CN107699698A - The method for handling copper ashes - Google Patents
The method for handling copper ashes Download PDFInfo
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- CN107699698A CN107699698A CN201710917697.2A CN201710917697A CN107699698A CN 107699698 A CN107699698 A CN 107699698A CN 201710917697 A CN201710917697 A CN 201710917697A CN 107699698 A CN107699698 A CN 107699698A
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- pelletizing
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- reducing agent
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
- C22B7/04—Working-up slag
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- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21B—MANUFACTURE OF IRON OR STEEL
- C21B13/00—Making spongy iron or liquid steel, by direct processes
- C21B13/0066—Preliminary conditioning of the solid carbonaceous reductant
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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
- C22B1/00—Preliminary treatment of ores or scrap
- C22B1/02—Roasting processes
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B1/00—Preliminary treatment of ores or scrap
- C22B1/14—Agglomerating; Briquetting; Binding; Granulating
- C22B1/24—Binding; Briquetting ; Granulating
- C22B1/2406—Binding; Briquetting ; Granulating pelletizing
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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
- C22B1/00—Preliminary treatment of ores or scrap
- C22B1/14—Agglomerating; Briquetting; Binding; Granulating
- C22B1/24—Binding; Briquetting ; Granulating
- C22B1/242—Binding; Briquetting ; Granulating with binders
- C22B1/243—Binding; Briquetting ; Granulating with binders inorganic
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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
- C22B1/00—Preliminary treatment of ores or scrap
- C22B1/14—Agglomerating; Briquetting; Binding; Granulating
- C22B1/24—Binding; Briquetting ; Granulating
- C22B1/242—Binding; Briquetting ; Granulating with binders
- C22B1/244—Binding; Briquetting ; Granulating with binders organic
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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
- C22B1/00—Preliminary treatment of ores or scrap
- C22B1/14—Agglomerating; Briquetting; Binding; Granulating
- C22B1/24—Binding; Briquetting ; Granulating
- C22B1/248—Binding; Briquetting ; Granulating of metal scrap or alloys
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
- C22B7/001—Dry processes
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
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- Organic Chemistry (AREA)
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Abstract
The invention discloses the method for processing copper ashes, including：Copper ashes, reducing agent, the first additive, binding agent are carried out being mixed to get copper ashes compound；Reducing agent is mixed with binding agent, is molded and obtains reducing agent pelletizing；Mixed using a part of reducing agent pelletizing as mother bulb with copper ashes compound, be molded and obtain copper ashes pelletizing；Second addition and binding agent are carried out being mixed to get additive compound；Mixed using another part reducing agent pelletizing as mother bulb with additive compound, be molded and obtain additive pelletizing；Additive pelletizing basis of formation layer is distributed into rotary hearth furnace；Copper ashes pelletizing is arranged on to basal layer, and oxidizing roasting and reduction roasting processing are carried out by preheating zone, high-temperature region successively in rotary hearth furnace, obtains the flue gas containing lead, zinc and copper and solid roasting product；Solid roasting product is subjected to coarse crushing and screening, obtains coarse granule iron and screenings；Screenings is subjected in small, broken bits and mill ore magnetic selection, obtains fine grained iron and tailings.High grade iron product can be obtained using this method.
Description
Technical field
The invention belongs to chemical engineering of materials field, and specifically, the present invention relates to the method for processing copper ashes.
Background technology
Copper ashes is copper smelting by pyrometallurgical process and a kind of caused " arenolite " waste residue, and the quantity of slag is with the increase of Copper making yield
And increase.Due to China's industry and economic rapid development, China's copper yield and consumption are all located at the first in the world now；Arrive
At present, the quantity of copper smelting by pyrometallurgical process formation slag has reached 150,000,000 tons, and the large enterprises such as adjoint river copper, Daye are coloured smelt
The raising of copper technology, the quantity of copper ashes are also being continuously increased.Copper ashes is a kind of grandidierite metallurgical slag containing divalent metal compound,
Have the characteristics that quantity is big, fine size, wide variety, complicated component, the valuable metal containing substantial amounts of recoverable.Example
Such as, wherein iron content is typically 40% or so, much larger than 29.1% average production-grade of iron ore.As environmental protection will
The raising asked and the increasingly depleted of mineral resources, how to reclaim and be of great significance using these valuable resources.
The content of the invention
It is contemplated that at least solves one of technical problem in correlation technique to a certain extent.Therefore, the present invention
One purpose is the method for proposing processing copper ashes.By using the method for present invention processing copper ashes, can not only effectively prepare
The iron product that steel-making needs is met, and reclaims the metals such as copper, lead, zinc, realizes the high-efficiency comprehensive utilization of copper ashes resource, also
Can effectively solve the problems, such as that caused fired slags are corroded the resistance to material of furnace bottom serious in roasting process.
The present invention is proposed based on problems with：
Copper ashes main mineral constituent is fayalite (2FeOSiO2), magnetic iron ore (Fe3O4) and some gangues composition nothing
Amorphous glass body.Because iron mainly exists in the form of silicate, the beneficiation method using routine is difficult that iron is enriched into iron product
Position more than 55%, the method that generally use carbon is reduced directly to obtain metallic iron is reclaimed.Yet with the raw material of copper ashes in itself
Property, containing a certain amount of sulphur and copper, copper, sulphur are easily entered among iron during high-temperature direct reduction so that iron product
Cupric, sulphur too high (average copper content be higher than 0.6 weight % higher than 1.5 weight %, mean content of sulfur) and be not suitable for steel-making and refine
Iron.When cupric is higher than 0.2% in iron, then more serious harm can be brought to the quality of iron, is also easy to produce copper brittleness phenomenon, iron
When middle sulfur content is too high, steel easily produce hot-short phenomenon.
Therefore, according to an aspect of the present invention, the present invention proposes a kind of method for handling copper ashes, including：
(1) copper ashes, reducing agent, the first additive, binding agent are mixed, to obtain copper ashes compound；
(2) reducing agent is mixed with binding agent and carries out the first forming processes, to obtain reducing agent pelletizing, and by described in
Reducing agent pelletizing is divided into two parts；
(3) mix and carry out at the second shaping with the copper ashes compound using a part of reducing agent pelletizing as mother bulb
Reason, to obtain copper ashes pelletizing；
(4) Second addition is mixed with binding agent, to obtain additive compound；
(5) mixed using reducing agent pelletizing described in another part as mother bulb with the additive compound and carry out the three one-tenth
Type processing, to obtain additive pelletizing；
(6) the additive pelletizing is distributed into rotary hearth furnace, so as to basis of formation layer；On to the basal layer described in arrangement
Copper ashes pelletizing, and carried out successively by preheating zone, high-temperature region at oxidizing roasting processing and reduction roasting in the rotary hearth furnace
Reason, to obtain the flue gas containing lead, zinc and copper and solid roasting product；
(7) the solid roasting product is subjected to coarse crushing and screening, to obtain coarse granule iron and screenings；And
(8) screenings is carried out into small, broken bits and mill ore magnetic selection to handle, to obtain fine grained iron and tailings.
Thus, the method for the processing copper ashes of the above embodiment of the present invention at least has the advantages of following method：First,
Oxidizing roasting processing can be carried out to copper ashes pelletizing and additive pelletizing under the oxidizing atmosphere of rotary hearth furnace preheating zone in advance, it is real
The now effect of the desulfurization of copper ashes, copper, lead and zinc；Second, by using the copper ashes pelletizing and additive of the above embodiment of the present invention
The special construction of pelletizing, can effectively solve pelletizing after oxidizing atmosphere is calcined, in pelletizing reducing agent residual volume it is very few without
It is enough the problem of branch iron brace is reduced into metallic iron, and carry out after oxidizing roasting processing adding reducing agent again can only be on pelletizing
Layer is covered, and then the problem of the heating effect and undesirable iron reduction effect of influence pelletizing；3rd, can be in rotary hearth furnace
Middle realization entirely oxidation, the integration of reducing roasting process, and then reduce production cost and energy consumption；4th, using additive ball
Group separates copper ashes pelletizing and rotary hearth furnace refractory material, effectively can solve during calcination process, fired slags are resistance to furnace bottom
Material corrodes the problem of serious, and then can extend the service life of resistance to material, reduces cost and improves the cycle of operation of rotary hearth furnace；
5th, it is possible to achieve using solid waste copper ashes prepare meet steel-making needs low copper low-sulfur iron particle product, and reclaim copper, lead,
The valuable metals such as zinc, realize the comprehensive utilization of copper ashes resource.
In addition, the method for processing copper ashes according to the above embodiment of the present invention can also have technology additional as follows special
Sign：
In some embodiments of the invention, in step (1), the copper ashes, the reducing agent, first additive and
The mass ratio of the binding agent is 100：(5-15)：(1-15)：(1-10).Copper ashes is taken off thus, it is possible to further improve
The quality of the efficiency of copper desulfurization and the iron product being finally prepared.
In some embodiments of the invention, Second addition quality accounts for 15-40% described in the additive pelletizing.Can
Further to promote the quality of the reduction efficiency of iron and the iron product being finally prepared in copper ashes, and beneficial to solid-state roasting production
The smooth discharging of thing.
In some embodiments of the invention, the average grain diameter of the reducing agent pelletizing is 2-16mm；The copper ashes pelletizing
Average grain diameter be 8-20mm；The average grain diameter of the additive pelletizing is 3-16mm.Thus, can not only significantly improve pair
Copper ashes pelletizing carries out the efficiency of oxidizing roasting processing and reduction roasting processing, moreover it is possible to further improves the iron being finally prepared
The quality of product, and substantially reduce corrosion of the caused liquid slag to resistance to material in roasting process.
In some embodiments of the invention, in step (6), the additive pelletizing that is distributed into the rotary hearth furnace with
The mass ratio of the copper ashes pelletizing is (20-60)：100.Thus, it is possible to provide more reducing agents for reduction roasting processing, enter
And effectively strengthen the reducing atmosphere of rotary hearth furnace high-temperature region and promote the reduction of iron.
In some embodiments of the invention, the reducing agent be the bituminous coal containing more than the weight % of fixed carbon 75, anthracite,
At least one of semi-coke, coke and lignite.Thus, it is possible to the reduction efficiency of iron when further improving reduction roasting processing.
In some embodiments of the invention, chloride, calcite and fluoride are contained in first additive.By
This, not only can effectively destroy the original difficulty of copper ashes and go back original structure, be allowed to be easier in follow-up reduction roasting processing procedure
Metallic iron is reduced into, can also effectively remove lead in copper ashes, zinc, copper and sulphur component.
In some embodiments of the invention, chloride, the calcite and the fluorine described in first additive
Compound mass ratio is (5-8)：(1-5)：(0.1-3).Thus, it is possible to make copper ashes pelletizing in oxidizing roasting processing procedure is carried out,
Cl2And F2It can uniformly, stably, persistently produce, ensure being smoothed out for decopper(ing), dezincification and the reaction of de- lead.
In some embodiments of the invention, the Second addition is the mineral containing calcium carbonate, magnesium carbonate.Thus,
Additive pelletizing can be not only set to promote the reduction of iron, also with the substance reaction such as fayalite in reducing roasting process
It can decompose and produce CaO and MgO, absorb and fix reducing agent caused sulphur composition in rotary hearth furnace roasting process, and then further
Improve the quality for the iron product being finally prepared.
In some embodiments of the invention, the temperature of the oxidizing roasting processing is 1000-1250 DEG C；The reduction roasting
The temperature for burning processing is 1300-1450 DEG C.Thus, can not only make in oxidizing roasting processing procedure copper in copper ashes, lead,
Zinc and sulphur are effectively removed, moreover it is possible to are reduced sufficiently iron in reduction roasting processing procedure for metallic iron.
Brief description of the drawings
Fig. 1 is the method for processing copper ashes according to an embodiment of the invention.
Fig. 2 is the method according to the processing copper ashes of another embodiment of the invention.
Embodiment
Embodiments of the invention are described below in detail, the example of the embodiment is shown in the drawings, wherein from beginning to end
Same or similar label represents same or similar element or the element with same or like function.Below with reference to
The embodiment of accompanying drawing description is exemplary, it is intended to for explaining the present invention, and is not considered as limiting the invention.
Therefore, according to an aspect of the present invention, the present invention proposes a kind of method for handling copper ashes, including：
(1) copper ashes, reducing agent, the first additive, binding agent are mixed, to obtain copper ashes compound；(2) will
Reducing agent mixes with binding agent and carries out the first forming processes, to obtain reducing agent pelletizing, and reducing agent pelletizing is divided into two
Part；(3) mixed using a part of reducing agent pelletizing as mother bulb with copper ashes compound and carry out the second forming processes, so as to
To copper ashes pelletizing；(4) Second addition is mixed with binding agent, to obtain additive compound；(5) with another portion
Reducing agent pelletizing is divided to be mixed as mother bulb with additive compound and carry out the 3rd forming processes, to obtain additive pelletizing；
(6) additive pelletizing is distributed into rotary hearth furnace, so as to basis of formation layer；Copper ashes pelletizing is arranged on to basal layer, and in rotary hearth furnace
Inside carry out oxidizing roasting processing by preheating zone, high-temperature region successively and reduction roasting is handled, to obtain containing lead, zinc and copper
Flue gas and solid roasting product；(7) solid roasting product is subjected to coarse crushing and screening, to obtain under coarse granule iron and sieve
Thing；And screenings is carried out in small, broken bits and mill ore magnetic selection and handled by (8), to obtain fine grained iron and tailings.
Thus, the method for the processing copper ashes of the above embodiment of the present invention at least has the advantages of following method：First,
Oxidizing roasting processing can be carried out to copper ashes pelletizing and additive pelletizing under the oxidizing atmosphere of rotary hearth furnace preheating zone in advance, it is real
The now effect of the desulfurization of copper ashes, copper, lead and zinc；Second, by using the copper ashes pelletizing and additive of the above embodiment of the present invention
The special construction of pelletizing, can effectively solve pelletizing after oxidizing atmosphere is calcined, in pelletizing reducing agent residual volume it is very few without
It is enough the problem of branch iron brace is reduced into metallic iron, and carry out after oxidizing roasting processing adding reducing agent again can only be on pelletizing
Layer is covered, and then the problem of the heating effect and undesirable iron reduction effect of influence pelletizing；3rd, can be in rotary hearth furnace
Middle realization entirely oxidation, the integration of reducing roasting process, and then reduce production cost and energy consumption；4th, using additive ball
Group separates copper ashes pelletizing and rotary hearth furnace refractory material, effectively can solve during calcination process, fired slags are resistance to furnace bottom
Material corrodes the problem of serious, and then can extend the service life of resistance to material, reduces cost and improves the cycle of operation of rotary hearth furnace；
5th, it is possible to achieve using solid waste copper ashes prepare meet steel-making needs low copper low-sulfur iron particle product, and reclaim copper, lead,
The valuable metals such as zinc, realize the comprehensive utilization of copper ashes resource.
It is described in detail below with reference to the method for processing copper ashes of the Fig. 1-2 to the above embodiment of the present invention.
S100：Prepare copper ashes pelletizing
According to an embodiment of the invention, copper ashes, reducing agent, the first additive, binding agent are mixed, to obtain copper
Dregs mixing material；Reducing agent is mixed with binding agent and carries out the first forming processes, to obtain reducing agent pelletizing, and will reduction
Agent pelletizing is divided into two parts；Mix and carry out at the second shaping with copper ashes compound using a part of reducing agent pelletizing as mother bulb
Reason, to obtain copper ashes pelletizing.
According to a particular embodiment of the invention, the reduction in the present invention by being obtained with reducing agent and bonding agent mixed-forming
Agent pelletizing is mother bulb, and copper ashes compound is mixed with copper ashes pelletizing, can make copper ashes pelletizing structure kernel containing reducing agent compared with
It is more, and outer layer is less containing reducing agent.Thus, it is possible to the reducing agent of pelletizing kernel is set to be carried over into reduction roasting processing procedure
In, provide carbon source for the direct-reduction of follow-up copper ashes.
According to a particular embodiment of the invention, reducing agent can be the bituminous coal containing more than the weight % of fixed carbon 75, anthracite,
At least one of semi-coke, coke and lignite.Thus, it is possible to the reduction efficiency of iron when further improving reduction roasting processing.
According to a particular embodiment of the invention, binding agent can be modified starch, CMC, syrup, bentonite, sodium humate
At least one of Deng.Thus, it is possible to make copper ashes pelletizing that there is certain intensity, fragmentation is avoided.
According to a particular embodiment of the invention, chloride and fluoride can be contained in the first additive, wherein, chloride
Can be selected from least one of calcium chloride, sodium chloride and potassium chloride；Fluoride can be selected from calcirm-fluoride, sodium fluoride and
At least one of potassium fluoride.Inventor's discovery, chlorion and fluorine ion can destroy the molecular structure of silicate, promote iron
The reduction process of olivine.In addition, the copper in copper ashes mainly exists in the form of copper sulfide, Cu oxide, in oxidizing atmosphere
Under when being calcined, the impurity in copper ashes can promote the additive containing sulfide to rely on vapor, oxygen in combustion product gases
With sulfur dioxide and decompose produce main component be chlorine, fluorine gas and hydrogen chloride and and hydrogen fluoride gas, the gas of generation can
Continue to occur with the copper in copper ashes chloride or fluoride (including stannous chloride, the chlorination of series of chemical generation copper
Copper, copper fluoride and copper fluoride etc.), copper chloride and copper fluoride boiling point are relatively low, and then can at high temperature volatilize and depart from ball
Group, into flue gas, so as to reach the effect of decopper(ing)；Further, added in the first compound of copper ashes pelletizing outer layer covers
Reducing agent can also promote the chloride of copper reaction and the volatilization process of fluoride in oxidizing roasting processing procedure, meanwhile,
Lead, zinc in copper ashes also can occur similar reaction and enter flue gas.In addition, inventor also found, the sulphur majority in copper ashes with
The form of metal sulfide is present, and when being calcined under oxidizing atmosphere, sulphur can be oxidized to sulfur dioxide or sulfur trioxide
Removed into flue gas；Meanwhile chlorine caused by additive and fluorine gas can react with metal sulfide, and metal is vulcanized
Sulphur in thing cements out, so as to further promote the subtractive process of sulphur.
According to a particular embodiment of the invention, calcite can be contained in the first additive.Inventor has found that decopper(ing) reacts
It is a progressive course of reaction, if Cl2And F2Deng gas in rotary hearth furnace if generation is too fast, then can be rapidly by flue gas band
Walk, leave body of heater, cause chlorinating agent and fluorization agent consumption excessive, and decopper(ing) effect is poor, therefore, Cl2And F2It is too early Deng gas
A large amount of generations be unfavorable for reaching good decopper(ing) effect.In addition, inventor also found, calcite can be catalyzed Cl2And F2It is raw
Into the lasting progress of reaction slowly, uniformly, stable, so reduce the dosage of chlorinating agent and fluorization agent and reach more preferable decopper(ing),
The effect of lead and zinc；Meanwhile the calcite in additive can also generate CaO compositions, a side in oxidizing roasting processing procedure
Face, the CaO reactivities just generated are higher, can further promote ferriferous oxide quick in reduction roasting processing procedure
Metallic iron is reduced into, and then the addition of additive can be substantially reduced and add species, saves production cost；On the other hand,
Part chlorion and fluorine ion are remained in slag phase, can destroy the structure system of silicate, reduce slag phase fusing point, Jin Eryou
Beneficial to the agglomeration of iron particle, the final quality for improving iron product.
According to a particular embodiment of the invention, chloride, calcite and fluoride can be contained in the first additive.Its
In, chloride can be selected from least one of calcium chloride, sodium chloride and potassium chloride；Fluoride can be selected from calcirm-fluoride,
At least one of sodium fluoride and potassium fluoride.Thus, it not only can effectively destroy the original difficulty of copper ashes and go back original structure, be allowed to
It is easier to be reduced into metallic iron in follow-up reduction roasting processing procedure, can be with can be by the copper in copper ashes, zinc and lead component
Reaction generation volatile matter departs from pelletizing, while may also function as the effect of desulfurization, promotes the sulphur component in copper ashes with sulfur dioxide shape
Formula or the form of sulfur trioxide are volatilized away, and then further improve the quality for the iron product being finally prepared.In addition, also
The addition of chloride and fluoride can be significantly reduced, and then reduces production cost.
According to a particular embodiment of the invention, the mass ratio of chloride, calcite and fluoride can be with the first additive
For (5-8)：(1-5)：(0.1-3).By using above-mentioned composition and the first additive of proportioning in the present invention, can not only have
Effect destroys the original difficulty of copper ashes and goes back original structure, is allowed to be easier to be reduced into metal in follow-up reduction roasting processing procedure
Iron, the removal effect to copper, lead and zinc in copper ashes can also be further improved, reduce production cost and significantly improve follow-up go back
The quality of the efficiency of former calcination process and the iron product being finally prepared.
According to a particular embodiment of the invention, in copper ashes compound, copper ashes, reducing agent, the first additive and binding agent
Mass ratio can be 100：(5-15)：(1-15)：(1-10).Inventor has found, when the addition of reducing agent in copper ashes compound
When measuring very few, the efficiency and effect of decopper(ing), lead and zinc etc. are influenceed, and then influences the quality of iron product being finally prepared, and
When the addition of reducing agent in copper ashes compound is excessive, not only bad for being smoothed out for oxidizing roasting processing, can also cause
Reducing agent wastes；When the addition of additive in copper ashes compound is very few, can influence to copper, lead and zinc and sulphur in copper ashes
Removal effect, and when the addition of additive is excessive, the quantity of slag increases, and increases energy consumption, also results in additive waste；Work as copper
When the addition of binding agent is very few in dregs mixing material, the intensity for the copper ashes pelletizing being prepared is poor, and when the addition of binding agent
When measuring excessive, binding agent is caused to waste.Thus, by controlling copper ashes in copper ashes compound, reducing agent, first to add in the present invention
It can be 100 to add the mass ratio of agent and binding agent：(5-15)：(1-15)：(1-10), it can further improve and copper ashes is taken off
Copper, lead, zinc and the efficiency of desulfurization and effect, and then further improve the efficiency of processing copper ashes and the iron production being finally prepared
The quality of product.
According to a particular embodiment of the invention, the average grain diameter of reducing agent pelletizing can be 2-16mm；Copper ashes pelletizing is put down
Equal particle diameter can be 8-20mm.Thus, it can not only significantly improve and oxidizing roasting processing and reduction roasting are carried out to copper ashes pelletizing
The efficiency of processing, moreover it is possible to control containing for reducing agent in copper ashes pelletizing by adjusting the particle diameter of reducing agent pelletizing and copper ashes pelletizing
Amount, and then effectively facilitate the direct-reduction of iron in reduction roasting processing procedure.
According to a particular embodiment of the invention, C/O mol ratios can be 1.4-2.4 in copper ashes pelletizing.Thus, it is possible to enter
One step improve to the decopper(ing) of copper ashes, lead, zinc and the efficiency of desulfurization and effect, and then further improve processing copper ashes efficiency and
The quality for the iron product being finally prepared.
S200：Prepare additive pelletizing
According to an embodiment of the invention, Second addition is mixed with binding agent, to obtain additive compound；
Mixed using another part reducing agent pelletizing as mother bulb with additive compound and carry out the 3rd forming processes, to be added
Add agent pelletizing.
According to a particular embodiment of the invention, the reduction in the present invention by being obtained with reducing agent and bonding agent mixed-forming
Agent pelletizing is mother bulb, and is mixed with additive pelletizing with additive compound, can make additive pelletizing structure kernel containing also
Former agent is more, and outer layer is less containing reducing agent.Thus, it is possible to the reducing agent of pelletizing kernel is set to be carried at reduction roasting
During reason, Primordial Qi is gone back when providing carbon source for the direct-reduction of follow-up copper ashes, and then can further strengthen reduction roasting processing
Atmosphere, iron in copper ashes is promoted to be reduced to metallic iron.
According to a particular embodiment of the invention, binding agent can be in modified starch, CMC, syrup, bentonite etc. at least
It is a kind of.Thus, it is possible to make copper ashes pelletizing that there is certain intensity.
According to a particular embodiment of the invention, Second addition can be the mineral containing calcium carbonate, magnesium carbonate.The present invention
In by using above-mentioned additive, additive pelletizing structure kernel can be made more containing reducing agent, outer layer is calcium carbonate, carbon
The integument of the mineralogical composition of sour magnesium, can be by additive when carrying out follow-up oxidizing roasting processing and reduction roasting is handled
Pelletizing spreads rotary furnace bottom and copper ashes pelletizing is arranged on additive pelletizing in advance, and then can protect and add in preheating zone
The not oxidized calcination atmosphere roasting of reducing agent inside agent pelletizing and largely consume, and additive pelletizing outer layer contain calcium carbonate,
The substance reactions such as the fayalite in CaO, MgO and upper strata copper ashes pelletizing caused by the thing phase decomposition of magnesium carbonate, can be further
Promote the reduction of iron in copper ashes, meanwhile, integument participates in reaction and is destroyed, and then can make the reduction of additive pelletizing kernel
Agent discharges reducing atmosphere when strengthening reduction roasting processing, promotes the reduction of iron in copper ashes.In addition, new caused CaO,
MgO reactivities are strong, can absorb and fix reducing agent caused sulphur composition in reduction roasting processing procedure, substantially reduce
Into the sulfur content in iron, and then further improve the quality for the iron product being finally prepared.In addition, inventor also found,
By using the Second addition containing calcium carbonate, carbonic acid magnesium mineral, it can make additive pelletizing that there is higher basicity and contain
There are a large amount of reducing agents, and then can be sufficiently spaced from the refractory material of copper ashes pelletizing and furnace bottom in roasting process, reduce roasting
During erosion of the caused liquid slag to resistance to material, meanwhile, additive pelletizing and furnace bottom adhesion, also help solid-state roasting
The smooth discharging of product.
According to a particular embodiment of the invention, the quality of Second addition can account for 15-40% in additive pelletizing.By
This, can further promote the quality of the reduction efficiency of iron and the iron product being finally prepared in copper ashes, and roast beneficial to solid-state
Burn the smooth discharging of product.
According to a particular embodiment of the invention, the average grain diameter of reducing agent pelletizing can be 2-16mm；Additive pelletizing
Average grain diameter can be 3-16mm.Thus, it can not only significantly improve and oxidizing roasting processing and reduction roasting are carried out to copper ashes pelletizing
Burn the efficiency of processing, moreover it is possible to added to control in additive pelletizing by the particle diameter for adjusting reducing agent pelletizing and additive pelletizing
The content of agent, and then further promote the reduction efficiency of iron and the quality for the iron product being finally prepared in copper ashes, and be beneficial to
The smooth discharging of solid-state product of roasting.
S300：Carry out oxidizing roasting processing and reduction roasting processing successively to copper ashes pelletizing and additive pelletizing
According to an embodiment of the invention, additive pelletizing is distributed into rotary hearth furnace, so as to basis of formation layer；To on basal layer
Copper ashes pelletizing is arranged, and is carried out successively by preheating zone, high-temperature region at oxidizing roasting processing and reduction roasting in rotary hearth furnace
Reason, to obtain the flue gas containing lead, zinc and copper and solid roasting product.
According to a particular embodiment of the invention, oxidizing roasting processing is carried out in preheating zone, and preheating zone is oxidizing atmosphere, oxidation
During calcination process, copper, zinc and lead in copper ashes mainly exist in the form of metal sulfide and metal oxide, copper ashes
In impurity promote the additive containing chloride and fluoride rely on combustion product gases in vapor, oxygen and sulfur dioxide
And decompose produce main component be chlorine, fluorine gas and hydrogen chloride and and hydrogen fluoride gas, the gas of generation continue with copper ashes
Copper, lead and zinc etc. the chloride or fluoride of series of chemical generation copper, lead or zinc occurs, and volatilize at high temperature
Depart from pelletizing, into flue gas, so as to reach the effect of decopper(ing), dezincification and de- lead；In addition, the sulphur in copper ashes is more with metal sulphur
The form of compound is present, and when being calcined under oxidizing atmosphere, sulphur can be oxidized to sulfur dioxide or sulfur trioxide enters flue gas
Removing；Meanwhile chlorine caused by additive and fluorine gas can react with metal sulfide, and by the sulphur in metal sulfide
Cement out, so as to further promote the subtractive process of sulphur.
Wherein, the reaction of metal oxide and chlorine and hydrogen chloride is as follows：
Metal sulfide and chlorine reaction equation are as follows：
In addition, the appropriate reducing agent having of copper ashes pelletizing outer layer can form appropriate reduction when oxidizing roasting is handled
Atmosphere, further promotes the chloride and fluoride and the process of volatilization of copper reaction, and then further improves decopper(ing), de- lead
With the efficiency and effect of dezincification, and the appropriate calcite having in additive can make Cl2And F2Reaction of formation slowly,
Even, stable lasting progress, and then the dosage of chlorinating agent and fluorization agent can be reduced and reach more preferable decopper(ing), lead and zinc
Effect.
According to a particular embodiment of the invention, reduction roasting processing is carried out in high-temperature region, and high-temperature region is strict also Primordial Qi
Atmosphere, in reduction roasting processing procedure, ferriferous oxide is reduced directly to metallic iron in high-temperature region in copper ashes.In addition, reducing
During calcination process, CaO and MgO caused by the Second addition decomposition that additive pelletizing outer layer has can further promote
Enter the direct-reduction of iron, and discharge the reducing agent of pelletizing kernel, strengthen reducing atmosphere, further promote the reduction of iron, meanwhile,
CaO or MgO activity is stronger caused by new, moreover it is possible to further absorbs sulphur composition caused by reducing agent, and then further improves final
The quality of the iron product of preparation.In addition, additive pelletizing basis of formation layer is distributed into rotary hearth furnace and copper is arranged on basal layer
The mode of slag pelletizing can also effectively avoid erosion of the caused liquid slag to resistance to material in roasting process, and be advantageous to solid-state roasting
Product is burnt smoothly to discharge.
According to a particular embodiment of the invention, the additive pelletizing and the moisture content of copper ashes pelletizing arranged in rotary hearth furnace are equal
Not higher than 1%, thus, it is possible to further improve the efficiency of oxidizing roasting processing and reduction roasting processing, and oxidizing roasting is reduced
Processing and the energy consumption of reduction roasting processing.
According to a particular embodiment of the invention, the mass ratio of the additive pelletizing being distributed into rotary hearth furnace and copper ashes pelletizing can
Think (20-60)：100.Thus, it can not only be handled for reduction roasting and more reducing agents are provided, and then effectively strengthen turning bottom
The reducing atmosphere of stove high-temperature region and the abundant reduction for promoting iron, basicity can also be further improved, and then react generation
CaO, MgO absorb sulphur composition caused by reducing agent, and then improve the quality for the iron product being finally prepared, and are beneficial to solid-state
Product of roasting smoothly goes out.
According to a particular embodiment of the invention, the temperature of oxidizing roasting processing can be 1000-1250 DEG C, at oxidizing roasting
The time of reason can be 20-40min；The temperature of reduction roasting processing is 1300-1450 DEG C, and the time of reduction roasting processing can
Think 20-40min.Thus, copper, lead, zinc and sulphur in copper ashes can not only effectively removed, moreover it is possible at reduction roasting
Iron is set to be reduced sufficiently as metallic iron during reason.
According to a particular embodiment of the invention, in rotary hearth furnace the angle of preheating zone be 120-140 °, the angle of high-temperature region be
140-160°.Thus, not only copper ashes pelletizing and additive pelletizing can be carried out at oxidizing roasting processing and reduction roasting successively
Reason, moreover it is possible to the time that oxidizing roasting processing and reduction roasting are handled is adjusted by adjusting the angle of preheating zone and high-temperature region, and
The temperature of oxidizing roasting processing and reduction roasting processing is controlled respectively, and then can be had copper, lead, zinc and sulphur in copper ashes
Effect removing, and it is reduced sufficiently iron for metallic iron in reduction roasting processing procedure.
According to a particular embodiment of the invention, rotary hearth furnace circumferentially can be sequentially arranged material charging region, preheating zone, height in direction
Warm area and cooling zone, the first wall can be used to obstruct between material charging region and preheating zone, can be adopted between preheating zone and high-temperature region
Obstructed with the second wall, high-temperature region and cooling zone can use the 3rd wall to obstruct.Wherein, the first wall can be pressure wall
Body, the highly total height close to additive pelletizing and copper ashes pelletizing, flee thus, it is possible to reduce preheating zone gas to material charging region
The erosion of furnace wall；Second wall can be pressure wall, thus, on the one hand can reduce corrosion, on the other hand be advantageous to preheat
Area keeps oxidizing atmosphere and high-temperature region to keep reducing atmosphere；3rd wall can be furnace wall, thus, it is possible to ensure cooling zone ball
Group's rapid drop in temperature；Preheating zone furnace wall can use special chlorine-resistant high-temperature material, and flue outlet is arranged at preheating zone, enters
And height of the preheating zone burner apart from pelletizing is reduced, furthermore, it is possible to rotary hearth furnace flue gas is reclaimed using cloth bag dedusting process, and then
Obtain the dusting product containing copper chloride, lead chloride, zinc chloride, copper fluoride, lead fluoride or zinc fluoride；Can preheating zone,
High-temperature region body of heater both sides set burner noz(zle) to be not provided with burner noz(zle) in cooling zone to meet the requirement of heat temperature raising；Can profit
High temperature flash baking is carried out to the wet bulb group in cloth area with the high temperature heat by cooling block transitive and high temperature furnace bottom.
S400：Carry out coarse crushing successively to solid roasting product, screening, in small, broken bits and mill ore magnetic selection handle to obtain iron product and
Tailings
According to an embodiment of the invention, solid roasting product is subjected to coarse crushing and screening, to obtain coarse granule iron and sieve
Lower thing；Screenings is subjected to the processing of in small, broken bits and mill ore magnetic selection, to obtain iron product and tailings.
According to a particular embodiment of the invention, coarse granule iron and the mixing of fine grained iron can obtain final iron product.
Embodiment 1
The copper ashes raw material used for the tailings after certain smeltery's slow cooling copper ashes Floatation of Copper, hereinafter referred to as copper ashes, wherein, this
The main component for the copper ashes selected in embodiment is：TFe content is that 36.84 weight %, FeO contents are 41.55 weight %,
SiO2Content is that 34.02 weight %, Cu contents are that 0.13 weight %, Pb content is that 0.56 weight %, Zn content is 1.41 weights
% is measured, S contents are 0.15 weight %；Reducing agent used is anthracite, is 79.19 weight % containing fixed carbon content；First addition
Agent is compound additive, the weight % of chloride containing calcium 70, the weight % of calcite 10, the weight % of calcirm-fluoride 20；Binding agent forms sediment to be modified
Powder；Second addition is lime stone.
(1) by copper ashes, reducing agent, the first additive and binding agent according to 100：8：15：15 mass ratio carries out dispensing,
And mixing is rolled in edge runner, obtain copper ashes compound；
(2) by reducing agent and binding agent according to 100:15 mass ratio carries out dispensing, and disk pelletizing is carried out after rolling mixing,
Reducing agent pelletizing is obtained, reducing agent pelletizing is divided into two parts；
(3) mixed using a part of reducing agent pelletizing as mother bulb with copper ashes compound and carry out disk pelletizing, drying, obtained
The copper ashes pelletizing that C/O mol ratios are 1.6, moisture content is 1%；
(4) by Second addition and binding agent according to 100:12 mass ratio is mixed, and obtains additive compound；
(5) mixed using another part reducing agent pelletizing as mother bulb with additive compound and carry out pelletizing, drying, obtained
The quality of Second addition accounts for 25% in additive pelletizing, wherein additive pelletizing, and the moisture content of additive pelletizing is 1%；
(7) coarse crushing will be carried out after the solid roasting product cooling of rotary hearth furnace discharge, and crosses 1mm screenings, obtain coarse granule iron
And screenings；
(8) screenings is in small, broken bits to 0.15mm, magnetic separation obtains fine grained iron, is left nonmagnetic product and can be used as producing cement
Raw material.
Wherein, coarse granule iron and fine grained iron are mixed to get final metal iron product, and copper content is reduced in product
0.008%, sulfur content is reduced to 0.026%, iron content 92.16%, iron recovery 94.07%, meets China and steel-making is refined
The standard of iron.
Embodiment 2
The copper ashes raw material used for the tailings after certain smeltery's slow cooling copper ashes Floatation of Copper, hereinafter referred to as copper ashes, wherein, this
The main component for the copper ashes selected in embodiment is：The content that TFe content is 39.14 weight %, FeO is 46.96 weights
Measure %, SiO2Content be 31.44 weight %, Cu content be 0.1 weight %, Pb content be containing for 0.43 weight %, Zn
The content measured as 0.4 weight %, S is 0.18 weight %；Reducing agent used is semi-coke, containing the weight % of fixed carbon 83.49；First
Additive is compound additive, the weight % of chloride containing calcium 80, the weight % of calcite 19, the weight % of potassium fluoride 1；Binding agent is swollen
Profit soil；Second addition is dolomite.
(1) by copper ashes, reducing agent, the first additive and binding agent according to 100：15：5：8 mass ratio carries out dispensing, and
Mixing is rolled in edge runner, obtains copper ashes compound；
(2) by reducing agent and binding agent according to 100:6 mass ratio carries out dispensing, and disk pelletizing is carried out after rolling mixing,
Reducing agent pelletizing is obtained, reducing agent pelletizing is divided into two parts；
(3) mixed using a part of reducing agent pelletizing as mother bulb with copper ashes compound and carry out disk pelletizing, drying, obtained
The copper ashes pelletizing that C/O mol ratios are 2.4, moisture content is 1%；
(4) by Second addition and binding agent according to 100:6 mass ratio is mixed, and obtains additive compound；
(5) mixed using another part reducing agent pelletizing as mother bulb with additive compound and carry out pelletizing, drying, obtained
The quality of Second addition accounts for 15% in additive pelletizing, wherein additive pelletizing, and the moisture content of additive pelletizing is 1%；
(6) additive pelletizing basis of formation layer is distributed into rotary hearth furnace, to basal layer on arrange copper ashes pelletizing, make additive
Pelletizing and copper ashes pelletizing carry out oxidizing roasting processing and reduction roasting processing by preheating zone, high-temperature region successively in rotary hearth furnace,
Obtain the flue gas containing lead, zinc and copper and solid roasting product.Wherein, the mass ratio of additive pelletizing and copper ashes pelletizing is 20:
100, the temperature of rotary hearth furnace preheating zone is 1000-1200 DEG C, and partition angles are 120 °, and the region is oxidizing atmosphere；High-temperature region
Temperature is 1200-1450 DEG C, and partition angles are 160 °, and the region is strict reducing atmosphere；The rotating speed of rotary hearth furnace is 70min/
Circle, flue is provided with rotary hearth furnace preheating zone, and flue gas is extracted out by flue, the bag collection after heat exchange cools, obtained cupric
The dust of lead zinc；
(7) coarse crushing will be carried out after the solid roasting product cooling of rotary hearth furnace discharge, and crosses 1mm screenings, obtain coarse granule iron
And screenings；
(8) screenings is in small, broken bits to 0.15mm, magnetic separation obtains fine grained iron, is left nonmagnetic product and can be used as producing cement
Raw material.
Wherein, coarse granule iron and fine grained iron are mixed to get final metal iron product, and copper content is reduced in product
0.009%, sulfur content is reduced to 0.03%, iron content 93.08%, iron recovery 93.49%, meets China and steel-making is refined
The standard of iron.
Embodiment 3
The copper ashes raw material used for the tailings after certain smeltery's slow cooling copper ashes Floatation of Copper, hereinafter referred to as copper ashes, wherein, this
The main component for the copper ashes selected in embodiment is：The content that TFe content is 38.49 weight %, FeO is 39.46 weights
Measure %, SiO2Content be 34.74 weight %, Cu content be 0.15 weight %, Pb content be containing for 0.57 weight %, Zn
The content measured as 1.49 weight %, S is 0.13 weight %；Reducing agent used is coking coal, is 85.42 weight % containing fixed carbon；The
One additive is compound additive, the weight % of chloride containing calcium 50, the weight % of calcite 40, the weight % of sodium fluoride 10；Binding agent is
CMC；Second addition is lime stone.
(1) by copper ashes, reducing agent, the first additive and binding agent according to 100：5：10：1 mass ratio carries out dispensing, and
Mixing is rolled in edge runner, obtains copper ashes compound；
(2) by reducing agent and binding agent according to 100:1 mass ratio carries out dispensing, and disk pelletizing is carried out after rolling mixing,
Reducing agent pelletizing is obtained, reducing agent pelletizing is divided into two parts；
(3) mixed using a part of reducing agent pelletizing as mother bulb with copper ashes compound and carry out disk pelletizing, drying, obtained
The copper ashes pelletizing that C/O mol ratios are 1.4, moisture content is 1%；
(4) by Second addition and binding agent according to 100:1 mass ratio is mixed, and obtains additive compound；
(5) mixed using another part reducing agent pelletizing as mother bulb with additive compound and carry out pelletizing, drying, obtained
The quality of Second addition accounts for 40% in additive pelletizing, wherein additive pelletizing, and the moisture content of additive pelletizing is 1%；
(6) additive pelletizing basis of formation layer is distributed into rotary hearth furnace, to basal layer on arrange copper ashes pelletizing, make additive
Pelletizing and copper ashes pelletizing carry out oxidizing roasting processing and reduction roasting processing by preheating zone, high-temperature region successively in rotary hearth furnace,
Obtain the flue gas containing lead, zinc and copper and solid roasting product.Wherein, the mass ratio of additive pelletizing and copper ashes pelletizing is 60:
100, the temperature of rotary hearth furnace preheating zone is 900-1150 DEG C, and partition angles are 130 °, and the region is oxidizing atmosphere；High-temperature region
Temperature is 1150-1400 DEG C, and partition angles are 150 °, and the region is strict reducing atmosphere；The rotating speed of rotary hearth furnace is 75min/
Circle, flue is provided with rotary hearth furnace preheating zone, and flue gas is extracted out by flue, the bag collection after heat exchange cools, obtained cupric
The dust of lead zinc；
(7) coarse crushing will be carried out after the solid roasting product cooling of rotary hearth furnace discharge, and crosses 1mm screenings, obtain coarse granule iron
And screenings；
(8) screenings is in small, broken bits to 0.15mm, magnetic separation obtains fine grained iron, is left nonmagnetic product and can be used as producing cement
Raw material.
Wherein, coarse granule iron and fine grained iron are mixed to get final metal iron product, and copper content is reduced in product
0.009%, sulfur content is reduced to 0.027%, iron content 92.48%, iron recovery 94.77%, meets China and steel-making is refined
The standard of iron.
In the description of this specification, reference term " one embodiment ", " some embodiments ", " example ", " specifically show
The description of example " or " some examples " etc. means specific features, structure, material or the spy for combining the embodiment or example description
Point is contained at least one embodiment or example of the present invention.In this manual, to the schematic representation of above-mentioned term not
Identical embodiment or example must be directed to.Moreover, specific features, structure, material or the feature of description can be any
Combined in an appropriate manner in individual or multiple embodiments or example.In addition, in the case of not conflicting, the skill of this area
Art personnel can be tied the different embodiments or example and the feature of different embodiments or example described in this specification
Close and combine.
Although embodiments of the invention have been shown and described above, it is to be understood that above-described embodiment is example
Property, it is impossible to limitation of the present invention is interpreted as, one of ordinary skill in the art within the scope of the invention can be to above-mentioned
Embodiment is changed, changed, replacing and modification.
Claims (10)
- A kind of 1. method for handling copper ashes, it is characterised in that including：(1) copper ashes, reducing agent, the first additive, binding agent are mixed, to obtain copper ashes compound；(2) reducing agent is mixed with binding agent and carries out the first forming processes, to obtain reducing agent pelletizing, and by the reduction Agent pelletizing is divided into two parts；(3) mixed using a part of reducing agent pelletizing as mother bulb with the copper ashes compound and carry out the second forming processes, To obtain copper ashes pelletizing；(4) Second addition is mixed with binding agent, to obtain additive compound；(5) mix and carry out at the 3rd shaping with the additive compound using reducing agent pelletizing described in another part as mother bulb Reason, to obtain additive pelletizing；(6) the additive pelletizing is distributed into rotary hearth furnace, so as to basis of formation layer；The copper ashes is arranged on to the basal layer Pelletizing, and oxidizing roasting processing and reduction roasting processing are carried out by preheating zone, high-temperature region successively in the rotary hearth furnace, so as to Obtain the flue gas containing lead, zinc and copper and solid roasting product；(7) the solid roasting product is subjected to coarse crushing and screening, to obtain coarse granule iron and screenings；And(8) screenings is carried out into small, broken bits and mill ore magnetic selection to handle, to obtain fine grained iron and tailings.
- 2. according to the method for claim 1, it is characterised in that in step (1), the copper ashes, the reducing agent, described the The mass ratio of one additive and the binding agent is 100：(5-15)：(1-15)：(1-10).
- 3. according to the method for claim 1, it is characterised in that Second addition quality accounts for described in the additive pelletizing 15-40%.
- 4. according to the method for claim 1, it is characterised in that the average grain diameter of the reducing agent pelletizing is 2-16mm；Institute The average grain diameter for stating copper ashes pelletizing is 8-20mm；The average grain diameter of the additive pelletizing is 3-16mm.
- 5. according to the method for claim 1, it is characterised in that in step (6), be distributed into the rotary hearth furnace described in add The mass ratio for adding agent pelletizing and the copper ashes pelletizing is (20-60)：100.
- 6. according to the method for claim 1, it is characterised in that the reducing agent is the cigarette containing more than the weight % of fixed carbon 75 At least one of coal, anthracite, semi-coke, coke and lignite.
- 7. according to the method for claim 1, it is characterised in that in first additive containing chloride, calcite and Fluoride.
- 8. according to the method for claim 7, it is characterised in that chloride described in first additive, side solution Stone and the fluoride mass ratio are (5-8)：(1-5)：(0.1-3).
- 9. according to the method for claim 1, it is characterised in that the Second addition is containing calcium carbonate, magnesium carbonate Mineral.
- 10. according to the method for claim 1, it is characterised in that the temperature of the oxidizing roasting processing is 1000-1250 ℃；The temperature of the reduction roasting processing is 1300-1450 DEG C.
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| CN111394593A (en) * | 2020-05-08 | 2020-07-10 | 中南大学 | Method for reducing fluorine and chlorine content in copper smelting flue gas |
| CN112795717A (en) * | 2020-12-28 | 2021-05-14 | 通辽市君致清科技有限公司 | Method for reducing iron scale by using waste heat of steel slag |
| CN112813277A (en) * | 2020-12-28 | 2021-05-18 | 中南大学 | Method for separating and recovering valuable metals from copper smelting slag through chlorination roasting |
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| CN112813277A (en) * | 2020-12-28 | 2021-05-18 | 中南大学 | Method for separating and recovering valuable metals from copper smelting slag through chlorination roasting |
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