CN104388986A - Production process for preparing copper-magnesium alloy by virtue of molten salt electrolysis method - Google Patents
Production process for preparing copper-magnesium alloy by virtue of molten salt electrolysis method Download PDFInfo
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- CN104388986A CN104388986A CN201410696123.3A CN201410696123A CN104388986A CN 104388986 A CN104388986 A CN 104388986A CN 201410696123 A CN201410696123 A CN 201410696123A CN 104388986 A CN104388986 A CN 104388986A
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
- C25C3/00—Electrolytic production, recovery or refining of metals by electrolysis of melts
- C25C3/36—Alloys obtained by cathodic reduction of all their ions
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Abstract
The invention relates to a production process for preparing copper-magnesium alloy by virtue of a molten salt electrolysis method. According to the production process, magnesium oxide or magnesium chloride or magnesium carbonate is taken as a raw material, pure copper is taken as a negative electrode, graphite is taken as a positive electrode, and an electrolysis system is formed by combining magnesium fluoride or magnesium chloride with chlorides and fluorides of alkali metals or alkaline-earth metals; MgO or MgCl2 or Mg2CO3 ionizes at 750-950 DEG C, Mg<2+> is separated from a copper negative electrode and is reduced into Mg, and Mg and Cu are alloyed to directly generate Cu-Mg, namely the copper-magnesium alloy. Compared with an existing smelting-doping method, the production process has the advantages that the energy is saved, the technological process is simplified, alloy segregation and secondary metal burning are avoided, and the like.
Description
Technical field
The present invention relates to a kind of production technique of copper-magnesium alloy, particularly the direct production technique of production of copper magnesium alloy on negative electrode in fused-salt bath, belongs to Non-ferrous Metallurgy fused salt electrolysis field.
Background technology
Copper alloy is a kind of very important engineering materials, there is the excellent electricity ﹑ that leads and lead many performances such as hot property ﹑ ductility and solidity to corrosion, be widely used in and make electrical material such as mother's line ﹑ transformer of sending out electric machine ﹑ and Re Jiao changes the heat conduction equipment such as the flat plate collector of device ﹑ solar heat collector.
The alloy material that magnesium and copper are formed has good electroconductibility, shock absorption, electromagnetic shielding, solidity to corrosion etc., its application mainly concentrates on aluminium alloy production, Die Casting, the large field of steel desulfurization three, application in the electronic product such as computer, communication is constantly increased, so copper-magnesium alloy will have wide application development prospect.
The preparation method of copper-magnesium alloy, namely forms mixing with pure magnesium and fine copper the method for mixing in the molten state according to a certain percentage based on melting.Like this, not only increase the hear rate of metal secondary remelting, also add the oxidational losses of metal, and easily segregation, cause the significant wastage of metal, add the production cost of alloy.
It is for raw material with magnesium oxide or magnesium chloride or magnesiumcarbonate that fused salt electrolysis process prepares copper-magnesium alloy, employing fine copper is negative electrode, graphite is anode, electrolyte system is formed by the muriate of magnesium fluoride or magnesium chloride and basic metal or alkaline-earth metal and fluoride combinations, at temperature 750 ~ 950 DEG C, direct production copper-magnesium alloy in fused-salt bath.The method can scale operation uniform composition, reduced in segregation copper-magnesium alloy.Meanwhile, alloy production cost is reduced.
Summary of the invention
The object of patent of the present invention is to provide a kind of fused salt electrolysis process to prepare the production technique of copper-magnesium alloy, it is characterized in that: with MgO or MgCl
2or Mg
2cO
3for raw material, put into electrolyzer, the electrolyte system of described electrolyzer is formed by the muriate of magnesium fluoride or magnesium chloride and basic metal or alkaline-earth metal and fluoride combinations, the employing fine copper of electrolyzer is negative electrode, graphite is anode, and described negative electrode selects upper plug type negative electrode, when temperature is 750 ~ 950 DEG C, under the effect of DC electric field, MgO or MgCl of dissolving
2or Mg
2cO
3ionize, through the electrolysis of 6-12 hour, Mg
2+separate out at copper cathode surface, be reduced to Mg, Mg and Cu alloying forms Cu-Mg, directly generates copper-magnesium alloy.
It is characterized in that: raw material is MgO or MgCl
2or Mg
2cO
3, in its raw material, the content of impurity component is: Fe < 0.1%, P < 0.1%, other composition summation≤0.5%.
It is characterized in that: electrolysis cathode adopts fine copper.
It is characterized in that: electrolyte system is selected from by MgF
2and MgCl
2, LiF, LiCl, KCl, KF, BaF
2, BaCl
2, CaF
2, CaCl
2, in NaF, NaCl two kinds or two or morely to combine.
It is characterized in that: with MgO or MgCl
2or Mg
2cO
3for raw material, MgO or MgCl in electrolytic process
2or Mg
2cO
3be decomposed, Mg
2+ion is separated out on cathode, and at this solution temperature of electricity with cathode copper alloying, form Cu-Mg alloy, be deposited on bottom ionogen;
O
2-or Cl
-in graphite anode surface-discharge, be oxidized to O
2or Cl
2, O
2cO and CO is reacted into graphite
2enter air:
Mg
2++2e→Mg Cu+Mg→Cu-Mg
2O
2-+4e→O
2O
2+C→CO
2O
2+C→CO
2Cl
-+2e→Cl
2
It is characterized in that: the mass percent of the solubleness of MgO in electrolyte system is 1 ~ 5%, MgCl
2solubleness in electrolyte system is mass percent is 1 ~ 5%, Mg
2cO
3solubleness in electrolyte system is mass percent is 1 ~ 25%.
It is characterized in that: electrolysis temperature is 750 ~ 950 DEG C, to ensure ionogen melting, electrolysis generation magnesium, and make copper-magnesium alloy.
It is characterized in that: in copper-magnesium alloy, Mg content is: 5-25%, in copper-magnesium alloy, copper content is: 75-95%, and other impurity component content is less than 1%.
It is characterized in that: electrolysis voltage is 2 ~ 4V, electrolysis temperature 750 ~ 950 DEG C.
Beneficial effect:
By the enforcement of technical solution of the present invention, can produce the copper-magnesium alloy of uniform composition as required, alloying constituent is determined by electrolysis time and proportioning raw materials.The method solving present production of copper magnesium alloy well exists that hear rate is large, the oxidational losses of alloyed metal is large, segregation serious, Metal Production high in cost of production shortcoming.
Production technique of the present invention is with MgO or MgCl of cheapness
2or Mg
2cO
3with fine copper raw material, in fused-salt bath, direct production goes out the copper-magnesium alloy of uniform composition.Low-alloyed production cost can be fallen significantly, reduce the labour intensity of workman.Meanwhile, electrolytic process is continuous, is that a kind of short route, cost are low, pollutes few alloy production technique.
Embodiment
Below in conjunction with specific embodiment, set forth the present invention further.
Fused salt electrolysis process prepares the production technique of copper-magnesium alloy with MgO or MgCl
2or Mg
2cO
3for raw material, electrolyte system is formed by the muriate of magnesium fluoride or magnesium chloride and basic metal or alkaline-earth metal and fluoride combinations, and when temperature is 750 ~ 950 DEG C, employing fine copper is negative electrode, and graphite is anode, under the effect of DC electric field, MgO or MgCl of dissolving
2or Mg
2cO
3ionize, Mg
2+separate out at copper cathode surface, be reduced to Mg, Mg and negative electrode Cu alloying form Cu-Mg, directly generate copper-magnesium alloy.Process is as follows: ionogen is by MgF
2and MgCl
2, LiF, LiCl, KCl, KF, BaF
2, BaCl
2, CaF
2, CaCl
2, in NaF, NaCl two kinds or two or morely to combine.At high temperature molten electrolyte, adds raw material, switches on power, and starts electrolysis.Separated in time, adds raw material to maintain magnesium ion concentration in electrolyzer a stable scope, takes out the copper-magnesium alloy that electrolysis generates simultaneously, ensure that electrolysis is normally carried out.
Electrolysis temperature: different according to ionogen composition, temperature-controllable is between 750 DEG C ~ 950 DEG C, different according to electrolytical liquidus temperature, and 20 DEG C on electrolyte primary crystal temperature ~ 100 DEG C can be selected to carry out electrolysis.
Embodiment 1:
With MgCl
2-CaCl
2-NaCl is electrolyte system, and the mass percent of each composition is respectively 10%, 35%, 55%, and magnesium chloride is raw material, and with metal copper rod for negative electrode, graphite is anode, have selected upper plug type negative electrode.Electrolysis temperature is 820 DEG C, and pole span is 15cm, and strength of current is 3000A, regularly supplements to electrolyzer and adds the magnesium oxide that mass percent is 1%, through the electrolysis of 4 hours, produced the copper-magnesium alloy of uniform composition at bottom of electrolytic tank.In alloy, Mg content mass percent reaches 8.6%, and copper content mass percent reaches 87.2%, metal recovery rate 98.8%.Cl is released in electrolytic process
2, generate without other gas.
Embodiment 2:
With MgCl
2-CaCl
2-NaCl-KCl is electrolyte system, and the mass percent of each composition is respectively 10%, 35%, 50%, 5%, and employing magnesium chloride is raw material, and with metal copper rod for negative electrode, graphite is anode, have selected upper plug type negative electrode.Electrolysis temperature is 850 DEG C, and pole span is 15cm, and strength of current is 3000A, regularly supplements to electrolyzer and adds the magnesium chloride that mass percent is 2%, through the electrolysis of 6 hours, produced the copper-magnesium alloy of uniform composition at bottom of electrolytic tank.In alloy, Mg content mass percent reaches 10.1%, and copper content mass percent reaches 86.2%, metal recovery rate 96%.Cl is released in electrolytic process
2.
Embodiment 3:
With MgF
2-BaF-LiF is electrolyte system, and the mass percent of each composition is respectively 25%, 55%, 25%, raw materials of magnesium oxide, and with metal copper rod for negative electrode, graphite is anode, have selected upper plug type negative electrode.Electrolysis temperature is 950 DEG C, and pole span is 20cm, and strength of current is 2000A, regularly supplements to electrolyzer and adds the magnesium oxide that mass percent is 1%, through the electrolysis of 8 hours, produced the copper-magnesium alloy of uniform composition in a cell.In alloy, Mg content mass percent reaches 15.4%, and copper content mass percent reaches 82.1%, metal recovery rate 98.2%.Only CO is released in electrolytic process
2, CO, generates without other gas.
Embodiment 4:
With MgF
2-NaF-LiF is electrolyte system, and the mass percent of each composition is respectively 25%, 65%, 10%.Magnesiumcarbonate is raw material, and with metal copper rod for negative electrode, graphite is anode, have selected down inserting type negative electrode.Electrolysis temperature is 850 DEG C, and pole span is 15cm, and strength of current is 3000A, regularly supplements to electrolyzer and adds the magnesiumcarbonate that mass percent is 3%, through the electrolysis of 12 hours, produced the copper-magnesium alloy of uniform composition in a cell.In alloy, Mg content mass percent reaches 20.4%, and copper content mass percent reaches 77.1%, metal recovery rate 97.5%.CO is released in electrolytic process
2, CO.
Embodiment 5:
With MgF
2-NaF-CaCl-KCl is electrolyte system, and the mass percent of each composition is 15%, 25%, 45% and 20%, and magnesium oxide is raw material, and with metal copper rod for negative electrode, graphite is anode, have selected upper plug type negative electrode.Electrolysis temperature is 800 DEG C, and pole span is 20cm, and strength of current is 3000A, regularly to electrolyzer supplement add mass percent be 1% magnesium oxide and through the electrolysis of 6 hours, produced the copper-magnesium alloy of uniform composition at bottom of electrolytic tank.In alloy, Mg content mass percent reaches 16.5%, and copper content mass percent reaches 81.1%, metal recovery rate 97%.CO is released in electrolytic process
2, CO.
Embodiment 6:
With MgCl
2-CaCl
2-NaCl-LiF is electrolyte system, and the mass percent of each composition is respectively 20%, 35%, 50% and 5%, take mass percent as the magnesiumcarbonate of 2% is raw material, and with metal copper rod for negative electrode, graphite is anode, have selected upper plug type negative electrode.Electrolysis temperature is 750 DEG C, and pole span is 20cm, and strength of current is 3000A, regularly supplements to electrolyzer and adds the magnesiumcarbonate that mass percent is 3%, through the electrolysis of 8 hours, produced the copper-magnesium alloy of uniform composition at bottom of electrolytic tank.In alloy, Mg content mass percent reaches 21.2%, and copper content mass percent reaches 78.1%, metal recovery rate 95.6%.CO is released in electrolytic process
2, CO.
Embodiment 7:
With MgF
2-NaF is electrolyte system, and the mass percent of each composition is 23% and 77%, and magnesium oxide is raw material, and with metal copper rod for negative electrode, graphite is anode, have selected upper plug type negative electrode.Electrolysis temperature is 850 DEG C, and pole span is 15cm, and strength of current is 3000A, regularly supplements to electrolyzer and adds the magnesium oxide that mass percent is 1%, through the electrolysis of 15 hours, produced the copper-magnesium alloy of uniform composition at bottom of electrolytic tank.In alloy, Mg content mass percent reaches 18.5%, and copper content mass percent reaches 82%, metal recovery rate 96%.CO is released in electrolytic process
2, CO.
Should be understood that these embodiments are only not used in for illustration of the present invention to limit the scope of the invention.In addition should be understood that those skilled in the art can make various changes or modifications the present invention, and these equivalent form of values fall within the application's appended claims limited range equally after the content of having read the present invention's instruction.
Claims (9)
1. fused salt electrolysis process prepares a production technique for copper-magnesium alloy, it is characterized in that: with MgO or MgCl
2or Mg
2cO
3for raw material, put into electrolyzer, the electrolyte system of described electrolyzer is formed by the muriate of magnesium fluoride or magnesium chloride and basic metal or alkaline-earth metal and fluoride combinations, the employing fine copper of electrolyzer is negative electrode, graphite is anode, and described negative electrode selects upper plug type negative electrode, when temperature is 750 ~ 950 DEG C, under the effect of DC electric field, MgO or MgCl of dissolving
2or Mg
2cO
3ionize, through electrolysis, Mg
2+separate out at copper cathode surface, be reduced to Mg, Mg and Cu alloying forms Cu-Mg, directly generates copper-magnesium alloy.
2. fused salt electrolysis process according to claim 1 prepares the production technique of copper-magnesium alloy, it is characterized in that: raw material is MgO or MgCl
2or Mg
2cO
3, in its raw material, the content of impurity component is: Fe < 0.1%, P < 0.1%, other composition summation≤0.5%.
3. fused salt electrolysis process according to claim 1 prepares the production technique of copper-magnesium alloy, it is characterized in that: electric tank cathode adopts fine copper.
4. fused salt electrolysis process according to claim 1 prepares the production technique of copper-magnesium alloy, it is characterized in that: electrolyte system is selected from by MgF
2and MgCl
2, LiF, LiCl, KCl, KF, BaF
2, BaCl
2, CaF
2, CaCl
2, in NaF, NaCl two kinds or two or morely to combine.
5. fused salt electrolysis process according to claim 1 prepares the production technique of copper-magnesium alloy, it is characterized in that: with MgO or MgCl
2or Mg
2cO
3for raw material, MgO or MgCl in electrolytic process
2or Mg
2cO
3be decomposed, Mg
2+ion is separated out on cathode, and at this solution temperature of electricity with cathode copper alloying, form Cu-Mg alloy, be deposited on bottom ionogen;
O
2-or Cl
-in graphite anode surface-discharge, be oxidized to O
2or Cl
2, O
2cO and CO is reacted into graphite
2enter air:
Mg
2++2e→Mg Cu+Mg→Cu-Mg
2O
2-+4e→O
2O
2+C→CO
2O
2+C→CO
2Cl
-+2e→Cl
2。
6. fused salt electrolysis process according to claim 1 prepares the production technique of copper-magnesium alloy, it is characterized in that: the mass percent of the solubleness of MgO in electrolyte system is 1 ~ 5%, MgCl
2solubleness in electrolyte system is mass percent is 1 ~ 5%, Mg
2cO
3solubleness in electrolyte system is mass percent is 1 ~ 25%.
7. fused salt electrolysis process according to claim 1 prepares the production technique of copper-magnesium alloy, it is characterized in that: electrolysis temperature is 750 ~ 950 DEG C, to ensure ionogen melting, electrolysis generation magnesium, and makes copper-magnesium alloy.
8. fused salt electrolysis process according to claim 1 prepares the production technique of copper-magnesium alloy, it is characterized in that: in copper-magnesium alloy, Mg content is: 5-25%, and in copper-magnesium alloy, copper content is: 75-95%, and other impurity component content is less than 1%.
9. fused salt electrolysis process according to claim 1 prepares the production technique of copper-magnesium alloy, it is characterized in that: electrolysis voltage is 2 ~ 4V, electrolysis temperature 750 ~ 950 DEG C.
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Cited By (3)
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|---|---|---|---|---|
| CN105220175A (en) * | 2015-10-12 | 2016-01-06 | 河南大学 | The method of the magnesium copper alloy of different phase composite is prepared in a kind of low-temperature molten salt galvanic deposit |
| CN105316708A (en) * | 2015-12-02 | 2016-02-10 | 河南大学 | Method for preparing aluminum-copper alloy consisting of different phases by molten salt electrolysis |
| CN115305506A (en) * | 2021-05-08 | 2022-11-08 | 中南大学 | Method for preparing metal magnesium by molten salt electrolysis |
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Cited By (3)
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|---|---|---|---|---|
| CN105220175A (en) * | 2015-10-12 | 2016-01-06 | 河南大学 | The method of the magnesium copper alloy of different phase composite is prepared in a kind of low-temperature molten salt galvanic deposit |
| CN105316708A (en) * | 2015-12-02 | 2016-02-10 | 河南大学 | Method for preparing aluminum-copper alloy consisting of different phases by molten salt electrolysis |
| CN115305506A (en) * | 2021-05-08 | 2022-11-08 | 中南大学 | Method for preparing metal magnesium by molten salt electrolysis |
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