CN1146469C - 制造中孔碳的方法 - Google Patents
制造中孔碳的方法 Download PDFInfo
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- CN1146469C CN1146469C CNB988116421A CN98811642A CN1146469C CN 1146469 C CN1146469 C CN 1146469C CN B988116421 A CNB988116421 A CN B988116421A CN 98811642 A CN98811642 A CN 98811642A CN 1146469 C CN1146469 C CN 1146469C
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- carbon
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Abstract
中孔碳和其制造方法，该方法先形成以固化后重量为基准的碳化产率大于约40%碳的高碳产率的碳前体和添加剂的混合物，所述添加剂可以是催化剂金属和/或以固化后重量为基准的碳化产率不大于约40%碳的低碳产率的碳前体。当使用催化剂金属时，以碳为基准，在随后碳化步骤后的催化剂金属的量不大于约1重量%。将混合物固化，将其中的碳前体碳化，再活化制成中孔活性炭。
Description
本申请要求由Kishor P.Gadkaree在1998年2月10日申请的题为“中孔碳体”的美国临时申请60/074,241和由Gadkaree等人在1998年7月20日申请的题为“制造孔径分布在中孔范围内的碳的方法”的美国临时申请60/093,396的权益。
本发明涉及一种使用低碳产率的碳前体和/或合适的金属催化剂化合物，从碳前体来制造各种孔径，一般大于30的碳的方法。这种按要求形成一定孔径分布的方法对提纯和催化用途来说是特别重要的。
发明的背景
活性炭可应用于各种用途，如空气和水的提纯、汽车挥发性排放物控制中的烃吸附和冷起动的烃吸附等。尽管微孔结构的碳(孔径小于20，并且BET表面积为1000-3000m2/g)适用于许多用途例如气相(如轻质烃和H2S)吸附，但某些用途却需要较大孔径的碳，以达到最佳的吸附量和/或催化活性。例如，除了常规的气态污染物如烃外，为除去液相中较大分子量的污染物如腐黑物、蛋白质等或某些种类的农药则需要特定的表面性能和孔径分布。当催化或化学反应受到传质和传热的限制时，孔径较大的碳是适宜的。碳中的中孔隙对于合适的催化剂加入量和分散度来说有时同样是需要的。
整体的活性炭，无论其形式是在基材上的涂层还是一定形状的活性炭结构体都可应用于各种用途，尤其是在要求耐用和低压力降的情况下，如某些使用强酸性或碱性溶剂或其它腐蚀性介质的化学反应中。
金属催化剂一直应用于制造活性炭负载的催化剂，如在美国专利5488023中所披露的那样。然而，到目前为止，没有一种能制造例如可用于某些气相和液相用途以及催化用途的具有要求性能和孔隙特征的活性炭的方法。
本发明的概述
按本发明的一个方面，提供一种中孔碳和制造中孔碳的方法，该方法包括先形成碳化产率大于约40％碳(以固化后重量为基准)的高碳产率的碳前体和添加剂的混合物，所述添加剂可以是催化剂金属和/或碳化产率不大于约40％碳(以固化后重量为基准)的低碳产率的碳前体。当使用催化剂金属作为添加剂时，在随后碳化步骤后的催化剂金属的量，以碳为基准不大于约1重量％；然后将此混合物固化，将其中的碳前体碳化，再活化制成中孔活性炭。
本发明的详细描述
本发明涉及制造中孔活性炭的方法，它是将高碳产率的碳前体、低碳产率的添加剂和/或催化剂金属化合物混合，随后固化、碳化，最后在活化剂如蒸汽和二氧化碳等气氛中进行热处理使碳活化。当使用催化剂金属化合物时，以碳化步骤后存在的碳为基准，所提供的催化剂金属的量不大于约1重量％。
在本发明中，中孔碳是指总孔容的至少约50％，更一般约60-90％的孔隙在20-500的范围内，并且在大孔范围(＞500)的孔隙不超过总孔容的25％。
碳前体是指一种在加热时能转变成连续结构的碳的含碳合成聚合物。使用碳前体比使用活性炭颗粒好，这是由于经过固化、碳化和活化过程，碳原子会排列成无规三维石墨片晶的连续不间断结构。
高碳产率的碳前体是指碳化后其转变成碳的产率大于约40％(以固化后重量为基准)。本发明中特别有用的高碳产率碳前体是一种合成聚合的碳前体，如在环境温度下是溶液或低粘度液体形式的或者通过加热或其它方式能液化的合成树脂。合成聚合的碳前体包括任何液体或可液化的含碳物质。有用碳前体的例子包括热固性树脂和某些热塑性树脂。
低粘度的碳前体(如热固性树脂)对于涂料用途较为适宜，因为其粘度低，所以能较好地渗透到基材中去。典型的树脂粘度约为50-100厘泊。任何高碳产率的树脂都可以使用。酚醛树脂和呋喃树脂最合适。酚醛树脂最好，因为与其它前体相比，其粘度低，碳产率高，在固化时的交联度高，并且成本低。合适的酚醛树脂是可熔性酚醛树脂如43250 polyophen树脂，和购自Occidental ChemicalCorporation的43290，以及购自Borden Chemical Company的Durite可熔性酚醛树脂。一种特别合适的呋喃液体树脂是购自QO Chemicals碳Inc.的Furcab-LP。
使用的高碳产率碳前体可以是一种的高碳产率的前体材料，或者两种或多种这种前体材料的混合物。也可以将先已制好的活性炭加到液体碳前体中，调节前体的粘度，以便成形为结构体或施加到结构体中。
为了获得所需孔隙特征的碳，在高碳产率的碳前体中加入催化剂金属和/或低碳产率的碳前体。
低碳产率的碳前体是碳化后其转变成碳的产率不大于约40％(以固化后重量为基准)的前体。某些特别有用的低碳产率的碳前体是交联添加剂，它们是甘油，三聚氰胺-甲醛，环氧，和/或聚乙烯醇。仅使用低碳产率碳前体而不使用催化剂金属的一个好处是，在最终产物中不希望有催化剂金属的情况下可以免去除去催化剂金属的步骤。
当碳基体中存在金属催化剂时，在活化过程中各金属添加剂会引发表面蚀刻、沟道和蚀坑的形成这些形貌效应，这取决于它们本身的物理和化学性能、碳结构体和反应条件如何。为了选择性地产生所需的中孔活性炭，需将这三种作用进行协调，以便获得所需的孔径。沟道和蚀坑的形成提供成孔的机会，而表面蚀刻则提供将孔扩大的机会。
合适的金属催化剂可以是碱金属、碱土金属、过渡金属和/或贵金属。催化齐剂金属较好是Pt、Pd、Rh、Ag、Au、Fe、Re、Sn、Nb、V、Zn、Pb、Ge、As、Se、Co、Cr、Ni、Mn、Cu、Li、Mg、Ba、Mo、Ru、0s、Ir、Ca、Y或这些金属的混合物。较好的金属是Pt、Co、Ni和/或Fe，特别是氧化态为+3的Fe，Co是特别好的。金属催化剂较好是前体或化合物的形式，例如在加热时能分解成催化剂金属或催化剂金属氧化物的有机或无机盐，如硫酸盐、硝酸盐等。采用金属化合物比用金属元素好，且较好是其细粒的形式，因为直接采用金属粉末往往会形成较大的石墨颗粒，而这是不适宜的。化合物的例子是氧化物，氯化物，(除了碱金属或碱土金属外的)硝酸盐，碳酸盐，硫酸盐，配合铵盐等。合适种类金属的有机金属化合物可与或不与低碳产率的碳前体一起使用。例如，乙酸盐如乙酸钴，和/或乙酰丙酮化物如乙酰丙酮化钴、铂和/或铁是特别合适的。尽管在此不准备结合什么理论，但可以认为，在树脂中引入的这些较大的有机结构物在固化于基体上后处于一种热定形(thermally set)的状态，在碳化过程中除去这些结构物可有助于形成较大的孔隙度。因此，在活化步骤中让更多的金属催化剂暴露于表面上，这有利于进一步控制孔径。
本发明所用的金属催化剂的量取决于金属催化剂的种类或活性，以及所需的最终孔隙度和孔径分布，但以碳化后存在的碳为基准，其用量不大于约1重量％，一般约为0.01-1重量％，最好约为0.01-0.2重量％。对于活性高的Co，浓度可低至50-100ppm。添加金属的量对产生的最终孔结构影响很大。然而，加入的金属太多会使金属的烧结速率明显提高。烧结的颗粒往往会堵塞孔隙并形成所谓的瓶颈式孔隙。而且当发生烧结时，催化剂的活性会下降，甚至去活化。
在某些情况下，要加入催化剂金属和低碳产率的碳前体这两种物质作为添加剂。例如，加入钴如乙酸钴或硝酸钴和/或铁化合物如硝酸铁与上述交联添加剂的混合物是有用的。特别好的是乙酸钴或乙酰丙酮化铁与甘油和/或聚乙烯醇的混合物。
一种制造中孔活性炭的有用方法是用碳前体和催化剂金属化合物的涂料悬浮液或溶液涂覆无机基材如蜂窝体，随后固化、碳化、将碳活化成活性炭的连续涂层。例如，首先将约7克催化剂前体即硝酸钴(II)溶解到少量的水中，而后将其倒入1000毫升低粘度的可熔性酚醛树脂中。将混合物均化成均匀的溶液。接着将此悬浮液或溶液涂覆到基材，如由堇青石制成的整片基材上。而后将其在约90-100℃干燥，在约150℃固化，碳化，最后在具有活化作用的气体如二氧化碳或蒸汽中活化。
基材的外表面上具有孔隙，这些孔隙延伸入基材内部。涂料渗入其中并分布到所有这些孔隙中，成为基材上的涂层。
很适用形式的整片基材具有能让流体通过的构造，例如从外部连通到内部的孔隙网络，和/或从整片基材的一面延伸到另一面可让流体从基材的一面流到另一面的透过通道。
基材还必须具有在其应用中能起作用的足够强度，并能经得起在形成活性炭涂层中所用的热处理温度。
希望基材所有的开孔孔隙度至少约为10％，较好为大于约25％，最好大于约40％。对于大多数用途来说，所希望的孔隙度范围约为45％-55％。较好的是基材的孔隙是“相连的孔隙”，其特征在于这些孔隙与其它孔隙相连和/或交叉，在基材内部形成一个曲折的孔隙网络。
合适的多孔基材包括陶瓷、玻璃陶瓷、玻璃、金属、粘土和它们的组合。组合是指物理或化学的组合，如混合物、化合物或复合物。
特别适用于本发明实践的一些材料(尽管应明白的是本发明并不局限于此)是那些由下述物质制成的材料，堇青石、富铝红柱石、粘土、镁氧，和金属氧化物、滑石、锆石、氧化锆、锆酸盐、氧化锆-尖晶石、硅铝酸镁、尖晶石、氧化铝、二氧化硅、硅酸盐、硼化物、硅铝酸盐，例如瓷、硅铝酸锂、氧化铝二氧化硅、长石、二氧化钛、熔凝硅石、氮化物、硼化物、碳化物如碳化硅、氮化硅，或这些材料的混合物。堇青石是较好的，因为其热膨胀系数与碳的热膨胀系数相似，从而可提高活性炭体的稳定性。某些典型的陶瓷基材披露于美国专利4,127,691和3,885,977中。这些专利参考结合于此。
合适的金属材料是任何金属或合金或金属间化合物，只要它能提供耐用的结构功能并且在低于约600℃时不软化。特别有用的是主要含铁系金属(即Fe、Ni和Co)的合金，可以含有碳(如钢，尤其是不锈钢或高温钢)，也可以不含碳。不含碳的用于较高温度用途的最典型合金是那些主要包含铁系金属和铝的合金，其中较好的铁系金属是铁。特别好的是Fe、Al和Cr。例如，含有其它可能添加物的Fe5-20A15-40Cr和Fe7-10A110-20Cr粉末是特别合适的。某些用于作为基材的典型的金属粉末组成披露于美国专利4,992,233、4,758,272和5,427,601中，其内容参考结合于此。美国专利4,992,233和4,758,272涉及的是从Fe和Al的金属粉末组合物来制造多孔烧结体的方法，其中还可加入Sn，Cu和Cr。美国专利5,427,601涉及具有下述组成的多孔烧结体，即主要由约5-40重量％Cr、约2-30重量％Al、0-约5重量％特种金属、0-约4重量％稀土金属氧化物添加剂以及余量的铁系金属和不可避免的杂质组成，其中较好的铁系金属是铁。当存在稀土金属氧化物时，特种金属是Y、镧系元素、Zr、Hf、Ti、Si、碱土金属、B、Cu和Sn中的至少一种。当不存在稀土金属氧化物时，特种金属是Y、镧系元素、Zr、Hf、Ti、Si和B中的至少一种，还或可添加碱土金属、Cu和Sn。
基材较好的是蜂窝体，其中的薄壁形成与蜂窝体两端连通的许多开口通道。
蜂窝体的通道密度一般为235个通道/厘米2(约1500个通道/英寸2)-1个通道/厘米2(约6个通道/英寸2)。除了这些蜂窝体外，一些常用的蜂窝体的例子(尽管应明白的是本发明并不局限于此)是约94个通道/厘米2(约600个通道/英寸2)，约62个通道/厘米2(约400个通道/英寸2)，或约47个通道/厘米2(约300个通道/英寸2)，和那些约31个通道/厘米2(约200个通道/英寸2)。对约62个通道/厘米2(约400个通道/英寸2)的蜂窝体来说，典型的壁厚例如约为0.15毫米。壁(网)的厚度一般约为0.1-1.5毫米。蜂窝体的外部尺寸和形状取决于其用途。
堇青石蜂窝体尤其适合于作为中孔活性炭的基材。
使碳前体和金属催化剂与无机基材紧密接触可以采用任何合适的方法。可作为例子的接触方法，包括将基材浸在一种或多种碳前体(含或不含催化剂金属)的溶液或淤浆中，或将一种或多种碳前体(含或不含催化剂金属)的溶液或淤浆直接喷在基材上。
另一种制造含有催化剂金属的活性炭的有用方法是诸如通过挤压使一种或多种碳前体(含或不含催化剂金属)、粘合剂和/或填料和成形助剂的混合物成形。
可以使用的某些粘合剂是具有增塑作用的暂时有机粘合剂如纤维素醚。某些典型的纤维素醚是甲基纤维素、乙基羟乙基纤维素、羟丁基纤维素、羟丁基甲基纤维素、羟乙基纤维素、羟甲基纤维素、羟丙基纤维素、羟丙基甲基纤维素、羟乙基甲基纤维素、羧基甲基纤维素钠和它们的混合物。甲基纤维素和/或甲基纤维素衍生物特别适合用于本发明中作为有机粘合剂，甲基纤维素、羟丙基甲基纤维素或这些纤维素的混合物是较好的。
某些合适的填料包括天然和合成的、疏水和亲水的、纤维状的或非纤维状的、可碳化或不可碳化的填料。
例如，某些天然填料是软木，如松树、云杉、红杉等，硬木如槐木、山毛榉、桦树、枫树、橡树等，锯屑，壳纤维如研磨的杏仁壳、椰子壳、杏树果核壳、花生壳、山核桃壳、胡桃壳等，棉花纤维如棉绒、棉织物、纤维素纤维、棉子纤维，切断的植物纤维如大麻、椰子纤维、黄麻、剑麻和其它物质如玉米棒子、柑橘浆(经干燥)、大豆粉、泥炭苔、小麦粉、羊毛纤维、玉米、马铃薯、稻谷、木薯粉、煤粉、活性炭粉等。某些合成材料是再生纤维素、人造纤维织物、玻璃纸等。
特别适用于液体树脂的可碳化填料例如是纤维素、棉花、木材和剑麻，或这些物质的混合物，所有这些物质较好是用其纤维的形式。
可以使用的某些无机填料有含氧矿物如粘土、沸石、滑石等，碳酸盐如碳酸钙，硅铝酸盐如高岭土(硅铝酸盐粘土)，飞灰(一种从发电厂燃煤后获得的硅铝酸盐)，硅酸盐如硅灰石(偏硅酸钙)，钛酸盐，锆酸盐，氧化锆，氧化锆尖晶石，硅酸镁铝，富铝红柱石，氧化铝，三水氧化铝，尖晶石，长石，绿坡缕石和硅铝酸盐纤维，堇青石粉末等。
特别合适的无机填料例如是堇青石粉末、滑石、粘土和硅铝酸盐纤维。
有机填料为成形结构体提供附加的支撑，并在碳化时产生壁上的孔隙，因为通常它所留下的碳残渣非常少。某些有机填料是聚丙烯腈纤维，聚酯纤维(短纤维)，尼龙纤维，聚丙烯纤维(短纤维)或粉末，丙烯酸类纤维或粉末，芳族聚酰胺纤维，聚乙烯醇等。
某些特别合适的粘合剂和填料描述于1996年5月20日提交的美国专利申请SN 08/650,685中。该申请参考结合于此。
某些成形用的助剂如挤出助剂是皂、脂肪酸如油酸、亚油酸等，聚氧乙烯硬脂酸酯等或这些物质的组合。特别好的是硬脂酸钠。一种或多种挤出助剂的最佳用量取决于其组成和所用的粘合剂。
然后对与恰当量的上述添加剂混合的碳前体和金属催化剂(若存在的话)进行热处理，将其中的碳前体转变成连续的碳即进行碳化。
而后对所得的碳再进行热处理活化，制得活性炭结构体。
当碳前体是热固性树脂时，在活化前，大部分情况下通常在碳化前，对碳前体还进行固化。固化一般是将前体加热到约100-200℃的温度约0.5-5.0小时完成的。固化通常是在空气中在大气压力下进行的。对于某些前体(如糠醇)，固化可以是在室温下加入固化催化剂如酸催化剂来完成。固化也有保持金属化合物催化剂在碳中均匀分布的作用。
碳化是含碳物质和与其混合的金属化合物催化剂(若存在的话)的热分解，从而排除所含的低分子量物质(如二氧化碳，水，气态烃等)，获得固定的碳质量并在碳中产生基本的孔隙结构。
经固化的碳前体的这种转变即碳化一般是在还原或惰性气氛(如氮气、氩气、氦气等)中加热到约400-800℃的温度约1-10小时完成的。
对碳前体进行固化和碳化后，获得的是其结构基本上不间断的碳结构体，其中含有均匀分散的催化剂颗粒(若存在的话)。其中催化剂通常聚集成较大的颗粒，这与固化步骤后其中催化剂还是分子程度分散的情况不同。催化剂颗粒的粒度取决于其加到起始树脂中的量。在初始树脂中的催化剂越多，则催化剂颗粒就越容易聚集。催化剂颗粒的大小也取决于碳化和活化的温度。碳化和活化的温度较高会引起明显的金属烧结，即使在金属浓度较低时。当碳是涂料的形式施加在基材上时，碳涂料就固定在基材的孔隙中，呈高度粘着的状态。碳涂层的上部表面是碳-碳键的不间断层。若在基材中存在互相连通的孔隙，则在组合物中将形成相互连接的碳网，碳涂层与基材的粘着就更牢。遍布整个基材外表面的这种不间断的碳涂层，其优点是提供了催化能力高(即使碳含量较低)强度大和使用温度高的结构。可以制成这样的结构体，它所含碳的量占基材和碳总重量的百分数小于约50％，经常小于约30％。
固化和碳化碳前体中的催化剂金属化合物可获得催化剂与不间断碳结构均匀而紧密的化学结合。决定于催化剂加入量、过程参数和催化剂本性等因素的所得催化剂颗粒的大小是决定活性炭中孔径的主要因素。分散良好的催化剂颗粒及其均匀的粒度在后面的活化步骤中有助于在活性炭中形成中孔。
以催化的方式进行活化，可以充分地产生中孔孔径范围的新孔隙，并扩大所形成的微孔孔径，结果就提高了孔容。若不按本发明所述使用金属催化剂或低碳产率的碳前体，形成微孔通常是无法避免的。活化一般在约400-900℃的二氧化碳或蒸汽中按标准方法进行。若活化在蒸汽中进行，温度约400-800℃为宜。
当碳化和活化含催化剂的树脂时，宜采用较低的碳化和活化温度。在碳化阶段，较低的温度不仅可避免形成烧结的大金属颗粒，而且有助于形成较松的碳结构。这两种因素对在活化步骤中的随后成孔来说都是非常重要的。由于相同的原因，活化温度也不宜太高。从上述要求来看，蒸汽活化比二氧化碳活化更好，因为蒸汽活化的反应速度较高，所以其需用的温度较低。有催化剂存在能提供新的催化活性点，能在活化过程中引发形成孔隙，而在非催化活化中只有碳点起作用。催化碳活化反应比非催化碳活化快。由于催化和非催化模式的反应速度不同，故在活化条件下，催化活化与非催化活化相比占主导地位。另外，有催化剂存在在催化活化过程中会对孔隙形成产生形貌效应。视反应条件和在碳表面上催化剂的本性不同，可以有选择性地产生大于约30的孔。
按一个实施方案，催化剂金属是Pt，如二氢氯铂酸的形式，在蒸汽中约为650-750℃的温度进行活化。这种条件能获得总孔隙度的大约60-95％在中孔范围的活性炭，并且中孔孔容的约80-90％在大约40-300的孔径范围。
按另一个实施方案，催化剂金属是Co，如硝酸钴的形式，蒸汽中约为650-750℃的温度进行活化。这种条件能获得总孔隙度的60-85％在中孔范围的活性炭，并且中孔孔容的约60-90％在大约100-400的孔径范围。
按再一个实施方案，催化剂金属是Fe，具体是+3氧化态的Fe，如六水合硝酸铁的形式，在蒸汽中约为650-800℃的温度进行活化。这种条件能获得总孔隙度的约80-95％在中孔范围的活性炭，并且中孔孔容的约85-95％在大约30-60的孔径范围。
合成聚合物基的碳前体如酚醛树脂在惰性气氛中碳化后一般形成具有近程石墨微晶结构的硬碳(也称为炭)。所形成的炭是非常富碳的，它含有在除去挥发性产物过程中形成的少量孔隙。虽然在这里不准备结合什么理论，但可以认为，加入有机和无机金属化合物形式的金属并用蒸汽或二氧化碳对炭进行活化，结果碳的孔径增加，这是由于下述原因：
1)提高了所得炭的湍层特性，甚至是在活化前。换句话说，与用其它方式所发生的情况相比，细分散的金属化合物在碳化过程中促进了更加无序结构的形成。
2)金属化合物在碳化后还原成金属状态。这种金属状态是高度活性的，能促进其邻近部位碳的活性。因此，在催化剂周围产生了较大的孔隙。有金属添加剂存在时的催化活化显著地提高了活化速度。而且，活化优先在金属颗粒的附近进行。当催化剂颗粒在整个碳体中产生蚀坑、沟道和表面蚀刻现象时，所形成的孔隙(沟和坑)的尺寸与催化剂颗粒的尺寸相同或更大。通过调节催化剂颗粒的粒度，可以有选择性地形成中孔，甚至是大孔。
3)在蒸汽中的活化比在二氧化碳中的好。与CO2相比，蒸汽能产生较宽分布的多孔构造和更多的中孔碳，所需的活化温度低得多。
催化剂金属(若存在的话)可以从所得的中孔活性炭体中去除，也可以让其保留下来，若它们在催化等操作中需要的话。去除催化剂金属是用一种液相试剂处理活性炭体，所述试剂能将金属浸出进入溶液中，而后洗去。这种试剂是能浸出大部分金属的酸和碱，如硝酸。对于能与氯化物形成配位化合物的金属如铂来说，盐酸代替硝酸能有效地起作用。乙酸可用于能容易形成乙酸盐的物质。若碳表面被氧化，使用硝酸或另一种氧化剂时这可能发生，可以在升高的温度下在氮气或氢气中对其进行随后的处理，形成还原的表面。
也可以这样去除金属，即在气相中加热或用一种气相试剂处理活性炭体，形成挥发性金属化合物，受热释放到气相中。视金属催化剂种类的不同，这种气相试剂可以是一氧化碳，氢和氯等。碱金属由于其高的挥发性可以通过热处理直接从碳体中去除。象镍、铁、钴等金属可以通过其与一氧化碳形成挥发性羰基化合物而去除。
为了更全面地说明本发明，给出下述一些实施例，这些实施例对本发明并不起限制作用。除非另有说明外，所有的份数、部分和百分数均按重量计。
催化剂金属实施例
实施例1：(对比)
将约100-150厘泊的低粘度酚醛树脂浸涂到开孔孔隙度约为50％的陶瓷堇青石蜂窝体上。然后以各种时间将它们在95℃干燥，在150℃固化，在N2中750℃碳化，然后在CO2中900℃活化。使用N2吸附方法测定三个范围中每个范围的体积孔隙度％。使用标准t-法测定微孔范围内的％孔容。使用BJH法确定中孔的％孔容。所得的活性炭主要具有微孔碳的特征。孔容的大约80％以上在微孔范围内。此表面积至少高于100m2/g碳。尽管活化时的烧去量增加，但中孔百分数只略微提高，与烧去的碳量相比，增加的幅度很小。常规的活性炭制造法往往制得的主要是微孔碳，不管烧去碳有多高。比表面积随烧去的量会明显增加。孔径分布随烧去量的增加往往没有多大改变。在本实施例的烧去量范围内，活化是一种稳态的碳去除反应。
实施例2：本发明：
使用硝酸铁作为催化剂金属。将约7克硝酸铁加到少量的水中。完全溶解后，将其混合到约1000毫升可熔性酚醛树脂(如上所述的相同的树脂)中，剧烈搅拌以确保催化剂前体的均匀分散。对开孔孔隙度约为50％的堇青石蜂窝体浸涂上述含金属的混合物，而后在约95℃干燥，在约150℃固化，在N2中约750℃碳化1小时，并在约700℃在蒸汽和氮的混合气体中活化1-4小时。使用N2吸附等温线测出所得活性炭样品的孔径分布。所得活性炭主要是中孔的，中孔含量占总孔隙度的80-90％。该碳含有约10％的微孔和大孔。大部分在中孔范围内的孔径大约是30-60(中孔的85％)，孔径峰值在38。此中孔碳的比表面积范围为500-650m2/g碳。
这种在催化剂帮助下的活化使总的比表面积有明显的下降，表明存在较大的孔隙。微孔的量随加入催化剂而明显下降。中孔的量随碳烧去的量有了增加。本实施例含Fe的碳是中孔范围峰值约为38的中孔碳。
实施例3：本发明：
使用硝酸钴作为催化剂金属。使用约7.0克Co，按实施例2所述相同的步骤。所得的活性炭含有约70-80％的中孔和20-25％的大孔。比表面积范围为450-550m2/g碳。这种含钴的碳在中孔范围内产生一个双峰分布，其峰值集中在约38和250。
实施例4：本发明：
按实施例2所述的步骤进行，所不同的是加入的金属化合物减少到约2.8克，也是在蒸汽和氮的混合气体中进行700℃活化。所得的活性炭含有60％的中孔和25％的大孔，比表面积约为600m2/g。这种碳在中孔范围内也具有一个单一的峰值，在250。峰值周围的孔径分布使得中孔孔容的大约75％是在100-400范围的孔隙。
实施例5：本发明：
使用二氢氯铂酸(CPA)作为催化剂金属。加入约5克CPA，按实施例2和3所述相同的步骤。所得的活性炭含有约70％的中孔和10％的大孔，比表面积接近550m2/g。这种碳在中孔范围内有一个100的特征峰。峰值周围的孔径分布使得中孔孔容的约80％是在40-300范围的孔隙。
实施例6：对比：
将购自Occidental Chemical Co.，Niagara Falls，N.Y的可熔性酚醛树脂涂覆到堇青石蜂窝体上，然后在约90℃干燥，在约125-150℃固化，在氮气中约900℃碳化，再在二氧化碳中约900℃活化。在Micrometrics(norcross，Ga)ASAP2000设备上通过氮气吸附等温线的测量来测定所得碳的孔径分布。碳基本上全都是微孔的，所有的孔隙均在10或更小的范围。
实施例7：本发明：
重复实施例6的步骤，不同的是涂覆前在树脂中加入约1％的乙酰丙酮化铁。将经涂覆的蜂窝体固化，碳化，再在二氧化碳中活化。约60％中孔的平均孔径约为90。
实施例8：对比：
将约55.6％购自Borden，Inc.的可熔性酚醛树脂与约14.7％堇青石陶渣，约22.2％纤维素纤维，约2％磷酸，约4.6％Methocel和约0.9％硬脂酸钠混合。将混合物挤压成为树脂蜂窝体。然后将所得的蜂窝体在约90℃干燥，固化，碳化，再在二氧化碳中约900℃活化。孔径分布表明，蜂窝体基本上都是微孔碳，其平均孔径约为5，很少或没有中孔。
实施例9：本发明：
重复实施例8的试验，不同的是混合前在树脂中加入约1％的乙酸钴。按实施例8所述处理样品。孔径分布表明，70体积％的孔隙约为400。
实施例10：本发明：
重复实施例6的过程，不同的是以涂料液的总重量为基准，在树脂中加入约50％甘油和约1％乙酸钴。在如实施例6所述的涂覆和处理后，孔径分布表明，约70％中孔孔容的平均孔径约为500。只有约20％的体积在微孔范围。
实施例11：本发明：
在与实施例10所述类似的实验中，在可熔性酚醛树脂中加入约20％聚乙烯醇，然后在涂覆前加入约1％的乙酸钴。按实施例6所述对样品进行处理，孔径分布表明，约69体积％的孔隙在中孔范围，约33体积％的孔隙在微孔范围。
实施例12：本发明：
在树脂中加入约34％三聚氰胺甲醛，重复实施例11的步骤。孔径分布表明，约50％的孔在中孔范围，其平均中孔孔径约为70。
上述实施例6-12表明，加入铁或钴盐或者交联添加剂如甘油、三聚氰胺甲醛或聚乙烯醇，可以改善孔径分布获得较大的孔隙，如大于约50，而这在可熔性酚醛树脂基的碳中用其它方式是无法达到的。
实施例13：(对比)：
在研磨机中将包含约55.5％购自Borden，Inc.的Durite液体酚醛树脂，约22.2％纤维素纤维BH40，约14.7％堇青石陶渣，约4.7％Methocel，约0.9％硬脂酸钠和约2％磷酸的批料进行混合，然后挤压成约400个通道/英寸2并且壁厚约为12密耳的蜂窝体。接着将样品在约90℃干燥，而后在约125-150℃固化。在氮气中约900℃碳化约6小时，再在二氧化碳中约850℃活化约4小时。所得蜂窝体的孔径分布在约2-20的范围内。不存在大于20的孔隙。
实施例14：(本发明)：
在实施例13的批料中加入约1％的乙酸钴。然后将样品固化，碳化，再在二氧化碳中约750℃活化约4小时。这时用了较低的活化温度，因为钴促进了碳的气化，而在约850℃活化会发生非常强的不受控制的烧去现象。有相当多的孔隙在50-110的范围，这表明可以使用催化剂制得中孔碳蜂窝体。
这种中孔体如蜂窝体在化学反应器或石化反应器中可用作催化剂载体，也可用于吸附或水的提纯用途。
实施例15：对比：
首先将约16.59克硝酸镍溶解在50毫升水中，然后将其混合到约1000毫升可熔性酚醛树脂中。按与实施例2类似的步骤，将这种高金属含量的树脂用浸涂方法，制造碳涂覆的蜂窝体。在最终碳中的金属含量总计高于1重量％。最终多孔碳的孔径分布为37％微孔，28％中孔和35％大孔。由于催化剂金属的含量高，所以生成明显较大的孔。
应明白的是，尽管本发明业已对其某些例举性和特定的实施方案作了详细描述，但不应认为本发明局限于此，在不偏离本发明的精髓和所附权利要求书的范围内可以以其它方式来使用本发明。
Claims (27)
1.一种制造中孔活性炭的方法，该方法包括：
a)先形成包含高碳产率的碳前体和添加剂的混合物，所述高碳产率的碳前体，以固化后重量为基准的碳化产率大于40％碳，所述添加剂选自催化剂金属、以固化后重量为基准的碳化产率不大于40％碳的低碳产率碳前体以及它们的混合物，当使用催化剂金属时，在随后碳化步骤后的催化剂金属的量，以碳为基准不大于1重量％，所述低碳产率的碳前体选自甘油、三聚氰胺甲醛、环氧、聚乙烯醇和它们的混合物；
b)将混合物固化；
c)将混合物中的碳前体碳化；
d)使碳活化，制得活性炭，在该活性炭中，总孔容的至少50％的孔隙在20-500的范围内，并且不超过总孔容的25％的孔隙在大于500的范围内；和
e)当所述金属催化剂与所述低碳产率的前体结合起来在步骤a)中作为添加剂使用时，再除去所述金属催化剂。
2.如权利要求1所述的方法，其中高碳产率的碳前体是热固性树脂。
3.如权利要求2所述的方法，其中所述高碳产率的碳前体是酚醛树脂。
4.如权利要求1所述的方法，其中添加剂是催化剂金属。
5.如权利要求4所述的方法，其中以碳为基准，催化剂金属的量为0.01-0.2重量％。
6.如权利要求4所述的方法，其中提供催化剂金属的是选自碱金属、碱土金属、过渡金属、贵金属和这些金属的组合的化合物。
7.如权利要求6所述的方法，其中催化剂金属选自Co、Fe、Ni、Pt和它们的组合。
8.如权利要求4所述的方法，其中催化剂金属是有机金属化合物的形式。
9.如权利要求8所述的方法，其中有机化合物选自乙酸钴、乙酰丙酮化铁和它们的混合物。
10.如权利要求1所述的方法，其中添加剂是低碳产率的碳前体。
11.如权利要求1所述的方法，其中添加剂是低碳产率的碳前体和催化剂金属的混合物。
12.如权利要求11所述的方法，其中提供催化剂金属的是选自铁、钴和它们组合的金属化合物。
13.如权利要求12所述的方法，其中催化剂金属是乙酸钴，低碳产率的碳前体选自甘油、聚乙烯醇和它们的混合物。
14.如权利要求1所述的方法，其中将碳前体和添加剂的混合物以涂料的形式施涂到基材上。
15.如权利要求14所述的方法，其中基材是蜂窝体。
16.如权利要求1所述的方法，其中将碳前体和添加剂与粘合剂混合，成形为一物体。
17.如权利要求16所述的方法，其中成形是通过挤压进行的。
18.如权利要求17所述的方法，其中将碳前体、添加剂和粘合剂的混合物挤压成蜂窝体。
19.如权利要求1所述的方法，其中活化是在选自蒸汽和二氧化碳的气氛中进行的。
20.如权利要求19所述的方法，其中活化是在蒸汽中进行的。
21.如权利要求20所述的方法，其中活化温度为400-800℃。
22.如权利要求21所述的方法，其中使用催化剂金属，该催化剂金属是Pt，并且活化温度为650-750℃。
23.如权利要求21所述的方法，其中使用催化剂金属，该催化剂金属是Co，并且活化温度为650-750℃。
24.如权利要求21所述的方法，其中使用催化剂金属，该催化剂金属是+3氧化态的Fe，并且活化温度为650-800℃。
25.一种具有某一定孔隙特征的活性炭，该特征在于总孔隙度的60-95％在中孔范围，并且中孔孔容的80-90％在40-300的孔径范围，所述活性炭由权利要求22所述的方法制得。
26.一种具有某一定孔隙特征的活性炭，该特征在于总孔隙度的60-85％在中孔范围，并且中孔孔容的60-90％在100-400的孔径范围，所述活性炭由权利要求23所述的方法制得。
27.一种具有某一定孔隙特征的活性炭，该特征在于总孔隙度的80-95％在中孔范围，并且中孔孔容的85-95％在30-60的孔径范围，所述活性炭由权利要求24所述的方法制得。
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| US60/093,396 | 1998-07-20 |
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| US5439864A (en) | 1993-12-27 | 1995-08-08 | Uop | Shaped carbonaceous composition |
| US5510063A (en) * | 1994-04-15 | 1996-04-23 | Corning Incorporated | Method of making activated carbon honeycombs having varying adsorption capacities |
| US5488023A (en) | 1994-08-12 | 1996-01-30 | Corning Incorporated | Method of making activated carbon having dispersed catalyst |
| TW377313B (en) | 1995-02-27 | 1999-12-21 | Corning Inc | The method of making extruded structures |
| CA2187490A1 (en) * | 1995-11-17 | 1997-05-18 | Kishor Purushottam Gadkaree | Method of making activated carbon bodies having improved adsorption properties |
| EP0930966A1 (en) * | 1996-10-11 | 1999-07-28 | Corning Incorporated | Supported activated carbon composites and method of making same |
| EP0894530B1 (en) * | 1997-07-28 | 2003-09-10 | Corning Incorporated | Mercury removal catalyst and method of making and using same |
| EP1109738A4 (en) * | 1998-07-20 | 2010-08-11 | Corning Inc | PROCESS FOR MAKING MESOPOROUS CARBON USING POROGENIC COMPOUNDS |
-
1998
- 1998-10-26 US US09/179,080 patent/US6248691B1/en not_active Expired - Lifetime
- 1998-12-10 AU AU19083/99A patent/AU1908399A/en not_active Abandoned
- 1998-12-10 KR KR1020007008720A patent/KR100616183B1/ko not_active IP Right Cessation
- 1998-12-10 CN CNB988116421A patent/CN1146469C/zh not_active Expired - Fee Related
- 1998-12-10 WO PCT/US1998/026269 patent/WO1999039818A1/en not_active Application Discontinuation
- 1998-12-10 BR BR9815188-6A patent/BR9815188A/pt not_active Application Discontinuation
- 1998-12-10 EP EP98963843A patent/EP1054729A4/en not_active Withdrawn
- 1998-12-10 JP JP2000530301A patent/JP2002502792A/ja active Pending
-
2000
- 2000-03-02 US US09/517,795 patent/US6228803B1/en not_active Expired - Lifetime
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106999907A (zh) * | 2014-08-11 | 2017-08-01 | 康宁股份有限公司 | 制造具有含多孔吸附剂的通道的蜂窝体的方法 |
| CN105837771A (zh) * | 2016-04-27 | 2016-08-10 | 四川理工学院 | 珊瑚状多孔吸附树脂的制备工艺 |
| CN105837771B (zh) * | 2016-04-27 | 2018-04-24 | 四川理工学院 | 珊瑚状多孔吸附树脂的制备工艺 |
Also Published As
| Publication number | Publication date |
|---|---|
| BR9815188A (pt) | 2000-10-17 |
| US6248691B1 (en) | 2001-06-19 |
| KR100616183B1 (ko) | 2006-08-25 |
| EP1054729A4 (en) | 2002-10-09 |
| CN1281383A (zh) | 2001-01-24 |
| KR20010040825A (ko) | 2001-05-15 |
| EP1054729A1 (en) | 2000-11-29 |
| JP2002502792A (ja) | 2002-01-29 |
| AU1908399A (en) | 1999-08-23 |
| US6228803B1 (en) | 2001-05-08 |
| WO1999039818A1 (en) | 1999-08-12 |
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