CN110983067A - Secondary copper refining process - Google Patents
Secondary copper refining process Download PDFInfo
- Publication number
- CN110983067A CN110983067A CN201911412919.0A CN201911412919A CN110983067A CN 110983067 A CN110983067 A CN 110983067A CN 201911412919 A CN201911412919 A CN 201911412919A CN 110983067 A CN110983067 A CN 110983067A
- Authority
- CN
- China
- Prior art keywords
- copper
- refining
- furnace
- copper liquid
- oxygen
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- 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
- C22B15/006—Pyrometallurgy working up of molten copper, e.g. refining
-
- 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
Landscapes
- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Manufacture And Refinement Of Metals (AREA)
Abstract
The invention discloses a secondary copper refining process, which comprises the following steps of S1 feeding: starting a total oxygen burner, putting an acidic solvent/an alkaline solvent and a cold charge into a refining furnace for heating treatment, and adding inert gas in real time; s2 melting: introducing oxidizing atmosphere into the refining furnace for melting, slagging off for the first time after the cold charge is melted, analyzing the content of impurities and the content of oxygen, and determining the addition amount of a refining agent; s3 oxidation refining: setting an impurity removal sequence according to the density, oxygen affinity and mutual fusibility of different impurity elements, and adding corresponding refining agents into a refining furnace in sequence for refining to remove impurities in the copper liquid; s4 reduction refining: inserting a reducing pipe into the copper liquid, and introducing reducing gas through the reducing pipe for reduction; s5 copper discharging: closing the burner, covering a layer of charcoal on the surface of the copper liquid, discharging the copper liquid from the furnace eye, and adding rare earth into the tundish. The invention can reduce the impurity element content of the regenerated copper, improve the grade of the regenerated copper and provide high-quality raw materials for further deep processing.
Description
Technical Field
The invention relates to the technical field of copper smelting, in particular to a secondary copper refining process.
Background
The nonferrous metal of metallurgical material is an important basic raw material industry of national economy, and plays an important role in economic construction, national defense construction and social development. The non-ferrous metal has good cyclic recycling performance, the energy-saving and emission-reducing effects of the non-ferrous metal recycling are obvious, and the method is an important trend for the industrial development of the non-ferrous metal of the metallurgical material. Develops the metallurgical material regenerated non-ferrous metal industry, recycles the non-ferrous metal for many times, protects the primary mineral resources, saves the energy and reduces the environmental pollution. The processing and manufacturing of the reclaimed copper are important energy-saving and environment-friendly industries in the recycling economy. At present, the refining processing industry in the reclaimed copper industry has no recommended technical specification standard, so that reclaimed copper processing enterprises are dispersed, small in scale, non-standard, large in energy consumption and serious in pollution.
In the scrap copper refining process, Pb, Sn, Fe, Zn and Ni are the most common impurity elements, which have important influence on the performance of scrap copper, and when the content of the impurity elements is too high, the defects of cracks, hard particles, surface foreign matters and the like are often generated, so that the product quality is influenced. However, the impurity content in the scrap copper is high, the components are complex, and the limiting factors are many, so that the conventional general refining agent cannot effectively remove the impurity elements in the scrap copper. Therefore, aiming at the characteristics of 'multi-component' and 'high impurity' of scrap copper, the development of a targeted and efficient refining composite method is urgently needed.
Disclosure of Invention
The invention aims to provide a refining process of reclaimed copper, which can solve the problem that the impurity elements in the prior common refining agent can not be effectively removed due to high impurity content, complex components and multiple limiting factors in the reclaimed copper, realize the reduction of the impurity element content of the reclaimed copper, improve the grade of the reclaimed copper and provide high-quality raw materials for the next deep processing.
The embodiment of the invention is realized by the following technical scheme:
a secondary copper refining process comprises the following steps,
s1 feeding: starting a total oxygen burner, putting the acidic solvent/alkaline solvent and cold charge regenerated copper into a refining furnace for heating treatment, and adding inert gas in real time for stirring;
s2 melting: introducing oxidizing atmosphere into the refining furnace for melting, carrying out first slag skimming after all cold materials are melted, analyzing the content of impurities and the content of oxygen, and determining the addition amount of a refining agent;
s3 oxidation refining: setting an impurity removal sequence according to the density, oxygen affinity and mutual fusibility of different impurity elements, and adding corresponding refining agents into a refining furnace in sequence for refining to remove impurities in the copper liquid, wherein the impurities comprise zinc, iron, lead, tin and nickel;
s4 reduction refining: inserting a reducing pipe into the copper liquid, and introducing reducing gas through the reducing pipe for reduction;
s5 copper discharging: closing the burner, covering a layer of charcoal on the surface of the copper liquid, discharging the copper liquid from the furnace eye, and adding rare earth into the tundish to optimize the crystalline structure.
In one embodiment, the acidic solvent in the feed of step S1 includes silica and fluorite, the alkaline solvent includes one or more of slaked lime, soda ash and caustic soda, and the input amount of the acidic solvent/alkaline solvent is 0.6-2% of the input amount of the furnace.
In one embodiment, the reclaimed copper for cold charge in the charging in the step S1 is fed into the refining furnace in five batches, when the furnace temperature reaches 1300-1400 ℃, the first batch of reclaimed copper for cold charge is fed, the feeding amount of the first batch of reclaimed copper accounts for 30-40% of the furnace capacity, the furnace temperature is controlled to 1100-1300 ℃ after 1.5-2 h intervals, then four batches of reclaimed copper for cold charge are fed, the interval between each batch of feeding is 1-1.5 h, the feeding amount of the reclaimed copper for cold charge in each batch in the second to fourth batches accounts for 20-25% of the furnace capacity, and the liquid level of copper water is aligned with the furnace door after the fifth batch of reclaimed copper for cold charge is fed.
In one embodiment, in the step S2, the oxidizing atmosphere in the melting is a mixed gas of natural gas and pure oxygen, the oxygen-fuel ratio of the oxidizing atmosphere is 2-2.5: 1, the furnace temperature during melting is controlled to be 1120-1150 ℃, and the melting time is 6-8 hours.
In one embodiment, after the first batch or the second batch of cold material secondary copper is melted in the melting of step S2, the melting pool is poked and stirred by using an oxygen stirring pipe to accelerate melting, so that the raw material is heated uniformly, partial copper and impurities are oxidized, and after the furnace boiling phenomenon disappears, glass slag or cryolite is added.
In one embodiment, the refining agent in the oxidation refining of step S3 includes one or more of silica, cryolite, fluorite, iron filings, glass slag, quartz sand, river sand, lime, soda ash and caustic soda.
In one embodiment, if the heavily oxidized copper liquid appears in the oxidation refining of step S3, the copper liquid which is oxidized excessively is treated by an oxidation-reduction-reoxidation-reoduction process;
in the oxidation stage, the surface of molten copper is covered with low-sulfur coke, zinc is steamed by blowing, an acid refining agent is added for refining, and an alkaline refining agent is added for refining.
In one embodiment, the temperature of a hearth in the oxidation refining in the step S3 is controlled to be 1200-1250 ℃, the temperature of the molten copper is controlled to be 1150-1180 ℃, the content of impurities and the content of oxygen in the molten copper are measured every 0.5-1 h, and the pressure of a flue is controlled to be-90 Pa;
and inserting an oxygen injection pipe into the 2/3 deep part of the copper liquid, and introducing 0.3-0.5 MPa of compressed air into the copper liquid through the oxygen injection pipe.
In one embodiment, in the step S4, a flue valve of the refining furnace is closed in the reduction refining, the reduction gas is kept continuously introduced, the flue pressure is controlled to be-40 to-20 Pa, the temperature of the copper liquid after reduction is 1180 to 1200 ℃, and the oxygen content is controlled to be 200-260 ppm;
the reducing gas comprises natural gas, water vapor and nitrogen.
In one embodiment, the system further comprises an atmospheric pollution source automatic monitoring system and a high-temperature flue waste heat recovery and raw material heat storage system, wherein the atmospheric pollution source automatic monitoring system is communicated with the refining furnace, and the high-temperature flue waste heat recovery and raw material heat storage system is communicated with the refining furnace.
The technical scheme of the embodiment of the invention at least has the following advantages and beneficial effects:
according to the invention, through a pure oxygen combustion process, a natural gas reduction process and reasonable refining process parameters, the purposes of reducing the content of impurity elements of the reclaimed copper, improving the grade of the reclaimed copper and providing high-quality raw materials for further deep processing are realized.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are some embodiments of the present invention, but not all embodiments. The components of embodiments of the present invention generally described and illustrated herein may be arranged and designed in a wide variety of different configurations.
Thus, the detailed description of the embodiments of the present invention provided below is not intended to limit the scope of the invention as claimed, but is merely representative of selected embodiments of the invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
In the description of the present invention, it should be noted that if the terms "center", "upper", "lower", "left", "right", "vertical", "horizontal", "inner", "outer", etc. indicate an orientation or positional relationship, or an orientation or positional relationship that the product of the present invention is ordinarily placed when in use, it is merely for convenience of describing and simplifying the description, and it is not intended to indicate or imply that the device or element referred to must have a specific orientation, be constructed and operated in a specific orientation, and therefore, should not be construed as limiting the present invention. Furthermore, the terms "first," "second," "third," and the like are used solely to distinguish one from another and are not to be construed as indicating or implying relative importance.
Furthermore, the terms "horizontal", "vertical", "overhang" and the like do not require that the components be absolutely horizontal or overhang, but may be slightly inclined. For example, "horizontal" merely means that the direction is more horizontal than "vertical" and does not mean that the structure must be perfectly horizontal, but may be slightly inclined.
In the description of the present invention, it should be further noted that unless otherwise explicitly stated or limited, the terms "disposed," "mounted," "connected," and "connected" should be interpreted broadly, and may be, for example, fixedly connected, detachably connected, or integrally connected; can be mechanically or electrically connected; they may be connected directly or indirectly through intervening media, or they may be interconnected between two elements. The specific meanings of the above terms in the present invention can be understood in specific cases to those skilled in the art.
Example 1
A secondary copper refining process comprises the following steps,
s1 feeding: starting a total oxygen burner, putting an acidic solvent/alkaline solvent accounting for 0.6 percent of the furnace charging amount into a refining furnace, adding inert gas in real time for stirring, wherein the inert gas can be nitrogen or argon, and the purpose is to increase the melting speed and promote the uniform temperature of the copper liquid. The acid solvent can be silicon dioxide and fluorite, the alkaline solvent can be one or more of slaked lime, soda ash and caustic soda, which one or more acid solvents/alkaline solvents are specifically adopted is selected according to the target grade of the reclaimed copper product, then the cold material reclaimed copper is put into a refining furnace in five batches, and the specific operation is as follows: when the furnace temperature is 1300 ℃, adding a first batch of cold charge regenerated copper, wherein the adding amount of the first batch of regenerated copper accounts for 30% of the furnace capacity, controlling the furnace temperature to 1100 ℃ after 1.5h, adding four batches of cold charge regenerated copper, wherein the adding amount of each batch of cold charge regenerated copper accounts for 20% of the furnace capacity, and adding a fifth batch of cold charge regenerated copper to enable the copper water level to be flush with the furnace door.
Because the melting point of copper is 1083 ℃, in order to improve the melting rate of the reclaimed copper and avoid the increase of energy consumption and cost caused by heating the refining furnace to an over-high temperature, the technical scheme controls the temperature of the refining furnace to be 1300 ℃, the first batch of cold material reclaimed copper is added, after the first batch of cold material reclaimed copper is put into the furnace, the second batch of cold material reclaimed copper is added at an interval of 1.5h, and the purpose is to reserve time for melting the first batch of cold material reclaimed copper so as to ensure that the first batch of cold material reclaimed copper can be uniformly heated, and the copper liquid in each part of the refining furnace is at the same temperature. When the second to fifth batches of cold material regenerated copper are put in, because molten copper liquid exists in the furnace, in order to reduce energy consumption, the cost is reduced, the furnace temperature is controlled to be reduced to 1100 ℃ after the first batch of cold material regenerated copper is put in for 1.5 hours, the second to fifth batches of cold material regenerated copper are put in, the interval between each batch is 1 hour, the cold material regenerated copper put in enters the copper liquid from the beginning of the second batch of cold material regenerated copper, the cold material regenerated copper put in subsequently is gradually melted by the copper liquid under the heating of the copper liquid, and the liquid level of the copper liquid is just level with the furnace door after the fifth batch of cold material regenerated copper is added.
In the technical scheme, the combustor adopts the mixed gas of natural gas and pure oxygen as combustion gas.
S2 melting: introducing oxidizing atmosphere into the refining furnace for melting, carrying out first slag skimming after all cold materials are melted, analyzing the content of impurities and the content of oxygen, and determining the addition amount of a refining agent and the refining time;
the oxidizing atmosphere is a mixed gas of natural gas and pure oxygen, the oxygen-fuel ratio of the oxidizing atmosphere is 2:1, the temperature of a hearth during melting is controlled to be 1120 ℃, and the melting time is 6 hours;
in order to improve the combustion efficiency of the natural gas and avoid heat loss, the technical scheme adopts a pure oxygen combustion process, the ratio of pure oxygen to the natural gas is 2:1, the natural gas can be completely combusted, and the natural gas is combusted to release all heat. The compressed air is generally adopted for combustion supporting in the prior art, however, oxygen in the air only accounts for about 21%, and nitrogen accounting for about 78% does not participate in combustion, that is to say, the compressed air is introduced for combustion supporting, so that natural gas is not sufficiently combusted, a large amount of smoke is generated, and a large amount of heat can be taken away by the discharge of the smoke, so that heat loss is caused.
When all batches of cold charge secondary copper are put into the refining furnace, the melting stage begins to enter, and the time length of the melting stage is 6h and is equal to the sum of the time of the two stages of oxidation refining and reduction refining.
After the first batch or the second batch of cold material regenerated copper is melted, stirring a molten pool by using an oxygen beating pipe to accelerate melting, so that the raw materials are uniformly heated, partial copper and impurities are oxidized, and after the phenomenon of boiling a furnace disappears, adding glass slag or cryolite.
The oxygen injection pipe is used for introducing compressed air into the copper liquid, and because the density of the air is smaller than that of the copper, the compressed air in the copper liquid can become bubbles and float to the surface of the copper liquid, then the bubbles break on the surface of the copper liquid, the air in the released bubbles stirs the copper liquid through the floating motion of the bubbles in the copper liquid, the effect of stirring the copper liquid is achieved, and the raw materials are heated uniformly. And the compressed air contains oxygen, when bubbles float in the copper liquid, part of impurities in the copper liquid are oxidized into slag under the high-temperature condition after contacting the oxygen, and then the bubbles are brought to the surface of the copper liquid by the slag. The furnace boiling phenomenon can occur when the oxygen beating pipe is used for poking and stirring a molten pool, and after the furnace boiling phenomenon disappears, glass slag or cryolite is added into copper liquid, so that the slag has viscosity, and the slag is separated from the copper liquid.
S3 oxidation refining: during oxidation refining, the temperature of a hearth is controlled to be 1200 ℃, the temperature of molten copper is controlled to be 1150 ℃, the content of impurities and the content of oxygen in the molten copper are measured every 0.5h, and the pressure of a flue is controlled to be-90 Pa; setting an impurity removal sequence according to the density, oxygen affinity and mutual fusibility of different impurity elements, and adding corresponding refining agents into a refining furnace in sequence for refining to remove impurities such as zinc, iron, lead, tin, nickel and the like in the copper liquid;
the refining agent in the oxidation refining comprises one or more of silicon dioxide, ice crystals, fluorite, scrap iron, glass slag, quartz sand, river sand, lime, calcined soda and caustic soda.
In the refining process of the secondary copper, Pb, Sn, Fe, Zn and Ni are the most common impurity elements,
for the removal of impurities of Zn: because the boiling point of Zn is only 907 ℃, most of Zn can be directly volatilized at the oxidation refining temperature of 1150 ℃, the Zn is discharged out of the refining furnace along with furnace gas and then enters a dust collecting system, and a small part of Zn can be oxidized and forms ZnO, ZnO and SiO together with silicon oxide and iron oxide in the molten copper2、 ZnO·Fe2O3The purpose of impurity removal is further realized. If the Zn in the copper liquid is high, the temperature of the furnace is raised to 1300 ℃ after the Zn is oxidized into ZnO, charcoal or coke particles are added into the copper liquid, the ZnO is reduced into the Zn through a reduction reaction, and the Zn is volatilized due to high temperature, so that the purpose of removing impurities is achieved.
For the removal of impurities of Fe: the products of the copper liquid after the Fe is oxidized are FeO and Fe2O3Adding SiO into the copper liquid2To ensure that FeO and SiO in the copper liquid2Formation of FeSiO2，Fe2O3With SiO2Formation of Fe2(SiO3)， FeSiO2、Fe2(SiO3) Exists in the form of slag, and further realizes the purpose of impurity removal.
For the removal of Pb: oxidizing Pb in the copper liquid into PbO, adding quartz sand into the copper liquid, and generating PbSiO with the PbO and the quartz sand3，PbSiO3In the form of slag.
Impurity removal of Sn: in the copper liquid, Sn is oxidized into SnO and SnO2Adding an acidic refining agent and an alkaline refining agent into the molten copper, wherein the acidic refining agent can be SiO2The alkaline refining agent can be lime, soda ash or calcium carbonate, SnO2Acid slag is generated with the acid refining agent, alkaline slag is generated with the SnO and the alkaline refining agent, and both the acid slag and the alkaline slag exist in the form of slag, so that the purpose of removing impurities is realized.
For the removal of Ni: ni in the copper solution is oxidized into NiO, scrap iron is added into the copper solution, and NiO and the scrap iron generate NiO & Fe2O3，NiO·Fe2O3In the form of slag, intoThereby realizing the purpose of removing impurities.
If the copper liquid with serious oxidation appears in the oxidation refining, the copper liquid with excessive oxidation is treated by adopting an oxidation-reduction-reoxidation-reoduction process; in the oxidation stage, the surface of molten copper is covered with low-sulfur coke, zinc is steamed by blowing, an acid refining agent is added for refining, and an alkaline refining agent is added for refining.
An oxygen injection pipe is inserted into 2/3 deep in the copper liquid, and compressed air of 0.3MPa is introduced into the copper liquid through the oxygen injection pipe.
In order to realize better impurity removal effect, the copper liquid is stirred in the oxidation refining process, the oxygen injection pipe is inserted into the copper liquid in the oxidation refining process, 0.3MPa of compressed air is introduced into the copper liquid through the oxygen injection pipe, and the stirring of the copper liquid is realized through the compressed air.
S4 reduction refining: in the reduction refining, a flue valve of a refining furnace is closed, reducing gas is kept continuously introduced, the pressure of a flue is controlled to be-40 Pa, a reducing pipe is inserted into copper liquid for reduction, the temperature of the original copper liquid is 1180 ℃, the oxygen content is controlled to be 200ppm, the reducing gas comprises natural gas, water vapor and nitrogen, and other gases can be added into the reducing gas according to actual conditions.
Natural gas is used as a reducing agent, and Cu in copper liquid2O and CH4Reaction to generate Cu and H2O and CO2， H2O in the form of water vapor and CO2And finally, Cu is left after being discharged from the flue.
In the prior art, the wood inserting reduction process is adopted to realize reduction, a large amount of wood is consumed, and a large amount of smoke and dust are generated in the reduction process.
S5 copper discharging: closing the burner, covering a layer of charcoal on the surface of the copper liquid, discharging the copper liquid from the furnace eye, and adding rare earth into the tundish to optimize the crystalline structure. The rare earth can be lanthanide rare earth or cerium rare earth, and because rare earth is expensive, waste materials of lanthanide rare earth or cerium rare earth can also be used.
After the refining of the regenerated copper is finished, the burner is closed, a layer of charcoal is covered on the surface of the copper liquid, the purpose of covering the charcoal is to avoid the oxidation of the copper liquid due to the contact of the copper liquid and oxygen, the fire clay of the refining furnace is chiseled, a furnace eye is opened to enable the copper liquid in the furnace to flow out, and meanwhile, a carbon rod is used for controlling the flow of the copper liquid. The produced copper liquid contains the following impurities: zn is less than or equal to 100ppm, Pb is less than or equal to 50ppm, Ni is less than or equal to 80ppm, and Sn is less than or equal to 100 ppm.
The secondary copper refining process further comprises an atmospheric pollution source automatic monitoring system and a high-temperature flue waste heat recovery and raw material heat storage system, wherein the atmospheric pollution source automatic monitoring system is communicated with the refining furnace, and the high-temperature flue waste heat recovery and raw material heat storage system is communicated with the refining furnace. The automatic monitoring system of the atmospheric pollution source and the waste heat recovery and raw material heat storage system of the high-temperature flue can adopt the prior art, and can also adopt a specific system designed aiming at specific environment-friendly process conditions.
Example 2
A secondary copper refining process comprises the following steps,
s1 feeding: starting a total oxygen burner, putting an acidic solvent/alkaline solvent accounting for 0.8 percent of the capacity of the refining furnace into the refining furnace, adding inert gas in real time for stirring, wherein the inert gas can be nitrogen or argon, and the purpose is to increase the melting speed and promote the uniform temperature of the molten copper. The acid solvent can be silicon dioxide and fluorite, the alkaline solvent can be one or more of slaked lime, soda ash and caustic soda, which one or more acid solvents/alkaline solvents are specifically adopted is selected according to the target grade of the reclaimed copper product, then the cold material reclaimed copper is put into a refining furnace in five batches, and the specific operation is as follows: when the furnace temperature is 1350 ℃, adding a first batch of cold charge regenerated copper, wherein the adding amount of the first batch of regenerated copper accounts for 35% of the furnace capacity, controlling the furnace temperature to 1200 ℃ after 1.8h, adding four batches of cold charge regenerated copper, wherein the adding amount of each batch of cold charge regenerated copper accounts for 23% of the furnace capacity, and after adding a fifth batch of cold charge regenerated copper, the copper water level is flush with the furnace door.
Because the melting point of copper is 1083 ℃, in order to improve the melting rate of the reclaimed copper and avoid the increase of energy consumption and cost caused by heating the refining furnace to an over-high temperature, the technical scheme controls the temperature of the refining furnace to be 1350 ℃, the first batch of cold material reclaimed copper is added, the smelting temperature of copper in the industry is generally not more than 1400 ℃, after the first batch of cold material reclaimed copper is added into the furnace, the second batch of cold material reclaimed copper is added at an interval of 1.8h, and the aim is to reserve time for melting the first batch of cold material reclaimed copper so as to ensure that the first batch of cold material reclaimed copper can be uniformly heated and ensure that the copper liquid in each part of the refining furnace is at the same temperature. When the second to fifth batches of cold material reclaimed copper are put in, because molten copper liquid exists in the furnace, in order to reduce energy consumption, the cost is reduced, the furnace temperature is controlled to be reduced to 1200 ℃ after the first batch of cold material reclaimed copper is put in for 1.8 hours, the second to fifth batches of cold material reclaimed copper are put in, the interval between each batch is 1.3 hours, the cold material reclaimed copper put in enters the copper liquid from the beginning of the second batch of cold material reclaimed copper, because the temperature of the copper liquid is higher than the melting temperature of the copper, the cold material reclaimed copper which is subsequently put in is gradually melted by the copper liquid under the heating of the copper liquid, and the liquid level of the copper liquid is just level with the furnace door after the fifth batch of cold material reclaimed copper is added. In the technical scheme, the combustor adopts the mixed gas of natural gas and pure oxygen as combustion gas.
S2 melting: introducing oxidizing atmosphere into the refining furnace for melting, carrying out first slag skimming after all cold materials are melted, analyzing the content of impurities and the content of oxygen, and determining the addition amount of a refining agent and the refining time;
the oxidizing atmosphere is a mixed gas of natural gas and pure oxygen, the oxygen-fuel ratio of the oxidizing atmosphere is 2.3:1, the temperature of a hearth during melting is controlled to be 1130 ℃, and the melting time is 7 hours;
in order to improve the combustion efficiency of the natural gas and avoid heat loss, the technical scheme adopts a pure oxygen combustion process, the ratio of pure oxygen to the natural gas is 2.3:1, the natural gas can be completely combusted, and the natural gas is combusted to release all heat. The compressed air is generally adopted for combustion supporting in the prior art, however, oxygen in the air only accounts for about 21%, and nitrogen accounting for about 78% does not participate in combustion, that is to say, the compressed air is introduced for combustion supporting, so that natural gas is not sufficiently combusted, a large amount of smoke is generated, and a large amount of heat can be taken away by the discharge of the smoke, so that heat loss is caused.
When all batches of cold charge secondary copper are put into the refining furnace, the melting stage begins to enter, and the time length of the melting stage is 7h and is equal to the sum of the time consumption of the oxidation refining stage and the reduction refining stage.
After the first batch or the second batch of cold material regenerated copper is melted, stirring a molten pool by using an oxygen beating pipe to accelerate melting, so that the raw materials are uniformly heated, partial copper and impurities are oxidized, and after the phenomenon of boiling a furnace disappears, adding glass slag or cryolite.
The oxygen injection pipe is used for introducing compressed air into the copper liquid, and because the density of the air is smaller than that of the copper, the compressed air in the copper liquid can become bubbles and float to the surface of the copper liquid, then the bubbles break on the surface of the copper liquid, the air in the released bubbles stirs the copper liquid through the floating motion of the bubbles in the copper liquid, the effect of stirring the copper liquid is achieved, and the raw materials are heated uniformly. And the compressed air contains oxygen, when bubbles float in the copper liquid, part of impurities in the copper liquid are oxidized into slag under the high-temperature condition after contacting the oxygen, and then the bubbles are brought to the surface of the copper liquid by the slag. The furnace boiling phenomenon can occur when the oxygen beating pipe is used for poking and stirring a molten pool, and after the furnace boiling phenomenon disappears, glass slag or cryolite is added into copper liquid, so that the slag has viscosity, and the slag is separated from the copper liquid.
S3 oxidation refining: during oxidation refining, the temperature of a hearth is controlled to be 1225 ℃, the temperature of the copper liquid is controlled to be 1165 ℃, the content of impurities and the content of oxygen in the copper liquid are measured every 0.7 hour, and the pressure of a flue is controlled to be-90 Pa; setting an impurity removal sequence according to the density, oxygen affinity and mutual fusibility of different impurity elements, and adding corresponding refining agents into a refining furnace in sequence for refining to remove impurities such as zinc, iron, lead, tin, nickel and the like in the copper liquid;
the refining agent in the oxidation refining comprises one or more of silicon dioxide, cryolite, fluorite, scrap iron, glass slag, quartz sand, river sand, lime, calcined soda and caustic soda.
In the refining process of the secondary copper, Pb, Sn, Fe, Zn and Ni are the most common impurity elements,
for the removal of impurities of Zn: because the boiling point of Zn is only 907 ℃, most of Zn can be directly volatilized at the oxidation refining temperature of 1165 ℃, the Zn is discharged out of the refining furnace along with furnace gas and then enters a dust collecting system, and a small part of Z isn is oxidized and forms ZnO, SiO with silicon oxide and iron oxide in the copper solution2、 ZnO·Fe2O3The purpose of impurity removal is further realized. If the Zn in the copper liquid is high, the temperature of the furnace is increased to 1325 ℃ after the Zn is oxidized into ZnO, charcoal or coke particles are added into the copper liquid, the ZnO is reduced into the Zn through a reduction reaction, and the Zn is volatilized due to high temperature, so that the purpose of removing impurities is achieved.
For the removal of impurities of Fe: the products of the copper liquid after the Fe is oxidized are FeO and Fe2O3Adding SiO into the copper liquid2To ensure that FeO and SiO in the copper liquid2Formation of FeSiO2，Fe2O3With SiO2Formation of Fe2(SiO3)， FeSiO2、Fe2(SiO3) Exists in the form of slag, and further realizes the purpose of impurity removal.
For the removal of Pb: oxidizing Pb in the copper liquid into PbO, adding quartz sand into the copper liquid, and generating PbSiO with the PbO and the quartz sand3，PbSiO3In the form of slag.
Impurity removal of Sn: in the copper liquid, Sn is oxidized into SnO and SnO2Adding an acidic refining agent and an alkaline refining agent into the molten copper, wherein the acidic refining agent can be SiO2The alkaline refining agent can be lime, soda ash or calcium carbonate, SnO2Acid slag is generated with the acid refining agent, alkaline slag is generated with the SnO and the alkaline refining agent, and both the acid slag and the alkaline slag exist in the form of slag, so that the purpose of removing impurities is realized.
For the removal of Ni: ni in the copper solution is oxidized into NiO, scrap iron is added into the copper solution, and NiO and the scrap iron generate NiO & Fe2O3，NiO·Fe2O3Exists in the form of slag, and further realizes the purpose of impurity removal.
If the copper liquid with serious oxidation appears in the oxidation refining, the copper liquid with excessive oxidation is treated by adopting an oxidation-reduction-reoxidation-reoduction process; in the oxidation stage, the surface of molten copper is covered with low-sulfur coke, zinc is steamed by blowing, an acid refining agent is added for refining, and an alkaline refining agent is added for refining.
An oxygen injection pipe is inserted into 2/3 deep in the copper liquid, and compressed air of 0.4MPa is introduced into the copper liquid through the oxygen injection pipe.
In order to realize better impurity removal effect, the copper liquid is stirred in the oxidation refining process, the oxygen injection pipe is inserted into the copper liquid in the oxidation refining process, 0.4MPa of compressed air is introduced into the copper liquid through the oxygen injection pipe, and the stirring of the copper liquid is realized through the compressed air.
S4 reduction refining: in the reduction refining, a flue valve of a refining furnace is closed, reducing gas is kept continuously introduced, the pressure of a flue is controlled to be-30 Pa, a reducing pipe is inserted into copper liquid, reducing gas mixed by a plurality of gases such as natural gas, water vapor, nitrogen and the like is introduced through the reducing pipe for reduction, the temperature of the copper liquid after reduction is 1190 ℃, the oxygen content is controlled to be 240ppm, the reducing gas comprises natural gas, water vapor and nitrogen, and other gases can be added into the reducing gas according to actual conditions.
Natural gas is used as a reducing agent, and Cu in copper liquid2O and CH4Reaction to generate Cu and H2O and CO2， H2O in the form of water vapor and CO2And finally, Cu is left after being discharged from the flue.
In the prior art, the wood inserting reduction process is adopted to realize reduction, a large amount of wood is consumed, and a large amount of smoke and dust are generated in the reduction process.
S5 copper discharging: closing the burner, covering a layer of charcoal on the surface of the copper liquid, discharging the copper liquid from the furnace eye, and adding rare earth into the tundish to optimize the crystalline structure. The rare earth can be lanthanide rare earth or cerium rare earth, and because rare earth is expensive, waste materials of lanthanide rare earth or cerium rare earth can also be used.
After the refining of the regenerated copper is finished, the burner is closed, a layer of charcoal is covered on the surface of the copper liquid, the purpose of covering the charcoal is to avoid the oxidation of the copper liquid due to the contact of the copper liquid and oxygen, the fire clay of the refining furnace is chiseled, a furnace eye is opened to enable the copper liquid in the furnace to flow out, and meanwhile, a carbon rod is used for controlling the flow of the copper liquid. The produced copper liquid contains the following impurities: zn is less than or equal to 100ppm, Pb is less than or equal to 50ppm, Ni is less than or equal to 80ppm, and Sn is less than or equal to 100 ppm.
The secondary copper refining process further comprises an atmospheric pollution source automatic monitoring system and a high-temperature flue waste heat recovery and raw material heat storage system, wherein the atmospheric pollution source automatic monitoring system is communicated with the refining furnace, and the high-temperature flue waste heat recovery and raw material heat storage system is communicated with the refining furnace. The automatic monitoring system of the atmospheric pollution source and the waste heat recovery and raw material heat storage system of the high-temperature flue can adopt the prior art, and can also adopt a specific system designed aiming at specific environment-friendly process conditions.
Example 3
A secondary copper refining process comprises the following steps,
s1 feeding: starting a total oxygen burner, putting an acidic solvent/alkaline solvent accounting for 1% of the amount of the refining furnace into the refining furnace, adding inert gas in real time for stirring, wherein the inert gas can be nitrogen or argon, and aims to increase the melting speed and promote the temperature of the copper liquid to be uniform. The acid solvent can be silicon dioxide and fluorite, the alkaline solvent can be one or more of slaked lime, soda ash and caustic soda, which one or more acid solvents/alkaline solvents are specifically adopted is selected according to the target grade of the reclaimed copper product, then the cold material reclaimed copper is put into a refining furnace in five batches, and the specific operation is as follows: when the furnace temperature is 1400 ℃, adding a first batch of cold charge regenerated copper, wherein the adding amount of the first batch of regenerated copper accounts for 40% of the furnace capacity, controlling the furnace temperature to 1300 ℃ after 2h, adding four batches of cold charge regenerated copper, wherein the adding amount of each batch of cold charge regenerated copper accounts for 25% of the furnace capacity, and adding a fifth batch of cold charge regenerated copper to enable the copper water level to be flush with the furnace door.
Because the melting point of copper is 1083 ℃, in order to improve the melting rate of the reclaimed copper and avoid the increase of energy consumption and cost caused by heating the refining furnace to an over-high temperature, the technical scheme controls the temperature of the refining furnace to 1400 ℃, the first batch of cold material reclaimed copper is added, after the first batch of cold material reclaimed copper is put into the furnace, the second batch of cold material reclaimed copper is added at an interval of 2 hours, and the purpose is to reserve time for melting the first batch of cold material reclaimed copper so as to ensure that the first batch of cold material reclaimed copper can be uniformly heated, and the copper liquid in each part of the refining furnace is at the same temperature. When the second to fifth batches of cold material regenerated copper are put in, because molten copper liquid exists in the furnace, in order to reduce energy consumption, the cost is reduced, the furnace temperature is controlled to be reduced to 1300 ℃ after the first batch of cold material regenerated copper is put in for 2 hours, the second to fifth batches of cold material regenerated copper are put in, the interval between each batch is 1.5 hours, the cold material regenerated copper put in enters the copper liquid from the beginning of the second batch of cold material regenerated copper, because the temperature of the copper liquid is higher than the melting temperature of the copper, the cold material regenerated copper which is subsequently put in is gradually melted by the copper liquid under the heating of the copper liquid, and the liquid level of the copper liquid is just level with the furnace door after the fifth batch of cold material regenerated copper is added. In the technical scheme, the combustor adopts the mixed gas of natural gas and pure oxygen as combustion gas.
S2 melting: introducing oxidizing atmosphere into the refining furnace for melting, carrying out first slag skimming after all cold materials are melted, analyzing the content of impurities and the content of oxygen, and determining the addition amount of a refining agent and the refining time;
the oxidizing atmosphere is a mixed gas of natural gas and pure oxygen, the oxygen-fuel ratio of the oxidizing atmosphere is 2.5:1, the temperature of a hearth during melting is controlled to 1150 ℃, and the melting time is 8 hours;
in order to improve the combustion efficiency of the natural gas and avoid heat loss, the technical scheme adopts a pure oxygen combustion process, the ratio of pure oxygen to the natural gas is 2.5:1, the natural gas can be completely combusted, and the natural gas is combusted to release all heat. The compressed air is generally adopted for combustion supporting in the prior art, however, oxygen in the air only accounts for about 21%, and nitrogen accounting for about 78% does not participate in combustion, that is to say, the compressed air is introduced for combustion supporting, so that natural gas is not sufficiently combusted, a large amount of smoke is generated, and a large amount of heat can be taken away by the discharge of the smoke, so that heat loss is caused.
When all batches of cold charge secondary copper are put into the refining furnace, the melting stage begins to enter, and the time length of the melting stage is 8h and is equal to the sum of the time consumption of the oxidation refining stage and the reduction refining stage.
After the first batch or the second batch of cold material regenerated copper is melted, stirring a molten pool by using an oxygen beating pipe to accelerate melting, so that the raw materials are uniformly heated, partial copper and impurities are oxidized, and after the phenomenon of boiling a furnace disappears, adding glass slag or cryolite.
The oxygen injection pipe is used for introducing compressed air into the copper liquid, and because the density of the air is smaller than that of the copper, the compressed air in the copper liquid can become bubbles and float to the surface of the copper liquid, then the bubbles break on the surface of the copper liquid, the air in the released bubbles stirs the copper liquid through the floating motion of the bubbles in the copper liquid, the effect of stirring the copper liquid is achieved, and the raw materials are heated uniformly. And the compressed air contains oxygen, when bubbles float in the copper liquid, part of impurities in the copper liquid are oxidized into slag under the high-temperature condition after contacting the oxygen, and then the bubbles are brought to the surface of the copper liquid by the slag. The furnace boiling phenomenon can occur when the oxygen beating pipe is used for poking and stirring a molten pool, and after the furnace boiling phenomenon disappears, glass slag or cryolite is added into copper liquid, so that the slag has viscosity, and the slag is separated from the copper liquid.
S3 oxidation refining: during oxidation refining, controlling the temperature of a hearth at 1250 ℃, controlling the temperature of molten copper at 1180 ℃, measuring the content of impurities and the content of oxygen in the molten copper once every 1 hour, and controlling the pressure of a flue to be-90 Pa; setting an impurity removal sequence according to the density, oxygen affinity and mutual fusibility of different impurity elements, and adding corresponding refining agents into a refining furnace in sequence for refining to remove impurities such as zinc, iron, lead, tin, nickel and the like in the copper liquid;
the refining agent in the oxidation refining comprises one or more of silicon dioxide, cryolite, fluorite, scrap iron, glass slag, quartz sand, river sand, lime, calcined soda and caustic soda.
In the refining process of the secondary copper, Pb, Sn, Fe, Zn and Ni are the most common impurity elements,
for the removal of impurities of Zn: because the boiling point of Zn is only 907 ℃, most of Zn can be directly volatilized at the oxidation refining temperature of 1180 ℃, the Zn is discharged out of the refining furnace along with furnace gas and then enters a dust collecting system, and a small part of Zn can be oxidized and forms ZnO, ZnO and SiO together with silicon oxide and iron oxide in the copper liquid2、 ZnO·Fe2O3The purpose of impurity removal is further realized. If the Zn content in the copper liquid is high, the temperature of the furnace is raised to 1350 ℃ after the Zn is oxidized into ZnO, charcoal or coke particles are added into the copper liquid, the ZnO is reduced into Zn through reduction reaction, and the Zn is volatilized due to high temperature, so that the impurity removal is realizedThe purpose of (1).
For the removal of impurities of Fe: the products of the copper liquid after the Fe is oxidized are FeO and Fe2O3Adding SiO into the copper liquid2To ensure that FeO and SiO in the copper liquid2Formation of FeSiO2，Fe2O3With SiO2Formation of Fe2(SiO3)， FeSiO2、Fe2(SiO3) Exists in the form of slag, and further realizes the purpose of impurity removal.
For the removal of Pb: oxidizing Pb in the copper liquid into PbO, adding quartz sand into the copper liquid, and generating PbSiO with the PbO and the quartz sand3，PbSiO3In the form of slag.
Impurity removal of Sn: in the copper liquid, Sn is oxidized into SnO and SnO2Adding an acidic refining agent and an alkaline refining agent into the molten copper, wherein the acidic refining agent can be SiO2The alkaline refining agent can be lime, soda ash or calcium carbonate, SnO2Acid slag is generated with the acid refining agent, alkaline slag is generated with the SnO and the alkaline refining agent, and both the acid slag and the alkaline slag exist in the form of slag, so that the purpose of removing impurities is realized.
For the removal of Ni: ni in the copper solution is oxidized into NiO, scrap iron is added into the copper solution, and NiO and the scrap iron generate NiO & Fe2O3，NiO·Fe2O3Exists in the form of slag, and further realizes the purpose of impurity removal.
If the copper liquid with serious oxidation appears in the oxidation refining, the copper liquid with excessive oxidation is treated by adopting an oxidation-reduction-reoxidation-reoduction process; in the oxidation stage, the surface of molten copper is covered with low-sulfur coke, zinc is steamed by blowing, an acid refining agent is added for refining, and an alkaline refining agent is added for refining.
An oxygen injection pipe is inserted into 2/3 deep in the copper liquid, and compressed air of 0.5MPa is introduced into the copper liquid through the oxygen injection pipe.
In order to realize better impurity removal effect, the copper liquid is stirred in the oxidation refining process, the oxygen injection pipe is inserted into the copper liquid in the oxidation refining process, 0.5MPa of compressed air is introduced into the copper liquid through the oxygen injection pipe, and the stirring of the copper liquid is realized through the compressed air.
S4 reduction refining: in the reduction refining, a flue valve of a refining furnace is closed, reducing gas mixed with various gases such as natural gas, water vapor and nitrogen is kept continuously introduced, the pressure of a flue is controlled to be-20 MPa, a reducing pipe is inserted into copper liquid, the reducing gas mixed with various gases such as natural gas, water vapor and nitrogen is introduced through the reducing pipe for reduction, the temperature of the reduced copper liquid is 1200 ℃, the oxygen content is controlled to be 260ppm, the reducing gas comprises natural gas, water vapor and nitrogen, and other gases can be added into the reducing gas according to actual conditions.
Natural gas is used as a reducing agent, and Cu in copper liquid2O and CH4Reaction to generate Cu and H2O and CO2， H2O in the form of water vapor and CO2And finally, Cu is left after being discharged from the flue.
In the prior art, the wood inserting reduction process is adopted to realize reduction, a large amount of wood is consumed, and a large amount of smoke and dust are generated in the reduction process.
S5 copper discharging: closing the burner, covering a layer of charcoal on the surface of the copper liquid, discharging the copper liquid from the furnace eye, and adding rare earth into the tundish to optimize the crystalline structure. The rare earth can be lanthanide rare earth or cerium rare earth, and because rare earth is expensive, waste materials of lanthanide rare earth or cerium rare earth can also be used.
After the refining of the regenerated copper is finished, the burner is closed, a layer of charcoal is covered on the surface of the copper liquid, the purpose of covering the charcoal is to avoid the oxidation of the copper liquid due to the contact of the copper liquid and oxygen, the fire clay of the refining furnace is chiseled, a furnace eye is opened to enable the copper liquid in the furnace to flow out, and meanwhile, a carbon rod is used for controlling the flow of the copper liquid. The produced copper liquid contains the following impurities: zn is less than or equal to 100ppm, Pb is less than or equal to 50ppm, Ni is less than or equal to 80ppm, and Sn is less than or equal to 100 ppm.
The secondary copper refining process further comprises an atmospheric pollution source automatic monitoring system and a high-temperature flue waste heat recovery and raw material heat storage system, wherein the atmospheric pollution source automatic monitoring system is communicated with the refining furnace, and the high-temperature flue waste heat recovery and raw material heat storage system is communicated with the refining furnace. The automatic monitoring system of the atmospheric pollution source and the waste heat recovery and raw material heat storage system of the high-temperature flue can adopt the prior art, and can also adopt a specific system designed aiming at specific environment-friendly process conditions.
The above is only a preferred embodiment of the present invention, and is not intended to limit the present invention, and various modifications and changes will occur to those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. A secondary copper refining process is characterized in that: comprises the following steps of (a) carrying out,
s1 feeding: starting a total oxygen burner, putting the acidic solvent/alkaline solvent and cold charge regenerated copper into a refining furnace for heating treatment, and adding inert gas in real time for stirring;
s2 melting: introducing oxidizing atmosphere into the refining furnace for melting, carrying out first slag skimming after all cold materials are melted, analyzing the content of impurities and the content of oxygen, and determining the addition amount of a refining agent;
s3 oxidation refining: setting an impurity removal sequence according to the density, oxygen affinity and mutual fusibility of different impurity elements, and adding corresponding refining agents into a refining furnace in sequence for refining to remove impurities in the copper liquid, wherein the impurities comprise zinc, iron, lead, tin and nickel;
s4 reduction refining: inserting a reducing pipe into the copper liquid, and introducing reducing gas through the reducing pipe for reduction;
s5 copper discharging: closing the burner, covering a layer of charcoal on the surface of the copper liquid, discharging the copper liquid from the furnace eye, and adding rare earth into the tundish to optimize the crystalline structure.
2. A secondary copper refining process according to claim 1, characterized in that: the acidic solvent in the feeding in the step S1 comprises silicon dioxide and fluorite, the alkaline solvent comprises one or more of slaked lime, soda ash and caustic soda, and the adding amount of the acidic solvent/the alkaline solvent accounts for 0.6-2% of the adding amount of the furnace.
3. A secondary copper refining process according to claim 2, characterized in that: and S1, feeding the cold material reclaimed copper into the refining furnace in five batches, feeding the first batch of cold material reclaimed copper when the furnace temperature reaches 1300-1400 ℃, wherein the feeding amount of the first batch of reclaimed copper accounts for 30-40% of the furnace capacity, controlling the furnace temperature to 1100-1300 ℃ after 1.5-2 h intervals, feeding the four batches of cold material reclaimed copper, wherein the feeding interval of each batch is 1-1.5 h, the feeding amount of each batch of cold material reclaimed copper accounts for 20-25% of the furnace capacity in the second-fourth batches, and after feeding the fifth batch of cold material reclaimed copper, enabling the copper water level to be flush with the furnace door.
4. A secondary copper refining process according to claim 1, characterized in that: in the step S2, the oxidizing atmosphere in melting is a mixed gas of natural gas and pure oxygen, the oxygen-fuel ratio of the oxidizing atmosphere is 2-2.5: 1, the temperature of a hearth during melting is controlled to be 1120-1150 ℃, and the melting time is 6-8 hours.
5. A secondary copper refining process according to claim 4, characterized in that: and (S2) after the first batch or the second batch of cold material secondary copper is melted in the melting process, poking and stirring the melting pool by using an oxygen stirring pipe to accelerate melting, heating the raw materials uniformly, oxidizing partial copper and impurities, and adding glass slag or cryolite after the boiling furnace phenomenon disappears.
6. A secondary copper refining process according to claim 1, characterized in that: and the refining agent in the oxidation refining in the step S3 comprises one or more of silicon dioxide, cryolite, fluorite, scrap iron, glass slag, quartz sand, river sand, lime, soda ash and caustic soda.
7. A secondary copper refining process according to claim 6, characterized in that: if the copper liquid with serious oxidation appears in the oxidation refining in the step S3, the copper liquid with excessive oxidation is treated by adopting an oxidation-reduction-reoxidation-reoducing process;
in the oxidation stage, the surface of molten copper is covered with low-sulfur coke, zinc is steamed by blowing, an acid refining agent is added for refining, and an alkaline refining agent is added for refining.
8. A secondary copper refining process according to claim 1, characterized in that: in the step S3, the temperature of a hearth in oxidation refining is controlled to be 1200-1250 ℃, the temperature of the copper liquid is controlled to be 1150-1180 ℃, the content of impurities and the content of oxygen in the copper liquid are measured every 0.5-1 h, and the pressure of a flue is controlled to be-90 Pa;
and inserting an oxygen injection pipe into the 2/3 deep part of the copper liquid, and introducing 0.3-0.5 MPa of compressed air into the copper liquid through the oxygen injection pipe.
9. A secondary copper refining process according to claim 1, characterized in that: in the step S4, a flue valve of the refining furnace is closed in the reduction refining, the reduction gas is kept continuously introduced, the pressure of the flue is controlled to be-40 to-20 Pa, the temperature of the copper liquid after reduction is 1180 to 1200 ℃, and the oxygen content is controlled to be 200-260 ppm;
the reducing gas comprises natural gas, water vapor and nitrogen.
10. A secondary copper refining process according to claim 1, characterized in that: the system also comprises an atmospheric pollution source automatic monitoring system and a high-temperature flue waste heat recovery and raw material heat storage system, wherein the atmospheric pollution source automatic monitoring system is communicated with the refining furnace, and the high-temperature flue waste heat recovery and raw material heat storage system is communicated with the refining furnace.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911412919.0A CN110983067A (en) | 2019-12-31 | 2019-12-31 | Secondary copper refining process |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911412919.0A CN110983067A (en) | 2019-12-31 | 2019-12-31 | Secondary copper refining process |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN110983067A true CN110983067A (en) | 2020-04-10 |
Family
ID=70079766
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201911412919.0A Pending CN110983067A (en) | 2019-12-31 | 2019-12-31 | Secondary copper refining process |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110983067A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113481381A (en) * | 2021-06-17 | 2021-10-08 | 张家港联合铜业有限公司 | Copper fire refining process based on carbon dioxide |
| CN116396101A (en) * | 2023-04-24 | 2023-07-07 | 大冶有色金属有限责任公司 | Method for maintaining reduction tube of regenerated copper refining reverberatory furnace |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4315775A (en) * | 1979-11-28 | 1982-02-16 | Southwire Company | Continuous melting and refining of secondary and/or blister copper |
| RU2391420C1 (en) * | 2009-06-24 | 2010-06-10 | Игорь Олегович Попов | Method of fire copper refinement |
| CN101914689A (en) * | 2010-09-03 | 2010-12-15 | 绵阳金鑫铜业有限公司 | Method for producing low-oxygen electro-technical copper wire blank with waste copper |
| CN102234725A (en) * | 2010-04-24 | 2011-11-09 | 大冶有色金属集团控股有限公司 | Continuous production technology for miscellaneous copper recycling and positive plate casting |
| CN103114208A (en) * | 2013-03-12 | 2013-05-22 | 绵阳铜鑫铜业有限公司 | Method for producing oxygen-free copper rod from secondary copper |
| CN103725897A (en) * | 2013-12-27 | 2014-04-16 | 中南大学 | Method for directly producing high-purity oxygen-free copper by pyrogenic process continuous refining of scrap copper |
-
2019
- 2019-12-31 CN CN201911412919.0A patent/CN110983067A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4315775A (en) * | 1979-11-28 | 1982-02-16 | Southwire Company | Continuous melting and refining of secondary and/or blister copper |
| RU2391420C1 (en) * | 2009-06-24 | 2010-06-10 | Игорь Олегович Попов | Method of fire copper refinement |
| CN102234725A (en) * | 2010-04-24 | 2011-11-09 | 大冶有色金属集团控股有限公司 | Continuous production technology for miscellaneous copper recycling and positive plate casting |
| CN101914689A (en) * | 2010-09-03 | 2010-12-15 | 绵阳金鑫铜业有限公司 | Method for producing low-oxygen electro-technical copper wire blank with waste copper |
| CN103114208A (en) * | 2013-03-12 | 2013-05-22 | 绵阳铜鑫铜业有限公司 | Method for producing oxygen-free copper rod from secondary copper |
| CN103725897A (en) * | 2013-12-27 | 2014-04-16 | 中南大学 | Method for directly producing high-purity oxygen-free copper by pyrogenic process continuous refining of scrap copper |
Non-Patent Citations (1)
| Title |
|---|
| 贺晓红等编: "《铜冶炼生产技术》", 28 February 2017, 冶金工业出版社 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113481381A (en) * | 2021-06-17 | 2021-10-08 | 张家港联合铜业有限公司 | Copper fire refining process based on carbon dioxide |
| CN116396101A (en) * | 2023-04-24 | 2023-07-07 | 大冶有色金属有限责任公司 | Method for maintaining reduction tube of regenerated copper refining reverberatory furnace |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101768670B (en) | Method for smelting lead-containing material | |
| CN101255500B (en) | Smelting method for separating value metals from anode mud by firing process and device thereof | |
| CN101880774B (en) | Process for removing copper slag and producing crude lead and lead copper matte by adopting melting treatment in bottom-blowing melting bath and device thereof | |
| CN101538629A (en) | Process and device for smelting chromium irons and chromium-containing molten iron by using chromium ore powder | |
| CN101760631B (en) | Process for smelting copper with infinity furnace | |
| CN102586618B (en) | Process of smelting iron pyrite | |
| CN111235388B (en) | Side-top-blown molten pool tin smelting process and smelting furnace | |
| CN102965509A (en) | Method and device for treating daub and iron-rich heavy metal solid waste of waste lead-acid storage battery | |
| CN102140585A (en) | Method for smelting nickel ore concentrate by using smelting furnace | |
| CN112981097B (en) | Furnace wall and slag adhering method of water-cooling-wall-free nickel-iron ore thermoelectric furnace | |
| CN201648490U (en) | Lead-containing material smelting device | |
| CN110983067A (en) | Secondary copper refining process | |
| CN111411234A (en) | Jet smelting electrothermal reduction furnace and method for smelting zinc-containing material | |
| CN111893310A (en) | Harmless recycling treatment method for solid hazardous waste | |
| JPH0215130A (en) | Utilization of zinc-containing metallurgical dust and sludge | |
| CN111254290A (en) | Full thermal state copper matte continuous converting method | |
| CN105420515B (en) | Process and device for melting laterite-nickel ore in oxygen-enriched reinforcement melting pool to obtain ferronickel | |
| CN101956035B (en) | Iron-containing material slag bath smelting reduction steelmaking technical method and device | |
| CN103205772A (en) | Method for producing electrolytic manganese dioxide | |
| CN116854489A (en) | Technological method for improving volume density of electrofusion compact corundum | |
| US3547623A (en) | Method of recovering iron oxide from fume containing zinc and/or lead and sulfur and iron oxide particles | |
| CN110656215A (en) | Method for preventing unsuccessful blowing and igniting of converter | |
| CN212247151U (en) | Jet smelting electric heating reduction furnace | |
| CN111850304B (en) | Copper slag treatment system and method | |
| CN111172409B (en) | Recovery smelting process of tin-containing material |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20200410 |