CN1183064C - 用合成气生产中的氢进行再生催化剂和烃类转化的气相转化反应 - Google Patents
用合成气生产中的氢进行再生催化剂和烃类转化的气相转化反应 Download PDFInfo
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Abstract
一种气体转化方法,其中由含有H2和CO混合物的合成气进料生产烃类和氢气,由一部分进料得到的氢气用于(i)烃类合成催化剂再生和(ii)至少一部分合成的烃类的加氢转化改质中的一个或多个过程。通过(i)物理分离方法例如变压吸附和化学方法例如水蒸气转换反应中的一个或多个,由送入烃类合成反应器的合成气滑流生产氢气。如果使用转换反应器,由于合成气生成器的生产能力不足,还可用物理分离方法例如变压吸附来由转换反应器的气体流出物中分离纯的氢气物流。
Description
发明背景
发明范围
本发明涉及一种由合成气生产烃类和氢的方法。更具体地说,本发明涉及一种由合成气合成烃类和生产氢的气相转化方法,氢气用于(i)烃类合成催化剂的再生和(ii)烃类产品改质中的至少一种。
发明背景
烃类合成方法是已知的,在这些方法中,将含有H2和CO混合物的合成气进料送入烃类合成反应器,在该反应器中,合成气进料在费托合成催化剂存在下,在有效生成更高分子量烃类的条件下反应。这些方法包括固定床烃类合成、流化床烃类合成和浆液烃类合成,所有这些方法都在各种技术文献和专利中发表。在许多情况下,希望合成的烃类主要含有C5+烃类(例如C5+-C200),优选C10+烃类,其中至少一部分在标准的室温和室压条件下是固体。在浆液烃类合成法中,优选烃类主要含有C5+烷烃。通过一种或多种加氢转化操作,使这些烃类改质成更有价值的产品,其中至少一部分的分子结构通过与氢反应而改变。所以,加氢转化操作都需要氢气。为了使烃类合成催化剂再生、以及有时还为了维持或改变用于烃类合成的合成气进料的H2/CO比,也需要氢气。希望有这样一种烃类合成方法,它生成用于烃类合成催化剂的再生以及合成的烃类的加氢转化改质所需要的氢气,而不依赖外界的氢源。
发明概述
本发明涉及一种用于烃类催化合成和由含有H2和CO混合物的合成气生产氢气以及合成的烃类改质的气体转化方法,其中氢气用于(a)烃类合成催化剂的再生和(b)通过至少一种加氢转化操作,使至少一部分合成的烃类进行改质中的至少一种。所谓的气体转化方法至少包括烃类合成、由合成气生产氢气以及至少一部分合成的烃类的转化。所谓的转化是指这样一种方法,其中至少一部分烃类的分子结构在转化段中被改变,如下所述,它包括催化法和非催化法,有氢气或没有氢气作为共反应物。所以,广义上,本发明包括烃类合成和由合成气生产氢气,以及合成气生产的氢气用于上述方法中至少一种的方法。更具体地说,本发明包括这样一种气体转化方法,它用于烃类合成和由含H2和CO混合物的合成气生产氢气,以及用于至少一部分所述的合成的烃类的转化,所述的方法包括,将所述的合成气与烃类合成催化剂接触;在所述的合成催化剂和可使所述的催化剂可逆失活的物质存在下,在有效生成烃类和使所述的催化剂可逆失活的反应条件下,使所述的H2和CO反应;通过至少一种转化操作,使至少一部分所述的合成烃类改质,以及涉及(a)通过所述的催化剂与由所述的合成气生产的所述氢气接触,使它再生和(b)通过至少一部分所述的烃类与由所述的合成气生产的所述氢气在加氢转化催化剂存在下反应,改变它们的分子结构,因而使它们改质中的至少一个。在另一些实施方案中,由合成气生产的氢气可用于烃类合成和/或氢气生产。用以下的一种或多种方法由合成气生产氢气:(a)物理分离方法,例如变压吸附(PSA)、膜分离或变温吸附(TSA);以及(b)化学方法,例如水蒸汽转换反应。氢气生产的物理方法通常用于从合成气中分离氢气,以便得到所需纯度(例如至少约99%)的氢气,不管是否使用化学方法,例如水蒸汽转换反应。虽然从外界来源得到合成气是可能的,但通常合成气的生产也是所述气体转化方法的一部分。因此,在合成气的生产是气体转化装置的一部分的实施方案中,本发明包括(a)在有效生成含有H2和CO混合物的合成气的条件下,使气态烃质材料、氧和任选的水蒸汽反应,(b)在有效使所述的H2和CO反应并生成烃类以及使所述催化剂可逆失活的反应条件下,使一部分所述的合成气与烃类合成催化剂接触,(c)由另一部分所述的合成气生产氢气,以及(d)氢气用于(i)使所述的催化剂再生和(ii)使至少一部分所述的合成烃类加氢转化中的至少一种。
通过在HCS(烃类合成)反应段或反应器中,在费托合成催化剂存在下,在有效生成烃类、优选C5+烃类的条件下,使合成气反应来实现烃类合成。正如已知的,在HCS反应过程中,由于使催化剂失活的物质例如含氮化合物在合成气中的存在(例如HCN和NH3)以及可能通过HCS反应生成的其他物质的存在,使HCS催化剂可逆失活。还已知,通过催化剂与氢气或含氢的气体接触,可使催化活性恢复。由HCS反应器排出的至少一部分合成的烃类产物通过至少一种转化方法进行改质,以便降低它的粘度或倾点,或使它们转化成有更高价值的馏分。一般来说,该转化至少包括一种加氢转化操作,其中在加氢转化催化剂存在下,使烃类与氢气反应。优选这样一种气体转化装置,它提供该装置内的一个或多个用途所需的氢气的至少一部分,而不依赖外部来源提供。
用物理分离方法,由合成气生产氢气得到相当纯的氢气,同时得到含有贫氢和富CO的H2和CO混合物的废气。这种富CO废气可用作燃料或送入HCS反应段。如果氢气的需要量比通过从合成气中分离的氢气量可以满足的要大,或者如果还希望生产氢气的辅助方法或替代方法,那么化学方法,例如水蒸汽转换反应器可用于从合成气生产所有的或一部分所需的氢气。在这一实施方案中,将(a)一部分合成气和(b)由合成气物理分离氢气得到的富CO废气中的至少一种送入水蒸汽转换反应器,在水蒸汽和水蒸汽转换催化剂存在下,由CO和水蒸汽生成H2和CO2的混合物,然后让它通过物理分离设备,从其余的气体中分离出H2,得到相当纯的H2以及富CO废气,将废气循环回HCS反应段,送入转换反应器,或者作为燃料。
附图简介
图1为本发明一个实施方案的简单方块流程图,其中由合成气生产的氢气用于催化剂再生和加氢转化。
图2提供了加氢转化更详细的细节。
图3说明这样一个实施方案,其中将氢气生产得到的富CO废气送入HCS反应器,而富氢的加氢转化尾气也用于催化剂再生。
图4为说明用水蒸汽转换反应和PSA生产氢气的简单方块图。
发明详述
正如大家熟悉的,用于合成气生产的进料的烃类组分虽然可方便地由主要含有甲烷作为烃类组分的天然气得到,但也可由任何一种适合的包括煤、焦炭、烃类液体和气体在内的烃质材料通过任何一种可利用的和方便的方法制得。一般来说,合成烃类的装置接近这样的烃类材料源,而合成气生产操作为该装置的一个组成部分。含有低分子量(例如C1-C4)烃类、优选烷烃、更优选主要是甲烷(例如在天然气中)的进料是优选的。天然气是特别优选的,因为它主要含有甲烷,它是方便的、清洁的进料,不会留下需要处理的大量厌分、岩页、含硫化合物等。合成气可用各种方法生成,包括热的碳质材料例如煤、焦炭或焦油与水蒸汽接触,以及在部分氧化条件下使这样的材料燃烧,生成甲烷或低分子量的烃类气体,作为合成气生成器进料的烃类组分,然后将甲烷或低分子量的烃类气体送入合成气生成器,在合成气生成器中,它用氧或空气部分氧化或者水蒸汽转换,或者送入水蒸汽转换反应器。用固定床或流化床水蒸汽转换催化剂来实现部分氧化和水蒸汽转换,固定床有更好的混合特性和传热特性。在部分催化氧化中,送入合成气生成器的进料的烃类组分预先与氧和任选和水蒸汽混合,然后通过合成气生成器,正如已知的,在合成气生成器中,在贵金属催化剂、优选负载型贵金属催化剂存在下,它进行反应。这些方法使用低分子量烃类,通常C1-C4烷烃、优选甲烷如天然气中的甲烷,它与水蒸汽、氧或空气一起送入合成气生成单元。在流化床合成气生成(FBSG)法中,部分氧化和水蒸汽转换都在水蒸汽转换催化剂存在下发生。FBSG例如在US4888131和5160456中公开。在自热转换中,部分氧化在没有催化剂存在下发生,并在固定床催化剂中进行绝热水蒸汽转换。反应器排出的合成气含有H2和CO与水蒸汽、氮、CO2和少量未反应甲烷的混合物。在合成气生成器进料中存在的CO2的数量将影响反应平衡,可与单元的反应条件一起使用,用来调节合成气中的H2/CO比。在合成气送入HCS反应器以前,将大部分水从合成气中除去。不管用于合成气生产的烃类来源或生产方法如何,这样的烃类进料总是含有元素氮或含氮的化合物,它们在合成气生成器中反应生成含氮物质,例如HCN和NH3,它们在HCS反应过程中使HCS催化剂失活。
在HCS法中,通过含有H2和CO混合物的合成气在转换或非转换条件下、优选在非转换条件下与费-托合成型HCS催化剂接触,来生成液态和气态烃类产品;在非转换条件下,有很少或没有水蒸汽转换反应发生,特别是当催化金属为Co、Ru或其混合物时。适合的费-托合成反应型催化剂例如包括一种或多种第VIII族催化金属,例如Fe、Ni、Co、Ru和Re。在一个实施方案中,催化剂在无机载体材料上,优选为一种或多种难熔金属氧化物的载体上含有催化有效数量的Co以及Re、Ru、Fe、Ni、Th、Zr、Hf、U、Ng和La中的一种或多种金属。含Co催化剂的优选载体为氧化钛,特别是当使用浆液HCS方法时,在这一方法中希望更高分子量的主要部分是烷烃的液体烃类产品。适用的催化剂及其制备方法是已知的,说明性的但非限制性的例子例如可在US4568663、4663305、4542122、4621072和5545674中找到。
就烃类合成来说,用于由含有H2和CO混合物的合成气生产烃类的固定床烃类合成(HCS)法、流化床烃类合成法和浆液烃类合成法是大家熟悉的,并在文献中发表。在所有这些方法中,合成气在适合的费-托合成型烃类合成催化剂存在下,在有效生成烃类的反应条件下反应。在25℃和1大气压的标准室温和室压条件下,特别是如果使用含有Co催化组分的催化剂时,这些烃类中一些为液体,一些为固体(例如蜡)和一些为气体。浆液HCS方法常常是优选的,因为对于强放热的合成反应来说,它们有更好的传热(和传质)特性,以及因为当使用钴催化剂时,它们能生产相对高分子量的烷烃。在浆液HCS方法中,含有H2和CO混合物的合成气作为第三相向上鼓泡通过反应器中的浆液,该浆液含有分散和悬浮在含有合成反应烃类产品——它们在反应条件下为液体——的浆液中的颗粒状费-托合成型烃类合成催化剂。氢与一氧化碳的摩尔比可有约0.5至4的宽范围,但更通常在约0.7至2.75、优选约0.7至2.5范围内。费-托合成HCS反应的化学计量摩尔比为2.0,但在本发明的实施中,可提高这一摩尔比,以便从合成气中得到用于除HCS反应以外所希望数量的氢气。在浆液HCS方法中,H2/CO的摩尔比通常为约2.1/1。浆液HCS法的条件随催化剂和所需的产品稍有变化。在使用含有负载型钴组分的催化剂的浆液HCS法中,有效生成主要含C5+烷烃(例如C5+-C200)、优选C10+烷烃的烃类的典型条件分别包括例如以下范围的温度、压力和气时空速:约320-600°F、80-600磅/平方英寸和100-40000体积/小时/体积,以每小时每单体体积催化剂的标准体积气态CO和H2混合物(0℃、1大气压)表示。在烃类合成操作过程中,通过在合成气中存在的和由烃类合成反应产生的上述失活物质使HCS催化剂失活。这一失活是可逆的,通过失活催化剂与氢气接触可使催化剂活性恢复(催化剂再生)。通过浆液与氢气或含氢的气体接触,在HCS反应器中就地生成或在外部的再生容器中生成再生的催化剂浆液的方法,使反应浆液中的HCS催化剂的活性断续或连续再生,例如在US5260239、5268344和5283216中公开的。
用于由合成气生产氢气的物理分离方法包括吸附-脱附法和膜分离,两者都是大家熟悉的,并在商业上可提供的。吸附-脱附法包括TSA和PSA,两者都有许多按循环方式操作的装有吸附剂的容器。吸附剂包括分子筛、硅胶和活性炭。变压吸附与变温吸附之间的差别在于,在操作周期的吸附部分中被吸附剂吸附的除氢以外的气体组分在PSA中通过变压周期再生时从吸附剂上脱附,与在变温吸附中的变温周期不同。吸附和脱附之间的压差通常至少为一个数量级。在操作过程中,将进料气体(在这种情况下为合成气的滑流)送入一个或多个容器或吸附段,除氢以外的合成气组分(和少量氢一起)在其中被吸附剂吸附。当吸附剂已达到吸附容量时,停止送入容器的进料流,降压,吸附的合成气中非氢组分被脱附并作为吹扫气体被除去。如果需要,在脱附周期结束时,可用一些氢气吹扫容器。再次给容器加压,进行下一次吸附周期操作。因此,吹扫气体含有CO和任何一种其他非氢的合成气组分以及少量氢气。这一吹扫气体为吸附废气,可将它送去处理或作为燃料烧掉,但优选将它循环回一个或多个HCS反应器作为进料的一部分,以便将有价值的CO用于烃类合成。在吸附过程中,从合成气中分离出的氢气的纯度通常为99%、甚至99%以上。典型的PSA装置有至少一个容器处于吸附操作,而至少另一个容器在减压和吹扫,此外至少还有一个容器正在重新加压。在膜分离中,在容器中有中空纤维束,并将合成气送入该容器,在容器中合成气在纤维的外侧流过并离开容器。在每一纤维的内部得到富氢的渗透物,并作为单独的渗透物流除去。在典型的装置中,将许多这样的容器串联,将每一容器的渗透物作为下一个容器的进料。通过使用多组并联的串联设备,可得到高的生产能力。氢气通常没有用PSA达到的那样纯,但纯度通常为至少约80%。将各非渗透物流出物合并,作为富CO废气,它可按PSA分离回收的富CO废气相同的方式利用。物理分离的另一实施方案是PSA或TSA吸附-脱附与膜分离的组合。在这种类型的典型分离方法中,合成气首先通过膜分离单元,生产富氢的气体流作为渗透物。然后将这一富氢的渗透物通过PSA或TSA单元,以便生产高纯度的氢气流和富CO的废气流。用这一方法,生成的废气数量比单独用这两个方法中任一种得到的要少。
当使用水蒸汽转换反应来生产氢时,将一部分合成气滑流送入水蒸汽转换反应器,在该反应器中,在转换催化剂例如镍/难熔金属氧化物载体存在下,在有效生成H2和CO2混合物的反应条件下,使CO与水蒸汽进行反应,H2和CO2的混合物与包括未反应的CO在内的其他合成气组分一起从转换反应器排出。如果需要,可用熟悉本专业的技术人员已知的方法例如胺洗涤法从转换反应器流出物中除去CO2。一种利用受阻胺洗涤除去CO2的商业上可提供的方法是Exxon公司的Flexsorb法。有或没有CO2脱除的富氢转换反应器流出物在冷却和闪蒸分离除去任何过量水份以后通过物理分离设备,从气体中存在的CO和非氢组分中分离出氢气,得到相当纯的氢气流和含CO的废气。这些气体物流然后按上述相同的方式利用,但由于废气中的CO含量较低,含CO的废气通常作为燃料烧掉。是否使用转换反应器取决于所需要的氢气数量和合成气生成器的生产能力,以满足烃类合成和氢气生产对合成气的需要量。
通过将全部或一部分C5+烃类转化,使本发明的HCS法生产的至少一部分烃类典型地改质成更有价值的产品。所谓转化是指这样一种或多种操作,在这些操作中,至少一部分烃类的分子结构被改变,以及这样的转化包括非催化加工(例如蒸汽裂解)和催化加工(例如催化裂化),其中馏分与适合的催化剂接触。如果氢气作为反应物存在,那么这样的工艺步骤通常称为加氢转化,例如包括加氢异构化、加氢裂化、加氢脱蜡、加氢精制以及称为加氢处理的更加苛刻的加氢精制,所有的都在文献中已知的条件下进行,所说条件是用于包括富含烷烃的烃类进料在内的各种烃类进料的加氢转化的。通过转化可生成的、更有价值的产品的说明性但非限制性的例子包括:合成原油、液体燃料、烯烃、溶剂、润滑油、工业用油或医药用油、含蜡烃类、含氮化合物和含氧化合物等中的一种或多种。液体燃料包括汽油、柴油、喷气燃料和煤油中的一种或多种,而润滑油例如包括汽车发动机油、喷气发动机油、涡轮发动机油和金属加工用油。工业用油包括钻井液、农用油、传热液等。适用于本发明实施的加氢转化法的说明性但非限制性的例子在US4832819、4943672、5059299、5378348和5457253中公开。
参考图1,气体转化装置10包括FBSG合成气生成单元12、浆液HCS反应器14、由合成气生产氢气的设备16以及有加氢转化单元18的方框18。将天然气、氧气和水蒸汽分别通过管线20、22和24送入FBSG单元,生成含有H2和CO混合物的合成气。以每小时送入浆液HCS反应器14的CO为100摩尔为基础计,从合成气生成器12送入管线26的合成气流含有218摩尔/小时氢气和104摩尔/小时CO,H2/CO摩尔比为约2.1∶1。工业规模装置要大得多,加工高达100,000摩尔/小时CO。下文中除非另加说明,所有的数字都指摩尔/小时。其中209摩尔氢和100摩尔CO通过管线26送入HCS反应器14。HCS反应器装有含负载的钴催化组分的催化剂,在CO转化率为80%下操作。从管线26抽出含有9摩尔氢和4摩尔CO的合成气滑流,并通过管线28送入氢生成单元16。在使用PSA单元的实施方案中,通常生产至少99%氢气的物流,其余为低分子量烃类和氮气。对于这一例子来说,用分子筛吸附分离,从滑流中分离出85%的氢气。8摩尔氢进入管线30,通过管线34抽出的通过氢分离得到的贫氢和富CO的废气含有1摩尔氢和4摩尔CO。在这一实施方案中,然后废气用作低英热单元热值(low BTU value)燃料气。在一实施方案中,这一富CO的废气通过管线35和26送入HCS反应器,为HCS反应提供另外的CO。在离开PSA单元的8摩尔氢中,5摩尔氢通过管线30送入加氢转化单元,为合成烃类中700°F+馏分的加氢异构化提供氢气,而3摩氢通过管线32送入HCS催化剂再生设备(未示出),用于HCS催化剂再生。正如已知的,HCS催化剂可连续再生或断续再生,或在HCS反应器中就地再生或在器外容器中外部再生。在HCS反应器中生成的烃类通过管线36除去,并送入加氢转化单元18,在那里它们与氢一起送入加氢异构化反应器(在图2中示为44),生产较低沸点的材料,其中700°F+烃类转化成700℃F-烃类。在适合的加氢异构化催化剂例如Co-Mo/SiO2-Al2O3催化剂存在下,在700°F+馏分转化率为50%(重量)下,通过与H2反应,使烃类加氢异构化。这就意味着每次通过反应器时,有50%(重量)的700°F+材料转化成沸点低于700°F的700°F-材料。然后将加氢异构化后的700°F-材料加工成各种产品馏分或用作更好运输的材料,用于进一步改质操作。将任何未转化的700°F+材料循环,并与新鲜进料混合,送入加氢异构化反应器。另一方面,从HCS反应器取出的合成液体的倾点和粘度可通过加氢异构化来降低,制得合成原油或更好泵送和运输的材料。
图2更详细地说明加氢异构化单元18。参考图2,加氢异构化单元18包括分馏塔40和42以及加氢异构化反应器44。从HCS反应器抽出的液体烃类产品与HCS反应器顶部产物冷凝的烃类液体(大约C11+)合并,并通过管线36送入分馏塔40,将进料分馏成较重馏分和较轻馏分,前者通过管线46除去,而后者通过管线48除去。将通过管线46取出的含有700°F+材料的较重馏分送入加氢异构化反应器44,在反应器中它与由合成气生产的氢气在如上所述的适合的加氢异构化催化剂存在下接触并反应,后者通过管线30送入反应器。通过管线50从反应器44中取出加氢异构化的烃类,它含有700°F+馏分和主要为未反应的氢、烃类气体和水的气体,经冷却(未示出)和在挡板式气-液分离罐52中气液分离后,其中烃类液体与水彼此分离,并与未反应的氢和少量未反应的甲烷、C2+烃类气体和氮气分离。通过管线55除去水,而通过管线58除去富氢的尾气。通过管线51除去加氢异构化的烃类,并送入分馏塔42。分馏塔42生产石脑油和柴油馏分,它们分别通过管线53和54除去,剩余的700°F+材料作为塔底产物通过管线56除去,并与来自分馏塔40的新鲜进料一起循环回加氢异构化反应器44。少量轻质烃类气体作为塔顶产物通过管线57除去。该单元用于实现沸点高于700°F的烃类的100%转化。典型的加氢异构化反应器条件包括LHSV约1.3、800-900磅/平方英寸(绝)(Psia)和温度约700至750°F。在这一特定的说明中,循环料对新鲜料的体积比为约0.5。在这些条件下,其中5摩尔氢送入加氢异构化反应器,4摩尔氢在反应器中与烃类反应。1摩尔未反应的氢作为尾气通过管线59,从反应器中除去。
图3说明图1的本发明方法的另一实施方案。在图3中,1摩尔从加氢异构化反应器中作为尾气取出的未反应氢气通过管线58、60和32返回HCS单元,用于催化剂再生(或送入HCS反应器外的催化剂再生容器)和/或通过管线58和26送入反应器,作为HCS反应的H2和CO进料的一部分。富氢的加氢异构化反应器尾气作为进料的一部分返回HCS反应器,使合成气生成的需要量和合成气生成器排出的合成气的H2/CO摩尔比稍有下降。在这一实施方案中,其中尾气用于催化剂再生,尾气中的氢气数量使氢气生成需要量减少。在另一实施方案中(未示出),其中将加氢异构化尾气循环到图1中的氢气生产单元16,在尾气中,相当高纯度的氢气使送入PSA单元的气流纯度提高,并使合成气生产所需的氢气数量稍有下降。再次参考图3,在图1的工艺流程图中通过由合成气滑流氢分离生产的富CO PSA废气通过管线34送入HCS反应段,作为合成气进料的一部分,而不是作为燃料消耗掉。在这一实施方案中,所有HCS进料的组成和速率都与图1说明的实施方案是相同的,不同的是,从合成气生成器排出的一部分HCS进料由207摩尔氢和96摩尔CO组成,通过废气管线34送入HCS进料管线26的PSA废气来提供为达到100摩尔CO所需的另外4摩尔CO。
图4说明本发明的另一实施方案,其中水蒸汽转换反应器用来从合成气滑流生产更多的氢气,然后将转换反应器流出物通过物理分离设备,以便分离和回收氢气。再参考图4,氢气生产设备16包括水蒸汽转换反应器62,合成气滑流通过管线28送入该水蒸汽转换反应器,如果合成气没有含有足够的水蒸汽,水蒸汽通过管线64进入。转换反应器装有水蒸汽转换催化剂,例如氧化铬助催化的氧化铁。在转换反应器中,在催化剂存在下,水蒸汽与CO反应,每1摩尔CO和H2O反应生成1摩尔H2和1摩尔CO2,生成含有CO2和任何未反应的CO和H2O的富氢气体,它从反应器中排出,经过冷却和闪蒸分离除去水以后,通过管线66送入洗涤塔68,以便除去CO2。洗涤塔68为装有惰性填料或分馏塔盘的传统接触塔。用于从气体中除去CO2的溶剂,例如在US 4112051公开的胺水溶液或受阻胺水溶液,例如含有2-哌啶和乙醇环丁砜的Flexsorb PS通过管线70送入,并除去CO2。特定的溶剂脱除CO2体系或其他脱除CO2设备取决于所需的脱除CO2程度。如果使用Flexsorb PS体系,实际上所有的CO2都从气体中除去。通过管线72将含CO2的溶液除去,送回去溶剂回收,而经洗涤减少CO2含量的气体通过管线74送入换热器和分离单元76。在那里将气体冷却到200°F以下,并通过管线78除去水。仍然含有水蒸汽但不含液体水的冷却气体通过管线80达入PSA单元82。PSA单元从其余的气体中分离出氢气,得到99%或更高纯度的氢气,它通过管线30除去,并按上述任何一个或全部实施方案使用。由氢气分离生成的废气通过管线34除,通常用作低英热单位热值的燃料。另一方面,不需要有CO2脱除体系,仅通过使用PSA来实现转换反应流出物的纯化。
虽然本发明特别详细地描述了使用经加工的天然气作为生成器的烃类进料的FBSG合成气生成器、用于烃类转化的浆液HCS单元和加氢异构化单元,但是正如熟悉本专业的技术人员已知的和理解的,本发明的实施不限于这些具体的实施方案。因此,任何适合的和方便的合成气来源、合成气生成器的进料和合成气生成方法都可使用,如可为流化催化剂床层或固定催化剂床层的非浆液HCS方法。同样,转化方法包括上述所列的那些方法中至少一个。
应当理解,在不违背上述本发明的范围和实质的条件下,对于熟悉本专业的技术人员来说,在本发明的实施中,各种其他的实施方案和改进是显而易见的和很容易做到的。因此,不打算把附后的权利要求书的范围限制到上述准确的描述上,而认为权利要求书包含了属于本发明的所有具有专利新颖性的特点,其中包括熟悉本专业的技术人员可作为本发明等价物的所有特点和实施方案。
Claims (13)
1.一种气体转化方法,包括,
(a)在有效地生成包含H2和CO混合物的合成气的条件下,使气态烃质物质、氧和任选的水蒸汽反应;
(b)在有效使H2和CO反应并生成烃类以及使所述的催化剂可逆失活的反应条件下,使一部分所说的合成气与烃类合成催化剂接触;
(c)由另一部分所述的合成气生产氢气,以及
(d)使用所述的氢气用于(i)使所述的催化剂再生和(ii)使至少一部分所述的合成烃类加氢转化中的至少一种过程中。
2.根据权利要求1的方法,其中所述的氢气通过(i)物理分离方法和(ii)化学方法中的至少一种、由所述的合成气来生产。
3.根据权利要求2的方法,其中所述的氢气通过包括物理分离的方法、由所述的合成气来生产。
4.根据权利要求2的方法,其中所述的氢气生产方法包括水蒸汽转换反应。
5.根据权利要求3的方法,其中所述的烃类合成催化剂为费-托合成型催化剂,以及其中至少一部分所述的合成烃类在标准的室温和室压条件下为固体。
6.根据权利要求5的方法,其中所述的催化剂含有钴催化组分。
7.根据权利要求6的方法,其中所述的烃类合成反应在这样的浆液中进行,所述的浆液含有所述的烃类合成催化剂和在浆液中的所述H2和CO的气泡,浆液含有在所述的反应条件下为液体的所述合成烃类。
8.根据权利要求7的方法,其中所述的氢气用于所述催化剂的再生。
9.根据权利要求3的方法,其中从所述的合成气中物理分离所述的氢气,得到含有富CO的废气,它用于所述的烃类合成。
10.根据权利要求8的方法,其中从所述的合成气中物理分离所述的氢气,得到含有富CO的废气,它用于所述的烃类合成。
11.根据权利要求3的方法,其中所述的物理分离包括,使所述的合成气通过膜分离设备生成富氢的渗透物;后者通过变压吸附设备生产高纯度的氢气流。
12.根据权利要求7的方法,其中所述的物理分离包括,使所述的合成气通过膜分离设备,生成富氢的渗透物;后者通过变压吸附设备,生产高纯度的氢气流。
13.根据权利要求8的方法,其中所述的物理分离包括,使所述的合成气通过膜分离设备,生成富氢的渗透物;后者通过变压吸附设备,生产高纯度的氢气流。
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-
1998
- 1998-02-13 US US09/023,581 patent/US6043288A/en not_active Ceased
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1999
- 1999-02-05 CA CA002320509A patent/CA2320509C/en not_active Expired - Fee Related
- 1999-02-05 BR BR9907821-0A patent/BR9907821A/pt not_active Application Discontinuation
- 1999-02-05 WO PCT/US1999/002543 patent/WO1999041217A1/en active IP Right Grant
- 1999-02-05 EP EP99906759A patent/EP1054851B9/en not_active Expired - Lifetime
- 1999-02-05 AU AU26593/99A patent/AU750915B2/en not_active Ceased
- 1999-02-05 DE DE69916794T patent/DE69916794T3/de not_active Expired - Lifetime
- 1999-02-05 CN CNB998029033A patent/CN1183064C/zh not_active Expired - Fee Related
- 1999-02-05 JP JP2000531416A patent/JP4174181B2/ja not_active Expired - Fee Related
- 1999-02-08 MY MYPI99000432A patent/MY116318A/en unknown
- 1999-02-10 ZA ZA9901071A patent/ZA991071B/xx unknown
- 1999-02-11 PE PE1999000125A patent/PE20000255A1/es not_active Application Discontinuation
- 1999-02-12 AR ARP990100605A patent/AR014573A1/es not_active Application Discontinuation
- 1999-04-06 TW TW088102350A patent/TW505619B/zh not_active IP Right Cessation
- 1999-06-09 SA SA99200231A patent/SA99200231B1/ar unknown
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2000
- 2000-08-11 NO NO20004054A patent/NO20004054L/no not_active Application Discontinuation
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2002
- 2002-03-28 US US10/109,621 patent/USRE38170E1/en not_active Expired - Fee Related
Also Published As
Publication number | Publication date |
---|---|
CA2320509C (en) | 2007-01-02 |
CA2320509A1 (en) | 1999-08-19 |
EP1054851B9 (en) | 2010-11-03 |
DE69916794D1 (de) | 2004-06-03 |
TW505619B (en) | 2002-10-11 |
MY116318A (en) | 2003-12-31 |
SA99200231B1 (ar) | 2006-05-13 |
EP1054851B2 (en) | 2010-05-05 |
AU2659399A (en) | 1999-08-30 |
DE69916794T2 (de) | 2005-01-13 |
EP1054851B1 (en) | 2004-04-28 |
US6043288A (en) | 2000-03-28 |
ZA991071B (en) | 1999-08-11 |
CN1295544A (zh) | 2001-05-16 |
WO1999041217A1 (en) | 1999-08-19 |
USRE38170E1 (en) | 2003-07-01 |
EP1054851A1 (en) | 2000-11-29 |
NO20004054D0 (no) | 2000-08-11 |
PE20000255A1 (es) | 2000-04-07 |
JP2002503731A (ja) | 2002-02-05 |
NO20004054L (no) | 2000-08-11 |
DE69916794T3 (de) | 2010-12-02 |
AU750915B2 (en) | 2002-08-01 |
JP4174181B2 (ja) | 2008-10-29 |
BR9907821A (pt) | 2000-10-24 |
AR014573A1 (es) | 2001-02-28 |
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