TW495500B - Continuous hydrolysis process for preparing 2-hydroxy-4- methylthiobutanoic acid or salts thereof - Google Patents

Abstract

A continuous process for the preparation of 2-hydroxy-4-methylthiobutanoic acid or a salt thereof which includes introducing an aqueous mineral acid into a nitrile hydrolysis reactor including a continuous stirred tank reactor and introducing 2-hydroxy-4-methylthiobutanenitrile into the nitrile hydrolysis reactor. 2-hydroxy-4-methylthiobutanenitrile is continually hydrolyzed within the nitrile hydrolysis reactor to produce a nitrile hydrolysis reactor product stream containing 2-hydroxy-4-methylthiobutanamide. The nitrile hydrolysis reactor product stream is continuously introduced into an amide hydrolysis flow reactor. 2-hydroxy-4-methylthiobutanamide is continually hydrolyzed within the amide hydrolysis flow reactor to produce an aqueous hydrolyzate product containing 2-hydroxy-4-methylthiobutanoic acid. 2-hydroxy-4-methylthiobutanoic acid is recovered from the aqueous hydrolyzate product.

Description

495500 A7 ----- B7 五、發明説明（i ) 有關申請案之表考 本申清案為美國專利申請案編號〇8/477,768 ( i 99 5，6 7 ^出申請）之部分接續申請案。 發明背景 本發明係有關製備2 -羥基-4 _甲硫丁酸或其鹽類，更特定 地有關製備包含2-羥基-4-甲硫丁酸之水性產物之改良方法 〇 2 ^基-4 -甲I 丁敌’通常稱為甲硫胺酸之幾基類似物且 亦％為2-羥基-4-甲硫丁酸或只…^八，為必須胺基酸甲硫胺酸 I類似物。曱硫胺酸類似物如1^1^]8入有效於供應甲硫胺酸供 營養用途，特別是作為家禽飼料補充。為有效地製造含 HMBA之飼料補充物，水解必須充分完全。 已藉各種方法製造HMBA，其包括2-羥基-4 -甲硫丁腈（亦 稱為Η Μ B N或2 -羥基-4 _甲硫丁腈，下文稱為，，HMBN，，或，，腈 π)足水解。HMBA已製備為外消旋d，L-混合物，藉由礦酸水 解ΗΜΒΝ，藉加鹼土氫氧化物或碳酸鹽沉澱酸殘留物，並藉 例如於Blake等人，美國專利第2,745,745號中所述之蒸發結晶 法，自水相中回收HMB A之鹽。 經濟部中央標準局員工消費合作社印製 (請先閲讀背面之注意事項再填寫本頁} 英國專利弟915，19j號$己述製備HMBA4弓鹽之方法，其中於 連績反混合之反應器用稀H2S〇“#液水解HMBN至HMB A， 藉醚抽提自反應液中分離Η Μ B A。由於使用連續之反混合之 反應系統，英國專利之方法不能達HMBN或醯胺中間物之完 全轉化成Η Μ B A。當要製造液體Η Μ B A產物時，顯著量之 未反應之物質之存在為不希望的。 本纸張尺度適用中國國家標準（CNS ) A4規格（210X 297公釐） 495500 A7 _ _ B7 五、發明説明（2 ) 近來’商業上已藉硫酸水解HMBN形成含HMBA之高品質 水解產物，自水解產物抽HMBA並藉Ruest等人，美國專利第 4,524,077號所述’自抽提物中回收^^6八製造11^^人。於此 方法中’將HMBN與具強度於約5 〇 %與約7 〇 %重量以（基於 無有機物之基礎）之間之硫酸於約2 5它與約6 5 之間之溫度 下混合。為控制反應速率，較好於約3 〇至約6 〇分之期間内 ’將Η Μ B N加至酸。於較佳之條件下，於約丨/ 2小時與約1 又1 / 2小時4間之期間内發生此腈之實質轉化成2 -經基_ 4 -甲 硫丁醯胺，且下文稱為"醯胺”）。其後，於約7 〇它與丨2 〇。〇 間之溫度下，藉另外之水解將醯胺轉化成HMBA。醯胺之最 後水解成酸於具最初強度於約3 〇 %與約5 0 %重量比（基於此 有機物之基礎）之間之H2S04中進行。為提供較佳之酸強度 ，在加熱反應混合物以前，藉加水稀釋水相。於相當稀之酸 強度及增加之溫度之條件下，於約1又1 / 2小時至3小時之期 間内，將醯胺轉化成酸。於進行水解中，每莫耳HMBN進料 使用約1莫耳硫酸，以0至1 0 %過量（較佳地〇至5 % )之酸，提 供令人滿意之結果。R u e s t等記述批次過程並陳遠批次過程 較好確保水解反應貫質上進行至完全。若使用連續反應系統 ，Ruest等記述應加以設計及操作，以確保實質上完全之轉 化。例如，連續操作可於插塞流動管式反應器或階式攪拌之 槽系統中實行。單一之反混合反應器由Ruest等所述，為只 於一般被認為不為商業製造所接受之駐留時間提供充分之轉 化。495500 A7 ----- B7 V. Description of the invention (i) Formal examination of the relevant application This application is part of the US Patent Application No. 08 / 477,768 (i 99 5, 6 7 ^ application). case. BACKGROUND OF THE INVENTION The present invention relates to the preparation of 2-hydroxy-4-methylthiobutanoic acid or a salt thereof, and more particularly to an improved method for preparing an aqueous product containing 2-hydroxy-4-methylthiobutanoic acid. -Methyl I-butadiene 'is usually called several amino analogs of methionine and is also 2-hydroxy-4-methylthiobutyric acid or only ... ^ 8, is an essential amino acid methionine I analog .曱 Thiamine analogs such as 1 ^ 1 ^] 8 are effective in supplying methionine for nutritional purposes, especially as a supplement to poultry feed. In order to effectively produce HMBA-containing feed supplements, hydrolysis must be sufficiently complete. HMBAs have been manufactured by various methods, which include 2-hydroxy-4-methylthiobutyronitrile (also known as ΗM BN or 2-hydroxy-4_methylthiobutyronitrile, hereinafter referred to as, HMBN, or ,, nitrile π) Foot hydrolysis. HMBA has been prepared as a racemic d, L-mixture, hydrolyzed ΗΜΝΒΝ by mineral acid, precipitated acid residue by addition of alkaline earth hydroxide or carbonate, and for example described in Blake et al., U.S. Patent No. 2,745,745 By evaporation crystallization, the salt of HMB A was recovered from the aqueous phase. Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs (please read the precautions on the back before filling out this page) British patent brother No. 915,19j $ has described a method for preparing HMBA4 bow salt, in which the reactor used for continuous mixing is diluted H2S〇 "# liquid hydrolyzes HMBN to HMB A, and Η Μ BA is separated from the reaction solution by ether extraction. Due to the use of a continuous reverse mixing reaction system, the method of the British patent cannot achieve the complete conversion of HMBN or amidine intermediates Μ Μ BA. When a liquid Η Μ BA product is to be produced, the presence of a significant amount of unreacted substances is undesirable. This paper size applies the Chinese National Standard (CNS) A4 specification (210X 297 mm) 495500 A7 _ _ B7 V. Description of the invention (2) Recently, 'HMBN has been commercially hydrolyzed by sulfuric acid to form a high-quality hydrolysate containing HMBA. The HMBA is extracted from the hydrolysate and borrowed from Ruest et al., US Patent No. 4,524,077. Recovered ^^ 6 VIII made 11 ^^ person. In this method 'HMBN and sulfuric acid with a strength between about 50% and about 70% by weight (based on the basis of no organic matter) in about 2 5 it Between about 6 and 5 Under mixing. To control the reaction rate, it is better to add Η Μ BN to the acid within a period of about 30 to about 60 minutes. Under better conditions, about ½ / 2 hours and about 1 / 1/2 The substantial conversion of this nitrile into 2-mercapto-4-methylthiobutamidamine occurred within a period of 4 hours and is hereinafter referred to as " fluorenamine "). Thereafter, it was at about 70 ° C and 20 ° C. At temperatures between 0 and 5%, amidine was converted to HMBA by additional hydrolysis. The final hydrolysis of amidine to acid is performed in H2S04 with an initial strength between about 30% and about 50% by weight (based on this organic matter). To provide better acid strength, the aqueous phase is diluted by adding water before heating the reaction mixture. Under the conditions of fairly dilute acid strength and increased temperature, amidine is converted to acid within a period of about 1 1/2 hours to 3 hours. In performing the hydrolysis, about 1 mole of sulfuric acid was used per mole of HMBN feed, with a 0 to 10% excess (preferably 0 to 5%) of acid, providing satisfactory results. R u e s t et al described the batch process and Chen Yuan batch process. It was better to ensure that the hydrolysis reaction proceeded qualitatively to completion. If a continuous reaction system is used, the description of Ruest et al. Should be designed and operated to ensure a substantially complete transformation. For example, continuous operation can be performed in a plug flow tube reactor or a cascade tank system. A single inverse mixing reactor, as described by Ruest et al., Provides a sufficient conversion only for dwell times that are generally considered unacceptable for commercial manufacturing.

Hernandez等，美國專利第4,912,257號記述其中HMBA藉由 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） (請先閲讀背面之注意事項再填寫本頁 ·裝· 經濟部中央標準局員工消費合作社印製 495500 A7 B7 五、發明説明（3 ) HMBN以單一步騾之硫酸水解所製造之方法。將Η Μ B N進料 至酸化容器中，於其中將其與98 %。H2S〇4以酸/腈莫耳比於 0.5與2之間混合，形成含2 0 - 5 0 %。重量比之H 2 S Ο 4之反應 混合物。當反應混合物分批製造時，將混合物於連續添加環 線中攪拌並冷卻至5 0 °C歷3 0 - 6 0分。反應混合物再進料至水 解反應器中並於6 0 °C與1 4 0 °C間之溫度加熱5分至6小時，同 時施加微真空至反應器。據說由Hernandez等所述之方法藉 由單一步騾將酸化之HMBN溶液水解製造HMBA，不像技藝 中已知之兩次步騾水解法。 經濟部中央標準局員工消費合作社印製 (請先閱讀背面之注意事項再填寫本頁) 為提供會最大量HMB A及最少量腈及醯胺組份之高品質水 解產物，必須得HMBN及2-羥基-4-甲硫丁醯胺高度轉化成 Η Μ B A。HMB A之分批製造提供高轉化。然而，習用之製造 HMB A之批次方法具數種缺點。批次方法之製造力由批次反 轉時間所限。另外地，由於當各批製造時反應條件可變化， 所以HMBA水解產物之品質在各批之間會有偏差。批次反應 器之充填及倒空及非穩定狀態情況造成蒸氣放射，其必須在 放出前處理。先前技藝方法所須之設備花費高。將H 2 S〇4與 水於酸稀釋桶中混合形成稀硫酸進料。須熱交換器以除去桶 中產生之稀釋熱。桶、熱交換器、泵、及再循環環線必須為 抗腐敍組成。 發明概要 於本發明之數種目的當中，為提供改良之HMB Α製備法； 提供可以連續方式操作之此種方法；提供可以高生產力操作 之此種方法；提供當與習用方法比較時，可有效地降低主要 本紙張尺度適用中國國家標準（CNS ) A4規格（210X 297公釐） 495500 A7 -*--- B7 五、發明説明（） (請先閱讀背面之注意事項再填寫本頁) 二、隹濩費用之此種方法；提供當與習用之批次水解系統比 ^時’改1〈控制反應條件之此種方法，·提供當與習用之批 、系、、克比較時，降低悉氣放射之此種方法；提供消除分開之 1酸稀釋< 須要之方法，尤其提供可使用濃H2S04進料流操 作而無先前稀釋之方法；提供實質上有效地完全轉化HMBN 成HMBA之方法；及提供可製造一致之品質之HMBA供用 於製備動物進料補充物之方法。 此等及其他目的經由製備HMBA或其鹽之方法得到，包括 將礦酸加入含連續之攪拌槽反應器之腈水解反應器中，及將 2-羥基-4-甲硫丁腈加入腈水解反應器中。在腈水解反應器 中’連續地水解2-羥基-4-甲硫丁腈，製造含2_羥基-4-甲硫 丁酿胺之腈水解反應器產物流。將腈水解反應器產物流連續 地引入醒胺水解流動反應器中。於醯胺水解流動反應器中連 、、’貝地水解2 -喪基-4 -甲硫丁酸胺產生含2 -經基-4 -甲硫丁酸之 το成之水性水解產物。自完成之水性水解產物中回收2 _幾基 -4 -甲硫丁酸。 經濟部中央標準局員工消費合作社印製 於本發明之另外具體實施例中，藉由其中2_羥基甲硫 丁腈、濃Η2 S Ο 4具約7 0 %重量比與約9 9 %重量比之間之強度 ，及同時加入水於容器中，於其中將2 -羥基-4 -甲硫丁腈水 解之方法製造2 -羥基-4-甲硫丁酸或其鹽。於容器中水解2一 羥基-4 -甲硫丁腈，產生含2 -羥基-4 -甲硫丁醯胺之水性水解 混合物。2 -羥基-4 -甲硫丁醯胺水解產生完成之水性水解產 物含2 -羥基-4 -甲硫丁酸。自完成之水性水解產物中回收2 -羥基-4 -甲硫丁酸。 本纸張尺度適用中國國家標準（CNS ) Α4規格（210X 297公釐） 經濟部中央標準局員工消費合作社印裝 495500 A7 B7 五、發明説明（5 ) 本發明之另外之具體實施例針對供用於製備HMBA之方法 之裝置。此裝置包括第一個連續攪拌槽反應器供於礦酸存在 下，連績水解2 -羥基-4 -甲硫丁腈，產生水性水解混合物含 2 -羥基-4 -甲硫丁醯胺。裝置亦包括醯胺水解流動反應器供 2-羥基-4-甲硫丁醯胺與H2S04連續水解，產生完成之水性 水解產物，含2 -羥基-4 -曱硫丁酸。 另外之本發明具體實施例係針對製備2 -羥基-4 -甲硫丁酸 或其鹽之方法，其包括導入2 -羥基-4 -甲硫丁腈及水性礦酸 於水性水解產物其中含2 -羥基-4 -甲硫丁醯胺、礦酸及未反 應之2 -羥基-4 -甲硫丁腈中。於水性水解混合物中之2 -羥基_ 4 -曱硫丁腈，於含回混反應區及與反混合反應區溝通之於流 體流動中之循環區之連續腈水解反應器中水解。循環區包含 循環線。將水性水解混合物於自反混合反應區抽回之循環流 中連續循環，通過循環區再回至回混反應區，當自回混反應 區抽回之循環流含未反應之2 -羥基-4 -甲硫丁腈。自循環區 中之向前流動口移除一部分水性水解混合物，形成腈水解反 應器產物流。將腈水解反應器產物流移至醯胺水解流反應器 。腈水解反應器產物流於向前流動口之下遊處以水稀釋得完 成之反應流。會於完成之反應流中之2 -經基-4 -甲硫丁陸胺 於醯胺水解流動反應器中水解產生含2 -羥基-4 -甲硫丁酸之 完成之水性水解產物。在稀釋以前，於向前流動口之上游之 循環區中之循環流駐留時間與向前流動口之下游之腈水解反 應器產物流之駐留時間之和，在腈水解反應器產物流稀釋以 前，足以實質上區別殘留之2 -羥基-4 -甲硫丁腈。 本纸張尺度適用中國國家標準（CNS ) Α4規格（210X297公釐） (請先閱讀背面之注意事項再填寫本頁) •I裝· 495500 經濟部中央標準局員工消費合作社印製 A7 B7 五、發明説明（< ) 6 圖之簡略說明 圖1為本發明方法之圖示流程圖’說明自HMBN、水及礦酸 連續製造HMBA ; 圖2為說明於圖1中之類型當經修飾以確保殘留之HMBN可 實質上被區別之較佳方法之圖示流程圖； 圖3為本發明方法之圖示流程圖，其中離開腈水解反應器 之2 -羥基-4 -甲硫丁醯胺於連續之攪拌槽反應器與連續操作 之醯胺水解流動反應器中轉化成HMB A ; 圖4為說明於圖3中之類型當經修飾以確保殘留之HMBN 可實質上被區別之較佳方法之圖示流程圖； 圖5為當將濃硫酸流引入反應器中時，適合將HMBN轉化 成2 -羥基-4 -曱硫丁醯胺之連續攪拌之槽反應器之圖示說明 圖6為如圖5所示適宜將HMBN轉化成醯胺，同時在稀釋 前可區別HMBN之連續攪摔槽反應器之圖示說明； 圖7為實驗室規模連續水解方法之圖示流程圖，其中離開 第一個循環反應器之2 -羥基-4 -甲硫丁醯胺於第二循環反應· 器及連續操作之插塞流動反應器中轉化成HMBA ; 圖8為顯示進料至第一反應器之醯胺濃度，腈濃度及水解 產物之加納爾顏色為酸/腈莫耳比之函數及插塞流動反應器 内之溫度（基於實驗室規模實驗）之圖；及 圖9為實驗室規模連續水解方法之圖示流程圖，其中離開 第一反應器之2 -羥基-4 -甲硫丁醯胺引入插塞流動反應器並 水解產生Η Μ B A。 本纸張尺度適用中國國家標準（CNS ) A4規格（210 χ 297公羞） (請先閱讀背面之注意事項再填寫本頁) 、-'tv 495500 A7 B7 經濟部中央標準局員工消費合作社印製 五、發明説明（7 ) 元件代號說明 10代表一連續攪摔槽反應器（CSTR); 1 2代表一回混反應區； 1 4代表一循環線； ]6代表一 SS胺水解流動反應器； 1 8代表一管線； 2 0代表一管線； 2 2代表一栗； 2 4代表一外部熱交換器； 2 6代表一向前流動口； 2 8代表一輸送線； 3 0代表一稀釋點； 3 2代表一線上混合器； 3 4代表一預熱器； 36 代表一CSTR ; 3 8代表一水加熱器； 40代表一冷卻器； 42代表一水解產物平衡槽； 4 4代表一管線； 4 6代表一再循環反應器； 4 8代表一栗； 5 0代表一再循環反應器； 5 2代表一泵； 5 4代表一線圈； (請先閲讀背面之注意事項再填寫本頁) ••I裝 訂‘ 本纸張尺度適用中國國家標準（CNS ) A4規格（210X 297公釐） 495500 Α7 Β7 五、發明説明（） -- 8 5 6代表一定溫烘箱； 5 8代表一線圈； 6 0代表〜小的混合圈； 6 2代表一泵；且 6 4代表一熱水浴。 輕體實施例之詳細j»昍 經濟部中央標準局員工消費合作社印製 (請先閱讀背面之注意事項再填寫本頁) 據本發月提供製備謂6八之方法，其中將HMbn於 水性礦酸中連續水解形成2•減·4_甲射酿胺（下文稱為" 腈水解”），醯連續水解形成111^.：6八（下文稱為"醯胺水解")’。 此方法使用包含第一連續攪拌槽反應器（下文稱為n c s τ r，，） 供腈水解及醯胺水解流動反應器，較好為插塞流動反應器（ 下又’’ P F R ’’），供後續之醯胺水解之裝置實施。腈水解放熱 大，因此最有效地於CSTR反混合供熱轉移及溫度控制下進 行。醯胺水解放熱較少但必須使幾乎完全以達所須之產物品 貝及產率。已發現PFR極適合_胺水解，因其可加以構型使 無實質之反混合下操作，但提供充分之駐留時間供反應而無 須過度之壓力降。例如，已發現工業規模之管線反應器可於 雷諾數過量約5000而在整個反應器中無過度之壓力降下操 作，而產生含基於Η Μ B A少於約0 . 1 %醯胺及少於約〇 . 1 %腈 之水解產物。 更特定言之，本發明針對包括含C S T R供接收含水礦酸及 Η Μ B N進料流之腈水解反應器之裝置。為本發明之目的，水 性礦酸由水及高至9 9重量％礦酸所組成。含水礦酸一般為硫 酸或鹽酸。硫酸尤佳。當Η Μ Β Ν與水於C S T R中反應，形成 -11 - 本紙張尺度適用中國國家標準（CNS) Α4規格（210Χ 297公楚） 495500 經濟部中央標準局員工消費合作社印製 Α7 Β7 五、發明説明（9 ) 含2-羥基-4-甲硫丁醯胺之水性水解混合物。醯胺典型地於 腈水解反應器中水解至一些程度，結果形成於水解混合物中 之銨鹽及Η Μ B A。自C S T R連續除去水性水解混合物，冷卻 並回至C S T R。自向‘流動口移除一部分循環之水性水解混 合物，形成腈水解反應器產物流。此流在引入流動反應器供 完成醯胺水解以前，加以稀釋形成完成反應流。因於腈水解 备中，醯胺水解至一些程度，所以一般較好稀釋腈水解反應 器產物溶液，可實用地提供水供醯胺水解及防止液相分離。 稀釋亦防止當使用硫酸時硫酸氫銨沉澱。然而，當稀釋點很 接近自CSTR抽回之水性水解溶液之點時，已發現可將殘留 之％引入元成反應流中。因為藉加稀釋水降低腈水解速率， 於產物中可增加殘留之腊。 已另外發現殘留之腈可藉由在稀釋以前，提供過度但重要 的流動制度駐留時間供貫質的完成腈水解反應而降至很低含 量。更特定言之’已發現殘留之腈實質上可區別，藉由提供 至少約2 0秒之腈水解流動制度駐留時間，且依反混合之程度 而定，較好於約3 0秒與約5分之間，當例如藉由自csTR抽 回之點與向前流動口之間之駐留時間加上向前流動口與稀釋 點之間之腈水解反應器產物流之駐留時間之和構成時。為本 發明之目的，當不多於約0 . 〇 5 %重量比之腈留於完成反應流 中時，可實質地區別殘留之腈。 亦已發現濃Ηθ〇4、水及HMBN可同時地且直接地引入 第一 CSTR中，以於CSTR内產生適宜ΗΜΒΝ水解之更稀之 有效硫酸強度。Η Μ Β Ν、水及濃H 2 S〇4可同時進料於第一 -12 - 本紙張尺度適用中國國家標隼（CNS ) Α4規格（210X 297公釐） (請先閲讀背面之注意事項再填寫本頁) 、1Τ 經濟部中央標準局員工消費合作社印製 495500 A7 _____B7 五、發明説明（1A )Hernandez et al., US Patent No. 4,912,257 describes that HMBA applies the Chinese National Standard (CNS) A4 specification (210X297 mm) by this paper size (please read the precautions on the back before filling this page. • Staff of the Central Bureau of Standards, Ministry of Economic Affairs Printed by the Consumer Cooperative 495500 A7 B7 V. Description of the invention (3) HMBN is produced by a single step of sulfuric acid hydrolysis. Η Μ BN is fed into an acidification vessel, where it is mixed with 98%. H2S〇4 to The acid / nitrile mole ratio is mixed between 0.5 and 2 to form a reaction mixture containing 20-50% by weight. H 2 S 0 4. When the reaction mixture is manufactured in batches, the mixture is added in a continuous addition loop. Stir and cool to 50 ° C for 30-60 minutes. The reaction mixture is then fed into the hydrolysis reactor and heated at a temperature between 60 ° C and 140 ° C for 5 minutes to 6 hours while applying Micro-vacuum to the reactor. It is said that the method described by Hernandez et al. Produced HMBA by hydrolyzing acidified HMBN solution in a single step, unlike the two-step hydrolysis method known in the art. Printed by the Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs System (read first Please fill in this page before filling in this page.) In order to provide high-quality hydrolysate with the maximum amount of HMB A and the minimum amount of nitrile and amidine components, HMBN and 2-hydroxy-4-methanbutamine must be highly converted into amidine. Μ BA. Batch manufacturing of HMB A provides high conversion. However, the conventional batch method of manufacturing HMB A has several disadvantages. The manufacturing power of the batch method is limited by the batch reversal time. In addition, because each The reaction conditions can be changed during batch manufacturing, so the quality of HMBA hydrolysate will vary from batch to batch. Filling and emptying of batch reactors and non-steady state conditions cause vapor emission, which must be processed before release. Previous techniques The equipment required for the method is expensive. Mix H 2 S04 with water in an acid dilution barrel to form a dilute sulfuric acid feed. A heat exchanger is required to remove the heat of dilution generated in the barrel. The barrel, heat exchanger, pump, and The recycling loop must be of anti-corrosive composition. SUMMARY OF THE INVENTION Among the several objects of the present invention, to provide an improved HMB A preparation method; to provide such a method that can be operated in a continuous manner; to provide such a method that can be operated with high productivity; When compared with the conventional method, it can effectively reduce the main paper size. Applicable to China National Standard (CNS) A4 specification (210X 297 mm) 495500 A7-* --- B7 V. Description of the invention () (Please read the back first Please pay attention to this page before filling in this page) 2. This method of 隹 濩 cost; provide a method to control the reaction conditions when changing compared with the conventional batch hydrolysis system ^, provide the method of batch and conventional, This method of reducing the gas emission when comparing gram and gram; provides the method to eliminate the separated 1 acid dilution < required method, especially provides a method which can be operated with concentrated H2S04 feed stream without previous dilution; provides substantially effective A method to completely convert HMBN to HMBA; and a method to provide a consistent quality HMBA for use in preparing animal feed supplements. These and other objects are obtained by a method of preparing HMBA or a salt thereof, including adding mineral acid to a nitrile hydrolysis reactor containing a continuous stirred tank reactor, and adding 2-hydroxy-4-methylthiobutyronitrile to a nitrile hydrolysis reaction. Device. In the nitrile hydrolysis reactor, 2-hydroxy-4-methylthiobutyronitrile is continuously hydrolyzed to produce a nitrile hydrolysis reactor product stream containing 2-hydroxy-4-methylthiobutamine. The nitrile hydrolysis reactor product stream is continuously introduced into the amine hydrolysis flow reactor. In the hydrazine hydrolysis flow reactor, hydrolyzation of 2- and 4-benzyl-4-methylthiobutyric acid amine to produce an aqueous hydrolysate containing το formed by 2-methyl-4-methylthiobutyric acid. From the completed aqueous hydrolysate, 2-kidoxy-4-methylthiobutanoic acid was recovered. The Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs printed in another specific embodiment of the present invention, in which 2-hydroxymethylthiobutyronitrile and concentrated osmium 2 S 〇 4 have a weight ratio of about 70% and a weight ratio of about 99%. The strength between the two, and the method of simultaneously adding water to a container, and hydrolyzing 2-hydroxy-4-methylthiobutyronitrile therein to produce 2-hydroxy-4-methylthiobutyric acid or a salt thereof. Hydrolysis of 2-hydroxy-4-methylthiobutyronitrile in a container yields an aqueous hydrolysis mixture containing 2-hydroxy-4-methylthiobutamide. The hydrolysis of 2-hydroxy-4-methylthiobutanamine produces a completed aqueous hydrolysis product containing 2-hydroxy-4-methylthiobutanoic acid. 2-Hydroxy-4-methylthiobutanoic acid was recovered from the completed aqueous hydrolysate. This paper size applies the Chinese National Standard (CNS) A4 specification (210X 297 mm) Printed by the Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs 495500 A7 B7 V. Description of the invention (5) Another specific embodiment of the present invention is intended for use in Apparatus for preparing HMBA. This unit includes the first continuous stirred tank reactor for the continuous hydrolysis of 2-hydroxy-4-methylthiobutyronitrile in the presence of mineral acid to produce an aqueous hydrolysis mixture containing 2-hydroxy-4-methylthiobutamine. The unit also includes a hydrazine hydrolysis flow reactor for the continuous hydrolysis of 2-hydroxy-4-methylthiobutane amine and H2S04 to produce a completed aqueous hydrolysate containing 2-hydroxy-4- thiosulfate. In addition, a specific embodiment of the present invention is directed to a method for preparing 2-hydroxy-4-methylthiobutanoic acid or a salt thereof, which includes introducing 2-hydroxy-4-methylthiobutyronitrile and an aqueous mineral acid into an aqueous hydrolysate, which contains 2 -Hydroxy-4-methylthiobutamide, mineral acid and unreacted 2-hydroxy-4-methylthiobutyronitrile. 2-Hydroxy-4-butyrothiobutyronitrile in an aqueous hydrolysis mixture is hydrolyzed in a continuous nitrile hydrolysis reactor containing a backmixing reaction zone and a circulation zone in a fluid flow communicating with the reverse mixing reaction zone. The loop area contains loop lines. The aqueous hydrolysis mixture is continuously circulated in the circulating flow withdrawn from the remixing reaction zone, and then returned to the backmixing reaction zone through the circulation zone. When the circulating flow withdrawn from the backmixing reaction zone contains unreacted 2-hydroxy-4 -Methiobutyronitrile. A portion of the aqueous hydrolysis mixture is removed from the forward flow port in the circulation zone, forming a nitrile hydrolysis reactor product stream. The nitrile hydrolysis reactor product stream is transferred to the amidine hydrolysis stream reactor. The nitrile hydrolysis reactor product stream is a reaction stream that is diluted with water downstream of the forward flow port to complete the reaction stream. Hydrolyzation of 2-methyl-4-methylthiobutyramine in the completed reaction stream in a hydrazine hydrolysis flow reactor produces a completed aqueous hydrolysate containing 2-hydroxy-4-methylthiobutyric acid. The sum of the residence time of the circulating stream in the circulation zone upstream of the forward flow port and the residence time of the product stream of the nitrile hydrolysis reactor downstream of the forward flow port before dilution, before the product stream of the nitrile hydrolysis reactor is diluted, It is sufficient to substantially distinguish the remaining 2-hydroxy-4-methylthiobutyronitrile. This paper size applies to China National Standard (CNS) Α4 size (210X297 mm) (Please read the precautions on the back before filling out this page) • I · 495500 Printed by the Consumer Standards Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs A7 B7 5. Description of the invention (<) 6 Brief description of the drawing Figure 1 is a schematic flow chart of the method of the present invention 'illustrates the continuous manufacturing of HMBA from HMBN, water and mineral acid; Figure 2 is the type illustrated in Figure 1 when modified to ensure Schematic flow chart of a preferred method in which residual HMBN can be substantially distinguished; Figure 3 is a schematic flow chart of the method of the present invention, in which the 2-hydroxy-4-methylthiobutanamine leaving the nitrile hydrolysis reactor is continuously The stirred tank reactor and the continuously operated ammonium hydrolysis flow reactor are converted to HMB A; Figure 4 is a diagram illustrating a preferred method of the type shown in Figure 3 when modified to ensure that residual HMBN can be substantially distinguished Figure 5 is a diagrammatic illustration of a continuous stirred tank reactor suitable for converting HMBN to 2-hydroxy-4-butathioamide when a concentrated sulfuric acid stream is introduced into the reactor. Figure 6 is a diagram As shown in Figure 5, it is suitable to convert HMBN to amidine. Schematic illustration of a continuous stirred tank reactor that can distinguish HMBN before dilution; Figure 7 is a schematic flow chart of a laboratory-scale continuous hydrolysis process, in which 2-hydroxy-4 -methanine leaves the first cycle reactor Amidine is converted to HMBA in the second cycle reactor and plug-flow reactor with continuous operation; Figure 8 shows the amidine concentration, nitrile concentration, and the Gardner color of the hydrolysate fed to the first reactor are acid. A graph of the function of the molar ratio of nitrile to nitrile and the temperature in the plug flow reactor (based on laboratory scale experiments); and Figure 9 is a diagrammatic flow chart of a laboratory scale continuous hydrolysis process, in which 2 leaving the first reactor -Hydroxy-4-methylthiobutamide is introduced into a plug flow reactor and hydrolyzed to produce ΜBA. This paper size applies to China National Standard (CNS) A4 specifications (210 x 297 male shame) (Please read the precautions on the back before filling out this page), -'tv 495500 A7 B7 Printed by the Staff Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs V. Description of the invention (7) Element code description 10 represents a continuous churning tank reactor (CSTR); 12 represents a back mixing reaction zone; 14 represents a circulation line;] 6 represents an SS amine hydrolysis flow reactor; 1 8 represents a pipeline; 2 0 represents a pipeline; 2 2 represents a pump; 2 4 represents an external heat exchanger; 2 6 represents a forward flow port; 2 8 represents a transfer line; 30 represents a dilution point; 3 2 represents an on-line mixer; 3 4 represents a preheater; 36 represents a CSTR; 38 represents a water heater; 40 represents a cooler; 42 represents a hydrolysate balance tank; 4 4 represents a pipeline; 4 6 Represents a recycling reactor; 4 8 represents a chestnut; 50 represents a recycling reactor; 5 2 represents a pump; 5 4 represents a coil; (Please read the notes on the back before filling out this page) •• I binding ' This paper size applies to Chinese National Standard (CNS) A4 Specifications (210X 297mm) 495500 Α7 Β7 V. Description of the invention ()-8 5 6 represents a certain temperature oven; 5 8 represents a coil; 60 represents a small mixing circle; 6 2 represents a pump; and 6 4 Represents a hot bath. The details of the light-weight embodiment are printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs (please read the precautions on the back before filling this page). Continuous hydrolysis in acid to form 2 • min · 4_methylpyramine (hereinafter referred to as " nitrile hydrolysis "), and continuous hydrolysis to form 111 ^ .: 6 eight (hereinafter referred to as " hydrazine hydrolysis ") '. This method uses a first continuous stirred tank reactor (hereinafter referred to as ncs τ r,), a nitrile hydrolysis and ammonium hydrolysis flow reactor, preferably a plug flow reactor (also referred to as `` PFR ''), It is used for the subsequent hydrolysis of amidine. The nitrile water liberation heat is large, so it is most effectively carried out under the CSTR reverse mixing heat transfer and temperature control. The amidine water liberation heat is less, but it must be almost completely to achieve the required Product quality and yield. PFR has been found to be very suitable for amine hydrolysis because it can be configured to operate without substantial backmixing, but provides sufficient dwell time for the reaction without undue pressure drop. For example, it has been found Industrial scale pipeline reaction It can be operated at an excess Reynolds number of about 5000 without excessive pressure drop throughout the reactor, resulting in a hydrolysate containing less than about 0.1% amidine and less than about 0.1% nitrile based on Η Μ BA. In particular, the present invention is directed to a device comprising a nitrile hydrolysis reactor containing a CSTR for receiving an aqueous mineral acid and a ΜM BN feed stream. For the purposes of the present invention, the aqueous mineral acid is water and up to 99% by weight mineral acid The composition of hydrous mineral acid is generally sulfuric acid or hydrochloric acid. Sulfuric acid is particularly preferred. When Μ Μ Β Ν reacts with water in CSTR to form -11-This paper size applies the Chinese National Standard (CNS) A4 specification (210 × 297). 495500 Printed by the Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs A7 B7 V. Description of the invention (9) Aqueous hydrolysis mixture containing 2-hydroxy-4-methylthiobutamide. The amidine is typically hydrolyzed to some in a nitrile hydrolysis reactor. To the extent that the ammonium salt and BA BA are formed in the hydrolysis mixture. The aqueous hydrolysis mixture is continuously removed from the CSTR, cooled and returned to the CSTR. A portion of the circulating aqueous hydrolysis mixture is removed from the 'flow port' to form nitrile water. Reactor product stream. This stream is diluted to form a complete reaction stream before being introduced into the flow reactor for completion of amidine hydrolysis. Because ammonium is hydrolyzed to some extent in nitrile hydrolysis preparations, it is generally preferred to dilute the nitrile hydrolysis reactor product. A solution that can practically provide water for ammonium hydrolysis and prevent liquid phase separation. Dilution also prevents the precipitation of ammonium bisulfate when sulfuric acid is used. However, it has been found when the dilution point is close to the point of the aqueous hydrolysis solution withdrawn from the CSTR. The residual% can be introduced into the elementary reaction stream. Because the nitrile hydrolysis rate can be reduced by adding dilution water, the residual wax can be increased in the product. It has also been found that residual nitrile can provide excessive but important flow before dilution. The dwell time of the system allows the nitrile hydrolysis reaction to be completed qualitatively and reduced to a very low content. More specifically, 'it has been found that the residual nitrile is substantially distinguishable by providing a residence time of the nitrile hydrolysis flow system of at least about 20 seconds, and depending on the degree of anti-mixing, preferably about 30 seconds and about 5 Between minutes, for example, by the sum of the residence time between the point withdrawn from the csTR and the forward flow port plus the residence time of the nitrile hydrolysis reactor product stream between the forward flow port and the dilution point. For the purposes of the present invention, residual nitriles can be substantially distinguished when no more than about 0.05% by weight nitrile is left in the completed reaction stream. It has also been found that concentrated Ηθ04, water, and HMBN can be simultaneously and directly introduced into the first CSTR to produce a more dilute effective sulfuric acid strength in the CSTR that is suitable for ΗΜΒΝ hydrolysis. Μ Μ Β Ν, water and concentrated H 2 S〇4 can be simultaneously fed to the first -12-This paper size applies to China National Standard (CNS) Α4 size (210X 297 mm) (Please read the precautions on the back first (Fill in this page again) 、 Printed by 495500 A7 _____B7 by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs 5. Description of the invention (1A)

1U C/TR内而無阻礙HMBN水解，儘管不同之密度及黏度之硫 酸及HBMN及當以水稀釋hso 挪 师拜時釋放放高稀釋熱。 ¥〇4於反應㈣稀釋祕如習用方法中使用之分開之酸稀 釋（須要，減少費用及水解系統之維護。水解反應所須之水 及酸可以任何實用之混合濃h2S〇4稀酸及水引入，以達第一 次水解所須之濃度及礦酸之比例。 於圖3中說明之本發明之具體實施例中，自腊水解反應器 中除去之腈水解反應器產物流，以水稀釋形成㈣水解流， 其在移至醯胺水解流動反應器以前，進料至第二cstr。替 代地，腈水解·反應器產物流及水流可直 。於第二⑴R中藉進—步水解將實質部分^胺^= HMBA，形成元成反應流。完成反應流再於位於第二csTr 之下流之醯胺水解流動反應器中水解，形成含11%8 A之完成 之水性水解產物。替代地，第二CSTR可加旁通管致使完成 反應流連續地直接進料於醯胺水解流動反應器中並水解形成 水解產物。已發現本發明之方法可以高生產力於一個以上之 連績之CSTRs與流動完成反應器中操作。因此，實行此方 法之主要費用，當與以前技藝中認為必要之批次方法比較， 為大大地降低，以高生產力提供充分之轉化。 已發現此種連續水解方法可提供有效地轉化hmbn成 HMBA，產生會很低量之HMBN及2-羥基-4-甲硫丁醯胺之 高品質水解產物。為產生含HMB A之高品質進料補充物，本 發明方法可以高生產力操作，產生完成之水性水解產物，其 έ至少約〇6重量％1^]\48八、至少約18重量％按鹽、至少約 本纸張尺度適用中國國家標準（CNs ) Α4規格（210X297公釐） (請先閱讀背面之注意事項再填寫本頁) 訂,' 495500 A7 B7 五、發明説明（u) 2 0重量％水、南至約〇 〇 5重量％醯胺及高至約〇 〇 5重量。/〇月膏 。於完成之水性水解產物内之HMBA包含HMBA單體及二 聚物及其他寡聚物。當用於水解之礦酸為Ηβ〇4時，完成水 性水解產物含至少約3 6重量％ η μ B A，至少約3 0重量％按 鹽’如硫酸氫銨或硫酸銨，至少約2 5重量％水，高至約〇 〇 5 重量醯胺及鬲至约005重量％腈。當於水解中用鹽酸時， 完成之水性水解產物含至少約5〇重量％11“[3八，至少約18 重I /〇氣化按、至少約2 0重量百分比水、高至約〇 〇 5重量％ 醯胺及咼至約〇 . 〇 5重量％腈。於本發明之特佳實施例中，於 以Ha S Ο)開始及於致使較佳之水解產物組成可在整個所有過 程操作中一致產生之穩定狀態當中，達成實質上完全之轉化。 根據本發明方法，藉使用較低之酸與腈比例供水解，亦可 製備較純度之水性水解產物。此種水性水解產物含至少約 3 0重量％ 2 -幾基_ 4 -甲硫丁酸、至少約2 〇重量％銨鹽如硫酸 銨或硫酸氫銨，至少約25重量％水、高至約5重量％醯胺及 咼至約0 . 1重量％腈，且具不超過約丨〇 (基於加納爾標度）之 顏色。 經濟部中央標準局員工消費合作社印製 (請先閲讀背面之注意事項再填寫本頁} 一般，在建立穩定情況以前，例如開始時，產生之水解產 物可含比向品質Η Μ B A產物所須較高之醯胺及腈。已發現此 種組成浮動可藉於開始反應當中以較高之礦酸對腈之莫耳比 操作’以很快建立穩定情況而防止。假定，所有礦酸及 HMBN引入第一CSTR反應器，但將礦酸流分開—部分直接 引入胺水解流動反應器。廣f之，因此，礦酸對·腈之莫耳 比係基於礦酸與腈總括引入製程中之累積速率。以較高之礦 本纸張尺度適用中國國家標準（ CNS ) A4規格（210X297公釐） B7 五、發明説明（12 ) 紅對骑之比例操作乏+圭士、 # 反應器中之速率，以致2措由控制錢流人醯胺水解流動 應器中之腈與醯胺之和 f上相▲入该反 莫耳比於約I。與約2·。之;=:=時，啊 ，較好於約U與約15之門開始至建立穩定狀態 。達穩定狀態後，H2S◦奸 ^1.15與約L25之間 4 +如义旲耳比於約0 . ό與約1 . 5之 間’車父佳地於約〇 9盘約〗 ，、、1 · 2 I間，且更佳於約0.9 5與約 1 . 〇 5又間。當用H c丨水解 醉咛％疋狀怨〈HC1對腈之莫耳比 21·0與約U之間’較好於社〇5與約K3之間，更佳地 ;、”’1、· 15與約1.2〈間。上述較佳之酸對腈之比例，對高生 屋力方法為最適當的。對於最有效之控制，礦酸速率較好至 少超過等於腈與醯胺之和之速率之5%。降低酸對腈之比例 可減少完成水性水解產物之顏色’及減少操作費用，以本文 所述之較低酸對腈之比例操作，若希望低#用，低生產力製 造芫成水性水解產物時則可為較佳。 經濟部中央標準局員工消費合作社印製 有關圖1 , 2-羥基-4_曱硫丁醯胺藉於CSTR 1〇中水解 HMBN連續產生。於此製程開始，將礦酸進料流引入反應器 1 0並於其中之回混反應區丨2混合。再將H M B N引入礦酸流 ，於其中其與水反應於水性水解混合物内形成醯胺。當 Η Μ B N與礦酸流連續進料於反應器丨〇内之水性水解混合物 中時，發生連續之腈水解。 礦較好為具強度於約5 〇 %重量比與約7 〇 %重量比之間較 好約60%重量比與約70%重量比之間之h2S〇4。H，s〇4作 為觸媒’且於腈水解反應中無消耗。然而，藉由醯胺水 -15 - 本纸張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） ^5500 Α7 Β7 五、發明説明（13 ) 解反應（其於腈水解反應器中一般發生至一些程度）消耗此酸 ，結果形成NH4HS04，當用H2S〇4於腈水解反應時。反應 於約4(TC與約70。〇間之溫度，較好約6〇。〇與約65。〇之間， 及於總壓力於約0與約15 psig之間進行。於水性水解混合 物含於反應器10内當中，駐留時間於約2〇分與約6〇分之間 ，較好於約2 5分與約4 5分之間。於c s T R 1 〇内之駐留時間 之計算由CSTR 10與循環線14中之水性水解混合物體積除 以腈水解反應器產物流經由向前流動口 2 6移至下流之體積流 動速率。於C S T R 1 0中製造之水性水解混合物含高至約i 6 重量％ Η Μ B A，高至約1 2重量％，銨鹽，至少約6重量％水 ，至少約3 0重量％醯胺及高至約2重量。/。腈。當用H 2 S〇4時 ’於C S T R 1 0中製造之水性水解混合物含高至約1 6重量 %ΗΜΒΑ ，高至約12重量％銨鹽，如NH4HS04或 (N H 4 ) 2 S Ο 4，至少約6重量％，至少約3 5重量％醯胺及高至 約2重量％腈，較佳於約5與約1 2重量％之間之Η Μ B A，於 約4與約9重量％之間銨鹽，於約1 0與約1 5重量％之間水， 於約3 5與約5 0重量％之間醯胺及高至約2重量％腈，且更佳 地，含約5與約1 1重量％之間之Η Μ B A，於約4與約8重量％ 之間之銨鹽，於約1 1與約1 3重量％之間之水，於約4 0與約 5 0重量％之間之酸胺及高至約1重量％腈。 當選H C 1為供腈水解反應用之礦酸時，酸較好具約3 0 %重 量比與約4 0 %重量比之間之強度，更佳地於約3 5 %重量比與 約3 7 %重量比之間。H C 1作為觸媒且於腈水解反應中不被消 耗。然而，H C 1藉由一般於腈水解反應器中發生至一些程度 -16 - 本紙張尺度適用中國國家標準（CNS ) Α4規格（210Χ 297公釐） (請先閲讀背面之注意事項再填寫本頁) 訂 經濟部中央樣準局員工消費合作社印製 經濟部中央標準局員工消費合作社印製 495500 A 7 B7 —-------—----------- 五、發明説明（14 ) 之酿胺水解反應而消耗，結杲於水性水解混合物中形成 NH4C1。在得到完成之水性水解產物後，任何NH4C1固體 可溶解。此反應於約2 5 °c與約6 0 °C之間之溫度，較好於約 4 5 °C與約5 5 °C之間，且於總壓力約2與約1 5 p s i g之間之下 •進行。於水性水解混合物含於反應器1 〇内當中，駐留時間為 約2 5分與約6 0分之間，較好約4 0分與約5 0分之間。當使用 H C 1時，於C S T R 1 0中產生之水性水解混合物，含高至約 1 0重量％ Η Μ B A，高至約5重量％ N H 4 C 1，至少約2 0重量〇/〇 水，至少約40重量％醯胺及高至約、2重量％腈，較好於約2與 約10重量％之間之ΗΜΒΑ，於約0.5與約5重量％之間之NH4C1 ，約2 0與約3 0重量％之間之水，約4 0與約6 0重量％之間之 酿胺及向至約0.5重里％腊’且更佳地，含約5與約9重量y 之間之HMBA，於約0·5與約4重量％之間之NH4C1，約25 與約3 0重量％之間水，約4 5與約6 0重量％之間之酿胺，及 高至約0 . 1重量％腊。 於本發明之替代具體實施例中，將礦酸流分開，致使將一 部分進料至CSTR 10，其餘經由如圖1，2與4中所示之線上 混合器3 2之入口之管線1 8上游進料，或經由管線2 〇進料於 被進料於連續醯胺水解反應器，如圖3中所示之Within 1U C / TR without hindering HMBN hydrolysis, despite the different densities and viscosities of sulfuric acid and HBMN and release of high dilution heat when dilute hso and worship with water. ¥ 〇4 Dilute the reaction in the same way as the separate acid used in the conventional method (required, reduce costs and maintain the hydrolysis system. The water and acid required for the hydrolysis reaction can be mixed with any practical concentrated h2S04 diluted acid and water Introduced to achieve the concentration required for the first hydrolysis and the proportion of mineral acid. In the specific embodiment of the invention illustrated in Figure 3, the nitrile hydrolysis reactor product stream removed from the wax hydrolysis reactor is diluted with water A hydrazone hydrolysis stream is formed, which is fed to the second cstr before moving to the hydrazine hydrolysis flow reactor. Alternatively, the nitrile hydrolysis · reactor product stream and water stream can be straightened. Borrowed in the second hydrazine—step hydrolysis will The substantial part of the amine ^ = HMBA forms the elementary reaction stream. The completed reaction stream is then hydrolyzed in a hydrazine hydrolysis flow reactor located below the second csTr to form a completed aqueous hydrolysate containing 11% 8 A. Alternatively The second CSTR can be supplemented with a bypass tube to cause the completed reaction stream to be continuously fed directly into the amidine hydrolysis flow reactor and hydrolyzed to form a hydrolysate. The method of the present invention has been found to be capable of producing more than one consecutive CSTRs with high productivity. Operate in a reactor with flow. Therefore, the main cost of implementing this method, when compared to batch methods deemed necessary in the prior art, is to greatly reduce and provide sufficient conversion with high productivity. This continuous hydrolysis method has been found It can provide high-quality hydrolysate that efficiently converts hmbn to HMBA, producing very low amounts of HMBN and 2-hydroxy-4-methanbutamine. To produce high-quality feed supplements containing HMB A, the method of the present invention It can be operated with high productivity to produce a completed aqueous hydrolysate, which is at least about 06% by weight 1 ^] \ 48, at least about 18% by weight, according to the national standard (CNs) Α4 specification according to the salt, at least about this paper size (210X297 mm) (Please read the notes on the back before filling this page) Order, '495500 A7 B7 V. Description of the invention (u) 20% by weight water, south to about 0.05% by weight amidine and up to Approx. 005 weight. / 0 month cream. The HMBA in the completed aqueous hydrolysate contains HMBA monomers and dimers and other oligomers. When the mineral acid used for hydrolysis is Ηβ04, the aqueous hydrolysis is completed Product contains at least about 36 weight % Η μ BA, at least about 30% by weight as a salt such as ammonium bisulfate or ammonium sulfate, at least about 25% by weight water, up to about 0.05% by weight amidine and rhenium to about 005% by weight nitrile. When used in When hydrochloric acid is used in the hydrolysis, the completed aqueous hydrolysate contains at least about 50% by weight 11 "[38, at least about 18% by weight I / O gasification, at least about 20% by weight water, and up to about 0.05% by weight % Ammonium and hydrazone to about 0.05% by weight nitrile. In a particularly preferred embodiment of the invention, starting with Ha S 0) and resulting in a better hydrolysate composition can be consistently produced throughout all process operations In the steady state, a substantially complete transformation is achieved. According to the method of the present invention, a relatively pure aqueous hydrolysate can also be prepared by using a lower ratio of acid to nitrile for hydrolysis. Such an aqueous hydrolysate contains at least about 30% by weight 2-isopropyl-4-methylthiobutanoic acid, at least about 20% by weight ammonium salts such as ammonium sulfate or ammonium bisulfate, at least about 25% by weight water, up to about 5% by weight of amidine and hydrazone to about 0.1% by weight of nitrile, and having a color not exceeding about 丨 0 (based on the Gardner scale). Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs (please read the notes on the back before filling out this page) In general, before establishing a stable situation, for example, at the beginning, the hydrolysate produced can contain specific quality Η Μ BA products required Higher ammonium amines and nitriles. It has been found that this compositional fluctuation can be prevented by operating at a higher molar ratio of mineral acid to nitrile in the beginning of the reaction to quickly establish a stable situation. Assume that all mineral acids and HMBN Introduced the first CSTR reactor, but separated the mineral acid flow-partly introduced directly into the amine hydrolysis flow reactor. Therefore, the molar ratio of mineral acid to nitrile is based on the accumulation of mineral acid and nitrile in the process. Rate. Applicable to China National Standard (CNS) A4 specification (210X297 mm) at higher mineral paper size. B7 V. Description of the invention (12) Red to ride ratio is lack of operation + Guishi, # Rate in the reactor So that the second measure is to control the flow of money to the sum of the nitrile and amidine in the amidine hydrolysis flow reactor. The anti-molar ratio is about I. and about 2 .... of; =: = Hour, ah , Better than about U and about 15 gates to establish stability After reaching a stable state, H2S ◦ ^ 1.15 and about L25 4 + Ruyi Er ear is better than about 0. ό and about 1.5 'Car father good place in about 0.99 set, ， Between 1 and 2 I, and more preferably between about 0.9 5 and about 1.05. When hydrolyzed with H c 丨% 咛 疋 resentment <HC1 to Molar ratio of nitrile 21.0 to about U It is better to be between S05 and K3, more preferably; "1, · 15 and 1.2". The above-mentioned preferred ratio of acid to nitrile is the most suitable for the high-energy housing method. For the most effective control, the rate of mineral acid is preferably at least more than equal to 5% of the rate of the sum of nitrile and amidine. Reducing the ratio of acid to nitrile can reduce the color of the finished aqueous hydrolysate and reduce the operating costs, as described herein The lower acid to nitrile ratio operation, if you want low # use, low productivity can be better when the production of water-soluble hydrolyzed products. Central Bureau of Standards of the Ministry of Economic Affairs, Consumer Cooperatives, printed Figure 1, 2-hydroxy-4 _ Thiobutamide is continuously produced by hydrolyzing HMBN in CSTR 10. At the beginning of this process, a mineral acid feed stream is introduced into reactor 10 and back mixed therein. The reaction zone 2 is mixed. Then HMBN is introduced into the mineral acid stream, where it reacts with water in the aqueous hydrolysis mixture to form ammonium amine. When Μ BN and mineral acid stream are continuously fed into the aqueous hydrolysis mixture in the reactor In the middle period, continuous nitrile hydrolysis occurs. The ore is preferably h2S04 with a strength between about 50% by weight and about 70% by weight, preferably between about 60% by weight and about 70% by weight. H, s〇4 as a catalyst 'and no consumption in the nitrile hydrolysis reaction. However, with ammonium water -15-This paper size applies the Chinese National Standard (CNS) A4 specification (210X297 mm) ^ 5500 Α7 Β7 V. Description of the invention (13) The decomposition reaction (which usually occurs to some extent in the nitrile hydrolysis reactor) consumes this acid, resulting in the formation of NH4HS04 when H2S04 is used in the nitrile hydrolysis reaction. The reaction is carried out at a temperature between about 4 ° C. and about 70 °, preferably between about 60 ° and about 65.0, and at a total pressure between about 0 and about 15 psig. The aqueous hydrolysis mixture contains In the reactor 10, the dwell time is between about 20 minutes and about 60 minutes, preferably between about 25 minutes and about 45 minutes. The calculation of the dwell time within cs TR 100 is made by CSTR The volume of the aqueous hydrolysis mixture in 10 and circulation line 14 is divided by the volumetric flow rate of the nitrile hydrolysis reactor product stream moving through the forward flow port 26 to the downstream. The aqueous hydrolysis mixture manufactured in CSTR 10 contains up to about 6 % By weight Η Μ BA, up to about 12% by weight, ammonium salt, at least about 6% by weight water, at least about 30% by weight amidine and up to about 2% by weight nitrile. When using H 2 S〇4 The aqueous hydrolysis mixture produced in CSTR 10 contains up to about 16% by weight ΗΜΒΑ, up to about 12% by weight ammonium salt, such as NH4HS04 or (NH4) 2 S 〇4, at least about 6% by weight, at least About 35% by weight ammonium amine and up to about 2% by weight nitrile, preferably between about 5 and about 12% by weight Η Μ BA, between about 4 and about 9% by weight Ammonium salt, between about 10 and about 15% by weight water, between about 35 and about 50% by weight amidine and up to about 2% by weight nitrile, and more preferably, containing about 5 Μ BA between about 11% by weight, ammonium salt between about 4 and about 8% by weight, water between about 11 and about 13% by weight, between about 40 and about 50 Acid amines between about 1% by weight and nitriles up to about 1% by weight. When HC 1 is selected as the mineral acid for the nitrile hydrolysis reaction, the acid preferably has a content between about 30% by weight and about 40% by weight. Strength, more preferably between about 35% by weight and about 37% by weight. HC 1 acts as a catalyst and is not consumed in the nitrile hydrolysis reaction. However, HC 1 is generally used in nitrile hydrolysis reactors. Occurred to some degree -16-This paper size applies to China National Standard (CNS) Α4 size (210 × 297 mm) (Please read the precautions on the back before filling this page) Order printed by the Central Consumer Bureau of the Ministry of Economic Affairs Printed by the Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs 495500 A 7 B7 ------------------------ 5. Description of the invention (14) Consumption of amine fermentation hydrolysis Stingy NH4C1 is formed in the alkaline hydrolysis mixture. After the finished aqueous hydrolysate is obtained, any NH4C1 solids are soluble. This reaction is at a temperature between about 25 ° C and about 60 ° C, preferably about 45 ° C and Between about 5 5 ° C, and under total pressure between about 2 and about 15 psig. • The aqueous hydrolysis mixture is contained in the reactor 10, and the residence time is about 25 minutes and about 60. It is preferably between about 40 minutes and about 50 minutes. When HC 1 is used, the aqueous hydrolysis mixture produced in CSTR 10 contains up to about 10% by weight BA BA, up to about 5% by weight NH 4 C 1 and at least about 20% by weight water / 0%, At least about 40% by weight amidine and up to about 2% by weight nitrile, preferably between about 2 and about 10% by weight of MGBA, between about 0.5 and about 5% by weight of NH4C1, about 20 and about 30% by weight of water, about 40% and about 60% by weight of fermented amines, and about 0.5% by weight of wax, and more preferably, HMBA of about 5 and about 9% by weight, NH4C1 between about 0.5 and about 4% by weight, water between about 25 and about 30% by weight, fermented amine between about 45 and about 60% by weight, and up to about 0.1% by weight % Wax. In an alternative embodiment of the present invention, the mineral acid stream is separated such that a portion is fed to CSTR 10 and the rest passes upstream of line 18 at the inlet of on-line mixer 32 as shown in Figures 1, 2 and 4 Feed, or via line 20 to be fed to a continuous amidine hydrolysis reactor, as shown in Figure 3

〜禾一 C S T R 3 6中之醯胺水解混合物。進料至^ s T R 1 0中之醢机拉_ 『^^鉍對腈莫耳 比於約0 · 6與約1 . 5之間，較佳地於約〇 . 8與約〗 卜 1 z &lt;間。總 莫耳酸對腈之比於約〇 . 7與約1 · 5之間，較好於約〇 9與系、 1 · 2之間，更佳於約〇 . 9 5與約1 . 〇 5之間。供本菸 、 x明目的之總 莫耳酸對腈之比為為任何礦酸進料流 &quot; ^和除以進 -17 - 本纸張尺度適用中國國家標準（CNS ) A4規格（210X 297公楚) &quot;-~ He amine hydrolyzed mixture of C S T R 3 6. Feeding to ^ s TR 1 0 _ "^^ Bismuth to Nitrile Molar ratio is between about 0.6 and about 1.5, preferably between about 0.8 and about 〖1 1 z &lt; between. The ratio of total molar acid to nitrile is between about 0.7 and about 1.5, preferably between about 0.9 and about 1.2, and more preferably between about 0.95 and about 1.0. between. The ratio of total molic acid to nitrile for the purpose of this cigarette is x for any mineral acid feed stream &quot; ^ and divided by -17-This paper size applies to China National Standard (CNS) A4 (210X 297) Gongchu) &quot;-

I (請先閎讀背面之注意事項再填寫本頁} 訂‘ 495500 A7 B7 五、發明説明（15 ) 料至腈水解反應器之腈。 當希望低費用，低生產力製造完成之水性水解產物時，較 低之酸對腈之莫耳比為佳。於此等情況下進料至cstr ι〇中 之酸對腈莫耳比於約0.5與約0.95之間，且較佳地於約〇8 與約0.9 5之間。總莫耳酸對腈之比例於約〇 . 6與約〇 . 9 5之間 ’較佳於約0.8 5與約〇 . 9 5之間。 於圖1中，連續之腈水解反應器亦包括於與回混反應區12 父通又流體流動中循環區。此循環區包括循環線丨4，經由其 將自回混反應區1 2抽回之水性水解混合物經由泵2 2連續循 環。外邯熱父換器2 4較好包含於循環線中，以藉轉移至冷卻 劑而除去放熱之反應熱。通過泵22及熱交換器24後，水性 水解混合物回至回混反應區1 2。於循環區中自向前流動口 2 6除去一部分水性水解混合物，形成腈水解反應器產物流， 其移至醯胺水解流動反應器1 6。 於整個循環區中循環之水性水解混合物之溫度至少3 ， 經濟部中央標準局員工消費合作社印製 (請先閲讀背面之注意事項再填寫本頁) 較好於4 0。(3與約6 0。(：之間。當使用Η2 S〇4時，溫度至少約 5 0。(3，較好於約55°C與約6CTC之間（於整個循環區），及當 使用H C 1時’於整個循環區之溫度至少約3 〇它，較好於約 40C與約50C之間。反應器1〇可備有套層，提供另外之冷 卻容量，且若在開始時所須，亦提供加熱反應器之内容物。 於反應器中之液體含量由含量控制器維持一定。雖然液體 含量亦可自反應器之重力溢流而控制，若使用正的含量控制 ’更易於设计水解系統，含量控制器亦佳，因水性水 本纸張尺度適用中國國家標準（CNS ) A4規格（210X 297公釐） 495500 A7 五、發明説明（Μ ) 解混合物為黏的。而且含量控制器之利用，使得以依操作者 之選擇改變反應器之工作容量及駐留時間，例如以適合物料 通過量之變化。 Μ於本發明之特佳具體實施例中，至少約2G秒之流動制度駐 田時間，在反應溶液稀釋供進行醯胺水解以前，提供來有效 地完成腈水解。圖2說明此種配置。離開回混反應區12之^ 性水解混合物較好不自泵22之抽氣侧除去，而替代地經由泵 2 2輸送通過循環線1 4至位於循環線上之向前流動口 2 6，為 泵足充分地下游之距離，提供流動反應制度，較佳地為其中 消耗一邵分殘留之腈之插塞流動段。有利地，將向前流動口 2 6如此選定位置，提供至少約3秒，一般於約3秒至約1 $秒 之間，且較佳地約5秒與約1 〇秒之間之駐留時間於循環系1 4 之流動口 2 6之上流，以促進殘留之腈之反應。由於實質體積 之水性水解混合物循環通過熱交換器2 4供除去反應熱，所以 循環線中之流動制度易於擾動之制度中維持，以致於自 CSTR 10抽回之點及流動口 26之間之循環系14之部分，實質 上作為插塞流動反應器用。 經濟部中央標準局員工消費合作社印製 (請先閲讀背面之注意事項再填寫本頁} 一部分之循環水性水解混合物如腈水解反應器產物流自向 前流動口 2 6除去，而其餘之循環流流回CSTR 1 〇。為確保殘 留之腈最有效地降低，提供至少約3 〇秒，較好約3 〇秒與約5 分鐘之間，更佳約3 〇秒與約3分鐘之間，更佳地約2分與約3 分之間之流動制度駐留時間供於流動制度腈消失反應區中完 成腈水解反應，該反應區由CSTR 10之出口與向前流動口 26 之間之部分循環線與腈水解反應器產物輸送線2 8稀釋點3 〇 本紙張尺度適用中國國家標準（CNS ) A4規格（210X 297公釐） 495500 經濟部中央標準局員工消費合作社印製 A7 B7 五、發明説明（17 ) 上游所組成，因此，如上述，在自CSTR 10抽回之點與流動 口 2 6之間，有利地提供約3秒與約1 5秒之間之駐留時間，輸 送線2 8較好加以構型以提供約1 〇秒與約5分鐘之間，更佳地 約3 0秒與約5分鐘之間，最佳地約1分鐘與約3分鐘之間之駐 留時間。為提供所須之駐留時間而無過度之流動速度及壓力 降，輸送線2 8可加以構型供薄層流動，但任何之流動情況， 輸送線中提供至少1個相等之回混反應區。輸送線2 8亦可加 以構型供擾動流動用。較佳地，速度為如此致使於前述之腈 消失反應區中提供至少約2個相等之回混反應區，更佳地約3 與約5個之間之依次回混反應區之同等區。於特佳之具體實 施例中，於腈水解反應器產物流中稀釋點3 0處之殘留 HMBN不高於基於含於腈水解反應器產物流中之HMBA與 醯胺之和之約0.01重量％。 輸送線28較好構型為垂直之下導管，致使於CSTR 10中被 水性水解產物混合物帶走之氮或其他氣體，可自向下流動之 液體中解放且放出通過下導管輸送線2 8之頂端。雖然可用水 平之構型，但於水平線中任何氣體可自向前流動中解放並聚 積，降低管線中之有效液體體積。 當腈水解反應器產物流被輸送至向前流動口 2 6下游時，其 於線上混合器3 2中與水流與礦酸流動中任何分開之部分混合 形成完成反應流。腈水解反應器產物流與水流及任何酸流混 合，確保均句之液體混合物引至醯胺水解流動反應器1 6。任 何水流亦再稀釋於完成反應流中之礦酸，於酸胺水解當中， 提供被消耗之反應水，並降低完成反應流之黏度。當用硫酸 本纸張尺度適用中國國家標準（CNS ) A4規格（210X 297公釐） (請先閱讀背面之注意事項再填寫本頁) 訂 -1¾ 495500 A7 _B7 五、發明説明（18 ) 時’腈水解反應器產物流之稀釋可避免在醯胺水解流動反應 器16内NH4HS〇4之液相分離或沉殿。當使用hcI供水解時 ，ΝΗ/Ι典型地會沉澱。將水流典型地以提供完成反應流中 之ΗθΟ*強度於基於無有機物約3 〇 %與約5 〇 %重量比之間， 較佳地約3 5 %至約4 5 %重量比之間，更佳地約4 3 %重量比之 速率引入。若使用約3 0 %至約3 8 %重量比之H C 1，無須加水 。於完成反應流中之H C 1強度於基於無有機物之約3 〇 %與約 4 0 %重量比之間，較好約3 5 %至約3 8 %重量比之間，更佳約 3 6 %重量比。 . 在與腈水解反應器產物流混合以形成完成反應流之前可將 水流加熱’或完成反應流在進料至醯胺水解流動反應器1 6以 前可加熱，提供所須之反應器操作溫度。典型地，水流加熱 至約6 0 °C與約1 0 0 °C之間，較佳於約7 〇。〇與約9 0。(：之間， 且更佳約75 °C與約80t之間之溫度。若水未預熱或完成反 應流之溫度太低，可將此流於預熱器3 4中帶至所須溫度。於 稀釋點3 0與至醯胺水解流反應器之入口之間之完成反應流之 駐留時間並不重要。完成反應流於此區中徹底混合再進入醯 胺水解流動反應器1 6。 經濟部中央標準局員工消費合作社印製 (請先閱讀背面之注意事項再填寫本頁) 於醯胺水解流動反應器中，一些殘留之HMBN水解形成另 外之酿胺，醯胺再實質上水解成HMBA。較佳地，進料至醯 胺水解流動反應器之水對醯胺之比例於約5與約丨〇之間。完 成反應流之流動速率較佳地操作以維持在醯胺水解流動反應 器中適宜之速度，於其中維持擾動並減少軸之反混合。 如上指示’於醯胺水解流動反應器中指定之駐留時間，已 本纸張尺度適用中國國家標隼（CNS ) A4規格Ul0X297公楚） 19^5500 A7 五、 發明説明（ 發現藉增加進料中礦酸/腈莫耳比，可實質上增加轉化。實 驗已顯示於一些例中，當H2S〇4/腈莫耳比為L0時於開始^ 2小時得穩定狀態，但當Η3〇4/腈莫耳比為u時，幾乎可 立刻得穩定狀態。快速建立穩定狀態使能一致地製造高品質 水解產物，其在離開醯胺水解流動反應器丨6後，含高至約 0.05重量％醯胺及高至約〇 〇5重量％腈。 然而，過量礦酸之消費，若在建立穩定狀態後，例行之製 %操作當中維持增加之礦酸/腈莫耳比，則可阻止。因此， 較好只在最初開始至在醯胺水解流動反應器中建立穩定狀態 時，使用Ηβο,/腈莫耳比於約ι·〇與約1 5之間，較好於= 1.15與約1·25之間，以避免在開始期間製備不合規格之水 解產物。當加至醯胺水解流動反應器16之莫耳過量之 為約〇與約50%之間，較好約15與約25%之間， 化學計量上與引入醯胺水解流動反應器之醯胺與同等 d，則可得此種莫耳比。建立穩定狀態後，I%/腊莫 耳比可再調至，並維持於更在費用上有效率之莫耳比約〇9 與約1·2之間，較好約0.95與約1〇5之間。水進料至混合機 32中之速率可增加以避免當使用¥〇4/腈莫耳比低於口1〇 時，有機及水相之液相分離。當用H c丨供水解時，於穩定狀 態當中，HC1對腈之莫耳比於約1〇與約15之間，較好約 1.05與約丨.3之間，更佳約丨丨與約12之間。當加至酿胺水 解流動反應器16之莫耳過量之HC1於約〇與約5〇%之間，較 好約5與約30%之間，更佳約1〇與約2〇%之間，超過化學計 量上與引入醯胺水解流動反應器之醯胺同等之量， 22 本纸張尺度適用中國國家標準（CNS ) A4規格（210X 297公餐 (請先閲讀背面之注意事項再填寫本頁} 丁、 、-*0 經濟部中央標準局員工消費合作社印製 495500 A7 B7 五、發明説明（） v 20 ; 則可得此種莫耳比。 已發現在開始時，以高礦酸/腈莫耳比操作醯胺水解流動 反應器，改進醯胺水解流動反應器16内醯胺之轉化成a ，而典使水解產物之顏色變暗。儘管藉由高酸/腈比提供增 加I反應條件之嚴苛性，出乎意料地發現酸/腈莫耳比並不 顯著影響水解產物顏色。而且，高之酸對腈莫耳比亦容許在 穩足操作期間，醯胺水解流動反應器於較低溫下操作，因此 產生色之水解產物。 經濟部中央標準局員工消f合作社印製 (請先閱讀背面之注意事項再填寫本頁) 離開酿胺水解流動反應器16之水解產物；使用加納爾比色 计測量時，具約5至約丨〇之間，較好約5至約7之間之淺色， 顏色不利地受醯胺水解流動反應器1 6中過度之醯胺水解流動 反應器溫度及駐留時間所影響。醯胺水解流動反應器於約7〇 C與約1 2 0 C之間操作。當醯胺水解流動反應器於絕熱下操 作時’當反應產物吸收絕熱之反應熱時，溫度沿著流動途徑 升高，達到流動途徑上之點（熱點），於其點溫度達平台，且 若情況沒那麼完全地絕熱，超過其點可微下降。於醯胺水解 流動反應器中之最高溫度較好於約9 〇 t與約丨2 〇。〇間，更佳 地約9 0 °C與約1 〇 5 °C之間。於醯胺水解流動反應器内之完成 反應/瓦之駐留時間約3 〇分與約1 〇 〇分之間，較佳地約5 〇分與 約7 0分之間。當醯胺水解流動反應器於高於丨丨〇它之溫度下 操作，可產.生較暗黑之水解產物。然而，醯胺水解流動反應 器溫度低於9 0 °C，可造成不完全之醯胺水解，除非使用較高 之酸對腈莫耳比。若駐留時間超過約丨2 〇分，亦可使水解產 物變深。當在開始時使用約1 · 1與約1 . 5之間之酸/月膏莫耳比 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） B7 21 五、發明説明 請 先 閱 讀 背 面 冬 I 事 項 再 填 寫 本 頁 及當醯胺水解流動反應器16於約7〇與約95它之間，較好約 8 〇°C與約90 °C之間之中等溫度下操作之正常操作，可產生 淺色之水解產物。當在絕熱下操作，藉降低進入混合器32之 水流溫度，可降低醯胺水解流動反應器溫1。若I完成反應 流引入醯胺水解流動反應器以前，將其引入預熱器以（圖〇 ，可減少應用於預熱器之熱，降低醯胺水解流動反應器操作 ’皿度替代地，當醯胺水解流動反應器於等溫下操作時，可 提供冷卻及/或加熱，控制醯胺水解流動反應器溫度。當第 一03丁1136亦圖3中所717，在醯胺水解流動反應器16之前， 右第一 CSTR之操作溫度太鬲，則可產生變深色之水解產物 。當使用上述之酸/腈莫耳比及於約7 〇與約9 5。匸之間，較佳 於約8(TC與約9(TC之間之中等溫度下操作第二cstr時，產 生淺色之水解產物。 最適且用於本發明之醯胺水解方法之流動反應器為插塞流 動反應器，經構型供於至少50之皮克里特準數，於至少9〇 C足PFR操作溫度下操作。皮克里特準數為量度pFR内之軸 反混合，由下式所定義：I (Please read the precautions on the back before filling out this page} Order '495500 A7 B7 V. Description of the invention (15) Nitrile feed to nitrile hydrolysis reactor. When you want low cost, low productivity to produce the finished hydrolysate A lower molar ratio of acid to nitrile is preferred. In these cases, the molar ratio of acid to nitrile fed to cstr 〇 is between about 0.5 and about 0.95, and preferably about 0. 8 And about 0.9 5. The ratio of total molate to nitrile is between about 0.6 and about 0.95 ', preferably between about 0.8 5 and about 0.95. In Figure 1, continuous The nitrile hydrolysis reactor also includes a circulation zone in the fluid flow with the back-mixing reaction zone 12. The circulation zone includes a circulation line 4 through which the aqueous hydrolysis mixture withdrawn from the back-mixing reaction zone 12 is pumped. 2 2 continuous circulation. The external heat exchanger 24 is preferably included in the circulation line to remove the exothermic reaction heat by transferring to the coolant. After passing through the pump 22 and the heat exchanger 24, the aqueous hydrolysis mixture returns to Mix the reaction zone 1 2. In the circulation zone, remove a part of the aqueous hydrolysis mixture from the forward flow port 2 6 to form a nitrile hydrolysis The product stream of the reactor is moved to the ammonium hydrolysis flow reactor 16. The temperature of the aqueous hydrolysis mixture circulating in the entire circulation zone is at least 3, printed by the Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs (please read the precautions on the back first) Fill out this page again) Better than 40. (3 and about 60. (: Between. When using Η2 S04, the temperature is at least about 50. (3, better than about 55 ° C and about 6CTC) Between (in the entire circulation zone), and when using HC 1 ', the temperature in the entire circulation zone is at least about 30 ° C, preferably between about 40C and about 50C. The reactor 10 can be provided with jackets, providing Additional cooling capacity, and if required at the beginning, the contents of the heating reactor are also provided. The liquid content in the reactor is maintained by the content controller. Although the liquid content can also be controlled from the gravity overflow of the reactor If you use positive content control, it is easier to design the hydrolysis system, and the content controller is also good. Because the size of the water-based paper is applicable to the Chinese National Standard (CNS) A4 specification (210X 297 mm) 495500 A7 V. Description of invention (M ) The solution mixture is sticky. The use of the controller makes it possible to change the working capacity and dwell time of the reactor according to the operator's choice, for example, to adapt to changes in the throughput of the material. In a particularly preferred embodiment of the present invention, a flow regime of at least about 2G seconds The dwell time is provided to effectively complete the nitrile hydrolysis before the reaction solution is diluted for ammonium hydrolysis. Figure 2 illustrates this configuration. The hydrolyzed mixture leaving the back-mixing reaction zone 12 is preferably not from the pumping side of the pump 22 Remove, and instead transport through the circulation line 14 through the circulation line 14 to the forward flow port 26 located on the circulation line via the pump 22, to provide a sufficient downstream distance of the pump foot, to provide a flow reaction system, preferably one of which is consumed Residual nitrile plug flow section. Advantageously, the forward flow port 26 is so selected to provide a residence time of at least about 3 seconds, typically between about 3 seconds and about 1 $ second, and preferably between about 5 seconds and about 10 seconds. Flow above the flow port 2 6 of the circulation system 1 4 to promote the reaction of the residual nitrile. Since the substantial volume of the aqueous hydrolysis mixture is circulated through the heat exchanger 24 to remove the reaction heat, the flow system in the circulation line is maintained in a system that is easily disturbed, so that the circulation between the point of withdrawal from CSTR 10 and the flow port 26 The part of the system 14 is substantially used as a plug flow reactor. Printed by the Consumer Cooperatives of the Central Bureau of Standards of the Ministry of Economic Affairs (please read the notes on the back before filling out this page) Part of the circulating aqueous hydrolysis mixture such as the nitrile hydrolysis reactor product stream is removed from the forward flow port 2 6 and the remaining circulating stream Flow back to CSTR 10. To ensure the most effective reduction of residual nitrile, provide at least about 30 seconds, preferably between about 30 seconds and about 5 minutes, more preferably between about 30 seconds and about 3 minutes, more The dwell time of the flow system between about 2 minutes and about 3 minutes is used to complete the nitrile hydrolysis reaction in the flow system nitrile disappearance reaction zone, which is part of the circulation line between the exit of CSTR 10 and the forward flow port 26 Product transfer line with nitrile hydrolysis reactor 2 8 Dilution point 3 〇 This paper size applies to Chinese National Standard (CNS) A4 (210X 297 mm) 495500 Printed by A7 B7, Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs 17) It is composed upstream, so, as mentioned above, between the point of withdrawal from the CSTR 10 and the flow port 26, it is advantageous to provide a residence time between about 3 seconds and about 15 seconds, and the conveyor line 2 8 is better Structured to improve Provide a residence time between about 10 seconds and about 5 minutes, more preferably between about 30 seconds and about 5 minutes, and most preferably between about 1 minute and about 3 minutes. To provide the required residence time Without excessive flow speed and pressure drop, the conveyor line 28 can be configured for thin layer flow, but for any flow conditions, the conveyor line provides at least one equivalent back-mixed reaction zone. The conveyor line 28 can also be structured Type for disturbing flow. Preferably, the speed is such that at least about two equal back-mixed reaction zones are provided in the aforementioned nitrile disappearance reaction zone, and more preferably between about 3 and about 5 back-mixed reactions in sequence The equivalent area of the zone. In a specific embodiment of the special, the residual HMBN at the dilution point 30 in the product stream of the nitrile hydrolysis reactor is not higher than the sum based on the sum of HMBA and amidine contained in the product stream of the nitrile hydrolysis reactor. About 0.01% by weight. The transport line 28 is preferably configured as a vertical lower duct, so that nitrogen or other gases taken away by the aqueous hydrolysate mixture in CSTR 10 can be liberated from the downward flowing liquid and released through the lower duct. Top of conveyor line 2 8. Although horizontal structure is available However, any gas in the horizontal line can be liberated and accumulated from the forward flow, reducing the effective liquid volume in the pipeline. When the nitrile hydrolysis reactor product stream is transported downstream of the forward flow port 26, it is in the on-line mixer 3 2 is mixed with any separated part of the water flow and mineral acid flow to form a complete reaction flow. The product stream of the nitrile hydrolysis reactor is mixed with the water flow and any acid flow to ensure that the homogeneous liquid mixture is led to the ammonium hydrolysis flow reactor 16. Any water stream is then diluted in the mineral acid in the completed reaction stream, which provides the consumed reaction water in the acid-amine hydrolysis, and reduces the viscosity of the completed reaction stream. When using sulfuric acid, the paper size applies the Chinese National Standard (CNS) A4 Specifications (210X 297mm) (Please read the notes on the back before filling out this page) Order-1¾ 495500 A7 _B7 V. Description of the invention (18) The dilution of the product flow of the nitrile hydrolysis reactor can avoid the hydrolysis of the ammonium amine Liquid phase separation or sinking of NH4HS04 in reactor 16. When hcI is used for hydrolysis, NQ / 1 will typically precipitate. The water stream is typically provided to provide a ΗθΟ * strength in the completed reaction stream between about 30% and about 50% by weight based on the absence of organic matter, preferably between about 35% and about 45% by weight, and more It is preferably introduced at a rate of about 43% by weight. If H C 1 is used at a weight ratio of about 30% to about 38%, no additional water is required. The strength of HC 1 in the completed reaction stream is between about 30% and about 40% by weight based on organic-free matter, preferably between about 35% and about 38% by weight, and more preferably about 36%. weight ratio. The water stream can be heated 'before being mixed with the nitrile hydrolysis reactor product stream to form a completed reaction stream, or the completed reaction stream can be heated before being fed to the amidine hydrolysis flow reactor 16 to provide the required reactor operating temperature. Typically, the water stream is heated to between about 60 ° C and about 100 ° C, preferably about 70 ° C. 〇 and about 90. (: Between, and more preferably between about 75 ° C and about 80t. If the water is not preheated or the temperature of the reaction stream is too low, this stream can be brought to the required temperature in the preheater 34. The residence time of the completed reaction stream between the dilution point 30 and the entrance to the amidine hydrolysis stream reactor is not important. The complete reaction stream is thoroughly mixed in this zone before entering the amidine hydrolysis flow reactor 16. Ministry of Economic Affairs Printed by the Consumer Standards Cooperative of the Central Bureau of Standards (please read the notes on the back before filling this page). In the amidine hydrolytic flow reactor, some residual HMBN is hydrolyzed to form another fermented amine, which is then hydrolyzed to HMBA. Preferably, the ratio of water to hydrazine fed to the amidine hydrolysis flow reactor is between about 5 and about 1.00. The flow rate to complete the reaction stream is preferably operated to maintain the amidine hydrolysis flow reactor. A suitable speed to maintain disturbances and reduce anti-mixing of the shaft. As indicated above, the dwell time specified in the amidine hydrolytic flow reactor has been adapted to the Chinese national standard (CNS) A4 specification Ul0X297. 19 ^ 5500 A7 five Description of the invention (It is found that by increasing the mineral acid / nitrile mole ratio in the feed, the conversion can be substantially increased. Experiments have shown in some cases that when the H2S04 / nitrile mole ratio is L0, it is stable at the beginning ^ 2 hours State, but when the molar ratio of 304 / nitrile is u, a stable state can be obtained almost immediately. The rapid establishment of a stable state enables consistent production of high-quality hydrolysate, which leaves the hydrazine hydrolysis flow reactor. Contains up to about 0.05% by weight ammonium amine and up to about 0.05% by weight nitrile. However, the consumption of excess mineral acid, if the steady state is established, the increased mineral acid / nitrile is maintained during the routine% production operation. Ear ratio can be prevented. Therefore, it is better to use Ηβο, / nitrile molar ratio between about ι · 〇 and about 15 only from the beginning to the establishment of a stable state in the hydrazine hydrolysis flow reactor. Better than = 1.15 and about 1.25 to avoid the production of substandard hydrolysates during the start. When the molar excess added to the amidine hydrolysis flow reactor 16 is between about 0 and about 50%, Between about 15 and about 25%, stoichiometrically reacted with the introduction of amidine hydrolytic flow Such a mole ratio can be obtained with the equivalent amine of the device. After the steady state is established, the I% / lamer ratio can be adjusted again and maintained at a more efficient mole ratio of about 0.99. Between about 1.2 and about 0.9, preferably between about 0.95 and about 105. The rate at which water is fed into the mixer 32 can be increased to avoid when using a molar ratio of 0.004 / nitrile below 10 The organic and aqueous phases are separated in the liquid phase. When H c is used for hydrolysis, in the steady state, the molar ratio of HC1 to nitrile is between about 10 and about 15, preferably about 1.05 and about 1.3. It is more preferably between about 丨 and about 12. When the molar excess of HC1 added to the amine hydrolysis flow reactor 16 is between about 0 and about 50%, preferably between about 5 and about 30% It is more preferably between about 10% and about 20%, which is more than the stoichiometric amount of amidine introduced into the amidine hydrolysis flow reactor. 22 This paper size is applicable to the Chinese National Standard (CNS) A4 specification (210X 297 public meals (please read the notes on the back before filling out this page) D,,-* 0 Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs 495500 A7 B7 V. Description of the invention () v 20; available Kind molar ratio. It has been found that at the beginning, the amidine hydrolysis flow reactor is operated with a high mineral acid / nitrile mole ratio, and the amidine conversion in the amidine hydrolysis flow reactor 16 is improved to a, which darkens the color of the hydrolysate. Despite the stringency of the increased I reaction conditions provided by the high acid / nitrile ratio, it was unexpectedly found that the acid / nitrile mole ratio did not significantly affect the color of the hydrolysate. Moreover, the high acid-to-nitrile molar ratio also allows the amidine hydrolysis flow reactor to operate at lower temperatures during stable operation, thus producing a colored hydrolysate. Printed by the Cooperative of the Central Bureau of Standards, Ministry of Economic Affairs (please read the notes on the back before filling out this page) The hydrolysate leaving the amine hydrolysis flow reactor 16; when measured with a Garner colorimeter, it has about 5 to about The light color between 1 and 0, preferably between about 5 and about 7, is adversely affected by the temperature and residence time of the amidine hydrolysis flow reactor 16 which is excessive in the amidine hydrolysis flow reactor 16. The amidine hydrolysis flow reactor is operated between about 70 ° C and about 120 ° C. When the amidine hydrolytic flow reactor is operated under adiabatic conditions, when the reaction product absorbs adiabatic reaction heat, the temperature rises along the flow path to reach a point (hot spot) on the flow path, and at that point the temperature reaches the platform, and if The situation is not so completely adiabatic, beyond which it can drop slightly. The maximum temperature in the amidine hydrolysis flow reactor is better than about 90 ° and about 20 °. 〇, more preferably between about 90 ° C and about 105 ° C. The completion reaction / watt residence time in the amidine hydrolysis flow reactor is between about 30 minutes and about 1000 minutes, preferably between about 50 minutes and about 70 minutes. When the amidine hydrolysis flow reactor is operated at a temperature higher than that, a darker hydrolysate can be produced. However, the temperature of the amidine hydrolysis flow reactor below 90 ° C can cause incomplete hydrolysis of amidine unless a higher acid to nitrile mole ratio is used. If the residence time exceeds about 20 minutes, the hydrolyzed product can also be deepened. When using acid / moon cream between about 1.1 and about 1.5 in the beginning, Morse ratio This paper size applies Chinese National Standard (CNS) A4 specification (210X297 mm) B7 21 5. Please read the description of the invention first Please fill in this page again on the back of the page and normal operation when the ammonium hydrolysis flow reactor 16 is between about 70 and about 95, preferably between about 80 ° C and about 90 ° C. , Can produce light-colored hydrolysis products. When operating under adiabatic conditions, the temperature of the ammonium hydrolysis flow reactor 1 can be reduced by reducing the temperature of the water stream entering the mixer 32. If I complete the reaction stream before introducing it to the amidine hydrolysis flow reactor, introduce it into the preheater (Figure 0, which can reduce the heat applied to the preheater and reduce the operation of the amidine hydrolysis flow reactor. Alternatively, when When the amidine hydrolysis flow reactor is operated at isothermal temperature, cooling and / or heating may be provided to control the temperature of the amidine hydrolysis flow reactor. When the first 03 but 1136 is also 717 shown in FIG. 3, in the amidine hydrolysis flow reactor Before 16, the operating temperature of the right first CSTR is too high, which can produce dark-colored hydrolysate. When using the above acid / nitrile mole ratio and between about 70 and about 95. It is better than When the second cstr is operated at an intermediate temperature between about 8 ° C and about 9 ° C, a light-colored hydrolysate is produced. The flow reactor most suitable and used in the amidine hydrolysis method of the present invention is a plug flow reactor, It is configured to provide a Picrete number of at least 50 and operate at a PFR operating temperature of at least 90 ° C. The Picrete number is a measure of backmixing of axes within pFR, as defined by:

P e = u L / D 經濟部中央標準局員工消費合作社印製 其中.u -速度，L =長度，及D =軸分散係數。pFR之皮克里 特準數與軸反混合成反比。當皮克里特準數至少5 0，較好約 5 〇與約2 〇 0之間或更多，及駐留時間約4 0與約1 〇 〇分之間， 較佳約5 0與約6 〇分之間，軸反混合有效地減少。 —本發明之PFR 16可為管道pFR或以充填材料充填之充填 巨柱P F R。醯胺水解反應非零級，但已發現反應之動力學充 本紙張尺度朝210X2“· 495500 A7 B7 五、發明説明（22 ) 分有利的，在上述相當適度之駐留時間内可了解高度轉化， 而無實質之壓力降。更特定言之，已發現其中腈已實質地轉 化成醯胺，且於進入插塞流動反應器之流中腊之濃度不高於 約2 %重量比，且於以反應流於擾動流動範圍制度，例如至 少約3 0 0 0，較佳地至少約5 0 0 0之雷諾數之下之速度操作之 管道反應器内；腈濃度各可降至基於Η Μ B A不高於約0.2 % 重量比。若進入反應器之完成反應流之腈/醯胺比於進入 P F R之反應流中不高於約1 %重量比，於反應產物中之醯胺 與腈濃度可各降至不高於約0 . 1 %重量比（基於Η Μ B A)。對 於達此轉化所須之相當適度之駐留時間，P F R反應器可以擾 動速度操作而無過度之壓力降。而且，已發現所須之轉化， 可以適度之操作溫度，於9 0 °C與約1 0 5 °C之間之範圍，達到 ，其不須高壓反應器，且其得以製備具淡色之產物。 經濟部中央標準局員工消費合作社印製 (請先閱讀背面之注意事項再填寫本頁) 替代地，可用充填管柱P F R進行最後之水解反應。藉使用 經結構好之充填，充填管柱反應器可以顯著地低於管道反應 器之速度操作，而無歸因於壁作用或溝流之顯著之反混合。 此充填促進擾動與放射狀混合，並減少軸之反混合，反應流 之死點及溝流，以致所有流體要素於約相同之駐留時間内通 過P F R。因此，充填之管柱反應器可具實質上較大之直徑及 比管道反應器更緊缴之構型。當反應物或產物為高黏度時， 其特別有利。 然而，為本發明之目的，已發現管道反應器，亦即，實質 上無内充填物或其他内流動障礙之延長管狀反應器為佳◦雖 然於管道反應器中，每單位長度可受到些微較高程度之軸反 -25 - 本纸張尺度適用中國國家標準（CNS ) A4規格（210X29*7公釐） 495500 經濟部中央標準局員工消費合作社印繁 A7 B7 五、發明説明（r) W 口，但腈與醯胺水解之動力學已發現以上述適度之駐留時 間及低壓力降，可得以幾乎定量性之轉化。由於於適宜本發 明=法之反應器中，甚至於高速度下遭受低壓力降，所以可 將管迢反應器加以構型，亦即具高L/D(長度直徑）比、以很 同之皮克里特準數，典型地以過量200，且容易地以過量 2000。另外，供本發明方法之管道反應器可構組為相當便利 之、、且成材料，例如襯以鐵弗龍之碳鋼管。供充填管柱反應器 用，眉要外國產之結構材料。管道反應器亦提供更高之撓性 ，因其可以比充填管柱高得多之調氣比操作，後者之轉化陡 降低於所定義之閥速度。於充填管柱中之閥速度達到薄層及 擾動流動之間。 將酿胺水解流動反應器丨6絕緣以補償熱流失至大氣。於醢 胺水解當中產生之反應熱足以供絕熱情況下之自熱操作。有 利地’芫成反應流可於低於醯胺水解之反應溫度下進入醯胺 水解流動反應器。於自熱操作當中，由醯胺水解產生之反應 熱，增加醯胺水解流動反應器内之溫度，減少於其中形成熱 點之可能性。於醯胺水解流動反應器中之溫度侧圖可透過數 種溫度察覺器Ti (圖1-4)沿著反應器之長度測得。水進料溫 度可調整以達醯胺水解流動反應器中所須之溫度侧圖，藉由 在進入混合器3 2以前，以水加熱器增加或減少供應至水進料 流中之熱，形成完成反應流。另外，離開混合器3 2之完成反 應流之溫度可經由使用預熱器34而提高，增加醯胺水解流動 反應器操作溫度。 雖然殘留之腈於醯胺水解流動反應器之入口部分中水解， 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） (請先閲讀背面之注意事項再填寫本頁) 訂 .噃： 495500 A7 B7 五、發明説明（ 24 經濟部中央標準局員工消費合作社印¾ 但腈水^於CSTR 1G中及於腈消失反應區包括向前 區上㈣分及腈水解反應器產物流在向前流動口 26 人稀釋點m流動之區巾充分地進行至完成 解流動反應器中之實質量之萨夕 &gt; 如' 曰I胺水 、 &lt;如 &lt; 水解I反應熱，可能造成於 反應器中之熱點。雖然高如&quot;代至約i2〇t之熱點溫度： 在媪胺水解流動反應器中可耐受，但水解產物於此等情況下 可顯耆變深巴。實質上使在腈水解反應器產物流中之腈消減 ，使得以以較低溫操作醯胺水解流動反應器，提供淺色之完 成水性水解產物。 ^ 醯胺水解流動反應器於約〇與約15 psig之間之壓力下操作 。於醯胺水解流動反應器出口之壓力控制閥提供高至i 5 psig反應，避免當醯胺水解流動反應器於高於1〇5它下操作時 ，於反應器系統中沸騰。 有利地，醯胺水解樣品可自樣品閥s(圖卜4)抽出並經由氣 體層析法分析，決定沿著醯胺水解流動反應器長度之醯胺水 解組成侧圖。一旦建立穩定狀態條件，每8至i 2小時可自醯 胺水解流動反應器出口除去水解產物樣品並定量性分析以監 測產物品質。 離開醯胺水解流動反應器1 6之完成水性水解產物，在貯存 於水解產物平衡槽4 2以前先流過冷卻器。用於本發明之腈水 解反應器，醯胺水解反應器及水解產物平衡槽，藉使用以氮 氣覆蓋及以壓力控制器控制之普通排氣集管於相同之頂壓下 操作，當壓力超過約15 ‘…巧時，藉排氣至烺燒爐集管解除壓 力。排氣可除去揮發性有機硫化合物如甲基硫、甲基二硫、 -27 本纸張尺度適用中國國家標準（CNS ) A4規格（210X 297公釐） f請先閲讀背面之注意事項再填寫本頁) ··裝· 訂 經濟部中央橾率局員工消費合作社印製 495500 A7 B7 五、發明説明（25 ) 及甲基硫醇’其為反應之副產物。蒸氣放射為少於每丨〇〇〇镑 0.5 scf。HMBA產物，通常少於每1〇〇〇碡產物〇3 scf°0 2 scf/1000镑HMBA之射出，甚玉更低為易於達成的，尤其當 只使用單一之CSTR時。 HMBA或其鹽或衍生物，可自水性水解產物回收供用於製 造動物飼料補充物水性水解產物回收。例如於水解產物中之 HMB A可回收供用於液相動物飼料補充物，包含總重量比例 之約8 0 %與約9 8 %重量比之間，較佳地約8 〇 %與約9 5 %重量 比之間之HMB A，及約2 %與約2 0 %重量比之間，較佳地約 5 %與約2 0 %重量比之間之水，及具顏色不高於約8 (當於加 納爾標度上測量時），以甘能-凡斯克（Cannon-Fenske)黏度計 測量於2 5 °C之運動黏度下高於約5 00厘沲，較佳地90厘泡， 且其經受到加速比色計後，於少於約丨5 〇它之任何溫度下， 顯示非放熱亦非吸熱之熱化學作用。 HMBA可自完成之水性水解產物回收，藉由如Heriiandez等 於美國專利第4,9 12,25 7號中所述之NH4〇Η中和（將其併入本 文供參考），或藉由如Ruest等於美國專利第4,524,〇77號中所 述之抽提法（將其併入本文供參考）。 WO 96/01808, W〇 96/01809及WO 96/05 173，將其併入本文 供參考，分別記述製備HMBA之銨鹽、腈之硫酸水解製備 HMBA及藉由薄膜蒸發與溶媒回收，回收hmbA之方法。更特 足言之，WO 96/0 1808記述藉中和完成之水性水解產物製備 按鹽並用溶媒抽提形成含Hmb a之有機相及銨酸鹽水相。該 申請案陳述再將有機相以氨處理形成含HMBA銨鹽之第二個 本纸張尺度適财_家轉（CNS )〜規格（2lQx 297公董） --------·裝！ (請先閱讀背面之注意事項再填寫本頁)P e = u L / D Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economics where .u-speed, L = length, and D = axis dispersion coefficient. The Pickeret number of pFR is inversely proportional to the inverse mixing of the axis. When the Pickeret number is at least 50, preferably between about 50 and about 2000 or more, and the residence time is between about 40 and about 100 minutes, preferably about 50 and about 6 Between 0 minutes, the shaft anti-mixing is effectively reduced. -The PFR 16 of the present invention may be a pipe pFR or a filling pillar P F R filled with a filling material. The hydrazine hydrolysis reaction is non-zero, but it has been found that the kinetics of the reaction is 210X2 "· 495500 A7 B7. V. The description of the invention (22) is advantageous, and the high conversion can be understood within the above-mentioned rather modest residence time. There is no substantial pressure drop. More specifically, it has been found that the nitrile has been substantially converted to amidine, and the concentration of wax in the stream entering the plug flow reactor is not higher than about 2% by weight, The reaction flows in a perturbed flow range regime, such as a pipeline reactor operating at a speed below a Reynolds number of at least about 3 0 0, preferably at least about 5 0 0; the nitrile concentrations can each be reduced to More than about 0.2% by weight. If the nitrile / fluorenamine ratio of the completed reaction stream entering the reactor is not higher than about 1% by weight in the reaction stream entering the PFR, the concentrations of fluorenamine and nitrile in the reaction product may be different. Reduced to no more than about 0.1% by weight (based on Η BA). For a reasonably dwell time required to achieve this conversion, the PFR reactor can operate at a perturbed speed without excessive pressure drop. Moreover, it has been found The required transformation can be moderately manipulated The operating temperature is between 90 ° C and 105 ° C. It does not require a high-pressure reactor and it can produce light-colored products. Printed by the Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs (please Read the notes on the back before filling this page.) Alternatively, you can use the packed column PFR for the final hydrolysis reaction. By using well-structured packing, the packed column reactor can be operated at a significantly lower speed than the pipeline reactor. There is no significant anti-mixing due to wall action or channel flow. This filling promotes perturbation and radial mixing, and reduces anti-axis mixing, reaction flow dead spots and channel flow, so that all fluid elements reside at about the same Passes PFR within time. Therefore, a packed column reactor can have a substantially larger diameter and a tighter configuration than a pipe reactor. It is particularly advantageous when the reactants or products are of high viscosity. However, For the purpose of the present invention, it has been found that a pipe reactor, that is, an extended tubular reactor that is substantially free of internal fillings or other internal flow obstacles is preferred. Although in a pipe reactor, per unit length Affected by a slightly higher degree of axis -25-This paper size applies to Chinese National Standard (CNS) A4 (210X29 * 7 mm) 495500 Employees' Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs, Consumer Cooperatives, India A7 B7 V. Description of the invention (r ) W port, but the kinetics of the hydrolysis of nitrile and amidine has been found to be able to be converted almost quantitatively with the above-mentioned modest residence time and low pressure drop. Because it is suitable for the reactor of the present invention, even high speed It suffers a low pressure drop, so the tube reactor can be configured, that is, with a high L / D (length-to-diameter) ratio, at a very similar Picrete number, typically with an excess of 200, and easily The excess is 2000. In addition, the pipeline reactor used in the method of the present invention can be configured into a relatively convenient and material, such as a carbon steel pipe lined with Teflon. For packing column reactors, foreign structural materials are needed. Pipeline reactors also provide higher flexibility because they can operate with a much higher gas-to-air ratio than packed strings, the latter of which has a sharply reduced conversion to a defined valve speed. The valve speed in the packed string reaches between thin layer and disturbed flow. The amine fermentation hydrolysis reactor 6 is insulated to compensate for heat loss to the atmosphere. The heat of reaction generated during the hydrolysis of amidine is sufficient for autothermal operation under adiabatic conditions. Advantageously, the 'halogenation reaction stream can enter the ammonium hydrolysis flow reactor at a temperature below the reaction temperature of the ammonium hydrolysis. During autothermal operation, the reaction heat generated by the amidine hydrolysis increases the temperature in the amidine hydrolysis flow reactor and reduces the possibility of hot spots forming in it. The temperature profile in the amidine hydrolysis flow reactor can be measured through several temperature sensors Ti (Figures 1-4) along the length of the reactor. The water feed temperature can be adjusted to achieve the required temperature profile in the ammonium hydrolysis flow reactor. Before entering the mixer 32, the water heater is used to increase or decrease the heat supplied to the water feed stream to form Complete the reaction stream. In addition, the temperature of the completed reaction stream leaving the mixer 32 can be increased by using a preheater 34, which increases the operating temperature of the ammonium hydrolysis flow reactor. Although the residual nitrile is hydrolyzed in the inlet part of the ammonium hydrolysis flow reactor, this paper size applies the Chinese National Standard (CNS) A4 specification (210X297 mm) (Please read the precautions on the back before filling this page). ： 495500 A7 B7 V. Description of the invention (24 Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs ¾ But nitrile water ^ in CSTR 1G and disappearance of nitrile The reaction zone includes decantation on the forward zone and the product flow of the nitrile hydrolysis reactor The front flow port has 26 dilution points, and the flow zone is fully carried out until the solid mass in the flow-resolving reactor has been completed, such as' I amine water, &lt; such as &lt; Hydrolysis I reaction heat, which may cause Hotspots in the reactor. Although the hotspot temperature is as high as &quot; substitute to about i20t: tolerable in the amidine hydrolysis flow reactor, the hydrolysate can be significantly deeper in these cases. In essence The nitrile in the product stream of the nitrile hydrolysis reactor is reduced so that the ammonium hydrolysis flow reactor is operated at a lower temperature to provide a light-colored, complete aqueous hydrolysate. The amidine hydrolysis flow reactor is between about 0 and about 15 psig. Pressure between The pressure control valve at the outlet of the amidine hydrolysis flow reactor provides a reaction up to i 5 psig to avoid boiling in the reactor system when the amidine hydrolysis flow reactor is operated above 105. Ground, the amidine hydrolysis sample can be drawn from the sample valve s (Figure 4) and analyzed by gas chromatography to determine the side profile of the amidine hydrolysis composition along the length of the amidine hydrolysis flow reactor. Once a steady state condition is established, each From 8 to i 2 hours, the hydrolysate sample can be removed from the outlet of the amidine hydrolytic flow reactor and quantitatively analyzed to monitor the product quality. The aqueous hydrolysate leaving the amidine hydrolytic flow reactor 16 is completed and stored in the hydrolysate equilibrium tank 4 2 flowed through the cooler before. The nitrile hydrolysis reactor, the amidine hydrolysis reactor and the hydrolysate balance tank used in the present invention, by using ordinary exhaust manifolds covered with nitrogen and controlled by a pressure controller on the same top Depressing operation, when the pressure exceeds about 15 '... coincidentally, exhaust the pressure to the header of the sintering furnace to relieve the pressure. The exhaust can remove volatile organic sulfur compounds such as methyl sulfur, methyl disulfide,- 27 This paper size applies to China National Standard (CNS) A4 (210X 297 mm) f Please read the notes on the back before filling out this page) ··· · Bookmark Printed by the Central Government Bureau of the Ministry of Economic Affairs and Consumer Cooperatives 495500 A7 B7 V. Description of the invention (25) and methyl mercaptan 'It is a by-product of the reaction. Vapor emission is less than 0.5 scf per 1000 pounds. The HMBA product is usually less than 0.3 scf ° 2 scf per 1000 pounds of HMBA product, and even lower jade is easier to achieve, especially when only a single CSTR is used. HMBA, or a salt or derivative thereof, can be recovered from the aqueous hydrolysate for recovery of the aqueous hydrolysate used in the manufacture of animal feed supplements. For example, HMB A in the hydrolysate can be recovered for use in liquid animal feed supplements, comprising between about 80% and about 98% by weight of the total weight ratio, preferably about 80% and about 95% by weight. HMB A between weight ratio, and water between about 2% and about 20% by weight, preferably between about 5% and about 20% by weight, and having a color not higher than about 8 (when When measured on the Garner scale), measured with a Cannon-Fenske viscometer at a kinematic viscosity at 25 ° C above about 500 centistokes, preferably 90 centimeters bubble, and its After being subjected to an accelerated colorimeter, it exhibits non-exothermic or endothermic thermochemical effects at any temperature less than about 50 ° C. HMBA can be recovered from the completed aqueous hydrolysate, by neutralization with NH4〇Η as described in Heriiandez equal to US Patent No. 4,9 12,25 7 (incorporated herein by reference), or by means such as Ruest Equivalent to the extraction method described in US Patent No. 4,524,077 (which is incorporated herein by reference). WO 96/01808, W〇96 / 01809, and WO 96/05 173, which are incorporated herein by reference, describe the preparation of HMBA ammonium salt, nitrile hydrolysis of sulfuric acid to prepare HMBA, and thin film evaporation and solvent recovery to recover hmbA Method. More specifically, WO 96/0 1808 describes the preparation of an aqueous hydrolysate completed by neutralization. The organic phase containing Hmb a and the aqueous ammonium salt phase are formed by extraction with a salt and a solvent. The application states that the organic phase is then treated with ammonia to form a second paper with HMBA ammonium salt. This paper is suitable for household use (CNS) ~ specifications (2lQx 297). !! (Please read the notes on the back before filling this page)

、1T 經濟部中央標準局—工消費合作社印製 495500 A7 B7 五、發明説明（26) 水相及有機溶媒相，自第二水相回收HMB A之銨鹽。據稱藉 NaOH處理銨酸鹽溶液回收氨，形成NaC1*Na2S〇4，其更易 於處理。W0 96/01809記述濃HMBA2形成藉由有機溶媒抽 提完成之水性硫酸水解產物形成含H M B A之有機相及水相並 蒸發含HMBA之有機相提供含少於4重量％水之濃9 8 %HMBA 。WO 96/05 173記述回收HMBA，藉由蒸發完成之水性硫酸水 解產物得實用上無水、含HMB A之鹽殘留物，以有機溶媒處 理此殘留物形成懸浮液，自懸浮液分離固體形成含Η μ B A之 落液’自含HMB A之溶液除去有機溶媒得hmBA殘留物，加 水至Η Μ B A殘留物形成Η Μ B A溶液。 先前技藝包括各種回收HMBA或HMBA鹽產物之其他方 法，包括至少數種已在商業上實用者。任何方法可由精於此 道者選擇供自水解產物回收HMBA產物，根據本發明自最初 製備水性水解產物自然產生好處。根據本發明製造之水解產 物高度適宜用於供回收產物酸或鹽之任何操作方法。 HMBA之鹽亦可自完成之水性水解產物製備，藉由 Cummins等於美國專利第4,310,69〇，Nufer美國專利第 3,272,860號，及 Blake等，美國專利第 2,938,053 及 2,745,745 號所述方法’將其併入本文供參考。Cummins記述HMBA之 鈣鹽之製備，藉由將含HMBA之水性水解產物與NaCl與C a 鹽之混合物混合，將此混合物與N a 〇 η反應，所得溶液與 Ca(OH)2之漿反應形成HMBA之#5鹽，再分離HMBA之躬鹽。 Blake等記述形成HMBA之銨及鈣鹽，藉由加Ca(〇H)2中和於 含HMBA之水性水解產物中之h2S〇4&amp;(NH4)2S〇4，過濾 本纸張尺度適用中國國家標準（CNS ) A4規格（210X 297公釐） (請先閲讀背面之注意事項再填寫本頁) 、11 經濟部中央標準局員工消費合作社印裂 495500 A7 B7 五、發明説明（27) 混合物，除去CaS04，濾液與Ca(OH)2漿反應，過濾混合 物除去CaS04，乾燥滤液回收含HMBA之躬鹽、HMBA之铵 鹽及少量CaS〇4與水之組合物。Blake等亦記述製備HMBA之 鈣鹽，藉將CaC03與含HMBA之水性水解產物、h2S〇4與 (1^^14)2304反應形成HMBA之銨鹽及CaS04，分離CaS04, 將剩下之液體與Ca(OH)2&amp;應形成HMBA之鈣鹽及NH4OH，加 熱混合物分解NH4〇H並驅除NH3，過濾所得混合物除去 CaS〇4&amp;Ca(〇H)2，自混合物蒸發水形成HMBA #5鹽之濃 漿，過濾此漿並乾燥濾餅得HMBA之鈣鹽。Nufer記述 HMBA鈣鹽之形成，藉由混合HMBA與乙二醇之單烷基醚， 將混合物與C a 0 -乙二醇醚漿反應，過濾所得之漿，乾燥濾 餅回收HMBA之鈣鹽。其他形成HMBA之鹽或衍生物之方法 為所熟知，且包括製備HMBA之鹽之方法，藉由金屬氧化物 或其他鹼之直接反應，及如美國專利第4,855，495，4,579,962 及4,335,357中所述（將其併入本文供參考）分離或部分分離 HMBA。 圖3說明本發明具體實施例，其中醯胺水解反應於醯胺水 解流動反應器1 6及醯胺水解流動反應器之第二C s T R 3 6上 游中進行。第二C S T R使能容易處理黏性醯胺，徹底混合醯 胺水解混合物與稀釋水及第二C S T R内之礦酸流之任何分開 之部分’及控制完成反應流之溫度，當後者引入醯胺水解流 動反應器時，造成相當低黏度之完成反應流。腈水解反應於 C S T R 1 〇中發生，將離開c S T R 1 0之腈水解反應器產物流 、水進料流及礦酸流之任何分開部分，經由管線2 〇引入第二 本纸張尺度適用中國國家標隼（CNS ) A4規格（210X 297公楚） (請先閱讀背面之注意事項再填寫本頁) 訂 495500 經濟部中央標準局員工消費合作社印裝 A7 B7 五、發明説明（28) ^ CSTR 36，於其中實質部分之醯胺水解成HMBA。為本發明 又目的，當多於5 0 %重量比，較好約5 〇 %與約8 〇 %重量比之 間I醯胺水解成HMBA時，實質部分之醯胺水解。醯胺水解 混合物含於第二CSTR 36内之駐留時間為約30分與約so分 之間，較好為約40分與約60分之間。於第二CStr 36中之 駐留時間之計算藉由第二CSTR之液體體積除以離開第二 CSTR之完成反應流之體積流動速率。第二cstr中之液體 含量可藉重力溢流至醯胺水解流動反應器丨6或較好地藉如前 述之正的含量控制來控制。 ’ 醯胺水解反應於第二C S T R中，於約7 0 °C與約1 2 0 °C間， 較好約90°C與約l〇5°C間之溫度，及約0與約15 psig間之 總壓力下開始。轉化至Η Μ B A之增進一般藉於提高溫度於约 90 °C與約110。(：之間操作第二CSTR。第二CSTR 36典型地 供以反應流加熱套層以維持操作溫度。若溫度察覺器T丨（圖3 ) 檢測在騷胺水解流動反應器内之熱點，則可降低第二CSTR之 操作溫度。 醯胺水解反應實質上於第二CSTR中進行，產生完成反應 流，其引入醯胺水解流動反應器丨6。完成反應流含至少約 3 0重量％ HMB A，至少約1 7重量％銨鹽，至少約1 5重量％水 ，高至約1 0重量％醯胺及高至約1重量％腈。較佳地，完成 反應流含約3 0與約5 0重量％之間Η Μ B A，約1 7與約3 0重量 %之間銨鹽，約1 5與約3 0重量％之間水，約1與約6重量％之 間醯胺及高至約0. 1重量％腈。當用H2S〇4時，完成反應流 含至少約3 1重量％ Η Μ B A，至少約2 0重量％銨鹽，如 本纸張尺度適用中國國家標準（CNS ) Α4規格（210X297公釐） ί請先閲讀背面之注意事項再填寫本頁} 訂 經濟部中央標準局員工消費合作社印製 495500 A7 B7____ 五、發明説明（29 ) NH4HS04或（NH4)2S〇4，至少約20重量0/〇水，高至約5重 量％醯胺及高至約1重量％腈，且較佳地約3 2與約4 2重量％ 之間Η Μ B A，約2 0與約3 0重量％之間兹鹽，約2 2與約3 0重 量％之間水，約2與約4重量％之間醯胺及高至約0 . 1重量％ 腈。當使用H C 1，完成反應流含至少約4 5重量％ Η Μ B A，至 少約1 7重量％N H4 C 1，至少約1 5重量％水，高至約8重量％ 醯胺及高至約1重量％腈，及較好約4 5與約5 0重量％之間 HMB A，約1 7與約1 9重量％之間NH4C1，約1 8與約22重量 %之間水，約2與約6重量％之間醯胺及高至約〇 . 1重量％腈 ’醯胺水解則於如對上面圖i所述之醯胺水解流動反應器内 完成。 圖4為圖3中所示方法之較佳、經修飾之方法。腈水解反應 器產物流於水解反應器出口與第二C S T R之間之駐留時間， 延長，如上述有關圖2使殘留之腈消滅。當腈水解反應器產 物流以水及/或礦酸之任何分開部分稀釋，形成醯胺水解流 其進料於第二CSTR。醯胺水解於第二CSTR中發生產生待 輸送至醯胺水解流動反應器之完成反應流。 固5與6 ά兒明本發明較佳具體實施例，其中可採用。$ τ r 10於圖1中所示之方法，通過4接受濃H.2S〇4、ΗΜΒΝ及水 ，料成。ΗΜΒΝ與水進料流直接進料至CSTR。濃 或、；循環、、泉中與循環流混合或直接進料至C S T R。濃Η 2 s〇4 流可直接進料至CSTR，但較好經由管線“進料至熱交換器 (、循裒、、泉下游，致使濃Η2 S〇4流在回至c s T R 1 〇以前與 水性水解混合物徹底混合。當所有之流回時進料至cstr， -32 - ) A4規格（210X29^^ --- (請先閱讀背面之注意事項再填寫本頁) 訂*丨 495500 A7 B7 30 五、發明説明（ 腈水解反應器發生時，Η4〇4於反應器中稀釋，於任一情形 中，不須分開之酸稀釋系統，而避免有關之安置及維護^用 。引入水性水解混合物之濃HJCU具約70%重量比與約99% 重量比I間之強度，較好約9 〇 %重量比與約98 %重量比之間 。CSTR 10内之水性水解混合物具約5〇%重量比與約 重量比之間之強度，較好約6〇%重量比與約7〇%重量比之間&quot; 足H2 S Ο# (基於無有機物）。將水性水解混合物以高猶環速率 連續用泵抽通過外面熱交換器24，除去反應熱。泵22使水 性水解混合物於C S T R 1 〇與外面之熱交換器2 4之間循環， 其中藉輸送至冷卻器除去反應之放熱之熱。當濃H2S〇4直接 進料至反應器10時，熱交換器亦除去由H2S〇4之稀釋所產 生之熱。 本發明方法提供製備HMBA之改良方法。用此種方法可達 鬲生產力，因其可連續操作，提供比習用批次方法更大之物 料通過量。此方法顯著降低與批次反應有關之主要及維護費 用’例如藉消除當Η2 S Ο 4引入反應器而無預先稀釋時，分開 之HdO4稀釋之須要。此方法與習用批次水解系統比較時， 亦提供改進之控制反應條件。此改進之控制水解反應，使能 衣k 一致足向品質之水解產物。此方法之排氣放射與習用批 次系統比較時，顯著降低，由於消除槽之充填與出空及於非 穩定狀態條件下之操作。 下面貫例提供說明本發明之較佳具體實施例及用途，而非 意指限制本發明，除非於附加之申請專利範圍中另外之陳述 ·1------1T----- (請先閲讀背面之注意事項再填寫本頁) 經濟部中央標準局員工消費合作社印製 495500 Α7 Β7 五、發明説明（31 ) 實例1 如圖7中所示之實驗室規模之設備用來証明連續水解方法 〇 腈（2 -經基-4 -甲硫丁腊）及6 5 %水性H 2 s〇4分別以1 〇 i克/ 分及1 . 1 6 7克/分之速率連續以泵抽入具液體體積4 2 . ^毫升 之徹底攪拌之再循環反應器46中。反應溫度經由於再循環反 應圈上提供之冷卻套層控制於65T：，後者除去由腈水解反應 釋放之熱。泵4 8使反應器圈中之水性水解混合物再循環。基 於總進料速率，反應器46之駐留時間為25.4分。於反應器 出口 ’在穩定狀況中週期性地除去樣品。所有採樣口於圖7 中足名為S。以氣體層析法分析樣品，決定離開反應器之水 解產物。氣體層析法結果顯示實務上所有腈進料水解並轉化 成醯胺，及約1 5 %之形成之醯胺再於此反應器中水解形成 Η Μ B A，最後之水解產物。 經濟部中央標準局員工消費合作社印製 離開再循環反應器4 6之富含醯胺之水解產物連續進料於第 —再循環反應器5 0 ’其類似於第一再循環反應器* 6，但具 液體禮積1 1 9.3毫升。〇 . 5 7克/分之水進料亦引入第二個徹 底邊摔之反應器，其提供52·6分之駐留時間。此反應器圈之 溫度經由再循環反應圈上提供之加熱流體套層維持於丨〇 2。〇 。系52使反應器圈内之水解產物再循環。自反應器5〇得出 口樣品’以氣體層析法分析，顯示進料醯胺約9 4.5 %水解成 ΗΜΒΑ。 自第二再循環反應器5〇出來之物連續進入最後之完成反應 备’其由一組4個鐵弗龍管子線圈5 4所組成。完成反應器置 本紙張尺度適用中國國家標隼（CNS ) Α4規格（210 X 29*7公瘦） 495500 A7 D-7 32 五、發明説明（ 於定溫烘箱5 6内，防止孰沪生，冃网， 、 。 ’、、、儿失又周圍，如此維持整個反應器 、、桌圈5 4於1 0 2 C之溫户。屮笔、w n r … 又此寺洫疋P F R具總液體體積9 1毫升 、’應之4 j刀之駐留時間被設計來確保醯胺水解之完全。於 此情形’酿胺水解於第三線圈58之出口完成。得自pfr出口 (水解產物經分析含35%HMBA ’其餘物質為水及副產品 NH4HS〇4。水解產物之顏色，基於加納爾色標為6_7。 實例2 - 9 4見例1所用之相同之連績實驗室規模設備亦用來測定駐 胃時間與反應溫度對轉化之影響。各樣品之酸對腈進料比維 持於約1 . 0莫耳化學計量比。於各再循環反應器之出口及各 PFR線圈之端，於穩定狀況時移除樣品（於下表卜8中分別指 π為RECIRC及S)，以氣體層析法分析，決定離開反應器或線 圈之水解混合物組成。於各反應器或線圈中之水解混合物組 成及溫度與駐留時間示於下表卜8，其餘產物包括水及 nh4hso4。結果，基於各種進料速度（丨〇1_2 33克/分，腈進 料）及溫度（60-65 °C供腈水解及90_12〇它供醯胺水解）說明增 加駐留時間及反應溫度，改進兩水解反應之轉化，然而，增 加溫度亦造成產物顏色之增加。 實例2 腈以1.01克/分進料至第一再循環反應器，連同115克/分 6 4 · 7 % H 2 S〇4 ’得〇 . 9 9酸/腈莫耳比。水進料亦以〇 5 5克/ 分引入第二再循環反應器。各反應器或線圈中之水解混合物 組成及溫度與駐留時間示於下表1。 表1 -35 本纸張尺度適用中國國家標準（CNS ) Α4規格（210X 297公釐） (請先閲讀背面之注意事項再填寫本頁) 訂 經濟部中央標準局員工消費合作社印製 495500 A7 B7 五、發明説明（ 33Printed by 1T Central Standards Bureau of the Ministry of Economic Affairs—Industrial and Consumer Cooperatives 495500 A7 B7 V. Description of the invention (26) Water phase and organic solvent phase. The ammonium salt of HMB A is recovered from the second water phase. It is said that the ammonia is recovered by treating the ammonium salt solution with NaOH to form NaC1 * Na2S04, which is easier to handle. W0 96/01809 describes the formation of concentrated HMBA2. The aqueous sulfuric acid hydrolysate completed by extraction with an organic solvent forms an organic phase containing HMBA and an aqueous phase and evaporates the organic phase containing HMBA. Provides a concentrated 98% HMBA with less than 4% by weight of water. . WO 96/05 173 describes the recovery of HMBA, and the practically anhydrous, HMB A-containing salt residue is obtained by evaporation of the aqueous sulfuric acid hydrolyzed product. The residue is treated with an organic solvent to form a suspension, and the solid is separated from the suspension to form rhenium. The solution of μ BA 'was removed from the solution containing HMB A to obtain the hmBA residue, and water was added to the BA BA residue to form a Μ BA solution. Previous techniques include various other methods for recovering HMBA or HMBA salt products, including at least a few that are already commercially available. Any method can be selected by those skilled in the art to recover the HMBA product from the hydrolysate, and according to the present invention there is a natural benefit from the initial preparation of the aqueous hydrolysate. The hydrolysate produced according to the present invention is highly suitable for any method of operation for recovering the product acid or salt. The salt of HMBA can also be prepared from the completed aqueous hydrolysate. Cummins are equal to US Patent No. 4,310,69, Nufer US Patent No. 3,272,860, and Blake et al., US Patent Nos. 2,938,053 and 2,745,745. This article is for reference. Cummins describes the preparation of the calcium salt of HMBA, by mixing an HMBA-containing aqueous hydrolysate with a mixture of NaCl and Ca salt, and reacting this mixture with Nao, the resulting solution is reacted with a slurry of Ca (OH) 2 to form # 5 salt of HMBA, and then separate the salt of HMBA. Blake et al. Described the formation of ammonium and calcium salts of HMBA, by adding Ca (〇H) 2 to neutralize h2S〇4 &amp; (NH4) 2S〇4 in HMBA-containing aqueous hydrolysate, filtering this paper is applicable to China Standard (CNS) A4 specification (210X 297 mm) (Please read the precautions on the back before filling out this page), 11 Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs 495500 A7 B7 V. Description of the invention (27) Mixture, except CaS04, the filtrate is reacted with Ca (OH) 2 slurry, the mixture is filtered to remove CaS04, and the filtrate is dried to recover the composition containing HMBA salt, ammonium salt of HMBA and a small amount of CaS04 and water. Blake et al also described the preparation of calcium salt of HMBA, by reacting CaC03 with HMBA-containing aqueous hydrolysate, h2S04 and (1 ^^ 14) 2304 to form ammonium salt of HMBA and CaS04, separating CaS04, and separating the remaining liquid with Ca (OH) 2 &amp; should form HMBA calcium salt and NH4OH, heat the mixture to decompose NH4OH and drive out NH3, filter the resulting mixture to remove CaS04 & Ca (〇H) 2, evaporate water from the mixture to form HMBA # 5 salt Thick slurry. Filter the slurry and dry the filter cake to obtain the calcium salt of HMBA. Nufer described the formation of HMBA calcium salt. The HMBA was mixed with the monoalkyl ether of ethylene glycol, the mixture was reacted with Ca 0 -glycol ether slurry, the resulting slurry was filtered, and the filter cake was dried to recover the calcium salt of HMBA. Other methods for forming HMBA salts or derivatives are well known and include methods for preparing HMBA salts, by direct reaction with metal oxides or other bases, and as described in U.S. Patent Nos. 4,855,495, 4,579,962 and 4,335,357 (Incorporated herein for reference) Isolation or partial isolation of HMBA. Fig. 3 illustrates a specific embodiment of the present invention, in which the amidine hydrolysis reaction is performed upstream of the amidine hydrolysis flow reactor 16 and the second Cs T R 3 6 of the amidine hydrolysis flow reactor. The second CSTR enables easy handling of viscose amidines, thoroughly mixes the amidine hydrolysis mixture with dilution water and any separate parts of the mineral acid stream in the second CSTR 'and controls the temperature of the completed reaction stream when the latter introduces amidine hydrolysis When the reactor is flowed, a relatively low-viscosity complete reaction stream is created. The nitrile hydrolysis reaction takes place in CSTR 10, and any separate part of the product stream, water feed stream and mineral acid stream leaving the nitrile hydrolysis reactor of c STR 10 will be introduced via pipeline 20. The second paper size applies to China National Standard (CNS) A4 specification (210X 297) (Please read the notes on the back before filling out this page) Order 495500 Printed on the A7 B7 of the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs 5. Description of the invention (28) ^ CSTR 36. Hydrolysis of amidine in a substantial portion thereof to HMBA. For the purpose of the present invention, when more than 50% by weight, preferably between about 50% and about 80% by weight, of the amidine is hydrolyzed to HMBA, a substantial portion of the amidine is hydrolyzed. The residence time of the amidine hydrolysis mixture contained in the second CSTR 36 is between about 30 minutes and about 60 minutes, preferably between about 40 minutes and about 60 minutes. The dwell time in the second CStr 36 is calculated by dividing the liquid volume of the second CSTR by the volume flow rate of the completed reaction stream leaving the second CSTR. The liquid content in the second cstr can be controlled by gravity overflow to the ammonium hydrolysis flow reactor 6 or better by positive content control as described above. '' Amidine hydrolysis reaction in a second CSTR at a temperature between about 70 ° C and about 120 ° C, preferably between about 90 ° C and about 105 ° C, and between about 0 and about 15 psig Begin under total pressure. The increase in conversion to BM B A is generally achieved by increasing the temperature to about 90 ° C and about 110. (: The second CSTR is operated in between. The second CSTR 36 is typically supplied with a reaction stream heating jacket to maintain the operating temperature. If the temperature sensor T 丨 (Figure 3) detects a hot spot in the hydrolyzed flow reactor, then The operating temperature of the second CSTR can be lowered. The amidine hydrolysis reaction is substantially performed in the second CSTR to generate a complete reaction stream, which is introduced into the amidine hydrolysis flow reactor. 6. The complete reaction stream contains at least about 30% by weight HMB A , At least about 17% by weight ammonium salt, at least about 15% by weight water, up to about 10% by weight amidine and up to about 1% by weight nitrile. Preferably, the completed reaction stream contains about 30 and about 5 Between 0% by weight BA Μ BA, between about 17 and about 30% by weight ammonium salt, between about 15 and about 30% by weight water, between about 1 and about 6% by weight fluoramine and up to About 0.1% by weight of nitrile. When using H2S04, the complete reaction stream contains at least about 31% by weight of BABA, and at least about 20% by weight of ammonium salt. If this paper is scaled to the Chinese National Standard (CNS) Α4 specification (210X297 mm) ί Please read the precautions on the back before filling out this page} Set the staff consumption of the Central Standards Bureau of the Ministry of Economic Affairs 495500 A7 B7____ printed by the company V. Description of the invention (29) NH4HS04 or (NH4) 2S04, at least about 20% by weight 0 / 〇 water, up to about 5% by weight amidine and up to about 1% by weight nitrile, and more than Preferably between about 32 and about 42% by weight Η BA, between about 20 and about 30% by weight salt, between about 22 and about 30% by weight water, about 2 and about 4% by weight % Fluorene and up to about 0.1% by weight nitrile. When using HC 1, the completed reaction stream contains at least about 45% by weight Η Μ BA, at least about 17% by weight N H4 C 1, at least about 15 Weight percent water, up to about 8 weight percent amidine and up to about 1 weight percent nitrile, and preferably between about 45 and about 50 weight percent HMB A, between about 17 and about 19 weight percent NH4C1 , Between about 18 and about 22% by weight of water, between about 2 and about 6% by weight of amidine and up to about 0.1% by weight of nitrile 'amidine is hydrolyzed as described above for iamine The hydrolysis flow reactor is completed. Figure 4 is a better and modified method of the method shown in Figure 3. The residence time of the product of the nitrile hydrolysis reactor flowing between the outlet of the hydrolysis reactor and the second CSTR is extended, as described above. Related to Figure 2 The nitrile is eliminated. When the nitrile hydrolysis reactor product stream is diluted with any separate portion of water and / or mineral acid to form the ammonium hydrolysate stream, it is fed to the second CSTR. The ammonium hydrolysate occurs in the second CSTR to produce and is delivered to The complete reaction stream of the ammonium hydrolysis flow reactor is shown in Figs. 5 and 6. The preferred embodiment of the present invention can be used. $ Τ r 10 The method shown in Fig. 1 is used to accept concentrated H.2S. 〇4, ΗΜΒΝ and water, material. The BMNB and the water feed stream are fed directly to the CSTR. Concentrated or, circulated, mixed with the circulating stream, or fed directly to CSTR. The concentrated Η 2 s〇4 stream can be directly fed to the CSTR, but it is preferably fed to the heat exchanger (, circulation, and downstream of the spring via a pipeline), so that the concentrated Η2 S〇4 stream is returned to cs TR 1 〇 Thoroughly mix with the aqueous hydrolysis mixture. When all flow back, feed to cstr, -32-) A4 size (210X29 ^^ --- (Please read the precautions on the back before filling this page) Order * 495500 A7 B7 30 V. Description of the invention (When the nitrile hydrolysis reactor occurs, Η44 is diluted in the reactor. In any case, it is not necessary to separate the acid dilution system, and to avoid the related installation and maintenance. Introduce the aqueous hydrolysis mixture The concentrated HJCU has a strength between about 70% by weight and about 99% by weight I, preferably between about 90% by weight and about 98% by weight. The aqueous hydrolysis mixture in CSTR 10 has about 50% by weight The strength between the weight ratio and the weight ratio is preferably between about 60% by weight and about 70% by weight. "H2S 0 # (based on no organic matter). The aqueous hydrolysis mixture is continuous at a high ring rate. The heat of reaction is removed by pumping through the outer heat exchanger 24. The pump 22 applies the aqueous hydrolysis mixture to the CSTR 10 and the external heat exchanger 24, which is transported to the cooler to remove the exothermic heat of the reaction. When concentrated H2S04 is directly fed to the reactor 10, the heat exchanger also removes H2S〇4 The heat generated by the dilution. The method of the present invention provides an improved method for preparing HMBA. With this method, the productivity can be achieved, because it can be continuously operated and provides a greater throughput of materials than the conventional batch method. This method significantly reduces the Major and maintenance costs related to batch reactions, such as by eliminating the need for separate HdO4 dilution when Η2 S Ο 4 is introduced into the reactor without pre-dilution. This method also provides improved control when compared to conventional batch hydrolysis systems Reaction conditions. This improved controlled hydrolysis reaction enables uniformly-oriented hydrolysates of uniform quality. The exhaust emission of this method is significantly reduced when compared with conventional batch systems, due to the elimination of tank filling and emptying, and non-standard Operation under steady-state conditions. The following examples provide preferred embodiments and uses of the present invention, but are not intended to limit the present invention, except in the scope of additional patent applications. Other statements in 1 ------ 1T ----- (Please read the notes on the back before filling this page) Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs 495500 Α7 Β7 V. Description of Invention (31 ) Example 1 A laboratory-scale apparatus as shown in FIG. 7 was used to demonstrate the continuous hydrolysis process. Nitrile (2-mercapto-4 -methylthiobutane) and 65% aqueous H 2 s0 4 were each 1 ％. Pumped continuously at a rate of 1 g / min and 1.1 67 g / min into a thoroughly stirred recirculation reactor 46 with a liquid volume of 4 2. ^ ml. The reaction temperature was controlled to 65T via a cooling jacket provided on the recirculation reactor, which removed the heat released by the nitrile hydrolysis reaction. Pump 48 recycles the aqueous hydrolysis mixture in the reactor loop. Based on the total feed rate, the residence time of reactor 46 was 25.4 minutes. Samples are periodically removed at the reactor outlet 'in a steady state. All sampling ports are named S in Figure 7. The sample was analyzed by gas chromatography and the hydrolysate leaving the reactor was decided. The gas chromatography results showed that in practice all the nitrile feedstocks were hydrolyzed and converted to amidine, and about 15% of the amidine formed was then hydrolyzed in this reactor to form ΜMBA, the final hydrolysis product. The Consumers Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs printed the hydrazine-rich hydrolysate leaving the recycle reactor 4 6 to be continuously fed to the first-recycle reactor 50 'which is similar to the first recycle reactor * 6, But with liquid gift 1 1 9.3 ml. A water feed of 57 g / min was also introduced into a second thoroughly dropped reactor, which provided a dwell time of 52.6 minutes. The temperature of this reactor ring was maintained at 0 2 via the heating fluid jacket provided on the recirculation reaction ring. 〇. Line 52 recycles the hydrolysate in the reactor loop. A sample from the reactor 50 was analyzed by gas chromatography, which showed that about 94.5% of the feed amine was hydrolyzed to 水解 ΜΒΑ. The contents from the second recycling reactor 50 continuously enter the final completion reaction device, which is composed of a group of four Teflon tube coils 54. The paper size of the finished reactor is set to the Chinese National Standard (CNS) Α4 size (210 X 29 * 7 male thin) 495500 A7 D-7 32 V. Description of the invention (in a constant temperature oven 5 6 to prevent shanghai students,冃 Net,,. ',,, and children are around, so to maintain the entire reactor, table ring 5 4 to 1 0 2 C. 屮 pen, wnr ... and this temple 洫 疋 PFR has a total liquid volume of 9 The dwell time of 1 ml, 'ying 4 knives is designed to ensure the complete hydrolysis of amidine. In this case, the hydrolysis of amine is completed at the exit of the third coil 58. It is obtained from the exit of pfr (the hydrolysis product contains 35% HMBA 'The remaining substances are water and by-products NH4HS〇4. The color of the hydrolysate is 6-7 based on the Garner color scale. Examples 2-9 4 See the same continuous laboratory-scale equipment used in Example 1 for measuring gastric residence time And the effect of reaction temperature on the conversion. The acid to nitrile feed ratio of each sample was maintained at about 1.0 Molar stoichiometric ratio. At the outlet of each recycle reactor and the end of each PFR coil, it was removed at steady conditions Samples (referred to as π RECIRC and S respectively in Table 8 below), gas chromatography The composition of the hydrolysis mixture leaving the reactor or coil was determined by method analysis. The composition, temperature and residence time of the hydrolysis mixture in each reactor or coil are shown in Table 8 below. The remaining products include water and nh4hso4. The results are based on various feeds The speed (丨 〇1_2 33 g / min, nitrile feed) and temperature (60-65 ° C for nitrile hydrolysis and 90-12 ° for amidine hydrolysis) indicate that increasing the residence time and reaction temperature, improving the conversion of the two hydrolysis reactions, however , Increasing the temperature also results in an increase in the color of the product. Example 2 Nitrile was fed to the first recycle reactor at 1.01 g / min, together with 115 g / min 6 4 · 7% H 2 S〇4 'to obtain 0.99 acid / Nitrile mole ratio. The water feed was also introduced into the second recycle reactor at 0.055 g / min. The composition, temperature and residence time of the hydrolysis mixture in each reactor or coil are shown in Table 1 below. Table 1 -35 This paper size applies to Chinese National Standard (CNS) A4 specification (210X 297 mm) (Please read the precautions on the back before filling this page) Ordered by the Central Consumers Bureau of the Ministry of Economic Affairs to print 495500 A7 B7 V. Description of the invention (33

RECIRC-I RECIRC-II S1 S2 S3 溫度(°C) 64 駐留時間(分） 25 103 53 104 11 104 11 104 11 水解混合物組成(重量％) 腈 0.11 痕量 痕量 痕量 痕量 HMBA 8.3 34 33 35 醯胺 38 2.7 0.70 0.12 0.03 水解產物顏色:6-7基於加納爾色標 請 先 閲 讀 背 面 冬 % 事 項 再 填 寫 本 頁 經濟部中央標準局員工消費合作社印褽 實例3 月青以1.01克/分進料至第一再循環反應器，連同1.16克/分 6 4.7%H2S〇4 ，得0.99酸/腈莫耳比。水進料亦以0.54克/ 分引入第二再循環反應器。各反應器或線圈中之水解混合物 組成及溫度及駐留時間示於下表2。 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） 495500 A7 B7 34 五、發明説明（ 表2 RECIRC-I RECIRC-II S1 S2 S3 溫度(°C) 62 駐留時間(分） 25 98 53 102 11 102 11 102 11 水解混合物組成(重量％) 腈 0.22 0.05 0,05 痕量 0.035 HMBA 7.8 33 38 38 38 醯胺 35 3.5 0.81 0.18 0.09 請 先 閔 讀 背 面 冬 意 事 項 再 填 寫 本 頁 水解產物顏色:5-6基於加納爾色標 溫度(°C) 65 駐留時間(分) 18 105 36 105 7.7 105 7.7 105 7.7 經濟部中央標準局員工消費合作社印製 水解混合物組成(重量％) 腈 0.36 0.06 0.05 痕量 痕量 HMBA 6.7 34 36 37 38 醯胺 39 3.1 0.79 0.28 痕量 水解產物顏色:6-7基於加納爾色標 本纸張尺度適用中國國家標準（CNS ) A4規格（210X 291 2 3 4公釐） 37 - 1 實例4 2 腈以1.4 3克/分進料至第一再循環反應器，連同1 . 6 5克/分 3 4.7 % H 2 S〇4，得0.9 9酸/腈莫耳比。水進料亦以0.7 6克/ 分引入第二再循環反應器。各反應器或線圈中之水解混合物 組成及溫度及駐留時間示於下表3。 表3 4 RECIRC-I RECIRC-II SI S2 S3 495500 A7 B7 五、發明説明（35) 實例5 (請先閲讀背面之注意事項再填寫本頁) 腈以1.45克/分進料至第一再循環反應器，連同1 . 69克/分 ，6 4.7%H2S04，得1.0酸/腈莫耳比。各反應器或線圈中之 水解混合物組成及溫度及駐留時間示於下表4。 表4 RECIRC-I RECIRC-II S1 S2 S3 S4 溫度(°c) 65 90 90 90 90 90 駐留時間(分） 18 37 7.7 7.7 7.7 7.3 水解混合物組成(重量°/〇) 腈 0.37 痕量 痕量 痕量 痕量 痕量 HMBA 6.1 32 36 37 36 37 醯胺 40 5.8 2.1 0.99 0.60 0.40 水解產物顏色:4基於加納爾色標 實例6 腈以2.0克/分進料至第一再循環反應器，連同2.33克/分 65%H2S〇4得1 . 0 1酸/腈莫耳比。水進料亦以1 .09克/分引 入第二再循環反應器。各反應器或線圈中之水解混合物組成 及溫度及駐留時間示於下表5。 經濟部中央標準局員工消費合作社印製 -38 - 本纸張尺度適用中國國家標準（CNS ) A4規格（210X 297公釐） 495500 A7 B7 五、發明説明（ 36 表5 RECIRC-I RECIRC-II S1 S2 S3 S4 溫度(°C) 65 駐留時間(分） 13 105 26 105 5.4 105 5.4 105 5.4 105 5.2 水解混合物組成(重量％) 腈 0.45 0.09 痕量 0.04 痕量 0.06 HMBA 5.3 34 36 36 36 37 醯胺 40 Ο 〇 0.84 0.28 0.12 0.07 請 先 閱 讀 背 ιέ 5 I 事 項 再 填 寫 本 頁 水解產物顏色:6-7基於加納爾色標 實例7 腈以1 . 4 2克/分進料至第一再循環反應器，連同1 . 6 5克/分 6 5 % H 2 S〇4得1 . 0 1酸/腈莫耳比。水進料亦以0.7 9 5克/分引 入第二再循環反應器。各反應器或線圈中之水解混合物組成 及溫度及駐留時間示於下表6。 表6 RECIRC-I RECIRC-II SI S2 S3 溫度fC) 60 駐留時間（分） 18 120 36 120 7.5 120 7.5 120 7.5 經濟部中央標準局員工消費合作社印製 水解混合物組成(重量％) 腈 0.23 0.05 痕量 痕量 痕量 HMBA 5.2 36 35 36 36 醯胺 39 1.5 痕量 痕量 痕量 水解產物顏色:17基於加納爾色標 本纸張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） 五、發明説明 37 A7 B7 實例8 腈以1.43克/分進料至第一再循環反應器，連同166克/分 酸/腈莫耳比。水進料亦以〇 78克/分引入 第二再循環反應器。各反應器或線圈中之水解混合物組成及 溫度及駐留時間示於下表7。 表7 RECIRC-I RECIRC-II Sl 幻 S4RECIRC-I RECIRC-II S1 S2 S3 Temperature (° C) 64 Dwell time (minutes) 25 103 53 104 11 104 11 104 11 Hydrolysis mixture composition (% by weight) Nitrile 0.11 Trace trace Trace trace HMBA 8.3 34 33 35 Phenylamine 38 2.7 0.70 0.12 0.03 Color of hydrolysate: 6-7 Based on the Garner color scale. Please read the winter% on the back before filling in this page. Example of printing by the Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs. Feed to the first recycle reactor, together with 1.16 g / min 6 4.7% H 2 SO 4, to obtain a 0.99 acid / nitrile mole ratio. The water feed was also introduced into the second recycle reactor at 0.54 g / min. The composition, temperature and residence time of the hydrolyzed mixture in each reactor or coil are shown in Table 2 below. This paper size applies Chinese National Standard (CNS) A4 specification (210X297 mm) 495500 A7 B7 34 V. Description of the invention (Table 2 RECIRC-I RECIRC-II S1 S2 S3 Temperature (° C) 62 Dwell time (minutes) 25 98 53 102 11 102 11 102 11 Hydrolysis mixture composition (% by weight) Nitrile 0.22 0.05 0,05 Trace 0.035 HMBA 7.8 33 38 38 38 Phenylamine 35 3.5 0.81 0.18 0.09 Please read the winter notes on the back before filling in the hydrolysate on this page Color: 5-6 Based on the temperature of the Garner color scale (° C) 65 Dwell time (minutes) 18 105 36 105 7.7 105 7.7 105 7.7 Composition of hydrolyzed mixture (wt%) printed by the Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs Nitrile 0.36 0.06 0.05 Trace Trace HMBA 6.7 34 36 37 38 Pyramine 39 3.1 0.79 0.28 Trace Hydrolysate Color: 6-7 Based on Garner Color Specimen Paper Size Applicable to Chinese National Standard (CNS) A4 Specification (210X 291 2 3 4 public %) 37-1 Example 4 2 Nitrile was fed to the first recycle reactor at 1.43 g / min, together with 1.65 g / min 3 4.7% H 2 S04, to obtain 0.9 9 acid / nitrile mol The water feed was also introduced into the second recycle reactor at 0.7 6 g / min. The composition, temperature and dwell time of the hydrolysis mixture in each reactor or coil are shown in Table 3. Table 3 4 RECIRC-I RECIRC-II SI S2 S3 495500 A7 B7 V. Description of the invention (35) Example 5 (Please read first Note on the back, please fill in this page again.) Nitrile was fed to the first recycle reactor at 1.45 g / min. Together with 1.69 g / min, 6 4.7% H2S04, 1.0 acid / nitrile mole ratio was obtained. Each reactor The composition, temperature and dwell time of the hydrolysis mixture in the coil are shown in Table 4. Table 4 RECIRC-I RECIRC-II S1 S2 S3 S4 Temperature (° c) 65 90 90 90 90 90 Dwell time (minutes) 18 37 7.7 7.7 7.7 7.3 Hydrolysis mixture composition (weight ° / 〇) nitrile 0.37 trace trace trace trace trace HMBA 6.1 32 36 37 36 37 amidine 40 5.8 2.1 0.99 0.60 0.40 color of hydrolysate: 4 based on Garner color scale example 6 Nitrile was fed to the first recycle reactor at 2.0 g / min, together with 2.33 g / min 65% H2SO4 to obtain a 1.0 acid / nitrile molar ratio. The water feed was also introduced into the second recycle reactor at 1.09 g / min. The composition, temperature and residence time of the hydrolysis mixture in each reactor or coil are shown in Table 5 below. Printed by the Employees' Cooperatives of the Central Bureau of Standards of the Ministry of Economic Affairs -38-This paper size applies to the Chinese National Standard (CNS) A4 (210X 297 mm) 495500 A7 B7 V. Description of the invention (36 Table 5 RECIRC-I RECIRC-II S1 S2 S3 S4 Temperature (° C) 65 Dwell time (minutes) 13 105 26 105 5.4 105 5.4 105 5.4 105 5.2 Hydrolysis mixture composition (% by weight) Nitrile 0.45 0.09 Trace 0.04 Trace 0.06 HMBA 5.3 34 36 36 36 37 37 Amidine 40 〇 〇0.84 0.28 0.12 0.07 Please read the 5th item before filling in this page Hydrolysate color: 6-7 based on the example of the Garner color scale 7 Nitrile was fed to the first recycling reaction at 1.4 2 g / min The reactor, together with 1.65 g / min and 65% H 2 S04, yielded an acid / nitrile molar ratio of 1.0. The water feed was also introduced into the second recycle reactor at 0.7 95 g / min. Each The composition, temperature and residence time of the hydrolysis mixture in the reactor or coil are shown in Table 6. Table 6 RECIRC-I RECIRC-II SI S2 S3 Temperature fC) 60 Residence time (min) 18 120 36 120 7.5 120 7.5 120 7.5 Economic Composition of the hydrolyzed mixture printed by the Consumer Standards Cooperative of the Ministry of Standards of the Ministry (wt%) Nitrile 0. 23 0.05 Trace Trace Trace HMBA 5.2 36 35 36 36 Phenamine 39 1.5 Trace Trace Trace Hydrolysate Color: 17 Based on Garner Color Specimen Paper Size Applicable to Chinese National Standard (CNS) A4 Specification (210X297 mm) 5. Description of the invention 37 A7 B7 Example 8 Nitrile was fed to the first recycle reactor at 1.43 g / min, together with 166 g / min acid / nitrile mole ratio. The water feed was also introduced into the second recycle reactor at 0.078 g / min. The composition, temperature and residence time of the hydrolysis mixture in each reactor or coil are shown in Table 7 below. Table 7 RECIRC-I RECIRC-II Sl Magic S4

水解混合物組成(重量0/〇) 腈 HMBA 醯胺 0.26 7.0 36 0.10 34 3.7 痕量 37 0.05Composition of hydrolysis mixture (weight 0 / 〇)

NA NA NANA NA NA

NA NA NA (請先閱讀背面之注意事項再填寫本頁) ·裝. 水解產物顏色:6基於加納爾色標 經濟部中央標準局員工消費合作杜印製 實例9 腈以1.04克/分進料至第一再循環反應器，連同丨^克/分 65%H2S〇4得0.96酸/腈莫耳比。水進料亦以〇57克/分引 入第二再循環反應器。各反應器或線圈中之水解混合物組成 及溫度及駐留時間示於下表8。 本紙張尺度適用中國國家標準（CNS ) A4規( 210X 297公釐） 38495500 A7 B7 五、發明説明（NA NA NA (Please read the notes on the back before filling in this page) · Packing. Hydrolysate color: 6 Based on the consumer cooperation of the Central Standards Bureau of the Ministry of Economic Affairs of the Garner Color Standard Du Printing Example 9 Nitrile feed at 1.04 g / min To the first recycle reactor, together with 65% H2SO4, a 0.96 acid / nitrile mole ratio was obtained. The water feed was also introduced into the second recycle reactor at 0.57 g / min. The composition, temperature and residence time of the hydrolysis mixture in each reactor or coil are shown in Table 8 below. This paper size applies Chinese National Standard (CNS) A4 Regulation (210X 297 mm) 38495500 A7 B7 V. Description of Invention (

(請先閱讀背面之注意事項再填寫本頁) 經濟部中央標準局員工消費合作社印裂 實例1 Ο - 2 Ο 、測足酸/腈進料莫耳比對反應轉化之影響，及此比例與反 應溫對之偶聯作用。於這些實例中，腈進料速率實質上為一 足，水進料速率為各種65%H2S〇4進料加以調整確保各次操 作之最後水解產物相同之水含量。於各反應器出口及PFR之 各線圈 &lt; 端，於穩定狀態中移除樣品並以氣體層析法分析， 決定離開反應器或線圈之水解產物組成。各反應器或線圈中 之水解產物組成及溫度及駐留時間示於下面。其餘水解產物 .包括水及NH4HS04。基於分析之變數範圍，亦即酸/腈莫耳 比由0.6至1.2，及醯胺水解溫度由90_12(rc，如圖8中所示 對所測試之固足駐留（或腈進料速率）衍生出最佳之條件範圍 。於9 0 ” 1 0 1 C及1 . 〇 - 1 . 2酸/腈比之範圍内，溫度與酸/腈莫 耳比之任何組合，致成令人滿意之產物含高至〇 〇 5 %重量比 醯胺，鬲至0 · 0 5 %重量比腈及具5與7之間之顏色（基於加納 本纸張尺度適用中國國家標準（CNS ) A4規格（210X 297公釐） 外 5500 A7 B7 五、發明説明（ 39 爾色標）。 實例1 0 腈以1.02克/分進料至第一再猶環反應器，連同IQ]克/分 64.75 %H2S〇4得0.88酸/腈莫耳比。進料水亦以〇 53克/分 引入第二再循環反應器。各反應器或線圈中之水解混合物組 成及溫度及駐留時間示於下表9。 表9 RECIRC-I RECIRC-II S1 S2 S3/S4 溫度(°c) 65 105 105 105 105 駐留時間C分) 27 53 11 11 11 水解混合物組成(重量％) 腈 0.80 0.31 0.35 0.40 NA HMBA 8.3 35 41 49 NA 醯胺 41 3.7 1.7 0.96 NA * 水解產物顏色:6-7基於加納爾色標 (請先閲讀背面之注意事項再填寫本頁} ··裝. ¾濟、郅中夬榡準局員工消費合作社印製 實例1 1 腈以0.99克/分進料至第一再循環反應器，連同0.70克/分 65%H2S〇4得0.62酸/腈莫耳比。水進料亦以0.94克/分引 入第二再循環反應器。各反應器或線圈中之水解混合物組成 及溫度及駐留時間不於下表1 〇。 42 - 本纸張尺度適用中國國家標準（CNS ) A4規格（210X 297公釐） t 495500 A7 B7 五、發明説明（4()) 表1 0 RECIRC-I RECIRC-II SI S2 S3 S4 溫度(°c) 65 90 90 90 90 90 請 駐留時間(分) 32 53 11 11 11 11 閲 讀 水解混合物組成(重量％) 5 腈 5.2 2.2 2.4 2.5 2.5 2.5 ί 事 HMBA 7.9 25 27 29 30 30 項 再 醯胺 45 9.5 7.4 5.9 5.2 4.6 填 馬 本 頁 水解產物顏色:5基於加納爾色標 實例1 2 腈以1 . 0 1克/分進料至第一再循環反應器，連同1 . 3 7克/分 64.7 5 %H2S〇d·^ 1.19酸/腈莫耳比。水進料亦以0.53克/分 引入第二再循環反應器。各反應器或線圈中之水解混合物組 成及溫度及駐留時間示於下表1 1。 表1 1 經濟部中央標準局員工消費合作社印製 RECIRC-I RECIRC-II S1 S2 S3 S4 溫度(°C) 65 90 90 90 90 90 駐留時間(分) 23 50 10 10 10 10 水解混合物組成(重量。/。） 腈 痕量 痕量 痕量 痕量 痕量 痕量 HMBA 7.7 31 35 34 35 35 醯胺 〇 〇 j j 2.8 0.72 0.17 0.03 痕量 水解產物顏色:5基於加納爾色標 本紙張尺度適用中國國家標準（CNS ) A4規格（210X 297公釐） 495500 A7 B7 五、發明説明（ 41 實例1 3 腈以1.0 1克/分進料至第一再循環反應器，連同〇7〇克/分 6 5 °/0 Η 2 S Ο 4得0 · 6 0酸/腈莫耳比。水進料亦以〇 9 〇克/分引 入第一再循環反應器。各反應器或線圈中之水解混合物組成 及溫度及駐留時間示於下表1 2。 表1 2 RECIRC-I RECIRC-II S1(Please read the precautions on the back before filling out this page) Example of printing cracks in the Consumer Cooperatives of the Central Bureau of Standards of the Ministry of Economic Affairs 1 〇-2 〇 The effect of measuring the molar ratio of acetic acid / nitrile feed on the reaction conversion, and the proportion and Coupling effect on reaction temperature. In these examples, the nitrile feed rate is substantially sufficient, and the water feed rate is adjusted to various 65% H2SO4 feeds to adjust to ensure the same water content of the final hydrolysate in each operation. At the reactor outlet and the coil &lt; end of the PFR, the sample is removed in a steady state and analyzed by gas chromatography to determine the composition of the hydrolysate leaving the reactor or coil. The composition, temperature and residence time of the hydrolysate in each reactor or coil are shown below. Other hydrolysates include water and NH4HS04. Based on the analysis of the variable range, that is, the acid / nitrile molar ratio is from 0.6 to 1.2, and the ammonium hydrolysis temperature is derived from 90-12 (rc, as shown in Figure 8 for the fixed foothold (or nitrile feed rate) tested The optimal conditions range. Any combination of temperature and acid / nitrile molar ratio within the range of 90 ″ 1 0 1 C and 1.0 ～ 1.2 acid / nitrile ratio, resulting in a satisfactory product Contains up to 5% by weight of ammonium amine, 0.5 to 5% by weight of nitrile and has a color between 5 and 7 (based on Ghana's paper size, applicable Chinese National Standard (CNS) A4 size (210X 297 (Mm) 5500 A7 B7 V. Description of the invention (39 mil color scale). Example 1 0 Nitrile was fed to the first ring reactor at 1.02 g / min, together with IQ] g / min 64.75% H2S〇4. 0.88 acid / nitrile molar ratio. The feed water was also introduced into the second recycling reactor at 053 g / min. The composition, temperature and residence time of the hydrolysis mixture in each reactor or coil are shown in Table 9 below. Table 9 RECIRC -I RECIRC-II S1 S2 S3 / S4 Temperature (° c) 65 105 105 105 105 Dwell time C minutes) 27 53 11 11 11 Hydrolysis mixture composition (% by weight) Nitrile 0.80 0.31 0.35 0.40 NA HMBA 8.3 35 41 49 NA Pyramine 41 3.7 1.7 0.96 NA * Hydrolysate color: 6-7 based on the Garner color scale (please read the notes on the back before filling this page) Example 1 printed by the Consumers' Cooperative of Huangzhong County Bureau of Standards 1 Nitrile was fed to the first recycling reactor at 0.99 g / min, and 0.70 g / min 65% H2S04 was obtained to obtain a 0.62 acid / nitrile molar ratio. The water feed was also introduced into the second recycling reactor at 0.94 g / min. The composition, temperature, and residence time of the hydrolyzed mixture in each reactor or coil are not in the following table 10. 42-This paper size applies Chinese national standards ( CNS) A4 specification (210X 297 mm) t 495500 A7 B7 V. Description of invention (4 ()) Table 1 0 RECIRC-I RECIRC-II SI S2 S3 S4 Temperature (° c) 65 90 90 90 90 90 Please stay time (Points) 32 53 11 11 11 11 Read the composition of the hydrolysis mixture (% by weight) 5 Nitrile 5.2 2.2 2.4 2.5 2.5 2.5 ί HMBA 7.9 25 27 29 30 30 Items Reamine 45 9.5 7.4 5.9 5.2 4.6 Color: 5 based on the Garner color scale example 1 2 nitrile to 1. 0.1 g / min was fed to the first recycle reactor, along with 1.3 g / min 64.7 5% H 2 SOd · ^ 1.19 acid / nitrile molar ratio. The water feed was also introduced into the second recycle reactor at 0.53 g / min. The composition, temperature and residence time of the hydrolyzed mixture in each reactor or coil are shown in Table 11 below. Table 1 1 Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs RECIRC-I RECIRC-II S1 S2 S3 S4 Temperature (° C) 65 90 90 90 90 90 Dwell time (minutes) 23 50 10 10 10 10 (/)) Nitrile Trace Trace Trace Trace Trace Trace HMBA 7.7 31 35 34 35 35 Amine 〇〇jj 2.8 0.72 0.17 0.03 Trace Hydrolysate Color: 5 Based on Garner Color Specimen Paper Size Applicable to China Standard (CNS) A4 specification (210X 297 mm) 495500 A7 B7 V. Description of the invention (41 Example 1 3 Nitrile was fed to the first recycle reactor at 1.0 1 g / min, together with 0.70 g / min 6 5 ° / 0 Η 2 S 〇 4 to obtain a 0.66 acid / nitrile molar ratio. The water feed was also introduced into the first recycle reactor at 0.90 g / min. The composition of the hydrolysis mixture in each reactor or coil and The temperature and dwell time are shown in Table 1 below. Table 1 2 RECIRC-I RECIRC-II S1

水解混合物組成(重量％) 腈 ΗΜΒΑ 醯胺 6.0 7.7 44 2.6 27 5.4 2.7 32 4.0 2.2 29 1.4 2.7 34 1.8 2.3 31 1.4 水解產物顏色:10基於加納爾色標 (請先閱讀背面之注意事項再填寫本頁) 經濟部中央標準局員工消費合作社印製 實例1 4 腈以1 · 0克/分進料至第一再循環反應器，連同丨3 7克/分 64.75 %H2S〇4得1.19酸/腈莫耳比。水進料亦以〇 513克/ 分引入第二再循環反應器。各反應器或線圈中之水解混合物 組成及溫度及駐留時間示於下表1 3。 -44 - 本纸張尺度適用中國國家標準（CNS ) A4規格（21〇&gt;&lt;297公釐） 495500 A7 B7 42 五、發明説明（ 表1 3 RECIRC-I RECIRC-Π S1 S2 S3 S4 溫度(°C) 65 駐留時間(分） 23 120 50 120 10 120 10 120 10 120 10 水解混合物組成(重量％) 腈 痕量 痕量 痕量 痕量 痕量 痕量 HMBA 8.5 34 34 35 35 34 醯胺 31 0.44 痕量 痕量 痕量 痕量 請 閱 讀 背 面 I 事 項 再 填 寫 本 頁 水解產物顏色:12+基於加納爾色標 實例1 5 腈以1 . 0克/分進料至第一再循環反應器，連同1 . 0 5克/分 6 4.7 5 % H 2 S〇4得0.9 1酸/腈莫耳比。水進料亦以0.6 7克/分 引入第二再循環反應器。各反應器或線圈中之水解混合物組 成及溫度及駐留時間示於下表1 4。 表14 RECIRC-I RECIRC-II SI S2 S3 S4 溫度(°C) 65 駐留時間（分） 27 105 53 105 105 11 11 105 1-5 11 11 經濟部中央標準局員工消費合作社印製 水解混合物組成(重量％) 腈 0.39 0.11 0.11 0.11 0.10 0.09 HMBA 8.9 34 34 37 38 38 醯胺 37 4.0 1.5 0.71 0.32 0.20 水解產物顏色:6基於加納爾色標 本紙張尺度適用中國國家標準（CNS ) A4規格（210X 297公釐） -45 哪500 A7 B7 五、發明説明（ 43 實例1 6 腈以1 . 0 2克/分進料至第一再循環反應器，連同〇 7丨克/分 64.75 %；»2804得0.6酸/腈莫耳比。水進料亦以〇93克/分 引入第二再循環反應器。各反應器或線圈中之水解混合物組 成及溫度及駐留時間示於下表1 5。 . 表1 5 RECIRC-I RECIRC-II SI S2 S4 溫度(°C) 駐留時間(分) 65 32 120 52 120 11 120 11 S3 120 11 120 11 (請先閲讀背面之注意事項再填寫本頁)Composition of hydrolysis mixture (wt%) Nitrile ΗΜΒΑ 醯 amine 6.0 7.7 44 2.6 27 5.4 2.7 32 4.0 2.2 29 1.4 2.7 34 1.8 2.3 31 1.4 Color of hydrolysate: 10 based on Garner color scale (please read the precautions on the back before filling in this Page) Example printed by the Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs 1 4 Nitrile was fed to the first recycle reactor at 1.0 g / min. Together with 37 g / min 64.75% H2S04, 1.19 acid / nitrile Morby. The water feed was also introduced into the second recycle reactor at 513 g / min. The composition, temperature and residence time of the hydrolysis mixture in each reactor or coil are shown in Table 13 below. -44-This paper size applies Chinese National Standard (CNS) A4 specification (21〇 &lt; 297 mm) 495500 A7 B7 42 V. Description of the invention (Table 1 3 RECIRC-I RECIRC-Π S1 S2 S3 S4 Temperature (° C) 65 Dwell time (minutes) 23 120 50 120 10 120 10 120 10 120 10 Hydrolysis mixture composition (% by weight) Nitrile trace trace trace trace trace trace HMBA 8.5 34 34 35 35 34 31 0.44 Traces Traces Traces Please read I on the back of the page and fill in this page Hydrolysate Color: 12+ Based on the example of the Garner color scale 1 5 Nitrile was fed to the first recycle reactor at 1.0 g / min Together with 1.05 g / min 6 4.7 5% H 2 S04, 0.9 1 acid / nitrile molar ratio was obtained. The water feed was also introduced into the second recycle reactor at 0.6 7 g / min. Each reactor or The composition, temperature and dwell time of the hydrolyzed mixture in the coil are shown in Table 14 below. Table 14 RECIRC-I RECIRC-II SI S2 S3 S4 Temperature (° C) 65 Dwell time (minutes) 27 105 53 105 105 11 11 105 1 -5 11 11 Composition of hydrolyzed mixture printed by the Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs (wt%) Nitrile 0.39 0.11 0.11 0.11 0.10 0.09 HMBA 8.9 34 34 37 38 38 Pyramine 37 4.0 1.5 0.71 0.32 0.20 Color of hydrolysate: 6 Based on the size of the Garner specimen Specimen size Applicable to Chinese National Standard (CNS) A4 specification (210X 297 mm) -45 Which 500 A7 B7 V. Description of the Invention (43 Example 16 Nitrile was fed to the first recycle reactor at 1.02 g / min, together with 0.77 g / min 64.75%; 2804 gave a 0.6 acid / nitrile mole ratio. Water feed It was also introduced into the second recycle reactor at 093 g / min. The composition, temperature and residence time of the hydrolyzed mixture in each reactor or coil are shown in Table 15 below. Table 1 5 RECIRC-I RECIRC-II SI S2 S4 Temperature (° C) Dwell time (minutes) 65 32 120 52 120 11 120 11 S3 120 11 120 11 (Please read the precautions on the back before filling this page)

水解混合物組成(重量％) 腈 5.7 2.5 2.7 2.6 HMBA 8.5 29 33 34 mm 45 6.2 4.3 2.6 2.6 35 2 0 2.5 35 1.5 訂 水解產物顏色:6基於加納爾色標 實例1 7 腈以1.02克/分進料至第一再循環反應器，連同〇69克/分 65%Ηβ〇4得0.59酸/腈莫耳比。水進料亦以〇9〇克/分引 入弟一再循環反應器。各反應器或線圈中之水解混合物組成 及溫度及駐留時間示於下表1 6。 濟 部 中 央 標 準 局 消 費 合 if 衽 印 製 本纸張尺度適用中國國家標準（CNs ) A4規格（210X 297公釐 495500 A7 B7 五、發明説明（ 44 表1 6 RECIRC-I RECIRC-II S1 S2 S3 S4 溫度(°C) 65 駐留時間(分） 32 90 53 90 11 90 11 90 11 90 10 水解混合物組成(重量°/〇) 腈 6.0 3.4 3.2 3.2 3.3 3.3 HMBA 8.2 25 27 28 29 30 醯胺 44 12 8.0 7.5 6.6 5.7 請 先 閱 讀 背 冬 i 事 項 再 填 寫 本 頁 水解產物顏色:5基於加納爾色標 實例1 8 腈以1.02克/分進料至第一再循環反應器，連同1.38克/分 65%H2S〇Jf 1 . 1 8酸/腈莫耳比。水進料亦以0.54克/分引 入第二再循環反應器。各反應器或線圈中之水解混合物組成 及溫度及駐留時間示於下表1 7。 表1 7 RECIRC-I RECIRC-II SI S2 S3 S4 溫度〇C) 65 駐留時間(分） 23 90 50 90 10 90 10 90 10 90 10 經濟部中央標準局員工消費合作社印製 水解混合物組成(重量％) 腈 痕量 痕量 痕量 痕量 痕量 痕量 HMBA 7.2 31 35 35 35 36 醯胺 34 2.9 0.75 0.24 痕量 痕量 水解產物顏色:5基於加納爾色標 本纸張尺度適用中國國家標準（CNS ) A4規格（210X 297公釐） Α7 Β7 i、發明説明（45 ) 實例1 9 腈以1.03克/分進料至第一再循環反應器，連同1.39克/分 6 5 % H 2 S〇4得1 . 1 7酸/腈莫耳比。水進料亦以〇 · 5 2克/分引 入第二再循環反應器。各反應器或線圈中之水解混合物組成 及溫度及駐留時間示於下表1 8。 表1 8 (請先閱讀背面之注意事項再填寫本頁) ··裝 腈 痕量 痕量 痕量 痕量 痕量 痕量 HMBA 7.1 Ο 〇 J J 33 34 34 48 醯胺 35 0.39 痕量 痕量 痕量 痕量 岁解產物顏色:&gt; 18基於加納爾色標 1 丁 RECIRC-I RECIRC-II S1 S2 S3 S4 溫度Cc), 65 120 120 120 120 120 時間(分） 23 50 10 10 10 10 水解混合物組成(重量％) 經濟部中央標準局員工消費合作社印製 實例2 0 腈以1 . 0 2克/分進料至第一再循環反應器，連同1 . 〇 5克/分 65%ΗΘ〇4得0.90酸/腈莫耳比。水進料亦以〇 63克/分引 入第一再彳盾環反應器。各反應器或線圈中之水解混合物組成 及溫度及駐留時間示於下表1 9。 本纸張尺度適用中國國家標準（CNS ) Α4規格（2丨0χ297公楚） 495500 A7 B7 五、發明説明（46 ) 表1 9 RECIRC-I RECIRC-II S1 S2 S3 S4 溫度(°c) 65 105 105 105 105 105 駐留時間(分） 27 53 11 11 11 11 混合物組成(重量％) 腈 0.38 0.06 0.09 0.06 0.09 0.09 HMBA 8.9 28 39 31 41 38 醯胺 40 2.5 0.97 0.31 0.18 0.10 水解產物顏色:7基於加納爾色標 (請先閱讀背面之注意事項再填寫本頁) 經濟部中央標準局員工消費合作社印製 495500 A7 B7 五、發明説明（47 ) 15.2分。於最後之PFR線圈中完成醯胺水解。 實例2 2 用於圖3中所示之連續水解方法中之設備由2個CSTRsA 一個充填管柱型PFR組成第一個CSTR致力於腈水解而第二 個CSTR及PFR供醯胺水解。pfr為以寇克（&amp;0()]1)8]^\^鐵 弗龍充填物充填之8英寸直徑襯以鐵弗龍之碳鋼管。PFr由 Koch Engmeering製造。SMVP充填物之閥速度為〇 95毫米/ . 秒。 、 1 〇 5磅/小時之腈與丨2 1磅/小時之6 5 % H 2 S 0 4連續進料於 第一個20加侖CSTR，其中13加崙之液體由控制反應器出口 經濟部中央標隼局員工消費合作社印製 (讀先閱讀背面之注意事項再填寫本頁) 動之含里控制器維持。反應器以產物再循環圈之外在冷卻 器維持於6 5 °C。基於總進料速率及反應器液體體積之駐留時 間為3 8分。出口水解產物樣品，基於氣體層析法分析，發現 含少於0 . 1 %腈，3 4.9 %醯胺及1 1.2 % Η Μ B A。將出口流引 入具液體體積2 7.7加侖之第二個3 0加侖C S T R。8 0 °C熱水 流亦以6 0.5磅/小時之速率進料至第二c S T R。反應器溫度 為1 〇 5 °C，駐留時間為9 1分。來自反應器之水解產物含 1 · 9 %醯胺，指示多於9 〇 %之進入之醯胺於此容器中轉化成 Η Μ B A。第二c S T R出口流再進入含結構充填及具總液體體 積2 5加侖之充填管柱反應器中，從沿管柱反應器之長度所得 之各種樣品，醯胺水解反應經發現，於反應器之7 0 %長處已 達完成。絕熱管柱反應器之溫度侧圖範圍由丨〇 〇至丨〇 2 °C， P F R中之駐留時間為5 2 9分，最後產物含少於〇 ·丨％腈，少 於〇 . 1 % g區胺，及4 8 % Η Μ B A。此水解方法之主要副產物， 本纸張尺度適用中國國家標準（CNS ) a4規格（210X29*7公釐） 495500 A7 B7 48 五、發明説明（ &gt;^11411304可自產物中以習用方法分離。 (請先閱讀背面之注意事項再填寫本頁) 實例23 用於實例2 2中之設備用以下面之水解方法，除了第二 C S T R接以旁道管以致充填管柱反應器為醯胺水解反應之主 要反應器。 訂 進料至第一 CSTR之速率如實例22中所述。然而，第一 C S T R中之溫度為6 0 °C。出口樣品之分析顯示中間水解混合 物含0 · 2 %腈、3 9.4 %醯胺及9.5 % Η Μ B A。較低之C S T R操 作溫度造成微較高之腈濃度，但較低之Η Μ B A濃度。中間水 解混合物於線上靜止之混合器中與熱水流（6 〇 . 5磅/小時）混 石。元成反應流進入P F R其維持穩定態，溫度侧圖由入口之 80°C，於中間處達最高溫之105°C，於充填管柱之出口降至 1 0 2 C。雖然管柱壁經熱追踪且為絕緣的，但亦遭到一些熱 流失。管柱反應器中之轾留時間為5 2 · 9分。管柱反應器出口 之最後之水解產物含水於〇 .丨％腈，〇 .丨％醯胺及 4〇.8%HMBA，其餘為副產物NH4HS〇4及水。 實例2 4 經濟部中央標準局員工消費合作社印製 用於實例23之設備被用於下面水解，除了濃h2S〇4直接 進料至第一 CSTR(圖5)而無以水預先稀釋至65%H2S〇4。 水流亦進料至反應器。因此，酸之稀釋熱及水解熱經由^在 之循環冷卻器除去。第二C s T R加以旁通管。 腈（72磅/小時），96%H2S〇4(56.2磅/小時）及稀釋水 (26.7磅/小時）同時進料至第一 cstr，於其中發生腈之水 解。操作液體體積為10加侖，其基於3次進料速率之總和提 51 - 495500 A7 B7 五、發明説明（49) 供4 2.5分之駐留時間。反應溫度控制於5 5 °C。水性水解混 合物之氣體層析法顯示其含0.5 %腈，4 0.6 %醯胺及 5.7 % Η Μ B A。水性水解混合物與4 1 . 3磅/小時熱水於線上靜 止之混合器中混合。完成反應流以如同實例2 3中所述進入充 填管柱反應器，除了管柱反應器中之絕熱反應溫度稍微較高 外，可能因為離開在較低溫度下操作之C S T R之較高含量之 未反應之腈所釋放之另外之熱。從管柱反應器抽出之樣品， 測定由管柱底面入口 70%之高度處，醯胺水解已完成。 實例2 5 - 3 8 於各CSTR之出口、PFR加入（SI)、PFR出口（S6)及沿著 P F R長度之4個取樣口（ S 2至S 5 )採取之水解混合物樣品如圖 3所示。於穩定狀態除去樣品，並以氣體層析法分析，決定 當離開C S T R s及當流過P F R時之水解混合物組成。於各 C S T R及各段之P F R内之水解混合物組成及溫度及駐留時間 示於下。水解混合物之其餘部分包括水及NH4 H S〇4。實例 無指示包含CSTR-II數據之設備，於其中第二CSTR加以旁 通管致使稀水性水解混合物直接從線上混合器流至P F R。 經濟部中央標準局員工消費合作社印製 (請先閔讀背面之注意事項再填寫本頁) 此數據証明轉化受插塞流動反應器中之溫度、酸/腈比及 軸反混合程度影響。反混合依次為反應混合物流過反應器之 速度之涵數。於其中反混合影響之轉化之例中，反應器以少 於其閥速度1 . 0毫米/秒操作，造成較低之平均驅動力，亦即 對此非零級反應醯胺濃度沿著反應器長度整合。於一些例中 ，可補償低於閥速度之操作，使用相對較高溫及/或酸/腊比 。速度對軸反混合之關係及結果對轉化之影響之進一步討論 -52 - 本紙張尺度適用中國國家標準（CNS ) A4規格（210X29*7公釐） 495500 A7 B7 五、發明説明（ 50 述於實例3 8之結束。實例2 5腈以105.0〇磅/小時進料至第„〇3711，連同12〇95磅/小時65%H2S〇d^.〇3酸/腈莫耳比。水進料亦以6〇 5〇磅/ 小時引入第二CSTR。對於各樣品之水解混合物組成及各位 置之溫度示於下表20。 體積(加俞 13 CSTR-I CSTR-II 27.7 S1 表20 S2 S3 S4 S5 S6 17.5 (總 PFR) (請先閲讀背面之注意事項再填寫本頁) 溫度Γ〇 103 103 102 月膏 0.02 0.02 0.01 0.01 0.01 ΗΜΒΑ 12 41 34 39 39 酿胺 34 2.0 0.5 0.27 0.04 經濟部中央標準局員工消費合作社印製 實例2 6 腈以105.00磅/小時進料至第一（：8丁11，連同12〇95镑 小時6 5 % H 2 S Ο 4得1.0 0酸/腈莫耳比。水進料亦以6 〇 5 〇辱 小時引入第二C S T R。對於各樣品之水解混合物組成及各位 置之溫度示於下表21。 -53 本紙張尺度適用中國國家標準（CNS ) Α4規格（210Χ 297公釐） 495500 A7 B7 51 五、發明説明（Composition of hydrolysis mixture (% by weight) Nitrile 5.7 2.5 2.7 2.6 HMBA 8.5 29 33 34 mm 45 6.2 4.3 2.6 2.6 35 2 0 2.5 35 1.5 Order hydrolysate color: 6 based on the example of the Garner color scale 1 7 Nitrile at 1.02 g / min The mixture was fed to the first recycle reactor and together with 0.69 g / min 65% ββ4, a 0.59 acid / nitrile mole ratio was obtained. The water feed was also introduced into the Brother-I recycle reactor at 0.90 g / min. The composition, temperature and residence time of the hydrolysis mixture in each reactor or coil are shown in Table 16 below. Consumption of the Central Bureau of Standards of the Ministry of Economic Affairs 衽 Printed paper sizes are applicable to Chinese national standards (CNs) A4 specifications (210X 297 mm 495500 A7 B7 V. Description of invention (44 Table 1 6 RECIRC-I RECIRC-II S1 S2 S3 S4 Temperature (° C) 65 Dwell time (minutes) 32 90 53 90 11 90 11 90 11 90 10 Hydrolysis mixture composition (weight ° / 〇) Nitrile 6.0 3.4 3.2 3.2 3.3 3.3 HMBA 8.2 25 27 28 29 30 Amines 44 12 8.0 7.5 6.6 5.7 Please read the following items before filling in this page Color of hydrolysate: 5 Based on the example of Garner color scale 1 8 Nitrile was fed to the first recycle reactor at 1.02 g / min, together with 1.38 g / min 65 % H2S〇Jf 1. 18 acid / nitrile molar ratio. The water feed was also introduced into the second recycling reactor at 0.54 g / min. The composition and temperature of the hydrolysis mixture in each reactor or coil and the residence time are shown below Table 1 7. Table 1 7 RECIRC-I RECIRC-II SI S2 S3 S4 Temperature 〇C) 65 Dwell time (minutes) 23 90 50 90 10 90 10 90 10 90 10 Hydrolyzed mixture printed by the staff consumer cooperative of the Central Standards Bureau of the Ministry of Economic Affairs Composition (wt%) Nitrile Trace Trace Trace Trace Trace Trace HMBA 7.2 31 35 35 35 36 Pyramine 34 2.9 0.75 0.24 Trace and trace hydrolysate Color: 5 Based on Garner color specimen Paper size Applicable to Chinese National Standard (CNS) A4 specification (210X 297 mm) Α7 Β7 i 、 Invention Explanation (45) Example 1 9 Nitrile was fed to the first recycle reactor at 1.03 g / min, together with 1.39 g / min 65% H 2 S04 to obtain a 1. 17 acid / nitrile mole ratio. Water feed The material is also introduced into the second recycling reactor at 0.52 g / min. The composition, temperature, and residence time of the hydrolysis mixture in each reactor or coil are shown in the following table 18. Table 1 8 (Please read the notes on the back first Please fill in this page again.) ·························································································································································································· 18 Based on Garner color scale 1 D RECIRC-I RECIRC-II S1 S2 S3 S4 Temperature Cc), 65 120 120 120 120 120 Time (minutes) 23 50 10 10 10 10 Composition of hydrolysis mixture (wt%) Central Bureau of Standards, Ministry of Economic Affairs Printed by Consumer Consumption Cooperative Example 2 Nitrile was fed to the first recycle reactor at 1.02 g / min, together with 1 .05 g / min 65% ΗΘ〇4 to obtain a 0.90 acid / nitrile mole ratio. The water feed was also introduced into the first re-shield ring reactor at 0.63 g / min. The composition, temperature and residence time of the hydrolysis mixture in each reactor or coil are shown in Table 19 below. This paper size applies to Chinese National Standard (CNS) A4 specification (2 丨 0 × 297), 495500 A7 B7 V. Description of invention (46) Table 1 9 RECIRC-I RECIRC-II S1 S2 S3 S4 Temperature (° c) 65 105 105 105 105 105 Dwell time (minutes) 27 53 11 11 11 11 Mixture composition (% by weight) Nitrile 0.38 0.06 0.09 0.06 0.09 0.09 HMBA 8.9 28 39 31 41 38 Amine 40 2.5 0.97 0.31 0.18 0.10 Hydrolysate Color: 7 based on Ghana Color Code (Please read the notes on the back before filling this page) Printed by the Consumer Cooperatives of the Central Bureau of Standards of the Ministry of Economic Affairs 495500 A7 B7 5. Description of Invention (47) 15.2 points. The amidine hydrolysis is completed in the final PFR coil. Example 2 2 The equipment used in the continuous hydrolysis process shown in Figure 3 consists of 2 CSTRsA and a packed column PFR. The first CSTR is dedicated to nitrile hydrolysis and the second CSTR and PFR are used for amidine hydrolysis. pfr is an 8-inch diameter carbon steel pipe lined with Teflon filled with Kirk (& 0 ()] 1) 8] ^ \ ^ iron. PFr is manufactured by Koch Engmeering. The SMVP filling has a valve speed of 0.95 mm / .sec. 1.05 lbs / hr of nitrile and 2 1 lbs / hr of 65% H 2 S 0 4 were continuously fed to the first 20 gallon CSTR, of which 13 gallons of liquid was controlled by the reactor outlet of the Ministry of Economy Central Standard Printed by the Bureau ’s Consumer Cooperative (read the precautions on the back before filling this page). The active controller is maintained. The reactor was maintained at 65 ° C outside the cooler outside the product recycle loop. The residence time based on the total feed rate and reactor liquid volume was 38 minutes. Exported hydrolysate samples were analyzed based on gas chromatography and found to contain less than 0.1% nitrile, 3 4.9% amidine and 11.2%% Μ B A. The outlet stream was directed into a second 30 gallon C S T R with a liquid volume of 2 7.7 gallons. The 80 ° C hot water stream was also fed to the second cS T R at a rate of 6 0.5 pounds per hour. The reactor temperature was 105 ° C, and the residence time was 91 minutes. The hydrolysate from the reactor contained 1.9% amidine, indicating that more than 90% of the incoming amidine was converted to ΗΜ B A in this vessel. The second c STR exit stream then enters the packed column reactor with structured packing and a total liquid volume of 25 gallons. From various samples obtained along the length of the column reactor, the amidine hydrolysis reaction was found in the reactor. 70% of the strengths have been completed. The temperature profile of the adiabatic column reactor ranges from 丨 〇〇 ～ 丨 〇2 ° C, the residence time in PFR is 529 minutes, and the final product contains less than 0.1% nitrile, less than 0.1% g Reoamine, and 48% Η Μ BA. The main by-product of this hydrolysis method, this paper size is applicable to the Chinese National Standard (CNS) a4 specification (210X29 * 7 mm) 495500 A7 B7 48 5. Description of the invention (&gt; ^ 11411304 can be separated from the product by conventional methods. (Please read the precautions on the back before filling this page) Example 23 The equipment in Example 2 was used for the following hydrolysis method, except that the second CSTR was connected to the bypass tube so that the column reactor was filled with ammonium hydrolysis reaction. The main reactor. The feed rate to the first CSTR was as described in Example 22. However, the temperature in the first CSTR was 60 ° C. Analysis of the exit sample showed that the intermediate hydrolysis mixture contained 0.2% nitrile, 3 9.4% ammonium amine and 9.5% Μ Μ BA. The lower CSTR operating temperature results in slightly higher nitrile concentrations, but lower Η Μ BA concentrations. The intermediate hydrolysis mixture is placed in a static mixer on the line with hot water flow (6 0.5 lb / hr) mixed stone. The Yuancheng reaction stream enters the PFR and maintains a steady state. The temperature profile is from 80 ° C at the inlet to 105 ° C, the highest temperature in the middle, and decreases to the outlet of the packed column. 1 0 2 C. Although the column wall is exposed to heat It is insulated, but it also suffers from some heat loss. The retention time in the column reactor is 5 2 · 9 minutes. The final hydrolysate at the outlet of the column reactor contains 0.1% nitrile, 〇.丨% ammonium amine and 40.8% HMBA, the rest are by-products NH4HS〇4 and water. Example 2 4 The equipment printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs was used for the following hydrolysis except for concentrated h2S 〇4 is directly fed to the first CSTR (Figure 5) without being pre-diluted with water to 65% H2S04. The water stream is also fed to the reactor. Therefore, the heat of dilution of the acid and the heat of hydrolysis pass through the circulating cooler Removed. The second C s TR was bypassed. Nitrile (72 lb / hr), 96% H2SO4 (56.2 lb / hr) and dilution water (26.7 lb / hr) were simultaneously fed to the first cstr, where Hydrolysis of nitrile occurs. The volume of the operating liquid is 10 gallons, which is based on the sum of the three feed rates. 51-495500 A7 B7 V. Description of the invention (49) Dwell time of 4 2.5 minutes. The reaction temperature is controlled at 5 5 ° C Gas chromatography of the aqueous hydrolysis mixture showed that it contained 0.5% nitrile, 4 0.6% amidine and 5.7% Η BA. Water The hydrolysis mixture was mixed with 4 1.3 lbs / hr of hot water in a static mixer on-line. The reaction flow was completed to enter the packed column reactor as described in Example 23, except that the adiabatic reaction temperature in the column reactor was slightly The higher outside may be due to the additional heat released by the higher content of unreacted nitrile leaving the CSTR operating at the lower temperature. The sample drawn from the column reactor was measured at a height of 70% from the inlet of the bottom of the column, and the hydrolysis of amidine was completed. Example 2 5-3 8 Samples of hydrolysis mixture taken at the exit of each CSTR, PFR addition (SI), PFR outlet (S6) and 4 sampling ports (S 2 to S 5) along the length of PFR are shown in Figure 3 . The sample was removed at steady state and analyzed by gas chromatography to determine the composition of the hydrolyzed mixture when leaving C S T R s and when flowing through P F R. The composition, temperature, and residence time of the hydrolyzed mixture in each CSRT and PFR of each segment are shown below. The rest of the hydrolysis mixture includes water and NH4HSO. Example There is no indication of a device containing CSTR-II data, where a bypass tube is placed on the second CSTR to cause the dilute aqueous hydrolysis mixture to flow directly from the in-line mixer to PF R. Printed by the Employees' Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs (please read the notes on the back before filling this page) This data proves that the conversion is affected by the temperature in the plug flow reactor, the acid / nitrile ratio, and the degree of shaft reverse mixing. Backmixing is in turn the number of speeds at which the reaction mixture flows through the reactor. In the example where the effect of anti-mixing is transformed, the reactor is operated at less than 1.0 mm / sec of its valve speed, resulting in a lower average driving force, i.e. the ammonium concentration of this non-zero reaction along the reactor Length integration. In some cases, operations below the valve speed can be compensated for using relatively high temperatures and / or acid / wax ratios. Further discussion on the relationship between speed and shaft anti-mixing and the effect of the result on the conversion -52-This paper size applies the Chinese National Standard (CNS) A4 specification (210X29 * 7mm) 495500 A7 B7 V. Description of the invention (50 described in the example The end of 3 8. Example 2 5 Nitrile was fed at 105.000 lbs / hr to No. 037111, together with 12.095 lbs / hr 65% H2S〇d ^ .〇3 Molar ratio. Water feed was also The second CSTR was introduced at 6050 lbs / hr. The composition of the hydrolysis mixture for each sample and the temperature at each location are shown in Table 20 below. Volume (plus 13 CSTR-I CSTR-II 27.7 S1 Table 20 S2 S3 S4 S5 S6 17.5 (Total PFR) (Please read the precautions on the back before filling in this page) Temperature Γ〇103 103 102 Moon paste 0.02 0.02 0.01 0.01 0.01 ΗΜΑ 12 41 34 39 39 Amines 34 2.0 0.5 0.27 0.04 Central Bureau of Standards, Ministry of Economic Affairs Printed by Consumer Consumption Cooperative Example 2 6 Nitrile was fed to the first at 105.00 lbs / hr (8:11, together with 125.095 lbs. Hrs 6 5% H 2 S 〇 4 to obtain 1.0 0 acid / nitrile molar ratio. Water The feed was also introduced into the second CSTR at 6050 hours. For the composition and position of the hydrolyzed mixture for each sample The temperature is shown in the following table 21. -53 This paper size is applicable to the Chinese National Standard (CNS) A4 specification (210 × 297 mm) 495500 A7 B7 51 V. Description of the invention (

CSTR-I CSTR-II S1 表2 1 S2 S3 S4 S5 S6 體積(加侖 13 溫度(°C) 13 27.7 17.5 (總 PFR) 65 105 101 102 102 102 102 101 PFR速度=10毫米/秒 腈.0.01 痕量 HMBA 11 36 醯胺 35 1.9 水解混合物組成(重量％) 痕量 痕量 痕量 痕量 痕量 0.01 37 29 26 30 31 47 1.1 0.21 0.05 0.05 0.05 0.05 水解產物顏色:6-7基於加納爾色標 請 先 閲 讀 背 ft 意 事 項 再 填 寫 本 頁CSTR-I CSTR-II S1 Table 2 1 S2 S3 S4 S5 S6 Volume (gallon 13 temperature (° C) 13 27.7 17.5 (total PFR) 65 105 101 102 102 102 102 101 101 PFR speed = 10 mm / sec nitrile. 0.01 mark HMBA 11 36 Phenamine 35 1.9 Composition of hydrolysis mixture (% by weight) Trace trace Trace trace Trace 0.01 37 29 26 30 31 47 1.1 0.21 0.05 0.05 0.05 0.05 Hydrolysate color: 6-7 based on Garner color scale Please read the notes before filling in this page

IT 經濟部中央標準局員工消費合作社印製 實例2 7 腈以1 0 5.0 0磅/小時進料至第一 C S T R，連同1 4 5 . 1 4磅/ 小時6 5 % H 2 S〇4得1.2 1酸/腈莫耳比。水進料亦以5 7.4磅/ 小時引入第二C S T R。對於各樣品之水解混合物組成及各位 置之溫度示於下表22 表22 CSTR-I CSTR-II SI S2 S3 S4 S5 S6 1 I 體積(加侖 13 ) 27.7 17.5 (總 PFR) 溫度(°C) 65 93 90 93 92 92 92 91 1 PFR速度=10毫米/秒 水解混合物組成(重量％) 腈 痕量 痕量 痕量 痕量 痕量 痕量 ΗΜΒΑ 11 33 34 35 36 36 醯胺 31 1.8 1.3 0.14 0.02 0.01 痕量 痕量 38 33 0.01 0.01 水解產物顏色:9-10基於加納爾色標 實例2 8 腈以7 2.0 0磅/小時進料至第一 C S T R，連同8 2.9 4磅/小時 -54 - 本纸張尺度適用中國國家標準（CNS ) A4規格（210X 297公釐） 495500 A7 B7 五、發明説明（52) 6 5%H2S〇dl 1.0酸/腈莫耳比。水進料亦以41.30磅/小時 引入線上混合器。對於各樣品之水解混合物組成及各位置之 溫度示於下表23。 表23 _CSTR-I_S1_S2_S3_S4_S5_S6 體積(加侖 10 19.9(總PFR) ) 溫度(°C) 65 80 96 97 97 97 97 _PFR速度=0.69毫米/秒_；_ 水解混合物組成(重量％) 腈 0.13 0.03 0.02 0.01 0.01 0.01 0.02 HMBA 14 22 28 24 27 25 44 醯胺 40_1_9_33_L6_1/7_L4_1.2 水解產物顏色:3基於加納爾色標 實例2 9 腈以7 2.0 0磅/小時進料至第一 C S T R，連同8 2.9 4磅/小時 6 5%H2S〇4得1 . 0酸/腈莫耳比。水進料亦以4 1 . 3 0磅/小時 引入線上混合器。對於各樣品之水解混合物組成及各位置之 溫度示於下表24。 表24 _CSTR-I_S1_S2_S3_S4_S5_S6 體積(加侖 10 19.9(總PFR) 經濟部中央標準局員工消費合作社印製 (請先閲讀背面之注意事項再填寫本頁) ) 溫度(°C) 60 81 103 103 101 101 100 PFR速度=0.69毫米/秒 水解混合物組成(重量％) 月t 0.19 0.01 痕量 痕量 痕量 痕量 痕量 HMBA 8.8 20 38 37 39 47 54 醯胺 38 22 1.4 0.59 -55 - 0.34 0.33 0.06 本纸張尺度適用中國國家標準（CNS ) A4規格（210X 297公釐） A7 B7 五 發明説明（ 53 水解產物顏色:6-7基於加納爾色標 貫例3 0 腈以150.00磅/小時進料至第一 CSTR，連同17279镑/ 小時65%H2S〇jl.〇4酸/腈莫耳比。水進料亦以86 4〇^/ J時引入弟一 C S T R。對於各樣品之水解混合物組成及各位 置之溫度示於下表25。 表25 ____ CSTR-I CSTR-U SI S2 S3 S4 S5 % 體積(加侖 10 277 25.0 (總PFR) ^ ) 溫度(°C) 65 1〇4 100 102 102 102 102 101 __ PFR速度=14毫米/秒 (請先閱讀背面之注意事項再填寫本頁}Printed by the Consumer Standards Cooperative of the Central Bureau of Standards, Ministry of IT and Economy 2 7 Nitrile was fed to the first CSTR at 105.0 0 lbs / hour, together with 145.14 lbs / hour 65.5% H 2 S〇4 1.2 1 acid / nitrile mole ratio. The water feed was also introduced into the second CSTR at 5 7.4 lbs / hour. The composition of the hydrolysis mixture for each sample and the temperature at each location are shown in Table 22 below. Table 22 CSTR-I CSTR-II SI S2 S3 S4 S5 S6 1 I Volume (Gal 13) 27.7 17.5 (Total PFR) Temperature (° C) 65 93 90 93 92 92 92 91 1 PFR speed = 10 mm / sec composition of hydrolysis mixture (% by weight) nitrile trace trace trace trace trace trace ΗΜΒΑ 11 33 34 35 36 36 amine 31 1.8 1.3 0.14 0.02 0.01 Traces Traces 38 33 0.01 0.01 Color of hydrolysate: 9-10 based on Garner color scale Example 2 8 Nitrile was fed to the first CSTR at 7 2.0 0 lbs / hour, together with 8 2.9 4 lbs / hour -54-Paper Zhang scale is applicable to Chinese National Standard (CNS) A4 specification (210X 297 mm) 495500 A7 B7 V. Description of the invention (52) 6 5% H2SOdl 1.0 acid / nitrile mole ratio. The water feed was also introduced into the inline mixer at 41.30 lbs / hour. The composition of the hydrolysis mixture for each sample and the temperature at each location are shown in Table 23 below. Table 23 _CSTR-I_S1_S2_S3_S4_S5_S6 Volume (gallon 10 19.9 (total PFR)) Temperature (° C) 65 80 96 97 97 97 97 97 _PFR speed = 0.69 mm / sec_; _ Hydrolysis mixture composition (% by weight) Nitrile 0.13 0.03 0.02 0.01 0.01 0.01 0.02 HMBA 14 22 28 24 27 25 44 Pyramine 40_1_9_33_L6_1 / 7_L4_1.2 Hydrolysate Color: 3 Based on the Garner Color Scale Example 2 9 Nitrile was fed to the first CSTR at 7 2.0 0 lbs / hour, together with 8 2.9 4 lbs 6 5% H2SO4 to obtain 1.0 acid / nitrile mole ratio. The water feed was also introduced into the on-line mixer at 4 1.30 lbs / hour. The composition of the hydrolysis mixture for each sample and the temperature at each location are shown in Table 24 below. Table 24 _CSTR-I_S1_S2_S3_S4_S5_S6 Volume (Gallon 10 19.9 (Total PFR) Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs (please read the precautions on the back before filling this page)) Temperature (° C) 60 81 103 103 101 101 100 PFR speed = 0.69 mm / sec Composition of hydrolysis mixture (% by weight) Month 0.19 0.01 Trace Trace Trace Trace Trace HMBA 8.8 20 38 37 39 47 54 Amidine 38 22 1.4 0.59 -55-0.34 0.33 0.06 Paper Zhang scale is applicable to Chinese National Standard (CNS) A4 specification (210X 297 mm) A7 B7 Five inventions description (53 Hydrolysate color: 6-7 based on the Garner Color Standard Example 3 0 Nitrile is fed to 15th A CSTR, together with 17,279 pounds / hour 65% H2S0jl.〇4 acid / nitrile molar ratio. The water feed was also introduced into the Cyi CSTR at 86 400 / J. For each sample, the composition and position of the hydrolysis mixture The temperatures are shown in Table 25 below. Table 25 ____ CSTR-I CSTR-U SI S2 S3 S4 S5% volume (gallon 10 277 25.0 (total PFR) ^) temperature (° C) 65 1〇4 100 102 102 102 102 101 __ PFR speed = 14 mm / s (Please read the precautions on the back before filling this page)

經濟部中央標隼局員工消費合作社印製 水解混合物組成(重量％) 腈 0.26 0.03 0.01 痕量 痕量 痕量 痕量 痕量 HMBA 8.1 35 37 39 37 37 39 38 38 3.0 1.5 0.21 0.03 0.02 0.02 0.02 __ 水解產物顏色:10-11基於加納爾色標 ' 實例3 1 腈以1 5 0 . 〇 0磅/小 時進料至第一 CSTR，連 同 1 72_ .7 9 磅 / 小時6 5 % Η 2 S〇4得1 . 0 2酸/腈莫耳比。水進料亦以8 6 .4 〇 磅 / 小時引入第. -CSTR 。對於各樣品之水解混合物組成及各位 置之溫度示於下表26 0 表26 — CSTR-] ：CSTR-II S1 S2 S3 S4 S5 S6 體積(加佘 10 ) 27.7 25.0 (總PFR) 溫度fc) 65 102 100 103 103 104 103 102 PFR速度=14毫米/秒 訂 t -56 本纸張尺度適用中國國家標準（CNS ) A4規格（210X 297公釐） 495500 A7 B7 ^ 發明説明（ 54 月青 0.13 〇.〇1 HMBA 7.0 36 酿胺 40 3.2 丞解混合物組成(言詈％) 〇-〇3 0.03 0.02 0.02 0.02 37 39 39 40 41 2.4 0.84 0.23 0.18 0.16 水解產物顏色:8-9基於加納爾色標 0.01 40 0.13 實例3 2 腈以105.0〇磅/小時進料至第一〇3丁11，連同12〇.95碡/ 小時6 5 % Η2 S〇4得1 . 〇 2酸/腈莫耳比。水進料亦以6 〇 . 5 〇镑/ 小時引入第一 C S T R。對於各樣品之水解混合物組成及各位 置之溫度示於下表27。 表27 _CSTR-I CSTR - II SI S2 S3 S4 體積(加侖 27.7 I7.5 (總PFR) (請先閱讀背面之注意事項再填寫本頁) 1·裝 S5 S6 溫度fc)Composition of the hydrolyzed mixture printed by the Consumer Cooperatives of the Central Bureau of Standards of the Ministry of Economic Affairs (wt%) Nitrile 0.26 0.03 0.01 Trace Trace Trace Trace Trace HMBA 8.1 35 37 39 37 37 39 38 38 3.0 1.5 0.21 0.03 0.02 0.02 0.02 __ Hydrolysate color: 10-11 based on the Garner color scale 'Example 3 1 Nitrile was fed to the first CSTR at 150.0 lbs / hr, along with 1 72_ .7 9 lbs / hr 65% Η 2 S. 4 gives 1.0 2 acid / nitrile mole ratio. The water feed was also introduced into the -CSTR at 86.4 lb / hr. The composition of the hydrolysis mixture for each sample and the temperature at each location are shown in Table 26 below. Table 26 — CSTR-]: CSTR-II S1 S2 S3 S4 S5 S6 Volume (plus 10) 27.7 25.0 (Total PFR) Temperature fc) 65 102 100 103 103 104 103 102 PFR speed = 14mm / s order t -56 This paper size applies Chinese National Standard (CNS) A4 specification (210X 297mm) 495500 A7 B7 ^ Description of the invention (54 Yueqing 0.13 〇. 〇1 HMBA 7.0 36 Fermented amine 40 3.2 Decomposition mixture composition (%) 〇-〇3 0.03 0.02 0.02 0.02 37 39 39 40 41 2.4 0.84 0.23 0.18 0.16 Hydrolysate color: 8-9 based on Garner color scale 0.01 40 0.13 Example 3 2 Nitrile was fed to the first 033 but 11 at 105.0 lbs / hr, together with 12.05 Torr / hr 65.5% Torr 2 S04 to give a 1.02 acid / nitrile mole ratio. Water feed The material was also introduced into the first CSTR at 60.5 pounds per hour. The composition of the hydrolyzed mixture for each sample and the temperature at each location are shown in Table 27 below. Table 27_CSTR-I CSTR-II SI S2 S3 S4 Volume (gallon 27.7 I7.5 (Total PFR) (Please read the precautions on the back before filling this page) 1 · Install S5 S6 temperature fc)

1〇1 103 1〇3 PFR速度二10毫米/秒 水解混合物組成(重|〇/n) 0.36 0.03 0.01 0.01 0.01 9.1 38 38 40 40 39 2.7 1.8 0.32 0.08 訂 經濟部中央標準局員工消費合作社印製 痕量 41 __ - 〇.仍 水解產物顏色:10-11基;^加納爾色標 &quot; —實例' 腈以72.00磅/小時進料至第一 CSTR，連同8 2.94於 6 5%1123〇4得1.〇酸/腈莫耳比。水進料亦以41.3〇^&amp; 引入線上混合器。對於各樣品之水解混合物組成及各 t 溫度不於下表2 8。 ' 〆1〇1 103 1〇3 PFR speed 2 10mm / s Hydrolysis mixture composition (weight 0 / n) 0.36 0.03 0.01 0.01 0.01 9.1 38 38 40 40 39 2.7 1.8 0.32 0.08 Trace 41 __-〇. Still hydrolysate color: 10-11 base; ^ Garner color scale &quot;-Example 'nitrile was fed to the first CSTR at 72.00 lbs / hour, together with 8 2.94 at 6 5% 1123〇4 A 1.0 acid / nitrile mole ratio was obtained. The water feed was also introduced into the inline mixer at 41.3%. For each sample, the composition of the hydrolysis mixture and the respective t temperatures are not lower than those in Table 28 below. '〆

CSTR-I S1CSTR-I S1

.噃 張 纸 I本 义度適用中國國家標準（CNS )八4規格（210/ 495500 7 Β 五、發明説明（55 ) 體積(加侖 ) 溫度(°c) 10 60 19·9(總 PFR) 84 103 105 105 PFR速度=0.69毫米/秒 105 103 水解混合物組成(重量％) 月f 0.41 0.02 0.01 0.01 0.01 0.01 0.01 HMBA 9.5 23 26 23 23 23 47 醯胺 43 17 2.3 0.63 0.62 0.61 0.72 水解產物顏色:5-6基於加納爾色標 實例3 4 月青以9 0.6 0磅/小 時進料至第 一 CSTR，連同 103.80磅/小 時 6 5 % H 2 S 〇 4 得1. 0 3酸/腈莫耳比。水進料亦以5 1 . 9 0磅/小 時引入線上混合器 。對於各樣 品之水解混合物組成及各位置 之溫度示於下表29 〇 表29 CSTR -1 SI S2 S3 S4 S5 S6 體積(加侖 12.6 25.0(總 PFR) ) 溫度(°C) 59 82 104 105 105 105 104 PFR速度=0.86毫米/秒 水解混合物組成(重量％) 月會 0.39 0.03 0.01 0.01 0.01 0.01 0.01 HMBA 9.1 23 33 30 31 31 38 醯胺 41 18 2.0 0.92 0.79 0.71 0.76 水解產物顏色:8-9基於加納爾色標 實例3 5 經濟部中央標準局員工消費合作社印裂 (請先閲讀背面之注意事項再填寫本頁) 腈以9 0.6 0磅/小時進料至第一 C S T R，連同1 2 4.8 0磅/小 時6 5 % H 2 S〇4得1 . 2 0酸/腈莫耳比。水進料亦以4 9.4 0磅/小 時引入線上混合器。對於各樣品之水解混合物組成及各位置 之溫度示於下表30。 -58 - 本紙張尺度適用中國國家標準（CNS ) A4規格（21 OX 297公釐） 495500 A7 B7 五、發明説明（56 ) 表3 0 _CSTR-I S1_S2_S3_S4_S5_S6 體積(加侖 12.6 25.0 (總PFR) ) 溫度 Γ〇 45 86 107 107 107 107 105 ,_PFR速度=0.86毫米/秒 _ 水解混合物組成(重量％) 月耷 0.07 0.01 痕量 痕量 痕量 痕量 痕量 HMBA 8.1 23 35 33 39 37 37 醯胺 36_12_1.0 痕量 痕量 痕量_0.01 _水解產物顏色:1 M2基於加納爾色標_ 實例3 6 腈以90.60磅/小時進料至第一 CSTR，連同124.80磅/小 時6 5 % H 2 S〇4得1.2 0酸/腈莫耳比。水進料亦以4 9.4 0磅/小 時引入線上混合器。對於各樣品之水解混合物組成及各位置 之溫度示於下表3 1。 表3 1 _CSTR-I_S1_S2_S3_S4_S5_S6 體積(加侖 12.6 25.0 (總PFR) ) 溫度(°C) 58 82 105 103 103 103 101 _PFR速度=0.86毫米/秒_ 水解混合物組成(重量％) 腈 痕量 痕量 痕量 痕量 痕量 痕量 痕量 經濟部中央標準局員工消費合作社印製 (請先閱讀背面之注意事項再填寫本頁) HMBA 8.3 20 38 37 38 38 39 酷胺 31 18 0.96 痕量 痕量 痕量痕量 水解產物顏色:1 M2基於加納爾色標 實例3 7 腈以9 0.6 0磅/小時進料至第一 C S T R，連同1 0 3 . 8 0磅/小 時6 5 % H 2 S〇4得1 . 0酸/腈莫耳比。水進料亦以5 1 . 9 0磅/小 本紙張尺度適用中國國家標準（CNS ) Α4規格（210X29*7公釐） 495500 A7 B7 五、發明説明（57 ) -時引入線上混合器。對於各樣品之水解混合物組成及各位置 之溫度示於下表32。 表32 _CSTR-I S1_S2_S3_S4_S5_S6 體積(加侖 12.6 25.0 (總PFR) ) 溫度(°C) 59 88 109 109 109 109 107 _PFR速度=0.86毫米/秒_ 水解混合物組成(重量％) 腈 〇.〇9 0.01 痕量 Q.01 痕量 痕量 0.01 HMBA 8.8 26 38 69 38 40 41 醯胺 37_13_0.30 0.02 0.01 0.01 痕量 水解產物顏色:1M2基於加納爾色標 (請先閱讀背面之注意事項再填寫本頁) 經濟部中央標準局員工消費合作社印製.Piece of paper I Original meaning applies to Chinese National Standard (CNS) 8 4 specifications (210/495500 7 Β V. Description of invention (55) Volume (gallon) Temperature (° C) 10 60 19 · 9 (Total PFR) 84 103 105 105 PFR speed = 0.69 mm / s 105 103 Hydrolysis mixture composition (wt%) Month f 0.41 0.02 0.01 0.01 0.01 0.01 0.01 0.01 HMBA 9.5 23 26 23 23 23 47 Phenamine 43 17 2.3 0.63 0.62 0.61 0.72 Hydrolysate color: 5- 6 Based on the Garner color scale example 3 April green was fed to the first CSTR at 9 0.6 0 lbs / hour, together with 103.80 lbs / hour 65% H 2 S 〇 4 to obtain a 1.03 acid / nitrile mole ratio. The water feed was also introduced into the on-line mixer at 5 1.90 pounds per hour. The composition of the hydrolyzed mixture for each sample and the temperature at each location are shown in Table 29 below. Table 29 CSTR -1 SI S2 S3 S4 S5 S6 Volume (Gallon 12.6 25.0 (Total PFR)) Temperature (° C) 59 82 104 105 105 105 104 PFR speed = 0.86 mm / sec Hydrolysis mixture composition (wt%) Monthly meeting 0.39 0.03 0.01 0.01 0.01 0.01 0.01 HMBA 9.1 23 33 30 31 31 38 Phenamine 41 18 2.0 0.92 0.79 0.71 0.76 Hydrolysate : 8-9 Based on the example of the Garner color scale. 3 5 Printed by the Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs (please read the precautions on the back before filling this page). Together with 1 2 4.80 lbs / hr and 65% H 2 S04, a 1.2 acid / nitrile mole ratio was obtained. The water feed was also introduced into the on-line mixer at 4 9.40 lbs / hr. For the hydrolysis mixture of each sample The composition and the temperature of each position are shown in the following table 30. -58-This paper size applies the Chinese National Standard (CNS) A4 specification (21 OX 297 mm) 495500 A7 B7 V. Description of the invention (56) Table 3 0 _CSTR-I S1_S2_S3_S4_S5_S6 Volume (gallon 12.6 25.0 (total PFR)) Temperature Γ〇45 86 107 107 107 107 105, _PFR speed = 0.86 mm / s_ Composition of hydrolysis mixture (wt%) Month 0.07 0.01 Trace trace Trace trace HMBA 8.1 23 35 33 39 37 37 Phenylamine 36_12_1.0 Traces Traces Traces_0.01 _ Hydrolysate Color: 1 M2 based on the Garner Color Scale_ Example 3 6 Nitrile was fed to the first CSTR at 90.60 lbs / hour Together with 124.80 lbs / hr of 65% H2SO4, a 1.20 acid / nitrile molar ratio was obtained. The water feed was also introduced into the inline mixer at 4 9.40 lbs / hr. The composition of the hydrolysis mixture for each sample and the temperature at each location are shown in Table 31 below. Table 3 1 _CSTR-I_S1_S2_S3_S4_S5_S6 Volume (gallon 12.6 25.0 (total PFR)) Temperature (° C) 58 82 105 103 103 103 103 _PFR speed = 0.86 mm / s_ Composition of hydrolysis mixture (wt%) Nitrile trace trace trace Traces Traces Traces Traces Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs (please read the precautions on the back before filling out this page) HMBA 8.3 20 38 37 38 38 39 Coolamine 31 18 0.96 Traces Traces Trace hydrolysate color: 1 M2 based on the Garner color scale example 3 7 Nitrile was fed to the first CSTR at 9 0.6 0 lbs / hour, together with 10 3.80 lbs / hour 65% H 2 S〇4 1.0 acid / nitrile mole ratio. The water feed is also 5 1.90 lbs / min. The paper size applies to the Chinese National Standard (CNS) A4 specification (210X29 * 7 mm) 495500 A7 B7 V. Description of the invention (57)-In-line mixer. The composition of the hydrolysis mixture for each sample and the temperature at each location are shown in Table 32 below. Table 32 _CSTR-I S1_S2_S3_S4_S5_S6 Volume (gallon 12.6 25.0 (total PFR)) Temperature (° C) 59 88 109 109 109 109 109 107 _PFR speed = 0.86 mm / s_ Composition of the hydrolysis mixture (% by weight) Nitrile 0.09 0.01 Q.01 Trace Trace 0.01 HMBA 8.8 26 38 69 38 40 41 Phenylamine 37_13_0.30 0.02 0.01 0.01 Trace Hydrolysate Color: 1M2 based on the Garner Color Scale (Please read the precautions on the back before filling this page) Printed by the Consumer Cooperatives of the Central Bureau of Standards of the Ministry of Economic Affairs

本纸張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） 495500 經濟部中央標準局員工消費合作社印製 A7 B7 五、發明説明（1 ) 實例3 8 腈以1 05 · 00磅/小時進料至第一 CS TR，連同1 20.95镑/ 小時6 5 % Η 2 S 0 4得1 . 〇酸/腈莫耳比。水進料亦以6 0 · 5 0镑/ 小時引入線上混合器。對於各樣品之水解混合物組成及各位 置之溫度示於下表33。 表3 3 --~~— CSTR-I S1 S2 S3 S4 S5 S6 體積(加侖 ) 14.6 25.0 (總PFR) 溫度(°c) 60 80 103 104 105 104 102 PFR速度=1.〇毫米/秒 水解混合物組成ί會·%、 月皆 0.22 0.02 0.01 0.01 0.01 0.01 0.01 HMBA 9.5 24 39 45 45 42 41 39 21 2.5 0.19 0.20 0.28 0.11 -_____水解產物顏色:8-9基於加納爾色標 如上述，於充填管拄PFR中所得之某些轉化不足以符合產 物水解產物中之標的殘留醯胺濃度。此等較低轉化可歸因於 車父低反應溫度或酸/腈比，過度之軸反混合，或這些因素之 一些組合。基於在足以提供高於約5〇之皮克里特準數之速度 下操作反應器所做之研究，測定於水解產物中之殘留醯胺濃 度’可一致地降低至少於上面對穩定狀態操作所討論之較佳 範圍之反應溫度與酸/腈比約0 03 %。但於皮克里特準數大 大地低於50時，一般發現更低之轉化，除非增加溫度及/或 酸/月f比來補償。 為研究於充填管柱PFR中，速度對反混合之影響，以變化 &lt;速度使用於管柱底（其中使自來水向上流）注射鹽之脈衝作 本纸張尺度適财國) (請先閲讀背面之注意事項再填寫本頁)This paper size applies to Chinese National Standard (CNS) A4 (210X297 mm) 495500 Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs A7 B7 V. Invention Description (1) Example 3 8 Nitrile at 1 05 · 00 lbs / hour Feeding to the first CS TR together with 1 20.95 pounds / hour 65% Η 2 S 0 4 gives a 1.0 acid / nitrile mole ratio. The water feed was also introduced into the inline mixer at 60.50 pounds / hour. The composition of the hydrolysis mixture and the temperature of each position for each sample are shown in Table 33 below. Table 3 3-~~-CSTR-I S1 S2 S3 S4 S5 S6 Volume (Gallon) 14.6 25.0 (Total PFR) Temperature (° c) 60 80 103 104 105 104 102 PFR Speed = 1.0 mm / s Hydrolyzed mixture The composition will be 0.2% 0.02 0.01 0.01 0.01 0.01 0.01 HMBA 9.5 24 39 45 45 42 41 39 21 2.5 0.19 0.20 0.28 0.11 -____ Hydrolysate Color: 8-9 Based on the Garner color scale as described above, in the filling Some of the conversions obtained in the pipette PFR were insufficient to meet the target residual amine concentrations in the product hydrolysate. These lower conversions can be attributed to the low reaction temperature or acid / nitrile ratio of the car parent, excessive axial backmixing, or some combination of these factors. Based on studies performed to operate the reactor at a speed sufficient to provide a pic Crete number higher than about 50, the determination of the residual amidine concentration in the hydrolysate can consistently reduce at least the steady state operation above. The preferred range of the reaction temperature and the acid / nitrile ratio in question is about 0.03%. However, when the Pickcrete number is below 50, lower conversions are generally found, unless increased by temperature and / or acid / month f ratios to compensate. In order to study the effect of velocity on anti-mixing in packed column PFR, the pulse of salt was injected at the bottom of the column (with tap water flowing upward) to change the velocity. (Notes on the back then fill out this page)

、1T -Am 495500 A7 五、發明説明（ B7 59 =追踪劑來進行駐留時間分佈試驗。於反應器之上面出口插 入傳導性探針供測量出口流動之傳導性，自其得追踪劑反應 數據，以鹽（NaCi)濃度對時間表示。依習用方法，做基於 反應數據之计算以決定平均駐留時間（第一分佈瞬間），變度 (第一刀、佈瞬間）、皮克里特準數，及連續之同等之攪拌槽之 對所/則武之反應器’流速（q p m )、平均駐留時間（㊀）…、因’入k度（σ2)、皮克里特準數（Pe)、及同等之攪拌槽 反應器之數目（j)述於表34。 ajpun 0.95 0.47 0.90 整 表34 θ__ σ2 P e 丄 29.5 0.0393 50.9 25.5 66.3 0.0681 29.4 14.7 25.1 0.0749 26.7 13.4 劑於反應器底部上 面留下之口 。對此因素調 (請先閱讀背面之注意事項再填寫本頁) 訂 經濟部中央標準局員工消費合作社印製 ，J=20.5 及 pe = 41 此等數據証明於這些試驗中所用之充填管柱之臨界速度閾 於〇 · 5 qpm之範圍。 基於對醯胺水解反應之動力計算，計算同等之攪拌槽反應 器數目與殘留之醱胺濃度之間之關係。亦計算同等之攪拌枰 反應器與：（a)對所指定之轉化程度所須之反應器長度）對（對 相同之轉化程度於完美之插塞流動條件下，所須之長度）之 比例（L/Lp);及（b)(對指定之反應器長度殘留之醯胺濃度）對 (对相同長度之反應器於冗美之插塞流動條件下殘留之酶胺 濃度）間之比例（c/cP)之間之相關性。此等計算述於表35。 本纸張尺度適用中國國家標準（CNS ) A4規格（210X 297公釐） 495500 A7 B7 五、發明説明（60) 表3 5 JL L/L^ C/Cl 來之醯胺％) 15 1.236 2.66 0 · 〇 5 8 1 % 20 1.177 2.25 0.0491 25 1.14 1 2.00 0.0436 3 0 1.178 1.83 0.03 99 40 1.088 1.62 〇·〇353 CO 1.000 1.00 0.0218 經濟部中央標準局員工消費合作、社印製 實例3 9 - 5 5 於穩疋狀®當中除去水解混合物樣品並以氣體層析法分析 ，測足當離開CSTR，進入PFR再離開pFR*對實例39_48 之圖2中所示及如對實例49-5 5之圖i中所示之水解混合物組 成。 數據證明HMBN之轉化成醯胺藉由在輸送反應流至pFR以 則，於C S T R之出口與稀釋點之間之區内增加約3分之駐留 時間而改進。實例44與Η為直接可與實例45，46及53比較 ，因為彼等於相同流速下操作並於p F R中顯示相同之高峰溫 度。實例3 9-4 8證明當流動反應器高峰溫度由1〇5或1〇6。(： 降至101或102C時’水解產物顏色改進。 實例3 9 如’ 9 6 % H 2 S〇4及水進料至c s τ R (如圖2所示）得丨〇酸/ 腑莫耳比形成水性水解混合物。於CsTR中60 t：下駐留37分 後’水解混合物含〇 · 〇 3 %腈及3 9 %醯胺重量比。於向前流動 口之循_區上游為於向前流動口與稀釋點之間之向前流動反 本紙張中國國家標準（CNS ) Α4^^ΤΤΪ0Χ297公ίΤ (請先閱讀背面之注意事項再填寫本頁) 訂 495500 A7 B7 五、發明説明（ 61 應區中之水性水解混合 ^ 物I駐留時間分別為4秒及3分。稀釋 後，將完成反應流進料 芊 竹至P F R，其於絕熱下8卜1 0 6。(：操作 且駐留時間為70分。旁ώ u U侏作 义成足水性水解產物含0 · 0 1 %醯胺及少 ;0 · 0 1 %如几成 &lt; 水性水解產物顏色為基於加納爾色標 8 · 5 〇 、 實例4 0 月月、9 6 % Η 2 S Ο 4及火；佳々立工p。 2 4夂水進科至CSTR(如圖2所示）得1()之酸 A莫耳比形成水性水解混合物。於CSTR中6(TC駐留37分 後水解奶合物含〇 . 〇 1 %腈及3 8 %醯胺重量比。於向前流動 口I# %區m於向前流動口與稀釋點間之向前流動反應 區中之水性水解混合物之駐留時間分別為4秒及3分。稀釋後 ，將完成反應流進料至PFR，其於絕熱下於81]〇5它操作 且駐留時間為70分。完成之水性水解產物奴Qi%g&amp;胺及少 於〇，〇 1 %腈。冗成之水性水解產物顏色基於加納爾色標為 8.5° 實例4 1 經濟部中央標準局員工消費合作社印製 (請先閲讀背面之注意事項再填寫本頁) 96%H2S〇4及水進料至CSTR(如圖2所示）得丨〇之酸 /腈莫耳比，形成水解混合物。於CSTR$6(rc下駐留37分 後，水解混合物含0.08%腈及38%醯胺重量比。於向前流^ 口心循環區上游中及於向前流動口與稀釋點之間之向前流動 反應區中之水性水解混合物之駐留時間分別為4秒及3分稀釋 後，芫成反應流進料至p F R，其於絕熱下8 〇 _丨〇 5它操作並 駐留7 0分。完成之水性水解產含少於〇 〇〗％醯胺及腈。完成 之水性水解產物之顏色基於加納爾色標為8 . 5。 本纸張尺度適用中國國家標準（CNS ) A4規格（210X 297公釐） 495500 Α7 Β7 62 五、發明説明（ 實例4 2 (請先閱讀背面之注意事項再填寫本頁) 腈96%H2S〇4及水進料至CSTR(如圖2所示）得丨〇酸/腈 莫耳比，形成水性水解混合物。於CSTR6〇〇C下駐留3〇分後 ，水解混合物含〇·〇8%腈及3 8%醯胺重量比。於向前流動口 之循環區上游中及於向前流動口與稀釋上間之向前流動反應 區中 &lt; 水性水解混合物之駐留時間分別為4秒及3分。稀釋後 ，凡成反應流進料至p F R，其於絕熱下，8 〇 _丨〇 5它操作， 駐留時間為70分。完成之水性水解產物含少於〇〇1%醯胺及 腊。冗成之水性水解產物之顏色基於加納爾包標為7.5。 實例4 3 夤 腊、96%H2S〇4及水進料至CSTR(铷圖2中所示）得1.0酸 /恥莫耳比’形成水性水解混合物。於C s τ r中，6 〇。(：下駐 田3 7分後’無分析水解混合物。於向前流動口之循環區上游 中及於向别/瓦動口與稀釋點間之向前流動反應區中之水性水 解混合物之駐留時間分別為4秒及3分。稀釋後，完成反應流 進料至P F R ’其於絕熱下於7 9 - 1 0 4 °C操作，駐留時間7 0分 。凡成之水性水解產物含〇 · 〇 1 %醯胺及少於0.0 1 %腈。完成 之水性水解產物之顏色基於加納爾色標為8 5。 實例4 4 經濟部中央標準局員工消費合作社印製 月膏、9 6 % H 2 S〇4及水進料至c S T R (如圖2所示）得1 . 0酸/ 月月莫耳比’形成水性水解混合物。於C S τ r、6 0 °C駐留3 7分 後’無分析水解混合物。於向前流動口之循環區上游中及於 向^ &quot;瓦動口與稀釋點間之向前流動反應區中之水性水解混合 物之駐留時間分別為4秒及3分。稀釋後，完成反應流進料至 - 65 - 本紙張^度適用( cNS) A4規格（公釐 ' 495500 A7 B7 五'發明説明（ 63 經濟部中央標準局員工消費合作社印製 PFR ’其於絕熱下’ 79_1〇4它操作，駐留時間7〇分。完成 &lt;水性水解產物含少於〇 . 0 1 %醯胺及腈。完成之水性水解產 物1顏色基於加納爾色標為8.5。 實例4 5 赌、9 6 % H 2 S〇4及水進料至c S τ R (如圖2所示）得1.0酸/ 月月莫耳比’形成水性水解混合物。於C s τ r、6 0 °C駐留3 7分 後’水解混合物含〇 〇 4 %腈及4 〇 %醯胺重量比。。於向前流 動口之循壤區上游中及於向前流動口與稀釋點間之向前流動 反應區中之水性水解混合物之駐留時間分別為4秒及3分。稀 釋後，完成反應流進料至p F R，其於絕熱下，7 7 _丨〇 2。〇操 作’駐留時間為7 〇分。完成之水性水解產物含〇 . 〇丨％醯胺及 少於0.0 1 %腊。芫成之水性水解產物之顏色基於加納爾色標 為 8.5。 實例4 6 月膏、96%H2S〇4及水進料至CSTR(如圖2所示）得1·〇酸/ 月月莫耳比’形成水性水解混合物。於C S T R、6 0 °C駐留3 7分 後’水解混合物含0.0 3 %腊及4 0 %醯胺重量比。於向前流動 口之循環區上游中及於向前流動π與稀釋點間之向前流動反 應區中之水性水解混合物之駐留時間分別為4秒及3分。稀釋 後，完成反應流進料至P F R，其於絕熱下，7 7 - 1 〇 2 °C操作 ’駐留時間為7 0分。冗成之水性水解產物含〇 · 〇 1 %醯胺及少 於0.0 1 %腈。完成之水性水解產物之顏色基於加納爾色標為 7.5 ° 實例4 7 本紙張尺唐」 尺度適用中國國家標準（CNS ) A4規格（210X 297公釐） (請先閲讀背面之注意事項再填寫本頁)1T-Am 495500 A7 V. Description of the invention (B7 59 = Tracer for dwell time distribution test. Insert a conductivity probe at the outlet of the reactor to measure the conductivity of the outlet flow, and obtain the tracer response data from it. Expressed as salt (NaCi) concentration versus time. According to customary methods, do calculations based on response data to determine the average dwell time (the first moment of distribution), the degree of variation (the first knife, the moment of cloth), the Picrit criterion, And continuous equivalent stirred tanks of the reactor / Noritake reactor's flow rate (qpm), average residence time (㊀), etc., because of the input k degrees (σ2), Pickeret number (Pe), and equivalent The number (j) of the stirred tank reactors is described in Table 34. ajpun 0.95 0.47 0.90 The entire table 34 θ__ σ2 P e 丄 29.5 0.0393 50.9 25.5 66.3 0.0681 29.4 14.7 25.1 0.0749 26.7 13.4 The mouth left on the bottom of the reactor. Adjust this factor (please read the precautions on the back before filling this page). Printed by the Consumer Standards Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs, J = 20.5 and pe = 41. These data prove the filling tube used in these tests. The critical speed threshold is in the range of 0.5 qpm. Based on the calculation of the kinetics of the amidine hydrolysis reaction, the relationship between the number of equivalent stirred tank reactors and the remaining amidine concentration is calculated. The equivalent agitated reactor and : (A) the ratio of the required reactor length to the specified degree of conversion) to (the required length for the same degree of conversion under perfect plug flow conditions) (L / Lp); and (b) Correlation between (residue concentration of ammonium amine for a specified reactor length) and ratio (c / cP) of (residual enzyme amine concentration for a reactor of the same length under tedious plug flow conditions). These calculations are described in Table 35. This paper size applies Chinese National Standard (CNS) A4 specification (210X 297 mm) 495500 A7 B7 V. Description of the invention (60) Table 3 5 JL L / L ^ C / Cl Pyramine%) 15 1.236 2.66 0 · 〇 5 8 1% 20 1.177 2.25 0.0491 25 1.14 1 2.00 0.0436 3 0 1.178 1.83 0.03 99 40 1.088 1.62 〇 · 〇353 CO 1.000 1.00 0.0218 Example of cooperation between employees of the Central Standards Bureau of the Ministry of Economic Affairs and social printing 3 9-5 5 A sample of the hydrolyzed mixture was removed in Stables® and analyzed by gas chromatography. When leaving the CSTR, enter the PFR and then leave the pFR * as shown in Figure 2 of Example 39_48 and as shown in Figure 49-5 The composition of the hydrolyzed mixture shown. The data demonstrate that the conversion of HMBN to amidine was improved by increasing the residence time by about 3 minutes in the zone between the exit of the C S T R and the dilution point in the reaction flow to pFR. Examples 44 and Η are directly comparable to Examples 45, 46, and 53 because they operate at the same flow rate and show the same peak temperature in p F R. Examples 3 9-4 8 demonstrate when the peak temperature of the flow reactor is from 105 or 106. (: The color of the hydrolysate is improved when it is lowered to 101 or 102C. Example 3 9 Such as '96% H 2 S04 and water was fed to cs τ R (as shown in Figure 2) to obtain the acid / mol. Ratio to form an aqueous hydrolysis mixture. 60 t in CsTR: 37 minutes after standing below, the 'hydrolysis mixture contains 0.03% nitrile and 39% ammonium amine by weight. It is in the forward direction of the forward flow port. The forward flow between the flow port and the dilution point is the Chinese National Standard for Paper (CNS) Α4 ^^ ΤΤΪ0 × 297 公 ίΤ (Please read the precautions on the back before filling this page) Order 495500 A7 B7 V. Description of the invention (61 shall The residence time of the aqueous hydrolysis mixture ^ in the zone is 4 seconds and 3 minutes, respectively. After dilution, the reaction stream is fed into the bamboo shoots to PFR, which is 8 b 10 6 under adiabatic conditions. (: Operation and residence time is 70 points. The water-soluble hydrolysate containing U. sylvestris is 0. 0 1% ammonium amine and less; 0. 0 1% such as a few percent &lt; the color of the water-based hydrolysate is based on the Garner color scale 8. 5 〇 Example 4 0 month, 96% Η 2 S 〇 4 and fire; Jia 々 Ligong p. 2 4 夂 water into the CSTR (as shown in Figure 2) to get 1 () acid A Mo An aqueous hydrolysis mixture is formed. The hydrolyzed milk compound contains 0.01% nitrile and 38% ammonium amine by weight in the CSTR after 37 minutes of TC residence. It flows forward in the I #% area of the forward flow port. The residence time of the aqueous hydrolysis mixture in the forward-flow reaction zone between the mouth and the dilution point were 4 seconds and 3 minutes, respectively. After dilution, the completed reaction stream was fed to PFR, which was operated at 81 ° under adiabatic conditions. And the residence time is 70 minutes. The finished aqueous hydrolysate is Qi% g &amp; amine and less than 0.01% nitrile. The color of the redundant aqueous hydrolysate is based on the Garner color scale of 8.5 ° Example 4 1 Central standard of the Ministry of Economic Affairs Printed by the Bureau ’s Consumer Cooperative (please read the precautions on the back before filling this page) 96% H2S〇4 and water is fed to the CSTR (as shown in Figure 2) to obtain the acid / nitrile mole ratio of 〇〇, which forms hydrolysis Mixture. After staying at CSTR $ 6 (rc for 37 minutes, the hydrolyzed mixture contains 0.08% nitrile and 38% amidine by weight. It is in the forward flow ^ upstream of the core-circulation zone and between the forward flow port and the dilution point. The residence time of the aqueous hydrolysis mixture in the forward flow reaction zone was 4 seconds and 3 minutes after dilution. It should be fed to p FR, which operates under adiabatic conditions for 80 minutes and stays for 70 minutes. The completed aqueous hydrolysis yields less than 0.00% amidine and nitrile. The color of the completed aqueous hydrolysis product Based on the Garner color scale, it is 8.5. This paper size applies the Chinese National Standard (CNS) A4 specification (210X 297 mm) 495500 Α7 Β7 62 5. Description of the invention (Example 4 2 (Please read the precautions on the back before Fill in this page) Nitrile 96% H2SO4 and water were fed to the CSTR (as shown in Figure 2) to obtain a molar ratio of acid / nitrile to form an aqueous hydrolysis mixture. After standing at CSTR600C for 30 minutes, the hydrolysis mixture contained 0.08% nitrile and 38% amidine by weight. The residence time of the aqueous hydrolysis mixture in the upstream of the circulation zone of the forward flow port and in the forward flow reaction zone between the forward flow port and the upper dilution are 4 seconds and 3 minutes, respectively. After dilution, Fancheng reaction stream was fed to p F R, which was operated under adiabatic conditions, with a residence time of 70 minutes. The finished aqueous hydrolysate contains less than 0.001% amidine and wax. The color of the redundant aqueous hydrolysate was 7.5 based on the Garner package. Example 4 3 Wax wax, 96% H2SO4, and water were fed to a CSTR (shown in Figure 2) to obtain an 1.0 acid / pubic mole ratio 'to form an aqueous hydrolysis mixture. In C s τ r, 60. (: After 37 minutes in Shimojota, there is no analysis of the hydrolysis mixture. Retention of the aqueous hydrolysis mixture in the upstream of the circulation zone of the forward flow port and in the forward flow reaction zone between the Xiangbei / Wadong port and the dilution point The time is 4 seconds and 3 minutes respectively. After dilution, the reaction stream is fed to PFR ', which is operated at 79-104 ° C under adiabatic conditions, with a residence time of 70 minutes. Fancheng's aqueous hydrolysate contains 0 · 〇1% ammonium amine and less than 0.01% nitrile. The color of the finished hydrolyzed hydrolysate is based on the Garner color scale of 8 5. Example 4 4 Monthly cream printed by employees' cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs, 96% H 2 S04 and water were fed to cSTR (as shown in Figure 2) to obtain a 1.0 acid / monthly mole ratio 'to form an aqueous hydrolysis mixture. After standing at CS τ r, 60 ° C for 37 minutes,' no Analyze the hydrolysis mixture. The residence time of the aqueous hydrolysis mixture in the upstream of the circulation zone of the forward flow port and in the forward flow reaction zone between the tile moving port and the dilution point are 4 seconds and 3 minutes, respectively. Dilution After that, complete the reaction flow feed to-65-this paper is suitable for (cNS) A4 size (mm '495500 A7 B7 'Explanation of the Invention (63 PFR printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs' It is adiabatic' 79_1104 It is operated with a dwell time of 70 minutes. Complete &lt; Aqueous hydrolysate contains less than 0.01% amine And nitrile. The color of the finished aqueous hydrolysate 1 was 8.5 based on the Garner color scale. Example 4 5 gamble, 96% H 2 S04 and water were fed to c S τ R (as shown in Figure 2) to give 1.0 acid / Month Mohr ratio 'forms an aqueous hydrolysis mixture. After staying for 37 minutes at C s τ r, 60 ° C, the' hydrolysis mixture contains 004% nitrile and 40% amide by weight. It flows forward The residence time of the aqueous hydrolysis mixture in the upstream region of the mouth and in the forward flow reaction zone between the forward flow port and the dilution point is 4 seconds and 3 minutes, respectively. After dilution, the reaction stream is fed to p FR , Its adiabatic, 7 7 _ 丨 〇2. 0 operation 'dwell time is 70 minutes. The completed aqueous hydrolysate contains 0.00 %% ammonium amine and less than 0.0 1% wax. Aqueous aqueous hydrolysis product The color is based on the Garner color scale as 8.5. Example 4: June cream, 96% H2SO4, and water were fed to the CSTR (as shown in Figure 2). Molar ratio of 1.0 mol / month forms an aqueous hydrolysis mixture. After staying at CSTR, 60 ° C for 37 minutes, the hydrolysis mixture contains 0.03% wax and 40% ammonium by weight. At the forward flow port The residence time of the aqueous hydrolysis mixture in the upstream of the circulation zone and in the forward-flow reaction zone between the forward flow π and the dilution point are 4 seconds and 3 minutes, respectively. After dilution, the reaction stream is fed to PFR, which Operating under adiabatic temperature, 7 7-10 ° C, the dwell time is 70 minutes. The redundant aqueous hydrolysate contains 0.001% amidine and less than 0.01% nitrile. The color of the finished water-based hydrolysate is 7.5 ° based on the Garner color scale. Example 4 7 This paper ruler ”applies to China National Standard (CNS) A4 (210X 297 mm) (Please read the precautions on the back before filling in this page)

、1T 會 495500 A7 _____B7 五、發明説明（64 ) 腈、9 6 % H 2 S Ο 4及水進料至c S T R (如圖2所示）得1.0酸/ 月青莫耳比’形成水性水解混合物。於C s τ R、6 0 °C駐留3 7分 後’水解混合物含〇 · 〇 6 %腈及3 7 %醯胺重量比。於向前流動 口之循環區上游中及於向前流動口與稀釋點間之向前流動反 應區中之水性水解混合物之駐留時間分別為4秒及3分。稀釋 後’芫成反應流進料至p F R，其於絕熱下，7 5 - 1 0 1 °C操作 ’駐留時間為7 0分。完成之水性水解產物含〇 . %醯胺及少 於〇 . 〇 1 %腈。完成之水性水解產物之顏色基於加納爾色標為 6.5。 實例4 8 腈、96%H2S〇4及水進料至CSTR(如圖2所示）得1()酸/ 腈莫耳比，形成水性水解混合物。於C s T R、6 0駐留3 7分 後’水解混合物含4 1 %醯腈重量比少於〇 . 〇 9 %骑。於向前流 動口之循環區上游中及於向前流動口與稀釋點間之向前流動 反應區中之水性水解混合物之駐留時間分別為4秒及3分。稀 釋後，完成反應流進料至PFR，其於絕熱下，75_1〇1^操 作，駐留時間為70分。完成之水性水解產物含〇〇1%醯胺2 少於〇.〇1 %腈。完成之水性水解產物之顏色基於加納 為6.5。 不 經濟部中央標準局員工消費合作、社印製 (請先閱讀背面之注意事項再填寫本頁) -Am 實例4 9 腈、96%H2S〇4及水進料至CSTR(如圖i所示）得工 腈莫耳比，形成水性水解混合物。於C s T R、6 9ff、 ^ t A 2 C駐留4 6分 仗’水解混合物含4 3 %醯胺及〇 · 〇 2 %腈。水性永如、 ,_ &gt;昆合物於 向刖流動口之循環區上游中及於向前流動口與 、 | 1千點間之向 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） ^5〇〇 A7, 1T will 495500 A7 _____B7 V. Description of the invention (64) Nitrile, 96% H 2 S 〇 4 and water are fed to c STR (as shown in Figure 2) to get 1.0 acid / moire green mole ratio 'to form aqueous hydrolysis mixture. After staying for 37 minutes at C s τ R and 60 ° C, the 'hydrolysis mixture contains 0.06% nitrile and 37% amidine by weight. The residence time of the aqueous hydrolysis mixture in the upstream of the circulation zone of the forward flow port and in the forward flow reaction zone between the forward flow port and the dilution point were 4 seconds and 3 minutes, respectively. After dilution, the reaction mixture was fed to p F R, which was operated at 7 5-101 ° C under adiabatic conditions and the residence time was 70 minutes. The finished aqueous hydrolysate contains 0.1% amidine and less than 0.01% nitrile. The color of the finished aqueous hydrolysate is 6.5 based on the Garner Color Scale. Example 4 8 Nitrile, 96% H2SO4, and water were fed to a CSTR (as shown in Figure 2) to obtain a 1 () acid / nitrile mole ratio to form an aqueous hydrolysis mixture. After C s T R, 60 dwells for 37 minutes, the hydrolyzed mixture contains 41% acetonitrile with a weight ratio of less than 0.9%. The residence times of the aqueous hydrolysis mixture in the upstream of the circulation zone of the forward flow port and in the forward flow reaction zone between the forward flow port and the dilution point were 4 seconds and 3 minutes, respectively. After dilution, the reaction stream was fed to PFR, which was operated under adiabatic conditions at 75-100, with a residence time of 70 minutes. The finished aqueous hydrolysate contained 0.01% amidine 2 and less than 0.01% nitrile. The color of the finished aqueous hydrolysate was 6.5 based on Ghana. Printed by employees of the Central Standards Bureau of the Ministry of Economic Affairs, printed by the society (please read the precautions on the back before filling this page) -Am Example 4 9 Nitrile, 96% H2S04 and water are fed to the CSTR (as shown in Figure i) ) Moironitrile is obtained to form an aqueous hydrolysis mixture. It resides in C s T R, 69 ff, ^ t A 2 C for 46 minutes. The 'hydrolysis mixture contains 43% ammonium amine and 0.2% nitrile. Water-based Yongru,, _ &gt; Kun compound is in the upstream of the circulation zone of Xiangxiang flow port and between the forward flow port and, | 1,000 points. The paper size applies Chinese National Standard (CNS) A4 specifications (210X297 Mm) ^ 500〇A7

65 五、 發明説明（ 糾 &gt;瓦動反應區中之水性水解混合物之駐留時間分別為1秒及 少於1分。稀釋後，完成反應流進料至p F R，其於絕熱下， 80-1 04 °C操作，駐留時間為88分。完成之水性水解產物含 〇·〇2%腈及少於0.0 1%醯胺。完成之水性水解產物之顏色^ 於加納爾色標為8。 實例5 0 腈、96%H2S〇4及水進料至CSTR(如圖i所示）得i 〇酸〆 腈莫耳比’形成水性水解混合物。於C s T R、6 η v『r： U駐邊4 9分 後，水解混合物含40%醯胺及〇.〇 4%腈。水性水解混合物於 向前流動口 &lt;循環區上游中及於向前流動口與稀釋點間之向 削流動反應區中之水性水解混合物之駐留時間分別為1种2 少於1分。稀釋後，完成反應流進料至p F R，其於絕熱 82-104。〇操作，駐留時間92分。完成之水性水解:厶 〇.〇3 %腈及0.0 1%醯胺。完成之水性水解產物之顏色 I 納爾色標為8 . 5。 ； 實例5 1 腈、96%H2S〇4及水進料至CSTR(如圖丨所示）得1 〇酸/ 腈莫耳比，形成水性水解混合物。於c s T R、6 敗 L駐留37分 後，水解混合物留35%醯胺及〇〇3%腈。水性水解混合物於 向前流動口之循環區上游中及於向前流動口與稀釋點^ 2向 前流動反應區中之水性水解混合物之駐留時間分別為1=。 少於1分。稀釋後，完成反應流進料至ρ F R，其於絕“執 S2-1〇rC操作及駐留時間7〇分。完成之水性水：：：丄 0 · 0 2 %腈及0.0 1 %醯胺。完成之水性水解產物之顏色其於力口 度適用中國國家標準（&amp;S ) A4規格 (請先閲讀背面之注意事項再填寫本頁) 訂 經濟部中央榡準局員工消費合作社印製 -68 495500 經濟部中央標率局員工消費合作社印製 A7 B7 五、發明説明（66) 一~— 納爾色標為8。 實例5 2 腈、96%H2S〇4及水進料至CSTR(如圖i所示）得！ 〇酸/ 腈旲耳比，形成水性水解混合物。於cstr、61。〇下駐切口 分後二峰昆合物含43%醯胺及〇.〇5%腈。水性水解混：物 於向則W動R &lt;循壤區上游中及於向前流動口與稀釋點間之 向前流動反應區中之水性水解混合物之駐留時間分別為… 及少於1分。稀釋後，完成反應流進料至PFR，其於絕熱下 ’ 7 8 - 1 G 3 C操作及駐留時間為7 Q分。完成之水性水解產物 含0 . 〇 2 %醯胺，而腈未測定。完成之水性水解產物之顏色基 於加納爾色標為5。 實例5 3 腈、9 6 % H 2 S〇4及水進料至c S T R (如圖1所示）得丨〇酸/ 腈莫耳比，形成水性水解混合物。於c s τ R中6丨它駐留3 7分 後，水解混合物含40%醯胺及〇.〇 4%腈。水性水解混合物於 向觔流動口之循環區上游中及於向前流動口與稀釋點間之向 前流動反應區中之水性水解混合物之駐留時間分別為丨秒及 少於1分。稀釋後，完成反應流進料至p F R，其於絕熱下， 7 7 - 1 0 2 °C操作，駐留時間為7 0分。完成之水性水解產物含 0.0 1 % St胺及0.0 5 %腈。完成之水性水解產物之顏色基於加 納爾色標為6。 實例5 4 腈、96%H2S〇4及水進料至CSTR(如圖1所示）得1〇酸/ 腈莫耳比，形成水性水解混合物。於C S T R中、6 4 t：駐留3 7 本纸張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） (請先閱讀背面之注意事項再填寫本頁) .·)裝· 訂 495500 A7 B7 五 發明説明（ 67 經濟部中央標準局員工消費合作社印製 分後，水解混合物含4 1 %醯胺及0·〇2 %腈。水性水解混合物 於向七流動口之循環區上游中及於向前流動口與稀釋點間之 向如/瓦動反應區中之水性水解混合物之駐留時間分別為1秒 及少於1分。稀釋後，完成反應流進料至PFR，其於絕熱下 ，7 9- 1 03 °C操作，及駐留時間為7〇分。完成之水性水解產 物含0.0 1 %醯胺及〇 · 〇 3 %腈。完成之水性水解產物之顏色未 測定。 實例5 5 腈、9 6 % H 2 S Ο 4及水進料至c S T R (如圖1所示）得丨〇酸/ 腈莫耳比，形成水性水解混合物。於CsTr、6(TC駐留49分 後，水解混合物含40%醯胺及0·04%腈。水性水解混合物於 向前流動口之循環區上游中及於向前流動口與稀釋點間之向 前流動反應區中之水性水解混合物之駐留時間分別為丨秒及 少於1分。稀釋後，完成反應流進料至PFR，其於絕熱下79_ 1 03 °C操作及駐留時間70分。完成之水性水解產物含〇 〇ι% 醯胺及0.04%腈。完成之水性水解產物之顏色基於加納爾色 標為9。 實例5 6 基於實驗室批次水解數據以計算機模擬連續水解系統之性 能。將96%HC1及腈連續料至CSTR，將1：15酸/腈莫耳比 ，形成水性水解混合物。於CSTR中，5〇。〇駐留6〇分後，水 解混合物含46%醯胺及0.1%腈。離開CSTR之腈水解反應 器產物流輸送至醯胺水解階式塔型反應器。其加以攪動增進 流體混合及將NH4C1固體懸浮於各階式隔室中。藉圍繞反應 表纸張尺度適用中國國家標準（CNS Γα4規格 ♦ m ·裝------1T-----Am (請先閲讀背面之注意事項再填寫本頁) 495500 A7 B7 五、發明説明（ 68 經濟部中央標準局員工消費合作社印製 器殼之套層或藉將產物流通過外面之進料預熱器而提供8〇t 之反應器溫度。此流於醯胺水解反應器中之駐留時間為4小 時°冗成之水性水解產物含〇 . 〇 4 %醯胺及〇 〇 4 %腈。 實例5 7 基於實驗室批次水解數據以計算機模擬連續水解系統之性 能。36%HC1及腈連續進料至CSTR，將115酸/腈莫耳比 ’形成水性水解混合物。於C s T R中，5 0 下駐留6 0分後， 水解混合物含46%醯胺及0.1 %腈。離開CSTR之腈水解反 應器產物流輸送至第二CSTR供完成80-90%之醯胺水解。 於第二CSTR中駐留4小時後，將會NlCl之醯胺水解漿冷 卻至5(TC，以離心除去NH4C1。離心之母液輸送至8〇它下 操作之插塞流動反應器，藉使用套層或外面之預熱器。pFR 未攪動，由於NH^l於該溫溶解且於PFR内以濃縮物存在。 於PFR中駐留2小時後，完成之水性水解產物含〇〇4%醯胺 及0.04 %腈。 虹 雖然尽發明易於接受各種修飾及替代之形式，但其特殊具 體實施例藉由附圖中之實例已顯示且已於本文詳細說明。然 而，應了解的是其並非表示限制本發明於所揭示之特別米'式 ，而相反地，本發明涵蓋在由附加之申請專利範園;所 之本發明之主旨及範圍内之所有修飾法、同等物及替代 71 - 本纸張尺度適用中國國家標準（CNS ) A4規格（21〇χ 297公釐） (請先閱讀背面之注意事項再填寫本頁)65 V. Description of the invention The residence time of the aqueous hydrolysis mixture in the tile reaction zone is 1 second and less than 1 minute. After dilution, the reaction stream is fed to p FR, which is 80- 1 04 ° C operation, dwell time is 88 minutes. The completed aqueous hydrolysate contains 0.02% nitrile and less than 0.0 1% amidine. The color of the completed aqueous hydrolysate is ^ on the Garner color scale. 8. Examples 5 0 Nitrile, 96% H2SO4 and water were fed to the CSTR (as shown in Figure i) to obtain an acidic nitrile mol ratio of iO acid to form an aqueous hydrolysis mixture. At C s TR, 6 η v "r: U After 49 minutes, the hydrolysis mixture contained 40% ammonium and 0.04% nitrile. The aqueous hydrolysis mixture reacted in the forward flow of the forward flow port &lt; upstream of the circulation zone and between the forward flow port and the dilution point. The residence time of the aqueous hydrolysis mixture in the zone is 1 type 2 less than 1 minute. After dilution, the reaction stream is fed to the p FR, which is operated at an adiabatic 82-104 °, and the residence time is 92 minutes. Complete aqueous hydrolysis : 0.03% nitrile and 0.01 1% amidine. The color I of the finished aqueous hydrolyzate is nal. The color scale is 8.5. Example 5 1 Nitrile, 96% H2SO4, and water were fed to the CSTR (as shown in Figure 丨) to obtain a molar ratio of 10 acid / nitrile to form an aqueous hydrolysis mixture. After 37 minutes in cs TR and 6 L, the hydrolysis mixture remained 35% ammonium amine and 03% nitrile. The residence time of the aqueous hydrolysis mixture in the upstream of the circulation zone of the forward flow port and in the forward flow port and the dilution point ^ 2 The residence time of the aqueous hydrolysis mixture in the forward flow reaction zone are 1 =. Less than 1 minute. After dilution, the reaction stream is fed to ρ FR, which is performed in S2-1〇rC operation and residence time 70 minutes. Aqueous water completed :: 丄 0 · 0 2 % Nitrile and 0.0 1% ammonium amine. The color of the finished aqueous hydrolysate is applicable to the national standard (&amp; S) A4 in terms of strength (please read the precautions on the back before filling this page). Printed by the Consumers 'Cooperatives of the quasi bureau-68 495500 Printed by the Consumers' Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs A7 B7 V. Description of the invention (66) I ~-The color scale of Nal is 8. Example 5 2 Nitrile, 96% H2S〇4 And water is fed to the CSTR (as shown in Figure i)! 〇Acid / nitrile ratio, forming an aqueous hydrolysis mixture. After tr, 61.0, the two-peak kun compound contains 43% ammonium amine and 0.05% nitrile. Aqueous hydrolyzed mixture: the material is moved to the upper part of the soil along the upstream and forward. The residence time of the aqueous hydrolysis mixture in the forward flow reaction zone between the flow port and the dilution point are… and less than 1 minute. After dilution, the reaction stream is fed to PFR, which is adiabatic '7 8-1 G 3 C operation and dwell time is 7 Q minutes. The finished aqueous hydrolysate contained 0.02% amidine, and the nitrile was not determined. The color of the finished aqueous hydrolysate is 5 based on the Garner color scale. Example 5 3 Nitrile, 96% H 2 S0 4 and water were fed to c S T R (as shown in FIG. 1) to obtain a molar ratio of acid / nitrile to form an aqueous hydrolysis mixture. After 6 丨 it stayed in c s τ R for 37 minutes, the hydrolysis mixture contained 40% amidine and 0.04% nitrile. The residence time of the aqueous hydrolysis mixture in the upstream of the circulation zone of the tendon flow port and in the forward flow reaction zone between the forward flow port and the dilution point were 丨 seconds and less than 1 minute, respectively. After dilution, the reaction stream was fed to p F R, which was operated at 7 7-102 ° C under adiabatic conditions with a residence time of 70 minutes. The finished aqueous hydrolysate contains 0.01% St amine and 0.05% nitrile. The color of the finished aqueous hydrolysate is 6 based on the Garner color scale. Example 5 4 Nitrile, 96% H2SO4, and water were fed to a CSTR (as shown in Figure 1) to obtain a 10 acid / nitrile mole ratio to form an aqueous hydrolysis mixture. In CSTR, 6 4 t: Resident 3 7 This paper size is applicable to Chinese National Standard (CNS) A4 specification (210X297 mm) (Please read the precautions on the back before filling this page). ·) Binding 495500 A7 B7 Fifth invention description (67 After printing by the Consumer Cooperatives of the Central Bureau of Standards of the Ministry of Economic Affairs, the hydrolysis mixture contains 41% ammonium amine and 0.02% nitrile. The aqueous hydrolysis mixture is located upstream of the circulation zone towards Qiliukou and in The residence time of the aqueous hydrolysis mixture between the forward flow port and the dilution point in the Ru / Wan reaction zone is 1 second and less than 1 minute. After dilution, the reaction stream is fed to PFR, which is adiabatic, 7 9-1 03 ° C operation, and dwell time is 70 minutes. The completed aqueous hydrolysate contains 0.01% ammonium amine and 0.03% nitrile. The color of the completed aqueous hydrolysate is not determined. Example 5 5 Nitrile , 96% H 2 S 〇 4 and water were fed to c STR (as shown in Figure 1) to obtain the acid / nitrile molar ratio to form an aqueous hydrolysis mixture. After CsTr, 6 (49 minutes in TC, hydrolyzed The mixture contains 40% ammonium amine and 0.04% nitrile. The aqueous hydrolysis mixture is in the circulation zone of the forward flow port. The residence time of the aqueous hydrolysis mixture in the forward flow reaction zone between the forward flow port and the dilution point is 丨 seconds and less than 1 minute. After dilution, the reaction flow is fed to the PFR, which is adiabatic Operating under 79_ 1 03 ° C and dwell time 70 minutes. The completed aqueous hydrolysate contains 0.00% ammonium amine and 0.04% nitrile. The color of the completed aqueous hydrolysate is based on the Garner color scale of 9. Example 5 6 Based on experiments The batch hydrolysis data in the chamber was simulated by computer to simulate the performance of continuous hydrolysis system. 96% HC1 and nitrile were continuously fed to CSTR, and the acid / nitrile molar ratio of 1:15 was formed to form an aqueous hydrolysis mixture. In the CSTR, 50% was resident. After 60 minutes, the hydrolysis mixture contained 46% ammonium and 0.1% nitrile. The product stream of the nitrile hydrolysis reactor leaving CSTR was sent to the amidine hydrolysis cascade reactor. It was agitated to enhance fluid mixing and suspend the NH4C1 solids in In various compartments. Chinese national standards (CNS Γα4 size ♦ m · pack ------ 1T ----- Am are applied around the paper size of the reaction table) (Please read the precautions on the back before filling this page ) 495500 A7 B7 V. Description of Invention (68 Economy The jacket of the printed shell of the Consumer Standards Cooperative of the Central Bureau of Standards may provide a reactor temperature of 80 t by passing the product stream through an external feed preheater. The residence time of this stream in the amidine hydrolysis reactor is 4 Hourly redundant aqueous hydrolysis product contains 0.04% ammonium amine and 0.004% nitrile. Example 5 7 Based on laboratory batch hydrolysis data, the performance of a continuous hydrolysis system is simulated by computer. 36% HC1 and nitrile continuous feed To the CSTR, the 115 acid / nitrile mole ratio 'was formed into an aqueous hydrolysis mixture. After standing in C s T R for 60 minutes at 50, the hydrolysis mixture contained 46% amidine and 0.1% nitrile. The product stream of the nitrile hydrolysis reactor leaving the CSTR is sent to a second CSTR for completion of 80-90% of the amidine hydrolysis. After staying in the second CSTR for 4 hours, the NlCl hydrochloride hydrolysis slurry was cooled to 5 ° C to remove NH4C1 by centrifugation. The mother liquor of the centrifugation was transferred to a plug flow reactor operated under 80 ° C by using a jacket. Or outside preheater. PFR is not agitated, because NH ^ l is dissolved at this temperature and exists as a concentrate in PFR. After standing in PFR for 2 hours, the completed aqueous hydrolysate contains 0.4% ammonium amine and 0.04 % Nitrile. Although the rainbow is easy to accept various modifications and alternative forms, its specific embodiments have been shown by the examples in the drawings and have been described in detail herein. However, it should be understood that it is not intended to limit the invention In the special meter's form disclosed, on the contrary, the present invention covers all modifications, equivalents, and substitutions within the spirit and scope of the present invention, which is covered by the attached patent application 71-This paper standard applies Chinese National Standard (CNS) A4 specification (21〇χ 297 mm) (Please read the precautions on the back before filling this page)

Claims (1)

495500495500 第085106567號專利申請案 中文申請專利範圍jipp私(⑴芊6月）六、申請專利範IPatent application No. 085106567 Chinese patent application scope jipp private (⑴ 芊 June) 1· 一種製備2 -羥基-4 -甲硫丁酸或其鹽之方法，其包括·· 將水性礦酸引入包含第一連續攪拌槽反應器之腈水解反 應器； 將2 -羥基-4 -甲硫丁腈引入該腈水解反應器； 於該腈水解反應器中連續水解2 -羥基-4 -甲硫丁腈，產 生含2 -羥基-4 -甲硫丁醯胺之腈水解反應器產物流； 將水及該腈水解反應器產物流引入醯胺水解流動反應器 :及 於該醯胺水解流動反應器中連續水解2 -羥基-4 -甲硫丁 醯胺，產生含2 - #i基-4 -甲硫丁酸之完成之水性水解產物 2·根據申請專利範圍第1項之方法，其中將該水及該腈水解 反應器產物流混合形成完成反應流，以致當該完成反應流 流過該醯胺水解流動反應器時，2 -羥基-4 -甲硫丁醯胺之 水解實質上已完成。 3·根據申請專利範圍第2項之方法，其中在該腈水解反應器 產物流引入該醯胺水解流動反應器以前，將該腈水解反應 產物流以該水稀釋。 4·根據申請專利範圍第2項之方法，其中在將該水流引入混 合器供稀釋該腈水解反應器產物流形成該完成反應流並防 止液相分離前先加以加熱。 5· —種分離2-羥基-4-甲硫丁酸或其鹽之方法，包括： 將水性礦酸引入包含第一連續攪拌槽反應器之腈水解反 應器； 本紙張尺度適用中國國家標準(CNS) A4規格（210 X 297公釐）1. A method for preparing 2-hydroxy-4-methylthiobutanoic acid or a salt thereof, comprising: introducing an aqueous mineral acid into a nitrile hydrolysis reactor containing a first continuous stirred tank reactor; and introducing 2-hydroxy-4- Methylthiobutyronitrile is introduced into the nitrile hydrolysis reactor; 2 -hydroxy-4-methylthiobutyronitrile is continuously hydrolyzed in the nitrile hydrolysis reactor to produce a nitrile hydrolysis reactor product containing 2-hydroxy-4-methylthiobutyramine Stream; introducing water and the product stream of the nitrile hydrolysis reactor into the amidine hydrolytic flow reactor: and continuously hydrolyzing 2-hydroxy-4-methylthiobutaneamine in the amidine hydrolytic flow reactor to produce a 2- # i Aqueous hydrolysate of methyl-4-methiobutyric acid 2. The method according to item 1 of the scope of patent application, wherein the water and the nitrile hydrolysis reactor product stream are mixed to form a complete reaction stream, so that when the complete reaction stream When flowing through the ammonium hydrolysis flow reactor, the hydrolysis of 2-hydroxy-4-methanebutanamine is essentially complete. 3. The method according to item 2 of the scope of patent application, wherein the nitrile hydrolysis reaction product stream is diluted with the water before the nitrile hydrolysis reactor product stream is introduced into the amidine hydrolysis flow reactor. 4. The method according to item 2 of the scope of patent application, wherein the water stream is heated before being introduced into the mixer for diluting the nitrile hydrolysis reactor product stream to form the completed reaction stream and preventing liquid phase separation. 5. · A method for separating 2-hydroxy-4-methylthiobutyric acid or a salt thereof, comprising: introducing an aqueous mineral acid into a nitrile hydrolysis reactor including a first continuous stirred tank reactor; the paper size is applicable to Chinese national standards ( CNS) A4 size (210 X 297 mm) 裝 訂 m 495500 A B c D 六、申請專利範圍 將2 -羥基-4 -甲硫丁腈引入該腈水解反應器； 於該腈水解反應器内連續水解2 -羥基-4 -甲硫丁腈產生 含2 -羥基-4 -甲硫丁醯胺之腈水解反應器產物流； 將離開該腈水解反應器之該腈水解反應器產物流及水引 入含第二連續攪拌槽反應器之連續醯胺水解反應器，以致 含於該腈水解反應器產物流中之實質部分之2-羥基-4 -甲 硫丁醯胺於該第二連續攪拌槽反應器中水解形成完成反應 流； 將該完成反應流連續引入醯胺水解流動反應器内；及 於該醯胺水解流動反應器中連續水解2 -羥基-4 -甲硫丁 醯胺，產生含2 -羥基-4 -甲硫丁酸之完成之水性水解產物 〇 6·根據申請專利範圍第1或5項之方法，其中將H 2 S Ο 4引入 該腈水解反應器中，於酸流中具5 0 %重量比與7 0 %重量 比間之強度之H2S04。 7·根據申請專利範圍第1或5項之方法，其中將112304引入 該腈水解反應器中，於酸流中具7 0 %重量比及9 9 %重量 比之間之強度&lt;H2S04，且將該酸流連續地引入該腈水 解反應器同時引入水，於該腈水解反應器中形成基於無有 機物5 0 %重量比與7 0 %重量比間之強度之H 2 S Ο 4。 8·根據申請專利範圍第1或5項之方法，其中於該腈水解反 應器中至少9 0 % 2 -羥基-4 -甲硫丁腈轉化成2 -羥基-4 -甲 硫丁醯胺。 9·根據申請專利範圍第1或5項之方法，其中該水性礦酸為 _ -2· 本紙張尺度適财國时標準(CNS) Α4規格(21GX 297公#) &quot; &quot; 申請專利範圍 H2S04，且引入該腈水解反應器中之h2s〇4對2-幾基-4-甲石危丁腈之莫耳比於〇 . 6與1 . 5之間。 ι〇·根據申凊專利範圍第1或5項之方法，其中該水性礦酸為 H2S04，且引入該腈水解反應器中之h2S04,2-幾基-4-甲石瓦丁腈之莫耳比為〇 . 9與1 . 2之間。 11·根據申請專利範圍第1或5項之方法，其中於該製程開始 至於該醯胺水解流動反應器中建立穩定狀況之間之期間中 ，引入該腈水解反應器中之H2S04對2-羥基-4 -甲硫丁腈 之莫耳比1.0與2.0之間，其後該H2S04對2-羥基-4-甲硫 丁腈之莫耳比0 · 6與1 . 5之間。 12.根據申請專利範圍第1或5項之方法，其中於該製程開始 至於該醯胺水解流動反應器中建立穩定狀況之間之期間内 ’引入該腈水解反應器中之H2S04對2-羥基-4-甲硫丁腈 之莫耳比於1·〇與1.5之間，且其後該112304與2-羥基-4-甲硫丁腈之莫耳比為〇 . 9輿1 . 2之間。 13·根據申請專利範圍第1或5項之方法，其中流入該醯胺水 解流動反應器之速率與流入該醯胺水解流動反應器中之2 -羥基-4 -甲硫丁醯胺與2 -羥基-4 -甲硫丁腈之速率之比加 以控制以提供比引入該醯胺水解流動反應器之2 -羥基-4 -甲硫丁醯胺及2 -羥基-4 -甲硫丁腈之化學計量上同等量之 至少5%莫耳過量之過量礦酸。 14·根據申請專利範圍第1 3項之方法，其中以能於該醯胺水 解流動反應器中有效地提供該過量之相對速率將礦酸及2 -羥基-4 -甲硫丁腈引人該腈水解反應器中。 本紙張尺度適用中國國家標準(CNS) Α4規格(210 X 297公釐） 495500Binding m 495500 AB c D VI. Application scope of patent Introducing 2-hydroxy-4-methylthiobutyronitrile into the nitrile hydrolysis reactor; Continuous hydrolysis of 2-hydroxy-4-methylthiobutyronitrile in the nitrile hydrolysis reactor produces Product stream of nitrile hydrolysis reactor of 2 -hydroxy-4-methanebutanidine; The product stream of nitrile hydrolysis reactor leaving the nitrile hydrolysis reactor and water are introduced into the continuous ammonium hydrolysis of the reactor containing the second continuous stirred tank The reactor, so that a substantial portion of the 2-hydroxy-4-methylthiobutanamine contained in the product stream of the nitrile hydrolysis reactor is hydrolyzed in the second continuous stirred tank reactor to form a complete reaction stream; Continuous introduction into the amidine hydrolysis flow reactor; and continuous hydrolysis of 2-hydroxy-4-methylthiobutaneamine in the amidine hydrolysis flow reactor to produce a finished aqueous solution containing 2-hydroxy-4-methylthiobutane acid Hydrolysate 06. The method according to item 1 or 5 of the scope of the patent application, wherein H 2 S 〇 4 is introduced into the nitrile hydrolysis reactor, and there is between 50% by weight and 70% by weight in the acid stream. The intensity of H2S04. 7. The method according to item 1 or 5 of the scope of patent application, wherein 112304 is introduced into the nitrile hydrolysis reactor, and has an intensity between 70% by weight and 99% by weight in the acid stream &lt; H2S04, and The acid stream is continuously introduced into the nitrile hydrolysis reactor while water is introduced, and H 2 S 0 4 is formed in the nitrile hydrolysis reactor based on the strength between 50% by weight and 70% by weight of no organic matter. 8. A method according to item 1 or 5 of the scope of the patent application, wherein at least 90% of 2-hydroxy-4-methylthiobutyronitrile is converted to 2-hydroxy-4-methylthiobutaneamine in the nitrile hydrolysis reactor. 9. The method according to item 1 or 5 of the scope of patent application, wherein the water-based mineral acid is _ -2. The paper size is suitable for the national standard (CNS) Α4 specification (21GX 297 公 #) &quot; &quot; The scope of patent application H2S04, and the molar ratio of h2s〇4 to 2-quinyl-4-methystyronitrile introduced into the nitrile hydrolysis reactor was between 0.6 and 1.5. ι〇. The method according to item 1 or 5 of the scope of the patent application, wherein the aqueous mineral acid is H2S04, and the mole of h2S04,2-quinyl-4-methyvalantonitrile introduced into the nitrile hydrolysis reactor The ratio is between 0.9 and 1.2. 11. The method according to item 1 or 5 of the scope of the patent application, wherein during the period between the start of the process and the establishment of a stable state in the amidine hydrolysis flow reactor, the H2S04-2-hydroxy group introduced into the nitrile hydrolysis reactor is introduced. -4-Molar ratio of methylthiobutyronitrile is between 1.0 and 2.0, and then the molar ratio of H2S04 to 2-hydroxy-4-methylthiobutyronitrile is between 0.6 and 1.5. 12. The method according to item 1 or 5 of the scope of patent application, wherein the H2S04-2-hydroxy group introduced into the nitrile hydrolysis reactor is introduced between the start of the process and the establishment of a stable condition in the amidine hydrolysis flow reactor. The molar ratio of -4-methylthiobutyronitrile is between 1.0 and 1.5, and then the molar ratio of 112304 and 2-hydroxy-4-methylthiobutyronitrile is 0.9 to 1.2. . 13. The method according to item 1 or 5 of the scope of the patent application, wherein the rate of flowing into the amidine hydrolytic flow reactor and the rate of flowing into the amidine hydrolytic flow reactor are 2-hydroxy-4-methylthiobutamine and 2- The ratio of the rate of hydroxy-4-methylthiobutyronitrile is controlled to provide a chemistry that is greater than that of the 2-hydroxy-4-methylthiobutyramine and 2-hydroxy-4-methylthiobutyronitrile introduced into the amidine hydrolysis flow reactor. Measure an equivalent amount of excess mineral acid in an excess of at least 5% mole. 14. A method according to item 13 of the scope of application for a patent, wherein the mineral acid and 2-hydroxy-4-methylthiobutyronitrile are introduced at a relative rate effective to provide the excess in the ammonium hydrolysis flow reactor. Nitrile hydrolysis reactor. This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) 495500 8 8 8 8 A B c D 15. 根據申請專利範圍第」或5項之方法，其中於穩定狀況下 ，於該醯胺水解流動反應器出口之該完成之水性水解產物 包含至少3 6重量％ 2 -羥基_ 4 -甲硫丁酸、至少丨8重量％銨 鹽、至少2 0重量％水、高至〇 · 〇 5重量％醯胺及高至〇 · 〇 5 重量％腈。 16. 根據申請專利範圍第丨5項之方法，其中於製程開始後， 所產生之該芫成之水性水解產物含高至〇 . 〇 5重量。/。及高至 0 · 0 5重量％腈。 17·根據申請專利範圍第1或5項之方法，其中該腈水解反應 器產物含高至16重量％ 2-羥基-4-甲硫丁酸，高至12重量 %銨鹽，至少6重量％水、至少3 〇重量❶/。醯胺及高至2重量 %腈。 18. 根據申請專利範圍第5項之方法，其中該醯胺水解流動反 應器為插塞流動反應器，且通過該插塞流動反應器之該完 成反應流之流動為擾動的。 19. 根據申請專利範圍第5項之方法，其中該腈水解反應器產 物流在引入該連續醯胺水解反應器以前，以該水加以稀釋 〇 20. 根據申請專利範圍第2或5項之方法，其中該醯胺水解流 動反應器包括充填之管柱反應器，且該完成反應流以等於 或高於該充填之管柱反應器之閾速度流過該充填之管柱反 應器。 21. 根據申請專利範圍第2或5項之方法，其中該醯胺水解流 動反應器包括管道反應器，且該完成反應流以擾動流動通 -4- 本紙張尺度適用中國國家標準(CNS) A4規格(210 X 297公釐）8 8 8 8 AB c D 15. The method according to item ”or 5 of the scope of patent application, wherein in a stable condition, the completed aqueous hydrolysate at the outlet of the ammonium hydrolysis flow reactor contains at least 36% by weight 2 -Hydroxy-4-methylthiobutyric acid, at least 8% by weight ammonium salt, at least 20% by weight water, up to 0.05% by weight amidine and up to 0.05% by weight nitrile. 16. The method according to item 5 of the scope of patent application, wherein after the process starts, the resulting aqueous hydrolysate contains up to 0.05 wt. /. And up to 0. 05 wt% nitrile. 17. The method according to item 1 or 5 of the scope of patent application, wherein the nitrile hydrolysis reactor product contains up to 16% by weight of 2-hydroxy-4-methylthiobutanoic acid, up to 12% by weight of ammonium salt, and at least 6% by weight Water, at least 30 wt.%. Amidine and up to 2% by weight nitrile. 18. The method according to item 5 of the application, wherein the ammonium hydrolysis flow reactor is a plug flow reactor, and the flow of the completed reaction flow through the plug flow reactor is disturbed. 19. A method according to item 5 of the patent application, wherein the product stream of the nitrile hydrolysis reactor is diluted with the water before being introduced into the continuous amidine hydrolysis reactor. 20. A method according to item 2 or 5 of the patent application Wherein the ammonium hydrolysis flow reactor includes a packed column reactor, and the completed reaction stream flows through the packed column reactor at a threshold speed equal to or higher than the threshold of the packed column reactor. 21. The method according to item 2 or 5 of the scope of patent application, wherein the ammonium hydrolysis flow reactor includes a pipeline reactor, and the completion of the reaction flow to disturb the flow path -4- The paper size applies to Chinese National Standard (CNS) A4 Specifications (210 X 297 mm) 495500 A8 B8 C8 ------- D8 __ 六、申請專利範圍 過該管道反應器。 22·根據申請專利範圍第2 1項之方法，其中該醯胺水解流動 反應备以雷諾數大於3，0 0 0操作。 23.根據申請專利範圍第2 1項之方法，其中該醯胺水解流動 反應器以雷諾數大於5，〇 〇 〇操作。 24·根據申請專利範圍第1或5項之方法，其中該醯胺水解流 動反應器為插塞流動反應器，其以皮克里特準數至少5〇 操作’高峰溫度9 0至1 2 0 °C及駐留時間3 0與9 0分之間。 25·根據申請專利範圍第1或5項之方法，其中該醯胺水解流 動反應器實質上於絕熱下操作。 26. 根據申請專利範圍第1或5項之方法，其中該醯胺水解流 動反應器實質上於等溫下操作。 27. 根據申請專利範圍第1或5項之方法，其中該醯胺水解流 動反應器於絕熱及自熱下操作。 28·根據申請專利範圍第1或5項之方法，其中2 _羥基_ 4 -甲硫 丁酸之回收藉由中和該完成之水性水解產物形成含2 _經 基-4 -甲硫丁酸之有機相及水相，分離該有機相與該水相 回收2 -幾基-4 -甲硫丁酸。 29·根據申請專利範圍第1或5項之方法，其中自該方法放射 之蒸氣不高於每1000碎產物2-經基-4-甲硫丁酸〇.5 scf 〇 30·根據申請專利範圍第2 9項之方法，其中自該方法放射之 蒸氣不高於每1000磅產物0.3 scf之2 -羥基-4-甲硫丁酸 -5- 本紙張尺度適用中國國家標準(CNS) A4規格(210X 297公釐）495500 A8 B8 C8 ------- D8 __ VI. Scope of patent application Pass the pipeline reactor. 22. The method according to item 21 of the scope of patent application, wherein the ammonium hydrolyzation flow reaction is prepared with a Reynolds number greater than 3,000. 23. A method according to item 21 of the scope of patent application, wherein the amidine hydrolysis flow reactor is operated with a Reynolds number greater than 5,000. 24. The method according to item 1 or 5 of the scope of the patent application, wherein the ammonium hydrolysis flow reactor is a plug flow reactor, which operates at a Pickeret number of at least 50. 'Peak temperature 9 0 to 1 2 0 ° C and dwell time between 30 and 90 minutes. 25. A method according to item 1 or 5 of the scope of patent application, wherein the amidine hydrolysis flow reactor is operated substantially adiabatically. 26. The method according to item 1 or 5 of the scope of patent application, wherein the amidine hydrolysis flow reactor is operated substantially at isothermal temperature. 27. The method according to item 1 or 5 of the scope of patent application, wherein the amidine hydrolysis flow reactor is operated under adiabatic and autothermal conditions. 28. The method according to item 1 or 5 of the scope of the patent application, wherein the recovery of 2-hydroxy-4-methylthiobutyric acid is carried out by neutralizing the completed aqueous hydrolysate to form 2-methyl-4-thiomethylbutanoic acid. The organic phase and the aqueous phase are separated, and the organic phase and the aqueous phase are separated to recover the 2-chido-4-methylthiobutanoic acid. 29. The method according to item 1 or 5 of the scope of patent application, wherein the vapor radiated from the method is not higher than 2-acryl-4-methylthiobutanoic acid 0.5 scf 〇30 per 1,000 broken products. 30. According to the scope of patent application The method of item 29, wherein the vapor radiated from the method is not higher than 0.3 scf 2-hydroxy-4-methylthiobutanoic acid-5- per 1,000 pounds of product. This paper is in accordance with China National Standard (CNS) A4 specifications ( 210X 297 mm) 495500 A8 B8 C8 ___D8 ____ 六、申請專利範圍 &quot; 31·根據申請專利範圍第5項之方法，其中於該腈水解反應器 中形成之至少8 0 %之2 -羥基-4 -甲硫丁醯胺於該連續之醯 胺水解反應器中轉化成2 -經基-4 -甲硫丁酸。 32·根據申請專利範圍第9項之方法，其中該連續醯胺水解反 應器於範圍由7 0 °C至1 2 0 °C之溫度下操作。495500 A8 B8 C8 ___D8 ____ 6. Scope of patent application &quot; 31. The method according to item 5 of the scope of patent application, wherein at least 80% of 2-hydroxy-4-methylthiobutane is formed in the nitrile hydrolysis reactor. Amines are converted into 2-mercapto-4 -methanethiobutyric acid in this continuous amidine hydrolysis reactor. 32. The method according to item 9 of the scope of patent application, wherein the continuous amidine hydrolysis reactor is operated at a temperature ranging from 70 ° C to 120 ° C. 33.根據申請專利範圍第5項之方法，其中將該水性礦酸、該 水流及該猜水解反應產物流混合形成酿胺水解混合物，將 其引入連續醯胺水解反應器中。 34· —種製備2-羥基-4-甲硫丁酸或其鹽之方法，包括： 將水性礦酸及2-輕基-4-甲硫丁腈引入腈水解反應器中 9 於該腈水解反應器中，連續水解2 -羥基-4 -甲硫丁腈， 產生含2-羥基-4-甲硫丁醯胺之腈水解反應器產物流； 將水、水性礦酸及該腈水解反應器產物流引入醯胺水解 流反應器中；及 鲁 於該醯胺水解反應器内連續水解2 -羥基-4 -甲硫丁醯胺 產生含2 -羥基-4 -甲硫丁酸之完成之水性水解產物。 35·根據申請專利範圍第3 4項之方法，其中加至該腈水解反 應器中之礦酸對2 -羥基-4 -甲硫丁腈之莫耳比於〇 . 5與 0.95之間，且礦酸對2-羥基-4-甲硫丁腈之總莫耳比〇.6 與〇 . 9 5之間。 36·根據申請專利範圍第3 5項之方法，其中加至該腈水解反 應器中之礦酸對2 -羥基-4 -甲硫丁腈之莫耳比，〇 . 8與 〇 · 9 5之間，且礦酸對2 -羥基-4 -甲硫丁腈之總莫耳比， -6- 本紙張尺度適用中國國家標準(CNS) A4規格(210X297公釐) &quot; ； 495500 A B c D 六、申請專利範圍 〇 · 8 5與0.9 5之間。 37. 根據申請專利範圍第3 4項之方法，其中該腈水解反應器 包括第一連續攪拌槽反應器，於該腈水解反應器内將2 -羥 基-4 -甲硫丁腈連續水解，該腈水解產物流引入該醯胺水 解反應器中，其中包含醯胺水解流動反應器，再於該醯胺 水解流動反應器中將2-羥基-4-甲硫丁醯胺連續水解。 38. 根據申請專利範圍第3 4項之方法，其中該腈水解反應器 包含第一連續攪拌槽反應器，於該腈水解反應器中2 -羥 基-4-甲硫丁腈連續水解，該腈水解反應器產物流引入含 第二連續攪拌槽反應器之連續醯胺水解反應器中，2 -羥 基-4 -甲硫丁醯胺於該第二連續攪拌槽反應器中連續水解 形成完成反應流，該完成反應流引入該含醯胺水解流動反 應器之醯胺水解反應器，且當該完成反應流流過該醯胺水 解流動反應器時，該2-羥基-4-甲硫丁醯胺之水解實質上 已完成。 39. —種製備2-羥基-4-甲硫丁酸或其鹽之方法，其包括： 同時地將2-羥基-4-甲硫丁腈、具70%重量比與99%重 量比之間強度之濃H2S04流及水引入其中水解2-羥基-4-甲硫丁腈之容器，水與硫酸以此相對比例添加，而得提供 含有具介於5 0重量％至7 0重量％之強度（以不含有機計）之 混合物； 於該容器内水解2 -羥基-4 -甲硫丁腈產生含2 -羥基-4 -甲硫丁醯胺之腈水解產物流；及 水解2 -羥基-4 -甲硫丁醯胺產生含2 -羥基-4 -甲硫丁酸 本紙張又度適用中國國家標準(CNS) A4規格(210 X 297公釐） 495500 六 Λ8 B8 C8 _____ D8 、申請專利範圍 之冗成之水性水解產物。 40·根據申凊專利範圍弟3 9項之方法，其中該容器為含第一 連續攪拌槽反應器之腈水解反應器，於該腈水解反應器中 2 -羥基-4 -甲硫丁腈連續水解，該腈水解產物流引入醯胺 水解流動反應器中，於該醯胺水解流動反應器中，2 _經 基-4 -甲硫丁縫胺連續水解。 41.根據申請專利範圍第3 9項之方法，其中該容器為含第一 連續攪拌槽反應器之腈水解反應器，於該腈水解反應器中 ，2 -羥基-4 -甲硫丁腈連續水解，該腈水解反應器產物流 引入含第二連續攪拌槽反應器之連續醯胺水解反應器，於 $亥弟一連績授摔槽反應器中，2 -經基-4 -甲硫丁酿胺連續 水解形成完成反應流，該完成反應流引入醯胺水解流動反 應器中，當該完成反應流流過該醯胺水解流動反應器時， 該2-羥基-4-甲硫丁醯胺之水解實質上已完成。 42·根據申請專利範圍第1、5或3 9項之方法，其另包括自該 完成之水性水解產物回收2 -羥基-4 -甲硫丁酸或其鹽或衍 生物。 43·根據申請專利範圍第1、5或3 9項之方法，其中藉由自該 完成之水性水解產物抽提2 -羥基-4 -甲硫丁酸而回收2 -羥 基-4-甲硫丁酸。 44·根據申請專利範圍第3 9項之方法，其中自該方法放射之 蒸氣不高於每1 000磅產物2-羥基-4 -甲硫丁酸0.5 scf。 45·—種製備2 -羥基-4 -甲硫丁酸或其鹽之方法，包括： 將2 -羥基-4 -甲硫丁腈及水性礦酸引入含2 -羥基-4 -甲 -8- 本紙張尺度適用中國國家標準(CNS) A4規格（210 X 297公釐） 8 8 8 8 A B c D 495500 六、申請專利範圍 硫丁醯胺、礦酸、及未反應之2 -羥基-4 -甲硫丁腈之水性 水解混合物中； 將於該水解混合物中之2 -羥基-4 -甲硫丁腈於包含回混 反應區及於流體流動中與該回混反應區交通之彳盾）衣區（该 循環區包含循環線）之連續腈水解反應器中水解； 將該水性水解混合物於自該回混反應區抽回之循環流中 連續循環，通過該循環區再回至該回混反應區，該循環流 當自該回混反應區抽回時含未反應之2 -羥基-4 -甲硫丁腈 j 自該循環區中之向前流動口除去該循環之水性水解混合 物之一部分為腈水解反應器產物流，並輸送該腈水解反應 器產物流至酿胺水解流動反應器； 將該腈水解反應器產物流於該向前流動口之下游處以水 稀釋提供完成反應流； 於該醯胺水解流動反應器中含於該完成反應流之2-羥 基-4 -甲硫丁醯胺水解，產生含2 -羥基-4 -甲硫丁酸之完成 之水性水解產物， 於該向前流動口之該循環區上游中之該循環流之駐留時 間與該向前流動口之該腈水解反應器產物流在稀釋以前之 駐留時間之和，在該腈水解反應器產物流稀釋以前，足以 實質上區別殘留之2 -羥基-4 -甲硫丁腈。 46.根據申請專利範圍第1或4 5項之方法，其中該水性礦酸、 該水流及該腈水解反應產物流混合形成完成反應流，將其 引入醯胺水解流動反應器。 -9- 本紙張尺度適用中國國家標準(CNS) A4規格（210 X 297公釐) &quot;~一33. The method according to item 5 of the scope of patent application, wherein the aqueous mineral acid, the water stream and the guess hydrolysis reaction product stream are mixed to form an amine fermentation hydrolysis mixture, which is introduced into a continuous hydrazine hydrolysis reactor. 34 · —A method for preparing 2-hydroxy-4-methylthiobutanoic acid or a salt thereof, comprising: introducing an aqueous mineral acid and 2-light-4-methylthiobutyronitrile into a nitrile hydrolysis reactor; 9 hydrolyzing the nitrile In the reactor, 2-hydroxy-4-methylthiobutyronitrile is continuously hydrolyzed to produce a product stream of a nitrile hydrolysis reactor containing 2-hydroxy-4-methylthiobutyramine; water, aqueous mineral acid, and the nitrile hydrolysis reactor The product stream is introduced into a hydrazone hydrolysis stream reactor; and continuous hydrolysis of 2-hydroxy-4-methylthiobutaneamine in the hydrazone hydrolysis reactor produces a finished aqueous solution containing 2-hydroxy-4-methylthiobutane acid. Hydrolyzate. 35. The method according to item 34 of the scope of patent application, wherein the molar ratio of mineral acid to 2-hydroxy-4-methylthiobutyronitrile added to the nitrile hydrolysis reactor is between 0.5 and 0.95, and The total molar ratio of mineral acid to 2-hydroxy-4-methylthiobutyronitrile is between 0.6 and 0.95. 36. A method according to item 35 of the scope of application for a patent, wherein the molar ratio of mineral acid to 2-hydroxy-4-methylthiobutyronitrile added to the nitrile hydrolysis reactor is 0.8 to 0.95. And the total molar ratio of mineral acid to 2-hydroxy-4 -methylthiobutyronitrile, -6- This paper size applies the Chinese National Standard (CNS) A4 specification (210X297 mm) &quot; 495500 AB c D 6 The scope of patent application is between 0.85 and 0.95. 37. The method according to item 34 of the scope of patent application, wherein the nitrile hydrolysis reactor includes a first continuous stirred tank reactor, and the 2-hydroxy-4-methylthiobutyronitrile is continuously hydrolyzed in the nitrile hydrolysis reactor. The nitrile hydrolysate stream is introduced into the amidine hydrolysis reactor, which comprises an amidine hydrolysis flow reactor, and the 2-hydroxy-4-methylthiobutane amidine is continuously hydrolyzed in the amidine hydrolysis flow reactor. 38. The method according to item 34 of the application, wherein the nitrile hydrolysis reactor comprises a first continuous stirred tank reactor in which the 2-hydroxy-4-methylthiobutyronitrile is continuously hydrolyzed, and the nitrile The product stream of the hydrolysis reactor is introduced into a continuous ammonium hydrolysis reactor containing a second continuous stirred tank reactor, and 2-hydroxy-4-methylthiobutamide is continuously hydrolyzed in the second continuous stirred tank reactor to form a completed reaction stream. The completion reaction stream is introduced into the hydrazine hydrolysis reactor containing the hydrazine hydrolysis flow reactor, and when the completion reaction stream flows through the hydrazine hydrolysis flow reactor, the 2-hydroxy-4-methanbutamine The hydrolysis is essentially complete. 39. A method for preparing 2-hydroxy-4-methylthiobutanoic acid or a salt thereof, comprising: simultaneously 2-hydroxy-4-methylthiobutyronitrile, having a weight ratio between 70% and 99% by weight The strength H2S04 stream and water are introduced into a container in which 2-hydroxy-4-methylthiobutyronitrile is hydrolyzed. Water and sulfuric acid are added in this relative proportion to provide a strength of 50 to 70% by weight. A mixture (exclusive of organics); hydrolyzing 2-hydroxy-4-methylthiobutyronitrile in the container to produce a nitrile hydrolysate stream containing 2-hydroxy-4-methylthiobutamide; and hydrolyzing 2-hydroxy- 4-Methiobutanamine produces 2-hydroxy-4-Methiobutanoic acid. This paper is again applicable to Chinese National Standard (CNS) A4 specifications (210 X 297 mm) 495500 Six Λ8 B8 C8 _____ D8, scope of patent application A redundant aqueous hydrolysis product. 40. The method according to item 39 of the scope of the patent application, wherein the container is a nitrile hydrolysis reactor containing a first continuous stirred tank reactor, and the 2-hydroxy-4-methylthiobutyronitrile is continuously in the nitrile hydrolysis reactor. Hydrolysis, the nitrile hydrolysate stream is introduced into the amidine hydrolysis flow reactor, and in this amidine hydrolysis flow reactor, 2-methyl-4-butanil is continuously hydrolyzed. 41. The method according to item 39 of the scope of patent application, wherein the container is a nitrile hydrolysis reactor including a first continuous stirred tank reactor, and in the nitrile hydrolysis reactor, 2-hydroxy-4-methylthiobutyronitrile is continuously For hydrolysis, the product stream of the nitrile hydrolysis reactor is introduced into a continuous ammonium hydrolysis reactor containing a second continuous stirred tank reactor. The amine is continuously hydrolyzed to form a complete reaction stream, which is introduced into the amidine hydrolysis flow reactor. When the complete reaction stream flows through the amidine hydrolysis flow reactor, the The hydrolysis is essentially complete. 42. The method according to claim 1, 5, or 39, which further comprises recovering 2-hydroxy-4-methylthiobutanoic acid or a salt or derivative thereof from the completed aqueous hydrolysate. 43. The method according to claim 1, 5, or 39, wherein 2-hydroxy-4-methylthiobutane is recovered by extracting 2-hydroxy-4-methylthiobutanoic acid from the completed aqueous hydrolysate. acid. 44. The method according to item 39 of the scope of the patent application, wherein the vapor radiated from the method is not higher than 0.5 scf of 2-hydroxy-4-methylthiobutyric acid per 1,000 pounds of product. 45 · —A method for preparing 2-hydroxy-4-methylthiobutyric acid or a salt thereof, comprising: introducing 2-hydroxy-4-methylthiobutyronitrile and an aqueous mineral acid into a solution containing 2-hydroxy-4-methyl-8-methyl This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) 8 8 8 8 AB c D 495500 6. Application scope of patents Thiobutamine, mineral acid, and unreacted 2-hydroxy-4- Methylthiobutyronitrile in an aqueous hydrolysis mixture; the 2-hydroxy-4-methylthiobutyronitrile in the hydrolysis mixture is covered with a backmixing reaction zone and is in communication with the backmixing reaction zone in fluid flow) Hydrolysis in a continuous nitrile hydrolysis reactor in a zone (the cycle zone includes a cycle line); the aqueous hydrolysis mixture is continuously circulated in a recycle stream withdrawn from the backmixing reaction zone, and passes back to the backmixing reaction through the cycle zone Zone, the recycle stream containing unreacted 2-hydroxy-4-methylthiobutyronitrile when withdrawn from the backmixing reaction zone, a portion of the aqueous hydrolysis mixture that removes the cycle from the forward flow port in the recycle zone is Nitrile hydrolysis reactor product stream and conveying the nitrile hydrolysis reactor product stream to the amine fermentation stream Reactor; the nitrile hydrolysis reactor product stream is provided downstream of the forward flow port and diluted with water to provide a completed reaction stream; the hydroxylamine hydrolysis flow reactor contains 2-hydroxy-4-methyl formamidine in the completed reaction stream Thiobutamide is hydrolyzed to produce a completed aqueous hydrolysate containing 2-hydroxy-4-methylthiobutyric acid. The residence time of the circulating stream in the upstream of the circulation zone of the forward flow port and the forward flow port The sum of the dwell times of the nitrile hydrolysis reactor product stream before dilution, and before the nitrile hydrolysis reactor product stream is diluted, is sufficient to substantially distinguish the remaining 2-hydroxy-4-methylthiobutyronitrile. 46. The method according to item 1 or 45 of the scope of the patent application, wherein the aqueous mineral acid, the water stream and the nitrile hydrolysis reaction product stream are mixed to form a completed reaction stream, which is introduced into the amidine hydrolysis flow reactor. -9- This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) &quot; ~ 一 495500 A8 B8 C8 D8 六、申請專利範圍 47.—種製備2 -羥基-4 -甲硫丁酸或其鹽之方法，包括： 2 -羥基-4 -甲硫丁腈與水性礦酸引入含2 -羥基-4 -甲硫 丁醯胺、礦酸及未反應之2 -羥基-4 -甲硫丁腈之水性水解 混合物中； 於含回混反應區及流體流動中與該回混反應區交通之循 環區（該循環區含循環線）之連續腈水解反應器中，水解於 該水解混合物中之2 -羥基-4 -甲硫丁腈； 將自該回混反應區抽回之循環流中之該水性水解混合物 連續通過該循環區，再回至該回混反應區，該循環流當自 該回混反應區抽回時含未反應之2 -羥基-4 -甲硫丁腈； 自該循環區中之向前流動口除去一部分之該循環水性水 解混合物為腈水解反應器產物流，再輸送該腈水解反應器 產物流至連續之醯胺水解反應器； 於該向前流動口之下游處以水稀釋該猜水解反應為產物 流，提供醯胺水解混合物； 將該醯胺水解混合物或該腈水解反應器產物流及水進料 至連續醯胺水解反應器，其中含於該醯胺水解混合物中實 質部分之2 -羥基-4 -甲硫丁醯胺水解形成完成反應流； 輸送該完成反應流至醯胺水解流動反應器； 於該醯胺水解流動反應器中水解於該完成反應流中之2 -羥基-4 -甲硫丁醯胺，產生含2 -羥基-4 -甲硫丁酸之完成之 水性水解產物； 於該向前流動口之該循環區上游中之該循環流之駐留時 間與該向前流動口之該腈水解反應器產物流下游在稀釋以 -10- 本紙張尺度適用中國國家標準(CNS) A4規格(210 X 297公釐)495500 A8 B8 C8 D8 6. Application for patent scope 47.—A method for preparing 2-hydroxy-4-methylthiobutanoic acid or its salt, including: 2-hydroxy-4-methylthiobutyronitrile and aqueous mineral acid introduced containing 2 -Hydroxy-4 -methanbutamine, mineral acid and unreacted 2-hydroxy-4-methylthiobutyronitrile in an aqueous hydrolysis mixture; communicate with the backmixed reaction zone in a backmixed reaction zone and fluid flow The continuous nitrile hydrolysis reactor in the circulation zone (the circulation zone contains the circulation line) is hydrolyzed to the 2-hydroxy-4-methylthiobutyronitrile in the hydrolysis mixture; it will be drawn back into the circulation stream from the back-mixed reaction zone. The aqueous hydrolysis mixture continuously passes through the circulation zone, and then returns to the back mixing reaction zone, and the circulating stream contains unreacted 2-hydroxy-4-methylthiobutyronitrile when withdrawn from the back mixing reaction zone; A portion of the circulating aqueous hydrolysis mixture in the forward flow port in the circulation zone is the product stream of the nitrile hydrolysis reactor, and the product of the nitrile hydrolysis reactor is sent to the continuous ammonium hydrolysis reactor; downstream of the forward flow port Dilute the guess hydrolysis reaction with water as the product stream to provide ammonium water Mixture; feeding the amidine hydrolysis mixture or the nitrile hydrolysis reactor product stream and water to a continuous amidine hydrolysis reactor containing a substantial portion of 2-hydroxy-4-methylthiobutane in the amidine hydrolysis mixture Amine hydrolysis forms a complete reaction stream; transports the complete reaction stream to the amidine hydrolysis flow reactor; and hydrolyzes 2-hydroxy-4 -methanbutamine in the amidine hydrolysis flow reactor in the amidine hydrolysis flow reactor to produce Completed hydrolysate containing 2-hydroxy-4-methylthiobutyric acid; residence time of the circulating stream in the upstream of the circulation zone at the forward flow port and production of the nitrile hydrolysis reactor at the forward flow port The downstream of the logistics is diluted to -10- This paper size applies the Chinese National Standard (CNS) A4 specification (210 X 297 mm) 裝 495500 A8 B8 C8 _ __ _ D8 六、申請專利範圍 _ ^ ' 前之駐留時間之和，在該腈水解反應器產物流稀釋以前足 以區別殘留之2 -羥基-4 -甲硫丁腈。 48·根據申請專利範圍第4 7項之方法，其中該腈水解反應器 產物流於該連續醯胺水解反應器中以水稀釋。 49·根據申請專利範圍第4 5或4 7項之方法，其中於該稀釋點 之該腈水解反應器產物流中之殘留之2 -羥基-4 -甲硫丁腈 ，基於含於該產物流中之2 -羥基-4 -甲硫丁醯胺及2 -罗至 基-4-甲硫丁酸之和，不高於〇.〇1重量％。 50·根據申請專利範圍第4 5或4 7項之方法，其中於離開該腈 水解反應為之该水性水解混合物中，殘留之2 —獲基· 4 ·甲 硫丁腈，基於含於該水性水解混合中之2 -經基· 4 ·甲硫丁 酿胺與2 -經基-4 -甲硫丁酸之和，至少〇 · 〇 5重量％。 51·根據申請專利範圍第45或47項之方法，其中於該循環線 中之泥動制度實質上為擾動的，該循環流之溫度於整個該 循環區中至少50°C，該循環流於該向前流動口之該循環 區上游中之駐留時間至少3秒。 52·根據申請專利範圍第45或47項之方法，其中於該向前流 動口與該稀釋點之間，該腈水解反應器產物流之溫度至少 5 0 °C，及駐留時間至少3 0秒。 53·根據申請專利範圍第52項之方法，其中於該醯胺水解流 動反應器與該稀釋點間之該區中之流動制為擾動的。 54·根據申請專利範圍第47項之方法，其中流動制度與駐留 時間為致使提供於包含該向前流動口之該循環區上游之部 分之腈消滅反應區中之至少一個依序回混反應區及於其中 -11 _ 本紙張尺度適《 f関家標準(cNS) A4^格(21G x 297公资) ------- 495500 A BCD 六、申請專利範圍 該腈反應器產物流於該向前流動口與該稀釋點或該連續醯 胺水解反應器之間流動之向前流動反應區之同等量。 55. 根據申請專利範圍第4 7項之方法，其中於向前流動反應 區，其中該腈反應器產物流流在該向前流動口與該稀釋點 或該連續醯胺水解反應器之間，之流動制為薄層的，且流 動制及駐留時間為致使提供於該向前流動反應區中至少一 個依序之回混反應區之同等量。 56. 根據申請專利範圍第4 5或4 7項之方法，其中於該醯胺水 解流動反應器中之溫度加以控制以維持該完成之水性水解 產物之顏色為基於加納爾色標少於1 0。 57. —種製備2-羥基-4-甲硫丁酸或其鹽之方法，包括： 將2 -羥基-4 -甲硫丁腈及水性礦酸引入含2 -羥基-4 -甲 硫丁醯胺、礦酸及未反應之2 -羥基-4 -甲硫丁腈之水性水 解混合物中； 於包含回混反應區及於流體流動中與該回混反應區交通 之循環區（該循環區含循環線）之連續腈水解反應器中，水 解於該水解混合物中之2 -羥基-4 -甲硫丁腈； 於自該回混反應區抽回之循環流中之該水性水解混合物 連續循環，通過該循環區並回至該回混反應區，自該回混 反應區抽回之該循環流含未反應之2 -羥基-4 -甲硫丁腈； 自該循環區中向前流動口除去一部分之該循環水性水解 混合物為腈水解反應器產物流，再輸送該腈水解反應器產 物流至醯胺水解流動反應器； 於該向前流動口之下游處以水稀釋該腈水解反應器產物 _-12-_ 本紙張尺度適用中國國家標準(CNS) A4規格（210 X 297公釐） 495500 六、申請專利範圍 流，提供完成反應流； 於該聽胺水解流動反應H巾水解含㈣完成反應流中之 2-羥基-4_甲硫丁醯胺，產生含2_羥基_4_甲硫丁酸之完 成之水性水解產物； 於該向前流動π之該循環區上游中之該循環流之駐留時 間與在稀釋以前該向前流動口之該腈水解反應器產物流下 游之駐留時間之和為至少2 〇秒。 58. 根據中請專㈣圍第則之方法，丨巾駐留時間之和於 3 0秒與5分之間。 、 59. 根據申，專利範圍第57項之方法，其中於該循環線中之 流動制實質上為擾動的，及於該向前流動口之該循環區上 游中之該循環流之駐留時間至少3秒。 60. 根據巾請專㈣圍第57項之线，其中於該向前流動口 與該稀釋點間之駐留時間至少3 0秒。 6L根據中請專利範圍第45或57項之方法，其中流動制與駐 留時間為致使提供於包含該向前流動口之該循環區上游之 部分之腈消滅反應區中之至少一個依次回混反應區及於其 中該腈反應器產物於該向前流動口與該稀釋口間流動流之 向前流動反應區之相等物。 62·根據申請專利範圍第45，47或57項之方法，其中外部熱 交換器位於該循環線中。 63.根據申請專利範圍第62項之方法，其中該向前流動口位 於該外部熱交換器之該循環線上游中。 64·根據申請專利範圍第62項之方法，其中該水性礦酸引入 495500 A8 B8 C8 D8 於位於該外部熱交換.器之該循環線下游中之口之該水性水 解混合物中。 65. 根據中請專利範圍第45、47或57項之方法，纟中該腊水 解反應器產物流經由垂直之下導管線輸送至該稀釋點。 66. 根據申請專利範圍第47或57項之方法，其中該水性礦酸 ，該水流及該腈水解反應產物流混合形成完成反應流，其 引入醯胺水解流動反應器中。 67. 根據申請專利範圍第4 6項之方法，其中礦酸對添加至該 月月水~反應為中之2-¾基-4-甲硫丁腈之莫耳比為於〇 6 與1.5之間，且礦酸對2-羥基-4-甲硫丁腈之總莫耳比於 0.7與1 . 5之間。 68. 根據申請專利範圍第6 6項之方法，其中礦酸對添加至該 猜水解反應器中之2-¾基-4-甲硫丁猜之莫耳比為於〇 6 與1 . 5之間，且礦酸對2 -羥基-4 -甲硫丁腈之總莫耳比於 0.7與1 . 5之間。 69. 根據申請專利範圍第6 7項之方法，其中礦酸對加至該月青 水解反應器之2 -羥基-4 -甲硫丁腈之莫耳比於0 · 8與丨.2之 間，且礦酸對2 -羥基-4 -甲硫丁腈之總莫耳比於〇 . 9與丨· 2 之間。 70·根據申請專利範圍第6 8項之方法，其中礦酸對加至該月青 水解反應器之2-羥基-4 -甲硫丁腈之莫耳比於〇.8與丨2之 間，且礦酸對2-羥基-4-甲硫丁腈之總莫耳比於09與12 之間。 71·根據申請專利範圍第4 5或5 7項之方法，其中於其中該赌 -14 - 本紙張尺度適用中國國家標準(CNS) A4規格(210X297公釐） 495500Packing 495500 A8 B8 C8 _ __ _ D8 VI. Patent Application Range _ ^ 'The sum of the dwell time before the patent application, before the product stream of the nitrile hydrolysis reactor is diluted, it is enough to distinguish the remaining 2-hydroxy-4-methylthiobutyronitrile. 48. The method according to item 47 of the scope of application, wherein the product of the nitrile hydrolysis reactor is diluted with water in the continuous amidine hydrolysis reactor. 49. A method according to item 45 or 47 of the scope of the patent application, wherein the 2-hydroxy-4-methylthiobutyronitrile remaining in the product stream of the nitrile hydrolysis reactor at the dilution point is based on the content contained in the product stream The sum of 2-hydroxy-4-methylthiobutaneamine and 2-rozyl-4-methylthiobutanoic acid is not more than 0.01% by weight. 50. The method according to item 45 or 47 of the scope of the application for a patent, wherein in the aqueous hydrolysis mixture leaving the nitrile hydrolysis reaction, the remaining 2—acid base · 4 · methylthiobutyronitrile is based on the water content The sum of 2-methyl-4-methylthiobutanamine and 2-methyl-4 -methylthiobutyric acid in the hydrolysis mixture is at least 0.05% by weight. 51. The method according to item 45 or 47 of the scope of patent application, wherein the mud movement system in the circulation line is substantially disturbed, and the temperature of the circulation flow is at least 50 ° C in the entire circulation area. The dwell time upstream of the circulation zone of the forward flow port is at least 3 seconds. 52. The method according to claim 45 or 47, wherein the temperature of the product stream of the nitrile hydrolysis reactor is at least 50 ° C and the residence time is at least 30 seconds between the forward flow port and the dilution point. . 53. The method according to item 52 of the scope of patent application, wherein the flow in the zone between the amidine hydrolysis flow reactor and the dilution point is disturbed. 54. The method according to item 47 of the scope of patent application, wherein the flow regime and dwell time are such that at least one of the nitrile elimination reaction zones provided in the upstream portion of the circulation zone including the forward flow port is sequentially backmixed to the reaction zone And among them -11 _ This paper is suitable for "Family Standards (cNS) A4 ^ grid (21G x 297 public funds) ------- 495500 A BCD VI. Patent application scope The product of this nitrile reactor flows in An equivalent amount of forward flow reaction zone flowing between the forward flow port and the dilution point or the continuous amidine hydrolysis reactor. 55. The method according to item 47 of the scope of patent application, wherein in the forward flow reaction zone, the product stream of the nitrile reactor is between the forward flow port and the dilution point or the continuous amidine hydrolysis reactor, The flow system is thin-layered, and the flow system and dwell time are the same amounts that result in at least one sequential backmixing reaction zone provided in the forward flow reaction zone. 56. The method according to item 45 or 47 of the scope of the patent application, wherein the temperature in the amidine hydrolysis flow reactor is controlled to maintain the color of the completed aqueous hydrolysate based on a Garner color scale of less than 10 . 57. A method for preparing 2-hydroxy-4-methylthiobutanoic acid or a salt thereof, comprising: introducing 2-hydroxy-4-methylthiobutyronitrile and an aqueous mineral acid into a solution containing 2-hydroxy-4-methylthiobutane In an aqueous hydrolysis mixture of amine, mineral acid and unreacted 2-hydroxy-4-methylthiobutyronitrile; in a circulation zone containing a backmixed reaction zone and communicating with the backmixed reaction zone in fluid flow (the circulation zone contains In the continuous nitrile hydrolysis reactor of the circulation line), the 2-hydroxy-4-methylthiobutyronitrile in the hydrolysis mixture is hydrolyzed; the aqueous hydrolysis mixture in the circulation stream withdrawn from the back-mixing reaction zone is continuously circulated, Pass through the circulation zone and back to the back mixing reaction zone, and the circulating stream withdrawn from the back mixing reaction zone contains unreacted 2-hydroxy-4-methylthiobutyronitrile; removed from the forward flow port in the circulation zone A part of the circulating aqueous hydrolysis mixture is the nitrile hydrolysis reactor product stream, and then the nitrile hydrolysis reactor product stream is transported to the amidine hydrolysis flow reactor; the nitrile hydrolysis reactor product is diluted with water downstream of the forward flow port -12-_ This paper size applies to China National Standard (CNS) A4 (21 0 X 297 mm) 495500 6. Apply for a patent scope stream and provide a complete reaction stream; In this amine hydrolysis flow reaction H towel hydrolyzes the 2-hydroxy-4_methanbutamine in the reaction stream containing tritium to produce Completed aqueous hydrolysis product of 2_hydroxy_4_methylthiobutyric acid; the residence time of the circulating stream in the upstream of the circulation zone of the forward flow π and the nitrile hydrolysis reaction of the forward flow port before dilution The sum of the residence times downstream of the reactor product stream is at least 20 seconds. 58. According to the method of the Chinese government, the sum of dwell time is between 30 seconds and 5 minutes. 59. According to the application, the method in the scope of patent No. 57 wherein the flow system in the circulation line is substantially disturbed, and the residence time of the circulation flow in the upstream of the circulation area of the forward flow port is at least 3 seconds. 60. According to the request, please enclose the line of item 57 in which the residence time between the forward flow port and the dilution point is at least 30 seconds. 6L The method according to item 45 or 57 of the patent application, wherein the flow system and the dwell time are such that at least one of the nitrile elimination reaction zones provided in the upstream portion of the circulation zone including the forward flow port is sequentially backmixed. Zone and the equivalent of a forward flow reaction zone in which the nitrile reactor product flows between the forward flow port and the dilution port. 62. The method according to claim 45, 47 or 57 in which the external heat exchanger is located in the circulation line. 63. The method according to item 62 of the application, wherein the forward flow port is located upstream of the circulation line of the external heat exchanger. 64. The method according to item 62 of the patent application scope, wherein the aqueous mineral acid is introduced into 495500 A8 B8 C8 D8 into the aqueous hydrolysing mixture at the mouth of the external heat exchange device downstream of the circulation line. 65. According to the method of claim 45, 47, or 57 of the patent application, the wax hydrolysate reactor product stream is transported to the dilution point through a vertically lower conduit. 66. The method according to item 47 or 57 of the scope of the patent application, wherein the aqueous mineral acid, the water stream and the nitrile hydrolysis reaction product stream are mixed to form a completed reaction stream, which is introduced into the amidine hydrolysis flow reactor. 67. The method according to item 46 of the scope of the patent application, wherein the molar ratio of the mineral acid to the 2--5-yl-4-methylthiobutyronitrile added to the water of the month is between 0.6 and 1.5. And the total molar ratio of mineral acid to 2-hydroxy-4-methylthiobutyronitrile is between 0.7 and 1.5. 68. The method according to item 66 of the scope of the patent application, wherein the molar ratio of the mineral compound to the 2-¾-4-methylthiobutanyl added to the hydrolytic reactor is between 0.6 and 1.5. The total molar ratio of mineral acid to 2-hydroxy-4-methylthiobutyronitrile is between 0.7 and 1.5. 69. The method according to item 67 of the scope of the patent application, wherein the molar ratio of the mineral acid to the 2-hydroxy-4-methylthiobutyronitrile added to the hydrocyanic hydrolysis reactor is between 0.8 and 2. And, the total molar ratio of mineral acid to 2-hydroxy-4-methylthiobutyronitrile is between 0.9 and 丨 · 2. 70. The method according to item 68 of the scope of the patent application, wherein the molar ratio of the mineral acid to the 2-hydroxy-4-methylthiobutyronitrile added to the moonlight hydrolysis reactor is between 0.8 and 2. And the total molar ratio of mineral acid to 2-hydroxy-4-methylthiobutyronitrile is between 09 and 12. 71. The method according to item 4 5 or 57 of the scope of patent application, in which the bet -14-This paper size applies the Chinese National Standard (CNS) A4 specification (210X297 mm) 495500 A B c D 反應器產物流流動於該向前流動口與該稀釋點之間之向前 流動反應區中之流動制為薄層的，且流動制與駐留時間為 致使供於该向前流動反應區中至少一個依次回混反應區 之同等物。 72. 根據申請專利範圍第5 5項之方法，其中流動制與駐留時 間為致使提供於該向前流動反應區中2與3之間之依次回 混反應區之相等物。 73. 根據申請專利範圍第71項之方法，其中流動制與駐留時 間為致使提供於該向前流動反應區中2與3之間之依次回 混反應區之相等物。 74·根據申請專利範圍第45、47或57項之方法，其中於其中 該腈反應器產物流動於該向前流動口與該稀釋點之間之向 前流動反應區中之流動制為擾動的，且流動制與駐留時間 為致使提供於該向前流動反應區中至少一個依次之回混反 應區之同等物。 75. 根據申請專利範圍第4 5、4 7或5 7項之方法，其中該完成 之水性水解產物含高至〇 . 〇 5重量％醯胺。 76. 根據中請專利範圍第45、47或57項之方法，其中該流動 制及駐留時間為致使提供於該酿胺水解流動反應器中至少 兩個依次回混反應區之同等物。 77·根據中請專利範圍第45、47或57項之方法，其中流動制 及駐留時間為致使提供於該醯胺水解流動反應器中至少 3 5個依次回混反應區之同等物。 78.—種水性水解產物組合物，其係用於製備為甲硫胺酸補充 -15- 本紙張尺度適用中國國家標準(CMS) A4規格（210 X 297公釐） t 丁 _ 申請專利範圍 ^ ( 2 -授基_ 4 -甲硫丁酸之濃水性溶液，該組合物含至少 36重1%2-羥基甲硫丁酸，至少18重量％銨鹽、至少 15 .香' &quot;W* ^/(\ -7^ 古 21 、南至0.〇5重量％醯胺及高至〇.〇5重量。/〇腈 ，该組合物具基於加納爾色標不多於10之顏色。 79·根據申凊專利範圍第7 8項之組合物，其包含至少$ 〇重量 %銨鹽及至少25重量％水。 80.根據申μ專利範圍第7 8項之組合物，其中該組合物之顏 色於基於加納爾色標之5與1 〇之間。 81· —種製備2-經基甲硫丁酸之方法，包括： 將礦酸引入含連續攪拌槽反應器之第一反應器； 將2-#里基-4-甲硫丁腈引入該第一反應器； ，、’貝水解该第一反應器中之2 -羥基-4 -甲硫丁腈，同時 連續移除來自該第一反應器中反應混合物之猜水解之熱， 以產生含有2-羥基甲硫丁醯胺之中間液態水解溶液， 於該第一反應器中2-羥基-4-甲硫丁腈轉化為2·羥基—4-甲硫丁醯胺係至少9 0 % ; 將水與中間液態水解溶液連續引入流動反應器； 連績水解該流動反應器中之2 _羥基f硫丁醯胺，以 產生含2-羥基甲硫丁酸之液態水解水解產物溶液。 82·根據申請專利範圍第81項之方法，其中該中間液態水解 /4液包含不大於2重量％之2 -經基-4 -甲硫丁猜。 83.根據申請專利範圍第82項之方法，其中該中間液態水解 /谷液包含南達1 1重量％之2 -羥基-4 -甲硫丁酸、至少丨〇重 量％之水與至少3 5重量％之醯胺。 __-16- 本紙張尺度適用中國國家標準(CNS) A4規格(210 X 297公釐) --------- 495500 A8 B8 C8 D8The flow of the AB c D reactor product flow in the forward flow reaction zone between the forward flow port and the dilution point is made as a thin layer, and the flow system and the dwell time are such that the forward flow reaction is provided for the forward flow reaction. At least one of the zones is sequentially back-mixed with the equivalent of the reaction zone. 72. The method according to claim 55, wherein the flow regime and the dwell time are equivalent to the sequential back-mixing reaction zone provided between 2 and 3 in the forward flow reaction zone. 73. The method according to item 71 of the scope of the patent application, wherein the flow regime and the dwell time are equivalent to the sequential back-mixing reaction zone provided between 2 and 3 in the forward flow reaction zone. 74. A method according to claim 45, 47, or 57 in which the flow of the nitrile reactor product in a forward flow reaction zone between the forward flow port and the dilution point is made turbulent And the flow system and dwell time are the equivalents of at least one sequential backmixing reaction zone provided in the forward flow reaction zone. 75. The method according to claims 4, 5, 47, or 57 in the scope of the patent application, wherein the completed aqueous hydrolysate contains up to 0.05 wt% amidine. 76. The method according to claim 45, 47, or 57 wherein the flow regime and residence time are equivalents that cause at least two of the amine hydrolysis flow reactors to be sequentially mixed back into the reaction zone. 77. The method according to item 45, 47, or 57 of the patent application, wherein the flow system and the dwell time are the equivalents of at least 35 sequentially back-mixed reaction zones provided in the amidine hydrolysis flow reactor. 78. An aqueous hydrolysate composition, which is used for the preparation of methionine supplement -15- This paper size is applicable to the Chinese National Standard (CMS) A4 specification (210 X 297 mm) t Ding_ Scope of patent application ^ (2 -Nitrate_ 4-A concentrated aqueous solution of methylthiobutyric acid, the composition contains at least 36% by weight of 1% 2-hydroxymethylthiobutyric acid, at least 18% by weight of ammonium salt, and at least 15. fragrant '&quot; W * ^ / (\ -7 ^ Gu 21, south to 0.05% by weight of amidine and up to 0.05% by weight. / 0 Nitrile, the composition has a color based on the Garner color scale of not more than 10. 79 A composition according to item 78 of the patent application scope, which comprises at least $ 0 wt% ammonium salt and at least 25% by weight of water. 80. A composition according to item 78 of the patent application scope, wherein the composition is The color is between 5 and 10 based on the Garner color scale. 81 · —A method for preparing 2-methyl methiobutanoic acid, comprising: introducing mineral acid into a first reactor containing a continuous stirred tank reactor; 2- # 里 基 -4-methylthiobutyronitrile is introduced into the first reactor; ′, molt hydrolyzes 2-hydroxy-4-methylthiobutyronitrile in the first reactor, and continuously moves The heat of guess hydrolysis from the reaction mixture in the first reactor to produce an intermediate liquid hydrolysis solution containing 2-hydroxymethylthiobutanamine, and the 2-hydroxy-4-methylthiobutyronitrile is converted in the first reactor It is at least 90% of 2-hydroxy-4-methylthiobutamide; it continuously introduces water and the intermediate liquid hydrolysis solution into the flow reactor; it continuously hydrolyzes 2_hydroxyf-thiobutamide in the flow reactor to A liquid hydrolyzed hydrolysate solution containing 2-hydroxymethylthiobutyric acid is produced. 82. The method according to item 81 of the scope of the claimed patent, wherein the intermediate liquid hydrolysis / 4 liquid contains not more than 2% by weight of 2-hydroxy group-4- Methidine. 83. The method according to item 82 of the scope of patent application, wherein the intermediate liquid hydrolysis / valley liquor contains Nanda 11% by weight of 2-hydroxy-4-methylthiobutanoic acid, at least Water and at least 35 wt% amidine. __16- This paper size applies to Chinese National Standard (CNS) A4 (210 X 297 mm) --------- 495500 A8 B8 C8 D8 六、申請專利範圍 84·—種製備2-羥基-4-甲硫丁酸之方法，包括： 將礦酸引入含連續攪拌槽反應器之第一反應器； 將2 -羥基-4 -甲硫丁腈引入該第一反應器；6. Application scope of patent 84 · —A method for preparing 2-hydroxy-4-methylthiobutanoic acid, comprising: introducing mineral acid into a first reactor containing a continuous stirred tank reactor; and introducing 2-hydroxy-4-methylthio Butyronitrile is introduced into the first reactor; 連續水解該第一反應器中之2 - #至基-4 -甲硫丁腈，同時 連續移除來自該第一反應器中反應混合物之腈水解之熱， 以產生含有2 -羥基-4 -甲硫丁醯胺之中間液態水解溶液， 於該第一反應器中2-羥基-4 -甲硫丁腈轉化為2-幾基_4-甲硫丁醯胺係至少9 0 % ; 將離開該第一反應器之中間液態水解溶液與水流連續引 入第二連續攪拌槽反應器，致使含於該中間溶液中之2_經 基-4 -甲硫丁醯胺之實質部分，在第二連續攪拌槽反應器 中水解形成最終反應溶液； 將最終反應溶液連續引入流動反應器； 翥 將該流動反應器中之2 - #垔基-4 -甲硫丁醯胺連績水解， 同時維持實質貫穿該流動反應器中實質單相反應混合物， 以產生含2 -羥基-4甲硫丁酸之液態水解產物溶液。 85·根據申請專利範圍第34、45、47、57、81或84項之方 法，其中該礦酸係硫酸。 -17- 本紙張尺度適用中國國家標準(CNS) A4規格(210X 297公釐）Continuously hydrolyzing 2- # to 4-methylthiobutyronitrile in the first reactor, while continuously removing the heat of nitrile hydrolysis from the reaction mixture in the first reactor to produce 2-hydroxy-4- An intermediate liquid hydrolysis solution of methotrexamide, in which the 2-hydroxy-4-methylthiobutyronitrile is converted to 2-epi-4-methylthiobutamide in the first reactor at least 90%; The intermediate liquid hydrolysis solution and water stream of the first reactor are continuously introduced into the second continuous stirred tank reactor, so that a substantial part of the 2-mercapto-4 -methanidine in the intermediate solution is continuously Hydrolysis in the stirred tank reactor to form the final reaction solution; the final reaction solution is continuously introduced into the flow reactor; A substantially single-phase reaction mixture in the flow reactor to produce a liquid hydrolysate solution containing 2-hydroxy-4 methiobutanoic acid. 85. The method according to item 34, 45, 47, 57, 81, or 84 of the scope of patent application, wherein the mineral acid is sulfuric acid. -17- This paper size applies to China National Standard (CNS) A4 (210X 297 mm)