CN1006788B - 羧酸氢化生产醇的方法 - Google Patents

羧酸氢化生产醇的方法

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CN1006788B
CN1006788B CN86102420A CN86102420A CN1006788B CN 1006788 B CN1006788 B CN 1006788B CN 86102420 A CN86102420 A CN 86102420A CN 86102420 A CN86102420 A CN 86102420A CN 1006788 B CN1006788 B CN 1006788B
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rhenium
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CN86102420A (zh
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米兰尼·基特森
彼得·塞夫顿·威廉姆斯
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BP Chemicals Ltd
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/132—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group
    • C07C29/136—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH
    • C07C29/147—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of carboxylic acids or derivatives thereof
    • C07C29/149—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of carboxylic acids or derivatives thereof with hydrogen or hydrogen-containing gases
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    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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    • Y10S502/525—Perovskite

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Abstract

从醋酸制备乙醇或从丙酸制备丙醇的方法，是在催化剂存在和升温下，于1-150巴压力下使醋酸或丙酸与氢气进行气相接触。该催化剂包括其基本组分(1)元素周期表中VIII族的贵金属和(11)铼。这些基本组分被载在一种载体上，如载在高表面的石墨化炭上。

Description

本发明涉及羧酸的氢化。更具体地说，本发明涉及在包含元素周期表第Ⅷ族贵金属和铼的催化剂存在下，将醋酸和丙酸分别氢化为乙醇和丙醇的方法。
应用被载的第Ⅷ族贵金属催化剂，将羧酸氢化为相应的醇已从例如USP-A-4524225;USP-A-4104478;GB-A-1534232;GB-A-155174和EP-A-147219而知。上述专利除GB-A-1534232外都涉及C1和更高羧酸的氢化，并且与GB-A-1534232一样都是在液相中进行反应。此外，由于比本申请有更早优先权日的EP-A-147219是在本申请要求的优先权日之后公开的，因此，EP-A-147219是一件中间公开专利。
GP-A-1534232涉及在升温和加压下，在水和/或其它溶剂存在下，用在载体上的钯铼催化剂催化氢化羧酸（包括乙酸和丙酸）生产醇。催化剂中钯与铼的重量比为0.01-5∶1。反应压力范围为50-1000个大气压。其唯一例举的方法是在非常高的压力下C4和更高二元酸的氢化。
我们已经发现在液相中使用第Ⅷ族贵金属催化剂有这样的缺点，即铼和第Ⅷ族贵金属从催化剂中被浸提。不仅仅催化金属被浸提，也会发生不希望的含氧化物的载体被浸提。我们已经意外地发现，在气相中使用上述催化剂与以前使用的方法相比，在低压下催化活性高，选择性好寿命也长。而且，在气相中反应基本上克服了与液相反应有关的浸提问题。
因此，本发明提供了一种从醋酸生产乙醇或从丙酸生产丙醇的方法，该方法包括，在升温和1-150巴压力下，在主要成分为（1）一种元素周期表第Ⅷ族的贵金属和（Ⅱ）铼的催化剂存在下，蒸气态的醋酸或丙酸与氢气接触。
除了醇之外，本发明的方法通常产生付产物-相应的酯，例如，醋酸氢化一般也产生醋酸乙酯，丙酸氢化一般也产生丙酸丙酯。如果需要，产物中酯的比例可以增加，通过例如低转化率的操作，如每通过一次的转化率小于50%，或者通过引入酸到催化剂中以促进“就地”酯化。另一方面，醇的比例可以增加，例如通过共供水或在每通过一次的高转化率下操作。
醋酸和丙酸都可大量地从市场上买到，并可以其市场上获得的形式不加提纯地用于本发明的方法中。如果需要的话，可以进一步提纯。
氢气，更可大规模地从市场上买到，可以提纯或不经提纯而使用。
催化剂包括第一个成分-一种第Ⅷ族的贵金属和第二成分-铼。
为了避免怀疑，可指出第Ⅷ族贵金属是锇、钯、铂、铑、钌和铱。如上所述，第Ⅷ族金属，钯和钌最好。
该催化剂最好还包括一种载体。适宜的载体包括高表面积的石墨化炭，石墨，硅胶，矾土和硅胶/矾土，其中高表面积的石墨化的炭和硅胶最好。最好的硅胶载体是表面积高的硅胶，典型的硅胶比表面大于50m2/g。
特别好的载体是在GB-A-2136704（BP    Case NO.5536）中所述的高表面积的石墨化的炭。最好的炭是颗粒状炭，例如粒炭。炭粒的大小取决于任何给定反应器的允许压降（给出最小颗粒大小1和在炭粒中反应剂的扩散常数（给出最大炭粒大小）。最小炭粒大小最好为0.5mm和最大炭粒大小最好为10mm，例如不大于5mm。
这种炭最好是多孔炭。在要求最好的炭粒大小的同时要求这种炭粒是多孔的，这样可满足最好的表面积特性。
这种炭可以通过它们的BET，底面表面积和边缘表面积表征。BET表面积是用Brunauer    Emmett和Teller在J.Am.Chem.Soc.60，309（1938）中的方法通过氮气吸收测定的表面积。底面表面积是用Proc.Poy.Soc    A314    P473-498（详见P489）所述的方法，由从正庚烷中三十二烷在炭上的吸附热测定的表面积。边缘表面积是用在Proc.Roy.Soc（详见P495）所述方法，由从正庚烷中正丁烷在炭上的吸附热测定的表面积。
本发明中所用的炭的BET表面积至少为100m2/g，较好的是至少200m2/g，最好的是至少300m2/g。BET表面积不大于1000m2/g为好，不大于750m2/g更好。
BET表面积与底面积的比不大于4∶1为好，不大于2.5∶1更好，这一比值最好是不大于1.5∶1。
所用炭粒的底面表面积与边缘表面积的比至少是10∶1为好，最好是至少100∶1。这一比值尽管没有上限，不过，实际上通常不超过200∶1。
最好的炭载体可以通过热处理含炭原材料来制备。所说的原材料可以是一种亲油石墨，如GB1168785中所述的制备方法，或者可以是炭黑。
然而，亲油石墨含有片状的非常细的粒炭，不适于作催化剂载体。我们最好避免使用这种炭。类似的考虑同样适用于细小颗粒的炭黑。
最好的原材料是来自植物材料的活性炭，如椰子炭或草炭，或者由煤或可碳化的聚合物所得的炭。这些物质经热处理，并且不小于上面指定的颗粒大小，是最好的炭载体。
最好的原料有如下特性：BET表面积至少为100m2/g，最好至少为500m2/g。
为了制备有指定特性的炭载体，最好的热处理过程包括连续地（1）在惰性气体保护下于900-3300℃加热炭材料，（2）在300-1200℃氧化此炭材料，（3）在惰性气体保护下于900-3000℃加热。
在氧化阶段，当用氧（如空气）作氧化剂时，最好在300-600℃下进行。
在惰性气体中加热的持续时间不是严格的。但加热炭到所需的最高温度所需的时间应足以在炭材料中产生所需的变化。
氧化阶段显热不必在炭完全氧化的条件下进行。为了避免过氧化，最好使用气态氧化剂在控制的速度下进行氧化。气态氧化剂的例子有：水蒸气，二氧化碳，和含分子氧的气体如空气。氧化作用进行到按被氧化碳的重量计算碳重量损失至少是10%为好，最好是至少15%（重量）的碳损失。碳重量损失不大于40%为好，最好不大于25%（重量）的碳损失。
氧化剂的进料速度最好是这样的，要求的碳重量损失至少在2小时内完成，最好是在至少4小时内完成。
需要惰性气体保护时，可以供给氮气或一种其它惰性气体。
适合的催化剂组成是0.1-10%（重量）第Ⅷ族贵金属，最好是0.5-5%（重量）第Ⅷ族贵金属;0.1-20%（重量）铼，最好是1-10%（重量）铼;其余部分是载体。
该催化剂可以通过加入一种或几种元素周期表的ⅠA族，ⅡA族或ⅣA族金属来改进，最好是加一种ⅠA族金属。一种适合的金属是钾。起改进作用的一种或几种金属的加入量，基于催化剂总量可以是0.1-20%（重量）。该催化剂中加入起改进作用的金属会有有益的效果，在氢化期间碳-碳键的氢解可以或大或小地被抑制，因此，改进了这一方法对要求产物的选择性。
这种催化剂可以用各种各样的方法制备。制备这种催化剂的方法之一是，用铼和Ⅷ族贵金属的可溶性化合物的水溶液浸渍载体，这些化合物可热分解/还原为金属和/或金属氧化物。
浸渍方法可以是共浸渍或相继浸渍，最好是采用相继浸渍法。相继浸渍法最好是先用Ⅷ族金属浸渍，然后再用铼浸渍。
为了生产用于本发明方法的催化剂的一种最好 方法由以下两步组成。
（A）用可溶性Ⅷ族贵金属化合物的溶液浸渍载体（该化合物可热分解/还原成Ⅷ族贵金属），然后除去溶剂，和
（B）Ⅷ族贵金属浸渍过的载体，再用Ⅷ族金属基本上不溶的而可溶铼化合物的溶剂配成的铼化合物溶液浸渍（该铼化合物可热分解/还原成铼金属和/或氧化物），然后除去溶剂。
水适合于作（A）步的溶剂，低级醇如乙醇可用作（B）步的溶剂。用上述方法生产的催化剂可以避免在（A）步浸渍的载体上的钯在（B）步中任何可察觉程度的浸提。
生产用于本发明方法中的催化剂的另一种最好方法由以下步骤组成：
（A′）用可溶性Ⅷ族贵金属化合物的溶液浸渍载体（该经合物可热分解/还原成Ⅷ族贵金属），然后除去溶剂。
（B′）加热载体上的Ⅷ贵金属，和
（C′）Ⅷ族贵金属浸渍过的载体再用可溶性铼化合物的溶液浸渍（该铼化合物可热分解/还原成金属铼和/或氧化物），然后除去溶剂。
在载体上的Ⅷ族贵金属可以在或者一种惰性气体如氮气，还原气体如氢气，或者含氧气体如空气存在下适当地加热。在惰性气体存在下的加热可在150-350℃范围内完成。在还原气体存在下的加热可在100-350℃的范围内完成。在含氧气体存在下的加热可在100-300℃的范围内完成。当用高表面积石墨化的炭作载体时，温度上限为200℃。
在本发明的具体情况下，在步骤（C′）中不一定要求使用Ⅷ族贵金属基本上不溶的溶剂。因此，任何适当的溶剂都可用于本方法的步骤（A′）和（C′）中。适宜的溶剂包括单独用水和醇类。
最好在步骤（A）和（B）之间或步骤（A′）和（B′）之间再增加一个Ⅷ族贵金属浸渍过的载体被干燥的步骤。干燥是在50-150℃范围内加热完成。如果需要，这一步骤可以插入步骤（B洌《校α舛杂谑煜ふ庖患际趿煊虻娜嗽笔呛芎美斫獾摹
分解/还原成金属的适合的Ⅷ族贵金属化合物包括这些金属的盐，例如羧酸盐，硝酸盐和Ⅷ族贵金属存在于阴离子部分的一些化合物，例如四氯钯酸铵和四硝基钯酸铵。分解/还原成铼金属和/或氧化物的适合的铼化合物包括癸酸二铼，高铼酸铵和七氧化铼。
元素周期表ⅠA族，ⅡA族或ⅣA族的金属可以在制备过程中的任何时候加到此催化剂组合物中。此载钯/铼催化剂可以用这种金属的可溶性化合物的溶液浸渍。另一方面，这种金属的可溶性化合物可以加到共浸渍溶液中或相继浸渍的溶液中。
一种较好的催化剂含有载于高表面积石墨化炭的钯和铼，这已叙述于前面提到的GB-A-2136704中。与此相反，应用前面提到的EP-A-0147219（参见对照C）技术，当钯晶平均大小为100
Figure 86102420_IMG1
或更小时，马来酸氢化时选择性损失不合格和生产能力损失不合要求。我们已经发现，在醋酸或丙酸氢化中，催化剂选择性和生产能力基本上与30-150A°范围内的钯晶平均大小无关。因此，我们可以用钯晶大小为30-99.9A°的催化剂。
在本发明的方法中，催化剂使用之前最好是于升温下与或者氢气或者氢气/惰性气体（如氮气）混合接触1-20小时来活化。升温可以是在200-350℃范围。另一方面，可以在反应剂存在下加热至反应温度来活化催化剂。
对于载体上催化剂的准确特性不可能给出极可靠的测定，但确信Ⅷ族贵金属成分是元素金属的形式而铼成分是处于元素金属和/或其氧化物的形式。
本发明的方法适合于在100-350℃下进行，最好是150-300℃。适宜的压力小于50巴。
本发明的方法可以批量或连续生产，最好是连续生产。催化剂可以固定床、移动床或流化床形式使用。连续生产的气体时空间速度以50-50，000h-为宜，最好是2000-30，000h-。
本发明的方法通过以下实施例可进一步地被阐明。
催化剂制备
催化剂按照下面概述的方法制备。在这些方法中，HSAG炭代表高表面积石墨化的炭，其制备和特性如下：
用作载体的炭由商业上可买到的活性炭制备，从Degussa购买牌号为BKIV的活性炭。活性炭用以下方法处理。该活性炭在氩气氛下于约1小时 中从室温加热到1700℃;加热到1700℃之后，在氩气氛下冷却至25℃;然后，在一个套炉中在空气下加热到大约520℃，加热时间由经验判断重量损失至20%为限;接着，在氩气氛下加热至1800-1850℃之间。最后，在氩气氛下冷却至室温。所得含石墨炭被磨成16-30目BSS。
所得炭具有如下性质：
BET表面积 710m2/g
底面表面积 389m2/g
边缘表面积 2.3m2/g
BET/底面表面积    1.83
底面表面积/边缘表面积    169
实施例1
在下列各方法中，标称承载量是指加在载体上的金属的重量（不是盐），并以占载体重量的百分数表示。
A.将溶有硝酸钯和七氧化二铼的水溶液加到HSAG炭中，然后用旋转蒸发器将水除去。所得浸渍过的炭在100℃下于真空烘箱过夜以将其烘干。四种催化剂选用的各种组分的数量（用标称承载量表示）如下：Al-Pd2.5%，Re5%;A2-Pd2.5%，Re2%;A3-Pd2.5%，Re10%;A4-Pd5%，Re已被除去。
B.采用制备催化剂A的方法，但其中用适量的高铼酸铵代替Re2O7，并且，四种催化剂所选用的各种组分的数量（用标称承载量表示）如下：B1-Re5%，Pd2.5%;B2-Re5%，Pd10%;B3-Re5%，Pd0.5%;B4-Re5%，Pd已去除。
C.将溶有硝酸钯的水溶液加到HSAG中，用旋转蒸发器除去水，将所得浸渍过的炭放置在100℃的真空烘箱中干燥过夜。然后将该催化剂冷却，并置入一玻璃管中，于6小时内在氢气流中将其从约30℃加热至280℃。保持280℃10小时后将其在氢气中冷却，并用氮气清洗数次。
将Re2O7水溶液和炭上的钯混合，再一次用旋转干燥器将溶剂除掉，并将催化剂在100℃的真空烘箱中干燥过夜。最终催化剂中硝酸钯和Re2O7的数量（标称承载量）为Pd2.5%，Re5%。
D.重复制备催化剂C的方法，但不同点是在铼的浸渍前，浸渍过钯的炭催化剂是在氮气环境中于300℃下处理，而不是在氢气中280℃下处理。
E.重复制备催化剂C的方法，不同点是将铼浸渍前的氢气处理步骤用空气处理代替，即在6个小时内于流动空气中将浸渍过钯的炭从20℃加热至180℃，保持180℃4小时，然后在空气中冷却至30℃。
F.本催化剂按方法C制备，不同点是在干燥后，炭催化剂上的钯不用在氢气中加热，浸渍铼所用的溶剂不是水，而是乙醇。
G.使用方法C，不同点是在铼的浸渍即进行之前，在三个小时内在流动氮气中将炭催化剂上的还原态钯从30℃加热至约650-700℃，并在650℃-700℃下继续保持6小时，然后冷却至30℃。这一附加步骤的作用是为了增加钯的晶粒大小（用XRD测量）从30A°（方法C中制备的催化剂）至150A°（本方法制备的催化剂）。
H.含、钯、钌、铼、钾的催化剂按如下方法制备：将HSAG炭和含有三氯化钌和高铼酸铵的溶液相混合，并用旋转蒸发器除去溶剂，将所得催化剂在约100℃的真空烘箱中干燥过夜。然后将催化剂在2小时内于流动的氢气中从约30℃加热至300℃，并在300℃下继续保持1小时，然后在氢气中冷却并用氮气清洗。此后，用醋酸钾水溶液将还原态催化剂浸渍上钾。四种催化剂中各种组分的数量（用标称承载量表示）如下：
H1-Re5%，Ru5%，（K已去除）;H2-Re5%，Ru5%，K10%;H3-Ru5%，K5%，（Re已去除）;H4-Ru5%（Re和K已被除去）。
I.含钌和铼的催化剂按方法C制备，但不同点是用亚硝基硝酸钌代替硝酸钯，炭催化剂上的钌是120℃下干燥，而不是在100℃下干燥，然后在氢气中以4℃/分的升温速度加热至300℃，并在300℃下继续保持1小时。各组分的数量（标称承载量）为钌1%，铼10%。
J.一种钌/铼催化剂是按方法I制备，所不同的是首先浸渍铼。
K.采用方法A，所不同的是用戴维逊57硅胶（Davison）代替HSAG炭，用四氯钯酸铵代替硝酸钯，用本方法制备了一种标称承载量为Pd2.5%，Re5%的催化剂。
L.一种含铂和铼的催化剂是用方法C制备，但是氢氧化四氨铂代替了硝酸钯，标称承载量为Pt1%，Re5%。
催化剂的测试
实验在1-11巴（表压）的压力下进行，在一个内径为6-7mm的防腐不锈钢管中装入2.5mls的催化剂，并将反应管装在一管状加热炉中。然后，在两小时内于常压下氢气流中将催化剂加热至280℃或300℃，并在终止温度下继续保持1小时将催化剂活化，活化后，将催化剂在氢气中冷却至所需要的反应温度。使羧酸蒸气和氢的混合气体通过催化剂，反应压力用回压调节阀调至所需要的数值。蒸气/氢气混合物在蒸发区形成，在该区液态醋酸和氢气分别进料。对离开反应器的产物蒸气和其他气体被取样，并用气一液色谱仪（glc）进行分析。
在11-50巴（表压）下进行的实验，使用类似的方法和设备，所不同的是反应管的内径为10mm，使用了高达10mls的催化剂，并且产品通过冷凝器，气态和液态的产物用glc分别测量。
在上述两种方法中，温度都是通过插入催化剂床的热电偶测量。
产品混合物一般含有相应的醇和酯（酯是由于醇和未反应的酸发生脂化反应而生成的），并且还含有微量相应的烷基醚，醛，付产物甲烷、乙烷和丙烷（仅在丙酸的情况下）。通常，在使用炭和硅胶的情况下，主要产物是醇，特别是在高转化率的情况下更是如此。
对每一个实施例，都分别计算了转化率和选择性，即已氢化羧酸的比例和未转化为烷烃付产物的氢化羧酸的比例。因而，选择性表示在没有烷化的情况下催化剂氢化作用的能力。在所有实例中（除非另有说明），仅有微量（≤2%）的烷基醚和醛生成。
定义
WHSV＝按重量计算的时空间速度＝千克液体进料/千克催化剂·小时。
LHSV＝按体积计算的时空间速度＝升液体进料/升催化剂·小时。
生产能力＝千克酸转化/千克催化剂·小时。
实施例2-7
用实例1的方法A和方法C中制备的催化剂将乙酸进行氢化。
WHSV约为1.1（LHSV＝0.35），氢气和醋酸的投料比约为11∶1（摩尔），压力为10.3巴（表压）。除实例7（c）的催化剂在280℃下活化外，其他催化剂都是在300℃下活化。结果列于表1。在所有的情况下都可以看到催化活性是稳定的，在长达24小时的操作过程中没有发现减活现象。
结果表明，pd和Re相继浸渍是非常有利的（实施例7），催化剂A4的性能很差（这施例6），该催化剂不是本发明的产品，它仅含有钯。
实施例8-13
采用和实施例2-7同样的方法，但使用实施例1的方法B制备的催化剂。所有的催化剂都在300℃下活化。结果列于表2。
实施例13的催化剂不是本发明的产品，对其进行测定是为了比较。
实施例14-17
在醋酸氢化中用实施例1的方法C、D、E、F制备的催化剂进行比较。采用和实施例2-7相同的方法，所不同的是WHSV约为4（LHSV＝1.34），氢对醋酸的投料比为9∶1（摩尔）。催化剂在使用前于280℃下活化，反应温度为228-230℃。结果列于表3。
结果表明：在实验误差内，利用不同的相继浸渍技术都能生产具有类似高活性的催化剂。
实施例18
使用实施例1方法G制备的催化剂并重复实施例14-17的方法。发现生产能力为1.0千克/千克催化剂/小时，选择性为92.7%。在实验误差内，这些结果和在实施例14中所得到的结果相类似，尽管本实施例催化剂的Pd晶体平均大于（用XRD测量）为150A°，而实施例14的催化剂的Pd晶体平均大小为30A°。结果表明：当使用含较小Pd晶体（＜100A°）的催化剂时，并不会引起活性和选择性的显著下降，这与EP-A-147219（比较例C）的观点是相反的。
实施例19
用方法C制备的催化剂，在50巴（表压）和227℃下进行醋酸氢化。WHSV为15，氢对醋酸的投料比为9∶1（摩尔）。催化剂在280℃下活化。
醋酸转化率为40%，选择性为96%，相应的生产能力为6千克/千克催化剂/小时。如其他条件类似，但WHSV＝3.6时，则转化率为74%，
表1
实施例号    催化剂    T/℃    转化率（%）    选择性（%）
2    A1    222    27.2    91
3    A1    202    15.0    90
4    A2    202    6.3    93.6
5    A3    201    38.2    95.9
6    A4    200    0.6    30.4
7    C    217    52.1    93
表2
实施例号    催化剂    T/℃    转化率（%）    选择性（%）
8    B1    180    15.4    97.0
9    B1    210    37.5    95.1
10    B1    239    69.0    89.0
11    B2    210    45.0    95.0
12    B3    210    18.5    96.9
13    B4    210    13.7    97.6
表3
实施例号    催化剂    生产能力（千克/千克催化剂·小时）    选择性（%）
14    C    1.2    92.2
15    D    1.3    92.1
16    E    1.1    87.0
17    F    0.95    94.5
表4
实施例号    催化剂    压力/巴（表压）    T/℃    转化率（%）    选择性（%）
20    H1    5    200    46    38
21    H2    5    202    43    53
22    H2    10    194    54    58.5
23    H3    10    203    35.2    8.7
24    H4    5    201    22.3    5.9
表5
实施例号    催化剂    T/℃    转化率（%）    选择性（%）    选择性（%醛）
25    I    202    22.5    97    4
26    I    223    32.0    94    3
27    J    201    12.5    97    5
28    J    222    23.0    96    5
表6
实施例号    催化剂    T/℃    转化率（%）    选择性（%）
29    K    209    12.2    91.7
30    K    210    10.5    95.3 选择性为96%。
实施例20-24
在醋酸氢化中采用方法H制备的催化剂。催化剂在300℃下活化。WHSV约为1.1）（LHSV＝0.35），氢对醋酸的投料比为11∶1（摩尔），结果列于表4。
结果表明：钾在改进选择性方面有良好的效果，而催化剂H3、H4的性能非常差。这几种催化剂不是本发明的产品。
实施25-28
在丙酸的氢化中采用实施例1方法I、J制备的催化剂进行。重复实施例2-7的方法，不同的是使用的催化剂量为2mls，LHSV＝1，丙酸对氢的投料比为1∶10（摩尔），压力为9巴（表压）。催化剂在280℃下活化。结果列于表5。在每种情况中，产品中醛的浓度比其他实施例要高，因而我们列出了对醛的单独选择性数据。
结果表明：先进行Ru浸渍然后再进行Re浸渍所制备的催化剂比先进行Re浸渍再进行Ru浸渍的情况要好。
实施例29和30
在醋酸的氢化中采用实施例1方法K制备的催化剂，并用实施例2-7的方法，所不同的是实施例30的催化剂在450℃下活化，实施例29的催化剂在300℃下活化。结果列于表6中。
实施例31
由方法L制备的催化剂用于醋酸的氢化，并采用实施例14-17的方法。转化率为11.0%（生产能力为0.5千克/千克催化剂/小时），选择性为93.8%。
实施例32
由方法B1制备的催化剂用于醋酸的液相氢化。将1.01克粉末状催化剂与50.2克醋酸一起装入100ml的不锈钢高压釜中。将高压釜清洗后用氢气增压至100巴（表压），搅拌下加热至200℃，并在该温度下继续保持6小时。冷却后，将液态产品移出并过滤，对有机产品及金属铼和钯进行分析。冷却后的最终压力为50巴（表压）。
我们发现产品中含有27.9%的醋酸乙酯和2%的乙醇（对应的氢化生产能力为1.5千克/千克催化剂/小时）。另外，发现原来在催化剂上的铼和钯分别有16%和0.06%已浸提到溶液中。
本实施例表明：在醋酸的液相氢化中发生大量的铼被浸提现象。这与该反应在气相中进行的情况相反。在气相反应的情况下，不会发生可察觉的铼损失。
该例不是本发明的实施例，因为它是在液相中进行的，仅仅是为了对比的目的而做。

Claims (8)

1、一种由醋酸制备乙醇或由丙酸制备丙醇的方法，该方法包括在气相中的醋酸或丙酸在催化剂存在下与氢气接触。接触温度为100-350℃和压力为1-150℃巴下进行，该催化剂的基本成分包括载于载体上的(Ⅰ)元素周期表中Ⅷ族的贵金属和(Ⅱ)铼。
2、权利要求1所述的方法，其中的Ⅷ族贵金属钯。
3、权利要求1所述的方法，其中的Ⅷ族贵金属为钌。
4、权利要求1所述的方法，其中所说的载体为高比表面的石墨化的炭。
5、权利要求1所述的方法，其中所说的载体为硅胶。
6、上述权利要求中任何一项所述的方法，其中催化剂用加入元素周期表中ⅠA族金属的方法来改进。
7、权利要求6所述的方法，其中改进用的金属为钾。
8、权利要求1所述的方法，该方法中有相应的酯或是乙酸乙酯或者丙酸丙酯与乙酸或丙酸一同生成，并且可通过每次的低转化率或在催化剂中引入酸组分的办法来提高酯的比例。
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AU5601386A (en) 1986-10-16
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DE3677809D1 (de) 1991-04-11
CN86102420A (zh) 1986-10-08
EP0198681B1 (en) 1993-09-22
GB8509530D0 (en) 1985-05-15
AU592981B2 (en) 1990-02-01
EP0198681A2 (en) 1986-10-22
JPH0825931B2 (ja) 1996-03-13
CN1008088B (zh) 1990-05-23
JPS61275234A (ja) 1986-12-05
CN86102452A (zh) 1986-12-03
NZ215766A (en) 1988-11-29
ATE61327T1 (de) 1991-03-15
CA1264727A (en) 1990-01-23
EP0198681A3 (en) 1988-05-04
EP0198682A3 (en) 1988-06-08
US4990655A (en) 1991-02-05
DE3689050D1 (de) 1993-10-28
EP0198682B1 (en) 1991-03-06
US5061671A (en) 1991-10-29
CA1262719A (en) 1989-11-07
US4777303A (en) 1988-10-11
AU592980B2 (en) 1990-02-01
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US4804791A (en) 1989-02-14
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