CN100406593C - 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
CN100406593C
CN100406593C CNB2005800302299A CN200580030229A CN100406593C CN 100406593 C CN100406593 C CN 100406593C CN B2005800302299 A CNB2005800302299 A CN B2005800302299A CN 200580030229 A CN200580030229 A CN 200580030229A CN 100406593 C CN100406593 C CN 100406593C
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CN
China
Prior art keywords
zinc
solution
preparation
dissolving
acid
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Legal status (The legal status 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 status listed.)
Expired - Fee Related
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CNB2005800302299A
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Chinese (zh)
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CN101014723A (en
Inventor
M·劳纳拉
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Metso Outotec Oyj
Outokumpu Engineering Oy
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Outokumpu Engineering Oy
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Publication of CN101014723A publication Critical patent/CN101014723A/en
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Publication of CN100406593C publication Critical patent/CN100406593C/en
Expired - Fee Related legal-status Critical Current
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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
    • C22B19/26—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

Abstract

The invention is a novel process arrangement for producing pure zinc chemicals from the minor flow of a calcining-dissolving-electrolysis type of a preparation process of zinc. The invention is based on the fact that part of the production of the zinc sulphate-containing solution obtained from the dissolution of the calcining-dissolving-electrolysis plant is directed to the preparation of zinc chemicals. The actual recovery process of zinc, which is based on electrolysis, is not disturbed, as only part of the production of the zinc sulphate solution is directed to the preparation of zinc chemicals. The extraction process is based on the use of any organically substituted phosphoric acid or organically substituted thiophosphinic acid. The strong acid solution, which is generated as a by-product in the extraction process of zinc, is recycled back to the calcining-dissolving-electrolysis type of a preparation process of zinc.

Description

Minor flows by flow process prepares zinc chemicals
Technical field
The present invention relates to prepare the method for zinc and zinc chemicals.More precisely, the present invention relates to prepare method setting and loop (the process arrangement andcircuit) of zinc chemicals, described method setting is relevant with the method for preparing zinc with the hydrometallurgical purifying with the loop.
Background technology
About the preparation of zinc, mention the preparation of primary production and secondary usually.Primary production refers to various dissolution process that the enriched material of zinc ore, zinc and calcined material are carried out and to the treating processes of thus obtained solution by various Wet-process metallurgy methods-comprise liquid-liquid extraction method-carried out.Secondary preparation refers to the raw material that uses various volumes less, for example will be from the particle of electric furnace, the oxide compound of VOLZ kiln process (Waeltz oxides) and plating residue as raw material.
In the primary production of zinc, the traditional raw material for example sulfide ore of zinc concentrates, and promptly becomes the enriched material of zinc, and, if desired, can also further prepare the zinc calcined material by it.In addition, the common vitriol oil zinc solution that is highly suitable for the electrolytic preparation metallic zinc by the enriched material and the preparation of zinc calcined material of zinc.The present invention relates to carry out the primary production of zinc with traditional hydrometallurgical.
Produce in the process of zinc in traditional hydrometallurgical, carry out complicated solution purification process, comprise the zinc-containing solution that preparation is pure needing behind the material dissolution.The process of electrolytic preparation zinc is very responsive to some impurity.Therefore, enough pure to be used for the electrolytic solution of zinc very important in preparation.
The preparation of zinc is extensive use of a kind of method, and wherein the zinc enriched material is dissolved in dilution heat of sulfuric acid, purifying zinc-containing solution through calcining formation zinc oxide, zinc oxide in so-called neutral dissolving step, and by the solution of electrolytic separation method behind purifying zinc being separated.
With the zinc calcined material dissolved stage, zinc is dissolved, and the most of iron that contains in the zinc calcined material is separated with the Zn ferrite form that is insoluble to diluted acid.The solution that is obtained by neutral dissolution also contains ferrous iron, cadmium, copper, cobalt, nickel, calcium, manganese and chlorine except zinc.
In order to obtain to be applicable to the solution of electrolytic recovery of zinc, the solution that is obtained by neutral dissolution carries out purifying by multistep solution purification process.The solution purification process generally included for three steps, in this process copper, cobalt, nickel, be that cadmium is removed at last.
The zinciferous sulfate liquor that neutral dissolution obtains also is suitable for the raw material as the leaching method of zinc.Up to this point, still to be used for mainly be the zinc preparation process of small-scale use secondary raw materials to liquid-liquid extraction method.For example United States Patent (USP) 5,135,652 have described a kind of solvent extraction method that can be used for selective separation zinc from solution of zinc sulfate, described solution of zinc sulfate can contain the zinc sulfate that is up to saturation concentration, and in the following material one or more: ferrous iron, ferric iron, calcium, magnesium, manganese, sodium, potassium, arsenic, antimony, copper, cadmium, germanium and indium.
Summary of the invention
The purpose of this invention is to provide a kind of being used for from the new method setting of the minor flows production zinc chemicals of calcining-dissolving-electrolysis-type zinc production method.The present invention based on the fact be: the part output of the solution of the sulfur acid zinc that is obtained from the dissolution process of calcining-dissolving-electrolyzer is used to prepare zinc chemicals by derivation.Because it is solution of zinc sulfate has only part output to be used to prepare zinc chemicals by derivation, therefore, unaffected based on the actual recovery process of the zinc of electrolytic process.In method of the present invention was provided with, the preparation process of zinc chemicals was based on utilizing known abstraction technique to extract and zinc being carried out selective separation.Known extracting process is based on the use of the thiophosphinic acid of the phosphoric acid of any organic replacement or organic replacement.Among the present invention, extraction process combines with above-mentioned calcining-dissolving-electrolytic process.
The present invention has multiple advantage.In routine calcining-dissolving-electrolytic process, the bottleneck of production process is an electrolytic process.Therefore, the technical solution of the present invention of minor flows being introduced the production line of zinc chemicals makes the actual production process increment of zinc.The invention provides a kind of favourable process program for preparing the less zinc chemicals of demand.In the extraction process of zinc used in the present invention, generate strong acid solution as by product, this strong acid solution can circulate simply to be used for the preparation process of zinc.In this case, do not need to invest in addition for the last processing of acid solution.
The present invention includes a kind of by extracting process and by the method and the setting of the formulations prepared from solutions zinc chemicals of sulfur acid zinc, wherein the feed stream of extraction process is separated after the neutral dissolving step of the calcining-dissolving-electrolysis-type technical process of the primary productoin of zinc with the form of minor flows.
Description of drawings
Fig. 1 illustrates the simplified flow chart of the preparation process of the calcining-dissolving-electrolysis-type preparation method of zinc and coupled zinc chemicals.
Embodiment
Below mode by the reference accompanying drawing describe the present invention.
In the preparation process of zinc, the calcined material 10 that contains zinc oxide is dissolved in the sulphuric acid soln in neutral dissolution.Neutral dissolution is divided into several steps usually and carries out.Solution residue 12 insoluble in dissolution process, wherein composition such as iron content is carried out the strong acid dissolving.The solution 11 of sulfur acid zinc is carried out the multistep solution purification, wherein use zinc powder 14 to make copper, cobalt, nickel and cadmium precipitation.To import in the electrolyzer through the solution of zinc sulfate 15 of solution purification, wherein on anode 16, reclaim zinc by electrolytic mode.By containing a large amount of sulfuric acid in the electrolytic solution 17 that wherein reclaims zinc, thereby sulfuric acid is carried out reuse by these sulfuric acid being imported wherein strong acid dissolution etc.In strong acid dissolution, acid is used up in reaction.Therefore except using restored acid, also need in flow process, to add a certain amount of pure acid.In neutral dissolution, the pH value of solution can not improve too highly.Reasonably be the pH value of using fresh acid 18 sour and that from strong acid dissolution, obtain to regulate in the neutral dissolution.
According to the present invention, the sulfur acid zinc solution that from neutral dissolution, obtains from main flow 11--in isolate one minor flows 13, and import the extraction process of zinc.In extraction process, use diethylhexyl phosphoric acid (DEHPA) or two-2-ethylhexyl phosphoric acid (D2EHPA).When dissolution process will finish, if desired, the pH value of the solution that will extract can be brought up to the level that is suitable for extracting with calcined material.By using acid-containing solution 21 to strip zinc is separated from organic phase.The raffinate 19 that produces in the extraction process contains sulfuric acid etc., introduces strong acid stage and carries out reuse.
In the reextraction process of using pure acid, can from sulphuric acid soln, reclaim pure zinc, wherein the content of zinc reaches as high as 150g/l.Can use any known method, for example chemical precipitation or evaporation is by the various pure zinc products that contain of solution 20 preparation.

Claims (4)

1. method that from the solution of sulfur acid zinc, prepares zinc chemicals by extraction process, it is characterized in that the feed stream of extraction process is separated after the neutral dissolving step of the calcining-dissolving-electrolysis-type technical process (11) of the primary productoin of zinc with the form of minor flows (13).
2. the method for claim 1 is characterized in that, the raffinate (19) that produces in the extraction process is back in the strong acid dissolution in described calcining-dissolving-electrolysis-type technology.
3. the method for claim 1 is characterized in that, uses diethylhexyl phosphoric acid or two-2-ethylhexyl phosphoric acid in extraction process.
4. the method for claim 1 is characterized in that, when dissolving step will finish, the pH value of the solution that will extract was brought up to the level that is suitable for extracting with calcined material.
CNB2005800302299A 2004-09-08 2005-09-06 Preparation of zinc chemicals from the minor flow of a process Expired - Fee Related CN100406593C (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FI20041163A FI117139B (en) 2004-09-08 2004-09-08 Production of zinc chemicals from process stream
FI20041163 2004-09-08

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CN101014723A CN101014723A (en) 2007-08-08
CN100406593C true CN100406593C (en) 2008-07-30

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Country Status (11)

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

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102102148B (en) * 2010-12-15 2012-10-24 河南豫光锌业有限公司 Recycling method of indium raffinate
CN103160688B (en) * 2013-04-17 2015-08-05 昆明奥赛美科技有限公司 Zinc replacement prepares the method for germanium concentrate from germanic leach liquor

Citations (3)

* 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
US5135652A (en) * 1990-10-25 1992-08-04 Cominco Ltd. Method for the solvent extraction of zinc
CN1107895A (en) * 1994-03-02 1995-09-06 张振逵 Technology and equipment for coproducing zinc sulfate and lead concentrate

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5084180A (en) * 1990-10-25 1992-01-28 Cominco Ltd. Method for treating zinc-containing sulfate solution
US5358700A (en) * 1992-10-05 1994-10-25 Cyprus Power Company Method of extracting zinc from brines

Patent Citations (3)

* 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
US5135652A (en) * 1990-10-25 1992-08-04 Cominco Ltd. Method for the solvent extraction of zinc
CN1107895A (en) * 1994-03-02 1995-09-06 张振逵 Technology and equipment for coproducing zinc sulfate and lead concentrate

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Publication number Publication date
WO2006027412A1 (en) 2006-03-16
MX2007002750A (en) 2007-05-18
AU2005281684A1 (en) 2006-03-16
US20070253878A1 (en) 2007-11-01
PE20060757A1 (en) 2006-09-14
EA200700420A1 (en) 2007-10-26
CN101014723A (en) 2007-08-08
JP2008512569A (en) 2008-04-24
FI20041163A (en) 2006-03-09
EP1794334A1 (en) 2007-06-13
CA2577863A1 (en) 2006-03-16
FI20041163A0 (en) 2004-09-08
FI117139B (en) 2006-06-30
EA010853B1 (en) 2008-12-30

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Granted publication date: 20080730

Termination date: 20100906