CN101631611A - 包含钴和氧化锌的费-托催化剂 - Google Patents

包含钴和氧化锌的费-托催化剂 Download PDF

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CN101631611A
CN101631611A CN200780019718.3A CN200780019718A CN101631611A CN 101631611 A CN101631611 A CN 101631611A CN 200780019718 A CN200780019718 A CN 200780019718A CN 101631611 A CN101631611 A CN 101631611A
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fischer
cobalt
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T·莱克尔
C·巴伊恩斯
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BASF Catalysts LLC
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Abstract

本发明涉及一种适用于催化费－托反应的催化剂，所述催化剂包含负载在氧化锌上的钴金属并且具有以下体积颗粒度分布：＜10％具有小于1微米的颗粒度，70－99％具有1和5微米之间的颗粒度，且＜20％具有大于5微米的颗粒度。

Description

包含钴和氧化锌的费-托催化剂
本发明涉及一种包含钴和锌的费-托催化剂，以及制备这种催化剂的方法。
从US-A-4,039,302中可知含有氧化钴和氧化锌的催化剂用于C1-C3脂肪族烃的合成。
USP 4,826,800描述了一种制备用于在还原活化后作为合成气体转化为烃的催化剂的含有钴和氧化锌的催化剂的方法。这种催化剂通过将可溶的锌盐和可溶的钴盐溶液与例如氢氧化铵或碳酸铵的沉淀剂混合并回收该沉淀而制备。在所述的方法中碳酸盐和金属的比较高，已经发现这对催化剂的强度是有害的。
USP 5,345,005涉及一种用于通过例如丙酮的氢化制备醇的氧化铝上的Cu-Zn催化剂。在对比实施例中描述了氧化铝上的Cu-Zn-Co催化剂的制备，其中使用了苏打灰。但是已经发现苏打灰的使用对催化剂的强度具有潜在的损害。在USP 5,345,005中描述的Cu-Zn-Co催化剂的90体积％的颗粒度分布范围并没有予以说明。但是认为在催化剂的制备中苏打灰的使用导致颗粒度分布变宽。
US-A-5,945,458和US-A-5,811,365描述了一种在VIII族金属的催化剂组合物、例如氧化锌载体上的钴存在下的费-托方法。通过首先采用将锌盐溶液和其它组分添加到碱性碳酸氢盐溶液中制备载体、然后通过过滤从碳酸氢盐溶液中分离沉淀以形成之后可以干燥、煅烧并承载VIII族金属的滤饼而制备。然后催化剂材料形成药片状，将这种药片状粉碎以形成具有250-500μm尺寸的颗粒，其可以用在费-托方法中。需要额外的后处理例如粉碎以便获得具有良好强度性质的催化剂粉末。但是正如上面说明的，获得的平均颗粒度仍然相对较大。此外，粉碎导致宽的颗粒度分布，且具有这种大颗粒度和宽颗粒度分布的催化剂倾向于并不适合包括泡罩塔、淤浆相反应器或回路反应器(loop reactor)的过程。
WO-A-01/38269描述了一种用于进行费-托过程的三相体系，其中液体基质中的催化剂悬浮液与气态反应物在高剪切混合区混合，这之后将混合物排出到后混合区。因此据说传质得以加强。其中提到了特别是无机载体例如氧化锌上的钴催化剂的合适的催化剂。用于制备这些已知催化剂的载体的表面积小于100g/m2。这些现有技术中的钴基催化剂可以通过在合适的载体例如氧化锌载体上通过浸渍方法沉积钴制备。其它传统的制备方法包括沉淀途径，这典型的包括粉碎硬的催化剂材料的滤饼，导致从催化剂的制备方法得到小颗粒。
WO-A-03/090925描述了一种包含钴和锌共沉淀颗粒的催化剂，所述颗粒具有小于150μm的体积平均颗粒度和至少90％的催化剂颗粒体积具有0.4到2.5倍于平均颗粒度之间的尺寸的颗粒度分布。虽然这种催化剂是先前已知催化剂的改进，但是其仍然存在改进的空间，特别是关于以下的所需要的性质之间的平衡，即一方面活化中需要的性质，另一方面FT操作中的活性以及磨损性质。
在淤浆相费-托催化剂的情况中，总是要调节活性(费-托性能)和分离性质之间良好的平衡。在这方面，(粉末)催化剂应当具有给出良好传质和分离性质的最佳的颗粒度分布。这些性质在过程中在在线期间基本不能改变，从而使活性和分离性质保持很长一段时间。
现有技术中带有载体的用于费-托的钴催化剂通常是基于机械性能坚固的载体，其中浸渍了钴溶液并且之后干燥、煅烧并还原。另外，机械性能坚固的钴-载体体系可以通过优化沉淀条件沉淀。虽然在费-托反应器中的磨损可以导致微粒(亚微米颗粒)形成并且因此造成分离的问题，但是这种配方在流化床催化剂活化和淤浆相费-托反应器中都是机械稳定的。为了在流化床活化期间获得良好的流态化行为，优选的颗粒度分布通常与优选用于费-托过程需要的颗粒度分布不同。新鲜催化剂的颗粒度分布的选择总是形成二者之间的折衷。
本发明是建立在基于氧化锌上的钴的具有非常特殊的颗粒度分布的(共沉淀的)费-托催化剂上的，其具有非常良好的性质平衡，特别是与活化和使用期间的行为有关的方面。
本发明的催化剂用根据以下的体积颗粒度分布来限定：
＜10％具有小于1微米的颗粒度，
70-99％具有1和5微米之间的颗粒度，以及
＜20％具有大于5微米的颗粒度。
令人惊奇的发现含有负载于氧化锌之上的钴金属且满足以上相对宽的颗粒度分布的费-托(FT)催化剂满足良好的FT-催化剂的需要，因为它具有良好的活化性质，在操作期间它具有强的耐磨损性，它具有良好的过滤性质且它具有良好的性能。
在优选的实施方案中，体积颗粒度分布如下：
＜10％具有小于1微米的颗粒度，
75-95，更优选75-85％具有1和5微米之间的颗粒度，以及
＜15％具有大于5微米的颗粒度。
本发明催化剂的特殊颗粒度分布可以进一步基于分布曲线峰高度一半处颗粒度分布曲线宽度和D50(体积％/微米)之比限定。这一值优选为至少0.85，且更优选为至少0.90。
体积平均颗粒度和颗粒度分布通过所谓的Fraunhofer衍射方法测定。在Sympatec HELOS激光衍射设备上进行分析，其装备有SUCELL自动湿分散单元，还装备有小体积适配器(SVA)。测量在十四碳烯中进行，其中测量过程包含以下参数：测量的颗粒度范围为0.25-87.5μm，测量持续时间为20sec，且循环时间为100msec，参见实施例。测量前不应用超声处理。
已经发现当将根据本发明的催化剂用于催化过程时，其具有特别好的传质和/或传热性质。
已经发现根据本发明的催化剂特别有利于用于搅拌的淤浆相反应器、泡罩塔反应器、回路反应器或流化床反应器。
根据本发明的催化剂表现出非常有利的分离性质且可以例如非常适用于通过过滤从反应混合物中分离出来。
根据本发明的催化剂在活性和分离性质之间具有极为良好的平衡。
优选催化剂的体积平均颗粒度小于50μm，更优选小于25μm。其下限没有特别严格的限制，只要其满足本发明的条件即可。对于特别的目的，优选该尺寸至少使颗粒仍然可以从液体反应混合物中分离出来。例如特别合适的是催化剂具有2μm或更大的体积平均颗粒度。用具有1.5-15μm范围内的体积平均颗粒度的催化剂获得了非常好的结果。
优选样品在180℃下脱气后在3.3Pa(25m Torr)的压力下在Ankersmit Quantachrome Autosorb-6设备上通过氮气吸附测定的(N2-BET)测量催化剂的孔容积至少主要由具有5-100nm范围内直径的孔形成。更优选其中基本没有具有小于5nm直径的孔(特别是小于5％的孔容积由具有小于5nm直径的孔组成)。已经发现这种催化剂对于反应物和产物具有特别好的扩散性质。还发现这种催化剂对费-托反应具有高度的选择性。
具有小于0.5ml/g孔容积的催化剂获得了非常好的结果。孔容积优选为至少0.05ml/g。特别合适的是具有小于0.45ml/g孔容积的催化剂。
已经发现这种催化剂具有特别好的物理强度性质，这有利于在不同类型的反应器中应用，包括淤浆相反应器、回路反应器、泡罩塔反应器和流化床反应器。
本发明的催化剂是建立在氧化锌上的钴的基础上的。催化剂的组成可以广泛的变化，本领域的技术人员将会知道确定这些组成，这取决于计划的目的。优选地，锌和钴原子的比例在75到0.1的范围内，优选为40到0.1且更优选在20到0.3的范围内。
催化剂可以基本由钴和氧化锌组成。但是还有可能的是催化剂含有一种或几种其它组分，例如通常用于费-托催化剂中的组分。例如这种催化剂可以含有一种或几种助催化剂，例如钌、铪、铂、锆、钯、铼、铈、镧或它们的组合。当存在时，助催化剂典型的以钴和助催化剂的原子比高达10∶1的量使用。
已经发现根据本发明的催化剂含有至少一种IIIa族元素的化合物，例如氧化物，优选基于催化剂的总重量其浓度为0.1-60，更优选为0.1-10重量％，这种催化剂具有非常有利的结构稳定性。优选第IIIa族元素包括铝(Al)、镓(Ga)和硼(B)，其中铝是特别优选的。
采用根据本发明的基本不含钠的催化剂获得了非常好的结果。已经发现含有相对较高量的钠的催化剂的强度有所降低。此外，已经发现钠的存在损害了催化剂的活性，降低了它的费-托活性。因此，优选具有钠含量基于催化剂的重量为小于0.5重量％、更特别为0到0.15重量％、甚至更特别为0到0.1重量％的催化剂。
采用根据本发明的具有低铜含量或基本不含铜的催化剂获得了非常好的结果。铜可能促进副反应，例如通过酮、醛或羧酸的氢化形成醇，而这是通常优选被避免或抑制的，特别是在费-托过程中。铜的含量基于催化剂的重量优选小于2重量％，更优选为0到0.5重量％，甚至更优选为0到0.2重量％。
本发明含有钴和氧化锌的催化剂的制备可以通过钴和锌离子的共沉淀进行。
为了制备具有特定结构的催化剂，可以利用多种选择。
非常合适的方法是基于WO 03/090925中描述的方法，因此该方法改进为获得本发明的结构的方法。例如这可以通过改变搅拌速度或溶液注射到反应容器中的速率或通过应用其它类型的搅拌而进行。由于本发明的催化剂颗粒与所述文献相比通常较小并具有不同的颗粒度分布，较高的搅拌速度、较短的接触时间和/或较高的注射速度是优选的。
另外，可以制备在WO 03/090925范围内的第一颗粒，然后将该颗粒粉碎以获得本发明的催化剂，例如通过超声处理或其它粉碎处理。
通常该过程包括共沉淀方法，其中含有锌离子和钴离子的酸性溶液和碱性溶液一起供给到包含水性介质的反应器中，优选为水或水溶液，其中酸性溶液和碱性溶液在水性介质中接触并且形成包含钴和锌的沉淀。之后将该沉淀从水性介质(该水性介质可以与沉淀一起形成淤浆)中分离出来。然后将分离的包含沉淀的钴和锌干燥并且可以进行后处理，例如煅烧等，以形成所述催化剂。
酸性溶液和碱性溶液的合并优选选择为酸性溶液和碱性溶液的组分可溶解于水性介质中，但是当它们与碱性溶液接触时，钴和锌沉淀，而锌和钴的反离子基本保留在溶液中。本领域技术人员知道增养选择合适的条件，例如用于每一种组分的反离子的类型和浓度。
已经发现这种方法特别适用于制备上述催化剂。
已经发现根据本发明的方法允许直接制备直接干燥后用作自由流动的催化剂前体的颗粒状沉淀，即该方法允许不必碾碎或其它机械相互利以形成颗粒材料的沉淀的制备。但是有可能以这样设计该过程，即首先制备材料，然后通过粉碎将其装化为最后的催化剂。
优选颗粒的沉淀在基本恒定的pH值下进行，特别是pH值在设定点值附近最多±0.2pH单位内变化。因此，已经发现有可能制得具有非常有利的自由流动特征和良好机械强度性质的催化剂。
优选地，碱性溶液和酸性溶液连续供应到反应器中(从分隔开的管路)。
任选将在分离和干燥的沉淀或煅烧产物中的钴还原为金属性的钴。
各自适用于离子化锌和离子化钴的原料包括以足够的浓度可溶于酸性溶液和水的它们的盐。优选这种盐的实例分别包括硝酸锌、硝酸钴和乙酸锌、乙酸钴以及其它在酸性溶液中具有相似溶解性的钴或锌的无机或有机盐。
适合用于与存在的钴离子和锌离子共沉淀的组分为能够以足够的浓度溶于碱性水溶液的无机盐和有机盐，例如氢氧化物，碳酸盐，脲，异氰酸酯以及任何其它盐，其可以用作碱来源，能够溶解于碱性溶液中的水。这种盐的优选实例包括碳酸铵，碳酸氢铵和在碱性溶液中具有至少相似溶解性的无机或有机碳酸盐。
优选在水性介质中锌和钴的总浓度选择在0.1到5摩尔/升的范围内。在沉淀步骤的过程中优选该浓度保持在这个范围内。
酸性溶液的pH值优选在1-5的范围内。碱性溶液的pH值优选在6-14的范围内。水性介质的pH值(在其中发生共沉淀)优选在4-9的范围内，这取决于用作用于钴、锌和碱性组分的前体盐的类型。
搅拌频率非常适合选择为获得1-300kW/l水性介质范围内的输入功率。采用10-100kW/1水性介质范围内的输入功率获得了非常好的结果。
共沉淀过程中的温度优选在5-98℃的范围内选择，更优选在15-75℃的范围内。
本发明还进一步涉及根据本发明的催化剂在淤浆反应器、回路反应器、泡罩反应器或流化床反应器中的用途。本发明还进一步涉及根据本发明的催化剂在费-托过程或官能团氢化的过程中的用途，例如腈氢化为胺。
本发明进一步通过以下实施例说明。
实施例1催化剂的制备
20％的Co/ZnO催化剂
将23.4kg的Zn(NO3)2.6H2O和8.3kg的Co(NO3)2.6H2O溶解于80升的水中。在80升的水中制备由11.68kg碳酸铵组成的分开的溶液。将两种溶液同时泵入水(130升)的底部(heel)，在75℃下搅拌溶液。沉淀过程完成后，加入额外量的碳酸铵溶液以使最后的pH值增加到7.1。
沉淀过程完成后，将沉淀转移到压滤器并彻底洗涤直到不含铵和硝酸根。然后在闪蒸干燥器中干燥滤饼并在500℃下煅烧5小时。
将2.5kg煅烧的催化剂前体装载于流化床反应器中并在含25％氢气的氮气中还原。还原反应在335℃下进行6小时。还原完成后，将流化床单元卸载到淤浆相费-托回路反应器中，其中充满了蜡作为反应介质。颗粒度分布分析显示初始颗粒在在线前30个小时内解离，因此平均颗粒度从24.9μm降低到2.6μm。催化剂显示出优异的费-托性能，同时在费-托运行期间还保留了良好的分离行为。
实施例2-颗粒度分布的测量
体积平均颗粒度和颗粒度分布通过所谓的Fraunhofer衍射方法测定。分心在Sympatec HELOS激光衍射设备上进行。分散在十四碳烯上的催化剂代表性样品装载于SUCELL分散单元的小体积适配器(SVA)中，并且用以下参数进行测量：测量的颗粒度范围为0.25-87.5μm，测量持续时间为20sec，且循环时间为100msec。将搅拌速度和泵速度分别调节为60％和70％。在测量前或测量期间不应用超声处理。颗粒度分布以体积分布计算。
实施例3-在费-托反应中催化剂的催化性能
制备钴含量为20重量％的催化剂。催化剂的制备条件和颗粒度分布基本与实施例1相同。
催化剂样品(20g)在3.5cm OD管式反应器中还原。在大气压下用1000h-1空速(GHSV)的氮气吹扫反应器。以2℃/分钟的速率将温度升高到60℃。然后将气体进料转换为1000GHSV的空气。之后以1℃/分钟的速率将温度升高到250℃并在该温度下保持3小时。然后将气体流改变为1000GHSV的氮气6分钟并且之后将供给的气体转换为1000 GHSV的一氧化碳并保持3.5小时。
然后将供给的气体变回氮气并且以4℃/分钟的斜率将温度升高到280℃，一旦到达280℃，将供给的气体转换为2500 GHSV的氢气并在该条件下保持10小时。然后将反应器冷却到室温并在转移到反应器中之前用氮气吹扫。
催化剂在氮气的吹扫下转移到600ml的连续搅拌釜式反应器(CSTR)中，其中充入了角鲨烷(300ml，Aldrich)。然后将反应器密封并用250ml/min的氮气流加热到125℃。然后将向反应器供应的气体转换为8000GHSV的合成气，搅拌速度增加到700rmp且以2℃/分钟的速率将温度升高到130℃。然后以30bar/hr的速度给反应器加压到20barg。然后以60℃/小时的速率将温度升高到160℃，5℃/小时的速率将温度升高到175℃，1℃/小时的速率将温度升高到185℃，0.5℃/小时的速率将温度升高到205℃以及以0.3℃/小时的速率将温度升高到212℃。然后使用自动温度控制器保持％CO的转化率为60％。
40小时在线后在226℃的温度下获得了608g/升催化剂/hr的C5+的生产能力。

Claims (11)

1.适合用于催化费-托反应的催化剂，所述催化剂含有负载在氧化锌上的钴金属，并且具有以下体积颗粒度分布：
＜10％具有小于1微米的颗粒度，
70-99％具有1和5微米之间的颗粒度，以及
＜20％具有大于5微米的颗粒度。
2.根据权利要求1的催化剂，其具有以下体积颗粒度分布：
＜10％具有小于1微米的颗粒度，
75-95，优选75-85％具有1和5微米之间的颗粒度，以及
＜15％具有大于5微米的颗粒度。
3.根据权利要求1或2的催化剂，其中体积平均颗粒度为小于25μm，优选为1.5到15μm。
4.根据权利要求1-3的催化剂，其中孔容积主要由直径在5-100nm范围内的孔形成。
5.根据前述权利要求中任一项的催化剂，其中孔容积小于0.5ml/g，优选小于0.45ml/g。
6.根据前述权利要求中任一项的催化剂，其中表面积小于120m2/g，优选在5-100m2/g的范围内。
7.根据前述权利要求中任一项的催化剂，其中锌和钴的原子比在75到0.1的范围内，优选为40到0.1。
8.根据权利要求1-7中任一项的催化剂，其中存在一种或几种助催化剂，例如钌、铪、铂、锆、钯、铼、铈、镧或它们的组合，典型的钴与助催化剂的原子比最高达10∶1。
9.根据权利要求1-9的催化剂，其进一步包含IIIa族元素的至少一组化合物，优选其浓度基于催化剂的总重量为0.1-60，更优选0.1-10重量％。
10.根据权利要求1-9中任一项的催化剂的用途，用于费-托方法或官能团的氢化中。
11.费-托方法，其特征在于使用根据权利要求1-9的催化剂。
CN200780019718.3A 2006-05-01 2007-04-30 包含钴和氧化锌的费-托催化剂 Pending CN101631611A (zh)

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