CN1326611C - 含有铼的载附催化剂以及使用该催化剂在液相中氢化羰基化合物的方法 - Google Patents

含有铼的载附催化剂以及使用该催化剂在液相中氢化羰基化合物的方法 Download PDF

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CN1326611C
CN1326611C CNB2003801030004A CN200380103000A CN1326611C CN 1326611 C CN1326611 C CN 1326611C CN B2003801030004 A CNB2003801030004 A CN B2003801030004A CN 200380103000 A CN200380103000 A CN 200380103000A CN 1326611 C CN1326611 C CN 1326611C
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rhenium
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M·舒伯特
M·黑塞
R-H·菲舍尔
T·康斯坦丁内斯库
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Abstract

本发明涉及一种在载附的含铼催化剂上将羰基化合物、特别是C4-二羧酸氢化为四氢呋喃和γ-丁内酯的混合物的方法。所述催化剂的特征在于铼和至少一种元素周期表VIII或Ib族的其它金属、特别是钌(Ru)、铑(Rh)、钯(Pd)、锇(Os)、铱(Ir)、铂(Pt)、铜(Cu)、银(Ag)或钴(Co)以至少一种双金属前体化合物的形式施加到载体上。本发明还涉及这些催化剂。

Description

含有铼的载附催化剂以及使用该催化剂在液相中氢化羰基化合物的方法
本发明涉及一种于液相中在载附的铼催化剂上氢化含羰基的化合物的方法，其中所述催化剂包括至少一种其它活性金属，该活性金属与所述铼一起以双金属化合物的形式施加到载体上。
工业上用氢气在铼催化剂上氢化含羰基的化合物例如醛、酮、羧酸、羧酸酐的方法已经公知了一段时间。
例如，DE-A100 09 817描述了一种载附的铼催化剂，该催化剂使用非氧化性预处理的活性炭作为载体材料。该催化剂还包含其它过渡金属、特别是铂族金属以提高活性。铼和其它过渡金属以它们各自盐的独立或合并溶液的形式施加到载体上。所述氢化的主要产物是醇。
DE-A 2 519 817公开了同时包含元素周期表VII和VIII族元素的催化剂。优选还包含铂或钯的载附的铼催化剂。这些催化剂尤其包含铼和钯，根据实施例，铼和钯优选在催化剂制备过程中同时施加到载体上。根据DE-A 2 519 817的公开内容，也可以首先将钯化合物施加到载体上。载附的钯-铼催化剂在将含羰基的化合物氢化为醇的反应中活性太低以致有必要同时使用高压和215-230℃的高温。由于能量和材料成本高，在高压和高温下进行氢化的经济可行性就低。另外，在这些条件下，腐蚀性、特别是羧酸溶液的腐蚀性提高。
EP-A 1112 776公开了一种使用催化剂氢化C4二羧酸、它们的酸酐或酯的方法，其中在所述催化剂中铼成分非常均匀地分布在载体材料上。但是，所存在的钯组分另外显示特殊的涂层形态，所以基于形成金属间相而假定的协同效应仅在有限程度上适用。所述催化剂形成具有良好选择性的γ-丁内酯。但是，所述产物混合物仅包含痕量的THF。
本发明的目的在于提供一种用于氢化羰基化合物的催化剂以及使用该催化剂氢化羰基化合物、特别是二羧酸如马来酸和/或琥珀酸或它们的酸酐或酯的方法，所述方法尤其能够制备具有大约等量的任选取代的γ-丁内酯(以下简称为”GBL”)和四氢呋喃(以下简称为”THF”)的混合物并且能够在良好转化率下以良好的总选择性制备这些混合物。
我们已经发现，通过用于将羰基化合物如二羧酸和/或它们的衍生物、特别是马来酸和/和琥珀酸、它们的酸酐和/或酯特别氢化为任选取代的γ-丁内酯和四氢呋喃混合物的一种载附的铼催化剂可以达到上述目的，其中铼和至少一种元素周期表VIII或Ib族的其它金属，特别是钌(Ru)、铑(Rh)、钯(Pd)、锇(Os)、铱(Ir)、铂(Pt)、铜(Cu)、银(Ag)或钴(Co)，以至少一种双金属前体化合物的形式施加到载体上。
在本文中，双金属前体化合物是一种其中既包含铼原子或阳离子也包含元素周期表VIII或Ib族金属原子或阳离子的化合物。
所用的双金属前体化合物优选是高铼酸盐复盐，更优选是通式I中的一种
[Mea(NH3)b(OH)c](ReO4)d·eH2O  (I)
或它们的混合物，其中Me是元素周期表VIII和Ib族金属，特别是Ru(钌)、Rh(铑)、Pd(钯)、Os(锇)、Ir(铱)、Pt(铂)、Cu(铜)、Ni(镍)、Ag(银)或Co(钴)，a是1或2，b是1-8的整数，c是0-5的整数，d是2、3或4，e是0-12的整数。
复盐是两种盐的混合晶体。离子晶体的阴离子和阳离子可以被其它阳离子和阴离子代替而不产生晶体结构类型改变。当互为代表的离子对(mutually representative ion pair)不是纯粹随机地分布于离子晶格中，而是以一定的分布计划排布时，结果就形成复盐。所述复盐的制备本身是公知的且已经例如描述在Pechenyuk，S.I..，Kuznetsov，V.Y.，Popova，R.A.，Zalkind，O.A.，Zh.Neorg.Khim.24(1979)3306。
本发明包括对下述的认识：使用这些复盐将催化活性组分施加到载体上实现了所有催化活性金属的均匀分布。
所用的双金属前体化合物更优选是Pd(NH3)4(ReO4)2和/或Pt(NH3)4(ReO4)2。
适用的载体材料是所有制备氢化催化剂的公知载体材料。优选二氧化硅，氧化铝、二氧化钛、二氧化锆、氧化镁、任选预处理的活性炭、石墨碳载体、氮化物、硅化物、碳化物或硼化物。所提到的预处理可以是氧化预处理，如例如在EP-A848 991中所述。优选使用任选预处理的活性炭载体。
铼(Re，按金属计)和元素周期表VII和Ib族其它金属的施加量各自是基于由载体和活性成分组成的催化剂的总重计的0.03-30重量％，优选1-12重量％，更优选2-5重量％。
其它元素可以存在于所述催化剂中。实例包括Zn(锌)、Sn(锡)、Au(金)、Fe(铁)、Mn(锰)、Cr(铬)、钼(Mo)、W(钨)和V(钒)。元素周期表的VII、VIII或Ib族元素如铼(Re)、铂(Pt)、钌(Ru)、银(Ag)和钯(Pd)同样可另外存在。这些元素基本上在活性和选择性(氢化产物)方面改进了催化剂但不是必要的。它们与铼的重量比可以是0-100，优选0.5-30，更优选0.1-5。根据本发明的催化剂特别优选是无铬的。
活性组分铼和元素周期表VII或Ib族其它金属在载体上的施加可通过下述方式进行：通过一步或多步骤用特别溶于水、醇或用其它有机溶剂制备的双金属前体化合物、更优选式I复盐的溶液浸渍；溶于水溶液或醇溶液的双金属前体化合物、更优选式I复盐在一步或多步骤中的平衡吸附。在这些方法中，活性组分被同时且均匀地施加到载体材料上。在浸渍和平衡吸附的各个步骤之间，在各种情况下均存在一个干燥步骤以除去溶剂。优选通过用盐的水溶液一步浸渍来施加活性组分。
为了在浸渍或平衡吸附步骤之后除去溶剂，干燥被浸渍的催化剂。干燥温度为30-350℃，优选40-280℃，更优选50-150℃。
活性组分在本发明催化剂载体上分布得特别均匀，并且铼与元素周期表VIII或Ib族金属(Me)的在全部催化剂颗粒上的强度比在超过99.9％的分析点特别具有低于系数10(a factor of 10)的偏差，优选在催化剂表面98％的分析点具有低于系数5的偏差，更优选在80％的分析点具有低于系数2的偏差，其中是所述值以统计平均为基础。
该系数通过SEM-EDX(扫描电子显微镜-能量弥散X-射线光谱)确定。该方法本身是公知的并且已经例如描述在Ulmanns Encylopedia ofIndustrial Chemistry，第6版，2000电子版本中。
所述催化剂通常在使用前活化。所述活化可通过向催化剂施加还原气氛进行。优选使用借助氢气的活化。活化温度一般为100-500℃，优选130-400℃，更优选150-400℃。可选择的还原方法是通过与液体还原剂如肼、甲醛或甲酸钠接触来还原金属成分。所述液体还原剂一般在10-100℃下接触。优选在20℃和80℃之间接触。
氢化一般在110-250℃下进行，优选在150-250℃下进行。氢化一般在5-220巴、优选40-150巴的反应压力下进行。所述氢化一般在液相中进行，优选在固定床中。
适用于氢化的原料一般是可另外包含C-C双键或三键的羰基化合物。醛的实例是丙醛、丁醛、巴豆醛、乙基己醛、壬醛和葡萄糖。羧酸的实例是琥珀酸、富马酸、马来酸。酯包括上述酸的酯，例如甲基酯、乙基酯、丙基酯或丁基酯，以及也可以使用内酯，例如γ-丁内酯、δ-戊内酯或己内酯。还可以使用酸酐如琥珀酸酐或马来酸酐。优选的原料是C4二羧酸和/或它们的衍生物，更优选琥珀酸、马来酸、琥珀酸酐、马来酸酐和这些酸的酯。优选的是，还可以使用醛、羧酸、酯、酸酐和/或内酯的混合物，优选羧酸的混合物。
要氢化的化合物可以在无溶剂的情况下或在溶液中氢化。可能的溶剂包括例如氢化产物或所使用材料的一种，例如醇如甲醇、乙醇、丙醇或丁醇，还合适的是醚如THF或乙二醇醚或γ-丁内酯。优选的溶剂是水，特别是在羧酸的氢化中。
所述氢化可以一步或多步在液相中进行。在液相中，悬浮和固定床两种方法都是可行的。在放热反应的情况下，热量可通过外部冷却剂除去(例如管式反应器)。在反应器内蒸发冷却也是可行的，尤其在没有产物循环的情况下氢化时。在产物循环的情况下，一种可能性是再循环物流中的冷却器。
本发明方法将通过下面的实施例进一步说明。
实施例
使用SEM-EDX确定强度系数
使用具有EDX探头的Philips ESEM-XL30-FGSEM-EDX分光计测定铼和钯的强度(与含量相对应)。分析电压是30kV。对于制备，所述颗粒应以能够获得光洁切割表面的方式分离。超过300μm的切割表面用于测量它们的Pd和Re含量，测量使用SEM-EDX以每步15μm的步骤进行。在每个测量点，可以计算Pd和Re的强度比。
实施例1
将15.83gPd(NO3)2与8g 25％的NH3溶液混合并与8.66g NH4ReO4在98g水中的溶液混合。化合物Pd(NO3)2(ReO4)2结晶析出。通过过滤获得的产物用水清洗并干燥。
实施例2：催化剂A
将依照实施例1制备的1.11g的Pd-Re盐在80℃下溶于20g水中。将30g经过活化的炭载体(Degussa 180，自Degussa AG，Düseldofd)在70℃用Pd-Re盐溶液饱和。然后在120℃下于100L(STP)/h的氮气(N2)中干燥该催化剂。随后，所述催化剂在相同温度下在包含0.5％氢气(H2)的N2(100L(STP)/h)中还原30分钟并在200℃下还原30分钟。然后将氢气量提高到5％处理1小时并提高到100％处理另外2小时。然后，将温度提高到400℃并流入3000L的H2/小时。加热速率在各种情况下都是5℃/小时。最后，在室温下在N2中冷却7小时后，所述催化剂在含5％空气的N2中钝化。该催化剂包含0.5重量％Pd和2重量％Re。
实施例3
将1.11g的Pd-Re盐在40℃下溶于130g水中。在搅拌下将10g该溶液施加到30g活化的的炭载体(Degussa 180)上。然后在120℃下干燥该催化剂1小时。在用水清洗步骤后，重复所述饱和和干燥步骤直到全部溶液被施加到载体上。随后，以与实施例2相似的方式干燥并还原催化剂。该催化剂包含0.5重量％Pd和2重量％Re。
实施例4
在管式反应器内装入20g催化剂A并在大气压力和150℃下用N2(240L(STP/h))吹扫2小时。然后，混入5％H2并在2小时后将温度提高到200℃并隔夜保持该温度。在转为50％H2-N2混合物后，温度被提高到230℃1小时，并且最后的还原在120L(STP/h)纯氢气中进行1小时。最后，将压力提高到40巴。经过活化的催化剂A用于在235℃和40巴压力下以连续操作方式氢化琥珀酸酐(SAN)，其中琥珀酸酐作为在γ-丁内酯中的20重量％的溶液以6.06g/h的量送入。H2∶SAN的摩尔比是35。以91％的转化率获得了81％的产物收率(39％的四氢呋喃(THF)和35％的γ-丁内酯)。
对比例1：催化剂C1
将60g的经过水预润湿的活化炭载体(Degussa 180)在室温搅拌下用0.78gPd(NO3)22H2O和1.52g HReO4(72.8重量％溶液)于20ml水中的溶液饱和。随后，该催化剂按照与实施例2中关于催化剂A所述相似的方式干燥并还原。该催化剂包含0.5重量％钯和2重量％铼。
对比例2：
将20g催化剂C1装入管式反应器并按照与实施例5相似的方式活化。经过活化的催化剂A用于在235℃和40巴压力下以连续操作方式氢化琥珀酸酐(SAN)，其中琥珀酸酐以5.94g/h的量作为在γ-丁内酯中的20重量％的溶液送入。H2∶SAN的摩尔比是35。以80％的转化率获得了77％的产物收率(9％的四氢呋喃(THF)和53％的γ-丁内酯)。

Claims (9)

1.一种载附的铼催化剂，其中以通式(I)的至少一种高铼酸盐复盐的形式使用铼和至少一种元素周期表VIII或Ib族的金属：
[ Mea(NH3)b(OH)c](ReO4)d·eH2O    (I)
其中Me是元素周期表VIII和Ib族金属，a是1或2，b是1-8的整数，c是0-5的整数，d是2、3或4，e是0-12的整数，
并将所述的高铼酸盐复盐作为双金属前体化合物施加到载体上。
2.如权利要求1所述的载附的铼催化剂，其中Me是Ru、Rh、Pd、Os、Ir、Pt、Cu、Ni、Ag或Co。
3.如权利要求1或2所述的载附的铼催化剂，其中所用的双金属前体化合物是Pd(NH3)4(ReO4)2和/或Pt(NH3)4(ReO4)2。
4.如权利要求1或2所述的载附的铼催化剂，其中铼和元素周期表VIII或Ib族的金属的各自存在量是基于全部催化剂计的0.03-30重量％。
5.如权利要求1或2所述的载附的铼催化剂，其中通过电子显微镜测定的铼与Me的在全部催化剂颗粒上的强度比率显示在98％的分析测量点中低于系数5的偏差。
6.一种通过催化氢化羰基化合物制备四氢呋喃和γ-丁内酯的混合物的方法，其中包括使用如权利要求1-5任一项所述的催化剂。
7.如权利要求6所述的方法，其中所述羰基化合物选自醛、羧酸、酯、酸酐和/或内酯。
8.如权利要求7所述的方法，其中所述羰基化合物选自马来酸、富马酸、琥珀酸或它们的酯或酸酐。
9.如权利要求6-8中任一项所述的方法，其中所述氢化在5-220巴的压力和110-250℃下在固定床催化剂上在液相中进行。
CNB2003801030004A 2002-11-11 2003-11-06 含有铼的载附催化剂以及使用该催化剂在液相中氢化羰基化合物的方法 Expired - Fee Related CN1326611C (zh)

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