CN109072091A - 在用于流化床反应器之前使携氧再生催化剂反应的方法 - Google Patents

在用于流化床反应器之前使携氧再生催化剂反应的方法 Download PDF

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CN109072091A
CN109072091A CN201780026086.7A CN201780026086A CN109072091A CN 109072091 A CN109072091 A CN 109072091A CN 201780026086 A CN201780026086 A CN 201780026086A CN 109072091 A CN109072091 A CN 109072091A
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CN109072091B (zh
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M·T·普雷茨
李力伟
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Dow Global Technologies LLC
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Abstract

提供了一种在用于流化床反应器之前使含氧再生催化剂流反应的方法，其包含提供再生催化剂流，所述再生催化剂流包含至少0.001重量％氧；使所述再生催化剂流与燃料源反应，从而形成氧化物并减少所述再生催化剂流中的氧的量，以产生可用的再生催化剂流；和将所述可用的再生催化剂流注入到烃流化床反应器中。

Description

在用于流化床反应器之前使携氧再生催化剂反应的方法
相关申请的交叉引用
本申请要求2016年5月9日提交的美国临时申请62/333,334的优先权，所述申请以全文引用的方式并入本文中。
技术领域
本发明涉及一种在用于流化床反应器之前使在再生催化剂中的氧反应的方法。
背景技术
流化床反应器用于许多工业化学方法，例如烃脱氢、流化催化裂化(FCC)和甲醇制烯烃(MTO)。
在烃脱氢生产烯烃的方法中，此项技术已教示，在注入到脱氢反应器之前，必须汽提再生催化剂以使再生催化剂流中的氧最小化。例如，可以用氮流汽提再生催化剂流。
包括氧汽提器增加了烃脱氢方法的资金投入、由于氮消耗而增加了操作成本和增加了单元操作的复杂性。因此，可以考虑消除单元操作。这引起了氧被转移到脱氢反应器和将有价值的原料降解为价值较低的产品的问题。
因此，用于最小化与再生催化剂一起到达流化床反应器中的氧量的方法是有用的。
发明内容
在一个实施例中，本公开提供了一种在用于流化床反应器之前使含氧再生催化剂流反应的方法，其包含提供再生催化剂流，所述再生催化剂流包含至少0.001重量％氧；使再生催化剂流与燃料源如甲烷、乙烷、乙烯、丙烷、丙烯、氢或焦炭反应，从而形成氧化物并减少再生催化剂流中的氧的量，以产生可用的再生催化剂流；和将可用的再生催化剂流注入到烃流化床反应器中。在一个实施例中，燃料的量将至少是反应生成可用氧所需的化学计算量。
附图说明
出于说明本发明的目的，在附图中示出了示例性的形式；然而，应理解，本发明不限于所示的精确布置和工具。
图1是说明用于操作本发明方法的实施例的一种设备配置的示意图。
具体实施方式
在第一实施例中，本公开提供了一种在用于流化床反应器之前使含氧再生催化剂流反应的方法，其包含提供再生催化剂流，所述再生催化剂流包含以再生催化剂流的总重量计，至少0.001重量％氧；使再生催化剂流与燃料源反应，从而形成氧化物并减少再生催化剂流中的氧的量，以产生可用的再生催化剂流；和将可用的再生催化剂流注入到烃流化床反应器中。本文中包括并公开了来自至少0.001重量％氧的所有个别值和子范围；例如，再生催化剂流中的氧的量可以为至少0.001、0.01、0.1或0.5重量％。本文中包括并公开了来自至少0.001重量％的所有个别值和子范围。在具体实施例中，再生催化剂流中的氧的量可以在0.001至0.5重量％，或在替代方案中，0.001至0.05重量％，或在替代方案中，0.001至0.1重量％，或在替代方案中，0.005至0.1重量％的范围内。
本公开还提供根据本文中所公开的任何实施例的方法，不同之处在于燃料源选自由以下组成的组：甲烷、氢、乙烷、乙烯、丙烷、丙烯、焦炭及其两种或更多种的任何组合。在某个实施例中，燃料源包含在用过的催化剂粒子上呈残余物形式的焦炭。在一个具体实施例中，燃料源包含甲烷。在又另一实施例中，燃料源包含焦炭。在又另一实施例中，燃料源包含甲烷和焦炭。
在另一实施例中，本公开提供了根据本文中所公开的任何实施例的使含氧再生催化剂流反应的方法，不同之处在于燃料源包含甲烷和合并的再生催化剂流并且甲烷包含至少0.001重量％甲烷。
在另一实施例中，本公开提供了根据本文中所公开的任何实施例的使含氧再生催化剂流反应的方法，不同之处在于燃料源包含含焦炭残余物的用过的催化剂和合并的再生催化剂流，并且用过的催化剂包含至少0.001重量％焦炭残余物。
在另一实施例中，本公开提供了根据本文中所公开的任何实施例的使含氧再生催化剂流反应的方法，不同之处在于再生催化剂流和蒸气燃料源在550℃至750℃的温度下反应。本文中包括并公开了来自550℃至750℃的所有个别值和子范围；例如反应温度可以为550、600、650或700℃的下限值至575、625、675、725或750℃的上限值。例如，反应温度可以在550℃至750℃，或在替代方案中，550℃至650℃，或在替代方案中，650℃至750℃，或在替代方案中，580℃至690℃，或在替代方案中，620℃至680℃的范围内。
在另一实施例中，本公开提供了根据本文中所公开的任何实施例的使含氧再生催化剂流反应的方法，不同之处在于在将可用的再生催化剂流注入到烃流化床反应器中的步骤之前，再生催化剂流和蒸气燃料源接触至少0.2秒的时间。本文中公开并包括了来自至少0.2秒的所有个别值和子范围；例如，反应时间可以为0.2、0.4、0.6、0.8、1.0、1.2、1.4或1.6秒的下限值。在一个具体实施例中，用于再生催化剂流和蒸气燃料源的反应时间可以为10秒的上限值。本文中包括并公开了来自不超过10秒的所有个别值和子范围。例如，反应时间可以为10、8、6、4、2或0.5秒的上限值。例如，用于再生催化剂流和蒸气燃料源的反应时间可以为0.40至2.00秒，或在替代方案中，0.40至1.20秒，或在替代方案中，1.20至2.00秒，或在替代方案中，0.40至1.60秒，或在替代方案中，0.70至2.00秒。
示例性蒸气燃料源包括乙烷、甲烷、乙烯、丙烷、丙烯、氢及其两种或更多种的任何组合。
在另一实施例中，本公开提供了根据本文中所公开的任何实施例的使含氧再生催化剂流反应的方法，不同之处在于在将可用的再生催化剂流注入到烃流化床反应器中的步骤之前，再生催化剂流和固体燃料源在400℃至700℃的温度下反应。本文中包括并公开了来自400℃至700℃的所有个别值和子范围；例如，反应时间可以为400、450、500、550、600或650℃的下限值至425、475、525、575、625、675或700℃的上限值。例如，用于再生催化剂流和固体燃料源之间的反应的反应温度可以在400℃至700℃，或在替代方案中，400℃至550℃，或在替代方案中，550℃至700℃，或在替代方案中，480℃至600℃，或在替代方案中，500℃至630℃的范围内。
在另一实施例中，本公开提供了根据本文中所公开的任何实施例的使含氧再生催化剂流反应的方法，不同之处在于在将可用的再生催化剂流注入到烃流化床反应器中的步骤之前，再生催化剂流和固体燃料源反应至少0.1秒的反应时间。本文中公开并包括了来自至少0.1秒的所有个别值和子范围；例如，反应时间可以为0.1、0.20、2.0、20或40秒的下限值。在一个具体实施例中，用于再生催化剂流和蒸气燃料源的反应时间可以为60秒的上限值。本文中包括并公开了来自不超过60秒的所有个别值和子范围。例如，反应时间可以为60、55、45、25、2或0.2秒的上限值。例如，用于再生催化剂流和蒸气燃料源的反应时间可以为0.1至60秒，或在替代方案中，0.1至40秒，或在替代方案中，20至60秒，或在替代方案中，0.10至10秒，或者在替代方案中，0.1至20秒。
示例性固体燃料源包括在用过的催化剂上的焦炭、焦炭残余物。
本公开的方法可以与用于对以下至少一种且优选两种进行脱氢的方法结合使用：1)链烷烃化合物，优选是具有2至6个碳原子但更优选少于5个碳原子的低碳烷烃，例如乙烷、丙烷、异丁烷和正丁烷，分别生成对应的烯烃，即乙烯、丙烯、异丁烯和正丁烯，和2)烷基芳烃化合物，优选低碳烷基芳烃化合物，如乙基苯、丙基苯、异丙基苯和甲基乙基苯，分别生成对应的乙烯基芳烃化合物(即“烯基芳族”)，即苯乙烯、异丙基苯或α-甲基苯乙烯。描述了本发明的几个实施例，包括低碳烷烃和烷基芳烃的同时和分别脱氢。本发明可用于分别由乙基苯和乙烷制备苯乙烯和乙烯。同样，异丙基苯和丙烯可分别由丙基苯和丙烷制备。
烃脱氢反应器的类型和条件公开于例如WO 2005/077867和PCT/US16/21127中，其公开内容以其全文并入本文中。
脱氢反应器产物混合物和流化催化剂在反应器圆筒中上升。在提升管反应器的顶部，分离出用过的催化剂和烃产物。用过的催化剂沉降在提升管外壁和反应器壳体内壁之间的环形空间中。然后通常将用过的催化剂传送至再生器(regenerator)/再活化器(reactivator)，其中催化剂与再生流体接触，再生流体通常是含氧气体和用于燃烧任何剩余烃并加热催化剂的补充燃料，且再生催化剂被送回脱氢反应器中。用过的催化剂也可以不经过再生就再循环到反应器中。
参考图1，显示了例如用于生产丙烯的专用催化脱氢系统1。催化脱氢系统1包括催化脱氢反应器10，通过进料管线15将一种或多种烃进料注入到所述催化脱氢反应器10中。再生催化剂可以首先通过管线20进料到管线25中，然后从管线25被传递到流化床脱氢反应器10中。产物流离开反应器10进入催化剂分离区30，其中流化催化剂粒子与产物流的气态组分分离。在图1所示的实施例中，催化剂分离区30包含多个旋风分离器35，每个旋风分离器35终止于浸入管40，所述浸入管40注入到汽提区段45中。流化气体通过进料管线75进入反应器再循环催化剂流化/汽提区段45，进料管线75在通常用于流化应用的分配器中将流化气体分布在整个环形横截面上。
在汽提内部区段45中，催化剂粒子可以浸泡在流化气体中，所述流化气体包含甲烷、天然气、乙烷、氢、氮、蒸汽或其任何组合。这种流化在美国专利申请第62/333,313号中公开，其公开内容以其全文并入本文中。在此实施例中，甲烷可任选地通过通向标准流化床分配器的进料管线75进入汽提内部区段45中，所述分配器将气体均匀地分布在环形横截面上。替代地，一部分分离的催化剂粒子可以进入用过的催化剂进料管线55并被传递到催化剂再生器系统60中。在本发明方法的一个实施例中，将一些任选地包括甲烷的用过的催化剂流传递到管线25，在管线25中，所述用过的催化剂流进入氧反应区65，在其中与再生催化剂流接触。通过控制再生催化剂和再循环的用过的催化剂的量对氧反应区65进行温度控制，使得氧与在用过的催化剂和/或甲烷和/或其它燃料上存在的焦炭残余物发生反应。然后将此反应的反应产物送回脱氢反应器10中。在氧反应区65中发生的反应减少了进入脱氢反应器10的氧的量。在一个具体实施例中，不使用氮从再生催化剂流中汽提氧。
实例
以下实例说明本发明但是并不意欲限制本发明的范围。
发明实例1：甲烷作为燃料源
表1中的数据是在内径为1.5英寸的竖直36英寸石英玻璃反应器上收集的。反应器装载有50克脱氢催化剂，其具有下列组成：在优选实施例中，催化剂包含0.1至34重量％，优选0.2至3.8重量％的氧化镓(Ga2O3)；按重量计百万分之1至300(ppm)，优选50至300ppm的铂；0至5重量％，优选0.01至1重量％的碱和/或碱土金属如钾；0.08至3重量％的二氧化硅；和补足到100重量％的氧化铝，其导致催化剂床高度为2.2英寸。将入口气体引入反应器的底部，并使用石英玻璃料沿反应器直径分配气体。入口气体的体积流量为1100标准立方厘米/分钟。入口气体流量导致催化剂流化。入口气体组成为9.6％O2、1.6％He，0.5-2％甲烷和补足到100％的氮。在475℃和700℃之间以及2psig的压力下测量甲烷与氧的燃烧。表2中的信息来自表1中的数据，具体地，在每个温度下的转化率是在1.3秒下50克催化剂在流化床中的气体停留时间来计算的。然后将转化率调节至100％并且在目标温度下计算新的所需停留时间，假设反应器中催化剂的沸腾床密度为66磅/英尺3，且操作密度为55磅/英尺3。
表1
温度 甲烷转化率
℃ (％)
500 13
550 30
600 60
650 80
700 100
表2
温度 约100％的甲烷转化率所需的蒸气燃料停留时间
℃ 秒
500 9.9
550 4.3
600 2.1
650 1.6
700 1.3
发明实例2：催化剂焦炭残余物作为燃料
如上所述，在热重量分析仪中进行测试以确定催化剂上焦炭的燃烧速率。将含有焦炭的催化剂在氩气中加热至目标温度。当达到目标温度时，将空气供应给单元并测量质量变化率。结果显示在表3中。在下列条件下制备含有焦炭的催化剂：在如上所述的反应器中，将1g不含稀释剂的催化剂装入反应器中，并且用2mm×2mm石英原料装满反应器，且反应器在700℃下运行1小时；丙烷流量46.24sccm；氮流量为5.14sccm；且WHSV为51/小时。
表3
温度，℃ 焦炭燃烧速率，磅O<sub>2</sub>/秒/磅催化剂
500 0.0001
600 0.0017
700 0.0020
为了计算在再生催化剂流中燃烧氧所需的时间，提供以下实例。将500,000磅/小时的再生催化剂和从反应器汽提器中再循环的500,000磅/小时的催化剂加入100磅/小时的氧。由于再循环催化剂是唯一含有燃料的催化剂，下表描述了除去氧将花费多少秒。结果显示在表4中。
表4
在不背离本发明精神和基本特质的情况下可以以其它形式实施本发明，并且因此，应参考所附权利要求书而非前文说明书来指定本发明的范围。

Claims (5)

1.一种在用于流化床反应器之前使含氧再生催化剂流反应的方法，其包含：
提供包含至少0.001重量％氧的再生催化剂流；
使所述再生催化剂流与燃料源反应，从而形成氧化物并减少所述再生催化剂流中的氧的量，以产生可用的再生催化剂流；和
将所述可用的再生催化剂流注入到烃流化床反应器中。
2.根据权利要求1所述的使含氧再生催化剂流反应的方法，其中所述燃料源包含甲烷和合并的再生催化剂流并且甲烷包含至少0.001重量％甲烷。
3.根据权利要求1所述的使含氧再生催化剂流反应的方法，其中所述燃料源包含含焦炭残余物的用过的催化剂和合并的再生催化剂流，并且用过的催化剂包含至少0.001重量％焦炭残余物。
4.根据权利要求1所述的使含氧再生催化剂流反应的方法，其中所述再生催化剂流和燃料源在580至750的温度下反应。
5.根据权利要求1所述的使含氧再生催化剂流反应的方法，其中所述燃料源包含蒸气燃料，并且在将合并的反应器再循环和再生催化剂流注入到所述烃流化床反应器中的步骤之前，所述再生催化剂流和蒸气燃料源反应0.2至10秒的反应时间，其中在氧化反应器之后的合并催化剂的活性是合并的反应器再循环和再生催化剂的至少70％。
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