TWI532703B - Blast furnace with castable refractory - Google Patents

Blast furnace with castable refractory Download PDF

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TWI532703B
TWI532703B TW103104701A TW103104701A TWI532703B TW I532703 B TWI532703 B TW I532703B TW 103104701 A TW103104701 A TW 103104701A TW 103104701 A TW103104701 A TW 103104701A TW I532703 B TWI532703 B TW I532703B
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blast furnace
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Kazuaki Haraguchi
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Krosakiharima Corp
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    • C21C5/00—Manufacture of carbon-steel, e.g. plain mild steel, medium carbon steel or cast steel or stainless steel
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    • C21C5/4653—Tapholes; Opening or plugging thereof
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
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    • F27B1/00—Shaft or like vertical or substantially vertical furnaces
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Description

高爐槽用可鑄性耐火物
本發明係有關於作為高爐槽之內襯使用的可鑄性耐火物。
高爐槽係具有使從高爐出爐的銑鐵到達澆桶、混鐵車等的通路的作用。其內襯材料，由加工性方面而言係使用可鑄性耐火物，其材質係以氧化鋁-碳化矽-碳質為主流。
在此種高爐槽用可鑄性耐火物中，添加碳化硼(B4C)作為抗氧化劑之技術已廣為人知(例如參照專利文獻1)。碳化硼藉由氧化，在耐火材料的表面形成被膜，且該被膜係具有防止碳材料氧化之機能。
此外，專利文獻2揭露，若併用B4C與氧化鋁微粉及氧化矽超微粉時，生成自B4C的B2O3與Al2O3及SiO2反應，使固溶有莫來石(3Al2O3．2SiO2)的9Al2O3．2B2O3(以下稱為「9A2B」)之柱狀結晶與基質部或空隙交纏而析出。由於9A2B在基質部或空隙析出，使材料之孔隙率大幅下降，同時高溫的熱強度提升，茲認為 可改善對爐渣或銑鐵的耐蝕性、耐磨耗性。
[先前技術文獻]
[專利文獻]
[專利文獻1]日本特開2000-203953號公報
[專利文獻2]日本特開平3-164479號公報
如專利文獻1所記載，B4C藉由氧化生成被膜(B2O3)，而發揮作為表面氧化保護膜之機能。另一方面，B2O3透過與可鑄性耐火物中的Al2O3進行反應，形成Al2O3與B2O3的固溶體(9A2B)。然，若形成此固溶體(9A2B)，則作為表面氧化保護膜的B2O3被消耗，導致表面氧化保護機能降低。表面氧化保護機能一降低，可鑄性耐火物的內部成分即暴露於氧化環境下，由此碳材料的氧化、及B2O3與Al2O3的反應同時進行發生，使得氧化層進一步深入至內部。
再者，在專利文獻2，其認為藉由9A2B的析出，耐蝕性、耐摩耗性獲得改善，但因9A2B為緻密的燒結體，生成9A2B時加工體的強度增加，與未氧化的完整組織之間便產生強度差。如此一來，成為因此強度差而容易引起龜裂剝離之組織劣化的加工體。尤其是在高爐槽的 爐渣管線部，因高爐作業而反覆加熱冷卻，由於反覆之熱歷程所產生的結構體變化及此時之熱衝擊而容易發生龜裂剝離。
鑒於以上所述，本發明所欲解決之課題在於提供一種不會使B4C所產生的抗氧化機能降低，且亦可防止加工體之龜裂剝離發生的高爐槽用可鑄性耐火物。
根據本發明一觀點，提供一種高爐槽用可鑄性耐火物，其係含有：40質量%以上且80質量%以下之SiC成分、10質量%以上且40質量%以下之粒徑45μm以上之原料所含的Al2O3成分、0.3質量%以上且3.0質量%以下之B4C成分，且粒徑未達45μm之原料所含的Al2O3成分之含量為6.9質量%以下。
本發明中，由於係將高爐槽用可鑄性耐火物之化學成分的總量100質量%中，粒徑未達45μm之原料所含的Al2O3成分之含量限制為6.9質量%以下，因此，可抑制源自B4C成分的B2O3與Al2O3反應生成9A2B。亦即，由於不容易使B2O3與Al2O3反應而被消耗，故不會使B4C所產生的抗氧化機能降低，可抑制9A2B的生成，因此，亦可防止加工體之龜裂剝離發生。
本發明高爐槽用可鑄性耐火物典型上為以氧化鋁原料、碳化矽原料及碳原料為主原料且進一步摻混有碳化硼(B4C)原料的氧化鋁-碳化矽-碳質，並對其添加分散劑及結合劑而成。而且，作為其化學成分，係含有：40質量%以上且80質量%以下之SiC成分、10質量%以上且40質量%以下之粒徑45μm以上之原料所含的Al2O3成分、0.3質量%以上且3.0質量%以下之B4C成分，且粒徑未達45μm之原料所含的Al2O3成分之含量為6.9質量%以下。粒徑未達45μm之原料所含的Al2O3成分之含量較佳為3.9質量%以下，B4C成分之含量較佳為0.3質量%以上且1.5質量%以下。此外，氧化鋁-碳化矽-碳質中亦含有自由之C成分，惟其含量為1~10質量%左右。
本發明高爐槽用可鑄性耐火物之特徵在於，將作為其化學成分的粒徑未達45μm之原料所含的Al2O3成分之含量限定為6.9質量%以下。該粒徑未達45μm之原料所含的Al2O3成分之含量，除源自氧化鋁原料的Al2O3成分外，尚包含源自作為結合劑廣泛使用的鋁氧火泥的Al2O3成分。亦即，「粒徑未達45μm之原料所含的Al2O3成分之含量」，係指高爐槽用可鑄性耐火物全體(高爐槽用可鑄性耐火物之化學成分的總量100質量%中)的粒徑未達45μm之原料所含的Al2O3成分之含量。此外，上述專利文獻1之表2所示之實施例5中係含有5質量%之預燒結氧化鋁，並額外含有3質量%之鋁氧火泥。該鋁氧 火泥中係至少含有70質量%之粒徑未達45μm之原料所含的Al2O3成分。更且，粒徑1mm以下之電熔氧化鋁中係含有2質量%左右之粒徑未達45μm之原料所含的Al2O3成分。因此，可鑄性耐火物全體的粒徑未達45μm之原料所含的Al2O3成分之含量成為7質量%以上。
作為本發明高爐槽用可鑄性耐火物所使用的氧化鋁原料，可列舉燒結氧化鋁、電熔氧化鋁、明礬頁岩、鋁礬土等。其中，較佳為品質穩定的燒結氧化鋁、電熔氧化鋁等的合成品。微粉部亦可使用預燒結氧化鋁。
就碳化矽原料而言，較佳為SiC純度為85質量%以上者，更佳為95質量%以上者。SiC成分之含量未達40質量%時，抗渣性效果差；超過80質量%時，因此必然使得碳、氧化鋁等的比例減少，耐銑鐵侵蝕性差。
作為碳原料，可列舉各種瀝青、碳黑、人造石墨、片狀石墨、土狀石墨、焦炭、無煙煤等的1種或2種以上。諸如上述，碳原料(自由之C成分)之含量為1~10質量%左右。
作為抗氧化劑，係使用碳化硼(B4C)。B4C成分之含量未達0.3質量%時，無法獲得抗氧化效果。又B4C成分之含量超過3.0質量%時則液相生成量變多，因過度燒結作用而容易發生龜裂剝離。
作為分散劑，可列舉三聚磷酸鈉、六偏磷酸鈉、超聚磷酸鈉、酸性六偏磷酸鈉、硼酸鈉、碳酸鈉、聚偏磷酸鹽等的無機鹽、檸檬酸鈉、酒石酸鈉、聚丙烯酸、 聚丙烯酸鈉、磺酸鈉、聚羧酸鹽、β-萘磺酸鹽類、萘磺酸等。
作為結合劑，可列舉鋁氧火泥、鎂氧水泥、膠體氧化矽、膠體氧化鋁等。其中，較佳為容易獲得加工體之組織強度的鋁氧火泥，鋁氧火泥較佳為JIS規格之耐火物鋁氧火泥的1種或2種相似物。
除上述各原料以外，在滿足上述化學成分之規定值的範圍內，尚可使用矽酸質粉末、乾燥促進劑、Al粉、Si粉、金屬纖維、有機纖維、陶瓷纖維、鹼性乳酸鋁、硼化合物、抗氧化劑、增黏劑、硬化劑、硬化延緩劑、耐火過大粒子等。
本發明高爐槽用可鑄性耐火物可與習知高爐槽用可鑄性耐火物同樣地添加加工水而進行加工。
[實施例]
表1示出本發明之實施例及比較例。
如表1之化學成分，摻混氧化鋁原料、碳化矽原料、碳原料、碳化硼(B4C)原料、分散劑及結合劑，添加適量的加工水後進行混練，再予以注入至模框而成形。接著施予熟化．乾燥，得到試驗加工體。此外，表1之實施例及比較例中係使用電熔氧化鋁作為氧化鋁原料、使用純度為95質量%以上的碳化矽作為碳化矽原料、使用碳黑及瀝青作為碳原料、使用碳化硼(B4C)作為抗氧化劑、使用聚丙烯酸作為分散劑，並使用鋁氧火泥2種相似物作為結合劑，以化學成分值表示。再者，表1中「其他」之成分係包含表1未記載之成分暨分散劑及各原料雜質之成分。
對所得試驗加工體，依以下要領進行氧化試驗並進行抗彎試驗，測定抗彎強度，進行綜合評定。
(氧化試驗)
製作直徑50mm、高度50mm的試片，經乾燥後在大氣中、1000℃進行燒成。對燒成後之試片，觀察外觀及從高度25mm位置朝水平方向切開的面的氧化狀態。就氧化狀態之觀察，係將略帶白色的部分視為氧化部分。茲將氧化未進行者評為「○」；氧化未進行但試片外觀呈多泡狀而性質較差者評為「△」；氧化已進行者評為「×」。
(抗彎試驗)
製作40mm×40mm×160mm之試片，經乾燥後在大氣 中、1000℃進行燒成。對燒成後之試片，依據JIS R2553進行抗彎試驗並測定抗彎強度。將實施例2供予實機測試，得到龜裂剝離獲抑制之結果，且在抗彎強度為15MPa以上的情況下發生了龜裂剝離，因此將「抗彎強度未達15MPa」定為較佳範圍。此外，將比較例2供予實機測試，結果有多處龜裂剝離。
(綜合評定)
氧化試驗及抗彎強度係評定緻密之燒結體(9A2B)的生成程度之項目，在此等項目中只要滿足氧化試驗○、抗彎強度未達15MPa，則不會發生緻密之燒結體(9A2B)的龜裂剝離，也不會使源自B4C成分的B2O3所產生的抗氧化機能降低。因此，在綜合評定中，茲將氧化試驗為○且抗彎強度未達15MPa的情況評為「○」；氧化試驗為△或×、或者抗彎強度為15MPa以上的情況評為「×」。
如表1所示，處於本發明所規定之化學成分之範圍的實施例1~6其綜合評定均為「○」。
與此相對，比較例1係含有0.8質量%之B4C成分，但含有粒徑未達45μm之原料所含的Al2O3成分多達7.2質量%之案例，相較於實施例，耐氧化性較差且抗彎強度變高。
比較例2係含有粒徑未達45μm之原料所含的Al2O3成分進一步多達11質量%之案例，其結果為耐氧化性更形劣化，且抗彎強度亦變高。
比較例3係B4C成分少至0.2質量%之案例；因B4C較少，致B2O3的生成量減少，與Al2O3之固溶體(9A2B)的生成獲抑制，可能因為此影響而未使抗彎強度變高，但結果為耐氧化性差。
比較例4係B4C多達3.1質量%之案例，試片的氧化獲抑制而耐氧化性提升，惟B4C過多，因為此影響而使表面呈多泡狀，試片之外觀性質差。又可能因液相生成量變多，使得抗彎強度變高。

Claims (3)

  1. 一種高爐槽用可鑄性耐火物，其係含有：40質量%以上且80質量%以下之SiC成分、10質量%以上且40質量%以下之粒徑45μm以上之原料所含的Al2O3成分、0.3質量%以上且3.0質量%以下之B4C成分，且粒徑未達45μm之原料所含的Al2O3成分之含量為6.9質量%以下。
  2. 如請求項1之高爐槽用可鑄性耐火物，其中粒徑未達45μm之原料所含的Al2O3成分之含量為3.9質量%以下。
  3. 如請求項1或2之高爐槽用可鑄性耐火物，其中B4C成分之含量為0.3質量%以上且1.5質量%以下。
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