CA2148923A1 - The method of manufacturing alloy by using aluminum residuum - Google Patents
The method of manufacturing alloy by using aluminum residuumInfo
- Publication number
- CA2148923A1 CA2148923A1 CA 2148923 CA2148923A CA2148923A1 CA 2148923 A1 CA2148923 A1 CA 2148923A1 CA 2148923 CA2148923 CA 2148923 CA 2148923 A CA2148923 A CA 2148923A CA 2148923 A1 CA2148923 A1 CA 2148923A1
- Authority
- CA
- Canada
- Prior art keywords
- aluminum
- alloy
- residuum
- blending
- manufacturing
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Abandoned
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Classifications
-
- 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
- C22C1/02—Making non-ferrous alloys by melting
-
- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21C—PROCESSING OF PIG-IRON, e.g. REFINING, MANUFACTURE OF WROUGHT-IRON OR STEEL; TREATMENT IN MOLTEN STATE OF FERROUS ALLOYS
- C21C7/00—Treating molten ferrous alloys, e.g. steel, not covered by groups C21C1/00 - C21C5/00
- C21C7/04—Removing impurities by adding a treating agent
- C21C7/06—Deoxidising, e.g. killing
-
- 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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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Mechanical Engineering (AREA)
- Manufacture And Refinement Of Metals (AREA)
- Refinement Of Pig-Iron, Manufacture Of Cast Iron, And Steel Manufacture Other Than In Revolving Furnaces (AREA)
Abstract
ABSTRACT
An object of the invention is to provide a method of manufacturing aluminum alloy by effectively using the aluminum residuum containing a low percentage of metal aluminum as industrial wastes. As the component ratio of a briquette of aluminum residuum, a mass of silica rock and a mass of anthracite, the weight percentage of Al2O3:SiO2:C=40:33:27 is maintained. The blending having a maintained weight percentage is continuously introduced into the electric furnace for producing carbide. The electric furnace is provided with three self-baking electrodes having a diameter of 1400mm, and a transformer capacity of 30,000KVA. While the electrodes are embedded at the depth of about 1m and the temperature in the electric arc range is kept between 2200°C and 2400°C, the melting reduction is carried out. When 170 tons of aluminum residuum briquette were completely introduced into the electric furnace, 100 tons of Al-Si-Fe alloy were obtained. The aluminum alloy can be used as deoxidizer or temperature raising agent in the iron and steel manufacture with variously developed manufacture processes and needs.
An object of the invention is to provide a method of manufacturing aluminum alloy by effectively using the aluminum residuum containing a low percentage of metal aluminum as industrial wastes. As the component ratio of a briquette of aluminum residuum, a mass of silica rock and a mass of anthracite, the weight percentage of Al2O3:SiO2:C=40:33:27 is maintained. The blending having a maintained weight percentage is continuously introduced into the electric furnace for producing carbide. The electric furnace is provided with three self-baking electrodes having a diameter of 1400mm, and a transformer capacity of 30,000KVA. While the electrodes are embedded at the depth of about 1m and the temperature in the electric arc range is kept between 2200°C and 2400°C, the melting reduction is carried out. When 170 tons of aluminum residuum briquette were completely introduced into the electric furnace, 100 tons of Al-Si-Fe alloy were obtained. The aluminum alloy can be used as deoxidizer or temperature raising agent in the iron and steel manufacture with variously developed manufacture processes and needs.
Description
`- 21~8923 SPECIFICAT:[ON
THE METHOD OF MANUFACTURING ALLOY BY USING ALUMINUM RESIDUUM
TECHNICAL FIELD
The present invention relates to a method of manufacturing alloy by using aluminum residuum.
BACKGROUND OF THE INVENTION
An aluminum alloy is classified roughly into a mass of alloy newly formed by electrolyzing alumina and a mass of alloy recovered from the recycling material. The former alloy is used as plates, cans or other materials, while the latter alloy is used as the material for die casting and molding or as an aluminous deoxidizer in the field of iron and steel manufacture.
Recently, in some countries since the cost of petroleum thermal power or other electric power was increased, the refining of aluminum by means of electrolysis was almost completely abolished. These countries buy aluminum materials from the other countries with low electric power cost incurred, and manufacture only the necessary component alloys~ Even during such manufacture, aluminum including recovered aluminum is melted. At the melting step, generally 3% to 5% of aluminum dross is generated. The aluminum dross usually contains 40% to 60% of metal aluminum. To effectively use aluminum dross, by pulverizing or screening 2148~2~
the dross, high-grade metal aluminum is separated from the dross. The metal aluminum is again melted to recover aluminum. The method for recycling the residuum resulting from the recovery of aluminum, however, was not known.
The aluminum residuum varies in the content of metal aluminum according to their particle sizes. Nowadays the aluminum residuum having the particle size of lmm at maximum and containing the high percentage (30-50%) of metal aluminum are used for the new purpose of desulfurization, deoxidizing and temperature raising. This has been realized by the improved blowing technique in the iron or steel making process.
On the other hand, the aluminum residuum having the particle size of no larger than 100 mesh and containing the low percentage (20% or less) of metal aluminum is only partly used as the slag producing agent alternative for fluorites at the time of iron steel manufacture.
In the present ladle refining (LF) process, however, since the aforementioned aluminum residuum containing the low percentage of metal aluminum contains nitrogen, the application range thereof is narrowly restricted. Therefore, practically most part of such aluminum residuum is not recycled. Not-recycled aluminum residuum is disposed of as industrial wastes. When aluminum nitride (AlN) contained in the industrial wastes comes in contact with water, undesirable ammonia is generated. Because only a few controlled terminal disposal plants are available, the ... . .
2lgL8~23 disposal cost soars and the management of companies is depressed. Thus, the aluminum industry is facing a serious problem.
DISCLOSURE OF INVENTION
The present invention has been developed to solve the aforementioned problem. The object of the invention is to provide a method of manufacturing alloy by using aluminum residuum, particularly a method of manufacturing aluminum alloy by effectively using the industrial wastes of aluminum residuum containing a low percentage of metal aluminum as industrial wastes.
To attain the aforementioned object, in the method of manufacturing alloy by using aluminum residuum according to the first invention, the molded aluminum residuum, a mass of raw material mainly composed of silicon dioxide and a mass of carbon reducing agent are blended and introduced in an electric furnace. Through the melting reducing reaction, an aluminum-silicon alloy is formed.
In the method of manufacturing alloy by using aluminum residuum according to the second invention, aluminum residuum, the raw material mainly composed of silicon dioxide and carbon reducing agent are blended molded and introduced in an electric furnace. Through the melting reducing reaction, an aluminum-silicon alloy is formed.
In the method of manufacturing alloy by using aluminum residuum according to the third invention, iron oxide is .
21~8~23 further added to the blending used in the first or second invention.
In the method of manufacturing alloy by using aluminum residuum according to the fourth invention, by adding carbide slag and/or quicklime to the blending used in the first, second or third invention, an aluminum-silicon-calcium alloy is formed.
In the method of manufacturing alloy by using aluminum residuum according to the fifth invention, the aluminum-silicon alloy resulting from either of the methods of first through third inventions are crystallized, separated and refined, thereby increasing the content of aluminum in the alloy.
Aluminum residuum, the raw material mainly composed of silicon dioxide and the carbon reducing agent in use for the present invention is each molded or massed. Alternatively, these three components are blended and molded. A ma~s or mold is preferred because the melting reducing reaction at high temperatures can be efficiently advanced. The gas generated in the course of reaction can be driven out.
Additionally, generated aluminum, silicon, aluminum-~ilicon or other vaporized metal can be adhered to the surface of the moid for recovery. The size of the mold or mass is not limited: each side of the mold or mass is preferably between 20mm and lOOmm for easy handling. Further, the powdered material is difficult to use, because powder is disper~ed in the flow of air at high temperature when introduced into the 2~8~23 electric furnace.
The aluminum residuum used in the present invention is generated on the surface of molten metal aluminum. The residuum is crushed into powder generally by a ball mill or other adequate device, and the powder is captured by a cyclone or a dust collector. The aluminum residuum generally has a particle size of 100 mesh at maximum and contains 20% or less of metal aluminum.
The raw material mainly composed of silicon dioxide for use in the present invention is, for example, silica rock, silica sand, clay, bentonite or other mineral. The grade of silicon dioxide is preferably 94% at minimum. Particularly, clay, bentonite or other mineral is desirable, because it also serves as a caking agent when molded together with the aluminum residuum and the carbon reducing agent.
The carbon reducing agent used in the present invention can be anthracite, coke or other. When the blending is molded, coke dust or carbon dust can be used.
The reducing reaction of alumina is suppo~ed to proceed in the following reaction mechanism: -2Al203~S)+3C(S) -> Al~04C(melt)+2C0 ......
l/2Al404C(melt)+3C(S) -> l/2Al4C3(S)+2C0 ......
l/2Al4 04 C(melt)+l/2Al4C3(S) -> 4Al(melt)+2C0 ......
The following formula~ is derived from formulas~ and ~ .
: : ,. . . :
21~8~2~
2Al203(S)+6C(S) -> 4Al(melt)+6CO ......
Where silicon dioxide is present, the following formula~
precedes the reaction of formula ~ . According to formula an aluminum-silicon alloy is generated.
SiO2(S)+3C(S) -> SiC(S)+2CO ......
Al4O4C(melt)+3SiC(S) -> 4Al-Si(melt)+4CO ...... ~
In the system of Al203-SiO2-C with iron oxide added thereto (the third invention) iron oxide is reduced at a relatively low temperature. In the alumina reducing step metal iron is present, thereby decreasing the activity of aluminum. Therefore, at the temperature lower by about 100C
than the temperature when the system contains no iron the reaction proceeds as in formula ~ without generating Al4C3.
Al404C(melt)+3C(S) -> 4Al(melt)+4CO ......
In the present invention when the aluminum-silicon alloy rich in aluminum is obtained, aluminum residuum preferably contains 50-60% of Al2 03 and 40-50% of SiO2. If 100 parts of these two materials are existing, 35-40 parts of C as the carbon reducing agent are appropriate. When the alloy rich in silicon is obtained, conversely to the aforementioned ratio, 50-60% of silica and 40-50% of alumina are appropriate.
The carbide slag used in the fourth invention is ' ~
, 6 ~ ;
'' ~ ;
. , ~ . .
-- 21~8~23 composed mainly of calcium oxide, calcium carbide and others, as is generally known.
In the crystallizing separation step carried out in the fifth invention, by filtering the molten alloy, the content of aluminum in the alloy is raised.
The aluminum alloy resulting from the first to ~ourth invention can be used for manufacturing steels, for example As an illustration, the temperature raising agent is used in the LF refining furnace having no electric arc heater. As another illustration, an inexpensive and efficient deoxidizer is used for removing the remaining oxygen from the steel in the electric furnace, when the peroxidizing operation is generally carried out during the steel making process.
The aluminum alloy obtained according to the fifth invention, which contains high percentage of aluminum, can be used as the mother alloy of aluminum for casting.
BEST MODES FOR PRACTICING TH~ INVENTION
The embodiments of the present lnvention are explained below.
The first embodiment is an example of the first invention. 100 mesh or smaller aluminum residuum having the composition of Table 1 is molded into a briquette having a size of 40x 40x 25mm. A mass of silica rock and anthracite have 20 to 50mm long sides and the compositions shown in Table 1, respectively. While the weight percentage of these materials was maintained as Al203 :SiO2 :C=40:33:27, the 2~4892~
materials were continuously fed into the electric furnace for producing carbide. The electric furnace includes three self-baking electrodes having a diameter of 1400mm and has a transformer capacity of 30,000K~A. The electrodes were retained at the embedding depth of about lm, and their temperature was kept between 2200C and 2400C in the electric arc region. On this condition the melting reduction was carried out. After 170 tons of the formed aluminum residuum had been completely fed into the electric furnace, 100 tons of Al-Si-Fe alloy were obtained.
: 21~8~23 <THE CHEMICAL COMPOSITION OF RAW MATERIALS>
ALUMINUM ' SILICA ' ANTHRACITE ' COKE
RESIDUUMUA ' ROCK
_, , , Al2 03 , 75.6 , 1.2 , -- , 3.5 METAL Al ' 10.6 ' 0.0 ' -- ' --SiO2 ' 5.2 ' 94.0 '7.6 ' 7.2 MgO ' 2.3 , 0.6 ' -- , --C ' 0.5 ' -- '76.0 ' 87.7 Fe203 ' 0.6 ' 2.5 '1.5 ' 0.2 .
N ' 3.2 ' -- ' -- ' --CaO ' 0.2 ' 0.5 ' -- ' --.
TiOz ' 0.2 ' Tr ' -- ' --Ig.Loss ' -- , 1.2 ' -- ' 1.0 ASH ' -- , -- ' 12.0 ' --I
(UNIT: WEIGHT %) . ~ . . - , : . ~ .:
- . . - : . . . - . . .
. . . ~: - , ' -~ 48~23 :
The produced metal was composed of 43.2% of Al, 39.2% of Si, 15.2% of Fe, 0.49% of C, less than 0.01% of S, 0.03% of P, 0.02% of N, 0.59% of Ti, 0.5% of Cr, 0.23% of Mn, 0.17% of Ca, 0.11% of Mg and other components (Ni, Zn, Cu, Sn, Pb).
The produced metal contains iron more than expected according to the reaction theory. Because the steel supports (casing material) of electrodes were thermally melted down and lost in the course of the melting reducing reaction.
Also, the steel tapping materials, past which the produced metal was discharged, were also melted into the composition.
The electric power consumption rate was 13,000KWH on average per ton of alloy.
The aluminum alloy resulting from the first embodiment can be used as a temperature raising agent for a converter or for the LF refining furnace having no electric arc heater in the iron and steel industry. In the steel industry in which the electric furnace is used and the peroxidizing operation is general, the aluminum alloy can be used as a deoxidizer for removing the remaining oxygen from steel.
As an illustration of the second invention, the second embodiment is now explained.
Instead of the mass of silica rock used in the aforementioned first embodiment, the silica rock was crushed into ~0 mesh or smaller particles. Instead of the mass of anthracite used in the first embodiment, powdered anthracite waæ used. The weight percentage of raw materials was the same as that in the first embodiment. Pulp waste liquid was - 21~8~23 used as a binder. First, a briquette of aluminum residuum, silica rock and anthracite was obtained. The briquette has a strength of 100kg/cm2 at minimum at normal temperatures and a size of 40x 40x 2~mm. The briquette was inserted into the electric furnace. On the condition same as that in the first embodiment, the melting reduction was carried out. After 160 tons of the briquette in terms of the weight of blended aluminum residuum was completely inserted into the electric furnace, 100 tons of Al-Si-Fe alloy was obtained. The produced metal had almost the same composition as that of the first embodiment. As compared with the first embodiment, the electric power consumption rate was decreased by 1500KWH per ton. Further, the reduction yielding was enhanced.
Therefore, the second embodiment is preferable for the mass production.
The aluminum alloy resulting from the second embodiment has the same industrial applications as the first embodiment.
As an illustration of the third invention, the third embodiment is now explained.
In the third embodiment the briquette was obtained by additionally blending 10% of scales (T-FeO 93.9%) with the blended raw materials of the second embodiment. The briquette was introduced into the electric furnace and the melting reduction was carried out on the same condition as the first embodiment. As compared with the first embodiment, the content of Fe in the produced metal was increased by 5.2%, and the electric power consumption rate was decreased :: , - . ~, . - ~ - - . .
^`" 214~
by 1800KWH per ton. Consequently, the reduction of Al203-SiO2 system was effectively promoted by the addition of iron oxide.
The aluminum alloy resulting from the third embodiment has the same industrial applications as the first embodiment.
As an illustration of the fourth invention, the fourth embodiment is now explained.
To obtain the aluminum alloy containing calcium, 10% of the carbide slag mainly composed of CaO, C, CaC2 and others was additionally blended with the material of the Eirst embodiment. The melting reduction was then carried out.
Consequently, the resulting Ca-Al-Si-Fe alloy has the representative components: 41.2% of Al; 36.5% of Si; 1~.8% of Fe; and 5.8% of Ca.
The most effective deoxidizer among the deoxidizers practical in the steel industry is metal calcium, which is used usually as an alloy because it is unsettled if used individually. Calcium-silicon alloy is used as a deoxidizer, and make spherical alumina, hercynite and other high-melting substances resulting from deoxidation. Thus, the calcium-silicon alloy controls the configuration of non-metal inclusion in steel. The alloy resulting from the fourth embodiment can be used as the practical deoxidizer in the steel industry.
Finally, as an illustration of the fifth invention, the fifth embodiment is now explained.
The Al-Si-Fe alloy resulting from the first embodiment i' : , ' . J
' ' ' ' ' ' :~` 2148923 was used. With a crystallizing separator, the aluminum content in the alloy was raised. The lower part of the crystallizing separator is provided with heating and pressure reducing functions and can hold a ladle for receiving the filtered alloy. The upper part of the crystallizing separator has a capacity for receiving the molten metal from the electric furnace. The bottom of the crystallizing separator is formed of the refractory filtering material.
First, the molten alloy of about 900C is poured into the upper container of the crystallizing separator. The pressure of the lower part of the crystallizing separator is reduced to 680mmHg. About 30% of the entire molten alloy is then filtered and flows into the ladle provided in the lower part :
of the separator. The iron content of the filtered alloy is reduced, while the aluminum content thereof is increased.
The molten alloy of lOOOkg resulting from the first embodiment was poured into the crystallizing separator, the pressure in the lower part of the separator was reduced, and 250kg of high-grade Al-Si alloy was obtained. The alloy was composed of 76.5% of Al, 20.3% of Si and 2.4% of Fe. The content of aluminum in the alloy was soared from 43.2% to 76.5%.
Since the aluminum alloy resulting from the fifth embodiment contains much aluminum, the alloy can be used as the mother alloy material for casting.
In the aforementioned embodiments, the invention provides the ultimate recycling of aluminum residuum as industrial wastes. The aluminum residuum of 100 mesh or a smaller size (containing 20% or le.ss of metal aluminum) is regenerated into aluminum alloy. The aluminum alloy resulting from the present invention can be effectively used in the field of iron and steel manufacture. Consequently, the invention brings a decisive advantage for recycling aluminum resources.
The invention is not limited to the aforementioned embodiments. Various modifications car. be put into practice in the range of the scope of the invention.
INDUSTRIAL APPLICABILITY
As detailed in the above, according to the method of the invention, the aluminum alloy can be manufactured by effectively using the aluminum residuum containing a low percentage of metal aluminum, as industrial wastes.
According to the invention, the aluminum residuum disposal cost, which was traditionally burdensome in the aluminum industry, can be reduced. Resources can be effectively used.
Consequently, the ideal recycling system can be realized.
14 :
THE METHOD OF MANUFACTURING ALLOY BY USING ALUMINUM RESIDUUM
TECHNICAL FIELD
The present invention relates to a method of manufacturing alloy by using aluminum residuum.
BACKGROUND OF THE INVENTION
An aluminum alloy is classified roughly into a mass of alloy newly formed by electrolyzing alumina and a mass of alloy recovered from the recycling material. The former alloy is used as plates, cans or other materials, while the latter alloy is used as the material for die casting and molding or as an aluminous deoxidizer in the field of iron and steel manufacture.
Recently, in some countries since the cost of petroleum thermal power or other electric power was increased, the refining of aluminum by means of electrolysis was almost completely abolished. These countries buy aluminum materials from the other countries with low electric power cost incurred, and manufacture only the necessary component alloys~ Even during such manufacture, aluminum including recovered aluminum is melted. At the melting step, generally 3% to 5% of aluminum dross is generated. The aluminum dross usually contains 40% to 60% of metal aluminum. To effectively use aluminum dross, by pulverizing or screening 2148~2~
the dross, high-grade metal aluminum is separated from the dross. The metal aluminum is again melted to recover aluminum. The method for recycling the residuum resulting from the recovery of aluminum, however, was not known.
The aluminum residuum varies in the content of metal aluminum according to their particle sizes. Nowadays the aluminum residuum having the particle size of lmm at maximum and containing the high percentage (30-50%) of metal aluminum are used for the new purpose of desulfurization, deoxidizing and temperature raising. This has been realized by the improved blowing technique in the iron or steel making process.
On the other hand, the aluminum residuum having the particle size of no larger than 100 mesh and containing the low percentage (20% or less) of metal aluminum is only partly used as the slag producing agent alternative for fluorites at the time of iron steel manufacture.
In the present ladle refining (LF) process, however, since the aforementioned aluminum residuum containing the low percentage of metal aluminum contains nitrogen, the application range thereof is narrowly restricted. Therefore, practically most part of such aluminum residuum is not recycled. Not-recycled aluminum residuum is disposed of as industrial wastes. When aluminum nitride (AlN) contained in the industrial wastes comes in contact with water, undesirable ammonia is generated. Because only a few controlled terminal disposal plants are available, the ... . .
2lgL8~23 disposal cost soars and the management of companies is depressed. Thus, the aluminum industry is facing a serious problem.
DISCLOSURE OF INVENTION
The present invention has been developed to solve the aforementioned problem. The object of the invention is to provide a method of manufacturing alloy by using aluminum residuum, particularly a method of manufacturing aluminum alloy by effectively using the industrial wastes of aluminum residuum containing a low percentage of metal aluminum as industrial wastes.
To attain the aforementioned object, in the method of manufacturing alloy by using aluminum residuum according to the first invention, the molded aluminum residuum, a mass of raw material mainly composed of silicon dioxide and a mass of carbon reducing agent are blended and introduced in an electric furnace. Through the melting reducing reaction, an aluminum-silicon alloy is formed.
In the method of manufacturing alloy by using aluminum residuum according to the second invention, aluminum residuum, the raw material mainly composed of silicon dioxide and carbon reducing agent are blended molded and introduced in an electric furnace. Through the melting reducing reaction, an aluminum-silicon alloy is formed.
In the method of manufacturing alloy by using aluminum residuum according to the third invention, iron oxide is .
21~8~23 further added to the blending used in the first or second invention.
In the method of manufacturing alloy by using aluminum residuum according to the fourth invention, by adding carbide slag and/or quicklime to the blending used in the first, second or third invention, an aluminum-silicon-calcium alloy is formed.
In the method of manufacturing alloy by using aluminum residuum according to the fifth invention, the aluminum-silicon alloy resulting from either of the methods of first through third inventions are crystallized, separated and refined, thereby increasing the content of aluminum in the alloy.
Aluminum residuum, the raw material mainly composed of silicon dioxide and the carbon reducing agent in use for the present invention is each molded or massed. Alternatively, these three components are blended and molded. A ma~s or mold is preferred because the melting reducing reaction at high temperatures can be efficiently advanced. The gas generated in the course of reaction can be driven out.
Additionally, generated aluminum, silicon, aluminum-~ilicon or other vaporized metal can be adhered to the surface of the moid for recovery. The size of the mold or mass is not limited: each side of the mold or mass is preferably between 20mm and lOOmm for easy handling. Further, the powdered material is difficult to use, because powder is disper~ed in the flow of air at high temperature when introduced into the 2~8~23 electric furnace.
The aluminum residuum used in the present invention is generated on the surface of molten metal aluminum. The residuum is crushed into powder generally by a ball mill or other adequate device, and the powder is captured by a cyclone or a dust collector. The aluminum residuum generally has a particle size of 100 mesh at maximum and contains 20% or less of metal aluminum.
The raw material mainly composed of silicon dioxide for use in the present invention is, for example, silica rock, silica sand, clay, bentonite or other mineral. The grade of silicon dioxide is preferably 94% at minimum. Particularly, clay, bentonite or other mineral is desirable, because it also serves as a caking agent when molded together with the aluminum residuum and the carbon reducing agent.
The carbon reducing agent used in the present invention can be anthracite, coke or other. When the blending is molded, coke dust or carbon dust can be used.
The reducing reaction of alumina is suppo~ed to proceed in the following reaction mechanism: -2Al203~S)+3C(S) -> Al~04C(melt)+2C0 ......
l/2Al404C(melt)+3C(S) -> l/2Al4C3(S)+2C0 ......
l/2Al4 04 C(melt)+l/2Al4C3(S) -> 4Al(melt)+2C0 ......
The following formula~ is derived from formulas~ and ~ .
: : ,. . . :
21~8~2~
2Al203(S)+6C(S) -> 4Al(melt)+6CO ......
Where silicon dioxide is present, the following formula~
precedes the reaction of formula ~ . According to formula an aluminum-silicon alloy is generated.
SiO2(S)+3C(S) -> SiC(S)+2CO ......
Al4O4C(melt)+3SiC(S) -> 4Al-Si(melt)+4CO ...... ~
In the system of Al203-SiO2-C with iron oxide added thereto (the third invention) iron oxide is reduced at a relatively low temperature. In the alumina reducing step metal iron is present, thereby decreasing the activity of aluminum. Therefore, at the temperature lower by about 100C
than the temperature when the system contains no iron the reaction proceeds as in formula ~ without generating Al4C3.
Al404C(melt)+3C(S) -> 4Al(melt)+4CO ......
In the present invention when the aluminum-silicon alloy rich in aluminum is obtained, aluminum residuum preferably contains 50-60% of Al2 03 and 40-50% of SiO2. If 100 parts of these two materials are existing, 35-40 parts of C as the carbon reducing agent are appropriate. When the alloy rich in silicon is obtained, conversely to the aforementioned ratio, 50-60% of silica and 40-50% of alumina are appropriate.
The carbide slag used in the fourth invention is ' ~
, 6 ~ ;
'' ~ ;
. , ~ . .
-- 21~8~23 composed mainly of calcium oxide, calcium carbide and others, as is generally known.
In the crystallizing separation step carried out in the fifth invention, by filtering the molten alloy, the content of aluminum in the alloy is raised.
The aluminum alloy resulting from the first to ~ourth invention can be used for manufacturing steels, for example As an illustration, the temperature raising agent is used in the LF refining furnace having no electric arc heater. As another illustration, an inexpensive and efficient deoxidizer is used for removing the remaining oxygen from the steel in the electric furnace, when the peroxidizing operation is generally carried out during the steel making process.
The aluminum alloy obtained according to the fifth invention, which contains high percentage of aluminum, can be used as the mother alloy of aluminum for casting.
BEST MODES FOR PRACTICING TH~ INVENTION
The embodiments of the present lnvention are explained below.
The first embodiment is an example of the first invention. 100 mesh or smaller aluminum residuum having the composition of Table 1 is molded into a briquette having a size of 40x 40x 25mm. A mass of silica rock and anthracite have 20 to 50mm long sides and the compositions shown in Table 1, respectively. While the weight percentage of these materials was maintained as Al203 :SiO2 :C=40:33:27, the 2~4892~
materials were continuously fed into the electric furnace for producing carbide. The electric furnace includes three self-baking electrodes having a diameter of 1400mm and has a transformer capacity of 30,000K~A. The electrodes were retained at the embedding depth of about lm, and their temperature was kept between 2200C and 2400C in the electric arc region. On this condition the melting reduction was carried out. After 170 tons of the formed aluminum residuum had been completely fed into the electric furnace, 100 tons of Al-Si-Fe alloy were obtained.
: 21~8~23 <THE CHEMICAL COMPOSITION OF RAW MATERIALS>
ALUMINUM ' SILICA ' ANTHRACITE ' COKE
RESIDUUMUA ' ROCK
_, , , Al2 03 , 75.6 , 1.2 , -- , 3.5 METAL Al ' 10.6 ' 0.0 ' -- ' --SiO2 ' 5.2 ' 94.0 '7.6 ' 7.2 MgO ' 2.3 , 0.6 ' -- , --C ' 0.5 ' -- '76.0 ' 87.7 Fe203 ' 0.6 ' 2.5 '1.5 ' 0.2 .
N ' 3.2 ' -- ' -- ' --CaO ' 0.2 ' 0.5 ' -- ' --.
TiOz ' 0.2 ' Tr ' -- ' --Ig.Loss ' -- , 1.2 ' -- ' 1.0 ASH ' -- , -- ' 12.0 ' --I
(UNIT: WEIGHT %) . ~ . . - , : . ~ .:
- . . - : . . . - . . .
. . . ~: - , ' -~ 48~23 :
The produced metal was composed of 43.2% of Al, 39.2% of Si, 15.2% of Fe, 0.49% of C, less than 0.01% of S, 0.03% of P, 0.02% of N, 0.59% of Ti, 0.5% of Cr, 0.23% of Mn, 0.17% of Ca, 0.11% of Mg and other components (Ni, Zn, Cu, Sn, Pb).
The produced metal contains iron more than expected according to the reaction theory. Because the steel supports (casing material) of electrodes were thermally melted down and lost in the course of the melting reducing reaction.
Also, the steel tapping materials, past which the produced metal was discharged, were also melted into the composition.
The electric power consumption rate was 13,000KWH on average per ton of alloy.
The aluminum alloy resulting from the first embodiment can be used as a temperature raising agent for a converter or for the LF refining furnace having no electric arc heater in the iron and steel industry. In the steel industry in which the electric furnace is used and the peroxidizing operation is general, the aluminum alloy can be used as a deoxidizer for removing the remaining oxygen from steel.
As an illustration of the second invention, the second embodiment is now explained.
Instead of the mass of silica rock used in the aforementioned first embodiment, the silica rock was crushed into ~0 mesh or smaller particles. Instead of the mass of anthracite used in the first embodiment, powdered anthracite waæ used. The weight percentage of raw materials was the same as that in the first embodiment. Pulp waste liquid was - 21~8~23 used as a binder. First, a briquette of aluminum residuum, silica rock and anthracite was obtained. The briquette has a strength of 100kg/cm2 at minimum at normal temperatures and a size of 40x 40x 2~mm. The briquette was inserted into the electric furnace. On the condition same as that in the first embodiment, the melting reduction was carried out. After 160 tons of the briquette in terms of the weight of blended aluminum residuum was completely inserted into the electric furnace, 100 tons of Al-Si-Fe alloy was obtained. The produced metal had almost the same composition as that of the first embodiment. As compared with the first embodiment, the electric power consumption rate was decreased by 1500KWH per ton. Further, the reduction yielding was enhanced.
Therefore, the second embodiment is preferable for the mass production.
The aluminum alloy resulting from the second embodiment has the same industrial applications as the first embodiment.
As an illustration of the third invention, the third embodiment is now explained.
In the third embodiment the briquette was obtained by additionally blending 10% of scales (T-FeO 93.9%) with the blended raw materials of the second embodiment. The briquette was introduced into the electric furnace and the melting reduction was carried out on the same condition as the first embodiment. As compared with the first embodiment, the content of Fe in the produced metal was increased by 5.2%, and the electric power consumption rate was decreased :: , - . ~, . - ~ - - . .
^`" 214~
by 1800KWH per ton. Consequently, the reduction of Al203-SiO2 system was effectively promoted by the addition of iron oxide.
The aluminum alloy resulting from the third embodiment has the same industrial applications as the first embodiment.
As an illustration of the fourth invention, the fourth embodiment is now explained.
To obtain the aluminum alloy containing calcium, 10% of the carbide slag mainly composed of CaO, C, CaC2 and others was additionally blended with the material of the Eirst embodiment. The melting reduction was then carried out.
Consequently, the resulting Ca-Al-Si-Fe alloy has the representative components: 41.2% of Al; 36.5% of Si; 1~.8% of Fe; and 5.8% of Ca.
The most effective deoxidizer among the deoxidizers practical in the steel industry is metal calcium, which is used usually as an alloy because it is unsettled if used individually. Calcium-silicon alloy is used as a deoxidizer, and make spherical alumina, hercynite and other high-melting substances resulting from deoxidation. Thus, the calcium-silicon alloy controls the configuration of non-metal inclusion in steel. The alloy resulting from the fourth embodiment can be used as the practical deoxidizer in the steel industry.
Finally, as an illustration of the fifth invention, the fifth embodiment is now explained.
The Al-Si-Fe alloy resulting from the first embodiment i' : , ' . J
' ' ' ' ' ' :~` 2148923 was used. With a crystallizing separator, the aluminum content in the alloy was raised. The lower part of the crystallizing separator is provided with heating and pressure reducing functions and can hold a ladle for receiving the filtered alloy. The upper part of the crystallizing separator has a capacity for receiving the molten metal from the electric furnace. The bottom of the crystallizing separator is formed of the refractory filtering material.
First, the molten alloy of about 900C is poured into the upper container of the crystallizing separator. The pressure of the lower part of the crystallizing separator is reduced to 680mmHg. About 30% of the entire molten alloy is then filtered and flows into the ladle provided in the lower part :
of the separator. The iron content of the filtered alloy is reduced, while the aluminum content thereof is increased.
The molten alloy of lOOOkg resulting from the first embodiment was poured into the crystallizing separator, the pressure in the lower part of the separator was reduced, and 250kg of high-grade Al-Si alloy was obtained. The alloy was composed of 76.5% of Al, 20.3% of Si and 2.4% of Fe. The content of aluminum in the alloy was soared from 43.2% to 76.5%.
Since the aluminum alloy resulting from the fifth embodiment contains much aluminum, the alloy can be used as the mother alloy material for casting.
In the aforementioned embodiments, the invention provides the ultimate recycling of aluminum residuum as industrial wastes. The aluminum residuum of 100 mesh or a smaller size (containing 20% or le.ss of metal aluminum) is regenerated into aluminum alloy. The aluminum alloy resulting from the present invention can be effectively used in the field of iron and steel manufacture. Consequently, the invention brings a decisive advantage for recycling aluminum resources.
The invention is not limited to the aforementioned embodiments. Various modifications car. be put into practice in the range of the scope of the invention.
INDUSTRIAL APPLICABILITY
As detailed in the above, according to the method of the invention, the aluminum alloy can be manufactured by effectively using the aluminum residuum containing a low percentage of metal aluminum, as industrial wastes.
According to the invention, the aluminum residuum disposal cost, which was traditionally burdensome in the aluminum industry, can be reduced. Resources can be effectively used.
Consequently, the ideal recycling system can be realized.
14 :
Claims (20)
PRELIMINARY EXAMINATION, SUBMISSION DATE OF THE DEMAND JUNE
15, 1994
1. A method of manufacturing alloy for use as deoxidizer for removing the remaining oxygen from the steel or as a temperature raising agent in a converter or a LF refining furnace comprising the steps of:
molding powder of aluminum residuum mainly composed of aluminum oxide and containing 30% or less by weight of aluminum into a desired configuration;
blending said molded aluminum residuum, a mass of raw material mainly composed of silicon dioxide and a mass of carbon reducing agent, thereby obtaining a blending; and introducing said blending into an electric furnace J
reducing aluminum oxide and silicon dioxide through melting reducing reaction, and forming an aluminum-silicon alloy.
molding powder of aluminum residuum mainly composed of aluminum oxide and containing 30% or less by weight of aluminum into a desired configuration;
blending said molded aluminum residuum, a mass of raw material mainly composed of silicon dioxide and a mass of carbon reducing agent, thereby obtaining a blending; and introducing said blending into an electric furnace J
reducing aluminum oxide and silicon dioxide through melting reducing reaction, and forming an aluminum-silicon alloy.
2. A method of manufacturing alloy using aluminum residuum according to claim 1, in which said powder of aluminum residuum is taken from the residuum from which high grade aluminum has been recovered, said residuum resulting from pulverization of aluminum dross made on the surface of molten aluminum.
3. A method of manufacturing alloy using aluminum residuum according to claim 1, in which said molded aluminum residuum, said mass of raw material mainly composed of silicon dioxide and said mass of carbon reducing agent have each side of between 20mm and 100mm.
4. A method of manufacturing alloy using aluminum residuum according to claim 1, in which said blending is composed of 100 parts of a blending containing 40 to 60% by weight of Al2O3 and 60 to 40% by weight of SiO2, and contains 35 to 40 parts of C.
5. A method of manufacturing alloy using aluminum residuum according to claim 1, in which iron oxide is further added to said blending.
6. A method of manufacturing alloy using aluminum residuum according to claim 1, in which by further adding one or two of carbide and quicklime to said blending, an aluminum-silicon-calcium alloy is formed.
7. A method of manufacturing alloy using aluminum residuum according to claim 5, in which by further adding one or two of carbide and quicklime to said blending, an aluminum-silicon-calcium alloy is formed.
8. A method of manufacturing alloy using aluminum residuum according to claim 1, in which by crystallizing, separating and refining the alloy, the content of aluminum in the alloy is increased.
9. A method of manufacturing alloy using aluminum residuum according to claim 5, in which by crystallizing, separating and refining said formed aluminum-silicon alloy, the content of aluminum in the alloy is increased.
10. A method of manufacturing alloy for use as deoxidizer for removing the remaining oxygen from the steel or as a temperature raising agent in a converter or a LF refining furnace comprising the steps of:
blending powder of aluminum residuum containing 30% or less by weight of aluminum, powdered raw material mainly composed of silicon dioxide, powdered carbon reducing agent and organic binder to be molded into a mold having a desired configuration; and introducing said mold into an electric furnace, reducing aluminum oxide and silicon dioxide through melting reducing reaction, and forming an aluminum-silicon alloy.
blending powder of aluminum residuum containing 30% or less by weight of aluminum, powdered raw material mainly composed of silicon dioxide, powdered carbon reducing agent and organic binder to be molded into a mold having a desired configuration; and introducing said mold into an electric furnace, reducing aluminum oxide and silicon dioxide through melting reducing reaction, and forming an aluminum-silicon alloy.
11. A method of manufacturing alloy using aluminum residuum according to claim 10, in which said powder of aluminum residuum is taken from the residuum from which high grade aluminum has been recovered, said residuum resulting from pulverization of aluminum dross made on the surface of molten aluminum.
12. A method of manufacturing alloy using aluminum residuum according to claim 10, in which said mold has each side of between 20mm and 100mm.
13. A method of manufacturing alloy using aluminum residuum according to claim 10, in which said powdered raw material mainly composed of silicon dioxide is at least one raw material selected from the group consisting of clay and bentonite.
14. A method of manufacturing alloy using aluminum residuum according to claim 10, in which said blending is composed of 100 parts of a blending containing 40 to 60% by weight of Al2O3 and 60 to 40% by weight of SiO2, and contains 35 to 40 parts of C.
15. A method of manufacturing alloy using aluminum residuum according to claim 10, in which iron oxide is further added to said blending.
16. A method of manufacturing alloy using aluminum residuum according to claim 10, in which by further adding one or two of carbide and quicklime to said blending, an aluminum-silicon-calcium alloy is formed.
17. A method of manufacturing alloy using aluminum residuum according to claim 15, in which by further adding one or two of carbide and quicklime to said blending, an aluminum-silicon-calcium alloy is formed.
18. A method of manufacturing alloy using aluminum residuum according to claim 10, in which by crystallizing, separating and refining said formed aluminum-silicon alloy, the content of aluminum in the alloy is increased.
19. A method of manufacturing alloy using aluminum residuum according to claim 15, in which by crystallizing, separating and refining said formed aluminum-silicon alloy, the content of aluminum in the alloy is increased.
20. An alloy for use as deoxidizer for removing the remaining oxygen from the steel or as a temperature raising agent in a converter or a LF refining furnace substantially containing:
42 to 48% by weight of aluminum;
37 to 43% by weight of silicon; and 12 to 18% by weight of iron.
42 to 48% by weight of aluminum;
37 to 43% by weight of silicon; and 12 to 18% by weight of iron.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP30546092A JPH06145836A (en) | 1992-11-16 | 1992-11-16 | Production of alloy utilizing aluminum slag |
| JP4-305460 | 1992-11-16 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2148923A1 true CA2148923A1 (en) | 1994-05-26 |
Family
ID=17945416
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA 2148923 Abandoned CA2148923A1 (en) | 1992-11-16 | 1993-11-12 | The method of manufacturing alloy by using aluminum residuum |
Country Status (5)
| Country | Link |
|---|---|
| JP (1) | JPH06145836A (en) |
| CN (1) | CN1088622A (en) |
| CA (1) | CA2148923A1 (en) |
| NO (1) | NO951918L (en) |
| WO (1) | WO1994011540A1 (en) |
Families Citing this family (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1308469C (en) * | 2000-10-19 | 2007-04-04 | 中国科学院福建物质结构研究所 | Comprehensive utilization of waste from aluminium smeltery |
| JP4532974B2 (en) * | 2004-04-26 | 2010-08-25 | 有限会社ダルコ | Processing method of granular aluminum oxide |
| CN101775492B (en) * | 2010-02-26 | 2012-10-31 | 上海海事大学 | Method for producing ferrum-silicon-aluminium alloy by aluminium ashes and copper slag |
| US8900341B2 (en) * | 2010-05-20 | 2014-12-02 | Dow Corning Corporation | Method and system for producing an aluminum—silicon alloy |
| CN102534237B (en) * | 2012-02-22 | 2013-05-01 | 郴州丰越环保科技股份有限公司 | Environment-friendly treatment method for aluminum slag from tin smelting |
| CN103526066B (en) * | 2013-11-01 | 2015-04-29 | 吉林铁合金股份有限公司 | Continuous process for producing manganese-silicon alloy and slag rich in silicomanganese and producing micro-and low-carbon manganese-silicon alloy by utilization of slag rich in silicomanganese |
| TW201518514A (en) * | 2013-11-15 | 2015-05-16 | Yi-Wen Chen | Manufacturing process of aluminum metal from reduction of aluminum slag |
| CN105986121A (en) * | 2015-03-02 | 2016-10-05 | 石嘴山市宝马兴庆特种合金有限公司 | Method for producing multi-component alloy by using hill-skill soil and dust removing micro-powder |
| CN106048241B (en) * | 2016-08-01 | 2018-08-07 | 中冶节能环保有限责任公司 | The method and apparatus that hot aluminium ash metal alum recovery and slag prepare steelmaking ingredient |
| CN109457113B (en) * | 2018-11-02 | 2020-09-04 | 唐山市丰润区明营再生资源有限公司 | Method for cooperatively disposing hazardous waste in metallurgical furnace |
| CN109182733B (en) * | 2018-11-19 | 2020-06-12 | 阳新鹏富矿业有限公司 | Smelting process of magnesium-containing hazardous waste/solid waste |
| CN109338110B (en) * | 2018-11-19 | 2020-06-12 | 阳新鹏富矿业有限公司 | Solid waste/dangerous waste smelting formula using iron agent and smelting method thereof |
| RU2746198C1 (en) * | 2020-04-12 | 2021-04-08 | Акционерное общество "Завод алюминиевых сплавов" | Alumina mixture for liquefaction of metallurgical slag |
| CN111455180B (en) * | 2020-04-17 | 2021-11-23 | 昆明铂锐金属材料有限公司 | Method for enriching platinum and co-producing metal aluminum from spent alumina platinum catalyst |
| CN114772625A (en) * | 2022-04-12 | 2022-07-22 | 四川大学 | Method for dissolving out calcium ions in carbide slag and method for mineralizing and storing CO by using calcium ions in carbide slag2Application of co-produced light calcium carbonate |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4053303A (en) * | 1976-12-06 | 1977-10-11 | Aluminum Company Of America | Method of carbothermically producing aluminum-silicon alloys |
| JPS53123321A (en) * | 1977-04-04 | 1978-10-27 | Hoshino Seiren Kougiyou Kk | Method of producing recovered aluminum alloy ingot |
| JPS5912731B2 (en) * | 1978-10-05 | 1984-03-26 | 株式会社神戸製鋼所 | Method for refining aluminum or aluminum alloy |
| JPS62222034A (en) * | 1986-03-24 | 1987-09-30 | Furukawa Alum Co Ltd | Method for adding ca to aluminum alloy |
-
1992
- 1992-11-16 JP JP30546092A patent/JPH06145836A/en active Pending
-
1993
- 1993-11-12 WO PCT/JP1993/001664 patent/WO1994011540A1/en active Application Filing
- 1993-11-12 CA CA 2148923 patent/CA2148923A1/en not_active Abandoned
- 1993-11-16 CN CN93114678A patent/CN1088622A/en active Pending
-
1995
- 1995-05-15 NO NO951918A patent/NO951918L/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| NO951918L (en) | 1995-07-14 |
| CN1088622A (en) | 1994-06-29 |
| WO1994011540A1 (en) | 1994-05-26 |
| NO951918D0 (en) | 1995-05-15 |
| JPH06145836A (en) | 1994-05-27 |
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