201130989 六、發明說明： 【發明所屬之技術領域】 本發明係關於適用於對轉爐型精煉容器內的熔融生鐵 (hot metal)或熔鋼實施脫磷處理（dephosphorization treatment)等的氧化精煉（oxidation refining)之精煉用 ' 上吹式噴管（top lance )，進一步關於使用該上吹式噴管 之熔融生鐵之精煉方法。本發明之上吹式噴管，由於含氧 氣體（oxygen containing gas)的供應路徑和氧化鐵等的 固體氧源（solid oxygen source)的供應路徑是分離的， 可從該等路徑將含氧氣體及固體氧源獨立地供應至轉爐型 精煉容器內的熔融生鐵或熔鋼的浴面。又本發明的上吹式 噴管，可將固體氧源以外的粉體和含氧氣體一起供應。再 者本發明的上吹式噴管，可從與噴管前端部隔離之噴管的 側面，將二次燃燒用的含氧氣體供應至轉爐型精煉容器的 爐內空間。 【先前技術】 在使用高爐熔融生鐵的製鋼過程中，在藉由轉爐（ converter)進行脫碳吹煉之前，一般是進行熔融生鐵的預 備脫磷處理（dephosphorization pretreatment))，以將 熔融生鐵中所含的磷（P )大部分藉由氧氣和固體氧化鐵 來予以氧化除去。特別是近年來，對鋼鐵製品的品質要求 比以前更爲嚴格’而要求進一步減低磷濃度。爲了因應該 品質要求’實施脫磷處理的熔融生鐵量必須比以往更多， -5- 201130989 又必須將脫磷處理後的磷濃度穩定地降低。 另一方面，爲了減輕以地球暖化爲代表之對環境造成 的影響，必須減少製鋼過程中熔渣（slag )排出量。在熔 融生鐵的預備脫磷處理中爲了減少熔渣的排出量，必須減 少脫磷用的精煉劑（以下稱「脫磷用精煉劑」）的投入量 ，該脫磷用精煉劑熔融後會成爲具備磷氧化物（P205 )吸 收用精煉劑（refining agent)的作用之熔渣（稱爲「脫磷 精煉用熔渣」）。熔融生鐵的預備脫磷處理之脫磷用精煉 劑的主體爲石灰（lime )。因此，爲了符合上述品質要求 並減少熔渣排出量，必須有能在減少石灰使用量下維持必 要脫磷量的技術，亦即必須有能在較少石灰使用量下高效 率地進行脫磷處理的技術。 在熔融生鐵的預備脫磷處理中，由於未進行滓化（ fluxing，熔渣化）的石灰無助於脫磷反應，爲了減少石灰 使用量，如何促進所添加的石灰之滓化是很重要的。以往 ，作爲包含石灰之熔渣滓化能力優異的滓化促進用的助熔 劑（滓化促進劑，fluxing agent )，蛋石（fluori te，以氣 化鈣爲主成分的礦石）是已知的，而在脫磷處理中也是使 用螢石。然而近年來，隨著環保法規的曰趨嚴格，已開始 限制含氟的助熔劑的使用。因此，針對不須使用螢石也能 促進石灰所形成的脫磷反應的手段已被探討，且有多數的 提案。 其中之一手段所提出的技術，是將石灰系的脫磷用精 煉劑，供應至與含氧氣體和氧化鐵等的氧源所供應的場所 -6- 201130989 相同的場所或接近的場所。該技術，是爲了促進石灰系的 脫磷用精煉劑之滓化，以在較少石灰系脫磷用精煉劑下高 效率地進行脫磷處理。 例如，在專利文獻1提出一種熔融生鐵之預備脫磷處 理方法，是在氧氣所供應的場所，添加石灰系的脫磷用精 煉劑及吸熱物質來進行。又在專利文獻2揭示一種上吹式 噴管，其適用於對藉由供應氧氣而形成於熔融生鐵表面的 火點（fire spot，hot spot)區域添加石灰系脫磷用精煉劑 。該上吹式噴管，是在軸心部位置配置用來供應石灰系脫 磷用精煉劑之粉體吹入噴嘴，在其周圍配置用來供應氣氣 之複數個噴嘴，而形成四層管構造。此外，專利文獻3提 出一種五層管構造的精煉用上吹式噴管，其中，將石灰系 脫磷用精煉劑和含氧氣體一起供應的供應路徑是與氧化鐵 的供應路徑分離，且從該等路徑將含氧氣體、石灰系脫磷 用精煉劑及氧化鐵供應至熔融生鐵浴面以對熔融生鐵實施 脫磷處理等的氧化精煉。在該專利文獻3中還提出，藉由 在氧化鐵供應路徑的周圍設置緩衝空間，以檢測出氧化鐵 供應路徑的破洞。 然而，由於熔鐵的脫磷反應是溫度越低越有利，脫磷 處理是在1 300〜1 400 °C左右的熔融生鐵階段進行。例如在 專利文獻1及專利文獻2，是揭示1300 °C弱〜1350 °C左右的 實施溫度。此外，最近，由於自由空間（free board，爐 內的靜置熔融生鐵以外的空間）變大而能實施強力攪拌， 因此熔融生鐵之預備脫磷處理，一般是在轉爐型精煉容器 201130989 內進行。然而，由於是在低溫下，在脫磷處理中飛散的熔 融生鐵會在轉爐型精煉容器的側壁、爐口等附著凝固而造 成基體金屬的堆積，導致熔融生鐵良率降低，且該基體金 屬的除去作業會導致生產性降低。 該基體金屬附著的問題，並不限於熔融生鐵的預備脫 磷處理，在轉爐中熔融生鐵的脫碳精煉也會造成問題。亦 即，在轉爐中進行熔融生鐵的脫碳精煉時，起因於吹煉中 的基體金屬飛散（spitting)及熔澄噴出（slopping)，在 轉爐的內壁和爐口發生基體金屬的堆積，而有熔融生鐵及 鐵屑要裝入爐內時受到阻害等的問題產生。 爲了解決該基體金屬附著的問題，已有許多手段被提 出。例如專利文獻4揭示一種精煉方法.是在與上吹式噴 管（在前端部具有主孔噴嘴）的前端部隔離既定間隔之上 吹式噴管的側面，配置朝水平或朝下方的二次燃燒用噴嘴 ’從前述主孔噴嘴供應氧氣而對轉爐內的熔融生鐵或熔鋼 實施氧化精煉的同時’從前述二次燃燒用噴嘴供應氧氣而 將附著於轉爐的基體金屬予以熔解。 〔專利文獻1〕日本特開2003-32802 1號公報 〔專利文獻2〕日本特開2006-336033號公報 〔專利文獻3〕日本特開2008-208407號公報 〔專利文獻4〕日本特闊2〇〇8_138271號公報 【發明內容】 現在’在製鋼過程中，包含熔融生鐵的預備脫磷處理 -8- 201130989 ，作爲氧源，是倂用含氧氣體等的氣體氧源和氧化鐵等的 固定氧源，並將其等添加至同一部位或接近的部位之氧化 精煉方法已成爲主流。而且，在此情況，利用前述氣體氧 源作爲搬運用氣體，藉由將脫磷用精煉劑等的助熔劑（ flux )和氣體氧源一起搬運（參照專利文獻3 )，以將助熔 劑投入氣體氧源的添加位置之精煉方法也已被實施。此外 ，在實施這種精煉的情況也是，對附著於轉爐型精煉容器 的內壁及爐口之基體金屬，藉由從上吹式噴管側面的二次 燃燒用噴嘴供應的氣體氧源來施以熔解，基於確保鐵良率 及生產性的觀點是極爲重要的。 作爲實施上述精煉之上吹式噴管，對於上述習知的各 種形狀的上吹式噴管加以驗證的結果，不管是哪個上吹式 噴管都無法採用。此外，即使將上述習知的上吹式噴管加 以組合，仍無法獲得令人滿足的上吹式噴管。例如，即使 連接於專利文獻3的上吹式噴管之含氧氣體供應路徑，來 設置專利文獻4的二次燃燒用噴嘴，若透過含氧氣體供應 路徑將助熔劑和含氧氣體一起搬運，會發生二次燃燒用噴 嘴被該助熔劑堵塞的問題。 本發明是有鑑於上述情事而開發完成的，其目的是提 供一種精煉用上吹式噴管，像熔融生鐵之預備脫磷處理那 樣在轉爐型精煉容器內實施熔融生鐵或熔鋼的氧化精'煉B寺 ，可高效率地進行氧化精煉，同時能將附著於轉爐型精，練 容器之基體金屬予以高效率地熔解。本發明的目的，是$ —步提供使用該精煉用上吹式噴管之熔融生鐵的精煉方法 -9 - 201130989 爲了解決上述課題之本發明的要旨如 (1)—種精煉用上吹式噴管，是用 型精煉容器之熔融生鐵或熔鋼實施氧化精 式噴管，其特徵在於：在上吹式噴管的前 垂下方或朝斜下方之吹煉用主孔噴嘴及固 孔噴嘴，在從前述前端部往上方隔離的位 的側面部，具有朝水平或朝斜下方之二次 且在上吹式噴管的內部設有第1供應路徑 第3供應路徑；該第1供應路徑，是將不同 體和吹煉用的含氧氣體一起通過前述主孔 是將吹煉用的含氧氣體通過前述主孔噴增 供應路徑，是將二次燃燒用的含氧氣體通 用噴嘴來供應；該第3供應路徑，是將粉 和搬運用氣體一起通過前述副孔噴嘴來供 亦即，第1供應路徑係具備：將與固 體（以下也稱「精煉用助熔劑」）導入該 熔劑導入部、以及將該含氧氣體導入該路 入部。精煉用助熔劑導入部，亦可爲將精 運氣體一起導入之導入部，該搬運氣體較 體。當然，也能做成將精煉用助熔劑和含 導入部導入（亦即，將前述精煉用助熔劑 混合成要通過前述主孔噴嘴供應時的比例 部導入）的構造。又在作業時，將精煉用 來將收容於轉爐 煉之精煉用上吹 端部，具有朝鉛 體氧源吹送用副 置之上吹式噴管 燃燒用噴嘴，而 •第2供應路徑及 於固體氧源的粉 噴嘴來供應，或 I來供應；該第2 過前述二次燃燒 體狀的固體氧源 應。 體氧源不同的粉 路徑之精煉用助 徑之含氧氣體導 煉用助熔劑和搬 佳爲也是含氧氣 氧氣體從同一個 和含氧氣體事先 後，再從該導入 助熔劑的導入停 -10- 201130989 止，而僅將含氧氣體從前述含氧氣體導入部導入第1供應 路徑亦可。 此外，第2供應路徑係具備：將含氧氣體導入該路徑 之含氧氣體導入部。再者，第3供應路徑係具備：將固體 氧源和搬運用氣體一起導入該路徑之固體氧源導入部。又 在作業時，將固體氧源的供應停止，而僅將搬運用氣體從 前述導入部導入第3供應路徑亦可。 在此，第1供應路徑及第2供應路徑是共有含氧氣體導 入部亦可。在此情況是設有：用來防止前述精煉用助熔劑 混入第2供應路徑之分隔構造。 (2) 在上述（1)記載的精煉用上吹式噴管中，前述 第2供應路徑的末端是封閉的，從第2供應路徑供應的含氧 氣體不與第1供應路徑及第3供應路徑合流。 又第2供應路徑的末端，是指該路徑中比最靠近噴管 前端部的二次燃燒用噴嘴更前方（噴管前端部側）的部分 〇 (3) 在上述（2)記載的精煉用上吹式噴管中，是對 前述第2供應路徑供應還原性氣體、二氧化碳氣體、非氧 化性氣體、惰性氣體當中之任一種或兩種以上的氣體。 亦即，第2供應路徑係具備：將前述任一種或兩種以 上的氣體導入該路徑之導入部。當然，亦可做成將該等氣 體從與前述含氧氣體相同的導入部導入的構造。 (4) 在上述（1) ~(3)任一者記載的精煉用上吹式 噴管中，在前述第3供應路徑的周圍具備緩衝空間，在該 -11 - 201130989 緩衝空間內存在空氣、還原性氣體、二氧化碳 化性氣體、惰性氣體當中之任一種或兩種以上 據存在於該緩衝空間之氣體壓力或流量的變化 3供應路徑之破洞。 (5) 在上述（1) ~(4)任一者記載的精 噴管中，前述第1供應路徑、前述第2供應路.谷 供應路徑是配置在同心圓上。 (6) —種熔融生鐵之精煉方法，其特徵 灰系脫磷用精煉劑添加至轉爐型精煉容器內所 生鐵，讓所添加的前述脫磷用精煉劑滓化成熔 生鐵實施氧化精煉時，使用上述（1)〜（5) 的精煉用上吹式噴管，在從第1供應路徑將吹 供應至熔融生鐵浴面的同時，從第3供應路徑 和搬運用氣體一起供應至吹煉用的氧氣的供應 熔融生鐵浴面，進一步從第2供應路徑將二次 供應至轉爐型精煉容器的爐內空間而進行氧化: 又較佳爲，將前述石灰系脫磷用精煉劑的 從前述第1供應路徑供應至前述熔融生鐵。 依據本發明，上吹式噴管係在內部具備黃 、第2供應路徑及第3供應路徑；該第1供應路 灰系脫磷用精煉劑等之不同於固體氧源的粉體 含氧氣體一起通過主孔噴嘴來供應，或是將吹 氣體通過主孔噴嘴來供應；該第2供應路徑， 燒用的含氧氣體通過二次燃燒用噴嘴來供應； 氣體、非氧 的氣體，根 來檢測出第 煉用上吹式 I及前述第3 在於：將石 收容的熔融 渣，對熔融 任一者記載 煉用的氧氣 將固體氧源 場所附近之 燃燒用氧氣 隋煉。 至少一部分 5 1供應路徑 徑，是將石 和吹煉用的 煉用的含氧 是將二次燃 該第3供應 -12- 201130989 路徑，是將粉體狀的固體氧源和搬運用氣體一起通過副孔 噴嘴來供應。因此，即使從第1供應路徑及第3供應路徑供 應粉體，從二次燃燒用噴嘴僅噴射出含氧氣體，因此二次 燃燒用噴嘴能不發生堵塞而長期間穩定地噴射二次燃燒用 含氧氣體。藉此，可抑制轉爐型精煉容器的基體金屬附著 ，可防止基體金屬附著所造成的弊害於未然，而能達成鐵 良率的提昇及生產性的提昇。此外，含氧氣體、固體氧源 及石灰系脫磷用精煉劑等的助溶劑可供應至同一部位或附 近，因此可實現高效率地進行熔融生鐵及熔鋼的氧化精煉 【實施方式】 以下參照附圖來具體地說明本發明。以下所例示的噴 管是典型的例子，但各部位（噴嘴、路徑等）的形狀、尺 寸 '數目、位置等並不限定於此。亦即，爲了適當地實現 各部位的目的，可參考公知的技術而設計成符合實際使用 環境的構造。 第1圖係顯示本發明之精煉用上吹式噴管的一例之槪 略截面圖。如第1圖所示，本發明之精煉用上吹式噴管1係 包含：圓筒狀的噴管主體2、藉由熔接等連接於該噴管主 體2的下端之噴管噴嘴3、屬於噴管主體2的上端部且構成 氣體 '粉體和冷卻水的導入部（噴管主體2之與各供應設 備的連接部）之噴管頂部4。噴管主體2係包含最外管5、 外管6、中管7、分隔管8、內管9、最內管1〇之同心圓的六 -13- 201130989 種鋼管，而由六層管所構成。在銅製的噴管噴嘴3，在其 軸心部設置朝鉛垂下方之副孔噴嘴12，在該副孔噴嘴12的 周圍，設置吐出方向朝鉛垂斜下方之複數個主孔噴嘴11。 此外，在噴管主體2的側面部，在從噴管噴嘴3的前端部往 上方隔離的位置，在噴管主體2的圓周方向大致等間隔地 設置複數個二次燃燒用噴嘴13 (吐出方向朝水平或斜下方 )。在第1圖，雖是沿鉛垂方向設有二段，但亦可爲一段 或三段以上。又在從上吹式噴管1的前端部往上方隔離的 位置的側面部設置朝水平或斜下方之二次燃燒用噴嘴13是 表示，選定噴管側面部上的位置及方向（角度）而使二次 燃燒用噴嘴的噴射方向朝向精煉容器的爐壁。此外，最靠 近噴管前端部之二次燃燒用噴嘴13與噴管前端部的距離較 佳爲，考慮一般轉爐上吹式噴管噴嘴3之冷卻水路等的設 計限制，而距離噴管前端300mm以上。 主孔噴嘴11，是將吹煉用氣體（含氧氣體），或是將 固體氧源以外的助熔劑等的粉體（「精煉用助熔劑」）、 亦即石灰系脫磷用精煉劑等的粉體和作爲搬運用氣體之含 氧氣體一起，吹送至轉爐等的精煉容器（未圖示）內部之 噴嘴。副孔噴嘴12，是將鐵礦石、軋鋼鱗片（mill scale) 等的固體氧源和搬運用氣體一起吹送至精煉容器內部之噴 嘴。此外，二次燃燒用噴嘴13，是將二次燃燒用的含氧氣 體吹送至精煉容器內部空間的噴嘴。主孔噴嘴11，如第1 圖所示，其截面往前端部擴大，而採用所謂拉瓦噴嘴（ Laval Nozzle )的形狀。另一方面，副孔噴嘴12及二次燃 -14 - 201130989 燒用噴嘴1 3是形成筆直形狀’但副孔噴嘴1 2及二次燃燒用 噴嘴13也能採用拉瓦形狀。該上吹式噴管1 ’是以能在精 煉容器的內部昇降的方式’在精煉容器的上方藉由支承裝 置（未圖示）所支承。 第1圖的噴管的情況，主孔噴嘴1 1的設置孔數及口徑 等雖沒有特別的限制’但受到對上吹式噴管1之供應氣體 壓力等的限制，根據所必要的含氧氣體供應量可決定其必 然的設置孔數及口徑，因此設定在可滿足其等的範圍內。 二次燃燒用噴嘴1 3也是’其設置孔數及口徑等雖沒有特別 的限制，但按照爐形狀等而設定成可適當熔解所附著的基 體金屬之配置。在此’含氧氣體是指’氧氣（純氧氣）、 富氧空氣、氧氣和惰性氣體等的混合氣體’且其氧氣濃度 比空氣高的氣體。作爲從副孔噴嘴12吹送的固體氧源’可 使用鐵礦石的燒結礦、軋鋼鱗片、集塵粉塵、砂鐵、鐵礦 石、錳礦石等。在此的集塵粉塵，是從高爐、轉爐、燒結 過程的排氣所回收之含有FeO或Fe203的粉塵。 又在本發明，屬於一種石灰系脫磷用精煉劑之生石灰 等的助熔劑，是從主孔噴嘴1 1以含氧氣體作爲搬運用氣體 而進行吹送，同樣地，從副孔噴嘴1 2也是，將生石灰等的 助熔劑和固體氧源一起吹送亦可。當然’從副孔噴嘴1 2噴 出之流量以及從主孔噴嘴1 1噴出的流量’分別藉由獨立的 流量計（未圖示）來獨立地進行流量控制。 最外管5和外管6的間隙以及外管6和中管7的間隙，是 構成冷卻上吹式噴管1之冷卻水的流路。從設置於噴管頂 -15- 201130989 部4之供水管（未圖示）供應的冷卻水’是通過外管6和中 管7的間隙而到達噴管噴嘴3的部位’在噴管噴嘴3的部位 反轉後通過最外管5和外管6的間隙而從設置於噴管頂部4 之排水管（未圖示）排出。將供排水的路徑形成相反亦可 〇 中管7和分隔管8的間隙，是構成將含氧氣體供應給二 次燃燒用噴嘴13的第2供應路徑。從設置於噴管頂部4且連 通於中管7之含氧氣體供應管14導入中管7內部之含氧氣體 ，通過第2供應路徑到達二次燃燒用噴嘴13’而從二次燃 燒用噴嘴13噴出。但分隔管8的上端部並未到達含氧氣體 供應管Μ的部位（含氧氣體的導入部）。亦即’從含氧氣 體供應管14導入中管7內部之含氧氣體，也流入分隔管8和 內管9的間隙（如後述般，分隔管8和內管9的間隙是構成 第1供應路徑），通過此間隙而從主孔噴嘴1 1噴出。此外 ，分隔管8的下端部並未到達噴管噴嘴3的部位。亦即，雖 然通過中管7和分隔管8的間隙（換言之第2供應路徑）但 並未從二次燃燒用噴嘴13噴出之含氧氣體，是與第1供應 路徑合流而從主孔噴嘴1 1噴出。 分隔管8和內管9的間隙是構成第1供應路徑，其用來 將吹煉用的含氧氣體，或不同於固體氧源之粉體（「精煉 用助熔劑」）、例如石灰系脫磷用精煉劑等的粉體和該含 氧氣體一起，供應給主孔噴嘴11。亦即，在噴管頂部4， 使用含氧氣體作爲搬運用氣體而供應精煉用助熔劑之粉體 供應管15 (該供應管的設置部位成爲精煉用助熔劑的導入 -16- 201130989 部）是設置成連通分隔管8，又前述般之含氧氣體供應管 14 (該供應管的設置部位成爲含氧氣體導入部）是設置成 連通中管7。 而且從主孔噴嘴Π將精煉用助熔劑和吹煉用含氧氣體 一起吹送的情況，從含氧氣體供應管Μ供應的含氧氣體和 從粉體供應管15供應的粉體及含氧氣體，是合流而通過第 1供應路徑。在此情況，由於分隔管8的下端位置在比二次 燃燒用噴嘴13的設置位置更下方，通過第1供應路徑的粉 體不致流入二次燃燒用噴嘴13。亦即，分隔管8可發揮分 隔構造的功能，而防止前述精煉用助熔劑混入第2供應路 徑。 從主孔噴嘴11僅吹送吹煉用含氧氣體的情況，只要將 粉體供應管1 5停止，或從粉體供應管1 5僅供應含氧氣體即 可。 作爲精煉用助熔劑，亦即與固體氧源不同的粉體，可 適用固體氧源以外而爲了實現高效率的精煉所投入之公知 (或可預見）的固體物質全部。例如，除了前述的石灰系 脫磷用精煉劑（生石灰（CaO ) '石灰石（CaC03 )、或 白雲石（CaC03. MgC03)、脫碳熔渣、二次精煉熔渣等 )以外，還包括熔渣的原料（例如含有二氧化矽（S i 02 ) '氧化鎂之碍屑等）、滓化促進劑（含有螢石、氧化鈦、 氧化鋁等的物質等）等等。又通常，至少石灰系脫磷用精 煉劑是作爲精煉用助熔劑來供應》 最內管10的內部，是構成將固體氧源和搬運用氣體一 -17- 201130989 起供應給副孔噴嘴1 2之第3供應路徑。亦即，從設置於噴 管頂部4且連通於最內管1〇之供應管（未圖示）和搬運用 氣體一起供應至最內管1〇的內部之固體氧源’通過最內管 1 0的內部而到達副孔噴嘴1 2後，從副孔噴嘴1 2噴出。在此 ，前述供應管的設置部（未圖示）是成爲固體氧源導入部 。作爲搬運固體氧源之搬運用氣體’宜爲氧含量爲空氣以 下的氣體，較佳爲使用空氣、還原性氣體、二氧化碳氣體 、非氧化性氣體、惰性氣體當中任一種或兩種以上的氣體 〇 作爲固體氧源之搬運用氣體’是使用空氣、還原性氣 體、二氧化碳氣體、非氧化性氣體、惰性氣體的理由如下 所述。空氣，相較於從主孔噴嘴11吹送的含氧氣體其含氧 量少，又還原性氣體、二氧化碳氣體、非氧化性氣體、惰 性氣體中實質上不含氧。因此，可防止固體氧源所含之微 量的金屬鐵（metallic iron)在搬運中發生燃燒，且能防 止在搬運中因固體氧源和最內管10的接觸所產生的火花造 成最內管10的燃燒。在此，還原性氣體是指丙烷氣體等的 烴系氣體及CO氣體，非氧化性氣體是指氮氣等的無氧化能 力的氣體，惰性氣體是指Ar氣體和He氣體等的非活性氣體 〇 內管9和最內管10的間隙，在前端部的噴管噴嘴3的部 位被密封，而成爲從設置於噴管頂部4之緩衝用氣體供應 管1 6所供應的空氣、還原性氣體、二氧化碳氣體、非氧化 性氣體、惰性氣體當中任一種或兩種以上的氣體所存在之 -18- 201130989 緩衝空間。在本發明，將存在於緩衝空間之氣體稱爲「緩 衝用氣體」。 朝向該緩衝空間之緩衝用氣體的供應路徑如第2圖所 示。如第2圖所示，在設置於噴管頂部4之緩衝用氣體供應 管16，連接著具備檢測器（detector ) 20、遙控操作閥21 、撓性軟管22以及複數個手動遮斷閥23之緩衝用氣體導入 裝置19。而且，透過該緩衝用氣體導入裝置19來對緩衝空 間供應緩衝用氣體。作爲檢測器20，是配置壓力計或流量 計，或是壓力計及流量計雙方。對緩衝空間導入緩衝用氣 體的方法，可遮斷遙控操作閥21而將緩衝用氣體密封於緩 衝空間，或打開遙控操作閥2 1而使緩衝用氣體的壓力始終 作用於緩衝空間。在第2圖的例子，是構成兩個操作皆可 。此外，撓性軟管22，是構成讓上吹式噴管1上下昇降時 的餘裕。此外，在第2圖的例子，是將檢測器20設置在比 撓性軟管22更接近上吹式噴管1側，但設置在比撓性軟管 22更靠近供應側亦可，檢測器20不管設在哪個部位皆可。 但要根據緩衝空間的壓力變動來檢測出破洞的情況，必須 將檢測器20配置在比遙控操作閥2 1更靠近上吹式噴管1側 。因此，基於作業彈性的觀點，較佳爲將檢測器20配置在 比遙控操作閥2 1更靠近上吹式噴管1側。 作爲緩衝用氣體，是使用空氣、還原性氣體、二氧化 碳氣體、非氧化性氣體、惰性氣體的理由，是與作爲固體 氧源的搬運用氣體是使用該等氣體的理由相同。亦即，隨 著固體氧源的搬運，即使該固體氧源的供應路徑（亦即作 -19- 201130989 爲第3供應路徑之最內管10)產生破洞而使緩衝用氣體和 固體氧源接觸，由於是使用該等氣體作爲緩衝用氣體，可 防止固體氧源中金屬鐵的燃燒，並防止因固體氧源和最內 管10的接觸所產生的火花造成最內管10的燃燒。因此，除 了上述氣體以外，只要氧含量比空氣低的氣體都能作爲緩 衝用氣體來使用。 最內管10在精煉中發生破洞之檢測，可採用以下方式 進行。亦即，當精煉中若在最內管10發生破洞，緩衝空間 和最內管10的內部會連通，而使緩衝空間內的壓力改變， 或對緩衝空間供應之緩衝用氣體的流量改變，因此可根據 該改變來檢測破洞。具體的檢測方法可採用以下兩種方法 。其中一種方法，作爲檢測計2 0，係設置壓力計或壓力計 和流量計雙方，對緩衝空間導入緩衝用氣體後，遮斷遙控 操作閥2 1而在緩衝空間封入緩衝用氣體，精煉中藉由檢測 器20來測定緩衝空間內的壓力，藉此檢測出破洞。另一方 法，作爲檢測器20是設置流量計，打開遙控操作閥21而使 緩衝用氣體的壓力始終作用於緩衝空間，在此狀態下藉由 檢測器20來測定流量，根據有破洞時的流量改變來檢測出 破洞。 以下說明，使用上述構造之本發明的上吹式噴管1來 在轉爐實施熔融生鐵的預備脫磷處理的例子。 將本發明的上吹式噴管1配置在轉爐內之熔融生鐵的 上方既定位置，從主孔噴嘴11將作爲含氧氣體之氧氣朝熔 融生鐵浴面吹送。在此同時，從副孔噴嘴12，將固體氧源- -20- 201130989 (使用空氣、還原性氣體、二氧化碳氣體、非氧化性氣體 、惰性氣體當中任一種或兩種以上的氣體作爲搬運用氣體 )朝熔融生鐵浴面吹送。從副孔噴嘴1 2吹送的固體氧源， 是供應至與氧氣所供應的場所相同場所的熔融生鐵浴面或 其附近。在脫磷處理時，必須使用脫磷精煉用熔渣以吸收 在脫磷反應所生成的磷氧化物（P205 )，因此也將構成該 脫磷精煉用熔渣之石灰系脫磷用精煉劑投入。 作爲石灰系脫磷用精煉劑，只要是含有CaO且能達成 本發明的脫磷處理即可，其CaO含量沒有特別的限定。通 常是由CaO單獨構成，或含有50質量％以上CaO且按照需要 而含有其他成分。作爲具體的例子，可使用生石灰（CaO )、石灰石（CaC03)、或白雲石（CaC03· MgC03)， 可進一步在該等物質中混合滓化促進劑，亦即含有氧化鈦 、氧化鋁、氧化鎂的物質。此外，脫碳熔渣（ decarburization slag)及桶精煉熔渣（ladle refining slag )等，由於也是以CaO爲主成分且磷含量少，而能作爲石 灰系脫磷用精煉劑充分地利用。 在熔融生鐵浴面，氧氣與熔融生鐵浴面碰撞的場所（ 「火點」），經由氧氣與熔融生鐵中的碳發生反應而變得 高溫，供應至火點或火點附近的固體氧源會迅速地熔融， 而使熔渣中的FeO成分增加。如此，熔渣中的氧勢（ oxygen potential)上昇，亦即迅速地形成適於脫磷反應的 熔渣，即使熔渣量少，即使在高溫下，仍能進行脫磷處理 。此外’藉由將石灰系脫磷用精煉劑投入火點或火點附近 -21 - 201130989 ，可促進石灰系脫磷用精煉劑的滓化而使脫磷精煉用熔渣 提早形成，而能進一步促進脫磷反應。因此較佳爲，石灰 系脫磷用精煉劑也是透過主孔噴嘴11或主孔噴嘴11及副孔 噴嘴1 2，投入火點或火點附近。 在進行吹煉時，從二次燃燒用噴嘴13供應二次燃燒用 的氧氣，以在脫磷精煉的同時將爐體的附著基體金屬熔解 ，或防止基體金屬附著。藉此，可防止基體金屬附著所造 成的弊害於未然，可實施鐵良率的提昇及生產性的提昇。 在此情況，來自二次燃燒用噴嘴13之氧氣供應量（Q )，較佳爲來自主孔噴嘴II之氧氣供應量（Qo)之5〜3 0% 的範圍》當100()/(5〇未達5%時，二次燃燒用的氧氣過少， 二次燃燒發熱量不足而無法熔解附著基體金屬。另一方面 ，若10 0Q/Qo超過3 0%，二次燃燒發熱量過多，會促進爐 體耐火物發生熔損。 此外，若來自二次燃燒用噴嘴13之氧氣的流速過快， 而使來自二次燃燒用噴嘴13的氧氣直接到達爐壁，則不僅 附著基體金屬發生局部熔解，爐體耐火物也會發生局部熔 損。因此，在來自二次燃燒用噴嘴1 3的氧氣噴流到達爐壁 爲止的期間，讓氧氣噴流和爐內所產生的CO氣體反應而使 二次燃燒熱在爐內均一分散是重要的。 如專利文獻4所揭示，在來自二次燃燒用噴嘴13的氧 氣流速衰減至30m/秒的時點，爐內產生的CO氣體會和來 自二次燃燒用噴嘴13的氧氣反應而產生二次燃燒反應。從 二次燃燒用噴嘴1 3供應的氧氣流速爲3 0m/秒時，與二次燃 -22- 201130989 燒用噴嘴13的噴嘴出口距離X(m)可由下式（1 γ de/1000 λΤ X =-xV〇BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to oxidation refining suitable for dephosphorization treatment of molten hot metal or molten steel in a converter type refining vessel. The refining process uses a 'top lance', and further relates to a refining method using molten pig iron of the upper blowing nozzle. In the above-described blow nozzle, since the supply path of the oxygen containing gas and the supply path of the solid oxygen source such as iron oxide are separated, the oxygen-containing gas can be taken from the paths And the solid oxygen source is independently supplied to the bath surface of the molten pig iron or molten steel in the converter type refining vessel. Further, the upper blow nozzle of the present invention can supply a powder other than a solid oxygen source together with an oxygen-containing gas. Further, in the upper blow type nozzle of the present invention, the oxygen-containing gas for secondary combustion can be supplied to the furnace space of the converter type refining vessel from the side surface of the nozzle which is separated from the tip end portion of the nozzle. [Prior Art] In the steel making process in which the blast furnace is used to melt the pig iron, before the decarburization and blowing by the converter, the dephosphorization pretreatment of the molten pig iron is generally performed to melt the pig iron. The phosphorus (P) contained is mostly oxidized and removed by oxygen and solid iron oxide. In particular, in recent years, the quality requirements for steel products have been stricter than before, and it is required to further reduce the phosphorus concentration. In order to meet the quality requirements, the amount of molten pig iron to be subjected to dephosphorization treatment must be more than ever. -5-201130989 The phosphorus concentration after dephosphorization treatment must be stably lowered. On the other hand, in order to reduce the environmental impact represented by global warming, it is necessary to reduce the amount of slag discharged during the steel making process. In the preliminary dephosphorization treatment of the molten pig iron, in order to reduce the discharge amount of the slag, it is necessary to reduce the amount of the refining agent for dephosphorization (hereinafter referred to as "refraction refining agent"), and the dephosphorization refining agent is melted. A slag (referred to as "slag for dephosphorization refining") which functions as a refining agent for phosphorus oxide (P205) absorption. The main body of the dephosphorization refining agent for the preliminary dephosphorization treatment of the molten pig iron is lime. Therefore, in order to meet the above quality requirements and reduce the slag discharge amount, it is necessary to have a technology capable of maintaining the necessary dephosphorization amount in reducing the amount of lime used, that is, it is necessary to efficiently perform dephosphorization treatment with less lime usage. Technology. In the preliminary dephosphorization treatment of molten pig iron, since the lime which is not subjected to fluxing does not contribute to the dephosphorization reaction, in order to reduce the amount of lime used, it is important to promote the deuteration of the added lime. . Conventionally, as a fluxing agent (fluxing agent) for promoting the purification of slag containing lime, fluorite is known as fluorite, ore containing calcium carbonate as a main component. Fluorite is also used in the dephosphorization treatment. However, in recent years, as environmental regulations have become more stringent, the use of fluorine-containing fluxes has begun to be limited. Therefore, the means for promoting the dephosphorization reaction of lime without using fluorite has been explored, and there are many proposals. One of the means proposed is to supply the lime-based dephosphorization refining agent to the same place or close to the place where the oxygen source such as oxygen-containing gas and iron oxide is supplied, -6-201130989. This technique is intended to promote the desulfurization of a lime-based dephosphorization refining agent, and to perform dephosphorization treatment efficiently under a rare lime-based dephosphorization refining agent. For example, Patent Document 1 proposes a preliminary dephosphorization treatment method for molten pig iron by adding a lime-based dephosphorization refining agent and an endothermic substance to a place where oxygen is supplied. Further, Patent Document 2 discloses an up-blowing nozzle which is suitable for adding a lime-based dephosphorization refining agent to a fire spot (hot spot) region formed on the surface of molten pig iron by supplying oxygen. The upper blow nozzle is a powder blowing nozzle for supplying a lime-based dephosphorization refining agent at a position of a shaft center, and a plurality of nozzles for supplying air gas are disposed around the shaft to form a four-layer tube. structure. Further, Patent Document 3 proposes a five-layer tube structure refining upper-blowing nozzle in which a supply path for supplying a lime-based dephosphorization refining agent together with an oxygen-containing gas is separated from an iron oxide supply path, and These paths supply an oxygen-containing gas, a lime-based dephosphorization refining agent, and iron oxide to the molten pig iron bath surface to perform oxidative refining such as dephosphorization treatment on the molten pig iron. Further, in Patent Document 3, it is proposed to detect a hole in the iron oxide supply path by providing a buffer space around the iron oxide supply path. However, since the dephosphorization reaction of the molten iron is advantageous as the temperature is lower, the dephosphorization treatment is carried out at a molten pig iron stage of about 1,300 to 1,400 °C. For example, Patent Document 1 and Patent Document 2 disclose an implementation temperature of 1300 ° C weak to about 1350 ° C. Further, recently, since the free space (free space, the space other than the static molten iron in the furnace) is increased, strong stirring can be performed. Therefore, the preliminary dephosphorization treatment of the molten pig iron is generally carried out in the converter type refining container 201130989. However, at a low temperature, the molten pig iron scattered in the dephosphorization treatment adheres to the side wall of the converter type refining vessel, the furnace mouth, and the like to cause accumulation of the base metal, resulting in a decrease in the yield of the molten pig iron, and the base metal is Removal of work can result in reduced productivity. The problem of adhesion of the base metal is not limited to the preliminary dephosphorization treatment of the molten pig iron, and decarburization refining of the molten pig iron in the converter also causes problems. That is, in the decarburization refining of the molten pig iron in the converter, due to the spitting and slopping of the base metal during the blowing, the base metal is deposited on the inner wall of the converter and the furnace mouth, and There is a problem that molten pig iron and iron filings are hindered when they are placed in the furnace. In order to solve the problem of adhesion of the base metal, many means have been proposed. For example, Patent Document 4 discloses a refining method in which the side surface of the blow nozzle is separated from the front end portion of the upper blow nozzle (having a main orifice nozzle at the front end portion) at a predetermined interval, and is disposed horizontally or downwardly. The combustion nozzle 'supply oxygen from the main orifice nozzle to oxidize and refine the molten pig iron or molten steel in the converter while supplying oxygen from the secondary combustion nozzle to melt the base metal adhering to the converter. [Patent Document 1] Japanese Patent Laid-Open Publication No. JP-A-2006-336033 (Patent Document 3) JP-A-2008-208407 (Patent Document 4) 〇8_138271号 [Summary of the Invention] Now, in the steel making process, the pre-dephosphorization treatment containing molten pig iron is used as an oxygen source, and is a gas oxygen source such as an oxygen-containing gas and a fixed oxygen such as iron oxide. The oxidative refining method in which the source is added to the same portion or in the vicinity is already mainstream. In this case, the gas oxygen source is used as a carrier gas, and a flux such as a dephosphorization refining agent is transported together with a gas oxygen source (see Patent Document 3) to introduce a flux into the gas. A refining method of the addition position of the oxygen source has also been carried out. Further, in the case of carrying out such refining, the base metal attached to the inner wall of the converter-type refining vessel and the furnace base is applied by a gas oxygen source supplied from the nozzle for secondary combustion of the side of the upper-blowing nozzle. It is extremely important to melt, based on the viewpoint of ensuring iron yield and productivity. As a result of performing the above-described refining upper blow nozzle, as a result of verifying the above-described conventional blow-up nozzles of various shapes, no upper blow nozzle can be used. Further, even if the above-described conventional upper-blowing nozzles are combined, a satisfactory upper-blowing nozzle cannot be obtained. For example, even if it is connected to the oxygen-containing gas supply path of the upper-blowing nozzle of Patent Document 3, the secondary combustion nozzle of Patent Document 4 is provided, and if the flux and the oxygen-containing gas are carried together through the oxygen-containing gas supply path, There is a problem that the nozzle for secondary combustion is blocked by the flux. The present invention has been developed in view of the above circumstances, and an object thereof is to provide an upper blow-off nozzle for refining, which is a oxidized fine iron of molten pig iron or molten steel in a converter type refining vessel like a preliminary dephosphorization treatment of molten pig iron. Refining B Temple can efficiently perform oxidative refining, and at the same time, it can efficiently melt the base metal attached to the converter type and the container. The object of the present invention is to provide a method for refining molten pig iron using the above-described refining upper nozzle. -9 - 201130989 The gist of the present invention for solving the above problems is as follows: (1) - a refining upper blow type spray The tube is an oxidized fine nozzle made of molten pig iron or molten steel of a refining vessel, and is characterized in that: a main orifice nozzle and a solid orifice nozzle for blowing under the front of the upper blow nozzle or obliquely downward, a side surface portion of the bit that is isolated upward from the front end portion has a second horizontally or obliquely downward direction, and a first supply path third supply path is provided inside the upper blow nozzle; the first supply path is Passing the different body and the oxygen-containing gas for blowing together through the main hole, the oxygen-containing gas for blowing is supplied through the main hole spray supply path, and is supplied by a general-purpose nozzle for oxygen-containing gas for secondary combustion; In the third supply path, the powder and the carrier gas are supplied through the sub-hole nozzle, and the first supply path includes a solid (hereinafter also referred to as "refining flux") introduced into the flux introduction unit. And including The gas introduction portion into the passage. The flux introduction portion for refining may be an introduction portion into which the fine gas is introduced together, and the carrier gas is relatively high. Of course, it is also possible to adopt a structure in which the refining flux and the introduction-introducing portion are introduced (i.e., the refining flux is mixed into a ratio portion to be supplied through the main orifice nozzle). At the time of the work, the refining is used for the upper end of the refining for blowing in the converter, and the nozzle for the blown nozzle for the lead gas source is blown, and the second supply path is A powder nozzle of a solid oxygen source is supplied, or I is supplied; and the second solid combustion source of the secondary combustion body is used. The oxygen source for the refining of different powder paths of the body oxygen source is used for the fluxing of the oxygen-containing gas to be used for the refining, and the oxygen-containing oxygen gas is also supplied from the same and the oxygen-containing gas in advance, and then the introduction of the flux is stopped. 10-201130989, but only the oxygen-containing gas may be introduced into the first supply path from the oxygen-containing gas introduction unit. Further, the second supply path includes an oxygen-containing gas introduction unit that introduces an oxygen-containing gas into the path. Further, the third supply path includes a solid oxygen source introduction unit that introduces a solid oxygen source and a carrier gas into the path. Further, during the operation, the supply of the solid oxygen source is stopped, and only the carrier gas may be introduced into the third supply path from the introduction portion. Here, the first supply path and the second supply path may be shared oxygen-containing gas introduction portions. In this case, a partition structure for preventing the above-mentioned refining flux from entering the second supply path is provided. (2) In the above-described refinery upper blow nozzle, the end of the second supply path is closed, and the oxygen-containing gas supplied from the second supply path is not supplied to the first supply path and the third supply. The path merges. The end of the second supply path is a part of the path (3) which is further forward (the nozzle tip end side) than the secondary combustion nozzle closest to the nozzle tip end portion, and is used for the refining described in the above (2). In the upper blow nozzle, any one or two or more kinds of reducing gas, carbon dioxide gas, non-oxidizing gas, and inert gas are supplied to the second supply path. In other words, the second supply path includes an introduction unit that introduces any one or more of the above gases into the path. Of course, it is also possible to adopt a structure in which the gas is introduced from the same introduction portion as the oxygen-containing gas. (4) In the above-described third embodiment, the buffering space is provided around the third supply path, and the air is present in the buffer space of the -11 - 201130989. Any one or two or more of a reducing gas, a carbon dioxide gas, and an inert gas may be caused by a change in gas pressure or flow rate in the buffer space. (5) In the fine nozzle according to any one of the above (1) to (4), the first supply path and the second supply path and valley supply path are arranged on a concentric circle. (6) A method for refining molten pig iron, characterized in that the ash-based dephosphorization refining agent is added to the iron produced in the converter-type refining vessel, and the added dephosphorization refining agent is converted into molten iron to perform oxidative refining, and is used. The above-described (1) to (5) refining upper-blowing nozzles are supplied to the molten pig iron bath surface from the first supply path, and are supplied from the third supply path together with the carrier gas to the blowing. The molten iron bath surface is melted and further supplied to the furnace space of the converter-type refining vessel from the second supply path to be oxidized: preferably, the lime-based dephosphorization refining agent is from the first The supply path is supplied to the aforementioned molten pig iron. According to the invention, the up-blowing nozzle has yellow, a second supply path, and a third supply path therein; and the first supply path is a powder oxygen-containing gas different from the solid oxygen source, such as a refining agent for dephosphorization of the first supply path. Cooperating through the main orifice nozzle or supplying the blowing gas through the main orifice nozzle; the second supply path, the burning oxygen-containing gas is supplied through the secondary combustion nozzle; the gas, the non-oxygen gas, the root It is detected that the first blowing type I and the third aspect are: the molten slag contained in the stone, and the oxygen for refining in either of the melting is used to knead the combustion oxygen in the vicinity of the solid oxygen source site. At least a part of the supply path of the 5 1 is that the oxygen used for the refining of the stone and the blowing is to re-burn the third supply -12-201130989 path, and the powdery solid oxygen source and the conveying gas are passed together. The secondary orifice nozzle is supplied. Therefore, even if the powder is supplied from the first supply path and the third supply path, only the oxygen-containing gas is ejected from the secondary combustion nozzle, so that the secondary combustion nozzle can stably inject the secondary combustion for a long period of time without clogging. Oxygen-containing gas. Thereby, the adhesion of the base metal of the converter type refining container can be suppressed, and the disadvantages caused by the adhesion of the base metal can be prevented, and the improvement of the iron yield and the improvement of the productivity can be achieved. Further, since the co-solvent such as an oxygen-containing gas, a solid oxygen source, and a lime-based dephosphorization refining agent can be supplied to the same portion or in the vicinity, oxidative refining of the molten pig iron and the molten steel can be efficiently performed. [Embodiment] The invention will be specifically described in the accompanying drawings. The nozzle exemplified below is a typical example, but the shape, the size 'number, the position, and the like of each part (nozzle, path, etc.) are not limited thereto. That is, in order to properly achieve the purpose of each part, it is possible to design a structure conforming to the actual use environment with reference to a known technique. Fig. 1 is a schematic cross-sectional view showing an example of the upper blow nozzle of the present invention. As shown in Fig. 1, the upper blow nozzle 1 for refining according to the present invention includes a cylindrical nozzle body 2, and a nozzle nozzle 3 connected to the lower end of the nozzle body 2 by welding or the like. The upper end portion of the nozzle body 2 constitutes a nozzle top portion 4 of a gas 'powder and a leading portion for cooling water (a connection portion of the nozzle body 2 to each supply device). The nozzle body 2 is a six-third-201130989 type steel pipe including the outermost pipe 5, the outer pipe 6, the middle pipe 7, the dividing pipe 8, the inner pipe 9, and the innermost pipe 1〇, and the six-layer pipe Composition. In the nozzle nozzle 3 made of copper, a sub-hole nozzle 12 which is vertically downward is provided in the axial center portion, and a plurality of main-hole nozzles 11 whose discharge direction is vertically downward is provided around the sub-hole nozzle 12. In the side surface portion of the nozzle body 2, a plurality of secondary combustion nozzles 13 are provided at substantially equal intervals in the circumferential direction of the nozzle body 2 at a position separated upward from the tip end portion of the nozzle body 3 (discharge direction) Towards horizontal or obliquely below). In Fig. 1, although two stages are provided in the vertical direction, they may be one or three or more stages. Further, the secondary combustion nozzle 13 that is disposed horizontally or obliquely downward from the side surface portion that is separated upward from the front end portion of the upper blow nozzle 1 is a position and a direction (angle) on the side surface portion of the nozzle. The injection direction of the secondary combustion nozzle is directed toward the furnace wall of the refining vessel. Further, the distance between the secondary combustion nozzle 13 closest to the tip end portion of the nozzle and the tip end portion of the nozzle is preferably set in consideration of the design restriction of the cooling water passage of the above-described upper blow nozzle 3 of the converter, and 300 mm from the tip end of the nozzle. the above. The main orifice nozzle 11 is a powder for blowing gas (oxygen-containing gas) or a flux other than a solid oxygen source ("refining flux"), that is, a lime-based dephosphorization refining agent. The powder is blown to a nozzle inside a refining vessel (not shown) such as a converter together with an oxygen-containing gas as a carrier gas. The sub-hole nozzle 12 is a nozzle that blows a solid oxygen source such as iron ore or a mill scale together with a carrier gas to the inside of the refining vessel. Further, the secondary combustion nozzle 13 is a nozzle that blows an oxygen-containing gas for secondary combustion to the internal space of the refining vessel. As shown in Fig. 1, the main orifice nozzle 11 has a cross section that is enlarged toward the front end portion and has a shape of a so-called laval nozzle. On the other hand, the sub-hole nozzle 12 and the secondary combustion -14 - 201130989 firing nozzle 13 are formed in a straight shape. However, the sub-hole nozzle 12 and the secondary combustion nozzle 13 can also be in the shape of a puller. The upper blow nozzle 1' is supported by a support device (not shown) above the refining container in such a manner that it can be lifted and lowered inside the refining container. In the case of the nozzle of the first embodiment, the number of holes and the diameter of the main orifice nozzle 1 are not particularly limited, but the pressure of the supply gas of the upper blow nozzle 1 is limited, and the oxygen is required according to the necessity. The gas supply amount can determine the number of holes and the diameter of the holes to be set, and therefore is set within a range that can satisfy them. The secondary combustion nozzles 13 are not particularly limited as long as the number of the holes to be provided, the diameter, and the like. However, the arrangement of the base metal to which the adhesion is applied is appropriately set in accordance with the shape of the furnace or the like. Here, the 'oxygen-containing gas' means a gas of a mixture of oxygen (pure oxygen), oxygen-enriched air, oxygen, and an inert gas, and whose oxygen concentration is higher than that of air. As the solid oxygen source blown from the sub-hole nozzle 12, sinter of iron ore, rolled scale, dust collecting dust, sand iron, iron ore, manganese ore, or the like can be used. The dust collecting dust here is dust containing FeO or Fe203 recovered from the exhaust of the blast furnace, the converter, and the sintering process. Further, in the present invention, a flux such as quicklime, which is a lime-based dephosphorization refining agent, is blown from the main orifice nozzle 1 1 with an oxygen-containing gas as a carrier gas, and similarly, the sub-hole nozzle 1 2 is also used. The flux such as quicklime may be blown together with the solid oxygen source. Of course, the flow rate discharged from the sub-hole nozzle 12 and the flow rate ejected from the main orifice nozzle 11 are independently controlled by flow rate by an independent flow meter (not shown). The gap between the outermost tube 5 and the outer tube 6 and the gap between the outer tube 6 and the middle tube 7 are flow paths constituting the cooling water for cooling the upper-blowing nozzle 1. The cooling water supplied from the water supply pipe (not shown) provided at the top of the nozzle -15-201130989 is the portion passing through the gap between the outer pipe 6 and the intermediate pipe 7 to the nozzle nozzle 3' at the nozzle 3 After the portion is reversed, it is discharged from the drain pipe (not shown) provided in the top portion 4 of the nozzle through the gap between the outermost tube 5 and the outer tube 6. The path of the water supply and drainage may be reversed. The gap between the middle pipe 7 and the partition pipe 8 constitutes a second supply path for supplying the oxygen-containing gas to the secondary combustion nozzle 13. The oxygen-containing gas introduced into the middle pipe 7 from the oxygen-containing gas supply pipe 14 provided in the nozzle top portion 4 and communicating with the intermediate pipe 7 passes through the second supply passage to the secondary combustion nozzle 13'. 13 spouted. However, the upper end portion of the partition pipe 8 does not reach the portion (the introduction portion of the oxygen-containing gas) of the oxygen-containing gas supply pipe. That is, the oxygen-containing gas introduced into the middle pipe 7 from the oxygen-containing gas supply pipe 14 also flows into the gap between the partition pipe 8 and the inner pipe 9. (As will be described later, the gap between the partition pipe 8 and the inner pipe 9 constitutes the first supply. The path is ejected from the main orifice nozzle 11 through this gap. Further, the lower end portion of the partition pipe 8 does not reach the portion of the nozzle nozzle 3. In other words, the oxygen-containing gas that has not been ejected from the secondary combustion nozzle 13 through the gap between the intermediate pipe 7 and the partition pipe 8 (in other words, the second supply path) merges with the first supply path and passes through the main orifice nozzle 1 . 1 spout. The gap between the dividing pipe 8 and the inner pipe 9 constitutes a first supply path for the oxygen-containing gas for blowing, or a powder different from the solid oxygen source ("refining flux"), such as lime. Phosphorus such as a refining agent is supplied to the main orifice nozzle 11 together with the oxygen-containing gas. In other words, in the nozzle top portion 4, the powder supply pipe 15 for supplying the refining flux using the oxygen-containing gas as the carrier gas (the portion where the supply pipe is installed is the introduction of the refining flux - 16-201130989) is It is provided so as to communicate with the partition pipe 8, and the above-described oxygen-containing gas supply pipe 14 (the portion where the supply pipe is provided is an oxygen-containing gas introduction portion) is provided to communicate with the intermediate pipe 7. Further, in the case where the refining flux and the oxygen-containing gas for blowing are blown together from the main orifice nozzle, the oxygen-containing gas supplied from the oxygen-containing gas supply pipe and the powder and oxygen-containing gas supplied from the powder supply pipe 15 are supplied. , is the first supply path through the merge. In this case, since the lower end position of the partition pipe 8 is lower than the installation position of the secondary combustion nozzle 13, the powder passing through the first supply path does not flow into the secondary combustion nozzle 13. That is, the partition pipe 8 can function as a partition structure to prevent the above-mentioned refining flux from being mixed into the second supply path. When only the oxygen-containing gas for blowing is blown from the main orifice nozzle 11, the powder supply pipe 15 may be stopped, or only the oxygen-containing gas may be supplied from the powder supply pipe 15. As the flux for refining, that is, a powder different from the solid oxygen source, it is possible to apply all of the known (or foreseeable) solid substances to be used in order to achieve high-efficiency refining other than the solid oxygen source. For example, in addition to the aforementioned lime-based dephosphorization refining agent (lime (CaO) 'limestone (CaC03), or dolomite (CaC03. MgC03), decarburization slag, secondary refining slag, etc.), slag is also included Raw materials (for example, containing cerium oxide (S i 02 ) 'magnesium oxide, etc.), sputum promoters (including fluorite, titanium oxide, aluminum oxide, etc.) and the like. In addition, at least the lime-based dephosphorization refining agent is supplied as a refining flux to the inside of the innermost tube 10, and is configured to supply a solid oxygen source and a carrier gas to the sub-hole nozzle 1 - 201130989. The third supply path. That is, the solid oxygen source 'supplied from the supply pipe (not shown) provided in the top portion 4 of the nozzle and communicating with the innermost pipe 1 to the innermost pipe 1 通过 passes through the innermost pipe 1 After the inside of 0 reaches the sub-hole nozzle 12, it is ejected from the sub-hole nozzle 12. Here, the installation portion (not shown) of the supply pipe is a solid oxygen source introduction portion. The carrier gas for transporting the solid oxygen source is preferably a gas having an oxygen content of not more than air, and preferably one or two or more gases using air, a reducing gas, a carbon dioxide gas, a non-oxidizing gas, and an inert gas. The reason why the carrier gas used as the solid oxygen source is air, a reducing gas, a carbon dioxide gas, a non-oxidizing gas, or an inert gas is as follows. The air contains less oxygen than the oxygen-containing gas blown from the main orifice nozzle 11, and the reducing gas, the carbon dioxide gas, the non-oxidizing gas, and the inert gas substantially do not contain oxygen. Therefore, it is possible to prevent the trace amount of metallic iron contained in the solid oxygen source from being burned during transportation, and to prevent the innermost tube 10 from being caused by the spark generated by the contact of the solid oxygen source and the innermost tube 10 during transportation. Burning. Here, the reducing gas means a hydrocarbon-based gas such as a propane gas or a CO gas, the non-oxidizing gas means a non-oxidizing gas such as nitrogen, and the inert gas means an inert gas such as an Ar gas or a He gas. The gap between the tube 9 and the innermost tube 10 is sealed at the portion of the nozzle nozzle 3 at the tip end portion, and is supplied with air, reducing gas, carbon dioxide supplied from the buffer gas supply pipe 16 provided at the top portion 4 of the nozzle. -18- 201130989 buffer space exists for any one or two or more gases including non-oxidizing gas and inert gas. In the present invention, the gas existing in the buffer space is referred to as "buffer gas". The supply path of the buffer gas toward the buffer space is as shown in Fig. 2. As shown in Fig. 2, a buffer gas supply pipe 16 provided at the top portion 4 of the nozzle is connected to a detector 20, a remote control valve 21, a flexible hose 22, and a plurality of manual shutoff valves 23. The gas introduction device 19 for buffering. Further, the buffer gas is supplied to the buffer space through the buffer gas introducing device 19. As the detector 20, a pressure gauge or a flow meter or a pressure gauge and a flow meter are disposed. The method of introducing the buffer gas into the buffer space can block the remote control valve 21 to seal the buffer gas in the buffer space, or open the remote operation valve 21 to always apply the pressure of the buffer gas to the buffer space. In the example of Fig. 2, it is possible to construct both operations. Further, the flexible hose 22 is configured to allow the upper blow nozzle 1 to move up and down. Further, in the example of Fig. 2, the detector 20 is disposed closer to the upper blow nozzle 1 than the flexible hose 22, but may be disposed closer to the supply side than the flexible hose 22, and the detector may be provided. 20 No matter which part is located. However, it is necessary to detect the hole according to the pressure fluctuation of the buffer space, and it is necessary to arrange the detector 20 closer to the upper blow nozzle 1 than the remote control valve 21. Therefore, from the viewpoint of work elasticity, it is preferable to arrange the detector 20 closer to the upper blow nozzle 1 than the remote control valve 21. The gas for buffering is the reason that air, a reducing gas, a carbon dioxide gas, a non-oxidizing gas, or an inert gas is used, and the reason why the gas for transportation as a solid oxygen source is used is the same. That is, with the transportation of the solid oxygen source, even if the supply path of the solid oxygen source (that is, the innermost tube 10 of the third supply path is -19-201130989), a hole is generated to make the buffer gas and the solid oxygen source. In the contact, since the gas is used as the buffer gas, the combustion of the metal iron in the solid oxygen source can be prevented, and the combustion of the innermost tube 10 due to the spark generated by the contact between the solid oxygen source and the innermost tube 10 can be prevented. Therefore, in addition to the above gases, a gas having a lower oxygen content than air can be used as a buffer gas. The detection of the occurrence of holes in the innermost tube 10 during refining can be carried out in the following manner. That is, when a hole is formed in the innermost tube 10 during refining, the buffer space and the innermost tube 10 communicate with each other, and the pressure in the buffer space is changed, or the flow rate of the buffer gas supplied to the buffer space is changed. Therefore, the hole can be detected based on the change. The following two methods can be used for the specific detection method. In one of the methods, as the detector 20, a pressure gauge, a pressure gauge, and a flowmeter are provided, and after the buffer gas is introduced into the buffer space, the remote control valve 21 is blocked, and the buffer gas is sealed in the buffer space. The pressure in the buffer space is measured by the detector 20, thereby detecting a hole. In another method, as the detector 20, a flow meter is provided, and the remote control valve 21 is opened to constantly apply the pressure of the buffer gas to the buffer space. In this state, the flow rate is measured by the detector 20, depending on the presence of a hole. The flow changes to detect a hole. Hereinafter, an example in which the upper blown nozzle 1 of the present invention having the above-described configuration is used to perform preliminary dephosphorization treatment of molten pig iron in a converter will be described. The upper blow nozzle 1 of the present invention is placed at a predetermined position above the molten pig iron in the converter, and oxygen as an oxygen-containing gas is blown from the main orifice nozzle 11 toward the molten pig iron bath surface. At the same time, from the auxiliary orifice nozzle 12, a solid oxygen source - -20 - 201130989 (using air, reducing gas, carbon dioxide gas, non-oxidizing gas, inert gas, or two or more gases as a carrier gas) ) Blowing toward the molten iron bath surface. The solid oxygen source blown from the sub-hole nozzle 12 is supplied to or near the molten pig iron bath surface in the same place as the place where oxygen is supplied. In the dephosphorization treatment, it is necessary to use the slag for dephosphorization refining to absorb the phosphorus oxide (P205) produced by the dephosphorization reaction, and therefore the lime-based dephosphorization refining agent constituting the dephosphorization refining slag is also put. . The lime-based dephosphorization refining agent is not particularly limited as long as it contains CaO and can achieve the dephosphorization treatment of the present invention. It is usually composed of CaO alone or contains 50% by mass or more of CaO and contains other components as needed. As a specific example, quicklime (CaO), limestone (CaC03), or dolomite (CaC03·MgC03) may be used, and further, a cerium promoter may be mixed in the materials, that is, containing titanium oxide, aluminum oxide, or magnesium oxide. Substance. In addition, decarburization slag and ladle refining slag are also used as a refining agent for dephosphorization of stone ash, because CaO is mainly contained and the phosphorus content is small. On the molten pig iron bath surface, where the oxygen collides with the molten pig iron bath surface ("fire point"), it reacts with carbon in the molten pig iron to become high temperature, and is supplied to a solid oxygen source near the fire point or the fire point. Melt rapidly, and the FeO component in the slag is increased. As a result, the oxygen potential in the slag rises, that is, the slag suitable for the dephosphorization reaction is rapidly formed, and even if the amount of slag is small, the dephosphorization treatment can be performed even at a high temperature. In addition, by using a refining agent for dephosphorization of lime-based dephosphorization, it is possible to promote the desulfurization refining agent to form an anti-desulfurization refining agent for lime dephosphorization, and to further form the dephosphorization refining slag. Promote dephosphorization reaction. Therefore, it is preferable that the lime-based dephosphorization refining agent is also passed through the main orifice nozzle 11 or the main orifice nozzle 11 and the sub-hole nozzle 12, and is placed near the fire point or the fire point. At the time of performing the blowing, oxygen for secondary combustion is supplied from the secondary combustion nozzle 13 to melt the adhering base metal of the furnace body or prevent the base metal from adhering while dephosphorization refining. Thereby, it is possible to prevent the defects caused by the adhesion of the base metal, and it is possible to improve the iron yield and improve the productivity. In this case, the oxygen supply amount (Q) from the secondary combustion nozzle 13 is preferably in the range of 5 to 30% of the oxygen supply amount (Qo) from the main orifice nozzle II" when 100 () / (5) When the enthalpy is less than 5%, the oxygen for secondary combustion is too small, and the secondary combustion heat is insufficient to melt the attached base metal. On the other hand, if 10 0Q/Qo exceeds 30%, the secondary combustion generates too much heat. In addition, if the flow rate of the oxygen from the secondary combustion nozzle 13 is too fast, and the oxygen from the secondary combustion nozzle 13 reaches the furnace wall directly, not only local melting of the attached base metal occurs. The furnace refractory is also partially melted. Therefore, during the period from when the oxygen jet from the secondary combustion nozzle 13 reaches the furnace wall, the oxygen gas jet reacts with the CO gas generated in the furnace to cause secondary combustion. It is important that the heat is uniformly dispersed in the furnace. As disclosed in Patent Document 4, when the oxygen flow rate from the secondary combustion nozzle 13 is attenuated to 30 m/sec, the CO gas generated in the furnace and the nozzle from the secondary combustion are 13 oxygen reacts to produce twice The combustion reaction. When the oxygen flow rate supplied from the secondary combustion nozzle 13 is 30 m/sec, the nozzle exit distance X (m) from the secondary combustion-22-201130989 firing nozzle 13 can be expressed by the following formula (1 γ de / 1000 λΤ X =-xV〇
6〇xC 式（1 )中，V 0 :二次燃燒用噴嘴的出口之 的流速（m/秒），de :二次燃燒用噴嘴的出口 ί » 0 = 0.016 + 0.19/ ( P〇-Pe ) ，P〇:二次燃燒用噴 壓表示之氧背壓（kgf/cm2) ，Pe:轉爐型精煉容 對壓表示之環境氣壓（kgf/cm2)。 只要以該距離X未到達爐壁之適當範圍來進 噴管的設計及吹煉條件的控制，即可避免局部發 屬熔解和爐壁耐火物的熔損，而使二次燃燒反應 散於爐內。 又第1圖所示的上吹式噴管1，分隔管8的下 到達噴管噴嘴3的部位，第2供應路徑是開口於負 徑。因此，從二次燃燒用噴嘴13噴出之含氧氣體 取決於主孔噴嘴11的總截面積和二次燃燒用噴嘴 面積的比，而無法獨立地控制來自二次燃燒用噴 出量。亦即，從含氧氣體供應管14及粉體供應管 含氧氣體的總量，是按照兩者的截面積比而分配 善此情況而進行更高精度的吹煉控制，也能將二 的含氧氣體流量實施獨立地控制。但在此情況， 吹式噴管的內部構造改變成與第1圖所示的上吹5 同的構造。 求出。 氧氣噴流 S ( mm ) 嘴的絕對 器內的絕 行上吹式 生基體金 熱均一分 端部尙未 i 1供應路 流量，是 1 3的總截 嘴1 3的噴 1 5供應的 。爲了改 次燃燒用 必須將上 ζ噴管1不 -23- 201130989 第3圖係顯示，能將二次燃燒用的含氧氣體流量與吹 煉用含氧氣體獨立地控制之上吹式噴管的例子。 在第3圖所示的上吹式噴管1A’分隔管8的下端到達噴 管噴嘴3的部位，在噴管噴嘴3的部位，中管7和分隔管8的 間隙（亦即第2供應路徑）是密封的。此外，在噴管頂部4 ，分隔管8的上端是位於比中管7的上端位置更上方’在中 管7和分隔管8之間設置密閉用的密封材而將第2供應路徑 密封。而且，在中管7連通著含氧氣體供應管18 (該供應 管的設置部成爲含氧氣體導入部）。亦即，從含氧氣體供 應管18供應至中管7內部的含氧氣體，通過中管7和分隔管 8的間隙（亦即第2供應路徑），而從二次燃燒用噴嘴1 3噴 出。 另一方面，在噴管頂部4，在分隔管8連通著含氧氣體 及粉體供應管17 (該供應管的設置部是構成精煉用熔渣導 入部兼含氧氣體導入部）。而且，從含氧氣體及粉體供應 管17朝分隔管8內部供應之吹煉用的含氧氣體、或是以含 氧氣體作爲搬運用氣體之精煉用熔渣，通過分隔管8和內 管9的間隙（亦即第1供應路徑）而從主孔噴嘴1 1噴出。在 從主孔噴嘴11僅吹送含氧氣體的情況，是從含氧氣體及粉 體供應管1 7僅供應含氧氣體；在從主孔噴嘴1 1吹送粉體（ 以含氧氣體作爲搬運用氣體）的情況，是從含氧氣體及粉 體供應管17供應含氧氣體及粉體。上吹式噴管1A’其他構 造是與第1圖所示的上吹式噴管1相同，對相同的部分是用 同一符號表示，而省略其說明。此外，使用該上吹式噴管 -24- 201130989 1A之熔融生鐵的預備脫磷處理，也是按照使用上吹式噴管 1的情況來進行即可。 又依吹煉的狀況，會有不須通過第2供應路徑而從二 次燃燒用噴嘴1 3噴出氧氣的情況。在此情況，在第3圖所 示的上吹式噴管1Α，爲了防止二次燃燒用噴嘴13堵塞而可 從第2供應路徑供應還原性氣體、二氧化碳氣體、非氧化 性氣體、惰性氣體當中之任一種或兩種以上的氣體。 如此般，依據本發明，上吹式噴管1、1 Α係在內部具 備第1供應路徑、第2供應路徑及第3供應路徑。該第1供應 路徑，是將不同於固體氧源的粉體（石灰系脫磷用精煉劑 等）和吹煉用的含氧氣體一起通過主孔噴嘴1 1來供應，或 是將吹煉用的含氧氣體通過主孔噴嘴11來供應；該第2供 應路徑，是將二次燃燒用的含氧氣體通過二次燃燒用噴嘴 1 3來供應；該第3供應路徑，是將粉體狀的固體氧源和搬 運用氣體一起通過副孔噴嘴12來供應。因此，即使從第1 供應路徑及第3供應路徑供應粉體，從二次燃燒用噴嘴1 3 僅噴射出含氧氣體，因此二次燃燒用噴嘴13能不發生堵塞 而長期間穩定地噴射二次燃燒用含氧氣體。藉此，可抑制 轉爐型精煉容器的基體金屬附著，可防止基體金屬附著所 造成的弊害於未然。 〔實施例〕 〔實施例1〕 從高爐送出之熔融生鐵，按照需要在高爐爐床進行脫 -25- 201130989 矽處理後，搬運至容量300噸的轉爐，在該轉爐使用第1圖 所示的上吹式噴管實施合計四次預備脫磷處理（本發明例 1 ~4 )。主孔噴嘴是在同心圓上均等地配置四個。此外， 二次燃燒用噴嘴，是在圓周上均等地配設上下各八個，二 次燃燒用噴嘴和上吹式噴管的夾角0 (°)設定成，在來 自二次燃燒用噴嘴的氧噴流流速爲3 0m/秒時，與二次燃燒 用噴嘴13的噴嘴出口之距離X(m)滿足下式（2)。 0_10<^^0.75…（2 ) Η 在此，X爲根據式（1 )所決定的與二次燃燒用噴嘴的 噴嘴出口的距離（m) ，Η爲從上吹式噴管中心至轉爐爐 壁在水平方向上的距離（m)。此外，角度0，是二次燃 燒用噴嘴的中心線和上吹式噴管的中心線的夾角，是以鉛 垂方向（=0°)爲基準（〇°<0 $90°)。因此，Xsin0表示 從二次燃燒用噴嘴起算之水平方向上的噴流到達距離（m )。 脫磷處理前的熔融生鐵的磷濃度統一爲0.12質量％， 脫磷處理後的熔融生鐵之磷濃度目標爲0.020質量％以下， 鐵良率目標爲98%以上。鐵良率（η)，是相對於裝入轉 爐內之熔融生鐵的質量（W〇 )和鐵屑質量（Ws )的總質 量（W〇 + Ws )，將脫磷處理後送出的熔融生鐵的質量（w )用百分率表示（n = ioow/(w〇+ws))的數値。 脫磷處理’是從含氧氣體供應管14供應氧氣，從粉體 -26- 201130989 供應管15以氧氣作爲搬運用氣體而供應生石灰粉（平均粒 徑1 mm以下），從最內管的內部（第3供應路徑）以氮氣 作爲搬運用氣體而供應粉體的固體氧源。在此情況，第1 供應路徑是構成氧氣和生石灰粉的供應路徑，第2供應路 徑是構成氧氣的供應路徑。 有別於上吹式噴管，從設置於轉爐爐上之料斗也朝爐 內投入塊狀的生石灰（從上吹式噴管之生石灰投入量：從 爐上料斗的生石灰投入量=8:2)。但作爲脫磷用精煉劑 ，並未使用CaF2等的氟化物而實施脫磷處理。此外，從轉 爐爐底的風口（ tuyere )，將作爲攬拌用氣體之氮氣以熔 融生鐵每噸0.03〜0.30Nm3/分的流量吹入。 從主孔噴嘴及二次燃燒用噴嘴供應之氧氣流量爲熔融 生鐵每噸0.6~2.5Nm3 /分。氧氣的單位用量，脫砂所需的氧 除外爲12Nm3/t。二次燃燒用噴嘴的氧氣流量（Q)相對於 主孔噴嘴的氧氣流量（Q〇 )，亦即1〇〇Q/Q0爲6%。作爲固 體氧源，可使用粉狀的鐵礦石（平均粒度50//m)、砂鐵 (平均粒度1〇〇 //m)、乳鋼鱗片（平均粒度5 00 #m)、 鐵礦石的燒結礦（平均粒度l〇〇Aim)當中任一種’而從副 孔噴嘴吹送。 最內管及內管是否有破洞，藉由根據緩衝用氣體流量 改變來檢測的方式進行監視，結果並未發生破洞。 此外，作爲比較例，是將第1圖所示的上吹式噴管之 二次燃燒用噴嘴予以機械性地堵塞’在未將二次燃燒用的 氣氣供應至爐內空間下實施脫磷處理（比較例1 )。比較 -27- 201130989 例之其他脫磷條件是依據本發明例來進行。表1顯示本發 明例及比較例之脫磷處理前後的熔融生鐵成分及作業條件 。表1中CaO的單位用量及固體氧源使用量，是熔融生鐵每 1 D頓的量。 表1 \ 熔融生鐵成分 (質量％) CaO單 位用量 (kg/t) 使用的固體氧源 二次燃燒 用噴嘴之 吹送比例 (%) 處理後的 熔融生鐵 溫度 (°C) 鐵良 率 (%) 處理前 rsii 處理前 ΓΡ1 處理後 ΓΡ1 種類 使用量 (kg/t) 本發明 例1 0.15 0.12 0.019 9.0 鐵礦石 10 6 1351 98.6 本發明 例2 0.15 0.12 0.017 9.0 燒結礦 10 6 1351 98.3 本發明 例3 0.15 0.12 0.019 9.0 鱗片 10 6 1355 98.8 本發明 例4 0.15 0.12 0.016 9.0 砂鐵 10 6 1350 98.3 比較例 1 0.15 0.12 0.019 9.0 鱗片 10 0 1350 97.9 如表1所示，在來自上吹式噴管的氧氣的吹送面附近 供應固體氧源之本發明例全部’脫磷處理後的熔融生鐵中 磷濃度爲〇 . 02 0質量％以下’且鐵良率爲9 8 %以上。相對於 此，在比較例脫磷處理後的熔融生鐵中磷濃度雖爲 0.020質量％以下，但鐵良率未達98%。亦即關於脫磷處理 中熔融生鐵的損失，相對於比較例之2· 1 %，本發明例爲 1.2~ 1.7 %，而有顯著的改善。 〔實施例2〕 -28 - 201130989 從高爐送出之熔融生鐵，按照需要在高爐爐床進行脫 矽處理後，搬運至容量300噸的轉爐，在該轉爐使用第3圖 所示的上吹式噴管實施合計兩次預備脫磷處理（本發明例 5 〜6 )。 脫磷處理中，將二次燃燒用噴嘴的氧氣流量控制成一 定的結果，二次燃燒用噴嘴的氧氣流量（Q )相對於主孔 噴嘴的氧氣流量（Q〇 )，亦即100Q/Qo爲12%。在此情況 也是，確認Xsi η 0可滿足前述式（2)的範圍。其他的脫 磷處理條件與實施例1相同。表2顯示脫磷處理前後之熔融 生鐵成分及作業條件。表2中CaO的單位用量及固體氧源使 用量，是熔融生鐵每1噸的量。又鐵良率的定義是與實施 例1相同。 表2 熔融生鐵成分(質量％) CaO單 位用量 (kg/t) 使用的固體氧源 二次燃燒 用噴嘴之 吹送比例 (%) 處理後的 熔融生鐵 溫度 ΓΟ 鐵良 率 (%) 處理前 [Si] 處理前 [P] 處理後 [P] 種類 使用量 (kg/t) 本發明 例5 0.15 0.12 0.019 9.0 鱗片 10 12 1355 98.9 本發明 例6 0.15 0.12 0.015 9.0 砂鐵 10 12 1351 98.9 如表2所示，由於二次燃燒用噴嘴的氧氣流量比實施 例1增多，二次燃燒發熱量增加，而能進一步抑制基體金 屬附著，脫磷處理之鐵良率成爲大致9 9% (亦即熔融生鐵 損失約1 % )，而確認具有更高的品質。 -29- 201130989 〔實施例3〕 從高爐送出之熔融生鐵’按照需要在高爐爐床進行脫 矽處理後，搬運至容量350噸的轉爐，在該轉爐使用第1圖 及第3圖所示的上吹式噴管實施預備脫磷處理（本發明例 7〜8 )。 從轉爐爐底的風口，將作爲攪拌用氣體之氧氣以熔融 生鐵每1噸0.3Nm3 /分的流量吹入。爐底的風口採用雙層管 構造，從內管吹送氧氣從外管是對應於氧氣流量而吹送冷 卻氣體（丙院氣體）。作爲固體氧源，對熔融生鐵每1噸 使用鐵礦石的燒結礦（平均粒度100 ym) 6kg，從上吹式 噴管的副孔噴嘴吹送。二次燃燒用噴嘴的氧噴流條件，是 滿足上述式（2)的範圍。其他脫磷處理條件是和實施例i 同樣條件。 此外’作爲比較例，是將第1圖所示的上吹式噴管之 二次燃燒用噴嘴予以機械性地堵塞，在未將二次燃燒用的 氣氣供應至爐內空間下實施脫磷處理（比較例2 )。比較 例之其他脫磷條件是依據本發明例來進行。 表3顯示脫磷處理前後之熔融生鐵成分及作業條件。 一倂顯示出脫磷處理中的二次燃燒用噴嘴的氧氣流量（Q )相對於主孔噴嘴的氧氣流量（Q〇)，亦即100Q/Qo。表3 中CaO的單位用量是熔融生鐵每1噸的量。又鐵良率的定義 是與實施例1相同。 -30- 201130989 表3 上吹式噴 管種類 熔融生鐵成分(S 『量％) CaO單 位用量 (kg/t) 二次燃燒用噴 嘴之吹送比例 (%) 處理後的熔 融生鐵溫度 ΓΟ 鐵良率 (%) 處理前 rsii 處理前 FP1 處理後 ΓΡ1 本發明 例7 第1圖型 0.15 0.12 0.018 9.0 6 1351 98.6 本發明 例8 第3圖型 0.15 0.12 0.016 9.0 15 1360 98.8 比較例 2 第1圖型 0.15 0.12 0.020 9.0 0 1350 97.9 如表3所示，在從爐底風口吹送氧氣之強攪拌條件下 也是，隨著二次燃燒發熱量的增加，可進一步抑制基體金 屬的附著，而使脫磷處理之鐵良率更高。 〔實施例4〕 將從高爐送出之熔融生鐵搬運至容量3 00噸的轉爐， 在該轉爐使用第3圖所示的上吹式噴管實施脫碳脫磷處理 而熔製成熔鋼（本發明例9 )。熔融生鐵之脫碳精煉，是 藉由提高所生成的爐內熔渣的鹼性，而和脫磷反應同時進 行。 脫碳脫磷處理，是從含氧氣體供應管18供應氧氣，並 從含氧氣體及粉體供應管I7以氧氣作爲搬運用氣體而供應 生石灰粉（平均粒徑1mm以下），從最內管的內部（第3 供應路徑）是以氬氣作爲搬運用氣體而供應粉體的固體氧 源。 有別於上吹式噴管，從設置於轉爐爐上的料斗也將塊 狀的生石灰投入爐內。但作爲精煉劑，並未使用CaF2等的 -31 - 201130989 氟化物而實施脫碳脫磷處理。此外，從轉爐爐底的風口， 將作爲攪拌用氣體之氬氣以熔融生鐵每噸0.1 5Nm3/分的流 量吹入。 從主孔噴嘴供應之氧氣流量爲熔融生鐵每噸3.2Nm3/ 分。從二次燃燒用噴嘴，在吹煉開始至結束爲止的期間的 前半段，是供應氧氣，在後半段供應氬氣。相對於主孔噴 嘴的氧氣流量（Qo)，二次燃燒用噴嘴的氧氣流量（Q) 爲5%。來自二次燃燒用噴嘴的氧噴流的條件爲滿足前述式 (2)條件的範圍。作爲固體氧源，對熔融生鐵每1噸使用 鐵礦石的燒結礦（平均粒度1 〇〇 V m ) 6kg，從副孔噴嘴吹 送。 此外，作爲比較例，是將第3圖所示的上吹式噴管之 二次燃燒用噴嘴予以機械性地堵塞，在未將二次燃燒用的 氣氣供應至爐內空間下實施脫磷處理（比較例3 )。比較 例之其他脫碳脫磷條件是依據本發明例來進行。 表4係顯示本發明例及比較例之脫磷處理前後的熔融 生鐵成分及作業條件。表4中的CaO單位用量及固體氧源使 用量是熔融生鐵每1噸的量。鐵良率（η)，是相對於裝入 轉爐內之熔融生鐵的質量（W〇 )和鐵屑質量（Ws )的總 質量（W〇 + Ws )，將脫碳脫磷處理後送出的熔鋼的質量（ W,)用百分率表示（ηΜΟΟλν,Μ W〇 + Ws ))的數値。 -32- 201130989 表4 上吹式噴 管麵 熔融生鐵成分(隻 F*%) CaO單 位用量 (kg/t) 二次燃燒用噴 嘴之吹送比例 (%) 處理後的熔 融生鐵溫度 CC) 鐵良率 (%) 處理前 rsn 處理前 ΓΡ1 處理後 ΓΡ1 本發明 例9 第3圖型 0.20 0.12 0.020 18.0 5 1650 94.5 比較例 3 第型 0.20 0.12 0.020 18.0 0 1651 94.2 如表4所示，本發明例9之鐵良率比起比較例3稍佳。 亦即即使在高溫處理之基體金屬附著較少的條件下，藉由 局部地援用二次燃燒，仍可改善良率。 依據本發明之上吹式噴管，即使從第1供應路徑及第3 供應路徑供應粉體，從二次燃燒用噴嘴僅噴射出含氧氣體 ，因此二次燃燒用噴嘴能不發生堵塞而長期間穩定地噴射 二次燃燒用含氧氣體。藉此，可抑制轉爐型精煉容器的基 體金屬附著，可防止基體金屬附著所造成的弊害於未然， 而能達成鐵良率的提昇及生產性的提昇。此外，含氧氣體 、固體氧源及石灰系脫磷用精煉劑等的助熔劑可供應至同 一部位或附近，因此可實現高效率地進行熔融生鐵及熔鋼 的氧化精谏。 【圖式簡單說明】 第1圖係本發明的精煉用上吹式噴管的例子之槪略截 面圖。 第2圖係顯示，本發明之精煉用上吹式噴管中，朝緩 -33- 201130989 衝空間之緩衝用氣體的供應路徑。 第3圖係本發明的精煉用上吹式噴管的其他例子之槪 略截面圖。 【主要元件符號說明】 1 :上吹式噴管 1A :上吹式噴管 2 :噴管主體 3 :噴管噴嘴 4 :噴管頂部 5 :最外管 6 :外管 7 :中管 8 :分隔管 9 :內管 1 〇 :最內管 1 1 :主孔噴嘴 1 2 :副孔噴嘴 13 :二次燃燒用噴嘴 1 4 :含氧氣體供應管 1 5 :粉體供應管 1 6 :緩衝用氣體供應管 17:含氧氣體及粉體供應管 1 8 :含氧氣體供應管 -34- 201130989 1 9 :緩衝用氣體導入裝置 2 〇 :檢測器 2 1 :遙控操作閥 22 :撓性軟管 23 :手動遮斷閥 -356〇xC In the formula (1), V 0 : flow rate of the outlet of the secondary combustion nozzle (m/sec), de : outlet of the secondary combustion nozzle ί » 0 = 0.016 + 0.19 / ( P〇-Pe ), P〇: oxygen back pressure (kgf/cm2) expressed by the pressure of the secondary combustion, and Pe: the ambient pressure (kgf/cm2) expressed by the pressure of the converter type refining capacity. As long as the distance X does not reach the proper range of the furnace wall to control the design of the nozzle and the control of the blowing conditions, local melting and melting of the furnace wall refractory can be avoided, and the secondary combustion reaction is dispersed in the furnace. Inside. Further, in the upper blow nozzle 1 shown in Fig. 1, the lower portion of the partition pipe 8 reaches the nozzle nozzle 3, and the second supply path is opened to the negative diameter. Therefore, the oxygen-containing gas ejected from the secondary combustion nozzle 13 depends on the ratio of the total cross-sectional area of the main orifice nozzle 11 to the area of the secondary combustion nozzle, and the discharge amount from the secondary combustion cannot be independently controlled. In other words, the total amount of oxygen-containing gas from the oxygen-containing gas supply pipe 14 and the powder supply pipe is distributed in accordance with the cross-sectional area ratio of the two, and the blowing control is performed with higher precision. The oxygen-containing gas flow is independently controlled. However, in this case, the internal structure of the blow nozzle is changed to the same structure as the upper blow 5 shown in Fig. 1. Find out. Oxygen jet S (mm) The absolute inside of the nozzle is blown to the base of the base. The heat is evenly distributed. The end is not the i 1 supply path. The flow is 1 3 of the total nozzle 1 3 of the spray 1 5 supply. In order to change the combustion, it is necessary to control the upper nozzle 1 not -23- 201130989. Fig. 3 shows that the flow rate of the oxygen-containing gas for secondary combustion and the oxygen-containing gas for blowing can be independently controlled. example of. The lower end of the upper blow nozzle 1A' partition pipe 8 shown in Fig. 3 reaches the nozzle nozzle 3, and the gap between the middle pipe 7 and the split pipe 8 at the nozzle nozzle 3 (i.e., the second supply) The path) is sealed. Further, in the nozzle top portion 4, the upper end of the partition pipe 8 is located above the upper end position of the intermediate pipe 7, and a sealing material for sealing is provided between the intermediate pipe 7 and the partition pipe 8, and the second supply path is sealed. Further, the intermediate pipe 7 is connected to the oxygen-containing gas supply pipe 18 (the installation portion of the supply pipe is an oxygen-containing gas introduction portion). That is, the oxygen-containing gas supplied from the oxygen-containing gas supply pipe 18 to the inside of the intermediate pipe 7 is ejected from the secondary combustion nozzle 13 through the gap between the intermediate pipe 7 and the partition pipe 8 (that is, the second supply path). . On the other hand, in the nozzle top portion 4, the oxygen-containing gas and the powder supply pipe 17 are connected to the partition pipe 8 (the installation portion of the supply pipe constitutes the refining slag introduction portion and the oxygen-containing gas introduction portion). Further, the oxygen-containing gas for blowing supplied from the oxygen-containing gas and the powder supply pipe 17 to the inside of the partition pipe 8, or the refining slag containing the oxygen-containing gas as the transport gas, passes through the partition pipe 8 and the inner pipe. The gap of 9 (i.e., the first supply path) is ejected from the main orifice nozzle 11. In the case where only the oxygen-containing gas is blown from the main orifice nozzle 11, only the oxygen-containing gas is supplied from the oxygen-containing gas and the powder supply pipe 17, and the powder is blown from the main orifice nozzle 1 (the oxygen-containing gas is used for transportation). In the case of gas, the oxygen-containing gas and the powder are supplied from the oxygen-containing gas and the powder supply pipe 17. The other configuration of the upper blow nozzle 1A' is the same as that of the upper blow nozzle 1 shown in Fig. 1, and the same portions are denoted by the same reference numerals, and the description thereof will be omitted. Further, the preliminary dephosphorization treatment of the molten pig iron using the above-described upper blow nozzle -24-201130989 1A may be carried out in accordance with the case of using the upper blow nozzle 1. Further, depending on the state of blowing, oxygen may be ejected from the secondary combustion nozzle 13 without passing through the second supply path. In this case, in the upper blow nozzle 1A shown in FIG. 3, in order to prevent clogging of the secondary combustion nozzle 13, the reducing gas, the carbon dioxide gas, the non-oxidizing gas, and the inert gas can be supplied from the second supply path. Any one or two or more kinds of gases. As described above, according to the present invention, the upper blow nozzles 1, 1 are internally provided with the first supply path, the second supply path, and the third supply path. In the first supply path, a powder (a lime-based dephosphorization refining agent or the like) different from the solid oxygen source and the oxygen-containing gas for blowing are supplied through the main orifice nozzle 1 1 or may be used for blowing. The oxygen-containing gas is supplied through the main orifice nozzle 11; the second supply path supplies the oxygen-containing gas for secondary combustion through the secondary combustion nozzle 13; the third supply path is powdery The solid oxygen source is supplied together with the carrier gas through the sub-hole nozzle 12. Therefore, even if the powder is supplied from the first supply path and the third supply path, only the oxygen-containing gas is ejected from the secondary combustion nozzles 1 3, so that the secondary combustion nozzle 13 can be stably ejected for a long period of time without clogging. Oxygen-containing gas for secondary combustion. Thereby, the adhesion of the base metal of the converter type refining container can be suppressed, and the disadvantages caused by the adhesion of the base metal can be prevented. [Examples] [Example 1] The molten pig iron sent out from the blast furnace was subjected to de--25-201130989 矽 treatment in a blast furnace hearth as needed, and then transferred to a converter having a capacity of 300 tons, and the converter was used as shown in Fig. 1 The upper blow nozzle was subjected to a total of four preliminary dephosphorization treatments (Inventive Examples 1 to 4). The main orifice nozzles are equally arranged four on the concentric circles. Further, in the secondary combustion nozzle, eight upper and lower portions are equally arranged on the circumference, and the angle 0 (°) between the secondary combustion nozzle and the upper blow nozzle is set to be oxygen in the nozzle for secondary combustion. When the jet flow rate is 30 m/sec, the distance X (m) from the nozzle outlet of the secondary combustion nozzle 13 satisfies the following formula (2). 0_10<^^0.75...(2) Η Here, X is the distance (m) from the nozzle outlet of the secondary combustion nozzle determined by the formula (1), and Η is from the center of the upper blow nozzle to the converter furnace The distance (m) of the wall in the horizontal direction. Further, the angle 0 is an angle between the center line of the secondary combustion nozzle and the center line of the upper blow nozzle, and is based on the vertical direction (=0°) (〇° < 0 $90°). Therefore, Xsin0 represents the jet arrival distance (m) in the horizontal direction from the nozzle for secondary combustion. The phosphorus concentration of the molten pig iron before the dephosphorization treatment is 0.12% by mass in total, the phosphorus concentration of the molten pig iron after the dephosphorization treatment is 0.020% by mass or less, and the iron yield target is 98% or more. The iron yield (η) is the mass of the molten pig iron (W〇) and the mass of the iron filings (Ws) (W〇+ Ws ) charged in the converter, and the molten pig iron sent out after the dephosphorization treatment The mass (w) is expressed as a percentage (n = ioow / (w 〇 + ws)). The dephosphorization treatment is to supply oxygen from the oxygen-containing gas supply pipe 14, and to supply the quicklime powder (average particle diameter of 1 mm or less) from the powder -26-201130989 supply pipe 15 with oxygen as a carrier gas, from the inside of the innermost pipe (Third Supply Path) A solid oxygen source that supplies powder using nitrogen as a carrier gas. In this case, the first supply path is a supply path constituting oxygen and quicklime powder, and the second supply path is a supply path constituting oxygen. Different from the upper blow nozzle, the slag placed on the converter furnace also puts massive lime into the furnace (the amount of quick lime from the upper blow nozzle: the amount of quick lime input from the hopper on the furnace = 8:2) ). However, as a refining agent for dephosphorization, dephosphorization treatment is carried out without using a fluoride such as CaF2. Further, nitrogen gas as a gas for mixing was blown in a flow rate of 0.03 to 0.30 Nm 3 /min per ton of molten iron from the tuyere of the bottom of the converter. The oxygen flow rate supplied from the main orifice nozzle and the secondary combustion nozzle is 0.6 to 2.5 Nm 3 /min per ton of molten pig iron. The unit dosage of oxygen, except for the oxygen required for sand removal, is 12 Nm3/t. The oxygen flow rate (Q) of the secondary combustion nozzle is 6% with respect to the oxygen flow rate (Q〇) of the main orifice nozzle, that is, 1 〇〇Q/Q0. As a solid oxygen source, powdered iron ore (average particle size 50/m), sand iron (average particle size 1 〇〇//m), milk steel scale (average particle size 500 00 #m), iron ore can be used. Any of the sinter (average particle size l〇〇Aim) is blown from the secondary orifice nozzle. Whether or not the innermost tube and the inner tube have a hole is monitored by detecting the flow rate of the buffer gas, and no hole is formed. Further, as a comparative example, the nozzle for secondary combustion of the upper-blowing nozzle shown in Fig. 1 is mechanically blocked. The dephosphorization is carried out without supplying the gas for secondary combustion to the space inside the furnace. Treatment (Comparative Example 1). Comparison -27- 201130989 Other dephosphorization conditions are carried out in accordance with the examples of the present invention. Table 1 shows the molten pig iron components and working conditions before and after the dephosphorization treatment of the examples and comparative examples of the present invention. The unit dosage of CaO in Table 1 and the amount of solid oxygen source used are the amount of molten pig iron per 1 D. Table 1 \ Melted pig iron composition (% by mass) CaO unit amount (kg/t) The ratio of blowing of the nozzle for secondary combustion of solid oxygen source used (%) The temperature of molten pig after treatment (°C) The yield of iron (%) ΓΡ1 type before use rs1 treatment ΓΡ1 type usage amount (kg/t) Inventive Example 1 0.15 0.12 0.019 9.0 Iron ore 10 6 1351 98.6 Inventive Example 2 0.15 0.12 0.017 9.0 Sinter ore 10 6 1351 98.3 Inventive Example 3 0.15 0.12 0.019 9.0 Scale 10 6 1355 98.8 Inventive Example 4 0.15 0.12 0.016 9.0 Sand iron 10 6 1350 98.3 Comparative Example 1 0.15 0.12 0.019 9.0 Scale 10 0 1350 97.9 As shown in Table 1, in the oxygen from the upper blow nozzle In the example of the present invention in which the solid oxygen source is supplied in the vicinity of the blowing surface, the phosphorus concentration in the molten pig iron after the dephosphorization treatment is 〇.00 0% by mass or less and the iron yield is 98% or more. On the other hand, in the molten pig iron after the dephosphorization treatment in the comparative example, the phosphorus concentration was 0.020% by mass or less, but the iron yield was less than 98%. That is, with respect to the loss of molten pig iron in the dephosphorization treatment, the present invention was 1.2 to 1.7% with a significant improvement with respect to 2.1% of the comparative example. [Example 2] -28 - 201130989 The molten pig iron sent out from the blast furnace was subjected to a degassing treatment in a blast furnace hearth as needed, and then transferred to a converter having a capacity of 300 tons, and the top blowing type spray shown in Fig. 3 was used in the converter. The tube was subjected to a total of two preliminary dephosphorization treatments (Examples 5 to 6 of the present invention). In the dephosphorization treatment, the oxygen flow rate of the secondary combustion nozzle is controlled to a certain result, and the oxygen flow rate (Q) of the secondary combustion nozzle is relative to the oxygen flow rate (Q〇) of the main orifice nozzle, that is, 100Q/Qo 12%. Also in this case, it is confirmed that Xsi η 0 can satisfy the range of the above formula (2). The other dephosphorization treatment conditions were the same as in the first embodiment. Table 2 shows the molten pig iron components and working conditions before and after the dephosphorization treatment. The unit dosage of CaO in Table 2 and the amount of solid oxygen source used are the amount of molten pig iron per ton. The definition of the iron yield is the same as in the first embodiment. Table 2 Melt pig iron component (% by mass) CaO unit amount (kg/t) The ratio of blowing of the nozzle for secondary combustion of the solid oxygen source used (%) The temperature of the molten pig after the treatment ΓΟ The yield of iron (%) before treatment [Si [P] type before use [P] Type of use (kg/t) Example 5 of the present invention 0.15 0.12 0.019 9.0 Scale 10 12 1355 98.9 Example 6 of the invention 0.15 0.12 0.015 9.0 Sand iron 10 12 1351 98.9 As shown in Table 2 It is shown that the oxygen flow rate of the nozzle for secondary combustion is larger than that of the first embodiment, and the calorific value of the secondary combustion is increased, and the adhesion of the base metal can be further suppressed, and the iron yield of the dephosphorization treatment is approximately 9 9% (that is, the molten iron loss is obtained). About 1%), and confirmed to have higher quality. -29- 201130989 [Example 3] The molten pig iron sent from the blast furnace was subjected to a degassing treatment in a blast furnace hearth as required, and then transferred to a converter having a capacity of 350 tons, and the converters shown in Figs. 1 and 3 were used. The upper blow nozzle was subjected to preliminary dephosphorization treatment (Inventive Examples 7 to 8). From the tuyere of the bottom of the converter, oxygen as a stirring gas was blown at a flow rate of 0.3 Nm 3 /min per ton of molten pig iron. The tuyere of the furnace bottom is constructed in a double pipe structure, and oxygen is blown from the inner pipe from the outer pipe to blow the cooling gas (silicon gas) corresponding to the oxygen flow rate. As a solid oxygen source, 6 kg of sintered ore (average particle size: 100 μm) of iron ore per ton of molten pig iron was blown from the sub-hole nozzle of the upper blow nozzle. The oxygen jet flow condition of the secondary combustion nozzle satisfies the range of the above formula (2). Other dephosphorization treatment conditions were the same as in Example i. In addition, as a comparative example, the nozzle for secondary combustion of the upper-blowing nozzle shown in Fig. 1 is mechanically blocked, and the degassing is performed without supplying the gas for secondary combustion to the space inside the furnace. Treatment (Comparative Example 2). Other dephosphorization conditions of the comparative examples were carried out in accordance with the examples of the present invention. Table 3 shows the molten pig iron composition and working conditions before and after the dephosphorization treatment. One shows the oxygen flow rate (Q) of the secondary combustion nozzle in the dephosphorization treatment with respect to the oxygen flow rate (Q〇) of the main orifice nozzle, that is, 100 Q/Qo. The unit dosage of CaO in Table 3 is the amount per ton of molten pig iron. The definition of the iron yield is the same as in the first embodiment. -30- 201130989 Table 3 Upper blown nozzle type molten pig iron composition (S 『%%) CaO unit amount (kg/t) Secondary combustion nozzle blowing ratio (%) After processing molten pig iron temperature ΓΟ Iron yield (%) Pre-treatment of rsii before treatment FP1 treatment ΓΡ1 Inventive Example 7 First Figure 0.15 0.12 0.018 9.0 6 1351 98.6 Inventive Example 8 Third Figure 0.15 0.12 0.016 9.0 15 1360 98.8 Comparative Example 2 First Figure 0.15 0.12 0.020 9.0 0 1350 97.9 As shown in Table 3, under the strong agitation conditions of blowing oxygen from the bottom of the furnace bottom, as the calorific value of the secondary combustion increases, the adhesion of the base metal can be further suppressed, and the dephosphorization treatment can be performed. The iron yield is higher. [Example 4] The molten pig iron sent from the blast furnace was transferred to a converter having a capacity of 300 tons, and the converter was subjected to decarburization and dephosphorization treatment using the up-blowing nozzle shown in Fig. 3 to be melted into molten steel. Inventive Example 9). The decarburization refining of the molten pig iron is carried out simultaneously with the dephosphorization reaction by increasing the alkalinity of the slag generated in the furnace. The decarburization and dephosphorization treatment is to supply oxygen from the oxygen-containing gas supply pipe 18, and supply the quicklime powder (average particle diameter of 1 mm or less) from the oxygen-containing gas and the powder supply pipe I7 using oxygen as a carrier gas, from the innermost tube. The inside (third supply path) is a solid oxygen source that supplies powder using argon gas as a carrier gas. Unlike the upper blow nozzle, the block of quicklime is also put into the furnace from the hopper provided on the converter furnace. However, as a refining agent, decarburization and dephosphorization treatment is carried out without using -31 - 201130989 fluoride of CaF2 or the like. Further, from the tuyere of the bottom of the converter, argon gas as a stirring gas was blown at a flow rate of 0.1 5 Nm 3 /min per ton of molten pig iron. The oxygen flow supplied from the main orifice nozzle is 3.2 Nm 3 /min per ton of molten pig iron. From the secondary combustion nozzle, oxygen is supplied in the first half of the period from the start to the end of the blowing, and argon is supplied in the second half. The oxygen flow rate (Q) of the secondary combustion nozzle is 5% with respect to the oxygen flow rate (Qo) of the nozzle of the main orifice. The condition of the oxygen jet from the secondary combustion nozzle is a range satisfying the condition of the above formula (2). As a solid oxygen source, 6 kg of sintered ore (average particle size 1 〇〇 V m ) of iron ore per ton of molten pig iron was used, and it was blown from the sub-hole nozzle. Further, as a comparative example, the nozzle for secondary combustion of the upper-blowing nozzle shown in Fig. 3 is mechanically blocked, and dephosphorization is performed without supplying the gas for secondary combustion to the space inside the furnace. Treatment (Comparative Example 3). Other decarburization and dephosphorization conditions of the comparative examples were carried out in accordance with the examples of the present invention. Table 4 shows the molten pig iron components and working conditions before and after the dephosphorization treatment of the inventive examples and comparative examples. The amount of CaO used in Table 4 and the amount of solid oxygen source used are the amount of molten pig iron per ton. The iron yield (η) is the total mass (W〇+ Ws ) relative to the mass of the molten pig iron (W〇) and the mass of the iron filings (Ws) charged in the converter, and the melting after the decarburization and dephosphorization treatment The mass (W,) of the steel is expressed as a percentage of (ηΜΟΟλν, Μ W〇 + Ws ). -32- 201130989 Table 4 Melting pig iron composition on the upper nozzle surface (F*% only) CaO unit dosage (kg/t) The blowing ratio of the nozzle for secondary combustion (%) The molten pig iron temperature after treatment CC) Rate (%) before treatment rsn before treatment ΓΡ1 treatment ΓΡ 1 Inventive Example 9 3rd pattern 0.20 0.12 0.020 18.0 5 1650 94.5 Comparative Example 3 Type 0.20 0.12 0.020 18.0 0 1651 94.2 As shown in Table 4, Example 9 of the present invention The iron yield was slightly better than Comparative Example 3. That is, even under the condition that the base metal adhesion is low in the high temperature treatment, the yield can be improved by partially applying the secondary combustion. According to the above-described upper blow nozzle, even if the powder is supplied from the first supply path and the third supply path, only the oxygen-containing gas is ejected from the secondary combustion nozzle, so that the secondary combustion nozzle can be blocked without clogging. The oxygen-containing gas for secondary combustion is stably injected during the period. Thereby, the adhesion of the base metal of the converter type refining container can be suppressed, and the disadvantages caused by the adhesion of the base metal can be prevented, and the improvement of the iron yield and the improvement of the productivity can be achieved. Further, a flux such as an oxygen-containing gas, a solid oxygen source, and a lime-based dephosphorization refining agent can be supplied to the same portion or in the vicinity, so that the molten iron and the molten steel can be efficiently oxidized. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a schematic cross-sectional view showing an example of an upper blown nozzle for refining of the present invention. Fig. 2 is a view showing the supply path of the buffer gas for the space of the -33-201130989 flushing in the upper-blowing nozzle for refining of the present invention. Fig. 3 is a schematic cross-sectional view showing another example of the upper blow-off nozzle for refining of the present invention. [Main component symbol description] 1 : Up-blowing nozzle 1A : Up-blowing nozzle 2 : Nozzle body 3 : Nozzle nozzle 4 : Nozzle top 5 : Outer tube 6 : Outer tube 7 : Middle tube 8 : Separator tube 9: inner tube 1 〇: innermost tube 1 1 : main hole nozzle 1 2 : sub-hole nozzle 13 : secondary combustion nozzle 1 4 : oxygen-containing gas supply tube 1 5 : powder supply tube 1 6 : buffer Gas supply pipe 17: Oxygen-containing gas and powder supply pipe 18: Oxygen-containing gas supply pipe -34- 201130989 1 9 : Buffer gas introduction device 2 〇: Detector 2 1 : Remote operation valve 22: Flexible soft Tube 23: manual shut-off valve -35