CN102548656B - 含磷沸石催化剂及其制备方法 - Google Patents

含磷沸石催化剂及其制备方法 Download PDF

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CN102548656B
CN102548656B CN201080043866.0A CN201080043866A CN102548656B CN 102548656 B CN102548656 B CN 102548656B CN 201080043866 A CN201080043866 A CN 201080043866A CN 102548656 B CN102548656 B CN 102548656B
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阿希姆·库马·高希
尼塔·库尔卡尼
帕梅拉·哈尔韦
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Abstract

通过用磷化合物处理沸石而制得可用于芳族烷基化的沸石催化剂。煅烧经磷处理过的沸石并使其与液体水接触，由此从所述经磷处理过的沸石去除一定量的磷。然后加热所述经磷处理过的沸石。通过在适于芳族烷基化的反应条件下使所制得的沸石催化剂与芳族化合物和烷基化试剂的芳族烷基化进料接触，也可进行制备芳族产物的方法。

Description

含磷沸石催化剂及其制备方法
技术领域
本发明一般性地涉及用于芳族烷基化的催化剂。
背景技术
芳族化合物可被烷基化而形成不同的烷基化芳族产物。一种具有特定价值的烷基化芳族产物为对二甲苯。由于非常需要将对二甲苯氧化成对苯二甲酸(其为形成聚酯纤维和树脂的主要组分)，因而对二甲苯为有价值的取代芳族化合物。其可由石脑油的加氢处理(催化重整)、石脑油或瓦斯油的蒸汽裂化和甲苯歧化反应来商业制得。
使用甲醇将甲苯烷基化(也称为甲苯甲基化)已用于实验室研究以制备对二甲苯。已知甲苯甲基化在酸性催化剂上，特别是在沸石或沸石型催化剂上进行。特别地，ZSM-5沸石、沸石β和磷酸硅铝(SAPO)催化剂已用于该工艺。通常，邻(o)-、间(m)-和对(p)-二甲苯的热力学平衡混合物可通过甲苯的甲基化来形成，如以下反应所示。
在约500℃的反应温度下，o-、m-和p-二甲苯的热力学平衡组成可分别为大约25摩尔％、50摩尔％和25摩尔％。然而，这种甲苯甲基化可在广泛温度范围内进行。诸如C9+和其他芳族产物的副产物可以通过二甲苯产物的二次烷基化来产生。
可通过吸附和异构化的循环从混合的二甲苯中分离对二甲苯。由于在平衡混合物中的异构浓度低，这种循环可能不得不重复数次。高纯级(99+％)的p-二甲苯对于其氧化成对苯二甲酸是期望的。然而，这种高纯级的p-二甲苯的生产成本可能极高。可使用采用结晶技术的不同方法，且所述方法可以更便宜，其中在初始二甲苯产物中p-二甲苯的浓度为大约80％以上。因此，高于p-二甲苯的平衡浓度可能是期望的。
如果催化剂具有形状选择性质，则可在甲苯甲基化反应中获得显著更高量的p-二甲苯。通过窄化沸石孔隙开口的尺寸、钝化沸石的外表面或控制沸石酸度，可在改性沸石催化剂中获得形状选择性质。甲苯甲基化可在改性ZSM-5沸石催化剂上进行从而得到含有比热力学浓度显著更高量的p-二甲苯的二甲苯产物。
本发明涉及催化剂和催化剂的制备方法，所述催化剂在用于芳族烷基化反应(如甲苯甲基化)时具有形状选择性质，并且还具有增加的催化剂稳定性。
附图说明
为了更完全地理解本发明，现在将参照结合附图的如下描述，在附图中：
图1示出了对于使用经磷处理过的ZSM-5沸石催化剂(催化剂A-H)的甲苯甲基化反应，甲苯转化率随时间变化的图，所述经磷处理过的ZSM-5沸石催化剂中的一些已经历液态水预处理，而其他未进行水预处理或已进行蒸汽水预处理。
具体实施方式
沸石为具有微孔结构的铝硅酸盐材料。它们可为天然存在的或合成的。沸石在多种不同的烃转化反应如异构化和烷基化反应中常用作催化剂。其中有芳族化合物的烷基化。
ZSM-5沸石为用于芳族烷基化的催化剂的最通用的沸石之一。可具体提及使用根据本发明进行改性的ZSM-5沸石，以用于甲苯甲基化中，对此所述改性沸石特别适合。然而，本发明也适用于其他沸石，特别是具有中孔(medium pore)尺寸的那些沸石(平均孔径为约至约的那些沸石)。ZSM-5沸石具有约至约的平均孔径。中孔沸石的非限制性例子包括ZSM-5、Ω沸石和丝光沸石。对于本领域技术人员也将显而易见的是，尽管本文描述的沸石催化剂用于甲苯甲基化，但它们可适用于其他类型的反应如烷基转移和其他芳族烷基化反应。特别地，本发明的催化剂可适用于在混合的二烷基化芳族产物中为对位异构体提供提高的选择性的反应。
ZSM-5沸石及它们的制备描述于美国专利No.3702886中，所述专利以引用方式并入本文。起始ZSM-5沸石可为NH4 +或H+形式，并且可含有痕量的其他阳离子。在本发明中，起始ZSM-5沸石在改性之前可具有约30以下至约1000以上的二氧化硅/氧化铝摩尔比，更具体而言，二氧化硅/氧化铝摩尔比可为约30、50、80、100、200、250、280、300、350、400、500至约1000以上，包括在该范围内的任意数据点和所有数据点，以及该范围的端点。在某些应用中，ZSM-5沸石在改性之前可具有约250以上，且仍更具体地约280至约1000以上的二氧化硅/氧化铝摩尔比。
应当理解的是，对于本文所列举或描述为可用、合适等的任何浓度或含量范围，其旨在包括在所述范围内的每个浓度或含量(包括端点)，并被视为已具体指明。例如，“1至10的范围”应理解为指在约1和约10之间的连续统(continuum)中每一个可能的数。因此，即使在所述范围内的具体数据点，或甚至在所述范围内没有数据点被明确确定或仅涉及具体的一些，但应理解，本发明人认识且理解在所述范围内的任意且所有数据点均被认为已被指定，且本发明人拥有整个范围以及在所述范围内的所有点。
为了对ZSM-5沸石或其他沸石提供对位选择性，通过用含磷化合物处理所述沸石而使其改性。这种含磷化合物可以包括但不限于膦酸、次亚膦酸、亚磷酸和磷酸、这些酸的盐和酯，以及卤化磷。特别地，磷酸(H3PO4)和磷酸氢二铵((NH4)2HPO4)可以用作含磷化合物，来为用于芳族烷基化或甲苯甲基化的催化剂提供形状选择性从而提供提高的对位选择性。这种改性催化剂可含有其量以沸石重量计为约0.01wt％至约15wt％或更高的磷(P)。在某些实施方案中，磷含量以沸石重量计可为约8wt％或9wt％或更高。
磷处理可通过多种技术进行。这可包括沸石的基于水的磷处理。所述处理可包括浆料蒸发、初湿(wet incipient)和喷雾干燥法。也可使用沸石和磷化合物的固-固混合，并随后使混合物接触作为液体或蒸汽相的水。
在浆料蒸发中，可以通过制备磷化合物的水溶液与沸石的浆料而将磷掺入催化剂中。可利用浆料的加热来促进沸石的处理以及使液体蒸发。在大多数情况下，将浆料加热至约25℃以上，约70℃至约100℃的温度可为合适的。在该步骤过程中也可搅拌或搅动所述浆料以确保均匀处理。将沸石浆料加热至接近完全蒸发液体导致料团的形成，可干燥或煅烧所述料团以形成粉末或粒子。或者，液体从沸石浆料中蒸发可以通过使用本领域公知的喷雾干燥技术来实现。
在初湿法中，例如通过喷雾将磷化合物的水溶液加入至干燥沸石中而不形成浆料。初始可为粉末形式的干燥沸石可与磷化合物或其水溶液混合。如果需要，可将水加入至沸石粉末和含磷化合物或其溶液的混合物中以促进它们之间的相互作用。
然后，在含有氧气(通常为空气)的环境中，在约250℃或更高的温度下，更特别地在约300℃至约700℃，更特别地约400℃至约570℃的温度下煅烧经磷处理过的沸石。煅烧可随时间进行，通常数分钟至1小时或更长。煅烧也可通过随时间逐渐升温而进行。
经磷处理过的ZSM-5沸石可提供总孔隙体积为约0.2ml/g以下的经处理的沸石。更特别地，总孔隙体积可为约0.07ml/g至约0.18ml/g，更特别地约0.11ml/g至约0.15ml/g。经磷处理过的ZSM-5沸石的BET表面积可为约10m2/g至约300m2/g，更特别地为约150m2/g至约250m2/g。
在磷处理和煅烧之后，所述经磷处理过的沸石可任选地用粘合剂来结合。所述粘合剂材料可包括无机氧化物材料，如氧化铝、粘土和二氧化硅材料。粘合剂可用于为催化剂提供所需的形状，例如1/16英寸圆柱体形挤出催化剂。特别地，含铝材料粘合剂可为特别有用的，所述含铝材料为如氧化铝、粘土、磷酸铝、二氧化硅-氧化铝或其他含铝材料或它们的组合。经结合的催化剂可含有以催化剂的总重量计为约1wt％至约99wt％的粘合剂材料。在一些应用中，所述粘合剂的存在量以催化剂的总重量计可以为约10wt％至约50wt％粘合剂。
在某些实施方案中，经P处理过的沸石可在结合之前在约300℃以上的温度下煅烧，然后可用合适的粘合剂来结合沸石，然后再次煅烧，如美国专利No.7,368,410中所述，所述专利以引用方式并入本文。
在一些实施方案中，即使在无粘合剂的情况下，所述经磷处理过的沸石(在煅烧之前)也可被成型为特定形状和尺寸以形成催化剂，例如1/16英寸圆柱体形挤出物。这种催化剂可被描述为“自结合(self-bound)”催化剂。
然后用液体水处理对经磷处理并煅烧过的沸石(未结合、自结合或用诸如氧化铝的粘合剂结合)进行处理。这通过用多种方法使经磷处理过的沸石与液体水接触而完成。本文所用的表述“液体水”意在涵盖主要为液相并处于水的凝固点以上并且处于水的沸点以下的条件下的水。在大多数情况下，液体水处理在高于0℃且低于100℃的温度下，在大气压条件或大约大气压条件的压力条件下进行。然而，可存在其他情况，其中压力低于或高于大气压。在这种情况下，对于特定的压力条件，在确保水温在水的凝固点以上且在沸点以下的温度下进行液体水处理，以确保水主要为液相。在许多应用中，液体水处理在约25℃(室温)至约100℃的温度下进行。
在一种方法中，通过将经磷处理过的沸石浸入液体水浴中而进行液体水处理。浸渍时间可为数分钟至数小时或甚至数天。在大多数实施方案中，浸渍时间将为约1小时至24小时或更长。所述浸渍可在浴内搅动或不搅动沸石的情况下进行。
在另一方法中，经磷处理过的沸石在流动液体水流中接触。这可通过将沸石浸入强制液体水流中而不使用任何气体稀释剂而完成。流动液流的持续时间可为数分钟至数小时或甚至数天。在不使用任何气体稀释剂下流动液流的持续时间可与水浴的持续时间相同或可以更短。
或者，液体水可混合于或夹带于气体稀释剂内。气体稀释剂可为氢气或其他气体(例如N2、CO2、轻质烷烃、空气等)，其可为惰性气体，或这些气体的组合。可以通过在高于水的凝固点且低于水的沸点的条件下使流动的氢气或其他气体鼓泡通过或经过液体水，使得一定量的液体水被夹带在流动气体稀释剂内，来进行这种处理。然后使含磷沸石与流动的液体水/气体混合物接触。夹带于气体内的流动液水流的持续时间可为数分钟至数小时或甚至数天。
在液体水处理之后，可以例如通过过滤、倾析等使沸石与任何残余液体水分离。也可以在液体水处理之后进行进一步的加热以干燥沸石。典型的干燥温度可为约70℃至100℃以及更高的温度。
含磷沸石的液体水处理可去除松散结合的磷。可通过液体水处理去除多达20％以上的初始磷含量。在一些实施方案中，可通过液体水处理去除约20％至约30％的初始磷含量。
在液体水处理之后，也可使用之前讨论的煅烧温度和时间来进行另外的煅烧步骤。
在最初使用新鲜沸石催化剂之前，所述沸石也可进行进一步的汽蒸步骤，如同许多沸石催化剂一样。在任何反应中使用催化剂之前，可在300℃或更低的温度下汽蒸所述催化剂。汽蒸可在反应器的原位或非原位进行。在一些实施方案中，在温和温度下汽蒸催化剂。可用于本发明的在温和温度下汽蒸的方法描述于美国专利No.7304194中，所述专利以引用方式并入本文。在其他实施方案中，在液体水处理之后可不进行进一步的汽蒸。
在干燥和/或煅烧和任何进一步的汽蒸处理之后，经液体水处理的含磷沸石可以用作芳族烷基化反应中的催化剂。本发明适用的烷基化反应的例子包括使用烷基化试剂(例如甲醇)进行的甲苯烷基化。其他反应可包括芳族烷基化和烷基转移。尽管本发明适用于许多芳族烷基化反应，但所述沸石催化剂特别适用于甲苯甲基化以通过使用ZSM-5沸石催化剂制备对二甲苯。尽管本文的大多数描述可能针对这种甲苯甲基化，但本领域技术人员会易于理解其不仅限于这种用途。
经液体水处理的含磷沸石催化剂可在合适的烷基化反应条件下与芳烃和烷基化试剂的适当进料接触，以进行芳族烷基化。在芳族烷基化中，可使用烷基化进料。也可使用气体共进料。共进料气体可包括氢气或惰性气体。本文所用的表述“烷基化进料”意在涵盖芳族化合物和烷基化试剂。本文关于甲苯甲基化所用的表述“甲基化进料”意在涵盖甲苯和甲醇的进料。
除了任何共进料气体之外，还可以将可为蒸汽形式的水作为共进料与烷基化进料一起引入反应器中。可在具有作为共进料的氢气或惰性气体下或在无作为共进料的氢气或惰性气体下，在烷基化反应的启动过程中将用于烷基化或甲基化反应的水或蒸汽与烷基化进料一起引入反应器，或者可在初始启动之后将用于烷基化或甲基化反应的水或蒸汽引入。在任一情况下，可在液体水与共进料气体(如果存在)和烷基化进料混合之前加入并蒸发液体水。在芳族烷基化中水共进料的使用描述于美国专利No.7060864中，所述专利以引用方式并入本文。在其他应用中，可以不使用水共进料。
用于甲苯甲基化或其他芳族烷基化的反应器压力可以改变，但通常为约10至约1000psig(磅/平方英寸，表压)。反应器温度可以改变，但通常为约400至约700℃。在将进料引入反应器后，可将催化剂床的温度调节至选定的反应温度以达到所需的转化率。温度可以以约0.1℃/分钟至约10℃/分钟的速率逐渐增加，以提供所需的最终反应器温度。如实施例中所用的反应器温度指在反应器的催化剂床的入口处测得的温度。
反应可在常用于进行芳族烷基化反应的多种不同的反应器中进行。单个反应器或串联和/或并联的多个反应器可适用于进行芳族烷基化或甲苯甲基化反应。
本文所用的催化活性可表示为转化的烃或反应物相对于烃或反应物进料的摩尔数的摩尔％。在甲苯转化为二甲苯的甲苯甲基化中，催化活性可通过转化的甲苯相对于甲苯进料的摩尔数而测得，并可由下式定义：
摩尔％甲苯转化率＝[(Ti-To)Ti]×100          (2)
其中，Ti为甲苯进料的摩尔数，To为未反应的甲苯的摩尔数。
本文所用的混合二甲苯的选择性可表示为：
摩尔％混合二甲苯选择性＝[Xtx/(Ti-To)]×100     (3)
其中Xtx为产物中的全部或混合(o-、m-或p-)二甲苯的摩尔数。
本文所用的p-二甲苯的选择性可表示为：
摩尔％p-二甲苯选择性＝(Xp/Xtx)×100         (4)
其中Xp为p-二甲苯的摩尔数。
本文所用的甲醇转化率可表示为：
摩尔％甲醇转化率＝[(Mi-Mo)Mi]×100           (5)
其中，Mi为甲醇进料的摩尔数，Mo为未反应的甲醇的摩尔数。
本文所用的甲苯甲基化的甲醇选择性可表示为：
摩尔％甲醇选择性＝[Xtx/(Mi-Mo)]×100          (6)
其中Xtx为混合(o-、m-或p-)二甲苯的摩尔数，Mi为甲醇进料的摩尔数，且Mo为未反应的甲醇的摩尔数。
如下实施例更好地用来说明本发明。
实施例
实施例1
比较催化剂A
SiO2/Al2O3摩尔比为约280的NH4-ZSM-5沸石粉末用含水H3PO4处理，然后在约530℃的温度下煅烧。将经磷处理过的ZSM-5沸石压碎为细粉，然后与约20重量％的氧化铝粘合剂组合，并挤出为1/16英寸直径的圆柱体形挤出物。然后将结合的沸石挤出物煅烧或加热至530℃的温度以形成基础催化剂(催化剂A)，所述基础催化剂含有以催化剂的总重量计为大约7.5wt％的磷。然后使用催化剂A(实施例2和3)评价不同的液体水处理对经磷处理过的沸石催化剂的性能的影响。
实施例2
催化剂B
将约30.1g的催化剂A浸入烧瓶(瓶口用铝箔覆盖)内的100ml水中，并置于约60℃的温度下的烘箱中过夜。催化剂通过倾析水而得以分离，并且在约530℃的温度下干燥并煅烧10小时以形成催化剂B。
实施例3
催化剂C
将约5.1g的催化剂A置于反应管中，并通过流动水进行处理。水以1.0ml/分钟与458立方厘米/分钟的H2气一起进料通过在室温下的催化剂床，持续约5小时。然后在约530℃的温度下煅烧所述催化剂10小时以形成催化剂C。
催化剂D
将约2.5g的催化剂A置于反应管中，并通过流动水进行处理。水以1.0ml/分钟与458立方厘米/分钟的H2气一起进料通过在约60℃下的催化剂床，持续约5小时。使用另一新鲜催化剂装料(2.5g)重复催化剂A的水处理，然后将两批装料混合在一起，并在约530℃的温度下煅烧10小时以形成催化剂D。
催化剂E
将约2.5g的催化剂A置于反应管中，并通过流动水进行处理。水以1.0ml/分钟与458立方厘米/分钟的H2气一起进料通过在约100℃下的催化剂床，持续约5小时。使用另一新鲜催化剂装料(2.5g)重复催化剂A的水处理，然后将两批装料混合在一起，并在约540℃的温度下煅烧10小时以形成催化剂E。
催化剂F
将约3.0g的催化剂A置于反应管中，并通过流动水进行处理。水以1.0ml/分钟与458立方厘米/分钟的H2气一起进料通过在约350℃下的催化剂床，持续约5小时。使用另一新鲜催化剂装料(3.0g)重复催化剂A的水处理，然后将两批装料混合在一起，并在约540℃的温度下煅烧10小时以形成催化剂F。
催化剂G
将约3.0g的催化剂A置于反应管中，并通过流动水进行处理。水以1.0ml/分钟与458立方厘米/分钟的H2气一起进料通过在约500℃下的催化剂床，持续约5小时。使用另一新鲜催化剂装料(3.0g)重复催化剂A的水处理，然后将两批装料混合在一起，并在约540℃的温度下煅烧10小时以形成催化剂G。
水处理催化剂A以制备催化剂B-G汇总在表1中。
表1
用水处理的P/ZSM-5催化剂
实施例4
上述催化剂A-G中的每一种都用于甲苯甲基化反应。在每一种情况下，均将5.4ml催化剂的新鲜装料装载至反应器中。通过在氢气流(50立方厘米/分钟)下以约5℃/分钟缓慢升高催化剂床温度至480℃来进一步干燥所述催化剂至少2小时。然后通过引入在200℃下的具有H2载气(459立方厘米/分钟)的水蒸汽(2.2毫摩尔/分钟)过夜而汽蒸所述催化剂。将预混合的甲苯和甲醇进料(摩尔比4.5)加入至在200℃下的反应器中，使催化剂床入口温度缓慢升高至485℃。将基于甲基化进料(甲苯+甲醇)的液时空速(liquid hourly space velocity，LHSV)保持在约2小时-1，进料并保持共进料H2气以提供约7～8的H2/甲基化进料的摩尔进料比。另外，水作为共进料被加入至反应器中，并在引入反应器之前蒸发。H2O/甲基化进料摩尔比为约0.8，并且反应器压力为约20psig。分析反应器流以计算转化率和选择性。结果表示于图1中。
如图1所示，非水处理的含磷沸石(催化剂A)在所用的条件下显示出约11.5摩尔％的甲苯转化率，并且所述转化率随着在流上的时间增加而缓慢下降。当利用流动液体水通过在室温下(催化剂C)、在60℃下(催化剂D)和在100℃下(催化剂E)的催化剂床进行处理时，或通过将催化剂浸入60℃下的水中(催化剂B)进行处理时，经磷处理过的沸石显示出约14摩尔％的显著更高的甲苯转化率。对于这些催化剂而言，也不存在转化率随着在流上的时间增加而明显下降。当使用高于其沸点(例如500℃(催化剂G))的水蒸汽处理含磷ZSM-5沸石时，经预处理的催化剂不显示改进的活性，并且显示出与未处理的催化剂(催化剂A)相同的失活属性。
参照如下表2，相比于非水处理的催化剂(催化剂A)，经水预处理的催化剂(催化剂B-G)中的每一种均显示出更低水平的磷含量。这表明水去除了松散结合的磷，或者磷可能堵塞沸石孔隙/通道。
表2
用水处理的P/ZSM-5催化剂
*由催化剂(B至G)的P含量和催化剂A的P含量计算得到的去除的P％(相对于在水处理之前的初始P含量)。
实施例5
显示出活性和稳定性的最大增加的那些催化剂(即催化剂B和E)含有以催化剂的重量计为约5.4～5.6wt％的磷。为了进行比较，在甲苯甲基化中使用以与表1中的催化剂A相同的方式制得、但仅含有5.3wt％的磷并且未用水处理的经磷处理过的ZSM-5沸石(催化剂H)。如图1所示，相比于具有类似量的磷的经水处理的沸石催化剂，催化剂H显示出明显更低的活性。
尽管仅以其形式中的一部分示出了本发明，但对于本领域技术人员显而易见的是本发明并不如此限制，而是在不偏离本发明的范围的前提下本发明可进行各种改变和修改。因此，适当的是广义地并以与本发明的范围一致的方式解释所附权利要求书。

Claims (21)

1.一种制备沸石催化剂的方法，包括：
用磷化合物处理沸石以提供经磷处理过的沸石，所述经磷处理过的沸石具有以所述沸石的重量计为8重量％或更高的初始磷含量；
煅烧经磷处理过的沸石；
使所述经煅烧的经磷处理过的沸石与液体水接触；
通过所述接触去除量为所述初始磷含量的20％以上的磷；以及
加热所述经磷处理过的沸石；
其中，在处理和煅烧之后，所述经煅烧的经磷处理过的沸石任选地用粘合剂结合。
2.根据权利要求1所述的方法，其中在25℃至100℃的温度下使所述经煅烧的经磷处理过的沸石与液体水接触。
3.根据权利要求1所述的方法，其中所述沸石为ZSM-5沸石。
4.根据权利要求1所述的方法，其中所述经磷处理过的沸石与粘合剂材料结合。
5.根据权利要求4所述的方法，其中所述粘合剂材料为含铝材料
6.根据权利要求1所述的方法，其中所述沸石具有至少250的二氧化硅/氧化铝摩尔比。
7.根据权利要求1所述的方法，其中通过将所述经磷处理过的沸石浸入在所述液体水中而使所述经磷处理过的沸石与所述液体水接触。
8.根据权利要求1所述的方法，其中通过使所述经磷处理过的沸石与流动液体水接触而使所述经磷处理过的沸石与所述液体水接触。
9.根据权利要求1所述的方法，其中所述经煅烧的经磷处理过的沸石与流动液体水接触并且其中所述流动液体水被携带在气体稀释剂流中。
10.根据权利要求1所述的方法，其中用磷化合物处理所述沸石包括基于水的磷处理。
11.根据权利要求10所述的方法，其中所述磷化合物为磷酸(H3PO4)、亚磷酸(H3PO3)和磷酸氢二铵((NH4)2HPO4)中的至少一种。
12.根据权利要求1所述的方法，其中在至少300℃的温度下煅烧所述经磷处理过的沸石催化剂。
13.根据权利要求1所述的方法，其中所述沸石为中孔沸石。
14.根据权利要求1所述的方法，其中被去除的磷的量为所述初始磷含量的20％至30％。
15.根据权利要求3所述的方法，其中所述ZSM-5沸石具有至少250的二氧化硅/氧化铝摩尔比。
16.根据权利要求15所述的方法，其中在用所述磷化合物处理ZSM-5沸石之后，使所述ZSM-5沸石与粘合剂材料结合。
17.根据权利要求1所述的方法，其中在所述用磷化合物处理沸石之后用任意的任选粘合剂来结合所述沸石。
18.一种包含经煅烧的经磷处理过的沸石的沸石催化剂，所述经磷处理过的沸石具有以所述沸石的重量计为8重量％或更高的初始磷含量，通过使所述经煅烧的经磷处理过的沸石与液体水接触，所述经磷处理过的沸石具有比初始磷含量降低20％至30％的初始磷含量。
19.一种制备沸石催化剂的方法，包括：
用磷化合物处理沸石以提供经磷处理过的沸石，所述经磷处理过的沸石具有以所述沸石的重量计为8重量％或更高的初始磷含量，然后用任意的任选粘合剂来结合所述沸石；
煅烧所述经磷处理过的沸石；和
通过(1)将所述经煅烧的经磷处理过的沸石浸入液体水中和(2)使所述经磷处理过的沸石与流动液体水接触中的至少之一来使所述经煅烧的经磷处理过的沸石与液体水接触；
其中通过所述接触去除量为所述初始磷含量的20％以上的磷。
20.根据权利要求19所述的方法，其中所述煅烧在250℃或更高的温度下进行。
21.一种制备沸石催化剂的方法，包括：
煅烧经磷处理过的沸石，所述经磷处理过的沸石具有以所述沸石的重量计为8重量％或更高的初始磷含量，然后进行结合；和
通过(1)将所述经煅烧的经磷处理过的沸石浸入液体水中和(2)使所述经磷处理过的沸石与流动液体水接触中的至少之一来使所述经煅烧的经磷处理过的沸石与液体水接触；
其中通过所述接触去除量为所述初始磷含量的20％以上的磷。
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Families Citing this family (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102011013908A1 (de) * 2011-03-15 2012-09-20 Süd-Chemie AG Modifizierter Katalysator zur Umwandlung von Oxygenaten zu Olefinen
DE102011013911A1 (de) 2011-03-15 2012-09-20 Süd-Chemie AG Verbessertes Verfahren zur Herstellung eines Katalysators auf Zeolithbasis zur Umwandlung von Methanol in Olefine
DE102011013909A1 (de) * 2011-03-15 2012-09-20 Süd-Chemie AG Verfahren zur Herstellung eines Katalysators auf Zeolithbasis zur Umwandlung von Methanol in Olefine
JP2015501209A (ja) * 2011-10-17 2015-01-15 エクソンモービル リサーチ アンド エンジニアリング カンパニーＥｘｘｏｎ Ｒｅｓｅａｒｃｈ Ａｎｄ Ｅｎｇｉｎｅｅｒｉｎｇ Ｃｏｍｐａｎｙ リン変性ゼオライト触媒の製造方法
US9278342B2 (en) 2012-07-02 2016-03-08 Saudi Basic Industries Corporation Method of modifying a phosphorus-containing zeolite catalyst
CN111437872A (zh) * 2013-01-23 2020-07-24 巴斯夫公司 通过改进的沸石和磷相互作用来增强zsm-5添加剂活性
US8969643B2 (en) * 2013-05-23 2015-03-03 Saudi Basic Industries Corporation Method for conversion of aromatic hydrocarbons
US9783462B2 (en) 2013-09-10 2017-10-10 Saudi Basic Industries Corporation Toluene methylation with transalkylation of heavy aromatics
US9364815B2 (en) 2013-11-07 2016-06-14 Saudi Basic Industries Corporation Method of preparing an alumina catalyst support and catalyst for dehydrogenation reactions, and its use
JP6545172B2 (ja) 2013-12-20 2019-07-17 クラリアント・プロドゥクテ・（ドイチュラント）・ゲゼルシャフト・ミト・ベシュレンクテル・ハフツング 含酸素化合物をオレフィンに転換するためのリン含有触媒
CN106395853A (zh) * 2015-07-27 2017-02-15 中国石油化工股份有限公司 一种含磷的zsm-5分子筛、制备方法和应用

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN85102828A (zh) * 1985-04-01 1986-07-23 大连工学院 用磷改性zsm-5催化剂制取对甲乙苯
CN101356138A (zh) * 2005-12-22 2009-01-28 沙特基础工业公司 粘结的磷改性的沸石催化剂，其制备方法和使用方法

Family Cites Families (219)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3562345A (en) * 1968-09-18 1971-02-09 Universal Oil Prod Co Crystalline aluminosilicate-alumina composition and transalkylation therewith
US3702886A (en) 1969-10-10 1972-11-14 Mobil Oil Corp Crystalline zeolite zsm-5 and method of preparing the same
US4025606A (en) * 1971-06-25 1977-05-24 Johnson Matthey & Co., Limited Catalysis
US4002697A (en) * 1973-12-03 1977-01-11 Mobil Oil Corporation Selective production of para-xylene
US3950242A (en) * 1974-04-02 1976-04-13 Mobil Oil Corporation Fluid catalytic cracking plus selective upgrading of cracked gasoline
US3962364A (en) * 1975-03-28 1976-06-08 Mobil Oil Corporation Alkylation in presence of phosphorus-modified crystalline luminosilicate catalyst
US4100215A (en) 1974-09-25 1978-07-11 Mobil Oil Corporation Selective production of para-xylene
US3965207A (en) * 1975-01-06 1976-06-22 Mobil Oil Corporation Selective production of para-xylene
US4007231A (en) * 1975-11-24 1977-02-08 Mobil Oil Corporation Selective production of para-xylene
US4086287A (en) * 1976-07-19 1978-04-25 Mobil Oil Corporation Selective ethylation of mono alkyl benzenes
US4115424A (en) 1976-12-22 1978-09-19 Monsanto Company Zeolite catalyst
US4250345A (en) * 1978-01-10 1981-02-10 Mobil Oil Corporation Selective production of para-xylene
US4152364A (en) * 1978-01-19 1979-05-01 Mobil Oil Corporation Selective production of para-xylene
US4444989A (en) * 1979-04-20 1984-04-24 E. I. Du Pont De Nemours And Company Methylation of toluene to para-xylene catalyzed by crystalline silica
US4417076A (en) 1979-12-27 1983-11-22 Rozovsky Alexandr Y Catalyst and process for dehydrogenation of oxygen-containing derivatives of the cyclohexane series into corresponding cyclic ketones and/or phenols
US4415477A (en) 1979-12-27 1983-11-15 Rozovsky Alexandr Y Catalyst for dehydrogenation oxygen-containing derivatives of the cyclohexane series into the corresponding cyclic ketones and/or phenols
US4278827A (en) 1980-04-07 1981-07-14 Mobil Oil Corporation Shape selective reactions with zeolite catalyst modified with group IVB metal
USRE31919E (en) * 1980-04-14 1985-06-18 Mobil Oil Corporation Aromatics processing catalysts
US4380685A (en) * 1980-05-19 1983-04-19 Mobil Oil Corporation Shape selective reactions with zeolite catalysts modified with iron and/or cobalt
JPS5726627A (en) * 1980-07-25 1982-02-12 Teijin Yuka Kk Preparation of p-xylene
EP0051318B2 (en) 1980-11-04 1990-03-21 Teijin Petrochemical Industries Ltd. A catalyst composition containing as catalytically active components alumina and a cristalline aluminosilicate zeolite, a process for isomerizing xylenes and ethylbenzene, and use of this catalyst composition
US4704495A (en) 1980-12-29 1987-11-03 Mobil Oil Corporation Catalytic conversions using shape selective metallic catalysts
US4409132A (en) 1982-03-18 1983-10-11 Mobil Oil Corporation Organophosphorus-treated zeolite catalysts for para-selective aromatics conversion
US4554394A (en) 1982-03-18 1985-11-19 Mobil Oil Corporation Organophosphorus-treated zeolite catalysts for para-selective aromatics conversion
DE3363367D1 (en) 1982-04-14 1986-06-12 Ici Plc Ammonia production process
US5248841A (en) 1982-04-30 1993-09-28 Mobil Oil Corporation Hydrocarbon conversion with ZSM-22 zeolite
US5254767A (en) 1982-04-30 1993-10-19 Mobil Oil Corp. Highly siliceous porous crystalline material and its use in conversion of oxygenates
US4902406A (en) * 1982-04-30 1990-02-20 Mobil Oil Corporation Synthesis of zeolite ZSM-22
US5336478A (en) 1982-04-30 1994-08-09 Mobil Oil Corp. Highly siliceous porous crystalline material
US5254770A (en) 1982-09-01 1993-10-19 Mobil Oil Corp. Isomerization of aromatic compounds over ZSM-22 zeolite
DE3371871D1 (en) 1982-10-18 1987-07-09 Mp United Drug Co Ltd Purification of gases
US4973781A (en) 1982-11-17 1990-11-27 Mobil Oil Corporation Zeolite ZSM-57 and catalysis therewith
US4781815A (en) 1983-05-02 1988-11-01 Union Carbide Corporation Catalytic cracking process
US4914067A (en) * 1983-05-02 1990-04-03 Uop Catalytic cracking catalysts and cracking process using mixed catalyst system
US4548914A (en) * 1983-08-26 1985-10-22 Mobil Oil Corporation Zeolite catalysts of improved activity and para-selectivity
US4891197A (en) * 1983-12-19 1990-01-02 Mobil Oil Corporation Silicophosphoaluminates and related crystalline oxides
US4694114A (en) 1984-01-11 1987-09-15 Mobil Oil Corporation Process for isomerizing alkyl aromatic hydrocarbons utilizing ZSM-23 zeolite and a hydrogenation/dehydrogenation metal
US4623633A (en) 1984-01-17 1986-11-18 Union Oil Company Of California Shock calcined aluminosilicate zeolites
US4758328A (en) 1984-01-17 1988-07-19 Union Oil Company Of California Shock calcined aluminosilicate zeolites
EP0157480B1 (en) 1984-03-02 1989-07-26 Imperial Chemical Industries Plc Process for producing ammonia synthesis gas
US4716135A (en) 1984-04-09 1987-12-29 Mobil Oil Corporation Organophosphorus-modified zeolites and method of preparation
US4638106A (en) * 1984-07-13 1987-01-20 Exxon Research & Engineering Co. Two stage process for improving the catalyst life of zeolites in the synthesis of lower olefins from alcohols and their ether derivatives
US5047141A (en) 1984-07-16 1991-09-10 Mobil Oil Corporation Larger pore molecular sieves of controlled activity
US4912073A (en) * 1984-07-16 1990-03-27 Mobil Oil Corp. Larger pore molecular sieves of controlled activity
US4873067A (en) 1984-08-21 1989-10-10 Mobil Oil Corporation Zeolite ZSM-57
IL73146A (en) 1984-10-02 1988-11-15 Yeda Res & Dev Catalysts and process for the production of hydrocarbons and substitution of hydrocarbons
US4891467A (en) * 1984-10-15 1990-01-02 Amoco Corporation Selective synthesis of pseudocumene and durene
DE3440646A1 (de) * 1984-11-07 1986-05-07 Hoechst Ag, 6230 Frankfurt Traegerkatalysator fuer die herstellung von monocarbonsaeureanhydriden
US4623530A (en) 1985-02-20 1986-11-18 United States Steel Corporation Crystalline magnesia-silica composites and process for producing same
US4721827A (en) * 1985-02-20 1988-01-26 Aristech Chemical Corportion Crystalline magnesia-silica composites and process for producing same
US4727209A (en) * 1985-06-11 1988-02-23 Uop Inc. Hydrocarbon alkylation processes employing a phosphorus-modified alumina composite
US4590321A (en) * 1985-06-12 1986-05-20 Mobil Oil Corporation Aromatization reactions with zeolites containing phosphorus oxide
US4665251A (en) * 1985-06-12 1987-05-12 Mobil Oil Corporation Aromatization reactions with zeolites containing phosphorus oxide
US4673767A (en) 1985-11-25 1987-06-16 Amoco Corporation AMS-1B crystalline borosilicate molecular sieve-based catalyst compositions and process for toluene alkylation
US4670616A (en) * 1985-11-25 1987-06-02 Amoco Corporation AMS-1B crystalline borosilicate molecular sieve-based catalyst compositions and process for toluene methylation
US4695666A (en) 1985-12-09 1987-09-22 Uop Inc. Phosphorus-containing alumina catalyst for the isomerization of aromatics
US4746763A (en) * 1987-04-22 1988-05-24 Uop Inc. Process for producing aromatic compounds from C2 -C6 aliphatic hydrocarbons
US4761513A (en) 1987-07-01 1988-08-02 Uop Inc. Temperature control for aromatic alkylation process
FR2623423B1 (fr) 1987-11-23 1990-03-30 Centre Nat Rech Scient Nouveaux catalyseurs a base de zeolithes modifiees par des elements alcalins sous forme metallique, leur preparation et leur application a l'alkylation des derives alkyl-aromatiques
US4935574A (en) 1988-03-29 1990-06-19 E. I. Du Pont De Nemours And Company Preparation of para-xylene by toluene methylation
FR2629444B1 (fr) 1988-04-01 1990-12-07 Rhone Poulenc Chimie Zeolites a base de silice et d'oxyde de germanium et procede de synthese de celles-ci
US4847223A (en) 1988-04-08 1989-07-11 Concordia University Superacidic catalysts for low temperature conversion of aqueous ethanol to ethylene
US4861930A (en) 1988-09-28 1989-08-29 Uop Combination process for the conversion of a C2 -C6 aliphatic hydrocarbon
US4980052A (en) 1988-12-05 1990-12-25 Mobil Oil Corporation Catalytic cracking of hydrocarbons
US5178748A (en) * 1988-12-22 1993-01-12 Imperial Chemical Industries Catalytic reactions using zeolites
GB8829923D0 (en) 1988-12-22 1989-02-15 Ici Plc Zeolites
US5124299A (en) 1989-08-02 1992-06-23 E. I. Du Pont De Nemours And Company Catalysis using blends of perfluorinated ion-exchange polymers with perfluorinated diluents
US5105047A (en) * 1989-08-02 1992-04-14 E. I. Du Pont De Nemours And Company Catalysis using blends of perfluorinated ion-exchange polymers with perfluorinated diluents
US5233102A (en) 1989-08-02 1993-08-03 E. I. Du Pont De Nemours And Company Olefin hydration
US5094995A (en) * 1989-08-02 1992-03-10 E. I. Du Pont De Nemours And Company Supported perfluorinated ion-exchange polymers
JP2909553B2 (ja) 1989-10-18 1999-06-23 トヨタ自動車株式会社 排気ガス浄化用触媒及び排気ガスの浄化方法
US4973399A (en) 1989-11-03 1990-11-27 Mobil Oil Corporation Catalytic cracking of hydrocarbons
US5043502A (en) 1990-03-16 1991-08-27 Uop Production of xylenes from light aliphatic hydrocarbons via dehydrocyclodimerization and methylation
US5173461A (en) 1990-03-21 1992-12-22 Mobil Oil Corporation Toluene disproportionation catalyst
US5534239A (en) 1990-03-23 1996-07-09 Societe Nationale Elf Aquitaine Process for the synthesis of a silica enriched crystalline aluminosilicate having the offretite structure, the aluminosilicate obtained and its use as a catalyst for the conversion of hydrocarbons
GB9013859D0 (en) 1990-06-21 1990-08-15 Ici Plc Zeolites
GB9013916D0 (en) * 1990-06-22 1990-08-15 Ici Plc Zeolites
EP0466545A1 (fr) * 1990-06-29 1992-01-15 Rhone-Poulenc Chimie Zéolithes à base de silice et d'oxydes d'éléments tétravalents, leur procédé de synthèse et leur application
EP0473509A3 (fr) 1990-08-29 1992-03-18 Rhone-Poulenc Chimie Procédé de préparation de zéolithes à base de silice et éventuellement d'oxydes d'éléments tétravalents
US5110776A (en) * 1991-03-12 1992-05-05 Mobil Oil Corp. Cracking catalysts containing phosphate treated zeolites, and method of preparing the same
US5231064A (en) 1991-03-12 1993-07-27 Mobil Oil Corp. Cracking catalysts comprising phosphorus and method of preparing and using the same
US5456821A (en) 1991-03-12 1995-10-10 Mobil Oil Corp. Catalytic conversion with improved catalyst
US5366948A (en) 1991-03-12 1994-11-22 Mobil Oil Corp. Catalyst and catalytic conversion therewith
US5348643A (en) 1991-03-12 1994-09-20 Mobil Oil Corp. Catalytic conversion with improved catalyst
US5171921A (en) 1991-04-26 1992-12-15 Arco Chemical Technology, L.P. Production of olefins
US5387732A (en) * 1991-10-15 1995-02-07 Fina Technology, Inc. Start-up process for improved selectivity in toluene disproportionation
US5210356A (en) * 1991-12-16 1993-05-11 Fina Technology, Inc. Toluene disproportionation employing modified omega zeolite catalyst
US5227558A (en) 1992-02-10 1993-07-13 Fina Technology, Inc. Aromatic alkylation process employing steam modified zeolite beta catalyst
US5498814A (en) * 1992-03-12 1996-03-12 Mobil Oil Corp. Regioselective methylation of toluene to para-xylene
US5516736A (en) * 1992-03-12 1996-05-14 Mobil Oil Corp. Selectivating zeolites with organosiliceous agents
US5321183A (en) 1992-03-12 1994-06-14 Mobil Oil Corp. Process for the regioselective conversion of aromatics to para-disubstituted benzenes
US5571768A (en) * 1992-03-12 1996-11-05 Mobil Oil Corporation Zeolite functionalized with organosiliceous groups
US5475179A (en) 1992-03-12 1995-12-12 Mobil Oil Regioselective production of para-dialkyl benzenes
EP0568913A3 (en) * 1992-05-03 1995-03-22 Dalian Chemical Physics Inst Process for the conversion of methanol into light olefins and catalyst used therefor.
US5294332A (en) * 1992-11-23 1994-03-15 Amoco Corporation FCC catalyst and process
US5318696A (en) 1992-12-11 1994-06-07 Mobil Oil Corporation Catalytic conversion with improved catalyst catalytic cracking with a catalyst comprising a large-pore molecular sieve component and a ZSM-5 component
US5294578A (en) * 1992-12-23 1994-03-15 Mobil Oil Corp. Supported acid catalysts, their preparation and use in organic compound conversion
US5336824A (en) 1993-01-29 1994-08-09 Fina Technology, Inc. Mordenite catalysts in toluene synthesis
DE4304821A1 (de) 1993-02-17 1994-08-18 Degussa Verfahren zum Modifizieren von Molekularsieben mittels Ionenaustausch
US5365003A (en) 1993-02-25 1994-11-15 Mobil Oil Corp. Shape selective conversion of hydrocarbons over extrusion-modified molecular sieve
US5349113A (en) 1993-02-25 1994-09-20 Mobil Oil Corp. Shape selective hydrocarbon conversion over pre-selectivated, activated catalyst
CN1034223C (zh) * 1993-03-29 1997-03-12 中国石油化工总公司 制取低碳烯烃的裂解催化剂
US5378670A (en) * 1993-04-16 1995-01-03 W. R. Grace & Co.-Conn. Phosphorus zeolites/molecular sieves
US5362697A (en) 1993-04-26 1994-11-08 Mobil Oil Corp. Synthetic layered MCM-56, its synthesis and use
US5430213A (en) 1993-05-06 1995-07-04 Exxon Chemical Patents Inc. Process for producing 1,4-dienes
US5476823A (en) 1993-05-28 1995-12-19 Mobil Oil Corp. Method of preparation of ex situ selectivated zeolite catalysts for enhanced shape selective applications and method to increase the activity thereof
US5698756A (en) 1993-05-28 1997-12-16 Mobil Oil Corporation Toluene alkylation with ethylene to produce para-ethyloluene
US6576582B1 (en) * 1993-05-28 2003-06-10 Exxonmobil Oil Corporation Binderless ex situ selectivated zeolite catalyst
US5523510A (en) 1993-08-30 1996-06-04 Texaco Inc. Treated bound ferrierite zeolites for skeletal isomerization of n-olefins to iso-olefins
US5563310A (en) 1993-09-14 1996-10-08 Mobil Oil Corporation Toluene alkylation with methanol
DE69421288T2 (de) 1993-10-18 2000-02-03 Mobil Oil Corp Poröses synthetisches kristallines material mcm-58, dessen synthese und verwendung
US5726114A (en) * 1993-10-27 1998-03-10 Mobil Oil Corporation Method of preparation of ex situ selectivated zeolite catalysts for enhanced shape selective applications and methods to increase the activity thereof
EP0655277A1 (en) * 1993-11-01 1995-05-31 Csir Amorphous aluminosilicate catalyst
US5457078A (en) 1993-11-29 1995-10-10 Mobil Oil Corporation Manufacture of improved zeolite Beta catalyst
US5512260A (en) * 1994-03-04 1996-04-30 Mobil Oil Corporation Reduction of sulfur content in a gaseous stream
US5561095A (en) 1994-03-31 1996-10-01 Exxon Chemical Patents Inc. Supported lewis acid catalysts for hydrocarbon conversion reactions
WO1995026814A1 (en) * 1994-03-31 1995-10-12 Exxon Chemical Patents Inc. Supported lewis acid catalysts derived from superacids useful for hydrocarbon conversion reactions
WO1995026818A1 (en) * 1994-03-31 1995-10-12 Exxon Chemical Patents Inc. Supported lewis acid catalysts for hydrocarbon conversion reactions
US5576256A (en) 1994-05-23 1996-11-19 Intevep, S.A. Hydroprocessing scheme for production of premium isomerized light gasoline
US5689024A (en) 1994-06-03 1997-11-18 Mobil Oil Corporation Use of crystalline SUZ-9
EP0777636B1 (en) * 1994-08-26 2000-05-31 Engelhard De Meern B.V. Process for the production of cyclohexane
US5939597A (en) 1994-11-10 1999-08-17 Mobil Oil Corporation Fluid bed process for para-xylene production
US5646314A (en) 1994-11-16 1997-07-08 Arco Chemical Technology, L.P. Process for titanium silicalite-catalyzed epoxidation
US5573746A (en) 1995-06-06 1996-11-12 Mobil Oil Corporation Zeolite synthesis with amino acid directing agents
US5602066A (en) * 1995-06-29 1997-02-11 Mobil Oil Corporation Method of making a liquid washed selectivated zeolite catalyst
US6060633A (en) * 1995-10-20 2000-05-09 Chen; Frank Joung-Yei Supported Lewis acid catalysts derived from superacids useful for hydrocarbon conversion reactions
US5811613A (en) 1996-04-05 1998-09-22 Indian Petrochemicals Corporation Limited Process for the production of para-diethylbenzene
CA2204461C (en) 1996-05-14 2006-07-04 Thomas V. Harris Process for producing an alkylated, non-oxygen-containing aromatic hydrocarbon
WO1997045387A1 (en) 1996-05-29 1997-12-04 Exxon Chemical Patents Inc. Methylation of toluene to para-xylene
US5952535A (en) 1996-09-18 1999-09-14 Catalytica, Inc. Selective catalytic conversion of a C9 aromatic feedstock containing substantial amounts of ethyl substituted aromatic components to a product rich in toluene and/or xylenes
US6048816A (en) * 1996-10-02 2000-04-11 Mobil Oil Corporation Catalyst and process for converting methanol to hydrocarbons
WO1998016468A1 (en) 1996-10-17 1998-04-23 Exxon Chemical Patents Inc. Hydrocarbon conversion using large crystal zeolite catalyst
US5990031A (en) 1996-11-26 1999-11-23 Fina Technology, Inc. Zeolite catalyst with enhanced dealkylation activity and method for producing same
WO1998023373A1 (fr) * 1996-11-27 1998-06-04 Idemitsu Kosan Co., Ltd. Procede de production d'un catalyseur pour l'epuration des gaz d'echappement
DE19653042A1 (de) 1996-12-19 1998-06-25 Basf Ag Flammgeschützte Formmassen
US5925586A (en) 1996-12-31 1999-07-20 Exxon Chemical Patents, Inc. Phosphorus modified small pore molecular sieve catalysts, and their use in the production of light olefins
CN1059133C (zh) 1997-03-24 2000-12-06 中国石油化工总公司 具有mfi结构的含磷分子筛
US5847255A (en) 1997-05-21 1998-12-08 Fina Technology, Inc. Gas phase alkylation-liquid phase transalkylation process
US5905051A (en) * 1997-06-04 1999-05-18 Wu; An-Hsiang Hydrotreating catalyst composition and processes therefor and therewith
US5898089A (en) 1997-07-09 1999-04-27 Phillips Petroleum Company Hydrocarbon aromatization process using a zeolite
US6034283A (en) * 1997-07-18 2000-03-07 Asahi Kasei Kogyo Kabushiki Kaisha Process for production of cyclic alcohols
US6047544A (en) * 1997-08-20 2000-04-11 Nissan Motor Co., Ltd. Engine exhaust gas purification catalyst and exhaust gas purifier
EP0903178B2 (en) 1997-09-17 2012-05-30 China Petro-Chemical Corporation A pentasil-type molecular sieve containing composition, its preparation method and use
US6423879B1 (en) * 1997-10-02 2002-07-23 Exxonmobil Oil Corporation Selective para-xylene production by toluene methylation
DE69832938T2 (de) * 1997-10-15 2006-08-10 China Petro-Chemical Corp. Krackkatalysator für die Produktion von leichten Olefinen und dessen Herstellung
US6040257A (en) * 1997-11-07 2000-03-21 Phillips Petroleum Company Hydrocarbon conversion catalyst composition and processes therefor and therewith
DE69805003T2 (de) 1997-12-03 2002-11-14 Exxonmobil Chem Patents Inc Herstellung einer durch eine zeolith von mfi-strukturtyp gebundenen zeolith und ihre verwendung
WO1999028031A1 (en) 1997-12-03 1999-06-10 Exxon Chemical Patents Inc. Catalyst comprising a zeolite partially coated with a second zeolite, its use for hydrocarbon conversion
CN1069682C (zh) * 1997-12-23 2001-08-15 中国石油化工总公司 重油催化热裂解层柱粘土催化剂及其制备
US6395664B1 (en) * 1998-02-19 2002-05-28 Uop Llc Process for reactivating a deactivated dehydrocyclodimerization catalyst with water
US5907073A (en) * 1998-02-24 1999-05-25 Fina Technology, Inc. Aromatic alkylation process
US6074975A (en) 1998-03-03 2000-06-13 Phillips Petroleum Company Hydrocarbon conversion catalyst composition and processes therefor and therewith
US6417421B1 (en) 1998-03-03 2002-07-09 Phillips Petroleum Company Hydrocarbon conversion catalyst composition and process therefor and therewith
US6080303A (en) 1998-03-11 2000-06-27 Exxon Chemical Patents, Inc. Zeolite catalyst activity enhancement by aluminum phosphate and phosphorus
US5955641A (en) 1998-03-16 1999-09-21 Chevron Chemical Company Llc Method of making dimethylnaphthalenes
US6294493B1 (en) 1998-05-26 2001-09-25 Exxon Mobil Chemical Patents Inc. Silicoaluminophosphates having an AEL structure
US5968463A (en) 1998-06-12 1999-10-19 Ford Global Technologies, Inc. NOx selective reduction catalyst with broadened active temperature range
US6100437A (en) 1998-07-10 2000-08-08 Albemarle Corporation Alkylation process of alkyl-benzene with olefin using a sodium-and-potassium catalyst
US6124227A (en) 1998-08-28 2000-09-26 Phillips Petroleum Company Hydrocarbon conversion catalyst composition and processes therefor and therewith
DE69907935T2 (de) 1998-09-22 2004-03-11 Exxonmobil Chemical Patents Inc., Baytown Verfahren zur herstellung von durch zeolith gebundenen zeolithen mit hohem sio2-gehalt und ihre verwendung
EP1117750B1 (en) * 1998-09-28 2004-06-30 BP Corporation North America Inc. Process for manufacturing olefins using a pentasil zeolite based catalyst
JP3868128B2 (ja) 1998-10-05 2007-01-17 新日本石油株式会社 軽油の水素化脱硫装置及び方法
US6642426B1 (en) 1998-10-05 2003-11-04 David L. Johnson Fluid-bed aromatics alkylation with staged injection of alkylating agents
JP3871449B2 (ja) * 1998-10-05 2007-01-24 新日本石油株式会社 軽油の水素化脱硫方法
CN1096296C (zh) 1998-11-13 2002-12-18 中国石油化工集团公司 一种生产中间馏分油的加氢裂化催化剂及其制备
US6057485A (en) * 1998-11-17 2000-05-02 Fina Technology, Inc. Gas phase alkylation with split load of catalyst
US6156949A (en) 1998-12-28 2000-12-05 Mobil Oil Corporation Selective pseudocumene production by xylene methylation
US6090274A (en) 1998-12-29 2000-07-18 Phillips Petroleum Company Hydrotreating catalyst composition and processes therefor and therewith
US6268305B1 (en) 1999-02-27 2001-07-31 Fina Technology, Inc. Catalysts with low concentration of weak acid sites
US6090991A (en) 1999-02-27 2000-07-18 Fina Technology, Inc. Gas phase alkylation method and catalyst
US6222084B1 (en) * 1999-04-09 2001-04-24 Fina Technology, Inc. Gas phase alkylation-liquid phase transalkylation process
US6699811B1 (en) * 1999-05-05 2004-03-02 Exxon Mobil Chemical Patents Inc. Tailored zeolite bound zeolite catalyst and its use for hydrocarbon conversion
US6459006B1 (en) 1999-05-14 2002-10-01 Exxonmobil Chemical Patents Inc. Selective methylation to para-xylene using fuel syngas
US6613708B1 (en) 1999-06-07 2003-09-02 Exxonmobil Chemical Patents Inc. Catalyst selectivation
US6388156B1 (en) * 1999-05-14 2002-05-14 Exxonmobil Chemical Patents Inc. Direct selective synthesis of para-xylene by reacting an aromatic compound with a methylating agent formed from CO, Co2 and H2
DE60003817T2 (de) 1999-05-20 2004-04-15 Exxonmobil Chemical Patents Inc., Baytown Kohlenwasserstoffumwandlungsverfahren und hierbei anwendbarer katalysator
JP3489049B2 (ja) 1999-07-15 2004-01-19 日産自動車株式会社 排気ガス浄化用触媒
JP3859940B2 (ja) * 1999-08-06 2006-12-20 日産自動車株式会社 排気ガス浄化用触媒及びその製造方法
US6613951B1 (en) 1999-09-23 2003-09-02 Mobil Oil Corporation Process for converting methanol to olefins
US6187982B1 (en) * 1999-10-15 2001-02-13 Mobil Oil Corporation Process for converting dienes and oxygenates to para-xylene and light olefins
US6726834B2 (en) * 1999-10-22 2004-04-27 Intevep, S.A. Process for catalytic cracking of a hydrocarbon feed with a MFI aluminisilcate composition
EP1116775A1 (en) * 2000-01-12 2001-07-18 Akzo Nobel N.V. Catalyst composition with high efficiency for the production of light olefins
US6319484B1 (en) 1999-12-14 2001-11-20 Engelhard Corporation Compositions for abatement of volatile organic compounds and apparatus and methods using the same
US6773694B1 (en) 1999-12-22 2004-08-10 Uop Llc Process for synthesizing molecular sieves
US6926882B2 (en) 2000-01-05 2005-08-09 Exxonmobil Chemical Patents Inc. Porous inorganic macrostructure materials and process for their preparation
JP3489048B2 (ja) * 2000-02-01 2004-01-19 日産自動車株式会社 排気ガス浄化用触媒
US6346190B1 (en) * 2000-03-21 2002-02-12 Phillips Petroleum Company Desulfurization and novel sorbents for same
US6506954B1 (en) * 2000-04-11 2003-01-14 Exxon Mobil Chemical Patents, Inc. Process for producing chemicals from oxygenate
JP3904802B2 (ja) 2000-04-26 2007-04-11 日産自動車株式会社 排気ガス浄化用触媒及びその製造方法
US6799089B2 (en) 2000-06-09 2004-09-28 Institut Francais Du Petrole Design of new materials whose use produces a chemical bond with a descriptor of said bond
EP1166856B1 (en) 2000-06-28 2006-08-16 ICT Co., Ltd. Exhaust gas purifying catalyst
TWI240716B (en) * 2000-07-10 2005-10-01 Bp Corp North America Inc Pressure swing adsorption process for separating paraxylene and ethylbenzene from mixed C8 aromatics
TW572784B (en) * 2000-10-18 2004-01-21 Fina Technology Silica-supported alkylation catalyst
US7510644B2 (en) 2000-10-20 2009-03-31 Lummus Technology Inc. Zeolites and molecular sieves and the use thereof
US7119239B2 (en) 2002-06-19 2006-10-10 Exxonmobil Chemical Patents Inc. Manufacture of xylenes using reformate
US7186873B2 (en) * 2002-06-19 2007-03-06 Exxonmobil Chemical Patents Inc. Manufacture of xylenes by reactive distillation of reformate
EP1523535A1 (en) 2002-06-19 2005-04-20 Exxonmobil Chemical Patents Inc. Manufacture of xylenes from reformate
US7449104B2 (en) * 2002-07-05 2008-11-11 Conocophilips Company Integrated catalytic cracking and desulfurization system
US7130948B2 (en) * 2002-08-02 2006-10-31 Bian Qiyong B Flexible interrupt handling methods for optical networking apparatuses with multiple multi-protocol optical networking modules
US7081556B2 (en) * 2002-11-01 2006-07-25 Exxonmobil Chemical Patents Inc. Aromatics conversion with ITQ-13
US7232516B2 (en) 2003-06-26 2007-06-19 Conocophillips Company Desulfurization with octane enhancement
US7238636B2 (en) * 2003-07-23 2007-07-03 Exxonmobil Chemical Patents Inc. High temperature calcination of selectivated molecular sieve catalysts for activity and diffusional modification
US7084318B2 (en) 2003-08-01 2006-08-01 Saudi Basic Industries Corporation Toluene methylation process
US7060864B2 (en) 2003-09-30 2006-06-13 Saudi Basic Industries Corporation Toluene methylation process
US7453018B2 (en) 2003-12-31 2008-11-18 Exxonmobil Chemical Patents Inc. Process for aromatic alkylation
US7060644B2 (en) 2004-01-08 2006-06-13 Saudi Basic Industries Corporation Aromatic alkylation catalyst and method
US6943131B1 (en) 2004-03-02 2005-09-13 Saudi Basic Industries Corporation Selective zeolite catalyst modification
US7285511B2 (en) 2004-04-23 2007-10-23 Saudi Basic Industries Corporation Method of modifying zeolite catalyst
US7399727B2 (en) 2004-04-23 2008-07-15 Saudi Basic Industries Corporation Zeolite catalyst and method
US7105713B2 (en) 2004-06-09 2006-09-12 Saudi Basic Industries Corporation Preparation of alkyl-aromatic products
WO2006068800A2 (en) * 2004-12-22 2006-06-29 Exxonmobil Chemical Patents Inc. Production of alkylated aromatic hydrocarbons from methane
US7473350B2 (en) 2005-01-13 2009-01-06 China Petroleum & Chemical Corporation Control methodology for desulfurization process
US7304194B2 (en) 2005-05-05 2007-12-04 Saudi Basic Industries Corporation Hydrothermal treatment of phosphorus-modified zeolite catalysts
US20070015658A1 (en) * 2005-07-15 2007-01-18 Turaga Uday T Fuzz reduction of sulfur sorbents
US7368410B2 (en) 2005-08-03 2008-05-06 Saudi Basic Industries Corporation Zeolite catalyst and method of preparing and use of zeolite catalyst
BRPI0503182B1 (pt) * 2005-08-04 2014-03-04 Petroleo Brasileiro Sa Aditivo multifuncional para maximização de propriedades relevantes a um processo de craqueamento catalítico fluido e processo de preparação do mesmo
WO2009016156A1 (en) * 2007-07-31 2009-02-05 Total Petrochemicals Research Feluy Cracking of olefins on phosphorus modified molecular sieves.
US8115041B2 (en) 2008-04-02 2012-02-14 Saudi Basic Industries Corporation Pretreatment of a phosphorus-modified zeolite catalyst for an aromatic alkylation process
US8846559B2 (en) * 2008-11-03 2014-09-30 Saudi Basic Industries Corporation Stable shape-selective catalyst for aromatic alkylation and methods of using and preparing

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN85102828A (zh) * 1985-04-01 1986-07-23 大连工学院 用磷改性zsm-5催化剂制取对甲乙苯
CN101356138A (zh) * 2005-12-22 2009-01-28 沙特基础工业公司 粘结的磷改性的沸石催化剂，其制备方法和使用方法

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