CN105451883A - 制造用于生成多壁碳纳米管的有效催化剂的方法、多壁碳纳米管和碳纳米管粉末 - Google Patents
制造用于生成多壁碳纳米管的有效催化剂的方法、多壁碳纳米管和碳纳米管粉末 Download PDFInfo
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- CN105451883A CN105451883A CN201480040958.1A CN201480040958A CN105451883A CN 105451883 A CN105451883 A CN 105451883A CN 201480040958 A CN201480040958 A CN 201480040958A CN 105451883 A CN105451883 A CN 105451883A
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Abstract
本发明涉及制造用于合成多壁碳纳米管的催化剂的方法。本发明还涉及制造多壁碳纳米管的方法以及包含这些碳纳米管并具有改进的性能的碳纳米管粉末。
Description
本发明涉及制造用于合成多壁碳纳米管的催化剂的方法。本发明还涉及制造多壁碳纳米管的方法以及包含这些碳纳米管并具有改进的性能的碳纳米管粉末。
根据现有技术,碳纳米管主要是直径1至100纳米且长度为直径的数倍的圆柱形碳管。这些管由一个或多个有序碳原子层构成并具有形态不同的芯。这些碳纳米管也被称作例如“碳原纤”或“中空碳纤维”。
碳纳米管早已从技术文献中获知。尽管Iijima(出版物: S.
Iijima, Nature 354, 56-58, 1991)通常被认为是纳米管的发现者,但这些材料,特别是具有多个石墨烯层的纤维状石墨材料早在七十年代或八十年代初已为人所知。Tates和Baker(GB 1469930A1,1977和EP 0056004A2,1982)首次描述由烃的催化分解沉积极细的纤维状碳。但是,基于短链烃制成的碳丝没有在其直径方面更详细表征。
在EP 205 556B1和WO
86/03455A1中首次描述直径小于100纳米的碳纳米管的制造。在此,使用轻质(即短链和中链脂族或单环或双环芳族)烃和铁基催化剂(经此碳载体化合物在800℃-900℃以上的温度下分解)制造它们。
如今已知用于制造碳纳米管的方法包括电弧法、激光消融法和催化法。在许多这些方法中,作为副产物形成炭黑、无定形碳和具有大直径的纤维。在催化法中,可以区分沉积在引入的催化剂颗粒上和沉积在原位形成并具有纳米范围直径的金属中心上(所谓的流动法(Flow-Verfahren))。在由在反应条件下为气态的烃催化沉积碳来制造的途径(下文称作CCVD;催化碳气相沉积)时,提到乙炔、甲烷、乙烷、乙烯、丁烷、丁烯、丁二烯、苯和其它含碳原材料作为可能的碳给体。
该催化剂通常包含金属、金属氧化物或可分解或可还原的金属组分。例如,在现有技术中提到Fe、Mo、Ni、V、Mn、Sn、Co、Cu等作为被考虑用于催化剂的金属。尽管各金属通常甚至独自具有催化纳米管形成的趋势。但是,根据现有技术,有利地使用含有上述金属的组合的金属催化剂实现纳米管的高收率和无定形碳的小含量。
根据现有技术,特别有利的催化剂体系基于含有Fe、Co或Ni的组合。碳纳米管的形成和所形成的管的性能以复杂方式取决于用作催化剂的金属组分或多种金属组分的组合、所用载体材料和催化剂与载体之间的相互作用、进料气体和进料气体分压、氢气或其它气体的添加、反应温度和停留时间和所用反应器。对工业方法而言优化是一个特别的挑战。
碳纳米管的典型结构是圆柱型的那些(管形结构)。在圆柱形结构的情况下,区分单壁碳纳米管(SWCNT)和多壁碳纳米管(MWCNT)。它们的常规制造方法是例如电弧法(电弧放电)、激光消融、化学气相沉积(CVD法)和催化化学气相沉积(CCVD法)。
同样可通过电弧法制造这种类型的圆柱形碳纳米管。Iijima (Nature 354, 1991, 56-8)报道了借助电弧法形成由卷绕形成无缝封闭圆柱体并相互嵌套的两个或更多个石墨烯层构成的碳管。根据卷绕矢量(Aufrollvektor),沿碳纤维纵轴的碳原子的手性和非手性排列是可能的。
可以通过WO 2009/036877 A2中描述的方法制造具有所谓的卷轴结构的碳纳米管,其中一个或多个石墨层(由两个或更多个彼此叠置的石墨层构成)形成卷绕结构。
在一份综述(Milne等人Encyclopedia of
Nanoscience and Nanotechnology, 2003, 第X卷, 第1-22页;ISBN
1-58883-001-2)中描述了碳纳米管的另一些已知结构并且是“鲱鱼骨(Herring-bone)”结构或杯叠(cup-stacked)结构和堆叠结构、竹子结构、薄片结构。碳纳米纤维同样可通过聚丙烯腈的电纺丝和随后的石墨化制造(Jo等人Macromolecular Research, 2005, 第13卷, 第521-528页)。
可以指出,CCVD中使用的并被称作催化剂的金属组分在合成法过程中消耗。这种消耗可归因于该金属组分的失活,例如由于碳沉积在整个颗粒上以致完全覆盖颗粒(这被本领域技术人员称作“盖帽(Encapping)”)。再活化通常不可能或在经济上不可行。通常,每克催化剂仅获得最多几克碳纳米管,其中此处的催化剂包含所用载体和催化剂的总和。由于催化剂的上述消耗,基于所用催化剂计的碳纳米管的高收率是对催化剂和方法的重要要求。
随着碳纳米管的工业和技术重要性提高,除对高效、经济和可规模化的CNT制造方法外,对该碳纳米管或由其构成的碳纳米管粉末的性质和性能(特别是在纯度、可加工性和性能方面)的要求也提高。为了实现尽可能高的经济效率,除原材料的成本,特别是催化剂成本外,时空收率,即在特定反应器体积中每单位时间可制造的CNT的量至关重要。
在现有技术中,Oberlin、Endo和Koyama描述了一种制造圆柱形碳纳米管的方式(Carbon
14, 1976, 133);在此,在气流床反应器(Flugstromreaktor)中使芳烃如苯在大约1100℃下在金属催化剂,特别是铁上反应。在此,形成具有石墨芯的碳纳米管,但该芯被无定形碳的涂层覆盖。这些纤维随后在通常高于1800℃的高温下的技术上复杂和昂贵的热处理则产生主要包含石墨碳的产物。在此,通常也除去催化剂的一部分,由此实现提纯。该产物仅非常轻微缠结或未缠结,这由于低堆积密度和极端成尘表现而使操作非常困难。
在US 7,198,772B2(Hyperion
Catalysis International)中描述了另一制造碳纳米管的方法;在此,使乙烯在大约680℃的温度下在含铁催化剂上反应。用于该CNT合成的催化剂通过活性金属(通常铁和钼)沉淀在载体(如氧化铝、氢氧化铝或氧化镁)上以及通过活性金属和载体的共沉淀而获得。由此制成的CNT以聚集体的形式以每1克催化剂11.4-46克CNT的产量分离。在此,共沉淀的催化剂通常表现出更高效率。
专利申请WO 2006/050903(Bayer
MaterialScience AG)描述了已可非常有效地用于制造碳纳米管的催化剂体系。在此,在碱性条件下同时共沉淀钴盐、锰盐、镁盐和铝盐。
专利申请WO 2009/043445A1描述了借助喷雾干燥制造催化剂;在此,原料盐也可部分以分散在溶剂中的形式存在。但是,不发生共沉淀,尤其在碱性条件下不发生。产量为使用的每克催化剂大约25至34克碳纳米管。
因此,上述现有技术只能在有限程度上以高纯度和低成本制造碳纳米管。
本发明的一个目的是提供负载型催化剂,其一方面本身可以低廉地制造,另一方面能以在所用催化剂以及反应器中的时空收率方面都提高的效率制造碳纳米管。
本发明的另一目的是提供改进的CNT制造方法,其中可以获得具有高品质和优异性能,例如极高表面积的碳纳米管。由于经济原因,还希望的是这样的催化剂,其能在其它方面几乎相同的反应器结构和工艺方式下通过CNT制造条件例如温度的仅轻微变化来制造为各预期用途目的而优化并尤其具有不同比表面积的不同CNT。
根据本发明,借助制造至少由一种或多种活性金属和一种或多种载体材料构成的催化剂的方法实现该目的,所述方法包含下列步骤:
a) 预先放置充当用于催化剂的载体材料的粉末形式的基材,通过机械作用将所述基材粉末分散在溶剂中,并将所述分散体设定至至少8,优选至少9,特别优选至少9.5和最大13的pH值,
b) 任选在重新设定所选pH值的情况下,添加一种或多种含有催化活性金属和载体金属的前体化合物的金属盐溶液以使它们共沉淀并同时沉积(aufgefällt)在预先分散的基材粉末上,c) 移除(Abtrennung)和分离沉淀的固体,
d) 任选用溶剂洗涤所述固体,
e) 喷雾干燥或干燥和任选研磨和/或筛分(分级),
f) 任选在200℃-950℃,优选400℃-900℃,特别优选400℃-850℃下煅烧,并还原或氧化和随后还原,
g) 还原所形成的催化剂材料。
作为催化活性金属的优选合适的前体化合物,优选使用一种或多种选自铁、钴、镍、锰或钼的金属的化合物。
特别优选使用钴和锰的化合物(其优选以混合形式)作为前体化合物。
用于载体材料的优选合适的前体化合物选自镁、铝、硅、钛、钡或钙的化合物的一种或多种化合物。
用于载体材料的特别优选的前体化合物是镁和/或铝的化合物。
来自步骤a)的预先放置的基材粉末的平均粒径优选小于1毫米,特别优选小于0.1毫米,特别小于0.02毫米。
用于催化剂或载体的优选前体化合物彼此独立地为上述金属的水溶性盐,特别是硝酸盐、亚硝酸盐、氯化物、硫酸盐、羧酸盐,特别是乙酸盐或柠檬酸盐。该金属化合物特别优选以硝酸盐或乙酸盐形式存在。
该新型方法的一个优选实施方案的特征在于该金属以它们的氧化物或氢氧化物、混合氧化物/氢氧化物、或混合氧化物或混合氢氧化物的形式存在于来自步骤c)的分离的固体中。
在一种更优选的方法中,在根据步骤e)的喷雾干燥和/或研磨和筛分后该催化剂的主要级分的粒径为0.01至1毫米,优选0.02至0.25毫米,特别是0.03至0.12毫米。
该新型催化剂制造方法优选使用一种或多种选自水、醇、醚、酮的溶剂作为用于步骤a)、b)和任选d)的溶剂来进行。特别优选使用水作为溶剂。
在该新型方法的另一个优选的变体中,在步骤b)中添加金属盐溶液的过程中,特别通过搅拌或借助高压分散,剧烈均化该分散体。
在该新型方法的另一个优选实施方案中,借助碱金属氢氧化物或氢氧化铵或碱金属碳酸盐或碳酸铵或碱金属碳酸氢盐或碳酸氢铵,特别借助碱金属氢氧化物或氢氧化铵实施该分散体中的pH值的设定和重新设定。这些物质特别以水溶液的形式添加到该分散体中。
优选的碱金属化合物是锂、钠或钾的化合物,特别优选的是钠化合物。
优选在最多100℃的分散体温度下,优选在环境温度下进行沉淀b)。
一种优选方法的特征在于,该催化剂中的催化活性金属与载体的金属的以摩尔%计的金属含量的比率为90/10至5/95,优选80/20至20/80,特别优选70/30至30/70。
预先放置的用于催化剂载体的基材金属与沉淀的用于催化剂载体的基材金属的以摩尔%计的含量的比率为1/99至95/5,在该方法的一个优选实施方案中为2/98至50/50。
本发明还提供由如上所述的新型催化剂制造方法获得的催化剂。
本发明还提供通过如上所述的新型催化剂制造方法制成的催化剂用于制造纤维状碳材料,特别是碳纳米管的用途。
本发明还提供制造纤维状碳(碳纳米管)的方法,其通过使用如上所述的新型催化剂制造方法制造催化剂,
将来自该催化剂制造方法的催化剂引入合适的反应器,该反应器优选具有移动反应床,特别是流化床,
通过含碳气体(前体)在该催化剂存在下在升高的温度,特别是至少500℃至1000℃,优选550℃至850℃,特别优选600℃至750℃下,任选在氢气和/或惰性气体,特别是氮气和/或稀有气体存在下的反应产生碳纳米管,并从该反应器中排出碳纳米管和其它反应产物。
在本发明中已经发现,不同于现有技术,具有这些步骤的方法以极高效率(即基于所用催化剂计极高的CNT收率以及在反应器中的时空收率方面)获得碳纳米管。此外,在使用本发明的催化剂时,可以通过CNT制造步骤中的温度变化有针对性地改变和设定形成的CNT的表面积。
原则上,所有类型的碳纳米管都可通过该新型碳纳米管制造方法获得。碳纳米管类型的实例是:具有单个类石墨烯层的单壁纳米管、具有多个类石墨烯层的多壁纳米管;具有管状结构、竹子结构、鲱鱼骨结构、杯叠结构、卷绕结构或卷轴结构的碳纳米管;所谓的盖帽的(capped)碳纳米管,其中至少一个管状类石墨烯层在其末端被富勒烯半球体封闭;或上述类型以及碳纳米纤维和含硼或氮的碳纳米管(B-CNT、N-CNT)的各种可能的组合。
下面一般而言和在特别的实施方案中更详细描述该碳纳米管制造方法。
该碳纳米管制造方法优选在反应器的移动床中进行。具有移动床的反应器在工艺工程上特别不同于固定床反应器以及没有床的反应器,例如气流床反应器。在具有床的反应器的情况下,基材在空间上位于载体之上。在固定床反应器的情况下,基材可以例如包含在顶部敞开的皿中,其中该皿在这种情况下充当载体。该基材因此在此过程中基本静止。
含碳前体优选含有或由任选取代的脂族、环状、杂环、芳族或杂芳族化合物或其混合物构成。
在此,脂族是指非支化、支化和/或环状的烷烃、烯烃或炔烃。该脂族分子优选具有大约1至大约20,特别是大约1至大约12,特别优选大约2至大约6个碳原子。
实际实验表明,当该含碳前体是至少部分不饱和或芳族化合物,或该前体含有这样的化合物或其混合物时,获得特别好的结果。
部分不饱和化合物的实例是可任选被取代的非支化、支化和/或环状烯烃或炔烃。
本文所用的术语“烯烃”是指含有至少一个碳-碳双键的烃基本部分(Grundelement)。可根据本发明使用的含碳前体是例如乙烯、丙烯、丁烯、丁二烯、戊烯、异戊二烯、己烯、1-, 2-或3-庚烯、1-, 2-, 3-或4-辛烯、1-壬烯或1-癸烯,其中它们可任选被取代,例如丙烯腈。
本文所用的术语“炔烃”是指含有至少一个碳-碳三键的烃基本部分。可优选使用的含碳前体是例如乙炔、丙炔、丁炔、戊炔、己炔、1-,
2-或3-庚炔、1-,
2-, 3-或4-辛炔、壬炔或癸炔,其中它们可任选被取代。
可考虑的环状烯烃或炔烃是具有例如大约3至大约10,优选大约5至大约10个碳原子的非芳族的单环或多环环体系,其在环烯烃的情况下含有至少一个碳-碳双键,在环炔烃的情况下含有至少一个碳-碳三键。单环环烯烃的实例是环戊烯、环己烯、环庚烯等。多环烯烃的一个实例是降冰片烯。
该含碳前体还可含有任选取代的杂环分子或由其构成。在此,术语“杂环”是指具有大约3至大约10,优选大约5至大约10,特别优选大约5至大约6个碳原子的单环或多环环体系,该环体系中的一个或多个碳原子被杂原子替代。
本文所用的术语“杂原子”是指一个或多个选自氧、氮或硼的原子,其中包含各自氧化的形式。
在本发明的一个特别优选的实施方案中,用作含碳前体的杂环化合物含有至少一个碳-碳或碳-杂原子双键。
本文所用的术语“芳族分子”或“芳族化合物”包括含有共轭双键体系的任选取代的碳环和杂环化合物。杂环芳族化合物也被称作“杂芳族化合物”。根据本发明的芳族分子的实例是具有0至3个彼此独立地选自O、N和B的杂原子的任选取代的单环芳环或具有0至5个彼此独立地选自O、N和B的杂原子的8-至12-元芳族双环环体系。可根据本发明使用的含碳前体是例如任选取代的苯、萘、蒽、吡啶、喹啉、异喹啉、吡嗪、喹喔啉、吖啶、嘧啶、喹唑啉、哒嗪、噌啉、呋喃、苯并呋喃、异苯并呋喃、吡咯、吲哚、异吲哚、咪唑、苯并咪唑、嘌呤、吡唑、吲唑、噁唑、苯并噁唑、异噁唑、苯并异噁唑。
当本文中论及术语“任选取代”时,这是指该分子或化合物可以是未取代的或带有多个,优选1至3个取代基。该取代基可以是纯脂族的或含有一个或多个杂原子。在一个优选实施方案中,该取代基选自C1至C10-脂族、C3至C10-脂环族、C6至C10-芳基、5-至10-元杂芳基和3-至10-元杂环基、C1至C6-卤烷基、C1至C10-烷氧基、卤素、NO2、-OH、-CN。
在实践中已实现良好至极好结果的含碳前体的特别优选的实例是不饱和烃,如乙烯或丙烯腈,和芳族分子,如苯或吡啶。
在通过已知方法制造碳纳米管中,特别使用使碳纳米管的长度增长的催化剂。对此常用的催化剂的实例是含铁、含钴或含镍的催化剂。
在碳纳米管的催化制造中,所用催化剂的残留物通常留在制成的碳纳米管粉末中。可以通过酸洗,特别借助盐酸从碳纳米管粉末中大部分地除去这些催化剂残留物,以使酸清洗的碳纳米管只有极低的催化剂残留物含量。
在该新型CNT制造方法的另一个实施方案中,使用流化床反应器的流化床作为移动床。经由在载体中设置的喷嘴开口将气体流导入CNT催化剂中(和任选导入辅助床中),以使CNT催化剂(和任选的辅助床)和气体流形成所谓的流化床。该流化床的特征在于类似液体的性状,其中该CNT催化剂的各颗粒在该气体流中充分混合。除该CNT催化剂的良好充分混合外,在流化床中还实现良好的热传递和质量传递,以在流化床中存在基本均匀的工艺条件。由此获得具有非常均匀的物理和化学性质的产物。在实验中,借助流化床反应器还获得相应高的收率。
作为流化床反应器,可以使用例如石英流化床反应器,其中该反应器基本由石英玻璃外壳,例如石英玻璃管形成。
在该方法的一个可选实施方案中,也可以借助旋转管反应器提供移动床。旋转管反应器具有纵轴与水平面呈例如1-5°的小角度设置的反应器管。安装该旋转管以可围绕其纵轴旋转并能驱动其围绕该轴旋转。为了进行该方法,首先将CNT催化剂施加到反应器管的内表面上。随后在将含碳前体引入反应器管的同时使反应器管围绕其纵轴旋转。该方法可以同流运行,即反应气体和催化剂或CNT同向移动,或对流运行。优选的是对流运行。
在使用流化床反应器的流化床作为移动床的该方法的另一个实施方案中,设定经过该流化床的气体流以得到稳定流化。在使用这种气体流动范围时已经凭实验发现良好收率。为了控制收率和该方法本身,也可以使用气体混合物,例如惰性载气与含碳前体的混合物。
稳定流化是指气体流动的速度大于或等于最小流化速度。关于最小流化速度的测定,参考WO 2007/118668A2,其内容经此引用应成为本说明书的部分。特别地,关于测定最小流化速度,参考WO 2007/118668A2的第7页上的公式(1)。
该碳纳米管制造方法可以连续、准连续或不连续地进行。在优选的连续方法方式中,将CNT催化剂连续送入流化床反应器和/或连续取出制成的碳纳米管。在不连续方法方式中,使用相继批次进行该方法。对于一个批次,首先预先放置CNT催化剂并在该方法结束时从流化床反应器中基本完全取出所得产物。在准连续方法方式中,在工艺进程结束时从流化床反应器中仅取出产物的一部分并相应地再次补充CNT催化剂。
在该方法的另一个实施方案中,特别在准连续或不连续的方法中,设定10至600分钟,优选10至120分钟,特别是20至50分钟的工艺时间。
优选设定工艺时间以使制成的碳纳米管或附聚物的堆积密度在该方法结束后为10至500 g/l,优选40至250 g/l,特别是60至150 g/l。
在该方法的另一个优选实施方案中,可以通过使用含有或由包含碳和至少一种选自氮或硼的杂原子的化合物构成的含碳前体,实现具有掺杂的类石墨烯层的碳纳米管的制造。或者,该含碳前体也可含有至少两种化合物,其中至少一种包含碳,至少另一种包含选自氮和硼的元素。
掺杂是指层的原本的类石墨烯结构除碳原子外还具有外来原子,优选至少1.5原子%,优选至少2原子%,更优选至少5原子%,特别是至少10原子%。这些可以例如代替碳原子位于石墨烯晶格的晶格格位或缺陷位点中。未掺杂的层是指未有意被外来原子掺杂的类石墨烯层,以使该层内的缺陷位点在天然缺陷位点范围,即特别在≤ 1原子%,特别≤ 0.5原子%的范围内。
还通过含有上述碳纳米管的碳纳米管粉末实现本发明的目的。
该碳纳米管粉末的碳纳米管优选具有1至100纳米,优选3至50纳米,特别是5至25纳米的平均直径。这一直径范围符合常见工业规定并可借助本发明容易实现。
该碳纳米管粉末优选具有至少90%,优选至少95%,特别是至少97%,特别优选至少98%的纯度。在此,纯度是指该粉末中的碳纳米管(相对于其它成分,特别例如无定形碳和无机金属氧化物)的重量%含量。已经发现,可以借助本发明制造具有高纯度的碳纳米管粉末。
特别优选获得具有大于5,优选大于100的长度/外径比的碳纳米管。
该碳纳米管特别优选以附聚物的形式获得,其中该附聚物特别具有0.05至5毫米,优选0.1至2毫米,特别优选0.2-1毫米的平均直径。
本发明因此还提供根据如上所述制造纤维状碳的新型方法制成的纤维状碳在电极材料、锂离子电池、聚合、陶瓷或金属复合材料中、在膜中、作为催化剂载体和用于改进复合材料的机械或导电性能的用途。
实施例
实验部分
实验1-9的一般规程。
a) 溶液的制备:由在50毫升去离子水中的19.4克Co(NO3)2*6H2O、在50毫升去离子水中的17.0克Mn(NO3)2*4H2O、在35毫升去离子水中的Al(NO3)3*9H2O(量参见表1)和在35毫升去离子水中的30.6克Mg(NO3)2*6H2O,制备四种溶液。随后合并水合硝酸锰溶液和水合硝酸钴溶液(溶液A),同样合并水合硝酸铝溶液和水合硝酸镁溶液(溶液B)。随后同样合并所得的两种溶液(A和B)并搅拌5分钟(溶液C)。通过将60克固体氢氧化钠(NaOH)搅拌到211毫升去离子水中以形成22.1重量%的NaOH溶液,制备下文被称作溶液D的溶液。
b) 沉淀:在室温(大约23℃)下,将两种溶液(C和D)在剧烈搅拌下计量加入预先放置有200毫升去离子水和氢氧化铝(Dadco公司的Reflamal®
S20;量参见表1)的多颈圆底烧瓶中,其中通过添加NaOH溶液使pH值保持在大约pH = 10。该沉淀进行大约30-40分钟。在计量加入完成后,再搅拌10分钟。
c) 过滤/洗涤:在沉淀后过滤所得固体。随后通过三次悬浮来洗涤该固体。洗涤水量为大约1升。
d) 干燥:该催化剂在空气中在120℃下干燥过夜。
e) 研磨/筛分:在用于在流化床中进行的CNT合成前,借助IKA磨机(M 20)研磨该干燥颗粒并随后借助Retsch公司的AS 20筛分机的辅助通过所属的空气喷射筛筛分。0.03-0.1毫米级分用于CNT合成。将基于所用研磨材料计的良好磨粒级分(Gutkornfraktion)百分率量作为可研磨性的品质,其中评定良好磨粒含量> 60% = 好,60-40% = 中等,< 40% = 差。
f) 煅烧(任选的):在一些情况中(见表1),该催化剂在研磨/筛分后和在CNT合成中测试前在空气中加热到400℃ 6小时。
g)
CNT合成:
在流化床装置中在实验室规模下测试如上所述制成的催化剂。为此,将特定量的催化剂(0.5克)预先放置于具有5厘米内径并借助管式炉从外加热的石英玻璃反应器中。借助PID调节法调节流化床的温度。借助热电偶测定流化床的温度。经由电子控制的质量流量调节器将进料气体和惰性稀释气体导入反应器。
然后借助氮气使该反应器惰性化并加热到预定温度(表1)。然后立即送入作为乙烯、氢气以及惰性氮气的混合物的进料气体。体积流量(基于标准升LN)设定如下:乙烯6 LN·min-1、氢气3 LN·min-1和氮气1 LN·min-1。向催化剂供应进料气体33分钟的时间。然后通过中断引入进料来停止进行中的反应,用氮气吹扫反应器,冷却并取出反应器内容物。结果概括在表1中。
基于催化剂的“不可燃 / 不可分解”部分的质量计的催化剂活性说明(“灼烧损失 - 收率”).
用于CNT合成的氧化催化剂始终含有一定量的水,其依赖于该催化剂的经历,特别是干燥和煅烧。为了更好地相互比较实验的实际收率,借助灼烧损失的测定法因此最合适。
通过称重测定沉积的碳量。通过在马弗炉中在空气中在650℃下加热6小时,测定CNT的“不可燃/不可分解”部分。基于催化剂残留物的质量(mkat)和反应后的重量增加(m总-mkat),规定基于不可燃部分(催化剂残留物)计的沉积碳量,下文称作生产率(Ertrag):生产率= (m总-mkat)/mkat。
根据
BET
法测定
CNT
的比表面积
如下预处理CNT:150℃/0.1 mbar/16 h;
根据多点BET法在-196℃下的N2吸附(类似于DIN
ISO 9277)
CNT
的堆积密度的测定
根据EN ISO 60进行测定。
Claims (19)
1.制造至少由一种或多种活性金属和一种或多种载体材料构成的催化剂的方法,其包含步骤:
a) 预先放置充当用于所述催化剂的载体材料的粉末形式的基材,通过机械作用将所述基材粉末分散在溶剂中,并将所述分散体设定至至少8,优选至少9,特别优选至少9.5和最大13的pH值,
b) 任选在重新设定所选pH值的情况下,添加一种或多种含有催化活性金属和载体金属的前体化合物的金属盐溶液,以使它们共沉淀并同时沉积在所述预先分散的基材粉末上,
c) 移除和分离所述沉淀的固体,
d) 任选用溶剂洗涤所述固体,
e) 喷雾干燥或干燥和任选研磨和/或筛分(分级),
f) 任选在200℃-950℃,优选400℃-900℃,特别优选400℃-850℃下煅烧,并还原或氧化和随后还原,
g) 还原所形成的催化剂材料。
2.如权利要求1中所述的方法,其特征在于使用一种或多种选自铁、钴、镍、锰或钼的金属的化合物作为所述催化活性金属的前体化合物。
3.如权利要求1或2中所述的方法,其特征在于使用钴和锰的化合物作为前体化合物。
4.如权利要求1至3任一项中所述的方法,其特征在于所述用于载体材料的前体化合物选自镁、铝、硅、钛、钡或钙的化合物的一种或多种化合物。
5.如权利要求1至4任一项中所述的方法,其特征在于所述用于载体材料的前体化合物是镁和/或铝的化合物。
6.如权利要求1至5任一项中所述的方法,其特征在于所述金属以它们的氧化物或氢氧化物、混合氧化物/氢氧化物、或混合氧化物或混合氢氧化物的形式存在于来自步骤c)的分离的固体中。
7.如权利要求1至6任一项中所述的方法,其特征在于在根据步骤e)的喷雾干燥和/或研磨和筛分后所述催化剂的主要级分的粒径为0.01至1毫米,优选0.02至0.25毫米,特别是0.03至0.12毫米。
8.如权利要求1至7任一项中所述的方法,其特征在于用于步骤a)、b)和任选d)的溶剂是一种或多种选自水、醇、醚、酮的溶剂。
9.如权利要求1至8任一项中所述的方法,其特征在于在步骤b)中添加所述金属盐溶液的过程中,特别通过搅拌或借助高压分散,剧烈均化所述分散体。
10.如权利要求1至9任一项中所述的方法,其特征在于借助碱金属氢氧化物或氢氧化铵或碱金属碳酸盐或碳酸铵或碱金属碳酸氢盐或碳酸氢铵,特别借助碱金属氢氧化物或氢氧化铵实施所述分散体中的pH值的设定和重新设定。
11.如权利要求10中所述的方法,其特征在于碱金属化合物是锂、钠或钾的化合物,优选钠的化合物。
12.如权利要求1至11任一项中所述的方法,其特征在于在最多100℃的分散体温度下,优选在环境温度下进行沉淀b)。
13.如权利要求1至12任一项中所述的方法,其特征在于所述催化剂中的催化活性金属与所述载体的金属的以摩尔%计的金属含量的比率为90/10至5/95,优选80/20至20/80,特别优选70/30至30/70。
14.如权利要求1至13任一项中所述的方法,其特征在于预先放置的用于所述催化剂载体的基材金属与沉淀的用于催化剂载体的基材金属的以摩尔%计的含量的比率为1/99至95/5,优选2/98至50/50。
15.如权利要求1至14任一项中所述的方法,其特征在于来自步骤a)的预先放置的基材粉末的平均粒径小于1毫米,特别优选小于0.1毫米,特别小于0.02毫米。
16.催化剂,其由如权利要求1至15任一项中所述的方法获得。
17.根据权利要求1至15制造的催化剂用于制造纤维状碳材料,特别是碳纳米管的用途。
18.制造纤维状碳的方法,其通过根据如权利要求1至15任一项中所述的方法制造所述催化剂,
将来自所述催化剂制造方法的催化剂引入合适的反应器,所述反应器优选具有移动反应床,特别是流化床,
通过含碳气体在所述催化剂存在下在升高的温度,特别是至少500℃至1000℃,优选550℃至850℃,特别优选600℃至750℃下,任选在氢气和/或惰性气体,特别是氮气和/或稀有气体存在下的反应产生碳纳米管,和
从所述反应器中排出碳纳米管和其它反应产物。
19.根据如权利要求18中所述的方法制造的纤维状碳材料在电极材料、锂离子电池、聚合、陶瓷或金属复合材料中、在膜中、作为催化剂载体和用于改进复合材料的机械或导电性能的用途。
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CN110662715B (zh) * | 2017-03-31 | 2023-10-27 | 魁北克电力公司 | 粗制碳纳米管的提纯方法 |
CN111356650A (zh) * | 2017-08-29 | 2020-06-30 | 纳瓦科技公司 | 垂直排列碳纳米管的制造方法以及使用这些纳米管作为电极的电化学电容器 |
Also Published As
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US20160160394A1 (en) | 2016-06-09 |
JP2016530083A (ja) | 2016-09-29 |
WO2015007670A1 (de) | 2015-01-22 |
KR20160034292A (ko) | 2016-03-29 |
DE102013214229A1 (de) | 2015-01-22 |
EP3021966A1 (de) | 2016-05-25 |
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