CN1896331A - Production of aluminum and copper-based alloy - Google Patents
Production of aluminum and copper-based alloy Download PDFInfo
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- CN1896331A CN1896331A CNA2006100468623A CN200610046862A CN1896331A CN 1896331 A CN1896331 A CN 1896331A CN A2006100468623 A CNA2006100468623 A CN A2006100468623A CN 200610046862 A CN200610046862 A CN 200610046862A CN 1896331 A CN1896331 A CN 1896331A
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Abstract
The present invention relates to a preparation process of aluminum-copper based alloy. In this process the anode material is pure copper or copper-based alloy, the electrolyte is 93-99wt% of cryolite mixed with 1-5wt% of Al2O3, the aluminum-copper based alloy is produced by electrolysis with the anode in the mentioned electrolyte. When using thermit reaction, the reactant are metallic aluminum and copper oxide, the aluminum-copper based alloy is obtained by adding copper oxide and aluminum orderly into the cryolite fusant and stirring in the temperature range of 850-1500DEG C, metallic aluminum takes 35-99.1% of the total weight of the reactants and the actual copper content of copper oxide takes 0.1-65%. The present invention aims at solving the problems with the carbon anodes such as air pollution, energy consumption, high cost and the recycling of waste copper catalyst.
Description
One, technical field: the present invention relates to a kind of is anode prepares aluminum and copper-based alloy in electrolyzer method with copper and alloy thereof, main development is a kind of to be anode prepares aluminum and copper-based alloy in electrolyzer preparation method with copper and alloy thereof, anodic product during preparation is an oxygen, belongs to Non-ferrous Metallurgy fused salt electrolysis field.
Two, background technology: Al-Cu is that alloy is a kind of casting alloy of using the earliest.Its importance is only second to the Al-Si alloy in various aluminium alloys, and its Main Feature is that room temperature and mechanical behavior under high temperature are good, and machinability is good, fine heat-resisting performance.Al-Cu is that alloy contains Cu amount 3%～11%, owing to Cu plays solution strengthening and the precipitation-hardening effect makes this aluminium alloy have high room temperature and mechanical behavior under high temperature, is the highest class aluminium alloy of intensity in all kinds of aluminium alloys.
But Al-Si is the intensity that adds the metallic copper reinforced alloys in the alloy, improve the resistance to air loss and the machinability of foundry goods, even and the Al-Si-Cu alloy is without thermal treatment, also can obtain the good mechanical performance, being particularly suited for being used for die casting, is one of developing direction of current high strength die-casting alloy.
Add Cu in the Al-Si-Mg alloy, along with the increase of Cu amount, its room temperature tensile strength and creep rupture strength significantly increase, and improve the machinability of alloy and improve surface smoothness.
In the Al-RE alloy, when adding Cu, can form Al
4Ce, Al
8Cu
4Ce, Al
24Cu
8Ce
3Complex compounds such as Mn, the changes in solubility of these compounds in αGu Rongti is very little, crystallization dot matrix complexity, thermohardening is higher, also more stable under the high temperature, the eutectic that these superfluous α form mutually is distributed on the crystal boundary with grid, can significantly improve the heat resistance of alloy.
Add proper C u in the Al-Zn-Mg alloy and can enlarge Zn and the solubleness of Mg in Al, also can form CuAl
2And Al
2The MgCu phase, the quantity of increase strengthening phase, the strengthening effect of raising alloy, Cu can also reduce intracrystalline and intergranular potential difference simultaneously, and corrosion process is evenly carried out, thereby improves erosion resistance.
Xantal is the Cu-Al binary alloy, and general aluminum content is no more than 11%, and xantal has than high-tensile and plasticity, its mechanical property can with cast steel quite or surpass cast steel; The wear resisting property of xantal under room temperature and hot conditions is better, has less wet friction coefficient; The xantal surface forms the fine and close and stable Al of one deck
2O
3The inertia protective membrane, this layer Al
2O
3Protective membrane is not only stable under general oxidizing condition; and under the reductive condition; certain corrosion resistance is also arranged, can prevent that interior metal is corroded, thereby the chemical machinery part that is widely used in steamer, oil engine and is in work under the high temperature.
Aluminum brass commonly used has ZHAl167-2.5, ZHAl166-6-3-2, ZHAl67-5-2-2.ZHAl167-2.5 contains 2～3%Al, 66～68Cu, flowability, resistance to air loss, solidity to corrosion all can be used as general corrosion resistant material well, when being used for die casting not sticking to mould, do not ftracture.Contain 5～7%Al, 64～68% Cu among the ZHAl166-6-3-2, be the highest alloy of intensity among the special Cu, have high strength, high rigidity, good wear resistance, moderate plasticity and good wear resistance, be mainly used to make the strength member that bears friction and high loading on the heavy-duty machine, as large gear, hold-down nut, heavy worm screw etc.Containing the Al amount among the ZHAl67-5-2-2 is 4.5～6.0%Al, microstructure is (alpha+beta), and the plasticity of alloy is guaranteed and improves, and therefore has very high comprehensive mechanical performance, can be used as the material of large ship and speedboat water screw, widespread use in shipbuilding industry.
Preparation Al-zn-mg-cu alloy, xantal and aluminum brass are that the master alloy form with Al-Cu joins in the aluminium alloy.
Produce at present aluminum-copper alloy and mainly contain metallic aluminium and copper, cause the oxidation of a large amount of metals during seasoning metal, waste a large amount of energy simultaneously the method for mixing.
The Hall-Heroult process that the metallic aluminium electrolytic industry adopts, anode all is carbon annode (also being graphite anode), when electrolysis, anode carbon is oxidized and consume, and wastes a large amount of high grade coke, refinery coke; And discharge a large amount of greenhouse gases and toxic gas, as CF
4, CF
6, PAH polynuclear aromatics (generation of anode production process), volatile organism VOC, HF, SO
x, COS and NO
xAnode change is frequent, and it is big to change anodic labour intensity.
Three, summary of the invention:
1, goal of the invention: the invention provides a kind of method for preparing aluminum and copper-based alloy, its purpose is to solve in the preparation aluminum and copper-based alloy process carbon anode and participates in electrolytic reaction and cause producing obnoxious flavour contaminate environment, a large amount of high grade coke, the refinery cokes of waste, solves the problem that the aspects such as production cost height of Solder for Al-Cu Joint Welding master alloy exist simultaneously.
2, technical scheme: the present invention is achieved through the following technical solutions:
A kind of method for preparing aluminum and copper-based alloy is characterized in that: this method is to be anode material with single fine copper or copper base alloy; Ionogen adopts the sodium aluminum fluoride of 95～99wt% and the Al of 1～5wt%
2O
3, the anode with single fine copper or copper base alloy during as electrolysis prepares aluminum and copper-based alloy put into above-mentioned ionogen electrolysis in electrolyzer after.
According to the content that will prepare required copper in the alloy, add the cupric oxide of 0～20wt% in the ionogen.
Dissolve in and in electrolyzer, add the appropriate amount of industrial fine aluminium in the aluminium liquid in advance for preventing that bottom of electrolytic tank from forming crust and being convenient to metallic copper.
In electrolyzer be to add AlF in the ionogen of base with the sodium aluminum fluoride
3, NaCl, LiF/Li
2CO
3, MgF
2, CaF
2, BaF
2In the combination of one or more additives.
In electrolyzer, add metal oxide nickel oxide, manganese oxide, ferric oxide or carbonate, preparation aluminum bronze nickel, aluminum bronze manganese and aluminium copper iron.
Every 20～30 minutes, in the electrolytic solution of electrolyzer, replenish a certain amount of Al of adding in the electrolytic process
2O
3And CuO.
Anodic current density is 0.8～1.0A/cm during electrolysis
2, interpole gap is 35～45mm, and electrolysis temperature is 960 ℃, and electrolysis time is 1～2 hour.
A kind of method for preparing aluminum and copper-based alloy; it is characterized in that: this method is under the provide protection of the melt of sodium aluminum fluoride; with metallic aluminium and cupric oxide as reactant; the weight of metallic aluminium accounts for 35～99.1% of reactant gross weight; cupric oxide is with the actual weight metering that contains copper; account for 0.1～65% of reactant gross weight by the actual weight that contains copper; in temperature is 850～1300 ℃ scope; in the melt of sodium aluminum fluoride, add cupric oxide earlier; add metallic aluminium again, prepare aluminum and copper-based alloy after the stirring.
The quality percentage composition of above-mentioned preparation copper is the aluminum and copper-based alloy of 0.1～65wt%.
3, advantage and effect: by the enforcement of technical solution of the present invention, can solve in the preparation aluminum and copper-based alloy process carbon anode well and participate in electrolytic reaction and cause producing obnoxious flavour contaminate environment, a large amount of high grade coke, the refinery cokes of waste, the problem that causes the aspects such as production cost height of Solder for Al-Cu Joint Welding master alloy to exist simultaneously.Inert anode when the present invention prepares aluminum and copper-based alloy and adopts copper and alloy thereof as electrolysis has reduced a large amount of greenhouse gases CO
2Discharging (1.65kgCO
2/ kgAl), reduce CO, PAH obnoxious flavour and carcinogenic substance CF such as (polynuclear aromaticss)
4And C
2F
6Discharging, discharge a large amount of O simultaneously
2Save the carbon consumption (by anode carbon consumption 400～500kg/tAl); Make the industry of part electrolytic aluminum be transformed into environmental type, produce bigger economic benefit, as reduce production costs, sell O from contamination type
2Also but the consumption of labor savings is raised labour efficiency, and has reduced environmental pollution.
Four, description of drawings: accompanying drawing 1 is electrolyzer principle schematic of the present invention;
Accompanying drawing 2 is electrolytic experiment apparatus structure synoptic diagram of the present invention;
Accompanying drawing 3 prepares the structural representation of the device of alloy for thermite reaction of the present invention.
Five, embodiment:
As follows below in conjunction with embodiment to the detailed description of the invention, but not because of content constraints the present invention of embodiment.
Embodiment 1:
A kind of is anode prepares aluminum and copper-based alloy in electrolyzer method with copper and alloy thereof, adopts plumbago crucible as electrolyzer, its negative electrode during also as electrolysis, with single fine copper or copper base alloy as anode material; Ionogen mainly adopts the sodium aluminum fluoride of 93～99wt% and the Al of 1～5wt%
2O
3, the anode with single fine copper or copper base alloy during as electrolysis is put into above-mentioned ionogen and is carried out electrolytic preparation and obtain aluminum and copper-based alloy in electrolyzer.
Anodic current density is 0.8～1.0A/cm during electrolysis
2, interpole gap is 35～45mm, and electrolysis temperature is 960 ℃, and electrolysis time is 1～2 hour.
Embodiment 2:
Among Fig. 1: 1, metallic crucible, the double cathode collector bar of doing; 2, metallic rod, the double anode rod of doing, the black patch of bottom are copper base anode; 3, process furnace; 4, plumbago crucible; 5, electrolytic solution; 6, insulated liner; 7, aluminum-copper alloy liquid.
As shown in Figure 1, the following black patch of metallic rod 2 is a copper base anode, and it is to be prepared from fine copper or copper base alloy, and what adopt among the present invention is that industrial electrolysis copper is as anode.The effect of plumbago crucible 4 is splendid attire electrolytic solution 5 double as graphite cathodes, and the ionogen in the electrolytic solution 5 is mainly by the sodium aluminum fluoride of 93～95wt%, the Al of 1～5wt%
2O
3, 5wt% CaF
2, the LiF of 2wt% and 0～10wt% CuO form, added a certain amount of Al every 20 minutes in the clockwise electrolytic solution
2O
3And CuO, to replenish the Al in the electrolyzer
2O
3Consume with CuO, replenish adding Al
2O
3With the electrochemical equivalent * electric current * time of quality=aluminium of CuO.In electrolyzer, add the appropriate amount of industrial fine aluminium in advance, purpose is metallic copper and the double as negative electrode that absorbs electrolysis and thermal reduction place, prevent the bottom of electrolytic tank crust simultaneously, adding is content and the electrolysis time according to required metallic nickel in the alloy in right amount, determine the add-on of aluminium, the bottom line that adds aluminium is under electrolysis temperature, does not separate out solid phase at bottom of electrolytic tank, forms crust.In actual production, can be by the aluminum liquid horizontal of general industry groove production adding.Negative electrode is vertical with anode to be placed in the crucible that is added with the corundum liner, 6 insulating effects of corundum liner, thus increase current density, help the gathering of aluminum alloy melt.In electrolyzer, add commercial-purity aluminium 50 grams during beginning earlier, form aluminium liquid after adding and absorb metal Cu, form aluminum-copper alloy liquid 7 after the electrolysis, just final required Al-Cu alloy.Anodic current density is 0.8～1.0A/cm during electrolysis
2, interpole gap is 35～45mm, and electrolysis temperature is 960 ℃, and electrolysis time is 1～2 hour.
Reaction in the electrolyzer can be summarized as:
In the electrolytic process, produce a large amount of oxygen (O around the anode
2).
Test result shows: electrolytic process is steady, the anodic erosion rate 30mm/ month.In aluminium manufacturer produced, Cu content can reach 1～38wt% in the alloy, the tool better industrial application prospects.
Embodiment 3:
Among Fig. 2: 8, anode rod and protective tube thereof; 9, aluminum oxide and cupric oxide (Lei Nitong) filling tube; 10, gas outlet; 11, cathode collector bar and protective tube thereof; 12, copper anode; 13, graphite cathode; 14, ionogen; 15, product aluminum-copper alloy, 16, temperature thermocouple; 17, temperature-control heat couple; 18, attemperator; 19, electric furnace; 20, iron crucible; 21, plumbago crucible; 22, aluminum oxide corundum.
As shown in Figure 2, during enforcement with plumbago crucible as electrolyzer, crucible lining corundum cover, the outside add the cover Stainless Steel Crucible to alleviate the oxidation of plumbago crucible under the high temperature.As negative electrode and anode rod, jig overcoat alundum tube is to reduce guide rod oxidation at high temperature with the stainless steel jig.By guide rod cathode and anode is linked to each other with anodal with the negative pole of rectifier power source respectively, series current table monitoring experiment electric current, the shunt voltage table is used for the mensuration of bath voltage.
The molecular ratio of the sodium aluminum fluoride that uses in the electrolysis is 2.2, and the ionogen in the adding mass percent electrolytic solution 5 is mainly by the sodium aluminum fluoride of 93～95wt%, the Al of 1～5wt%
2O
3, 5wt% CaF
2, the LiF of 2wt% and 0～10wt% CuO form, after they mixed, oven dry was 4 hours under 250 ℃ of temperature condition, removes the moisture in the ionogen.Ionogen powder after the oven dry is poured in the electrolyzer, and fusing heats up in electric furnace.After ionogen melts fully, by shown in Figure 2 electrode is immersed in the ionogen, the potential electrode immersion depth calculates the electrode area that immerses in the ionogen, regulates strength of current and makes the current density on negative electrode and the anode reach the electrolysis requirement, the record electrolysis time.Be to guarantee stable alumina concentration in the ionogen, in the electrolytic process every 20 minutes additional once oxidation aluminium.
The operating parameters of electrolysis test sees Table 1:
Table 1 electrolysis procedure experiment parameter
| Electrolysis temperature (℃) | Strength of current (A) | Cathode current density (A/cm 2) | Anodic current density (A/cm 2) | Pole span (cm) | Alumina concentration (wt%) | Cupric oxide concentration (wt%) |
| 960 | 16.00 | 0.80 | 1.30 | 4.0 | 2 | 3 |
Test result shows: electrolytic process is steady, the anodic erosion rate 20mm/ month.Cu content can reach 1～55wt% in the alloy, the tool better industrial application prospects.
Embodiment 4: Fig. 3 is the apparatus structure synoptic diagram of aluminothermy Al-Cu prepared in reaction alloy, among the figure 23, Stainless Steel Crucible; 24, resistance furnace; 25, plumbago crucible; 26, cryolite melts; 27, Al-Cu mother alloy.
A00 aluminium ingot, a stage cryolite (Na
3AlF
6), CuO.
The ionogen CuO that proportioning is good puts into crucible, is warming up to after ionogen melts fully, stirs cryolite melts 5～10 minutes, reach preset temperature after, add metallic aluminium.Carry out thermal reduction under 850～1300 ℃ constant temperature, the recovery time is 0.2～2 hour, should note making cryolite melts to cover the surface of metal aluminium liquid fully, in order to avoid atmospheric pollution alloy liquid.Reduction is together poured out ionogen and aluminium liquid after finishing, and copper content can reach 1～65wt% in the alloy.
Claims (9)
1, a kind of method for preparing aluminium-copper base alloy is characterized in that: this method is to be anode material with single fine copper or copper base alloy; Ionogen adopts the sodium aluminum fluoride of 95～99wt% and the Al of 1～5wt%
2O
3, the anode with single fine copper or copper base alloy during as electrolysis prepares aluminium-copper base alloy put into above-mentioned ionogen electrolysis in electrolyzer after.
2, the method for preparing aluminium-copper base alloy according to claim 1 is characterized in that: according to the content that will prepare required copper in the alloy, add the cupric oxide of 0～20wt% in the ionogen.
3, the method for preparing aluminium-copper base alloy according to claim 1 is characterized in that: dissolve in add the appropriate amount of industrial fine aluminium in the aluminium liquid in advance in electrolyzer for preventing that bottom of electrolytic tank from forming crust and being convenient to metallic copper.
4, the method for preparing aluminium-copper base alloy according to claim 1 is characterized in that: in electrolyzer be to add AlF in the ionogen of base with the sodium aluminum fluoride
3, NaCl, LiF/Li
2CO
3, MgF
2, CaF
2, BaF
2In the combination of one or more additives.
5, the method for preparing aluminium-copper base alloy according to claim 1 is characterized in that: add metal oxide (as nickel oxide, manganese oxide, ferric oxide) or carbonate in electrolyzer, preparation aluminum bronze nickel, aluminum bronze manganese and aluminium copper iron.
6, the method for preparing aluminium-copper base alloy according to claim 1 is characterized in that: every 20～30 minutes, replenish a certain amount of Al of adding in the electrolytic solution of electrolyzer in the electrolytic process
2O
3And CuO.
7, the method for preparing aluminium-copper base alloy according to claim 1 is characterized in that: anodic current density is 0.8～1.0A/cm during electrolysis
2, interpole gap is 30～50mm, electrolysis temperature is 960 ℃.
8, a kind of method for preparing aluminium-copper base alloy; it is characterized in that: this method is under the provide protection of the melt of sodium aluminum fluoride; with metallic aluminium and cupric oxide as reactant; the weight of metallic aluminium accounts for 35～99.1% of reactant gross weight; cupric oxide is with the actual weight metering that contains copper; account for 0.1～65% of reactant gross weight by the actual weight that contains copper; in temperature is 850～1300 ℃ scope; in the melt of sodium aluminum fluoride, add cupric oxide earlier; add metallic aluminium again, prepare aluminium-copper base alloy after the stirring.
9, the method for preparing aluminium-nickel-base alloy according to claim 8 is characterized in that: the quality percentage composition of above-mentioned preparation copper is aluminium-copper base alloy of 0.1～65wt%.
Priority Applications (1)
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|---|---|---|---|
| CNA2006100468623A CN1896331A (en) | 2006-06-09 | 2006-06-09 | Production of aluminum and copper-based alloy |
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|---|---|---|---|
| CNA2006100468623A CN1896331A (en) | 2006-06-09 | 2006-06-09 | Production of aluminum and copper-based alloy |
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|---|---|
| CN1896331A true CN1896331A (en) | 2007-01-17 |
Family
ID=37608969
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|---|---|---|---|---|
| CN101857962A (en) * | 2010-06-13 | 2010-10-13 | 中国铝业股份有限公司 | Method for increasing current efficiency of aluminum electrolysis cell |
| CN103264222A (en) * | 2013-05-24 | 2013-08-28 | 合肥荣事达三洋电器股份有限公司 | Welding method for aluminium wire and copper wire for motor |
| CN104328293A (en) * | 2014-11-07 | 2015-02-04 | 山东大学 | Aluminum crystal grain heterogeneous nucleation enhancer in aluminum alloy melt as well as preparation method and application thereof |
| CN104388804A (en) * | 2014-12-03 | 2015-03-04 | 中北大学 | Preparation method of aluminum, copper and iron quasicrystal |
| CN104962954A (en) * | 2015-07-30 | 2015-10-07 | 江西理工大学 | Method for preparing rare earth-aluminum-copper interalloy by fused salt electrolysis and alloy thereof |
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| CN105603463A (en) * | 2016-02-25 | 2016-05-25 | 周俊和 | Technology for producing aluminum alloy in aluminum electrolysis cell from aluminum reduction alloy oxide |
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| CN101857962A (en) * | 2010-06-13 | 2010-10-13 | 中国铝业股份有限公司 | Method for increasing current efficiency of aluminum electrolysis cell |
| CN103264222A (en) * | 2013-05-24 | 2013-08-28 | 合肥荣事达三洋电器股份有限公司 | Welding method for aluminium wire and copper wire for motor |
| CN104328293A (en) * | 2014-11-07 | 2015-02-04 | 山东大学 | Aluminum crystal grain heterogeneous nucleation enhancer in aluminum alloy melt as well as preparation method and application thereof |
| CN104388804A (en) * | 2014-12-03 | 2015-03-04 | 中北大学 | Preparation method of aluminum, copper and iron quasicrystal |
| CN104388804B (en) * | 2014-12-03 | 2016-08-24 | 中北大学 | The preparation method that a kind of aluminum bronze ferrum standard is brilliant |
| CN105177632A (en) * | 2015-07-30 | 2015-12-23 | 江西理工大学 | Molten salt electrolysis method for preparing copper-aluminum-rare earth intermediate alloy in rare-earth modification manner and alloy |
| CN104962954A (en) * | 2015-07-30 | 2015-10-07 | 江西理工大学 | Method for preparing rare earth-aluminum-copper interalloy by fused salt electrolysis and alloy thereof |
| CN104962954B (en) * | 2015-07-30 | 2017-06-09 | 江西理工大学 | A kind of molten-salt electrolysis prepares the method and its alloy of rare earth aluminum bronze intermediate alloy |
| CN105177632B (en) * | 2015-07-30 | 2017-06-06 | 江西理工大学 | It is rare earth modified to prepare copper aluminium rare earth intermediate alloy molten salt electrolysis method and alloy |
| 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 |
| CN105821450A (en) * | 2016-02-25 | 2016-08-03 | 周俊和 | Technology for producing alloy aluminum in electrolytic tank based on electrolytic method and aluminum reduction method |
| CN105603463A (en) * | 2016-02-25 | 2016-05-25 | 周俊和 | Technology for producing aluminum alloy in aluminum electrolysis cell from aluminum reduction alloy oxide |
| CN105603464A (en) * | 2016-02-25 | 2016-05-25 | 周俊和 | Process for achieving mix-melting method alloy aluminum production based on electrolytic method and aluminum reduction method |
| CN109996906A (en) * | 2016-11-24 | 2019-07-09 | 俄铝工程技术中心有限责任公司 | Aluminum alloy production method |
| US11634829B2 (en) | 2016-11-24 | 2023-04-25 | Obshchestvo S Ogranichennoy Otvetstvennost'Yu “Obedinennaya Kompaniya Rusal Inzhenerno-Tekhnologicheskiy Tsentr” | Method for producing aluminum alloys |
| CN110484765A (en) * | 2019-09-26 | 2019-11-22 | 河南科技大学 | A kind of aluminium bronze and preparation method thereof |
| CN110541085A (en) * | 2019-09-26 | 2019-12-06 | 河南科技大学 | Preparation method of aluminum cupronickel alloy |
| CN110484765B (en) * | 2019-09-26 | 2020-10-20 | 河南科技大学 | Aluminum bronze alloy and preparation method thereof |
| CN110541085B (en) * | 2019-09-26 | 2020-11-03 | 河南科技大学 | Preparation method of aluminum cupronickel alloy |
| CN110983380A (en) * | 2019-12-10 | 2020-04-10 | 中南大学 | Preparation method of aluminum-copper alloy |
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