CN101018751A - 用于将气态烷烃转化为液态烃的方法 - Google Patents

用于将气态烷烃转化为液态烃的方法 Download PDF

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CN101018751A
CN101018751A CNA2005800113352A CN200580011335A CN101018751A CN 101018751 A CN101018751 A CN 101018751A CN A2005800113352 A CNA2005800113352 A CN A2005800113352A CN 200580011335 A CN200580011335 A CN 200580011335A CN 101018751 A CN101018751 A CN 101018751A
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J·J·威库里斯
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Marathon GTF Technology Ltd
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Abstract

将气态烷烃转化为液态烃的方法,其中包含烷烃的气态原料与干燥的溴蒸气反应以形成烷基溴和氢溴酸蒸气。然后将烷基溴和氢溴酸的混合物在合成的结晶硅铝酸盐催化剂(例如ZSM-5沸石)上,在约150℃到约450℃的温度下反应,从而形成较高分子量烃类和氢溴酸蒸气。包含一部分产物的丙烷和丁烷可以通过本方法被回收或再循环以生成另外的C5+烃类。本发明公开了用于本方法的多种从较高分子量烃类中除去氢溴酸蒸气和从氢溴酸中产生溴的方法。

Description

用于将气态烷烃转化为液态烃的方法
相关专利申请的参考:
本申请是一个共同未决的美国专利申请系列号10/826,885(该申请于2004年4月16日提交,名称为“用于将气态烷烃转化为液态烃的方法”)的部分继续申请。
发明背景
发明领域:
本申请涉及一种将较低分子量的气态烷烃转化为用于生产燃料的液态烃的方法,更具体而言,涉及一种方法,其中使包含较低分子量烷烃的气体与干燥的溴蒸气反应以形成烷基溴和氢溴酸,随后将它们在结晶的硅铝酸盐催化剂上反应从而形成液态烃。
相关技术描述:
天然气已经在全世界大量地发现,其主要由甲烷和其它轻烷烃组成。许多已经发现天然气的地区都远离具有重要的天然气管道基础设施或对天然气的市场需求的居住区。由于天然气的低密度,以气态的形式通过管道运输天然气或作为压缩气体在容器中运输天然气都是昂贵的。因此,实践和经济上的限制在于天然气能够以气态的形式运输的距离。天然气的低温液化(LNG)经常用于更加经济地长距离运输天然气。然而,该LNG过程是昂贵的,并且仅有几个国家装备了再气化设血备用以输入LNG。
在天然气中发现的甲烷的另一个用途是作为甲醇生产过程的原料。甲醇在商业上是通过在高温(大约1000℃)下将甲烷转化为合成气(CO和H2)然后在高压(约100大气压)下合成来制备的。有多种技术用于从甲烷生产合成气(CO和H2)。其中包括蒸汽-甲烷重整(SMR)、部分氧化(POX)、自热重整(ATR)、气-热重整(GHR)以及它们的各种组合。SMR和GHR在高温高压下操作,通常超过600℃,并且需要昂贵的包含专门的耐热和抗腐蚀合金管的炉或反应器,所述合金管中装有昂贵的重整催化剂。POX和ATR方法在高压和甚至更高温度下操作,通常温度超过1000℃。由于没有可在这些温度下操作的已知实用金属或合金,因此要求使用复杂且昂贵的具有耐火衬里的反应器和高压废热锅炉来猝灭&冷却所述合成气流出物。并且,大量的资本费用和大量的电能需要用来将氧气或空气压缩到这些高压的工艺过程中。因此,由于使用高温高压,合成气技术是昂贵的,得到高成本的甲醇产品,这限制了其更高价值的使用,例如作为化学原料和溶剂。而且,合成气的生产在热力学和化学上是低效率的,产生大量的额外的废热和不需要的二氧化碳,这往往降低总加工过程的转化效率。Fischer-Tropsch气液(GTL)技术也可以被用于将合成气转化为较重的液态烃,然而该方法的投资费用甚至更高。在每一种情况下,合成气的生产都代表着用于这些甲烷转化过程的资本费用的一大部分。
许多用于替代合成气传统生产方法的方法已经被提出,该生产方法是作为一条制备甲醇或合成液态烃的路线的。然而,迄今为止,由于种种原因这些替代方法中没有一个已经获得商业应用。一些较早的替代现有技术的方法,例如公开于Miller的美国专利号Nos.5,243,098或5,334,777的方法,教导了将较低烷烃,例如甲烷,和金属卤化物反应从而形成金属卤化物和氢卤酸,它们又被氧化镁还原从而形成相应的烷醇。然而,使用氯作为优选的卤素的对甲烷进行卤化导致对一氯甲烷(CH3Cl)的低选择性,产生不需要的副产品例如CH2Cl2和CHCl3,这些副产品难以转化或者要求对单程转化率的严格限制,因此具有很高的再循环率。
其它现有技术方法提出甲烷的催化氯化或溴化作为产生合成气(CO和H2)的替代方法。为了改善在甲醇生产方法总过程中的甲烷卤化步骤的选择性,Miller的美国专利号No.5,998,679教导使用通过金属溴化物的热分解所产生的溴,从而在过量烷烃存在的条件下溴化烷烃,这使得改善了对一卤化中间体例如溴化甲烷的选择性。为了避免使用移动固体流化床的缺陷,所述方法中使用了一种金属氯化物水合物和金属溴化物的循环液混合物。Grosso的美国专利号Nos.6,462,243B1、US6,472,572B1和US6,525,230中描述的方法通过使用溴化也能获得较高的对一卤化中间体的选择性。通过在移动固体循环床中与金属氧化物反应将所得到的烷基溴中间体例如溴化甲烷进一步转化为相应的醇和酯。美国专利号No.6,525,230的另一个具体实施方案通过使用区域反应容器避免了移动床的缺陷,该区域反应容器包含了金属氧化物/金属溴化物的固定床,其是在四个步骤中周期性操作的。这些方法也往往与任何醇一起产生大量的二甲醚(DME)。虽然DME是一种有前途的潜在的柴油机燃料代用品,然而,现在还没有对于DME的实际市场,因此要求有一种昂贵的额外催化方法转化步骤来将DME转化成目前可市场化的产品。不需要产生合成气的其它方法已经被提出,例如在Olah的美国专利号Nos.4,655,893和4,467,130中,通过使用过酸催化剂的催化缩合将甲烷催化缩合成汽油范围的烃类。然而,这些较早的替代方法中没有一个进入商业过程。
众所周知,取代的烷烃,尤其是甲醇,能够在多种形式的结晶硅铝酸盐,又名沸石上,被转化为烯烃和汽油沸程的烃类。在从甲醇到汽油(MTG)的方法中,一种择形沸石催化剂,ZSM-5,被用于将甲醇转化为汽油。煤或甲烷气因此能通过使用常规的技术被转化为甲醇,随后再转化为汽油。然而,由于甲醇生产的高成本,和当前或预计的汽油价格,该MTG方法不被认为是经济可行的。因此,需要一种将天然气中发现的甲烷和其它烷烃转化为有用的液态烃产品的经济的方法,这些液态烃产品由于其较高的密度和价值而被更经济地运输,因此显著地帮助偏远的天然气储量的开发。进一步需要一种在操作中是相对廉价、安全和简单的转化存在于天然气中的烷烃的方法。
发明概述
为了获得上述和其它目标,以及根据本发明的目的,如本文体现和一般描述的那样,本发明的一个方面涉及一种用于将气态烷烃转化为液态烃的方法。该方法包括将具有较低分子量烷烃的气体原料和溴蒸气反应以形成烷基溴和氢溴酸。所述烷基溴和氢溴酸在合成的结晶硅铝酸盐催化剂的存在下以及在足够的温度下反应从而形成较高分子量的烃类和氢溴酸蒸气。通过将所述氢溴酸蒸气与金属氧化物反应形成金属溴化物和水蒸汽而将所述氢溴酸蒸气从所述较高分子量的烃类中除去。
在本发明的另一方面,提出了一种方法,用来将气态烷烃转化为液态烃,其中使具有较低分子量烷烃的气态原料与溴蒸气反应从而形成烷基溴和氢溴酸。所述烷基溴和氢溴酸在合成的结晶硅铝酸盐催化剂的存在下以及在足够的温度下反应从而形成较高分子量的烃类和氢溴酸蒸气。所述氢溴酸蒸气和所述较高分子量烃类被输送到具有金属氧化物颗粒的床的第一容器中,所述氢溴酸蒸气与金属氧化物颗粒的床反应从而形成金属溴化物颗粒和水蒸汽。
在本发明的又一方面,提出了一种方法,用来将气态烷烃转化为液态烃,其中使具有较低分子量烷烃的气态原料与溴蒸气反应从而形成烷基溴和氢溴酸。所述烷基溴和氢溴酸在合成的结晶硅铝酸盐催化剂的存在下以及在足够的温度下反应从而形成较高分子量的烃类和氢溴酸蒸气。通过与金属氧化物反应从而形成第一金属溴化物和水蒸汽而将所述氢溴酸蒸气从所述的较高分子量烃类中除去。使用含氧气体氧化第一金属溴化物从而形成溴蒸气。将所述溴蒸气与还原的金属溴化物反应从而形成第二金属溴化物。
附图简述
并入本说明书并且构成本说明书的一部分的附图举例说明了本发明的实施方案,并与本说明书一起,用来解释本发明的原理。
在附图中:
图1是本发明所述的方法的简化方框流程图;
图2是本发明所述的方法的一个实施方案的示意图;
图3是本发明所述的方法的另一个实施方案的示意图;
图4是本发明所述方法的溴代甲烷转化率和低聚(oigimerization)反应的产物选择性作为温度的函数的图;
图5是对于溴代甲烷、干燥氢溴酸和甲烷的实施例相对于仅有溴代甲烷和甲烷的转化率和选择性的对比图;
图6是来自溴代甲烷和二溴甲烷的反应的产物选择性相对于来自仅有溴代甲烷的反应的产物选择性的对比图;
图7是本发明所述方法的一般冷凝产物样品的链烷烃-烯烃-环烷烃-芳香烃(PONA)分析图;
图8是本发明另一个一般冷凝产物样品的PONA分析图;
图9A是本发明所述的方法的另一个实施方案的示意图;
图9B是图9A中所示的本发明所述方法的实施方案的示意图,它描述了一种替代处理方案,其可以在氧化阶段用氧气代替空气时被使用;
图10A是图9A中所示的本发明所述方法的实施方案的示意图,其中,通过金属氧化物床的料流被逆转;
图10B是图10A所示的本发明所述方法的实施方案的示意图,它描述了一种替代处理方案,其可以在氧化阶段用氧气代替空气时被使用;
图11A是本发明所述方法的另一个实施方案的示意图;
图11B是图11A所示的本发明所述方法的实施方案的示意图,它描述了一种替代处理方案,其可以在氧化阶段用氧气代替空气时被使用;
图12是本发明所述方法的另一个实施方案的示意图;
图13是图12中所示的本发明所述方法的实施方案的示意图,其中通过金属氧化物床的料流被逆转;和
图14是本发明所述方法的另一个实施方案的示意图。
优选实施方案详述
如同在整个说明书中所使用的,术语“较低分子量烷烃”是指甲烷、乙烷、丙烷、丁烷、戊烷或其混合物。如同在整个说明书中所使用的,“烷基溴化物”是指一、二、和三溴代烷烃。同时,在图2和3所示的本发明所述方法的实施方案中在管线11和111中的原料气分别优选是可能经处理除去了硫化合物和二氧化碳的天然气。在任何情况下重要的是注意,在本发明所述方法的原料气中的少量二氧化碳,例如少于约2mol%,是可以允许的。
一般性描述本发明的方法的方框流程图示于图1中,而本发明方法的具体实施方案示于图2和3中。参阅图2,由原料气和再循环气流在约1bar到约30bar范围内的压力下的混合物组成的包含较低分子量烷烃的气流被通过管线、管或导管62运输或传送,被与通过管线25和泵24输送的干燥的溴液混和,并且被转入热交换器26,所述液态溴在此处被蒸发。所述较低分子量烷烃和干燥的溴蒸气的混合物被供给反应器30。优选地,在被引入反应器30的混合物中的较低分子量烷烃对干燥溴蒸气的摩尔比大于2.5∶1。反应器30具有入口预热器区28,其加热所述混合物至约250℃到约400℃范围内的反应引发温度。
在第一反应器30中,所述较低分子量烷烃与干燥的溴蒸气在约250℃到约600℃范围内的较低温变和约1bar到约30bar范围内的压力条件下发生放热反应从而产生气态烷基溴化物和氢溴酸蒸气。所述操作温度范围的上限高于所述反应引发温度范围的上限,由于所述溴化反应的放热特性使得所述原料混合物被加热到所述反应引发温度。就甲烷来说,溴代甲烷的形成是按照以下一般反应发生的:
CH4(g)+Br2(g)→CH3Br(g)+HBr(g)
该反应的发生具有极高的溴代甲烷选择性。例如,就甲烷的溴化来说,在甲烷对溴的比例约为4.5∶1时,对一卤代的溴代甲烷的选择性在90到95%的范围内。少量的二溴甲烷和三溴甲烷也在所述溴化反应中形成。较高的烷烃,例如乙烷、丙烷和丁烷,也轻易被溴化,产生一和多溴代的产物。如果使用烷烃对溴的比例明显地小于约2.5∶1,则发生对溴代甲烷的选择性显著地低于90%并且观察到大量不需要的炭黑形成。也已经显示,可以存在于对所述溴化反应器的原料气中的其它的烷烃,例如乙烷、丙烷和丁烷,被轻易地溴化从而形成乙基溴化物、丙基溴化物和丁基溴化物。此外,所述被进料入第一反应器30的干燥的溴蒸气基本上是无水的。申请人已经发现,来自第一反应器30中的溴化步骤的基本上所有水蒸汽的除去基本上消除不需要的二氧化碳的形成,因此增加烷烃溴化为烷基溴化物的选择性,并且消除由烷烃形成二氧化碳过程中产生的大量的废热。
所述包含烷基溴化物和氢溴酸的流出物被通过管线31从第一反应器排出以及在流至第二反应器34之前在热交换器32中被部分地冷却到约150℃到约350℃的温度范围内。在第二反应器34中,所述烷基溴化物被在约150℃到约450℃的温度范围下,以及在约1到30bar的压力范围下,在结晶硅铝酸催化剂,优选沸石催化剂,以及最优选ZSM-5沸石催化剂的固定床33上发生放热反应。虽然所述沸石催化剂优选以氢、钠或镁的形式被使用,但该沸石也可以通过与其它碱金属阳离子(例如Li、Na、K或Cs),与碱土金属阳离子(例如Mg、Ca、Sr或Ba),或与过渡金属阳离子(例如Ni、Mn、V、W)进行离子交换,或至所述氢的形式而被改性。具有不同孔径和酸性的其它沸石催化剂可以用于第二反应器34,这对于熟练的技术人员来说将是显而易见的,所述具有不同孔径和酸性的沸石催化剂是通过改变所述铝硅比合成的。在该反应器中,所述烷基溴化物被低聚以制备较高分子量烃类产品(主要是C3、C4和C5+汽油-范围和更重的烃馏分)以及额外的氢溴酸蒸气的混合物。
第二反应器34的操作温度是决定所述低聚反应对多种较高分子量液态烃产品选择性的一个重要参数。第二反应器34的操作温度优选在约150℃到450℃的范围内。第二反应器中温度高于约300℃导致轻烃类,例如不需要的甲烷的产率增加,而更低的温度增加较重分子量烃产品的产率。在所述温度范围的低端,如果溴代甲烷在ZSM-5沸石上在低至150℃的温度下反应,注意到在20%左右的显著溴化甲烷转化率,并且有对C5+产品具有高选择性。也注意到,溴代甲烷相对于氯代甲烷或其它取代的甲基化合物例如甲醇而言在较低的温度范围内呈现出更高的反应活性。值得注意的是,就在优选的沸石ZSM-5催化剂上的烷基溴反应来说,环化反应也会发生,以致于C7+馏分主要由取代的芳香化合物组成。在接近300℃的升高温度下,溴代甲烷的转化率提高到90%或更高,然而对C5+产品的选择性降低以及对较轻产品,特别是不需要的甲烷的选择性增加。令人惊奇地,仅有很少的乙烷或C2-C3烯烃组分形成。在接近450℃的温度下,溴代甲烷几乎全部都转化为甲烷。在约300℃到400℃之间的最佳操作温度范围内,作为所述反应的副产物,在操作期间随着时间的过去少量的碳将在催化剂上积累,由此会导致在数小时到数百小时的范围内催化剂活性的降低,这取决于所述反应的条件和所述原料气的组成。据信,高于约400℃的较高反应温度,伴随甲烷的形成,有利于烷基溴化物的热裂解和碳或焦炭的形成,由此增加催化剂的失活速率。相反地,在所述温度范围低端的温度,特别是低于约300℃,也会有助于焦化,这归因于较重产品从所述催化剂上脱附速率的降低。因此,在第二反应器34中的在约150℃到约450℃的范围内,但是优选在约300℃到约400℃的范围内的操作温度范围解决了所需C5+产品的提高选择性和归因于碳形成的更低失活速率与较高的单程转化率之间的矛盾,这使催化剂的量、循环率以及要求的设备规模最小化。
催化剂可以在原位被周期性地再生,方法是:将反应器34与正常操作流路隔离,在约1到约5bar范围内的压力下、在约400℃到约650℃范围内的提高的温度下用惰性气体通过管线70吹洗从而在实际可能的程度上除去吸附在所述催化剂上的未反应的物料,接着通过在约1bar到约5bar的压力下和约400℃到约650℃范围内的温度下由管线70向反应器34中加入空气或惰性气体稀释的氧气来将沉积的碳氧化成CO2。在所述再生期过程中通过管线75将二氧化碳和剩余的空气和惰性气体从反应器34中排出。
包含所述较高分子量烃类产品和氢溴酸的流出物通过管线35从第二反应器34排出,并在交换器36中被冷却到0℃到约100℃范围内的温度以及与来自烃类汽提塔47的管线12中的蒸气流出物混合,该蒸气流出物包含原料气和在烃类汽提塔47中通过与所述原料气接触而汽提出的剩余烃产品。所述混合的蒸气混合物被送入洗涤塔38,并且与浓缩的含水的部分氧化的金属溴化物盐溶液接触,该盐溶液包含金属氢氧化物和/或金属氧化物和/或金属溴氧化物物质,其被通过管线41输送到洗涤塔38。所述溴化物盐的优选金属是Fe(III)、Cu(II)或Zn(II),或其混合物,因为这些金属价格比较低廉并且在约120℃到约180℃范围的较低温度下轻易氧化,于是允许使用氟聚合物衬里的设备;虽然本发明所述方法也可以使用形成可氧化的溴化物盐的Co(II)、Ni(II)、Mn(II)、V(II)、Cr(II)或其它过渡金属。作为选择,可以使用也形成可氧化的溴化物盐的碱土金属,例如Ca(II)或Mg(II)。在洗涤塔38中冷凝的任何液态烃产品可以被撇清和在管线37中排出,并且在管线54中被加入到从产品回收单元52流出的液态烃产品中。氢溴酸被溶于所述水溶液并且被所述金属氢氧化物和/或金属氧化物和/或金属溴氧化物物质中和,从而在溶液中得到金属溴化物盐以及水,其被通过管线44从洗涤塔38中除去。
作为流出物从洗涤塔38中除去的包含所述较高分子量烃类产物的剩余蒸气相被通过管线39送到脱水器50,从而通过管线53从所述蒸气流中除去基本上所有的水。然后通过管线53将所述水从脱水器50除去。包含所述较高分子量烃类产物的干燥的蒸气流被进一步通过管线51输送到产品回收单元52中,从而回收需要的丙烷和丁烷,而作为液体产物的主要是C5+馏分在管线54中。任何脱水和液体回收的常规方法都可以用于本发明的方法中,例如固体-床干燥剂吸附继而冷冻冷凝,低温膨胀,或循环吸收油,这些对于熟练的技术人员来说是显而易见的,用于处理天然气或炼厂气流的方法。来自产品回收单元52的剩余蒸气流出物然后被分成可以作为燃料用于本方法的清洗气流57和通过压缩器58压缩的再循环剩余蒸气。从压缩器58排出的再循环剩余蒸气被分成两个部分。等于至少所述原料气摩尔体积2.5倍的第一部分被通过管线62输送,并被与通过泵24输送的干燥的液态溴混合,被在交换器26中加热从而蒸发所述溴并且被送入第一反应器30。第二部分被通过管线63从管线62接出并且被通过控制阀60调节,其速率足够稀释所述烷基溴浓缩物入反应器34并且吸收所述反应热致使反应器34维持在所选定的操作温度,优选在约300℃到约400℃的范围,从而最佳化转化率对选择性以及最小化由于碳沉积而导致的催化剂的失活速率。这样,由再循环蒸气流出物提供的稀释作用不仅缓和了第二反应器34中的温度还使第一反应器30中的溴化的选择性得以控制。
溶液中包含金属溴化物盐的水被输送到烃类汽提塔47中,这些水是通过管线44从洗涤塔38中被除去的,在汽提塔47中剩余的溶解的烃类被通过与由管线11输送进入的原料气接触而从水相中汽提。所述汽提过的水溶液被通过管线65从烃类汽提塔47中输出,以及在热交换器46中被冷却到约0℃到约70℃范围的温度,然后被输送到吸收器48中,在此剩余的溴被从管线67中的排出流中回收。来自洗涤塔48的含水溶液流出物被通过管线49输送到热交换器40从而被预热到约100℃到600℃范围的温度,以及最优选的范围是约120℃到约180℃,并且被送入第三反应器16中。氧气或空气通过管线10被鼓风机或压缩机13在约环境压力到约5bar范围的压力下被送入到溴汽提塔14中,从而从水中汽提剩余的溴,所述水从汽提塔14在管线64中被除掉并与来自脱水器50的水流53混合从而在管线56中形成水流出物流,其被从所述过程中除去。离开溴汽提塔14的氧气或空气被通过管线15供入反应器16,该反应器在约环境压力到约5bar范围的压力下和约100℃到约600℃范围的温度下操作,但是最优的范围是约120℃到约180℃,以便氧化含水金属溴化物盐溶液从而得到单质溴和金属氢氧化物和/或金属氧化物和/或金属溴氧化物物质。如上所述,虽然可以使用形成可氧化的溴化物盐的Co(II)、Ni(II)、Mn(II)、V(II)、Cr(II)或其它过渡金属,但是所述溴化物盐的优选金属是Fe(III)、Cu(II)或Zn(II),或其混合物,因为这些金属费用较低并且在约120℃到约180℃范围的较低温度下轻易氧化,允许使用氟聚合物衬里的设备。作为选择,可以使用也形成可氧化的溴化物盐的碱土金属,例如可以使用Ca(II)或Mg(II)。
氢溴酸与所形成的金属氢氧化物和/或金属氧化物和/或金属溴氧化物物质反应,从而再一次形成所述金属溴化物盐和水。在反应器16中的热交换器18供热以蒸发水和溴。因此,整个反应的结果是,在由在催化循环中操作的所述金属溴化物/金属氧化物或金属氢氧化物催化的液相中,将在第一反应器30和第二反应器34中产生的氢溴酸净氧化为单质溴和水蒸汽。在所述金属溴化物是Fe(III)Br3的情况下,所述反应被认为是:
1)Fe(+3a)+6Br(-a)+3H(+a)+3/2O2(g)=3Br2(g)+Fe(OH)3
2)3HBr(g)+H2O=3H(+a)+3Br(-a)+H2O
3)3H(+a)+3Br(-a)+Fe(OH)3=Fe(+3a)+3Br(-a)+3H2O
所述通过管线19从第三反应器16的出口作为蒸气离开的单质溴和水以及任何剩余的氧气或氮气(如果使用空气作为氧化剂),在约0℃到约70℃范围的温度下和约环境压力到5bar范围的压力下,在冷凝器20中被冷却,从而冷凝所述溴和水,并被输送到三相分离器22中。在三相分离器22中,因为液态水具有对溴的有限溶解度,大约3%重量的任何额外的被冷凝的溴形成分离的且稠密的液态溴相。但是,所述液态溴相具有特别低的对水的溶解度,大约小于0.1%。因此,通过冷凝液态溴和水、借助简单的物理分离而滗析水以及接着再蒸发液态溴,可以轻易地得到基本上干燥的溴蒸气。
液态溴被通过泵24从三相分离器22泵入管线25中,以达到足够与蒸气流62混合的压力。因而,溴在该过程中被回收并再循环。所述剩余的氧气和氮气以及任何未被冷凝的剩余溴蒸气从三相分离器22离开并通过管线23被输送到溴洗涤塔48,在此剩余的溴通过溶解入以及通过与在含水金属溴化物溶液流65中的被还原的金属溴化物反应而被回收。水通过管线27从分离器22中被除去,并被引入汽提塔14。
在本发明的另一个实施方案中,参见图3,由原料气和再循环气流在约1bar到约30bar范围内的压力下的混合物组成的包含较低分子量烷烃的气流,被通过管线、管或导管162输送或传送,被与通过泵124输送的干燥的溴液体混合,并被输送到热交换器126中,在此所述液态溴被蒸发。所述较低分子量烷烃与干燥溴蒸气的混合物被供给反应器130。优选地,被引入反应器130的混合物中较低分子量烷烃对干燥的溴蒸气的摩尔比大于2.5∶1。反应器130具有入口预热器区128,其加热所述混合物至约250℃到约400℃范围的反应引发温度。在第一反应器130中,所述较低分子量烷烃与干燥的溴蒸气在约250℃到约600℃范围的相对较低温度下和约1bar到约30bar范围的压力下发生放热反应,产生气态的烷基溴化物和氢溴酸蒸气。所述操作温度范围的上限高于所述进料混合物被加热至的反应引发温度范围的上限,这是由于所述溴化反应的放热特性。就甲烷来说,溴代甲烷的形成是按照以下一般反应发生的:
CH4(g)+Br2(g)→CH3Br(g)+HBr(g)
该反应的发生具有极高的对溴代甲烷的选择性。例如,在溴与摩尔过量的甲烷以4.5∶1的甲烷对溴的比例反应的情况下,对所述一卤化的甲基溴化物的选择性在90到95%范围内。少量的二溴甲烷和三溴甲烷也在溴化反应中形成。较高的烷烃,例如乙烷、丙烷和丁烷,也被轻易地溴化,产生一和多溴化物质。如果使用的烷烃对溴的比例明显小于2.5∶1,则发生对溴代甲烷的选择性显著地低于90%,并且观察到不需要的碳黑大量形成。也已经显示,可以存在于对于所述溴化的原料气中的其它的烷烃,例如乙烷、丙烷和丁烷,被轻易地溴化从而形成乙基溴化物、丙基溴化物和丁基溴化物。此外,被输送入第一反应器130的所述干燥的溴蒸气基本上是无水的。申请人已经发现,来自第一反应器130中的溴化步骤的基本上所有的水蒸汽的除去基本上消除了不需要的二氧化碳的形成,因此增加烷烃溴化为烷基溴化物的选择性,并且消除产生自由烷烃形成二氧化碳过程的大量的废热。
所述包含烷基溴化物和氢溴酸的流出物被通过管线131从第一反应器130排出,并且在流向第二反应器34之前在热交换器132中被部分地冷却到约150℃到约350℃范围的温度。在第二反应器134中,所述烷基溴化物被在约150℃到约450℃范围的温度下,以及在约1到30bar范围的压力下,在结晶硅铝酸盐催化剂,优选沸石催化剂,以及最优选ZSM-5沸石催化剂的固定床上发生放热反应。虽然所述沸石催化剂优选以氢、钠或镁的形式被用,但该沸石也可以通过与其它碱金属阳离子(例如Li、Na、K或Cs),与碱土金属阳离子(例如Mg、Ca、Sr或Ba),或与过渡金属阳离子(例如Ni、Mn、V、W)进行离子交换,或至所述氢的形式而被改性。具有不同孔径和酸性的其它沸石催化剂可以用于第二反应器134,这对于熟练的技术人员来说将是显而易见的,这些具有不同孔径和酸性的沸石催化剂是通过改变所述铝硅比而合成的。在该反应器中,所述烷基溴化物被低聚以制备较高分子量烃类产品以及额外的氢溴酸蒸气的混合物。
第二反应器134的操作温度是决定所述低聚反应对多种较高分子量液态烃产品的选择性的一个重要参数。第二反应器134的操作温度优选在约150℃到450℃的范围内,但更优选约300℃到400℃的范围内。第二反应器中温度高于约300℃导致轻质烃类(例如不需要的甲烷)的产率增加,而较低的温度则增加较重分子量烃类产品的产率。在所述温度范围的低端,在溴代甲烷在ZSM-5沸石上在低至150℃的温度下反应的情况下,注意到在20%左右的显著溴代甲烷转化率,并且其对C5+产品具有高选择性。值得注意的是,就在优选的沸石ZSM-5催化剂上反应的烷基溴化物来说,环化反应发生,以致于产生的C7+馏分包含高比率的取代的芳香化合物。在接近300℃的升高的温度下,溴代甲烷的转化率提高到90%或更高,然而对C5+产品的选择性降低,而对较轻产品,特别是不需要的甲烷的选择性增加。令人惊奇地,仅产生很少的乙烷或C2-C4烯烃化合物。在接近450℃的温度下,溴代甲烷几乎全部都转化为甲烷。在约300℃到400℃之间的最佳操作温度范围内,作为所述反应的副产物,在操作期间随着时间的过去少量的碳将在所述催化剂上积累,由此导致在数百小时的范围内催化剂活性的降低,这取决于所述反应的条件和原料气的组成。人们发现,高于约400℃的较高的反应温度有利于烷基溴化物的热裂解和碳的形成,因此增加所述催化剂的失活率。相反地,在所述温度范围的低端、特别是在低于约300℃下操作,也会促进焦化,这可能是由于烃类产品的降低的脱附率。因此,在第二反应器134中的在约150℃到450℃的范围内,但更优选在约300℃到400℃的范围内的操作温度权衡了对需要的产品的增加的选择性和归因于碳形成的更低的失活率与较高的单程转化率,这使催化剂的量、循环率以及要求的设备规模最小化。
催化剂可以在原位被周期性地再生,方法是:从正常操作流路中隔离反应器134,在约1bar到约5bar范围的压力下和在400℃到650℃范围的提高的温度下用惰性气体通过管线170吹洗从而在可操作的范围内除去吸附在所述催化剂上的未反应的原料,接着通过在约1bar到约5bar范围的压力下和400℃到650℃范围的温度下由管线170向反应器134中加入空气或惰性气体稀释的氧气来将沉积的碳氧化成CO2。在所述再生期间通过管线175将二氧化碳和剩余的空气或惰性气体从反应器134中排出。
包含所述较高分子量烃类产品和氢溴酸的流出物通过管线135从第二反应器134中排出,在交换器136中被冷却到约0℃到约100℃范围的温度,并与来自烃类汽提塔147的管线112中的蒸气流出物混合。然后将所述混合物送入洗涤塔138,并且与汽提过的循环水接触,所述汽提过的循环水是用任何合适的方法,例如泵143,在管线164中被输送到洗涤塔138的并且在热交换器155中被冷却到约0℃到约50℃范围内的温度。任何在洗涤塔138中被冷凝的液态烃产品可以作为物流137被撇清并排出,并被入到液态烃产品154中。氢溴酸在洗涤塔138中被溶解到水溶液中,该水溶液被通过管线144从所述洗涤塔138中除去,然后被送入烃类汽提塔147,在该汽提塔中溶于所述水溶液中的剩余烃被通过与原料气111接触而汽提出。来自烃类汽提塔147的汽提过的水相流出物在热交换器146中被冷却到约0℃到约50℃范围内的温度,然后通过管线165被送到吸收器148中,在该吸收器148中剩余的溴被从排出物流167中回收。
包含所述较高分子量烃类产物的剩余蒸气相被作为流出物从洗涤塔138中除去,并且被送入脱水器150以从所述气流中除去基本上全部的水。所述水然后被通过管线153从脱水器150除去。包含所述较高分子量烃类产物的干燥的气流被进一步通过管线151输送到产品回收单元152中,从而回收需要的C3和C4,但在管线154中作为液体产物的主要是C5+馏分。任何脱水和液体回收的常规方法都可以被用于本发明的实施,例如固体-床干燥剂吸附后接着进行,例如,冷冻冷凝,低温膨胀,或循环吸收油,这些熟练技术人员公知的用于处理天然气或炼厂气流的方法。来自产品回收单元152的剩余蒸气流出物然后被分成可以作为燃料用于本方法的清洗气流157和通过压缩机158被压缩的再循环剩余蒸气。从压缩机158排出的再循环剩余蒸气被分成两个部分。等于至少所述原料气体积2.5倍的第一部分被通过管线162输送,与在管线125中输送的液态溴混合,以及输送至热交换器126中,在此处蒸发所述溴并且被送入第一反应器130。第二部分被通过管线163从管线162排出,以及被通过控制阀160调节,在足够稀释所述烷基溴浓缩物入反应器134并吸收所述反应热的速度下进行,致使反应器134维持在所选定的操作温度,优选在约300℃到约400℃范围的温度,从而最佳化转化率对选择性以及最小化由于碳沉积而导致的催化剂的失活率。这样,由再循环蒸气流出物提供的稀释作用允许在第一反应器130中的溴化的选择性被控制,而且缓和了第二反应器134中的温度。
氧气、富氧空气或空气110被通过鼓风机或压缩机113在压力为约环境压力到约5bar的范围输送到溴汽提塔114中,从而从水中汽取剩余的溴,该水通过管线164离开汽提塔114并被分成两个部分。第一部分汽提过的水被通过管线164再循环,在热交换器155中被冷却到约20℃到约50℃范围的温度,并通过任何适当的方法,例如泵143,被维持在足够进入洗涤塔138的压力。对再循环水的比例进行选择,以致于通过管线144从洗涤塔138中除掉的氢溴酸溶液流出物具有按氢溴酸重量计的约10%到约50%范围的浓度,但更优选在按重量计约30%到约48%的范围从而最小化必须在交换器141和预热器119中蒸发的水的量以及最小化在所得到的酸上的HBr的蒸气压。第二部分来自汽提塔114的水被通过管线156从管线164和所述过程中除掉。
包含于来自洗涤塔148的水溶液流出物中的溶解的氢溴酸被通过管线149输送,并且与在管线115中离开溴汽提塔114的氧气、富氧空气或空气混合。所述混合的水溶液流出物与氧气、富氧空气或空气被输送到热交换器141的第一侧,以及通过预热器119,在该预热器中所述混合物被预热到约100℃到约600℃,以及最优选在约120℃到约180℃范围的温度,以及被送入包含金属溴化物盐的第三反应器117。虽然可以使用形成可氧化的溴化物盐的Co(II)、Ni(II)、Mn(II)、V(II)、Cr(II)或其它过渡金属,但所述溴化物盐的优选金属是Fe(III)、Cu(II)或Zn(II)。作为选择,可以使用也可以形成可氧化的溴化物盐的碱土金属,例如Ca(II)或Mg(II)。氧化反应器117中的金属溴化物盐能够作为浓缩的水溶液使用,或者优选地,所述浓缩的含水盐溶液可以被吸入多孔的高表面积且耐酸的惰性载体中,例如硅胶。氧化反应器117在约环境压力到约5bar范围的压力下和在约100℃到600℃范围的温度下操作,但最优选约120℃到180℃的范围;在其中,所述金属溴化物被氧气氧化,产生单质溴和金属氢氧化物、金属氧化物或金属溴氧化物物质或者,在水可以主要以蒸汽的形式存在的更高温度和更低压力条件下操作的负载金属溴化物盐的情况下,产生金属氧化物。在这两种情况的任一种下,所述氢溴酸与所述金属氢氧化物、金属溴氧化物或金属氧化物物质反应并被中和,复原所述金属溴化物盐并产生水。因此,整个反应导致第一反应器130和第二反应器134中产生的氢溴酸净氧化为单质溴和水蒸汽,这由催化循环中操作的所述金属溴化物/金属氢氧化物或金属氧化物催化。在所述金属溴化物为水溶液中的Fe(III)Br2,且在其中水可以以液态形式存在的压力和温度范围内操作的情况下,所述反应被认为是:
1)Fe(+3a)+6Br(-a)+3H(+a)+3/2O2(g)=3Br2(g)+Fe(OH)3
2)3HBr(g)+H2O=3H(+a)+3Br(-a)+H2O
3)3H(+a)+3Br(-a)+Fe(OH)3=Fe(+3a)+3Br(-a)+3H2O
在所述金属溴化物为负载在惰性载体上的Cu(II)Br2,并且在水主要以蒸汽的形式存在的较高温度和较低压力条件下操作的情况下,所述反应被认为是:
1)2Cu(II)Br2=2Cu(I)Br+Br2(g)
2)2Cu(I)Br+O2(g)=Br2(g)+2Cu(II)O
3)2HBr(g)+Cu(II)O=Cu(II)Br2+H2O(g)
从第三反应器117的出口以蒸气的形式离开的单质溴和水以及任何剩余的氧气或氮气(如果使用空气或富氧空气作为所述氧化剂),被在交换器141的第二侧和冷凝器120中冷却到约0℃到约70℃范围的温度,在此所述溴和水被冷凝并输送到三相分离器122中。在三相分离器122中,因为液体水对溴具有有限的溶解度,约为3%重量,任何额外的被冷凝的溴形成分离的且稠密的液态溴相。但是,所述液态溴相具有特别低的对水的溶解度,约为小于0.1%。因此,通过冷凝液态溴和水,用简单的物理分离而倾析水以及接着再蒸发液态溴,可以轻易地得到基本上干燥的溴蒸气。重要的是,在能导致HBr接近完全反应的条件下操作,从而避免在冷凝的液态溴和水中出现明显的残余HBr,因为HBr增加水相中溴的互溶性,以及在足够高的浓度下,产生单一的三元液相。
液态溴被通过泵124从三相分离器122泵送至足够与蒸气流162混合的压力。因此,所述溴在该过程中被回收并再循环。所述剩余的空气、富氧空气或氧气以及任何未被冷凝的剩余溴蒸气离开三相分离器122并且被通过管线123输送到溴洗涤塔148,在此剩余的溴通过溶解于由管线165被送至洗涤塔148的氢溴酸溶液流而被回收。水被通过管线129从三相分离器122中除去,并被输送到汽提塔114。
以下实施例证明本发明的实施和效用,但不能被认为是对其范围的限制。
实施例1
使干燥的溴和甲烷的多种混合物在459℃到491℃范围的温度下以大约7200hr-1的气时空速(GHSV,其定义为:以标准升每小时为单位的气体流速除以以升为单位的包括催化剂床孔隙在内的总反应器催化剂床的体积)均匀地反应。本实施例的结果表明,对于甲烷对溴的摩尔比大于4.5∶1时,对溴代甲烷选择性在90%到95%的范围内,溴接近完全转化。
实施例2
图7和图8阐明两个C6+液体产物样品的两个示范性的PONA分析,这两个样品是在以溴代甲烷和甲烷在ZSM-5沸石催化剂上反应进行的两个试运行期间回收的。这些分析显示所制得的C6+馏分的实质芳烃含量。
实施例3
使溴代甲烷在ZSM-5沸石催化剂上以大约94hr-1的气时空速(GHSV),在约100℃到约460℃的温度范围,约为2bar的压力下反应。如图4所示,其是溴代甲烷转化率和对于低聚反应的产物选择性作为温度的函数的图,溴代甲烷转化率在约200℃到约350℃的范围内迅速地增加。在约100℃到约250℃范围内的较低温度有利于对较高分子量产品的选择性,但此时转化率低。约250℃到约350℃范围内的较高温度显示在50%到接近100%范围内的较高转化率,但观察到增加对较低分子量产品、特别是不需要的甲烷的选择性。在高于350℃的较高温度下,对甲烷的选择性迅速地增加。在约450℃,发生向甲烷的几乎完全转化。
实施例4
使溴代甲烷、溴化氢和甲烷在ZSM-5沸石催化剂上在约2bar的压力下反应,反应温度约为250℃,也可以是约260℃,GHSV大约76hr-1。也进行比较试验,比较试验使用仅有溴代甲烷与甲烷而不含溴化氢的混合物,在相同的ZSM-5催化剂上在大约相同的压力和约250℃以及约260℃温度下,以大约73hr-1的GHSV进行。图5,其是说明若干实施例试运行的对比转化率和选择性的图,显示由于HBr的存在而对产品选择性产生的影响十分微弱。因为氢溴酸对转化率和选择性的影响十分微弱,因此在所述烷基溴化物的转化反应之前不必除去在所述溴化反应中产生的氢溴酸,其中总之要形成额外的氢溴酸。这样,所述方法可以被充分地简化。
实施例5
使溴代甲烷在230℃在ZSM-5沸石催化剂上反应。二溴甲烷被加入到该反应器。图6,其是产物选择性的图,指出相对于仅有溴代甲烷的情况,溴代甲烷和二溴甲烷的反应导致选择性向C5+产物转移。由此,这些结果证明,二溴甲烷也是反应性的,因此,本发明的方法不要求在所述溴化步骤中的对溴化甲烷的非常高的选择性。然而,已经观察到二溴甲烷的存在增加催化剂失活率,相对于纯的溴代甲烷,要求较高的操作温度从而最佳化选择性和失活率之间的平衡。
实施例6
使甲烷中含12.1mol%溴代甲烷和2.8mol%丙基溴的混合物在295℃在ZSM-5沸石催化剂上以大约260hr-1的GHSV反应。观察到大约86%的溴代甲烷转化率和大约98%的丙基溴转化率。
这样,依照本发明上述的所有实施方案,所述金属溴化物/金属氢氧化物、金属溴氧化物或金属氧化物在催化循环中操作,其允许溴轻易地在所述过程中再循环。所述金属溴化物轻易地被氧气、富氧空气或空气氧化,这既可发生在水相也可发生在蒸气相,在约100℃到约600℃范围的温度、并且最优选在约120℃到约180℃的范围,从而得到单质溴蒸气和金属氢氧化物、金属溴氧化物或金属氧化物。在低于约180℃的温度下操作是有利的,因此允许使用廉价的耐腐蚀的氟聚合物衬里的设备。氢溴酸被通过与金属氢氧化物或金属氧化物反应而中和,产生水蒸汽和金属溴化物。
所述单质溴蒸气和水蒸汽被冷凝,并且通过简单的物理分离被轻易地在所述液相中分离,产生基本上干燥的溴。没有大量水的存在允许烷烃的选择性溴化,不产生CO2,并且允许接着的有效且选择性的烷基溴化物的低聚和环化反应,主要产生丙烷和更重的产物,其C5+镏分包含基本上支化的烷烃和取代的芳香化合物。从所述溴化和低聚反应中得到的副产物氢溴酸蒸气被容易地溶解到水相中,并被金属溴化物氧化产生的金属氢氧化物或金属氧化物中和。
依照图9A中所示的本发明方法的另一个实施方案,所述烷基的溴化和烷基溴的转化阶段是以与上述图2和3描述的相应阶段基本上相似的方式操作的。更具体地,由原料气和再循环气流在约1bar到约30bar范围内的压力下的混合物组成的包含较低分子量烷烃的气流被分别通过管线、管或导管262和211运输或传送,并与管线225中的干燥的溴液混合。所得到的混合物被通过泵224输送以及送至热交换器226中,在此所述液态溴被蒸发。较低分子量烷烃和干燥溴蒸气的混合物被供给反应器230。优选地,在被引入反应器230的混合物中较低分子量烷烃对干燥溴蒸气的摩尔比大于2.5∶1。反应器230具有入口预热器区228,其加热所述混合物至约250℃到约400℃范围内的反应引发温度。在第一反应器230中,所述较低分子量烷烃与干燥的溴蒸气在约250℃到约600℃范围内的较低温度和约1bar到约30bar范围的压力下发生放热反应,从而产生气态的烷基溴化物和氢溴酸蒸气。所述操作温度范围的上限高于所述反应引发温度范围的上限,由于所述溴化反应的放热特性使所述原料混合物被加热至所述反应引发温度。在甲烷的情况下,溴代甲烷的形成是按照以下一般反应发生的:
CH4(g)+Br2(g)→CH3Br(g)+HBr(g)
该反应的发生具有极高程度的溴代甲烷选择性。例如,在溴与摩尔过量的甲烷以4.5∶1的甲烷对溴的比例反应的情况下,对一卤化的溴代甲烷的选择性在90到95%范围内。少量的二溴甲烷和三溴甲烷也在溴化反应中形成。较高的烷烃,例如乙烷、丙烷和丁烷,也轻易地溴化产生一和多溴化物质。如果使用的烷烃对溴的比例明显小于2.5∶1,则发生对溴代甲烷的选择性显著地低于90%,并且观察到不需要的炭黑大量形成。也已经显示,可以存在于对于所述溴化的原料气中的其它的烷烃例如乙烷和丙烷,被容易地溴化从而形成乙基溴化物和丙基溴化物。此外,被输送入第第一反应器230的所述干燥的溴蒸气基本上是无水的。申请人已经发现,来自第一反应器230中的溴化步骤的基本上所有的水蒸汽的除去基本上消除了不需要的二氧化碳的形成,因此增加烷烃溴化为烷基溴化物的选择性,并且消除由烷烃形成二氧化碳过程中产生的大量废热。
所述包含烷基溴化物和氢溴酸的流出物被通过管线231从第一反应器230排出,并且在流向第二反应器234之前在热交换器232中被部分地冷却到约150℃到350℃范围的温度。在第二反应器234中,所述烷基溴化物被在约150℃到约450℃范围的温度下,以及在约1到30bar范围的压力下,在结晶硅铝酸盐催化剂,优选沸石催化剂,以及最优选ZSM-5沸石催化剂的固定床上发生放热反应。虽然所述沸石催化剂优选以氢、钠或镁的形式使用,但该沸石也可以通过与其它碱金属阳离子(例如Li、K、Na或Cs),与碱土金属阳离子(例如Mg、Ca、Sr或Ba),与过渡金属阳离子(例如Li、Mn、V、W)进行离子交换,或至所述氢的形式而被改性。具有不同孔径和酸性的其它沸石催化剂可以用于第二反应器234,这对于熟练的技术人员来说将是显而易见的,这些具有不同孔径和酸性的沸石催化剂是通过改变所述铝硅比而合成的。在该反应器中,所述烷基溴化物被低聚以产生较高分子量烃类产品和额外的氢溴酸蒸气的混合物。
第二反应器234的操作温度是决定所述低聚反应对多种较高分子量液态烃产品的选择性的一个重要参数。第二反应器234的操作温度优选在约150℃到约450℃的范围内,但更优选约300℃到约400℃的范围内。第二反应器中温度高于约300℃导致轻质烃类(例如不需要的甲烷)的产率增加,而较低的温度则增加较重分子量烃类产品的产率。在所述温度范围的低端,在溴代甲烷在ZSM-5沸石上在低至约150℃的温度下反应的情况下,20%左右的显著溴化甲烷转化率被注意到,并且其对C5+产品具有高选择性。值得注意的是,就在优选的ZSM-5沸石催化剂上反应的烷基溴化物来说,环化反应发生,以至于产生的C7+馏分包含高百分比的取代的芳香化合物。在接近约300℃的升高的温度下,溴代甲烷的转化率提高到90%或更高,然而对C5+产品的选择性降低,以及对较轻产品,特别是不需要的甲烷的选择性增加。令人惊奇地,仅有很少的乙烷或C2-C4烯烃混合物形成。在接近约450℃的温度下,溴代甲烷几乎全部都转化为甲烷。在约300℃到约400℃之间的最佳温度范围内,作为所述反应的副产物,在操作期间随着时间的过去少量的碳将在所述催化剂上积累,导致在数小时到数百小时的范围内催化剂活性的降低,这取决于所述反应的条件和原料气的组成。据信,高于约400℃的较高的反应温度有利于碳的形成,因此增加所述催化剂的失活率。相反地,在所述温度范围的低端,特别是在低于约300℃下操作,也会促进焦化,这可能是由于烃类产品的降低的脱附率。因此,在第二反应器234中的在约150℃到约400℃的范围内,但是更优选在约300℃到约400℃的范围内的操作温度平衡了对需要的产品的增加的选择性和由于碳形成的更低的失活率与较高的单程转化率,这最小化催化剂的量、循环率以及要求的设备规模。
催化剂可以在原位被周期性地再生,方法是:从正常操作流路中隔离反应器234,在约1bar到约5bar范围的压力下和约400℃到约650℃范围的提高的温度下用惰性气体通过管线270吹洗从而在可操作的范围内除去吸附在所述催化剂上的未反应的原料,接着通过在约1bar到约5bar范围的压力下和约400℃到约650℃范围的提高的温度下由管线270向反应器234中加入空气或惰性气体稀释的氧气来将沉积的碳氧化成CO2。在所述再生期间通过管线275将二氧化碳和剩余的空气或惰性气体从反应器234中排出。
包含所述较高分子量烃类产品和氢溴酸的流出物通过管线235从第二反应器234中排出,并且在交换器236中被冷却至约100℃到约600℃范围的温度。如图9A所示,所述冷却的流出物被通过带有处于打开状态的阀238和处于关闭状态的阀239和243的管线235和241输送,并引入到包含固相金属氧化物床298的容器或反应器240中。所述金属氧化物的金属选自镁(Mg)、钙(Ca)、矾(V)、铬(Cr)、锰(Mn)、铁(Fe)、钴(Co)、镍(Ni)、铜(Cu)、锌(Sn)或锡(Sn)。所述金属的选择是根据与要求的操作温度有关的物理和热力学特性进行的,同时也考虑潜在的环境和健康影响以及价格因素。作为所述金属优选使用镁、铜和铁,最优选使用镁。这些金属具有不但形成氧化物而且形成溴化物盐的特性,而且在低于约500℃的温度范围所述反应是可逆的。所述固体金属氧化物优选固定化在适当的耐磨载体上,例如,合成的无定形二氧化硅,例如马里兰州哥伦比亚戴维森催化剂公司(Davison Catalysts of Columbia,Maryland)制造的Davicat Grade 57。在反应器240中,使氢溴酸与所述金属氧化物在低于600℃以及优选300℃到450℃之间的温度下依照以下通式发生反应,其中M代表所述金属:
2HBr+MO→MBr2+H2O
使该反应中产生的蒸汽与管线244、218和216中的高分子量烃类产品一起通过打开的阀219输送到热交换器220中,在此所述混合物被冷却到约0℃到约70℃范围的温度内。该冷却了的混合物被送到脱水器250以从所述气流中除去基本上全部的水。所述水然后被通过管线253从脱水器250中除去。所述包含较高分子量烃类产物的干燥了的气流进一步被通过管线251送入产品回收单元252,从而回收需要的C3和C4产品,但管线254中作为液体产物的主要是C5+馏分。任何脱水和液体回收的常规方法都可以被用于本发明的实施,例如固体-床干燥剂吸附后接着进行,例如,冷冻冷凝,低温膨胀,或循环吸收油,这些熟练的技术人员公知的用于处理天然气或炼厂气流的方法。来自产品回收单元252的剩余蒸气流出物然后被分成可以作为燃料用于本方法的清洁气流257和通过压缩机258被压缩的再循环剩余蒸气。从压缩机258排出的再循环剩余蒸气被分成两个部分。等于至少所述原料气体积1.5倍的第一部分被通过管线262输送,与在管线225中输送的液态溴和原料气混合,然后被输送至热交换器226,在此所述液溴被蒸发并且以上述方式被送入第一反应器230。第二部分被通过管线263从管线262排出并被通过控制阀260进行调节,在足够稀释所述烷基溴浓缩物入反应器234并吸收所述反应热的速度下进行,致使反应器234维持在所选定的操作温度,优选在约300℃到约400℃的温度范围,从而最佳化转化率与选择性,以及最小化由于碳沉积而导致的催化剂的失活率。这样,由再循环蒸气流出物提供的稀释作用允许在第一反应器230中的溴化的选择性被控制,而且缓和了第二反应器234中的温度。
氧气、富氧空气或空气210被通过鼓风机或压缩机213在对于溴的约环境压力到约10bar范围的压力下经由管线214、管线215和阀249通过热交换器215送至包含固相金属溴化物床299的第二容器或反应器246,氧气、富氧空气或空气在所述热交换器215中被预热到约100℃到约500℃范围内的温度。氧气与所述金属溴化物依照以下的通式反应,其中M代表所述金属:
MBr2+1/2O2→MO+Br2
用这样的方法,产生干燥的、基本上不含HBr的溴蒸气,因此消除了对水或氢溴酸与所述液态溴的后续分离的需要。反应器246在低于600℃下操作,以及更优选在约300℃到约500℃之间操作。所得到的溴蒸气被通过管线247、阀248和管线242从反应器246输送到热交换器或冷凝器221,在此所述溴被冷凝成液体。所述液态溴被通过管线242输送到分离器222中,在此液态溴通过管线225被除去,并通过任何适当的方法,例如通过泵224,由管线225被送至热交换器226和第一反应器230。所述剩余的空气或未反应的氧气被通过管线227从分离器222输送到溴洗涤单元223中,例如包含由熟练技术人员选定的适当溶剂或适当固体吸附介质的文丘里洗气系统(venturi scrubbingsystem),在此所述剩余的溴被捕获。所捕获的溴通过加热或其它适当的方法从所述洗涤溶剂或吸附剂脱附,由此回收的溴被通过管线212输送到管线225中。所述清洁过的空气或氧气被通过管线229排出。用这样的方法,氮气和任何其它基本上无反应活性的组分被从本发明的系统中除掉,因此不允许进入本方法的含有烃类的部分,也避免溴损失进入周围环境中。
按照本实施方案通过化学反应而不是通过简单的物理溶解性除去HBr的一个优点是,在较高的处理温度下将HBr基本上完全清除到低水平。另一个明显的优点是从所述被除去的溴中脱水,这样消除了对于溴与水相的分离以及对于从所述水相汽提剩余的溴的需要。
反应器240和246能够以周期方式操作。如图9A所示,阀238和219被以开启的状态操作,从而允许从第二反应器234排除的流出物中除掉氢溴酸,同时阀248和249被以开启的状态操作从而允许空气、富氧空气或氧气流过反应器246,从而氧化那里包含的固体金属溴化物。一旦反应器240和246中的金属氧化物和金属溴化物分别发生明显的转化,这些阀门被关闭。在这一点上,反应器246中的床299是基本上固体金属溴化物的床,而反应器240中的床298是基本上固体金属氧化物的床。如图10A所示,然后阀245和243被打开从而允许氧气、富氧空气或空气流过反应器240,从而氧化那里包含的固体金属溴化物,同时阀239和217被打开,从而允许包含所述较高分子量烃类产品和从第二反应器234中排出的氢溴酸的流出物被引入反应器246。这些反应器被以这样的方式操作直到反应器246和240中的金属氧化物和金属溴化物分别发生明显的转化,然后所述反应器被通过按如前所述开关阀门而循环回到图9A所示的流程简图。
当氧气被用作氧化气体,其被通过管线210输送到反应器用来氧化那里包含的固体金属溴化物时,图9A和10A所示的本发明方法的实施方案可以被修改,使得从反应器246(图9B)或240(图10B)中产生的溴蒸气被通过管线242和225直接输送到第一反应器230中。既然氧气是具有反应活性的并且不会在所述系统中累积,因此不再需要冷凝所述溴蒸气到液态以除去不反应的组分,例如氮气。压缩机213未显示在图9B和10B中,因为氧气的基本上全部商用来源,例如商用的空气分离单元,将在所需压力下提供氧气至管线210。如果不是,压缩机213可以被用于获得这样的压力,这对熟练的技术人员来说将是显而易见的。
在图11A所示的本发明的实施方案中,分别包含在反应器240和246中的固体金属氧化物颗粒和固体金属溴化物颗粒的床,被以如下所述的方式流化和连接从而保证所述床的连续操作而不需要提供设备(例如阀)来改变流入和流出每一个反应器的流向。根据此实施方案,包含所述较高分子量烃类产品和氢溴酸的流出物通过管线235从第二反应器234中排出,在交换器236中冷却到约100℃到约500℃范围的温度内,以及被引入包含固体金属氧化物颗粒的床298的反应器240的底部。在所述氢溴酸被与所述金属氧化物按照如上图9A所述的方式反应时,该引入的流体的流动引导在床298中的颗粒在反应器240内向上移动。处于或接近床298的顶端,包含归因于在反应器240中的固体金属氧化物与氢溴酸基本上完全的反应的在耐磨载体上的基本上固体金属溴化物的颗粒,被通过溢流堰或旋风分离器或其它常规的固/气分离方式收回,接着在重力下由管线259向下流动,以及在处于或接近反应器246中的固体金属溴化物颗粒的床299的底部被引入。在图11A所示的实施方案中,氧气、富氧空气或空气210被通过鼓风机或压缩机213在约环境压力到约10bar范围的压力内输送,由管线214被输送通过热交换器215,在此所述氧气、富氧空气或空气被预热到约100℃到约500℃范围内的温度,以及被引入在固相金属溴化物的床299之下的第二容器或反应器246中。氧气与所述金属溴化物被按以上关于图9A所述的方式反应从而制备干燥的、基本上不含HBr的溴蒸气。当氧气与所述金属溴化物反应时,该被引入的气体的流动引导床299中的颗粒在反应器246内向上流动。处于或接近床298的顶端,包含归因于在反应器246中的固体金属溴化物与氧气基本上完全的反应的在耐磨载体上的基本上固体金属氧化物的颗粒,被通过溢流堰口或旋风分离器或其它常规的固/气分离方式收回,接着在重力下由管线264向下流动,以及在处于或接近反应器240中的固体金属氧化物颗粒的床298的底部被引入。用这样的方法,反应器240和246可以被连续操作而不改变所述操作的参数。
在图11B所示的实施方案中,氧气被用作所述氧化气体,以及被通过管线210运送至反应器246。相应地,图11A所示的本发明所述方法的实施方案被修改,以致于从反应器246产生的溴蒸气被通过管线242和225直接地输送到第一反应器230。由于氧气是具有反应活性的并且不会在所述系统中累积,因此不再需要冷凝所述溴蒸气到液态来除去不反应的组分,例如氮气。压缩机213未在图11B中显示,因为氧气的基本上全部商用来源,例如商用的空气分离单元,将在所需压力下提供氧气至管线210。如果不是,压缩机213可以用于获得这样的压力,这对熟练的技术人员来说将是显而易见的。
依照图12所示的本发明所述方法的另一个实施方案,所述烷基的溴化和烷基溴的转化阶段以与关于图9A详细描述的相应阶段基本上相似的方式被操作,除了以下所讨论的。从反应器246中流出的剩余的空气或氧气和溴蒸气被通过管线247、阀248和管线242和阀300输送至热交换器或冷凝器221,在此所述包含溴的气体被冷却到约30℃到约300℃范围内的温度。所述包含溴的蒸气然后被通过管线242输送至包含被还原的价态的固相金属溴化物的床322的容器或反应器320中。被还原价态的金属溴化物的金属选自铜(Cu)、铁(Fe)或钼(Mo)。所述金属的选择是根据与要求的操作温度有关的物理和热力学特性进行的,同时也考虑潜在的环境和健康影响以及价格因素。作为所述金属优选使用铜或铁,最优选使用铜。所述固体金属溴化物优选固定在适当的耐磨载体上,例如合成的无定形二氧化硅,如马里兰州哥伦比亚戴维森催化剂公司(Davison Catalysts of Columbia,Maryland)制造的Davicat Grade 57。在反应器320中,溴蒸气被与所述固相金属溴化物反应,优选保持在适当的耐磨载体上在低于约300℃,以及优选约30℃到约200℃之间的温度下,依照以下通式发生反应,其中M2代表所述金属:
2M2Brn+Br2→2M2Brn+1
在此方法中,溴被作为反应器320中的第二金属溴化物,即2M2Brn+1,而储存,同时所得到的包含剩余的空气或氧气的蒸气被从反应器320中通过管线324、阀326和管线318排出。
所述包含较低分子量烷烃的气流,其是由原料气(管线211)和再循环气流的混合物所组成,被通过管线262、热交换器352、阀304和管线302运输或传送至包含被氧化价态的固相金属溴化物的床312的第二容器或反应器310中,所述气流在热交换器352中被预热到约150℃到约600℃范围内的温度。被氧化价态的金属溴化物中的金属选自铜(Cu)、铁(Fe)或钼(Mo)。所述金属的选择是根据与要求的操作温度有关的物理和热力学特性进行的,同时也考虑潜在的环境和健康影响以及价格因素。作为所述金属优选使用铜或铁,最优选使用铜。所述氧化态的固体金属溴化物优选固定在适当的耐磨载体上,例如,合成的无定形二氧化硅,如马里兰州哥伦比亚戴维森催化剂公司(DavisonCatalysts of Columbia,Maryland)制造的Davicat Grade 57。所述气流的温度是从约150℃到约600℃,以及优选从约200℃到约450℃。在第二反应器310中,所述气流的温度热分解所述呈氧化价态的固相金属溴化物,从而产生单质溴蒸气和呈还原价态的固体金属溴化物,反应依照以下通式发生,其中M2代表所述金属:
2M2Brn+1→2M2Brn+Br2
所得到的溴蒸气在被引入烷基溴化反应器230之前,被与所述包含较低分子量烷烃的气流一起通过管线314、315、阀317、管线330、热交换器226输送。
反应器310和320能够以周期方式被操作。如图12所示,阀304被以开启的状态操作,从而允许所述包含较低分子量烷烃的气流被输送到第二反应器310,同时阀317被以开启的状态操作从而允许此气流和在反应器310中产生的溴蒸气一起被输送到烷基溴化反应器230中。同样地,阀306被以开启的状态操作从而允许来自反应器246的溴蒸气被输送到反应器320中,同时阀326被以开启的状态操作从而允许剩余的空气或氧气被从反应器320中排出。一旦发生反应器320和310中的被还原的金属溴化物和被氧化的金属溴化物分别明显转化为相应的被氧化和被还原态,这些阀门如图13所示被关闭。在这一点上,反应器320中的床322基本一是呈氧化价态的金属溴化物的床,而反应器310中的床312基本上是被还原价态的金属溴化物的床。如图13所示,阀304、317、306和326是关闭的,然后阀308和332被打开以允许所述包含较低分子量烷烃的气流被通过管线262、热交换器352、阀308和管线309运输或传送至反应器320来热分解所述被氧化价态的固相金属溴化物,从而产生单质溴蒸气和被还原态的固体金属溴化物,所述气流在热交换器352中被加热到约150℃到约600℃的范围内。阀332也被开启,从而允许所得到的溴蒸气在被引入烷基溴化反应器230之前,被与所述包含较低分子量烷烃的气流一起通过管线324和330和热交换器226输送。此外,阀300被打开,从而允许从反应器246散发的溴蒸气由管线242通过交换器221被输送至反应器310中,在此所述被还原价态的固相金属溴化物与溴反应从而以金属溴化物的形式有效地存储溴。此外,阀316被开启,从而允许所得到的基本上不含溴的气体通过管线314和318被排出。所述反应器被以这样的方式操作,直到发生了反应器310和320中的被还原的金属溴化物和被氧化的金属溴化物的床分别明显转化为相应的被氧化态和被还原态,然后所述反应器通过按如前所述开关阀门而循环回到图12所示的流程简图。
在图14所示的本发明的实施方案中,包含在反应器310和320中的床312和322,分别被以如下所述的方式流化和连接从而保证所述床的连续操作而不需要提供设备,例如阀,来改变流入和流出每一个反应器的流向。根据此实施方案,从反应器246通过管线242排出的含溴气体在交换器370和372中被冷却到约30℃到约300℃范围内的温度,以及被引入到反应器320的底部,该反应器320包含处于流化状态的移动固相床322。在所述溴蒸气与进入床322底部的被还原的金属溴化物按照如上关于图12所述的方式反应时,该引入的流体的流动引导在床322中的颗粒在反应器320内向上移动。处于或接近床322的顶端,基本上包含归因于在反应器320中被还原的金属溴化物与溴蒸气基本上完全的反应的在耐磨载体上的被氧化的金属溴化物的颗粒,被通过溢流口、旋风分离器或其它常规的固/气分离方式收回,接着在重力下由管线359向下流动,以及被引导处于或接近反应器310中的床312的底部。在图14所示的实施方案中,所述包含较低分子量烷烃的气流,其是由原料气(管线211)和再循环气流的混合物组成的,被通过管线262和热交换器352运输或传送,在该热交换器352中所述气流被加热到约150℃到约600℃的范围内,以及被引入到反应器310中。所述被加热过的气流使在位于或接近床312的底部的位置进入的以被氧化价态存在的固相金属溴化物热分解,从而产生单质溴蒸气和被还原态的固体固金属溴化物。当所述被氧化了的金属溴化物被热分解时,该引入的气体的流动引导在床312中的颗粒在反应器310内向上流动。处于或接近床312的顶端,基本上包含归因于在反应器310中基本上完全的热分解反应的在耐磨载体上的被还原的固体金属溴化物的颗粒,被通过溢流口或旋风分离器或其它常规的气/固分离方式收回,以及在重力下由管线364向下流动,以及在处于或接近反应器310中的颗粒的床322的底部被引入。用这样的方法,反应器310和320可以被连续操作,改变所述操作的参数。
本发明的方法比传统的方法节省费用,这是由于其在约1bar到约30bar范围内的低压下以及在针对气相的约20℃到约600℃范围内以及针对液相的优选的约20℃到约180℃范围内的相对低温下操作的。这些操作条件允许使用价格比较低廉的且设计相对简单的设备,其中对于气相,所述设备可以使用容易获得的合金建造,以及对于液相,所述设备使用聚合物衬里的容器、管道和泵建造。本发明的方法也由于操作需要较低的能量和产生作为不需要的副产物的过量二氧化碳的最小化而变得更加高效。该方法能够直接产生混合的烃类产品,其包含处于液化石油气(LPG)和动力汽油燃料范围内的多种分子量的组分,其具有足够的芳烃含量,因此明显地增加所述汽油-范围燃料组分的辛烷值。
上文已经描述和显示了本申请的优选实施方案,可以理解的是,所述替换方法或改进,例如那些已经被提出的或其它的,可以从本发明的范围内得到并且是落入本发明的范围之内的。

Claims (42)

1、一种用于将气态烷烃转化为液态烃的方法,包括:
将具有较低分子量烷烃的气态原料与溴蒸气反应从而形成烷基溴和氢溴酸;和
将所述的烷基溴和氢溴酸在合成的结晶硅铝酸盐催化剂的存在下和足够形成较高分子量烃类和氢溴酸蒸气的温度下反应。
2、权利要求1所述的方法,其中所述的溴蒸气是基本上干燥的,因此避免伴随所述的烷基溴形成大量的二氧化碳。
3、权利要求1所述的方法,其中所述的气态原料是天然气。
4、权利要求3所述的方法,其中所述的天然气在与所述的溴蒸气反应前被处理从而去除基本上所有的二氧化碳和硫化合物。
5、权利要求1所述的方法,其中所述的温度是从约150℃到约400℃。
6、权利要求5所述的方法,其中所述的温度是从约250℃到约350℃。
7、权利要求1的方法,其中所述的结晶硅铝酸盐催化剂是一种沸石催化剂。
8、权利要求7所述的方法,其中所述的沸石催化剂是ZSM-5沸石催化剂,并且所述的较高分子量烃类包含主要由取代的芳族化合物组成的C7+馏分。
9、权利要求8所述的方法,其中所述的ZSM-5沸石催化剂被用至少一种改性阳离子进行改性,该改性阳离子选自氢以及IA族碱金属,或IIA族碱土金属。
10、权利要求9所述的方法,其中所述的ZSM-5沸石催化剂被通过与至少一种阳离子进行离子交换而改性,该阳离子选自氢、钠、钾、铯、镁、钙或钡。
11、权利要求1所述的方法,进一步包括:
通过与包含反应产物的水溶液的中和反应而从所述的较高分子量烃类中除去所述的氢溴酸蒸气,该反应产物是通过氧化包含金属溴化物盐的水溶液而得到的,所述金属溴化物盐中的金属选自Cu、Zn、Fe、Co、Ni、Mn、Ca或Mg溴化物。
12、权利要求1所述的方法,其中所述的溴蒸气是通过氧化含水的金属溴化物盐溶液而制备的,所述金属溴化物盐的金属选自Cu、Zn、Fe、Co、Ni、Mn、Ca或Mg。
13、权利要求1所述的方法,进一步包括:
通过溶入水中形成氢溴酸而从所述的较高分子量烃类中除去所述氢溴酸蒸气,所述的氢溴酸溶液通过与包含金属氢氧化物的水溶液反应而被中和,该金属氢氧化物是通过用氧气氧化含水的金属溴化物盐溶液而得到的,所述金属溴化物盐的金属选自Cu、Zn、Fe、Co、Ni、Mn、Ca或Mg。
14、权利要求1所述的方法,其中所述的氢溴酸蒸气通过溶入水中形成氢溴酸而从所述较高分子量烃类中除去,所述氢溴酸溶液被蒸发并与金属氧化物反应,所述金属氧化物是通过氧化包含在多孔载体上的金属溴化物盐获得的,所述金属溴化物盐的金属选自由Cu、Zn、Fe、Co、Ni、Mn、Ca或Mg组成的组。
15、权利要求1所述的方法,其中所述的溴蒸气是通过氧化包含在多孔载体上的金属溴化物盐被制备的,所述金属溴化物盐的金属选自Cu、Zn、Fe、Co、Ni、Mn、Ca或Mg所组成的组。
16、权利要求1所述的方法,其中所述的较高分子量烃类在具有过量的低级烷烃的混合物中包含C3、C4和C5+馏分,该方法进一步包括:
对所述的较高分子量烃类进行脱水至约-20℃或更低的露点,以便回收液体形式的所述C5+馏分。
17、权利要求16所述的方法,进一步包括:
在在所述合成的结晶硅铝酸盐催化剂上反应的步骤之前,将至少一部分所述C3和C4馏分与所述的烷基溴和所述的氢溴酸混和。
18、一种用于将气态较低分子量烷烃转化为液态烃的方法,包括:
将包含较低分子量烷烃的气态原料与溴蒸气反应以形成烷基溴和氢溴酸;
将所述的烷基溴和氢溴酸在合成的结晶硅铝酸盐催化剂的存在下反应以形成较高分子量的烃类和氢溴酸;和
将所述的氢溴酸转化为溴。
19、权利要求18所述的方法,进一步包括:
对所述的较高分子量的烃类进行脱水。
20、权利要求18所述的方法,进一步包括:
将所述的从所述的氢溴酸转化成的溴再循环到所述的与所述气态原料反应的步骤,所述的溴以蒸气的形式被再循环。
21、一种用于将气态烷烃转化为液态烃的方法,包括:
将具有较低分子量烷烃的气态原料与溴蒸气反应以形成烷基溴和氢溴酸;
将所述的烷基溴和氢溴酸在合成的结晶硅铝酸盐催化剂存在下以及在足够形成较高分子量烃类和氢溴酸蒸气的温度下反应;
通过将所述的氢溴酸蒸气与金属氧化物反应形成金属溴化物和水蒸汽而由所述的较高分子量烃类中除去所述的氢溴酸蒸气。
22、权利要求21所述的方法,其中所述的金属氧化物的所述金属是镁、钙、钒、铬、锰、铁、钴、镍、铜、锌或锡。
23、权利要求22所述的方法,其中所述的金属氧化物被负载在固相载体上。
24、权利要求23所述的方法,其中所述的金属氧化物被包含在反应器中的床中。
25、权利要求21所述的方法,进一步包括:
将所述的金属溴化物与含氧气体反应从而得到金属氧化物和所述的溴蒸气。
26、权利要求25所述的方法,其中所述的溴蒸气被用在反应所述的具有较低分子量烷烃的气态原料的步骤中。
27、一种用于将气态烷烃转化为液态烃的方法,包括:
将具有较低分子量烷烃的气态原料与溴蒸气反应以形成烷基溴和氢溴酸;
将所述的烷基溴和氢溴酸在合成的结晶硅铝酸盐催化剂存在下以及在足够形成较高分子量的烃类和氢溴酸蒸气的温度下反应;和
将所述的氢溴酸蒸气和所述的较高分子量烃类输送到具有金属氧化物颗粒的床的第一容器,所述的氢溴酸蒸气与所述的金属氧化物颗粒的床反应以形成金属溴化物颗粒和水蒸气。
28、权利要求27所述的方法,进一步包括:
使含氧气体流过具有金属溴化物颗粒的床的第二容器以形成金属氧化物颗粒和溴蒸气。
29、权利要求8所述的方法,进一步包括:
将所述的溴蒸气输送到所述的反应所述气态原料的步骤。
30、权利要求28所述的方法,其中在基本上全部的在所述第一反应器中的所述床中的所述金属氧化物颗粒已经被转化为所述的金属溴化物颗粒以后,所述方法进一步包括:
使含氧气体流过具有金属溴化物颗粒的床的所述第一容器以形成金属氧化物颗粒和溴蒸气。
31、权利要求30所述的方法,进一步包括:
将所述的溴蒸气输送到所述的反应所述气体原料的步骤。
32、权利要求30所述的方法,其中在基本上全部的在所述第二容器中的所述床中的所述金属溴化物颗粒已经被转化为所述金属氧化物颗粒和所述溴蒸气以后,所述方法进一步包括:
将所述的氢溴酸蒸气和所述的较高分子量的烃类输送到所述的第二容器,所述的氢溴酸蒸气与所述的第二容器中的所述金属氧化物颗粒反应以形成金属溴化物颗粒和水蒸气。
33、权利要求28所述的方法,进一步包括:
同时将所述的金属氧化物颗粒从所述的第二容器输送到所述的第一容器,以及将所述的金属溴化物颗粒从所述的第一容器输送到所述的第二容器。
34、权利要求28所述的方法,其中所述的金属氧化物和所述的金属溴化物的所述金属是镁、钙、钒、铬、锰、铁、钴、镍、铜、锌或锡。
35、一种用于将气态烷烃转化为液态烃的方法,包括:
将具有较低分子量的烷烃的气态原料与溴蒸气反应以形成烷基溴和氢溴酸;
将所述的烷基溴和氢溴酸在合成的结晶硅铝酸盐催化剂存在下以及在足够形成较高分子量烃类和氢溴酸蒸气的温度下反应;
通过与金属氧化物反应形成第一金属溴化物和水蒸气而从所述的较高分子量烃类中除去所述的氢溴酸蒸气;
用含氧气体氧化所述的第一金属溴化物以形成溴蒸气;和
将所述的溴蒸气与被还原了的金属溴化物反应从而形成第二金属溴化物。
36、权利要求35所述的方法,进一步包括:
将所述的第二金属溴化物与所述的气态原料接触,由此将所述的第二金属溴化物热分解为所述的溴蒸气和所述的被还原了的金属溴化物。
37、权利要求36所述的方法,其中将所述的由所述的第二金属溴化物的热分解产生的溴蒸气和所述的气态原料反应从而形成烷基溴和氢溴酸。
38、权利要求35所述的方法,其中所述的被还原了的金属溴化物被包含于在第三容器中的床中以及溴蒸气被与所述的被还原了的金属溴化物在所述的第三容器中反应从而形成第二金属溴化物。
39、权利要求38所述的方法,其中在基本上全部的在所述第三容器中的所述床中的所述的被还原了的金属溴化物已经被转化为第二金属溴化物以后,所述的方法进一步包括:
将所述的第二金属溴化物与所述的气态原料接触,由此将所述第二金属溴化物热分解成所述溴蒸气和所述被还原了的金属溴化物。
40、权利要求38所述的方法,其中所述的第二金属溴化物被包含于在第四容器中的床中以及所述的第二金属溴化物被在所述的第四容器中热分解为所述的溴蒸气和所述的被还原了的金属溴化物。
41、权利要求40所述的方法,其中在基本上全部的在所述第四容器中的所述床中的所述第二金属溴化物已经被热分解为所述的溴蒸气和所述的被还原了的金属溴化物以后,所述的方法进一步包括:
将所述的溴蒸气与所述的被还原了的金属溴化物反应从而形成第二金属溴化物。
42、权利要求28所述的方法,进一步包括:
同时将所述的第二金属溴化物从所述的第三容器输送到所述的第四容器,以及将所述的被还原了的金属溴化物从所述的第四容器输送到所述的第三容器。
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