CN109070071A - 纳米级沸石负载型催化剂和其制备方法 - Google Patents

纳米级沸石负载型催化剂和其制备方法 Download PDF

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Publication number
CN109070071A
CN109070071A CN201780022853.7A CN201780022853A CN109070071A CN 109070071 A CN109070071 A CN 109070071A CN 201780022853 A CN201780022853 A CN 201780022853A CN 109070071 A CN109070071 A CN 109070071A
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carrier material
nano
catalyst
zeolite
sized zeolites
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CN201780022853.7A
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Inventor
丁连辉
埃萨姆·阿尔-萨伊德
马纳尔·阿尔-埃德
哈娜·哈布比
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Saudi Arabian Oil Co
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Saudi Arabian Oil Co
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Publication of CN109070071A publication Critical patent/CN109070071A/zh
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Abstract

根据所描述的一个或多个实施例，沸石负载型催化剂可以通过包括以下的方法合成：将胶体混合物与金属氧化物载体材料组合以形成载体前体材料；加工所述载体前体材料以形成载体材料；以及用一种或多种金属浸渍所述载体材料，以形成所述沸石负载型催化剂。所述胶体混合物可包括纳米级沸石晶体，并且所述纳米级沸石晶体的平均尺寸可小于100nm。

Description

纳米级沸石负载型催化剂和其制备方法
相关申请的交叉参考
本申请要求2016年4月11日提交的美国临时申请序列号62/320,938的优先权，其全部内容通过引用并入本文中。
技术领域
本公开涉及用于石化燃料化学转化的催化剂。更具体来说，本公开涉及可用于加氢处理的催化剂的制备方法。
背景技术
加氢裂化是一种多用的催化方法，其通过在氢气存在下的芳族饱和、裂化以及异构化反应将重油转化为较轻产物。这些加氢裂化处理需要加氢裂化催化剂，其可以至少部分地裂化重油中存在的大分子。例如，环烷烃和多芳烃可以在加氢裂化过程中部分转化。大多数加氢裂化催化剂使用沸石作为载体材料。然而，这些催化剂在重油转化率和稳定性方面存在限制。例如，常规的加氢裂化催化剂可能具有差的多环芳烃裂化转化率。另外，这类催化剂的制造可能是昂贵且耗时的。
发明内容
沸石可用作加氢裂化催化剂的裂化组分。根据本发明所描述的实施例，减小沸石粒度可以有效地减小或甚至消除重油分子扩散到沸石中的限制，从而提高催化剂活性和选择性。然而，纳米级粒子难以洗涤和分离，导致分离成本高且沸石产率降低。此外，纳米级粒子在煅烧过程和水热处理过程中容易聚集。本发明所描述的制备它们的催化剂和方法不需要从合成的胶体混合物中分离纳米级沸石。因此，避免了分离所需的成本和时间。
根据本公开的一个实施例，沸石负载型催化剂可以通过包含以下的方法合成：将胶体混合物与金属氧化物载体材料组合以形成载体前体材料；加工载体前体材料以形成载体材料；以及用一种或多种金属浸渍载体材料以形成沸石负载型催化剂。胶体混合物可包含纳米级沸石晶体，并且纳米级沸石晶体的平均尺寸可小于100nm。
根据本公开的另一个实施例，沸石负载型催化剂可以通过包含以下的方法合成：提供包含纳米级沸石晶体的胶体混合物；将包含纳米级沸石晶体的胶体混合物与氧化铝组合以形成载体前体材料；加工载体前体材料以形成载体材料；以及用一种或多种金属浸渍载体材料以形成沸石负载型催化剂。纳米级沸石晶体的平均尺寸可小于100纳米(nm)。
根据本公开的另一个实施例，沸石负载型催化剂可包含20wt.％(wt.％)至75wt.％的多孔氧化铝、20wt.％至30wt.％的金属催化剂材料的％以及5wt.％to 50wt.％的纳米级沸石。纳米级沸石的平均尺寸可小于100nm。沸石负载型催化剂的表面积可为至少180平方米/克(m2/g)。
根据本公开的另一个实施例，沸石负载型催化剂可以通过包含以下的方法合成：提供包含纳米级沸石晶体的胶体混合物；将包含纳米级沸石晶体的胶体混合物与金属氧化物载体材料组合以形成载体前体材料；加工载体前体材料以形成载体材料；以及用一种或多种金属浸渍载体材料以形成沸石负载型催化剂。加工载体前体的步骤可包含：干燥载体前体材料以形成可挤出材料；塑形载体前体材料；以及水热处理载体前体材料。纳米级沸石晶体的平均尺寸可小于100nm。
本公开中所描述的实施例的其它特征和优点将在下文中的详细描述中阐述，并且对所属领域的技术人员而言，一部分根据所述描述是显而易见的，或由如本公开中(包括下文中的详细描述、权利要求书以及附图)所描述地实践所述技术而意识到。
附图说明
当结合以下附图阅读时，可最好地理解下文中的本公开具体实施例的详细描述，其中相同的结构用相同的指代编号表示，并且其中：
图1是根据本公开中所描述的一个或多个实施例的用于合成沸石负载型催化剂的方法的概括流程图。
具体实施方式
本公开描述一种合成纳米级沸石负载型催化剂的方法。在一个或多个实施例中，纳米级沸石负载型催化剂包括纳米级沸石晶体。本发明所描述的合成方法可以消除制备常规的包括纳米级沸石的纳米级沸石负载型催化剂所需的加工步骤，如从胶体混合物中分离纳米级沸石。如本公开中所使用，常规的纳米级沸石催化剂是指包括纳米级沸石的催化剂，并且其由掺入所述催化剂中的干燥颗粒纳米级沸石制备。本公开中描述的方法不需要将纳米级沸石分离成固体干燥颗粒形式。此外，本发明所描述的纳米级沸石负载型催化剂的实施例可具有改善的物理特性，例如增加的表面积、孔体积和孔径。这些改进的物理特性中的一种或多种可能使纳米级沸石负载型催化剂产生增强的催化活性。
如本公开中所使用，“纳米级沸石”是指以最长维度测量，尺寸小于100nm的沸石粒子。在一些实施例中，沸石粒子(即纳米级沸石)作为单晶结构存在。本公开中描述的纳米级沸石的尺寸可为1nm至100nm，如30nm至100nm。沸石的“平均尺寸”是指给定纳米级沸石负载型催化剂中的所有沸石粒子的尺寸的平均值。应理解，涵盖各种沸石结构用于所述催化剂中。例如，掺入所述催化剂中的纳米级沸石可以是沸石A、β、丝光沸石、Y或ZSM-5型沸石。
现在参考图1，其描绘了合成纳米级沸石负载型催化剂的方法的工艺流程图。根据一个或多个实施例，所描述的纳米级沸石负载型催化剂可通过方法100合成，所述方法100至少包含：提供包含纳米级沸石晶体110的胶体混合物的步骤112；将包含纳米级沸石晶体的胶体混合物与金属氧化物载体材料组合以形成载体前体材料120的步骤122；加工载体前体材料以形成载体材料130的步骤132；以及用一种或多种金属浸渍载体材料以形成纳米级沸石负载型催化剂140的步骤142。
在一个实施例中，合成方法可由提供包含纳米级沸石晶体的胶体混合物的步骤开始。提供包含纳米级沸石晶体的胶体混合物的步骤可包括但不限于如下方法：在胶体混合物中制造纳米级沸石晶体或直接得到这种包含纳米级沸石晶体的胶体混合物。应理解，可以使用多种方法来制造含有纳米级沸石晶体的胶体混合物，并且在本公开中涵盖未明确描述的用于制造含有纳米级沸石晶体的胶体混合物的方法。如本公开中所使用，“胶体混合物”是指至少两种材料的混合物，其中混合物具有细分状态，使得分散在介质中的分子或多分子粒子的至少一个维度处于约1nm与1微米(μm)之间。
根据提供包含纳米级沸石晶体的胶体混合物的一个实施例，包含纳米级沸石晶体的胶体混合物可通过以下来制备：提供至少含有季铵盐、二氧化硅、氧化铝以及水的混合物；并且将至少含有季铵盐、二氧化硅、氧化铝以及水的混合物进行高压釜处理以在胶体混合物中形成纳米级沸石晶体。在一个实施例中，季铵盐可为四甲基氢氧化铵(TEAOH)。根据一个或多个实施例，至少含有季铵盐、二氧化硅、氧化铝以及水的混合物的这些成分的摩尔比为：1摩尔氧化铝；6摩尔至120摩尔季铵盐(例如20摩尔至50摩尔，或22摩尔至36摩尔)；15摩尔至200摩尔二氧化硅(例如30摩尔至80摩尔，或40摩尔至60摩尔)；以及250摩尔至1000摩尔水(例如400摩尔至850摩尔，或500摩尔至750摩尔)。季铵盐与二氧化硅的摩尔比可为0.4至0.6。根据一个实施例，如本公开中前文所述，可将至少含有季铵盐、二氧化硅、氧化铝以及水的混合物在100摄氏度(℃)至180℃(如130℃至150℃，或140℃)下以40转/分钟(rpm)至80rpm(如60rpm)高压釜处理2至4天，以形成纳米级沸石晶体。在高压釜处理之前，可将至少含有季铵盐、二氧化硅、氧化铝以及水的混合物在室温下搅拌，如4小时。应理解，所描述的高压釜处理和搅拌步骤可根据高压釜处理的混合物的确切组分和待形成的期望沸石晶体而作出某种程度上的修改。
在提供包含纳米级沸石晶体110的胶体混合物的步骤之后，可将包含纳米级沸石晶体的胶体混合物与金属氧化物载体材料(如氧化铝)组合以形成载体前体材料。在一个或多个实施例中，与包含纳米级沸石的胶体混合物组合的金属氧化物载体材料包含两种不同的孔径。例如，一些金属氧化物载体材料的孔径可为0.4毫升/克(mL/g)至0.6mL/g(如0.45mL/g至0.55mL/g)，且一些金属氧化物载体材料的孔径可为0.8mL/g至1.2mL/g(例如0.85mL/g至1.1mL/g)。具有小孔径(即0.4mL/g至0.6mL/g)的金属氧化物载体材料在本公开中可称为“小孔径金属氧化物”，且具有大孔径(即0.8mL/g至1.2mL/g)的金属氧化物载体材料在本公开中可称为“大孔径金属氧化物”。
与包含纳米级沸石的胶体混合物组合的金属氧化物载体材料可包括单一金属氧化物化学物种，或可为两种或更多种金属氧化物化学物种的组合。在一个或多个实施例中，至少一部分金属氧化物是氧化铝，或金属氧化物载体材料由氧化铝组成。
除金属氧化物载体材料之外，可将硝酸(即HNO3)与包含纳米级沸石的胶体混合物组合，以使载体前体材料还包含HNO3。不受理论束缚，据信HNO3的添加可以使金属氧化物载体材料(如氧化铝)胶溶，其在载体前体材料中起到粘合剂的作用，为本发明所描述的沸石负载型催化剂增加了物理完整性。在煅烧过程中HNO3可分解。在煅烧后，可向催化剂中掺入其它酸，如盐酸(HCl)。然而，如果掺入HCl，则催化剂中可能存在来自HCl的氯(Cl)，这会使催化剂更快失活。因此，因为HNO3的粘合功能性且不显着降低催化持久性，一些实施例可使用HNO3作为示例性酸。
根据一个实施例，可在大孔径金属氧化物与包含纳米级沸石的胶体混合物组合之前，将小孔径金属氧化物与包含纳米级沸石的胶体混合物组合。例如，在一个实施例中，可将小孔径金属氧化物、大孔径金属氧化物或两者与HNO3混合，然后与包含纳米级沸石晶体的胶体混合物组合以形成载体前体材料。
应理解，与一些常规纳米级沸石催化剂的制备不同，在本发明公开的实施例中，载体的材料(例如，如多孔氧化铝的金属氧化物)与沸石组合，而沸石处于胶体系统中。相比之下，常规纳米级沸石催化剂可以通过以下方法制备：将纳米级沸石与胶体混合物分离(如通过离心)，并制成颗粒形式。然后必须通过加热来干燥分离的纳米级沸石粒子。无需分离步骤，本发明所描述的合成方法具有若干优点。例如，由于不使用分离步骤，可以提高纳米级沸石的产率并且可以节省时间。另外，可以避免将纳米级粉末从胶体混合物中分离出时可能存在的环境和健康问题。另外，在一些实施例中，可以避免添加的步骤，如纳米级沸石粒子的离子交换和多次洗涤步骤。
在将包含纳米级沸石晶体的胶体混合物与金属氧化物载体材料组合以形成载体前体材料的步骤之后，可加工载体前体材料以形成载体材料。载体前体材料的加工可包括：一次或多次干燥载体前体材料以形成可挤出材料；塑形载体前体材料；以及将载体前体材料进行水热处理。在一些实施例中，载体前体材料可依次进行干燥以形成可挤出材料，成形，然后水热处理。载体前体材料的干燥可包括加热载体前体材料，并且所得的干燥、可挤出的载体前体材料可具有面团状稠度且可具有非牛顿流体的特性。加热的时间和温度可取决于载体前体材料中的水分量，但应足以除去足够使载体前体材料可挤出的水分。然后可将载体前体材料挤出成三维形状，例如但不限于球体、丸粒、圆柱体、三叶形以及四叶形片，并且可以涵盖其它合适的几何形状。在塑形之后，可在高温下将载体前体材料进行一段长时间的水热处理。在一个实施例中，水热处理可包括在2巴(bar)至4巴的压力下将载体前体材料暴露于450℃至600℃的温度0.5小时至3小时。水热处理会由载体前体材料中含有的水产生自生蒸汽。在一个替代实施例中，在水热处理期间也可施加额外水分。
在加工载体前体材料以形成载体材料的步骤之后，可用一种或多种金属浸渍载体材料以形成纳米级沸石负载型催化剂。根据所描述的实施例，载体材料的浸渍可包含使载体材料与包含一种或多种金属催化剂前体的溶液接触。例如，可将载体材料浸没在包含一种或多种金属催化剂前体的溶液中，浸渍方法有时称为饱和浸渍。在饱和浸渍的实施例中，可将载体浸没在一定量的溶液中，所述溶液所包含的金属催化剂前体是由载体吸收的金属催化剂前体的2至4倍，随后除去剩余的溶液。根据另一个实施例，浸渍可以通过初湿含浸，有时称为毛细浸渍或干浸渍。在初湿含浸的实施例中，含金属催化剂前体的溶液与载体接触，其中溶液的量约等于载体的孔体积且毛细作用会将溶液吸入孔中。在将载体材料与溶液接触后，可将载体材料在至少500℃(如500℃至600℃)的温度下煅烧至少3小时(如3小时至6小时)。例如，煅烧可在500℃的温度下进行4小时。通常，浸渍过程将允许金属催化剂附着到载体材料(即沸石和金属氧化物载体)上。金属催化剂前体可包括Ni、W、Mo、Co中的一种或多种，并且在浸渍之后，作为包含Ni、W、Mo、Co或其组合的化合物存在于催化剂载体上。当需要两种金属催化剂时，可以使用两种或更多种金属催化剂前体。然而，一些实施例可仅包括Ni、W、Mo或Co中的一个。例如，如果需要W-Ni催化剂，则催化剂载体材料可通过六水合硝酸镍(即Ni(NO3)2·6H2O)与偏钨酸铵(即(NH4)6H2W12O40)的混合物浸渍。然而应理解，本发明的范围不应受所选金属催化剂前体的限制，其它合适的金属催化剂前体可包括六水合硝酸钴(Co(NO3)2·6H2O)，七钼酸铵((NH4)6Mo7O24·4H2O)或钼酸铵((NH4)2MoO4)。在浸渍之后，经浸渍的金属催化剂可作为金属氧化物，例如WO3、MoO3、NiO以及CoO存在，且在本公开中称为“金属催化剂材料”。虽然这些金属催化剂材料可包括金属氧化物，但应理解，金属催化剂材料不同于催化剂的金属氧化物载体材料，后者在一些实施例中为多孔氧化铝。
本公开中描述的纳米级沸石负载型催化剂的材料组成可包含：20wt.％至90wt.％的一种或多种金属氧化物载体材料(即例如多孔载体材料，如多孔氧化铝)；20wt.％至30wt.％的金属催化剂材料；以及5wt.％至50wt.％的沸石。如本公开中前文所述，一种或多种金属氧化物载体材料可由多孔氧化铝组成。根据一个或多个实施例，本发明所描述的催化剂可包含组成量为10wt.％至65wt.％的大孔径氧化铝和组成量为15wt.％至25wt.％的小孔径氧化铝。而且，如先前在本公开中所述，金属催化剂材料可包含WO3、MoO3、NiO和CoO中的一种或多种。根据一个或多个实施例，本发明所描述的催化剂可包含：组成量为13wt.％至18wt.％的MoO3、组成量为20wt.％至25wt.％的WO3或组合组成量为3wt.％至8wt.％的NiO与CoO中的一种或多种。通常，催化剂载体材料由安置在多孔金属氧化物载体上和其中的纳米级沸石形成，且金属催化剂材料设置在载体上。
所描述的纳米级沸石负载型催化剂，如通过本公开中前文所描述的方法合成的那些，相比于常规制备的纳米级沸石负载型催化剂，可具有以下中的一种或多种：更大表面积、更大孔体积或更大孔径。根据一个实施例，本发明的纳米级沸石负载型催化剂的表面积可为至少180m2/g(如至少190m2/g、至少200m2/g、至少210m2/g或甚至至少220m2/g)。根据另一个实施例，本发明所描述的纳米级沸石负载型催化剂的孔体积可为至少0.45mL/g(如至少0.5mL/g或甚至至少0.55mL/g)。根据另一个实施例，本发明所描述的纳米级沸石负载型催化剂的孔径可为至少9.5nm(如至少9.7nm、至少9.9nm或甚至至少10.1nm)。如本公开中所使用，“孔径”是指平均孔径，“孔体积”是指测量的总孔体积。
根据本公开的另一个实施例，纳米级沸石负载型催化剂可用作加氢裂化反应以及其它加氢加工反应的催化剂。加氢裂化反应可用于裂化烃进料或馏分，且可并入加氢处理中。可通过本发明所描述的催化剂加工的示例原料包括减压瓦斯油、脱沥青瓦斯油以及轻循环油。通常，加氢加工单元可利用加氢处理反应和底床加氢裂化反应。在加氢处理反应中，主要反应可以是硫、氮以及金属去除(有时分别称为加氢脱硫(HDS)、加氢脱氮(HDN)以及加氢脱金属(HDM))。除加氢裂化功能之外，所述催化剂可具有HDS，HDN或HDM功能中的一种或多种。在加氢裂化反应中，主要反应是大烃转化为小烃(即裂化)。加氢处理可用于升级石油馏分，其中石油馏分的烃的裂化和转化率通常低于10wt.％。应理解，本发明所描述的纳米级沸石负载型催化剂可用作加氢裂化的其它功能的催化剂，并且不应限于特定用途，如所述加氢处理单元中的加氢裂化催化剂。
实例
通过以下实施例进一步阐明纳米级沸石负载型催化剂的制备方法的各种实施例。这些实施例本质上是说明性的且不应被理解为限制本发明的主题。
实例1-本发明所公开的催化剂的合成
为了形成纳米级沸石，分别使用气相二氧化硅(200，可获自赢创工业(Evonic Industries))、铝粉以及四乙基氢氧化铵(TEAOH)(35wt.％水溶液，可获自奥德里奇(Aldrich))作为二氧化硅源、铝源以及模板剂。前体胶的氧化物摩尔组成比为30TEAOH:50SiO2:Al2O3:750H2O。将金属铝溶解在一部分含TEAOH的水溶液中以形成澄清溶液，然后将其加入到由气相二氧化硅和另一部分含TEAOH的水溶液制成的浆料中。将形成的硅铝酸盐流体胶在环境温度下在烧杯中搅拌4小时，然后转移到125毫升(mL)聚四氟乙烯(PTFE)衬里的不锈钢高压釜中。在413开尔文(K)下进行，或者在烘箱中在的静态下进行，或者在油浴中在60rpm的旋转状态下进行结晶。在不同时间段的结晶之后，淬火高压釜以终止结晶过程。
将小孔径氧化铝(孔径0.4-0.6mL/g)与稀释的HNO3混合，然后将大孔径氧化铝(孔径0.8-1.2mL/g)添加到小孔径氧化铝与HNO3的混合物中。。然后，将由盛装有纳米级沸石晶体的高压釜形成的纳米级沸石浆料添加到小孔径与大孔径氧化铝的混合物中。通过加热来从混合物中除去一些水直到形成面团稠度。然后将此面团状材料挤出并在550℃下在1巴自生蒸汽下进行水热处理1小时。然后将水热处理、挤出后的载体材料用适量六水合硝酸镍[Ni(NO3)2·6H2O]与偏钨酸铵[(NH4)6H2W12O40]的水溶液浸渍，形成具有22-26wt.％WO3和3-6wt.％NiO的催化剂。然后将浸渍后的载体材料在383K下干燥隔夜，然后在773K下煅烧4小时。
实例2-常规催化剂的合成
通过如下方法制备常规的纳米级沸石催化剂。分别使用气相二氧化硅(200，可获自赢创工业)、铝粉以及TEAOH(35wt.％水溶液，可获自奥德里奇)作为二氧化硅源、铝源以及模板剂前体胶的氧化物摩尔组成为30TEAOH:50SiO2:Al2O3:750H2O。将金属铝溶解在一部分含TEAOH的水溶液中以形成澄清溶液，然后将其加入到由气相二氧化硅和另一部分含TEAOH的水溶液制成的浆料中。将形成的硅铝酸盐流体胶在环境温度下在烧杯中搅拌4小时，然后转移到125mL PTFE衬里的不锈钢高压釜中。在413K下进行，或者在烘箱中在静态下进行，或者在油浴中在旋转状态(60rpm)下进行结晶。在不同时间段的结晶之后，淬火高压釜以终止结晶过程。使用16,000rpm离心将最终产物与液体分离，用去离子水洗涤几次，直到pH<9.0，并在烘箱中在383K下干燥。
将干燥沸石粉末样品在高压釜中在823K且0.1兆帕(MPa)“自蒸汽”压力下处理1小时。将上述水热处理后的β沸石与大孔氧化铝(SasolTH100/150，孔体积0.96mL/g，比表面积201.6m2/g)和粘合剂(部分酸胶溶氧化铝，Sasol,B)混合，挤出形成圆柱形挤出物，在383K下干燥隔夜，然后在823K下在空气中煅烧4小时，以形成载体。WNi催化剂通过以下来制备：使用初湿含浸法使用适当量的六水合硝酸镍(即Ni(NO3)26H2O)与偏钨酸铵(即(NH4)6H2W12O40)的水溶液与上述载体共浸渍，在383K下干燥隔夜，并在773K下煅烧4小时。
实例3-实例1催化剂和实例2催化剂的分析
测量实例1催化剂和实例2催化剂的各种特性，包括表面积、孔体积以及孔径，并显示在表1中。
表1
催化剂 实例1催化剂 实例2催化剂(常规)
表面积，m<sup>2</sup>/g 220 179
孔体积，mL/g 0.56 0.42
孔径，nm 10.2 9.4
另外，测试了本发明所描述的实例1催化剂和实例2常规催化剂的催化活性。催化剂活性评估在1升(L)搅拌式高压釜反应器(Autoclave Engineers Division of Snap-tite，Inc.的搅拌反应器)中进行。轻循环油(Light cycle oil，LCO)用作反应物，LCO的特性列于表2中。然后，将20克(g)催化剂装入反应器中的催化剂篮中。反复抽空反应器并重新注入氢气以替换高压釜中的空气。此后，向反应器中添加5mL硫化剂、二甲基二硫化物(DMDS)。DMDS分解的理论计算和实验结果表明，5mL的DMDS足以硫化20g催化剂。在加热反应器之前，将反应器加压到3.4MPa。将催化剂在593K下原位硫化2小时，并在633K下再硫化2小时。硫化后，通过安装在反应器顶部的进料加料罐将LCO加入分批高压釜反应器中。在1000rpm搅拌下，将反应器加压到4.8MPa并以3开尔文每分钟(K/min)的速率将温度升到648K。当温度达到设定温度(648K)时，将氢气压力调节到6.8MPa并在搅拌下保持2小时。反应后，收集并分析液体产物。分别根据ASTM D4629、ASTM D4294以及ASTM D6591分析氮、硫以及芳烃。凭借气相色谱通过模拟蒸馏测量LCO和液体产物的沸程。催化剂的HDS、HDN以及HDA活性由下式确定：
其中xF和xP分别代表进料和产物中的硫、氮以及饱和烃(来自烃组成分析)的含量。实例1催化剂和实例2催化剂的催化活性测试结果显示在表3中。
表2
表3
实例2常规催化剂 实例1催化剂
密度(g/mL，15.6℃) 0.9129 0.9087
总氮(重量百万分率) 40.2 1.51
总硫(重量百万分率) 893.4 665.9
烃分布(wt.％)
饱和烃 21.7 27.6
单环芳烃 46.5 46.3
二环芳烃 25.6 20.2
多环芳烃 6.2 5.9
HDN(％) 92.1 99.7
HDS(％) 94.4 95.8
HDA(％) 11.6 18.3
与实例2常规催化剂相比，实例1催化剂具有增加的HDN、HDS以及HDA活性。与常规催化剂相比，二环芳烃和多环芳烃含量均降低。
注意，以下权利要求中的一个或多个使用术语“其中”作为过渡短语。出于定义本技术的目的，应注意，所述术语在权利要求中作为开放式过渡短语引入，所述短语用于引入结构的一系列特征的叙述，并且应当以与更常用的开放式前导词术语“包含”同样方式地理解。
应理解，赋予特性的任何两个定量值可以构成所述特性的范围，并且在本公开中涵盖由给定特性的所有规定的定量值形成的范围的所有组合。另外，应理解，制备所公开的催化剂所涉及的具体加热温度和时间可以根据催化剂的具体组分而变化，并且不应限制于所公开的本发明所描述的催化剂的制备方法。
已经详细地并且通过参考特定实施例描述了本公开的主题，应注意，本公开中描述的各种细节不应被视为暗示这些细节与作为本公开中所描述的各种实施例的基本组分的元件相关，即使在本说明书随附的每个附图中示出了特定元件的情况下也是如此。而是，应将所附权利要求视为本公开的范围的唯一表示以及本公开中描述的各种实施例的对应范围。此外，显然在不脱离所附权利要求的范围的情况下可以进行修改和变化。

Claims (20)

1.一种合成沸石负载型催化剂的方法，所述方法包含：
将胶体混合物与金属氧化物载体材料组合以形成载体前体材料，其中所述胶体混合物包含纳米级沸石晶体，且所述纳米级沸石晶体的平均尺寸小于100nm；
加工所述载体前体材料以形成载体材料；以及
用一种或多种金属浸渍所述载体材料以形成所述沸石负载型催化剂。
2.根据权利要求1所述的方法，其中所述胶体混合物是通过将至少含有季铵盐、二氧化硅、氧化铝以及水的混合物进行高压釜处理形成的。
3.根据权利要求2所述的方法，其中所述季铵盐是四甲基氢氧化铵(TEAOH)。
4.根据权利要求2所述的方法，其中所述至少含有季铵盐、二氧化硅、氧化铝以及水的混合物具有以下摩尔比：
1摩尔氧化铝；
15摩尔至35摩尔所述季铵盐；
20摩尔至80摩尔二氧化硅；以及
250摩尔至1000摩尔水。
5.根据权利要求1所述的方法，其中与所述包含纳米级沸石的胶体混合物组合的所述金属氧化物载体材料包含：
孔径为0.4mL/g至0.6mL/g的小孔径金属氧化物；以及
孔径为0.8mL/g至1.2mL/g的大孔径金属氧化物。
6.根据权利要求5所述的方法，其中在所述大孔径金属氧化物与所述包含纳米级沸石的胶体混合物组合之前，将所述小孔径金属氧化物与所述包含纳米级沸石的胶体混合物组合。
7.根据权利要求1所述的方法，其中所述载体前体材料还包含硝酸。
8.根据权利要求1所述的方法，其中所述金属氧化物载体材料是氧化铝。
9.根据权利要求1所述的方法，其中所述金属氧化物载体材料是多孔氧化铝。
10.根据权利要求1所述的方法，其中所述加工所述载体前体材料的步骤包含干燥所述载体前体材料以形成可挤出材料。
11.根据权利要求1所述的方法，其中所述加工所述载体前体材料的步骤包含塑形所述载体前体材料。
12.根据权利要求11所述的方法，其中挤出所述载体前体材料。
13.根据权利要求1所述的方法，其中所述加工所述载体前体材料的步骤包含将所述载体前体材料进行水热处理。
14.根据权利要求13所述的方法，其中将所述载体前体材料进行水热处理包含将所述载体前体材料暴露于2巴至4巴的压力且450℃至600℃的温度下0.5小时至3小时。
15.根据权利要求13所述的方法，其中所述水热处理产生自生蒸汽。
16.根据权利要求1所述的方法，其中所述浸渍所述载体材料的步骤包含使所述载体材料与包含一种或多种金属催化剂前体的溶液接触，其中所述金属催化剂前体包含Ni、W、Mo、Co中的一种或多种。
17.一种沸石负载型催化剂，其包含：
20wt.％至75wt.％多孔氧化铝；
20wt.％至30wt.％金属催化剂材料；以及
5wt.％至50wt.％纳米级沸石；
其中：
所述纳米级沸石的平均尺寸小于100nm；以及
所述沸石负载型催化剂的表面积为至少180m2/g。
18.根据权利要求17所述的方法，其中所述沸石负载型催化剂的孔体积为至少0.45mL/g。
19.根据权利要求17所述的方法，其中所述沸石负载型催化剂的孔径为至少9.5nm。
20.根据权利要求17所述的方法，其中所述金属催化剂材料包含WO3、MoO3、NiO以及CoO中的一种或多种。
CN201780022853.7A 2016-04-11 2017-04-07 纳米级沸石负载型催化剂和其制备方法 Pending CN109070071A (zh)

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