CN103952564A - Copper smelting slag processing method - Google Patents
Copper smelting slag processing method Download PDFInfo
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- CN103952564A CN103952564A CN201410127112.3A CN201410127112A CN103952564A CN 103952564 A CN103952564 A CN 103952564A CN 201410127112 A CN201410127112 A CN 201410127112A CN 103952564 A CN103952564 A CN 103952564A
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/10—Reduction of greenhouse gas [GHG] emissions
- Y02P10/143—Reduction of greenhouse gas [GHG] emissions of methane [CH4]
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
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Abstract
The invention discloses a copper smelting slag processing method. The method comprises the following steps: mixing copper smelting slag with a first slag forming agent and a first reducing agent, and carrying out first reduction treatment in order to obtain copper and first smelting slag; mixing the first melting slag with a second slag forming agent and a second reducing agent, and carrying out second reduction treatment in order to obtain iron and second smelting slag; and sequentially carrying out heat insulation and silk making treatment on the second smelting slag in order to obtain inorganic fibers. The method can effectively recover copper and iron from the copper smelting slag, and has the advantages of simple process, less energy consumption, low cost, high treatment efficiency and high byproduct utilization value.
Description
Technical field
The present invention relates to copper smelting slag application technology as the second resource field, particularly, the present invention relates to copper smelting slag treatment process.
Background technology
World's Copper Resources is due to long-term exploitation, and primary resources is poor lacking gradually, and developing secondary resource is the important channel that colored metallurgical industrial is realized Sustainable development.Copper smelting slag is the important secondary resource of copper, improves copper smelting recovery, reduces waste cupric, and therefrom reclaims other valuable metals, thereby realize the abundant recycling of copper smelting slag, has become expert and technician's common recognition.
Yet current copper smelting slag treatment process still haves much room for improvement.
Summary of the invention
The present invention is that the following discovery based on contriver completes:
Copper smelting slag has higher added value: copper smelting slag complicated component, except containing the precious metals such as a small amount of copper, zinc, sulphur, cobalt, also contains a large amount of iron, silicon-dioxide, calcium oxide and partial oxidation magnesium, aluminium sesquioxide etc.Copper smelting slag is processed, therefrom reclaimed the valuable metals such as copper, iron, can make copper smelting slag obtain abundant recycling, thereby realize the value maximization of copper smelting slag.
In order effectively to utilize copper smelting slag, adopt traditionally electric furnace sulfonium or slow cooling ore-dressing technique, electric furnace sulfonium metallization processes is that copper smelting slag is joined in electric furnace, by adding sulfonium agent and a small amount of reductive agent, utilize heated by electrodes by the temperature raising of copper smelting slag, copper in copper smelting slag settles down with the form of copper matte regulus, separated with waste; Slow cooling ore-dressing technique is that copper smelting slag is placed in to cinder ladle, by water spray, makes slag slow cooling, and after fragmentation, ore dressing obtains copper ore concentrates, iron ore concentrate and waste.Yet, traditional treatment process waste cupric high (sulfoniumization is processed between 0.6～1%, and ore dressing is processed between 0.3～0.4%), cannot reclaim with oxide form and be present in the copper in slag, iron in slag cannot obtain effective recycling, and waste also cannot be utilized effectively.
The present invention one of is intended to solve the problems of the technologies described above at least to a certain extent or at least provides a kind of useful business to select.For this reason, one object of the present invention be to propose a kind of can be from copper smelting slag high efficiente callback copper, iron realize the copper smelting slag treatment process of residue waste recycling.
According to an aspect of the present invention, the invention provides a kind of copper smelting slag treatment process.According to embodiments of the invention, the method comprises: copper smelting slag is mixed with the first slag former and the first reductive agent, and carry out the first reduction processing, to obtain copper and the first smelting slag; Described the first smelting slag is mixed with the second slag former and the second reductive agent, and carry out the second reduction processing, to obtain iron and the second smelting slag; And described the second smelting slag is incubated successively and throwing processing, to obtain inorganic fibre.According to embodiments of the invention, utilize copper smelting slag treatment process of the present invention can effectively from copper smelting slag, reclaim copper, iron, and technique is simple, needing can be less, cost is low, processing efficiency is high, by-product utilized is worth high.
According to embodiments of the invention, the treatment process of above-mentioned copper smelting slag can also have following additional technical feature:
According to one embodiment of present invention, described the first reduction is processed and to be carried out under 1250-1350 degree Celsius.Thus, the efficiency that the first reduction is processed can be improved, and then the processing efficiency of copper smelting slag can be further improved.
According to one embodiment of present invention, described the second reduction is processed and to be carried out under 1350-1450 degree Celsius.Thus, the efficiency that the second reduction is processed can be improved, and then the processing efficiency of copper smelting slag can be further improved.
According to one embodiment of present invention, under 1450-1500 degree Celsius, carry out described insulation processing.Thus, high insulating effect, be conducive to the carrying out that follow-up throwing is processed, and then the second smelting slag utilization ratio is high, and the Quality and yield of inorganic fibre is good.
According to one embodiment of present invention, in slag cleaning furnace, carry out described the first reduction and process, in electric reduction furnace, carry out described the second reduction and process, in electric mantle heater, carry out described insulation processing.
According to one embodiment of present invention, in slag cleaning furnace, carrying out successively described the first reduction processing, described the second reduction processing and described insulation processes.Thus, in an equipment, can realize three steps, thereby technical process is simple, easy to operate, and cost is low, easily popularization.
According to one embodiment of present invention, described the first slag former and the second slag former one of at least for being selected from least one of Wingdale and slag.Thus, the efficiency that the first reduction is processed and the second reduction is processed can be improved, and then the processing efficiency of copper smelting slag can be further improved.
According to one embodiment of present invention, described the first slag former is Wingdale, and the CaO content of described the first smelting slag is 10-30 % by weight, and the weight ratio of FeO and silicon-dioxide is 1.2～1.8, Cu content is below 0.05 % by weight, and the viscosity of described the first smelting slag is below 5 pools.Thus, can guarantee efficiency, blister copper grade and the copper recovery that the first reduction is processed.
According to one embodiment of present invention, described the first reductive agent is to be selected from least one of carbon monoxide and coal dust.Thus, the efficiency that the first reduction is processed can be improved, and then the processing efficiency of copper smelting slag can be further improved.
According to one embodiment of present invention, described the second slag former is Wingdale, in described the second smelting slag, CaO and MgO weight sum are M1, silicon-dioxide and alchlor weight sum are M2, wherein the ratio of M1 and M2 is 0.6～0.8, and the content of FeO is 8～15 % by weight in described the second smelting slag, the viscosity of the second smelting slag is 10～25 pools.Thus, the efficiency of the second reduction processing and the rate of recovery of iron can be guaranteed, and then the processing efficiency of copper smelting slag can be further improved.
According to one embodiment of present invention, described the second reductive agent is to be selected from least one of coal dust, Sweet natural gas, heavy oil.Thus, the efficiency that the second reduction is processed can be improved, and then the processing efficiency of copper smelting slag can be further improved.
According to one embodiment of present invention, further comprise that the first reduction is processed to the waste gas producing burns, to carry out waste heat recovery.Thus, can improve the utilising efficiency of resource, and then can further improve the processing efficiency of copper smelting slag, reduce processing cost.
According to one embodiment of present invention, further comprise that the second reduction is processed to the tail gas producing to be returned as the first reductive agent.Thus, can improve the utilising efficiency of resource, and then can further improve the processing efficiency of copper smelting slag, reduce processing cost.
Additional aspect of the present invention and advantage in the following description part provide, and part will become obviously from the following description, or recognize by practice of the present invention.
Accompanying drawing explanation
Above-mentioned and/or additional aspect of the present invention and advantage accompanying drawing below combination obviously and is easily understood becoming the description of embodiment, wherein:
Fig. 1 has shown the schematic flow sheet of copper smelting slag treatment process according to an embodiment of the invention.
Fig. 2 has shown the schematic flow sheet of copper smelting slag treatment process in accordance with another embodiment of the present invention.
Embodiment
Describe embodiments of the invention below in detail.Below by the embodiment being described with reference to the drawings, be exemplary, be intended to for explaining the present invention, and can not be interpreted as limitation of the present invention.
Wherein, term " first ", " second " be only for describing object, and can not be interpreted as indication or hint relative importance or the implicit quantity that indicates indicated technical characterictic.Thus, one or more these features can be expressed or impliedly be comprised to the feature that is limited with " first ", " second ".
According to an aspect of the present invention, the invention provides a kind of copper smelting slag treatment process.According to embodiments of the invention, with reference to Fig. 1, the method comprises:
First, copper smelting slag is mixed with the first slag former and the first reductive agent, and carry out the first reduction processing, to obtain copper and the first smelting slag.Wherein, the copper of acquisition is low-grade blister copper.
It should be noted that, in copper smelting slag treatment process of the present invention, the copper smelting slag adopting can be the high temperature copper smelting slag of coming out of the stove, thus, can effectively utilize the high-temperature residual heat of this copper smelting slag, thereby can effectively improve the level of resources utilization, reduce processing cost.
According to embodiments of the invention, the condition of carrying out the first reduction processing is not particularly limited, as long as can guarantee reaction efficiency, effectively obtains copper and the first smelting slag.According to one embodiment of present invention, described the first reduction is processed and to be carried out under 1250-1350 degree Celsius.Thus, can improve the efficiency that the first reduction is processed, guarantee the mobility of slag, and then can further improve the processing efficiency of copper smelting slag.According to embodiments of the invention, described the first slag former is to be selected from least one of Wingdale and slag.This be because, in Wingdale and slag, all contain a large amount of CaO, can be in the first reduction treatment process, supplement basic oxide, guarantee the mobility of slag, increase the activity of FeO, improve the efficiency that the first reduction is processed.According to concrete examples more of the present invention, described the first slag former is Wingdale, and the CaO content of described the first smelting slag is 10-30 % by weight, and the weight ratio of FeO and silicon-dioxide is 1.2～1.8, Cu content is below 0.05 % by weight, and the viscosity of described the first smelting slag is below 5 pools.Thus, can guarantee efficiency, blister copper grade and the copper recovery that the first reduction is processed.According to embodiments of the invention, described the first reductive agent is to be selected from least one of carbon monoxide and coal dust.Thus, the efficiency that the first reduction is processed can be improved, and then the processing efficiency of copper smelting slag can be further improved.
Then, described the first smelting slag is mixed with the second slag former and the second reductive agent, and carry out the second reduction processing, to obtain iron and the second smelting slag.
According to embodiments of the invention, the condition of carrying out the second reduction processing is not particularly limited, as long as can guarantee reaction efficiency, effectively obtains iron and the second smelting slag.According to one embodiment of present invention, described the second reduction is processed and to be carried out under 1350-1450 degree Celsius.Thus, can improve the efficiency that the second reduction is processed, guarantee the mobility of slag, and then can further improve the processing efficiency of copper smelting slag.According to embodiments of the invention, described the second slag former is to be selected from least one of Wingdale and slag.Thus, can in the second reduction treatment process, by unslaked lime stone and slag, supplement CaO, guarantee the mobility of slag, increase the activity of FeO, improve the efficiency that the second reduction is processed.According to one embodiment of present invention, described the second slag former is Wingdale, in described the second smelting slag, CaO and MgO weight sum are M1, silicon-dioxide and alchlor weight sum are M2, wherein the ratio of M1 and M2 is 0.6～0.8, and the content of FeO is 8～15 % by weight in described the second smelting slag, the viscosity of the second smelting slag is 10～25 pools.Thus, the efficiency of the second reduction processing and the rate of recovery of iron can be guaranteed, and then the processing efficiency of copper smelting slag can be further improved.According to one embodiment of present invention, described the second reductive agent is to be selected from least one of coal dust, Sweet natural gas, heavy oil.Thus, the efficiency that the second reduction is processed can be improved, and then the processing efficiency of copper smelting slag can be further improved.
Then, described the second smelting slag is incubated successively and throwing processing, to obtain inorganic fibre.
According to embodiments of the invention, be incubated concrete grammar and the reaction conditions processed with throwing and be not particularly limited, as long as can guarantee, effectively from the second smelting slag, prepare inorganic fibre.According to one embodiment of present invention, under 1450-1500 degree Celsius, carry out described insulation processing.Thus, high insulating effect, be conducive to the carrying out that follow-up throwing is processed, and then the second smelting slag utilization ratio is high, and the Quality and yield of inorganic fibre is good.According to one embodiment of present invention, described throwing is processed by winding-up or centrifugal drying silk and is processed and realize.Thus, the second smelting slag that can process through insulation effectively be prepared into inorganic fibre, and the inorganic fibre preparing can reach the standard of rock wool for building exterior wall heat preserving, thereby has improved by-product utilized rate, reduce environmental pressure, and increased economic benefit.
In addition for implementing the equipment of each step of copper smelting slag treatment process of the present invention, be not particularly limited.According to one embodiment of present invention, can in slag cleaning furnace, carry out described the first reduction and process, in electric reduction furnace, carry out described the second reduction and process, in electric mantle heater, carry out described insulation processing.According to another embodiment of the invention, can in slag cleaning furnace, carry out successively described the first reduction processing, described the second reduction processing and described insulation processes.Thus, in an equipment, can realize three steps, thereby technical process is simple, easy to operate, and cost is low, easily popularization.
In addition, for convenience of understanding, the main chemical equation relating to will be enumerated below in method of the present invention, wherein, suppose that the first slag former and the second slag former are coal, the first reductive agent and the second reductive agent are unslaked lime stone, and the main chemical reaction occurring comprises:
The principal reaction that the first reduction treatment step relates to:
Reduction reaction: C+Fe
3o
4=3FeO+CO (g),
CO(g)+Fe
3O
4=3FeO+CO
2(g)；
Slag making reaction: 2FeO+SiO
2=2FeOSiO
2,
CaCO
3=CaO+CO2(g)，
CaO+SiO
2=CaO·SiO
2。
The principal reaction that the second reduction treatment step relates to:
Reduction reaction: 2C+2FeOSiO
2=2Fe+2CO (g)+SiO
2,
Slag making reaction: CaCO
3=CaO+CO2 (g);
CaO+SiO
2=CaO·SiO
2。
According to embodiments of the invention, by product of the present invention also has higher utility value, particularly:
First, the first reduction is processed the waste gas producing and is contained a large amount of CO, through secondary combustion, can produce a large amount of waste heats.And then, according to concrete examples more of the present invention, further comprise that the first reduction is processed to the waste gas producing burns, to carry out waste heat recovery.Thus, not only can efficient recovery heat energy, save industrial energy, improve the utilising efficiency of resource, reduce processing cost, and waste gas is through gathering dust and desulfurization can reach emptying requirement after processing, and then can reduce pollution, make the present invention obtain the effect of energy-saving and emission-reduction.
Secondly, the CO that also contains 40 volume %-60 volume % in the tail gas producing is processed in the second reduction, can return in copper smelting slag treatment process of the present invention, as the first reductive agent.And then, according to one embodiment of present invention, further comprise that the second reduction is processed to the tail gas producing to be returned as the first reductive agent.Thus, can improve the utilising efficiency of resource, and then can further improve the processing efficiency of copper smelting slag, reduce processing cost.
Contriver is surprised to find, and utilizes copper smelting slag treatment process of the present invention can effectively from copper smelting slag, reclaim copper, iron, and technique is simple, needing can be less, cost is low, processing efficiency is high, by-product utilized is worth high.
Below by specific embodiment, describe the present invention, it should be noted that, these specific embodiments do not limit the present invention in any way, and are only used to the object of explanation.In addition, the device adopting in embodiment is below known, unless otherwise indicated, the condition of not listing in the following example or device, those skilled in the art can select as required.
General method:
According to embodiments of the invention, with reference to Fig. 1, copper smelting slag treatment process of the present invention can comprise:
First, copper smelting slag is mixed with the first slag former and the first reductive agent, and carry out the first reduction processing, to obtain copper and the first smelting slag.
Secondly, described the first smelting slag is mixed with the second slag former and the second reductive agent, and carry out the second reduction processing, to obtain iron and the second smelting slag.
Then, described the second smelting slag is incubated successively and throwing processing, to obtain inorganic fibre.
Embodiment 1:
See figures.1.and.2, according to copper smelting slag treatment process of the present invention, process copper smelting slag, specific as follows:
First, by the 3t copper smelting slag (Fe/SiO just having discharged
2=1.3, Cu:1.2%, CaO:4.5%, Al
2o
34.1%, MgO:2.7%) from return slag chute, join slag cleaning furnace (400kVA), then in slag cleaning furnace, add 600kg Wingdale as slag former, simultaneously, from slag cleaning furnace top, with spray gun, spray into 60kg coal dust, the winding-up time is 3h, and winding-up finishes rear clarification 0.5h, control slag temperature between 1250-1300 ℃, sampling analysis first slag and blister copper composition (table 1); First slag is returned from discharge slag cleaning furnace bottom again and in slag cleaning furnace, carry out drastic reduction operation (carrying out the second reduction processing), add Wingdale 160kg, from slag cleaning furnace top pulverized coal injection 720kg, winding-up time 4.5h, winding-up finishes rear clarification 0.5h, control slag temperature between 1350-1400 ℃, the high white residue composition of sampling analysis and hot metal composition (table 2); Molten iron is emptying from furnace bottom; This slag cleaning furnace is continued to heat up, control slag temperature 1450 ℃ of left and right, insulation 0.5h, then emits high white residue from cinder notch, after chute drainage, with four, roll whizzer throwing, obtains the inorganic fibre of 6 microns of left and right of diameter.
Wherein, the tail gas that slag cleaning furnace is produced (comprise the first reduction process waste gas and the second reduction produce and process the tail gas a producing) part is returned as the first reductive agent of copper smelting slag treatment scheme next time, another part carries out burn processing, and utilizes boiler to reclaim burner exhaust heat.It should be noted that, the per-cent described in the present embodiment is all weight percentage (wt.%), 1Pas=10 pool.
Table 1 first slag and blister copper composition
The high white residue of table 2 and hot metal composition
In the description of this specification sheets, the description of reference term " embodiment ", " some embodiment ", " example ", " concrete example " or " some examples " etc. means to be contained at least one embodiment of the present invention or example in conjunction with specific features, structure, material or the feature of this embodiment or example description.In this manual, the schematic statement of above-mentioned term is not necessarily referred to identical embodiment or example.And the specific features of description, structure, material or feature can be with suitable mode combinations in any one or more embodiment or example.
Although illustrated and described embodiments of the invention above, be understandable that, above-described embodiment is exemplary, can not be interpreted as limitation of the present invention, those of ordinary skill in the art can change above-described embodiment within the scope of the invention in the situation that not departing from principle of the present invention and aim, modification, replacement and modification.
Claims (13)
1. a copper smelting slag treatment process, is characterized in that, comprising:
Copper smelting slag is mixed with the first slag former and the first reductive agent, and carry out the first reduction processing, to obtain copper and the first smelting slag;
Described the first smelting slag is mixed with the second slag former and the second reductive agent, and carry out the second reduction processing, to obtain iron and the second smelting slag; And
Described the second smelting slag is incubated successively and throwing processing, to obtain inorganic fibre.
2. method according to claim 1, is characterized in that, described the first reduction is processed and carried out under 1250-1350 degree Celsius.
3. method according to claim 1, is characterized in that, described the second reduction is processed and carried out under 1350-1450 degree Celsius.
4. method according to claim 1, is characterized in that, carries out described insulation processing under 1450-1500 degree Celsius.
5. method according to claim 1, is characterized in that, carries out described the first reduction and process in slag cleaning furnace, carries out described the second reduction and process in electric reduction furnace, carries out described insulation processing in electric mantle heater.
6. method according to claim 1, is characterized in that, carries out successively described the first reduction processing, described the second reduction processing and described insulation and process in slag cleaning furnace.
7. method according to claim 1, is characterized in that, described the first slag former and the second slag former one of at least for being selected from least one of Wingdale and slag.
8. method according to claim 7, it is characterized in that, described the first slag former is Wingdale, the CaO content of described the first smelting slag is 10-30 % by weight, the weight ratio of FeO and silicon-dioxide is 1.2～1.8, Cu content is below 0.05 % by weight, and the viscosity of described the first smelting slag is below 5 pools.
9. method according to claim 1, is characterized in that, described the first reductive agent is to be selected from least one of carbon monoxide and coal dust.
10. method according to claim 7, it is characterized in that, described the second slag former is Wingdale, in described the second smelting slag, CaO and MgO weight sum are M1, silicon-dioxide and alchlor weight sum are M2, wherein the ratio of M1 and M2 is 0.6～0.8, and in described the second smelting slag, the content of FeO is 8～15 % by weight, and the viscosity of the second smelting slag is 10～25 pools.
11. methods according to claim 1, is characterized in that, described the second reductive agent is to be selected from least one of coal dust, Sweet natural gas, heavy oil.
12. methods according to claim 1, is characterized in that, further comprise that the first reduction is processed to the waste gas producing burns, to carry out waste heat recovery.
13. methods according to claim 1, is characterized in that, further comprise that the second reduction is processed to the tail gas producing to be returned as the first reductive agent.
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| CN104232818A (en) * | 2014-10-14 | 2014-12-24 | 钢铁研究总院 | Effective comprehensive utilization method for steel slag |
| CN104878216A (en) * | 2015-05-21 | 2015-09-02 | 金隆铜业有限公司 | Copper smelting slag depletion method and system |
| CN104232818B8 (en) * | 2014-10-14 | 2016-05-11 | 钢铁研究总院 | A kind of method of slag high-efficiency comprehensive utilization |
| CN108165755A (en) * | 2017-12-26 | 2018-06-15 | 中国恩菲工程技术有限公司 | Copper weld pool slag for comprehensive recovery method |
| CN108396151A (en) * | 2017-06-14 | 2018-08-14 | 中国恩菲工程技术有限公司 | Copper weld pool slag for comprehensive retracting device |
| CN108504875A (en) * | 2017-06-14 | 2018-09-07 | 中国恩菲工程技术有限公司 | Short route copper smelting method |
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| CN110257643A (en) * | 2019-07-01 | 2019-09-20 | 东营方圆有色金属有限公司 | The technique and recovery system of iron and zinc are recycled from copper weld pool slag |
| CN110423861A (en) * | 2019-09-11 | 2019-11-08 | 中国恩菲工程技术有限公司 | Produce the application of the method and copper ashes of copper bearing steel as coolant in production copper bearing steel |
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| CN115141938A (en) * | 2021-03-29 | 2022-10-04 | 东北大学 | Method for diluting copper smelting slag by using copper refining slag |
| CN116162846A (en) * | 2023-03-07 | 2023-05-26 | 江西理工大学 | Desulfurization method of high-sulfur copper-iron alloy produced by copper smelting slag and copper-iron alloy |
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