CN107427817A - 催化剂前体,其制备方法和用途 - Google Patents
催化剂前体,其制备方法和用途 Download PDFInfo
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- CN107427817A CN107427817A CN201680020250.9A CN201680020250A CN107427817A CN 107427817 A CN107427817 A CN 107427817A CN 201680020250 A CN201680020250 A CN 201680020250A CN 107427817 A CN107427817 A CN 107427817A
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- cobalt
- catalyst
- catalyst precarsor
- foams
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Abstract
描述了一种适于费托反应的催化剂前体,其包含负载在多孔载体上的氧化钴,其中该多孔载体是包含闭孔结构的陶瓷泡沫体。
Description
本发明涉及钴基费托催化剂,特别是负载在发泡载体上的钴基费托催化剂。
费托反应使用包含一氧化碳和氢气的合成气来产生烃,特别是长链烃产物和含氧物。合适的催化剂包含负载在金属氧化物载体上的钴。钴典型地以氧化物形式提供,并且原位还原成活性金属形式,或者催化剂可以预还原和钝化。金属氧化物载体可以为喷雾干燥的粉末、颗粒或成形挤出物的形式。
US6558634和US6750258公开了一种用于费托反应的微通道反应器,其中该微通道内优选的催化剂结构使用金属泡沫体载体来制造,该载体具有开放孔结构以允许气体流过该催化剂。该金属泡沫体结构涂覆有费托催化剂浆料,并且经干燥以形成催化剂结构。但是,金属泡沫体载体的效用是有限的,并且必需预处理该金属以确保催化剂浆料必需的粘合性。
CN102728359(A)公开了一种钴基费托催化剂,其使用中孔氧化硅泡沫体作为载体来制备。该中孔载体具有三维有序孔结构,其孔尺寸是20-50nm和孔体积是1.5-3.0cm3/g。该泡沫体具有开放孔结构,其中球形孔通过窗口连接。
US5217939公开了一种氧化钴涂覆的陶瓷泡沫体,其中该陶瓷泡沫体是网状陶瓷泡沫体,其例如通过聚氨酯铸塑来制造。这样的泡沫体具有开放孔结构。
我们已经发现,令人惊讶地有效的钴基费托催化剂可以负载在包含闭孔结构的陶瓷泡沫体载体上。
因此,本发明提供一种适于费托反应的催化剂前体,其包含负载在多孔载体上的氧化钴,其中该多孔载体是包含闭孔结构的陶瓷泡沫体。
本发明进一步提供一种由该催化剂前体生产的催化剂,制造该催化剂和催化剂前体的方法,和该催化剂在费托方法中的用途。
催化剂前体中的氧化锆可以是Co3O4和/或CoO,不过Co3O4更合适。氧化钴可以作为微晶存在于多孔催化剂载体上,并且平均微晶尺寸是5-25nm。
催化剂前体以Co表示的钴含量可以是5-50wt%,优选10-40wt%,更优选10-30wt%。
催化剂前体可以进一步包含一种或多种促进剂金属或金属化合物,来增强该催化剂的活性或选择性和/或增强氧化钴到钴金属的还原。合适的促进剂金属包括Pt、Pd、Ru和Re中的一种或多种。促进剂金属可以以0.01-1.0wt%,优选0.01-0.50wt%的量包含在催化剂前体中。
陶瓷泡沫体是一种固体多孔材料,通常其中具有许多形成气体填充的孔或空隙,以使得该载体的密度低于常规催化剂载体。可以通过用陶瓷浆料内部浸渍开放孔聚合物泡沫体,然后在窑炉中煅烧,仅留下陶瓷材料,来制造开放孔陶瓷泡沫体。在本发明中,陶瓷泡沫体包含闭孔结构,因此通过不同的方法制备。术语“闭孔结构”表示泡沫体内的孔或空隙通常不互连,不过小比例的,例如至多约20%的孔体积,但是优选小于10%的孔体积可以互连。在闭孔结构中,不同于开孔结构,通常不存在从一侧到另一侧穿过泡沫体的开放流路,所以流过该泡沫体的气体必须扩散穿过孔壁从一个孔到下一个孔。闭孔结构中孔的形状将取决于制造方法和条件,但是典型地是球形或者具有圆形横截面的扭曲球形。孔的直径可以是0.1-500μm,不过大部分(即数目>50%)的孔理想的直径是0.1-250μm。平均孔径可以是0.2-150μm,优选1-100μm。孔径可以使用显微镜法测量。
泡沫体的空隙分数可以是50-95vol%,优选75-90vol%。因此,泡沫体的固体含量可以是5-50%,优选10-25vol%。
因为载体具有闭孔结构,所以孔之间存在壁。孔壁是多孔的,即该孔壁可以包含气体可以穿过的孔。孔尺寸或宽度可以直径>50nm,不过优选孔的直径≤50nm。氧化钴存在于孔壁上和存在于孔壁中至少部分的孔中,其经过活化能够催化费托反应。费托反应受到反应气体的接触时间的影响,因此可以控制孔壁厚度来提供反应气体穿过催化剂的优化扩散路径,以使得选择性最大化。还可以控制孔壁厚度来赋予最终催化剂所需的强度。孔壁厚度可以至多500μm,优选至多200μm,并且平均是10-100μm,优选25-85μm。可以例如通过在陶瓷泡沫体的制造过程中控制它的空隙分数来控制壁厚度。
陶瓷泡沫体中的陶瓷可以使用金属氧化物或者适于负载费托催化剂的其他陶瓷材料例如SiC来形成。优选金属氧化物,并且合适的金属氧化物泡沫体可以使用氧化铝、金属铝酸盐、二氧化硅、二氧化铈、二氧化钛、氧化锆和它们的混合物来制备。不太优选二氧化硅。氧化铝可以通过与用于生产氧化锆的钴化合物反应来形成铝酸钴。铝酸钴还原性不如氧化钴,因此在氧化铝存在于催化剂载体中的情况中,该载体优选涂覆有另一金属氧化物例如二氧化硅、二氧化钛或氧化锆的层,或者氧化铝可以通过与合适的二价金属例如Ni反应来转化成另一金属铝酸盐。特别优选二氧化钛,这是由于它与钴的低相互作用和它形成发泡结构的能力。二氧化钛可以包含不同量的金红石和锐钛矿。优选高锐钛矿材料,例如锐钛矿含量>60wt%。
本发明进一步提供一种制备催化剂前体的方法,其包括步骤:(i)形成包含闭孔结构的陶瓷泡沫体,(ii)将钴化合物施用到该陶瓷泡沫体,和(iii)加热含钴的陶瓷泡沫体以形成催化剂前体。
可以使用不同的已知方法来形成包含闭孔结构的陶瓷泡沫体。例如,可以使用牺牲模板方法,其中将液体形式的陶瓷前体与牺牲模板材料(通常是另一液体)混合,并且将形成的组合物加热来分解该牺牲材料和在最终的陶瓷泡沫体中产生空隙。一种制备陶瓷泡沫体的优选方法是直接发泡方法,其中通过添加气体使液体陶瓷前体或者陶瓷粉末在合适液体中的悬浮液发泡以产生湿泡沫体,随后加热该湿泡沫体以产生最终的陶瓷泡沫体。一种特别优选的方法包括(i)形成陶瓷粉末在液体中的悬浮液,(ii)将气体添加到该液体以产生湿泡沫体,和(iii)加热该湿泡沫体以形成陶瓷泡沫体。该悬浮液可以含有一种或多种表面活性剂型的分子(可以称作“两亲物”),其与陶瓷粉末作用以稳定该湿泡沫体。因此,优选稳定化的湿泡沫体可以使用含有两亲物的陶瓷粉末的悬浮液来制备。生产这样的颗粒稳定化的泡沫体的方法是已知的。
EP1960097A1描述了一种制备表现出长期稳定性的湿泡沫体的方法,其中使用部分疏液的(lyophobized)胶体颗粒来稳定化气体-液体界面。在一方面中,通过在悬浮液的液相中用特定溶解度的两亲物处理初始亲水的颗粒,以使该颗粒部分原位疏液。已经发现这种方法对于制备本发明的催化剂前体特别有用。
因此,一种制备陶瓷泡沫体载体的适当方法可以包括步骤,其中:
1.将陶瓷粉末悬浮在含水相中;
2.将两亲物包含在悬浮液中。这在颗粒表面吸附,形成不太亲水的改性颗粒。
3.然后将空气或另一气体包含在该悬浮液中,形成气泡和使该改性颗粒结合到湿泡沫体的气体/含水相界面处,由此稳定化该湿泡沫体,和,
4.进一步加工该湿泡沫体,例如通过成形、干燥和/或煅烧。
因此,上面所列的粉末形式的陶瓷载体材料可以用于制备湿泡沫体。悬浮液中陶瓷颗粒的平均粒度可以是1nm-20μm,但是优选是2nm-10μm,更优选2nm-2μm。在使用平均粒度较大的陶瓷粉末的情况中,优选悬浮液经过研磨以获得在这些范围内的所需平均粒度。可以获得具有窄的以及宽的粒度分布的良好的泡沫体。可以使用已经经过表面改性剂预处理的陶瓷粉末,包括已经用两亲物预处理的陶瓷粉末。
稳定化的陶瓷胶体颗粒初始时是亲水的,并且通过将两亲分子吸附到颗粒表面来部分疏水化,优选原位进行。
两亲分子由偶联到头基团的尾部组成。该尾部通常可以描述为非极性的,并且可以是脂族(直链烷基或环烷基)或芳族(苯基或萘基),并且可以带有一种或多种取代基。这样的取代基可以是烷基,例如-CnH2n+1(n<8),芳基(例如苯基或取代的苯基),-OH,或–NH2。优选的尾部是任选取代的包含2-8个碳原子的直链碳链。偶联到尾部上的头基团优选是离子或极性基团,并且可以选自磷酸酯、膦酸酯、亚膦酸酯、硫酸酯、磺酸酯、羧化物(即COOH)、羧酸酯、没食子酸酯、酰胺、胺(包括环胺)和-OH。对于费托催化剂,优选羧酸和酯作为引入硫或磷的头基团。
特别优选的两亲物是C2-C6羧酸及其酯,例如戊酸、丁酸和丙酸,和C2-C6没食子酸酯例如没食子酸丙酯。此外,已经发现特别稳定的泡沫体可以使用氨基酸,特别是α-氨基酸来制备,其中胺基连接到与羧酸酯头基团相邻的碳原子。优选的α-氨基酸包括缬氨酸、异亮氨酸、亮氨酸、苯基丙胺酸和色氨酸中的一种或多种。可以使用蛋氨酸,其中形成的泡沫体的硫含量是可以容忍的。不太优选的α-氨基酸包括丙胺酸和酪氨酸。特别优选的α-氨基酸两亲物包括亮氨酸、异亮氨酸和苯基丙胺酸中的一种或多种。可以使用每种的D、L或DL形式。一种特别合适的氨基酸是苯基丙胺酸。可以使用DL-苯基丙胺酸。使用氨基酸两亲物具有以小气泡生产稳定的泡沫体的优点,而没有羧酸的处理困难,或者由羧酸的酸性pH引起的问题。
悬浮液的pH可以在包含两亲物之前进行调节,不过可以不是必需的。例如,pH可以调节到陶瓷粉末的表面电荷对于静电稳定是足够高时的pH。可以添加酸例如硝酸,或碱,但是对于费托催化剂来说不期望用碱金属调节pH,因为碱金属降低催化剂活性。
取决于要涂覆的表面的电荷,可以选择带负电或带正电的头基团。对于例如Al2O3,带负电的头基团适于低pH条件,即pH低于等电位点,其中pH<9,特别是pH4-5。上述头基团和另外的类似基团可以用于对广泛多种的陶瓷颗粒,特别是金属氧化物进行改性。
可以通过带负电或带正电的两亲物分子在合适的,优选相反电荷的表面上物理或化学吸附来实现表面改性,留下与含水相接触的疏水尾部。对于例如带正电的氧化铝颗粒,吸附可以用水中的羧酸在pH4.75进行。通过改变两亲物的锚极性头基团,也可以在碱性pH条件使用例如没食子酸烷基酯作为吸附分子来改性氧化铝表面。这种两亲物也可以用于使多种其他两性的和碱性的氧化物的表面疏液。可选地,酸性类氧化物例如二氧化硅、碳化硅和氮化硅的表面可以使用含胺的头基团两亲物来疏液。
对于颗粒的原位疏液来说,两亲物可以以小于颗粒的1wt%的量,优选<0.8wt%的量来施用。应当存在的两亲物的最小量可以是约0.001%,优选约0.1%。可以使用0.2-1.0mmol两亲物/g颗粒的量。因为两亲物除了悬浮液的其他成分之外,还影响泡沫体的粘度,所以所用改性剂的实际量根据所需的最终粘度来选择。
已经发现不同形状的陶瓷颗粒可以用作泡沫体稳定剂,即该陶瓷颗粒可以是球形、多边形平板、针状、纤维、棒状、单晶等,条件是它们的粒度在合适的尺寸内。颗粒本身可以是致密的,即非多孔的,或者是多孔的,或者可以使用致密和多孔颗粒的混合物。
颗粒优选的存在量是悬浮液中的至少约5%v/v。上限由粘度来确定,其必须不能过高。通常所述粘度在100s-1的剪切速率不应当超过10Pa·s。发泡整个悬浮液所需的最小量取决于粒度,并且可以由本领域技术人员容易地确定。通常颗粒越小,生产稳定化的湿泡沫体的颗粒的量越少。在本发明中,悬浮液的固体浓度优选是10-45wt%,优选25-35wt%。
湿泡沫体合适地在至多90℃的温度形成。较低的温度受限于含水相的冻结。该方法在它在低于所讨论的两亲物的克拉夫特温度操作的情况中表现最佳。克拉夫特温度(也称作克拉夫特点,或临界胶团温度)是表面活性剂形成胶团时的最小温度。低于克拉夫特温度时,不存在临界胶团浓度(CMC)值,即不能形成胶团。
可以使用不同的方法制备湿泡沫体,例如将气泡引入悬浮液中。引入的气泡可以是小气泡,或者它们可以是大气泡,其经过剪切悬浮液而分成所需量的小气泡。
可以将空气或另一气体例如氮气、氧气、氩气和二氧化碳引入该悬浮液中,以通过任何合适的手段产生湿泡沫体。例如,泡沫体可以通过将悬浮液经过高强度和/或高速搅拌,同时暴露于大气来产生。搅拌可以使用混合器例如高速旋转的机械混合器来进行。根据最终产品的所需的物理和其他性质,搅拌进行足够的时间,以将空气气泡引入悬浮液中,直到实现膨胀。膨胀率,即形成的泡沫体的体积与起始悬浮液的体积之比,可以是约1.5-约15。因此,可以使用汲取管或喷洒器设备。在一个实施方案中,可以使用气体诱导叶轮。当在悬浮液内旋转时,气体诱导叶轮将气泡从叶轮的叶片引入。气体诱导叶轮是已知的,但是以前没有被用于生产陶瓷泡沫体材料。可选地,可以在搅拌的同时,通过将气体鼓泡穿过规定孔尺寸的过滤器进入悬浮液中来引入该气体。在这种情况中,泡沫体最终的孔尺寸可以取决于过滤器的孔尺寸。在一种变化中,驱使高压气体穿过细过滤器,然后在合适的腔室中与悬浮液紧密混合,然后将充气的混合物从喷嘴射出。可选地,可以使用气溶胶方法,其中将悬浮液置于加压容器中,并且将气体例如空气或二氧化碳在压力下注入悬浮液中,以在压力例如经由喷嘴释放时产生泡沫。
也可以在悬浮液中通过将气体形成试剂包含在该悬浮液中,并且通过加热或化学反应激活它来形成气体,从而形成气泡。这样的气体形成试剂包括叠氮化钠和过氧化氢。
悬浮液中气泡的形成可以以间歇方式或连续方式来完成。
含水相包含水,例如自来水(mains water)或软化水,其可以进一步包含亲水溶剂例如醇、二醇等及其混合物。可以添加另外的添加剂例如酸或碱例如来调节pH和/或离子强度。
如上所述,优选的pH或pH范围取决于用于原位疏液化的头基团和要改性的颗粒表面。应当是至少约1.5%,优选至少约10%,更优选约50%的头基团是带负电的(脱质子的)或带正电的(质子化的)。
可以调节离子强度以促使结合的颗粒在界面处的紧密填充和泡沫薄片内颗粒的吸引。但是,离子强度应当保持得足够低以确保悬浮液存在足够低的粘度,以允许充分引入空气或者良好发泡。
悬浮液粘度优选是该粘度小于不能发生气体引入的水平并且高于捕获的气泡倾向于逸出的水平。在不添加两亲物时,在100s-1的剪切速率时粘度可以是5mPa·s-1000mPa·s。当存在两亲物时,在100s-1的剪切速率时悬浮液的粘度可以是约5mPa·s-约10,000mPa·s,优选25mPa·s-约5000mPa·s。优选的范围取决于气体捕获方法。
湿泡沫体的气泡尺寸取决于全部上述参数,特别是粘度、添加剂的量、颗粒的量和用于将空气带入悬浮液中的设备或依赖于该设备的方法参数。气泡尺寸例如直径可以是1μm-1mm,优选1μm-500μm。气泡最终提供催化剂前体中的孔。
湿泡沫体可以浇铸到模具中以成形,或者可以使用适于对湿泡沫体粘度进行调节的常规挤出装置通过挤出来成形。然后铸塑的或挤出的泡沫体可以经过干燥步骤,以产生具有足够的生坯强度用于进一步加工的固体泡沫体。
干燥可以使用常规烘箱在至多约120℃进行。干燥时间可以根据需要在0.1-48小时变化以保存泡沫体结构。干燥可以在大气压或减压进行。在减压时,泡沫体可以在形成生坯强度之前膨胀。膨胀度和因此泡沫体孔尺寸将取决于所选的压力。在升高的温度干燥也会引起泡沫体轻微膨胀。优选控制干燥步骤中的湿度,以防止不均匀收缩和干燥裂纹。温度辅助的或真空辅助的单向干燥使样品均匀收缩,而不引起会导致裂纹的应力。还可以使用冷冻干燥。
悬浮液可以包含其他成分,其在干燥阶段起作用。这样的成分的例子包括粘结剂如树脂,例如聚氯乙烯、树胶、纤维素、淀粉、聚乙烯醇、寡糖和多糖,以增强生坯强度。还可以包含可聚合材料,不过这不太优选。虽然添加粘结剂通常不是生产合适的湿泡沫体所必需的,但是如果需要干燥后高的生坯强度,则这样的添加剂会具有优势。在粘结剂或可聚合材料存在下干燥后的形成体相当坚固,并且当要形成的制品是复杂形状时,优选添加粘结剂或可聚合材料。
铸塑的或挤出的泡沫体可以经过另外的成形步骤,包括例如将陶瓷泡沫体研磨或磨碎到所需粒度,筛分,粒化造粒和本领域已知的其他成形程序。
泡沫体可以经过加热步骤或煅烧,其中陶瓷颗粒熔合在一起以形成多孔催化剂载体材料。这样的加热可以在500-1600℃或更高的温度进行,这取决于陶瓷,不过为了在孔壁中保持合适的孔结构,期望的是在低于约1200℃煅烧陶瓷泡沫体。煅烧可以进行1-24小时,优选1-8小时,这取决于所选的温度。加热步骤可以在空气或者惰性气氛例如氮气或氩气下进行。在预期有机残留物分解的情况中,优选后者。
本发明包括将氧化钴或其前体施用到陶瓷泡沫体的步骤。这可以通过施用含有氧化钴的载体涂层(wash-coat)浆料来完成,但是这不太优选,因为泡沫体包含闭孔结构,所以钴将不能渗透泡沫体超过表面孔。所以,优选使用一种或多种可溶性钴化合物的溶液来制备催化剂前体。钴化合物可以是有机钴化合物例如乙酰丙酮钴,钴络合物例如碳酸氨合钴,或者可以是钴盐例如醋酸钴和/或硝酸钴。可以使用一种或多种可溶性钴化合物。因此,在一种优选的方法中,将可溶性钴化合物溶解在合适的溶剂例如水中,以形成钴溶液,并且例如通过喷涂或浸涂,将该钴溶液施用到陶瓷泡沫体,以浸渍孔和孔壁孔。除了可溶性钴化合物之外,一种或多种可溶性促进剂化合物可以包含在钴溶液中,或者可以在分别的浸渍步骤中施用到泡沫体。优选Pt、Pd、Ru和Re的可溶性化合物。
然后浸渍的陶瓷泡沫体可以经过干燥以除去溶剂,并留下沉积在泡沫体内的钴。钴可以作为盐或络合物来沉积,或者可以是氧化钴,这取决于用于浸渍陶瓷泡沫体的方法。优选钴和任何促进剂最终沉积在陶瓷泡沫体内。一种特别合适的沉积钴的方法使用碳酸氨合钴络合物,其经过氧化和加热,将氧化钴直接沉积到陶瓷泡沫体的孔腔和孔中。
如果需要,钴化合物可以经过加热步骤或煅烧以使它们分解来形成氧化钴。这可以通过干燥步骤来完成,或者煅烧步骤可以单独进行。可以通过将浸渍的或干燥的含钴陶瓷泡沫体在空气或惰性气体例如氮气或氩气下加热到至多约800℃,优选200-800℃,更优选200-600℃,最优选200-400℃的温度,以方便地实现钴化合物向氧化钴的转化。钴化合物的煅烧可以进行0.5-8小时,这取决于温度。
可以提供钴为氧化物形式的催化剂前体用于费托方法。在使用前,通过将催化剂前体中的氧化钴还原成钴金属来活化催化剂前体,以产生适于费托反应的催化剂。
可选地,可以预还原和包封催化剂前体,以提供用于费托方法的催化剂产品。
可以通过在升高的温度使含氢气体例如氢气、合成气或者氢气与氮气、甲烷或其他惰性气体的混合物流过催化剂前体来进行还原,例如通过在150-600℃,优选250-600℃,优选275-500℃的温度使含氢气体流过组合物1-24小时。可以在大气压或至多约25绝对巴的更高压力进行还原。
还原态的催化剂会难以处理,因为它们会与空气中的氧气自发反应,这会导致不期望的自加热和活性损失。对于适于费托方法的催化剂来说,优选通过用合适的隔离涂层包覆还原的催化剂颗粒来保护该还原的催化剂。在费托催化剂的情况中,这可以合适地是FT-烃蜡。可选地,催化剂可以以还原态提供,并且用含氢气体原位还原。
在陶瓷泡沫体载体上制备的钴催化剂的钴表面积(在425℃还原后,通过在150℃的氢气化学吸附来测定)可以≥1m2/g催化剂。钴表面积可以合适地通过H2化学吸附来测定。优选的方法如下;首先将约0.2-0.5g的样品材料脱气,并且通过在流动氦气中以10℃/min加热到140℃来干燥,并且将它在140℃保持60min。然后,脱气的和干燥的样品如下来还原:在50ml/min氢气流下将它以3℃/min的速率从140℃加热到425℃,然后将它在相同的氢气流下在425℃保持6小时。在还原后和在真空下,将该样品以10℃/min加热到450℃,并且在这些条件下保持2小时。然后将该样品冷却到150℃和在真空下保持另外30分钟。在150℃使用纯氢气来进行化学吸附分析。使用自动分析程序来测量在100mmHg到760mmHg的氢气压力上的全等温线。进行两次分析:第一次测量“总”氢气吸附(即包括化学吸附的氢气和物理吸附的氢气),并且在第一次分析之后立即将该样品置于真空(<5mmHg)下30min。然后重复该分析来测量物理吸附的吸附量。因此可以将线性回归用于“总”吸附数据,并且外推回零压力来计算化学吸附的气体体积(V)。
在全部情况中,使用以下等式来计算钴表面积:
Co表面积=(6.023×1023×V×SF×A)/22414
其中V=H2吸收量,ml/g
SF=化学计量因子(对于Co上的H2化学吸附,假定为2)
A=一个钴所占据的面积(假定是0.0662nm2)
这个等式描述在Operators Manual for the Micromeretics ASAP2010ChemiSystem V 2.01,附录C,第201-42808-01部分,1996年10月中。
该催化剂可以用于烃的费托合成。因此,本发明进一步提供一种费托合成烃的方法,其包括使含有氢气和一氧化碳的气体混合物与包含含有闭孔结构的陶瓷泡沫体载体的钴催化剂接触。
使用钴催化剂的烃的费托合成是公知的。费托合成将一氧化碳和氢气的混合物转化成烃。一氧化碳和氢气的混合物典型地是氢气:一氧化碳之比是1.6-3.0:1,优选1.7-2.5:1的合成气。该反应可以使用一个或多个固定床反应器、搅拌浆料相反应器、喷射回路反应器、鼓泡塔反应器或流化床反应器,在连续或间歇方法中进行。该方法可以在0.1-10Mpa的压力和150-350℃,优选200-250℃的温度操作。用于连续操作的气体时空速度(GHSV)是100-25000h-1。一个优选的操作范围是1000-15000h-1。
本发明的催化剂能够提供对于所需的C5+烃出人意料地高的选择性,例如二氧化钛泡沫体负载的FT催化剂的C5+选择性可以超过90%。
现在将参考下面的实施例来进一步描述本发明。
实施例1 二氧化钛泡沫体制备
a)使用含有30wt%固体的二氧化钛悬浮液来制备陶瓷泡沫体。将128g二氧化钛粉末(P25,可获自Evonik)缓慢添加到搅拌容器中的300ml软化水中。然后,不调节pH,基于每克二氧化钛添加0.36mmol的DL-苯基丙胺酸(7.6g的DL-苯基丙胺酸)。悬浮液的pH是4.59。然后使用气体诱导叶轮30分钟将空气引入该悬浮液来形成气泡。将泡沫浇铸到盘中,并且在室温和大气压干燥。然后通过以2℃/min加热到600℃,用氮气吹扫来煅烧它。在600℃45分钟后,将用空气替代氮气流。在600℃的总停留时间是4小时。将形成的陶瓷泡沫体载体压碎和筛分到0.5mm。
如下来进行孔隙率测量:将该陶瓷泡沫体在室温在软化水中浸泡4天,并且通过重量增加来测量吸水量。以此方式测量的孔隙率包括空腔和可达的孔的体积,并且指示了可以用于制备催化剂的钴溶液的体积。发泡二氧化钛在4天后的孔隙率是0.8cm3/g。
b)如下来对悬浮液中不同的二氧化钛含量重复该方法;
c)重复该方法,用正丁酸代替苯基丙胺酸。在空气捕获之前需要使用氢氧化钾调节pH。
*pH没有进一步增加,因为观察到粘度增加
d)重复该方法,用其他α-氨基酸代替苯基丙胺酸。除非另有指示,否则在空气捕获之前没有进行pH调节。
*通过添加硝酸来调节pH
实施例2催化剂前体制备
a)实施例1(a)的二氧化钛泡沫体的硝酸钴浸渍。
将7g硝酸钴六水合物(Co(NO3)2·6H2O)和2.2ml软化水加热,直到盐完成熔融和溶解。将其按等份添加到塑料袋中实施例1(a)的15g陶瓷泡沫体产物中。在每次添加后,将材料捏合成载体。将浸渍的泡沫体在105℃干燥2小时和在300℃煅烧2小时。然后重复该方法。将5.5g的Co(NO3)2·6H2O和2.74ml软化水加热,直到盐完成熔融和溶解。将其按等份添加到塑料袋中来自于第一次浸渍的16.5g浸渍的陶瓷泡沫体产物中。在每次添加后,将材料捏合成载体。将形成的材料在105℃干燥2小时和在300℃煅烧2小时。通过ICPAES测定的催化剂前体的钴含量是10.8wt%。通过氢气化学吸附测量的钴表面积是1.0m2/g催化剂。
b)实施例1(a)的二氧化钛泡沫体的碳酸氨合钴浸渍。
如下来制备碳酸氨合钴溶液:将198ml的28%氨溶液添加到圆底烧瓶中20.4g的碳酸铵中,并且用193.4ml软化水稀释。将形成的溶液搅拌20分钟,然后在15分钟内添加23.7g碱式碳酸钴,并且将溶液以150rpm搅拌另外2.5h以产生紫色溶液。逐滴添加30%过氧化氢溶液,同时以234rpm搅拌该溶液,直到氧化还原电势(Metler Toledo transmitter M 700)接近-100mV。继续搅拌另外10分钟,然后过滤该溶液。
将385ml的碳酸氨合钴溶液(2.6%w/w Co)添加到2L四颈圆底烧瓶中。将搅拌器、温度探针、封泥和冷凝器安装到该烧瓶。添加52g实施例1(a)的陶瓷泡沫体产物。然后将这个混合物用385mL水和165mL氨稀释,随后加热和搅拌80分钟以使氨析出和氧化钴沉积在陶瓷泡沫体的孔腔和孔中。将该混合物过滤和用80ml软化水清洗。将催化剂前体在105℃干燥8小时。未煅烧。通过ICPAES测定的催化剂前体的钴含量是11.2wt%。通过氢气化学吸附测量的钴表面积是1.1m2/g催化剂。
c)实施例1(d)(i)-(iv)的二氧化钛泡沫体的碳酸氨合钴浸渍。
代替使用实施例1(d)(i)-(iv)获得的二氧化钛泡沫体,来重复实施例2(b)的方法。在每种情况中目标钴含量是13wt%。通过氢气化学吸附测量的催化剂前体的钴表面积如下所述。
泡沫体 | 钴表面积(m2/g催化剂) |
1(d)(i) | 3.9 |
1(d)(ii) | 1.6 |
1(d)(iii) | 1.5 |
1(d)(iv) | 1.5 |
实施例3催化剂测试
对0.5g的实施例2(a)的催化剂进行费托合成中催化性能测试。反应条件是合成气(H2:CO是2:1)流速30mlN/min,20巴和210℃,并且GHSV是3590mlN合成气·g催化剂-1·h-1和目标转化率是50%。对C5+的选择性是92%。
对0.25g的实施例2(b)的催化剂进行费托合成中催化性能测试。反应条件是合成气(H2:CO是2:1)流速44mlN/min,20巴和210℃,并且GHSV是10338mlN合成气·g催化剂-1·h-1和目标转化率是50%。对C5+的选择性是91%。
对0.25g的实施例2(c)的每个催化剂进行费托合成中催化性能测试。反应条件是合成气(H2:CO是2:1),20巴和210℃,和目标转化率是50%。对于基于不同的泡沫体材料的催化剂,其余反应条件和对C5+的选择性如下:
Claims (20)
1.适于费托反应的催化剂前体,其包含负载在多孔载体上的氧化钴,其中该多孔载体是包含闭孔结构的陶瓷泡沫体。
2.根据权利要求1所述的催化剂前体,其中该催化剂前体以Co表示的钴含量是5-50wt%,优选10-40wt%,更优选10-30wt%。
3.根据权利要求1或2所述的催化剂前体,其中至多20%的孔体积,优选小于10%的孔体积是互连的。
4.根据权利要求1-3中任一项所述的催化剂前体,其中该平均孔径是10-150μm,优选10-100μm。
5.根据权利要求1-4中任一项所述的催化剂前体,其中该泡沫体的孔分数是50-95vol%,优选75-90vol%。
6.根据权利要求1-5中任一项所述的催化剂前体,其中孔壁厚度是至多500μm,优选至多200μm,并且平均是10-100μm,优选25-85μm。
7.根据权利要求1-6中任一项所述的催化剂前体,其中该陶瓷泡沫体包含二氧化钛。
8.制备根据权利要求1-7中任一项所述的催化剂前体的方法,其包括步骤:(i)形成包含闭孔结构的陶瓷泡沫体,(ii)将钴化合物施用到该陶瓷泡沫体,和(iii)加热含钴的发泡金属氧化物以形成该催化剂前体。
9.根据权利要求8所述的方法,其中该陶瓷泡沫体通过包括以下的步骤形成:(i)形成陶瓷粉末在液体中的悬浮液,(ii)将气体添加到该液体以产生湿泡沫体,和(iii)加热该湿泡沫体以形成该陶瓷泡沫体。
10.根据权利要求9所述的方法,其中该悬浮液中的陶瓷粉末粒度是1nm-20μm,优选2nm-10μm,更优选2nm-2μm。
11.根据权利要求9或10所述的方法,其中该悬浮液含有一种或多种两亲物,其与该陶瓷粉末作用以稳定化该湿泡沫体。
12.根据权利要求11所述的方法,其中该两亲物包括C2-C6羧酸及其酯、C2-C6没食子酸酯和α氨基酸中的一种或多种。
13.根据权利要求11或12所述的方法,其中该两亲物包括缬氨酸、异亮氨酸、亮氨酸、苯基丙胺酸或色氨酸中的一种或多种,优选亮氨酸、异亮氨酸和苯基丙胺酸中的一种或多种,更优选苯基丙胺酸。
14.根据权利要求9-13中任一项所述的方法,其中将该湿泡沫体在加热前成形。
15.根据权利要求14所述的方法,其中使成形的泡沫体经过500-1600℃的温度的加热步骤。
16.根据权利要求8-15中任一项所述的方法,其中施用到陶瓷泡沫体的该钴化合物是有机钴化合物、钴络合物或钴盐。
17.催化剂,其使用根据权利要求1-7中任一项所述的催化剂前体制备,或者根据权利要求8-16中任一项制备,该催化剂包含负载在多孔载体上的单质形式的钴,其中该多孔载体是包含闭孔结构的陶瓷泡沫体。
18.根据权利要求17所述的催化剂,其包封在烃蜡中。
19.制备根据权利要求17或18所述的催化剂的方法,其包括步骤:根据权利要求9-16中任一项制备催化剂前体,和将还原性气流施用到该催化剂前体,以将氧化钴的至少一部分转化成单质形式。
20.通过费托反应生产烃的方法,其包括使包含一氧化碳和氢气的合成气与根据权利要求17或18所述的催化剂接触。
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