CN101484406A - 天然气转化为液体烃的连续方法 - Google Patents

天然气转化为液体烃的连续方法 Download PDF

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CN101484406A
CN101484406A CNA200780010896XA CN200780010896A CN101484406A CN 101484406 A CN101484406 A CN 101484406A CN A200780010896X A CNA200780010896X A CN A200780010896XA CN 200780010896 A CN200780010896 A CN 200780010896A CN 101484406 A CN101484406 A CN 101484406A
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S·B·加德沃
M·D·维尔斯塔
P·格罗索
张爱华
E·麦克法兰
Z·J·A·科蒙
J·H·舍曼
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Abstract

提供一种通过使烷烃卤化、产物形成(碳－碳偶联)、产物分离和卤素再生步骤连续循环进行而将甲烷、天然气或其它烃原料转化为高级烃或烯烃的改进连续方法。优选地，通过将氢溴酸与空气或氧气反应来连续回收卤素。本发明提供获得芳烃化合物、脂族化合物、脂族与芳族化合物的混合物、烯烃、汽油等级物质和其它有用产品的有效途径。

Description

天然气转化为液体烃的连续方法
发明领域
本发明广义涉及碳-碳偶联方法，更具体地说涉及烃原料转化为有用产品的方法。
发明背景
科学家们长期以来一直在寻找将甲烷和其它烃转化为长链烃、烯烃、芳烃和其它产品的有效途径。数十年来CH键活化反应一直是广泛研究的焦点，结果各式各样。较为有效的方法能够在几个方面产生价值，包括使偏远地区的烃原料(如标准天然气)通过转化反应变成便于运输和使用的燃料和原料，和能够将廉价原料(如甲烷和其它轻质烃)用于通常是由高级烃制成的产品。
US 6525230公开了使用一种由中空的、界定出第一、第二和第三区的非隔离式内腔构成的“分区式反应器”将烷烃转化为其它化合物的方法。在第一区中氧气与金属溴化物进行反应来提供溴，在第二区中溴与烷烃反应来形成烷基溴化物和溴化氢，和在第三区中烷基溴化物与金属氧化物反应形成相应的产品。在一个实施方案中，流经反应器的气体逆向将金属氧化物转化回金属溴化物和金属溴化物转化回金属氧化物。反应器基本是以循环模式操作的。
US 6452058公开一种使用稀土金属卤化物或卤氧化物催化剂从烷烃、卤化氢和优选氧气来生产烷基卤化物的氧化卤化方法。也提及使用分子卤的替代方法。其它专利，如US 3172915、3657367、4769504和4795843公开了金属卤化物应用于烷烃氧化卤化反应的方法。但是，氧化卤化反应有几个缺点，包括生成全卤化产物和不能接受量的深度氧化产物(CO和CO2)。
三个已公开美国专利申请，公开号2005/0234276、2005/0234277和2006/0100469(都为Waycuilis的)描述了气态烷烃转化为液体烃的基于溴的方法。描述了几个基本步骤，包括(1)将溴与烷烃反应来生产烷基溴化物和氢溴酸(溴化反应)，(2)将烷基溴化物和氢溴酸产物与结晶铝硅酸盐催化剂反应来形成更高分子量的烃和氢溴酸(偶联反应)，(3)通过与部分氧化的金属溴化物盐(金属氧化物/溴氧化物/溴化物)水溶液进行反应生成金属溴化物盐或者通过在金属溴化物催化剂上氢溴酸与空气的反应来将氢溴酸中和，和(4)通过金属溴化物盐与氧反应得到溴和氧化盐来再生成溴。该方法的可能缺点包括低甲烷转化率；短空时速率；结果有可能溴转化率低于100％；乙烷、丙烷和更高烷烃的挥霍性过度溴化反应，导致形成二溴甲烷和其它多溴化烷烃，这有可能在公开条件下形成焦炭；较低的烷基溴化物转化率；需要将烃产物料流与氢卤酸水溶液料流分离；和催化剂再生移去含卤焦炭的过程中不能充分捕获卤素。此外，这一排放含卤料流的提案在经济和环境上都不能接受。
Waycuilis法显然还需要在较低温度下操作以避免显著的甲烷选择性。可能的结果是烷基溴化物种的不完全转化，且因为所描述的方法依赖于物料分割成回收产物，大量未转化的烷基溴化物可能会与产物一起离开过程。这表明有不能接受的溴损失(以未转化的甲基溴的形式)和碳效率的降低。
按Waycuilis所公开的方法，通过与部分氧化的金属溴化物盐水溶液进行反应来中和氢溴酸和随后将形成的烷基溴化物盐与氧反应来得到溴和氧化盐也有若干缺点。第一，所存在的任何二氧化碳将在淤浆液中形成不能再生的碳酸盐。第二，由于在约200℃以上时压力的增加不能耐受而使最高温度受限，这样就妨碍了卤素的完全回收。第三，尽管中和氢溴酸的过程中使用氧化还原活性的金属氧化物(如V、Cr、Mn、Fe、Co、Ce和Cu)能有助于分子溴的形成，但由于使用固体溴盐会使HBr转化反应不完全，这又将导致体系会有显著的溴损失(在水相中)。在使用过量空气的条件下，溴盐可能最终转化为氧化形式，停止排水中任何进一步的HBr损失。
为将水与溴分离，Waycuilis公开了使用冷凝和相分离步骤来生成半无水液体溴和水/溴混合物的方法。其它人也曾提出过溴与水分离的另一些方法，如使用惰性气体从水相中汽提出溴或者使用基于吸附作用的方法，但是这些方法的效率很低且导致卤素总损失较高。
先有技术的氧氯化方法首先将水从HCl中移出(高成本步骤)，然后将HCl与氧和烃直接反应。氧氯化方法依靠用水吸收法将HCl与未反应烷烃和高级烃产物分离，然后从盐酸中回收无水HCl。美国专利2220570公开了吸附水中HCl的方法和装置，通过将HCl气体与环境空气接触使吸收过程的热耗散，也可通过水蒸发法。美国专利4488884公开了一种通过在水中吸收气态HCl来生产浓度至少35.5wt％盐酸的方法。美国专利3779870提及一种通过使用氯化物盐进行萃取蒸馏来回收无水HCl气体的方法。美国专利4259309提及一起使用胺和水不溶性溶剂从稀HCl水溶液来生产气态HCl的方法。
尽管研究人员已在寻找更有效的CH键活化途径用以将天然气和其它烃原料转化为燃料和其它产品方面取得了一些进展，但仍然非常需要连续的、经济可行的和更有效的方法。
发明概述
本发明的一个方面中，提供一种将甲烷、天然气和其它烃原料转化为高级烃或烯烃的连续方法。在本发明的一个实施方案中，该方法包括烷烃卤化步骤、多卤代化合物“再均衡(reproportionation)”来提高所形成的单卤代物量的步骤、烷基卤化物(和任选烯烃)低聚(C-C偶联)来形成更高碳原子数产物的步骤、将产物与卤化氢分离步骤、卤素连续再生步骤和将分子卤从水中分离出来并回收的步骤。
本发明揭示以下发现：在烷烃卤化反应器中基本所有分子卤都消耗掉之后，可将所形成的多卤代烃与未卤代的烷烃反应来提高单卤代物的收率，在后续步骤中单卤代物比多卤化物种能更有效地反应-和形成更理想的产物。在初始烷烃卤化反应，消耗了基本所有分子卤之后，通过将多卤代烷烃的卤原子转移到未卤代的烷烃上来进行附加卤化反应，从而减少碳损失和焦炭形成。例如，二溴乙烷可与甲烷再均衡来形成甲基溴，二溴甲烷可与乙烷或丙烷再均衡来形成乙基溴和乙烯和/或丙基溴和丙烯。尽管不受任何任何理论束缚，据信在一些实施方案中，通过形成烯烃然后与多卤代烷烃反应也能获得更多的单卤代物。在某些实施方案中，通过催化剂来促进再均衡反应。
本发明提供许多独特的子过程、改进和优点，包括多卤化物的再均衡、在必要的烧焦过程中回收所释放的卤素、通过在催化剂上使氢氯酸和氧分子反应来连续再生卤素(能允许总过程连续操作)和使用仔细选择的抗蚀材料来实施本身有腐蚀性的基于卤素的过程(能使过程可以工业化实际操作)以及使用适合可靠的长期卤素生成催化剂。溴化反应器可在绝热和宽温度范围条件下操作。二氧化碳和水很容易忍受(tolerated)，因为是痕量烃杂质。通过优选将单卤代物在偶联催化剂(如沸石或其它活性金属-氧材料)上进行反应的设计使因形成焦炭而造成的碳损失最小化。完全回收卤素再用也是本发明的重要优点。
这些集成于总过程的发现是本发明的基础，为诸如天然气转化为液体燃料(包括汽油和汽油添加剂)和化学品(包括芳烃如苯、二甲苯和甲苯，以及轻质烯烃如乙烯和丙烯)的应用提供了真正先进性。
附图简述
图1是按本发明的连续法将甲烷或天然气转化为烃化学品的一个实施方案的示意图；
图2是按本发明的连续法将甲烷或天然气转化为烃燃料的一个实施方案的示意图；
图3是按本发明另一实施方案的多卤化物再均衡子过程的示意图；
图4是一个单溴化物分离塔实施方案的示意图；
图5是一个用于本发明实际操作的萃取蒸馏系统实施方案的示意图；
图6是按本发明的连续法将烷烃转化为烃产品的一个实施方案的简单方框图，其中水与烃产物分离；
图7是按本发明的连续法将烷烃转化为烃产品的一个实施方案的简单方框图，其中水是在烷烃溴化步骤之后分离出来；
图8是按本发明的一个实施方案进行的实验中溴苯转化率和苯收率随时间变化的曲线；和
图9是按本发明的一个实施方案进行的实验中催化剂效率随时间变化的曲线。
发明详述
本发明提供一种使用分子卤来活化原料中的C-H键，能够将天然气和其它烃原料转化为更高分子量烃产物的化学方法。按照本发明的一个方面，将烃原料转化为一或多种高级烃的连续方法包括以下步骤：(a)通过在足以形成烷基卤化物和卤化氢的工艺条件下将分子卤与烃原料(优选含甲烷的原料)进行反应来形成烷基卤化物，其中基本所有分子卤都被消耗掉；(b)通过将一些或全部所述烷基卤化物与烷烃进料进行反应来形成再均衡烷基卤化物，其中所存在的单卤代烃比例提高；(c)在足以形成高级烃和额外的卤化氢的工艺条件下将所述再均衡烷基卤化物与第一催化剂接触；(d)将所述高级烃与所述卤化氢分离；(e)通过有氧源存在、足以形成分子卤和水的工艺条件下将所述卤化氢与第二催化剂接触；(f)将所述分子卤与水分离，使所述卤素得以再利用；和(g)重复步骤(a)-(f)期望的次数。这些步骤可按上述顺序实施，或者按不同的顺序实施。
按照本发明的第二方面，将烃原料转化为一或多种高级烃的连续方法包括以下步骤：(a)通过在足以形成烷基卤化物和卤化氢的工艺条件下将分子卤与含甲烷烃原料在卤化反应器中进行反应来形成烷基卤化物，其中基本所有分子卤都被消耗掉；(b)将未反应的甲烷与烷基卤化物分离并将其直接送回卤化反应器；(c)通过将一些或全部烷基卤化物与含至少1％(体积)一或多种C2-C5烃的烷烃进料进行反应来形成再均衡烷基卤化物，其中所存在的单卤代烃比例提高；(d)在足以形成高级烃和额外的卤化氢的工艺条件下将所述再均衡烷基卤化物与第一催化剂接触；(e)将所述高级烃与所述卤化氢分离；(f)通过有氧源存在、足以形成分子卤和水的工艺条件下将所述卤化氢与第二催化剂接触；(g)将所述分子卤与水分离，使卤素得以再利用；和(h)重复步骤(a)-(g)期望的次数。
本发明每一方面和实施方案中，预期步骤(a)中形成的烷基卤化物可全部相同(如100％为溴甲烷)，或者更典型地可以不同(如溴甲烷、二溴甲烷、二溴乙烷等的混合物)。类似地，预期步骤(c)中形成的“高级烃”可全部相同(如100％异辛烷)，或者更典型地可以不同(如脂族和/或芳族化合物的混合物)。本文所用术语“高级烃”是指具有碳原子数大于烃原料的一或多种组分的烃，以及具有碳原子数等于或大于烃原料的一或多种组分的烯属烃。例如，若原料是天然气--一般是轻质烃的混合物，主要是甲烷与较少量乙烷、丙烷和丁烷以及更少量的长链烃如戊烷、己烷等--按本发明所生产的“高级烃”可包括C2或更高级烃如乙烷、丙烷、丁烷、C5+烃、芳烃等，且任选包括乙烯、丙烯和/或更长链烯烃。术语“轻质烃”(有时缩写为“LHC”)是指C1-C4烃，如甲烷、乙烷、丙烷、乙烯、丙烯、丁烷和丁烯，它们在室温和大气压下常规全都是气体。
适用于本发明的烃原料的非限定性实例包括烷烃如甲烷、乙烷、丙烷甚至更大的烷烃，烯烃，天然气和其它的烃混合物。大部分情况下，原料主要是脂族性质。某些炼油工艺过程能获得轻质烃料流(所谓的“轻馏分”，一般是C1-C3烃的混合物)，在本发明一个实施方案中将其另加或不加甲烷来用作烃原料。
代表性的卤素包括溴(Br2)和氯(Cl2)。预计也可使用氟和碘，尽管不一定能得到相同的结果。通过使用氟稀释气流(氦气、氮气或其它稀释剂载带的氟气)有可能处理氟相关的一些问题。但是，因为氟-碳键的强度，预计要将烷基氟化物偶联和形成高级烃需要更剧烈的反应条件。类似地，通过在高温和/或高压下进行卤化和/或偶联反应有可能处理碘相关的一些问题。优选使用溴或氯，最优选溴。
图1和2图示说明按本发明方法的两个非限定性实施方案，图1示出制备烃化学品(如苯、甲苯、二甲苯、其它芳烃化合物等)的方法，图2示出制备燃料级烃如包含主要量C5以及高级脂族烃和(任选)芳烃的方法。两个方案的主要不同点是图2所示方法没有第一分离单元且不将多溴化物返回溴化反应器进行“再均衡反应”。在图2所示的流程图中，通过将轻质气体引入溴化反应器而使所生成的多溴化物量显著减少。多溴化物(来自甲烷溴化步骤)与轻质气体反应来形成单溴代烷烃。为方便起见，附图示出的是基于溴的过程。但在本发明另外的实施方案中，使用氯或其它卤素。
如图1所示，天然气(或其它烃原料)和分子溴经不同管线1，2送入热的溴化反应器3中并使其进行反应。产物(HBr，烷基溴化物，任选烯烃)和可能的未反应烃从反应器出去并经管线4送入第一分离单元5，其中单溴代烃和HBr与多溴代烃分离。多溴代烃经管线6返回溴化反应器，在其中与天然气中存在的和/或如下所述引入溴化反应器的甲烷或其它轻质烃进行“再均衡反应”。
溴化反应所形成的多溴化物的再均衡反应使出口料流富含单溴化物和烯烃物种，并减少了进入偶联反应器的多溴代烃量。这又能减少碳-碳偶联反应过程中形成的焦炭量。对大规模芳烃生产过程来说，可以采用附加分离单元，通过分离和再循环多溴化物来对送入偶联反应器的进料流进一步纯化，从而减少焦炭量和溴的总需要量。
未反应的烃原料、溴化反应器中形成的HBr、单溴化物和(任选)烯烃通过管线7经热交换器8进入热的偶联反应器9，在偶联催化剂存在下单溴化物(任选和存在的任何烯烃)进行反应形成高级烃。HBr、高级烃和(可能的)未反应烃及烷基溴化物从偶联反应器出去并通过管线10经另一热交换器11进入HBr吸收单元12。将水经单独管线13引入此单元。HBr在此单元中被吸收，此单元可以是填料塔或其它气-液接触设备。含液体烃和HBr水溶液的出料经管线14进入液-液分离器15，使液体烃与HBr水溶液进行相分离。然后将液体烃产物经管线16送入产物纯化单元17得到最终的烃产品。
在HBr吸收单元中HBr与烃产物和未反应的甲烷(和可能存在的任何其它轻质烃)分离后，甲烷(和可能有的任何其它轻质烃)经管线18送入第二分离单元19，此单元采用变温或变压吸附技术、基于膜的分离技术、低温蒸馏技术(优选用于大规模生产过程)或其它适宜的分离技术。将甲烷和可能的其它轻质烃借助一或多根管线20，21返回溴化反应器。在所示的方案中，甲烷被送到溴化反应器的上游区域或“区”，而其它轻质烃被送到反应器的中或下游区(后者是要有利于多溴化物的再均衡反应)。
自液-液分离器出来的HBr水溶液料流经管线22送入溴再生单元23。氧气、空气或富氧气体经单独管线24也送入此单元。通过在适宜催化剂存在下将HBr与氧反应使溴再生。得到的料流含水、分子溴、氧气、氮气(若使用空气作为氧源)和可能的其它气体。此产物料流通过管线25经热交换器26进入闪蒸单元27，将绝大部分分子溴与水、氧气、氮气和存在的其它气体(若有的话)分离开来。分子溴以液体或汽体(和含不多于痕量水)通过管线28经热交换器29然后返回溴反应器。
从闪蒸单元出来的水(含最高达3wt％分子溴)经管线30送到蒸馏单元31，得到水作为塔底料流，溴和溴-水共沸物作为馏出物。馏出物经管线32返回闪蒸单元。
闪蒸单元的气态产物(如氧气、氮气、任选其它气体和不多于微量或痕量的溴)经管线33送入除溴单元34，在此将分子溴与其它气体分离。然后将回收的溴通过管线35经热交换器29再引入溴化反应器。通过使用溴溶液和直接接触冷却使所用温度低于0℃来提高闪蒸步骤中回收的溴量可使进入除溴器的溴量进一步减少。其它气体(如氮气、氧气)可排放到大气中。
下面将更详细地描述实施本发明的各个子过程和其它改进方法的不同实施方案和特点。
溴化反应
烃原料的溴化反应是在固定床、流化床或其它适宜反应器中于能使溴化产物和反应物为气态的温度和压力条件下实施的，如在1-50atm和150-600℃、更优选400-600℃、甚更优选450-515℃的条件下实施，停留时间为1-60秒、更优选1-15秒。更高的温度往往会易倾向于形成焦炭，而低温则需要更大的反应器。使用流化床能提供改进传热的好处。
可使用热或光来引发烷烃的溴化反应，优选热法。在一个实施方案中，反应器还包含卤化催化剂，如沸石、无定形氧化铝-氧化硅、酸性氧化锆、钨酸盐、固体磷酸、金属氧化物、混合金属氧化物、金属卤化物、混合金属卤化物(在此情形下，金属例如是镍、铜、铈、钴等)和/或如美国专利3935289和4971664中所述的其它催化剂。在另一个实施方案中，反应器包含多孔性或无孔的惰性材料，能提供足够的表面积来保留所形成的焦炭而避免其漏出。惰性材料还可促进形成多卤代烃如二溴丙烷。在还有一个实施方案中，反应器中既有催化剂又有惰性材料。任选地，反应器包含不同区域或区，以使分子溴在一或多个区内完全转化生成烷基溴化物和溴化氢。
溴化反应也可在异构化催化剂如金属溴化物(如NaBr、KBr、CuBr、NiBr2、MgBr2、CaBr2)、金属氧化物(如SiO2、ZrO2、Al2O3)或金属(Pt、Pd、Ru、Ir、Rh)存在下实施，以帮助生成所期望的溴化异构体。由于异构化反应和溴化反应条件类似，溴化反应和异构化反应可在同一反应容器内实施。或者，可采用单独的异构化反应器，位于溴化反应器的下游和偶联反应器的上游。
再均衡反应
在一些实施方案中，本发明的关键特征是多卤代烃(多卤化物)即每分子含两或多个卤原子的卤代烃的“再均衡反应”。卤化反应过程中生成的单卤代烷烃(单卤化物)对于后续的偶联反应和更高分子量烃的形成是理想的主要反应物物种。对某些产物选择性来说，多卤代烷烃可能是理想的。再均衡反应能够通过通常在基本无分子卤存在的条件下将多卤代的烷基卤化物与未卤代的烷烃进行反应以控制单-多卤化物种的比例来达到所期望的使单卤代物变丰的目的。例如，二溴甲烷与甲烷反应生成甲基溴，二溴甲烷与丙烷反应生成甲基溴和丙基溴和/或丙烯，等等。
通过使烃原料和/或再循环烷烃与来自卤化反应器的多卤化物种反应来实施活性再均衡反应，优选基本无分子卤存在下反应。实际上，基本所有进入卤化反应器的分子卤被快速消耗掉了，形成单-和多卤化物，因此高碳溴化物的再均衡反应可简单地通过将多溴化物引入卤化反应器的中-或下游区域或“区”，任选其加热的温度与反应器其余部分的温度不同。
或者，再均衡反应可在独立的“再均衡反应器”内实施，使多卤化物与未卤代的烷烃进行反应，优选在基本无分子卤存在下反应。图3例示一个这样的方案，为明了起见，仅示出了主要系统单元。如图1所示，天然气或另外的烃原料和分子溴经单独管线1，2送入热的溴化反应器3中并使其进行反应。产物(HBr，烷基溴化物)和可能的未反应烃从反应器出去并经管线4送入第一分离单元5，其中单溴代烃和HBr与多溴代烃分离。单溴化物、HBr和可能的未反应烃通过管线7经热交换器8进入偶联反应器9并使其反应，如图1所示。多溴化物经管线6送入再均衡反应器36。将另外的天然气或其它烷烃原料经管线37也引入再均衡反应器。在再均衡反应器中多溴化物与未溴代烷烃进行反应来形成单溴化物，将其经管线38，第一次通过热交换器后送到偶联反应器9中。
在本发明的另一实施方案中(未示出)，烃原料包括含可观量C2和高级烃的天然气，将“新鲜的”天然气进料直接引入再均衡反应器，并将再循环甲烷(通过再均衡反应器未转化的)送回卤化反应器。
再均衡反应是热驱动和/或使用催化剂来促进。适宜催化剂的非限定性实例包括金属氧化物、金属卤化物和沸石。US 4654449公开了使用酸性沸石催化剂催化的多卤代烷烃与烷烃的再均衡反应。US2979541和3026361公开了使用四氯化碳作为甲烷、乙烷、丙烷及其氯代物的氯化试剂的方法。这三个专利都全文引为参考。在我们的知识中，连续法富集活性原料来生产高级烃的内容中采用再均衡反应是从未公开过的。
C1-C5烷烃与二溴甲烷和/或其它多溴化物的再均衡反应是在350-550℃范围的温度下进行的，最佳温度取决于所存在的多溴化物和要溴代的烷烃。此外，在升压(如2-30bar)下再均衡反应会进行得更快。通过在卤化反应器中达到高初始甲烷转化率，生成大量二-和三溴甲烷，然后可以将这些物种在再均衡步骤中用作溴化试剂。使用二-和三溴甲烷能够控制C1-C5烷烃转化为单溴化的C1-C5溴化烷烃和C2-C5烯烃。二-和三溴甲烷的再均衡反应有利于溴化反应过程中的高初始甲烷转化率，这将减少甲烷循环流量比和使反应物气流富含C2-C5单溴代烷烃和烯烃，使其在包括沸石在内的各种催化剂上偶联成液体产物。这是新方法的主要优点。
在本发明另一个实施方案中，再均衡反应是在分离单元不先将多卤化物分离出去的条件下实施的。通过将催化剂如沸石装填入“再均衡区”有利于使反应在较低温度下进行。例如，尽管丙烷与二溴甲烷反应形成溴甲烷和溴丙烷(再均衡反应的实例)，但在温度低于约500℃下反应不能进行到合适的程度。使用沸石可使再均衡反应在较低温度下进行，能使要溴化的物种如甲烷和乙烷在反应器的一个区，而要进行再均衡反应的二、三和其它多溴化物在反应器的另一区。
除焦过程中回收溴
不可避免地，卤化和再均衡反应过程中将会再生形成焦炭现象，若反应器或反应区中使用催化剂，则会因焦炭而使催化剂失活，因此需要周期性去除碳质沉积。此外，我们发现在所形成的焦炭中还有溴，非常希望这些溴能回收，以使总过程的溴损失最小化，从经济和环境原因考虑这一点很重要。
有几种形式的溴化物存在：HBr、有机溴化物如甲基溴和及二溴甲烷和分子溴。本发明提供从除焦过程中回收这些溴的方法。在优选的方案中，将指定的反应器关闭离线并将空气或氧气引入来燃烧碳沉积物和由残留的溴残渣来生成HBr。将排出气体加入到要送入溴再生反应器的空气(或氧气)反应物料流中，从而促使溴的完全回收。这一过程周期性重复进行。
尽管指定反应器是离线的，但通过使用备用反应器可使总过程不中断操作，备用反应器与其对应的反应器并排布置。例如，可采用双溴化反应器和双偶联反应器，当要进行除焦操作时，过程气体自一个而不是两个溴化反应器(或偶联反应器)移开。使用流化床可减少焦炭形成且有利于撤热和催化剂再生。
除焦过程的另一方案包括使用烷烃或烷烃混合物的非氧化除焦法，这可同时减少吸附产物的损失和过程的氧需求量。在除焦过程的另一方案中，在溴化反应过程中，将氧化剂如氧气、空气或浓缩空气一起送入溴化段，使焦炭转化为二氧化碳和/或一氧化碳，这样就可省去或减少离线除焦的需求。
烷基溴化物的分离
偶联反应器的进料中存在高浓度多卤化物种会导致焦炭形成量增加。在许多应用中，如生产芳烃和轻质烯烃的过程中，希望仅将单卤化物送入偶联反应器，以提高向产物的转化率。在本发明的一个实施方案中，卤化/再均衡反应器与偶联反应器之间加了一个特殊的分离步骤。
例如，可利用各化合物的较大沸点差异，使用蒸馏塔和相伴的热交换器(图1和2中的第一分离单元)来将单溴化物与多溴化物种分离。以塔底料流回收的多溴化物种可在溴化反应器中或单独的再均衡反应器中与烷烃进行再均衡反应来形成单溴化物物种和烯烃。蒸馏塔可在1-50bar的任何压力下操作。较高的压力将允许采用较高的冷凝器温度，因而减少了制冷需求量。
图4例示一个用来将单溴化物与多溴化物种分离的分离单元实施方案。来自溴化反应器的烷基溴化物自热交换器50通过来进行冷却，然后提供给配有两个热交换器52和53的蒸馏塔51。塔底处的热交换器52起再沸器作用，而塔顶处的热交换器53起部分冷凝器作用。这种构造能使自蒸馏塔取出的液体“塔底物”富含多溴化物(和含不多于微量的单溴化物)。将多溴化物通过另一个热交换器54，在它们返回溴化反应器(或送至单独的再均衡反应器)与未溴化烷烃进行再均衡反应之前将其变回气体。在塔顶处，热交换器53便于从回流罐进行液体部分回流，得到包括甲烷和HBr在内的富含轻质组分的蒸气和由单溴化物和HBr(和含不多于微量的多溴化物)组成的液流。
另一蒸馏过程布局包括有或没有侧线精镏塔或汽提塔的侧线蒸馏塔。若来自溴化反应器的进料含水，则蒸馏塔的塔底料流也将含有水，可采用对塔底料流进行液液相分流来使水与多溴化物种分离。由于水料流中存在HBr，将其送到HBr吸收塔或是送到溴再生反应器。
烷基卤化物催化偶联成更高分子量产物
将卤化/再均衡步骤中生成的烷基卤化物在催化剂上进行反应来生成高级烃和卤化氢。反应物进料也可含来自溴化反应器的卤化氢和未卤代的烷烃。按照本发明，使用许多催化剂的任一种来促进由卤代烃形成高级烃产物的反应。非限定性实例包括非晶硅铝酸盐(无定形固体酸)、钨/氧化锆超酸、硫酸化氧化锆、磷铝酸盐如SAPO-34及其骨架取代类似物(例如用Ni或Mn取代的)、沸石如SZM-5及其离子交换类似物和骨架取代的ZSM-5(用Ti、Fe、Ti+Fe、B或Ga取代的)。优选用于生产室温液体烃的催化剂包括离子交换的ZSM-5，其SiO2/Al2O3比低于300、优选低于100且最优选低于30或更低。优选的交换离子的非限定性实例包括Ag、Ba、Bi、Ca、Fe、Li、Mg、Sr、K、Na、Rb、Mn、Co、Ni、Cu、Ru、Pb、Pd、Pt和Ce的离子。这些离子可以纯盐或混合盐形式进行交换。制备掺杂型沸石和它们用作碳-碳偶联催化剂的方法描述于美国专利公开号2005/0171393A1的4-5页，全文引入作为参考。
在本发明的一个实施方案中，使用SiO2/Al2O3比为30的Mn交换ZSM-5作为偶联催化剂。在某些工艺条件下，它可产生液体烃产物的定制选择性。
卤代烷烃的偶联反应是在固定床、流化床或其它适宜反应器中于适当温度(如150-600℃，优选275-425℃)和压力(如0.1-35atm)以及1-45秒的停留时间(τ)的条件下实施的。一般来说，长停留时间将有利于反应物转化为产物以及产物的选择性，而短停留时间则意味着更高生产能力和(可能)经济上得到改进。通过改变催化剂、变动反应温度和/或变动在反应器中的停留时间可以调控产物选择性。例如，当将甲烷溴化反应的产物送入一个装填有金属-离子-浸渍的ZSM-5催化剂的偶联反应器时，其中所述的浸渍金属是Ag、Ba、Bi、Ca、Co、Cu、Fe、La、Li、Mg、Mn、Ni、Pb、Pd或Sr，且ZSM-5催化剂是Zeolyst CBV 58，2314，3024，5524或8014(得自ZeolystInternational(Valley Forge，PA))，在10秒的中等停留时间和350℃的中等温度条件下，二甲苯和均三甲苯是所生成的芳烃馏分的主要组分(苯+甲苯+二甲苯+均三甲苯，“BTXM”)。在425℃的反应温度和40秒停留时间的条件下，甲苯和苯是BTXM馏分的主要产物。产物选择性也可通过控制所生成的或送入偶联反应器的二溴甲烷浓度进行改变。流化床反应器构造用于偶联反应器时，预计对撤除反应热和连续除焦及催化剂再生会有一些好处。
在一个实施方案中，偶联反应是在一对并联布置的偶联反应器中实施的。这能使总过程连续运行，即使偶联反应器之一因除焦或其它原因关闭离线时也不会中断。类似的备用设备可应用于溴化、产物分离、卤素再生和其它总过程所用的单元中。
烃产物的分离和卤素回收
偶联产物包括高级烃和HBr。在图1和2所示的方案中，从偶联反应器出去的产物先在热交换器中进行冷却，然后送至吸收塔。使用填料塔或其它接触设备使HBr吸收到水中。送入的水和产物料流可以并流或逆流方式进行接触，优选逆流接触以便提高效率。HBr吸收过程以基本绝热或基本等温方式实施。在一个实施方案中，吸收后氢溴酸的浓度在5-70wt％范围，优选在20-50wt％范围。操作压力为1-50bar、更优选1-30bar。在实验室中，使用装有陶瓷或玻璃填料的玻璃塔或玻璃衬里塔。在中试和工业装置中，使用一或多种耐用的耐腐蚀(下文描述)材料。
在本发明的一个实施方案中，烃产物以液体形式从HBr吸收塔回收。使用液-液分流器将此液体烃料流与HBr水溶液料流进行相分离并送至产物净化单元。在另一个方案中，将烃产物以气体形式随未反应的甲烷和其它轻质烃一起从HBr塔回收。然后使用许多技术的任一种将产物与甲烷和轻质烃进行分离并回收。非限定性实例包括蒸馏、变压吸附和膜分离技术。
在一些方案中，产物净化单元包含或包括用于将产物料流中存在的卤代烃转化为未卤代烃的反应器。例如，在某些条件下，形成少量C1-C4溴化烷烃、溴苯和/或其它溴化物种，将其从偶联反应器送到液-液分流器16，然后送到产物净化单元17。这些溴化物种可在适当反应器中进行“加氢脱卤反应”。在一个实施方案中，该反应器包括一个连续固定床、装填有负载型金属或金属氧化物催化剂的催化转化器。活性成分的非限定性实例包括铜、氧化铜、钯和铂，优选钯。载体材料的非限定性实例包括活性碳、氧化铝、氧化硅和沸石，优选氧化铝。反应器在0-150psi、优选0-5psi和250-400℃、优选300-350℃的温度下操作，GHSV为1200-60小时-1、优选约240小时-1。当溴苯经此反应器通过时，很容易转化为苯和HBr，生成一些轻质烃(如C3-C7)作为副产物。尽管碳沉积(结焦)可使催化剂失活，但可通过将催化剂分别在如500℃和400℃下置于氧气然后氢气中处理的方法将催化剂再生。
在HBr与烃产物分离后，未转化的甲烷与轻质气体以蒸气形式自HBr吸收单元的出口离开。在本发明的一个实施方案中，未反应的甲烷在分离单元(附图中的第二分离单元)与轻质气体分离开来，此单元采用变温或变压吸附法、基于膜的分离法、低温蒸馏法(优选用于大规模生产过程)或其它适宜的分离方法进行操作。溴化反应器中甲烷转化率低会导致偶联产物带有轻质气体，这样就必须将这些物种从轻质气体中回收。可用于此目的的分离技术包括但不限于蒸馏、变温或变压吸附和基于膜的技术。
在本发明的另一方面，提供一种从HBr水溶液中分离出无水HBr的方法。HBr与水形成高沸点的共沸物，因此要从水溶液中分离出HBr就需要使用萃取剂来破坏共沸物或者使用变压蒸馏法来绕过共沸物。图5例示一个用来将HBr与水分离的萃取蒸馏单元的实施方案。在蒸馏塔200中萃取出水且得到HBr作为馏出物料流201。馏出物料流还含有少量水。在一个实施方案中，蒸馏塔200是一个盘式塔或填料塔。常规陶瓷填料优于整装填料。将溴化物盐如CaBr2水溶液在蒸馏塔顶部加入，使得水从HBr水溶液中萃提出来。此塔不需要冷凝器。再沸器203用来维持蒸馏塔的蒸气流。稀CaBr2水溶液料流202被送至蒸发段206，其任选有盘式或填料段。塔底料流在进入蒸发段之前要进行加热。大部分为水(和不多于痕量的HBr)的料流207离开蒸发段。
在一个实施方案中，HBr是在一种共享一个共离子(Br-或H+)或水合能高于HBr的离子(如Ca2+或SO4 2-)的电解质存在下从其水溶液中移出成为气体的。电解质的存在使HBr水溶液←→HBr气体平衡向气体析出方向移动，通过加热溶液效果会更好。
诸如CaBr2、MgBr2还有KBr、NaBr、LiBr、RbBr、CsBr、SrBr2、BaBr2、MnBr2、FeBr2、FeBr3、CoBr2、NiBr2、CuBr2、ZnBr2、CdBr2、AlBr3、LaBr3、YBr3和BiBr3的金属溴化物水溶液可用作萃取剂，优选CaBr2、MgBr2、KBr、NaBr、LiBr或它们的混合物的水溶液。蒸馏塔塔底料流含萃取剂稀溶液。将此料流送至另一蒸馏塔或蒸发器，蒸出水和在将萃取剂送回萃取蒸馏塔之前将其浓缩。若硫酸与HBr反应形成溴和二氧化硫可以最小化的话，则其可用作萃取剂。实施例1和2描述了一些从HBr水溶液中分离出无水HBr的演示实验。
在本发明另一方面中，提供各种净化产物的方法(分离和/或纯化)。在未纯化的产物料流中存在许多种溴化物：HBr，有机溴化物如甲基溴及二溴甲烷和溴化芳烃。在本发明的一个实施方案中，将产物料流经铜金属、NiO、CaO、ZnO、MgO、BaO或它们的组合上通过来使烃产物与溴化物种分离。优选地，产物是在一或多种上列材料上于25-600℃、更优选400-500℃的温度下运行。此过程能容忍可能存在的CO2。
在另一个实施方案中，特别适用于烃的大规模生产过程，采用蒸馏法将未反应的甲烷与其它轻质烃以及重质产物(如苯、甲苯等)分离开来。例如，图1和2中，甲烷和其它轻质烃经气体出口从吸收塔出去，送到分离单元(第二分离单元)。任何未转化的甲基溴将随轻质气体移出并可再循环回溴化/再均衡反应器。重质烃作为液体馏出物移出。
分子卤再生
在本发明一个实施方案中，通过将氢卤酸与分子氧在适当催化剂上进行反应来实施催化作用卤素再生的反应。再生反应可由下列方程式(1)代表：
Figure A200780010896D00211
此工艺过程是在一定温度范围和一定的氢氯酸(HX)与分子氧(O2)摩尔比即HX/O2为4:1-0.001:1、优选4:1(符合反应化学计量比)、更优选3.5:1(避免最后HBr超限)下进行的。
使用纯氧、空气或富氧气体可将卤素再生，反应可在有各种惰性非活性气体如氮气、二氧化碳、氩气、氦气和水蒸汽存在下进行。这些气体可以纯气体或选定的混合物形式按任何比例并入来满足工艺过程的要求。
许多材料已确定可用作卤素再生催化剂。可以使用一种催化剂或者将任意种类数、构造或比例的催化剂组合使用。一或多种金属如Cu、Ag、Au、Fe、Co、Ni、Mn、Ce、V、Nb、Mo、Pd、Ta或W的氧化物、卤化物和/或卤氧化物是代表例，更优选是Mg、Ca、Sr、Ba、V、Cr、Mn、Fe、Co、Ni、Cu、Zn或Ce的氧化物、卤化物和/或卤氧化物。最优选的催化剂是Cu的氧化物、卤化物和/或卤氧化物。
尽管不受任何任何理论束缚，下列方程式据信被认为是代表这些材料用于催化卤素形成反应时所发生的化学过程：
CaO+2HBr→CaBr2+H2O            (2)
CaBr2+1/2 O2→CaO+Br2          (3)
金属氧化物中的金属未改变氧化态，和
Co3O4+8HBr→3CoBr2+4H2O+Br2　 (4)
3CoBr2+2O2→Co3O4+3Br2        (5)
金属氧化物中的金属未改变氧化态。(2)+(3)和(4)+(5)的净反应是(7)：
Figure A200780010896D00221
等价于(1)。
在本发明一个实施方案中，使用氯作为卤化剂，二氧化铈(CeO2)用来催化从氢氯酸再生氯的反应。被认为由下列方程式表示：
CeO2+4HCl→CeCl2+2H2O+Cl2             (8)
CeCl2+O2→CeO2+Cl2                    (9)
总反应：2HCl+1/2O2→H2O+Cl2          (10)
也等价于(1)。
这种使用二氧化铈的方法非常新颖，因为它能使HCl基本完全消耗掉。相反，前面的金属氧化物、HCl和氧气的反应一般是得到HCl/Cl2混合物。因此，二氧化铈能很好地用作卤素再生催化剂，特别是烷烃卤化反应使用氯的情形下，氯的附带好处是低成本且为工业界广为熟知。
在本发明一个实施方案中，卤素再生催化剂负载于多孔或无孔的氧化铝、氧化硅、氧化锆、氧化钛或它们的混合物或者其它适宜载体上。可采用能使工艺过程效率最高的温度范围，如200-600℃、更优选350-450℃。
分子卤的回收和再循环
卤素再生反应同时生成水和分子卤。可在卤素与烃原料进行反应之前将水与卤素分离并移出。在卤素为溴的情形下，当冷凝这些物种的混合物时得到液-液相分层物即溴-水。例如，在本发明一个实施方案中，液-液闪蒸单元简单和经济地用来将大部分溴与水分离。溴相一般含极少量水，可直接送至溴化反应器。而水相则含1-3wt％溴。但是，若在溴再生步骤使用空气，则进入闪蒸单元的溴和水料流中同时存在氮气和未转化的氧气。
离开闪蒸单元的气体主要由氮气和未转化的氧气组成，但也带有一些溴和水。随蒸气相离开的溴量取决于闪蒸单元的温度和压力。闪蒸步骤可在0-50℃的温度范围操作，但优选低温(约2-10℃)以减少留在蒸气料流中的溴。将蒸气料流送至除溴段来回收溴。在一个实施方案中，操作压力为1-50bar、更优选1-30bar。由于水的冰点为0℃，不可能大幅度降低闪蒸罐19的温度。但是，可将闪蒸罐的蒸气料流与温度为-30℃到10℃的冰盐水接触。冰盐水的温度低于闪蒸罐可大大减少净化单元的除溴需求量。然后可以通过加热盐水来使溴蒸发，进一步加热来使盐水浓缩再用。此回收溴的方法可以连续或间歇方式实施。
离开液-液闪蒸罐的富水相中所含的溴可通过蒸馏法进行有效回收。如使用惰性气体从水相中汽提出溴(Waycuilis的描述)和基于吸附的方法的其它手段不是很有效，且有可能会导致溴损失较大。本文所述的蒸馏子过程产出溴或溴-水共沸物作为馏出物，又循环回闪蒸单元。水包含于塔底料流中。溴可与水发生逆反应形成少量HBr和HOBr。因此，在蒸馏系统中，塔底料流可存在ppm量的HBr(和/或HOBr)。可使用侧线精镏塔或汽提塔来减少塔底的溴含量以便产出纯水料流。其它可使水中溴含量降低到10ppm范围以下的替换方法包括但不限于加入极少量诸如硫酸、盐酸和磷酸的酸来降低水料流的pH值。降低pH值能使HBr和HOBr料流变回溴和水，因而大大减少了水料流中溴的损失。水料流中存在的HBr也可用离子交换树脂或电化学手段进行回收。
回收所有卤素再用。从经济和环境考虑，优选使总过程中使用的卤素损失即便不能完全消除，也要使其最小化。若在Br2再生后没有捕集，则分子溴有可能随排放的氮气和未转化的氧气一起离开。可在含负载于载体或是粉末状使用的固体CuBr或MnBr2床层中实施除溴操作来从气流中捕集Br2，所述气流还含有H2O、CO2、O2、甲烷和/或N2。在本发明一个实施方案中，除溴步骤优选在一定温度范围即-10℃到200℃范围进行操作。当除溴步骤完成后，可通过将床层温度升到220℃或更高、优选约275℃来从床层释放出分子溴。重要的是在释放溴的过程中，几乎不能有O2，因为O2会氧化金属且随着时间增加床层除溴能力会降低。
采用特种耐腐蚀材料的关键工艺元件构造
含卤工艺过程，无论是冷凝相还是蒸气相中所引起的腐蚀性对选择构造反应器、泵和辅助设备的耐用材料提出了很大挑战。陶瓷如氧化铝、氧化锆和碳化硅为本文所述过程遇到的大部分条件提供了极佳的耐腐蚀性。但是，陶瓷也有一些缺点，包括在张应变下结构强度不够、很难完全容纳气相反应(因为会沿接缝表面扩散或传质)和可能是大部分陶瓷固有的传热特性不理想。在高温和高压下和经历特长周期操作的结构耐用、气密和耐腐蚀性工艺控制设备(即壳管型热交换器、阀、泵等)可能需要使用可模锻金属如Au、Co、Cr、Fe、Nb、Ni、Pt、Ta、Ti和/或Zr，或是这些基本金属含诸如Al、B、C、Co、Cr、Cu、Fe、H、Ha、La、Mn、Mo、N、Nb、Ni、O、P、Pd、S、Si、Sn、Ta、Ti、V、W、Y和/或Zr元素的合金。
按照本发明的一个实施方案，本文所述过程是在强度和耐腐蚀性都足以经历长期连续操作的反应器、泵和辅助设备中实施的，适宜构造材料的选择强烈依赖于每一工艺控制部件所处的温度和环境。
各部件处于循环条件(如氧化和还原过程)与处于单一条件(氧化或还原过程)下所适用的材料有很大不同。已确定适用于温度范围在150-550℃处于循环条件下操作的材料的非限定性实例包括Au和Ti与Ni的合金，最适合的是Al/V合金型钛(更具体地说是Ti Grd-5)以及高Cr、低Fe低C含量的Ni-Cr-Mo合金(更具体地说是
Figure A200780010896D0024095556QIETU
，Alloy 59、C22、625和HX)。已确定适用于温度范围在150-550℃处于酸性卤化物至空气或者分子卤至空气循环条件下操作的材料的非限定性实例包括Fe与Ni的合金，最适用的是Ni-Cr-Mo合金和Ni-Mo系列。已确定适用于温度范围在100-550℃的单一环境条件的材料的非限定性实例包括Ta、Au以及Fe、Co和Ni的合金。对低温(<280℃)条件来说，可使用适宜的聚合物内衬如PTFE、FEP和更适宜是PVDF。所有材料都可以单独使用或与支持材料联用如涂布、覆层或化学/物理沉积于适宜的低成本材料如低合金钢上。
图6图示说明连续法将甲烷、天然气或其它烷烃原料转化为高级烃的另一操作模式。在溴再生过程中形成的水包括循环水存在下将烷烃在溴化段进行溴化反应。溴化产物或是通过再均衡反应器或是通过溴化反应器的再均衡段，通过用多溴化物作为溴化试剂使轻质气体进行再均衡来形成烯烃和烷基溴化物。再均衡产物包括烯烃、烷基单溴化物、一些多溴化物和HBr，将其随同任何未反应的烷烃一起送至偶联反应器。偶联产物被送至汽-液-液闪蒸罐。较高级烃作为有机相从汽-液-液闪蒸罐移出，而HBr水溶液作为较重相移出。气体料流从闪蒸罐送至分离系统来回收甲烷和轻质气体，分别循环回溴化段和再均衡段。
若使用空气作为溴再生过程的氧化剂，则必须从气体循环系统中移出氮气。从汽-液-液闪蒸罐出去的HBr水溶液被送至溴-水分离系统，在其中回收水。分离步骤可在蒸馏塔内实施，纯水作为馏出物被取出，塔底料流是HBr水溶液(HBr浓度高于蒸馏塔进料)。将HBr水溶液料流送回溴再生段，在空气或氧气存在下从HBr水溶液中再生出溴。
或者，使用萃取蒸馏法来将HBr与水分离。分离出的HBr被送至溴再生反应器并在空气或氧气存在下从HBr水溶液中再生出溴。在溴再生反应器中HBr不必完全转化。可对溴化、再均衡和/或偶联反应器定期进行除焦，含溴的除焦产物料流被送至溴再生反应器。
图7示出另一连续法可选方案。在溴再生过程中形成的水包括循环水存在下将烷烃在溴化段进行溴化反应。溴化产物(包括单溴化物和多溴化物)或是通过再均衡反应器或是通过溴化反应器的再均衡段，通过用多溴化物作为溴化试剂使轻质气体进行再均衡来形成烷基溴化物，然后将再均衡产物-烷基单溴化物、烯烃、少量多溴化物和HBr-和任何未反应的烷烃送至分离单元，将HBr水溶液与烷基溴化物分离。将烷基溴化物料流中的单溴化物与多溴化物分离。多溴化物循环到再均衡段，在其中多溴化物与循环气体进行反应来形成烯烃和单溴化物。
HBr水溶液与烷基溴化物的分离过程可在蒸馏塔联合液-液闪蒸罐中实施。烷基溴化物料流可含有HBr。将单溴化物送至偶联反应段，偶联产物被送至水吸收塔，使偶联反应器中生成的HBr从产物和未转化气体中移出。吸收塔的液体出料被送到汽-液-液闪蒸分离单元，高级烃产物作为有机相移出，HBr水溶液作为较重相移出。从吸收塔出来的气体被送至分离系统使甲烷与轻质气体分离。回收的甲烷循环回溴化段，而轻质气体则循环回再均衡段。
若使用空气作为溴再生过程的氧化剂，则必须从气体循环系统中移出氮气。从汽-液-液闪蒸罐出去的HBr水溶液料流与来自烷基溴化物分离段的HBr水溶液料流合并，被送至HBr/H2O分离系统。分离步骤可在蒸馏塔内实施，纯水作为馏出物被取出，塔底料流是HBr浓度高于蒸馏塔进料的HBr水溶液。将HBr水溶液料流送回溴再生段，在空气或氧气存在下从HBr水溶液中再生出溴。
或者，使用萃取蒸馏法来将HBr与水分离。分离出的HBr被送至溴再生反应器，在空气、氧气或富空气存在下从HBr水溶液中再生出溴。在溴再生反应器中HBr不必完全转化。可对溴化、再均衡和偶联反应器定期进行除焦，含溴的除焦产物料流被送至溴再生反应器。
下面是本发明的非限定性实施例和本发明实际操作的不同子过程。
实施例1  二溴甲烷与丙烷的再均衡反应
室温下将甲烷(11sccm，1atm)与氮气(15sccm，1atm)借助混合三通管进行混合并通过一个装满溴的室温鼓泡器。将CH4/N2/Br2混合物泵送至预热到500℃的玻璃管中，开始进行甲烷溴化反应，停留时间(“tres”)为60秒，主要生成溴甲烷、二溴甲烷和HBr。在混合三通管中将氮气、HBr和部分溴代烃与丙烷合并(0.75sccm，1atm)并通过525℃的第二玻璃管中，停留时间(“tres”)为60秒。在第二反应器管中，多溴代烃(即CH2Br2，CHBr3)与丙烷反应生成溴丙烷。理想化的再均衡反应为下列反应式
CH2Br2+C3H8→CH3Br+C3H7Br
当产物离开第二反应器，通过一系列含4M NaOH(中和HBr)和十六烷(含十八烷作为内标)的捕集使尽可能多的烃产物溶解来将它们收集起来。HBr/烃收集后，像甲烷和丙烷类挥发性组分收集于气袋中。用气相色谱量化所有产物。结果(实施例1)总结于表1。为进行比较，还进行了用两个反应器但没有与丙烷进行再均衡反应(对照A)和仅有第一反应器且无丙烷(“对照B”)的实验。
表1  二溴甲烷的再均衡反应
 
实施例1(溴化/再均衡) 对照A(溴化) 对照B(溴化)
溴化tres 60 60 60
再均衡tres 60 60 0
CH4转化率 40％ 47％ 45％
CH3Br/(CH3Br+CH2Br2) 93％ 84％ 74％
C3H8转化率 85％ N/A N/A
碳平衡 96％ 97％ 96％
实施例2  分离无水HBr
将20ml HBr水溶液原料加入到20gCaBr2·H2O中，然后加热到70℃。观察到有大量HBr释放出来(用AgNO3沉淀反应和NH3烟化试验来测定)。因为反应是在开口容器中进行的，没有测定释放出的HBr量。
实施例3  分离无水HBr
向HBr中加入浓H2SO4溶液来尝试用H2SO4脱水。将不同浓度的H2SO4加入HBr来测定不再发生HBr氧化反应的极限浓度，进行定性试验。
2HBr+H2SO4→Br2+SO2+2H2O
经测定，H2SO4浓度低于～70wt％就不发生氧化反应。将30ml的70％ H2SO4加入到30ml HBr共沸物(48wt％)原料中，将混合物加热至沸腾。用AgNO3沉淀法和测量AgBr重量来定量测定等分溶液混合时、沸腾15分钟后和30分钟后的HBr含量。
实施例4  溴甲烷在选定催化剂上的转换反应
按基本相同或类似于实施例1所述方式进行一系列甲烷溴化实验(10sccm甲烷自室温溴通过进行鼓泡，然后将混合物送至预热到500℃的反应器中)，然后在大气压(总压)和350-450℃温度下将溴化产物通过不同的金属-离子交换或浸渍的沸石催化剂，停留时间为40秒。表2总结了转换反应产物的分布。催化剂用金属离子(如Ba、Co、Mn等)且沸石用Zeolyst Int的沸石类型(如5524、58、8014等)表示。给出了每一实验中各产物的质量以及总产物质量。缩写B、PhBr、T、X和M分别是指苯、溴苯、甲苯、二甲苯和均三甲苯。
表2  溴甲烷在选定催化剂上的转换反应
Figure A200780010896D00281
Figure A200780010896D00291
Figure A200780010896D00301
实施例5  溴苯的加氢脱卤和催化剂再生
将用N2稀释(1.1ml/min)的包括1.9wt％的溴苯(PhBr)溶于十二烷的试验溶液(1.5ml/小时)送入装载有3.6g高分散的贵金属催化剂(Pd/Al2O3，0.5wt％)的管式石英反应器中。反应在325℃下进行，停留时间为15秒。将反应流出物捕集到一个预先加入8ml 4M NaOH溶液的鼓泡器中。载气以及气态产物收集于气袋中。将气相中的所有碳基产物和液体产物中的油相用GC进行分析。对基础捕集溶液，用离子选择电极测定HBr浓度。根据所有这些测定结果，计算碳和溴平衡。
实验连续运行300小时直到PhBr的转化率从最初70小时的100％下降到低于30％(图8)。在催化剂床层上发生PhBr的加氢脱溴反应，形成苯(“BZ”)和HBr作为主产物，还伴随检测出有一些轻质烃(C3-C7)作为副产物，这源于溶剂分解反应。催化剂失活的主要原因是碳沉积。验证催化剂可通过在500℃下用O2氧化(5ml/min)脱焦10小时然后在400℃下用H2还原(20ml/min)3小时得到再生。再生的催化剂的效率等同于新鲜催化剂，这可通过它催化同一加氢脱溴反应时最初70小时活性没有损失(图9)得到证实。
本发明已参照不同实施例和优选实施方案进行了描述，但不限于此。本领域技术人员根据所公开内容显见的其它改动和设备布局也可包括在本发明范围内。例如，在本发明的一个替换方案中，将溴再生反应器的产物25直接送到溴化反应器3。这样布置的好处是省去了闪蒸单元27中需要提出的溴，因而减少了液体溴的处理步骤。另外，通过取消包括单元26、27、31和34的除溴段，能大大降低过程的投资成本。对能量效率来说，希望溴再生过程的出口温度等于溴化反应温度。对溴再生过程来说，铈基催化剂要优于该方案的铜基催化剂，因为溴化铈的熔点(722℃)要高于溴化铜(I)(504℃)。溴化反应和偶联反应中存在氧会降低所期望产物的选择性，因此溴再生反应器必须要消耗掉进料中的所有氧。在此方案中，单溴化物分离过程5必须要改成使用液-液分流器在蒸馏塔51的塔底料流上移出水。液-液分流器移出的水含HBr，可采用萃取蒸馏法将其从水中移出(参见图5)，然后再循环回溴再生段。
还有一些其它改动属于所附的权利要求书及其等价方案所限定的本发明范围。

Claims (23)

1.将烃原料转化为一或多种高级烃的连续方法，包括：
(a)通过在足以形成烷基卤化物和卤化氢的工艺条件下将分子卤与含甲烷的烃原料进行反应来形成烷基卤化物，其中基本所有分子卤都被消耗掉；
(b)通过将一些或全部烷基卤化物与烷烃进料进行反应来形成再均衡烷基卤化物，其中所存在的单卤代烃比例提高；
(c)在足以形成高级烃和额外的卤化氢的工艺条件下将再均衡烷基卤化物与第一催化剂接触；
(d)将所述高级烃与所述卤化氢分离；
(e)通过有氧源存在、足以形成分子卤和水的工艺条件下将所述卤化氢与第二催化剂接触；
(f)将所述分子卤与水分离，使卤素得以再利用；和
(g)重复步骤(a)-(f)期望的次数。
2.权利要求1所述的连续方法，进一步包括步骤(a)和/或(b)后将单卤代烷基卤化物与多卤代烷基卤化物分离的步骤。
3.权利要求1所述的连续方法，其中所述烃原料包含一或多种C1-C4烃。
4.权利要求1所述的连续方法，其中所述烃原料包含天然气。
5.权利要求1所述的连续方法，其中所述卤素包含溴。
6.权利要求1所述的连续方法，其中所述卤素包含氯。
7.权利要求1所述的连续方法，其中所述烷烃进料含至少1％(体积)的一或多种C2-C5烃。
8.权利要求1所述的连续方法，其中在再均衡催化剂存在下单卤代烷基卤化物的存在量得以提高。
9.权利要求1所述的连续方法，其中所述再均衡催化剂包含金属、金属-氧材料或金属卤化物。
10.权利要求1所述的连续方法，其中第一催化剂包含沸石。
11.权利要求1所述的连续方法，其中所述沸石包含金属掺杂的或离子交换的沸石。
12.权利要求1所述的连续方法，其中所述沸石用锰掺杂。
13.权利要求1所述的连续方法，其中第二催化剂包含选自由CaO、CeO2、Co3O4、CuO、NiO、MgO、碳化物、氮化物、碳和粘土组成的组的至少一种材料。
14.权利要求1所述的连续方法，其中第二催化剂包含CuO或CeO2。
15.权利要求1所述的连续方法，其中第二催化剂包含选自由Ag、Au、Ba、Ca、Ce、Co、Cr、Cu、Fe、Mg、Mn、Mo、Nb、Ni、Pb、Pt、Sr、Ta、V、W、Mg、V、或Zn的卤化物、氧化物和卤氧化物组成的组的至少一种材料。
16.权利要求1所述的连续方法，其中采用变压蒸馏或萃取蒸馏法将HBr与氢溴酸水溶液分离。
17.权利要求16所述的连续方法，其中采用萃取蒸馏法，CaBr2、MgBr2、KBr、NaBr、LiBr或它们的混合物用作萃取剂。
18.权利要求16所述的连续方法，其中采用萃取蒸馏法，硫酸用作萃取剂。
19.权利要求1所述的连续方法，其中用于再均衡反应的所述烷烃进料包含有大量C2-C5烃的烃原料气。
20.权利要求1所述的连续方法，其中所述烃原料的卤化反应和再均衡烷基卤化物的形成反应是在不同的反应器中进行的。
21.将烃原料转化为一或多种高级烃的连续方法，包括：
(a)通过在足以形成烷基卤化物和卤化氢的工艺条件下将分子卤与含甲烷烃原料在卤化反应器中进行反应来形成烷基卤化物，其中基本所有分子卤都被消耗掉；
(b)将未反应的甲烷与烷基卤化物分离并将其送回到所述卤化反应器；
(c)通过将一些或全部烷基卤化物与含至少1％(体积)一或多种C2-C5烃的烷烃进料进行反应来形成再均衡烷基卤化物，其中所存在的单卤代烃比例提高；
(d)在足以形成高级烃和额外的卤化氢的工艺条件下将所述再均衡烷基卤化物与第一催化剂接触；
(e)将所述高级烃与卤化氢分离；
(f)通过有氧源存在、足以形成分子卤和水的工艺条件下将所述卤化氢与第二催化剂接触；
(g)将所述分子卤与水分离，使所述卤素得以再利用；和
(h)重复步骤(a)-(g)期望的次数。
22.权利要求20所述的连续方法，其中所述烃原料的卤化反应和再均衡烷基卤化物的形成反应是在不同的反应器中进行的。
23.将烃原料转化为一或多种高级烃的连续方法，包括：
(a)在足以形成烷基卤化物的工艺条件下将烃原料与分子卤进行反应来形成一或多种烷基卤化物；
(b)在足以形成高级烃和卤化氢的工艺条件下将所述一或多种烷基卤化物与第一催化剂接触来形成一或多种高级烃和卤化氢；
(c)将所述一或多种高级烃与卤化氢分离；
(d)通过有氧源存在、足以形成卤素的工艺条件下将所述卤化氢与第二催化剂接触来使卤素再生；和
(e)重复步骤(a)-(d)期望的次数。
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