CN109971967A - A method of valuable metal is recycled from Copper making blowing clinker - Google Patents
A method of valuable metal is recycled from Copper making blowing clinker Download PDFInfo
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- CN109971967A CN109971967A CN201910208457.4A CN201910208457A CN109971967A CN 109971967 A CN109971967 A CN 109971967A CN 201910208457 A CN201910208457 A CN 201910208457A CN 109971967 A CN109971967 A CN 109971967A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B03—SEPARATION OF SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS; MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
- B03C—MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
- B03C1/00—Magnetic separation
- B03C1/02—Magnetic separation acting directly on the substance being separated
- B03C1/30—Combinations with other devices, not otherwise provided for
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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
- C22B15/0026—Pyrometallurgy
- C22B15/0056—Scrap treating
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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
- 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
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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
- 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
- C22B7/04—Working-up slag
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- 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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Abstract
The invention discloses a kind of methods that valuable metal is recycled from Copper making blowing clinker, the hot blowing slag melt of copper pyrometallurgy is poured into smelting furnace by cinder ladle or chute, reducing agent, copper concentrate and slag former, melting are added into smelting furnace obtains cobalt matte melt, slag melt；Cobalt matte solid obtains the copper concentrate containing cobalt higher cobalt concentrate and low cobalt high-copper by broken, ore grinding, magnetic separation separation；The copper concentrate of low cobalt high-copper send copper works' copper smelter, recycles copper therein using existing copper smelting technique and produces copper products, and further cobalt therein is enriched in blowing clinker, forms the circulation and stress of cobalt, copper.Not only smelting temperature is low, and low energy consumption, and metal recovery rate is high, and obtained cobalt concentrate fine size, cobalt content height, silicone content is low, product subsequent processing is easy, and can handle copper concentrate while valuable metal in recycling copper metallurgy blowing clinker with melting.
Description
Technical field
The present invention relates to valuable metal Comprehensive Recovery Technology fields in the metallurgical slag of non-ferrous metal metallurgical industry, more particularly to
A method of valuable metal is recycled from Copper making blowing clinker.
Background technique
During copper pyrometallurgy, cobalt that copper concentrate is brought into, there are about 50~70% after matte smelting-blowing process for nickel
Into in blowing clinker.The especially copper concentrate of the African countries such as Congo (Congo-Kinshasa), Zambia and northwest China area output contains
Cobalt, nickel are higher, and nickel, cobalt total content are about 0.5~1.2%, and cobalt is enriched in blowing clinker during Copper making.Containing cobalt, nickel
The main mine phase composition that copper concentrate smelts blowing clinker is fayalite and a small amount of magnetic iron ore, weight of iron content usually 40~
55%, SiO2Mass content is usually 20~35%, cobalt, nickel total content about 0.5~4%, and cupric 2~10%.Wherein copper
Mechanical entrainment enters slag phase mainly in the form of sulfide and metallic copper, and cobalt, nickel are mainly with oxidation state and with lattice substitution
There are in fayalite and magnetic iron ore phase for form.
For in Copper making production process containing nickel in cobalt, nickel convering clinker, cobalt, copper recycling at present be able to apply it is main
There are pressure leaching process, reducing smelting process etc..
1, pressurized acid leaching method: being valuable metal in the method recycling clinker using oxygen pressure acidleach.At 160~250 DEG C of temperature
Left and right, sulfuric acid dosage are the 40~70% of former slag amount, and control partial pressure of oxygen is 0.3~0.6MPa, by blowing clinker cobalt,
The valuable metals such as nickel, copper are leached into solution, and iron, which is dissolved out under oxygen pressure condition and is oxidized simultaneously, is hydrolyzed to hematite precipitation,
Realize the Selectively leaching of valuable metal, copper leaching rate > 90%, cobalt leaching rate 70~85%, nickel leaching rate 60~80%.So
And the acidproof high-tension apparatus of pressurized acid leaching method, equipment investment and maintenance cost are larger；Due to valuable metal in blowing clinker
Content is low, causes material handling capacity big, and operation cost is high.
2, reducing smelting process: be under 1500 DEG C or so of smelting temperature, be added reducing agent, slag former, by slag cobalt,
Nickel, copper reduction form alloy at metallic state and iron, are layered with slag phase, and the alloy of formation is mutually discharged from furnace, are closed after water quenching
Gold particle realizes the separating-purifying of cobalt, nickel, copper using leaching-removal of impurities.Using the shortcoming of this method processing copper slag
Have:
1) alloy melting point that reduction melting obtains is high (1400~1550 DEG C of fusing point), and operation temperature is high, and energy consumption is high, however copper
Blowing clinker is lower melting-point FeO-SiO2It is slag type, Yao Shixian high melt needs to be incorporated a large amount of slag formers；
2) reduction melting, iron reduction rate is high, and the additive amount of reducing agent and consumption are big；
3) granularity is thicker after the alloy water quenching of reduction melting output, and general granularity is in 2mm or more, and toughness is more difficult broken greatly
Broken and ore grinding；
4) reduction melting due to smelting temperature and reducing agent additive amount it is high, the Silicon In Alloys content thus restored compared with
Height, silicon subsequent cobalt, copper wet-leaching separation process in easily form silica gel, increase difficulty for leaching process.
To sum up, for the recycling of cobalt, nickel, copper still lacks conjunction in the clinker of nickel convering containing cobalt in Copper making production process
Manage effective method.
Summary of the invention
The object of the present invention is to provide a kind of methods that valuable metal is recycled from Copper making blowing clinker.
The purpose of the present invention is what is be achieved through the following technical solutions:
The method that valuable metal is recycled in slave Copper making blowing clinker of the invention, comprising steps of
Step 1: the hot blowing slag melt of copper pyrometallurgy is poured into smelting furnace by cinder ladle or chute, to melting
Reducing agent, copper concentrate and slag former are added in furnace；
Step 2: smelting temperature be 1200~1350 DEG C, smelting time be 15~300 minutes (preferably 30~120 points
Clock), to obtain cobalt matte melt, slag melt and flue gas；
Step 3: the cobalt matte being discharged in the step two is put into the copper-clad with heat preservation by chute, control 1~5
DEG C/rate of temperature fall of min slowly cools to 700~1000 DEG C of skin temperature, the uncooled matte in upper layer in copper-clad is melted later
Body driving is poured into blowing, obtained blowing slag in copper metallurgy converting furnace and is poured into smelting furnace with cinder ladle again, and the circulation of cobalt, nickel is formed
Recycling, copper converting is at blister copper.The cobalt matte solid condensed in copper-clad is natural or forces to be cooled to 100~200 DEG C or so, using row
Vehicle pours out cobalt matte solid；
Step 4: the cobalt matte solid of output uses broken crusher machine and ball mill ore grinding to granularity-in the step 3
0.074mm accounts for 60~95%, and ore pulp is separated using magnetic separator magnetic separation.Part is chosen during magnetic separation as containing the higher cobalt concentrate of cobalt,
Containing Co 5~20%, Ni 1~10%, Cu 8~25%, Fe 40~70%, S < 10%, Si < 1.5%, granularity -0.074mm is accounted for
Than > 80%.It selects lower part to be divided into the copper concentrate of low cobalt high-copper during magnetic separation, contains Co 0.1~1.0%, Cu45~50%；
Step 5: the copper concentrate of output send copper works' copper smelter in the step 4, returned using existing copper smelting technique
Copper production copper products therein are received, and further cobalt therein is enriched in blowing clinker, form the circulation and stress of cobalt, copper.
As seen from the above technical solution provided by the invention, provided in an embodiment of the present invention from Copper making blowing clinker
The method of middle recycling valuable metal, not only smelting temperature is low, and low energy consumption, and metal recovery rate is high, obtained cobalt concentrate fine size, cobalt
Content is high, silicone content is low, product subsequent processing is easy, and can be with while valuable metal in recycling copper metallurgy blowing clinker
Melting handles copper concentrate.
Detailed description of the invention
Fig. 1 is the method flow signal provided in an embodiment of the present invention that valuable metal is recycled from Copper making blowing clinker
Figure.
Specific embodiment
The embodiment of the present invention will be described in further detail below.What is be not described in detail in the embodiment of the present invention is interior
Appearance belongs to the prior art well known to professional and technical personnel in the field.
The method that valuable metal is recycled in slave Copper making blowing clinker of the invention, preferable specific embodiment is:
Include:
Step 1: the hot blowing slag melt of copper pyrometallurgy is poured into smelting furnace by cinder ladle or chute, to melting
Reducing agent, copper concentrate and slag former are added in furnace；
Step 2: smelting temperature be 1200~1350 DEG C, smelting time be 15~300 minutes (preferably 30~120 points
Clock), to obtain cobalt matte melt, slag melt and flue gas；
Step 3: the cobalt matte being discharged in the step two is put into the copper-clad with heat preservation by chute, control 1~5
DEG C/rate of temperature fall of min slowly cools to 700~1000 DEG C of skin temperature, the uncooled matte in upper layer in copper-clad is melted later
Body driving is poured into blowing, obtained blowing slag in copper metallurgy converting furnace and is poured into smelting furnace with cinder ladle again, and the circulation of cobalt, nickel is formed
Recycling, copper converting is at blister copper.The cobalt matte solid condensed in copper-clad is natural or forces to be cooled to 100~200 DEG C or so, using row
Vehicle pours out cobalt matte solid；
Step 4: the cobalt matte solid of output uses broken crusher machine and ball mill ore grinding to granularity-in the step 3
0.074mm accounts for 60~95%, and ore pulp is separated using magnetic separator magnetic separation.Part is chosen during magnetic separation as containing the higher cobalt concentrate of cobalt,
Containing Co 5~20%, Ni 1~10%, Cu 8~25%, Fe 40~70%, S < 10%, Si < 1.5%, granularity -0.074mm is accounted for
Than > 80%.It selects lower part to be divided into the copper concentrate of low cobalt high-copper during magnetic separation, contains Co 0.1~1.0%, Cu45~50%；
Step 5: the copper concentrate of output send copper works' copper smelter in the step 4, returned using existing copper smelting technique
Copper production copper products therein are received, and further cobalt therein is enriched in blowing clinker, form the circulation and stress of cobalt, copper.
The reducing agent is at least one of granular coke, charcoal or anthracite；The copper concentrate be sulfur-bearing 15~
30% copper concentrate or copper cobalt concentrate；The slag former is at least one of quick lime, lime stone, dolomite or quartz sand.
The dosage of the reducing agent is 1~10% (preferably 2~4%) of blowing clinker gross mass, the dosage of copper concentrate
For 10~45% (preferably 20~35%) of the clinker gross mass that blows, the dosage of slag former is the 0.1 of blowing clinker gross mass
~20%.
The smelting furnace includes closed burried arc furnace and/or swivel furnace.
The blowing clinker is poured into smelting furnace by cinder ladle or chute, auxiliary material reducing agent, copper concentrate and slag former difference
By conveyer, feed bin, feed weigher, uniformly put into from melting furnace roof, and in smelting furnace melt upper layer formed 0.5~
1.2m thickness auxiliary material layer.
The cobalt matte of the smelting furnace discharge is discharged into the copper-clad with heat preservation or copper-clad is put into Slow cooling in intermediate frequency furnace
To 700~1000 DEG C of skin temperature, copper-clad is taken out, uncooled matte is poured into converting furnace and is blown.
Output cobalt matte melt in the step 2 directlys adopt casting machine casting cooling, forms cobalt matte solid, investment
In step 4, production contains the higher cobalt concentrate of cobalt and the lower copper concentrate containing cobalt.
The cobalt matte solid of output is that embedding one of the matte that is distributed in of Fe-Co-Ni-Cu alloying pellet collects in the step 3
It is fit.
It includes the crushing system for being crushed-sieving composition that the cobalt matte solid of output is broken in the step 3, and control is broken
5~15mm of discharging-material size；The ore grinding includes that ball mill-grader-magnetic separator combines the grinding system to be formed, and controls ore grinding grain
Degree -0.074mm accounts for 60~95%；
The wet magnetic separator includes the magnetic separation system of more magnetic separators composition.
Blowing in converting furnace of the copper concentrate of output by being directly added into copper works after pelletizer pelletizing in the step 4
Blister copper is produced, cobalt, nickel are enriched in blowing clinker.
The method that valuable metal is recycled in slave Copper making blowing clinker of the invention, not only smelting temperature is low, and low energy consumption, gold
Belong to rate of recovery height, obtained cobalt concentrate fine size, cobalt content are high, silicone content is low, product subsequent processing is easy, and refine in recycling
In copper converting clinker copper concentrate can be handled with melting while valuable metal.
Specific embodiment:
Firstly the need of explanation, the method master provided by the present invention that valuable metal is recycled from Copper making blowing clinker
If for copper pyrometallurgy Industrial Output contain cobalt, nickel convering clinker, wherein containing cobalt, nickel gross mass percentage be 0.5~
4%, cupric mass percent is 2~10%, and mass percent containing Fe is 40~55%, contains SiO2Mass percent be 20~
35%.But in practical applications, which is the molten state warm sludge being discharged in converting furnace converting process.Below to the present invention
The method that valuable metal is recycled in the slave Copper making blowing clinker provided is described in detail.
As shown in Figure 1, a kind of method for recycling valuable metal from Copper making blowing clinker, includes the following steps:
Step 1: the hot blowing clinker of copper pyrometallurgy is poured into smelting furnace by cinder ladle or chute, into smelting furnace
Add reducing agent, copper concentrate and slag former.Wherein, the reducing agent is at least one of granular coke, charcoal or anthracite；
The copper concentrate is the copper concentrate or copper cobalt concentrate of sulfur-bearing 15~30%；The slag former is lime, lime stone, dolomite or stone
At least one of sand.The dosage of reducing agent is 1~10% (preferably 2~4%) of blowing clinker gross mass, copper concentrate
Dosage is 10~45% (preferably 20~35%) of blowing clinker gross mass, and the dosage of slag former is blowing clinker gross mass
0~20%.
Step 2: using smelting furnace to described low to the progress of the hot blowing clinker of melting, reducing agent, copper concentrate and slag former
Warm reduction-sulfurization melting, smelting temperature be 1200~1350 DEG C, smelting time be 15~300 minutes (preferably 30~120 points
Clock), to obtain cobalt matte melt, slag melt and flue gas.Wherein, described to be fallen to melting converting furnace slag by cinder ladle or chute
Enter in smelting furnace, auxiliary material reducing agent, copper concentrate and slag former pass through respectively conveyer (such as: the conveyer can use existing
Belt conveyor or bucket elevator in technology, can also according to landform arrange selection can convey in the prior art powder and
The conveyer of pellet) it is sent in the feed bin (the feed buffer bin i.e. at the top of smelting furnace) of smelting furnace, it is fed and is counted by feed bin
Scale is measured, according to blowing clinker input amount, the control of melting residence time of material into the auxiliary material delivery rate in smelting furnace, and
Melt upper layer forms 0.5~1.2m thickness auxiliary material layer in smelting furnace.Cobalt, nickel in reduction-sulfurization fusion process, in the clinker that blows
It is reduced, and there is part iron to be reduced to metallic state, trapping cobalt, nickel, copper form Fe-Co-Ni-Cu alloy；Copper concentrate melting is simultaneously
Copper forms copper matte regulus in trapping blowing clinker, and copper matte regulus forms the lower melting-point mutual solution of melting with Fe-Co-Ni alloy again, i.e., described
Cobalt matte.Cobalt matte melt is relied on to be separated with the realization of the density contrast of slag melt, and cobalt matte fusant density is bigger than slag melt, sinks
In the molten bath lower part of smelting furnace, therefore the cobalt matte melt can periodically be discharged from the lower outlet of smelting furnace by chute,
The slag melt can periodically be discharged from the eminence outlet of smelting furnace by chute, the flue gas by smelting furnace top flue
Discharge, this can make the rate of recovery of cobalt be greater than 95%, and nickel recovery is greater than 92%, and the rate of recovery of copper is greater than 95%.In practical application
In, the smelting furnace is configured with transformer, rectifier, electrode, electrode lifting dress preferably with submerged arc closed electric furnace
It sets, furnace structure and thermal insulation material, furnace roof cover board, dust gas gathering mask, furnace body cooling system, row's cobalt matte mouth and chute, deslagging
The facilities such as mouth and chute, flue gas discharge opening.
Step 3: the cobalt matte being discharged in the step two is put into the copper-clad with heat preservation by chute, control 1~5
DEG C/rate of temperature fall of min slowly cools to 700~1000 DEG C of skin temperature, the uncooled matte in upper layer in copper-clad is melted later
Body driving is poured into blowing, obtained blowing slag in copper metallurgy converting furnace and is poured into smelting furnace with cinder ladle again, and the circulation of cobalt, nickel is formed
Recycling, copper converting is at blister copper.The cobalt matte solid condensed in copper-clad is natural or forces to be cooled to 100~200 DEG C or so, using row
Vehicle pours out cobalt matte solid.
Step 4: the cobalt matte solid of output uses broken crusher machine and ball mill ore grinding to granularity-in the step 3
0.074mm accounts for 60~95%, and ore pulp is separated using magnetic separator magnetic separation.Part is chosen during magnetic separation as containing the higher cobalt concentrate of cobalt,
Containing Co 5~20%, Ni 1~10%, Cu 8~25%, Fe 40~70%, S < 10%, Si < 1.5%, granularity -0.074mm is accounted for
Than > 80%.It selects lower part to be divided into the copper concentrate of low cobalt high-copper during magnetic separation, contains Co 0.1~1.0%, Cu 45~50%.
Step 5: the copper concentrate of output send copper works' copper smelter in the step 4, returned using existing copper smelting technique
Copper production copper products therein are received, and further cobalt therein is enriched in blowing clinker, form the circulation and stress of cobalt, copper.
The principles of science of the invention:
Fe is mainly with Fe in copper smelting by pyrometallurgy blowing clinker3O4And 2FeOSiO2Form exists；Co, Ni are mainly with oxidation
State, class matter are present in ferriferous oxide crystal phase with the form of phase；Cu mainly exists with metallic copper, copper sulphide form.
Reduction-sulfurization melting is Co, Ni to be reduced to metallic state using reducing agent, while part Fe is reduced into metallic state
And it traps cobalt, nickel, copper and forms Fe-Co-Ni-Cu alloy；Meanwhile copper concentrate traps copper in blowing clinker in fusion process and is formed
Matte；Matte fusing point is low, and the Fe-Co-Ni-Cu alloy that formation is restored in good fluidity, with slag forms lower melting-point metallization
The cobalt matte melt that dissolves each other is separated with slag, is discharged.Realize that alloy is precipitated simultaneously during Slow cooling after the mutual solution discharge of cobalt matte
It grows up, is formed and have magnetic Fe-Co-Ni-Cu alloying pellet.Alloy and matte are dissociated by broken, ore grinding after cooling, adopted
It is enriched with Fe-Co-Ni-Cu alloy with the method for magnetic separation, realizes the separation of cobalt, nickel, copper.Main chemical reactions are as follows:
CoO+C=Co+CO
NiO+C=Ni+CO
Fe3O4+ C=3FeO+CO
FeO+C=Fe+CO
Fe+CoO=Co+FeO
Fe+NiO=Ni+FeO
Fe+Fe3O4=4FeO
Fe(L)+Co(L)+Ni(L)+Cu(L)=Fe-Co-Ni-Cu(L alloy)
CuFeS2+2Fe3O4+3SiO2=CuFeS(matte)+3(2FeO·SiO2)+SO2
CuFeS(matte)+Fe-Co-Ni-Cu(L alloy)=CuFeS- (Fe-Co-Ni-Cu)(the mutual solution of L)
CuFeS-(Fe-Co-Ni-Cu)(mutual solution)=CuFeS(S)+Fe-Co-Ni-Cu(S alloy)
Compared with prior art, the method provided by the present invention that valuable metal is recycled from copper-smelting thermal blowing clinker
At least have following technical effect that
(1) present invention directly handles copper-smelting thermal blowing clinker using smelting furnace, makes full use of hot blowing clinker
Thermal energy, melting energy consumption is lower, and energy consumption reduces by 100~200kwh/t than traditional meltingSlag。
(2) present invention had both been suitble to current copper metallurgy blowing clinker type, had been made using low-temperature reduction vulcanizing treatment copper metallurgy blowing clinker
Slag agent consumption is low, and reduces smelting temperature.
(3) cobalt matte melt is put into Slow cooling in copper-clad by the present invention, and partial condensation part returns to converting furnace blowing, shape
At converting furnace blowing and the electro-smelting circulatory system, by copper converting at blister copper, cobalt, nickel return to electric reduction furnace into blowing clinker,
Not only it had recycled copper but also had realized the circulation and stress of cobalt, nickel, and improved the rate of recovery of cobalt, nickel.
(4) smelting reduction degree of the present invention is low, and the alloying pellet formed in smelting furnace is small, it is not easy to occur alloy in furnace
With the layering of matte.
(5) the cobalt matte structure that melting of the present invention obtains is distributed in matte for ferrocobalt particle is embedding, and alloying pellet is thinner
Generally -0.074mm or so, the structure is easily broken and ore grinding, is more advantageous to the Refining of subsequent cobalt and nickel.
(6) the cobalt matte obtained after low smelting heat of the present invention uses copper-clad slow cooling, and alloying pellet is further grown up, more favorably
The dissociation sorting of copper, cobalt, nickel during subsequent magnetic separation.
(7) present invention realizes the separation of cobalt, nickel and copper in cobalt matte that melting obtains using broken, ore grinding, magnetic separation, obtains
Cobalt concentrate be up to 5~20% containing cobalt, and Si content is lower than 1.5%, and copper content is 8~25%, granularity -0.074mm accounting >
80%, it is very beneficial for the Refining of subsequent cobalt.
(8) present invention not only can be with cobalt, nickel, copper in synthetical recovery copper metallurgy blowing clinker, the cobalt rate of recovery >=95%, nickel recycling
Rate >=92%, copper recovery >=95%, and simultaneously copper concentrate can be handled with melting.
In order to more clearly from show technical solution provided by the present invention and generated technical effect, below with tool
The method provided by the present invention that valuable metal is recycled from Copper making blowing clinker is described in detail in body embodiment.
Embodiment 1
A method of valuable metal being recycled from Copper making blowing clinker, using the converting furnace of Zambia's copper smelting plant
Slag is raw material, and the essential element ingredient of the blowing clinker is as shown in table 1 below:
Table 1:
| Element | Co | Ni | Cu | SiO2 | Fe |
| Content/% | 2.20 | 0.44 | 10.56 | 20.16 | 52.99 |
This method comprises: take the 5kg copper metallurgy blow clinker, first melted with burried arc furnace, take later 0.2kg anthracite,
1.25kg is added into electric furnace after mixing containing the copper concentrate that Cu and S are respectively 15% and 25%, 0.25kg quartz sand, is continued
Melting, and 1350 DEG C of smelting temperature are controlled, 90min is kept the temperature, after slowly cooling to 800 DEG C later with the rate of temperature fall of 3 DEG C/min
Room temperature is naturally cooled to, to obtain completing isolated cobalt matte and clinker.It takes cobalt matte to be crushed, be milled to granularity -0.074mm
80% is accounted for, ball milling slurry uses wet magnetic separator magnetic separation.
The cobalt concentrate for taking smelting slag and magnetic separation to obtain respectively carries out Element detection, wherein Co, Ni, Cu content point in smelting slag
Not Wei 0.11%, 0.06% and 0.48%, the slag meter rate of recovery is respectively Co 97.25%, Ni 92.5% and Cu 97.5%；Magnetic
Obtained cobalt concentrate group is selected to become Co 13.5%, Ni 2.5%, Cu 15.4%, Si 0.5%.
Embodiment 2
A method of valuable metal being recycled from Copper making blowing clinker, using the converting furnace of certain golden copper smelting plant of the Congo
Slag is raw material, and the essential element ingredient of the blowing clinker is as shown in table 1 below:
Table 2:
| Element | Co | Ni | Cu | SiO2 | Fe |
| Content/% | 1.32 | 0.38 | 5.48 | 24.10 | 48.85 |
This method comprises: take the 5kg copper metallurgy blow clinker, first melted with burried arc furnace, take later 0.15kg coke,
1.5kg is added in electric furnace after mixing containing the copper concentrate that Cu and S are respectively 25% and 15%, continues melting, and control melting
1300 DEG C of temperature, 120min is kept the temperature, naturally cools to room temperature after slowly cooling to 700 DEG C later with the rate of temperature fall of 2 DEG C/min,
To obtain completing isolated cobalt matte and clinker.It takes cobalt matte to be crushed, be milled to granularity -0.074mm and account for 85%, ball milling slurry
Using wet magnetic separator magnetic separation.
The cobalt concentrate for taking smelting slag and magnetic separation to obtain respectively carries out Element detection, wherein Co, Ni, Cu content point in smelting slag
Not Wei 0.12%, 0.05% and 0.41%, the slag meter rate of recovery is respectively Co 95.00%, Ni 92.76% and Cu 95.89%；
The cobalt concentrate group that magnetic separation obtains becomes Co 10.5%, Ni 2.5%, Cu 13.6%, Si 0.4%.
Embodiment 3
A method of valuable metal being recycled from Copper making blowing clinker, using the blowing clinker of Yunnan copper smelting plant
Essential element ingredient for raw material, the blowing clinker is as shown in table 1 below:
Table 3:
| Element | Co | Ni | Cu | SiO2 | Fe |
| Content/% | 0.92 | 0.21 | 3.52 | 23.46 | 47.62 |
This method comprises: take the 5kg copper metallurgy blow clinker, first melted with burried arc furnace, take later 0.125kg charcoal,
1.75kg is added in electric furnace after mixing containing the copper concentrate that Cu and S are respectively 20% and 21%, continues melting, and control melting
1250 DEG C of temperature, 180min is kept the temperature, naturally cools to room temperature after slowly cooling to 850 DEG C later with the rate of temperature fall of 2 DEG C/min,
To obtain completing isolated cobalt matte and clinker.It takes cobalt matte to be crushed, be milled to granularity -0.074mm and account for 90%, ball milling slurry
Using wet magnetic separator magnetic separation.
The cobalt concentrate for taking smelting slag and magnetic separation to obtain respectively carries out Element detection, wherein Co, Ni, Cu content point in smelting slag
Not Wei 0.08%, 0.03% and 0.32%, the slag meter rate of recovery is respectively Co 95.22%, Ni 92.14% and Cu 95.00%；
The cobalt concentrate group that magnetic separation obtains becomes Co 9.8%, Ni 1.8%, Cu 16.9%, Si 0.3%.
To sum up, not only smelting temperature is low for the embodiment of the present invention, and slag former additive amount is low, cobalt, nickel, copper synthetical recovery
Rate is high, obtained cobalt concentrate cobalt, nickel content height, while can melting processing copper concentrate.
The foregoing is only a preferred embodiment of the present invention, but scope of protection of the present invention is not limited thereto,
Within the technical scope of the present disclosure, any changes or substitutions that can be easily thought of by anyone skilled in the art,
It should be covered by the protection scope of the present invention.Therefore, protection scope of the present invention should be with the protection model of claims
Subject to enclosing.
Claims (10)
1. a kind of method for recycling valuable metal from Copper making blowing clinker characterized by comprising
Step 1: the hot blowing slag melt of copper pyrometallurgy is poured into smelting furnace by cinder ladle or chute, into smelting furnace
Add reducing agent, copper concentrate and slag former；
Step 2: smelting temperature is 1200~1350 DEG C, smelting time is 15~300 minutes, to obtain cobalt matte melt, furnace
Slag melt and flue gas；
Step 3: the cobalt matte being discharged in the step two is put into the copper-clad with heat preservation by chute, 1~5 DEG C of control/
The rate of temperature fall of min slowly cools to 700~1000 DEG C of skin temperature, later uses the uncooled matte melt in upper layer in copper-clad
Driving pours into blowing, obtained blowing slag in copper metallurgy converting furnace and poured into smelting furnace with cinder ladle again, forms cobalt, nickel is recycled back to
It receives, copper converting is at blister copper, and the interior cobalt matte solid condensed of copper-clad is natural or forces to be cooled to 100~200 DEG C or so, using driving
Cobalt matte solid is poured out；
Step 4: the cobalt matte solid of output uses broken crusher machine and ball mill ore grinding to granularity-in the step 3
0.074mm accounts for 60~95%, and ore pulp is separated using magnetic separator magnetic separation, part is chosen during magnetic separation as containing the higher cobalt concentrate of cobalt,
Containing Co 5~20%, Ni 1~10%, Cu 8~25%, Fe 40~70%, S < 10%, Si < 1.5%, granularity -0.074mm is accounted for
Than > 80%, lower part is selected to be divided into the copper concentrate of low cobalt high-copper during magnetic separation, contains Co 0.1~1.0%, Cu 45~50%；
Step 5: the copper concentrate of output send copper works' copper smelter in the step 4, it is recycled using existing copper smelting technique
In copper produce copper products, and further by cobalt therein be enriched in blowing clinker in, formed cobalt, copper circulation and stress.
2. the method according to claim 1 for recycling valuable metal from Copper making blowing clinker, which is characterized in that described
Reducing agent is at least one of granular coke, charcoal or anthracite；The copper concentrate be sulfur-bearing 15~30% copper concentrate or
Copper cobalt concentrate；The slag former is at least one of quick lime, lime stone, dolomite or quartz sand.
3. the method according to claim 1 for recycling valuable metal from Copper making blowing clinker, which is characterized in that described
The dosage of reducing agent is the 1~10% of blowing clinker gross mass, and the dosage of copper concentrate is the 10~45% of blowing clinker gross mass,
The dosage of slag former is the 0.1~20% of blowing clinker gross mass.
4. the method according to claim 3 for recycling valuable metal from Copper making blowing clinker, which is characterized in that described
The dosage of reducing agent is the 2~4% of blowing clinker gross mass, and the dosage of copper concentrate is the 20~35% of blowing clinker gross mass.
5. the method according to claim 1 for recycling valuable metal from Copper making blowing clinker, which is characterized in that described
Smelting furnace includes that closed burried arc furnace and/or swivel furnace, the blowing clinker are poured into smelting furnace by cinder ladle or chute, auxiliary material
Reducing agent, copper concentrate and slag former pass through conveyer, feed bin, feed weigher respectively, uniformly put into from melting furnace roof, and
Melt upper layer forms 0.5~1.2m thickness auxiliary material layer in smelting furnace.
6. the method according to claim 1 for recycling valuable metal from Copper making blowing clinker, which is characterized in that described
The cobalt matte of smelting furnace discharge, which is discharged into the copper-clad with heat preservation or copper-clad is put into intermediate frequency furnace, slowly cools to skin temperature 700
~1000 DEG C, copper-clad is taken out, uncooled matte is poured into converting furnace and is blown.
7. the method according to claim 1 for recycling valuable metal from Copper making blowing clinker, which is characterized in that described
In step 2, smelting time is 30~120 minutes, output cobalt matte melt, directlys adopt casting machine casting cooling, forms cobalt ice
Copper solid is put into step 4, and production contains the higher cobalt concentrate of cobalt and the lower copper concentrate containing cobalt.
8. the method according to claim 1 for recycling valuable metal from Copper making blowing clinker, which is characterized in that described
The cobalt matte solid of output is distributed in one of matte aggregate for Fe-Co-Ni-Cu alloying pellet is embedding in step 3.
9. the method according to claim 1 for recycling valuable metal from Copper making blowing clinker, which is characterized in that described
In step 3 the cobalt matte solid of output it is broken include broken-screening composition crushing system, control broken discharging-material size 5~
15mm；The ore grinding includes that ball mill-grader-magnetic separator combines the grinding system to be formed, and control ore grinding goes out granularity-
0.074mm accounts for 60~95%；
The wet magnetic separator includes the magnetic separation system of more magnetic separators composition.
10. the method according to claim 1 for recycling valuable metal from Copper making blowing clinker, which is characterized in that institute
Blowing production blister copper in converting furnace of the copper concentrate of output in step 4 by being directly added into copper works after pelletizer pelletizing is stated,
Cobalt, nickel are enriched in blowing clinker.
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| CN113481376B (en) * | 2021-05-31 | 2022-09-06 | 金川集团股份有限公司 | Method for sorting, recovering and treating copper and nickel in copper smelting furnace slag |
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