[go: up one dir, main page]

TW201134795A - Processes for maximizing ethanol formation in the hydrogenation of acetic acid - Google Patents

Processes for maximizing ethanol formation in the hydrogenation of acetic acid Download PDF

Info

Publication number
TW201134795A
TW201134795A TW100103896A TW100103896A TW201134795A TW 201134795 A TW201134795 A TW 201134795A TW 100103896 A TW100103896 A TW 100103896A TW 100103896 A TW100103896 A TW 100103896A TW 201134795 A TW201134795 A TW 201134795A
Authority
TW
Taiwan
Prior art keywords
acetic acid
crude ethanol
weight
ethanol product
product
Prior art date
Application number
TW100103896A
Other languages
Chinese (zh)
Other versions
TWI588121B (en
Inventor
Trinity Horton
Radmila Jevtic
Victor J Johnston
Tianshu Pan
R Jay Warner
Heiko Weiner
Nathan Bower
Josefina T Chapman
Gerald Grusendorf
Original Assignee
Celanese Int Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from US12/940,595 external-priority patent/US8552224B2/en
Application filed by Celanese Int Corp filed Critical Celanese Int Corp
Publication of TW201134795A publication Critical patent/TW201134795A/en
Application granted granted Critical
Publication of TWI588121B publication Critical patent/TWI588121B/en

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/132—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group
    • C07C29/136—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH
    • C07C29/147—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of carboxylic acids or derivatives thereof
    • C07C29/149—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of carboxylic acids or derivatives thereof with hydrogen or hydrogen-containing gases
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/74—Separation; Purification; Use of additives, e.g. for stabilisation
    • C07C29/76—Separation; Purification; Use of additives, e.g. for stabilisation by physical treatment
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/74—Separation; Purification; Use of additives, e.g. for stabilisation
    • C07C29/76—Separation; Purification; Use of additives, e.g. for stabilisation by physical treatment
    • C07C29/80—Separation; Purification; Use of additives, e.g. for stabilisation by physical treatment by distillation

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

In one embodiment, the invention is to a process for purifying a crude ethanol product. The process comprises the step of hydrogenating acetic acid in a reactor in the presence of a catalyst to form the crude ethanol product. The process further comprises the step of separating at least a portion of the crude ethanol product in a purification zone. The purification zone preferably comprises a first column, which yields a first distillate comprising ethanol, water and ethyl acetate, and a first residue comprising acetic acid. The at least a portion of the crude ethanol product has a residence time from the reactor to the purification zone from 5 minutes to 5 days.

Description

201134795 代號 說明 ~~ 117 管路 118 管路 ~~: 120 管路 121 管路 130 儲存槽 131 管路 132 管路 五、 本案若有化學式時，請揭示最能顯示發明特徵的化 無0 \ 六、 發明說明： 優先權主張 本發明申5月案主張優先權基於2〇1〇年2月2日提出之美國專利暫 請案第61/300,815號，2010年5月7日提出之美國專利暫時申嗜案第 61/332,726號，及2⑽年u月5日提出之美國專利申請案第12/94〇,595 號’此等專利申請案之揭露均可納入做為參考。 【發明所屬之技術領域】 本發明涉及用於一般生產乙醇製程，和特別是在醋酸氩化製程中滅少 醋酸乙酯的形成為，而最大限度地發揮乙醇形成為的製程。 201134795 【先前技術】 工業上使用的乙醇係以傳統方式由石化原料，如石油，天然氣和煤户， 由進料中間體，如合成為氣，或由澱粉質原料材料或纖維素原料材料， 如玉米或甘蔗，生產之。來自石油化工原料以及來自纖維素原料的傳 統方法生產乙醇，包括乙烯之酸催化水合，甲醇同系化，直接醇合成 為和”費托合成"(Fischer-Tropsch synthesis)。不穩定性石化原料材料價格 會引起傳統方式生產乙醇的成本波動，當原料材料價格的上漲時，使 得需要替代來源的乙醇生產更有所需求。殿粉原料以及纖維素原料， 可經由發酵轉化成為乙醇。但是，通常發酵是用於消費性乙醇生產， 該乙醇係作為燃料或消費者之用。此外，;殿粉或纖維素原料的發酵和 食物來源競爭’而限制乙醇可用於工業生產的量。 經由烷酸和/或其他羰棊的化合物之還原生產乙醇已被廣泛研究，以及 各種組合的觸媒，支撐體和操作條件在文獻中被提及。烷酸，如醋酸， 與其他化合物之縣會職為乙醇或在其副反齡縣為乙醇曰。夂例 如：在氫化反應和/或其後的副反應中，酯連同乙醇和/或水一起產出， 形成為共沸物(azeotrope)，這是很難分開的。這些雜質可能會限制乙醇 生產，並可能需要昂貴和複雜的純化體系才能由乙醇中分離出雜質。 此外’當轉換不完整’未反應的酸停留在乙醇粗製品巾。這些殘餘的 醋酸可隨著時間的推移，促進更多有害的不良反應，此^留的萨 酸必須從乙醇粗製品移除，才能產出純化乙醇。 曰 因此’仍需要改善由粗製品回收乙醇之技術，該乙醇粗製品係通過产 酸’如醋酸，和/或其他絲化合物還原得之。此外，需要改進製程二 以減少或抑制通過不良副反應形成為的雜質。 【發明内容】 在第-實施方式巾’本發明是騎—種⑽粗製品的純化製程 於反應器中在㈣存在下氫化醋酸，形成為乙醇粗製品；和下游 化區分離至少-部份乙雜製品形成為—支衫支衍生物物流佳 為’純化區包括第-蒸娜，這將產生第―似物，其包括 和醋酸乙S旨’第-殘留物，其包括猶）^在優選的實施方式中，至少 4 201134795 -部分乙醇粗製品從反應器到第—蒸娜的停留時間從5分鐘至5 天:在-些實施方式巾，儲存槽配置在反應器和第—蒸娜之間，而 乙醇粗製品從反應器到第-蒸館塔的停留時間從！小時至5天，例如： 從1天至3天。在其它沒有儲存槽之實施方式中，乙醇粗製品從反應 器到純化區的停留時間，從1秒至H、時，例如：從5分鐘至3〇分鐘 或從5分鐘至15分鐘。 在第一實施方式中，本發明製程的步驟包括於反應器中在觸媒存在下 使醋酸氫化，縣為乙_製品m塔分離乙軸產品成為蒸氣 流和液體流；將至少-部分的顏朗下游純化區。在純化區分離 至少一部分的液體流成為至少一衍生物流。較佳為，純化區域包括第 一蒸餾塔，這將產生第一餾出物，其包括乙醇、水和醋酸乙酯，及第 一殘留物，其包括醋酸。該至少一部份的液體流從閃蒸塔到純化區之 停留時間從5分鐘至5天。 在第三實施方式中，本發明製程包括於反應器中在觸媒的存在下氫化 醋酸’形成乙醇粗製品；在閃蒸塔分離乙醇粗產品成為蒸氣流和液體 流，冷卻至少一部分液體流的溫度至0〜40。(：；引導至少一部分的液體 流至純化區，及在純化區分離至少一部分的液體流成為至少一衍生物 流。 本發明涉及從乙醇粗製品回收乙酵之製程。特別是，本發明涉及到從 乙醇粗製品回收和/或純化乙醇的製程，該乙醇粗製品較佳為於醋酸氫 化製程中在觸媒存在下形成。乙醇粗製品一旦形成是就導入純化區分 離其中所含各個成分，如乙醇，水和殘餘醋酸。 特別是’本發明的製程涉及到在純化區去除殘留醋酸之前，在乙醇粗 製品中制止和/或降低醋酸乙酯之形成。乙醇粗產品發生非催化反應， 推動乙醇粗製品到乙醇/醋酸和醋酸乙醋/水之間的平衡，如下式所示： EtOH + HOAc t; EtOAc + H20 在包括比醋酸乙酯和水更多的乙醇和醋酸的產品混合物中，例如乙酵 粗製品’這種平衡反應會導致不必要的額外醋酸乙酯和水的形成，而 損失所欲乙醇的產量。這種效應降低乙醇產率，提高廢物產出。這個 201134795 平衡反應之反應速率隨溫度上升而變大。 在首選的實施方射，乙_製品—旦形就導續倾，對包含在 乙醇粗製品中之成分加以分離。純化區產出至少—種，例如：至少有 兩種或至少三種衍㈣流。純化區從產品乙醇中分離殘留的醋酸。較 佳為，純化區包括第-顏塔，這將產生第，出物，其包括乙醇、 水和醋酸乙g旨，及第-殘留物，其包括醋酸。在這種情況下，第一顧 出物和第一殘留物可被視為衍生物流。 在另-實施方式中，通過其他純化單元，從產品乙醇中分離殘餘醋酸。 在許多化學製程巾’例如：驗塔消耗因此，減少能源消 耗的實施方式是理㈣，-種或多種膜分離單元用來純化乙醇粗製 品。較佳為，膜分離單元包括—滲透汽化膜如卿⑽如娜他麵）。 乙醇粗製品和/或-種或多贿生驗可通賴分離單元。在一實施方 式中，膜分離單元是配用蒸餾塔。在一些實施方式中，膜可替代一座 或多座，如兩座或兩座以上之蒸餾塔。使用一種或多種膜提供一種替 代蒸餾塔之低能耗分離單元。此外，利用膜分離單元可提供有利的，，， 打破"共沸物之能力’無需使用爽帶劑（entrai麵）。對於包括乙醇和水 的乙醇粗產品之應用，一種或多種膜可打破乙醇_水共沸物。乙醇_水共 沸物=制蒸解回收包含約92~96重量％乙醇的乙醇產品。膜較佳為 適合提供乙醇產品，如無水乙醇產品，具有較高的乙醇量，例如含至 少有96重量％或大於或至少有99重量％或更高的乙醇。 通常情況下，在純化區幾乎所有殘留的醋酸先自乙醇粗製品中分離和/ 或移除。一旦去除殘留醋酸，根據上述平衡反應的醋酸乙酯形成有效 地中止。根據本發明首選的實施方式，形成乙醇粗製品至在純化區分 離和/或去除殘留醋酸之停留時間保持足夠低，從而有效減少醋酸乙酯 的形成。在一些實施方式中，由於反應平衡之反應速率隨溫度上升而 變大’或者維持乙醇粗製品在足以減緩或抑制醋酸乙酯產出之溫度， 直到殘留醋酸可以有效地移走。 因此’在一實施方式中，在形成乙醇粗製品到純化區大量由此去除殘 留醋酸之間的滯留時間減少，則乙醇粗製品中醋酸乙酯含量可盡量減 低。應該指出’於純化區的具體的分離方案，可能有很大的不同。因 6 201134795 餘醋酸步驟可料純化系統的第-步驟或後續步 的時門和乙i/Γ⑽私方式’ 4目_時間段係指乙醇粗製品形成 = 至純化區的分離裝置由此清除殘留醋酸之間的 止乙醇二乙:二:疋極為气要’。因為去除殘餘醋酸的主要功能是中 責清除_醋酸s也統1=^。’如，純纖塔，這主要是負 方式中，停留時間為乙醇粗製品離開反應器103 = 進入酸清除單元(第-蒸德塔)107 (Β點）之間 天，如低於3長施方式中，乙醇粗製品較佳為有一停留時間不超過5 分鐘。就r圍t低於1小時’低於30分鐘，低於15分鐘，或低於5 j 2圍:吕，選擇性地停留時間為5分鐘至5天 從 刀鐘至3天，或從5分鐘至1λΙ、時。 伙 如第1圖所示，來自反應請之_製品在 塔_°。在氣和輕烴之後才以酸清除單元(第一蒸館 在某此方^士 1蒸塔⑽排出流也可稱為乙醇粗製品流。因此， 它被&入酸、月的特點是在於乙醇粗製品在閃蒸塔106 (點C)到 Γ粗製品可有一停留時間，不超過5天，如低於3天， 藉由·t G分鐘’倾15分鐘，或低於5分鐘。 除單元㈣時間’在狀純倾102及更具體地5丨人到酸清 ϊίΙΐΓ07之前，額外醋酸乙醋形成量也可有效地減少。 式中’反應區101緊密偶合純化區102。 部分=醇id’提供儲存槽130介於這兩區之間’例如：允許一 引入純化區1=運朗分離位置缝。全部或部分乙_製品可在 槽。乙醇酸/除單元(第一蒸顧塔卿之前，保存在儲存 佳為低於在的—個或多個儲存射停留時間較 如：從5分鐘至^ 時間，可能是從5分鐘至5天，例 的典型停5分鐘至1小時。在點C和點B之間储存槽 至1祕〇 /々日刀鐘至5天’例如：從5分鐘至3天，從5分鐘 種任意的實施方式中’於點A和點C，點C和點B之 7 201134795 間，或點A和點C及點C和點B之間均提供—個或多個儲存槽。 =些沒有儲存槽的實施方式中，和有儲存槽的情況味起來，乙醇 ，製品可能擁短的從A關B點或c _ B點之停㈣間。例如. ^一些沒有儲存槽的實施方式中，粗醋酸產品停留時間可能低於}小 例如：低於30分鐘，低於15分鐘，或低於5分鐘。就範圍而言， 舰A靡B或點C到點B的停㈣間範圍可從丨秒至丨小時，例如： 從5分鐘至30分鐘，或從5分鐘至15分鐘。 用儲存槽的實施方式t，乙醇粗製品比沒有儲存槽的的情況 下可有較長的從點A到點B _ C到點B之停留時間。例如：在一些 有用儲存槽的實施方式中，粗醋酸產品停留時間可低於過5天，^ ^天，或低於丨天。就細而言，從點A到點B或點c到點b之停 留=範圍可以從！小時至5天，例如：從i天至3天。就低限而言， 1情況的停留時間可至少有i小時，例如：至少有！天。比較有和 沒有儲存槽的停留時間’財使用儲存槽，則停留時間可至少比沒使 用儲存槽長10% ’例如：至少有25% ’至少有萬，至少有 或至少有200%。 在另：在實施方式中，如上所述，在乙醇粗製品中額外形成的醋酸乙 醋可藉由轉乙軸製品㈣產品麵度聽机，如低於贼或低 於20C，並額外或選擇性地進行控制之。就範圍而言，乙醇粗製品可 維持在溫度為0°C至40。(：，例如：從〇qC至3〇〇c，或代至2〇〇c的 溫度。溫度較佳為保持在閃蒸塔和純化區，例如：酸清除單元，之間 的溫度’例如：。在第1 _點c和點B之間的溫度…個或多個冷卻 裝^或熱交換器可來維持或降低，必要時，乙醇粗製品的溫度達 此等溫度。在-實施方式+，冷卻乙醇粗製品到這些溫度，並在一個 或多個儲存槽中保持符合上述規定的停留時間。 在-些實施方式中，乙醇姆品的溫度取決於乙雜製品在點Α到點 B或點C到點B之停留時間。例如：储乙醇粗製品在更低的溫度， 可允許更長的停留時間’也;j；會形成額外的醋酸⑽^反之，當乙醇 粗製品沒有冷卻或保持在較高溫度下，可能會更快形成額外的醋酸乙 S曰因此’為了避免額外的醋酸乙酷形成，較佳為停留時間較短。 8 201134795 此外，當乙醇粗製品的溫度上升，非催化反應速率會增大。例如：隨 著管路115中乙醇粗製品的溫度從代上升到21°C，醋酸乙酯每小時形 成率會增加約0.01重量％至約〇〇5重量％。因此，在一實施方式中， 於官路115或任意的儲存槽中液體成分的溫度維持在低於21〇c的溫 度。 由於乙醇粗製品通常是含有豐富的乙醇和殘留醋酸，乙醇粗製品中醋 酸乙酯濃度可能有增加的趨勢，直到殘留醋酸被移除。在首選的本發 ，實施方式中，在除酸之前乙醇粗製品中醋酸乙酯比引出反應器之乙 酵粗製品巾醋酸乙S旨含量增加到不超過5重量％，例如不超過3重量 %或不超過2重#%。例如··當乙醇粗製品由反應^ 1G3排出包括5 ，量％醋酸乙酯，而被饋入酸清除單元（第一蒸餾塔107)的乙醇粗製 品，佳為包括;^超過1G重量％之醋酸乙醋。較佳為，在反應器和酸清 除單元之間實質上沒有形成額外的醋酸乙酯。 本發明的實施方式可偷卫業細，缝壯可行的纖回收乙醇。 合適的氫化觸媒包括金屬觸媒，其包含第―金屬和任意的__種或一種 以上的第二金屬’第三金屬或其他金屬，隨意承載於娜支樓體上。 第-金屬和«的第二金屬和第三金屬選自包含元素週期表IB、皿、 IIIB、IVB、VB、VIB、νπΒ，或vm族過渡金屬、爛系金屬荆系金 屬之群組或選自元素週期表IHA、IVA、VA或VIA族之群組的任何金 屬。-些典型㈣組成物中首_金屬組合包括如錫、你釕、翻/鍊、 名巴釕把/銖姑/纪、銘/鉑、始/鉻、钻/釘、銀絶、銅他、錄/紐、金 ，巴、釕/鍊及釕/鐵。典型觸媒進一步記載於美國專利號第7,6〇8,744號 、7,863,489號’與美國專利申請公開案號2〇10/0197485，其全部内 Ί實施方式中’觸媒包括第—金屬，選自包含銅、鐵、銘、錄、 為了第=選:！、鈦、鋅、鉻、銖、钥、和鎢之群組。較佳 舍盆-么思，自纪、姑、錄和.更優選為第一金屬選自翻和纪。 彳^，較佳為觸媒幅含量低於5重魏，如低於3重量 /6或低於1重量％，由於㈣貴的價格。 如上所述，相媒任意地還包括第二金屬，其通常會作為—種促進劑。 201134795 如果存在，第二金屬較佳為選自包含銅、鉬、錫、鉻、鐵、姑、奴、 鎢、鈀、鉑、鑭、鈽、錳、釕、鍊、金及鎳之群組。尤佳為，第二金 屬選自包含銅、錫'鈷、銖及鎳之群組。更佳為，第二金屬選自錫或 鍊。 如果觸媒包括兩種或更多種的金屬，例如第一金屬和第二金屬，則第 一金屬用量可從0.1至10重量％，例如從0J至5重量％，或從〇 i至 3重量％。第二金屬較佳的用量從0.1至20重量％，例如從〇1至1〇 重量％ ’或者從G.1至5重量％。對於含兩種或兩種以上金屬的觸媒而 言，兩種或更多種的金屬可能是互相的合金或可包括非合金之金' 液或混合物。 ' 較佳金屬比例可能略有不同，取決於使用在觸媒中的金屬種類。在一 些實施方式中，第一金屬對第二金屬的摩爾比較佳為1〇 :〖至丨：1〇， 例如：4 : 1 至 1 : 4，2 : 1 至 1 : 2，1.5 : 1 至丨：丨.5，或 la : i 至 i : U。 觸媒亦可包括第三金屬，第三金屬可以選自上面列出的任何第一金屬 或第二金屬，只要第三金屬不同於第一金屬和第二金屬即可。在較佳 方面，第三金屬是選自包含钻、把、訂、銅、鋅、鉑、錫及銖之群組。 尤佳為第三金屬選自鈷、鈀或釕。如果存在，第三金屬總重量在〇〇5 和4重量％，例如：〇.1至3重量％，或〇.1至2重量％ » 除了一種或更多種的金屬外，典型觸媒進一步包括支撐體或改質後的 支撐體，這意味著支撐體包括一個支撐體材料和支撐體改性劑，該改 性劑調節支撐體材料的酸度。支撐體或改質支撐體的總重量較佳為觸 媒總重量的75重量％至99.9重量％，例如：從78重量％至97重量％， 或從80重量％至95重量％。在使用改質支撐體的首選實施例方式中， 支撐體改性劑含量為觸媒總重量的0.1重量％至50重量％，例如：從 0_2重量％至25重量％，由0_5重量％至15重量％，或從1%重量至8 重量％。 適當的支撐體材料可包括’例如：穩定的金屬氧化物為基礎的支榜體 或陶瓷系支撐體。較佳的支撐體包括含矽支撐體，如二氧化石夕，氧化 矽/氧化鋁，IIA族矽酸鹽，如偏矽酸弼，熱解二氧化矽、高純度二氧化 201134795 矽及其混合物 化鈦、氧化錯 混合物。 其他的支碰’包括但不限於氧化鐵、氧她、二氧 氧化鎮、碳、石墨、高表面積石墨化炭、活性炭及其 路支舰可用支樓體改性劑改質。較佳為支撐體 如爾發性的驗性改性劑。此種的驗性改性劑，例 驗土金屬氧化物，（ii)驗金屬氧化物，㈤ 物，（viii) 1 ί ϋΒ族金屬偏石夕酸鹽，（Vii)週期表ΙΙΙΒ族金屬氧化 物和偏顧miiB族金屬偏赠鹽，及其混合物之群組。除氧化 和i:= 卜’其他類型的改性劑包括侧、亞硝酸鹽、醋酸鹽 納，^於本發明實施方式中。較佳為支㈣改性継自包含 ^ 及鋅的氧化物和偏碎酸鹽，以及任何上述的 之群組。為支賴改性劑切_，尤佳為偏石夕酸弼 她侧咖侧，触㈣,的财 ίΐΐΐ氧切支揮體材料是SS61138高表面（hsa)的二氧化石夕觸 寒載體(Saint-Gobain NorPro公司）。此SS01138二氧化石夕包含約％重 ，的高表面積二氧化碎；表面積約25G平柿克；以汞式孔隙分析 儀測定射位孔徑約12奈米，平均孔_躺1Q立方鮮/克；而堆 積密度（packingdensity)約0.352公克/立方厘米（二碎/立方呎）。 較佳的氧化梦/氧化銘支擇體材料是KA·⑽二氧化碎（Sud Chemie公 司），具有標稱直徑約5毫米，密度約0.562克/毫升，吸收度約〇 583 克水/克支撐體’表面積約16G 175平方米/克’和孔隙體積（p〇re volume)約 0.68 毫升/克。 對此領域之熟悉技藝者即知選擇支撐體材料，使得該觸媒體系在形成 乙醇的製程條件下具有適當活性，選擇性和穩定強勁性。 觸媒的金属可分散在整個的支撐體，包覆在支撐體的外層（似雞蛋殼) 或裝飾在支撐體的表面上。 本發明觸媒組成物較佳為改性支撐體浸潰金屬而得，但其他製程，如 化學氣相沉積也可使用。ϋ：樣的浸潰技術描述在美國專利號7,6〇8,744 11 201134795 和7,863,489，與美國專利申請公開案號2010/0197485，其全部内容在 此納入參考。 根據一本發明實施方式之醋酸氫化成乙醇製程，可使用對此領域之熟 悉技藝者所知之多種配置：固定床反應器或流化床反應器。在許多本 發明之實施方式中，可以使用"絕熱"反應器，也就是說，很少有或根本 沒有必要在反應區通入内部管道加熱或除熱。在其它實施方式中，徑 向流動反應器或反應器組，或一系列蒸餾塔的反應器可以使用，其具 熱交換，淬火’或引進更多的進料。另外，可以使用具有傳熱介質之 管殼式反應器。在許多情況下，反應區可安置在一個容器或一系列蒸 餾塔的容器，其中介入熱交換器。 在首選的實施方式中，觸媒用於固定床反應器中，反應器例如呈管道 或管形狀，其中反應物通常以蒸氣的形式，傳遞或通過觸媒。可以採 用其他反應器，如流化或奔放床反應器。在某些情況下，氫化觸媒可 同時配用惰性物料’以調節反應物流通過觸媒床之壓降和反應物與觸 媒顆粒的接觸時間。 氫化反應可以在液相或氣相進行。較佳為在下列情況下進行氣相反 應。反應溫度可介於125°C至350°C，例如：從200。(：至325。(：，從225°C 至30(TC左右，或從250。(：至約300°C。壓力範圍從1〇千帕（kpa)至 3,000千帕（約1.5至435 psi)，例如：從50千帕至2,300千帕，或從 100千帕至1，500千帕。反應物饋入反應器的"氣體每小時空間速度,， (GHSV)可為大於500/小時，例如：大於〗，〇〇〇/小時，大於2 5〇〇/小 時’甚至大於5,〇〇〇/小時。就範圍而言，GHSV可以從5〇/小時至5〇,〇〇〇/ 小時，例如：從500/小時至30.000/小時，從} 〇〇〇/小時至1〇 〇〇〇/小時， 或1，000/小時至6,5〇〇/小時。 在本發明製程的另-方面’氫化係在足以克服在所選空間速度通過催 化^的壓降之壓力下進行，雖然沒有翻較高的壓力，但不言而喻， 在间空間速度’例如：5，_/小時，或6,5⑻/小時通過反應器床可能會 遇到相當大的壓降。 ，然每摩爾騎反應雜兩摩爾氫氣，生產_摩㈣乙醇，實際在進 ;斗流中氫氣對醋酸之摩爾比可能會有所不同：約1〇〇 : i至i :咖，例 12 201134795 :二…至…。，從20:1至1:2,或從⑴…：卜最佳 為風氣對醋酸之摩H比大於2 :卜例如：大於4 :丨或大於8小 不同，料崎4，_，反應器，溫 it力等變數。典型的接觸時間範圍從不到1秒，到幾個小時以上， ^用固定床以外的觸媒系統，氣相反應首選接觸時間為在至少有約 场和100秒之間’例如：從0 3至8〇秒或〇 4至3〇秒。 =於本發明製程的原料，醋酸和氫氣，可能來自任何合適的來源，包 括天然氣、石油、煤炭、生物料等。舉例而言，通過甲_基化、乙 醛氧化、乙烯氧化、氧化發酵、厭氧發酵等，可生產醋酸。舉例而士， 通過甲醇幾基化、乙路氧化、乙烯氧化'氧化發酵、厭氧發酵等，可 生產醋酸。由於石油和天然錢得波動，價格忽起忽落，用於從備用 碳源生產醋酸和巾間體如曱醇和—氧化碳的方法，已引起越來越大的 興趣。特別是’當石油價格比天織較高時，由任何合適的碳源所衍 生的合成氣（"syngas")生產醋酸可能成為有利。例如美國專利第 6,232,352號揭露改裝甲醇麻以生產醋酸的方法，可納入做為參考。通 過改裝曱醇廠，可顯著減少或大部分消除新醋酸廠產生一氧化碳的所 需的大型資本成本。由曱醇合成循環轉出全部或部分合成氣，並提供 給回收一氧化碳和氫氣單元，然後再用於生產醋酸。除了醋酸，這個 製程也可以用來製造本發明有應用關連之氫氣。 適合於生產醋酸之曱醇羰化製程記載於美國專利號7,2〇8,624、 7，115,772、7,005,54卜 6,657,078 ' 6,627,770、6，143,930、5,599,976、 13 201134795 在此納入參考。 在一任意的實施方式中’饋入氫化反應之醋酸也可包括其他羧酸和酐 類，以及乙醛和丙酮。較佳為合適的醋酸進料流包括一種或多種化合 物選自包含醋酸、醋酐、乙醛、醋酸乙酯及其混合物之群組。這些其 他的化合物也可在本發明製程中氫化。在一些實施方式中，羧酸，如 丙酸或其酸酐’也許有利於丙醇之生產。 另外，蒸氣形式的醋酸可從甲醇羰化單元之閃蒸塔取出，直接以粗製 品形式採用，參閱美國專利第6,657,078號中所描述，其全文在此納入 參考。蒸氣粗製品可直接饋入乙醇合成反應區，而不需要冷凝醋酸和 輕餾份或移除水，節約整體處理成本。 醋酸可在反應溫絲發’而蒸狀醋酸可隨著狀以未轉或用相對 惰性之承載氣體’如氮氣'氬氣、氦氣和二氧化碳等等稀釋之方式馈 入反應器。為反應能在氣相中運行，在系統中應控制溫度，使得它不 低於醋酸n在-個實财^巾在特㈣壓力下猶可在彿點、、气 化，然後蒸發的暖可進-步加制反應器人口溫度^在另一實施方 式中’醋酸藉由通過氫氣，循環氣，另-合義氣體或其混合物，在 低於醋酸義之溫度下’獅成微統狀態，從而㈣酸加濕載氣， 其^是加熱混合氣制反絲人口溫度。優選地，在溫度等於或低於 耽’通過氩氣和/或循環氣使醋酸汽化，其次是加熱合併後氣體流到 反應器入口溫度。 特別是，醋酸氫化可達職好的轉化率和良好的乙醇_率 ^發明的目的，”轉化率是指在進料中醋酸轉化為_以^化 :物之比^轉化率係佔進料中醋酸摩爾數之百分率表示^轉 在10%以上，例如：至少有20%，至少有40%，至少有 ί 少有^或至少有_。雖然觸媒具有㈣_化率“ =二如在至付8。％或至少有9。％，但在—些實施方式中， Ζ尚選擇率’雌低的轉化率可以接受4許多情 理解，通過適當的魏錢使職大的絲 補低選擇賴更難。 ㈣f轉化率，但彌 201134795 應舰姻每-種由錯酸 為，觸雜織咖_ w 6 ;== 所使用的術語‘‘乙氡基化合物“，具丄= 路和醋酸乙.較佳為乙醇的選擇率在80%以上，例如：S少有娜 =少:本發明實施方式中’亦較佳為對不期待的產品，如 曱烧，乙院和-氧化碳有較低之選神。這些不期待產品的選擇率是 低於4% ’如低於2臟低於1%。較佳為在氫化過程中沒有檢測至 這些不期待產品。在-些本發明實财式巾，胁形鱗低，通常低 於2/6 ’往往疋低於1%，而且在許多情況下低於〇5%的醋酸通過觸 媒轉換為烷烴，而烷烴除了作為燃料外沒有多大價值。 “產率”是指氫化過程中每公斤觸媒每小時所形成特定的產品 ，如乙醇， 的，數。產率每公斤觸媒每小時至少有200克乙醇，例如：每公斤觸 媒每小時至少有4〇〇克乙醇或較佳為乙醇至少有6〇〇克。以範圍而言， 產率較佳為每公斤觸媒每小時有200至3，_克的乙醇，例如：4〇〇至 2,5〇〇克或600至2,000克的乙醇。 在不同的實施例方式中’由氫化製簡得的乙醇粗製品，在任何後續 加工-純化和分離之前，通常包括未反應的醋酸，乙醇和水。本文中所 使用的術語“乙醇粗製品“是指任何包括5重量％至7〇重量％乙醇和5 重量％至35重量％水的組成物。在一些典型實施方式中，乙醇粗製品 包括乙醇’其含量佔乙醇粗製品總重量之5重量％至7〇重量％，例如： 1〇重量％至60重量％，或從15重量％至5〇重量％，該百分率係對乙 醇粗製品總重量而言。較佳為乙醇粗製品含有至少1〇重量％乙醇，至 少15重量％乙醇或至少2〇重量％的乙醇。乙醇粗製品通常將進一步 包括未反應醋酸’視轉化率而定，其重量例如低於90%，例如：重量 低於80%或低於7〇重量％。就範圍而言，未反應醋酸含量從〇至9〇 重量％ ’例如：從5至80重量％，從15至70重量％，從20至70重 量％或從25至65重量％。由於水是反應製程中形成的，乙醇粗製品 一般包括水’例如：含量從5重量％至35重量％，例如：‘從10重量 15 201134795 %至30重量％或10重量％至26重量％。醋酸乙g旨也可能是醋酸氫化 反應或通綱反應產生的。在這讀施方式中，乙醇粗製品包括醋酸 乙醋’其含量從〇%至20重量％ ’例如：從〇重量％至15重量％，從 1重量％至I2重量％ ’或3重量％至1G重量.通過副反應可能也會 產生乙路。在ϋ·些實施方式中，乙醇粗製品包括乙路，其含量從〇重 量％至10重量％ ’例如.從0重量％至3重量％，從〇 i重量％至3 重量％，或0.2重量％至2重量％。其他成分，例如：醋、鱗、酿、嗣 類、烷烴、二氧化碳，如果檢測到，其總含量可低於1()重量％，例如： 低於6重量％，或低於4重量％。就範圍而言，乙醇粗製品組成物可 能包括其他成分，其含量從0.1重量％至1〇重量％，例如：從〇1重 量％至6重量％ ’或從G.l f量％至4重量％。乙雜製品組成範圍典 型例載於表1。 1 表1 二醇粗製品之組成 成分 濃度(重量％) 濃度(重量〇/〇) 濃度(重量 濃度(重量％) 乙醇 5至70 10 至 60 15 至 50 25 至 50 醋酸 0至90 5至80 15 至 70 20 至 70 水 5至35 5至30 10 至 30 10 至 26 醋酸乙酯 0至20 0至15 1至12 3至10 乙醛 0至10 0至3 0.1 至 3 〇_2 至 2 其他 0.1 至 10 0.1 至 6 0.1 至 4 —--- 第1圖顯示-種按本發_-實施方式錢化纽丨⑻適合氫化醋酸 和自乙醇粗製品中分離乙醇。系統100包括反應區1〇1，純化區1〇2， 及位於反應區ιοί和純化區102之間的儲存槽13〇β反應區1()1包括反 應，103 ’氫氣饋入管路1〇4和醋酸饋入管路1〇5。純化區1〇2包括閃 X塔106 ’第-蒸飽& 1〇7，第二蒸顧塔1〇8和第三蒸館塔。氮氣 和醋酸分別通過管路104和管路105供給到蒸發器11〇，在管路ui中 建立氣趙麟流引到反應H 1G3。在—實施方式巾，管路1G4和管路 105可以結合，共同送入蒸發器11〇，例如：在一進料流中同時含有氫 201134795 氣在g路ni蒸汽進料流的溫度較佳為線從ι〇〇β〇至⑽。c， 至31〇°C ’或15〇°C至3〇〇°C。任何不發進料將從蒸 攸川2丨移出，如第1圖所示，可再回收。此外，雖然第1圖顯示管 反應器1〇3的頂部，管路111，可引入反應器103側邊，上 部或底部。反應區1()1之進—步修改和附加元件介紹如下。 反，,1。3包含觸媒’其是用於_，較佳為醋酸的氫化。在一實施 —或錄賴床（未顯示）可以絲紐娜免於接觸到在 —循軸中所含之毒物或不期待的雜質。這樣的保護床可用 在蒸氧或液體流4適的保護床材料為文獻上已知，包括，例如：碳、 氧化㉟、喊或_。—方面，倾床介質用來捕獲特定 ώ其’如硫或鹵素。在氫化製程中’較佳為不斷地從反應$ 103經 g路1曰12取出乙醇粗製品流。乙醇粗製品流可冷凝並送到閃蒸塔 於疋又k供蒸氣流和液體流。在一實施方式中，閃蒸塔1〇6較佳 為操作/m度從50 C至5GG°C，例如:從7G°C至40〇。〔或1GG°C至350。〇 在實，方式中，閃蒸塔106的壓力較佳為從50千帕至2,000千帕， 例如.從75千帕至i，·千帕或從1〇〇至I·千帕。在一優選的實 施方式^，Pj蒸塔1〇6的溫度和壓力類似反魅1〇3的溫度和壓力。 由閃蒸'1〇6逸出的蒸氣流可包括氫氣及破氫化合物，其可加以清除 和/或經由f路113送酬反應區ω卜如第i _示，蒸氣流返回部 刀經由壓縮機114，和氫氣進料結合一起送入蒸發器11〇。 在-實施方式中，將閃蒸塔1〇6排出的液體作為進料組成物經由管路 =5泵送到第—蒸餾塔1〇7其也被稱為酸分離單元。經由管路us例如 J饋^第-蒸顧塔1〇7的側邊。管路115的内容通常大致綱於直接從 反應器，得的產品’並可以實際上也定性為—種乙醇粗製品。 如上，述’儲存槽130置於反應區101和純化區102之間。於管路115 中一部分或全部的液體進料可經由管路131通向儲存槽130,並經由管 路1：>2回到官路115。儲存在儲存槽130的部分液體進料可以經由管路 132直接饋入酸清除單元(第一蒸餾塔)丨〇7,或和管路ιΐ5的液體進料之 其餘部分共同馈入β 任意地，在管路112中部分的乙醇粗製品也可送入獨立的儲存槽（未顯 17 201134795 示）。 ，然第1 _示-個儲存槽’也可考慮使賴外的儲存槽。例如：若 管路112乙醇粗製品和管路115液體進料要分開儲存，則可以使用額外 的儲存槽。 =了健存槽13〇,在管路m乙醇粗製品和/或在管路m液體進料之溫 =’於狀酸清除單元(第―_塔师之料予轉或將其冷卻。在 路,112或115的乙醇粗製品可維持溫度或冷卻，或儲存槽13〇可維持 f冷卻溫度’例如：低於贼，如低於赃或低於耽，或就範圍而 言’從0T至40T，例如：從〇。〇：至3〇τ或〇τ至2〇〇c。如果管路 112和/或管路m溫度超過這些溫度，管路ιΐ2和/或出的内容物可 根據需要進行冷卻。—種衫種傳《和制儀表，可配合冷卻裝置 以保持溫度。 在實施方式中，管路出的内容物大致和從反應器獲得的乙醇粗製品 相同’只要送進酸清除單元(第一蒸館塔)1〇7之進料中醋酸乙醋的不會 比反應器取出乙雜製品巾猶㈣含量增加超過5重频以上，例 ^不超過3重量％或2重量^此外，賴進料可能不同於乙醇粗 製品’因為組成物較佳騎f上沒有氫氣，二氧化碳，甲烧和乙院， 2上這些都被閃蒸塔106移除。管路115内容物典型組成列於表2。 它應該被理解為該管路115可能包含其他未列出的成分，如在進料中的 rii 公。 18 201134795 濃度(重晋％、 表2 進料組成 濃度(重量％)201134795 Code Description~~ 117 Pipeline 118 Pipeline~~: 120 Pipeline 121 Pipeline 130 Storage Tank 131 Pipeline 132 Pipeline 5. If there is a chemical formula in this case, please reveal the best indication of the characteristics of the invention. BRIEF DESCRIPTION OF THE INVENTION: PRIORITY PRIORITY The present invention claims priority based on US Patent Provisional No. 61/300,815 filed on February 2, 2010, and US patent filed on May 7, 2010. U.S. Patent Application Serial No. U.S. Patent Application Serial No. No. No. No. No. No. No. No. No. No. No. No. No. No. No. No. No. No. No. No. No. No. No. No. No. BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a process for generally producing an ethanol process, and particularly for the formation of ethyl acetate in the acetylation process of acetic acid to maximize the formation of ethanol. 201134795 [Prior Art] The ethanol used in the industry is traditionally derived from petrochemical feedstocks such as petroleum, natural gas and coal, from feed intermediates such as synthetic gas, or from starchy feedstock materials or cellulosic feedstock materials such as Corn or sugar cane, produced. Traditional methods from petrochemical feedstocks and from cellulosic feedstocks produce ethanol, including acid catalyzed hydration of ethylene, homologation of methanol, direct alcohol synthesis and "Fischer-Tropsch synthesis". Unstable petrochemical feedstock materials The price will cause the cost of the traditional way of producing ethanol to fluctuate. When the price of the raw material increases, the demand for ethanol from the alternative source will be more demanded. The powdered raw material and the cellulose raw material can be converted into ethanol via fermentation. However, usually fermentation It is used in the production of consumer ethanol, which is used as a fuel or consumer. In addition, the fermentation of the powder or cellulose raw material competes with the food source to limit the amount of ethanol that can be used in industrial production. Or the reduction of other carbonyl hydrazine compounds for the production of ethanol has been extensively studied, as well as various combinations of catalysts, supports and operating conditions are mentioned in the literature. Alkanoic acids, such as acetic acid, and other compounds are held in the county for ethanol or In its secondary anti-age county is ethanol hydrazine. For example: in the hydrogenation reaction and / or its subsequent side reactions, the ester Produced with ethanol and/or water to form an azeotrope, which is difficult to separate. These impurities may limit ethanol production and may require expensive and complicated purification systems to separate impurities from ethanol. In addition, 'when the conversion is incomplete' the unreacted acid stays in the crude ethanol towel. These residual acetic acid can promote more harmful adverse reactions over time, and this residual acid must be removed from the crude ethanol product. In addition, purified ethanol can be produced. 曰 Therefore, there is still a need to improve the technology for recovering ethanol from crude products which are reduced by acid production such as acetic acid, and/or other silk compounds. In addition, process 2 needs to be improved. In order to reduce or suppress impurities formed by adverse side reactions. [Summary of the Invention] In the first embodiment, the present invention is a process for purifying a crude product of a race (10) in a reactor in the presence of (iv) to hydrogenate acetic acid to form ethanol. The crude product; and the downstream zone are separated at least - part of the ethylidene product is formed as - the branch of the derivative stream is preferably a 'purification zone including the first - steamed na, which will produce "Immediate, which includes and the acetic acid, "the residue - the residue, including the helium" ^ In a preferred embodiment, at least 4 201134795 - part of the crude ethanol from the reactor to the first - steaming residence time from 5 Minutes to 5 days: In some embodiments, the storage tank is disposed between the reactor and the first steaming, while the residence time of the crude ethanol product from the reactor to the first steaming tower is from ! hours to 5 days, for example : from 1 day to 3 days. In other embodiments without a storage tank, the residence time of the crude ethanol product from the reactor to the purification zone is from 1 second to H, for example, from 5 minutes to 3 minutes or from 5 minutes to 15 minutes. In the first embodiment, the steps of the process of the present invention include hydrogenating acetic acid in a reactor in the presence of a catalyst, and the county is a product of a vapor stream and a liquid stream; At least part of the Yanlang downstream purification zone will be used. At least a portion of the liquid stream is separated in the purification zone into at least one derivative stream. Preferably, the purification zone comprises a first distillation column which will produce a first distillate comprising ethanol, water and ethyl acetate, and a first residue comprising acetic acid. The residence time of the at least a portion of the liquid stream from the flash column to the purification zone is from 5 minutes to 5 days. In a third embodiment, the process of the present invention comprises hydrogenating acetic acid in a reactor in the presence of a catalyst to form a crude ethanol product; separating the crude ethanol product into a vapor stream and a liquid stream in a flash column to cool at least a portion of the liquid stream. The temperature is from 0 to 40. (:; directing at least a portion of the liquid to the purification zone, and separating at least a portion of the liquid stream in the purification zone into at least one derivative stream. The present invention relates to a process for recovering ethylene glycol from a crude ethanol product. In particular, the invention relates to a process for recovering and/or purifying ethanol from a crude ethanol product, which is preferably formed in the presence of a catalyst in a hydrogenation process of acetic acid. Once formed, the crude ethanol product is introduced into a purification zone to separate various components contained therein, such as ethanol. , water and residual acetic acid. In particular, the process of the present invention involves stopping and/or reducing the formation of ethyl acetate in a crude ethanol product prior to removal of residual acetic acid in the purification zone. The crude ethanol product undergoes a non-catalytic reaction that promotes crude ethanol. The equilibrium between the product and ethanol/acetic acid and ethyl acetate/water is as follows: EtOH + HOAc t; EtOAc + H20 in a product mixture comprising more ethanol and acetic acid than ethyl acetate and water, eg B The fermented crude product's equilibrium reaction leads to unnecessary formation of additional ethyl acetate and water, which loses the yield of the desired ethanol. Reduce the ethanol yield and increase the waste output. The reaction rate of the 201134795 equilibrium reaction increases with the temperature rise. In the preferred implementation, the B-products are continuously poured and are included in the crude ethanol product. The components are separated. The purification zone produces at least one species, for example, at least two or at least three derivative streams. The purification zone separates the residual acetic acid from the product ethanol. Preferably, the purification zone comprises a phenanthrene column, which will The first and the excipients are produced, which include ethanol, water, and acetic acid, and the first residue, which includes acetic acid. In this case, the first drug and the first residue can be regarded as a derivative stream. In another embodiment, the residual acetic acid is separated from the product ethanol by other purification units. In many chemical processing rolls, for example, the column is consumed. Therefore, the embodiment for reducing energy consumption is (4), one or more membrane separation units. It is used to purify crude ethanol. Preferably, the membrane separation unit comprises a pervaporation membrane such as qing (10) such as Nata. Alcohol crude products and / or - or more than a bribe can be relied on the separation unit. In one embodiment, the membrane separation unit is equipped with a distillation column. In some embodiments, the membrane may be substituted for one or more, such as two or more distillation columns. A low energy separation unit of an alternative distillation column is provided using one or more membranes. In addition, the use of a membrane separation unit can provide an advantageous, "capability of azeotrope' without the use of an entrai surface. For applications of crude ethanol products including ethanol and water, one or more membranes can break the ethanol-water azeotrope. Ethanol_water azeotrope = by distillation to recover an ethanol product containing about 92 to 96% by weight of ethanol. The membrane is preferably suitable for providing an ethanol product, such as an anhydrous ethanol product, having a relatively high amount of ethanol, e.g., ethanol having at least 96% by weight or greater than or at least 99% by weight or greater. Typically, almost all of the residual acetic acid in the purification zone is separated and/or removed from the crude ethanol product. Once the residual acetic acid is removed, the formation of ethyl acetate according to the above equilibrium reaction is effectively stopped. According to a preferred embodiment of the invention, the crude ethanol product is formed until the residence time of the separation and/or removal of residual acetic acid is kept sufficiently low to effectively reduce the formation of ethyl acetate. In some embodiments, the reaction rate due to the equilibrium of the reaction becomes larger as the temperature rises' or the crude ethanol product is maintained at a temperature sufficient to slow or inhibit the production of ethyl acetate until the residual acetic acid can be effectively removed. Thus, in one embodiment, the residence time between the formation of the crude ethanol product to the purification zone and the removal of residual acetic acid thereby reducing the ethyl acetate content in the crude ethanol product can be minimized. It should be noted that the specific separation schemes in the purification zone may vary widely. Because of the 6 201134795 residual acetic acid step, the first step or the subsequent step of the purification system can be used to clean the residue. The 4th_time period refers to the formation of crude ethanol = the separation device to the purification zone to remove the residue. Stopping ethanol between acetic acid: two: 疋 is extremely angry. Because the main function of removing residual acetic acid is to remove _ acetic acid s also unified 1 = ^. 'For example, pure fiber tower, which is mainly in the negative mode, the residence time is the crude ethanol product leaving the reactor 103 = entering the acid removal unit (the first - steamed tower) 107 (Β point) between days, such as less than 3 long In the embodiment, the crude ethanol product preferably has a residence time of no more than 5 minutes. In the case of r circumference t less than 1 hour 'below 30 minutes, less than 15 minutes, or less than 5 j 2 circumference: Lu, selective residence time is 5 minutes to 5 days from knife to 3 days, or from 5 Minutes to 1λΙ, hour. As shown in Figure 1, the product from the reaction is in the tower _°. After the gas and light hydrocarbons are used, the acid removal unit (the first steaming plant in a certain side of the steaming tower (10)) can also be called the crude ethanol product stream. Therefore, it is characterized by &acid; The crude ethanol product may have a residence time in the flash column 106 (point C) to the upset product, no more than 5 days, such as less than 3 days, by 'tg minutes' for 15 minutes, or less than 5 minutes. In addition to the unit (d) time 'in the pure pour 102 and more specifically 5 to the acid clear ϊ ΙΐΓ 07, the amount of additional ethyl acetate formation can also be effectively reduced. In the formula 'reaction zone 101 tightly coupled to the purification zone 102. Part = alcohol Id' provides a storage tank 130 between the two zones', for example: allowing a lead-in purification zone 1 = Yunlang separation position seam. All or part of the B-product can be in the tank. Glycolic acid / division unit (first steam tower Before Qing, the storage time of the storage is better than the storage time of one or more storage shots, such as from 5 minutes to ^ time, which may be from 5 minutes to 5 days, for example, the typical stop is 5 minutes to 1 hour. Store the slot between point C and point B to 1 tip/day knife to 5 days' for example: from 5 minutes to 3 days, from 5 points In any of the embodiments, one or more storage slots are provided between point A and point C, point C and point B 7 201134795, or between point A and point C and point C and point B. In some embodiments without storage tanks, and in the case of storage tanks, ethanol, products may be short between A and B points or c _ B points (four). For example.  ^ In some embodiments without a storage tank, the residence time of the crude acetic acid product may be less than a small amount, for example: less than 30 minutes, less than 15 minutes, or less than 5 minutes. In terms of scope, the range between the ship A 靡 B or the point C to the point B (four) can range from leap seconds to 丨 hours, for example: from 5 minutes to 30 minutes, or from 5 minutes to 15 minutes. With the embodiment t of the storage tank, the crude ethanol product can have a longer residence time from point A to point B _ C to point B than without the storage tank. For example, in some embodiments of useful storage tanks, the residence time of the crude acetic acid product can be less than 5 days, ^^ days, or less than days. In more detail, the stop from point A to point B or point c to point b = range can be from! Hours to 5 days, for example: from i days to 3 days. In terms of the lower limit, the residence time of 1 case can be at least i hours, for example: at least! day. Comparing with and without the storage tank residence time, the residence time can be at least 10% longer than the unused storage tank', for example: at least 25% 'at least 10,000, at least or at least 200%. In another embodiment, as described above, the ethyl acetate formed separately in the crude ethanol product may be obtained by translating the product (4), the product is less than a thief or below 20C, and additionally or alternatively Control it sexually. In terms of range, the crude ethanol product can be maintained at a temperature of from 0 °C to 40 °C. (:, for example, from 〇qC to 3〇〇c, or to a temperature of 2〇〇c. The temperature is preferably maintained at a temperature between the flash column and the purification zone, for example, an acid removal unit, for example: The temperature between the 1st point c and the point B... one or more cooling devices or heat exchangers can be maintained or lowered, if necessary, the temperature of the crude ethanol product reaches these temperatures. In the embodiment + Cooling the crude ethanol product to these temperatures and maintaining a residence time in accordance with the above specified conditions in one or more storage tanks. In some embodiments, the temperature of the ethanol product depends on the point in point B to point B or The residence time from point C to point B. For example: crude ethanol stored at a lower temperature, allowing a longer residence time 'also; j; will form additional acetic acid (10) ^ Conversely, when the crude ethanol product is not cooled or maintained At higher temperatures, additional ethyl acetate may be formed more quickly. Therefore, in order to avoid additional formation of acetic acid, it is preferred to have a shorter residence time. 8 201134795 In addition, when the temperature of crude ethanol increases, non-catalytic The reaction rate will increase. For example: with The temperature of the crude ethanol product in line 115 increases from generation to 21 ° C, and the formation rate of ethyl acetate increases by about 0. 01% by weight to about 5% by weight. Thus, in one embodiment, the temperature of the liquid component in the official road 115 or any storage tank is maintained at a temperature below 21 〇c. Since the crude ethanol product is usually rich in ethanol and residual acetic acid, the concentration of ethyl acetate in the crude ethanol product may increase until the residual acetic acid is removed. In a preferred embodiment, in the embodiment, the ethyl acetate in the crude ethanol product before the acid removal is increased to not more than 5% by weight, for example, not more than 3% by weight, based on the ethyl acetate raw material of the extraction reactor. Or no more than 2 weights #%. For example, when the crude ethanol product is discharged from the reaction ^1G3, including 5, the amount of ethyl acetate, and the crude ethanol product fed to the acid removal unit (the first distillation column 107), preferably includes; ^ more than 1 G% by weight Acetate acetate. Preferably, no additional ethyl acetate is formed between the reactor and the acid removal unit. The embodiment of the invention can steal the fine industry and sew the viable fiber to recover the ethanol. Suitable hydrogenation catalysts include a metal catalyst comprising a first metal and any or more of a second metal 'third metal or other metal, optionally carried on the Nattrium building. The second metal and the third metal and the third metal are selected from the group consisting of IB, Dish, IIIB, IVB, VB, VIB, νπΒ, or vm transition metals, rotten metal genus metals or Any metal from the group of the IHA, IVA, VA or VIA family of the Periodic Table of the Elements. - Some typical (four) composition of the first _ metal combination including such as tin, you 钌, turn / chain, Ming Ba 钌 / 铢 Gu / Ji, Ming / Platinum, start / chrome, drill / nail, silver, copper, Record / New Zealand, Gold, Pakistan, 钌 / chain and 钌 / iron. A typical catalyst is further described in U.S. Patent Nos. 7,6,8,744, 7,863,489, and U.S. Patent Application Publication No. 2,10/01,97, 485, the entire disclosure of which is incorporated herein by reference. Contains copper, iron, Ming, recorded, for the first choice:! , a group of titanium, zinc, chromium, bismuth, molybdenum, and tungsten. It is better to think about pots - thinking, self-discipline, aunt, recorded and. More preferably, the first metal is selected from the group consisting of Turnip.彳^, preferably the catalyst medium content is less than 5 wei, such as less than 3 weight / 6 or less than 1% by weight, due to (four) expensive price. As noted above, the phase media optionally includes a second metal which will generally act as a promoter. 201134795 If present, the second metal is preferably selected from the group consisting of copper, molybdenum, tin, chromium, iron, australis, tungsten, palladium, platinum, rhodium, ruthenium, manganese, osmium, chains, gold, and nickel. More preferably, the second metal is selected from the group consisting of copper, tin 'cobalt, antimony and nickel. More preferably, the second metal is selected from the group consisting of tin or a chain. If the catalyst comprises two or more metals, such as a first metal and a second metal, the first metal may be used in an amount of from zero. 1 to 10% by weight, for example, from 0 J to 5% by weight, or from 〇 i to 3% by weight. The second metal is preferably used in an amount of from 0. 1 to 20% by weight, for example from 〇1 to 1% by weight ’ or from G. 1 to 5% by weight. For a catalyst containing two or more metals, the two or more metals may be alloys of each other or may comprise a non-alloyed gold liquid or mixture. The preferred metal ratio may vary slightly depending on the type of metal used in the catalyst. In some embodiments, the molar ratio of the first metal to the second metal is preferably 1 〇 : 丨 to 〇: 1 〇, for example: 4 : 1 to 1 : 4, 2 : 1 to 1 : 2, 1. 5 : 1 to 丨: 丨. 5, or la : i to i : U. The catalyst may also include a third metal, which may be selected from any of the first or second metals listed above, as long as the third metal is different from the first metal and the second metal. In a preferred aspect, the third metal is selected from the group consisting of drill, handle, set, copper, zinc, platinum, tin, and antimony. More preferably, the third metal is selected from the group consisting of cobalt, palladium or rhodium. If present, the total weight of the third metal is 〇〇5 and 4% by weight, for example: 〇. 1 to 3 wt%, or 〇. 1 to 2% by weight » In addition to one or more metals, a typical catalyst further comprises a support or a modified support, which means that the support comprises a support material and a support modifier. The agent adjusts the acidity of the support material. The total weight of the support or the modified support is preferably from 75% to 99% by weight based on the total weight of the catalyst. 9% by weight, for example: from 78% by weight to 97% by weight, or from 80% by weight to 95% by weight. In a preferred embodiment in which the modified support is used, the support modifier content is 0. 1% by weight to 50% by weight, for example, from 0-2% by weight to 25% by weight, from 0% by weight to 15% by weight, or from 1% by weight to 8% by weight. Suitable support materials can include, for example, a stable metal oxide based support or ceramic support. Preferred supports include ruthenium-containing supports such as cerium oxide, cerium oxide/alumina, Group IIA cerates, such as bismuth bismuth citrate, pyrogenic cerium oxide, high purity dioxide 201134795 hydrazine and mixtures thereof. Titanium, oxidized mixture. Other supports include, but are not limited to, iron oxide, oxygen, oxidized towns, carbon, graphite, high surface area graphitized carbon, activated carbon, and road support vessels that can be modified with a building bulk modifier. Preferably, the support is an inotropic modifier. Such an organic modifier, such as a soil metal oxide, (ii) a metal oxide, (5), (viii) 1 ί steroid metal bismuth, (Vii) periodic table ΙΙΙΒ metal oxidation And a group of mieB group metal partial salts, and mixtures thereof. Other types of modifiers including oxidation and i:= Bu's include side, nitrite, acetate, in embodiments of the invention. Preferably, the (4) modified ruthenium consists of oxides and metatheids of zinc and zinc, as well as any of the groups described above. Cut the _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ Saint-Gobain NorPro). The SS01138 dioxide dioxide comprises about 6% by weight of high surface area oxidized granules; the surface area is about 25 gram per gram of persimmon; the pore size of the pores is about 12 nm measured by a mercury pore analyzer, and the average pore size is 1 Q cubic gram per gram; And the packing density is about 0. 352 grams / cubic centimeter (two broken / cubic 呎). The preferred oxidized dream/oxidized indwelling material is KA·(10) dioxide (Sud Chemie) having a nominal diameter of about 5 mm and a density of about 0. 562 g / ml, absorbance of about 583 grams of water / gram of support body surface area of about 16G 175 square meters / gram ' and pore volume (p〇re volume) about 0. 68 ml / g. Those skilled in the art will recognize that the support material is selected such that the contact medium has suitable activity, selectivity and stability in the process conditions for forming ethanol. The metal of the catalyst can be dispersed throughout the support, coated on the outer layer of the support (like an egg shell) or on the surface of the support. The catalyst composition of the present invention is preferably obtained by impregnating a metal with a modified support, but other processes such as chemical vapor deposition may also be used. ϋ: The type of impregnation technique is described in U.S. Patent Nos. 7,6,8,744, 11, 2011, 349, and 7, 863, 489, and U.S. Patent Application Publication No. 2010/0197485, the entire disclosure of which is incorporated herein by reference. According to one embodiment of the invention, the hydrogenation to acetic acid process can be carried out using a variety of configurations known to those skilled in the art: fixed bed reactors or fluidized bed reactors. In many embodiments of the invention, "insulation" reactors may be used, i.e., little or no need to pass internal piping to heat or remove heat in the reaction zone. In other embodiments, a radial flow reactor or reactor train, or a series of distillation column reactors, may be used with heat exchange, quenching or introducing more feed. Alternatively, a shell and tube reactor having a heat transfer medium can be used. In many cases, the reaction zone can be placed in a vessel or a series of distillation column vessels in which the heat exchanger is interposed. In a preferred embodiment, the catalyst is used in a fixed bed reactor, for example in the form of a pipe or tube, wherein the reactants are typically passed in the form of a vapor, or passed through a catalyst. Other reactors can be used, such as fluidized or bunk bed reactors. In some cases, 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 reactants with the catalyst particles. The hydrogenation reaction can be carried out in the liquid phase or in the gas phase. It is preferred to carry out the gas reaction in the following cases. The reaction temperature may range from 125 ° C to 350 ° C, for example from 200. (: to 325. (:, from 225 ° C to 30 (about TC, or from 250. (: to about 300 ° C. Pressure range from 1 〇 kPa (kpa) to 3,000 kPa (about 1. 5 to 435 psi), for example: from 50 kPa to 2,300 kPa, or from 100 kPa to 1,500 kPa. The "gas hourly space velocity of the reactants fed into the reactor, (GHSV) may be greater than 500/hour, for example: greater than 〗, 〇〇〇/hour, greater than 2 5 〇〇 / hour 'or even greater than 5, 〇 〇〇 / hour. In terms of range, GHSV can range from 5 mph to 5 〇, 〇〇〇 / hour, for example: from 500 / hour to 30. 000/hour, from } 〇〇〇 / hour to 1 〇 小时 / hour, or 1,000 / hour to 6, 5 〇〇 / hour. In another aspect of the process of the present invention, the hydrogenation is carried out at a pressure sufficient to overcome the pressure drop at the selected space velocity by the catalyst, although without the higher pressure, it goes without saying that the inter-space velocity 'e.g. : 5, _ / hour, or 6, 5 (8) / hour through the reactor bed may encounter a considerable pressure drop. However, every mole of hydrogen is mixed with two moles of hydrogen to produce _Mo (tetra) ethanol, which is actually in the process; the molar ratio of hydrogen to acetic acid in the bucket stream may be different: about 1 〇〇: i to i: coffee, example 12 201134795 : Two...to... , from 20:1 to 1:2, or from (1)...: Bu is the best for the atmosphere of acetic acid, the H ratio is greater than 2: Bu, for example: greater than 4: 丨 or greater than 8 small difference, Qiqi 4, _, reactor , temperature it force and other variables. Typical contact times range from less than 1 second to more than a few hours. ^With a catalyst system other than a fixed bed, the preferred contact time for a gas phase reaction is between at least about 100 seconds. For example: from 0 3 Up to 8 sec or 〇 4 to 3 sec. The raw materials for the process of the present invention, acetic acid and hydrogen, may come from any suitable source, including natural gas, petroleum, coal, biomass, and the like. For example, acetic acid can be produced by methylation, acetaldehyde oxidation, ethylene oxidation, oxidative fermentation, anaerobic fermentation, and the like. For example, acetic acid can be produced by methanol radicalization, ethylene oxidation, ethylene oxidation 'oxidation fermentation, anaerobic fermentation, and the like. As oil and natural money fluctuate, prices have risen and fallen, and methods for producing acetic acid and towels such as sterols and carbon monoxide from alternate carbon sources have generated increasing interest. In particular, 'syngas produced by any suitable carbon source ("syngas") to produce acetic acid may be advantageous when the price of oil is higher than that of Tianzhi. For example, U.S. Patent No. 6,232,352 discloses the modification of methanol to produce acetic acid, which can be incorporated by reference. By modifying the methanol plant, the large capital cost required to eliminate carbon monoxide from the new acetic acid plant can be significantly reduced or largely eliminated. All or part of the synthesis gas is recycled from the sterol synthesis cycle and is supplied to the recovery unit for carbon monoxide and hydrogen, which is then used to produce acetic acid. In addition to acetic acid, this process can also be used to make hydrogen useful in the application of the present invention. The oxime carbonylation process suitable for the production of acetic acid is described in U.S. Patent Nos. 7,2,8,624, 7,115,772, 7,005,54, 6,657, 078, 6, 627, 770, 6, 143, 930, 5, 599, 976, and s. In any of the embodiments, the acetic acid fed to the hydrogenation reaction may also include other carboxylic acids and anhydrides, as well as acetaldehyde and acetone. Preferably, a suitable acetic acid feed stream comprises one or more compounds selected from the group consisting of acetic acid, acetic anhydride, acetaldehyde, ethyl acetate, and mixtures thereof. These other compounds can also be hydrogenated in the process of the invention. In some embodiments, a carboxylic acid, such as propionic acid or an anhydride thereof, may be advantageous for the production of propanol. Alternatively, the acetic acid in vapor form can be removed from the flash column of the methanol carbonylation unit and used directly in the form of a crude product, as described in U.S. Patent No. 6,657,078, the disclosure of which is incorporated herein by reference. The crude vapor product can be fed directly into the ethanol synthesis reaction zone without the need to condense acetic acid and light ends or remove water, saving overall processing costs. The acetic acid can be fed to the reactor while the vaporized acetic acid can be fed as it is unconverted or diluted with a relatively inert carrier gas such as nitrogen 'argon, helium and carbon dioxide. In order to be able to operate in the gas phase, the temperature should be controlled in the system so that it is not lower than the acetic acid n in a special (four) pressure under the pressure of the Buddha, gasification, and then evaporation of the warm Step-addition reactor population temperature ^ In another embodiment, 'acetate is passed through hydrogen, recycle gas, another-sense gas or a mixture thereof, at a temperature below the temperature of acetic acid, (4) Acid humidifying the carrier gas, which is the temperature of the anti-wire population of the heated mixed gas. Preferably, the acetic acid is vaporized by argon and/or recycle gas at a temperature equal to or lower than 耽', followed by heating and combining the gas to the reactor inlet temperature. In particular, acetic acid hydrogenation can achieve good conversion rate and good ethanol _ rate ^ the purpose of the invention," conversion rate refers to the conversion of acetic acid into _ in the feed: the ratio of the ratio ^ conversion rate of the feed The percentage of the molar amount of acetic acid in the middle means that the conversion is above 10%, for example: at least 20%, at least 40%, at least ί have at least ^ or at least _. Although the catalyst has a (four) _ rate "= as in To pay 8. % or at least 9. %, but in some embodiments, the conversion rate of the female's choice rate can be accepted by a lot of people. It is more difficult to make the choice of the junior high school through the appropriate Wei Qian. (4) f conversion rate, but the 201134795 should be married to each of the species by the wrong acid, touch the weaving coffee _ w 6 ; == The term ‘‘acetyl compound” used, with 丄 = road and acetic acid B. Preferably, the selectivity of ethanol is 80% or more, for example, S is less than Na = less: in the embodiment of the invention, it is also preferred that the products are not expected, such as simmering, sputum, and - carbon oxide are lower. The choice of God. The rate of selection of these unanticipated products is less than 4% 'if less than 2 dirty below 1%. It is preferred that these undesired products are not detected during the hydrogenation process. In some of the inventions of the invention, the scales are low, usually less than 2/6 'often less than 1%, and in many cases less than 5% of acetic acid is converted to alkanes by catalysts, while alkanes There is not much value other than being a fuel. "Yield" means the number of specific products, such as ethanol, per kilogram of catalyst per hour during hydrogenation. The yield is at least 200 grams of ethanol per kilogram of catalyst per hour, for example, at least 4 grams of ethanol per kilogram of catalyst per hour or preferably at least 6 grams of ethanol. In terms of range, the yield is preferably from 200 to 3, -g of ethanol per kg of catalyst, for example, 4 to 2,5 g or 600 to 2,000 g of ethanol. In a different embodiment, the crude ethanol product prepared by hydrogenation typically includes unreacted acetic acid, ethanol and water prior to any subsequent processing-purification and separation. The term "crude crude product" as used herein refers to any composition comprising from 5% by weight to 7% by weight ethanol and from 5% by weight to 35% by weight water. In some typical embodiments, the crude ethanol product comprises ethanol in an amount of from 5% by weight to 7% by weight based on the total weight of the crude ethanol product, for example: from 1% by weight to 60% by weight, or from 15% by weight to 5% by weight % by weight, based on the total weight of the crude ethanol product. Preferably, the crude ethanol product contains at least 1% by weight of ethanol, at least 15% by weight of ethanol or at least 2% by weight of ethanol. The crude ethanol product will generally further comprise unreacted acetic acid depending on the conversion, and its weight is, for example, less than 90%, for example, less than 80% by weight or less than 7% by weight. In terms of ranges, the unreacted acetic acid content is from 〇 to 9 重量% by weight, for example, from 5 to 80% by weight, from 15 to 70% by weight, from 20 to 70% by weight or from 25 to 65% by weight. Since water is formed in the reaction process, the crude ethanol product generally includes water 'e.g., content from 5% by weight to 35% by weight, for example: 'from 10 weight 15 201134795% to 30% by weight or 10% by weight to 26% by weight. The ethyl acetate may also be produced by a hydrogenation reaction or a general reaction. In this reading mode, the crude ethanol product comprises ethyl acetate in an amount from 〇% to 20% by weight 'for example: from 〇% by weight to 15% by weight, from 1% by weight to 12% by weight ' or 3% by weight to 1G weight. It is also possible to generate an E-way through a side reaction. In some embodiments, the crude ethanol product comprises an ethylene route in an amount from 〇% by weight to 10% by weight ’. From 0% by weight to 3% by weight, from 〇i% by weight to 3% by weight, or 0. 2% by weight to 2% by weight. Other ingredients, such as vinegar, scaly, brewed, terpenoids, alkanes, carbon dioxide, if detected, may be present in a total amount of less than 1% by weight, for example: less than 6% by weight, or less than 4% by weight. In terms of ranges, the crude ethanol composition may include other ingredients in an amount from 0. 1% by weight to 1% by weight, for example, from 〇1% by weight to 6% by weight or from G. l f amount from % to 4% by weight. Typical examples of the composition range of the product are shown in Table 1. 1 Table 1 Composition concentration of diol crude product (% by weight) Concentration (weight 〇 / 〇) Concentration (weight concentration (% by weight) ethanol 5 to 70 10 to 60 15 to 50 25 to 50 acetic acid 0 to 90 5 to 80 15 to 70 20 to 70 water 5 to 35 5 to 30 10 to 30 10 to 26 ethyl acetate 0 to 20 0 to 15 1 to 12 3 to 10 acetaldehyde 0 to 10 0 to 3 0. 1 to 3 〇_2 to 2 other 0. 1 to 10 0. 1 to 6 0. 1 to 4 —--- Figure 1 shows that the seed is liquefied according to the present invention. (8) It is suitable for hydrogenating acetic acid and separating ethanol from crude ethanol. System 100 includes a reaction zone 1〇1, a purification zone 1〇2, and a storage tank 13 between the reaction zone ιοί and the purification zone 102. The reaction zone 1()1 includes a reaction, and the 103' hydrogen feed line 1〇4 And acetic acid is fed into the line 1〇5. The purification zone 1〇2 includes a flash X column 106'--steamed & 1〇7, a second steaming tower 1〇8 and a third steaming tower. Nitrogen and acetic acid are supplied to the evaporator 11 through line 104 and line 105, respectively, and a gas turbulent flow is introduced in the line ui to the reaction H 1G3. In the embodiment towel, the line 1G4 and the line 105 can be combined and fed together to the evaporator 11〇, for example, the temperature of the steam feed stream in the feed stream is preferably contained in a feed stream. Lines range from ι〇〇β〇 to (10). c, to 31 ° ° C ' or 15 ° ° C to 3 ° ° C. Any unfilled material will be removed from the steamed sorghum 2, as shown in Figure 1, and can be recycled. Further, although Fig. 1 shows the top of the tube reactor 1〇3, the line 111 can be introduced into the side, upper or bottom of the reactor 103. The step-by-step modification and additional components of reaction zone 1 () 1 are described below. In contrast, 1.3 contains a catalyst 'which is used for _, preferably hydrogenation of acetic acid. In one implementation - or recording a bed (not shown), the silk may be protected from exposure to poisons or undesirable impurities contained in the shaft. Such guard beds can be used in steamed oxygen or liquid streams. Suitable material for the guard bed is known in the literature, including, for example, carbon, oxidation 35, shouting or _. In contrast, the tilting medium is used to capture a specific hydrazine such as sulfur or halogen. In the hydrogenation process, it is preferred to continuously withdraw the crude ethanol stream from the reaction of $103 via g path 1曰12. The crude ethanol stream can be condensed and sent to a flash column to provide a vapor stream and a liquid stream. In one embodiment, flash column 1 6 preferably operates from 50 C to 5 GG ° C, for example, from 7 G ° C to 40 Torr. [or 1GG ° C to 350. In actual mode, the pressure of the flash column 106 is preferably from 50 kPa to 2,000 kPa, for example. From 75 kPa to i, · kPa or from 1 to I kPa. In a preferred embodiment, the temperature and pressure of the Pj steam column 1〇6 are similar to the temperature and pressure of the anti-enchantment 1〇3. The vapor stream escaping from the flash '1〇6 may include hydrogen and a hydrogen absorbing compound, which may be removed and/or sent via the f-path 113 to the reaction zone ω, as shown in the figure, the vapor stream returning the knife via compression The machine 114, in combination with the hydrogen feed, is fed to the evaporator 11A. In the embodiment, the liquid discharged from the flash column 1〇6 is pumped as a feed composition to the first distillation column 1〇7 via line =5, which is also referred to as an acid separation unit. The side of the first steaming tower 1〇7 is fed via a line us, for example, J. The contents of line 115 are generally broadly derived from the product directly from the reactor' and may in fact be characterized as a crude ethanol product. As above, the storage tank 130 is placed between the reaction zone 101 and the purification zone 102. A portion or all of the liquid feed to line 115 may pass through line 131 to storage tank 130 and return to official passage 115 via line 1:>2. A portion of the liquid feed stored in the storage tank 130 may be fed directly into the acid removal unit (first distillation column) 丨〇7 via line 132, or may be fed into the arbitrarily with the remainder of the liquid feed of line ι5, A portion of the crude ethanol product in line 112 can also be fed to a separate storage tank (not shown in Figure 17 201134795). However, the first storage tank can also be considered as a storage tank. For example, if line 112 ethanol crude and line 115 liquid feed are to be stored separately, an additional storage tank can be used. = the storage tank 13 〇, in the pipeline m ethanol crude and / or in the pipeline m liquid feed temperature = 'acid-like acid removal unit (the _ _ tower of the material to turn or cool it. Road, 112 or 115 crude ethanol can maintain temperature or cooling, or storage tank 13 can maintain f cooling temperature 'for example: lower than thief, such as below or below 耽, or in terms of range 'from 0T to 40T, for example: from 〇.〇: to 3〇τ or 〇τ to 2〇〇c. If the temperature of the line 112 and/or the line m exceeds these temperatures, the contents of the line ιΐ2 and/or the output can be as needed. Cooling is carried out. - The seedlings are transmitted and the instrument can be combined with a cooling device to maintain the temperature. In the embodiment, the contents of the pipeline are substantially the same as the crude ethanol obtained from the reactor, as long as the acid removal unit is fed. (The first steaming tower) The acetic acid acetate in the feed of 1〇7 will not increase more than 5 times or more than the weight of the ethylene product in the reactor. The sample does not exceed 3% by weight or 2% by weight. , Lai feed may be different from ethanol crude 'because the composition is better to ride on the hydrogen without hydrogen, carbon dioxide, burnt and B These are all removed by flash column 106. The typical composition of line 115 is listed in Table 2. It should be understood that line 115 may contain other unlisted ingredients, such as rii in the feed. 18 201134795 Concentration (% of re-entry, Table 2 Concentration of feed composition (% by weight)

10 至 60 至80 於（<)顯示的量較佳為不存在，如杲存在，可能 存在微：!：，或重量大於〇.〇〇〇〗％。 Ϊ2/酸ίΠΓ包括但不限於丙酸㈣、醋酸賢醋酸異丙 或其混合物。表2中“其傾，，可以包括但不 I 、異τ基乙喊其混合物。表2中“其他醇類”可能 甲醇、異丙醇、正丙醇、正丁醇或其混合物。在一實施 2中立5組成物，例如：管路115可包括丙醇，如異丙醇和/或正 從議1 2至αι重量％，從咖至⑽3重量％或_ι 物式舰了解，這些其他成分可關由這麵述任何館出 ^殘留物流携帶之，在此不會進一步陳述，除非特別註明。 二ΐ醋酸含量低於3重量％，酸分離蒸潑塔(第一蒸肺酸清 稱為輕餾份蒸餾塔。 丹隹此也 1 1 ^示的，方式中’管路115引入酸清除單元-第—蒸娜107 d 下半部或更低的三分之一處。在第一蒸鱗107中，未 2 ’’的醋酸’一部分的水’和其他重館份，如果存在，將於管路115 3 可較佳為不斷㈣當作殘留物。部分或所有的殘留物 吕路117取回，冷凝和回流’例如.其回流比從】〇·】 201134795 至1:10，例如：從3:1至1:3或從1:2至2:1。 任何蒸館塔107 ’ 108，或109可為任何能夠分離和/或純化之蒸館塔。 較佳為蒸餾塔包括塔盤蒸餾塔，其具有丨至15〇分餾塔盤，例如：具 f 1〇至100分餾塔盤，20至95分餾塔盤或30至75分餾塔盤。分餾 4盤可為筛盤、固㈣塔盤、移動閥塔盤、或具有文獻上已知的任何 其他適的設計。在其它實施方式巾，可以使用填絲娜。就填充 蒸館塔而言’規整频和零散填料均可朗。這祕盤或填料可安排 f連續的蒸德塔，也可能安排在兩座或更多座的蒸德塔，使得蒸氣 從第一座進入第二座，而液體從第二座進入第一座等等。 ，己用於每-純化塔的相關冷凝器和液體分離槽可以是任何傳統的設 计’並簡化於第1圖。如第i圖所示，熱可以提供給每個蒸鱗或使 底部流循環通過敝換器或_[其他類型的再沸器，如内部再沸 器’也可用於-些實施方式中。提供再滞器的熱量可來自任何製程中 ^的熱量，該製程可和再彿器整合或_外部熱源，如其他發熱化 學製程或域。雖然、如第1圖所示只具-反應器和-閃蒸塔，但是在 些本發明實施方式中可以用附加的反應器、閃蒸塔、冷凝器、加孰 轉、和其他元件。對此領域之熟悉技藝者即知通㈣用化學製程: 各種冷凝器、泵、壓職、㈣器（―）、、 分離容科，也可進行讀，並祕本發_製財。逆接器 用^娜的溫度和壓力可能會有解.就實際問題而言 =ff施方式中次大氣壓力及超大氣壓力均可使用，但在這此區忒 =會2的壓力從Π)千帕至3，_千帕。不同區域内的溫度—般介= 勿Γ成物和移除，知組成物的彿點之間。對此領域之 ϋ ί %卩α在操作蒸顧塔某一點的溫度是依賴於在該位置的物料 合^和_塔壓力。此外’視生絲程魏模而定，進料速率奸 會有所不同，如果加以财，可能舰 b ==氣壓操作第一蒸齡_，由第一蒸館塔=出管路116 留物之溫度較佳為從㈣至12(Γ(：，例如：從朦C至⑴ 1〇7#ώ^117 促《 C至110 c ’例如：從75〇c至95〇c或8〇〇c至9〇〇c。在其它實 201134795 施方式中’第-蒸館塔收壓力範圍從〇1千帕至训千帕，例如：從 帕至475千帕或從1千帕至375千帕。第—_塔ig7餾出物和殘 組成物之典型成分蒸鱗於下面表3。應該理解的是，館出物和殘 =物還可能包含未列出的其他成分，如在鱗巾的成分^為方便起見， 第厂蒸顧塔的德出物和殘留物可能也被稱為“第一飽出物，，或“第一殘留 物^其他蒸館塔的館出物或殘留物也可具有類似數字修飾語（第二， 第三等）D彼此，但這樣的㈣糾驗娜為要求任何 分離順序。 表3 第一蒸餾塔10 to 60 to 80 The amount shown by (<) is preferably absent. If 杲 exists, there may be micro:!:, or the weight is greater than 〇.〇〇〇〗. Ϊ2/acid ΠΓ includes, but is not limited to, propionic acid (iv), isopropyl acetate, or a mixture thereof. In Table 2, "the pour, which may include but not I, is a mixture of different groups. The "other alcohols" in Table 2 may be methanol, isopropanol, n-propanol, n-butanol or a mixture thereof. Implementing a 2 Neutral 5 composition, for example, the line 115 can include propanol, such as isopropanol and/or from 1 to a% by weight, from coffee to (10) 3 wt% or _ι, which are known to the other components. It can be carried out by any of the museum's residual logistics, and will not be further stated here unless otherwise specified. The diacetic acid content is less than 3% by weight, and the acid separation tower is steamed. Light distillate distillation column. Tanjung is also shown in 1 1 ^, in the way 'line 115 introduced acid removal unit - the first - steamed na 107d lower half or lower one third. In the first steaming In the scale 107, the water 'part of the water' and other heavy parts that are not 2'', if present, will preferably be continuously (iv) as a residue in the line 115 3 . Part or all of the residue Lu Lu 117 Retrieve, condense and reflux 'for example. its reflux ratio from 〇·】 201134795 to 1:10, for example: from 3:1 to 1:3 or from 1:2 to 2 : 1. Any steaming tower 107 '108, or 109 may be any steam tower that can be separated and/or purified. Preferably, the distillation column comprises a tray distillation column having a 丨 to 15 〇 fractionation tray, for example: Having a f 1 〇 to 100 fractionation tray, a 20 to 95 fractionation tray or a 30 to 75 fractionation tray. The fractionation 4 tray can be a sieve tray, a solid (four) tray, a moving valve tray, or any of the known in the literature. Other suitable designs. In other embodiments, the towel can be used. In terms of filling the steaming tower, the regular frequency and the scattered filler can be used. This secret plate or packing can be arranged as a continuous steaming tower. Arranged in two or more steamed towers, so that the vapor enters the second seat from the first seat, and the liquid enters the first seat from the second seat, etc., has been used in the relevant condenser of each purification tower and The liquid separation tank can be of any conventional design' and is simplified in Figure 1. As shown in Figure i, heat can be supplied to each steaming scale or the bottom stream can be circulated through the converter or _[other types of reboiling A device such as an internal reboiler can also be used in some embodiments. The heat that provides the reciprocator can come from The heat in the process, the process can be integrated with the re-fog or external heat source, such as other heating chemical processes or domains. Although, as shown in Figure 1, there are only - reactor and - flash tower, but in some Additional reactors, flash towers, condensers, twisting, and other components may be used in embodiments of the invention. Those skilled in the art will be aware of the chemical processes used in the art: various condensers, pumps, and pressures. , (4), (-), separation of the subject, can also be read, and secrets _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ Both force and superatmospheric pressure can be used, but in this area 忒 = will 2 pressure from Π) kPa to 3, _ kPa. Temperature in different areas - general = do not smash and remove, know Between the Buddha points of the composition. The temperature at which a certain point in the operation of the steaming tower is dependent on the material and column pressure at that location. In addition, depending on the raw silk process, the feeding rate will be different. If you make a fortune, the ship b == air pressure operation first steaming age _, the temperature of the first steaming tower = outlet pipe 116 Good from (four) to 12 (Γ (:, for example: from 朦C to (1) 1〇7#ώ^117 to promote "C to 110 c ' for example: from 75〇c to 95〇c or 8〇〇c to 9〇 〇c. In the other real 201134795 mode, the pressure of the first steaming tower ranges from 〇1 kPa to kPa, for example: from Pa to 475 kPa or from 1 kPa to 375 kPa. The typical components of the tower ig7 distillate and the residual composition are steamed in the following Table 3. It should be understood that the museum and the residue may also contain other ingredients not listed, such as the composition of the scale towel. For the first time, the first product and residue of the first steaming tower may also be referred to as “the first residue, or “the first residue ^ other museums or residues of the steaming tower may also have similar The digital modifiers (second, third, etc.) D are each other, but such (four) corrective Na is required for any separation order. Table 3 First distillation tower

如表3所示’而不被理論約束’驚人的意外地發現#在狀酸分離蒸 傲塔（酸清除單元/第-蒸顧塔107)的進料中發現任何量之乙縮搭， 會在蒸傭塔中分解，使得在餾出物和/或殘留物中乙縮醛 有檢測到。 另外，現在已經發現上述描述的平衡反應也可能有利於在第一蒸镏塔 107頂部區域乙酵的形成。 … ° 如第1圖所示’第一蒸鱗107的傲出物，如塔頂顧出物，任意地冷 21 201134795 凝和回流，較佳為其回流比為1:5至削 ，乙醇、醋酸乙醋和水，以及其他雜在^_出物較佳為 物，這是難以分離的。 貝田於形成一凡和三元共沸 管路117的第一傲出物引到第二 ”，較佳為引到第二蒸館塔1〇8*^門·； 108 ’其也稱為"輕館份蒸娜 之一處。在一實施方式中，第二如中間二分之一或中間三分 塔。萃取劑，諸如水，可添蝴第^8可1 是一種萃取純化蒸館 可從外部來源錢由-座❹卜水’用作萃取劑， 第:顏物™ :盤’具有5至7。塔一 Ϊ然諸塔⑽度和壓力可能會有·化，當在大氣壓力下 至_或_至9〇。。。在第二蒸顧塔1〇8引 5〇〇C ^ 9〇00"^60〇c ^ «〇°C60〇c 帛—蒸術1G8可在大氣壓力下操作。在其它實施方式中， 第二蒸娜1G8之勤範圍從αι千怕至別千帕，例如：從1千帕至 =5千帕或從！千帕至375千帕。第二蒸祕1〇8顧出物和殘留物乡且成 物典型成分列於下面表4中。應該理解的是，《物和殘留物還可能 包含未列出的其他成分，如在進料中的成分。 22 201134795 ------ ——_______________ 表4 二蒸餾塔 濃度（重量％) 濃度（重量％) 麗u物 醋酸乙酿 i^iTon 25 至 90 50 至 90 乙搭 5- 1至25 ---- 1至15 1至8 1至25 1至20 4至16 乙醇 输狀 ~^3〇" -----— 卜 0.001 至 15 0.01 至 5 <5 —----- 0.001 至 2 0.01 至 1 殘留物 -—--- -------- 水 30 iT70 30 至 60 30 至 50 乙醇 20 至 75 30 至 70 40 至 70 醋酸乙酯 胳舱 <3 ------ 0.001 至 2 0.001 至 0.5 «Β S3C <0.5 --------_ 0.001 至 0.3 0.001 至 0.2 在第二殘留物中乙醇對第二顧出物中乙_重量比較佳為至少有3: 1例如.至）、有6 . 1，至少有8 : }，至少有1〇 ·」或至少有15 :卜 在第二前物中醋酸乙㈣第二顧出物中醋酸乙狀重量味佳為低 於0.4.1 ’如.低於〇·2:ι或低於〇1:1。在如同第二蒸館塔1〇8使用水 作為萃取綱萃取塔之實施方式巾，在第二殘留物巾醋酸乙醋對第二 餾出物中醋酸乙酯之重量比趨近於零。 沒^局限於理論’妇丨人酸清除單元1G7(第—蒸娜)之前，嫉醋酸 乙自曰3量較低可提⑧第二細塔1G8效率，故維持或防止乙醇粗製品 中醋酸乙酯增加。 如，所示’第一蒸顧塔108底部之第二殘留物，其包括乙醇和水，通 過管路118饋入第三蒸餾塔109，其也被稱為“產品蒸餾塔，、更佳為， 管，118中第二殘留物引入第三蒸娜1〇9下部，如底部一半或更低的 三分之一處。由第三蒸餾塔109回收之乙醇較佳為實質上純化乙醇， 而不像管路119餾出物含共沸水。第三蒸餾塔1〇9餾出物較佳為如第ι 圖所示加以回流，例如：其回流比從〗:〗〇至10:1，例如：從1:3至成 為3:1或從1:2至成為2:1。在管路121中第三殘留物，其較宜為主要 包含水，該水較佳為從系統1〇〇中移除或可能部分送回系統丨⑻的任 23 201134795 ί：-109 «物和_物還可能包含未咐的其他成分，如在進料中 表 5 '-- ____^第=蒸餾尨 — 餾出物 _濃度（重量。/。） 濃度 濃度（重量％) 乙醇 75 至 96 <12 80至％ 1 ~ 水 85 至 96 醋酸 醋酸乙酯 <1 Α 土 y 3至8 0·001 至 0.1 0.005 至 〇.〇1 <5 0.00 Γϊ~4 0.01 至 3 殘留物 — 水 75 至 1〇〇 80 ϋοό~ 90 至 100 乙醇 <0.8 Λ --- αυϋΐ 至 0.5 〇 〇〇< $ π 醋酸乙酯 <1 ο.οοι 至 0.5 v.v/vJ 王 U.VJD 0.005 至 0.2 _ 0.005 至 0.2 醋酸 <2 0.001 至 o s — 通過純化製程的進料或反應粗產物中任何的化合物一般保持在第三餾 出物之量佔第三餾出物組成物總重量低於0.1重量％，例如··低於0.05 重量％或低於0.02重量％。在一實施方式中，一支或更多支的側流可 除去系統100中的任一蒸顧塔107 ’ 108和/或1〇9的雜質。較佳為在一 實施方式中，至少一側流用於從第三蒸餾塔1〇9去除雜質。雜質可被 清除和/或保留在系統100内。 在管路119中第三餾出物可使用一種或多種額外的分離系統，例如：蒸 館塔（例如：精餾塔）或分子篩進一步純化’以形成無水乙醇產品流， 亦即“完成的無水乙醇產品“》 24 201134795 管路120中館出物送回第二蒸娜108，較佳為，如第i圖所_ ^ 3回比從1:1°至_，，從Μ至5:: 3 第二蒸^:的館出物可被清除。或者，因為它包含醋酸乙醋， 101，‘以轉或部分的餾出物可通過管路120再回到反應區 回輸㈣，撕_物可循環再 乂 y if i 路120所示’並可和醋酸饋人管路105共同饋入。 (i顯干)2方ί: ’第二餾出物120可使用—座或多座其他蒸餾塔 (禾顯不）進-步靴以移除其他成分如乙搭。 乙醇完成品 ^發Ρ製程元成的乙醇城触齡包触75重量％至96重量％乙 醇列如.從8〇重量％至96重量％或85重量％至％重量％乙醇， „對完成的乙醇組成物總重量而言。典型的乙醇組成物完成 品成分範圍如下表6。 表6 r-.. 乙醇完成品組成 成分 濃度（重量％) 濃度（重量％) 濃度（重量％) 乙醇 75 to 96 80 to 96 85 to 96 水 <12 1 to 9 3 to 8 醋酸 <1 <0.1 <0.01 醋酸乙醋 <2 <0.5 <0.05 乙縮路 <0.05 <0.01 <0.005 丙酮 <0.05 <0.01 < 0.005 異丙醇 <0.5 <0.1 <0.05 正丙醇 <0.5 <0.1 <0.05 本發明實施方式的乙醇完成品組成物適合使用在多種應用，包括燃 料、溶劑、化工原料、藥品、清潔劑、消毒劑、氫化運輸或消費品。 在燃料應用，變性乙醇組成物可與汽油混合用於機動運載工具，如汽 車、船隻和小型活塞式發動機飛機。在非燃料應用上，變性乙醇組成 物可用作化妝品和美容製劑之溶劑，洗滌劑，消毒劑，塗料，油墨， 25 201134795 和藥品。乙醇完成品組成物還可以用作製程溶劑，供醫藥產品，食品 製劑’染料，光化學和乳膠加工之用。 < :乙醇完成品組成物還可以用作化學原料，製造其他化學材料，如醋、 丙烯酸乙酯、醋酸乙酯、乙烯、乙二醇醚、乙胺、醛、高級醇，尤其 是丁醇。在生產醋酸乙酯中，乙醇完成品組成物可藉由醋酸進行酯化 或與聚醋酸乙觸反應4醇完成品組成物可脫水生產任何已 知的脫水觸媒可以用來使乙醇脫水，如描述於美國專利申請公開案號 2010/0030002和2010/003_，其全部内容及揭露在此納入參考^ 石觸媒，例如：可用為脫水觸媒。較佳為，沸石具有孔隙直徑至少有 〇.6奈米，較佳沸石包括脫水觸媒，選自包含絲光沸石，ZSM_5，沸石 X和彿石Y之群組。沸;5 X，例如：描述於美國專 2,882,244號和 沸石Y描述於美國專利第3，130,007號，其全部内容在此納入參考。 【實施方式】 為了使在此揭露之本發明可更有效地理解，提供一些實施例如下。 實施例1 藉由鉑/_職_統制乙馳製品。反祕件包含3 66克/分鐘 的醋酸、10.53升/分鐘的回收流’其包括醋酸，和1〇5升/分鐘的氮氣 進=’馈入反應器’其溫度分佈22〇〜齋c。從反應器至第一純化蒸 館塔的停留時間為2天，沒有溫度控制。由反應器抽取乙醇粗製品個 點樣本，並且以氣相層析儀(GC)測定其組成。亦抽取饋入純化蒸餾 =料液的第二樣本’亦即大玻璃瓶樣本，並且以氣相騎儀(Gc)測 疋其組成。比較個別樣本和第二個樣本，結果顯示在第2圖。可看出 在樣品間増加L2重量％的醋酸乙酿含量。 實施例2 ^由钻/锡觸媒使醋酸氫化得到乙醇粗製品。測量乙醇粗製品的穩定性 過57天。在此期間，醋酸乙酯含量增加，乙醇和醋酸含量下降如 3圖所示。 26 201134795 實施例3 藉由始/錫觸媒使醋酸氫化得到乙醇粗製品。測量乙醇粗製品在4〇C的 穩定性超過27天。在此期間測量乙醇，水，及醋酸的含量，並顯示在 第4圖》 實施例4 藉由鉑/錫觸媒使醋酸氫化得到乙醇粗製品。測量乙醇粗製品在40C冰 箱（F)中的穩定性超過61天，並和乙醇粗製品存放在室溫（RT，例 如.21。(：）的穩定性比較。測量在此期間乙醇，醋酸乙酯和醋酸的含 量，並且顯示在第5圖。在頂部線（RT)醋酸乙酯形成量的增加，大 於在底部線（F)醋酸乙酯形成量的增加。 實施例5 藉由鉑/錫觸媒使醋酸氫化得到乙醇粗製品。在下列三種不同的溫度測 量乙醇粗製品的儲存穩定性。在室溫（RT)，例如：21。〇 ;在4〇c冰箱 中（F);並在-78°C乾冰（DI)中分析乙醇粗製品。在此期間，測定醋 酸乙酯含量，並且載於第6圖。乙醇粗製品組成物存放在室溫（RT) 下醋酸乙醋形成量的增加大於儲存在冰箱（F)中醋酸乙酯形成量的增 加’後者又大於儲存在乾冰（DI)中醋酸乙酯形成量的增加。 雖然本發明已詳細描述’但在本發明精義和範圍内之各種修改對此領 域之熟悉技藝者而言係顯而易。以上討論相關的知識和技術文獻的背 景及詳細說明，其中揭露均可在此納入參考❶此外，還應該認識到本 發明層面和各實施方式的部分和以下各種特色和/或所附申請專利範 圍，是可以合併或互換全部或部分。在前面各種實施方式的描述中， 提到的另一種實施方式可以適當結合其他實施方式，對此領域之熟悉 技藝者將能理解。再者，那些知悉普通的技蚊獻者都明白前面描述 只是舉例說明，不是為了限制本發明範圍。 27 201134795 【圖式簡單說明】 以下參考各種圖式詳細解說本發明，其中相同之 。，示-種按照本發明實施方式具有儲存槽的氫 第2圖顯示醋酸乙酯含量之增加。 第3圖顯示乙醇粗製品在室溫之穩定性。 第4圓顯不乙醇粗製品在在40C之穩定性。 第5圖顯不乙醇粗製品在40c和210c的穩定性比較。 第6圖顯示比較在-78 C，40C和210C醋酸乙酯濃度的比較。 【主要元件符號說明】 代號 說明 100 氫化系統 101 反應區 102 純化區 103 反應器 104 氫氣饋入管路 105 醋酸饋入管路 106 閃蒸塔 107 第一蒸餾塔/酸清除單元 108 第一蒸顧塔 109 第三蒸餾塔 110 蒸發器 111 管路 28 201134795 代號 說明 112 管路 113 管路 114 壓縮機 115 管路 116 管路 117 管路 118 管路 120 瞢路 121 管路 130 儲存槽 131 管路 132 管路 29As shown in Table 3, 'not bound by theory', it is surprisingly discovered that in the feed of the acid-storing separation tower (acid removal unit / the first steaming tower 107), any amount of shrinkage is found. Decomposition in the steamer tower allows acetal to be detected in the distillate and/or residue. In addition, it has now been found that the equilibrium reaction described above may also facilitate the formation of ethylene glycol in the top region of the first distillation column 107. ... ° As shown in Fig. 1 'the first steamed scale 107 proud, such as the top of the tower, arbitrarily cold 21 201134795 condensation and reflux, preferably its reflux ratio of 1:5 to cut, ethanol, Ethyl acetate and water, as well as other impurities, are preferred, which are difficult to separate. Bayfield's first arrogant in forming a ternary and ternary azeotrope line 117 leads to the second", preferably to the second steaming tower 1〇8*^门·; 108 'which is also known as &quot One part of the light shop steaming. In one embodiment, the second is like the middle half or the middle three-point tower. The extractant, such as water, can add the first ^8 can be an extraction purification steaming hall It can be used as an extractant from the external source of money - ❹ ❹ 水 water, the first: 颜物TM: 盘' has 5 to 7. Towers and towers (10) degrees and pressure may be available, when at atmospheric pressure Down to _ or _ to 9 〇... in the second steaming tower 1〇8 cited 5〇〇C ^ 9〇00"^60〇c ^ «〇°C60〇c 帛—steaming 1G8 can be at atmospheric pressure In other embodiments, the second steaming 1G8 range from αι to 千kPa, for example: from 1 kPa to = 5 kPa or from ! kPa to 375 kPa. The typical ingredients of the recipes and residues are listed in Table 4 below. It should be understood that the substances and residues may also contain other ingredients not listed, such as ingredients in the feed. 22 201134795 ------ —_______________ Table 4 Distillation column concentration (% by weight) Concentration (% by weight) Liwu acetic acid B. i^iTon 25 to 90 50 to 90 Either 5- 1 to 25 ---- 1 to 15 1 to 8 1 To 25 1 to 20 4 to 16 Ethanol Loss ~^3〇" ------ Bu 0.001 to 15 0.01 to 5 < 5 —----- 0.001 to 2 0.01 to 1 Residue --- -- -------- Water 30 iT70 30 to 60 30 to 50 Ethanol 20 to 75 30 to 70 40 to 70 Ethyl acetate Cabin <3 ------ 0.001 to 2 0.001 to 0.5 « « Β S3C <0.5 -------- 0.001 to 0.3 0.001 to 0.2 In the second residue, the ethanol is preferably at least 3:1, for example, to the weight of the second take. There are 6.1, at least 8 : }, at least 1 〇 ·" or at least 15 : Bu in the second precursor, acetic acid B (four) second take-off, the acetic acid sigmoid weight is preferably less than 0.4.1 '如. Below 〇·2:ι or below 〇1:1. In the same manner as in the second steaming tower 1 8 using water as the extracting column of the extracting column, the weight ratio of ethyl acetate to the ethyl acetate in the second residue in the second residue was brought to near zero. Not limited to the theory 'Women's acid removal unit 1G7 (the first - steaming Na), before the lower amount of acetic acid B from the 曰3 can raise the efficiency of the second fine tower 1G8, so maintain or prevent ethyl acetate in the crude ethanol The ester is increased. For example, a second residue at the bottom of the first vapor column 108, which includes ethanol and water, is fed through line 118 to a third distillation column 109, which is also referred to as a "product distillation column, and more preferably , the second residue in the tube 118 is introduced into the lower portion of the third steaming unit 1 , such as one half of the bottom half or lower. The ethanol recovered from the third distillation column 109 is preferably substantially purified ethanol, and Unlike the distillate of the line 119, the distillate contains azeotropic water. The distillate of the third distillation column 1〇9 is preferably refluxed as shown in Fig. ι, for example, the reflux ratio is from 〖: 〇 to 10:1, for example : from 1:3 to 3:1 or from 1:2 to 2:1. The third residue in the line 121, preferably containing mainly water, is preferably from the system 1 Any 23 201134795 ί:-109 that is removed or may be partially returned to the system 8 (8) «Materials and _ objects may also contain other components of the ruthenium, such as in the feed table 5 '-- ____ ^ = distillation 尨 - distillation Concentration _ concentration (% by weight) Concentration concentration (% by weight) Ethanol 75 to 96 < 12 80 to % 1 ~ Water 85 to 96 Acetate acetate <1 Α soil y 3 to 8 0·001 0.1 0.005 to 〇.〇1 <5 0.00 Γϊ~4 0.01 to 3 Residue - Water 75 to 1〇〇80 ϋοό~ 90 to 100 Ethanol <0.8 Λ --- αυϋΐ to 0.5 〇〇〇< $ π Ethyl acetate <1 ο.οοι to 0.5 vv/vJ King U.VJD 0.005 to 0.2 _ 0.005 to 0.2 acetic acid < 2 0.001 to os - any compound in the crude product or the reaction crude product is generally maintained in the purification process The amount of the third distillate is less than 0.1% by weight, such as less than 0.05% by weight or less than 0.02% by weight, based on the total weight of the third distillate composition. In one embodiment, one or more branches The side stream can remove impurities from any of the steaming columns 107'108 and/or 1〇9 in the system 100. Preferably, in one embodiment, at least one side stream is used to remove impurities from the third distillation column 1〇9. The impurities may be purged and/or retained within system 100. The third distillate in line 119 may be further purified using one or more additional separation systems, such as a steaming tower (eg, a rectification column) or molecular sieves. 'To form a stream of anhydrous ethanol products, ie "completed ethanol products" 24 201134795 The discharge from the hall in the pipeline 120 is sent back to the second steamer 108, preferably, as in the figure i, the ratio of _ ^ 3 is from 1:1 ° to _, from Μ to 5:: 3 second The steamed food can be removed. Or, because it contains ethyl acetate, 101, 'the distillate can be recycled or returned to the reaction zone through line 120 (4), and the tear can be recycled. Then y y if i road 120 is shown 'and can be fed together with the acetic acid feed line 105. (i) The 2nd ί: 'The second distillate 120 can be used in a seat or a plurality of other distillation columns (Wu Xian) to enter the step shoes to remove other ingredients such as slap. Ethanol-finished product Ρ Ρ 的 的 的 的 乙醇 乙醇 乙醇 乙醇 乙醇 乙醇 乙醇 乙醇 乙醇 75 75 75 75 75 75 75 75 75 75 75 75 75 75 75 75 75 75 75 75 75 75 75 75 75 75 75 75 75 75 75 75 75 75 75 75 75 75 75 75 75 75 75 75 75 75 75 75 75 75 75 75 75 75 75 75 75 75 75 75 The total weight of the ethanol composition is as follows. The composition of the typical ethanol composition is shown in Table 6. Table 6 r-.. Ethanol finished product component concentration (% by weight) Concentration (% by weight) Concentration (% by weight) Ethanol 75 to 96 80 to 96 85 to 96 Water <12 1 to 9 3 to 8 Acetic acid <1 <1 <0.01 Acetate <2 <2 <0.5 <0.05 Elongation <0.05 <0.01 < 0.005 Acetone <0.05 <0.01 < 0.005 Isopropanol <0.5 < 0.1 < 0.05 n-propanol <0.5 < 0.1 < 0.05 The ethanol finished product composition of the embodiment of the present invention is suitable for use in various applications Including fuels, solvents, chemicals, pharmaceuticals, detergents, disinfectants, hydrogenated transport or consumer goods. In fuel applications, denatured ethanol compositions can be mixed with gasoline for use in motor vehicles such as automobiles, boats and small piston engine aircraft. In non-fuel applications, denaturation Alcohol composition can be used as a solvent for cosmetics and beauty preparations, detergents, disinfectants, coatings, inks, 25 201134795 and pharmaceuticals. Ethanol finished products can also be used as process solvents for pharmaceutical products, food preparations, dyes, light For chemical and latex processing. < : Ethanol finished product composition can also be used as a chemical raw material to make other chemical materials such as vinegar, ethyl acrylate, ethyl acetate, ethylene, glycol ether, ethylamine, aldehyde, Higher alcohols, especially butanol. In the production of ethyl acetate, the ethanol finished product can be esterified by acetic acid or reacted with polyacetate. The alcohol can be dehydrated to produce any known dehydration catalyst. It can be used to dehydrate the ethanol, as described in U.S. Patent Application Publication Nos. 2010/0030002 and 2010/003, the entire contents of which are incorporated herein by reference. The zeolite has a pore diameter of at least 66 nm. Preferably, the zeolite comprises a dehydration catalyst selected from the group consisting of mordenite, ZSM_5, zeolite X and buddha Y. Boiling; 5 X, for example: U.S. Patent No. 2,882,244, issued to U.S. Patent No. 3,130, 007, the entire disclosure of which is incorporated herein by reference. Example 1 A platinum product was prepared by platinum/_ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ 'Feed in the reactor' its temperature distribution 22 〇 ~ fast c. The residence time from the reactor to the first purified steam tower was 2 days with no temperature control. A sample of the crude ethanol product was taken from the reactor and its composition was determined by gas chromatography (GC). A second sample fed to the purified distillation = feed liquid was also taken, i.e., a large glass bottle sample, and its composition was measured by a gas phase rider (Gc). Comparing individual samples with the second sample, the results are shown in Figure 2. It can be seen that an L2% by weight acetic acid content is added between the samples. Example 2 ^ Hydrogenation of acetic acid from a drill/tin catalyst to give a crude ethanol product. The stability of the crude ethanol product was measured over 57 days. During this period, the ethyl acetate content increased, and the ethanol and acetic acid contents decreased as shown in Fig. 3. 26 201134795 Example 3 Hydrogenation of acetic acid by means of a start/tin catalyst gave a crude ethanol product. The stability of the crude ethanol product at 4 ° C was measured over 27 days. The contents of ethanol, water, and acetic acid were measured during this period and are shown in Figure 4 Example 4 Hydrogenation of acetic acid by platinum/tin catalyst to obtain a crude ethanol product. The stability of the crude ethanol product in the 40C refrigerator (F) was measured for more than 61 days and compared with the storage of the crude ethanol product at room temperature (RT, for example, .21. (:). During this period, ethanol, acetic acid B was measured. The content of ester and acetic acid, and is shown in Figure 5. The increase in the amount of ethyl acetate formed at the top line (RT) is greater than the increase in the amount of ethyl acetate formed at the bottom line (F). Example 5 by platinum/tin The catalyst hydrogenates acetic acid to obtain a crude ethanol product. The storage stability of the crude ethanol product is measured at three different temperatures: at room temperature (RT), for example: 21. 〇; in a 4 〇c refrigerator (F); The crude ethanol product was analyzed in -78 ° C dry ice (DI). During this period, the ethyl acetate content was determined and shown in Figure 6. The crude ethanol composition was stored at room temperature (RT) under the conditions of ethyl acetate. The increase is greater than the increase in the amount of ethyl acetate formed in the refrigerator (F). The latter is greater than the increase in the amount of ethyl acetate formed in dry ice (DI). Although the invention has been described in detail, it is within the spirit and scope of the present invention. Various modifications to those skilled in the art The above discussion discusses the background and detailed description of the relevant knowledge and technical literature, which may be incorporated herein by reference. In addition, it should be understood that the aspects of the present invention and the various embodiments and various features and/or The scope of the appended claims may be combined or interchanged in whole or in part. In the foregoing description of the various embodiments, the other embodiments mentioned may be combined with other embodiments as appropriate, and will be understood by those skilled in the art. Those skilled in the art will understand that the foregoing description is for illustrative purposes only and is not intended to limit the scope of the invention. 27 201134795 [Simplified Description of the Drawings] The present invention will be explained in detail below with reference to various drawings, wherein the same. Hydrogen in the storage tank according to an embodiment of the present invention shows an increase in the ethyl acetate content. Figure 3 shows the stability of the crude ethanol product at room temperature. The fourth round shows the stability of the crude ethanol product at 40C. Figure 5 shows a comparison of the stability of crude ethanol in 40c and 210c. Figure 6 shows the comparison of -78 C, 40C and 210C acetic acid. Comparison of Concentrations [Explanation of main components] Code description 100 Hydrogenation system 101 Reaction zone 102 Purification zone 103 Reactor 104 Hydrogen feed line 105 Acetic acid feed line 106 Flash column 107 First distillation column / acid removal unit 108 First Steam tower 109 third distillation column 110 evaporator 111 line 28 201134795 code description 112 line 113 line 114 compressor 115 line 116 line 117 line 118 line 120 line 121 line 130 line 130 storage tank 131 tube Road 132 pipeline 29

Claims (1)

201134795 七、申請專利範圍： 1. 一種純化乙醇粗製品之方法，包括： 在反應器中於觸媒存在下，使醋酸進行氩化形成乙醇粗製品；及 在純化區分離至少一部分的乙醇粗製品成為一支或多支衍生物流， 其中至少有一部份乙醇粗製品從反應器到純化區的停留時八 鐘至5天。 ’’’刀 2. 如申請專利範圍第1項所述之方法，其中純化區包括第一蒸鱗。 3. 如申請專利範圍第上和2項任一項所述之方法，其中分離包括在第 -蒸解分離至少部分乙醇粗製品成為第—顧出物，其包括乙醇、 水及醋酸乙酯，和第一殘留物，其包括醋酸。 4. 如申μ專利獅第3項所述之方法，還包括至少回收部 物到反應器。.㈣ 5. 圍第3和4項任一項所述之方法，其中第—殘留物包 重量。/。至1G〇重量％的醋酸，該百分率係對第—殘留物總重 重而s。 6. 如申明專利範圍第3至5項任一項所述之方法，還包括： 在閃蒸塔分離乙醇粗製品成為蒸氣流和液體流， 返回至少部分的蒸氣流至反應器；及 引導至少部分的液體流至第一蒸餾塔。 7. 如申請專概M 3至6項任—項所述之方法 部分的液體流至從至贼的溫度。 ^栝冷部b 8·如申請專利範圍第i至3項任一項所述之方法，其中 化區，其具膜分離單元，而乙醇粗製品及少一/ 是 通過該膜分離單元。 支何生物流疋 9·=申請__ 8雜之紋，_分料桃括渗透汽化 10.如申睛專利範圍第〗至9 醋酸乙奸人县, 法，其中乙醇粗製品中 曰酸乙自曰3量在引入純化區之前，不增加超過 11·如申請專利範圍第！至10項任一項所述之 〇 ° 粗製品從反應器至純化區的停留時間為丨秒至丨=至）、部分乙醇 201134795 12. 如申請專利範圍第1至11項任一項所述之方法，其中至少有部份乙 醇粗製品是導入儲存槽。 Π 13. 如申請專利範圍第1至12項任一項所述之方法，其中至少部分導入 儲存槽的乙醇粗製品從反應器到純化區之停留時間從 M.如申請細瓣i至項所狀方法=^製^包 括乙醇、水、醋酸乙酯和醋酸。 15·如申請專利範圍第1至14項任一項所述之方法，還包括： 冷卻至少部分乙醇粗製品至至40«c的溫度。 16.—種乙醇粗製品的純化方法，包括： 在反應器中於觸媒存在下，氫化醋酸形成為乙醇粗製品； 在閃蒸塔中分離乙醇粗製品成為蒸氣流和液體流； 引導至少部分的液體流到純化區；及 在純化區分離至少部分的液體流成為至少一衍生物流，其中至少 部份的液體流從閃蒸塔器到純化區的停留時間從5分鐘至5天。 17·如申請專利範圍第16項所述之方法，其中純化區包括第—蒸館塔。 18. 如申請專利範圍第16和17項所述任—項之方法，其中分離包^ -蒸镏塔中至少有部分的液體流分離成為第—館出物，其包 醇、水及醋酸乙酯，及第一殘留物，其包括醋酸。 19. 如申請專利_第16至18項任-項所述之方法，其中至 的液體流從閃蒸塔至第一蒸德塔之停留時間從5分鐘至5天。 20. 如申請專利細第16至19項任—項所述之方法，還包括返回至小 部分的蒸氣流到反應器之步驟。 夕 2L如申請專利綱第16至2G項任—項職之方法，還包括： 少部分的液體流到0至40°C的溫度。 7 22. 如申請專利範圍第16至21項任—項所述之方法，其中在 區之前乙醇粗製品中的醋酸乙酿含量不增加超過5重量％。 23. —種純化乙醇粗製品之方法，包括： 在反應器中於觸媒存在下氫化醋酸形成乙醇粗製品； 在閃蒸塔中分離乙醇粗製品成為蒸氣流和液體流； 冷卻至'少部分的液體流到從〇°C至4〇°c的溫度； 31 201134795 引導至少部分的液體流到純化區；及 在純化區分離至少部分的液體流成為至少一衍生物流。 24. 如申請專利範圍第23項所述之方法，其中純化區包括第一蒸餾塔。 25. 如申請專利範圍第23和24項任一項所述之方法，其中分離包括在 第一蒸餾塔分離至少部分的乙醇粗製品成為第一餾出物，其包括乙 醇、水及醋酸乙醋，及第一殘留物，其包括醋酸。 26. 如申凊專利範圍第23至25項任一項所述之方法，還包括將至少部 分第一殘留物返回反應器。 ° 27. 如申4專利範圍第23至26項項所述之方法，其$第—殘留物 包括從60重量％至1〇〇重量％的醋酸，該百分率係對總重量而士。 28. 如申請專利範圍第23至27雜—項所述之方法，還包括送回 部分的蒸氣流到反應器之步驟。 29. 如申請專利範圍第23至28項任-項所述之方法，其中在引入純化 區之前乙醇粗製品中醋酸乙醋含量不增加超過5重量％。 3〇_如申請專利範圍第23至29 _-項所述之方法，其中至 乙醇粗製品流是導入儲存槽中。 °物 31.如申請專利範圍第23至3〇項任一項所述之方法，其中乙醇粗 包括乙醇、水、醋酸乙酯和醋酸。 °σ 32201134795 VII. Patent application scope: 1. A method for purifying crude ethanol product, comprising: argonizing acetic acid into a crude ethanol product in a reactor in the presence of a catalyst; and separating at least a portion of the crude ethanol product in the purification zone. It becomes one or more derivative streams in which at least a portion of the crude ethanol product stays from the reactor to the purification zone for eight to five days. 2. The method of claim 1, wherein the purification zone comprises a first steaming scale. 3. The method of any of the preceding claims, wherein the separating comprises: separating, at the first part, the at least a portion of the crude ethanol product into a first product comprising ethanol, water and ethyl acetate, and A first residue comprising acetic acid. 4. The method of claim 3, wherein the method further comprises at least recovering the portion to the reactor. (4) 5. The method of any of items 3 and 4, wherein the first residue is of a weight. /. To 1% by weight of acetic acid, the percentage is the total weight of the first residue and s. 6. The method of any of claims 3 to 5, further comprising: separating the crude ethanol product into a vapor stream and a liquid stream in a flash column, returning at least a portion of the vapor stream to the reactor; and directing at least Part of the liquid flows to the first distillation column. 7. If the application part of the method specified in Sections M3 to 6 is to flow to the temperature of the thief. The method according to any one of claims 1 to 3, wherein the chemical zone has a membrane separation unit, and the crude ethanol product and the less than one are passed through the membrane separation unit. What is the biological flow 疋 9 · = application __ 8 miscellaneous lines, _ separate material peach pervaporation 10. If the application of the scope of the patent range 〖 to 9 acetic acid, the county, the law, which in the crude ethanol products The amount of 曰3 is not increased beyond 11 before being introduced into the purification zone. The residence time of the crude product of any one of the above-mentioned items from the reactor to the purification zone is from leap seconds to 丨= to), and the partial ethanol 201134795 is as described in any one of claims 1 to 11. The method wherein at least a portion of the crude ethanol product is introduced into a storage tank. The method according to any one of claims 1 to 12, wherein the residence time of the crude ethanol product introduced into the storage tank at least partially from the reactor to the purification zone is from M. Method = ^ system ^ includes ethanol, water, ethyl acetate and acetic acid. The method of any one of claims 1 to 14, further comprising: cooling at least a portion of the crude ethanol product to a temperature of 40 «c. 16. A method for purifying a crude ethanol product, comprising: forming a crude ethanol product in the presence of a catalyst in a reactor; separating the crude ethanol product into a vapor stream and a liquid stream in a flash column; guiding at least a portion The liquid flows to the purification zone; and at least a portion of the liquid stream is separated into at least one derivative stream in the purification zone, wherein at least a portion of the liquid stream has a residence time from the flash column to the purification zone from 5 minutes to 5 days. 17. The method of claim 16, wherein the purification zone comprises a first steaming tower. 18. The method of any one of clauses 16 and 17, wherein at least part of the liquid stream in the separation package is separated into a first-column, which comprises alcohol, water and acetic acid. An ester, and a first residue comprising acetic acid. 19. The method of claim 16, wherein the residence time of the liquid stream from the flash column to the first vaporization column is from 5 minutes to 5 days. 20. The method of any of claims 16 to 19, further comprising the step of returning a small portion of the vapor stream to the reactor.夕 2L, as applied for in the 16th to 2Gth of the patent program, includes: a small portion of the liquid flows to a temperature of 0 to 40 °C. The method of claim 16, wherein the ethyl acetate content in the crude ethanol product prior to the zone does not increase by more than 5% by weight. 23. A method of purifying a crude ethanol product, comprising: hydrogenating acetic acid in a reactor in the presence of a catalyst to form a crude ethanol product; separating the crude ethanol product into a vapor stream and a liquid stream in a flash column; cooling to a small portion The liquid flows to a temperature from 〇 ° C to 4 ° ° C; 31 201134795 directs at least a portion of the liquid to the purification zone; and separates at least a portion of the liquid stream in the purification zone into at least one derivative stream. 24. The method of claim 23, wherein the purification zone comprises a first distillation column. 25. The method of any of claims 23 and 24, wherein separating comprises separating at least a portion of the crude ethanol product in the first distillation column into a first distillate comprising ethanol, water, and ethyl acetate. And a first residue comprising acetic acid. 26. The method of any of claims 23 to 25, further comprising returning at least a portion of the first residue to the reactor. 27. The method of claim 23, wherein the $-residue comprises from 60% by weight to 1% by weight of acetic acid, the percentage being the total weight. 28. The method of claim 23, wherein the method further comprises the step of returning a portion of the vapor stream to the reactor. 29. The method of any of clauses 23 to 28, wherein the ethyl acetate content in the crude ethanol product does not increase by more than 5% by weight prior to introduction of the purification zone. The method of claim 23, wherein the crude ethanol product stream is introduced into the storage tank. The method of any one of claims 23 to 3, wherein the crude ethanol comprises ethanol, water, ethyl acetate and acetic acid. °σ 32
TW100103896A 2010-02-02 2011-02-01 Processes for maximizing ethanol formation in the hydrogenation of acetic acid TWI588121B (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
US30081510P 2010-02-02 2010-02-02
US33270210P 2010-05-07 2010-05-07
US12/940,595 US8552224B2 (en) 2010-05-07 2010-11-05 Processes for maximizing ethanol formation in the hydrogenation of acetic acid

Publications (2)

Publication Number Publication Date
TW201134795A true TW201134795A (en) 2011-10-16
TWI588121B TWI588121B (en) 2017-06-21

Family

ID=45945433

Family Applications (1)

Application Number Title Priority Date Filing Date
TW100103896A TWI588121B (en) 2010-02-02 2011-02-01 Processes for maximizing ethanol formation in the hydrogenation of acetic acid

Country Status (9)

Country Link
EP (1) EP2531469A2 (en)
CN (2) CN105367382A (en)
AU (1) AU2011213126B2 (en)
BR (1) BR112012019371A2 (en)
CA (1) CA2787404A1 (en)
MX (1) MX2012008929A (en)
SG (1) SG182666A1 (en)
TW (1) TWI588121B (en)
WO (1) WO2011097190A2 (en)

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8884080B2 (en) 2010-07-09 2014-11-11 Celanese International Corporation Reduced energy alcohol separation process
US9126125B2 (en) 2010-07-09 2015-09-08 Celanese International Corporation Reduced energy alcohol separation process having water removal
AR086134A1 (en) * 2011-04-26 2013-11-20 Celanese Int Corp SEPARATION PROCESS OF REDUCED ENERGY ALCOHOL WITH WATER REMOVAL
EP4059916A1 (en) 2021-03-15 2022-09-21 Linde GmbH Method and plant for the production of a product hydrocarbon
WO2023104963A1 (en) 2021-12-08 2023-06-15 Linde Gmbh Process and plant for producing one or more hydrocarbons

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2607807A (en) * 1950-02-24 1952-08-19 Du Pont Preparation of alcohols from carboxylic acids
DE3221077A1 (en) * 1982-06-04 1983-12-08 Basf Ag, 6700 Ludwigshafen METHOD FOR THE CONTINUOUS PRODUCTION OF ETHANOL
EP0990638A1 (en) * 1998-10-01 2000-04-05 Kvaerner Process Technology Limited Process
WO2004073841A1 (en) * 2003-02-21 2004-09-02 Bussan Nanotech Research Institute, Inc. Method for concentrating water-soluble organic material
WO2009009322A1 (en) * 2007-07-06 2009-01-15 Best Energies, Inc. Integrated facility for producing alcohol using homoacidogenic fermentation
EP2060553A1 (en) * 2007-11-14 2009-05-20 BP p.l.c. Process for the conversion of hydrocarbons into alcohol

Also Published As

Publication number Publication date
BR112012019371A2 (en) 2018-05-22
EP2531469A2 (en) 2012-12-12
CN102421729A (en) 2012-04-18
WO2011097190A2 (en) 2011-08-11
MX2012008929A (en) 2012-08-15
CA2787404A1 (en) 2011-08-11
SG182666A1 (en) 2012-08-30
AU2011213126B2 (en) 2015-07-23
TWI588121B (en) 2017-06-21
CN105367382A (en) 2016-03-02
AU2011213126A1 (en) 2012-08-02
WO2011097190A3 (en) 2011-11-24

Similar Documents

Publication Publication Date Title
US9051238B2 (en) Process for recovering ethanol
TW201134805A (en) Process for producing an ester feed stream for esters production and co-production of ethanol
AU2011213130B2 (en) Ethanol compositions
JP2013518818A (en) Ethanol purification method
US8552225B2 (en) Process for vaporizing acetic acid for hydrogenation processes to produce ethanol
TW201204694A (en) Weak acid recovery system for ethanol separation processes
CN102421736B (en) Processes for producing anhydrous ethanol compositions
TW201134795A (en) Processes for maximizing ethanol formation in the hydrogenation of acetic acid
AU2011213125B2 (en) Process for purifying ethanol
US8314272B2 (en) Process for recovering ethanol with vapor separation
HK1164269A (en) Processes for producing anhydrous ethanol compositions
HK1169647B (en) Process for the production of ethanol by hydrogenation of vaporized acetic acid
HK1169384A (en) Processes for maximizing ethanol formation in the hydrogenation of acetic acid
HK1169373A (en) Process for recovering ethanol

Legal Events

Date Code Title Description
MM4A Annulment or lapse of patent due to non-payment of fees