CN101227978B - 制备催化剂的方法和使用所述催化剂的反应器 - Google Patents

制备催化剂的方法和使用所述催化剂的反应器 Download PDF

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CN101227978B
CN101227978B CN2006800269346A CN200680026934A CN101227978B CN 101227978 B CN101227978 B CN 101227978B CN 2006800269346 A CN2006800269346 A CN 2006800269346A CN 200680026934 A CN200680026934 A CN 200680026934A CN 101227978 B CN101227978 B CN 101227978B
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coating
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CN101227978A (zh
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M·J·鲍
D·L·塞加尔
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GTL Microsystems AG
CompactGTL PLC
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Abstract

制备催化剂载体，做法是使用包含陶瓷前体和两亲化合物的溶液涂布金属底材，随后处理所述涂层，使其形成胶束结构。随后处理所述涂层以在所述金属底材上形成中孔陶瓷涂层。所述胶束结构用作模板，使得孔具有规则的大小。随后可在孔内沉积活性催化材料。所述金属底材可例如为能使反应热从发热处散出的波纹箔。

Description

制备催化剂的方法和使用所述催化剂的反应器
本发明涉及一种催化剂和催化剂载体、制备所述催化剂和催化剂载体的方法以及包含所述催化剂的催化反应器。所述催化剂例如可用于费-托合成，例如作为用于将天然气转化为较长链烃的工艺的一部分。
一种方法见述于WO 01/51194和WO 03/048034(Accentus plc)，其中在第一催化反应器中，甲烷与蒸汽反应，产生一氧化碳和氢，随后所得到的气体混合物在第二催化反应器中进行费-托合成。总体结果是将甲烷转化为高分子量的烃，在周围环境下该高分子量烃通常为液体或蜡状物。该方法的两个阶段—蒸汽/甲烷转化和费-托合成需要不同催化剂，且由于两个反应分别为吸热反应和放热反应，因此需要将热转移至反应气体或从反应气体中转移走。用于这些反应的反应器可加工成堆叠的板，在各板之间限定流道，用于不同流体的流道在堆中交替存在。在那些需要催化剂的通道中，优选为在陶瓷涂层中携带催化剂的金属底材形式，当催化剂用尽时，这种结构能从通道中移出。所述催化剂结构提供了用于反应气体与催化材料接触的大表面积。最好确保活性催化材料的粒径均匀，但常规的陶瓷载体孔径分布宽，因此催化金属的微晶大小变化宽。
本发明提供了一种用于制备与金属底材结合的催化剂结构的方法，所述方法包括：
a)制备包含溶剂、两亲化合物、陶瓷前体和/或催化材料前体的溶液，其中如果所述金属的表面上没有陶瓷层，则所述溶液包含陶瓷前体；
b)在所述底材上形成所述溶液的涂层；
c)处理所述溶液，使其形成胶束结构；随后
d)处理所述涂层以从所述溶液中除去溶剂，因此形成由胶束的结构确定的表面沉积物。
通常进行步骤(b)和(c)的顺序不是关键的。如果溶液包含陶瓷前体，则所述表面沉积物为中孔陶瓷涂层。通过溶液中的胶束结构确定这些孔的分布和大小。
两亲化合物也称为两亲物、表面活性试剂或表面活性剂，为包含至少一个极性或亲水基团和至少一个非极性或疏水基团的分子。在水溶液中，两亲化合物可互相缔合，形成称为胶束的结构。这些胶束通常为球形结构，其中亲水基团形成外表面，疏水基团形成内部。通常仅在超过两亲化合物的极限浓度(可称为临界胶束浓度)时形成这种胶束。术语“中孔”和“中孔的”是指直径为2nm-50nm的孔。
为了确保陶瓷与金属底材牢固相连，金属最好形成稳定和粘合的氧化物表面，优选底材的金属为当加热时形成氧化铝表面涂层的钢合金，例如含铝的铁素体钢，例如含有15％的铬、4％的铝和0.3％的钇的铁(例如Fecralloy(TM))。当该金属在空气中加热时，形成粘合的氧化铝氧化物涂层，该涂层保护合金以免进一步氧化和腐蚀。当陶瓷涂层为氧化铝时，看起来与表面上的氧化物涂层粘合。
金属底材可为线网或毡片，但优选的底材为薄金属箔(例如厚度小于100μm)，可将底材起波纹、皱褶或成型。
随后可用活性催化材料浸渍中孔陶瓷，活性催化材料例如为钴(用于费-托合成的催化剂)或铂/铑(用于蒸汽/甲烷转化)或钯/铂(用于燃烧)或镍钨(用于氢化裂解)，在每种情况下，金属微晶的大小对于催化剂的活性是重要的，且应避免微晶附聚。或者最初涂在底材上的溶液还可包含活性催化材料或其前体。例如除了两亲化合物以外，所述溶液还可包含形成氧化铝溶胶的盐(作为陶瓷前体)和活性催化材料的盐(例如硝酸钴)。作为另一种选择，两亲化合物本身可结合有所需催化材料的原子。
在另一种选择中，在使用形成胶束的溶液之前金属底材首先涂有多孔陶瓷层例如氧化铝层。可例如通过浸涂或喷涂薄漆膜(washcoat)、干燥和煅烧进行。在这种情况下，形成胶束的溶液包含活性催化材料或其前体，对其进行处理以形成胶束结构，随后形成溶液的涂层(即步骤(c)在步骤(b)前进行)，因此胶束位于多孔陶瓷层的孔内。胶束用作催化活性材料(即钴)离子的笼(cage)，使得最佳量的钴原子(形成最佳大小的微晶所需的量)施用于陶瓷层的各孔，条件是孔足够大以容纳胶束。
这种结合催化材料的催化剂结构可插入反应器的流道内，其中用于反应的流道与用于除去或提供热量的流道交替存在。在流道内的催化剂结构的金属底材提高传热和催化剂表面积。所述催化剂结构可从反应器中的通道移出，因此如果催化剂用尽，可进行替换。
所述反应器可包括堆叠的板。例如可由各板中的槽限定第一和第二流道，将板堆叠，随后粘合在一起。或者可由堞形(castellated)且与平面片材交替堆叠的薄金属片限定流道，该流道的边缘可由密封条限定。形成反应器的堆叠的板例如通过扩散粘合、铜焊或热等静压粘合在一起。
现仅通过实施例的方式并参考附图来进一步和更具体地说明本发明，其中：
图1a-1e表示在沉积催化涂层中的各连续步骤中金属箔部分的截面图，各图不成比例。
该实施例使用厚度为10μm的Fecralloy合金的箔2作为底材。通过下段所述的方法在箔的两个表面上沉积催化涂层，随后将箔起波纹或成型以提供合适的催化剂负载和空隙率，例如通过堆叠插入费-托反应器流道的起波纹的箔和平面的箔。箔与通道长度相同(例如0.6m)，起波纹后箔的高度和宽度与流道的高度和宽度相同(例如0.1m×2mm)。在涂布前，将箔2在空气中进行热处理，形成氧化铝表面涂层(未显示)。
如图1a所示，首先使用包含少量镧盐的铝盐以及两亲化合物(例如氢氧化十六烷基三甲基铵)的水溶液的薄膜4涂布箔2，该溶液还可与有机化合物例如辛烷混合。该初始含水薄膜4的厚度为100nm-5000nm(0.1-5.0μm)，例如为1μm。如图1b所示，将薄膜4温热，使得两亲化合物6(和有机化合物，如果存在)形成胶束结构，例如为垂直于箔2表面的六边形柱8的形式，且具有规则的六边形间距。或者通过代之以从薄膜4蒸发一些水份可形成胶束结构，或者在温热的同时从薄膜4蒸发一些水份可形成胶束结构。
随后将箔2置于包含气态氨的气氛中，气态氨溶解于薄膜4的含水部分7，使得在用作模板的胶束周围的水合氧化铝沉淀。如图1c所示，随后将薄膜干燥，加热至高温例如500℃，分解有机分子并使氧化铝凝胶脱羟基，留下微孔氧化铝粘着的层或涂层10。孔隙率具有精密控制的孔径分布，具有规则的六边形单元图案和形态。根据形成胶束的两亲化合物的结构、有机化合物(如果存在)的比例和铝盐的浓度，孔径可为约3nm-最高达14nm。因此例如可选择这些参数使得孔的大小为约10-14nm。通常孔径范围不超过平均孔径的50％。烧结后，氧化铝涂层10的厚度为30nm-140nm。
当需要形成费-托催化剂时，将钴盐以及较少量(通常为钴盐重量的1％-5％)的助催化剂例如钌盐溶解于溶剂(例如水或与丙酮混合的水或与表面活性剂混合的水)中，以降低表面张力。如图1d所示，将该溶液12施用于氧化铝涂层10的表面，通过毛细作用使溶液12流入孔中。随后将氧化铝干燥，随后在可控热梯度下煅烧，使得形成氧化钴，可重复浸涂、干燥和煅烧步骤，直至得到所需的氧化钴负载。随后使用包含氢的还原气氛进行还原步骤，将温度逐步升至约330-450℃，在该温度下保持较长时间(例如12-36小时)。该方法将超过80％的氧化钴还原为金属。优选在包含惰性气体和小于20％的氢的气氛(例如含有5％的氢的氩气)中进行初始还原，在接近还原步骤结束时，优选氢浓度例如升至100％，且压力也可升至数巴。如图1e所示，氧化钴负载应使得有足够的金属产生，在还原步骤后，在各孔内的一种或多种钴微晶16的大小为约2-11nm。
根据氧化铝涂层10中孔的大小(直径和深度两者)以及氧化钴的负载确定钴微晶16的大小，氧化钴的负载取决于钴盐溶液的浓度。因此，氧化铝孔径用作形成钴微晶16的模板。微晶大小对提供活性、稳定和选择性的费-托催化剂是关键的。如果微晶太小，由于其表面能非常高，因此易氧化和中毒，且还易形成更多的甲烷。另一方面，如果微晶太大，则表面能低，因此为不太有效的催化剂(由于低表面能抑制为引发费-托链增长的必需前体的金属表面氢化物和碳化物的形成)。合适的微晶大小可为5-10nm。
通过将少量助催化剂的盐与包含催化剂金属盐的溶液混合，如上所述的助催化剂可与催化剂金属共沉积。因此将助催化剂进行煅烧，随后与催化剂金属一起还原。或者可在沉积催化剂金属盐之后沉积助催化剂，并优选在催化剂金属盐已干燥和煅烧后沉积助催化剂。
用于制备微孔陶瓷涂层的上述方法仅通过实施例的方式给出，可采用各种方式进行变化。例如初始溶液中的铝盐如硝酸铝可用水合氯化铝或脱硝硝酸铝溶液代替，使得至少部分初始为溶胶形式。后者可如下制备，例如热处理硝酸铝，使得部分分解，随后将残余物溶解于水中以形成溶胶。
通过两亲化合物的分子量和结构和不混溶的有机化合物(如果存在)的比例确定胶束和因此形成的柱的直径，这样确定了沉积在胶束结构周围的材料内的孔径，因此确定了在所得到的陶瓷中的孔径。应理解的是，可使用宽范围的不同的同时具有阴离子性和阳离子性的两亲化合物。阴离子两亲化合物例如通式为R-O-SO3 -且缔合小阳离子例如钠或氢的那些化合物。另一种合适的阴离子两亲化合物为钴AOT，即[双(2-乙基己基)琥珀酸酯磺酸]2钴(Co([bis-2-ethylhexyl]-sulphosuccinate)2)。存在许多不同的铵衍生物，如上述氢氧化十六烷基三甲基铵，这类铵衍生物为阳离子性，具有通式R4N+，含有小阴离子例如羟基，通常三个R为CH3-，第四个R为较长链。链R的长度对两亲化合物的性能是关键的，这是由于在含水溶液中链长小于C6的化合物太易溶于水，而不能形成胶束结构，而链长大于C36的化合物不能充分溶解。
向溶液中掺入在加热时分解释放氨的材料可避免使用气态氨。合适的材料例如为尿素或六亚甲基四胺。
该方法还可随后制备结合其他氧化物例如二氧化钛或二氧化硅的陶瓷。例如可使用二氧化钛盐或溶胶(例如氯化钛和脱氯氯化钛)代替上述铝盐或溶胶或与上述铝盐或溶胶组合使用。类似地，二氧化硅溶胶例如衍生自热解法(flame-hydrolysed)粉末在水中的分散体的二氧化硅溶胶可与铝盐组合使用。
综上所述，本发明提供的部分技术方案如下：
1.一种用于制备与金属底材结合的催化剂结构的方法，所述方法包括：
a)制备包含
·溶剂和两亲化合物，以及
·陶瓷前体和/或活性催化材料前体的溶液，
其中
如果所述金属底材的表面上没有陶瓷层，则所述溶液包含陶瓷前体，
而如果所述金属底材的表面具有多孔陶瓷层，则所述溶液包含活性催化材料前体；
b)在所述底材上形成所述溶液的涂层，
c)对溶液进行处理，以确保所述两亲化合物的浓度高于临界胶束浓度以便形成胶束结构；
其中如果所述金属底材的表面具有多孔陶瓷层，则步骤c)在步骤b)之前进行；随后
d)处理所述涂层以从所述溶液中除去溶剂，因此形成由胶束的结构确定的表面沉积物；随后
e)如果所述溶液不包含催化材料前体，但是含有陶瓷前体，使得所述表面沉积物包括中孔陶瓷涂层，则使用活性催化材料浸渍所述中孔陶瓷涂层；随后
f)将所述活性催化材料还原成为金属形式。
2.技术方案1的方法，其中所述底材的金属为当加热时形成氧化铝表面涂层的钢合金。
3.技术方案1的方法，其中所述底材包括线网、毡片或金属箔。
4.技术方案1-3中任一项的方法，其中在以所述溶液涂布之前，金属底材涂有多孔陶瓷层，且在形成所述溶液的涂层之前处理所述溶液以形成胶束结构，使得胶束至少部分位于所述多孔陶瓷层的孔内。
5.技术方案1-3中任一项的方法，其中所述溶液包含陶瓷前体，使得所述表面沉积物包括中孔陶瓷涂层，其中在所述中孔陶瓷的各孔内形成活性催化材料的单一的金属微晶。
6.技术方案1-3中任一项的方法，其中所述溶液包含陶瓷前体，以使所述表面沉积物包含中孔陶瓷涂层，且其中在所述中孔陶瓷的孔内沉积大小为2-11nm的微晶形式的所述活性催化材料。
7.技术方案1-3中任一项的方法，其中随后使所述金属底材起波纹以位于化学反应器的流道内。
8.一种紧凑的催化反应器，所述反应器限定了交替出现的用于反应的流道与除去或提供热量的流道，其中用于反应的各流道包含通过技术方案1-7中任一项的方法制备的催化剂结构。

Claims (8)

1.一种用于制备与金属底材结合的催化剂结构的方法，所述方法包括：
a)制备包含
·溶剂和两亲化合物，以及
·陶瓷前体和/或活性催化材料前体的溶液，
其中
如果所述金属底材的表面上没有陶瓷层，则所述溶液包含陶瓷前体，
而如果所述金属底材的表面具有多孔陶瓷层，则所述溶液包含活性催化材料前体；
b)在所述底材上形成所述溶液的涂层，
c)对溶液进行处理，以确保所述两亲化合物的浓度高于临界胶束浓度以便形成胶束结构；
其中如果所述金属底材的表面具有多孔陶瓷层，则步骤c)在步骤b)之前进行；随后
d)处理所述涂层以从所述溶液中除去溶剂，因此形成由胶束的结构确定的表面沉积物；随后
e)如果所述溶液不包含催化材料前体，但是含有陶瓷前体，使得所述表面沉积物包括中孔陶瓷涂层，则使用活性催化材料浸渍所述中孔陶瓷涂层；随后
f)将所述活性催化材料还原成为金属形式。
2.权利要求1的方法，其中所述底材的金属为当加热时形成氧化铝表面涂层的钢合金。
3.权利要求1的方法，其中所述底材包括线网、毡片或金属箔。
4.权利要求1-3中任一项的方法，其中在以所述溶液涂布之前，金属底材涂有多孔陶瓷层，且在形成所述溶液的涂层之前处理所述溶液以形成胶束结构，使得胶束至少部分位于所述多孔陶瓷层的孔内。
5.权利要求1-3中任一项的方法，其中所述溶液包含陶瓷前体，使得所述表面沉积物包括中孔陶瓷涂层，其中在所述中孔陶瓷的各孔内形成活性催化材料的单一的金属微晶。
6.权利要求1-3中任一项的方法，其中所述溶液包含陶瓷前体，以使所述表面沉积物包含中孔陶瓷涂层，且其中在所述中孔陶瓷的孔内沉积大小为2-11nm的微晶形式的所述活性催化材料。
7.权利要求1-3中任一项的方法，其中随后使所述金属底材起波纹以位于化学反应器的流道内。
8.一种紧凑的催化反应器，所述反应器限定了交替出现的用于反应的流道与除去或提供热量的流道，其中用于反应的各流道包含通过权利要求1-7中任一项的方法制备的催化剂结构。
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