CN108950215A - Low-grade nickle contained discarded material processing method - Google Patents
Low-grade nickle contained discarded material processing method Download PDFInfo
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- CN108950215A CN108950215A CN201810847578.9A CN201810847578A CN108950215A CN 108950215 A CN108950215 A CN 108950215A CN 201810847578 A CN201810847578 A CN 201810847578A CN 108950215 A CN108950215 A CN 108950215A
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- clinker
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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
- 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
- C22B7/001—Dry processes
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
- C03B37/00—Manufacture or treatment of flakes, fibres, or filaments from softened glass, minerals, or slags
- C03B37/01—Manufacture of glass fibres or filaments
- C03B37/04—Manufacture of glass fibres or filaments by using centrifugal force, e.g. spinning through radial orifices; Construction of the spinner cups therefor
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C13/00—Fibre or filament compositions
- C03C13/06—Mineral fibres, e.g. slag wool, mineral wool, rock wool
-
- 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
- C22B23/00—Obtaining nickel or cobalt
- C22B23/02—Obtaining nickel or cobalt by dry processes
- C22B23/025—Obtaining nickel or cobalt by dry processes with formation of a matte or by matte refining or converting into nickel or cobalt, e.g. by the Oxford process
-
- 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
- C22B23/00—Obtaining nickel or cobalt
- C22B23/04—Obtaining nickel or cobalt by wet processes
- C22B23/0453—Treatment or purification of solutions, e.g. obtained by leaching
- C22B23/0461—Treatment or purification of solutions, e.g. obtained by leaching by chemical methods
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
- C25C1/00—Electrolytic production, recovery or refining of metals by electrolysis of solutions
- C25C1/06—Electrolytic production, recovery or refining of metals by electrolysis of solutions or iron group metals, refractory metals or manganese
- C25C1/08—Electrolytic production, recovery or refining of metals by electrolysis of solutions or iron group metals, refractory metals or manganese of nickel or cobalt
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
- C25C1/00—Electrolytic production, recovery or refining of metals by electrolysis of solutions
- C25C1/12—Electrolytic production, recovery or refining of metals by electrolysis of solutions of copper
-
- 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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- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Metallurgy (AREA)
- Life Sciences & Earth Sciences (AREA)
- Manufacturing & Machinery (AREA)
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- General Life Sciences & Earth Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
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Abstract
The invention discloses a kind of low-grade nickle contained discarded material processing methods, comprising the following steps: (1) dehydrates nickle contained discarded material to water content 10-15%；(2) nickle contained discarded material after dehydration and drying is pressed into brick；(3) gained nickle contained discarded material brick is used into oxygen-enriched side-blowing furnace melting, obtains nis matte and clinker；(4) by nis matte founding obtained by step (3) at anode plate, anode plate is electrolysed using diaphragm process, obtains metallic nickel and nickel electrowinning waste liquid；(5) by clinker obtained by step (3) for producing rock wool；(6) oxidation of nickel electrowinning waste liquid obtained by step (4) is neutralized and removes iron, except liquid uses strike decopper(ing) after iron, obtain metallic copper；(7) nickelous carbonate of liquid after decopper(ing) obtained by step (6) decopper(ing) is adjusted into pH value to 4.8, is sent into chlorine hybrid reaction, obtains cobalt.Using method of the invention, low-grade nickle contained discarded material can be efficiently treated through, the rate of recovery of nickel can achieve 95% or more.
Description
Technical field
The present invention relates to a kind of reuse of solid waste method more particularly to a kind of low-grade nickle contained discarded material processing methods.
Background technique
Nickel can generate the waste materials such as clinker after smelting or processing, these waste materials also contain a certain amount of nickel, but nickeliferous grade
Lower, general nickel content is 1-15%.
Now, very low for these low-grade nickle contained discarded material utilization rates, it is at high cost；But hesitate to discard, and pollute ring
Border.
Currently, there are mainly two types of processing methods for low-grade nickle contained discarded material: first, producing ferronickel using fire reduction melting
Alloy, this method energy consumption is high, investment is big, and production cost is higher；Second, producing metallic nickel, this method processing using wet-treating
Low-grade nickle contained discarded material generally uses sulfuric acid leaching to obtain nickel sulfate solution, and nickel sulfate solution is passed through except iron, copper removal, arsenic removal antimony, removed
The processes such as cobalt obtain qualified nickel sulfate solution, and nickel sulfate solution produces metallic nickel, the technique mistake using the method for electrolytic deposition
Journey long flow path, nickel recovery are low, and nickel recovery is less than 80%, and high production cost.
It finds that a kind of nickel recovery is high, low-grade nickle contained discarded material processing method at low cost, is that those skilled in the art compel
Be essential technical problems to be solved.
Summary of the invention
High, low-grade nickle contained discarded material processing method at low cost that the purpose of the present invention is to provide a kind of nickel recoveries.
In order to solve the above-mentioned technical problem, low-grade nickle contained discarded material processing method of the invention the following steps are included:
(1) nickle contained discarded material is dehydrated to water content 10-15%；
(2) nickle contained discarded material after dehydration and drying is pressed into brick；
(3) gained nickle contained discarded material brick is used into oxygen-enriched side-blowing furnace melting, obtains nis matte and clinker；
(4) by nis matte founding obtained by step (3) at anode plate, anode plate is electrolysed using diaphragm process, obtains metallic nickel
With nickel electrowinning waste liquid；
(5) by clinker obtained by step (3) for producing rock wool；
(6) oxidation of nickel electrowinning waste liquid obtained by step (4) is neutralized and removes iron, except liquid uses strike decopper(ing) after iron, obtain gold
Belong to copper；
(7) nickelous carbonate of liquid after decopper(ing) obtained by step (6) decopper(ing) is adjusted into pH value to 4.8, is sent into chlorine hybrid reaction, obtains
Cobalt.
The earth of positive pole after step (4) electrolysis is subjected to advanced treating, extracts the noble metal being rich in.These noble metals are such as
Gold, silver, lead, bismuth etc..Processing method can use the prior art.
The lime of the nickle contained discarded material supplying weight ratio 5-10% makees binder and is pressed into brick through brick machine.
The sequence of the oxygen-enriched side-blowing furnace charging is first to add coke, then plus nickel brick.
1250-1350 DEG C of the smelting temperature of the oxygen-enriched side-blowing furnace, oxygen-rich concentration 24-28%.
The nis matte nickel content of the melting output is 10-30%, cupric 5-15%.
The main chemical compositions of the oxygen-enriched side-blowing furnace clinker be NiO0.1-0.5%, FeO3-9%, SiO242-55%,
MgO3-16%、CaO5-25%、Al2O32-8%。
The nickle contained discarded material nickel content is 1-15%.
Clinker obtained by the step (3) includes the following steps: a. by clinker with white clouds for producing rock wool, preparation method
Stone, coke, which enter, carries out melting in hardening and tempering furnace；B. the iron of melting output is separated, through cooling ingot casting；C. by the melt after separation iron
Wire drawing is at rock wool fibers in feeding multiple roll centrifuge.
It is preferred that the coke of dolomite, 8-15% by clinker with weight ratio 20-40% enters to carry out melting in hardening and tempering furnace, it is quenched
The temperature of melting is 1250-1280 DEG C in furnace.
Using method of the invention, low-grade nickle contained discarded material can be efficiently treated through, the rate of recovery of nickel can achieve
95% or more, and the valuable metals such as copper, cobalt can also be comprehensively utilized, clinker can also continue to be used in production rock wool, and it is at low cost,
The defect for overcoming the prior art, takes full advantage of solid waste, turns waste into wealth, and not only improves environment, and has saved big
Resource is measured, is increased economic efficiency.
Specific embodiment
Method of the invention is described in detail below.
Low-grade nickle contained discarded material processing method the following steps are included:
(1) nickle contained discarded material is dehydrated to water content 10-15%；
(2) nickle contained discarded material after dehydration and drying is pressed into brick；
(3) gained nickle contained discarded material brick is used into oxygen-enriched side-blowing furnace melting, obtains nis matte and clinker；
(4) by nis matte founding obtained by step (3) at anode plate, anode plate is electrolysed using diaphragm process, obtains metallic nickel
With nickel electrowinning waste liquid；
(5) by clinker obtained by step (3) for producing rock wool；
(6) oxidation of nickel electrowinning waste liquid obtained by step (4) is neutralized and removes iron, except liquid uses strike decopper(ing) after iron, obtain gold
Belong to copper；
(7) nickelous carbonate of liquid after decopper(ing) obtained by step (6) decopper(ing) is adjusted into pH value to 4.8, is sent into chlorine hybrid reaction, obtains
Cobalt.
The earth of positive pole after step (4) electrolysis is subjected to advanced treating, extracts the noble metal being rich in.These noble metals are such as
Gold, silver, lead, bismuth etc..Processing method is the prior art.
Nickle contained discarded material nickel content is 1-15%.
The lime of nickle contained discarded material supplying weight ratio 5-10% makees binder and is pressed into brick through brick machine.Lime weight ratio is again
Preferably 6-9%；More preferably 7-8%；Preferably 10%.
The sequence of oxygen-enriched side-blowing furnace charging preferably first adds coke, then plus nickel brick.
The smelting temperature of oxygen-enriched side-blowing furnace is preferably 1250-1350 DEG C, and oxygen-rich concentration is preferably 24-28%.
The nis matte nickel content of melting output is 10-30%, cupric 5-15%.
The main chemical compositions of oxygen-enriched side-blowing furnace clinker are NiO0.1-0.5%, FeO3-9%, SiO242-55%, MgO3-
16%、CaO5-25%、Al2O32-8%。
These clinkers are for producing rock wool.Preparation method includes the following steps: that clinker is entered to adjust by a. with dolomite, coke
Melting is carried out in matter furnace；B. the iron of melting output is separated, through cooling ingot casting；C. the melt after separation iron is sent into multiple roll centrifugation
Wire drawing is at rock wool fibers in machine.The coke of dolomite, 8-15% by clinker with weight ratio 20-40% enters in hardening and tempering furnace to melt
It refines, the temperature of melting is 1250-1280 DEG C in hardening and tempering furnace.
Such as using electroplating sludge as raw material, main chemical compositions Ni8.60%, Cu8.13%, Au3g/t, Ag500g/t,
Fe7.93%、Al2O34.31%、S3.48%、CaO7.87%、MgO3.42%、SiO26.95%.The electroplating sludge is aqueous after drying
10%, the lime for being incorporated 10% makees binder and is pressed into the brick with some strength through brick machine, and brick is after drying using richness
Oxygen side-blown converter melting produces nis matte, and fusion process is incorporated silica sand, troilite to adjust the slag type of side-blown converter, oxygen-enriched side-blowing furnace drum
The oxygen-enriched air concentration entered is 26%.
1350 DEG C of side-blown converter smelting temperature, the nis matte nickeliferous 21.18% of institute's output, cupric 20.04%.Nis matte is cast into
Metallic nickel is produced using diaphragm electrolysis after anode plate, the main technologic parameters of electrorefining are Ni2+Concentration 60-65g/L, Na+It is dense
Spend 45-60g/L, H3BO4Concentration 4-6g/L, organic matter 1g/L, Cl-Concentration 70-100g/L, electrolyte ph 2-2.5, electrolysis electricity
Current density 160-180A/m2, 60-65 DEG C of electrolyte temperature, homopolarity center is away from 190mm, anode life 6-9d, cathode deposition period 4-
5d, anode and cathode liquid level difference 30-50mm, slotting period 2-3 month.
Nickel electrowinning waste liquid removes iron using oxidation neutralisation, blasts sky into used anolyte at a temperature of 343-353K
Gas, Fe2+It is oxidized to Fe3+；And nickelous carbonate adjustment pH to 3.5-4.2 is added, make Fe3+It is hydrolyzed into the Fe (OH) of indissoluble3Precipitating is removed
It goes.
Except liquid uses one section of strike decopper(ing) after iron, copper stripping electrolysis uses insoluble anode, and insoluble anode is using lead silver
Alloy anode plate, cathode use stainless steel plate, decopper(ing) process important technological parameters are as follows: tank voltage 1.8-2.3V, current density
120A/m2, 40-55 DEG C of electrolyte temperature, electrolyte circulation rate 20-25L/(min. slot), homopolarity center is away from 120mm.
Liquid nickelous carbonate adjusts pH value to after 4.8 after copper removal, is sent into chlorine mixing reactor with centrifugal pump, chlorine with remove
Enter reacting pipe after liquid is sufficiently mixed in reactor after copper, subsequently enter in air stirring slot, except cobalt process keeps solution
PH value 4.5-5.0.
The rate of recovery 95%, the rate of recovery of copper of entire process flow nickel are 94%.
Clinker is for producing rock wool.
Such as using the smelted furnace cinder of certain domestic nickel smelter as raw material, wherein NiO0.1%, FeO7.08%, SiO254.74%、
MgO10.30%、Al2O34.48%、Cr2O30.22%,CaO12.84%.The dolomite of supplying 20%, the main chemical compositions of dolomite
CaO30.0%、MgO21.0%、SiO20.8%、Fe2O30.1%、Al2O31.0%.The amount of allocating of coke is 8%.Nickel fibers clinker is by slipping
Slot flows into hardening and tempering furnace, coke is added in hardening and tempering furnace from furnace roof, while into furnace passing to combustion air (combustion air can be cold
Wind is also possible to the hot wind that temperature is up to 500 DEG C or so).The smelting temperature of hardening and tempering furnace is 1260 DEG C.
The iron of melting output is separated, through cooling ingot casting.
By wire drawing in the melt feeding multiple roll centrifuge after separation iron at rock wool fibers.Melt primary chemical after separating iron
Ingredient is SiO2: 43.92%, MgO10.00%, Al2O3: 3.74%, Cr2O3: 0.176%, CaO15.07%.
Rock wool fibers obtain qualified rock wool board after pleating machine, curing oven, slice, cooling treatment.
Claims (10)
1. a kind of low-grade nickle contained discarded material processing method, it is characterised in that the following steps are included:
(1) nickle contained discarded material is dehydrated to water content 10-15%；
(2) nickle contained discarded material after dehydration and drying is pressed into brick；
(3) gained nickle contained discarded material brick is used into oxygen-enriched side-blowing furnace melting, obtains nis matte and clinker；
(4) by nis matte founding obtained by step (3) at anode plate, anode plate is electrolysed using diaphragm process, obtains metallic nickel
With nickel electrowinning waste liquid；
(5) by clinker obtained by step (3) for producing rock wool；
(6) oxidation of nickel electrowinning waste liquid obtained by step (4) is neutralized and removes iron, except liquid uses strike decopper(ing) after iron, obtain gold
Belong to copper；
(7) nickelous carbonate of liquid after decopper(ing) obtained by step (6) decopper(ing) is adjusted into pH value to 4.8, is sent into chlorine hybrid reaction, obtains
Cobalt.
2. the method according to claim 1, it is characterised in that: the lime of the nickle contained discarded material supplying weight ratio 5-10% bonds
Agent is pressed into brick through brick machine.
3. the method according to claim 1, it is characterised in that: the sequence of oxygen-enriched side-blowing furnace charging be first plus coke, then plus
Nickel brick.
4. the method according to claim 1, it is characterised in that: 1250-1350 DEG C of the smelting temperature of the oxygen-enriched side-blowing furnace, it is oxygen-enriched
Concentration is 24-28%.
5. the method according to claim 1, it is characterised in that: the nis matte nickel content of the melting output is 10-30%, cupric
5-15%。
6. the method according to claim 1, it is characterised in that: the main chemical compositions of the oxygen-enriched side-blowing furnace clinker are
NiO0.1-0.5%、FeO3-9%、SiO242-55%、MgO3-16%、CaO5-25%、Al2O32-8%。
7. the method according to claim 1, it is characterised in that: the nickle contained discarded material nickel content is 1-15%.
8. the method according to claim 1, it is characterised in that: clinker obtained by the step (3) is for producing rock wool, preparation side
Method includes the following steps: that clinker is entered to carry out melting in hardening and tempering furnace by a. with dolomite, coke；B. the iron of melting output is separated,
Through cooling ingot casting；C. by wire drawing in the melt feeding multiple roll centrifuge after separation iron at rock wool fibers.
9. method according to claim 8, it is characterised in that: the coke of dolomite, 8-15% by clinker with weight ratio 20-40%
Enter and carry out melting in hardening and tempering furnace, the temperature of melting is 1250-1280 DEG C in hardening and tempering furnace.
10. the method according to claim 1, it is characterised in that: the earth of positive pole after step (4) electrolysis is carried out advanced treating, is mentioned
Take out the noble metal being rich in.
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| CN201810847578.9A CN108950215A (en) | 2018-07-27 | 2018-07-27 | Low-grade nickle contained discarded material processing method |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109988919A (en) * | 2019-04-08 | 2019-07-09 | 江苏源翔合金材料科技有限公司 | A kind of smelting furnace bottom nickel block recovery process |
| CN110819810A (en) * | 2019-11-21 | 2020-02-21 | 株洲冶炼集团股份有限公司 | Comprehensive recovery method for purifying cobalt-nickel slag by zinc hydrometallurgy arsenic salt |
| CN111826522A (en) * | 2020-06-24 | 2020-10-27 | 济源豫光有色冶金设计研究院有限公司 | Method for treating electroplating sludge by adopting gypsum residues |
| CN111961880A (en) * | 2020-07-28 | 2020-11-20 | 中国恩菲工程技术有限公司 | Method for producing metallized nickel anode plate by using bottom blowing furnace |
| CN111992729A (en) * | 2020-08-26 | 2020-11-27 | 甘肃高能中色环保科技有限公司 | Method for producing nickel-copper alloy particles from low-grade nickel-copper solid hazardous waste material |
| CN114717424A (en) * | 2022-01-24 | 2022-07-08 | 池州西恩新材料科技有限公司 | Smelting method for recovering copper, cobalt and nickel by utilizing low-grade solid waste raw materials containing copper, cobalt and nickel |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN109988919A (en) * | 2019-04-08 | 2019-07-09 | 江苏源翔合金材料科技有限公司 | A kind of smelting furnace bottom nickel block recovery process |
| CN110819810A (en) * | 2019-11-21 | 2020-02-21 | 株洲冶炼集团股份有限公司 | Comprehensive recovery method for purifying cobalt-nickel slag by zinc hydrometallurgy arsenic salt |
| CN111826522A (en) * | 2020-06-24 | 2020-10-27 | 济源豫光有色冶金设计研究院有限公司 | Method for treating electroplating sludge by adopting gypsum residues |
| CN111961880A (en) * | 2020-07-28 | 2020-11-20 | 中国恩菲工程技术有限公司 | Method for producing metallized nickel anode plate by using bottom blowing furnace |
| CN111992729A (en) * | 2020-08-26 | 2020-11-27 | 甘肃高能中色环保科技有限公司 | Method for producing nickel-copper alloy particles from low-grade nickel-copper solid hazardous waste material |
| CN111992729B (en) * | 2020-08-26 | 2023-02-28 | 甘肃高能中色环保科技有限公司 | Method for producing nickel-copper alloy particles from low-grade nickel-copper solid hazardous waste material |
| CN114717424A (en) * | 2022-01-24 | 2022-07-08 | 池州西恩新材料科技有限公司 | Smelting method for recovering copper, cobalt and nickel by utilizing low-grade solid waste raw materials containing copper, cobalt and nickel |
| CN114717424B (en) * | 2022-01-24 | 2024-07-09 | 池州西恩新材料科技有限公司 | Smelting method for recycling copper, cobalt and nickel by utilizing low-grade solid waste raw materials containing copper, cobalt and nickel |
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