CN105722588A - 用于实施吸热反应且在反应管中形成流化层的方法和装置 - Google Patents

用于实施吸热反应且在反应管中形成流化层的方法和装置 Download PDF

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CN105722588A
CN105722588A CN201480061446.3A CN201480061446A CN105722588A CN 105722588 A CN105722588 A CN 105722588A CN 201480061446 A CN201480061446 A CN 201480061446A CN 105722588 A CN105722588 A CN 105722588A
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reaction
reaction tube
catalyst
tube
reaction tubes
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K·巴赫曼
F·格伦克
G·科利欧斯
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BASF SE
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BASF SE
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Abstract

本发明涉及一种实施吸热反应的方法，包括如下方法步骤：a)外部加热至少两根反应管(5)，其中反应管(5)垂直设置在加热室(3)中，且各反应管(5)至少部分填充有可流化材料，b)将至少一种气态反应物(E)引入反应管(5)中，c)在反应管(5)中形成流化床(7)，d)在反应管(5)中在第一温度(T1)和第一压力(P1)下实施吸热反应，其中反应体积分布在至少两根反应管(5)中，和e)从反应管(5)中排出反应产物(P)。本发明还涉及一种用于实施吸热反应的装置(1)，其包括：至少一个加热室(3)；至少两根反应管(5)，其中反应管(5)垂直设置在加热室(3)中，且各反应管(5)至少部分填充有可流化材料；对各反应管(5)的至少一个气态反应物(E)进入点(9)；对各反应管(5)的至少一个反应产物(P)排出点(11)，和至少一个用于外部加热反应管(5)的加热装置(13)。本发明还涉及本发明的装置(1)用于C1?C4脂族化合物的非氧化性脱氢芳构的用途。

Description

用于实施吸热反应且在反应管中形成流化层的方法和装置
本发明涉及一种用于实施吸热反应，特别是需要大量能量的强吸热反应的方法和装置。
吸热催化反应通常处于化学工业价值链的顶端，例如原油级分的裂化、天然气或石脑油的重整、丙烷的脱氢或甲烷脱氢芳构化以获得苯。这些反应是强吸热的。从烷烃分子中消去两个氢原子所需的能量为约100-125kJ/mol。必须使用500-1200℃的温度以获得工业和经济上有吸引力的产率。这主要是由于平衡转化的热力学限制所致。在该温度水平下提供反应所需的热量是一个巨大的技术挑战。有机化合物在高温下的结焦倾向提供了另一个挑战。焦炭沉积在催化剂表面上，优先沉积在反应器内部表面上，例如沉积在传热表面上。这使得催化剂失活且还降低传热性能。这导致反应器生产能力降低。现有技术的吸热非均相催化气相反应在固定床反应器或流化床反应器中实施。
在固定床反应器中，所需的工艺热量通常由盐熔体或烟道气提供，且由传热介质通过管壁间接传递给催化剂(Ullmann’s Encyclopedia of Industrial Chemistry，第7版，Wiley，2010；Catalytic Fixed-bed Reactors，Gerhart Eigenberger，WilhelmRuppel)。间接传热避免了产物料流因废气燃烧而造成的污染或稀释。为了实现有效的温度控制，固定床反应器包括组合以形成管束的薄反应管。管束反应器的容量可可靠地放大，这是因为这可通过反应管的数量实现。该构造可归因于固定床的λ径向≤10W/(m·K)的低径向热导率，即固定床中的传输因热导率的有效径向系数而受到限制。因此，尽管反应管具有高长细比，在产生大量热量的反应中，在管壁和管轴之间产生明显的热径向温度梯度。这可导致选择性损失和非均匀的催化剂失活。工业管束反应器包括至多35000个直径为16mm至不超过100mm的单独管。其缺点在于，管束反应器的构造变得不便且昂贵。不仅设备变得极其复杂，而且尽管使用精细程序来用催化剂填充反应管，也极难确保流动在所有反应管中均匀分布。
特别是对高生产能力的方法而言，已证明流化床反应器本身是优选的技术理念。特别是对产生大量热量的反应而言，流化床反应器提供了高轴向和横向热导率(λ>100W/(m·K))的优点，这导致在反应室中获得均匀的温度范围。
通常构造的流化床是连续的。该构造的优点是使得横向流动平衡成为可能。然而，该构造还具有各种缺点。例如，流化床反应器具有小长细比或长径比(L/D比)。L/D比通常为1-3。这导致在可流化材料和反应混合物二者中产生显著的轴向反混，这通常对反应产率具有不利影响。此外，反应器壁的强度必须非常高，从而确保机械稳定性，尤其是当在压力下运行时。
现有技术公开了各种用于将热量引入流化床中的技术方案。热量通常由浸没式管状线圈提供(参见“Handbook of Fluidization and Fluid-Particle Systems”，Wen-Ching Yang；Marcel Dekker，Inc.，2003)。该理念需要很少的资金支出，且类似于管束固定床反应器，提供了间接传热的优点，即反应气体和传热介质之间的物料隔离。该类反应器是不利的，因为在吸热反应期间，在换热器管内部上产生高温。因此，金属管壁直接暴露于热传热介质(燃料气，废气)中。该事实以及使用合适且昂贵的高温合金这一要求通常使得方法变得不经济。
此外，由于其高长细比，换热器管对由流化床脉动所引发的共振敏感。成泡流化床振动/脉动的频率主要取决于气泡的频率。这通常为2-14Hz(参见FluidizationEngineering，第2版，Butterworth-Heinemann，1991；Daizo Kunii，Octave Levenspiel)。通常所用的长度L＝10m且外径Da＝100mm的钢制换热器管的本征频率为约3Hz。由于换热器管的该本征频率与流化床振动/流化床脉动的频率具有相同的数量级，因此存在共振且因此破坏换热器管的可能性。
现有技术所提出的一种替代方案(参见Fluidization Engineering，第2版，Butterworth-Heinemann，1991；Daizo Kunii，Octave Levenspiel)是使用循环颗粒料流，例如催化剂颗粒来引入热量。在该技术中，催化剂颗粒以循环流化床的形式交替通过生产循环和再生循环。因此颗粒不仅用作催化剂，而且用作传热介质，从而为吸热反应提供热量。在反应室中，催化剂颗粒由于反应的吸热性以及连续负载的碳质沉积物(焦炭)而冷却。为了将它们加热并移除碳质层，在再生区中用热再生气体处理所述颗粒。然而，该技术要求颗粒，特别是催化剂颗粒耐氧和机械影响。
作为替代方案，US2012/0022310A1提出了使用满足化学和机械要求的惰性颗粒作为传热介质。此处，催化剂颗粒作为固定流化床的活性组分操作，其中加热的惰性颗粒从上至下通过该流化床，从而将能量引入流化床中。在流化床的下端，将惰性颗粒排出、再次加热(例如通过直接燃烧燃料)并从反应管的顶部，即反应器头部返回至该流化床中。该方法的一个缺点是催化剂颗粒因与惰性颗粒碰撞而经历机械应力，这可导致催化剂磨损或者甚至导致催化剂颗粒破碎。
例如，现有技术(参见Ullmann’s Encylopedia of Industrial Chemistry，第7版，Wiley，2010；Benzene；Hillis O.Folkins)公开了在流化床反应器中使用粉状催化剂作为可流化材料实施甲烷的脱氢芳构化。需要超过520℃的反应温度。此时，从流化床反应器的反应管下端供应烷烃并在反应空间内(在流化床中)转化成苯和作为副产物的其他烃。理想地，必须将反应所需的能量直接供应给该体系，从而避免因过热表面上的不受控反应而导致选择性损失。
US2007/0249880A1描述了由甲烷制备芳族化合物。此时，在催化剂材料的流化床中实施脱氢芳构化，所述催化剂材料除其作为可流化材料的特性之外，还通过在生产和再生步骤之间循环而用作传热材料。US2008/0249343A1提出了类似的技术。
因此，已知的现有技术的缺点包括高资金支出和反应器的复杂性(特别是对管束反应器而言)，以及因可流化材料(催化剂)和/或传热介质的限制所导致的流化床反应器的有限应用潜力。特别地，流化床反应器不能直接放大。
因此，本发明的目的是提供一种实施吸热反应的改进方法和一种用于实施吸热反应的改进装置，其可用于克服现有技术的缺点。特别地，所述目的能以可接受的资金支出和理想的最佳资源利用率实施吸热反应。
所述目的通过一种实施吸热反应的方法实现，其包括如下方法步骤：
a)外部加热至少两根反应管(5)，其中反应管(5)垂直设置在至少一个加热室(3)中，且各反应管(5)至少部分填充有可流化材料，
b)将至少一种气态反应物(E)引入反应管(5)中，
c)在反应管(5)中形成流化床(7)，
d)在反应管(5)中在第一温度(T1)和第一压力(P1)下实施吸热反应，其中反应体积分布在至少两根反应管(5)中，和
e)从反应管(5)中排出反应产物(P)。
本发明的方法可使用本发明的装置(1)实施。用于实施吸热反应的本发明装置(1)包括：
-至少一个加热室(3)，
-至少两根反应管(5)，其中反应管(5)垂直设置在加热室(3)中，且各反应管(5)至少部分填充有可流化材料，
-对各反应管(5)的至少一个气态反应物(E)进入点(9)，
-对各反应管(5)的至少一个反应产物(P)排出点(11)，和
-至少一个用于外部加热反应管(5)的加热装置(13)。
本发明的方法兼具在流化床中反应和在管束反应器中反应的优点，即催化剂材料的间接加热通过间接加热位于各反应管中的多个流化床而实现。此处，反应体积无需是连续的，而是可分布在多个垂直安装在燃烧室中的反应管中。通过反应管(5)壁间接加热而供应反应热量以及由流化床提供的高传热系数(从流化床至管壁的传热，α～100-1000W/(m2·K))使得可获得分布在反应管内的基本上等温的反应区。与现有技术方法相比，这显著简化了方法程序，同时降低了成本。
本发明的另一个优点是由于流化床的长度L与其直径D之间的约3-30的高L/D比(也称为L/D比或长细比)而具有降低的颗粒和气体反混，与之相比，常规流化床具有1-3的L/D比。这使得可获得更高的选择性和提高的产率。
本发明的装置(1)显示出与常规固定床反应器(管束固定床反应器)相比明显改善的传热。本发明装置(1)的结构具有与使用惰性颗粒作为传热介质的流化床反应器相比降低的设备复杂性，这是因为无需提供用于循环惰性颗粒的颗粒系统。这也降低了因循环通过惰性颗粒而造成的催化剂颗粒上的机械磨损。此外，由于无惰性颗粒堵塞一部分反应体积，反应器的时空产率得以提高。最后，由于不再需要处理惰性颗粒，显著简化了工艺程序。
与常规管束反应器相比的另一显著优点是各反应管(5)可具有大得多的直径(高达1500mm，在一些情况下高达3000mm)。因此管数量显著减少，由此简化了反应器的结构。此外，能更简单地通过用相同的催化剂质量填充装置(1)的所有管而确保流动在反应管(5)中的相等分布。
在本发明的装置(1)中，不需要内部换热器表面，即反应管中的配件。因此，可流化材料沿基本上平行于反应管(5)壁的方向运动。出于下述两个原因，这是特别有利的：
1.对反应管(5)磨损的敏感性显著降低；
2.在具有沉积碳质材料(结焦)倾向的反应中，抑制了反应管(5)壁上的沉积物的形成，因此抑制了流动横截面的堵塞。
此外，在本发明的装置(1)中，结构材料上的载荷得以降低，这是因为反应管(5)的大直径消除了流化床脉动所引发的共振风险。因此，所用材料的本征频率显著高于流化床的脉动频率。例如，长度L＝10m且外径D＝1000mm的管的本征频率为约26Hz。因此，在本发明的装置(1)中，该振动(即共振)导致结构材料中的应力且最终导致任何裂纹的产生加速，由此破坏管壁微结构的风险明显降至最低。
下文更详细地描述本发明。
本发明首先提供了(如上文已述的那样)一种实施吸热反应的方法，其包括方法步骤a)-e)。本发明的方法优选使用本发明的装置(1)(同样如上文所述)实施。如果就本发明的方法而言，下文还描述了装置特征，则该装置特征优选涉及就本发明方法而言更特别地定义的本发明装置(1)。
就本发明而言，术语“吸热反应”通常应理解为意指具有(-ΔHr)<0的反应焓的反应(参见Ullmann’s Encylopedia of Industrial Chemistry，第7版，Wiley，2010；Principles of Chemical Reaction Engineering，K.RoelWesterterp，RuudJ.Wijngaarden)。该类反应可为消去反应、脱氢、脱水、烃裂解反应、分解反应、烃的碳-碳偶联反应或其组合。
方法步骤a)包括外部加热至少两根反应管(5)，其中反应管(5)垂直设置在至少一个加热室(3)中，且各反应管(5)至少部分填充有可流化材料。所述外部加热特别为间接加热。
术语“加热室”应理解为意指以各种方式引入能量的基本上密闭的空间，其中所述能量传递给设置在加热室(3)中的反应管(5)。特别地，本发明加热室(3)的目的是确保反应管(5)的均匀加热。在本发明的情况下，“均匀”意指反应管(5)圆周上的热流密度分布的波动应不超过30％，优选应不超过15％，且反应管之间的热流波动必须不超过30％，优选必须不超过15％。
例如，100K的温度波动对脱氢方法是有害的。当温度降低过大时，反应物停止反应，且当温度升高过大时，形成碳质沉积物(焦炭)的选择性也提高，由此降低目标产物的产率。这显示在下文的实施方案中。
存在至少两根反应管(5)。在本发明的方法中，优选使用2-15 000根管，特别是10-10 000根管，优选20-10 000根管，特别是50-5000根管，更优选100-5000根管。
根据本发明，可使用选自分类组Geldart A和/或Geldart B和/或Geldart C和/或Geldart D及其混合物的颗粒作为可流化材料，所述分组是本领域技术人员所已知的。Geldart A包含具有小平均粒度和小于1.4g/cm3密度的颗粒，Geldart B包含具有40-500μm粒度和1.4-4.0g/cm3密度的颗粒，Geldart C包含具有20-30μm粒度的颗粒，Geldart D包含具有>500μm粒度和1.4-4.0g/cm3密度的颗粒(参见“Types of Gas Fluidization”，D.Geldart，Powder Technology，7(1973)285-292)。
至少50％的颗粒优选包含至少一种对本发明反应呈活性的组分。
甲烷脱氢芳构化以获得苯的反应可使用例如包含其上施加有至少一种金属的多孔载体的催化剂进行。根据本发明，优选载体包含至少一种沸石，特别优选载体具有选自结构类型pentasil和MWW的结构，尤其优选载体具有选自结构类型MFI、MEL、混合MFI/MEL和MWW结构类型的结构。非常特别优选使用ZSM-5或MCM-22型沸石。沸石结构类型的描述对应于W.M.Meier，D.H.Olson和Ch.Baerlocher的那些(参见“Atlas of Zeolite StructureTypes”，Elsevier，第3版，Amsterdam 2001)。这些沸石颗粒可归类为Geldart A组。
催化剂(例如用于脱氢芳构化)通常包含至少一种选自周期表第3-12族的金属。根据本发明，优选催化剂包含至少一种选自第6-11主族的过渡金属的元素。特别优选催化剂包含Mo、W、Re、Fe、Ru、Os、Co、Rh、Ir、Ni、Pd、Pt、Cu。非常特别优选催化剂包含至少一种选自Mo、W和Re的元素。根据本发明，还优选催化剂包含至少一种金属作为活性组分和至少一种其他金属作为掺杂剂。根据本发明，活性组分选自Mo、W、Re、Ru、Os、Rh、Ir、Pd、Pt。根据本发明，掺杂剂选自Cr、Mn、Fe、Co、Ni、C、V、Zn、Zr和Ga，优选选自Fe、Co、Ni、Cu。根据本发明，催化剂可包含超过一种金属作为活性组分，和超过一种金属作为掺杂剂。这些各自选自对活性组分和掺杂剂所列的金属。
此外，对其他反应体系而言，可使用非金属催化剂。
已证明当吸热反应是非均相催化的且可流化材料是可用于该吸热反应的可流化催化剂时，这对本发明方法的效率是有利的。与现有技术方法相反，本发明的催化剂不暴露于用于产生热量的烟道气燃烧中，因此所述催化剂无需对该条件是化学和机械稳定的。这拓宽了可工业应用的催化剂的范围。
方法步骤b)包括将至少一种气态反应物(E)引入反应管(5)中。可用的气态反应物根据待实施的具体吸热反应选择。合适反应物的范围是本领域技术人员所已知的。实例包括：用于将甲烷脱氢芳构化以获得苯的CH4；用于将丙烷脱氢以获得丙烯的C3H8、H2O和H2；用于将丁烷脱氢以获得丁烯的C4H10、H2O和H2；用于合成苯乙烯的C8H10和H2O；用于蒸气重整的CH4和H2O；和用于天然气干重整以获得合成气的CH4和CO2；用于天然气热解的CH4。除反应物之外，原料中还包含杂质，这可为化学惰性的或化学活性的。化学惰性的材料在不发生改变下离开反应器，而化学活性组分在反应器中完全或部分转化。
根据本发明，方法步骤c)包括在反应管(5)中形成流化床(7)。流化床(7)可以以成泡和湍流方案或者以“快速流化”方案运行。所述方案根据本领域技术人员已知的Grace图(参见Fluidization Engineering，第2版，Butterworth-Heinemann，1991；Daizo Kunii，Octave Levenspiel)分类。
方法步骤d)包括在反应管(5)中在第一温度(T1)和第一压力(P1)下实施吸热反应，其中反应体积分布在至少两根反应管(5)中。方法步骤d)中所选的第一温度(T1)和第一压力(P1)主要取决于待实施的吸热反应。可用于特定反应的温度和压力范围是本领域技术人员所已知的。优选温度(T1)为500-1000℃，优选为500-900℃，更优选为600-850℃。第一压力(P1)为0.1-30巴，优选为0.1-20巴，更优选为0.1-10巴。压力(P1)特别为绝对压力。
方法步骤e)包括从反应管(5)中排出反应产物(P)。具体的反应产物(P)，即反应产物的组成是本领域技术人员所已知的，且包含根据所实施的具体吸热反应形成的挥发性、在反应条件下为气态的物质。反应产物(P)可为单一产物，或者为两种或更多种产物。反应产物还包含副产物和/或杂质。
由于在本发明的方法期间，碳质材料(焦炭)可沉积在催化剂上，因此本发明的方法优选包括方法步骤f)，在第二温度(T2)和第二压力(P2)下使用合适的再生气体(R)再生催化剂。
适于再生催化剂材料，即移除催化剂颗粒上的碳质沉积物的条件，例如第二温度(T2)、第二压力(P2)和进料组成通常不同于吸热反应所需的温度和压力(T1和P1)及其进料组成。因此，有利地是提供独立的方法步骤来再生催化剂。
进料组成为在方法步骤b)和/或f)中引入反应管中的流体料流的组成。
优选温度(T2)为500-1000℃，优选为500-900℃，更优选为600-850℃。第二压力(P2)为0.1-30巴，优选为0.1-20巴，更优选为0.1-10巴。特别地，这适用于脱氢芳构化。
尽管对温度(T1，T2)和压力(P1，P2)所述的范围似乎并无不同，然而实际的温度(T1，T2)和压力(P1，P2)可根据具体方法而不同地调节。例如，在脱氢芳构化的情况下，吸热反应特别地在低压力下实施，而再生特别地在高压力下有效。
特别地，方法步骤f)可与方法步骤b)、c)、d)和e)完全或部分平行地进行，因此在任何时候都无需中断吸热反应。就此而言，额外有利的是处于生产模式的反应管(5)的数量可变，且一根或多根反应管(5)可根据吸热反应要求而联机或脱机。就此而言，“可变”意指根据所需的反应体积，一根或多根反应管(5)用于吸热反应，而剩余的反应管(5)用于再生或者待机。
在一个方案中，反应管(5)可组合，从而形成彼此独立地以生产模式和/或再生模式或待机交替运行的组。
根据本发明，“生产模式”应理解为意指包括一种或多种反应类型的工艺步骤，其中这些反应类型包括例如消去反应、脱氢、烃裂解、脱水、芳构化或分解反应。
根据本发明，“再生模式”应理解为意指包括一个或多个如下步骤的工艺步骤：用惰性气体吹扫、用贫空气或未稀释空气氧化催化剂的一种或多种组分、还原催化剂的一种或多种组分、用例如CO2、H2或H2O气化催化剂上的碳质沉积物。
根据本发明，“待机”应理解为意指一根或多根反应管(5)或组合成组的反应管(5)既不以生产模式运行，也不以再生模式运行的状态。
各反应管(5)或组合成组的反应管(5)的可变运行使得可根据需要设置本发明方法的生产量，而无需额外的资金支出且无需显著改变反应程序。可进一步将多根反应管(5)切换至再生循环，而其他反应管(5)以生产循环运行。这意味着无需停止吸热反应以再生催化剂材料，相反，其可以以基本上连续运行的模式实施。此外，当各反应管(5)或组合成组的反应管(5)不是特定时刻所需容量所需要的时，各反应管(5)或组合成组的反应管(5)可待机。
在本发明方法的一个方案中，将气态反应物(E)和再生气体(R)在至少两个不同的点处引入相应的反应管(5)中。优选将所述气体同时引入。此处，流化床(7)为垂直分区且具有生产区和再生区(催化剂颗粒在其间周期性地循环)的流化床。这降低了因压力和温度随时间波动所导致的机械应力。
由于本发明的方法预期用于实施强吸热反应，方法步骤a)包括引入至少5MW，特别是50-500MW的功率。
本发明的方法特别用于C1-C4脂族化合物的非氧化性脱氢芳构化，这是因为该吸热反应的能量需求特别大。
C1-C4脂族化合物的非氧化性脱氢芳构化优选使用包含其上施加有至少一种金属的多孔载体的催化剂。根据本发明，优选载体包含至少一种沸石，特别优选载体具有选自结构类型pentasil和MWW的结构，尤其优选载体具有选自结构类型MFI、MEL、混合MFI/MEL和MWW结构类型的结构。非常特别优选使用ZSM-5或MCM-22型沸石。沸石结构类型的描述对应于W.M.Meier，D.H.Olson和Ch.Baerlocher的那些(参见“Atlas of Zeolite StructureTypes”，Elsevier，第3版，Amsterdam 2001)。这些沸石颗粒可归类为Geldart A组。
所述催化剂通常包含至少一种选自周期表第3-12族的金属。根据本发明，优选催化剂包含至少一种选自第6-11主族的过渡金属的元素。特别优选催化剂包含Mo、W、Re、Fe、Ru、Os、Co、Rh、Ir、Ni、Pd、Pt、Cu。非常特别优选催化剂包含至少一种选自Mo、W和Re的元素。根据本发明，还优选催化剂包含至少一种金属作为活性组分和至少一种其他金属作为掺杂剂。根据本发明，活性组分选自Mo、W、Re、Ru、Os、Rh、Ir、Pd、Pt。根据本发明，掺杂剂选自Cr、Mn、Fe、Co、Ni、C、V、Zn、Zr和Ga，优选选自Fe、Co、Ni、Cu。根据本发明，催化剂可包含超过一种金属作为活性组分，和超过一种金属作为掺杂剂。这些各自选自对活性组分和掺杂剂所列的金属。
对上述非氧化性脱氢芳构化而言，第一温度(T1)为600-800℃，第二温度(T2)为500-800℃，第一压力(P1)为0.1-10巴，第二压力(P2)为0.1-30巴。压力(P1，P2)特别为绝对压力。
本发明进一步提供了用于实施吸热反应的装置(1)(如上文所述)，其包括：
-至少一个加热室(3)，
-至少两根反应管(5)，其中反应管(5)垂直设置在加热室(3)中，且各反应管(5)至少部分填充有可流化材料，
-对各反应管(5)的至少一个气态反应物(E)进入点(9)，
-对各反应管(5)的至少一个反应产物(P)排出点(11)，和
-至少一个用于外部加热反应管(5)的加热装置(13)。
本发明的装置(1)优选用于上文所述的实施吸热反应的方法中。如果在下文中就装置(1)描述了方法特征，则参考上文所述的本发明方法的相应描述，除非另有说明。
装置(1)有利地为单元结构的，因此至少两根反应管(5)可与吸热反应联机或脱机。这明显提高了本发明装置(1)的灵活性。正如已就所述方法所解释的那样，气态反应物(E)的生产量可根据要求通过使各反应管(5)或组合成组的反应管(5)联机或脱机而调节。以此方式，在较小规模上优化的吸热反应可容易地复制成较高生产量的反应。常规流化床反应器需要昂贵且不便的“放大”，而在本发明的情况下，“增加数量”就足够了，这是因为此时所涉及的仅仅是将多根包含流化床(7)且已就其生产量和足够热传导而言优化的反应管(5)彼此组合。因此可在宽限度内改变设备的尺寸，且因此改变反应的生产量。因此，本发明的装置具有极宽的负载范围。
当发生可逆失活时，可在本发明的装置(1)中再生催化剂。为此，装置(1)可分成可在生产模式和再生模式之间彼此独立地切换的段。在多根反应管(5)上分割反应体积提供了如下优点：这些反应管(5)中的一些以再生模式运行，而剩余的反应管(5)以生产模式运行。这使得可以以周期性的时间间隔再生催化剂而无需中断生产。
现有技术的常规固定床反应器通常包括直径至多为100mm的反应管，而本发明装置(1)中的各反应管(5)优选具有大于100mm的直径，特别是125-1500mm的直径，在一些情况下高达3000mm的直径。这显著减少了本发明装置(1)中所需的管数量。例如，对脱氢芳构化而言，本发明的装置(1)需要使用约3000根管直径为500mm的管，而在相同容量和相同运行条件下，具有不超过100mm直径的管的管束固定床反应器需要使用约75 000根管。用作该计算的基础的运行数据是550℃的气体进入温度、700℃的反应温度和4巴的运行绝对压力。此处，将8％甲烷转化成苯的反应所需的热量为几乎140MW。总气体流速为约960t/h CH4。
为了能最佳地实施吸热反应，已证明有利的是对本发明装置(1)的加热装置(13)进行设置，从而提供至少5MW，特别是50-500MW的热输出。
本发明装置(1)的另一方案提出将至少两根反应管(5)彼此连接。该连接特别是在反应管(5)的入口和/或出口处进行。这实现了连通管的原理，因此所有彼此连接的反应管(5)中的流化床水平基本上相平。因此独立于初始填料地确保了相等分布。此外，该方案可实现装置的更简单、更快速且因此更有效地填充。
本发明进一步提供了上述装置(1)用于非氧化性脱氢芳构化C1-C4脂族化合物的用途。C1-C4脂族化合物的非氧化性脱氢芳构化本身(如上文已述的那样)是本领域技术人员所已知的。
强吸热反应如C1-C4脂族化合物的非氧化性脱氢芳构化无法再在常规管束反应器或流化床反应器中使用常规换热器以更大的规模经济地实施。因此，使用本发明的装置(1)来非氧化性脱氢芳构化C1-C4脂族化合物提供了明显的经济优势。
下文将本发明的装置(1)描述为“管束流化床反应器”。
其他目的、特征、优点和可能的应用将由本发明工作实施例的下文描述且参照附图悉知。附图中所描述和/或示意的所有特征单独或以任意组合形成本发明的主题，而与它们在权利要求或它们回引的权利要求中的组合无关。
图1显示了本发明一个实施方案中的管束流化床反应器(1)的示意图，和
图2显示了本发明反应管(5)的三个不同的实施方案a)、b)和c)的示意图，
图3a以俯视图显示了通过共用入口和共用出口彼此连接的反应管组的示意图，和
图3b显示了沿图3a的反应管组的线A-A的剖面示意图。
图1显示了用于高温吸热反应的本发明管束流化床反应器1的示意图。反应管5垂直设置在燃烧室3中。反应管5包含可流化材料以形成流化床7。在优选实施方案中，将反应物料流E从下方经由进入点9引入反应管5中以将可流化材料流化，从而形成流化床7，且还在吸热反应中转化成产物P。产物料流P在反应管5的顶部经由排出点11取出。
在图1所示的实施方案中，燃烧室3借助作为加热装置的喷射燃烧器13燃烧。喷射燃烧器13可例如使用天然气、来自分离步骤的保留物料流、来自纯化步骤的尾气或者来自其他工艺的燃料状产物作为燃料。
当将加热装置13从上方和下方导入燃烧室3中时，图1所示的设置可在反应管5的长度上实现不同的温度，特别是温度梯度。
图2a、2b和2c显示了反应管5的三个实施方案。
图2a显示了反应管5中的浸没管15，在反应期间可通过浸没管15提供和/或取出催化剂颗粒。这可补偿因在例如流化床7中磨损而导致的催化剂质量损失。此外，可取出催化剂颗粒，从而改变流化床7的体积或者在外部再生催化剂材料。由于在本实施方案中，在运行期间可连续取出催化剂且用新鲜催化剂置换，因此催化剂的更换也还更简单，而在固定床反应器中，例如更换催化剂需要停车、冷却并打开反应器。本实施方案明显减少了停工时间，且明显提高了反应器的利用率。催化剂更换通常每隔两年进行。
图2b显示了横截面在其长度上变化的反应管5。该设置使得对体积增大的反应而言，可保持流化方案基本上恒定。
图2c显示了具有两个进入点9a和9b的反应管5，由此可将流化床7分成两个区域。这提高了在一根且同一根反应管5中建立反应区和再生区的可能性。在这种情况下，将再生气体R经由进入点9a引入，从而再生已被碳质沉积物(结焦的)失活的催化剂颗粒。颗粒在两个区域之间的传输由于所述颗粒在流化床中的自然运动而进行。气态反应物E经由进入点9b供应。
在图2b和2c中，可通过选择合适的管横截面和通过靶向调节流动速率而在流化床7中形成两个区域。当在下部区域中形成再生区且在上部区域中形成反应区时，此时在反应期间可有利地以连续运行的方式再生催化剂颗粒。
图3a以俯视图显示了反应管5组的示意图。反应管5经由共用入口17和共用出口19彼此连接。这实现了连通管的原理。所示的该组形成了一个单元反应器的单元。
图3b显示了沿图3a的线A-A的剖面示意图。入口和出口的互联确保了在该组的所有反应管5中的均一催化剂填充度，即流化床7的均一水平。
下文所给的是可用本发明方法和本发明装置1实施的吸热反应的具体工作实施例。
脱氢芳构化反应和催化剂的再生
脱氢芳构化反应和催化剂的再生在反应器中在表1所示的条件下进行。WHSV(重量时空速率)以甲烷(对反应而言)或氢气(对再生而言)的质量流速除以装置中的催化剂量给出。
所用的催化剂为喷雾干燥的ZSM-5，其包含6％的钼和1％的镍。粒度为45-200μm。
反应在750℃和2.5巴(绝对)下进行。这转化了5％的甲烷。苯选择性为80％。
在10小时的反应时间后，将催化剂再生。再生使用氢气在810℃和4巴(绝对)下进行。氢气转化率为5％，且仅形成甲烷。
两种反应均在弱起泡流化状态下进行。
表1
反应 再生
T[℃] 750 810
p[巴，表压] 1.5 3
WHSV[kg/kg/h] 0.13 0.071
XCH4或H2[％] 5(CH4) 5(H2)
SC6H6[％] 80
丙烷脱氢
化学计量方程：
催化剂：
负载在Al2O3或ZrO2上的Pt/Sn(以及其他VIII族金属)
负载在Al2O3或ZrO2上的Cr2O3
负载在沸石(丝光沸石，MCM-41，SAPO)、TiO2或Al2O3上的Ga2O3生产阶段：
进料组成
C3H8(30-100体积％)，H2(0-50体积％)，H2O(0-50体积％)，C2H6(＜5体积％)，CH4(＜5体积％) (II)
运行条件：温度：500-650℃，压力：0.3-5巴(绝对)
再生阶段：
进料组成
O2(0-30体积％)，H2(0-100体积％)，H2O(0-100体积％)，N2(0-100体积)
(III)
运行条件：温度：500-700℃，压力：0.3-5巴(绝对)
丁烷氢化
化学计量方程：
C4H10：正丁烷或异丁烷
C4H8：1-丁烯或异丁烯
用于方程(IV.1)的催化剂：
负载在Al2O3或ZrO2上的Pt/Sn(以及其他VIII族金属)
负载在Al2O3或ZrO2上的Cr2O3
负载在沸石(丝光沸石，MCM-41，SAPO)、TiO2或Al2O3上的Ga2O3用于方程(IV.1)和(IV.2)的催化剂：
负载在Al2O3或ZrO2上的Cr2O3
生产阶段：
进料组成
C4H10(30-100体积％)，H2(0-50体积％)，H2O(0-50体积％)，C2H6(＜5体积％)，CH4(＜5体积％) (V)
运行条件：温度：500-650℃，压力：0.3-5巴(绝对)
再生阶段：
进料组成
O2(0-30体积％)，H2(0-100体积％)，H2O(0-100体积％)，N2(0-100体积)
(VI)
运行条件：温度：500-700℃，压力：0.3-5巴(绝对)
乙苯氢化
化学计量方程：
催化剂：
Fe2O3/Cr2O3/K2CO3
生产阶段：
进料组成
C8H10(10-50体积％)，H2(0-10体积％)，H2O(50-90体积％)，C6H6(＜5体积％)，C7H8(＜5体积％) (VIII)
运行条件：温度：550-650℃，压力：0.3-2巴(绝对)
再生阶段(很少使用)：
进料组成
O2(0-30体积％)，H2(0-100体积％)，H2O(0-100体积％)，N2(0-100体积)
(IX)
运行条件：温度：500-700℃，压力：0.3-5巴(绝对)
烃重整(天然气，石脑油)
化学计量方程：
催化剂：
负载在α-Al2O3、MgO或Al-Mg尖晶石上的Ni
六铝酸Ni，Co
生产阶段：
进料组成
H2O：CnHm(n：4n)，CO2：CnHm(0：2n) (XI)
运行条件：温度：700-1000℃，压力：5-50巴(绝对)
再生阶段(很少使用)：
进料组成
O2(0-30体积％)，H2(0-100体积％)，H2O(0-100体积％)，N2(0-100体积)
(XII)
运行条件：温度：500-1000℃，压力：1-50巴(绝对)。

Claims (15)

1.一种实施吸热反应的方法，包括如下方法步骤：
a)外部加热至少两根反应管(5)，其中反应管(5)垂直设置在加热室(3)中，且各反应管(5)至少部分填充有可流化材料，
b)将至少一种气态反应物(E)引入反应管(5)中，
c)在反应管(5)中形成流化床(7)，
d)在反应管(5)中在第一温度(T1)和第一压力(P1)下实施吸热反应，其中反应体积分布在至少两根反应管(5)中，和
e)从反应管(5)中排出反应产物(P)。
2.根据权利要求1的方法，其中所述吸热反应为非均相催化的且所述可流化材料为可用于所述吸热反应的可流化催化剂。
3.根据权利要求2的方法，进一步包括如下方法步骤：
f)在第二温度(T2)和第二压力(P2)下使用合适的再生气体(R)再生催化剂。
4.根据权利要求3的方法，其中方法步骤f)与方法步骤b)、c)、d)和e)完全或部分平行地进行。
5.根据权利要求1-4中任一项的方法，其中处于生产模式的反应管(5)的数量可变，且一根或多根反应管(5)根据需要与所述吸热反应联机或脱机。
6.根据权利要求1-5中任一项的方法，其中在至少两个不同的点处将气态反应物(E)和再生气体(R)引入相应的反应管(5)中。
7.根据权利要求1-6中任一项的方法，其中方法步骤a)包括引入至少5MW，特别是50-500MW的功率。
8.根据权利要求1-7中任一项的方法，其中所述吸热反应为C1-C4脂族化合物的非氧化性脱氢芳构化。
9.根据权利要求8的方法，其中用于C1-C4脂族化合物的非氧化性脱氢芳构化的催化剂为包含多孔载体的催化剂，所述多孔载体具有至少一种施加于其上的金属。
10.根据权利要求8或9的方法，其中第一温度(T1)为500-1000℃，第二温度(T2)为500-900℃，第一压力(P1)为0.1-10巴和/或第二压力(P2)为0.1-30巴。
11.一种用于实施吸热反应的装置(1)，其包括：
-至少一个加热室(3)，
-至少两根反应管(5)，其中反应管(5)垂直设置在加热室(3)中，且各反应管(5)至少部分填充有可流化材料，
-对各反应管(5)的至少一个气态反应物(E)进入点(9)，
-对各反应管(5)的至少一个反应产物(P)排出点(11)，和
-至少一个用于外部加热反应管(5)的加热装置(13)。
12.根据权利要求11的装置(1)，其中装置(1)为单元结构的，因此每根反应管(5)可独立地与所述吸热反应联机和脱机。
13.根据权利要求11或12的装置(1)，其中各反应管(5)具有大于100mm的直径，特别是125-1500mm的直径。
14.根据权利要求11-13中任一项的装置(1)，其中至少两根反应管(5)彼此连接。
15.根据权利要求11-14中任一项的装置(1)用于C1-C4脂族化合物的非氧化性脱氢芳构的用途。
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