TW201247301A - Extractive distillation of crude alcohol product - Google Patents

Extractive distillation of crude alcohol product Download PDF

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Publication number
TW201247301A
TW201247301A TW101114975A TW101114975A TW201247301A TW 201247301 A TW201247301 A TW 201247301A TW 101114975 A TW101114975 A TW 101114975A TW 101114975 A TW101114975 A TW 101114975A TW 201247301 A TW201247301 A TW 201247301A
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Taiwan
Prior art keywords
ethanol
acetic acid
residue
stream
water
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TW101114975A
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Chinese (zh)
Inventor
R Jay Warner
Victor J Johnston
David Lee
Adam Orosco
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Celanese Int Corp
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Priority claimed from US13/094,588 external-priority patent/US8686200B2/en
Priority claimed from US13/162,034 external-priority patent/US8748675B2/en
Application filed by Celanese Int Corp filed Critical Celanese Int Corp
Publication of TW201247301A publication Critical patent/TW201247301A/en

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    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00Preparation of carboxylic acid esters
    • C07C67/48Separation; Purification; Stabilisation; Use of additives
    • C07C67/52Separation; Purification; Stabilisation; Use of additives by change in the physical state, e.g. crystallisation
    • C07C67/54Separation; Purification; Stabilisation; Use of additives by change in the physical state, e.g. crystallisation by distillation
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/132Preparation 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
    • C07C29/136Preparation 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
    • C07C29/147Preparation 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
    • C07C29/149Preparation 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
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/74Separation; Purification; Use of additives, e.g. for stabilisation
    • C07C29/76Separation; Purification; Use of additives, e.g. for stabilisation by physical treatment
    • C07C29/80Separation; Purification; Use of additives, e.g. for stabilisation by physical treatment by distillation
    • C07C29/84Separation; Purification; Use of additives, e.g. for stabilisation by physical treatment by distillation by extractive distillation
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00Preparation of carboxylic acid esters
    • C07C67/08Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides with the hydroxy or O-metal group of organic compounds

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Vaporization, Distillation, Condensation, Sublimation, And Cold Traps (AREA)

Abstract

Recovery of ethanol from a crude ethanol product obtained from the hydrogenation of acetic acid using an extractive distillation column. The column yields a first residue that comprises ethanol, ethyl acetate, acetic acid, and water. The first residue is separated in a second column to yield a second distillate comprising ethanol and ethyl acetate. The second distillate is then separated in a third column to yield a third distillate comprising ethyl acetate and a third residue comprising ethanol.

Description

201247301 五、本案若有化學式時,請揭示最能顯示發明特徵的化學式: 無。 六、發明說明: 申請案交互參考(優先權主張) 本發明申請案主張優先權基於2011年12月2日提出之美國專利申請 案第61/566,442號,整個内容和揭露在此納入參考Q該申請案亦有關於 2011年4月26曰提出之美國專利申請案第13/094,641號及2〇11年6月16曰 提出之美國專利申請案第13/162,〇34號。 【發明所屬之技術領域】 b本發明一般涉及到在氫化反應器中由醋酸生產乙醇的製程,尤其 是,涉及到從萃取蒸餾回收乙醇的製程。 【先前技術】 工業使用的乙醇傳統生產方式是來自石化原料、例如石油、天然氣 ^炭’或者是從進射題,例如合減,或者是·㈣料或纖維 ^原料,例如玉米或賴,而得t傳統上來自石化原料以及纖維 原料來生產乙_方法—之雜化水合、甲醇綱祕反應、 直接醇類合成法以及,,費托合成法”(Fischer_Tr〇psch synthesis)。不穩定性 ^化肩料價格會引起傳統方式生產乙醇的成本波動,#原料價格上潘 =,會使得以替代來源來生產乙_需求更騎加,粉原料以及纖維 素原料可發酵轉化為乙醇。然而發酵方法通常用於消費性乙醇生產,由 ϊΐίϋΐϊί可以適用於供燃料之用或人類食用。此外,殿粉或纖維 2料的發酵會和作為食物來源相競爭,因而限制乙醇可用於工業生產 的量。 藉由紐類和/或其域基化合物的還原以生產乙醇已被廣泛研究, 201247301 而已在文獻中提到各種觸媒及支撐體的組合和操作條件。在還原烷酸(例 如醋酸)時,其他化合物會和乙醇一起形成或藉由副反應形成。這些雜質 會限制從這樣的反應混合物來生產和回收乙醇。例如,在氫化製程中, 酯、乙醇和/或水一起產出,而形成共沸物,而這是很難分離的。此外, 當轉化率是不完全的’未反應的醋酸仍然會殘存在於反應器產物令,而 其必須予以移除以回收乙醇。 歐洲專利EP02060553描述碳氫化合物轉成乙醇的製程,包括將碳氫 化合物轉成為醋酸,然後使醋酸氫化而得乙醇。分離來自氫化反應器的 物流,以獲取乙醇流及醋酸和醋酸乙酯的物流,而該物流再循環到氫化 反應器。 美國專利第7,842,844號描述在微粒觸媒的存在下於碳氫化合物轉化 為乙醇和可視情況選擇轉化為的醋酸之反應中,其可提高選擇率、觸媒 的活性和使用壽命之製程,_轉化餘由生成合成氣的㈣步驟。、 其他人士已倡議各種用來分離乙醇、醋酸乙g旨和水的混合物之萃取 劑。美國專利第4,654,1Z3號描述-種藉由運用萃取劑來從水分離乙醇的 製程。美國專利第4,379,028號和第4,569,726號描述藉由運用萃輔來從 醋酸乙g旨/乙醇/水的混合物來回收醋酸乙g|的製程。美國專利第6,375,8〇7 號描述藉由運用萃取劑分離乙醇和醋酸乙酯的方法。 ,, 目前仍需要改善從例如_之驗類,和/或其齡絲化合物還原 所獲得之粗產物中回收乙醇的製程。 【發明内容】 ,在第-實施方式中,本發明針對麟生產乙_製程,這個製程包 括從反應^巾麟_料錢化辦,而產生粗趋流 技 2-種或歸萃取_存在下,分離至少—部分的⑽粗產物:絲 ^ 3乙祕醋酸乙輯的第-餘出物,和包含乙醇、醋戈 多種萃取劑的第-殘留物,而該萃取劑係選自由水、二甲基2 4 201247301 (dimethylsulfoxide)、甘油、二甘醇、! _蔡酚、對苯二酚、Ν,Ν’_:曱基 甲醯胺、1,4-丁二醇、甘醇_丨,5_戊二醇,丙二醇_四甘醇_聚乙二醇、甘油 -丙二醇-四甘醇_1,4_ 丁二醇、乙醚、甲酸甲酿、環己院、N,N,_二甲基以 -丙二胺、N,N’-二甲基乙二胺胺、二乙三胺、己二胺、丨齐二胺戊烷、烷 基噻吩、十二烷、十三烷、十四烷、氣化石蠟、及其混合物所組成之群 組。在一實施方式中’第一殘留物可以包含低於5重量%的醋酸乙酯。製 程中還包括在第二蒸餾塔中分離至少一部分的第一殘留物,而產生包含 乙醇和醋酸乙酯的第二餾出物,和包含一種或多種萃取劑的第二殘留 物刀離至夕口P刀的第一館出物,而產生包含醋酸乙醋的第三顧出物 和包含乙醇的第三殘留物。在—實施方式帽至少—部分的第二殘留物 送回,第-蒸娜,作為—種或多種萃取劑,而第二殘留物可包含低於 3〇重量%的醋酸。在-實施对巾,帛—蒸齡可在低於銜帕(咖), 例如低於50千帕,或低於2〇千帕的壓力下操作。 在第二實施方式中,本發明是針對一種用於生產乙醇的製程,其包 括如下的步驟:提供-種乙醇粗產物,該乙醇減物包含乙醇、醋酸、 醋酸乙醋、乙跡水;在第-縫塔中於—種或多種萃取_存在下 離至少-部分的乙醇粗產物,而成為包含㈣和醋酸乙_第—顧 物’及包含乙醇、醋酸乙醋、和一種或多種萃取劑的第一殘留物;在 -蒸館塔分離第-殘留物,而產生包含乙醇和醋酸乙醋的第二潑出物第 =包含:種或多種萃取劑的第二殘留物’並分離至少—部分的第 物,而產生包含醋酸乙醋的第三顧出物,和包含乙醇的第三殘留物。 牛现在Ϊ三實施方式中’本發明是針對生產乙醇的製程,其包括如下的 =驟.在反應器中氫化醋酸進料流中的醋酸,形成乙醇粗產物 — 蒸解於水萃取_存在下分離至少—部分私雜產物 ^ =和:酸乙醋的第,出物’及包含乙醇、水:3 在第二蒸鱗分離第-殘留物,而產生包含乙醇 殘=人 水和醋酸的第二殘留物,並從第二館出物回收 出物’及包含 201247301 實施方式中,製程可包括分離至少—部分的第二殘留物而形成 水性物k和醋酸I醋酸流可返贩廳,而水性物流返回第一蒸德塔 7為萃取劑。可使用吸附裝置、分離臈、蒸解及其組合來分離水和醋 酸0 在另-實施方式中,這製程還包括在醋化單元使來自第二殘留物的 =和的至少-種醇(較佳者為甲醇)反應,而產生至少一種醋和水,從水 ^離出至少-種醋’而產生包含至少—種醋的醋產物流,和包含水的 水溶液物流。將水溶液物流送回第一蒸餾塔作為萃取劑。 在第四實施方式中,本發明涉及到生產乙醇的製程,其包括如下的 步驟··在反應器中氫化來自醋酸進料流中的醋酸,而形成乙醇粗產物, 在第-蒸顧塔巾於水萃輔畴在下並在低於7G千帕,例如低於5〇千 帕’或低於20千帕的磨力下操作,分離至少一部分的乙醇粗產物,而形 成包含乙链和醋酸乙_第—館出物,及包含乙醇、水和醋酸的第一殘 留物;在第二蒸齡分離第—殘留物,而產生包含乙醇的第二館出物, 及包含水和醋酸的第二殘留物,並從第二餾出物回收乙醇。 ,詳而言之,本發明涉及到回收在觸媒存在下氫化醋酸所獲得之乙醇 的製程。氫化反應產生乙醇粗產物,其包含乙醇、水、醋酸乙酿、醋酸、 和其他雜質。因為醋酸乙g旨和乙醇_錄接近,藉由蒸讎以從醋酸 乙酯和乙醇的混合物中分離醋酸乙酯。在乙醇粗產物中其他成分的存 在,例如醋酸乙酯、醋酸和乙醛的存在,取決於濃度的多寡,會進一步 使得乙醇和醋酸乙酯的分離複雜化。 為了改善從乙醇粗產物回收乙醇的效率,本發明的製程涉及在初始 (第一)分離蒸餾塔中藉由一種或多種萃取劑從乙醇粗產物回收乙醇。 抽移乙醇、水和醋酸以做為殘留物。抽移醋酸乙酯和其他輕有機物以作 為餾出物。萃取劑的存在使得乙醇產物可更有效地從醋酸乙酯副產物分 離。根據本發明實施方式使用萃取劑,可使大部分的醋酸乙酯從乙醇粗 產物回收。較佳者為在乙醇粗產物中至少有9〇%,例如至少有%%或至 6 201247301 /、有98/6的醋酸乙g旨經由第-|g出物回彳卜回收大部分的醋酸乙醋,可 使來自初始蒸館塔的殘留物中醋酸乙醋為低濃度,例如,低於i重量%, 低於0.3重魏或低於議重鄕。藉由制—種或彡種萃賴,可回收 醋酸乙自旨含量減少的乙醇產物。較佳者為在乙醇粗產物巾至少有5〇%的 乙醇,尤佳者為至少90%的乙醇回收於第一殘留物流。 有利的是,這種使用萃取劑的分離方法結果能在從乙醇粗產物回收 乙醇的操作中減少能源需求。 在本發明中使用的萃取劑可以有所不同。較佳者為萃取劑具有比餾 出物中主要成分更高的沸點。在較佳的實施方式十,所使用的萃取劑沸 點高於80°C,例如高於85°C,或高於1〇〇。〇。沸點高於2〇〇〇c的萃取劑也 可考量。一種較佳的萃取劑包括水。水可在氫化反應器產生,並回收作 為萃取劑。較佳者為至少一種萃取劑是氫化醋酸生產乙醇製程的副產 物。使用副產物作為萃取劑,則萃取劑的添加和回收成本可減少。 在一實施方式中,副產物是水’而藉由去除乙醇和/或醋酸以純化水。 純化水可減少回收在蒸餾塔中將會導致副反應的其他成分β使用水分離 裝置,例如吸附裝置或分離膜,或使醋酸反應的酯化單元可用來純化水。 水的純化也允許回收醋酸,其可返回到反應器。 在另一實施方式中,副產物水可以是稀酸流的一部分,而不需要加 強的純化。雖然並不限於稀酸流,但當氫化達成醋酸之高轉化率,高於 80% ’高於90%或高於95%時,則較佳者為稀酸流。因此,稀酸流可降 低整體的能源需求,同時在初始蒸餾塔維持高效的分離。稀酸流可包含 至少40重量%的水’例如,至少60重量%的水,或至少8〇重量%的水。 稀酸流可以包含醋酸。例如,萃取劑可以包含低於30重量%,例如低於 20重量% ’低於1〇重量%或低於5重量%的醋酸。未被理論所約束地,在 稀酸流中的醋酸不一定作為萃取劑,而該萃取劑可以減少攜入初始蒸餾 塔餾出物中的乙醇、水、和/或醋酸量。 其他合適的萃取劑也可使用,包括例如,二曱基亞颯、甘油、二甘 201247301 醇_ 1萘酚、對苯二酚、N,N,_:甲基甲酿胺、i,4_ 丁二醇、甘醇-丨,5-戊 醇丙—醇-四甘醇_聚乙二醇,甘油-丙二醇四甘醇-1,4-丁二醇、乙醚、 :酸甲酉曰、環已燒、N,N,-二甲基-1,3 -丙二胺,N,N'-二甲基乙二胺、二乙 一胺己—胺、丨,3 _二胺戊烷,烧基化嗟吩、十二燒、十三烷、十四烷、 氣化石蠟、及其混合物。這些其他萃取劑可配用水。一些合適的萃取劑 包括那些描述於美國專利號4,379,〇28、4,569,726、5,993,610和6,375,807 者,其全部内容在此納入參考。 在實施方式中,萃取劑可饋入初始蒸餾塔,以便處理乙醇粗產物。 ^實施方式中,萃取劑先饋入並結合乙醇粗產物,才引入初始蒸飽 ^較佳者為,报大部分的乙醇、水和醋酸從乙醇粗產物移出作為從初 蒸〇趨塔的殘留物。殘留物流,例如可包含來自乙醇粗產物中的30%至 99.5/的水,和挪幻⑻細雜。殘留物賴可包含萃輔和水,而 f此在殘留物巾水濃度可以高於在乙醇粗產物巾的水濃度。例如,藉由 多鋼外的分離顯塔,萃糊可從触财喊,並送回初始 般來說來自初始蒸鶴塔的館出物可包含醋酸 物可全部或—部分義_喊減《。在4實施方式巾,來= :::的館出物還可包含乙醇和較佳者為低於15重量%的水,低於Μ 0、7,低於4重量%的水或低於2重量%的 萃 餾塔從餾出物去W at &amp; 另卜的卒取蒸 步分_出物成為醋酸』式中,輕傲份蒸館塔可用於進-應器。 w啊乙s日流和乙醇流’而該醋酸乙S旨流回收到氫化反 -步3本=的t施方式通常可減少殘留物中醋酸乙s旨量,但由於進 以分二產:二物:的任何醋酸乙醋較佳者為加 若醋酸乙酯低201247301 V. If there is a chemical formula in this case, please disclose the chemical formula that best shows the characteristics of the invention: None. </ RTI> </ RTI> </ RTI> </ RTI> </ RTI> </ RTI> </ RTI> </ RTI> </ RTI> </ RTI> </ RTI> </ RTI> </ RTI> </ RTI> <RTIgt; U.S. Patent Application Serial No. 13/094,641, filed on Apr. 26, 2011, and No. 13/162, No. 34, filed on Jun. 16, 2011. TECHNICAL FIELD OF THE INVENTION The present invention generally relates to a process for producing ethanol from acetic acid in a hydrogenation reactor, and more particularly to a process for recovering ethanol from extractive distillation. [Prior Art] The traditional production method of ethanol used in industry is from petrochemical raw materials, such as petroleum, natural gas, charcoal, or from injection problems, such as reduction or reduction, or (four) materials or fiber materials, such as corn or Lai. It has traditionally come from petrochemical feedstocks and fiber raw materials to produce B-methods - hybrid hydration, methanol colloidal reactions, direct alcohol synthesis and, Fischer_Tr〇psch synthesis. Instability ^ The price of the shoulder material will cause the cost fluctuation of the traditional way of producing ethanol. #The raw material price on Pan = will make it possible to substitute the source to produce B. The demand is more riding, the powder raw material and the cellulose raw material can be fermented into ethanol. However, the fermentation method Usually used in consumer ethanol production, ϊΐίϋΐϊί can be used for fuel or human consumption. In addition, the fermentation of the powder or fiber 2 will compete with the food source, thus limiting the amount of ethanol that can be used in industrial production. The reduction of saccharides and/or their domain-based compounds for the production of ethanol has been extensively studied, 201247301, and various catalysts have been mentioned in the literature. The combination and operating conditions of the support. When alkanoic acid (e.g., acetic acid) is reduced, other compounds are formed with or formed by a side reaction which limits the production and recovery of ethanol from such a reaction mixture. In the hydrogenation process, esters, ethanol and/or water are produced together to form an azeotrope, which is difficult to separate. In addition, when the conversion is incomplete, 'unreacted acetic acid still remains in the reactor product. And it must be removed to recover ethanol. European Patent EP02060553 describes a process for the conversion of hydrocarbons to ethanol, which involves converting hydrocarbons to acetic acid and then hydrogenating the acetic acid to obtain ethanol. Separating the stream from the hydrogenation reactor, In order to obtain a stream of ethanol and a stream of acetic acid and ethyl acetate, the stream is recycled to the hydrogenation reactor. U.S. Patent No. 7,842,844 describes the conversion of hydrocarbons to ethanol in the presence of a particulate catalyst and optionally converted to In the reaction of acetic acid, it can improve the selectivity, the activity of the catalyst and the service life of the catalyst. (4) Steps. Others have proposed various extractants for separating ethanol, acetic acid, and water. U.S. Patent No. 4,654,1Z3 describes a process for separating ethanol from water by using an extractant. U.S. Patent Nos. 4,379,028 and 4,569,726 describe the use of extracts to recover ethyl acetate from a mixture of ethyl acetate/ethanol/water. U.S. Patent No. 6,375,8,7 is described by A method for separating ethanol and ethyl acetate by an extracting agent, and there is still a need to improve a process for recovering ethanol from a crude product obtained by, for example, a reduction of the silk compound, and/or a silk compound thereof. - In the embodiment, the present invention is directed to the production process of Lin, which comprises from the reaction of the chemical processing, and the production of the coarse flow technique 2 or the extraction, the separation of at least part (10) Crude product: the first residue of the acetaminophen acetate series, and the first residue containing various extractants of ethanol and vinegar, and the extractant is selected from water, dimethyl 2 4 201247301 (dimethylsulfoxide) ),glycerin, Glycol,! _ phenol, hydroquinone, hydrazine, Ν '_: mercaptocarbamide, 1,4-butanediol, glycol 丨, 5-pentanediol, propylene glycol _ tetraethylene glycol _ polyethylene glycol , glycerol-propylene glycol-tetraethylene glycol _1,4-butanediol, diethyl ether, formic acid, brewing, cyclohexyl, N,N, dimethyl-propylamine, N,N'-dimethylethylene A group consisting of amine amines, diethylenetriamine, hexamethylenediamine, oxadiamine pentane, alkylthiophene, dodecane, tridecane, tetradecane, gasified paraffin, and mixtures thereof. In one embodiment, the first residue may comprise less than 5% by weight ethyl acetate. The process further includes separating at least a portion of the first residue in the second distillation column to produce a second distillate comprising ethanol and ethyl acetate, and a second residue comprising one or more extractants. The first pavilion of the mouth P knife produces a third take-up containing ethyl acetate and a third residue containing ethanol. At least part of the second residue of the embodiment cap is returned, the first steaming, as one or more extractants, and the second residue may comprise less than 3% by weight acetic acid. In the implementation of the towel, the steaming age can be operated at a pressure below the level, for example below 50 kPa, or below 2 kPa. In a second embodiment, the present invention is directed to a process for producing ethanol comprising the steps of: providing a crude ethanol product comprising ethanol, acetic acid, ethyl acetate, and ethyl acetate; In the first-seam column, the crude product of at least part of the ethanol is present in the presence or absence of extraction, and comprises (4) and ethyl acetate, and comprises ethanol, ethyl acetate, and one or more extractants. a first residue; separating the first residue in a steaming tower to produce a second precipitate comprising ethanol and ethyl acetate; a second residue comprising: one or more extractants' and separating at least - Part of the first product, resulting in a third drug comprising ethyl acetate, and a third residue comprising ethanol. In the present invention, the present invention is directed to a process for producing ethanol, which comprises the following steps: hydrogenation of acetic acid in a acetic acid feed stream in a reactor to form a crude ethanol product - distillation in the presence of water extraction At least - part of the private product ^ = and: the first, the output of the acid vinegar 'and contains ethanol, water: 3 in the second steaming scale to separate the first residue, resulting in a second containing ethanol residue = human water and acetic acid Residues, and recovering from the second museum's and '201220121. In the embodiment, the process may include separating at least a portion of the second residue to form an aqueous material k and an acetic acid I acetic acid stream. The stream is returned to the first steaming tower 7 as an extractant. The adsorption device, the separation enthalpy, the digestion, and combinations thereof may be used to separate the water and the acetic acid. In another embodiment, the process further comprises at least the alcohol of the = and the second residue in the acetating unit (preferably The reaction is methanol) to produce at least one vinegar and water, and at least one vinegar is removed from the water to produce a vinegar product stream comprising at least one vinegar, and an aqueous stream comprising water. The aqueous stream is returned to the first distillation column as an extractant. In a fourth embodiment, the invention relates to a process for producing ethanol comprising the steps of: hydrogenating acetic acid from an acetic acid feed stream in a reactor to form a crude ethanol product, in a first steaming tower Working under the water extracting subdomain and at a grinding force below 7G kPa, for example below 5 〇 kPa ' or below 20 kPa, separating at least a portion of the crude ethanol product to form a chain comprising ethyl acetate and ethyl acetate _The first library, and the first residue containing ethanol, water and acetic acid; the first residue is separated at the second steaming age to produce a second museum containing ethanol, and a second containing water and acetic acid The residue is recovered from the second distillate. In particular, the present invention relates to a process for recovering ethanol obtained by hydrogenating acetic acid in the presence of a catalyst. The hydrogenation reaction produces a crude ethanol product comprising ethanol, water, acetic acid, acetic acid, and other impurities. Since ethyl acetate was similar to ethanol, the ethyl acetate was separated from the mixture of ethyl acetate and ethanol by distillation. The presence of other components in the crude ethanol product, such as the presence of ethyl acetate, acetic acid and acetaldehyde, further complicates the separation of ethanol and ethyl acetate depending on the concentration. In order to improve the efficiency of recovering ethanol from the crude ethanol product, the process of the present invention involves recovering ethanol from the crude ethanol product by one or more extractants in an initial (first) separation distillation column. Ethanol, water and acetic acid were pipetted as a residue. Ethyl acetate and other light organics were pipetted as a distillate. The presence of the extractant allows the ethanol product to be more efficiently separated from the ethyl acetate by-product. Most of the ethyl acetate can be recovered from the crude ethanol product using an extractant in accordance with an embodiment of the present invention. Preferably, at least 9% by weight of the crude ethanol product, for example at least %% or to 6 201247301 /, 98/6 of ethyl acetate is used to recover most of the acetic acid via the first -|g product Ethyl vinegar can make the ethyl acetate in the residue from the initial steaming tower low concentration, for example, less than i% by weight, less than 0.3 wei or lower than the weight. The ethanol product having a reduced content of acetic acid can be recovered by the production or the extraction. Preferably, at least 5% by weight of ethanol is present in the crude ethanol product, and particularly preferably at least 90% of the ethanol is recovered in the first residue stream. Advantageously, this separation process using an extractant results in reduced energy requirements in the operation of recovering ethanol from the crude ethanol product. The extractant used in the present invention may vary. Preferably, the extractant has a higher boiling point than the main component of the distillate. In the preferred embodiment 10, the extractant used has a boiling point above 80 ° C, such as above 85 ° C, or above 1 Torr. Hey. An extractant having a boiling point higher than 2 〇〇〇c can also be considered. A preferred extractant includes water. Water can be produced in the hydrogenation reactor and recovered as an extractant. Preferably, at least one of the extractants is a by-product of the process for producing ethanol from hydrogenated acetic acid. By using by-products as an extractant, the cost of addition and recovery of the extractant can be reduced. In one embodiment, the by-product is water&apos; and the water is purified by removing ethanol and/or acetic acid. The purified water can reduce the recovery of other components in the distillation column which will cause side reactions, such as a water separation device, such as an adsorption device or a separation membrane, or an esterification unit that reacts acetic acid can be used to purify water. Purification of the water also allows the recovery of acetic acid, which can be returned to the reactor. In another embodiment, the by-product water can be part of a dilute acid stream without the need for enhanced purification. Although not limited to dilute acid streams, when hydrogenation achieves a high conversion of acetic acid, above 80% 'more than 90% or above 95%, a dilute acid stream is preferred. Therefore, the dilute acid stream can reduce the overall energy demand while maintaining efficient separation in the initial distillation column. The dilute acid stream may comprise at least 40% by weight of water 'e.g., at least 60% by weight of water, or at least 8% by weight of water. The dilute acid stream can comprise acetic acid. For example, the extractant may comprise less than 30% by weight, such as less than 20% by weight 'less than 1% by weight or less than 5% by weight of acetic acid. Without being bound by theory, the acetic acid in the dilute acid stream is not necessarily an extractant, and the extractant can reduce the amount of ethanol, water, and/or acetic acid carried into the distillate of the initial distillation column. Other suitable extractants may also be used, including, for example, dimercaptopurine, glycerin, digan 201247301 alcohol _ 1 naphthol, hydroquinone, N, N, _: methyl ketoamine, i, 4 _ Glycol, glycol-indole, 5-pentanol-propanol-tetraethylene glycol_polyethylene glycol, glycerol-propylene glycol tetraethylene glycol-1,4-butanediol, diethyl ether, acid methyl hydrazine, ring Burning, N,N,-dimethyl-1,3-propanediamine, N,N'-dimethylethylenediamine, diethylamine-amine, hydrazine, 3-diamine pentane, alkylation Porphin, dodecan, tridecane, tetradecane, gasified paraffin, and mixtures thereof. These other extractants can be formulated with water. Some suitable extractants include those described in U.S. Patent Nos. 4,379, 〇28, 4, 569, 726, 5, 993, 610, and 6, 375, 807, the entire disclosures of which are incorporated herein by reference. In an embodiment, the extractant can be fed to an initial distillation column to treat the crude ethanol product. In the embodiment, the extractant is fed first and combined with the crude ethanol product, and the initial steaming is introduced. Preferably, most of the ethanol, water and acetic acid are removed from the crude ethanol product as residues from the initial steaming tower. Things. The residual stream, for example, may comprise from 30% to 99.5 per cent of water in the crude ethanol product, and unpredictable (8) fine impurities. The residue may comprise extract and water, and f may have a higher concentration of water in the residue than in the crude ethanol towel. For example, with the separation tower outside the multi-steel, the paste can be shouted from the touch of wealth, and sent back to the original. Generally speaking, the output from the original steaming tower can contain all or part of the acetic acid. . In the 4th embodiment towel, the gallery output of :::: may further comprise ethanol and preferably less than 15% by weight of water, less than Μ 0, 7, less than 4% by weight of water or less than 2 The % by weight of the extractive column is taken from the distillate to Wat &amp; another stroke of the steaming step to the output of acetic acid, and the lightly proud steaming tower can be used for the inlet and outlet. w ah s s day flow and ethanol flow 'and the acetic acid B S stream to the hydrogenation counter-step 3 = t application method can generally reduce the amount of ethyl acetate in the residue, but because of the second production: Two substances: any ethyl acetate is preferred as ethyl acetate

於50重量醇,則可以不必使用另-蒸解分離醋酸獅乙^自E 殘 8 201247301 =物分離的乙s旨可送_初始_塔,並移出作為第一館出物 種返回_酸乙自旨流可在萃取劑進料位置的下面送人初始蒸館塔。 的材rmr用於任何氫化生產乙醇之製程。可用於醋酸氫化 的材料、麟、反應條件和分離製程進—步說明如下。 這 用於本發明餘_料,鑛和絲,可靖生自任何合適的來源, =^然氣、石油、煤炭、生物料等。舉例而言,通過甲_基化、乙 酸氧化'乙烯氧化、氧化發酵、厭氣發酵等,可以生產醋酸。適合於生 產醋酸之曱賴基化製程描述於美國專利號7,208,624、7,115,772、 7,005,541 ^ 6,657,078 &gt; 6,627,770 &gt; 6,143,930 ^ 5,599,976 ^ 5,144,068 ' 5,026,9G8、5輝,259和4,994,6G8,其全部揭露在此納人參考^者可視 情況選擇地’乙醇生產可和這些甲醇化製程整合在―起。可視情況 選擇地,乙醇生產可和此種甲醇之絲化製程整合在一起。 由於石油和天然氣價格忽起忽落,利用備用碳源來生產醋酸和例如 甲醇和-氧化碳之巾聰的方法,已引起越來越大的興趣。特別是,當 石/‘由價格比天然氣較南時’由任何合適的碳源所魅的合成氣〇 gas )生產醋酸可以成為有利。例如美國專利第6,232,352號揭露改裝甲醇 廠以生產醋酸的方法’在此可納入做為參考。通過改裝甲醇廠,可顯著 地減〉'或大部分的移除新建醋g纖大量的資本成本以及其所伴隨產生一 氧化碳。由甲醇合成循環(methanol synthesis loop)衍生產出全部或一部 分的合成氣,其並被提供至隨—氧化碳之分離裝置,紐再用於生產 醋酸。以類似的方式,麟氫化步驟的氫氣可由合航來提供。 在一些實施方式中,上述的醋酸氫化製程中一部分的或全部的原料 可一部分或全部衍生自合成氣。例如,醋酸可由甲醇和一氧化碳形成, 它們都可來自合成氣藉由部分氧化重整或賊重整形成合成氣, 以及-氧化碳可從合成氣分離。同樣地,祕氫化醋酸形成乙醇粗產物 的氫氣可由合成氣分離得之。相應地,合成氣可來自不同的碳源。碳源, 例如’可以選自由城氣、原油、石油、煤炭、生物料及其組合所組成 201247301 之群組。合成氣或氫氣’也可得自生物衍生曱減體,如賴填埋場或 農業廢棄物生物產生之生物衍生的甲烷氣體。 ,較於;ε化燃料如煤或天然氣而言,生物料衍生之合成氣含有可檢 =的14c同位素。地球大氣之間怪定新形成及恆定衰魏解之間會形成平 衡,而因此在地球上大氣中的碳原子核中mc核的比例係長期恆定。因活 有機體係存在於厢大氣巾,因此相同分WM_14C:12C&amp;例會建立於 活有機體中’而此分布比例會在活有機體死亡時停止改變,但MC會以約 6000年之半衰期衰變分解。㈣、醋酸和/或乙義從生物料衍生之合成 氣所形成,預計將會具有大致類似活生物體的HC的含量。例如,曱醇、 醋酸和/或乙醇的14c : 12c比例可為活有機體之14C :,比例之〇 5至約i。 在其它實施方式中,其所述的合成氣、甲醇、醋酸和/或乙醇全部衍生自 化石燃料’亦’生自6G’GGG年前所產生之碳源者,則不具有可伽得 之14c含量》 在另一實施方式中,用於氫化步驟之醋酸可從生物料發酵形成。發 酵製程中較佳者為採用醋化(acetogenJc)製程或藉由同質醋化 (homoacetogenic)微生物來使糖發酵而產生醋酸,以及產生如果存有的 話,也會是很少的作為副產物之二氧化碳。發酵製程的碳效率較佳者為 高於7〇%,高於8〇臟高於9〇% ’而#統的酵母製程其通常碳效率約為 67%。可視情況選擇地,麟發酵製程的微生物為__簡(卿如)選自 由梭狀芽祕1、概桿g、摩雷拉梭狀軸_、嗜雛觀性細菌、 丙酸菌、丙酸梭狀芽抱桿菌、革蘭氏陰性厭氧菌和絲桿菌所組成之群組, 且尤其是菌種(species)係選自由蘋果酸梭菌、酪酸梭菌、摩雷拉嗜熱 性梭菌1奇韋嗜熱性嫌氣性_、德布魯基乳酸菌、丙酸細帛、丙酸^ 旋菌、蘇辛尼克厭氧菌、乳酸菌類桿菌和内切葡聚醣酶桿菌所組成之群 組。在這個製程中可視情況選擇性地全部或部分來自主物料未發酵的殘 留物,例如:木酚素(lignans),可氣化形成氫氣,其可用於本發明之 步驟。形成醋酸之典型發酵製程揭露於美國專利號6,5〇9,18〇,其全部内 201247301 谷在此納入參考。另見美國專利申請公開案號2008/0193989和 2009/0281354,其全部内容在此納入參考。 例如,生物料可包含但不限於農業廢棄物、森林產物、草及其他纖 維素材料、木材採伐殘留物、軟木片、硬木片、樹枝、樹樁、樹葉、樹 皮、鑛木屑、不合格紙漿、玉米、玉米稍稈、小麥結样、稻草、甘顧 留物柳枝稷、^:草、動物糞便、城市垃圾、城市生活污水、商業廢物、 葡萄殘留物糾一殼、核桃殼'椰子殼、咖啡殘留物、草顆粒、草球、 木球、紙板、纟、歸和布料。另—生物騎是驗,其為木質 留物、半纖維素和無機化學品的水溶液。 美國再發證專利RE35,377號,在此也納入參考,其提供藉由炭素材 料’例如像是石油、煤炭、天然氣和生物料轉化來生產甲醇之方法。這 製程匕3固體和/或液體炭素材料之灸化氣化以獲取 製程氣體’雜由額外天織進行統麵而形成合成氣。合成氣轉化 為甲醇’該曱醇再,贿基化則可得_。該方法也同獅可產生氮氣, f如上所述可用於本發明4國專利第说训^其中揭示廢棄生物 料通過氣化轉化成合航的製程,和美國專㈣⑽5,754號揭示含氮氣 體態組成物’例如包含氫氣和—氧化碳之合成氣之製法,其全部内容在 此納入參考。 -饋入氫化反應的醋酸也可包含其他羧酸類及其酸酐類,以及乙醛和 =嗣。較佳者為,合適的醋酸進料流包含一種或更多種化合物選自由醋 酸、醋酐、乙醛、醋酸乙酯、及其混合物所組成之群組。這些其他化合 物也可在本發明的製程中被氫化。在一些實施方式中,羧酸類,例如丙 酸或其醛,的存在,可以是有益於生產丙醇。水也可存在於醋酸進料中。 另外’可直接採用來自美國專利第6,657,078號所描述的甲醇羰基化 裝置的閃蒸槽之蒸汽形式的醋酸來作為粗產物,其美國專利全部内容在 此納入參考。例如,該粗蒸汽產物可直接饋入本發明乙醇合成反應區而 不需要冷凝醋酸和輕餾份’或者移除水,進而可節約總處理成本。 201247301 醋酸可在反應溫度蒸發’隨後蒸發的醋酸可連同未稀釋狀態之氮或 以例如氮氣、氬氣、氦氣、二氧化碳之類的相對惰性載氣所稀釋之氫一 起饋入反應器。為使反應在氣相中操作,應控制系統中溫度使得溫度不 低於醋酸之露點。在一實施方式中,醋酸可在特定壓力下的醋酸沸點蒸 發’然後蒸發的醋酸可進一步被加熱至反應器入口溫度。在另—實施方 式中,該醋酸於蒸發前與其他氣體混合,然後加熱該混合蒸汽到反應器 入口溫度。較佳者為,在溫度等於或低於125°C,使氫氣和/或回收氣體通 過醋酸,而將醋酸轉移至蒸汽狀態,接著將該合併後氣體流加熱到反應 器入口溫度。 一些醋酸氫化形成乙醇製程的實施方式中可使用多種配置,包含固 定床反應器或流化床反應器。在本發明許多的實施方式中,可以使用,,絕 熱”反應器;亦即在此些實施方式中,幾乎沒有或根本沒有必要在反應區 通入内部管道作熱量之添加或移除。在其他實施方式中,可以使用徑向 流動反應器(radial flow reactor)或反應器組,或者可以使用一系列反應 器,無論其具有或不具有熱交換、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 個容器之内或一系列其中介入熱交換器之容器(組)。 在較佳的實施方式中,觸媒用於固定床反應器中,反應器,例如其 呈管道或管形狀,其中反應物通常以蒸汽的形式來傳送或通過觸媒。可 以採用其他反應器,例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。 _氩化反應可以在液相或氣相中進行。較佳者為反應在下列情況下以 氣相進行。反應溫度可介於125°C至350°C,例如:從2〇〇。(:至325。(:,從 225C至300C ’或從250°C至300°C。壓力範圍從1〇千帕(kpa)至3,〇〇〇千 帕,例如.從50千帕至2,300千帕,或從1〇〇千帕至^500千帕。反應物饋 入反應器的”蒸汽每小時空間速度’,(GHSV)可為高於至少5〇〇/小時,例 12 201247301 如:高於至少脚/小時,高於至少I·小時,甚至高於 就範圍而言,GHSV可以從料時至5_小時,例如:㈣/ ^時至 3議:、時,小時至10._/小時,或丨,_、時 雖然反應每莫耳醋酸會消耗兩莫耳氫氣,而產生-莫耳的乙醇在 進料流中氫氣對醋酸的實際莫耳比可能會有所不同,可從ι〇〇 ·⑷. 100,例如,從50 :山·· 5〇,從20 :…:2,或從18 :㈤:工。 接觸或滞留賴也雜大的不同,取決於醋酸f、觸媒、反應器、 溫度和壓力錢數。典觸接_____數小_上, 用固定床以外的觸媒系統,職相反應較佳的接觸時間為從αι秒至ι〇〇 秒。 醋酸氫化形成乙醇較佳者為在氫化觸媒存在下進行。典型的觸媒進 -步記載於美國專利第7,6〇8,744號和第7,863.號,和美國專利申請公 ,案號wio/omm和2〇10/0197985,其全部内容在此納人參考。在另 —實施方式中’觸媒係美國專射請公開魏2_/_6()9所描述的始/ 麵/硫型觸媒,其全部内容在此納入參考。在一些實施方式中,觸媒可為 塊體散裝的觸媒(bulk catalyst) ..... 在一實施方式中,觸媒包含第一金屬,選自由銅、鐵、鈷、鎳、釕、 錢、免、鐵、錄、紐、鈦、鋅、路、銖、翻和鶴所組成之群組。較佳者 為第一金屬選自由翻、把、銘、錄和釕所組成之群組。 如上所述,在一些實施方式中,該觸媒還包含第二金屬,其通常會 作為—種促進劑。如果存在的話,第二金屬較佳者為選自由銅、鉬、錫、 =鐵、結、奴'鎢、把、始、網'飾、猛、釕、銖'金及錄所組成之 、且。尤佳者為’第二金屬選自由銅、錫、鈷、銖及鎳所組成之群組。 如果觸媒包含兩種或更多種的金屬,例如第一金屬和第二金屬,則 f—金屬用量可從0.1至重量%,例如從〇.1至5重量%,或從0.1至3重量 ^。第二金屬較佳的用量從0.1至20重量%,例如從0.1至10重量%,或 者從〇·1至7.5重量%。 〆 13 201247301 峰、中較佳金屬組合包括觸’釕,銖、蝴、 纪金侍简、綠、她、銅㈣ 第三金屬,第三金屬可以選自上面列出的任何第—金 樣I,ini'要第三金射同於第-金屬和第二金屬即可。在較佳 Ϊ如!;2fr…、釕、銅、辞,、錫及鍊所組成之群 除了 ί稽^。在一實施方式中,觸媒可包紛白、錫及姑。 金屬外,在本發明—些實施方式中觸媒進一步 ===,。difiedsupp呤本文中所使用、^ 體。Ί係k 3續雜料和調敎舰材繼錢支顧改_之支撐 叫οίΓο?或改質續體的總重量較佳者為觸媒總重量的75重量%至 滅:&amp;78ί _至,或獅重量駐97.5重量. ΪΪ _體,例如二氧切、氧化魏化銘、ΠΑ族石夕 ::支=,、熱解二氧化梦、高純度二氧化魏其混合物。其 龍,包含但不限於氧化鐵、氧化|g、二氧献、氧化錯、氧化 鎂炭、石墨、咼表面積石墨化炭、活性炭及其混合物。 支擇體可极質體,其技f规體存在量觀丨㈣重魏, =^=量%,從1至2〇重魏,或3至15重魏,該百分率係 在一些實施方式中’支撐體改性劑可為酸性改性劑,其可增加觸媒 的酸度》_ _性支顧雜劑可輯自由ινβ族金雜化物、仰族 金屬氧化物、VIB族金屬氧化物、νπΒ族金屬氧化物、…皿族金屬氧化 物:氧化師其混合物所域之群組。酸性績體改性劑包含那些選自 由二氧化邮〇2)、氧德(Zf〇2)、祕銀⑽你、卩她(Ta你、氧化 鋁(ai2o3)、氧化棚(B2〇3)、五氧化二麟(p2〇5)、三氧化二錄帥㈣、氧化 201247301 鎢(W03)、氧化鉬(Mo〇3)、二氧化二鐵(Fe2〇3)、三氧化二鉻(Cr2〇3)、氧 化釩(V2〇5)、二氧化錳(Mn〇2)、氧化銅(Cu〇)、氧化鈷(c〇2〇3)或氧化鉍 (Bi2〇3)所組成之群組。較佳的支撐體改性劑包括鎢、鉬、及釩之氧化物。 在另-實施方式中,支撑體改性劑可為一種具有低揮發性或無揮發 性的鹼性改性劑。此種的驗性改性劑,例如,可以選自由(丨)驗土金屬 氧化物’(11)驗金屬氧化物,(iii)鹼土金屬偏石夕酸鹽,㈤鹼金屬偏矽 酸鹽’(v)週期表ΠΒ族金屬氧化物,(vi)週期表ΠΒ族金屬偏矽酸鹽, (vii)週期表ΙΙΙΒ族金屬氧化物’(νϋί)週期表1113族金屬偏矽酸鹽,及 其混舍物所組成之群組《除氧化物和偏矽酸鹽外,其他類型的改性劑包 含猶鹽、亞硝酸鹽、醋酸鹽和魏鹽亦可用。雜性支撐體改性劑係 選自由納 '卸、m纪及鋅的氧化物和偏鹽,以及任何上 述的混合物顺狀群組-較佳的支禮體改_切_,尤佳者為偏 矽酸鈣(CaSi03)。偏矽酸鈣可呈結晶或無定形(am〇rph〇us)的形式。 適合使用於本發明的觸媒組成物較佳者為改質支樓體浸潰金屬 (metal i—egnatkm)而得’但其他製程,如化學氣相沉積(ehemieal叫沉 deposition)也可使用。此浸潰技術描述在美國專利號7,6〇8,744和 7,863,489,與美國專射請公開案號2G1G/G197485,其全部内容在此納入 參考。 觸媒經過洗務、乾燥和培燒,該觸媒可被還勒活化。還原係在還 原性氣體存在下進行,触者為統之存在下進行。在初始的環境溫度 (ambienttemperature)上升到400。(:下,將還原性氣體不斷地通過觸媒。 在-實施方^巾’難者餘麟已加到氫化反應容雜再進行還原反 應。 特別疋,醋酸氫化可達成良好的醋酸轉化率和良好的對乙醇選擇率 和產率。就本發明目的而言,“轉化率’,_詞是指在鱗巾的醋酸轉換成 醋酸以外之化合物量。轉化率以在進料中醋酸之百分率表示。轉化率至 少可在4〇%以上’例如,至対观’至少細%,至対娜或至 15 201247301 ㈣赌二ί的醋酸之莫耳百分率來表應該賴到每一種 =曰,轉變之化。物具有獨立的選擇率,而選擇率也和轉化率無關。例 二經轉化6G莫耳%的醋酸為乙醇,我們指乙醇的選擇率為6〇%。較 佳者為’觸媒對乙醇之選擇率至少有6〇%,例如:至少有聽,或至, 有80%。在本發明實施方式中亦較佳者為,對不被期待的產物,例如甲 院、乙烧和三氧化碳紐低之選擇〜對這些不被麟的產物的選擇率, 較佳者為低於4%,例如,低於2%或低於丨%。 “產率’’是減化餘巾每仟克觸縣小時_成敏物,例如 乙醇’的克數。產率可為每仟克觸媒每小時1〇〇至3,〇〇〇克的乙醇。 在各種本發明實施方式中’在進行任何後續處理之前,如純化和分 離之前,氫化製程所生產的乙醇粗產物通常包含未反應的醋酸,乙醇和 水。本文中所使用的術語“乙醇粗產物”是指任何包含從5至7〇重量%的 乙醇和5至40重量%的权組成物。乙醇粗產物的典型組成範圍提供於表 1。表1中定義的“其他,,可以包含,例如,g旨類、喊類、駿類、綱類十 烴類和二氧化碳。 表1 :乙醇粗產物組成 !度(重量%). 濃度(重量%)道…舌令 《萃 70 z; ,产 一&quot;&quot;~ ------For 50 weights of alcohol, it is possible to separate the acetic acid lion from the E-residue 8 201247301 = the separation of the substance can be sent _ initial _ tower, and removed as the first museum species return _ acid B The stream can be sent to the initial steaming tower below the extractant feed location. The material rmr is used in any hydrogenation process to produce ethanol. The materials, the lining, the reaction conditions and the separation process which can be used for the hydrogenation of acetic acid are described below. This is used in the present invention for the remainder of the material, minerals and silk, which can be produced from any suitable source, = gas, petroleum, coal, biomass, and the like. For example, acetic acid can be produced by methylation, acetic acid oxidation, ethylene oxidation, oxidative fermentation, anaerobic fermentation, and the like. A ruthenium-based process suitable for the production of acetic acid is described in U.S. Patent Nos. 7,208,624, 7,115,772, 7,005,541 ^ 6,657,078 &gt; 6,627,770 &gt; 6,143,930 ^ 5,599,976 ^ 5,144,068 ' 5,026,9G8, 5 Hui, 259 and 4,994,6G8, all It is revealed that the ethanol production can be integrated with these methanolization processes. Optionally, ethanol production can be integrated with this methanol filamentization process. As oil and natural gas prices fluctuate, the use of alternative carbon sources to produce acetic acid and methods such as methanol and carbon monoxide has attracted increasing interest. In particular, it can be advantageous to produce acetic acid when the stone / 'synthesis gas from the price of natural gas is more south than by any suitable carbon source." For example, a method of modifying a methanol plant to produce acetic acid is disclosed in U.S. Patent No. 6,232,352, the disclosure of which is incorporated herein by reference. By modifying the methanol plant, it is possible to significantly reduce the capital cost of the new vinegar and the carbon dioxide associated with it. Derived from a methanol synthesis loop produces all or a portion of the syngas, which is supplied to a separator for carbon monoxide, which is then used to produce acetic acid. In a similar manner, the hydrogen in the hydrogenation step can be provided by a combination. In some embodiments, some or all of the feedstock in the above-described acetic acid hydrogenation process may be derived from syngas. For example, acetic acid can be formed from methanol and carbon monoxide, both of which can be derived from syngas by partial oxidation reforming or thief reforming to form syngas, and - carbon monoxide can be separated from the syngas. Similarly, the hydrogen which forms the crude ethanol product from the hydrogenated acetic acid can be separated from the synthesis gas. Accordingly, the syngas can be from a different carbon source. The carbon source, for example, may be selected from the group consisting of city gas, crude oil, petroleum, coal, biomass, and combinations thereof 201247301. Syngas or hydrogen can also be obtained from biologically derived reduced bodies, such as biologically derived methane gas produced by landfills or agricultural waste organisms. Compared to; ε-fuels such as coal or natural gas, the bio-derived syngas contains a detectable 14c isotope. There is a balance between the new formation of the Earth's atmosphere and the constant decay of the Wei, and therefore the proportion of the mc core in the carbon nuclei in the atmosphere on Earth is long-term constant. Since the living organic system exists in the air, the same score WM_14C:12C&amp; will be established in the living organism' and this distribution will stop changing when the living organism dies, but the MC will decompose with a decay of about 6,000 years. (iv) Acetic acid and/or sulphur is formed from syngas derived from biological materials and is expected to have a substantially similar HC content to living organisms. For example, the 14c:12c ratio of sterol, acetic acid, and/or ethanol can be 14C: of the living organism, in the range of 〇5 to about i. In other embodiments, the syngas, methanol, acetic acid, and/or ethanol are all derived from a fossil fuel 'also' from the carbon source produced by 6G'GGG years ago, and there is no glycerable 14c. Content In another embodiment, the acetic acid used in the hydrogenation step can be formed from the fermentation of the biomass. Preferably, in the fermentation process, acetic acid is produced by fermentation using an acetogen Jc process or by homoacetogenic microorganisms, and if present, there are few as by-products. carbon dioxide. The carbon efficiency of the fermentation process is preferably higher than 7〇%, and higher than 8〇 is higher than 9〇%. The yeast process generally has a carbon efficiency of about 67%. Optionally, the microorganisms of the lining fermentation process are __Jian (Qingru) selected from the group consisting of fusiform buds, stalks g, Morerads, stalks, larvae, propionic acid, propionate a group consisting of Clostridium clostridium, Gram-negative anaerobic bacteria, and Mycelia, and especially species selected from Clostridium malic acid, Clostridium butyricum, and Clostridium thermophilus 1 Chivi's thermophilic anaerobic _, Debruchi lactic acid bacteria, propionate fine sputum, propionic acid serotonin, Susinick anaerobic bacteria, lactic acid bacteria and endoglucanase groups. Optionally, in this process, all or part of the unfermented residue from the main material, such as lignans, can be gasified to form hydrogen, which can be used in the steps of the present invention. A typical fermentation process for the formation of acetic acid is disclosed in U.S. Patent No. 6,5,9,18, the entire disclosure of which is incorporated herein by reference. See also U.S. Patent Application Publication Nos. 2008/0193989 and 2009/0281354, the entire contents of each of which are incorporated herein by reference. For example, biological materials may include, but are not limited to, agricultural waste, forest products, grass and other cellulosic materials, wood harvest residues, softwood chips, hardwood chips, branches, stumps, leaves, bark, ore chips, substandard pulp, corn. , corn stalks, wheat knots, straw, stalks, stalks, grass, animal waste, municipal waste, urban domestic sewage, commercial waste, grape residue, shell, walnut shell, coconut shell, coffee residue , grass particles, grass balls, wood balls, cardboard, enamel, return and cloth. In addition, the bio ride is an aqueous solution of wood residues, hemicellulose and inorganic chemicals. U.S. Reissue Patent No. RE35,377, which is incorporated herein by reference, which is incorporated herein by reference in its entirety in its entirety in the the the the the the the the This process 匕3 is a moxibustion of a solid and/or liquid carbon material to obtain a process gas, which is formed by additional weaving to form a syngas. The synthesis gas is converted to methanol. The sterol is then obtained by brittle. The method can also generate nitrogen gas with the lion, and f can be used in the invention of the four patents of the present invention as described above, which discloses a process for converting waste biomass into gasification by gasification, and discloses a nitrogen-containing body composition in the United States (4) (10) 5,754. The preparation of a product such as a synthesis gas comprising hydrogen and carbon monoxide is incorporated herein by reference. - The acetic acid fed to the hydrogenation reaction may also contain other carboxylic acids and their anhydrides, as well as acetaldehyde and = hydrazine. Preferably, a suitable acetic acid feed stream comprising 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 present invention. In some embodiments, the presence of a carboxylic acid, such as propionic acid or an aldehyde thereof, can be beneficial for the production of propanol. Water can also be present in the acetic acid feed. Further, acetic acid in the form of a vapor from a flash tank of a methanol carbonylation unit as described in U.S. Patent No. 6,657,078, which is incorporated herein by reference in its entirety, is incorporated herein by reference. For example, the crude steam product can be fed directly into the ethanol synthesis reaction zone of the present invention without the need to condense acetic acid and light ends' or remove water, thereby saving overall processing costs. 201247301 Acetic acid can be evaporated at the reaction temperature. Subsequent evaporation of acetic acid can be fed to the reactor along with undiluted nitrogen or hydrogen diluted with a relatively inert carrier gas such as nitrogen, argon, helium or carbon dioxide. In order for the reaction to operate in the gas phase, the temperature in the system should be controlled so that the temperature is not below the dew point of acetic acid. In one embodiment, acetic acid can be vaporized at the boiling point of acetic acid at a particular pressure. The then evaporated acetic acid can be further heated to the reactor inlet temperature. In another embodiment, the acetic acid is mixed with other gases prior to evaporation and the combined vapor is then heated to the reactor inlet temperature. Preferably, the hydrogen and/or recovery gas is passed through the acetic acid at a temperature equal to or lower than 125 ° C to transfer the acetic acid to a vapor state, and then the combined gas stream is heated to the reactor inlet temperature. A number of configurations can be used in some embodiments of the hydrogenation of acetic acid to form an ethanol process, including fixed bed reactors or fluidized bed reactors. In many embodiments of the invention, an adiabatic "reactor" can be used; that is, in such embodiments, there is little or no need to pass an internal conduit into the reaction zone for heat addition or removal. In embodiments, a radial flow reactor or a reactor set may be used, or a series of reactors may be used, with or without heat exchange, quenching or introducing more feed. A shell and tube reactor having a heat transfer medium is used. In many cases, the reaction zone can be disposed within a vessel or a series of vessels (sets) in which the heat exchanger is interposed. In a preferred embodiment, the catalyst For use in a fixed bed reactor, the reactor, for example in the form of a pipe or tube, wherein the reactants are typically passed in the form of steam or passed through a catalyst. Other reactors may be employed, 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 argonization reaction can be carried out in the liquid phase or in the gas phase. Preferably, the reaction is carried out in the gas phase under the following conditions: The reaction temperature can be between 125 ° C and 350 ° C, for example: from 2 〇〇. To 325. (:, from 225C to 300C ' or from 250 ° C to 300 ° C. Pressures range from 1 〇 kPa (kpa) to 3, 〇〇〇 kPa, for example. From 50 kPa to 2,300 kPa , or from 1 kPa to ^500 kPa. The "vapor hourly space velocity" of the reactants fed into the reactor, (GHSV) can be higher than at least 5 〇〇 / hr, Example 12 201247301 eg higher than At least feet/hour, above at least I·hour, even above the range, GHSV can be from material time to 5_hour, for example: (four) / ^ to 3::, hour, hour to 10._ / hour , or 丨, _, although the reaction will consume two moles of hydrogen per mole of acetic acid, and the actual molar ratio of hydrogen to acetic acid in the feed stream may be different from the ethanol produced in the feed stream, from ι〇 〇·(4). 100, for example, from 50: mountain··5〇, from 20:...:2, or from 18:(f): work. The difference between contact or stagnation depends on acetic acid f, catalyst, reactor The temperature and the amount of pressure. The number of the contact _____ is small. On the catalyst system other than the fixed bed, the contact time of the phase reaction is preferably from αιsec to ι〇〇sec. It is carried out in the presence of a hydrogenation catalyst. Typical catalysts are described in U.S. Patent Nos. 7,6,8,744 and 7,863, and U.S. Patent Application Serial No. Wio/omm and 2〇10/ 0197985, the entire contents of which are hereby referred to. In the other embodiment, the 'catalyst system US special shot, please disclose the start/face/sulfur type catalyst described in Wei 2_/_6()9, the entire contents of which are here. In some embodiments, the catalyst may be a bulk catalyst. In one embodiment, the catalyst comprises a first metal selected from the group consisting of copper, iron, cobalt, and nickel. Groups of 钌, 钌, money, exempt, iron, record, New Zealand, titanium, zinc, road, scorpion, turn and crane. Preferably, the first metal is selected from the group consisting of flipping, turning, inscription, recording, and sputum. As noted above, in some embodiments, the catalyst further comprises a second metal that will generally act as a promoter. If present, the second metal is preferably selected from the group consisting of copper, molybdenum, tin, iron, knot, slave 'tungsten, put, start, net 'decoration, fierce, 钌, 铢' gold and recorded, and . More preferably, the second metal is selected from the group consisting of copper, tin, cobalt, rhodium, and nickel. If the catalyst comprises two or more metals, such as a first metal and a second metal, the f-metal can be used in an amount from 0.1 to 5% by weight, for example from 0.1 to 5% by weight, or from 0.1 to 3 by weight. ^. The second metal is preferably used in an amount of from 0.1 to 20% by weight, for example from 0.1 to 10% by weight, or from 〇·1 to 7.5% by weight. 〆13 201247301 The best metal combinations in the peak and middle include the touches of '钌, 铢, 、, 纪金 简, green, her, copper (four) third metal, the third metal can be selected from any of the above-mentioned gold-like I,ini 'To be the third gold shot is the same as the first metal and the second metal. In a group such as 2fr..., 钌, copper, rhetoric, tin, and chain, except for ί ^. In one embodiment, the catalyst may be white, tin, and australis. In addition to the metal, in the present invention - in some embodiments the catalyst is further ===. Difiedsupp呤 is used in this article. Ί系 k 3 Continued miscellaneous materials and 敎 敎 继 继 继 继 _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ To, or the weight of the lion is 97.5 weight. ΪΪ _ body, such as dioxotomy, oxidized Wei Huaming, Dai Shishi:: branch =, pyrolysis dioxide dream, high purity dioxide Wei mixture. The dragons include, but are not limited to, iron oxide, oxidized |g, dioxane, oxidized, magnesium oxide, graphite, cerium surface area graphitized carbon, activated carbon, and mixtures thereof. The selected body can be a very plastid, and its technical formula has a quantitative effect (4) heavy Wei, =^=%, from 1 to 2 〇 heavy Wei, or 3 to 15 wei, the percentage is in some embodiments 'Support modifier can be an acidic modifier, which can increase the acidity of the catalyst. _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ Group metal oxides, ... metal oxides of the family: the group of the domain of the mixture of the oxidizer. Acidic modifiers include those selected from the group consisting of 2), oxygen (Zf〇2), Mithril (10), 卩 her (Ta you, alumina (ai2o3), oxidation shed (B2〇3), Bismuth pentoxide (p2〇5), bismuth oxide (four), oxidation 201247301 tungsten (W03), molybdenum oxide (Mo〇3), ferric oxide (Fe2〇3), chromium oxide (Cr2〇3) ), a group consisting of vanadium oxide (V2〇5), manganese dioxide (Mn〇2), copper oxide (Cu〇), cobalt oxide (c〇2〇3) or bismuth oxide (Bi2〇3). Preferred support modifiers include oxides of tungsten, molybdenum, and vanadium. In other embodiments, the support modifier can be an alkaline modifier having low or no volatility. An exemplary modifier, for example, may be selected from the group consisting of (丨) soil-measured metal oxides (11) metal oxides, (iii) alkaline earth metal bismuth salts, (5) alkali metal bismuth phthalates (v ) periodic table of lanthanide metal oxides, (vi) periodic table lanthanide metal bismuth citrate, (vii) periodic table lanthanide metal oxide '(νϋί) periodic table 1113 metal bismuth citrate, and its mixture Group of objects In addition to metabolites and other salts, other types of modifiers may also be used, including sulphate, nitrite, acetate and Wei salt. The hybrid support modifier is selected from the oxidation of Na's unloading, m- and zinc. And partial salt, as well as any of the above-mentioned mixtures, a preferred group of modified _ cut_, especially preferred is calcium metasilicate (CaSi03). Calcium metasilicate can be crystalline or amorphous (am The form of 〇rph〇us). The catalyst composition suitable for use in the present invention is preferably a metal i-egnatkm modified by a building body, but other processes such as chemical vapor deposition (ehemieal) This is also known in U.S. Patent Nos. 7,6,8,744 and 7,863,489, and to the United States, the disclosure of which is incorporated herein by reference. After drying and simmering, the catalyst can be activated. The reduction is carried out in the presence of a reducing gas, and the contact is carried out in the presence of the system. The initial ambient temperature rises to 400. (: The reducing gas is continuously passed through the catalyst. The hydrogenation reaction is carried out to carry out the reduction reaction. In particular, the acetic acid hydrogenation can achieve good acetic acid conversion rate and good selectivity to ethanol and yield. For the purpose of the present invention, "conversion rate", _ word means The acetic acid of the scale towel is converted into the amount of compound other than acetic acid. The conversion rate is expressed as the percentage of acetic acid in the feed. The conversion rate can be at least 4% or more 'for example, to at least 'fine%', to 対娜 or to 15 201247301 (4) The percentage of the mole of acetic acid in the gambling of the two sheets should depend on each type of 曰, transformation. The object has an independent selection rate, and the selection rate is also independent of the conversion rate. Example 2: After converting 6G mol% of acetic acid to ethanol, we mean that the selectivity of ethanol is 6〇%. The better is that the catalyst has a selectivity to ethanol of at least 6%, for example, at least listening, or up to 80%. Also preferred in the embodiments of the present invention is the selection of products that are not expected, such as the choice of a hospital, an ethylene bromide, and a carbon monoxide. The selectivity to these non-lin products is preferably low. At 4%, for example, less than 2% or less than 丨%. The "yield" is the number of grams of the reduced amount of towels per gram of the county, such as ethanol. The yield can be from 1 to 3 per gram of catalyst per kilogram of ethanol. In various embodiments of the invention 'Before any subsequent treatment, such as purification and separation, the crude ethanol product produced by the hydrogenation process typically comprises unreacted acetic acid, ethanol and water. The term "alcoholic acid" is used herein. "Product" means any composition comprising from 5 to 7 wt% ethanol and from 5 to 40 wt%. A typical composition range of the crude ethanol product is provided in Table 1. "Others, as defined in Table 1, may contain, For example, g is a class, a shout, a class, a class of ten hydrocarbons, and carbon dioxide. Table 1: Composition of crude ethanol product ! Degree (% by weight). Concentration (% by weight) Road... tongue order "Cleavage 70 z; , Production One" &quot;&quot;~ ------

201247301 實施方式中,表1的乙醇粗產物可以有更高的轉化率,形成低濃 ^曰酸,該醋酸濃度範圍可以從_重量%至2()重魏,例如, 醋以至1〇重魏,侧到5趣。在較低 式巾,較佳者减脑__鱗高於75%,例如, 高於9〇%。此外,較佳者為對乙醇的選擇率也可以較高,尤 者為是高於75%,例如,高於8视或高於9〇% η $小在*7實施方式中’乙醇對水的重量比可至少〇.18:1或更高,例如, 夕〇.5 · 1或至少1小就範圍而言,乙醇對水的重量比可從〇.m至 .1,例如,從0.5 : 1至3 :丨,或從丨:i至2 :。 之土醇粗產物優於傳統乙醇發酵製程之產物,因含乙醇量多於 實施方式中’水含量較低,則需要較少的能源即可分離乙醇,而提 的整體效率。因此,在較佳的實施方式中,乙醇在乙醇粗產物中 县3篁從I5重量%至7〇重量% ’例如,從2G重量駐7G重量%或從25重 量%至70重量%。特佳的是較高的乙醇重量百分率。 根據本發明實施方式的典型乙醇败祕如第Μ騎示。每一氮化 ^統1〇〇包括—個合適的氫化反應器和—種從所獲得之乙醇粗混合物中 分離乙醇的製程。系統100包括反應區1〇1和分離區1〇2。第卜2、4、5和 7圖說明贼純化水的典娜統,而該純化水是作為萃取劑之副產物。第 3和6圖說明回收稀酸流作為萃取劑的典型系統。 ,在第1-7圖所示,反應區1〇1包括反應器1〇3、氫氣進料管路1〇4和醋 酸進料管路105。氫氣和醋酸分別經由通過管路1〇4和1〇5送入蒸發器 110,在官路111建立蒸氣進料流並導向反應器103。反應器103的進料包 含新鮮的醋酸《在一實施方式中,管路104和1〇5可結合並共同送入蒸發 器γο,例如,在一支物流中含有氫氣和醋酸。較佳者為在管路1U中的 蒸’/飞進料流溫度是從100。c至350。0例如,從120。C至310。C,或從150。c 至300。(:。任何未蒸發的進料是經由洩料流從蒸發器11〇移出。此外,雖 然如圖所顯示管路111導向反應器1〇3的頂部,但亦可導向反應器1〇3的侧 17 201247301 邊,上部或底部。 已薛反媒’其用於氫化羧酸,較佳者為氫化醋酸,而形成 乙醇。在-實施方式令,可於反應器上游或任意之蒸發器11〇的上游用一 張或多張保護床(未顯示),以防止觸媒細到含於進料或返回/循環流中 的毒物或不良雜質。4樣的保護床可用於統独4或液體流⑴。適合 保護床材料可包含,例如:碳、二氧化石夕 '氧她、陶究或樹脂。在一 方面,保護床介質加以官能化(WiGnalized),例如,銀官能化,以捕 獲特定的物種’如硫或自素。在氫赠財,較佳者為不斷地從反應器 103通過管路112取出乙醇粗產物。 ‘ 在管路112巾的乙鞠產物可冷凝,並輸朝錄㈣6,這反, 由分離器提供蒸氣流114和液體流⑴。分離器1〇6,例如,可包括一個或 多個閃蒸塔或分絲(knoekout pot)。分離Hi崎作溫度可從2〇。〇至 %(rc ’例如’從3(rc至32代或從的乂至挪乂。分離器1〇6_力可 從1〇〇千帕至3,〇〇〇千帕,例如,從125千帕至2,5〇〇kPa或從⑼千帕至2,2〇〇 :帕。或者’在管路!财的乙醇粗產物可通過一種或多種分離膜分離氫 氣和/或其他非冷凝性氣體(n〇n_c〇ndensablegases)。 ,分離器106排出的蒸氣流1M可包含魏和碳氫化合物,其可加以吹 ,清除(purge)和/或返回到反應區1〇卜如圖所顯示,蒸氣流ιΐ4結合氮 並共噴人紐如0。在—些實财式中,返_蒸氣流 114在結合氫氣進料104之前可加以壓縮。 ,抽來自分離器106的液體流113,並輸送到第一蒸餾塔1〇7,其也簡 稱為」‘萃取蒸鱗”。可加熱液體流113從環境溫度到溫度高達賊,例 如,高達5&lt;TC或4〇。〇:。液體流⑴預熱至高於7〇γ所需要的額外能量, f沒有達到在第一蒸顧塔⑽中再沸器的負荷所欲達成之能源效率。在另 二種實施方式中,液體流113並不另外預熱,但由分離出,而且 、果需要的話,在低於7(rc,例如低於5(rc,或低於4〇&lt;t的溫度,加以 冷卻,並直接送入第一蒸餾塔1〇7 ^ 201247301 在-實施方式巾’液黯113敝成和從反顧巾獲得的管路112的 乙醇粗產物A致相同,除了組成物中已耗盡(depleted)氫氣、二氧化碳、 曱院和/或乙烧’健者為其等被分離㈣6移除。因此,液體流113可以 也被稱為6SI粗產物。表2提供㈣流113的典魏分組成。應#理解液 體流113可包含未列於表2中的其他成分。 表2 :蒸餾塔107之進料組成 (液體流113) 濃度(重量%、 濃度(重量 濃度(重量 乙醇 5至72 10 至 70 15 至 65 醋酸 &lt;90 5至80 0至35 水 5至40 5至30 10 至 26 醋酸乙酯 &lt;30 1 至25 3至20 乙醛 &lt;10 0.001 至 3 0.1 至 3 縮醛 &lt;5 0.01 至 5 0.01 至 3 丙酮 &lt;5 0.0005 至 0.05 0.001 至 0.03 在整份申請說明書表中低於(&lt;)顯示的量較佳為不存在,如果存在 的話,僅僅可以存在微量,或高於0.0001重量%。 在一實施方式中,於液體流113中的醋酸乙酯濃度可以影響第一蒸餾 4107再滞器的負荷和尺寸。減少醋酸乙醋的濃度可允許減少再沸器的負 荷和尺寸。在一實施方式中,為減少醋酸乙酯的濃度:(a)在反應器的 觸媒除了可轉化醋酸亦可轉化醋酸乙酯,(b)該觸媒對醋酸乙酯的選擇 率可較低,和/或(c)反應器進料,包括回收料,可含有較少的醋酸乙酯。 如圖所顯示,液體流113引入第一蒸餾塔107的上部,例如,上半部 或上面三分之一處。如圖所示,一種或多種萃取劑115,例如上所述,亦 5丨入第一蒸餾塔107,以幫助乙醇與水(和其他成分)分離。較佳者為, 直接或間接從第一殘留物回收萃取劑115 ’並且如圓所顯示,可視情況選 201247301 擇性地加人鱗萃_125。萃取船15触者為狀賴如3進料點的 上方。萃取劑115較佳者為引入於接近第_蒸潑塔的頂部,並向下泣 動,直到抵達再滞器。在-些實施方式中,萃取細可從環境溫度加^ ,達7(TC,例如,高達5(rc,或高義。c的溫度。在另—實施方式中了 卒取劑115不單獨預熱,但如第丨_7_示,從其他_塔移出,如果必 要的話,冷卻到溫度至低於7(TC,|列如低於贼,或低於4代,並直接 送入第-蒸館塔107。如第6圖所示,取決於醋酸乙醋循環流147中醋酸乙 酯濃度,此物流可引入液體流進113進料點的上方或下方。此外,萃取劑 115可加入於_乙醋循環流147的上方。根據第—蒸趨塔ι〇7顧出物中目 知;醋酸乙酯的漠度,醋酸乙酯循環流147的進料點會有所不同。 萃取劑115較佳者為包含已健在纽㈣水。如本文所述,萃取劑 115可從第二殘留物的一部分獲得。萃取劑115可以是稀酸流,包含高達 20重量%的醋酸,例如,高達1〇重量%的醋酸或高達5重量%的醋酸。在 -實施方式中,在萃取劑115中水的f量流量對液蠢⑴的質量流量比 範圍可從G.G5 : 1至2 :卜例如’從0.07 : 1至G.9 : 1,或從G.l : 1至〇.7 : !。 較佳的是萃取劑115的質量流量低於液體流113的質量流量。 在一實施方式中,第一蒸餾塔107有5至9〇個理論塔盤,例如從1〇至 60個理論塔盤,或從^至5〇個理論塔盤^每座蒸館塔的實際塔盤數可以 有所不同,取決於塔盤效率,其通常是從〇 5到〇.7,而該塔盤效率則取決 於塔盤類型。塔盤可為篩盤、固定閥塔盤、移動閥塔盤或具有文獻上已 知的任何其他合適的設計。在其他實施方式中,可以使用規整填料 (structured packing)和隨機零散填料(ran(jom pacing)的填充式蒸顧 塔。 … 當在50 kPa操作第一蒸餾塔1〇7,由管路丨16排出的殘留物溫度較佳者 為從20°C至100°C,例如,從3〇。〇:至9(TC,或4(TC到8(TC。藉由移出包 含乙醇、醋酸乙酯、水和醋酸的殘留物流,第一蒸餾塔1〇7的底部可維持 在相對的低溫度,從而提供能源效率的優勢。在5〇千帕操作壓力下,從 20 201247301 —蒸館塔1G7的管路117排出之潑出物溫度較佳者為1(rc細。c,例 如20 C至70 C或30 C至6(TC。第-蒸館塔1〇7的壓力範圍可從〇j千帕 至510千帕,例如,從丨千帕至475千帕或從丨千帕至375千帕。在一些實施 方式中,第-蒸德塔107操作壓力可低於7〇咖,例如低於5〇千帕,或低 =20千帕。真空狀態下操作,可減少再沸器的負荷和第—蒸鱗ι〇7的回 流比。然而’在減少第-蒸館塔1〇7的操作壓力,不會大幅影響蒸館 徑。 ° 送入萃取細塔1〇7的萃取劑量可以有很A的不同。例如,當萃取劑 115包含稀酸的水,水對乙醇粗產物的質量流量比可從〇〇5 :出:卜例 如’從0.07 : 1 至0.9 : 1 或者(U : β〇 7 :卜 在液體流113中的乙醇粗產物包含醋酸乙酯、乙醇和水。這些化合物 可形成不_二元共沸物和三元共沸物。例如,—三元共_可以有彿 點低於其成分㈣點’ ffij其他三元㈣物可以有沸點介於純成分的海點 之間。在本發職有使用萃取劑的實施方式中,大部分的乙醇將轉到管 路117的第-働物巾。藉由在第—蒸齡1G7的萃取劑,可促進乙醇分 離到管路116的第-殘留物中,因而増加管路116中第一殘留物 醇產量。 在這種方式下’乙醇、水、未反應的醋酸、以及如果存在的話之其 他重成分會從紐流113巾娜iB,較佳者為連續地獅ώ,以作為管路 116中的第一殘留物。 第-蒸瓣107也形成第-働物,其經由管路U7移出,並可以加 以冷凝和以回流比來回流之,例如以回流比從3() : i至i : 3Q,像是從 10 . 1至1 · 10或從5 . 1至1 : 5之回流比來回流之。較高之水對有機 進料的質量流量比(mass flow mtb)可允料—__7雜低的回流 比操作》 較佳者為在管路117的第-館出物包含來自液體流113中大部分的重 量的乙.醋酸乙醋。在-實施方式中,在管路117的第一館出物包含醋 21 201247301 ,並尤佳者 s曼乙醋的濃度是低於财乙s旨和水絲物巾乙醋的濃产 為低於75重量% * &amp; 在-些實施方式中,管路117中的第—顧出物還包含乙醇。乙醇返回 反應器103可以需要增加反應器的容量,以保持乙醇的效率在同一水平。 為=收乙醇,可視情況選擇性地’管路117的第—顧出物可送人萃取器, 而殘液可有較低濃度的乙醇,回收到反應器1〇3。 面的中的第—德出物和第-殘留物之典魅成提供在下 物也猶她表3中的其他成 其他細塔的嶋蝴物也可具有類l 要求任鱗定—的=序.彼此,但雜_語不麵解釋為 表3 :蒸館塔1〇7 乙醇 水 醋酸 醋酸乙酯 乙醛 縮醛 &lt;25 0.1 至 20 &lt;2 10 至 85 0.1 至 70 &lt;3 〇·〇〇1 至 20 1至15 &lt;0.1 15 至 80 0.2 至 65 0.01 to 2 濃度(重晋 〇.〇1 至 15 2至10 &lt;0.05 20 至 75 0.5 至 65 0.05 to 1.5 第一殘留物 醋酸 水 乙醇 醋酸乙酯 0.1 至 50 20 至 85 10 至 75 0.005 至 30 0.5 至 40 25 至 80 15 至 70 0.03 至 25 1至30 30 至 75 20 至 65 0.08 至 1 22 201247301 在本發明的一實施方式中,由於形成二元共沸物和三元共沸物,第 蒸顧塔107可在大部分的水、乙醇、和醋酸被移入殘留物流條件下,而 只有少量乙醇和水收集於餾出物流的溫度下操作。管路118殘留物中的水 對管路119館出物中的水之重量比可高於丨:丨,例如高於2 :丨。殘留物中 的乙騎鶴出物中的乙醇之重量比高於1 : 1,例如高於2 : ;1。 ^在第一殘留物中的醋酸量可以有所不同,主要取決於反應器1〇3的轉 化率。在一實施方式中,若轉化率高,例如,高於90%,則在第一殘留 物中的醋酸量可以低於1Gil:%,例如低於5重量%或册2重量% 〇在 其他實施方式中,若轉化率較低,例如低於90% ,則在第一殘留物中的 醋酸量可以高於1〇重量%。 較佳者為在管路117的第—潑出物實質上不含醋酸,例如,包含低於 1,000重量ppm ’低於500重量ppm,或低於100重量ppm的醋酸。餾出物可 從系統中吹氣清除或全部或一部分再循還到反應器1〇3。在一些實施方式 中,若餾出物包含醋酸乙酯和乙醛,則餾出物可,例如,在蒸餾塔(未 顯示)進一步分離成為乙醛流和醋酸乙酯流。醋酸乙酯流也可水解或藉 由氮解’以氫氣還原’以生產乙醇。這些物流可以返回到反應器1〇3或從 系統100分離作為額外的產物。 有些物種,例如縮醛類,可在第一蒸餾塔107中分解,故其量很低, 甚至在蒸餾物或殘留物中沒有檢出量的縮醛類。此外,醋酸/乙醇和醋酸 乙酯之間的平衡反應可以發生在乙醇粗產物排出反應器103後。根據醋酸 在乙醇粗產物巾喊度,這種平衡可明向醋酸乙g旨的雜。這種平衡 可藉由乙醇粗產物的滯留時間和/或溫度調節之。 在一實施方式中,由於管路117中的組成,平衡可以有利於酯化反應 生產醋酸乙酯。雖然酯化反應,無論是在液相或氣相,都可以消耗乙醇, S曰化反應也可減少需要從製程中移除的醋酸量。醋酸乙酯可從第一蒸餾 塔1〇7或藉由第-蒸顧塔107和第二蒸館塔1〇8之間的醋化現場形成(匕 situ)醋酸乙自旨。可藉由-部分管路u中的第—殘留物通旨化反應器(未 23 201247301 ti’人而進一步促進醋化反應。醋化反應器可以是液相或氣相反應器, 媒。較佳的是獅氣相反應器使—些第―殘留物轉化成中 間蒸氣進料,而引入第二蒸餾塔108。 如第1圓所示’為时乙醇,在管路116的殘留物可進_步分離,取 決於醋酸和/或醋酸乙醋的濃度。在本發明大部分的實施方式中,管路ιι6 的殘留物引到第二蒸館塔108,其也被稱為“酸蒸 自的酸,職可在第:蒸細 殘=物中的醋酸濃度高於!重量% ,例如高於5重量%,則可用酸分離 ‘篇館:在些實施方式中,若醋酸濃度低,例如低於重量%,則可 以使用第3圓所示的水分離蒸館塔。 在第1圓中,將管路116的第一殘留物引入第二蒸餾塔1〇8,較佳者為 引入蒸館塔1G8的中間部分,例如,中間二分之—處或中間三分之一處。 第二蒸館塔108產生管路1财包含醋酸和水的第二殘留物,和管路ιΐ9中 有包含乙醇第二鐵物。在__實施方式中,大部分重量的水和/或送入第 二蒸解108的醋酸在管路118的第二殘留物被移除,例如,至少_%, 較佳者為至少有8〇% ’的水和/或醋酸在第二麵物被移除。例如,若在 第殘留物的醋酸濃度是高於5〇重量ppm,如,高於〇1重量%,高於1重 量%,如高於5重量%,則酸蒸餾塔是可必要的。 在一實施方式中,管路116第一殘留物在引入第二蒸餾塔1〇8前可預 熱:在管路116中的第-殘留物可和第二蒸趨塔⑽的殘留物或和第二蒸 餾f 108的蒸氣顧出物作熱量整合在一起。在一些實施方式中,如果醋酸 乙酯存在的話,則可在氣相(未顯示)進行酯化,結果預熱在管路ιΐ6的 第一殘留物,以形成一種中間蒸氣進料。為本發明之目的,當預熱時, 則較佳者為管路116中低於3G莫耳%第-殘_呈氣相,例如低於乃莫耳 %或低於2G莫耳第-殘留物呈氣相。較多的氣相含量造成能源消耗 增加和顯著地增加第二蒸餾塔1〇8的尺寸。 在管路116中第一殘留物的醋酸酯化增加醋酸乙酯的濃度,從而增加 24 201247301 第二蒸餾塔108的尺寸以及增加再沸器的負荷。因此,醋酸轉化率的控 制,取決於從第一蒸餾塔107移出的醋酸乙酯初始濃度。為維持高效分 離,饋入第二蒸餾塔1〇8的管路116進料中第一殘留物的醋酸乙酯濃度較 佳者為低於1,000重量ppm,例如’低於800重量ppm或低於6〇〇重量 ppm ° 操作第一蒸顧塔1〇8以濃縮來自第一殘留物丨16的乙醇,故大部分的 乙醇由塔頂«。因此,第二_塔1〇8的_物可有低乙醇濃度,低於 5重量%,例如低於1重量%,或低於〇.5重量%。不必顯著增加再沸器 的負荷或蒸餾塔的尺寸,即可使乙醇的濃度降低。因此,在一些實施方 式中,有效的是減少殘留物中乙醇的濃度至低於5〇重量ppm,較;^者為低 於25重量ppm。正如本文所述,第二蒸餾塔1〇8中的殘留物可加以處理,· 而低濃度的乙醇允許殘留物之處理不產生其他的雜質。 雖然第二蒸餾塔108的溫度和壓力可以有所不同,但在大氣壓力時, 較佳者為在管路118的第二殘留物溫度從^(^至丨⑼乂,例如,從i〇yc 至15〇。〇或從11(rc^145»c。在一實施方式中,管路116的第一殘留物 預熱到管路118的第二殘留物的溫度之2(rc,例如,在^乂或⑺弋,之 範圍内。第二蒸館塔108的管路119排出的第二餾出物溫較 阶幻阶,例如,從75mrc,或8(rc[irc。在第二 108的底部溫度梯度可以更清晰。 第二蒸餾塔108的壓力範圍可從0j千帕至51〇千帕,例如,從丨千帕至 47=帕,或從i千帕至375千帕。在一實施方式令,第二蒸館塔⑽於高 於大氣壓力,例如,高於17〇千帕或高於375千帕的壓力下操作。 顧塔108的建造材料可以是例如316LSS、A··、或細紐抓,取決 ,操作壓力。再㈣的負荷和第二細塔的尺寸保持相對穩定,直到在 管路119的第二館出物乙醇濃度高於9〇重量%。 ^文=述的第-蒸㈣1〇7 ’較佳者為採用水的萃取蒸鱗。額外的 水在第一蒸鱗108分離。雖然使用水作為萃取劑,可減少第一蒸顧剛7 的再沸器之貞荷,但若水財機補(即親細雨錢量比^於 25 201247301 0.65 · 1,例如’南於〇6 : j或高於〇 54 : i,則會造成第二蒸鱗⑽再满 器的負荷增加,而抵消第一蒸餾塔1〇7帶來的任何好處。 第二蒸餾塔108也形成塔頂餾出物,其經由管路118移出,可加以々 凝和回流,例如回流比從12 : i至i : 12,例如,從1〇 : i至i : / 或從8 · 1至1 : 8。較佳者為管路119的塔頂德出物包含沾至兇重量%, 例如,87至90重量%的乙醇,餘額為水和醋酸乙酯。 第二蒸麟1G8_出物和殘留物的典型成分組成提供於下面的表 。應當理解’館出物和殘留物也可包含未列在表4中的其他成分。 表4 :酸蒸餾塔1〇8(第1圖) 第二餾出物 乙醇 醋酸乙酯 乙醛 水 70 至 99.9 &lt;10 &lt;5 0.1 至 30 滬度(罝重%) 75 至 98 0.001 至 5 0.001 至 1 1至25 濃度(重量%) 80 至 95 0.01 至 3 0.005 至 0.5 5至20 第二殘留物 醋酸 水 醋酸乙酯 乙醇 0.1 至 45 45 至 1〇〇 &lt;2 &lt;5 0.2 至 40 55 至 99.8 &lt;1 0.001 5. S 0.5 至 35 65 至 99.5 &lt;0.5 &lt;2 曹晉中第二触物的乙醇對在管路118中第二殘留物的乙醇之 2 Ξΐί 35 :卜在—實施方式中,在第二殘⑽118中的水 中的水之重量比高於2 : 1,例如高於1 2 : 1,或高於6 : 1。 =者為第二殘留物118中的醋酸對管路ιι9中第二触物的醋酸 26 1 1 ’例如高於15 ·· 1 ’或高於20 : 1。較佳者為,管路⑽ 2 、- 實質上*含醋酸,如果有的話,可以是只含微量的醋酸。 201247301 酸濃度降低則有利於提供無醋酸含量或《醋酸的^ 119的第二顧_質上不含醋編旨。管路= 在^1圖中,為回收水作為使用在第一蒸館塔丨 =二殘留物進-步分離成為水性物流和醋酸流 裝,r管路i财的第二殘留物,然而,如第4圖:的丁其= ―綠留ϊ ϊΐ裝置、分子篩、或分離膜,亦可用於分離管路118中的第 的第二㈣物狀第三細獅,較佳者為引Ϊ 蒸潑4的頂端部分,例如’上半部分或上面三分之—處。在管路⑵ 較佳者為包含水和非常低的醋酸,其含量例如低於5重量 ^低^重旗嘁低於〗重量.在管路121的第三_物可返回 一蒸餾塔107作為萃取劑115,或必要時加以吹氣清除。 W f三ί顧f1G9可以是—種塔盤式蒸_或填充式蒸娜。在一實施 方式令’第三蒸麟109是塔盤式蒸解,其具5至15〇個塔盤,例如奴 50個塔盤或從20至45個塔盤。雖然第三蒸館塔1〇9的溫度和壓力可以 ^同’但在大氣壓力下由管路120排出的第三殘留物溫度,較佳者為從 115 C至140 C ’例如’從咖⑶阶,或從125。⑶价。在大氣 ’力^由管路m排出的第三館出溫度較佳者為從9〇e(^li(rc,例如, =5 C至110 c ’或10CTC至litre 〇第三蒸館塔⑽的壓力範圍可從〇】 千帕至510千帕,例如,從丨千帕至475千帕,或丨千帕至375千帕。 在另-實施方式中,也可操作酸蒸鱗使得移出的第二殘留物包含 醋酸’而第二_物包含乙醇和水,由分離乙醇和水可以回收水。在 第2圖中,第二蒸顧塔122可以是一種塔盤式蒸館塔或填充式蒸德塔。在 -實施方式中,第二顯·2是塔盤式蒸麟,其具有從5錢個塔盤, 例如從15至50個塔盤或從20至45個塔盤。當蒸顧塔m在鮮的大氣壓下 操作’則在管路123排出的殘留物溫度,較佳者為從,例如, 從105。(:至117。〇或從11(TC至115。〇由第二蒸瓣122管路124排出的 餾出物溫度,較佳者為從7(TC至1UTC,例如,從乃^至的它,或8(rc 27 201247301 至90°C。在其他實施方式中’第二蒸餾塔122壓力範圍可從〇1千帕至51〇 千帕,例如,從1千帕至475千帕,或1千帕至375千帕。在下面的表5提供 第二蒸餾塔122餾出物和殘留物的典型成分組成。 表5 :酸蒸餾塔122(第2圖)201247301 In the embodiment, the crude ethanol product of Table 1 can have a higher conversion rate to form a low concentration of citric acid, and the concentration of the acetic acid can range from _% by weight to 2 (), for example, vinegar to 1 〇 wei , side to 5 interesting. In the lower style, it is preferred to reduce the brain __ scale by more than 75%, for example, above 9〇%. In addition, it is preferred that the selectivity to ethanol can also be higher, especially higher than 75%, for example, higher than 8 or higher than 9〇% η $ small in the *7 embodiment, 'ethanol to water The weight ratio may be at least 1818:1 or higher, for example, 〇 〇 .5 · 1 or at least 1 small, the weight ratio of ethanol to water may be from 〇.m to .1, for example, from 0.5. : 1 to 3 : 丨, or from 丨:i to 2 :. The crude soil alcohol product is superior to the traditional ethanol fermentation process. Because the ethanol content is higher than that in the embodiment, the lower water content requires less energy to separate the ethanol, and the overall efficiency is improved. Accordingly, in a preferred embodiment, the ethanol is from 1 to 5 wt% in the crude ethanol product, e.g., from 7 g wt% or from 25 wt% to 70 wt%. Particularly preferred is a higher weight percentage of ethanol. A typical ethanol scum according to an embodiment of the present invention is shown as the first ride. Each of the nitriding systems includes a suitable hydrogenation reactor and a process for separating ethanol from the crude mixture of ethanol obtained. System 100 includes a reaction zone 1〇1 and a separation zone 1〇2. Figures 2, 4, 5 and 7 illustrate the sinister purified water, which is a by-product of the extractant. Figures 3 and 6 illustrate a typical system for recovering a dilute acid stream as an extractant. As shown in Figures 1-7, the reaction zone 1〇1 includes a reactor 1〇3, a hydrogen feed line 1〇4, and an acetic acid feed line 105. Hydrogen and acetic acid are fed to the evaporator 110 via lines 1〇4 and 1〇5, respectively, and a vapor feed stream is established at the official line 111 and directed to the reactor 103. The feed to reactor 103 contains fresh acetic acid. In one embodiment, lines 104 and 1 5 can be combined and fed together to evaporator γ, for example, containing hydrogen and acetic acid in a single stream. Preferably, the steaming/flying feed stream temperature in line 1U is from 100. c to 350. 0, for example, from 120. C to 310. C, or from 150. c to 300. (: Any unvaporized feed is removed from the evaporator 11 via a blowdown stream. Further, although the line 111 is shown as directed to the top of the reactor 1〇3 as shown, it can also be directed to the reactor 1〇3 Side 17 201247301 Side, upper or bottom. Has been used to hydrogenate carboxylic acid, preferably hydrogenated acetic acid, to form ethanol. In the embodiment, it can be used upstream of the reactor or any evaporator 11〇 One or more guard beds (not shown) are used upstream to prevent the catalyst from becoming fine to poisons or undesirable impurities contained in the feed or return/circulation streams. 4 guard beds can be used for unification 4 or liquid flow (1) Suitable protective bed materials may include, for example, carbon, dioxide, oxygen, or ceramics. In one aspect, the guard bed media is functionalized (WiGnalized), for example, silver functionalized to capture specific The species 'such as sulfur or self-supply. In the hydrogen donation, it is preferred to continuously withdraw the crude ethanol product from the reactor 103 through the line 112. 'The acetonitrile product in the line 112 can be condensed and transferred to the record (4) 6 In contrast, the vapor stream 114 and the liquid stream are provided by the separator. Separator 1〇6, for example, may include one or more flash towers or knoekout pots. The separation Hi-synthesis temperature can be from 2〇.〇 to %(rc 'eg 'from 3(rc to 32) Generation or from the 乂 to the 乂. The separator 1 〇 6_ force can be from 1 〇〇 kPa to 3, 〇〇〇 kPa, for example, from 125 kPa to 2,5 kPa or from (9) kPa Up to 2, 2 〇〇: Pa. Or 'in the pipeline! The crude ethanol product can be separated from hydrogen and/or other non-condensable gases (n〇n_c〇ndensablegases) by one or more separation membranes. The vapor stream 1M may contain Wei and hydrocarbons, which may be blown, purged, and/or returned to the reaction zone. As shown, the vapor stream is combined with nitrogen and co-sprayed. In some real-life formulas, the return-vapor stream 114 can be compressed prior to combining the hydrogen feed 104. The liquid stream 113 from the separator 106 is pumped and sent to the first distillation column 1〇7, which is also referred to as " 'Extractive steaming scales. The heatable liquid stream 113 can be heated from ambient temperature to temperature up to thief, for example, up to 5 &lt; TC or 4 〇. 〇: Liquid stream (1) preheated above The additional energy required for 7 〇 γ, f does not reach the energy efficiency to be achieved by the load of the reboiler in the first steaming tower (10). In the other two embodiments, the liquid stream 113 is not additionally preheated, but Separated, and if necessary, at a temperature below 7 (rc, for example below 5 (rc, or below 4 〇 &lt; t, cooled, and sent directly to the first distillation column 1〇7 ^ 201247301 In the embodiment of the invention, the liquid 黯 113 is the same as the crude ethanol product A of the line 112 obtained from the backing towel, except that the composition has depleted hydrogen, carbon dioxide, broth and/or B. Burning 'health is removed for its separation (four) 6). Thus, liquid stream 113 can also be referred to as a 6SI crude product. Table 2 provides (iv) the composition of the flow of the 113. It should be understood that the liquid stream 113 may contain other components not listed in Table 2. Table 2: Feed composition of distillation column 107 (liquid stream 113) Concentration (% by weight, concentration (weight concentration (weight ethanol 5 to 72 10 to 70 15 to 65 acetic acid &lt; 90 5 to 80 0 to 35 water 5 to 40 5 to 30 10 to 26 ethyl acetate &lt; 30 1 to 25 3 to 20 acetaldehyde &lt; 10 0.001 to 3 0.1 to 3 acetal &lt; 5 0.01 to 5 0.01 to 3 acetone &lt; 5 0.0005 to 0.05 0.001 to 0.03 Preferably, the amount shown below (&lt;) in the entire application specification sheet is absent, if present, may be present in minor amounts, or above 0.0001% by weight. In one embodiment, in liquid stream 113 The ethyl acetate concentration can affect the load and size of the first distillation 4107 re-retenterator. Reducing the concentration of ethyl acetate can allow for a reduction in the load and size of the reboiler. In one embodiment, to reduce the concentration of ethyl acetate: a) The catalyst in the reactor can be converted to ethyl acetate in addition to acetic acid, (b) the catalyst can have a lower selectivity to ethyl acetate, and/or (c) the reactor feed, including the regrind Can contain less ethyl acetate. As shown, the liquid 113 is introduced into the upper portion of the first distillation column 107, for example, the upper half or the upper third. As shown, one or more extractants 115, such as described above, also enter the first distillation column 107, To help separate the ethanol from the water (and other ingredients). Preferably, the extractant 115' is recovered directly or indirectly from the first residue and, as indicated by the circle, optionally, 201247301 optionally adds scale _125. The extractor 15 is positioned above the feed point of 3. For example, the extractant 115 is introduced near the top of the first steaming tower and is weighed down until it reaches the re-rear. In the mode, the extraction fine can be increased from the ambient temperature to 7 (TC, for example, a temperature of up to 5 (rc, or high meaning. c. In another embodiment, the stroke agent 115 is not separately preheated, but as in the first丨_7_ indicates that it is removed from the other _ tower, if necessary, cooled to a temperature below 7 (TC, | column is lower than thief, or less than 4 generations, and directly sent to the first steaming tower 107. As shown in Figure 6, depending on the concentration of ethyl acetate in the acetic acid recycle stream 147, this stream can be introduced into the liquid feed to the 113 feed point. In addition, the extracting agent 115 may be added to the above-mentioned acetonitrile circulating stream 147. According to the first steaming tower 〇7, it is known; the ethyl acetate indifference, ethyl acetate circulating flow The feed point will vary from 147. The extractant 115 preferably comprises water that has been hydrated. As described herein, the extractant 115 can be obtained from a portion of the second residue. The extractant 115 can be a dilute acid stream. Containing up to 20% by weight of acetic acid, for example up to 1% by weight of acetic acid or up to 5% by weight of acetic acid. In an embodiment, the mass flow ratio of water in the extractant 115 to the liquid stupid (1) may range from G.G5:1 to 2: for example, 'from 0.07:1 to G.9: 1, or From Gl: 1 to 〇.7: !. Preferably, the mass flow rate of the extractant 115 is lower than the mass flow rate of the liquid stream 113. In one embodiment, the first distillation column 107 has 5 to 9 theoretical trays, for example, from 1 to 60 theoretical trays, or from ^ to 5 theoretical trays. The number of trays can vary, depending on the efficiency of the tray, which is usually from 〇5 to 〇.7, and the tray efficiency depends on the tray type. The tray can be a sieve tray, a fixed valve tray, a moving valve tray or any other suitable design known in the literature. In other embodiments, a structured packing and a random packing of ran (jom pacing) may be used. When the first distillation column 1〇7 is operated at 50 kPa, the line 16 The temperature of the discharged residue is preferably from 20 ° C to 100 ° C, for example, from 3 〇 to 9: to 9 (TC, or 4 (TC to 8 (TC) by removing ethanol, ethyl acetate, The residual stream of water and acetic acid, the bottom of the first distillation column 1〇7 can be maintained at a relatively low temperature, thereby providing an energy efficiency advantage. Under the operating pressure of 5 kPa, from 20 201247301 - the tube of the steaming tower 1G7 The temperature of the effluent discharged from the road 117 is preferably 1 (rc is fine. c, for example, 20 C to 70 C or 30 C to 6 (TC. The pressure range of the first steaming tower 1 〇 7 can be from 〇 j kPa) Up to 510 kPa, for example, from 丨 kPa to 475 kPa or from 丨 kPa to 375 kPa. In some embodiments, the first steaming tower 107 operating pressure may be less than 7 ,, for example less than 5 〇 kPa, or low = 20 kPa. Operating under vacuum, can reduce the load of the reboiler and the reflux ratio of the first steaming scale. However, 'reducing the first steaming hall The operating pressure of the column 1〇7 does not significantly affect the steaming chamber diameter. ° The extraction dose fed to the extraction column 1〇7 can be very different. For example, when the extractant 115 contains dilute acid water, water to ethanol The mass flow ratio of the crude product can be from 〇〇5: out: for example, 'from 0.07:1 to 0.9:1 or (U:β〇7: the crude ethanol in liquid stream 113 contains ethyl acetate, ethanol and Water. These compounds can form non-binary azeotropes and ternary azeotropes. For example, ternary total _ can have a point lower than its composition (four) point ' ffij other ternary (four) can have a boiling point between pure Between the seaweeds of the ingredients. In the embodiment where the extractant is used, most of the ethanol will be transferred to the first wipe of the tube 117. By the first steaming age 1G7 extractant, Promoting the separation of ethanol into the first residue of line 116, thereby increasing the yield of the first residue alcohol in line 116. In this manner 'ethanol, water, unreacted acetic acid, and other heavy components if present Will be from the Newstream 113 towel Na iB, preferably the continuous gryphon, as the first in the pipeline 116 The first vapor bar 107 also forms a first weir, which is removed via line U7 and can be condensed and refluxed at a reflux ratio, for example with a reflux ratio from 3(): i to i: 3Q, like It is refluxed from 10.1 to 1 · 10 or from 5.1 to 1: 5. The higher the mass to mass flow ratio of the organic feed (mass flow mtb) is allowed to be -__7 low Reflux ratio operation" preferably, the first-column in line 117 contains the majority of the weight of ethyl acetate from the liquid stream 113. In the embodiment, the first library in the pipeline 117 contains vinegar 21 201247301, and the concentration of the siemen vinegar is lower than that of the vinegar and the concentrated production of the water silk towel vinegar. 75% by weight * &amp; In some embodiments, the first product in line 117 also comprises ethanol. Ethanol Return Reactor 103 may require an increase in reactor capacity to maintain ethanol at the same level. For the purpose of = ethanol recovery, optionally, the first product of line 117 can be sent to the extractor, and the residual liquid can have a lower concentration of ethanol and recovered to reactor 1〇3. The first-de-sent and the first-residue of the face are provided in the lower part, and the other scorpions of other fine towers in Table 3 can also have the class 1 requirement. , but the miscellaneous _ language is explained as Table 3: steaming tower 1〇7 ethanol water acetic acid ethyl acetate acetaldehyde acetal &lt;25 0.1 to 20 &lt; 2 10 to 85 0.1 to 70 &lt; 3 〇 · 〇〇 1 to 20 1 to 15 &lt; 0.1 15 to 80 0.2 to 65 0.01 to 2 concentration (repeated 〇.〇1 to 15 2 to 10 &lt; 0.05 20 to 75 0.5 to 65 0.05 to 1.5 first residue acetic acid ethanol Ethyl acetate 0.1 to 50 20 to 85 10 to 75 0.005 to 30 0.5 to 40 25 to 80 15 to 70 0.03 to 25 1 to 30 30 to 75 20 to 65 0.08 to 1 22 201247301 In an embodiment of the present invention, Due to the formation of the binary azeotrope and the ternary azeotrope, the first vapor column 107 can be moved to the residual stream under most of the water, ethanol, and acetic acid, while only a small amount of ethanol and water are collected at the temperature of the distillate stream. The weight ratio of the water in the residue of the line 118 to the water in the column 119 can be higher than 丨: 丨, for example, higher than 2 : 丨. The weight ratio of ethanol in the E. serrata in the residue is higher than 1: 1, for example higher than 2: 1. 1. The amount of acetic acid in the first residue may vary, depending on The conversion rate of the reactor 1〇3. In one embodiment, if the conversion rate is high, for example, higher than 90%, the amount of acetic acid in the first residue may be less than 1 Gil:%, for example less than 5% by weight. Or 2% by weight 〇 In other embodiments, if the conversion is low, such as less than 90%, the amount of acetic acid in the first residue may be greater than 1% by weight. Preferred in line 117 The first precipitate is substantially free of acetic acid, for example, containing less than 1,000 ppm by weight 'less than 500 ppm by weight, or less than 100 ppm by weight of acetic acid. The distillate can be purged from the system or all Or a portion is recycled to reactor 1〇 3. In some embodiments, if the distillate comprises ethyl acetate and acetaldehyde, the distillate can be further separated into acetaldehyde, for example, in a distillation column (not shown). Stream and ethyl acetate flow. The ethyl acetate stream can also be hydrolyzed or reduced by hydrogen to reduce hydrogen to produce B. These streams can be returned to reactor 1〇3 or separated from system 100 as an additional product. Some species, such as acetals, can be decomposed in first distillation column 107, so the amount is very low, even in distillate or There is no detectable amount of acetal in the residue. Further, an equilibrium reaction between acetic acid/ethanol and ethyl acetate may occur after the crude ethanol product is discharged from the reactor 103. According to the degree of acetic acid in the crude ethanol product, this balance can be clearly indicated to the acetic acid. This balance can be adjusted by the residence time and/or temperature of the crude ethanol product. In one embodiment, the balance may facilitate esterification to produce ethyl acetate due to the composition in line 117. Although the esterification reaction, whether in the liquid phase or the gas phase, can consume ethanol, the S-deuteration reaction also reduces the amount of acetic acid that needs to be removed from the process. The ethyl acetate may be formed from the first distillation column 1〇7 or by the acetalization between the first steaming tower 107 and the second steaming tower 1〇8. The acetification reaction can be further promoted by the first residue in the -partial line u (the acetalization reactor can be a liquid phase or a gas phase reactor, medium. Preferably, the lion gas phase reactor converts some of the first residue into an intermediate vapor feed and introduces it into the second distillation column 108. As shown in the first circle, 'the time is ethanol, and the residue in the line 116 can enter. The step separation depends on the concentration of acetic acid and/or ethyl acetate. In most embodiments of the invention, the residue of line ι6 is directed to a second vapor column 108, which is also referred to as "acid evaporation. Acid, job can be in the first: steaming fine residue = acetic acid concentration is higher than !% by weight, for example, higher than 5% by weight, can be separated by acid. In some embodiments, if the acetic acid concentration is low, for example Below the weight%, the water separation column shown in the third circle can be used. In the first circle, the first residue of the line 116 is introduced into the second distillation column 1〇8, preferably introduced into the steam. The middle part of the hall tower 1G8, for example, the middle two-point or the middle third. The second steaming tower 108 The raw tubing contains a second residue of acetic acid and water, and the tubing 9 contains an ethanol second iron. In the embodiment, most of the weight of water and/or is fed to the second distillate 108 The second residue of acetic acid in line 118 is removed, for example, at least _%, preferably at least 8% by weight of water and/or acetic acid is removed in the second side. For example, if The acid concentration of the residue is higher than 5 〇 ppm by weight, for example, more than 〇1% by weight, more than 1% by weight, such as more than 5% by weight, an acid distillation column may be necessary. In one embodiment, The first residue of line 116 may be preheated prior to introduction into second distillation column 1 8 : the first residue in line 116 may be the residue of the second distillation column (10) or the second distillation f 108 The vapor is integrated as heat. In some embodiments, if ethyl acetate is present, esterification can be carried out in the gas phase (not shown), with the result that the first residue in the line ΐ6 is preheated to Forming an intermediate vapor feed. For the purposes of the present invention, when preheating, it is preferably less than 3G mole % in line 116 - _ is in the gas phase, for example, less than or less than 2 mol of Mohr-residue in the gas phase. More gas phase content causes an increase in energy consumption and a significant increase in the size of the second distillation column 1〇8. The acetic acid esterification of the first residue in line 116 increases the concentration of ethyl acetate, thereby increasing the size of the second distillation column 108 of 201224301 and increasing the load on the reboiler. Therefore, the control of acetic acid conversion depends on The initial concentration of ethyl acetate removed from the first distillation column 107. To maintain efficient separation, the concentration of ethyl acetate in the first residue fed to the feed line 116 of the second distillation column 1 8 is preferably less than 1,000. The ppm by weight, for example 'below 800 ppm by weight or less than 6 〇〇 ppm ppm °, operates the first distillation column 1〇8 to concentrate the ethanol from the first residue 丨16, so most of the ethanol is from the top of the column «. Therefore, the material of the second column 1 8 may have a low ethanol concentration, less than 5% by weight, such as less than 1% by weight, or less than 5% by weight. The concentration of ethanol can be lowered without significantly increasing the load of the reboiler or the size of the distillation column. Thus, in some embodiments, it is effective to reduce the concentration of ethanol in the residue to less than 5 ppm by weight, more preferably less than 25 ppm by weight. As described herein, the residue in the second distillation column 1〇8 can be treated, and the low concentration of ethanol allows the residue to be processed without generating other impurities. Although the temperature and pressure of the second distillation column 108 may vary, at atmospheric pressure, it is preferred that the temperature of the second residue in the line 118 is from ^(^ to 丨(9)乂, for example, from i〇yc To 15〇.〇 or from 11(rc^145»c. In one embodiment, the first residue of line 116 is preheated to 2 of the temperature of the second residue of line 118 (rc, for example, at ^乂 or (7)弋, within the range of the second distillate discharged from the line 119 of the second steaming tower 108, such as from 75mrc, or 8(rc[irc. in the second 108 The bottom temperature gradient can be sharper. The pressure of the second distillation column 108 can range from 0 j kPa to 51 kPa, for example, from 丨 kPa to 47 kPa, or from i kPa to 375 kPa. By way of example, the second steaming tower (10) is operated at a pressure above atmospheric pressure, for example, above 17 〇 kPa or above 375 kPa. The building material of the Guta 108 may be, for example, 316LSS, A··, or Fine load, depending on the operating pressure. The load of the (4) and the size of the second fine tower remain relatively stable until the ethanol concentration in the second hall of line 119 is higher than 9〇. %. ^文=The first steaming (four)1〇7' is preferred to extract steamed scales with water. The additional water is separated in the first steaming scale 108. Although water is used as the extractant, the first steaming can be reduced. 7 of the reboiler's load, but if the water machine is compensated (ie, the amount of money is 2, 2012, 2012, 301, 0.65, 1, for example, 'Nan Yu 〇6: j or higher than 〇54: i, it will cause the first The steaming scale (10) refills the load of the full vessel and counteracts any benefit from the first distillation column 1 〇 7. The second distillation column 108 also forms an overhead which is removed via line 118 and can be condensed. And reflux, for example, a reflux ratio from 12:i to i:12, for example, from 1〇: i to i: / or from 8 · 1 to 1: 8. Preferably, the top of the line 119 contains Percentage by weight, for example, 87 to 90% by weight of ethanol, the balance is water and ethyl acetate. The typical composition of the second steaming 1G8_seeds and residues is provided in the table below. It should be understood The residue and the residue may also contain other components not listed in Table 4. Table 4: Acid distillation column 1〇8 (Fig. 1) Second distillate ethanol ethyl acetate acetaldehyde water 70 to 99.9 &lt;10 &lt;5 0.1 to 30 Shanghai (% by weight) 75 to 98 0.001 to 5 0.001 to 1 1 to 25 Concentration (% by weight) 80 to 95 0.01 to 3 0.005 to 0.5 5 to 20 Second residue Acetic acid ethyl acetate ethyl alcohol 0.1 to 45 45 to 1 〇〇 &lt; 2 &lt; 5 0.2 to 40 55 to 99.8 &lt; 1 0.001 5. S 0.5 to 35 65 to 99.5 &lt; 0.5 &lt; 2 Cao Jinzhong second touch The ethanol is in the second residue of the ethanol in the line 118. In the embodiment, the weight ratio of water in the water in the second residue (10) 118 is higher than 2:1, for example, higher than 1 2 : 1, or higher than 6: 1. = is the acetic acid in the second residue 118 to the acetic acid 26 1 1 ' of the second touch in the line ι9, for example above 15 · 1 ' or higher than 20: 1. Preferably, the conduit (10) 2, - substantially * contains acetic acid, if any, may contain only traces of acetic acid. 201247301 The decrease in acid concentration is conducive to the supply of no acetic acid content or the second _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ Pipeline = In the figure of ^1, for the recovery of water as a second residue in the first steaming tower 丨 = two residues into the aqueous stream and the acetic acid stream, the second residue of the r pipe, however, As shown in Fig. 4: Dingqi = "green ϊ ϊΐ device, molecular sieve, or separation membrane, can also be used to separate the second (four) traits of the third lion in the pipeline 118, preferably Ϊ Ϊ steam Splash the top part of 4, such as the 'top half or the upper third. Preferably, in the line (2), water and very low acetic acid are contained, the content of which is, for example, less than 5 weights, and the weight is lower than the weight. The third material in the line 121 can be returned to a distillation column 107 as Extractant 115, or if necessary, blown off. W f three 顾 Gu f1G9 can be a kind of tray steaming _ or filling steaming. In one embodiment, the third steaming 109 is tray-type steaming, which has 5 to 15 trays, such as 50 trays or 20 to 45 trays. Although the temperature and pressure of the third steaming tower 1〇9 may be the same as the third residue temperature discharged by the line 120 at atmospheric pressure, preferably from 115 C to 140 C 'eg 'from coffee (3) Order, or from 125. (3) Price. In the atmosphere, the temperature of the third hall discharged by the pipe m is preferably from 9〇e (^li(rc, for example, =5 C to 110 c ' or 10 CTC to litre 〇 third steaming tower (10) The pressure range can range from 千 kPa to 510 kPa, for example, from 丨 kPa to 475 kPa, or 丨 kPa to 375 kPa. In another embodiment, the acid steamed scale can also be manipulated to remove The second residue comprises acetic acid and the second material comprises ethanol and water, and the water can be recovered by separating the ethanol and the water. In the second figure, the second steaming tower 122 can be a tray type steaming tower or a filling type. In the embodiment, the second display is a tray-type steamer having from 5 to 5 trays, for example from 15 to 50 trays or from 20 to 45 trays. The temperature at which the gas m is operated at fresh atmospheric pressure' is then discharged from the line 123, preferably from, for example, 105. (: to 117. 〇 or from 11 (TC to 115. 〇 by the second The temperature of the distillate discharged from the steaming valve 122 line 124 is preferably from 7 (TC to 1 UTC, for example, from it to, or 8 (rc 27 201247301 to 90 ° C. In other embodiments) Second distillation The pressure range of 122 can range from 千1 kPa to 51 kPa, for example, from 1 kPa to 475 kPa, or 1 kPa to 375 kPa. The second distillation column 122 distillate is provided in Table 5 below. Typical composition of the residue. Table 5: Acid distillation column 122 (Fig. 2)

餾出物 乙醇 水 醋酸 醋酸乙S! 乙醛 殘留物 醋酸 水 乙醇 10 至 85 5至60 &lt; 2 &lt;0.5 &lt;2 60 至 1〇〇 &lt;30 &lt; 1 15 至 85 10 至 50 0.001 至 〇.5 &lt;0.01 &lt;0.01 20 至 85 10 至 45 〇·〇1 至 0,2 0·001 至 〇.〇1 〇·〇〇ΐ 至 0.01 65 至 1〇〇 〇.5 至 30 &lt;0.9 85 至 95 1至15 &lt;0.07 在管路123的第二殘留物可再循環回到反應區ι〇ι 中,在第二殘留物123的水,如果有的話, 一貫&amp;方式 力S 一奋aw — . 可朗收’作為萃取劑使用。 則第:殘留二’右—殘留物包含極少量醋酸,例如,低於5重量%, 出物中所含的有機質,例如醋酸,可 處理設施之微錄。 了^有繼來粉讀養餘廢水 如第2圖所示’剩餘的水’如果有的話 中,從管路124的第二物中移除。減發蝴實施方式 路以中的第二館出物一些應用除例===广醇產物可得自管 心水而其他細,例如燃料應用,則可能需用無水乙醇。使用幾 28 201247301 種不同的分離驗,可從管路124㈣二糾物移除水 技術包括使用蒸館塔、分離膜、吸附單元及其組合。特J優先考慮的 …上一實施山方式中,去除水後可回收乙醇產物二第2圖所示,在管路 124的第二館出物送入第三蒸解126,例如乙醇產物蒸顧拉, 餾出物成為管路⑶中的第三館出物(乙_出物),和管路 =一 殘留物(水殘留物)。管路127中的第三殘留物或其部分可返回到3 = 齡107作為萃取·根據水作為萃取劑的需要量,_部分在管路⑵的 第二殘留物也可加財氣清I在管路124的第二 以的底部’例如,下半部或下面三分之_處。概者為管路 餾出物以回流比加以回流,例如,其回流比從丨:1〇至1〇 :丨,像是從广 ,或1 2至2 . 1。第二蒸館塔126較佳者為如上所述的塔盤 式蒸顧塔,較佳者為在大氣壓力下操作。從第三蒸顧塔⑼排出的第^餾 出,溫度較佳者為從6〇°C至ll(Tc,例如,從7〇。(:至l〇〇°C,或75°C至 95 C。當蒸館塔在大氣壓力下操作時,在管路127的第三殘留物溫度較 佳者為從70 C至115°C,例如’從8〇。〇:到lKTc,或85eC至105。〇:。第三 蒸顧塔126的顧出物和殘留物之典型成分組成提供在下面的表6。應當理 解的是’館出物和殘留物也可以包含未列在表中的其他成分,例如在進 料中的成分。 29 201247301 表6 :乙醇產物蒸餾塔126 濃度(重詈〇/〇) 濃度(重量%) 濃度(曹晉〇/Λ 餾出物 乙醇 水 醋酸 醋酸乙酯 75至% &lt;12 &lt;1 &lt;5 80 至 96 1至9 0.001 至 0.1 0.001 至 4 幻至96 3至8 0.005 至 〇.〇1 0.01 至 3 殘留物 水 乙醇 醋酸乙酯 醋酸 75 至 1〇〇 &lt;0.8 &lt;1 &lt;2 80 至 100 0.001 至 0.5 0.001 至 0.5 0,001 至 0.5 9〇 至 1〇〇 0.005 至 〇.〇5 0.005 至 〇.2 0.005 至 〇,2 在另-實施方式t,較佳者為反應器103中酸的轉化率為高的,一座 蒸顧塔可驗喊乙醇產物和以水作解輔^在第顶巾,將在管路Μ 的第-殘留物送人第二蒸餾塔129,其被稱為“稀酸回收難塔,,。第3 圖的第二蒸娜129以類似幻圖第二顏塔的方式操作,㈣除殘留物 中大。P/7的水。來自管路116中第—殘留物的水可分離為管路132中的第 二殘留物,並返回到第一蒸顧塔107。在管路132可以有-些第二殘留物 中的酷酸(也稱為為稀酸流),必要時可加上吹氣清除133。在一些實施 方式中’稀酸流132可包含來自乙醇粗產物113中至少85%,例如,至少 90% ’尤佳者為至少99觸醋酸。就範_言,稀酸流132可視情況選擇 =地包含85%至99.5%或90%至99.99%的來自乙醇粗產物的未反應的醋 I。在-些實施方式中,稀酸流132包含從2至6〇重量%的醋酸和從4〇到 98重量%的水。在-實施方式中,管路m的第二前物,即使它含有醋 酸’仍可返回到第一蒸德塔107。例如,稀酸流132可含有低於30重量%, 例如’低於15重量%,低於1〇重量%,或低於5重量%的醋酸。 30 201247301 断用二1 留物132(第3圖)中存在有高濃度醋酸的情況下,水分離器 膜縣。财分_38可為,例如是鑛裝置、分離 ΐ酸ίΓ/ ί他合適的水/酸分離器或其組合。壓變吸附裝置可用於從 °也可㈣酸的水渗透膜°在第4圖中,管路H6的第-殘留 塔134,其操作方式類似於第1圖中的第二蒸娜。來自 的第-殘留物的水和酸可分離成為f路⑶的第二殘留物,並饋 離器138。水分離器138分離管路136中的第二殘留物成為在管路 3=水性物流和在管糾醋酸流m施方式中,水性物流可 包3少量的醋酸,並可稱為稀酸流。水性物流可包含醋酸,其含量低於 20重量%,例如低於15重量%,低於1〇重量%,或低於5重量%。在一 些實施方式中’根據在第二殘留物136的酸量,第二殘留物可在管路印 藉由吹氣清除’可再賊到反應,或可如上述討論絲處理之。如 第4圖所示,水性物流139可返回到第一蒸顧塔1〇7作為萃取劑。可以有一 些黯酸在水性誠139卜在倾方式巾,祕驗139可結合新鮮水 125 ’然後返回第一蒸館塔1〇7。來自水分離器1;38的醋酸流⑽較佳者為 含有尚濃度的醋酸。醋酸流140可返回到反應區1〇1。 在一實施方式中,來自醋酸蒸餾塔的第二殘留物流中的醋酸可以反 應耗盡,從而留下純淨水性物流。在第5圖中,第二殘留物132導向第三 蒸餾塔141進行酯化。在一實施方式中,實質上全部未反應的醋酸均在第 —殘留物132中反應耗盡。根據本發明,在第二殘留物132中的醋酸與在 5a化單元141中管路142的甲醇反應,而產生在管路143醋酸甲酯。雖然前 面採用甲醇,但是應當理解也可使用其他醇類,包含乙醇或醇類的混合 物。例如,果使用乙醇代替甲醇,將在管路143產生醋酸乙酯。如第5圖 所示,酯化單元係反應蒸餾塔(第三蒸餾塔)141。第二殘留物132和甲 醇流142—起饋入第三蒸餾塔141,而產生包含醋酸甲酯的第三殘留物流 145,和包含水的第三餾出物流。至少一部分的第三殘留物流可通過管路 145從系統中加以吹氣清除。第5圖顯示甲醇進料流.142送入第三蒸館塔 31 201247301 的位置在第二殘留物132送入第三蒸顧塔點之下面。在其他實施方式 甲醇進料流可送入第二蒸顧塔141的位置與第二殘留物送入第三 蒸館塔點的同一水平,或在其下面。 “若第三蒸顧塔141是一種反應性蒸顧塔,如第5圖所示,則第三蒸德 塔141包含離子交換樹月旨床、酸性觸媒、或其組合。適用於本發明中離子 交換樹脂之非限制範圍的例子包括大孔強酸性陽離子交換樹脂 OnaeiOpomus stroi^add eati〇n exchange resins) ’ 例如那些得自陶氏化學 公司(Dow Chemical Company)的Amberlyst® (例如,如__5® ’ Amberlysm®和Amberlyst 36®)。適用於在本發明令的其他離子交換樹脂 揭露在美國專利號4,615,806、5,139981和7 58869〇,其全部内容在此納 入參考。在另一實施方式中,酸添加到第三蒸餾塔141,以催化酯化反應。 在此樣態,酸可以選自由硫酸 '磷酸、磺酸,雜多酸(heter〇p〇lyadds)、 其他無機酸及它們的混合物所組成之群組。在其他實施方式中,酸觸媒 包括沸石和支撐體,其係經礦物酸及雜多酸處理。 在一些實施方式中,若離子交換樹脂存在於第三蒸餾塔141,則第二 殘留物132在饋入第三蒸餾塔141之前,可先送入保護床(未顯示)。在一 實施方式令,保護床包含,如上述揭露的離子交換樹脂。雖然不局限於 任何特定的理論,但保護床能移除一種或多種在第二殘留物132中的腐蝕 性金屬,從而最大限度地減少在第三蒸餾塔141中交換樹脂的任何離子交 換樹脂催化位點之純化。 第三蒸餾塔141的操作參數可加以修改,以達成在第三餾出物143和/ 或殘留物流144所需的組成。例如,在一些實施方式中,溫度、壓力、進 料速率和滯留時間可以變化,以增加醋酸變酯的轉化率,以減少雜質的 形成,以達成更有效的分離,以降低能源消耗,或者其綜合效果。 在一實施方式中,第三蒸餾塔141底部操作溫度從100。(:至15〇。(:,例 如,從100°C至130°C,或從10(TC至120t。在壓力方面,反應蒸餾塔可 以在常壓、次大氣壓力(subatmospheric pressure)、或超大氣壓力下操作。 32 201247301 til施方式巾,反顧鱗操作的壓力,從财帕建千柄, 例如,從50千帕至400千帕’或從5〇千帕至2〇〇千帕。 在一些實施方式中,第三蒸鱗141的醋酸和醇進料速率可以 整二制輸送到第三蒸鱗141的錯酸對醇之莫耳比。例如,在_些二 施方式中’送人反應顯塔中醋酸對甲醇之莫耳比從i :丨至-例如’從1 : 1至1 ·· 5,或從i : 1 ’ 第三蒸鶴塔141的滯留時間會影響醋酸轉化率。例如,在一 式中,在第三蒸顧塔中的滯留時間是從i至5小時,例如,從 小時,或低於1小時。 由第三蒸餾塔141排出在管路143中的第三顧出物較佳者為包含 I5重量%的_曱§旨,尤佳者紅少%重魏的騎f自旨,或最佳者 至v65重量%的醋酸甲g旨《就翻而言,來自第三蒸祕⑷的第三 物143可包知至99重量%,例如,%至_量%,敏5师q重量%的 醋酸甲酷。 若過量曱醇與從稀酸流中的醋酸反應,則一些甲醇也可存在於第三 镏出物143中。因此,第三館出物143可包含從〇 重量%,例如,1〇 至60重量%,或從1至3〇重量%的曱醇。 在第二蒸餾塔129反應過程中,可以形成一些雜質,例如二甲醚。在 第二餾出物流143中,這些雜質的含量可以非常低,甚至沒有檢出的量。 在一些實施方式中,第三餾出物143包含低於1,〇〇〇重量ppm,例如,低於 750重量ppm,或低於5〇〇重量ppm的二甲醚。 第二館出物流143可饋入到艘基化反應器,用於生產醋酸,這可以反 過來,可用為乙醇合成反應的原料。在一些實施方式中,第三餾出物流 143在送入羰基化反應器之前,可隨意加以冷凝、加工、或精煉。 在一實施方式中,由於在第二餾出物131中醋酸乙酯的存在,可使用 額外的第三蒸餾塔146。第三蒸餾塔146,亦稱為“輕餾份蒸餾塔,,,用 於從第二餾出物131移除醋酸乙酯,和在管路148的第三殘留物中製造乙 33 201247301 醇產物。輕館份蒸顧塔M6可以是一種塔盤式蒸館塔或填充式蒸館塔 第6圖中,第三蒸趨塔146可以有5至9〇個理論塔盤,例如,1〇至^ 塔盤,或15至50個理論塔盤。 第二館出物131的進料位置可以有所不同,取決於醋酸乙醋的濃卢, 較佳者為第二傲出物饋人第三顏塔竭上面部分。高濃度的醋酸&amp;旨 可饋入第三蒸瓣146的更高位置。進料的位置應避免在非常頂部的拔 盤’接近回流以避免_塔的再㈣太多的負荷和驗塔的尺押加^ 要求。例如’在具有45個實際塔盤的蒸館塔中,進料的位置應^ 部算起第10至第I5個塔盤之間。若在這上面點饋 荷和輕館份蒸娜146之尺寸。 h力Α弗㈣負 一第二傲出物131可饋入溫度高達7(rc,例如,高達阶或4〇 二蒸顧塔14卜在-些實施方式中,沒有必要進—步預熱第二軸物⑶。 醋酸乙S旨可在管路147的第三顧出物中濃'缩。由於相當低量的醋酸乙 醋饋入第三蒸鰣⑽,故管路147的第三鶴出物還包含大量的 回收乙醇’在管路147的第三館出物可饋入第一蒸顧塔1〇7,作輕酸2 醋循環流。因為如此會增加第一蒸館塔⑽和第 佳者為在管細㈣三邮財乙·舰職_量% :求從$ 到88重量%,或從75到85重量%。 從2 在其他實施方式中,-部分在管路147的第三顧出物可從 吹氣清除,作為另一種產物,例如醋酸乙酯溶劑。 、 選的實施方式中,第三殘留物148可進—步處理,以回收所需 量的水與乙醇,例如,賴另i驗塔、吸附 U需 ,要時,可進-步從管咖的第三殘留物去除水。在大部 式中,於進入第三蒸餾塔146之前,先使用水八雜 實包方 進-步鶴乙醇。 先使脉移除水,從而不需要 第三蒸鱗146較佳者為如上所述的缝式蒸麟 壓力下操作。從第王蒸解撕管路148的第三殘^物溫度較佳^ 34 201247301 從65°C至110°C,例如,從7(T(^10(rc,或乃沱到⑽乂。從 塔146管路147排出的第三顧出物溫度較佳者為從3(rc至7〇&lt;&gt;c ’、 40°C至65°C,或50°C至65°C。 第三蒸餾塔146的壓力範圍可從0.1千帕至510千帕,例如,從〗千帕至 475千帕,或丨千帕至375千帕。在一些實施方式巾,第三蒸館塔⑷可在 低於70kPa,例如低於5〇千帕,或低於2〇千帕的壓力下操作。操作壓力 降將實質上減少驗塔的紐為和第三細塔146巾再沸器的負荷。 、在下面的表7提供乙醇混合流和第三蒸餾塔146的殘留物的典型成分 組成。應當理解’館出物和殘留物也可包含未列在表7中之其他成分。刀 濃度(重量%) 濃度(重量%) 濃度Γ曹晉%、 70至 99 72 至 90 Μ至85 0.5至 30 1至25 1至15 &lt;15 0.001 至 10 0.1 至 5 &lt;10 0.001 至 2 〇.〇1 至 1 &lt;2 0.001 至 1 〇.〇1 至 0_5 80至 99.5 85 至 97 90 至 95 &lt;8 0.001 至 3 0.01 至 1 &lt;1.5 0.0001 至 1 0.001 至 0.5 ^0.5 &lt;0.01 0.0001 至 0.01 第三餾出物 乙醇 醋酸乙酉旨 乙醛 水 縮醛 第三殘留物 乙醇 水 醋酸乙酯 醋酸 148。在些實施方式中,水可存在於131餾出物中,其可轉入乙醇產物流 式中在施方式中’於回收乙醇產物之前,可先移除水。在一實施方 ^ 於管路131中的餾出物可包含低於L5重量%的水,例如低於10重量 35 201247301 %的水或低於8重量%的水。在管路131中的餾出物可送入水分離器,其 可以是一種吸附裝置、分離膜、分子篩、萃取蒸餾塔或其組合。在一實 施方式_,至少有50%管路131的第二飽出物加以冷凝,並可導入第三篆 餾塔146。 一〜 第7圖是顯示使用反應蒸餾塔M1和乙醇產物蒸餾塔146組合的一種 不意圖。在這種示意圖中,第二餾出物131饋入乙醇產物蒸餾塔146,而 第二殘留物132饋入反應蒸餾塔14卜結果純化乙醇回收作為管路148中的 第二殘留物,而醋酸乙酯回收作為第三餾出物147,並送回到第一蒸餾塔 107。第二殘留物132送入反應蒸餾塔141,使第二殘殘留物中的醋酸和甲 醇反應’產生繼f g旨,其时於管路143。回收水性物流144作為第四 殘留物’並返酬第-_物7作鱗取劑。至少有—部分的水性 144在管路145中可從系統吹氣清除。 再回到-管路117的第-條出物,其包含醋酸乙醋和/或乙链,較佳者為 如第1圖所示以回流比加以回流之,例如,其回流比從i : 3〇至3〇:卜 如,從1 : 5至5 :卜幻:3至3 :卜在一樣態,於此處未顯示,第 -館出物或其部份可返回到反應器阳。在一些實施方式中,糊的是第 -傲出物的-部分返回反應器跡來自第—似物的醋酸乙醋和/或乙駿 可進-步在氫化反應器⑽或第二反應器反應。來自第二反應器流出物可 送入反應H1G3 ’以產生更多的乙醇,或送人蒸館塔回收額外乙醇。 在-些實施方式中,在管路117的第一顧出物可以還包含少量的水。 如果全部或-部分的第—触物返回反應㈣3,則必須從管路ιΐ7移除 ^胳例如’來自管路117中第一餘出物的水可藉由吸附裝置、一種或多種 为離膜、分子筛、萃取蒸顧塔或其組合加以移除。例如,吸附裝置 =)可用於從管路117中的第_館出物絲水性物流,從而產生一種 里組分流,較佳者為包含低於1重量%的水,尤佳者為低於0.5重量 吸附裝置可從管路117中的第一館出物去除高達99 的水較 ^為從從第-«物去除95%至99 99%的水。精煉的輕組分 分可返回到反應器1〇3。 1 36 201247301 在一實施方式中,在管路117的第一餾出物或一部分的兩物流之一或 全。卩可進一步分離而產生含乙搭流和含醋酸乙醋流。這可使含乙路流或 含醋酸乙酯流的一部分回收到反應器1〇3,同時吹氣清除其他物流。吹氣 清除流可作為寶貴的醋酸乙酯和/或乙醛的來源。 ^在本發明中使用的蒸餾塔可包含能夠執行所欲分離和/或純化的任何 蒸餾塔。較佳者為蒸餾塔包括塔盤式蒸餾塔,具有從丨到〗%個塔盤,例 ,,從20到95個塔盤,或從30到75個塔盤,從1〇到ι00個塔盤。塔盤可為 篩盤、固㈣塔盤、移關塔盤或具有文獻上已知的任何其他^適的設 計。在其他實施方式中,可以使用填充式蒸娜。就填充式蒸顧塔而言, 規整,料和賴零散填料均可朗。這些塔盤或㈣可安排在—連續的 蒸餾塔,也可以安排在兩座或衫座的蒸娜使得統從第—段進入第 二段’而液體從第二段進入第一段等。 配用於每一蒸娜的相關冷凝器和液體分離槽可以是任何傳統的設 化於圖巾。熱可以提供給每蒸娜底部,或使底部流循環通過 或再_(rebc)ilel0°也可用其他類型的再彿器’如内部再沸器。 入/、f 5的熱量可來前何製程中生成的熱量,該製程可和再沸器整 2-=配用夕㈣熱源,如其他發熱化學製程或鍋爐。雖然如囷所示 閃蒸塔’但是在本發明各種實施方式中可以用附加的 者即知、冷凝器、加熱70件和其他元件。對此領域之熟悉技藝 閥門該55化學製程之各種冷凝器、泵、壓縮機、再沸器、轉筒、 的製程中 分離容器等’也可進行合併並整合在—起使祕本發明 合於麟的溫度和壓力可以有所不同。不顾域⑽溫度一般 於在該位置的物料组成和暮餾试厭士 「冰h皿汉疋細賴 進料速率可以有所不t ,視ί產製程的規模而定, 表示。 』 果加以^述的話,可籠統地以進料重量比率 所屬技術領域和移出之殘留物組成物的沸點之間。對 於在=番通常識者即知在操作蒸餾塔某-點的溫度是端賴 37 201247301 在管路119、128和131的鶴出物包含乙醇,如上所述,藉由—種 =額外的,離系統,例如’蒸顧(例如,精顧塔)、壓變吸附系統、分 醇產ί:篩s、1取蒸餾塔’或其組合,可以進一步純化’以形成無水乙 醇產物》;IL,即完成之無水乙醇”。 應產物的任何通過細製程之化合物—般保持在乙 重量卜卞百iL ί於ο.1重量% ’例如,低於0.05重量% ’或低於〇.〇2 重ft該百分率係對乙醇_物組成物總重量而言。在-實施方式中, 少二汽中移除任何蒸德塔的雜質。較佳者為採用至 ί系除絲f。這·f可加財_除和/或保留 ㈣由i發明的製程中獲得的最終乙醇組成物可經由管路U9、131或135 -峰取出,或可視情況選擇性地經由 8 留 成分 濃度帚 乙醇 85 至 99.9 水 &lt;8 醋酸 &lt;1 醋酸乙酯 &lt;2 縮醛 &lt;0.05 丙_ &lt;0.05 異丙醇 &lt;0.5 正丙醇 &lt;0.5 .濃度(重量%) 90 至 99.5 0.1至 &lt;0.1 &lt;0.5 &lt;0.01 &lt;0.01 &lt;0.1 &lt;0.1 濃度(重·§·%) 92 至 99.5 0.1至 &lt;0.01 &lt;0.05 &lt; 0.005 &lt;0.005 &lt;0,05 &lt;0.05 醇。在一實=3如甲f、正丁醇、異丁醇、異戊醇等的其他c4-c20 式令’在成品乙醇組成物中異丙醇含量是從⑽至…⑽重 38 201247301 量ppm ’例如’從95至1,〇〇〇重量ppm,從獅至γόο重量ppm,或從丨5〇至 500重量ppm。在一實施方式中,成品乙醇組成物較佳者為實質上不含乙 酸,並可以包含低於8重量ppm乙醛,如低於5重量乙醛或低於丨重量 ppm乙路。 本發明實施方式完成的乙醇組成物適合使用在多種應用,包含燃 料、溶劑、化工原料、藥品、清潔劑、消毒劑、氫化傳送或消費品。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、 船隻和小無塞式發械賴。在非燃料顧上,完制乙醇組成物可 ,作化妝品和美容製劑之溶劑、洗蘇劑、消毒劑、塗料、油墨、和藥品。 完成的乙醇組成物還可以用作製程溶劑,其可供醫藥產品、食品製劑、 染料、光化學和乳膠加工之用。 完成的乙醇組成物還可以用作化學原料,製造其他化學材料,如醋、 丙稀酸乙醋、醋酸乙醋、乙稀、乙二醇峨、乙胺類、賴、高碳醇類, 尤其是丁醇。在生產醋酸乙g旨巾’完成的乙雜成物可藉㈣酸進行醋 化。在另一個應用中,完成的乙醇組成物可脫水生產乙烯。 【實施方式】 為了使本發明的揭露可更有效地理解,提供下面實施例。應該了解, 這些實施例僅作制之用,不應被觸為難何形式關本發明。 實施例 八雜^本發明的—種分離製程。將乙醇粗產物饋人包含三座蒸顧塔之 刀離系統。使用水作為萃取劑操作第—蒸,並和不使用萃取 :蒸解相I也在大氣壓力和約33仟帕的真空下測試第—蒸顧塔的壓 能源需求和乙醇產量在表9中揭露。 39 201247301 沒有水, _ __大氣壓力下 能源需求 1.66 [百萬英熱單 元/噸乙醇] 在殘留物中回87.1〇/〇 收的乙醇 表9 沒有水 真空 0.68 7jC, 水萃取 真空 0,75 0.53 90.1% 98.3% 99.3% 如表9所示,當水作為第-細塔的萃取劑,_塔的輯 下降到0‘75。同時,乙醇回收量從87 1%上升到98 3 二從.砧 作蒸顧塔’操作成本降條%。 0 &amp;外’烕壓下操 雖穌發明已詳細贿’但在本發簡義和範_之各種 屬領域之熟悉技藝者而言係顯而易見。以上討論&amp;女 本發,面和各實施方式的-部分和以下各種特色和/或所二 可以合併或互換全部或部分。在前面各種實施 可!:適當結合其他實施方式,對所屬領域之熟悉技 =2=,其中揭露均可在此納入參考 =理:是;==通技術者都明白前面描述只是 【圓式簡單說明】 件。以下參考各種圖式詳細解說本發明,其中相同之數字係指相同的元 第1圖顯示按照本發明-實施方式的乙醇生產系統示意圖, 從醋酸回收萃取劑的蒸餾塔。 、 第2圖顯示按照本發明—實施方式的乙醇生產系統示意圖,其 從乙醇回收萃取劑的蒸餾塔。 、 第3圓顯示按照本發明一實施方式的乙醇生產系統示意圖,其中包含 201247301 回收稀酸流的蒸餾塔,而該稀酸流是適合作為萃取劑。 第4圖顯示按照本發明一實施方式的乙醇生產系統示意圖,其中包含 回收萃取劑的蒸餾塔,並藉由一種或多種水分離裝置分離成為返回到反 應器的醋酸,和回收作為萃取劑的水。 第5圖顯示按照本發明一實施方式的乙醇生產系統示意圖,其中包含 回收萃取劑的蒸餾塔,和酯化單元。 第6圖顯示按照本發明一實施方式的乙醇生產系統示意圖,其中包含 回收稀酸流的蒸德塔,和分離醋酸乙酯和乙醇的另一蒸顧塔。 第7圖顯示按照本發明一實施方式的乙醇生產系統示意圖類似於第6 圖’其中在反應蒸館塔有酯化單元。 【主要元件符號說明】 代號 說明 100 氫化系統 101 反應區 102 分離區 103 反應器 104 氫氣進料管路/管路/氫氣進料 105 醋酸進料管路/管路 106 分離器 107 第一蒸餾塔/萃取蒸餾塔 108 第一蒸館塔/酸蒸顧塔 109 第三蒸餾塔 110 蒸發器 111 管路 *---------—--—----- 41 201247301 代號 說明 112 管路 113 液體流/乙醇粗產物 114 蒸氣流 115 萃取劑 117 管路 118 第二殘留物/管路 119 第二餾出物 120 管路/第三殘留物流 121 管路 122 第二蒸餾塔 123 管路 124 管路 125 新鮮水 126 第三蒸餾塔 127 管路/第三殘留物流 128 管路 129 第二蒸餾塔/稀酸回收蒸餾塔 131 第二餾出物/管路 132 管路/稀酸流/第二殘留物 133 吹氣清除 134 第二蒸餾塔 135 管路 136 管路 137 管路 42 201247301 代號 說明 138 水分離器 139 管路 140 管路/醋酸流 141 第三蒸餾塔/酯化單元/反應蒸餾塔 142 管路/甲醇流 143 管路/第三餾出物流 144 第三殘留物流 145 管路/第三殘留物流 146 額外的第三蒸餾塔/輕餾份蒸餾塔 147 管路/醋酸乙酯循環流 148 管路/乙醇產物流/第三殘留物流 43Distillate Ethanol Water Acetic Acid Acetic Acid Acetic Acid S! Acetaldehyde Residue Acetic Acid Water Ethanol 10 to 85 5 to 60 &lt; 2 &lt;0.5 &lt; 2 60 to 1 〇〇 &lt;30 &lt; 1 15 to 85 10 to 50 0.001 To 〇.5 &lt;0.01 &lt;0.01 20 to 85 10 to 45 〇·〇1 to 0,2 0·001 to 〇.〇1 〇·〇〇ΐ to 0.01 65 to 1〇〇〇.5 to 30 &lt ; 0.9 85 to 95 1 to 15 &lt; 0.07 The second residue in line 123 can be recycled back to the reaction zone ι〇ι, the water in the second residue 123, if any, consistent &amp; Force S Yifuaw — . Can be used as an extractant. Then, the residue: two right-residues contain a very small amount of acetic acid, for example, less than 5% by weight, and the organic matter contained in the product, such as acetic acid, can be micro-recorded. The residual water is continuously read as shown in Fig. 2, and the remaining water, if any, is removed from the second material of the line 124. The implementation of the reduction of the butterfly in the second hall of the road to some applications in addition to the example == = wide alcohol product can be obtained from the tube water and other fine, such as fuel applications, may need to use anhydrous ethanol. The use of several 28 201247301 different separation tests to remove water from line 124 (d) two corrections includes the use of steaming towers, separation membranes, adsorption units, and combinations thereof. Priority J is preferred. In the previous implementation of the mountain method, after the water is removed, the ethanol product can be recovered. As shown in Fig. 2, the second plant in the line 124 is sent to a third distillation 126, such as an ethanol product. The distillate becomes the third museum output (B_exit) in the pipeline (3), and the pipeline = a residue (water residue). The third residue in the line 127 or a portion thereof can be returned to 3 = age 107 as the extraction. According to the required amount of water as the extractant, the second residue in the line (2) can also be added to the gas in the tube. The second bottom of the road 124 is 'for example, the lower half or the lower third. In general, the pipe distillate is refluxed at a reflux ratio, for example, the reflux ratio is from 丨:1〇 to 1〇:丨, such as from broad, or from 12 to 2.1. The second steaming tower 126 is preferably a tray type steaming tower as described above, preferably operated at atmospheric pressure. The temperature is preferably from 6 〇 ° C to ll (Tc, for example, from 7 〇. (: to l 〇〇 ° C, or 75 ° C to 95) from the third distillation column (9). C. When the steaming tower is operated at atmospheric pressure, the third residue temperature in line 127 is preferably from 70 C to 115 ° C, for example 'from 8 〇. 〇: to lKTc, or 85 eC to 105 〇: The typical composition of the precursors and residues of the third steaming tower 126 is provided in Table 6 below. It should be understood that 'the exhibits and residues may also contain other ingredients not listed in the table. For example, the ingredients in the feed. 29 201247301 Table 6: Ethanol Product Distillation Column 126 Concentration (Heavy/詈〇) Concentration (% by weight) Concentration (Cao Jinyu/Λ Distillate Ethanol Water Acetate Acetate 75 to % &lt;12 &lt;1 &lt;5 80 to 96 1 to 9 0.001 to 0.1 0.001 to 4 phantom to 96 3 to 8 0.005 to 〇.〇1 0.01 to 3 Residue water ethanol ethyl acetate acetic acid 75 to 1 〇〇 &lt;0.8 &lt;1 &lt;2 80 to 100 0.001 to 0.5 0.001 to 0.5 0,001 to 0.5 9 to 1 to 0.005 to 〇.〇5 0.005 to 〇.2 0.005 to 〇, 2 in another In the mode t, it is preferred that the conversion rate of the acid in the reactor 103 is high, and a steaming tower can detect the ethanol product and use water as a solution to the top scarf, which will be the first residue in the pipeline. The second distillation column 129 is sent, which is called "dilute acid recovery refractory tower." The second steaming 129 of Fig. 3 operates in a manner similar to the second phenotype of the magical figure, and (4) large in addition to the residue. /7 of water. The water from the first residue in line 116 can be separated into a second residue in line 132 and returned to first steam column 107. There can be some second residues in line 132 The sour acid (also referred to as a dilute acid stream) may be added with a blow purge 133 if desired. In some embodiments, the dilute acid stream 132 may comprise at least 85% from the ethanol crude product 113, for example, at least 90% 'especially at least 99-touch acetic acid. In the meantime, the dilute acid stream 132 may optionally comprise 85% to 99.5% or 90% to 99.99% of unreacted vinegar I from the crude ethanol product. In some embodiments, the dilute acid stream 132 comprises from 2 to 6 wt% acetic acid and from 4 to 98 wt% water. In an embodiment, the second front of the conduit m Even if it contains acetic acid', it can be returned to the first vaporization deuteration 107. For example, the dilute acid stream 132 can contain less than 30% by weight, such as 'less than 15% by weight, less than 1% by weight, or less than 5 Weight % of acetic acid. 30 201247301 Broken with 2 1 Residue 132 (Fig. 3) In the presence of high concentrations of acetic acid, the water separator membrane county. The wealth _38 can be, for example, a mining device, a separate water/acid separator or a combination thereof. The pressure swing adsorption device can be used to permeable membranes from water of (4) acid. In Fig. 4, the first-residual column 134 of line H6 operates in a manner similar to the second steaming in Figure 1. The water and acid from the first residue can be separated into a second residue of the path (3) and fed to the 138. The second separator in the water separator 138 separation line 136 becomes in the line 3 = aqueous stream and in the tube acetic acid stream m mode, the aqueous stream may contain a small amount of acetic acid and may be referred to as a dilute acid stream. The aqueous stream may comprise acetic acid in an amount of less than 20% by weight, such as less than 15% by weight, less than 1% by weight, or less than 5% by weight. In some embodiments 'based on the amount of acid in the second residue 136, the second residue may be purged by blow-off in the pipeline to the reaction, or may be treated as discussed above. As shown in Figure 4, the aqueous stream 139 can be returned to the first vapor column 1〇7 as an extractant. There may be some tannic acid in the water, 139 in the tilting towel, and the secret 139 can be combined with fresh water 125 ’ and then returned to the first steaming tower 1〇7. The acetic acid stream (10) from the water separator 1; 38 preferably contains acetic acid at a still present concentration. The acetic acid stream 140 can be returned to the reaction zone 1〇1. In one embodiment, the acetic acid in the second residual stream from the acetic acid distillation column can be depleted by reaction, leaving a pure aqueous stream. In Fig. 5, the second residue 132 is directed to the third distillation column 141 for esterification. In one embodiment, substantially all of the unreacted acetic acid is depleted in the first residue 132. According to the present invention, acetic acid in the second residue 132 is reacted with methanol in the line 142 in the 5a unit 141 to produce methyl acetate in the line 143. Although methanol is used in the foregoing, it should be understood that other alcohols may be used, including mixtures of ethanol or alcohols. For example, if ethanol is used instead of methanol, ethyl acetate will be produced in line 143. As shown in Fig. 5, the esterification unit is a reactive distillation column (third distillation column) 141. The second residue 132 and the methanol stream 142 are fed to the third distillation column 141 to produce a third residual stream 145 comprising methyl acetate, and a third distillate stream comprising water. At least a portion of the third residual stream can be purged from the system by line 145. Figure 5 shows the methanol feed stream .142 fed to the third steaming tower 31. The location of 201247301 is sent to the second residue 132 below the third steaming tower point. In other embodiments, the methanol feed stream may be sent to the second vapor column 141 at the same level as or below the second residue feed point to the third vapor column. "If the third steaming tower 141 is a reactive steaming tower, as shown in Fig. 5, the third steaming tower 141 comprises an ion exchange tree, an acid catalyst, or a combination thereof. Examples of non-limiting ranges of medium ion exchange resins include OnaeoOpomus stroi^add eati〇n exchange resins) ' For example, those obtained from Dow Chemical Company (for example, _ _5® 'Amberlysm® and Amberlyst 36®.) Other ion exchange resins suitable for use in the present invention are disclosed in U.S. Patent Nos. 4,615,806, 5,139,981 and 7, 588, the entire disclosure of each of The acid is added to the third distillation column 141 to catalyze the esterification reaction. In this state, the acid may be selected from the group consisting of sulfuric acid 'phosphoric acid, sulfonic acid, heteropolyacids, other inorganic acids, and their A group of mixtures. In other embodiments, the acid catalyst comprises a zeolite and a support which is treated with a mineral acid and a heteropolyacid. In some embodiments, if an ion exchange resin is present The third distillation column 141, before being fed to the third distillation column 141, may be fed to a guard bed (not shown). In one embodiment, the guard bed comprises an ion exchange resin as disclosed above. Although not limited to any particular theory, the guard bed can remove one or more corrosive metals in the second residue 132, thereby minimizing any ion exchange resin catalysis of the exchange resin in the third distillation column 141. Purification of the sites The operating parameters of the third distillation column 141 can be modified to achieve the desired composition at the third distillate 143 and/or the residual stream 144. For example, in some embodiments, temperature, pressure, progress The feed rate and residence time can be varied to increase the conversion of the acetic acid ester to reduce the formation of impurities to achieve more efficient separation to reduce energy consumption, or a combination thereof. In one embodiment, the third distillation column 141 bottom operating temperature from 100. (: to 15 〇. (:, for example, from 100 ° C to 130 ° C, or from 10 (TC to 120 t. In terms of pressure, the reaction distillation column can be at atmospheric pressure, times Operating at subatmospheric pressure or superatmospheric pressure. 32 201247301 til application method, countering the pressure of scale operation, build a thousand handles from Caipa, for example, from 50 kPa to 400 kPa' or from 5 〇 From kilopascals to 2 kPa. In some embodiments, the acetic acid and alcohol feed rates of the third distillation scale 141 can be delivered to the molar ratio of the acid to alcohol of the third distillation scale 141. For example, In the second two modes, the molar ratio of acetic acid to methanol in the reaction tower is from i: 丨 to - for example 'from 1:1 to 1 · · 5, or from i : 1 ' the third steamed crane tower The residence time of 141 affects the conversion of acetic acid. For example, in one formula, the residence time in the third steaming tower is from i to 5 hours, for example, from hours, or less than one hour. The third take-off product discharged from the third distillation column 141 in the line 143 is preferably 1-5%, which is preferably 5% by weight, and preferably the red is less than the weight of the wei, or the best To v65 wt% of acetic acid, the third substance 143 from the third steaming secret (4) can be known to 99% by weight, for example, % to _% by weight, sensitive to 5 parts by weight of acetic acid A cool. If excess sterol is reacted with acetic acid from the dilute acid stream, some methanol may also be present in the third effluent 143. Therefore, the third library outlet 143 may contain sterols from 〇% by weight, for example, from 1 至 to 60% by weight, or from 1 to 3% by weight. During the reaction of the second distillation column 129, some impurities such as dimethyl ether may be formed. In the second distillate stream 143, the content of these impurities can be very low, even without the amount detected. In some embodiments, the third distillate 143 comprises less than 1, 〇〇〇 by weight ppm, for example, less than 750 ppm by weight, or less than 5% by weight of dimethyl ether. The second library outlet stream 143 can be fed to a basement reactor for the production of acetic acid, which in turn can be used as a feedstock for the ethanol synthesis reaction. In some embodiments, the third distillate stream 143 can be optionally condensed, processed, or refined prior to being fed to the carbonylation reactor. In one embodiment, an additional third distillation column 146 can be used due to the presence of ethyl acetate in the second distillate 131. A third distillation column 146, also referred to as a "light fraction distillation column," is used to remove ethyl acetate from the second distillate 131, and a third residue in line 148 is used to make B 33 201247301 alcohol product. The light museum steam tower M6 can be a tray type steam tower or a filled steam tower tower 6th, and the third steam tower 146 can have 5 to 9 theoretical trays, for example, 1 to ^ Tray, or 15 to 50 theoretical trays. The feeding position of the second museum's 131 may vary, depending on the concentration of ethyl acetate, and the second is the second. The upper part of the yam tower is exhausted. The high concentration of acetic acid & is intended to feed into the higher position of the third steaming valve 146. The position of the feed should be avoided at the very top of the tray 'close to the reflux to avoid _ tower again (four) too much The load and the tower's stipulations are required. For example, in a steaming tower with 45 actual trays, the position of the feed should be between the 10th and the 1stth of the trays. The above point feeds and the size of the light shop steamed Na 146. h force Α ( (four) negative one second proud product 131 can feed the temperature up to 7 (rc, for example, up to order or 4 〇 two steaming In some embodiments, it is not necessary to preheat the second shaft (3). The acetic acid B is intended to be concentrated in the third take-up of line 147. Due to the relatively low amount of ethyl acetate Feeding the third steaming mash (10), the third crane product of the pipeline 147 also contains a large amount of recovered ethanol. The third museum output in the pipeline 147 can be fed into the first steaming tower 1〇7, which is lightly acid. 2 vinegar circulation flow. Because this will increase the first steaming tower (10) and the best one is in the tube fine (four) three postal money · ship's position _ quantity%: seeking from $ to 88% by weight, or from 75 to 85% by weight From 2 in other embodiments, the third portion of the portion in line 147 can be purged from the blow as another product, such as an ethyl acetate solvent. In an alternative embodiment, the third residue 148 It can be further processed to recover the required amount of water and ethanol. For example, it is necessary to inspect the tower and adsorb the U. If necessary, the water can be removed from the third residue of the tube coffee. In the process of entering the third distillation column 146, the water is firstly used to feed the ethanol into the step. The water is first removed from the vein, so that the third steaming scale is not required. The preferred one is operated under the slit steam pressure as described above. The temperature of the third residue from the first steaming and tearing line 148 is preferably ^ 34 201247301 from 65 ° C to 110 ° C, for example, from 7 (T (^10(rc, or 沱 to (10)乂. The temperature of the third donor discharged from the line 147 of the column 146 is preferably from 3 (rc to 7 〇 &lt;&gt;c ', 40 ° C to 65 ° C, or 50 ° C to 65 ° C. The pressure of the third distillation column 146 may range from 0.1 kPa to 510 kPa, for example, from 千 kPa to 475 kPa, or 丨 kPa to 375 kPa. In some embodiments, the third steaming tower (4) can be operated at a pressure below 70 kPa, such as below 5 kPa, or below 2 kPa. The operating pressure drop will substantially reduce the load on the column and the third column 146. The typical composition of the residue of the ethanol mixed stream and the third distillation column 146 is provided in Table 7 below. It should be understood that the exhibits and residues may also contain other ingredients not listed in Table 7. Knife concentration (% by weight) Concentration (% by weight) Concentration Γ Cao Jin%, 70 to 99 72 to 90 Μ to 85 0.5 to 30 1 to 25 1 to 15 &lt; 15 0.001 to 10 0.1 to 5 &lt; 10 0.001 to 2 〇.〇1 to 1 &lt;2 0.001 to 1 〇.〇1 to 0_5 80 to 99.5 85 to 97 90 to 95 &lt;8 0.001 to 3 0.01 to 1 &lt;1.5 0.0001 to 1 0.001 to 0.5 ^0.5 &lt;0.01 0.0001 to 0.01 Third distillate Ethyl acetate Acetate acetaldehyde Water acetal Third residue Ethyl alcohol ethyl acetate acetic acid 148. In some embodiments, water may be present in the 131 distillate, which may be transferred to the ethanol product stream in a mode prior to recovering the ethanol product prior to removal of the water. In one embodiment, the distillate in line 131 may comprise less than L5 wt% water, such as less than 10 wt% 35 201247301% water or less than 8 wt% water. The distillate in line 131 can be fed to a water separator, which can be an adsorption unit, a separation membrane, a molecular sieve, an extractive distillation column, or a combination thereof. In one embodiment, at least 50% of the second saturated material of line 131 is condensed and can be directed to third retort 146. One to Fig. 7 are diagrams showing the combination of the use of the reactive distillation column M1 and the ethanol product distillation column 146. In this schematic diagram, the second distillate 131 is fed to the ethanol product distillation column 146, and the second residue 132 is fed to the reactive distillation column 14 as a result of the purified ethanol recovery as a second residue in line 148, while acetic acid The ethyl ester is recovered as the third distillate 147 and sent back to the first distillation column 107. The second residue 132 is sent to the reactive distillation column 141, and the acetic acid and the methanol in the second residue are reacted to generate a subsequent gg, which is then in the line 143. The aqueous stream 144 is recovered as a fourth residue&apos; and the first item is returned as a scale. At least a portion of the aqueous 144 can be purged from the system by blowing in the line 145. Returning to the first strip of line 117, which comprises ethyl acetate and/or ethyl acetate, preferably refluxed at a reflux ratio as shown in Figure 1, for example, the reflux ratio from i: 3〇 to 3〇: Bu Ru, from 1: 5 to 5: Bud: 3 to 3: Bu is in the same state, not shown here, the No. Hall or its part can be returned to the reactor Yang. In some embodiments, the paste is a portion of the first-out-return reactor trace from the first-case acetic acid ethyl acetate and/or the reaction can be advanced in the hydrogenation reactor (10) or the second reactor reaction. . The effluent from the second reactor can be sent to the reaction H1G3' to produce more ethanol, or sent to a steaming tower to recover additional ethanol. In some embodiments, the first take-up at line 117 may further comprise a small amount of water. If all or part of the first touch is returned to reaction (4) 3, then it must be removed from line ι 7 such as 'the water from the first residue in line 117 can be removed by the adsorption device, one or more , molecular sieve, extraction steam tower or a combination thereof is removed. For example, the adsorption unit =) can be used to discharge the aqueous stream from the first column of the conduit 117 to produce a stream of intermediate components, preferably containing less than 1% by weight of water, and more preferably less than 0.5. The weight absorbing device can remove up to 99 water from the first faucet in line 117 to remove 95% to 99 99% of the water from the first item. The refined light component can be returned to the reactor 1〇3. 1 36 201247301 In one embodiment, one or both of the first distillate or a portion of the stream in line 117 is complete. The hydrazine can be further separated to produce a stream containing ethylene and a stream containing acetic acid. This allows a portion of the stream containing or containing the ethyl acetate stream to be recovered to reactor 1〇3 while blowing to purge other streams. Blowing off the stream can be used as a valuable source of ethyl acetate and/or acetaldehyde. The distillation column used in the present invention may comprise any distillation column capable of performing the desired separation and/or purification. Preferably, the distillation column comprises a tray distillation column having from 丨 to 〖% of trays, for example, from 20 to 95 trays, or from 30 to 75 trays, from 1 to ι00 towers plate. The trays can be sieve trays, solid (four) trays, transfer trays or any other suitable design known in the literature. In other embodiments, a filled steam can be used. As far as the filled steaming tower is concerned, the regular material, the material and the loose packing can be used. These trays or (iv) may be arranged in a continuous distillation column, or may be arranged in two or a seat, so that the liquid enters the second stage from the first stage and the liquid enters the first stage from the second stage. The associated condenser and liquid separation tank associated with each steaming can be any conventionally designed for use in a towel. Heat can be supplied to each bottom of the steam, or the bottom stream can be circulated through or _(rebc)ilel0° can also be used with other types of refills such as internal reboilers. The heat input into /, f 5 can come to the heat generated in the previous process, the process can be combined with the reboiler 2-= with the fourth (four) heat source, such as other heating chemical process or boiler. Although flash towers are shown as shown in the drawings, additional components, condensers, heaters 70 and other components may be used in various embodiments of the invention. The familiar art valve in this field can be combined and integrated in various condensers, pumps, compressors, reboilers, drums, process separation vessels, etc. of the 55 chemical process. The temperature and pressure of Lin can vary. Regardless of the temperature of the domain (10), the composition of the material at the position and the smelting of the smelting tester may be different. The rate of the feed may vary depending on the scale of the process. In general, the feed weight ratio can be between the technical field and the boiling point of the removed residue composition. For the general knowledge of the distillation, it is known that the temperature at the point of operation of the distillation column is 3737 201247301 in the tube. The cranes of roads 119, 128, and 131 contain ethanol, as described above, by means of additional = off-system, such as 'steaming (eg, towering towers), pressure swing adsorption systems, and alcohol production: The sieves s, 1 take the distillation column' or a combination thereof, and can be further purified 'to form an anhydrous ethanol product; IL, that is, the completed anhydrous ethanol". Any compound that passes through the fine process should be kept at a weight of B. ii. ί. ο.1% by weight 'for example, less than 0.05% by weight ' or less than 〇.〇2 ft. The percentage is ethanol. In terms of the total weight of the composition. In an embodiment, the impurities of any of the steaming towers are removed from the second steam. Preferably, it is used to remove the filament f. This f can be added _ _ and / or retained (d) The final ethanol composition obtained in the process of the invention of i can be taken out via the peak of the line U9, 131 or 135 - or optionally via the concentration of 8 residual components 帚Ethanol 85 to 99.9 water &lt;8 acetic acid &lt;1 ethyl acetate &lt;2 acetal &lt; 0.05 propylene &lt; 0.05 isopropyl alcohol &lt; 0.5 n-propanol &lt; 0.5 . concentration (% by weight) 90 to 99.5 0.1 To &lt;0.1 &lt;0.5 &lt;0.01 &lt;0.01 &lt;0.1 &lt;0.1 concentration (weight·§·%) 92 to 99.5 0.1 to &lt;0.01 &lt;0.05 &lt; 0.005 &lt;0.005 &lt;0,05 &lt;;0.05 alcohol. In the case of a real = 3 such as a f, n-butanol, isobutanol, isoamyl alcohol, etc., the isopropanol content in the finished ethanol composition is from (10) to ... (10) weighs 38 201247301 ppm 'For example' from 95 to 1, 〇〇〇 weight ppm, from lion to γ ό ο ppm by weight, or from 丨 5 〇 to 500 ppm by weight. In one embodiment, the finished ethanol composition is preferably substantially free of acetic acid and may comprise less than 8 ppm by weight acetaldehyde, such as less than 5 weight acetaldehyde or less than hydrazine ppm. The ethanol compositions completed in accordance with embodiments of the present invention are suitable for use in a variety of applications, including fuels, solvents, chemical materials, pharmaceuticals, detergents, disinfectants, hydrogenated delivery or consumer products. In fuel applications, denatured ethanol compositions can be blended with gasoline for use in motor vehicles such as cars, boats and small plug-in machines. In the non-fuel, the finished ethanol composition can be used as a solvent, a detergent, a disinfectant, a paint, an ink, and a drug for cosmetic and cosmetic preparations. The finished ethanol composition can also be used as a process solvent for pharmaceutical products, food preparations, dyes, photochemicals, and latex processing. The completed ethanol composition can also be used as a chemical raw material to make other chemical materials such as vinegar, ethyl acetoacetate, ethyl acetate, ethylene glycol, ethylene glycol oxime, ethylamine, lysine, high carbon alcohol, especially It is butanol. The ethylene compound which is produced in the production of acetic acid can be vinegared by (iv) acid. In another application, the finished ethanol composition can be dehydrated to produce ethylene. [Embodiment] In order to make the disclosure of the present invention more understandable, the following embodiments are provided. It should be understood that these examples are for purposes of illustration only and should not be construed as a limitation. EXAMPLES Eight kinds of separation processes of the present invention. The crude ethanol product was fed into the system containing three steaming towers. The first steaming operation was carried out using water as the extractant, and the extraction was not carried out: the vapor phase I was also tested under atmospheric pressure and a vacuum of about 33 kPa. The pressure demand and ethanol yield of the first steaming tower are disclosed in Table 9. 39 201247301 No water, _ __ Atmospheric pressure energy demand 1.66 [million British thermal units / ton of ethanol] Back to 87.1 〇 / 〇 ethanol in the residue Table 9 No water vacuum 0.68 7jC, water extraction vacuum 0,75 0.53 90.1% 98.3% 99.3% As shown in Table 9, when water is used as the extractant of the first-fine column, the number of _ towers drops to 0'75. At the same time, the amount of ethanol recovered rose from 87 1% to 98 3 II. The anvil was used as a steaming tower. 0 &amp; outside the pressure of the operation, although he has invented the details of the bribe, but it is obvious to those skilled in the art of this genre. The above discussion &amp; the present invention, the aspects and the various parts of the various embodiments and/or the various features and/or the following may be combined or interchanged in whole or in part. Various implementations in front! : Appropriately combined with other implementations, familiar with the field of technology = 2 =, which can be incorporated herein by reference. =: Yes; == The technical person understands that the foregoing description is only a [round simple description]. The invention is explained in detail below with reference to the various drawings, wherein like numerals refer to the same elements. Figure 1 shows a schematic diagram of an ethanol production system according to the present invention - an extractive distillation column for recovering extractant from acetic acid. Figure 2 is a schematic view showing an ethanol production system according to the present invention, which is a distillation column for recovering an extractant from ethanol. The third circle shows a schematic diagram of an ethanol production system according to an embodiment of the present invention, which comprises a distillation column for recovering a dilute acid stream of 201247301, and the dilute acid stream is suitable as an extractant. Figure 4 is a schematic view showing an ethanol production system according to an embodiment of the present invention, which comprises a distillation column for recovering an extractant, and is separated into acetic acid returned to the reactor by one or more water separation devices, and recovers water as an extractant. . Fig. 5 is a view showing an ethanol production system according to an embodiment of the present invention, which comprises a distillation column for recovering an extractant, and an esterification unit. Fig. 6 is a view showing an ethanol production system according to an embodiment of the present invention, which comprises a steaming tower for recovering a dilute acid stream, and another steaming tower for separating ethyl acetate and ethanol. Fig. 7 is a view similar to Fig. 6 in which an ethanol production system according to an embodiment of the present invention has an esterification unit. [Main component symbol description] Code description 100 Hydrogenation system 101 Reaction zone 102 Separation zone 103 Reactor 104 Hydrogen feed line/line/hydrogen feed 105 Acetic acid feed line/line 106 Separator 107 First distillation column /Extractive distillation column 108 First steaming tower / acid steaming tower 109 Third distillation tower 110 Evaporator 111 Pipeline *------------------ 41 201247301 Code description 112 Line 113 Liquid stream / ethanol crude product 114 vapor stream 115 extractant 117 line 118 second residue / line 119 second distillate 120 line / third residual stream 121 line 122 second distillation column 123 tube Road 124 Line 125 Fresh Water 126 Third Distillation Column 127 Line / Third Residual Stream 128 Line 129 Second Distillation Column / Dilute Acid Recovery Distillation Column 131 Second Distillate / Line 132 Pipeline / Dilute Acid Stream /Second residue 133 Blowing purge 134 Second distillation column 135 Line 136 Line 137 Line 42 201247301 Code description 138 Water separator 139 Line 140 Line / acetic acid stream 141 Third distillation column / esterification unit / Reactive distillation column 142 pipe / methanol Stream 143 Line / Third Distillate Stream 144 Third Residue Stream 145 Line / Third Residue Stream 146 Additional Third Distillation Column / Light Fraction Distillation Column 147 Pipe / Ethyl Acetate Recycling Stream 148 Pipe / Ethanol Product stream / third residue stream 43

Claims (1)

201247301 七 申請專利範圍: 1· -種用於生產乙醇的製程,包括: 酸進料流之醋酸’而形成乙醇粗產物; 粗產物成為於一種或多種萃取劑存在下,分離至少—部分的乙醇 醋及-種:酸和醋酸乙醋的第一潑出物,和包含乙醇、醋酸乙 或夕種萃取劑的第—殘留物; 醋:乙至少-部分的第-殘留物’而產生包含乙醇和 及 一館出物’和包含一種或多種萃取劑的第二殘留物;以 物’而產生包含醋酸乙_第三德出物’ 2.二=利範圍第!項所述之製程,其中一種或多種萃取劑選自由水、 1,4-丁二^風、甘^、二甘醇、1 ·萘㉒、對苯二盼、N,N’_二甲基甲醯胺、 醇-四^t、甘醇_1,5 -戊二醇、丙二醇·四甘醇·聚乙二醇、甘油-丙二 丙-吐Ά 丁二醇、乙醚、甲酸甲醋、環己烧、N,N’-二甲基-1,3-烷基嗅甲基乙二胺胺、二乙三胺、己二胺、以二胺戍烧、 之群組!7、十二院、十三院、十吨 '氯化码、及其混合物所組成 ★申請專利範圍任—項所述之製程,其中在第二殘留物回收一種 4次f種卒取劑,並送回到第一蒸餾塔。 2述中請專利範圍任―項所述之製程,其中至少—部分的第二殘留 5 細到第-錢塔,作為一種或多種萃取劑β •=申請專利範圍任一項所述之製程,其中第二殘留物之返 6 L 3低於3〇重量%之醋酸。 .^述巾請專利範圍任-項所述之製程,其中第-殘留物包含低於5 里重%的醋酸乙酯。 · 月』述申清專利範圍任一項所述之製程,其中一種或多種萃取劑至少 201247301 之一種是在反應器中一起產出。 ^述巾st專利朗任—項所狀製程,其巾至少娜在乙醇粗產物 中的乙醇被抽移到第一殘留物流。 9. 如讀巾清專利範圍任—項所述之製程,其中第—賊物包含從〇〇〇1 至2〇重量%的乙醇和從!至15重量%的水。 10. 如前述申請專利範圍任一項所述之製程,還包括分離至少一部分的第 一殘留物’而形成水性物流和醋酸流。 11. 如則述中料利範圍任_項所述之製程,還包括送回至少—部分的醋 酸流至反應器。 2.如别述申6青專利範圍任—項所述之製程,還包括送回至少一部分的水 性物流到第—猶塔,作為-種或多種的萃取劑。 13. 如前述申請專利範圍任—項所述之製程,還包括 在酯化單元中使來自第二殘留物的醋酸和至少一種醇反應,而產生至 少一種酯和水;以及 從水中分離至少-種酿,而產生包含至少一種醋的酉旨產物流,和包含 水的水溶液物流。 14. 如前述申請專利範圍任一項所述之製程,還包括返回至少一部分的水 溶液物流到第一蒸顧塔,作為一種或多種的萃取劑。 15. 如前述申請專利範圍任—項所述之製程,其中第一蒸餾塔在低於7〇千 帕的壓力下操作。 45201247301 Seven patent application scope: 1. A process for producing ethanol, comprising: acetic acid in the acid feed stream to form a crude ethanol product; the crude product is in the presence of one or more extracting agents, separating at least part of the ethanol Vinegar and - species: the first splash of acid and ethyl acetate, and the first residue containing ethanol, acetic acid or Ethyl extractant; vinegar: B at least - part of the first residue - resulting in the inclusion of ethanol And a library of 'and a second residue containing one or more extractants; produced by the product 'containing acetic acid _ third German exports' 2. two = profit range! In the process described, wherein one or more extracting agents are selected from the group consisting of water, 1,4-butane, glycerol, diethylene glycol, 1 naphthalene 22, p-phenylene, N, N'-dimethyl Formamide, alcohol-tetrazide, glycol-1,5-pentanediol, propylene glycol, tetraethylene glycol, polyethylene glycol, glycerol-propylenedipropene-tetrahydrobutanol, diethyl ether, methyl formate, Cyclohexene, N,N'-dimethyl-1,3-alkyl succinylethylenediamine, diethylenetriamine, hexamethylenediamine, diamine oxime, group! 7. The process described in the 12th, 13th, and 10th ton 'chlorination codes, and their mixtures>> the scope of application of the patent application, wherein a 4th f-type stroke agent is recovered in the second residue. And returned to the first distillation column. (2) The process described in the scope of the patent, wherein at least part of the second residue 5 is fined to the first-thousand tower, as one or more extractants β •= the process described in any one of the patent claims, Wherein the second residue returns 6 L 3 of less than 3% by weight of acetic acid. The invention described in the scope of the patent, wherein the first residue comprises less than 5 liters of ethyl acetate. The process described in any one of the patent scopes, wherein one of the one or more extractants at least 201247301 is produced together in the reactor. In the process described in the patent, the method of the invention is that the ethanol of at least the crude ethanol product is pumped to the first residue stream. 9. The process of claim 1, wherein the first thief comprises from 1 to 2% by weight of ethanol and from ! to 15% by weight of water. 10. The process of any of the preceding claims, further comprising separating at least a portion of the first residue&apos; to form an aqueous stream and a stream of acetic acid. 11. The process as described in the section above, further comprising returning at least a portion of the acetic acid stream to the reactor. 2. The process of claim 6, wherein the process of returning at least a portion of the aqueous stream to the first step is used as an extractant of one or more species. 13. The process of any of the preceding claims, further comprising reacting acetic acid from the second residue with at least one alcohol in the esterification unit to produce at least one ester and water; and separating at least from the water - Seeding produces a stream of product comprising at least one vinegar, and an aqueous stream comprising water. 14. The process of any of the preceding claims, further comprising returning at least a portion of the aqueous solution stream to the first vapor column as one or more extractants. 15. The process of any of the preceding claims, wherein the first distillation column is operated at a pressure of less than 7 kPa. 45
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