200936236 六、發明說明： L 明所屬 3 技術領域 本發明關於對隔熱型反應器供給原料’藉伴隨發熱之 5 平衡反應而製造目的物時進行反應器内部之溫度控制方法 與反應裝置及二甲醚之製造方法。 【先前技術3 背景技術 φ 於製造工廠中，有在反應器内設置觸媒層’使原料流 10 通其中並使其反應而獲得其反應生成物之製品的情形。用 以使反應器内適切地進行反應之重要的運轉條件之一，巧· 舉出有反應器内的溫度管理。一般係將原料調整至預先設 定之溫度後，供給至反應器。 上述反應為發熱反應時，隨著原料朝向反應器内之下 15 游侧流通，即隨著進行反應，原料的溫度會上昇起來。一 旦原料的溫度較適合於主反應之溫度範圍高時，會產生不 ® 好的副生成物(不純物）而造成原料的損失，或是因會促進填 縫(caulking)而使觸媒變差，另一方面，一旦原料之溫度低 於前述溫度範圍則收率會降低，因此已提出了將觸媒層内 20之溫度維持在目的之溫度範圍内之各種方法。已知用以維 持如此反應器内之溫度之代表的例子有以下的手法。 第14圖為多管式反應器100，建構成於多管式反應器 100内將原料供給至多數垂設的管1〇丨内，而於此管101内進 行反應’藉冷媒而從外部冷卻該管丨01。雖然此多管式反應 3 200936236 器100可確實且快速地冷卻原料，但是必須有多量的冷媒， 又，反應器100的構造複雜，因此裝置之成本變高而不適於 更大型化。 第15圖表示連接多數座反應器102,並於此反應器 5 102、012之間中介設置有熱交換器（中間熱交換器）1〇3的裝 置。此裝置中，已供給至第1段之反應器102内的原料在此 第1段的反應器102内因反應而發熱，接著藉熱交換器1〇3冷 卻後被供給至第2段的反應器1〇2，而在此第2段之反應器 102反應進行起來。之後，雖然省略圖式，然而原料進而以 10 熱交換器為中介而被供給至第3段以後的反應器。如此的構 造中，為了提昇在反應器102内之溫度的控制性，必須增加 反應器102及熱交換器103的座數，且必須有連接配管，因 此裝置的成本變高，又，裝置構造變複雜。又，如此的熱 交換器103，係建構成大多使用供給第丨段之反應器1〇2前之 15反應前的原料作為熱交換用的冷媒，而將與反應生成物之 間熱交換之後的原料供給至第1段的反應器1〇2。如此情形 下，反應器102之出口的的溫度會影響反應器1〇2之入口的 溫度’而存在有難以控制反應器1〇2内之溫度的問題。 因此’專利文獻1提出了將固定地板流通式之隔熱型反 20應器内之觸媒層分割成複數層’並於各層間設置用以冷卻 原料的淬媳區’於此淬熄將淬熄流體的原料以液體狀來供 給而冷卻反應器内的手法。此裝置中，一旦被加熱之原料 被供給至上側，則於上游側之觸媒層進行發熱反應，原料 的溫度會上昇。原料於淬熄區藉淬熄而冷卻，之後流向下 200936236 游側的觸媒層，同樣進行反應。淬熄流體的流量係被調整 * 成在供給淬熄流體後之淬熄區的下游側測定原料的溫度， 而§亥部位的溫度在適合主反應的溫度範圍。 此裝置以一座反應器構成，又，由於不需要熱交換器’ 5因此可抑制成本。又’使用非活性成分作為淬熄流體時， 必須非活性成分之精製與分離，但是由於是利用原料，因 此具有不需要如此操作的優點。 然而’伴隨著上述發熱之平衡反應的一例，係例如從 Ο 曱醇製造二甲醚之反應器的話，反應器之出口溫度較通常 10運轉時之溫度稍微上昇的情形下，因不良的副反應而會產 生副生成物。因此有必要使反應器内的溫度穩定化。 - 上述專利文獻1記载之反應器，係依據下游側之觸媒層 之入口侧的溫度調整淬熄流體的供給量，而控制反應器之 内部溫度，但是，在控制系統的特性上難以將前述入口侧 15之溫度一定化，且加上原料之溫度變化等要因而無法避免 該入口侧之溫度變化。 ® 在如此的狀況下，一旦如專利文獻1將原料作為淬熄流 體來供給時，由於原料多，因此平衡偏向反應生成物侧。 如此一來，相對於觸媒層之入口側的溫度變化，反應速度 20會敏感地改變，故觸媒層之入口側之溫度對反應器之出口 侧之溫度的影響大，結果則反應器之出口溫度的上下幅度 大，轉化率的變化也大。因此，反應器之出口溫度變得過 高會因不好的副反應而產生副生成物，會降低製品的純 度，又，反應器之出口溫度變得過低會導致無法達到作為 5 200936236 目的之收率。 因此’企盼著在可大型化之單純構造的反應器，能以 簡便的方法控制反應器内之溫度的技術。 專利文獻 1:特開 2004 — 298768(段落0014、0020、0021) 5 【^^明内】 發明揭示 本發明係鑑於上述情形而完成者，其目的在於提供將 原料供給至隔熱型之反應器，當藉伴隨此反應器内之發熱 的平衡反應而製造目的物時，可提昇反應器内之溫度之控 10 制性’且可抑制因溫度上昇所導致之產生副生成物與因溫 度降低所導致之收率降低的技術。 本發明之反應器内部的溫度控制方法，係將反應區域 分割成複數，經分割之複數反應區域分配於一個或二個以 上的隔熱型反應器，將原料供給至隔熱型反應器内，且藉 15 伴隨發熱之平衡反應而製造目的物時進行的溫度控制方 法，特點在於包含有以下步驟：將原料供給至第1段的反應 區域，獲得包含目的物之反應生成物；接著’將從前段側 之反應區域取出之反應生成物與從未反應之原料所構成之 混合物，供給至順序為後段侧的反應區域，獲得包含目的 20 物之反應生成物；及於前述各反應區域之間之至少一處， 將淬熄流體供給至前述混合物，且藉混合而冷卻該混合 物，又，前述淬熄流體包含在較前述淬熄流體之供給區域 後段側之反應區域所獲得之前述反應生成物的一部分、及 在前述隔熱型反應器以外所獲得之與前述目的物相同化合 200936236 物之至少一者。 * 前述淬熄流體也可包含將最後段之反應區域所獲得之 反應生成物冷卻後之反應生成物的一部分。 前述複數反應區域分別由觸媒層所構成為佳。 5 經分割之前述反應區域為三個為佳。 前述冷卻步驟係調整前述淬熄流體之供給量、組成及 溫度之至少一者而進行為佳。 前述伴隨發熱之平衡反應，也可以甲醇作為原料而獲 ® 得水與目的物之二甲醚所構成之反應生成物的反應。此情 10 形下’前述淬熄流體以包含二甲醚與二曱醚及水之混合流 體之其中任一者為佳。 -· 本發明之反應裝置，係將原料供給至隔熱型反應器内 . 且藉伴隨發熱之平衡反應而製造目的物之反應裝置’特點 在於包含有：一個或二個以上的隔熱型反應器，將反應區 15 域分割成複數，且分配經分割之複數反應區域者；原料供 給機構，係將原料供給至第1段的反應區域者；淬熄區’係 ® 介於前述各反應區域之間之至少一處，用以將淬熄流體供 給至從前段側之反應區域取出之前述反應生成物與未反應 之原料所構成之混合物，且藉混合而冷卻該混合物者；及’ 20淬熄流體供給機構，係將包含較前述淬熄區後段側之反應 區域所獲得之前述反應生成物的一部分、及在前述隔熱型 反應器以外所獲得之與前述目的物相同化合物之至少一者 之流體作為谇熄流體供給至淬熄區者。 前述反應裝置以包含有用以將最後段之反應區域所獲 7 200936236 得之反應生成物冷卻的冷卻機構，且前述淬熄流體係包含 以前述冷卻機構冷卻後之前述反應生成物之一部分的流體 為佳。 前述複數反應區域分別由觸媒層所構成為佳。 5 經分割之前述反應區域為三個為佳。 又，本發明之反應裝置以包含有調整前述淬熄流體之 供給量、組成及溫度之至少一者，並將前述淬熄流體供給 至前述淬媳區之控制部為佳。 前述伴隨發熱之平衡反應，也可以甲醇作為原料而獲 © 10 得水與目的物之二甲醚所構成之反應生成物的反應。此情 形下，前述淬熄流體以包含二甲醚與二甲醚及水之混合流 體之其中任一者為佳。 ·_ 本發明之二甲醚之製造方法，係將反應區域分割成複 數，經分割之複數反應區域分配於一個或二個以上的隔熱 15 型反應器，將曱醇供給至隔熱型反應器内，且藉脫水縮合 反應而製造二甲醚之方法，特點在於包含有以下步驟：將 甲醇供給至第1段的反應區域，獲得包含二甲醚與水所構成 〇 之反應生成物；接著，將從前段側之反應區域取出之反應 生成物與從未反應之甲醇所構成之混合物，供給昱順序為 20 後段側的反應區域’獲得二甲醚與水所構成之反應生成 物；及於前述各反應區域之間之至少一處，將泮媳^IL體供 給至前述混合物，且藉混合而冷卻該混合物，又’前述淬 熄流體包含在較前述淬熄流體之供給區域後段侧之反應區 域所獲得之二甲醚及水之至少一者、及在前述隔熱型反應 8 200936236 • 器以外所獲得之二甲醚之其中任一者。 ’ 前述冷卻步驟係調整前述淬熄流體之供給量、組成及 溫度之至少一者而進行為佳。 前述淬總流體以在最後段之反應區域獲得，且包含& 5 卻後之二甲醚及水之其中任一者為佳。 前述複數反應區域分別由觸媒層所構成為佳。 經分割之前述反應區域為三個為佳。 前述淬熄流體以除去混合存在於二甲醚之副生成物之 φ 水與未反應之甲醇後之二甲醚的一部分為佳。 10 依據本發明，建構成將反應區域分割成複數，經分巧 . 之複數反應區域分配於一個或二個以上的隔熱型反應器， 將原料供給至隔熱型反應器内，且藉伴隨發熱之平衡反應 而製造目的物時，將包含原料供給至第1段的反應區域所獲 得包含目的物之反應生成物與未反應之原料所構成之混合 15物’從此第1段之反應區域供給至順序為後段側的反應區域 而獲得包含目的物之反應生成物，且於各反應區域之間之 ® 至少一處’將在較該反應區域後段侧所獲得之反應生成物 之一部分及在前述隔熱型反應器以外所獲得之與前述目的 物相同化合物之至少一者作為淬熄流體來供給，而冷卻該 20混合物。因此，混合物中之反應生成物的量增加，平衝偏 向於示料側’反應穩定地進行，故反應區域之入口側的溫 度變化所造成之反應速度的變化少。其結果，可提昇反應 器内之溫度的控制性，能抑制因温度上昇而造成非預定之 副生成物的產生，可簡便地抑制因溫度降低所造成收率的 9 200936236 降低。 圖式簡單說明 第1圖表示用以實施本發明之製造方法之反應裝置之 一例的概略構造圖。 5 第2圖表示上述反應裝置之反應器内原料之溫度變化 之一例的概略圖。 第3圖表示上述反應裝置之其他例的縱剖面圖。 第4圖表示上述反應裝置之其他例的縱剖面圖。 第5圖表示上述反應裝置之其他例的縱剖面圖。 10 第6圖表示上述反應裝置之其他例的縱剖面圖。 第7圖表示上述反應裝置之其他例的縱剖面圖。 第8圖表示上述反應裝置之其他例的縱剖面圖。 第9圖表示上述反應裝置之其他例的縱剖面圖。 第10圖表示上述反應裝置之其他例的縱剖面圖。 15 第11圖表示上述反應裝置之其他例的縱剖面圖。 第12圖表示使用於本發明之實施例之比較例之裝置的 概略圖。 第13圖表示使用於本發明之實施例之比較例之裝置的 概略圖。 20 第14圖表示使用於合成反應之習知裝置的概略圖。 第15圖表示使用於合成反應之習知裝置的概略圖。 【實施方式3 實施發明之最佳樣態 參照第1圖及第2圖來說明本發明之反應裝置及使用此 10 200936236 - 裝置之溫度控制方法的實施樣態。第1圖表示包含用以製造 ， 目的物之反應裝置2之製造工廠全體的概要。反應裝置2具 有例如固定地板流通式之隔熱型反應器之縱型的反應器 20。此反應器20之塔頂部連接著供給原料之機構之原料氣 5體供給管20&之一端側，此原料氣體供給管20a之另一端侧 藉由熱父換器2a及蒸發器2b而連接著貯存有液體原料的原 料貯存源4。蒸發器2b係用以使液體原料氣化而獲得原料氣 體者。 φ 反應器20之底部連接著生成氣體流出管20b之一端 10側，此生成氣體流出管20b連接著上述熱交換器2a。於此熱 交換器2a建構成原料氣體供給管2〇a内的原料，與生成氣體 流出管20b内之反應生成物及原料所構成之混合物之間，原 料被加熱’混合物被冷卻並進行熱交換。此生成氣體流出 管20b之另一端側連接於將於後述之第1蒸德塔3〇之侧壁。 15 反應器20的内部，用以獲得作為目的之反應收率所必 須之反應區域’例如分割設成上游侧與下游侧，上游側之 φ 反應區域藉第1觸媒層22a而形成作為第1反應區域，下游侧 之反應區域藉第2觸媒層22b而形成作為第2反應區域。此等 觸媒層22(22a、22b)係藉多數未以圖式顯示之形成有氣體供 20 給孔的支撐構件23所支撐著。 反應器20内之第1觸媒層22a與第2觸媒層22b之間的區 域設有用以藉淬熄流體冷卻反應器2 0内之混合物的淬熄區 Q。將反應生成物之一部分作為淬熄流體而供給至淬媳區之 機構的淬熄流體供給管24連接於此淬熄區Q之反應器20側 11 200936236 面，此淬熄流體供給管24於反應器20内之淬熄區Q之上方側 之接近第1觸媒層22a的部位’連接著用以將淬熄流體均一 地分散供給之形成有多數吐出孔24b的噴灑部24a。 又，於反應器20的侧面設有溫度檢測部29 ’建構成其 5 一端侧突出於反應器20内，例如於第2媒體層22b之上部側 附近檢測已在淬熄區Q冷卻之混合物的溫度。建構成控制部 3連接於此溫度檢測部29，此控制部3依據溫度檢測部29之 檢測溫度而控制淬熄流體的流量，藉將於後述之流量調整 閥27以使原料氣體之溫度在適於反應的溫度範圍。 1〇 於反應器20之後段設有用以將從反應器20獲得之混合 物取出作為目的之反應生成物，並將其一部分作為淬熄流 體而供給至反應器20的設備，於第1圖中設有包含用以獲得 例如將二甲醚作為目的物之二條蒸餾塔30、40的設備。 第1蒸餾塔30係用以從未反應之原料與反應生成物所 15 構成之混合物，分離精製目的物者，冷卻機構之目的物取 出管31連接著塔頂部，排出管32之一端侧連接著下端部。 建構成從目的物取出管31排出之目的物被作為製品而被取 出至系統外，但是，其一部分藉從此目的物取出管31分歧 之前已說明之淬熄流體供給管24，使淬熄流體回到已說明 20之淬熄區Q。於淬熄流體供給管24中介設有流量調整閥27。 已說明之排出管32之另一端侧連接著第2蒸餾塔4〇的 侧壁。此第2蒸餾塔4〇係用以從上述第1蒸餾塔30中已除去 目的物之混合物，分離精製未反應的原料者，原料排出管 41之一端側連接於塔頂部，排出管42連接於下端部。建構 200936236 ' 成原料排出管41之另一端部連接於已說明之蒸餾器2b之上 ， 游側的原料氣體供給管20a，將未反應之原料回復再使用。 排出管42係用以廢棄已從混合物去除目的物及未反應之原 料後所殘留之副生成物與不純物等者，此等物被排出至系 5 統外。 接著參照第1圖及第2圖來說明運轉上述反應裝置2的 方法。 以一種物質或多種物質構成之液體原料，在設置於前 _ 段之蒸發器2b被氣化，又，於熱交換器2a中，從反應器20 1〇 取出之未反應的原料與反應生成物所構成之混合物之間進 行熱交換而被加熱至溫度T1。 之後，原料氣體藉由原料氣體供給管20a而被供給至反 應器20，而在此反應器20内從上朝下方向流動。在第1觸媒 ' 層22a内依據以下式子（1)的平衡反應而產生包含目的物的 15 反應生成物，構成包含此反應生成物與未反應之原料氣體 的混合物的氣體。 φ 原料氣體〇反應生成物（目的物+副生成物）+反應 熱……(1) 藉此時產生之反應熱，混合物之氣體溫度上昇而達溫 20 度 T2。 製造二甲醚時，液體原料之甲酵氣化’在第1觸媒層22a 内藉以下記載之式子(2)的平衡反應而產生二甲醚與水。 2CH3OH ^ CH3〇CH3 + Η2〇 + ΔΗ ...(2) ΔΗ= — 23.4kj//mol 13 200936236 接著於淬熄區Q，一旦從喷灑部24a供給淬熄流體，則 此淬熄流體與藉前段的觸媒層22a的發熱反應而達高溫(T2) 的混合物的氣體混合，混合物的溫度會達T3。此淬熄流體 係在該反應裝置2獲得之反應生成物的一部分所構成的流 5 體，而以液體狀或氣體狀供給。製造二甲醚時，淬熄流體 係使用例如氣體的二甲醚。 如上所述，以將反應生成物之一部分作為淬熄流體來 供給而於第2觸媒層22b内，上述式子（1)、（2)之右側之反應 生成物的量變多，因此，式子（1)、（2)之平衡反應偏向原料 10 侧而抑制目的物產生之反應，故上述反心應可穩定地進行。 如此一來，已冷卻之混合物氣體，更詳細者為包含淬 熄流體之混合物被供給至第2觸媒層22b，於第2觸媒層22b 藉同樣的反應而穩定地產生反應生成物。此反應生成物與 未反應的原料所構成之混合物藉在此第2觸媒層22b之反應 15 所產生之反應熱而上昇至溫度T4。 之後’混合物藉由生成氣體流出管20b而從反應器20被 取出’於熱交換器2a與原料之間進行熱交換。 以製造二甲醚的情形為例說明之後的流程，從反應器 20排出之反應生成物之二甲醚及水與未反應原料之甲醇所 20 構成之混合物被供給至第1蒸餾塔30，可分離目的物之二甲 醚。從混合物分離精製之二曱醚從目的物取出管31被取 出，在目的物取出管31之管壁等散熱而達已說明之溫度T2 以下的溫度’ 一部分藉由淬熄流體供給管24作為淬熄流體 而回到反應器20。剩餘的二甲醚當作製品而被取出至系統 200936236 - 外。 ' 已被除去二甲鍵的混合物從第1蒸德塔30的下側排出 而供給至第2蒸餾塔40 ’於此第2蒸餾塔40分離精製未反應 之原料的甲醇。如已說明的情形，未反應的原料回到原料 5 氣體供給管20a與從原料貯存源4供給之原料一同再次供給 至反應器20。又，已去除目的物及未反應之原料之副生成 物的廢棄物於此例子中被排出至系統外。 藉溫度檢測部29檢測出觸媒層22b之入口的溫度T3，因 φ 應該溫度檢測值並藉由控制部3及流量調整閥27而控制淬 10 德流體的供給流量，因此可達到觸媒層22b之入口溫度T3 的穩定化，但是，無法避免此入口溫度T3因某變動幅而變 ， 動。但是，由於本發明使用反應生成物作為淬熄流體，因 此如已說明的情形，平衡反應偏向示料側而抑制目的物之 產生的反應，對於觸媒層22b之出口溫度T4之觸媒層22a的 15 入口溫度T1的影響變小。即，相對於觸媒層22a之入口溫度 T1的變化，對目的生成物之反應速度的變化小，因此觸媒 〇 層22b之出口溫度T4的變化變得遲鈍，轉化率之變動幅變 小〇 依據上述實施樣態，建構成將原料供給至隔熱型之反 20 應器20内，要藉伴隨發熱之平衡反應而製造目的物時，於 用以進行原料之反應的第1反應區域與第2反應區域之間設 有淬熄區Q，將從第2反應區域取出之反應生成物的一部分 冷卻而作為淬熄流體供給至此淬熄區Q，而冷卻原料與反應 生成物所構成之混合物。因此，如已詳細說明的情形，混 15 200936236 合物中的反應生成物的量增加，平衡偏向原料側而反應穩 定地進行，因此容易進行反應器20内的溫度控制，其結果 可抑制因溫度上昇而產生非預定的副生成物’且能抑制因 溫度降低所造成收率的降低。而且，可抑制觸媒之填縫， 5 可使觸媒之壽命長。而且，可抑制反應裝置2之急劇的溫度 上昇（暴走反應），可安全地運轉反應裝置2。爰此，與已知 之方法比較，本發明可簡略化反應器20的構造’容易大型 化，又，構成反應器20之構件數量少。 上述淬熄流體可為氣體也可為液體。使用氣體之淬熄 10 流體時，由於無法利用蒸發潛熱，因此較使用液體時必須 更多的供給量，但是，由於反應器20内之反應生成物的量 變多，因此抑制反應速度的效果大。相對於此，使用液體 之淬熄流體時，比使用氣體時少的供給量即能混合物的溫 度。又，例如原料之供給量少，因反應所造成之混合物之 15 溫度上昇小的情形下，也可不使反應生成物冷卻而作為淬 熄流體來供給。此情形下，反應器20内之反應生成物的量 變多，因此可抑制反應速度。 又，上述例子中，將觸媒層22設為兩層，惟，例如第3 圖及第4圖所示，也可為此等以上的觸媒層。第3圖表示包 20 含有三層觸媒層（2a、2b、2c)之反應器20，第4圖表示包含 有五層觸媒層（22a、22b、22c、22d、22e)之反應器20。於 第3圖、第4圖中，在各觸媒層22之間的淬熄區q，藉溫度檢 測部29檢測出混合物的溫度，而調整從喷灑部24a供給之泮 熄、流體的流量。如此的反應器20亦與上述的例子同樣係藉 200936236 * 泮媳流體抑制反應速度的狀態進行反應。如此地將觸媒層 、 22設為多數層的狀態，可獲得與上述例子同樣的效果。 又，於一座反應器20内設置多數層觸媒層22的情形以 外，例如也可如第5圖、第6圖所不’將設置一層觸媒層22 5之反應器20連接多數座。第5圖、第6圖分別表示連接三座、 五座反應器20的例子，淬熄流體供給管24連接著用以連接 各個反應器20之間的生成氣體流出管20b。而且，於如此的 反應器20以外，也可如第7圖、第8圖所示組合並連接多數 赢 座設有至少一層觸媒層22之反應器20。第7圖表示串聯連接 醫 10 設有一層觸媒層22之反應器20與設有二層觸媒層（22a、22b) 之反應器20的例子。第8圖表示串聯連接設有三二層觸媒層 (22a、22b)之反應器20與設有三層觸媒層（22a、22b、22c) 之反應器20的例子。此等觸媒層22之間也同樣建構成在淬 ' 熄區Q供給淬熄流體。於如此的構造中，也可獲得與上述例 15 子同樣的效果。 上述各例子中，各觸媒層22、22之間全部的觸媒層最 0 好是設置淬熄區Q，但是，例如在溫度變化幅度小的情形下 等’也可減少淬熄區Q的數量，亦即只要有至少一個以上的 淬熄區Q即可。第9圖表示於已說明之第4圖所示之反應器20 20中’省略了徒上游側起第2個觸媒層22b與第3個觸媒層22c 之間的淬媳區Q的例子。於如此的反應器2〇中，也可獲得同 樣的效果。 又’上述的例子中，利用系統内的目的物作為淬熄流 體’但疋’也可利用與系統外之目的物相同的化合物作為 17 200936236 淬媳流體。如此的例子中，也可例如第1 〇圖所示’設置多 數反應裝置2,而從一反應裝置2對另一反應裝置2供給淬熄 流體。如此的情形下，係另一反應裝置2之淬熄流體供給管 24連接一反應裝置2的目的物取出管31。又’以上第3圖至 5第10圖中，對於與第1圖相同的構造賦與相同符號。也可於 此等淬熄流體之目的物混入未反應的原料。 又，利用目的物作為淬熄流體以外，也可例如從原料 產生目的物以外之反應生成物（副生成物）的情形下（於目的 物以外也有於式子（1)之右邊側生成的物質的情形下）’可利 10用該反應生成物作為淬熄流體，例如於獲得二甲醚之反應 中，可使用水作為淬熄流體。此情形下如第1圖所示，從目 的物取出管31取出目的物之全量，廢棄物之一部分作為淬 熄流體回到淬熄區Q。於此情形下，與上述例子同樣由於式 子（1)、（2)之右邊侧之反應生成物增加而可抑制反應，因此 15 反應穩定地進行，反應器20出口之混合物的溫度的變化幅 度變小。又，第11圖中，對於與第1圖相同的構造賦與相同 符號。 又，也可將目的物與此副生成物一同作為淬熄流體使 用，例如’在從甲醇獲得二甲醚的反應中，可將二甲醚與 20 水作為淬熄流體使用。而且，也可將來自系統外之二曱醚 作為淬媳流體使用。 又，上述各例子中，使用與反應生成物或目的物相同 之系統外化合物作為泮媳流體’但是’只要是在可抑制反 應速度之程度包含與反應生成物或目的物相同系統外之化 200936236 • 合物的話，也可於此淬熄流體包含有未反應的原料。此情 、 形下，也可例如於第1圖中，將中介設置有閥之分歧管（均 未以圖式顯示）之一端側連接原料排出管41，而將此分歧管 之另一端側連接淬熄流體供給管24，藉調整此閥之開度而 5 積極地將未反應的原料作為淬熄流體之一部分使用。 而且，上述各例子中，藉控制部3而控制淬熄流體的流 量而使反應器20之入口温度T3穩定化，但是，也可建構成 將淬熄流體之流量設為一定，藉由控制部3例如調整前述分 φ 歧管之閥及流量調整閥27之開度，並以調整淬熄流體所包 10 含之反應生成物或與目的物相同系統外之化合物比率，亦 即’以調整淬熄流體之組成而使入口温度T3穩定化。又， 也可建構成於淬熄流體供給管24設置未以圖式顯示之冷卻 機構，而將淬熄流體之流量設為一定，藉由控制器3調整淬 ' 熄流體之溫度而使反應器20之入口溫度T3穩定化。而且， 15也可建構成藉由控制部3調整淬熄流體之流量、淬熄流體之 組成及淬媳流體之溫度之複數組合而使反應器2〇之入口溫 φ 度T3穩定化》 本發明之目的物之溫度控制方法及反應裝置如上所 述，也可適用於藉伴隨發熱之平衡反應而產生目的物時， 20例如從後述之實施例之f酵脫水所構成之二甲醚的合成反 應，或氫與氮所構成之氨的合成反應。又，前述合成反應 之其他，也可適用於伴隨發熱之平衡反應例如氧化反應、 氫化反應以外的反應，也可適用於液相中的此等反應。 實施例 19 200936236 以下說明用以確認本發明之方法的效果而進行的實 驗。此實施例係使用甲醇作為上述原料，進行以已說明之 式子(2)之伴隨發熱之平衡反應獲得作為目的物之二甲醚的 實驗。 5 又，雖然以下各實驗設定了標準條件，但是此標準條 件係將最終觸媒層出口之甲醇的轉化率及各觸媒層之出口 的溫度設定為在分別的標準條件下為相等的條件。 用以進行上述反應之裝置係使用已說明之第1圖所示 之反應裝置2,而於反應器20之入口及觸媒層22a、22b之各 10 個入口與出口設置溫度計。 於此反應裝置2，供給流量F1的曱醇，將二甲醚作為淬 熄、流體並以流量F2供給至淬媳區Q，又，將未反應之甲醇以 流量F3返回。副生成物之水從已說明之排出管42排出。又， 各流量F1〜F3表示分別流體的質量流量。 15 實驗條件係決定如以下的各條件使反應器20之出口之 甲醇的轉化率及溫度分別為75%、340°C，並將此條件作為 標準條件。又，將反應器20之入口的原料溫度從上述標準 條件上下分別改變1°C，並對此等以外的條件，以與標準條 件相同的條件進行了實驗。於各個條件下，比較反應器2〇 20之出口的溫度（第2觸媒層22bt出口側的溫度)及、又反應器 20之出口之甲醇的轉化率。又，對於淬熄流體之二曱醚的 流量F2及從原料排出管41回來之未反應的原料之甲酵的流 量F3，設成與標準條件相同的流量。 (標準條件） 20 200936236200936236 VI. Description of the Invention: Technical Field The present invention relates to a temperature control method and a reaction apparatus for a reactor inside a reactor for supplying a raw material to a heat-insulating reactor by an equilibrium reaction with heat generation. A method of producing an ether. [Prior Art 3] In the manufacturing plant, there is a case where a catalyst layer is provided in a reactor to pass a raw material stream therethrough and react to obtain a product of the reaction product. One of the important operating conditions for allowing the reaction to proceed appropriately in the reactor is exemplified by temperature management in the reactor. Generally, the raw materials are adjusted to a predetermined temperature and then supplied to the reactor. When the above reaction is an exothermic reaction, as the raw material flows toward the lower side of the reactor, the temperature of the raw material rises as the reaction proceeds. Once the temperature of the raw material is higher than the temperature range suitable for the main reaction, a by-product (impurity) which is not good may be caused to cause loss of the raw material, or the catalyst may be deteriorated by promoting caulking. On the other hand, once the temperature of the raw material is lower than the above temperature range, the yield is lowered. Therefore, various methods have been proposed in which the temperature in the catalyst layer 20 is maintained within the intended temperature range. An example of a representative for maintaining the temperature in such a reactor is known as follows. Fig. 14 is a multi-tubular reactor 100 constructed in a multi-tubular reactor 100 to supply raw materials into a plurality of vertically disposed tubes 1 , and the reaction in the tubes 101 is cooled from the outside by a refrigerant. The tube is 01. Although the multi-tube reaction 3 200936236 can reliably and rapidly cool the raw material, it is necessary to have a large amount of refrigerant, and the structure of the reactor 100 is complicated, so that the cost of the apparatus becomes high and it is not suitable for a larger size. Fig. 15 shows a device in which a plurality of reactors 102 are connected, and a heat exchanger (intermediate heat exchanger) 1〇3 is interposed between the reactors 5 102 and 012. In this apparatus, the raw material supplied to the first stage reactor 102 is heated by the reaction in the reactor 102 of the first stage, and then cooled by the heat exchanger 1〇3 and supplied to the reactor of the second stage. 1〇2, and the reactor 102 in this second stage reacts. Thereafter, although the drawings are omitted, the raw materials are further supplied to the reactors after the third stage by the 10 heat exchangers. In such a configuration, in order to improve the controllability of the temperature in the reactor 102, it is necessary to increase the number of seats of the reactor 102 and the heat exchanger 103, and it is necessary to have a connection pipe, so that the cost of the device becomes high, and the device configuration becomes complex. In addition, the heat exchanger 103 is configured to use a raw material before the reaction of 15 before the reactor 1〇2 supplied to the second stage as a refrigerant for heat exchange, and after heat exchange with the reaction product. The raw material was supplied to the reactor 1〇2 of the first stage. In this case, the temperature at the outlet of the reactor 102 affects the temperature of the inlet of the reactor 1〇, and there is a problem that it is difficult to control the temperature in the reactor 1〇2. Therefore, Patent Document 1 proposes to divide a catalyst layer in a fixed-floor flow-type heat insulating type reactor into a plurality of layers and to provide a quenching zone for cooling the raw materials between the layers. The raw material of the quenching fluid is supplied in a liquid form to cool the inside of the reactor. In this apparatus, when the material to be heated is supplied to the upper side, the catalyst layer on the upstream side undergoes an exothermic reaction, and the temperature of the raw material rises. The raw material is quenched and quenched in the quenching zone, and then flows down to the catalyst layer on the side of 200936236, and the reaction is also carried out. The flow rate of the quenching fluid is adjusted. * The temperature of the raw material is measured on the downstream side of the quenching zone after the quenching fluid is supplied, and the temperature of the sea portion is in a temperature range suitable for the main reaction. This apparatus is constituted by one reactor, and further, since the heat exchanger '5 is not required, the cost can be suppressed. Further, when an inactive component is used as the quenching fluid, refining and separation of the inactive component are required. However, since the raw material is used, there is an advantage that such an operation is not required. However, an example of the equilibrium reaction with the above-mentioned heat generation is, for example, a reactor in which dimethyl ether is produced from decyl alcohol, and the outlet temperature of the reactor is slightly higher than the temperature at the time of normal operation, due to undesirable side reactions. And it produces by-products. It is therefore necessary to stabilize the temperature inside the reactor. - In the reactor described in Patent Document 1, the supply amount of the quenching fluid is adjusted according to the temperature of the inlet side of the catalyst layer on the downstream side, and the internal temperature of the reactor is controlled. However, it is difficult to control the characteristics of the control system. The temperature of the inlet side 15 is constant, and the temperature change of the raw material is added, so that the temperature change on the inlet side cannot be avoided. In such a case, when the raw material is supplied as a quenching fluid as in Patent Document 1, since the amount of the raw material is large, the equilibrium is biased toward the reaction product side. As a result, the reaction rate 20 is sensitively changed with respect to the temperature change on the inlet side of the catalyst layer, so the temperature on the inlet side of the catalyst layer has a large influence on the temperature of the outlet side of the reactor, and as a result, the reactor The temperature of the outlet is large and the conversion rate is also large. Therefore, if the outlet temperature of the reactor becomes too high, by-products may be generated due to poor side reactions, the purity of the product may be lowered, and the outlet temperature of the reactor may become too low, which may result in failure to achieve the purpose of 5 200936236. Yield. Therefore, there is a technology that can control the temperature in the reactor in a simple manner in a reactor of a simple structure that can be enlarged. Patent Document 1: JP-A-2004-298768 (paragraphs 0014, 0020, 0021) 5 [Completely] The present invention has been made in view of the above circumstances, and an object thereof is to provide a reactor for supplying a raw material to a heat insulating type. When the object is produced by the equilibrium reaction accompanying the heat generation in the reactor, the temperature control in the reactor can be increased, and the occurrence of by-products and temperature drop due to temperature rise can be suppressed. A technique that results in a reduced yield. The temperature control method inside the reactor of the present invention divides the reaction zone into a plurality of plural, and the divided plural reaction zones are distributed to one or more heat insulation type reactors, and the raw materials are supplied to the heat insulation type reactor. Further, a temperature control method which is carried out when the target product is produced by an equilibrium reaction with heat generation is characterized in that the method comprises the steps of: supplying a raw material to the reaction zone of the first stage to obtain a reaction product containing the target product; a mixture of the reaction product taken out from the reaction zone on the front side and the unreacted raw material is supplied to the reaction zone in the order of the subsequent stage to obtain a reaction product containing the target 20; and between the respective reaction zones At least one portion, the quenching fluid is supplied to the mixture, and the mixture is cooled by mixing, and the quenching fluid is contained in the reaction product obtained in the reaction region on the rear side of the supply region of the quenching fluid. a part, and the same as the foregoing object obtained in addition to the above-mentioned heat insulation type reactor, 200936236 Little one. * The quenching fluid may also contain a part of the reaction product obtained by cooling the reaction product obtained in the reaction zone of the last stage. Preferably, the plurality of reaction regions are each composed of a catalyst layer. 5 The above reaction zone divided by three is preferred. Preferably, the cooling step is performed by adjusting at least one of a supply amount, a composition, and a temperature of the quenching fluid. In the above-mentioned equilibrium reaction with heat generation, methanol may be used as a raw material to obtain a reaction of a reaction product of water and a dimethyl ether of a target. In this case, the quenching fluid is preferably any one of a mixed fluid comprising dimethyl ether and dioxane and water. - The reaction apparatus of the present invention is a reaction apparatus for supplying a raw material into a heat-insulating reactor, and producing an object by an equilibrium reaction with heat generation, which is characterized by comprising: one or two or more heat-insulating reactions , dividing the reaction zone 15 into a plurality and distributing the divided plurality of reaction zones; the raw material supply mechanism supplies the raw materials to the reaction zone of the first stage; the quenching zone 'system® is between the respective reaction zones At least one of the portions for supplying the quenching fluid to the mixture of the reaction product and the unreacted raw material taken out from the reaction zone on the front side, and cooling the mixture by mixing; and '20 quenching The deactivating fluid supply means includes at least one of the reaction product obtained from the reaction region on the rear side of the quenching zone and at least one of the same compounds as the above-mentioned target obtained outside the heat insulating reactor The fluid is supplied to the quenching zone as a quenching fluid. The foregoing reaction apparatus includes a cooling mechanism for cooling a reaction product obtained by the reaction zone obtained in the last stage of the reaction zone, and the quenching flow system includes a portion of the reaction product cooled by the cooling mechanism as a part of the reaction product. good. Preferably, the plurality of reaction regions are each composed of a catalyst layer. 5 The above reaction zone divided by three is preferred. Further, it is preferable that the reaction apparatus of the present invention includes at least one of adjusting a supply amount, a composition, and a temperature of the quenching fluid, and supplying the quenching fluid to the quenching zone. In the above-mentioned equilibrium reaction with heat generation, methanol may be used as a raw material to obtain a reaction product of a reaction product composed of water and a dimethyl ether of a target. In this case, the quenching fluid is preferably any one of a mixed fluid comprising dimethyl ether and dimethyl ether and water. _ The method for producing dimethyl ether according to the present invention is that the reaction zone is divided into a plurality of plural, and the divided plural reaction zones are distributed to one or two heat-insulating 15-type reactors to supply decyl alcohol to the heat-insulating reaction. A method for producing dimethyl ether by a dehydration condensation reaction, comprising the steps of: supplying methanol to a reaction zone of the first stage to obtain a reaction product comprising hydrazine and water; and then a mixture of a reaction product taken out from the reaction zone on the front side and a mixture of unreacted methanol, and a reaction zone in which the ruthenium order is 20 on the rear side to obtain a reaction product composed of dimethyl ether and water; At least one of the foregoing reaction zones, the ILIL body is supplied to the mixture, and the mixture is cooled by mixing, and the 'the quenching fluid is included in the reaction of the rear side of the supply region of the quenching fluid. At least one of dimethyl ether and water obtained in the region, and any of the dimethyl ether obtained in addition to the above-mentioned heat-insulating reaction 8 200936236. The cooling step is preferably performed by adjusting at least one of the supply amount, composition, and temperature of the quenching fluid. The aforementioned quenching total fluid is obtained in the reaction zone of the last stage, and it is preferred to include any of & 5 followed by dimethyl ether and water. Preferably, the plurality of reaction regions are each composed of a catalyst layer. The aforementioned reaction zone divided by three is preferred. It is preferred that the quenching fluid is a part of dimethyl ether which is mixed with φ water present in the by-product of dimethyl ether and unreacted methanol. According to the invention, the reaction zone is divided into a plurality of complexes, and the complex reaction zone is distributed to one or more heat-insulating reactors, and the raw materials are supplied to the heat-insulating reactor, and When the target product is produced by the equilibrium reaction of the heat, the raw material is supplied to the reaction zone of the first stage, and the mixture of the reaction product containing the target product and the unreacted raw material is obtained, and the mixture is supplied from the reaction zone of the first stage. To the reaction zone in the order of the latter stage, a reaction product containing the target product is obtained, and at least one portion of the reaction product between the respective reaction regions is to be part of the reaction product obtained on the latter side of the reaction region and in the foregoing At least one of the same compounds as the above-mentioned object obtained other than the heat-insulating reactor is supplied as a quenching fluid, and the 20 mixture is cooled. Therefore, the amount of the reaction product in the mixture increases, and the flattening is biased toward the side of the substrate. The reaction proceeds stably, so that the change in the reaction rate due to the temperature change on the inlet side of the reaction zone is small. As a result, the controllability of the temperature in the reactor can be improved, and the occurrence of unintended by-products due to temperature rise can be suppressed, and the decrease in the yield due to the temperature drop can be easily suppressed. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a schematic structural view showing an example of a reaction apparatus for carrying out the production method of the present invention. 5 Fig. 2 is a schematic view showing an example of temperature change of the raw material in the reactor of the above reaction apparatus. Fig. 3 is a longitudinal sectional view showing another example of the above reaction apparatus. Fig. 4 is a longitudinal sectional view showing another example of the above reaction apparatus. Fig. 5 is a longitudinal sectional view showing another example of the above reaction apparatus. Fig. 6 is a longitudinal sectional view showing another example of the above reaction apparatus. Fig. 7 is a longitudinal sectional view showing another example of the above reaction apparatus. Fig. 8 is a longitudinal sectional view showing another example of the above reaction apparatus. Fig. 9 is a longitudinal sectional view showing another example of the above reaction apparatus. Fig. 10 is a longitudinal sectional view showing another example of the above reaction apparatus. 15 Fig. 11 is a longitudinal sectional view showing another example of the above reaction apparatus. Fig. 12 is a schematic view showing an apparatus used in a comparative example of an embodiment of the present invention. Fig. 13 is a schematic view showing an apparatus used in a comparative example of an embodiment of the present invention. 20 Fig. 14 is a schematic view showing a conventional apparatus used for a synthesis reaction. Fig. 15 is a schematic view showing a conventional apparatus used for the synthesis reaction. [Embodiment 3] BEST MODE FOR CARRYING OUT THE INVENTION A reaction apparatus of the present invention and an embodiment of the temperature control method using the same will be described with reference to Figs. 1 and 2 . Fig. 1 shows an outline of the entire manufacturing plant including the reaction device 2 for manufacturing the object. The reaction apparatus 2 has a vertical reactor 20 of, for example, a floor-mounted heat insulating type reactor. The top of the reactor 20 is connected to one end side of the raw material gas supply pipe 20 & and the other end side of the raw material gas supply pipe 20a is connected by the hot parent 2a and the evaporator 2b. A raw material storage source 4 in which a liquid raw material is stored. The evaporator 2b is used to vaporize a liquid raw material to obtain a raw material gas. The bottom of the φ reactor 20 is connected to one end 10 of the generated gas outflow pipe 20b, and the generated gas outflow pipe 20b is connected to the heat exchanger 2a. In the heat exchanger 2a, a raw material constituting the raw material gas supply pipe 2a is formed, and a mixture of the reaction product and the raw material in the generated gas outflow pipe 20b is heated, and the mixture is cooled and exchanged for heat exchange. . The other end side of the generated gas outflow pipe 20b is connected to a side wall of a first steaming tower 3 which will be described later. 15 In the inside of the reactor 20, a reaction zone necessary for obtaining a desired reaction yield is formed, for example, on the upstream side and the downstream side, and the φ reaction zone on the upstream side is formed as the first by the first catalyst layer 22a. The reaction zone and the reaction zone on the downstream side are formed as the second reaction zone by the second catalyst layer 22b. These catalyst layers 22 (22a, 22b) are supported by a plurality of support members 23 which are not shown in the drawings and which are formed with gas supply holes. A region between the first catalyst layer 22a and the second catalyst layer 22b in the reactor 20 is provided with a quenching zone Q for cooling the mixture in the reactor 20 by quenching fluid. A quenching fluid supply pipe 24 for supplying a portion of the reaction product as a quenching fluid to the quenching zone is connected to the reactor 20 side 11 200936236 of the quenching zone Q, and the quenching fluid supply pipe 24 is reacted A portion 24A close to the first catalyst layer 22a on the upper side of the quenching region Q in the device 20 is connected to a shower portion 24a in which a plurality of discharge holes 24b are formed to uniformly disperse and supply the quenching fluid. Further, a temperature detecting portion 29' is formed on the side surface of the reactor 20 so that the one end side thereof protrudes into the reactor 20, and for example, the mixture cooled in the quenching zone Q is detected in the vicinity of the upper side of the second dielectric layer 22b. temperature. The configuration control unit 3 is connected to the temperature detecting unit 29, and the control unit 3 controls the flow rate of the quenching fluid based on the detected temperature of the temperature detecting unit 29, and the flow rate adjusting valve 27 to be described later is used to adjust the temperature of the material gas. In the temperature range of the reaction. In the subsequent stage of the reactor 20, a reaction product for taking out the mixture obtained from the reactor 20 as a purpose, and supplying a part thereof as a quenching fluid to the reactor 20 is provided in the first stage. There is an apparatus comprising two distillation columns 30, 40 for obtaining, for example, dimethyl ether as a target. The first distillation column 30 is a mixture of an unreacted raw material and a reaction product 15 and separates and purifies the object. The object extraction tube 31 of the cooling mechanism is connected to the top of the column, and one end side of the discharge pipe 32 is connected. Lower end. The object to be discharged from the object take-out pipe 31 is taken out as a product and taken out of the system, but a part thereof is taken out from the object take-out pipe 31 by the quenching fluid supply pipe 24 which has been described before, so that the quenching fluid is returned. To the quenching zone Q of 20 has been explained. A flow rate adjustment valve 27 is interposed in the quenching fluid supply pipe 24. The other end side of the discharge pipe 32, which has been described, is connected to the side wall of the second distillation column 4''. The second distillation column 4 is used to separate and purify the unreacted raw material from the mixture of the target product in the first distillation column 30. One end side of the raw material discharge pipe 41 is connected to the top of the column, and the discharge pipe 42 is connected to Lower end. Construction 200936236 The other end of the raw material discharge pipe 41 is connected to the raw material gas supply pipe 20a on the upstream side of the distiller 2b, and the unreacted raw material is returned for reuse. The discharge pipe 42 is for discarding by-products, impurities, and the like remaining after the object and the unreacted raw material have been removed from the mixture, and the objects are discharged to the outside of the system. Next, a method of operating the above reaction device 2 will be described with reference to Figs. 1 and 2 . The liquid raw material composed of one substance or a plurality of substances is vaporized in the evaporator 2b disposed in the former stage, and the unreacted raw material and the reaction product taken out from the reactor 20 1 in the heat exchanger 2a The resulting mixture is heated to a temperature T1 by heat exchange. Thereafter, the material gas is supplied to the reactor 20 through the material gas supply pipe 20a, and flows in the reactor 20 from the top to the bottom. In the first catalyst 'layer 22a, a reaction product containing the target product is produced according to the equilibrium reaction of the following formula (1), and a gas containing a mixture of the reaction product and the unreacted source gas is formed. φ Raw material gas 〇 reaction product (target + by-product) + reaction heat... (1) The heat of reaction generated by this, the temperature of the gas of the mixture rises and reaches 20 degrees T2. In the production of dimethyl ether, the methylation of the liquid material is carried out, and dimethyl ether and water are produced by the equilibrium reaction of the formula (2) described below in the first catalyst layer 22a. 2CH3OH ^ CH3〇CH3 + Η2〇+ ΔΗ (2) ΔΗ = - 23.4kj//mol 13 200936236 Next, in the quenching zone Q, once the quenching fluid is supplied from the spraying portion 24a, the quenching fluid is The gas mixture of the high temperature (T2) mixture is mixed by the exothermic reaction of the catalyst layer 22a in the preceding stage, and the temperature of the mixture reaches T3. This quenching fluid is supplied to a stream of a part of the reaction product obtained in the reaction apparatus 2, and is supplied in a liquid or gas state. In the production of dimethyl ether, the quenching fluid is, for example, a dimethyl ether of a gas. As described above, a part of the reaction product is supplied as a quenching fluid, and the amount of the reaction product on the right side of the above formulas (1) and (2) is increased in the second catalyst layer 22b. Since the equilibrium reaction of the sub-groups (1) and (2) is biased toward the side of the raw material 10 to suppress the reaction of the target substance, the above-mentioned anti-centering can be stably performed. In this way, the cooled mixture gas is supplied to the second catalyst layer 22b in more detail, and the mixture containing the quenching fluid is stably generated by the same reaction in the second catalyst layer 22b. The mixture of the reaction product and the unreacted raw material rises to a temperature T4 by the heat of reaction generated by the reaction 15 of the second catalyst layer 22b. Thereafter, the mixture is taken out from the reactor 20 by generating the gas outflow pipe 20b, and heat exchange is performed between the heat exchanger 2a and the raw material. In the subsequent process, the dimethyl ether is produced as an example, and a mixture of the dimethyl ether of the reaction product discharged from the reactor 20 and the methanol 20 of the unreacted raw material is supplied to the first distillation column 30. The dimethyl ether of the target substance is isolated. The diterpene ether separated and purified from the mixture is taken out from the target take-out tube 31, and is radiated to the wall of the target take-out tube 31 and the like to a temperature lower than the temperature T2 described above. A part is quenched by the quenching fluid supply pipe 24 The fluid is returned to the reactor 20. The remaining dimethyl ether was taken out as a product to the system 200936236 - outside. The mixture in which the dimethyl bond has been removed is discharged from the lower side of the first vapor deuterate 30 and supplied to the second distillation column 40. The second distillation column 40 separates and purifies the methanol of the unreacted raw material. As has been explained, the unreacted raw material is returned to the raw material 5, and the gas supply pipe 20a is supplied again to the reactor 20 together with the raw material supplied from the raw material storage source 4. Further, the waste from which the target product and the by-product of the unreacted raw material have been removed is discharged to the outside of the system in this example. The temperature detecting unit 29 detects the temperature T3 of the inlet of the catalyst layer 22b, and controls the supply flow rate of the quenching fluid by the control unit 3 and the flow rate adjusting valve 27 because φ should be the temperature detection value, so that the catalyst layer can be reached. The inlet temperature T3 of 22b is stabilized, but it is unavoidable that the inlet temperature T3 changes due to a certain variation. However, since the present invention uses the reaction product as the quenching fluid, as described above, the equilibrium reaction is biased toward the sample side to suppress the reaction of the target, and the catalyst layer 22a for the outlet temperature T4 of the catalyst layer 22b. The influence of the 15 inlet temperature T1 becomes smaller. In other words, the change in the reaction rate with respect to the target product is small with respect to the change in the inlet temperature T1 of the catalyst layer 22a. Therefore, the change in the outlet temperature T4 of the catalyst layer 22b becomes dull, and the variation in the conversion rate becomes small. According to the above-described embodiment, the raw material is supplied to the heat insulating type counter 20, and the first reaction zone for the reaction of the raw material is produced when the object is produced by the equilibrium reaction with heat generation. 2 A quenching zone Q is provided between the reaction zones, and a part of the reaction product taken out from the second reaction zone is cooled and supplied as a quenching fluid to the quenching zone Q, and a mixture of the raw material and the reaction product is cooled. Therefore, as described in detail, the amount of the reaction product in the mixed compound of 200936236 is increased, the equilibrium is biased toward the raw material side, and the reaction proceeds stably, so that the temperature control in the reactor 20 is easily performed, and as a result, the temperature can be suppressed. It rises to produce an unintended by-product' and can suppress a decrease in yield due to a decrease in temperature. Moreover, the caulking of the catalyst can be suppressed, and the life of the catalyst can be long. Further, the rapid temperature rise (runaway reaction) of the reaction device 2 can be suppressed, and the reaction device 2 can be safely operated. Accordingly, in comparison with the known method, the present invention can simplify the construction of the reactor 20 to be easily enlarged, and the number of components constituting the reactor 20 is small. The quenching fluid may be a gas or a liquid. When the gas is quenched by the gas, since the latent heat of vaporization cannot be utilized, a larger amount of supply is required than when the liquid is used. However, since the amount of the reaction product in the reactor 20 is increased, the effect of suppressing the reaction rate is large. On the other hand, when a quenching fluid of a liquid is used, the supply amount smaller than that when the gas is used is the temperature of the mixture. Further, for example, when the supply amount of the raw material is small and the temperature rise of the mixture 15 due to the reaction is small, the reaction product may be cooled and supplied as a quenching fluid. In this case, since the amount of the reaction product in the reactor 20 is increased, the reaction rate can be suppressed. Further, in the above example, the catalyst layer 22 is provided in two layers. However, for example, as shown in FIGS. 3 and 4, the catalyst layer may be used. Figure 3 shows a reactor 20 comprising a three-layer catalyst layer (2a, 2b, 2c), and Figure 4 shows a reactor 20 comprising five catalyst layers (22a, 22b, 22c, 22d, 22e). . In the quenching zone q between the respective catalyst layers 22, the temperature detecting unit 29 detects the temperature of the mixture, and adjusts the flow rate of the quenching and the fluid supplied from the sprinkler 24a. . Such a reactor 20 is also reacted in the same manner as the above-described example by the state in which the fluid is inhibited by the reaction rate of 200936236. By setting the catalyst layers 22 to a plurality of layers in this manner, the same effects as those of the above-described examples can be obtained. Further, in the case where a plurality of layers of the catalyst layer 22 are provided in one reactor 20, for example, the reactor 20 provided with one catalyst layer 22 may be connected to a plurality of seats as shown in Figs. 5 and 6 . Figs. 5 and 6 show an example in which three reactors and five reactors 20 are connected, and a quenching fluid supply pipe 24 is connected to a generated gas outflow pipe 20b for connecting between the respective reactors 20. Further, in addition to the reactor 20, as shown in Figs. 7 and 8, a plurality of reactors 20 having at least one catalyst layer 22 may be combined and connected. Fig. 7 shows an example in which a reactor 20 provided with a catalyst layer 22 and a reactor 20 provided with a two-layer catalyst layer (22a, 22b) are connected in series. Fig. 8 shows an example in which a reactor 20 provided with three or two catalyst layers (22a, 22b) and a reactor 20 provided with three catalyst layers (22a, 22b, 22c) are connected in series. Similarly, between these catalyst layers 22, a quenching fluid is supplied to the quenching zone Q. In such a configuration, the same effects as those of the above example 15 can be obtained. In each of the above examples, it is preferable that all of the catalyst layers between the respective catalyst layers 22 and 22 are provided with the quenching region Q. However, for example, in the case where the temperature variation range is small, the quenching region Q can be reduced. The quantity, that is, as long as there is at least one quenching zone Q. Fig. 9 is a view showing an example in which the quenching zone Q between the second catalyst layer 22b and the third catalyst layer 22c from the upstream side is omitted in the reactor 20 20 shown in Fig. 4 which has been described. . The same effect can be obtained in such a reactor 2〇. Further, in the above example, the target substance in the system is used as the quenching fluid, but 疋' can also use the same compound as the object outside the system as the 17 200936236 quenching fluid. In such an example, the plurality of reaction devices 2 may be provided as shown in Fig. 1, and the quenching fluid may be supplied from the one reaction device 2 to the other reaction device 2. In such a case, the quenching fluid supply pipe 24 of the other reaction device 2 is connected to the object take-out pipe 31 of the reaction device 2. Further, in the above Figs. 3 to 5 and 10, the same configurations as those in Fig. 1 are assigned the same reference numerals. It is also possible to mix the unreacted raw material with the object of the quenching fluid. In addition, when the target product is used as a quenching fluid, for example, a reaction product (by-product) other than the target product may be produced from the raw material (the substance produced on the right side of the formula (1) in addition to the target product) In the case of 'Kelly 10', the reaction product is used as a quenching fluid. For example, in the reaction for obtaining dimethyl ether, water can be used as the quenching fluid. In this case, as shown in Fig. 1, the entire amount of the object is taken out from the object take-out pipe 31, and a part of the waste is returned to the quenching zone Q as a quenching fluid. In this case, as in the above example, the reaction product on the right side of the formulas (1) and (2) is increased to suppress the reaction, so that the reaction proceeds stably, and the temperature of the mixture at the outlet of the reactor 20 changes. Become smaller. In the eleventh embodiment, the same configurations as those in the first embodiment are denoted by the same reference numerals. Further, the target product may be used together with the by-product as a quenching fluid. For example, in the reaction for obtaining dimethyl ether from methanol, dimethyl ether and 20 water may be used as the quenching fluid. Further, diterpene ether from outside the system can also be used as a quenching fluid. Further, in each of the above examples, an off-system compound which is the same as the reaction product or the target product is used as the hydrazine fluid. However, as long as it can suppress the reaction rate, it contains the same system as the reaction product or the target product. 200936236 In the case of a compound, the quenching fluid may also contain unreacted starting materials. In this case, for example, in FIG. 1, one end side of the branch pipe (not shown in the figure) in which the valve is disposed is connected to the raw material discharge pipe 41, and the other end side of the branch pipe is connected. The quenching fluid supply pipe 24 positively uses the unreacted raw material as part of the quenching fluid by adjusting the opening degree of the valve. Further, in each of the above examples, the flow rate of the quenching fluid is controlled by the control unit 3 to stabilize the inlet temperature T3 of the reactor 20. However, the flow rate of the quenching fluid may be set to be constant by the control unit. 3, for example, adjusting the opening degree of the valve of the above-mentioned φ manifold and the flow regulating valve 27, and adjusting the ratio of the compound contained in the quenching fluid 10 or the compound outside the same system as the target, that is, 'to adjust the quenching The composition of the fluid is extinguished to stabilize the inlet temperature T3. Further, a quenching fluid supply pipe 24 may be provided with a cooling mechanism not shown in the drawing, and the flow rate of the quenching fluid may be constant, and the controller 3 adjusts the temperature of the quenching fluid to make the reactor. The inlet temperature T3 of 20 is stabilized. Further, 15 may be configured to stabilize the inlet temperature φ degree T3 of the reactor 2 by adjusting the flow rate of the quenching fluid, the composition of the quenching fluid, and the temperature of the quenching fluid by the control unit 3 The temperature control method and the reaction apparatus of the object are also applicable to the synthesis reaction of dimethyl ether formed by the dehydration of the fermented material of the following example, when the target product is produced by an equilibrium reaction with heat generation. , or the synthesis reaction of ammonia and hydrogen. Further, the other synthesis reaction may be applied to a reaction other than an equilibrium reaction such as an oxidation reaction or a hydrogenation reaction, or may be applied to such a reaction in a liquid phase. Example 19 200936236 An experiment conducted to confirm the effect of the method of the present invention will be described below. In this example, methanol was used as the above-mentioned raw material, and an experiment for obtaining a dimethyl ether as a target product by an equilibrium reaction with heat generation of the above formula (2) was carried out. 5 Further, although the following conditions set standard conditions, the standard condition is to set the conversion ratio of methanol at the outlet of the final catalyst layer and the temperature of the outlet of each catalyst layer to be equal under the respective standard conditions. The apparatus for carrying out the above reaction was carried out by using the reaction apparatus 2 shown in Fig. 1 described above, and a thermometer was provided at each of the inlets and outlets of the inlet of the reactor 20 and the catalyst layers 22a and 22b. In the reaction apparatus 2, decyl alcohol of a flow rate F1 is supplied, dimethyl ether is quenched, fluid is supplied to the quenching zone Q at a flow rate F2, and unreacted methanol is returned at a flow rate F3. The water of the by-product is discharged from the discharge pipe 42 which has been described. Further, each of the flow rates F1 to F3 indicates the mass flow rate of each fluid. 15 Experimental conditions The conversion rates and temperatures of methanol at the outlet of the reactor 20 were determined to be 75% and 340 °C, respectively, under the following conditions, and this condition was taken as a standard condition. Further, the temperature of the raw material at the inlet of the reactor 20 was changed from the above-mentioned standard conditions by 1 °C, and the conditions were the same as those under the standard conditions. The temperature of the outlet of the reactor 2 20 (the temperature at the outlet side of the second catalyst layer 22bt) and the conversion rate of methanol at the outlet of the reactor 20 were compared under various conditions. Further, the flow rate F2 of the dioxane of the quenching fluid and the flow rate F3 of the unreacted raw material returned from the raw material discharge pipe 41 are set to the same flow rate as the standard conditions. (standard conditions) 20 200936236
反應器20之入口溫度：279°C 反應器20之入口的壓力：l_55Mpa(量規壓） 對原料之流量之淬熄量的比(F2/(F1 + F3)) ·· 0.18 淬熄二曱醚條件：1.5Mpa(量規壓） 二甲醚飽和蒸氣（100%) (實驗結果） 表1表示實驗結果。 ❹ (表1) 與標準運轉條件之第1觸媒 層入口溫度變化(°c) 一 1 0 (標準運轉條件） + 1 轉化率(％) 73 75 77 第1觸媒層 入口溫度(°C) 278 279 280 出口溫度(°C) 334 338 342 第2觸媒層 入口溫度(°c) 296 299 303 出口溫度(°c) 336 340 342 與標準運轉條件之第2觸媒 層出口溫度變化(°C) -4 0 + 2 10 ο 其結果，對應反應器20之入口溫度（第1觸媒層22a之入 口側溫度）的變化，反應器20内的溫度也變化了。又，可得 知反應器20之出口之溫度的變化較反應器20之入口之溫度 的變化大。一旦反應器20内之溫度變高，則轉化率增加， 又，一旦反應器20内之溫度變低，則轉化率減少。 (比較例1 一 1) 接著將蒸餾塔30、40連接於在已說明之第15圖之多數 反應器102、102之間中介設置熱交換器103之裝置，並進行 實驗以作為比較例1 — 1。第12圖表示此裝置。又，對於與 已說明之第1圖相同構造的部位則賦與相同符號。於此裝置 也測定了上游侧之反應器（第1反應器）102及下游側之反應 21 15 200936236 器（第2反應器）ι〇2之個別的入口及出口之原料的溫度。 此裝置係建構成從供給路200將在蒸發器2b氣化後之 原料氣體供給至熱交換器103，於此熱交換器1〇3，此原料 氣體，與因上游側之反應器102的反應而呈高溫的原料及反 5應生成物所構成之混合物之間進行熱交換（冷卻混合物）。 又，建構成將在此熱交換器103已熱交換(被加熱)之後的原 料氣體，於上游側之反應器102之前侧回到原料氣體供給管 20a。又’關於供給至此熱交換器1〇3之流體以外的原料與 反應生成物等的流動，設為與已說明之第1圖的反應裝置2 10 同樣。 與上述實施例1同樣，決定以下的條件使下游侧之反應 器102之出口之甲醇的轉化率及原料的溫度分別為乃％、 340°C，並以此條件作為標準條件。又，同樣將上游側之反 應器102之入口的原料溫度從標準條件上下分別改變1£>(：， 15並對此等以外的條件，以與標準條件相同的條件進行了實 驗。 同樣測定下游側之反應器102之出口的溫度，又，比較 了轉化率。而且，從原料排出管41回來之甲醇的量設成與 標準條件相同流量。又，熱交換器103之淬熄流體與混合物 20之間之熱交換量（傳熱量）係設成即使改變上游侧之反應器 102之入口的溫度也不會變化者。 (標準條件）Inlet temperature of reactor 20: 279 ° C Pressure at inlet of reactor 20: ratio of l_55 MPa (gauge pressure) to quenching amount of raw material flow rate (F2/(F1 + F3)) ·· 0.18 quenching Ether conditions: 1.5 MPa (gauge pressure) Dimethyl ether saturated vapor (100%) (Experimental results) Table 1 shows the experimental results. ❹ (Table 1) The first catalyst layer inlet temperature change (°c) with standard operating conditions - 1 0 (standard operating conditions) + 1 conversion rate (%) 73 75 77 1st catalyst layer inlet temperature (°C ) 278 279 280 outlet temperature (°C) 334 338 342 2nd catalyst layer inlet temperature (°c) 296 299 303 outlet temperature (°c) 336 340 342 2nd catalyst layer outlet temperature change with standard operating conditions ( °C) -4 0 + 2 10 ο As a result, the temperature in the reactor 20 also changes in accordance with the change in the inlet temperature of the reactor 20 (the inlet side temperature of the first catalyst layer 22a). Further, it can be seen that the change in the temperature of the outlet of the reactor 20 is larger than the change in the temperature of the inlet of the reactor 20. When the temperature in the reactor 20 becomes higher, the conversion rate increases, and once the temperature in the reactor 20 becomes lower, the conversion rate decreases. (Comparative Example 1 - 1) Next, the distillation columns 30, 40 were connected to a device in which a heat exchanger 103 was interposed between a plurality of reactors 102, 102 of the above-described Fig. 15, and an experiment was conducted as Comparative Example 1 - 1. Figure 12 shows this device. Further, the same components as those of the first embodiment described above are assigned the same reference numerals. In this apparatus, the temperature of the raw material of the inlet and outlet of the reactor (the first reactor) 102 on the upstream side and the reaction of the downstream side 21 15 200936236 (the second reactor) ι 2 was also measured. This apparatus is constructed to supply the raw material gas vaporized by the evaporator 2b from the supply path 200 to the heat exchanger 103, where the heat exchanger 1〇3 reacts with the reactor 102 on the upstream side. Heat exchange (cooling of the mixture) is carried out between the high-temperature raw material and the mixture of the anti-5 product. Further, the raw material gas after the heat exchanger 103 has been heat-exchanged (heated) is constructed to return to the raw material gas supply pipe 20a on the upstream side of the reactor 102 on the upstream side. Further, the flow of the raw material other than the fluid supplied to the heat exchanger 1〇3, the reaction product, and the like is the same as that of the reaction device 2 10 of Fig. 1 described above. In the same manner as in the above-mentioned Example 1, the following conditions were determined such that the conversion ratio of methanol at the outlet of the reactor 102 on the downstream side and the temperature of the raw material were respectively 5% and 340 °C, and the conditions were used as standard conditions. Further, the raw material temperature at the inlet of the reactor 102 on the upstream side was changed from the standard conditions up and down by 1 £> (:, 15 and the conditions other than these were tested under the same conditions as the standard conditions. The temperature of the outlet of the reactor 102 on the downstream side, in turn, compares the conversion rate. Moreover, the amount of methanol returned from the raw material discharge pipe 41 is set to the same flow rate as the standard condition. Further, the quenching fluid and the mixture of the heat exchanger 103 The heat exchange amount (heat transfer amount) between 20 is set so as not to change even if the temperature of the inlet of the reactor 102 on the upstream side is changed. (Standard conditions)
反應器102之入口溫度：279°C 反應器102之入口的壓力：i_55Mpa(量規壓） 22 200936236 (實驗結果） 表2表示實驗結果。 (表2) 與標準運轉條件之第1觸媒 層入口溫度變化(°c) —1 0 ^ (標準運轉條件） + 1 WitWi%) — 71 75~ 78" 第1反應器 入口溫度(°C) 278 279~ 280 出口溫度(°c) 334 338" ^ &42 第2反應器 入口溫度（°c) 287 tel 〜 296 出口溫度(°c) 333 340 345 興知準運轉條件之第2反應 器出口溫廑變化(。〇 -7 0 ^ + 5 其結果與實施例1同樣，對應上游側之溫度變化，各部 的溫度及轉化率變化了，然而，其變化量較實施例1之變化 ❹ 5 量多。由此得知實施例〖的話，使用反應生成物之二甲醚作 為淬熄流體，藉此可抑制反應，而反應器20之内部的溫度 與轉化率的控制性提昇了。 (比較例1〜2) 10 >其-人，使用第1圖記載之裝置作為與已說明之專利文獻 U己載之裝置同樣構造的裝置並進行了實驗。此裝置概略上 具有與第1圖之反應器2G約同樣構造之反應器2G，惟，建構 &從原料4媳供給器細供給液體狀原料作為淬總流體。 又-*方〜itl·势1勹 15 圖中’對於第I圖相同構造的部位也賦與相同 符號。 出口側 上述實驗同樣，決定以下的條件使反應器300之 並以此的轉化率及原料的溫度分別為75%、34〇°C ’ 产 :作為標準條件’同樣將反應器300之入口側的溫 ^ ”H變rcji進行了實驗。X，此情形τ，從原料 23 200936236 排出管41回來之未反應的甲醇的流量及淬熄流體的流量為 一定。於此例子也表示F1為甲醇供給量，F2為淬熄甲醇之 供給董’ F3為再循ί展之甲酵流量。 (標準條件）Inlet temperature of reactor 102: 279 ° C Pressure at inlet of reactor 102: i_55 MPa (gauge pressure) 22 200936236 (Experimental results) Table 2 shows the experimental results. (Table 2) Temperature change of the first catalyst layer inlet (°c) with standard operating conditions — 1 0 ^ (standard operating conditions) + 1 WitWi%) — 71 75~ 78" 1st reactor inlet temperature (°C ) 278 279~ 280 outlet temperature (°c) 334 338" ^ &42 2nd reactor inlet temperature (°c) 287 tel ~ 296 outlet temperature (°c) 333 340 345 Xingzhi 2nd reaction of quasi-operating conditions Temperature change at the outlet of the vessel (. 〇-7 0 ^ + 5 The result is the same as in the first embodiment, and the temperature and conversion rate of each part are changed corresponding to the temperature change on the upstream side. However, the amount of change is different from that of the first embodiment. In the case of the Example, the dimethyl ether of the reaction product was used as the quenching fluid, whereby the reaction was suppressed, and the controllability of the internal temperature and the conversion rate of the reactor 20 was improved. Comparative Examples 1 to 2) 10 > The person described above was experimented with the apparatus described in Fig. 1 as a device having the same structure as the device described in the patent document U, which has been described. The reactor 2G is about the same reactor 2G, but the construction & The liquid material is supplied as a quenching total fluid in a fine manner. - * square to itl · potential 1 勹 15 In the figure, the same reference numerals are given to the same structures in the first drawing. The same conditions as above are determined on the outlet side. The conversion rate of the reactor 300 and the temperature of the raw material were respectively 75%, 34 ° C C 'Production: As a standard condition, the temperature of the inlet side of the reactor 300 was changed to rcji. In this case, τ, the flow rate of unreacted methanol and the flow rate of the quenching fluid returned from the raw material 23 200936236 discharge pipe 41 are constant. This example also shows that F1 is the supply amount of methanol, and F2 is the supply of quenching methanol. In order to follow the flow of the fermentation of the yeast (standard conditions)
5 反應器300之入口溫度：279°C 反應器300之入口的壓力：155Mpa(量規壓） 對原料之流量之淬熄量的比(F2/(F1+F3)) : 0.09 淬熄甲醇條件：1.6Mpa(量規壓）、沸點中的液體 (實驗結果） 1〇 表3表示實驗結果。 (表3) 與標準運轉條件之第1觸媒 層入口溫度變化(。〇 -1 0 (標準運轉條件） + 1 轉化率（％) 71 75 78 第1觸媒層 入口溫度(°C) 278 279 280 出口溫度(°C) 336 341 345 第2觸媒層 入口溫度(°C) 286 290 294 出口溫度(°C) 334 340 345 與標準運轉條件之第2觸媒 層出口溫度變化(。〇 -6 0 + 5 其結果，依據反應器300之入口溫度，反應器300内部 之各部的溫度及轉化率改變了，與比較例1一1同樣，其變 化量較實施例1大。 15 從以上的結果得知在使用原料作為淬熄流體時，平衡 反應偏向反應生成物，朝向目的生成物之反應速度變高 了，因此發熱量變多，其結果雖然反應器102之出口的混合 物温度不鈞勻情形變大，但是，由於將反應生成物之一部 分作為淬熄流體使用，因此可抑制向目的生成物的反應， 24 200936236 - 能將反應器102之出口的混合物溫度的上下幅度設得小。 - (實施例2) 其次，如已說明夂第3圖所示，將觸媒層22設為三層 時，進行確認反應器2〇之出口的溫度與轉化率如何變化的 5 實驗。 實驗上使用第3圖之反應器20，決定以下的各條件使反 應器20之出口之甲醇的轉化率及的溫度分別為75涔、340 V，並以此條件作為標準條件，又，將反應器20之入口之 Φ 原料的溫度上T分别改變rc ,並就此等以外的條件，以輿 10 標準條件相同的條件進行了實驗。在分别的條件下測定反 應器20之各觸媒層22之入α的溫度與出口的溫度，又’比 — 較在反應器20之出口之甲醇的轉化率。又，對於從淬熄流 體之二甲醚的流量F2及原料排出管41回到未反應之原科之 甲醇之流量F3的流量，設為與標準條件相同的流量。 15 (標準條件）5 Inlet temperature of reactor 300: 279 °C Pressure at inlet of reactor 300: 155 MPa (gauge pressure) Ratio of quenching amount of raw material flow rate (F2/(F1+F3)): 0.09 Quenching methanol condition : 1.6 Mpa (gauge pressure), liquid in boiling point (experimental result) 1 〇 Table 3 shows the experimental results. (Table 3) Change in inlet temperature of the first catalyst layer with standard operating conditions (.〇-1 0 (standard operating conditions) + 1 conversion (%) 71 75 78 1st catalyst layer inlet temperature (°C) 278 279 280 outlet temperature (°C) 336 341 345 2nd catalyst layer inlet temperature (°C) 286 290 294 outlet temperature (°C) 334 340 345 2nd catalyst layer outlet temperature change with standard operating conditions (.〇 -6 0 + 5 As a result, the temperature and the conversion ratio of the respective portions inside the reactor 300 were changed depending on the inlet temperature of the reactor 300, and the amount of change was larger than that of the first embodiment as in Comparative Example 1-1. 15 From the above As a result, when the raw material is used as the quenching fluid, the equilibrium reaction is biased toward the reaction product, and the reaction rate toward the intended product is increased. Therefore, the amount of heat generation is increased, and as a result, the temperature of the mixture at the outlet of the reactor 102 is not uniform. In the case where a part of the reaction product is used as the quenching fluid, the reaction to the intended product can be suppressed, 24 200936236 - The upper and lower ranges of the mixture temperature at the outlet of the reactor 102 can be set small. (Example 2) Next, as shown in Fig. 3, when the catalyst layer 22 is set to three layers, 5 experiments are performed to confirm how the temperature and conversion rate of the outlet of the reactor 2 are changed. Experiment 3 is used. In the reactor 20, the following conditions are determined such that the conversion rate and the temperature of the methanol at the outlet of the reactor 20 are 75 Torr and 340 V, respectively, and this condition is taken as a standard condition, and the inlet Φ of the reactor 20 is again obtained. The temperature T of the raw material was changed by rc, and experiments were carried out under the same conditions as the standard of 舆10 under the conditions other than these. The temperature and the outlet of α of each catalyst layer 22 of the reactor 20 were measured under respective conditions. The temperature, and the ratio - the conversion rate of methanol to the outlet of the reactor 20. In addition, the flow rate of the methanol from the quenching fluid dimethyl ether F2 and the raw material discharge pipe 41 back to the unreacted original methanol The flow rate of F3 is set to the same flow rate as the standard condition. 15 (Standard condition)
反應器20之入口溫度：279°C • 反應器20之入口的壓力：1.55Mpa(量規壓） 對原料之流量之淬熄量的比(F2/(F1 + F3)) ·· 〇·18 淬熄二甲醚條件：1.5Mpa(量規壓） 20 二曱醚飽和蒸氣(100%) (實驗結果） 表4表不實驗結果。 (表 4) _ 與標準運轉條件之第1觸媒 Γ-ι 0 十1 層入口溫度變化(°c) (標準運轉條件） ——— — 25 200936236 轉化 73 75 77 第1觸媒層 入口溫度(°c) 278 279 280 出口溫度(°c) 302 304 306 第2觸媒層 入口溫度(°c) 284 286 288 出口溫度(°c) 320 324 329 第3觸 入口溫度（C) 202 206 311 出口溫度(°c) 337 340 343 與標準運轉條件之第2觸媒 層出口溫度變化(°C) —3 0 + 3 其結果，可得知以使用生成物作為淬熄流體，而與實 驗例1的結果同樣，即使反應器20之入口側的溫度變化，也 可·抑制反應器20之出口側的溫度與轉化率的變化。 I圖式簡單説明】 5 第1圖表示用以實施本發明之製造方法之反應裝置之 一例的概略構造圖。 第2圖表示上述反應裝置之反應器内原料之溫度變化 之一例的概略圖。 第3圖表示上述反應裝置之其他例的縱剖面圖。 10 第4圖表示上述反應裝置之其他例的縱剖面圖。 第5圖表示上述反應裝置之其他例的縱剖面圖。 第6圖表示上述反應裝置之其他例的縱剖面圖。 第7圖表示上述反應裝置之其他例的縱剖面圖。 第8圖表示上述反應裝置之其他例的縱剖面圖。 15 第9圖表示上述反應裝置之其他例的縱剖面圖。 第W圖表示上述反應裝置之其他例的縱剖面圖。 第11圖表示上述反應裝置之其他例的縱剖面圖。 第12圖表示使用於本發明之實施例之比較例之裝置的 概略圖。 26 200936236 第13圖表示使用於本發明之實施例之比較例之裝置的 概略圖。 第14圖表示使用於合成反應之習知裝置的概略圖。 第15圖表示使用於合成反應之習知裝置的概略圖。 5 【主要元件符號說明】 2…反應裝置 27…流量調整閥 3…控制部 29…溫度檢測部 4…原料貯存源 30…第1蒸餾塔 A 2a…熱交換器 31···目的物取出管 2b…蒸發器 32…排出管 20…反應器 40…第2蒸餾塔 20a…原料氣體供給管 41…原料排出管 20b…生成氣體流出管 42…排出管 ' 22…觸媒層 100…多管式反應器 22a…第1觸媒層 101…管 22b…第2觸媒層 102…反應器 φ 23···支撐構件 103…熱交換器 24…淬熄流體供給管 200…原料淬熄供給路 24a…喷灑部 24b…吐出孔 Q…淬媳區 300···反應器 27 200936236 - 4.如申請專利範圍第1項之反應器内部之溫度控制方法，其 * 中經分割之前述反應區域為三個。 5. 如申請專利範圍第1項之反應器内部之溫度控制方法，其 中前述冷卻步驟調整前述淬熄流體之供給量、組成及溫 度之至少一者而進行。 6. 如申請專利範圍第1項之反應器内部之溫度控制方法，其 中前述伴隨發熱之平衡反應係以甲醇作為原料而獲得水 與目的物之二甲醚所構成之反應生成物的反應。 φ 7.如申請專利範圍第1項之反應器内部之溫度控制方法，其 中前述淬熄流體包含二甲醚與二甲醚及水之混合流體之 其中任一者。 8. —種反應裝置，係將原料供給至隔熱型反應器内且藉伴 隨發熱之平衡反應而製造目的物者，包含有： ’ 一個或二個以上的隔熱型反應器，係將反應區域分 割成複數，且分配有經分割之複數反應區域者； 原料供給機構，係將原料供給至第1段的反應區域 φ 者·， 淬熄區，係介於前述各反應區域之間之至少一處， 用以藉將淬熄流體供給至從前段侧之反應區域取出之前 述反應生成物與未反應之原料所構成之混合物，且進行 混合而冷卻該混合物者；及 淬熄流體供給機構，係將包含較前述淬熄區後段側 之反應區域所獲得之前述反應生成物的一部分、及在前 述隔熱型反應器以外所獲得之與前述目的物相同化合物 29 200936236 之至少一者之流體作為淬熄、流體供給至淬熄區者。 - 9. 如申請專利範圍第8項之反應裝置’其中更包含有用以將 . 在最後段之反應區域所獲得之反應生成物冷卻的冷卻機 構，且前述淬熄流體係包含以前述冷卻機構冷卻後之前 述反應生成物之一部分的流體。 10. 如申請專利範圍第8項之反應裝置，其中前述複數反應 區域分別由觸媒層所構成。 11. 如申請專利範圍第8項之反應裝置，其中經分割之前述 反應區域為三個。 12. 如申請專利範圍第8項之反應裝置，其中更包含有調整 前述淬熄流體之供給量、組成及溫度之至少一者，並將 前述淬熄流體供給至前述淬熄區域之控制部。 13. 如申請專利範圍第8項之反應裝置，其中前述伴隨發熱 之平衡反應係以甲醇作為原料而獲得水與目的物之二甲 醚所構成之反應生成物的反應。 14. 如申請專利範圍第8項之反應裝置，其中前述淬熄流體 包含二甲醚與二甲醚及水之混合流體之其中任一者。 ❹ 15. —種二曱醚之製造方法，係將反應區域分割成複數，經 分割之複數反應區域分配於一個或二個以上的隔熱型反 應器，將甲醇供給至隔熱型反應器内，且藉脫水縮合反 應而製造二甲醚之方法，包含有以下步驟： 一獲得反應生成物步驟，係將甲醇供給至第1段的反 應區域，獲得二曱醚與水所構成之反應生成物； 另一獲得反應生成物步驟，係接著將從前段側之反 30 200936236 應區域取出之反應生成物與未反應之甲醇所構成之混合 物，供給至順序為後段侧的反應區域，獲得二甲醚與水 所構成之反應生成物；及 冷卻步驟，係藉於前述各反應區域之間之至少一 處，將淬熄流體供給至前述混合物，且進行混合而冷卻 該混合物， 又，前述淬熄流體包含在較前述淬熄流體之供給區 域後段側之反應區域所獲得之二甲醚及水之至少一者、 及在前述隔熱型反應器以外所獲得之二甲醚之其中任一 者。 16.如申請專利範圍第15項之二甲醚之製造方法，其中前述 冷卻步驟係調整前述淬熄流體之供給量、組成及溫度之 至少一者而進行。 17·如申請專利範圍第15項之二甲醚之製造方法，其中前述 淬熄流體係在最後段之反應區域獲得，且包含冷卻後之 —曱謎及水之其中任—者。 18.如申请專利範圍第15項之二甲醚之製造方法，其中前述 複數反應區域分別由觸媒廣所構成。 19·如申4專利圍第15項之二甲驗之製造方法，其中經分 割之前述反應區域為三個。 2〇·如申請專她11第15項之二甲_之製造方法，其中前述 淬熄流體係除去現雜於二甲_之副生成物之水與未反應 之甲醇後之二甲鱗的1分。 31Inlet temperature of reactor 20: 279 ° C • Pressure at inlet of reactor 20: 1.55 MPa (gauge pressure) Ratio of quenching amount of flow rate of raw material (F2/(F1 + F3)) ·· 〇·18 Quenching dimethyl ether conditions: 1.5 Mpa (gauge pressure) 20 Dimethyl ether saturated vapor (100%) (Experimental results) Table 4 shows the experimental results. (Table 4) _ 1st catalyst with standard operating conditions ι-ι 0 1st layer inlet temperature change (°c) (standard operating conditions) ——— — 25 200936236 Conversion 73 75 77 1st catalyst layer inlet temperature (°c) 278 279 280 Outlet temperature (°c) 302 304 306 2nd catalyst layer inlet temperature (°c) 284 286 288 Outlet temperature (°c) 320 324 329 3rd inlet temperature (C) 202 206 311 The outlet temperature (°c) 337 340 343 and the second catalyst layer outlet temperature change under standard operating conditions (°C) — 3 0 + 3 As a result, it is known that the product is used as the quenching fluid, and the experimental example As a result of 1, the temperature and the change in the conversion rate on the outlet side of the reactor 20 can be suppressed even if the temperature on the inlet side of the reactor 20 changes. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a schematic structural view showing an example of a reaction apparatus for carrying out the production method of the present invention. Fig. 2 is a schematic view showing an example of temperature change of the raw material in the reactor of the above reaction apparatus. Fig. 3 is a longitudinal sectional view showing another example of the above reaction apparatus. Fig. 4 is a longitudinal sectional view showing another example of the above reaction apparatus. Fig. 5 is a longitudinal sectional view showing another example of the above reaction apparatus. Fig. 6 is a longitudinal sectional view showing another example of the above reaction apparatus. Fig. 7 is a longitudinal sectional view showing another example of the above reaction apparatus. Fig. 8 is a longitudinal sectional view showing another example of the above reaction apparatus. Fig. 9 is a longitudinal sectional view showing another example of the above reaction apparatus. Fig. W is a longitudinal sectional view showing another example of the above reaction apparatus. Fig. 11 is a longitudinal sectional view showing another example of the above reaction apparatus. Fig. 12 is a schematic view showing an apparatus used in a comparative example of an embodiment of the present invention. 26 200936236 Fig. 13 is a schematic view showing an apparatus used in a comparative example of an embodiment of the present invention. Fig. 14 is a schematic view showing a conventional apparatus used for the synthesis reaction. Fig. 15 is a schematic view showing a conventional apparatus used for the synthesis reaction. 5 [Description of main component symbols] 2: Reaction device 27: Flow rate adjustment valve 3: Control unit 29: Temperature detecting unit 4: Material storage source 30: First distillation column A 2a... Heat exchanger 31··· Object removal tube 2b...Evaporator 32...Exhaust pipe 20...Reactor 40...Second distillation column 20a...Material gas supply pipe 41...Material discharge pipe 20b...Generation gas outflow pipe 42...Discharge pipe '22...catalyst layer 100...multi-tube type Reactor 22a...first catalyst layer 101...tube 22b...second catalyst layer 102...reactor φ 23···support member 103...heat exchanger 24...quenching fluid supply pipe 200...material quenching supply path 24a ...spray portion 24b...discharge hole Q...hardening zone 300···reactor 27 200936236 - 4. The temperature control method inside the reactor of claim 1 of the patent scope, wherein the above-mentioned reaction region divided by Three. 5. The method of controlling the temperature inside a reactor according to the first aspect of the invention, wherein the cooling step is performed by adjusting at least one of a supply amount, a composition, and a temperature of the quenching fluid. 6. The method for controlling the temperature inside a reactor according to the first aspect of the invention, wherein the equilibrium reaction with heat generation is a reaction of a reaction product of water and a dimethyl ether of a target product using methanol as a raw material. φ 7. The temperature control method inside the reactor according to the first aspect of the invention, wherein the quenching fluid comprises any one of a mixture of dimethyl ether and dimethyl ether and water. 8. A reaction apparatus for supplying a raw material into a heat-insulating reactor and producing an object by an equilibrium reaction with heat generation, comprising: 'one or two heat-insulating reactors, which are reactions The region is divided into plural numbers, and the divided plural reaction regions are allocated; the raw material supply mechanism supplies the raw materials to the reaction region φ of the first stage, and the quenching region is at least between the respective reaction regions. a place for supplying a quenching fluid to a mixture of the reaction product and the unreacted raw material taken out from the reaction zone on the front side, and mixing to cool the mixture; and quenching the fluid supply mechanism, And a fluid comprising at least one of the reaction product obtained from the reaction region on the rear side of the quenching zone and at least one of the same compound 29 200936236 obtained from the heat-insulating reactor Quenching, fluid supply to the quenching zone. - 9. The reaction device of claim 8 wherein the reaction device further comprises a cooling mechanism for cooling the reaction product obtained in the reaction zone of the last stage, and the quenching flow system comprises cooling with the aforementioned cooling mechanism The fluid of a portion of the aforementioned reaction product. 10. The reaction apparatus of claim 8, wherein the plurality of reaction regions are each composed of a catalyst layer. 11. The reaction apparatus of claim 8, wherein the divided reaction zone is three. 12. The reaction apparatus of claim 8, further comprising adjusting at least one of a supply amount, a composition, and a temperature of the quenching fluid, and supplying the quenching fluid to a control portion of the quenching region. 13. The reaction apparatus of claim 8, wherein the equilibrium reaction with heat generation is a reaction of a reaction product of water and a dimethyl ether of a target product using methanol as a raw material. 14. The reaction apparatus of claim 8, wherein the quenching fluid comprises any one of a mixture of dimethyl ether and dimethyl ether and water. ❹ 15. A method for producing a diterpene ether by dividing a reaction zone into a plurality of divided reaction zones and distributing the plurality of reaction zones to one or more insulated reactors to supply methanol to the insulated reactor And a method for producing dimethyl ether by a dehydration condensation reaction, comprising the steps of: obtaining a reaction product step of supplying methanol to a reaction zone of the first stage to obtain a reaction product of dioxane and water; And another step of obtaining a reaction product, which is followed by supplying a mixture of the reaction product taken out from the reverse zone of the front side of the third zone, and the unreacted methanol, to the reaction zone in the order of the rear side to obtain dimethyl ether. a reaction product composed of water; and a cooling step of supplying a quenching fluid to the mixture by at least one of the foregoing reaction zones, and mixing to cool the mixture, and further, the quenching fluid At least one of dimethyl ether and water obtained in a reaction zone on the rear side of the supply region of the quenching fluid, and the heat insulating reactor Any of the dimethyl ethers obtained outside. 16. The method for producing dimethyl ether according to claim 15, wherein the cooling step is performed by adjusting at least one of a supply amount, a composition, and a temperature of the quenching fluid. 17. The method of producing a dimethyl ether according to claim 15 wherein the quenching flow system is obtained in the reaction zone of the last stage and comprises a cooled one of the mystery and the water. 18. The method for producing dimethyl ether according to claim 15, wherein the plurality of reaction regions are each composed of a catalyst. 19. The manufacturing method of the dimethyl test according to Item 15 of the patent of claim 4, wherein the aforementioned reaction zone is divided into three. 2〇·If you apply for the manufacturing method of the 11th item of the 11th item, the quenching and extinguishing system removes the dimethyl scales which are mixed with the water of the by-product of the dimethyl group and the unreacted methanol. Minute. 31