CN102442883A - 使用钴催化剂由乙酸制备乙醇 - Google Patents

使用钴催化剂由乙酸制备乙醇 Download PDF

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CN102442883A
CN102442883A CN2011102958280A CN201110295828A CN102442883A CN 102442883 A CN102442883 A CN 102442883A CN 2011102958280 A CN2011102958280 A CN 2011102958280A CN 201110295828 A CN201110295828 A CN 201110295828A CN 102442883 A CN102442883 A CN 102442883A
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converted
ethanol
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V·J·约翰斯顿
J·T·查普曼
L·陈
B·F·基米希
J·H·津克
J·C·范登瓦尔
V·祖扎尼克
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    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
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    • C07C29/147—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of carboxylic acids or derivatives thereof
    • C07C29/149—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of carboxylic acids or derivatives thereof with hydrogen or hydrogen-containing gases
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    • Y02E50/30—Fuel from waste, e.g. synthetic alcohol or diesel

Abstract

公开并要求保护了用于由乙酸在加氢催化剂组合物上的气相反应以生成乙醇而选择性制备乙醇的方法。在本发明的实施方案中，乙酸和氢气在负载在石墨上的钴和钯或负载在二氧化硅上的钴和铂上的反应在气相中在约250℃的温度选择性制备了乙醇。

Description

使用钴催化剂由乙酸制备乙醇
本申请是申请日为2009年7月20日、申请号为200980134837.2、发明名称为“使用钴催化剂由乙酸制备乙醇”的发明专利申请的分案申请。
优先权
本申请基于2008年7月31日提交的相同名称的美国专利申请序列号12/221,239，由此要求其优先权，且其内容通过参考引入此处。
技术领域
本发明总的来讲涉及用于由乙酸制备乙醇的方法。更特别地，本发明涉及包括使用由负载在适合的催化剂载体上的钴构成并任选地包含一种或多种金属的催化剂对乙酸加氢以高选择性制备乙醇的方法。
背景技术
对经济上可行的用于将乙酸转化为乙醇的方法存在长期的迫切需要。乙醇是多种工业产品的重要商品原料，且还用作汽油的燃料添加剂。乙醇能够容易地脱水成为乙烯，然后能够将其转化为聚合物或小分子基的各种产品。乙醇传统上是由其价格波动变得更加显著的原料制备的。即天然气和原油价格的波动有助于传统上制备的石油、天然气或玉米或其它农产品来源的乙醇的成本波动，因此需要在石油价格和/或农产品价格升高时乙醇的全部(all the greater)可替代来源。
已经报道了能够由乙酸的加氢制备乙醇，但大多数这些方法具有一些商业操作的缺点。例如，美国专利号2,607,807公开了能够由乙酸在钌催化剂上在700-950巴的超高压力生成乙醇以达到约88％的产率，而在约200巴的压力仅得到约40％的低产率。然而，这两种条件都是商业操作不可接受和不经济的。
更近以来，已经报道了能够使用钴催化剂再次在超大气压力(例如约40-120巴)下由乙酸的加氢制备乙醇。例如参见授予Shuster等的美国专利号4,517,391。然而，此处公开的唯一实施例使用在约300巴范围内的反应压力，仍使该方法不适用于商业操作。此外，该方法要求包含不少于50wt％的钴以及选自由铜、锰、钼、铬和磷酸构成的组的一种或多种组分的催化剂，由此使得该方法经济上不可行。尽管公开了使用简单惰性催化剂载体以负载催化剂材料，但没有负载金属催化剂的具体实施例。
授予Kitson等的美国专利号5,149,680公开了用于使用铂族金属合金催化剂由羧酸及其酸酐催化加氢制备醇和/或酯的方法。该催化剂是由至少一种周期表的VIII族贵金属和至少一种能够与VIII族贵金属组成合金的金属的合金与包含金属铼、钨或钼的至少一种的组分混合组成的。尽管此处并未要求保护与现有技术对比实现了醇选择性的提高，但仍报道在其最适宜的催化剂条件下在乙酸加氢为乙醇的过程中生成了3-9％的烷烃(例如甲烷和乙烷)作为副产物。
授予Kitson等的美国专利号4,777,303描述了用于由羧酸加氢制备醇的方法。该例中所用的催化剂是非均相催化剂，包括是钼或钨的第一组分和是元素周期表的VIII族的贵金属的第二组分，任选地在载体(例如高表面积石墨化碳)上。报道乙醇和酯的组合混合物的选择性仅在约73-87％范围内，羧酸的低转化率为约16-58％。此外，未提供乙酸转化为乙醇的具体实施例。
授予Kitson等的美国专利号4,804,791描述了另一种用于由羧酸加氢制备醇的方法。在该方法中，通过将乙酸或丙酸在气相中在升高温度和在1-150巴的范围内的压力在包括作为必要组分的(i)元素周期表的VIII族贵金属；和(ii)铼且任选地在载体(例如高表面积石墨化碳)上的催化剂的存在下与氢气接触，从而由乙酸制备乙醇或由丙酸制备丙醇。该乙酸转化为乙醇的转化率在0.6％-69％范围内，乙醇的选择性在约6％-97％范围内。
综上所述，显然现有的方法都没有所需的乙醇选择性，或者现有技术使用的催化剂是昂贵的和/或对乙醇的生成不是选择性的并产生不希望的副产物。
发明内容
现在未曾预期地发现能够在工业规模上由乙酸以非常高的选择性和产率直接制备乙醇。更特别地，本发明提供了用于由乙酸选择性生成乙醇的方法，包括：在氢气存在下在适合的加氢催化剂上对乙酸加氢。适用于本发明的方法的催化剂是由负载在适合的催化剂载体上的约0.1wt％-约20wt％的钴与一种或多种选自由钯、铂、铑、钌、铼、铱、铬、铜、锡、钼、钨、钒和锌构成的组的金属催化剂相结合构成的。适合的催化剂载体包括但不局限于：二氧化硅、氧化铝、硅酸钙、二氧化硅-氧化铝、碳、氧化锆和氧化钛。
具体实施方式
下面参照多个仅用于举例和解释的实施方案对本发明进行详细描述。在后附权利要求中提出的本发明的精神和范围内对特别实施方案的改进对于本领域技术人员将是容易显而易见的。
除非下面有更特别的定义，此处所用的术语以其普通含义给出。除非另外指出，摩尔百分比(摩尔％或％)和类似的术语表示摩尔百分比。除非另外指出，重量百分比(wt％或％)和类似的术语表示重量百分比。
“转化率”表示为基于原料中的乙酸的摩尔百分比。乙酸(AcOH)的转化率是使用以下方程由气相色谱(GC)数据计算的：
Figure BDA0000095556550000031
“选择性”表示为基于转化的乙酸的摩尔百分比。例如，如果转化率为50摩尔％且有50摩尔％的转化的乙酸转化为乙醇，那么我们称乙醇的选择性为50％。乙醇(EtOH)的选择性是使用以下方程由气相色谱(GC)数据计算的：
Figure BDA0000095556550000041
催化剂金属的重量百分比是基于金属重量以及金属和载体的总干重的。
该反应依照以下化学方程进行：
Figure BDA0000095556550000042
依照本发明，乙酸转化为乙醇能够在多种构造中进行，例如如果需要，在单一反应区中，其可以为分层固定床。能够使用绝热反应器，或者能够使用具有传热介质的壳管式反应器。该固定床能够包括不同催化剂颗粒的混合物或者包括此处进一步描述的多种催化剂的催化剂颗粒。该固定床也可以包括组成反应物的混合区的颗粒材料层。将包括乙酸、氢和任选的惰性载气的反应混合物作为到达混合区的在压力下的物流供给该床。然后将该物流供给反应区或层(通过压力降低)。反应区包括催化组合物，催化组合物包含适合的加氢催化剂，其中将乙酸加氢以制备乙醇。根据反应器的类型、处理量需求等可以使用任意适合的粒度。
尽管在本发明的方法中在将乙酸加氢生成乙醇中能够使用本领域技术人员已知的各种加氢催化剂，但优选所用的加氢催化剂包含在适合的催化剂载体上的约0.1wt％-约20wt％的钴。如前所述，进一步优选适用于本发明的方法的催化剂任选地包含负载在同一催化剂载体上的第二和/或第三金属。可以非限定性地提及以下金属作为适用作第二和/或第三金属的那些金属：钯、铂、铑、钌、铼、铱、铬、铜、锡、钼、钨、钒、锌及其混合物。典型地，优选能够使用在适合载体上的钴与至少一种其它金属的组合作为加氢催化剂。因此，特别优选钴与钯或铂的组合。类似地，钴与钌、铬或钒的组合也是优选的。能够与钴一起使用作为第三金属的金属实例非限定性地包括上面所列的其它任意金属，例如铑、铱、铜、锡、钼、和锌。
现有技术中已知的各种催化剂载体都能够用于负载本发明的催化剂。这种载体的实例包括但不局限于：沸石、氧化铁、二氧化硅、氧化铝、氧化钛、氧化锆、二氧化硅-氧化铝、氧化镁、硅酸钙、碳、石墨及其混合物。优选的载体是二氧化硅、氧化铝、硅酸钙、碳、氧化锆和氧化钛。更优选使用二氧化硅作为本发明的方法中的催化剂载体。还重要地指出二氧化硅的纯度越高，其优选作为本发明的载体越好。另一种优选的催化剂载体是硅酸钙。
在本发明的另一实施方案中，该优选的催化剂载体是碳。现有技术中已知适用作催化剂载体的各种形式的碳都能够用于本发明的方法中。特别优选的碳载体是石墨化碳，特别是英国专利号2,136,704中所述的高表面积石墨化碳。该碳优选是颗粒状的，例如作为粒料。碳颗粒的尺寸将取决于任意给定反应器中可接受的压降(其给出最小粒料尺寸)和粒料内反应物的扩散限制(其给出粒料尺寸)。
适用于本发明的方法中的碳催化剂载体优选是多孔碳催化剂载体。具有该优选的粒度，该碳将需要是多孔的以满足优选的表面积特征。
包括碳催化剂载体的催化剂载体可以由其BET、基面和边缘表面积表征。该BET表面积是使用Brunauer Emmett and Teller J.Am.Chem.Soc.60，309(1938)的方法由氮气吸附测定的表面积。基面表面积是通过Proc.Roy.Soc.A314第473-498页(特别参照第489页)中所述的方法由正三十二烷从正庚烷吸附在碳上的吸附热测定的表面积。边缘表面积(edge surface area)是如上述Proc.Roy.Soc.文章中特别参照第495页公开的由正丁醇从正庚烷吸附在碳上的吸附热测定的表面积。
优选用于本发明的碳催化剂载体具有至少100m2/g的BET表面积，更优选至少200m2/g，最优选至少300m2/g。该BET表面积优选不大于1000m2/g，更优选不大于750m2/g。
该优选的碳载体可以由含碳原料的热处理制备。该原料可以是亲油石墨，例如如英国专利号1,168,785中所述制备的，或者可以是碳黑。
然而，亲油石墨包含薄片形式的非常微细的颗粒形式的碳，因此并不是非常适用作催化剂载体的材料。申请人优选避免使用它们。类似的考虑适用于也具有非常微细粒度的碳黑。
优选的材料是源自植物材料(例如椰子木炭)或源自泥煤或煤或源自可碳化的聚合物的活性炭。该材料经过热处理优选具有不小于上述优选用于碳载体的那些的粒度。
优选的原料具有以下特征：BET表面积至少100，更优选至少500m2/g。
用于制备具有所限定特征的碳载体的优选热处理程序包括连续的以下：(1)在惰性气氛中在900℃-3300℃的温度加热该碳；(2)在300℃-1200℃的温度氧化该碳；(3)在惰性气氛中在900℃-3000℃的温度加热。
在使用氧气(例如作为空气)作为氧化剂时，该氧化步骤优选在300℃-600℃的温度进行。
在惰性气体中的加热持续时间并不严格。加热该碳到所需的最大温度所需的时间是足以在该碳中产生所需的改变。
该氧化步骤显然不能在使得该碳完全燃烧的条件下进行。其优选使用气态氧化剂以受控速率进料从而避免过度氧化。气态氧化剂的实例是蒸汽、二氧化碳和包含分子氧的气体(例如空气)。该氧化优选进行以给出基于经过该氧化步骤的碳重量的至少10wt％的碳重量损失，更优选至少15wt％。
该重量损失优选不大于经过该氧化步骤的碳的40wt％，更优选不大于该碳的25wt％。
氧化剂的供给速率优选使得所需的重量损失发生至少2小时，更优选至少4小时。
在需要惰性气氛的情况下，其可以由氮气或惰性气体提供。
如上所述，在该催化剂载体上钴的负载量水平通常在约0.1wt％-约20wt％的范围内。在载体上的第二或第三金属的负载量在本发明中并不非常严格，能够在约0.1wt％-约10wt％范围内变化。特别优选基于载体重量约1wt％-约6wt％的金属负载量。因此，例如在包含约4-12wt％钴的石墨上负载0.5-2wt％钯是特别优选的催化剂。类似地，在包含约4-12wt％钴的高纯度二氧化硅上负载0.5-2wt％铂的催化剂也是特别优选的催化剂。
如上所述，能够优选用作与钴一起使用的第二金属的其它金属包括钌、铬和钒。在各种这些实例中，具有约0.5-2wt％的第二金属(即钌、铬或钒)的负载量的4-12wt％钴负载量是优选的。如果使用第三金属，其负载量也能够在约0.5wt％-约2wt％范围内，然而，根据所用的金属和催化剂载体的类型，也能够使用更高的金属负载量水平。
能够使用本领域中任意已知方法进行金属浸渍。典型地，在浸渍之前，将该载体在120℃干燥并成型为具有在约0.2-0.4mm范围内的粒度分布的颗粒。任选地，可以将该载体挤压、压碎并筛分到所需的粒度分布。能够使用任意已知的用于将该载体材料成型为所需粒度分布的方法。
对于具有低表面积的载体，例如α-氧化铝，过量添加金属溶液直至完全润湿或过量液体浸渍以得到所需的金属负载量。
如上所述，本发明的方法中所用的加氢催化剂至少是具有钴作为主金属的双金属加氢催化剂。通常，尽管不意于被任何理论所束缚，认为一种金属用作促进剂金属，而另一种金属是主金属。例如，在本发明的方法中，钴被认为是用于制备本发明的加氢催化剂的主金属。该主金属能够与促进剂金属(例如钨、钒、钼、铬或锌)相结合。然而，应当指出有时主金属也用作促进剂金属或反之亦然。例如，当使用铁作为主金属时，镍能够用作促进剂金属。类似地，铬能够与铜相结合用作主金属(即Cu-Cr作为主双金属)，其能够进一步与促进剂金属(例如铈、镁或锌)相结合。
该双金属催化剂通常是在两个步骤中浸渍的。首先添加“促进剂”金属，然后添加“主”金属。各浸渍步骤之后是干燥和煅烧。该双金属催化剂也可以通过共浸渍制备。在上述含Cu/Cr的三金属催化剂的情况中，可以使用顺序浸渍，开始添加“促进剂”金属。第二浸渍步骤可以包括两种主要金属(即Cu和Cr)的共浸渍。例如，Cu-Cr-Co在SiO2上可以由以下制备：首先浸渍硝酸铬，然后共浸渍硝酸铜和钴。再次，各浸渍之后是干燥和煅烧。在大多数情况中，该浸渍可以使用金属硝酸盐溶液进行。然而，也能够使用一旦煅烧就会释放出金属离子的各种其它可溶盐。其它适用于浸渍的金属盐的实例包括金属氢氧化物、金属氧化物、金属乙酸盐、铵基金属氧化物(例如七钼酸铵六水合物)、金属酸(例如高铼酸溶液)、金属草酸盐等。
因此在本发明的一种实施方案中，提供了加氢催化剂，其中该催化剂载体是石墨，具有钴和钯的双金属负载。在本发明的该方面中，钴的负载量为约10wt％，钯的负载量为约1wt％。如果需要，也能够使用5wt％的钴负载量水平和0.5wt％的钯负载量水平。
在本发明的另一实施方案中，另外提供了加氢催化剂，其中催化剂载体是高纯度的二氧化硅，具有钴和铂的双金属负载。在本发明的该方面中，钴的负载量为约10wt％，铂的负载量为约1wt％。再次在本发明的该方面中，也能够使用5wt％的钴负载量水平和0.5wt％的铂负载量水平。
通常，通过实施本发明，乙酸能够以非常高的速率选择性地转化为乙醇。乙醇的选择性通常非常高，且可能为至少40％。在优选的反应条件下，在约60％的选择性下或更优选在至少80％的选择性下，乙酸选择性转化为乙醇。最优选乙醇的选择性为至少95％。
在本发明的方法的另一方面，该加氢是在刚好足以克服沿催化床的压降的压力下进行的。
该反应可以在多种条件下在气态或液态中进行。优选地，该反应在气相中进行。可以使用的反应温度例如在约200℃-约300℃，优选约225℃-约275℃的范围内。压力通常对该反应不是关键的，可以使用低于大气压、大气压或高于大气压。然而，在大多数情况中，该反应的压力将在约1-30大气压的绝对压力范围内，最优选反应区的压力在约10-25大气压的绝对压力范围内。
尽管该反应每摩尔乙酸消耗2摩尔氢气生成1摩尔乙醇，但进料流中的乙酸∶氢气的实际摩尔比可以在宽限制内变化，例如约100∶1-1∶100。然而，优选该比例在约1∶20-1∶2范围内。更优选地，乙酸与氢气的摩尔比为约1∶5。
与本发明的方法结合使用的原料可以来自任意适合的来源，包括天然气、石油、煤、生物质等。通过甲醇羰基化、乙醛氧化、乙烯氧化、氧化发酵和厌氧发酵等制备乙酸是公知的。因为石油和天然气变得更加昂贵，因此由可替代的碳源制备乙酸和中间产物(例如甲醇和一氧化碳)的方法获得了更多的关注。受到特别关注的是由可以来自任意适合的碳源的合成气制备乙酸。例如授予Vidalin的美国专利号6,232,352(其公开内容通过参考引入此处)教导了改装甲醇装置用于制备乙酸的方法。通过改装甲醇装置，显著降低或大大消除了与新型乙酸装置的CO产生相关的大的资金成本。该合成气的所有或部分是由甲醇合成回路分流而来的且被送往分离器装置以回收CO和氢气，其然后用于制备乙酸。除乙酸之外，该方法也能够用于制备与本发明相关使用的氢气。
Steinberg等的美国专利号RE35,377(也通过参考引入此处)提供了通过转化碳质材料(例如油、煤、天然气和生物质材料)制备甲醇的方法。该方法包括将固体和/或液体碳质材料加氢气化以得到工艺气体，用另外的天然气将其蒸汽热解以生成合成气。将该合成气转化为甲醇，可以将其羰基化为乙酸。该方法同样产生了可以如上所述与本发明结合使用的氢气。也参见Grady等的美国专利号5,821,111，其公开了用于将废生物质通过气化转化为合成气的方法，以及Kindig等的美国专利号6,685,754，其公开内容通过参考引入此处。
可以在反应温度将该乙酸气化，然后将其与氢气一起以未稀释状态或用较为惰性的载气(例如氮气、氩气、氦气、二氧化碳等)稀释供给。
可替代地，蒸气形式的乙酸可以直接取自Scates等的美国专利号6,657,078中描述的一类甲醇羰基化装置的闪蒸容器的粗产物，其公开内容通过参考引入此处。可以直接将该粗蒸气产物供给本发明的反应区，而不需要冷凝该乙酸和轻馏分或除水，节省总体方法成本。
接触或停留时间也能够根据一些变量(例如乙酸的量、催化剂、反应器、温度和压力)广泛变化。当使用非固定床的催化剂系统时，典型的接触时间在几分之一秒到超过几小时的范围内变化，优选的接触时间至少对于气相反应为约0.5-100秒。
典型地，该催化剂用于固定床反应器中，例如在细长管道或管子的形状中，其中典型地为蒸气形式的反应物在催化剂上通过或穿过催化剂。如果需要，也能够使用其它反应器，例如流化床或沸腾床反应器。在一些情况中，有利地使用该加氢催化剂与惰性材料相结合以调节该催化剂床中的压降、流量、热平衡或其它过程参数，包括反应物化合物与该催化剂颗粒的接触时间。
在一种优选实施方案中，还提供了用于由乙酸选择性直接生成乙醇的方法，包括：将包含乙酸和氢气的进料流在升高温度与适合的加氢催化剂接触，所述加氢催化剂包含在适合的催化剂载体上的约1wt％-约15wt％钴和负载在所述载体上的第二金属，其中所述第二金属选自由钯、铂、铜、锡、钼和钨构成的组。
在本发明的方法的该实施方案中，优选的加氢催化剂包含约1wt％的钯或铂和约10wt％的钴。在本发明的方法的该实施方案中，优选加氢催化剂在固定床中是分层的，且反应是使用摩尔比为约1∶20-1∶2的乙酸和氢气的进料流在范围为约225℃-275℃的温度和在约10-25大气压绝对压力范围内的反应区压力下在气相中进行的，反应物的接触时间在约0.5-100秒范围内。
以下实施例描述了用于制备在本发明的方法中使用的各种催化剂的程序。
实施例A
制备10wt％钴和1wt％钯在石墨上
在烘箱中在氮气气氛下在120℃对经磨粉和筛分的具有约0.2mm的均匀粒度分布的石墨(100g)干燥整晚，然后冷却到室温。向其中添加硝酸钯(Heraeus)(2.2g)在蒸馏水(22ml)中的溶液。将所得到的浆液在逐渐加热到110℃(＞2小时，10℃/min)的烘箱中干燥。然后将经浸渍的催化剂混合物在500℃煅烧(6小时，1℃/min)。向该经煅烧和冷却的材料中添加硝酸钴六水合物(49.4g)在蒸馏水(50ml)中的溶液。将所得到的浆液在逐渐加热到110℃(＞2小时，10℃/min)的烘箱中干燥。然后将经浸渍的催化剂混合物在500℃煅烧(6小时，1℃/min)。
实施例B
制备5wt％钴和0.5wt％钯在石墨上
在烘箱中在氮气气氛下在120℃对经磨粉和筛分的具有约0.2mm的均匀粒度分布的石墨(100g)干燥整晚，然后冷却到室温。向其中添加硝酸钯(Heraeus)(1.1g)在蒸馏水(11ml)中的溶液。将所得到的浆液在逐渐加热到110℃(＞2小时，10℃/min)的烘箱中干燥。然后将经浸渍的催化剂混合物在500℃煅烧(6小时，1℃/min)。向该经煅烧和冷却的材料中添加硝酸钴六水合物(24.7g)在蒸馏水(25ml)中的溶液。将所得到的浆液在逐渐加热到110℃(＞2小时，10℃/min)的烘箱中干燥。然后将经浸渍的催化剂混合物在500℃煅烧(6小时，1℃/min)。
实施例C
制备10wt％钴和1wt％铂在高纯度二氧化硅上
在烘箱中在氮气气氛下在120℃对经磨粉和筛分的具有约0.2mm的均匀粒度分布的高纯度二氧化硅(100g)干燥整晚，然后冷却到室温。向其中添加硝酸铂(Chempur)(1.64g)在蒸馏水(16ml)中的溶液。将所得到的浆液在逐渐加热到110℃(＞2小时，10℃/min)的烘箱中干燥。然后将经浸渍的催化剂混合物在500℃煅烧(6小时，1℃/min)。向该经煅烧和冷却的材料中添加硝酸钴六水合物(49.4g)在蒸馏水(50ml)中的溶液。将所得到的浆液在逐渐加热到110℃(＞2小时，10℃/min)的烘箱中干燥。然后将经浸渍的催化剂混合物在500℃煅烧(6小时，1℃/min)。
实施例D
制备10wt％钴和1wt％铂在硅酸钙上
在烘箱中在氮气气氛下在120℃对经磨粉和筛分的具有约0.2mm的均匀粒度分布的硅酸钙(100g)干燥整晚，然后冷却到室温。向其中添加硝酸铂(Chempur)(1.64g)在蒸馏水(16ml)中的溶液。将所得到的浆液在逐渐加热到110℃(＞2小时，10℃/min)的烘箱中干燥。然后将经浸渍的催化剂混合物在500℃煅烧(6小时，1℃/min)。向该经煅烧和冷却的材料中添加硝酸钴六水合物(49.4g)在蒸馏水(50ml)中的溶液。将所得到的浆液在逐渐加热到110℃(＞2小时，10℃/min)的烘箱中干燥。然后将经浸渍的催化剂混合物在500℃煅烧(6小时，1℃/min)。
实施例E
制备10wt％钴和1wt％铬在石墨上
在烘箱中在氮气气氛下在120℃对经磨粉和筛分的具有约0.2mm的均匀粒度分布的石墨(100g)干燥整晚，然后冷却到室温。向其中添加硝酸铬九水合物(Alfa Aesar)(6.5g)在蒸馏水(13ml)中的溶液。将所得到的浆液在逐渐加热到110℃(＞2小时，10℃/min)的烘箱中干燥。然后将经浸渍的催化剂混合物在500℃煅烧(6小时，1℃/min)。向该经煅烧和冷却的材料中添加硝酸钴六水合物(49.4g)在蒸馏水(50ml)中的溶液。将所得到的浆液在逐渐加热到110℃(＞2小时，10℃/min)的烘箱中干燥。然后将经浸渍的催化剂混合物在500℃煅烧(6小时，1℃/min)。
产物的气相色谱(GC)分析
用在线GC进行产物的分析。使用装备有1个火焰离子检测器(FID)和2个热传导检测器(TCD)的三通道小型GC分析反应物和产物。前通道装备有FID和CP-Sil 5(20m)+WaxFFap(5m)柱并用于定量以下：
乙醛
乙醇
丙酮
乙酸甲酯
乙酸乙烯酯
乙酸乙酯
乙酸
乙二醇二乙酸酯
乙二醇
亚乙基二乙酸酯
三聚乙醛
中通道装备有TCD和Porabond Q柱并用于定量：
CO2
乙烯
乙烷
后通道装备有TCD和Molsieve 5A柱并用于定量：
氦气
氢气
氮气
甲烷
一氧化碳
在反应之前，通过用单一化合物形成尖峰测定不同组分的保留时间，用已知组成的校准气体或用已知组成的液体溶液校准该GC。这可以测定各种组分的响应因子。
实施例1
所用的催化剂是依照实施例A的程序制备的10wt％钴和1wt％钯在石墨上。
在具有30mm的内径并能够提升到受控温度的由不锈钢制成的管状反应器中，设置50ml石墨上的10wt％钴和1wt％钯。装载之后催化剂床的长度约为70mm。
进料液体基本上由乙酸构成。将该反应进料液体蒸发并与氢气和作为载气的氦气一起以约2500hr-1的平均组合气时空速(GHSV)在约250℃的温度和22巴的压力下加入该反应器中。所得到的进料流包含约4.4％-约13.8％的乙酸摩尔百分比和约14％-约77％的氢气摩尔百分比。蒸气流出物的一部分通过气相色谱，用于分析该流出物的含量。在乙酸转化率为18.5％下，乙醇选择性为97.5％。
实施例2
所用的催化剂是依照实施例B的程序制备的5wt％钴和0.5wt％铂在石墨上。
以蒸发的乙酸和氢气的进料流的2500hr-1的平均组合气时空速(GHSV)在225℃的温度和22巴的压力基本重复实施例1中提出的程序。蒸气流出物的一部分通过气相色谱，用于分析该流出物的含量。乙酸转化率为20％，乙醇选择性为95％。
实施例3
所用的催化剂是依照实施例C的程序制备的10wt％钴和1wt％铂在高纯度二氧化硅上。
以蒸发的乙酸和氢气的进料流的2500hr-1的平均组合气时空速(GHSV)在250℃的温度和22巴的压力基本重复实施例1中提出的程序。蒸气流出物的一部分通过气相色谱，用于分析该流出物的含量。乙酸转化率为71％，乙醇选择性为96％。
实施例4
所用的催化剂是依照实施例D的程序制备的10wt％钴和1wt％铂在硅酸钙上。
以蒸发的乙酸和氢气的进料流的2500hr-1的平均组合气时空速(GHSV)在250℃的温度和22巴的压力基本重复实施例1中提出的程序。蒸气流出物的一部分通过气相色谱，用于分析该流出物的含量。乙酸转化率为50％，乙醇选择性为94％。
实施例5
所用的催化剂是依照实施例E的程序制备的10wt％钴和1wt％铬在石墨上。
以蒸发的乙酸和氢气的进料流的2500hr-1的平均组合气时空速(GHSV)在250℃的温度和22巴的压力基本重复实施例1中提出的程序。蒸气流出物的一部分通过气相色谱，用于分析该流出物的含量。乙酸转化率为38％，乙醇选择性为96％。
尽管已经结合特别实施例描述了本发明，但在本发明的精神和范围内的对这些实施例的改变对于本领域技术人员将是容易显而易见的。鉴于以上讨论，上面结合背景技术和发明详述所讨论的其公开内容全部通过参考引入此处的现有技术和参考文献的相关知识，相信不需要进一步的描述。

Claims (15)

1.用于由碳源选择性直接生成乙醇的方法，包括：
(a)将碳源转化为乙酸；和
(b)将蒸气形式的包含乙酸和氢气的进料流在升高温度与适合的加氢催化剂接触，所述加氢催化剂包含在适合的催化剂载体上的约0.1wt％-约20wt％的钴和任选的负载在所属载体上的第二或第三金属，其中所述第二或第三金属选自由以下构成的组：钯、铂、铑、钌、铼、铱、铬、铜、锡、钼、钨、钒和锌。
2.权利要求1的方法，其中任选的第二或第三金属选自钯、铂和铬。
3.权利要求1的方法，其中任选的第二或第三金属选自钯、铂、铜、锡、钼和钨。
4.权利要求1-3任一项的方法，其中加氢催化剂还包含选自铑、铱、铜、锡、钼和锌的第三金属。
5.权利要求1-3任一项的方法，其中该催化剂载体选自二氧化硅、氧化铝、二氧化硅-氧化铝、硅酸钙、碳、氧化锆、氧化钛及其组合。
6.权利要求1-3任一项的方法，其中消耗的乙酸的至少约80重量％转化为乙醇。
7.权利要求1-3任一项的方法，其中所述碳源选自天然气、石油和煤。
8.权利要求1-3任一项的方法，其中所述碳源是生物质。
9.权利要求8的方法，其中将生物质转化为乙酸包括以下步骤：
(i)将所述生物质转化为包含合成气的第一物流；
(ii)将至少一些所述合成气催化转化为包含甲醇的第二物料；
(iii)将一些所述合成气分离成氢气和一氧化碳；和
(iv)将至少一些所述甲醇与一些所述一氧化碳催化转化为包含乙酸的第三物流，和其中所述接触包括用一些所述氢气将至少一些乙酸还原成包含乙醇的第四物流。
10.权利要求1-3任一项的方法，还包括将碳源转化为甲醇和将甲醇转化为乙酸，其中所述接触包括将至少一些乙酸还原成乙醇。
11.权利要求1-3任一项的方法，还包括将碳源转化为合成气，将至少一些合成气转化为甲醇，和将甲醇转化为乙酸，其中所述接触包括将至少一些乙酸物流还原成乙醇。
12.权利要求1-3任一项的方法，还包括将碳源转化为合成气，将一部分合成气分离成氢气物流和一氧化碳物流，使一部分一氧化碳物流与甲醇反应成乙酸，其中所述接触包括用一些所述氢气物流将至少一些乙酸还原成乙醇。
13.权利要求1-3任一项的方法，还包括将碳源转化为合成气，将一部分合成气分离成氢气物流和一氧化碳物流，将至少一些合成气转化为甲醇，使一部分一氧化碳物流与一部分甲醇反应成乙酸，其中所述接触包括用一些所述氢气物流将至少一些乙酸还原成乙醇。
14.权利要求1-3任一项的方法，其中反应物由摩尔比在100∶1-1∶100的范围内的乙酸和氢气构成，反应区的压力在1-30大气压绝对压力的范围内。
15.权利要求1-3任一项的方法，其中该催化剂载体包含Pt/Sn重量比在0.1-2的范围内的铂和锡的组合。
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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106995363A (zh) * 2016-01-25 2017-08-01 河南顺达化工科技有限公司 一种醋酸加氢耦合制备乙醇的工艺

Families Citing this family (236)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8268604B2 (en) * 2007-12-20 2012-09-18 Abbott Point Of Care Inc. Compositions for forming immobilized biological layers for sensing
US8241697B2 (en) 2007-12-20 2012-08-14 Abbott Point Of Care Inc. Formation of immobilized biological layers for sensing
US8304586B2 (en) 2010-02-02 2012-11-06 Celanese International Corporation Process for purifying ethanol
US8338650B2 (en) 2008-07-31 2012-12-25 Celanese International Corporation Palladium catalysts for making ethanol from acetic acid
US8309772B2 (en) * 2008-07-31 2012-11-13 Celanese International Corporation Tunable catalyst gas phase hydrogenation of carboxylic acids
US7816565B2 (en) 2008-07-31 2010-10-19 Celanese International Corporation Direct and selective production of acetaldehyde from acetic acid utilizing a supported metal catalyst
US8546622B2 (en) 2008-07-31 2013-10-01 Celanese International Corporation Process for making ethanol from acetic acid using acidic catalysts
US8309773B2 (en) 2010-02-02 2012-11-13 Calanese International Corporation Process for recovering ethanol
US8471075B2 (en) 2008-07-31 2013-06-25 Celanese International Corporation Processes for making ethanol from acetic acid
US8637714B2 (en) 2008-07-31 2014-01-28 Celanese International Corporation Process for producing ethanol over catalysts containing platinum and palladium
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
US8680317B2 (en) 2008-07-31 2014-03-25 Celanese International Corporation Processes for making ethyl acetate from acetic acid
US8501652B2 (en) 2008-07-31 2013-08-06 Celanese International Corporation Catalysts 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
US8178715B2 (en) 2008-12-31 2012-05-15 Celanese International Corporation Integrated process for the production of vinyl acetate from acetic acid via acetaldehyde
US8450535B2 (en) 2009-07-20 2013-05-28 Celanese International Corporation Ethanol production from acetic acid utilizing a cobalt catalyst
US8710277B2 (en) 2009-10-26 2014-04-29 Celanese International Corporation Process for making diethyl ether from acetic acid
US8680321B2 (en) 2009-10-26 2014-03-25 Celanese International Corporation Processes for making ethanol from acetic acid using bimetallic catalysts
AU2010313767A1 (en) * 2009-10-26 2012-05-17 Celanese International Corporation Processes for making ethanol from acetic acid
AU2010315554A1 (en) 2009-10-26 2012-05-17 Celanese International Corporation Process for making ethanol from acetic acid using acidic catalysts
CN102333588B (zh) * 2009-10-26 2014-04-09 国际人造丝公司 用于由乙酸制备乙醇的催化剂
US8211821B2 (en) 2010-02-01 2012-07-03 Celanese International Corporation Processes for making tin-containing catalysts
US8394984B2 (en) 2010-02-02 2013-03-12 Celanese International Corporation Process for producing an ethyl acetate solvent and co-production of ethanol
WO2012039840A2 (en) 2010-02-02 2012-03-29 Celanese International Corporation Processes for producing alcohols from a mixed acid feed
US8314272B2 (en) 2010-02-02 2012-11-20 Celanese International Corporation Process for recovering ethanol with vapor separation
BR112012019310A2 (pt) 2010-02-02 2018-05-08 Celanese Int Corp processos para purificação de etanol
WO2012039841A1 (en) 2010-02-02 2012-03-29 Celanese International Corporation Integrated process for producing alcohols from a mixed acid feed
WO2011097222A2 (en) 2010-02-02 2011-08-11 Celanese International Corporation Processes for producing ethanol from acetaldehyde
EP2531477A2 (en) * 2010-02-02 2012-12-12 Celanese International Corporation Process for purifying a crude ethanol product
US8460405B2 (en) * 2010-02-02 2013-06-11 Celanese International Corporation Ethanol compositions
WO2011097217A2 (en) 2010-02-02 2011-08-11 Celanese International Corporation Processes for producing denatured ethanol
US8575403B2 (en) 2010-05-07 2013-11-05 Celanese International Corporation Hydrolysis of ethyl acetate in ethanol separation process
US8680343B2 (en) 2010-02-02 2014-03-25 Celanese International Corporation Process for purifying ethanol
CA2787419A1 (en) 2010-02-02 2011-08-11 Celanese International Corporation Preparation and use of a catalyst for producing ethanol comprising a crystalline support modifier
US8318988B2 (en) 2010-05-07 2012-11-27 Celanese International Corporation Process for purifying a crude ethanol product
US8552224B2 (en) 2010-05-07 2013-10-08 Celanese International Corporation Processes for maximizing ethanol formation in the hydrogenation of acetic acid
US8394985B2 (en) * 2010-02-02 2013-03-12 Celanese International Corporation Process for producing an ester feed stream for esters production and co-production of ethanol
WO2011097220A2 (en) 2010-02-02 2011-08-11 Celanese International Corporation Process for producing ethanol using an extractive distillation column
US8858659B2 (en) 2010-02-02 2014-10-14 Celanese International Corporation Processes for producing denatured ethanol
US8541633B2 (en) 2010-02-02 2013-09-24 Celanese International Corporation Processes for producing anhydrous ethanol compositions
US8344186B2 (en) 2010-02-02 2013-01-01 Celanese International Corporation Processes for producing ethanol from acetaldehyde
US8728179B2 (en) 2010-02-02 2014-05-20 Celanese International Corporation Ethanol compositions
US8747492B2 (en) 2010-02-02 2014-06-10 Celanese International Corporation Ethanol/fuel blends for use as motor fuels
US8668750B2 (en) 2010-02-02 2014-03-11 Celanese International Corporation Denatured fuel ethanol compositions for blending with gasoline or diesel fuel for use as motor fuels
WO2011097193A2 (en) 2010-02-02 2011-08-11 Celanese International Corporation Hydrolysis of ethyl acetate in ethanol separation process
US8932372B2 (en) 2010-02-02 2015-01-13 Celanese International Corporation Integrated process for producing alcohols from a mixed acid feed
US8552226B2 (en) 2010-02-02 2013-10-08 Celanese International Corporation Process for heat integration for ethanol production and purification process
US8222466B2 (en) 2010-02-02 2012-07-17 Celanese International Corporation Process for producing a water stream from ethanol production
US8552225B2 (en) 2010-02-02 2013-10-08 Celanese International Corporation Process for vaporizing acetic acid for hydrogenation processes to produce ethanol
WO2011140477A2 (en) 2010-05-07 2011-11-10 Celanese International Corporation Process for separating acetaldehyde from ethanol-containing mixtures
US8704011B2 (en) 2010-05-07 2014-04-22 Celanese International Corporation Separating ethanol and ethyl acetate under low pressure conditions
US8569551B2 (en) 2010-05-07 2013-10-29 Celanese International Corporation Alcohol production process integrating acetic acid feed stream comprising water from carbonylation process
US8680342B2 (en) 2010-05-07 2014-03-25 Celanese International Corporation Process for recovering alcohol produced by hydrogenating an acetic acid feed stream comprising water
US8754267B2 (en) 2010-05-07 2014-06-17 Celanese International Corporation Process for separating acetaldehyde from ethanol-containing mixtures
US8604255B2 (en) 2010-05-07 2013-12-10 Celanese International Corporation Process for recovering ethanol with sidedraws to regulate C3+ alcohols concentrations
US8575404B2 (en) 2010-05-07 2013-11-05 Celanese International Corporation Process for recycling gas from acetic acid hydrogenation
US8704010B2 (en) 2010-05-07 2014-04-22 Celanese International Corporation Alcohol production process with impurity removal
US8859827B2 (en) 2011-11-18 2014-10-14 Celanese International Corporation Esterifying acetic acid to produce ester feed for hydrogenolysis
US8846988B2 (en) 2010-07-09 2014-09-30 Celanese International Corporation Liquid esterification for the production of alcohols
AU2011274524A1 (en) 2010-07-09 2012-11-15 Celanese International Corporation Finishing reactor for purifying ethanol
US9272970B2 (en) 2010-07-09 2016-03-01 Celanese International Corporation Hydrogenolysis of ethyl acetate in alcohol separation processes
US8884080B2 (en) 2010-07-09 2014-11-11 Celanese International Corporation Reduced energy alcohol separation process
US9126125B2 (en) 2010-07-09 2015-09-08 Celanese International Corporation Reduced energy alcohol separation process having water removal
US8846986B2 (en) 2011-04-26 2014-09-30 Celanese International Corporation Water separation from crude alcohol product
US8809597B2 (en) 2010-07-09 2014-08-19 Celanese International Corporation Separation of vapor crude alcohol product
US9150474B2 (en) 2010-07-09 2015-10-06 Celanese International Corporation Reduction of acid within column through esterification during the production of alcohols
WO2012148509A1 (en) 2011-04-26 2012-11-01 Celanese International Corporation Process for producing ethanol using a stacked bed reactor
US20120010445A1 (en) 2010-07-09 2012-01-12 Celanese International Corporation Low Energy Alcohol Recovery Processes
US8536384B2 (en) 2010-07-09 2013-09-17 Celanese International Corporation Recovering ethanol sidedraw by separating crude product from hydrogenation process
US8710279B2 (en) 2010-07-09 2014-04-29 Celanese International Corporation Hydrogenolysis of ethyl acetate in alcohol separation processes
US8664454B2 (en) 2010-07-09 2014-03-04 Celanese International Corporation Process for production of ethanol using a mixed feed using copper containing catalyst
US8901358B2 (en) 2010-07-09 2014-12-02 Celanese International Corporation Esterification of vapor crude product in the production of alcohols
US8710280B2 (en) 2010-07-09 2014-04-29 Celanese International Corporation Weak acid recovery system for ethanol separation processes
BR112012066480A2 (pt) * 2010-08-06 2019-09-24 Celanese Int Corp composições de etanol
BR112012033297A2 (pt) 2010-08-06 2016-11-22 Celanese Int Corp misturas de etanol/combustível para uso como combustíveis para motor
CN102811990B (zh) 2010-08-06 2015-05-27 国际人造丝公司 用于与汽油或柴油燃料调合用作发动机燃料的变性燃料乙醇组合物
US8678715B2 (en) 2010-11-15 2014-03-25 B&J Rocket America, Inc. Air cooled spacer for multi-blade abrading wheel
US20120253084A1 (en) 2011-04-01 2012-10-04 Celanese International Corporation Vent scrubbers for use in production of ethanol
US8350098B2 (en) 2011-04-04 2013-01-08 Celanese International Corporation Ethanol production from acetic acid utilizing a molybdenum carbide catalyst
CN102229520B (zh) * 2011-04-25 2013-12-11 江苏索普（集团）有限公司 一种由醋酸气相加氢制备乙醇的方法
US8927784B2 (en) 2011-04-26 2015-01-06 Celanese International Corporation Process to recover alcohol from an ethyl acetate residue stream
US8884081B2 (en) 2011-04-26 2014-11-11 Celanese International Corporation Integrated process for producing acetic acid and alcohol
WO2012149156A2 (en) 2011-04-26 2012-11-01 Celanese International Corporation Process to reduce ethanol recycled to hydrogenation 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
US8927787B2 (en) 2011-04-26 2015-01-06 Celanese International Corporation Process for controlling a reboiler during alcohol recovery and reduced ester formation
US8927780B2 (en) 2011-04-26 2015-01-06 Celanese International Corporation Process for removing aldehydes from ethanol reaction mixture
WO2012149135A2 (en) 2011-04-26 2012-11-01 Celanese International Corporation Using a dilute acid stream as an extractive agent
US9024084B2 (en) 2011-04-26 2015-05-05 Celanese International Corporation Reduced energy alcohol separation process having controlled pressure
US9024082B2 (en) 2011-04-26 2015-05-05 Celanese International Corporation Using a dilute acid stream as an extractive agent
US8748675B2 (en) 2011-06-16 2014-06-10 Celanese International Corporation Extractive distillation of crude alcohol product
US9073816B2 (en) 2011-04-26 2015-07-07 Celanese International Corporation Reducing ethyl acetate concentration in recycle streams for ethanol production processes
US8686200B2 (en) 2011-04-26 2014-04-01 Celanese International Corporation Process to recover alcohol from an acidic residue stream
US8592635B2 (en) 2011-04-26 2013-11-26 Celanese International Corporation Integrated ethanol production by extracting halides from acetic acid
TW201242936A (en) 2011-04-26 2012-11-01 Celanese Int Corp Process for producing ethanol and reducing acetic acid concentration
US8927788B2 (en) 2011-04-26 2015-01-06 Celanese International Corporation Process to recover alcohol with reduced water from overhead of acid column
US8686199B2 (en) 2011-04-26 2014-04-01 Celanese International Corporation Process for reducing the concentration of acetic acid in a crude alcohol product
US8933278B2 (en) 2011-04-26 2015-01-13 Celanese International Corporation Process for producing ethanol and reducing acetic acid concentration
MX2013012537A (es) 2011-04-26 2013-12-02 Celanese Int Corp Reduccion de acido dentro de la columna a traves de la esterificacion durante la produccion de alcoholes.
WO2012149148A1 (en) 2011-04-26 2012-11-01 Celanese International Corporation Extractive distillation of crude ethanol
WO2012148465A1 (en) 2011-04-26 2012-11-01 Celanese International Corporation Recovering ethanol with sidestreams to regulate c3+ alcohols concentrations
TW201249790A (en) 2011-04-26 2012-12-16 Celanese Int Corp Reduced energy alcohol separation process having controlled pressure
US9000232B2 (en) 2011-04-26 2015-04-07 Celanese International Corporation Extractive distillation of crude alcohol product
WO2012149140A1 (en) 2011-04-26 2012-11-01 Celanese International Corporation Reduced energy alcohol separation process having water removal
CN103119010B (zh) 2011-04-26 2015-07-29 国际人造丝公司 通过分离来自加氢过程的粗产物回收乙醇侧线馏分
US20120277482A1 (en) 2011-04-26 2012-11-01 Celanese International Corporation Removing Water from an Acetic Acid Stream in the Production of Alcohols
US9024085B2 (en) 2011-04-26 2015-05-05 Celanese International Corporation Process to reduce ethanol recycled to hydrogenation reactor
US9000233B2 (en) 2011-04-26 2015-04-07 Celanese International Corporation Process to recover alcohol with secondary reactors for hydrolysis of acetal
US8754268B2 (en) 2011-04-26 2014-06-17 Celanese International Corporation Process for removing water from alcohol mixtures
US8461399B2 (en) 2011-04-26 2013-06-11 Celanese International Corporation Separation process having an alcohol sidestream
US8927783B2 (en) 2011-04-26 2015-01-06 Celanese International Corporation Recovering ethanol with sidestreams to regulate C3+ alcohols concentrations
US8907141B2 (en) 2011-04-26 2014-12-09 Celanese International Corporation Process to recover alcohol with secondary reactors for esterification of acid
EP2702027B1 (en) 2011-04-26 2014-12-24 Celanese International Corporation Process to recover alcohol with secondary reactors for esterification of acid
US8704012B2 (en) 2011-06-16 2014-04-22 Celanese International Corporation Distillation of crude alcohol product using entrainer
US8440866B2 (en) 2011-08-03 2013-05-14 Celanese International Corporation Process for separating ethanol having low acid
US8481792B2 (en) 2011-08-03 2013-07-09 Celanese International Corporation Reducing acetals and/or esters during ethanol separation process
US8558034B2 (en) 2011-08-03 2013-10-15 Celanese International Corporation Reducing acetals during ethanol separation process using high pressure distillation column
WO2013019229A1 (en) 2011-08-03 2013-02-07 Celanese International Corporation Reducing impurities in ethanol in hydrogenation processes with multiple reaction zones
US8575405B2 (en) 2011-08-03 2013-11-05 Celanese International Corporation Reducing acetals during ethanol separation process
WO2013019238A1 (en) 2011-08-03 2013-02-07 Celanese International Corporation Reducing acetals during ethanol separation process using high pressure distillation column
WO2013019239A1 (en) 2011-08-03 2013-02-07 Celanese International Corporation Ethanol separation process having stripping section for reducing acetals
MX2014001326A (es) 2011-08-03 2014-05-30 Celanese Int Corp Reduccion de acetales durante el proceso de separacion de etanol.
US8877986B2 (en) 2011-08-03 2014-11-04 Celanese International Corporation Process for recovering alcohol
US8748676B2 (en) 2011-08-03 2014-06-10 Celanese International Corporation Process for purifying a crude ethanol product
US8846987B2 (en) 2011-08-03 2014-09-30 Celanese International Corporation Ethanol separation process having stripping section for reducing acetals
WO2013019233A1 (en) 2011-08-03 2013-02-07 Celanese International Corporation Process for producing anhydrous ethanol using extractive distillation column
WO2013019235A1 (en) 2011-08-03 2013-02-07 Celanese International Corporation Process for purifying a crude ethanol product
US8884079B2 (en) 2011-08-03 2014-11-11 Celanese International Corporation Reducing impurities in hydrogenation processes with multiple reaction zones
WO2013019237A1 (en) 2011-08-03 2013-02-07 Celanese International Corporation Reducing acetals and/or esters during ethanol separation process
WO2013019236A1 (en) 2011-08-03 2013-02-07 Celanese International Corporation Process for recovering ethanol in a side draw distillation column
US8927782B2 (en) 2011-08-03 2015-01-06 Celanese International Corporation Vapor separation in alcohol production
CN103796979A (zh) 2011-08-03 2014-05-14 国际人造丝公司 用于分离具有低酸的乙醇的方法
WO2013019231A1 (en) 2011-08-03 2013-02-07 Celanese International Corporation Vapor separation in ethanol production
US8895786B2 (en) 2011-08-03 2014-11-25 Celanese International Corporation Processes for increasing alcohol production
US8877987B2 (en) 2011-08-03 2014-11-04 Celanese International Corportation Process for producing anhydrous ethanol using extractive distillation column
WO2013019234A1 (en) 2011-08-03 2013-02-07 Celanese International Corporation Processes for improving ethanol production via hydrolysis of ester contaminants
US8853466B2 (en) 2011-08-19 2014-10-07 Celanese International Corporation Integrated process for producing ethanol from methanol
US8829253B2 (en) 2011-08-19 2014-09-09 Celanese International Corporation Integrated process for producing ethanol from methanol
US8853467B2 (en) 2011-08-19 2014-10-07 Celanese International Corporation Integrated process for producing ethanol
US8658843B2 (en) 2011-10-06 2014-02-25 Celanese International Corporation Hydrogenation catalysts prepared from polyoxometalate precursors and process for using same to produce ethanol while minimizing diethyl ether formation
US8536382B2 (en) 2011-10-06 2013-09-17 Celanese International Corporation Processes for hydrogenating alkanoic acids using catalyst comprising tungsten
US8648220B2 (en) 2011-10-11 2014-02-11 Celanese International Corporation Process for producing ethanol using a crude vinyl acetate feed
US8809598B2 (en) 2011-11-09 2014-08-19 Celanese International Corporation Producing ethanol using two different streams from acetic acid carbonylation process
US8686201B2 (en) 2011-11-09 2014-04-01 Celanese International Corporation Integrated acid and alcohol production process having flashing to recover acid production catalyst
WO2013070211A1 (en) 2011-11-09 2013-05-16 Celanese International Corporation Integrated process for producing ethanol from methanol
WO2013070209A1 (en) 2011-11-09 2013-05-16 Celanese International Corporation Integrated carbonylation and hydrogenation process to obtain ethanol
WO2013070216A1 (en) 2011-11-09 2013-05-16 Celanese International Corporation Integrated ethanol production from methanol via carbonylation and hydrogenation by extracting halides from acetic acid
US8809599B2 (en) 2011-11-09 2014-08-19 Celanese International Corporation Integrated process for producing ethanol and water balance control
WO2013070213A1 (en) 2011-11-09 2013-05-16 Celanese International Corporation Iintegrated process for producing ethanol from methanol with water balance control
WO2013070212A1 (en) 2011-11-09 2013-05-16 Celanese International Corporation Producing ethanol using two different streams from acetic acid carbonylation process
US8614359B2 (en) 2011-11-09 2013-12-24 Celanese International Corporation Integrated acid and alcohol production process
US8704013B2 (en) 2011-11-09 2014-04-22 Celanese International Corporation Integrated process for producing ethanol
WO2013070210A1 (en) 2011-11-09 2013-05-16 Celanese International Corporation Integrated carbonylation and hydrogenation process to obtain ethanol having flashing to recover acid production catalyst
US8829251B2 (en) 2011-11-18 2014-09-09 Celanese International Corporation Liquid esterification method to produce ester feed for hydrogenolysis
US9024089B2 (en) 2011-11-18 2015-05-05 Celanese International Corporation Esterification process using extractive separation to produce feed for hydrogenolysis
US8853468B2 (en) 2011-11-18 2014-10-07 Celanese International Corporation Vapor esterification method to produce ester feed for hydrogenolysis
US8829249B2 (en) 2011-11-18 2014-09-09 Celanese International Corporation Integrated esterification and hydrogenolysis process for producing ethanol
US8802901B2 (en) 2011-11-18 2014-08-12 Celanese International Corporation Continuous ethyl acetate production and hydrogenolysis thereof
US8748673B2 (en) 2011-11-18 2014-06-10 Celanese International Corporation Process of recovery of ethanol from hydrogenolysis process
WO2013078207A1 (en) 2011-11-22 2013-05-30 Celanese International Corporation Esterifying an ethanol and acetic acid mixture to produce an ester feed for hydrogenolysis
EP2782891A1 (en) 2011-11-22 2014-10-01 Celanese International Corporation Hydrogenating acetic acid to produce ethyl acetate and reducing ethyl acetate to ethanol
US8703868B2 (en) 2011-11-28 2014-04-22 Celanese International Corporation Integrated process for producing polyvinyl alcohol or a copolymer thereof and ethanol
US8927785B2 (en) 2011-11-29 2015-01-06 Celanese International Corporation Treatment of recycle gas from acid hydrogenation
US20130143973A1 (en) * 2011-12-02 2013-06-06 Celanese International Corporation Biomass gasification and integrated processes for making industrial chemicals through an ester intermediate
US9029614B2 (en) 2011-12-14 2015-05-12 Celanese International Corporation Phasing reactor product from hydrogenating acetic acid into ethyl acetate feed to produce ethanol
US8927790B2 (en) 2011-12-15 2015-01-06 Celanese International Corporation Multiple vapor feeds for hydrogenation process to produce alcohol
MX362499B (es) 2011-12-16 2019-01-21 Celanese Int Corp Produccion de acido acetico con estabilidad mejorada del catalizador.
US20130165704A1 (en) 2011-12-21 2013-06-27 Celanese International Corporation Process for producing ethanol in a reactor having a constant temperature
US9000234B2 (en) 2011-12-22 2015-04-07 Celanese International Corporation Calcination of modified support to prepare hydrogenation catalysts
US9233899B2 (en) 2011-12-22 2016-01-12 Celanese International Corporation Hydrogenation catalysts having an amorphous support
US8575406B2 (en) 2011-12-22 2013-11-05 Celanese International Corporation Catalysts having promoter metals and process for producing ethanol
US8907142B2 (en) 2011-12-29 2014-12-09 Celanese International Corporation Process for promoting catalyst activity for ethyl acetate conversion
US9079172B2 (en) 2012-03-13 2015-07-14 Celanese International Corporation Promoters for cobalt-tin catalysts for reducing alkanoic acids
US8455702B1 (en) 2011-12-29 2013-06-04 Celanese International Corporation Cobalt and tin catalysts for producing ethanol
MX2014007394A (es) * 2011-12-29 2014-08-21 Celanese Int Corp Catalizador de cobalto y estaño para producir etanol.
US9333496B2 (en) 2012-02-29 2016-05-10 Celanese International Corporation Cobalt/tin catalyst for producing ethanol
WO2013101304A1 (en) 2011-12-29 2013-07-04 Celanese International Corporation Process for producing ethanol from impure methanol
WO2013101305A1 (en) 2011-12-30 2013-07-04 Celanese International Corporation Pressure driven distillation for producing and recovering ethanol from hydrogenation process
US20130178663A1 (en) 2012-01-06 2013-07-11 Celanese International Corporation Cobalt-containing hydrogenation catalysts and processes for making same
WO2013103396A1 (en) 2012-01-06 2013-07-11 Celanese International Corporation Processes for making catalysts with oxalate precursors
WO2013103398A1 (en) 2012-01-06 2013-07-11 Celanese International Corporation Modified catalyst supports and process for producing ethanol using the catalyst
US9024086B2 (en) 2012-01-06 2015-05-05 Celanese International Corporation Hydrogenation catalysts with acidic sites
US8841230B2 (en) 2012-01-06 2014-09-23 Celanese International Corporation Processes for making catalysts with metal halide precursors
WO2013103395A1 (en) 2012-01-06 2013-07-11 Celanese International Corporation Precious metal, active metal and modified support - containing hydrogenation catalysts and acetic acid hydrogenation process using the same
US8937203B2 (en) 2012-01-06 2015-01-20 Celanese International Corporation Multifunctional hydrogenation catalysts
US8802588B2 (en) 2012-01-23 2014-08-12 Celanese International Corporation Bismuth catalyst composition and process for manufacturing ethanol mixture
US9051235B2 (en) 2012-02-07 2015-06-09 Celanese International Corporation Process for producing ethanol using a molar excess of hydrogen
US9353034B2 (en) 2012-02-07 2016-05-31 Celanese International Corporation Hydrogenation process with reduced residence time for vapor phase reactants
BR112013007324B1 (pt) 2012-02-08 2020-10-20 Celanese International Corporation produção de ácido acético com alta taxa de conversão
US8729311B2 (en) 2012-02-10 2014-05-20 Celanese International Corporaton Catalysts for converting acetic acid to acetone
US9050585B2 (en) 2012-02-10 2015-06-09 Celanese International Corporation Chemisorption of ethyl acetate during hydrogenation of acetic acid to ethanol
US9126194B2 (en) 2012-02-29 2015-09-08 Celanese International Corporation Catalyst having support containing tin and process for manufacturing ethanol
US8927786B2 (en) 2012-03-13 2015-01-06 Celanese International Corporation Ethanol manufacturing process over catalyst having improved radial crush strength
US8802903B2 (en) 2012-03-13 2014-08-12 Celanese International Corporation Stacked bed reactor with diluents for producing ethanol
US20130245131A1 (en) 2012-03-14 2013-09-19 Celanese International Corporation Hydrogenation of Mixed Oxygenate Stream to Produce Alcohol
US9073042B2 (en) 2012-03-14 2015-07-07 Celanese International Corporation Acetic acid hydrogenation over a group VIII metal calcined catalyst having a secondary promoter
US8536383B1 (en) 2012-03-14 2013-09-17 Celanese International Corporation Rhodium/tin catalysts and processes for producing ethanol
US20130261349A1 (en) 2012-03-28 2013-10-03 Celanese International Corporation Hydrogenation Catalysts and Processes for Making Same
US8975452B2 (en) 2012-03-28 2015-03-10 Celanese International Corporation Process for producing ethanol by hydrocarbon oxidation and hydrogenation or hydration
US8912367B2 (en) 2012-06-21 2014-12-16 H R D Corporation Method and system for liquid phase reactions using high shear
US8772553B2 (en) 2012-10-26 2014-07-08 Celanese International Corporation Hydrogenation reaction conditions for producing ethanol
CN103785417B (zh) * 2012-10-31 2016-08-17 中国石油化工股份有限公司 用于羧酸高选择性加氢制备醇的钴催化剂
CN103785415B (zh) * 2012-10-31 2016-03-30 中国石油化工股份有限公司 羧酸加氢制备醇的钴铋催化剂
CN103785414B (zh) * 2012-10-31 2016-03-30 中国石油化工股份有限公司 羧酸加氢催化剂、制备方法及其应用
CN103785416B (zh) * 2012-10-31 2016-04-27 中国石油化工股份有限公司 一种羧酸加氢催化剂、制备方法及其应用
CN103785418B (zh) * 2012-10-31 2016-05-25 中国石油化工股份有限公司 羧酸加氢制备醇的钴锡催化剂
CN103785412B (zh) * 2012-10-31 2016-04-27 中国石油化工股份有限公司 羧酸加氢催化剂、制备方法及其应用
CN103787828B (zh) * 2012-10-31 2015-10-07 中国石油化工股份有限公司 一种应用钴硼催化剂将羧酸气相加氢制备醇的方法
CN103787829B (zh) * 2012-10-31 2015-10-07 中国石油化工股份有限公司 一种钴银催化剂羧酸加氢制备醇的方法
CN103785413B (zh) * 2012-10-31 2016-03-30 中国石油化工股份有限公司 一种加氢催化剂、制备方法及其应用
CN103787827B (zh) * 2012-10-31 2015-10-07 中国石油化工股份有限公司 羧酸选择加氢制备醇的方法
US8729318B1 (en) 2012-11-20 2014-05-20 Celanese International Corporation Process for producing ethanol from methyl acetate
US9000237B2 (en) 2012-12-20 2015-04-07 Celanese International Corporation Ethanol refining process using intermediate reboiler
US9598342B2 (en) 2013-03-15 2017-03-21 Celanese International Corporation Production of acetic acid with enhanced catalyst stability
SG11201507677VA (en) 2013-03-15 2015-10-29 Celanese Int Corp Process for separating product gas using carbonylation processes
US8975451B2 (en) 2013-03-15 2015-03-10 Celanese International Corporation Single phase ester feed for hydrogenolysis
US8926718B2 (en) 2013-03-15 2015-01-06 Celanese International Corporation Thermochemically produced ethanol compositions
US20140275619A1 (en) 2013-03-15 2014-09-18 Celanese International Corporation Process for Producing Acetic Acid and/or Ethanol By Methane Oxidation
CN104109080B (zh) * 2013-04-16 2016-08-24 中国石油化工股份有限公司 经醋酸气相催化加氢制备乙醇的方法
US9150475B2 (en) 2013-11-08 2015-10-06 Celanese International Corporation Process for producing ethanol by hydrogenation with carbon monoxide controls
US9266095B2 (en) 2014-01-27 2016-02-23 Celanese International Corporation Hydrogenation catalysts with cobalt and alkaline-earth metal modified supports
US9382177B2 (en) 2014-04-28 2016-07-05 Celanese International Corporation Hydrogenation catalysts comprising a mixed oxide comprising a promoter metal
WO2015168021A1 (en) 2014-04-28 2015-11-05 Celanese International Corporation Process for producing ethanol with zonal catalysts
US9353035B2 (en) 2014-04-28 2016-05-31 Celanese International Corporation Process for producing ethanol with zonal catalysts
US9073815B1 (en) 2014-04-28 2015-07-07 Celanese International Corporation Hydrogenation catalysts comprising a mixed oxide and processes for producing ethanol
US9024088B1 (en) 2014-04-28 2015-05-05 Celanese International Corporation Hydrogenation catalysts comprising a mixed oxide comprising nickel
WO2016122465A1 (en) 2015-01-27 2016-08-04 Celanese International Corporation Process for producing ethanol using solid catalysts
US9670120B2 (en) 2015-01-27 2017-06-06 Celanese International Corporation Process for producing ethanol using a solid catalyst
WO2016175745A1 (en) 2015-04-27 2016-11-03 Celanese International Corporation Ruthenium-bismuth mixed oxide hydrogenation catalysts and processes for producing ethanol
WO2016175747A1 (en) 2015-04-27 2016-11-03 Celanese International Corporation Hydrogenation catalysts comprising a mixed oxide having bismuth and process for producing ethanol
US9540297B2 (en) 2015-04-27 2017-01-10 Celanese International Corporation Ruthenium-bismuth mixed oxide hydrogenation catalysts and processes for producing ethanol
CN105289601B (zh) * 2015-12-07 2018-01-02 中国科学院广州能源研究所 一种山梨醇水相加氢制取直链c5/c6烷烃催化剂及其制备方法
CN105688882A (zh) * 2016-02-29 2016-06-22 苏州莱特复合材料有限公司 一种稀土催化剂及其粉末冶金制备方法
US10472303B2 (en) * 2017-08-30 2019-11-12 Uchicago Argonne, Llc Alkane activation with single and bi-metallic catalysts
CN107649146B (zh) * 2017-09-18 2019-11-29 北京华福工程有限公司 乙炔环三聚制苯用催化剂及其制备方法和应用
CN114160145A (zh) * 2021-11-24 2022-03-11 厦门大学 一种乙酸加氢制备乙醇的催化剂及其制备方法
WO2023104963A1 (de) 2021-12-08 2023-06-15 Linde Gmbh Verfahren und anlage zur herstellung eines oder mehrerer kohlenwasserstoffe

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4517391A (en) * 1982-06-04 1985-05-14 Basf Aktiengesellschaft Continuous preparation of ethanol
JP2001004687A (ja) * 1999-06-22 2001-01-12 Chubu Electric Power Co Inc 高調波特性測定用計測装置
US6232352B1 (en) * 1999-11-01 2001-05-15 Acetex Limited Methanol plant retrofit for acetic acid manufacture
CN1772719A (zh) * 2004-11-12 2006-05-17 埃塞泰克斯（塞浦路斯）有限公司 用于乙酸和甲醇一体化制造的自热重整方法

Family Cites Families (81)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2607807A (en) 1950-02-24 1952-08-19 Du Pont Preparation of alcohols from carboxylic acids
US2744939A (en) 1954-11-26 1956-05-08 Standard Oil Co Production of alcohols of high purity by improved oxo process
DE1235879B (de) 1964-03-17 1967-03-09 Basf Ag Verfahren zur Herstellung von Alkoholen durch katalytische Hydrierung von Carbonsaeuren
GB1168785A (en) 1965-09-24 1969-10-29 British Petroleum Co Graphite
US3990952A (en) 1974-10-10 1976-11-09 Raphael Katzen Associates International, Inc. Alcohol distillation process
US4048096A (en) 1976-04-12 1977-09-13 E. I. Du Pont De Nemours And Company Surface impregnated catalyst
GB1583084A (en) * 1977-05-27 1981-01-21 British Petroleum Co Hydrocarbonylation of methanol to ethanol in the presence of added compounds
US4317918A (en) 1979-11-05 1982-03-02 Sumitomo Chemical Co., Ltd. Process for preparing alcohols
NL8003405A (nl) 1980-06-12 1982-01-04 Shell Int Research Werkwijze voor het bereiden van ethanol.
DE3101750A1 (de) * 1981-01-21 1982-08-26 Basf Ag, 6700 Ludwigshafen Verfahren zur kontinuierlichen herstellung von ethanol
US4398039A (en) 1981-05-18 1983-08-09 The Standard Oil Company Hydrogenation of carboxylic acids
US4443639A (en) 1981-05-18 1984-04-17 The Standard Oil Company (Indiana) Hydrogenation of carboxylic acids
DE3303571C2 (de) 1982-03-11 1984-07-26 Buckau-Walther AG, 4048 Grevenbroich Verfahren und Anlage zur Herstellung von Äthanol
JPS59500516A (ja) 1982-03-26 1984-03-29 デイビ−　マツキ−　（ロンドン）　リミテツド エタノ−ルの生成方法
US4421939A (en) 1982-10-15 1983-12-20 Union Carbide Corporation Production of ethanol from acetic acid
US4480115A (en) 1983-03-17 1984-10-30 Celanese Corporation Direct hydrogenation of carboxylic acids to alcohol and esters
GB8307612D0 (en) 1983-03-18 1983-04-27 British Petroleum Co Plc Ammonia production and catalysts
US5124004A (en) 1983-08-22 1992-06-23 Trustees Of Dartmouth College Distillation process for ethanol
BR8404579A (pt) 1983-09-14 1985-08-06 Halcon Sd Group Inc Processo para tratamento de acido acetico aquoso diluido
US4550185A (en) 1983-12-22 1985-10-29 E. I. Du Pont De Nemours And Company Process for making tetrahydrofuran and 1,4-butanediol using Pd/Re hydrogenation catalyst
EP0167300A1 (en) 1984-06-06 1986-01-08 Humphreys & Glasgow Limited Process for the production of alcohols
GB8509530D0 (en) 1985-04-13 1985-05-15 Bp Chem Int Ltd Hydrogenation of carboxylic acids
GB8707595D0 (en) * 1987-03-31 1987-05-07 British Petroleum Co Plc Chemical process
US5149680A (en) 1987-03-31 1992-09-22 The British Petroleum Company P.L.C. Platinum group metal alloy catalysts for hydrogenation of carboxylic acids and their anhydrides to alcohols and/or esters
GB8828616D0 (en) 1988-12-07 1989-01-11 Bp Chem Int Ltd Chemical process
US5008235A (en) 1989-12-21 1991-04-16 Union Carbide Chemicals And Plastics Technology Corporation Catalysts of Cu-Al-third metal for hydrogenation
DE4025525A1 (de) 1990-08-11 1992-02-20 Hoechst Ag Traegerkatalysatoren und ein verfahren zu ihrer herstellung
JP2704165B2 (ja) * 1990-09-10 1998-01-26 工業技術院長 有機含酸素化合物製造用触媒の調製方法
US5137861A (en) 1991-01-22 1992-08-11 Mobil Oil Corp. Catalyst comprising a hydrogenation metal and a delaminated layered silicate
US5243095A (en) 1992-04-24 1993-09-07 Engelhard Corporation Hydrogenation catalyst, process for preparing and process for using said catalyst
JPH06116182A (ja) 1992-10-09 1994-04-26 Mitsubishi Kasei Corp 有機カルボン酸及び／又は有機カルボン酸エステルの水素化方法
US5821111A (en) 1994-03-31 1998-10-13 Bioengineering Resources, Inc. Bioconversion of waste biomass to useful products
US5350504A (en) 1992-12-18 1994-09-27 Mobil Oil Corporation Shape selective hydrogenation of aromatics over modified non-acidic platinum/ZSM-5 catalysts
USRE35377E (en) 1993-05-27 1996-11-12 Steinberg; Meyer Process and apparatus for the production of methanol from condensed carbonaceous material
JP3630734B2 (ja) 1994-10-28 2005-03-23 キヤノン株式会社 情報処理方法
JPH08245444A (ja) * 1995-03-09 1996-09-24 Mitsubishi Chem Corp カルボン酸類の水素化方法及びそれに用いる水素化触媒
US5977010A (en) 1995-06-15 1999-11-02 Engelhard Corporation Shaped hydrogenation catalyst and processes for their preparation and use
DK136196A (da) * 1996-11-29 1998-05-30 Haldor Topsoe As Fremgangsmåde til fremstilling af eddikesyre
JPH10306047A (ja) 1997-03-04 1998-11-17 Mitsubishi Chem Corp １，６−ヘキサンジオールの製造方法
JP3780669B2 (ja) 1997-11-17 2006-05-31 三菱化学株式会社 アルデヒド類及び、又はアルコール類の製造方法
US6294703B1 (en) 1998-06-22 2001-09-25 Mitsubishi Chemical Company Process for the manufacture of cycloalkyldimethanol
EP0990638A1 (en) 1998-10-01 2000-04-05 Kvaerner Process Technology Limited Process
EP0992484A1 (en) 1998-10-01 2000-04-12 Kvaerner Process Technology Limited Process
EP0992482A1 (en) 1998-10-01 2000-04-12 Kvaerner Process Technology Limited Process
US5945570A (en) 1998-10-29 1999-08-31 Arhancet; Juan Pedro Catalyst and process for preparing 1,3-propanediol
US7074603B2 (en) 1999-03-11 2006-07-11 Zeachem, Inc. Process for producing ethanol from corn dry milling
US6509180B1 (en) 1999-03-11 2003-01-21 Zeachem Inc. Process for producing ethanol
JP4282829B2 (ja) 1999-06-16 2009-06-24 株式会社クラレ カルボン酸及びアルコールの製造方法
JP2001046874A (ja) 1999-08-17 2001-02-20 Mitsubishi Chemicals Corp 水素化用触媒、及びこれを用いるカルボン酸類からのアルコール類の製造方法
KR100460371B1 (ko) 1999-09-21 2004-12-08 아사히 가세이 가부시키가이샤 카르복실산 수소첨가용 촉매
JP4472109B2 (ja) 1999-09-21 2010-06-02 旭化成ケミカルズ株式会社 カルボン酸水添用触媒
CZ292620B6 (cs) 1999-10-14 2003-11-12 Sulzer Chemtech Ltd. Způsob výroby etylacetátu a zařízení k provádění tohoto způsobu
DE10009817A1 (de) 2000-03-01 2001-09-06 Basf Ag Verfahren zur Herstellung von Alkoholen an rheniumhaltigen Aktivkohle-Trägerkatalysatoren
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
JP3786007B2 (ja) 2001-05-29 2006-06-14 住友金属鉱山株式会社 炭化水素油中に含む芳香族化合物の水素化処理用触媒
US7297236B1 (en) 2001-06-30 2007-11-20 Icm, Inc. Ethanol distillation process
EP1277826A1 (en) 2001-07-18 2003-01-22 ATOFINA Research Hydrogenation and dehydrogenation processes and catalysts therefor
GB0118553D0 (en) 2001-07-30 2001-09-19 Bp Chem Int Ltd Process for removing an alcohol impurity
WO2003097523A2 (en) 2002-05-20 2003-11-27 Acetex (Cyprus) Limited Integrated process for making acetic acid and methanol
JP4410481B2 (ja) * 2003-04-18 2010-02-03 三菱重工業株式会社 酢酸の製造方法、及び酢酸の製造装置
GB0311091D0 (en) 2003-05-14 2003-06-18 Bp Chem Int Ltd Process
JP2007534477A (ja) 2004-04-26 2007-11-29 ハーテーエー・アクチェンゲゼルシャフト・ザ・ハイ・スループット・イクスペリメンテイション・カンパニー 酸素リッチな排ガスから一酸化炭素および炭化水素を同時除去するための触媒、ならびにその製造方法
GB0410408D0 (en) 2004-05-11 2004-06-16 Johnson Matthey Plc Catalysts
US20080207953A1 (en) 2005-07-13 2008-08-28 Basf Aktiengesellschaft Catalyst and Method for Hyrogenating Carbonyl Compounds
EP2004583B1 (en) 2006-04-05 2015-06-03 Woodland Biofuels Inc. System and method for converting biomass to ethanol via syngas
EP1923380A1 (en) 2006-10-20 2008-05-21 BP Chemicals Limited Process for the conversion of hydrocarbons to alcohols
US7538060B2 (en) 2007-02-14 2009-05-26 Eastman Chemical Company Palladium-copper chromite hydrogenation catalysts
MY149064A (en) 2007-02-16 2013-07-15 Kao Corp Catalyst for producing alcohol
US7425657B1 (en) 2007-06-06 2008-09-16 Battelle Memorial Institute Palladium catalyzed hydrogenation of bio-oils and organic compounds
ES2443025T3 (es) 2007-11-14 2014-02-17 Bp P.L.C. Procedimiento para la producción de alcohol a partir de una materia prima carbonosa
US20090166172A1 (en) 2007-12-28 2009-07-02 Leonard Ray Casey Ethanol plant process
EP2242735A2 (en) 2008-01-07 2010-10-27 Danmarks Tekniske Universitet - DTU A catalyst, a process for selective hydrogenation of acetylene to ethylene and a method for the manufacture of the catalyst
US20090221725A1 (en) 2008-02-28 2009-09-03 Enerkem, Inc. Production of ethanol from methanol
US8080693B2 (en) 2008-02-28 2011-12-20 Enerkem, Inc. Production of ethanol from methanol
US7608744B1 (en) * 2008-07-31 2009-10-27 Celanese International Corporation Ethanol production from acetic acid utilizing a cobalt catalyst
US7820852B2 (en) 2008-07-31 2010-10-26 Celanese International Corporation Direct and selective production of ethyl acetate from acetic acid utilizing a bimetal supported catalyst
US8309772B2 (en) 2008-07-31 2012-11-13 Celanese International Corporation Tunable catalyst gas phase hydrogenation of carboxylic acids
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
EP2186787A1 (en) 2008-11-13 2010-05-19 BP p.l.c. Hydrogenation of ethanoic acid to produce ethanol
US7884253B2 (en) 2008-12-11 2011-02-08 Range Fuels, Inc. Methods and apparatus for selectively producing ethanol from synthesis gas

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4517391A (en) * 1982-06-04 1985-05-14 Basf Aktiengesellschaft Continuous preparation of ethanol
JP2001004687A (ja) * 1999-06-22 2001-01-12 Chubu Electric Power Co Inc 高調波特性測定用計測装置
US6232352B1 (en) * 1999-11-01 2001-05-15 Acetex Limited Methanol plant retrofit for acetic acid manufacture
CN1772719A (zh) * 2004-11-12 2006-05-17 埃塞泰克斯（塞浦路斯）有限公司 用于乙酸和甲醇一体化制造的自热重整方法

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106995363A (zh) * 2016-01-25 2017-08-01 河南顺达化工科技有限公司 一种醋酸加氢耦合制备乙醇的工艺
CN106995363B (zh) * 2016-01-25 2018-07-10 河南顺达化工科技有限公司 一种醋酸加氢耦合制备乙醇的工艺

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