CN107299220A - A kind of processing method of copper ashes - Google Patents
A kind of processing method of copper ashes Download PDFInfo
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- CN107299220A CN107299220A CN201710396123.5A CN201710396123A CN107299220A CN 107299220 A CN107299220 A CN 107299220A CN 201710396123 A CN201710396123 A CN 201710396123A CN 107299220 A CN107299220 A CN 107299220A
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B1/00—Preliminary treatment of ores or scrap
- C22B1/02—Roasting processes
- C22B1/08—Chloridising roasting
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B03—SEPARATION OF SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS; MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
- B03C—MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
- B03C1/00—Magnetic separation
- B03C1/02—Magnetic separation acting directly on the substance being separated
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Abstract
The present invention relates to a kind of processing method of copper ashes.Methods described includes：Pelletizing after copper ashes, chlorinating agent, binding agent are uniformly mixed, obtains the first pelletizing, wherein, iron, zinc, lead, copper metal element are contained in copper ashes；The oxidized calcination process of first pelletizing, obtains acid pellet, meanwhile, zinc, lead, copper metal element formation chloride flue dust in copper ashes；Pelletizing after acid pellet, reducing agent, binding agent are uniformly mixed, obtains the second pelletizing；Second pelletizing is handled through reduction roasting, obtains metallized pellet, meanwhile, remaining zinc, lead, copper metal element formation chloride flue dust in copper ashes；Metallized pellet is handled through mill ore magnetic selection, obtains iron powder.The method of the present invention can realize the separation and recovery of iron and rare metal in copper ashes at a lower temperature, especially realize the separation of iron and copper, can significantly improve the Iron grade and economic value of iron powder, and realize energy-saving technique effect.
Description
Technical field
The present invention relates to field of solid waste treatment, and in particular to a kind of processing method of copper ashes.
Background technology
Copper ashes is the clinker that copper metallurgy process is produced, and 2.2 tons of copper ashes are produced while smelting 1 ton of refined copper.China's copper slag
Yield is big, produces 1500000 tons or so per year.Copper ashes bulk deposition can bring serious water pollution and soil contamination problem, strengthen pair
The comprehensive utilization of copper ashes is extremely important.The main component of copper ashes is ferriferous oxide and silica, and main thing is mutually fayalite
And a small amount of magnetic iron ore.At present, the utilization on copper ashes be concentrated mainly on extract copper ashes in valuable metal element, such as copper,
Cobalt, zinc, iron.Extracting method has the technological means such as beneficiating method, pyrometallurgical smelting, hydrometallurgy.
Copper ashes is the eutectic of each oxide melting mutually in furnace charge and fuel during pyrometallurgical smelting, wherein
The rich content of the valuable metals such as copper, cobalt, iron, recovery value is higher.Particularly, copper ashes iron content rate is 35% or so, is much larger than
Smelt the average mining grade of iron ore 29.1%.At present, reclaiming the method for iron in copper ashes has：High-temperature fusion oxidation-normal temperature is crushed
Magnetic method, Staged grinding and staged separation method and direct smelting reduction process.First method is that oxidisability is blown into molten copper slag
Gas, and control in cooling procedure certain rate of temperature fall (5Kmin-1), this method can make magnetic iron ore accumulation rate in copper ashes
More than 85% is brought up to from 22%, but this method can not separate copper, iron, it is more difficult to further realize the utilization of iron.Second of side
In method, the rate of recovery of iron is relatively low, main chalybeate phase fayalite (Fe2SiO4) enter mine tailing during magnetic separation.The third side
In method, the rate of recovery of iron is up to 90% or so, but gained molten iron cupric is higher, is of limited application, and carries out the deep decopper(ing) of molten iron
It is more difficult.
The content of the invention
It is contemplated that the processing of copper ashes is realized, by causing the iron in copper ashes with addition of a certain amount of chlorinating agent into copper ashes
Separate, so that iron, copper, lead, the zinc metallic element in copper ashes are separately separated, the grade for extracting iron is higher, improve with copper
Value.
The invention provides a kind of processing method of copper ashes, including step：
Copper ashes, chlorinating agent, binding agent uniformly mixing after pelletizing, obtain the first pelletizing, wherein, in copper ashes containing iron, zinc,
Lead, copper metal element.
The oxidized calcination process of first pelletizing, obtains acid pellet, meanwhile, zinc, lead in the copper ashes, copper metal
Element formation chloride flue dust.
Pelletizing after the acid pellet, reducing agent, binding agent are uniformly mixed, obtains the second pelletizing.
Second pelletizing is handled through reduction roasting, obtains metallized pellet, meanwhile, remaining zinc, lead in the copper ashes,
Copper metal element formation chloride flue dust.
The metallized pellet is handled through mill ore magnetic selection, obtains iron powder.
It is preferred that, all iron content is 35.18~38.05wt% (wt% is mass percent), Zn content in the copper ashes
For 1.17~2.91wt%, lead content is 0.058~0.62wt%, and copper content is 0.22~4.05wt%.The grain of the copper ashes
Spend≤200 mesh.
Further, the chlorinating agent is calcium chloride.The granularity of the chlorinating agent is the mesh of 200 mesh~100.
Further, the binding agent is bentonite.The mesh of the granularity of the binding agent≤200.
It is preferred that, in first pelletizing, the copper ashes, chlorinating agent, the quality accounting of binding agent are 100:(5~12)：
(5~10).
Further, the temperature of the oxidizing roasting processing procedure be 700~1100 DEG C, oxidizing roasting time be 15~
30min。
Further, the reducing agent is semi-coke.The mesh of the granularity of the reducing agent≤200.
It is preferred that, in second pelletizing, the quality of fixed carbon and the oxygen in the acid pellet in the reducing agent
Than for：C/O=1.2~2.0：1.
Further, a diameter of 5~12mm of first pelletizing.A diameter of 10~24mm of second pelletizing.
Further, the temperature of the reduction roasting processing procedure be 1100~1300 DEG C, the reduction roasting time be 15~
30min。
The method of the present invention is related to balling process twice, and the first obtained pelletizing carries out oxidizing roasting reaction so that copper ashes
The low oxide of middle iron is oxidized to high oxide, because the high oxide of iron is difficult chlorination and is present in the oxidation of solid-state
In pelletizing, copper, lead, zinc in copper ashes occur chlorination reaction and form corresponding chloride flue dust respectively, so as to realize iron in copper ashes
With copper, zinc, lead initial gross separation；The second obtained pelletizing carries out reduction roasting reaction so that remaining copper, zinc, lead in copper ashes
Further occur chlorination reaction and form corresponding chloride flue dust, iron rule occurs reduction reaction and is present in the metallization ball of solid-state
In group.The characteristics of copper, zinc, the chloride of lead have low boiling, high volatile, iron in copper ashes can be realized at a lower temperature
With the separation and recovery of rare metal, the separation of iron and copper is especially realized, the iron powder obtained after mill ore magnetic selection can be significantly improved
Iron grade and economic value, and realize energy-saving technique effect.
Brief description of the drawings
Fig. 1 is the process flow schematic diagram of copper ashes in the embodiment of the present invention.
Embodiment
Below in conjunction with drawings and examples, the embodiment to the present invention is described in more details, so as to energy
Enough more fully understand the solution of the present invention and the advantage of its various aspects.However, specific embodiments described below and reality
Apply the purpose that example is only explanation, rather than limitation of the present invention.
In view of utilization of the prior art to copper ashes is understood, the intractability of copper ashes is how to realize copper and iron independent point
From so as to improve the grade and value of extracted copper and ferro element, the present invention proposes a kind of processing side of copper ashes with regard to this
Method, as shown in figure 1, comprising the following steps：
(1) pelletizing is prepared
By pelletizing after copper ashes, chlorinating agent, binding agent uniformly mixing, the first pelletizing is obtained.In embodiments of the invention, each group
Point mass ratio be：Copper ashes：Chlorinating agent：Binding agent=100:(5~12)：(5~10).Also, control the diameter of the first pelletizing
For 5~12mm.It is preferred that, control a diameter of 6~10mm of the first pelletizing.
In the copper ashes that the present invention is selected, all iron content is 35.18~38.05wt%, and Zn content is 1.17~2.91wt%,
Lead content is 0.058~0.62wt%, and copper content is 0.22~4.05wt%.Also, the mesh of the granularity of copper ashes≤200, the granularity
Copper ashes be conducive to copper ashes pelletizing to obtain the first pelletizing, while the contact area of copper ashes and chlorinating agent can be increased, promote chlorination
The progress of reaction.
In the present invention, the granularity of chlorinating agent is the mesh of 200 mesh~100.Chlorinating agent preferably calcium chloride, the fusing point of calcium chloride is
782℃。
In the present invention, the mesh of the granularity of binding agent≤200, preferably bentonite.
(2) first pelletizings carry out oxidizing roasting
First pelletizing carries out oxidizing roasting processing after drying, obtains acid pellet and chloride flue dust.
In the present invention, the temperature of oxidizing roasting process is 700~1100 DEG C, and the time is 15~30min.It is excellent as the present invention
The embodiment of choosing, the temperature of oxidizing roasting process is 800~1100 DEG C, and the time is 20~30min.
The oxidizing roasting process of the present invention, can make the low oxide of iron in copper ashes be oxidized to high oxide so that
Ferro element in copper ashes is not susceptible to chlorination reaction and is fixed in slag, i.e. the iron in copper ashes is deposited in the form of high oxide
It is in acid pellet.Meanwhile, oxidation reaction occurs for chlorinating agent, is continuously generated the chlorine source needed for chlorination reaction so that in copper ashes
Zinc, lead, copper metal element constantly occur chlorination reaction, form zinc, lead, copper chloride respectively.Due to zinc, lead, copper chlorination
Thing boiling point is relatively low, can be volatilized with chloride flue dust, so as to be collected.Therefore, oxidizing roasting process can be tentatively real
Iron and zinc, lead, the separation of copper in existing copper ashes.
(3) the second pelletizing is prepared
Pelletizing after the acid pellet that above-mentioned steps are obtained uniformly is mixed with reducing agent, binding agent, obtains the second pelletizing.And
And, control a diameter of 10~24mm of the second pelletizing.It is preferred that, control a diameter of 12~20mm of the second pelletizing.
In the present invention, the mesh of the granularity of binding agent≤200, preferably bentonite.
In the present invention, the mesh of the granularity of reducing agent≤200, preferably semi-coke.It is furthermore preferred that in the semi-coke that the present invention is selected, Gu
It is that 82.14wt%, volatile matter content are that 6.41wt%, content of ashes are that 8.32wt%, moisture are to determine carbon content
3.10wt%, sulfur content are 0.26wt%.
In the step, the addition of reducing agent is controlled according to following ratio：In fixed carbon and acid pellet in reducing agent
The mass ratio of oxygen be：C/O=1.2~2.0：1.In the step, the addition of binding agent is not limited, to enable to oxidation
Pelletizing and reducing agent the second pelletizing of formation are defined.
(4) second pelletizings carry out reduction roasting
Second pelletizing directly carries out reduction roasting processing, obtains metallized pellet and chloride flue dust.In the present invention, reduction
The temperature of calcination process process is 1100~1300 DEG C, and the time is 15~30min.It is used as the preferred embodiment of the invention, reduction
The temperature of calcination process process is 1150~1280 DEG C, and the time is 20~25min.
A part is there remains after oxidizing roasting process step, in copper ashes the lead, zinc, copper coin of chlorination reaction do not occur
Chlorination reaction occurs for element, in this step, residual lead, zinc, the oxide of copper, and corresponding chloride flue dust is generated respectively.Meanwhile,
Reduction reaction generation iron occurs for the high oxide of iron in acid pellet, and is present in metallized pellet.
In the present invention, volatility >=95.8wt% of lead in copper ashes, volatility >=95.6wt% of zinc, the rate of recovery of copper >=
95.5wt%.
(5) iron is separated
Metallized pellet after crushing, carries out mill ore magnetic selection processing, obtains iron powder and tailings.In iron powder, Iron grade >=
97.8%, the rate of recovery >=97.5% of iron.That is, the iron that the present invention is reclaimed from copper ashes, grade is high, and the rate of recovery is high, with notable
Economic use value.
Embodiment 1
In the copper ashes of the present embodiment, all iron content is 35.28wt%, and Zn content is 1.78wt%, and lead content is
0.26wt%, copper content is 1.54wt%.By copper ashes, bentonite pulverizing and jevigating to granularity below 200 mesh, the broken mill of calcium chloride
Thin is the mesh of 200 mesh~100 to granularity, and copper ashes, calcium chloride, bentonite are 100 according to mass ratio：5：5 uniform mixing, are then placed in
Pelletizing in disc balling machine, obtains a diameter of 6mm the first pelletizing.First pelletizing is aoxidized at a temperature of 800 DEG C after drying
The iron being calcined in 30min, copper ashes is present in acid pellet in the form of high price iron oxide.Meanwhile, with chlorination reaction removing
Copper and most lead and zinc in copper ashes, form corresponding chloride flue dust respectively.
Into acid pellet with addition of semi-coke and bentonite, the mass ratio of fixed carbon and oxygen in acid pellet is in semi-coke：C/O
=1.5：1, a diameter of 12mm the second pelletizing is obtained after pelletizing.Second pelletizing reduces 30min at a temperature of 1250 DEG C, obtains
To the metallized pellet containing iron and respectively containing lead, zinc, copper chloride flue dust.Wherein, the volatility of lead is 95.80%,
The volatility of zinc is 95.62%, and the rate of recovery of copper is 95.52%.After metallized pellet cooling, and through broken, mill ore magnetic selection, obtain
To metal iron powder.Iron grade is 97.86% in iron powder, and the rate of recovery of iron is 97.80%.
Embodiment 2
In the copper ashes of the present embodiment, all iron content is 36.78wt%, and Zn content is 2.01wt%, and lead content is
0.56wt%, copper content is 2.35wt%.By copper ashes, bentonite pulverizing and jevigating to granularity below 200 mesh, the broken mill of calcium chloride
Thin is the mesh of 200 mesh~100 to granularity, and copper ashes, calcium chloride, bentonite are 100 according to mass ratio：8：6 uniform mixing, are then placed in
Pelletizing in disc balling machine, obtains a diameter of 8mm the first pelletizing.First pelletizing is aoxidized at a temperature of 1000 DEG C after drying
The iron being calcined in 25min, copper ashes is present in acid pellet in the form of high price iron oxide.Meanwhile, with chlorination reaction removing
Copper and most lead and zinc in copper ashes, form corresponding chloride flue dust respectively.
Into acid pellet with addition of semi-coke and bentonite, the mass ratio of fixed carbon and oxygen in acid pellet is in semi-coke：C/O
=1.5：1, a diameter of 15mm the second pelletizing is obtained after pelletizing.Second pelletizing reduces 30min at a temperature of 1250 DEG C, obtains
To the metallized pellet containing iron and respectively containing lead, zinc, copper chloride flue dust.Wherein, the volatility of lead is 96.23%,
The volatility of zinc is 95.85%, and the rate of recovery of copper is 96.02%.After metallized pellet cooling, and through broken, mill ore magnetic selection, obtain
To metal iron powder.Iron grade is 97.98% in iron powder, and the rate of recovery of iron is 98.25%.
Embodiment 3
In the copper ashes of the present embodiment, all iron content is 37.25wt%, and Zn content is 2.86wt%, and lead content is
0.62wt%, copper content is 4.05wt%.By copper ashes, bentonite pulverizing and jevigating to granularity below 200 mesh, the broken mill of calcium chloride
Thin is the mesh of 200 mesh~100 to granularity, and copper ashes, calcium chloride, bentonite are 100 according to mass ratio：10：8 uniform mixing, Ran Houfang
Enter pelletizing in disc balling machine, obtain a diameter of 10mm the first pelletizing.The first pelletizing oxygen at a temperature of 900 DEG C after drying
The iron changed in roasting 30min, copper ashes is present in acid pellet in the form of high price iron oxide.Meanwhile, taken off with chlorination reaction
Except the copper in copper ashes and most lead and zinc, corresponding chloride flue dust is formed respectively.
Into acid pellet with addition of semi-coke and bentonite, the mass ratio of fixed carbon and oxygen in acid pellet is in semi-coke：C/O
=1.5：1, a diameter of 18mm the second pelletizing is obtained after pelletizing.Second pelletizing reduces 30min at a temperature of 1280 DEG C, obtains
To the metallized pellet containing iron and respectively containing lead, zinc, copper chloride flue dust.Wherein, the volatility of lead is 96.82%,
The volatility of zinc is 96.02%, and the rate of recovery of copper is 96.85%.After metallized pellet cooling, and through broken, mill ore magnetic selection, obtain
To metal iron powder.Iron grade is 98.08% in iron powder, and the rate of recovery of iron is 98.86%.
Embodiment 4
In the copper ashes of the present embodiment, all iron content is 35.58wt%, and Zn content is 1.24wt%, and lead content is
0.16wt%, copper content is 0.25wt%.By copper ashes, bentonite pulverizing and jevigating to granularity below 200 mesh, the broken mill of calcium chloride
Thin is the mesh of 200 mesh~100 to granularity, and copper ashes, calcium chloride, bentonite are 100 according to mass ratio：12：5 uniform mixing, Ran Houfang
Enter pelletizing in disc balling machine, obtain a diameter of 8mm the first pelletizing.The first pelletizing oxygen at a temperature of 1100 DEG C after drying
The iron changed in roasting 20min, copper ashes is present in acid pellet in the form of high price iron oxide.Meanwhile, taken off with chlorination reaction
Except the copper in copper ashes and most lead and zinc, corresponding chloride flue dust is formed respectively.
Into acid pellet with addition of semi-coke and bentonite, the mass ratio of fixed carbon and oxygen in acid pellet is in semi-coke：C/O
=1.2：1, a diameter of 20mm the second pelletizing is obtained after pelletizing.Second pelletizing reductase 12 5min at a temperature of 1150 DEG C, is obtained
To the metallized pellet containing iron and respectively containing lead, zinc, copper chloride flue dust.Wherein, the volatility of lead is 95.85%,
The volatility of zinc is 95.64%, and the rate of recovery of copper is 95.60%.After metallized pellet cooling, and through broken, mill ore magnetic selection, obtain
To metal iron powder.Iron grade is 97.84% in iron powder, and the rate of recovery of iron is 97.56%.
Embodiment 5
In the copper ashes of the present embodiment, all iron content is 37.86wt%, and Zn content is 2.57wt%, and lead content is
0.59wt%, copper content is 3.98wt%.By copper ashes, bentonite pulverizing and jevigating to granularity below 200 mesh, the broken mill of calcium chloride
Thin is the mesh of 200 mesh~100 to granularity, and copper ashes, calcium chloride, bentonite are 100 according to mass ratio：9：10 uniform mixing, Ran Houfang
Enter pelletizing in disc balling machine, obtain a diameter of 7mm the first pelletizing.The first pelletizing oxygen at a temperature of 1050 DEG C after drying
The iron changed in roasting 25min, copper ashes is present in acid pellet in the form of high price iron oxide.Meanwhile, taken off with chlorination reaction
Except the copper in copper ashes and most lead and zinc, corresponding chloride flue dust is formed respectively.
Into acid pellet with addition of semi-coke and bentonite, the mass ratio of fixed carbon and oxygen in acid pellet is in semi-coke：C/O
=2.0：1, a diameter of 14mm the second pelletizing is obtained after pelletizing.Second pelletizing reductase 12 0min at a temperature of 1260 DEG C, is obtained
To the metallized pellet containing iron and respectively containing lead, zinc, copper chloride flue dust.Wherein, the volatility of lead is 96.58%,
The volatility of zinc is 95.96%, and the rate of recovery of copper is 96.48%.After metallized pellet cooling, and through broken, mill ore magnetic selection, obtain
To metal iron powder.Iron grade is 97.88% in iron powder, and the rate of recovery of iron is 98.84%.
Finally it should be noted that：Obviously, above-described embodiment is only intended to clearly illustrate example of the present invention, and simultaneously
The non-restriction to embodiment.For those of ordinary skill in the field, it can also do on the basis of the above description
Go out other various forms of changes or variation.There is no necessity and possibility to exhaust all the enbodiments.And thus drawn
Among the obvious changes or variations that Shen goes out is still in protection scope of the present invention.
Claims (10)
1. a kind of processing method of copper ashes, it is characterised in that including step：
Pelletizing after copper ashes, chlorinating agent, binding agent are uniformly mixed, obtains the first pelletizing, wherein, iron, zinc, lead, copper are contained in copper ashes
Metallic element；
The oxidized calcination process of first pelletizing, obtains acid pellet, meanwhile, zinc, lead, copper metal element in the copper ashes
Form chloride flue dust；
Pelletizing after the acid pellet, reducing agent, binding agent are uniformly mixed, obtains the second pelletizing；
Second pelletizing is handled through reduction roasting, obtains metallized pellet, meanwhile, remaining zinc, lead, copper gold in the copper ashes
Belong to element formation chloride flue dust；
The metallized pellet is handled through mill ore magnetic selection, obtains iron powder.
2. according to the method described in claim 1, it is characterised in that in the copper ashes all iron content be 35.18~
38.05wt%, Zn content be 1.17~2.91wt%, lead content be 0.058~0.62wt%, copper content be 0.22~
4.05wt%；The mesh of the granularity of the copper ashes≤200.
3. according to the method described in claim 1, it is characterised in that the chlorinating agent is calcium chloride；The granularity of the chlorinating agent
For the mesh of 200 mesh~100.
4. according to the method described in claim 1, it is characterised in that the binding agent is bentonite；The granularity of the binding agent
≤ 200 mesh.
5. according to the method described in claim 1, it is characterised in that in first pelletizing, the copper ashes, chlorinating agent, bonding
The quality accounting of agent is 100:(5~12)：(5~10).
6. according to the method described in claim 1, it is characterised in that the temperature of the oxidizing roasting processing procedure is 700~
1100 DEG C, oxidizing roasting time is 15~30min.
7. according to the method described in claim 1, it is characterised in that the reducing agent is semi-coke；The granularity of the reducing agent≤
200 mesh.
8. according to the method described in claim 1, it is characterised in that in second pelletizing, the fixed carbon in the reducing agent
Mass ratio with the oxygen in the acid pellet is：C/O=1.2~2.0：1.
9. according to the method described in claim 1, it is characterised in that a diameter of 5~12mm of first pelletizing；Described second
A diameter of 10~24mm of pelletizing.
10. according to the method described in claim 1, it is characterised in that the temperature of the reduction roasting processing procedure is 1100~
1300 DEG C, the reduction roasting time is 15~30min.
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| CN113106249A (en) * | 2021-03-25 | 2021-07-13 | 北京大学 | Treatment method of gold tailings |
| CN113604664A (en) * | 2021-08-10 | 2021-11-05 | 江苏艾利特资源环境科技有限公司 | Method for recovering zinc product and/or iron product from ferrous metallurgy zinc-containing solid waste |
| CN115504676A (en) * | 2022-09-28 | 2022-12-23 | 安徽工业大学 | Method for extracting valuable metals from copper slag and utilizing high value of residue |
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Application publication date: 20171027 |