CN106244813A - A kind of zinc abstraction nickel cobalt slag recoverying and utilizing method - Google Patents

A kind of zinc abstraction nickel cobalt slag recoverying and utilizing method Download PDF

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Publication number
CN106244813A
CN106244813A CN201610768032.5A CN201610768032A CN106244813A CN 106244813 A CN106244813 A CN 106244813A CN 201610768032 A CN201610768032 A CN 201610768032A CN 106244813 A CN106244813 A CN 106244813A
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CN
China
Prior art keywords
cobalt
slag
cadmium
nickel cobalt
nickel
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
CN201610768032.5A
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Chinese (zh)
Inventor
张恩明
姜国敏
陈意达
陈景升
苗应龙
刘继海
张云程
杨开明
肖永生
周滨
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.)
Jiangxi Copper Corp
Jiangxi Copper Co Ltd
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Jiangxi Copper Co Ltd
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Publication date
Application filed by Jiangxi Copper Co Ltd filed Critical Jiangxi Copper Co Ltd
Priority to CN201610768032.5A priority Critical patent/CN106244813A/en
Publication of CN106244813A publication Critical patent/CN106244813A/en
Pending legal-status Critical Current

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    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22BPRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B7/00Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
    • C22B7/006Wet processes
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22BPRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B17/00Obtaining cadmium
    • C22B17/04Obtaining cadmium by wet processes
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22BPRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B23/00Obtaining nickel or cobalt
    • C22B23/04Obtaining nickel or cobalt by wet processes
    • CCHEMISTRY; METALLURGY
    • C25ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25CPROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
    • C25C1/00Electrolytic production, recovery or refining of metals by electrolysis of solutions
    • C25C1/16Electrolytic production, recovery or refining of metals by electrolysis of solutions of zinc, cadmium or mercury
    • CCHEMISTRY; METALLURGY
    • C25ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25CPROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
    • C25C7/00Constructional parts, or assemblies thereof, of cells; Servicing or operating of cells
    • C25C7/06Operating or servicing
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02PCLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P10/00Technologies related to metal processing
    • Y02P10/20Recycling

Abstract

A kind of zinc abstraction nickel cobalt slag recoverying and utilizing method, three sections of inverse antimony purification two-stage nitration purify the nickel cobalt slag produced and add one section of purification after pulp, utilizing the zinc powder of remaining in nickel cobalt slag to purify copper removal cadmium at one section, the slag after using forms copper cadmium cobalt residue, purifies no longer output nickel cobalt slag.Copper cadmium cobalt residue is reclaimed by cadmium after carrying out copper cadmium cobalt residue leaching separation copper, cadmium, and solution is containing between cobalt 150 1000mg/l, and after using organic reagent Call Provision, solution returns main system.The method can make full use of remaining zinc powder, reduction purification zinc consumption in nickel cobalt slag;The recovery of the dangerous solid waste nickel cobalt slag for producing in wet method zinc abstraction opens up a new way;Simplifying cadmium remanufacture technological process, production operation is simple, there is no precedent report both at home and abroad.

Description

A kind of zinc abstraction nickel cobalt slag recoverying and utilizing method
Technical field
The invention belongs to zinc hydrometallurgy industry, for the dangerous solid waste of zinc hydrometallurgy Industrial Output--the recycling of nickel cobalt slag is opened Having warded off a new approach, the method can make full use of the zinc powder of remaining in nickel cobalt slag, reduces one section and purifies zinc powder use The purpose of amount, in turn simplify cadmium remanufacture technique, has saved production cost.
Background technology
In the neutral leaching process of zinc hydrometallurgy, the foreign metal major part such as Fe, As, Sb, Ge can be by neutralizing water Solution preocess removes from solution, but the impurity such as Cu, Cd, Co, the Ni in solution cannot remove at neutral leaching stage, these impurity Relatively big to Zinc electrolysis harm, before electrodeposition, have to pass through purification.Commonly used three sections of (inverse) antimonic salts of most enterprises are clean now Change method, first low temperature is except Cu, Cd, then high temperature is imitated except Co, Ni, its good purification, product quality and electrodeposition electricity and all can be reached satisfied Effect.Three sections of antimony trioxide purification method one two-stage nitration purify output copper-cadmium slag and two kinds of slags of nickel cobalt slag respectively.In industry generally by this two Planting slag individual processing, copper-cadmium slag is after leaching, replace and separating copper cadmium, and solution of zinc sulfate returns main system after except cobalt;Nickel cobalt slag Nickel cobalt slag is remained after pickling.Thus make the dangerous solid waste of zinc hydrometallurgy Industrial Output--nickel cobalt slag.Along with environmental requirement Raising day by day, the process of dangerous solid waste, transport more and more difficult, many enterprises are forced to process self-produced dangerous solid waste voluntarily, Reach the purpose that cleaning produces.The process of nickel cobalt slag, many enterprises self-built zinc sulfate production line of employing or cobalt remanufacture line The problems such as mode recycles, and does not only exist one-time investment big, and production cost is high, often production marketing difficulty, obtain not Repay mistake.
Summary of the invention
The purpose of the present invention is exactly that the dangerous solid waste for zinc hydrometallurgy Industrial Output--the recycling of nickel cobalt slag opens Article one, new approach, makes comprehensive utilization, recovery nickel cobalt slag be possibly realized.
Zinc powder consumption is an important economic indicator in Zinc Hydrometallurgy Process, reduces zinc consumption, is also to reduce electricity Zinc cost, the important channel increased economic efficiency.
According to zinc powder purification by arsenate except the thermodynamic argument of cobalt, Co2+/ Co current potential-0.277V, Cu2+/ Cu current potential+ 0.344V、Zn2+/ Zn current potential-0.762V, when displacement is except cobalt, containing a small amount of antimony in solution, as except the activator of cobalt process, Co can be effectively improved2+Deposition potential, and separate out Co Yu Sb be easily formed CoSb and CoSb2, reduce the precipitation supervoltage of Co, more Be conducive to except Co.But zinc powder utilization rate is the lowest when zinc powder purification by arsenate removes cobalt, two-stage nitration high temperature need to add cobalt 200 times except nickel cobalt Nickel cobalt could be removed to the requirement meeting Zinc electrolysis, containing the zinc that a large amount of unreacteds are complete in the nickel cobalt slag of output by above zinc powder Powder.For these years, the effort through several generations technical staff does not the most solve this problem, causes zinc hydrometallurgy zinc powder consumption always High, production cost is higher.
Through chemical examination, fresh two-stage nitration nickel cobalt slag metal-containing zinc is up to more than 35% (chemical examination composition is shown in Table 1).Through testing Card, this portion of residual zinc powder may be used for one section of purification replacement zinc powder and carries out the displacement reaction of copper removal cadmium, thus reaches nickel cobalt slag The purpose recycled and reclaim, and other operating conditions are the most constant.
The nickel cobalt slag result of laboratory test (unit: %) that table 1 is fresh
Accompanying drawing explanation
Fig. 1 former zinc abstraction purification artwork,
Fig. 2 zinc abstraction of the present invention purifies process chart
Detailed description of the invention
A kind of zinc abstraction nickel cobalt slag recoverying and utilizing method, returns one section including purifying Ni and Co slag and purifies as zinc powder recycling, Cadmium reclaims cancels nickel cobalt slag pickling production, reclaims the cobalt-carrying solution after copper cadmium and uses three parts such as organic reagent Technology for removing cobalt.
The method is a new approach of the recycling of nickel cobalt slag, can effectively reduce purification zinc consumption.
1, the method first using send cadmium to reclaim after oleo stock to carry out the two-stage nitration nickel cobalt slag of pickling change deliver to one section purify as Zinc powder uses, and one section purifies minimizing zinc powder consumption more than 70%, and other control process conditions and do not change, it may be assumed that reaction temperature 50-90 DEG C, response time 1 3h, flow 100-160m3/ h, pH value 5.0-5.4.
2, after two-stage nitration nickel cobalt slag is used for one section of purification by step 1, purification one section of purification slag of an output, thus no longer output two Section nickel cobalt slag, one section of purification slag is the mixing slag (can be copper cadmium cobalt residue) of copper-cadmium slag and nickel cobalt slag.
3, after two-stage nitration nickel cobalt slag is used for one section of purification by step 1, cadmium reclaims cancels former nickel cobalt slag acid cleaning process.
4, step 1 two-stage nitration nickel cobalt slag is used for one section purify after, the copper cadmium cobalt residue of output send cadmium recovery process fully according to Former technical operation flow produces, and copper-cadmium slag leaches, the technology condition of displacement production cadmium cake is constant, and last cobalt-carrying solution (lean cadmium solution) uses organic reagent Technology for removing cobalt except cobalt.
5, organic reagent described in step 4 is that the specialty that certain enterprise produces removes cobalt nickel reagent, black liquor, proportion 1.05 1.1, consumption is 15 20 times of cobalt amount of metal.
6, organic reagent Technology for removing cobalt described in step 4, controls reaction temperature 50-80 DEG C, response time 0.5 1.5h, removes Cobalt nickel reagent addition is 15 20 times of cobalt amount of metal.
7, step 6 reaction terminates cobalt concentrate 3-6% Han cobalt, the zinc 10-18% of rear output, can reclaim metal further Cobalt.
The method uses over 2 years in Qian Xin enterprise of Jiangxi Province, and two-stage nitration nickel cobalt slag is able to all of and reclaims, this enterprise No longer output danger solid waste--nickel cobalt slag.In the case of quantity-produced, it can be ensured that qualified rate of new solution more than 99%.Two-stage nitration is clean Changing after nickel cobalt slag returns one section of purification and fully recycled the remaining Zn powder in nickel cobalt slag, one section of purification the most all need not list Solely add zinc powder, one section of zinc powder consumption 60 80% can be saved.Cadmium reclaims the pickling operation no longer carrying out nickel cobalt slag, annual output 100-150 ton cobalt concentrate, becomes new profit growth point.

Claims (4)

1. three sections of inverse antimony are purified two-stage nitration and purify the nickel cobalt slag produced after pulp by a zinc abstraction nickel cobalt slag recoverying and utilizing method Adding one section of purification, utilize the zinc powder of remaining in nickel cobalt slag to purify copper removal cadmium at one section, the slag after using forms copper cadmium cobalt residue, only Change no longer output nickel cobalt slag, it is achieved dangerous solid waste--nickel cobalt slag recycles, it is possible to decrease one section purifies zinc powder consumption.
A kind of zinc abstraction nickel cobalt slag recoverying and utilizing method the most according to claim 1, it is characterised in that (1), the method first First delivering to one section of purification use sending cadmium to reclaim after oleo stock to carry out the two-stage nitration nickel cobalt slag of pickling to change as zinc powder, one section of purification subtracts Few zinc powder consumption more than 70%, controlling process conditions is: reaction temperature 50-90 DEG C, response time 1 3h, flow 100- 160m3/ h, pH value 5.0-5.4;
(2), step 1 two-stage nitration nickel cobalt slag is used for one section purify after, purify one section of purification slag of an output, thus no longer output two-stage nitration Nickel cobalt slag, one section of purification slag is the mixing slag of copper-cadmium slag and nickel cobalt slag;
(3), step 1 two-stage nitration nickel cobalt slag is used for one section purify after, cadmium reclaim cancel former nickel cobalt slag acid cleaning process;
(4), step 1 two-stage nitration nickel cobalt slag is used for one section purify after, the copper cadmium cobalt residue of output send cadmium recovery process fully according to former Technical operation flow produces, and copper-cadmium slag leaches, the technology condition of displacement production cadmium cake is constant, and last cobalt-carrying solution removes Cobalt uses organic reagent Technology for removing cobalt;
(5), organic reagent described in step 4 is that consumption is cobalt amount of metal except cobalt nickel reagent, black liquor, proportion 1.05 1.1 15 20 times;
(6), organic reagent Technology for removing cobalt described in step 4, control reaction temperature 50-80 DEG C, response time 0.5 1.5h, except cobalt Nickel reagent addition is 15 20 times of cobalt amount of metal;
(7), step 6 reaction terminate cobalt concentrate 3-6% Han cobalt, the zinc 10-18% of rear output, metallic cobalt can be reclaimed further.
A kind of zinc abstraction nickel cobalt slag recoverying and utilizing method the most according to claim 2, it is characterised in that owing to purifying no longer Output nickel cobalt slag, cadmium recovery process is no longer necessary to nickel cobalt slag pickling except cobalt operation, simplification cadmium remanufacture technique.
A kind of zinc abstraction nickel cobalt slag recoverying and utilizing method the most according to claim 2, it is characterised in that cadmium recovery process returns After receiving the copper in copper cadmium cobalt residue, cadmium, solution, containing between cobalt 150 1000mg/L, uses organic reagent Call Provision, produces containing cobalt The cobalt concentrate of about 5%.
CN201610768032.5A 2016-08-29 2016-08-29 A kind of zinc abstraction nickel cobalt slag recoverying and utilizing method Pending CN106244813A (en)

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Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107400781A (en) * 2017-07-21 2017-11-28 安阳市岷山有色金属有限责任公司 A kind of recovery method of lead smelting waste material containing zinc
CN107557580A (en) * 2017-08-18 2018-01-09 西北矿冶研究院 Method for removing copper and cadmium by zinc hydrometallurgy purification
CN108977666A (en) * 2018-08-30 2018-12-11 河南豫光锌业有限公司 The recovery method of zinc cobalt in a kind of purification slag of zinc hydrometallurgy
CN109371244A (en) * 2018-11-07 2019-02-22 江西理工大学 A method of be enriched with and open a way from zinc hydrometallurgy leachate using zinc powder purification slag impurity
CN110629024A (en) * 2019-08-23 2019-12-31 白银有色集团股份有限公司 Process for inhibiting cobalt and cadmium redissolution in zinc hydrometallurgy purification process
CN113462898A (en) * 2021-06-19 2021-10-01 西部矿业股份有限公司 Novel oxygen pressure leaching zinc smelting purification impurity removal process
CN113621829A (en) * 2021-08-23 2021-11-09 云南金鼎锌业有限公司 Purifying method for zinc smelting powdery purifying agent
CN114703379A (en) * 2022-02-21 2022-07-05 云锡文山锌铟冶炼有限公司 Deep purification method for neutral leaching solution of zinc hydrometallurgy

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CN104593600A (en) * 2014-12-26 2015-05-06 云南永昌铅锌股份有限公司 Method for processing zinc sulfate solution purification residue

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Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107400781A (en) * 2017-07-21 2017-11-28 安阳市岷山有色金属有限责任公司 A kind of recovery method of lead smelting waste material containing zinc
CN107400781B (en) * 2017-07-21 2019-07-12 安阳市岷山有色金属有限责任公司 A kind of recovery method of lead smelting waste material containing zinc
CN107557580A (en) * 2017-08-18 2018-01-09 西北矿冶研究院 Method for removing copper and cadmium by zinc hydrometallurgy purification
CN108977666A (en) * 2018-08-30 2018-12-11 河南豫光锌业有限公司 The recovery method of zinc cobalt in a kind of purification slag of zinc hydrometallurgy
CN108977666B (en) * 2018-08-30 2020-01-07 河南豫光锌业有限公司 Method for recovering zinc and cobalt in zinc hydrometallurgy purification slag
CN109371244A (en) * 2018-11-07 2019-02-22 江西理工大学 A method of be enriched with and open a way from zinc hydrometallurgy leachate using zinc powder purification slag impurity
CN110629024A (en) * 2019-08-23 2019-12-31 白银有色集团股份有限公司 Process for inhibiting cobalt and cadmium redissolution in zinc hydrometallurgy purification process
CN113462898A (en) * 2021-06-19 2021-10-01 西部矿业股份有限公司 Novel oxygen pressure leaching zinc smelting purification impurity removal process
CN113462898B (en) * 2021-06-19 2022-09-06 西部矿业股份有限公司 Oxygen pressure leaching zinc smelting purification impurity removal process
CN113621829A (en) * 2021-08-23 2021-11-09 云南金鼎锌业有限公司 Purifying method for zinc smelting powdery purifying agent
CN114703379A (en) * 2022-02-21 2022-07-05 云锡文山锌铟冶炼有限公司 Deep purification method for neutral leaching solution of zinc hydrometallurgy
CN114703379B (en) * 2022-02-21 2023-09-22 云锡文山锌铟冶炼有限公司 Method for deeply purifying neutral leaching solution of zinc hydrometallurgy

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Application publication date: 20161221