201245126 代號 說明 130 第二塔/輕烴塔 131 管線/第二殘留物 132 管線 135 管線/乙醇產物側餾分 五、ί案若有化學式時’請_最織示發明特_化學式： …、0 六、發明說明： 相關交互參考文獻 本中請案主張2G11年12月Μ日於美國提㈣請之美國臨時申請 Τ 61/570,604之優先權，其整體併入本文供參考。本申請g亦係2011 年4月26曰申請之美國專利號13/〇94,537之部分連續申請案，其又主 張2010年7月9日申請之美國臨時申請號61/363,109之優先權，且其 整體併入本文供參考。 【發明所屬之技術領域】 本發明大體上係有_收由乙酸、乙酸乙敝其齡物經氣化所 產生之乙醇之製程。 【先前技術】 ，工業用乙醇習知係自有機料源如石油、天然氣或煤炭所製得、或 自料源中間物如合成氣或自澱粉質材料或纖維素材料如玉米或甘蔗所 製得。自有機料源以及自纖維素材料製造乙醇之習知方法包含乙烯之 酸催化水合、甲醇同系化反應(h〇m〇】〇gati〇n)、直接醇.合成、及費托 (Fischer-Tropsch)合成。石化料源價格不穩定會造成習知製得之乙醇之 價格浮動，使得在料源價格提高時反而對乙醇製造之替代能源更具需 3 201245126 求。澱粉㈣料以及纖維素材料係藉發酵轉化成乙醇L發酵一 般係使用於消費性乙醇之製造，由此所產生的乙醇則適用於供作辦料 或人類>肖費之用。此外，婦質或纖維素材料之發酵會與食物來源相 競爭並使得可被製造於工業用途之乙醇量受到限制。 經由貌酸類及/或其他含幾基化合物之還原反應製造乙醇已廣泛 被研究’ J·觸媒、擔體(supports)及操作條件之各種组合已述於文獻中。 在還原賊類例如還原乙_ ’其他化合物會隨乙醇—起形成，或者 在副反應巾形成。該等雜質限制了乙醇自此反應混合物之生產及回 收。例如在氫化製程中會與乙或水_起產出而形成共沸 物，其將是難以分離的。此外，當轉化不完全時，未反應之酸會殘留 在粗製乙醇產物中，而其必須予以移除以回收乙醇。 EP02060553描述一種將烴類轉化成乙醇之方法，其包含將烴類轉 化成乙酸及將乙酸氫化成⑽。練自氫化反絲之液辭以分離以 獲得乙醇產物，以及乙贿乙n液流，其將被再娜至該氮化 反應器中。 US專利7’842,844號，則描述一種在顆粒狀觸媒存在下將烴類轉 化成乙醇及視情況轉化成乙酸巾，縣擇率及_雜麟作壽命改 良之製程’該轉化係經由合成氣(syng^)產生中間步驟進行。 自藉由還原烷酸如乙酸及/或其他含羰基化合物所得之粗產物以 回收乙醇之改良製程仍有需要。 【發明内容】 第一具體例中，本發明係關於一種製造乙醇之製程，其包括：在 觸媒存在下於反應器中氫化乙酸及/或其酯，而形成粗製乙醇產物；於 第一蒸餾塔中分離至少部份之該粗製乙醇產物，以產生包括乙酸之第 一殘留物及包括乙醇、乙酸乙酯及水之第一餾出物；自至少部份之該 第一餾出物移除水以產生包括少於1〇加％(重量％)水之乙醇混合物液 流；及於第二蒸餾塔中分離部份之該乙醇混合物液流以產生呈蒸汽相 或液相之乙醇侧餾分、包括水之第二殘留物及包括乙酸乙酯之第二餾 4 201245126 出物。一具體例中，該乙醇產物側餾分相較於該第二殘留物更富含乙 醇。該乙醇混合物液流中之至少40〇/〇乙醇可在該乙醇產物侧餾分中被 移除。該乙醇產物側顧分包括少於5〇〇wppm(重量ppm)乙酸及少於 l〇〇wppm乙酸乙酯。該乙醇產物側餾分可在比乙醇混合物液流饋入該 第二蒸餾塔之位置低的位置被抽出。一具體例中，該乙醇產物側餾分 為包括少於12wt%水，其較佳者為少於8wt%水之工業級乙醇。有些 具體例中，該6酸係自曱醇及一氧化碳所形成，其中該甲醇、一氧化 碳及用於氫化步驟之氫各係衍生自合祕，且其巾該合成氣係衍生自 碳源，其係選自由天然氣、油、石油、煤炭、生質材料及其組合所組 成之群組。 第二具體例中’本發明有關-種製造乙醇之製程，其包括：在觸 媒存在下於反應ft巾氫化乙酸，秘成粗製乙醇產物；於第—蒸館塔 中分離至少部份之該粗製乙醇產物，以產生包括乙酸之第__殘留物及 包括乙醇、&酸乙S旨及水之第—細物；自至少部份之該第—德出物 移除水以產生包括少於1Gwt%水之合物較；於第二蒸館塔中 分離部份之該乙醇混合物液流以產生呈蒸汽相或液相之乙醇側德^、 包括水之第二殘留物及包括乙酸乙自旨之第二顧出物.；及減少乙醇產物 ，分之水含量而產生具有水含量⑽低之乙醇餘減。該具有水 含$已降低之乙醇產物液流可具有少於域之水。可使用吸附單元或 ，，該水濃度一具體例中，該具有水含量已降低之乙醇產物液 〜可為包括少於2wt%水’較佳者為少於〇 5域％水之料斗級乙醇。 第三具體例中’本發明有關一種製造乙醇之製程，其包括：在觸 媒存在下於反絲巾氫化乙酸，而形絲製乙醇產物；於—塔中將至 之該粗製〔醇產物分離成包括乙醇之第一 _物及包括乙酸及 ί之’其中饋人該塔之粗製乙醇產物中之大部份的水在該 =一^射祕除；及於第二_塔巾錄部份之該乙醇混合物液 2二呈ί汽相或液相之乙醇側顧分、包括水之第二殘留物及包括 乙酸乙S日之第二館出物…具體例中，該第二殘留物亦可包括乙酸。 201245126 【實施方式】 本發明有關純化乙醇之製程’其係有關純化在觸媒存在下氫化乙 酸所製得之乙醇的純化乙醇製程。該鼓化反應產生包括乙醇、水、乙 酸及其他雜質如乙酸乙8旨、乙链及二乙基縮链之粗製乙醇產物。粗製 乙醇產物中之乙醇及乙酸之就地(in situ)酯化可產生額外的乙酸乙醋 雜質。為有效地移除該等雜質，本發明製程涉及將該粗製乙醇產物分 離成包括水及未反應乙酸之殘留物，以及包括乙醇之餾出物液流。該 餾出物接著於第二塔中分離而產生包括乙酸乙酯之第二餾出物、包括 水之第一殘留物及乙醇產物側顧分。該乙醇產物側顧分可在比對該第 一塔之饋入位置還要低之位置被抽出。一具體例中，雖然該第二殘留 物亦可包括乙醇，但該乙醇產物側餾分較佳者為比該第二殘留物更富 含乙醇。該乙醇產物側餾分可為蒸汽或液體。較佳者為，該乙醇產物 側餾分為蒸汽。 回收乙醇中，本發明之製程使用一個或多個蒸餾塔。乙酸自初始 (第一)塔之殘留物液流中之粗製乙醇產物移除，以減少將會消耗所需 乙醇產物之酯化反應。在較佳具體例中，該第一殘留物包括來自該粗 製乙醇產物之大部份之水及乙酸。一具體例中，操作該初始塔使得少 量且較佳者為無乙酸被帶^至触物巾’及少量且較佳者為無乙醇被 漏至該殘留物卜_物中所移除之大部份的水取決_粗製乙醇產 物之組成，而據以改變其部份量，此係為乙酸轉化及對乙醇選擇率之 結果。移除_物巾之較少量的賴可增加抽出物巾攜載。 此外’殘留物中留下太多水亦可引起漏至該_物中之乙醇量增加。 且’依據轉化率喊，當館出物中留下太多水時能量需求亦會增加。 有些具體例中，在將第一餾出物液流導入第二塔之前，進而自該 第-顧出物液流移除水啵利地，此分離方法減少了自粗製乙醇產物 I收乙醇之能量需求。較佳者為，可經由水移除單_除第一館出物 ^量的相產生乙醇混合物液流及水H該乙軌合物液流接 著破導入該第二塔中。水移除單元如吸附單元、膜、萃取蒸顧塔、分 子筛或其組合’其可自第—働物之經處理部分移除至少·的水， 6 201245126 為95%至".99%。水液流亦可與來自系統之任何其他水液流組 °較佳者為自該系統被移除。該水液流亦可包括乙醇，在此情形， 有可能其較佳者為將全部或部份的水液流饋送回至第一塔中以供進一 步的乙醇回收。視情況，至少部份之水液流被饋入該第二塔中。更佳 者為，將至少部份之該第一餾出物饋入該第二塔中。導入第二塔之額 ^將作鱗取蒸侧來雜作用，其可進-频良自粗製乙醇產物 製造乙醇之效率。導入該第二塔之水可來自包括在本製程中產生之水 之任何液流，或者視情況來自本製程外部。 由本發明製程產生之乙醇產物侧餾分相較於第二殘留物將更富含 醇 具體例中。該乙醇混合物液流及/或第一顧出物中之至少4〇% 乙醇在乙醇產物側餾分中被移除，如至少5〇%、至少6〇%或至少7〇〇/〇。 其較佳者為，該乙醇產物側餾分亦包括少於500wppm乙酸，如少於 400wppm、少於3〇〇wppm或少於25〇wppm。其較佳者為，該乙醇產 物側餾分包括少於lOOwppm乙酸乙酯，如少於9〇wppm或少於 75wppm。有些具體例中，該乙醇產物側餾分為包括少於12wt%水之工 業級乙醇。一具體例中，該乙醇產物側餾分係於比乙醇混合物液流之 饋入位置更低之位置被抽出。 ” 有些具體例中，本發明之製程進而包括減少乙醇產物側館分中水 含量以產生具有水含量已降低之乙醇產物液流之步驟。有些具體例 中，該減少步驟係使用吸附單元、膜、分子篩或其組合。一具^例中， 該吸附單元可為壓變吸附(PSA)單元。例舉的具體例中，至少部份之乙 醇產物側餾分以膜分離成包括水之滲透液流及包括乙醇之潭留.液流 (retentate stream^該滯留液流較佳者為具有比乙醇產物侧餾分更低2 水濃度。較佳者為’該滯留液流包括少於3wt%水。較佳者為，該滞留 液流可使用作為燃料級乙醇，因該滯留液流可能包括少於2wt%水，如 少於0.5wt%水。 本發明之製程可與製造乙醇之任何氫化製程一起使用。可用於乙 酸之氫化中之材料'觸媒、反應條件及分離製程詳述如下。 可與本發明製程一起使用之原料乙酸及氫可衍生自任何適宜來 201245126 源，包含天然氣、石油、煤厌、生質材料等。例如，乙酸可經由曱醇 幾化、乙醛氧化、乙烯氧化、氧化性發酵及厭氣發酵而製得。適於製 造乙酸之甲#羰化製程述於美國專利號7,208,624; 7，115,772; 7,005,541; 6,657,078; 6,627,770; 6,143,930; 5,599,976; 5,144,068; 5,026,908;5,001，259;及4,994,608,其等之全部揭示併入本文供參考。 視情況’乙醇製造可與該甲醇羰化製程整合在一起。 由於石油及天然氣價格浮動而變貴或變便宜，故自其他碳源製造 乙酸及中間物如曱醇及一氧化碳之方法逐漸受到矚目。尤其，當石油 相當昂貴時，自衍生自其他可用碳源之合成氣體("合成氣")製造乙酸將 變得有利。例如美國專利號6,232,352(其全文併入本文供參考)教示用 以改良製造乙酸之甲醇工廠之方法。藉由改裝曱醇工廠，對於新建乙 酸工廠所產生相關之較大成本，以及伴隨而來的一氧化碳產生的問 題，均可顯著地降低或大幅省去。所有或部分合成氣係衍生自甲醇合 成路徑並供應至分離器單元以回收一氧化碳，其接著被用以製造乙 酸。以類似方式，可自合成氣供應氫化步驟之氫。 於有些具體例中，上述乙酸的氫化製程中有些或所有原料可部分 或全部衍生自合成氣。例如，乙酸可自曱醇及一氧化碳形成，兩者均 衍生自合成氣。該合成氣可由部分氧化重排(〇xidati〇n ref〇rming)或蒸 汽重排(steam reforming)而形成’且一氧化碳可分離自合成氣。類似 地，使乙酸經氫化而形成粗製乙醇產物之步驟中所使用之氫可分離自 合成氣。此合成氣又可衍生自各種碳源^該碳源例如可選自由天然氣、 汽油、石油、煤炭、生質材料及其組合所組成之群組。合成氣或氫亦 可獲自生物衍生之曱烷氣體如由廢棄物掩埋或農業廢棄物所製得之生 物衍生之曱烷氣體。 相較於石化燃料如煤或天然氣而言，生質材料衍生之合成氣具有 可偵測之14C同位素含量。於地球大氣中於恆定新形成及恆定衰變降 解之間會形成平衡，而因此在地球大氣中碳原子核之HC核比例係長 期值定。因活有機體係存在於周圍大氣中，因此相同分布比例的14c:12c 比例會建立於活有機體中，而此分布比例會在活有機體死亡時停止改 8 201245126 變，但14C會以約6000年之半衰期衰變分解。。自生質材料衍生之合 成，所形成之甲醇、乙軌/或乙醇職將具有實質上難於活有機體 之14C含量。例如，甲醇、乙酸及/或乙醇之uc : 12(：比例可為活有機 體之14C : 12C比例之-半至，約！。其他具體例中，本文所述之合成氣、 曱醇、乙酸及/或乙醇’其全部衍生自石化燃料，亦即衍生自6〇，_ 年前所產生之碳源，則不具有可偵測之!4C含量。 於另一具體例中，氫化步驟中使用之乙酸可自生質材料發酵而形 成。該發酵製程較佳者為利用產乙酸製程或同型產乙酸微生物 (homoacetogenic microorganism)而將糖發酵成乙酸，並產生極少量(若 有的話)二氧化碳作為副產物。相較於習知酵母製程(其一般具有約 67%之碳效率），發酵製程之碳效率，較佳者為大於7〇%、大於8〇%或 大於90%。視情況，發酵製程中使用之微生物為一菌屬(genus)選自由 梭菌屬(Clostridium)、乳酸菌屬(Lact〇bacillus)、穆爾氏菌屬(^⑽血）、 嗜熱厭氧菌屬(Thermoanaerobacter)、丙酸桿菌屬(propi〇nibacterium)、 丙酸孢菌屬(Propicmispera)、厭氧螺菌屬(Anaer〇bi〇spirillum)及擬桿菌 屬(Bacteriodes)所組成之群組，且尤其是菌種(speciesM自由甲醯乙酸 梭菌(Clostridium formicoaceticum)、丁 酸桿菌(Clostridium butyricum)、 穆爾氏熱乙酸菌（Moorella thermoacetica)、飢伍產醋菌 (Thermoanaerobacter kivui)、保加利亞乳酸菌（Lact〇bacillus delbrueckii)、丙酸桿菌(Propionibacterium acidipropi〇nici)、丙酸孢菌 (Propionispera arboris)、產琥珀酸放線桿菌（Anaer〇bi〇spirmum succiniqDmducens)、似澱粉擬桿菌(Bacteri〇des及栖瘤胃擬 桿菌(Bacteroides ruminicola)所組成之群組。視情況，於本製程中，所 有或部分之自生質材料(如木酚素)之該未發酵之殘留物可經氣化以形 成可用於本發明氫化步驟中之氫。形成乙酸之例舉發酵製程述於美國 專利號6,509，180及美國公開號2008/0193989及2009/0281354，其全 文併入本文供參考。 生質材料實例包含(但不限於)農業廢棄物、森林產物、草皮及其 他纖維素材料、儲木場木材剩餘物、軟木片、硬木片、樹枝、樹幹、 201245126 葉子、樹皮、木屑、不合規格紙漿、玉米、玉米穗稈、小麥屑、米屑、 甘蔗渣、柳枝稷、芒草、動物***物、城市垃圾肥、城市汙水、商業 廢棄物、葡萄浮石、杏核殼、大胡桃殼、椰子殼、咖徘渣、草粒、乾 草粒、木粒、紙板.、紙、塑膠及布。其他生質材料來源為草漿黑液广 其為木質素殘留物、半纖維素及無機化學品之水溶液。 美國再發證專利號RE 3 5.,377(亦併入本文供參考)提供一種藉由轉 化碳質材料如油、煤炭、天然氣及生質材料而製造曱醇之方法。該製 程包含使固體及/或液體碳質材料經氫氣化(hydr〇gasiflcati〇n)以獲彳$製 程氣體，其與其他天然氣蒸汽裂解而形成合成氣。該合成氣轉化成f 醇’其可再經数化成乙酸。該方法同樣會產生氫氣，其可與上述本發 明聯用。美國專利號5,821，111揭示經由氣化將廢棄生質材料轉化成合 成氣之製程，及美國專利號6,685,754揭示製造含氫氣體組成物如包; 氫及一氧化碳之合成氣之方法，該等專利併入本文供參考。 饋入氫化反應器之乙酸亦包括其他叛酸類及酸酐類以及乙路及丙 酮。較佳者為，適宜乙酸進料液流包括一種或多種化合物，其係選自 由乙酸、乙酸Sf、乙酿、乙酸乙自旨及其混合物所組成之群組。該等其 他化合物亦可在本發明製程中經氫化。有些具體例中，舰如丙酸或 丙醛之存在可能有利於製造丙醇。水亦可存在於乙酸進料中。 或者’蒸汽態之乙酸可自美國專利號6,657,〇78(其全文併入本文供 參考)所述之甲醇幾化單元之閃蒸容器中以粗製產物直接取得。該粗製 蒸汽產物修可直接饋人本發^㈣合成反舰_而無須將乙酸及 輕烴物冷凝或移除水，而可節省總加工成本。 乙酸可在反應溫度下蒸汽化(vap〇rized)，接著該蒸汽化乙酸可與 未稀釋狀ϋ之氫或以姆惰性龍如纽、統、氦氣、三氧化碳等 稀，之氫-起饋人。系統巾之蒸汽相巾之反應運轉、溫度應被控制以 使得不會低於乙酸之露點。於—具酬巾，乙酸可在特定壓力下在乙 ，之彿點下航化，且接著將該航化之乙酸進*加熱至反應器入口 溫度/_具_巾，該乙齡紐化賴其他氣航合，接著將混 合蒸/飞加熱至反應器入口溫度。較佳者為藉由使氫及/或循環氣體在 201245126 125 C或低於125°C之溫度通過乙酸而將乙酸轉移至蒸汽態，接著將該 組合之氣體流加熱至反應器入口溫度。 氫化乙酸而形成乙醇之製程有些具體例可包含使用固定床反應器 或流體床反應器之各種組態。本發明許多具體例中，可使用"絕熱,,反 應器，亦即極少或不需要將内部管道導入反應區以加入或移除熱。於 ^他具體例中，可利用輻射流反應器或諸反應器，或可使用串聯反應 器，無論其可含或不含熱交換、淬滅或導入額外進料材料。或者，可 使用設有熱轉移介質之殼式及管型反應||。在許多例中，該反應區可 谷置於單-容器之巾’或容置於-序列其間具有熱交㈣之容器中。 於較佳具體例中，於固定床反應器中例如於直管或管型反應器中 使用觸媒，於該處一般成蒸汽態之反應物通過該觸媒上或其内。可使 用其他反應器如流體或'/弗騰床反應器。於有些例中，該氫化觸媒可與 惰性材料聯用以調節反應物液流通過觸媒床之壓降及反應物化合物與 觸媒顆粒之接觸時間。201245126 Code Description 130 Second Tower / Light Hydrocarbon Tower 131 Pipeline / Second Residue 132 Pipeline 135 Pipeline / Ethanol Product Side Fraction 5, ί If there is a chemical formula 'Please _ the most weaving invention _ chemical formula: ..., 0 6 Description of the invention: Relevant cross-references. The present application claims priority to U.S. Provisional Application No. 61/570,604, the entire disclosure of which is hereby incorporated by reference. This application is also a continuation-in-part of U.S. Patent No. 13/94,537, filed on Apr. 26, 2011, which is incorporated herein by reference. This article is incorporated by reference in its entirety. TECHNICAL FIELD OF THE INVENTION The present invention generally relates to a process for producing ethanol produced by vaporization of acetic acid and acetaminophen. [Prior Art] Industrial ethanol is prepared from organic sources such as petroleum, natural gas or coal, or from source intermediates such as syngas or from starchy materials or cellulosic materials such as corn or sugar cane. . Conventional methods for the production of ethanol from organic sources and from cellulosic materials include ethylene acid catalyzed hydration, methanol homologation (h〇m〇) 〇gati〇n), direct alcohol synthesis, and Fischer-Tropsch )synthesis. The unstable price of petrochemical sources will cause the price of ethanol produced by the law to fluctuate, which makes it more necessary to make alternative energy sources for ethanol production when the source price increases. Starch (four) materials and cellulosic materials are converted into ethanol by fermentation. L fermentation is generally used in the manufacture of consumer ethanol, and the ethanol produced is suitable for use as a material or human. In addition, fermentation of the cellulite or cellulosic material will compete with the food source and limit the amount of ethanol that can be made for industrial use. The manufacture of ethanol via reduction reactions of anamorphic acids and/or other group-containing compounds has been extensively studied. Various combinations of J-catalysts, supports, and operating conditions have been described in the literature. In the case of reducing thieves, for example, reducing other compounds may form with ethanol or form a side reaction towel. These impurities limit the production and recovery of ethanol from this reaction mixture. For example, in the hydrogenation process, it will form an azeotrope with B or water, which will be difficult to separate. In addition, when the conversion is incomplete, the unreacted acid will remain in the crude ethanol product, which must be removed to recover the ethanol. EP 0 020 553 describes a process for the conversion of hydrocarbons to ethanol comprising the conversion of hydrocarbons to acetic acid and the hydrogenation of acetic acid to (10). The liquid from the hydrogenated anti-filament is separated to obtain an ethanol product, and a stream of bribes, which will be re-introduced into the nitriding reactor. US Patent No. 7 '842,844 describes a process for converting hydrocarbons into ethanol in the presence of a particulate catalyst and, if appropriate, into an acetic acid towel, a county selectivity and a process for improving the life of the mixture. (syng^) produces an intermediate step. There is still a need for an improved process for recovering ethanol by reducing the crude product obtained from the reduction of an alkanoic acid such as acetic acid and/or other carbonyl-containing compound. SUMMARY OF THE INVENTION In a first embodiment, the present invention is directed to a process for producing ethanol comprising: hydrogenating acetic acid and/or its ester in a reactor in the presence of a catalyst to form a crude ethanol product; Separating at least a portion of the crude ethanol product from the column to produce a first residue comprising acetic acid and a first distillate comprising ethanol, ethyl acetate and water; removing at least a portion of the first distillate Water to produce a liquid mixture comprising less than 1% by weight (% by weight) of water; and separating a portion of the ethanol mixture stream in the second distillation column to produce an ethanol side stream in a vapor phase or a liquid phase, Including a second residue of water and a second distillation 4 201245126 including ethyl acetate. In one embodiment, the ethanol product side draw is more enriched in ethanol than the second residue. At least 40 〇/〇 ethanol in the ethanol mixture stream can be removed in the ethanol product side draw. The ethanol product side considerations include less than 5 〇〇 wppm (ppm by weight) acetic acid and less than 1 〇〇 wppm ethyl acetate. The ethanol product side draw can be withdrawn at a lower position than the ethanol mixture stream is fed to the second distillation column. In one embodiment, the ethanol product side cut is an industrial grade ethanol comprising less than 12 wt% water, preferably less than 8 wt% water. In some embodiments, the 6 acid is formed from decyl alcohol and carbon monoxide, wherein the methanol, carbon monoxide, and hydrogen used in the hydrogenation step are derived from a combination, and the synthetic gas system is derived from a carbon source. Choose from a group of natural gas, oil, petroleum, coal, biomass materials and combinations thereof. In a second specific example, the invention relates to a process for producing ethanol, which comprises: hydrogenating acetic acid in a reaction ft towel in the presence of a catalyst to secrete a crude ethanol product; and separating at least part of the first steaming tower Crude ethanol product to produce a first residue comprising acetic acid and a first residue comprising water, & acid <RTIgt;acid<s> and water; removing water from at least a portion of the first German product to produce less Separating a portion of the ethanol mixture stream in a second vapor column to produce an ethanol side in a vapor phase or a liquid phase, a second residue comprising water, and comprising acetic acid B The second consideration of the purpose is to reduce the ethanol product, and to separate the water content to produce an ethanol reduction with a low water content (10). The ethanol product stream having a reduced water content may have less than domain water. The adsorption unit or the water concentration may be used. In a specific example, the ethanol product liquid having a reduced water content may be a hopper-grade ethanol comprising less than 2% by weight of water, preferably less than 〇5% by weight of water. . In a third embodiment, the present invention relates to a process for producing ethanol, which comprises: hydrogenating acetic acid in a reverse scarf in the presence of a catalyst, and forming an ethanol product in the form of a filament; and separating the crude product from the column in the column Forming the first substance including ethanol and the water containing acetic acid and ί's which are most of the crude ethanol product fed to the tower, in the case of the second _ tower towel The ethanol mixture liquid 2 is in the vapor phase or the liquid phase of the ethanol side, including the second residue of water and the second museum including the acetic acid B. In the specific example, the second residue is also Acetic acid can be included. 201245126 [Embodiment] The present invention relates to a process for purifying ethanol, which is a process for purifying ethanol obtained by purifying acetic acid obtained by hydrogenating acetic acid in the presence of a catalyst. The drumization reaction produces a crude ethanol product comprising ethanol, water, acetic acid and other impurities such as acetic acid, ethyl acetate and diethyl condensate. In situ esterification of ethanol and acetic acid in the crude ethanol product can produce additional ethyl acetate impurities. To effectively remove such impurities, the process of the present invention involves separating the crude ethanol product into a residue comprising water and unreacted acetic acid, and a distillate stream comprising ethanol. The distillate is then separated in a second column to produce a second distillate comprising ethyl acetate, a first residue comprising water and an ethanol product side. The ethanol product side draw can be withdrawn at a lower position than the feed point to the first column. In one embodiment, although the second residue may also comprise ethanol, the ethanol product side draw is preferably more ethanol-rich than the second residue. The ethanol product side draw can be steam or liquid. Preferably, the ethanol product side cut is divided into steam. In the recovery of ethanol, the process of the present invention uses one or more distillation columns. The acetic acid is removed from the crude ethanol product in the residue stream of the initial (first) column to reduce the esterification reaction which will consume the desired ethanol product. In a preferred embodiment, the first residue comprises a substantial portion of the water and acetic acid from the crude ethanol product. In a specific example, the initial column is operated such that a small amount and preferably no acetic acid is taken to the contact towel' and a small amount and preferably no ethanol is leaked to the residue. Part of the water depends on the composition of the crude ethanol product, which is used to change the partial amount, which is the result of acetic acid conversion and selectivity to ethanol. Removing a smaller amount of the towel can increase the carrying of the towel. In addition, leaving too much water in the residue can also cause an increase in the amount of ethanol leaking into the _. And according to the conversion rate, the energy demand will increase when too much water is left in the museum. In some specific examples, before the first distillate stream is introduced into the second column, the water is removed from the first feed stream, and the separation method reduces the ethanol from the crude ethanol product I. Energy demand. Preferably, the ethanol mixture stream and the water H are discharged through the water to remove the phase of the first column. A water removal unit, such as an adsorption unit, membrane, extraction vapor column, molecular sieve, or a combination thereof, can remove at least water from the treated portion of the first analyte, 6 201245126 being 95% to ".99%. The water stream can also be removed from the system with any other water stream from the system. The aqueous stream may also include ethanol, in which case it may be preferred to feed all or part of the aqueous stream back to the first column for further ethanol recovery. Optionally, at least a portion of the aqueous stream is fed into the second column. More preferably, at least a portion of the first distillate is fed to the second column. The amount of the second column is introduced into the scale. The steaming side of the scale is used for the miscellaneous action, which can be used to increase the efficiency of ethanol production from the crude ethanol product. The water introduced into the second column may be from any liquid stream included in the water produced in the process or, as the case may be, from outside the process. The ethanol product side cut produced by the process of the present invention will be more enriched in alcohol than the second residue. The ethanol mixture stream and/or at least 4% ethanol in the first take-up is removed in the ethanol product side draw, such as at least 5%, at least 6%, or at least 7 Torr. Preferably, the ethanol product side draw also comprises less than 500 wppm acetic acid, such as less than 400 wppm, less than 3 〇〇 wppm or less than 25 〇 wppm. Preferably, the ethanol product side draw comprises less than 100 wppm ethyl acetate, such as less than 9 〇 wppm or less than 75 wppm. In some embodiments, the ethanol product side cut is an industrial grade ethanol comprising less than 12 wt% water. In one embodiment, the ethanol product side draw is withdrawn at a lower position than the feed point of the ethanol mixture stream. In some embodiments, the process of the present invention further includes the step of reducing the water content of the side product of the ethanol product to produce a liquid stream having a reduced water content. In some embodiments, the reducing step uses an adsorption unit, membrane. a molecular sieve or a combination thereof. In one embodiment, the adsorption unit may be a pressure swing adsorption (PSA) unit. In a specific embodiment, at least a portion of the ethanol product side fraction is separated into a permeate stream comprising water. And comprising a retentate stream (retentate stream) preferably having a lower water concentration than the ethanol product side cut. Preferably, the retentate stream comprises less than 3 wt% water. Preferably, the retentate stream can be used as fuel grade ethanol, as the retentate stream may include less than 2 wt% water, such as less than 0.5 wt% water. The process of the present invention can be used with any hydrogenation process for making ethanol. The materials which can be used in the hydrogenation of acetic acid 'catalyst, reaction conditions and separation process are detailed below. The raw materials acetic acid and hydrogen which can be used together with the process of the invention can be derived from any suitable source of 201245126, including natural Gas, petroleum, coal rot, raw materials, etc. For example, acetic acid can be obtained by decyl alcoholization, acetaldehyde oxidation, ethylene oxidation, oxidative fermentation and anaerobic fermentation. It is described in U.S. Patent Nos. 7,208,624; 7,115,772; 7,005,541; 6,657,078; 6,627,770; 6,143,930; 5,599,976; 5,144,068; 5, 026, 908; 5, 001, 259; and 4,994, 608, the entire disclosure of each of which is incorporated herein by reference. The methanol carbonylation process is integrated. As oil and natural gas prices become expensive or cheaper, methods for producing acetic acid and intermediates such as sterols and carbon monoxide from other carbon sources are gaining attention. Especially when oil is quite expensive. It is advantageous to produce acetic acid from a synthesis gas derived from other available carbon sources ("syngas"). For example, U.S. Patent No. 6,232,352, the entire disclosure of which is incorporated herein by reference in its entirety, is incorporated herein by reference. Method. By modifying the methanol plant, the associated costs associated with the new acetic acid plant, and the accompanying carbon monoxide generation , can be significantly reduced or substantially eliminated. All or part of the syngas is derived from the methanol synthesis pathway and supplied to the separator unit to recover carbon monoxide, which is then used to make acetic acid. In a similar manner, hydrogenation can be supplied from syngas Hydrogen in the step. In some embodiments, some or all of the starting materials in the hydrogenation process of the above acetic acid may be derived partially or completely from the syngas. For example, acetic acid may be formed from decyl alcohol and carbon monoxide, both derived from syngas. The gas may be formed by partial oxidation rearrangement or steam reforming and carbon monoxide may be separated from the synthesis gas. Similarly, the hydrogen used in the step of hydrogenating acetic acid to form a crude ethanol product can be separated from the synthesis gas. The syngas can in turn be derived from a variety of carbon sources, such as a group of free natural gas, gasoline, petroleum, coal, biomass materials, and combinations thereof. Syngas or hydrogen can also be obtained from biologically derived decane gases such as bio-derived decane gas produced from waste burial or agricultural waste. Biomass-derived syngas has a detectable 14C isotope content compared to fossil fuels such as coal or natural gas. A balance is formed between constant new formation and constant decay degradation in the Earth's atmosphere, and thus the HC nuclear ratio of carbon nuclei in the Earth's atmosphere is determined by long-term values. Since the living organic system exists in the surrounding atmosphere, the 14c:12c ratio of the same distribution ratio will be established in the living organism, and the distribution ratio will stop changing when the living organism dies, but the 14C will be about 6000 years. Half-life decay decomposition. . The synthesis of the self-generating material will result in a 14C content that is substantially difficult to survive in the methanol, orbital/or ethanol jobs. For example, uc: 12 of methanol, acetic acid and/or ethanol (the ratio may be 14C of a living organism: a ratio of 12C to half to about, about! In other specific examples, the synthesis gas, sterol, acetic acid and / or ethanol's all derived from fossil fuels, that is, derived from 6〇, the carbon source produced _ years ago, is not detectable! 4C content. In another specific example, used in the hydrogenation step Acetic acid can be formed by fermentation of a self-generating material. The fermentation process preferably utilizes an acetic acid production process or a homoacetogenic microorganism to ferment the sugar to acetic acid and produce a very small amount, if any, of carbon dioxide as a by-product. Compared to the conventional yeast process (which generally has a carbon efficiency of about 67%), the carbon efficiency of the fermentation process is preferably greater than 7%, greater than 8%, or greater than 90%. Optionally, during the fermentation process The microorganism to be used is a genus selected from the group consisting of Clostridium, Lactobacillus, M. genus (^(10) blood), Thermoanaerobacter, and propionic acid. Propi〇nibacterium, propionic acid a group consisting of Propicmispera, Anaer〇bi〇spirillum, and Bacteriodes, and especially a species (speciesM free Clostridium formicoaceticum, Clostridium butyricum, Moorella thermoacetica, Thermoanaerobacter kivui, Bulgarian lactic acid bacteria (Lact〇bacillus delbrueckii), Propionibacterium acidipropi〇nici, propionic acid Propionispera arboris, Anaer〇bi〇spirmum succiniqDmducens, Bacteri〇des and Bacteroides ruminicola. Depending on the situation, in this process The unfermented residue of all or part of the autogenous material (such as lignan) may be gasified to form hydrogen which can be used in the hydrogenation step of the present invention. An exemplary fermentation process for forming acetic acid is described in U.S. Patent No. 6,509,180 and U.S. Publication Nos. 2008/0193989 and 2009/0281354, the entire contents of each of which are hereby incorporated by reference. Agricultural waste, forest products, turf and other cellulosic materials, wood residues in wood yards, cork sheets, hardwood chips, branches, trunks, 201245126 leaves, bark, sawdust, substandard pulp, corn, corn stalks, wheat Chips, rice chips, bagasse, switchgrass, miscanthus, animal waste, municipal waste, municipal sewage, commercial waste, grape pumice, apricot shell, large walnut shell, coconut shell, curry residue, grass, hay Grain, wood, cardboard, paper, plastic and cloth. Other sources of biomass material are straw black liquor, which is an aqueous solution of lignin residues, hemicellulose and inorganic chemicals. U.S. Reissue Patent No. RE 3, 377, which is incorporated herein by reference in its entirety, is incorporated herein by reference in its entirety in its entirety in the the the the the the the the The process involves liquefying a solid and/or liquid carbonaceous material to obtain a process gas which is cleaved with other natural gas vapor to form a syngas. The syngas is converted to the f alcohol, which can be further converted to acetic acid. This process also produces hydrogen which can be used in conjunction with the above described invention. U.S. Patent No. 5,821,111 discloses a process for the conversion of waste biomass material to syngas via gasification, and U.S. Patent No. 6,685,754, the disclosure of which is incorporated herein by reference. This article is hereby incorporated by reference. The acetic acid fed to the hydrogenation reactor also includes other retinoids and anhydrides as well as ethylene and acetone. Preferably, the suitable acetic acid feed stream comprises one or more compounds selected from the group consisting of acetic acid, acetic acid Sf, ethyl acetate, acetic acid, and mixtures thereof. These other compounds may also be hydrogenated in the process of the invention. In some specific cases, the presence of a ship such as propionic acid or propionaldehyde may be beneficial in the manufacture of propanol. Water can also be present in the acetic acid feed. Alternatively, the 'vaporated acetic acid can be obtained directly from the crude product in a flash vessel of a methanol numbering unit as described in U.S. Patent No. 6,657, the entire disclosure of which is incorporated herein by reference. The crude steam product repair can directly feed the hair (4) synthetic anti-ship _ without the need to condense or remove water from acetic acid and light hydrocarbons, thereby saving overall processing costs. The acetic acid can be vaporized at the reaction temperature, and then the vaporized acetic acid can be diluted with hydrogen in an undiluted hydrazine or an inert gas such as ruthenium, ruthenium, ruthenium or carbon trioxide. Feed people. The reaction of the steam towel of the system towel and the temperature should be controlled so as not to fall below the dew point of the acetic acid. In the -paid towel, acetic acid can be aired under the specific pressure at the point of B, and then the vaporized acetic acid is heated into the reactor inlet temperature / _ with a towel, the B-in The other gas is combined and the mixed steam/fly is heated to the reactor inlet temperature. Preferably, the acetic acid is transferred to the vapor state by passing hydrogen and/or recycle gas through acetic acid at a temperature of 201245126 125 C or below 125 ° C, and then heating the combined gas stream to the reactor inlet temperature. Processes for Hydrogenation of Acetic Acid to Form Ethanol Some specific examples may include various configurations using fixed bed reactors or fluid bed reactors. In many embodiments of the invention, "insulation,", reactor, i.e., little or no internal piping may be introduced into the reaction zone to add or remove heat. In his specific example, a radial flow reactor or reactors may be utilized, or a series reactor may be used, whether or not with or without heat exchange, quenching or introduction of additional feed materials. Alternatively, a shell and tubular reaction with a heat transfer medium can be used. In many instances, the reaction zone may be placed in a single-container towel or in a container having a heat-crossing (four) between them. In a preferred embodiment, a catalyst is used in a fixed bed reactor, e.g., in a straight or tubular reactor, where the generally gaseous reactant passes over or within the catalyst. Other reactors such as fluids or '/Furton bed reactors can be used. In some instances, the hydrogenation catalyst can be combined with an inert material to adjust the pressure drop of the reactant stream through the catalyst bed and the contact time of the reactant compound with the catalyst particles.
氩化反應可在液相或蒸汽相中進行。較佳者為，反應係在下列條 件下於蒸汽相進行。反應溫度可在125。(：至350ec之範圍，如自200°C 至325 C、自225 C至30(TC、或自250°C至300。〇。壓力可在i〇kPa(千 巴)至3000kPa之範圍，例如自5〇kPa至2300kPa、或自l〇〇kPa至 2100kPa。反應物可以自50小時» 5〇〇〇〇hr\氣體時空速度 (GHSV)饋入反應器中’如自500hr-i至3〇〇〇〇1^，自至 ΙΟ,ΟΟΟΙιγ·1，或自 lOOOhr·1 至 6500hr-1 雖然反應每莫耳乙酸消耗兩莫耳氫而製得一莫耳乙醇，但進料液 流中之氫對乙酸之實際莫耳比可在約100:1至1:1〇〇間變化，如自5〇:1 至 1:50、自 20:1 至 1:2、或自 18:1 至 2:1。 接觸或滯留時間亦可廣泛變化，視各種變數而定，如乙酸量、觸 媒、反應器、溫度及壓力。當使用觸媒系統而非固定床時，一般接觸 時間自數毫秒至超秘，丨、時之範® ’而至少縣汽減應之較佳接觸 時間係自0.1至100秒。 乙酸IL化成乙醇較佳者為在氫化觸媒存在下進行。例舉之觸媒進 11 201245126 而述於美國專利號7,608,744及7,863,489，及美國公開號2010AU211M 及2010/0197985，其全文併入本文供參考。於另一具體例中，該觸媒 包括述於美國公開號2009/0069609所述類型之Co/Mo/S觸媒，該文獻 全文併入本文供參考。有些具體例令，該第一觸媒及第二觸媒可為塊 體觸媒》 一具體例中’該觸媒包括第一金屬係選自由銅、鐵、鈷、鎳、釕、 鍺、鈀、锇、銥、鉑、鈦、鋅、鉻、銖、鉬及鎢所組成之群組。較佳 者為該第一金屬係選自由鉑、鈀、鈷、鎳及釕所組成之群組。 如所述，有些具體例中，觸媒進而包括第二金屬，其一般作為促 進劑之功能。若存在有第二金屬，其較佳者為係選自由銅、鉬、錫、 鉻、鐵、鈷、釩、鎢、鈀、鉑、鑭、鈽、錳、釕、銖、金及鎳所組成 之群組。更好，第二金屬係選自由銅、錫、鈷、銖及鎳所組成之群組。 在某些具體例中’其中觸媒包含兩種或多種金屬，如第一金屬及 第二金屬’該第-金屬在觸媒中存在量為〇1至1〇wt%，如自〇1至 5罐，或自（U至3wt%。第三金屬存在量較佳者為為〇」至2〇感， 如自0.1至10wt%，或自0_i至7 5wt%。 舉例之較佳金屬組成之觸媒組成物包含⑭/錫、如釕、似鍊、把/ 釕、鈀/銖、鈷/鈀、鈷/鉑、鈷/鉻、鈷/釕、鈷/錫、銀/鈀、銅/鈀、銅, 鋅、鎳/纪、金/把、釕/銖、或釕/鐵。 觸媒亦可包括選自上述第一金屬或第二金屬中所列之任何金屬之 與第一金屬及第二金屬不同即可。較= 二。==、㈣、辞、鉬、錫及銖所組成之 群，當存在第二金屬時，第三金屬總量較佳者 如自 0.1 至 10wt%，或自 Ol57wo/ a A 1 玍 2Uwt/〇 锡及姑。 至7.5编。—具體辦，觸媒可包油、 除了-種或多種金屬以外，本發明有些具 擔體或改質_。本文所用之，，改^觸媒進而包括 及調整擔體材料酸性之擔體改_之擔體。擔體=包含擔趙材料以 以觸媒齡鱗，触者^ 75 i 99 S 舰之總重， 邪目78至97wt%，或 12 201245126 自80至95wt。/。。較佳的擔體包含石夕質龍，如氧化石夕、氧化石夕/氧化 銘、IIA族矽酸鹽如偏矽酸詞、熱解氧化石夕、高純度氧化石夕及其混合 物。其他擔體可包含(但不限於)氧化鐵、氧化銘、氧化欽、氧化錄、 氧化鎮、碳、石墨、〶表面積石墨化碳、活性碳及其混合物。The argonization reaction can be carried out in the liquid phase or in the vapor phase. Preferably, the reaction is carried out in the vapor phase under the following conditions. The reaction temperature can be at 125. (: to 350ec range, such as from 200 ° C to 325 C, from 225 C to 30 (TC, or from 250 ° C to 300. 〇. Pressure can range from i 〇 kPa (kilogram) to 3000 kPa, for example From 5 kPa to 2300 kPa, or from 1 kPa to 2100 kPa. The reactants can be fed into the reactor from 50 hours » 5 hr / gas hourly space velocity (GHSV) 'from 500 hr-i to 3 〇. 〇〇〇1^, from ΙΟ, ΟΟΟΙιγ·1, or from lOOOOhr·1 to 6500hr-1 Although the reaction consumes two moles of hydrogen per mole of acetic acid to produce one mole of ethanol, but the hydrogen in the feed stream The actual molar ratio to acetic acid can vary from about 100:1 to 1:1, such as from 5:1 to 1:50, from 20:1 to 1:2, or from 18:1 to 2: 1. Contact or residence time can also vary widely, depending on various variables, such as acetic acid amount, catalyst, reactor, temperature and pressure. When using a catalyst system instead of a fixed bed, the general contact time is from a few milliseconds to super The secret, the 丨, the time of the Fan® 'and at least the county steam reduction should be the preferred contact time from 0.1 to 100 seconds. The formation of acetic acid IL into ethanol is preferably carried out in the presence of a hydrogenation catalyst. 20124 5 126 and U.S. Patent Nos. 7,608,744 and 7, 863, 489, and U.S. Publication Nos. 2010 AU 211M and 2010/0197985, the entire contents of each of each of each of each of The type of Co/Mo/S catalyst is incorporated herein by reference in its entirety. In some specific examples, the first catalyst and the second catalyst may be block catalysts. In a specific example, the catalyst includes The first metal is selected from the group consisting of copper, iron, cobalt, nickel, ruthenium, rhodium, palladium, osmium, iridium, platinum, titanium, zinc, chromium, ruthenium, molybdenum and tungsten. The metal is selected from the group consisting of platinum, palladium, cobalt, nickel, and ruthenium. As described, in some embodiments, the catalyst further includes a second metal that generally functions as a promoter. If a second metal is present Preferably, it is selected from the group consisting of copper, molybdenum, tin, chromium, iron, cobalt, vanadium, tungsten, palladium, platinum, rhodium, ruthenium, manganese, osmium, iridium, gold, and nickel. The second metal is selected from the group consisting of copper, tin, cobalt, rhodium, and nickel. In some specific examples, The medium catalyst comprises two or more metals, such as a first metal and a second metal. The first metal is present in the catalyst in an amount of from 1 to 1% by weight, such as from 1 to 5 cans, or from (U). Up to 3 wt%. The third metal is preferably present in an amount of from 〇" to 2 〇, such as from 0.1 to 10% by weight, or from 0_i to 7.5 % by weight. For example, a preferred metal composition of the catalyst composition comprises 14/ Tin, such as ruthenium, chain-like, palladium/ruthenium, palladium/ruthenium, cobalt/palladium, cobalt/platinum, cobalt/chromium, cobalt/ruthenium, cobalt/tin, silver/palladium, copper/palladium, copper, zinc, nickel/ Ji, Jin/Peng, 钌/铢, or 钌/Iron. The catalyst may also comprise any metal selected from the group consisting of the first metal or the second metal described above, which may be different from the first metal and the second metal. Compared with = two. a group consisting of ==, (4), rhetoric, molybdenum, tin and antimony. When a second metal is present, the total amount of the third metal is preferably from 0.1 to 10 wt%, or from Ol57wo/ a A 1 玍 2 Uwt/〇 Tin and aunt. To 7.5 series. - Specifically, the catalyst may be oil-containing, with the exception of one or more metals, the invention may have some support or modification. As used herein, the modifier further includes and adjusts the carrier of the carrier material to be acidic. The carrier = contains the material of the Zhao to the age of the catalyst, the total weight of the ship ^ 75 i 99 S, the evil spirits 78 to 97 wt%, or 12 201245126 from 80 to 95 wt. /. . Preferred supports include Shihuaxilong, such as oxidized stone, oxidized stone, oxidized, IIA bismuth, such as bismuth citrate, pyrolytic oxidized oxidized stone, high purity oxidized oxide, and mixtures thereof. Other supports may include, but are not limited to, iron oxide, oxidized, oxidized, oxidized, oxidized, carbon, graphite, ruthenium surface graphitized carbon, activated carbon, and mixtures thereof.
擔體可為改質擔體，且擔體改質劑存在量，係基於觸媒總重，為 0.1 至 50wt% ’ 如自 0.2 至 25wt%，自 1 至 20wt%，或自 3 至 15wt〇/〇 C 有些具體射’ _改_可騎加觸酸性之_改制。適宜的 酸性擔體改_可選自下列所雜群：IVB族金屬之氧化物、仰族 金屬之氧杨、vm族金屬之氧化物、VIIB金屬之氧化物、權8族 金屬之氧化物、銘氧化物及其混合物。酸性擔體改質劑包含選自由 Ti02、Zr02、Nb205、Ta2〇5、Aj2〇3、b2〇3、p2〇5、Sb2〇3、w〇3、M〇〇3、The support may be a modified support, and the amount of the support modifier present is from 0.1 to 50% by weight based on the total weight of the catalyst, such as from 0.2 to 25 wt%, from 1 to 20 wt%, or from 3 to 15 wt. /〇C Some specific shots ' _ change _ can ride and touch the acid _ restructuring. A suitable acidic support may be selected from the group consisting of oxides of Group IVB metals, oxygen yang of the Yang family metals, oxides of the Vm group metals, oxides of the VIIB metals, oxides of the Group 8 metals, Ming oxide and its mixture. The acidic carrier modifier comprises a compound selected from the group consisting of Ti02, Zr02, Nb205, Ta2〇5, Aj2〇3, b2〇3, p2〇5, Sb2〇3, w〇3, M〇〇3,
Fe203、Cr203、V205、Mn02、CuO、C〇2〇3 及 Bi2〇3 所組成之群組。較 佳的擔體改質劑包含鎢、鉬及釩之氧化物β 另一具體例中，擔體改質劑可為具有低揮發性或無揮發性之鹼性 改質劑。此鹼性改質劑例如可選自由(i)鹼土金屬氧化物，（ii)鹼金屬氧 化物’（iii)鹼土金屬偏矽酸鹽，（iv)鹼金屬偏矽酸鹽，（v)Iffi族金屬氧 化物，（vi)Iffi族金屬偏矽酸鹽，（vii)mB族金屬氧化物，（viii)mB族金 屬偏石夕酸鹽及其混合物所組成之群組。該驗性擔體改質劑可選自_由 鈉、鉀、鎂、鈣、钪、釔及鋅任一者之氧化物及偏矽酸鹽以及前述任 何之氧化物所組成之群組。於一具體例中，鹼性改質劑為矽酸約如偏 石夕酸鈣(CaSi〇3) 〇偏矽酸鈣可為結晶或非晶形_〇_〇113)。 於改質擔體上之觸媒可包含一種或多種金屬選自由鉑、鈀、鈷、 錫或銖所組成之群組，而係擔持在氧化矽擔體上，視情況藉一或多種 改質劑選自由偏矽酸約、及鎢、鉬及/或釩之一種或多種氧化物所組成 之群組予以改質。 適用於本發明之觸媒組成物較佳者為經由金屬飽浸(metal impregnation)於改質擔體中而形成’但亦可使用其他製程如化學氣相 沉積(chemical vapor deposition)。此飽浸技術述於前述之美國專利號 7,608,744及7,863,489及美國公開號2010/0197485，其全文併入本文 13 201245126 供參考。 原係於Z 燒’ _可經還原以活化觸媒。還 4〇〇t之Λ者錢，存在下蹄。㈣聽體在增加至 4〇〇 C之細觸溫度下連續通過觸。於 在觸=被f進人㈣進行氫蚊反躲ϋ k後才進行ΪΪ為 及吝座、ϋt酸氫化可達成有利的乙酸轉鱗及有利的乙醇選擇率 物之明目的而言，名詞，,轉化"表示轉化成乙酸以外之化合 , 之量。轉化係基於進料中乙酸之百分比表示。轉化可A group consisting of Fe203, Cr203, V205, Mn02, CuO, C〇2〇3, and Bi2〇3. A preferred bulk modifier includes oxides of tungsten, molybdenum and vanadium. In another embodiment, the bulk modifier may be an alkaline modifier having low or no volatility. The alkaline modifier may, for example, be selected from (i) an alkaline earth metal oxide, (ii) an alkali metal oxide '(iii) an alkaline earth metal metasilicate, (iv) an alkali metal metasilicate, (v) Iffi Groups of metal oxides, (vi) Iffi metal metasilicates, (vii) mB metal oxides, (viii) mB metal bismuth salts, and mixtures thereof. The test carrier modifier may be selected from the group consisting of oxides and metasilicates of any of sodium, potassium, magnesium, calcium, strontium, barium, and zinc, and any of the foregoing oxides. In one embodiment, the alkaline modifier is tannic acid such as calcium citrate (CaSi〇3). The calcium metasilicate may be crystalline or amorphous _〇_〇 113). The catalyst on the modified support may comprise one or more metals selected from the group consisting of platinum, palladium, cobalt, tin or antimony, and supported on the cerium oxide support, optionally by one or more The massing agent is selected from the group consisting of abietic acid, and one or more oxides of tungsten, molybdenum and/or vanadium. The catalyst composition suitable for use in the present invention is preferably formed by metal impregnation in a modified support. However, other processes such as chemical vapor deposition may also be used. This saturation technique is described in the aforementioned U.S. Patent Nos. 7,608,744 and 7,863,489, and U.S. Patent Publication No. 2010/0197485, the entire disclosure of which is incorporated herein by reference. The original system is Z-fired and can be reduced to activate the catalyst. Also the money of 4〇〇t, there is a lower hoof. (4) The listening body continuously passes through the touch at a temperature of 4 〇〇 C. After the contact = being entered into the person (four) to carry out the hydrogen mosquito anti-hidden k, only the sputum and sputum, ϋt acid hydrogenation can achieve favorable acetic acid conversion scale and favorable ethanol selectivity rate, the noun, , conversion " indicates the amount of conversion into a chemical other than acetic acid. The conversion is expressed as a percentage of acetic acid in the feed. Conversion can
4〇：° * 5〇% > ^ s〇〇/o 0 IZ ，轉化率之，媒較為，如至少8。%或至少9Q%，但有些具體二 中，對乙醇為㊣選擇率之低轉化麵媒為可接受^ 、 選擇率係表示基於經轉化乙酸之莫耳百分I應了解自乙酸轉化 ^各化合物具有獨立之選神且該獅率與轉化率亦彼此獨立。例 ，，若經轉化乙酸之60莫耳％轉化成乙醇，則稱該乙醇轉化率為60%。 較佳者為’對乙醇之觸媒選擇率至少為6G%，如至少·，或至少 80%。氫化製程之較佳具體例紐非所需餘具魏選擇率，如對甲 烷、乙肢二祕碳。對鱗摘需產物之選擇輪佳者為小於作。， 如小於2%或小於ι〇/0。 /本文所用之名詞"產率"表示基於每小時所用觸媒公斤重於氫化期 間形成之特定產物如乙醇之克數。產率可在1〇〇至3 〇〇〇克乙醇/公 觸媒/小時之範圍。 本發明各種具體例中，由氫化製程製得之粗製乙醇產物，在任何 隨後加工如純化及分離之前，一般包括乙酸、乙醇及水。對粗製乙醇 產物之例舉組成範圍見於表卜但氫除外。表1中標示之，'其他，，可包含 例如酯類、醚類、醛類、酮類、烷烴類及二氧化碳。 201245126 組份 濃度(Wt.°/〇) _J農度(wt.°/〇) 乙醇 5至72 15 至 72 乙酸 0至90 〇至50 水 5至40 5至30 乙酸乙酯 0至30 1至25 乙醛 0至10 〇至3 其他 0.1 至 10 一 〇·1 至 6 濃度(Wt.0/〇、 ~Ϊ?Ϊ70~~ 〇至35 10 至 30 3至20 0.1 至 3 〇·1 至 4 濃度(wt%) 25 至 65 0至15 10 至 26 5至18 0.2 5.2 -具體财，表1之輔乙醇產物可具有低濃度乙酸但高轉化 率，且表1之乙酸濃度可在0.01爾至2〇wt%之範圍，如〇 〇5奶％至 〇•滅至咖％，或】讓至城。於具有較低量乙酸之具 例乙酸轉化率較佳者為大於75%，如大於85%或大於9〇〇/。。此 外’對乙醇之選擇率亦較佳者為較高，且較佳者為大於75%，如大於 85%或大於90%。 該等圖中齡之塔可包括任何可精分離及/或純化之蒸潑 塔。各塔較佳者為包括具有i至15〇板㈣s)，如自1〇至1〇〇板自 20至95板或自30至75板之板蒸館塔。該板可為篩板、固定間板、 可移動閥板或本技藝已知之任何其他適宜設計。其他具酬中，可使 用具有結構化填充或賴填充之填充塔。該域填充可制於連續塔 中或其等可_於兩個«個塔中，使得來自第-段之航進入該第 二段中同時使來自第二段之液體進入第一段等。 … 可與各蒸館塔-起利用之相闞冷凝器及液體分離容器可為任何習 知言f計且簡化於圖式中。可經由熱交換器或再彿11對各塔之基底或對 循環塔底液流供給熱。亦可使用其他麵之再魅如㈣㈣器。供 給至該再滞器之熱可獲自整合有該再締之製程綱產生之任何熱^ 獲自=部來源如其他熱產生化學製程或再沸器。雖朗式中顯示二個 反應器及一個閃蒸器，但於本發明各種具體例中可使用額外反應器、 閃蒸器、冷凝器、加熱元件及其他構件。如熟知本技藝者所理解，本 發明製程中亦可組合及利用各種冷凝器、泵、壓縮機、再沸器、滾筒、 閥、連接器、分離容器等之一般用以進行化學製程者。 15 201245126 塔中所使用之溫度及壓力係為可變動的。由於實務上在該等區中 一般係利用自10kPa至3000kPa之壓力，但有些具體例中可利用次大 氣壓或超大氣壓。各種區内之溫度—般將在作⑽出物被移除之組成 物之沸點與作為殘留物被移除之組成物之沸點間之範圍。如熟知本技 藝者所理解’在操作細軸既定位置之溫度與齡置之物質組成及 塔之壓力有關。此外，饋入速率可隨製造製程規模而變，且若有所描 述的話，則一般表示為饋入重量比例。 依據本發明之例舉乙醇回收系統示於第1A、ib、2A、2B、3A及 3B圓。各氫化系統loo提供依據本發明具體例之適宜之氫化反應器及 自粗反應混合物分離乙醇之製程。系統1〇〇包括反應區1〇1及分離區 102。反應區101包括反應器110、氫進料管線1〇3及乙酸進料管線 104。反應區102包括分離器115及蒸餾塔12〇及13〇。 氫化系統100包含反應區1〇1及分離區1〇2。分別經由管線1〇3 及104之氫及乙酸被饋入汽化器1〇5中而於被導致反應器11〇之管線 106中產生蒸汽進料液流、及排出(bbwdown)液流1〇7。於一具體例 中，管線103及104可組合並聯合饋入汽化器1〇5。管線1〇6中之蒸 汽進料液流之溫度較佳者為自l〇〇°C至35〇°C，如自120°C至310°C或 自150°C至300°〇未被蒸汽化之任何進料則經由排出液流1〇7自汽化 器105移除。此外，雖然管線1〇6顯示為導向反應器11〇頂端，但管 線106亦可導向反應器11〇側邊、上端部分或底部。 反應器110含有用以使羧酸較佳者為使乙酸氫化之觸媒。一具體 例中，可於反應器上游(視情況為汽化器丨05上游)使用一個或多個防 護床(guard beds)(未顯示)以避免觸媒受進料或流回/循環液流中所含之 毒害或不期望雜質。此防護床可於蒸汽或液體液流中使用。適宜防護 床材料可包含例如碳、氧化矽、氧化鋁、陶瓷或樹脂一目的中，該 防護床介質經功能化(functionalized)如經銀功能化以捕捉特定物種如 硫或鹵素。氫化製程期間’經由管線111自反應器110抽出(較佳者為 連續抽出)粗製乙醇產物。 管線111中之粗製乙醇產物可經冷凝並饋入分離器U5中，其隨 201245126 後提供蒸汽流112及液體流113。有些具體例中，分離器ι15可包括 閃蒸器或分液釜(]〇1(^〇1^〇〇。分離器115可在自2〇。(：至250。(：，如 自30C至225°C或自60。(：至200溫度下操作。分離器ns之壓力可自 50kPa 至 2500kPa，如自 75kPa 至 2250kPa 或自 i〇〇kPa 至 2100kPa。 視情況，管線111中之粗製乙醇產物可通過一個或多個膜以分離氫及/ 或其他非可冷凝氣體。 自分離器115流出之蒸汽流112可包括氫及烴類，且可經清除 (purged)及/或回到反應區101。當回到反應區ι〇1時，蒸汽流112與氫 進料103組合並共饋入(co_fed)汽化器1〇卜有些具體例中，返回之蒸 汽流112在與氫進料1〇3組合之前可經壓縮。 來自分離器115之液體流113可被抽出且作為進料組成物被導入 第一蒸餾塔120之側邊，該第一蒸餾塔12〇亦稱為，，酸分離塔，，^ 一 具體例中，該液體流113之内容物實質上類似於獲自反應器之粗製乙 醇產物，但組成中移除氫、二氧化碳、甲烷及/或乙院，其等已由分離 器115移除。據此，液體流113亦可稱為粗製乙醇產物。液體流ιΐ3 之例舉組成見於表2。應轉液職113可含有未列於表2中之其他 組份。 、 表120之&組成物 (液體流113) 濃度(Wt.〇/〇、 濃度(wt.%、 15 至 65 10 至 70 〇.〇1 至 20 〇·〇5 至 15 5至30 10 至 26 1至25 3至20 0.001 至 3 〇-1 JL3 0.01 至 5 0.01 至 3 0.0005 至 〇.〇5 〇 至 0.03 濃度(wt.%) 乙醇 5至72 乙酸 <90 水 5至40 乙酸乙酯 <30 乙趁 <10 縮醛 <5 _丙酮 <5 或若存在 整個說明書之表中以小於(<)表示之量較佳者為不存在 的話。則表示大於O.OOOlwt%之量。 一具體例中’反應區101在高於80%乙酸轉化率下操作，如高於 17 201245126 =轉峨高於·轉化率。因此，液體流出中之乙酸濃度可能 液體流113係導入第一塔12〇(亦稱為酸-水塔 各;舉的分離製程中之塔可稱為第-：第 塔120中並未添加夾帶劑(entrainers) >第 °中，水及未反應乙酸與任合其他若存在之重質組分-起自液 第一殘留物被抽出，較佳者為連續 第一殘留物中被移除，例如移除來自該粗製乙醇產物之水之 。第—塔120亦形成第—館出物，其於管線122中被抽 出。部伤之第一餾出物可經由管線123返回至第一塔12〇。 ㈣ίϊΓϋ低於約驗a_F操作時，於管線⑵流出之殘留物溫 度較佳者為自9QC至赋，如自阶至12(rc或自赋至賦。 於管線122流出之館出物溫度較佳者為自贼至机，如自机至 机或自7(TC至8(TC。有些具體例中，第一塔12〇之壓力可在〇鳥 至510kPa之範圍，如自廳至475咖或自跳至37她。 自分離區102抽出之有些殘留物包括乙酸及水。視第一幻2〇之 殘留物中所含之水及乙酸量而定，該殘留物可於一個或多個；列製程 中經處理。下顺進-步處理該_物之舉例製程，且應理解可使用 任何下列製細無_乙酸敍1殘留物包括大部份乙酸如大於 70wt%乙酸’則賴留物可被再魏至反廳巾而無縣離任何水。 -具體例中，當該殘留物包括大部份乙酸如大於5_%時，該殘留物 可为離成乙酸液流及水液流。於有些具體例中亦可自具有較低乙酸濃 度之殘留物中回收乙酸。該殘留物可藉蒸餾塔或一個或多個膜分離成 乙酸及水液流。若使用膜或膜陣列使乙酸與水分離，則該膜或膜陣列 可選自任何可移除滲透水液流之適宜的耐酸性臈。所得乙酸液流視情 況返回到反應器110。所得水液流可使用作為萃取劑或用以在水解單 元中水解含酯液流。 其他具體例中’例如當該殘留物包括少於5〇财％之乙酸時，可能 201245126 的選項包含下列之一種或多種：⑴將部分殘留物返回至反應器108，⑼ 中和該乙酸，（iii)使乙酸與醇反應，或(iv)將殘留物丟棄於廢水處理廠 中。亦可能使用其中可添加溶劑(視情況作用為共沸劑)之弱酸回收蒸 餾塔分離包括少於50wt°/〇乙酸之殘留物。適於此目的之舉例溶劑包含 乙酸乙醋、乙酸丙醋、乙酸異丙醋、乙酸丁醋、乙酸乙稀醋、二異丙 謎、二硫化碳、四氫°夫喃、異丙醇、乙醇及烧烴類。當中和乙 酸時，較佳者為殘留物包括少於l〇wt%乙酸。乙酸可以任何適宜驗金 屬或驗土金屬驗如氫氧化納或氫氧化_中和。當乙酸與醇反應時，較 佳者為殘留物包括少於50wt%乙酸。醇可為任何適宜醇，如曱醇、乙 醇、丙醇、丁醇或其混合物。反應形成酯，其可與其他系統整合，如 叛化製造或酯製造製程。較佳者為醇包括乙醇且所得酯包括乙酸乙 醋。視情況’所得酯可饋入氫化反應器中。 有些具體例中，當殘留物包括極微量乙酸，如少於5加％時，則殘 ，物可在丟棄於廢水處理廠中而無須進一步處理。殘留物之有機物内 容物如乙酸内容物可能有利地適用於培育廢水處理廠中之微生物。4〇:° * 5〇% > ^ s〇〇/o 0 IZ , conversion rate, media comparison, such as at least 8. % or at least 9Q%, but in some specific two, the low conversion conversion medium with positive selectivity for ethanol is acceptable, and the selectivity is based on the percentage of moles of converted acetic acid. It has an independent choice and the lion rate and conversion rate are also independent of each other. For example, if 60 mole % of converted acetic acid is converted to ethanol, the ethanol conversion is said to be 60%. Preferably, the catalyst selectivity for ethanol is at least 6 G%, such as at least, or at least 80%. A preferred embodiment of the hydrogenation process is the desired remainder of the selection of the Wei, such as para-methane, and the second carbon of the limb. The selection of the product for scale picking is less than the best. , such as less than 2% or less than ι〇/0. / The term "yield" as used herein refers to the number of grams of a specific product such as ethanol formed based on the kilogram of catalyst used per hour over the hydrogenation period. The yield can range from 1 Torr to 3 gram ethanol/mass catalyst/hour. In various embodiments of the invention, the crude ethanol product produced by the hydrogenation process generally comprises acetic acid, ethanol, and water prior to any subsequent processing, such as purification and separation. An exemplary composition range for the crude ethanol product is shown in the table except for hydrogen. As indicated in Table 1, 'others' may include, for example, esters, ethers, aldehydes, ketones, alkanes, and carbon dioxide. 201245126 Component concentration (Wt.°/〇) _J agricultural degree (wt.°/〇) Ethanol 5 to 72 15 to 72 acetic acid 0 to 90 〇 to 50 water 5 to 40 5 to 30 ethyl acetate 0 to 30 1 to 25 acetaldehyde 0 to 10 〇 to 3 other 0.1 to 10 〇·1 to 6 concentration (Wt.0/〇, ~Ϊ?Ϊ70~~ 〇 to 35 10 to 30 3 to 20 0.1 to 3 〇·1 to 4 Concentration (wt%) 25 to 65 0 to 15 10 to 26 5 to 18 0.2 5.2 - specific money, the auxiliary ethanol product of Table 1 may have a low concentration of acetic acid but high conversion, and the acetic acid concentration of Table 1 may be 0.01 Å to 2% wt% range, such as 〇〇5 milk% to 〇•灭至咖%, or 】 to the city. In the case of a lower amount of acetic acid, the acetic acid conversion rate is preferably greater than 75%, such as greater than 85 % or greater than 9 〇〇 /. In addition, the selection rate for ethanol is also higher, and preferably greater than 75%, such as greater than 85% or greater than 90%. Including any refining and/or purification of the steaming tower. Each tower preferably comprises from 1 to 15 plates (four) s), such as from 1 to 1 plate from 20 to 95 plates or from 30 to 75 plates. The steaming tower of the board. The panel can be a screen deck, a fixed partition, a movable valve panel, or any other suitable design known in the art. For other gains, a packed tower with structured filling or immersion filling can be used. The domain fill can be made in a continuous column or the like, in two columns, such that the flight from the first segment enters the second segment while the liquid from the second segment enters the first segment and the like. ... The condenser and liquid separation vessel that can be used with each steaming tower can be any conventional and simplified in the drawings. Heat may be supplied to the substrate of each column or to the recycle bottoms stream via a heat exchanger or a further reactor. You can also use other re-enchantments such as (4) (4). The heat supplied to the re-reservoir can be obtained from any heat generated by the integrated process, such as other heat generating chemical processes or reboilers. Although two reactors and one flasher are shown in the Lang type, additional reactors, flashers, condensers, heating elements and other components may be used in various embodiments of the invention. As understood by those skilled in the art, various condensers, pumps, compressors, reboilers, drums, valves, connectors, separation vessels, and the like, which are generally used for chemical processes, may be combined and utilized in the process of the present invention. 15 201245126 The temperature and pressure used in the tower are variable. Since it is practical to utilize pressures from 10 kPa to 3000 kPa in these zones, sub-atmospheric or super-atmospheric pressures may be utilized in some specific examples. The temperature in each zone will generally range between the boiling point of the composition from which (10) the removed material is removed and the boiling point of the composition from which the residue is removed. As is well understood by those skilled in the art, the temperature at the location of the operating fine axis is related to the composition of the aged material and the pressure of the column. In addition, the feed rate can vary with the size of the manufacturing process and, if described, is generally expressed as the weight ratio of the feed. An ethanol recovery system according to the invention is shown in Figures 1A, ib, 2A, 2B, 3A and 3B. Each hydrogenation system loo provides a suitable hydrogenation reactor in accordance with a specific embodiment of the invention and a process for separating ethanol from the crude reaction mixture. System 1 includes a reaction zone 1〇1 and a separation zone 102. Reaction zone 101 includes reactor 110, hydrogen feed line 1〇3, and acetic acid feed line 104. The reaction zone 102 includes a separator 115 and distillation columns 12A and 13A. The hydrogenation system 100 comprises a reaction zone 1〇1 and a separation zone 1〇2. Hydrogen and acetic acid via lines 1〇3 and 104, respectively, are fed into vaporizer 1〇5 to produce a vapor feed stream and a bbwdown stream 1〇7 in line 106 which results in reactor 11〇. In one embodiment, lines 103 and 104 can be combined and fed into vaporizer 1〇5. The temperature of the steam feed stream in line 1 〇 6 is preferably from 10 ° C to 35 ° C, such as from 120 ° C to 310 ° C or from 150 ° C to 300 ° 〇 no steam Any feed is removed from the vaporizer 105 via the effluent stream 1〇7. Further, although the line 1 〇 6 is shown as being directed to the top end of the reactor 11 , the line 106 can also be directed to the side, upper end or bottom of the reactor 11 . Reactor 110 contains a catalyst for making the carboxylic acid preferred for hydrogenating acetic acid. In one embodiment, one or more guard beds (not shown) may be used upstream of the reactor (as appropriate upstream of the vaporizer 丨05) to avoid catalyst loading or flow back/circulation flow. Contains poisonous or undesirable impurities. This guard bed can be used in a vapor or liquid stream. Suitable protective bed materials may include, for example, carbon, cerium oxide, aluminum oxide, ceramics or resins which are functionalized, such as functionalized with silver, to capture a particular species such as sulfur or halogen. The crude ethanol product is withdrawn (preferably continuously withdrawn) from reactor 110 via line 111 during the hydrogenation process. The crude ethanol product in line 111 can be condensed and fed to separator U5, which provides a vapor stream 112 and a liquid stream 113 after 201245126. In some embodiments, the separator ι15 may include a flasher or a liquid separator (1). The separator 115 may be at a temperature of 2 〇. (: to 250. (:, as from 30C to 225 °C or from 60. (: to 200 temperature operation. The pressure of the separator ns can be from 50kPa to 2500kPa, such as from 75kPa to 2250kPa or from i〇〇kPa to 2100kPa. Depending on the situation, the crude ethanol product in line 111 can be The hydrogen and/or other non-condensable gases are separated by one or more membranes. The vapor stream 112 exiting the separator 115 can include hydrogen and hydrocarbons and can be purged and/or returned to the reaction zone 101. When returning to reaction zone ι〇1, steam stream 112 is combined with hydrogen feed 103 and co-fed into (co_fed) vaporizer 1 . In some embodiments, return steam stream 112 is combined with hydrogen feed 1〇3. The liquid stream 113 from the separator 115 can be withdrawn and introduced as a feed composition to the side of the first distillation column 120, which is also referred to as an acid separation column, ^ In one embodiment, the contents of the liquid stream 113 are substantially similar to the crude ethanol product obtained from the reactor, but the group The removal of hydrogen, carbon dioxide, methane and/or benzene, etc., has been removed by separator 115. Accordingly, liquid stream 113 may also be referred to as a crude ethanol product. The exemplary composition of liquid stream ιΐ3 is shown in Table 2. The liquid transfer job 113 may contain other components not listed in Table 2. Table & Composition (Liquid Flow 113) Concentration (Wt.〇/〇, concentration (wt.%, 15 to 65 10 to 70) 〇.〇1 to 20 〇·〇5 to 15 5 to 30 10 to 26 1 to 25 3 to 20 0.001 to 3 〇-1 JL3 0.01 to 5 0.01 to 3 0.0005 to 〇.〇5 〇 to 0.03 concentration (wt. %) Ethanol 5 to 72 acetic acid <90 water 5 to 40 ethyl acetate <30 acetonitrile <10 acetal <5 _acetone < 5 or if present in the table of the entire specification as less than (<) If the amount is not present, it means that it is greater than 0.01% by weight. In a specific example, 'reaction zone 101 is operated at a conversion rate higher than 80% acetic acid, such as higher than 17 201245126 = higher than The conversion rate. Therefore, the concentration of acetic acid in the liquid outflow may be introduced into the first column 12〇 (also referred to as the acid-water tower); the tower in the separation process may be called No: no entrainers are added to the column 120 > in the °°, water and unreacted acetic acid and any other heavy components present if present are extracted from the liquid first residue, preferably The continuous first residue is removed, for example, water from the crude ethanol product is removed. The first column 120 also forms a first museum output which is withdrawn in line 122. The first distillate of the partial injury can be returned to the first column 12 via line 123. (4) When the operation is lower than the a_F operation, the temperature of the residue flowing out of the pipeline (2) is preferably from 9QC to the assignment, such as from the order to 12 (rc or self-assigned to the assignment. The temperature of the outlet flowing out of the pipeline 122 is better. For self-thief to machine, such as self-machine to machine or from 7 (TC to 8 (TC. In some specific cases, the pressure of the first tower 12 可 can range from ostrich to 510 kPa, such as from the hall to 475 coffee or Self-jumping to 37. Some of the residue extracted from the separation zone 102 includes acetic acid and water. Depending on the amount of water and acetic acid contained in the residue of the first illusion, the residue may be in one or more; Processed in the column process. The process of the article is processed in the next step, and it should be understood that any of the following processes can be used without any acetic acid, including a large portion of acetic acid, such as greater than 70% by weight of acetic acid. It can be further applied to the anti-office towel without any water from the county. In a specific example, when the residue includes most of the acetic acid, such as greater than 5%, the residue may be a mixture of acetic acid and aqueous streams. In some embodiments, acetic acid may also be recovered from residues having a lower acetic acid concentration. The residue may be by distillation column or one or The membrane is separated into an acetic acid and aqueous stream. If a membrane or membrane array is used to separate the acetic acid from the water, the membrane or membrane array can be selected from any suitable acid-resistant hydrazine of the removable permeate stream. Return to reactor 110 as appropriate. The resulting aqueous stream can be used as an extractant or to hydrolyze an ester-containing stream in a hydrolysis unit. In other embodiments, for example, when the residue comprises less than 5% acetic acid The option of 201245126 may include one or more of the following: (1) returning a portion of the residue to reactor 108, (9) neutralizing the acetic acid, (iii) reacting acetic acid with the alcohol, or (iv) discarding the residue in a wastewater treatment plant It is also possible to use a weak acid recovery distillation column in which a solvent (as the case may be an azeotropic agent) can be used to separate a residue comprising less than 50 wt/acetic acid. An exemplary solvent suitable for this purpose comprises ethyl acetate, acrylic acid Vinegar, isopropyl acetate, butyl acetate, ethyl acetate, diisopropyl mystery, carbon disulfide, tetrahydrofuran, isopropanol, ethanol and hydrocarbons. When neutralizing acetic acid, it is preferably residue. Including less than l〇w T% acetic acid. Acetic acid can be neutralized by any suitable metal or soil test such as sodium hydroxide or hydroxide. When acetic acid is reacted with an alcohol, preferably the residue comprises less than 50% by weight of acetic acid. The alcohol can be any Suitable alcohols, such as decyl alcohol, ethanol, propanol, butanol or mixtures thereof, react to form esters which can be integrated with other systems, such as rebel manufacturing or ester manufacturing processes. Preferred alcohols include ethanol and the resulting esters include acetic acid. Ethyl vinegar. As the case may be, the obtained ester can be fed into the hydrogenation reactor. In some specific examples, when the residue includes a very small amount of acetic acid, such as less than 5% by weight, the residue can be discarded in the wastewater treatment plant. No further treatment is required. The organic content of the residue, such as the acetic acid content, may be advantageously suitable for cultivating microorganisms in a wastewater treatment plant.
管線122中之該第―館出物除了乙醇及及他有機物以外亦包括 水。以範®表心管線丨22巾之第—_物巾之水濃餘佳者為自 4痛至38wt% ’如自7wt%至32wt%或自7痛至25奶％。管線122 中之部分第一館出物可以例如自約1〇:1至1:1〇，如自3q至U或自 1:2^ 2:1之比例，冷凝及回流。若需要額外水以改良該輕烴塔125中 之分離則此可能必要。應了朗航可輯階段數、鱗位置、塔效 率及/或進料組成而異。以大於3:1之回流比操作可能較不佳，因^能 ^要更多Hb量以操作該第-塔12〇。第，出物 第二塔13〇中。 J 入圖及第2B圖中，將管線122中之至少部份的第一館出物饋 取水分離單元15G可為吸附單元、膜、分子筛、萃 亦可使舰或猶列以使水_出物分離。該膜 選自任何可自液包括乙醇及乙酸乙酷之液流中移除滲透水 液流之任合適宜膜。該水分離器150可自管線122中之部份第一德出 201245126 物„夕95/〇之水，且較佳者為自該第一館出物移除99%至99 99。/ 之水至水液流151卜所有或部份之水㈣⑸可歸線⑸中。 至塔120，於該處水較佳者為最終自塔12㈣收至管線^ : 此外笛或另外，所有或部分水液流151可經由管線155被清除。 =餘^之第-德出物作為乙醇混合物液流152離開該水分離器 之合物錢152包齡於_，如少於_或少於减 及3B圖令顯示之具體例中，該水分離11160可為屢變吸附 們⑸單7°。該PSA單元⑽她兄在自贼至靴，如自8〇^ 作该PSA單凡160可包括二個至五個床。ps 可於營始·9/°Γ 移除至水液流161。所有或部分的水液流161 τ於管線163巾返回至塔120，於該處較佳者為水最 ===，—殘留物中爾或另外，所有或部分編⑹ 離門2 Γ 剩餘部分之第—触物作為乙醇混合物液流162 60。乙醇混合物液流162可具有少於1_%，如少於 中之之低水濃度。乙醇混合物液流152/162及管線121 未列出之例舉組分見於下表3。亦應理解該等液流亦可含有 禾歹J出之其他組分，如衍生自進料之組分。 201245126 乙醇混合物液流 表3 ·經水分離之第一塔12〇 _____ 乙醇 水 乙酸 乙酸乙酯 乙醛 縮醛 丙嗣 20 至 95 30 至 95 <10 〇〇1 至 6 < 2 0.001 至 0.5 <60 1至55 <10 0.001 至 5 <0.1 <0.1 <0.05 〇·〇〇1 至 0.03 濃度 40 至 95 0.1 至 2 0.01 至 0.2 5至55 0.01 至 4 <0.05 0.01 至 0.025 殘留物 1至50 45 至 95 <0.9 2至35 60 至 90 <0.3 乙酸 <90 水 30至1〇〇 ;醇 <1 參見第2A、2B、3A及3B圖’較佳者為乙醇混合物液流152/162 並未返回或回流至第一塔12〇β管線124中之第一館出物之冷凝部份 可與乙醇混合物液流152或162組合以控制饋人第二塔⑼之水濃 度°例如’有些具體射，第_概物可分流為相等部份，而其他具 體例中’所有第-德出物可經冷凝或所有第，出物可於水分離單元 中被加工。第2A及2B圖中，管線124中之冷凝部份及乙醇混合物液 流152共同饋入第二塔13〇。其他具體例中，管線124中之冷凝部份 及乙醇混合物液流152可分別饋入第二塔13〇。於第3A及3B圖中， 管線124中之冷凝部份及乙醇混合物液流162共同饋入第二塔13〇 中。其他具體例中，管線124中之冷凝部份及乙醇混合物液流162可 分別镄入第二塔130。該組合之餾出物及乙醇混合物具有大於 0.5wt% ’如大於2wt%或大於5wt%之總水濃度。以範圍表示時，該組 合之館出物及乙醇混合物之總水濃度可自0.5至15wt%，如自2至 12wt%或自 5 至 10wt%。 第二塔130(亦稱為”輕烴塔”）自管線122中之第一餾出物及/或 自乙醇混合物液流152或162移除乙酸乙酯及乙醛。乙酸乙酯及乙醛 21 201245126 係作為管線132中之第二餾出物被移除且水作為管線131中之第二殘 留物被移除。該乙醇產物側餾分經由管線135作為蒸汽或液體，較佳 者為作為蒸汽側餾分被移除。第二塔13〇可為板狀塔或填 。一 體例中，第二塔130為具有5至70板’如自15至5〇板或自°2〇至衫 板之板狀塔》 第二塔130係在自〇.ikpa至51〇kPa，如自1〇咖至45〇kpa或自 50kPa至350kPa之壓力範圍下操作。雖然第二塔13〇之溫度為可變 動，但當在20kPa至70kPa操作時，管線131中流出之第二殘留物溫 度較佳者為自30°C至75t，如自35°C至70°C或自40°C至65t。管線 132中流出之第二餾出物溫度較佳者為自2〇6(：至分它，如自25t至 50°C 或自 30°C 至 45。〇 視情況，水可經由管線125饋入第二塔130。饋入第二塔13〇之 水總濃度較佳者剔、於i_%m22巾之第__邮物及/或管線 152或162中之乙醇混合物液流包括少量水，如少於丨加％或少於 0.5wt%時’可對帛二塔13G饋人額外水作為該塔上端部份之萃取劑。 較佳者為經由萃取劑添加足量水因而饋入第二塔13〇之水總濃度係佔 饋入第二塔130之所有組份之總重之自丨至1〇加％，如自2至6斯％。 若萃取劑包括水，則水可獲自外部來源或或自來自—個或多個其他其 他塔或水分離器之内部回流/循環。 適宜萃取劑亦可包含例如二曱基亞硬、甘油、二乙二醇、μ蔡紛、 氣醒、Ν，Ν’·二甲基甲醯胺、Μ_丁二醇、乙二醇妙戍二醇、丙二醇· 四乙二醇·聚乙二醇、甘油-丙二醇_四乙二醇山心丁二醇、乙趟、甲酸 甲5旨、環己烧、Ν，Ν-二曱基·1，3-丙二胺、Ν，Ν’_二曱基乙二胺、二伸乙 三胺、己二胺及1,3-二胺基戊烧、燒化售吩、十二烧、十三烧、十四烧、 IUb；5蠟(chlorinated paraffins)或其組合。當使用萃取劑時，可使用適 且回收系統如其他蒸飽塔將萃取劑再循環。 第二塔130之第二趨出物、乙醇側傲分及第二殘留物組成物之例 4 〇 _解_出物及殘留物亦可含有未列於表4之 其他組分。 22 201245126 表4 :第二塔130 度(Wt.0/〇) 濃度(wt·%) 濃度 iwt.0/。、 笫二餾出物----~^- 乙酸？，瞄 C ^ 乙醛 乙醇 水 j主yu 10 至 80 15 至 75 <60 1至40 1至35 <45 0.001 A 40 〇·〇1 至 35 <20 0.01 至 10 0.1 至 5 乙醇側餾分 乙醇 水 80 至 99.5 85 至 97 60 至 95 <20 0.001 至 15 0.01 至 1〇 乙酸乙酯 乙酸 <1 0.001 至 0.5 〇顧至0.01 <0.05 <0.01 0-001 至 0.01 第二殘留物 乙醇 水 5至80 10 至 75 20 至 70 5至80 10 至 75 20 至 70 乙酸乙酯 乙酸 —-—--- <1 __<2 0施至2 <1 0顧至〇·5 0.001 至 1 t、一具體例中，呈蒸汽或液體之該乙醇侧餾分可實質上不含乙酸乙 酿或乙，。相對於該乙醇側館分，該第二殘留物可富含水。此外，自 該第一塔載出之任何乙酸可濃縮於第二殘留物中。 管線132中之包括乙酸乙酯及/或乙醛之該第二顧物物較佳者為以 例如自+ 1:30至30:1 ’如自1:10至10:1或自1:3至3:1之回流比予以回 流。若必要亦可使用較高回流比。—目的中，管線132中之該第二顧 出物或其-部份可返回至反應H 11Q，但未顯示H出物中之乙 酸乙酯及/或乙醛可於氫化反應器110中進一步反應。 -具體例中’管線132中之該第二顧出物可進而被分離而產生含 乙醛之液流及含乙酸㈤之紐。此可使得部份之騎含乙链之液流 或含乙酸乙S旨之液流被補環至反絲11Q同時清除其他液流。該清 除液流具有作為乙酸乙酯及/或乙醛來源之價值。 23 201245126 有些具體例中，管線131中之第二殘留物可進而被分離以回收乙 醇或被使用以作為乙醇溶劑。 管線135中之該乙醇產物側餾分可在比該第一餾出物122及/或乙 醇混合物液流152或162之進料位置低的位置被抽出。較佳者為乙醇 混合物液流中之至少40%乙醇於在乙醇產物側餾分中被移除，如至少 50%、至少60%或至少70%。該乙醇產物側餾分135相較於該第二殘 留物131較富含乙醇。由本發明製程製得之該乙醇產物側餾分135可 為包括占該乙醇產物總重之75至96wt%乙醇，如自80至96wt%或自 85至96%乙醇之工業級乙醇。較佳者為，該乙醇產物側餾分亦包括少 於500wppm乙酸，如少於400wppm、少於300wppm或少於250wppm。 較佳者為’該乙醇產物側餾分包括少於100wppm乙酸乙酯，如少於 90wppm或少於75wppm。例舉之乙醇產物側餾分組成範圍見於下表5。 組分 表5 : 濃度(wt.%) 乙醇產物組成物 濃度(wt.%) 濃度(Wt.°/〇) 乙醇 75 至 96 80 至 96 85 至 96 水 <12 1至9 3至8 乙酸 <1 <0.1 <0.01 乙酸乙酯 <2 <0.5 <0.05 縮醛 <0.05 <0.01 < 0.005 丙嗣 <0.05 <0.01 < 0.005 異丙醇 <0.5 <0.1 <0.05 正丙醇 <0.5 <0.1 <0.05 本發明之乙醇產物側餾分135組成物較佳者為含有極少量如少於 〇.5wt%之其他醇如甲醇、丁醇、異丁醇、異戊醇及其他C4_C2〇醇類。 一具體例中，乙醇產物側德分組成物中之異丙醇量係自8〇至 l，000wppm ’ 如自 95 至 l，000wppm ' 自 1〇〇 至 700wppm、或自 15〇 至500wppm。一具體例中，該乙醇產物侧餾分組成物實質上不含乙 路’視情況包括少於8wppm乙醛’如少於5wppm或少於iwppm。 如第1B、2B及3B圖所示，可利用進一步的水分離以產生乙醇產 24 201245126 物液流。乙醇產物側顧分135可導入水分離器140中。水分離單元140 可為吸附單元、臈、分子篩、萃取蒸餾塔或其組合。亦可使用膜或膜 陣列將水與德出物分離。該膜或膜陣列可選自可自亦包括乙醇及乙酸 乙醋之液流移除滲透水液流之任何適宜膜。水分離器14〇可自管線135 中之乙醇產物側館分移除至少9〇%之水，且更好自乙醇產物側館分口5 移除95%至99.99%水，移除至水液流141中《所有或部分水液流14ι 可自系統被清除或可全部或部份返回至第二塔13〇並在管線131中之 第二殘留物中被移除。剩餘部份之乙醇產物側餾分作為乙醇產物液流 142離開該水分離器14〇。此具體例中，乙醇產物液流之乙醇濃度可高 於表5所示者’且較佳者為為高於97奶％乙醇，如高於或高於 99.5wt°/Wt目的之乙醇產物較佳者為包括少於3加％水，如少於2加％ 或少於0.5wt%。 ' 由本發明具體例所製造之乙醇可使用於各種用途，包含作為燃 料、溶劑、化學·、Μ產品、清雜、赫劑、賴傳輸或氫氣 消耗等用途。於燃料應財，完成之乙醇組成物可與汽油摻合用於交 通工具如汽車、船及小型活塞式㈣飛機。於義侧途巾，此完成 之乙醇，成物可用作為衛生及化妝製劑、清潔劑、殺随、塗料、油 墨及醫藥之溶劑。該完成之乙醇組成物亦可使用作為醫藥產品、食品 製劑、，料、光化學品及乳膠加卫之製造製程中之加工溶劑。 該完成之乙軸祕亦可使料為化學·以製造其他化學品如 醋、丙稀酸乙自旨、乙酸乙9旨、乙稀、二賴、乙胺類、_、及高級 醇類尤其疋丁醇。製dg旨巾，該完成之乙雜成物可藉乙酸醋 化其他用途中’該凡成之乙醇組成物可經脫水而製造乙稀。可利用 任何已知之脫水觸媒如沸石觸媒使乙醇脫水。 a 士iff就本發明進行詳述’但在本發鴨神及範_之改質對熟 工 =3=為顯而易見。此外，應了解本文及/或附屬申請專利 ^ ^ %目献部分各種淑各瓣徵可全部或部分 等二斑在ί種具體例之前述描述中’表示其他具體例之該 等具趙例可適個或多個其他具體例組合，其為熟知本技藝者可 25 201245126 了解。再者， 限制本發明。 熟知本技藝者將了解前述描述僅為舉例綱且並不用以 【圖式簡單說明】 本發明將參考關於下列贿巾純城，其巾，洲編號表示 類似構件。 第1A圖及第1B圖為依據本發明具體例之氫化製程及兩個塔分離 製程之示意圖。 第2A圖及第2B圖為依據本發明具體例之另一氫化製程及具有介 隔水分離器以移除水之兩個塔分離製程之示意圖。 第3A圖及第3B圖為依據本發明具體例之另一氫化製程及具有介 隔膜以移除水之兩個塔分離製程之示意圖。 【主要元件符號說明】 代號 說明 100 氫化系統 101 反應區 102 分離區 103 氫進料管線/管線 104 乙酸進料管線/管線 105 汽化器 106 管線 107 排出液流 110 反應器 111 管線 112 蒸汽流 113 液體流 26 201245126 代號 說明 115 分離器 120 第一蒸餾塔/第一塔/酸 分離塔 121 管線 122 管線/第一餾出物 123 管線 124 管線 125 管線 130 第二塔/輕烴塔 131 管線/第二殘留物 132 管線 135 管線/乙醇產物側餾分 140 水分離器 141 水液流 142 乙醇產物液流 150 水分離器 151 水液流 152 乙醇混合物液流 153 管線 155 管線 160 水分離器/PSA單元 161 水液流 162 乙醇混合物液流 163 管線 165 管線 27The first library in line 122 also includes water in addition to ethanol and other organic matter. In the case of the Fan® Concentric Pipeline, the water content of the towel is from 4% to 38% by weight, such as from 7% to 32% by weight or from 7 to 25%. Portions of the first library in line 122 may be condensed and refluxed, for example, from about 1 〇:1 to 1:1 〇, such as from 3q to U or from 1:2^2:1. This may be necessary if additional water is needed to improve the separation in the light hydrocarbon column 125. It should vary depending on the number of miles available, the position of the scale, the efficiency of the tower, and/or the composition of the feed. Operating at a reflux ratio greater than 3:1 may be less desirable because more Hb is required to operate the first column. First, the second tower 13 is in the middle. In the drawing of Fig. 2 and Fig. 2B, the first library feed water separating unit 15G of at least a portion of the pipeline 122 may be an adsorption unit, a membrane, a molecular sieve, or a sifter or a water tank. Separation of matter. The membrane is selected from any suitable membrane that removes the permeate stream from a liquid stream comprising ethanol and ethyl acetate. The water separator 150 may be from the first part of the pipeline 122 to the water of 201245126, and preferably from the first museum, 99% to 99 99. To the water stream 151 all or part of the water (4) (5) can be returned to line (5). To the tower 120, where the water is preferably from the tower 12 (four) to the pipeline ^: In addition to flute or otherwise, all or part of the liquid Stream 151 can be purged via line 155. = _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ In the specific example of display, the water separation 11160 can be a single-adsorption (5) single 7°. The PSA unit (10) her brother is in the thief to the boot, such as from 8〇^, the PSA single 160 can include two to Five beds. ps can be removed to the water stream 161 at the beginning of the camp. 9/° 。. All or part of the water stream 161 τ is returned to the tower 120 in line 163, where the water is the best = ==, - Residue or otherwise, all or part of (6) from the remaining part of the door 2 触 - the contact as an ethanol mixture stream 162 60. The ethanol mixture stream 162 may have less than 1%, such as The low water concentration in the middle. The ethanol mixture stream 152/162 and the optional components not listed in line 121 are shown in Table 3 below. It should also be understood that the streams may also contain other components from the group. Such as the component derived from the feed 201245126 Ethanol mixture flow table 3 · The first column separated by water 12 〇 _____ Ethanol acetic acid ethyl acetate acetaldehyde acetal acetonitrile 20 to 95 30 to 95 < 10 〇 〇1 to 6 < 2 0.001 to 0.5 < 60 1 to 55 < 10 0.001 to 5 < 0.1 < 0.1 < 0.05 〇·〇〇1 to 0.03 Concentration 40 to 95 0.1 to 2 0.01 to 0.2 5 to 55 0.01 to 4 < 0.05 0.01 to 0.025 Residue 1 to 50 45 to 95 < 0.9 2 to 35 60 to 90 < 0.3 acetic acid < 90 water 30 to 1 Torr; alcohol < 1 See 2A, 2B 3A and 3B 'better' is the ethanol mixture stream 152/162 that is not returned or returned to the first column 12〇β line 124. The condensation portion of the first library can be mixed with the ethanol mixture stream 152 or 162 is combined to control the water concentration of the second tower (9) to be fed. For example, 'some specific shots, the first object can be split into equal parts, and in other specific examples' There may be a first-deuterate product which may be condensed or all of which may be processed in a water separation unit. In Figures 2A and 2B, the condensed portion of line 124 and the ethanol mixture stream 152 are fed together to the second column. 13〇. In other embodiments, the condensed portion of line 124 and the ethanol mixture stream 152 can be fed to second column 13A, respectively. In Figures 3A and 3B, the condensed portion of line 124 and the ethanol mixture stream 162 are fed together into second column 13A. In other embodiments, the condensed portion of line 124 and the ethanol mixture stream 162 can be drawn into second column 130, respectively. The combined distillate and ethanol mixture has a total water concentration of greater than 0.5 wt%, such as greater than 2 wt% or greater than 5 wt%. When expressed in terms of the range, the total water concentration of the combination and the ethanol mixture of the combination may be from 0.5 to 15% by weight, such as from 2 to 12% by weight or from 5 to 10% by weight. The second column 130 (also referred to as the "light hydrocarbon column") removes ethyl acetate and acetaldehyde from the first distillate in line 122 and/or from the ethanol mixture stream 152 or 162. Ethyl acetate and acetaldehyde 21 201245126 was removed as the second distillate in line 132 and water was removed as the second residue in line 131. The ethanol product side draw is removed via line 135 as steam or liquid, preferably as a steam side cut. The second column 13 can be a plate tower or filled. In an integrated example, the second tower 130 is a plate-shaped tower having 5 to 70 plates 'such as from 15 to 5 〇 plates or from ° 2 〇 to the shirt plate. The second tower 130 is at 〇.ikpa to 51 kPa, Such as from 1 〇 coffee to 45 〇 kpa or from 50 kPa to 350 kPa pressure range. Although the temperature of the second column 13 is variable, when operating at 20 kPa to 70 kPa, the temperature of the second residue flowing out of the line 131 is preferably from 30 ° C to 75 t, such as from 35 ° C to 70 ° C or from 40 ° C to 65 t. The temperature of the second distillate flowing out of line 132 is preferably from 2〇6 (: to its fraction, such as from 25t to 50°C or from 30°C to 45. Depending on the situation, water can be fed via line 125. Into the second column 130. The total concentration of water fed into the second column 13 is preferably the same as that in the first stream of the i_%m22 towel and/or the ethanol mixture stream in the line 152 or 162 includes a small amount of water, If less than 5% or less than 0.5% by weight, the additional water may be fed to the second column 13G as the extractant at the upper part of the column. Preferably, a sufficient amount of water is added via the extractant to feed the second The total concentration of water in the column 13 is from the total weight of all components fed into the second column 130 to 1% plus %, such as from 2 to 6 s%. If the extractant includes water, the water can be obtained from External source or internal recirculation/circulation from one or more other towers or water separators. Suitable extractants may also contain, for example, dimercapto, hard, glycerol, diethylene glycol, μ Cai, awakening ,Ν,Ν'· dimethylformamide, Μ-butanediol, ethylene glycol, propylene glycol, tetraethylene glycol, polyethylene glycol, glycerol-propylene glycol_tetraethylene glycol Alcohol, ethyl hydrazine, formic acid methyl 5, cyclohexane, hydrazine, hydrazine-dimercapto-1,3-propanediamine, hydrazine, Ν'_didecylethylenediamine, diethylenetriamine, hexan Amine and 1,3-diaminopentane, burnt benzene, dodecacin, thirteen, fourteen, IUb; chlorinated paraffins or combinations thereof. When using an extractant, use And the recovery system, such as other steaming towers, recycles the extractant. Example 2 of the second enthalpy of the second column 130, the ethanol side and the second residue composition 〇 _ solution _ output and residue may also Contains other components not listed in Table 4. 22 201245126 Table 4: Second Tower 130 Degrees (Wt.0/〇) Concentration (wt·%) Concentration iwt.0/., Distillate---- ~^- acetic acid?, aiming C ^ acetaldehyde ethanol water j main yu 10 to 80 15 to 75 < 60 1 to 40 1 to 35 < 45 0.001 A 40 〇 · 〇 1 to 35 < 20 0.01 to 10 0.1 To 5 ethanol side cut ethanol water 80 to 99.5 85 to 97 60 to 95 < 20 0.001 to 15 0.01 to 1 〇 ethyl acetate acetic acid < 1 0.001 to 0.5 〇 to 0.01 < 0.05 < 0.01 0-001 to 0.01 second residue ethanol water 5 to 80 10 to 75 20 to 70 5 to 80 10 to 75 20 to 70 ethyl acetate acetic acid -------- <1 __<2 0 to 2 <1 0 to 〇·5 0.001 to 1 t, one In a specific example, the ethanol side fraction in the form of steam or liquid may be substantially free of acetic acid or B. The second residue may be enriched with water relative to the ethanol side pavilion. Additionally, any acetic acid carried from the first column can be concentrated in the second residue. Preferably, the second item comprising ethyl acetate and/or acetaldehyde in line 132 is, for example, from +1 to 30:30:1 'from 1:10 to 10:1 or from 1:3 The reflux ratio to 3:1 was refluxed. A higher reflux ratio can also be used if necessary. In the event that the second moiety or a portion thereof in line 132 can be returned to reaction H 11Q, but ethyl acetate and/or acetaldehyde in H product is not shown to be further in hydrogenation reactor 110. reaction. - In the specific example, the second take-up in line 132 can be further separated to produce an acetaldehyde-containing liquid stream and a acetic acid-containing (f)-containing feed. This allows a portion of the liquid stream containing the ethyl chain or the liquid stream containing the acetic acid to be replenished to the counter wire 11Q while removing other liquid streams. The purge stream has a value as a source of ethyl acetate and/or acetaldehyde. 23 201245126 In some embodiments, the second residue in line 131 can be further separated to recover ethanol or used as an ethanol solvent. The ethanol product side draw in line 135 can be withdrawn at a lower position than the feed point of the first distillate 122 and/or the ethanol mixture stream 152 or 162. Preferably, at least 40% of the ethanol in the ethanol mixture stream is removed in the ethanol product side draw, such as at least 50%, at least 60%, or at least 70%. The ethanol product side fraction 135 is richer in ethanol than the second residue 131. The ethanol product side fraction 135 produced by the process of the present invention can be comprised of industrial grade ethanol comprising from 75 to 96 wt% ethanol, such as from 80 to 96 wt% or from 85 to 96% ethanol, based on the total weight of the ethanol product. Preferably, the ethanol product side draw also comprises less than 500 wppm acetic acid, such as less than 400 wppm, less than 300 wppm or less than 250 wppm. Preferably, the ethanol product side draw comprises less than 100 wppm ethyl acetate, such as less than 90 wppm or less than 75 wppm. An exemplary ethanol product side cut composition range is shown in Table 5 below. Composition Table 5: Concentration (wt.%) Ethanol Product Composition Concentration (wt.%) Concentration (Wt.°/〇) Ethanol 75 to 96 80 to 96 85 to 96 Water <12 1 to 9 3 to 8 Acetic Acid <1 <1 < 0.1 < 0.01 ethyl acetate < 2 < 0.5 < 0.05 acetal < 0.05 < 0.01 < 0.005 propylene < 0.05 < 0.01 < 0.005 isopropyl alcohol < 0.5 <; 0.1 < 0.05 n-propanol < 0.5 < 0.1 < 0.05 The ethanol product side fraction 135 composition of the present invention preferably contains a very small amount, such as less than 0.5% by weight of other alcohols such as methanol, butanol, Isobutanol, isoamyl alcohol and other C4_C2 sterols. In one embodiment, the amount of isopropanol in the ethanol product side component is from 8 Torr to 1,000 wppm 'e from 95 to 1,500 wppm ' from 1 Torr to 700 wppm, or from 15 Torr to 500 wppm. In one embodiment, the ethanol product side draw composition is substantially free of ethylene path' as the case includes less than 8 wppm acetaldehyde', such as less than 5 wppm or less than iwppm. As shown in Figures 1B, 2B and 3B, further water separation can be utilized to produce a liquid stream of ethanol 201224126. The ethanol product side 135 can be introduced into the water separator 140. The water separation unit 140 may be an adsorption unit, a helium, a molecular sieve, an extractive distillation column, or a combination thereof. It is also possible to separate the water from the German product using a membrane or membrane array. The film or array of membranes can be selected from any suitable membrane that can remove the permeate stream from a stream that also includes ethanol and ethyl acetate. The water separator 14A can remove at least 9% water from the ethanol product side column in line 135, and preferably remove 95% to 99.99% water from the ethanol product side hall junction 5, and remove to the water liquid. In flow 141, "all or part of the aqueous stream 14i may be removed from the system or may be returned in whole or in part to the second column 13" and removed in the second residue in line 131. The remaining portion of the ethanol product side stream exits the water separator 14 as an ethanol product stream 142. In this specific example, the ethanol product stream may have an ethanol concentration higher than that shown in Table 5' and preferably higher than 97 milk% ethanol, such as ethanol products above or above 99.5 wt/Wt. The preferred ones include less than 3 plus % water, such as less than 2 plus or less than 0.5 wt%. The ethanol produced by the specific examples of the present invention can be used for various purposes, including as a fuel, a solvent, a chemical, a hydrazine product, a hydrazine, a granule, a hydrazine, or a hydrogen gas. In the case of fuel, the completed ethanol composition can be blended with gasoline for transportation vehicles such as automobiles, boats and small piston (4) aircraft. The Yuyi side towel, the finished ethanol, can be used as a solvent for hygiene and cosmetic preparations, detergents, killing, coatings, inks and pharmaceuticals. The finished ethanol composition can also be used as a processing solvent in the manufacturing process of pharmaceutical products, food preparations, materials, photochemicals, and latex. The completion of the B-axis can also make the material chemical. To make other chemicals such as vinegar, acrylic acid, acetic acid, ethylene, bismuth, ethylamine, _, and higher alcohols. Butanol. The dg towel is prepared, and the finished b product can be made into acetic acid by other uses. The ethanol composition can be dehydrated to produce ethylene. The ethanol can be dehydrated using any known dehydration catalyst such as a zeolite catalyst. a Shi iff is described in detail in the present invention, but it is obvious that the modification of the duck god and the model is correct for the mature worker =3=. In addition, it should be understood that the various patents and/or sub-applications of the patents may be in whole or in part, and in the foregoing description of the specific examples, A suitable combination of one or more other specific examples is known to those skilled in the art and can be found at 25 201245126. Furthermore, the invention is limited. It will be understood by those skilled in the art that the foregoing description is by way of example only and not for the purpose of the description of the drawings. Fig. 1A and Fig. 1B are schematic views showing a hydrogenation process and two column separation processes according to a specific example of the present invention. 2A and 2B are schematic views of another hydrogenation process according to a specific example of the present invention and two column separation processes having a water separator to remove water. 3A and 3B are schematic views of another hydrogenation process according to a specific example of the present invention and two column separation processes having a membrane to remove water. [Main component symbol description] Code description 100 Hydrogenation system 101 Reaction zone 102 Separation zone 103 Hydrogen feed line/line 104 Acetic acid feed line/line 105 Vaporizer 106 Line 107 Drain stream 110 Reactor 111 Line 112 Steam stream 113 Liquid stream 26 201245126 Code Description 115 Separator 120 First Distillation Column / First Column / Acid Separation Tower 121 Line 122 Pipe / First Distillate 123 Line 124 Line 125 Line 130 Second Tower / Light Hydrocarbon Tower 131 Pipe / Second Residue Element 132 Line 135 Line / Ethanol Product Side Fraction 140 Water Separator 141 Water Stream 142 Ethanol Product Stream 150 Water Separator 151 Water Stream 152 Ethanol Mixture Stream 153 Line 155 Line 160 Water Separator / PSA Unit 161 Water Stream 162 ethanol mixture stream 163 line 165 line 27