CN85109343A - The manufacture method of aluminium oxynitride refractory - Google Patents
The manufacture method of aluminium oxynitride refractory Download PDFInfo
- Publication number
- CN85109343A CN85109343A CN85109343.4A CN85109343A CN85109343A CN 85109343 A CN85109343 A CN 85109343A CN 85109343 A CN85109343 A CN 85109343A CN 85109343 A CN85109343 A CN 85109343A
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- CN
- China
- Prior art keywords
- aluminium
- aluminum oxide
- refractory
- dross
- mixture
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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
Abstract
The aluminum oxide of Bayer method mixes with aluminium dross, and the method for molten mixture in electric furnace is produced the cheap sufficiently high aluminium oxynitride refractory of nitrogen content efficiently.
Description
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
3, the nAIN representative aluminium oxynitride.The aluminium oxynitride of Sheng Chaning in this way shows good fire-resistant, thermotolerance, 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, be very expensive with aluminium oxynitride as raw material.
So, recommended additive method, these methods are as the raw material of producing aluminium oxynitride refractory with Bayer method gained aluminum oxide.The Bayer method industrial be scale operation, thereby can cheap obtain.Clear and the 53(1978 at the Japanese patent specification publication) disclose a kind of method in-14,247, this method is to get the aluminum oxide of Bayer method, and electricity consumption makes it fusing, or in nitrogen atmosphere, with this aluminum oxide of electrofusion, thereby realizes the infiltration of nitrogen.Yet, in this way, can not obtain the high refractory materials of nitrogen content, because infiltrating, high nitrogen-containing is difficult to realize.
Clear and the 52(1977 in Japanese patent specification) in-50,040, the preparation method of nitrogenous alumina refractory is disclosed.This method is by the aluminum oxide of Bayer method gained and mixing of metallic aluminium powder, (includes clean atmosphere) in nitrogen containing atmosphere, the mixture of electrofuse gained.The disclosed method of this specification sheets, mainly be in the electrofuse alumina process, mix metal powder in advance, and be seeped in the aluminum oxide that will transform and go, by the nitriding reaction, become aluminium nitride and the mixture of aluminum oxide is mixed in the fused aluminum oxide.This method is clear and 53(1978 than Japanese patent specification publication)-14,247 produce the refractory materials of suitable high nitrogen-containing easily.However, also there is following shortcoming in this method.
Or rather, the clear and 52(1977 of Japanese Patent Publication) disclosed method in-50,040 specification sheetss comprises aluminum oxide and metallic aluminium powder uniform mixing that the Bayer method gets, and (includes clean atmosphere) in nitrogen containing atmosphere, the mixture of electrofuse gained.Therefore, 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, the metallic aluminium powder that mixes in the aluminum oxide is oxidized.Meanwhile, Da Bufen metallic aluminium powder and airborne oxygen effect and oxidized.So this method has shortcoming.That is, in this process, metallic aluminium powder does not effectively utilize, its result, and between difference product in batches, nitrogen content is not easy stdn.In order to eliminate above-mentioned shortcoming, guarantee effective utilization of metallic aluminium powder, 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 aluminum oxynitride than the more effectively cheap lot production of usual way, has constantly carried out big quantity research, and they notice 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 AIN 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.AIN 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 aluminum oxide.According to above understanding, the present invention has dropped into production.
Specifically, this production method that is to provide aluminium oxynitride refractory of the present invention 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, the aluminum oxide of the non-modified that the Bayer method of having bought on the market generates.
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 exhausted major part of scum silica frost 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 AIN 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 AIN 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 AIN, 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 the scum silica frost of Bayer method aluminum oxide must be sufficiently big, when used aluminium dross was so big as described above, 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, requires aluminium dross to carry out nitriding in advance and handle, to obtain giving fixed sufficiently high nitrogen content.For example, the nitriding of scum silica frost can be carried out like this, that is, scum silica frost is put in the container of alumina refractory, makes it be heated to about 600～700 ℃ in the atmosphere of nitrogen.By heating, the metallic aluminium that remains in the scum silica frost begins nitriding, and this reaction further improves the temperature of reaction system, thereby the metallic aluminium in the scum silica frost is converted into AIN 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 nitriding, 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 (fine garanules), thin slice (fine foil Strips), or slag in small, broken bits (fine Chips) etc.If the metallic aluminium that is added in the aluminium dross is too big, because its heating and melting and sintering may make nitriding be interfered, metallic aluminium still exists in the residue of nitriding 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 osmotic treated
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, AIN 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 can direct pouring Cheng Mo, thereby produces casting refractory.In addition, melt substance also can be frozen into solid; Be ground into suitable granularity then, as making the grain sample component that sintered refractory and casting refractory are used.
As previously mentioned, main points of the present invention are that the aluminium dross that cheap a large amount of aluminum oxide that obtain of Bayer method and aluminium metallurgy factory and molten aluminium manufacturer molten aluminum are generated is a raw material, produce 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 the Japanese patent specification publication) on-50040 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 illustrate 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%, AIN13.5%, 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 kilograms.
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 1100 parts of heavy aluminium dross of example 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 24%.
Embodiment 3
Aluminium dross (analytical results: Al
2O
370%, AIN6%, 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, make to produce the nitriding processing, the analytical results of gained nitrogenize scum silica frost sees Table 2.
Table 2
Al
2O
3The AIN metallic aluminium
68% 21% -
Preparation contains the 100 parts heavy Bayer method aluminum oxide and the above-mentioned oxide compound 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 aluminium 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 carries out handling as the nitriding of embodiment 3 in nitrogen atmosphere.
The analytical results of nitrogenize scum silica frost sees Table 3
Al
2O
3The AIN metallic aluminium
54% 37% -
Preparation contains the mixture of the above-mentioned nitride scum silica frost 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 (1)
- The production method of aluminium oxynitride refractory is characterized in that mixing the mixture of fusion gained with the aluminum oxide scum silica frost.
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 |
| JP101487/85 | 1985-05-15 | ||
| JP60101487A JPS61261273A (en) | 1985-05-15 | 1985-05-15 | Manufacture of aluminum oxonitride refractories |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN85109343A true CN85109343A (en) | 1986-05-10 |
| CN1003587B CN1003587B (en) | 1989-03-15 |
Family
ID=26442359
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN85109343.4A Expired CN1003587B (en) | 1984-10-26 | 1985-10-26 | Method for manufacturing aluminium oxynitride refractory |
Country Status (5)
| Country | Link |
|---|---|
| CN (1) | CN1003587B (en) |
| AU (1) | AU565630B2 (en) |
| BR (1) | BR8505356A (en) |
| DE (1) | DE3538044A1 (en) |
| FR (1) | FR2572393B1 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN115894044A (en) * | 2021-08-24 | 2023-04-04 | 财团法人工业技术研究院 | Ceramic composite and method for preparing same |
Families Citing this family (3)
| 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 |
Family Cites Families (6)
| 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 |
-
1985
- 1985-10-25 BR BR8505356A patent/BR8505356A/en not_active IP Right Cessation
- 1985-10-25 AU AU49096/85A patent/AU565630B2/en not_active Ceased
- 1985-10-25 FR FR8516007A patent/FR2572393B1/en not_active Expired
- 1985-10-25 DE DE19853538044 patent/DE3538044A1/en active Granted
- 1985-10-26 CN CN85109343.4A patent/CN1003587B/en not_active Expired
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN115894044A (en) * | 2021-08-24 | 2023-04-04 | 财团法人工业技术研究院 | Ceramic composite and method for preparing same |
Also Published As
| Publication number | Publication date |
|---|---|
| BR8505356A (en) | 1986-08-05 |
| AU4909685A (en) | 1986-05-01 |
| AU565630B2 (en) | 1987-09-24 |
| FR2572393B1 (en) | 1988-10-28 |
| DE3538044C2 (en) | 1989-03-16 |
| FR2572393A1 (en) | 1986-05-02 |
| CN1003587B (en) | 1989-03-15 |
| DE3538044A1 (en) | 1986-04-30 |
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