CN102066257A - 用于芳族化合物转化的选择性催化剂 - Google Patents

用于芳族化合物转化的选择性催化剂 Download PDF

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CN102066257A
CN102066257A CN2009801238495A CN200980123849A CN102066257A CN 102066257 A CN102066257 A CN 102066257A CN 2009801238495 A CN2009801238495 A CN 2009801238495A CN 200980123849 A CN200980123849 A CN 200980123849A CN 102066257 A CN102066257 A CN 102066257A
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aggregate material
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CN102066257B (zh
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J·G·莫斯科索
E·P·博尔丁格
M·G·加特
S·C·柯斯特
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Honeywell UOP LLC
Universal Oil Products Co
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Abstract

本发明包括一种包含微晶的球状聚集体的新型UZM-14催化材料，其具有MOR骨架型、60纳米或更小的平行于12环通道方向的平均微晶长度、以及至少0.10立方厘米/克的中孔体积。由该新型材料形成的催化剂对芳族化合物的烷基转移特别有效。

Description

用于芳族化合物转化的选择性催化剂
发明领域
本发明涉及用于芳烃转化的催化剂。更特别地，本发明包括对于制备C8芳族化合物具有高活性的催化剂。
发明背景
大多数新型芳烃联合装置被设计用于获得苯和对二甲苯。苯为在包括乙基苯、枯烯和环己烷的许多不同产品中使用的万能石油化学产品结构单元。对二甲苯也是重要的结构单元，其主要用于制备通过对苯二酸或对邻苯二甲酸二甲酯中间体形成的聚酯纤维、树脂和薄膜。由于苯和对二甲苯的相对产率通常与由芳族化合物生成方法如催化重整和裂化获得的比例不相匹配，因此用于获得这些优选产物的芳烃联合装置通常包括各种方法，例如烷基转移、歧化、异构化和脱烷基化中的一种或多种。
Meyers在2003年由McGraw-Hill编辑的第3版Handbook of Petroleum Refining Processes中示例了用于说明应用芳族化合物转化方法的芳烃联合装置流程图。
已知的技术包括对将芳族进料转化为所需产物有效的各种催化剂。特别地，已经公开了用于烷基转移以将较轻芳族化合物，特别是甲苯，和较重芳族化合物，尤其是C9芳族化合物转化得到C8芳族化合物从而提高由芳烃联合装置得到对二甲苯的产率的催化剂。这类烷基转移方法通常在它们可将比C9重的芳族化合物转化为较轻产物的程度上被限制，因此在工业上需要更有效的催化剂。
发明概述
概括地，本发明包括一种包含微晶的球状聚集体的UZM-14聚集体材料，所述UZM-14聚集体材料具有包含12环通道的MOR骨架型、至少0.10立方厘米/克的中孔体积、以及60纳米或更小的平行于12环通道方向的平均微晶长度。
在一个具体的实施方案中，本发明包括适合芳烃转化的催化剂，所述催化剂包含含有微晶的球状聚集体的UZM-14聚集体材料、选自氧化铝、二氧化硅和二氧化硅-氧化铝中的一种或多种的粘合剂、以及包含选自周期表的VIB(6)、VIIB(7)、VIII(8-10)和IVA(14)族中的一种或多种元素的金属组分，所述UZM-14聚集体材料具有包含12环通道的MOR骨架型、至少0.10立方厘米/克的中孔体积、以及60纳米或更小的平行于12环通道方向的平均微晶长度。
在一个更具体的实施方案中，本发明包括适合芳烃转化的催化剂，所述催化剂包含含有微晶的球状聚集体的UZM-14聚集体材料、选自MFI、MEL、EUO、FER、MFS、MTT、MTW、MWW、MAZ、TON、FAU和UZM-8中的一种或多种的另外的沸石组分、选自氧化铝、二氧化硅和二氧化硅-氧化铝中的一种或多种的粘合剂、以及包含选自周期表的VIB(6)、VIIB(7)、VIII(8-10)、IB(11)和IVA(14)族中的一种或多种元素的金属组分，所述UZM-14聚集体材料具有包含12环通道的MOR骨架型、至少0.10立方厘米/克的中孔体积、以及60纳米或更小的平行于12环通道方向的平均微晶长度。
优选地，在以上每个实施方案中的UZM-14聚集体材料包括如下特征中的一个或多个特征：(1)球形聚集体具有至少0.13立方厘米/克的中孔体积；(2)UZM-14微晶具有至少1×1019个12环通道开口/克UZM-14材料；(3)平行于12环通道方向的平均微晶长度为50纳米或更小。
附图简述
附图为由几个试样获得的平行于12环通道方向的平均微晶长度、中孔体积和转化率的三维比较。
发明详述
本发明的UZM-14为具有独特吸附性能和催化活性的新型铝硅酸盐沸石，其具有如在Atlas of Zeolite Framework Types，第6修订版，C.H.Baerlocher，L.B.McCusker和D.H.Olson编辑，Elsevier(2007)，第218-219页中所述的MOR骨架型。MOR结构包含SiO4和AlO4四面体的4元和5元环，它们如此排列使得晶格包含与晶轴平行的12环通道而得到管状结构。通常，沸石的特征在于二氧化硅-氧化铝的摩尔比为8-50、优选不超过30。本发明基于如下发现：特定的晶体特征能够提高对内部微孔体积的可进入性，从而在烷基转移芳族化合物方面获得改进的活性和选择性。
本发明的UZM-14聚集体材料具有如下一个或多个区别特征：
(1)球形聚集体具有至少0.10立方厘米/克、优选至少0.13立方厘米/克、以及特别地至少0.2立方厘米/克的中孔体积；
(2)UZM-14微晶具有至少1×1019个12环通道开口/克UZM-14材料；
(3)平行于12环通道方向的平均微晶长度为60纳米或更小、优选50纳米或更小；
(4)UZM-14聚集体材料的Si/Al2比通常为8-50、优选不超过30。
本发明的UZM-14具有由如下经验式表示的无水基合成形式的经验组成：
Mm n+Rr p+Al1-xSiyOz
其中M为至少一种可交换阳离子，且M选自碱和碱土金属，其包括但不限于锂、钠、钾、铷、铯、钙、锶、钡及其混合物。R为选自质子化胺、质子化二胺、季铵离子、双季铵离子、质子化烷醇胺和季铵化烷醇铵离子中的至少一种有机阳离子。在该组成中，“m”为M与Al的摩尔比，其为0.05-0.95，“r”为R与Al的摩尔比，其具有0.05-0.95的值，“n”为M的重均化合价，其具有1-2的值，“p”为R的重均化合价，其具有1-2的值，“y”为Si与Al的摩尔比，其为3-50，“z”为O与Al的摩尔比，其具有通过如下方程式确定的值：
z＝(m·n+r·p+3+4·y)/2
对通过结合M、R、铝和硅的反应性来源而制得的反应混合物进行水热结晶，由此制得本发明的UZM-14聚集体材料。铝的来源包括但不限于烷醇铝、沉淀氧化铝、铝金属、铝盐和铝溶胶。烷醇铝的具体实例包括但不限于邻仲丁醇铝(aluminum ortho sec-butoxide)和邻异丙醇铝(aluminum ortho isopropoxide)。二氧化硅的来源包括但不限于四乙基正硅酸盐、胶体二氧化硅、沉淀二氧化硅、碱金属硅酸盐、HiSil和Ultrasil。M金属的来源包括卤盐、硝酸盐、醋酸盐和碱金属或碱土金属各自的氢氧化物。当R为季铵阳离子或季铵化烷醇铵阳离子时，所述来源包括氢氧化物、氯化物、溴化物、碘化物和氟化物。具体实例包括但不限于氢氧化四乙铵、溴化四乙铵、二乙基二甲基氢氧化铵等。R也可被引入作为胺、二胺或烷醇胺如N，N，N′，N′-四甲基-1，6-己二胺、三乙胺和三乙醇胺。
包含所需组分的反应性来源的反应混合物(任选地包含UZM-14种子)在自压下，在密封的反应容器中，在85-225℃、优选110-170℃的温度下反应1天至2周的时间、优选2-6天的时间。为实现本发明，100-1000转/分钟且优选200-500转/分钟的有效混合是重要的。在完全结晶后，通过例如过滤或离心手段分离固体产物与非均相混合物，然后用去离子水洗涤固体产物，并在空气中在至多100℃的环境温度下进行干燥。
如此合成的UZM-14在其通道中将包含一些可交换的或电荷平衡的阳离子。这些可交换的阳离子可以用其它阳离子进行交换，或者在有机阳离子的情况下，可以在受控条件下通过加热将它们除去。由于UZM-14为大孔沸石，其还可以通过离子交换，例如在10-12的pH下通过氨水处理直接除去一些有机阳离子。
本发明的催化剂通常包含耐火无机氧化物粘合剂和金属组分。还优选对催化剂进行预硫化步骤以引入以元素计0.05-2重量％的硫。
本发明的无机氧化物粘合剂组分包括如下材料：例如氧化铝、二氧化硅、氧化锆、氧化钛、氧化钍、氧化硼、氧化镁、氧化铬、氧化锡等以及其组合和复合物，例如氧化铝-二氧化硅、氧化铝-氧化锆、氧化铝-氧化钛、磷酸铝等。粘合剂优选包括氧化铝、二氧化硅和二氧化硅-氧化铝中的一种或多种。氧化铝是在此使用的特别优选的耐火无机氧化物，特别是对于制造用于烷基芳烃的烷基转移中的复合催化剂而言。氧化铝可以是各种水合氧化铝或氧化铝凝胶如勃姆石结构的α-氧化铝一水合物、三水铝石结构的α-氧化铝三水合物、三羟铝石结构的β-氧化铝三水合物等中的任意种，优选的是首先提及的α-氧化铝一水合物。
粘合剂和沸石可以以任何常规或其它适宜的方式进行结合以形成球状、丸剂、片剂、粒剂、压出物或其它合适的颗粒形状。例如，细碎的沸石和金属盐颗粒可以被分散在氧化铝溶胶中，然后将混合物以小滴形式分散在热油浴中，其中发生胶凝而形成球状凝胶颗粒。在US 2,620,314中较详细地描述了该方法。优选的方法包括将细碎形式的所选沸石、耐火无机氧化物和金属盐与粘合剂和/或润滑剂混合，并将混合物压缩成统一尺寸和形状的丸剂或片剂。可替代地，且更优选地，沸石、耐火无机氧化物和金属盐与胶溶剂在混合-研磨机中进行结合和掺合，稀释的硝酸是合适胶溶剂的一个实例。可使所得捏塑体经过预定尺寸的模具或小孔进行压制以形成压出物颗粒，所述压出物颗粒可经过干燥和煅烧，然后被利用。多种不同的压出物形状是可能的，包括但不限于圆柱形、三叶草形、哑铃形以及对称和非对称多叶形，其中优选的是三叶形。还可以借助转盘或鼓使压出物形成球形，然后进行干燥和煅烧。
本发明的催化剂任选地可包含另外的沸石组分。另外的沸石组分优选选自MFI、MEL、EUO、FER、MFS、MOR、MTT、MTW、MWW、MAZ、TON和FAU(IUPAC沸石命名委员会)和UZM-8(参见WO2005/113439，将其作为参考引入本文中)中的一种或多种。更优选地，特别是当催化剂用于烷基转移方法时，另外的沸石组分基本由MFI组成。在催化剂中合适的总沸石量为1-100重量％，优选10-95重量％，更优选60-90重量％。
催化剂优选包含金属组分，所述金属组分包含选自周期表的VIB(6)、VIIB(7)、VIII(8-10)、IB(11)、IIB(12)、IIIA(13)和IVA(14)族中的一种或多种元素。优选地，当催化剂用于烷基转移方法时，所述金属组分选自铼、镍、钴、钼和钨中的一种或多种。特别优选的金属组分包括镍和钼中的一种或两种。在烷基转移催化剂中合适的金属量为以元素计0.01-15重量％，优选0.1-12重量％，高度优选0.1-10重量％。催化剂还可包含磷组分，任选的粘合剂包含如在US 6,008,423中所述的磷酸铝，在此作为参考引入该专利。还优选对催化剂进行预硫化步骤以引入以元素计0.05-2重量％的硫。可以在制造催化剂的过程中或者在将催化剂装载至工艺设备中之后进行该预硫化步骤。
优选在空气气氛下，在425-750℃的温度下，优选在475-550℃的温度下将完成的复合物煅烧0.5-10小时的时间。
本发明的UZM-14聚集体材料可用于催化剂中以影响本领域中已知的各种反应。这些反应包括但不限于芳族化合物和异链烷烃的裂化、加氢裂化、烷基化、异构化、聚合、重整、脱蜡、氢化、脱氢、烷基转移、脱烷基、水合、脱水、加氢处理、加氢脱氮、加氢脱硫、甲烷化和合成气变换法。优选的烃转化方法包括芳族化合物和异链烷烃的烷基化以及芳族化合物的异构化，特别是芳族化合物的烷基转移。
加氢裂化条件通常包括200-650℃、优选310-510℃的温度。反应压力为大气压至25兆帕、优选1.4-20兆帕表压。接触时间通常对应于0.1-15小时-1、优选0.2-3小时-1的液体时空速(LHSV)。氢循环率为180-9000标准立方米/立方米、优选350-5000标准立方米/立方米。合适的加氢处理条件通常在如上所述的宽范围加氢裂化条件内。
催化裂化法优选将进料如瓦斯油、重石脑油和脱沥青渣油转化为汽油作为主要所需产物。450-600℃的温度条件、0.5-小时-1的LHSV和大气压至350千帕的压力是合适的。
在-30℃至40℃的温度下、大气压至7兆帕的压力下以及0.1-120小时-1的重时空速(WHSV)下进行烯烃对异链烷烃的烷基化以制得适合作为发动机燃料组分的烷基化物。可在US 5,157,196和US 5,157,197中找到链烷烃烷基化的详情，在此作为参考引入这两篇专利。
可通过包含UZM-14的催化剂催化其它反应，包括将石脑油重整为汽油、将乙基苯脱氢为苯乙烯、将苯氢化为环己烷、烷基芳族化合物的碱催化侧链烷基化、羟醛缩合、烯烃双键异构化和乙炔类的异构化、醇脱氢、以及烯烃二聚、低聚反应和将醇转化为烯烃。这些材料的合适的离子交换形式可催化汽车和工业排出流中的NOx还原成N2。在US 5,015,796和H.Pines的The Chemistry Of Catalytic Hydrocarbon Conversions，Academic Press(1981)，第123-154页以及其中包含的参考文献中描述了可用于这些方法中的一些反应条件和进料类型，在此作为参考引入它们。
本发明的沸石能够基于分子尺寸分离分子物种的混合物(动力学直径；通过较小分子物种进入晶体内空隙空间完成分离同时把较大物种排除在外)。在D.W.Breck，Zeolite Molecular Sieves，John Wiley and Sons(1974)的第636页提供了各种分子如氧气、氮气、二氧化碳、一氧化碳和各种烃的动力学直径。烃也可基于分子尺寸进行分离。
芳族化合物的烷基化，优选单烷基化包括利用上述沸石催化剂使芳族化合物与烯烃反应。可用于该方法中的烯烃为包含2-20个碳原子的任意那些。这些烯烃可以为支化或线性烯烃，且为末端烯烃或内烯烃。优选的烯烃为乙烯、丙烯和包含6-20个碳原子且具有内双键或末端双键的被称为洗涤剂用烯烃的那些烯烃。在至少部分液相条件下进行反应。因此，调节反应压力以保持烯烃至少部分溶解在液相中。对于高级烯烃，可在自压力下进行反应。实际上，压力一般为1.4-7兆帕，但是通常为2-4兆帕。就烯烃而言，可在60-400℃、优选90-250℃的温度以及0.1-3小时-1的重时空速下进行C2-C20范围内的烯烃对可烷基化芳族化合物的烷基化。可在200-250℃的温度下进行乙烯对苯的烷基化，在90-200℃的温度下进行丙烯对苯的烷基化。用于该方法中的可烷基化芳族化合物与烯烃的比例取决于具体的反应。在乙烯或丙烯对苯的烷基化中，苯-烯烃比可以为1-10。对于洗涤剂用烯烃，5∶1-30∶1的苯-烯烃比通常足以确保所需的单烷基化选择性。
烷基芳族化合物，特别是包含乙基苯和二甲苯的C8-芳族混合物的异构化是包含UZM-14的催化剂的一个优选应用。使烷基芳族化合物的进料混合物，优选C8芳族化合物的非平衡混合物与异构化催化剂在合适的烷基芳族化合物异构化条件下接触。这类条件包括0-600℃或更高，优选100-500℃的温度。压力通常为大气压至10千帕、优选小于5千帕的绝对压力。在异构化区包含充足的催化剂以提供就烃进料混合物而言0.1-30小时-1、优选0.5-10小时-1的液体时空速。最佳地，使烃进料混合物与氢以0.5∶1-25∶1或更高的氢/烃摩尔比在混合中进行反应。在US 7,091,390中可找到该方法的进一步详情，在此作为参考引入该专利。
包含UZM-14的催化剂对于烷基芳烃的烷基转移和歧化特别有效。因此，在烷基转移反应条件下处理每分子具有6-15个碳原子的烷基芳烃，使其与本发明的包含UZM-14的催化剂接触以形成相比于所述烷基芳烃具有较高和较低数目碳原子的产物。复合催化剂对于用重芳族化合物对甲苯和苯进行烷基转移以形成高产率的二甲苯特别有效。
用于烷基转移或歧化法的富芳族化合物原料流可以获自各种来源，所述来源包括但不限于用于获得轻烯烃和较重富芳族化合物副产物的石脑油、馏出物或其它烃的催化重整、热解，以及用于获得汽油范围内产物的重油催化或热裂解。由热解或其它裂解操作获得的产物在进料至联合装置之前，通常根据工业中公知的方法对其进行加氢处理以除去硫、烯烃及其它将影响产品质量的化合物。还可对轻循环油有利地进行加氢裂化以获得较轻组分，可对所述较轻组分进行催化重整以获得富芳族化合物原料流。如果原料流为催化重整产品，则优选高度严格地操作重整装置以在产物中获得高的芳族化合物产率和低浓度的非芳族化合物。还有利的是使重整产品经受烯烃饱和以除去在烷基转移方法中可聚合为重的非转化型产物的潜在产物污染物和物质。在US 6,740,788 B1中公开了这类工艺步骤，在此作为参考引入本发明。
烷基转移或歧化反应可通过以任何常规或其它适宜的方式与本发明的复合催化剂接触而实现，且可包括间歇或连续型操作，优选连续操作。将催化剂有利地置于垂直管式反应器的反应区的固定床中，其中烷基芳族化合物原料以上流或下流方式进料经过该床。在烷基转移区使用的条件通常包括200-540℃、优选200-480℃的温度。在100千帕至6兆帕适度升高的宽范围绝对压力下操作烷基转移区。烷基转移反应可以在宽的空速(即，每小时进料的体积/催化剂体积)范围内进行，液体时空速通常为0.1-20小时-1。优选在氢的存在下在汽相中对原料进行烷基转移；如果在液相中进行烷基转移，则氢的存在是任选的。如果存在氢，则游离氢与原料和循环烃的关联量为每摩尔烷基芳族化合物0.1摩尔的游离氢至每摩尔烷基芳族化合物10摩尔的游离氢。氢与烷基芳族化合物的该比例也称作氢烃比。特别值得注意的是催化剂在高活性水平下具有相对高的稳定性。
已经发现反应物进入UZM-14的12环通道的通路是影响用于芳烃烷基转移的催化剂的活性和稳定性的最重要参数。已经发现该通路与每单位沸石的微晶长度、中孔体积和12环通道开口相关。最重要的参数显然是平行于12环通道方向的微晶长度，其应该为60纳米或更小，优选50纳米或更小。
实施例
如下实施例基于在铵交换和煅烧的UZM-14上测量的试验结果和特性。所附权利要求书涵盖了在制造或配制的任何阶段的UZM-14，包括如此合成的或在离子交换之前或之后和/或在煅烧之前或之后的UZM-14。呈现的实施例用以说明本发明，不应该将其理解为限制如所附权利要求书中所述的本发明的广泛宽的范围。
在实施例1中制备UZM-14的两个试样，并将其命名为UZM-14A和UZM-14B以配制催化剂和进行详细的试验。由NaOH、铝酸钠、SiO2(Ultrasil)和溴化四乙铵(TEABr)以及充足的去离子水制备试样，在指定的温度下进行结晶，并以指定的每分钟转数(RPM)搅拌指定的一段时间。用去离子水洗涤所得微晶的球形聚集体3次，并在100℃的温度下进行干燥。
实施例1：
  UZM-14-A   UZM-14-B
  NaOH(克)   625   625
  铝酸钠(克)   450   451
  SiO2(Ultrasil)(克)   3212   3241
  TEABr(克)   506   506
  H2O(克)   16,850   16,975
  温度(℃)   150   150
  混合(RPM)   200   300
  时间(小时)   66   76
已知技术水平的丝光沸石的试样获自Zeolyst International和Tosoh Corporation，其用于与UZM-14试样进行比较。在实施例2中比较了两个UZM-14试样以及Zeolyst和Tosoh试样的特性。
通过对X射线衍射数据应用Scherrer公式来测量平行于12环通道方向的平均微晶长度。在分析之前，通过将NH4交换形式在氮气中加热至540℃保持2小时，然后在空气中保持5小时而使UZM-14和商用丝光沸石均转化为氢形式。特别地，在CuKα辐射下测量MOR组分的(002)衍射峰在23.8°2θ处的极大值半处的全宽度(FWHM)，接着由Scherrer公式计算平行于12环通道方向的平均微晶长度L002。
L002＝0.9*λ/(β*cos(θ))
其中λ为CuKα辐射的波长，θ为衍射角的1/2，β为使用如下公式校正仪器加宽的峰的FWHM：
β1/2＝B1/2-b1/2
其中B为峰的测量FWHM，b为仅显示仪器加宽的仪器标准的测量FWHM。假设峰在形状上部分为高斯峰，部分为柯西峰。
每克MOR骨架型沸石的12环通道开口的数目Np反比于平行于12环通道方向的平均微晶长度，且利用如下公式进行估计：
Np＝(4*N0*c)/(L002*MW)
其中N0为阿伏伽德罗常数(6.023*1023)，c为c轴晶胞长度，L002为平行于12环通道方向的平均微晶长度，MW为晶胞内容物的分子量。对于本发明的试样，该公式简化为(利用以纳米计测量的L002)：
Np＝6.2×1020/L002
由高分辨率SEM图估计颗粒尺寸。UZM-14试样和商用丝光沸石的SEM颗粒尺寸通常大于微晶尺寸，这是由于颗粒可包含多个微晶。
如下所述，根据氮吸附等温线确定这些材料中每种材料的中孔体积。在分析之前，通过将NH4交换形式在氮气中加热至540℃保持2小时，然后在空气中保持5小时而使UZM-14和商用丝光沸石均转化为氢形式。然后测量吸附等温线，并根据在P/P0最高值(～0.98)处的氮摄入确定总孔体积。使用t图估计微孔体积。自总孔体积中减去微孔体积从而获得中孔体积。
为了进一步试验，将上述的UZM-14粉末和商用丝光沸石粉末均形成催化剂，其中包含0.15％的Re、25％的Al2O3粘合剂和75％的UZM-14或商用丝光沸石材料。在通常的催化剂制备中，用胶溶的Catapal B氧化铝压出100克铵交换沸石以制备75％沸石/25％氧化铝的配制剂。在空气中，在550℃下煅烧压出物3小时，然后用HReO4水溶液旋转浸渍以在催化剂上浸渍0.15％的Re。然后在空气中，在540℃下煅烧含Re的压出物2小时。
对在芳族化合物烷基转移测试中的这些催化剂试样的每个试样进行活性测试。在350℃，反应器压力为250psig，重时空速为4和H2∶HC比为6下测量烷基转移、脱烷基和歧化反应的总转化率的权重平均。在试验的第一小时，通过用过量的二甲基二硫化物(250ppm S)掺杂进料而在试验装置中将催化剂硫化。在废催化剂上的S/Re摩尔比通常在0.5-0.8的范围。进料具有以重量百分比计的如下标称组成：
甲苯                    75
丙基苯                  2
甲基乙基苯              10
三甲基苯                9.7
1，2-二氢化茚           0.8
甲基丙基苯              1.0
二乙苯                  0.4
二甲基乙基苯            1.0
C11+芳族化合物          0.1
前述进料对于这些催化剂中每个的烷基转移的转化率的比较结果以及Zeolyst和Tosoh试样的特性示于实施例2。
实施例2：
Figure BPA00001279472200111
实施例3：
以与UZM-14A和UZM-14B相似的方式制备另外的UZM-14试样，仅与实施例1中所述的参数略有变化，确定每个试样的平行于12环通道方向的微晶长度、中孔体积和转化率：
Figure BPA00001279472200121
上述结果示于所附三维图中，其中在每个点以下的垂直线表示在25％基准以上的百分转化率。上述结果清楚地显示平行于12环通道方向的较低微晶长度以及增加的中孔体积的优势。
实施例4：
通过使50％UZM-14、25％MFI沸石和25％胶溶的Catapal B的混合物与硝酸镍、七钼酸铵和磷酸的溶液共混，使得如上所述的UZM-14-A和UZM-14-B材料形成催化剂，由此获得包含0.45％Ni、2％Mo和0.3％P的催化剂。在压出后，在空气中在500℃下煅烧催化剂2小时。
然后在与实施例9中所用的相同条件下测试这些催化剂的活性，但将硫化阶段延长至20小时以获得足够的时间使较大量的金属完全硫化。在350℃下所得的转化率如下：
UZM-14-A     39.7％.
UZM-14-B     44.5％。
实施例5
将如此合成的UZM-14-B材料在550℃的空气下煅烧12小时，进行离子交换，然后在550℃下煅烧另外的12小时。在该处理之后，材料的总酸度为0.500毫摩尔/克(通过NH3-TPD确定)，26％的Al为非骨架的(通过Al-NMR确定)。这表明UZM-14材料的酸度是热稳定的。

Claims (10)

1.一种包含微晶的球状聚集体的UZM-14聚集体材料，所述UZM-14聚集体材料具有包含12环通道的MOR骨架型、至少0.10立方厘米/克的中孔体积、以及60纳米或更小的平行于12环通道方向的平均微晶长度。
2.根据权利要求1所述的UZM-14聚集体材料，其中所述平行于12环通道方向的平均微晶长度为50纳米或更小。
3.根据权利要求1或2所述的UZM-14聚集体材料，其中所述中孔体积为至少0.13立方厘米/克。
4.根据权利要求1、2或3中任一项所述的UZM-14聚集体材料，其中所述UZM-14微晶具有至少1x1019个12环通道开口/克聚集体材料。
5.根据权利要求1-4中任一项所述的UZM-14聚集体材料，其进一步特征在于二氧化硅-氧化铝的摩尔比为8-50。
6.根据权利要求1-5中任一项所述的UZM-14聚集体材料，其进一步包含选自氧化铝、二氧化硅和二氧化硅-氧化铝中的一种或多种的粘合剂、以及包含选自周期表的VIB(6)、VIIB(7)、VIII(8-10)和IVA(14)族中的一种或多种元素的金属组分以形成适合芳烃转化的催化剂。
7.根据权利要求6所述的UZM-14聚集体材料，其中所述粘合剂包含磷酸铝。
8.根据权利要求6或7所述的UZM-14聚集体材料，其中所述催化剂包括油滴球形。
9.根据权利要求6、7或8中任一项所述的UZM-14聚集体材料，其中所述金属组分基本由铼、镍和钼中的至少一种组成。
10.根据权利要求6-9中任一项所述的UZM-14聚集体材料，其进一步包含选自MFI、MEL、EUO、FER、MFS、MTT、MTW、TON、MOR和FAU中的一种或多种的另外的沸石组分。
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JP5676438B2 (ja) 2015-02-25
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