CN108559855B - Continuous refining device of blister copper pyrogenic process - Google Patents
Continuous refining device of blister copper pyrogenic process Download PDFInfo
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Abstract
The invention provides a crude copper fire continuous refining device, which comprises: the furnace comprises a furnace body and a flue port arranged at the top of the furnace body, wherein a charging oxidation area, a reduction area and a casting area which are separated by a partition wall and are communicated with each other at the bottom are arranged in the furnace body, and the reduction area is positioned between the charging oxidation area and the casting area. The device for continuously refining the blister copper by the fire method has the advantages of low energy consumption, environmental friendliness, high automation level, high production efficiency and the like, can realize continuous feeding of the blister copper and continuous casting of anode copper, can simultaneously carry out oxidation and reduction processes during operation, can shorten the operation time, improve the utilization rate of equipment, has stable smoke gas amount and smoke gas components, and can intensively treat and recover waste heat.
Description
Technical Field
The invention relates to the technical field of non-ferrous metallurgy, in particular to a crude copper fire continuous refining device.
Background
The pyrometallurgical process for copper generally comprises three steps of copper concentrate smelting, copper matte converting and blister copper refining. The crude copper produced by copper matte converting generally contains 98.5-99.5% of copper, and the other impurity elements comprise sulfur, oxygen, iron, arsenic, antimony, zinc, tin, lead, bismuth, nickel, cobalt and the like, and usually also contain rare and dispersed metals such as selenium, tellurium, gold, silver and the like and noble metals. Impurity elements can have adverse effects on the conductivity and mechanical properties of copper, and valuable elements such as rare metals, precious metals and the like need to be comprehensively recovered, so that the resource utilization rate is improved. The purpose of the crude copper fire refining is to remove impurity elements as much as possible so as to reduce the influence of the impurity elements on electrolytic refining; on the other hand, the anode plate with flat and smooth plate surface, uniform thickness, no flash and burr and good verticality is cast to meet the process requirement of electrolytic refining.
The fire refining of the blister copper mainly comprises two processes of oxidation and reduction. The oxidation stage is to feed an oxidant into the molten blister copper at an elevated temperature, the Cu in the melt being first oxidized to Cu2O，Cu2The O reacts with other metal impurity elements to oxidize the O, and the generated metal oxide has low solubility in copper water and light specific gravity, and can quickly float out of the liquid surface to form slag and be discharged. After the oxidation is completed, the copper liquid contains 0.5-1.5% of oxygen, and Cu is used during solidification2The O is precipitated in the form and distributed on the grain boundary of Cu, which causes harm to electrolytic refining and needs reduction deoxidation. The reduction stage is to feed a reducing agent into the molten copper at a high temperature, the reducing agent and Cu in the melt2And (4) deoxidizing through an O reaction, and casting after the oxygen content in the copper liquid is reduced to 0.1-0.2%.
At present, a reverberatory furnace, a rotary refining furnace and a tilting furnace are commonly adopted at home and abroad for the fire refining of the blister copper. The reverberatory furnace has low automation degree, high labor intensity of manual pipe insertion oxidation reduction, poor working environment caused by much smoke leakage, high energy consumption and low production efficiency; the rotary refining furnace has higher automation level, large processing capacity and higher production efficiency, but is not suitable for processing cold materials due to deep molten pool, small heated area and slow material melting, and the converter control system is complicated; the tilting furnace combines the characteristics of a reverberatory furnace and a rotary refining furnace, but has special furnace body shape, complex structure and high investment, and the furnace body tilts during operation, thereby having great influence on the stability of the furnace top and the furnace wall. More importantly, the three widely-applied crude copper fire refining processes have the common defect that the process is periodically operated, and the refining process is divided into four periods, namely a charging melting period, an oxidation slagging-off period, a reduction period and a casting period. When periodic operation is adopted, the flue gas in the oxidation period contains SO2The concentration is high and needs to be treated independently, the concentration of CO contained in the flue gas in the reduction period is high and needs to be combusted secondarily, the fluctuation of the flue gas amount in four periods is large, the centralized treatment cannot be realized, the subsequent flue gas treatment system is complex, and the heat brought away by the flue gas cannot be recovered. Meanwhile, the periodic operation results in long operation time of each furnace, large fuel consumption, low equipment utilization rate of the casting device and influence on the production efficiency.
Disclosure of Invention
Aiming at the defects in the prior art, the invention aims to provide a crude copper fire continuous refining device which can realize continuous feeding of crude copper and continuous casting of anode copper and can intensively treat smoke.
In order to achieve the purpose, the invention adopts the following technical scheme:
a crude copper pyro-continuous refining apparatus comprising: the furnace comprises a furnace body and a flue port arranged at the top of the furnace body, wherein the furnace body is internally provided with a charging oxidation area, a reduction area and a casting area which are separated by partition walls and are mutually communicated at the bottoms, and the reduction area is positioned between the charging oxidation area and the casting area.
In one embodiment of the pyro-continuous refining apparatus for blister copper according to the present invention, the partition walls are disposed between the charging oxidation zone and the reduction zone and between the reduction zone and the casting zone.
In another embodiment of the crude copper pyrometallurgical continuous refining apparatus of the present invention, the partition wall has a gap with the bottom of the furnace body to allow the molten copper to flow therethrough.
In another embodiment of the crude copper pyrometallurgical continuous refining apparatus of the present invention, the partition wall has a gap with the top of the furnace body to pass flue gas generated during refining.
In another embodiment of the pyro-continuous refining apparatus for blister copper according to the present invention, the side wall and/or the top wall of the charging oxidation zone is provided with a cold charge feeding port and a hot charge feeding port.
In another embodiment of the crude copper fire continuous refining device, a slag discharge port is arranged on the side wall of the charging oxidation zone, and sampling observation ports are arranged on the side walls of the reduction zone and the casting zone.
In another embodiment of the pyro-continuous refining apparatus for blister copper according to the present invention, a plurality of lances are provided on the side walls of the charging oxidation zone and the reduction zone to inject an oxidizing agent or a reducing agent into the molten copper.
In another embodiment of the bullion continuous refining apparatus of the present invention, burners are provided on the side walls of the feed oxidation zone and the casting zone.
In another embodiment of the inventive pyro-continuous refining apparatus for blister copper, the flue opening is arranged in the feed oxidation zone or the casting zone.
In another embodiment of the pyro-continuous refining apparatus for blister copper according to the present invention, the bottom of the furnace body is provided with a plurality of gas blowing devices.
The device for continuously refining the blister copper by the fire method has the advantages of low energy consumption, environmental friendliness, high automation level, high production efficiency and the like, can realize continuous feeding of the blister copper and continuous casting of anode copper, can simultaneously carry out oxidation and reduction processes during operation, can shorten the operation time, improve the utilization rate of equipment, has stable smoke gas amount and smoke gas components, and can intensively treat and recover waste heat.
Drawings
FIG. 1 is a schematic structural view of a crude copper pyro-continuous refining apparatus according to an embodiment of the present invention;
FIG. 2 is a flowchart of continuous refining by the pyro-continuous refining apparatus for blister copper according to the present invention.
Wherein the reference numerals are as follows:
1: furnace body
101: feed oxidation zone
102: reduction zone
103: casting zone
2: partition wall
3: cold charge inlet
4: hot material feeding port
5: slag discharge port
6: flue mouth
7: copper discharge port
8: first spray gun
9: second spray gun
11: gas blowing device
12: burner with a burner head
13: sampling observation port
Detailed Description
The technical solution of the present invention is further explained below according to specific embodiments. The scope of protection of the invention is not limited to the following examples, which are set forth for illustrative purposes only and are not intended to limit the invention in any way.
Fig. 1 is a schematic structural view of a raw copper fire continuous refining apparatus according to an embodiment of the present invention, and as shown in fig. 1, the raw copper fire continuous refining apparatus includes a furnace body 1 and a flue port 6 disposed at the top of the furnace body 1, the furnace body 1 has a charging oxidation zone 101, a reduction zone 102 and a casting zone 103 separated by a partition wall but communicating with each other at the bottom, and simultaneously performs charging melting, oxidation, reduction and casting processes, and four cycles are simultaneously performed in the same furnace, wherein the reduction zone 102 is located between the charging oxidation zone 101 and the casting zone 103, so that during operation, copper liquid sequentially passes through the charging oxidation zone 101, the reduction zone 102 and the casting zone 103.
The furnace body 1 is constructed of refractory material, and its furnace space is partitioned from each other by a feed oxidation zone 101, a reduction zone 102 and a casting zone 103 by partition walls 2, but the bottoms communicate with each other, i.e., the partition walls 2 are disposed between the feed oxidation zone 101 and the reduction zone 102 and between the reduction zone 102 and the casting zone 103.
The partition walls 2 are fixed on the side walls of the two sides of the furnace body 1 and are not contacted with the bottom wall and the top wall of the furnace body 1, namely, a gap is arranged between the partition walls 2 and the bottom of the furnace body 1, and the gap can have a certain height enough to enable copper liquid to flow through, so that crude copper hot materials can be continuously added into the furnace, the refining process is continuously carried out, the continuous feeding of crude copper and the continuous casting of anode copper can be realized, the total operation time is shortened, the equipment utilization rate and the production efficiency are improved, and the continuous converting process is objectively ensured not to be influenced by the refining operation.
A gap is also arranged between the partition wall 2 and the top of the furnace body 1, the gap can enable the upper part of the hearth to form a uniform gas space, so that flue gas generated in the refining process (namely, charging melting, oxidation, reduction and casting) can pass through and be collected in the upper hearth space of the furnace body 1, and finally the flue gas generated in the charging oxidation area 101, the reduction area 102 and the casting area 103 can be discharged through the same flue port 6.
The height of the partition wall 2 depends on the liquid level of the molten copper at different scales, and should be higher than the theoretical highest liquid level of the molten copper and maintain a certain safety height, so as to separate the molten copper in the charging oxidation zone 101, the reduction zone 102 and the casting zone 103 from each other at the upper layer, the molten copper can only flow through three zones through the gap between the partition wall 2 and the bottom of the furnace body 1, and the slag generated in the charging oxidation zone 101 is blocked by the partition wall 2 due to the floating of the molten slag.
The side walls and/or the ceiling of the feed oxidation zone 101 are provided with a cold charge inlet 3 and a hot charge inlet 4 through which molten copper (hot charge) or solid charge (cold charge) containing copper can be fed into the feed oxidation zone 101, while the cold charge inlet 3 and the hot charge inlet 4 can also serve as flux inlets through which flux can be fed into the feed oxidation zone 101 to adjust the slag form as necessary. In view of the hot feed specificity, the hot feed inlet 4 is typically located on the top wall of the feed oxidation zone 101, while the cold feed inlet 3 is located without special requirement, either on the top wall of the feed oxidation zone 101 or on the side wall of the feed oxidation zone 101.
Still be equipped with on the lateral wall of reinforced oxidation area 101 and arrange slag notch 5, arrange slag notch 5 and be close to partition wall 2 setting usually, can discharge the slag that floats out the liquid level, arrange slag notch 5 simultaneously and also can regard as the sample viewing aperture to the operator observes the state of copper liquid in reinforced oxidation area 101 at any time, but on-line monitoring oxygen content or sample observation.
The cold charge inlet 3 and the slag discharge port 5 are both provided with furnace doors to ensure the tightness of the furnace body 1 and prevent the flue gas from escaping.
The flue opening 6 is arranged at the top of the furnace body 1 and is usually arranged in the area close to the charging oxidation area 101 or the casting area 103, so that the flue gas generated by the reduction area 102 is discharged outwards through the charging oxidation area 101 or the casting area 103, and the incompletely combusted gas in the reduction process is combusted in the charging oxidation area 101 or the casting area 103, thereby effectively saving fuel and reducing production cost while simplifying the flue gas treatment.
The side walls of the reduction zone 102 and the casting zone 103 are also respectively provided with a sampling observation port 13, so that an operator can observe the state of the molten copper in the reduction zone 102 and the casting zone 103 at any time, and the oxygen content can be monitored on line.
The side wall of the charging oxidation zone 101 is provided with a plurality of first spray guns 8, and the side wall of the reduction zone 102 is provided with a plurality of second spray guns 9.
The first lance 8 is an oxidant lance, and an oxidant, such as compressed air or oxygen-enriched air with oxygen concentration of 22-80 volume percent (vol%), can be injected into the feed oxidation zone 101, and the oxidation depth, i.e. the oxygen content of the copper liquid, can be controlled by the addition amount of the oxidant.
The second spray gun 9 is a reducing agent spray gun, and can spray reducing agents, such as natural gas, liquefied petroleum gas, ammonia, propane, pulverized coal, heavy oil and the like, into the reduction zone 102 and the casting zone 103, and the reduction depth, namely the oxygen content of the copper liquid, is controlled by the adding amount of the reducing agents.
The oxidant and the reducer are sprayed into the melt through the spray gun, the melt is fully stirred, the oxidizing atmosphere and the reducing atmosphere are respectively controlled in the oxidizing zone and the reducing zone, the mass and heat transfer conditions are good, the utilization rate of the oxidant and the reducer is high, the automation level of the process and the device is high, and the spraying condition of the oxidant and the reducer can be automatically controlled.
The first lance 8 and the second lance 9 are angled from the horizontal by-90 deg. -0-90 deg., for example 60 deg., and are not normally located close to the partition wall 2 to ensure a steady flow of melt. As shown in FIG. 1, six first lances 8 and five second lances 9 are provided on both side walls of the feed oxidation zone 101 and the reduction zone 102, respectively.
A copper discharging opening 7 is arranged below the end wall of the casting area 103 so as to continuously discharge anode copper liquid in the casting area 103 to a casting device, and the anode plate is cast to be electrolyzed. The anode copper is continuously discharged, so that the equipment utilization rate of the casting device can be improved, and the production efficiency is improved.
The bottom of the furnace body is provided with a plurality of gas blowing devices 11 which can blow gas which can not react with copper, such as nitrogen or inert gas, into the copper liquid, thereby stirring the melt, improving the conditions of mass and heat transfer and strengthening the smelting reaction strength.
Fig. 2 is a flow chart illustrating continuous refining by the apparatus for the continuous refining of blister copper according to the present invention, and as shown in fig. 2, the process for the continuous refining of blister copper by the fire method comprises the following steps:
and step S101, adding the crude copper into a charging oxidation area, and melting to obtain copper liquid.
And step S102, introducing oxidizing gas into the copper liquid to oxidize impurity elements in the copper liquid to generate oxidized refining slag.
And step S103, discharging the oxidized refining slag, and enabling the oxidized copper liquid to flow into a reduction zone.
And step S104, adding a reducing agent into the reduction region to perform reduction reaction on the oxidized copper liquid.
And step S105, enabling the reduced copper liquid to flow into a casting area.
In step S101, molten blister copper is continuously fed into the charging oxidation zone 101 through the hot charge inlet 4, cold charge is fed into the charging oxidation zone 101 through the cold charge inlet 3, the cold charge is melted by the high temperature of the hot charge itself or the heat generated by the burner 12, and finally all blister copper is melted to obtain molten copper. The process can add cold materials while processing hot materials of the crude copper, and has strong adaptability to raw materials.
Because the charging oxidation zone 101, the reduction zone 102 and the casting zone 103 are communicated with each other and are in the same furnace body 1, the charging melting, oxidation, reduction and casting processes can be continuously carried out, thus realizing the continuous refining of the blister copper and the continuous casting of the anode copper, shortening the total operation time, and improving the equipment utilization rate and the production efficiency.
The temperature of the charging oxidation area 101 is controlled to be 1150-1250 ℃, the temperature is increased according to the actual situation during cold charging, and the combustor 12 arranged on the end wall can burn fuels such as natural gas, heavy oil and the like to supplement heat to the furnace so as to adjust the temperature.
In step S102, an oxidizing gas may be introduced into the molten copper by feeding the first lance 8 of the oxidation zone 101.
The oxidizing gas used may be compressed air or oxygen-enriched air with an oxygen concentration of 22 to 80 vol%. The Cu is first oxidized to form Cu2O，Cu2And then the O reacts with impurity elements (such as other metal elements) to generate oxidized refining slag which can be separated from the copper liquid, or the impurity elements are oxidized into metal oxides and then combined with the flux to form the oxidized refining slag.
In step S103, the oxidized refining slag is continuously or periodically discharged intermittently through the slag discharge port 5, and then the oxidized copper liquid flows into the reduction zone 102 through the lower gap of the partition wall 2 between the charging oxidation zone 101 and the reduction zone 102.
Before the oxidized copper liquid flows into the reduction zone 102, the oxygen content in the oxidized copper liquid is controlled to be 0.5-1.5 wt%, such as 0.8 wt%. The oxidation depth can be controlled by the blowing amount of compressed air or oxygen-enriched air, namely the oxygen content of the copper liquid is controlled, and the oxygen content can be detected on line at the slag discharging port 5 or sampled and observed.
In step S104, a reducing agent is added to the copper bath through the second lance 9 of the reduction zone 102, and the oxidized copper bath is subjected to a reduction reaction.
The reducing agent is one or more of natural gas, liquefied petroleum gas, ammonia, propane, pulverized coal and heavy oil, and the saturated Cu in the copper liquid2The reaction of O with a reducing agent produces Cu.
In step S105, the reduced copper liquid flows into the casting zone 103 through the lower gap of the partition wall 2 between the reduction zone 102 and the casting zone 103, and after the anode copper liquid meets the casting requirement, the anode copper liquid is continuously discharged to a subsequent casting device through a copper discharge port 7 at the bottom of the casting zone 103, and cast into an anode plate for electrolysis. In the process, the anode copper is continuously discharged, so that the equipment utilization rate of the casting device can be improved, and the production efficiency is improved.
The oxygen content in the reduced copper bath is controlled to be 0.1-0.2 wt%, such as 0.12 wt%, before the reduced copper bath flows into the casting zone 103. The reduction depth can be controlled by the addition amount of the reducing agent, namely the oxygen content of the copper liquid is controlled, and the oxygen content is detected on line in the sampling observation hole 13, or sampling observation is carried out.
The burners 12 on the end wall of the casting zone 103 can maintain the temperature of the molten copper in the casting zone 103 at 1150-1250 ℃ by burning fuel such as natural gas, heavy oil, etc., thereby smoothly performing the subsequent casting operation.
The flue gas generated by the charging oxidation area 101, the reduction area 102 and the casting area 103 is collected in the upper space of the hearth and then discharged through the same flue port 6, because the three areas operate simultaneously, the flue gas components, the flue gas amount and the flue gas temperature are stable after the flue gas is collected, CO generated by combustion in the flue gas of the reduction area 102 can be supplemented and combusted by the oxygen-containing flue gas of the charging oxidation area 101 and the casting area 103, the process and the device for adding secondary combustion air are omitted, and simultaneously the flue gas can be sent to a waste heat utilization device to recover waste heat.
In addition, a proper amount of nitrogen or inert gas can be further blown into the copper liquid in the charging oxidation zone 101, the reduction zone 102 and the casting zone 103 through a gas blowing device 11 arranged at the bottom of the furnace, so that the melt is fully stirred, the mass and heat transfer conditions are improved, the smelting reaction strength is enhanced, and the utilization rate and the production efficiency of an oxidant and a reducing agent are improved.
In conclusion, the device for continuously refining the blister copper by the pyrogenic process can realize continuous feeding of the blister copper and continuous casting of anode copper, oxidation and reduction processes are carried out simultaneously during operation, so that the operation time can be shortened, the utilization rate of equipment is improved, the smoke gas quantity and smoke gas components are stable, and waste heat can be intensively treated and recovered. In conclusion, the crude copper pyrogenic process continuous refining device has the advantages of low energy consumption, environmental friendliness, high automation level, high production efficiency and the like.
It should be noted by those skilled in the art that the described embodiments of the present invention are merely exemplary and that various other substitutions, alterations, and modifications may be made within the scope of the present invention. Accordingly, the present invention is not limited to the above-described embodiments, but is only limited by the claims.
Claims (6)
1. A crude copper fire continuous refining device is characterized by comprising: the furnace comprises a furnace body, a flue port, a hot material feeding port, a cold material feeding port, a first burner, a second burner, a first partition wall, a second partition wall, a first sampling observation port, a second sampling observation port, a slag discharge port, a copper discharge port, a plurality of first spray guns, a plurality of second spray guns and a plurality of gas blowing devices, wherein the furnace body is sequentially divided into a feeding oxidation area, a reduction area and a casting area, the bottoms of which are communicated with each other, by the first partition wall and the second partition wall, the reduction area is positioned between the feeding oxidation area and the casting area, a first gap is formed between the first partition wall and the bottom of the furnace body, the first gap has a certain height which is enough for copper liquid to flow through, a second gap is formed between the first partition wall and the top of the furnace body, and the second gap enables the upper part of the furnace body to form a uniform gas space, so that the flue gas generated in the charging oxidation zone, the reduction zone and the casting zone is collected and discharged through the flue opening;
the slag discharging port is arranged on the side wall of the charging oxidation zone and is close to the first partition wall, and the slag discharging port is simultaneously used as a sampling observation port for online detection of oxygen content;
the first sampling observation port and the second sampling observation port are respectively arranged on the side walls of the reduction zone and the casting zone and are used for detecting the oxygen content on line;
in the charging oxidation zone, copper is oxidized to form cuprous oxide, the cuprous oxide reacts with impurity elements to generate oxidized refining slag which can be separated from copper liquid, the oxidized refining slag is discharged through the slag discharge port, and the oxygen content in the oxidized copper liquid is controlled to be 0.5-1.5 wt%;
in the reduction zone, a reducing agent is added into the copper liquid through the plurality of second spray guns, saturated cuprous oxide in the copper liquid is reduced to obtain copper, and the oxygen content in the reduced copper liquid is controlled to be 0.1-0.2 wt%;
the flue port is arranged at the top of the furnace body and is close to the charging oxidation zone or the casting zone, and the copper discharge port is arranged below the end wall of the casting zone.
2. The bullion pyrometallurgical continuous refining device in accordance with claim 1, wherein the first and second partition walls are disposed between the feed oxidation zone and the reduction zone and between the reduction zone and the casting zone, respectively.
3. The blister copper pyro-continuous refining apparatus according to claim 1, wherein the hot charge addition port is provided on a top wall of the charge oxidation zone, and the cold charge addition port is provided on a side wall and/or a top wall of the charge oxidation zone.
4. The bullion pyrometallurgical continuous refining device of claim 1, wherein the plurality of first lances and the plurality of second lances are provided on the side walls of the feed oxidation zone and the reduction zone, respectively, to inject an oxidizing agent or a reducing agent into the molten copper.
5. The bullion pyrometallurgical continuous refining apparatus in accordance with claim 1, wherein the first and second burners are disposed on the side walls of the feed oxidation zone and the casting zone, respectively.
6. The bullion continuous refining apparatus of any one of claims 1 to 5, wherein the plurality of gas blowing devices are provided at the bottom of the furnace body.
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| CN109317654B (en) * | 2018-11-13 | 2020-08-04 | 临沂市凯星水表有限公司 | High-precision casting equipment for copper industry processing |
| CN110760691B (en) * | 2019-11-26 | 2020-11-06 | 新乡灵越电子技术有限公司 | Fire refining blister copper machine |
| CN113355531B (en) * | 2021-05-28 | 2022-11-04 | 河南豫光金铅股份有限公司 | Production method for directly smelting brass raw material into copper anode plate |
| CN114350975B (en) * | 2022-01-06 | 2022-09-02 | 高诺(衡阳)新材料有限责任公司 | Reverberatory furnace fire refining method for high-arsenic and high-antimony crude copper |
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|---|---|---|---|---|
| US4127408A (en) * | 1975-05-22 | 1978-11-28 | Klockner Humboldt Deutz Aktiengesellschaft | Method for the continuous refinement of contaminated copper in the molten phase |
| JPH0693351A (en) * | 1992-09-16 | 1994-04-05 | Mitsubishi Materials Corp | Production of tough pitch copper |
| CN105039738A (en) * | 2015-07-27 | 2015-11-11 | 王泊远 | Crude copper fire refining furnace and process |
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| CN103952571B (en) * | 2014-04-18 | 2015-08-12 | 东营鲁方金属材料有限公司 | One step copper metallurgy technique and device thereof |
| CN107287442A (en) * | 2017-05-23 | 2017-10-24 | 西北矿冶研究院 | Continuous copper smelting device and copper smelting method |
| CN208087704U (en) * | 2018-04-08 | 2018-11-13 | 中国恩菲工程技术有限公司 | A kind of blister copper pyrogenic process continuous refining device |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4127408A (en) * | 1975-05-22 | 1978-11-28 | Klockner Humboldt Deutz Aktiengesellschaft | Method for the continuous refinement of contaminated copper in the molten phase |
| JPH0693351A (en) * | 1992-09-16 | 1994-04-05 | Mitsubishi Materials Corp | Production of tough pitch copper |
| CN105039738A (en) * | 2015-07-27 | 2015-11-11 | 王泊远 | Crude copper fire refining furnace and process |
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