CN1245526C - Noncontact type metal element carbon hot melt reduction method - Google Patents
Noncontact type metal element carbon hot melt reduction method Download PDFInfo
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- CN1245526C CN1245526C CN 03121189 CN03121189A CN1245526C CN 1245526 C CN1245526 C CN 1245526C CN 03121189 CN03121189 CN 03121189 CN 03121189 A CN03121189 A CN 03121189A CN 1245526 C CN1245526 C CN 1245526C
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- oxide
- solid electrolyte
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- slag
- reduction method
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Abstract
The present invention belongs to the field of metallurgy materials, and is especially suitable for melting and reducing pure metal. The present invention comprises a solid electrolyte 2 for conducting oxygen ions, a metal-C fused mass 3, slag 5 containing a reduced substance, the reduced substance 6 and electrodes 7. The present invention is characterized in that the method uses coal and carbon as a reducing agent 1; a metallic protective isolation layer 4 is arranged between the slag and the solid electrolyte; the two electrodes 7 are connected by an electrochemical controller 8. Compared with the traditional contact type reduction, the method of the present invention avoids the problem that reduced products are polluted by the reducing agent, and shortens metallurgy flow processes. Compared with the traditional electrolysis reduction method, the method of the present invention overcomes the problems of large energy consumption, environment pollution, etc. brought by low thermoelectric conversion efficiency. Compared with the existing method of using the solid electrolyte or a mixed conductor as 'the isolation layer', the method of the present invention uses coal as the reducing agent, and has the advantages of convenient application, large activity and stable oxygen pressure division. The protective isolation layer is introduced between the solid electrolyte and the slag containing the reduced substance, and thus, the problem that the solid electrolyte and the electrodes are eroded by the slag is solved.
Description
Technical field:
The invention belongs to the metallurgical material field, be specially adapted to the melting and reducing of clean metal.
Technical background:
The metallic element reduction is an important step in the metallurgy, it is the atoms metal with positive charge, become the process of free atom by certain approach electron gain, the method of reducing that adopts on the traditional mode of production mainly contains two classes, one class offers by reductive agent and is reduced the thing electronics and reduces, by reductive agent be reduced thing and directly contact and carry out electron exchange, speed of response is fast, but there be the problem of reductive agent to reduzate " pollution ", part carbon also enters molten iron when generating iron as carbon reduction ferriferous oxide in the blast furnace, in order to improve the performance of ferrous materials, also to carry out decarburization thereafter, impurity elimination brings the wasting of resources, problems such as environmental pollution.Another kind of directly the supply by reductive agent is reduced the thing electronics and reduces, electronics passes to by electronic conductor (electrode) from power supply and is reduced thing, there is not the problem of reductive agent " pollution " reduzate in it, but electricity belongs to secondary resource, from thermal power generation, water power or nuclear energy power generation, wherein major portion is from thermal power generation, get by the conversion of heat-electricity by coal burning, heat-photoelectric transformation efficiency is very low under existing technical qualification, cause the ample resources waste, excessive coal burning produces CO
2Deng also having aggravated atmospheric pollution.
Forefathers utilize oxygen ion conduction solid electrolyte and mixed conductor, as reductive agent (reductor, provide the electronics end) be reduced " sealing coat " of thing (by the deoxidation thing, obtain the electronics end), avoided being reduced the problem that product is subjected to reductive agent " pollution ", can carry out degree of depth deoxidation or restore high pure metal, particularly adopt solid electrolyte self " electrical short " deoxidation, current density has improved tens times, and application potential is very big.But adopting reductive agent is secondary resource, is secondary resource equally during electricity consumption, has first resource reprocessing process, causes fund, labor force's overlapping investment, the waste of resource, has also aggravated atmospheric pollution; Also exist solid electrolyte or mixed conductor to be subjected to the problem of slag corrosion simultaneously.
Summary of the invention:
The present invention seeks to find out a kind of is with utilizing the oxygen ion conduction solid electrolyte equally, but reductive agent obtains the method for clean metal or sub-compound with the first resource reduction, solve the wasting of resources, aggravate atmospheric pollution problem, solid electrolyte is subjected to the problem of slag corrosion, and the reduction of traditional contact brings the problem of reductive agent to reduzate " pollution ".
A kind of contactless metallic element carbon hot melting reduction method; comprise oxygen ion conduction solid electrolyte 2, metal-C melt 3, contain the slag 5 that is reduced thing, be reduced thing 6, electrode 7; it is characterized in that present method makees reductive agent 1 with coal; be provided with between slag and solid electrolyte between metal protection sealing coat 4, two electrodes 7 and connect by electrochemistry controller 8.
Principle as shown in Figure 1; it with oxygen ion conduction solid electrolyte, metal-C melt, contain the slag and the electrochemistry controller that are reduced thing; form concentration cell; reductive agent is reduced thing slag separation solid electrolyte both sides with containing; oxygen potential difference by both sides is carried out electrochemical reduction, and metal " protecting insulating layer " wherein is set between slag and solid electrolyte.Metal-C melt can be produced by coal and metal, and the dissolved carbon of lower oxygen partial pressure and greater activity can be provided; Slag is to contain to be reduced the thing slag system, is reduced thing MO and becomes M at the slag internal disintegration
2+And O
2-Solid electrolyte had both played a part to isolate reductive agent and had been reduced product, can guarantee oxonium ion (O simultaneously
2-) transmission, outer circuit electronic conduction is eliminated the restraining effect of electric field to oxygen ion conduction; External circuit connects the electrochemistry controller, plays and regulates and the monitoring effect; In addition, " protecting insulating layer " solved solid electrolyte and electrode and has been subjected to slag etch problem.
Metal is Fe in metal-C melt 3, Co, and the molten metal of energy such as Ni dissolved carbon, oxygen ion conduction solid electrolyte 2 is with ZrO
2To mainly contain with CaO, MgO be the alkaline earth metal oxide of representative and with Y to doping oxide in the base two component system
2O
3, Sc
2O
3Be the rare-earth oxide of representative, also have ZrO in addition
2-Y
2O
3Add Yb in the system
2O
3, Sc
2O
3Deng metal suboxide, ZrO
2-Y
2O
3Add Al in the system
2O
3, Bi
2O
3Deng, or mixing and doping.
Metal protection sealing coat 4 is Ag, Cu, and Fe, metals such as Sn are specifically decided on being reduced product, during as reducing iron oxides, wish to be reduced into pure iron available metal iron, wish to form Cu-Fe alloy available metal copper etc.
Reducing metal oxide such as bismuth oxide compound, sb oxide, lead oxides, tin-oxide, copper oxide, nickel oxide, cobalt/cobalt oxide, ferriferous oxide or Mn oxide obtain pure metal, metal protection sealing coat 4 corresponding bismuth metal, antimony, lead, tin, copper, nickel, cobalt, iron or the manganese of being respectively.
Reducing non-ferriferous oxide such as Si oxide, nickel oxide, Mn oxide, chromated oxide, titanium oxide, molybdenum oxide or tungsten oxide obtains iron alloy, and metal protection sealing coat 4 be metallic iron or iron alloy accordingly.
Reducing copper oxides, tin-oxide or sb oxide obtain iron alloy, and metal protection sealing coat 4 is corresponding iron alloy.
Reduction magnesium oxide or calcium oxide obtain magnesium steam or calcium steam, and metal protection sealing coat 4 is a metallic iron.
Electrode: anode Graphite Electrodes, negative electrode Mo-ZrO
2, Co-ZrO
2, Ni-ZrO
2, Ru-ZrO
2, W-ZrO
2, and W-CeO
2-ZrO
2, W-Y
2O
3-ZrO
2, W-La
2O
3-ZrO
2Deng sintering metal, concrete Yin Wendu and protecting insulating layer 4 and decide are as Mo-ZrO
2Pottery can be used for iron liquid " protecting insulating layer ", Co-ZrO
2, Ni-ZrO
2Pottery is used for copper liquid " protecting insulating layer ", and Ru-ZrO
2Pottery can be used for the metal melt protecting insulating layer of higher temperature.
Electrochemistry controller 8 voltage-regulation scopes, 0-1.2V.
The present invention compares with traditional contact reduction, and it, has been avoided being reduced the produce thing and be subjected to reductive agent " pollution " problem as reductive agent and " sealing coat " that be reduced thing with solid electrolyte, can shorten metallurgical process; Compare with traditional electrolytic process reduction, using coal is main reductive agent and heat-generating agent, has overcome problems such as the low energy consumption of bringing of conversion efficiency of thermoelectric is big, environmental pollution; Compare for the method for " sealing coat " with existing solid electrolyte or the mixed conductor of adopting, can use first resource-coal, be convenient to use, and activity is big, oxygen partial pressure is stable as reductive agent; Solid electrolyte and containing is reduced introduces " protecting insulating layer " between the thing slag, solved solid electrolyte and electrode and be subjected to slag etch problem.In addition, the solid electrolyte container constitutes CO generator, above the outer surface vessel be slag, below be metal, can feed continuously and discharge, for operate continuously, improve output, provide possibility.
Description of drawings:
Fig. 1 is a principle of the invention synoptic diagram, 1. reductive agents-coal wherein, and 2. oxygen conducting solid ionogen, 3. metal-C melt, 4. protecting insulating layer 5. contains and is reduced the thing slag, 6. is reduced thing, 7. electrode, 8. electrochemistry controller.
Fig. 2 uses reductive agent and is reduced the contactless carbon hot melting reduction method of thing embodiment under impressed voltage equals zero condition, wherein I is the reduction result under the saturated Fe-C melt of non-carbon, and II is the reduction result under the saturated melt of carbon,
The reduction ratio of iron content slag under the saturated Fe-C melt of Fig. 3 carbon.
Embodiment:
The contactless Fe elemental carbon of a kind of Fe and FeO hot melting reduction method; by oxygen ion conduction solid electrolyte, Fe-C melt, the slag that contains FeO and electrochemistry controller; form concentration cell; the Fe-C melt with contain FeO slag separation solid electrolyte both sides; oxygen potential difference by both sides is carried out electrochemical reduction, and metal " protecting insulating layer " wherein is set between slag and solid electrolyte.The Fe-C melt can be produced by coal and Fe, and the dissolved carbon of lower oxygen partial pressure and greater activity can be provided; Be reduced thing FeO and become Fe at the slag internal disintegration
2+And O
2-Solid electrolyte had both played a part to isolate reductive agent and had been reduced product, can guarantee oxonium ion (O simultaneously
2-) transmission, outer circuit electronic conduction is eliminated the restraining effect of electric field to oxygen ion conduction; External circuit connects the electrochemistry controller, plays and regulates and the monitoring effect; In addition, " protecting insulating layer " solved solid electrolyte and electrode and has been subjected to slag etch problem.
The oxygen ion conduction solid electrolyte is ZrO
2MgO has mixed in the base two component system.The metal protection sealing coat is a metallic copper, and reduzate is the Cu-Fe alloy.Electrode: anode Graphite Electrodes, negative electrode Mo-ZrO
2Electrochemistry controller voltage-regulation scope, 0-1.2V.
Claims (5)
1. contactless metallic element carbon hot melting reduction method; comprise oxygen ion conduction solid electrolyte (2), metal-C melt (3), contain the slag (5) that is reduced thing, be reduced thing (6), electrode (7); it is characterized in that present method makees reductive agent (1) with coal; metal protection sealing coat (4) is set between slag and solid electrolyte, connects by electrochemistry controller (8) between two electrodes (7).
2. metallic element carbon hot melting reduction method as claimed in claim 1; it is characterized in that reducing metal oxide is that bismuth oxide compound, sb oxide, lead oxides, tin-oxide, copper oxide, nickel oxide, cobalt/cobalt oxide, ferriferous oxide or Mn oxide obtain pure metal, corresponding bismuth metal, antimony, lead, tin, copper, nickel, cobalt, iron or the manganese of being respectively of metal protection sealing coat (4).
3. metallic element carbon hot melting reduction method as claimed in claim 1; the non-ferriferous oxide that it is characterized in that reducing is that Si oxide, nickel oxide, Mn oxide, chromated oxide, titanium oxide, molybdenum oxide or tungsten oxide obtain iron alloy, and metal protection sealing coat (4) is metallic iron or corresponding iron alloy.
4. metallic element carbon hot melting reduction method as claimed in claim 1 is characterized in that reducing copper oxides, tin-oxide or sb oxide obtain iron alloy, and metal protection sealing coat (4) is corresponding iron alloy.
5. metallic element carbon hot melting reduction method as claimed in claim 1 is characterized in that reducing magnesium oxide or calcium oxide to obtain magnesium steam or calcium steam, and metal protection sealing coat (4) is a metallic iron.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 03121189 CN1245526C (en) | 2003-03-27 | 2003-03-27 | Noncontact type metal element carbon hot melt reduction method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 03121189 CN1245526C (en) | 2003-03-27 | 2003-03-27 | Noncontact type metal element carbon hot melt reduction method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1442497A CN1442497A (en) | 2003-09-17 |
| CN1245526C true CN1245526C (en) | 2006-03-15 |
Family
ID=27797239
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 03121189 Expired - Fee Related CN1245526C (en) | 2003-03-27 | 2003-03-27 | Noncontact type metal element carbon hot melt reduction method |
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| Country | Link |
|---|---|
| CN (1) | CN1245526C (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4803282B2 (en) * | 2009-06-18 | 2011-10-26 | トヨタ自動車株式会社 | Nanocomposite thermoelectric conversion material and method for producing the same |
| CN106380229B (en) * | 2016-08-27 | 2017-11-28 | 武汉科技大学 | A kind of method and device for improving magnesia carbon refractory resistance to slag corrosion |
-
2003
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| Publication number | Publication date |
|---|---|
| CN1442497A (en) | 2003-09-17 |
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Granted publication date: 20060315 Termination date: 20110327 |