CN110527859A - Aluminium alloy free-floride is without the granular refining agent of sodium hollow ball shape and preparation method and application - Google Patents
Aluminium alloy free-floride is without the granular refining agent of sodium hollow ball shape and preparation method and application Download PDFInfo
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- CN110527859A CN110527859A CN201910875654.1A CN201910875654A CN110527859A CN 110527859 A CN110527859 A CN 110527859A CN 201910875654 A CN201910875654 A CN 201910875654A CN 110527859 A CN110527859 A CN 110527859A
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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
- C22B21/00—Obtaining aluminium
- C22B21/06—Obtaining aluminium refining
- C22B21/062—Obtaining aluminium refining using salt or fluxing agents
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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
- C22B26/00—Obtaining alkali, alkaline earth metals or magnesium
- C22B26/20—Obtaining alkaline earth metals or magnesium
- C22B26/22—Obtaining magnesium
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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
- C22B9/00—General processes of refining or remelting of metals; Apparatus for electroslag or arc remelting of metals
- C22B9/10—General processes of refining or remelting of metals; Apparatus for electroslag or arc remelting of metals with refining or fluxing agents; Use of materials therefor, e.g. slagging or scorifying agents
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C1/00—Making non-ferrous alloys
- C22C1/06—Making non-ferrous alloys with the use of special agents for refining or deoxidising
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C21/00—Alloys based on aluminium
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C23/00—Alloys based on magnesium
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Abstract
The present invention provides a kind of aluminium alloy free-floride without the granular refining agent of sodium hollow ball shape, belongs to aluminum refining agent technical field.It is made of the raw material for including following components: MgCl2Powder: 30%~40%, KCl powder: 30%~40%, MgCO3Powder: 5%~10%, BaCl2Powder: 4%~8%, CaCl2Powder: 4%~8%, Mg3N2Powder: 3%~10%.The preparation method of refining agent: 1) by MgCl2Powder and KCl powder mixture are put into electrical crucible；2) electrical crucible is powered and is heated up, and be passed through inert gas shielding, mixture gradually heats and starts to melt；3) after material fusing to be mixed, melt temperature is controlled at 450 DEG C~500 DEG C, by MgCO3Powder, BaCl2Powder, CaCl2Powder, Mg3N2Powder is added in fused salt；4) after powder is completely melt, melt is stirred evenly, control temperature is no more than 500 DEG C, stands 8~15min；5) melt of melted completion is transferred to pelletizer, and is blown inert gas into pelletizer, under inert gas shielding effect, spheric granules is made in melt.
Description
Technical field
The invention belongs to aluminium alloy refining agent technical field, specially a kind of aluminium alloy free-floride is without sodium hollow ball shape grain
Shape refining agent and preparation method and application.
Background technique
Metallurgical imperfection in aluminium, such as field trash, hydrogen, impurity element directly influence its mechanical property and are processed into
Type.Cleaning molten is the key technology for improving aluminium quality.During aluminum alloy melt casting, by refining, skimming, degasification and
Filtering, inclusion content significantly reduces, if but refining effect it is bad, still with the presence of micro field trash, and eventually enter into ingot casting, it is right
Blank following process and the physical property of final products, mechanical property, corrosion resistance and presentation quality are brought and are significantly affected.Cause
This research and development new high-efficiency refining agent, is the target that aluminium industry is pursued jointly.
Refining agent currently used in the market is usually powdery refining agent, and contains fluorine and chlorine, can be generated in use big
Fluorine-containing pernicious gas and flue dust are measured, is caused serious pollution to the environment, powder admixture refining agent is present in melt in solid form, to folder
The absorption of slag object and solute effect are unobvious, and degasification, slagging-off effect are limited.If misoperation easily forms flux field trash, pollution
Aluminium alloy melt；Localized hyperthermia's chemical reaction when refining treatment can generate serious aluminium oxidization burning loss etc..In current reinforcing ring
Border is protected under main trend, and smokeless, floride-free or low fluorine necessarily becomes aluminium processing industry refining agent market without the serial refining agent such as sodium
Development trend.
Granular refining agent ingredient is uniform, and fusing point is lower, there is slagging-off well, removal of impurities effect in aluminum melt.Work as solid grain
After shape refining agent sprays into aluminum melt by inert gas, solid particle can be melted into rapidly drop, since the density of these drops is small
It is smaller with Slag inclusion surface tension in the density of aluminum melt, the ability with very strong wetting and absorption Slag inclusion；Work as Slag inclusion
After the absorption of flux drop, floats and be excluded from melt.Meanwhile one layer of liquid level is formd after flux drop floating and is covered on
Aluminium melt surface, to also reduce the oxidization burning loss of aluminum melt.
Summary of the invention
The purpose of the present invention is to provide a kind of aluminium alloy free-florides without the granular refining agent of sodium hollow ball shape and preparation method
And application.It is not fluorine-containing in the granular refining agent of the present invention to be free of sodium, prevent the generation of the fluorine in refining process from polluting environment；Pass through this
The granular refining agent that invention preparation method obtains is that open circles are spherical, hollow interior package inert gas, when to refining aluminium fusant
With rapid melting and it can will not bring air into, so that in refining aluminium fusant, it is small to aluminum melt oxidization burning loss, it is easier to by aluminium
Being mingled in melt takes out of, achievees the effect that refining.
The object of the invention is achieved through the following technical solutions:
A kind of aluminium alloy is floride-free without the granular refining agent of sodium hollow ball shape, by the raw material system including following weight percent
At:
MgCl2Powder: 30%~40%
KCl powder: 30%~40%
MgCO3Powder: 5%~15%
BaCl2Powder: 5%~12%
CaCl2Powder: 5%~12%
Mg3N2Powder: 5%~10%.
A kind of aluminium alloy is floride-free without the granular refining agent of sodium hollow ball shape, by the raw material system including following weight percent
At:
MgCl2Powder: 35%
KCl powder: 35%
MgCO3Powder: 10%
BaCl2Powder: 8%
CaCl2Powder: 6%
Mg3N2Powder: 6%.
A kind of aluminium alloy is floride-free without the granular refining agent of sodium hollow ball shape, by the raw material system including following weight percent
At:
MgCl2Powder: 33%
KCl powder: 37%
MgCO3Powder: 8%
BaCl2Powder: 6%
CaCl2Powder: 8%
Mg3N2Powder: 8%.
A kind of floride-free preparation method without the granular refining agent of sodium hollow ball shape of aluminium alloy, comprising the following steps:
1) by MgCl2Powder is uniformly mixed to obtain mixture with KCl powder, and mixture is put into electrical crucible；
2) electrical crucible is powered and is heated up, and be passed through inert gas shielding, mixture gradually heats and starts to melt；
3) after material to be mixed is completely melt, melt temperature is controlled at 450 DEG C~500 DEG C, by MgCO3Powder, BaCl2Powder,
CaCl2Powder, Mg3N2Powder is added in fused salt；
4) after powder is completely melt, melt is stirred evenly, control temperature is no more than 500 DEG C, stands 8~15mi n；
5) melt of melted completion is transferred to pelletizer, and is blown inert gas into pelletizer, in inert gas shielding
Under effect, spheric granules is made in melt；
6) spheric granules Vacuum Package is stand-by.
The preparation method of refining agent of the present invention, innovation are broadly divided into two o'clock:
1, common refining agent mostly uses open tanning (fusion process), and fused salt is directly exposed to air, and fused salt holds very much
Easily evaporation, especially villaumite and the moisture content in air at high temperature HCl gas easily generated and vapor away, the present invention is in resistance crucible
(step 2) during tanning, 3), 4)) by the protection of inert gas, the volatilization loss of fused salt when can not only reduce tanning,
The generation of HCl gas can also be reduced, so that the refining agent stable components of tanning, guarantee its service performance.
2, the granulation process of this method is fused salt to be dispelled into drop by the inert gas of high speed blowing, and incite somebody to action a small amount of lazy
Property gas wrapping be formed by spheric granules in the fused salt of rapid cooling, spheric granules is due to comprising inert gas and in hollow
Shape.Faster, introduced inert gas exists burn-off rate refining agent with this characteristic with fused salt disperse in use
In aluminum melt, it is easier to take being mingled in melt out of.Furthermore air will not be brought into when to refining aluminium fusant, oxidation is reduced and burn
Damage.
Further, the inert gas is N2Or Ar, 300~500L/min of injecting velocity, inert gas pressure 3MPa
~5MPa.
Further, the pelletizer is granulated under the conditions of blowing inert gas, prilling temperature 450 DEG C~480
℃。
Further, further include screening before the Vacuum Package, 6 mesh~60 purposes are picked out into the screening of manufactured spheric granules
Spheric granules.
A kind of floride-free application without the granular refining agent of sodium hollow ball shape of aluminium alloy, the refining agent are molten in aluminium and aluminium alloy
Application in body refining process.
Further, application of the refining agent in magnesium and magnesium alloy fused mass refining process.
Further, when 700 DEG C~760 DEG C of temperature of aluminum liquid to be processed, granular refining agent, the addition of granular refining agent is added
Amount is the 0.025~0.1% of aluminum amount to be processed.Refining agent particle is equably sprayed into inside melt using blowing device, is stirred
Uniformly, charging rate is unsuitable too fast, per minute no more than 1 kilogram, after standing 10~15 minutes, skims.
Compared with prior art, the invention has the following advantages:
It is not fluorine-containing in the granular refining agent of the present invention to be free of sodium, prevent the generation of the fluorine in refining process from polluting environment；Pass through
The granular refining agent that preparation method of the present invention obtains is that open circles are spherical, hollow package inert gas, when to refining aluminium fusant
It can quickly melt, the inert gas being introduced into is with fused salt disperse in aluminum melt, it is easier to being mingled in melt be taken out of, reached
To the effect of refining.Furthermore air will not be brought into when to refining aluminium fusant, reduce oxidization burning loss.
The granular refining agent of the present invention is smokeless without dust in use, has no adverse effects to human body, equipment and environment；It is empty
Heart particle melts in the melt discharges small inertia bubble, can significantly improve refining effect；Hollow granular refining agent dosage is big
Width reduces.
Specific embodiment
In order to make the objectives, technical solutions, and advantages of the present invention clearer, with reference to embodiments, to the present invention
It is further elaborated.It should be appreciated that described herein, specific examples are only used to explain the present invention, is not used to limit
The fixed present invention.
Embodiment 1
By MgCl2Powder: 35%, KCl powder: 35%, MgCO3Powder: 10%, BaCl2Powder: 8%, CaCl2Powder:
6%, Mg3N2Powder: the 6% granular refining agent of group assignment system；
By load weighted MgCl2It is uniformly mixed to obtain mixture with KCl powder, mixture is put into electrical crucible and is added
Heat fusing leads to nitrogen protection melt, after material to be mixed is completely melt, controls melt temperature at 450 DEG C~500 DEG C, and by MgCO3
Powder, BaCl2Powder, CaCl2Powder, Mg3N2It is added in fused salt, is stirred continuously in three times after powder mixing, control after boiling sufficiently
Temperature processed is no more than 500 DEG C, stands 10min, is transferred to pelletizer granulation；
Pelletizer hopper is preheated to 250 DEG C or more, and the melt temperature being transferred to is controlled at 450 DEG C~480 DEG C, and continues to protect
Temperature, the nitrogen-blow into pelletizer, nitrogen pressure control are 4Mpa, under inert gas shielding effect, melt are made hollow
Spheric granules；
Cooling spheric granules is filtered out into the qualified hollow granular refining agent of 6~60 mesh by industry.
The granular refining agent of hollow ball shape that the present embodiment is prepared is tested in 30t aluminium melting furnace, aluminum water is about
30t (50% or more waste material), 730 DEG C of aluminum water temperature, by refining agent blowing device by 24kg (dosage 0.08%) granular refining
Agent addition aluminium melting furnace, refining 30min, I grade of degree of purity of sampling microscopic structure detection (it detects according to GB/T32186-2015, under
Together).
Embodiment 2
By MgCl2Powder: 33%, KCl powder: 37%, MgCO3Powder: 8%, BaCl2Powder: 6%, CaCl2Powder:
8%, Mg3N2Powder: the 8% granular refining agent of group assignment system.
By load weighted MgCl2It is uniformly mixed to obtain mixture with KCl powder, mixture is put into electrical crucible and is added
Heat fusing leads to nitrogen protection melt, after material to be mixed is completely melt, controls melt temperature at 450 DEG C~500 DEG C, and by MgCO3
Powder, BaCl2Powder, CaCl2Powder, Mg3N2It is added in fused salt, is stirred continuously in three times after powder mixing, control after boiling sufficiently
Temperature processed is no more than 500 DEG C, stands 10min, is transferred to pelletizer granulation；
Pelletizer hopper is preheated to 250 DEG C or more, and the melt temperature being transferred to is controlled at 450 DEG C~480 DEG C, and continues to protect
Temperature is blown argon gas into pelletizer, and argon pressure control is 3Mpa, and under inert gas shielding effect, spherical shape is made in melt
Particle；
Cooling spheric granules is filtered out into the qualified hollow granular refining agent of 6~60 mesh by industry.
The spherical granular refining agent that the present embodiment is prepared is turned to test in water packet in 1t, aluminum water about 800Kg, aluminium
720 DEG C of coolant-temperature gage, the granular refining agent of 0.5kg (dosage 0.06%) is added by aluminium melting furnace, refining by refining agent blowing device
10min, sampling microscopic structure detect I grade of degree of purity.
Embodiment 3
By MgCl2Powder: 40%, KCl powder: 40%, MgCO3Powder: 5%, BaCl2Powder: 5%, CaCl2Powder:
5%, Mg3N2Powder: the 5% granular refining agent of group assignment system.
By load weighted MgCl2It is uniformly mixed to obtain mixture with KCl powder, mixture is put into electrical crucible and is added
Heat fusing leads to nitrogen protection melt, after material to be mixed is completely melt, controls melt temperature at 450 DEG C~500 DEG C, and by MgCO3
Powder, BaCl2Powder, CaCl2Powder, Mg3N2It is added in fused salt, is stirred continuously in three times after powder mixing, control after boiling sufficiently
Temperature processed is no more than 500 DEG C, stands 10min, is transferred to pelletizer granulation.
Pelletizer hopper is preheated to 250 DEG C or more, and the melt temperature being transferred to is controlled at 450 DEG C~480 DEG C, and continues to protect
Temperature, the nitrogen-blow into pelletizer, nitrogen pressure control are 5Mpa, and under inert gas shielding effect, spherical shape is made in melt
Particle.
Cooling spheric granules is filtered out into the qualified hollow granular refining agent of 6~60 mesh by industry.
The spherical granular refining agent that the present embodiment is prepared is tested in 30t aluminium melting furnace, aluminum water about 27t
730 DEG C of aluminum water temperature, aluminium is added by refining agent blowing device in 14kg (dosage 0.05%) granular refining agent by (waste material 30%)
Smelting furnace, refines 25min, and sampling microscopic structure detects I grade of degree of purity.
Comparison example one:
Refining agent is prepared according to testing program shown in example 1, a furnace is made fully according to described in example 1 in melting process
It is standby, nitrogen protection is not added in another furnace melting process, other processes are consistent, do stokehold refining test, spray respectively to two kinds of products
It is all the same to blow speed, temperature of aluminum liquid, refining agent dosage.The comparison of two furnace melt purification testing results is shown in Table 1.
Different melted mode (the whether inert gas being added) comparing results of table 1
Note: degree of purity detection method is according to GB/T32186-2015 " aluminium and aluminium alloy cast ingot degree of purity detection method " in table
Can be seen that the addition inert gas in melting process by upper 1 data of table can be improved the property of granular refining agent
Can, aluminum melt is refined with the granular refining agent being prepared under identical circumstances, inert gas shielding is added and obtains
Granular refining agent can reduce the scaling loss of melting process, improve aluminum melt purity level grade, reach better clean-up effect.
Comparison example two:
Refining agent is prepared also according to testing program shown in example 1, a furnace is fully according to described in example 1 in melting process
Preparation, another furnace not nitrogen-blow in granulation process, other processes are consistent, do stokehold refining test respectively to two kinds of products,
Injecting velocity, temperature of aluminum liquid, refining agent dosage are all the same.And the appearance of two kinds of products is compared, test process is consistent, examination
It tests and the results are shown in Table 2.
It can be seen that granulation process by the following table 2 data and blowing inert gas be not added, the granular size produced is uneven,
And easy adhesion, it influences using by way of adding nitrogen-blow when being granulated, the granulation uniformity produced is good, in granulation process
The granular refining agent that middle addition inert gas shielding obtains can reduce the scaling loss of melting process, save refining agent to the greatest extent
Effective component.Therefore two kinds of refining agents are under equal conditions used, it is obtaining the result is that passing through indifferent gas in granulation process
The granular refining agent of body protection has better refining effect.
Different granulation mode (the whether inert gas being added) comparing results of table 2
Note: degree of purity detection method is according to GB/T32186-2015 " aluminium and aluminium alloy cast ingot degree of purity detection method " in table
The foregoing is merely illustrative of the preferred embodiments of the present invention, is not intended to limit the invention, all in essence of the invention
Made any modifications, equivalent replacements, and improvements etc., should all be included in the protection scope of the present invention within mind and principle.
Claims (10)
1. a kind of aluminium alloy free-floride is without the granular refining agent of sodium hollow ball shape, which is characterized in that by including following weight percent
Raw material be made:
MgCl2Powder: 30%~40%
KCl powder: 30%~40%
MgCO3Powder: 5%~10%
BaCl2Powder: 4%~8%
CaCl2Powder: 4%~8%
Mg3N2Powder: 3%~10%.
2. a kind of aluminium alloy free-floride is without the granular refining agent of sodium hollow ball shape as described in claim 1, which is characterized in that by including
The raw material of following weight percent is made:
MgCl2Powder: 35%
KCl powder: 35%
MgCO3Powder: 10%
BaCl2Powder: 8%
CaCl2Powder: 6%
Mg3N2Powder: 6%.
3. a kind of aluminium alloy free-floride is without the granular refining agent of sodium hollow ball shape as described in claim 1, which is characterized in that by including
The raw material of following weight percent is made:
MgCl2Powder: 33%
KCl powder: 37%
MgCO3Powder: 8%
BaCl2Powder: 6%
CaCl2Powder: 8%
Mg3N2Powder: 8%.
4. a kind of floride-free preparation side without the granular refining agent of sodium hollow ball shape of aluminium alloy as described in any one of claims 1 to 3
Method, which comprises the following steps:
1) by MgCl2Powder is uniformly mixed to obtain mixture with KCl powder, and mixture is put into electrical crucible；
2) electrical crucible is powered and is heated up, and be passed through inert gas shielding, mixture gradually heats and starts to melt；
3) after material to be mixed is completely melt, melt temperature is controlled at 450 DEG C~500 DEG C, by MgCO3Powder, BaCl2Powder,
CaCl2Powder, Mg3N2Powder is added in fused salt；
4) after powder is completely melt, melt is stirred evenly, control temperature is no more than 500 DEG C, stands 8~15min；
5) melt of melted completion is transferred to pelletizer, and is blown inert gas into pelletizer, acted in inert gas shielding
Under, spheric granules is made in melt；
6) spheric granules Vacuum Package is stand-by.
5. the floride-free preparation method without the granular refining agent of sodium hollow ball shape of a kind of aluminium alloy as claimed in claim 4, feature
It is, the inert gas is N2Or Ar, 300~500L/min of injecting velocity, inert gas pressure are 3MPa~5MPa.
6. the floride-free preparation method without the granular refining agent of sodium hollow ball shape of a kind of aluminium alloy as claimed in claim 4, feature
It is, the pelletizer is granulated under the conditions of blowing inert gas, 450 DEG C~480 DEG C of prilling temperature.
7. the floride-free preparation method without the granular refining agent of sodium hollow ball shape of a kind of aluminium alloy as claimed in claim 4, feature
It is, further includes screening before the Vacuum Package, 6 mesh~60 mesh spheric granules is picked out into the screening of manufactured spheric granules.
8. the floride-free application without the granular refining agent of sodium hollow ball shape of a kind of aluminium alloy as described in claim 1, which is characterized in that
Application of the refining agent in aluminium and aluminium alloy melt refining process.
9. the floride-free application without the granular refining agent of sodium hollow ball shape of a kind of aluminium alloy as claimed in claim 8, which is characterized in that
Application of the refining agent in magnesium and magnesium alloy fused mass refining process.
10. a kind of floride-free application without the granular refining agent of sodium hollow ball shape of aluminium alloy, feature exist as claimed in claim 8
In when 700 DEG C~760 DEG C of temperature of aluminum liquid to be processed, being added granular refining agent, the additional amount of granular refining agent is aluminium to be processed
The 0.025~0.1% of amount.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN112048634A (en) * | 2020-09-11 | 2020-12-08 | 四川兰德高科技产业有限公司 | Fluorine-free chlorine-free environment-friendly granular refining agent for aluminum alloy and preparation and application thereof |
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| CN109207767A (en) * | 2017-07-06 | 2019-01-15 | 王再青 | A kind of aluminium alloy sodium-free refining agent and preparation method thereof |
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| CN109097618A (en) * | 2018-08-07 | 2018-12-28 | 湖南金联星特种材料股份有限公司 | Aluminium alloy floride-free particle refining agent and its manufacturing method |
| CN109454210A (en) * | 2018-12-24 | 2019-03-12 | 江苏嘉耐高温材料有限公司 | A kind of ultra-thin band double-layer tundish covering agent |
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| CN112048634A (en) * | 2020-09-11 | 2020-12-08 | 四川兰德高科技产业有限公司 | Fluorine-free chlorine-free environment-friendly granular refining agent for aluminum alloy and preparation and application thereof |
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