CN104870089A - 脱氢芳构化催化剂及其制备方法和用途 - Google Patents

脱氢芳构化催化剂及其制备方法和用途 Download PDF

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Publication number
CN104870089A
CN104870089A CN201380066745.1A CN201380066745A CN104870089A CN 104870089 A CN104870089 A CN 104870089A CN 201380066745 A CN201380066745 A CN 201380066745A CN 104870089 A CN104870089 A CN 104870089A
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catalyst
boron
zsm
ethane
yield
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A·M·玛德加夫卡
A·M·劳里岑
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Shell Internationale Research Maatschappij BV
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Shell Internationale Research Maatschappij BV
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    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • 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
    • B01J29/42—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 containing iron group metals, noble metals or copper
    • B01J29/44—Noble metals
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Abstract

一种用于低级烷烃脱氢芳构化的含硼催化剂，其中所述硼以少于1wt％的量载带在无机载体上。所述催化剂可用于由低级烷烃生产芳烃。

Description

脱氢芳构化催化剂及其制备方法和用途
技术领域
本发明提供可用于烷烃脱氢芳构化以形成芳族化合物的催化剂。所述催化剂包含硼。
背景技术
预期生产主要石化产品如苯乙烯、苯酚、尼龙和聚氨酯等必须的苯会全球性短缺。通常，苯和其它芳烃通过应用溶剂萃取方法使富含芳族化合物的原料馏分(例如经过催化重整过程生产的重整产品和通过石脑油裂解过程生产的热解汽油)与非芳烃分离而获得。
为了满足对苯和其它芳烃日益增长的全球需求，许多工业和学术研究人员几十年来一直在开发由成本有利的轻链烷烃(C1-C4)原料生产轻芳烃(苯、甲苯、二甲苯或BTX)的催化剂和方法。设计用于此用途的现有技术催化剂通常包含酸性沸石材料如ZSM-5和一种或多种金属如Pt、Ga、Zn、Mo等来提供脱氢功能。乙烷和其它低级烷烃的芳构化在高温和低压下不向原料中加氢时是热力学有利的。但遗憾的是，这些工艺条件也有利于催化剂快速失活，这是由于形成不希望的表面焦炭沉物堵塞进入活性位的通道的缘故。
对于许多烃处理应用，降低由于结焦导致的催化剂性能下降速率的一种方法是增加催化剂金属的负载，以促进表面上更快的加氢/大的焦炭前体分子分解。另一种方法包括加入添加剂如磷酸盐或稀土，以调节表面酸性和降低反应条件下的结焦速率。这些方法对于以固定或慢速移动催化剂床为特征的方法来说是合适的，此时在两次再生期间(焦炭烧掉步骤)在反应器区催化剂颗粒的平均停留时间相对较长(至少几天)。例如，参见美国专利US 4855522和US 5026937，其中分别描述了用Ga促进且还包含稀土金属或含磷氧化铝的ZSM-5型低级烷烃芳构化催化剂。
克服该问题的另一种方法是设计一种低级烷烃芳构化方法，其中催化剂在反应条件下经历相对短的时间(少于一天)，随后进行烧焦和/或其它处理，以恢复全部或部分原始催化活性。这种方法的一个例子的特征是包含固定或不动催化剂床层的两个或更多个并联反应器，其中至少一个反应器在任意给定时间离线进行催化剂再生，而另外的反应器在芳构化条件下处理低级烷烃原料以生产芳烃。这种方法的另一个例子的特征是流化催化剂床层，其中催化剂颗粒在发生芳构化的反应区和从催化剂上烧掉积碳以恢复活性的再生区之间迅速且连续地循环。例如，美国专利US 5053570描述了用于转化低级链烷烃混合物为芳烃的流化床方法。
对于其中在每次再生处理之间催化剂相对较短时间暴露于反应条件下的方法如流化床方法，最优催化剂性能要求可能不同于固定床或移动床方法，后者要求在再生处理之间催化剂更长时间地暴露于反应条件下。具体地，在涉及短的催化剂暴露时间的方法中，重要的是催化剂不能表现出过度的初始裂化或氢解活性，否则会将太多原料转化为不希望的价值偏低的副产品如甲烷。
开发表现出高芳烃收率和烷烃转化率且性能随时间降低较少的催化剂将是有利的。
发明内容
本发明提供一种用于低级烷烃脱氢芳构化的含硼催化剂，其中所述硼以少于1wt％的量载带于无机载体上。
本发明还提供制备脱氢芳构化催化剂的方法，所述方法包括：制备无机载体；用硼或其化合物浸渍载体从而使硼在载体上的存在量为0.005-1wt％；和干燥和煅烧所述经过浸渍的载体。
本发明还提供生产芳烃的方法，所述方法包括：在反应器中使一种或多种低级烷烃与脱氢芳构化催化剂接触，其中所述催化剂包含约0.005-1wt％的硼、约10-99.9wt％的铝硅酸盐和粘结剂；和收集来自接触步骤的产品并分离和回收C6+芳烃。
附图说明
图1描述了在实施例1中由性能测试1和2获得的乙烷转化率、苯收率和总芳烃收率。
图2描述了在性能测试11-14中获得的乙烷转化率。
图3描述了在性能测试11-14中获得的苯收率。
图4描述了在性能测试11-14中获得的总芳烃收率。
具体实施方式
本发明提供可用于生产芳烃的方法中的催化剂。所述方法包括在约550-730℃的温度和约0.01-1.0MPa的压力下使含至少约50wt％的乙烷或其它C2烃或其它低级烷烃的烃原料与含硼的脱氢芳构化催化剂接触，以促进低级烷烃反应为芳烃如苯。本发明方法的主要希望产品为苯、甲苯和二甲苯。
原料中的烃可以是乙烷、乙烯或其它低级烷烃或它们的混合物。优选地，原料的大部分为乙烷和约0-20wt％、优选约5-10wt％的原料可以为乙烯。低级烷烃可以为乙烷、丙烷、丁烷、戊烷等。另外原料可以包含至多约40wt％的含有3-8个碳原子的其它开链烃作为共反应剂。这种附加的共反应剂的具体例子有丙烯、异丁烷、正丁烯和异丁烯。所述烃原料优选包含至少约60wt％的乙烷或低级烷烃，更优选为至少约70wt％。为了方便反应原料在这里通常被称为乙烷，但是其含义包括上面提到的可能必须或希望存在的所有其它烃物质。
在一个优选的实施方案中，反应器包括包含催化剂颗粒的区、容器或室，含乙烷的原料流过其中并发生反应。反应器系统可以包括固定、移动或流化催化剂床层。然后反应产品流出床层并且被收集。然后分离反应产品并回收C6+芳烃。任选地，回收甲烷和氢，和任选地C2-5烃循环回步骤(a)。
固定床反应器是一种反应器，其中催化剂在反应器中保持固定，和将催化剂颗粒排布在容器(通常为立式圆筒状)中，反应物和产品流过固定床。在固定床反应器中，催化剂颗粒原位保持，且相对于固定的参比框架不发生移动。固定床反应器可以是单个绝热床、被换热流体包围的多个管子或者带有中间换热的多个绝热床层，等等。固定床反应器也可以被称为填充床反应器。固定床反应器提供良好的气固接触。固定床反应器的构造可以包括在不同区域内的至少两个单独的固定床，从而至少一个床层可以处于反应条件下的正在运行的操作状态，而其它床层中的催化剂处于再生状态。
在移动床催化反应器中，重力驱使催化剂颗粒流动，同时保持它们相互之间的相对位置。床层相对于包含它的容器壁移动。反应物可以以并流、逆流或错流方式流过该床层。活塞流是优选的流型。移动床有能力连续或间断地取出催化剂颗粒，从而它们能够在反应器外再生并随后再次引入循环回路。因此，当催化剂具有短的活性寿命和可以连续再生时应用移动床是有利的。移动床反应器可以包括至少一个用于一个或多个催化剂床层的塔盘以及支撑设施。支撑设施对于气体可渗透而对于催化剂颗粒不可渗透。
流化床反应器是一类可用于实施各种多相化学反应的反应器。在这类反应器中，气体以足够高的速度流过颗粒状催化剂，由此足以悬浮固体颗粒并使它的行为就象是流体。催化剂颗粒可以由多孔板支撑。可以强迫气体流过多孔板向上流过固体物质。在较低的气速下，固体原位保持而气体流过物质中的空隙。随气速增加，反应器达到一种状态，此时流体作用于固体上的力足以平衡固体物质的重量，和大于该速度时，反应器床层的内容物开始膨胀和旋转，更象是搅拌釜反应器或烧开的水壶。对于本发明的应用来说，流化床反应器是优选的，因为它提供了均匀的颗粒混合、均匀的温度梯度和以连续状态操作反应器的能力。催化剂与反应产品一起离开反应区并与之分离，从而在循环回反应区之前进行再生。
乙烷接触时间可以为约0.1秒至约1分钟。乙烷接触时间是乙烷原料分子在反应区中的平均时间。优选的乙烷接触时间为约1秒至约5秒。更长的乙烷接触时间是不太希望的，因为它们倾向于发生二次反应，这些导致不太希望的副产品如甲烷和降低对苯和/或总芳烃的选择性。
以金属计，催化剂包含约0.005-0.09wt％的铂。在催化方面铂是高活性的，不仅对于希望的脱氢芳构化反应来说是这样，对于导致较低价值副产品甲烷等不希望的氢解反应也是这样，因此最好的是在催化剂中铂的浓度不超过0.1wt％，因为否则会产生太多的甲烷。在一个实施方案中，应用约0.005-0.05wt％的铂。
还可以向本发明的催化剂中加入减活金属。虽然减活金属可能具有其自身的催化活性，但其主要作用是调节铂的催化活性，从而减少具有较低价值的甲烷副产品的产生。合适的减活金属的例子包括但不限于锡、铅、锗和镓。以金属计，减活金属占催化剂的不大于约0.5wt％，更优选应用不大于约0.2wt％，和最优选使用不大于约0.1wt％的减活金属，因为超过该量时，可能会造成至芳烃的总转化率太低而没有工业应用价值。
催化剂包含小于1wt％的硼。硼量可以为0.005-1wt％，优选为0.01-0.6wt％，更优选为0.02-0.4wt％。
催化剂还包含约10-99.9wt％的一种或多种铝硅酸盐物质，优选为约30-99.9wt％，以铝硅酸盐计。铝硅酸盐优选具有约20-80的二氧化硅:三氧化二铝(SiO2:Al2O3)摩尔比。所述铝硅酸盐可以优选为具有MFI或MEL类结构的沸石，和可以为ZSM-5、ZSM-8、ZSM-11、ZSM-12或ZSM-35。优选将沸石或沸石混合物转化为氢型，以提供足够的酸度来辅助催化脱氢芳构化反应。这可以通过在至少约400℃的温度下在空气中煅烧铵型沸石来实现。
粘结剂材料用于使单个沸石晶体颗粒保持在一起，以维持整个催化剂颗粒粒度在流化床操作的最优范围或者防止固定床或移动床操作中压降过大。粘结剂可以选自氧化铝、二氧化硅、二氧化硅/氧化铝、各种粘土材料如高岭土或它们的混合物。优选地，可以包括无定形无机氧化物:γ-氧化铝、二氧化硅、二氧化硅/氧化铝或它们的混合物。最优选地，氧化铝和/或二氧化硅被用作粘结剂材料。
含硼的铝硅酸盐晶体如ZSM-5可以通过如下方法合成：制备在骨架中含铝和硅的铝硅酸盐、在所述铝硅酸盐上沉积硼和随后煅烧所述铝硅酸盐。在加入硼之前、同时或之后，还可以通过相同程序加入铂和/或减活金属。可以通过通常已知的用于向这种结构中加入金属的任意方法加入金属，包括在合成晶体的过程中向铝硅酸盐框架中加入、或随后通过离子交换或者本领域熟练技术人员已知的各种浸渍方法加入已经合成的晶体框架中。硼、铂和减活金属可以通过相同或不同的方法加入。
在一个优选的实施方案中，煅烧铝硅酸盐晶体以脱除水分。然后，通过使铝硅酸盐与含硼的水溶液接触而用硼浸渍铝硅酸盐。所述水溶液优选为硼酸的水溶液。再一次煅烧铝硅酸盐，和然后用含铂和减活金属的水溶液浸渍而加入铂和减活金属。当减活金属为镓时，该水溶液优选为四胺硝酸铂和硝酸镓(III)的水溶液。
在本发明的一个优选的实施方案中，将乙烷或低级烷烃原料物流引入脱氢芳构化反应器中。然后原料物流与催化剂颗粒接触预定段的时间。反应产品离开反应器并转移至分离器。分离器脱除芳烃产品和主要的副产品、甲烷和氢气(其可以优选进行回收)，和还脱除C2-5副产品和未反应的乙烷或其它低级烷烃(其可以任选地再循环回脱氢芳构化反应器)。
如下实施例只作为描述的目的提供，和不用于限定本发明的范围。
实施例1
用含80wt％沸石ZSM-5CBV 2314粉末(23:1的SiO2/Al2O3摩尔比，由Zeolyst International获得)和20wt％氧化铝粘结剂的直径为1.6mm的圆柱状挤出物颗粒制备催化剂A。在用于制备催化剂前，按如下温度程序在空气中将所述挤出物样品煅烧至650℃以脱除残余水分：在100℃保持10分钟，以3℃/min从100℃升温至650℃，在650℃保持3小时，然后冷却至100℃。
为了制备催化剂，通过首先混合合适量的四胺硝酸铂和硝酸镓(III)的原料水溶液、用去离子水稀释该混合物至体积正好足以填充挤出物的孔隙、和在室温和常压下用该溶液浸渍所述挤出物，从而在上述的ZSM-5/氧化铝挤出物的25-100克样品上沉积金属。将浸渍后的样品在室温下老化2-3小时和然后在100℃下干燥过夜。对于催化剂A来说，目标金属负载量为0.09wt％Pt和0.25wt％Ga。在催化剂A的制备中未使用硼化合物。因此，催化剂A不是按本发明制备的。
按本发明制备的催化剂B应用与催化剂A相同的材料和程序制备，只是使在650℃下煅烧后的挤出物经受利用硼酸水溶液的初始孔体积浸渍，在室温下老化2-3小时，在100℃下干燥过夜，然后在在650℃下在空气中煅烧。在该第二煅烧步骤后，以上面针对催化剂A所述的方式用四胺硝酸铂和硝酸镓的水溶液浸渍所述含硼的挤出物。将经过浸渍的样品在室温下老化2-3小时，然后在100℃下干燥过夜。对于催化剂B来说，目标金属负载量为0.09wt％Pt、0.25wt％Ga和0.1wt％B。
对如上所述制备的催化剂A和B样品在性能测试1和2中分别进行测试。对于每次性能测试来说，将15-cc新鲜(之前未测试过的)催化剂进料装入石英管(1.40cm内径)中，并放入与自动气流系统相连的三区炉中。
在性能测试1和2之前，在常压(约0.1MPa绝压)下以如下方式原位预处理所述催化剂进料：
(a)用空气在约60升/小时(L/hr)下煅烧，在这期间反应器壁温在12小时内从25℃提升至510℃，在510℃下保持4小时，然后进一步在1小时内从510℃升至621℃，然后在621℃保持30min；
(b)用氮气以约60L/hr在621℃下吹扫20min；
(c)用氢气以60L/hr在621℃还原30min。
在上述预处理结束时，使催化剂进料经受157次如下循环：按如下程序在常压(约0.1MPa)和621℃的反应器壁温下交替暴露于100％的乙烷原料和100％的氢气：
(a)1000GHSV下5分钟100％的乙烷原料
(b)4000GHSV下10分钟100％的氢气。
在该测试方案下催化剂暴露于乙烷原料的总累积时间为13.3小时。上述原料/氢气气提的157次循环的总运行时间为39.9小时。
为了监测这些测试期间催化剂性能的变化，约每三小时一次在接近选择的5分钟乙烷暴露间隔结束时利用在线气相色谱分析仪系统对每个反应器的总出口物流进行取样和分析。基于由气相色谱分析获得的组成数据，按如下公式计算乙烷转化率：
乙烷转化率％＝100-出口物流中的乙烷wt％。
各单独产品组分的单程收率由反应器出口物流中产品wt％量给出。按如下公式计算每种产品组分的归一化收率：
产品P的归一化收率＝(100*产品P的单程收率wt％)/乙烷转化率％。
测试结束时，终止进入反应器的乙烷流量，并以60L/hr的流量再次引入氢。切断反应器炉加热器，并在约8小时的时间段内将催化剂冷却至约38℃。
性能测试1和2中获得的乙烷转化率、苯收率和总芳烃收率数据在图1中进行比较。正如该图中所示，按本发明制备的催化剂B在乙烷转化率、苯收率和总芳烃收率方面表现出比催化剂A明显更低的性能下降速率。具体地，在这些测试条件下测量的催化剂B的初始和最终乙烷转化率分别为50.9％和44.7％，而催化剂A的对应值分别为51.6％和37.9％。催化剂B获得的初始和最终苯收率分别为14.7wt％和11.5wt％，而催化剂A分别为15.3wt％和9.3wt％。催化剂B获得的初始和最终总芳烃收率分别为33.9wt％和28.3wt％，而催化剂A分别为33.4wt％和22.4wt％。
另外，性能测试1和性能测试2中整个运行期间获得的平均乙烷转化率和归一化产品收率在下表1中列出。
表1
性能测试 1 2
催化剂 A B
平均乙烷转化率，％ 44.04 47.58
平均归一化收率，wt％
氢气 9.66 9.92
甲烷 13.50 12.36
乙烯 9.80 8.74
丙烯 1.67 1.53
丙烷 2.17 1.95
C4化合物 0.40 0.37
C5化合物 0.05 0.04
苯 26.96 26.49
甲苯 18.81 21.86
C8芳烃 4.35 4.99
C9+芳烃 12.64 11.74
总芳烃 62.75 65.08
如表1所示，在这里所应用的测试条件下，相对于催化剂A，按本发明制备的催化剂B不仅表现出更高的平均乙烷转化率(与图1所示的较低的性能降低速率一致)，而且给出更高的归一化总芳烃收率。
实施例2
应用与实施例1中制备催化剂A所用的相同材料和程序制备催化剂C，只是所述浸渍水溶液除了四胺硝酸铂和硝酸镓之外还包含硼酸。将浸渍后的挤出物在室温下老化2-3小时，然后在100℃下干燥过夜。催化剂C的目标金属负载量为0.09wt％Pt、0.25wt％Ga和0.05wt％B。
用与制备催化剂C相同的材料、程序和目标负载量制备催化剂D，只是在100℃浸渍后干燥步骤后，按如下温度程序在高达650℃的空气中煅烧催化剂D：在100℃保持10分钟，以3℃/min将温度从100℃升至650℃，在650℃下保持3小时，然后冷却至100℃。
使15-cc催化剂C和D的新鲜进料分别经受性能测试3和4。性能测试3和4应用与上述实施例1的性能测试1和2所用的相同原料、操作条件和程序实施。性能测试3和4中整个运行期间获得的平均乙烷转化率和归一化产品收率在下表2中列出。性能测试1的对应数据也在表2中列出以作比较。
表2
性能测试 1 3 4
催化剂 A C D
平均乙烷转化率，％ 44.04 45.62 47.39
平均归一化收率，wt％
氢气 9.66 9.77 10.02
甲烷 13.50 12.54 11.48
乙烯 9.80 10.37 9.24
丙烯 1.67 1.71 1.63
丙烷 2.17 2.00 1.97
C4化合物 0.40 0.43 0.41
C5化合物 0.05 0.07 0.06
苯 26.96 26.88 26.54
甲苯 18.81 20.14 22.26
C8芳烃 4.35 4.76 5.27
C9+芳烃 12.64 11.32 11.13
总芳烃 62.75 63.11 65.19
如表2所示，在这里所应用的测试条件下，相对于催化剂A或C，按本发明制备的加入硼化合物且随后高温煅烧的催化剂D给出更高的平均乙烷转化率和更高的归一化总芳烃收率。
实施例3
应用与上述实施例1中制备催化剂A所用的相同材料和程序制备催化剂E，只是催化剂E的目标金属负载量为0.025wt％Pt和0.09wt％Ga。在催化剂E的制备中未使用硼化合物，因此催化剂E不是按本发明制备的。
应用与上述实施例1中制备催化剂B所用的相同材料和程序制备催化剂F，只是催化剂F的目标金属负载量为0.025wt％Pt、0.09wt％Ga和0.10wt％B。
应用与上述实施例2中制备催化剂C所用的相同材料和程序制备催化剂G，只是催化剂G的目标金属负载量为0.025wt％Pt、0.09wt％Ga和0.05wt％B。
应用与上述实施例2中制备催化剂D所用的相同材料和程序制备催化剂H，只是催化剂H的目标金属负载量为0.025wt％Pt、0.09wt％Ga和0.05wt％B。
使15-cc催化剂E、F、G和H的新鲜进料分别经受性能测试5、6、7和8。性能测试5-8应用与上述实施例1和2的性能测试1-4所用的相同原料、操作条件和程序来实施。性能测试5-8中整个运行期间获得的平均乙烷转化率和归一化产品收率在下表3中列出。
表3
性能测试 5 6 7 8
催化剂 E F G H
平均乙烷转化率，％ 44.08 43.96 42.51 42.42
平均归一化收率，wt％
氢气 9.63 9.70 9.55 9.89
甲烷 12.26 12.07 13.02 10.83
乙烯 11.89 11.05 11.07 11.11
丙烯 2.19 2.11 2.01 2.10
丙烷 2.26 2.31 2.38 2.50
C4化合物 0.52 0.50 0.48 0.51
C5化合物 0.07 0.07 0.07 0.08
苯 27.08 26.97 27.45 27.39
甲苯 19.42 20.66 19.15 21.04
C8芳烃 4.69 4.93 4.69 5.41
C9+芳烃 9.98 9.62 10.13 9.15
总芳烃 61.18 62.18 61.43 62.99
如表3所示，在这里所应用的测试条件下，相对于催化剂E和G，按本发明制备的催化剂F和H给出更高的归一化总芳烃收率。
实施例4
应用与上述实施例1中制备催化剂B所用的相同材料和程序制备催化剂I，只是催化剂I的目标金属负载量为0.09wt％Pt、0.25wt％Ga和0.20wt％B。
使15-cc催化剂A(按上述实施例1中所述制备)和催化剂I的新鲜进料分别经受性能测试9和10。性能测试9和10按与上述实施例1-3的性能测试1-8相同的方式实施，只是有以下例外：
a)最终的预处理温度为580℃而不是621℃。
b)烃原料由乙烷和丙烷各50wt％组成而不是100％乙烷；总的烃进料流量为1000GHSV。
c)运行期间反应器壁温保持在580℃而不是621℃。
d)5/10分钟的原料/H2循环的次数为313而不是157。因此，总的烃原料暴露时间为26.08小时而不是13.3小时。
为了监测这些测试期间催化剂性能的变化，约每三小时一次在接近选择的5分钟乙烷暴露间隔结束时利用在线气相色谱分析仪系统对每个反应器的总出口物流进行取样和分析。基于由气相色谱分析获得的组成数据，按如下公式计算乙烷和丙烷的净转化率：
乙烷转化率％＝100x(原料中乙烷wt％-出口物流中乙烷wt％)/(原料中乙烷wt％)。
丙烷转化率％＝100x(原料中丙烷wt％-出口物流中丙烷wt％)/(原料中丙烷wt％)。
乙烷+丙烷的总转化率％＝((原料中乙烷wt％x乙烷转化率％)+(原料中丙烷wt％x丙烷转化率％))/100
各单独产品组分的单程收率由反应器出口物流中产品wt％给出。按如下公式计算每种产品组分的归一化收率：
产品P的归一化收率＝(100*产品P的单程收率wt％)/(乙烷+丙烷的总转化率％)。
性能测试9和10中整个运行期间获得的平均原料转化率和归一化产品收率在下表4中列出。
表4
性能测试 9 10
催化剂 A I
平均乙烷转化率，％ -6.34 -7.96
平均丙烷转化率，％ 95.14 94.43
平均乙烷+丙烷总转化率，％ 44.38 43.22
平均归一化收率，wt％
氢气 6.94 7.92
甲烷 18.65 12.73
乙烯 4.72 4.69
丙烯 2.20 2.47
C4化合物 0.39 0.40
C5化合物 0.05 0.05
苯 28.73 30.27
甲苯 24.88 26.68
C8芳烃 7.61 9.80
C9+芳烃 5.83 4.98
总芳烃 67.06 71.74
如表4所示，在这里所应用的测试条件下，按本发明制备的催化剂I的归一化总芳烃收率比催化剂A的值大四个百分点。
实施例5
应用与上述实施例1中制备催化剂B所用的相同材料和程序制备催化剂J，只是催化剂J的目标金属负载量为0.09wt％Pt、0.25wt％Ga和0.30wt％B。
使15-cc催化剂A(按上述实施例1中所述制备)、催化剂B(按上述实施例1中所述制备)、催化剂I(按上述实施例4中所述制备)和催化剂J的新鲜进料分别经受性能测试11-14。性能测试11-14应用与上述实施例1的性能测试1和2相同的预处理程序实施。
预处理过程结束时，使催化剂在1000GHSV、0barg压力和621℃反应器壁温下连续暴露于100％乙烷原料。测试运行的长度为原料暴露约13.8-21.3小时。对于每个测试，在开始5分钟时对反应器出口总物流进行在线气相色谱取样，随后约每1.25小时一次，直到运行结束。基于由气相色谱分析获得的组成数据，按上述实施例1所述计算乙烷转化率、单程产品收率和归一化产品收率。
性能测试11-14获得的乙烷转化率、单程苯收率和单程总芳烃收率数据分别在图2-4中进行了比较。
如图2-4所示，相比于催化剂A，按本发明制备的催化剂B、I和J在乙烷转化率、苯收率和总芳烃收率方面表现出明显较低的性能降低速率。在这些测试中获得的乙烷转化率、苯收率和总芳烃收率的初始值和最终值在下表5中进行了总结。
表5
性能测试 11 12 13 14
催化剂 A B I J
测试小时数 13.83 13.83 17.58 21.33
初始乙烷转化率％ 47.85 46.47 47.70 35.45
最终乙烷转化率％ 10.67 21.77 27.72 28.13
初始单程苯收率％ 14.59 14.21 12.73 9.57
最终单程苯收率％ 0.19 2.58 5.44 6.18
初始单程总芳烃收率％ 30.49 29.82 27.00 19.62
最终单程总芳烃收率％ 0.33 5.51 11.40 12.80
性能测试11-14期间获得的平均乙烷转化水平和归一化产品收率在下表6中给出。
表6
性能测试 11 12 13 14
催化剂 A B I J
测试运行时间，小时 13.83 13.83 17.58 21.33
平均乙烷转化率，％ 26.40 33.82 38.07 32.05
平均归一化收率，wt％
氢气 8.15 9.03 9.23 9.08
甲烷 6.62 8.95 10.01 8.56
乙烯 46.10 25.14 19.39 23.23
丙烯 3.84 4.03 3.59 4.40
丙烷 1.68 2.73 2.62 3.02
C4化合物 1.58 1.21 0.99 1.35
C5化合物 0.19 0.17 0.12 0.16
苯 15.18 22.65 25.42 24.23
甲苯 9.82 16.75 20.68 19.38
C8芳烃 2.21 3.72 4.09 4.12
C9+芳烃 4.62 5.61 3.87 2.46
总芳烃 31.84 48.73 54.05 50.20
如表6所示，在这些性能测试中，与未按本发明制备的催化剂A相比，按本发明制备的催化剂B、I和J保持明显更高的平均乙烷转化率及更高的归一化苯收率和总芳烃收率。

Claims (20)

1.一种用于低级烷烃脱氢芳构化的含硼催化剂，其中所述硼以少于1wt％的量载带在无机载体上。
2.权利要求1的催化剂，其中所述无机载体包含至少10wt％选自如下的沸石：ZSM-5、ZSM-11、ZSM-12、ZSM-23和ZSM-35。
3.权利要求1的催化剂，其中所述无机载体包含ZSM-5。
4.权利要求1的催化剂，其中硼量为0.005-0.5wt％。
5.权利要求1的催化剂，其中硼量为0.05-0.3wt％。
6.权利要求1的催化剂，还包含浓度为0.005-1wt％的铂。
7.权利要求1的催化剂，还包含浓度为0.005-1wt％的镓。
8.权利要求1的催化剂，其中所述无机载体不含硼。
9.一种制备脱氢芳构化催化剂的方法，所述方法包括：
(a)制备无机载体，
(b)用硼或其化合物浸渍载体从而使硼在载体上的存在量为0.005-1wt％；和
(c)干燥和煅烧所述经过浸渍的载体。
10.权利要求12的方法，其中在温度大于400℃下实施煅烧。
11.权利要求12的方法，其中温度为500-800℃下实施煅烧。
12.权利要求12的方法，其中所述无机载体包含ZSM-5。
13.权利要求12的方法，其中所述无机载体不含硼。
14.权利要求12的方法，还包括用铂浸渍所述无机载体。
15.一种生产芳烃的方法，所述方法包括：
(a)在反应器中使一种或多种低级烷烃与脱氢芳构化催化剂接触，其中所述催化剂包含约0.005-1wt％的硼、约10-99.9wt％的铝硅酸盐和粘结剂；和
(b)收集来自(a)的产品并分离和回收C6+芳烃。
16.权利要求18的方法，其中所述催化剂包含约0.05-0.5wt％的硼。
17.权利要求18的方法，其中在所述反应器中不存在氧。
18.权利要求18的方法，还包括回收甲烷和氢气。
19.权利要求18的方法，还包括将C2-5烃循环回步骤(a)。
20.权利要求18的方法，其中所述催化剂还包含浓度为0.005-1wt％的铂。
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