CN105695749A - Method for recycling lead, zinc, arsenic, antimony, bismuth and tin from high-purity copper smelting slag - Google Patents

Method for recycling lead, zinc, arsenic, antimony, bismuth and tin from high-purity copper smelting slag Download PDF

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Publication number
CN105695749A
CN105695749A CN201610085047.1A CN201610085047A CN105695749A CN 105695749 A CN105695749 A CN 105695749A CN 201610085047 A CN201610085047 A CN 201610085047A CN 105695749 A CN105695749 A CN 105695749A
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described
refining furnace
copper smelting
smelting slag
copper
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CN201610085047.1A
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Chinese (zh)
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杨伟燕
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杨伟燕
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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
    • C22B13/00Obtaining lead
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22BPRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B15/00Obtaining copper
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22BPRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B19/00Obtaining zinc or zinc oxide
    • C22B19/30Obtaining zinc or zinc oxide from metallic residues or scraps
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22BPRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B25/00Obtaining tin
    • C22B25/06Obtaining tin from scrap, especially tin scrap
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22BPRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B30/00Obtaining antimony, arsenic or bismuth
    • C22B30/02Obtaining antimony
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22BPRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B30/00Obtaining antimony, arsenic or bismuth
    • C22B30/04Obtaining arsenic
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22BPRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B30/00Obtaining antimony, arsenic or bismuth
    • C22B30/06Obtaining bismuth
    • 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
    • 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
    • C22B7/001Dry processes
    • 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
    • Y02P10/20Process efficiency
    • Y02P10/21Process efficiency by recovering materials
    • Y02P10/212Recovering metals from waste
    • Y02P10/214Recovering metals from waste by pyro metallurgy
    • 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
    • Y02P10/20Process efficiency
    • Y02P10/21Process efficiency by recovering materials
    • Y02P10/212Recovering metals from waste
    • Y02P10/214Recovering metals from waste by pyro metallurgy
    • Y02P10/22Recovering metals from waste by pyro metallurgy of Cu
    • 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
    • Y02P10/20Process efficiency
    • Y02P10/21Process efficiency by recovering materials
    • Y02P10/212Recovering metals from waste
    • Y02P10/214Recovering metals from waste by pyro metallurgy
    • Y02P10/228Recovering metals from waste by pyro metallurgy of Sn
    • 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
    • Y02P10/20Process efficiency
    • Y02P10/21Process efficiency by recovering materials
    • Y02P10/212Recovering metals from waste
    • Y02P10/214Recovering metals from waste by pyro metallurgy
    • Y02P10/232Recovering metals from waste by pyro metallurgy of Zn or ZnO
    • 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
    • Y02P10/20Process efficiency
    • Y02P10/21Process efficiency by recovering materials
    • Y02P10/212Recovering metals from waste
    • Y02P10/234Recovering metals from waste by hydro metallurgy
    • 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
    • Y02P10/20Process efficiency
    • Y02P10/21Process efficiency by recovering materials
    • Y02P10/212Recovering metals from waste
    • Y02P10/234Recovering metals from waste by hydro metallurgy
    • Y02P10/236Recovering metals from waste by hydro metallurgy of Cu

Abstract

The invention discloses a method for recycling lead, zinc, arsenic, antimony, bismuth and tin from high-purity copper smelting slag. The method comprises the following steps: re-blowing external oxygen-containing gas under a vacuum state in a refining furnace to realize a process of removing impurity elements from the copper smelting slag, and removing the impurity elements in the copper smelting slag to facilitate producing a downstream product with higher purity and better quality; and then, recycling impurity elements in the forms of oxides to obtain a mixture of oxides of the impurity elements in a condensed state, and selling the mixture in the form of a metal product. According to the method, hot melt copper smelting slag is sufficiently oxidized, copper minerals and iron minerals are completely oxidized and copper-iron combined minerals are oxidized for being separated, so that various copper mineral phases are converted into a copper oxide phase, and various iron mineral phases are converted into a hematite phase, and therefore, a mineral dressing treatment process is adopted subsequently for recycling copper, iron and silicon in a facilitated manner; economical benefits are brought to the copper smelting enterprises, the profitability of the copper smelting enterprises is improved, resource waste is reduced, and environmental pollution is reduced.

Description

A kind of method reclaiming lead, zinc, arsenic, antimony, bismuth and stannum from high impurity copper metallurgical slag

Technical field

The present invention relates to resource reclaim environmental technology field, especially relate to a kind of method reclaiming lead, zinc, arsenic, antimony, bismuth and stannum from high impurity copper metallurgical slag。

Background technology

In Copper making industry, putting forward, from copper sulfide concentrate, the method that copper generally adopts pyrometallurgy, its flow process is generally: copper sulfide ore → selecting and purchasing operation → copper concentrate → melting operation → matte+smelting slag → blowing operation → blister copper+blowing slag → anode refining operation → anode copper → electrorefining operation → Cu-CATH-1。

Copper smelting slag includes the multiple slag of output in Copper making production process, is mostly smelting slag, also has least a portion of blowing slag etc.。Wherein copper weld pool slag mainly includes the Cu of 0.90%~3.0%, the Fe of 35%~44%, the SiO of 25%~35%2

Copper smelting slag processing intent now is to reclaim the copper in copper smelting slag, the slag concentrate (a kind of copper concentrate reclaiming generation from slag) that output copper content is higher, in copper smelting slag, original ferrum, silicon etc. remain in mine tailing, are applied in as solid waste in the industries such as building trade。Along with technological progress, indivedual forward positions patented technology proposes modified model copper smelting slag processing method, while output slag concentrate, and output iron ore concentrate and higher SO2The siliceous product of content。

It is known that also include the impurity elements such as lead, zinc, arsenic, antimony, bismuth and/or stannum in copper smelting slag。This part of impurity elements derives from the copper concentrate putting into smelting furnace。From the element balance angle calculation of whole Copper making flow process, in smelting process, the impurity element significant portion in raw copper concentrate enters in copper smelting slag, wherein, enters the impurity element ratio in copper weld pool slag maximum。

This part of impurity elements, on the one hand, affect the iron ore concentrate of institute's output and the quality of siliceous product and purity after subsequent copper metallurgical slag processes, such as: the impurity elements such as lead, zinc, arsenic, antimony, bismuth and stannum are the element kinds of the strict limited content upper limit in iron ore concentrate, impurity content in iron ore concentrate has been carried out strict classification requirement by GB, ironmaking processes and steelmaking process can be produced the negative influence of highly significant by impurity element, have a strong impact on production process, equipment life and product quality etc.。

On the other hand, mentioning that impurity element, industry technology personnel habitually thinking are " bad thing, the things as far as possible removed ", hardly realize, changing a thought angle, this part of impurity elements is also a kind of resource that can produce economic benefit。If this part of impurity elements is reclaimed by cupper smelting preferably, then to sell outside the form of metal product, the same with selling outward cathode plate, it is also possible to produce significant economic benefit。At present, prior art is not also had to propose this part of impurity elements in copper smelting slag is reclaimed。

To sum up, current copper smelting slag processing method, and the modified model copper smelting slag processing method mentioned in the patented technology of forward position, the problem all not considering a large amount of impurity elements contained in copper smelting slag。This part of impurity elements brought very big negative influence both to existing product quality, expend ample resources and the energy, improve the production cost of cupper smelting, do not play again itself intrinsic economic worth, it does not have bring due economic benefit for cupper smelting, be that cost raises, while being there is no output economic benefit, both sides are added, and bring significant negative influence to the economic profit space of cupper smelting, reduce the profitability of cupper smelting。

Furthermore, in recent years, along with Copper making industry develops rapidly, old smeltery and new smelter are tapped the potential and upgrade technologically and are made copper yield increase comparatively fast, and this trend also can be sustained, and cause the supply of high-quality copper concentrate to become more and more nervous。For Mai Kuang enterprise, the copper concentrate of buying high-quality is more much higher than purchasing impure high copper concentrate cost。Therefore, cupper smelting is from self benefit, and the raw material of buying becomes to become increasingly complex, and impurity component is more and more higher, mainly has the impurity elements such as lead, zinc, arsenic, antimony, bismuth, stannum。The copper concentrate that impurity content is high is more cheap than the copper concentrate price of high-quality to a certain degree, and impurity content is more high, and copper concentrate is more cheap。These high impurity copper concentrate further increasing the impurity content in copper smelting slag after putting into production。According to above-mentioned, change a thought angle, impurity element is also a kind of resource, economic benefit can also be produced, if cupper smelting purchases high impurity copper concentrate with relatively low price, then, again by impurity element contained therein to sell outside the form of metal product, output economic benefit, one-in-and-one-out, two combines, both cost of material had been reduced, adding again extra income, this will significantly increase the profitability of cupper smelting, and this will be a management mode with very big captivation for Copper making industry low at present。

Therefore, how the impurity element elimination in copper smelting slag is beneficial to the output purity better downstream product of more high-quality, impurity element is reclaimed to sell outside the form of metal product simultaneously, economic benefit is brought for cupper smelting, improve the profitability of cupper smelting, reducing the wasting of resources, reducing environmental pollution is that those skilled in the art need badly and solve the technical problem that simultaneously。

Summary of the invention

Based on described above, it is an object of the invention to provide a kind of method reclaiming lead, zinc, arsenic, antimony, bismuth and stannum from high impurity copper metallurgical slag, impurity element in copper smelting slag can be removed and be beneficial to the output purity better downstream product of more high-quality by the method, impurity element is reclaimed to sell outside the form of metal product simultaneously, economic benefit is brought for cupper smelting, improve the profitability of cupper smelting, reduce the wasting of resources simultaneously, reduce environmental pollution。

For solving above-mentioned technical problem, the present invention adopts the following technical scheme that

A kind of method reclaiming lead, zinc, arsenic, antimony, bismuth and stannum from high impurity copper metallurgical slag, comprises the following steps:

1) melted copper smelting slag liquation is joined in the container containing slag for containing copper smelting slag liquation;Then the upper liquid level certain depth below being immersed in described container containing slag by the feed tube being arranged on refining furnace diapire and drain pipe copper smelting slag liquation, being then turned on the vacuum pump that connects with described refining furnace by the cavity vacuum state in described refining furnace, now in refining furnace, under the effect of atm difference between vacuum residual voltage and external atmosphere pressure, the cavity passage along described feed tube and described drain pipe of the copper smelting slag liquation in described container containing slag rises in the cavity flowing into described refining furnace;

The profile of described refining furnace is vertical type columnar, and inner hollow forms cavity, and described refining furnace includes steel shell and builds the refractory lining at described steel shell inner surface by laying bricks or stones, and the top of described refining furnace is provided with the gas outlet for being connected with described vacuum pump;

Described feed tube and described drain pipe all include steel-made inner shell, be arranged on the refractory lining of the inner surface of described steel-made inner shell and be arranged on the refractory material outer lining of outer surface of described steel-made inner shell;

Described feed tube and described drain pipe are fixedly installed on the diapire of described refining furnace and are tightly connected with the diapire of described refining furnace, cavity in described refining furnace is interconnected with the cavity passage in described feed tube, cavity in described refining furnace is interconnected with the cavity passage in described drain pipe, and the device that all and described refining furnace is connected all carries out encapsulation process to prevent from destroying the vacuum state in described refining furnace at the position being connected with described refining furnace;

2) jet in the copper smelting slag liquation in described feed tube driving gas with pressure, then under the drive of atm difference and driving gas, the copper smelting slag liquation in described container containing slag is constantly risen in the described refining furnace of inflow by described feed tube, then the copper smelting slag liquation in described refining furnace is constantly flowed out by described refining furnace again through described drain pipe and is back in described container containing slag, forms circulating of copper smelting slag liquation between described container containing slag, feed tube, refining furnace and drain pipe;

Meanwhile, in described refining furnace, blow oxygen-containing gas to the copper smelting slag liquation in described refining furnace;

Utilize the oxygen element in oxygen-containing gas that impurity element included in the copper smelting slag liquation in described refining furnace is oxidized to the oxide of corresponding impurity element, the oxide of the impurity element that oxidation is formed becomes the volatilization elimination of gaseous oxygen compound under vacuum conditions, it is achieved the process of impurity element in elimination copper smelting slag;

Then it is mixed with the gas of the oxide of the impurity element of gaseous state to enter the condenser that connects with described refining furnace and be condensed, obtains the oxide mixture of the impurity element of condensed condensed state, it is achieved the process of impurity element in recovery copper smelting slag;

Described impurity element include in lead, zinc, arsenic, antimony, bismuth and tin element one or more or all;

Copper smelting slag liquation is aoxidized by the Oxidation utilizing the oxygen element in oxygen-containing gas so that the copper smelting slag liquation after oxidation includes bloodstone, cupric oxide ore and quartz mine, it is achieved the process aoxidized by copper smelting slag;

3) described step 2) carry out a period of time after, the component of the copper smelting slag liquation after sample examination removing impurities and oxidation and content, if result of laboratory test reaches target design requirement, then first abolish the vacuum state in described refining furnace, then the feed tube being arranged on described refining furnace diapire and drain pipe being departed from the copper smelting slag liquation in described container containing slag, removing impurities oxidation processes terminates;If result of laboratory test miss the mark designing requirement, continue removing impurities oxidation processes, until result of laboratory test reaches target design requirement;

Removing impurities oxidation processes terminate to obtain removing impurities and oxidation after copper smelting slag liquation, the oxide mixture of impurity element of condensed state and the flue gas discharged by described vacuum pump;

4) by step 3) copper smelting slag liquation after the removing impurities that obtains and oxidation first passes around slow cooling and processes, then the copper smelting slag processed through slow cooling is first carried out flotation, obtain major part bloodstone and flotation tailing, then described flotation tailing is carried out magnetic separation, obtain remaining bloodstone and magnetic tailing, again described magnetic tailing is leached, obtain containing copper products and leached mud, finally described leached mud is sequentially carried out washing and filters, obtain siliceous product, it is achieved reclaim the process of ferrum, copper and element silicon in copper smelting slag。

Preferably, described step 2) in, by described oxygen-containing gas below the upper liquid level blowing the copper smelting slag liquation to described refining furnace in the way of submergence blows, the gas outlet spraying described oxygen-containing gas is positioned at below the upper liquid level of copper smelting slag liquation of described refining furnace。

Preferably, described step 2) in, by oxygen rifle in the copper smelting slag liquation blowed by described oxygen-containing gas in the way of top-blown gas to described refining furnace, the gas outlet of described oxygen rifle is positioned at more than the upper liquid level of the copper smelting slag liquation of described refining furnace and with the upper liquid level of copper smelting slag liquation in a distance;

Described oxygen rifle is the multilamellar internal and external casing structure of the hollow pipe including multiple inside and outside suit, described oxygen rifle include by inside and outside the cavity in hollow pipe or adjacent two suit hollow pipe tube wall between cavity formed and for carrying the oxygen-containing gas passage of described oxygen-containing gas, described oxygen-containing gas passage connects with the compressed air source unit of described oxygen-containing gas;

That described oxygen rifle also includes being formed by cavity between the tube wall of the hollow pipe of suit inside and outside adjacent two and for described oxygen rifle carries out the cool cycles aquaporin of cooling protection, described cool cycles aquaporin connects with apparatus for supplying cool water;

Described oxygen rifle also includes for improving described oxygen-containing gas spouting velocity and controlling the shower nozzle of described oxygen-containing gas injection direction, and described shower nozzle is arranged on the bottom of described oxygen rifle, and the gas outlet of described oxygen rifle is arranged on described shower nozzle;

Described oxygen rifle is arranged on the roof of described refining furnace and can slide up and down along the roof of described refining furnace。

Preferably, described step 2) in, when the cavity in described refining furnace is in vacuum state, by oxygen rifle by the way of top-blown gas to winding-up fuel gas and oxygen-containing gas in described refining furnace, described fuel gas and described oxygen-containing gas are lighted burning, copper smelting slag liquation in described refining furnace is carried out supplementary heating process by the combustion reaction liberated heat utilizing described fuel gas and described oxygen-containing gas, the combustion reaction liberated heat of described fuel gas and described oxygen-containing gas is utilized to be purged processing to the dross thing formed after splash copper smelting slag liquation cooling on described refining furnace inwall;

The gas outlet of described oxygen rifle is positioned at more than the upper liquid level of the copper smelting slag liquation of described refining furnace and with the upper liquid level of copper smelting slag liquation in a distance;

Described oxygen rifle is the multilamellar internal and external casing structure of the hollow pipe including multiple inside and outside suit, described oxygen rifle include by inside and outside the cavity in hollow pipe or adjacent two suit hollow pipe tube wall between cavity formed and for carrying the fuel gas passage of described fuel gas, described fuel gas passage connects with the compressed air source unit of described fuel gas;

Described oxygen rifle also include by inside and outside the cavity in hollow pipe or adjacent two suit hollow pipe tube wall between cavity formed and for carrying the oxygen-containing gas passage of described oxygen-containing gas, described oxygen-containing gas passage connects with the compressed air source unit of described oxygen-containing gas;

That described oxygen rifle also includes being formed by cavity between the tube wall of the hollow pipe of suit inside and outside adjacent two and for described oxygen rifle carries out the cool cycles aquaporin of cooling protection, described cool cycles aquaporin connects with apparatus for supplying cool water;

Described oxygen rifle is arranged on the roof of described refining furnace and can slide up and down along the roof of described refining furnace。

Preferably, when the cavity in described refining furnace is in atmospheric pressure state, by oxygen rifle by the way of top-blown gas to winding-up fuel gas and oxygen-containing gas in described refining furnace, described fuel gas and described oxygen-containing gas are lighted burning, utilize the combustion reaction liberated heat of described fuel gas and described oxygen-containing gas that the dross thing formed after splash copper smelting slag liquation cooling on described refining furnace inwall is carried out fusing removing to process, utilize the combustion reaction liberated heat of described fuel gas and described oxygen-containing gas that described refining furnace is carried out baker process;

Described oxygen rifle is the multilamellar internal and external casing structure of the hollow pipe including multiple inside and outside suit, described oxygen rifle include by inside and outside the cavity in hollow pipe or adjacent two suit hollow pipe tube wall between cavity formed and for carrying the fuel gas passage of described fuel gas, described fuel gas passage connects with the compressed air source unit of described fuel gas;

Described oxygen rifle also include by inside and outside the cavity in hollow pipe or adjacent two suit hollow pipe tube wall between cavity formed and for carrying the oxygen-containing gas passage of described oxygen-containing gas, described oxygen-containing gas passage connects with the compressed air source unit of described oxygen-containing gas;

That described oxygen rifle also includes being formed by cavity between the tube wall of the hollow pipe of suit inside and outside adjacent two and for described oxygen rifle carries out the cool cycles aquaporin of cooling protection, described cool cycles aquaporin connects with apparatus for supplying cool water;

Described oxygen rifle is arranged on the roof of described refining furnace and can slide up and down along the roof of described refining furnace。

Preferably, described step 1) in, the copper grade of described copper smelting slag liquation is more than 3%。

Compared with prior art, the invention provides a kind of method reclaiming lead, zinc, arsenic, antimony, bismuth and stannum from high impurity copper metallurgical slag, the method has following useful technique effect:

1. the present invention is directed to the direct refined copper metallurgical slag liquation of vacuum distilling, the problem that the elimination speed of the impurity element in copper smelting slag and removal effect are all very undesirable, propose improved technique scheme: in vacuum distillation process, blow oxygen-containing gas to the copper smelting slag liquation in described refining furnace, utilize the oxygen element in oxygen-containing gas that impurity element included in the copper smelting slag liquation in described refining furnace is oxidized to the oxide of corresponding impurity element, impurity element is freed from complicated mineral facies, the oxide of the corresponding impurity element of output, the oxide of this impurity element can be individually present, the oxide of the impurity element that oxidation is formed becomes the volatilization elimination of gaseous oxygen compound under vacuum conditions, volatilization process is no longer influenced by copper smelting slag liquation the obstruction of other material, the boiling characteristics volatilization itself having can be relied on, and described impurity element includes lead, zinc, arsenic, antimony, in bismuth and tin element one or more or all, the oxide of above-mentioned impurity element is respectively provided with relatively low boiling point, volatility is fine under vacuum conditions, there is higher elimination speed and removal effect, some combines above, achieve the process of impurity element in elimination copper smelting slag。

2. in the present invention, in described refining furnace, oxygen-containing gas is blowed to the copper smelting slag liquation in described refining furnace, utilize the oxygen element in oxygen-containing gas that impurity element included in the copper smelting slag liquation in described refining furnace is oxidized to the oxide of corresponding impurity element, the oxide of the impurity element that oxidation is formed becomes the volatilization elimination of gaseous oxygen compound under vacuum conditions, then it is mixed with the gas of the oxide of the impurity element of gaseous state to enter the condenser that connects with described refining furnace and be condensed, obtain the oxide mixture of the impurity element of condensed condensed state, owing to the fusing point of oxide is more much higher than the fusing point of simple substance, after making the air-flow carrying a large amount of oxide enter condenser, this oxide is directly condensed into the solid granulates or powder that there is no adhesive, this solid granulates or powder are cooled further in dropping process, adhesive is thoroughly lost after to condenser, obtain a pile loose, it is similar to oxide particle or the oxide powder of the tiny grains of sand, this oxide particle or oxide powder are above-mentioned oxide mixture。It should be evident that loose, to be similar to tiny grains of sand oxide particle or oxide powder can transport easily from condenser, time saving and energy saving, thoroughly solve the problem that the too big multicomponent alloy of above-mentioned volume is difficult to transport from condenser;And this oxide mixture inherently graininess or Powdered, orcible entry pulverizing is carried out again without follow-up, time saving and energy saving, thoroughly solve above-mentioned multicomponent alloy to be difficult to owing to quality is softer pulverize for graininess or Powdered simultaneously, thus improve the work efficiency of refine removing impurities operation, it is ensured that the normal rhythm of production of whole Copper making flow process。

3. compared with prior art, the present invention with temperature 1000 DEG C~1350 DEG C hot copper smelting slag for process object, first with oxygen, slag is aoxidized, then carries out slow cooling process, finally realize the separation of copper, ferrum and silicon dioxide mainly through technique of preparing。Described hot copper smelting slag has been carried out pretreating process by the present invention, including oxidation and slow cooling two parts。The oxidizing process of the present invention makes full use of the sensible heat energy of hot melt copper smelting slag, under the Oxidation of oxygen, makes the delafossite thing in copper smelting slag carry out aoxidizing, copper ferrum is sufficiently separated in conjunction with mineral。Along with being performed continuously over of hot melt copper smelting slag slag oxidation reaction, fayalite (the 2FeO SiO in copper smelting slag2) it is converted into Fe3O4And SiO2, magnetic iron ore in slag, limonite and pyrites are converted into Fe2O3;When peroxidating, fayalite the Fe converted3O4It is further oxidized to Fe2O3。Further, the copper sulfide mineral such as a small amount of matte in slag also can be oxidized to CuO and SiO2, metallic copper is oxidized to copper oxide。Finally, the present invention makes the unified bloodstone being converted into easily choosing of iron mineral in copper smelting slag by aoxidizing, and copper mineral is unified, and be converted into can the cupric oxide ore of active flotation or leaching。After oxidation, the present invention is by carrying out mineral enrichment crystallization to the retarded cooling process of copper smelting slag, ready for recyclings such as ore dressings。In the present invention, hot melt copper smelting slag is after above-mentioned pretreatment, substantially with bloodstone (Fe2O3) and cupric oxide ore (CuO) and quartz (SiO2) mineral forms exist;Bloodstone is reclaimed by flotation and magnetic separation, and copper oxide can pass through sodium sulfide activation and carry out flotation recovery, reclaims as quartz mineral after last tailing filtration。The present invention adopts oxidation and retarded cooling process to carry out hot melt copper smelting slag pretreatment, take full advantage of the sensible heat resource of copper smelting slag self, by hot melt copper smelting slag is fully oxidized, copper mineral, iron mineral all being aoxidized and copper ferrum separates in conjunction with mineral oxide, to make each copper mineral inversion of phases be copper oxide phase, each iron mineral inversion of phases is bloodstone thing phase;It is enriched with by retarded cooling process and promotes that mineral grain is grown up, being beneficial to follow-up employing ore dressing and process technique recovery copper, ferrum and silicon。Therefore, method flow provided by the invention is short, technique is simple, be easily achieved and control, and has substantially met the demand of the copper smelting slag recycling treatment of Copper making industry, has had the advantages such as use scope is wide and practical。It addition, the method reclaiming copper, ferrum and silicon from copper smelting slag provided by the invention does not produce secondary refuse, pollution-free, save the input of mass energy。

Accompanying drawing explanation

Fig. 1 is the operation principle schematic diagram of the method reclaiming lead, zinc, arsenic, antimony, bismuth and stannum from high impurity copper metallurgical slag provided by the invention。

In figure: 1 refining furnace, 2 feed tubes, 201 drive gas tube, 3 drain pipes, 4 oxygen rifles, 5 containers containing slag。

Detailed description of the invention

For making the object, technical solutions and advantages of the present invention clearly, below in conjunction with the accompanying drawing in the present invention, the technical scheme in the present invention is clearly and completely described, it is clear that, described embodiment is a part of embodiment of the present invention, rather than whole embodiments。Based on the embodiment in the present invention, the every other embodiment that those of ordinary skill in the art obtain under the premise not making creative work, broadly fall into the scope of protection of the invention。

In describing the invention, it will be appreciated that, term " " center ", " axially ", " radially ", " longitudinal direction ", " transverse direction ", " length ", " width ", " on ", D score, " front ", " afterwards ", " left side ", " right side ", " top ", " end ", " interior ", " outward ", " clockwise ", " counterclockwise ", " level ", orientation or the position relationship of the instruction such as " vertically " are based on the orientation shown in accompanying drawing or in practical application or position relationship, it is for only for ease of the description present invention and simplifies description, rather than the device of instruction or hint indication or element must have specific orientation, with specific azimuth configuration and operation, therefore it is not considered as limiting the invention。

According to above-mentioned analysis conclusion, the invention provides a kind of method reclaiming lead, zinc, arsenic, antimony, bismuth and stannum from high impurity copper metallurgical slag, comprise the following steps:

1) melted copper smelting slag liquation is joined in the container containing slag 5 for containing copper smelting slag liquation;Then the upper liquid level certain depth below being immersed in container containing slag 5 by the feed tube 2 being arranged on refining furnace 1 diapire and drain pipe 3 copper smelting slag liquation, being then turned on the vacuum pump that connects with refining furnace 1 by the cavity vacuum state in refining furnace 1, now in refining furnace 1, under the effect of atm difference between vacuum residual voltage and external atmosphere pressure, the cavity passage along feed tube 2 and drain pipe 3 of the copper smelting slag liquation in container containing slag 5 rises in the cavity flowing into refining furnace 1;

The profile of refining furnace 1 is vertical type columnar, and inner hollow forms cavity, and refining furnace 1 includes steel shell and builds the refractory lining at steel shell inner surface by laying bricks or stones, and the top of refining furnace 1 is provided with the gas outlet for being connected with vacuum pump;

Feed tube 2 and drain pipe 3 all include steel-made inner shell, be arranged on the refractory lining of the inner surface of steel-made inner shell and be arranged on the refractory material outer lining of outer surface of steel-made inner shell;

Feed tube 2 and drain pipe 3 are fixedly installed on the diapire of refining furnace 1 and are tightly connected with the diapire of refining furnace 1, cavity in refining furnace 1 is interconnected with the cavity passage in feed tube 2, cavity in refining furnace 1 is interconnected with the cavity passage in drain pipe 3, and all devices being connected with refining furnace 1 all carry out encapsulation process to prevent from destroying the vacuum state in refining furnace 1 at the position being connected with refining furnace 1;

2) jet in the copper smelting slag liquation in feed tube 2 driving gas with pressure, then under the drive of atm difference and driving gas, the copper smelting slag liquation in container containing slag 5 is constantly risen in inflow refining furnace 1 by feed tube 2, then the copper smelting slag liquation in refining furnace 1 is constantly flowed out by refining furnace 1 again through drain pipe 3 and is back in container containing slag 5, forms circulating of copper smelting slag liquation between container containing slag 5, feed tube 2, refining furnace 1 and drain pipe 3;

Meanwhile, in refining furnace 1, blow oxygen-containing gas to the copper smelting slag liquation in refining furnace 1;

Utilize the oxygen element in oxygen-containing gas that impurity element included in the copper smelting slag liquation in refining furnace 1 is oxidized to the oxide of corresponding impurity element, the oxide of the impurity element that oxidation is formed becomes the volatilization elimination of gaseous oxygen compound under vacuum conditions, it is achieved the process of impurity element in elimination copper smelting slag;

Then it is mixed with the gas of the oxide of the impurity element of gaseous state to enter the condenser that connects with refining furnace 1 and be condensed, obtains the oxide mixture of the impurity element of condensed condensed state, it is achieved the process of impurity element in recovery copper smelting slag;

Impurity element include in lead, zinc, arsenic, antimony, bismuth and tin element one or more or all;

Copper smelting slag liquation is aoxidized by the Oxidation utilizing the oxygen element in oxygen-containing gas so that the copper smelting slag liquation after oxidation includes bloodstone, cupric oxide ore and quartz mine, it is achieved the process aoxidized by copper smelting slag;

3) step 2) carry out a period of time after, the component of the copper smelting slag liquation after sample examination removing impurities and oxidation and content, if result of laboratory test reaches target design requirement, then first abolish the vacuum state in refining furnace 1, then the feed tube 2 being arranged on refining furnace 1 diapire and drain pipe 3 depart from the copper smelting slag liquation in container containing slag 5, and removing impurities oxidation processes terminates;If result of laboratory test miss the mark designing requirement, continue removing impurities oxidation processes, until result of laboratory test reaches target design requirement;

Removing impurities oxidation processes terminate to obtain removing impurities and oxidation after copper smelting slag liquation, the oxide mixture of impurity element of condensed state and the flue gas discharged by vacuum pump;

4) by step 3) copper smelting slag liquation after the removing impurities that obtains and oxidation first passes around slow cooling and processes, then the copper smelting slag processed through slow cooling is first carried out flotation, obtain major part bloodstone and flotation tailing, then described flotation tailing is carried out magnetic separation, obtain remaining bloodstone and magnetic tailing, again described magnetic tailing is leached, obtain containing copper products and leached mud, finally described leached mud is sequentially carried out washing and filters, obtain siliceous product, it is achieved reclaim the process of ferrum, copper and element silicon in copper smelting slag。

Utilize the method that the principle of vacuum distilling carries out refine removing impurities, had a lot in the prior art。But, in prior art, the object handled by vacuum distilling refine removing impurities is usually multicomponent alloy, and element is many to volatilize with metal simple-substance state。And in the present invention pending to as if copper smelting slag, being a kind of slag, carrying out vacuum distilling refine removing impurities if being placed directly under vacuum environment by this copper smelting slag, the elimination speed of impurity element and removal effect are all very undesirable。Reason is: it is known that, slag is a kind of very complicated thing phase, it is a kind of mineral facies, impurity element therein is substantially absent from independent phase, but be easy to the host element with other and form mineral facies, for instance: form the copper mineral phase containing a large amount of impurity elements and iron mineral phase, when vacuum distillatory refining, these mineral facies can seriously hinder the volatilization of its contained impurity element, thus having severely impacted rate of volatilization and the volatility of impurity element。For this, the present invention proposes improved technique scheme: blow oxygen-containing gas to the copper smelting slag liquation in refining furnace 1 in vacuum distillation process, utilize the oxygen element in oxygen-containing gas that impurity element included in the copper smelting slag liquation in refining furnace 1 is oxidized to the oxide of corresponding impurity element, impurity element is freed from complicated mineral facies, the oxide of the corresponding impurity element of output, the oxide of this impurity element can be individually present, the oxide of the impurity element that oxidation is formed becomes the volatilization elimination of gaseous oxygen compound under vacuum conditions, volatilization process is no longer influenced by copper smelting slag liquation the obstruction of other material, the boiling characteristics volatilization itself having can be relied on, and impurity element includes lead, zinc, arsenic, antimony, in bismuth and tin element one or more or all, the oxide of above-mentioned impurity element is respectively provided with relatively low boiling point, volatility is fine under vacuum conditions, there is higher elimination speed and removal effect, some combines above, achieve the process of impurity element in elimination copper smelting slag。

In vacuum distilling refine removing impurities process now, above-mentioned lead impurity element, zinc, arsenic, antimony, bismuth and/or tin element mainly directly volatilize with elemental form, secondly directly volatilize with oxide morphology。After above-mentioned simple substance and sulfide become the free space that gaseous volatilization enters refining furnace 1 top, owing to the temperature in the free space on refining furnace 1 top is higher, and due to lead, zinc, arsenic, antimony, the sulfide of bismuth and/or tin element at high temperature instability easily thermally decomposes, the overwhelming majority making above-mentioned sulfide correspondingly thermally decomposes as simple substance plumbous, zinc, arsenic, antimony, bismuth and/or stannum and elemental sulfur, then the simple substance thermally decomposing generation is plumbous, zinc, arsenic, antimony, bismuth and/or stannum, elemental sulfur and the simple substance lead volatilized with elemental form at the very start, zinc, arsenic, antimony, bismuth and/or stannum enter follow-up condenser condensation with one piece of air-flow, owing to fusing point and the boiling point of elemental sulfur are all relatively low, typically not condense within the condenser, and be to continue with flowing into follow-up device with gaseous state, therefore condenser generally only condenses above-mentioned simple substance plumbous, zinc, arsenic, antimony, bismuth and/or stannum。Owing to simple substance is plumbous, zinc, arsenic, antimony, the fusing point of bismuth and/or stannum is relatively low, and further, in condensation process, simple substance is plumbous, zinc, arsenic, antimony, bismuth and/or stannum blend mutually, are formed and include lead, zinc, arsenic, antimony, the multicomponent alloy of bismuth and/or tin element, the fusing point of this multicomponent alloy is lower, compares Element Lead, zinc, arsenic, antimony, in bismuth and stannum, any one fusing point is all low, though making multicomponent alloy be condensed, but it is usually liquid after condensation, it it is at most semi liquid state semisolid, substantially the solid-state without adhesive it is not likely to form, condensed multicomponent alloy is made still to have mobility and adhesive, the droplet of multicomponent alloy or semi liquid state semisolid and there is the little granule of very strong adhesive finally come together in the bottom of condenser, it is condensed further, finally it is easy to condensation form sufficiently bulky one and stick together greatly or a bulk of solid-state multicomponent alloy, owing to volume is too big, this solid-state multicomponent alloy is difficult to transport from the material outlet of condenser design originally, it is necessary to first quit work by condenser, then wait that condenser internal temperature is down to close to room temperature, then open condenser, allow workman enter condenser and carry out orcible entry bulk, waste time and energy;And owing to volume is too big, even if after this solid-state multicomponent alloy transports from condenser, it must also be carried out orcible entry to pulverize to facilitate subsequent treatment, waste time and energy, and owing to the hardness of the metal simple-substance of lead, zinc, arsenic, antimony, bismuth and/or tin element is relatively low, make above-mentioned multicomponent alloy quality softer, be therefore difficult to this bulk multicomponent alloy is ground into graininess or Powdered。To sum up, current technique makes the impurity element becoming gaseous volatilization elimination be condensed within the condenser with elemental form, it is readily formed sufficiently bulky a bulk of multicomponent alloy, this multicomponent alloy is due to reasons such as volume are too big, quality is softer, a lot of negative influences is brought to follow-up process, seriously reduce the work efficiency of refine removing impurities operation, have a strong impact on the normal rhythm of production of whole Copper making flow process。For this, in the present invention, step 2) in, in refining furnace 1, oxygen-containing gas is blowed to the copper smelting slag liquation in refining furnace 1, utilizing the oxygen element in oxygen-containing gas that impurity element included in the copper smelting slag liquation in refining furnace 1 is oxidized to the oxide of corresponding impurity element, the oxide of the impurity element that oxidation is formed becomes the volatilization elimination of gaseous oxygen compound under vacuum conditions;Then it is mixed with the gas of the oxide of the impurity element of gaseous state to enter the condenser that connects with refining furnace 1 and be condensed, obtains the oxide mixture of the impurity element of condensed condensed state, it is achieved the process of impurity element in recovery copper smelting slag;Owing to the fusing point of oxide is more much higher than the fusing point of simple substance; after making the air-flow carrying a large amount of oxide enter condenser; this oxide is directly condensed into the solid granulates or powder that there is no adhesive; this solid granulates or powder are cooled further in dropping process; adhesive is thoroughly lost after to condenser; obtaining a pile is loose, be similar to the tiny grains of sand oxide particle or oxide powder, this oxide particle or oxide powder are above-mentioned oxide mixture。It should be evident that loose, to be similar to tiny grains of sand oxide particle or oxide powder transport easily from condenser, time saving and energy saving, thoroughly solve the problem that the too big multicomponent alloy of above-mentioned volume is difficult to transport from condenser;And this oxide mixture inherently graininess or Powdered, orcible entry pulverizing is carried out again without follow-up, time saving and energy saving, thoroughly solve above-mentioned multicomponent alloy to be difficult to owing to quality is softer pulverize for graininess or Powdered simultaneously, thus improve the work efficiency of refine removing impurities operation, it is ensured that the normal rhythm of production of whole Copper making flow process。

In the present invention, the process of refine removing impurities is only the lead impurity element in elimination copper smelting slag liquation, zinc, arsenic, antimony, bismuth and/or tin element, does not change the character of copper smelting slag liquation;Oxidation processes is only that each iron mineral in copper smelting slag is oxidized to bloodstone, and each copper mineral in copper smelting slag liquation is oxidized to cupric oxide ore, make the copper smelting slag liquation after oxygen-containing gas oxidation include bloodstone, cupric oxide ore and quartz mine, be only the thing phase state changing contained element;Above-mentioned steps 3) in " removing impurities oxidation processes terminate to obtain removing impurities and oxidation after copper smelting slag liquation " " removing impurities and the copper smelting slag liquation after oxidation " mentioned remain copper smelting slag liquation, it is the copper smelting slag liquation being stripped of part of impurity elements, is the thing phase state copper smelting slag liquation that obtains change。

In the present invention, above-mentioned oxygen-containing gas is preferably air or oxygen-enriched air, and in oxygen-enriched air, the percent by volume of oxygen is 25%~95%。Preferably, with oxygen stoichiometry, the blowing volume controlling oxygen is 7m3/ t slag~10m3/ t slag。

In the present invention, target design requirement for result of laboratory test, apparently, plumbous, zinc, arsenic, antimony, the volatility of bismuth and these six kinds of elements of stannum varies, these six kinds of elements are unlikely removed to ideal value simultaneously, therefore, above-mentioned target design requires can only using the content of some element in element in above-mentioned 6 or certain several element as object reference, can only using the content of some element that Influence of production is maximum or certain several element as object reference, such as: plumbous the highest with two kinds of element content in copper concentrate of arsenic, the two is to having the greatest impact of producing, therefore can using the content of lead and arsenic both elements as the target design requirement of above-mentioned result of laboratory test, as long as the content of the lead of sample examination and arsenic has reached target design requirement, mean that removing impurities process terminates, then first abolish the vacuum state in refining furnace 1;Whether the removal effect as all the other impurity elements reaches desired level, does not make to go into seriously。Can also so that whether the content of cupric oxide ore in copper smelting slag or bloodstone reaches the ideal value target design requirement as above-mentioned result of laboratory test。

In the present invention, above-mentioned driving gas is nitrogen or argon, it is preferred to nitrogen。

In the present invention, namely above-mentioned vacuum residual voltage refers to the pressure of the remaining under vacuum conditions gas of refining furnace 1 internal cavity, the same with the meaning of noun vacuum。Preferably, step 2) in vacuum residual voltage be 100Pa~1000Pa。

In the present invention, structure and type to the container containing slag 5 for containing copper smelting slag liquation are not limited as, and meet for containing this function of copper smelting slag liquation, and this container containing slag 5 end face at least has an opening to allow refining furnace 1 oscilaltion。

In the present invention, by being arranged on feed tube 2 drive gas tube 201 to driving gas with pressure of jetting in the copper smelting slag liquation in feed tube 2。

In the present invention, it is higher that high impurity copper concentrate means the content of impurity element in copper concentrate, impurity element include in lead, zinc, arsenic, antimony, bismuth and tin element one or more or all, the content of impurity element exceedes the industry general claimed range to its content。In the present invention, in actual production, above-mentioned copper concentrate not necessarily includes whole above-mentioned six kinds of impurity elements, it is possible to include one or more of above-mentioned six kinds of impurity elements, it is also possible to include whole above-mentioned six kinds of elements。In actual production, even if above-mentioned copper concentrate comprises a certain kind of above-mentioned six kind impurity element, but the content of this impurity element is likely to also less than industry universal standard, but the content of other contained certain impurity element exceedes industry universal standard。In actual production, as long as impurity element contained in above-mentioned copper concentrate is one of above-mentioned six kinds of impurity elements and this impurity content exceedes industry universal standard, this copper concentrate is just for high impurity copper concentrate。The smelting slag of high impurity copper concentrate smelting operation output is exactly generally high impurity smelting slag。

In the accessible high impurity copper metallurgical slag of the present invention, the preferred higher limit of the percentage by weight of above-mentioned six kinds of impurity elements that may be present is: lead≤5.0%, zinc≤10.0%, arsenic≤5.0%, antimony≤3.0%, bismuth≤5.0%, stannum≤1.0%。

The invention provides a kind of method reclaiming lead, zinc, arsenic, antimony, bismuth and stannum from high impurity copper metallurgical slag, apparently, the method is not to process high impurity copper metallurgical slag, process the ratio in numerous functions that high impurity copper metallurgical slag is only the method more prominent a bit;Since the method can process high impurity copper metallurgical slag, it is clear that it also is able to the normal copper smelting slag of processing element content。Adopt the method normal copper smelting slag of processing element content provided by the invention also in protection scope of the present invention。As long as namely adopting method provided by the invention to process copper smelting slag, all in protection scope of the present invention。

The principle that in the present invention, copper smelting slag liquation circulates: when the upper liquid level certain depth below that the feed tube 2 being arranged on refining furnace 1 bottom surface and drain pipe 3 are immersed in container containing slag 5 inner melt, being then turned on the vacuum pump that connects with refining furnace 1 by the cavity vacuum state in refining furnace 1, now in refining furnace 1, under the effect of atm difference between vacuum residual voltage and external atmosphere pressure, the liquation in container containing slag 5 rises along the cavity flowing into refining furnace 1 along the cavity passage of feed tube 2 and drain pipe 3;Copper smelting slag liquation now does not circulate;For making copper smelting slag liquation circulate, jet in the liquation in feed tube 2 driving gas with pressure, owing to expanded by heating and pressure decline after driving gas to enter the liquation in feed tube 2, cause isothermal expansion, in feed tube 2, moment produces substantial amounts of nuclei of bubbles and expands rapidly, the gas-powered copper smelting slag liquation expanded rises, under the drive of atm difference and driving gas, the liquation in container containing slag 5 is constantly risen in inflow refining furnace 1 by feed tube 2, then the liquation in refining furnace 1 is constantly flowed out by refining furnace 1 again through drain pipe 3 and is back in container containing slag 5, at container containing slag 5, feed tube 2, circulating of liquation is formed between refining furnace 1 and drain pipe 3。

In the present invention, above-mentioned lead impurity element, zinc, arsenic, antimony, bismuth and/or tin element occur mainly in the upper surface vicinity of copper smelting slag liquation in container containing slag 5 with this process that oxide form volatilizees, after impurity element near copper smelting slag liquation upper surface is removed, it is positioned at internal and bottom the impurity element of copper smelting slag liquation and starts upwards near surface place diffusion by diffusion kinetics, recover to improve the impurity content of copper smelting slag liquation upper surface vicinity, the state of the eliminations to be evaporated such as the impurity element entrance making this place, obviously, at container containing slag 5, feed tube 2, circulating of liquation is formed between refining furnace 1 and drain pipe 3, the such big cycle volume ground flowing of liquation is that the above-mentioned impurity element in elimination copper smelting slag liquation improves extremely advantageous dynamic conditions, the flowing of big cycle volume improves internal and bottom the impurity element of copper smelting slag liquation and diffuses to the speed of liquid level vicinity, decrease diffusion time, also internal and bottom the impurity element of copper smelting slag liquation is made can to rise to the upper liquid level vicinity of copper smelting slag liquation substantially, thus improve removing impurities speed and the removing impurities degree that refine removing impurities processes, reduce the removing impurities cycle that refine removing impurities processes。

In the present invention, the temperature of copper smelting slag is at 1000 DEG C~1350 DEG C, it is preferable that within the scope of 1100 DEG C~1250 DEG C。The source of hot copper smelting slag is not particularly limited by the present invention, it is possible to process the copper grade smelting slag less than or equal to 3%, vessel slag and electric dilution slag etc., it is also possible to process a copper grade step copper slag more than 3% and blowing slag。

In above-mentioned oxidizing process, the present invention makes full use of the sensible heat energy of hot slag, under the Oxidation of oxygen, makes delafossite thing in slag aoxidize, makes copper ferrum be sufficiently separated in conjunction with mineral simultaneously。Along with being performed continuously over of hot melt copper smelting slag oxidation reaction, fayalite (the 2FeO SiO in copper smelting slag2) it is converted into Fe3O4And SiO2, magnetic iron ore in slag, limonite and pyrites are converted into Fe2O3;When peroxidating, fayalite the Fe converted3O4It is further oxidized to Fe2O3。Further, the copper sulfide mineral such as a small amount of matte in slag also can be oxidized to CuO and SiO2, metallic copper is oxidized to copper oxide。Finally, the present invention by aoxidize make iron mineral in slag unified be converted into unified being converted into of the easy bloodstone of choosing, copper mineral can the cupric oxide ore of active flotation or leaching。

Fayalite oxidation Decomposition in copper smelting slag liquation is Fe by the Oxidation utilizing the oxygen element in oxygen-containing gas3O4And SiO2And ferrum copper is decomposed into independent iron mineral and independent copper mineral in conjunction with mineral oxide, and the ferrum element controlled in the quantity delivered copper smelting slag liquation the most at last of oxygen-containing gas is oxidized to Fe2O3So that the various iron minerals in copper smelting slag are oxidized to bloodstone, and the copper in copper smelting slag liquation is oxidized to copper oxide so that the various copper minerals in copper smelting slag liquation are oxidized to cupric oxide ore, copper smelting slag liquation after oxygen-containing gas oxidation includes bloodstone, cupric oxide ore and quartz mine, it is achieved the process aoxidized by copper smelting slag。

After the oxidation of certain time, the copper smelting slag that oxidation is obtained by the present invention carries out slow cooling process。The present invention is by carrying out mineral enrichment crystallization to the retarded cooling process of slag, ready for recyclings such as ore dressings。In one embodiment of the invention, slow cooling processes and includes successively: natural slow cooling 24 hours and the cooling 36 hours that adds water。Wherein, the cooling that adds water can adopt the mode adding Water spray to carry out。

The present invention adopts oxidation and retarded cooling process to carry out hot slag pretreatment, take full advantage of the sensible heat resource of copper smelting slag self, by to hot melt copper smelting slag aerobic oxidation, copper mineral, iron mineral all being aoxidized and by copper ferrum in conjunction with minerals separation, to make each copper mineral inversion of phases be copper oxide phase, each iron mineral inversion of phases is bloodstone thing phase;Then pass through retarded cooling process enrichment and promote that mineral grain is grown up。In the present invention, hot melt copper smelting slag is after above-mentioned pretreatment, substantially with bloodstone (Fe2O3) and cupric oxide ore (CuO) and quartz (SiO2) mineral forms exist, namely obtain the copper smelting slag processed through slow cooling, enhance the washability of various resource mineral in slag, be beneficial to follow-up employing ore dressing and process technique and reclaim copper, ferrum and silicon。

After slow cooling processes, before ore dressing processes, the present invention preferably also includes: the copper smelting slag processed through slow cooling is carried out grinding。Grinding is technological means well known to those skilled in the art, and in an embodiment of the present invention, after grinding, the fineness of copper smelting slag is 85 order~325 orders, it is preferred to 100 order~300 orders。After slow cooling process terminates, the slag in container containing slag 5 can be poured out by the present invention, sends into ore grinding ore-sorting system with after crusher in crushing by belt, slag through grinding ore grinding, become the ore pulp of certain fineness laggard enter ore-sorting system。

The copper smelting slag processed through slow cooling is first carried out flotation by the present invention, obtain major part bloodstone and flotation tailing, then described flotation tailing is carried out magnetic separation, obtain remaining bloodstone and magnetic tailing, again described magnetic tailing is leached, obtain containing copper products and leached mud, finally described leached mud is sequentially carried out washing and filters, obtain siliceous product, it is achieved reclaim the process of ferrum, copper and element silicon in copper smelting slag。

The present invention is directed to high-grade copper smelting slag, after adopting flotation, magnetic separation bloodstone to carry out synthetical recovery and improves the iron mineral response rate, before leaching carries copper, also it is extracted iron mineral, decrease the harmful effect of iron ion in leaching process, lay the foundation for simplifying subsequent implementation such as the copper-extracting process extracted with electrodeposition。

Wherein, the collecting agent used by flotation can be oxidized paraffin wax soap, and its consumption is preferably 100g/t slag~800g/t slag, more preferably 200g/t slag~500g/t slag。Magnetic separation is not particularly limited by the present invention, and iron selection tailings enters and puies forward the techniques such as copper。

In above-mentioned technique, after carrying ferrum, the iron selection tailings obtained again through leach copper-extracting process to leach copper。In an embodiment of the present invention, extract technology is sulphuric acid slurry soaking technology, for technological means well known to those skilled in the art。According to containing copper grade, it is 15g/L~80g/L that the present invention can control to leach the concentration of sulphuric acid in ore pulp, it is preferred to 20g/L~60g/L;The time leached is preferably 20min~120min, more preferably 50min~110min。

After leaching, the leaching slag obtained reclaims as quartz mineral after sequentially passing through washing and filtering;And the leachate obtained extracts copper sulfate preferably through extracting, then passing through electrodeposition and obtain electro deposited copper, electro deposited copper is acceptable cathodic copper or blister copper。The present invention can be the interference of the copper-extracting process eliminating iron ion of leaching extraction after carrying ferrum, puies forward copper better effects if。And, the present invention is first by floating magnetic, leaching, extraction and electrodeposition process organic assembling, namely adopt floating magnetic leaching extraction electrodeposition flow process, copper smelting slag resource is separated into copper concentrate or tough cathode and electro deposited copper, iron ore concentrate and siliceous product, it is achieved that the maximum resource of copper smelting slag。

In above-mentioned technique, flotation, magnetic separation, high intensity magnetic separation, reverse flotation and filtration etc. are technological means well known to those skilled in the art, and the present invention is not particularly limited。

The iron ore concentrate obtained by this technique is according to purity and fineness situation, it is possible to as iron-smelting raw material and the raw material producing extraction of superpure concentrate of magnetite or iron oxide red;The siliceous product silicon content obtained and fineness are higher, for high siliceous product, it is possible to as smelting dispensing and making the construction materials such as glass, cast stone and dry powder and mortar, product market scope is widely;The copper concentrate, electro deposited copper or the copper smelting slag that obtain can return Copper making。

To sum up, method flow provided by the invention is short, and technique is simple, be easily achieved and control, and has substantially met the demand of the copper smelting slag recycling treatment of Copper making industry, the feature such as have that use scope is wide and practicality is strong。It addition, the method reclaiming copper, ferrum and silicon from copper smelting slag provided by the invention does not produce secondary refuse, pollution-free, save the input of mass energy。

For blowing the mode that specifically blows of oxygen-containing gas to the copper smelting slag liquation in refining furnace 1, in one embodiment of the invention, provide one and blow mode: step 2) in, by oxygen-containing gas below the upper liquid level blowing the copper smelting slag liquation to refining furnace 1 in the way of submergence blows, the gas outlet of ejection oxygen-containing gas is positioned at below the upper liquid level of copper smelting slag liquation of refining furnace 1。

In one embodiment of the invention, additionally provide another and blow mode: step 2) in, by oxygen rifle 4 in the copper smelting slag liquation blowed by oxygen-containing gas in the way of top-blown gas to refining furnace 1, the gas outlet of oxygen rifle 4 is positioned at more than the upper liquid level of the copper smelting slag liquation of refining furnace 1 and with the upper liquid level of copper smelting slag liquation in a distance;Oxygen rifle 4 is the multilamellar internal and external casing structure of the hollow pipe including multiple inside and outside suit, oxygen rifle 4 include by inside and outside the cavity in hollow pipe or adjacent two suit hollow pipe tube wall between cavity formed and for carrying the oxygen-containing gas passage of oxygen-containing gas, oxygen-containing gas passage connects with the compressed air source unit of oxygen-containing gas;That oxygen rifle 4 also includes being formed by cavity between the tube wall of the hollow pipe of suit inside and outside adjacent two and for oxygen rifle 4 carries out the cool cycles aquaporin of cooling protection, cool cycles aquaporin connects with apparatus for supplying cool water;Oxygen rifle 4 also includes for improving oxygen-containing gas spouting velocity and controlling the shower nozzle of oxygen-containing gas injection direction, and shower nozzle is arranged on the bottom of oxygen rifle 4, and the gas outlet of oxygen rifle 4 is arranged on shower nozzle;Oxygen rifle 4 is arranged on the roof of refining furnace 1 and can slide up and down along the roof of refining furnace 1。

Preferably, in actual production, it is possible to adopt above-mentioned two kind oxygen-containing gas to blow mode simultaneously。

Oxygen-containing gas is not suitable on the wall of container containing slag 5 to be blown in the copper smelting slag liquation in container containing slag 5 in the way of top blast, side-blown and/or bottom blowing, because this oxygen-containing gas is to be blown into Copper making liquation in the outside of refining furnace 1, the a large amount of oxygenous cognition being present in copper smelting slag liquation affects copper smelting slag liquation and smoothly enters the refining furnace 1 being in vacuum state, circulating of copper smelting slag liquation can be affected, and then affect removing impurities oxid-reclamatiom effect。

Removing impurities oxid-reclamatiom process needs certain time, and within this time period, the temperature of copper smelting slag liquation can inevitably decline, it is therefore desirable to copper smelting slag liquation is heated additional heat。Mode of heating general in current industry is: the copper smelting slag liquation in container containing slag 5 is heated insulation by the burner arranging several burn combustible things and oxygen-containing gas on the furnace wall, side of container containing slag 5, the upper liquid level of the copper smelting slag liquation in burner and container containing slag 5 is in a distance, there is Railway Project in this mode of heating: 1. so mode of heating is similar to the pattern of " broad irrigation ", the heat that burner produces is let drift, the heat that burner produces is not applied in the place of real needs fully, heat waste phenomenon is serious, heat utilization ratio is relatively low;2. first the heat that burner produces will heat in copper smelting slag liquation liquid level space above, then the heat in upper space passes to the copper smelting slag liquation of lower section in the way of radiant heat transfer, heat transfer modes has and only has this one of radiant heat transfer pattern in this process, and according to metallurgical thermodynamics principle, radiant heat transfer pattern is minimum one of several of heat transfer efficiency in numerous heat transfer modes, therefore, there is the problem that heat utilization ratio is low and heat transfer rate is less in current mode of heating;3. owing to the length and width face area of usual container containing slag 5 is bigger, it is irrational for only arranging several burners on the furnace wall, side of container containing slag 5, obviously, better near the copper smelting slag liquation heating and thermal insulation effect of burner, from burner more away from copper smelting slag liquation, heating and thermal insulation effect is more poor, and for the whole copper smelting slag liquations in container containing slag 5, heating and thermal insulation effect is extremely uneven。It should be evident that there is the current mode of heating of above-mentioned multiple problem, it is unfavorable for solving the above-mentioned technical problem mentioned in the present invention, is unfavorable for the carrying out of removing impurities oxid-reclamatiom process。For this, in one embodiment of the invention, in removing impurities oxid-reclamatiom process, when the cavity in refining furnace 1 is in vacuum state, by oxygen rifle 4 by the way of top-blown gas to winding-up fuel gas and oxygen-containing gas in refining furnace 1, fuel gas and oxygen-containing gas are lighted burning, copper smelting slag liquation in refining furnace 1 is carried out supplementary heating process by the combustion reaction liberated heat utilizing fuel gas and oxygen-containing gas, utilize the combustion reaction liberated heat of fuel gas and oxygen-containing gas that the dross thing formed after splash copper smelting slag liquation cooling on refining furnace 1 inwall is carried out fusing removing to process;The gas outlet of oxygen rifle 4 is positioned at more than the upper liquid level of the copper smelting slag liquation of refining furnace 1 and with the upper liquid level of copper smelting slag liquation in a distance;Oxygen rifle 4 is the multilamellar internal and external casing structure of the hollow pipe including multiple inside and outside suit, oxygen rifle 4 includes that the cavity between the tube wall by the hollow pipe being set with inside and outside the cavity in hollow pipe or adjacent two is formed and for transporting combustible gases fuel gas passage, and fuel gas passage connects with the compressed air source unit of fuel gas;Oxygen rifle 4 also include by inside and outside the cavity in hollow pipe or adjacent two suit hollow pipe tube wall between cavity formed and for carrying the oxygen-containing gas passage of oxygen-containing gas, oxygen-containing gas passage connects with the compressed air source unit of oxygen-containing gas;That oxygen rifle 4 also includes being formed by cavity between the tube wall of the hollow pipe of suit inside and outside adjacent two and for oxygen rifle 4 carries out the cool cycles aquaporin of cooling protection, cool cycles aquaporin connects with apparatus for supplying cool water;Oxygen rifle 4 is arranged on the roof of refining furnace 1 and can slide up and down along the roof of refining furnace 1。

Preferably, fuel gas is natural gas or coal gas。

The present invention, when cavity in refining furnace 1 is in vacuum state, by oxygen rifle 4 by the way of top-blown gas to winding-up fuel gas and oxygen-containing gas in refining furnace 1, fuel gas and oxygen-containing gas are lighted burning, copper smelting slag liquation in refining furnace 1 is carried out supplementary heating process by the combustion reaction liberated heat utilizing fuel gas and oxygen-containing gas, so heating, owing to oxidation operation all carries out in refining furnace 1 and completes, and also all carried out in refining furnace 1 by the combustion heating of oxygen rifle 4, heat supplier and heat need Fang Jun in refining furnace 1, therefore the heat produced can be transferred to this part copper metallurgical slag liquation carrying out oxidation operation in refining furnace 1 fully and directly, the heat amount produced significantly reduces compared to before improving, but this part copper metallurgical slag liquation for carrying out oxidation operation process in refining furnace 1 is enough, a small amount of and sufficient heat is adopted only this part copper metallurgical slag liquation carrying out oxidation operation accurately to be supplemented, the heat produced all is used in the place of needs, avoid the heating mode of original " broad irrigation ", inexcessive, do not waste, improve heat utilization ratio, decrease the consumption of combustible and oxygen-containing gas;Unnecessary heat can be delivered to refining furnace 1 along with the big cycle volume of copper smelting slag liquation flows in refining furnace 1, pass to the copper smelting slag liquation at all the other positions of container containing slag 5, copper smelting slag liquation in container containing slag 5 was carried out preheating insulation before entrance refining furnace 1 carries out oxidation operation, big cycle volume flowing heat transfer belongs to convection heat transfer' heat-transfer by convection in metallurgical thermodynamics, the heat transfer efficiency of convection heat transfer' heat-transfer by convection compared to radiant heat transfer want high many, therefore the present invention is except the relatively low heat transfer modes of this heat transfer efficiency of radiant heat transfer, also there is the heat transfer modes that this heat transfer efficiency of convection heat transfer' heat-transfer by convection is higher, thus considerably improving the heat transfer efficiency of mode of heating of the present invention;Owing to this part copper metallurgical slag liquation carrying out oxidation operation in refining furnace 1 is only directly heated insulation by the present invention, it should be apparent that, do not have the phenomenon that above-mentioned heating is uneven。To sum up, the mode of heating of the present invention ensure that the copper smelting slag liquation the carrying out removing impurities oxidation operation requirement to temperature, and what improve removing impurities oxidation operation carries out speed and performance level。

After entering the vacuum environment in refining furnace 1 doped with the copper smelting slag liquation driving gas, and when re-blowing extraneous oxygen-containing gas, copper smelting slag liquation in refining furnace 1 will not be circulate imperturbably, but violent splash, so, inevitably with regard in the copper smelting slag liquation splash of some to the inwall of refining furnace 1, owing to the temperature of refining furnace 1 upper space and upper inside wall is relatively low, the copper smelting slag liquation meeting cooled and solidified of liquid, in the course of time, just dross thing one layer hard is formed in the inner wall surface of refining furnace 1。Apparently, this cold conditions dross thing to removing impurities oxid-reclamatiom process and to service life of refining furnace 1 all without positive role, such as: owing to dross thing is contained within the elements such as higher lead, zinc, arsenic, antimony, bismuth, after removing impurities oxid-reclamatiom terminates, this dross thing can cause the copper smelting slag liquation having reached target component requirement to return lead, Hui Xin, return arsenic etc., causes plumbous in copper smelting slag liquation, zinc or arsenic element again to raise;Dross thing can corrode the refractory lining of refining furnace 1;Dross thing also can reduce the dischargeable capacity of refining furnace 1。For this, in the present embodiment, in removing impurities oxid-reclamatiom process, when the cavity in refining furnace 1 is in vacuum state, by oxygen rifle 4 by the way of top-blown gas to winding-up fuel gas and oxygen-containing gas in refining furnace 1, fuel gas and oxygen-containing gas are lighted burning, the combustion reaction liberated heat of fuel gas and oxygen-containing gas is utilized to be purged processing to the dross thing formed after splash copper smelting slag liquation cooling on refining furnace 1 inwall, the temperature improving refining furnace 1 internal upper part space and upper inside wall prevents the copper smelting slag liquation cooled and solidified of splash from forming dross thing, thus decreasing the generation of dross thing;The temperature improving refining furnace 1 internal upper part space and upper inside wall makes dross thing melted by heat again become liquid, inwall along refining furnace 1 flows downward, again it is back in the copper smelting slag liquation circulated, complete removing impurities oxid-reclamatiom process, thus decreasing the quantity of the dross thing generated, thus reducing a series of negative influences that above-mentioned dross thing brings。

At present, no matter in removing impurities oxid-reclamatiom process, how to optimize refinery practice, after removing impurities oxid-reclamatiom terminates, still can remaining a certain amount of dross thing on refining furnace 1 inwall。Currently for this dross thing, it is typically employed in blowing out gap, mechanically removes, for instance use chisel to cut, use spatula to root out etc.。There is several drawback in mechanical removal mode: 1. owing to dross thing or dross nitride layer hardness are significantly high, and mechanical removal mode is difficult to remove totally;2. mechanical removal mode is easy to refining furnace 1 inwall is caused damage, and causing must follow-up repairing furnace wall;3. mechanical removal mode, wastes time and energy so that the off time between adjacent two heats is longer, so that the removing impurities oxid-reclamatiom cycle is longer, has had a strong impact on rhythm of production and production efficiency。For this, in one embodiment of the invention, when the cavity in refining furnace 1 is in atmospheric pressure state, by oxygen rifle 4 by the way of top-blown gas to winding-up fuel gas and oxygen-containing gas in refining furnace 1, fuel gas and oxygen-containing gas are lighted burning, utilize the combustion reaction liberated heat of fuel gas and oxygen-containing gas that the dross thing formed after splash copper smelting slag liquation cooling on refining furnace 1 inwall is carried out fusing removing to process, utilize the combustion reaction liberated heat of fuel gas and oxygen-containing gas that refining furnace 1 is carried out baker process;Oxygen rifle 4 is the multilamellar internal and external casing structure of the hollow pipe including multiple inside and outside suit, oxygen rifle 4 includes that the cavity between the tube wall by the hollow pipe being set with inside and outside the cavity in hollow pipe or adjacent two is formed and for transporting combustible gases fuel gas passage, and fuel gas passage connects with the compressed air source unit of fuel gas;Oxygen rifle 4 also include by inside and outside the cavity in hollow pipe or adjacent two suit hollow pipe tube wall between cavity formed and for carrying the oxygen-containing gas passage of oxygen-containing gas, oxygen-containing gas passage connects with the compressed air source unit of oxygen-containing gas;That oxygen rifle 4 also includes being formed by cavity between the tube wall of the hollow pipe of suit inside and outside adjacent two and for oxygen rifle 4 carries out the cool cycles aquaporin of cooling protection, cool cycles aquaporin connects with apparatus for supplying cool water;Oxygen rifle 4 is arranged on the roof of refining furnace 1 and can slide up and down along the roof of refining furnace 1。

The present invention is when the cavity in refining furnace 1 is in atmospheric pressure state, by oxygen rifle 4 by the way of top-blown gas to winding-up fuel gas and oxygen-containing gas in refining furnace 1, fuel gas and oxygen-containing gas are lighted burning, utilize the combustion reaction liberated heat of fuel gas and oxygen-containing gas that the dross thing formed after splash copper smelting slag liquation cooling on refining furnace 1 inwall is carried out fusing removing to process, the temperature improved in refining furnace 1 upper space makes dross thing melted by heat again become liquid, inwall along refining furnace 1 flows downward, final outflow refining furnace 1;It is arranged on the roof of refining furnace 1 due to oxygen rifle 4 and can slide up and down along the roof of refining furnace 1, after having made to remove the dross thing at a certain position, other position in refining furnace 1 ascending motion or descending motion can be carried out fusing removing and processes by oxygen rifle 4, the fusing of dross thing on whole refining furnace 1 inwall is removed by final realization, thus reducing a series of negative influences that above-mentioned mechanical removal mode is brought。

In order to be further appreciated by the present invention, below in conjunction with embodiment, a kind of method reclaiming lead, zinc, arsenic, antimony, bismuth and stannum from high impurity copper metallurgical slag provided by the invention being described in detail, protection scope of the present invention is not limited by the following examples。

Embodiment 1

With the hot molten slag of a step copper smelter discharge for processing object, temperature is within the scope of 1250 DEG C, and this copper smelting slag liquation includes following components in percentage by weight: the copper of 3%, the lead of 0.36%, 3.88% zinc, 0.89% arsenic, 0.039% antimony, 0.051% bismuth, 0.02% stannum。Comprise the following steps:

1) melted copper smelting slag liquation is joined in container containing slag 5;Then the upper liquid level certain depth below being immersed in container containing slag 5 by feed tube 2 and drain pipe 3 copper smelting slag liquation, being then turned on vacuum pump by the cavity vacuum state in refining furnace 1, now the cavity passage along feed tube 2 and drain pipe 3 of the copper smelting slag liquation in container containing slag 5 rises in the cavity flowing into refining furnace 1;

2) jet in the copper smelting slag liquation in feed tube 2 driving gas with pressure, between container containing slag 5, feed tube 2, refining furnace 1 and drain pipe 3, form circulating of copper smelting slag liquation;Meanwhile, in refining furnace 1, blow oxygen-containing gas to the copper smelting slag liquation in refining furnace 1;Controlling vacuum residual voltage is 100Pa~300Pa;The blowing volume controlling oxygen is 10m3/ t slag, the copper smelting slag liquation after oxidation includes bloodstone, cupric oxide ore and quartz mine;

3) step 2) carry out a period of time after, the component of the copper smelting slag liquation after sample examination removing impurities and oxidation and content, if lead content is less than 0.01%, and arsenic content is less than 0.05%, result of laboratory test reaches target design requirement, removing impurities oxidation processes terminates, and recording whole process time is 30min;Removing impurities oxidation processes terminate to obtain removing impurities and oxidation after copper smelting slag liquation, the oxide mixture of impurity element of condensed state and the flue gas discharged by vacuum pump;Gained removing impurities and oxidation after copper smelting slag liquation include following components in percentage by weight: the lead of 0.0033%, the zinc of 0.0019%, 0.009% arsenic, 0.01% antimony, 0.0042% bismuth, 0.0019% stannum;Corresponding removal efficiency is respectively as follows: lead: 99.08%, zinc: 99.95%, arsenic: 98.99%, antimony: 74.36%, bismuth: 91.76%, stannum: 90.5%;

4) then, with cinder ladle car, above-mentioned container containing slag 5 is transported to slag slow cooling field, by the copper smelting slag liquation elder generation natural cooling after removing impurities and oxidation 24 hours, adds water spraying cooling 36 hours。Slag in container containing slag 5 is poured out after terminating by above-mentioned slow cooling process, sends into ore grinding-ore-sorting system with after crusher in crushing by belt。Slag becomes fineness ore pulp within the scope of 85 order~325 orders through grinding ore grinding。

The copper smelting slag processed through slow cooling is introduced into ferrum floatation system: ore pulp is introduced into medicament agitator tank, the terpenic oil of the oxidized paraffin wax soap and 200g/t slag that add 600g/t slag in medicament agitator tank mixes with ore pulp, carry out flotation subsequently into flotation device, obtain most of bloodstone iron ore concentrate and flotation tailing that grade is 65%。The ore pulp of flotation tailing enters strong magnetic separator and carries out magnetic separation, obtains remaining bloodstone iron ore concentrate and magnetic tailing that grade is 65%。

The iron ore concentrate that flotation and magnetic separation obtain is filtered after merging, and obtains final iron ore concentrate;The mine tailing that magnetic separation obtains enters copper agitator tank and leaches, and controls to leach the concentration 60g/L of sulphuric acid in ore pulp, obtains leachate and leaching slag。

Leaching slag sequentially passes through concentrator washing and filter filters, and obtains SiO2Content is the siliceous product of 85%。

Leachate extracts through the extractant that model is Lix984N, obtain copper-bath, then copper-bath is sent into Winning cell and carries out electrodeposition, electrodeposition condition includes: tank voltage is 2V~3V, it is 100mm with die opening, bath temperature is 45 DEG C~55 DEG C, and electric current density is 200A~350A, obtains the electro deposited copper of cupric 98%。

Embodiment 2

With the hot molten slag of a step copper smelter discharge for processing object, temperature is within the scope of 1240 DEG C。This copper smelting slag liquation includes following components in percentage by weight: the copper of 10%, the lead of 0.24%, 2.83% zinc, 0.63% arsenic, 0.032% antimony, 0.028% bismuth, 0.02% stannum。Comprise the following steps:

1) melted copper smelting slag liquation is joined in container containing slag 5;Then the upper liquid level certain depth below being immersed in container containing slag 5 by feed tube 2 and drain pipe 3 copper smelting slag liquation, being then turned on vacuum pump by the cavity vacuum state in refining furnace 1, now the cavity passage along feed tube 2 and drain pipe 3 of the copper smelting slag liquation in container containing slag 5 rises in the cavity flowing into refining furnace 1;

2) jet in the copper smelting slag liquation in feed tube 2 driving gas with pressure, between container containing slag 5, feed tube 2, refining furnace 1 and drain pipe 3, form circulating of copper smelting slag liquation;Meanwhile, in refining furnace 1, blow oxygen-containing gas to the copper smelting slag liquation in refining furnace 1;Controlling vacuum residual voltage is 100Pa~300Pa;The blowing volume controlling oxygen is 10m3/ t slag, the copper smelting slag liquation after oxidation includes bloodstone, cupric oxide ore and quartz mine;

3) step 2) carry out a period of time after, the component of the copper smelting slag liquation after sample examination removing impurities and oxidation and content, if lead content is less than 0.01%, and arsenic content is less than 0.05%, result of laboratory test reaches target design requirement, removing impurities oxidation processes terminates, and recording whole process time is 35min;Removing impurities oxidation processes terminate to obtain removing impurities and oxidation after copper smelting slag liquation, the oxide mixture of impurity element of condensed state and the flue gas discharged by vacuum pump;Gained removing impurities and oxidation after copper smelting slag liquation include following components in percentage by weight: the lead of 0.0028%, the zinc of 0.0023%, 0.008% arsenic, 0.009% antimony, 0.0039% bismuth, 0.0015% stannum;Corresponding removal efficiency is respectively as follows: lead: 98.83%, zinc: 99.92%, arsenic: 98.73%, antimony: 71.88%, bismuth: 86.07%, stannum: 92.5%;

4) then, with cinder ladle car, above-mentioned container containing slag 5 is transported to slag slow cooling field, by the copper smelting slag liquation elder generation natural cooling after removing impurities and oxidation 24 hours, adds water spraying cooling 36 hours。Slag in container containing slag 5 is poured out after terminating by above-mentioned slow cooling process, sends into ore grinding-ore-sorting system with after crusher in crushing by belt。Slag becomes fineness ore pulp within the scope of 85 order~325 orders through grinding ore grinding。

The copper smelting slag processed through slow cooling is introduced into ferrum floatation system: ore pulp is introduced into medicament agitator tank, the terpenic oil of the oxidized paraffin wax soap and 200g/t slag that add 600g/t slag in medicament agitator tank mixes with ore pulp, carry out flotation subsequently into flotation device, obtain most of bloodstone iron ore concentrate and flotation tailing that grade is 65%。The ore pulp of flotation tailing enters strong magnetic separator and carries out magnetic separation, obtains remaining bloodstone iron ore concentrate and magnetic tailing that grade is 65%。

The iron ore concentrate that flotation and magnetic separation obtain is filtered after merging, and obtains final iron ore concentrate;The mine tailing that magnetic separation obtains enters copper agitator tank and leaches, and controls to leach the concentration 60g/L of sulphuric acid in ore pulp, obtains leachate and leaching slag。

Leaching slag sequentially passes through concentrator washing and filter filters, and obtains SiO2Content is the siliceous product of 85%。

Leachate extracts through the extractant that model is Lix984N, obtain copper-bath, then copper-bath is sent into Winning cell and carries out electrodeposition, electrodeposition condition includes: tank voltage is 2V~3V, it is 100mm with die opening, bath temperature is 45 DEG C~55 DEG C, and electric current density is 200A~350A, obtains the electro deposited copper of cupric 98%。

The present invention is directed to and want to solve the technical problem that, provide multiple laddering technical scheme, multiple laddering technical schemes are mutually combined superposition, cooperate, mutually promote, forming an overall plan, the technique effect of acquirement is much better than the technique effect of an any of the above described technical scheme, and synergistic effect is notable。

The method and apparatus of the not detailed description of the present invention is prior art, repeats no more。

In this specification, each embodiment adopts the mode gone forward one by one to describe, and what each embodiment stressed is the difference with other embodiments, between each embodiment same or similar part mutually referring to。

The explanation of above example is only intended to help to understand method and the core concept thereof of the present invention。It should be pointed out that, for those skilled in the art, under the premise without departing from the principles of the invention, it is also possible to the present invention carries out some improvement and modification, these improve and modify in the protection domain also falling into the claims in the present invention。

Described above to the disclosed embodiments, makes professional and technical personnel in the field be capable of or uses the present invention。Multiple amendment for these embodiments is apparent from for those skilled in the art, and generic principles defined herein can without departing from the spirit or scope of the present invention, realize in other embodiments。Therefore, the present invention is not intended to be limited to the embodiments shown herein, and is to fit to the widest range consistent with principles disclosed herein and features of novelty。

Claims (6)

1. the method reclaiming lead, zinc, arsenic, antimony, bismuth and stannum from high impurity copper metallurgical slag, it is characterised in that comprise the following steps:
1) melted copper smelting slag liquation is joined in the container containing slag for containing copper smelting slag liquation;Then the upper liquid level certain depth below being immersed in described container containing slag by the feed tube being arranged on refining furnace diapire and drain pipe copper smelting slag liquation, being then turned on the vacuum pump that connects with described refining furnace by the cavity vacuum state in described refining furnace, now in refining furnace, under the effect of atm difference between vacuum residual voltage and external atmosphere pressure, the cavity passage along described feed tube and described drain pipe of the copper smelting slag liquation in described container containing slag rises in the cavity flowing into described refining furnace;
The profile of described refining furnace is vertical type columnar, and inner hollow forms cavity, and described refining furnace includes steel shell and builds the refractory lining at described steel shell inner surface by laying bricks or stones, and the top of described refining furnace is provided with the gas outlet for being connected with described vacuum pump;
Described feed tube and described drain pipe all include steel-made inner shell, be arranged on the refractory lining of the inner surface of described steel-made inner shell and be arranged on the refractory material outer lining of outer surface of described steel-made inner shell;
Described feed tube and described drain pipe are fixedly installed on the diapire of described refining furnace and are tightly connected with the diapire of described refining furnace, cavity in described refining furnace is interconnected with the cavity passage in described feed tube, cavity in described refining furnace is interconnected with the cavity passage in described drain pipe, and the device that all and described refining furnace is connected all carries out encapsulation process to prevent from destroying the vacuum state in described refining furnace at the position being connected with described refining furnace;
2) jet in the copper smelting slag liquation in described feed tube driving gas with pressure, then under the drive of atm difference and driving gas, the copper smelting slag liquation in described container containing slag is constantly risen in the described refining furnace of inflow by described feed tube, then the copper smelting slag liquation in described refining furnace is constantly flowed out by described refining furnace again through described drain pipe and is back in described container containing slag, forms circulating of copper smelting slag liquation between described container containing slag, feed tube, refining furnace and drain pipe;
Meanwhile, in described refining furnace, blow oxygen-containing gas to the copper smelting slag liquation in described refining furnace;
Utilize the oxygen element in oxygen-containing gas that impurity element included in the copper smelting slag liquation in described refining furnace is oxidized to the oxide of corresponding impurity element, the oxide of the impurity element that oxidation is formed becomes the volatilization elimination of gaseous oxygen compound under vacuum conditions, it is achieved the process of impurity element in elimination copper smelting slag;
Then it is mixed with the gas of the oxide of the impurity element of gaseous state to enter the condenser that connects with described refining furnace and be condensed, obtains the oxide mixture of the impurity element of condensed condensed state, it is achieved the process of impurity element in recovery copper smelting slag;
Described impurity element include in lead, zinc, arsenic, antimony, bismuth and tin element one or more or all;
Copper smelting slag liquation is aoxidized by the Oxidation utilizing the oxygen element in oxygen-containing gas so that the copper smelting slag liquation after oxidation includes bloodstone, cupric oxide ore and quartz mine, it is achieved the process aoxidized by copper smelting slag;
3) described step 2) carry out a period of time after, the component of the copper smelting slag liquation after sample examination removing impurities and oxidation and content, if result of laboratory test reaches target design requirement, then first abolish the vacuum state in described refining furnace, then the feed tube being arranged on described refining furnace diapire and drain pipe being departed from the copper smelting slag liquation in described container containing slag, removing impurities oxidation processes terminates;If result of laboratory test miss the mark designing requirement, continue removing impurities oxidation processes, until result of laboratory test reaches target design requirement;
Removing impurities oxidation processes terminate to obtain removing impurities and oxidation after copper smelting slag liquation, the oxide mixture of impurity element of condensed state and the flue gas discharged by described vacuum pump;
4) by step 3) copper smelting slag liquation after the removing impurities that obtains and oxidation first passes around slow cooling and processes, then the copper smelting slag processed through slow cooling is first carried out flotation, obtain major part bloodstone and flotation tailing, then described flotation tailing is carried out magnetic separation, obtain remaining bloodstone and magnetic tailing, again described magnetic tailing is leached, obtain containing copper products and leached mud, finally described leached mud is sequentially carried out washing and filters, obtain siliceous product, it is achieved reclaim the process of ferrum, copper and element silicon in copper smelting slag。
2. method according to claim 1, it is characterized in that, described step 2) in, by described oxygen-containing gas below the upper liquid level blowing the copper smelting slag liquation to described refining furnace in the way of submergence blows, the gas outlet spraying described oxygen-containing gas is positioned at below the upper liquid level of copper smelting slag liquation of described refining furnace。
3. method according to claim 1 and 2, it is characterized in that, described step 2) in, by oxygen rifle in the copper smelting slag liquation blowed by described oxygen-containing gas in the way of top-blown gas to described refining furnace, the gas outlet of described oxygen rifle is positioned at more than the upper liquid level of the copper smelting slag liquation of described refining furnace and with the upper liquid level of copper smelting slag liquation in a distance;
Described oxygen rifle is the multilamellar internal and external casing structure of the hollow pipe including multiple inside and outside suit, described oxygen rifle include by inside and outside the cavity in hollow pipe or adjacent two suit hollow pipe tube wall between cavity formed and for carrying the oxygen-containing gas passage of described oxygen-containing gas, described oxygen-containing gas passage connects with the compressed air source unit of described oxygen-containing gas;
That described oxygen rifle also includes being formed by cavity between the tube wall of the hollow pipe of suit inside and outside adjacent two and for described oxygen rifle carries out the cool cycles aquaporin of cooling protection, described cool cycles aquaporin connects with apparatus for supplying cool water;
Described oxygen rifle also includes for improving described oxygen-containing gas spouting velocity and controlling the shower nozzle of described oxygen-containing gas injection direction, and described shower nozzle is arranged on the bottom of described oxygen rifle, and the gas outlet of described oxygen rifle is arranged on described shower nozzle;
Described oxygen rifle is arranged on the roof of described refining furnace and can slide up and down along the roof of described refining furnace。
4. method according to claim 1, it is characterized in that, described step 2) in, when the cavity in described refining furnace is in vacuum state, by oxygen rifle by the way of top-blown gas to winding-up fuel gas and oxygen-containing gas in described refining furnace, described fuel gas and described oxygen-containing gas are lighted burning, copper smelting slag liquation in described refining furnace is carried out supplementary heating process by the combustion reaction liberated heat utilizing described fuel gas and described oxygen-containing gas, the combustion reaction liberated heat of described fuel gas and described oxygen-containing gas is utilized to be purged processing to the dross thing formed after splash copper smelting slag liquation cooling on described refining furnace inwall;
The gas outlet of described oxygen rifle is positioned at more than the upper liquid level of the copper smelting slag liquation of described refining furnace and with the upper liquid level of copper smelting slag liquation in a distance;
Described oxygen rifle is the multilamellar internal and external casing structure of the hollow pipe including multiple inside and outside suit, described oxygen rifle include by inside and outside the cavity in hollow pipe or adjacent two suit hollow pipe tube wall between cavity formed and for carrying the fuel gas passage of described fuel gas, described fuel gas passage connects with the compressed air source unit of described fuel gas;
Described oxygen rifle also include by inside and outside the cavity in hollow pipe or adjacent two suit hollow pipe tube wall between cavity formed and for carrying the oxygen-containing gas passage of described oxygen-containing gas, described oxygen-containing gas passage connects with the compressed air source unit of described oxygen-containing gas;
That described oxygen rifle also includes being formed by cavity between the tube wall of the hollow pipe of suit inside and outside adjacent two and for described oxygen rifle carries out the cool cycles aquaporin of cooling protection, described cool cycles aquaporin connects with apparatus for supplying cool water;
Described oxygen rifle is arranged on the roof of described refining furnace and can slide up and down along the roof of described refining furnace。
5. method according to claim 1, it is characterized in that, when the cavity in described refining furnace is in atmospheric pressure state, by oxygen rifle by the way of top-blown gas to winding-up fuel gas and oxygen-containing gas in described refining furnace, described fuel gas and described oxygen-containing gas are lighted burning, utilize the combustion reaction liberated heat of described fuel gas and described oxygen-containing gas that the dross thing formed after splash copper smelting slag liquation cooling on described refining furnace inwall is carried out fusing removing to process, described refining furnace is carried out baker process by the combustion reaction liberated heat utilizing described fuel gas and described oxygen-containing gas;
Described oxygen rifle is the multilamellar internal and external casing structure of the hollow pipe including multiple inside and outside suit, described oxygen rifle include by inside and outside the cavity in hollow pipe or adjacent two suit hollow pipe tube wall between cavity formed and for carrying the fuel gas passage of described fuel gas, described fuel gas passage connects with the compressed air source unit of described fuel gas;
Described oxygen rifle also include by inside and outside the cavity in hollow pipe or adjacent two suit hollow pipe tube wall between cavity formed and for carrying the oxygen-containing gas passage of described oxygen-containing gas, described oxygen-containing gas passage connects with the compressed air source unit of described oxygen-containing gas;
That described oxygen rifle also includes being formed by cavity between the tube wall of the hollow pipe of suit inside and outside adjacent two and for described oxygen rifle carries out the cool cycles aquaporin of cooling protection, described cool cycles aquaporin connects with apparatus for supplying cool water;
Described oxygen rifle is arranged on the roof of described refining furnace and can slide up and down along the roof of described refining furnace。
6. method according to claim 1, it is characterised in that described step 1) in, the copper grade of described copper smelting slag liquation is more than 3%。
CN201610085047.1A 2016-02-14 2016-02-14 Method for recycling lead, zinc, arsenic, antimony, bismuth and tin from high-purity copper smelting slag CN105695749A (en)

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