CN1003587B - Method for manufacturing aluminium oxynitride refractory - Google Patents

Method for manufacturing aluminium oxynitride refractory Download PDF

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Publication number
CN1003587B
CN1003587B CN85109343.4A CN85109343A CN1003587B CN 1003587 B CN1003587 B CN 1003587B CN 85109343 A CN85109343 A CN 85109343A CN 1003587 B CN1003587 B CN 1003587B
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CN
China
Prior art keywords
aluminium
aluminum oxide
silica frost
scum silica
refractory
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Expired
Application number
CN85109343.4A
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Chinese (zh)
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CN85109343A (en
Inventor
栗原道
关侃
粟田熙
门胁仁志
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Nikkei Kako KK
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Nikkei Kako KK
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Publication date
Priority claimed from JP59224046A external-priority patent/JPS61106461A/en
Priority claimed from JP60101487A external-priority patent/JPS61261273A/en
Application filed by Nikkei Kako KK filed Critical Nikkei Kako KK
Publication of CN85109343A publication Critical patent/CN85109343A/en
Publication of CN1003587B publication Critical patent/CN1003587B/en
Expired legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/515—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics
    • C04B35/58—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on borides, nitrides, i.e. nitrides, oxynitrides, carbonitrides or oxycarbonitrides or silicides
    • C04B35/581—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on borides, nitrides, i.e. nitrides, oxynitrides, carbonitrides or oxycarbonitrides or silicides based on aluminium nitride
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B21/00—Nitrogen; Compounds thereof
    • C01B21/082—Compounds containing nitrogen and non-metals and optionally metals
    • C01B21/0821—Oxynitrides of metals, boron or silicon
    • C01B21/0825—Aluminium oxynitrides

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Ceramic Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Structural Engineering (AREA)
  • Ceramic Products (AREA)
  • Manufacture And Refinement Of Metals (AREA)
  • Vertical, Hearth, Or Arc Furnaces (AREA)
  • Compositions Of Oxide Ceramics (AREA)

Abstract

An aluminum oxynitride refractory of a sufficiently high nitrogen content is produced efficiently and inexpensively by a method which comprises mixing alumina of Bayer Process with aluminum dross and electrically fusing the resultant mixture in an electric furnace.

Description

The manufacture method of aluminium oxynitride refractory
The present invention relates to the manufacture method of aluminium oxynitride, particularly make raw material, draw the method that required nitride is made aluminium oxynitride refractory with aluminium dross.
Up to the present, people recognize, with the heat-agglomerating micronization the aluminum oxide and the mixture of powdered aluminum oxide, acquisition is with chemical formula mAl 2O 3The aluminium oxynitride of nAlN representative.The aluminium oxynitride of Sheng Chaning shows good fire-resistant, thermotolerance in this way, in melt metal, has outstanding corrosion resistance nature.So, wish to find a kind of refractory materials that extensive practicality is arranged, particularly be used in the reducing atmosphere.
As mentioned above, under the agglomerating condition,, can obtain aluminium oxynitride by the mixture of heated oxide aluminium powder and aluminum nitride powder.The cost of gained refractory materials inevitably can be very expensive in this way.This is because the raw alumina of this special required usefulness of sintering method must be ground into very thin particle, and its particle diameter is not more than several microns.Therefore, aluminum oxide is very expensive as the raw material of aluminium oxynitride.
So, recommended additive method, these methods are as the raw material of producing aluminium oxynitride refractory with Bayer method gained aluminum oxide.The aluminum oxide of Bayer method industrial be scale operation, thereby can cheap obtain.Clear and the 53(1978 in Japanese patent laid-open publication gazette) disclose a kind of method in-14,247 specification sheetss, this method is to get the aluminum oxide of Bayer method and make it to use electrofusion in nitrogen atmosphere, thereby realizes nitrogenize in the electrofuse aluminum oxide.Yet, in this way, can not obtain the high refractory materials of nitrogen content, because be difficult to be implemented in the infiltration of the nitrogen of sufficient quantity in the aluminum oxide.
Clear and the 52(1977 in Japanese patent laid-open publication gazette) in-50,040 specification sheetss, the preparation method of nitrogenous alumina refractory is disclosed.This method comprises that the aluminum oxide with Bayer method gained mixes with metallic aluminium powder, in nitrogen containing atmosphere (clean atmosphere is interior), and the mixture of electrofuse gained.The disclosed method of this specification sheets mainly is in aluminum oxide, mixes metallic aluminium powder in advance, makes aluminium powder be transformed into aluminium nitride and the mixture of aluminium nitride is mixed in the fused aluminum oxide by oxidizing reaction.This method is clear and 53(1978 than Japanese patent laid-open publication gazette)-14,247 produce the refractory materials of suitable high nitrogen-containing easily.However, also there is following shortcoming in this method.
Or rather, clear and the 52(1977 of Japanese patent laid-open publication gazette)-50, disclosed method comprises aluminum oxide and the metallic aluminium powder uniform mixing that the Bayer method gets in 040 specification sheets, and the mixture of the electrofuse gained that in nitrogen containing atmosphere, (comprises clean atmosphere), metallic aluminium powder is mixed in the aluminum oxide, be converted into aluminium nitride, and aluminium nitride is mixed in the fused aluminum oxide.Reaction method when making nitrogen containing atmosphere with air mixes metallic aluminium powder in the aluminum oxide by nitrogenize.Meanwhile, most metallic aluminium powder and airborne nitrogen effect and oxidized.So this method has shortcoming, promptly used metallic aluminium powder does not effectively utilize in this process, its result, and between difference product in batches, nitrogen content is not easy stdn.In order to eliminate above-mentioned shortcoming, guarantee that metallic aluminium powder effectively utilizes aborning, so the electric furnace of dress aluminum oxide is in hermetic closed state fully in must keeping, and require in stove, to be full of under the situation of nitrogen, carry out the electric furnace melting operation.Like this, become complicated, cost of equipment of operation becomes very high.
Consider above-mentioned practical situation, the inventor makes raw material with the aluminum oxide that the Bayer method obtains, and at going out aluminium oxynitride than the more effectively cheap lot production of usual way, has constantly carried out big quantity research, notices this fact finally.So-called aluminium dross is produced resulting residue from aluminium metallurgy factory or molten aluminium manufacturer exactly, and it contains a large amount of Al 2O 3Microparticle, these Al 2O 3Microparticle is fused aluminium autoxidation and producing.In addition, also have direct and Al 2O 3The nitrogen component of microparticle blended AlN form.Thereby find that the aluminum oxide that obtains from the Bayer method mixes with this scum silica frost, in the electric furnace identical with common melt oxidation aluminium production process, the mixture of fusion gained.AlN component in the scum silica frost and as the Al of the main component in the scum silica frost 2O 3Microparticle by heating, is an agglutinating mutually, and the adhesive composite of gained mixes soon from the fused alumina that the Bayer method gets and goes, with the nitrogen content of raising high-alumina.According to above situation, the present invention has dropped into production.
Specifically, the object of the invention is to provide the production method of aluminium oxynitride refractory, it is characterized in that mixing with aluminium dross with the aluminum oxide of Bayer method gained, and in electric furnace the mixture of fusion gained.
As mentioned above, the invention belongs to the manufacture method of aluminium oxynitride refractory.This method is to make raw material with the aluminum oxide of Bayer method, and this aluminum oxide and aluminium dross are mixed, and the mixture of electrofuse gained, thereby goes in the aluminum oxide that nitrogen is mixed melt.
As for the source of used aluminum oxide in the inventive method, can adopt the commercially available aluminum oxide that passes through the non-modified of Bayer method generation.
As the aluminium dross of the source usefulness of nitrogen, be to reclaim the residue that stays after the metallic aluminium component.This component exists at most in the scum silica frost of aluminium metallurgy factory or the production of molten aluminium manufacturer.The scum silica frost overwhelming majority is the Al that the molten aluminum autoxidation generates 2O 3Micropartical in addition, also contains the nitrogen component, this component, with above-mentioned Al 2O 3The tight blended AlN of micropartical form exists, and sticky metals aluminium composition is as residue on it.Listed the composition of typical aluminium dross below.
The typical case of table 1 aluminium dross forms
Al 2O 3The AlN metallic aluminium other
60～80% 5～15% 5～15% surplus
In the methods of the invention, the aluminum oxide of aluminium dross and Bayer method mixes, then, and with the mixture electrothermal melting.In this case, the mixture ratio of scum silica frost and aluminum oxide can suitably be fixed, and can consider to be determined by the last nitrogen content of scum silica frost nitrogen content and fused refractory.Because a kind of waste material that aluminium dross generates when being aforementioned aluminium fusion, but it does not have fixed to form, thus the nitrogen content of scum silica frost from a collection of to another batch, in AlN, roughly in 5～15% scopes, change.
In the method for the invention, be selected as the aluminium dross of nitrogen-containing material, nitrogen content is lower, and the refractory materials that makes wishes that high nitrogen content is arranged, so, with the amount of Bayer method aluminum oxide blended scum silica frost must be sufficiently big, when used aluminium dross was so big as previously mentioned, following possibility will take place.That is, during the electrofuse mixture, fine grain aluminium dross will be disperseed and be lost greatly.Simultaneously, the impurity of bringing into owing to aluminium dross will be easy to enter the purity that the refractory materials that makes influences product.
When the aluminium dross nitrogen content of selecting for use is low, when the aluminum oxide that makes wishes to have quite high nitrogen content, require aluminium dross to carry out nitriding treatment in advance, to obtain giving fixed sufficiently high nitrogen content.For example, the scum silica frost nitrogenize can be carried out like this, that is, scum silica frost is put in the container of alumina refractory, makes it heat about 600～700 ℃ in the atmosphere of nitrogen.By heating, the metallic aluminium that remains in the scum silica frost begins nitrogenize, and this reaction further improves the temperature of reaction system, thereby the metallic aluminium in the scum silica frost is converted into AlN fully.As a result, the nitrogen content of scum silica frost increases.
When used scum silica frost containing metal aluminium is low, or wish aluminium oxynitride refractory when extra high nitrogen content is arranged, can before the aluminium dross nitrogenize, add proper metal aluminium in the aluminium slag, like this, just can improve the nitrogen content of refractory materials.In this case, the easy degree that the nitriding of aluminium dross reaction is proceeded down reduces and increases proportionally along with being added in the aluminium dross particulate of metallic aluminium.Even so, the metallic aluminium that adds does not so often need very thin.It can be tiny particle, thin slice, or slag in small, broken bits etc.If the metallic aluminium that is added in the aluminium dross is too big, because its heating and melting and sintering, possible nitrogenize is interfered, and metallic aluminium still exists in the residue of nitrogenizing reaction with former state.So the amount that is added to the metallic aluminium in the aluminium dross should be no more than 50%(weight).
The aluminum oxide of electrofuse Bayer method and the mixture of unmodified aluminium dross, or electrofuse Bayer method Al 2O 3Al with above-mentioned nitriding treatment 2O 3Mixture.Electrofuse can be used carbon dioxide process carbon electrode, carries out in the alternating current arc environment.For example, very as conventional melt oxidation aluminium production process.Since this electrofuse effect, AlN component in the scum silica frost and the major ingredient Al in the scum silica frost 2O 3Bond each other between fine particle.The gained adhesive composite mixes in the fused Bayer method aluminum oxide and goes, to improve the nitrogen content of fused alumina.
The melt substance that obtains at last, direct casting, thus produce casting refractory.In addition, melt substance also can be frozen into solid; Be ground into suitable granularity then, as the filler component of making sintered refractory and casting refractory.
As previously mentioned, main points of the present invention are that making the aluminium dross of the cheap a large amount of aluminum oxide that obtain of Bayer method and aluminium metallurgy factory and the molten aluminum production of molten aluminium manufacturer is raw material, produces aluminium oxynitride refractory.So raw material is cheap.The fusion of aluminum oxide and aluminium dross mixture does not need the clear and 52(1977 as Japanese patent laid-open publication gazette) on-10040 specification sheetss disclosed, carry out in the electric furnace under airtight nitrogen atmosphere.But, in air atmosphere, carry out effectively as common fused alumina production.Advantage of the present invention is that equipment cost is low, and processing ease is realized, and can be born the fused refractory of a large amount of high nitrogen-containings.
Now, more clearly set forth the present invention with following working example.
Embodiment 1
Preparation is by the aluminium dross (analytical results: Al of 100 parts of weights 2O 375%, AlN13.5%, metallic aluminium 6%) and the mixture formed of the Bayer method aluminum oxide of 50 parts of weights.At rated output is in the three-phase alternating current electric arc smelting furnace of 30KVA, under 75 volts and 200 amperes, and the about 20 kilograms mixture of fusion two hours.Thereby obtain the aluminium oxynitride ingot casting that weight is about 19 grams.
Pulverize and analyze this ingot casting, find that its averaged nitrogen content is about 3.1%.
Embodiment 2
Preparation is as the mixture of the Bayer method aluminum oxide of 100 parts of example 1 heavy aluminium dross and 100 parts of weights, in the electric arc smelting furnace identical with example 1, and the about 20 kilograms of mixtures of fusion 2 hours, thus obtain about 19 kilograms aluminium oxynitride ingot casting.
Find that by analysis its averaged nitrogen content of this ingot casting is about 2.4%.
Embodiment 3
Aluminium dross (analytical results: Al 2O 370%, AlN6%, metallic aluminium 11%) put into the container of the refractory materials that contains high-alumina, the gas of receptacle imports nitrogen replacement downwards by the top.In the nitrogen atmosphere that generates, heated aluminium dross about 20 minutes with stove, carry out nitriding treatment, the analytical results of gained nitrogenize scum silica frost sees Table 2.
Table 2
Al 2O 3The AlN metallic aluminium
68% 21% -
Preparation contains the 100 parts heavy Bayer method aluminum oxide and the above-mentioned nitride scum silica frost of 80 parts of weights, is in the electric arc smelting furnace of three-phase alternating current of 30KVA at rated output, under 75 volts and 200 amperes, and about 2 hours of 20 kilograms of said mixtures of fusion.Thereby obtain about 19 kilograms aluminum oxynitride ingot casting.
Grinding is also analyzed this ingot casting, finds that its averaged nitrogen content is 3.2%.
Embodiment 4
The aluminium dross that 100 parts of heavy examples 3 are used and metal aluminum strip (about 4mm of 20 parts of weights 2) thorough mixing, the mixture of gained is put in the airtight alumina refractory container to heat with stove and was carried out nitriding treatment in about 30 minutes.
The analytical results of nitrogenize scum silica frost sees Table 3
Al 2O 3The AlN metallic aluminium
54% 37% -
Preparation contains the above-mentioned nitride dross mixture of 100 parts heavy Bayer method aluminum oxide and 40 parts of weights.According to the method for embodiment 3,, thereby obtain the aluminium oxynitride ingot casting of about 19 kiloponds to about 2 hours of gained mixture fusions in electric smelter of 20 kilograms.
Analyze this ingot casting and find that averaged nitrogen content is about 3.9%.

Claims (8)

1, the production method of aluminium oxynitride refractory is characterized in that the aluminum oxide that obtained by the Baycr method and contains the AIN aluminium dross and mix, and in electric furnace the mixture of electric smelting gained.
2, according to the process of claim 1 wherein described scum silica frost before mixing with described aluminum oxide and melting, must be in nitrogen-containing atmosphere through heating.
3, according to the method for claim 2, wherein the content of free aluminum replenishes by adding extra metallic aluminium in described scum silica frost.
4, according to the method for claim 2, wherein said protective atmosphere Heating temperature is 600～700 ℃.
5, according to the method for claim 2, wherein the metallic aluminium that contains in the scum silica frost is AIN by described thermal conversion.
6, according to the process of claim 1 wherein that described heating carries out in electric arc.
7, according to the process of claim 1 wherein the mixture ratio of aluminum oxide of scum silica frost and Bayer method, with the amount that contains AIN in the scum silica frost with final fusion refractory materials in the content of AIN determine.
8, according to the process of claim 1 wherein that described electrofuse carries out in protective atmosphere.
CN85109343.4A 1984-10-26 1985-10-26 Method for manufacturing aluminium oxynitride refractory Expired CN1003587B (en)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
JP224046/84 1984-10-26
JP59224046A JPS61106461A (en) 1984-10-26 1984-10-26 Manufacture of aluminum oxynitride refractories
JP60101487A JPS61261273A (en) 1985-05-15 1985-05-15 Manufacture of aluminum oxonitride refractories
JP101487/85 1985-05-15

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CN85109343A CN85109343A (en) 1986-05-10
CN1003587B true CN1003587B (en) 1989-03-15

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AU (1) AU565630B2 (en)
BR (1) BR8505356A (en)
DE (1) DE3538044A1 (en)
FR (1) FR2572393B1 (en)

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5132246A (en) * 1990-01-22 1992-07-21 Alcan International Limited Process for using dross residues to produce refractory products
DE4330955A1 (en) * 1993-09-09 1995-03-16 Reetz Teja Prof Dr Rer Nat Hab Refractory material for the thermal insulation of high-temperature furnaces having a non-oxidising heat-treatment atmosphere
DE4420450C2 (en) * 1994-06-10 1996-05-15 Thermoselect Ag Coolable delivery for a high-temperature gasification reactor
CN110684916A (en) * 2019-10-08 2020-01-14 徐州鑫博金属制品有限公司 Environment-friendly aluminum alloy refractory material and preparation method thereof
TWI769913B (en) * 2021-08-24 2022-07-01 財團法人工業技術研究院 Ceramic composite and method of preparing the same

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3274009A (en) * 1966-09-20 Refractory composition
US2480475A (en) * 1946-03-12 1949-08-30 Reynolds Metals Co Refractory
JPS5250040B2 (en) * 1974-04-22 1977-12-21
JPS58135112A (en) * 1982-02-03 1983-08-11 Toshiba Corp Production of aluminum oxynitride
JPH05250040A (en) * 1992-03-06 1993-09-28 Fujitsu Ltd Pulse train generating circuit
JPH05314247A (en) * 1992-05-12 1993-11-26 Fujitsu Ltd Image data processor

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AU4909685A (en) 1986-05-01
AU565630B2 (en) 1987-09-24
DE3538044A1 (en) 1986-04-30
CN85109343A (en) 1986-05-10
BR8505356A (en) 1986-08-05
FR2572393B1 (en) 1988-10-28
FR2572393A1 (en) 1986-05-02
DE3538044C2 (en) 1989-03-16

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