CN110184468A - A method of recycling copper from secondary zinc oxide - Google Patents

A method of recycling copper from secondary zinc oxide Download PDF

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Publication number
CN110184468A
CN110184468A CN201910610501.4A CN201910610501A CN110184468A CN 110184468 A CN110184468 A CN 110184468A CN 201910610501 A CN201910610501 A CN 201910610501A CN 110184468 A CN110184468 A CN 110184468A
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CN
China
Prior art keywords
copper
zinc oxide
secondary zinc
oxygen
section
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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.)
Pending
Application number
CN201910610501.4A
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Chinese (zh)
Inventor
张梅
晋家强
张殿彬
邹利明
闫建英
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Yunnan Hongchi Resource Integration Utilization Co Ltd
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Yunnan Hongchi Resource Integration Utilization Co Ltd
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Priority to CN201910610501.4A priority Critical patent/CN110184468A/en
Publication of CN110184468A publication Critical patent/CN110184468A/en
Pending legal-status Critical Current

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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
    • C22B15/00—Obtaining copper
    • C22B15/0063—Hydrometallurgy
    • C22B15/0065—Leaching or slurrying
    • C22B15/0067—Leaching or slurrying with 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
    • C22B15/00—Obtaining copper
    • C22B15/0063—Hydrometallurgy
    • C22B15/0084—Treating solutions
    • C22B15/0089—Treating solutions by chemical methods
    • C22B15/0091—Treating solutions by chemical methods by cementation
    • 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
    • C22B7/00—Working 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
    • C22B7/006—Wet processes
    • C22B7/007—Wet processes by acid leaching
    • 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

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Environmental & Geological Engineering (AREA)
  • General Life Sciences & Earth Sciences (AREA)
  • Geology (AREA)
  • Manufacture And Refinement Of Metals (AREA)

Abstract

The method that the present invention relates to a kind of to recycle copper from secondary zinc oxide, belong to non-ferrous metal field of hydrometallurgy, the present invention presses process secondary zinc oxide using+two sections of oxygen of one section of normal pressure, copper is precipitated into slag when one section of normal pressure acidleach, copper is leached again when two sections of oxygen leachings, oxygen leaching liquid returns to one section of normal pressure acidleach, it is enriched with copper in oxygen leaching liquid gradually, using iron replacement copper, in secondary zinc oxide 90% or more copper can be made to be recycled, the copper ashes of output contains Cu60-75%, Fe8-20%, and copper is recycled from secondary zinc oxide to realize.

Description

A method of recycling copper from secondary zinc oxide
Technical field
The invention belongs to non-ferrous metal field of hydrometallurgy, specifically, is related to a kind of recycling copper from secondary zinc oxide Method.
Background technique
Acid leaching residue, the low-grade lead Zinc oxide stone etc. that zinc hydrometallurgy generates, using rotary kiln, fuming furnace and Ao Simai The stoves such as special furnace volatilizing and enriching lead zinc and the rare precious metal of association, output secondary zinc oxide.Secondary zinc oxide is except leaded zinc and germanium indium silver Outside equal rare precious metals, Shang Hantong 0.05-0.4%, iron content 2-6%.Secondary zinc oxide is using two sections of normal pressure acidleach or is one section normal When pressing+two sections of oxygen leaching zinc and germanium indium, according to the difference that Process configuration and technical parameter control, copper enters leached mud (lead skim) Or enter and neutralize iron dross removing loss, copper is not recycled.
Copper is more valuable non-ferrous metal, and COPPER IN CHINA natural resources shortage.Therefore, zinc is recycled in secondary zinc oxide wet-treating When, method that is a kind of while recycling copper is found, the recycling of copper in secondary zinc oxide is realized, improves the economic benefit of enterprise, have It is of great significance.
Summary of the invention
In order to solve the problems, such as background technique, the present invention provides a kind of from secondary zinc oxide recycles the side of copper Method presses process secondary zinc oxides using+two sections of oxygen of one section of normal pressure, and copper is precipitated into slag, two sections of oxygen pressure leachings when one section of normal pressure acidleach Copper is leached again when out, and oxygen leaching liquid returns to one section of normal pressure acidleach, is enriched with copper in oxygen leaching liquid gradually, is used Iron replacement copper can be such that in secondary zinc oxide 90% or more copper is recycled, and copper is recycled from secondary zinc oxide to realize.
To achieve the above object, the present invention is achieved through the following technical solutions:
The method that copper is recycled in the slave secondary zinc oxide, specifically includes the following steps: the secondary oxygen containing Cu0.05-0.1% Change zinc and be precipitated into slag through copper when one section of normal pressure acidleach, copper is leached again when two sections of oxygen leachings, every wheel oxygen leaching liquid Cu2+It is rich Integrate concentration as 0.2-0.4g/L, oxygen leaching liquid returns to one section of normal pressure acidleach, every wheel oxygen leaching liquid Cu2+Concentration is all being enriched with； Control Cu in oxygen leaching liquid2+Concentration, as Cu in oxygen leaching liquid2+When concentration enrichment is to 2-3g/L, addition iron powder carries out copper Displacement recycling, iron powder additional amount are (Cu2++Fe3+) × 0.9g/L, output replacement slag contain Cu60-75%, Fe8-20%.
By testing and verification and preferably, the highest for controlling copper in oxygen leaching liquid allows content to be Cu2+≤ 3g/L, it is therefore an objective to Cu when preventing one section of acidleach2+Not exclusively, into one section of pickle liquor, copper enters iron to precipitating in one section of pickle liquor air blast and when except iron arsenic Slag loss.
Beneficial effects of the present invention:
The present invention presses process secondary zinc oxides using+two sections of oxygen of one section of normal pressure, and copper is precipitated into slag when one section of normal pressure acidleach, Copper is leached again when two sections of oxygen leachings, and oxygen leaching liquid returns to one section of normal pressure acidleach, make in oxygen leaching liquid copper obtain by Step enrichment, using iron replacement copper, can be such that in secondary zinc oxide 90% or more copper is recycled, and the copper ashes of output contains Cu60- 75%, Fe8-20% avoid the copper in secondary zinc oxide from entering leached mud or iron dross removing loss, return from secondary zinc oxide to realize Receive copper.
Detailed description of the invention
Fig. 1 is process flow chart of the invention.
Specific embodiment
It, below will be to preferred reality of the invention in order to keep the purpose of the present invention, technical scheme and beneficial effects clearer It applies example to be described in detail, to facilitate the technical staff to understand.
Embodiment 1
Secondary zinc oxide (Cu 0.05%) 1kg passes through one section of normal pressure leaching, leaching condition are as follows: and 75 DEG C of reaction temperature, terminal pH =2.5, reaction time 2h, liquid-solid ratio 5:1 generate leached mud and contain Cu 0.1%；Using two sections of oxygen leachings, leaching condition Are as follows: it is continuously passed through oxygen, controls partial pressure of oxygen 0.3Mpa, 150 DEG C of reaction temperature, terminal acidity 20g/L, reaction time 2h, liquid is solid Than 5:1, leachate is obtained containing Cu2+192mg/L, then by after solution one section of normal pressure leaching of return, Cu enters slag again, and so circulation is rich Collection, until Cu in oxygen hydraulic fluid2+Reach 2300mg/L, add 0.9 times of iron powder displacement, obtain Cu slag, containing Cu68.75%, Fe18.92%, the Cu rate of recovery are 93.5%.
Embodiment 2
Secondary zinc oxide (Cu 0.1%) 1kg passes through one section of normal pressure leaching, leaching condition are as follows: and 75 DEG C of reaction temperature, terminal pH =3.5, reaction time 2h, liquid-solid ratio 5:1 generate leached mud and contain Cu 0.2%, using two sections of oxygen leachings, leaching condition Are as follows: it is continuously passed through oxygen, controls partial pressure of oxygen 0.3Mpa, 150 DEG C of reaction temperature, terminal acidity 15g/L, reaction time 2h, liquid is solid Than 5:1, leachate is obtained containing Cu2+396mg/L, then by after solution one section of normal pressure leaching of return, Cu enters slag again, and so circulation is rich Collection, until Cu in oxygen hydraulic fluid2+Reach 2960mg/L, add 0.9 times of iron powder displacement, obtain Cu slag, containing Cu 75.23%, Fe7.83%, the Cu rate of recovery are 94.5%.
Experimental analysis
1, copper circulation collection in secondary zinc oxide leachate
When (1) one section of normal pressure acidleach, the copper and ferrous iron being leached react, and are precipitated into slag, reaction equation are as follows:
ZnO+2H+=Zn2++H2O (1)
Cu2++Fe2+=Cu++Fe3+ (2)
2Cu++ ZnO=Cu2O+Zn2+ (3)
2Fe3++ ZnS=2Fe2++Zn2++S↓ (4)
When (2) one sections of normal pressure leaching slag oxygen leachings, the copper for being precipitated into slag is leached again, reaction equation are as follows:
Cu2O+1/2O2+4H+=2Cu2++2H2O (5)
Copper is leached again in oxygen leaching, when returning to one section of normal pressure acidleach with oxygen leaching liquid, is deposited once more Enter slag and enter oxygen leaching, when secondary zinc oxide when containing Cu0.05-0.1%, every wheel oxygen leaching liquid copper ion rises 0.2-0.4g/ L, to realize copper circulation collection in leachate.
2, the highest for controlling copper in oxygen leaching liquid allows content to be Cu2+≤3g/L
After reaction equation (2) to limiting value, extra Cu in leachate2+One section of normal pressure leaching liquid will be entered, in one section of normal pressure Leachate air blast enters scum loss when neutralizing except iron, need to determine, control that the highest of copper in oxygen leaching liquid allows content, avoid Cu2+Into being lost in one section of normal pressure leaching liquid.
By testing and verification, work as Cu2+When content is 0.6 times of iron content in secondary zinc oxide, one section of normal pressure leaching liquid contains Cu2 +≤ 5mg/L, corresponding oxygen leaching liquid contain Cu2+≤ 3g/L, works as Cu2+When content is greater than 0.6 times of iron content in secondary zinc oxide, One section of normal pressure leaching liquid Cu2+It rises with it.Therefore, Cu2+≤ 3g/L is that the highest of oxygen leaching liquid one section of normal pressure acidleach of return permits Perhaps content.
3, using iron replacement from oxygen leaching liquid separation removal copper
There is copper-removing method in solution: hydroxide precipitation method, displacement method, electrodeposition method, solvent extraction, ion-exchange And the methods of sulphide precipitation.By Experimental Comparison, final choice displacement method, by using zinc powder and iron powder comparative test, It is preferred that going out iron replacement removes copper.The determining iron powder additional amount of test=
(Cu2++Fe3+)×(0.8-1.0)g/L。
Influence by Experimental Comparison oxygen leaching liquid copper content to copper ashes grade, iron powder additional amount are (Cu2++Fe3+)× 0.9g/L, such as table 1.
Table 1
As seen from Table 1, Cu is contained in oxygen leaching liquid2+When < 2.0g/L, the copper ashes grade of output is low, and the quantity of slag is big, works as Cu2+ When >=2.0g/L, copper ashes cupric is high, and the quantity of slag is small.Therefore, reasonable copper ion concentration is 2-3g/L when iron replacement copper, is both guaranteed Copper ashes grade, and avoid copper ion from entering one section of normal pressure pickle liquor and be lost.
By circulation collection copper, content of copper ion 2-3g/L in oxygen leaching liquid is controlled, using iron replacement, controls iron powder Additional amount=(Cu2++Fe3+) × (0.8-1.0) means such as g/L, in secondary zinc oxide 90% or more copper can be made to obtain recycling benefit With the copper ashes of output contains Cu60-75%, Fe8-20%.
Finally, it is stated that preferred embodiment above is only used to illustrate the technical scheme of the present invention rather than limits, although logical It crosses above preferred embodiment the present invention is described in detail, however, those skilled in the art should understand that, can be Various changes are made to it in form and in details, without departing from claims of the present invention limited range.

Claims (6)

1. a kind of method for recycling copper from secondary zinc oxide, it is characterised in that: specifically includes the following steps: secondary zinc oxide is through one section Copper is precipitated into slag when normal pressure acidleach, is leached again using copper when two sections of oxygen leachings, returns to one section often with oxygen leaching liquid Press acidleach, every wheel oxygen leaching liquid Cu2+Concentration is all being enriched with；As Cu in oxygen leaching liquid2+Concentration enrichment is added to 2-3g/L Iron powder carries out displacement recycling to copper.
2. a kind of method for recycling copper from secondary zinc oxide according to claim 1, it is characterised in that: contain in secondary zinc oxide Cu0.05-0.1%。
3. a kind of method for recycling copper from secondary zinc oxide according to claim 1, it is characterised in that: every wheel oxygen leaching Liquid Cu2+Enriched concentration is 0.2-0.4g/L.
4. a kind of method for recycling copper from secondary zinc oxide according to claim 1, it is characterised in that: control oxygen leaching The highest of copper allows content to be Cu in liquid2+≤3g/L。
5. a kind of method for recycling copper from secondary zinc oxide according to claim 1, it is characterised in that: iron replacement copper When, iron powder additional amount is (Cu2++Fe3+) × 0.9g/L.
6. a kind of method for recycling copper from secondary zinc oxide according to claim 1, it is characterised in that: the replacement slag of output Containing Cu60-75%, Fe8-20%.
CN201910610501.4A 2019-07-08 2019-07-08 A method of recycling copper from secondary zinc oxide Pending CN110184468A (en)

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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20100086455A1 (en) * 2007-05-07 2010-04-08 Kevin Clais Metohd of producing oxide and power thus obtained
CN103014350A (en) * 2012-12-22 2013-04-03 泸溪蓝天冶化有限责任公司 Recycling method of zinc hypoxide
EP2706578A1 (en) * 2011-06-10 2014-03-12 Tokyo Ohka Kogyo Co., Ltd. HYDRAZINE-COORDINATED Cu CHALCOGENIDE COMPLEX AND METHOD FOR PRODUCING SAME, APPLICATION LIQUID FOR FORMING LIGHT-ABSORBING LAYER, AND METHOD FOR PRODUCING APPLICATION LIQUID FOR FORMING LIGHT-ABSORBING LAYER
CN107058751A (en) * 2017-02-17 2017-08-18 中国恩菲工程技术有限公司 The method that zinc, copper and germanium are reclaimed from zinc oxide fumes
CN109897966A (en) * 2019-03-29 2019-06-18 何耀 A kind of secondary zinc oxide raw material high-efficiency resource recycling method
CN109943722A (en) * 2019-04-03 2019-06-28 徐州市正峰锌业有限公司 A kind of reuse method of secondary zinc oxide

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20100086455A1 (en) * 2007-05-07 2010-04-08 Kevin Clais Metohd of producing oxide and power thus obtained
EP2706578A1 (en) * 2011-06-10 2014-03-12 Tokyo Ohka Kogyo Co., Ltd. HYDRAZINE-COORDINATED Cu CHALCOGENIDE COMPLEX AND METHOD FOR PRODUCING SAME, APPLICATION LIQUID FOR FORMING LIGHT-ABSORBING LAYER, AND METHOD FOR PRODUCING APPLICATION LIQUID FOR FORMING LIGHT-ABSORBING LAYER
CN103014350A (en) * 2012-12-22 2013-04-03 泸溪蓝天冶化有限责任公司 Recycling method of zinc hypoxide
CN107058751A (en) * 2017-02-17 2017-08-18 中国恩菲工程技术有限公司 The method that zinc, copper and germanium are reclaimed from zinc oxide fumes
CN109897966A (en) * 2019-03-29 2019-06-18 何耀 A kind of secondary zinc oxide raw material high-efficiency resource recycling method
CN109943722A (en) * 2019-04-03 2019-06-28 徐州市正峰锌业有限公司 A kind of reuse method of secondary zinc oxide

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Application publication date: 20190830