445250 A7 B7 經濟部智慧財產局員工消費合作社印製 五、發明說明（1 ) [技術領域] 本發明涉及將在生 體、液體或者超臨界 件下進行水解，轉變 胺的固體殘餘物分解 本發明缠涉及從生 收異氰酸酯，製成固 物的方法。 [先前之技術] 異氰酸酯一般通過 的胺和碳醸氯反應， 焦油成份，製成粗異 得到精製的異氰酸酯 份是通過在碳醢氛化 聚等生成的，可Μ認 氟尿酸酯等複雜的縮 進一步回收其中所含 棄物處置，或者將蒸 如上所述，目前雖 蒸餾殘餘物可作為工 效利用進行研究。近 點出發，關於工業廢 現有的翮於異氰酸 告第79690/1993號公 產異氰酸酯時副產的固體殘餘物在氣 狀態的水或者酵和水的混合物存在條 成與固體殘餘物的組成化合物相應的 方法。 產異氰酸酯時副產的Μ豳殘餘物中回 體殘餘物，如上所述水解該固體殘餘 下面的方 蒸餾反應 氰酸酯， 。作為蒸 工序中的 為是尿素 聚物的混 的異氰酸 餾殘餘物 然在生產 業廢棄物 年來從降 棄物的有 酯蒸餾殘 報中記載 法生產* 生成物* 將該粗異 餾殘餘物 副反懕和 、縮二脲 合物。該 酯，將其 直接作為 異氰酸酿 處置*但 低環境負 效利用的 餘物的研 了下面的 將與異 分別除 氰酸醋 得到的 蒸餾工 、碳化 蒸餾殘 殘餘物 工業廢 時副產 是同時 荷和資 研究已 究可擧 技術方 氰酸酯相應 去副產物和 進行精餾， 這種焦油成 序中的熟緬 二亞胺、異 餘物通常是 作為工業駿 棄物處理。 的異氣酸酷 也對其的有 源再生的観 經加緊進行。 出在專利公 案：往甲苯 (請先閱讀背面之注意事項再填寫本頁) 本紙張尺度適用中國國家標準<CNS)A4規格（210 X 297公釐） A7 4452 5 0 __B7_ 五、發明說明（2 ) 二異氟酸醅蒸餾殘餘物中加入一元酵*生成氨基甲酸磨之 後，製成加入多元酵形成的混合物，往其中加人發泡劑等 ，製成聚胺賄發泡髏。該方法就將蒸餾殘餘物變成更有效 的有用物質。 另一方面·作為從異氰酸_生產工睡開始的方法*進行 了通過從現有的蒸餾殘餘物中進一步回收異氛酸酯*或者 分解蒸餾殘餘物*回收相懕的胺的方法來降低生產成本的 官試。 例如，在專利公開第1 4250 1 / 1975號公報、專利公開第 1 30525/ 1 979號公報和專利公開第201751 / 1 983號公報中· 記載了瘅過在晚性水溶液存在情況下水解異氰酸酯蒸餾殘 餘物，分離分解液鬅中的固體部分來得到相應的胺。更詳 细地說*専利公開第1 42501 / 1 975號公報記載了將異鎮酸 酯蒸鎇殘餘物在水、醇和胺類的至少一種和鐮或者β(土金 靨的氫氧化物、氧化物和胺的至少一種存在情況下以100 〜200TC的飽和溶液形式加熱30分鐘〜5個小時，分離析出 的固體•得到相應的胺。但是，由於這些方法的任意一種 都要採用驗來促進水解，而且析出固髖的分離等工序複雜 ►因此不可避兔地增大成本，不能稱為是經濟性的方法。 最近，作為改良方法，專利公開第15 1 270/ 1 997號公報 記載了將熔融的或者疲鍰狀態的廢棄物用臨界點附近的水 採用所謂10分鐘的規有技術中不可預料的短時間分解對象 化合物*生成相應的原料化合物或者其衍生物進行回收。 該技術將熔融或者液體狀態的廢棄物不探用琨有的水解助 ‘紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） n I I I I I I I I I · I ϋ I I I n ϋ I n 1 n n ϋ n I (猜先《讀背面之注意事項再填寫本頁) 經濟部智慧財產局員工消費合作社印製 -5 - A7 4452 5 0 B7_ 五、發明說明（3 ) 催化劑，只採用水進行分解，而在水的臨界點附近的條件 下進行分解，由於時間短，建設費用不那麼高。 (請先閱讀背面之注意事項再填寫本頁) 但是*在該方法中*熔融或者疲體狀態的廢棄物例如由 於在其生產工序中含有能循環的異氰酸酯等有用的物質， 將其水解轉變成與異氰酸酯相應的胺，在異氰酸酯的生產 工序中*為了再利用，必須再次與碳醯氯反應，從這方面 來看是不經濟的。 如上所述，這些現有方法是不Μ圃體廢棄物，即固體殘 餘物為對象，结果是固體殘餘物殘留下來，最後不得不作 為產業廢棄物處置。 [發明之揭示] 本發明的目的是提供一種向至今僅進行廢棄處置的異氰 酸酯生產時副產的固體殘餘物中不加入鹼等水解肋催化劑 *轉變成可Κ再利用的相應的胺的方法。 本發明的現在的一個目的是提供從生產異氰酸酯時副產 的蒸餾殘餘物有效地分鑼異氰酸酯，不加鹼，有效地水解 所得到的固體殘餘物，轉變成可再利用的相應的胺的方法。 經濟部智慧財產局員工消費合作社印製 本發明者們為解決上述課題進行了努力研究，結果是發 現生產異氰酸_時副產的固體殘餘物通過在氣體、液體或 者超臨界狀態的水或者酵和水的混合物存在情況下加熱| 轉變成與固體殘餘物的組成化合物相懕的胺*並且為此所 必須的合逋條件，從而完成本發明。 即•本發明涉及下面（1)〜（12)中記載的固體殘餘物分 解方法。 6 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） 4452 ο Ο A7 B7 經濟部智慧財產局員工消費合作社印製 五、發明說明（4) (1) 固體殘餘物分解方法，其將生產異氟酸酯時副產的 固體殘餘物在氣體、液體或者超臨界狀態的水或者醇和水 的混合物存在情況下*在loot以上的溫度下、O.lfiPaK 上的壓力下加熱，轉變成與該固體殘餘物中的組成化合物 相應的胺。 (2) 上述（1)中記載的固體殘餘物分解方法，將前述固體 殘餘物在20托、180 t保持1個小時時•該固體殘餘物的重 量減少為3 Si Μ下。 (3>上逑（1)中記載的固體殘餘物分解方法，水相對於前 逑固體殘餘物的重量比為0.1以上。 (4) 上逑（1)或者（3)中記載的固體殘餘物分解方法，醇 相對於前述水的摩爾比為5以下。 (5) 上述（1)記載的画體殘餘物分解方法•前述壓力為 0.5〜40MPa、前逑溫度為150〜450Τ。 (6) 固體殘餘物分解方法，其從生產異氰酸酯時副產的 、含有揮發成份的蒸餾殘餘物中分離揮發成份，將得到的 固體殘餘物在氣體、液體或者超臨界狀態的水或者酵和水 的绲合物存在情況下，在100CK上的溫度下、O.IMPaM 上的壓力下加熱，轉變成與該固體殘餘物中的組成化合物 相應的胺化合物。 (7) 上逑（6)中記載的固體殘餘物分解方法*前述揮發成 份的分離是在具有活塞滑動性的兩相流型蒸發裝置中進行。 (8) 上述（7)中記載的固體殘餘物分解方法，前述兩相流 型蒸發裝置是雙重1型蒸發裝置。 本紙張尺度適用中國國家¥準（CNS)A4規格（210 X 297公釐) -Ί ~ ------------政 II------訂---------線1 (請先閲讀背面之注意事項再填寫本頁) 4452 5 0 A7 _B7_ 五、發明說明（5 ) (9) 上述（7)或者（8)中記載的固體殘餘物分解方法，前 述揮發成份的分離是在溫度為120〜35012，壓力為1〜200 毫米汞柱，在兩相流型蒸發裝置出口的氣體流速為100〜 700公尺/秒進行的。 (10) 上逑（6)中記載的固體殘餘物分解方法，水相對於 前述固體殘餘物的重量比為0.1以上。 U1)上述（6)或者（10)中記載的固體殘餘物分解方法， ί 產 副 時 酯 酸 氰 異 £T1 產 生 將 ο 下其M， 5>法 為方 比理 爾處 © 的 的物 水餘 述殘 前箱 於蒸 劈2) 相(1 酵 (請先閱讀背面之注意事項再填寫本頁) 相 ， 兩酯 的酸 性氰 動異 滑離 塞分 活中 有物 具餘 在殘 物餾 餘蒸 殘該 餾從 蒸， 的熱 酯加 酸中 氟置 異裝 有發 含蒸 、 型 的流 或 水 的 態 狀 臨 超 者 或 體 液’ 、 下 體況 氣情 在在 物存 餘物 殘合 體混 固的 的水 到和 得酵 將者 ο*成 、 組 度的 溫中 的物 上餘 Μ 殘 V 體 ο ί ο 固 丨該 與 成 變 轉 觸 接 下 力 壓 的 上 % 在 胺 的 應 相 物 合Ϊ:圖 化 明重 說雙 單過 ffv As 簡通 之是 式丨 圖 發 fm 揮 去 除 中 物 餘 殘 餾 蒸 從 器 換 交 熱 型 管 經濟部智慧財產局員工消費合作社印製 圖 意 示 的 0Η 的 份圈 成 圖 意 示 的 藝Η 的 物 餘 殘 體 固 解 水 是 態 形 最 的 施 霣 之 明 發 指一 是個 鍊-殘有 體種 固 一 的少 產至 副等 時醅 酯酸 酸氰 氰異 異二 產 、 生酷 謂酸 所氰 , 異 中 一 明的 發載 本記 在面 下 物 餘 殘 的 生 產 時 產 生 物合 的 基 為 式 通 如 例 出 舉 Μ 可 酯 酸 氰 異 團 基 族 肪 脂 是 8 本紙張尺度適用中國圉家標準（CNS)A4規格（210 X 297公釐） 445250 A7 _B7_ 五、發明說明（6 ) 或者芳香族基團）所表示的腊肪族一異氰酸酯、芳香族一 異氰酸酯等。 (請先閱讀背面之注意事項再填寫本頁) 脂肪族一異氰酸酿的具體例子可以舉出甲基異氰酸酷、 正丁基異氰酸酯等。而芳香族一異氰酸酷的具體例子可Μ 舉出笨基異氰酸酯等。 二異氰酸酯可Κ舉出通式OCH— R— HC0(R是上逑基團或 者脂環基）表示的脂肪族二異氰酸酯、芳香族二異氰酸酷 、脂環二異観酸酯等。 經濟部智慧財產局員工消費合作社印製 脂肪族二異氰酸酷的具體例子可以舉出六甲撐二異氰酸 酯等。芳香族二異氰酸酯可Μ舉出苯二甲基二異氰酸酯、 甲苯撐二異氰酸醅、萘撐二異氰酸酯、二苯甲基二異氰酸 酯等。脂環式二異氰酸酯可Μ擧出異氟爾嗣二異氟酸酯、 降冰片烷二異鼠酸酯等η除了上述異氰酸酯之外*還可以 採用例如三異氰酸酷等具有三個以上的一 NC0基團的異氰 酸酯化合物生產時副產的固體殘餘物。本發明分解所採用 的囿體殘餘物如果是在生產異氰酸酯時副產的固體殘餘物 ，則可Μ探用任何工藝所產生的。具體地說，是在胺生產 工藝、胺和碳醯氯的反應工序、異氰酸酯精製工序或者回 收異氰酸醅的工序等任意一種工藝中副產的固體殘餚#。這 些固體殘餘物在各個工藝中可以是熔融、溶解的。適用於 本發明的固體殘餘物不限於採用碳醯氛生產的異氟酸賄， 在用非碳_氛法生產的情況下*也可Μ分解這些各工序的 任意一個中副產的固體殘餘物。 固體殘餘物可Μ採用任何一種，但通常是在將各工序產 9 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） 445250 A7 B7 經濟部智慧財產局員工消費合作社印製 五、發明說明（7 ) 生的固體殘豫物通過固液分離工序、蒸餾工序等與液體成份 分離之後採用。優選經過異氰酸酯精製工序的固體殘餘物 。特別是在通過蒸餾精製異氰酸酯的情況下，其蒸餾殘餘 物（即異氰酸酯精製蒸餾工序）是優選的，從這些蒸餾殘餘 物中回收揮發成份直至實際上不含有揮發成份是特別儍遘 的。 所說的實際上不含有揮發成份的固體是指在20托、180 υ保持一個小時之後重量減少在3¾重量Μ内的固體。 這些在生產異氰酸酯時副產的固體殘餘物是主要成份為 胺、異氰酸酯等熱縮聚物構成的混合物。熱縮聚物有例如 尿素（尿烷}、縮二脲、碳化二亞胺、異氰尿酸酯等的基團 或者環。特別是包括許多具有多個造樣的基團或者環的複 雜结構的化合物。上述固體殘t勒和氣體、液體或者超臨界 狀態的水或者醇和水的溫合物在高溫、高壓下接觸，水解 成與固體殘鍊物的組成化合物相應的胺。 對該固體殘餘物的分解工序參照画1進行說明。將固體 殘餘物通過管線101加入到製漿轉鼓102中。水通過管線 103加入。水可Μ根據需要含有定量的酵。在102中製備的 漿料用熱交換器10 4升溫，加人反應器105中，分解物用 106抽出，根據需要精製*循環作為異氰酸酯原料等。 從管線107排出由固體殘飯构分解副產的氣體，主要是二 氧化碳。 所用的固體殘餘物根據前文所述，可Μ是任意一種生產 異氰酸酯時產生的固體殘餘物。其中，特別儍選採用通過 --f ---------^ —1------訂---------線 《請先閱讀背面之注意事項再填寫本頁) 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） 10 1 Λ _ A7 445250 B7 五、發明說明（8 ) 具有活塞滑動性的兩相流型蒸發裝置分離了揮發成份的固 體殘餘物。實際上不含揮發成份的固體殘餘物（即，從殘 存的異氰酸酯單體數是10¾的焦油狀蒸餾殘餘物中進一步 回收異氰酸酯單體至極限之後的上述副產物構成的熱縮聚 物等的混合物形成的殘餘物）是特別優選。 這些固體殘餘物通過在高溫高壓下與水接觸進行分解。 高溫高壓具體地說是指溫度在100 °C以上，壓力在0.1 MPa Μ上。埴時，水根據溫度、壓力可具有氣體、液體、超臨 界的任意一棰狀態。水可Κ是單獨的水，或者是含有酵等 的水。 將固體殘餘物在高溫高壓下與水接觸進行分解時*為了 增加其接觸的界面，固體殘t坳優選是微粉狀，在是塊狀的 情況下，優選預先粉碎成適當的大小。 為了分解固體殘餘物，儍選的溫度和壓力條件是在150 它以上，0.5MPa以上。特別是溫度和壓力沒有上限，優選 45¾ Μ 下 * 40MPaK 下。 固體殘餘物的分解時間沒有特別的限定，達到給定的溫 度後，在1分鐘〜300分鐘，優選1分鐘〜30分鐘的範圍内 進行。 水和固體殘餘物的混合加熱可以採用下面的任何一種方 法，優選3)。 1) 水和固體殘餘物在預先給定的溫度下混合。 2) 將水與固體殘餘物混合 時，加熱到給定的溫度*通 過將加熱的水和固體殘餘物涓合，達到分解溫度。 -11- (請先閲讀背面之法意事項再填寫本頁) . I,------訂---------線丨 經濟部智慧財產局員工消費合作社印製 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） A7 445250 _B7_ 五、發明說明（9 ) 3)將水和固體殘餘物預先在製漿滾筒等中以給定的濃度 混合，製成漿料，然後加熱到分解溫度。 相對於固體殘餘物的水的重量比（水/固體殘镓物）優選 1/10M上，更優選1/2M上。在水相對於固體殘餘物的重 量比不到1/10的情況下，分解生成物不僅大部分變成了瀝 青狀殘留物，相應的胺的收獲率也有降低的趨向*因此是 不太好的。 在本發明中，醇相對於水的摩爾比（酵/水）優選在5以下 ，更優選在3M下。如果醇相對於水的摩爾比超過了 5，胺 的收獲率容易降低，由於大有生成從氨基甲酸酷體和其它 醇而來的副產物的趨勢，所K是不太好的。在本發明中， 通過在反應體系内共存有酵，分解後的生成物可作為均一 的水溶液來回收。通過將分解後的生成物製成均一的水溶 液*從分解物可Μ簡便地回收胺。 在本發明中使用的酵沒有特別的限制，具體地可以舉出 例如甲醇、乙醇、異丙醇、正丁醇、叔丁酵、1-辛酵等一 元酵，乙二醇、丙二醇、二乙醇等二元酵、三甲酵丙烷、 1,2,6-己三醇等三元酵和季戊四醇等四元醇。這些醇可以 單獨或者兩種以上混合•知水混合使用。 在這些酵中，Μ和水的溶解性高的甲酵、乙醇、異丙酵 、乙二醇、丙二醇為代表的醇更為優選。在本發明中，通 過將這些酵輿水同時使用，可Μ使固體殘餘物分解之後的 回收物中的瀝青狀殘留物溶化。 這盛固體殘餘物和水或者醇和水的混合溶液可各自分別 ‘紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） (請先閱讀背面之注意事項再填寫本頁) * II------訂 *-------- 經濟部智慧財產局員工消費合作社印製 -12 - A7 445250 _B7_ 五、發明說明（10) 或者製成漿料加入到反應器中。 在分解上述固體殘餘物得到的水溶液中，除了水或者醇 和水之外，不用說堪含有作為主要成份的與異氰酸酯相應 的胺，將相應的胺探用普通的蒸豳或抽出等方法可K容易 地回收。回收的胺在根據需要進一步精製之後，可在異氟 酸酯生產工序中作為原料循環*與碳醸氯反應。 在分離胺的水溶液中溶解以二氧化碳為主要成份的低沸 點成份•將其通過通行汽提等除去之後，或者不除去*根 據霜要補加醇之後*作為水解用的水而循環使用。或者， 在通常的顆水處理之後排水。 在本發明中，生產異氰酸酯時的蒸餾殘餘物可以是在異 氰酸酯的生產設備中的任意一個工序中通過蒸餾產生的蒸 餾殘餘物。通常，通過主要是胺生產工序或者胺和羰基源 ，例如碳醯氯反應的工序得到的反應疲蒸餾生成的。 該蒸餾殘餘物的副產量根據製備方法而不同，一般來說 ，相對於從精製蒸豳塔的塔頂部分抽出的異氰酸酯約為 10¾重量。該蒸餾殘餘物通常是液體，含有數10¾，例如50 〜10¾重量的揮發成份。 在本發明中，從上述蒸餾殘餘物中回收直至實際上不含 揮發成份的狀態的裝置可Μ舉出薄膜蒸發器、混合攢拌機 或具有加熱部件的裝置等常用的揮發回收工序中所用的裝 置。其中，特別優選的是採用具有活塞溜滑性的兩相流型 蒸發裝置。 具有活塞潤滑性的蒸發裝置是指被蒸發體從裝置的上流 ^張尺度中國國家標準（CNS)A4規格（210 X 297公釐） ~ 1 3 - ------------^.,1------訂---------線 (請先閱讀背面之注意事項再填寫本頁) 經濟部智慧財產局員Η消費合作社印製 4452 5 Ο A7 B7 五、發明說明（η) (請先閱讀背面之注意事項再填寫本頁> 向下流的一定方向流動的設備。兩相流型蒸發裝置是至少 具有氣液、氣固的任意一種的兩相流的蒸發裝置，也可Μ 氣液固三相共存。 其代表例可Κ舉出桌€攪拌機或雙重管型熱交換器等。其 中特別優遘可形成波狀流、渣狀流、環狀流、噴露流的至 少一種流動狀態的管型蒸發裝置。最優選上述流動狀態是 由在蒸發裝置内部產生的氣體而形成的裝置*例如雙重管 型熱交換器等是適合採用的。 參見圖2，對適用於本發明的具有活塞滑動性的蒸發裝 置以雙重管型熱交換器為例進行說明。 經濟部智慧財產局員工消費合作社印製 從蒸餾塔出來的蒸餾殘餘物通過泵201加入到雙重管型 熱交換裝置202中。蒸餾殘餘物可Μ預先採用其它熱交換 器（未圖示）進行預熱。在雙重管型熟交換器的入口，根據 需要可設置壓力控制閥門203。加入到雙重管型熱交換器 中的蒸餾殘餘物採用蒸汽（STH)等加熱。在雙重管型熱交 換器内部的流動狀態根據加入到雙重管型熱交換器中的蒸 餾殘餘物的溫度、揮發成份、壓力等而不同，具有下面的 流動狀態。 1) 在揮發成份多、蒸餾殘餘物的溫度低的情況下 在雙重管型熱交換器入口附近蒸餾殘餘物被預熱、全部 變成疲態。通過該預熱流被蒸汽等熱介質加熱，揮發成份 經蒸發、經氣泡流，形成波狀流、渣狀流、環狀流、噴霧 流。 2) 在揮發成份少|通過預熱等蒸餾殘餘物的溫度高的情 14 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） 4452 5 0 A7 _B7 五、發明說明（12) 況下 通常，從雙重管型熱交換器的給料口存在氣相，形成氣 泡流、波狀流、渣狀流》後後通過將其用蒸汽等熱介質加 熱，揮發成份經過蒸發、經氣泡流*形成波吠流、渣狀流 、環狀流、噴霧流。特別是在進行預熱的情況下，在預熱 交換器中抑制氣泡的發生是優選的，因此優選在雙重管型 熱交換器人口設置閥門。 在具有活塞潤滑性的兩相流型蒸發裝置中，這些流動狀 態通過蒸發揮發成份，體積膨脹，其是通過加速蒸發裝置 内部的流體移動而產生。由此•即使揮發成份蒸發*粘度 上升，保持其氣相的蓮動能量不會閉塞熱交換器，可Μ達 到揮發成份的分離《特別是·如果在兩相流型蒸發裝置内 部形成噴霧流，得到的固體殘餘物在兩相流型蒸發裝置的 出口已經形成了微粉狀，因此是優選的。得到的固體殘餘 物根據爾要可以進行粉碎。 (請先閲讀背面之注意事項再填寫本頁) 經濟部智慧財產局員工消費合作杜印製 發持不即可物以速 蒸保， 。 ，聚可的 被以溫失關低，聚 即可低損有制份縮 立，的的度抑成熱 量升質料港，發制 熱上 介材和 度揮抑 加度熱原度速發而 所溫持制溫聚蒸進 ， 的保抑其縮次 ， 中部 >M與其依度 置内 述可度制來濃 裝置 所遷速抑量低 發裝上-聚，熱的 蒸發如本舖溫的物 的蒸。成熱低人聚 性了 溫的的 的加縮 滑制低量等質外熱 潤抑的能酯介另等 塞，源位酸熱過酯 活掉熱單氰持通酸 有耗需 了異保。瘰 具消所低於過成異 在熱發降由 通生持 。 潛蒸僅 ，Μ 的保度 本紙張尺度適用中國國家標準（CNS)A4規格（210x 297公釐） ~ 15 _ 445250 A7 _B7_ 五、發明說明（I3) (請先閱讀背面之注意事項再填寫本頁) 通過依次蒸發揮發成份可以進行沸騰傳熱，長時間保持 其狀態。進而，通過前述的體積膨脹，蒸發設備內部的流 體的線速度急剌升高*促進傳熱界面上的表面更新。表面 更新的促進、沸騰傳熱的利用進一步提高了傳熱效率，可 K抑制副產難Μ分解画收的熱縮聚物，根摟情況實際上也 可以不使其發生。對上述蒸發設備中的溫度、壓力等沒有 特別的限定，溫度通常為120〜350 *更優選180〜23〇υ 。壓力陲著揮發成份的沸點而變化，對於減壓優遘1〜20 0 毫米汞柱，更優選絕對壓力為5〜15毫米汞柱。具有活塞 潤滑性的兩相流型蒸發裝置的氣體線速度通常是100〜700 n/s，優選200〜600m/s。即氣體的線速度在兩相流型蒸發 裝置中逐漸變化 > 因此用在兩相流型蒸發裝置的出口的氣 體線速度來規定。 具有活塞滑動性的兩相流型蒸發裝置的熱介質可Μ是蒸 汽、電熱裝置、熱油等的任意一種*優選蒸汽。 經濟部智慧財產局員工消費合作社印製 在上逑雙重管型熱交換器202中*將分難了揮發成份的 蒸餾殘餘物加入漏斗204中*分離成氣相和固體殘餘物， 氣相從管媒205抽出*固體殘餘物經固體排出裝置206輸送 到分解工序207(例如圖1的製漿轉鼓102)，進行上述水解 反應•轉變成胺。在貉斗204中根據需要可Κ設置袋濾器 等粉末捕集器（圖中未示出）。將通過管線20 5抽出的氣相 根據需要冷凝精製，回收作為異氰酸酯成份或者異氰酸酯 生產用原料。對固體排出裝置沒有特別的限定，可Μ採用 常用的螺旋式粉末加料機、氣流式粉末輸送裝置等〇 -16 - 表紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） 445250 經濟部智慧財產局員工消費合作社印製 A7 B7 五、發明說明（l4) 通過以下的實施例對本發明進行更進一步的說明，下面 的實_例不是對本發明的任何限制。 實施例1 將含有約50¾的甲苯二異氰酸酯的蒸餾殘餘物*採用雙 重管型蒸發裝置，管内的蒸發殘餘物的溫度為2001 *絕 對壓力為1 0毫米汞柱的條件下分離揮發成份之後，得到含 有0.5¾的甲苯二異氰酸酯的固體殘餘物。這時，在雙重管 型蒸發裝置出口·氣體線速度為4 0 0公尺/秒。將4 . 0克該 固體殘餘物填充到反應器中，加入25 . 4克真空脫氣後的水 ，在380T：加熱，在該溫度下分解固體殘餘物。這時，壓 力為27 MPa。10分鐘後，快速冷卻到室溫，在取出內容物 時*回收液體24.6克。在反應管的内壁上附著黒色的粘性 瀝青狀殘存物。往該瀝青狀殘存物中加人甲醇，完全回收 瀝青狀殘存物。 其结果是從回收疲和加入甲醇的瀝青狀殘存物中可獲得 分別K相對於填充固體殘餘物的甲笨二胺以重量計分別為 16.7¾和5.8¾，二者加在一起共為22,5¾的收獲率，可確定 將固體殘餘物轉變成與其中的組成化合物相應的肢。 實陁例2 水相對於固體的重量比保持與實施例1相同的比例，在 380 °C、壓力為19MPa條件下加熱10分鐘，與實施例1同樣 回收分解的生成物。 其結果是從回收液和加入甲醇的瀝青狀殘存物中可獲得 分別K相對於填充固體殘餘物的甲苯二胺Μ重量計分別為 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） 17 (請先閱讀背面之注意事項再填寫本頁) 裘*·'--I!丨訂---------線 445250 A7 B7 五、發明說明（is) (請先閱讀背面之注意事項再填寫本頁) 15.6¾和5.7%，二者加在一起共為21, 4¾的收獲率，可確定 將固體殘餘物轉變成與其中的組成化合物相應的胺。 實施例3 水相對於固體的重量比保持與實陁例1相同的比例，在 3001C、壓力為23MPa條件下加熱10分鐘，與實施例1同樣 回收分解的生成物。 其結果是從回收液和加人甲醇的瀝青狀殘存物中可獲得 分別K相對於填充固體殘餘物的甲苯二胺以重量計分別為 29.6¾和6.8¾，二者加在一起共為36.4%的收獲率，可確定 將固體殘餘物轉變成 與其中的組成化合物相應的胺。 實施例4 水相對於固體的重量比為3倍*在30 、壓力為8,8HPa 絛件下加熱10分鐘，與實施例1同樣回收分解的生成物。 其結果是從回收液和加入甲醇的瀝青吠殘存物中可獲得 分別Μ相對於填充固體殘餘物的甲笨二胺以重量計分別為 39.6¾和5.6¾，二者加在一起共為45.2¾的收獲率，可確定 將固體殘鍊彻轉變成與其中的組成化合物相應的胺。 經濟部智慧財產局員工消費合作社印製 實施例5 水相對於固體的重量比保持與實施例4相同的比例*在 2 20 1、壓力為2. 4MPa條件下加熱60分鐘*與實施例1同樣 回收分解的生成物。 其結果是從回收液和加入甲酵的瀝青狀殘存物中可獲得 分別以相對於填充固體殘餘物的甲苯二胺Μ重量計分別為 30.3%和5.2¾，二者加在一起共為35.5¾的收獲率，可確定 18 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） 4452 5 0 A7 _B7_ 五、發明說明（16) 將固體殘餘物轉變成與其中的組成化合物相應的胺。 賁施例6 將4.0克從甲苯二異氰酸酯蒸餾殘舞构中進一步回收異氰 酸酯後的固體殘鎵彻加人到反應器中，加入33.0克水和甲醇 的混合液*使水與具空脫氣後固體的重量比為3倍。這時 甲醇與水的摩爾比例為1倍。然後將反應管在300 °C加熱到 分解溫度。這時，壓力為1 5 Μ P a。1 0分鐘後，快速冷卻到 室溫，取出内容物時，回收液體36.5克。在反應管内除水 之外沒有發現什麼。 分析回收液的結果是得到的收獲率為以甲苯二胺相對於 填充固體殘餘物的重量計為35.8%*確認轉變成與固體殘 餘物相懕的胺。 比較例1 水相對於固體的重量比為3倍，在9 0 t、0 . 2 Η P a的條件 下加熱60分鐘之外，進行與實施例1同樣的處理。其結果 是固體Μ保持填充時的形態殘存*不是瀝青吠殘留物。從 ------------1·,!------訂---------線 .-. , (請先閱讀背面之注意事項再填寫本頁) 經濟部智慧財產局員工消費合作社印製 異 變兩熱 的轉的的固 置地 性份的 處效滑成解 物有潤的水 棄 Μ 塞聚於 ο 廢可活縮適 胺業-有熱備 二 工劑具易製 苯的加用容步 甲有 添採等 一 出現等過酯進 檢為 鹼通酸 ， 有作入。氰 酯 沒將加胺異酸 中，不的制氟 體法物應抑異 液 方餘相，收 的的殘物置回 後明體餘裝地 之發固殘發效 。 離本的體蒸有物 分據 酯固型，餘 液根酸與流聚殘 固氟成相縮體 19 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） 五、發明說明（17) 101 管線 102 製漿轉鼓 103 管線 104 熱交換器 105 反應器 106 分解物 107 管線 201 泵 202 雙重管型熱交換裝置 203 壓力控制閥門 204 漏斗 205 管線 206 固體排出裝置 207 分解工序 (請先閱讀背面之注意事項再填寫本頁) 裝--------訂---------線 經濟部智慧財產局員工消費合作社印製 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） 20 修正頁445250 A7 B7 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs V. Description of the Invention (1) [Technical Field] The present invention relates to the decomposition of solid residues that are hydrolyzed under living, liquid or supercritical parts to transform amines. Entangling involves the process of collecting isocyanates from raw materials to produce solids. [Previous technology] Isocyanate generally reacts with amine and carbochlorine, and the tar component is made into crude oil to obtain refined isocyanate. The isocyanate is produced by carbonization and polymerization. Recycling the waste contained in it, or steaming as described above, although the distillation residue can be used as ergonomic research. Starting from a near point, regarding industrial waste, the existing solid residues produced as a by-product of isocyanate report No. 79690/1993 are produced in the gaseous state of water or a mixture of ferment and water, forming a compound with the solid residue. The corresponding method. The isocyanate is produced as a by-product of the M 豳 residue which is a by-product. The solid residue is hydrolyzed as described above. The mixed isocyanate residue that is a urea polymer in the steaming process is produced in the production industry from the ester distillation residue report of the waste in the past year. Reverse reaction and biuret compounds. This ester was directly treated as an isocyanic acid brewer *, but the residue of low environmental negative utilization was studied. The following distillers and carbonized distillation residues obtained from isocyanate removal of industrial acetic acid residues are by-products of industrial waste. It is researched in the same period of time, and the research can be done by the corresponding technology of cyanate esters to remove by-products and carry out distillation. The cooked burylene diimide and iso-residue in this tar sequence are usually treated as industrial waste. The isotonic acid is also stepping up its active regeneration. In the patent case: Toluene (please read the notes on the back before filling this page) The paper size is applicable to the Chinese national standard < CNS) A4 specification (210 X 297 mm) A7 4452 5 0 __B7_ V. Description of the invention ( 2) After adding mono-enzyme * to the carbamic acid distillate residue in the distillation residue of diisofluoric acid, a mixture of poly-enzyme is added, and a foaming agent is added to the mixture to make a polyamine briquette. This method turns the distillation residue into a more effective and useful substance. On the other hand, as a method to start from isocyanate production nights *, production was reduced by further recovering isocyanate esters from existing distillation residues * or decomposing distillation residues * by recovering amines of similar amines. The official test of cost. For example, in Patent Publication No. 1 4250 1/1975, Patent Publication No. 1 30525/1 979, and Patent Publication No. 201751/1 983, it is described that isocyanate distillation is hydrolyzed in the presence of a late aqueous solution. The residue was separated to decompose the solid portion of the liquid mash to give the corresponding amine. In more detail, * Kuriri Publication No. 1 42501/1 975 describes the steaming of isotonic acid ester residues in at least one of water, alcohols, and amines, and sickle or beta (hydrogen oxide of earth gold tincture, oxidation In the presence of at least one of amines and amines, it is heated in the form of a saturated solution of 100 to 200 TC for 30 minutes to 5 hours, and the precipitated solid is separated to obtain the corresponding amine. However, since any of these methods must be tested to promote hydrolysis Moreover, the processes such as the separation of the solid hips are complicated ► Therefore, it is inevitable to increase the cost of the rabbit and cannot be called an economical method. Recently, as an improvement method, Patent Publication No. 15 1 270/1 997 describes that the molten Alternatively, the water near the critical point of the exhausted waste uses the so-called 10-minute conventional technology to decompose the target compound in a short period of time * to generate the corresponding raw material compound or its derivative for recovery. This technology will melt or liquid state The use of certain hydrolyzing aids for the detection of wastes is not applicable. The paper size is applicable to China National Standard (CNS) A4 (210 X 297 mm) n IIIIII III · I III n ϋ I n 1 nn ϋ n I (Guess first, read the notes on the back, then fill out this page) Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs-5-A7 4452 5 0 B7_ V. Description of the invention (3) Catalyst , Only use water to decompose, and decompose under the conditions near the critical point of water, because the time is short, the construction cost is not so high. (Please read the precautions on the back before filling this page) But * In this method * Wastes in the melted or tired state, for example, contain useful substances such as recyclable isocyanate in the production process, which are hydrolyzed and converted into amines corresponding to isocyanate. In the production process of isocyanate *, it must be reused for reuse. The carbohydrate-chlorine reaction is uneconomical from this point of view. As mentioned above, these existing methods are not targeted at waste, that is, solid residues. As a result, solid residues remain, and they have to be discarded as an industry. [Disclosure of the invention] The object of the present invention is to provide a solid residue that is by-produced in the production of isocyanate that has been only discarded. A method for converting a hydrolytic rib catalyst * into a corresponding amine that can be reused without adding alkali. One of the present objects of the present invention is to provide an isocyanate that is efficiently separated from the distillation residue by-produced during the production of isocyanate, without adding alkali, Method for effectively hydrolyzing the obtained solid residue and converting it into the corresponding amine that can be reused. Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs. The solid residue produced as a by-product of cyanic acid is heated in the presence of gas, liquid or supercritical water or a mixture of yeast and water | converted to an amine * which is similar to the constituent compounds of the solid residue * and for this purpose The necessary combination of conditions to complete the present invention. That is, the present invention relates to a solid residue decomposition method described in (1) to (12) below. 6 This paper size is in accordance with Chinese National Standard (CNS) A4 (210 X 297 mm) 4452 ο ο A7 B7 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 5. Description of the invention (4) (1) Method for decomposing solid residues , Which heats by-product solid residues produced in the production of isofluorates in the presence of gas, liquid or supercritical water or alcohol and water mixtures * at temperatures above loot, under pressure on O.lfiPaK, Conversion to the amine corresponding to the constituent compound in the solid residue. (2) The method for decomposing a solid residue described in (1) above, when the solid residue is maintained at 20 torr and 180 t for 1 hour • The weight of the solid residue is reduced to 3 SiM. (3) The method for decomposing the solid residue described in (1) above, wherein the weight ratio of water to the solid residue of the former is 0.1 or more. (4) The solid residue described in (1) or (3) In the decomposition method, the molar ratio of the alcohol to the water is 5 or less. (5) The method for decomposing the painting residue described in (1) above. The pressure is 0.5 to 40 MPa, and the front temperature is 150 to 450 T. (6) Solid Residue decomposition method, which separates the volatile components from the distillation residue containing volatile components by-produced during the production of isocyanate, and the obtained solid residue is in gas, liquid or supercritical water or a mixture of fermentation and water When present, it is heated at a temperature of 100CK and a pressure of 0.1MPa to convert it into an amine compound corresponding to the constituent compound in the solid residue. (7) The solid residue described in (6) above Decomposition method * The aforementioned volatile components are separated in a two-phase flow type evaporation device having piston sliding properties. (8) The solid residue decomposition method described in (7) above, the two-phase flow type evaporation device is double 1 Type evaporation equipment . This paper size is applicable to Chinese national standard (CNS) A4 (210 X 297 mm) -Ί ~ ------------ 政 II ------ Order ----- ---- Line 1 (Please read the precautions on the back before filling this page) 4452 5 0 A7 _B7_ V. Description of the invention (5) (9) The method for decomposing the solid residue described in (7) or (8) above The separation of the aforementioned volatile components is performed at a temperature of 120 to 35012, a pressure of 1 to 200 mm Hg, and a gas flow rate of 100 to 700 meters per second at the outlet of the two-phase flow type evaporation device. (10) 上 逑(6) The method for decomposing a solid residue, wherein the weight ratio of water to the solid residue is 0.1 or more. U1) The method for decomposing a solid residue according to (6) or (10) above, Acid cyanide £ T1 will produce ο below its M, 5 > method of Fang Billier's material water and residual residue in the steam box 2) phase (1 leaven (please read the precautions on the back before filling This page) phase, the acidic cyanide of the two esters has a residual residue in the distillate, and there is a residue in the residue. The residue is distilled. Sending steam, water, or water in a state of being near super or body fluids, and under the condition of the body, the mood is in the water mixed with the residues of the residues, and the temperature of the fermented will be formed. The remaining M on the body of the residual V body ο ί ο solid 丨 the upper% of the pressure under the contact with the change of the combination of the amine phase: the picture clearly states that double over ffv As simply the formula is丨 Figure fm remove the residual residue distillation steam from the device to exchange the heat pipe tube of the Intellectual Property Bureau of the Ministry of Economic Affairs employee consumer cooperative printed a plot of 0Η shown in the picture circled into the art of the remaining waste Dehydration is the most important form of Shi Zhiming. One is a chain-residual species, which has a low yield to a secondary isochronous acid, cyanoisocyanate, isocyanate, isocyanate, etc. The paper published in the book states that the bases that are produced during the production of the remaining residues are as follows. For example, the esterable cyanoisocyanate group fat is 8. The paper size is applicable to the Chinese standard (CNS) ) A4 size (210 X 297 male A wax fatty aliphatic isocyanate) 445250 A7 _B7_ V. invention is described in (6) or an aromatic group) represented by an aromatic isocyanate. (Please read the notes on the back before filling this page.) Specific examples of aliphatic monoisocyanate include methyl isocyanate, n-butyl isocyanate, and so on. Specific examples of the aromatic monoisocyanate include a aryl isocyanate and the like. Examples of the diisocyanate include aliphatic diisocyanates, aromatic diisocyanates, and alicyclic diisocyanates represented by the general formula OCH-R-HC0 (R is a fluorene group or an alicyclic group). Specific examples of aliphatic diisocyanate produced by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs include hexamethylene diisocyanate. Examples of the aromatic diisocyanate include xylylene diisocyanate, toluene diisocyanate, naphthalene diisocyanate, and diphenylmethyl diisocyanate. Examples of the alicyclic diisocyanate include isoflurane diisofluorate, norbornane diisomurate, etc. In addition to the above isocyanates *, for example, triisocyanate and the like having three or more A NCO group of isocyanate compound is produced as a by-product solid residue. If the carcass residue used in the decomposition of the present invention is a solid residue by-produced in the production of isocyanate, it can be produced by any process. Specifically, it is a solid residue # produced as a by-product in any of the amine production process, the reaction process of amine and carbochlorine, the isocyanate purification process, or the process of recovering thallium isocyanate. These solid residues can be molten and dissolved in various processes. The solid residues suitable for use in the present invention are not limited to isofluoric acid briquettes produced by carbon atmospheres. In the case of non-carbon atmosphere production, * solid residues that are by-produced in any of these processes can also be decomposed. . Any of the solid residues can be used, but it is usually produced in each process. 9 paper sizes are applicable to China National Standard (CNS) A4 specifications (210 X 297 mm) 445250 A7 B7 printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 5. Description of the invention (7) The raw solid residue is separated from the liquid components through a solid-liquid separation process, a distillation process, and the like. A solid residue that has undergone an isocyanate purification step is preferred. Particularly in the case where the isocyanate is purified by distillation, the distillation residue (i.e., the isocyanate purification distillation step) is preferable, and it is particularly stupid to recover the volatile components from these distillation residues until the volatile components are not actually contained. The solid that does not actually contain volatile matter refers to a solid whose weight is reduced to 3¾ weight M after being held at 20 Torr for 180 hours. These solid residues, which are by-produced in the production of isocyanates, are mixtures composed mainly of thermal condensation polymers such as amines and isocyanates. Thermal polycondensates have groups or rings such as urea (urethane), biuret, carbodiimide, isocyanurate, etc. In particular, they include many complex structures with multiple shaped groups or rings. Compound. The solid residue mentioned above is contacted with gas, liquid or supercritical water or a warm compound of alcohol and water at high temperature and pressure to hydrolyze to an amine corresponding to the constituent compound of the solid residue. The decomposition process is described with reference to Figure 1. The solid residue is added to the pulp drum 102 through line 101. Water is added through line 103. Water may contain a certain amount of yeast as needed. The slurry prepared in 102 is heated with heat. The exchanger 104 is heated up and added to the reactor 105, and the decomposed product is extracted with 106, and is purified as needed as a raw material for isocyanate, etc. From the line 107, the by-product gas, mainly carbon dioxide, which is decomposed from the solid residue structure is discharged. Solid residues According to the foregoing description, M can be any solid residue produced during the production of isocyanates. Among them, particularly foolproof use of --f --------- ^ --1 ------ Order- ------- line "Please read the precautions on the back before filling this page) This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) 10 1 Λ _ A7 445 250 B7 V. Invention Explanation (8) The two-phase flow-type evaporation device with piston sliding property separated the solid residue of volatile components. A solid residue that is practically free of volatile components (that is, a mixture of thermal polycondensates and the like formed by further recovering isocyanate monomers to the limit from a tar-like distillation residue having a residual number of isocyanate monomers of 10¾ is formed. Residues) are particularly preferred. These solid residues are decomposed by contact with water at high temperature and pressure. High temperature and high pressure specifically means that the temperature is above 100 ° C and the pressure is above 0.1 MPa Μ. At the moment, water can have any state of gas, liquid, or supercritical according to temperature and pressure. The water may be water alone or water containing leaven or the like. When the solid residue is decomposed by contacting it with water at high temperature and pressure * In order to increase the contact interface, the solid residue t 坳 is preferably in a fine powder form, and in the case of a block, it is preferably pulverized in advance to an appropriate size. In order to decompose the solid residue, the temperature and pressure conditions selected are above 150 and above 0.5 MPa. In particular, there is no upper limit for temperature and pressure, preferably 45 ¾ M * 40 MPaK. The decomposition time of the solid residue is not particularly limited, and after reaching a given temperature, it is performed within a range of 1 minute to 300 minutes, preferably 1 minute to 30 minutes. The mixed heating of water and solid residues can be performed by any of the following methods, preferably 3). 1) Water and solid residues are mixed at a predetermined temperature. 2) When mixing water with solid residue, heat to a given temperature * The decomposition temperature is reached by trickling the heated water and solid residue. -11- (Please read the French and Italian matters on the back before filling in this page). I, ------ Order --------- Line 丨 Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs The scale applies to the Chinese National Standard (CNS) A4 specification (210 X 297 mm) A7 445250 _B7_ V. Description of the invention (9) 3) Water and solid residues are mixed in a pulping drum, etc. at a given concentration in advance to prepare Form a slurry and then heat to decomposition temperature. The weight ratio of water to the solid residue (water / solid gallium residue) is preferably 1 / 10M, more preferably 1 / 2M. In the case where the weight ratio of water to the solid residue is less than 1/10, not only most of the decomposition products become bitter residues, but the corresponding amine yield also tends to decrease * so it is not good. In the present invention, the molar ratio (alcohol / water) of alcohol to water is preferably 5 or less, and more preferably 3M. If the molar ratio of alcohol to water exceeds 5, the yield of amine is liable to decrease. Since there is a tendency to generate by-products from carbamate and other alcohols, K is not very good. In the present invention, by co-existing fermentation in the reaction system, the decomposed product can be recovered as a uniform aqueous solution. By making the decomposed product into a homogeneous aqueous solution *, the amine can be easily recovered from the decomposed product. The yeast used in the present invention is not particularly limited, and specific examples thereof include monovalent yeasts such as methanol, ethanol, isopropanol, n-butanol, tert-butyrate, and 1-octyl yeast, ethylene glycol, propylene glycol, and diethanol. Such as dibasic yeast, trimethanol propane, tribasic yeast such as 1,2,6-hexanetriol, and tetrahydric alcohol such as pentaerythritol. These alcohols can be used alone or in combination of two or more. Among these yeasts, formic acid, ethanol, isopropanol, ethylene glycol, and propylene glycol, which are highly soluble in M and water, are more preferred. In the present invention, by using these fermented water together, the pitch-like residue in the recovered material after the solid residue is decomposed can be dissolved. This mixed solid residue and water or alcohol and water mixed solution can be individually 'paper size applicable to Chinese National Standard (CNS) A4 specifications (210 X 297 mm) (Please read the precautions on the back before filling out this page) * II ------ Order * -------- Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs -12-A7 445250 _B7_ V. Description of the invention (10) Or make a slurry and add it to the reactor. In addition to water or alcohol and water, it is needless to say that it contains an amine corresponding to isocyanate as the main component in the aqueous solution obtained by decomposing the solid residue, and the corresponding amine can be easily extracted by ordinary steaming or extraction methods. Ground recycling. The recovered amine can be further refined as required, and then can be recycled as a raw material * in the isofluoroester production process to react with carbochlorine. Dissolve low-boiling components containing carbon dioxide as the main component in the aqueous amine separation solution. • After removing it by steam stripping, etc., or without removing * after adding alcohol in accordance with frost *, recycle it as water for hydrolysis. Alternatively, the water is drained after the usual particle water treatment. In the present invention, the distillation residue during the production of isocyanate may be a distillation residue generated by distillation in any step in the isocyanate production facility. Usually, it is produced by reaction distillation mainly obtained by the amine production process or the amine and carbonyl source process, such as the carbochlorine reaction process. The by-product of the distillation residue varies depending on the preparation method. Generally, it is about 10 ¾ weight based on the isocyanate extracted from the top portion of the refined distillation column. The distillation residue is usually a liquid and contains volatile ingredients of several 10¾, such as 50 to 10¾ by weight. In the present invention, the device for recovering from the above-mentioned distillation residue to a state where it is practically free of volatile components includes thin-film evaporators, mixers, mixers, and devices having heating means. Device. Among them, it is particularly preferable to use a two-phase flow type evaporation device having piston slippage. Evaporation device with piston lubricity refers to the upper body of the body to be evaporated from the device ^ Zhang size Chinese National Standard (CNS) A4 specification (210 X 297 mm) ~ 1 3------------- ^., 1 ------ Order --------- line (Please read the notes on the back before filling this page) Printed by the Intellectual Property Bureau of the Ministry of Economic Affairs and Consumer Cooperatives 4452 5 〇 A7 B7 5 、 Explanation of invention (η) (Please read the precautions on the back before filling in this page> The equipment that flows downward in a certain direction. The two-phase flow type evaporation device is a two-phase flow with at least one of gas-liquid and gas-solid The evaporation device can also coexist with three phases of gas, liquid and solid. Its representative examples include table mixers or double tube heat exchangers. Among them, it is particularly good to form wavy, slag, and annular flows. A tube-type evaporation device with at least one flow state of the dew flow. Most preferably, the above-mentioned flow state is formed by the gas generated inside the evaporation device. For example, a double tube type heat exchanger is suitable. See FIG. 2 A double-tube type heat exchanger for a piston sliding device suitable for the present invention The printing residue printed from the distillation column by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs is added to the double-tube type heat exchange device 202 through the pump 201. The distillation residue can be used in advance by other heat exchangers (not shown) (Shown) for preheating. At the inlet of the double tube type heat exchanger, a pressure control valve 203 can be set as required. The distillation residue added to the double tube type heat exchanger is heated by steam (STH), etc. In the double tube type The flow state inside the heat exchanger varies depending on the temperature, volatile components, and pressure of the distillation residue added to the double-tube type heat exchanger, and has the following flow conditions. 1) The temperature of the distillation residue is high when there are many volatile components. At low conditions, the distillation residue is preheated near the inlet of the double tube heat exchanger, and all become fatigued. The preheated stream is heated by a heat medium such as steam, and the volatile components are evaporated and bubbled to form a wave-like stream, a slag-like stream, an annular stream, and a spray stream. 2) In the case of low volatile components | high temperature of the distillation residue through preheating, etc. 14 This paper size applies the Chinese National Standard (CNS) A4 specification (210 X 297 mm) 4452 5 0 A7 _B7 V. Description of the invention (12 ) In general, there is a gas phase from the feed port of the double tube heat exchanger, which forms a bubble flow, wave flow, slag flow. After that, it is heated by a heat medium such as steam, and the volatile components are evaporated and passed through the bubbles. The flow * forms wave bark flow, slag flow, annular flow, spray flow. In particular, in the case of preheating, it is preferable to suppress the occurrence of bubbles in the preheating exchanger. Therefore, it is preferable to provide a valve in a double-tube type heat exchanger. In a two-phase flow-type evaporation device having piston lubricity, these flow states expand by volume by evaporating volatile components, which are generated by accelerating the movement of the fluid inside the evaporation device. As a result, even if the volatile component evaporates * the viscosity increases, the lotus energy that maintains its gas phase will not block the heat exchanger, and the separation of volatile components can be achieved. "Especially if a spray stream is formed inside a two-phase flow type evaporation device, The obtained solid residue is finely powdered at the outlet of the two-phase flow type evaporation device, and is therefore preferable. The obtained solid residue can be pulverized according to the requirements. (Please read the notes on the back before filling out this page.) Consumption cooperation by employees of the Intellectual Property Bureau of the Ministry of Economic Affairs. , Ju Ke's temperature is low, Ju can reduce the loss of the system shrinks, the degree of suppression into the heat to upgrade the material port, the heating medium and the degree of fluctuation and increase the degree of pyrogenicity The temperature is controlled by the temperature, the temperature is reduced, and the reduction of the temperature is reduced. The central part of the M &M; Warm things are steaming. Heat generation, low polymerization, warm shrinkage, low-quality isothermal heat-suppressing energy esters, and other plugs. Source-acid heat passes through the ester to activate the hot monocyanate. Guarantee.消 The elimination is lower than the excessive difference. Latent steaming only, dimensionality of M This paper size applies to Chinese National Standard (CNS) A4 (210x 297 mm) ~ 15 _ 445 250 A7 _B7_ V. Description of the invention (I3) (Please read the notes on the back before filling in this Page) Evaporation of volatile components in sequence allows for boiling heat transfer and maintains its state for a long time. Furthermore, through the aforementioned volume expansion, the linear velocity of the fluid inside the evaporation device sharply increases * to promote surface renewal at the heat transfer interface. The promotion of surface renewal and the use of boiling heat transfer have further improved the heat transfer efficiency. K can suppress by-product thermal condensation polymers that are difficult to decompose and collect. In fact, the root cause may not be caused. There is no particular limitation on the temperature, pressure, etc. in the above-mentioned evaporation equipment, and the temperature is usually 120 ~ 350 * more preferably 180 ~ 23〇υ. The pressure varies depending on the boiling point of the volatile component. For a reduced pressure, 1 to 20 mm Hg is more preferable, and the absolute pressure is more preferably 5 to 15 mm Hg. The gas linear velocity of a two-phase flow type evaporation device with piston lubricity is usually 100 to 700 n / s, preferably 200 to 600 m / s. That is, the linear velocity of the gas is gradually changed in the two-phase flow type evaporation device. Therefore, the linear velocity of the gas at the outlet of the two-phase flow type evaporation device is used for regulation. The heat medium of the two-phase flow type evaporation device having piston sliding property may be any one of steam, electric heating device, hot oil, etc. * preferably steam. Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs on the upper dual-tube heat exchanger 202 * Distillation residues that have separated the volatile components are added to the funnel 204 * Separated into gas phase and solid residue, and the gas phase is removed from the tube The medium 205 is extracted * The solid residue is sent to the decomposition step 207 (for example, the pulping drum 102 of FIG. 1) through the solid discharge device 206, and the above-mentioned hydrolysis reaction is performed to convert it into an amine. A powder trap (not shown) such as a bag filter may be provided in the bucket 204 as needed. The gas phase extracted through line 20 5 is condensed and purified as necessary, and recovered as an isocyanate component or a raw material for isocyanate production. There is no particular limitation on the solids discharge device. The commonly used screw powder feeder, air-flow type powder conveying device can be used. -16-The paper size is applicable to China National Standard (CNS) A4 (210 X 297 mm) 445250 Printed by the Consumer Property Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs A7 B7 V. Description of the Invention (14) The present invention is further explained by the following examples. The following examples are not intended to limit the present invention in any way. Example 1 A distillation residue containing about 50¾ of toluene diisocyanate * was subjected to a double tube type evaporation device, and the temperature of the evaporation residue in the tube was 2001. The volatile components were separated under the condition of an absolute pressure of 10 mmHg to obtain Solid residue containing 0.5¾ of toluene diisocyanate. At this time, the linear velocity of the gas at the outlet of the double-tube type evaporator was 400 m / s. 4.0 g of the solid residue was charged into the reactor, 25.4 g of vacuum degassed water was added, and heating was performed at 380T: at this temperature, the solid residue was decomposed. At this time, the pressure was 27 MPa. After 10 minutes, it was quickly cooled to room temperature and 24.6 grams of liquid was recovered * when the contents were removed. To the inner wall of the reaction tube, ochre-colored viscous asphalt-like residue was attached. Methanol was added to the pitch-like residue to completely recover the pitch-like residue. As a result, from the asphalt-like residues recovered from the methanol and methanol additions, K was 16.7¾ and 5.8¾, respectively, relative to the weight of methylbendiamine filled with solid residues, which together amounted to 22, With a yield of 5¾, it can be determined that the solid residue is converted into limbs corresponding to the constituent compounds therein. Practical Example 2 The weight ratio of water to solids was maintained at the same ratio as in Example 1, and it was heated at 380 ° C and a pressure of 19 MPa for 10 minutes. In the same manner as in Example 1, the decomposed product was recovered. As a result, K is obtained from the recovered liquid and the asphalt-like residue with methanol added. K is relative to the toluene diamine filled with the solid residue. The weight is based on the Chinese paper standard (CNS) A4 (210 X 297). Mm) 17 (Please read the precautions on the back before filling this page) Qiu * · '-I! 丨 Order --------- line 445250 A7 B7 V. Description of the invention (is) (Please first Read the notes on the back and fill in this page again) 15.6¾ and 5.7%, which together add up to a yield of 21, 4¾, which confirms that the solid residue is converted into the amine corresponding to the constituent compounds in it. Example 3 The weight ratio of water to solids was maintained at the same ratio as in Example 1, and heating was performed at 3001C and a pressure of 23 MPa for 10 minutes, and the decomposed product was recovered in the same manner as in Example 1. As a result, K was 29.6¾ and 6.8¾, respectively, relative to the weight of toluene diamine filled with solid residue from the recovered liquid and the asphalt-like residue with methanol added, and the total was 36.4%. The yield can be determined to convert the solid residue into an amine corresponding to the constituent compounds therein. Example 4 The weight ratio of water to solids was 3 times * Heating was performed for 10 minutes under a pressure of 30 and a pressure of 8,8 HPa, and the decomposed product was recovered in the same manner as in Example 1. As a result, from the recovered liquid and the methanol-added asphalt bark residue, the methylbenzenediamines relative to the filled solid residue were respectively 39.6¾ and 5.6¾ by weight, and the total of the two was 45.2¾. The yield can be determined to completely transform the solid residues into amines corresponding to the constituent compounds therein. Printed in Example 5 by the Consumers ’Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs. The weight ratio of water to solids is maintained at the same ratio as in Example 4 * Heating for 60 minutes under the conditions of 2 20 1 and a pressure of 2. 4 MPa * Same as in Example 1. The decomposed product is recovered. As a result, 30.3% and 5.2¾, respectively, of the toluene diamine M relative to the solid residue filling were obtained from the recovered liquid and the asphalt-like residue added with formazan, and the total of the two was 35.5¾. The harvest rate can be determined. 18 This paper size is applicable to the Chinese National Standard (CNS) A4 specification (210 X 297 mm) 4452 5 0 A7 _B7_ V. Description of the invention (16) The solid residue is converted to correspond to the constituent compounds in it Amine. Example 6 4.0 g of solid residual gallium after further recovering isocyanate from the toluene diisocyanate distillation residue was added to the reactor, and 33.0 g of a mixed solution of water and methanol was added. After degassing the water and the air The solids have a weight ratio of 3 times. At this time, the molar ratio of methanol to water is doubled. The reaction tube was then heated to a decomposition temperature at 300 ° C. At this time, the pressure was 15 M Pa. After 10 minutes, it was quickly cooled to room temperature. When the contents were taken out, 36.5 g of liquid was recovered. Nothing was found in the reaction tube other than water. As a result of the analysis of the recovered liquid, the obtained yield was 35.8% based on the weight of toluenediamine relative to the weight of the filled solid residue. It was confirmed that the conversion into an amine that was comparable to the solid residue was obtained. Comparative Example 1 The same ratio as in Example 1 was performed except that the weight ratio of water to the solid was three times, and heating was performed under conditions of 90 t and 0.2 Η Pa for 60 minutes. As a result, the solid M remained in the form at the time of filling *, and was not a residue of asphalt bark. From ------------ 1 ·,! ------ Order --------- line.-., (Please read the notes on the back before filling this page ) The Intellectual Property Bureau of the Ministry of Economic Affairs, the Consumer Cooperative Co., Ltd. prints the heat-retaining parts of the heat-retaining parts that have been transformed into two kinds. The addition of the second agent for easy production of benzene, Rongbu Jia, etc. appeared, waited for the ester to pass the inspection, and it was effective. The cyanate ester does not add the amine isoacid, the fluorine-reducing substance should suppress the remaining phase of the liquid phase, and the collected residue is returned to the body to restore the hair to the hair. The separated body is based on the ester solid type, and the residual liquid acid forms a condensed body with the residual polyfluoride. This paper size is applicable to the Chinese National Standard (CNS) A4 (210 X 297 mm). 5. Invention Explanation (17) 101 pipeline 102 pulp drum 103 pipeline 104 heat exchanger 105 reactor 106 decomposition product 107 pipeline 201 pump 202 double tube heat exchange device 203 pressure control valve 204 funnel 205 pipeline 206 solid discharge device 207 decomposition process ( Please read the precautions on the back before filling out this page) Packing -------- Order --------- Printed on paper standards of the Ministry of Economic Affairs Intellectual Property Bureau Staff Consumer Cooperatives This paper applies Chinese national standards ( CNS) A4 size (210 X 297 mm) 20 correction page