201247618 六、發明說明： 【發明所屬之技術領域】 本發明係關於一種藉由異丁醛（IBA)與甲酿（FA)反應製 備羥基新戊醛（ΗΡΑ)的方法。本申請案進一步係關於一種 藉由氫化按照本發明製備之經基新戊酿製備新戊二醇 (NPG)的方法及將如此獲得之NPG進一步轉化成聚酯樹 脂、不飽和聚酯樹脂、潤滑劑或增塑劑。 本申請案以引用之方式併入在2012年4月19曰申請之美 國臨時申請案第61/476,793號。 【先前技術】 新戊二醇係用作製備用於粉末塗佈材料或玻璃纖維加強 聚合物之飽和聚酯樹脂的原材料。 一般在，階段方法中製備新戊二醇，其中首先異丁醛 (ΙΒΛ)與曱醛（FA)以醇醛加成反應，以獲得經基新戊路 (ΗΡΑ) ’其可在第二製程階段中直接氫化為新戊二醇 (NPG)。 在第一製程階段（醇醛反應）中，異丁醛一般與甲醛在作 為催化劑之三級胺存在下以醇醛反應進行反應。醇醛反應 的產物一般包括ΗΡΑ及未轉化的起始化合物，諸如曱醛、 ΙΒΑ以及使用之三級胺催化劑及水。產物一般亦包括雜質 及醇酿反應的副產物，諸如可藉由Cannizzaro或Tishchenko 反應自甲醛形成之甲酸，及所用胺催化劑之甲酸鹽，諸如 甲酸三曱基銨。在醇醛反應後，未轉化的醛類及一部份胺 鹼通常藉由蒸餾除去並且再循環進入醇醛反應。 163421.doc 201247618 例如，WO 97/173 13敘述一種藉由對應醛類與呈水溶液 之甲醛在三級胺存在下，在由若干串聯連接的攪拌容器所 組成之反應器級聯中反應來製備羥基烷之方法。所得反應 混合物一般在若干個塔中純化。 WO 98/28253同樣揭示一種製備羥基烷之多階段方法， 其中在第一階段中，使對應起始醛在三烷基胺類存在下與 FA反應，及在第二階段中，來自階段丨之反應混合物藉由 蒸館分離成包括反應產物的底部物及由可再次循環進入第 一階段之較低沸點組份所組成之頂部產物。在第三階段 中，將來自第二階段之底部餾分引入反應後或蒸餾階段， 其中未完全羥甲基化之化合物被轉化成對應亞曱基化合物 及頂部蒸餾掉。在蒸餾中所獲得之底部產物送至氫化。 US 4,036,888、GB 1219162 及 JP-A 3193738 亦敘述用於 製備NPG之兩階段方法，其中IBA首先在鹼催化劑下與甲 醛反應以產生ΗΡΑ，其接著催化氫化成npg。 用於製備NPG之兩階段方法之總述可見於例如w〇_Ai_ 2010079187中 〇 【發明内容】 本發明之目的在於提供一種製備Ηρα之方法，ΗΡΑ可直 接引入其中ΗΡΑ被轉化為NPG之下游氫化階段而實質上避 免ΗΡΑ之熱分解。應該提供一種醇酸反應產物，其在下游 氫化階段會產生更高NPG產率及更低程度之非所需副反 應。本發明之另一目的在於減少在醇醛反應中所用之曱醛 δ量數，從而節省原料成本。本發明之另一目的在於提供 163421.doc 201247618 具有低含量未轉化異丁醛之醇醛反應產物。此外，欲提供 一種可減少ΗΡΝ(羥基新戊酸與NPG之酯（=ΗΡΝ))形成之方 法。根據本發明之方法亦能產生無需添加其他pH調節劑而 具有7.5至8.5之pH值之氫化進料。 【實施方式】 本發明之目的係藉由一種製備羥基新戊醛（HPA)之方法 而達成，其包括在第一階段中，異丁醛（IBA)與甲醛（FA) 在三級胺存在下反應及在第二階段中，將在第一階段中所 獲得之反應產物引入汽提塔’並且將汽提氣體引入汽提 塔。 根據本發明，在第一反應階段中，異丁醛與曱醛在三級 胺存在下反應。 甲酿一般以甲醛水溶液用於該方法中。工業可利用的曱 醛一般以30、37及49重量％之濃度的水溶液出售。然而， 在該方法中亦可使用多達60重量％之甲醛溶液。 工業甲醛一般包括製備所產生的甲酸。甲酸之降解產物 可降低在下游氫化階段中之氫化催化劑的使用壽命從而造 成NPG產率的下降。在一個特定實施例中，使用含有15〇 ppm或更少甲酸含量之曱醛。如在申請案w〇 2〇〇81〇7333 中所述，可藉由利用鹼性離子交換劑處理曱醛或曱醛水溶 液而獲得此甲路。有用陰離子交換劑包括本身已知的離子 交換W，為強鹼性、弱鹼性或中度鹼性及係呈膠體形式或 大孔形式。此等為例如具有三級胺基團作為官能團之與二 乙烯苯父聯之聚苯乙烯樹脂結構的陰離子交換劑。亦有用 I63421.doc 201247618 者為基於與二乙烯笨交聯之丙烯酸或甲基丙烯酸之離子交 換劑或藉由甲醛及笨酚縮合所製備之樹脂。具體有用的實 例包括市售產品：來自 Rohm and Haas，Philadelphia，USA 之 Ambersep® 900、Amberlyst® 及 Amberlite® 及來自 Lanxess，Leverkusen之 Lewatit®。 異丁醛亦用於根據本發明之方法中》 異丁酿之製法钦述於例如章節「Butanals」（Ullmann之 Encyclopedia of Industrial Chemistry, Published Online : 2000 年 9 月 15 日，DOI: 10.1002/14356007.a04_447)中。其 可例如藉由丙稀之氫甲酿化反應而製備。 所用異丁醛之純度較佳地大於95重量％，更佳言之大於 97重量％及更佳言之大於99重量％。 所用之三級胺可為如敘述於例如DE-A 28 13 201及DE-A 27 02 582中之胺。特別佳者係三正烷基胺，尤其三乙胺、 三正丙胺、三正丁胺及三曱胺。 極佳者係三曱胺（「TMA」）、三乙胺（ΓΤΕΑ」）及三正 丙胺（「TPA」）’因為此類化合物一般具有比npg更低的 /弗點及因此有利於自反應混合物蒸傲除去。特別佳係利用 三甲胺（「TMA」）作為反應中之三級胺。 醇醛反應（第一階段）可在添加或不添加有機溶劑或增溶 劑下進行。在根據本發明之方法之各蒸餾中，與低沸點化 合物形成適當低彿點共彿混合物之溶劑之使用可能降低在 此類蒸餾中之能量消耗及/或有利於自高沸點化合物中蒸 餾除去低沸點物》 163421.doc -6· 201247618 適當溶劑為例如環狀及非環狀醚諸如THF、二噁烷、甲 基第二丁基醚或醇類諸如甲醇、乙醇或2_乙基己醇。 在醇醛反應中，在各情形下以新製形式添加之異丁醛與 甲醛之添加量之莫耳比約在1:1至1:5之範圍内、較佳言之 在1:1.01至1:3.5之範圍内及更佳言之在1:1〇2至1:丨5之範 圍内及尤佳在1:1,03至1:1.1之範圍内。 相對於添加之異丁醛，在醇醛反應中添加之三級胺觸媒 的量一般為0.001至0.2，較佳言之〇.〇1至〇 07當量’這表示 一般係以催化含量使用該胺。 一般在5至100t，較佳言之15至80°C之溫度下進行該醇 酿反應。 可在一般而言1至30巴，較佳言之1至15巴，更佳言之j 至5巴之壓力，適宜地在有關反應系統之自生麼力下進行 針對該醇酿反應所述之反應。 可分批或連續進行該醇醛反應。 較佳地在連續攪拌槽式反應器或連續槽級聯中進行該醇 醛反應。為調整滯留時間，可將來自一個攪拌槽之一部份 反應產物再循環至特定攪拌槽式反應器。 第一階段（醇醛反應）之總滞留時間較佳係0.25至12小 時，更佳言之0.5至8小時及尤佳係1至3小時《在一個較佳 實施例中’較佳地選擇在反應器級聯中之單個反應器的滞 留時間以使總滯留時間在各反應器之間平分。 來自醇搭反應之產物一般包括未轉化的起始化合物，諸 如曱醛、烷醛以及所用之三級胺催化劑及可能的水。 163421.doc 201247618 產物另外包括羥基新戊醛（ΗΡΑ)。 產物一般亦包括雜質及來自醇醛反應之副產物，諸如甲 酸’其可因Cannizzaro或Tishchenko反應由曱搭產生，諸 如HPN，及所用胺催化劑之甲酸鹽，諸如曱酸三曱基敍。 來自醇醛反應之產物較佳地包括40至80重量％之ΗΡΑ及 更佳言之50至70重量％之ΗΡΑ。 在一個較佳實施例中，來自醇醛反應之產物具有下列組 成： ΗΡΑ : 40至 80重量 ％ ; 水：10至50重量％ ; ΙΒΑ : 0至20重量％ ; FA : 0至10重量％ ; 三級胺：0至10重量〇/〇。 在另一個較佳實施例中，來自醇醛反應之產物具有下列 組成： ΗΡΑ : 50至 70重量 ％ ; 水：15至40重量〇/〇 ; ΙΒΑ : 1至10重量％ ; FA : 0.5至5重量％ ; 三級胺：0 · 5至5重量〇/〇。 根據本發明’在第二反應階段中’將來自第一階段（醇 酸反應）之產物引入汽提塔中，其中亦引入汽提氣體。 汽提塔較佳地為一種用於分離低沸點及高沸點組份之裂 置’來自第一階段之包含ΗΡΑ之反應產物較佳地被馈入塔 163421.doc 201247618 之上部區域，及含ΗΡΑ之反應產物在塔的下部區域（例如在 塔底）抽離。 在塔頂或塔的上部區域，例如在1 〇至1 〇〇%、較佳言之 50至1 〇〇%之理論板的空間面積中，一般可抽離包括除汽 提氣體外作為重要組分之未轉化的異丁醛、三級胺、甲醇 及可能的水及曱醛之氣體流。 根據所用塔之分離性能，熟習此項技術者可以常規方 式’在來自第一階段之產物中所存在之組份之已知蒸汽壓 及蒸發平衡的基礎上’藉由常規計算方法確定汽提塔之提 取操作條件。 較佳地在具有用於提高分離性能之内件的汽提塔中進行 第二反應階段》 更佳地在盤式塔中進行第二反應階段。在盤式塔中，質 量轉移發生之中間盤位於塔的内部。不同盤之類型的實例 為篩塔盤、槽形罩盤、雙流盤、泡罩盤、閥盤或Streuber 盤。所用泡罩盤亦可為具有偏轉板之改良泡罩盤，諸如所 稱之LORD盤或LORD反應器，其敘述於例如DE_A1_ 10120801中。 較佳盤為槽形罩盤、泡罩盤、Streuber盤及改良泡罩盤 (lord盤）。 然而，在另一實施例中，分離用内件亦可呈結構填充 物，例如呈薄片金屬填充物，諸如Mellapak 250 Y或M〇ntz Pak，B 1 -250類型’或呈結構陶瓷填充物或任意填充物，例 如包括Pall環、IMTP環（來自Koch-Glitsch)、拉西超級環 163421.doc 201247618 (Raschig Superring)等而存在。結構或任意填充物可排列 在一個床中或較佳言之複數個床中。 來自第一階段之反應產物較佳地供應給5〇%及丨〇〇%之汽 提塔之理論板之空間區域（自底部計數）、更佳言之9〇%及 100%之汽提塔之理論板之空間區域，尤其在最上面的 盤。熟習此項技術者利用常規計算工具，可以確定作為來 自第一階段之反應產物之組成之函數的最佳饋入點β 理論版的數目一般在2至100塊，較佳言之2至8〇塊，更 佳言之20至70塊及最佳言之25至60塊之範圍内。 塔中的滯留時間較佳係15分鐘至3 〇〇分鐘，更佳言之3〇 分鐘至240分鐘及最佳言之6〇分鐘至240分鐘。 頂部壓力更佳係500至3000毫巴，更佳言之goo至2〇〇〇毫 巴及最佳言之1000至1500毫巴。 在塔底或在汽提氣體之供應點，較佳地建立高於所用三 級胺的蒸發溫度之溫度，以使其他低沸點物及一部份水完 全轉化或實質上完全轉化成氣相。 根據本發明，建立不超過90eC，較佳言之80°C及更佳言 之75°C的溫度。 塔底的溫度較佳係50至90X：，更佳言之55至80°C及最佳 言之60至75°C。 例如，可以建立1〇13毫巴之塔頂壓力及較佳言之7〇t的 塔底溫度。 /飞k氣體為在存在反應條件下主要為情性且不與反應混 合物中存在之物質反應的氣體。所用汽提氣體可為惰性氣 16342 丨.doc 201247618 體’諸如lilt或稀有氣體，尤其係氦氣、氖氣、氬氣或氣 氣。較佳使用氮氣.然而，此處亦可使用氫氣。所用惰性 氣體亦可為前述氣體的混合物。 較佳將汽提氣體引入蒸餾塔的下部區域及因此以與液體 流相反的流向流動。 可以藉由例如分配環或喷嘴達成進入塔底的引入，但亦 可引入至蒸餾塔的下部區域，較佳言之在至多30%、較佳 言之至多20%及更佳言之至多1G%之蒸顧塔之理論板的空 間區域中（自底部計數）。引入之汽提氣體通常藉由塔内存 在之内件與以相反方向流動之液體完全混合。 在汽提塔之一個較佳實施例中，所用之汽提氣體可為來 自NPG製程之氫化反應排氣，其主要包括氫氣。在一個特 别佳的實施例中，在引入汽提塔之前，可藉由排氣洗條純 化此氫化反應氣體以除掉雜質，尤其三級胺。 供應之惰性氣體之流率較佳係每kg/h饋料0 001至i、更 佳言之0.005至0.1及最佳言之〇 〇1至〇 〇5 ^化惰性氣體。 在塔的上部區域，一般將未轉化的異丁醛、曱醛、甲醇 及可能的水作為氣體流抽離及在冷凝器令冷凝及一部份 冷凝物流較佳作為返回流再循環至塔中。一部份異丁醛可 視需要再循環至第一反應階段（醇醛反應）。 一般調整位於塔頂的返回流，以使佔優勢含量之HpA、 IBA及水保留在塔中，如此幾乎完全作為底部產物獲得 ΗΡΑ »在冷凝器中獲得之冷凝物較佳地以小於兄％之程 度，更佳言之小於25%之程度再循環至蒸餾塔頂部。 163421.doc 201247618 在 >飞提塔的下部區域，一般獲得包括較佳言之4〇至8〇重 量0/〇之ΗΡΑ及更佳言之60至70重量％之ΗΡΑ之產物。 在一個較佳實施例中，來自汽提塔的產物具有下列組 成： ΗΡΑ : 40至80重量％ ; 水：10至50重量％ ; 剩餘物：其他有機化合物。 在另一個較佳實施例中，來自汽提塔的產物真有下列組 成·· ΗΡΑ : 60至 70 重量 〇/〇 ; 水：15至40重量％ ; 剩餘物：其他有機化合物。 在一個較佳實施例中，來自第二反應階段之產物的pH為 5至9’更佳言之6至8。 異丁醛含量較佳少於2重量％，更佳言之少於1重量。/〇， 甚至更佳言之少於0.5重量％及尤佳言之少於0.1重量％。 三燒基胺含量較佳少於2重量。/❶，更佳言之少於1重量〇/〇 及最佳言之少於〇.5重量％。 曱链含量較佳少於8重量❹/。，更佳言之少於5重量°/。及最 佳言之少於2.5重量％。 經基新戊酸及NPG之酯（=HPN)的含量較佳少於2重量 % ’更佳言之少於1重量％及最佳言之少於0.5重量％。 藉由根據本發明之方法，可獲得包括ΗΡΑ之產物，其可 直接用於下游氫化階段（第三反應階段）以製備新戊二醇 16342 丨.doc 12 201247618 (NPG)。在一個較佳實施例中，在第二反應階段之後及第 二反應階段之前，因而不再需要其他處理步驟。 藉由根據本發明之方法，另外可獲得一種不需另外添加 pH調節劑的產物，其可直接用於另一反應階段中，其中在 氫化催化劑存在下利用氫氫化來自階段2中之產物（第三反 應階段=氫化反應）。 然而’亦可利用pH調節劑（例如三級胺、無機鹼、無機 酸或有機酸）混合來自第二反應階段的產物，從而調整pH 直至氫化產物（來自第三反應階段之產物）具有7至9的ppj 值°亦可將氫化進料與pH調節劑分開饋入反應器中及在其 中混合之。所用三級胺可為上述三級胺，尤其Tma。 在氫化反應（第三反應階段）中，較佳地利用較佳位於支 撐材料上之催化劑，其包括元素週期表之第8至12過渡族 中之至少一種金屬’諸如Fe、Ru、〇s、c〇、Rh、Ir、Ni、 Pd、Pt、Cu、Ag、An、Zn、Cd、Hg，較佳言之 Fe、Co、 Ni、Cu、RU、Pd、pt，更佳言之 Cu e 所用支撐材料較佳係由鈦、鍅、铪、矽及/或鋁氧化物 組成之支撐材料。 可藉由自用於製備此類經支撐之催化劑之先前技術已知 的方法，製備可用催化劑。較佳亦可利用包括存在或缺乏 或多種元素鎮、鋇、鋅或鉻下，位於含氧化銘或二氧化 鈦之支撐材料上之銅的經支撐催化劑。此類催化劑及其製 法可自WO 99/44974中知曉。 此外，敘述於例如WO 95/32171中之經支撐銅催化劑及 16342 丨.d〇c -13- 201247618 揭示於EP-A 44 444及DE 19 57 591 t之催化劑適用於氫化 反應中。 可在例如填充催化劑床之反應器管中分批或連續進行氫 化反應’其中反應溶液流經例如呈喷淋或液體相模式的催 化劑床，如在DE-A 19 41 633或DE-A 20 40 501中所述。 有利地，可視需要在冷卻後，使反應產物子流再循環，及 將其再次通過固定催化劑床《同樣有利地，在複數個串聯 連接的反應器中（例如在2至4個反應器中）進行氫化反應， 在此情形下，在末反應器之上游之各反應器中之氫化反應 僅進行至多例如50至98%之部份轉化，且僅在末反應器中 完成氫化反應。適當的是，在進入下一反應器之前，可藉 由例如冷卻裝置或藉由喷射冷卻氣體（諸如氫氣或氮氣）或 引入冷反應溶液之子流’冷卻來自前一反應器之氫化產 物。 氫化溫度一般介於50與180°C ’較佳言之90與140°C之 間。所採用之氫化壓力一般為1 〇至250巴，較佳言之20至 120巴。 來自第三反應階段（氫化反應）之反應產物包括含有NPg 的混合物，其較佳具有下列組成： 20至90重量％之NPG， 〇至5重量〇/〇之甲醇， 〇至5重量。/〇之三級胺， 0至5重量％之有機二級化合物， 0.01至5重量％之三級胺及曱酸之加成物（胺曱酸鹽）， 163421.doc 14 201247618 剩餘物水。 含水NPG混合物更佳具有下列組成： 50至 80重量 ％(NPG、 0.1至3重量％之甲醇、 〇·〇1至5重量％之三級胺、 0至5重量％之有機二級化合物、 0.01至5重量％之三級胺及甲酸之加成物（胺甲酸鹽）、 剩餘物水。 存在之有機二級化合物可為例如異丁醇。 較佳可藉由自NPG除去低沸點物，純化含水nPg混合 物0 更佳藉由蒸德自含水NPG混合物中除去低沸點物。 較佳以使低沸點物（諸如水、異丁醇、甲醇及三級胺）在 減壓下，經由頂部除去之方式進行蒸餾，尤其當所用胺具 有比所形成之NPG更低的沸點時，如針對tmA、TEA及 TPA之情形。 當使用具有比所形成之NPG更高沸點的三級胺時，一起 除去在底部之三級胺及所形成之NP G及在下游蒸館階段中 在塔底富集，而NPG作為頂部產物抽離。 一般而言，蒸餾期間，一部份胺曱酸鹽在塔底或在塔之 汽提區與NPG反應產生游離胺及NPG之甲酸醋〇此較佳形 成甲•及NPG之单醋，其在本揭示案之範圍内稱為npg甲 酸0旨。 一般在蒸顧中在塔頂與其他低沸點物一起除去藉由轉醋 化反應所釋放之胺。 163421.doc -15- 201247618 因而’應該調整蒸餾以使在底部產物中之所形成的NPG 甲酸酯保持低濃度及目標產物（NPG)具有最大純度。 較佳藉由在蒸餾中選擇高於NPG甲酸酯之蒸發溫度的底 部溫度，以藉由蒸發將NPG甲酸酯完全或實質上完全轉化 成氣相而達成此。 藉由此措施所達成之產率及產物品質之改良很可能歸因 於多經甲基甲酸酯一般具有比其他低沸點物更高的沸點且 多羥甲基甲酸酯因而係以適當回流速率在塔之精餾區段沉 澱的事實。在精餾區段中沉澱之NPG甲酸酯可利用水進行 水解以再次形成甲醆及Npg。一般在塔頂除去甲酸，而一 般可自塔底排出NPG。 在一個較佳實施例中，因而較佳如下進行蒸餾： 一般在化優勢部份之低沸點物在對應頂部壓力下冷凝之溫 度下操作冷凝器。 一般而言，冷凝器之操作溫度在〇至80°c，較佳言之2〇至 50°C之範圍内。 此處所用冷卻介質較佳可為極冷的水（例如約5°c )或冷卻劑 混合物（例如，在例如_2〇。(：下之乙二醇-水）。 頂部壓力更佳係0.001至〇.9巴，更佳言之〇,〇1至〇 5巴。 在工業規模上’一般藉由蒸汽喷射器獲得真空。 在塔底，較佳建立高於NPG甲酸酯之蒸發溫度之溫度， 以使NPG甲酸酯完全轉化或實質上完全轉化成氣相。 特別佳建立比NPG甲酸酯之沸騰溫度高5°/。至5〇%及最佳 言之比NPG甲酸酯之沸騰溫度高10%至20%的溫度。 163421.doc -16· 201247618 例如，在利用TMA作為三級胺及在丨75毫巴之塔頂壓力 下製備NPG的情形下，可建立較佳言之15〇至17〇艽，更佳 言之160至165°C的塔底溫度。 —般調整在塔頂之回流以使佔優勢含量的NPG甲酸酯保 留在塔中。 在冷凝器中獲得之冷凝物較佳再循環至蒸餾塔，達大於 3〇重量❶/。之程度，較佳達大於6〇重量％之程度。冷凝物較 佳再循環至塔頂。 一般藉由在塔底中之蒸發器引入蒸發所需能量。 蒸發器一般為自然循環蒸發器或強制循環蒸發器。然 而，亦可使用具有短滯留時間的蒸發器、降膜式蒸發器、 螺旋管式蒸發器、刮膜式蒸發器或短通道蒸發器。蒸發器 可以適當方式例如藉由16巴蒸汽或熱載體油供熱。 蒸館塔較佳地具有用於提高分離性能之内件。蒸餾内件 可例如以結構填充物，例如以薄片金屬填充物諸如201247618 VI. Description of the Invention: [Technical Field of the Invention] The present invention relates to a process for preparing hydroxypivalaldehyde (oxime) by reacting isobutyraldehyde (IBA) with a brewing (FA). The application further relates to a method for preparing neopentyl glycol (NPG) by hydrogenation according to the invention, and further converting the NPG thus obtained into a polyester resin, an unsaturated polyester resin, and lubricating Agent or plasticizer. The present application is hereby incorporated by reference in its entirety in its entire entire entire entire entire entire entire entire entire entire entire entire entire entire entire entire entire entire entire entire content [Prior Art] Neopentyl glycol is used as a raw material for preparing a saturated polyester resin for a powder coating material or a glass fiber reinforced polymer. Generally, neopentyl glycol is prepared in a stage process, wherein first, isobutyraldehyde (ΙΒΛ) and furfural (FA) are reacted by aldol addition to obtain a ketone group (ΗΡΑ) which can be used in the second process. Direct hydrogenation to neopentyl glycol (NPG) in the stage. In the first process stage (aldol reaction), isobutyraldehyde is generally reacted with formaldehyde in the presence of a tertiary amine as a catalyst in an aldol reaction. The products of the aldol reaction generally include hydrazine and unconverted starting compounds such as furfural, hydrazine and the tertiary amine catalyst used and water. The product generally also includes impurities and by-products of the alcoholic reaction, such as formic acid which can be formed from formaldehyde by the Cannizzaro or Tishchenko reaction, and the formate of the amine catalyst used, such as trimethylammonium formate. After the aldol reaction, the unconverted aldehyde and a portion of the amine base are usually removed by distillation and recycled to the aldol reaction. 163421.doc 201247618 For example, WO 97/173 13 describes the preparation of a hydroxyl group by reacting a corresponding aldehyde with an aqueous formaldehyde in the presence of a tertiary amine in a reactor cascade consisting of several stirred vessels connected in series. The method of the alkane. The resulting reaction mixture is typically purified in several columns. WO 98/28253 likewise discloses a multistage process for the preparation of hydroxyalkanes in which, in the first stage, the corresponding starting aldehyde is reacted with FA in the presence of a trialkylamine, and in the second stage, from the stage The reaction mixture is separated by a steaming plant into a bottoms comprising the reaction product and a top product consisting of a lower boiling component which can be recycled to the first stage. In the third stage, the bottom fraction from the second stage is introduced into the post-reaction or distillation stage, wherein the compound which is not completely methylolated is converted into the corresponding mercapto compound and the top is distilled off. The bottom product obtained in the distillation is sent to hydrogenation. Also described in US 4,036,888, GB 1219162 and JP-A 3,193,738 are two-stage processes for the preparation of NPG, wherein IBA is first reacted with formaldehyde under a base catalyst to produce hydrazine, which is then catalytically hydrogenated to npg. A general description of a two-stage process for the preparation of NPG can be found, for example, in W〇_Ai_2010079187. [Invention] It is an object of the present invention to provide a process for preparing Ηρα, which can be directly introduced into a downstream hydrogenation in which ruthenium is converted into NPG. At the stage, the thermal decomposition of the crucible is substantially avoided. An alkyd reaction product should be provided which produces a higher NPG yield and a lower degree of undesirable side reactions during the downstream hydrogenation stage. Another object of the present invention is to reduce the amount of furfural δ used in the aldol reaction, thereby saving raw material costs. Another object of the present invention is to provide an alcoholic reaction product of 163421.doc 201247618 having a low content of unconverted isobutyraldehyde. Further, a method for reducing the formation of hydrazine (an ester of hydroxypivalic acid and NPG (=ΗΡΝ)) is provided. The process according to the invention also produces a hydrogenation feed having a pH of from 7.5 to 8.5 without the addition of other pH adjusting agents. [Embodiment] The object of the present invention is achieved by a process for preparing hydroxypivalaldehyde (HPA), which comprises, in the first stage, isobutyraldehyde (IBA) and formaldehyde (FA) in the presence of a tertiary amine. In the second stage, the reaction product obtained in the first stage is introduced into the stripper' and the stripping gas is introduced into the stripper. According to the invention, in the first reaction stage, isobutyraldehyde is reacted with furfural in the presence of a tertiary amine. The brewing is generally carried out in an aqueous solution of formaldehyde. Industrially available furfural is generally sold as an aqueous solution having a concentration of 30, 37 and 49% by weight. However, up to 60% by weight of formaldehyde solution can also be used in the process. Industrial formaldehyde generally involves the preparation of the formic acid produced. The degradation product of formic acid can reduce the service life of the hydrogenation catalyst in the downstream hydrogenation stage to cause a decrease in NPG yield. In a particular embodiment, furfural containing 15 〇 ppm or less of formic acid is used. This method can be obtained by treating a furfural or furfural aqueous solution with a basic ion exchanger as described in the application of WO 〇 2〇〇81〇7333. Useful anion exchangers include the ion exchange W known per se, which is strongly basic, weakly basic or moderately basic and is in the form of a colloid or a macroporous form. These are, for example, anion exchangers having a polystyrene resin structure having a tertiary amine group as a functional group and a divinylbenzene parent. Also useful is I63421.doc 201247618 which is an ion exchange agent based on acrylic acid or methacrylic acid crosslinked with diethylene or a resin prepared by condensation of formaldehyde and phenol. Specific useful examples include commercially available products: Ambersep® 900 from Rohm and Haas, Philadelphia, USA, Amberlyst® and Amberlite®, and Lewatit® from Lanxess, Leverkusen. Isobutyraldehyde is also used in the process according to the invention. The process of isobutylation is described, for example, in the section "Butanals" (Ullmann's Encyclopedia of Industrial Chemistry, Published Online: September 15, 2000, DOI: 10.1002/14356007. A04_447). It can be prepared, for example, by a hydrogenation reaction of propylene. The purity of isobutyraldehyde used is preferably greater than 95% by weight, more preferably greater than 97% by weight and more preferably greater than 99% by weight. The tertiary amines used may be the amines as described, for example, in DE-A 28 13 201 and DE-A 27 02 582. Particularly preferred are tri-n-alkylamines, especially triethylamine, tri-n-propylamine, tri-n-butylamine and tridecylamine. Very good are triterpenic amines ("TMA"), triethylamine ("T") and tri-n-propylamine ("TPA") because these compounds generally have lower/frozen points than npg and thus facilitate self-reaction The mixture is steamed and removed. Particularly preferred is the use of trimethylamine ("TMA") as the tertiary amine in the reaction. The aldol reaction (first stage) can be carried out with or without the addition of an organic solvent or solubilizer. In the various distillations according to the process of the present invention, the use of a solvent which forms a suitable low-point mixture with the low-boiling compound may reduce the energy consumption in such distillation and/or facilitate the distillation of low-boiling compounds. Boiling Point 163421.doc -6· 201247618 Suitable solvents are, for example, cyclic and acyclic ethers such as THF, dioxane, methyl second butyl ether or alcohols such as methanol, ethanol or 2-ethylhexanol. In the aldol reaction, the molar ratio of isobutyraldehyde to formaldehyde added in a fresh form in each case is in the range of about 1:1 to 1:5, preferably 1:1:1. Within the range of 1:3.5 and, more preferably, within the range of 1:1 〇 2 to 1: 丨 5 and especially preferably within the range of 1:1, 03 to 1:1.1. The amount of the tertiary amine catalyst added in the aldol reaction is generally from 0.001 to 0.2, preferably 〇1 to 〇07 equivalents, relative to the added isobutyraldehyde. This means that the catalyst is generally used in a catalytic amount. amine. The alcoholic reaction is generally carried out at a temperature of from 5 to 100 t, preferably from 15 to 80 °C. Generally speaking, the pressure of from 1 to 30 bar, preferably from 1 to 15 bar, more preferably from j to 5 bar, is suitably carried out under the self-generating force of the relevant reaction system. reaction. The aldol reaction can be carried out batchwise or continuously. The aldol reaction is preferably carried out in a continuous stirred tank reactor or continuous tank cascade. To adjust the residence time, a portion of the reaction product from one of the stirred tanks can be recycled to a specific stirred tank reactor. The total residence time of the first stage (aldol reaction) is preferably from 0.25 to 12 hours, more preferably from 0.5 to 8 hours and particularly preferably from 1 to 3 hours. In a preferred embodiment, the preferred residence is preferably selected. The residence time of a single reactor in the reactor cascade is such that the total residence time is equally divided between the reactors. The product from the alcohol complex reaction generally comprises unconverted starting compounds such as furfural, alkanal and the tertiary amine catalyst used and possibly water. 163421.doc 201247618 The product additionally includes hydroxypivalaldehyde (ΗΡΑ). The product generally also includes impurities and by-products from the aldol reaction, such as formic acid, which may be produced by the use of a Cannizzaro or Tishchenko reaction, such as HPN, and the formate of the amine catalyst used, such as triterpene citrate. The product from the aldol reaction preferably comprises from 40 to 80% by weight and more preferably from 50 to 70% by weight. In a preferred embodiment, the product from the aldol reaction has the following composition: ΗΡΑ: 40 to 80% by weight; water: 10 to 50% by weight; ΙΒΑ: 0 to 20% by weight; FA: 0 to 10% by weight; Tertiary amine: 0 to 10 weight 〇 / 〇. In another preferred embodiment, the product from the aldol reaction has the following composition: ΗΡΑ: 50 to 70% by weight; water: 15 to 40 parts by weight/〇; ΙΒΑ: 1 to 10% by weight; FA: 0.5 to 5 Weight %; tertiary amine: 0 · 5 to 5 weight 〇 / 〇. According to the invention 'in the second reaction stage' the product from the first stage (alcoholic acid reaction) is introduced into a stripping column, wherein a stripping gas is also introduced. The stripper is preferably a split for separating low boiling and high boiling components. The reaction product comprising ruthenium from the first stage is preferably fed into the upper region of the column 163421.doc 201247618, and contains ruthenium The reaction product is withdrawn in the lower region of the column (e.g., at the bottom of the column). In the upper part of the tower or the upper part of the tower, for example, in the space area of the theoretical plate of 1 〇 to 1 〇〇%, preferably 50 to 1 〇〇%, it is generally possible to extract as an important group except for the stripping gas. A gas stream of unconverted isobutyraldehyde, tertiary amine, methanol, and possibly water and furfural. Depending on the separation performance of the column used, those skilled in the art can routinely determine the stripper by conventional calculations based on the known vapor pressure and evaporation equilibrium of the components present in the product from the first stage. The extraction operating conditions. Preferably, the second reaction stage is carried out in a stripping column having internals for improving separation performance. More preferably, the second reaction stage is carried out in a tray column. In the tray tower, the intermediate tray where mass transfer occurs is located inside the tower. Examples of different types of discs are sieve trays, trough trays, double flow discs, blister trays, valve discs or Streuber discs. The blister disk used may also be a modified blister disk having a deflector plate, such as the so-called LORD disk or LORD reactor, which is described, for example, in DE_A1_10120801. Preferred trays are trough-shaped hoods, blister trays, Streuber trays, and modified blister trays. However, in another embodiment, the separating inner member may also be in the form of a structural filler, such as a sheet metal filler, such as a Mellapak 250 Y or M〇ntz Pak, a B 1 -250 type ' or a structured ceramic filler or Any filler, for example, includes a Pall ring, an IMTP ring (from Koch-Glitsch), a Lacy Super Ring 163421.doc 201247618 (Raschig Superring), and the like. The structure or any of the fillers may be arranged in a bed or, preferably, in a plurality of beds. The reaction product from the first stage is preferably supplied to the space zone of the theoretical plate of the stripper of 5〇% and 丨〇〇% (counted from the bottom), more preferably 9〇% and 100% of the stripper The space area of the theoretical board, especially at the top of the disc. Those skilled in the art, using conventional calculation tools, can determine that the number of theoretical feeds of the optimal feed point β as a function of the composition of the reaction product from the first stage is generally from 2 to 100, preferably 2 to 8 Blocks, better in the range of 20 to 70 and best in the range of 25 to 60. The residence time in the tower is preferably from 15 minutes to 3 minutes, more preferably from 3 minutes to 240 minutes and from 6 minutes to 240 minutes. The top pressure is preferably 500 to 3000 mbar, more preferably goo to 2 mbar and best of 1000 to 1500 mbar. At the bottom of the column or at the point of supply of the stripping gas, it is preferred to establish a temperature above the evaporation temperature of the tertiary amine used to completely or substantially completely convert the other low boilers and a portion of the water to the gas phase. According to the present invention, a temperature of not more than 90 eC, preferably 80 ° C and more preferably 75 ° C is established. The temperature at the bottom of the column is preferably from 50 to 90X: more preferably from 55 to 80 ° C and most preferably from 60 to 75 ° C. For example, a tower top pressure of 1 〇 13 mbar and, preferably, a bottom temperature of 7 〇t can be established. The /fly k gas is a gas which is mainly in the presence of a reaction condition and does not react with a substance present in the reaction mixture. The stripping gas used may be inert gas 16342 丨.doc 201247618 body 'such as lilt or a rare gas, especially helium, neon, argon or gas. Nitrogen is preferably used. However, hydrogen gas can also be used herein. The inert gas used may also be a mixture of the foregoing gases. Preferably, the stripping gas is introduced into the lower region of the distillation column and thus flows in a flow direction opposite to the liquid flow. The introduction into the bottom of the column can be achieved by, for example, a distribution ring or a nozzle, but can also be introduced into the lower region of the distillation column, preferably at most 30%, preferably at most 20% and more preferably at most 1 G%. The steam is in the space area of the theoretical plate of the tower (counted from the bottom). The stripping gas introduced is usually completely mixed with the liquid flowing in the opposite direction by the internals of the column. In a preferred embodiment of the stripping column, the stripping gas used may be a hydrogenation reaction vent from an NPG process, which primarily comprises hydrogen. In a particularly preferred embodiment, the hydrogenation reaction gas can be purified by vent strips to remove impurities, particularly tertiary amines, prior to introduction to the stripper. The flow rate of the inert gas supplied is preferably from 0 001 to i per kg/h of feed, more preferably from 0.005 to 0.1, and most preferably from 〇1 to 〇5. In the upper region of the column, unconverted isobutyraldehyde, furfural, methanol and possibly water are typically withdrawn as a gas stream and the condenser is condensed and a portion of the condensate stream is preferably recycled to the column as a return stream. . A portion of the isobutyraldehyde can be recycled to the first reaction stage (aldol reaction) as needed. The return flow at the top of the column is generally adjusted so that the predominant amount of HpA, IBA and water remain in the column, so that ΗΡΑ is obtained almost completely as a bottom product. » The condensate obtained in the condenser is preferably less than the % of the brother. The degree, and more preferably less than 25%, is recycled to the top of the distillation column. 163421.doc 201247618 In the lower region of the > Fettitta, a product comprising, in particular, 4〇 to 8〇 weight 0/〇, and more preferably 60 to 70% by weight of the crucible is generally obtained. In a preferred embodiment, the product from the stripper has the following composition: ΗΡΑ: 40 to 80% by weight; water: 10 to 50% by weight; Residue: Other organic compounds. In another preferred embodiment, the product from the stripping column has the following composition: 60: 60 to 70% by weight 〇/〇; water: 15 to 40% by weight; Residue: other organic compounds. In a preferred embodiment, the pH of the product from the second reaction stage is from 5 to 9', more preferably from 6 to 8. The isobutyraldehyde content is preferably less than 2% by weight, more preferably less than 1% by weight. /〇, even better than 0.5% by weight and especially less than 0.1% by weight. The trialkylamine content is preferably less than 2% by weight. /❶, more preferably less than 1 weight 〇 / 〇 and best said less than 〇 5% by weight. The hydrazine chain content is preferably less than 8 weight ❹/. More preferably, it is less than 5 weights /. And preferably less than 2.5% by weight. The content of pivalic acid and NPG ester (=HPN) is preferably less than 2% by weight, more preferably less than 1% by weight and most preferably less than 0.5% by weight. By the process according to the invention, a product comprising ruthenium can be obtained which can be used directly in the downstream hydrogenation stage (third reaction stage) to prepare neopentyl glycol 16342 丨.doc 12 201247618 (NPG). In a preferred embodiment, after the second reaction stage and before the second reaction stage, no further processing steps are required. By means of the process according to the invention, it is additionally possible to obtain a product which does not require the addition of a pH adjusting agent, which can be used directly in another reaction stage, wherein the product from stage 2 is hydrohydrogenated in the presence of a hydrogenation catalyst (first) Three reaction stages = hydrogenation reaction). However, it is also possible to mix the product from the second reaction stage with a pH adjusting agent (for example a tertiary amine, an inorganic base, a mineral acid or an organic acid) to adjust the pH until the hydrogenated product (product from the third reaction stage) has 7 to The ppj value of 9 can also be fed into and mixed with the hydrogenation feed separately from the pH adjuster. The tertiary amine used may be the above tertiary amine, especially Tma. In the hydrogenation reaction (third reaction stage), it is preferred to use a catalyst preferably on a support material comprising at least one metal of the transitional groups 8 to 12 of the periodic table, such as Fe, Ru, 〇s, C〇, Rh, Ir, Ni, Pd, Pt, Cu, Ag, An, Zn, Cd, Hg, preferably Fe, Co, Ni, Cu, RU, Pd, pt, more preferably used by Cu e The support material is preferably a support material composed of titanium, tantalum, niobium, tantalum and/or aluminum oxide. Useful catalysts can be prepared by methods known from the prior art for preparing such supported catalysts. It is also preferred to utilize a supported catalyst comprising copper on a support material comprising oxidized or titanium dioxide in the presence or absence of or a plurality of elements of strontium, barium, zinc or chromium. Such catalysts and processes for their preparation are known from WO 99/44974. Further, the supported copper catalysts described in, for example, WO 95/32171 and 16342 丨.d〇c -13 - 201247618 are disclosed in EP-A 44 444 and DE 19 57 591 t for use in hydrogenation reactions. The hydrogenation reaction can be carried out batchwise or continuously in, for example, a reactor tube filled with a catalyst bed, wherein the reaction solution flows through a catalyst bed, for example in a spray or liquid phase mode, as in DE-A 19 41 633 or DE-A 20 40 Said in 501. Advantageously, the reaction product substream can be recycled after cooling and passed through the fixed catalyst bed as desired. Also advantageously, in a plurality of reactors connected in series (for example in 2 to 4 reactors) The hydrogenation reaction is carried out, in which case the hydrogenation reaction in each reactor upstream of the final reactor is only subjected to at most a partial conversion of, for example, 50 to 98%, and the hydrogenation reaction is completed only in the final reactor. Suitably, the hydrogenation product from the previous reactor may be cooled by, for example, a cooling device or by spraying a cooling gas (such as hydrogen or nitrogen) or a substream into which the cold reaction solution is introduced before entering the next reactor. The hydrogenation temperature is generally between 50 and 180 ° C', preferably between 90 and 140 ° C. The hydrogenation pressure employed is generally from 1 Torr to 250 bar, preferably from 20 to 120 bar. The reaction product from the third reaction stage (hydrogenation reaction) comprises a mixture containing NPg, which preferably has the following composition: 20 to 90% by weight of NPG, 〇 to 5 parts by weight of hydrazine/hydrazine, and hydrazine to 5 parts by weight. a tertiary amine of hydrazine, 0 to 5% by weight of an organic secondary compound, 0.01 to 5% by weight of a tertiary amine and an adduct of citric acid (amine citrate), 163421.doc 14 201247618 Residual water. The aqueous NPG mixture preferably has the following composition: 50 to 80% by weight (NPG, 0.1 to 3% by weight of methanol, 〇·〇1 to 5% by weight of tertiary amine, 0 to 5% by weight of organic secondary compound, 0.01 Up to 5% by weight of the tertiary amine and formic acid adduct (amine carbamate), residue water. The organic secondary compound present may be, for example, isobutanol. Preferably, the low boilers are removed from the NPG, Purification of the aqueous nPg mixture 0 is preferably carried out by steaming the low boilers from the aqueous NPG mixture. Preferably, the low boilers (such as water, isobutanol, methanol and tertiary amines) are removed via the top under reduced pressure. Distillation is carried out in a manner such that when the amine used has a lower boiling point than the formed NPG, as in the case of tmA, TEA and TPA. When a tertiary amine having a higher boiling point than the formed NPG is used, it is removed together The tertiary amine at the bottom and the formed NP G are enriched at the bottom of the column in the downstream steaming stage, while the NPG is withdrawn as the overhead product. In general, during the distillation, a portion of the amine citrate is at the bottom of the column. Or react with NPG in the stripping zone of the column to produce free amines and NPG The formic acid vinegar preferably forms a single vinegar of A and NPG, which is referred to as npg formic acid in the scope of the present disclosure. Generally, it is removed at the top of the column together with other low boilers by steaming. The amine released by the reaction. 163421.doc -15- 201247618 Thus the distillation should be adjusted so that the formed NPG formate in the bottom product is kept at a low concentration and the target product (NPG) has the maximum purity. The bottom temperature above the evaporation temperature of the NPG formate is selected in the distillation to achieve complete or substantially complete conversion of the NPG formate to the gas phase by evaporation. The yield and product achieved by this measure The improvement in quality is most likely due to the fact that poly-methane formates generally have a higher boiling point than other low-boiling substances and that the polymethylolformate is precipitated in the rectification section of the column at a suitable reflux rate. The NPG formate precipitated in the rectification section can be hydrolyzed with water to form formazan and Npg again. Typically, the formic acid is removed overhead and the NPG can generally be withdrawn from the bottom of the column. In a preferred embodiment, Therefore, it is preferred to steam as follows : The condenser is generally operated at a temperature at which the lower boiling point of the catalytic advantage condenses at the corresponding top pressure. In general, the operating temperature of the condenser is between 〇 and 80 ° C, preferably 2 〇 to 50 ° C. The cooling medium used herein may preferably be extremely cold water (e.g., about 5 ° C) or a coolant mixture (e.g., at 2 〇 (. (: ethylene glycol-water). More preferably 0.001 to 9.9 bar, more preferably 〇1 to 〇5 bar. On a commercial scale, a vacuum is generally obtained by a steam ejector. At the bottom of the column, it is preferred to establish a higher than NPG formate. The temperature of the evaporation temperature is such that the NPG formate is completely converted or substantially completely converted to the gas phase. It is particularly preferable to establish a boiling temperature of 5 ° / higher than the boiling temperature of NPG formate. Up to 5〇% and optimally the temperature at which the boiling temperature of the NPG formate is 10% to 20% higher. 163421.doc -16· 201247618 For example, in the case of using TMA as a tertiary amine and preparing NPG at a top pressure of 75 mbar, a better 15 to 17 can be established, more preferably The bottom temperature of 160 to 165 °C. The reflux at the top of the column is generally adjusted to maintain the predominant amount of NPG formate in the column. The condensate obtained in the condenser is preferably recycled to the distillation column to a weight greater than 3 Torr. The extent is preferably greater than 6% by weight. The condensate is preferably recycled to the top of the column. The energy required for evaporation is typically introduced by an evaporator in the bottom of the column. The evaporator is typically a natural circulation evaporator or a forced circulation evaporator. However, an evaporator having a short residence time, a falling film evaporator, a spiral tube evaporator, a wiped film evaporator or a short passage evaporator can also be used. The evaporator can be heated in a suitable manner, for example by means of 16 bar steam or heat carrier oil. The steaming tower preferably has an inner member for improving separation performance. The distillation internals may for example be structured packing, for example in a sheet metal filling such as
Mellapak 250 Υ或Montz Pak Β1-250類型存在。亦可存在 具有相對低或增加比表面積的結構填充物，或可使用織物 填充物或具有另一幾何形狀之結構填充物，如MeHapak 252 Y.。相比例如閥盤，在利用此類蒸餾内件之情形中的優 點為低壓降及低比持液量。内件可存在於一或多個區段 中。 來自II化反應之產物較佳地饋入位於蒸顧塔之％及％之 理論板的空間區域’更佳言之位於蒸餾塔之丨/3及2/3之理 論板的空間區域内。例如，饋入可在稍高於理論板中部 163421.doc 201247618 (3:4比）處。 較佳言之10至20的範圍 理論板的數目一般在5至30, 内。 在冷凝器中，…寻之冷凝物為如上所述作為返回流主要 供應至塔中的低沸點物混合物。例如，低彿點物混合物可 包括胺、水及式（III)之醇類，諸如來自異丁醛之異丁醇或 來自正丁醛之正丁醇以及來自曱醛之甲醇。 未冷凝的殘質蒸汽可以能量有利地方式直接呈氣態送至 燃燒’或供應至在接近環境壓力下操作之蒸餾塔。此下游 塔用於進一步對冷凝物進行蒸餾分離。 較佳自蒸發器底部排出主要包括NPG之產物。亦可自| 發器之循環流中排出。底部產物在本發明範圍中稱為「粗 NPG」。 如此獲得之粗NPG包括小比例之多經曱基甲酸自旨。多經 甲基甲酸酯之比例較佳地少於1 500 ppm(按重量計算），較 佳言之少於1200 ppm(按重量計算）、更佳言之少於8〇〇 ppm(按重量計算）及尤佳言之少於600 ppm(按重量計算）。 粗NPG另外包括NPG。 粗NPG較佳具有下列組成： 90至99重量°/❶之NPG⑴， 0.01至5重量％之羥基新戊酸， 0至5重量％之有機二級化合物。 粗NPG更佳具有下列組成： 95 至 99 重量 ％2NPG， 163421.doc • 18· 201247618 0.1至2重量％之羥基新戊酸， 0至3重量％之有機二級化合物。 為除去在底部物中存在之相對較高沸點的酸性組份（尤 其係羥基新戊酸)而較少損失NPG，纟蒸餾中所用之底部 . 蒸發器較佳地為至少一個具有短滯留時間的蒸發器，例如 有殘質排放之降膜式蒸發器、薄膜蒸發器或螺旋管式蒸 發器。 、 在-個特定實施例中’塔底可以g己置成錐形底，從而進 一步縮短在塔底之滯留時間。 較佳地在下列條件下進行粗NpG之蒸館： 有利〇之，在冷凝器中獲得之冷凝物再循環至蒸餾塔 (返回流）達大於30重量％之程度、更佳言之達大於5〇重量 %之程度。冷凝物較佳地再循環至塔頂。 較佳地在50至180°C，較佳言之130至16〇。(：範圍内之溫 度下操作冷凝器。 此處所用冷卻介質較佳地儘可能為水，其同時蒸發。 頂部壓力更佳係0.001至0_9巴，更佳言之〇〇1至〇5巴及 最佳言之0.02至0.4巴。 一般藉由蒸汽噴射器產生工業規模的真空。 一般選擇底部溫度以使NPG轉化成氣相而羥基新戊酸保 留在塔底。 較佳地建立為100至150%，較佳言之1〇5至14〇%，更佳 言之110至130%之NPG之沸騰溫度的底部溫度。 例如，在利用TM A作為三級胺及在15〇毫巴之塔頂壓力 163421.doc -19- 201247618 下製備NPG之情形下，較佳地建立i5〇至2〇CTc，更佳言之 160至190°C的塔底溫度。 蒸館塔之底部較佳地連接至至少一個具有短滯留時間的 蒸發器。 蒸餾塔之底部及具有短滯留時間之蒸發器一起按定義之 方式組成蒸發階段。 根據本揭示案’蒸發階段之滯留時間係藉由將在塔之受 熱部份中之持液體積（V待液）除以塔之返回流及饋入體積流 之總和而計算（\U；a/(饋入流+返回流）），塔之受熱部份中之 持液體積（V* *)係甴塔底之持液體積（Vm部）加上蒸發器 之持液體積（V将液，》發8 )而計算（V持A =v待液，底ip ，"a)。 蒸發階段之滞留時間宜少於45分鐘，較佳言之少於3〇分 鐘’更佳言之少於15分鐘，尤其較佳言之少於1〇分鐘及最 佳言之少於5分鐘。 一般而言，較佳地選擇蒸發階段之滞留時間，以致在較 高底部溫度下相應地建立較短滯留時間。 在處於NPG之沸騰溫度之130至150%範圍内的底部溫度 下’蒸發階段之滞留時間較佳係5分鐘及更少，更佳言之4 分鐘及更少’及最佳言之3分鐘及更少。 在處於NPG之沸騰溫度之！ 2〇至130%範圍内的底部溫度 下’蒸發階段之滞留時間較佳係3 0分鐘及更少，更佳+之 15分鐘及更少及最佳言之1〇分鐘及更少，及尤佳言之5分 鐘及更少。 在處於NPG之沸騰溫度之100至120%範圍内的底部溫产 16342 丨,doc -20- 201247618 下’蒸發階段之滯留時間較佳係45分鐘及更少，更佳言之 30分鐘及更少及最佳言之15分鐘及更少，及尤佳言之1〇分 鐘及更少。 在另一特定實施例中’具有短滯留時間的蒸發器連接至 具有短滯留時間的至少一個其他蒸發器。 在該較佳實施例中，蒸餾塔之底部及具有短滯留時間的 蒸發器根據定義一起構成第一蒸發階段。 具有短滞留時間的其他蒸發器根據定義形成第二或第 (1+n)個（其中於2)蒸發階段。 具有知滯留時間的蒸發器較佳地連接至具有短滯留時間 的一個其他蒸發器（二階段結構）。 在該實施例中，蒸發所需之能量的主要部份通常在第一 蒸發階段引人。在第二蒸發卩皆段中，蒸發所需之更高溫度 接著可利用更短的滯留時間達成，使得在第二蒸發階段的 滯留時間更短β m第一階段較佳地酉己置成降膜#蒸發胃或螺旋f式蒸發 M該特實施例之第二階段較佳係降膜式蒸發器、螺旋 管式蒸發器或薄層蒸發器。 根據本揭示案，第一蒸發階段之滯留時間係藉由在塔之 ^熱部份中之持液體積（D除以塔之返回流及饋入體積 机：總和而計算(V⑼/(饋入流+返回流”，塔之受熱部份中 :之：體積(V係由塔底之持液體積(v“…)加上蒸發 、液體積而計算H "心_)。 艮本揭不案，第二蒸發階段之滞留時間係藉由在第 163421,doc -21 · 201247618 蒸發器中之持液量除以第二蒸發器之饋入流而計算。根據 本揭示案’第（l+n)蒸發階段之滯留時間係藉由在第（1+η) 蒸發器中之持液量除以第（丨+η)蒸發器之饋入流而計算。 在該較佳實施例中’第一蒸發階段之底部溫度宜高於 NPG之蒸發溫度。 第一蒸發階段之底部溫度較佳地高出NPG之沸騰溫度 100至130°/。’更佳言之110至丨25〇/〇。 一般選擇第二蒸發階段之溫度以使ΝΡ(3幾乎完全轉化成 氣相。 第二蒸發階段之溫度較佳地高出NPG之沸騰溫度1〇5至 150/〇，更佳s之120至15〇〇/0，尤其較佳言之13〇至14〇0/〇。 第一蒸發階段之滯留時間宜少於45分鐘，較佳言之少於 30刀鐘，更佳s之少於15分鐘，尤其較佳言之少於分鐘 及最佳言之少於5分鐘。 第一蒸發階段之滯留時間宜少於3 〇分鐘，較佳言之少於 15分鐘，更佳言之少於5分鐘，尤其較佳言之少於2分鐘及 最佳言之少於1分鐘。 一般而言，較佳地選擇蒸發階段之滞留時間以使在更高 的底部溫度下相應地建立更短的滯留時間。 如上所述，具有短滯留時間之蒸發器可連接至超過一個 ”有短滯留時間之其他蒸發器，例如2或3個蒸發器，在該 隋形下蒸發器鏈中之最後—者構成所稱之最後蒸發階 段0 最後蒸發階段之滯留時間 及溫度對應於兩階段結構中之 163421.doc •22· 201247618 第二蒸發階段的滯留時間及溫度。 在利用TMA作為三級胺製備NPG時，在第一蒸發階段， 可較佳地在少於45分鐘，較佳言之少於30分鐘之滞留時間 下建立135至170°C ’更佳言之150至16〇t之底部溫度。在 第二蒸發階段，較佳地在少於15分鐘，較佳言之少於1〇分 鐘及更佳言之少於5分鐘之滞留時間下建立16〇至220。〇， 較佳言之180至200°C之溫度。 蒸餾塔較佳地具有用於提高分離性能之内件。蒸館内件 可例如以結構填充物’例如以薄片金屬填充物諸如Mellapak 250 Υ or Montz Pak Β1-250 type exists. Structural fillers having a relatively low or increased specific surface area may also be present, or fabric fillers or structural fillers having another geometry, such as MeHapak 252 Y., may be used. The advantages in the case of utilizing such a distillation internals are, for example, a low pressure drop and a low specific liquid hold capacity compared to, for example, a valve disc. The internals may be present in one or more sections. The product from the II reaction is preferably fed into the spatial region of the theoretical plate at % and % of the distillation column. More preferably, it is located in the spatial region of the theoretical plate at /3 and 2/3 of the distillation column. For example, the feed can be slightly higher than the middle of the theoretical plate at 163421.doc 201247618 (3:4 ratio). Preferably, the range of 10 to 20 is generally between 5 and 30. In the condenser, the condensate is the low boiler mixture which is mainly supplied to the column as a return stream as described above. For example, the low bud mixture may include an amine, water, and an alcohol of formula (III), such as isobutanol from isobutyraldehyde or n-butanol from n-butyraldehyde and methanol from furfural. The uncondensed residual vapor can be sent to the combustion directly or in a gaseous manner in an energy-efficient manner or to a distillation column operating at near ambient pressure. This downstream column is used to further distill off the condensate. Preferably, the product comprising primarily NPG is discharged from the bottom of the evaporator. It can also be discharged from the circulating flow of the hair dryer. The bottom product is referred to as "crude NPG" within the scope of the present invention. The crude NPG thus obtained includes a small proportion of polythiocarbamate. The proportion of polymethylformate is preferably less than 1,500 ppm (by weight), preferably less than 1200 ppm (by weight), more preferably less than 8 〇〇ppm (by weight) Calculated) and especially better than 600 ppm (by weight). The crude NPG additionally includes NPG. The crude NPG preferably has the following composition: 90 to 99 wt/N of NPG (1), 0.01 to 5% by weight of hydroxypivalic acid, and 0 to 5% by weight of an organic secondary compound. The crude NPG preferably has the following composition: 95 to 99% by weight 2NPG, 163421.doc • 18·201247618 0.1 to 2% by weight of hydroxypivalic acid, 0 to 3% by weight of the organic secondary compound. In order to remove the relatively higher boiling acidic component (especially hydroxypivalic acid) present in the bottom portion, the NPG is less lost, the bottom used in the distillation. The evaporator is preferably at least one having a short residence time. Evaporators, such as falling film evaporators with residual emissions, thin film evaporators or spiral tube evaporators. In a particular embodiment, the bottom of the column can be placed into a conical bottom to further reduce the residence time at the bottom of the column. Preferably, the distillation of the crude NpG is carried out under the following conditions: Advantageously, the condensate obtained in the condenser is recycled to the distillation column (return flow) to a degree of more than 30% by weight, more preferably greater than 5 〇% by weight. The condensate is preferably recycled to the top of the column. It is preferably 50 to 180 ° C, preferably 130 to 16 Torr. (The condenser is operated at a temperature within the range. The cooling medium used herein is preferably water as much as possible, which evaporates at the same time. The top pressure is preferably 0.001 to 0_9 bar, more preferably 〇〇1 to 〇5 bar and Preferably, it is 0.02 to 0.4 bar. An industrial scale vacuum is typically produced by a steam ejector. The bottom temperature is generally selected to convert the NPG to the gas phase and the hydroxypivalic acid remains at the bottom of the column. Preferably, it is established as 100 to 150. %, preferably 1〇5 to 14〇%, more preferably 110 to 130% of the bottom temperature of the boiling temperature of NPG. For example, using TM A as a tertiary amine and at the top of 15 mbar In the case of preparing NPG under pressure 163421.doc -19- 201247618, it is preferred to establish a bottom temperature of i5 〇 to 2 〇 CTc, more preferably 160 to 190 ° C. The bottom of the steaming tower is preferably connected to At least one evaporator having a short residence time. The bottom of the distillation column and the evaporator with a short residence time together form the evaporation phase in a defined manner. According to the disclosure, the residence time of the evaporation phase is carried out by the heating section of the tower. The liquid holding volume (V waiting liquid) divided by the return of the tower Calculated by the sum of the flow and the feed volume flow (\U;a/(feed flow + return flow)), the liquid hold volume (V* *) in the heated portion of the tower is the liquid hold volume at the bottom of the tower (Vm Part) plus the liquid holding volume of the evaporator (V will be liquid, "8") and calculate (V holding A = v to be liquid, bottom ip, " a). The retention time in the evaporation stage should be less than 45 minutes, Good words are less than 3 minutes 'better than 15 minutes, especially better than 1 minute and best less than 5 minutes. In general, it is better to choose the retention of evaporation Time, so that a shorter residence time is established correspondingly at a higher bottom temperature. The residence time of the 'evaporation phase' is preferably 5 minutes and less at the bottom temperature in the range of 130 to 150% of the boiling temperature of the NPG, more 4 minutes and less of good words and 3 minutes and less of the best words. At the boiling temperature of NPG! The bottom temperature in the range of 2〇 to 130% is better than the retention time of the evaporation stage. Minutes and less, better + 15 minutes and less and best 1 minute and less, and especially good for 5 minutes and less. The bottom temperature is 16342 丨 in the range of 100 to 120% of the boiling temperature of the NPG, and the retention time in the evaporation stage is preferably 45 minutes and less in the doc -20-201247618, more preferably 30 minutes and less. Preferably, 15 minutes and less, and especially 1 minute and less. In another particular embodiment, an evaporator having a short residence time is connected to at least one other evaporator having a short residence time. In the preferred embodiment, the bottom of the distillation column and the evaporator having a short residence time are combined to define a first evaporation stage. Other evaporators with short residence times form a second or (1+n)th (of which 2) evaporation stages by definition. The evaporator having a known residence time is preferably connected to one other evaporator (two-stage structure) having a short residence time. In this embodiment, the major portion of the energy required for evaporation is typically introduced during the first evaporation stage. In the second evaporation zone, the higher temperature required for evaporation can then be achieved with a shorter residence time, so that the residence time in the second evaporation stage is shorter. The first stage of the β m is preferably set to lower. Membrane #vaporizing stomach or spiral f-evaporation M. The second stage of this particular embodiment is preferably a falling film evaporator, a spiral tube evaporator or a thin layer evaporator. According to the present disclosure, the residence time of the first evaporation stage is calculated by dividing the liquid holding volume in the hot portion of the column (D divided by the return flow of the column and the feed volume: sum (V(9)/(feed flow) + return flow", in the heated part of the tower: volume: V is calculated from the liquid holding volume at the bottom of the tower (v "...) plus evaporation, liquid volume, and H "heart_). The residence time of the second evaporation stage is calculated by dividing the liquid holding capacity in the evaporator of 163421, doc - 21 · 201247618 by the feed stream of the second evaporator. According to the present disclosure '(l+n) The residence time in the evaporation stage is calculated by dividing the liquid holding capacity in the (1+η) evaporator by the feed stream of the (丨+η) evaporator. In the preferred embodiment, the first evaporation stage The bottom temperature is preferably higher than the evaporation temperature of the NPG. The bottom temperature of the first evaporation stage is preferably higher than the boiling temperature of the NPG by 100 to 130 ° /. 'More preferably 110 to 丨 25 〇 / 〇. Generally choose the second The temperature of the evaporation stage is such that the enthalpy (3 is almost completely converted into the gas phase. The temperature of the second evaporation stage is preferably higher than the boiling temperature of the NPG 1 5 to 150 / 〇, more preferably s 120 to 15 〇〇 / 0, especially preferably 13 〇 to 14 〇 0 / 〇. The retention time of the first evaporation stage is preferably less than 45 minutes, preferably less 30 knives, more preferably less than 15 minutes, especially preferably less than minutes and best less than 5 minutes. The residence time of the first evaporation stage should be less than 3 〇 minutes, preferably Less than 15 minutes, more preferably less than 5 minutes, especially preferably less than 2 minutes and best less than 1 minute. In general, it is preferred to select the residence time of the evaporation phase to make it more A shorter residence time is established correspondingly at a high bottom temperature. As mentioned above, an evaporator with a short residence time can be connected to more than one other evaporator with a short residence time, for example 2 or 3 evaporators, where The last in the evaporator chain of the 隋 shape constitutes the final evaporation phase of the final evaporation phase. The residence time and temperature of the final evaporation phase correspond to the two-stage structure of the 163421.doc •22·201247618 The retention time and temperature of the second evaporation phase In the preparation of NPG using TMA as a tertiary amine, in the first evaporation stage Preferably, a bottom temperature of 135 to 170 ° C, more preferably 150 to 16 〇t, is established at a residence time of less than 45 minutes, preferably less than 30 minutes. In the second evaporation stage, Preferably, the temperature is established between 16 and 220 in less than 15 minutes, preferably less than 1 minute and more preferably less than 5 minutes. 〇, preferably 180 to 200 °C. The distillation column preferably has internals for improved separation performance. The vapour chambers may, for example, be structurally filled with, for example, a sheet metal fill such as
Mellapak 250 Y或Montz Pak，B1-250類型存在。亦可存在 具有相對低或增加比表面積的結構填充物，或可使用織物 填充物或具有另一幾何形狀之結構填充物，諸如Meiiapak 252Y。相比於例如閥盤，在利用該類蒸餾内件之情形中的 優勢為低壓降及低比持液量^内件可存在於一或多個區段 中〇 來自氫化反應之產物較佳地饋入位於蒸餾塔之1/4及％之 理論板的空間區域’更佳言之位於蒸顧塔之1 /3及2/3之理 論板的空間區域内。例如，饋入可在稍高於理論板中部 (3:4比）處。 理論板的數目一般在5至30，較佳言之1〇至20的範圍 内。 在該類條件下，一般自更高沸點的羥基新戊酸中除去 NPG。 在冷凝器中，純化之NPG較佳地作為冷凝物獲得。 16342I.doc •23- 201247618 NPG之純度較佳係至少99.0重量0/。，更佳言之至少99 2 重量％。 較佳自蒸發器底部排出包括大部份高沸點化合物（如經 基新戊酸）的產物。 底部產物可在焚燒中被熱利用或藉由將其分餾成若干顧 分而饋入下游蒸餾塔。 例如，在製備NPG之情形下，底部產物可以分餾成低沸 點餾分（特定言之包含羥基新戊酸）、中沸點餾分（特定言之 包含HPN(>97% HPN))及高沸點餾分（特定言之ηρα及hpn 之酷）。 未冷凝的殘留蒸汽一般包括洩露空氣及微量的水、大部 份NPG，及宜呈氣態直接再循環至蒸餾階段d)e NPG主要用作用於合成聚醋樹脂、不飽和聚醋樹脂、潤 滑劑及增塑劑之組份。 因此，本發明亦係關於一種製備聚酯樹脂、不飽和聚酿 樹脂、潤滑劑或增塑劑之方法，其包括按照本發明製備 NPG及利用如此製備之NPG以製備聚酯樹脂、不飽和聚酿 樹脂、潤滑劑或增塑劑。 本發明之優勢在於可藉由根據本發明之方法製備ΗΡΑ， 其可直接引入ΗΡΑ轉化成NPG的下游氫化階段中。 按照本發明製備之ΗΡΑ在用於下游氫化反應之前一般不 需要任何進一步的純化。按照本發明製備之ΗΡΑ—般具有 低含量的ΗΡΝ。較佳而言，亦不需要添加任何1)]^調節劑至 氫化反應饋料以獲得位於7.0至9.0範圍内之ρΗ值。根據本 163421.doc -24· 201247618 發明之方法另外使得可製備在下游氫化階段中產生更高產 率及NPG之選擇性之ΗΡΑ。此外，可減少在醇搭反應中所 用曱醛當量數以節省原料成本。此外，來自醇醛反應之第 二反應階段之產物中之未轉化之異丁醛的含量較低。 實例： 下列實例係基於利用（^11611^3丨1111^軟邀達成之模擬結果。 在程序中針對反應物、產物及副產物所用之熱動力參數係 基於公開之熱動力數據或内部測量。針對主反應所使用之 動力常數係經實驗證明；評估副反應之動力常數。 所用之具體裝置之規格及模擬受軟體中所包括之常規程 序影響。 為使模擬模型最佳，將模擬結果與實驗結果對比，在可 利用的情形下，及使模擬模型與實驗結果相符，以使模擬 與實驗數據之間可以達成良好的一致。 下列實例係利用最佳模擬模型計算。 對照實例（模擬）： 在兩階段攪拌槽級聯反應器中，約75〇 g/h異丁醛（約〉 99,5 GC面積％之汨八）與約7〇〇 g/h甲醛（約49% ^，ι 5% 甲醇，剩餘物水）及80 g/h三甲基胺溶液（5〇% TMA水溶液） 反應。 接著，藉由在塔中蒸餾自溶液除去低沸點物。 2該，配有精餾段中之1,5 m織物填充物（比表面積5〇〇 =2/m3)及4 m薄片金層填充物（25〇 一/^)。醇醛反應產物 提供在薄片金屬填充物上方；在塔頂，使用含有冷卻水 16342 丨.doc •25· 201247618 (約⑽）之冷凝器及下游相分離器。在頂部，蒸顧物係呈 氣態供應至冷凝器。獲得約255 g/h液體冷凝物。在下游相 分離器中，除去95 g/h之水相及全部供應至塔内。此外， 來自相分離器之135 g/h被供應至第一授摔槽。爲了維持 85 C下之塔内調節溫度’將25 g/h有機相另外供應至塔 内。在冷凝器之冷卻收集器下游，獲得W g/h之液體(約 80% IBA，約20〇/〇 TMA)，其同樣地再循環。 在約i巴頂㈣對廢力T進行說之除去1肖蒸發器為 降膜式蒸發器。建立1〇〇。(:之塔底之底部溫度。藉由織物 填充物中部的溫度調整至塔内之回流速率；建立85t之溫 度。 藉由泵自塔底抽離約15 kg/h液體。將該液體供應至降膜 式蒸發器（由油熱不銹鋼管組成，長25 m，内徑約21 mm，壁厚約2 mm)。自降膜式蒸發器之底部抽離約Μ kg/h之產物。將蒸汽及過量液體供應至塔底。排出之底部 產物包括約70重量％之ΗΡΑ、約1重量％之HPN、〇 7重量％ 之IB A、剩餘水。 實例1 (模擬） 在兩階段攪拌槽級聯反應器中，約750 g/h異丁醛（約 >99.5 GC 面積 〇/〇之 IBA)與約 700 g/h 甲醛（約 49% Fa、1 5% 甲醇、剩餘物水）及80 g/h三甲胺溶液（5〇〇/〇 TMa水溶液）反 應。 接著，藉由添加汽提氣體，在汽提塔中除去溶液的低沸 點物。 16342 丨.doc -26 - 201247618 該塔配有12塊理論板（板效率約3〇%，相當於約4〇個泡罩 盤）。將醇链反應產物供應至最上面的盤；在塔頂，利用 冷水（約2°C )操作冷凝器。在頂部排出之氣體流被供應至冷 凝器。獲得約60 g/h之液體冷凝物。將冷凝物完全供應至 塔之最上面的盤。在約1巴之頂部絕對壓力下操作汽提 塔。在底部，供應60 g/h之汽提氣體（氮氣）。藉由痕量加 熱’將底部溫度調整至651之數值。 藉由泵自塔底抽離約1.5 kg/h之液體。排出之底部產物 包括約70重量％iHPA、約0.4重量％2ΗΡΝ ' 〇,7重量％之 IBA、剩餘水。 16342I.doc -27-Mellapak 250 Y or Montz Pak, B1-250 type exists. Structural fillers having relatively low or increased specific surface areas may also be present, or fabric fillers or structural fillers having another geometry, such as Meiapak 252Y, may be used. An advantage in the case of utilizing such a type of distillation internals is that a low pressure drop and a low specific liquid hold capacity may be present in one or more sections, preferably from a product of the hydrogenation reaction, as compared to, for example, a valve disc. Feeding into the spatial region of the theoretical plate at 1/4 and % of the distillation column is more preferably located in the spatial region of the theoretical plates of 1/3 and 2/3 of the steaming tower. For example, the feed can be slightly above the middle of the theoretical plate (3:4 ratio). The number of theoretical plates is generally in the range of 5 to 30, preferably 1 to 20. Under such conditions, NPG is typically removed from the higher boiling hydroxypivalic acid. In the condenser, the purified NPG is preferably obtained as a condensate. 16342I.doc •23- 201247618 The purity of NPG is preferably at least 99.0 wt%. More preferably, at least 99 2% by weight. Preferably, the product comprising a majority of high boiling compounds such as pivalic acid is discharged from the bottom of the evaporator. The bottom product can be used thermally in incineration or fed to the downstream distillation column by fractionating it into several considerations. For example, in the case of the preparation of NPG, the bottom product can be fractionated into a low boiling fraction (specifically containing hydroxypivalic acid), a medium boiling fraction (specifically containing HPN (>97% HPN)), and a high boiling fraction ( Specifically, ηρα and hpn are cool). Uncondensed residual steam generally includes leaking air and traces of water, most of the NPG, and should be directly recycled to the distillation stage in a gaseous state. d) e NPG is mainly used for the synthesis of polyester resins, unsaturated polyester resins, lubricants. And plasticizer components. Accordingly, the present invention is also directed to a method of preparing a polyester resin, an unsaturated poly-resin resin, a lubricant or a plasticizer, which comprises preparing NPG according to the present invention and using the NPG thus prepared to prepare a polyester resin, unsaturated poly-polymer Stuffed with resin, lubricant or plasticizer. An advantage of the present invention is that ruthenium can be prepared by the process according to the invention, which can be directly introduced into the downstream hydrogenation stage of the conversion of ruthenium into NPG. The ruthenium prepared in accordance with the present invention generally does not require any further purification prior to use in the downstream hydrogenation reaction. The crucibles prepared in accordance with the present invention generally have a low level of antimony. Preferably, it is also not necessary to add any 1) adjusting agent to the hydrogenation reaction feed to obtain a pH value in the range of 7.0 to 9.0. The process according to the invention of 163421.doc -24·201247618 additionally makes it possible to produce a higher yield and selectivity for NPG in the downstream hydrogenation stage. In addition, the number of aldehyde equivalents used in the alcohol reaction can be reduced to save raw material costs. Further, the content of unconverted isobutyraldehyde in the product from the second reaction stage of the aldol reaction is low. EXAMPLES The following examples are based on simulation results using (^11611^3丨1111^ soft invitations. The thermodynamic parameters used in the program for reactants, products, and by-products are based on published thermodynamic data or internal measurements. The dynamic constants used in the main reaction are experimentally proven; the dynamic constants of the side reactions are evaluated. The specifications and simulations of the specific devices used are influenced by the normal procedures included in the software. To optimize the simulation model, the simulation results and experimental results are obtained. Contrast, in the available cases, and to match the simulation model with the experimental results, so that a good agreement can be achieved between the simulation and the experimental data. The following examples are calculated using the best simulation model. Control example (simulation): In two In the stage stirred tank cascade reactor, about 75 〇g / h isobutyraldehyde (about > 99, 5 GC area% 汨 eight) and about 7 〇〇 g / h formaldehyde (about 49% ^, ι 5% methanol , the remaining water) and 80 g / h trimethylamine solution (5% aqueous solution of TMA) reaction. Next, the low boilers are removed from the solution by distillation in a column. 2, with 1 in the rectification section , 5 m fabric Filler (specific surface area 5 〇〇 = 2 / m3) and 4 m thin gold layer filling (25 〇 / /). Aldol reaction product is provided above the sheet metal filling; at the top of the tower, using cooling water 16342丨.doc •25· 201247618 (approximately (10)) condenser and downstream phase separator. At the top, the steam system is supplied to the condenser in a gaseous state. Approximately 255 g/h of liquid condensate is obtained. In the downstream phase separator , remove 95 g / h of the aqueous phase and supply all to the tower. In addition, 135 g / h from the phase separator is supplied to the first drop tank. In order to maintain the temperature within the tower under 85 C '25 g The /h organic phase is additionally supplied to the column. Downstream of the condenser's cooling collector, a W g/h liquid (about 80% IBA, about 20 〇/〇 TMA) is obtained, which is likewise recycled. Top (four) said to remove the waste force T 1 Xiao evaporator is a falling film evaporator. Establish 1 〇〇. (: the bottom temperature of the bottom of the tower. Adjust the temperature in the fabric fill to the reflux rate in the tower Establish a temperature of 85t. Pump approximately 15 kg/h of liquid from the bottom of the column. Supply the liquid to the falling film evaporator ( It consists of oil-heated stainless steel tube with a length of 25 m, an inner diameter of about 21 mm and a wall thickness of about 2 mm. The product is separated from the bottom of the falling film evaporator by about Μ kg/h. The steam and excess liquid are supplied to the bottom of the tower. The discharged bottom product comprises about 70% by weight of hydrazine, about 1% by weight of HPN, 〇7% by weight of IB A, and residual water. Example 1 (Simulation) In a two-stage stirred tank cascade reactor, about 750 g /h isobutyraldehyde (about >99.5 GC area 〇 / 〇 IBA) with about 700 g / h formaldehyde (about 49% Fa, 1 5% methanol, residual water) and 80 g / h trimethylamine solution (5 〇〇/〇TMa aqueous solution) reaction. Next, the low boiling point of the solution is removed in the stripper by the addition of a stripping gas. 16342 丨.doc -26 - 201247618 The tower is equipped with 12 theoretical plates (the board efficiency is about 3〇%, which is equivalent to about 4 blister disks). The alcohol chain reaction product was supplied to the uppermost tray; at the top of the column, the condenser was operated with cold water (about 2 ° C). The gas stream exiting at the top is supplied to the condenser. Approximately 60 g/h of liquid condensate was obtained. The condensate is completely supplied to the uppermost tray of the tower. The stripper was operated at a top pressure of about 1 bar. At the bottom, 60 g/h of stripping gas (nitrogen) was supplied. The bottom temperature was adjusted to a value of 651 by trace heating. Approximately 1.5 kg/h of liquid was withdrawn from the bottom of the column by means of a pump. The bottom product discharged included about 70% by weight of iHPA, about 0.4% by weight of 2 ΗΡΝ '〇, 7% by weight of IBA, and water remaining. 16342I.doc -27-