1300803 玖、發明說明： 【潑^明所屬領域^ 本申請案提申該於2〇〇2年12月％日提申之日本專利申 請案編號：2002-376817的優先權，該案在此以其全立 ^ 5 併入本案作為參考資料。 發明領域 本發明係關於一種藉由添加石灰來降低乾法娟焦&備 (以下簡稱為CDQ)所產生之氣體中硫化物濃度的技術。 ίο 發明背景 一座焦炭爐是一種外部加熱型式之火爐，其體積龐大 且具有良好的加熱功率。依照能源回收之進步來看，現代 的焦炭爐已整合非常先進的能源回收技術。能源回收主要 是使用CDQ設備來施行，其中冷卻焦碳是藉由大量循流之 15氣體（通常是氮氣），且受熱之循流氣體可於其後供用以產生 蒸汽，該蒸汽於其後會經由一部蒸汽渦輪引擎來發電。 於CDQ設備中，來自焦炭爐之熾紅焦炭會被擲入（例 如：添加至）一個預備槽中，其後通過一個居於底部之冷卻 槽。循流狀體被飼入該冷卻槽中，有如一道冷卻氣體，藉 2〇 此熄焦並受熱。該受熱之循流氣體會被飼入一部諸如蒸汽 鍋爐之熱交換器中，藉此產生蒸汽。該蒸汽被使用來使蒸 汽渦輪引擎運作發電。因此CDQ設備展現兩種功能：a)冷 卻焦炭、以及b)回收熱能源。該卸載自冷卻槽之冷卻焦炭 會被送進一座熔爐中，俾以供用為一種節約之加熱燃料並 1300803 減少燒結礦物。 將空氣導入預備槽之技術已被提出，該技術可安定氣 ϋ組份’並增加得自燃燒焦炭之熱量回收數量。 I知之製造生石灰方法，是使用一座燃料油鋼爐來加 5熱分解石灰（主要成份是碳酸鈣，熟石灰），燃燒燃料油產生 一氧化破，並分解石灰。因此，習知方法是一種產生二氧 化碳之製程。 然而’尚未被研究的問題是由焦炭燃燒預備槽内空氣 所產生之微量硫化物。1300803 玖, invention description: [Purchase ^ Ming field] This application claims the priority of Japanese Patent Application No. 2002-376817, which was filed on December 2, 2012. Its full set ^ 5 is incorporated into this case as a reference. FIELD OF THE INVENTION The present invention relates to a technique for reducing the concentration of sulfide in a gas produced by dry coke & (hereinafter referred to as CDQ) by adding lime. Ίο BACKGROUND OF THE INVENTION A coke oven is an externally heated type of furnace that is bulky and has good heating power. According to the progress of energy recovery, modern coke ovens have integrated very advanced energy recovery technologies. Energy recovery is mainly carried out using CDQ equipment, in which the cooled coke is supplied by a large amount of 15 gases (usually nitrogen), and the heated circulating gas can be subsequently supplied to generate steam, which will be followed by Power is generated via a steam turbine engine. In CDQ equipment, the blushing coke from the coke oven is thrown (for example, added) into a preparation tank and then passed through a cooling tank located at the bottom. The flow-through body is fed into the cooling tank, which is like a cooling gas, which is quenched and heated. The heated circulating gas is fed into a heat exchanger such as a steam boiler, thereby generating steam. This steam is used to operate the steam turbine engine. The CDQ device therefore exhibits two functions: a) cooling coke, and b) recovering thermal energy. The cooled coke unloaded from the cooling tank is sent to a furnace for use as an economical fuel and 1300803 to reduce sintered minerals. A technique for introducing air into a preparation tank has been proposed which stabilizes the gas composition and increases the amount of heat recovered from the combustion coke. I know that the method of making quicklime is to use a fuel oil steel furnace to add 5 thermal decomposition lime (the main component is calcium carbonate, slaked lime), burning fuel oil to produce an oxidation break, and decomposing lime. Therefore, the conventional method is a process for producing carbon dioxide. However, the problem that has not been studied is the trace amount of sulfide produced by the coke burning air in the preparation tank.
10 、經由焦炭燃燒所產生之硫化物會隨循流氣體流通CDQ 設備之循流裝置，且於鍋爐（熱交換器）之溫度較低的部分 (出口）會部分地沉積成硫酸(H2S〇4)或亞硫酸(H2S03)，這會 於該裝置之金屬部分表面上引發金屬銹蝕。因此，需要週 期性維護，於維護期間，運作停機，俾以進行修繕工作(例 15如：研磨及拋光銹蝕金屬表面部分），且設若需要，必須更 換深度銹蝕之部分。設若能夠防制此種金屬銹蝕，則可降 低維護之頻率，這可大幅減輕工作、時間及成本。然而， 可供用以防止C D Q設備之循流裝置（特別是鍋爐之低溫度 部分)產生金屬銹蝕的有效技術尚未被提出。 2〇 【曰月内】 發明概要 一項本發明標的是提供一種可供用以減少CDQ設備之 氣體中硫化物的方法，該經由燃燒焦炭所產生之硫化物是 存在於預備槽之空氣中。 1300803 本發明人驚訝地發現：當添加石灰至CDQ設備預備槽 日守·可以（1)在不需要額外數量之其他燃料（例如：重油）之 下’藉由添加石灰至CDQ設備預備槽，來達到足夠的溫度 以及供用以加熱分解石灰之滞留時間、（2)由於只有使用熾 5紅焦炭之實用熱量來分解石灰，因此不會增加二氧化碳的 數ϊ、且(3)較諸個別地使用燃油鍋爐來分解石灰製造生石 灰’然後將該製造之生石灰添加入CDq設備而言，添加石 灰至CDQ設備預備槽會具有可預期之熱量高回收效率。 本發明可藉由下列1〇種方法之任何一種來減少CDQ設 1〇 備之氣體中硫化物。 依據本發明的第一個方面，該可供用以減少CDQ設備 之氣體中硫化物的方法係包含一個將石灰擲入CDQ設備之 步驟。 依據本發明的第二個方面，該擲入石灰之預備槽，會 15 接續地擲入熾紅焦炭。 依據本發明的第三個方面，石灰是以槽桶及/或槽桶車 來運載及擲入，然後擲入熾紅焦炭。 依據本發明的第四個方面，該居於部分或整體預備槽 内部空間之氣體溫度是1000-1100°c。 20 依據本發明的第五個方面，石灰包含超過10wt%是具 有顆粒尺寸小於l〇nm之石灰。 依據本發明的第六個方面，擲入石灰數量是每噸焦炭 擲入25-640克。 依據本發明的第七個方面，石灰是於間隔擲入熾紅焦 1300803 炭之期間被擲入預備槽，或者與熾紅焦炭同時被掷入預備 槽。 、 依據本發明的第八個方面，擲入石灰是經由一個配置 於CDQ設備頂端之焦炭擲人口，及/或一個或數個配置 5 備槽之石灰擲入口。 依據本發明的第九個方面，擲入石灰是藉由該等使用 氮氣及/或循流氣體做為一種載體氣體之氣體移動力量。 依據本發明的第十個方面，石灰是於織紅焦炭被载入 槽桶及/或槽桶車之前、同時、及/或之後被掷入槽桶及 !〇 槽桶車。 ^ 圖式簡單說明 第1圖是本發明所使用之典型CDQ設備之示意圖。 第2(A)圖是一部供用以碾碎團塊之碾碎機的示意圖。 第2(B)-(E)圖闡釋兩個裝設於第2(A)圖碾碎機出口部 15分之出口筛網之篩孔圖案及篩孔尺寸，以及供用以區分儀 碎石灰、界定顆粒尺寸、及特定顆粒尺寸所佔百分比之區 分筛網。 I：實施方式3 較佳實施例之詳細說明 20 於一個本發明具體例中，該具體例是一種可供用以減 少CDQ設備之氣體中硫化物的方法，其中該載入（擲 入)CDQ設備之石灰可供用以減少氣體中之硫化物。 於燃燒焦炭期間，該包含於焦炭之硫會轉變為該移入 氣體中之硫化物（S Ο X)。經由一槽桶車直接或間接擲入預備 1300803 槽之石灰會因為熾熱焦炭之加熱而依照加熱分解反應來進 行熱分解，意即於7〇〇-900°C之下，CaC〇3—Ca0+c〇2。居 於氣體(循流氣體及預備槽内之氣體）中之硫化物（例如：二 氧化硫(S〇2)或硫化氫(Hj))會經由與石灰進行熱分解所產 5生之氧化鈣(CaO)反應，而轉變為石膏(硫酸鈣(CaS〇4))，意 即：OCaO+SC^+XC^—CaS〇4 以及（2)Ca0+S02+H2S~> CaS+H20、CaS+2〇2—CaS04。由於擲入之石灰需費時大約 1小時來通過CDQ設備之溫度80〇-l〇〇〇°c的區域，因此有充 裕的時間來進行反應。二氧化硫(S〇2)或硫化氫(h2S)是以石 10膏來積聚於焦炭表面。其結果是，氣體中之硫化物大量減 少（例如：SOx會減少92%)，藉此大幅減少系統内銹蝕。因 此，系統變成幾近於一種不需要維護之狀態。於本發明中， 居於氣體中之硫化物是藉由擲入石灰來予以固定，且剩餘 未反應之碳酸鈣(CaC03)以及氧化鈣（CaO)可供用為燒結製 15 程中替代石灰之可選擇性材料，二者皆能夠於CDQ及燒結 製程中去除硫化物。 於一個本發明具體例中，石灰可以是任何一種碳酸鈣 (CaC03)、熟石灰（氫氧化妈（Ca(0H)2))、一種或數種由上述 諸等與生石灰（氧化鈣(CaO))所構成之混合物、以及一種可 20 利用之主要組份是碳酸鈣之天然石灰岩。 對於石灰之顆粒尺寸並沒有特別的限制。較佳是超過 10wt%之石灰必須具有一個小於10mm之顆粒尺寸。更精確 是l(M00wt%(較佳是50-100%)的石灰必須具有一個小於 10mm之顆粒尺寸，且必須包含〇_9〇wt%(較佳是〇_50wt0/〇) 13〇〇8〇3 疋具有一個小於10-200mm之顆粒尺寸。其理由是某些大尺 寸石灰顆粒會難以於CDq設備中進行熱分解，然後助益去 示瓜化物製程，這會導致減低硫固化。因此需要額外的石 火換句°舌5兒，當石灰的尺寸範圍是居於較佳之尺寸範圍 4石灰可以於被擲入預備槽之後，在維持於溫度超過700 °C之高溫區域中，歷時大約丨小時内，進行熱分解，然後充 足地助益於去除硫化物製程。設若顆粒尺寸太大時，於石 灰顆粒離開高溫區域之前，熱分解反應將不會由顆粒表面 深入其中心（一部分的石灰將轉變為二氧化碳(c〇2)氣體，該 ⑺氣體會使該部分脆化為細顆粒）；因此，該使用焦炭回收熱 之熱分解反應不足，且石灰與循流氣體之間的接觸將不足 以促進一種與氣體中硫化物之反應。因此，將難以藉由固 定來減少硫化物。 然而，本發明可使用該具有一個超過2〇〇mm顆粒尺寸 15之石灰。一般而言，可以在通過CDQ設備時，將此種大尺 寸石灰顆粒研磨成尺寸落在上文所述範圍内之程度。當添 加額外數量的石灰時，於某些部分石灰保持不進行熱分解 之情形下，剩餘的石灰可以供用於一燒結製程中。由於需 求之正常通過CDQ設備的焦炭，較佳是具有一狹窄尺寸分 20佈之45-55mm平均顆粒尺寸，以焦炭碾碎機碾碎大尺寸焦 炭，然後使用一個具有一個25-30mm篩孔之篩網來篩分。 設若石灰被碾碎成細顆粒，則該小尺寸可容許該顆粒以粉 末狀焦炭來被送入一燒結製程中。 石灰必須包含超過1 〇wt%之石灰（較佳是5 〇_丨〇〇wt%)是 10 1300803 具有小於1Gmm難尺相理由是因為··此種尺寸會因為燒 結製程所使用之石灰尺寸通常是小於l〇mm而方便於處 基於此以及其他情形會使用小於15mm之石灰尺寸的因 素，因此較佳之條件如下：1(MQQwt%(㈣是5(MQQwt%) 火必H自小於繞結製程所使用石灰尺寸之顆粒 寸且必/頁包3 〇__9〇wt%(較佳是卜漸⑽之石灰是 一個大於燒結製程所使用石灰尺寸但小於細職之顆粒 寸0 石灰尺寸之界定如下。 10 15 20 之箭頭戶^ ^猎由師網之筛孔縱向尺寸(如第2(BME)圖 =Γ= 界定，俾以供用於以區分礙碎機礙碎 传/…疋亚非視篩孔形狀而定，某些_孔形狀示例 係如弟2(Β)·(Ε)圖所闡釋。 碾碎機是使用壓迫、摩捧、 成小尺寸。使用壓迫力之;型二=將_ 她、/、型機杰疋一部槌磨機及球磨 枝，使用摩擦力之典型機器是一部研磨機 之血型機哭目卩H 而使用切割力 近;;H一部切割機。由於大部分碼碎石灰之型狀 近似一球型或立方型（如煤炭或食物之情形 ^狀 乎是—個碾碎顆粒尺寸之良好的量測。：： 地疋義代表粒徑或平均粒徑之觀念。然而，表奋 石灰尺寸是藉由碾碎石灰通過篩:：、&明中’ 疋’供用以區分尺寸之篩網不是連接第 末予以界 網，而是分別地製備之另-個只供用 不碾碎機之篩 篩網。進行巴八3將石^顆私 扣刀已碾碎石灰之 Μ刀疋將石灰顆粒通過一個筛網，然後盡可能 1300803 地減少與該篩網垂直方向之振動。設若篩網傾斜角度為 零’則呈水平方向來進行振動。 小尺寸石灰之製備是如下列，例如：第2圖所顯示：將 石灰材料301沿箭號粗線載入碾碎機3〇2(槌打型）中。一部方^ 5轉器303係沿箭號細線，呈旋轉方向305，來旋轉載入之石 灰。被旋轉之石灰會受該装設於碾碎機内之擊槌3〇4撞擊， 而被碾碎成較小尺寸，或者通過撞槌3〇4與旋轉器3〇3之間 的空隙。尺寸減小之石灰會由於離心力而通過一個固定於 該旋轉路徑外壁之篩網飛出。設若該篩網3 〇 7具有特定形狀 10 308及篩孔尺寸（如第2(BHE)圖所顯示之實例）時，則只有能 夠通過篩孔之縮小尺寸之石灰3〇6會飛出篩網3〇7。 篩網之實例描述如下。 碾碎石灰是以一部槌打型碾碎機(碾碎數量是1〇〇公斤/ 小時、旋轉速度是200 rpm、擊槌寬度是1〇mm、擊槌數量 15是12、出口篩網篩網尺寸是5〇mm(方形篩孔))來進行。已碾 碎之石灰是使用一個振動篩網（篩網尺寸1〇mm(方形篩 孔）、傾斜5。、水平及垂直方向振幅為1〇mm，且頻率為3〇/ 分鐘）來篩選。設若於3次試驗測試時，尚未通過篩孔之石 灰分別是10、9、l〇wt%，則該碾碎石灰被界定為包含1〇糾％ 20之具有一個小於10mm之顆粒尺寸（平均3次試驗測試之wt% 數值並四捨五入）。呈類似之方式，設若尚未通過篩孔之石 灰分別是20、20、20wt%，其中該出口篩網篩網尺寸是 30mm且振動篩網之篩孔尺寸是，則該碾碎石灰 樣品被界定為包含20wt%之具有一個小於1〇mmt顆粒尺 12 1300803 寸。同時，設若於尚未通過篩孔之石灰分別是8〇、79、 79wt%，該出口篩網篩網尺寸是l〇mm，且振動篩網之篩扎 尺寸是10mm時，則該碾碎石灰樣品被界定為包含8〇_。/〇之 具有一個小於10mm之顆粒尺寸。 藉由使用另一種更小型的礙碎機（碾碎數量是別公斤/ 小時、200 rpm、擊槌寬度是i〇mm、擊槌數量是12)，玎提 升數據的可信度。 如上文所述，該具有一個小於1〇mm尺寸之石灰的百分 比被界定為未通過篩孔篩網之石灰的重量百分比(wt%”為 1〇 了改變該重量百分比(wt%)，因此改魏連接碾碎機之筛網 的篩孔尺寸。顆粒尺寸可藉由改變上文所述之··幻擊槌形 狀、b)擊槌寬度、c)旋轉速度、句篩網位置、輕碎機之型 m例如：研磨切割機或切割研磨機）、以及〇礙碎機筛網之 篩孔尺寸來予以改變。於任何一種情形中，顆粒尺寸皆是 15以過篩來予以界定。過篩本身可以藉由改變振動型態或條 ，（例如：凸輪脈衝、圓形/橢圓形移動之篩網、頻率）以及 ^網之師孔形狀(方形、圓形或橢圓形）來改變。然而，只要 疋，用上文所述之振動筛網，顆粒尺寸皆可被界定為 正常的數值。 20 物的==:!:沒有特㈣限制。氣體中硫化 ”添加數讀比例。較佳是每炭必須添 克，640公克。設若每镇焦炭添加之石灰數量少於％公 %則硫化物可能無法完全去除。相反地，設若每-嘲隹 厂^加之石灰數量超過_公克，則硫化物可以完全去除'，、 13 1300803 但某些數里之石灰會維持未反應。然而只要剩餘的石灰數 量是落在某些可以完全地供用於上述燒結製程之數量，則 將是無害的。 石灰車父仏疋’备在免廣數篁範圍的理由是因為：焦炭燃 5燒所產生之石’1L化物的數置是視存在於每一 镇焦炭之空氣數 量而定。某些空氣是自然地被導入該焦炭擲入口，而某些 空氣則是故意地予以導入，俾以供用於某些目的。 例如，當5-20立方公尺(1113)(以周遭條件量測）之空氣被 飼入預備槽時，燃燒1.13-4.5公斤之焦炭會將4·5_2〇·3克之 10該包含於焦炭中的硫轉變為3.2-14.2公升之硫化物（s〇x)。 依據貫際產生系統之试驗數據而言，這相當於卸載氣體包 含13-52 ppm之硫化物（SOx)。 假設有如流動基床地以循流氣體來將居於焦炭周圍之 石灰與熱分解產物氧化鈣（CaO)予以流體化，鈣/硫(Ca/s) 15 ，思即·添加石灰之飼(Ca)組份數量是循流氣體中硫(s) 組份數量的2倍。於此條件下，可有效地去除硫。因此，每 一噸焦炭適合添加之石灰數量應該是25_13〇克的碳酸鈣 (CaC03)。 假設居於焦炭周圍之石灰與熱分解產物氧化鈣（Ca〇) 20是有如填充基床地被填充時，飼/硫(Ca/S)—1〇是一個可有 效去除硫之條件，這是因為減少與氣體接觸。因此，對於 填充基床而言，每一噸焦炭適合添加之石灰數量應該是 140-640克的碳酸鈣（CaC03)。 焦炭於CDQ設備中的表現像居於一個移動基床中。換 14 1300803 句話說，氣體接觸的程度是居於一種流動基床與一種填充 基床之間。基於此，每一噸焦炭適合添加之石灰數量應該 是25-640克的碳酸鈣（CaC03)。然而，較佳是施行前行測 試，該測試是使用一種生產系統，在移動基床條件下，以 5 任何一種空氣數量改變，來測定適合添加之石灰數量。 本發明人提出一種使用一種生物質量而非焦炭來擲入 預備槽之技術。於可選擇燃料之情形中，例如使用生物質 量，添加之石灰數量可以將空氣中數量與添加之生物質量 的數量或類似物之間的差異列入考量之下，藉由估計氣體 10 中所產生的硫化物數量來測定。然而，較佳是使用生產設 備施行驗證測試，俾以針對空氣及生物質量之數量而言， 測定出適合添加之石灰數量。 石灰不需要被擲入預備槽中。本發明精義是以石灰、 特別是石灰岩、碳酸鈣、及熟石灰經熱分解所產生之氧化 15 鈣（CaO)與硫化物反應，來固定CDQ氣體中之硫化物。甚至 於諸等可被分解者當中最硬的碳酸鈣皆可以於一個超過 900°C之溫度分解。為了維持進行熱分解反應，可使用預備 槽中熾紅焦炭（大約l〇〇〇°C)的熱量，以及使用該被裝載於一 槽桶或槽桶車之移取自焦碳爐之熾紅焦炭的熱量，該熾紅 20 焦炭的熱量（於擲入預備槽之前）尚未被利用。該熱量在裝載 於槽桶或槽桶車至到達CDQ之前的時間内（大約5分鐘），會 因為輻射至空氣中而浪費掉。本發明方法包含：將石灰與 熾紅焦炭一起置放於槽桶中，藉此有效利用熱量來預熱石 灰，俾以進行熱分解。 15 1300803 詳細内容是依照圖式來解說。第i圖是本發明所使用之 典型CDQ設備的示意圖。 於-焦碳爐2(Π製成之大約刚叱的熾紅焦炭i5i被推 擠入-個槽桶或槽桶車(以下簡稱為_車或類似物）1〇2， 5俾以運送至CDQ設備而。該熾紅焦炭是藉由開啟一個居於 CDQ設備1G1頂部且通常覆蓋該焦炭擲人口崩之頂蓋 來、、、工由個頂部焦厌擲入口 1〇4卸载入預備槽奶。於 擲入熾紅线⑸之後，關_蓋⑼來阻斷自然流入的空 氣。空的槽桶車或類似物1〇2返回焦碳爐2〇ι來進行下 10 載運。 、居於預備槽1G2之高溫焦炭151會通過—個居於較底部 之冷卻槽1G6來向下掉落，俾以藉由循流氣體撕來予以冷 部至200 C，其後自_個居於底部之冷卻槽觸之卸載出口 15 20 1〇8卸出。於第中，箭號粗線代表被擲人CDQ設備之前 的熾紅焦炭’數字153代表居於CDQ設備中之焦炭，實線箭 餘線表示移動方向，而財155職表自CDQ設備卸載之 焦厌（包含石灰及石膏）。 熱量是藉由一部熱交換器（蒸汽銷爐)1〇9，並經由循流 乳體107，來^时。熱㈣產生之蒸汽⑴會推動蒸汽 。輪機113來發電。外部空氣117會被添加入一個環狀導管 個氣體排放出口，在諸轉發性組份或粉 末=焦炭（以及於本發明中為粉末狀石灰及石膏）到達熱交 、ά\ Γ引&結焦或某些熱傳導問題之情形下，該導管會燃 、凡以之揮發性組份及焦炭粉末。_個粉塵搜錢123被裝 16 l3〇〇8〇3 設於一個居於環狀導管115與熱交換器l〇9之間的循流通路 121内，俾以供用於搜集焦炭粉末、石灰粉末及石膏粉末， 該被收集之粉末將被使用於接續之燒結製程中。該通過具 有蒸汽鍋爐之熱交換器109後的循流氣體109會藉由使用該 5居於循流通路121内之循流氣體鼓風機125來調整氣體壓 力’藉此經由一個循流氣體入口 127返回至冷卻槽1〇6。一 個供用以排出部分循流氣體之氣體排放通路129可予以裝 设於該居於循流氣體鼓風機丨2 5與循流氣體入口 12 7之循流 通路121内，俾以維持循流氣體進入CDq設備1〇1之流動速 10率。當適宜時，可以將一個流動控制閥、流動計量器及/或 廢氣純化裝置裝設於氣體排放通路129上。 一種可供用以減少CDQ設備中氣體中硫化物之本發明 方法將更進一步參照第1圖來做解說。 如第1圖所顯示，該被擲入一個擲入熾紅焦炭151之 15 CDQ設備101預備槽1〇5之石灰i8ia(稱為擲入型（A))，或者 該被置入一個槽桶及/或一個槽桶車102之石灰181b(稱為擲 入型（B))二者可以呈（A)型與（B)型之組合來予以置入預備 槽及槽桶及/或槽桶車。 現在來討論某些擲入型（A)之具體例。 20 於擲入型（A-1)中，熾紅焦炭151是以間隔數分鐘至數十 分鐘來予以批次載入（以一種批次運作來予以擲入）。石灰 181a之添加可以落在邊等經由適合石灰擲入裝置183來予 以擲入熾紅焦炭15丨之間，這可以使擲入時間變容易。然而 較佳地，石灰之添加應該迅即於熾紅焦炭被載入預備槽1〇5 17 1300803 之後。CDQ設備101之正常内部空間溫度會由於熾紅焦炭之 熱量而居於酬-llGGt：，因此不需要均句攙混焦炭及石 灰。此外，由於擲入之石灰需費時大約丨小時來通過CDq設 備之溫度800-1000 C的區域，因此反應時間（滯留時間）充 5裕。因此，擲入時間並沒有特定限制。然而，迅即於熾紅 焦炭151擲入後擲入之石灰可以於氣體中硫化物流入氣體 循流通路之前，增加一個固定硫化物的數量，藉此減少該 包含於氣體中之硫組份聚集於蒸汽鋼爐之出口部分，因此 可減少系統内產生酸銹姓。 10 一個“焦炭批次載入間期，，是將所有居於第一個槽桶車 或類似物102内之熾紅焦炭擲入預備槽ι〇5，至開啟第二個 槽桶車或類似物102底部開始擲入下一批次之熾紅焦炭所 經歷之時間。 當石灰在居於熾紅焦炭被擲入間期被擲入時，焦炭厣 15與石灰層會於CDQ設備内進行沉降，二者會像三明治一费 交疊，同時該進行一種熱分解反應及一種去除硫反應之石 灰層會轉變為石膏，然後於沉積於焦炭時被固定，其後自 底部卸載出口 108卸出。 於擲入型（A-2)中，石灰181a可以使用擲入裝置183，與 20 擲入熾紅焦炭151同時予以擲入預備槽105。此種同時掷入 是一個較佳具體例。由於石灰散落於熾紅焦炭層，因此包 圍石灰之熾紅焦炭所具有的熱量會被有效地利用來促進熱 分解反應。受熱分解之石灰會容易地接觸該居於流動通過 焦炭間隙之間之循流氣體内的硫化物，藉此可有效固定石穿 1300803 組份。 “同時擲入，，係意指開始與結束擲入石灰都落在自槽桶 車或類似物102開始至兀成卸載熾紅焦炭之期間。同時掷入 可容許良好的焦炭與石灰攙混，這可增加石灰與焦炭之間 5接觸機會（這會增加熱傳導效力及促進熱分解反應）且同時 會增加循流氣體之接觸機會（這會增加氧化鈣(Ca〇)與居於 氣體中之硫化物的反應效率，藉此促進硫之固定）。 於同時擲入之情形中，每一個批次之熾紅焦炭151與石 灰181a會層疊形成一個多層體。該多層體會於cdq設備内 10進行沉降，石灰會持續經由一種熱分解反應以及一種去除 石瓜反應而被轉變為沉積於焦炭表面之石膏，直至最後自底 部卸載出口 108卸出。 擲入型(A-3)是擲入型(A-1)與擲入型(A_2)之組合。於某 些階段時，石灰是在擲入熾紅焦炭之間被擲入，而於某些 15階段時，則予以同時擲入。添加所需數量之石灰，藉此形 成由焦炭與石灰所構成之分層或混合層，俾以達到利甩該 個別擲入型態功效優點之目的。 於任何一種上文所述之擲入型態中，每一個批次擲入 之石灰lSla與熾紅焦炭⑸的數量可以一次全數掷入，或者 20於-段固定的期間内連續掷入，或者於一段期間内間隔地 掷入。擲入之方式並沒有特定的限制。於連續或間隔掷入 之情形L速率可以是維持固定或具有變化。 於上述擲入型中，石灰丨汉^可以經由一個居 設備101頂部之頂部焦炭掷入口 108，及/或一個或數個裝設 19 1300803 於預備槽105之石灰擲入口 i85，來予以擲入預備槽。 對於該裝設於預備槽105之石灰擲入口 185的數目並沒 有特定的限制。然而，預備槽較佳地具有2個或更多個石灰 擲入口，較佳是3個或更多個，且更佳是4-6個以等間距配 5置於周邊之石灰擲入口，藉此達到均勻地將石灰分散於預 備槽105之目的，而增加與居於循流氣體中之硫化物接觸的 機會（這可導致增加反應效率）。可以裝設17或更多個擲入 口，但其配置及控制會很複雜，因此少於17個擲入口通常 是足夠的。較佳是將數個擲入口裝設於相同的周邊上，意 10 即：居於相同高度之位置，俾以容易地於個別之擲入口來 控制石灰181a之擲入數量或飼入速率、載體氣體流動速 率、擲入流動速度、以及擲入角度。 於諸等個別擲入口之擲入數量、擲入時間、擲入物流 動速度及其他事項可以是相同，或個別地予以改變，只要 15 該居於氣體中之硫化物可使用該存在於焦炭之熱量來有效 地被固定即可。例如：可以改變個別擲入口之擲入數量、 掷入時間、掷入物流動速度及其他事項，措此避免石灰不 均等分佈（例如：居於預備槽之中央區域與周邊區域之間， 由於缺少石灰所產生的差異，會導致整體與硫化物之反應 20 效率下降）。再者，該將被擲入之石灰型態或其攙混物可以 隨擲入時間而改變。 如第1圖所顯示，該裝設石灰擲入口 185之位置較佳是 坐落在該居於環狀導管115頂部之預備槽部分，於該處除了 預備槽頂蓋103之外，橫剖面是向下擴大。 20 1300803 於擲入型（A)中，每一項因素(例如）：於諸等個別擲入 擲入數里、擲入物流動速度（流動速率）、以及擲入角度 I以依妝所有擲入之石灰數量、擲入時間、擲入位置（自頂 自預備槽之向下擴大部分）、及/或所使用之掷入口數 目來予以決定。可藉由前行測試或電腦模擬來決定最佳條 件’ I又佳地應該是於最後使用生產設備來施行驗證測試。 本I明建4可以藉由改變下文說明之載體氣體流動速率來 6周整特定之擲入數量、掷入物流動速度(流動速率）、以及擲 入角度’俾使石灰能夠均勻地分佈於預備槽中。 1〇 於該石灰在擲入熾紅焦炭105之間，通過一個頂部焦炭 擲入口 10來予以擲入(擲入型（A))之情形中，該擲入口 1〇4 不必須完全開啟，且可以開啟足夠令石灰通過即可。其亦 可以於頂蓋的一部分製造一個個別的石灰擲入口（沒有顯 示）。可以裝設數個石灰擲入口來包圍頂部焦炭擲入口，但 15 由於會造成裝置複雜化，因此較容易且較便利地是利用頂 蓋103之擲入口。 於經由該等裝設於預備槽105周邊之焦炭擲入口 1〇4或 石灰擲入口來擲入石灰18“之情形中，可以增大擲入口尺 寸或於擲入口邊緣裝設一種可移動機制或喷嘴’藉此使石 20 灰能夠容易地均勻分散於預備槽105之中。然而，由於已存 在之驅動裝置或機制（即使可供使用）必須是以高度絕熱組 件製成，這將增添成本，因此更佳是使用載體氣體(描述於 下文）來進行分散。 於熾紅焦炭151與石灰！81a同時擲入之擲入型（A-2)的 21 1300803 情形中，石灰181a較佳是與熾紅焦炭151同時經由掷入口 104—起被擲入，而不是經由該等裝設於預備槽周邊之石灰 擲入口 185來予以擲入，這是因為降落之熾紅焦炭151會阻 礙擲入之石灰朝向中央區域而導致石灰難以均勻分散。 5 以掷入(輸送）焦厌之方式而言，有很多種方法。舉例而 吕’第一種方法是使用適合的擲入裝置183，例如：遞送穿 置（例如：一部螺旋進料機或一部藉由重力降落石灰之平台 進料機）。第二種方法是使用載體氣體來輸送及擲入(吹入) 石灰。氮氣及/或一部分的循流氣體可供用為載體氣體。 1〇 於第二種使用載體氣體之方法中，會降低氣體的溫 度。一個實例是令已通過循流氣體鼓風機125之氣體分流， 然後經由管路186來予以飼入一部遞送裝置（例如：一部平 台進料機）之擲入裝置183，其後遞送裝置與飼入氣體共同 運作’藉此將供用為一種輸送氣體之氣體飼入一個自遞送 装置延伸至石灰擲入口 185之石灰輸送管路。於該使用氮氣 之情形中，來自一氮氣供應源之氣體會經由管路188來供廣、 〜部遞送裝置（例如：一部平台進料機）之擲入裝置183，且 如同該使用上述循流氣體之情形，遞送裝置與飼入氣體會 2〇 共同運作，藉此將供用為一種輸送氣體之氣體詞入一個自 遞咬襄置延伸至石灰擲入口 185之石灰輸送管路187。再者 、 使用氮氣與循流氣體此二者之情形中，會裝設可供用 ;此〜者之管路。藉由此種方法，可藉由切換管路路徑來 同^或交替使用氮氣與循流氣體，俾以有效地飼入載體氣 22 1300803 除了氮氣與循流氣體之外，對於可供用為一種輸送氣 體之氣體而言，可使用下列氣體（意即）：諸如氬氣之惰性氣 體、空氣（導入部分的空氣是為了達成其他特定的目的）、數 種於製鐵製程中所產生的氣體(例如：焦碳爐氣體、熔爐氣 5 體以及轉換器氣體）皆是可供用於具有目的性被導入空氣 之可選擇之氧氣供應源。 較諸簡單地藉由重力來降落石灰而言，氣體流動輸送 可以使用較少數的擲入口來大面積分散石灰，且將導致所 產生之石灰層厚度更均勻（於同時擲入之情形中，可提供更 10 佳的分散度）。使用循流氣體107來做為一種載體氣體，可 以將該使用氮氣所造成之不利於成本降至最低。 由於沒有使用載體氣體，因此使用重力來降落石灰之 方式具有低運作成本之優點。較佳是自頂部焦炭擲入口 104 擲入石灰，因為即使石灰是藉由重力降落，石灰仍然會由 15 於預備槽105内的氣體熱對流而適度地分散(散佈）。 於擲入型（B)之情形中，一個槽桶是一個可供用以輸送 熾紅焦炭之容器。一輛槽桶車是如第1圖所顯示之一輛具有 槽桶之車輛。可瞭解的是：本發明可以使用其他的輸送及 擲入設備。 20 於擲入型（B)之情形中，居於槽桶及/或槽桶車上的石灰 181b與熾紅焦炭151被放置在一起，俾以利用該裝載於一槽 桶及/或槽桶車之卸載自焦碳爐之熾紅焦炭於被擲入預備 槽之前所具有的有感熱量，其後將裝載之石灰及熾紅焦炭 輸送至CDQ設備101之預備槽105(精確地對準該居於一個 23 1300803 焦厌掷入口 104頂部之位置），俾以擲入該裝置的這個部 z專可供用以將石灰掷入一 CDQ設備之方法係包含： 擲入型(A)與擲入型(B)。 對於將石灰放置於槽桶及/或槽桶車之時間並不要求 4寸疋的時間。可以於任何的時間將石灰放置於槽桶及/或槽 桶車内(例如）··於該來自一焦碳爐熾紅焦炭被裝載於槽桶車 或類似物102之前、與裝載熾紅焦炭同時或於裝載熾紅焦炭 ’這是因為於所有的情形中都可利用焦炭的熱量來預 熱石灰。 15 20 (1)於裝載熾紅焦炭151之前，先將石灰181b裝載入槽桶 車或*貞似物。例如：在槽桶車或類似物1Q2將熾紅焦炭掷入 Qn又備101之後，返回焦碳爐時，將石灰放置入空的槽桶 s、員U物1G2。將石灰放置人空的槽桶車或類似物脱是 藉由—部使用重力或空氣輸送之石灰擲人裝置(例如：除了 Μ供用於擲人型（A)之—部職進料機或—部平台進料 機之外’可使用—部旋轉進料機），其後將 織紅焦炭⑸裝載入該載有石灰之槽桶車或類似物:爐 ，似(:：灰_裝載入已載有熾紅焦炭151之槽桶車或 、 用—部推擠機器將欲被載人槽桶車或類 ，102之熾紅线自焦碳爐㈣，其 個居於-石灰掷入裂置下方之位置(例如:二= 御入型㈧之-部螺旋進料機或一部平台進料=:、= 用-部旋轉進料機)’於該位置使用重力或' ° 咖放置域已财熾“、叙_車或;將3 24 υυ〇8〇3 =方式都很簡單容易運作且^會干擾石麵人裝置、焦炭 推挤機器以及CDQ設備。 於上述方式⑴中’於裝載熾紅焦炭之後，槽桶車或類 以物1〇2能夠在到達CDQ設備1〇1之前，不花費夺士載石灰之 5時間1上述方式⑺中，該被裝裁於槽桶車或類似物1〇2 之熾紅焦炭會被石灰mb覆蓋，這會促進石灰熱分解並 限制熾紅焦炭熱輕射，同時還會防止熾紅焦炭151與空氣接 觸而使熾紅焦炭燃燒。 上述兩種擲入型（A)與(B)可予以合併。於一個較佳具體 例中，在限制熾紅焦炭151熱輻射之下，只有將一個僅足夠 促進石灰181b進行熱分解之特定數量的石灰添加入槽桶車 或類似物1〇2(擲入型(B))，其後將其餘之所需數量以擲入型 (A)來予以擲入，藉此使石灰能夠與熾紅焦炭均勻地攙混及 分散。 15 於預備槽内部，所有或至少部分空間内的氣體是居於 一個較佳為100(M100°C之溫度。基於石灰熱分解以及該以 石膏（硫酸鈣(CaSCU))來固定硫組份之居於氣體中之硫化物 與熱刀解產物氧化#5(CaO)之間的反應而言，較高的溫度會 增加反應速率。因此，可預測會產生較高的去除硫效力。 20沉積於焦炭表面以石膏（硫酸鈣(CaS04))來被固定之硫會與 已冷卻之焦炭155以及剩餘未反應之碳酸鈣 氧化鈣（CaO)—併自一個CDQ設備之底部卸載出口 1〇8卸 出。大尺寸焦炭會被一焦炭切割機礙碎且以一篩網篩分， 收集該等無法通過篩孔之粉末焦炭，具有均一尺寸之焦炭 25 1300803 顆粒則於通過篩孔之後予以收集。石膏（硫酸鈣(CaS04))與 碳酸鈣（CaC03)及/或氧化鈣（CaO)是與粉末焦炭—起被送 至下列燒結製程。該通過篩孔之具有均一尺寸之焦炭被飼 入一熔爐中。一般而言，燒結礦(特別是一種自熔性燒結礦 5或者包含石灰的燒結礦會預先予以燒成氧化鈣(CaO)(通常 疋石灰石粉末）’藉此容爐不需要添加溶礦）會藉由添加粉末 焦炭及添加石灰來燒結鐵礦。於本發明中，已包含碳酸躬 (CaCCb)與氧化鈣(Ca〇)之粉末焦炭可供用為一種可取代石 灰之材料，這可減少燒結製程之添加石灰的耗用。因此， 10石灰可有效地供用為製鐵製程中的一種去除硫試劑。於 CDQ及燒結這兩種製程中，石灰都轉變為硫酸鈣(CaS〇4)。 没若預備槽内部空間的氣體溫度低於1〇〇〇。〇，則難以 進行熱分解反應· CaC〇3〜CaO+C02(於超過9〇〇°C時，產生 分解）。除此之外，去除硫之反應效率難以提高，這會導致 15低的去除硫化物比例（去除硫之百分比）。相反地，設若溫度 超過謂。C，則CDQ之冷卻效率會由於增加熱散失(例如·· 熱幸田射）而下降，這會導致整體熱功率下降。 預備槽内部空間並不必須於整體空間具有一個均一的 溫度分佈。甚至於小區域具有超過上述溫度範圍時，對整 20 體並無損害。 實施例 本發明將就下列特定實施例來做說明。然而，對於那 t沾白此項技勢人士而言，由於多種涵概於本發明精義及 範壽内之變化及修改可以由本說明書來明顯知悉，因此在 26 1300803 指定本發明較佳具體例之下，應瞭解特定實施例僅供用以 闡釋。 比車父貫施例丨（沒有擲入石灰）-於第1圖所顯示之正常 CDQ設備運作是假設導入預備槽之每丨噸焦炭為5立方公尺 5 (m3)(以周遭條件量測）。該5立方公尺(m3)(以周遭條件量測） 之數值疋在開啟頂盖103來掷入焦厌時，會自然導入預備槽 之空氣數$ ’該依據CDQ生產設備之運作記錄估算之數量 是一個相當精確的數值。這個比較實施例所使用之焦炭的 硫含量是〇 · 4wt%(乾燥）而揮發物質（Vm)内的硫含量則為 10 3%。預備槽内部空間之氣體溫度於運作期間是1〇〇〇-11〇〇 °C。此空間氣體溫度是以一個配置於如第丨圖所顯示之居於 預備槽105内部位置之溫度感應器來進行量測。載入焦炭爐 201之焦炭皆具有小於l〇mm之顆粒尺寸。 居於載入5立方公尺(m3)(以周遭條件量測）之氧氣數量 15 (〇2)為1 立方公尺(πι )(以周遭條件1測）’此等氧氣於燃 燒1.13公斤之熾紅焦炭下，會產生4.5公克之含硫(S)氣體。 藉此產生3.2公升之硫化物（SOx)(以周遭條件量測）。所產生 之硫化物（SOx)是以經由第1圖之氣體排放通路丨29排放之 氣體所具有之硫化物（SOx)濃度來予以量測。於沒有使用石 2〇 灰之情形下，其結果是排放氣體内具有之硫化物（SOx)濃度 為13ppm(於CDQ運作期間内排放氣體内具有之平均硫化物 (SOx)濃度）。 實施例1(擲入石灰)-同比較實施例1之情形，假設導入 預備槽之每1噸焦炭為5立方公尺(m3)(以周遭條件量測）。石 27 1300803 灰疋使用擲入裝置183、一部平台進料機以及一部使用空氣 做為載體氣體之氣體輸送系統，經由4個等距設置於預備槽 周邊之石灰擲入口 185，於間隔施行擲入熾紅焦炭151之間 予以擲入預備槽。更特別地，等量的石灰是藉由控制平台 5進料機以及輸送氣體流動速率，來經由4個石灰擲入口 185 吹入預備槽，藉此於焦炭上形成一層均勻的石灰層。擲入 每1°頓熾紅焦炭之石灰數量是3〇〇公克。其他的條件則同比 較貫施例1之條件。於此實施例1所使用之焦炭的硫含量是 0.4wt%(乾燥）而揮發物質（VM)内的硫含量則為3%。所使用 1〇 的石灰都是碳酸鈣(CaC03)。載入焦炭爐201之焦炭皆具有 小於10mm之顆粒尺寸。於此實施例丨所使用之石灰則包含 10〇/〇之顆粒尺寸小於l〇mm之石灰。更特別地，如第2圖所 顯示，所使用之石灰是以一部槌打型碾碎機（碾碎數量是 100公斤/小時、旋轉速度是2〇〇 rpm、擊槌寬度是10mm、擊 15 槌數量是丨2、出口篩網篩網尺寸是50mm(方形篩孔))來製 造。已礙碎之石灰是使用一個振動篩網（篩網尺寸10mm(方 形師孔）、傾斜5。、與傾斜水平及垂直方向之振幅為l〇mm， 且頻率為30/分鐘）來篩選。於進行3次測試之每一次試驗 中，尚未通過篩孔之石灰分別是10、9、l〇wt%。因此，該 20 礙碎石灰被界定為包含1 Owt%是具有一個小於10mm之顆 粒尺寸，然後予以使用於實施例1之運作中。 於此實施例中，CDQ設備之運作是每1噸熾紅焦炭擲入 300克石灰(碳酸鈣(CaC03))。量測排放氣體之硫化物（SOx) 濃度，該氣體是經由一個如第1圖之氣體排放通路129來予 28 1300803 以排放。經6豆貝δ亥排放氣體之硫化物（S〇x)濃度被減低至 lppm(於CDQ運作期間内排放氣體内具有之平均硫化物 (SOx)濃度）。換句話說’硫化物之排除或回收比例（去除硫 之百分比）是92%。 5 因此，可大幅地減少該由於硫酸（H2S04)或亞硫酸 (H2S〇3)積聚於蒸汽鍋爐109之熱交換管路表面或蒸汽鍋爐 109之出口部分所引發之酸銹蝕。 實施例2-本實施例使用與實施例1相同之石灰。本實施 例之石灰被置放入已裝載有熾紅焦炭之槽桶車1〇2。一般而 10言，於CDQ運作時，以1〇〇嘲/小時來予以擲入預備槽之焦 炭是具有一個1000°C之氣體溫度，藉此產生70·2噸/小時之 蒸汽（意即0.702嘲-蒸汽Λ頓-焦炭），且當30克/小時之石灰與 熾紅焦炭同時被添加入預備槽時，該CDQ設備會產生0 635 噸-蒸汽/4員-焦炭。然而，本發明人已發現：當預先以3〇克/ 15小時將石灰置放入槽桶車，其後再與熾紅焦炭同時予以擲 入預備槽時，該CDQ設備會產生0.64噸-蒸汽/噸-焦炭。因 此’於被擲入CDQ之前，於槽桶車分解之石灰百分比是： (0·64-0.635)/(0·702-0·635)χ100=7·5%。換句話說，當熾紅焦 厌仍停遠於槽桶車日守’邊織紅焦厌輪射入周遭氣體之熱量 20 可藉由分解7.5%之石灰數量來予以回收。 如上文所述，本發明可減少CDQ氣體之硫化物。於預 備槽每1噸焦炭導入5立方公尺(m3)(以周遭條件量測）空氣 之情形中，硫化物（SOx)濃度會由13ppm減少至lppm。這可 容許酸銹蝕維護頻率由每3年減少為至少每5年，藉此大幅 29 1300803 減少維修時間、工作及成本。早期，由於維修會涉及磨打 錢姓部分且必要之磨打會使該部分較預期更薄，因此錢蝕 金屬部分必須於預期之前予以更換。本發明亦將容許該等 通系會快速銹姓之裝置’能夠較長期運作。減少排放硫化 5 物（SOx)數|將導致降低氣體純化裳置之運作成本。 藉由CDQ冷卻之後的焦炭會被篩選。相同尺寸之焦炭 顆粒會於通過一筛孔之後被收集，然後被送入一個溶爐， 而諸等沒有通過筛孔之粉末焦炭則被送入燒結製程來予以 製成燒結礦。於燒結製程中，以粉末焦炭與石灰來燒結鐵 10礦，藉此製成10_20mm尺寸之燒結礦。於本發明中，添加 至CDQ設備之石灰會以石膏（硫酸鈣（CaS〇4))來固定硫組 份，其後自CDQ設備排出，並與沒有通過篩孔之粉末焦炭 一併被收集。因此，石膏（硫酸鈣(CaSO4))亦被飼入一燒結 製程中，這提供一種本發明衍生效用是將添加入燒結製程 15之石灰數量大幅降低至零，這是因為於燒結製程中，除了 未反應之碳酸鈣(CaC〇3)與氧化鈣(Ca0)可供用一種可替代 石灰之材料之外，石膏（硫酸鈣（Cash))亦可以藉由熱分解 產生氧化鈣(CaO)來供用為一種可替代石灰之材料。一旦被 固定之後，石膏（硫酸鈣（CaSCU))之硫會被送入一熔爐及一 ‘I，於忒4製私中，石I之硫組份會被氣化，然後 被再度排放。然而，石膏内之硫的數量是包含於焦炭内之 硫的一部分，因此該等裝設於燒結製程及熔爐内之存在的 硫排除裝置皆具有足以純化製程焦炭硫組份之能力。因 此’燒結製程（暫且不論、j：容爐）並不需要任何一種可供用以處 30 1300803 理來自CDQ設備之硫組份之額外的設備。 【圖式簡舉說明】 第1圖是本發明所使用之典型CDQ設備之示意圖。 第2(A)圖是一部供用以碾碎團塊之碾碎機的示意圖。 第2(B)-(E)圖闡釋兩個裝設於第2(A)圖碾碎機出口部 二之出口篩網之_孔圖案及篩孔尺寸，以及供用以區分礙 碎石灰、敎顆粒尺寸、及歡齡尺寸所佔百分比之區 分篩網。 【圖式之主要元件代表符號表】 101 · · .CDQ 設備 129···氣體排放通路 102···槽桶或槽桶車 103···頂蓋 151···熾紅焦炭 153…居於CDQ設備中之焦炭 1〇4···焦炭擲入口 155…自CDQ設備卸載之焦炭 105···預備槽 18 la···擲入型(A)石灰 106..·冷卻槽 181b…擲入型(B)石灰 107…循流氣體 183…石灰掷入裝置 108···卸載出口 188···管路 ···熱交換器(蒸汽鍋爐） 2〇1···焦碳爐 111…蒸汽 301.··石灰材料 113···蒸汽渦輪機 302…碾碎機 115.··環狀導管 303…旋轉器 117··.外部空氣 304.··擊槌 121··.循流通路 305…旋轉方向 123···粉塵搜集器 307···篩網 125··.鼓風機 127···循流氣體入口 308···篩孔 3110. Sulfide produced by coke combustion will follow the circulation device of the CDQ equipment with the circulating gas, and will be partially deposited into sulfuric acid (H2S〇4) in the lower temperature part (outlet) of the boiler (heat exchanger). Or sulfurous acid (H2S03), which causes metal rust on the surface of the metal part of the device. Therefore, periodic maintenance is required, and during maintenance, the machine is shut down for repair work (Example 15: grinding and polishing the surface of the rusted metal surface), and if necessary, the part of the deep rust must be replaced. If it is possible to prevent such metal corrosion, the frequency of maintenance can be reduced, which can greatly reduce the work, time and cost. However, an effective technique for preventing metal rusting of a circulating device of a C D Q device, particularly a low temperature portion of a boiler, has not been proposed. 2〇 [In the month of the invention] SUMMARY OF THE INVENTION One object of the present invention is to provide a method for reducing sulfide in a gas of a CDQ device which is produced in the air of a preliminary tank by burning coke. 1300803 The inventors have surprisingly discovered that when adding lime to the CDQ equipment, the tank can be (1) without the need for an additional amount of other fuel (eg, heavy oil) 'by adding lime to the CDQ equipment preparation tank, Achieving sufficient temperature and retention time for heating the decomposed lime, (2) decomposing lime by using only the practical heat of the blaze 5 red coke, so it does not increase the number of carbon dioxide, and (3) uses fuel more individually. Boiler to decompose lime to make quicklime' Then add the produced quicklime to the CDq equipment, adding lime to the CDQ equipment preparation tank will have a high heat recovery efficiency that can be expected. The present invention can reduce the sulfide in the gas of the CDQ device by any of the following methods. According to a first aspect of the invention, the method for reducing sulfur in a gas of a CDQ device comprises the step of throwing lime into a CDQ device. According to a second aspect of the invention, the pre-groove thrown into the lime will be successively thrown into the red hot coke. According to a third aspect of the invention, the lime is carried and thrown in a tank and/or a tank truck and then thrown into the blushing coke. According to the fourth aspect of the invention, the gas temperature in the inner space of the partial or integral preparation tank is 1000-1100 ° C. According to a fifth aspect of the invention, the lime comprises more than 10% by weight of lime having a particle size of less than 10 nm. According to a sixth aspect of the invention, the amount of thrown lime is 25-640 grams per ton of coke. According to a seventh aspect of the invention, the lime is thrown into the preparation tank during the interval of throwing into the red 焦 1300803 charcoal or is thrown into the preparation tank simultaneously with the blushing coke. According to an eighth aspect of the invention, the throwing lime is via a coke throwing population disposed at the top of the CDQ device, and/or one or more lime throwing inlets of the configuration. According to a ninth aspect of the invention, the throwing lime is a gas moving force by using the nitrogen gas and/or the circulating gas as a carrier gas. According to a tenth aspect of the invention, the lime is thrown into the tank and the hopper tank before, during, and/or after the woven red coke is loaded into the tank and/or the tank truck. ^ BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a schematic illustration of a typical CDQ device used in the present invention. Figure 2(A) is a schematic view of a mill for crushing agglomerates. Figure 2(B)-(E) illustrates the mesh pattern and mesh size of the two outlet screens installed at the exit of the mill of Figure 2(A), and for distinguishing the crushed lime A screen that defines the particle size and the percentage of a particular particle size. I: Embodiment 3 Detailed Description of the Preferred Embodiment 20 In one embodiment of the present invention, the specific example is a method for reducing sulfide in a gas of a CDQ device, wherein the loading (throwing) CDQ device The lime is used to reduce sulfide in the gas. During the combustion of coke, the sulfur contained in the coke is converted into the sulfide (S Ο X) in the shifted gas. The lime that is directly or indirectly thrown into the 1300803 tank through a tank truck will be thermally decomposed according to the heating decomposition reaction due to the heating of the hot coke, that is, at 7〇〇-900°C, CaC〇3—Ca0+ C〇2. Sulfide (such as sulfur dioxide (S〇2) or hydrogen sulfide (Hj)) in the gas (gas in the circulating gas and the pre-floating tank) will produce calcium oxide (CaO) produced by thermal decomposition with lime. The reaction is converted to gypsum (calcium sulfate (CaS〇4)), which means: OCaO+SC^+XC^-CaS〇4 and (2) Ca0+S02+H2S~> CaS+H20, CaS+2〇 2-CaS04. Since the thrown lime takes about one hour to pass through the temperature of the CDQ device at a temperature of 80 〇 - l 〇〇〇 ° c, there is sufficient time for the reaction to proceed. Sulfur dioxide (S〇2) or hydrogen sulfide (h2S) is accumulated on the surface of coke by a stone paste. As a result, the amount of sulfide in the gas is greatly reduced (for example, SOx is reduced by 92%), thereby greatly reducing rust in the system. As a result, the system becomes almost in a state that does not require maintenance. In the present invention, the sulfide in the gas is fixed by throwing lime, and the remaining unreacted calcium carbonate (CaC03) and calcium oxide (CaO) are available as an alternative to the lime in the sintering process. Sex materials, both of which are capable of removing sulfides during CDQ and sintering processes. In one embodiment of the present invention, the lime may be any calcium carbonate (CaC03), slaked lime (Ca(0H)2), one or more kinds of lime and calcium oxide (CaO). The resulting mixture, and a major component that can be utilized, is a natural limestone of calcium carbonate. There is no particular limitation on the particle size of the lime. Preferably, more than 10% by weight of the lime must have a particle size of less than 10 mm. More precisely, l (M00wt% (preferably 50-100%) of lime must have a particle size of less than 10 mm and must contain 〇_9〇wt% (preferably 〇50wt0/〇) 13〇〇8 〇3 疋 has a particle size of less than 10-200 mm. The reason is that some large-sized lime particles can be difficult to thermally decompose in CDq equipment, and then help to show the guar compounding process, which leads to a reduction in sulfur solidification. The stone fire is in other words. When the size of the lime is in the preferred size range, the lime can be held in the preheating zone and maintained in a high temperature region of over 700 °C for about 丨 hours. Thermal decomposition, and then sufficient to help remove the sulfide process. If the particle size is too large, the thermal decomposition reaction will not penetrate the center of the particle surface before the lime particles leave the high temperature zone (a part of the lime will be converted into carbon dioxide). (c〇2) gas, which (7) gas embrittles the part into fine particles); therefore, the thermal decomposition reaction using the coke recovery heat is insufficient, and the contact between the lime and the circulating gas is insufficient Promotes a reaction with sulfides in the gas. Therefore, it will be difficult to reduce the sulfide by fixing. However, the present invention can use the lime having a particle size of more than 2 mm. 15 Generally, it can pass the CDQ. In the case of equipment, such large-sized lime particles are ground to such an extent that the size falls within the range described above. When an additional amount of lime is added, in the case where some portions of the lime remain not thermally decomposed, the remaining lime may For use in a sintering process. Since the demand is normal through the coke of the CDQ equipment, it is preferred to have a narrow size of 20-45 mm average particle size, crush the large size coke with a coke mill, and then use one with A sieve of 25-30 mm mesh is used for sieving. If the lime is crushed into fine particles, the small size allows the granules to be fed into the sintering process as powdered coke. The lime must contain more than 1 〇wt % lime (preferably 5 〇 丨〇〇 % wt%) is 10 1300803. The reason for having a hardness of less than 1 Gmm is because the size of the lime used in the sintering process is It is often less than l〇mm and is convenient to use a lime size of less than 15mm based on this and other situations, so the preferred conditions are as follows: 1 (MQQwt% ((4) is 5 (MQQwt%) Fire must H from less than the knot The lime size of the process is used in the size of the grain and must be / page pack 3 〇 __9 〇 wt% (preferably the gradual (10) lime is a larger than the lime size used in the sintering process but less than the fine grain size 0 lime size definition The following is the following: 10 15 20 arrow household ^ ^ hunting by the screen of the mesh vertical dimension (such as the 2 (BME) map = Γ = defined, 俾 for use to distinguish between the broken machine jam / ... 疋 非 视Depending on the shape of the mesh, some examples of the shape of the hole are illustrated in the diagram of the 2 (Β)·(Ε). The mill is made of oppressed, rolled, and small. The use of pressure; type two = will _ her, /, type machine Jie Jie a honing machine and ball grinding branch, the typical machine using friction is a grinding machine blood type machine crying H and using cutting force near ;;H a cutting machine. Since the shape of most of the coded lime is similar to a spherical or cubic type (such as coal or food), it is a good measure of the size of the crushed particles.:: The mantle represents the particle size or average. The concept of particle size. However, the size of the surface lime is prepared by crushing lime through the sieve::, & Mingzhong '疋' is used to distinguish the size of the screen is not connected to the end of the boundary network, but separately prepared The other one is only used for the sieve screen of the non-crusher. The Ba 8 3 will be used to crush the lime and the lime particles will pass through a sieve and then reduce as much as possible to 1300803. The screen vibrates in the vertical direction. If the screen inclination angle is zero, the vibration is performed in the horizontal direction. The preparation of the small-sized lime is as follows, for example, as shown in Fig. 2: the lime material 301 is along the thick line of the arrow Loaded into the crusher 3〇2 (bashing type). A square 5 rotator 303 is rotated along the arrow line in the direction of rotation 305 to rotate the loaded lime. The rotated lime will be installed. Hit 3 in 4 in the crusher and crushed to a smaller size, or By slamming the gap between the 3〇4 and the rotator 3〇3, the reduced size lime will fly out due to centrifugal force through a screen fixed to the outer wall of the rotating path. If the screen 3 〇7 has a specific shape 10 308 and mesh size (as in the example shown in the 2nd (BHE) diagram), only the reduced size of the lime 3〇6 that can pass through the mesh hole will fly out of the screen 3〇7. The example of the screen is as follows The crushed lime is a beat-type crusher (the crushing quantity is 1 〇〇 kg / hour, the rotating speed is 200 rpm, the hitting width is 1 〇 mm, the number of shots is 15 is 12, the outlet screen The size of the mesh screen is 5 mm (square mesh). The crushed lime is a vibrating screen (screen size 1 mm (square mesh), tilt 5, horizontal and vertical amplitude) Screened for 1 〇mm and frequency of 3 〇/min. If the lime that has not passed through the sieve is 10, 9, or 10% by weight in 3 test tests, the crushed lime is defined as Contains 1% of the 20% with a particle size of less than 10mm (average 3% of the test's wt% value and rounded off) In a similar manner, if the lime that has not passed through the sieve hole is 20, 20, 20 wt%, respectively, wherein the outlet screen mesh size is 30 mm and the sieve size of the vibrating screen is, the crushed lime sample is It is defined as containing 20% by weight and having a particle size of less than 1〇mmt 12 1300803 inches. Meanwhile, if the lime which has not passed through the sieve hole is 8〇, 79, 79wt%, respectively, the size of the outlet screen mesh is l〇mm. And when the sieve size of the vibrating screen is 10 mm, the crushed lime sample is defined to contain 8 〇. / 〇 having a particle size of less than 10 mm. By using another smaller crusher ( The number of crushing is other kilograms/hour, 200 rpm, the width of the shot is i〇mm, the number of shots is 12), and the reliability of the data is increased. As described above, the percentage of lime having a size of less than 1 mm is defined as the weight percentage (wt%) of lime that does not pass through the mesh screen is changed by 1%, thereby changing the weight percentage (wt%), thus changing The size of the mesh of the mesh connecting the mill. The particle size can be changed by changing the shape of the above-mentioned illusion, b) the width of the shot, c) the speed of rotation, the position of the screen, the light crusher The type m is changed, for example, by a grinding cutter or a cutting mill, and by the size of the mesh of the crusher screen. In either case, the particle size is 15 to be defined by sieving. It can be changed by changing the vibration pattern or strip (for example: cam pulse, circular/elliptical moving screen, frequency) and the shape of the hole (square, round or elliptical) of the net. However, as long as疋, with the vibrating screen described above, the particle size can be defined as a normal value. 20 ==::: There is no special (four) limit. Vulcanization in gas" adds the ratio of reading. Preferably, it is necessary to add 640 grams per charcoal. If the amount of lime added to coke per town is less than %%, the sulfide may not be completely removed. Conversely, if the amount of lime added to each plant is more than _gram, the sulfide can be completely removed, 13130040, but some of the lime will remain unreacted. However, it will be harmless as long as the amount of lime remaining falls in some amount which can be completely supplied to the above sintering process. The reason why the lime car father's 备 备 备 备 免 免 是 是 是 是 焦 焦 焦 焦 焦 焦 焦 焦 焦 焦 焦 焦 焦 焦 焦 焦 焦 焦 焦 焦 焦 焦 焦 焦 焦 焦 焦 焦 焦 焦 焦 焦 焦 焦 焦Some of the air is naturally introduced into the coke throwing inlet, and some air is intentionally introduced for use for some purposes. For example, when 5-20 cubic meters (1113) of air (measured by ambient conditions) is fed into the preparation tank, it burns. 13-4. 5 kg of coke will convert 4·5_2〇·3g of 10 of the sulfur contained in coke to 3. 2-14. 2 liters of sulfide (s〇x). According to the test data of the continuous production system, this corresponds to the unloading gas containing 13-52 ppm of sulfide (SOx). It is assumed that the flow of gas around the coke is used to fluidize the lime around the coke with the thermal decomposition product calcium oxide (CaO), calcium/sulfur (Ca/s) 15 , thinking that adding lime (Ca) The number of components is twice the amount of sulfur (s) components in the circulating gas. Under these conditions, sulfur can be effectively removed. Therefore, the amount of lime that should be added per ton of coke should be 25_13 grams of calcium carbonate (CaC03). It is assumed that the lime and the thermal decomposition product calcium oxide (Ca〇) 20 existing around the coke are filled with a bed, and the feed/sulfur (Ca/S)-1 is a condition for effectively removing sulfur because Reduce contact with gases. Therefore, for a packed bed, the amount of lime suitable for addition per ton of coke should be 140-640 grams of calcium carbonate (CaC03). Coke appears in a CDQ device as if it were in a moving bed. In the case of 14 1300803, the degree of gas contact is between a fluid bed and a packed bed. Based on this, the amount of lime suitable for addition per ton of coke should be 25-640 grams of calcium carbonate (CaC03). Preferably, however, a pre-test is performed which uses a production system to determine the amount of lime suitable for addition under varying conditions of the amount of air in a moving bed condition. The inventors have proposed a technique of using a biological mass rather than coke to throw into a preparation tank. In the case of alternative fuels, such as the use of biomass, the amount of lime added may take into account the difference between the amount of air and the amount or analog of the added biomass, as estimated by the gas 10 The amount of sulfide is measured. However, it is preferred to use a production facility to perform a verification test to determine the amount of lime suitable for addition in terms of the amount of air and biomass. The lime does not need to be thrown into the preparation tank. The essence of the present invention is to react oxidized 15 calcium (CaO) generated by thermal decomposition of lime, particularly limestone, calcium carbonate, and slaked lime, with sulfide to fix sulfide in CDQ gas. Even the hardest calcium carbonate among the decomposable can be decomposed at a temperature exceeding 900 °C. In order to maintain the thermal decomposition reaction, the heat of the red coke (about l ° ° C) in the preparation tank can be used, and the blushing of the self-coke furnace used in the tank or the tank truck can be used. The heat of the coke, the heat of the red 20 coke (before being thrown into the preparation tank) has not been utilized. This heat is wasted by radiation into the air (about 5 minutes) before being loaded in the tank or drum to reach the CDQ. The method of the present invention comprises placing lime in a tank together with blistering coke whereby heat is utilized to preheat the stone ash for thermal decomposition. 15 1300803 The details are explained in terms of drawings. Figure i is a schematic illustration of a typical CDQ device used in the present invention. In the coke oven 2 (the simmered red coke i5i made of sputum is pushed into a tank or tank car (hereinafter referred to as _ car or similar) 1 〇 2, 5 俾 to transport to The blushing coke is unloaded into the pre-slot milk by opening a top cover of the CDQ device 1G1 and generally covering the top of the coke throwing population. After throwing the red line (5), close the cover (9) to block the natural inflowing air. The empty tank car or the like 1〇2 returns to the coke oven 2〇ι for the next 10 carry. The high-temperature coke 151 will fall downward through a cooling tank 1G6 located at the bottom, and the cold portion is to be cooled to 200 C by the circulating gas, and then the unloading outlet is touched from the cooling tank at the bottom. 15 20 1〇8 unloading. In the middle, the thick line of the arrow represents the red hot coke before the throwing CDQ equipment. The number 153 represents the coke in the CDQ equipment, and the remaining line of the solid arrow indicates the moving direction, while the wealth 155 The job is unloaded from CDQ equipment (including lime and gypsum). The heat is supplied by a heat exchanger (steaming) The steaming furnace) is 1〇9 and is passed through the circulating emulsion 107. The steam generated by the heat (4) (1) will push the steam. The turbine 113 generates electricity. The external air 117 is added to a circular duct gas discharge outlet. In the case where the transmissive components or powder = coke (and powdered lime and gypsum in the present invention) reach the heat, ά Γ amp &; coking or some heat conduction problems, the duct will ignite The volatile component and the coke powder are contained in the circulation passage 121 between the annular duct 115 and the heat exchanger l〇9. For collecting coke powder, lime powder and gypsum powder, the collected powder will be used in a subsequent sintering process. The passing gas 109 after passing through the heat exchanger 109 having a steam boiler will be used by using the The circulating gas blower 125 living in the circulation passage 121 adjusts the gas pressure 'by returning to the cooling tank 1〇6 via a circulating gas inlet 127. A gas discharge passage 129 for discharging a part of the circulating gas can be loaded Located in the residence The flow gas blower 丨25 and the circulating gas inlet 12 7 are in the flow path 121 to maintain the flow rate of the circulating gas into the CDq device 1〇1. When appropriate, a flow control valve can be flowed The meter and/or exhaust gas purification device is disposed on the gas exhaust passage 129. One method of the present invention that can be used to reduce sulfide in a gas in a CDQ device will be further explained with reference to Figure 1. As shown in Figure 1 , the lithium i8ia (called throw-in type (A)), which is thrown into a CDQ device 101, which is thrown into the blistering coke 151, is placed in a tank and/or a tank. The lime 181b of the vehicle 102 (referred to as the throw-in type (B)) may be placed in the preparation tank and the tank and/or the tank truck in a combination of the types (A) and (B). Let me now discuss a specific example of some throw-in type (A). 20 In the throw-in type (A-1), the blushing coke 151 is batch-loaded by a few minutes to tens of minutes (throwing in a batch operation). The addition of the lime 181a may fall between the edges and the like by throwing it into the blushing coke 15 via the suitable lime throwing device 183, which makes the throwing time easy. Preferably, however, the addition of lime should be immediately after the blistering coke is loaded into the preparation tank 1〇5 17 1300803. The normal internal space temperature of the CDQ device 101 is at the expense of llGGt: due to the heat of the blistering coke, so that no coke and ash are required. In addition, since the thrown lime takes about an hour to pass through the area of the CDq device at a temperature of 800-1000 C, the reaction time (residence time) is sufficient. Therefore, there is no specific limit to the throw time. However, the lime that is thrown in immediately after the red coke 151 is thrown in can add a fixed amount of sulfide before the vulcanization of the gas into the gas circulation path, thereby reducing the concentration of the sulfur component contained in the gas. The outlet part of the steam steel furnace can therefore reduce the occurrence of acid rust in the system. 10 A “coke batch loading interval” is to throw all the red charcoal in the first tank car or the like 102 into the preliminary tank 〇5 to open the second tank car or the like. The time elapsed at the bottom of 102 at the beginning of the next batch of blushing coke. When the lime is thrown in the blistering coke, the coke enthalpy 15 and the lime layer will settle in the CDQ equipment, both It will overlap like a sandwich, and a layer of lime which undergoes a thermal decomposition reaction and a sulfur removal reaction will be converted into gypsum, which will then be fixed when deposited on coke, and then discharged from the bottom unloading outlet 108. In the type (A-2), the lime 181a can be thrown into the preparation tank 105 by using the throwing device 183 at the same time as the 20 throwing of the red hot coke 151. This simultaneous throwing is a preferred example. Since the lime is scattered on the blaze The red coke layer, so the heat of the red coke surrounding the lime will be effectively utilized to promote the thermal decomposition reaction. The thermally decomposed lime will easily contact the sulfide in the circulating gas flowing between the coke gaps. , This effectively seals the stone through the 1300803 component. “Tossing at the same time, means that the start and end of the throwing lime falls from the tank car or the like 102 to the time of unloading the red charcoal. At the same time, throwing in can allow good coke and lime to mix, which can increase the chance of contact between lime and coke (which will increase the heat transfer efficiency and promote thermal decomposition reaction) and at the same time increase the chance of contact with the circulating gas (this will increase the calcium oxide) (Ca〇) The reaction efficiency with the sulfides in the gas, thereby promoting the fixation of sulfur). In the case of simultaneous throwing, each batch of blushing coke 151 and stone 181a are laminated to form a multilayer body. The multilayer body is settled in the cdq apparatus 10, and the lime is continuously converted into gypsum deposited on the surface of the coke via a thermal decomposition reaction and a removal of the melon reaction until finally discharged from the bottom unloading outlet 108. The throw-in type (A-3) is a combination of a throw-in type (A-1) and a throw-in type (A_2). At some stage, the lime is thrown between throwing red incand, and in some 15 stages, it is thrown at the same time. The desired amount of lime is added to form a layered or mixed layer of coke and lime for the purpose of benefiting the individual throwing type. In any of the throwing patterns described above, the amount of lime 1Sla and blushing coke (5) thrown in each batch may be thrown in at all times, or 20 consecutively thrown during a fixed period of -, or Throw in at intervals during a period of time. There is no specific limit to the way to throw. The L rate may be maintained fixed or varied in the case of continuous or intermittent throwing. In the above-mentioned throw-in type, the lime can be thrown through the top coke throwing inlet 108 at the top of the house device 101, and/or one or more lime throwing inlets i85 of 19 1300803 in the preliminary tank 105. Prepare the trough. There is no particular limitation on the number of the lime throwing inlets 185 installed in the preliminary tank 105. However, the preliminary tank preferably has 2 or more lime throwing inlets, preferably 3 or more, and more preferably 4-6, with equal spacing, 5 placed at the periphery of the lime throwing inlet, This achieves the purpose of uniformly dispersing the lime in the preliminary tank 105, increasing the chance of contact with the sulfide in the circulating gas (which may result in an increase in reaction efficiency). It is possible to install 17 or more throws, but its configuration and control can be complicated, so less than 17 throws are usually sufficient. Preferably, a plurality of throwing inlets are installed on the same periphery, meaning 10: at the same height, and the number of throwing or feed rate of the lime 181a, the carrier gas, is easily controlled at the individual throwing inlets. Flow rate, throwing flow rate, and throw angle. The amount of throwing at each of the individual throwing entrances, the throwing time, the throwing speed, and other matters may be the same, or may be changed individually, as long as the sulphide living in the gas can use the heat present in the coke It can be effectively fixed. For example, you can change the number of throws in individual throwing entrances, the time of throwing, the speed of throwing objects, and other things, so as to avoid uneven distribution of lime (for example, between the central area of the preparation tank and the surrounding area, due to the lack of lime The resulting difference will result in a reduction in the overall efficiency of the reaction with sulfides. Furthermore, the lime type to be thrown or its mash can change with the throw time. As shown in Fig. 1, the position of the lime throwing inlet 185 is preferably located at the portion of the preliminary groove at the top of the annular duct 115, where the cross section is downward except for the preliminary tank top cover 103. expand. 20 1300803 In throw-in type (A), each factor (for example): in each individual throw-in number, throwing object flow rate (flow rate), and throwing angle I to make all throws The amount of lime entered, the time of throwing, the position of the throw (from the top to the downward extent of the preparation tank), and/or the number of throws used are determined. The best condition can be determined by forward testing or computer simulation. I should also use the production equipment to perform the verification test. The present invention can be used to uniformly distribute the lime in the preparation by changing the carrier gas flow rate described below to 6 weeks of the specific throwing amount, the throwing material flow rate (flow rate), and the throwing angle '俾In the slot. 1 In the case where the lime is thrown between the red hot coke 105 and thrown through a top coke throwing inlet 10 (throw type (A)), the throwing inlet 1〇4 does not have to be fully opened, and It can be opened enough to allow the lime to pass. It is also possible to create an individual lime throwing inlet (not shown) in a portion of the top cover. A plurality of lime throwing inlets may be provided to surround the top coke throwing inlet, but 15 is easier and more convenient to utilize the throwing entrance of the top cover 103 due to the complexity of the device. In the case where the lime 18" is thrown through the coke throwing inlet 1 or 4 or the lime throwing inlet installed around the preliminary tank 105, the throwing inlet size may be increased or a movable mechanism may be installed at the edge of the throwing inlet or The nozzle ' thereby allows the stone 20 ash to be easily and evenly dispersed in the preparation tank 105. However, since the existing drive means or mechanism (even if available) must be made of a highly insulated component, this will add cost, Therefore, it is more preferable to use a carrier gas (described below) for dispersion. In the case of 21,300,803 of the red-type coke 151 and the lime-type 81a thrown into the throw type (A-2), the lime 181a is preferably blazed. The red coke 151 is simultaneously thrown through the throwing inlet 104 instead of being thrown through the lime throwing inlet 185 installed around the preliminary groove, because the falling red blister 151 hinders the thrown lime. Facing the central area, it is difficult to disperse the lime evenly. 5 There are many ways to throw (transport) the caries. For example, the first method is to use a suitable throwing device 183, for example: Sending through (for example: a screw feeder or a platform feeder that drops lime by gravity). The second method is to use carrier gas to transport and throw (inject) lime. Nitrogen and / or A portion of the circulating gas is available as a carrier gas. In the second method of using a carrier gas, the temperature of the gas is lowered. One example is to split the gas that has passed through the circulating gas blower 125, and then via line 186. Feeding device 183 into a delivery device (eg, a platform feeder), after which the delivery device operates in conjunction with the feed gas 'by feeding a gas for delivery as a carrier gas into a self-delivery The apparatus extends to the lime transfer line of the lime throwing inlet 185. In the case of the use of nitrogen, the gas from a nitrogen supply source is supplied via the line 188 to the wide delivery unit (eg, a platform feeder) The throwing device 183, and as in the case of using the above-mentioned circulating gas, the delivery device and the feed gas will work together, thereby providing a gas input into the gas as a transport gas. The self-delivery biting device extends to the lime conveying line 187 of the lime throwing inlet 185. Further, in the case of using both nitrogen gas and circulating gas, it is provided for use; In this method, the nitrogen and the circulating gas can be used alternately or alternately by switching the pipeline path, so as to effectively feed the carrier gas 22 1300803, in addition to the nitrogen gas and the circulating gas, it can be used as a conveying gas. For gas, the following gases (meaning) can be used: inert gases such as argon, air (introduced part of the air for other specific purposes), and several gases produced in the iron making process (eg, coke) The carbon furnace gas, the furnace gas 5 and the converter gas are all available alternative oxygen sources for purposeful introduction of air. Compared to simply landing the lime by gravity, the gas flow transport can use a smaller number of throwing inlets to disperse the lime over a large area and will result in a more uniform thickness of the resulting lime layer (in the case of simultaneous throwing, Provides 10 better dispersions). The use of the circulating gas 107 as a carrier gas can minimize the disadvantage of the use of nitrogen. Since no carrier gas is used, the use of gravity to lower the lime has the advantage of low operating costs. Preferably, the lime is thrown from the top coke throwing inlet 104, because even if the lime is dropped by gravity, the lime is moderately dispersed (spread) by the thermal convection of the gas in the preliminary tank 105. In the case of the throw-in type (B), a tank is a container for conveying blistering coke. A tank truck is a vehicle with a tank as shown in Figure 1. It will be appreciated that other delivery and throwing devices can be used with the present invention. 20 In the case of the throw-in type (B), the lime 181b and the blushing coke 151 living on the tank and/or the tank truck are placed together to be loaded in a tank and/or a tank truck. The sensible heat of the blistering coke unloaded from the coke oven before being thrown into the preparation tank, and then the loaded lime and blush coke are delivered to the preparation tank 105 of the CDQ apparatus 101 (accurately aligned with the residence) A 23 1300803 focus on the top of the inlet 104, the method of throwing the part into the device for throwing lime into a CDQ device includes: throw-in type (A) and throw-in type ( B). The time required to place the lime in the tank and/or the tank is not required to be 4 inches. The lime can be placed in the tank and/or the tanker at any time (for example). - Before the red coke from a coke oven is loaded in the tank car or the like 102, simultaneously with the loading of the red charcoal Or loading smouldering cokes' because the coke heat can be used to preheat the lime in all cases. 15 20 (1) Prior to loading the blushing coke 151, the lime 181b is loaded into the tank car or *贞. For example, after the tank car or the like 1Q2 throws the red hot coke into the Qn and prepares the 101, when returning to the coke oven, the lime is placed into the empty tank s, the member U 1G2. The removal of the lime into the empty tank car or the like is carried out by means of a gravity or air transported lime throwing device (for example: in addition to the Μ Μ for the throwing type (A) - the part feeder or - Outside the platform feeder, the machine can be used as a rotary feeder, after which the woven red coke (5) is loaded into the tank containing the lime or the like: furnace, like: (:: ash_loading Into a tank truck that has been loaded with blazing coke 151, or a pushing machine that will be carried by a tank truck or a class, 102 blazing red line from a coke oven (four), one of which resides in - lime thrown into the crack Position below (for example: 2 = Royal Type (8) - Partial Screw Feeder or 1 Platform Feed =:, = Use - Partial Rotary Feeder) 'Use gravity or ' ° coffee placement field at this location It’s already squandering, and it’s about 3 24 υυ〇 8〇 3 = the way is very simple and easy to operate and ^ will interfere with the stone face device, the coke push machine and the CDQ device. In the above way (1) 'loading After the red coke, the tank car or the class 1〇2 can reach the CDQ device 1〇1, and does not spend 5 times of the lime load. In the above manner (7), the The blushing coke packed in a tank car or the like 1〇2 will be covered by lime mb, which will promote the thermal decomposition of lime and limit the heat of the red coke, while preventing the red coke 151 from coming into contact with the air. Red coke combustion. The above two throw-in types (A) and (B) can be combined. In a preferred embodiment, under the heat radiation of the limited red coke 151, only one is only sufficient to promote the heat of the lime 181b. The specific amount of lime decomposed is added to the tank car or the like 1 〇 2 (throw type (B)), after which the remaining required amount is thrown in the throw-in type (A), thereby making the lime It can be uniformly mixed and dispersed with blazing coke. 15 Inside the preparation tank, all or at least part of the space of the gas is at a temperature of preferably 100 (M100 ° C. Based on thermal decomposition of lime and the gypsum (sulphuric acid) Calcium (CaSCU)) is used to fix the reaction between the sulfide component of the sulfur component in the gas and the hot knife solution oxidation #5 (CaO). Higher temperatures increase the reaction rate. Therefore, it is predicted to be produced. Higher sulfur removal efficiency. 20 deposited on coke surface with gypsum Calcium sulphate (CaS04) to be fixed sulfur will be discharged from the cooled coke 155 and the remaining unreacted calcium carbonate (CaO) - and discharged from the bottom unloading outlet 1 〇 8 of a CDQ plant. Large size coke It is crushed by a coke cutter and sieved by a sieve to collect the powdered coke which cannot pass through the sieve hole. The coke of the uniform size 25 1300803 is collected after passing through the sieve. Gypsum (calcium sulfate (CaS04) And calcium carbonate (CaC03) and/or calcium oxide (CaO) are sent to the following sintering process together with powdered coke. The coke having a uniform size through the mesh is fed into a furnace. Generally, sintering Minerals (especially a self-fluxing sinter 5 or a sinter containing lime will be pre-fired into calcium oxide (CaO) (usually slaked limestone powder) 'so that the furnace does not need to be added to the ore) will be added by adding powder coke And adding lime to sinter the iron ore. In the present invention, powdered coke which has contained barium carbonate (CaCCb) and calcium oxide (Ca〇) can be used as a material which can replace stone dust, which can reduce the consumption of lime added in the sintering process. Therefore, 10 lime can be effectively used as a sulfur removal reagent in the iron making process. In both CDQ and sintering processes, lime is converted to calcium sulfate (CaS〇4). The gas temperature in the internal space of the preparation tank is less than 1〇〇〇. 〇, it is difficult to carry out thermal decomposition reaction · CaC〇3~CaO+C02 (decomposition occurs when it exceeds 9 °C). In addition, the efficiency of removing sulfur is difficult to increase, which results in a low sulfur removal ratio (percent of sulfur removal). Conversely, if the temperature exceeds the stated value. C, the cooling efficiency of the CDQ will decrease due to the increase of heat loss (for example, the heat of the field), which will cause the overall heat power to drop. The internal space of the preparation tank does not have to have a uniform temperature distribution in the entire space. Even when the small area has a temperature range exceeding the above, there is no damage to the whole body. EXAMPLES The present invention will be described with respect to the following specific examples. However, it is obvious to those skilled in the art that the various changes and modifications within the spirit and scope of the present invention are apparent from the present specification. Therefore, a preferred embodiment of the present invention is designated at 26 1300 803. In the following, it should be understood that the specific embodiments are only illustrative. More than the parent's example (no throwing lime) - the normal CDQ equipment shown in Figure 1 is assumed to be 5 cubic meters (5 m3) per ton of coke introduced into the preparation tank (measured by ambient conditions) ). The value of 5 cubic meters (m3) (measured by the surrounding conditions) 自然 the amount of air naturally introduced into the preparation tank when the top cover 103 is opened for throwing into the anomaly is estimated based on the operational record of the CDQ production equipment. The quantity is a fairly accurate value. The coke used in this comparative example had a sulfur content of 〇 · 4 wt% (dry) and a volatile matter (Vm) having a sulfur content of 10 3%. The gas temperature in the interior space of the preparation tank is 1〇〇〇-11〇〇 °C during operation. This space gas temperature is measured by a temperature sensor disposed at a position inside the preliminary tank 105 as shown in the figure. The coke loaded into the coke oven 201 has a particle size of less than 10 mm. The amount of oxygen in a load of 5 m ^ 3 (measured by ambient conditions) 15 (〇 2) is 1 m ^ 3 (πι ) (measured by ambient condition 1) 'These gases are burned 1. Under 13 kilograms of red charcoal, it will produce 4. 5 grams of sulfur (S) gas. This produces 3. 2 liters of sulfide (SOx) (measured by ambient conditions). The produced sulfide (SOx) is measured by the concentration of sulfide (SOx) in the gas discharged through the gas discharge passage 第29 of Fig. 1. In the absence of stone 2 ash, the result is a sulfur oxide (SOx) concentration of 13 ppm in the exhaust gas (the average sulfide (SOx) concentration in the exhaust gas during the CDQ operation). Example 1 (throwing lime) - In the same manner as in Comparative Example 1, it was assumed that 1 ton of coke introduced into the preliminary tank was 5 m ^ 3 (m 3 ) (measured by ambient conditions). STONE 27 1300803 ash uses a throw-in device 183, a platform feeder, and a gas delivery system that uses air as a carrier gas, via four lime-throw inlets 185 that are equidistantly disposed around the preparation tank, at intervals Throw into the red coke 151 and throw it into the preparation slot. More specifically, an equal amount of lime is blown into the preparation tank via four lime throwing inlets 185 by controlling the platform 5 feeder and the conveying gas flow rate, thereby forming a uniform layer of lime on the coke. The amount of lime thrown into every 1° of blistering red coke is 3 gram. Other conditions are comparable to the conditions of Example 1 year-on-year. The sulfur content of the coke used in this Example 1 is 0. The sulfur content in the volatile matter (VM) is 4 wt% (dry) and 3%. The 1 〇 lime used is calcium carbonate (CaC03). The coke loaded into the coke oven 201 has a particle size of less than 10 mm. The lime used in this example contains 10 〇/〇 of lime having a particle size of less than 10 mm. More specifically, as shown in Fig. 2, the lime used is a beat-type mill (milling quantity is 100 kg/hr, rotation speed is 2 rpm, shot width is 10 mm, hitting) The number of 15 槌 is 2, and the size of the outlet screen is 50 mm (square mesh)). The crushed lime is screened using a vibrating screen (mesh size 10 mm (square hole), tilt 5, amplitude with tilt horizontal and vertical directions l〇mm, and frequency 30/min). In each of the three tests, the lime that had not passed through the sieve was 10, 9, and 1% by weight, respectively. Therefore, the 20 slaked lime is defined to contain 1 Owt% which has a particle size of less than 10 mm and is then used in the operation of Example 1. In this embodiment, the operation of the CDQ device is to throw 300 grams of lime (calcium carbonate (CaC03)) per ton of blushing coke. The sulfide (SOx) concentration of the exhaust gas is measured, and the gas is discharged through a gas discharge passage 129 as shown in Fig. 1 to 28 1300803. The concentration of sulfide (S〇x) in the 6 Beans δ Hai emission gas was reduced to 1 ppm (the average sulfide (SOx) concentration in the exhaust gas during the CDQ operation period). In other words, the exclusion or recovery ratio of sulfur (the percentage of sulfur removed) was 92%. 5 Therefore, the acid rust caused by the accumulation of sulfuric acid (H2S04) or sulfurous acid (H2S〇3) on the surface of the heat exchange line of the steam boiler 109 or the outlet portion of the steam boiler 109 can be greatly reduced. Example 2 - This example used the same lime as in Example 1. The lime of this embodiment is placed in a tank car 1〇2 which has been loaded with blazing red coke. Generally speaking, in the CDO operation, the coke thrown into the preparation tank at 1 〇〇 / / hour has a gas temperature of 1000 ° C, thereby generating 70. 2 tons / hour of steam (meaning 0 . 702 ridicule - steam Λ - coke), and when 30 grams / hour of lime and blister coke are added to the preparation tank at the same time, the CDQ equipment will produce 0 635 tons - steam / 4 members - coke. However, the inventors have found that the CDQ device generates 0 when the lime is placed in the tank car at 3 gram / 15 hours in advance and then thrown into the preparation tank simultaneously with the blushing coke. 64 tons - steam / ton - coke. Therefore, before being thrown into the CDQ, the percentage of lime decomposed in the tank car is: (0·64-0. 635) / (0·702-0.635) χ 100 = 7.5%. In other words, when the blushing sorrow is still far away from the tanker's day, the side of the woven red focus is injected into the heat of the surrounding gas. 20 can be broken down by 7. 5% of the amount of lime is recycled. As described above, the present invention can reduce sulfides of CDQ gas. In the case where the inlet tank introduces 5 cubic meters (m3) of air per minute (measured by ambient conditions), the sulfide (SOx) concentration is reduced from 13 ppm to 1 ppm. This allows the acid rust maintenance frequency to be reduced from every 3 years to at least every 5 years, thereby significantly reducing maintenance time, work and costs by 29 1300803. In the early days, since the repair would involve grinding the part of the money and the necessary grinding would make the part thinner than expected, the metal part of the money must be replaced before it is expected. The present invention will also allow such devices to be rapidly rusted to operate longer. Reducing the amount of sulfur vulcanization (SOx) will result in lower operating costs for gas purification. The coke after cooling by CDQ will be screened. The coke particles of the same size are collected after passing through a sieve and then sent to a furnace, and the powder coke which has not passed through the sieve holes is sent to a sintering process to form a sintered ore. In the sintering process, iron ore is sintered by powder coke and lime, thereby producing a sintered ore having a size of 10-20 mm. In the present invention, the lime added to the CDQ apparatus fixes the sulfur component with gypsum (calcium sulfate (CaS〇4)), and thereafter is discharged from the CDQ apparatus and collected together with the powdered coke which has not passed through the sieve. Therefore, gypsum (calcium sulfate (CaSO4)) is also fed into a sintering process, which provides a derivative effect of the present invention in that the amount of lime added to the sintering process 15 is greatly reduced to zero because, in the sintering process, Unreacted calcium carbonate (CaC〇3) and calcium oxide (Ca0) can be used as a substitute for lime. Gypsum (calcium sulfate) can also be produced by thermal decomposition to produce calcium oxide (CaO). A material that can replace lime. Once fixed, the sulfur of the gypsum (calcium sulphate (CaSCU)) is sent to a furnace and an ‘I, in the 忒4 system, the sulfur component of the stone I is vaporized and then re-discharged. However, the amount of sulfur in the gypsum is part of the sulfur contained in the coke, so that the sulfur removal means present in the sintering process and in the furnace have sufficient capacity to purify the process coke sulfur component. Therefore, the 'sintering process (for the time being, j: furnace) does not require any additional equipment for the sulphur component from the CDQ equipment. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a schematic diagram of a typical CDQ device used in the present invention. Figure 2(A) is a schematic view of a mill for crushing agglomerates. The second (B)-(E) diagram illustrates the two hole patterns and mesh sizes of the outlet screens installed at the exit portion 2 of the second (A) crusher, and is used to distinguish between crushed lime, A screen that differentiates the particle size and the percentage of the age of the sensation. [The main components of the diagram represent the symbol table] 101 · · . CDQ equipment 129···Gas discharge passage 102···Slot drum or tank truck 103···Top cover 151···Glowing red coke 153...Coke in the CDQ equipment 1〇4···Coke throwing inlet 155 ...coke unloaded from CDQ equipment 105···preparation tank 18 la···throw type (A) lime 106. . - Cooling tank 181b... Throwing type (B) Lime 107... Circulating gas 183... Lime throwing device 108··· Unloading outlet 188··· Pipeline···Heat exchanger (steam boiler) 2〇1·· ·Coke oven 111... steam 301. ··Lime material 113···Steam turbine 302...Milling machine 115. ··Circular conduit 303...rotator 117··. Outside air 304. ··Knocking 121··. Circulation path 305...Rotation direction 123···Dust collector 307···Screen 125··. Blower 127···Circulating gas inlet 308···Screening hole 31