CN102307657B - Acetic acid using an acid catalyst prepared by the method of ethanol - Google Patents

Acetic acid using an acid catalyst prepared by the method of ethanol Download PDF

Info

Publication number
CN102307657B
CN102307657B CN201080003928.5A CN201080003928A CN102307657B CN 102307657 B CN102307657 B CN 102307657B CN 201080003928 A CN201080003928 A CN 201080003928A CN 102307657 B CN102307657 B CN 102307657B
Authority
CN
China
Prior art keywords
metal
method
catalyst
ethanol
acetic acid
Prior art date
Application number
CN201080003928.5A
Other languages
Chinese (zh)
Other versions
CN102307657A (en
Inventor
R·耶夫蒂奇
V·J·约翰斯顿
R·J·沃纳
H·魏纳
Original Assignee
国际人造丝公司
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority to US12/588,727 priority Critical
Priority to US12/588,727 priority patent/US8309772B2/en
Priority to US12/698,947 priority patent/US8471075B2/en
Priority to US61/300,815 priority
Priority to US30081510P priority
Priority to US12/699,024 priority patent/US8680317B2/en
Priority to US12/699,024 priority
Priority to US12/698,947 priority
Priority to US61/332,696 priority
Priority to US61/332,699 priority
Priority to US33269610P priority
Priority to US33269910P priority
Priority to US12/852,227 priority
Priority to US12/852,269 priority
Priority to US12/852,269 priority patent/US8304586B2/en
Priority to US12/852,227 priority patent/US8309773B2/en
Application filed by 国际人造丝公司 filed Critical 国际人造丝公司
Priority to PCT/US2010/054136 priority patent/WO2011056597A2/en
Publication of CN102307657A publication Critical patent/CN102307657A/en
Application granted granted Critical
Publication of CN102307657B publication Critical patent/CN102307657B/en

Links

Classifications

    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/002Mixed oxides other than spinels, e.g. perovskite
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J21/00Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/02Boron or aluminium; Oxides or hydroxides thereof
    • B01J21/04Alumina
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J21/00Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/06Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J21/00Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/06Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
    • B01J21/063Titanium; Oxides or hydroxides thereof
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J21/00Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/12Silica and alumina
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/54Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/56Platinum group metals
    • B01J23/62Platinum group metals with gallium, indium, thallium, germanium, tin or lead
    • B01J23/622Platinum group metals with gallium, indium, thallium, germanium, tin or lead with germanium, tin or lead
    • B01J23/626Platinum group metals with gallium, indium, thallium, germanium, tin or lead with germanium, tin or lead with tin
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/54Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/56Platinum group metals
    • B01J23/64Platinum group metals with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/656Manganese, technetium or rhenium
    • B01J23/6567Rhenium
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02Impregnation, coating or precipitation
    • B01J37/0201Impregnation
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02Impregnation, coating or precipitation
    • B01J37/0201Impregnation
    • B01J37/0205Impregnation in several steps
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02Impregnation, coating or precipitation
    • B01J37/0201Impregnation
    • B01J37/0207Pretreatment of the support
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/08Heat treatment
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C1/00Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
    • C07C1/20Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms
    • C07C1/24Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms by elimination of water
    • 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
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J21/00Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/16Clays or other mineral silicates
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2523/00Constitutive chemical elements of heterogeneous catalysts
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02PCLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00Technologies relating to chemical industry
    • Y02P20/50Improvements relating to the production of products other than chlorine, adipic acid, caprolactam, or chlorodifluoromethane, e.g. bulk or fine chemicals or pharmaceuticals
    • Y02P20/52Improvements relating to the production of products other than chlorine, adipic acid, caprolactam, or chlorodifluoromethane, e.g. bulk or fine chemicals or pharmaceuticals using catalysts, e.g. selective catalysts

Abstract

一种在催化剂存在下通过将乙酸加氢由乙酸选择性形成乙醇的方法,所述催化剂包含在酸性载体上的第一金属。 A method of selectively hydrogenating acetic acid to form ethanol from acetic acid in the presence of a catalyst, said catalyst comprising a first metal on an acidic support. 所述酸性载体可以包含酸性载体材料或者可以包含具有酸性载体改性剂的载体。 The acidic carrier may comprise an acidic support material or may comprise a carrier having an acidic support modifier. 所述催化剂可以单独使用或者与另一种催化剂组合使用以通过加氢生产乙醇。 The catalyst may be used alone or in combination with another catalyst by hydrogenation to produce ethanol. 此外,将粗乙醇产物分离以获得乙醇。 Further, the crude product was separated from ethanol to obtain ethanol.

Description

使用酸性催化剂由乙酸制备乙醇的方法 Acetic acid using an acid catalyst prepared by the method of ethanol

[0001] 优先权要求 [0001] PRIORITY CLAIM

[0002] 本申请要求以下申请的优先权:(1) 2009年10月26日提交的美国申请No. 12/588,727 ;(2) 2010年2 月2 日提交的美国申请No. 12/698,947 ;(3) 2010年2月2 日提交的美国申请No. 12/699,024 ;(4)2010年2月2日提交的美国临时申请No. 61/300,815 ; (5)2010年5月7日提交的美国临时申请No. 61/332, 696; (6)2010年5月7日提交的美国临时申请No. 61/332,699 ; (7)2010年8月6日提交的美国申请No. 12/852, 269 ;和(8) 2010年8月6日提交的美国申请No. 12/852,227。2009年10月26日提交的美国申请No. 12/588, 727是2008年7月31日提交的美国申请No. 12/221,141的继续部分。 [0002] This application claims priority of: (1) United States October 26, 2009 filed No. 12 / 588,727; (2) 2010 Nian 2 filed May 2 US Application No. 12 / 698,947; (3) United States February 2, 2010 filed No. 12 / 699,024; (4) United States 2 February 2010 provisional application No. 61 / 300,815; (5) filed May 7, 2010 in US provisional application No. 61/332, 696; (6) the United States May 7, 2010 provisional application No. 61 / 332,699; United States (7) August 6, 2010 filed No. 12/852, 269; and the United States (8) August 6, 2010 filed No. 12 / 852,227, US application No. 2009 filed May 26 in 10 of 12/588, 727 in the United States July 31, 2008 filed. No. continuation of 12 / 221,141 in. 通过引用将这些申请全文并入本文。 By reference in their entirety incorporated herein. 发明领域 Field of the Invention

[0003] 本发明总体上涉及生产乙醇的方法,特别涉及使用酸性催化剂由乙酸加氢生产乙醇的方法。 [0003] The present invention relates generally to a method for producing ethanol, particularly to a method using an acid catalyst consisting of acetic acid hydrogenation to produce ethanol.

[0004] 发明背景 [0004] Background of the Invention

[0005] 用于工业用途的乙醇按照常规由石油化工原料例如油、天然气或煤生产,由原料中间体例如合成气生产,或者由淀粉质材料或纤维素材料例如玉米(corn)或甘鹿生产。 [0005] ethanol for industrial use is conventionally from petrochemical feed stocks such as oil, natural gas or coal, the raw synthesis gas production intermediates such as, for example maize or (Corn) or Gan Lusheng production from starchy materials or cellulose materials . 由石油化工原料以及由纤维素材料生产乙醇的常规方法包括乙烯的酸催化水合、甲醇同系化、直接醇合成和费-托合成。 From petrochemical feedstocks and a conventional process for producing ethanol from cellulosic material comprising the acid-catalyzed hydration of ethylene, methanol homologation, direct alcohol synthesis, and Fischer - Tropsch synthesis. 石油化工原料价格的不稳定性促使按照常规生产的乙醇成本波动,在原料价格升高时使对乙醇生产的替代来源的需要比以往更大。 Petrochemical raw materials price volatility prompted in accordance with conventional ethanol production cost fluctuations, the need for alternative sources of ethanol production in the prices of raw materials increased more than ever. 淀粉质材料以及纤维素材料通过发酵转化为乙醇。 Starchy material and cellulosic material are converted to ethanol by fermentation. 然而,发酵通常用于燃料用或消费用乙醇的消费性生产。 However, fermentation is typically used in fuel consumption or consumption of ethanol production. 此外,淀粉质或纤维素材料的发酵与食品来源构成竞争并且对用于工业用途所可生产的乙醇的量施加了限制。 Moreover, fermentation of starchy or with food sources and cellulosic materials competes for industrial use amount of ethanol that can be produced is limited.

[0006] 通过链烷酸和/或其它含羰基化合物的还原生产乙醇得到广泛研究,在文献中提及了催化剂、载体和操作条件的各种组合。 [0006] been studied extensively by alkanoic acid and / or other reducing production of ethanol-containing carbonyl compound, various combinations of catalysts are mentioned, the carrier and operating conditions in the literature. 在链烷酸例如乙酸的还原期间,其它化合物随乙醇一起生成或者以副反应生成。 During the reduction, for example, acetic acid, other compounds are formed with an alkanoic acid in ethanol or in side reactions. 这些杂质和副产物限制了乙醇的生产和从这类反应混合物的回收。 These impurities and by-products limit the production of ethanol and the reaction mixture is recovered from such. 例如,在加氢期间,产生的酯与乙醇和/或水一起形成难以分离的共沸物。 For example, during the hydrogenation, it is difficult to separate azeotropes are formed together with an ester of ethanol and / or water generated. 此外, 当转化不完全时,未反应的酸保留在粗乙醇产物中,必须将其加以移除以回收乙醇。 Further, when the conversion is incomplete, unreacted acid remains in the crude ethanol product, which must be removed to recover ethanol.

[0007] 因此,仍需要改进的通过链烷酸还原生产乙醇的方法,该方法产生含有较少杂质和副产物的粗乙醇产物。 [0007] Thus, there remains a need for improved alkanoic acid by reduction process for producing ethanol, the process produces a crude ethanol product containing less by-products and impurities.

[0008] 发明概述 [0008] Summary of the Invention

[0009] 在第一实施方案中,本发明涉及生产乙醇的方法,该方法包括在催化剂存在下将乙酸加氢形成乙醇,其中所述加氢具有至少65%的乙醇选择性,其中所述催化剂包含在酸性载体上的第一金属,所述酸性载体选自:(i)选自铁氧化物(ironoxide)、氧化错、二氧化硅/氧化铝、二氧化钛、氧化锆和它们的混合物的酸性载体材料,以及(ii)用酸性改性剂改性的载体材料。 [0009] In the first embodiment, the present invention relates to a process for producing ethanol, in the presence of a catalyst comprising hydrogenating acetic acid to form ethanol, wherein said hydrogenation having at least 65% selectivity to ethanol, wherein said catalyst comprising a first metal on an acidic carrier, the acidic support is selected from: (i) is selected from iron oxides (ironoxide), the wrong oxidation, acidic support silica / alumina, titania, zirconia, and mixtures thereof materials, and (ii) a support material modified with an acidic modifier.

[0010] 在第二实施方案中,本发明涉及生产乙醇的方法,该方法包括:在第一催化剂存在下将乙酸加氢形成包含乙醇和未反应的乙酸的中间产物;在第二催化剂存在下将未反应的乙酸加氢形成乙醇。 [0010] In a second embodiment, the present invention relates to a process for producing ethanol, said method comprising: a first catalyst in the presence of hydrogenating acetic acid to form an intermediate product containing unreacted ethanol and acetic acid; in the presence of a second catalyst the unreacted acetic acid is hydrogenated to form ethanol. 所述第一催化剂包含含有一种或多种金属、含硅载体和至少一种碱性载体改性剂的催化剂。 The first catalyst comprises a catalyst comprising one or more metals, silicon-containing carrier and at least one basic support modifier. 所述第二催化剂包含在酸性载体上的第一金属,所述酸性载体选自: (i)选自铁氧化物、氧化铝、二氧化硅/氧化铝、二氧化钛、氧化锆和它们的混合物的酸性载体材料,以及(ii)用酸性改性剂改性的载体材料。 The second catalyst comprises a first metal on an acidic carrier, the acidic support is selected from: (i) selected from iron oxide, alumina, silica / alumina, titania, zirconia, and mixtures thereof acidic carrier material, and (ii) a support material modified with an acidic modifier.

[0011] 在第三实施方案中,本发明涉及生产乙醇的方法,该方法包括:在反应器中于第一催化剂和第二催化剂存在下将乙酸加氢形成乙醇。 [0011] In a third embodiment, the present invention relates to a process for producing ethanol, said method comprising: at the first catalyst and the second catalyst is present in hydrogenating acetic acid to form ethanol in the reactor. 所述第一催化剂可以在第一反应器区域中并且所述第二催化剂可以在与所述第一反应器区域隔开的第二反应器区域中。 And the first catalyst in the first reactor may be in the second catalyst zone may be spaced apart from the first reactor zone in the second reactor zone. 所述第一催化剂包含含有一种或多种金属、含娃载体和至少一种碱性载体改性剂的催化剂。 The first catalyst comprises a catalyst comprising one or more metals, comprising at least one basic baby carrier and support modifier. 所述第二催化剂包含在酸性载体上的第一金属,所述酸性载体选自:(i)选自铁氧化物、氧化铝、 二氧化硅/氧化铝、二氧化钛、氧化锆和它们的混合物的酸性载体材料,以及(ii)用酸性改性剂改性的载体材料。 The second catalyst comprises a first metal on an acidic carrier, the acidic support is selected from: (i) selected from iron oxide, alumina, silica / alumina, titania, zirconia, and mixtures thereof acidic carrier material, and (ii) a support material modified with an acidic modifier.

[0012] 在第四实施方案中,本发明涉及回收乙醇的方法,该方法包括在包含催化剂的反应器中将乙酸进料流加氢形成粗乙醇产物。 [0012] In a fourth embodiment, the present invention relates to a process for recovering ethanol, the method comprising a catalyst in a reactor comprising hydrogenating a feed stream of acetic acid to form a crude ethanol product. 所述催化剂包含在酸性载体上的第一金属,所述酸性载体选自:(i)选自铁氧化物、氧化铝、二氧化硅/氧化铝、二氧化钛、氧化锆和它们的混合物的酸性载体材料,以及(ii)用酸性改性剂改性的载体材料。 The catalyst comprises a first metal on an acidic carrier, the acidic support is selected from: an acidic support (i) is selected from iron oxide, alumina, silica / alumina, titania, zirconia, and mixtures thereof materials, and (ii) a support material modified with an acidic modifier. 该方法还包括在第一塔中将至少部分粗乙醇产物分离成包含乙醇、水和乙酸乙酯的第一馏出物,以及包含乙酸的第一残余物;在第二塔中将至少部分第一馏出物分离成包含乙酸乙酯的第二馏出物以及包含乙醇和水的第二残余物;使至少部分第二馏出物返回到所述反应器;并且在第三塔中将至少部分第二残余物分离成包含乙醇的第三馏出物和包含水的第三残余物。 The method further comprises at least a portion of the crude ethanol product to contain ethanol, ethyl acetate and water, a first distillate and a first residue comprising acetic acid in a first column; at least a part in the second column a distillate comprising ethyl acetate is separated into a second distillate and a second residue comprising ethanol and water; at least a portion of the second distillate is returned to the reactor; in the third column and at least the residue was separated into a second portion comprising ethanol distillate and a third third residue comprising water.

[0013] 用于本发明实施方案的酸性改性剂优选选自IVB族金属的氧化物、VB族金属的氧化物、VIB族金属的氧化物、VIIB族金属的氧化物、VIIIB族金属的氧化物、铝氧化物和它们的混合物。 Oxidation [0013] acidic modifier for the embodiment of the present invention is preferably selected from oxides of Group IVB metals, Group VB metal oxides, Group VIB metal oxides, Group VIIB metal oxides, VIIIB metals of , aluminum oxides and mixtures thereof.

[0014] 附图简要描述 [0014] BRIEF DESCRIPTION OF THE

[0015] 下面参考附图详细地描述本发明,其中相同的数字指示类似的部件。 [0015] The present invention will be described in detail with reference to the accompanying drawings, wherein like numerals indicate like parts.

[0016] 图1是根据本发明一个实施方案的加氢系统的示意图。 [0016] FIG. 1 is a schematic diagram of a hydroprocessing system according to the present invention embodiments only.

[0017] 图2A是根据本发明一个实施方案的具有双反应器的反应区的示意图。 [0017] FIG. 2A is a schematic view of a reaction zone having a dual reactor in accordance with one embodiment of the present invention.

[0018] 图2B是根据本发明另一个实施方案的具有反应器的反应区的示意图,所述反应器带有两个反应器区域。 [0018] FIG. 2B is a schematic view of a reactor having a reaction zone according to another embodiment according to the present invention, the reactor having two reactor zones.

[0019] 图3是根据本发明实施例的乙酸转化率的坐标图。 [0019] FIG. 3 is a graph of acetic acid conversion according to embodiments of the present invention.

[0020] 图4是根据本发明实施例的不同催化剂的乙酸转化率的坐标图。 [0020] FIG. 4 is a graph of the conversion of acetic acid of different catalysts according to embodiments of the present invention.

[0021] 发明详述 [0021] DETAILED DESCRIPTION

[0022] 本发明涉及生产乙醇的方法和从粗乙醇产物回收乙醇的方法。 [0022] The present invention relates to a process for the production of ethanol and a process for recovering ethanol from crude ethanol product. 在一个实施方案中,粗乙酸产物通过包括在酸性催化剂存在下将乙酸加氢的加氢方法进行生产。 In one embodiment, the crude acetic acid product produced by the hydrogenation process carried out in the presence of an acidic catalyst comprising hydrogenating acetic acid. 在一个实施方案中,所述酸性催化剂包含在酸性载体的第一金属。 In one embodiment, the acidic catalyst comprises a first metal in an acidic support. 在一个实施方案中,所述酸性催化剂包含在载体上的第一金属和酸性载体改性剂。 In one embodiment, the acidic catalyst comprises a first metal and an acidic support modifier on a support.

[0023] 在乙酸加氢期间,存在产生杂质和副产物的其它副反应。 [0023] During the hydrogenation of acetic acid, the presence of impurities and other side reactions generate by-products. 一个主要的副反应是乙酸/乙醇和乙酸乙酯/水之间还发生的平衡反应。 A major side reaction is also an equilibrium reaction between acetic acid / ethanol and ethyl acetate / water. 这两个主反应是: The two main reaction is:

[0024]HOAc+ 2H2 3EtOH十H20反应1 [0024] HOAc + 2H2 3EtOH ten H20 Reaction 1

[0025] HOAe+EtOH达Et0Ac+H20反应2 [0025] HOAe + EtOH reaction of 2 Et0Ac + H20

[0026] 反应2是可逆的并且平衡常数{(^^通过如下方程式1给出: [0026] 2 The reaction is reversible and the equilibrium constant {(^^ are given by the following Equation 1:

[0027] [0027]

Figure CN102307657BD00071

[0028] 通常,为产生乙醇,与消耗乙醇并且提高粗乙醇产物中的乙酸乙酯副产物的第二反应相比反应条件较有利于第一反应。 [0028] Typically, to produce ethanol, ethanol consumption than the second reaction byproducts and improve the crude product in ethyl acetate in ethanol with the reaction conditions more favorable to the first reactor. 在美国公开No. 2010/0197985(通过引用将其全文并入本文)中,通过使用包含碱性改性剂的催化剂有利于和促进第一反应。 In U.S. Publication No. 2010/0197985 (which is incorporated herein by reference), by using a catalyst comprising an alkaline modifier facilitate and promote the first reaction.

[0029] 在一些实施方案中,本发明使用酸性催化剂,该酸性催化剂优选包含在酸性载体上的第一金属。 [0029] In some embodiments, the present invention is the use of an acidic catalyst, the acidic catalyst preferably comprises a first metal on an acidic support. 虽然不受理论束缚,但认为在酸存在下促进第二反应。 While not being bound by theory, it is believed to promote the second reaction in the presence of an acid. 同样在气相中,认为在较高温度下降低。 Also in the gas phase, that decreases at higher temperatures. 在本发明的实施方案中,可以小于20,例如,小于15或小于12。 In an embodiment of the present invention, it may be less than 20, e.g., less than 15 or less than 12. 优选地,KT«可以小于6,例如小于4或小于3。 Preferably, KT «may be less than 6, less than 4 or less than 3. 照此,酸性催化剂提高了该平衡反应的正向和逆向反应速率。 As such, the acid catalyst increases the reaction rate of the forward and reverse equilibrium reactions. 在其中KTW> 1的实施方案中,和在有利于高的乙酸转化率的反应条件下,乙醇的选择性出人意料地和意想不到地高。 In embodiments where KTW> 1's, and in favor of a high acetic acid conversion reaction conditions, the selectivity of ethanol surprisingly and unexpectedly high. 在高转化率下乙醇的产率也提高。 Ethanol at high conversion yield also increased. 提高转化率和乙醇选择性有利地减少粗乙醇产物中副产物的量,其结果是,可以提高回收乙醇的效率。 Improve the conversion rate and selectivity to ethanol in the crude ethanol product an amount of advantageously reduces by-product, as a result, can improve the efficiency of recovering ethanol.

[0030] 就本发明而言,术语"转化率"是指进料中转化为除乙酸外的化合物的乙酸的量。 [0030] For purposes of the present invention, the term "conversion" refers to the amount of feed that is converted to a compound other than acetic acid. 转化率按基于进料中乙酸的摩尔百分数表示。 Conversion is expressed as a mole percent based on the feed acetic acid. 选择性按基于转化的乙酸的摩尔百分数表示。 Selectivity is expressed as a mole percent based on converted acetic acid. 应理解由乙酸转化的每种化合物具有独立的选择性并且该选择性不依赖于转化率。 It should be understood that each compound has an independent converted from acetic acid selectivity and that the selectivity is not dependent on the conversion rate. 例如,如果所转化的乙酸的50摩尔%转化为乙醇,则乙醇选择性为50%。 For example, if 50 mol% of the converted acetic acid is converted to ethanol, the ethanol selectivity as 50%.

[0031] 在较低的乙酸转化率下,例如小于约50%,酸性催化剂倾向于显示出对于乙酸乙酯比对于乙醇高的提高的选择性。 [0031] The conversion of acetic acid at lower rates, e.g., less than about 50%, tend to exhibit an acidic catalyst selectivity to ethyl acetate ratio of ethanol to improve high. 因此,在本发明的一些实施方案中,为生产乙醇,乙酸的转化率优选大于70 %,例如大于80 %、大于90 %或大于95 %。 Thus, in some embodiments of the present invention, for the production of ethanol, conversion of acetic acid is preferably greater than 70%, such as greater than 80%, greater than 90% or greater than 95%.

[0032] 在本发明的方法中,乙醇的选择性优选为至少65%,例如至少70%,至少80%,至少85 %,或至少90 %。 [0032] In the method of the present invention, preferably ethanol selectivity is at least 65%, at least 70%, at least 80%, at least 85%, or at least 90%. 在约70 %的较低乙酸转化率下,乙醇的选择性可以为约30 % -40 %。 Acetic acid at lower conversion of about 70%, the selectivity of ethanol can be about 30% -40%. 优选地,随着乙酸转化率提高,乙醇的选择性也提高。 Preferably, as the acetic acid conversion rate, selectivity to ethanol also improved. 此外,乙酸乙酯的选择性可以是低的, 例如小于35%、小于30%、小于10%或小于5%。 In addition, selectivity to ethyl acetate may be low, for example less than 35%, less than 30%, less than 10%, or less than 5%. 优选地,该加氢过程还具有对不期望的产物例如甲烷、乙烷和二氧化碳的低选择性。 Preferably, the hydrogenation process also has a low selectivity to undesirable products such as methane, ethane, and carbon dioxide. 对这些不期望的产物的选择性优选小于4%,例如小于2%或小于1%。 The selectivity to these undesirable products is preferably less than 4%, for example less than 2%, or less than 1%. 更优选地,这些不期望的产物在粗乙醇产物不易于检测到。 More preferably, these undesirable products is not easily detected in the crude ethanol product. 烷烃的形成可以是低的。 Formation of alkanes may be low. 理想地,穿过催化剂的乙酸小于2%例如小于1 %或小于0. 5%转化为烷烃。 Ideally, the acid catalyst is less than 2% through, for example, less than 1%, or less than 0.5% is converted to alkanes.

[0033] 本发明的实施方案在高的乙酸转化率下提供了提高的乙醇产率。 [0033] Embodiments of the invention provide improved ethanol yield at high conversion of acetic acid. 当乙酸转化率优选大于90%时,乙醇的选择性优选为至少70%。 When the acid is preferably greater than 90% conversion, preferably ethanol selectivity is at least 70%. 选择性可以随着乙酸转化率的提高而持续提1¾。 Selectivity can improve as the conversion of acetic acid continuously mention 1¾.

[0034] 如本文中所使用的术语"产率"是指加氢期间每千克所用催化剂每小时所形成的规定产物例如乙醇的克数。 [0034] As used herein, the term "yield" refers to a predetermined per kilogram of catalyst per hour, during hydrogenation the product is formed, for example, the number of grams of ethanol. 优选每千克催化剂每小时的乙醇产率为至少200克,例如至少400克或至少600克。 The yield of ethanol per kilogram of catalyst per hour, preferably at least 200 grams, for example at least 400 or at least 600 grams. 就范围而言,所述产率优选为每千克催化剂每小时200-3, 000克乙醇,例如400-2, 500 或600-2, 000。 In terms of ranges, the yield per kilogram of catalyst per hour, preferably 200-3, 000 g of ethanol, e.g. 400-2, 600-2 or 500, 000.

[0035] 本发明的实施方案在高的乙酸转化率下提供了提高的生产率。 [0035] The embodiments of the present invention provides increased throughput at high conversions of acetic acid. 在70%以上的乙酸转化率下,乙醇的产率为每千克催化剂每小时至少350克乙醇。 At a conversion rate of 70% acetic acid, the yield of ethanol per kilogram of catalyst per hour at least 350 grams of ethanol. 产率可以随着乙酸转化率的提1¾而持续提1¾。 Yield can be mentioned as the conversion of acetic acid to 1¾ mention 1¾ continuously.

[0036] 在酸性催化剂存在下进行乙酸加氢形成乙醇和水。 [0036] hydrogenating acetic acid to form ethanol and water in the presence of an acidic catalyst. 在一个实施方案中,加氢催化剂包含在酸性载体上的第一金属和可选的一种或多种第二金属、第三金属或其它金属。 In one embodiment, the hydrogenation catalyst comprising a first metal and optionally one or more of a second metal on an acidic support, third or other metal. 第一与可选的第二和第三金属可以选自:IB、IIB、IIIB、IVB、VB、VIB、VIIB、VIII族过渡金属, 镧系金属,锕系金属或者选自ΠΙΑ、IVA、VA和VIA族中任意族的金属。 The first and optional second and third metals may be selected from: IB, IIB, IIIB, IVB, VB, VIB, VIIB, VIII transition metals, lanthanide metals, or actinide metal selected ΠΙΑ, IVA, VA and group VIA metal of any of Groups. 就一些示例性催化剂组合物而言的优选金属组合包括钼/锡、钼/钌、钼/铼、钯/钌、钯/铼、钴/钯、钴/钼、 钴/铬、钴/钌、银/钯、铜/钯、镍/钮,金/钯、钌/铼和钌/铁。 Preferred metal combinations on some exemplary terms catalyst composition comprising molybdenum / tin, molybdenum / ruthenium, molybdenum / rhenium, palladium / ruthenium, palladium / rhenium, cobalt / palladium, cobalt / molybdenum, cobalt / chromium, cobalt / ruthenium, silver / palladium, copper / palladium, nickel / button, gold / palladium, ruthenium / rhenium and ruthenium / iron. 示例性的催化剂还描述于美国专利No. 7, 608, 744以及美国公布No. 2010/0029995和2010/0197985中,通过引用将它们全文并入本文。 Exemplary catalysts are further described in U.S. Patent No. 7, 608, 744 and U.S. Pub. No. 2010/0029995 and 2010/0197985, incorporated by reference in their entirety herein.

[0037] 在一个示例性实施方案中,该催化剂包含选自铜、铁、钴、镍、钌、铑、钯、锇、铱、钼、 钛、锌、铬、铼、钥和鹤的第一金属。 [0037] In one exemplary embodiment, the catalyst comprises selected from copper, iron, cobalt, nickel, ruthenium, rhodium, first palladium, osmium, iridium, molybdenum, titanium, zinc, chromium, rhenium, and key crane metal. 优选地,第一金属选自钼、钮、钴、镍和钌。 Preferably, the first metal is selected from molybdenum, button, cobalt, nickel and ruthenium. 更优选地,第一金属选自钼和钯。 More preferably, the first metal is selected from molybdenum and palladium. 当第一金属包含钼时,由于对钼的高需求,催化剂优选包含小于5重量% 例如小于3重量%或小于1重量%的量的钼。 When the first metal comprises molybdenum, molybdenum is due to the high demand, the catalyst preferably comprises less than 5 wt%, for example less than 3 wt%, or less than 1 wt% molybdenum.

[0038] 如上文所示,该催化剂任选还包含第二金属,该第二金属通常可起促进剂的作用。 [0038] As indicated above, the catalyst optionally further comprises a second metal, the second metal may generally function as a promoter. 如果存在,弟-金属优选选自铜、钥、锡、络、铁、钻、钥;、鹤、钮、销、綱、铺、猛、钉、鍊、金和镇。 If present, brother - preferably a metal selected from copper, keyhole, tin, complex, iron, cobalt, keyhole;, crane, button, pin, outline, shop, Meng, nails, chains, gold town. 更优选地,第二金属选自铜、锡、钴、铼和镍。 More preferably, the second metal selected from copper, tin, cobalt, rhenium, and nickel. 更优选地,第二金属选自锡和铼。 More preferably, the second metal selected from tin and rhenium.

[0039] 如果该催化剂包括两种或更多种金属,例如第一金属和第二金属,则第一金属任选在催化剂中以0. 1-10重量%例如0. 1-5重量%或0. 1-3重量%的量存在。 [0039] If the catalyst comprises two or more metals, for example, a first metal and a second metal, the first metal catalyst optionally in a 0.5 to 10% by weight, for example 0. 1-5% by weight, or present in an amount of 0. 1-3% by weight. 第二金属优选以0. 1-20重量%例如0. 1-10重量%或0. 1-5重量%的量存在。 Second metal preferably is present in an amount of 0.5 to 20 wt%, or 0. 1-5% by weight of 0. 1-10 wt%. 在一个实施方案中,可以降低酸性催化剂的金属载量。 In one embodiment, it can reduce the amount of the acidic catalyst metal loading. 这可以有利地降低与金属载量较高的催化剂有关的费用。 This may advantageously reduce the costs associated with higher metal loading of the catalyst. 因此,在具有降低的金属载量的实施方案中,第一金属可以按0. 1-1. 7重量%的量存在而第二金属可以按〇. 1-1. 3重量%的量存在。 Thus, in embodiments having a reduced metal loading, the first metal may be in amounts of 0. 1-1. 7% by weight of the second metal may be present in an amount billion. 1-1. 3% by weight. 对于包含两种或更多种金属的催化剂,所述两种或更多种金属可以彼此合金化或者可以包含非合金化金属固溶体或混合物。 For catalysts comprising two or more metals, the two or more metals may be alloyed with one another or may comprise non-alloyed metal solid solution or a mixture thereof.

[0040] 优选的金属比率可以取决于催化剂中所用的金属而变动。 [0040] The preferred metal ratios may depend on the metal used in the catalyst varies. 在一些示例性实施方案中,第一金属与第二金属的摩尔比为10 : 1-1 : 10,例如4 : 1-1 : 4, 2 : 1-1 : 2,1. 5 : 1-1 : 1.5或1.1 : 1-1 : 1.1。 In some exemplary embodiments, the molar ratio of the first metal and the second metal is from 10: 1 to 1: 10, for example 4: 1 to 1: 4, 2: 1-1: 2, 5: 1- 1: 1.5 or 1.1: 1 to 1: 1.1. 在一个实施方案中,在催化剂包含钼和锡时为有利于对乙醇的选择性,Pt/Sn摩尔比优选为0.4 : 0.6-0. 6 : 0.4,例如0. 45 : 0.55-0. 55 : 0.45或约1 : 1。 In one embodiment, when the catalyst comprises molybdenum and tin to favor selectivity to ethanol, Pt / Sn molar ratio is preferably 0.4: 0.6-0 6: 0.4, for example 0.45: 0.55-0 55: 0.45 or about 1: 1. 在另一个实施方案中,在其中催化剂包含铼和钯的实施方案中为有利于对乙醇的选择性,Re/Pd摩尔比优选为0.6 : 0.4-0. 85 : 0.15,例如0.7 : 0.3-0.85 : 0.15,或者约0.75 : 0.25 的摩尔比。 In another embodiment, in embodiments wherein the catalyst comprises rhenium and palladium are to favor selectivity to ethanol, Re / Pd molar ratio is preferably 0.6: 0.4-0. 85: 0.15, for example 0.7: 0.3 to 0.85 : 0.15, or about 0.75: 0.25 molar ratio.

[0041] 该催化剂还可以包含第三金属,该第三金属选自上文关于第一或第二金属所列出的任意金属,只要该第三金属不同于第一和第二金属。 [0041] The catalyst may further comprise a third metal, the third metal is selected from any of the metals above in relation to the first or the second metal listed, as long as the first and second metal different from the third metal. 在优选方面,第三金属选自钴、钮、 钌、铜、锌、钼、锡和铼。 In a preferred aspect, the third metal is selected from cobalt, button, ruthenium, copper, zinc, molybdenum, tin, and rhenium. 更优选地,第三金属选自钴、钯和钌。 More preferably, the third metal is selected from cobalt, palladium, and ruthenium. 当存在时,第三金属的总重量优选为0. 05-4重量%,例如0. 1-3重量%或0. 1-2重量%。 When present, the total weight of the third metal is preferably 0. 05-4 wt%, for example 1-3 wt%, 0.5 wt% or 0. 1-2.

[0042] 在一些实施方案中,除一种或多种金属外,本发明的酸性催化剂还包含酸性载体材料或改性的载体材料。 [0042] In some embodiments, one or more metals in addition to, the acidic catalyst of the present invention further comprises an acidic support material or a modified support material. 改性的载体材料包含载体材料和酸性载体改性剂。 Modified support material comprises a support material and an acidic support modifier. 酸性载体改性剂调节载体材料的酸度。 Acidic support modifier adjust the acidity of the support material. 载体材料或改性的载体材料的总重量基于该催化剂总重量计优选为75重量% -99. 9重量%,例如78重量% -97重量%或80重量% -95重量%。 The total weight of the carrier material, carrier material or modified based on the total weight of the catalyst is preferably 75 wt% -99. 9% by weight, e.g. 78 wt% to 97 wt%, or 80 wt% to 95 wt%. 在使用改性载体材料的实施方案中,催化剂可以包含基于该催化剂总重量计0. 1重量% -50重量%, 例如0. 2重量% -25重量%、0. 5重量% -15重量%或1重量% -8重量%的量的载体改性剂。 In embodiments where the modified support material, the catalyst may comprise 0.1 Total wt% to 50 wt% based on the total weight of the catalyst, e.g. 0.2 wt% to 25 wt%, 0.5 wt% to 15 wt% or an amount of 1 wt% to 8 wt% of the support modifier.

[0043] 合适的载体材料可以包括例如稳定的金属氧化物基载体或陶瓷基载体。 [0043] Suitable support materials may include, for example, metal oxide-based ceramic matrix support or supports. 优选的载体材料包括选自二氧化娃、二氧化娃/氧化错、偏娃酸興(calciummetasilicate)、热解二氧化硅、高纯度二氧化硅、碳、铁氧化物、氧化铝、二氧化硅/氧化铝、二氧化钛、氧化锆和它们的混合物。 Preferred support materials include silica selected baby, baby dioxide / wrong oxidation, partial acid baby Hing (calciummetasilicate), fumed silica, high purity silica, carbon, iron oxide, alumina, silica / alumina, titania, zirconia, and mixtures thereof. 在一个优选的实施方案中,对于该催化剂可以使用酸性载体材料。 In a preferred embodiment, the catalyst may be used for the acidic support material. 酸性载体材料选自铁氧化物、氧化铝、二氧化硅/氧化铝、二氧化钛、氧化锆和它们的混合物。 Acidic support material selected from iron oxide, alumina, silica / alumina, titania, zirconia, and mixtures thereof.

[0044] 在乙醇的生产中,催化剂载体材料可以用载体改性剂进行改性。 [0044] In the production of ethanol, the catalyst support material may be modified with a support modifier. 优选地,用酸性载体改性剂将呈碱性或中性的催化剂载体材料例如二氧化硅、偏硅酸盐、热解二氧化硅、高纯度二氧化硅、碳或它们的混合物进行改性。 Preferably, with an acidic support modifier will show a basic or neutral catalyst support material such as silica, metasilicates, fumed silica, high purity silica, carbon, or a mixture thereof is modified . 酸性载体材料还可以用酸性载体改性剂进行改性。 Acidic support material may also be modified with an acidic support modifier. 在一些实施方案中,酸性载体改性剂通过提高酸位的数量或可及性来调节载体材料。 In some embodiments, the acidic support modifier to adjust the support material by increasing the number of acid sites, or availability. 酸性位促进酯化平衡的动力学速率。 Acidic sites to promote the kinetic rate of the esterification equilibrium. 优选地,载体改性剂是具有低挥发性或无挥发性的酸性改性剂。 Preferably, the support modifier is an acidic modifiers having low volatility or non-volatile. 合适的酸性载体改性剂可以选自:IVB族金属的氧化物、VB族金属的氧化物、VIB族金属的氧化物、VIIB族金属的氧化物、VIIIB族金属的氧化物,铝氧化物和它们的混合物。 Suitable acidic support modifier can be selected from: oxides of Group IVB metal oxides, Group VB metal oxides, Group VIB metal oxides, Group VIIB metal oxides, VIIIB metals, aluminum oxides, and mixtures thereof. 酸性载体改性剂包括选自Ti02、Zr02、Nb205、Ta205、A1203、B203、P205和Sb203的那些。 Acidic support modifiers include those selected from Ti02, Zr02, Nb205, Ta205, A1203, B203, P205, and the Sb203. 优选的酸性载体改性剂包括选自Ti02、Zr02、Nb205、Ta205和A1203的那些。 Preferred acidic support modifiers include those selected from Ti02, Zr02, Nb205, Ta205 and the A1203. 酸性改性剂还可以包括W03、Mo03、Fe203、Cr203、V205、Mn02、CuO、C〇203、Bi203〇 Acidic modifier may further include W03, Mo03, Fe203, Cr203, V205, Mn02, CuO, C〇203, Bi203〇

[0045] 在本发明的一个优选方面中,酸性催化剂包括: [0045] In a preferred aspect of the present invention, the acidic catalyst comprises:

[0046] (i)包含VIII族金属的第一金属, [0046] (i) a first metal comprising a Group VIII metal,

[0047] (ii)包含铜、钥、锡、铬、铁、钴、钒、钨、钯、钼、镧、铈、锰、钌、铼、金和镍的第二金属,以及 [0047] (ii) comprises copper, keyhole, tin, chromium, iron, cobalt, vanadium, tungsten, palladium, molybdenum, lanthanum, cerium, manganese, ruthenium, rhenium, nickel, gold and the second metal, and

[0048] (iii)酸性载体,其包含选自铁氧化物、氧化铝、二氧化硅/氧化铝、二氧化钛、氧化锆和它们的混合物的酸性载体材料。 [0048] (iii) an acidic support, which comprises an acidic support material selected from iron oxide, alumina, silica / alumina, titania, zirconia, and mixtures thereof.

[0049] 酸性载体还可以包含酸性载体改性剂。 [0049] The acidic support may further comprise an acidic support modifier.

[0050] 在本发明的另一个优选方面中,酸性催化剂包括: [0050] In another preferred aspect of the present invention, the acidic catalyst comprises:

[0051] (i)包含VIII族金属的第一金属, [0051] (i) a first metal comprising a Group VIII metal,

[0052] (ii)包含铜、钥、锡、铬、铁、钴、钒、钨、钯、钼、镧、铈、锰、钌、铼、金和镍的第二金属,以及 [0052] (ii) comprises copper, keyhole, tin, chromium, iron, cobalt, vanadium, tungsten, palladium, molybdenum, lanthanum, cerium, manganese, ruthenium, rhenium, nickel, gold and the second metal, and

[0053] (iii)包含载体材料和酸性载体改性剂的酸性载体。 [0053] (iii) an acidic support comprising a support material and an acidic support modifier.

[0054] 优选的二氧化娃载体材料是来自Saint-GobainNorPro的SS61138高表面积(HSA)二氧化娃催化剂载体。 [0054] The preferred support material is silica baby SS61138 from Saint-GobainNorPro high surface area of ​​the (HSA) baby dioxide catalyst support. Saint-GobainNorProSS61138二氧化娃含有约95重量%的高表面积二氧化娃;约250m2/g的表面积;约12nm的中值孔径;通过压萊孔隙测量法(mercury intrusionporosimetry)测量的约1. 0cm3/g的平均孔体积,和约0· 352g/cm3(221b/ft3)的堆积密度。 Saint-GobainNorProSS61138 baby dioxide comprises from about 95 wt% high surface area baby dioxide; from about 250m2 / g surface area; the median pore diameter of about 12nm; Levin pressure measured by porosimetry (mercury intrusionporosimetry) from about 1. 0cm3 / g the average pore volume, and from about 0 · 352g / cm3 (221b / ft3) bulk density.

[0055] 优选的氧化娃/氧化错载体材料是KA-160(SudChemie)二氧化娃球,其具有约5mm的标称直径,约0· 562g/ml的密度,约0· 583gH20/g载体的吸收率,约16〇-175m2/g的表面积和约0. 68ml/g的孔体积。 [0055] Preferred baby oxide / oxide support material is wrong KA-160 (SudChemie) baby dioxide spheres having a nominal diameter of about 5mm, a density of about 0 · 562g / ml, and from about 0 · 583gH20 / g carrier absorption rate, about 16〇-175m2 / g surface area of ​​about 0. 68ml / g, a pore volume.

[0056] 本领域技术人员可意识到,对载体材料进行选择使得催化剂体系在用于生成乙醇的工艺条件下具有合适的活性、选择性和稳健性(robust)。 [0056] Those skilled in the art may be appreciated, support materials are selected such that the catalyst system has a suitable activity, selectivity, and robustness (Robust) at the process conditions for the formation of ethanol.

[0057] 催化剂的金属可以分散遍及整个载体,涂覆在载体的外表面上(蛋壳)或修饰(decorate)在载体表面上。 [0057] The metal catalyst may be dispersed throughout the support, coated on the outer surface of the support (shell) or modified (the decorate) the surface of the support.

[0058] 适用于本发明的催化剂组合物优选通过改性载体的金属浸渍形成,尽管还可以使用其它方法例如化学气相沉积。 [0058] suitable form, in the catalyst compositions of the invention preferably by impregnating the metal-modified support may be used although other methods such as chemical vapor deposition. 这种浸渍技术描述于美国专利No. 7, 608, 744、美国公布No. 2010/0029995和2010/0197985中,通过引用将它们全文并入本文。 This impregnation techniques are described in U.S. Patent No. 7, 608, 744, U.S. Pub. No. 2010/0029995 and 2010/0197985, incorporated by reference in their entirety herein.

[0059] 如本领域技术人员将容易地意识到的,本发明的实施方案可以包括使用固定床反应器或流化床反应器的各种反应器构造。 [0059] As those skilled in the art will readily appreciate, embodiments of the present invention may comprise various reactor configurations using a fixed bed reactor or a fluidized bed reactor. 在本发明的许多实施方案中,可以使用"绝热"反应器;即,具有很少或不需要穿过反应区的内部管道装置(plumbing)来加入或除去热。 In many embodiments of the present invention may be used "adiabatic" reactor; i.e., has little or no means through the inner tubing (plumbing) the reaction zone to add or remove heat. 在其它实施方案中,可以使用径向流动的一个反应器或多个反应器,或者可以使用具有或不具有热交换、冷却或引入另外进料的系列反应器。 In other embodiments, one reactor can be used or a plurality of radial flow reactors, or may be used with or without heat exchange, introduction of additional cooling, or series of reactor feed. 或者,可以使用配设有热传递介质的壳管式反应器。 Alternatively, you can use a shell and tube reactor heat transfer medium. 在许多情形中,反应区可以容纳在单个容器中或之间具有换热器的系列容器中。 In many cases, the reaction zone may be housed in a heat exchanger having a series of vessels in a single vessel or in between.

[0060] 在优选的实施方案中,催化剂在例如管道或导管形状的固定床反应器中使用,其中典型地为蒸气形式的反应物穿过或通过所述催化剂。 [0060] The catalyst used in a fixed bed reactor, for example, the shape of the pipe or tube In a preferred embodiment, which is typically passed over or through the catalyst is in the form of vapor reactants. 可使用其它反应器,例如流化床或沸腾床反应器。 Other reactors may be used, such as fluid or ebullient bed reactors. 在一些情形中,加氢催化剂可以与惰性材料结合使用以调节反应物料流通过催化剂床的压降和反应物化合物与催化剂颗粒的接触时间。 In some cases, the hydrogenation catalyst may drop and a contact time of the reactant compounds with the catalyst particles in order to adjust the reactant stream through the catalyst bed with an inert binding material.

[0061] 可以在液相或气相中进行加氢反应。 [0061] The hydrogenation reaction can be carried out in liquid or gas phase. 优选地,在气相中于如下条件下进行该反应。 Preferably, the reaction is carried out under the following conditions in the gas phase. 反应温度可以为125°C_350°C,例如200°C_325°C、225°C_300°C或250°C_300°C。 The reaction temperature may be 125 ° C_350 ° C, e.g. 200 ° C_325 ° C, 225 ° C_300 ° C or 250 ° C_300 ° C. 压力可以为10KPa-3000KPa(约L5-435psi),例如50KPa-2300KPa或100KPa-1500KPa。 The pressure may range 10KPa-3000KPa (about L5-435psi), e.g. 50KPa-2300KPa or 100KPa-1500KPa. 可以将反应物以大于500hr4,例如大于l〇〇〇hr'大于2500hf1或甚至大于5000hf1的气时空速(GHSV) 给进到反应器。 The reactants may be greater than 500hr4, for example greater than l〇〇〇hr 'is greater than 2500hf1 or even greater than 5000hf1 a gas hourly space velocity (a GHSV) fed to the reactor. 就范围而言,GHSV可以为50hf150,OOOhr'例如500hf130, 000hr' 1000hr-1-10, 000hr-1 或1000hr-1-6500hr' In terms of ranges, GHSV may 50hf150, OOOhr 'e.g. 500hf130, 000hr' 1000hr-1-10, 000hr-1, or 1000hr-1-6500hr '

[0062] 任选在刚刚足以克服穿过催化床的压降的压力下以所选择的GHSV进行加氢,尽管不限制使用较高的压力,但应理解,在高的空速例如5000hrH或6, 500hrH下可能经历通过反应器床的相当大的压降。 [0062] optionally in just sufficient to overcome the pressure drop across the catalytic bed at the selected pressure hydrogenation GHSV, although the use of higher pressures is not limited, it should be appreciated that, at high space velocities, for example, 6 or 5000hrH , under 500hrH may experience considerable pressure drop through the reactor bed.

[0063] 虽然该反应每摩尔乙酸消耗2摩尔氢气从而产生1摩尔乙醇,但进料流中氢气与乙酸的实际摩尔比可以为约100 : 1-1 : 100,例如50 : 1-1 : 50、20 : 1-1 : 2或12 : 1-1 : 1。 [0063] Although the reaction consumes two moles of acid per mole of hydrogen to produce a mole of ethanol, the actual molar ratio of hydrogen to the feed stream of acetic acid may be from about 100: 1 to 1: 100, for example, 50: 1-1: 50 , 20: 1-1: 2 or 12: 1 to 1: 1. 最优选地,氢气与乙酸的摩尔比大于2 : 1,例如大于4 : 1或大于8 : 1。 Most preferably, the molar ratio of hydrogen to acetic acid is greater than 2: 1, eg, greater than 4: 1 or greater than 8: 1.

[0064] 接触或停留时间也可以宽泛地变化,这些取决于如乙酸的量、催化剂、反应器、温度和压力的变量。 [0064] Contact or residence time can also vary widely, depending on such variables as amount of acetic acid, catalyst, reactor, temperature and pressure. 当使用除固定床外的催化剂系统时,典型的接触时间为几分之一秒到大于若干小时,至少对于气相反应,优选的接触时间为〇. 1-100秒,例如〇. 3-80秒或0. 4-30 秒。 When a fixed bed catalyst systems in addition to the typical contact time is greater than a fraction of a second to several hours, at least for vapor phase reactions, the contact time is preferably square. 1-100 seconds, such as square. 3-80 seconds or 0. 4-30 seconds.

[0065] 有关本发明方法所使用的原料、乙酸和氢气可以衍生自任何合适的来源,包括天然气、石油、煤、生物质等。 [0065] The starting material, acetic acid and hydrogen used in the method of the present invention may be derived from any suitable source including natural gas, petroleum, coal, biomass, and the like. 作为实例,可以通过甲醇羰基化、乙醛氧化、乙烯氧化、氧化发酵和厌氧发酵生产乙酸。 As an example, via methanol carbonylation, acetaldehyde oxidation, ethylene oxidation, oxidative fermentation, and anaerobic fermentation of acetic acid. 由于石油和天然气价格波动,或多或少变得昂贵,所以由替代碳源生产乙酸和中间体例如甲醇和一氧化碳的方法已逐渐引起关注。 As petroleum and natural gas prices fluctuate, it becomes more or less expensive, such as methanol and carbon monoxide has been increasing interest from alternate carbon sources producing acetic acid and intermediates. 特别地,当石油与天然气相比相对昂贵时,由衍生自任何可用碳源的合成气体("合成气")生产乙酸可能变得有利。 In particular, when a relatively expensive compared to oil and gas, the carbon source is derived from any of the available synthesis gas ( "syngas") may become advantageous to produce acetic acid. 例如,美国专利No. 6, 232, 352(通过引用将其公开内容并入本文)教导了改造甲醇工厂用以制造乙酸的方法。 For example, U.S. Pat. No. 6, 232, 352 (the disclosure of which is incorporated by reference herein) teaches a method of retrofitting a methanol plant for the manufacture of acetic acid. 通过改造甲醇工厂,对于新的乙酸工厂,与C0产生有关的大量资金费用得到显著降低或在很大程度上消除。 By retrofitting a methanol plant, the new plant acetate, and C0 generate a lot of money costs associated significantly reduced or largely eliminated. 使所有或部分合成气从甲醇合成环路发生转向并供给到分离器单元以回收C0和氢气,然后将它们用于生产乙酸。 All or part of the syngas from the methanol synthesis loop shift occurs and supplied to a separator unit to recover hydrogen and C0, are then used to produce acetic acid. 除乙酸外,这种方法还可以用于制备有关本发明所可利用的氢气。 In addition to acetic acid, this method can also be used for hydrogen which may be prepared using the present invention.

[0066] 适合于乙酸生产的甲醇羰基化方法描述于美国专利No. 7, 208, 624、7, 115, 772、 7, 005, 541、6, 657, 078、6, 627, 770、6, 143, 930、5, 599, 976、5, 144, 068、5, 026, 908、 5, 001,259和4, 994, 608中,通过引用将它们的公开内容并入本文。 [0066] suitable for the carbonylation of methanol to produce acetic acid is described in U.S. Patent No. 7, 208, 624,7, 115, 772, 7, 005, 541,6, 657, 078,6, 627, 770,6, 143, 930,5, 599, 976,5, 144, 068,5, 026, 908, 5, 001,259 and 4, 994, 608, by reference the disclosures of which are incorporated herein. 任选地,可以将乙醇生产与这种甲醇羰基化方法进行整合。 Optionally, the ethanol production can be integrated with such a methanol carbonylation.

[0067] 美国专利No.RE35, 377 (也通过引用将其并入本文)提供了一种通过使含碳材料例如油、煤、天然气和生物质材料转化生产甲醇的方法。 [0067] U.S. Patent No. No.RE35, 377 (also incorporated herein by reference) provides a method of oil, coal, natural gas and biomass materials produced by the carbonaceous material, for example, methanol. 该方法包括使固体和/或液体含碳材料加氢气化以获得工艺气体,用另外的天然气将该工艺气体蒸汽热解以形成合成气。 The method comprises contacting a solid and / or liquid carbonaceous materials to obtain hydrogasification process gas which is steam pyrolized with additional natural gas the process gas to form synthesis gas. 将该合成气转化为可以羰基化为乙酸的甲醇。 The synthesis gas can be converted to a carbonyl group to acetic acid in methanol. 该方法同样产生如上述有关本发明所可使用的氢气。 The method likewise produces hydrogen which may be used above in relation to the present invention. 美国专利No. 5, 821,111以及美国专利No. 6, 685, 754公开了一种将废生物质通过气化转化为合成气的方法,通过引用将它们的公开内容并入本文。 U.S. Patent No. 5, 821,111 and US Patent No. 6, 685, 754 discloses a method for converting waste biomass through gasification into synthesis gas method, by reference the disclosures of which are incorporated herein.

[0068] 在一个任选的实施方案中,给进到加氢反应的乙酸还可以包含其它羧酸和酸酐, 以及乙醛和丙酮。 [0068] In one optional embodiment, the hydrogenation reaction is fed to the acetic acid may also comprise other carboxylic acids and anhydrides, as well as acetaldehyde and acetone. 优选地,合适的乙酸进料流包含一种或多种选自乙酸、乙酸酐、乙醛、乙酸乙酯和它们的混合物的化合物。 Preferably, a suitable acetic acid feed stream comprises one or more compounds selected from acetic acid, acetic anhydride, acetaldehyde, ethyl acetate, and mixtures thereof. 在本发明的方法中还可以将这些其它化合物加氢。 In the method of the present invention, these other compounds may also be hydrogenated. 在一些实施方案中,在丙醇生产中羧酸例如丙酸或其酸酐的存在会是有益的。 In some embodiments, for example in the presence of a carboxylic acid producing propanol propionic acid or its anhydride may be beneficial.

[0069] 或者,可以直接从美国专利No. 6, 657, 078 (通过引用将其全文并入本文)中所描述的一类甲醇羰基化单元的闪蒸器取出蒸气形式的乙酸作为粗产物。 [0069] Alternatively, directly from the U.S. Patent No. 6, 657, 078 (the entirety of which is incorporated herein by reference) flash vessel of a methanol carbonylation unit type as described in the extraction in vapor form acetic acid as a crude product. 例如,可以将粗蒸气产物直接给进到本发明的乙醇合成反应区而不需要冷凝乙酸和轻馏分或者除去水,从而节省总体工艺费用。 For example, the crude vapor product may be fed directly to the alcohol synthesis reaction zone of the present invention without the need for condensing the acetic acid and light ends or removing water, saving overall processing costs.

[0070] 可以使乙酸在反应温度下气化,然后可将气化的乙酸随同未稀释状态或用相对惰性的载气例如氮气、氩气、氦气、二氧化碳等稀释的氢气一起给进。 [0070] The acetic acid may be vaporized at the reaction temperature, and acetic acid may be vaporized along with undiluted state or diluted with a relatively inert carrier gas, such as nitrogen fed together, argon, helium, carbon dioxide diluted hydrogen. 为使反应在气相中运行, 应控制系统中的温度使得其不下降到低于乙酸的露点。 The reaction is run in the gas phase, the temperature control system should be such that it does not fall below the dew point of acetic acid. 在一个实施方案中,可以在特定压力下使乙酸在乙酸沸点气化,然后可以将气化的乙酸进一步加热到反应器入口温度。 In one embodiment, the acetic boiling point at a particular pressure vaporized acetic acid and acetic acid may be vaporized further heated to reactor inlet temperature. 在另一个实施方案中,通过使氢气、循环气、另一种合适的气体或它们的混合物穿过在低于乙酸沸点的温度下的乙酸而使乙酸转变为蒸气状态,从而用乙酸蒸气润湿载气,接着将混合的蒸气一直加热到反应器入口温度。 In another embodiment, the hydrogen gas, recycle gas, another suitable gas or mixtures thereof at a temperature below the boiling point passes through the acetate the acetic acid converted to the vapor state, thereby wetted with acetic acid vapor carrier gas, followed by heating the mixed vapors to the reactor inlet temperature. 优选地,通过使氢气和/或循环气穿过处于或低于125°C 的温度下的乙酸而使乙酸转变为蒸气,接着将合并的气态料流加热到反应器入口温度。 Preferably, the hydrogen and / or recycle gas through the acetic acid at or below at a temperature of 125 ° C into a vapor, then the combined gaseous stream is heated to reactor inlet temperature. [0071] 在各种实施方案中,由加氢方法产生的粗乙醇产物,在任何随后处理例如纯化和分离之前,将典型地包含未反应的乙酸、乙醇和水。 [0071] In various embodiments, the crude ethanol product produced by the hydrogenation process, before any subsequent purification and separation process, will typically contain acetic acid, ethanol and unreacted water, for example. 如本文所使用的,术语"粗乙醇产物"是指包含5-70重量%乙醇和5-35重量%水的任何组合物。 As used herein, the term "crude ethanol product" refers to any composition comprises 5-70 wt% of ethanol and 5-35% by weight of water. 在一些示例性实施方案中,粗乙醇产物包含基于该粗乙醇产物总重量计5重量% -70重量%,例如10重量% -60重量%或15重量% -50重量%的量的乙醇。 In some exemplary embodiments, the crude ethanol product comprising, based on the total weight of the crude product was ethanol 5 wt% to 70 wt%, e.g. 10 wt% or the amount of 15 wt% -60 wt% to 50 wt% of ethanol. 优选地,粗乙醇产物含有至少10重量%乙醇、至少15 重量%乙醇或至少20重量%乙醇。 Preferably, the crude ethanol product containing at least 10% by weight ethanol, at least 15 wt% of ethanol or at least 20% by weight ethanol. 取决于转化率,粗乙醇产物典型地还将包含未反应的乙酸,例如小于90重量%,例如小于80重量%或小于70重量%的量。 Depending on the conversion, the crude ethanol product typically will contain unreacted acetic acid, for example, less than 90 wt%, such as less than 80 wt%, or less than 70% by weight. 就范围而言,未反应的乙酸优选为0-90重量%,例如5-80重量%、15-70重量%、20-70重量%或25-65重量%。 In terms of ranges, the unreacted acetic acid is preferably 0-90 wt%, for example 5-80 wt%, 15-70 wt%, 20-70 wt% or 25-65 wt%. 因为在反应过程中形成水,水将通常例如以5-35重量%,如10-30重量%或10-26重量% 的量存在于粗乙醇产物中。 As for example in the generally 5-35 wt%, such an amount of 10-30 wt% or 10-26 wt% of ethanol present in the crude product to form water during the reaction. 在乙酸加氢期间或通过副反应也可以产生乙酸乙酯,并且其可以例如以0-20重量%,如0-15重量%、1-12重量%或3-10重量%的量存在。 Or ethyl acetate may also be produced by side reactions during the hydrogenation of acetic acid, and which may be 0-20 wt%, such as 0-15 wt%, an amount of 1 to 12 wt.% Or 3-10 wt.% Is present, for example. 通过副反应也可以产生乙醛并且其可以例如以0-10重量%,如0-3重量%、0. 1-3重量%或0. 2-2重量%的量存在。 Acetaldehyde may also be produced by a side reaction and which may be 0-10 wt%, such as%, 0 1-3 wt%, or 0. 2-2% by weight, for example 0-3 wt. 其它组分例如酯、醚、醛、酮、烷烃和二氧化碳,如果可检测到,可以总共以小于10重量%,例如小于6重量%或小于4重量%的量存在。 Other components such as esters, ethers, aldehydes, ketones, alkanes, and carbon dioxide, if detectable, may be present in amounts less than 10 wt%, for example less than 6 wt% or less than 4% by weight. 就范围而言,其它组分可以按0. 1-10重量%,例如0. 1-6重量%或0. 1-4重量%的量存在。 In terms of ranges, other components may be 0.5 to 10 wt% by, for example, an amount of 0.5 wt% or 0. 1-6 1-4 weight percent. 表1中提供了粗乙醇组成范围的示例性实施方案。 Table 1 provides an exemplary embodiment of the crude ethanol composition range.

[0072] [0072]

Figure CN102307657BD00121

[0073] 图1显示了根据本发明的一个实施方案适合于乙酸加氢和从粗反应混合物分离乙醇的加氢系统100。 [0073] FIG 1 depicts a hydroprocessing system according to one embodiment of the present invention is suitable for the hydrogenation of acetic acid and separation of ethanol from the crude reaction mixture of 100. 系统100包含反应区101和蒸馏区102。 The system 100 comprises a reaction zone and a distillation zone 101 102. 反应区101包含反应器103、 氢气进料管线104和乙酸进料管线105。 The reaction zone 101 comprises a reactor 103, hydrogen feed line 104 and acetic acid feed line 105. 蒸馏区102包含闪蒸器106、第一塔107、第二塔108和第三塔109。 Distillation zone 102 comprises flasher 106, first column 107, second column 108 and a third column 109. 分别通过管线104和105将氢气和乙酸给进到蒸发器110以在导向到反应器103的管线111中产生蒸气进料流。 Respectively, to produce a vapor feed stream in line 111 directed to reactor 103 through line 104 and acetic acid and hydrogen 105 fed to the evaporator 110. 在一个实施方案中,管线104和105可以合并且例如以一种含有氢气和乙酸的料流共同给进到蒸发器110。 In one embodiment, lines 104 and 105 may be combined and, for example, in a stream containing acetic acid and hydrogen co-fed to vaporizer 110. 管线111中蒸气进料流的温度优选为l〇〇°C-350°C,例如120°C-310°C或150°C-300°C。 Vapor in line 111 feed stream temperature is preferably l〇〇 ° C-350 ° C, e.g. 120 ° C-310 ° C or 150 ° C-300 ° C. 如图1中所示,将没有气化的任何进料从蒸发器110移出,并可以将其再循环到其中。 Any feed shown in Figure 1, is not vaporized from the evaporator 110 is removed and may be recycled thereto. 此外,虽然图1显示了管线111导向反应器103的顶部,但是管线111可以导向反应器103的侧部、上部或底部。 Furthermore, while Figure 1 shows the reactor top guide 111 in line 103, line 111 can be directed to the side portion of the reactor 103, top or bottom. 在下面图2A 和2B中描述了反应区101的其它修改和另外组成部分。 In the following Figures 2A and 2B are described in further modifications and additional components to the reaction zone 101.

[0074] 反应器103含有用于使羧酸,优选乙酸加氢的催化剂。 [0074] Reactor 103 contains a carboxylic acid, preferably acetic acid to the hydrogenation catalyst. 在一个实施方案中,可以使用一个或多个保护床(未示出)保护催化剂免于遭受进料或返回/再循环料流中所含的有毒物质或不期望的杂质。 In one embodiment, using one or more guard beds (not shown) protect the catalyst from the feed or return toxic or undesirable impurities / contained in the recycle stream. 这类保护床可以在蒸气料流或液体料流中使用。 Such guard beds may be used in a vapor stream or a liquid stream. 合适的保护床材料在本领域是已知的并且包括例如碳、二氧化硅、氧化铝、陶瓷或树脂。 Suitable guard bed materials are known in the art and include, for example, carbon, silica, alumina, ceramic, or resin. 在一方面,使保护床介质官能化以捕集特殊物质例如硫或卤素。 In one aspect, the guard bed media is functionalized to trap particular species such as sulfur or halogens. 在加氢过程期间,通过管线112将粗乙醇产品流优选连续地从反应器103取出。 During the hydrogenation process, the crude ethanol product stream 112 preferably is continuously withdrawn from the reactor through line 103. 可以将粗乙醇产品流冷凝并且给进到闪蒸器106,这进而提供了蒸气流和液体料流。 The crude alcohol product stream may be condensed and fed to flasher 106, which provides a vapor stream and a liquid stream. 在一个实施方案中,闪蒸器106优选在50°C-500°C,例如70°C_400°C或100°C_350°C的温度下操作。 In one embodiment, the flasher 106 is preferably 50 ° C-500 ° C, for example, operating at a temperature of 70 ° C_400 ° C or of 100 ° C_350 ° C. 在一个实施方案中,闪蒸器106的压力优选为50KPa-2000KPa,例如75KPa-1500KPa或100-1000KPa。 In one embodiment, the flasher 106 is preferably a pressure 50KPa-2000KPa, e.g. 75KPa-1500KPa or 100-1000KPa. 在一个优选的实施方案中,闪蒸器的温度和压力类似于反应器103的温度和压力。 In a preferred embodiment, the temperature and pressure in the flasher and the pressure of the reactor similar to the temperature of 103.

[0075] 离开闪蒸器106的蒸气料流可以包含氢气和烃,可以将其进行清洗和/或通过管线113返回到反应区101。 [0075] The vapor stream exiting the flasher 106 may comprise hydrogen and hydrocarbons, which may be purged and / or returned to reaction zone 101 via line 113. 如图1中所示,蒸气料流的返回部分穿过压缩机114并且与氢气进料合并,共同给进到蒸发器110。 As shown in FIG. 1, a vapor return stream passes through the compressor section 114 and combined with the hydrogen feed, co-fed to vaporizer 110.

[0076] 将来自闪蒸器106的液体取出并且作为进料组合物通过管线115泵送到第一塔1〇7(也称作酸分离塔)的侧部。 [0076] The liquid 106 is withdrawn from the flasher and a feed composition through the side portion 115 is pumped to the first column line 1〇7 (also referred to as the acid separation column). 管线115的内容物典型地将基本上类似于直接从反应器获得的产物,并且实际上还可以称作粗乙醇产物。 The contents of line 115 will typically be substantially similar product is obtained directly from the reactor, and indeed may also be referred to as a crude ethanol product. 然而,管线115中的进料组合物优选基本上不含氢气、二氧化碳、甲烷或乙烷,它们通过闪蒸器106被移出。 However, line 115 feed composition is preferably substantially free of hydrogen, carbon dioxide, methane or ethane, which are removed by the flasher 106. 表2中提供了管线115中液体的示例性组分。 Table 2 provides exemplary components of the liquid in line 115. 应理解的是,液体管线115可以含有其它组分(未列出)例如进料中的组分。 It should be understood that the liquid line 115 may contain other components (not shown), for example, components in the feed.

[0077] [0077]

Figure CN102307657BD00131

[0078] 在整个本申请的表中小于(<)所示的量是优选不存在并且如果存在则可以按痕量或以大于〇. 0001重量%的量存在。 The amount of [0078] less than the entire table shown in the present application (<) is preferably absent and, if present, may be presence of an amount of 0001% by weight greater than trace or square.

[0079] 表2中的"其它酯"可以包括但不限于丙酸乙酯、乙酸甲酯、乙酸异丙酯、乙酸正丙酯、乙酸正丁酯或它们的混合物。 [0079] Table 2 "other esters" may include but are not limited to, ethyl propionate, methyl acetate, isopropyl acetate, n-propyl, n-butyl acetate or mixtures thereof. 表2中的"其它醚"可以包括但不限于二乙基醚、甲基乙基醚、异丁基乙基醚或它们的混合物。 Table 2 "other ethers" may include but are not limited to, diethyl ether, methyl ethyl ether, isobutyl ethyl ether, or mixtures thereof. 表2中的"其它醇"可以包括但不限于甲醇、异丙醇、 正丙醇、正丁醇或它们的混合物。 Table 2 "Other alcohol" may include but is not limited to, methanol, isopropanol, n-propanol, n-butanol or mixtures thereof. 在一个实施方案中,进料组合物例如管线115可以包含以0. 001-0. 1重量%、0. 001-0. 05重量%或0. 001-0. 03重量%的量的丙醇如异丙醇和/或正丙醇。 In one embodiment, the feed composition may comprise, for example, in line 115 0. 001-0. 1% by weight, 0. 001-0. 001-0 0. 05 wt% or 03 wt% of the amount of propanol such as isopropanol and / or n-propanol. 应理解,这些其它组分可以载带在本文所描述的任何馏出物流或残余物流中,并且除非另外说明,本文将不作进一步描述。 It should be understood that other components may be in any of the distillate tape described herein carrier or residue stream, and unless specified otherwise, will not be further described herein.

[0080] 在一个实施方案中,乙酸的转化率可以大于95%,并且管线115中的粗乙醇产物可以含有小于5重量%乙酸。 [0080] In one embodiment, conversion of acetic acid may be greater than 95%, and a crude ethanol product in line 115 can contain less than 5 wt% acetic acid. 在这种实施方案中,可以略过酸分离塔107并且可以将管线115直接引入到第二塔108 (本文还称作轻馏分塔)。 In such embodiments, it may be skipped and the acid separation column 107 in line 115 may be introduced directly into the second column 108 (also referred to herein light ends column).

[0081] 在图1A中所示的实施方案中,将管线115引入第一塔107的下部,例如下半部或下三分之一。 [0081] In the embodiment shown in FIG. 1A, a lower portion of the first column in line 115 is introduced 107, for example, lower half or lower third. 在第一塔107中,将未反应的乙酸、部分水和其它重质组分(如果存在)从管线115中的组合物移出并优选连续地作为残余物取出。 The first column 107, unreacted acetic acid, water, and other portions of heavy components (if present) is removed from the line 115 and the composition preferably continuously removed as the residue. 可以使一些或全部残余物通过管线116返回和/或再循环回到反应区101。 Some or all of the residue was returned through line 116 and / or recycled back to the reaction zone 101. 第一塔107还形成了塔顶馏出物,将其在管线117 中取出,并且可以将其例如以10 : 1-1 : 10,如3 : 1-1 : 3或1 : 2-2 : 1的比率冷凝和回流。 First column 107 also forms an overhead distillate, which is removed in line 117, and may be for example 10: 1 to 1: 10, such as 3: 1 to 1: 3 or 1: 2-2: condensing and reflux ratio of 1.

[0082] 塔107、108或109中的任何一个可以包含能够进行分离和/或纯化的任何蒸馏塔。 [0082] any one of 107, 108 or 109 may comprise a column capable of separation and / or purification of any distillation column. 所述塔优选包含具有1-150个塔板,例如10-100个塔板、20-95个塔板或30-75个塔板的板式塔。 The column preferably contains trays having from 1 to 150, for example from 10 to 100 trays, trays 20-95 30-75 trays or tray column. 塔板可以是筛板、固定浮阀塔板、移动浮阀塔板或本领域已知的任何其它合适的设计。 Sieve trays may be, any other suitable design, fixed valve trays, or valve trays moves known in the art. 在其它实施方案中,可以使用填料塔。 In other embodiments, a packed column may be used. 对于填料塔,可以使用规整填料或无规填料。 For packed columns, structured packing or random packing. 可以将所述塔或填料按一种连续塔进行排列或者可以将它们按两个或更多个塔进行排列使得来自第一段的蒸气进入第二段并同时使来自第二段的液体进入第一段,等等。 The trays or packing may be arranged in one continuous column or they can be arranged such that two or more vapor from the first column into the second section while the liquid from the second section into the first for some, and so on.

[0083] 可以与各个蒸馏塔一起使用的有关冷凝器和液体分离容器可以具有任何常规设计并且在图1中加以简化。 [0083] For a condenser and a liquid may be used with each of the distillation column separation vessel may be of any conventional design and are simplified in FIG. 如图1中所示,可以将热供给到各个塔的底部或者通过换热器或再沸器供给到循环塔底料流。 As shown in FIG. 1, heat may be supplied to the base of each column or to a circulating bottom stream through a heat exchanger or reboiler. 在一些实施方案中,还可以使用其它类型的再沸器,例如内部再沸器。 In some embodiments, also other types of reboilers, such as internal reboiler. 提供给再沸器的热可以得自于与所述再沸器整合的过程期间所产生的任何热或者得自于外部来源例如另一种产生热的化学方法或锅炉。 Any heat generated during the process heat supplied to the reboiler may be derived from the integration of the reboiler or obtained from an external source such as another chemical process or boiler to produce heat. 虽然在图1中显示了一个反应器和一个闪蒸器,但是在本发明的实施方案中可以使用附加的反应器、闪蒸器、冷凝器、加热元件和其它部件。 Although one reactor and a flasher in FIG. 1, an additional reactor may be used in embodiments of the present invention, the flashers, condensers, heating elements, and other components. 如本领域技术人员所可认识到的,还可以将通常用于进行化学方法的各种冷凝器、泵、压缩机、再沸器、转鼓、阀、连接器、分离容器等进行组合并且用于本发明的方法中。 As those skilled in the art may be appreciated, it may also be commonly used for a variety of chemical methods condenser, a pump, a compressor, reboiler, drum, valves, connectors, separation vessel and the like in combination with in the process of the present invention.

[0084] 任何塔中所用的温度和压力可以变动。 [0084] any temperature and pressure used in the column may vary. 作为实际情况,在这些区域中可通常使用10KPa-3000KPa的压力,尽管在一些实施方案中可以使用低于大气压的压力以及超过大气压的压力。 As a practical matter in these areas may be generally used 10KPa-3000KPa pressure, although subatmospheric pressure may be used in some embodiments and in excess of atmospheric pressure. 各个区域内的温度将通常在作为馏出物被除去的组合物的沸点和作为残余物被除去的组合物的沸点之间的范围内。 The temperature in the various zones will normally as a distillate in a range between the boiling points are removed as a residue of the composition was removed compositions. 本领域技术人员将认识到,运行的蒸馏塔中给定位置的温度取决于在该位置处的物料组成和塔的压力。 Those skilled in the art will recognize that the distillation column operating temperature at a given location depends on the pressure in the material at that location and the composition of the column. 此外,进料速率可以取决于生产工艺规模而变化,如果进行描述,则可以一般是指按照进料重量比。 In addition, feed rates may vary depending on the production scale process, if described, it may generally refers to a weight ratio in terms of feed.

[0085] 当塔107在标准大气压下操作时,在管线116中从塔107离开的残余物的温度优选为95°C_120°C,例如105°C_117°C或110°C_115°C。 [0085] When the column 107 is operated at normal atmospheric pressure, the temperature in the column 107 in line 116 from exiting the residue is preferably 95 ° C_120 ° C, e.g. 105 ° C_117 ° C or 110 ° C_115 ° C. 在管线117中从塔107离开的馏出物的温度优选为70°C-1KTC,例如75°C-95°C或80°C-90°C。 In column 107 in line 117 exiting from the distillate temperature is preferably 70 ° C-1KTC, e.g. 75 ° C-95 ° C or 80 ° C-90 ° C. 在其它实施方案中,第一塔107 的压力可以为0·lKPa-510KPa,例如lKPa-475KPa或lKPa-375KPa。 In other embodiments, the pressure of first column 107 may be 0 · lKPa-510KPa, e.g. lKPa-475KPa or lKPa-375KPa.

[0086] 下表3中提供了第一塔107的馏出物和残余物组合物的示例性组分。 Providing Exemplary components distillate and residue compositions for first column 107 3 [0086] in the following table. 还应该理解的是,所述馏出物和残余物还可以含有未列出的其它组分,例如进料中的组分。 It should also be appreciated that other components of the distillate and residue not listed may also contain, for example, components in the feed. 为了方便, 第一塔的馏出物和残余物也可以称作"第一馏出物"或"第一残余物"。 For convenience, the first column distillate and residue may also be referred to as "a first distillate" or "first residue." 其它塔的馏出物或残余物也可以用类似的数字修饰语(第二、第三等)被提及以便将它们彼此区分开,但是这类修饰语不应该解释为要求任何特殊的分离顺序。 Other column distillate or residue may be similar numeric modifiers (second, third, etc.) in order to distinguish them from one another, but such modifiers should not be construed as requiring any particular separation order .

[0087] [0087]

Figure CN102307657BD00151

[0088] 如表3中所示,虽然不受理论束缚,出人意料和意想不到地发现,当在引入到酸分离塔(第一塔107)的进料中检测出任意量的乙缩醛时,乙缩醛似乎在该塔中分解使得在馏出物和/或残余物中存在较少或甚至没有可检测的量。 [0088] As shown in the table, while not being bound by theory, surprisingly and unexpectedly been found that 3, when introduced into the acid separation in any amount of feed detected column (first column 107) when the acetal, acetal decomposition appears in the column such that there is less amount of the distillate and / or residue or even no detectable.

[0089] 取决于反应条件,在管线112中离开反应器103的粗乙醇产物可以包含乙醇、乙酸(未转化)、乙酸乙酯和水。 [0089] Depending on the reaction conditions, exiting reactor 112 in line 103 may crude ethanol product comprising ethanol, acetic acid (unconverted), ethyl acetate and water. 在离开反应器103之后,粗乙醇产物在加入到闪蒸器106和/ 或第一塔107之前其中所包含的组分之间可以发生非催化的平衡反应。 After leaving the reactor 103, the crude product was added to ethanol uncatalyzed reaction can occur between the equilibrium and / or components 107 contained therein prior to the first flasher column 106. 正如以下所示(反应2),该平衡反应趋向于驱动粗乙醇产物达到乙醇/乙酸和乙酸乙酯/水之间的平衡。 As shown below (Scheme 2), which tends to drive the equilibrium reaction crude ethanol product equilibrium between ethanol / acetic acid and ethyl acetate / water.

[0090] EtOH+HOAcηEtOAc+H20反应2 [0090] EtOH + HOAcηEtOAc + H20 Reaction 2

[0091] 在该情形中,粗乙醇产物在导向蒸馏区102之前暂时贮存在例如储罐中,所以可以遭遇延长的停留时间。 [0091] In this case, the crude ethanol product distillation zone in the guide, for example, temporarily stored in the accumulator 102 before, it is possible to encounter a prolonged residence time. 通常,反应区101和蒸馏区102之间的停留时间越长,乙酸乙酯形成得越多。 Typically, the reaction zone 101 and distillation zone between the longer the residence time 102, the more the formation of ethyl acetate. 例如,当反应区101和蒸馏区102之间的停留时间大于5天时,会以乙醇的损失形成显著较多的乙酸乙酯。 For example, when the residence time between reaction zone and a distillation zone 101 102 greater than 5 days, will form significantly more loss of ethanol in ethyl acetate. 因此,通常优选反应区101和蒸馏区102之间较短的停留时间以使形成的乙醇的量最大化。 Thus, the shorter the reaction zone preferably is generally between 102 and 101 distillation zone residence time so that the amount of ethanol formed maximized. 在一个实施方案中,储罐(未示出)包括在反应区101和蒸馏区102之间用于临时贮存来自管线115的液体组分持续至多5天,例如至多1天或至多1小时。 In one embodiment, a holding tank (not shown) comprised between the reaction zone and a distillation zone 101 for temporarily storing a liquid component 102 from line 115 of up to 5 days, for example up to 1 day, or up to 1 hour. 在优选的实施方案中,不包括罐并且将冷凝的液体直接给进到第一蒸馏塔107。 In a preferred embodiment, the tank is not included and the condensed liquids are fed directly to the first distillation column 107. 此夕卜,非催化反应进行的速率可以随着例如在管线115中的粗乙醇产物的温度提高而提高。 Bu this evening, the non-catalyzed reaction rate may increase as the temperature of the crude ethanol product in line 115 is increased to improve. 在超过30°C,例如超过40°C或超过50°C的温度下这些反应速率可特别产生问题。 More than 30 ° C, for example, exceeds 40 ° C, or the reaction rates may be particularly problematic in excess of 50 ° C temperature. 因此,在一个实施方案中,使管线115中或可选储罐中的液体组分的温度维持处于小于40°C,例如小于30°C或小于20°C的温度。 Thus, in one embodiment, line 115, or alternatively the liquid component in the tank is maintained at a temperature of less than 40 ° C, for example less than 30 ° C or less than a temperature of 20 ° C. 可以使用一种或多种冷却装置来降低管线115中液体的温度。 Using one or more cooling devices to reduce the temperature of the liquid in line 115.

[0092] 如上所讨论的,储罐(未示出)可以包括在反应区101和蒸馏区102之间用于任选在约21°C的温度下临时贮存来自管线115的液体组分例如1-24小时,并且分别对应于0. 01重量% -1. 0重量%的乙酸乙酯形成。 [0092] As discussed above, the tank (not shown) may be included in the reaction zone between 101 and 102 for the optional distillation zone at a temperature of about 21 ° C for temporarily storing the liquid component from line 115, for example, 1 24 hours, and correspond to 0.01 wt.% to 1 0 wt% ethyl acetate is formed. 此外,非催化反应进行的速率可以随着粗乙醇产物的温度提高而提高。 In addition, the non-catalyzed reaction rate as the temperature of the crude ethanol product can be increased and improved. 例如,随着管线115中的粗乙醇产物温度从4°C提高到21°C,形成乙酸乙酯的速率可以从约〇. 01重量% /小时提高到约〇. 005重量% /小时。 For example, as the temperature of the crude ethanol product in line 115 is increased from 4 ° C to 21 ° C, the rate of formation of ethyl acetate may be 01% by weight increased from about square / square hour to about 005 wt% / hr. 因此,在一个实施方案中,使管线115中或可选储罐中的液体组分温度维持处于温度小于21°C,例如小于4°C或小于-10°C。 Thus, in one embodiment, the temperature of the liquid component in line 115 or in the optional holding tank is maintained at a temperature less than 21 ° C, for example less than 4 ° C or less than -10 ° C.

[0093] 此外,现已发现,上述平衡反应还可以促进在第一塔107的顶部区域中形成乙醇。 [0093] In addition, it has been found that the equilibrium reaction may also favor ethanol formation in the top region of the first column 107.

[0094] 如图1中所示,任选将塔107的馏出物例如塔顶料流进行冷凝并优选以1 : 5-10 : 1的回流比进行回流。 As shown in FIG. 1 [0094], optionally in the column 107, for example, overhead distillate stream is condensed and preferably 1: 5-10: 1 reflux ratio of reflux. 管线117中的馏出物优选包含乙醇、乙酸乙酯和水以及其它杂质,其由于二元和三元共沸物的形成而可能难于分离。 The distillate in line 117 preferably comprises ethanol, ethyl acetate and water, and other impurities, which is due to the formation of binary and ternary azeotropes may be difficult to separate.

[0095] 将管线117中的第一馏出物引入到第二塔108 (也称作"轻馏分塔"),优选在塔108 的中间部分例如中间二分之一或中间三分之一引入。 [0095] The first distillate in line 117 is introduced to the second column 108 (also referred to as "light ends column"), such as an intermediate is preferably one-half or at the intermediate portion of the third column 108 is introduced . 作为一个实例,当以没有水抽提的塔中使用25个塔板的塔时,将管线117在塔板17处引入。 As one example, when a column without water extraction using a 25 tray column, in line 117 is introduced at tray 17. 在一个实施方案中,第二塔108可以是提取蒸馏塔。 In one embodiment, the second column 108 may be an extractive distillation column. 在这种实施方案中,可以将提取剂例如水加入到第二塔108。 In this embodiment, for example, water extraction agent may be added to the second column 108. 如果提取剂包含水,则其可以从外部来源获得或者从来自一个或多个其它塔的内部返回/再循环管线例如通过任选管线12Γ获得。 If the extraction agent comprises water, it may be obtained from an external source or return / recycle line from the inside from one or more other columns, for example, obtained by optionally 12Γ line.

[0096] 第二塔108可以是板式塔或填料塔。 [0096] The second column 108 may be a tray column or packed column. 在一个实施方案中,第二塔108是具有5-70 个塔板,例如15-50个塔板或20-45个塔板的板式塔。 In one embodiment, the second column 108 trays having 5-70, for example 15-50 or 20-45 trays trays tray column.

[0097] 虽然第二塔108的温度和压力可以变动,但当在大气压下在管线118中从第二塔108离开的第二残余物的温度优选为60°C-90°C,例如70°C-90°C或80°C-90°C。 [0097] Although the temperature and pressure of second column 108 may vary, but at atmospheric pressure in line 118 exiting column 108 from the second residue of the second temperature is preferably 60 ° C-90 ° C, 70 ° e.g. C-90 ° C or 80 ° C-90 ° C. 在管线120中从第二塔108离开的第二馏出物的温度优选为50°C-90°C,例如60°C-80°C或60°C-70°C。 In line 120 from second temperature is preferably 108 to leave the second column distillate is 50 ° C-90 ° C, e.g. 60 ° C-80 ° C or 60 ° C-70 ° C. 塔108可以在大气压下操作。 Column 108 may be operated at atmospheric pressure. 在其它实施方案中,第二塔108的压力可以为0.lKPa-510KPa,例如lKPa-475KPa或lKPa-375KPa。 In other embodiments, the pressure of second column 108 may 0.lKPa-510KPa, e.g. lKPa-475KPa or lKPa-375KPa. 下表4 中提供了第二塔108 的馏出物和残余物组合物的示例性组分。 Table 4 below provides exemplary components of the distillate and residue compositions for second column 108. 应理解的是,所述馏出物和残余物还可以含有未列出的其它组分,例如进料中的组分。 It should be understood that other components of the distillate and residue not listed may also contain, for example, components in the feed.

[0098] [0098]

Figure CN102307657BD00171

[0099] 第二残余物中的乙醇与第二馏出物中的乙醇的重量比优选为至少3 : 1,例如至少6 : 1、至少8 : 1、至少10 : 1或至少15 : 1。 [0099] weight of the second residue to a second ethanol distillate ethanol is preferably at least 3: 1, such as at least 6: 1, at least 8: 1, at least 10: 1 or at least 15: 1. 第二残余物中的乙酸乙酯与第二馏出物中的乙酸乙酯的重量比优选为小于0.4 : 1,例如小于0.2 : 1或小于0.1 : 1。 By weight of ethyl acetate in the second residue in ethyl acetate in the second distillate is preferably less than 0.4: 1, such as less than 0.2: 1 or less than 0.1: 1. 在使用用水作为提取剂的提取塔作为第二塔108的实施方案中,第二残余物中的乙酸乙酯与第二馏出物中的乙酸乙酯的重量比接近零。 Using water as an extraction agent in the extraction column as the column of the second embodiment 108, the second residue weight of ethyl acetate to ethyl acetate in the second distillate ratio close to zero.

[0100] 如所示,将来自第二塔108底部的第二残余物(其包含乙醇和水)通过管线118 给进到第三塔109 (也称作"产物塔")。 [0100] As shown, the second residue from the bottom of the second column 108 (containing ethanol and water) fed through line 118 to the third column 109 (also referred to as "product column"). 更优选地,将管线118中的第二残余物引入第三塔109的下部,例如下半部或下三分之一。 More preferably, the second residue in line 118 was introduced in the lower third of the column 109, for example, lower half or lower third. 第三塔109以管线119中的馏出物回收乙醇(优选除共沸水含量外基本上是纯的)。 The third column 109 in line 119 to distillate recovering ethanol (a total water content, preferably in addition to substantially pure). 第三塔109的馏出物优选按图1A中所示,例如以1 : 10-10 : 1如1 : 3-3 : 1或1 : 2-2 : 1的回流比进行回流。 Third column distillate 109 is preferably press shown in FIGS. 1A, for example, 1: 10-10: 1 reflux ratio of reflux: 1, such as 1: 3-3: 1 or 1: 2-2. 管线121中的第三残余物(优选主要包含水)优选从系统100移出或者可以部分返回到系统100的任何部分。 The third line 121 residues (preferably mainly comprising water) is preferably removed from the system 100 or may be partially returned to any portion of the system 100. 第三塔109优选为如上所述的板式塔并且优选在大气压下操作。 The third column 109 is preferably a tray column as described above and is preferably operated at atmospheric pressure. 在管线119中从第三塔109 离开的第三馏出物的温度优选为60°C-110°C,例如70°C-KKTC或75°C-95°C。 The temperature in the line 119 leaving from the third column a third distillate 109 is preferably 60 ° C-110 ° C, e.g. 70 ° C-KKTC or 75 ° C-95 ° C. 当该塔在大气压下操作时,离开第三塔109的第三残余物的温度优选为70°C-115°C,例如80°C-110°C 或85°C_105°C。 When the column is operated at atmospheric pressure, leaving the residue of the third temperature of the third column 109 is preferably 70 ° C-115 ° C, e.g. 80 ° C-110 ° C or 85 ° C_105 ° C. 下表5中提供了第三塔109的馏出物和残余物组合物的示例性组分。 Table 5 below provides exemplary components and residue compositions for third column distillate 109. 应理解的是,馏出物和残余物还可以含有未列出的其它组分,例如进料中的组分。 It should be understood that the distillate and residue may also contain other components, not listed, for example, components in the feed.

[0101] [0101]

Figure CN102307657BD00181

[0102] 蒸馏过程中从进料或粗反应产物载带的任何化合物通常以基于第三馏出物组合物的总重量计小于0.1重量%,例如小于0.05重量%或小于0.02重量%的量保留在第三馏出物中。 [0102] Any compound during distillation feed or from the carrier tape crude reaction product is generally present in a third distillate composition with a total weight of less than 0.1 wt%, such as less than 0.05 wt.% Or less than 0.02 wt% retention in a third distillate. 在一个实施方案中,一种或多种侧线料流可以从系统100的塔107、108和/或109中的任一个中除去杂质。 In one embodiment, the one or more side streams may remove impurities from / to any one of the 109 column system 107, 108 and 100 or. 优选使用至少一个侧线料流从第三塔109除去杂质。 Preferably stream 109 to remove impurities from the third column to use at least one side. 可以将杂质进行清洗和/或保留在系统100内。 Impurities may be purged and / or retained within the system 100.

[0103] 可以使用一种或多种附加分离系统,例如蒸馏塔(如精加工塔)或分子筛进一步纯化管线119中的第三馏出物以形成无水乙醇产品流,即"成品无水乙醇"。 [0103] using one or more additional separation system such as distillation column (e.g., finishing column) or third distillate was further purified effluent in line 119 to form an anhydrous ethanol product stream, i.e. "finished ethanol . "

[0104] 返回到第二塔108,管线120中的馏出物优选按图1中所示,例如以1 : 10-10 : 1, 如1 : 5-5 : 1或1 : 3-3 : 1的回流比进行回流。 [0104] returned to, as shown in the second column 108 in line 120 preferably distillate by FIG. 1, for example 1: 10-10: 1, such as 1: 5-5: 1 or 1: 3-3: 1 reflux ratio of reflux. 在一个实施方案中,可以通过管线120 将来自第二塔108的全部或部分馏出物再循环到反应区101。 In one embodiment, it can be from the second column 120 in line 108 of all or part of the distillate is recycled to the reaction zone 101 through. 如图1中所示,全部或部分馏出物可以如管线120所示再循环到反应器103,并且可以与乙酸进料管线105 -起共同给进。 As shown in FIG. 1, all or a portion of the distillate may be recycled as shown in line 120 to reactor 103, and may be the acetic acid feed line 105-- from co-fed. 在一个实施方案中,管线120中的乙酸乙酯由于包含酸性载体的催化剂的存在而没有积累在反应区101和/或蒸馏区102中。 In one embodiment, the line 120 due to the presence of ethyl acetate containing an acidic support catalyst without accumulation and / or distillation zone 102 in reaction zone 101. 由于平衡反应动力学的提高,本发明的实施方案还能够处理进料和/或再循环料流中的乙酸乙酯。 Due to increased equilibrium reaction kinetics, embodiments of the present invention is also capable of processing the feed and / or recycle stream ethyl acetate. 因此,由于提高的动力学,可以使管线120中的再循环乙酸乙酯转化为乙醇,或者产生的乙酸乙酯可以等于转化的乙酸乙酯,因此将存在相对快速获得的一定稳态并且再循环的乙酸乙酯的浓度将保持恒定;而不积累在循环回路中。 Thus, due to the improved kinetics, can be recycled in line 120 is converted to ethanol in ethyl acetate, ethyl acetate or ethyl acetate may be equal to the generated conversion, thus there will be obtained a certain steady-state relatively quickly and recycled concentration will remain constant with ethyl acetate; not accumulate in the recycle loop. 可以通过管线122将来自第二塔108的部分馏出物进行清洗。 It may be part 108 from the second column distillate through line 122 for cleaning. 任选地,如共同未决的美国申请No. 12/852, 269中所描述(通过引用将其全文并入本文),管线120中的第二馏出物在返回到反应区之前可以使用一种或多种另外的塔(未示出)进一步纯化以除去杂质例如乙醛。 Optionally, as described in co-pending U.S. Application No. 12/852, 269 as described (incorporated by reference in its entirety herein), the second distillate in line 120 may be used prior to a return to the reaction zone one or more additional columns (not shown) is further purified to remove impurities such as acetaldehyde.

[0105] 图2A和2B分别显示了改进的反应区130和140。 [0105] Figures 2A and 2B show an improved reaction zone 130 and 140. 如上文所讨论的,本发明的一些实施方案可以使用多个反应器。 As discussed above, some embodiments of the present invention may use a plurality of reactors. 在图2A的反应区130中,将蒸气进料流111给进到第一反应器131。 In the reaction zone 130 of FIG. 2A, the vapor feed stream 111 fed to the first reactor 131. 将反应器流出物133给进到第二反应器132。 The reactor effluent 133 is fed to the second reactor 132. 优选地,反应器流出物133包含乙醇和未反应的乙酸并且可以具有如上表1所述的组成。 Preferably, the reactor effluent 133 comprising ethanol and unreacted acetic acid and may have a composition according to Table 1 above. 任选地,可以将新鲜反应物(未示出)给进到第二反应器132。 Optionally, fresh reactants (not shown) is fed to the second reactor 132. 将第二反应器的粗乙醇产物134给进到闪蒸器106。 The crude ethanol product of the second reactor 134 is fed to flasher 106. 出于说明目的,图2A显示了2个反应器。 For illustrative purposes, Figure 2A shows two reactors. 然而,在其它实施方案中,可以具有多于2个反应器,例如多于3个或多于4个。 However, in other embodiments, may have more than two reactors, for example, more than three or more than four. 图2A的反应器131和132中的每一个在上文所述的反应条件内操作。 The reactor of FIG. 2A, 131 and 132 operating within each of the reaction conditions described above.

[0106] 在图2B的反应区140中,将蒸气进料流111给进到包含多个反应区域的反应器141。 [0106] In the reaction zone 140 in FIG. 2B, the vapor feed stream 111 fed to the reactor 141 comprises a plurality of reaction regions. 反应器141至少包含第一反应区域142和第二反应区域143。 The reactor 141 comprises at least a first reaction zone 142 and second reaction zone 143. 每个区域可以具有不同的催化剂。 Each region may have different catalysts. 如图2B中所示,第一反应区域142和第二反应区域143可以在反应器141中隔开。 As shown in FIG. 2B, the first reaction zone 142 and second reaction zone 143 may be spaced in the reactor 141. 在其它实施方案中,第一反应区域142和第二反应区域143交叠并且各自的催化剂可以分散在所述区域之间。 In other embodiments, the first reaction zone and second reaction zones 142 and 143 overlap each catalyst may be dispersed in the region between. 可以将反应器141例如第二反应器区域143的粗乙醇产物144给进到闪蒸器106。 The reactor 141 may be, for example, the second reactor zone is a crude ethanol product 144 143 106 fed to the flasher. 区域142和区域143在如上文所述的反应条件内操作。 Region 142 and region 143 operate within the reaction conditions as described above.

[0107] 在优选的实施方案中,不同的催化剂可以用于图2B中反应区130的各个反应器或者用于图2B中所示反应区140的各个反应区域中。 [0107] In a preferred embodiment, different catalysts may be used in each reactor the reaction zone of FIG. 2B 130 or for each reaction zone the reaction zone shown in FIG. 2B 140. 不同的催化剂可以具有不同的金属和/ 或不同的载体。 Different catalysts may have different metals and / or different vectors. 在优选的实施方案中,第一反应器131或第一反应器区域142中的催化剂可以是美国专利No. 7, 608, 744中所描述的钴催化剂,美国公开No. 2010/0029995中所描述的钼/锡催化剂,或美国公开No. 2010/0197959中所描述的包含碱性改性剂的金属催化剂, 在此通过引用将它们全文并入本文。 In a preferred embodiment, the first reactor or the first reactor catalyst 131 in region 142 may be U.S. Patent No. 7, 608, 744 cobalt catalysts described in U.S. Publication No. 2010/0029995 described molybdenum / tin catalyst, or US Publication No. comprises a basic metal catalyst modifier as described in 2010/0197959, herein incorporated by reference in their entirety herein.

[0108] 在一些实施方案中,第一反应器131或第一反应器区域142中的催化剂是碱性催化剂。 [0108] In some embodiments, the first reactor or the first reactor zone 131 142 the catalyst is a basic catalyst. 包含碱性改性剂的合适的金属催化剂包括具有第一金属和可选的第二金属的那些。 Suitable metal catalyst comprises a basic modifiers include those having optionally a first metal and a second metal. 这些金属可以与上文关于本发明的酸性负载型催化剂所描述的那些相同。 These metals can be about the same as those above described acidic supported catalyst of the present invention. 优选地,第一金属为VIII族金属,选自铁、钴、镍、钌、铑、钯、锇、铱和钼。 Preferably, the first metal is a Group VIII metal selected from iron, cobalt, nickel, ruthenium, rhodium, palladium, osmium, iridium and molybdenum. 任选第二金属优选可以选自铜、 锡、钴、铼和镍。 The second metal preferably may be optionally selected from copper, tin, cobalt, rhenium, and nickel. 所述催化剂可以包含0. 1-10重量%第一金属和0.卜10重量%第二金属。 The catalyst may comprise 0.5 to 10 wt% of a first metal and a 0.5 wt.% Of the second metal 10 BU.

[0109] 合适的载体材料可以包括例如稳定的金属氧化物基载体或陶瓷基载体。 [0109] Suitable support materials may include, for example, metal oxide-based ceramic matrix support or supports. 优选的载体包括含硅载体,例如二氧化硅、二氧化硅/氧化铝、ΠΑ族硅酸盐如偏硅酸钙、热解二氧化硅、高纯度二氧化硅和它们的混合物。 Preferred supports include silicon-containing carrier, such as silica, silica / alumina, ΠΑ group silicates such as calcium metasilicate, pyrogenic silica, high purity silica, and mixtures thereof. 其它载体可以包括但不限于铁氧化物、氧化铝、二氧化钛、氧化锆、氧化镁、碳、石墨、高表面积石墨化碳、活性炭和它们的混合物。 Other carriers may include, but are not limited to, iron oxide, alumina, titania, zirconia, magnesia, carbon, graphite, high surface area graphitized carbon, activated carbon, and mixtures thereof.

[0110] 催化剂载体可以用载体改性剂进行改性。 [0110] The catalyst support may be modified with a support modifier. 优选地,载体改性剂是具有低挥发性或无挥发性的碱性改性剂。 Preferably, the support modifier is a basic modifier has a low volatility or non-volatility. 这类碱性改性剂例如可以选自:(i)碱土金属氧化物、(ii)碱金属氧化物、(iii)碱土金属偏娃酸盐、(iv)碱金属偏娃酸盐、(V)ΠΒ族金属氧化物、(vi)IIB族金属偏硅酸盐、(vii)ΠΙΒ族金属氧化物、(viii)IIIB族金属偏硅酸盐和它们的混合物。 Such basic modifiers may be selected, for example: (i) an alkaline earth metal oxide, (ii) an alkali metal oxide, (iii) an alkaline earth metal partial salts baby, (iv) an alkali metal salt of the partial baby, (V ) ΠΒ metal oxides, (vi) IIB metal metasilicates, (vii) ΠΙΒ metal oxides, (viii) IIIB metal metasilicates and mixtures thereof. 除氧化物和偏硅酸盐之外,可以使用包括硝酸盐、亚硝酸盐、乙酸盐和乳酸盐在内的其它类型的改性剂。 In addition to oxides and metasilicates, other types of modifiers include nitrates, nitrites, acetates and lactates. 优选地,载体改性剂选自钠、钾、镁、钙、钪、钇和锌中任意元素的氧化物和偏硅酸盐,以及前述的任意混合物。 Preferably, the support modifier is selected from sodium, potassium, magnesium, calcium, scandium, yttrium, and zinc oxide and any element metasilicates, and mixtures of any of the foregoing. 优选地,载体改性剂是硅酸钙,更优选偏硅酸钙(CaSi03)。 Preferably, the support modifier is calcium, more preferably calcium metasilicate (CaSi03). 如果载体改性剂包含偏硅酸钙,则偏硅酸钙的至少一部分优选为结晶形式。 If at least a portion of the support modifier comprises calcium metasilicate, calcium metasilicate is preferably in crystalline form. 在使用碱性载体改性剂的优选实施方案中,碱性载体改性剂以基于催化剂总重量计0. 1重量% -50重量%, 例如0. 2重量% -25重量%、0. 5重量% -15重量%或1重量% -8重量%的量存在。 In a preferred embodiment using an alkaline support modifier, the basic support modifier based on the total weight of the catalyst 0.1 wt% to 50 wt%, for example 0.2 wt% to 25 wt%, 0.5 present an amount by weight to 15% by wt% or 1 wt% to 8% by weight.

[0111] 本发明的酸性催化剂优选用于第二反应器132或第二反应器区域143中。 [0111] present invention is preferably acidic catalyst for the second reactor, the second reactor zone 132 or 143. 在一个示例性实施方案中,第一反应器131或第一反应器区域142可以包含Si02-CaSi03_Pt-Sn催化剂,而第二反应器133或第二反应器143可以包含Si02-Ti02_Pt-Sn催化剂。 In one exemplary embodiment, the first reactor, the first reactor zone 131 or 142 may comprise Si02-CaSi03_Pt-Sn catalysts, while the second reactor 133 and second reactor 143 may comprise Si02-Ti02_Pt-Sn catalysts. 在替代实施方案中,酸性催化剂可以用于第一反应器131或第一反应器区域142中。 In alternative embodiments, the acidic catalyst may be used in the first reactor or the first reactor zone 131 142.

[0112] 第一反应器131或第一反应器区域142中的乙酸转化率可以分别相对低于第二反应器132或第二反应器区域143中的乙酸转化率。 [0112] The first reactor or the first reactor zone 131 conversion of acetic acid, respectively, relative to 142 may be lower than the second reactor a second reactor acetic acid conversion region 143 or 132. 第一反应器131或第一反应区域142的乙酸转化率可以为至少10 %,例如至少20 %、至少40 %、至少50 %、至少60 %、至少70 %或至少80%。 The first reactor 131, or conversion of the acid first reaction zone 142 may be at least 10%, such as at least 20%, at least 40%, at least 50%, at least 60%, at least 70% or at least 80%. 在一个实施方案中,第一反应器131或第一反应器区域142中的乙酸转化率为10% -80%并且低于第二反应器132或第二反应器区域143中未反应乙酸的转化率。 In one embodiment, the first reactor 131, or acetic acid conversion was first reactor zone 142 and lower than 10% -80% conversion of the second reactor unreacted acetic acid 132 or 143 in the second reactor zone rate. 在第二反应器132或第二反应器区域143中,可以使未反应乙酸的转化率提高到至少70%,例如至少80%或至少90%。 In the second reactor zone 132 or 143 of the second reactor, the conversion rate can be increased to the unreacted acetic acid is at least 70%, such as at least 80% or at least 90%. 有利地是,第一反应器131或第一反应器区域142中较低的乙酸转化率使第一反应器131或第一反应器区域142的未反应的酸在第二反应器132或第二反应器区域143中进行加氢而没有加入新鲜乙酸。 Advantageously, the lower the 142 first reactor or the first reactor zone 131 acetic acid conversion 131 the first reactor or the first reactor zone unreacted acid in the second reactor 142 or the second 132 reactor zone 143 without hydrogenating fresh acetic acid was added.

[0113] 图2A中所示的双反应器和/或图2B中所示的双反应器区域的总乙醇选择性可以为至少65%,例如至少70%、至少80%、至少85%或至少90%。 [0113] bis reactor shown in FIG. 2A total selectivity to ethanol and / or dual reactor zone illustrated in FIG. 2B may be at least 65%, at least 70%, at least 80%, at least 85%, or at least 90%. 可以通过第一反应器131 或第一反应器区域142产生的乙酸乙酯可以在第二反应器132或第二反应器区域143中被消耗。 Ethyl acetate can be produced by the 142 first reactor or the first reactor zone 131 may be consumed in the second reactor, the second reactor zone 132 or 143.

[0114] 成品乙醇 [0114] The finished ethanol

[0115] 通过本发明方法获得的成品乙醇组合物优选包含基于该成品乙醇组合物总重量计75-96重量%乙醇,例如80-96重量%或85-96重量%的乙醇。 [0115] obtained by the process of the present invention is finished ethanol composition preferably comprises 75-96% by weight ethanol meter based on the total weight of the finished ethanol composition, e.g. 80-96 wt% or 85-96 wt% of ethanol. 下表6中提供了示例性成品乙醇组成范围。 Table 6 below provides an exemplary compositional ranges finished ethanol.

[0116] [0116]

Figure CN102307657BD00201

[0117] 本发明的成品乙醇组合物优选含有非常低量,例如小于0.5重量%的其它醇,例如甲醇、丁醇、异丁醇、异戊基醇和其它c4-c2(l醇。在一个实施方案中,成品乙醇中异丙醇的量为80-1,OOOwppm,例如95-1,OOOwppm、100-700wppm或150_500wppm。在一个实施方案中, 成品乙醇组合物优选基本上不含乙醛,可以包含小于8wppm的乙醛,例如小于5wppm或小于lwppm。 [0117] The finished ethanol composition of the present invention preferably contains very low amounts, for example less than 0.5 weight percent of other alcohols, for example methanol, butanol, isobutanol, amyl alcohol and other c4-c2 (l-ol. In one embodiment embodiment, the amount of ethanol isopropanol is finished 80-1, OOOwppm, e.g. 95-1, OOOwppm, 100-700wppm or 150_500wppm. in one embodiment, the finished composition is preferably substantially free of ethanol and acetaldehyde can be acetaldehyde 8wppm comprising less than, for example, less than or less than 5wppm lwppm.

[0118] 由本发明实施方案生产的成品乙醇组合物可以用于各种应用,包括燃料、溶剂、化学原料、药物产品、清洁剂、消毒杀菌剂、加氢转化或消费。 [0118] produced by the embodiments of the present invention may be used in the finished ethanol composition in various applications, including fuel, solvent, chemical raw materials, pharmaceutical products, detergents, sanitizers, hydroconversion or consumption. 在燃料应用中,可以使该成品乙醇组合物与汽油调合用于机动车辆例如汽车、船只和小型活塞发动机飞机。 In fuel applications, the finished ethanol composition may be blended with gasoline for motor vehicles as automobiles, boats and small piston engine aircraft, for example. 在非燃料应用中,该成品乙醇组合物可以用作化妆品和化妆品制剂、清净剂、消毒剂、涂料、油墨和药品的溶剂。 In the non-fuel applications, the finished ethanol may be used as a solvent cosmetic compositions and cosmetic preparations, detergents, disinfectants, paints, inks, and pharmaceuticals. 该成品乙醇组合物还可以在药用产品、食品制备、染料、光化学和乳胶处理的制造过程中用作处理溶剂。 The finished ethanol composition may also be used as a processing solvent in the manufacturing process of a pharmaceutical product, food preparation, dyes, photochemical and latex processing.

[0119] 该成品乙醇组合物还可以用作化学原料以制备其它化学品例如醋、丙烯酸乙酯、 乙酸乙酯、乙烯、二醇醚、乙胺、醛和高级醇,特别是丁醇。 [0119] The finished ethanol composition may also be used as a chemical feedstock to make other chemicals such as vinegar, ethyl acrylate, ethyl acetate, ethylene, glycol ethers, amine, aldehyde, and higher alcohols, in particular butanol. 在乙酸乙酯的制备中,可以将该成品乙醇组合物用乙酸酯化或者使其与聚乙酸乙烯酯反应。 In the production of ethyl acetate, the finished composition was esterified with ethanol, acetic acid or reacted with polyvinyl acetate ester. 可以使该成品乙醇组合物脱水以生产乙烯。 The composition may be finished ethanol was dehydrated to produce ethylene. 可使用任何已知的脱水催化剂使乙醇脱水,所述脱水催化剂例如在共同未决的美国申请No. 12/221,137和美国申请No. 12/221,138中所描述的那些,在此通过引用将它们的全部内容和公开内容并入本文。 Any known dehydration catalysts ethanol dehydration, the dehydration catalyst, for example, in copending U.S. Application No. 12 / 221,137 and those described in U.S. Application No. 12 / 221,138 described herein by reference in their entirety and the disclosure of which is incorporated herein. 例如,沸石催化剂可以用作脱水催化剂。 For example, a zeolite catalyst may be used as the dehydration catalyst. 优选地, 所述沸石具有至少约〇. 6nm的孔径,优选的沸石包括选自丝光沸石、ZSM-5、沸石X和沸石Y的脱水催化剂。 Preferably, the zeolite has at least approximately square. Pore size, the zeolite preferably 6nm dehydration catalyst comprises a zeolite selected from mordenite, ZSM-5, zeolite X and zeolite Y. 例如沸石X描述于美国专利No. 2, 882, 244中,沸石Y描述于美国专利No. 3, 130, 007中,在此通过引用将它们全文并入本文。 Zeolite X is described, for example, in U.S. Patent No. 2, 882, 244, the zeolite Y is described in U.S. Patent No. 3, 130, 007, herein incorporated by reference in their entirety herein.

[0120] 为了可以更有效地理解本文公开的发明,下面提供以下实施例。 [0120] In order to be more efficiently understood that the invention disclosed herein, the following examples are provided below. 实施例 Example

[0121] 实施例1 [0121] Example 1

[0122] 在包含Si02_Ti02(10重量%)_Pt(1.6重量%)_Sn(1.0重量%)的酸性催化剂存在下将乙酸加氢。 [0122] hydrogenating acetic acid in the presence of an acidic catalyst comprising Si02_Ti02 (10 wt%) _ Pt (1.6 wt%) _ Sn (1.0 wt%). 在反应器中于200pSig、250°C下用该催化剂进行2个轮次。 In 200pSig, for two rounds in a reactor at 250 ° C with the catalyst. 第一个轮次是以ASOOhfGHSV,第二个轮次是以ZZOOh^GHSV。 The first round is ASOOhfGHSV, the second round is ZZOOh ^ GHSV. 在图3中,理论计算结果KTW为4,和K τ«为12。 In Figure 3, the theoretical results KTW to 4, and K τ «12. 如图3中所示,在较低的乙酸转化率下乙酸乙酯的量大于乙醇的量。 As shown in FIG. 3, in ethyl acetate at lower conversions of acetic acid greater than the amount of ethanol. 然而,在较高的乙酸转化率下,平衡反应动力学出人意料地使乙酸乙酯含量降低而提高乙醇含量。 However, at higher conversion of acetic acid, the equilibrium reaction kinetics surprisingly The ethyl acetate content is increased to reduce the ethanol content. 表7汇总了结果。 Table 7 summarizes the results.

[0123] [0123]

Figure CN102307657BD00211

[0124] 实施例2 [0124] Example 2

[0125] 在包含Si02-Ti02(10重量%)-Pt(L6重量%)-Sn(L0重量% )的酸性催化剂和包含Si02-Al203(7重量% )-Pt(1.6重量% )-Sn(1.0重量% )的酸性催化剂存在下将乙酸加氢。 [0125] comprising Si02-Ti02 (10 wt%) - Pt (L6 wt%) - acidic catalyst Sn (L0 wt%), and comprising Si02-Al203 (7 wt%) -Pt (1.6 wt%) -Sn ( hydrogenating acetic acid in the presence of 1.0% by weight) of an acidic catalyst. 在不同的乙酸转化率水平下进行每种加氢若干次。 For each of the several hydrogenation of acetic acid at different conversion levels. 在图4中比较了结果。 The results are compared in FIG. 4. 在较低的转化率下,Si02-Al203 (7重量% )-Pt(1.6重量% )-Sn(1.0重量% )催化剂显示出提高的乙醇选择性。 At lower conversions, Si02-Al203 (7 wt%) -Pt (1.6 wt%) -Sn (1.0 wt%) catalyst exhibits enhanced selectivity to ethanol. 然而,在较高的转化率下,Si02-Ti02(10重量% )-Pt(1.6重量% )-Sn(1.0重量% )催化剂显示出类似的乙醇选择性。 However, at higher conversions, Si02-Ti02 (10 wt%) -Pt (1.6 wt%) -Sn (1.0 wt%) catalyst exhibit similar selectivity to ethanol. 此外,出人意料和意想不到地,在较高的乙酸转化率下酸性催化剂的产率显示出明显改进。 Furthermore, surprisingly and unexpectedly, at higher conversion of acetic acid yields an acidic catalyst exhibit significantly improved.

[0126] 实施例3 [0126] Example 3

[0127] 在表8中给出的以下不同的反应条件下也以若干轮次使用来自实施例2的包含Si02-Al203 (7重量% )-Pt(l. 6重量% )-Sn(l. 0重量% )的酸性催化剂将乙酸加氢。 [0127] Table 8 given in the following under different reaction conditions used in several rounds from Example contains Si02-Al203 (7 wt%) -Pt 2 is (l. 6 wt.%) -Sn (l. 0% by weight) of acetic acid hydrogenation catalyst.

[0128] [0128]

Figure CN102307657BD00221

[0129] 虽然详细描述了本发明,但在本发明的精神和范围内的各种修改对于本领域技术人员而言将是显而易见的。 [0129] While the invention has been described in detail, but within the spirit and scope of the invention modifications to those skilled in the art will be apparent. 鉴于上述讨论,上文关于背景技术和详细描述所讨论的本领域相关知识和参考文献,通过引用将它们的公开内容全部并入本文。 In view of the above discussion, the background art above with respect to the art and discussed in the detailed description of the relevant knowledge and references by reference in their disclosures are all incorporated herein by reference. 此外,应理解在下文和/ 或在所附权利要求书中引述的本发明的各个方面以及多个实施方案和多个特征的各个部分可以部分或全部地进行组合或者互换。 Further, it should be understood that, and / or may be partially or entirely in a plurality of parts of various aspects and embodiments and features of the present invention, a plurality of the appended claims recited hereinafter combined or interchanged. 在前述各个实施方案的描述中,如本领域技术人员所可认识到的,引用另一个实施方案的实施方案可以与其它实施方案适当地组合。 In the foregoing descriptions of the various embodiments, as those skilled in the art may be appreciated, reference to another embodiment of the embodiment may be appropriately combined with other embodiments. 此外, 本领域技术人员将认识到前述描述仅仅是举例方式,并且不意欲限制本发明。 Moreover, those skilled in the art will recognize that the foregoing description is by way of example only, and not intended to limit the present invention.

Claims (31)

1. 一种生产乙醇的方法,该方法包括在催化剂存在下、在2 50°C- 3Ο0 °C的温度和100KPa-1500KPa的压力下将乙酸加氢形成乙醇,其中将反应物以1000hr4-6500hrH的气时空速给进,其中乙酸转化率为大于80%且乙醇选择性为至少65%,其中所述催化剂包含在用酸性改性剂改性的载体材料上的第一金属和第二金属,所述第一金属选自铜、铁、钴、镍、 铑、钯、锇、铱、钼、钛、锌、铬、铼、钥和鹤,第二金属选自锡和铼,条件是第二金属不同于第一金属。 A method for producing ethanol, which comprises the presence of a catalyst at a pressure and temperature 2 50 ° C- 3Ο0 ° C and 100KPa-1500KPa hydrogenating acetic acid to form ethanol wherein the reactants 1000hr4-6500hrH feed gas hourly space velocity, wherein the acetic acid conversion was greater than 80% and ethanol selectivity is at least 65%, wherein the catalyst comprises a first metal and a second metal on the support material with an acidic modifier-modified, the first metal is selected from copper, iron, cobalt, nickel, rhodium, palladium, osmium, iridium, molybdenum, titanium, zinc, chromium, rhenium, and key crane, a second metal selected from tin and rhenium, with the proviso that the second metal different from the first metal.
2. 权利要求1的方法,其中所述载体材料选自二氧化硅、二氧化硅/氧化铝、偏硅酸钙、 碳、铁氧化物、氧化铝、二氧化钛、氧化锆和它们的混合物。 2. The method of claim 1, wherein said support material is selected from silica, silica / alumina, calcium metasilicate, carbon, iron oxide, alumina, titania, zirconia, and mixtures thereof.
3. 权利要求2的方法,其中所述二氧化硅选自热解二氧化硅、高纯度二氧化硅和它们的混合物。 The method of claim 2, wherein the silica is selected from fumed silica, high purity silica and mixtures thereof.
4. 权利要求1的方法,其中所述酸性改性剂选自IVB族金属的氧化物、VB族金属的氧化物、VIB族金属的氧化物、VIIB族金属的氧化物、VIIIB族金属的氧化物、铝氧化物和它们的混合物。 The process of oxidation of the oxide of Group VB metals, Group VIB metal oxides, Group VIIB metal oxides, VIIIB metals of claim 1, wherein the acidic modifier selected from oxides of Group IVB metals, , aluminum oxides and mixtures thereof.
5. 权利要求1的方法,其中所述酸性改性剂选自Ti02、Zr02、Nb205、Ta205、A1203、B203、 P205 和Sb203。 The method of claim 1, wherein the acidic modifier is selected from Ti02, Zr02, Nb205, Ta205, A1203, B203, P205, and Sb203.
6. 权利要求1的方法,其中所述酸性改性剂选自W03、Mo03、Fe203、Cr203、V205、Mn02、Cu0、 C〇203、Bi203〇 6. The method of claim 1, wherein the acidic modifier selected W03, Mo03, Fe203, Cr203, V205, Mn02, Cu0, C〇203, Bi203〇
7. 权利要求1的方法,其中所述催化剂包含0. 1重量%-50重量%酸性改性剂。 The method of claim 1, wherein the catalyst comprises 0.1 wt% -50 wt% acidic modifier.
8. 权利要求1的方法,其中所述催化剂包含25重量%-99重量%载体材料。 The method of claim 1, wherein the catalyst comprises 25 wt% to 99 wt% carrier material.
9. 权利要求1的方法,其中所述催化剂包含25重量%-99重量%酸性载体材料。 9. The method of claim 1, wherein the catalyst comprises 25 wt% to 99 wt% acidic support material.
10. 权利要求1的方法,其中催化剂包含0. 1-25重量%第一金属。 10. The method of claim 1, wherein the catalyst comprises 0.5 to 25 wt% of the first metal.
11. 权利要求1的方法,其中所述第一金属是钼,第二金属是锡。 11. The method of claim 1, wherein said first metal is molybdenum, the second metal is tin.
12. 权利要求11的方法,其中钼与锡的摩尔比为0. 4:0. 6-0. 6:0. 4。 12. The method of claim 11, wherein the molar ratio of the molybdenum and tin is 0.4: 06-06:... 04.
13. 权利要求1的方法,其中所述第一金属是钯,第二金属是铼。 13. The method of claim 1, wherein the first metal is palladium and the second metal is rhenium.
14. 权利要求13的方法,其中铼与钯的摩尔比为0. 7:0. 3-0. 85:0. 15。 14. The method of claim 13, wherein the molar ratio of rhenium to palladium is 0.7: 03-085:... 015.
15. 权利要求1的方法,其中所述催化剂包含0. 1-10重量%第二金属。 15. The method of claim 1, wherein the catalyst comprises 1-10 wt% of the second metal 0.05.
16. 权利要求1的方法,其中所述加氢具有小于35%的乙酸乙酯选择性。 16. The method of claim 1, wherein said hydrogenation having less than 35% selectivity to ethyl acetate.
17. 权利要求1的方法,其中所述加氢在大于4:1的氢气与乙酸摩尔比下进行。 17. The method of claim 1, wherein the hydrogenation of greater than 4: acetic acid molar ratio of hydrogen to 1.
18. -种生产乙醇的方法,该方法包括: 在第一催化剂存在下将乙酸加氢形成包含乙醇和未反应的乙酸的中间产物;以及在第二催化剂存在下将未反应的乙酸加氢形成乙醇,其中第二催化剂不同于第一催化齐U,其中所述第二催化剂包含在酸性载体上的第一金属和第二金属,所述第一金属选自铁、 钴、镍、铭、钮、锇、铱、钼、钛、锌、铬、铼、钥和鹤,第二金属选自钥、锡、铬、铁、钴、银、鹤、钮、 钼、镧、铈、锰、钌、铼、金和镍,条件是第二金属不同于第一金属,所述酸性载体选自: 选自铁氧化物、氧化铝、二氧化硅/氧化铝、二氧化钛、氧化锆和它们的混合物的酸性载体材料,以及用酸性改性剂改性的载体材料。 18. The - method for producing ethanol, said method comprising: a first catalyst in the presence of hydrogenating acetic acid to form an intermediate product containing unreacted ethanol and acetic acid; and acetic acid in the presence of a second hydrogenation catalyst is formed unreacted ethanol, wherein the second catalyst a first catalyst is different from the aligned U, wherein the second catalyst comprises a first metal on an acidic support and a second metal, said first metal selected from iron, cobalt, nickel, Ming Niu , osmium, iridium, molybdenum, titanium, zinc, chromium, rhenium, and cranes key, the second key is selected from metal, tin, chromium, iron, cobalt, silver, crane, button, molybdenum, lanthanum, cerium, manganese, ruthenium, rhenium, gold, and nickel, with the proviso that the second metal different from the first metal, the acidic support is selected from: an acid selected from iron oxide, alumina, silica / alumina, titania, zirconia, and mixtures thereof support material, and a support material modified with an acidic modifier.
19. 权利要求18的方法,其中在第一反应器中进行乙酸的加氢,在第二反应器中进行未反应的乙酸的加氢。 19. The method of claim 18, wherein the hydrogenation of acetic acid in the first reactor, hydrogenation of unreacted acetic acid in the second reactor.
20. 权利要求19的方法,其中在第一反应器中使至少10%的乙酸转化,在第二反应器中使至少70%的未反应的乙酸转化。 20. The method of claim 19, wherein at least 10% acetic acid is converted in a first reactor, at least 70% acetic acid conversion unreacted a second reactor.
21. -种生产乙醇的方法,该方法包括: 在反应器中于第一催化剂和第二催化剂存在下将乙酸加氢形成乙醇,其中第二催化剂不同于第一催化剂,其中所述第二催化剂包含在酸性载体上的第一金属和第二金属,所述第一金属选自铁、钴、镍、铭、钮、锇、铱、钼、钛、锌、铬、铼、钥和鹤,第二金属选自钥、锡、铬、 铁、钴、钒、钨、钯、钼、镧、铈、锰、钌、铼、金和镍,条件是第二金属不同于第一金属,所述酸性载体选自: 选自铁氧化物、氧化铝、二氧化硅/氧化铝、二氧化钛、氧化锆和它们的混合物的酸性载体材料,以及用酸性改性剂改性的载体材料。 21. The - method for producing ethanol, the method comprising: at the first catalyst and the second catalyst is present in the reactor in the hydrogenation of acetic acid to form ethanol, wherein the first catalyst is different from the second catalyst, wherein the second catalyst on an acidic support comprising a first metal and a second metal, said first metal selected from iron, cobalt, nickel, Ming Niu, osmium, iridium, molybdenum, titanium, zinc, chromium, rhenium, and key crane, the two metal selected key, tin, chromium, iron, cobalt, vanadium, tungsten, palladium, molybdenum, lanthanum, cerium, manganese, ruthenium, rhenium, gold, and nickel, with the proviso that the second metal different from the first metal, the acidic carrier is selected from: selected from iron oxides, alumina, silica / alumina, titania, zirconia, and mixtures thereof acidic support material, and the acidic modifier with modified support material.
22. 权利要求21的方法,其中所述第一催化剂在第一反应器区域中,第二催化剂在第二反应器区域中,其中第一区和第二区是隔开的。 22. The method of claim 21, wherein said first catalyst in a first reactor zone, a second catalyst in the second reactor zone, wherein the first and second regions are spaced apart.
23. 权利要求18或21的方法,其中所述第一催化剂包含含有一种或多种金属、含硅载体和至少一种碱性载体改性剂的催化剂。 23. A method as claimed in claim 18 or 21, wherein the first catalyst comprises a catalyst comprising one or more metals, silicon-containing carrier and at least one basic support modifier.
24. 权利要求23的方法,其中所述至少一种碱性载体改性剂选自(i)碱土金属氧化物、 (ii)碱金属氧化物、(iii)碱土金属偏娃酸盐、(iv)碱金属偏娃酸盐、(ν)ΠΒ族金属氧化物、(vi)IIB族金属偏硅酸盐、(vii)IIIB族金属氧化物、(viii)IIIB族金属偏硅酸盐和它们的混合物。 24. The method of claim 23, wherein said at least one basic support modifier is selected from (i) an alkaline earth metal oxide, (ii) an alkali metal oxide, (iii) an alkaline earth metal partial salts baby, (iv ) an alkali metal salt of the partial baby, (ν) ΠΒ metal oxide, (vi) IIB metal metasilicates, (vii) IIIB metal oxides, (viii) IIIB metal metasilicates and their mixture.
25. 权利要求23的方法,其中所述含硅载体选自二氧化硅、二氧化硅/氧化铝、偏硅酸钙和它们的混合物。 25. The method of claim 23, wherein the silicon-containing support is selected from silica, silica / alumina, calcium metasilicate, and mixtures thereof.
26. 权利要求25的方法,其中所述二氧化硅选自热解二氧化硅、高纯度二氧化硅和它们的混合物。 26. The method of claim 25, wherein the silica is selected from fumed silica, high purity silica and mixtures thereof.
27. -种回收乙醇的方法,该方法包括在包含催化剂的反应器中将乙酸进料流加氢形成粗乙醇产物,其中所述催化剂包含在酸性载体上的第一金属,所述酸性载体选自: 选自铁氧化物、氧化铝、二氧化硅/氧化铝、二氧化钛、氧化锆和它们的混合物的酸性载体材料,以及用酸性改性剂改性的载体材料; 在第一塔中将至少部分粗乙醇产物分离成包含乙醇、水和乙酸乙酯的第一馏出物,以及包含乙酸的第一残余物; 在第二塔中将至少部分第一馏出物分离成包含乙酸乙酯的第二馏出物以及包含乙醇和水的第二残余物; 使至少部分第二馏出物返回到所述反应器;并且在第三塔中将至少部分第二残余物分离成包含乙醇的第三馏出物和包含水的第三残余物。 27. - recovering ethanol method, which comprises a catalyst in a reactor comprising hydrogenating acetic acid feed stream to form a crude ethanol product, wherein the catalyst comprises a first metal on an acidic carrier, the carrier is selected from acidic from: selected from iron oxides, acidic support material is alumina, silica / alumina, titania, zirconia, and mixtures thereof, and a carrier material with a modified acidic modifier; at least in a first column the crude product was separated into the ethanol part comprising ethanol, ethyl acetate and water, a first distillate and a first residue comprising acetic acid; in a second column at least partially separated into a first distillate comprising ethyl acetate the second distillate and a second residue comprising ethanol and water; at least a portion of the second distillate is returned to the reactor; and at least partially separated into a second residue of the ethanol contained in the third column three distillate comprising water and a third residue.
28. 权利要求27的方法,其中所述乙酸进料流包含选自乙酸、乙酸酐、乙醛、乙酸乙酯和它们的混合物的一种或多种化合物。 28. The method of claim 27, wherein the acetic acid feed stream comprises one selected from acetic acid, acetic anhydride, acetaldehyde, ethyl acetate, and mixtures of one or more compounds thereof.
29. 权利要求27的方法,其中所述粗乙醇产物的至少一部分包含乙酸。 29. The method of claim 27, wherein said at least a portion of the crude ethanol product comprises acetic acid.
30. 权利要求27的方法,该方法还包括直接或间接地使至少部分第一残余物返回到所述反应器,其中所述第一残余物包含基于该第一残余物总重量计60-100重量%的乙酸。 30. The method of claim 27, further comprising directly or indirectly at least a first portion of the residue was returned to the reactor, wherein the first residue comprises based on total weight of the first residue meter 60-100 wt% acetic acid.
31. 权利要求27的方法,其中所述第二馏出物包含10-90重量%乙酸乙酯。 31. The method of claim 27, wherein the second distillate comprises 10-90% by weight of ethyl acetate.
CN201080003928.5A 2008-07-31 2010-10-26 Acetic acid using an acid catalyst prepared by the method of ethanol CN102307657B (en)

Priority Applications (17)

Application Number Priority Date Filing Date Title
US12/588,727 2009-10-26
US12/588,727 US8309772B2 (en) 2008-07-31 2009-10-26 Tunable catalyst gas phase hydrogenation of carboxylic acids
US30081510P true 2010-02-02 2010-02-02
US12/699,024 US8680317B2 (en) 2008-07-31 2010-02-02 Processes for making ethyl acetate from acetic acid
US12/698,947 US8471075B2 (en) 2008-07-31 2010-02-02 Processes for making ethanol from acetic acid
US61/300,815 2010-02-02
US12/699,024 2010-02-02
US12/698,947 2010-02-02
US33269610P true 2010-05-07 2010-05-07
US33269910P true 2010-05-07 2010-05-07
US61/332,696 2010-05-07
US61/332,699 2010-05-07
US12/852,269 US8304586B2 (en) 2010-02-02 2010-08-06 Process for purifying ethanol
US12/852,227 US8309773B2 (en) 2010-02-02 2010-08-06 Process for recovering ethanol
US12/852,227 2010-08-06
US12/852,269 2010-08-06
PCT/US2010/054136 WO2011056597A2 (en) 2009-10-26 2010-10-26 Process for making ethanol from acetic acid using acidic catalysts

Publications (2)

Publication Number Publication Date
CN102307657A CN102307657A (en) 2012-01-04
CN102307657B true CN102307657B (en) 2014-10-08

Family

ID=56291204

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201080003928.5A CN102307657B (en) 2008-07-31 2010-10-26 Acetic acid using an acid catalyst prepared by the method of ethanol

Country Status (12)

Country Link
EP (1) EP2493610A2 (en)
JP (1) JP2013508424A (en)
KR (1) KR20120086717A (en)
CN (1) CN102307657B (en)
AU (1) AU2010315554A1 (en)
BR (1) BR112012009824A2 (en)
CA (1) CA2778959A1 (en)
MX (1) MX2012004842A (en)
NZ (1) NZ599463A (en)
RU (1) RU2012121872A (en)
WO (1) WO2011056597A2 (en)
ZA (1) ZA201202850B (en)

Families Citing this family (19)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9272970B2 (en) 2010-07-09 2016-03-01 Celanese International Corporation Hydrogenolysis of ethyl acetate in alcohol separation processes
US8704008B2 (en) * 2010-07-09 2014-04-22 Celanese International Corporation Process for producing ethanol using a stacked bed reactor
WO2012149137A1 (en) 2011-04-26 2012-11-01 Celanese International Corporation Process for the production of ethanol from an acetic acid feed and a recycled ethyl acetate feed
US9073816B2 (en) 2011-04-26 2015-07-07 Celanese International Corporation Reducing ethyl acetate concentration in recycle streams for ethanol production processes
US8895786B2 (en) 2011-08-03 2014-11-25 Celanese International Corporation Processes for increasing alcohol production
WO2013019230A1 (en) * 2011-08-03 2013-02-07 Celanese International Corporation Process for separating ethanol having low acid
US8440866B2 (en) 2011-08-03 2013-05-14 Celanese International Corporation Process for separating ethanol having low acid
DE102012002274A1 (en) * 2012-02-06 2013-08-08 Oxea Gmbh Process for the combined production of Vinylestern and acetic acid derived products or Propionsäurefolgeprodukten
US9051235B2 (en) * 2012-02-07 2015-06-09 Celanese International Corporation Process for producing ethanol using a molar excess of hydrogen
CN102584524A (en) * 2012-02-29 2012-07-18 付顺林 Alcohol recovery tower
US8802903B2 (en) * 2012-03-13 2014-08-12 Celanese International Corporation Stacked bed reactor with diluents for producing ethanol
CN103373899B (en) * 2012-04-27 2016-01-06 上海浦景化工技术股份有限公司 A method and apparatus acetic acid or catalytic hydrogenation reaction of acetate to ethanol
CN103570495B (en) * 2012-07-25 2016-02-17 上海浦景化工技术股份有限公司 Apparatus and method for multi-stage catalytic hydrogenation of acetic acid or acetate to ethanol
CN103664524B (en) * 2012-09-05 2016-01-13 中国石油化工股份有限公司 1,4-cyclohexanedicarboxylic acid hydrogenation method of 1,4-cyclohexane dimethanol
DE102013106790A1 (en) 2013-06-28 2014-12-31 Oxea Gmbh A process for the production of 1,3-butanediol
DE102013106787A1 (en) 2013-06-28 2014-12-31 Oxea Gmbh A process for the preparation of n-butane derivatives
JP2016026864A (en) * 2014-06-25 2016-02-18 積水化学工業株式会社 Catalyst for synthesis of ethyl acetate, device of producing ethyl acetate and method for producing ethyl acetate
CN104307557B (en) * 2014-09-19 2016-08-17 东营海纳新材料有限公司 A method for preparing a catalyst hydrogenation of methyl difluoroacetate difluoroethanol
WO2016175747A1 (en) * 2015-04-27 2016-11-03 Celanese International Corporation Hydrogenation catalysts comprising a mixed oxide having bismuth and process for producing ethanol

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN86102452A (en) 1985-04-13 1986-12-03 Bp化学有限公司 Alcohols production by hydrogenation of carboxylic acids

Family Cites Families (25)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2882244A (en) 1953-12-24 1959-04-14 Union Carbide Corp Molecular sieve adsorbents
US3130007A (en) 1961-05-12 1964-04-21 Union Carbide Corp Crystalline zeolite y
US5144068A (en) 1984-05-03 1992-09-01 Hoechst Celanese Corporation Methanol carbonylation process
US5001259A (en) 1984-05-03 1991-03-19 Hoechst Celanese Corporation Methanol carbonylation process
US5026908A (en) 1984-05-03 1991-06-25 Hoechst Celanese Corporation Methanol carbonylation process
CA1299195C (en) 1986-06-16 1992-04-21 G. Paull Torrence Addition of hydrogen to carbon monoxide feed gas in producing acetic acid by carbonylation of methanol
GB8828616D0 (en) * 1988-12-07 1989-01-11 Bp Chem Int Ltd Chemical process
JPH06116182A (en) * 1992-10-09 1994-04-26 Mitsubishi Kasei Corp Hydrogenation of organic carboxylic acid and/or organic carboxylic acid ester
USRE35377E (en) 1993-05-27 1996-11-12 Steinberg; Meyer Process and apparatus for the production of methanol from condensed carbonaceous material
US5821111A (en) 1994-03-31 1998-10-13 Bioengineering Resources, Inc. Bioconversion of waste biomass to useful products
US5599976A (en) 1995-04-07 1997-02-04 Hoechst Celanese Corporation Recovery of acetic acid from dilute aqueous streams formed during a carbonylation process
IN192600B (en) 1996-10-18 2004-05-08 Hoechst Celanese Corp An improved process for the carbonylation of methanol to produce acetic acid
US6232352B1 (en) 1999-11-01 2001-05-15 Acetex Limited Methanol plant retrofit for acetic acid manufacture
US6627770B1 (en) 2000-08-24 2003-09-30 Celanese International Corporation Method and apparatus for sequesting entrained and volatile catalyst species in a carbonylation process
US6657078B2 (en) 2001-02-07 2003-12-02 Celanese International Corporation Low energy carbonylation process
US6685754B2 (en) 2001-03-06 2004-02-03 Alchemix Corporation Method for the production of hydrogen-containing gaseous mixtures
US7115772B2 (en) 2002-01-11 2006-10-03 Celanese International Corporation Integrated process for producing carbonylation acetic acid, acetic anhydride, or coproduction of each from a methyl acetate by-product stream
US7005541B2 (en) 2002-12-23 2006-02-28 Celanese International Corporation Low water methanol carbonylation process for high acetic acid production and for water balance control
US7208624B2 (en) 2004-03-02 2007-04-24 Celanese International Corporation Process for producing acetic acid
SG185947A1 (en) * 2007-11-14 2012-12-28 Bp Plc Process for the production of alcohol from a carbonaceous feedstock
US8680317B2 (en) 2008-07-31 2014-03-25 Celanese International Corporation Processes for making ethyl acetate from acetic acid
US7863489B2 (en) * 2008-07-31 2011-01-04 Celanese International Corporation Direct and selective production of ethanol from acetic acid utilizing a platinum/tin catalyst
US8471075B2 (en) 2008-07-31 2013-06-25 Celanese International Corporation Processes for making ethanol from acetic acid
US7608744B1 (en) 2008-07-31 2009-10-27 Celanese International Corporation Ethanol production from acetic acid utilizing a cobalt catalyst
US7855303B2 (en) * 2008-11-14 2010-12-21 Celanese International Corporation Integrated process for the production of vinyl acetate from acetic acid via ethylene

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN86102452A (en) 1985-04-13 1986-12-03 Bp化学有限公司 Alcohols production by hydrogenation of carboxylic acids

Also Published As

Publication number Publication date
AU2010315554A1 (en) 2012-05-17
NZ599463A (en) 2014-05-30
KR20120086717A (en) 2012-08-03
BR112012009824A2 (en) 2016-11-22
ZA201202850B (en) 2013-06-26
CA2778959A1 (en) 2011-05-12
WO2011056597A2 (en) 2011-05-12
RU2012121872A (en) 2013-12-10
JP2013508424A (en) 2013-03-07
WO2011056597A3 (en) 2011-07-14
CN102307657A (en) 2012-01-04
EP2493610A2 (en) 2012-09-05
MX2012004842A (en) 2012-05-29

Similar Documents

Publication Publication Date Title
US8884080B2 (en) Reduced energy alcohol separation process
US20120010445A1 (en) Low Energy Alcohol Recovery Processes
US9102581B2 (en) Process for producing ethanol using an extractive distillation column
US8304586B2 (en) Process for purifying ethanol
US8318988B2 (en) Process for purifying a crude ethanol product
US8704015B2 (en) Process for recovering ethanol
US8394985B2 (en) Process for producing an ester feed stream for esters production and co-production of ethanol
US8754268B2 (en) Process for removing water from alcohol mixtures
EP2590918B1 (en) Liquid esterification for the production of alcohols
US9024083B2 (en) Process for the production of ethanol from an acetic acid feed and a recycled ethyl acetate feed
US8829250B2 (en) Finishing reactor for purifying ethanol
US8546622B2 (en) Process for making ethanol from acetic acid using acidic catalysts
US8884081B2 (en) Integrated process for producing acetic acid and alcohol
CN102958882B (en) Ethanol production from acetic acid utilizing a molybdenum carbide catalyst
US8680342B2 (en) Process for recovering alcohol produced by hydrogenating an acetic acid feed stream comprising water
US8858659B2 (en) Processes for producing denatured ethanol
CN103080053B (en) Use stacked bed reactor for producing ethanol
US8704011B2 (en) Separating ethanol and ethyl acetate under low pressure conditions
US8710279B2 (en) Hydrogenolysis of ethyl acetate in alcohol separation processes
AU2011213058B2 (en) Process for purifying a crude ethanol product
WO2011097220A2 (en) Process for producing ethanol using an extractive distillation column
US8653308B2 (en) Process for utilizing a water stream in a hydrolysis reaction to form ethanol
US20130131400A1 (en) Hydrogenating Acetic Acid to Produce Ethyl Acetate and Reducing Ethyl Acetate to Ethanol
US8927788B2 (en) Process to recover alcohol with reduced water from overhead of acid column
KR20120086717A (en) Process for making ethanol from acetic acid using acidic catalysts

Legal Events

Date Code Title Description
C06 Publication
C10 Entry into substantive examination
REG Reference to a national code

Ref country code: HK

Ref legal event code: DE

Ref document number: 1165751

Country of ref document: HK

C14 Grant of patent or utility model
REG Reference to a national code

Ref country code: HK

Ref legal event code: WD

Ref document number: 1165751

Country of ref document: HK

CF01