CN1064474A - 轻质烃转化成烯烃、汽油和甲醇的方法 - Google Patents
轻质烃转化成烯烃、汽油和甲醇的方法 Download PDFInfo
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Abstract
本发明提供了一种把轻质烃转化成烯烃、汽油和
甲醇的方法。在第一步中,把含一种或多种轻质烃的
气体合成包括粗汽油的高级烃,未被合成的轻质烃和
碳的氧化物被用于生产甲醇,其可用于几种目的,包
括合成汽油或乙烯。
Description
本发明涉及轻质烃合成高级烃包括汽油的方法,其以补充二级产物应用的转化量进行转化。该方法用未合成的轻质烃与作为二级产物得到的碳的氧化物一起制备甲醇。然后,甲醇和/或该高级烃可用于制备汽油或乙烯。
以前对汽油的合成的研究都集中在甲烷上,因为甲烷是一种大量供应的化学品,天然气就主要是由甲烷组成的。一种公知的并最初由Mobil Oil Company开发的由甲烷生产汽油的方法是首先转化脱硫的天然气,形成氢、一氧化碳和二氧化碳,换句话说是众所周知的合成气。然后,用非常确定的低压技术由合成气合成甲醇。用合适的催化剂把甲醇制成汽油,us3894107,3931349和有关专利公开了这方面的内容。
由Atlantic Richfield Company(ARCO)开发的另一种方法包括用合适的氧化催化剂,先由甲烷合成高级烯烃,参见us4777313和其中所列的专利。有些汽油是用这种合成法生产的,该合成法生产的低级烃也可转化成汽油。该方法的主要缺点是工业上可接受的选择性、甲烷的转化率比较低。ARCO采用的解决办法是循环未转化的甲烷,这需要很大的反应器/再生器系统。另外,在该合成法中生成的大量二氧化碳未被利用,而排放到大气中了。这就意谓着甲烷产生的许多碳未转化成有用的产物。另外,大量的二氧化碳排放到大气中对环境是有害的。
本发明提供一种把轻质烃,最好是有多达4个碳原子的轻质烃转化成高级烃和甲醇的方法,其包括把含有一种或多种轻质烃的气体在合成条件下与氧化合成剂接触,把至少部分轻质烃合成高级烃,回收该高级烃,回收在合成过程中生成的二氧化碳,将回收的二氧化碳与氢气混合,然后,在合成甲醇的条件下把该混合气与可合成甲醇的试剂接触,并回收甲醇。
最好,该气体不循环,即仅接触一次,该单次接触之后,回收剩余的未合成的轻质烃。然后,把回收的轻质烃与合成过程中生成的一氧化碳一起转化成氢、一氧化碳和二氧化碳,其在轻质烃合成之后与回收的二氧化碳混合,以便合成甲醇。作为另一种可选择的回收该轻质烃的方法,在除去高级烃和水之后,把合成反应器流出物的所有剩余组分通到转化器中。
在优选的实施方案中,氧化合成剂包括至少一种选自锰、锡、铟、锗、铅、锑和铋,最好是锰的金属的至少一种可还原的氧化物。如果该氧化合成剂另外含有至少一种选自碱金属、碱土金属和它们的化合物,最好是锂的化合物的助催化剂是比较好的。该氧化合成剂另外含有至少一种硼或硼化物组分甚至是更好的。
本发明的方法可特别用于由轻质烃生产汽油。在一个实施方案中,含有一种或多种轻质烃的气体在合成条件下与氧化合成剂接触,把至少部分轻质烃合成高级烃包括汽油,分别回收该汽油和高级烃。用回收的二氧化碳和转化的未合成的轻质烃合成甲醇,回收甲醇,,并且至少部分甲醇转化成汽油。另外,该方法可用于由轻质烃生产乙烯,既可作为轻质烃合成的一种产物,也可把至少部分甲醇转化成乙烯。
在另一个实施方案中,合成反应器的全部流出物在合适的条件下与可由烯烃合成汽油的催化剂接触。这种催化剂最好是适于流化的沸石催化剂。除去水之后,回收汽油和其他比甲烷和乙烷更高级的烃。剩余的未反应的甲烷、乙烷和二氧化碳可以利用,或用于制取甲醇或用作发电厂的燃料或其他用途。
本方法的优点是在高级烃的合成中生成的二氧化碳可以利用,而不是作为废物排放到大气中造成潜在的有害环境的影响。该优选的实施方案的另一个优点是在第一次通过反应器中未被合成的轻质烃原料不循环到该合成反应器中,因此,允许使用需要较少催化剂的较小和便宜的反应器,但仍可用于较高产率地生产有用的产物甲醇,因为二氧化碳可以利用。该方法的另一个优点是在由所使用的装置生产产品方面具有一定的灵活性,随着商业经济的变化允许在产物的混合物方面立即改变。
图1是表示该过程流程的草图,其用并流进料反应器进行轻质烃合成。
图2是设计用在本方法的轻质烃合成步骤中的并流进料反应器的正面图。
图3是两段反应系统的示意图。
图4是表示使用轻质烃合成产物的另一种方法的过程流程的草图。
本发明的方法可以使用任何来源的轻质烃,最好是含有多达4个碳原子的烃,或是纯的或是混合的其他轻质烃和/或与少量惰性物质的混合物。在优选的实施方案中,原料是天然气,该天然气在油田已进行脱硫处理并除去水和部分可冷凝的烃,一般是丙烷和高级烃。在另一个实施方案中可以利用炼厂废气。
图1是本发明方法的优选实施方案的草图。轻质烃原料2进到并流进料反应器4,在此与催化剂接触。该催化剂含有载有氧化合成剂的常规载体物质。优选催化剂的组成和制备方法公开在us4499322和4777313中,这些文献在此列出作为参考文献,但是其他合适的公知催化剂也可以使用。最好该催化剂含有氧化锰作为氧化剂,锂化合物和硼或硼化合物作为助催化剂。
在并流进料反应器中,通过向反应器中引入氧气源催化剂被就地再次氧化,氧气源是与轻质烃原料并流引入。在优选的实施方案中,使用压缩富氧空气6,但是空气或纯氧是其他可以使用的氧气源。用合适的氮提取装置10可由压缩空气8提供富氧空气。可以用任何公知的提供富氧空气的技术,包括压力回转吸附(PSA)脱氮法和/或低温空气分离装置。最好收集氮气12并销售或做他用。
催化剂由催化剂分离装置12进到反应器4,最好在富氧空气流6中引入反应器4。用压缩空气提供流化的上流催化剂。轻质烃原料2引入反应器的下部,当催化剂和原料一起向上输送时就发生了合成反应,优选的转化率为25%~35%。
反应器4的流出物通过催化剂分离装置12,分离的催化剂循环通过反应器4。冷却并急冷气体14,冷凝粗汽油15并在这一步进行分离。然后,气体通到二氧化碳脱除装置16,除去二氧化碳后,该气体通到冷冻装置18除去未反应的轻质烃和二级合成产物。在这一步骤也可以分离出氮,如果这样,或把氮20排出或收集使用或出售。轻质烃22和在装置16排出的二氧化碳24一起在常规甲醇装置26中用于合成甲醇。
把冷冻装置18的烯烃混合物通到常规烯烃回收装置28,由其回收乙烯、丙烯和其他烃如液化石油气(LPG)。
图2是优选的并流进料反应器系统的正面图。优选的实施方案使用两列装置,每列装置含有反应器100、反应器汽提装置102和连带的旋风分离器,设计该旋风分离器回收20μm固粒可达到大于99.5%。虽然图2中画出单个旋风分离器,但固粒分离专业的熟练的技术人员会了解到可以用附加的旋风分离器达到由流出物气体中分离固粒所要求的水平。
催化剂由汽提装置102通过重力,由滑阀108控制通过催化剂进料管106。然后,通过从入口管114喷射到反应器100的提升管底部112的压缩空气、氧或富氧空气110,最好以约12.2m(40英尺)/秒的速度高速提升催化剂。
在部位118把轻质烃进料气116引入反应器100,在118处,反应器的直径开始增加。增加反应器直径的作用是降低气体和催化剂混合物的速度,以便增加催化剂的停留时间。本专业熟练的技术人员可以对任何实际条件的装置计算出给定要求转化程度所需的停留时间。在优选的实施方案中,在最大直径120那一点的速度是约2.1m(7英尺)/秒。
最好反应器的操作条件为温度760-870℃(1400-1600°F),压力约30~80PSIA。在开始运转及对低转化率下的操作,原料气在引入反应器之前要预热。但是,在高转化率下,反应是放热的,所以原料气可以是在环境温度下。
在点120之后,反应器直径减小,由此加速流出物流流向反应器出口管122。这种加速有助于减少二级反应的催化作用。在优选的实施方案中,流出物流被加速到约12.2m(40英尺)/秒。含有催化剂和包括未合成的轻质烃及合成产物的气体的流出物流通过喷咀124切线方向喷入汽提装置102,其再次把该物流加速。在该优选的实施方案中,进入汽提装置102的物流的速度约16.8m(55英尺)/秒。
在汽提装置102中达到大部分催化剂与气体的分离。用蒸汽汽提除去残留的烃类之后,该催化剂通过催化剂进料管106排出汽提装置,循环通过反应器100。仍含有催化剂细粉的气体组分通过压力送气系统126提升,并通过压力送气系统出口管128排出,切线方向喷射到旋风分离器104中。为了把二级反应减少到最小,在反应器出口管122和压力送气系统出口管128中用水急冷流出物流到约760℃(1400°F)。在旋风分离器中进一步分离催化剂颗粒,分离的催化剂颗粒通过管130输送到汽提装置102。由旋风分离器104顶部排出的气体使其通过串联的两级并联的旋风分离器进一步与残留的催化剂细粉分离,达到所需求的回收固粒的水平,最好直径为20微米及更大的固粒99.5%以上得到回收。
代替并流进料反应器,可以用两段氧化还原反应器,在其中,催化剂在一个与反应器分开的容器中再氧化。这样的一个反应器系统示于图3。轻质烃原料200进到含催化剂的反应器202的下部。流出物气体离开反应器并通过串联的旋风分离器,这里用旋风分离器204和206表示,分离出催化剂细粉。废催化剂通过管208离开反应器,并通过汽提装置210,在其进入再生器212之前从催化剂中汽提出烃类。在此处,在约816℃(1500°F)的高温下,废催化剂与氧源接触,氧源可以是空气或蒸汽/空气的混合物,以使催化剂再氧化。通过汽提装置214除去氮之后,用部分原料200,通过提升原料管216把催化剂提升到反应器202中,该部分原料200通过提升原料气体供应管线218管线输送。
众所周知,在高温下,轻质烃合成催化剂会被铁中毒,因此,最好反应器系统的所有湿表面都涂上合适的衬里,如高氧化铝耐热物质。
气体离开催化剂除去系统之后,在串联热交换器中冷却到约49℃(120°F)。如果需要的话,这种通过使气体与喷淋水接触然后使其通过塔盘塔的冷却之后,可以从反应器中最终除去所有所携带的固粒。在优选的实施方案中,然后把气体物流压缩到约1.03MPa(150psi)。在这一过程中,物流中的大部分水和重烃被液化并被除去。适当的处理除去烃类和其他污染物之后,所生成的大量的水可以在工业上使用。
下一步是除去二氧化碳16,最好是用基于含水甲醇胺、DEA、MDEA等的常规酸性气体除去系统进行。
然后,把脱除二氧化碳后的烃气体冷却到约7℃(45°F)。分离在这些条件下冷凝的烃类和水,最好用分子筛脱水系统除去剩余的水蒸汽和二氧化碳。
然后,在常规冷箱系统18中把烃物流进一步冷冻。从该系统中作为一种产物物流回收乙烯和丙烯。把该物流压缩到约400psi,进一步提纯除去微量化合物,然后用常规乙烯分离技术从丙烯中分离出乙烯。在该优选的实施方案中,使用适于生产聚合物级己烯和丙烯的冷冻技术。在冷箱系统之前冷凝粗汽油并作为一种分离的物流得到粗汽油。
将未反应的轻质烃与二级合成产物特别是一氧化碳一起分别从冷箱系统回收。回收之后,它们仍可以与氮混合,但是在优选的实施方案中指定冷箱系统分离氮,其或者被清除或者被收集。把回收的气体压缩到约3.1Mpa(450psi),然后通到转化器中把轻质烃转化成合成气。在优选的实施方案中,使用常规管式蒸汽转化器,然后把转化器的合成气冷却到32℃(90°F),与在装置16回收的已压缩到相似压力的二氧化碳混合,该混合物压缩到约8.3MPa(1200psi)并通到甲醇合成系统。可以使用任何合适的公知的甲醇合成系统,优选的实施方案是用Linde AG类型等温反应器。
为了冷凝甲醇和水,把离开甲醇合成反应器的气体冷却,部分剩余的气体循环到合成反应器。然后,用常规技术,最好是蒸馏,把甲醇与水分离并提纯,需要的提纯程度取决于最终对甲醇的使用。可以按上述方法处理水,以便进一步使用。
在另一个示于图4的实施方案中,用常规冷却和急冷装置302把轻质烃合成反应器300的产物冷却到约427℃(800°F),然后直接加到含有沸石催化剂最好是ZSM-5或相当的催化剂的流化床304中,在此,烯烃转化成汽油和LPG。为了分离水和所有的比甲烷和乙烷高级的烃类,冷却反应器的产物,并用常规设备306,回收该产物。压缩未反应的气体、初级甲烷和二氧化碳,并送到传统的蒸汽转化甲醇装置308中。此外,未反应的气体可以直接送到燃气轮机辅助发生装置以发电和/或生产蒸汽,或用作其他用途的燃料。该实施方案的优点是费用低,其需要比较小的冷却设备。此外,所需的催化剂细粉的分离程度不太大,需要较少的分离设备。
在上述两个方案的任何一个方案中,用合适的沸石催化剂至少部分甲醇可以转化成汽油。该优选的方法在Mobil Oil Corporation的美国专利3894107中有所描述,此专利在此列为参考文献,这些催化剂在美国专利3702886和3709979中作了描述。在该优选的实施方案中,用相当于Mobil ZSM-5催化剂的沸石催化剂,其可以从许多卖主买到。此外,甲醇可用于制取乙烯。最好用两段法进行这种转化,在第一段用合适的沸石催化剂把甲醇转化成DMA,然后在第二段用活性氧化铝催化剂把DMA转化成乙烯。
Claims (15)
1、转化轻质烃成高级烃和甲醇的方法,该方法包括:
(a)含有至少一种轻质烃的气体与氧化合成剂接触,由至少部分所说的轻质烃合成高级烃;
(b)回收合成步骤(a)中生成的高级烃;
(c)单独回收合成步骤(a)中生成的二氧化碳;
(d)回收的二氧化碳与氢混合;
(e)步骤(d)的混合物与能合成甲醇的催化剂接触合成甲醇;
(f)回收甲醇。
2、根据权利要求1的方法,其中轻质烃是甲烷、乙烷、丙烷、正丁烷和异丁烷中的至少一种。
3、根据权利要求1或2的方法,其中在步骤(a)中气体仅与氧化合成剂接触一次。
4、根据权利要求1,2或3的方法,其中氧化合成剂包括至少一种可还原的至少一种选自Mn、Sn、In、Ge、Pb、Sb和Bi的金属的氧化物。
5、根据权利要求4的方法,其中氧化合成剂还包括至少一种选自碱金属、碱土金属及其化合物的助催化剂。
6、根据权利要求5的方法,其中助催化剂是Li的化合物。
7、根据权利要求5或6的方法,其中氧化合成剂还含有硼和/或硼的化合物。
8、根据上述权利要求的任意一项的方法,其中步骤(d)中所用的混合物是由下述步骤制备的:
(g).回收在合成步骤(a)之后剩余的未合成的轻质烃和生成的一氧化碳;
(h)转化步骤(g)的至少部分未合成的轻质烃和一氧化碳,得到氢、一氧化碳和二氧化碳;
(i)把从步骤(c)回收的二氧化碳与步骤(h)的产物包括氢混合。
9、根据上述权利要求的任何一项的方法,还包括回收在步骤(a)和/或(f)产生的水的步骤。
10、根据权利要求9的方法,其中从在步骤(a)中所用的反应器排出的物流中除去水。
11、根据上述权利要求的任意一项的方法,其中,步骤(a)生成的高级烃包括由此回收的汽油,并且至少部分步骤(f)的甲醇转化成汽油。
12、根据权利要求1-11的任意一项的方法,其中至少步骤(f)的甲醇转化成乙烯。
13、由轻质烃生产汽油的方法,该方法包括:
(a)含有至少一种轻质烃的气体在合成条件下通过反应器,以使气体与氧化合成剂接触,由至少部分所说的轻质烃合成包括烯烃的高级烃;
(b)排出反应器的流出物与能够由烯烃合成汽油的催化剂接触,合成汽油;
(c)从汽油合成的产物中除去水;
(d)回收所有比甲烷和乙烷高级的烃;
(e)转化步骤(d)之后剩余的甲烷、乙烷和二氧化碳,得到氢、一氧化碳和二氧化碳;
(f)使转化步骤(e)的产物与能够合成甲醇的催化剂接触,合成甲醇;
(g)回收甲醇。
14、根据权利要求13的方法,其中能够由烯烃合成汽油的催化剂是沸石。
15、根据权利要求13或14的方法,包括权利要求2-7中的至少一个权利要求的特征。
Priority Applications (6)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US07/479,086 US5026934A (en) | 1990-02-12 | 1990-02-12 | Method for converting light hydrocarbons to olefins, gasoline and methanol |
NZ237096A NZ237096A (en) | 1990-02-12 | 1991-02-12 | Method for synthesis of light hydrocarbons to higher hydrocarbons |
CA002075891A CA2075891A1 (en) | 1990-02-12 | 1991-02-12 | Circulating bed cofeed conversion reactor and method for converting light hydrocarbons to olefins, gasoline and methanol |
PCT/US1991/000937 WO1991012224A2 (en) | 1990-02-12 | 1991-02-12 | Circulating bed cofeed conversion reactor and method for converting light hydrocarbons to olefins, gasoline and methanol |
EP91904659A EP0515500A1 (en) | 1990-02-12 | 1991-02-12 | Circulating bed cofeed conversion reactor and method for converting light hydrocarbons to olefins, gasoline and methanol |
CN91101783.6A CN1064474A (zh) | 1990-02-12 | 1991-02-25 | 轻质烃转化成烯烃、汽油和甲醇的方法 |
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Application Number | Priority Date | Filing Date | Title |
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US07/479,086 US5026934A (en) | 1990-02-12 | 1990-02-12 | Method for converting light hydrocarbons to olefins, gasoline and methanol |
US53191090A | 1990-06-01 | 1990-06-01 | |
CN91101783.6A CN1064474A (zh) | 1990-02-12 | 1991-02-25 | 轻质烃转化成烯烃、汽油和甲醇的方法 |
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CN1064474A true CN1064474A (zh) | 1992-09-16 |
Family
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CN91101783.6A Pending CN1064474A (zh) | 1990-02-12 | 1991-02-25 | 轻质烃转化成烯烃、汽油和甲醇的方法 |
Country Status (6)
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US (1) | US5026934A (zh) |
EP (1) | EP0515500A1 (zh) |
CN (1) | CN1064474A (zh) |
CA (1) | CA2075891A1 (zh) |
NZ (1) | NZ237096A (zh) |
WO (1) | WO1991012224A2 (zh) |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
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Families Citing this family (40)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2925963B2 (ja) | 1994-12-05 | 1999-07-28 | 石油公団 | メタンの酸化カップリング方法とその装置 |
US5861441A (en) * | 1996-02-13 | 1999-01-19 | Marathon Oil Company | Combusting a hydrocarbon gas to produce a reformed gas |
US6201029B1 (en) | 1996-02-13 | 2001-03-13 | Marathon Oil Company | Staged combustion of a low heating value fuel gas for driving a gas turbine |
US6313361B1 (en) | 1996-02-13 | 2001-11-06 | Marathon Oil Company | Formation of a stable wax slurry from a Fischer-Tropsch reactor effluent |
US5733941A (en) * | 1996-02-13 | 1998-03-31 | Marathon Oil Company | Hydrocarbon gas conversion system and process for producing a synthetic hydrocarbon liquid |
US6130259A (en) * | 1996-02-13 | 2000-10-10 | Marathon Oil Company | Hydrocarbon gas conversion system and process for producing a synthetic hydrocarbon liquid |
BR9709857A (pt) * | 1996-06-21 | 2002-05-21 | Syntroleum Corp | processo e sistema de produção de gás de sìntese |
MY118075A (en) | 1996-07-09 | 2004-08-30 | Syntroleum Corp | Process for converting gas to liquids |
US5950732A (en) * | 1997-04-02 | 1999-09-14 | Syntroleum Corporation | System and method for hydrate recovery |
AU9690298A (en) | 1997-10-10 | 1999-05-03 | Syntroleum Corporation | System and method for converting light hydrocarbons to heavier hydrocarbons withseparation of water into oxygen and hydrogen |
US6096934A (en) * | 1998-12-09 | 2000-08-01 | Uop Llc | Oxidative coupling of methane with carbon conservation |
US7838708B2 (en) | 2001-06-20 | 2010-11-23 | Grt, Inc. | Hydrocarbon conversion process improvements |
US6794417B2 (en) | 2002-06-19 | 2004-09-21 | Syntroleum Corporation | System and method for treatment of water and disposal of contaminants produced by converting lighter hydrocarbons into heavier hydrocarbon |
US7151198B2 (en) * | 2002-12-30 | 2006-12-19 | Exxonmobil Chemical Patents Inc. | Integration of a methanol synthesis system with a methanol to olefin reaction system |
US7161051B2 (en) * | 2002-12-30 | 2007-01-09 | Exxonmobil Chemical Patents Inc. | Integration of a methanol synthesis system with a methanol to olefin reaction system |
RU2366642C2 (ru) | 2003-07-15 | 2009-09-10 | Джи Ар Ти, Инк. | Синтез углеводородов |
US20050171393A1 (en) | 2003-07-15 | 2005-08-04 | Lorkovic Ivan M. | Hydrocarbon synthesis |
US20080275284A1 (en) | 2004-04-16 | 2008-11-06 | Marathon Oil Company | Process for converting gaseous alkanes to liquid hydrocarbons |
US7244867B2 (en) | 2004-04-16 | 2007-07-17 | Marathon Oil Company | Process for converting gaseous alkanes to liquid hydrocarbons |
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US20060100469A1 (en) | 2004-04-16 | 2006-05-11 | Waycuilis John J | Process for converting gaseous alkanes to olefins and liquid hydrocarbons |
US8642822B2 (en) | 2004-04-16 | 2014-02-04 | Marathon Gtf Technology, Ltd. | Processes for converting gaseous alkanes to liquid hydrocarbons using microchannel reactor |
WO2007092410A2 (en) | 2006-02-03 | 2007-08-16 | Grt, Inc. | Separation of light gases from halogens |
EP1993979A4 (en) | 2006-02-03 | 2011-07-06 | Grt Inc | CONTINUOUS PROCESS FOR CONVERTING NATURAL GAS TO LIQUID HYDROCARBONS |
US8921625B2 (en) | 2007-02-05 | 2014-12-30 | Reaction35, LLC | Continuous process for converting natural gas to liquid hydrocarbons |
US7998438B2 (en) | 2007-05-24 | 2011-08-16 | Grt, Inc. | Zone reactor incorporating reversible hydrogen halide capture and release |
US7989507B2 (en) * | 2008-05-20 | 2011-08-02 | Siemens Aktiengesellschaft | Production of fuel materials utilizing waste carbon dioxide and hydrogen from renewable resources |
US8282810B2 (en) | 2008-06-13 | 2012-10-09 | Marathon Gtf Technology, Ltd. | Bromine-based method and system for converting gaseous alkanes to liquid hydrocarbons using electrolysis for bromine recovery |
US8198495B2 (en) | 2010-03-02 | 2012-06-12 | Marathon Gtf Technology, Ltd. | Processes and systems for the staged synthesis of alkyl bromides |
US8367884B2 (en) | 2010-03-02 | 2013-02-05 | Marathon Gtf Technology, Ltd. | Processes and systems for the staged synthesis of alkyl bromides |
US8815050B2 (en) | 2011-03-22 | 2014-08-26 | Marathon Gtf Technology, Ltd. | Processes and systems for drying liquid bromine |
US8436220B2 (en) | 2011-06-10 | 2013-05-07 | Marathon Gtf Technology, Ltd. | Processes and systems for demethanization of brominated hydrocarbons |
US8829256B2 (en) | 2011-06-30 | 2014-09-09 | Gtc Technology Us, Llc | Processes and systems for fractionation of brominated hydrocarbons in the conversion of natural gas to liquid hydrocarbons |
US8802908B2 (en) | 2011-10-21 | 2014-08-12 | Marathon Gtf Technology, Ltd. | Processes and systems for separate, parallel methane and higher alkanes' bromination |
US9193641B2 (en) | 2011-12-16 | 2015-11-24 | Gtc Technology Us, Llc | Processes and systems for conversion of alkyl bromides to higher molecular weight hydrocarbons in circulating catalyst reactor-regenerator systems |
WO2015081122A2 (en) | 2013-11-27 | 2015-06-04 | Siluria Technologies, Inc. | Reactors and systems for oxidative coupling of methane |
US10793490B2 (en) | 2015-03-17 | 2020-10-06 | Lummus Technology Llc | Oxidative coupling of methane methods and systems |
EP4071131A1 (en) | 2016-04-13 | 2022-10-12 | Lummus Technology LLC | Apparatus and method for exchanging heat |
US10870810B2 (en) | 2017-07-20 | 2020-12-22 | Proteum Energy, Llc | Method and system for converting associated gas |
Family Cites Families (18)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB634102A (en) * | 1949-08-05 | 1950-03-15 | Standard Oil Dev Co | An improved process for carrying out vapor phase chemical reactions in the presence of a suspended catalyst |
US3041273A (en) * | 1953-09-09 | 1962-06-26 | Sinclair Research Inc | Process for the conversion of hydrocarbons with the use of an expanding transfer line reactor |
US3894102A (en) * | 1973-08-09 | 1975-07-08 | Mobil Oil Corp | Conversion of synthesis gas to gasoline |
US3894107A (en) * | 1973-08-09 | 1975-07-08 | Mobil Oil Corp | Conversion of alcohols, mercaptans, sulfides, halides and/or amines |
US3931349A (en) * | 1974-09-23 | 1976-01-06 | Mobil Oil Corporation | Conversion of methanol to gasoline components |
US3969426A (en) * | 1974-10-17 | 1976-07-13 | Mobil Oil Corporation | Conversion of methanol to products comprising gasoline boiling components |
US4035430A (en) * | 1976-07-26 | 1977-07-12 | Mobil Oil Corporation | Conversion of methanol to gasoline product |
US4499322A (en) * | 1983-08-12 | 1985-02-12 | Atlantic Richfield Company | Methane conversion |
US4544784A (en) * | 1982-08-30 | 1985-10-01 | Atlantic Richfield Company | Methane conversion |
US4665260A (en) * | 1982-08-30 | 1987-05-12 | Atlantic Richfield Company | Methane conversion |
US4567307A (en) * | 1982-08-30 | 1986-01-28 | Atlantic Richfield Company | Two-step methane conversion process |
US4560821A (en) * | 1982-08-30 | 1985-12-24 | Atlantic Richfield Company | Methane conversion |
US4777313A (en) * | 1983-08-12 | 1988-10-11 | Atlantic Richfield Company | Boron-promoted reducible metal oxides and methods of their use |
US4634800A (en) * | 1984-04-16 | 1987-01-06 | Atlantic Richfield Company | Methane conversion process |
US4926006A (en) * | 1985-11-01 | 1990-05-15 | Director General Of Agency Of Industrial Science And Technology | Aluminoborosilicate containing alkaline earth metal, a method for the preparation thereof and a method for the catalytic preparation of a lower olefin therewith |
US4788372A (en) * | 1987-02-13 | 1988-11-29 | Atlantic Richfield Company | Methane conversion process |
US4795849A (en) * | 1987-08-04 | 1989-01-03 | Atlantic Richfield Company | Methane conversion process |
US4888131A (en) * | 1988-03-28 | 1989-12-19 | Exxon Research And Engineering Company | Synthesis gas preparation and catalyst therefor |
-
1990
- 1990-02-12 US US07/479,086 patent/US5026934A/en not_active Expired - Lifetime
-
1991
- 1991-02-12 EP EP91904659A patent/EP0515500A1/en not_active Withdrawn
- 1991-02-12 CA CA002075891A patent/CA2075891A1/en not_active Abandoned
- 1991-02-12 WO PCT/US1991/000937 patent/WO1991012224A2/en not_active Application Discontinuation
- 1991-02-12 NZ NZ237096A patent/NZ237096A/en unknown
- 1991-02-25 CN CN91101783.6A patent/CN1064474A/zh active Pending
Cited By (5)
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Also Published As
Publication number | Publication date |
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NZ237096A (en) | 1992-09-25 |
EP0515500A1 (en) | 1992-12-02 |
US5026934A (en) | 1991-06-25 |
WO1991012224A3 (en) | 1992-04-02 |
CA2075891A1 (en) | 1991-08-13 |
WO1991012224A2 (en) | 1991-08-22 |
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