CN1871065A - 新型沸石组合物,其制备方法和其催化应用 - Google Patents

新型沸石组合物,其制备方法和其催化应用 Download PDF

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Publication number
CN1871065A
CN1871065A CNA2004800308040A CN200480030804A CN1871065A CN 1871065 A CN1871065 A CN 1871065A CN A2004800308040 A CNA2004800308040 A CN A2004800308040A CN 200480030804 A CN200480030804 A CN 200480030804A CN 1871065 A CN1871065 A CN 1871065A
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zeolite
mesopore
zsm
inorganic oxide
mixture
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单志平
彼得·威廉·格哈德·瓦勒
布当·乔治·曼盖
菲利普·J·安杰文
雅各布斯·科尼利斯·詹森
叶春渊
托马斯·马施迈尔
弗里茨·M·道岑贝格
莱昂纳多·马尔凯塞
埃洛伊兹·德·奥利韦拉·帕斯托
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CB&I Technology Inc
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ABB Lummus Global Inc
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Publication of CN1871065A publication Critical patent/CN1871065A/zh
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Abstract

一种催化材料，包括负载于中孔无机氧化物载体上的微孔沸石。该微孔沸石能够包括Beta沸石、Y沸石(包括“超稳定的Y”－USY)、丝光沸石、L沸石、ZSM.5、ZSM－11、ZSM－12、ZSM－20、Theta－1、ZSM－23、ZSM－34、ZSM－35、ZSM－48、SSZ－32、PSH－3、MCM－22、MCM－49、MCM－56、ITQ－1、ITQ－2、ITQ－4、ITQ－21、SAPO－5、SAPO－11、SAPO－37、Breck－6、ALPO4－5等。该中孔无机氧化物能够为例如二氧化硅或硅酸盐。通过引入一些金属，例如铝、钛、铝、镍、钴、铁、钨、钯和铂，能够对该催化材料进一步改性。它能够作为催化剂用于酰化、烷基化、二聚、低聚、聚合、氢化、脱氢、芳构化、异构化、加氢处理、催化裂化和氢化裂化反应。

Description

新型沸石组合物，其制备方法和其催化应用
互相参考的相关申请
本申请是2001年11月27日提交的美国专利申请第09/995,227号的部分继续申请，美国专利申请第09/995,227号是1999年9月7日提交的美国专利申请第09/390,276号的部分继续申请，美国专利申请第09/390,276号现在被授予美国专利第6,358,486号，本申请要求美国专利第6,358,486号的优先权，在此引入所述的两份申请作为参考。
背景
1.技术领域
本发明公开了涉及独特的含包埋于催化剂载体中的沸石的独特的催化材料，特别涉及包埋于中孔载体中的微孔沸石。
2.技术背景
许多目前的烃加工技术基于沸石催化剂。在本领域中沸石催化剂为人们所熟知且具有孔径大小均匀的排列良好的孔体系。但是，这些材料倾向于只具有微孔或只具有中孔，在大多数情况下只具有微孔。微孔的定义为孔的直径小于2nm。中孔的定义为孔的直径范围从约2nm至约50nm。小的微孔限制外来分子接近微孔内的催化活性中心，或减慢向催化活性中心的扩散过程。许多烃的催化反应传质受限，从而降低了催化剂的有效利用。一种解决办法是减小催化剂粒度，从而缩短扩散途径和增加催化剂颗粒的外表面。
在实践中，不能直接使用小的沸石催化剂颗粒，因为该尘状材料难以处理，并且它将在固定床反应器中造成压力下降问题。因此，通常将沸石与无机氧化物混合并挤压成特定的形状和尺寸。然后该经煅烧整理的催化剂具有好的物理整体性(physical integrity)和多孔结构。但是，取决于具体的反应，结合剂(binder)可以限制向埋于结合剂内的沸石颗粒传质。如果能以高度多孔的载体代替较少孔的结合剂，将提高外来分子对沸石中的活性中心的易接近性。
非常需要具有理想的孔径分布的催化剂，其将有利于向活性催化中心传送反应物并把产物传出催化剂。
发明概述
本文提供了一种用于催化加工烃的材料。该材料包括沸石和多孔无机氧化物，该多孔无机氧化物包括，以无机氧化物的微孔和中孔为基准，至少97体积％的中孔。沸石优选为微孔沸石，例如，Beta沸石、Y沸石(包括“超稳定的Y”-USY)、丝光沸石、L沸石、ZSM-5、ZSM-11、ZSM-12、ZSM-20、Theta-1、ZSM-23、ZSM-34、ZSM-35、ZSM-48、SSZ-32、PSH-3、MCM-22、MCM-49、MCM-56、ITQ-1、ITQ-2、ITQ-4、ITQ-21、SAPO-5、SAPO-11、SAPO-37、Breck-6、ALPO4-5等。本文还描述了该材料的制备和使用方法。沸石颗粒被随机相互连接的中孔通道(channel)所包围，该中孔通道提供对沸石的高的可接近性。在一些情况下沸石颗粒和中孔载体之间的相互作用可能在一定程度上改变沸石和中孔载体的性质。
本文所述的催化材料有利于向活性催化中心传送反应物，并且取决于具体应用，其活性比单独使用的沸石高约2-5倍。
附图简要说明
下面结合附图说明几个实施方案，其中，
图1表示如下：含具有Beta沸石的中孔无机氧化物载体的样品1的X射线衍射(XRD)图(曲线1-a)，Beta沸石的XRD图(曲线1-b)，和样品1的延长扫描时间(EST)的XRD图像(曲线1-c)；
图2是具有Beta沸石的中孔无机氧化物载体(样品1)的高分辨率透射电子显微镜(TEM)图像，和显示沸石区域(domain)的电子衍射图的一个插页；
图3是一个图表，表示具有Beta沸石的中孔无机氧化物载体(样品1)和没有Beta沸石的对比样品的程序升温NH3脱附(NH3-TPD)分析；
图4是一个图表，表示在本文实施例3、4和5中制备的材料以及纯Beta沸石的中孔孔径分布；
图5是一个图表，表示在本文实施例2至5中制备的材料以及纯Beta沸石的XRD图；
图6表示中孔材料(曲线6-a)、MCM-22(曲线6-b)和实施例7的复合材料(曲线6-c)的XRD图；
图7表示实施例7、8和10中所制备的材料的中孔孔径分布；
图8表示中孔材料(曲线8-a)、纯MCM-56(曲线8-b)和复合物8(曲线8-c)的XRD图；
图9表示纯ITQ-2沸石(曲线9-a)、中孔材料(曲线9-b)、复合物9材料(曲线9-c)，和复合物10材料(曲线9-d)的XRD图；
图10表示对于在538℃下以样品3、4、5和纯Beta沸石来裂化正己烷的基于沸石质量的准一级反应速率常数；
图11表示在实施例4和5中所制备的材料的NH3-IR光谱；和
图12表示在本文实施例18中制备的材料(曲线12-a)以及纯USY沸石(曲线12-b)的XRD图。
优选实施方案的详细描述
本文所述的催化剂包括包埋于中孔载体中的微孔沸石。该微孔沸石可以是任意类型的微孔沸石。一些例子如Beta沸石、Y沸石(包括“超稳定的Y”-USY)、丝光沸石、L沸石、ZSM-5、ZSM-11、ZSM-12、ZSM-20、Theta-1、ZSM-23、ZSM-34、ZSM-35、ZSM-48、SSZ-32、PSH-3、MCM-22、MCM-49、MCM-56、ITQ-1、ITQ-2、ITQ-4、ITQ-21、SAPO-5、SAPO-11、SAPO-37、Breck-6(也称为EMT)、ALPO4-5。这些沸石是本领域中已知的，并且许多可在市场上买到。在本发明中，可以向中孔载体内引入沸石，或在催化剂载体中原位合成沸石。
可以把金属引入沸石骨架内作为晶格原子的替代，或使金属位于沸石微孔内。这些金属可以包括，例如，铝、钛、钒、锆、镓、硼、锰、锌、铜、金、镧、铬、钼、镍、钴、铁、钨、钯和铂。可以以组合的方式引入这些金属，例如，NiMo、NiW、PtPd等。
所述催化剂载体优选为三维中孔无机氧化物材料，该无机氧化物材料含有，以该无机氧化物材料(即，其中没有引入任何沸石)的微孔和中孔为基准，至少97体积％的中孔(即，不多于3体积％的微孔)，并且通常含有占至少98体积％的中孔。在美国专利第6,358,486中描述了制备优选的含多孔二氧化硅的催化剂载体的方法。如N2-孔隙度测定法所测定的，优选催化剂的平均中孔孔径大小为从约2nm至约25nm。
一般地，通过加热下列物质的混合物来制备中孔无机氧化物：(1)水中的无机氧化物前体，和(2)有机模板剂(templating agent)，其与氧化物前体或从该前体中生成的氧化物良好地混合，并且优选与它形成氢键。起始物通常为无定形材料，并且可包括一种或多种无机氧化物，例如氧化硅或氧化铝，有或没有其它金属氧化物。硅原子可部分地被其它金属原子所取代。这些金属包括，但不限于，铝、钛、钒、锆、镓、硼、锰、锌、铜、金、镧、铬、钼、镍、钴、铁、钨、钯和铂。可以把它们引入无机氧化物内的至少一个中孔壁上的和/或在至少一个中孔面上。在含中孔的结构的制备过程开始之前，可以非必须地把其它金属引入材料内。在制备材料后，也可以非必须地以其它离子如碱金属(例如，钠、钾、锂等)的离子来代替体系中的阳离子。
所述有机模板剂，一种形成中孔的有机化合物，优选为甘醇(一种包括两个或更多个羟基的化合物)，例如，丙三醇、二甘醇、三甘醇、四甘醇、丙二醇等等，或由三乙醇胺、三异丙醇胺、环丁砜、四亚乙基五胺和二苯甲酸二乙二醇酯组成的组中的成员。优选地，有机模板剂的沸点为至少约150℃。
所述中孔催化剂载体为假晶材料(即，通过现有X射线衍射技术观察不到结晶性)。中孔的直径优选为从约3nm至约25nm。如BET(N2)所测定的，催化剂载体的表面积优选从约400m2/g至约1200m2/g。催化剂孔容积优选从约0.3cm3/g至约2.2cm3/g。
催化剂中的沸石含量可以从低于约1％重量比至高于约99％重量比。但是，优选从约3％重量比至90％重量比，更优选为从约4％重量比至约80％重量比。含沸石的催化剂优选含有不大于(no more than)10体积％的微孔。
更具体地，制备催化剂的方法包括在水中悬浮沸石。然后向水中添加无机氧化物前体并混合。该无机氧化物前体可以是含硅化合物例如原硅酸四乙酯(TEOS)，或是铝源例如异丙醇铝，其与水反应形成无机氧化物。在市场上从已知的供应商那里可买到TEOS和异丙醇铝。
优选使上述混合物的pH值保持在约7.0。非必须地，含水混合物可以含有例如那些如上所述的其它金属离子。经搅拌后，向混合物中添加并混合有机模板剂。如下所述，有机模板剂在成孔步骤中帮助形成中孔。有机模板剂不应太憎水以致于在混合物中形成分离相。有机模板剂可以是如上所列的一种或多种化合物。优选向无机氧化物水溶液中逐滴添加有机模板剂并搅拌。一段时间后(例如，从约1至4小时)混合物形成浓稠凝胶。优选在该段时间内搅拌混合物以促进组分的混合。该溶液优选包括醇，其能被添加到混合物中和/或通过分解无机氧化物前体而原位形成。例如，当加热TEOS时产生乙醇。可通过分解异丙醇铝产生丙醇。
非必须地，可以通过预处理来改变沸石。例如，在一种预处理方式中，可以通过离子交换、浸渍、功能性物质的定位以及蒸热来改性沸石。另外，通过适当的处理，可以使层状结构的沸石如MCM-22分层剥落(exfoliate)成为新型沸石如ITQ-2。通过在碱的存在下用阳离子表面活性剂使前体膨胀，可以进行某些处理，如插层(intercalation)或分层，(Corma等人，J.Catal.191(1)：218-224，2000)。非必须地，通过例如带有或不带机械搅拌的超声处理可以使膨胀的材料分层。最后，分离并煅烧分层的材料，形成新型沸石。
本发明提供了一种新方法，以在多孔基体/载体内引入或稳定或负载分层沸石。首先能在水中悬浮膨胀材料，然后能向水中添加无机氧化物前体或中孔载体并如上所述地混合。非必须地，在其它组分(例如，成孔剂)的添加过程中和/或在形成凝胶的过程中，可以通过带有或不带机械搅拌的超声处理使膨胀材料分层。凝胶形成后，可以把与膨胀前所添加的沸石不同的新型沸石引入凝胶。
然后可选择地在从约5℃至约45℃的温度下，优选在室温下老化凝胶，以完成无机氧化物源的水解和缩聚。优选可以进行老化达约48小时，通常从约0小时至30小时，更优选从约2小时至20小时。老化步骤后，在空气中在约98℃至100℃下加热凝胶，加热时间(例如，从约6至约48小时)为足以通过驱除水而干燥凝胶。优选地，在干燥过程中，帮助形成中孔的有机模板剂应留在凝胶中。从而，优选有机模板剂的沸点为至少约150℃。
把仍含有有机模板剂的经干燥的材料加热至大量形成中孔的温度。成孔步骤在高于水的沸点并直至约为有机模板剂沸点的温度下进行。一般地，在从约100℃至约250℃，优选从约150℃至约200℃的温度下形成中孔。水热成孔步骤可以可选择地在密封容器中在自生压力下进行。最后产品中的中孔孔径和中孔容积受水热步骤的时间长短与温度的影响。一般地，提高处理温度和增加处理的持续时间将提高最终产品中的中孔直径和中孔容积百分比。
成孔步骤后，在约300℃至约1000℃之间煅烧所述材料。煅烧温度优选从约400℃至约700℃，更优选从约500℃至约600℃。保持煅烧温度足够长的时间以除去有机模板剂/成孔剂。部分取决于煅烧温度，煅烧步骤的持续时间通常为从约2小时至约40小时，优选5小时至15小时。
为防止过热点，应逐渐升高温度。优选地，应当以从约0.1℃/min至约25℃/min，更优选从约0.5℃/min至约15℃/min，最优选从约1℃/min至约5℃/min的速率使催化剂材料的温度向上(ramp)升至煅烧温度。
在煅烧过程中，最终形成催化剂材料的结构，同时把有机分子从该材料中除去并分解。
可以用有机溶剂如乙醇进行萃取来代替煅烧步骤以除去有机模板剂。在这种情况下，模板化剂可以被回收以再利用。
另外，本发明的催化剂粉末可以与结合剂如二氧化硅和/或氧化铝混合，然后通过挤出或其它适当的方法形成所需的形状(例如，压出型材、球丸、环等)。通过浸渍、离子交换、或通过如G.W.Skeels andE.M.Flanigen in M.Occelli，et al.，eds.，A.C.S.Symposium Series，Vol.398，Buttersworth，pp.420-435(1989)中所述替代部分晶格原子，可向催化剂中添加金属离子，例如铝、钛、钒、锆、镓、铜、锰、锌、镍、铁、钴、锗、铬和钼。
通过XRD、气体吸附、27Al-NMR和NH3-IR(红外)来表征本发明的组合物。XRD和27Al-NMR显示在硅质中孔材料上引入或负载沸石后，所述沸石的结构没有改变。但是，NH3-IR显示引入Beta沸石后羟基改变。羟基改变的程度也取决于最终复合物中沸石的装料量(loading)。虽然不希望局限于任何特定理论，据信沸石与中孔基体/载体的相互作用导致了独特的结构，该结构明显不同于沸石和中孔材料的简单线性组合。另外，FTIR显示了与酸性改性相一致的羟基频率位移。
原则上，本文所描述的催化剂可以用于所有其中通常使用基于沸石的催化剂的方法中。例如，ZSM-11可以用于被ZSM-5所催化的基本上所有的反应(例如，芳香族化合物烷基化、二甲苯异构化、脱蜡等)；ZSM-12可以用于芳香族化合物烷基化(例如，对二异丙基苯的制备)、芳构化、异构化、脱蜡等的方法中；ZSM-20可以用于异构化、烯烃制备、氢化裂化和芳构化；ZSM-22和ZSM-23用于异构化、烯烃制备、氢化裂化和芳构化；ZSM-34用于催化甲醇成为烯烃；ZSM-35用于脱蜡、异构化、芳构化、裂化和氢化；ZSM-48用于异构化；PSH-3和MCM-22对于芳香族化合物烷基化、裂化、异构化、芳构化等有活性；ITQ-1可以用于裂化、氧化等；ITQ-2对于裂化、水合、烷基化等尤其有活性；ITQ-21是用于裂化的非常好的催化剂；SAPO-5用于异构化、脱水、裂化；SAPO-34用于脱氢；SAPO-11用于脱蜡和芳香族化合物异构化。
例如，使用本文所述的催化剂，在FCC或TCC单元中，在从约400℃至约650℃的温度下，以从约3∶1至10∶1的催化剂对进料的重量比，可以催化裂化石油进料(例如，瓦斯油和真空瓦斯油)。用于催化裂化的进料可以包括初沸点(IBP)从约200℃至约260℃、终沸点(EBP)从约400℃至约455℃的石油馏分。非必须地，进料可以包括具有沸点高于540℃组分的石油馏分，例如脱沥青或未脱沥青的石油残渣、焦油砂油(tan sand oil)、页岩油、沥青或煤油。
在从约90℃至约250℃的温度、从约0.5巴至约35巴的压力、和从约1WHSV至约20WHSV的空速下，使用本文所述的催化剂可以以烯烃对有机化合物进行烷基化。
在从约200℃至约400℃的温度、从约10巴至约70巴的压力、和从约0.4WHSV至约50WHSV的空速下，使用本文所述的催化剂可以进行烃的氢化裂化。
在从约150℃至约500℃的温度、从约1巴至约240巴的压力、和从约0.1WHSV至约20WHSV的空速下，使用本文所述的催化剂可以进行烃的加氢异构化。
在较宽反应条件下，例如，在从约150℃至约500℃的温度、从约6巴至约110巴的压力、和从约0.1WHSV至约20WHSV的空速下，使用本文所述的催化剂可以进行烃的催化脱蜡。
在包括从约20℃至约350℃的温度、从约1巴至约110巴的压力、和从约0.1WHSV至约20WHSV的空速的反应条件下，使用本文所述的催化剂可以进行有机化合物(例如芳香化合物，烷基芳香化合物)的酰化。酰化剂包括，例如羧酸酐以及酰卤。
优选在包括从约600℃至约800℃的温度、小于约14巴的压力、和从约0.1WHSV至约10WHSV的空速的反应条件下，使用本文所述的催化剂进行轻质烃的芳构化。
在一些特别的应用中，本发明的组合物将比传统的催化剂表现出甚至更大的优势。例如，重质进料(heavy feeds)的催化裂化理想上需要中孔基体/载体上有一些弱酸性，以使非常大的分子预裂化为中等大小的分子，然后该中等大小的分子进一步裂化为所需的产品。本发明的组合物在中孔基体/载体的骨架中可以含有金属(例如，铝)，从而提供弱酸性。另外，中孔基体/载体所提供的高的孔容积和高的表面积可以改善对金属(例如，V、Ni、Fe)和对硫、氮和氧类物质的耐受性(tolerance)。另外，通过改变所用的沸石类型、沸石装料量和中孔度，可以容易地调整本发明的组合物，以满足过程的一些特别要求。
含一些具有(脱)氢化功能的金属(例如，Ni、W、Pt、Pd及其组合)的本发明的组合物可以用作氢化裂化的催化剂。通过适当地选择沸石装料、中孔基体/载体中提供酸性的金属的量、和具有氢化功能的金属的量，可以容易地实现裂化活性和氢化活性的平衡。通常地，沸石材料具有高的裂化活性，中孔材料具有较低的裂化活性。从而，可以调节沸石和中孔基体的组合，以提供所需的裂化活性。因此可以优化产率和选择性。例如，可以实现对中间馏分或柴油的高选择性。在润滑油基础油(lube base oil)的生产中，因为中孔基体/载体提供预裂化作用，所以本发明的组合物使进料范围得以扩展；它也改善了对重金属和其它有毒物质的耐受性。
通过下列实施例说明本发明的制备催化剂组合物的方法和催化剂组合物的应用，但是本发明并不限于这些实施例。在这些实施例中组合物的量为重量份。
实施例1
首先，在16.3份水中悬浮Si/Al摩尔比为25且平均粒度为1μm的1.5份经煅烧的Beta沸石，并搅拌30分钟。然后在搅拌下向悬浮液中添加20.3份原硅酸四乙酯(TEOS)。又持续搅拌30分钟后，添加9.3份三乙醇胺。再搅拌30分钟后，向混合物中逐滴添加4.0份氢氧化四乙铵水溶液(从Aldrich购得的35％溶液)，以提高pH值。搅拌约2小时后，混合物形成浓稠的不流动的凝胶。在室温静止状态下老化该凝胶17小时。然后，在100℃下干燥凝胶28小时。将经干燥的凝胶转移到高压釜中，并在170℃下水热处理17.5小时。最后，以1℃/min升温速率在空气中在600℃下煅烧凝胶10小时。
把最终产品命名为样品1。样品1中存在的Beta沸石的理论量为20wt％。样品1用XRD、TEM氮孔隙度测定法、氩孔隙度测定法和程序升温NH3脱附(TPD)表征。为比较目的也用XRD表征了纯的Beta沸石。
参照图1，以33分钟的扫描时间，曲线1-b所示的纯Beta沸石的XRD图在约7.70和2θ中的22.2°处显示了最明显的特征反射。图1-a表示具有Beta沸石晶体的中孔无机氧化物载体的(样品1)的XRD图。在小角度观察到强峰，说明样品1是中孔结构的材料。Beta沸石的峰相对小，因为最终产品中沸石的最大理论含量仅为20wt％。当把样品1的扫描时间延长至45小时，如曲线1-c所示，Beta沸石的特征峰变得清楚可见。
现在参照图2，其中描绘了样品1的高分辨率TEM图像，其显示了中孔基体12中的暗灰区域11。插图“ED”描绘了证实暗灰区域11为Beta沸石晶体的电子衍射图。
氮吸附显示样品1具有主要集中在约9.0nm的窄的中孔孔径分布、710m2/g的高表面积和1.01cm3/g的高的总孔容积。氩吸附在约0.64nm周围显示了微孔孔径分布的峰，对应于Beta沸石中的微孔孔径。直径小于0.7nm的孔的微孔容积为0.04cm3。这是纯Beta沸石的微孔容积的约16％。以最终复合物为基准，起初添加的未煅烧的Beta沸石占20wt％。由于在煅烧过程中除去模板，Beta沸石的重量降低了约20wt％。考虑到煅烧过程中沸石的质量损失，最终复合物中Beta沸石的预期含量为约16％，这与从微孔容积得到的值相一致。
参照图3，样品1的NH3-TPD测量显示了两个解吸峰，说明有和沸石中相似的强酸部位。
实施例2
首先，在85.0份水中悬浮Si/Al比为150且平均粒度为0.2μm的3.4份经煅烧的Beta沸石，并搅拌30分钟。然后在搅拌下向悬浮液中添加105.8份TEOS。又持续搅拌30分钟后，添加38.3份三乙醇胺。再搅拌30分钟后，向混合物中逐滴添加20.9份氢氧化四乙铵水溶液(35％)。搅拌约2小时后，混合物形成浓稠的不流动的凝胶。在室温静止状态下老化该凝胶24小时。然后，在空气中在98-100℃下干燥凝胶24小时。将经干燥的凝胶转移到高压釜中，并在180℃下水热处理4小时。最后，以1℃/min升温速率在空气中在600℃下煅烧凝胶10小时。图5显示了命名为样品2的所得产品的XRD图。最终复合物中有约10wt％的Beta沸石。
实施例3
首先，在51.02份水中悬浮Si/Al比为150且平均粒度为0.2μm的4.6份经煅烧的Beta沸石，并搅拌30分钟。然后在搅拌下向悬浮液中添加23.0份三乙醇胺。又持续搅拌30分钟后，添加63.5份TEOS。再搅拌30分钟后，向混合物中逐滴添加12.6份氢氧化四乙铵水溶液(35％)。搅拌约2小时后，混合物形成浓稠的不流动的凝胶。在室温静止状态下老化该凝胶24小时。然后，在空气中在100℃下干燥凝胶24小时。将经干燥的凝胶转移到高压釜中，并在180℃下水热处理4小时。最后，以1℃/min升温速率在空气中在600℃下煅烧凝胶10小时。图5显示了命名为样品3的所得产品的XRD图，其清楚地显示了Beta沸石的两个特征峰。最终复合物中有约20wt％的Beta沸石。氮吸附表明它的表面积为约730m2/g，孔容积为约1.08cm3/g。图4显示了样品3的中孔孔径分布。
实施例4
首先，在51.0份水中悬浮Si/Al比为150且平均粒度为0.2μm的12.2份经煅烧的Beta沸石，并搅拌30分钟。然后在搅拌下向悬浮液中添加23.0份三乙醇胺。又持续搅拌30分钟后，添加63.5份TEOS。再搅拌30分钟后，向混合物中逐滴添加12.7份氢氧化四乙铵水溶液(35％)。搅拌约2小时后，混合物形成浓稠的不流动的凝胶。在室温静止状态下老化该凝胶24小时。然后，在空气中在100℃下干燥凝胶24小时。将经干燥的凝胶转移到高压釜中，并在180℃下水热处理4小时。最后，以1℃/min升温速率在空气中在600℃下煅烧凝胶10小时。图5显示了命名为样品4的所得产品的XRD图，其清楚地显示了Beta沸石的两个特征峰。最终复合物中有约40wt％的Beta沸石。氮吸附表明它的表面积为约637m2/g，孔容积为约1.07cm3/g。图4显示了它的中孔孔径分布。
实施例5
首先，在17.0份水中悬浮Si/Al比为150且平均粒度为0.2μm的9.2份经煅烧的Beta沸石，并搅拌30分钟。然后在搅拌下向悬浮液中添加7.6份三乙醇胺。又持续搅拌30分钟后，添加21.2份TEOS。再搅拌30分钟后，向混合物中逐滴添加4.2份氢氧化四乙铵水溶液(35％)。搅拌约2小时后，混合物形成浓稠的不流动的凝胶。在室温静止状态下老化该凝胶24小时。然后，在空气中在100℃下干燥凝胶24小时。将经干燥的凝胶转移到三个50ml的高压釜中，并在180℃下水热处理4小时。最后，以1℃/min升温速率在空气中在600℃下煅烧凝胶10小时。图5显示了命名为样品5的所得产品的XRD图，其清楚地显示了Beta沸石的两个特征峰。最终复合物中有约60wt％的Beta沸石。氮吸附表明它的表面积为约639m2/g，孔容积为约0.97cm3/g。图4显示了它的中孔孔径分布。
实施例6
使八份样品1与两份Nyacol形式的氧化铝混合，以提供催化剂。通过下列过程干燥并煅烧混合物：以5℃/min的速率升温至120℃，保持120℃的温度一小时，然后以5℃/min的速率升温至500℃并保持五小时，最后以5℃/min的速率降温至150℃，然后在干燥器中使催化剂冷却至室温。然后将催化剂人工粉碎并筛分至-12/+20筛目以检测活性。该催化剂在中孔载体中含有16wt％的Beta沸石。用1.0克催化剂对再循环差动(differential)固定床反应器装料。再循环速率(200g/min)为进料速率(6.1g/min)的约33倍。开始时用苯填充已装料的反应器，当反应器温度达到190℃时，用计量泵计量量取进料(含0.35wt％乙烯的苯)。运行七小时。反应条件包括：温度190℃、压力350psig和空速6WHSV。在运行的开始、中间和结束时对进料取样。每隔三分钟对产品取样并用气相色谱仪分析。对于采用含16wt％Beta沸石的催化剂，用乙烯使苯烷基化形成乙基苯的反应，根据一阶速率方程得到了速率常数为0.30cm3/g-sec。或者，对于80wt％Beta沸石催化剂而言，该数值相当于1.50cm3/g-sec。
比较实施例A
除了不引入沸石外，根据实施例1中所述的方法制备全硅质中孔载体。把所得载体命名为比较样品A。对比较样品A进行NH3-TPD测量，图3显示了所得测量结果。
比较实施例B
将购自商业供应商的且含有80wt％Beta沸石(Si/Al比为4.9)和20wt％结合剂的样品调整大小至-12/+20筛目。图4表示Beta沸石的孔径分布。使用如实施例6所述的同样的方法和设备，检测在相同的烷基化反应中该比较实施例中的纯Beta沸石的活性。得到一阶速率常数0.29cm3/g-sec。
将实施例6的结果与比较实施例B对比，对于用乙烯使苯烷基化而言，根据本发明实施例6的催化剂具有比单独的同等量Beta沸石高约五倍的活性。这些结果表明，在样品1的合成过程中，中孔催化剂载体中沸石晶体的完整性得以保持。结果还表明，合成催化剂后，样品1的中孔载体中的微孔Beta沸石依然是可达的，并且在芳香族化合物烷基化反应中载体的中孔有利于传质。
实施例7
该实施例说明了引入MCM-22。首先，在10.5份水中悬浮Si/Al比为12.8且平均粒度为2.5μm的2.4份已合成(as synthesized)的MCM-22沸石，并搅拌30分钟。然后在搅拌下向上述悬浮液中添加9.2份三乙醇胺。又持续搅拌30分钟后，添加12.7份TEOS。再搅拌30分钟后，向混合物中逐滴添加2.52份氢氧化四乙铵水溶液(35％)。搅拌约2小时后，混合物形成浓稠的不流动的凝胶。在室温静止状态下老化该凝胶24小时。然后，在空气中在98℃下干燥凝胶24小时。将经干燥的凝胶转移到高压釜中，并在180℃下水热处理4小时。最后，以1℃/min升温速率在空气中在600℃下煅烧凝胶10小时。
命名为复合物7并以图6中的曲线6-c表示的所得产品的XRD图清楚地显示了MCM-22沸石(曲线6-b)和中孔材料(曲线6-a)的特征峰。在复合物7中有约40wt％的MCM-22沸石，假设没有铝来自硅质中孔材料，根据铝的含量，元素分析证实了这一数字。氮吸附表明它的表面积为约686m2/g，孔容积为约0.82cm3/g。图7显示中孔孔径分布集中在10nm左右。氩吸附显示微孔主要为0.5nm左右。
实施例8
该实施例说明了引入MCM-56。首先，使7.7份三乙醇胺与8.5份蒸馏水混合半小时。然后，在搅拌下向上述溶液中添加2.0份NH4 +形式的MCM-56沸石(Si/Al摩尔比为12.5)。又持续搅拌2小时后，在搅拌下添加10.6份TEOS。再搅拌30分钟后，向混合物中逐滴添加2.1份氢氧化四乙铵水溶液(35％)。继续搅拌直至混合物形成浓稠的不流动的凝胶。如实施例7中一样处理凝胶，得到白色粉末。
命名为复合物8并以图8中的曲线8-c表示的所得产品的XRD图清楚地显示了MCM-56沸石和中孔材料的两个特征峰。曲线8-b表示MCM-56沸石的XRD图，曲线8-a表示中孔材料的XRD图。元素分析表明最终复合物的总Si/Al比为43，最终复合物中沸石的装料为约33.3wt％。氮吸附表明它的表面积为约712m2/g，孔容积为约0.96cm3/g。图7显示它的中孔孔径分布主要为2.0nm左右。
实施例9
该实施例说明了引入ITQ-2。首先，将15.2份溴化十六烷基三乙基铵(CTAB)溶于31.7份水和32.7份氢氧化四丙铵中。然后，向上述溶液中添加2.7份已合成的MCM-22，得到悬浮液。在置于80℃油浴里带回流冷凝的烧瓶中搅拌悬浮液，以膨胀层状结构的MCM-22沸石。在超声槽(135w，40KHz)里使膨胀的MCM-22分层1小时得到ITQ-2沸石。洗涤并离心分离ITQ-2沸石直至悬浮液的pH值降至8。
将ITQ-2再悬浮于10份水中，然后在搅拌下添加到由9.2份TEA和12.7份TEOS组成的混合物中。约45分钟后形成浓稠凝胶。如实施例7中一样处理凝胶。命名为复合物9并以图9中的曲线9-c表示的最终产品的XRD图清楚地显示了ITQ-2沸石和中孔材料的两个特征峰。曲线9-b表示中孔材料的XRD图，曲线9-a表示ITQ-2沸石的XRD图。元素分析表明最终复合物的总Si/Al比为36.9，最终复合物中沸石的装料为约32.3wt％。氮吸附表明它的表面积为约685m2/g，孔容积为约0.40cm3/g。它的中孔孔径分布主要为2.1nm。
实施例10
该实施例说明了“原位”引入ITQ-2，其中在中孔形成的过程中进行MCM-22向ITQ-2的转化。所用的药品和它们的量与实施例9中一样。首先，以和实施例9相同的方法膨胀已合成的MCM-22。但是，不立即使膨胀的MCM-22分层。将它洗涤并随后离心分离直至用硝酸银溶液检测不到溴化物。在水中再悬浮膨胀的MCM-22。
把装有由TEA和TEOS组成的混合物的瓶置于超声槽中。既用声波振荡又用机械聚四氟乙烯搅拌器来搅拌混合物，同时添加膨胀的MCM-22悬浮液。搅拌约一小时后，添加2.5份TEAOH(35％，氢氧化四乙铵)，最终形成浓稠的凝胶。以和实施例7相同的方法处理凝胶。命名为复合物10并以图9中的曲线9-d表示的最终复合物的XRD图清楚地显示了ITQ-2沸石(曲线9-a)和中孔材料(曲线9-b)的两个特征峰。元素分析表明复合物10的总Si/Al比为32.4，最终复合物中沸石的装料为约50wt％。氮吸附表明它的表面积为约726m2/g，孔容积为约0.78cm3/g。如图7所示，中孔孔径分布主要为2.2nm。
实施例11
在有搅拌的间歇式反应器中进行2-甲氧基萘的酰化以得到2-乙酰基-6-甲氧基萘。将具有16.5份催化剂的反应器，即具有实施例10中制备的复合物10的反应器，在真空下在240℃下加热2小时，然后充满干氮气。待反应器冷却至120℃后，向反应器内注射250份萘烷(作为溶剂)、31.6份2-甲氧基萘、40份乙酸酐和10份正十四烷(作为内标)。反应六小时后，通过带WAX 52CB柱的GC来分析反应器混合物，发现2-甲氧基萘以100％的选择性和56％的转化率转化为2-乙酰基-6-甲氧基萘。
实施例12
使用上述实施例中制备的各种催化剂进行2-甲氧基萘的酰化以得到2-乙酰基-6-甲氧基萘。反应条件和实施例11中相同。在所有实验中反应器中沸石的量和实施例11中的相同。也就是说，催化剂(复合物)的量不同是因为复合物中沸石装料的不同。表1比较了在不同催化剂上的反应效果。
表1
在不同催化剂上酰化2-甲氧基萘的比较
  催化剂   催化剂描述   沸石装料％   沸石中的Si/Al比   转化率(％)   选择性(％)
  复合物7   MCM-22复合物   40.0   12.8   28.5   96
  复合物8   MCM-56复合物   33.3   12.5   53.4   96
  复合物10   ITQ-2复合物   50.0   12.8   56.2   96
实施例13
在固定床反应器中进行正己烷的裂化。向反应器内引入约1g通过粉碎和筛分得到的粒度为125-250μm的样品3。为活化，在50ml/min的气流中以10℃/min的加热速率把样品从室温加热至600℃，并保持在该温度下8小时。在大气压力下，以氮气中6.6mol％浓度的正己烷进行正己烷的裂化反应。以10℃为一级把反应温度从500℃改变至570℃。基于催化剂质量的经修改的接触时间稳定保持在1.4gcat*min*1-1。对于所有的测量，正己烷的转化率低于15％以避免失活作用。已发现可以用明显的一阶动力学来描述正己烷的裂化，并且对于不同的反应温度计算了基于沸石质量的一阶反应速率常数。为比较催化剂活性，用从四个一阶反应速率常数中确定的阿累尼乌斯(Arrhenius)方程计算对于538℃的反应速率常数。对于样品3所得反应速率为0.19g沸石 -1*min-1*1。
如下与纯Beta沸石，以及样品4和样品5进行比较：
把市场上的Si/Al比为150的Beta沸石压成片并筛分至125-250μm。使用与上面实施例7所述同样的方法和设备检测纯Beta沸石，以及样品4和样品5的活性。图10显示了表征催化剂活性的基于沸石质量的反应速率常数。样品3、4和5的活性比纯Beta沸石的活性高约两倍。所测150kJ/mol的相对高的活化能说明传质不影响相对小的正己烷分子的反应。
实施例14
用Brucker IFS88分光计以4cm-1的分辨率记录中孔载体和纯Beta沸石(样品3、4和5)的FTIR光谱。将所有的样品与KBr制成丸状，并置于永久连接到真空管道(最终压力≤10-5托)的石英池中，以在原位条件下热处理。
参照图11，传统上在3745cm-1处的强峰被指认为硅烷醇基团，在3610cm-1处(尤其对于Beta沸石)的非常小的峰可以被指认为它的布朗斯台德(Bronsted)酸性部位，在3725-3650cm-1区域的宽的吸收峰可以被指认为H-键合的硅烷醇或邻近路易斯酸中心的硅烷醇。通常，与单独考虑的所用Beta沸石和中孔载体相比，本发明的组合物(样品3、4、5)在3725-3650cm-1范围显示宽的吸收峰。有趣之处在于具有40wt％Beta沸石的复合物在3725-3650cm-1范围处具有最宽的羟基分布。另外，这些羟基的强度比其它样品中的更高。图11清楚地表明具有40wt％沸石的复合物与中孔载体或纯Beta沸石明显不同。
虽然不希望局限于任何特定理论，据信纳米大小的沸石与中孔基体的相互作用形成独特的第三结构，其不同于沸石和中孔材料的简单线性组合。另外，有与酸性改性相一致的羟基频率位移。这可以解释为什么40wt％沸石装料的酸性变化显著。这可能是与实施例13中正己烷裂化相关的催化活性。
实施例15
向含铝中孔基体中引入Si/Al摩尔比为14.8且表面积为606m2/g的超稳定Y(USY)。首先，在17.0份水中悬浮9.2份超稳定Y沸石，并搅拌30分钟。然后在搅拌下向上述悬浮液中添加7.7份三乙醇胺。又持续搅拌30分钟后，在搅拌下添加由21.2份TEOS和3.3份异丙醇铝组成的混合物。再搅拌30分钟后，向混合物中逐滴添加4.2份氢氧化四乙铵水溶液(35％)。搅拌约2小时后，混合物形成浓稠的不流动的凝胶。在室温静止状态下老化该凝胶24小时。然后，在空气中在100℃下干燥凝胶24小时。将经干燥的凝胶转移到高压釜中，并在180℃下水热处理2小时。最后，以1℃/min升温速率在空气中在600℃下煅烧凝胶10小时。把最终材料命名为复合物15。
图12的曲线12-a表示复合物15的XRD图，其清楚地显示了Y沸石和中孔材料的两个特征峰。曲线12-b表示Y沸石的XRD图。最终复合物中有约60wt％的Y沸石。氮吸附表明它的表面积为约689m2/g，孔容积为约0.99cm3/g。
实施例16
用复合物15制备催化裂化催化剂。通过离子交换，在搅拌下使一份复合物15与十份1N硝酸铵溶液在60℃下混合6小时，得到复合物的质子形式(H+-)。过滤、洗涤并在110℃下干燥固体材料，得到白色粉末。经过第二次离子交换后，在空气中在550℃下煅烧固体材料6小时。
使八份H+-复合物15与两份Nyacol形式的氧化铝混合，以提供催化剂。通过下列步骤干燥并煅烧混合物：(a)以5℃/min的速率升温至120℃，(b)在120℃的温度下保持一小时，(c)以5℃/min的速率升温至500℃并保持五小时，(d)以5℃/min的速率降温至150℃，和(e)然后在干燥器中使催化剂冷却至室温。催化剂含有约48％USY沸石。
然后在大气压力下以50％蒸汽在760℃下汽蒸催化剂10小时。把最终催化剂(含USY、中孔基体、和氧化铝结合剂)命名为CAT16A。
为比较裂化活性，通过与CAT16A的制备方法相同的离子交换、挤出和汽蒸来制备含48％USY和氧化铝结合剂(没有中孔基体)的命名为CAT16B的催化剂。
以甲苯中的环烷酸钒浸渍这两种催化剂的每种的一半，造成在工业条件下FCC催化剂的5000ppm钒失活。这两种经浸渍的催化剂分别被命名为CAT16AV和CAT16BV。
实施例17
以在400℃下的固定式流化床FCC单元、催化剂/油的比率2、投入生产(on stream)5分钟，使用流化活性测试(“FAI”)来评比实施例16中制备的四种催化剂的裂化活性。进料为东德克萨斯轻瓦斯油(Light East Texas Gas Oil)(LETGO)，其性质见表2。催化性能的比较见表3。
表2
东德克萨斯轻瓦斯油(LETGO)的性质
              API   36.4
  蒸馏(D1160)：IBP，(vol％)10％30％50％70％90％EBP溴数KV@100℃，cSt平均分子量倾点(pour point)，℃CCR，wt％折射率@70℃苯胺点，℃氢，wt％硫，wt％总氮量，ppm碱性氮(Basic Nitrogen)，ppm镍，ppm钒，ppm铁，ppm铜，ppm石蜡，wt％环烷芳香族化合物，wt％ 235℃254℃268℃287℃307℃341℃364℃0.501.30269-70.021.44927613.30.13300450.10.10.770.0544.733.222.1
表3
催化表现
  催化剂   钒含量％   FAI％转化率   活性保持率％
  CAT16A   0   65.6
  CAT16AV   0.52   51.3   78.7
  CAT16B   0   48.3
  CAT16BV   0.53   23.8   49.3
表3中的结果说明，由于酸性中孔基体，本发明的组合物改善了对重金属的耐受性。沸石与酸性中孔基体的新型组合也提高了裂化活性。
实施例18
以与实施例15中同样的方法合成含USY沸石的、命名为复合物18的复合物。仅有的区别在于所用的化学品的量：2.9份USY沸石、28份异丙醇铝、171.4份原硅酸四乙酯、34份氢氧化四乙铵、124份三乙醇胺和138份水。图12显示了复合物18的XRD图，其清楚地显示了Y沸石和中孔材料的两个特征峰。复合物含有约5wt％的USY沸石，表面积为约694m2/g，孔容积为约1.1cm3/g。
如实施例16中所述，将复合物18离子交换为质子形式(H+-)并挤出。最后，复合物形成直径为1.6mm的圆柱形状，并含有约4wt％USY、76wt％含Al的中孔材料和20wt％Al2O3。
以Ni和W浸渍使复合物18进一步功能化。在搅拌下使五(5)份硝酸镍水溶液(14wt％Ni)与8.4份偏钨酸铵溶液(39.8wt％W)混合。然后在搅拌下用9份水稀释混合物。以上述Ni/W溶液浸渍12.5份复合物18，在118℃下干燥2小时并在500℃下煅烧2小时。所得改性复合物18被命名为CAT 18，并含有4.0wt％的Ni和18.7wt％的W。它的主要特征在于大量的弱酸性中孔基体。
实施例19
本实施例说明了实施例18中的材料作为氢化裂化催化剂的用途。评价实施例18中制备的复合物18在氢化裂化中对中间馏分的选择性。以预硫化的复合物18(以常规方法)使用加氢处理的重真空瓦斯油(heavy vacuum gas oil)作为进料，在流动反应器中进行评价。在LHSV1.5千克/升·小时、总压140巴(H2S分压5.5巴，氨分压0.075巴)和气体/进料比1500NL/kg的条件下操作。进料的性质见表4。
表4
加氢处理的重真空瓦斯油的性质
  蒸馏(D1160)：IBP，℃(vol％) 345
  10％30％50％70％90％EPKV@100℃，cSt碳，wt％氢，wt％总硫量，wt％总氮量，ppm   4024414725085647418.8186.713.40.00816.1
在65wt％的组分的净转化条件下，确定对中间馏分(例如，沸点范围从175℃至345℃)的选择性。出人意料地，选择性达到72.6wt％。
虽然上面的描述包含许多细节，这些细节不应理解为限制本发明的范围，而仅仅是作为本发明的优选实施方案的示例。本领域所属技术人员将能预见如实施例所定义的本发明的范围与精神内的其它许多可能性。

Claims (55)

1.一种组合物，包括：
a)至少一种有序的、结晶的和微孔的材料，其平均孔径小于15埃；
b)至少一种非结晶的无机氧化物，所述无机氧化物具有中孔或中孔和微孔，其中所述无机氧化物在X射线衍射图中具有2θ中在0.3与3度之间的峰，并且其中所述中孔为相互连接的中孔。
2.如权利要求1所述的组合物，其中所述的结晶微孔材料选自Beta沸石、Y沸石、USY、丝光沸石、L沸石、ZSM-5、ZSM-11、ZSM-12、ZSM-20、Theta-1、ZSM-23、ZSM-34、ZSM-35、ZSM-48、SSZ-32、PSH-3、MCM-22、MCM-49、MCM-56、ITQ-1、ITQ-2、ITQ-4、ITQ-21、SAPO-5、SAPO-11、SAPO-37、Breck-6和ALPO4-5组成的组。
3.如权利要求1所述的组合物，其中至少一种无机氧化物具有，以该无机氧化物的微孔和中孔为基准，占至少97体积％的中孔，400-1100m2/g的表面积，和约0.3-2.2cm3/g的总的孔容积。
4.如权利要求3所述的组合物，其中所述中孔的孔径大小范围为从约2nm至约25nm。
5.如权利要求3所述的组合物，其中所述的多孔无机氧化物为氧化硅。
6.如权利要求1所述的组合物，进一步包括至少一种金属。
7.如权利要求6所述的组合物，其中把所述金属引入沸石骨架内作为晶格原子的替代和/或使所述金属位于沸石微孔内。
8.如权利要求6所述的组合物，其中把所述金属引入无机氧化物内的至少一个中孔壁内和/或在至少一个中孔面上。
9.如权利要求6所述的组合物，其中所述金属为选自铝、钛、钒、锆、镓、硼、锰、锌、铜、金、镧、铬、钼、镍、钴、铁、钨、钯和铂组成的组的至少一种金属。
10.如权利要求1所述的组合物，其中按所述结晶微孔材料的重量计算组分的百分比范围为从约3％至约90％。
11.如权利要求1所述的组合物，其中按所述微孔沸石的重量计算组分的百分比范围为从约4％至约80％。
12.制备催化材料的方法，包括如下步骤：
a)预处理沸石；
b)使所述经预处理的沸石与水、无机氧化物或无机氧化物前体、以及至少一种形成中孔的有机化合物组合形成混合物；
c)干燥所述混合物；
d)加热所述经干燥的混合物，加热温度和加热时间足以形成中孔无机氧化物结构。
13.如权利要求12所述的方法，其中所述的沸石为层状沸石，并且预处理包括该层状沸石的分层或插层。
14.如权利要求13所述的方法，其中在允许层状沸石膨胀和分层的条件下使层状沸石与阳离子表面活性剂的碱性溶液接触，以实现所述的分层。
15.如权利要求13所述的方法，其中所述沸石的分层包括对沸石进行超声处理。
16.如权利要求12所述的方法，其中所述的预处理包括离子交换、浸渍、功能性物质的固定和/或汽蒸。
17.如权利要求12所述的方法，其中所述的形成中孔的有机化合物选自丙三醇、二甘醇、三甘醇、四甘醇、丙二醇、三乙醇胺、三异丙醇胺、淀粉、环丁砜、四亚乙基五胺和二苯甲酸二乙二醇酯组成的组。
18.如权利要求12所述的方法，其中所述的形成中孔的有机化合物的沸点为至少150℃。
19.如权利要求12所述的方法，其中通过使无机氧化物前体与水反应形成所述的无机氧化物。
20.如权利要求12所述的方法，其中保持所述混合物的pH值高于约7.0。
21.如权利要求14所述的方法，其中如下干燥所述混合物：在空气中加热混合物，加热温度和加热时间为足以去除至少大部分的水和形成中孔的有机化合物。
22.如权利要求12所述的方法，其中所述加热步骤(d)包括把经干燥的混合物加热至从约100℃至约250℃的温度。
23.如权利要求12所述的方法，进一步包括如下步骤：在从约300℃至约1000℃的温度下煅烧所述经加热干燥的混合物，煅烧时间为至少足以从中孔无机氧化物载体中除去形成中孔的有机化合物。
24.如权利要求12所述的方法，进一步包括组合金属离子与混合物，所述金属选自铝、钛、钒、锆、镓、硼、锰、锌、铜、金、镧、铬、钼、镍、钴、铁、钨、钯和铂组成的组。
25.如权利要求12所述的方法，进一步包括使结合剂与催化材料混合并使该催化材料形成预定形状的步骤。
26.制备催化材料的方法，包括如下步骤：
a)使层状结构的沸石与阳离子表面活性剂的碱性溶液在允许该层状沸石膨胀的条件下接触；
b)使所述膨胀的沸石与水、无机氧化物或无机氧化物前体、和至少一种形成中孔的有机化合物组合，以形成混合物；
c)使所述层状沸石分层；
d)干燥所述混合物；
e)加热所述经干燥的混合物，加热温度和加热时间为足以形成中孔氧化物结构。
27.如权利要求26所述的方法，其中所述的形成中孔的有机化合物选自丙三醇、二甘醇、三甘醇、四甘醇、丙二醇、三乙醇胺、三异丙醇胺、环丁砜、四亚乙基五胺和二苯甲酸二乙二醇酯组成的组。
28.如权利要求26所述的方法，其中所述的形成中孔的有机化合物的沸点为至少150℃。
29.如权利要求26所述的方法，其中通过使无机氧化物前体与水反应形成所述的无机氧化物。
30.如权利要求29所述的方法，其中所述的无机氧化物前体选自二氧化硅源和氧化铝源组成的组。
31.如权利要求26所述的方法，其中保持所述混合物的pH值高于约7.0。
32.如权利要求26所述的方法，其中如下干燥所述的混合物：在空气中加热混合物，加热温度和加热时间为足以去除至少大部分的水和形成中孔的有机化合物。
33.如权利要求26所述的方法，其中所述的加热步骤(e)包括把经干燥的混合物加热至从约100℃至约250℃的温度。
34.如权利要求26所述的方法，其中加热步骤(e)包括把经干燥的混合物加热至从约150℃至约200℃的温度。
35.如权利要求26所述的方法，进一步包括在从约300℃至约1000℃的温度下煅烧所述经加热干燥的混合物的步骤。
36.如权利要求26所述的方法，进一步包括在从约400℃至约700℃的温度下煅烧所述经加热干燥的混合物约2小时至约40小时的步骤。
37.如权利要求26所述的方法，进一步包括组合金属离子与混合物，所述金属选自铝、钛、钒、锆、镓、硼、锰、锌、铜、金、镧、铬、钼、镍、钴、铁、钨、钯和铂组成的组。
38.如权利要求26所述的方法，进一步包括使结合剂与催化材料混合并使该催化材料形成预定形状的步骤。
39.处理烃进料的方法，包括：
使含有至少一种烃组分的进料与催化有效量的催化剂在足以转化所述烃组分的反应条件下接触，所述催化剂包括至少一种在多孔无机氧化物上负载的沸石，所述多孔无机氧化物具有，以该多孔无机氧化物的微孔和中孔为基准，占至少97体积％的中孔，具有约400-1100m2/g的表面积，并具有2θ在0.3与3度之间的至少一个X射线衍射峰。
40.如权利要求39所述的方法，其中通过反应实现烃组分的转化，所述反应选自酰化、烷基化、二聚、低聚、聚合、脱蜡、水合、脱水、歧化、氢化、脱氢、芳构化、选择性氧化、异构化、加氢处理、催化裂化和氢化裂化组成的组。
41.如权利要求39所述的方法，其中所述的进料包括芳香族化合物和酰化剂，并且所述反应为酰化反应，该酰化反应在足以使所述芳香族化合物与酰化剂进行酰化的酰化反应条件下进行。
42.如权利要求41所述的方法，其中所述的酰化剂包括羧酸酐、酰卤。
43.如权利要求41所述的方法，其中所述的酰化反应条件包括温度从约20℃至约350℃、压力从约1巴至约110巴、和空速从约0.1WHSV至约20WHSV。
44.如权利要求39所述的方法，其中所述的进料包括石油馏分，并且所述反应条件为足以实现馏分的催化裂化。
45.如权利要求44所述的方法，其中所述的石油馏分包括至少一种初沸点从约200℃至约260℃且终沸点从约400℃至约455℃的组分。
46.如权利要求45所述的方法，其中所述的石油馏分进一步包括至少一种沸点高于约540℃的组分。
47.如权利要求46所述的方法，其中所述的沸点高于540℃的组分为未脱沥青的石油残渣、脱沥青的石油残渣、焦油砂沥青、页岩油、或煤油液体。
48.如权利要求44所述的方法，其中所述的反应条件包括温度从约440℃至约650℃，催化剂对进料的重量比从约3∶1至10∶1。
49.如权利要求39所述的方法，其中所述的进料包括石油馏分，并且所述反应条件为足以实现馏分的氢化裂化以生产相对较轻质的烃产品。
50.如权利要求49所述的方法，其中所述的石油馏分含有至少一种沸点高于约260℃的组分。
51.如权利要求49所述的方法，其中所述的石油馏分含有至少一种沸点高于约290℃的组分。
52.如权利要求49所述的方法，其中所述的石油馏分含有至少一种沸点高于约340℃的组分。
53.如权利要求50所述的方法，其中所述的石油馏分进一步包括至少一种组分，该组分选自未脱沥青的石油残渣、脱沥青的石油残渣、焦油砂沥青、页岩油、和煤油液体组成的组。
54.如权利要求49所述的方法，其中所述的相对较轻质的烃产品包括组分，该组分选自沸点范围为从150℃至400℃的中间馏分、柴油和润滑油基础油组成的组。
55.如权利要求39所述的方法，其中通过加氢异构化实现所述烃组分的转化，并且所述反应条件包括温度从约150℃至约500℃、压力从约1巴至约240巴、和WHSV从约0.1至约20。
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