GB2147287A - Alkali-resistant refractory compositions - Google Patents
Alkali-resistant refractory compositions Download PDFInfo
- Publication number
- GB2147287A GB2147287A GB08423318A GB8423318A GB2147287A GB 2147287 A GB2147287 A GB 2147287A GB 08423318 A GB08423318 A GB 08423318A GB 8423318 A GB8423318 A GB 8423318A GB 2147287 A GB2147287 A GB 2147287A
- Authority
- GB
- United Kingdom
- Prior art keywords
- refractory
- silica
- alumina
- zirconia
- present
- 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.)
- Granted
Links
- 239000000203 mixture Substances 0.000 title claims abstract description 22
- 239000003513 alkali Substances 0.000 title claims description 12
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 29
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims abstract description 24
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000011521 glass Substances 0.000 claims abstract description 15
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 14
- 229910052845 zircon Inorganic materials 0.000 claims abstract description 9
- GFQYVLUOOAAOGM-UHFFFAOYSA-N zirconium(iv) silicate Chemical compound [Zr+4].[O-][Si]([O-])([O-])[O-] GFQYVLUOOAAOGM-UHFFFAOYSA-N 0.000 claims abstract description 9
- 238000004519 manufacturing process Methods 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- 238000000034 method Methods 0.000 claims 5
- 239000003792 electrolyte Substances 0.000 claims 1
- 238000000465 moulding Methods 0.000 claims 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 abstract description 4
- 239000011734 sodium Substances 0.000 abstract description 4
- 229910052708 sodium Inorganic materials 0.000 abstract description 4
- 229910000503 Na-aluminosilicate Inorganic materials 0.000 abstract description 3
- 229910000323 aluminium silicate Inorganic materials 0.000 abstract description 3
- 235000012217 sodium aluminium silicate Nutrition 0.000 abstract description 3
- 239000011819 refractory material Substances 0.000 description 13
- KZHJGOXRZJKJNY-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Si]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O KZHJGOXRZJKJNY-UHFFFAOYSA-N 0.000 description 8
- 229910052863 mullite Inorganic materials 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 6
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 4
- INJRKJPEYSAMPD-UHFFFAOYSA-N aluminum;silicic acid;hydrate Chemical compound O.[Al].[Al].O[Si](O)(O)O INJRKJPEYSAMPD-UHFFFAOYSA-N 0.000 description 3
- 229910052850 kyanite Inorganic materials 0.000 description 3
- 239000010443 kyanite Substances 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000005356 container glass Substances 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 239000012530 fluid Substances 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 239000002893 slag Substances 0.000 description 2
- 238000004901 spalling Methods 0.000 description 2
- 239000005995 Aluminium silicate Substances 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 229910052570 clay Inorganic materials 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000001627 detrimental effect Effects 0.000 description 1
- 230000009429 distress Effects 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000006060 molten glass Substances 0.000 description 1
- 239000011505 plaster Substances 0.000 description 1
- 229920000867 polyelectrolyte Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000000979 retarding effect Effects 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 229910002076 stabilized zirconia Inorganic materials 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
- C03B5/00—Melting in furnaces; Furnaces so far as specially adapted for glass manufacture
- C03B5/16—Special features of the melting process; Auxiliary means specially adapted for glass-melting furnaces
- C03B5/42—Details of construction of furnace walls, e.g. to prevent corrosion; Use of materials for furnace walls
- C03B5/43—Use of materials for furnace walls, e.g. fire-bricks
-
- 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
- C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
- C04B35/10—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on aluminium oxide
- C04B35/101—Refractories from grain sized mixtures
- C04B35/106—Refractories from grain sized mixtures containing zirconium oxide or zircon (ZrSiO4)
Abstract
A refractory composition particularly useful in constructing glass furnaces is based primarily on silica (16-20%), alumina (67-75%), and zirconia (14-20%), wherein the silica content is primarily tied up in zircon. As a result of the silica content being bound in zirconia, less silica is available to form alumino-silicates which have a tendency to react with sodium vapors to form sodium alumino-silicates, which, during furnace operation, causes the refractory to spall or flake off. The composition can be formed using inorganic bubbles having reduced weight and, accordingly, is particularly advantageous in forehearth superstructures of glass furnaces.
Description
SPECIFICATION
Alkali-resistant refractory compositions
The present invention relates to the manufacture of refractories which are resistant to attack by sodium vapors. More particularly, the invention is directed to the manufacture of refractories useful in glass furnaces and, because of the ability to form the refractories in a form having reduced weight, highly advantageous in forehearths and superstructures of glass furnaces.
Refractories useful in glass furnaces which are highly resistant to thermal shock and to corrosion by molten glass have been described in U.S. Patent No. 3,437,499, issued April 8, 1969, and assigned to the assignee of the present invention. The '499 patent describes the use of a mixture composed of zircon, stabilized zirconia, alumina, mullite, clay, and calcined kyanite in water. The mixture is molded and then sintered at a temperature below the decomposition temperature of zircon. It has been found that the aforesaid refractory compositions are not completely satisfactory as refractories in certain furnaces due to their tendency to spall because of the mullite component. In such glass furnaces (for example, those where alkali vapors are formed) the mullite is unstable in the presence of alkali vapors.Moreover, conventional mullite refractories are also unsatisfactory in such furnaces.
The distress of conventional mullite refractories used in a glass furnace was determined to be the result of (1 ) rapid temperature change, and (2) mineralogical alteration of the mullite structure due to the presence of alkalis at elevated temperatures. Alkali vapors cause decomposition of the mullite, resulting in the formation of compounds which, because of accompanying volume changes, are detrimental to service life, primarily as a result of spalling or flaking off of the refractory. The volume change has been found to be as high as 4.5% under optimum conditions. The volume change has been found to take place at approximately 2200 to 2300OF. or lower, depending upon ambient conditions within the range of temperature changes that normally occur in container glass furnaces.The rate of reaction may vary depending upon the physical characteristics of the refractory, i.e., density, porosity, pore structure, and the like.
A primary object of the present invention is to provide a refractory which can be produced by conventional methods and can be used in high alkali vapor conditions such as those found in industrial operations utilizing and/or producing slags and glasses containing compounds of sodium, potassium, calcium, magnesium, and boron.
Another object of the present invention is to provide complex refractory shapes such as those useful in glass furnace forehearth and/or superstructures having reduced weight.
These and other objects of the present invention will be more apparent from the following disclosure and working embodiment. According to the present invention, a refractory is provided comprising as essential components silica (SiO2), alumina (Al203), and zirconia (ZrO2) with traces of other components such as titania (TiO2) and iron (Fe203). Compositions formulated in accordance with the present invention provide refractories which have good resistance to attack by alkali vapors, such as sodium and potassium vapors, normally associated with the manufacture of glass in a glass furnace.It is theorized that the high resistance to alkali vapors at the conditions of industrial operations utilizing and/or producing slags and glasses is a result of having substantially all of the silica present in the formulation tied up or bound in the zircon which limits the availability of silica available to form sodium alumino-silicates, which, it has been found, at temperatures of certain furnace operations, are accompanied by large volume changes. By reducing the reaction of silica to form the sodium alumino-silicates it was possible to reduce the tendency of the reaction layer of the refractory to spall or flake off especially when the furnace of a part thereof, such as a glass furnace forehearth, is cooled down and then heated to operating temperatures.
Accordingly, the present invention eliminates mullite as the major component and eliminates other components (such as free silica) from the formulation in percentages which will form alumino-silicates, thereby preventing the reaction of the refractory with alkali vapors and, thus, eliminating the slabbing off or spalling problem associated with the reaction of mullite-type refractories with alkali vapors. The alumina-zirconia-silica bond of the refractories of the present invention will reach equilibrium and/or stabilization during furnace operation, retarding further reaction of the alkalis with the refractory due to the absence of extensive alumino-silicates found in mullite-type or mullite-bonded refractories.
The chemical composition and analysis of the alumina-zirconia-silica refractories of the present invention are as follows:
Materials Operable Range
Ball Clay or Kaolin 0- 6%
Ultrox 2 microns Wet Milled (Zircon)
Zircopex A 2 microns Wet Milled (Zircon) 15 - 25%
Calcined Alumina - 325 Mesh 20 - 30%
Calcined Kyanite - 35 Mesh 0 - 23%
Tabular Alumina - 14 Mesh 0 - 25%
Fused Alumina Bubbles - 4 Mesh & Finer 30 - 40%
ChemicalAnalysis Operable Range
Silica (SlO2) 10-16% Alumina (AI203 67-75% Zirconia (ZrO2) 14-20% Other Oxides 1 - 2%
The compositions of the present invention can be formed into refractories utilizing conventional techniques.The compositions can be employed as dense powders, flakes, or they can be formed using inorganic refractory bubbles. Utilization of bubbles permits the formation of lightweight refractory structures having particular application in lightweight super-structures for container glass forehearths. Alternatively, however, the structures can be utilized with advantage in any refractory where alkali vapors are likely to be present.
Example
A refractory having the composition
Materials
Ball Clay or Koalin 4.0%
Ultrox 2 microns Wet Milled (Zircon) 6.5%
Zircopax A 2 microns Wet Milled (Zircon) 13.3%
Calcined Alumina - 325 Mesh 21.5%
Calcined Kyanite - 35 Mesh 22.7%
Tabular Alumina - 14 Mesh 0% Fused Alumina Bubbles - 4 Mesh & Finer 32.0%
ChemicalAnalysis
Silica (SiO2) 15.9% Alumina (Al203 68.3%
Zirconia (ZrO2) 15.7%
Other Oxides 0.8% was placed in a paddle mixer and blended at a low mixer speed. A polyelectrolyte and water was added to the dry mix, and mixing continued to form a semi-fluid mass. The semi-fluid mass, after thorough mixing, was placed in a plaster mold and air dried after removal from the mold. The molded refractory was then heated at about 220 F. to remove remaining water and thereafter fired to approximately 2600"F. at a controlled cycle for, for example, fifteen (15) to twenty-six (26) hours to produce a ceramic bond. The refractory so used can be utilized in a conventional manner as a refractory in a glass furnace.
As will be apparent to one skilled in the art, various modifications can be made within the scope of the aforesaid description. Such modifications being within the ability of one skilled in the art form a part of the present invention and are embraced by the appended claims.
Claims (12)
1. The method of making a refractory which is resistant to alkali vapors comprising: forming a mixture comprising as essential components silica 10-16%, alumina 67-75%, and zirconia 14-20%, said silica being essentially tied up in zircon; forming said mixture into a moldable mass; and molding said mass into a shaped refractory.
2. The method of claim 1 wherein said moldable mass includes an electrolyte and water.
3. The method of claim 2 wherein at least one of the essential components is in the form of inorganic bubbles.
4. The method of either of claims 2 or 3 wherein said alumina is at least partially in the form of bubbles.
5. The method of any one of claims 1 to 4 wherein said refractory is shaped to form at least a part of the superstructure of a glass furnace forehearth.
6. A method of making a refractory substantially as hereinbefore described and illustrated by the foregoing example.
7. A refractory composition consisting essentially of silica (SiO2) 10-16%, alumina (awl203) 67-75%, zirconia (ZrO2) 14-20%, and other oxides 0-2%.
8. The refractory of claim 7 wherein said silica is present at 15.9%, said alumina is present at 68.3%, and said zirconia is present at 15.7%.
9. The refractory composition of either of claims 7 or 8, with said composition being partially in the form of inorganic bubbles.
10. A refractory composition substantially as hereinbefore described and illustrated by the foregoing
Example.
11. A refractory composition when produced by a method in accordance with any one of claim 1 to 6.
12. An article formed from a refractory composition according to any one of claims 7 to 11.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US53750683A | 1983-09-30 | 1983-09-30 |
Publications (3)
| Publication Number | Publication Date |
|---|---|
| GB8423318D0 GB8423318D0 (en) | 1984-10-17 |
| GB2147287A true GB2147287A (en) | 1985-05-09 |
| GB2147287B GB2147287B (en) | 1987-03-11 |
Family
ID=24142932
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| GB08423318A Expired GB2147287B (en) | 1983-09-30 | 1984-09-14 | Alkali-resistant refractory compositions |
Country Status (6)
| Country | Link |
|---|---|
| JP (1) | JPS6090867A (en) |
| AU (1) | AU574720B2 (en) |
| DE (1) | DE3435002A1 (en) |
| FR (1) | FR2552756A1 (en) |
| GB (1) | GB2147287B (en) |
| IT (1) | IT1181220B (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2859203A1 (en) * | 2003-09-01 | 2005-03-04 | Saint Gobain Ct Recherches | RAW PIECE FOR THE MANUFACTURE OF A FRITTE REFRACTORY PRODUCT WITH IMPROVED BULLAGE BEHAVIOR |
| US20090062106A1 (en) * | 2003-09-01 | 2009-03-05 | Saint-Gobain Centre De Recherches Et D ' Etudes Europeen | Hollow piece for producing a sintered refractory product exhibiting improved bubbling behaviour |
| US7943541B2 (en) | 2005-09-26 | 2011-05-17 | Saint Gobain Centre De Recherches Et D'etudes Europeen | Sintered refractory product exhibiting enhanced thermal shock resistance |
| US20150158770A1 (en) * | 2012-08-24 | 2015-06-11 | Refractory Intellectual Property Gmbh & Co. Kg | Fused cast refractory material based on aluminium oxide, zirconium dioxide and silicon dioxide, and use of such a material |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6350364A (en) * | 1986-08-20 | 1988-03-03 | 株式会社神戸製鋼所 | High slag resistance alumina brick |
| DE4031467C1 (en) * | 1990-10-05 | 1992-01-02 | Dyko Industriekeramik Gmbh, 4000 Duesseldorf, De |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3437499A (en) * | 1966-03-04 | 1969-04-08 | Emhart Corp | Glass contact refractory and method of making the same |
| US4045233A (en) * | 1975-12-10 | 1977-08-30 | N L Industries, Inc. | Refractory composition and method for preparation |
| US4117055A (en) * | 1977-09-20 | 1978-09-26 | The Babcock & Wilcox Company | Low mass, high alumina-silica refractories |
| BE859264A (en) * | 1977-09-30 | 1978-01-16 | Inst Nat Interuniversitaire De | MANUFACTURING PROCESS OF NEW REFRACTORY PRODUCTS |
-
1984
- 1984-09-14 GB GB08423318A patent/GB2147287B/en not_active Expired
- 1984-09-18 IT IT83417/84A patent/IT1181220B/en active
- 1984-09-24 DE DE19843435002 patent/DE3435002A1/en not_active Withdrawn
- 1984-09-27 FR FR8414830A patent/FR2552756A1/en not_active Withdrawn
- 1984-09-28 JP JP59203893A patent/JPS6090867A/en active Pending
- 1984-09-28 AU AU33686/84A patent/AU574720B2/en not_active Ceased
Non-Patent Citations (1)
| Title |
|---|
| NONE * |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2859203A1 (en) * | 2003-09-01 | 2005-03-04 | Saint Gobain Ct Recherches | RAW PIECE FOR THE MANUFACTURE OF A FRITTE REFRACTORY PRODUCT WITH IMPROVED BULLAGE BEHAVIOR |
| WO2005023726A1 (en) * | 2003-09-01 | 2005-03-17 | Saint-Gobain Centre De Recherches Et D'etudes Europeen | Hollow piece for producing a sintered refractory product exhibiting improved bubbling behaviour |
| US20090062106A1 (en) * | 2003-09-01 | 2009-03-05 | Saint-Gobain Centre De Recherches Et D ' Etudes Europeen | Hollow piece for producing a sintered refractory product exhibiting improved bubbling behaviour |
| CN1835897B (en) * | 2003-09-01 | 2011-05-18 | 圣戈班欧洲设计研究中心 | Blank for manufacturing sintered refractory product with improved foaming performance |
| US8187990B2 (en) | 2003-09-01 | 2012-05-29 | Saint-Gobain Centre De Recherches Et D'etudes Europeen | Hollow piece for producing a sintered refractory product exhibiting improved bubbling behaviour |
| US7943541B2 (en) | 2005-09-26 | 2011-05-17 | Saint Gobain Centre De Recherches Et D'etudes Europeen | Sintered refractory product exhibiting enhanced thermal shock resistance |
| US20150158770A1 (en) * | 2012-08-24 | 2015-06-11 | Refractory Intellectual Property Gmbh & Co. Kg | Fused cast refractory material based on aluminium oxide, zirconium dioxide and silicon dioxide, and use of such a material |
| US10000417B2 (en) * | 2012-08-24 | 2018-06-19 | Refel S.P.A. | Fused cast refractory material based on aluminium oxide, zirconium dioxide and silicon dioxide, and use of such a material |
Also Published As
| Publication number | Publication date |
|---|---|
| AU574720B2 (en) | 1988-07-14 |
| FR2552756A1 (en) | 1985-04-05 |
| GB2147287B (en) | 1987-03-11 |
| IT8483417A0 (en) | 1984-09-18 |
| JPS6090867A (en) | 1985-05-22 |
| GB8423318D0 (en) | 1984-10-17 |
| IT1181220B (en) | 1987-09-23 |
| DE3435002A1 (en) | 1985-04-25 |
| AU3368684A (en) | 1985-04-04 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PCNP | Patent ceased through non-payment of renewal fee |