CN104603087A - 从重质芳烃生产二甲苯和轻质烯烃的方法 - Google Patents

从重质芳烃生产二甲苯和轻质烯烃的方法 Download PDF

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Publication number
CN104603087A
CN104603087A CN201380018869.2A CN201380018869A CN104603087A CN 104603087 A CN104603087 A CN 104603087A CN 201380018869 A CN201380018869 A CN 201380018869A CN 104603087 A CN104603087 A CN 104603087A
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Prior art keywords
transalkylation
weight
scope
zsm
reaction
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Inventor
Y·王
杰马尔·埃尔詹
穆罕默德·阿什拉夫·阿里
苏莱曼·S·阿勒-哈塔夫
赛义德·艾哈迈德·阿里
阿卜杜拉·穆罕默德·艾塔尼
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Saudi Arabian Oil Co
King Fahd University of Petroleum and Minerals
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Saudi Arabian Oil Co
King Fahd University of Petroleum and Minerals
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Publication of CN104603087A publication Critical patent/CN104603087A/zh
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Abstract

本发明提供了重质重整产物的烷基转移方法。所述重质重整产物在烷基转移反应器中与烷基转移催化剂和氢气接触，以将所述重质重整产物选择性转化为富二甲苯产物流。在所述反应期间产生的轻质烷烃可提供给蒸汽裂解器，其中它们被转化为轻质烯烃。

Description

从重质芳烃生产二甲苯和轻质烯烃的方法
技术领域
本发明涉及利用重质重整产物生产二甲苯。更具体地说，本发明涉及利用重质重整产物通过烷基转移生产二甲苯，并且还涉及利用副产物轻气体作为原料生产乙烯、丙烯和丁二烯。
背景技术
将通常包含大于约90重量％的C9+芳烃的重质重整产物掺混在汽油流中。然而，根据对汽油的芳烃含量和高的终沸点的现行法规，不可能再在汽油中掺混重质重整产物。考虑到对于对二甲苯需求的市场增长速度，通过烷基转移将重质芳烃转化为对二甲苯被认为是利用重质重整产物的一种经济可行的方式。
对汽油中芳烃含量的限制迫使炼油厂寻找利用从石脑油的催化重整得到的多余重质重整产物的替代途径。重质重整产物流通常包含高浓度的C9+芳烃，通常包含至少90重量％的C9芳烃。因此，由于对汽油中芳烃含量的严格限制，必须找到芳烃、例如在重质重整产物流中存在的芳烃的另外用途。
发明内容
总的来说，本发明提供了将重质重整产物烷基转移以产生富二甲苯流的方法。
重质重整产物的烷基转移方法包括以下步骤：向烷基转移反应器提供包含至少约90重量％的C9+芳烃的重质重整产物和氢气，所述烷基转移反应器载有烷基转移催化剂以将所述C9+芳烃选择性地转化为富二甲苯产物流，所述烷基转移催化剂包含选自由丝光沸石、β-沸石、ZSM-5、ZSM-11、ZSM-12、ZSM-22、ZSM-23、MFI拓扑沸石、NES拓扑沸石、EU-1、MAPO-36、SAPO-5、SAPO-11、SAPO-34、和SAPO-41构成的组中的至少两种固体-酸沸石，和选自元素周期表的第4族镧系元素、第6族和第10族中的至少三种金属；将所述富二甲苯产物流分离成轻气体再循环流、C9+重质芳烃再循环流和混合芳烃产物流；将所述混合芳烃产物流分离成苯流、甲苯流和二甲苯流；和从所述轻气体再循环流分离轻质烷烃并将所述轻质烷烃供应到蒸汽裂解器，其中所述轻质烷烃转化为混合烯烃。
在某些实施方式中，所述方法还包括从所述轻气体再循环流分离氢气并将所述氢气再循环到所述烷基转移反应器。在某些实施方式中，烷基转移反应区保持在从约200℃至约540℃范围的温度下。在某些实施方式中，所述烷基转移反应区保持在从约1MPa至约5MPa范围的压力下。在某些实施方式中，氢气与重质重整产物的比率在约0.1:1至约10:1的范围内。在某些实施方式中，所述蒸汽裂解器包括温度保持在从约600℃至约850℃范围内的反应区。在某些实施方式中，所述轻质烷烃在所述蒸汽裂解器反应区中的停留时间小于约0.1秒。在某些实施方式中，所述催化剂的两种固体酸沸石组分具有不同的物理和化学特性。在某些实施方式中，所述烷基转移催化剂包含第一种固体酸沸石，其存在量在催化剂总重量的约10重量％至约90重量％范围内。在某些实施方式中，所述烷基转移催化剂包含第二种固体酸沸石，其存在量在催化剂总重量的约10重量％至约90重量％范围内。在某些实施方式中，所述烷基转移催化剂还包含选自无机氧化物的粘结剂。在某些实施方式中，所述金属组分的存在量在总催化剂重量的约0.01重量％至约5重量％范围内。
附图简要说明
根据以下优选实施方式、所附权利要求和附图的详细说明，本发明的这些和其他特征、方面和优点得以更好地理解，其中：
图1表示希望的烷基转移反应；
图2表示不希望的烷基转移副反应；和
图3是烷基转移设备实施方式的示意图。
具体实施方式
虽然以下详细描述为了说明的目的包含许多具体细节，但要理解，本领域普通技术人员将认识到，以下细节的许多例子、变化和修改在本发明的范围和精神之内。因此，阐述本文中描述和附图中提供的本发明的示例性实施方式对请求保护的本发明不会有通用性的任何损失，并且不施加局限。
如前面所述，重质重整产物流通常具有高浓度的C9+芳烃。由于对汽油中可包含的芳烃量的严格限制，部分这些流不能直接用作汽油添加剂。利用存在于重质重整产物流中的所述芳烃的一种经济可行的选择是将存在于所述流中的C9+芳烃通过烷基转移转化为二甲苯。
烷基转移允许整合某些精炼方法并导致产生经济有价值的石化产品。例如，因为环境法规和最高沸点限制，从所述精炼方法产生的多余的C9+芳烃通常是废弃的并从汽油掺混池中除去，那么其可用作生产有价值的石化产品(例如对二甲苯)以及某些轻质烯烃(例如乙烯、丙烯和丁烯)的原料。
蒸汽裂解是一种石油化工方法，通过它饱和烃可分解为较小的、经常是不饱和的烃。它是生产低碳链烯(即烯烃)、包括乙烯和丙烯的最常用工业方法。
提供给所述烷基转移方法的原料可包括重质重整产物。示例性的重质重整产物组成在表1中提供。
主要化合物 组成(重量％)
异丙苯 1.7
正丙苯 4.3
1-甲基-2-乙基苯 6.5
1-甲基-3-乙基苯 18.5
1-甲基-4-乙基苯 9.1
1,2,3-三甲基苯 6.6
1,2,4-三甲基苯 39.0
1,3,5-三甲基苯 10.0
总C9芳烃 95.9
正丁苯 0.5
1,4-二乙基苯 0.8
1,3-二乙基苯 0.4
1,3-二甲基-5-乙基苯 0.8
1,4-二甲基-2-乙基苯 0.4
其它C10化合物 1.2
总C10芳烃 4.1
表1.有用的重质重整产物组成
在某些实施方式中，提供了集成方法，其中重质重整产物原料可用作烷基转移方法的烃进料以产生二甲苯和副产物轻气体。所述副产物轻气体可包含低碳链烷烃，所述低碳链烷烃可进给到蒸汽裂解器中用于生产轻质烯烃。在重质重整产物原料的烷基转移期间，如图1所示，最理想的反应导致产生混合的二甲苯、苯和甲基芳烃。不希望的副反应显示在图2中。在所述烷基转移反应期间，存在产生的大约10-20重量％的轻气体，其通常包含C1-C5链烷烃。表2中列出了通过重质重整产物的烷基转移产生的轻气体的典型组成。
化合物 浓度(重量％) 校正浓度(重量％)
甲烷 0.2206 1.44
乙烷 10.4601 68.41
丙烷 3.7252 24.36
异丁烷 0.5212 3.41
正丁烷 0.308 2.01
异戊烷 0.0558 0.37
表2.在400℃反应温度下重质重整产物的催化烷基转移中产生的轻气体的组成
在某些实施方式中，提供了利用重质重整产物通过烷基转移生产二甲苯的方法，以及随后利用副产物轻气体作为蒸汽裂解器的原料用于生产轻质烯烃，例如乙烯、丙烯和丁二烯。在这方面，在某些其他实施方式中提供了用于烷基转移方法和蒸汽裂解方法的集成设备。从所述烷基转移方法产生的链烷烃气体然后可用作蒸汽裂解器的原料。
图3提供了重质重整产物的烷基转移和随后的轻气体蒸汽裂解的集成方法的实施方式示意图。重质重整产物进料和氢气通过管线102提供给烷基转移反应器104。烷基转移反应器104可包含如在烷基转移反应区中所述的烷基转移催化剂。出自烷基转移反应器104的烷基转移流出产物流可通过管线106供应给分离器108，所述分离器将所述产物流分离成轻气体再循环流110、C9+重质芳烃再循环流116、混合芳烃产物流，后者然后可分离成苯流118、甲苯流120和二甲苯流122。轻气体再循环流110可包含氢气、以及轻质烷烃，并可通过管线114供应给乙烷蒸汽裂解器124的反应区，产生轻质烯烃，包括乙烯、丙烯和丁二烯，它们分别通过管线126、128和130收集。或者，所述低碳再循环流可转为其他用途，例如苯和甲苯回收，或者可以部分再循环到所述烷基转移区。任选地，一部分所述轻质烯烃流可以与氢气一起从分离器108通过管线112再循环到烷基转移反应器104。类似地，C9+重质芳烃再循环流116可以部分或全部再循环到烷基转移反应器104，在此它可以与通过管线102供应的原料和氢气合并。或者，C9+重质芳烃再循环流可以从工艺中除去以供处置或其他加工。
“混合二甲苯”是指用于生产对二甲苯和邻二甲苯的一类C8芳烃，并在某些应用中作为溶剂。这些化合物具有许多不同用途并且可以用作制备某些工业规模化学反应的原料。
例如，对二甲苯可用作制备聚酯的主要原料，由于大量基本需求聚酯一直享有高增长速度；邻二甲苯可用作制备邻苯二甲酸酐的原料，邻苯二甲酸酐用量大并具有成熟的市场；并且间二甲苯可用于制备各种产品，包括增塑剂、染料和木材防腐剂，但是与邻二甲苯和对二甲苯比较，通常量较低但是也在增长。乙苯是可存在于二甲苯混合物中的另一种化合物，并且偶尔回收用于生产苯乙烯。然而，乙苯通常被认为是不太希望的C8芳烃组分，因此并不总是分离和回收。
一般而言，可用各种各样的已知方式增加二甲苯的生产。例如，可通过以下方式增加二甲苯生产：(i)二甲苯异构化，(ii)甲苯歧化，和(iii)甲苯和C9+芳烃的烷基转移。用于增加二甲苯生产的各种不同方法的经济情况比较取决于各种因素，包括当前市场情况、分离成本、C9+芳烃可利用性、和环境隐患。甲苯的烷基转移是最佳二甲苯生产方式和歧化是最佳苯生产方式。所选择的反应方式的灵活性使得烷基转移装置能够根据市场动态和原料可利用性来运行。
如前面所述的重芳烃烷基转移成二甲苯是顺应当前严格的汽油规格的一种方法，从而响应了未来在汽油需求中的减少并符合二甲苯和苯的市场需求增长。在以前利用重质芳烃作为添加剂的情况中，现在重质芳烃的烷基转移允许实现精炼和石化操作之间的某些协作。重质芳烃的烷基转移的经济情况取决于汽油和二甲苯之间的价格差，并且在某些情况下还受到当地具体约束的影响。虽然与经典的二甲苯生产相比投资较高，但烷基转移可在重整产物利用度低的环境下获得成功。
通常的芳烃生产方法产生的二甲苯混合物具有接近热力平衡的比率(即，对-二甲苯、间-二甲苯和邻-二甲苯异构体分别约24:53:23)，而当前对这些二甲苯异构体各自的市场需求处于约80:2:18的比率。已经努力调节所述二甲苯混合物的组成超过所述热力学值。这些工作已经包括在催化剂开发和方法设计两方面的特定创新。
通常，混合二甲苯的生产可通过石脑油催化重整来实现，在用于邻二甲苯或对二甲苯的回收和提纯时尤其是如此。或者，混合二甲苯还可以从热解汽油(乙烯裂解器工艺的富芳烃副产物)回收，但是所生成的流的乙苯含量通常过高，限制了在溶剂市场中的应用。
在某些实施方式中，希望增加二甲苯的收率并且削弱苯的生产。要理解，对二甲苯衍生物的需求的增长速率比对苯衍生物的需求更大。在某些方法中，工业化国家可实现精炼改进以减少汽油的苯含量，这将进而增加可用的苯的供应来满足需求。以苯为代价的较高二甲苯收率是有利的目标和所描述的某些方法的结果。在某些实施方式中，C9+芳烃用苯或甲苯烷基转移的方法已经商业化，产生高二甲苯收率。
在某些实施方式中，混合二甲苯可从甲苯的歧化或C9芳烃的烷基转移得到。各种生产途径(和考虑事项)可包括：蒸馏混合二甲苯(处于掺混值的C8芳烃进料)；提取二甲苯(汽油掺混值的C8芳烃，和按比例分配收率基准在苯、甲苯和二甲苯(BTX)之间分配的提取成本)；常规甲苯岐化(甲苯的提取成本和相关的市场价值)；选择性甲苯岐化产生比例类似的苯和二甲苯，同时容许选择性产生对二甲苯(甲苯的提取成本和相关市场价值)；联合甲苯岐化和C9烷基转移(甲苯的化学价值和市场价值以及C9芳烃的相关汽油掺混值；和仅烷基转移(其处理包含重质重整产物C9+的进料并主要产生二甲苯和较低量的苯和液化石油气)。
二甲苯生产的复杂性可基本上根据所使用的方法而变化。通过设计和装置协作，可以非常灵活地改变产物构成，无论来自重整装置的芳烃的分布如何。这些方法可包括芳烃的烷基化、脱烷基、异构化、歧化和烷基转移方法，使得能够从所述重整装置产生的分布中增加想要的芳烃的生产。在某些实施方式中，二甲苯生产可通过分离想要的组分和重建剩余二甲苯的平衡分布而选择性转变成任何想要的对、间或邻二甲苯异构体。
在世界化学市场中有许多用于二甲苯生产的已知烷基转移方法可用。所有这些方法的主要功能是通过与苯环相连的烷基的重排将过剩的低价值重质芳烃流转化为另外的二甲苯，从而增加从芳烃复合物的对二甲苯生产。所使用的方法或技术的选择取决于许多考虑事项，并且通常所述选择是从新鲜的原料提供对二甲苯最高总收率的技术。表3提供了与某些主要烷基转移方法有关的各种优点和缺点、以及不同烷基转移技术的各种性质的列表。
表3.不同烷基转移技术的性质
在某些实施方式中，提供了从廉价的重质重整产物原料生产有价值的二甲苯的解决方案。预期在此使用的重质重整产物原料的典型组成总结在表1中。作为烷基转移方法的副产物并且主要包括低碳链烷烃的轻气体，可在蒸汽裂解器中进一步加工以产生乙烯、丙烯和丁二烯。在某些实施方式中，所述烷基转移方法中利用的催化剂可以是美国公布的专利申请No.2010/0029467中描述的任何催化剂。所述方法的烷基转移反应温度可在约200℃至约540℃的范围，反应压力可在约1MPa至约5MPa的范围，液时空速(LHSV)可在约1/小时至约5/小时的范围。氢气与重质重整产物的比率可在约1至约4的范围。
如图3所示，来自烷基转移的液体产物包括苯、甲苯和二甲苯。氢气和C9+烃可分别再循环回到所述烷基转移反应器中。所述轻气体，例如可以从所述分离器顶部收集的，将回收并且供应到在典型的蒸汽裂解器反应条件下的蒸汽裂解器中以产生乙烯、丙烯和丁二烯。如本领域已知的，蒸汽裂解是一种方法，饱和烃通过它可分解为较小的、经常是不饱和的烃。蒸汽裂解是生产低碳链烯(或烯烃)，包括乙烯和丙烯的主要工业方法。
通常，在蒸汽裂解期间，气态或液态烃进料如石脑油、LPG或乙烷用蒸汽稀释，然后在炉子中加热。反应温度通常很高，大于约600℃并通常约850℃，但是反应停留时间很短，通常小于0.1秒并更经常小于约0.01秒，导致气体速度达到超过音速的速度，以试图改善目标产物的收率。在已经达到裂解温度之后，所述气体在输送管线换热器中迅速骤冷以停止反应。
通过蒸汽裂解反应产生的产物将取决于原料的具体组成、烃与蒸汽比率、裂解温度和炉内停留时间。
在某些实施方式中，基于所述烷基转移反应条件，所述低碳烃原料(其可包括乙烷、LPG或轻质石脑油)可产生富含低碳链烯(例如乙烯、丙烯和丁二烯)的产物流。
表4和5提供了北美洲和欧洲的汽油规格趋势的近期趋势。如每个表中所示，芳烃含量的量已经稳定减少。这使得需找到在精炼厂中催化重整装置生产的重质重整产物的其他用途。RVP(Reid蒸气压)降低也指示汽油中重整产物浓度降低。
表4北美汽油规格的趋势
表5.欧洲汽油规格的趋势
在所述系统的实施方式中，烷基转移反应器包含为了将重质重整产物原料转化为苯、甲苯和二甲苯(以下称为“BTX”)、并特别是商业上有价值的二甲苯而开发的新的多金属沸石基催化剂。另外，所述多金属沸石基催化剂作为所述烷基转移反应的副产物产生石油化工原料，特别是C2和C3烃。
在某些实施方式中，所述多金属催化剂可通过混合选自丝光沸石、β-沸石、ZSM-5、ZSM-11、ZSM-12、ZSM-22、ZSM-23、MFI拓扑沸石、NES拓扑沸石、EU-1、MAPO-36、SAPO-5、SAPO-11、SAPO-34、和SAPO-41的至少两种沸石，并添加选自元素周期表的第4族镧系元素和第10族的至少三种金属组分而形成。所述两种沸石应该具有不同的物理和化学特性，例如，孔隙尺寸和酸度。一种示例性的催化剂包含沸石例如沸石β和ZSM-5，和金属例如铈、镍和铂。
所述烷基转移反应可在有固定床、移动床或径向流动反应器的一个或多个反应器中进行。反应温度在约200℃至约540℃范围内，或者在约200℃至约400℃范围内，或者在约350℃至约540℃范围内，或者在约200℃至约300℃范围内，或者在约300℃至约400℃范围内，或者在约400℃至约500℃范围内，或者在约450℃至约540℃范围内。反应压力可在约1MPa至约5MPa范围内，或者在约1MPa至约3MPa范围内，或者在约3MPa至约5MPa范围内，或者在约1MPa至约2MPa范围内，或者在约2MPa至约3MPa范围内，或者在约3MPa至约4MPa范围内，或者在约4MPa至约5MPa范围内。液时空速可在约1/小时(hr-1)至约5hr-1范围内，或者在约1hr-1至约3hr-1范围内，或者在约3hr-1至约5hr-1范围内，或者在约1hr-1至约2hr-1范围内，或者在约2hr-1至约3hr-1范围内，或者在约3hr-1至约4hr-1范围内，或者在约4hr-1至约5hr-1范围内。
所述转化过程的重质芳烃进料流可以是重质重整产物，通常包含碳数范围为C9至C11+的烷基芳烃，其可以包括，例如，如丙苯、乙基甲苯、四甲基苯、乙基二甲苯、二乙苯、甲基丙苯及其混合物的烃。
主要以C9+芳烃为特征的重质芳烃进料流致使轻质芳烃例如苯和甲苯与所述重质C9+芳烃的有效烷基转移，得到另外的C8芳烃，优选二甲苯。所述重质芳烃流优选包含至少约95重量％的C9芳烃。在某些实施方式中，所述重质芳烃进料流可来源于相同或不同的已知精炼和石油化工工艺。在某些实施方式中，所述重质芳烃进料流可至少部分包括从分离烷基转移的产物流和轻气体中再循环的进料流。
所述进料流的烷基转移可在蒸气相中并在氢气存在下发生。所述氢气通常与进料流和任何任选的再循环烃一起供应，量为约0.1摩尔氢气/摩尔烷基芳烃直至约十摩尔/摩尔烷基芳烃(亦即，氢气:烷基芳烃的比率在约0.1:1至约10:1的范围内)。在某些实施方式中，氢气:烷基芳烃比率可在约0.1:1至约2:1的范围内；或者在约2:1至约5:1的范围内，或者在约5:1至约10:1的范围内。氢气与烷基芳烃的比率也可以称为氢烃比。
在某些实施方式中，供应给烷基转移反应区的重质芳烃进料可加热。例如，在某些实施方式中，所述原料可首先通过针对反应区流出物的间接热交换加热，然后加热到反应温度。所述原料然后可通过反应区，所述反应区可以包括一个或多个独立反应器。在某些实施方式中，所述反应器包含具有固定的圆柱形催化剂床的单个反应容器。在别的实施方式中，可使用移动催化剂床或径向流动反应器，或者一种或多种上述反应器的组合。联合的氢气和重质芳烃进料通过所述反应区导致产生包含未转化的进料和目标产物烃的流出物流。
所述烷基转移反应在至少一个区中利用所述的烷基转移催化剂。所述方法还可以包括使用其他的催化剂。存在于原料中的较重质芳烃化合物容易进行转化成为较轻质的芳烃。用于所述烷基转移区的条件通常包括温度在约200℃至约540℃范围内，和适度升高的压力，广义上在约1MPa至约5MPa的范围内。
本文使用的烷基转移催化剂是基于与金属组分相结合的固体酸性材料。通常，所述催化剂可包括两种固体酸沸石材料。第一种固体酸沸石可包括丝光沸石、β-沸石、ZSM-5、ZSM-11、ZSM-12、ZSM-22、ZSM-23、MFI拓扑沸石、NES拓扑沸石、EU-1、MAPO-36、SAPO-5、SAPO-11、SAPO-34、和SAPO-41的所有形式和类型，和这样的固体酸的二氧化硅-氧化铝或离子交换形式。第一种沸石的存在量可在催化剂以其最终干燥和锻烧形式的总量的约10至约90重量％范围内。
掺入所述催化剂配方的第二种沸石在物理和化学特性两方面不同于第一种沸石，通常具有较高的酸度，并且是同样选自丝光沸石、β-沸石、ZSM-5、ZSM-11、ZSM-12、ZSM-22、ZSM-23、MFI拓扑沸石、NES拓扑沸石、EU-1、MAPO-36、SAPO-5、SAPO-11、SAPO-34、和SAPO-41的沸石。第二种沸石的存在量可在催化剂以其最终干燥和锻烧形式的总量的约10至约90重量％范围内。
所述催化剂可任选包含耐高温的粘结剂或基质以促进所述催化剂的制造、赋予催化剂强度并降低制造成本。所述粘结剂应组成均一并且比较能够耐受用于所述方法的条件。合适的粘结剂可包括无机氧化物，例如氧化铝、氧化镁、氧化锆、氧化铬、二氧化钛、氧化硼、磷酸盐、氧化锌和二氧化硅的一种或多种。在某些实施方式中，氧化铝可用作粘结剂。通常，所述两种沸石材料与干粉形式的所述氧化铝粘结剂混合，产生均匀混合物，从而确保由此形成的挤出物的均匀组成。
所述多金属沸石基催化剂还包含至少三种金属组分，选自第4族镧系元素、以及第6和10族金属。在某些实施方式中，两种所述优选金属组分选自第10族，例如镍和铂金属，但是钯可以代替或补充铂使用。在某些实施方式中，所述催化剂中可包含第6族金属，例如钼、铬或钨。第三种金属组分可选自第4族镧系元素，例如铈。在某些实施方式中，所述金属组分可与催化复合物的一种或多种其他成分化合，作为氧化物、硫化物或卤化物包含在最终的催化复合物内。在某些实施方式中，可包含元素形式的第4族镧系元素。所述金属组分在最终催化剂复合物中以催化有效量存在，例如以元素基准计算，在所述最终催化剂的约0.01和约5重量％之间。所述金属组分可通过任何适当的方式，例如与载体材料共沉淀或共凝胶、离子交换或浸渍，掺入所述催化剂中。
实施例
在所提供的实施例中，用于试验的示例性重质重整产物具有表6提供的组成。
主要烃 量(重量％)
异丙苯 1.8
正丙苯 4.4
1-甲基-3-乙基苯 18.5
1-甲基-4-乙基苯 9.1
1,3,5-三甲基苯 10.1
1-甲基-2-乙基苯 6.5
1,2,4-三甲基苯 39.1
1,2,3-三甲基苯 6.6
总C9组分 96.1
总C10组分 3.9
总组分 100
表6.典型的重质重整产物的组成
为了示例的意图，制备本发明的沸石混合沸石多金属催化剂，命名为实施例1的催化剂，并测试。实施例1的催化剂具有沸石混合沸石载体，并包含负载在所述沸石上的三种金属组分以及预定样式的氧化铝粘结剂，然后混合和粘结在一起形成挤出物。
实施例1：制备所述催化剂
在所述催化剂制备中使用β沸石(铵形式，HSZ-940NHA，得自日本Tosoh Chemical株式会社)，SiO2/Al2O3摩尔比为37，BET表面积为570m2/g，平均粒度6微米和标称Na2O含量为0.05重量％。根据以下过程，将所述β沸石与六水合硝酸镍水溶液一起搅拌以离子交换镍，并且干燥所得到的固体并用氯化铂水溶液浸渍以产生Ni-β-Pt：将六水合硝酸镍Ni(NO3)2·6H2O溶解在蒸馏水中以产生200mL的10重量％溶液。向该溶液添加30g未煅烧的β沸石并连续搅拌1小时，然后过滤，并最后洗涤两次以除去硝酸根离子。所生成的固体在室温下干燥2小时，然后在120℃烘干3小时。所述Ni-β然后用0.1重量％铂溶液浸渍。在这种基于润湿性试验的方法中，将0.038g氯化铂，Pt(Cl)2，溶解在36.1g蒸馏水中。为了完全溶解所述氯化铂，在搅拌下向所述混合物添加2.5mL氢氧化铵溶液。然后利用该溶液通过初始润湿方法(incipient wetness)浸渍所述Ni-β。所生成的固体在室温下干燥2小时，然后在120℃烘干3小时。然后4g干粉形式的氧化铝粘结剂(Cataloid AP-3，得自日本CCIC)分散在16mL含有0.62g硝酸铈Ce(NO3)3.6H2O的水溶液中，并连续搅拌30分钟，制备均匀分散的氧化铝。向该混合物添加粉末形式的4g未煅烧和未处理的ZSM-5(CT-435，得自英国CATAL)，以成为浆液，其中ZSM-5的二氧化硅与氧化铝摩尔比为27。随后添加12g的Ni-β-Pt并彻底混合，产生稠糊，其然后转变成1.0毫米(mm)挤出物。β与ZSM-5与AP3的比率是3:1:1。所述挤出物在室温下干燥过夜，然后在空气流通的烘箱中120℃下干燥，然后在500℃的炉子中锻烧3小时。产生的催化剂表示如下：[(Ni-β-Pt)+ZSM5+(Ce-AP3)]。
实施例2；测试实施例1的催化剂
实施例1的催化剂在台式反应系统中利用重质重整产物测试烷基转移反应，以检验所述催化剂对C9转化和产物选择性的有效性。试验方法构成如下：用2.0mL所述催化剂挤出物装填竖直反应器的反应器中部，同时惰性氧化铝球装填反应器的下部和上部。反应器总体积是5mL。所述催化剂在50mL/min气体的纯氢气流量下活化和还原并在400℃温度下保持2小时。然后，所述反应器温度减低到340℃和20巴压力，并以4.8mL/h的速率提供重质重整产物。所述重质重整产物的组成在表6中提供。在收集样品之前，反应在这个温度下运行3小时。然后反应产物直接注入配备火焰电离检测器的联机气相色谱中。烃分离在50米长和0.15mm直径的柱上在温度程控条件下进行。所述温度增加到360℃并且在分析气体和液体产物之前所述反应继续2小时。所述反应还在380℃和400℃的反应温度下运行。以这种方式，分析在340℃、360℃、380℃和400℃反应温度下的反应产物。所述组分根据它们的沸点分离。利用标定来鉴别所述组分，所述标定利用具有已知组成的组分的标准烃混合物样品完成。通过配备火焰电离检测器和热导检测器的14B型Shimadzu气相色谱脱机分析气态产物的组成。所述气态烃和氢气在50米毛细管柱的氧化铝PLOT上分离。得到在不同温度下的各种进料转化水平，结果表示C9组分的低和高苛刻度转化。C9总转化率(重量％)利用以下方程式计算。类似的表达式还用于计算各个C9化合物的转化率。
表7和8表明，实施例1的催化剂显示了在340℃和360℃的低苛刻度反应温度以及380℃和400℃的高苛刻度反应温度下比较高的C2-C4石油化工原料产量。
在表9和10中显示的C6-C8组成数据表明，实施例1的催化剂显示出在340℃和360℃的低苛刻度反应温度以及380℃和400℃的高苛刻度反应温度下高产量的混合二甲苯。所述数据显示了所述催化剂相当有活性并且在低温下产生高二甲苯收率。所述数据还显示苯和甲苯产量低，表明对C6和C7组分的选择性低。在低和高苛刻度这两种反应条件下，乙苯产量均可以忽略。
表11和12提供了在低反应温度340℃和360℃以及高反应温度380℃和400℃下的C9-C10产物组成数据。
表13和14表示在340℃和360℃的低苛刻度反应温度以及380℃和400℃的高苛刻度反应温度下各种C9烃相对较高的转化率。所述数据还表示即使在低苛刻度下C9烃转化率仍相当高。甲基乙苯(MEB)的转化率比三甲苯(TMB)转化率高，从而显示了二甲苯的生产选择性。
实施例1的催化剂 实施例1的催化剂
温度 340℃ 360℃
C2 4.88 6.41
C3 4.63 6.08
C4 3.02 3.96
表7.利用实施例1的催化剂在340℃和360℃的低苛刻度反应温度、LHSV 2.4h-1和20巴氢气压力下得到的反应产物的C2-C4组成(体积％)
实施例1的催化剂 实施例1的催化剂
温度 380℃ 400℃
C2 7.98 11.52
C3 3.25 4.03
C4 1.22 0.45
表8.利用实施例1的催化剂在380℃和400℃的高苛刻度反应温度、20巴氢气压力和LHSV 2.4h-1下得到的反应产物的C2-C4组成(体积％)
实施例1的催化剂 实施例1的催化剂
温度 340℃ 360℃
LHSV 2.4 2.4
苯 0.87 1.19
甲苯 10.49 13.10
乙苯 0.75 0.31
对二甲苯 6.69 7.38
间二甲苯 14.88 16.44
邻二甲苯 5.96 6.63
总二甲苯 27.53 30.45
表9.利用实施例1的催化剂在340℃和360℃的低苛刻度反应温度、20巴氢气压力和LHSV 2.4h-1下得到的反应产物的C6-C8组成(重量％)
实施例1的催化剂 实施例1的催化剂
温度 380℃ 400℃
苯 1.86 1.32
甲苯 15.26 13.57
乙苯 0.17 0.00
对二甲苯 7.65 7.74
间二甲苯 16.90 17.06
邻二甲苯 6.94 7.17
总二甲苯 31.49 31.97
表10.利用实施例1的催化剂在380℃和400℃的高苛刻度反应温度、20巴氢气压力和LHSV 2.4h-1下得到的反应产物的C6-C8组成(重量％)
实施例1的催化剂 实施例1的催化剂
温度 340℃ 360℃
1-甲基-4-乙基苯 0.60 0.43
1-甲基-3-乙基苯 1.77 1.18
1,3,5-三甲基苯 6.08 6.44
1-甲基-2-乙基苯 0.43 0.34
1,2,4-三甲基苯 13.49 15.02
1,4-二乙基苯 1.03 0.58
1,2,3-三甲基苯 1.66 2.01
1,2-二乙基苯 0.83 0.39
1,2,4,5-四甲基苯 1.91 1.52
1,2,3,5-四甲基苯 2.42 1.93
1,2,3,4-四甲基苯 0.54 0.54
表11.利用实施例1的催化剂在340℃和360℃的低苛刻度反应温度、20巴氢气压力和LHSV 2.4h-1下得到的反应产物的C9-C10组成(重量％)
实施例1的催化剂 实施例1的催化剂
温度 380℃ 400℃
1-甲基-4-乙基苯 0.00 0.00
1-甲基-3-乙基苯 0.36 0.20
1,3,5-三甲基苯 6.20 6.15
1-甲基-2-乙基苯 0.00 0.00
1,2,4-三甲基苯 14.02 14.12
1,4-二乙基苯 0.22 0.00
1,2,3-三甲基苯 1.81 1.87
1,2-二乙基苯 0.18 0.00
1,2,4,5-四甲基苯 1.41 1.42
1,2,3,5-四甲基苯 1.77 1.77
1,2,3,4-四甲基苯 0.42 0.42
表12.利用实施例1的催化剂在380℃和400℃的高苛刻度反应温度、20巴氢气压力和LHSV 2.4h-1下得到的反应产物的C9-C10组成(重量％)
实施例1的催化剂 实施例1的催化剂
温度 340℃ 360℃
LHSV 2.4 2.4
123TMB转化率 74.85 69.55
124TMB转化率 65.50 62.07
135TMB转化率 39.80 36.24
总TMB转化率 61.95 57.94
1M2EB转化率 93.38 94.77
1M3EB转化率 90.43 93.62
1M4EB转化率 93.41 95.27
总MEB转化率 91.79 94.28
表13.利用实施例1的催化剂，在340℃和360℃的低苛刻度反应温度、和LHSV 2.4h-1下的C9烃转化率(重量％)
实施例1的催化剂 实施例1的催化剂
温度 380℃ 400℃
123TMB转化率 72.58 71.67
124TMB转化率 64.60 64.34
135TMB转化率 38.61 39.11
总TMB转化率 60.52 60.32
1M2EB转化率 100.00 100.00
1M3EB转化率 98.05 98.92
1M4EB转化率 100.00 100.00
总MEB转化率 98.94 99.41
表14.利用实施例1的催化剂，在380℃和400℃的高苛刻度反应温度、和LHSV 2.4h-1下的各种C9烃转化率(重量％)
所提供的方法和组合物解决了经常遇到的若干问题。
虽然本发明已经详细描述，但应该理解对此可以做出各种改变、替代和修改而不背离本发明的原理和范围。因此，本发明的范围应该由以下权利要求和它们适当的法律意义等同物确定。
没有数量指示的单数形式指称物包括多个指称物，除非上下文另有明确指示。
任选的或任选地是指随后描述的事件或情况可以出现或可以不出现。该描述包括所述事件或情况出现的例子和它不出现的例子。
范围在本文中可以表示为从大约一个特定值和/或到大约另一个特定值。当表示这样的范围时，要理解另一种实施方式是从所述一个特定值和/或到另一个特定值，以及在所述范围内的所有组合。
在本申请之中，参考专利或出版物之处，意指这些参考文献的公开内容以它们的全文通过引用并入本申请，以便更充分地说明本发明所属领域的状态，除非这些参考文献与本文中做出的陈述相悖。
在本文中和在所附权利要求中使用时，单词“包含”、“具有”和“包括”及其所有语法变化各自意指具有开放的非限制含义，不排除另外的要素或步骤。
在本文中使用时，术语例如“第一”和“第二”是任意分派的，并且仅仅意在区分设备的两个或更多个部件。要理解单词“第一”和“第二”没有其他目的，并且不是所述组件名称或部件的描述，它们也不一定限定所述组件的相对位置或部位。此外，要理解仅仅使用术语“第一”和“第二”不要求有任何“第三”组件，虽然在本发明的范围下预期有此可能性。

Claims (12)

1.一种用于重质重整产物的烷基转移方法，所述方法包括以下步骤：
向烷基转移反应器提供包含至少90重量％的C9+芳烃的重质重整产物和氢气，所述烷基转移反应器载有烷基转移催化剂以将所述C9+芳烃选择性地转化为富二甲苯产物流，所述烷基转移催化剂包含选自由丝光沸石、β-沸石、ZSM-5、ZSM-11、ZSM-12、ZSM-22、ZSM-23、MFI拓扑沸石、NES拓扑沸石、EU-1、MAPO-36、SAPO-5、SAPO-11、SAPO-34、和SAPO-41构成的组中的至少两种沸石，和选自元素周期表的第4族镧系元素、第6族和第10族中的至少三种金属；
将所述产物流分离成轻气体再循环流、C9+重质芳烃再循环流和混合芳烃产物流；
将所述混合芳烃产物流分离成苯流、甲苯流和二甲苯流；和
从所述轻气体再循环流分离轻质烷烃并将所述轻质烷烃供应到蒸汽裂解器，其中所述轻质烷烃被转化为混合烯烃。
2.权利要求1的方法，其还包括从所述轻气体再循环流分离氢气并将所述氢气再循环到所述烷基转移反应器的步骤。
3.权利要求1或权利要求2的方法，其中烷基转移反应区保持在200℃至540℃范围内的温度。
4.权利要求1至3任一项的方法，其中烷基转移反应区保持在1MPa至5MPa范围内的压力。
5.权利要求1至4任一项的方法，其中所述氢气与重质重整产物的比率在0.1:1至10:1的范围内。
6.权利要求1至5任一项的方法，其中所述蒸汽裂解器包括温度保持在600℃至850℃范围内的反应区。
7.权利要求1至6任一项的方法，其中所述轻质烷烃在所述蒸汽裂解器的反应区中的停留时间小于0.1秒。
8.权利要求1至7任一项的方法，其中所述催化剂的两种固体酸沸石组分具有不同的物理和化学特性。
9.权利要求1至8任一项的方法，其中所述烷基转移催化剂包含第一种固体酸沸石，其存在量在催化剂总重量的10重量％至90重量％范围内。
10.权利要求1至9任一项的方法，其中所述烷基转移催化剂包含第二种固体酸沸石，其存在量在催化剂总重量的10重量％至90重量％范围内。
11.权利要求1至10任一项的方法，其中所述烷基转移催化剂还包含选自无机氧化物的粘结剂。
12.权利要求1至11任一项的方法，其中所述金属组分的存在量在催化剂总重量的0.01重量％至5重量％范围内。
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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
PT3105201T (pt) 2014-02-13 2019-12-24 Bp Corp North America Inc Processo de fracionamento eficiente de energia para separar o efluente de um reator dos processos de translaquilação de tol/a9+
JP6280995B2 (ja) * 2014-04-30 2018-02-14 エクソンモービル・ケミカル・パテンツ・インク 金属含浸触媒性能を改善する方法
US20150353447A1 (en) * 2014-06-04 2015-12-10 Exxonmobil Chemical Patents Inc. Transalkylation of Heavy Aromatic Hydrocarbon Feedstocks
US10472305B2 (en) * 2014-08-06 2019-11-12 Bp Corporation North America Inc. Heat integration in disproportionation or transalkylation processes
US20160221897A1 (en) * 2015-02-04 2016-08-04 Exxonmobil Chemical Patents Inc. Transalkylation of Heavy Aromatic Hydrocarbon Feedstocks
EP3539652A1 (en) 2018-03-14 2019-09-18 Saudi Arabian Oil Company Method of heavy reformate conversion into btx over metal-impregnated zsm-5+mesoporous mordenite zeolite composite catalyst
EP3785797B1 (en) 2018-03-14 2024-04-24 Saudi Arabian Oil Company Heavy reformate conversion into xylenes using composite zeolite catalysts
EP3539650B1 (en) 2018-03-14 2021-03-31 Saudi Arabian Oil Company Methods of producing composite zeolite catalysts for heavy reformate conversion into xylenes
EP3539651A1 (en) 2018-03-14 2019-09-18 Saudi Arabian Oil Company Method of heavy reformate conversion into btx over metal-impregnated zsm-5+layered mordenite zeolite composite catalyst; said composite catalyst
US10696609B2 (en) 2018-10-15 2020-06-30 Saudi Arabian Oil Company Integrated process for maximizing production of para-xylene from full reformate
US10894755B2 (en) 2018-10-15 2021-01-19 Saudi Arabian Oil Company Integrated process for optimum production of para-xylene
US10501389B1 (en) 2018-10-25 2019-12-10 Saudi Arabian Oil Company Process and system for the production of para-xylene and benzene from streams rich in C6 to C12+ aromatics
US11001773B1 (en) 2019-10-30 2021-05-11 Saudi Arabian Oil Company System and process for steam cracking and PFO treatment integrating selective hydrogenation and selective hydrocracking
US11220637B2 (en) 2019-10-30 2022-01-11 Saudi Arabian Oil Company System and process for steam cracking and PFO treatment integrating selective hydrogenation and FCC
US11220640B2 (en) 2019-10-30 2022-01-11 Saudi Arabian Oil Company System and process for steam cracking and PFO treatment integrating selective hydrogenation, FCC and naphtha reforming
US11091709B2 (en) 2019-10-30 2021-08-17 Saudi Arabian Oil Company System and process for steam cracking and PFO treatment integrating selective hydrogenation, ring opening and naphtha reforming
US11377609B2 (en) 2019-10-30 2022-07-05 Saudi Arabian Oil Company System and process for steam cracking and PFO treatment integrating hydrodealkylation and naphtha reforming
US11091708B2 (en) 2019-10-30 2021-08-17 Saudi Arabian Oil Company System and process for steam cracking and PFO treatment integrating selective hydrogenation and ring opening
US11390818B2 (en) 2019-10-30 2022-07-19 Saudi Arabian Oil Company System and process for steam cracking and PFO treatment integrating hydrodealkylation
US11046898B1 (en) 2020-05-15 2021-06-29 Saudi Arabian Oil Company Systems and processes for separating and upgrading hydrocarbons integrating a refinery system with steam cracking of an aromatic bottoms stream
US11377400B1 (en) 2021-07-01 2022-07-05 Saudi Arabian Oil Company Three stage catalytic process for pyrolysis oil upgrading to xylenes
US11578276B2 (en) 2021-07-01 2023-02-14 Saudi Arabian Oil Company Two stage catalytic process for pyrolysis oil upgrading to BTX

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101190866A (zh) * 2006-11-21 2008-06-04 中国石油化工股份有限公司 低乙苯副产物的芳烃烷基转移和脱烷基反应方法
CN101208412A (zh) * 2005-06-21 2008-06-25 Sk能源株式会社 提高由碳氢化合物原料制备轻质烯烃碳氢化合物的产率的方法
US20100029467A1 (en) * 2008-07-30 2010-02-04 Tomoyuki Inui Multiple zeolite catalyst

Family Cites Families (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5439003A (en) * 1977-08-30 1979-03-24 Nippon Petrochemicals Co Ltd Thermal decomposition method oh light hydrocarbon
DE3201457A1 (de) * 1982-01-19 1983-07-28 Basf Ag, 6700 Ludwigshafen Verfahren zur herstellung von olefinen
US4486296A (en) * 1983-10-13 1984-12-04 Mobil Oil Corporation Process for hydrocracking and dewaxing hydrocarbon oils
TW482751B (en) * 1997-06-06 2002-04-11 China Petro Chemical Technolog Catalysts and processes for the conversion of aromatic hydrocarbons and uses thereof in the production of aromatic hydrocarbons
ES2913654T3 (es) * 2004-03-08 2022-06-03 China Petroleum & Chem Corp Procedimiento de FCC con dos zonas de reacción
CN101172924B (zh) * 2006-11-02 2010-09-01 中国石油化工股份有限公司 高选择性芳烃烷基转移和脱烷基增产二甲苯反应方法
US7629498B2 (en) * 2007-06-28 2009-12-08 Exxonmobil Chemical Patents, Inc. Process of manufacturing para-xylene
JP5498720B2 (ja) * 2009-03-30 2014-05-21 一般財団法人石油エネルギー技術センター １環芳香族炭化水素の製造方法

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101208412A (zh) * 2005-06-21 2008-06-25 Sk能源株式会社 提高由碳氢化合物原料制备轻质烯烃碳氢化合物的产率的方法
CN101190866A (zh) * 2006-11-21 2008-06-04 中国石油化工股份有限公司 低乙苯副产物的芳烃烷基转移和脱烷基反应方法
US20100029467A1 (en) * 2008-07-30 2010-02-04 Tomoyuki Inui Multiple zeolite catalyst

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110913986A (zh) * 2017-06-15 2020-03-24 沙特阿拉伯石油公司 用于将重质重整产物转化成二甲苯的沸石复合催化剂

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