CN106555060A - It is a kind of to adopt the method dechlorinated from zinc solution except surface autoxidation copper ashes after cadmium - Google Patents

It is a kind of to adopt the method dechlorinated from zinc solution except surface autoxidation copper ashes after cadmium Download PDF

Info

Publication number
CN106555060A
CN106555060A CN201611004822.2A CN201611004822A CN106555060A CN 106555060 A CN106555060 A CN 106555060A CN 201611004822 A CN201611004822 A CN 201611004822A CN 106555060 A CN106555060 A CN 106555060A
Authority
CN
China
Prior art keywords
cadmium
copper ashes
copper
zinc solution
autoxidation
Prior art date
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.)
Pending
Application number
CN201611004822.2A
Other languages
Chinese (zh)
Inventor
蒋荣生
马云川
顾利坤
邹坤呈
李云
陈波
吴红林
张鸭林
吕亚彪
张特
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Yunnan Chihong Zinc and Germanium Co Ltd
Original Assignee
Yunnan Chihong Zinc and Germanium Co Ltd
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
Application filed by Yunnan Chihong Zinc and Germanium Co Ltd filed Critical Yunnan Chihong Zinc and Germanium Co Ltd
Priority to CN201611004822.2A priority Critical patent/CN106555060A/en
Publication of CN106555060A publication Critical patent/CN106555060A/en
Pending legal-status Critical Current

Links

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
    • 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 present invention relates to it is a kind of using the method that surface autoxidation copper ashes dechlorinates from zinc solution after cadmium is removed, belong to zinc field of hydrometallurgy, comprise the following steps that：1）The fresh copper-cadmium slag of zinc solution is leached into cadmium in sulfuric acid, except after cadmium copper ashes Cu contents be 15 ~ 70%, Cd contents be 0.2% ~ 1%；2）Except copper ashes is stored up to surface autoxidation after cadmium, autoxidation degree is 5 ~ 35%；3）Chloride zinc solution adjusts initial sulfuric acid concentration, is subsequently adding 5 ~ 50kg/m3Oxidation copper ashes stirring, NCu/NCl is 1.4 ~ 2.0, and it is 30 ~ 80 DEG C to control except chlorine temperature, and the dechlorination time is in 0.5 ~ 1h；4）After reaction terminates, zinc solution and dechlorination slag after being dechlorinated are separated by filtration.The present invention except the technique of cadmium, is reduced copper ashes impurity content, improves copper ashes copper grade using preferential；Replace fresh copper ashes using autoxidation copper ashes in surface after cadmium is removed, eliminate addition copper sulphate or Oxidation Leaching copper ashes Sulphuric acid copper solution operation；It is effectively simplified technique and reduces production cost, improves the economic benefit of enterprise.

Description

It is a kind of to adopt the method dechlorinated from zinc solution except surface autoxidation copper ashes after cadmium
Technical field
The invention belongs to zinc field of hydrometallurgy, specifically, is related to a kind of employing except surface autoxidation copper ashes after cadmium The method dechlorinated from zinc solution.
Background technology
Zinc lixiviating solution chloride ion-containing up to 1g/L after wet method system accumulation, causes equipment corrosion and electrolytic process Anodic Plate corrodes, and causing corrosion product is deposited on minus plate, affects zine plate yield rate, negative electrode power consumption to increase, and zinc metal sheet is peeled off difficult. The particularly application of the big pole plate of zinc electrolysis, it is desirable to chloride ion content<300mg/L.Industrially conventional chlorine removal from copper residue method is at present Using the disproportionated reaction of copper, concrete chemical reaction is as follows：
Cu+Cu2++2Cl-=Cu2Cl2↓
1～5g/L cupric sulfate pentahydrates, initial 30～100g/L of sulfuric acid content, fresh copper are often added in industrial zinc solution dechlorination Slag 20～100kg/m of consumption3,NCu/NCl1h or so is reacted under the conditions of 3,60 DEG C of ≈, solution chlorinity drops to 300mg/L after filtration Hereinafter, chlorine removal rate can reach more than 50%., there is disproportionated reaction in the copper sulphate in elemental copper and solution in fresh copper ashes, Precipitate into stannous chloride with chloride binding, so as to reach dechlorination effect.
The content of the invention
To overcome the shortcomings of in background technology, the present invention propose it is a kind of using except after cadmium surface autoxidation copper ashes from zinc The fresh copper ashes of zinc solution removal of impurities is stored up surface autoxidation by the method dechlorinated in solution, and its operation is simple, need not add sulphur Sour copper or its solution, under equal leaching condition, only need to put into half of original copper ashes addition or so, you can contain solution chlorine Amount drops to 300mg/L, without the need for the expensive cupric sulfate pentahydrate of purchase, is aoxidized with manganese dioxide etc. without under the conditions of high temperature peracid Copper ashes is leached in agent, so as to being effectively simplified technique and reducing production cost, is a kind of removing from zinc solution for economic and simplicity The method of chlorine.
To reach above-mentioned purpose, the present invention is implemented by following technical scheme：
A kind of to adopt the method dechlorinated from zinc solution except surface autoxidation copper ashes after cadmium, specific operating procedure is such as Under：
1) the fresh copper-cadmium slag of zinc solution is leached into cadmium in sulfuric acid, reduces impurity content in copper ashes, improve copper in copper ashes Grade；
2) except after cadmium copper ashes store up to surface autoxidation；
3) chloride zinc solution adjusts initial sulfuric acid concentration, is subsequently adding step 2) obtained by the stirring of oxidation copper ashes；
4), after reaction terminates, zinc solution and dechlorination slag after being dechlorinated are separated by filtration.
Further, step 1) described in zinc solution copper-cadmium slag Cu contents be 13～50%, Cd contents be 0.5～10%.
Further, step 1) described in sulfuric acid be waste electrolyte, initial concentration be 10～100g/L.
Further, step 1) in, except after cadmium copper ashes Cu contents be 15～70%, Cd contents be 0.2%～1%.
Further, step 2) in, autoxidation degree is 5～35%.
Further, step 3) described in chloride zinc solution Cl-Ion concentration is 0.5～5g/L.
Further, step 3) described in copper ashes addition be 3～50kg/m3, NCu/NCl is 1.4～2.0.
Further, step 3) in, except chlorine temperature is 30～80 DEG C, the dechlorination time is in 0.5～1h.
Beneficial effects of the present invention：The present invention effectively reduces the anti-of cadmium during dechlorination using preferential except the technique of cadmium It is molten, copper ashes impurity content is reduced, copper ashes copper grade is improve；Replace fresh copper using autoxidation copper ashes in surface after cadmium is removed Slag, eliminates the operation of addition copper sulphate or Oxidation Leaching copper ashes Sulphuric acid copper solution；Copper ashes addition is reduced, is effectively simplified Technique simultaneously reduces production cost, improves the economic benefit of enterprise.
Description of the drawings
Fig. 1 is the process chart of the present invention.
Specific embodiment
A kind of to adopt the method dechlorinated from zinc solution except surface autoxidation copper ashes after cadmium, specific operating procedure is such as Under：1) by the fresh copper-cadmium slag of zinc solution (Cu contents be 13～50%, Cd contents be 0.5～10%) sulfuric acid (waste electrolyte, Initial concentration is 10～100g/L) in leach cadmium, except after cadmium copper ashes Cu contents be 15～70%, Cd contents be 0.2%～1%, Impurity content in copper ashes is reduced, the grade of copper in copper ashes is improved；2) except after cadmium copper ashes store up to surface autoxidation, autoxidation Degree is 5～35%；3) chloride zinc solution (Cl-Ion concentration is 0.5～5g/L) initial sulfuric acid concentration is adjusted, it is subsequently adding 3 ～50kg/m3Step 2) obtained by aoxidize copper ashes stirring, NCu/NCl be 1.4～2.0, control except chlorine temperature be 30～80 DEG C, dechlorinate Time is in 0.5～1h；4), after reaction terminates, zinc solution and dechlorination slag after being dechlorinated are separated by filtration.
Embodiment 1
Zinc neutral leachate configures the solution of zinc sulfate that a small amount of waste electrolyte obtains initial sulfuric acid concentration 10g/L, adds 10kg/m3 Not except cadmium surfaces aoxidize copper ashes, 60 DEG C of reaction 0.8h, liquid chloride ion-containing after filtration are heated to<200mg/L, data are as follows：
g/L Cl Zn Cu Cd
Liquid before dechlorination 1.06 145 0.30 0.24
Liquid after dechlorination 0.17 147 1.65 0.53
Embodiment 2
Zinc neutral leachate configures the solution of zinc sulfate that a small amount of waste electrolyte obtains initial sulfuric acid concentration 10g/L, adds 3kg/m3 Not except cadmium surfaces aoxidize copper ashes, 60 DEG C of reaction 0.8h, liquid chloride ion-containing after filtration are heated to>300mg/L, data are as follows：
g/L Cl Zn Cu Cd
Liquid before dechlorination 1.06 145 0.30 0.24
Liquid after dechlorination 0.55 146 2.14 0.47
Embodiment 3
Zinc neutral leachate configures the solution of zinc sulfate that a small amount of waste electrolyte obtains initial sulfuric acid concentration 5g/L, adds 10kg/m3 Except cadmium surfaces aoxidize copper ashes, 60 DEG C of reaction 0.8h are heated to, liquid chloride ion-containing is 300mg/L after filtration, and data are as follows：
Embodiment 4
Zinc neutral leachate configures the solution of zinc sulfate that a small amount of waste electrolyte obtains initial sulfuric acid concentration 10g/L, adds 10kg/m3 Except surface oxidation copper ashes after cadmium, 60 DEG C of reaction 0.8h, liquid chloride ion-containing after filtration are heated to<200mg/L, data are as follows：
g/L Cl Zn Cu Cd
Liquid before dechlorination 1.06 145 0.30 0.24
Liquid after dechlorination 0.16 146 1.66 0.26
Embodiment 5
Zinc neutral leachate configures the solution of zinc sulfate that a small amount of waste electrolyte obtains initial sulfuric acid concentration 10g/L, adds 3kg/m3 Except surface oxidation copper ashes after cadmium, 60 DEG C of reaction 0.8h, liquid chloride ion-containing after filtration are heated to>300mg/L, data are as follows：
g/L Cl Zn Cu Cd
Liquid before dechlorination 1.06 145 0.30 0.24
Liquid after dechlorination 0.53 146 2.14 0.25
Embodiment 6
Zinc neutral leachate configures the solution of zinc sulfate that a small amount of waste electrolyte obtains initial sulfuric acid concentration 5g/L, adds 10kg/m3 Except surface oxidation copper ashes after cadmium, 60 DEG C of reaction 0.8h, liquid chloride ion-containing after filtration are heated to<300mg/L, data are as follows：
g/L Cl Zn Cu Cd
Liquid before dechlorination 1.06 145 0.30 0.24
Liquid after dechlorination 0.29 146 1.31 0.26
The present invention except the technique of cadmium, is effectively reduced the anti-molten of cadmium during dechlorination, reduces copper ashes impurity using preferential Content, improves copper ashes copper grade；Replace fresh copper ashes using autoxidation copper ashes in surface after cadmium is removed, eliminate addition copper sulphate Or Oxidation Leaching copper ashes Sulphuric acid copper solution operation；Copper ashes addition is reduced, technique is effectively simplified and is reduced and produce into This, improves the economic benefit of enterprise.
Finally illustrate, preferred embodiment above is merely to illustrate technical scheme and unrestricted, although logical Cross above preferred embodiment to be described in detail the present invention, it is to be understood by those skilled in the art that can be Various changes are made to which in form and in details, without departing from claims of the present invention limited range.

Claims (8)

  1. It is 1. a kind of to adopt the method dechlorinated from zinc solution except surface autoxidation copper ashes after cadmium, it is characterised in that：It is specific to grasp Make step as follows：
    1）The fresh copper-cadmium slag of zinc solution is leached into cadmium in sulfuric acid, impurity content in copper ashes is reduced, the product of copper in copper ashes are improved Position；
    2）Except copper ashes is stored up to surface autoxidation after cadmium；
    3）Chloride zinc solution adjusts initial sulfuric acid concentration, is subsequently adding step 2）The oxidation copper ashes stirring of gained；
    4）After reaction terminates, zinc solution and dechlorination slag after being dechlorinated are separated by filtration.
  2. 2. the method that surface autoxidation copper ashes dechlorinates from zinc solution after a kind of employing according to claim 1 removes cadmium, It is characterized in that：Step 1）Described in zinc solution copper-cadmium slag Cu contents be 13 ~ 50%, Cd contents be 0.5 ~ 10%.
  3. 3. the method that surface autoxidation copper ashes dechlorinates from zinc solution after a kind of employing according to claim 1 removes cadmium, It is characterized in that：Step 1）Described in sulfuric acid be waste electrolyte, initial concentration be 10 ~ 100g/L.
  4. 4. the method that surface autoxidation copper ashes dechlorinates from zinc solution after a kind of employing according to claim 1 removes cadmium, It is characterized in that：Step 1）In, except after cadmium copper ashes Cu contents be 15 ~ 70%, Cd contents be 0.2% ~ 1%.
  5. 5. the method that surface autoxidation copper ashes dechlorinates from zinc solution after a kind of employing according to claim 1 removes cadmium, It is characterized in that：Step 2）In, autoxidation degree is 5 ~ 35%.
  6. 6. the method that surface autoxidation copper ashes dechlorinates from zinc solution after a kind of employing according to claim 1 removes cadmium, It is characterized in that：Step 3）Described in chloride zinc solution Cl-Ion concentration is 0.5 ~ 5g/L.
  7. 7. the method that surface autoxidation copper ashes dechlorinates from zinc solution after a kind of employing according to claim 1 removes cadmium, It is characterized in that：Step 3）Described in aoxidize copper ashes addition be 3 ~ 50kg/m3, NCu/NCl is 1.4 ~ 2.0.
  8. 8. the method that surface autoxidation copper ashes dechlorinates from zinc solution after a kind of employing according to claim 1 removes cadmium, It is characterized in that：Step 3）In, except chlorine temperature is 30 ~ 80 DEG C, the dechlorination time is in 0.5 ~ 1h.
CN201611004822.2A 2016-11-15 2016-11-15 It is a kind of to adopt the method dechlorinated from zinc solution except surface autoxidation copper ashes after cadmium Pending CN106555060A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201611004822.2A CN106555060A (en) 2016-11-15 2016-11-15 It is a kind of to adopt the method dechlorinated from zinc solution except surface autoxidation copper ashes after cadmium

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201611004822.2A CN106555060A (en) 2016-11-15 2016-11-15 It is a kind of to adopt the method dechlorinated from zinc solution except surface autoxidation copper ashes after cadmium

Publications (1)

Publication Number Publication Date
CN106555060A true CN106555060A (en) 2017-04-05

Family

ID=58444771

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201611004822.2A Pending CN106555060A (en) 2016-11-15 2016-11-15 It is a kind of to adopt the method dechlorinated from zinc solution except surface autoxidation copper ashes after cadmium

Country Status (1)

Country Link
CN (1) CN106555060A (en)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107586969A (en) * 2017-08-11 2018-01-16 赤峰中色锌业有限公司 A kind of method using one section of pulp slag alternative dry chlorine removal from copper residue of purification
CN108456785A (en) * 2018-02-01 2018-08-28 云南云铜锌业股份有限公司 A kind of method and device using copper ashes dechlorination
CN114481222A (en) * 2022-02-11 2022-05-13 新疆紫金有色金属有限公司 Method for deeply removing chlorine from zinc electrolyte

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101113015A (en) * 2007-07-13 2008-01-30 株洲冶炼集团股份有限公司 Method for removing chlorine from zinc sulfate solution
CN101457295A (en) * 2007-12-10 2009-06-17 巴彦淖尔紫金有色金属有限公司 Dechlorination method in zinc hydrometallurgy circulation solution system
CN101633982A (en) * 2009-08-15 2010-01-27 蒙自矿冶有限责任公司 Method for circularly removing chlorine in zinc sulphate solution by copper slag
CN102796869A (en) * 2012-09-12 2012-11-28 葫芦岛锌业股份有限公司 Method for removing chlorine in zinc sulfate solution with high chlorine content
CN104046793A (en) * 2014-06-27 2014-09-17 湖南水口山有色金属集团有限公司 Method of removing chlorine in zinc sulfate solution

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101113015A (en) * 2007-07-13 2008-01-30 株洲冶炼集团股份有限公司 Method for removing chlorine from zinc sulfate solution
CN101457295A (en) * 2007-12-10 2009-06-17 巴彦淖尔紫金有色金属有限公司 Dechlorination method in zinc hydrometallurgy circulation solution system
CN101633982A (en) * 2009-08-15 2010-01-27 蒙自矿冶有限责任公司 Method for circularly removing chlorine in zinc sulphate solution by copper slag
CN102796869A (en) * 2012-09-12 2012-11-28 葫芦岛锌业股份有限公司 Method for removing chlorine in zinc sulfate solution with high chlorine content
CN104046793A (en) * 2014-06-27 2014-09-17 湖南水口山有色金属集团有限公司 Method of removing chlorine in zinc sulfate solution

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
申永强等: "铜渣法除电解锌溶液中氯的工艺研究", 《洛阳理工学院学报（自然科学版）》 *

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107586969A (en) * 2017-08-11 2018-01-16 赤峰中色锌业有限公司 A kind of method using one section of pulp slag alternative dry chlorine removal from copper residue of purification
CN108456785A (en) * 2018-02-01 2018-08-28 云南云铜锌业股份有限公司 A kind of method and device using copper ashes dechlorination
CN114481222A (en) * 2022-02-11 2022-05-13 新疆紫金有色金属有限公司 Method for deeply removing chlorine from zinc electrolyte

Similar Documents

Publication Publication Date Title
CN102912138B (en) Method of recycling zinc, manganese, lead and silver from zinc electrowinning anode mud
US9630844B2 (en) Hydrometallurgical process for the recovery of tellurium from high lead bearing copper refinery anode slime
WO2008053616A1 (en) Method for collection of valuable metal from ito scrap
CN105648214B (en) It is a kind of to control the method that current potential vulcanization separates valuable metal in solution
JP6471912B2 (en) Method for producing high purity cobalt sulfate aqueous solution
CN101519727A (en) Method for treating zinc smelting by-products
Zhang et al. Manganese metallurgy review. Part III: Manganese control in zinc and copper electrolytes
CN105603190A (en) Method for purifying and recovering valuable metal by copper electrolyte
CN101974765A (en) Comprehensive method for separating stibium from materials containing stibium, tin and lead
CN106555060A (en) It is a kind of to adopt the method dechlorinated from zinc solution except surface autoxidation copper ashes after cadmium
NO772810L (en) PROCEDURES FOR RECYCLING ZINC AND MANGANDICOXIDE
CN113862479A (en) Resource recovery processing method for lead plaster in waste lead storage battery
US4030990A (en) Process for recovering electrolytic copper of high purity by means of reduction electrolysis
CN104561558A (en) Method for treating selenium-containing mercury acid mud
CN104419826B (en) The method that ammonia soaks Zinc Oxide electrowinning zinc
CN103498169A (en) Preparation method for reducing sulfur impurities in electrolytic nickel
CN108910958A (en) A method of manganese sulfate is produced using aniline reduction electrolytic manganese anode mud
CN107815540A (en) A kind of method of hydrometallurgy metal nickel cobalt and its salt product
CN103060842A (en) Method for preparing electrodeposited cobalt under large flow
CN102851508B (en) Method for producing electrolytic lead powder through alkali immersion rotational flow electrolysis of wet electrolytic zinc acid dipping residues
CN113278795A (en) Wet smelting method for high nickel matte
CN104805468A (en) Process for preparing zinc by using zinc oxide material containing complex components like Cu, Pb, Zn, and Ag
JP6489378B2 (en) Method for producing low chlorine concentration mixed aqueous solution of nickel sulfate and cobalt sulfate
CN105018726B (en) A kind of lead zinc mineral intergrowth processing method
JP2017066520A (en) Method for refining bismuth

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
RJ01 Rejection of invention patent application after publication
RJ01 Rejection of invention patent application after publication

Application publication date: 20170405