CN1509811A - 含铜材料 - Google Patents

含铜材料 Download PDF

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CN1509811A
CN1509811A CNA2004100013417A CN200410001341A CN1509811A CN 1509811 A CN1509811 A CN 1509811A CN A2004100013417 A CNA2004100013417 A CN A2004100013417A CN 200410001341 A CN200410001341 A CN 200410001341A CN 1509811 A CN1509811 A CN 1509811A
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copper
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surface area
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carbonate
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CN1261208C (zh
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C·M·洛克
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Johnson Matthey PLC
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Abstract

一种含有载负在多孔过渡型氧化铝上的含铜物质的组合物，所述组合物的铜铝原子比在0.14－0.5范围内，在250℃用氢气还原所述含铜物质后，所述组合物具有至少60m2/g铜的铜表面积。

Description

含铜材料
技术领域
本发明涉及含铜材料，尤其是含有载负在多孔过渡型氧化铝上的含铜物质的组合物。
背景技术
含铜组合物(其中一些或全部的铜是元素铜的形式或者氧化物的形式，即二价铜和/或一价铜的氧化物，或者其它含铜物质的形式，例如，硫化物、碱式碳酸盐等)广泛用在工业过程中作为催化剂或吸附剂。例如，其中部分或全部的铜为元素铜的组合物常用作涉及氢气反应的催化剂。作为实例，可以提出其中一氧化碳与水蒸气反应形成二氧化碳和氢气的变换反应；其中氢气和一氧化碳和/或二氧化碳的混合物反应形成甲醇或更高级的链醇的醇合成反应；加氢反应；酯的氢解反应。其中部分或全部的铜为元素铜、铜的氧化物、氢氧化铜或碱式碳酸铜的组合物可以用作气体和液体除去污染物(如硫的化合物)的提纯的吸附剂。其中铜为硫化铜形式的组合物可以用作吸附剂，从气体和液体中除去砷的化合物和汞。
对于这些用途，一般希望所述含铜物质以高度分散的形式存在，使得所述活性物质容易与反应物或待处理的材料接触。可以通过确定每克铜的暴露表面积(在所述含铜物质还原成元素铜之后)来估计所述含铜物质的分散程度。每克铜的高的铜表面积代表高度分散。铜的表面积可以通过氮的氧化物分解法方便地确定，例如Evas等人在“应用催化”，7，(1983)，第75-83页中所述——在EP 0 202 824中提出了一种特别合适的技术。
已知用金属的碳酸盐氨配合物溶液浸渍过渡型氧化铝载体，然后加热分解所述碳酸盐氨配合物可以制备具有每克金属高表面积的组合物(在还原时)。因此，EP 0 092 878描述了氧化铝组合物上镍的生产，W0 96 04 072描述了类似的钴组合物的生产。然而，通过用金属盐溶液或金属配合物溶液浸渍载体(如氧化铝)获得的金属的分散程度取决于所述配合物的分解难易程度或者所述盐的溶解度。如果所述盐太容易溶解或者所述配合物太稳定，在所述氧化铝载体的气孔表面上容易形成所述金属物质的团聚体而不是所述分解产物的薄层。这样的团聚体在还原成金属时，将获得具有低金属表面积的材料。在上述EP 0 092 878或WO 96 04 072中使用的镍和钴的碳酸盐氨配合物具有较低的稳定性。因此它们分解非常容易。
我们已经发现，虽然碳酸铜氨配合物是明显不同的并且比类似的钴或镍要稳定得多，但是通过这种方法仍然可以获得令人惊奇的高表面积铜材料。而钴和镍形成六元氨配合物，铜形成四元氨配合物。所述铜、钴和镍的氨配合物的络合常数如下：
    Co     Ni     Cu
    K1     M(NH3)1     130     630     14000
    K2     M(NH3)2     43     170     3200
    K3     M(NH3)3     11     54     780
    K4     M(NH3)4     6     16     135
    K5     M(NH3)5     2     6     -
    K6     M(NH3)6     0     1     -
当加热所述组合物分解所述氨配合物，当只排出部分氨时，所述钴和镍材料容易沉淀。另一方面，在加热所述铜配合物时，由于它们稳定得多，可以预期在水和氨的蒸发过程中，所述的铜可以在溶液中保持更长的时间，并且容易不均匀地沉积在排出最后的水的位置上，因此在所述氧化铝载体的气孔上产生铜组合物的团聚而不是形成要求的薄涂层。实际上，在EP 0259 911中，提出通过混合盐的氨溶液(如金属碳酸盐)和铝化合物的水溶液并把所述混合物加热沸腾，或者接近沸腾，来沉淀一种所述金属和铝的混合碱式碳酸盐。而这种方法在还原时，当所述金属为镍时，获得具有每克金属高金属表面积的组合物，当所述金属是铜时，所述金属表面积仅为1-20m2/克金属。
发明内容
因此，本发明提供一种含有载负在多孔过渡性氧化铝上的铜化合物的组合物的制造方法，包括用碳酸铜氨配合物水溶液浸渍多孔过渡型氧化铝载体，排出任何多余的浸渍溶液，然后加热所浸渍的载体到80℃以上的温度来分解所述配合物，从而在所述过渡型氧化铝载体的气孔表面上沉积一种碱式碳酸铜化合物。
在本发明的一个技术方案中，提供一种含有载负在多孔过渡型氧化铝上的含铜物质的组合物，所述组合物的铜铝原子比在0.14-0.5范围内，在250℃用氢气还原所述含铜物质后，所述组合物具有至少60m2/g铜的铜表面积。
在本发明的另一个技术方案中，提供一种根据上述技术方案的成型体，具有80m2/g以上的BET表面积。
在本发明的又一个技术方案中，提供一种根据任一上述技术方案的成型体，具有至少0.16的铜铝原子比。
所述过渡型氧化铝可以是γ-氧化铝族的氧化铝，例如，η-氧化铝或χ-氧化铝。在400-750℃煅烧氢氧化铝可以获得这些材料，一般具有150-400m2/g的BET表面积。另外，所述过渡型氧化铝可以是δ-氧化铝族，包括δ-和θ-氧化铝等高温型，可以通过把γ-族氧化铝加热到高于约800℃的温度形成。δ-氧化铝族一般具有50-150m2/g范围内的BET表面积。所述过渡型氧化铝中每摩尔Al2O3含有小于0.5mol的水，水的实际含量取决于其加热温度。所述载体应该是多孔的，优选具有至少0.2ml/g的气孔体积，特别优选在0.3-1ml/g范围内。
所述载体可以是粉末形式的，但是优选为成型体的形式，例如近似的球、片、圆柱片、大块。所述成型体优选具有至少1mm的最小尺寸，并且优选具有1-15mm范围内的最大和最小尺寸，优选为3-10mm。所述最大尺寸优选不大于所述最小尺寸的3倍。在使用粉末氧化铝时，所述氧化铝优选具有1-100μm范围内的表面加权平均直径。[术语表面加权平均直径D[3，2]，另外称为Sauter平均直径，由M.Alderliesten在文章“平均颗粒直径的命名法”，Anal.Proc.，Vol 21 May 1984第167-172页中定义，并且可以用例如Malvern Mastersizer激光衍射方便地进行的颗粒尺寸分析计算]。另外，所述载体可以是整块的形式，例如，蜂窝。在后一种情况下，所述蜂窝可以用陶瓷或带有过渡型氧化铝涂层的金属载体形成。
所使用的碳酸铜氨配合物的量优选使得所述组合物具有在0.025-0.5范围内的铜铝原子比，在二元含铜物质/氧化铝组合物中，对应于约3-40wt％的铜含量(在所述含铜物质还原成元素铜之后)。
本发明的成型体可以通过下列过程制造，即用碳酸铜氨配合物水溶液浸渍所述载体，在排出任何多余的浸渍溶液之后，把所浸渍的载体加热来分解所述碳酸铜氨配合物。在80℃以上的温度加热足以分解所述碳酸铜氨配合物，随着氨和二氧化碳的排出，获得碱式碳酸铜。在约200℃以上的温度加热，特别是在高于250℃的温度加热，将导致所述碱式碳酸铜分解形成氧化铜物质。所述碱式碳酸铜物质或氧化铜物质可以转变成其它含铜物质，例如通过还原转变为元素铜，或者通过用合适的硫的化合物(如硫化氢或在该技术中已知的碱或铵的硫化物或多硫化物溶液)硫化形成硫化铜。
通过把碱式碳酸铜溶解在含有过量氢氧化铵的碳酸铵水溶液中可以制备所述碳酸铜氨配合物溶液。所述相对含量应该使得所述溶液的pH值在7-12范围内，优选为8-11。所述溶液每升优选含有1-5，特别优选为2-4，尤其是1.5-2.5摩尔的铜配合物。当铜的浓度增大时，一般应该增大在所述碱式碳酸铜物料中的碳酸根离子与氢氧根离子的比例。
当所述过渡型氧化铝为成型体形式时，所述成型体可以用所述碳酸铜氨配合物多次浸渍，在两次浸渍之间加热进行所述碳酸铜氨配合物的分解。通过这种方法，所述碱式碳酸盐薄层沉积在所述过渡型氧化铝成型体的气孔表面，另一方面，当所述氧化铝以粉末形式使用时，所述过渡型氧化铝粉末可以与适量的碳酸铜氨配合物水溶液混合成为浆料，获得要求铜含量的产品。然后从水介质中过滤出带有沉积的含铜化合物的氧化铝并加热。然后，如果需要，所得的产物可以成型为成型体，如小球。
如果希望所述含铜物质为氧化物的形式，所述产物可以在200-500℃，尤其是250-450℃范围内的温度下煅烧。在某些情况下，当要求为所述氧化物并且所述过渡型氧化铝多次浸渍时，可以在两次浸渍之间煅烧所浸渍的物料。当希望所述铜为元素金属形式时，干燥的浸渍载体可以用合适的还原剂(例如氢气，优选用惰性气体稀释)在150-400℃，特别是200-300℃范围内的温度下直接还原。此外，所述还原可以在所沉积的碱式碳酸铜煅烧成氧化铜之后进行。
可以通过已知的过程进行所述铜金属、氧化铜或碱式碳酸铜向其它含铜物质(如硫化物)的转变。
取决于所述载体的气孔体积，和所使用的浸渍溶液的浓度，有可能生产含有在很宽范围内变化的含铜物质含量的组合物。例如，可以生产以所述过渡型氧化铝和所述含铜物质的总重量为基准，含铜物质含量在3-40wt％(用铜表示)范围内的组合物。对于在二元含铜物质/氧化铝组合物中铜与铝的原子比在约0.09以上的组合物，对应于约10wt％的铜含量(在所述含铜物质还原成元素铜之后)，可能需要多次浸渍。在所述含铜物质还原时，例如在150-250℃范围内的温度下通过氢还原时，可以获得具有40m2/g铜的铜表面积的组合物。优选地，所述铜表面积在50m2/g以上，特别是在60m2/g铜以上。
某些含有大量所述含铜物质并且在所述含铜物质还原时每克铜具有高的铜表面积的过渡型氧化铝上的含铜物质的组合物是新型的。
Robinson等人在“应用催化”，44，(1988)，第165-177页中描述了通过用硝酸铜浸渍γ-氧化铝，然后干燥并煅烧获得的这样的铜组合物。这篇文章的图5表明每克未还原的催化剂的最大铜表面积约为9m2/g，并且由含有约8wt％铜的组合物给出(Cu/Al原子比约0.07)。这对应于每克铜约112m2的铜表面积。但是在更高的铜含量时，铜表面积降低。因此在约24wt％的铜含量(Cu/Al原子比约0.25)时，每克未还原的催化剂的表面积约为3m2，即每克铜约12.5m2的铜表面积。
希望生产在所述含铜物质还原时每克铜具有高的铜表面积同时具有丰富铜含量的铜组合物。
在“ACS Division of Fuel Chemistry”，29，No.5，(1984)，第178-188页中，Chinchen等人列出了用于甲醇合成的铜/氧化铝催化剂，铜含量为20％、40％合60％，铜表面积分别为11.7、19.9和12.7m2/克未还原催化剂，对应于约58.5m2、49.8m2和21.2m2/克铜的铜表面积。没有提到这些铜/氧化铝催化剂的生产方法，但是由于它们与传统的铜/氧化锌/氧化铝甲醇合成催化剂相比较，它们大概通过甲醇合成催化剂常用的共沉淀法制备，而不是通过浸渍预成型的过渡型氧化铝载体的方法制备。
US 5 302 569中描述了具有铜表面积在35m2/g铜以上的铜催化剂。通过铜、锌和铝化合物的共沉淀然后煅烧制备这些铜催化剂。在所煅烧的催化剂中氧化铝的比例较小，在所煅烧的组合物中，氧化铝含量在每100份重量氧化铜含2-50份重量氧化铝范围内。所述实施例描述了组合物的生产，所述组合物在还原时，铜表面积在54-76m2/g铜范围内。
US 4 863 894中描述了具有大于70m2/g铜的更大的铜表面积的铜催化剂。通过铜化合物与锌和任选的铝化合物以碱式碳酸盐的形式共沉淀，然后把所述含铜物质还原成元素形式而没有把所述碱式碳酸盐组合物加热到200℃以上来制备那些催化剂。然而，这样的技术难以获得适当物理形式的催化剂。因此，所述碱式碳酸盐组合物球形化在还原时产生低强度的产品，而在还原后球形化需要在惰性气氛中进行。该文献的催化剂含有少量(如果有)的氧化铝，但是含有大量的锌和/或镁。
在本发明中，优选的是所述组合物含有大量铜，但是在还原后还含有至少60wt％的氧化铝，优选基本不含锌和镁的化合物，并且在所述含铜物质还原时，每克铜具有高的铜表面积。所述组合物优选为适用于固定床催化剂或吸附剂的成型体的形式。
因此，本发明还提供一种含有含铜物质和多孔过渡型氧化铝的组合物，优选的是最小尺寸为至少1mm的载体的形式，所述组合物的铜铝原子比在0.14-0.5范围内，并且在所述含铜物质在250℃还原时，具有至少60m2，优选至少80m2/g铜的铜表面积。
所述组合物优选具有80m2/g的BET表面积。优选地，所述铜铝原子比为至少0.16。
本发明的产品可以用作催化剂或吸附剂。使用还原形式的含铜物质，它们用于涉及氢气的反应催化剂。对于这些用途，在某些情况下，可以希望使所述产品包含贵金属(如铂、钯或铑)。用碱式碳酸盐或氧化物形式的含铜物质，它们用于通过去除硫的化合物提纯气体和液体。用硫化物形式的含铜物质，它们用作从气体和液体蒸气中除去汞和砷等杂质的吸附剂。
具体实施方式
通过下列实施例说明本发明
实施例1
在600ml氨水(浓度35％，比重0.88)中溶解250g碳酸铵，然后缓慢加入244g碱式碳酸铜(55wt％的Cu，CuCO3/Cu(OH)2重量比为1.2)并在室温下搅拌直至溶解制备一种浸渍溶液。然后过滤所述溶液。
把200g长3mm，直径1.2mm的BET表面积(A)为294m2/g、气孔体积(Vp从0.98的相对压力下的氮气物理吸附等温线的脱附分支推出)为0.65ml/g、平均气孔直径(4Vp/A)为88的γ-氧化铝挤出体(载体S-A)在室温下浸在400ml的浸渍液中。然后过滤所浸渍的挤出体，去掉多余的溶液并在120℃干燥一整夜。这种干燥的物料命名为产品1-A-1。
然后把150g产品1-A-1在300ml的所述浸渍液中浸渍10分钟，然后通过过滤除去多余的溶液。所述再浸渍的物料在120℃干燥一整夜，获得产品1-A-2。
然后把100g产品1-A-2在200ml的所述浸渍液中浸渍10分钟，然后通过过滤除去多余的溶液。所述再浸渍的物料在120℃干燥一整夜，获得产品1-A-3。把部分产品1-A-3在300℃在空气中煅烧2小时，获得产品1-A-3c。
实施例2
重复实施例1的过程，但是使用BET表面积为111m2/g、气孔体积为0.45ml/g和平均气孔直径(4V/A)为163的长3mm、直径为1.2mm的θ-氧化铝挤出体(载体S-B)。所述产物命名为2-B-1，2-B-2，2-B-3和2-B-3c。
实施例3
重复实施例2的过程，但是使用略小浓度的铜配合物溶液，因此，使用700ml的30％浓度的氢氧化铵溶液代替600ml浓度为35％的氢氧化铵。同时在每次浸渍之后在300℃煅烧所干燥的物料。在三次浸渍并且在每次浸渍之后煅烧的产物命名为3-B-3c。
实施例4
重复实施例1，但是使用BET表面积为248m2/g、0.77ml/g气孔体积和平均气孔直径(4V/A)为120的长3mm、直径为1.2mm的γ-氧化铝挤出体(载体S-C)作为载体。在两个浸渍步骤之后的干燥物料命名为4-C-2。在三次浸渍后干燥并煅烧的物料命名为4-C-3c。
实施例5
重复实施例4，但是所述载体进行4次浸渍并且每次浸渍后在120℃干燥。最后未煅烧的物料命名为5-C-4。
通过XRF分析某些产物的试样，通过氧化亚氮化学吸附确定某些产物的铜表面积。通过在用氩气稀释的氢气(67vol％H2/33vol％Ar)流中以200K/h的速度把所述试样加热到393K的温度，并在该温度下保温30分钟，然后以100K/h的速度把温度提高到要求的还原温度并在要求的还原温度下保温1h，在确定铜表面积之前进行所述试样的还原。在还原之后，把所述试样冷却到90℃，在该温度下使用氧化亚氮和氩气的混合物(1vol％N2O/99vol％Ar)进行所述氧化亚氮的化学吸附。假定Cus/Oads的吸附计量比为2并且一个铜原子占有的面积为5.182，即为73％的堆积密度，每平方米有1.46×1019个表面铜原子。
所得结果表示于下表。
    Cu(％wt)     BET表面积(m2/g)     还原温度下的铜表面积(m2/g铜)
    150℃     200℃     250℃
    S-A     0.0     294
    1-A-1     12.1     238     96.7
    1-A-2     17.1     230
    1-A-3     18.8     198
    1-A-3c     20.7     218     81.2     90.8     87.4
    S-B     0.0     111
    2-B-1     9.0     90
    2-B-2     12.8     97     80.5
    2-B-3     15.1     108
    2-B-3c     15.5     99     60.6     77.4     82.6
    3-B-3     14.1     -
    3-B-3c     14.5     -     94.8
    S-C     0.0     248
    4-C-2     14.4     -     75.6
    4-C-3c     18.4     -     74.3
    5-C-4     22.0     170     42.3
所述铜含量是未还原的催化剂的所述含铜物质的含量，用元素铜表示。
实施例6
试验了未煅烧的试样5-C-4从气流中吸附硫醇的能力。把30ml的未还原物料装入直径25mm的反应管中形成一个吸附床。含有20ppm(体积)的丙基硫醇的甲醇在25℃以14升/小时(即467h-1的空间速度)的速度在大气压下向下通过所述的床，分析所述流出物含硫化合物。对于450小时的时间，在所述流出物中没有检测到硫的化合物(检测极限为0.5ppm)，表明除去了全部的硫。
为了加速试验，然后把流入气体的丙基硫醇含量增加到100ppm(体积)并继续试验。再进行235小时的试验后，在排出的气流中检测到6ppm(体积)的二丙基二硫化物。在另外进行221小时的试验后，所述二丙基二硫化物含量增加到35ppm(体积)。在该阶段，用氮气以相同的流速代替进料气体。在随后的1054小时的过程中，二丙基二硫化物逐渐从所述吸附床上脱附直至在所述排出气体中降低到小于2ppm(体积)。在喂入含有丙基硫醇的甲醇或氮气时，在排出的气流中都没有检测到丙基硫醇。然后卸出所述吸附床并分析总的硫含量。所述吸附床上部的10ml平均硫含量为4.41wt％，中间的10ml平均硫含量为3.12wt％，底部的10ml平均硫含量为0.99wt％。
这表明除了吸附丙基硫醇之外，所述物料还有效催化丙基硫醇的二聚反应。
实施例7(对比)
通过类似的途径制备含有约14.5wt％的类似的镍物料2-B-3。在420℃煅烧并还原后，其镍表面积在150-160m2/g镍范围内。与实施例6中一样试验所述未煅烧物料，但是所述丙基硫醇含量为总体积的100ppm。仅231小时就除去了全部的硫，然后在所述排出气体中检测丙基硫醇和二丙基二硫化物分别为37ppm(体积)和21ppm(体积)。在330小时的总试验时间之后，所述体系用氮气清洗，花费189小时从所述吸附剂上脱附硫的化合物使得排出气体的硫含量低于2ppm(体积)。分析所述10ml部分的吸附剂得到平均硫含量为0.92％(上部)、0.87％(中间)和0.83％(底部)，所有的都是用重量表示。
与实施例6比较可以看出，镍类物质远不如所述含铜物料有效。
实施例8(对比)
为了单独评价过渡型氧化铝的有效性，用直径在3.3-4.7mm范围内、表面积为300m2/g的γ-氧化铝球并使用含有20ppm(体积)的丙基硫醇的甲醇重复实施例6的过程。仅过了17小时后，所述排出气体含有10ppm(体积)的丙基硫醇。然后用氮气清洗所述体系24小时。所述10ml部分的吸附剂分析得到平均硫含量为0.04％(上部)、0.03％(中部)和0.03％(底部)，所有的都是用重量表示，表明所述氧化铝作为丙基硫醇的吸附剂不是有效的。

Claims (3)

1.一种含有载负在多孔过渡型氧化铝上的含铜物质的组合物，所述组合物的铜铝原子比在0.14-0.5范围内，在250℃用氢气还原所述含铜物质后，所述组合物具有至少60m2/g铜的铜表面积。
2.根据权利要求1的成型体，具有80m2/g以上的BET表面积。
3.根据权利要求1或2的成型体，具有至少0.16的铜铝原子比。
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EP1069946A1 (en) 2001-01-24
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CA2320035A1 (en) 1999-10-14
CN1140342C (zh) 2004-03-03
CA2320035C (en) 2007-09-18
KR100560037B1 (ko) 2006-03-13
WO1999051340A1 (en) 1999-10-14
KR20010071134A (ko) 2001-07-28
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BR9908955A (pt) 2000-12-05
ZA200004519B (en) 2002-02-27
JP4611522B2 (ja) 2011-01-12

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