinc products can be prepared from this solution 20 by any known methods, such as by chemical precipitation or evaporation.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Metallurgy (AREA)
  • Environmental & Geological Engineering (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Geology (AREA)
  • General Life Sciences & Earth Sciences (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Inorganic Chemistry (AREA)
  • Electrolytic Production Of Metals (AREA)
  • Manufacture And Refinement Of Metals (AREA)
  • Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
US11/662,061 2004-09-08 2005-09-06 Preparation of Zinc Chemicals from the Minor Flow of a Process Abandoned US20070253878A1 (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
FI20041163A FI117139B (fi) 2004-09-08 2004-09-08 Sinkkikemikaalien valmistaminen prosessin sivuvirrasta
FI20041163 2004-09-08
PCT/FI2005/000380 WO2006027412A1 (en) 2004-09-08 2005-09-06 Preparation of zinc chemicals from the minor flow of a process

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US20070253878A1 true US20070253878A1 (en) 2007-11-01

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US11/662,061 Abandoned US20070253878A1 (en) 2004-09-08 2005-09-06 Preparation of Zinc Chemicals from the Minor Flow of a Process

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US (1) US20070253878A1 (ru)
EP (1) EP1794334A1 (ru)
JP (1) JP2008512569A (ru)
CN (1) CN100406593C (ru)
AU (1) AU2005281684A1 (ru)
CA (1) CA2577863A1 (ru)
EA (1) EA010853B1 (ru)
FI (1) FI117139B (ru)
MX (1) MX2007002750A (ru)
PE (1) PE20060757A1 (ru)
WO (1) WO2006027412A1 (ru)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103160688A (zh) * 2013-04-17 2013-06-19 昆明奥赛美科技有限公司 锌粉置换法从含锗浸出液中制备锗精矿的方法

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102102148B (zh) * 2010-12-15 2012-10-24 河南豫光锌业有限公司 铟萃余液的回收处理方法

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3989607A (en) * 1975-08-21 1976-11-02 Bush Philip D Solvent extraction and electrowinning of zinc and copper from sulfate solution
US5084180A (en) * 1990-10-25 1992-01-28 Cominco Ltd. Method for treating zinc-containing sulfate solution
US5135652A (en) * 1990-10-25 1992-08-04 Cominco Ltd. Method for the solvent extraction of zinc
US5358700A (en) * 1992-10-05 1994-10-25 Cyprus Power Company Method of extracting zinc from brines

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1040554C (zh) * 1994-03-02 1998-11-04 张振逵 联产硫酸锌与铅精矿的工艺与装置

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3989607A (en) * 1975-08-21 1976-11-02 Bush Philip D Solvent extraction and electrowinning of zinc and copper from sulfate solution
US5084180A (en) * 1990-10-25 1992-01-28 Cominco Ltd. Method for treating zinc-containing sulfate solution
US5135652A (en) * 1990-10-25 1992-08-04 Cominco Ltd. Method for the solvent extraction of zinc
US5358700A (en) * 1992-10-05 1994-10-25 Cyprus Power Company Method of extracting zinc from brines

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103160688A (zh) * 2013-04-17 2013-06-19 昆明奥赛美科技有限公司 锌粉置换法从含锗浸出液中制备锗精矿的方法

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WO2006027412A1 (en) 2006-03-16
MX2007002750A (es) 2007-05-18
AU2005281684A1 (en) 2006-03-16
PE20060757A1 (es) 2006-09-14
EA200700420A1 (ru) 2007-10-26
CN101014723A (zh) 2007-08-08
JP2008512569A (ja) 2008-04-24
FI20041163A (fi) 2006-03-09
EP1794334A1 (en) 2007-06-13
CA2577863A1 (en) 2006-03-16
FI20041163A0 (fi) 2004-09-08
FI117139B (fi) 2006-06-30
EA010853B1 (ru) 2008-12-30
CN100406593C (zh) 2008-07-30

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Owner name: OUTOKUMPU TECHNOLOGY OYJ, FINLAND

Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNOR:RUONALA, MIKKO;REEL/FRAME:019015/0229

Effective date: 20070208

STCB Information on status: application discontinuation

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