TW200417611A - A method of recycling converter dust to a rotary hearth type reduction furnace - Google Patents
A method of recycling converter dust to a rotary hearth type reduction furnace Download PDFInfo
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200417611 玖、發明說明 (發明說明應敘明：發明所屬之技術領域、先前技術、内容、實施方式及圖式簡單說明） L發明所屬之技術領域3 技術領域 本發明係有關於一種利用旋轉爐床式還原爐回收處理 5 在一貫製程煉鐵廠中所產生之由非燃燒式氣體處理裝置集 塵之轉爐灰燼作為鐵原料的方法。 I：先前技術3 背景技術 以高爐轉爐所作之一貫煉鐵作業中，1間煉鐵廠一年 10 可生產300萬〜1000萬噸之鋼鐵，這是非常有效率之煉鐵 法。在轉爐中，將氧喷出至由高爐製造之熔融狀態的生鐵 和廢料，並利用生鐵中之碳和矽等之燃燒熱使溫度上昇， 而獲得低碳濃度之熔鋼。此時，轉爐會產生以一氧化碳為 主體之氣體，氣體量係每1噸生鐵為l〇〇Nm3。該轉爐氣體 15 摻雜有約100g/Nm3，即約10kg/t_steel之鐵灰燼。 摻雜於轉爐氣體之鐵灰燼（以下稱為轉爐灰燼）有粒 子粗者和粒子細者。粗粒之轉爐灰燼是粒徑約從30# m到 1mm者，這些灰燼是轉爐中溶化之鐵被吹起者，約包含有 80〜90質量％之金屬鐵和10質量％之氧化鐵。細粒之轉爐 20 灰燼是粒徑約1〜5/zm者。這些灰燼是轉爐中熔化之鐵因 氧之燃燒熱而蒸發，並凝集而與氣體一起被吹起者，包含 有70質量％之金屬鐵和約30質量％之氧化鐵。微粒轉爐 灰燼中亦摻雜有同樣由轉爐爐内蒸發之來自廢料的鋅。依 照所使用之廢料之鋅含有率等而有所不同，通常，鋅濃度 6 200417611 玫、發明說明 係約0.2〜1質量％ 。 轉爐氣體由非燃燒式之氣體處理裝置，所謂〇G ( Oxygen converter gas recovery;氧氣轉爐氣體回收）裝置 ♦ τκ木塵之後，使用作為發電和鋼材之加熱的燃料氣體 °〇G裝置具有文氏洗氣器方式之集塵裝置，其係一邊灑 水一邊收集灰燼。首先，利用一次沉殿槽，分離集塵水中 之轉爐灰爐的粗粒部分，並注入至增稠劑。在增稠劑内， 使微粒轉爐灰燼沉澱，並利用脫水機將濃度變濃者脫水成 含水分為20〜30質量％ 。 粗粒轉爐灰燼由於粒徑大，且金屬鐵比率高，鋅比率 低，所以是有用之鐵資源，有各種回收方法可將其回收。 特別是回收使用作為燒結機之原料和使用其取代轉爐中之 廢料。 然而’另一方面，微粒轉爐灰燼由於粒徑為極細小之 15 1〜5 Am，所以比表面積大，且保存時金屬鐵之氧化劇烈。 由於這種氧化伴隨有發熱，故很難簡單地使用微粒轉爐灰 爐。又’鋅等成分之問題也成為回收上之障礙。 首先’回收微粒轉爐灰燼之有效方法有將微粒轉爐灰 燼供給至由高爐卸出後之熔化生鐵之中，而除去熔化生鐵 中之石夕和辦的方法等。又，亦有一部分人係挑選鋅少之部 刀，再藉由燒結機回收至高爐。如前所述，為了微粒轉爐 灰燼之回收，以往已嘗試過各種方法。然而，使用於高爐 以外之習知方法中，因為可回收使用之微粒轉爐灰燼之量 有限，所以僅靠該等方法係不可能回收利用全部之微粒轉 7 玖、發明說明 爐灰燼。在此，為了使用大量之微粒轉爐灰燼，回收至高 爐係較有效的。 然而，微粒轉爐灰燼中含有鋅，要在高爐直接使用是 有所限制的。即，由於微粒轉爐灰燼之鋅多，故當藉由燒 5結機回收至高爐時，鋅會在高爐爐内之高溫部蒸發，而成 為氧化鋅或氣化鋅，且附著於高爐之爐壁。結果，造成高 爐中之礦石和焦炭於爐内落下消失的問題。 對應該問題之方法係若對微粒轉爐灰燼作脫鋅處理， 則在高爐亦可使用。因此，也有人嘗試利用旋轉窯（Waelz 10 klln)法和旋轉爐床法來脫鋅，而使高爐可使用。又，其 中，凝轉爐床法由於脫鋅率高達90%以上，且可獲得還原 鐵故利用其作為脫辞製程之例逐漸增加。最近，如本發 明人所申請之日本專利公開公報特開2000-34526號中所揭 示者，開發出一種將利用旋轉爐床法還原之粒的強度提高 15至在高爐可使用程度的方法，因此微粒轉爐灰燼已可在高 爐中使用。 此外’旋轉爐床法係在固定之对火物之頂部及侧壁之 下’令中央部有缺口之圓盤狀耐火物之爐床以一定速度於 執道上旋轉之型式的燒成爐作為主體的製程，可用於氧化 20金屬之還原和煉鐵灰燼之處理。旋轉爐床式還原爐之爐床 直徑係10〜50公尺，且寬度係2〜6公尺。原料一般係使用 以旋轉之鍋狀造粒裝置將粉體造粒形成之球形粒。為了利 用旋轉爐床式還原爐使用微粒轉爐灰燼，故單獨將微粒轉 爐灰燼’或者，將其與其他含氧化鐵之粉體之混合物與粉 8 200417611 玖、發明說明 焦炭等含碳之粉體混合而製成球形粒。 由於微粒轉爐灰燼脫水後也還含有20〜35質量％之水 分，且非常細微，所以呈黏土狀，且有處理性和與其他粉 體之混合性不佳的問題。若使微粒轉爐灰燼之含水分亦降 5 低，便可改善處理性和混合性。然而，習知技術中，僅有 只要使微粒轉爐灰燼乾燥即可的認知，因此產生了如後所 述之種種問題。 如曰本專利公開公報特開2000-54034號所示，以往係 利用旋轉爐床式還原爐進行微粒轉爐灰燼之處理。然而， 10 首先，簡單而言，若使微粒轉爐灰燼過度乾燥，微粒狀態 中比表面積大之金屬鐵便開始與空氣發生反應而氧化並發 熱。特別是習知技術中，因為重視微粒轉爐灰燼作為粉體 之處理性和防止其黏附於儲備槽内，所以使其過度乾燥， 而導致發熱問題變大。嚴重時，溫度甚至會上昇至800°c 15 左右，有引起火災之危險。 再者，亦有目的在於防止發生使用步驟中之發熱問題 ，而事前使微粒轉爐灰爐完全氧化的方法。然而，此時， 在為了回收利用之前置處理當中的氧化處理中，嚴重時， 微粒轉爐灰燼之堆會被加熱至800°C以上，且微粒轉爐灰 20 燼之細微粒子間發生燒結反應，造成平均粒徑變大的問題 。由於燒結現象，依粒子情況不同，有變成數mm〜數十 mm以上者，也有變成堅固之燒結塊。因此必須將其粉碎 ，才可與其他粉體混合而造粒，又，即使如此做，平均粒 子徑還是過大，難以造粒成為粒。尤其是，若使用粒徑數 9 200417611 玖、發明說明 十〜100//m之微粒轉爐灰燼，便有無法製成良質之粒的問 題。即，使氧化完全地進行之方法也有技術上的問題。 以往，因為前述伴隨氧化而來之發熱問題，所以限制 了可與其他粉體混合而使用的比率。又，若要使用已大致 5 完全氧化之微粒轉爐灰燼，則有須花費事前使其氧化之操 作之費用和用以粉碎處理燒結之微粒轉爐灰燼之費用的問 題。又，因為係特別地將回收之含金屬鐵之灰燼氧化並作 為原料，所以用以利用旋轉爐床式還原爐還原之還原能量 消耗率大，不能說是一個經濟的方法。 10 為了解決伴隨微粒轉爐灰燼氧化反應之發熱，故將大 半金屬鐵氧化並利用旋轉爐床式還原爐回收使用的方法中 ，特別地將含多量之金屬鐵之微粒轉爐灰燼氧化，而將其 還原，就能量消耗而言係不利的。因此，需要一種可將微 粒轉爐灰燼作為旋轉爐床式還原爐之原料，而儘可能地不 15 使其氧化的技術。 由於微粒轉爐灰燼係平均1〜5//m之微粒，故當含有 水分時便成為黏土狀，而其處理困難之問題就變成微粒轉 爐灰燼之回收上重大的障礙。即，在儲備槽等之内部，微 粒轉爐灰燼黏附（附著而難以去除），造成排出不良之問題 20 。因為若為了因應該問題而使微粒轉爐灰燼乾燥，所含有 之金屬鐵便容易氧化，所以產生了儲備槽等之内部之微粒 轉爐灰燼的氧化發熱問題。 由於該等問題沒有解決，故習知技術中，係在地面使 用重機械，將微粒轉爐灰燼與其他含有鐵之灰燼等混合， 10 200417611 玖、發明說明 再將該混合物作為旋轉爐床式還原爐之原料。然而，該方 法中，無法定量且穩定地混合原料。結果，無法充分達成 定量地混合原料而實現適當之混合比率，藉此使粉體造粒 穩定，以及使旋轉爐床式還原爐中之還原反應穩定。即， 5 當利用微粒轉爐灰燼作為一部分原料時之旋轉爐床式還原 爐的處理未必一定是穩定的。 此外，對於利用旋轉爐床式還原爐之微粒轉爐灰爐的 還原方法也未具備充足之知識，習知技術中，僅有只要以 高溫將混合微粒轉爐灰燼與碳粉而製成之粒還原即可的認 10 知，因此還沒有有效率且可大量地使用之還原爐的處理。 如前所述，欲以微粒轉爐灰燼作為原料製成旋轉爐床 法可使用之未加工之粒，技術上頗為困難。因此，需要一 種以微粒轉爐灰燼作為一部分原料製成適於旋轉爐床式還 原爐之粒，再將其還原的新技術。 15 因此，本發明提供一種如前述之以微粒轉爐灰燼作為 原料，且利用旋轉爐床式還原爐有效率地將其還原的方法 ，係提供1)可使用微粒轉爐灰燼作為旋轉爐床式還原爐 之原料，而盡量不使其氧化的回收技術，2)可以適當之混 合比率混合微粒轉爐灰燼，使造粒穩定且旋轉爐床式還原 20 爐之還原反應穩定的回收技術。 【發明内容】 發明揭示 本發明係為了解決前述課題而作成者，其要旨如下。 (1) 一種將轉爐灰燼回收至旋轉爐床式還原爐的方法 11 200417611 玖、發明說明 ，係於由轉爐氣體之非燃燒式集塵機所集塵而收集作為增 稠劑沉澱物之轉爐灰燼，混合含氧化鐵之粉體和含碳之粉 體之後，將含水分調整成17〜27質量％ ，且製成孔隙率為 40〜54%之成形體，並將該成形體裝入旋轉爐床式還原爐而 5 使其還原者。 (2) —種將轉爐灰燼回收至旋轉爐床式還原爐的方法 ’係於由轉爐氣體之非燃燒式集塵機所集塵而收集作為增 稠劑沉殿物之轉爐灰燼，混合含氧化鐵之粉體和含碳之粉 體之後，製成含水分為55質量％以上之漿體，且將該漿體 10脫水而製成含水分為17〜27%質量之脫水物，並使該脫水 物成形而製成孔隙率為4〇〜54%之成形體，再將該成形體 裝入旋轉爐床式還原爐而使其還原者。 (3) 如第（2)項之將轉爐灰燼回收至旋轉爐床式還 原爐的方法’其中前述轉爐灰燼係由轉爐氣體之非燃燒式 15集塵機所集塵’且利用粗粒分離槽分離該轉爐灰燼之粗粒 之後’收集作為增稠劑沉澱物者。 (4) 如第（2)項之將轉爐灰燼回收至旋轉爐床式還 原爐的方法’其中前述轉爐灰燼係由轉爐氣體之非燃燒式 集塵機所集塵’且利用粗粒分離槽分離該轉爐灰燼之粗粒 後收木作為增稠劑沉激物，且，脫水成含水分為 20〜35質量％之範圍内者。 (5) 如第（1)〜（4)項中任一項之將轉爐灰燼回收 至方疋轉爐床式還原爐的方法，其中前述轉爐灰爐之金屬鐵 比率為35質量％以上。 12 200417611 玖、發明說明 (6) 如苐（2)〜（5)項中任一項之將轉爐灰燼回收 至旋轉爐床式還原爐的方法，其係使用擠壓式之成形裝置 來使前述脫水物成形，且製成成形體。 (7) —種將轉爐灰燼回收至旋轉爐床式還原爐的方法 5 係將由轉爐氣體之非燃燒式集塵機所集塵而收集作為增 稠劑沉澱物之轉爐灰燼，調整成含水分為5〜16質量％且金 屬鐵比率為8〜35質量％的狀態，且混合含氧化鐵之粉體和 έ炭之叙體而製成混合物之後，使該混合物成形而製成成 形體，並將該成形體裝入旋轉爐床式還原爐而使其還原者 10 ° (8) 如第（7)項之將轉爐灰燼回收至旋轉爐床式還 原爐的方法，其中前述混合物係將調整成含水分為5〜16質 量％且金屬鐵比率為8〜35質量％之狀態的前述轉爐灰爐， 儲備於儲備槽，且利用定量分出裝置由該儲備槽分出前述 15轉爐灰燼’並以預定之混合比率，與含氧化鐵之粉體和含 碳之粉體混合者。 (9) 如第（7)或（8)項之將轉爐灰燼回收至旋轉爐 床式還原爐的方法，其係使用鍋式造粒裝置將前述混合物 製成為球形粒之成形體。 2〇 ( 1〇)如第（7)或（8)項之將轉爐灰燼回收至旋轉 爐床式還原爐的方法，其係將含氧化鐵之粉體和含碳之粉 體與刖述轉爐灰燼混合，並且粉碎而製成混合物之後，使 用鍋式造粒裝置將該混合物製成為球形粒之成形體。 (11)如第（7)或（8)項之將轉爐灰燼回收至旋轉 13 200417611 玖、發明說明 爐床式還原爐的方法，其係使用包含有一對具有多數凹狀 成形模之滾輪的成形裝置將前述混合物製成為壓塊之成形 體。 (12)如第（1)〜（11)項中任一項之將轉爐灰燼回 5 收至旋轉爐床式還原爐的方法，其中前述成形體中含有之 石反，與鐵、巍、錄、鉻、錯及鋅之氧化物之氧的原子莫爾 比係在0.5〜1.5之範圍内。 〇3)如第〜（12)項中任一項之將轉爐灰燼回 收至旋轉爐床式還原爐的方法，其係將前述成形體供給至 10前述旋轉爐床式還原爐，且在1200°C以上之環境溫度中加 熱6分鐘以上而使其還原。 (14) 如第（1)〜（13)項中任一項之將轉爐灰燼回 收至旋轉爐床式還原爐的方法，其係令用以供給前述成形 體之前述旋轉爐床式還原爐之供給部的環境溫度在115(TC 15 以下。 (15) 如第（8)項之將轉爐灰燼回收至旋轉爐床式還 原爐的方法’其中調整成含水分為5〜16質量％且金屬鐵比 率為8 35質里％之狀態的前述轉爐灰燼係儲備於其下部之 隹卩被力…、且使掺雜之氧濃度在5%以下之惰性氣體流 20 入的儲備槽。 (16) 如第（15)項之將轉爐灰燼回收至旋轉爐床式 還原爐的方法，其中前述儲備槽中，平均每噸所儲備之轉 爐灰燼，使接雜+与π & ^ ^ > y、之氧》辰度在5%以下之氣以母小時〇.5Nm3 以上流入。 14 200417611 玖、發明說明 圖式簡單說明 第1圖係一用以實施本發明之旋轉爐床式還原爐和其 附帶設備之例，且係顯示處理高含水分之微粒轉爐灰燼時 之設備結構的圖。 5 第2圖係另一用以實施本發明之旋轉爐床式還原爐和 其附帶設備之例，且係顯示將微粒轉爐灰燼處理成含水分 5〜16質量％時之設備結構的圖。 第3圖係用以實施本發明之微粒轉爐灰燼之儲備槽之 加熱裝置和惰性氣體吹入口的圖。 10 【實施方式】 用以實施本發明之最佳形態 首先，說明可回收微粒轉爐灰燼，而盡量不使其氧化 之本發明的方法。 第1圖顯示用以實施本發明之具有鍋式粉體造粒裝置 15 之旋轉爐床法之灰燼還原製程設備的一例。該設備包含有 由微粒轉爐灰燼儲備坑1，漿體儲備槽2及粉焦炭儲備槽3 所構成之原料之儲備設備。又，更包含有由漿體混合槽4 ，脫水機5及成形裝置6所構成之原料設備，又，也包含 有作為燒成還原裝置之旋轉爐床式還原爐7,該還原爐附 20 加有還原鐵冷卻裝置8和排氣處理裝置9。 首先，說明作為原料之微粒轉爐灰爐的事前處理。與 轉爐氣體一起產生之微粒轉爐灰燼由文氏洗氣器進行濕式 集塵。利用粗粒分離裝置，分離該轉爐灰燼與水之漿體中 約10/zm以上之大粒子之後，再利用增稠劑將灰燼濃縮， 15 200417611 玖、發明說明 且利用脫水機使含水分成為20〜3 5質量％ 。此時，微粒轉 爐灰燼之化學成分約係金屬鐵為60〜75質量％ ，氧化鐵為 20質量％ ，而平均粒徑係約1〜5//m。又，因為在轉爐所 使用之廢料之鋅被濃縮於微粒轉爐灰燼中，所以鋅濃度一 5 般而言係0.2〜1質量％ 。 接著，說明利用旋轉爐床法將微粒轉爐灰燼還原之本 發明的方法。本發明之方法中，係使微粒轉爐灰燼之含水 分降低至15〜20質量％以下，藉此將所含有之金屬鐵之氧 化抑制到最小限度，再利用旋轉爐進行還原和脫鋅處理。 10 首先，將已完成脫水之含水分為20〜35質量％之微粒 轉爐灰燼放入微粒轉爐灰爐儲備坑1。又，視情況而定， 亦可使用不作脫水處理而是利用增稠劑濃縮之漿體狀態之 微粒轉爐灰爐。此時，微粒轉爐灰燼之含水分係約70〜90 質量％ 。在混合槽4將此種微粒轉爐灰燼與由漿體儲備槽 15 2及粉焦炭儲備槽3供給之其他淤渣類和粉焦炭混合，而 製成含水分為55質量％以上之混合漿體。本發明中，可將 此時之微粒轉爐灰燼之金屬鐵調整成30〜70質量％。 本發明中，不使微粒轉爐灰燼之含水分降低，而是將 其與其他粉體混合而使含水分成為55質量％以上的理由係 20 在高含水分之狀態中，可解決金屬鐵之氧化問題。即，舉 例而言，雖然金屬鐵比率高，但是在水中，微粒轉爐灰燼 和空氣之接觸不良，可使金屬鐵之氧化緩慢，又，也有因 為水之熱容的關係，所以即使金屬鐵氧化時，依舊不會變 成高溫的效果。更進一步，其理由還有若使含水分成為55 16 200417611 玖、發明說明 質量％以上時，則濕式之混合頗為良好。結果，可使作為 原料之微粒轉爐灰燼之金屬鐵比率變高，而獲得減少用於 回收處理之還原此置消耗的效果。 利用脫水裝置5將該混合漿體脫水。令脫水後之含水 5分為17〜27質量％ 。脫水裝置5只要可使脫水後之含水分 成為前述之值者，則任一型式皆可，不過以將漿體注入到 濾、布上’且利用上下一對之壓搾滚輪搾乾該漿體和濾布之 型式的脫水機，壓濾機式脫水機，真空轉筒式脫水機，或 離心分離式脫水機為佳。再者，與含水分多之微粒轉爐灰 10燼混合時，若其他粉體之含水分低，可省略脫水步驟而在 單純地混合之後成形。特別是，將已脫水之微粒轉爐灰燼 與比較上含水分較少之粉體混合使用時，使用這種方法較 為有利。 利用成形裝置6將該脫水物製成約1 〇〜4〇mm之圓筒或 15 粒狀之成形體。宜令成形體之孔隙率為40〜53% 。令成形 體之孔隙率為40〜53%的理由留待後述。成形方法中，使 用一種於桶型外筒之端板有孔型，且該外筒之内部具有螺 旋式擠壓裝置的擠壓成形機是有效之方法。又，亦可使用 其他方式之擠壓成形機和壓塊成形機。 2〇 又’若利用脫水機5製成厚10〜25mm之脫水餅狀物時 ’可省略成形步驟。此時，利用脫水機5令含水分為 17〜27質量％ ，孔隙率為40〜53% 。有將其粉碎而成為長 15〜30mm之粒狀，藉此製成旋轉爐床式還原爐7之原料成 形體的方法。此時所用之脫水機宜為壓濾機式之脫水機。 17 200417611 玖、發明說明 接下來，將該成形體供給至旋轉爐床式還原爐7，使 其燒成還原。本發明之方法中，因為成形體含有較多之水 分，所以必須防止成形體之爆裂。本發明人進行了種種實 驗，發現由於孔隙率愈高，水蒸氣愈易消失，内部壓力不 5會變高，故不會產生爆裂。實驗結果中，得知若孔隙率為 40%以上時，則即使是在約115〇。〇之高溫之爐内，也不會 引起爆裂。另一方面，亦得知若孔隙率為54%以上時，則 成形體多孔質太過，使成形體之強度降低，無法承受從脫 水機5搬送至旋轉爐床式還原爐7。 1〇 旋轉爐床式還原爐7中，在高溫之爐内，利用所混合 之碳，將成形體内部之微粒轉爐灰燼和其他氧化物粉體所 含之氧化鐵、氧化錳、氧化鉻、氧化鋅等還原。 接著，說明以適當之混合比率將微粒轉爐灰燼混合， 使造粒穩定之回收之本發明的方法。 15 第2圖顯示用以實施本發明之具有鍋式粉體造粒裝置 之旋轉爐床法之灰燼還原製程設備的一例。該設備包含有 微粒轉爐灰燼儲備槽，其他粉體儲備槽1〇，粉焦炭儲 備槽3，黏結劑儲備槽u等原料之儲備設備，又，更包含 有勑體輪送機12，粉體粉碎混合裝置13，粉碎物輸送機 〇 14及鍋式造粒裝置6 。另，還包含有經由粒輸送機15而 將灰燼燒成還原之裝置的旋轉爐床式還原爐7，該還原爐 附加有排氣處理裝置9和還原鐵冷卻裝置8。 首先，說明作為原料之微粒轉爐灰燼的事前處理。另 ，该事前處理係與前述之方法一樣。與轉爐氣體一起產生 18 200417611 玖、發明說明 之微粒轉爐灰燼中由文氏洗氣器進行濕式集塵之轉爐灰燼 與水的漿體，係利用粗粒分離裝置分離其中約l〇//m以上 之大粒子之後，再利用增稠劑將灰燼濃縮，且利用脫水機 使含水分成為20〜35質量％。此時，微粒轉爐灰燼之化學 5 成分約係金屬鐵為60〜75質量％ ，氧化鐵為20質量％ ，而 平均粒徑係約1〜5/zm。又，因為在轉爐所使用之廢料之鋅 被濃縮於微粒轉爐灰爐中，所以鋅濃度一般而言係0.2〜1 質量％ 。 接著，說明利用旋轉爐床法將前述微粒轉爐灰燼還原 10 之本發明的方法。 使前述微粒轉爐灰燼乾燥，俾含水分成為5〜16質量％ 。令含水分在5〜16質量％之範圍内的理由，留待說明微粒 轉爐灰燼儲備方法時再詳述。微粒轉爐灰燼之乾燥，以利 用金屬鐵之氧化熱的方法為佳。乾燥方式不拘，不過，將 15 微粒轉爐灰燼裝入有圓筒旋轉之裝置之内部，且令空氣通 過而使微粒轉爐灰燼之金屬鐵氧化的方法，以及將微粒轉 爐灰燼舖開於廣場，令空氣通過而使微粒轉爐灰燼之金屬 鐵氧化的方法等，藉著這些利用鐵之氧化熱使含水分蒸發 的方法等係較為經濟的。 20 此時，調整微粒轉爐灰燼之氧化程度，令殘留之金屬 鐵為8〜35質量％。調整氧化程度，有測量微粒轉爐灰燼之 含水分變化率（水分蒸發量）而加以控制等的方法。當為 了去除含水分而使金屬鐵比率變得太低時，可事前利用曰 曬乾燥等方法，預先調整處理前之含水分。 19 200417611 玖、發明說明 若令乾無後之金屬鐵比率為8質量％以下，則造成因 為通常條件下，金屬鐵之燃燒熱會較乾燥相關之熱產生更 夕’所以微粒轉爐灰爐之溫度變得過高，導致一部分燒結 且產生難處理之塊的問題。又，亦造成由於氧化進行過 5度，故後續步驟之利用旋轉爐床式還原爐之還原能量增多 的問題。另一方面，若乾燥後之金屬鐵比率為35質量％以 上，則當乾燥前之微粒轉爐灰燼之含水分在25質量％以上 時，便不能確保乾燥所須之發熱量，而必須由外部供給用 以乾燥之能量。結果，^ 了乾燥，需有另外之裝置和能量 10 ，並非經濟的方法。因此，本發明之微粒轉爐灰燼之性質 中，金屬鐵之比率為8〜35質量％之點很重要。更進一步， 由於若含水分較低，且金屬鐵比率超過35 f量〇/❻時，將有 健備中之金屬鐵之氧化的發熱劇烈，損壞機械之問題，故 金屬鐵比率為35質量％以下是很重要的。 15 將含水分為5〜16質量％且金屬鐵比率為8〜35質量％ 之微粒轉爐灰燼收納於微粒轉爐灰爐儲備槽i.。因為微 粒轉爐灰爐係係細微到平均粒徑約之程度，所以 =含水分較5%彡日夺，從卡車上卸下或在廣場處理時激烈 2塵’將產生環境上之問題。又，如前所述，含水分為^ 2〇質以下之微粒轉爐灰爐與空氣之接觸良好，會使金屬 鐵氧化熱之發熱劇烈，導致設備損壞 。因此，宜作管理， 使含水分成為5質量％以上。 又，由於微粒轉爐灰燼係微粒，故水分含量多之狀態 之微粒轉爐灰燼容易變成黏土狀，而造成難以由微板轉爐 20 200417611 玖、發明說明 灰燼儲備槽排出之問題。本發明人發現若含水分為16 質量％以上時，便會頻頻發生微粒轉爐灰燼黏附於微粒轉 爐灰燼儲備槽内部之現象（附著而難以去除）。因此， 微粒轉爐灰燼之含水分為16質量％以下。 5 又，在微粒轉爐灰燼儲備槽1 >之内部，微粒轉爐灰200417611 发明 Description of the invention (The description of the invention should state: the technical field to which the invention belongs, the prior art, the content, the embodiments, and the drawings are briefly explained.) L The technical field to which the invention belongs 3 TECHNICAL FIELD The present invention relates to a method of using a rotary hearth Reduction furnace recovery process 5 A method of using converter ash collected by a non-combustion gas treatment device as iron raw material in a conventional ironmaking plant. I: Prior art 3 Background technology In a continuous ironmaking operation using a blast furnace converter, one ironmaking plant can produce 3 million to 10 million tons of steel a year. This is a very efficient ironmaking method. In the converter, oxygen is sprayed to the molten pig iron and scrap produced in the blast furnace, and the combustion heat of carbon and silicon in the pig iron is used to raise the temperature to obtain a molten steel with a low carbon concentration. At this time, the converter generates carbon monoxide-based gas, and the amount of gas is 100 Nm3 per 1 ton of pig iron. The converter gas 15 is doped with iron ash of about 100 g / Nm3, that is, about 10 kg / t steel. Iron ash doped with converter gas (hereinafter referred to as converter ash) includes coarse particles and fine particles. Coarse-grained converter ash has a particle size of about 30 # m to 1mm. These ash are blown by molten iron in the converter, and contain about 80-90% by mass of metallic iron and 10% by mass of iron oxide. Fine-grained converter 20 Ash has a particle size of about 1 to 5 / zm. These ashes are those in which molten iron in the converter evaporates due to the combustion heat of oxygen and is condensed to be blown up with the gas, and contains 70% by mass of metallic iron and about 30% by mass of iron oxide. Particulate converter ash is also doped with zinc from waste material which is also evaporated in the converter furnace. It varies according to the zinc content of the waste material used, etc. Generally, the zinc concentration 6 200417611 is about 0.2 to 1% by mass. The converter gas is a non-combustion gas processing device, so-called 〇G (Oxygen converter gas recovery) device. ♦ τκ wood dust is used as fuel gas for power generation and steel heating. ° G device has Venturi washing The dust collector of the air device method collects ashes while spraying water. First, the coarse-grained part of the converter ash furnace in the dust-collecting water is separated by a primary sink tank and injected into the thickener. In the thickener, the particulate converter ash is precipitated, and the thickened concentration is dehydrated by a dehydrator to a water content of 20 to 30% by mass. Coarse-grain converter ash is a useful iron resource due to its large particle size, high metal-iron ratio, and low zinc ratio, and there are various recovery methods to recover it. In particular, they are recycled as raw materials for sintering machines and used to replace waste materials in converters. However, on the other hand, since the particle size of the particulate converter ash is extremely small, from 15 to 5 Am, the specific surface area is large, and the metallic iron is oxidized violently during storage. Since this oxidation is accompanied by heat generation, it is difficult to simply use a particulate converter ash furnace. Also, the problem of components such as zinc has become an obstacle to recycling. First, an effective method of recovering the particulate converter ash is to supply the particulate converter ash to the molten pig iron discharged from the blast furnace, and to remove the stone material from the molten pig iron. In addition, some people select the knife with a small amount of zinc, which is then recycled to the blast furnace by a sintering machine. As mentioned above, various methods have been tried in the past for the recovery of ash from the particulate converter. However, in conventional methods other than blast furnaces, the amount of particulate converter ash that can be recycled is limited, so it is impossible to recover all of the particulate converter by these methods alone. Here, in order to use a large amount of particulate converter ash, it is more effective to recycle it to the blast furnace system. However, the particulate converter ash contains zinc, and its use in the blast furnace is limited. That is, because there is a lot of zinc in the ash of the particulate converter, when it is recovered to the blast furnace by the 5-burner, the zinc will evaporate in the high temperature part of the blast furnace, become zinc oxide or vaporized zinc, and attach to the furnace wall . As a result, the problem that ore and coke in the blast furnace fall and disappear in the furnace is caused. The method to deal with the problem is that if the particulate converter ash is dezincified, it can also be used in a blast furnace. Therefore, some people have also tried to use the rotary kiln (Waelz 10 klln) method and the rotary hearth method to dezincify, so that the blast furnace can be used. Among them, the condensing hearth method has been used as an off-line process because the dezincification rate is as high as 90% or more and reduced iron is available. Recently, as disclosed in Japanese Patent Laid-Open Publication No. 2000-34526 filed by the present inventor, a method has been developed to increase the strength of the granules reduced by the rotary hearth method by 15 to a level that can be used in a blast furnace. Particulate converter ash is ready for use in a blast furnace. In addition, the 'rotating hearth method is under the top and side walls of a fixed pair of firearms'. The hearth-shaped firing furnace with a disc-shaped refractory at the center is rotated at a certain speed as the main body. The process can be used to reduce the oxidation of 20 metals and iron ash treatment. The hearth of the rotary hearth reduction furnace is 10 to 50 meters in diameter and 2 to 6 meters in width. The raw materials are generally spherical granules formed by granulating powder with a rotating pan-shaped granulator. In order to use the rotary furnace hearth type reduction furnace to use the particulate converter ash, the particulate converter ash is mixed separately or it is mixed with other iron oxide-containing powders and powder 8 200417611 发明, invention description coke and other carbon-containing powders And made into spherical particles. Since the particulate converter ash also contains 20 to 35% by mass of water after dehydration, and it is very fine, it is clay-like, and has problems of poor handling and miscibility with other powders. If the moisture content of the particulate converter ash is also lowered, the handling and mixing properties can be improved. However, in the conventional technology, there is only the recognition that the particulate converter ash can be dried, and thus various problems arise as described later. As shown in Japanese Patent Laid-Open Publication No. 2000-54034, conventionally, a rotary hearth type reduction furnace has been used to process particulate converter ash. However, 10 First, simply, if the particulate converter ash is excessively dried, the metallic iron with a large specific surface area in the particulate state starts to react with the air to oxidize and generate heat. In particular, in the conventional technology, the importance of handling of the particulate converter ash as a powder and preventing it from adhering to the storage tank are caused, so that it is excessively dried, which causes a problem of heat generation. In severe cases, the temperature may even rise to about 800 ° c 15 and there is a danger of fire. In addition, there is also a method for preventing the occurrence of heating problems in the use step, and completely oxidizing the particulate converter ash furnace beforehand. However, at this time, in the oxidation treatment in the previous treatment in order to recycle, when serious, the pile of particulate converter ash will be heated above 800 ° C, and the sintering reaction occurs between the fine particles of particulate converter ash 20 embers. This causes a problem that the average particle diameter becomes large. Due to the sintering phenomenon, depending on the particle conditions, it may become several mm to several tens mm or more, or it may become a solid sintered block. Therefore, it must be pulverized before it can be mixed with other powders to be granulated. Moreover, even if this is done, the average particle diameter is still too large to be granulated into granules. In particular, if a particle converter ash having a particle size of 9 200417611 玖 and a description of the invention of ten to 100 // m is used, there is a problem that it cannot be made into good quality particles. That is, there is a technical problem in the method of completely performing the oxidation. Conventionally, because of the aforementioned problem of heat generation due to oxidation, the ratio that can be used in combination with other powders has been limited. In addition, if the particulate converter ash which has been completely oxidized is used, there are problems in that the cost of the operation for oxidizing it beforehand and the cost for crushing and processing the sintered particulate converter ash are problems. In addition, since the recovered metal-containing iron ash is specifically oxidized and used as a raw material, the reduction energy consumption rate for reduction using a rotary hearth type reduction furnace is large and cannot be said to be an economical method. 10 In order to solve the heat generation accompanying the oxidation reaction of the particulate converter ash, in the method of oxidizing most of the semi-metallic iron and recycling it using a rotary hearth type reduction furnace, the particulate converter ash containing a large amount of metallic iron is particularly oxidized to reduce it , Which is disadvantageous in terms of energy consumption. Therefore, there is a need for a technology that can use the granulated converter ash as the raw material of the rotary hearth type reduction furnace without oxidizing it as much as possible. Since the particle converter ash is an average particle of 1 to 5 // m, when it contains moisture, it becomes clay-like, and the problem of difficult handling becomes a major obstacle to the recovery of the particle converter ash. That is, inside the storage tank and the like, the particulate converter ash is stuck (attached and difficult to remove), causing a problem of poor discharge 20. If the particulate converter ash is dried to cope with the problem, the metallic iron contained therein is easily oxidized, so the problem of oxidative heat generation of the particulate converter ash inside the storage tank and the like occurs. Since these problems have not been solved, in the conventional technology, heavy machinery is used on the ground to mix particulate converter ash with other iron-containing ash, etc. 10 200417611 玖, description of the invention, and then using this mixture as a rotary hearth type reduction furnace Of raw materials. However, in this method, the raw materials cannot be mixed quantitatively and stably. As a result, it is not possible to sufficiently mix the raw materials quantitatively to achieve an appropriate mixing ratio, thereby stabilizing the powder granulation and stabilizing the reduction reaction in the rotary hearth type reduction furnace. That is, the treatment of the rotary hearth type reduction furnace when the particulate converter ash is used as a part of the raw material is not necessarily stable. In addition, there is not enough knowledge about the reduction method of the particle converter ash furnace using a rotary hearth type reduction furnace. In the conventional technology, only the particles made by mixing the particle converter ash and carbon powder at a high temperature are reduced. It can be recognized that there is no efficient and large-scale reduction furnace treatment. As mentioned above, it is technically difficult to make raw granules that can be used in the rotary hearth method using particulate converter ash as a raw material. Therefore, there is a need for a new technology that uses particulate converter ash as part of the raw materials to make granules suitable for a rotary hearth type reduction furnace, and then reduces it. 15 Therefore, the present invention provides a method for using particulate converter ash as a raw material and reducing it efficiently using a rotary hearth type reduction furnace, which provides 1) a particulate converter ash can be used as a rotary hearth type reduction furnace Recycling technology that minimizes the oxidation of raw materials, and 2) can mix particulate converter ash with an appropriate mixing ratio to stabilize granulation and stabilize the reduction reaction of a rotary hearth reduction 20 furnace. SUMMARY OF THE INVENTION The present invention has been made in order to solve the aforementioned problems, and the gist thereof is as follows. (1) A method for recovering converter ash to a rotary hearth type reduction furnace 11 200417611 玖, description of the invention, the converter ash is collected by the non-combustion dust collector of converter gas to collect the converter ash as a thickener precipitate, and mixed After the iron oxide-containing powder and the carbon-containing powder, the moisture content was adjusted to 17 to 27% by mass, and a formed body having a porosity of 40 to 54% was prepared, and the formed body was charged into a rotary hearth type Reduction furnace and 5 to restore it. (2) —A method for recovering converter ash to a rotary hearth type reduction furnace 'is collected by converter ash collected by converter non-combustion dust collector and used as thickener sink ash, mixed with iron oxide-containing After the powder and the carbon-containing powder, a slurry having a water content of 55% by mass or more is prepared, and the slurry 10 is dehydrated to produce a dehydrated product having a water content of 17 to 27%, and the dehydrated product is prepared. The molded body is formed into a shaped body having a porosity of 40 to 54%, and the shaped body is charged into a rotary hearth type reduction furnace and reduced. (3) The method for recovering converter ash to a rotary hearth type reduction furnace as in item (2), wherein the converter ash is collected by a non-combustion type 15 dust collector of converter gas, and the coarse particle separation tank is used to separate the The coarse particles of converter ash are 'collected' as thickener deposits. (4) The method for recovering converter ash to a rotary hearth type reduction furnace as in item (2), wherein the converter ash is collected by a non-combustion dust collector of converter gas, and the converter is separated using a coarse-grained separation tank. After the coarse grains of ash are collected as a thickener sink, and dehydrated to a moisture content within the range of 20 to 35% by mass. (5) The method for recovering converter ash to a square-converter hearth-type reduction furnace as in any one of items (1) to (4), wherein the metal-iron ratio of the converter ash furnace is 35% by mass or more. 12 200417611 发明, description of the invention (6) As in any one of 苐 (2) to (5), a method for recovering converter ash to a rotary hearth type reduction furnace, which uses an extrusion-type forming device to make the foregoing The dehydrated product is shaped and formed into a shaped body. (7) — A method for recovering converter ash to a rotary hearth type reduction furnace 5 The converter ash collected as dust by the thickener collected by the non-combustion dust collector of converter gas is adjusted to a water content of 5 ~ 16% by mass and a metal-iron ratio of 8 to 35% by mass, and after mixing a powder containing iron oxide and a sintered charcoal to form a mixture, the mixture is formed into a formed body, and the formed body is formed. (8) A method for recovering converter ash to a rotary hearth type reduction furnace as described in item (7), wherein the aforementioned mixture is adjusted to contain water into The converter ash furnace in a state of 5 to 16% by mass and a metal-iron ratio of 8 to 35% by mass is stored in a storage tank, and the foregoing 15 converter ash is separated from the storage tank by a quantitative dispensing device and mixed with a predetermined mixture. Ratio, mixed with iron oxide powder and carbon powder. (9) The method for recovering converter ash to a rotary hearth type reduction furnace according to item (7) or (8), which uses a pot granulator to form the aforementioned mixture into a spherical pellet. 20 (10) The method for recovering converter ash to a rotary hearth type reduction furnace as described in item (7) or (8), which is a method of converting powder containing iron oxide and carbon-containing powder to the converter The ash is mixed and pulverized to form a mixture, and then the mixture is formed into a spherical pellet shaped body using a pot granulator. (11) Recovery of converter ash to rotation as described in item (7) or (8) 13 200417611 发明 Description of the invention The method of hearth type reduction furnace is formed by using a pair of rollers with a plurality of concave forming dies The device makes the aforementioned mixture into a compacted compact. (12) The method for returning converter ash to 5 as described in any one of items (1) to (11) to a rotary hearth type reduction furnace, wherein the stone contained in the aforementioned compact is in combination with iron, towers, and towers. The atomic mole ratio of oxygen of chromium, chromium, zinc and zinc oxide is in the range of 0.5 to 1.5. 〇3) The method for recovering converter ash to the rotary hearth type reduction furnace according to any one of the items (12), which is to supply the aforementioned compact to the aforementioned rotary hearth type reduction furnace at 1200 ° It is reduced by heating at an ambient temperature of C or more for 6 minutes or more. (14) The method for recovering converter ash to a rotary hearth type reduction furnace as described in any one of items (1) to (13), which is a method of making the rotary hearth type reduction furnace for supplying the foregoing formed body The ambient temperature of the supply unit is 115 (TC 15 or less. (15) The method for recovering converter ash to a rotary hearth type reduction furnace as described in item (8), where the moisture content is adjusted to 5 to 16% by mass and metallic iron is adjusted. The aforementioned converter ash with a ratio of 8 35 mass% is a reserve tank in which the lower part of the compressive force is reserved, and an inert gas with a doped oxygen concentration of 5% or less flows into the reserve tank. (16) Such as Item (15): A method for recovering converter ash to a rotary hearth type reduction furnace, wherein in the aforementioned storage tank, an average of converter ash stored per ton is used to couple + and π & ^ ^ > y, of Oxygen gas with a temperature of less than 5% flows in at a rate of more than 0.5 Nm3 for the mother hour. 14 200417611 玖 Brief description of the invention, the diagram 1 is a rotary hearth type reduction furnace for implementing the present invention and its accompanying equipment This is an example, and shows the structure of the equipment when processing high-moisture particulate converter ash Fig. 5 Fig. 2 is another example of a rotary hearth type reduction furnace for implementing the present invention and its accompanying equipment, and shows the structure of the equipment when the particulate converter ash is processed to 5 to 16% by mass of water Fig. 3 is a diagram of a heating device and an inert gas blowing inlet of a storage tank for implementing the particulate converter ash of the present invention. [Embodiment] The best form for implementing the present invention First, the recoverable particulate converter ash will be described. FIG. 1 shows an example of an ash reduction process equipment for implementing the rotary hearth method of the pot-type powder granulation device 15 of the present invention. The equipment includes Raw material storage equipment composed of particulate converter ash storage pit 1, slurry storage tank 2 and powder coke storage tank 3. It also includes raw material equipment composed of slurry mixing tank 4, dehydrator 5 and forming device 6. In addition, it also includes a rotary hearth type reduction furnace 7 as a firing reduction device, and the reduction furnace is provided with 20 reduced iron cooling device 8 and exhaust treatment device 9. First, the particle conversion as a raw material will be described. Pre-treatment of the ash furnace. The particulate converter ash generated with the converter gas is wet-dusted by a Venturi scrubber. Using a coarse particle separation device, the converter ash and water slurry is separated by about 10 / zm. After the particles, the thickener is used to thicken the ash. 15 200417611 玖, the description of the invention and the use of a dehydrator to make the water content 20 ~ 35 mass%. At this time, the chemical composition of the particulate converter ash is about 60 ~ 75 Mass%, iron oxide is 20 mass%, and the average particle size is about 1 ~ 5 // m. In addition, the zinc used in the converter is concentrated in the particulate converter ash, so the zinc concentration is 5 Department 0.2 to 1% by mass. Next, a method of the present invention for reducing particulate converter ash by a rotary hearth method will be described. In the method of the present invention, the moisture content of the particulate converter ash is reduced to 15 to 20% by mass, thereby suppressing the oxidation of the contained metallic iron to a minimum, and then using a rotary furnace for reduction and dezincification. 10 First, the dehydrated water content is divided into particulate matter ash of 20 to 35% by mass and placed in the particulate matter converter ash furnace pit 1. In addition, depending on the circumstances, a particulate converter ash furnace in a slurry state which is not concentrated to a dehydration treatment but thickened with a thickener may be used. At this time, the moisture content of the particulate converter ash is about 70 to 90% by mass. In the mixing tank 4, such particulate converter ash is mixed with other sludges and powder coke supplied from the slurry storage tank 15 2 and the powder coke storage tank 3 to prepare a mixed slurry having a water content of 55% by mass or more. In the present invention, the metallic iron in the particulate converter ash at this time can be adjusted to 30 to 70% by mass. In the present invention, instead of reducing the moisture content of the particulate converter ash, the reason for mixing it with other powders to make the moisture content more than 55% by mass is 20 In a state of high moisture content, the oxidation of metallic iron can be solved problem. That is, for example, although the ratio of metallic iron is high, the poor contact between particulate converter ash and air in water can slow the oxidation of metallic iron, and because of the heat capacity of water, even when metallic iron is oxidized , Still does not become the effect of high temperature. Furthermore, the reason is that if the moisture content is set to 55 16 200417611 发明, and the mass ratio is at least mass%, the wet mixing is quite good. As a result, the metal-iron ratio of the particulate converter ash as a raw material can be increased, and the effect of reducing the consumption of the reduction unit for recovery processing can be obtained. The mixed slurry is dewatered by the dewatering device 5. The water content after dehydration was divided into 17 to 27% by mass. As long as the dewatering device 5 can make the moisture content after the dehydration become the aforementioned value, any type is possible, but the slurry is injected into the filter and cloth 'and the slurry is squeezed out by a pair of upper and lower pressing rollers Filter cloth type dehydrators, filter press type dehydrators, vacuum drum type dehydrators, or centrifugal separator type dehydrators are preferred. In addition, when mixing with the fine-grained converter ash 10 ash containing a large amount of water, if the water content of other powders is low, the dehydration step can be omitted and the powder can be simply mixed. In particular, it is advantageous to use this method when mixing dehydrated particulate converter ash with powder with relatively low moisture content. This dehydrated product was formed into a cylinder of about 10 to 40 mm or a 15-shaped molded body by the molding device 6. The porosity of the formed body should preferably be 40 ~ 53%. The reason why the formed body has a porosity of 40 to 53% will be described later. In the forming method, it is effective to use an extruder having a hole type in the end plate of the barrel-shaped outer cylinder and having a screw-type extrusion device inside the outer cylinder. Alternatively, other types of extrusion molding machines and briquetting machines may be used. 2 ′ If forming a dehydrated cake with a thickness of 10 to 25 mm using the dehydrator 5, the forming step may be omitted. At this time, the water content was divided into 17 to 27% by mass using a dehydrator 5 and the porosity was 40 to 53%. There is a method of pulverizing it into a pellet shape having a length of 15 to 30 mm, thereby forming a raw material shaped body of the rotary hearth type reduction furnace 7. The dehydrator used at this time should be a filter press type dehydrator. 17 200417611 (ii) Description of the invention Next, the formed body is supplied to a rotary hearth-type reduction furnace 7 to be calcined and reduced. In the method of the present invention, since the formed body contains a large amount of water, it is necessary to prevent the formed body from bursting. The inventors carried out various experiments and found that the higher the porosity, the easier it is for water vapor to disappear, and the internal pressure will increase, so no burst will occur. From the experimental results, it was found that when the porosity was 40% or more, it was about 115 °. It will not cause a burst in a high temperature furnace. On the other hand, it was also found that if the porosity is 54% or more, the formed body is too porous, which reduces the strength of the formed body, and cannot withstand the transfer from the dehydrator 5 to the rotary hearth type reduction furnace 7. 10 In the rotary hearth type reduction furnace 7, in the high-temperature furnace, the mixed carbon is used to convert the particulate converter ash inside the formed body and other oxide powders to iron oxide, manganese oxide, chromium oxide, and oxide. Reduction of zinc, etc. Next, the method of the present invention will be described in which particulate converter ash is mixed at an appropriate mixing ratio to stabilize the granulation. 15 Fig. 2 shows an example of an ash reduction process equipment for implementing a rotary hearth method having a pot-type powder granulating device of the present invention. This equipment includes storage equipment for raw materials such as particulate converter ash storage tanks, other powder storage tanks 10, powder coke storage tanks 3, binder storage tanks u, and also includes a carcass carousel 12 for powder crushing. Mixing device 13, pulverized material conveyor 014, and pan granulation device 6. It also includes a rotary hearth type reduction furnace 7 which is a device for burning and reducing ash through a pellet conveyor 15. The reduction furnace is additionally provided with an exhaust treatment device 9 and a reduced iron cooling device 8. First, the pre-treatment of particulate converter ash as a raw material will be described. In addition, the pre-processing is the same as the aforementioned method. With the converter gas, 18 200417611 玖, the particulate converter converter ash described in the invention, the wet ash of the converter ash and water slurry is collected by a Venturi scrubber, which is about 10 // m separated by a coarse particle separator After the above large particles, the thickener is used to concentrate the ash, and the water content is adjusted to 20 to 35% by mass using a dehydrator. At this time, the chemical 5 component of the particulate converter ash is approximately 60 to 75% by mass of metallic iron, 20% by mass of iron oxide, and the average particle size is approximately 1 to 5 / zm. In addition, the zinc concentration of the waste used in the converter is concentrated in the particulate converter ash furnace, so the zinc concentration is generally 0.2 to 1% by mass. Next, a method of the present invention for reducing the particle converter ash 10 by a rotary hearth method will be described. The particulate converter ash was dried, and the moisture content of the mash was 5 to 16% by mass. The reason why the moisture content is in the range of 5 to 16% by mass will be described in detail when the method for storing the particulate converter ash is described. The drying of the particulate converter ash is preferably performed by using the oxidation heat of metallic iron. The drying method is not limited, but a method of charging 15 particles of converter ash into the inside of a device with a rotating cylinder and passing air through to oxidize the metal iron of the particles of converter ash, and spreading the particles of converter ash on the square to make air The method of oxidizing metallic iron of the particulate converter ash by this method, etc., and the method of evaporating moisture by utilizing the heat of oxidation of iron are economical. 20 At this time, the degree of oxidation of the particulate converter ash is adjusted so that the residual metallic iron is 8 to 35% by mass. To adjust the degree of oxidation, there are methods such as measuring and controlling the moisture content change rate (water evaporation amount) of the particulate converter ash. When the metal-iron ratio becomes too low in order to remove moisture, the moisture content before treatment can be adjusted in advance by means such as sun drying. 19 200417611 发明 Description of the invention If the ratio of metal iron after drying is 8% by mass or less, the temperature of the particulate converter ash furnace will be higher because the combustion heat of metal iron will be generated more than the heat related to drying under normal conditions. It becomes too high, causing a problem that a part is sintered and difficult to handle. In addition, since the oxidation progressed to 5 degrees, the reduction energy of the rotary hearth type reduction furnace in the subsequent step was increased. On the other hand, if the metal-iron ratio after drying is 35% by mass or more, when the moisture content of the particulate converter ash before drying is 25% by mass or more, the amount of heat required for drying cannot be ensured, but must be supplied from the outside For drying energy. As a result, drying requires additional equipment and energy, which is not an economical method. Therefore, in the properties of the particulate converter ash of the present invention, it is important that the ratio of metallic iron is 8 to 35% by mass. Furthermore, if the water content is low and the metal-iron ratio exceeds 35 f 〇 / ❻, there will be severe heat generation due to the oxidation of the metal iron in the health and damage to the machine, so the metal-iron ratio is 35 mass% or less Is very important. 15 Particulate converter ash containing 5 to 16% by mass of water and a metal-iron ratio of 8 to 35% by mass is stored in a particulate converter ash furnace storage tank i. Because the micro-converter ash furnace system is so small that it has an average particle size, the moisture content is less than 5%, so it will cause environmental problems when it is unloaded from a truck or treated intensely in a square. In addition, as mentioned above, the fine-converter ash furnace with a water content of less than ^ 20 is in good contact with the air, which will cause the metal iron to oxidize heat and cause equipment damage. Therefore, it is advisable to manage it so that the moisture content becomes 5 mass% or more. In addition, since the particulate converter ash is a kind of particulates, the particulate converter ash with a high moisture content easily becomes clay-like, which makes it difficult to be discharged from the micro-plate converter 20 200417611 2004, description of the invention ash storage tank. The inventors have found that if the water content is 16% by mass or more, the phenomenon that the particulate converter ash adheres to the interior of the particulate converter ash storage tank (attachment and difficult to remove) occurs frequently. Therefore, the moisture content of the particulate converter ash is 16% by mass or less. 5 And inside the particulate converter ash storage tank 1 >, the particulate converter ash
燼和空氣中之氧漸漸地發生反應，藉此槽内部之溫度稍微 昇高。藉該反應，微粒轉爐灰燼儲備槽内部之微粒轉 爐灰燼之溫度會較外面空氣昇高10〜40°c。結果，雖然是 以緩慢之速度，但微粒轉爐灰燼之水分將會蒸發。一旦該 10 水蒸氣到達微粒轉爐灰燼儲備槽1 >之鐵皮，便在此凝結 。此現象亦在第3圖所示之微粒轉爐灰燼儲備槽下部 之錐部16發生。結果，導致在錐部16之微粒轉爐灰燼不 能排出。如前所述，即使微粒轉爐灰燼之含水分為16質量 %以下，還是會產生粉體不易由錐部16排出的問題。The embers and the oxygen in the air gradually react, whereby the temperature inside the tank rises slightly. By this reaction, the temperature of the particulate converter ash inside the particulate converter ash storage tank will rise by 10 to 40 ° C compared to the outside air. As a result, although at a slow rate, the moisture of the particulate converter ash will evaporate. Once the 10 water vapor reaches the iron sheet of the particulate converter ash storage tank 1 >, it condenses there. This phenomenon also occurs in the cone portion 16 at the lower portion of the particulate converter ash storage tank shown in FIG. As a result, the particulate converter ashes in the cone portion 16 cannot be discharged. As described above, even if the moisture content of the particulate converter ash is 16% by mass or less, there is a problem that the powder is not easily discharged from the cone portion 16.
15 為了解決該問題，所以加熱微粒轉爐灰燼儲備槽1 / 下部之錐部16。加熱方法可以是任何方法，不過以利用電 熱器和蒸氣加熱器加熱者為佳。第3圖之裝置之例中，顯 示利用電熱器之加熱裝置17。在錐部16中，由於目的在 於防止凝結，故宜令錐部16之加熱溫度為50〜80°C。 20 藉加熱錐部16防止凝結時，在該部分，無法變回水之 水蒸氣會上昇到微粒轉爐灰燼儲備槽之内部。若微粒 轉爐灰燼含有之水分少時，問題較少，但是若含水分多時 ，該水蒸氣會上昇到内部，並積聚於微粒轉爐灰燶儲備槽 1 >之側壁等。結果，在該部分產生微粒轉爐灰爐之黏附現 21 200417611 玖、發明說明 象（附著而難以去除）。為了解決該問題，所以使惰性氣體 流入微粒轉爐灰燼儲備槽1 /之内部。氣體之流入口宜位 於錐部16。為本發明之設備之例的第3圖中，係由氣體供 給管18供給惰性氣體，利用惰性氣體稀釋水蒸氣再使其流 5 入，藉此可順利地將水蒸氣排出至微粒轉爐灰燼儲備槽1 一之外部。 氣體之所以必須為惰性氣體，也是為了不使微粒轉爐 灰燼之金屬鐵氧化。因此，惰性氣體宜為氮和二氧化碳， 不過氧濃度在5%以下之不純氮和燃燒排氣等也有相同之 10 效果。又，若平均每1噸所儲備之微粒轉爐灰燼為每小時 0.5當量立方公尺/以上之流量，即可獲得充分之排出水蒸 氣之效果。 至於其他之粉體，係將高爐氣體灰燼和粉礦石裝入其 他粉體儲備槽10,作為還原劑之粉焦炭裝入粉焦炭儲備槽 15 3，又，膨土等黏結劑裝入黏結劑儲備槽11。若原料之種 類多，可設置更多之儲備槽。 將各儲備槽儲備之粉體定量地分出至粉體輸送機12上 ，俾成為預定之比率。利用粉體輸送機12搬運前述，且利 用粉體粉碎混合裝置13進行混合和粉碎。混合機械有好幾 20 種，不過球磨機式之粉碎混合裝置最適合。又，亦有通過 粉碎裝置後再將粉體混合的方法。 接著，利用粉碎物輸送機14將已粉碎混合之粉體運送 至鍋式造粒裝置。鍋式造粒裝置中，在直徑3〜6公 尺之中華鍋型旋轉鍋之上滾動含水分調整成8〜13質量％之 22 200417611 玖、發明說明 粉體’藉此製成球形之未加工粒。未加工粒之直徑宜為 5〜30mm。為了可穩定地製成高強度之未加工粒，以適當地 比率混合1〜10//m之微粒部分和5〇//m以上之粗粒部分是 很重要的。因此，若可以20〜80質量％之比率混合粒徑小 5 之微粒轉爐灰燼，便可製成良好之未加工粒。 又，成形體之製造方法中，使用包含有一對具有多數 凹狀成形模之滾輪的成形裝置，且在該凹狀之内部將混合 物體成形，藉此製成壓塊的方法係適於製造本發明之成形 體。該成形方法中，由一對具有凹狀成形模之滾輪的上部 10 供給混合粉體，並利用滾輪壓過。此時，在凹狀成形模之 内部，粉體被壓縮而製成成形體。另，為了保持成形體之 強度，所以一般會使用黏結劑。 利用粒輸送機15將前述成形體運送至旋轉爐床式還原 爐7。在旋轉爐床式還原爐7中將前述成形體燒成還原。 15由於有時在旋轉爐床式還原爐7之爐内加熱之時，會有因 成形體之水分蒸發造成之爆裂問題，故宜使成形體乾燥之 後’再供給至旋轉爐床式還原爐7。旋轉爐床式還原爐7 中’在高溫之爐内，利用所混合之碳，將微粒轉爐灰燼和 其他氧化物粉體所含之氧化鐵、氧化錳、氧化鉻、氧化鋅 20 等還原。 如前所述，本發明之方法中，不論何者皆是將轉爐灰 爐與含氧化鐵之粉體和含峡之粉體混合而製成粒、壓塊等 成形體，再利用旋轉爐床式還原爐將該成形體還原。 在旋轉爐床式還原爐之爐内，當粒和壓塊等成形體溫 23 200417611 玖、發明說明 度達到1100°C以上時，便會發生還原反應。特別是l2〇〇DC 以上之溫度中，反應變得活潑。為了令成形體内部之溫度 成為1100°C以上，且使反應活潑，所以爐内之環境溫度必 須為1200°c以上。本發明人發現藉由使在爐内之環境溫度 ‘ 5為1200°C以上之時間為6分鐘以上，可使鋅之去除率在8〇 質量％以上，且鐵之還原率在70質量％以上。因此，宜設 定處理時間，使含有微粒轉爐灰燼之成形體於12〇(rc以上 之爐内滯留6分鐘以上。 · 在旋轉爐床法之處理條件下，必須令利用旋轉爐床式 10還原爐7還原之物質和碳之比率適當。即，若成形體中之 碳，與鐵、錳、鎳、鉻、鉛及鋅等氧化物之氧的原子莫爾 比（石反當篁）係在0.5〜1.5之範圍内，如前所述，便可進 行高還原率且高脫鋅率之處理。若碳當量為〇·5以下，還 原不會完全地進行，無法令鐵之還原率在7〇質量％以上， 15又，脫鋅率亦變成約60〜80質量％ ，不能充分地實施本發 明目的之一的脫鋅。又，若碳當量為L5以上，因為碳過 ® 剩，反應結束後，碳還是殘留，而阻礙還原粒（成形體） 内部之粒子的結合，所以造成還原鐵粒（成形體）之強度 - 變低，無法在高爐使用的問題。 20 在旋轉爐床式還原爐7之爐内，業經還原之成形體係 利用螺旋式之排出裝置由爐内排出。排出之還原成形體係 利用還原鐵冷卻裝置8冷卻，再供給至高爐作為原料而成 為炫化生鐵。由於還原劑是使用粉焦炭和石炭，所以還原 鐵之硫含有率高’因此還原成形體之回收目的地以具有脫 24 200417611 玖、發明說明 硫功能之高爐最佳。不過，即使回收至轉爐和電爐也還是 可發揮效果。排氣係利用排氣處理裝置9除塵，再散布至 空氣中。 實施例 5 以下，依實施例詳細地說明本發明。 實施例1〜2 首先，說明回收轉爐灰燼而盡量不使其氧化之方法之 例。 將微粒轉爐灰燼和其他粉體混合，並製成含水分 10 17〜27質量％且孔隙率40〜54%之成形體，再將其還原處理 之結果係顯示於表1之實施例1、2。又，將其還原之方法 ，係顯示於以本發明之方法和類似之習知技術所作之處理 結果。設備係使用第1圖所示者。 本發明方法中，因為微粒轉爐灰燼是浸於水中之狀態 15 ，所以金屬鐵與氧之接觸少以及含有水之熱容大，故不會 有金屬鐵氧化發熱之問題，實施例1和2中，即使微粒轉 爐灰燼之金屬鐵比率是66〜67質量％ ，也沒有發熱之問題 〇 實施例1中，係使用僅將脫水物脫水之成形體之例。 20 將混合有32質量％之前述微粒轉爐灰燼之混合脫水物粉碎 ，製成厚20mm且平均長25mm之成形體。以本發明之條 件將其還原。結果，爐内之粉化比率少，為6質量％ ，處 理良好。然而，由於1200°C以上之還原溫度只有5分鐘之 短，故還原率和脫鋅率稍低，為75質量％和81質量％ 。 25 200417611 玖、發明說明 又’製品之壓碎強度為67kg，比較良好。 此外，所謂粉化比率，係指3mm篩下物之重量相對於 裝入重量的比率（質量％ )。 實施例2中，利用螺旋式擠壓成形裝置，將混合有32 5質之前述微粒轉爐灰燼之混合脫水物製成直徑12mm 且長16〜25mm之圓筒狀成形體。成形體之含水分係21質 里％ ，孔隙率係46質量％。利用旋轉爐床式還原爐7將該 成形體作還原處理。成形體之供給部之溫度為1〇5〇1，係 在本發明之範圍内。又，還原溫度為124〇t，還原時間為 10 10分鐘，皆是本發明之反應條件範圍内之處理。結果，粉 化率少，為6質量％ ，且還原率、脫鋅率和製品壓碎強度 都很良好。 另一方面’比較例1中，係利用第1圖之裝置進行處 理之例。不過，這是微粒轉爐灰燼之成分和含水分等雖大 15致和實施例1相同，但成形體之孔隙率低之處理之例。該 處理例中，由於成形體之孔隙率低，故在旋轉爐床式還原 爐7中成形體之粉化劇烈，竟有56質量％之原料變成粉。 因為鈿述影響，製品之還原率和脫鋅率也低。這是因為成 為粉者之周圍，由碳產生之一氧化碳無法形成充分之還原 20 環境，而造成粉之還原率降低。 比較例2亦是利用第1圖之裝置進行處理之例，其也 是微粒轉爐灰燼之成分和含水分等雖大致和實施例丨相同 ，但成形體之含水分過高之處理之例。該處理例中，成形 體之含水分過多，使得成形體變柔軟，而造成成形體間產 26 200417611 玖、發明說明 生黏著問題。結果，裝入旋轉爐床式還原爐7時，爐床上 之成形體之分散不均，而產生無法順利地接受上部空間之 氣體輻射的問題。又，因為成形體之含水分多，所以亦有 成形體粉化劇烈之問題。結果，製品粉化率高達37質量％ 5 ，又，還原率為48質量％ ，脫鋅率為61質量％ ，反應不 充分。再者，製品之強度不佳，為25kg。 因為本發明之處理方法中，係利用旋轉爐床式還原爐 7進行處理，而不使微粒轉爐灰燼之金屬鐵氧化，所以亦 達成即使微粒轉爐灰燼中用以還原之氧化鐵量少，且還原 10 相關之能量少也無妨的效果。表2所示之比較例3中，係 習知方法之使微粒轉爐灰燼之金屬鐵氧化，再將其與其他 粉體混合，並以此製成球形粒且將其還原之處理之例。由 於比較例3中係使用將微粒轉爐灰燼氧化至金屬鐵比率為 11質量％者，故還原能量消耗率係每1噸原料為6.44GJ。 15 另一方面，表2所示之利用本發明之方法進行處理之實施 例2中，雖然令原料混合率、還原條件等與比較例3之處 理大致相同，但是能量消耗少了約5% ，為6.11GJ。 如以上所說明，使用本發明之微粒轉爐灰燼之處理中 ，可有效地進行還原處理並去除鋅，同時還原率高，且可 20 製成高強度之還原鐵。結果，可大量地回收微粒轉爐灰燼 作為高爐原料。 27 200417611 玖、發明說明 〔表1〕 單位 實施例1 實施例2 比較例1 比較例2 灰微 A Ml 性轉 質爐 含水分 質量％ 56 57 51 51 金屬鐵比率 質量％ 66 67 64 63 微粒轉爐灰燼混合率 質量％ 33 32 32 33 有·無利用成形裝置成 形 無 有 有 有 成形體（脫水物）含水分 質量％ 22 21 22 32 成形體（脫水物）孔隙率 % 49 46 36 48 碳當量 1.1 1.1 0.88 1.1 還原溫度 °c 1215 1240 1240 1240 還原時間（1200°C以上） 分鐘 5 10 10 10 成形體粉化率 質量％ 6 6 56 37 製 品 性 質 還原率 質量％ 75 81 57 48 脫鋅率 質量％ 81 93 71 61 壓碎強度 kg 67 87 22 2515 In order to solve this problem, the particulate converter ash storage tank 1 / the lower cone portion 16 is heated. The heating method may be any method, but it is preferable to use an electric heater and a steam heater for heating. In the example of the device of Fig. 3, a heating device 17 using an electric heater is shown. Since the purpose of the taper portion 16 is to prevent condensation, the heating temperature of the taper portion 16 should preferably be 50 to 80 ° C. 20 When condensation is prevented by the heating cone portion 16, the water vapor that cannot be changed back to water rises to the inside of the particulate converter ash storage tank in this part. If the moisture contained in the particulate converter ash is small, there are fewer problems, but if the moisture content is high, the water vapor will rise to the inside and accumulate on the side walls of the particulate converter ash storage tank 1 >. As a result, the adhesion of the particulate converter ash furnace to this part is generated. 21 200417611 发明, description of the invention (adhesion and difficult to remove). To solve this problem, an inert gas is allowed to flow into the inside of the particulate converter ash storage tank 1 /. The gas inlet is preferably located at the cone 16. In Figure 3, which is an example of the equipment of the present invention, the inert gas is supplied from the gas supply pipe 18, and the water vapor is diluted by the inert gas and then allowed to flow in, thereby the water vapor can be smoothly discharged to the particulate converter ash reserve. Slot 1 is outside. The reason why the gas must be inert is not to oxidize the metallic iron in the ash of the particulate converter. Therefore, the inert gas is preferably nitrogen and carbon dioxide, but impure nitrogen and combustion exhaust with an oxygen concentration of less than 5% also have the same effect. In addition, if the average converter ash per 1 ton of particulate converter ash is at a flow rate of 0.5 equivalent cubic meters per hour or more, a sufficient effect of exhausting water vapor can be obtained. As for other powders, blast furnace gas ash and powder ore are charged into other powder storage tanks 10, and powder coke as a reducing agent is charged into powder coke storage tanks 15 3, and binders such as bentonite are loaded into the binder storage. Slot 11. If there are many kinds of raw materials, more reserve tanks can be set. The powder stored in each storage tank is quantitatively distributed to the powder conveyor 12 to form a predetermined ratio. The powder conveyor 12 is used to carry the foregoing, and is mixed and pulverized by a powder pulverizing and mixing device 13. There are several 20 types of mixing machines, but ball mill-type pulverizing mixing devices are the most suitable. There is also a method in which the powder is mixed after passing through a pulverizing device. Next, the pulverized and mixed powder is transported to the pan granulator by the pulverized material conveyor 14. In a pot-type granulation device, the moisture content is adjusted to 8 to 13% by mass on a Chinese pot-type rotating pot with a diameter of 3 to 6 meters. 22,176,176 发明, description of the invention powder to make a spherical unprocessed grain. The diameter of unprocessed pellets should be 5 ~ 30mm. In order to stably produce high-strength raw granules, it is important to mix a fine particle portion of 1 to 10 // m and a coarse grain portion of 50 // m or more at an appropriate ratio. Therefore, if the converter ash with a small particle size of 5 can be mixed at a ratio of 20 to 80% by mass, a good unprocessed pellet can be produced. In addition, in the method for manufacturing a molded body, a molding device including a pair of rollers having a plurality of concave forming dies is used, and a mixture is formed in the concave shape to form a briquette. Invented shaped body. In this forming method, the mixed powder is supplied from the upper portion 10 of a pair of rollers having a concave forming die, and pressed by the rollers. At this time, the powder is compressed inside the concave molding die to form a molded body. In order to maintain the strength of the molded body, a binder is generally used. The pellets are conveyed to a rotary hearth type reduction furnace 7 by a pellet conveyor 15. In the rotary hearth type reduction furnace 7, the formed body is fired and reduced. 15 Since heating may occur in the furnace of the rotary hearth type reduction furnace 7, there may be a problem of burst due to the evaporation of the moisture of the formed body, so it is appropriate to dry the formed body before supplying it to the rotary hearth type reduction furnace 7. . In the rotary hearth type reduction furnace 7, the iron oxide, manganese oxide, chromium oxide, zinc oxide 20 and the like contained in the particulate converter ash and other oxide powders are reduced in the high-temperature furnace by using the mixed carbon. As mentioned above, in the method of the present invention, in any case, the converter ash furnace is mixed with iron oxide-containing powder and gorge-containing powder to form shaped bodies such as granules and briquettes, and then the rotary hearth type is used. The compact is reduced in a reduction furnace. In the furnace of a rotary hearth type reduction furnace, a reduction reaction occurs when the body temperature of pellets and briquettes, etc. 23 200417611 玖, the description of the invention reaches above 1100 ° C. In particular, the reaction becomes lively at a temperature of 12 000 DC or more. In order to make the temperature inside the molded body above 1100 ° C and make the reaction active, the ambient temperature in the furnace must be above 1200 ° C. The inventors have found that by setting the ambient temperature in the furnace '5 to 1200 ° C or more for 6 minutes or more, the removal rate of zinc can be 80% by mass or more, and the reduction rate of iron can be 70% by mass or more. . Therefore, it is appropriate to set the processing time so that the shaped body containing particulate converter ash stays in the furnace at 120 ° C or more for more than 6 minutes. · Under the processing conditions of the rotary hearth method, a rotary hearth type 10 reduction furnace must be used 7 The ratio of the reduced substance to carbon is appropriate. That is, if the carbon in the formed body and the oxygen atomic mole ratio of iron, manganese, nickel, chromium, lead, and zinc are in the range of 0.5 In the range of ~ 1.5, as described above, high reduction and high dezincification treatments can be performed. If the carbon equivalent is 0.5 or less, the reduction will not be completed and the reduction rate of iron cannot be reduced to 70%. Above 15% by mass, the dezincification rate also becomes about 60 to 80% by mass, and the dezincification that is one of the objectives of the present invention cannot be fully implemented. If the carbon equivalent is L5 or more, carbon residues remain after the reaction ends. Carbon still remains, which prevents the combination of particles inside the reduced pellets (formed bodies), which causes the strength of the reduced iron pellets (formed bodies) to become low and cannot be used in a blast furnace. 20 In a rotary hearth type reduction furnace 7 In the furnace, the reduced forming system benefits It is discharged from the furnace by a spiral discharge device. The discharged reduction forming system is cooled by a reduced iron cooling device 8 and then supplied to the blast furnace as a raw material to become dazzling pig iron. Because the reducing agent uses powder coke and charcoal, The sulfur content rate is high, so the recovery destination of the reduced shaped body is the best for a blast furnace with a desulfurization function of 24 200417611 发明. The invention shows that it can still be effective even if it is recycled to a converter and an electric furnace. Device 9 removes dust and spreads it into the air. Example 5 Hereinafter, the present invention will be described in detail according to examples. Examples 1 to 2 First, an example of a method for recovering converter ash without oxidizing it as much as possible will be described. It is mixed with other powders and formed into a molded body having a moisture content of 10 17 to 27% by mass and a porosity of 40 to 54%. The results of the reduction treatment are shown in Examples 1 and 2 in Table 1. Furthermore, the results are shown in Table 1. The method of reduction is shown in the processing results by the method of the present invention and similar conventional techniques. The equipment is shown in Figure 1. In the method of the present invention Because the particulate converter ash is immersed in water, 15 there is less contact between metallic iron and oxygen, and the heat capacity containing water is large, so there is no problem of oxidation and heat generation of metallic iron. In Examples 1 and 2, even the particulate converter ash The metal-iron ratio is 66 to 67% by mass, and there is no problem of heat generation. In Example 1, a molded body that only dehydrates a dehydrated product is used. 20 Mixed dehydration in which 32% by mass of the aforementioned particulate converter ash is mixed The material was pulverized to form a molded body with a thickness of 20 mm and an average length of 25 mm. It was reduced under the conditions of the present invention. As a result, the pulverization ratio in the furnace was small, 6% by mass, and the treatment was good. However, since The reduction temperature is only 5 minutes, so the reduction rate and dezincification rate are slightly lower, which are 75% by mass and 81% by mass. 25 200417611 发明, description of the invention The crushing strength of the product is 67kg, which is relatively good. In addition, the pulverization ratio refers to the ratio (mass%) of the weight of the 3 mm sieve to the charged weight. In Example 2, a spiral-shaped extrusion molding device was used to form a cylindrical shaped body having a diameter of 12 mm and a length of 16 to 25 mm by mixing a mixed dehydrated product of the above-mentioned fine particle converter ash with 325 mass. The water content of the formed body was 21% by mass, and the porosity was 46% by mass. This formed body was subjected to reduction treatment in a rotary hearth type reduction furnace 7. The temperature of the supply part of the molded body was 1050, which is within the scope of the present invention. In addition, the reduction temperature is 1240 t and the reduction time is 10 to 10 minutes, which are all treatments within the range of the reaction conditions of the present invention. As a result, the pulverization rate was small, being 6% by mass, and the reduction rate, the dezincification rate, and the crushing strength of the product were all good. On the other hand, 'Comparative Example 1' is an example in which processing is performed using the apparatus shown in Fig. 1. However, this is an example in which the composition and moisture content of the particulate converter ash are substantially the same as those in Example 1 but have a low porosity in the formed body. In this treatment example, since the formed body has a low porosity, the formed body is pulverized violently in the rotary hearth type reduction furnace 7, and 56% by mass of the raw material is turned into a powder. Because of the effects described, the reduction rate and dezincification rate of the product are also low. This is because around the person who made the powder, carbon monoxide produced by carbon could not form a sufficient reduction environment, resulting in a reduction in the reduction rate of the powder. Comparative Example 2 is also an example of processing using the apparatus shown in FIG. 1. It is also an example of processing in which the moisture content of the molded body is too high, although the components and moisture content of the particulate converter ash are substantially the same as those in Example 丨. In this treatment example, the molded body has too much moisture, which makes the molded body soft, which results in the production of molded bodies. 26 200417611 玖 Description of the invention The problem of sticking occurs. As a result, when the rotary hearth type reduction furnace 7 is installed, there is a problem that the formed bodies on the hearth are unevenly dispersed, and the gas radiation from the upper space cannot be smoothly received. In addition, since the molded body has a large amount of water, there is also a problem that the powder of the molded body is severely powdered. As a result, the pulverization rate of the product was as high as 37% by mass, and the reduction rate was 48% by mass, and the dezincification rate was 61% by mass. The reaction was insufficient. Furthermore, the strength of the product was poor, being 25 kg. Because the treatment method of the present invention uses the rotary hearth type reduction furnace 7 for processing without oxidizing the metallic iron of the particulate converter ash, it is achieved that even if the amount of iron oxide in the particulate converter ash is small, and the reduction 10 There is no harm in related energy. In Comparative Example 3 shown in Table 2, a conventional method is used to oxidize the metallic iron of the converter ash, and then mix it with other powders to form spherical particles and reduce them. In Comparative Example 3, the particle converter ash was oxidized to a metal iron ratio of 11% by mass, so the reduction energy consumption rate was 6.44 GJ per 1 ton of raw material. 15 On the other hand, in Example 2 which is processed by the method of the present invention shown in Table 2, although the raw material mixing ratio, reduction conditions, etc. are made approximately the same as those of Comparative Example 3, the energy consumption is reduced by about 5%. Is 6.11GJ. As described above, in the process of using the particulate converter ash of the present invention, reduction treatment can be effectively performed and zinc can be removed. At the same time, the reduction rate is high, and reduced iron can be made with high strength. As a result, a large amount of particulate converter ash can be recovered as a blast furnace raw material. 27 200417611 发明, Description of the invention [Table 1] Unit Example 1 Example 2 Comparative Example 1 Comparative Example 2 Gray micro A Ml moisture converter mass% 56 57 51 51 metal iron ratio mass% 66 67 64 63 particulate converter Ash mixing ratio mass% 33 32 32 33 Yes / No Molding using molding device No mass of molded body (dehydrated material) moisture content 22 21 22 32 Porosity of molded body (dehydrated material)% 49 46 36 48 Carbon equivalent 1.1 1.1 0.88 1.1 Reduction temperature ° c 1215 1240 1240 1240 Reduction time (above 1200 ° C) minutes 5 10 10 10 Molding powder reduction rate mass% 6 6 56 37 Product properties reduction rate mass% 75 81 57 48 Dezincification rate mass% 81 93 71 61 Crushing strength kg 67 87 22 25
〔表2〕 單位 實施例2 比較例3 灰微 燼粒 性# 質爐 含水分 質量％ 57 13 金屬鐵比率 質量％ 67 12 微粒轉爐灰燼混合率 質量％ 32 32 還原溫度 °C 1240 1240 還原時間 分鐘 10 10 製 品 性 質 還原率 質量％ 81 80 脫鋅率 質量％ 93 90 壓碎強度 kg 87 86 製造能量消耗率 GJ/T-原料 6.11 6.44[Table 2] Unit Example 2 Comparative Example 3 Ash ash granularity # Mass furnace water content mass% 57 13 Metal iron ratio mass% 67 12 Particle converter ash mixing rate mass% 32 32 Reduction temperature ° C 1240 1240 Reduction time minutes 10 10 Product quality reduction rate mass% 81 80 Dezincification rate mass% 93 90 Crush strength kg 87 86 Manufacturing energy consumption rate GJ / T-raw material 6.11 6.44
28 200417611 玖、發明說明 實施例3〜6 接下來，說明實施可以適當之比率混合轉爐灰燼，使 還原穩定而將其回收之本發明之例。表3顯示進行使用含 水分為5〜16質量％且金屬鐵比率為8〜35質量％之微粒轉 5 爐灰燼製成球狀之粒，且將其還原之方法的結果。又，表 4顯示類似於本發明之方法，不過是以習知技術所行之處 理結果。這是設備為第2圖所示者，而成形方法則使用鍋 式之造粒機的結果。 首先，實施例3中，令微粒轉爐灰爐之含水分為12質 10 量％ ，金屬鐵比率為21質量％ ，係本發明之範圍之處理。 結果，微粒轉爐灰燼儲備槽内部之金屬鐵並未產生發 火現象。又，由於含水分適當，故可比較順暢地進行分出 操作。然而，因為大致幾天會發生1次輕微黏附現象（附 著而難以去除），所以利用鎚擊來對應。由於反應條件係在 15 本發明之範圍内，所以造粒和還原順暢地進行。結果，獲 得良好之製品，粒製品之還原率為81質量％ ，脫鋅率為 93質量％ ，又，壓碎強度為110kg。該製品可直接使用於 高爐。 又，實施例4中，係本發明之範圍，不過係使用含水 20 分較少且金屬鐵比率較多之微粒轉爐灰燼之例。由於含水 分少，故由微粒轉爐灰燼儲備槽1 /分出微粒轉爐灰燼時 ，完全沒有問題。另一方面，為了目的在於防止當含水分 少時會成為問題之金屬鐵氧化反應，所以保持微粒轉爐灰 燼儲備槽1 >之良好氣密，因此沒有金屬鐵氧化之發熱。 29 200417611 玖、發明說明 又，由於還原條件適當，故製品之還原粒之反應佳，金屬 化率為82質量％ ，脫鋅率為96質量％ ，又，壓碎強度為 133kg，完全沒有問題。 接著，實施例5顯示原料之微粒轉爐灰燼之性質雖大 5 致和實施例3相同，但碳當量為0.43，碳混合較不足之處 理之結果。該例中，雖然造粒處理實施沒有問題，但是由 於氧化鐵和氧化鋅之還原所需的碳稍稍不足，所以結果雖 是可使用作為製品之狀態，不過製品之還原率為73質量％ ，脫鋅率為81質量％ ，還原略為不足。 10 實施例6中，係利用電熱器17加熱微粒轉爐灰爐儲備 槽1 >之下部的錐部16，且使97%純度之氮流入65當量 立方公尺之處理之例。另，微粒轉爐灰燼儲備槽1 >之微 粒轉爐灰燼儲備量係95噸。本實施例中，雖是使用與實施 例3相同之微粒轉爐灰燼，但錐部16中並沒有發生微粒轉 15 爐灰燼附著，由微粒轉爐灰燼儲備槽1 /分出微粒轉爐灰 燼時，完全沒有問題。即使是外面空氣溫度為l〇°C以下之 凝結嚴重之狀態，在本實施例中，也可毫無問題地處理。 接著，以下顯示使用與實施例3〜6之設備相同設備之 比較例的處理結果。比較例4係轉爐灰燼含水分低，為3 · 5 20 質量％ ，且金屬鐵比率多，為37質量％之時的例子。在該 含水分中，空氣和金屬鐵之反應劇烈，在供給至微粒轉爐 灰燼儲備槽1 /前之廣場處理階段時，發熱劇烈，又，揚 塵亦激烈。此外，在微粒轉爐灰燼儲備槽1 /之内部發熱 也劇烈，使得槽内溫度變成330°c，一定須緊急排出。因 30 200417611 玖、發明說明 此，不能進行之後的處理。比較例5中，顯示含水分為18 質量％ ，含水分較本發明之範圍多之處理之例。此時，微 粒轉爐灰燼儲備槽1 >中微粒轉爐灰燼之黏附嚴重，無法 分出槽内之微粒轉爐灰燼。因此，該例也是無法實施之後 5 的處理。 接著，顯示反應條件超出本發明之範圍之處理之例。 比較例6係用以使反應發生之1200°C以上之反應時間為5 分鐘之短之處理的例子，而比較例7則顯示反應溫度為 1145°C之較1200°C低之處理。如表4所示，該等條件之處 10 理中，製品之還原率和脫鋅率低。又，製品之還原粒之強 度亦低，欲在高爐中直接使用仍有問題。 如以上所說明，使用本發明之微粒轉爐灰燼之處理中 ，可有效地進行還原處理並去除鋅，同時還原率高，且可 製成高強度之還原鐵。結果，可大量地回收微粒轉爐灰燼 15 作為高爐原料。 31 20 200417611 玖、發明說明 〔表3〕 單位 實施例3 實施例4 實施例5 實施例6 灰微 粒 性轉 質爐 含水分 質量％ 12 7 11 12 金屬鐵比率 質量％ 21 34 21 21 微粒轉爐灰燼混合率 質量％ 32 48 42 42 碳當量 1.1 1.3 0.43 0.63 錐部加熱和氮之有無 無 無 無 有 儲備槽内有無發火 無 無 無 無 由儲備槽分出時有無 堵塞 偶而，利 用鍵擊來 對應 良好 偶而，利 用鎚擊來 對應 良好 還原溫度 °c 1230 1230 1230 1230 還原時間 分鐘 7.7 7.7 9 9 製 品 性 質 還原率 質量％ 81 82 73 72 脫鋅率 質量％ 93 96 81 83 壓碎強度 kg 110 133 93 90 〔表4〕 單位 比較例4 比較例5 比較例6 比較例7 灰微 燼粒 性轉 質爐 含水分 質量％ 3.5 18 12 12 金屬鐵比率 質量％ 37 19 21 21 微粒轉爐灰燼混合率 質量％ 17 33 40 40 碳當量 1.1 0.95 0.91 0.88 儲備槽内有無發火 330〇C 無 無 無 由儲備槽分出時有無 堵塞 良好 堵塞頻頻 發生 利用鍵擊 來對應 同左 還原溫度 °c 無法處理 無法處理 1230 1145 還原時間（1200°C以上） 分鐘 5.8 1100〇C 以 上9分鐘 製 品 性 質 還原率 質量％ 43 33 脫鋅率 質量％ 46 41 壓碎強度 kg 31 2228 200417611 发明. Description of the invention Examples 3 to 6 Next, an example of the present invention will be described in which converter ash can be mixed in an appropriate ratio to stabilize the reduction. Table 3 shows the results of a method of converting 5 furnace ashes into fine-grained pellets by using particles containing 5 to 16% by mass of water and a metal-iron ratio of 8 to 35% by mass, and reducing them. In addition, Table 4 shows a method similar to that of the present invention, but the results of processing performed by conventional techniques. This is a result of the apparatus shown in Fig. 2 and the forming method uses a pan type granulator. First, in Example 3, the moisture content of the particulate converter ash furnace was 12 mass% and 10% by mass, and the metal-iron ratio was 21 mass%, which is a treatment within the scope of the present invention. As a result, the metallic iron inside the ash storage tank of the particulate converter did not ignite. In addition, since the moisture content is appropriate, the separating operation can be performed relatively smoothly. However, a slight sticking phenomenon (attachment is difficult to remove) occurs approximately every few days, so use a hammer to deal with it. Since the reaction conditions are within the scope of the present invention, granulation and reduction proceed smoothly. As a result, a good product was obtained. The reduction rate of the granular product was 81% by mass, the dezincification rate was 93% by mass, and the crushing strength was 110 kg. The product can be used directly in a blast furnace. In addition, Example 4 is within the scope of the present invention, but it is an example of using a particulate converter ash with less water content of 20 minutes and a higher ratio of metallic iron. Since the moisture content is small, there is no problem when the particulate converter ash is separated from the particulate converter ash storage tank 1 /. On the other hand, for the purpose of preventing the oxidation reaction of metallic iron, which would be a problem when the moisture content is small, the fine converter ash storage tank 1 is kept airtight, so there is no heat generation due to the oxidation of metallic iron. 29 200417611 发明 、 Explanation of the invention Also, because the reduction conditions are appropriate, the reaction of the reduced particles of the product is good. The metallization rate is 82% by mass, the dezincification rate is 96% by mass, and the crushing strength is 133kg. Next, Example 5 shows the results of the fact that although the properties of the particulate converter ash of the raw material are substantially the same as those of Example 3, the carbon equivalent is 0.43, and the carbon mixing is insufficient. In this example, although there is no problem in the implementation of the granulation treatment, the carbon required for the reduction of iron oxide and zinc oxide is slightly insufficient. As a result, although it can be used as a product, the reduction rate of the product is 73% by mass. The zinc ratio was 81% by mass, and the reduction was slightly insufficient. 10 In the sixth embodiment, the electric heater 17 is used to heat the particulate converter ash furnace reserve tank 1 > the lower cone portion 16 and let 97% purity nitrogen flow into 65 equivalent cubic meters. In addition, the particulate converter ash reserve tank 1 > has a particulate converter ash reserve of 95 tons. In this embodiment, although the same particle converter ash as in Example 3 is used, the particle converter 15 does not have the particle converter 15 furnace ash adhesion. When the particle converter ash storage tank 1 / particle converter converter ash is separated from the particle converter ash, it is completely absent. problem. Even in a severely condensed state where the outside air temperature is 10 ° C or lower, in this embodiment, it can be handled without any problems. Next, the processing results of a comparative example using the same equipment as those of Examples 3 to 6 are shown below. Comparative Example 4 is an example when the converter ash has a low moisture content of 3.520% by mass and a large ratio of metallic iron to 37% by mass. In this moisture content, the reaction between air and metallic iron is violent. When it is supplied to the particulate converter ash storage tank 1 / front square treatment stage, the heat is intense and the dust is also intense. In addition, the internal heat in the particulate converter ash storage tank 1 / is also intense, so that the temperature in the tank becomes 330 ° c, which must be discharged immediately. Since 30 200417611, the description of the invention Therefore, the subsequent processing cannot be performed. Comparative Example 5 shows an example of a treatment having a water content of 18% by mass and a water content greater than the scope of the present invention. At this time, the micro converter ash storage tank 1 > the medium converter ash adhesion was severe, and the micro converter converter ash in the tank could not be separated. Therefore, this example also cannot implement the subsequent 5 processing. Next, examples of treatments in which the reaction conditions are out of the scope of the present invention are shown. Comparative Example 6 is an example of a treatment for making the reaction time of 1200 ° C or higher to be shorter than 5 minutes, while Comparative Example 7 shows a treatment with a reaction temperature of 1145 ° C and lower than 1200 ° C. As shown in Table 4, the reduction and dezincification rates of the products are low in these conditions. In addition, the strength of the reduced particles of the product is also low, and there are still problems in using it directly in a blast furnace. As described above, in the process of using the particulate converter ash of the present invention, reduction treatment can be effectively performed and zinc can be removed. At the same time, the reduction rate is high, and reduced strength iron can be made. As a result, a large amount of particulate converter ash 15 can be recovered as a blast furnace raw material. 31 20 200417611 发明, Description of the invention [Table 3] Unit Example 3 Example 4 Example 5 Example 6 Water content% of ash particulate converter 12 7 11 12 Metal iron ratio mass% 21 34 21 21 Particulate converter ash Mixing ratio by mass% 32 48 42 42 Carbon equivalent 1.1 1.3 0.43 0.63 Cone heating and nitrogen presence or absence of presence or absence of igniting in the storage tank No ignorance no clogging Occasionally when separated from the storage tank Occasionally, good response by key stroke Occasionally, use a hammer to correspond to a good reduction temperature ° c 1230 1230 1230 1230 Reduction time minutes 7.7 7.7 9 9 Product property reduction rate mass% 81 82 73 72 Dezincification rate mass% 93 96 81 83 Crush strength kg 110 133 93 90 [Table 4] Unit Comparative Example 4 Comparative Example 5 Comparative Example 6 Comparative Example 7 Moisture content of ash micro-granular converter 3.5% by mass 18 18 12 12 Metal-iron ratio mass% 37 19 21 21 Particle converter ash mixing rate mass% 17 33 40 40 Carbon equivalent 1.1 0.95 0.91 0.88 Is there any ignition in the storage tank 330 ° C No No No No clogging when separated from the storage tank Good blockages occur frequently using key strokes to correspond to the left reduction temperature ° c Cannot handle cannot be processed 1230 1145 Reduction time (above 1200 ° C) minutes 5.8 1100 ° C or more 9 minutes Product properties reduction rate mass% 43 33 Dezincification rate mass% 46 41 Crushing strength kg 31 22
A 32 200417611 玖、發明說明 產業上可利用性 藉進行本發明之方法，可有效地利用旋轉爐床式還原 爐處理將含鋅之轉爐灰燼集塵而獲得之微粒轉爐灰燼，且 將其脫鋅，同時可將其還原而回收作為鐵原料。又，因為 5 可去除鋅和鉛，所以可由微粒轉爐灰爐製成良質之還原鐵 〇 【圖式簡單說明】 第1圖係一用以實施本發明之旋轉爐床式還原爐和其 附帶設備之例，且係顯示處理高含水分之微粒轉爐灰燼時 10 之設備結構的圖。 第2圖係另一用以實施本發明之旋轉爐床式還原爐和 其附帶設備之例，且係顯示將微粒轉爐灰燼處理成含水分 5〜16質量％時之設備結構的圖。 第3圖係用以實施本發明之微粒轉爐灰燼之儲備槽之 15 加熱裝置和惰性氣體吹入口的圖。 200417611 玖、發明說明 【圖式之主要元件代表符號表】 1…微粒轉爐灰燼儲備坑 1'.·微粒轉爐灰燼儲備槽 2…漿體儲備槽 3…粉焦炭儲備槽 4.. .漿體混合槽 6··.成形裝置 6'..锅式造粒裝置 7.. .旋轉爐床式還原爐 8.. .還原鐵冷卻裝置 9·. J纟氣處理裝置 10…其他粉體儲備槽 11.. .黏結劑儲備槽 12…粉體輸送機 13…粉體粉碎混合裝置 14…粉碎物輸送機 15…粒輸送機 16···錐部 17.. .加熱裝置 18…氣體供給管A 32 200417611 发明 Description of the invention The industrial applicability By carrying out the method of the present invention, a rotary hearth type reduction furnace can be effectively used to treat particulate converter ash obtained by collecting zinc-containing converter ash and dezincify it. At the same time, it can be reduced and recovered as iron raw materials. In addition, because 5 can remove zinc and lead, good reduced iron can be made from a particulate converter ash furnace. [Simplified illustration of the drawing] FIG. 1 is a rotary hearth type reduction furnace and its accompanying equipment for implementing the present invention This is an example, and is a diagram showing the structure of the equipment when processing high-moisture particulate converter ash. Fig. 2 is another example of a rotary hearth type reduction furnace and ancillary equipment for implementing the present invention, and is a diagram showing the structure of the equipment when the particulate converter ash is processed to a moisture content of 5 to 16% by mass. Fig. 3 is a diagram of a heating device and an inert gas blowing inlet of a storage tank for the particulate converter ash for carrying out the present invention. 200417611 发明. Description of the invention [Schematic representation of the main components of the drawing] 1 ... Particulate converter ash storage pit 1 '. · Particulate converter ash storage tank 2 ... Pulp storage tank 3 ... Powder coke storage tank 4. Tank 6 ·· Forming device 6 '.. Pot granulation device 7. Rotary hearth type reduction furnace 8. Reduced iron cooling device 9. J 纟 Gas processing device 10… Other powder storage tank 11 ... Binder storage tank 12 ... Powder conveyor 13 ... Powder crushing and mixing device 14 ... Pulverized material conveyor 15 ... Pellet conveyor 16 ... cone section 17. Heating device 18 ... Gas supply pipe
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| Application Number | Priority Date | Filing Date | Title |
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| JP2001279054A JP2003089823A (en) | 2001-09-14 | 2001-09-14 | Converter dust recycling method to rotary hearth type reducing furnace |
| JP2001279053A JP2003082418A (en) | 2001-09-14 | 2001-09-14 | Method for recycling converter dust to rotary hearth type reducing furnace |
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| TW200417611A true TW200417611A (en) | 2004-09-16 |
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