TW201210968A - Refractory block and glass furnace - Google Patents
Refractory block and glass furnace Download PDFInfo
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- TW201210968A TW201210968A TW100121693A TW100121693A TW201210968A TW 201210968 A TW201210968 A TW 201210968A TW 100121693 A TW100121693 A TW 100121693A TW 100121693 A TW100121693 A TW 100121693A TW 201210968 A TW201210968 A TW 201210968A
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- 239000011521 glass Substances 0.000 title claims description 22
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims abstract description 30
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 24
- KKCBUQHMOMHUOY-UHFFFAOYSA-N Na2O Inorganic materials [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 claims abstract description 22
- 229910052681 coesite Inorganic materials 0.000 claims abstract description 18
- 229910052906 cristobalite Inorganic materials 0.000 claims abstract description 18
- 229910052682 stishovite Inorganic materials 0.000 claims abstract description 18
- 229910052905 tridymite Inorganic materials 0.000 claims abstract description 18
- 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 14
- 239000000203 mixture Substances 0.000 claims abstract description 12
- 239000000126 substance Substances 0.000 claims abstract description 11
- JKWMSGQKBLHBQQ-UHFFFAOYSA-N diboron trioxide Chemical compound O=BOB=O JKWMSGQKBLHBQQ-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 5
- 235000012239 silicon dioxide Nutrition 0.000 claims abstract description 5
- 238000002844 melting Methods 0.000 claims description 9
- 230000008018 melting Effects 0.000 claims description 9
- 229910000420 cerium oxide Inorganic materials 0.000 claims description 6
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 claims description 6
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 4
- 229910052902 vermiculite Inorganic materials 0.000 claims description 4
- 239000010455 vermiculite Substances 0.000 claims description 4
- 235000019354 vermiculite Nutrition 0.000 claims description 4
- 210000000078 claw Anatomy 0.000 claims 1
- 229910052593 corundum Inorganic materials 0.000 abstract description 7
- 229910001845 yogo sapphire Inorganic materials 0.000 abstract description 7
- 230000000295 complement effect Effects 0.000 abstract 1
- 239000000047 product Substances 0.000 description 32
- 239000000463 material Substances 0.000 description 9
- 230000007797 corrosion Effects 0.000 description 7
- 238000005260 corrosion Methods 0.000 description 7
- 239000012535 impurity Substances 0.000 description 7
- 238000004519 manufacturing process Methods 0.000 description 7
- 239000000155 melt Substances 0.000 description 7
- 238000000034 method Methods 0.000 description 7
- 238000001816 cooling Methods 0.000 description 5
- 239000013078 crystal Substances 0.000 description 5
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- 230000001590 oxidative effect Effects 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 239000000292 calcium oxide Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000010891 electric arc Methods 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000000740 bleeding effect Effects 0.000 description 2
- 229910052810 boron oxide Inorganic materials 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(iv) oxide Chemical compound O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 229910052684 Cerium Inorganic materials 0.000 description 1
- 101100348017 Drosophila melanogaster Nazo gene Proteins 0.000 description 1
- 101000690503 Homo sapiens Protein argonaute-3 Proteins 0.000 description 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 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 102100026791 Protein argonaute-3 Human genes 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- 102100031083 Uteroglobin Human genes 0.000 description 1
- 108090000203 Uteroglobin Proteins 0.000 description 1
- 238000000137 annealing Methods 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- XFWJKVMFIVXPKK-UHFFFAOYSA-N calcium;oxido(oxo)alumane Chemical compound [Ca+2].[O-][Al]=O.[O-][Al]=O XFWJKVMFIVXPKK-UHFFFAOYSA-N 0.000 description 1
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000001627 detrimental effect Effects 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 230000009970 fire resistant effect Effects 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000010309 melting process Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910001950 potassium oxide Inorganic materials 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000012265 solid product Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
Classifications
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- 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
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
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- 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
- C04B35/107—Refractories by fusion casting
- C04B35/109—Refractories by fusion casting containing zirconium oxide or zircon (ZrSiO4)
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- 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
- C04B35/48—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 zirconium or hafnium oxides, zirconates, zircon or hafnates
- C04B35/484—Refractories by fusion casting
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- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
- C04B2235/3201—Alkali metal oxides or oxide-forming salts thereof
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- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
- C04B2235/3205—Alkaline earth oxides or oxide forming salts thereof, e.g. beryllium oxide
- C04B2235/3208—Calcium oxide or oxide-forming salts thereof, e.g. lime
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- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
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- C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
- C04B2235/3217—Aluminum oxide or oxide forming salts thereof, e.g. bauxite, alpha-alumina
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- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
- C04B2235/3224—Rare earth oxide or oxide forming salts thereof, e.g. scandium oxide
- C04B2235/3225—Yttrium oxide or oxide-forming salts thereof
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- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
- C04B2235/3231—Refractory metal oxides, their mixed metal oxides, or oxide-forming salts thereof
- C04B2235/3244—Zirconium oxides, zirconates, hafnium oxides, hafnates, or oxide-forming salts thereof
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- C04B2235/34—Non-metal oxides, non-metal mixed oxides, or salts thereof that form the non-metal oxides upon heating, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
- C04B2235/3409—Boron oxide, borates, boric acids, or oxide forming salts thereof, e.g. borax
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- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/34—Non-metal oxides, non-metal mixed oxides, or salts thereof that form the non-metal oxides upon heating, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
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Description
201210968 六、發明說明: 【發明所屬之技術領域】 本發明係關於一種熔融AZS(礬土 ·氧化鍅-矽石)耐火製 品° 【先前技術】 在耐火製品之中,已區別熟知用於構成玻璃熔爐的熔融 製品及燒結製品》 不同於燒結製品,熔融製品通常包含結合結晶顆粒之晶 粒間的玻化相。因此,由燒結製品及熔融製品所產生的問 題及解決問題所採取的技術方法一般係不同的。因而,為 製造燒結製品所發展之組合物基本上不能用於製造熔融製 品,反之亦然。 熔融製品(經常稱為電熔製品)係藉由在電弧爐中熔化適 當批次材料之混合物或藉由任何其他適合用於該類製品的 技術而獲得。然後,熔料在模子中鑄造且所獲得之產物經 歷一控制冷卻循環》 在熔融製品之中,主要包括礬土(Al2〇3)、氧化锆(Zr〇2) 及矽石(Si〇2)之AZS電熔製品已為人所知數十年。專利us_ A-2 438 552描述首次對這類製品所做之一種改良。作者建 議添加Na2〇 (1-2.2%)及Mg〇/Ca〇 (〇2〇8%)以解決包括小 於70。/。Αία”從14至4〇% Zr〇2及從9至12% si〇2之產品相 關可行性之問題。 EP 0 939 065 B1建議藉由添加b2〇3、p2〇5及至少一種選 自Sn02、ZnO、CuC^Mn〇2之群的氧化物減少包含2〇至 156974.doc 201210968 59%氧化锆之AZS製品的滲出程度。添加慣用起始材料中 不以雜質存在之該類氧化物導致生產成本過高並可能帶來 著色的問題。 FR 2 875 497建議藉由選擇化學分析使得Zr〇2: 15.5至 * 22%,Si02: 10.5 至 15%及 Na20+K20+Li20: 1.0至 2.5%,尤 • 其Α1203/Ζγ02重量比等於或高於2.9,及如果Si02/ (NazO+KzO+LbO)重量比高於7及/或小於9來減少AZS製品 之滲出程度。 法國申請案FR 08 58914或申請案WO 2010/073 195建議 藉由添加Y203而使化學分析之Zr02: 30至46%,Si02: 10至 16%及Na2〇+K20: 〇_5至5%來改良抗腐姓性。 在所有根據此等申請案之發明的實例中(實例4至10), Si02/(Na20+K20+B203)<5*Y203。相反地,除實例 η 之 外,沒有一個滿足標準 Si02/(Na20+K20+B203)25*Y203 之 實例符合該類申請案之發明。 如今由Saint-Gobain SEFPRO所出售之AZS製品,比如 ER-1681、ER-1685 及 ER-1711 包含 45 至 50% Al2〇3,32 至 41〇/〇 Zr02,12至 16% Si02及約 1% Na20。ER-2001 SLX 包含 , 約 68% Al2〇3, 17% Zr02, 13% Si02及 1.7% Na20。 . 該類製品係適合用於製造玻璃熔爐。更特定言之,當前 可購得之AZS製品主要係用於與玻璃熔料接觸的區域及用 於玻璃熔爐之上部構造中。 儘管此等製品係有效的,但始終需改良控制玻璃熔爐及 玻璃品量的條件。 156974.doc 201210968 特定言之,對於組成玻璃熔爐容器之AZS熔融製品塊, 重要的是限定工作溫度下之滲出問題。 因此’需要一種具有優良抗玻璃熔料腐蝕性及在工作溫 度下不會發生任何玻璃熔爐容器滲出問題的AZS熔融製 品。 本發明的目的在於滿足該需要。 【發明内容】 更特疋s之,本發明係關於一種包括下列化學組成之溶 融对火製品,以下組成係以基於氧化物之重量百分比表示 且總共為100% :
Zr02: 30-50% ;
Si02: 8-16% ; A1203: 1〇〇〇/0 之餘額; Y2O3之50/ΖγΟ2及 y2〇3s5〇/0 ;
Na20+K20+B2〇3>〇.2〇/〇A Si02/(Na20+K20+B203)>5*Y203 ;
CaO: <0.5% ; 其他氧化物種類:$ 1 5%。 如下文更加詳細的敘述般,此製品具有優良的抗玻璃熔 料腐蝕性及在工作溫度下不會發生任何玻璃熔爐容器滲出 的問題。 根據本發明之製品可以進一步具有下列可選特性中之一 或多個: -ΖΓ〇232% ’ 或 Zr〇235%,及 / 或 Zr〇<45%,或 Ζγ〇2<42% ; 156974.doc 201210968 -Si022l〇%,或 Si〇2>ll%及/或81〇2$150/〇; -A12〇b>38% » 或 Al2〇3之40% 及 / 或 A12〇3S52°/〇 ’ 或 A12〇3<50°/〇 ; -Y2〇3含量高於60/ZrO2,或高於70/ZrO2 ; -Y2O3含量等於或高於1.2%,或等於或高於1.5°/。,或等 於或高於2.0%,或等於或高於2.5%,或等於戒高於 2.7% ; -Y2〇3含量低於或等於4.5%,或低於或等於4.0% ; -Na20+K20+B203含量高於0.3%,高於0.4%,或高於 0.5°/。及/或低於4.0°/。,低於3.0%,低於2.5%,低於 2.0%,低於1.5%,或低於1.2%,或低於1.1%,或低於 1.0%,低於0.9%,低於 0.8% ; -Na20含量高於〇.3。/0,高於0.4%,或高於0.5%,及/或 低於4.0%,低於3.0%,低於2.5%,低於2.0%,低於 1.5% ’或低於1 _2。/0,或低於1 1 %,或低於1 〇%,低於 0.9%,低於 0.8% ; _ Si02/Na20重量比高於5.3*y2〇3,或高於5 5*γ2〇3,或 南於 5.7*Y203,或高於 6*γ2〇3; -SiOVNkO重量比高於u,或高於12,或高於13,或高 於14,或高於15 ; 其他氧化物種類"為雜質; -製品呈塊狀。 在一較佳實施例中:
Zr02:32-45% ;及 156974.doc 201210968
SiO2:10-15% ;及 Al2〇3:40-5〇% ;及 Υ2〇3:2·2-4.〇〇/0 ;及 Na2O:0.4-l ,2% 〇 本發明進步係關於一種製造根據本發明之耐火製品的 方法,其包括下列連續步驟: a) 混合批次材料以形成起始批次, b) 將該起始批次熔化直到獲得一熔料, c) 經控制冷卻,將該熔料鑄造並固化以獲得熔融耐火製 品,該方法之特徵在於選擇該批次材料,以便使該熔融 耐火製品具有與根據本發明製品一致的組成。 本發明進一步係關於一種玻璃熔爐,其包括根據本發明 之製品,特定言之係藉由本發明方法製造或可製造的產 °°尤其係在该製品容易與玻璃熔料或玻璃融化釋放的氣 體接觸之熔爐區域中,及特定言之在上部構造(爐冠)中。 【實施方式】 定義 一般言之,術語「熔融製品」、「熔融及鑄造產品」或 「經熔化獲得」意指經由冷卻熔料完全固化而獲得之視需 要經退火的固態產物。「熔料」係為保持其形狀必須限定 在谷器中之物質。表觀上為液體之熔料可包含固體部分, 但其量不足以構成該物質。 根據本發明之製品可包含自然存在於氧化銼源中之二氧 化铪Hf〇2。其在根據本發明製品中之重量含量為低於或等 156974.doc 201210968 於二,-般低於或等於2%。「Zr〇2」通常意指氧化結及 彼等从量之二氧化給。Hf〇2因此未包括在「其他氧化物種 類」内。 雜質」意指必定會隨批次材料引入或由與該類組分反 應而引起之不可避免的組分。特定言之,已知鐵及欽之氧 Γ?有害且其含量必須限制於隨批次材料作為雜質引入的 微置較佳而各,Fe2〇3+Ti〇2之重量含量係小於U%。 在包括組分之重量百分比之間之比率(無單爛如 2〇+K2〇+B2〇3))及另一組分之含量(以重量百分比 的式中’該關係純粹為數學性以約束組成 σ二的式了樣適用於包括含量的倒數(5。卿 除非另有朗,㈣本文敘述巾 化物之重量百分比。 $百刀比為基於氧 詳細說明 造根據本發明之製品可藉由遵循如下所述步驟〇至〇)而製 a) 混合批次㈣以形成起始批次, b) 將該起始批切化直到獲得熔料, 以獲得根據本發明 c) 經由控制冷卻將該溶料鑄造並固化 之耐火製品。 明在步叫中,決定批次材料以保證成品之組成符合本發 氧化紀必需存在於本發明之製品中,但其含量不能超過 J56974.doc 201210968 5% ’否則有降低可行性的風險。 專於或尚於50/Zr〇2之Y2〇3含量對獲得優良的抗玻璃溶 料腐触性是必要的。 納及/或鉀及/或氧化硼之存在對賦予玻化相適當物理及 化學性質是必要的。然而,Na2〇+K2〇+B2〇3含量不能超過 使得Si02/(Na20+K20+B203)》5*Y2〇3之值,否則在玻璃熔 爐的工作溫度下,玻化相容易在製品表面上流動,從而損 失其黏性及其抗腐蝕性《在一個實施例中,Κ2〇及/或 僅以雜質形式存在。 氧化鈣存在於本發明之製品中為有害的,因為其容易在 玻化相中產生鋁酸鈣晶體。該類晶體之存在可能致使製品 破裂。此外’極高Ca◦含量可導致氧化結晶體溶解,降低 製品之抗腐蝕性。因此,CaO含量不可超過〇.5%。 在步驟b)中,熔化較佳係藉由相當長電弧之組合作用實 施,其不會導致還原及促進製品再次氧化之混合。 為將具有金屬外觀之節結的形成減至最小及為預防最故 產品中形成***或裂縫,以在氧化條件下進行熔化為佳。 較佳係使用描述在法國專利i 2〇8 577及其增補案7测 及823 10中之長弧炼化製程。 該方法在於則-在進料及與該進料分離之至少叫I 極之間向上射入電弧之電弧爐及調節電弧長度以使其¥ 作用減至最小,同時藉由電弧本身的作用,或藉由向, ,入氧化氣體(例如空氣或氧氣),乃至藉由朝炫料添力, 虱釋放物質(比如^氧化物)混合該熔肖,以在熔料上2 156974.doc •10· 201210968 持一氧化氛圍。 在步驟中C)中,溶料較佳係在適合用於製造模塊之模子 中鑄造。冷卻較佳係在每小時約lot之下降溫度速率下進 行0 如果起始批次之組合物可以用來獲得與根據本發明之製 品一致之組成的產品,就可以使用任何用於製造待應用於 玻璃熔爐中之AZS熔融製品的慣用方法。 根據本發明之製品可以全部或部份由模塊組成。 特定言之,模塊可以具有超過10公斤、超過2〇公斤,或 甚至多於50公斤、多於150公斤、多於3〇〇公斤或甚至多 於900公斤及/或小於2噸的質量。特定言之,其可以具^ 約1噸的質量。 八 模塊的形狀無限定。 模塊可具有至少15〇毫米、較佳至少2〇〇毫米,或甚至至 少400毫米、或甚至至少600毫米,或甚至至少8〇〇毫来、 或甚至至少1000毫米,或甚至至少16〇〇毫米之至少一維 (厚度、長度或寬度)^ 在-有利的實施例中,模塊之厚度、長度及寬度至少 150毫米,或甚至至少200毫米、或甚至至少3〇〇毫米或 甚至至少400毫米。 狀 亦可使用呈薄製品形式,換言之具有5〇及15〇毫米之間 :厚度、特定言之低於120毫米之厚度,或甚至低於1〇〇毫 :、之厚度之根據本發明製品。特定言之,其可以呈平板 156974.doc 201210968 較佳而言’模塊或平板形成部份或構成熔爐,尤其係玻 璃熔爐之爐壁或爐膛。 實例 提供下列非限制性實例以說明本發明。 在該類實例中,已經使用下列批次材料: -經Soci0t6 Europ0enne des Produits R0fractaires出售之氧 化結CC10,其按重量計平均主要包含98 5% Zr〇2、〇 5% Si02及 0.2% Na20, -包含33%矽石之結砂, -經Pechiney出售及平均包含99·4% ΑΙΑ3之類型从料的 礬土, -包含58.5% Na20之碳酸納, -具有純度超過99°/。之氧化釔。 產品係藉由慣用電弧爐熔化製程所製成,然後鑄造以獲 得規格為200x400x150立方釐米的模塊。 表1列出所獲得製品的化學分析;這是平均化學分析, 以重量百分比提供。實例9進一步包括2.1重量%之氧化硼 (1〇3);礬土 AGO3及構成100%之餘額的雜質。對於其他 實例’礬土 Al2〇3及雜質構成1〇0%之餘額。 滲出抗性之評估(測試A) 製成模塊之樣本係採用具有100釐米之長度及24釐米之 直徑的圓柱體狀,然後加熱至1550。(:。藉由相機觀察樣本 之行為並記錄相當於玻化相在樣本表面上之起始流動的溫 度。此溫度係以。C列於表1中。 156974.doc •12- 201210968 表1
與實例1至3比較’本發明之實例4至7清楚地表示Si〇2及 (Na2〇+B2〇3)之間之重量比的作用。事實上,當該比率升 至超過5倍之氧化釔含量時,玻化相於樣本表面上起始流 動之溫度顯著地增加。 比較實例8與實例1〇、實例丨〗或實例4顯示當該比率低於 5倍之氧化釔含量時,該溫度下降。 比較實例9與實例7或實例6亦說明該比率對該溫度的影 響〇 實例1在測試A中顯示令人非常滿意的溫度,但低於本發 明製品之抗腐触性。 明顯而S,轉明不限於以說明性及非限制性實例所描 述及提供之實施例。 特定言之’根據本發明之製品不限於特定的形狀或尺 寸’也不限於玻璃熔爐之應用。 156974.doc -13·
Claims (1)
- 201210968 七、申請專利範圍: 1. 一種包括下列化學組成之熔融耐火製品,以下組成係以 基於氧化物之重量百分比表示且總共為100% : ZrO2:30-50% ; , Si02:8-16% ; , ai2o3:ioo% 之餘額; Y2O3250/ZrO2及 Y2〇3S5〇/〇 ; Na2O+K2O+B2O3》0.2%及Si02/(Na20+K20+B203)>5*Y203 ; CaO:<0.5% ; 其他氧化物種類:SI .5%。 2. 如先前請求項之製品,其中該氧化釔含量係高於比率 60/ZrO2 。 3 ·如先則請求項中任一項之製品,其中該氧化記含量係高 於比率70/Zr〇2。 4. 如先前請求項中任一項之製品,其中鹼性氧化物之總含 量 Na20+K20+B203係低於 1.5%。 5. 如請求項4之製品,其中鹼性氧化物之總含量 Na20+K20+B2〇3係低於} 1〇/〇。 • 6.如先前請求項中任一項之製品,其中8102爪&20上5.5*丫2〇3。 ,7·如先前請求項中任一項之製品,其中Si02/Na20之重量比 率係高於12。 8.如先刖5青求項中任一項之製品,其中氧化鍅含量係高於 32%及/或矽石含量係高於1〇%及/或礬土含量係高於38% 及/或氧化釔含量係高於2.0%及/或鹼性氧化物之總含量 I56974.doc 201210968 Na20+K20+B203係高於 0.3%。 9_如先前請求項中任一項之製品,其中氧化锆含量係低於 45%及/或矽石含量係低於15%及/或礬土含量係低於52〇/〇 及/或氧化纪含量係低於4 · 5 %及/或驗性氧化物之含量 Na20+K20+B2〇3係低於 ι .20/〇。 1 0.如先前請求項中任一項之製品,其中 Zr〇2:32-45% ;及 Si〇2:l〇-15% ;及 A12〇3:40-5〇〇/〇 ;及 Υ203:2·2-4·〇〇/〇 ;及 Na2O:0.4-1.2%。 11.如先前請求項中任一項之劁0 盆 ή心取σσ,具係呈具有超過丨〇 kg質 量的塊狀。 12· 一種^㈣爐’其包括如先前請求項中任-項之製品。 13·如先月j -月求項之熔爐’其中該製品係置於易於與玻璃熔 料或玻璃熔化所釋放之氣體接觸的熔爐區域中。 156974.doc 201210968 四、 指定代表圖: (一) 本案指定代表圖為:(無) (二) 本代表圖之元件符號簡單說明: 五、 本案若有化學式時,請揭示最能顯示發明特徵的化學式: (無) 156974.doc
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WO2016068111A1 (ja) * | 2014-10-31 | 2016-05-06 | 旭硝子株式会社 | アルミナ・ジルコニア・シリカ質溶融鋳造耐火物、ガラス溶融窯、およびガラス板の製造方法 |
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EP3453689B1 (en) * | 2017-09-08 | 2020-08-26 | AGC Ceramics Co., Ltd. | High-zirconia electrocast refractory and method for manufacturing the same |
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FR1208577A (fr) | 1958-07-07 | 1960-02-24 | Electro Refractaire | Perfectionnements à la fabrication de produits réfractaires électrofondus contenant des oxydes minéraux |
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US20130125593A1 (en) | 2013-05-23 |
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FR2961506A1 (fr) | 2011-12-23 |
EA024833B1 (ru) | 2016-10-31 |
CN103097311B (zh) | 2015-07-01 |
CN103097311A (zh) | 2013-05-08 |
BR112012032338A2 (pt) | 2016-11-08 |
WO2011161588A1 (fr) | 2011-12-29 |
EP2582637A1 (fr) | 2013-04-24 |
EA201291337A1 (ru) | 2013-05-30 |
JP5782118B2 (ja) | 2015-09-24 |
BR112012032338B1 (pt) | 2019-11-19 |
US9233867B2 (en) | 2016-01-12 |
JP2013534895A (ja) | 2013-09-09 |
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