CN1083412C - 甲苯甲基化制备对二甲苯 - Google Patents

甲苯甲基化制备对二甲苯 Download PDF

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CN1083412C
CN1083412C CN97195736A CN97195736A CN1083412C CN 1083412 C CN1083412 C CN 1083412C CN 97195736 A CN97195736 A CN 97195736A CN 97195736 A CN97195736 A CN 97195736A CN 1083412 C CN1083412 C CN 1083412C
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zeolite
catalyzer
toluene
silicon oxide
weight
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CN1224408A (zh
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G·D·默尔
R·S·史密斯
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ExxonMobil Chemical Patents Inc
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Exxon Chemical Patents Inc
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    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G11/00—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
    • C10G11/02—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils characterised by the catalyst used
    • C10G11/04—Oxides
    • C10G11/05—Crystalline alumino-silicates, e.g. molecular sieves
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    • B01J29/005—Mixtures of molecular sieves comprising at least one molecular sieve which is not an aluminosilicate zeolite, e.g. from groups B01J29/03 - B01J29/049 or B01J29/82 - B01J29/89
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    • B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
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Abstract

提供了一种在沸石粘结沸石的催化剂存在下通过甲基化甲苯制备对二甲苯的方法。该催化剂含有用第二沸石晶体粘结在一起的第一沸石晶体。当用于甲基化甲苯制备对二甲苯时，沸石粘结沸石的催化剂具有大于热力学平衡的对二甲苯选择性，该选择性可通过选择性化催化剂来提高。

Description

甲苯甲基化制备对二甲苯
本发明涉及在沸石粘结沸石的催化剂存在下通过甲苯的催化甲基化制备二甲苯的方法。另外，本发明涉及在选择性化(selectivated)的沸石粘结沸石的催化剂存在下通过甲苯的催化甲基化选择制备二甲苯的方法。
在二甲苯异构体，即邻二甲苯、间二甲苯和对二甲苯中，对二甲苯在用于制备对苯二酸的许多应用中是特别有价值的中间体，对苯二酸是制备合成纤维的中间体。制备对二甲苯的一种方法是将甲苯歧化成二甲苯，该方法的一个缺点是还产生了大量的苯。用于得到对二甲苯的另一种方法包括异构化进料物流，该进料物流含有非平衡量的混合的邻二甲苯和间二甲苯但贫含对二甲苯，该方法的缺点是对二甲苯与其他异构体的分离是昂贵的。
沸石由氧化硅晶格和任意的结合有可交换阳离子如碱金属或碱土金属离子的氧化铝构成。虽然术语“沸石”包括含有氧化硅和任意的氧化铝的物质，但认为氧化硅和氧化铝部分可全部或部分被其他氧化物替换。例如，氧化锗、氧化锡、氧化磷和其混合物可替换氧化硅部分。氧化硼、氧化铁、氧化镓、氧化铟和其混合物可替换氧化铝部分。因此本文所用的术语“沸石”，和“沸石物质”不但是指在其晶体晶格结构中含有硅和任意的铝原子的物质，而且是指含有硅和铝的适合替换原子的物质，例如硅镓酸盐(gallosilicates)、  硅铝磷酸盐(SAPO)和铝磷酸盐(aluminophosphates)(ALPO)。本文所用的术语“硅铝酸盐沸石”是指在其晶体晶格结构中主要含有硅和铝原子的沸石物质。
已经提出了通过使用沸石催化剂甲基化甲苯制备二甲苯的方法。例如，US3965207涉及使用沸石催化剂如ZSM-5甲基化甲苯。US4670616涉及使用用如氧化铝、氧化硅或氧化铝-氧化硅粘结剂粘结的硼硅酸盐分子筛甲基化甲苯制备二甲苯。
合成沸石通常是由过饱和合成混合物通过沸石结晶制备的，然后将得到的结晶产物干燥和焙烧制成沸石粉末。虽然沸石粉末具有好的吸收性能，但其实际应用受到严重限制，因为用沸石粉末难以进行固定床操作。因此在用于工业方法之前沸石催化剂通常要进行粘结。
沸石一般是通过形成沸石聚集体如丸、球或挤出物而粘结的。通常是在非沸石粘结剂存在下通过挤压沸石，和干燥和焙烧得到的挤出物形成该挤出物。所用的粘结剂是耐各种烃转化过程中发生的温度和其他条件的，例如机械摩擦。粘结剂的例子包括无定形物质如氧化铝、氧化硅、氧化钛和各种类型的粘土。通常有必要的是，沸石应是耐机械摩擦的，即不会形成小颗粒如颗粒尺寸小于20微米的细粉。
虽然这种粘结的沸石聚集体比沸石粉末具有好的多的机械强度，但是当这种粘结的沸石用于甲苯甲基化时，该催化剂的性能，例如活性、选择性、活性维持性能或它们的综合性能会因为粘结剂而降低。例如，因为无定形粘结剂通常的存在量高达沸石的约50％(重量)，所以粘结剂减弱了沸石聚集体的吸收性能。另外，因为粘结的沸石是通过将沸石和粘结剂挤压或其他方式成形和随后进行干燥和焙烧挤出物而制备的，因此无定形粘结剂可以渗透沸石的孔或堵塞沸石的孔通道，或者降低传质到沸石孔的速度，这些都可能在沸石用于烃转化过程时降低沸石的效力。此外，当这种粘结的沸石用于催化转化过程如甲苯甲基化过程中时，粘结剂可影响在沸石中发生的化学反应，其本身也可催化不需要的反应，该反应可形成不需要的产物。
本发明涉及在转化条件下使用沸石粘结沸石的催化剂通过甲苯与甲基化试剂反应制备对二甲苯的方法，该沸石粘结沸石的催化剂含有第一中等孔径沸石的第一晶体和一种含有第二沸石的第二晶体的粘结剂。
在另一个实施方案中，提供了优先于间二甲苯或邻二甲苯选择性地制备对二甲苯的方法，该方法是在转化条件下在沸石粘结沸石的催化剂存在下甲苯与甲基化试剂反应，该催化剂已通过将选择性化试剂(selectivationagent)沉积在其上选择性化了。
与其中对∶间∶邻比约为1∶2∶1的常规热力学平衡二甲苯混合物相比，本发明得到的二甲苯产物中的对二甲苯含量可超过70％。对二甲苯收率的改善降低了对二甲苯与其他二甲苯异构体分离的费用。
用于本发明方法的沸石粘结沸石的催化剂含有酸性中等孔径第一沸石的第一晶体和一种包括第二沸石的第二晶体的粘结剂。使用第二沸石晶体作为粘结剂使得催化剂提供了控制在第一沸石晶体表面上或附近发生的不需要反应的手段，并且能够改善反应物的传质和更容易进出沸石孔的通道。
与用无定形物质如氧化硅或氧化铝粘结以提高沸石机械强度的沸石催化剂不同，用于本发明方法的沸石粘结沸石的催化剂不含明显量的非沸石粘结剂。优选的是，沸石粘结沸石的催化剂含有少于10％(重量)(以第一和第二沸石的总重量计)的非沸石粘结剂，更优选含有少于5％(重量)，最优选的是第一和第二沸石基本上不含非沸石粘结剂。优选的是，通过粘合到第一沸石晶体的表面上从而形成基质或桥式结构使第二沸石晶体粘结第一沸石晶体，该基质或桥式结构也使第一晶体颗粒保持在一起。更优选的是，通过交互生长以便在较大的第一沸石晶体上形成包层或部分包层使第二沸石晶体粘结第一沸石，最优选的是，通过交互生长以便在第一沸石晶体上形成耐摩擦的附晶生长使第二沸石晶体粘结第一沸石晶体。
虽然本发明不想受到任何操作理论的限制，但我们相信当沸石粘结沸石的催化剂用于本发明方法时，可得到的一个优点是第二沸石晶体控制了第一沸石的外表面上的酸性中心对反应物的可接近性。因为存在于沸石催化剂的外表面上的酸性中心不是形状选择性的，这些酸性中心对反应物进入沸石的孔和产物退出沸石的孔可能产生不利的影响。按照这种观点，由于第二沸石的酸性可被精心选择，所以第二沸石对使用常规粘结的沸石催化剂可能发生的反应物退出第一沸石的孔的现象不会产生明显不利的影响，并且对脱氢方法的芳族化合物的选择性和反应物退出第一沸石的孔产生有利的影响。另外，由于第二沸石不是无定形的，而是分子筛，因此在芳构化过程中烃接近第一沸石的孔的机会增加了。
用于沸石的术语“酸度”、“低酸度”和“高酸度”是本领域技术人员已知的。沸石的酸性是公知的。然而，对于本发明来说，必须区别酸强度和酸性中心密度。沸石的酸性中心可以是质子酸或路易斯酸。酸性中心的密度和酸性中心的数量对确定沸石的酸度是重要的。直接影响酸强度的的因素是(i)沸石骨架的化学组成，即四面体原子的相对浓度和类型，(ii)骨架之外的阳离子和所得的骨架之外物质的浓度，(iii)沸石的局部结构，例如晶体中或沸石表面/沸石表面附近的孔径和位置，和(iv)预处理条件和存在的共吸附分子。酸度值涉及提供的同晶替代的程度，然而，对于纯SiO2组分，这种酸度限于酸性中心的损失。本文所用的术语“酸度”、“低酸度”和“高酸度”是指酸性中心的浓度，与这种酸性中心的强度无关，该酸性中心浓度可用氨吸附法测定。
用于沸石粘结沸石的催化剂的第一沸石是中等孔径沸石。中等孔径沸石的孔径为约5-约7埃，并且包括，例如AEL，MFI，MEL，MFS，MEI，MTW，EUO，MTT，HEU，FER和TON结构类型的沸石。这些沸石描述于“Atlas ofZeo1ite Structure Types”，eds.W.H.Meier and D.H.O1son，Butterworth-Heineman，第三版，1992，该文献在此引入作为参考。具体的中等孔径沸石的例子包括ZSM-5，ZSM-11，ZSM-12，ZSM-22，ZSM-23，ZSM-34，ZSM-35，ZSM-38，ZSM-48，ZSM-50和ZSM-57。优选的第一沸石是具有MFI结构的硅酸镓沸石和具有MFI结构的硅铝酸盐沸石。
本文所用的术语“平均粒径”是指晶体的平均直径，例如长轴和短轴的数均值。
第一沸石晶体的平均粒径大于0.1微米，优选为约0.1-约15微米，更优选约1-6微米。
测定晶体大小的方法是本领域技术人员已知的，例如，晶体大小可通过采集晶体有代表性样品的适合的扫描电子显微镜(SEM)图象直接测定。
中等孔径第一沸石通常将包括具有下列摩尔关系式的成分：
X2O3∶(n)YO2
其中X是三价元素如铝和镓，Y是四价元素如硅、锡和/或锗；n是大于12的值，该值取决于特定沸石的类型。当中等孔径沸石是MFI结构类型沸石时，n优选大于20。
正如本领域技术人员所已知的，可用许多技术如通入蒸汽来降低沸石的酸度。另外，沸石的酸度取决于具有最高酸性的氢型的沸石形式和沸石的其他形式如具有比酸形式更低酸度的钠形式。因此本文公开的具有氧化硅与氧化铝和氧化硅与氧化镓的摩尔比的沸石不但将包括具有已公开摩尔比的沸石，而且还包括不具有已公开摩尔比但具有同等催化酸度的沸石。
当第一沸石是硅铝酸盐沸石时，第一沸石将优选具有的氧化硅与氧化铝的摩尔比为10∶1-300∶1。
当第一沸石是硅酸镓沸石时，沸石优选包括具有下列摩尔关系式的成分：
Ga2O3∶ySiO2
其中y在约10-约150之间。沸石骨架可以仅含有镓和硅原子，或者还可以含有镓、铝和硅的结合物。当第一沸石是MFI结构型硅酸镓沸石时，第二沸石将优选是具有氧化硅与氧化镓的摩尔比大于100的中等孔径沸石。第二沸石也可以具有更高的氧化硅与氧化镓的摩尔比，例如大于200，500，1000等。
第二沸石通常将具有中等孔径并且具有比第一沸石更低的酸度。优选的是，第二沸石将是基本上非酸性的，并且具有与第一沸石相同的结构。优选的第二沸石是具有氧化硅与氧化铝的摩尔比大于100的硅铝酸盐如低酸度ZSM-5。如果第二沸石是硅铝酸盐沸石，那么第二沸石通常具有的氧化硅与氧化铝的摩尔比将大于200∶1，例如500∶1，1000∶1等，在某些应用中将含有不多于痕量的氧化铝。第二沸石也可以是硅质岩，即基本上无氧化铝的MFI型，或硅质岩2，基本上无氧化铝的MEL型。在沸石粘结沸石的催化剂中第二沸石的存在量通常为约10％-60％(重量)(以第一沸石的重量计)，更优选为约20％-约50％(重量)。
第二沸石晶体优选具有比第一沸石晶体更小的尺寸，更优选具有的平均粒径小于1微米，最优选约0.1-约0.5微米。第二沸石催化剂除了粘结第一沸石颗粒和使催化剂的性能最大提高外，还将优选交互生长和形成包覆或部分包覆第一沸石催化剂的附晶生长。优选的是，晶体将是耐摩擦的。
用于本发明方法的沸石粘结沸石的催化剂优选通过三步法制备的，第一步包括在第一沸石转化成沸石粘结沸石的催化剂之前合成第一沸石催化剂。制备第一沸石的方法是本领域已知的，例如对于制备MFI型硅铝酸盐沸石，优选的方法包括制备含有四丙基铵氢氧化物或溴化物、碱金属氧化物、铝氧化物、硅氧化物和水的溶液，然后加热反应混合物至80-200℃温度约4小时-8天，将得到的凝胶状的固体晶体颗粒与反应介质分离，用水洗涤并干燥，然后将得到的产物在400-550℃的空气中任意的焙烧10-40小时以除去四丙基铵(TPA)阳离子。
接着，优选用下列方法制备氧化硅粘结的硅铝酸盐沸石：混合含有硅铝酸盐沸石晶体、氧化硅胶或硅溶胶、水和任意的挤出助剂和任意的金属组分直到形成以可挤出膏形式的均匀组合物。用于制备氧化硅粘结的沸石聚集体的氧化硅粘结剂优选是硅溶胶并优选仅含有非常少量的氧化铝或镓，例如少于2000ppm。氧化硅的用量是这样的以致在干燥的挤出物中沸石的量为约40-90％(重量)，更优选约50-80％(重量)，余量主要是氧化硅，例如约20-50％(重量)的氧化硅。
可将得到的膏成形，例如挤出，和切成小的条，例如约2毫米直径的挤出物，该挤出物可在100-150℃下干燥4-12小时，然后在约400-550℃温度的空气中焙烧约1-10小时。
任选的是，可将氧化硅粘结的聚集体制成非常小的颗粒，该颗粒可用于如催化裂化的流化床方法中。优选包括混合沸石和含有氧化硅的基质溶液以便形成沸石和氧化硅粘结剂的含水溶液，可将该含水溶液喷雾干燥得到小的可流化的氧化硅粘结的聚集体颗粒。制备这种聚集体颗粒的方法是本领域技术人员已知的。Scherzer(Octane-Enhancing Zeolitic FCCCatalysts，Julius Scherzer，Marcel Dekker，Inc.New York，1990)介绍了这种方法的例子。然后使可流化的氧化硅粘结的聚集体颗粒，如上述氧化硅粘结的挤出物进行下述的最后步骤以转化氧化硅粘结剂成为第二沸石。
在三步催化剂制备方法中的最后步骤是将存在于氧化硅粘结的催化剂中的氧化硅转化成第二沸石，该第二沸石是用来将第一沸石晶体粘结在一起。这样粘结在一起的第一沸石晶体不需使用大量的非沸石粘结剂。为了制备沸石粘结沸石的催化剂，可先将氧化硅粘结的聚集体在适当的含水溶液和升高的温度下老化，接着，选择溶液的成分和聚集体老化的温度使无定形氧化硅粘结剂转化成第二沸石。优选的是第二沸石是与第一沸石相同的类型。新形成的沸石以晶体形式产生。晶体可生长在和/或粘附在初始沸石晶体上，并且还可以以新的交互生长晶体的形式产生，该晶体通常比初始晶体，例如亚微米尺寸小的多。这些新形成的晶体可以一起生长和相互连接。
在氧化硅第二次合成转化成沸石中形成的硅铝酸盐沸石的性质可随第二合成溶液的成分和合成老化条件而变化。第二合成溶液优选是含有足以将氧化硅转化成所需沸石的氢氧根离子来源的含水离子溶液。
沸石粘结沸石的催化剂通常是酸性或部分中和的酸性形式。为了得到酸性形式，可离子交换沸石生成铵盐形式，通过焙烧制成沸石粘结沸石的催化剂的酸形式。
在更优选的实施方案中，沸石粘结沸石的催化剂被选择性化以改善它的对二甲苯选择性。
选择性化催化剂的方法是本领域技术人员已知的。例如，可在下列条件下将反应器床层中的催化剂暴露于可热分解的有机化合物如甲苯中来进行选择性化，所用的条件为：温度超过所述有机化合物的分解温度，例如约480-约650℃，更优选540-650℃，WHSV为每磅催化剂每小时约0.1-20磅进料，压力为约1-100大气压，在每摩尔有机化合物0-约2摩尔氢气，更优选约0.1-约1摩尔氢气存在下，任意的在每摩尔有机化合物0-10摩尔氮气或其他惰性气体存在下。该方法进行一段时间直到足够量的焦炭沉积在催化剂表面上，通常至少约2％(重量)，更优选约8-约40％(重量)的焦炭。在一个优选实施方案中，在氢气存在下进行该选择性化方法以防止催化剂上过快地形成焦炭。当催化剂表面上已沉积了显著量的焦炭之后，在选择性改善方法中可降低存在于甲苯进料物流中的氢气与甲苯的初始摩尔比。
也可以使用有机硅化合物进行催化剂选择性化。硅化合物可包括：包括硅氧烷(silicones)的聚硅氧烷，硅氧烷(siloxane)和包括乙硅烷和烷氧基硅烷的硅烷。
可用于本发明的硅氧烷化合物可用下列通式表示：
其中R1是氢、氟化物、羟基、烷基、芳烷基、烷芳基或氟代烷基。烃取代基通常含有1-10个碳原子，优选是甲基或乙基。R2选自与R1相同的基团，n是至少2的整数，通常为2-1000。所用硅氧烷化合物的分子量通常为80-20000，优选为150-10000。有代表性的硅氧烷化合物包括二甲基硅氧烷、二乙基硅氧烷、苯甲基硅氧烷、甲基氢硅氧烷、乙基氢硅氧烷、苯基氢硅氧烷、甲基乙基硅氧烷、苯乙基硅氧烷、二苯基硅氧烷、甲基三丙基硅氧烷、乙基三氟丙基硅氧烷、四氯苯基甲基硅氧烷、四氯苯基乙基硅氧烷、四氯苯基氢硅氧烷、四氯苯基苯基硅氧烷、甲基乙烯基硅氧烷和乙基乙烯基硅氧烷。硅氧烷化合物不需要是线性的，但可以是环状的，例如六甲基环三硅氧烷、八甲基环四硅氧烷、六苯基环三硅氧烷和八苯基环四硅氧烷。也使用这些化合物的混合物以及具有其他官能基团的硅氧烷。
有效的硅氧烷或聚硅氧烷包括(作为非限制性例子)六甲基环三硅氧烷、八甲基环四硅氧烷、十甲基环五硅氧烷、六甲基二硅氧烷、八甲基三硅氧烷、十甲基四硅氧烷、六乙基环三硅氧烷、八乙基环四硅氧烷、六苯基环三硅氧烷和八苯基环四硅氧烷。
有效的硅烷、乙硅烷或烷氧基硅烷包括具有下列通式的有机取代的硅烷：
Figure C9719573600111
其中R是活性基团如氢、烷氧基、卤素、羧基、氨基、乙酰胺、三烷基甲硅烷氧基，R1，R2和R3可与R相同，或者可以是有机基团，该有机基团可包括1-40个碳原子的烷基，烷基或芳基羧酸，其中有机部分的烷基含有1-30个碳原子，可被进一步取代的芳基含有6-24个碳原子，含有7-30个碳原子的烷芳基和芳烷基。优选的是，烷基硅烷的烷基是1-4个碳原子的链长度。也可使用混合物。
硅烷或乙硅烷包括(作为非限制性例子)二甲基苯基硅烷、苯基三甲基硅烷、三乙基硅烷和六甲基乙硅烷。有效的烷氧基硅烷是具有至少一个硅-氢键的那些烷氧基硅烷。
甲基化方法可以使用固定床或移动床系统以间隙式、半连续或连续操作进行。可以使用多点注入甲基化试剂。
通常将甲苯和甲基化试剂预混合并一起加入到反应容器中，以保持它们之间的所需比例，而不会形成破坏反应动力学的任一反应物的局部聚集。然而，如果能精心地确保反应物蒸汽在反应容器中很好的混合，则可以使用单个进料。通过分阶段加入可以使甲基化试剂的瞬间浓度保持较低。通过分阶段加入，甲苯/甲基化试剂浓度可保持在最佳水平以得到好的甲苯转化率。可将氢气加入反应作为防焦剂和稀释剂。
在进行该方法中，可将催化剂和反应物分别或一起加热到反应温度，反应温度为约300-700℃，优选为约400-700℃。反应优选在下列条件下进行：压力为约1-1000psig，重时空速为约1-2000，甲基化试剂与甲苯的摩尔比为约0.05-5，重时空速为每催化剂重量每小时约1-200，优选约5-150重量进料。反应产物可用任何适合的方法分离。
典型的甲基化试剂包括甲醇、二甲基醚、甲基氯、甲基溴和二甲硫。根据本文所提供的说明，本领域的技术人员知道其他甲基化试剂也可用于本发明方法。优选的甲基化试剂是甲醇和二甲基醚，甲醇是最优选的。
下列实施例说明了本发明：
实施例1
I.催化剂A
催化剂A含有70％(重量)氧化硅与氧化铝摩尔比为75∶1的H-ZSM-5核心晶体(平均粒径为3.5微米)和30％(重量)氧化硅与氧化铝摩尔比为约900∶1的ZSM-5粘结剂晶体。通过先将ZSM-5核心晶体与含有痕量氧化铝的无定形氧化硅混合，然后将该混合物挤压成氧化硅粘结的挤出物来制备该催化剂。接着，通过在升高的温度下在含有模板和足以使氧化硅转化成粘结剂晶体的羟基离子的水溶液中老化该聚集体将挤出物的氧化硅粘结剂转化成第二沸石。然后将得到的沸石粘结的沸石洗涤、干燥、焙烧和离子交换成氢形式。
II.催化剂B
催化剂B含有70％(重量)氧化硅与氧化铝摩尔比为75∶1的H-ZSM-5(平均粒径为3.5微米)和30％(重量)无定形氧化硅粘结剂。
使用催化剂A和催化剂B进行甲苯甲基化试验。在开始试验之前，磨碎每种催化剂并在30U.S.目和+40U.S.目之间的筛筛分。然后将1.5克催化剂与3克14/20目筛分的石英片混合并放入管式反应器中。接着，蒸发甲苯与甲醇摩尔比为3.8/1的混合物并加入到反应器中。试验的条件包括WHSV为12，温度为400℃，450毫升/分N2，和总压力为6.0psig。得到的结果示于下表I：
表I催化剂 进行生产的 甲苯转化率 二甲苯收率 对二甲苯选   C1-C3
   时间(小时)   (％)        ％       择性(％)   (重量％)
A     1.55      11.7       73.3       57.6        1.6
B     9.45      19         70.7       30.9        0.9
*PX选择性＝(PX/[PX+MX+OX]×100
数据表明催化剂A的对二甲苯选择性明显的大于热力学平衡，并且还大于无定形氧化硅粘结的催化剂。
用六甲基二硅氧烷(HMDS)选择性化催化剂A。进料含有4.7％(重量)六甲基二硅氧烷，1.0％(重量)正丙基硫醇，和甲苯与甲醇的摩尔比为3.8∶1。将进料泵入加热管线，在加热管线中在325℃下蒸发并加入到管式反应器中。试验的条件包括温度为400℃，WHSV为12，450毫升/分N2，和总压力为6.0psig。
用于选择性化催化剂的进料具有一定比例的甲苯和甲醇并含有4.7％(重量)六甲基二硅氧烷和1％(重量)正丙基硫醇。蒸发进料，然后加入到1.5克催化剂A中，该催化剂A是与3.0克石英片一起装在管式反应器中的。选择性化的条件为400℃，WHSV为7.9，8毫升/分的在N2中的54％H2，和总压力为0.3-0.5Psig。通过管线内气相色谱分析产物。结果示于表II。
表II进行生产的 甲苯转化率 二甲苯收率 对二甲苯选   C1-C3时间(小时)    ％      (％)       择性(％)   (重量％)0.25      29.4     53.4       42.6        0.21.48      29.4     53.6       48.2        0.22.72      28.5     55         51.4        0.23.95      27.4     57.8       52.3        0.25.18      26.6     58         53.3        0.26.42      25.9     60.3       52.8        0.2
选择性化催化剂之后，使用与实施例1相同的方法，只是WHSV为7.9和总压力为5.3-5.6psig，试验催化剂A对于甲苯的甲基化.结果示于下表III中：
表III进行生产的 甲苯转化率 二甲苯收率 对二甲苯选  C1-C3时间(小时)    ％      (％)       择性(％)   (重量％)0.38      11.3     91.4       74.1        1.51.57      10.7     91.6       71.7        1.6
数据表明通过选择性化，催化剂A的活性和对二甲苯的选择性提高了。
实施例2
焙烧后的沸石粘结沸石的催化剂含有H-ZSM-5核心晶体(氧化硅与氧化铝的摩尔比为约75)并用ZSM-5核心晶体(氧化硅与氧化铝的摩尔比为约900)粘结，通过在下表IV列出的条件下加入甲苯通过催化剂来选择性化该催化剂：
表IV选择性化的条件
    小时     267
    温度(°F)     1100
    压力(Psig)     225
 WHSV(#进料/#催化剂/小时)     1
 H2：进料甲苯之比(摩尔)     初始最终     0.21∶10.35∶1
    烃分压     初始最终     64.6Psig62.2Psig
选择性化之后，使用该选择性化的催化剂用甲醇烷基化甲苯。试验条件和在油中催化剂性能示于表V。
表V
    试验     1     2     3
    平均床层温度(°F)     957     962     937
    WHSV(磅进料/磅催化剂/小时)     4.4     4.4     4.4
    甲苯/甲醇进料比(重量∶重量)     8∶1     8∶1     8∶1
    时间(小时)     1     4     7
    甲苯转化率(重量％)     37.2     29.1     21.4
    甲醇转化率(重量％)     100     100     ＞98
    PX选择性(％)     81.1     81.0     80.1
    Xs∶BZ(摩尔)     1.1     1.74     5.2
    二甲苯收率(重量％对于甲苯)     16.4     15.0     12.9
PX选择性＝(PX/[PX+MX+OX]×100
表V的数据表明催化剂具有对对二甲苯高的选择性，二甲苯∶苯的比例随着进行生产的时间而增加。

Claims (20)

1.一种制备对二甲苯的方法，该方法是在沸石粘结沸石的催化剂存在下在甲基化条件下甲苯与甲基化试剂反应，该催化剂含以第一沸石和第二沸石的总重量计小于10％(重量)的非沸石粘结剂并含有：
(a)第一中等孔径沸石的第一晶体；和
(b)含有第二沸石的第二晶体的粘结剂。
2.根据权利要求1的方法，其中第二晶体是交互生长的，并在第一晶体上形成至少部分包层。
3.根据权利要求1或2的方法，其中以第一沸石和第二沸石的合并重量计，催化剂含有少于5％(重量)的非沸石粘结剂。
4.根据权利要求2的方法，其中第一晶体的平均粒径大于0.1微米，第二晶体的平均粒径小于第一晶体的平均粒径。
5.根据权利要求4的方法，其中第一晶体的平均粒径为1-6微米和/或第二晶体的平均粒径为0.1-0.5微米。
6.根据权利要求2的方法，其中第一沸石和/或第二沸石是硅铝酸盐沸石或硅酸镓沸石。
7.根据权利要求6的方法，其中第一沸石是具有氧化硅与氧化铝摩尔比为10∶1-300∶1的硅铝酸盐或具有氧化硅与氧化镓摩尔比为10∶1-150∶1的硅酸镓。
8.根据权利要求7的方法，其中第二沸石是具有氧化硅与氧化铝摩尔比大于200∶1的硅铝酸盐或具有氧化硅与氧化镓摩尔比大于100∶1的硅酸镓。
9.根据权利要求2的方法，其中第一沸石和第二沸石的结构类型独立地选自AEL，MFI，MEL，MTW，MTT，FER，TON和EUO。
10.根据权利要求9的方法，其中第一沸石具有MFI结构和/或第二沸石具有MFI或MEL结构。
11.根据权利要求10的方法，其中第二沸石是硅质岩或硅质岩2。
12.根据权利要求2的方法，其中催化剂可通过在升高的温度下、在含有足以将聚集体中的氧化硅转化成第二沸石的羟基离子来源的含水离子溶液中老化含有第一沸石的第一晶体的氧化硅粘结的聚集体来制备。
13.根据权利要求2的方法，其中催化剂被选择性化。
14.根据权利要求13的方法，其中催化剂是用含有硅化合物的选择性化试剂选择性化的。
15.根据权利要求13的方法，其中催化剂在温度为480-650℃(900-1200°F)，压力为0.10-10.1MPa(1-100大气压)和重时空速为0.1-20的条件下通过催化剂与甲苯物流接触来预选择性化的，其中甲苯物流还任意地含有氢气，H2/甲苯摩尔比高达2。
16.根据权利要求15的方法，其中在甲苯物流中氢气与甲苯的摩尔比为0.1-1。
17.根据权利要求15的方法，其中催化剂含有至少2％(重量)焦炭。
18.根据权利要求2的方法，其中甲基化试剂是甲醇、甲基氯、甲基溴、二甲醚或二甲硫。
19.根据权利要求2的方法，其中甲基化条件包括温度为300-700℃和/或压力为0.10-6.9MPag(1大气压-1000psig)和/或重时空速为1-200和/或甲基化试剂与甲苯的摩尔比为0.05-5。
20.根据权利要求13的方法，该方法制备了含有大于平衡量的对二甲苯的产物物流。
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CA2255873A1 (en) 1997-12-04
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