CN105671325A - Dilution treatment method for copper smelting slag - Google Patents

Dilution treatment method for copper smelting slag Download PDF

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Publication number
CN105671325A
CN105671325A CN201610144794.8A CN201610144794A CN105671325A CN 105671325 A CN105671325 A CN 105671325A CN 201610144794 A CN201610144794 A CN 201610144794A CN 105671325 A CN105671325 A CN 105671325A
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China
Prior art keywords
copper smelting
smelting slag
slag
copper
dilution
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Pending
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CN201610144794.8A
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Chinese (zh)
Inventor
张廷安
牛丽萍
刘燕
豆志河
张保敬
吕国志
赵秋月
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Northeastern University China
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Northeastern University China
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Priority to CN201610144794.8A priority Critical patent/CN105671325A/en
Publication of CN105671325A publication Critical patent/CN105671325A/en
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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
    • C22B7/04—Working-up slag
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B15/00—Obtaining copper
    • C22B15/0026—Pyrometallurgy
    • C22B15/0054—Slag, slime, speiss, or dross treating
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
    • C22B7/001—Dry processes
    • C22B7/002—Dry processes by treating with halogens, sulfur or compounds thereof; by carburising, by treating with hydrogen (hydriding)
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P10/00—Technologies related to metal processing
    • Y02P10/20—Recycling

Abstract

The invention provides a dilution treatment method for copper smelting slag. The dilution treatment method includes the technological steps that firstly, a mechanical stirring device is introduced into a dilution furnace, the high-temperature molten state copper smelting slag at the temperature ranging from 1150 DEG C to 1350 DEG C is guided into the dilution furnace, a stirring paddle is adjusted to stretch to the part from the 1/3 position of the liquid level of the copper smelting slag to the 1/2 position of the liquid level of the copper smelting slag, heating and stirring are started, the temperature of the copper smelting slag is controlled to range from 1200 DEG C to 1350 DEG C, the stirring speed ranges from 50 r/min to 200 r/min, and a vortex with the diameter height ratio ranging from 0.5 to 3 is formed; secondly, a vulcanizing agent is carried through carrier gas and injected to the position, close to the center of the vortex, of the surface of a copper smelting slag pool through a nozzle above the liquid level of the high-temperature molten state copper smelting slag, the adding amount of the vulcanizing agent is 0.3-8% of the mass of the copper smelting slag, and heat-preservation stirring is conducted for 10-60 min; and thirdly, standing layering is conducted, and copper matte on the lower layer and diluted slag on the upper layer are collected. The copper content of the diluted slag obtained after treatment is below 0.3%.

Description

The dilution treatment process of a kind of copper smelting slag
Technical field
The invention belongs to metallurgical technology field, it is specifically related to the dilution treatment process of a kind of copper smelting slag.
Background technology
Various copper making technology differs from one another, never with aspect with meet modern copper metallurgy industry in various degree to the ability of Energy efficiency, environment protection and process complicated ore and synthetical recovery level. Along with the development of Copper making technology, the taste of smelting intensity, copper matte regulus improves constantly, and melting once Copper in Slag also improves constantly, and in smelting process, output abandons Copper in Slag up to 0.4%-0.8%, oxygen-enriched bottom-blowing Copper in Slag sometimes up to 3-4%, far above the copper mining grade of current 0.3%.
The method of industrial copper smelting slag dilution has two classes: slow cooling ore dressing method and pyrometallurgical smelting method. First slow cooling ore dressing method copper smelting slag carries out slow cooling process after slagging tap, in promotion copper ashes, copper mineral crystal grain grows up, copper ashes finally obtains copper ore concentrates through the process of ore dressing method, the widespread use in copper metallurgy industry Slag treatment of ore dressing method, but the requirement height for the treatment of processes slag slow cooling cycle length, awkward silence at a meeting floor space that cinder ladle quantity is eased up, and slag cooling can cause huge energy dissipation, it is necessary to great Liang Shui, its environmental benefit is also lower.
Pyrometallurgical smelting method thermal slag direct electric heating dilution is carried out sedimentation be separated with slag sulfonium, it is possible to the copper content in copper smelting slag is reduced to slag-sulfonium balance level, and electric furnace waste only can reach 0.8-1.2% level, controls preferably about 0.6%. But vulcanizing agent is generally directly add in dilution furnace roof portion in fire method dilution process, and vulcanizing agent floats on slag surface, contacting with copper smelting slag insufficient and volatilize serious, utilization ratio is lower, and easily pollutes environment.
Application number be 200910088879.9 patent propose a kind of electrothermal impoverishment process for copper smelting slag, vulcanizing agent and copper weld pool slag is added in electric heating dilution stove, the temperature of copper weld pool slag is improved by electrifying electrodes, spray into oxygen to dilution furnace bottom simultaneously, and/or CO (carbon monoxide converter) gas and nitrogen mixture improve the rate of recovery and the resource utilization of copper, but this patent does not consider fully mixing and reaction problem of vulcanizing agent and copper weld pool slag, vulcanizing agent utilising efficiency is low, and owing to adding of oxygen has a large amount of sulfur dioxide gas to generate in treating processes, environmental pollution is more serious.
Therefore, need a kind of new copper smelting slag dilution treatment process badly, it is possible to abundant solution vulcanizing agent mixes problem with copper smelting slag, other material of the least possible introducing or generation waste gas, and can effectively reduce the copper content in tailings, and improve on-the-spot environment.
Summary of the invention
For prior art Problems existing, the present invention proposes the dilution treatment process of a kind of copper smelting slag, whipping device introduced by melting copper smelting slag dilution stove, stirring rake is stretched into the 1/3 to 1/2 of copper smelting slag liquid level sentence in be formed centrally the centrifugal vortex that blade diameter length ratio is 0.5 ~ 3, then vulcanizing agent is carried winding-up to copper smelting slag weld pool surface by whirlpool center by carrier gas, in vulcanizing agent and copper smelting slag, Red copper oxide reaction forms matte, simultaneously Fe in slag3O4Being reduced, viscosity coefficient of dross reduces, and slag fluidity improves, matte in slag is mutually fast bottom flocking settling to molten bath, achieving the high efficiency separation of matte and slag, reach the object of copper smelting slag dilution, after dilution, in copper smelting slag, copper content can be down to less than 0.3%. It is as follows that the present invention proposes technical scheme:
A dilution treatment process for copper smelting slag, carries out according to following processing step:
(1) in dilution stove, mechanical stirring equipment is introduced, the high-temperature molten-state copper smelting slags of 1150 ~ 1350 DEG C are imported in dilution stove, adjustment stirring rake stretches to 1/3 to 1/2 place of copper smelting slag liquid level, open heating and stir, the temperature of control copper smelting slag is 1200 ~ 1350 DEG C, stirring velocity is 50 ~ 200r/min, and forming blade diameter length ratio is the whirlpool of 0.5 ~ 3;
(2) vulcanizing agent being carried winding-up to copper smelting slag weld pool surface by whirlpool center by the nozzle of high-temperature molten-state copper smelting slag ullage by carrier gas, vulcanizing agent add-on is the 0.3 ~ 8% of copper smelting slag quality, insulated and stirred 10 ~ 60min;
(3) stratification, collects slag after lower floor's matte and upper strata dilution respectively.
In aforesaid method, described vulcanizing agent comprises copper ore concentrates or pyrite.
In aforesaid method, described carrier gas comprises rare gas element or nitrogen.
In aforesaid method, the grade of described lower floor matte more than 70%, after the dilution of upper strata in slag copper content below 0.3%.
In aforesaid method, the high-temperature flue gas that copper smelting slag produces in dilution process passes through boiler recovery waste heat and cyclone dust removal, zinc in recovered flue gas, lead, molybdenum and arsenic easily volatilize valuable component, remove sulfur dioxide gas contained in flue gas finally by washing device, after reaching emptying requirement, enter air.
The vulcanizing agent of the present invention adds in copper smelting slag melt, and pyrolytic decomposition produces FeS, FeS and Cu2O reaction generates Cu2S forms matte, FeS and Fe3O4And SiO2Reaction generates 2FeO SiO2, make Fe in slag3O4Content reduces, and the utilization ratio of this process vulcanizing agent can reach more than 80%, and after dilution, in slag, copper content is down to less than 0.3%. The reaction equation that the present invention relates to is as follows:
Cu2O+FeS=Cu2S+FeO
2FeO+SiO2=2FeO?SiO2
3Fe3O4+FeS+5SiO2=5(2FeO?SiO2)+SO2
Compared with existing copper smelting slag dilution technology, feature and the useful effect of the present invention are as follows:
1, the present invention introduces mechanical stirring equipment and nozzle at dilution stove, control mixing speed forms the whirlpool that blade diameter length ratio is 0.5 ~ 3 in high-temperature molten-state copper smelting slag, vulcanizing agent is made to carry winding-up to copper smelting slag weld pool surface by whirlpool center by nozzle by carrier gas, what utilize that eddy effect solves vulcanizing agent and copper smelting slag mixes problem, improve vulcanizing agent and the dynamic conditions of copper smelting slag solid-liquid reaction, while reducing vulcanizing agent consumption, improve its utilization ratio.
2, the present invention introduces other material at the least possible and produce on the basis of waste gas, utilize the mode stirring and carrying with vulcanizing agent carrier gas by stirring the winding-up of whirlpool center, effectively reduce the copper content in copper smelting slag, and decrease environmental pollution, compared with the copper content of existing copper metallurgical slag treatment process is between 0.4 ~ 0.8, the copper smelting slag copper content of the present invention's process can be down to less than 0.3%.
Accompanying drawing illustrates:
Fig. 1 is the structural representation of the dilution stove that the dilution treatment process of the copper smelting slag of the embodiment of the present invention adopts, wherein: 1-slag-drip opening, 2-arranges matte mouth, 3-stirring rake, 4-stirring rake lifting system, 5-copper smelting slag chute, 6-vulcanizing agent injection system, 7-cyclone system, 8-residual neat recovering system, 9-washing tower.
Embodiment
The dilution stove adopted in the embodiment of the present invention is home-built equipment.
In the embodiment of the present invention 1 and 2, copper smelting slag used is oxygen-enriched bottom-blowing copper weld pool slag, and concrete composition is as shown in table 1;
The copper smelting slag multielement analysis result (massfraction, %) that table 1 embodiment 1 and 2 adopts
Component TFe FeO Cu Zn S Al2O3 CaO MgO SiO2 Au g/t As
Content 42.47 43.14 4.51 5.67 1.55 3.02 0.96 1.09 20.82 1.2 0.075
In the embodiment of the present invention 3 and 4, copper smelting slag used is oxygen-enriched bottom-blowing copper weld pool slag, and concrete composition is as shown in table 2;
The copper smelting slag multielement analysis result (massfraction, %) that table 2 embodiment 3 and 4 adopts
Component TFe FeO Cu Zn S Al2O3 CaO MgO SiO2 As
Content 45.50 45.99 2.36 1.67 0.86 3.35 0.74 0.74 27.54 0.018
Embodiment 1
The molten state Copper making quantity of slag is 20t, forms as shown in table 1, and as shown in Figure 1, dilution treatment process carries out the dilution stove of employing according to following processing step:
(1) in dilution stove, mechanical stirring equipment is introduced, the high-temperature molten-state copper smelting slags of 1150 ~ 1350 DEG C are imported, adjustment stirring rake stretches to 1/3 place of copper smelting slag liquid level, open heating and stir, the temperature of control copper smelting slag is 1250 DEG C, stirring velocity is 50r/min, and forming blade diameter length ratio is the whirlpool of 3;
(2) 600kg copper ore concentrates, 400kg calcium oxide by nitrogen, are carried winding-up by the nozzle of high-temperature molten-state copper smelting slag ullage and lean on whirlpool center to copper smelting slag weld pool surface, insulated and stirred 40min;
(3) stratification, collects slag after lower floor's matte and upper strata dilution respectively, and wherein after dilution, Copper in Slag amount is 0.26%, discard slag with copper % (Cu) 74.
The high-temperature flue gas that copper smelting slag produces in dilution process passes through boiler recovery waste heat and cyclone dust removal, zinc in recovered flue gas, lead, molybdenum and arsenic easily volatilize valuable component, remove sulfur dioxide gas contained in flue gas finally by washing device, after reaching emptying requirement, enter air.
Embodiment 2
The molten state Copper making quantity of slag is 22t, forms as shown in table 1, and as shown in Figure 1, dilution treatment process carries out the dilution stove of employing according to following processing step:
(1) in dilution stove, mechanical stirring equipment is introduced, the high-temperature molten-state copper smelting slags of 1150 ~ 1350 DEG C are imported, adjustment stirring rake stretches to 1/2 place of copper smelting slag liquid level, open heating and stir, the temperature of control copper smelting slag is 1280 DEG C, stirring velocity is 200r/min, and forming blade diameter length ratio is the whirlpool of 0.5;
(2) 660kg pyrite, 440kg calcium oxide by argon gas, are carried winding-up by the nozzle of high-temperature molten-state copper smelting slag ullage and lean on whirlpool center to copper smelting slag weld pool surface, insulated and stirred 60min;
(3) stratification, collects slag after lower floor's matte and upper strata dilution respectively, and wherein after dilution, Copper in Slag amount is 0.28%, discard slag with copper % (Cu) 72.
The high-temperature flue gas that copper smelting slag produces in dilution process passes through boiler recovery waste heat and cyclone dust removal, zinc in recovered flue gas, lead, molybdenum and arsenic easily volatilize valuable component, remove sulfur dioxide gas contained in flue gas finally by washing device, after reaching emptying requirement, enter air.
Embodiment 3
The molten state Copper making quantity of slag is 1t, forms as shown in table 2, and as shown in Figure 1, dilution treatment process carries out the dilution stove of employing according to following processing step:
(1) in dilution stove, mechanical stirring equipment is introduced, the high-temperature molten-state copper smelting slags of 1150 ~ 1350 DEG C are imported, adjustment stirring rake stretches to 1/2 place of copper smelting slag liquid level, open heating and stir, the temperature of control copper smelting slag is 1260 DEG C, stirring velocity is 80r/min, and forming blade diameter length ratio is the whirlpool of 2;
(2) 17kg pyrite and 15kg calcium oxide are carried winding-up by the nozzle of high-temperature molten-state copper smelting slag ullage by nitrogen and lean on whirlpool center to copper smelting slag weld pool surface, insulated and stirred 30min;
(3) stratification, collects slag after lower floor's matte and upper strata dilution respectively, and wherein after dilution, Copper in Slag amount is 0.29%, discard slag with copper % (Cu) 76.
The high-temperature flue gas that copper smelting slag produces in dilution process passes through boiler recovery waste heat and cyclone dust removal, zinc in recovered flue gas, lead, molybdenum and arsenic easily volatilize valuable component, remove sulfur dioxide gas contained in flue gas finally by washing device, after reaching emptying requirement, enter air.
Embodiment 4
The molten state Copper making quantity of slag is 1t, forms as shown in table 2, and as shown in Figure 1, dilution treatment process carries out the dilution stove of employing according to following processing step:
(1) in dilution stove, mechanical stirring equipment is introduced, the high-temperature molten-state copper smelting slags of 1150 ~ 1350 DEG C are imported, adjustment stirring rake stretches to 1/3 place of copper smelting slag liquid level, open heating and stir, the temperature of control copper smelting slag is 1280 DEG C, stirring velocity is 90r/min, and forming blade diameter length ratio is the whirlpool of 1;
(2) 25kg copper ore concentrates, 20kg calcium oxide by nitrogen, are carried winding-up by the nozzle of high-temperature molten-state copper smelting slag ullage and lean on whirlpool center to copper smelting slag weld pool surface, insulated and stirred 30min;
(3) stratification, collects slag after lower floor's matte and upper strata dilution respectively, and wherein after dilution, Copper in Slag amount is 0.28%, discard slag with copper % (Cu) 70.
The high-temperature flue gas that copper smelting slag produces in dilution process passes through boiler recovery waste heat and cyclone dust removal, zinc in recovered flue gas, lead, molybdenum and arsenic easily volatilize valuable component, remove sulfur dioxide gas contained in flue gas finally by washing device, after reaching emptying requirement, enter air.

Claims (4)

1. the dilution treatment process of a copper smelting slag, it is characterised in that carry out according to following processing step:
(1) in dilution stove, mechanical stirring equipment is introduced, the high-temperature molten-state copper smelting slags of 1150 ~ 1350 DEG C are imported in dilution stove, adjustment stirring rake stretches to 1/3 to 1/2 place of copper smelting slag liquid level, open heating and stir, the temperature of control copper smelting slag is 1200 ~ 1350 DEG C, stirring velocity is 50 ~ 200r/min, and forming blade diameter length ratio is the whirlpool of 0.5 ~ 3;
(2) vulcanizing agent being carried winding-up to copper smelting slag weld pool surface by whirlpool center by the nozzle of high-temperature molten-state copper smelting slag ullage by carrier gas, vulcanizing agent add-on is the 0.3 ~ 8% of copper smelting slag quality, insulated and stirred 10 ~ 60min;
(3) stratification, collects slag after lower floor's matte and upper strata dilution respectively.
2. the dilution treatment process of a kind of copper smelting slag according to claim 1, it is characterised in that described vulcanizing agent comprises copper ore concentrates or pyrite.
3. the dilution treatment process of a kind of copper smelting slag according to claim 1, it is characterised in that described carrier gas comprises rare gas element or nitrogen.
4. the dilution treatment process of a kind of copper smelting slag according to claim 1, it is characterised in that after the dilution of described upper strata in slag copper content below 0.3%.
CN201610144794.8A 2016-03-15 2016-03-15 Dilution treatment method for copper smelting slag Pending CN105671325A (en)

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Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106824543A (en) * 2017-03-15 2017-06-13 中南大学 A kind of method that copper smelting slag reclaims copper
CN106834738A (en) * 2017-03-15 2017-06-13 中南大学 A kind of compound additive and application that copper is reclaimed for copper smelting slag
CN110004352A (en) * 2019-05-11 2019-07-12 东北大学 A method of cupric chromium abrasion-proof cast iron is prepared using melting dilution copper ashes reduction
CN110106433A (en) * 2019-05-11 2019-08-09 东北大学 A kind of method of comprehensive utilization melting dilution copper ashes and cadmia
CN110257643A (en) * 2019-07-01 2019-09-20 东营方圆有色金属有限公司 The technique and recovery system of iron and zinc are recycled from copper weld pool slag
CN112322902A (en) * 2020-09-18 2021-02-05 中南大学 Resource recovery method of copper smelting slag
CN113151692A (en) * 2021-04-28 2021-07-23 东北大学 Thermal state vortex dilution furnace for copper smelting slag
CN113151690A (en) * 2021-04-28 2021-07-23 东北大学 Copper slag dilution-reduction integrated furnace
CN113186404A (en) * 2021-04-28 2021-07-30 东北大学 Copper slag thermal state eddy dilution method
CN115141935A (en) * 2021-03-29 2022-10-04 东北大学 Dilution method for copper refining slag
CN115141938A (en) * 2021-03-29 2022-10-04 东北大学 Method for diluting copper smelting slag by using copper refining slag
WO2022227180A1 (en) * 2021-04-28 2022-11-03 东北大学 Copper smelting-thermal state vortex depletion integrated method

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Cited By (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106824543A (en) * 2017-03-15 2017-06-13 中南大学 A kind of method that copper smelting slag reclaims copper
CN106834738A (en) * 2017-03-15 2017-06-13 中南大学 A kind of compound additive and application that copper is reclaimed for copper smelting slag
CN110004352A (en) * 2019-05-11 2019-07-12 东北大学 A method of cupric chromium abrasion-proof cast iron is prepared using melting dilution copper ashes reduction
CN110106433A (en) * 2019-05-11 2019-08-09 东北大学 A kind of method of comprehensive utilization melting dilution copper ashes and cadmia
CN110257643A (en) * 2019-07-01 2019-09-20 东营方圆有色金属有限公司 The technique and recovery system of iron and zinc are recycled from copper weld pool slag
WO2022057882A1 (en) * 2020-09-18 2022-03-24 中南大学 Resource recycling method for copper smelting residue
CN112322902A (en) * 2020-09-18 2021-02-05 中南大学 Resource recovery method of copper smelting slag
CN115141935A (en) * 2021-03-29 2022-10-04 东北大学 Dilution method for copper refining slag
CN115141938A (en) * 2021-03-29 2022-10-04 东北大学 Method for diluting copper smelting slag by using copper refining slag
CN113151692A (en) * 2021-04-28 2021-07-23 东北大学 Thermal state vortex dilution furnace for copper smelting slag
CN113151690A (en) * 2021-04-28 2021-07-23 东北大学 Copper slag dilution-reduction integrated furnace
CN113186404A (en) * 2021-04-28 2021-07-30 东北大学 Copper slag thermal state eddy dilution method
WO2022227183A1 (en) * 2021-04-28 2022-11-03 东北大学 Copper slag thermal-state eddy current dilution method
WO2022227180A1 (en) * 2021-04-28 2022-11-03 东北大学 Copper smelting-thermal state vortex depletion integrated method

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Application publication date: 20160615