CN102781881A - 用于分阶段合成烷基溴的方法和系统 - Google Patents
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Abstract
本发明涉及由烷基溴合成烃产物如高分子量烃、烯烃或其混合物的方法和系统,其中烷基溴的一个或多个流股可在不同温度下在先后或同时进行的阶段中发生反应。用于所述合成阶段中的催化剂可以相同或不同且至少在一种情况中,对所述催化剂进行选择以生成具有大量C6+链烷烃含量的烃产物。所述阶段可在一个或多个反应器中进行且所述催化剂可用于固定床或流化床中。
Description
相关专利申请的参考
本申请是2010年3月2日提交的且题目为“用于分阶段合成烷基溴的方法和系统”的未决的美国专利申请序号12/715,526的部分继续申请。
发明背景
技术领域
本发明涉及在至少两个连续或并行阶段中将烷基溴合成为高分子量烃的方法和系统,更具体地,在一个或多个实施方案中,本发明涉及在不同进料和不同温度下运行的至少两个顺序或并行阶段中合成烷基溴的方法和系统。
相关技术描述
例如通过在足以生成高分子量C3+烃的温度下在合适催化剂如合成的结晶硅铝酸盐催化剂上进行转化,可将单溴化烷烃用于生产高分子量烃如C5+汽油范围和更重的烃、以及烯烃,在所述C3+烃中的C6+馏分主要是取代的芳族化合物。由于得自这种方法的高分子量烃的C6+馏分的芳族化合物含量高于用于生产“纯净”汽油发动机燃料所期望的含量,所以作为与石油衍生的石脑油或得自天然气加工的天然汽油的高辛烷共混组分以产生发动机燃料,C6+馏分是有价值的。石油衍生的石脑油或得自天然气加工的天然汽油典型地含有大量链烷烃且辛烷等级低。由此,需要一种方法,以在合适催化剂并在合适温度下合成单溴化烷烃以产生更高分子量的C3+烃,所述C3+烃的C6+馏分含有大量C6+链烷烃并由此芳族化合物的含量下降。
在更低分子量的烷烃的溴化期间通常生成多溴化烷烃,尤其是二溴化的甲烷、三溴化的甲烷及其混合物,以及优选的单溴化烷烃。在如上所述在合适催化剂上转化烷基溴期间,这些多溴化烷烃的存在明显加快了焦炭的生成速率。这种焦炭的生成更快速地使得催化剂失活,导致在所述方法的碳功效的再生与下降之间的循环时间缩短。由此还需要明显减少在合成单溴化烷烃期间由于多溴化烷烃导致的焦炭的生成并提高更高分子量C3+烃的收率。
发明概述
为了实现上述和其他目的,且根据本发明的目的,如本文中所体现的且广泛描述的,本发明的一个特征是一种方法,所述方法包括:提供烷基溴并在第一催化剂存在下并在足以生成第一烃产物的第一温度下使得所述烷基溴的至少第一部分发生反应,所述第一烃产物至少含有具有至少5个碳原子的烃并具有大量C6+链烷烃含量。在第二催化剂的存在下并在足以生成第二烃产物的第二温度下使得所述烷基溴的第二部分发生反应,所述第二烃产物至少含有具有至少5个碳原子的烃并具有大量取代的芳族化合物含量。
在本发明的另一个特征中,一种方法包括:提供含有较低分子量烷烃并具有小于约4.0mol%C2+组分的第一进料气体流股并将溴与所述第一进料气体流股反应以生成第一烷基溴。在第一催化剂存在下并在足以生成第一烃产物的第一温度下,使得至少第一烷基溴反应,所述第一烃产物至少含有具有至少5个碳原子的烃并具有大量C6+链烷烃含量。将含有较低分子量链烷烃并主要具有C2+组分的第二进料气体流股与溴反应以生成第二烷基溴。在第二催化剂存在下并在足以生成第二烃产物的第二温度下,使得至少第二烷基溴反应,所述第二烃产物至少含有具有至少5个碳原子的烃并具有大量取代的芳族化合物含量。
在本发明还另一个特征中,提供一种系统,所述系统具有第一合成区域和第二合成区域。所述第一合成区域含有合适的催化剂并经构造以在第一温度下由包含烷基溴的合成反应物生成含有链烷烃的烃产物。所述第二合成区域与所述第一合成区域流体连通,其含有第二合适催化剂并经构造以在第二温度下由包含烷基溴的未反应部分的合成反应物生成含有取代的芳族化合物的烃产物。
在本发明的还另一个特征中,提供一种系统,其具有第一溴化反应器、第一合成反应器、第二溴化反应器和第二合成反应器。第一溴化反应器经构造以由第一溴化反应物生成包含烷基溴的第一溴化产物,所述第一溴化反应物包含具有小于约4.0mol%C2+组分的较低分子量烷烃。所述第一合成反应器与所述第一溴化反应器流体连通,其含有合适的催化剂并经构造以由第一溴化产物生成含有链烷烃的烃产物。所述第二溴化反应器经构造以由第二溴化反应物生成包含烷基溴的第二溴化产物,所述第二溴化反应物包含主要含有C2+组分的较低分子量烷烃。所述第二合成反应器与所述第二溴化反应器流体连通,其含有合适的催化剂并经构造以由第一溴化产物生成含有取代的芳族化合物的烃产物。所述第二合成反应器在高于所述第一溴化反应器的温度下运行。
附图简述
并入并构成说明书一部分的附图显示了本发明的实施方案,并与说明书一起用于解释本发明的原理。
在所述附图中:
图1是本发明方法和系统的一个实施方案的简化的方块流程图。
图2是本发明方法和系统的另一个实施方案的示意图。
图3是本发明方法和系统的另一个实施方案的示意图。
图4是本发明方法和系统的另一个实施方案的示意图。
图5是本发明方法和系统的还另一个实施方案的示意图。
图6是本发明方法和系统的还另一个实施方案的示意图。
图7是本发明方法和系统的另外实施方案的示意图。
图8是本发明方法和系统的还另外实施方案的示意图。
优选实施方案详述
如本文中所使用的,术语“烷基溴”是指单-、二-和三-溴化的较低分子量烷烃及其组合。如本文中所使用的术语“高分子量烃”是指包含C3链和更长烃链的烃。在某些实施方案中,可将高分子量烃直接用作产物(例如LPG、发动机燃料等)。在其他情况中,可将高分子量烃用作中间产物或用作进一步加工的原料。在其他情况中,可对高分子量烃进一步加工,从而例如生产汽油等级的燃料、柴油等级的燃料和燃料添加剂。在某些实施方案中,通过本发明的方法得到的高分子量烃能够直接用作具有大量链烷烃含量的发动机汽油燃料、用作燃料共混原料、或用作进一步加工的原料,例如为产生芳族化合物的聚合物如聚苯乙烯或相关聚合物的方法的芳族化合物、或进料到产生聚烯烃的方法的烯烃。如本文中所使用的术语“烯烃”是指含有2~6个碳原子和至少一个碳-碳双键的烃。如果需要,可对烯烃进行进一步加工。在某些情况中,通过本发明的方法产生的烯烃可在聚合反应(例如,使用金属茂催化剂的反应)中进一步反应以产生聚烯烃,所述聚烯烃可用于许多最终产物如塑料或合成润滑剂中。
高分子量烃、烯烃或其混合物的最终用途可取决于用于下述方法和系统的合成部分中所使用的具体催化剂、以及所述方法中所使用的运行参数。受益于本发明,其他用途对本领域技术人员是显而易见的。
较低分子量的烷烃可用作本文中所述方法的原料。如同整个本说明书所利用的,术语“较低分子量的烷烃”是指甲烷、乙烷、丙烷、丁烷、戊烷或两种以上这些单独烷烃的混合物。较低分子量的烷烃可以源自任意合适源如提供较低分子量烷烃的气体的任意一种源,无论其是自然发生的还是合成制得的。用于本发明方法中的较低分子量烷烃的源的实例包括但不限于,天然气、煤层甲烷、重新气化的液化天然气、得自气体水合物和/或水合甲烷(chlathrates)的气体、得自有机物质或微生物厌氧分解的气体、在加工沥青砂中得到的气体以及合成产生的天然气或烷烃。这些物质的组合在某些实施方案中可良好适用。在某些实施方案中,期望对进料气体进行处理以除去不期望的化合物如硫化合物和二氧化碳。在任何情况中,重要的是要注意,对本发明的方法,在进料气体中能够容忍少量二氧化碳,例如小于约2mol%。
用于本发明各种实施方案中的溴的合适源包括但不限于,元素溴、溴盐、含水氢溴酸、金属溴化物盐等。组合是合适的,但是如同本领域技术人员所理解的,使用多种源会造成额外的复杂化。下面对本发明的方法和系统的某些实施方案进行描述。尽管对所认为的所述方法所涉及的主要化学反应的主要方面按照所认为其应发生的进行了详细讨论,但是应理解,会发生副反应。不能认为本文中不能讨论任何特殊的副反应就意味着不发生副反应。相反,所讨论的内容不应认为是详尽的或限制性的。另外,尽管附图示意性显示了本发明方法的特定方面,但是不能将这些图看做对本发明的任意一种具体方法的限制。
图1中显示了通常描绘本发明方法和系统的某些实施方案的一些方面的方块流程图。用作图1中描绘的实施方案中的进料的烷基溴可由对含有较低分子量烷烃的进料气体流股进行溴化而生成,所述较低分子量的烷烃主要是甲烷并具有可接受浓度的C2+较低分子量烷烃组分。这种溴化可通过热、催化或其组合的方式进行。典型地,在较低分子量的烷烃的溴化中还会生成溴化氢。根据图1中所示本发明方法的实施方案,在引入第一阶段合成反应器4中之前,通过任意一种合适手段如换热器3可将含有烷基溴的气体流股2冷却或加热至约150℃~约300℃,更优选约225℃~约275℃。在第一阶段合成反应器中,在合适催化剂5上,在约150℃~约300℃且更优选约225℃~约275℃的温度范围并在约1~约100巴的压力下,烷基溴发生放热反应以产生期望产物(例如高分子量烃、烯烃或其混合物)。据认为,在这些条件下,在合适催化剂上,丙基溴的反应性比甲基溴和乙基溴高,由此优选合成丙基单元以生成烃产物如高分子量烃、烯烃或其混合物,所述烃产物含有大量C6+链烷烃含量并由此减少了芳族化合物的含量。在第一阶段合成反应器4中,存在于烷基溴中的单溴化烷烃中仅有一部分被转化,且可能存在的任何多溴化烷烃不易转化为重质产物或沉积到催化剂上的“焦炭”,因为存在丙基溴和温度条件更低。
在引入第二阶段合成反应器8中之前,可通过任意合适手段如换热器7对源自第一阶段合成反应器的流出物6进行加热。在第二阶段合成反应器中,在合适催化剂9上,在约300℃~约450℃的范围内且更优选在约350℃~约425℃的范围内的温度下并在约1~约100巴范围内的压力下使得流出物中所含有的甲基溴和乙基溴发生放热反应,以产生期望的烃产物(例如高分子量烃、烯烃或其混合物),将其作为烃产物流股10从第二阶段合成反应器8中移出。据认为,在这些条件下,在合适催化剂上,甲基溴和乙基溴可优先反应以使得甲基和乙基单元发生低聚,由此生成产物如高分子量烃、烯烃或其混合物,所述产物含有主要具有取代的芳族化合物的C6+馏分以及主要在C3~C5+范围的轻质烷烃。
用于第一和第二阶段合成反应器4和8中的催化剂分别为用于将烷基溴催化转化成产物烃的多种合适材料中的任意一种。在某些实施方案中,所述第一和第二阶段合成反应器可包含催化剂的固定床。在特定情况中尤其是在更大的应用中还可使用合成催化剂的流化床,所述流化床具有特定的优势如恒定地除去焦炭和对产物组合物的稳定的选择性。合适催化剂的实例包括具有作为酸性离子交换者的普通功能且还含有合成的结晶硅铝酸盐氧化物骨架的相当宽范围的材料。在某些实施方案中,结晶硅铝酸盐氧化物骨架中的一部分铝可以被镁、硼、镓和/或钛取代。在某些实施方案中,结晶硅铝酸盐氧化物骨架中的一部分硅可以任选地被磷取代。所述结晶硅铝酸盐催化剂在结晶硅铝酸盐氧化物骨架结构内通常具有大量阴离子电荷,所述阴离子电荷例如通过Na阳离子来平衡。尽管沸石催化剂通常以钠的形式得到,但是优选质子或氢形式(通过与氢氧化铵进行离子交换并随后进行煅烧),或还可使用混合的质子/钠形式。另外,通过与其他元素的阳离子进行离子交换可对沸石进行改性。可用于沸石离子交换的元素包括第一行的过渡金属、第1族(IA)、第2族(IIA)、La、Ce、Mo、V、Ag或其组合。这种随后的离子交换可代替平衡电荷的对离子,但另外可还部分代替氧化物骨架中的离子,导致对氧化物骨架的晶体构成和结构进行改性。结晶硅铝酸盐或取代的结晶硅铝酸盐可包括微孔或中孔结晶硅铝酸盐,但在某些实施方案中,可包括合成的微孔结晶沸石,例如可以为MFI结构如ZSM-5。而且,在某些实施方案中,可利用Mg、Ca、Sr、Ba、V、Ag、La或Ce的盐如Ce(NO3)3的水溶液对结晶硅铝酸盐或取代的结晶硅铝酸盐进行浸渍,干燥并在空气中进行煅烧。在某些实施方案中,所述盐可以为卤化物盐如溴化物盐,例如MgBr2。任选地,所述结晶硅铝酸盐或取代的结晶硅铝酸盐可还含有处于金属状态的约0.1~约1重量%的Pt、约0.1~5重量%的Pd或约0.1~约5重量%的Ni。尽管这种沸石材料主要是原始晶体,但是应注意,一部分结晶催化剂会由于初始离子交换或浸渍或由于在反应条件下或再生期间的操作而发生结晶度的部分损失,因此,所述催化剂可还含有明显的无定形特性,还另外保持明显的且在某些情况中是改进的活性。
用于第一和第二阶段合成反应器4和8中的具体催化剂5和9分别取决于例如所期望的具体产物烃。例如当期望主要具有C3、C4和C5+汽油范围链烷烃化合物和更重的烃馏分的产物烃时,可使用ZSM-5沸石催化剂。当期望产生包含烯烃和C6+产物的混合物的产物烃时,可使用X型或Y型沸石催化剂或SAPO沸石催化剂。合适的沸石的实例包括X型如10-X或Y型沸石,但在本发明的实施方案中可使用具有不同孔径和酸度的其他沸石。用于第一和第二阶段合成反应器中的催化剂不需要相同,只要对用于两个反应器中的催化剂进行选择以生成类似产物例如进行选择以生成主要具有C3、C4和C5+汽油范围链烷烃化合物和更重的烃馏分的烃即可。
除了催化剂,运行第一和第二阶段合成反应器的温度在决定反应向期望的具体产物的选择性和转化方面是重要的参数。例如,当使用X型或Y型沸石催化剂并期望产生烯烃时,主张在约250℃~400℃范围内的温度下运行第一阶段合成反应器并在约400℃~450℃范围内的温度下运行第二阶段合成反应器。或者,在涉及ZSM-5沸石催化剂的实施方案中,在第一阶段合成反应器中在约150℃~300℃的稍微更低的温度范围下运行且在第二阶段合成反应器中在约300℃~400℃下运行,会导致产生更高分子量的烃。在两种情况中,通过如图1中所示的本发明的方法和系统产生的高分子量烃产物将含有大量C6+的链烷烃含量。
将描绘本发明方法和系统某些实施方案的某些方面的方块流程图示于图2中,且除了在含有合适催化剂15和19的同一反应器或容器11内在截然不同的区域或床14和18内分别含有第一阶段合成和第二阶段合成之外,所述方块流程图与图1中和上述的类似。各个区域或床可以是固定的或流化的且所述反应器可具有合适的装置如内部或外部换热器以对源自第一阶段合成区域或床的流出物进行加热,然后将其引入同一反应器内的第二阶段合成区域或床内。可将内部换热器16分别安置在第一阶段和第二阶段合成区域或床14和18之间,如图2中所示。在使用外部加热器构造的情况中,内部挡板可例如将一个反应器内所含有的两个催化剂床或区域分开。从位于内部挡板上游的第一阶段合成区域或床中排出的蒸气流出物可通过合适的端口或喷嘴排出并在外部换热器中加热。然后,通过在内部挡板下方但在第二阶段合成区域或床上方的合适端口或喷嘴将加热的蒸气引入反应器中。通过将先后进行的合成阶段并入一个反应器11中,可降低设备成本和运行成本。
将通常描绘本发明方法和系统某些实施方案的某些方面的方块流程图示于图3中。可对含有较低分子量烷烃的进料气体流股20进行预处理以除去C2+组分,然后与溴蒸气合并并传送至溴化反应器中。引入溴化反应器24中的进料气体流股中C2+组分的浓度可小于约4.0mol%,更优选小于约2.0mol%,最优选小于约0.5mol%。尽管在图3的实施方案中的溴化反应器中可容忍一部分C2+烃,但是其浓度较高导致快速生成含碳的焦炭状固体,造成明显结垢和堵塞溴化反应器以及下游组件。如图3中所示,可将进料气体流股与源自第二阶段合成反应器36的流出物、产物烃和残留的烃合并,并在产物分离阶段40中进行预处理以选择性除去C2+组分和烃产物。更具体地,可将进料气体、残留的烃和产物烃如高分子量烃、烯烃或其混合物传送至产物分离阶段40。然后,可将高分子量烃、烯烃或其混合物以及一些C2+组分与进料气体和工艺循环气体分离以生成C4+液体产物流股21。对所述进料气体和循环气体进一步处理以生成用于溴化反应器24的进料流股22和气体流股23,所述气体流股23主要是C3+较低分子量烷烃组分和过量的C2,所述C2由于C2+的浓度限制而不能包括在进料流股22中。在引入溴化反应器之前或引入过程中,或在溴化反应器内,通过流股48将进料流股22与溴合并,所述进料流股22主要是甲烷并同时具有如上所述的可接受浓度的C2+较低分子量的烷烃组分。气体流股23可以以下文中所述的方式与变换反应器26结合使用,同时可将液体烃产物21从产物分离阶段中除去以加以使用或进一步进行石化加工或燃料加工。
如图3中所示,主要含有甲烷和可接受量的C2+较低分子量烷烃组分的进料流股22可在溴化反应器中在约250℃~约600℃范围的相对低温度下并在约1巴~约30巴范围内的压力下与干燥溴蒸气发生放热反应,以产生气体烷基溴和溴化氢蒸气。受益于本发明,本领域技术人员可显而易见的是,在溴化反应器24中的溴化反应可以是均相(热)反应或非均相催化反应。可用于第一反应器30中的合适催化剂的非限制性实例包括铂、钯或负载的非化学计量的金属氧-卤化物如FeOxBry或FeOxCly或负载的金属氧-卤化物如TaOF3、NbOF3、ZrOF2、SbOF3,如同在Olah,et al.,J.Am.Chem.Soc.1985,107,7097-7105中所述的。由于溴化反应的放热本性,运行温度范围的上限大于将进料混合物加热至的反应引发温度范围的上限。在甲烷的情况中,认为根据如下一般反应生成甲基溴:
CH4(g)+Br2(g)→CH3Br(g)+HBr(g)
由于气相溴化反应的自由基机理,还可生成二溴甲烷和一些三溴甲烷以及其他多溴化的较低分子量烷烃。溴化通常在溴化反应器中发生且由于所使用的烷烃对溴的比例,对甲基溴具有相对高程度的选择性。例如,在甲烷溴化的情况中,认为甲烷与溴的比例为约6:1会将单卤代的甲基溴的选择性提高至平均约88%,这取决于反应条件如小于约15秒的停留时间、低于约450℃的温度和湍流混合的程度。在这些条件下,在溴化反应中还生成一些二溴甲烷和接近检测限的仅极少量的三溴甲烷。如果使用约3:1的较低的甲烷与溴的比例,则在小于约15秒的停留时间和低于约450℃的温度下对单卤代的甲基溴的选择性落在约65%~75%的范围内。然而,如果将温度升至约490℃~530℃并将停留时间提高至约60秒,则甲基溴的选择性会升至约90%。然而,在甲烷与溴的比例明显小于约2.5:1时,甲基溴的选择性不可接受地低,而且,观察到明显生成不期望的二溴甲烷、三溴甲烷和炭烟灰。在溴化反应器中使用约450℃~530℃相对更高的温度范围还可确保了溴基本在溴化反应器中消耗,由此有效抑制由于存在元素溴而在本发明方法的随后阶段中随后生成自由基溴化。实现几乎完全溴反应所需要的反应物在溴化反应器中的停留时间相对短且在绝热反应条件下可小至1~5秒。通往溴化反应器中的进料气体中含有的任何更高分子量的烷烃如乙烷、丙烷和丁烷也发生溴化,导致单-和多-溴化的物种如乙基溴、丙基溴和丁基溴。此外,在某些实施方案中,进料至溴化反应器中的干燥溴蒸气基本不含水。申请人已经发现,至少在某些实施方案中,这是优选的,因为呈现,从溴化步骤中基本消除所有的水蒸气会基本消除不希望的二氧化碳的生成。这会提高烷烃溴化对烷基溴的选择性,由此可能消除在由烷烃生成二氧化碳中产生的大量废热。
可将气体流股23与从溴化反应器排出的包含烷基溴、溴化氢和未反应的溴的流出物25合并并引入转化/歧化反应器26中。此外,尽管溴通常快速反应,但是由于不完全混合或更短的停留时间而在溴化反应器中未反应且存在于源自溴化反应器的流出物中的任何少量的未反应的溴,通过在引入转化/歧化反应器之前或之时与C2+烃的热溴化反应而易于被消耗。在转化/歧化反应器26中,存在于源自溴化反应器的流出物25中所含有的烷基溴中的二-和三-溴化烷烃中的大部分,可在与C2+组分反应时选择性转化成单溴化烷烃。作为实例,在C3和二溴甲烷是反应物的情况中,认为根据如下一般反应发生转化:
C3H8+CH2Br2→CH3Br+C3H7Br
尽管该反应可在不使用催化剂的条件下热实施,但是已经确定,这种热反应在转化/歧化反应器内需要不可接受的长的停留时间且不会实现向单溴化烷烃的良好转化速率。因此,优选的是,转化/歧化反应器含有选自VIII族金属、VIB族金属、IB族金属、铝、锌、钒、镁、钙、钛及其混合物中的合适催化剂的床(未示出)。VIII族金属包括铁、钴、镍、铂、钯、铑、钌、铱、锇或其两种以上物质的混合物。VIB族金属包括钨、钼或铬。IB族金属包括铜或银。优选地,用于本发明该实施方案中的VIII族金属为选自铂、钯、铑、钌、铱、锇或其两种以上物质的混合物的贵金属,更优选VIII族金属是铂。最优选地,VIII族金属是作为金属溴化物、金属氧化物或非化学计量的金属氧-溴化物使用的铁。优选地,VIB族金属是钼或钨。优选地,IB族金属是作为金属溴化物、金属氧化物或金属氧-溴化物使用的铜。可生成用于本发明方法中超过一种热可逆溴化物盐的上述合适金属催化剂的非限制性实例是铁、钼、钨、铜、钒、铬或其两种以上物质的混合物。可生成用于本发明方法中的单种溴化物盐的上述合适催化剂的非限制性实例是钴、镍、银、锌、镁、钙、钛、铝或其两种以上物质的混合物。生成超过一种热可逆溴化物盐或单种溴化物盐的这些金属可最初用于本发明的方法中以作为溴化物盐或氧化物,因为这些金属由于在用于转化/歧化反应器中的条件下通过与溴化氢反应转化为溴化物的盐而存在并充当转化/歧化反应器中的溴化物。选择合适的载体以具有相对低的酸度而抑制多溴化烷烃的热分解和劣化并具有相对低的表面积以抑制多溴化烷烃吸附在载体上。在转化/歧化反应器中与催化剂一起使用的合适载体的非限制性实例包括二氧化硅、氧化钛、氧化锆或低表面积的氧化铝,优选具有小于约50m2/g的比表面积。
催化剂担载并分散在合适载体上,从而以成本高效的方式产生高活性,如同本领域技术人员所理解的。例如,当在转化/歧化反应器床中使用铂作为催化剂时优选使用约0.1重量%~约1重量%且更优选约0.3重量%~约0.5重量%的担载量,而当使用钯作为催化剂时使用约1重量%~约10重量%且更优选3重量%~约10重量%的担载量。在优选的非贵金属如铁、钼、钒或其混合物的情况中,使用约10%~约20%以上(作为金属氧化物)的更高担载量是成本高效的。当在转化/歧化反应器26中使用催化剂时,优选在约200℃~约500℃、更优选约300℃~约400℃下运行反应器26。实现向单溴化烷烃的期望选择性所需要的反应物在转化/歧化反应器26中的停留时间相对短且可小至2~8秒。
在引入第一阶段合成反应器32中之前,通过任意一种合适手段如换热器28,可将源自转化/歧化反应器的含有明显提高的单溴化烷烃与二-或三-溴化烷烃比例的烷基溴的流出物27冷却或加热至约150℃~约300℃,更优选约225℃~约275℃。在第一阶段合成反应器32中,在合适催化剂33上,在约150℃~约300℃的温度范围且更优选在约225℃~约275℃的温度范围下并在约1~约100巴范围内的压力下使得烷基溴发生放热反应以产生期望的烃产物(例如高分子量烃、烯烃或其混合物)。据认为,在这些条件下,在合适催化剂上,丙基溴的反应性比甲基溴和乙基溴高,由此丙基单元优先发生低聚,由此生成产物如高分子量烃、烯烃或其混合物,所述产物含有大量C6+链烷烃含量和由此下降的芳族化合物含量。在第一阶段合成反应器32中,仅有一部分存在于烷基溴中的单溴化烷烃发生转化,且所存在的任何多溴化烷烃具有更低的向重质产物或沉积在催化剂上的“焦炭”转化的倾向,因为存在丙基溴和温度条件更低。
在引入第二阶段合成反应器36中之前,通过任意一种合适手段如换热器35,可对源自第一阶段合成反应器的流出物34进行加热。流出物34含有烃产物和未反应的烷基溴如甲基溴和乙基溴。在第二阶段合成反应器36中,在合适催化剂上,可在约300℃~约450℃的范围内且更优选在约350℃~约425℃的范围内的温度下并在约1~约100巴范围内的压力下使得甲基溴和乙基溴发生放热反应以产生期望的烃产物(例如高分子量烃、烯烃或其混合物)。据认为,在这些条件下,在合适催化剂上,甲基溴和乙基溴的具有的反应性会优先使得甲基和乙基单元发生低聚,由此生成产物如高分子量烃、烯烃或其混合物,所述产物含有具有大部分被取代的芳族化合物的C7+组分以及主要在C3~C5+范围的轻质烷烃。
用于第一和第二阶段合成反应器32和36中的催化剂33和37分别为按上述用于将烷基溴催化转化成产物烃的多种合适材料中的任意一种。在某些实施方案中,所述第一和第二阶段合成反应器可包含催化剂的固定床。在特定情况中尤其是在更大的应用中还可使用合成催化剂的流化床,所述流化床具有特定的优势如恒定地除去焦炭和对产物组合物的稳定的选择性。用于第一和第二两个阶段合成反应器32和36中的具体催化剂取决于例如所期望的具体产物烃。例如当期望主要具有C3、C4和C5+汽油范围链烷烃化合物和更重的烃馏分的产物烃时,可使用ZSM-5沸石催化剂。当期望产生包含烯烃和C5+产物的混合物的产物烃时,可使用X型或Y型沸石催化剂或SAPO沸石催化剂。合适的沸石的实例包括X型如10-X或Y型沸石,但在本发明的实施方案中可使用具有不同孔径和酸度的其他沸石。用于第一和第二阶段合成反应器32和36中的催化剂不需要相同,只要对用于两个反应器中的催化剂进行选择以生成类似产物如进行选择以生成主要具有C3、C4和C5+汽油范围链烷烃化合物和更重的烃馏分的烃即可。
通过合适手段如换热器39可对源自第二阶段合成反应器36的流出物38进行冷却以回收热,从而用于所述方法中的其他别处,例如用于产生蒸气或对所述方法的进料进行预热(未示出)、或用于本领域技术人员所确定的其他用途,然后将所述流出物38传送至产物分离阶段40。在产物分离阶段中可从烃产物如高分子量烃、烯烃或其混合物中回收溴化氢并将分离的溴化氢的流股42传送至溴化物氧化阶段44,其中通过部分氧化的金属溴化物盐对溴化氢进行中和以制得金属溴化物盐和蒸汽。向本发明的溴化物氧化阶段44中引入氧气或空气的流股46以接触制得的金属溴化物盐,从而制得元素溴。可将作为干燥的溴蒸气和部分氧化的金属溴化物盐的溴流股48循环至溴化阶段,其可将源自于由所述方法产生的烃中的额外溴化氢中和并除去。可对利用部分氧化的金属溴化物盐对HBr进行氧化而得到的蒸汽进行冷凝、汽提出所有残留的溴并作为副产物液体水流股49排出。
图3中所示的方法实施方案的第一阶段合成反应器32和第二阶段合成反应器36可容纳在图2中所描绘的同一反应器内的不同的区域或床中。各个区域或床可以是固定的或流化的且所述反应器可具有合适的装置如内部或外部换热器以对源自第一阶段合成区域或床的流出物进行加热,然后使其流入同一反应器内的第二阶段合成区域或床内。
将通常描绘本发明方法和系统的某些实施方案的某些方面的方块流程图示于图4中。尽管在图1~3中的和上述的各个实施方案使用了以串联构造安排的第一阶段合成反应器和第二阶段合成反应器、区域或床,但是在图4中通常显示的本发明方法和系统的实施方案描绘以并联方式安排的第一合成反应器(低温)和第二合成(高温)反应器。在这种并联构造中,用作图4中所描绘的实施方案中第二合成反应器进料的C1+烷基溴的流股55可由对含有较低分子量烷烃的进料气体流股进行溴化而生成,所述较低分子量烷烃主要是甲烷且同时含有可接受浓度的C2+较低分子量烷烃组分。如上述关于图1~3所讨论的,可对含有较低分子量烷烃的进料气体流股进行预处理以除去C2+组分,然后与溴蒸气合并并传送至溴化反应器中。引入溴化反应器中的进料气体流股中C2+组分的浓度可小于约4.0mol%,更优选小于约2.0mol%,最优选小于约0.5mol%。尽管在图3的实施方案中的溴化反应器中可容忍一些C2+烃,但是其较高浓度导致快速生成含碳的焦炭状固体,造成结垢和堵塞溴化反应器以及下游组件。在引入第二合成反应器57之前,可通过任意合适手段如换热器56对C1+烷基溴的流股55进行加热。在第二合成反应器57中,在合适催化剂58上,在约300℃~约450℃的范围内且更优选在约350℃~约425℃的范围内的温度下并在约1~约100巴范围内的压力下使得甲基溴和乙基溴发生放热反应以产生期望的烃产物(例如高分子量烃、烯烃或其混合物)。据认为,在这些条件下,在合适催化剂58上,甲基溴和乙基溴具有反应性而使得甲基和乙基单元发生低聚,由此生成烃产物如高分子量烃、烯烃或其混合物的流股59,所述产物含有具有主要被取代的芳族化合物的C6+组分以及主要在C3~C5+范围的轻质烷烃。
用作图4中所描绘实施方案中的第一合成反应器52的进料的主要是C3+烷基溴的分离流股50可由对主要含有C3+组分和可接受量的C2组分的进料气体流股进行溴化而生成。在引入第一合成反应器52中之前,通过任意一种合适手段如换热器可将主要含有C3+烷基溴的气体流股冷却或加热至约150℃~约300℃,更优选约225℃~约275℃。在第一合成反应器52中,在合适催化剂53上,在约150℃~约300℃且更优选约225℃~约275℃的温度范围下且在约1~约100巴范围内的压力下使得烷基溴发生放热反应以产生期望的烃产物54(例如高分子量烃、烯烃或其混合物)。据认为,在这些条件下,在合适催化剂上,丙基溴的反应性比甲基溴和乙基溴高,由此优选使得丙基单元发生低聚,由此生成烃产物如高分子量烃、烯烃或其混合物,所述烃产物含有大量C6+链烷烃含量和由此减少的芳族化合物含量。在第一合成反应器52中,存在于烷基溴中的单溴化烷烃中仅有一部分被转化,且存在的所有多溴化烷烃不易转化为重质产物或沉积到催化剂上的“焦炭”,因为存在丙基溴和温度条件更低。
如上所述,用于图4的第一和第二两个合成反应器52和57中的具体催化剂取决于例如所期望的具体产物烃。例如当期望主要具有C3、C4和C5+汽油范围链烷烃化合物和更重的烃馏分的产物烃时,可使用ZSM-5沸石催化剂。当期望产生包含烯烃和C5+产物的混合物的产物烃时,可使用X型或Y型沸石催化剂或SAPO沸石催化剂。合适的沸石的实例包括X型如10-X或Y型沸石,但在本发明的实施方案中可使用具有不同孔径和酸度的其他沸石。用于第一和第二阶段合成反应中的催化剂不需要相同,特别地,在源自第一和第二反应器的流出物含有不同的烃产物的情况中,可以以不同方式对所述催化剂进行进一步处理,或上述两者。
将通常描绘本发明方法和系统某些实施方案的某些方面的方块流程图示于图5中。可对含有较低分子量烷烃的进料气体流股60进行预处理以除去C2+组分,然后与溴蒸气合并并传送至至少一个C1+溴化反应器64中。在引入C1+溴化反应器64中的进料气体流股中C2+组分的浓度可小于约4.0mol%,更优选小于约2.0mol%,最优选小于约0.5mol%。尽管在图5的实施方案中的C1+溴化反应器64中可容忍一些C2+烃,但是浓度超过上述值可导致快速生成含碳的焦炭状固体,造成结垢和堵塞溴化反应器以及下游组件。可将图5中所示的方法和系统的进料气体与源自合成反应器76和68的流出物79合并,并在产物分离阶段中进行预处理以选择性除去C2+组分和烃产物。更具体地,将进料气体、残留的烃和产物烃如高分子量烃、烯烃或其混合物传送至产物分离单元80。然后,将高分子量烃、烯烃或其混合物以及C2+组分与进料气体分离,得到C1+烃流股62,如上所述其主要是甲烷并同时具有可接受浓度的C2+较低分子量烷烃组分。所述C2+组分还可在产物分离单元80中从产物烃中分离并以与下文中所述的方式与C2+溴化反应器结合使用,同时可将液体烃产物从产物分离单元80中的产物稳定塔(未示出)中作为流股61移出以加以使用或进一步进行石化加工或燃料加工。
在引入至少一个C1+溴化反应器64之前、之时或在所述至少一个溴化反应器64内,可将C1+流股62与溴流股88合并。在C1+溴化反应器的进料中可利用的甲烷与溴之比是C1+流股的C2+含量以及温度的函数。C1+流股中C2+的含量越低且在更低温度下运行可使得在更低的甲烷与溴之比下运行。
因此,在适当控制C1+流股的C2+含量的条件下,在去往C2+溴化反应器64的进料中甲烷与溴的摩尔比为小于约7:1但大于约1.25:1,优选小于约4:1但大于约2:1,更优选小于或等于约3:1但大于约2.5:1。可将C1+流股62与液体溴流股88混合并传送至换热器(未示出),其中将混合物加热至约300℃~约550℃的温度,但更优选约450℃~约500℃的范围内,其中将液体溴蒸发并引发溴化反应。
此外,在某些实施方案中,进料至C1+溴化反应器中的混合物中干燥溴蒸气可基本不含水。申请人已经发现,至少在某些情况中,这是优选的,因为呈现,从溴化步骤中基本消除所有的水蒸气会基本消除不需要的二氧化碳的生成。这会提高烷烃溴化对烷基溴的选择性,由此可能消除在由烷烃生成二氧化碳中产生的大量废热。
将主要含有甲烷、可接受量的C2+较低分子量烷烃组分和溴蒸气的经加热的混合物引入C1+溴化反应器64中,其中对混合物中存在的较低分子量烷烃,主要是甲烷和可接受量的C2+较低分子量烷烃,进行热溴化。如果需要,C1+溴化反应器64可含有进口预加热器区域(未示出)以确保混合物保持加热至约300℃~约550℃范围内的反应引发温度。在甲烷的情况中,认为根据如下一般反应生成甲基溴:
CH4(g)+Br2(g)→CH3Br(g)+HBr(g)
在基本所有元素溴都已经反应掉的情况下,源自C1+溴化反应器64的流出物流股65是烷基溴与溴化氢和未反应的较低分子量烷烃主要是甲烷的混合物。可将所述流出物流股65从C1+溴化反应器64中移出并直接引入高温合成反应器68中。所述C1+溴化反应器64可还含有催化转化区域。向催化转化区域中供应的这种进料的温度为约350℃~约570℃,更优选500℃~约570℃,最优选530℃~约570℃。由于C1+热溴化反应放热,所以将引入到C1+溴化反应器中的进料气体和溴加热至约300℃~约550℃的范围内的温度下以确保源自C1+溴化反应器64的热溴化区域中的流出物在期望范围内以引入催化转化区域中,所述催化转化区域给定了本领域技术人员所显而易见的热溴化反应器的反应器运行条件。或者,可通过本领域技术人员所显而易见的任意一种合适手段(未示出)将源自热溴化区域或反应器的流出物混合物加热或冷却至约350℃~约570℃范围内的温度,然后与催化转化区域中所使用的催化剂接触。
可用于通常示于图5中的本发明方法实施方案中的C1+溴化反应器的催化转化区域中的催化剂可以为能够生成金属卤化物或金属氧-卤化物两者或其混合物的金属元素,且包括Fe、Mo、La、Ce、W、Cr、Co、Ni、Cu、Ag、Zn、Mn、V、Nb、Ta、Ti、Y、Zr、Mg和Ca。可用于生成催化活性金属卤化物或金属氧-卤化物的卤素是Br、Cl和F,优选Br。
尽管可将催化剂最初制备成分散在催化剂载体上的金属溴化物,但一般更通常的是利用金属硝酸盐溶液前体通过初始润湿技术分散金属氧化物,随后在空气或其他氧化性气体混合物中于高温下进行干燥并煅烧。此外,由于许多金属溴化物盐吸湿,所以处理、存储和运输需要特殊措施。因此,用于催化转化区域中的催化剂最实际地是仅以金属氧化物状态商购获得。将这种金属氧化物催化剂最初用于图5的反应器64内的催化转化区域中,因为由于其与溴化氢、甲基溴、二溴甲烷或其他烷基溴反应而转化成金属溴化物或金属氧-溴化物或其混合物。然而,由于催化转化区域中金属氧化物催化剂的活性略低于金属溴化物或金属氧-溴化物的活性且在转化完成之前碳的损失或焦化增多,所以期望通过任意一种合适手段如通过与溴化氢和载气如甲烷或氮气反应,在将进料引入催化转化区域或反应器之前,将最初的金属氧化物催化剂原位转化成金属溴化物或金属氧-溴化物或其混合物。
在催化转化区域中,存在于源自热溴化区域中的流出物中所含的烷基溴中的大部分二-和三-溴化烷烃,在与进料中存在的未反应的烷烃组分、主要是甲烷反应时,选择性地转化成单溴化烷烃。作为实例,在C1和二溴甲烷是反应物的情况中,认为根据如下一般反应发生转化:
CH4+CH2Br2→2CH3Br
由于在热区域和催化区域两者中的高温,元素溴易于基本完全转化。据认为,用于催化转化区域或反应器中的催化剂会促进二溴甲烷与甲烷的选择性反应,从而通过溴(通过二溴甲烷在催化剂表面上的离解吸附而供应)与甲烷的选择性催化反应得到甲基溴。然后可将源自C1+溴化反应器的催化转化区域的流出物传输至高温合成反应器68中,所述流出物含有明显更高比例的单溴化烷烃:二-或三-溴化烷烃。尽管上面已经将热和催化转化区域描述为容纳在单个C1+溴化反应器64内,但是如同本领域技术人员所显而易见的,这些区域能够各自容纳在串联安排的至少两个分开的反应器中。
在引入高温合成反应器68中之前,通过任意一种合适手段如换热器66,可对源自C1+溴化反应器的流出物流股65进行冷却或加热。在高温合成反应器中,在合适催化剂上,在约300℃~约450℃的范围内且更优选在约350℃~约425℃的范围内的温度下并在约1~约100巴范围内的压力下使得甲基溴和乙基溴发生放热反应以产生期望的烃产物(例如高分子量烃、烯烃或其混合物)流股67。据认为,在这些条件下,在合适催化剂上,甲基溴和乙基溴的具有的反应性会优先使得甲基和乙基单元发生低聚,由此生成产物如高分子量烃、烯烃或其混合物,所述产物含有具有主要被取代的芳族化合物的C7+组分以及主要在C3~C5+范围的轻质烷烃。
C2+组分的流股70可通过所述方法制得或所述流股70可包含在产物分离单元80中所移出的进料气体中,使得去往C1+溴化反应器的进料含有可接受量的C2+。使用液体溴进料的滑流89,可在C2+热溴化反应器72中单独对过量的C2+且尤其是C3+进行处理。C2+热溴化反应器72在约4:1~约1.25:1的范围内且优选在约2:1~约1.5:1的范围内的烷烃与溴之比以及在约250℃~550℃范围内的温度下运行。C2+溴化反应器72可还含有催化转化区域,如以上就C1+溴化反应器64所述。
在引入低温合成反应器76中之前,通过任意一种合适手段如换热器74可将源自C2+热溴化反应器的含有各种烷基溴和溴化氢的流出物73冷却或加热至约150℃~约300℃,更优选约225℃~约275℃。在低温合成反应器中,在合适催化剂77上,在约150℃~约300℃且更优选约225℃~约275℃的温度范围下且在约1~约100巴范围内的压力下使得烷基溴发生放热反应以产生期望的烃产物(例如高分子量烃、烯烃或其混合物)。据认为,在这些条件下,在合适催化剂上,丙基溴的反应性比甲基溴和乙基溴高,由此优选使得丙基单元发生低聚,由此生成烃产物如高分子量烃、烯烃或其混合物,所述烃产物含有大量C6+链烷烃含量和由此减少的芳族化合物含量。在第一阶段合成反应器中,存在于烷基溴中的单溴化烷烃中仅有一部分被转化,且存在的所有多溴化烷烃不易转化为重质产物或沉积到催化剂上的“焦炭”,因为存在丙基溴和温度条件更低。
分别用于低温和高温合成反应器76和68中的催化剂77和69为按上述用于将烷基溴催化转化成产物烃的多种合适材料中的任意一种。在某些实施方案中,所述低温和高温合成反应器可包含催化剂的固定床。在某些情况中尤其是在更大的应用中还可使用合成催化剂的流化床,所述流化床具有特定的优势如恒定地除去焦炭和对产物组合物的稳定的选择性。用于低温和高温合成反应器两者中的具体催化剂取决于例如所期望的具体产物烃。例如当期望主要具有C3、C4和C5+汽油范围链烷烃化合物和更重的烃馏分的产物烃时,可使用ZSM-5沸石催化剂。当期望产生包含烯烃和C5+产物的混合物的产物烃时,可使用X型或Y型沸石催化剂或SAPO沸石催化剂。合适的沸石的实例包括X型如10-X或Y型沸石,但在本发明的实施方案中可使用具有不同孔径和酸度的其他沸石。用于低温和高温合成反应器中的催化剂不需要相同,只要对用于两个反应器中的催化剂进行选择以生成类似产物如进行选择以生成主要具有C3、C4和C5+汽油范围链烷烃化合物和更重的烃馏分的烃即可。
可将分别源自低温和高温合成反应器76和68的流出物流股78和67与一个合成流出物流股79合并,并通过合适手段如换热器71进行冷却以回收热,从而用于所述方法中的其他用途如产生蒸汽或对所述方法的进料进行预热(未示出)、或用于本领域技术人员所确定的其他用途,然后传送至产物分离阶段80。从烃产物如高分子量烃、烯烃或其混合物中回收溴化氢并将溴化氢的流股82传送至溴化物氧化阶段84,其中通过部分氧化的金属溴化物盐对溴化氢进行中和以制得金属溴化物盐和蒸汽。向溴化物氧化阶段84中引入氧气或空气的流股86以接触制得的金属溴化物,从而制得元素溴。将作为干燥的溴蒸气的溴流股88和部分氧化的金属溴化物盐循环至溴化阶段,其可将源自由所述方法产生的烃中的其他溴化氢中和并除去。可对利用部分氧化的金属溴化物盐对HBr进行氧化而得到的蒸汽进行冷凝、汽提所有残留的溴并作为副产物液体水产物87除去。
将通常描绘本发明方法和系统某些实施方案的某些方面的方块流程图示于图6中,且除了将源自C1+溴化反应器的流出物与循环的多溴化物合并、加热并热反应以将存在于烷基溴流股中的多溴化烷烃转化成单溴化烷烃,然后引入高温合成反应器68中之外,所述方块流程图与图5中所示的和上述的类似。如图6中所示,将源自C1+溴化反应器的作为烷基溴和溴化氢的混合物的流出物流股65与循环的多溴化物合并并随后通过任意一种合适手段如换热器将混合物加热至约450℃~约570℃的温度下,并传送至歧化反应器92中,其中将存在于流出物流股中的多溴化烷烃中的至少一部分转化成单溴化烷烃。歧化反应器92可以是相对长、末端开口的管,以使得具有足够长的停留时间,优选约15~60秒,从而使得存在于流出物流股中的多溴化烷烃中的至少一部分转化成单溴化烷烃。然后,通过任意一种合适手段如换热器94将源自歧化反应器92的流出物流股93冷却,并引入分馏塔95中,其中将多溴化烷烃如二-和三-溴化的烷烃从流出物中除去。将含有这种多溴化烷烃的分馏塔塔底液体流股99通过分馏塔再沸器100,使得一部分液体蒸发,从液体中更重的多溴化烷烃中汽提残留的更轻的单溴化烷烃。可将所述残留的轻质单溴化烷烃作为流股101循环至分馏塔95。将含有多溴化烷烃的流股102与源自C1+溴化反应器的流出物流股65合并并预热至约450℃~约570℃的温度,然后引入歧化反应器92中,其中将所述多溴化烷烃与C1+反应以进一步主要生成单溴化烷烃。将已经在分馏塔中与多溴化烷烃分开的分馏塔塔顶蒸气流股96传送至冷凝器97,其中所有残留的多溴化烷烃发生冷凝并作为流股98回流至分馏塔95中。根据上述详细描述的图4和5中所示的本发明方法和系统的实施方案,在引入高温合成反应器68中之前,通过任意一种合适手段如换热器66对主要包含烷基溴和溴化氢的残留流股96进行加热。根据上述详细描述的图5中所示的本发明方法和系统的实施方案,运行图6中所示的残留流股和工艺设备。
将通常描绘本发明方法和系统某些实施方案的某些方面的方块流程图示于图7中且除了在与溴化的进料气体流股合并并通过两个合成阶段之前将C2+组分单独溴化之外,所述流程图与图3中所示的和上述的相类似。此外,在图7中所示的实施方案中未利用转化/歧化反应器。
如图7中所示,可对含有较低分子量烷烃的进料气体流股120进行预处理以除去C2+组分,然后与溴蒸气合并并传送至溴化反应器124中。引入溴化反应器124中的进料气体流股122中C2+组分的浓度可小于约4.0mol%,更优选小于约2.0mol%,最优选小于约0.5mol%。尽管在图7的实施方案中的C1+溴化反应器124中可容忍一些C2+烃,但是其浓度越高导致快速生成含碳的焦炭状固体,造成明显结垢和堵塞溴化反应器以及下游组件。如图7中所示,可将进料气体流股与源自第二阶段合成反应器136的流出物如产物烃和残留的烃合并,并在产物分离阶段140中进行预处理以选择性除去C2+组分和烃产物。更具体地,将进料气体、残留的烃和产物烃如高分子量烃、烯烃或其混合物传送至产物分离阶段140。然后,将高分子量烃、烯烃或其混合物以及一些C2+组分与进料气体和工艺循环气体分离以生成C4+液体产物流股121。对所述进料气体和循环气体进一步处理以生成用于C1+溴化反应器124的进料流股122和气体流股123,所述气体流股123主要是C3+较低分子量烷烃组分和过量的C2,所述C2由于C2+的浓度限制而不能包括在进料流股122中。在引入溴化反应器之前或之时,或在溴化反应器内,通过流股148将进料流股122与溴合并,所述进料流股122主要是甲烷并同时具有如上所述的可接受浓度的C2+较低分子量烷烃组分。主要是C3+较低分子量烷烃组分以及过量C2的气体流股123可以以下文中所述的方式与C2+溴化反应器126结合使用,同时将液体烃产物121从产物分离阶段中除去以加以使用或进一步进行石化加工或燃料加工。
如图7中所示,主要含有甲烷和可接受量的C2+较低分子量烷烃组分的进料流股122可在C1+溴化反应器124中在约250℃~约600℃范围的相对低温度下并在约1巴~约30巴范围内的压力下与干燥的溴蒸气发生放热反应,以产生气体烷基溴和溴化氢蒸气。受益于本发明,本领域技术人员显而易见的是,在C1+溴化反应器124中的溴化反应可以是均相(热)反应或非均相催化反应。用于C1+溴化反应器124中的合适催化剂、运行温度范围和烷烃与溴之比为如上文关于图3中溴化反应器24所述。
主要是C3+较低分子量烷烃组分和过量C2的气体流股123可在C2+热溴化反应器126中在约250℃~约600℃范围的相对低温度下并在约1巴~约30巴范围内的压力下与干燥的溴蒸气发生放热反应,以与上述就C1+溴化反应器124所述的方式产生气体烷基溴和溴化氢蒸气。所述C2+溴化反应器126可还含有催化转化区域,如同上面关于图5中的C1+溴化反应器64所述描述的。
将流股127与流股125合并,所述流股127含有源自C2+溴化反应器126的流出物,其包含高级烷基溴、溴化氢和未反应的烷烃,所述流股125含有从C1+溴化反应器124排出的流出物,其包含烷基溴、溴化氢和未反应的甲烷。在引入第一阶段合成反应器132中之前,通过任意一种合适手段如换热器128,可将这种合并的流股冷却或加热至约150℃~约350℃,更优选约225℃~约325℃。在第一阶段(低温)合成反应器132中,在合适催化剂33上,在约150℃~约350℃且更优选约225℃~约325℃的温度范围下并在约1~约100巴范围内的压力下使得烷基溴发生放热反应以产生期望的烃产物(例如高分子量烃、烯烃或其混合物)。据认为,在这些条件下,在合适催化剂上,丙基溴的反应性比甲基溴或乙基溴高,由此丙基单元优先发生低聚,由此生成产物如高分子量烃、烯烃或其混合物,所述产物含有大量C6+链烷烃含量和由此下降的芳族化合物含量。此外,据认为,丙基溴和未反应的丙烷可充当氢供体,由此使得所有多溴化烷烃中的大部分、尤其是二溴甲烷在这些较低温度条件下和在合适催化剂上转化成更高分子量的烃产物,而不是重质产物或沉积在催化剂上的“焦炭”。由此,有用产物的收率和本发明方法的运行效率可提高。然而,在第一阶段合成反应器132中的相对低的运行温度下,仅有一部分存在于烷基溴中的单溴化烷烃可发生转化。
在引入第二阶段(高温)的合成反应器136中之前,通过任意一种合适手段如换热器135,可对源自第一阶段合成反应器的流出物134进行加热。流出物134含有烃产物和未反应的烷基溴(甲基溴和乙基溴)。在第二阶段合成反应器136中,在合适催化剂上,在约350℃~约450℃的范围内且更优选在约375℃~约425℃的范围内的温度下并在约1~约100巴范围内的压力下使得甲基溴和乙基溴发生放热反应以产生期望的烃产物(例如高分子量烃、烯烃或其混合物)。据认为,在这些条件下,在合适催化剂上,甲基溴和乙基溴的具有的反应性会优先使得甲基和乙基单元发生低聚,由此生成产物如高分子量烃、烯烃或其混合物,所述产物含有具有主要被取代的芳族化合物的C7+组分以及主要在C3~C5+范围的轻质烷烃。由于大部分多溴化烷烃可在低温合成反应器132中反应或除去,所以在第二阶段(高温)合成反应器136中产物选择性可提高且焦炭的生成减少。
用于第一和第二阶段合成反应器132和136中的催化剂133和137分别为按上述用于将烷基溴催化转化成产物烃的多种合适材料中的任意一种。在某些实施方案中,所述第一和第二阶段合成反应器可包含催化剂的固定床。在特定情况中尤其是在更大的应用中还可使用合成催化剂的流化床,所述流化床具有特定的优势如恒定地除去焦炭和对产物组合物的稳定选择性。用于第一和第二两个阶段合成反应器132和136中的具体催化剂取决于例如所期望的具体产物烃。例如当期望主要具有C3、C4和C5+汽油范围链烷烃化合物和更重的烃馏分的产物烃时,可使用ZSM-5沸石催化剂。当期望产生包含烯烃和C5+产物的混合物的产物烃时,可使用X型或Y型沸石催化剂或SAPO沸石催化剂。合适的沸石的实例包括X型如10-X或Y型沸石,但在本发明的实施方案中可使用具有不同孔径和酸度的其他沸石。用于第一和第二阶段合成反应器132和136中的催化剂不需要相同,只要对用于两个反应器中的催化剂进行选择以生成类似产物如进行选择以生成主要具有C3、C4和C5+汽油范围链烷烃化合物和更重的烃馏分的烃即可。
通过合适手段如换热器139可对源自第二阶段合成反应器136中的流出物138进行冷却以回收热,从而用于所述方法中的其他用途如产生蒸汽或对所述方法的进料进行预热(未示出)、或用于本领域技术人员所确定的其他用途,然后将所述流出物138传送至产物分离阶段140。在产物分离阶段中从烃产物如高分子量烃、烯烃或其混合物中回收溴化氢并可将分离的溴化氢的流股142传送至溴化物氧化阶段144,其中通过部分氧化的金属溴化物盐对溴化氢进行中和以制得金属溴化物盐和蒸汽。向本发明的溴化物氧化阶段144中引入氧气或空气的流股146以接触制得的金属溴化物盐,从而制得元素溴和部分氧化的金属溴化物盐,所述部分氧化的金属溴化物盐可将源自于由所述方法产生的烃中的其他溴化氢中和并除去。可将溴的流股148作为干燥的溴蒸气循环至溴化阶段。可对利用部分氧化的金属溴化物盐对HBr进行氧化而得到的蒸汽进行冷凝、汽提所有残留的溴并作为副产物液体水流股149进行提取。
在与图2中所描绘的和上述相同的反应器内在不同区域或床中可含有图7中所示的方法实施方案的第一阶段合成反应器132和第二阶段合成反应器136。各个区域或床可以是固定的或流化的且所述反应器可具有合适的装置如内部或外部换热器以对源自第一阶段合成区域或床的流出物进行加热,然后将其流入同一反应器内的第二阶段合成区域或床内。
将通常描绘本发明方法和系统某些实施方案的某些方面的方块流程图示于图8中,且除了将源自C1+溴化反应器的流出物与C2+组分合并并然后引入低温合成反应器中和将源自低温合成反应器的流出物与源自C2+溴化反应器的流出物合并并然后引入高温合成反应器中之外,所述方块流程图与图5中所示的和上述的类似。
如图8中所示,可对含有较低分子量烷烃的进料气体流股160进行预处理以除去C2+组分,然后在引入至少一个C1+溴化反应器164之前或之时或在至少一个C1+溴化反应器164内通过流股188与溴合并。引入C1+溴化反应器164中的进料气体流股中C2+组分的浓度可小于约4.0mol%,更优选小于约2.0mol%,最优选小于约0.5mol%。尽管在图8的实施方案中的C1+溴化反应器164中可容忍一些C2+烃,但是其浓度超过上述值会导致快速生成含碳的焦炭状固体,造成结垢和堵塞溴化反应器以及下游组件。可将图8中所示方法和系统的进料气体与源自高温合成反应器168的流出物167合并并在产物分离阶段中进行预处理以选择性除去C2+组分和产物烃。更具体地,将进料气体、残留的烃和产物烃如高分子量烃、烯烃或其混合物传送至产物分离单元180。然后,可将高分子量烃、烯烃或其混合物以及C2+组分与进料气体分离,得到C1+烃流股162,其如上所述主要是甲烷并同时具有可接受浓度的C2+较低分子量烷烃组分。所述C2+组分还可在产物分离单元180中从产物烃中分离并以与下文中所述的方式与C2+溴化反应器结合使用,同时将液体烃产物从产物分离单元180中的产物稳定塔(未示出)中作为流股161移出以加以使用或进一步进行石化加工或燃料加工。
在引入至少一个C1+溴化反应器164之前、之时或在所述至少一个溴化反应器164内,将C1+流股162与溴流股188合并。在C1+溴化反应器的进料中可利用的甲烷与溴之比是C1+流股的C2+含量以及温度的函数。C1+流股中C2+的含量越低且在更低温度下运行可使得在更低的甲烷与溴之比下运行。
因此,在适当控制C1+流股的C2+含量的条件下,在去往C2+溴化反应器164的进料中甲烷与溴的摩尔比为小于约7:1但大于约1.25:1,优选小于约4:1但大于约2:1,更优选小于或等于约3:1但大于约2.5:1。可将C1+流股162与液体溴流股188混合并传送至换热器(未示出),其中将混合物加热至约300℃~约550℃的温度,但更优选约450℃~约500℃的范围内,且其中将液体溴蒸发并引发溴化反应。
此外,在某些实施方案中,进料至C1+溴化反应器中的混合物中的干燥溴蒸气基本不含水。申请人已经发现,至少在某些情况中,这是优选的,因为呈现,从溴化步骤中基本消除所有的水蒸气会基本消除不希望的二氧化碳的生成。这会提高烷烃溴化对烷基溴的选择性,由此可能消除在由烷烃生成二氧化碳中产生的大量废热。
可将主要含有甲烷、可接受量的C2+较低分子量烷烃组分和溴蒸气的经加热的混合物引入C1+溴化反应器164中,其中对混合物中存在的较低分子量烷烃、主要是甲烷和可接受量的C2+较低分子量烷烃进行热溴化。如果需要,C1+溴化反应器164可含有进口预加热器区域(未示出)以确保混合物保持加热至约300℃~约550℃范围内的反应引发温度。受益于本发明,本领域技术人员显而易见的是,在C1+溴化反应器164中的溴化反应可以是均相(热)反应或非均相催化反应。用于C1+溴化反应器124中的合适催化剂、运行温度范围和烷烃与溴之比为关于图5中溴化反应器24所述的。
C2+组分的流股170可通过所述方法制得或所述流股170可包含在在产物分离单元180中所除去的进料气体中,使得C1+溴化反应的进料含有可接受量的C2+。使用液体溴进料的滑流189,可在C2+热溴化反应器172中单独对过量的C2+且尤其是C3+进行处理。C2+热溴化反应器172在约4:1~约1.25:1的范围内且优选在约2:1~约1.5:1的范围内的烷烃与溴之比以及在约250℃~550℃范围内的温度下运行。C2+溴化反应器172可还含有以上就图5的C1+溴化反应器64所述的催化转化区域。
可将C2+组分的滑流171与源自C1+溴化反应器中的流出物流股165合并,并在引入低温合成反应器176中之前,通过任意一种合适手段如换热器174,可将这种合并的流股冷却或加热至约150℃~约350℃,更优选约225℃~约325℃。在低温合成反应器中,在合适催化剂33上,在约150℃~约350℃且更优选约225℃~约325℃的温度范围下并在约1~约100巴范围内的压力下使得烷基溴发生放热反应以产生期望的烃产物(例如高分子量烃、烯烃或其混合物)。据认为,在这些条件下,在合适催化剂上,丙基溴的反应性比甲基溴或乙基溴高,由此丙基单元优先发生低聚,由此生成产物如高分子量烃、烯烃或其混合物,所述产物含有大量C6+链烷烃含量和由此下降的芳族化合物含量。此外,据认为,C2+组分、尤其是丙烷可充当氢供体,使得所有多溴化烷烃中的大部分、尤其是二溴甲烷在这些较低温度条件下和在合适催化剂上转化成更高分子量的烃产物,而不是重质产物或沉积在催化剂上的“焦炭”。由此,有用产物的收率和本发明方法的运行效率提高。然而,在第一阶段合成反应器176中的相对低的运行温度下,仅有一部分存在于烷基溴中的单溴化烷烃可发生转化。
可将源自低温合成反应器176的流出物178与源自C2+热溴化反应器的含有各种烷基溴和溴化氢的流出物173合并,并在引入第二阶段或高温合成反应器168中之前,通过任意一种合适手段如换热器166,对混合物进行冷却或加热。在期望提高链烷烃收率的情况中,将源自C2+热溴化反应器的流出物引入单独的低温合成反应器中并将源自该低温反应器的流出物与源自反应器176的流出物合并,并将混合物传输至第二阶段或高温合成反应器168中。在高温合成反应器中,在合适催化剂上,在约350℃~约450℃的范围内且更优选在约375℃~约425℃的范围内的温度下并在约1~约100巴范围内的压力下使得甲基溴和乙基溴发生放热反应以产生期望的烃产物(例如高分子量烃、烯烃或其混合物)的流股67。据认为,在这些更高温度的条件下,实现了甲基溴和其他烷基溴如乙基溴和丙基溴向烃产物的更完全转化。
分别用于低温和高温合成反应器176和168中的催化剂177和169可为按上述用于将烷基溴催化转化成产物烃的多种合适材料中的任意一种。在某些实施方案中,所述低温和高温合成反应器可包含催化剂的固定床。在某些情况中尤其是在更大的应用中还可使用合成催化剂的流化床,所述流化床具有特定的优势如恒定地除去焦炭和对产物组合物的稳定选择性。用于低温和高温合成反应器两者中的具体催化剂取决于例如所期望的具体产物烃。例如当期望主要具有C3、C4和C5+汽油范围链烷烃化合物和更重的烃馏分的产物烃时,可使用ZSM-5沸石催化剂。当期望产生包含烯烃和C5+产物的混合物的产物烃时,可使用X型或Y型沸石催化剂或SAPO沸石催化剂。合适的沸石的实例包括X型如10-X或Y型沸石,但在本发明的实施方案中可使用具有不同孔径和酸度的其他沸石。用于低温和高温合成反应器中的催化剂不需要相同,只要对用于两个反应器中的催化剂进行选择以生成类似产物例如进行选择以生成主要具有C3、C4和C5+汽油范围链烷烃化合物和更重的烃馏分的烃即可。
在与图2中所描绘的和上述相同的反应器内在不同的区域或床中可含有图8中所示的方法实施方案的低温合成反应器176和高温合成反应器168,并进行改进以提供用于引入流出物173的侧面进料,如本领域技术人员所显而易见的。各个区域或床可以是固定的或流化的且所述反应器可具有合适的装置如内部或外部换热器以对源自第一阶段合成区域或床的流出物进行加热,然后将其流入同一反应器内的第二阶段合成区域或床内。
通过合适手段如换热器171可对源自高温合成反应器168中的流出物流股167进行冷却以回收热,从而用于所述方法中的其他用途如产生蒸汽或对所述方法的进料进行预热(未示出)、或用于本领域技术人员所确定的其他用途,然后将所述流出物流股167传送至产物分离阶段180。从烃产物如高分子量烃、烯烃或其混合物中回收溴化氢并将溴化氢的流股182传送至溴化物氧化阶段184,其中通过部分氧化的金属溴化物盐对溴化氢进行中和以制得金属溴化物盐和蒸汽。向溴化物氧化阶段184中引入氧气或空气的流股186以接触制得的金属溴化物,从而制得元素溴和部分氧化的金属溴化物盐,所述部分氧化的金属溴化物盐可将源自于由所述方法产生的烃中的其他溴化氢中和并除去。可将溴的流股188作为干燥的溴蒸气循环至溴化阶段。可对利用部分氧化的金属溴化物盐对HBr进行氧化而得到的蒸汽进行冷凝、汽提所有残留的溴并作为副产物液体水流股187除去。
在进料气体含有大量适合用作液化石油气(LPG)的气体的情况中,可将这种LPG与进料气体分离以用作终端产品或用作另一种工艺的中间原料。或者,期望将这种LPG转化成烃产物如C5+汽油范围的链烷烃化合物和更重的烃馏分,从而具有更大的价值和用途。通常描绘图5和6中所示的和上述的本发明的某些实施方案的某些方面的方块流程图提供了将进料气体的C3+组分即LPG组分转化成产物烃的方法和系统。
尽管已经对本发明的上述优选实施方案进行了描述和显示,但是应理解,可对本发明完成诸如所提出的替代和改变等且所述替代和改变落在本发明的范围内。
Claims (44)
1.一种方法,包括
提供烷基溴;
在第一催化剂存在下并在足以生成第一烃产物的第一温度下使得所述烷基溴的至少第一部分发生反应,所述第一烃产物至少含有具有至少5个碳原子的烃并具有大量C6+链烷烃含量;和
在第二催化剂的存在下并在足以生成第二烃产物的温度下使得所述烷基溴的第二部分发生反应,所述第二烃产物至少含有具有至少5个碳原子的烃并具有大量取代的芳族化合物含量。
2.权利要求1的方法,其中所述第一温度为约150℃~约300℃。
3.权利要求2的方法,其中所述第一温度为约225℃~约275℃。
4.权利要求1的方法,其中所述第二温度为约300℃~约450℃。
5.权利要求4的方法,其中所述第二温度为约350℃~约425℃。
6.权利要求1的方法,其中使得所述烷基溴的至少第一部分发生反应和使得所述烷基溴的至少第二部分发生反应的步骤同时发生。
7.权利要求1的方法,其中使得所述烷基溴的至少第一部分发生反应和使得所述烷基溴的至少第二部分发生反应的步骤先后发生。
8.权利要求7的方法,其中在使得所述烷基溴的至少第二部分发生反应的步骤期间,所述第一烃产物与所述烷基溴的所述第二部分同时存在。
9.权利要求1的方法,其中所述第一催化剂和第二催化剂相同。
10.权利要求1的方法,其中所述第一催化剂是结晶硅铝酸盐催化剂。
11.权利要求10的方法,其中所述第一催化剂是沸石催化剂。
12.权利要求1的方法,其中所述第二催化剂是结晶硅铝酸盐催化剂。
13.权利要求12的方法,其中所述第二催化剂是沸石催化剂。
14.一种方法,包括:
提供含有较低分子量烷烃并具有约0.1mol%~约10.0mol%C2+组分的第一进料气体流股;
将溴与所述第一进料气体流股反应以生成第一烷基溴;
在第一催化剂存在下并在足以生成第一烃产物的第一温度下,使得至少所述第一烷基溴反应,所述第一烃产物至少含有具有至少5个碳原子的烃并具有大量C6+链烷烃含量;
提供第二进料气体流股,其含有较低分子量烷烃并主要具有C2+组分;
将溴与所述第二进料气体流股反应以生成第二烷基溴;和
在第二催化剂存在下并在足以生成第二烃产物的第二温度下,使得至少所述第二烷基溴反应,所述第二烃产物至少含有具有至少5个碳原子的烃并具有大量取代的芳族化合物含量。
15.权利要求14的方法,其中所述第一温度为约150℃~约300℃。
16.权利要求15的方法,其中所述第一温度为约225℃~约275℃。
17.权利要求14的方法,其中所述第二温度为约300℃~约450℃。
18.权利要求17的方法,其中所述第二温度为约350℃~约425℃。
19.一种系统,包含:
第一合成区域,所述第一合成区域含有合适的催化剂并经构造以在第一温度下由包含烷基溴的合成反应物生成含有链烷烃的烃产物;和
第二合成区域,所述第二合成区域与所述第一合成区域流体连通,其含有第二合适催化剂并经构造以在第二温度下由包含所述烷基溴的未反应部分的合成反应物生成含有取代的芳族化合物的烃产物。
20.权利要求19的系统,其中所述第二温度高于所述第一温度。
21.权利要求19的系统,还包含:
换热器,用于在所述第二合成区域之前加热所述烷基溴的未反应部分。
22.权利要求19的系统,其中所述第一合成区域和第二合成区域包含在一个反应器中。
23.权利要求19的系统,其中所述第一合成区域和第二合成区域包含在分开的反应器中。
24.一种系统,包含:
第一溴化反应器,其经构造以由第一溴化反应物生成包含烷基溴的第一溴化产物,所述第一溴化反应物包含具有约0.1mol%~约10.0mol%C2+组分的较低分子量烷烃;
第一合成反应器,所述第一合成反应器与所述第一溴化反应器流体连通、其含有合适的催化剂并经构造以由所述第一溴化产物生成含有链烷烃的烃产物;
第二溴化反应器,其经构造以由第二溴化反应物生成包含烷基溴的第二溴化产物,所述第二溴化反应物包含主要含有C2+组分的较低分子量烷烃;
第二合成反应器,所述第二合成反应器与所述第二溴化反应器流体连通、其含有合适的催化剂并经构造以由所述第一溴化产物生成含有取代的芳族化合物的烃产物,所述第二合成反应器在高于所述第一溴化反应器的温度下运行。
25.一种方法,包括:
提供含有较低分子量烷烃并具有小于约4.0mol%C2+组分的第一进料气体流股;
将溴与所述第一进料气体流股反应以生成含有多溴化烷烃的第一烷基溴;
提供含有较低分子量烷烃并主要具有C2+组分的第二进料气体流股;
将溴与所述第二进料气体流股反应以生成第二烷基溴;和
在第一催化剂存在下并在足以至少生成含有高分子量烃的第一烃产物的第一温度下,使得所述第一烷基溴和所述第二烷基溴反应,其中在所述第一催化剂和所述第二烷基溴的存在下使得所述多溴化烷烃的一部分发生转化以至少生成一部分所述第一产物。
26.权利要求25的方法,还包括:
在第二催化剂存在下并在足以至少生成第二烃产物的第二温度下,使得至少所述第二烷基溴反应,所述第二烃产物含有高分子量烃并具有比所述第一烃产物更高的芳族化合物含量。
27.权利要求25的方法,其中所述第一温度为约150℃~约350℃。
28.权利要求27的方法,其中所述第一温度为约225℃~约325℃。
29.权利要求26的方法,其中所述第二温度为约350℃~约450℃。
30.权利要求29的方法,其中所述第二温度为约375℃~约425℃。
31.权利要求25的方法,其中所述第一进料气体流股具有小于约2.0mol%的C2+组分。
32.权利要求31的方法,其中所述第一进料气体流股具有小于约0.5mol%的C2+组分。
33.权利要求26的方法,其中在所述第一催化剂存在下使得所述第一烷基溴和所述第二烷基溴反应的步骤和在所述第二催化剂存在下使得至少所述第二烷基溴反应的步骤在两个分开的反应器中进行。
34.权利要求26的方法,其中在所述第一催化剂存在下使得所述第一烷基溴和所述第二烷基溴反应的步骤和在所述第二催化剂存在下使得至少所述第二烷基溴反应的步骤在单个反应器中进行。
35.一种方法,包括:
提供含有较低分子量烷烃并具有小于约4.0mol%C2+组分的第一进料气体流股;
将溴与所述第一进料气体流股反应以生成含有多溴化烷烃的第一烷基溴;
提供含有较低分子量烷烃并主要具有C2+组分的第二进料气体流股;
将溴与所述第二进料气体流股的第一部分反应以生成第二烷基溴;和
在第一催化剂存在下并在足以生成含有包含高分子量烃的第一烃产物的流出物的第一温度下,使得所述第一烷基溴和所述第二进料气体流股的第二部分反应,其中在所述第一催化剂和所述C2+组分的存在下使得所述多溴化烷烃的一部分发生转化以生成至少一部分所述第一烃产物。
36.权利要求35的方法,还包括:
在所述第二催化剂存在下并在足以生成含有第二烃产物的第二流出物的第二温度下,使得所述流出物和至少所述第二烷基溴反应,所述第二烃产物含有高分子量烃并具有比所述第一烃产物更高的芳族化合物含量。
37.权利要求35的方法,其中所述第一温度为约150℃~约350℃。
38.权利要求37的方法,其中所述第一温度为约225℃~约325℃。
39.权利要求36的方法,其中所述第二温度为约350℃~约450℃。
40.权利要求39的方法,其中所述第二温度为约375℃~约425℃。
41.权利要求35的方法,其中所述第一进料气体流股具有小于约2.0mol%的C2+组分。
42.权利要求41的方法,其中所述第一进料气体流股具有小于约0.5mol%的C2+组分。
43.权利要求36的方法,其中在所述第一催化剂存在下使得所述第一烷基溴与所述第二进料气体流股的第二部分反应的步骤和在所述第二催化剂存在下使得所述流出物和至少所述第二烷基溴反应的步骤在两个分开的反应器中进行。
44.权利要求36的方法,其中在所述第一催化剂存在下使得所述第一烷基溴与所述第二进料气体流股的第二部分反应的步骤和在所述第二催化剂存在下使得所述流出物和至少所述第二烷基溴反应的步骤在单个反应器中进行。
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US13/030,053 US8367884B2 (en) | 2010-03-02 | 2011-02-17 | Processes and systems for the staged synthesis of alkyl bromides |
US13/030,053 | 2011-02-17 | ||
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-
2011
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AR080445A1 (es) | 2012-04-11 |
US20130102820A1 (en) | 2013-04-25 |
US8367884B2 (en) | 2013-02-05 |
EP2545017A2 (en) | 2013-01-16 |
US9133078B2 (en) | 2015-09-15 |
AU2011223957A1 (en) | 2012-09-13 |
JP2013521375A (ja) | 2013-06-10 |
EP2545017A4 (en) | 2013-08-21 |
AU2011223957B2 (en) | 2016-04-28 |
EA201290853A1 (ru) | 2013-03-29 |
WO2011109244A3 (en) | 2011-10-27 |
WO2011109244A2 (en) | 2011-09-09 |
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