CN104032135A - Method for recycling waste foamed magnesium - Google Patents
Method for recycling waste foamed magnesium Download PDFInfo
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- CN104032135A CN104032135A CN201410282650.XA CN201410282650A CN104032135A CN 104032135 A CN104032135 A CN 104032135A CN 201410282650 A CN201410282650 A CN 201410282650A CN 104032135 A CN104032135 A CN 104032135A
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- magnesium
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- foam magnesium
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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
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Abstract
The technical scheme disclosed by the invention is to provide a method for recycling waste foamed magnesium. The method comprises the following steps of firstly, carrying out pre-treatment on a waste material; secondly, smelting the waste material: evenly spreading a layer of bottom flux at the bottom of a crucible, then adding the foamed magnesium waste material treated in the first step into the crucible, then evenly spreading a layer of bottom flux on the surface of the foamed magnesium waste material, repeating the two steps, and introducing a gas mixture of SF6 and CO2 while melting; thirdly, refining liquid: adding a refining flux into the liquid obtained by the second step, refining, standing, and drossing to remove the surface material to obtain purified magnesium alloy liquid; fourthly, casting: casting the magnesium alloy liquid into magnesium alloy ingots. By virtue of the method disclosed by the invention, foamed magnesium is recycled and regenerated, and the recovery rate can reach above 80%. Based on conventionally prepared foamed magnesium, the waste of a magnesium alloy is greatly reduced by recycling the waste foamed magnesium, the utilization rate of the material is improved and the recycling of the foamed magnesium material is achieved.
Description
Technical field
The invention belongs to porous metal material regeneration field, aim to provide a kind of method that waste foam magnesium reclaims.
Background technology
Foam magnesium has metal and bubble feature concurrently, have that density is little, impact-absorbing ability is strong, damping shock absorption, sound insulation and noise reduction, thermal conductivity is low, electromagnetic wave shielding is high and the characteristic such as biocompatibility, it is had broad application prospects at current Material Field, engineering and the raw doctor's material that has very much exploitation future, particularly at aspects such as communications and transportation industry, aerospace industry, building structure industry and biomedical sectors.
But foam magnesium production cost is higher has at present restricted the universal of it, and can produce a large amount of waste foam magnesium in preparation and application process.Therefore, these foam magnesium waste refusions regenerated and carry out foamed preparation and can significantly reduce undoubtedly the production cost of foam magnesium.From long term growth angle, the recovery of waste foam magnesium and comprehensive utilization will become the important step of putting into practice Sustainable development, but up to the present rarely have the report about this problem.Only have CN101082093B to disclose a kind of method of remelting recycle of waste foamed aluminium.In addition, CN1614045 discloses a kind of recovery method of waste magnesium alloy, compared with the recovery of the pore space structure of foam magnesium uniqueness and complicated preparation technology and magnesium alloy waste material, can produce a lot of problems, and remelting is more difficult.So far, there is no the bibliographical information about foam magnesium waste recovery both at home and abroad.If the recovery to useless foam magnesium is furtherd investigate, will contribute to the reduction of foam magnesium production cost, and reduce the pollution of waste material rubbish.
Summary of the invention
The object of the invention is to for the higher problem of current foam magnesium production cost, a kind of recoverying and utilizing method of waste foam magnesium is provided, the method is utilized flux and reacting between infusibility phase and impurity in foam magnesium, and by the adding from level to level of end flux, thereby the material of removing the useless foam magnesium melting process of impact is realized the recovery of foam magnesium.The present invention can not only save material, reduces costs, and can meet the requirement of MAGNESIUM METAL starting material Sustainable development.
Technical scheme of the present invention is:
The method that useless foam magnesium reclaims, comprises the following steps:
The first step: the pre-treatment of waste material
Useless foam magnesium is cut into length and width and the block of Gao Jun within the scope of 5～50mm;
Second step: the melting of waste material
Crucible is preheated in resistance furnace to 400～500 DEG C, flux at the bottom of crucible bottom sprinkles one deck equably, then in crucible, add the foam magnesium waste material of processing through the first step, flux at the bottom of foam magnesium scraped surface sprinkles one deck equably again, again add the foam magnesium waste material that the first step was processed, so flux at the bottom of one deck, one deck scrap loop is added, and topmost one deck is end flux; Then the melting that heats up passes into SF simultaneously
6and CO
2mixed gas, heating makes material melting become liquid; Wherein, the thickness of every layer of end flux is approximately 0.5～4mm, and the waste material number of plies is 3～6 layers, and the consumption of end flux is 10～40% of the magnesia amount of waste foam;
The 3rd step: the refining of solution
In the time that solution temperature reaches 680～720 DEG C, in the solution being obtained by second step, add refining flux, refining time is 10～20min, stirs with the speed of 200～300r/min simultaneously; Then leave standstill 10～20min, the removal surface mass of skimming, thus obtain pure liquid magnesium alloy;
Wherein, the add-on of refining flux is 1.0～5.0% of foam magnesium waste material quality.
The 4th step: casting
The pure liquid magnesium alloy that the 3rd step is obtained is cast into magnesium alloy ingot;
Described end flux consist of mass percent 40～50%MgCl
2, 30～50%KCl, 5～20%NaCl, the mass percent summation of above each component is 100%,
Described refining flux is pressed massfraction by 85～95% end recited above flux and 5～15%CaF
2composition, the mass percent summation of each component is 100%.
Described mixed gas SF
6and CO
2volume ratio be 1:100～1:1.
Length and width and the height of the block that in the described the first step, the cutting of useless foam magnesium obtains are all preferably 10～30mm.
Beneficial effect of the present invention is:
Due to the pore space structure of foam magnesium uniqueness and complicated preparation technology, make some infusibility phases and impurity remelting more difficult, the present invention utilizes the interaction between infusibility phase and impurity in end flux and foam magnesium, thereby the material of removing the useless foam magnesium melting process of impact is realized the recovery of foam magnesium.
1, the magnesium chloride that contains significant proportion in the end flux of employing, it has very strong adsorption for the impurity such as magnesium oxide and magnesium nitride, can effectively remove oxide film and the oxidation particle of melt.In addition Repone K add surface tension and the force of cohesion that can reduce flux, can make the complete moistening melt of flux.On the basis of flux of original end, the present invention's end flux used forms simpler, and raw-material purchase and proportioning while having reduced recovery, avoided the more interference of multielement, and cheap, pollution-free.In addition, the density of this end flux and magnesium alloy density are very nearly the same, after reacting with impurity, form the larger bits of particle, on reducing, density floats on fluid surface, be sunken to crucible bottom than previous magnesium alloy recovery like this and more easily remove bits, and the method is applicable to the refusion regeneration of various foam magnesiums and magnesium alloy.Reclaim directly foamed of magnesium, the uniform foam magnesium of production pore structure.And then, for foam magnesium application provides more wide prospect, for suitability for industrialized production is brought huge economic and social benefit.
2, adopting the effect of refining flux is to wash liquid magnesium alloy with flux, utilizes flux and the next moistening inclusion of fully contacting of solution, and by its polymerization in flux, float to solution surface, finally make the impurity such as harmful element in liquid magnesium alloy separate with liquid magnesium alloy, thereby purify liquid magnesium alloy.
3, flux at the bottom of employing one deck, the useless foam magnesium circulation of one deck is added, and is conducive to fully contacting of end flux and useless foam magnesium, promotes effect each other, finally makes foam magnesium melt and is more prone to.
The present invention carries out the reclaiming of foam magnesium, and the rate of recovery can reach more than 80%.And prepare in routine on the basis of foam magnesium, the recovery of useless foam magnesium greatly reduces the waste of magnesium alloy, has improved material use efficiency, has realized the recycle of foam magnesium material.
Brief description of the drawings
Fig. 1 foam magnesium recovery process schema that gives up.
Fig. 2 is useless, and foam magnesium reclaims melting schematic diagram.
Fig. 3 is the foam magnesium that the recycling magnesium alloy that obtains in embodiment 1 makes again.
Fig. 4 is the compression curve of the foam magnesium that again makes of the recycling magnesium alloy that obtains in embodiment 1.
Embodiment
Embodiment 1:
The first step: material is prepared
Press massfraction preparation end flux 400g, shared mass percent example is respectively: 50%MgCl
2, 30%KCl, 20%NaCl, refining flux 100g, shared mass percent example is respectively: 90% end recited above flux and 10%CaF
2.With sawing machine by 1 kilogram of useless foam magnesium cut into length and width and high be block within the scope of 10～30mm (wherein, length and width and high measure-alike or different, following examples with.), wherein the body material of foam magnesium waste material is AZ31, Al is containing 3～3.2%; Zn is containing 0.8～1%; Mn is containing 0.4%; All the other are Mg.
Second step: melting
The crucible that is 100mm by internal diameter is preheated to garnet (400 DEG C) in resistance furnace, flux 40g at the bottom of crucible bottom sprinkles one deck equably, then in crucible, add the foam magnesium waste material 200g processing through the first step, sprinkle equably flux 40g at the bottom of one deck from foam magnesium scraped surface again, continue again to add waste material 200g, so flux at the bottom of one deck, one deck scrap loop is added, ensure that end flux fully contacts with waste material, wherein the thickness of every layer of end flux is approximately 1.7mm (taking the vertex of the useless foam magnesium that covers as benchmark, ), five layers of waste material altogether, flux at the bottom of six layers, at the bottom of 1 kilogram of useless foam magnesium that the first step was processed the most at last and 240g, flux joins crucible.Intensification melting, passes into SF taking volume ratio as 1:50 simultaneously
6and CO
2mixed gas, make with this understanding its fusing, from the solid-state liquid state that becomes.
The 3rd step: refining
In the time that solution temperature reaches 680 DEG C, add refining flux 10g, refining 20min stirs with the speed of 200r/min simultaneously, makes inclusion fully contact and be adsorbed by flux with flux.The liquid magnesium alloy that refining is good leaves standstill 10min, makes impurity flux reunion wherein float to solution surface, the removal surface mass of skimming, thus obtain pure liquid magnesium alloy.Wherein liquid magnesium alloy composition is that Al contains 3%; Zn is containing 0.8%; Mn is containing 0.4%; Foreign matter content is less than 0.1%, and all the other are Mg.
The 4th step: casting
The pure liquid magnesium alloy that the 3rd step is obtained is cast into magnesium alloy ingot 821g, and calculating the gained rate of recovery is 82.1%.
The 5th step: produce again
Weigh the magnesium ingot that 800g reclaims, in resistance furnace, melt, after melting, add that to account for magnesium ingot massfraction be 2% tackifier simple substance calcium particle, stir melt 8 minutes with the speed of 400 revs/min simultaneously, add subsequently that to account for magnesium ingot massfraction be 2% whipping agent calcium carbonate, stir melt 2 minutes with the speed of 800 revs/min simultaneously, propose stirring rake, be incubated by 5 minutes (in stove), propose mould, air cooling, obtains foam magnesium.
As can be seen from Figure 3, the foam magnesium again making.Its pore structure is even, and what make with most of starting material magnesium alloy is similar.
The compression curve of the foam magnesium again being made by Fig. 4 gained recycling magnesium alloy can find out, compression specimen size is 25*25*25mm, and strain rate is 0.001/s, and its compression curve is consistent with typical froth magnesium compression curve.
Embodiment 2:
The first step: material is prepared
Press massfraction preparation end flux 400g, proportion is respectively: 30%MgCl
2, 40%KCl, 10%NaCl, 10%CaCl
2, 10%BaCl
2.Refining flux 100g, proportion is respectively: 85% end flux and 15%CaF
2.1 kilogram of useless foam magnesium is cut into length and width and be the block within the scope of 30～50mm with high, wherein the body material of foam magnesium waste material is AZ91, and Al is containing 9～9.2%; Zn is containing 0.8～1%; Mn is containing 0.4%; All the other are Mg.
Second step: melting
The crucible that is 100mm by internal diameter is preheated to garnet (450 DEG C) in resistance furnace, flux 60g at the bottom of crucible bottom sprinkles one deck equably, then in crucible, add the foam magnesium waste material 200g processing through the first step, sprinkle equably flux 60g at the bottom of one deck from foam magnesium scraped surface again, continue again to add waste material 200g, so flux at the bottom of one deck, one deck scrap loop is added, ensure that end flux fully contacts with waste material, wherein the thickness of every layer of end flux is approximately 2.9mm, five layers of waste material altogether, flux at the bottom of six layers, at the bottom of 1 kilogram of useless foam magnesium that the first step was processed the most at last and 360g, flux joins crucible.Intensification melting, passes into SF taking volume ratio as 1:100 simultaneously
6and CO
2mixed gas, make with this understanding its fusing, from the solid-state liquid state that becomes.
The 3rd step: refining
In the time that solution temperature reaches 700 DEG C, add refining flux 30g, refining 15min stirs with the speed of 250r/min simultaneously, makes inclusion fully contact and be adsorbed by flux with flux.The liquid magnesium alloy that refining is good leaves standstill 15min, makes it be sunken to crucible bottom, thereby obtains pure liquid magnesium alloy.Wherein liquid magnesium alloy composition is that Al contains 9.1%; Zn is containing 0.9%; Mn is containing 0.4%; Foreign matter content is less than 0.1%, and all the other are Mg.
The 4th step: casting
The pure liquid magnesium alloy that the 3rd step is obtained is cast into magnesium alloy ingot 749g, and calculating the gained rate of recovery is 74.9%.
The 5th step: produce again
Weigh the magnesium ingot that 700g reclaims, in resistance furnace, melt, after melting, add that to account for magnesium ingot massfraction be 2% tackifier simple substance calcium particle, stir melt 8 minutes with the speed of 400 revs/min simultaneously, add subsequently that to account for magnesium ingot massfraction be 2% whipping agent calcium carbonate, stir melt 2 minutes with the speed of 800 revs/min simultaneously, propose stirring rake, be incubated by 5 minutes (in stove), propose mould, air cooling, obtains foam magnesium.
Embodiment 3:
The first step: material is prepared
Press massfraction preparation end flux 400g, proportion is respectively: 45%MgCl
2, 40%KCl, 15%NaCl, refining flux 100g, proportion is respectively: 95% end flux and 5%CaF
2.1 kilogram of useless foam magnesium is cut into length and width and be the block within the scope of 5～10mm with high, wherein the body material of foam magnesium waste material is AM60, and Al is containing 5.8～6.2%; Mn is containing 0.24～0.3%; Zn content is less than 0.22%, and all the other are Mg.
Second step: melting
The crucible that is 100mm by internal diameter is preheated to garnet (500 DEG C) in resistance furnace, flux 60g at the bottom of crucible bottom sprinkles one deck equably, then in crucible, add the foam magnesium waste material 1000g processing through the first step, waste material is not carried out to layering, sprinkle equably flux 60g at the bottom of one deck from foam magnesium scraped surface again, the thickness that wherein at every turn spreads end flux is approximately 2.4mm.Intensification melting, passes into SF taking volume ratio as 1:1 simultaneously
6and CO
2mixed gas, make with this understanding its fusing, from the solid-state liquid state that becomes.
The 3rd step: refining
In the time that solution temperature reaches 720 DEG C, add refining flux 50g, refining 10min stirs with the speed of 300r/min simultaneously, makes inclusion fully contact and be adsorbed by flux with flux.The liquid magnesium alloy that refining is good leaves standstill 20min, makes impurity flux reunion wherein float to solution surface, the removal surface mass of skimming, thus obtain pure liquid magnesium alloy.Wherein liquid magnesium alloy composition is that Al contains 6%; Mn is containing 0.25%; Zn content 0.2%, foreign matter content is less than 0.1%, and all the other are Mg.
The 4th step: casting
The pure liquid magnesium alloy that the 3rd step is obtained is cast into magnesium alloy ingot 705g, and calculating the gained rate of recovery is 70.5%.
The 5th step: produce again
Weigh the magnesium ingot that 700g reclaims, in resistance furnace, melt, after melting, add that to account for magnesium ingot massfraction be 2% tackifier simple substance calcium particle, stir melt 8 minutes with the speed of 400 revs/min simultaneously, add subsequently that to account for magnesium ingot massfraction be 2% whipping agent calcium carbonate, stir melt 2 minutes with the speed of 800 revs/min simultaneously, propose stirring rake, be incubated by 5 minutes (in stove), propose mould, air cooling, obtains foam magnesium.
Unaccomplished matter of the present invention is known technology.
Claims (4)
1. the method that useless foam magnesium reclaims, is characterized by and comprise the following steps:
The first step: the pre-treatment of waste material
Useless foam magnesium is cut into length and width and the block of Gao Jun within the scope of 5～50mm;
Second step: the melting of waste material
Crucible is preheated in resistance furnace to 400～500 DEG C, flux at the bottom of crucible bottom sprinkles one deck equably, then in crucible, add the foam magnesium waste material of processing through the first step, flux at the bottom of foam magnesium scraped surface sprinkles one deck equably again, again add the foam magnesium waste material that the first step was processed, so flux at the bottom of one deck, one deck scrap loop is added, and topmost one deck is end flux; Then the melting that heats up passes into SF simultaneously
6and CO
2mixed gas, heating makes material melting become liquid; Wherein, the thickness of every layer of end flux is approximately 0.5～4mm, and the waste material number of plies is 3～6 layers, and the consumption of end flux is 10～40% of the magnesia amount of waste foam;
The 3rd step: the refining of solution
In the time that solution temperature reaches 680～720 DEG C, in the solution being obtained by second step, add refining flux, refining time is 10～20min, stirs with the speed of 200～300r/min simultaneously; Then leave standstill 10～20min, the removal surface mass of skimming, thus obtain pure liquid magnesium alloy;
The 4th step: casting
The pure liquid magnesium alloy that the 3rd step is obtained is cast into magnesium alloy ingot;
Described end flux consist of mass percent 40～50%MgCl
2, 30～50%KCl, 5～20%NaCl, the mass percent summation of above each component is 100%.
2. the method that useless foam magnesium as claimed in claim 1 reclaims, it is characterized by described refining flux by massfraction by 85～95% end recited above flux and 5～15%CaF
2composition, the mass percent summation of each component is 100%, add-on is 1.0～5.0% of foam magnesium waste material quality.
3. the method that useless foam magnesium as claimed in claim 1 reclaims, is characterized by described mixed gas SF
6and CO
2volume ratio be 1:100～1:1.
4. the method that useless foam magnesium as claimed in claim 1 reclaims, length and width and the height of the block that in the first step described in it is characterized by, the cutting of useless foam magnesium obtains are all preferably 10～30mm.
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|---|---|---|---|
| CN201410282650.XA CN104032135B (en) | 2014-06-23 | 2014-06-23 | A kind of method that useless foam magnesium reclaims |
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| CN104032135B CN104032135B (en) | 2016-08-24 |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105671320A (en) * | 2016-03-30 | 2016-06-15 | 河北工业大学 | Recycling method of foamed magnesium |
| CN106222420A (en) * | 2016-08-14 | 2016-12-14 | 河北工业大学 | A kind of recycle and reuse method of waste foam magnesium |
| CN106939380A (en) * | 2017-02-19 | 2017-07-11 | 山东银光钰源轻金属精密成型有限公司 | A kind of recovery method of the exceeded magnesium alloy scurf of iron content |
| CN107429318A (en) * | 2015-02-16 | 2017-12-01 | 湖南斯瑞摩科技有限公司 | Method based on magnesium alloy waste material production national standard magnesium alloy ingot |
| CN114934184A (en) * | 2022-06-15 | 2022-08-23 | 郑州轻研合金科技有限公司 | Magnesium-lithium alloy waste recycling and vacuum regeneration method |
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|---|---|---|---|---|
| CN1088268A (en) * | 1993-09-30 | 1994-06-22 | 卢建德 | Process for recovering magnesium from magnesium slag |
| CN1614045A (en) * | 2004-10-10 | 2005-05-11 | 中国铝业股份有限公司 | Recovering method for waste magnesium alloy |
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2014
- 2014-06-23 CN CN201410282650.XA patent/CN104032135B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1088268A (en) * | 1993-09-30 | 1994-06-22 | 卢建德 | Process for recovering magnesium from magnesium slag |
| CN1614045A (en) * | 2004-10-10 | 2005-05-11 | 中国铝业股份有限公司 | Recovering method for waste magnesium alloy |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107429318A (en) * | 2015-02-16 | 2017-12-01 | 湖南斯瑞摩科技有限公司 | Method based on magnesium alloy waste material production national standard magnesium alloy ingot |
| CN105671320A (en) * | 2016-03-30 | 2016-06-15 | 河北工业大学 | Recycling method of foamed magnesium |
| CN106222420A (en) * | 2016-08-14 | 2016-12-14 | 河北工业大学 | A kind of recycle and reuse method of waste foam magnesium |
| CN106939380A (en) * | 2017-02-19 | 2017-07-11 | 山东银光钰源轻金属精密成型有限公司 | A kind of recovery method of the exceeded magnesium alloy scurf of iron content |
| CN114934184A (en) * | 2022-06-15 | 2022-08-23 | 郑州轻研合金科技有限公司 | Magnesium-lithium alloy waste recycling and vacuum regeneration method |
| CN114934184B (en) * | 2022-06-15 | 2023-11-07 | 郑州轻研合金科技有限公司 | Magnesium-lithium alloy waste recycling and vacuum regenerating method |
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|---|---|
| CN104032135B (en) | 2016-08-24 |
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