TW201742851A - 焦爐用預製塊耐火材料 - Google Patents

焦爐用預製塊耐火材料 Download PDF

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TW201742851A
TW201742851A TW106106679A TW106106679A TW201742851A TW 201742851 A TW201742851 A TW 201742851A TW 106106679 A TW106106679 A TW 106106679A TW 106106679 A TW106106679 A TW 106106679A TW 201742851 A TW201742851 A TW 201742851A
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mass
coke oven
component
less
refractory
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Hidetoshi Terashima
Yasushi Tsutsui
Hironao Takemoto
Taijiro Matsui
Takashi Matsunaga
Yutaka Kitazawa
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Nippon Steel & Sumitomo Metal Corp
Krosakiharima Corp
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Abstract

本發明係提供具有高熱強度，並且於高溫時之荷重下膨縮舉動為安定的焦爐用預製塊耐火材料。亦即，本發明係一種焦爐用預製塊耐火材料，其特徵為，於二氧化矽質之焦爐用預製塊耐火材料中，含有0.3質量%以上、2質量%以下之P2O5成分。

Description

焦爐用預製塊耐火材料
本發明係關於適宜使用於焦爐中的預製塊耐火材料。
以往，於焦爐中係將矽石磚作襯裹來使用。但，在使用矽石磚的情況，由於必須對多數個磚進行施工，因此有著在施工上需要時間的問題。因此，近年來，尤其是於熱修補施工中，大多實施使用有相較於矽石磚更容易大型化的矽石質之預製塊耐火材料的施工。
對於如此之預製塊耐火材料係要求作為構造體之熱特性。尤其，於焦爐中，除了熱強度以外，亦要求高溫時之荷重下膨脹舉動及荷重下收縮舉動(以下，統稱為荷重下膨縮舉動)的安定化。在高溫之荷重下膨縮舉動不安定的情況(伴隨著高溫之荷重下膨脹或荷重下收縮而來的變形為大的情況)，在將煤焦擠出時阻抗會變大，恐有對作業帶來障礙，並且預製塊耐火材料自體破損之虞。
於專利文獻1中係記載有以熔融石英作為主原料，並使用波特蘭水泥作為黏結劑的技術。但，在於焦 爐用預製塊耐火材料中使用多量(例如，相對於主原料，為2~10重量%)的波特蘭水泥作為黏結劑的情況，會有因波特蘭水泥之水合反應，而於高溫之荷重下大幅收縮的問題。
又，於專利文獻2中，作為黏結劑(硬化劑)，係取代以往一般所使用的氧化鋁水泥，而使用膠體二氧化矽及矽酸鈉，藉此想要抑制高溫之荷重下收縮。但，在使用膠體二氧化矽及矽酸鈉的情況，會有熱強度降低的問題。
[先前技術文獻] [專利文獻]
[專利文獻1]日本特開昭56-78476號公報
[專利文獻2]日本特開2013-189322號公報
本發明所欲解決之課題，係提供具有高熱強度，並且於高溫時之荷重下膨縮舉動為安定的焦爐用預製塊耐火材料。
本發明者們為了解決上述課題而進行努力探討。例如，如專利文獻1所記載般，在使用多量的水泥作 為黏結劑的情況，因水泥導致的水合反應而使高溫下之荷重下收縮舉動不安定。又，在使用膠體二氧化矽及矽酸鈉作為黏結劑的情況，熱強度會降低。因此，本發明者們得到下述見解：於二氧化矽質之焦爐用預製塊耐火材料中，並非使用多量的水泥作為黏結劑，或使用膠體二氧化矽及矽酸鈉作為黏結劑，而是適用P2O5成分作為黏結劑成分，藉此可一面維持高熱強度，一面安定地控制高溫時之荷重下膨縮舉動。
亦即，本發明之焦爐用預製塊耐火材料，其特徵為，於二氧化矽質之焦爐用預製塊耐火材料中，含有0.3質量%以上、2質量%以下之P2O5成分。
依據本發明，可得到發揮高熱強度，並且於高溫時之荷重下膨縮舉動為安定的焦爐用預製塊耐火材料。
[第1圖]係顯示實施例及比較例之荷重下膨縮舉動的圖表。
本發明之焦爐用預製塊耐火材料，係二氧化矽質，亦即以SiO2成分作為主成分的焦爐用預製塊耐火 材料。具體的SiO2成分之含量雖為技術常識之範圍內，但較佳為65質量%以上、99質量%以下，更佳為80質量%以上、99質量%以下。
作為SiO2成分源係可使用熔融二氧化矽、矽石(煅燒矽石、生矽石等)、氣相二氧化矽等各種之二氧化矽質原料，但於本發明中，於原料摻合中，熔融二氧化矽之摻合量較佳為65質量%以上，更佳為72質量%以上。又，較佳係矽石之摻合量為17質量%以下，氣相二氧化矽之摻合量為0.5質量%以上、15質量%以下。亦即，就可消除因乾燥時之脫水導致之收縮的點而言，較佳係熔融二氧化矽之摻合量為65質量%以上，且矽石之摻合量為17質量%以下。於此情況中，矽石之摻合量亦可為0質量%。又，就維持高熱強度的點而言，較佳係氣相二氧化矽之摻合量為0.5質量%以上、15質量%以下。又，二氧化矽質原料之粒度，較佳係考慮填充性及作業性，將最大尺寸5mm之骨材至次微米之粒子組合使用。進而，為了使荷重下熱膨脹/收縮率(以下稱為「荷重下膨縮率」)更安定，較佳係將1mm以上之粗粒設為25質量%以上。
另外，作為主骨材之二氧化矽質原料以外的原料亦可併用氧化鋁質原料。作為氧化鋁質原料係可使用電熔氧化鋁、燒結氧化鋁等。但，若SiO2成分為未達65質量%，則由於熱強度會降低，因此添加多量之氧化鋁質原料者較不理想。
於本發明之焦爐用預製塊耐火材料中，P2O5成分係如上述般發揮作為黏結劑的功能，但，其含量係為0.3質量%以上、2質量%以下。於P2O5成分之含量為未達0.3質量%時係無法發揮作為黏結劑成分之黏著功能。若P2O5成分之含量超過2質量%，則低熔點物質(SiO2-P2O5系)會過剩地生成，而於高溫之荷重下伴隨著收縮而來的變形會變大。
作為P2O5成分源雖可使用磷酸鹽，但於此情況中，於磷酸鹽中作為雜質而包含的Na2O成分及K2O成分，就抑制低熔點物質之生成的點而言，較佳係作為預製塊耐火材料中之含量為合量0.5質量%以下。
又，於本發明之焦爐用預製塊耐火材料的原料摻合中，硬化促進劑之摻合量，就提高預硬化處理時之強度的點而言，較佳為0.05質量%以上，且就維持高熱強度的點而言，較佳為1.9質量%以下。作為硬化促進劑係可列舉：氧化鎂微粉、消石灰等。
進而，本發明之焦爐用預製塊耐火材料較佳係不包含水泥。在包含水泥的情況，會因水泥之水合反應而產生荷重下收縮，但在不包含水泥的情況，可抑制荷重下收縮。
本發明之焦爐用預製塊耐火材料，係可藉由摻合作為主原料之上述的二氧化矽質原料(SiO2成分源)及作為黏結劑之磷酸鈉(P2O5成分源)，又因應需要而摻合作為其他添加劑之有機纖維、分散劑、硬化促進劑、硬 化延遲劑、燒結輔助劑等，並於所得到的原料摻合物中添加適量(例如5質量%~7質量%)的施工水之後，進行混練、成形、預硬化處理、脫模、乾燥之通常的預製塊耐火材料之製造方法而得。
[實施例]
使用按照表1之原料摻合來摻合各原料，並添加6.5質量%之施工水之後，進行混練、成形、預硬化處理、脫模、乾燥所得之焦爐用預製塊耐火材料的試驗片，測定荷重下膨縮舉動及熱彎曲強度，而進行綜合評估。一併對所得之試驗片的化學成分進行分析。在此，熔融石英、鍛燒矽石、生矽石及電熔氧化鋁的粒度分別使用將5-1mm與未達1mm以6：4之比率混合而成者。又，氣相二氧化矽之粒度係使用平均粒徑0.5μm者。另外，原料之化學成分係使用分別為熔融石英含有SiO2成分99.7質量%、煅燒矽石含有SiO2成分99.5質量%、生矽石含有SiO2成分99.7質量%、氣相二氧化矽含有SiO2成分96質量%、Na2O成分0.2質量%、電熔氧化鋁含有Al2O3 100質量%、磷酸鈉含有P2O5成分65質量%、Na2O成分23質量%、矽酸鈉含有SiO2成分64質量%、Na2O成分22質量%、膠體二氧化矽含有SiO2成分40質量%、波特蘭水泥含有SiO2成分24質量%、氧化鎂微粉含有MgO成分100質量%、消石灰含有CaO 100質量%者。
荷重下膨縮舉動係於室溫至1300℃為止的溫 度區域中，根據JIS R 2207-2，施加0.2MPa之荷重來進行測定。荷重下收縮率係將-0.1%以上、未達0.5%之範圍的情況設為優(◎)、將-0.3%以上、未達-0.1%之範圍的情況或者+0.5%以上、未達+0.7%之範圍的情況設為良(○)、將-0.5%以上、未達-0.3%之範圍的情況或者0.7%以上、未達+0.8%之範圍的情況設為可(△)、將未達-0.5%或者+0.8%以上設為不可(×)，且將可(△)以上視為合格。另外，-(負)係意味著荷重下收縮，+(正)係意味著荷重下膨脹。
熱彎曲強度係於1000℃時，根據JIS R 2213來進行測定。另外，為了使試驗片成為測定溫度，而在爐內進行1小時保持，測定熱彎曲強度。熱彎曲強度係將10MPa以上設為優(◎)、將5MPa以上、未達10MPa設為良(○)、將3MPa以上、未達5MPa設為可(△)、將未達3MPa設為不可(×)，且將可(△)以上視為合格。
接著，綜合評估係於上述2個評估中，將優(◎)為2個的情況設為優(◎)、將優(◎)與良(○)之組合的情況設為良(○)、將優(◎)或是良(○)與可(△)之組合的情況設為可(△)、將具有不可(×)的情況設為不可(×)，且將可(△)以上視為合格。
將此等之評估結果一併顯示於表1。
表1中，實施例1~15皆為範圍內之焦爐用預製塊耐火材料。綜合評估為可(△)以上，荷重下膨縮舉動、熱彎曲強度皆為合格水準。
比較例1係P2O5成分之含量為低的例子。無法得到充分的黏結功能，熱彎曲強度未達合格水準。另一方面，比較例2係P2O5成分之含量為高的例子。由於低熔點物質(SiO2-P2O5)過剩地生成，因此荷重下膨縮舉動為未達合格水準。
比較例3係於以Al2O3成分作為主成分之焦爐用預製塊耐火材料中，適用P2O5成分作為黏結劑成分的例子。荷重下膨縮舉動為未達合格水準。
比較例4係相當於上述專利文獻1的例子，且適用膠體二氧化矽及矽酸鈉作為黏結劑的例子。熱彎曲強度為未達合格水準。
比較例5係僅使用波特蘭水泥作為黏結劑的例子。荷重下膨縮舉動為未達合格水準。
又，第1圖係顯示實施例1及比較例5之室溫至1300℃為止之荷重下膨縮舉動的圖表。滿足摻合磷酸鹽(P2O5成分源)作為黏結劑之本發明的範圍之實施例1，係荷重下膨縮舉動為安定，摻合有多量(5質量%)之波特蘭水泥作為黏合劑之比較例5係從1000℃附近起明顯地荷重下收縮。

Claims (7)

  1. 一種焦爐用預製塊耐火材料，其特徵為，於二氧化矽質之焦爐用預製塊耐火材料中，含有0.3質量%以上、2質量%以下之P2O5成分。
  2. 如請求項1之焦爐用預製塊耐火材料，其係含有65質量%以上、99質量%以下之SiO2成分。
  3. 如請求項1之焦爐用預製塊耐火材料，其係含有80質量%以上、99質量%以下之SiO2成分。
  4. 如請求項1至3中任一項之焦爐用預製塊耐火材料，其中，於原料摻合中，熔融二氧化矽的摻合量為65質量%以上。
  5. 如請求項1至4中任一項之焦爐用預製塊耐火材料，其中，於原料摻合中，矽石的摻合量為17質量%以下，氣相二氧化矽(fumed Silica)的摻合量為0.5質量%以上、15質量%以下。
  6. 如請求項1至5中任一項之焦爐用預製塊耐火材料，其中，於原料摻合中，硬化促進劑的摻合量為0.05質量%以上、1.9質量%以下。
  7. 如請求項1至6中任一項之焦爐用預製塊耐火材料，其中，作為黏結劑係不包含水泥。
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