CN110129574A - The production method of cupric cast iron - Google Patents
The production method of cupric cast iron Download PDFInfo
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- CN110129574A CN110129574A CN201910432636.6A CN201910432636A CN110129574A CN 110129574 A CN110129574 A CN 110129574A CN 201910432636 A CN201910432636 A CN 201910432636A CN 110129574 A CN110129574 A CN 110129574A
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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
- C22B15/00—Obtaining copper
- C22B15/0026—Pyrometallurgy
- C22B15/0028—Smelting or converting
- C22B15/0052—Reduction smelting or converting
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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
- C22B15/00—Obtaining copper
- C22B15/0026—Pyrometallurgy
- C22B15/0054—Slag, slime, speiss, or dross treating
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
- C22B7/001—Dry processes
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
- C22B7/04—Working-up slag
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C33/00—Making ferrous alloys
- C22C33/04—Making ferrous alloys by melting
- C22C33/06—Making ferrous alloys by melting using master alloys
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/02—Ferrous alloys, e.g. steel alloys containing silicon
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/04—Ferrous alloys, e.g. steel alloys containing manganese
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
- C22C38/40—Ferrous alloys, e.g. steel alloys containing chromium with nickel
- C22C38/42—Ferrous alloys, e.g. steel alloys containing chromium with nickel with copper
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
- C22C38/40—Ferrous alloys, e.g. steel alloys containing chromium with nickel
- C22C38/46—Ferrous alloys, e.g. steel alloys containing chromium with nickel with vanadium
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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
Abstract
The disclosure provides a kind of production method of cupric cast iron, include: settlement treatment: copper ashes to be processed being placed in heating reducing zone and is warming up to 1300 DEG C~1500 DEG C, then the copper ashes after making heating flows into decanting zone and carries out settlement treatment, so that noble metal and copper matte regulus are separated from copper ashes；Melting and reducing processing: being placed in reduction furnace for the copper ashes after settlement treatment, and it is molten state that slag former, which is added, and is warming up to the material in reduction furnace, then carries out reduction reaction to reduction furnace blowing reducing agent, obtains cupric molten iron；Metallurgy: being placed in smelting furnace for cupric molten iron, and auxiliary agent, heating is added to carry out metallurgy；Casting processing: the cupric molten iron after metallurgy is subjected to casting processing, obtains cupric cast iron.This method has not only recycled noble metal, and can comprehensively utilize copper and iron in copper ashes, reduces smelting link, greatly reduces and smelts difficulty and production cost, has good industrial prospect.
Description
Technical field
The present invention relates to field of metallurgy, and in particular to a kind of production method of cupric cast iron.
Background technique
Copper ashes is the metallurgical slag discharged in pyrometallurgic copper process from copper smelter, is that various oxides are mutual in furnace charge and fuel
Eutectic made of melting.Currently, the every annual emissions in China are more than 10,000,000 tons, in addition, it is more than 1.2 that quantity is also stacked in the whole nation
Hundred million tons of copper ashes, copper ashes have become a fairly large number of industrial solid castoff generated in metallurgy industry.Although containing in copper ashes
A small amount of noble metal such as a variety of valuable metals such as Fe, Cu, Zn, Pb, Co and Ni and Au, Ag, but most of copper ashes is dumped there are cinder field,
Not only land occupation, pollution environment, but also cause the huge waste of resource.It, can be as can make full use of the iron and copper in copper ashes
Alleviate the imbalance between supply and demand of iron ore and copper mine to a certain extent；And as can a small amount of noble metal contained in the copper ashes effectively extracted,
Also economic benefit will preferably be promoted.Therefore comprehensive utilization copper ashes has important strategic importance and market prospects, is current
The important channel of Copper making industry value chain.
Iron in copper ashes is mainly with ferrosilite (2FeO ﹒ SiO2) and magnetic iron ore (Fe3O4) form exist, most of is silicon
Sour iron, copper is mainly with Cu2S, the form of CuO, Cu exist.Since the iron in copper ashes mainly exists in the form of fayalite,
It is difficult to effectively recycle weak magnetic mineral fayalite by conventional magnetic selection method.The iron recycled in copper ashes just needs elder generation
By the 2FeO ﹒ SiO in copper ashes2It is transformed into Fe3O4, then the method recycling for passing through magnetic separation.There is much the method for copper in recycling slag, main
There are pyrogenic process dilution, wet underwater welding and Mineral separation etc..However, copper ashes is focused mostly on using the research of technology in independent copper at present
Using or individually iron utilization two aspect.Extraction for copper metal in the dreg, beneficiating method application is wider, but resource utilization rate
It is low；Pyrometallurgical smelting metal recovery rate is high, but processing cost is high；The potential secondary pollution of wet-treating and costly.Although copper ashes is also
Devitrified glass, mineral wool can be prepared；For producing cement, valuable iron and copper and other metal resources are all greatly wasted.
With the development of science and technology influence of the people to copper to steel performance has new understanding, production is no longer stopped at already
Raw " copper brittleness " harm, there are also many beneficial effects in steel for copper, such as improve corrosion resistance, intensity, impact resistance.As can effectively
Using the copper and iron in copper ashes, and copper is played to the beneficial effect of iron, will provide a new approach using copper ashes to be efficient.
For example, Chinese patent application 200910163234.7, which discloses one kind, passes through blowing inert gas fusing and reducing iron
Method, although the method avoids thermal loss, but only individually consider the recycling of iron, considers returning for noble metal and copper
Receipts and Utilizing question, and impurity present in iron is not considered；Chinese patent application 201010167157.5 and
201010216133.4 improve the technique for mentioning iron on the basis of preceding patent, but do not consider that the recycling of noble metal and copper is asked still
Topic.Although Chinese patent application 201110380257.0 considers the problems of that copper recycles, villaumite is added in technique, still there is pollution
Problem.Chinese patent application 201410345197.2 propose using copper ashes produce copper-bearing antibacterial stainless steel, but its do not consider it is expensive
The extraction of metal, and it is complicated to prepare copper-bearing antibacterial stainless steel process, it is not easy to it realizes and utilizes higher cost.Chinese patent Shen
Please 201510390607.X propose to prepare cupric cast iron using containing copper ashes, but itself and to be mentioned to noble metal (Zn, Ag, Au etc.)
It takes, and cupric iron impurities in water is not handled, so that its product and undesirable.
It is noted that information disclosed in aforementioned background art part is only used for reinforcing understanding background of the invention, because
This it may include the information not constituted to the prior art known to persons of ordinary skill in the art.
Summary of the invention
One main purpose of the disclosure is to overcome at least one defect of the above-mentioned prior art, provide a kind of containing casting in bronze
The production method of iron, this method have not only recycled noble metal, and can comprehensively utilize copper and iron in copper ashes, the method reduce
Link is smelted, greatly reduces and smelts difficulty and production cost, there is good industrial prospect.
To achieve the goals above, the disclosure adopts the following technical scheme that
The disclosure provides a kind of production method of cupric cast iron, comprising: settlement treatment, melting and reducing processing, metallurgy
And casting processing, wherein
Settlement treatment includes: to provide a heating sedimentation furnace, and heating sedimentation furnace includes heating reducing zone and decanting zone, will be wait locate
The copper ashes of reason is placed in heating reducing zone and is warming up to 1300 DEG C~1500 DEG C, and the copper ashes after then making heating flows into decanting zone and sunk
Drop processing, so that noble metal and copper matte regulus are separated from copper ashes；Melting and reducing processing includes: to be placed in the copper ashes after settlement treatment also
Former furnace, it is molten state that slag former, which is added, and is warming up to the material in reduction furnace, is then melted to reduction furnace blowing reducing agent
Reduction reaction obtains cupric molten iron；Metallurgy includes: cupric molten iron to be placed in smelting furnace, and auxiliary agent, heating is added to carry out smelting
Refining processing；Casting processing includes: that the cupric molten iron after metallurgy is carried out casting processing, obtains cupric cast iron.
In accordance with one embodiment of the present disclosure, in settlement treatment, heating sedimentation furnace is using continuous blowing heating or electricity
Pole heating, wherein continuously the blowing raw material in blowing heating is natural gas, oil or carbon monoxide, jetting pressure 100kPa
~1000kPa.
In accordance with one embodiment of the present disclosure, settlement treatment further include: be blown inert gas to decanting zone, wherein this is lazy
Property gas be selected from nitrogen or argon gas, be blown inert gas pressure be 100kPa~1000kPa.
In accordance with one embodiment of the present disclosure, have respectively in settlement treatment, in copper ashes 85%~96% noble metal,
85%~96% copper matte regulus is separated from copper ashes.
In accordance with one embodiment of the present disclosure, in settlement treatment, the copper matte regulus isolated carries out Copper making to recycle.
In accordance with one embodiment of the present disclosure, the temperature of copper ashes to be processed is 1100 DEG C~1300 DEG C.
In accordance with one embodiment of the present disclosure, the temperature of fusion reduction reaction is 1400 DEG C~1650 DEG C.
In accordance with one embodiment of the present disclosure, in melting and reducing processing, slag former includes calcium oxide, the addition of slag former
Amount is determined according to basicity, in which:
In formula, MgO and SiO2Copper ashes after being all from settlement treatment, the scope control of basicity R is between 1.1~2.6, ω
(CaO) % indicates that the mass fraction of CaO, ω (MgO) % indicate the mass fraction of MgO, ω (SiO2) % expression SiO2Quality point
Number.
In accordance with one embodiment of the present disclosure, in melting and reducing processing, slag former includes calcium oxide and calcirm-fluoride, with matter
Percentages are measured, the content of calcirm-fluoride is the 8%~20% of slag former total amount.
In accordance with one embodiment of the present disclosure, in melting and reducing processing, reducing agent is selected from coal dust, carbon monoxide, natural
One of gas, hydrogen and tar are a variety of, by quality ratio, the additional amount of reducing agent according in reducing agent phosphorus content C with
Iron-content Fe in copper ashes after settlement treatmentx+Ratio determine, the scope control of ratio between 1.1~2.9, X be 2 or 3.
In accordance with one embodiment of the present disclosure, melting and reducing processing in, further include fusion reduction reaction carry out when, to
Reduction furnace is blown inert gas and/or is stirred to the material of molten state, and inert gas is selected from nitrogen or argon gas, is blown inertia
The pressure of gas is 100kPa~1000kPa.
In accordance with one embodiment of the present disclosure, in metallurgy, auxiliary agent is selected from steel scrap, carburant, desulfurizing agent, dephosphorization
One of agent, manganese iron, ferrosilicon or inovulant are a variety of；The temperature of metallurgy is 1300 DEG C~1580 DEG C.
In accordance with one embodiment of the present disclosure, casting processing includes forming the cupric molten iron casting after metallurgy,
Wherein pouring temperature is 1280 DEG C~1500 DEG C, and the mode for casting processing is sand casting or Special Processes of Metal Castings.
In accordance with one embodiment of the present disclosure, cupric cast iron is cupric Elverite, and by percentage to the quality, cupric is resistance to
The carbon content for losing cast iron is not more than 2.11%.
In accordance with one embodiment of the present disclosure, metallurgy further include: into smelting furnace be added fine copper, manganeisen,
One of Antaciron, ferrochrome, dilval or ferro-molybdenum are a variety of.
As shown from the above technical solution, the advantages of production method for the cupric cast iron that the disclosure proposes and good effect exist
In:
Present disclose provides a kind of production method of cupric cast iron, this method is before fusion reduction reaction by sedimentation
Reason obtains most noble metal and copper matte regulus, and recycling noble metal can directly bring economic benefit, and copper matte regulus can return to copper metallurgy stream
Journey not only takes full advantage of copper, and has taken away a large amount of sulphur, lays a good foundation, can subtract for the subsequent smelting process that enters
Few sulfur removal technology and desulphurization cost.Disclosed method greatly reduces the smelting difficulty of cupric cast iron, can also pass through addition
The alloys such as manganese, silicon, copper, chromium, nickel and molybdenum obtain cupric Elverite, can greatly promote the value of product, increase economic efficiency.
Detailed description of the invention
Fig. 1 is the production system schematic diagram of the cupric cast iron of one embodiment of the disclosure；
Fig. 2 is the production technological process of the cupric cast iron of one embodiment of the disclosure.
Wherein, the reference numerals are as follows:
100: heating sedimentation furnace
101: heating reducing zone
102: decanting zone
103: partition
200: reduction furnace
300: smelting furnace
400: casting device
500: tundish
Specific embodiment
The disclosure is illustrated by specific embodiment with reference to the accompanying drawing, but the disclosure is not limited to following reality
Apply example.The endpoint of disclosed range and any value are not limited to the accurate range or value in the disclosure, these ranges or
Value should be understood as comprising the value close to these ranges or value.For numberical range, between the endpoint value of each range, respectively
It can be combined with each other between the endpoint value of a range and individual point value, and individually between point value and obtain one or more
New numberical range, these numberical ranges should be considered as specific open herein.
Copper ashes is that a fairly large number of industrial solid castoff is generated in metallurgy industry, and Fe, Cu, Zn, Pb, Co are contained in copper ashes
With a small amount of noble metal such as a variety of valuable metals such as Ni and Au, Ag, but most of copper ashes is dumped there are cinder field, not only land occupation,
Environment is polluted, and causes the huge waste of resource.The copper ashes ingredient obtained by different smelting processes has certain difference,
Range is as shown in table 1.
Chemical component/% of 1 clinker of table
| TFe | TCu | Fe3O4 | SiO2 | Al2O3 | CaO | S | Au* |
| 29~45 | 0.45~3.0 | 1~20 | 25~40 | ≤10 | ≤10 | 0.6~2.8 | <0.5 |
* unit is g/t
As shown in Table 1, iron content 29%~45% in copper ashes, and all iron ore grade average value of China's Iron industry is only
It is 29.1%, needs a large amount of import Wai Kuang to arrange in pairs or groups with it and be sintered and pelletizing；The many copper mine copper mining grades in China have been at present
There was only 0.2%~0.3%, and copper content is then 0.5% or more in copper ashes.As can the iron and copper in copper ashes are made full use of, it can
Alleviate the imbalance between supply and demand of iron ore and copper mine to a certain extent.
Iron in copper ashes is mainly with ferrosilite (2FeO ﹒ SiO2) and magnetic iron ore (Fe3O4) form exist, most of is silicon
Sour iron, copper is mainly with Cu2S, the form of CuO, Cu exist.Since the iron in copper ashes mainly exists in the form of fayalite,
It is difficult to effectively recycle weak magnetic mineral fayalite by conventional magnetic selection method.The iron recycled in copper ashes just needs elder generation
By the 2FeO ﹒ SiO in copper ashes2It is transformed into Fe3O4, then the method recycling for passing through magnetic separation.There are many disadvantages for such method, such as
Can not recycle noble metal, by high temperature copper ashes it is cooling after high-temperature roasting (temperature of general copper ashes is 1200 DEG C) again, cause heat
The problems such as significant wastage, the not high rate of recovery of iron.And there is complex process, at high cost, nothing in wet underwater welding and Mineral separation etc.
Method realizes the disadvantages of industrialization.Although copper ashes can also prepare devitrified glass, mineral wool, for producing cement, all greatly waste
Valuable iron and copper and other metal resources.Copper ashes is focused mostly on using the research of technology in the utilization of independent copper or single at present
Two aspects of utilization of only iron.Extraction for noble metal in copper ashes, and it is less using the copper and iron research in slag simultaneously, and deposit
In certain deficiency.
For this purpose, present disclose provides a kind of production methods of cupric cast iron.Wherein, Fig. 1 representatively illustrates the disclosure
The production system schematic diagram of the cupric cast iron of one embodiment；Fig. 2 representatively illustrates an embodiment of the disclosure
Cupric cast iron production technological process.Below in conjunction with Fig. 1 and Fig. 2 to the production method of the cupric cast iron of the disclosure into one
Walk explanation.It will be readily appreciated by those skilled in the art that disclosed method can also be applied to other coloured slag systems.To under
The specific embodiment stated is made a variety of remodeling, addition, substitution, deletion or other variations, these variations and should still be mentioned in the disclosure
In the concept of the production method of cupric cast iron out.
As shown in fig.1, in the present embodiment, the production system of cupric cast iron includes: heating sedimentation furnace 100, reduction
Furnace 200, smelting furnace 300, casting device 400, the life of cupric cast iron is illustrated below with reference to the production system of the cupric cast iron
Production method:
Referring to figs. 1 and 2, the production method of the cupric cast iron of the disclosure include settlement treatment, melting and reducing processing,
Metallurgy, casting processing, are described as follows:
(1) settlement treatment
Settlement treatment is carried out using heating sedimentation furnace 100 above-mentioned, which includes heating reducing zone 101
It heats in some embodiments with decanting zone 102 and is equipped with partition 103 between reducing zone 101 and decanting zone 102, and partition 103
There is gap with the bottom of heating sedimentation furnace 100, so that two portions that heating reducing zone 101 is connected to decanting zone 102 for bottom
Point.The material outlet of decanting zone 102 includes the first liquid outlet and the first slag notch (not shown).
Firstly, copper ashes to be processed, which is placed in heating reducing zone 101, is warming up to 1300 DEG C~1500 DEG C, in decanting zone 102
Settlement treatment is carried out, since copper ashes is different with the density of copper matte regulus, sedimentation separation can be completed in decanting zone 102, is contained in copper ashes
Some noble metals are discharged with liquid form from the first liquid outlet together with copper matte regulus, and the high temperature furnace slag after settlement treatment is slagged tap from first
Mouth discharge.Processing is extracted to above-mentioned noble metal, is then recycled the copper sulphur after extraction noble metal, such as return
Copper making is carried out into converting furnace.By above-mentioned settlement treatment, make 85%~96% copper matte regulus and 85%~96% noble metal
It is separated from copper ashes, reduces the sulfur content of copper ashes, created condition for further reduction cupric molten iron, reduce sulfur removal technology
Process and desulphurization cost.
In some embodiments, copper ashes to be processed can be the high temperature copper of coming out of the stove that temperature is 1100 DEG C~1300 DEG C
Slag, the high temperature copper ashes of coming out of the stove are transferred in the heating reducing zone 101 of heating sedimentation furnace 100 by tundish 500.Pass through directly benefit
With high temperature copper ashes, its own waste heat can be made full use of, meets the requirement of energy-saving and emission-reduction.
In some embodiments, top, bottom and/or the side for heating sedimentation furnace 100 offer the first blowing mouth.It should
First blowing mouth is furnished with spray gun, for being blown reducing gas, such as natural gas, oil or carbon monoxide to the heating sedimentation furnace 100
Deng.According to the position of the first blowing mouth setting, injection method can be top blast, bottom blowing, side-blown or composite blowing mode, and different
Position may be provided with one or more first and be blown mouth.Jetting pressure can be 100kPa~1000kPa, can continuously be sprayed
It blows.Advantage using blowing reducing gas is: the heat for heating sedimentation furnace can provide heat by being blown above-mentioned reducing gas,
Cost is relatively low for this raising temperature；Further, since the gas of blowing is reducibility gas, the reducing atmosphere of formation can will be to
Ferroso-ferric oxide (the Fe contained in the copper ashes of processing3O4) it is reduced to ferrous oxide (FeO), to reduce the viscosity of copper ashes, favorably
In the progress of sedimentation separation.But the heating method of the disclosure is not limited to this, for example, it is also possible to be added using electrode approach
Heat.It, can be with after flowing into decanting zone after copper ashes to be processed is heated to certain temperature in addition, in some embodiments
Continue to heat using electrode, for keeping the temperature in furnace, to complete sedimentation separation treatment process.
In some embodiments, it can also be blown inert gas to the decanting zone 102, wherein the inert gas is selected from
The pressure of nitrogen or argon gas, the blowing inert gas is 100kPa~1000kPa.By being blown into indifferent gas in infall process
Body stirring can make copper matte regulus collision grow up, and be more advantageous to sedimentation.
(2) melting and reducing is handled
Melting and reducing processing is carried out using reduction furnace 200 above-mentioned.Wherein, the material inlet of reduction furnace 200 is connected to heavy
First slag notch in area 102 drops, and the material outlet of reduction furnace 200 includes the second liquid outlet and the second slag notch (not shown).
Copper ashes after settlement treatment above-mentioned is transferred in the reduction furnace 200, slag former is added and is warming up to reduction furnace
Material in 200 is molten state, is then blown reducing agent to reduction furnace 200 and carries out fusion reduction reaction, obtains cupric molten iron and furnace
Slag.The cupric molten iron of its high temperature is flowed out from the second liquid outlet, into steelmaking process；Clinker is discharged by the second slag notch.?
In some embodiments, reduction furnace 200 is additionally provided with exhanst gas outlet, and exhanst gas outlet is connected to off-gas recovery processing unit, to also
Flue gas and harmful element during original carry out special processing and recycling.By above step, iron and copper are reduced, and
The lower melting-point metals such as zinc (Zn) are then recovered into flue gas.The main chemical reactions that smelting reduction process occurs are as follows:
Cu2S+CaO+C=2Cu+CaS+CO (1)
Fe2SiO4+ 2CaO+2C=2Fe+Ca2SiO4+2CO (2)
Fe3O4+ 4C=3Fe+4CO (3)
2 [P]+5 (FeO)+4 (CaO)=(4CaOP2O5)+[Fe] (4)
[FeS]+(CaO)=(CaS)+(FeO) (5)
CuO+C=Cu+CO (6)
In some embodiments, the temperature of fusion reduction reaction is 1400 DEG C~1650 DEG C.
In some embodiments, the side or top or bottom of reduction furnace 200 offer one or more second and are blown
Mouthful, for example, reduction furnace shown in FIG. 1 is side-blown converter, it is equipped with multiple second blowing mouths.Material in furnace 200 to be restored reaches
It states when being in molten condition after temperature range, reducing agent is blown into reduction furnace 200 by the second blowing mouth using spray gun,
In, reducing agent is selected from one of coal dust, carbon monoxide, natural gas, hydrogen and tar or a variety of, it is preferable that with coal injection
Based on, it is lower compared to other technical costs.By quality ratio, the additional amount of reducing agent according in reducing agent phosphorus content C with
Iron-content Fe in copper ashes after settlement treatmentx+Ratio determine, the scope control of ratio between 1.1~2.9, X be 2 or 3.
In some embodiments, agitating device (not shown) can also be increased in the reduction furnace 200, to the melting
The material of state is stirred, or the modes such as blowing inert gas increase reaction rate to improve the dynamic conditions of reaction.
Wherein, inert gas can be nitrogen (N2) or argon gas (Ar), jetting pressure is 100kPa~1000kPa.
In some embodiments, slag former includes calcium oxide, also can choose addition calcium carbonate, calcium carbonate is through thermally decomposing
After can produce calcium oxide for slag making.The additional amount of slag former is determined according to basicity R, in which:
In formula, MgO and SiO2Copper ashes after being all from settlement treatment, the scope control of basicity R is between 1.1~2.6, ω
(CaO) % indicates that the mass fraction of CaO, ω (MgO) % indicate the mass fraction of MgO, ω (SiO2) % expression SiO2Quality point
Number.
In some embodiments, in order to carry out frit reaction preferably, a small amount of calcirm-fluoride (CaF can be added2) in
In slag former.With the raising of calcium oxide additional amount, the viscosity of copper ashes can be increased, and then reduce contact of the calcium oxide with copper ashes
Face is degrading reducing condition and reduces reaction rate, and CaF2Addition can destroy the silicon oxygen four sides of silicate ion in slag
Body structure reduces viscosity coefficient of dross, increases contact area, and then improves the dynamic conditions that reduction reaction occurs.Preferably, with matter
Percentages are measured, calcirm-fluoride additional amount is the 8%~20% of slag former total amount.
In the art, reduction furnace is commonly used for the smelting of copper, the disclosure further use the reduction furnace and meanwhile carry out copper and
The smelting of iron makes the ferriferous oxide in copper ashes be reduced to iron, and the oxide of copper is reduced to copper, has carried out comprehensive benefit to copper and iron
With, and the rate of recovery is higher, reduces production cost.Due to it have passed through fusion reduction reaction processing after, sulfur content in copper ashes compared with
It is low, greatly reduce desulfurization burden；Zinc, lead, arsenic etc. enter flue gas in reduction process, can pass through setting since fusing point is lower
System recycling, and flue gas is discharged into atmosphere after treatment；In addition, the clinker generated can also be used to produce cement, mineral wool, use
In paving the way.
(3) metallurgy
Cupric molten iron after fusion reduction reaction is placed in smelting furnace 300, and auxiliary agent, heating is added to be smelted
Processing；Wherein, the material inlet of smelting furnace 300 is connected to the second liquid outlet of reduction furnace 200.
In some embodiments, smelting furnace 300 can be electric furnace or induction furnace.The auxiliary agent include but is not limited to steel scrap,
One of carburant, desulfurizing agent, Dephosphorising agent, manganese iron, ferrosilicon or inovulant are a variety of.By auxiliary agent to cupric molten iron carry out at
Divide adjustment to meet the component requirements of foundry iron.The temperature of metallurgy is unsuitable excessively high, also unsuitable too low, suitable for producing cupric
The smelting temperature of cast iron is 1300 DEG C~1580 DEG C.
(4) casting is handled
Casting processing includes that the cupric molten iron after metallurgy is placed in casting device 400 to carry out moulding by casting.Wherein,
The material inlet of casting device 400 is connected to the material outlet of smelting furnace 300.
In some embodiments, pouring temperature is 1280 DEG C~1500 DEG C, and the mode for casting processing can be sand casting
Or Special Processes of Metal Castings, the Special Processes of Metal Castings can be precision-investment casting, plaster precision foundry, ceramic precision casting, disappear
Lost pattern casting, permanent mold casting, compression casting, low pressure casting, counter-pressure casting, suction pouring, extrusion casint, centrifugal casting, company
Continuous casting, semi-continuous casting, shell moulded casting, graphite mold casting, electroslag smelting casting etc..But the present disclosure is not limited thereto.
In some embodiments, disclosed method can produce cupric Elverite.It specifically, can be by smelting
When processing, the requirement according to different cupric Elverites to copper, manganese, silicon, chromium, nickel and molybdenum etc. carries out the alloy of heterogeneity
Change.Specifically, it may include: during metallurgy to smelting furnace be added fine copper, manganeisen, Antaciron, ferrochrome,
One of dilval or ferro-molybdenum are a variety of.Cupric Elverite can also be carried out by the change to carbon content
Production, by percentage to the quality, can by the carbon content control of cupric Elverite 2.11% hereinafter, other contents are by adding
Copper, manganese, silicon, chromium, nickel and molybdenum etc. is added to realize.
The disclosure is described in detail below with reference to embodiment, but the protection scope of the disclosure is not by following embodiment institutes
Limit.
Embodiment 1:
(1) settlement treatment extracts noble metal and copper matte regulus
First by 1130 DEG C high temperature copper ashes (TFe:42.65%, TCu:1.12%, Fe3O4: 16.2%, SiO2:
25.9%, Al2O3: 1.35%, CaO:2.66%, S:1.26%, Au:0.48g/t) heating sedimentation furnace is transferred to by tundish
In heating reducing zone in, provided by side-blown natural gas and heat and restore Fe3O4, jetting pressure 180kPa, mode is side
It blows, raises the temperature to 1380 DEG C；Then copper ashes flows into decanting zone by partition, so that copper matte regulus is grown up by nitrogen-blow, is blown
Pressure is 180kPa, and mode is side-blown；It is elevated the temperature using electrode and is maintained at 1380 DEG C, then start infall process, this process
For continuous process；In infall process 87% copper and 88% noble metal it is recyclable；It recycles obtained copper matte regulus and reenters copper metallurgy
Process；And remaining copper ashes enters Smelting Reduction Process.
(2) fused reduction iron-smelting obtains cupric molten iron
High temperature copper ashes after sedimentation is flowed into reduction furnace, a certain amount of slag former CaO is then added；The addition of slag former
Amount is calculated by basicity, and the basicity of the present embodiment is 1.4；CaF2Additional amount be slag former 12%；Pass through heated by electrodes
Mode furnace temperature is risen to 1480 DEG C.When material and slag former in furnace to be restored are in molten state, to molten bath coal injection, add
Enter amount with C/Fex+(x=2,3) is than being 1.6.After blowing, to molten bath nitrogen-blow, changes Burners Positions during blowing, make
Stirring reaches optimum efficiency；Keep slag iron interfacial reaction more abundant with addition of agitating device, reaction speed is faster.
(3) metallurgy and casting processing
Cupric molten iron is transferred in electric furnace, metallurgy is carried out.Pass through steel scrap, carburant, desulfurizing agent, Dephosphorising agent, manganese
Ferroalloy, Antaciron carry out composition adjustment to cupric molten iron to meet the component requirements of foundry iron.Further, by temperature
1500 DEG C are risen to, alloying is realized by addition fine copper, ferrochrome, dilval and ferro-molybdenum etc., is then cast
Processing.Wherein, pouring temperature is 1300 DEG C in casting processing.
Finally obtained cupric cast iron composition are as follows: C:3.2%, Si:1.6%, Mn:0.7%, S:0.12%, P:0.02%,
Cu:1.2%, Mo:0.5%.
Embodiment 2:
(1) settlement treatment extracts noble metal and copper matte regulus
First by 1200 DEG C high temperature copper ashes (TFe:50.45%, TCu:1.2%, Fe3O4: 12.2%, SiO2: 26.9%,
Al2O3: 1.15%, CaO:2.86%, S:1.36%, Au:0.43g/t) by tundish be transferred to heating sedimentation furnace in heating
In reducing zone, heat is provided by side-blown natural gas and restores Fe3O4, jetting pressure 160kPa, mode be it is side-blown, make temperature
It is increased to 1440 DEG C；Then decanting zone is flowed by partition, so that copper matte regulus is grown up by nitrogen-blow, jetting pressure 160kPa,
Mode is side-blown；It is elevated the temperature using electrode and is maintained at 1440 DEG C, then start infall process, this process is continuous process；It is heavy
During drop 90% copper and 90% noble metal it is recyclable；It recycles obtained copper matte regulus and reenters copper metallurgy process；And it is remaining
Copper ashes enters Smelting Reduction Process.
(2) fused reduction iron-smelting obtains cupric molten iron
High temperature copper ashes after sedimentation is flowed into reduction furnace, a certain amount of slag former CaO is then added；The addition of slag former
Amount is calculated by basicity, and the present embodiment basicity is 1.8；CaF2Additional amount be slag former 15%；Pass through heated by electrodes
Furnace temperature is risen to 1520 DEG C by mode.When furnace charge and slag former are in molten state, to molten bath coal injection, additional amount is with C/Fex+
(x=2,3) is than being 1.7.After blowing, to molten bath nitrogen-blow, change Burners Positions during blowing, stirring is made to reach best
Effect；Keep slag iron interfacial reaction more abundant with addition of agitating device, reaction speed is faster.
(3) metallurgy and casting processing
Cupric molten iron is transferred in electric furnace, metallurgy is carried out.Pass through steel scrap, carburant, desulfurizing agent, Dephosphorising agent, manganese
Ferroalloy, Antaciron carry out composition adjustment to cupric molten iron to meet the component requirements of foundry iron.Further, by temperature
1550 DEG C are risen to, alloying is realized by addition fine copper, ferrochrome, dilval and ferro-molybdenum etc., is then cast
Processing, wherein pouring temperature is 1380 DEG C.
Final cupric cast iron composition are as follows: C:3.3%, Si:2.2%, Mn:0.6%, S:0.04%, P:0.08%, Cu:
4.5%, Ni:1.8%, Cr:0.8%.
Embodiment 3:
(1) settlement treatment extracts noble metal and copper matte regulus
First by 1100 DEG C high temperature copper ashes (TFe:48.45%, TCu:1.3%, Fe3O4: 15.2%, SiO2: 28.9%,
Al2O3: 1.33%, CaO:2.88%, S:1.66%, Au:0.42g/t) by tundish be transferred to heating sedimentation furnace in heating
In reducing zone, heat is provided by side-blown natural gas and restores Fe3O4, jetting pressure 250kPa, mode be it is side-blown, make temperature
It is increased to 1500 DEG C；Then decanting zone is flowed by partition, so that copper matte regulus is grown up by nitrogen-blow, jetting pressure 250kPa,
Mode is side-blown；It is elevated the temperature using electrode and is maintained at 1500 DEG C, then start infall process, this process is continuous process；It is heavy
During drop 92% copper and 90% noble metal it is recyclable；It recycles obtained copper matte regulus and reenters copper metallurgy process；And it is remaining
Copper ashes enters Smelting Reduction Process.
(2) fused reduction iron-smelting obtains cupric molten iron
High temperature copper ashes after sedimentation is flowed into reduction furnace, a certain amount of slag former CaO is then added；The addition of slag former
Amount is calculated by basicity, and the present embodiment basicity is 2.0；CaF2Additional amount be slag former 14%；Pass through heated by electrodes
Furnace temperature is risen to 1580 DEG C by mode.When furnace charge and slag former are in molten state, to molten bath coal injection, additional amount is with C/Fex+
(x=2,3) is than being 1.8.After blowing, to molten bath nitrogen-blow, change Burners Positions during blowing, stirring is made to reach best
Effect；Keep slag iron interfacial reaction more abundant with addition of agitating device, reaction speed is faster.
(3) metallurgy and casting processing
Cupric molten iron is transferred in electric furnace, metallurgy is carried out.Pass through steel scrap, carburant, desulfurizing agent, Dephosphorising agent, manganese
Ferroalloy, Antaciron carry out composition adjustment to cupric molten iron to meet the component requirements of foundry iron.Further, by temperature
1580 DEG C are risen to, alloying is realized by addition fine copper, ferrochrome, dilval and ferro-molybdenum etc., is then cast
Processing, wherein pouring temperature is 1400 DEG C.
Final cupric cast iron composition are as follows: C:0.11%, Si:0.22%, Mn:0.8%, S:0.01%, P:0.01%, Cu:
1.2%, Ni:1.6%, Cr:0.2%, V:0.1%.
Embodiment 4:
(1) settlement treatment extracts noble metal and copper matte regulus
First by 1200 DEG C high temperature copper ashes (TFe:51.45%, TCu:1.5%, Fe3O4: 14.2%, SiO2: 25.6%,
Al2O3: 1.23%, CaO:2.38%, S:1.36%, Au:0.42g/t) by tundish be transferred to heating sedimentation furnace in heating
In reducing zone, heat is provided by side-blown natural gas and restores Fe3O4, jetting pressure 240kPa, mode be it is side-blown, make temperature
It is increased to 1400 DEG C；Then decanting zone is flowed by partition, so that copper matte regulus is grown up by nitrogen-blow, jetting pressure 240kPa,
Mode is side-blown；It is elevated the temperature using electrode and is maintained at 1400 DEG C, then start infall process, this process is continuous process；It is heavy
During drop 92% copper and 93% noble metal it is recyclable；It recycles obtained copper matte regulus and reenters copper metallurgy process；And it is remaining
Copper ashes enters Smelting Reduction Process.
(2) fused reduction iron-smelting obtains cupric molten iron
High temperature copper ashes after sedimentation is flowed into reduction furnace, a certain amount of slag former CaO is then added；The addition of slag former
Amount is calculated by basicity, and the present embodiment basicity is 1.8；CaF2Additional amount be slag former 16%；Pass through heated by electrodes
Furnace temperature is risen to 1570 DEG C by mode.When furnace charge and slag former are in molten state, to molten bath coal injection, additional amount is with C/Fex+
(x=2,3) is than being 1.6.After blowing, to molten bath nitrogen-blow, change Burners Positions during blowing, stirring is made to reach best
Effect；Keep slag iron interfacial reaction more abundant with addition of agitating device, reaction speed is faster.
(3) metallurgy and casting processing
Cupric molten iron is transferred in electric furnace, metallurgy is carried out.Pass through steel scrap, carburant, desulfurizing agent, Dephosphorising agent, manganese
Ferroalloy, Antaciron carry out composition adjustment to cupric molten iron to meet the component requirements of foundry iron.Further, by temperature
1570 DEG C are risen to, alloying is realized by addition fine copper, ferrochrome, dilval and ferro-molybdenum etc., is then cast
Processing, wherein pouring temperature is 1390 DEG C.
Final cupric cast iron composition are as follows: C:0.12%, Si:0.28%, Mn:0.7%, S:0.02%, P:0.01%, Cu:
1.3%, Ni:1.7%, Cr:0.3%, V:0.13%.
In summary, the production method of the cupric cast iron of the disclosure makes most copper by carrying out settlement treatment first
Sulfonium and noble metal can be separated from copper ashes, and noble metal can be recycled directly and bring economic benefit, and in copper ashes sulfur content reduction,
It is created condition further to restore cupric molten iron, reduces desulfurization process and desulphurization cost.In addition, the disclosure also uses
Reduction furnace carries out the recycling of iron and copper simultaneously, produces cupric cast iron, greatly reduces the smelting difficulty of cupric cast iron, can be with
Cupric Elverite is obtained by alloys such as addition manganese, silicon, copper, chromium, nickel and molybdenums, the value of product can be greatly promoted, improve warp
Ji benefit.
Those skilled in the art should be noted that embodiment described in the invention is only exemplary, can be
Various other replacements, changes and improvements are made in the scope of the present invention.Thus, the present invention is not limited to the above embodiments, and only
It is defined by the claims.
Claims (15)
1. a kind of production method of cupric cast iron characterized by comprising
Settlement treatment: providing a heating sedimentation furnace, and the heating sedimentation furnace includes heating reducing zone and decanting zone, will be to be processed
Copper ashes is placed in the heating reducing zone and is warming up to 1300 DEG C~1500 DEG C, and the copper ashes after then making the heating flows into the sedimentation
Area carries out settlement treatment, so that noble metal and copper matte regulus are separated from the copper ashes；
Melting and reducing processing: being placed in reduction furnace for the copper ashes after the settlement treatment, and slag former is added and is warming up to the reduction
Material in furnace is molten state, then carries out fusion reduction reaction to reduction furnace blowing reducing agent, obtains cupric molten iron；
Metallurgy: being placed in smelting furnace for the cupric molten iron, and auxiliary agent, heating is added to carry out metallurgy；
Casting processing: the cupric molten iron after the metallurgy is subjected to casting processing, obtains cupric cast iron.
2. production method according to claim 1, which is characterized in that in the settlement treatment, the heating sedimentation furnace is adopted
With continuous blowing heating or electrode heating, wherein the blowing raw material in the continuous blowing heating be natural gas, oil or
Carbon monoxide, jetting pressure are 100kPa~1000kPa.
3. production method according to claim 1, which is characterized in that the settlement treatment further include: the decanting zone Xiang Suoshu
Be blown inert gas, wherein the inert gas be selected from nitrogen or argon gas, it is described blowing inert gas pressure be 100kPa~
1000kPa。
4. production method according to claim 1, which is characterized in that in the settlement treatment, have respectively in the copper ashes
85%~96% noble metal, 85%~96% copper matte regulus separated from the copper ashes.
5. production method according to claim 1, which is characterized in that in the settlement treatment, the copper matte regulus isolated
Copper making is carried out to recycle.
6. production method according to claim 1, which is characterized in that the temperature of the copper ashes to be processed be 1100 DEG C~
1300℃。
7. production method according to claim 1, which is characterized in that the temperature of the fusion reduction reaction be 1400 DEG C~
1650℃。
8. production method according to claim 1, which is characterized in that in the melting and reducing processing, the slag former packet
Calcium oxide is included, the additional amount of the slag former is determined according to basicity, in which:
In formula, MgO and SiO2Copper ashes after being all from the settlement treatment, the scope control of the basicity R 1.1~2.6 it
Between, ω (CaO) % indicates that the mass fraction of CaO, ω (MgO) % indicate the mass fraction of MgO, ω (SiO2) % expression SiO2's
Mass fraction.
9. production method according to claim 8, which is characterized in that in the melting and reducing processing, the slag former packet
Calcium oxide and calcirm-fluoride are included, by percentage to the quality, the content of the calcirm-fluoride is the 8%~20% of the slag former total amount.
10. production method according to claim 1, which is characterized in that in the melting and reducing processing, the reducing agent choosing
From one of coal dust, carbon monoxide, natural gas, hydrogen and tar or a variety of, by quality ratio, the additional amount of the reducing agent
According to the iron-content Fe in the copper ashes after the phosphorus content C and the settlement treatment in reducing agentx+Ratio determine, the ratio
For scope control between 1.1~2.9, X is 2 or 3.
11. production method according to claim 1, which is characterized in that further include melting in the melting and reducing processing
When reduction reaction carries out, Xiang Suoshu reduction furnace is blown inert gas and/or is stirred to the material of the molten state, described lazy
Property gas be selected from nitrogen or argon gas, it is described blowing inert gas pressure be 100kPa~1000kPa.
12. production method according to claim 1, which is characterized in that in the metallurgy, the auxiliary agent is selected from useless
One of steel, carburant, desulfurizing agent, Dephosphorising agent, manganese iron, ferrosilicon or inovulant are a variety of；The temperature of the metallurgy is
1300 DEG C~1580 DEG C.
13. production method according to claim 1, which is characterized in that the casting processing includes by the metallurgy
Cupric molten iron casting molding afterwards, wherein the pouring temperature is 1280 DEG C~1500 DEG C, the mode of the casting processing is sand
Mold casting or Special Processes of Metal Castings.
14. production method according to claim 1, which is characterized in that the cupric cast iron is cupric Elverite, with matter
Percentages are measured, the carbon content of the cupric Elverite is not more than 2.11%.
15. production method according to claim 14, which is characterized in that the metallurgy further include: to the smelting
One of fine copper, manganeisen, Antaciron, ferrochrome, dilval or ferro-molybdenum or a variety of are added in furnace.
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