TWI729513B - 熱用乾式噴塗材料及熱乾式噴塗施工方法 - Google Patents

熱用乾式噴塗材料及熱乾式噴塗施工方法 Download PDF

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TWI729513B
TWI729513B TW108135450A TW108135450A TWI729513B TW I729513 B TWI729513 B TW I729513B TW 108135450 A TW108135450 A TW 108135450A TW 108135450 A TW108135450 A TW 108135450A TW I729513 B TWI729513 B TW I729513B
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大野洋輔
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日商黑崎播磨股份有限公司
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Abstract

本發明係以在熱用乾式噴塗材料及熱乾式噴塗施工方法中，提升耐蝕性為目的。亦即，本發明為一種熱乾式噴塗施工方法，其係將包含耐火材料及黏合劑的摻合物，透過配管朝噴塗噴嘴加壓輸送，並在前述噴塗噴嘴的前端部添加水而於熱環境下進行噴塗，其特徵為：前述摻合物，在前述耐火材料及前述黏合劑的合計量100質量%中，包含10質量%以上50質量%以下之粒徑0.075mm以上且未達1mm的苦土石灰石，在前述耐火原料及黏合劑的合計量100質量%中，粒徑未達0.075mm的苦土石灰石的含量為35質量%以下(包含0)。

Description

熱用乾式噴塗材料及熱乾式噴塗施工方法
本發明係有關於一種尤其適用於熔鋼鍋或電爐之爐體(爐壁)等工業窯爐的熱修補的熱用乾式噴塗材料(不定形耐火物)及其施工方法。 此外，「熱環境」係指被施工面的溫度約為600℃以上的環境。
不定形耐火物的施工方法係隨使用用途而異。例如，將不定形耐火物作為工業窯爐之內襯用的可鑄性材料使用時，係經過耐火材料與水之混煉步驟、澆鑄步驟、熟化步驟、乾燥步驟而進行施工。
另一方面，亦有時會將不定形耐火物作為工業窯爐之築爐或修補用的噴塗材料使用。此時，施工方法可大致區分為濕式噴塗施工方法與乾式噴塗施工方法。濕式噴塗施工方法係藉由混合機等機械式混煉機構預先將噴塗材料與水充分混煉，將該混煉之混煉物以幫浦朝噴塗噴嘴加壓輸送，並於此噴塗噴嘴的前端部導入空氣與速凝劑而進行噴塗的施工方法。乾式噴塗施工方法則是未經由機械式混煉機構，而於噴塗噴嘴的前端部對乾粉狀的噴塗材料添加水而進行噴塗的施工方法。
一般而言，使用噴塗材料之噴塗施工係於熱及冷的任一種環境下進行，而乾式噴塗施工方法則是適用於此兩種環境。然而，濕式噴塗施工方法，一般而言非適用於熱環境下。這是因為，若採濕式噴塗施工方法時，由於需要事前的混煉作業，而於施工後需要以混煉機或泵加壓輸送時所使用之搬送軟管的洗淨作業等清理作業。因此，濕式施工方法非適用於在熱環境下的噴塗施工，而較常應用屬簡易的施工方法之乾式噴塗施工方法。
使用於此乾式噴塗施工方法之噴塗材料(乾式噴塗用不定形耐火物)，專利文獻1中揭示一種包含苦土石灰石的噴塗材料。然而，本案發明人等使用包含苦土石灰石之噴塗材料進行熱噴塗施工的結果獲知，尤其是耐蝕性尚有改善的空間。 [先前技術文獻] [專利文獻]
[專利文獻1]日本特開昭58-145660號公報
[發明所欲解決之課題]
本發明所欲解決之課題在於在熱用乾式噴塗材料及熱乾式噴塗施工方法中，提升耐蝕性。 [解決課題之手段]
本案發明人等為了在熱用乾式噴塗材料及熱乾式噴塗施工方法中提升耐蝕性，特別著眼於耐熔渣滲透性而累積多次研究的結果發現，粒徑0.075mm以上且未達1mm的苦土石灰石極有助於提升耐熔渣滲透性，終至完成本發明。
亦即，根據本發明一觀點，係提供以下之熱用乾式噴塗材料。 一種熱用乾式噴塗材料，其係包含耐火原料與黏合劑的熱用乾式噴塗材料，其中， 在前述耐火材料及前述黏合劑的合計量100質量%中，包含10質量%以上50質量%以下之粒徑0.075mm以上且未達1mm的苦土石灰石， 在前述耐火原料及黏合劑的合計量100質量%中，粒徑未達0.075mm的苦土石灰石的含量為35質量%以下(包含0)。
又，根據本發明另一觀點，係提供以下之熱乾式噴塗施工方法。 一種熱乾式噴塗施工方法，其係將包含耐火材料及黏合劑的摻合物，透過配管朝噴塗噴嘴加壓輸送，並在前述噴塗噴嘴的前端部添加水而於熱環境下進行噴塗，其中， 前述摻合物，在前述耐火材料及前述黏合劑的合計量100質量%中，包含10質量%以上50質量%以下之粒徑0.075mm以上且未達1mm的苦土石灰石， 在前述耐火原料及黏合劑的合計量100質量%中，粒徑未達0.075mm的苦土石灰石的含量為35質量%以下(包含0)。
此外，本發明中所稱粒徑，係指將耐火材料粒子以篩子篩濾而分離時的孔徑大小，例如粒徑未達0.075mm的苦土石灰石係指可通過孔徑為0.075mm的篩子之苦土石灰石；粒徑0.075mm以上的苦土石灰石則指無法通過孔徑為0.075mm的篩孔之苦土石灰石。 [發明之效果]
根據本發明，藉由使粒徑0.075mm以上且未達1mm的苦土石灰石的含量處於特定範圍，可提升耐熔渣滲透性，其結果可提升耐蝕性。
[實施發明之形態]
本發明之熱用乾式噴塗材料，在耐火材料及黏合劑的合計量(下稱「合計量」)100質量%中包含10質量%以上50質量%以下之粒徑0.075mm以上且未達1mm的苦土石灰石(下稱「中粒苦土石灰石」)。
此中粒苦土石灰石(CaCO3 ・MgCO3 )會因運轉受熱時的脫氣反應(CaCO3 ・MgCO3 →CaO・MgO+2CO2 )，於其內部生成空隙，並生成高反應性的游離CaO。如此一來，自運轉面滲透而至的熔渣被生成的空隙捕捉，進而與游離CaO反應，生成高熔點組成物2CaO・SiO2 (熔點2130℃)，而抑制熔渣的滲透。 中粒苦土石灰石的含量若未達10質量%，則無法充分發揮熔渣滲透抑制效果(耐熔渣滲透性提升效果)，而無法獲得充分的耐蝕性提升效果。另一方面，苦土石灰石的含量若超過50質量%，則會因脫氣反應而過度生成空隙(開放氣孔)，結果助長熔渣滲透而導致耐蝕性變差。 中粒苦土石灰石的含量，在合計量100質量%中較佳為20質量%以上40質量%以下。
本發明之熱用乾式噴塗材料可包含粒徑未達0.075mm的苦土石灰石(下稱「微粒苦土石灰石」)。 於此，微粒苦土石灰石亦會因前述之脫氣反應而生成CaO，而此CaO由於係由與水之接觸面積較大的微粒苦土石灰石所生成而容易發生水合反應(CaO+2H2 O→Ca2+ + 2OH- )，研判藉此水合反應所生成的Ca2+ 會與黏合劑等反應而有助於噴塗施工體之基質部的結合強化(高強度化)，且研判無益於前述之高熔點組成物的生成。 惟，若含有大量微粒苦土石灰石，比起前述基質部的結合強化(高強度化)作用，前述脫氣反應所造成的影響(空隙形成的影響)較強，而於基質部過度生成空隙，結果導致噴塗施工體強度顯著降低且亦導致耐蝕性降低。從而，微粒苦土石灰石的含量，在合計量100質量%中係取35質量%以下(包含0)。
另一方面，微粒苦土石灰石由於如前述可發揮基質部的結合強化(高強度化)作用，由積極利用此基質部的結合強化(高強度化)作用而提升接著性(於噴塗後工業窯爐運轉後之噴塗材料與被施工面的接著性)而言，微粒苦土石灰石的含量，在合計量100質量%中較佳取5質量%以上35質量%以下，更佳取5質量%以上25質量%以下。
本發明之熱用乾式噴塗材料亦可包含粒徑1mm以上的苦土石灰石(下稱「粗粒苦土石灰石」)。惟，由於粗粒苦土石灰石會因前述之脫氣反應而生成大的空隙，若含有大量粗粒苦土石灰石則熔渣更容易滲透而有耐蝕性變差的傾向。從而，粗粒苦土石灰石的含量，在合計量100質量%中較佳取未達50質量%(包含0)。
如以上所述，本發明之前述熔渣滲透抑制效果(耐熔渣滲透性提升效果)可藉由使各粒度之苦土石灰石當中尤其是中粒苦土石灰石的含量處於特定範圍而獲得。
本發明之熱用乾式噴塗材料，作為苦土石灰石以外的耐火材料，可包含一般使用於噴塗材料的各種耐火材料；考量到與苦土石灰石的契合性，其主體較佳採氧化鎂或橄欖石(olivine)、用畢之氧化鎂-碳質磚屑等的鹼性耐火材料(鹼性氧化物)。作為鹼性耐火材料以外的耐火材料，可包含氧化鋁等。
黏合劑可使用作為結合材料而一般使用於乾式噴塗材料者，可舉出例如磷酸鹽、矽酸鹽、瀝青、粉末樹脂、鋁氧火泥等；典型上係使用包含選自磷酸鹽及矽酸鹽之中的至少1種者。磷酸鹽有磷酸鈉、磷酸鉀、磷酸鋰、磷酸鈣、磷酸鎂、磷酸鋁等；矽酸鹽則有矽酸鈉、矽酸鉀、矽酸鈣等。又，黏合劑的用量(含量)亦可與一般的乾式噴塗材料相同，例如在合計量100質量%中為1質量%以上10質量%以下。 此外，黏合劑中亦可使用添加劑。作為添加劑，可使用硬化劑、分散劑、增黏劑等各種的添加劑。例如，硬化劑可使用消石灰，分散劑可使用磷酸鹽，增黏劑則可使用黏土。
如以上之本發明之熱用乾式噴塗材料係供予熱乾式噴塗施工方法，此方法係將如前述之包含耐火材料及黏合劑的摻合物，透過配管朝噴塗噴嘴加壓輸送，並在此噴塗噴嘴的前端部添加水而於熱環境下進行噴塗。 水的添加量可與一般的熱乾式噴塗施工方法相同，例如相對於合計量100質量%額外添加10質量%以上40質量%以下。 [實施例]
表1示出本發明之熱用乾式噴塗材料之實施例及比較例的材料構成與評定結果。此外，表1中黏合劑的「其他」係指黏土、消石灰、分散劑等。 評定項目與評定方法如下。
＜耐蝕性＞ 將各例之熱用乾式噴塗材料由噴塗噴嘴，以15kg/分之噴塗量朝作為被施工面之經加熱至1000℃的氧化鎂磚的表面進行噴塗1分鐘。此時，在噴塗噴嘴的前端部添加之水的添加量，相對於合計量100質量%係額外添加20質量%。 藉由實施1分鐘的噴塗，可獲得包含約50mm厚的噴塗材料之施工體的噴塗施工體。將由此噴塗施工體切出之既定尺寸的試料，使用旋轉侵蝕試驗機，以C/S=1.0的合成熔渣作為侵蝕劑，於1650～1700℃下侵蝕3小時。測定各例之最大熔損量，並求出將實施例1之最大熔損量設為100的相對量。此相對量愈小意指耐蝕性(耐熔渣滲透性)愈高。就耐蝕性之評定，係將此相對量為100以下時評為◎(良好)、超過100且為110以下時評為○(尚可)、超過110時評為×(不良)。
＜噴塗施工體強度＞ 針對由依前述要領所得之各例之噴塗施工體切出之既定尺寸的試料，依循JISR2575測定常溫下的壓縮強度，並求出將實施例1之壓縮強度設為100的相對值。此相對值愈大意指噴塗施工體強度愈高。就噴塗施工體強度之評定，係將此相對值為80以上時評為◎(良好)、為70以上且未達80時評為○(尚可)、未達70時評為×(不良)。
＜接著性＞ 如圖1之上層所示，在羊羹狀氧化鎂磚的中央開設15mm的間隔，於其之間對各例之噴塗材料添加水(相對於合計量100質量%額外添加20質量%)並予以混煉後再進行澆鑄、熟化、乾燥後，如圖1之下層所示在從羊羹的前端施加0.25MPa之負載的狀態下以1400℃進行3小時燒成而獲得試片。針對各例之試片根據3點彎曲試驗測定接著面的彎曲強度，並求出將實施例1之彎曲強度設為100的相對值。此相對值愈大意指接著性愈高。就接著性之評定，係將此相對值為100以上時評為◎(良好)、超過60且未達100時評為○(尚可)。 此接著性之評定係表示在實際的噴塗施工中，於噴塗後且工業窯爐運轉後之噴塗材料與被施工面的接著強度之指標。
＜綜合評定＞ 在前述各評定中，將全為◎時評為◎(良好)；無×且任一項有○時評為○(尚可)；任一項均為×時評為×(不良)。此綜合評定係表示實際的噴塗施工體的耐用性之指標。
Figure 02_image001
實施例1～9係處於本發明範圍內的熱用乾式噴塗材料。綜合評定皆為◎(良好)或○(尚可)，可獲得良好的結果。
比較例1係中粒苦土石灰石的含量偏少之實例。無法充分獲得熔渣滲透抑制效果(耐熔渣滲透性提升效果)，耐蝕性之評定為×(不良)。 比較例2係中粒苦土石灰石的含量偏多之實例。因前述脫氣反應導致空隙(開放氣孔)過度生成而助長熔渣滲透，結果耐蝕性之評定為×(不良)。 比較例3係微粒苦土石灰石的含量偏多之實例。由於前述脫氣反應的影響，於基質部過度生成空隙，結果耐蝕性及噴塗施工體強度之評定為×(不良)。
[圖1]為表示接著性之評定方法的說明圖。

Claims (4)

  1. 一種熱用乾式噴塗材料，其係包含耐火原料與黏合劑的熱用乾式噴塗材料，其中， 在前述耐火材料及前述黏合劑的合計量100質量%中，包含10質量%以上50質量%以下之粒徑0.075mm以上且未達1mm的苦土石灰石， 在前述耐火原料及黏合劑的合計量100質量%中，粒徑未達0.075mm的苦土石灰石的含量為35質量%以下(包含0)。
  2. 如請求項1之熱用乾式噴塗材料，其中前述黏合劑係包含選自磷酸鹽及矽酸鹽之中的至少1種。
  3. 如請求項1或2之熱用乾式噴塗材料，其中前述粒徑未達0.075mm的苦土石灰石的含量為5質量%以上35質量%以下。
  4. 一種熱乾式噴塗施工方法，其係將包含耐火材料及黏合劑的摻合物，透過配管朝噴塗噴嘴加壓輸送，並在前述噴塗噴嘴的前端部添加水而於熱環境下進行噴塗，其中， 前述摻合物，在前述耐火材料及前述黏合劑的合計量100質量%中，包含10質量%以上50質量%以下之粒徑0.075mm以上且未達1mm的苦土石灰石， 在前述耐火原料及黏合劑的合計量100質量%中，粒徑未達0.075mm的苦土石灰石的含量為35質量%以下(包含0)。
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