CN101981162B - 低排放发电和烃采收系统及方法 - Google Patents

低排放发电和烃采收系统及方法 Download PDF

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CN101981162B
CN101981162B CN200980111361.0A CN200980111361A CN101981162B CN 101981162 B CN101981162 B CN 101981162B CN 200980111361 A CN200980111361 A CN 200980111361A CN 101981162 B CN101981162 B CN 101981162B
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F·赫什科维茨
E·D·纳尔逊
P·D·麦克马洪
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ExxonMobil Upstream Research Co
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Abstract

提供用于烃采收方法中低排放发电的方法和系统。一个系统包括以低排放发电的集成的压力保持和混相驱动系统。该系统也可包括集成变压重整装置(PSR)、吹气式自热重整单元(ATR)或吹氧式ATR与燃气发电轮机系统，优选地为组合循环燃气发电轮机系统。这样的系统可被用来捕获和利用温室气体(GHG)并产生用于烃采收操作中的电力。

Description

低排放发电和烃采收系统及方法
交叉引用相关申请
本申请要求2008年3月28日提交的名称为LOW EMISSIONPOWER GENERATION AND HYDROCARBON  RECOVERYSYSTEMS AND METHODS(低排放发电和烃采收系统及方法)的美国临时专利申请61/072,292和2009年2月18日提交的名称为LOWEMISSION POWER  GENERATION  AND HYDROCARBONRECOVERY SYSTEMS AND METHODS(低排放发电和烃采收系统及方法)的美国临时专利申请61/153,508以及2009年2月23日提交的名称为LOW  EMISSION POWER  GENERATION  ANDHYDROCARBON RECOVERY SYSTEMS AND METHODS(低排放发电和烃采收系统及方法)的美国临时专利申请61/154,675的权益，其全部内容通过引用并入本文。
技术领域
本发明的实施方式涉及烃采收方法中的低排放发电(产生能量)。更具体而言，本发明的实施方式涉及利用氮、氧、二氧化碳和烃燃料以及重整技术在极低排放的烃采收方法中发电(产生能量)的方法和装置。
背景技术
本节意图介绍可能与本发明的示例性实施方式相关的本领域的各个方面。相信该讨论有助于提供一个基本概念，以利于更好地理解本发明的特定方面。因此，应该理解，本节应该基于此进行阅读，并不必承认其为现有技术。
多种强化烃采收操作可以被分类为以下类型之一：压力保持和混相驱动(miscible flooding)。在压力保持操作中，惰性气体如氮被注入主要为气态的油藏，以在该油藏内至少保持最低压力，阻止反凝析并提高总采收量。在混相驱动操作中，混相气体如二氧化碳被注入主要为液态的油藏以与液体混合，降低其粘度并增加压力以提高采收率。
许多产油国正在经历强烈的国内电力需求增长，并关注于提高采收率法采油(EOR)，以提高从其油藏采油。两种常见的EOR技术包括用于油藏压力保持的氮气(N2)注入和用于EOR混相驱动的二氧化碳(CO2)注入。还有全球关注的温室气体(GHG)排放问题。这种关注与许多国家的总量控制与交易政策(cap-and-trade)或碳税政策的执行相结合，使得减少CO2排放成为这些和其它国家以及其中操作烃采出系统的公司优先考虑的事情。有效采出烃同时减少GHC排放是世界上最严酷的能源挑战之一。
减少CO2排放的一些方法包括燃料脱碳或燃烧后捕集。但是，这两种方法成本都高并且降低发电效率，导致较低发电，为满足国内电力需求而增加了燃料的需求并增加了电的成本。另一种方法是联合循环方式(in a combined cycle)的含氧燃料燃气轮机(例如，来自燃气轮机Brayton循环的废热被捕集以在Rankin循环中产生蒸汽并产生额外电力)。然而，没有商业可得的燃气轮机能够在这样的循环内进行操作，并且产生高纯氧所需的电力显著降低了该方法的总效率。
提出的一个方法使用自热重整单元(ATR)以产生用于捕集和/或注入的烃燃料和二氧化碳。这样的系统在许多出版物中公开，其包括例如国际专利申请号WO2008/074980(′980申请)和Ertesvag，Ivar S.等的″Exergy Analysis of a Gas-Turbine Combined-Cycle Power Plant WithPrecombustion CO2Capture，″Elsivier(2004)(Ertesvag参考文件)，其相关部分通过引用从而并入。′980申请和Ertesvag参考文件公开用于在自热重整装置(ATR)中重整天然气以形成合成气，然后从合成气分离CO2，并将富含氢的燃料送至传统的联合循环(CC)过程。
因此，仍然十分需要低排放、高效率的烃采收方法。
发明内容
本公开的一个实施方式包括集成系统。所述集成系统包括变压重整单元，其被配置为利用空气流、天然气流和蒸汽流以产生主要包含氮气的再生流和包含一氧化碳、二氧化碳和氢气的合成气流；和压力保持油藏，其接收至少一部分的主要包含氮气的再生流。集成系统也可包括水煤气变换反应器，其被配置为将至少一部分一氧化碳转化为二氧化碳；分离单元，其被配置为将合成气流分离成二氧化碳流和氢气流；和提高采收率法采油油藏，其接收至少一部分的二氧化碳流。另外，本系统的一些实施方式可包括燃气轮机，其被配置为使用氢气流以产生能量(发电)和气态排出流(gaseous exhaust stream)。
本公开的另一个实施方式包括采出烃的方法。该方法包括在变压重整装置中产生主要包含氮气的再生流和包含一氧化碳、二氧化碳和氢气的合成气流；将至少一部分主要包含氮气的再生流注入压力保持油藏；和从压力保持油藏采出烃。该方法的其他实施方式可包括在水煤气变换反应器中将至少一部分一氧化碳转化为二氧化碳；将合成气流分离成二氧化碳流和氢气流；在燃气轮机中产生能量(发电)，其中燃气轮机被配置为使用至少一部分氢气流作为燃料；将至少一部分二氧化碳流注入提高采收率法采油油藏；和从提高采收率法采油油藏采出烃。进一步的实施方式可包括将至少一部分从提高采收率法采油油藏采出的烃再循环到变压重整装置；和将至少一部分从压力保持油藏采出的烃再循环到变压重整装置。
在本公开的第三实施方式中，提供可选的集成系统。该集成系统包括反应器单元，其被配置为利用空气流、烃燃料流和蒸汽流产生包含一氧化碳、二氧化碳、氮气和氢气的合成气流；水煤气变换反应器，其被配置为将至少一部分一氧化碳转化为二氧化碳以形成变换流(shifted stream)；第一分离单元，其被配置为将二氧化碳流与变换流分离以产生基本是二氧化碳的流和主要包含氮气和氢气的混合产物流；燃气轮机，其被配置为利用混合产物流以产生能量(发电)和包含氮气和蒸汽的气态排出流；第二分离单元，其被配置为将氮气与蒸汽分离以至少产生气态氮气流；和压力保持油藏，其接收至少一部分的气态氮气流。
在本公开的第四实施方式中，公开采出烃的可选方法。该方法包括利用反应器单元产生包含一氧化碳、二氧化碳、氮气和氢气的合成气流；在水煤气变换反应器中将至少一部分一氧化碳转化为二氧化碳以形成变换流；将二氧化碳与变换流分离以产生基本是二氧化碳的流和主要包含氮气和氢气的混合产物流；在燃气轮机中，产生能量(发电)和包含氮气和蒸汽的气态排出流，其中燃气轮机被配置为利用主要包含氮气和氢气的混合产物流作为燃料；将氮气与蒸汽分离以至少产生气态氮气流；将至少一部分气态氮气流注入压力保持油藏；和从压力保持油藏采出烃。
在本公开的第五实施方式中，提供集成系统的另一可选实施方式。该系统包括空气分离单元，其被配置为产生基本是氮气的流和基本是氧气的流；反应器单元，其被配置为利用基本是氧气的流、烃燃料流和蒸汽流产生包含一氧化碳、二氧化碳和氢气的合成气流；水煤气变换反应器，其被配置为将至少一部分一氧化碳转化为二氧化碳；分离单元，其被配置为将合成气流分离成二氧化碳流和氢气流；和提高采收率法采油油藏，其接收至少一部分分离的二氧化碳流。
在本公开的第六实施方式中，提供采出油的另外可选的方法。该方法包括在空气分离单元中分离空气，所述空气分离单元被配置为产生基本是氮气的流和基本是氧气的流；使用反应器单元产生包含一氧化碳、二氧化碳和氢气的合成气流，所述反应器单元被配置为利用基本是氧气的流、烃燃料流和蒸汽流；在水煤气变换反应器中将至少一部分一氧化碳转化为二氧化碳以形成变换流；将变换流分离成二氧化碳流和氢气流；将至少一部分分离的二氧化碳流注入提高采收率法采油油藏；和从提高采收率法采油油藏采出烃。
附图说明
研读以下详细说明和实施方式的非限制性实例的附图后，本发明的前述和其它优势将变得明显，附图中：
图1图解了利用变压重整单元的用于低排放发电和烃采收的集成系统；
图2图解了利用类似图1所示的变压重整单元的用于低排放发电和烃采收的集成系统的示意图；
图3是操作利用类似图1-2所示的变压重整单元的用于低排放发电和烃采收的集成系统的方法的示例性流程图；
图4是利用反应器单元的用于低排放发电和烃采收的集成系统的图解；
图5图解了利用类似图4所示的反应器单元的用于低排放发电和烃采收的集成系统的示意图；
图6是操作利用类似图4-5所示的反应器单元的用于低排放发电和烃采收的集成系统的方法的示例性流程图；
图7是利用与图4-5所示的反应器单元相似的反应器单元的用于低排放发电和烃采收的集成系统的可选实施方式的图解；
图8图解了利用类似图7所示的反应器单元的用于低排放发电和烃采收的集成系统的示意图；和
图9是操作利用类似图7-8所示的反应器单元的用于低排放发电和烃采收的集成系统的可选方法的示例性流程图。
具体实施方式
在以下发明详述部分，结合优选的实施方式描述本发明的具体实施方式。但是，就以下描述特定于本发明的具体实施方式或具体使用而言，这意图仅为示例性的目的并仅仅提供示例性实施方式的描述。因此，本发明并不限于以下所描述的具体实施方式，而是，其包括落入所附权利要求的精神和范围内的所有可选项、改型和等同物。
本系统的至少一个益处是集成两种采收方法以产生两种注入气体(氮和CO2)用于另外的烃采收。产生N2、CO2和能量的一个示例性方法利用变压重整(PSR)方法中的催化燃烧步骤，从空气流中反应性除去氧气，并同时产生高压合成气，所述高压合成气容易分成为用于石油采出操作的CO2流和在高效发电中使用的氢气(H2)流。在PSR系统和方法的该意料之外的应用中，再生步骤可在与重整压力相似的高压下有利地进行。在本发明的一个实施方式中，重整和再生步骤都在相似的高压(例如300-500psig)下进行。在另一实施方式中，再生步骤中产生的小量的氮气被用于稀释氢气，然后在燃气轮机系统中，将氢气用作燃料。变压重整方法已至少在美国专利号7,491,250和美国专利申请号2005/0201929中公开，后者通过引用并入本文。
本公开系统和方法的另外的实施方式包括使用基于空气的自热重整装置(ATR)、部分氧化反应器(POX)或其他反应器单元，产生用于石油采出操作的N2、CO2和能量。在ATR中，甲烷的放热部分氧化和吸热催化蒸汽重整(endothermic catalytic steam reforming)产生高压合成气，高压合成气容易通过水煤气变换反应转化为CO2和氢气(H2)，并分离成用于石油采出操作的CO2流和在高效发电中使用的氢气(H2)流。POX进行与ATR相似的部分氧化，但是其在更高温度和无催化剂的情况下进行。
本公开系统和方法的进一步另外的实施方式包括通过使用传统的空气分离单元(ASU)，产生氮气(N2)、CO2和能量，所述空气分离单元产生富N2或纯N2流以代替N2，并同时产生富氧或纯氧流作为自热重整装置(ATR)的进料，在所述重整装置(ATR)中，甲烷的放热部分氧化和吸热催化蒸汽重整产生高压合成气，高压合成气容易通过水煤气变换反应转化为CO2和氢气(H2)，并分离成用于石油采出操作的CO2流和在高效发电中使用的氢气(H2)流。
尽管完全独立地生产用于油藏压力保持的氮和用于EOR的二氧化碳是可能的，但本公开系统和方法的实施方式利用了这样的协同作用——当以集成方法产生氮和二氧化碳以低得多的成本产生这些气体同时也以超低排放产生能量(发电)和/或脱盐水时其是可能的。值得注意的是，如果EOR利用是不可能的，则通过发电产生的CO2可以从再循环流中清除并被分离或储存。这允许各种实施方式被用于以超低排放发电。
在一个实施方式中，能量可经由在升高压力下进行燃烧由氢气流产生，以使燃烧产物膨胀通过燃气轮机的膨胀器，产生附加能量。布雷顿循环(Brayton cycle)的效率是跨过膨胀器的压力比和膨胀器的入口温度的函数。因此，达到更高的压力比和更高的膨胀器入口温度增加燃气轮机效率。膨胀器的入口温度可由部件表面的材料因素和冷却所限定。在高压燃烧器中利用这类燃料，然后在膨胀器阶段膨胀它们可导致高效率并提供利用此类油藏的经济方式。取决于可用的井口压力，膨胀也可在升高的压力下停止，以减少与用于井增压操作的压缩氮气相关的成本。
现在参考附图，图1图解了利用变压重整单元的用于低排放发电和烃采收的集成系统。系统100包括变压重整单元102，其被配置为利用空气流110a、天然气流106和蒸汽流108来产生主要包含氮气(N2)的再生流112、二氧化碳(CO2)流116和氢气流120。该系统100可进一步包括：提高采收率法采油油藏118以接收二氧化碳流116并任选地采出烃流117；和压力保持油藏114以接收再生流112并任选地采出烃流115。在一些实施方式中，也提供燃气轮机单元104，其利用空气流110b和氢气流120以产生能量136和气态排出流122，其可被导向热回收单元126，所述热回收单元被配置为利用水124以冷却气态排出流122来形成冷却的排出流130，产生至少一单位的蒸汽128用于蒸汽发生器132中以产生能量134。
在一些可选的实施方式中，至少一部分再生流112可被重新导向以经由流112′与氢气流120组合。在另一可选的实施方式中，至少一部分流128可被重新导向以经由流128′与蒸汽流108组合。在又一可选的实施方式中，空气流110b可被集成入燃气轮机104的压缩机压缩。
图2图解了利用类似图1所示的变压重整单元的用于低排放发电和烃采收的集成系统的示意图。因此，可参考图1最好地理解图2。系统200是系统100的可选的示例性实施方式，并且包括入口空气压缩机201、压缩的入口流202，其可包含一些经由压缩机210从流208再循环的氮气，其中入口流202被引入PSR再生单元204。PSR 102也包括用于接收蒸汽108和天然气106的PSR重整单位206，其产生包含一氧化碳、二氧化碳和氢气的合成气流211，其被供应给水煤气变换反应器212以将至少一部分一氧化碳转化为二氧化碳，然后送至分离器214，分离器214将尽可能多的二氧化碳分离为流116，以产生氢气流120。燃气轮机104包括集成压缩机220a、燃烧器220b和膨胀器220c。任选地，至少一部分氢气流120可经由流216被重新导向到PSR再生单元204，在该情况下，氢气流120′被供应给燃烧器220b。任选地，压缩空气可从进口压缩机220a经由流221到入口流202。
图3是操作利用类似图1-2所示的变压重整单元的用于低排放发电和烃采收的集成系统的方法的示例性流程图。因此，可参考图1-2最好地理解图3。方法300包括在变压重整装置102中产生主要包含氮气的再生流208和包含一氧化碳、二氧化碳和氢气的合成气流211的步骤302；将至少一部分主要包含氮气的再生流112注入压力保持油藏114的步骤304(注意，流112是流208的任选部分，其可被分成送入烃采出操作的流112和与新鲜空气110a组合以产生PSR再生氧化剂流202的再循环流)；和从压力保持油藏114采出烃的步骤306。任选地，方法300可进一步包括将采出的烃的至少一部分经由流115再循环至用于PSR 102的烃进料流106。
在一个可选的实施方式中，方法300可进一步包括在水煤气变换反应器212中将至少一部分一氧化碳转化为二氧化碳以产生包含氢气和二氧化碳的变换流213的步骤308；将变换流213分离成二氧化碳流116和氢气流120的步骤310；将至少一部分二氧化碳流116注入提高采收率法采油油藏118的步骤314；从提高采收率法采油油藏118采出烃的步骤316；和任选地，将采出的烃的至少一部分经由流117再循环至用于PSR 102的烃进料流106的步骤318。另外，方法300可进一步包括在燃气轮机104中产生能量136的步骤312，其中燃气轮机104被配置为使用至少一部分氢气流120作为燃料。
在系统100和200以及方法300的一个示例性实施方式中，PSR重整步骤302可在足以将燃料(例如，氢气流120或120′)供应到燃气轮机104的压力下进行(例如，在燃气轮机燃烧压力以上大约50到大约200磅/平方英寸表压(psig))。至重整步骤的进料106、108可由天然气和蒸汽构成。来自重整步骤302的产品是包含CO、H2、CO2、H2O和其他组分(例如污染物)的合成气混合物。在任选的H2O加入后，将该流变换——步骤304——以将大多数CO转化为CO2(产生更多的氢气)，并且进行分离——步骤306——以移出CO2。分离可经由传统的酸气洗涤、膜分离、物理或化学吸收溶剂或任何其他有效方法进行。按石油采出操作所需调节移出的CO2116(未示出)，并输送至该应用。
在CO2移出步骤306后保留的氢气120被用于发电(产生能量)。氢气120可用于任何发电循环中，但是有利地用作燃气轮机发电系统的进料，更有利地用于组合循环燃气轮机发电系统。在组合循环燃气轮机发电系统中产生的蒸汽128′的一些部分可被用作重整进料蒸汽108。在本公开的一个实施方式中，可通过在再循环前冷却再生烟道气208产生蒸汽，并且该蒸汽用作重整进料蒸汽108。在本公开的另一可选实施方式中，产生的氢气216的一些部分在PSR再生步骤302中用作燃料。
在PSR方法300的一个出乎意料的布置中，在与重整单元206相似的操作压力下，有利地运行再生单元204。在本发明的一个实施方式中，重整和再生步骤都在相似的且高(例如300-500psig)的压力下进行。在又一可选的实施方式中，在再生步骤208中产生的少量氮气被用于稀释氢气120，然后氢气在燃气轮机系统104中用作燃料。
本系统的一个优点是PSR重整步骤302对杂质例如高级烃、氮气、硫和CO2相对不敏感。如此，到重整装置102的天然气进料106可以是作为石油采出操作的一部分产生的较低纯度流(例如，来自采出/再循环流115或117)。这可以节省大量的用于石油采出操作的气体净化(cleanup)成本。
在传统的重整装置中，高级烃通常将引起烟灰或焦炭生成，但是通过PSR系统102更容易重整。有利地，PSR重整进料中的氮气可通过重整装置并最后作为送到发电燃气轮机104的氢气120中的可接受的(甚至优选的)燃料稀释剂112′。PSR重整进料中的二氧化碳可以减少重整需要的蒸汽108的量，但是将使产品分配移向CO。一些另外的蒸汽可加入到变换反应器212中，以驱动所有的一氧化碳成为二氧化碳，但是存在的分离将俘获该二氧化碳以在石油采出操作中再次使用。此外，PSR 102比传统的重整方法，对硫更容忍得多。在烃进料中10到100ppm水平的硫可以容许。然而，该硫将在PSR产品中出现，一些为基本是氮气的流208中的SOx，并且一些为二氧化碳流116中的H2S。因此，只有流208和116中的硫存在不干涉石油采出操作，才应该允许硫进入PSR重整装置206。
尽管提及二个油藏114和118，但油藏可以是同一个油藏，是两个、三个、四个或更多不同的油藏，并可以包括多个用于注入或采出的油藏。此外，来自油藏115和117的采出流的内含物可能随时间改变，特别是在注入气体开始生成的“突破点”。
一般而言，EOR油藏118是包含基本上是液体烃如原油的油藏或其一部分并且通常位于含水层之上。液体烃在适当的温度和压力下与注入的压缩二氧化碳流116可混相。高CO2浓度(例如多至约90体积％或以上)以这样的混相驱动操作是优选的，因为CO2用作稀释剂以降低油的粘度和作为溶剂以从地层岩石中除去油以及其它原因。此外，如果混合适当，将气体116泵入油藏需要更少的动力。注入流116中的氧水平优选地保持非常低。
一般而言，压力保持油藏114是在产油层上包括气顶的油藏或其一部分。当产生液体时，气顶压力和地层压力被减少，导致较低的生产力并且可能在气体部分导致反缩合。注入气体1112被配置为保持油藏内的压力以至少保持采收压力并避免反缩合。混相能力不是这种操作中的问题。因此，惰性气体如氮是优选的。在至少注入油藏114和118是同一个的具体示例性情况中，氮可以被注入油藏的气顶，二氧化碳被用作混相注入物，以在同一油藏中用于EOR。
采出流115和117可以是相同的或不同的，或者包括来自多个油藏的生产并且可以包括任何种类的轻烃组分和重液体烃组分和气态烃组分以及其它非烃组分如二氧化碳、硫化氢、氮、硫化羰及其组合。在最初或早期阶段的生产期间，预期在采出流115和117中具有比酸或非烃组分明显多的重烃组分。在任选的分离和净化后，流117可包含从至少约70摩尔百分比(mol％)的烃至约99mol％烃、从约1mol％至约5mol％CO2、从约0mol％N2至约5mol％N2以及一些其它组分。
在烃被采出时以及特别地一旦气体冲出发生，流115和117的组成可以发生急剧变化。例如，在CO2冲出之后，示例性采出流117可以具有以下含量：约5摩尔百分比(mol％)的烃至约60mol％的烃，从约40mol％至约95mol％的CO2，从约0mol％N2至约10mol％N2以及一些其它组分。在氮冲出之后，示例性采出流115可以具有以下含量：约5摩尔百分比(mol％)的烃至约60mol％的烃，从约5mol％至约20mol％的CO2，从约40mol％的N2至约95mol％N2以及一些其它组分。要注意的是，冲出是个瞬时过程而不是逐步过程，逐步过程相对快但产生的气体冲出量逐步增加。例如，油藏在早期生产期间可以稳定地产生约5mol％的CO2，然后在过渡期(从一个月到几年)产生渐增量的CO2，直至CO2的产生达到约95mol％CO2的高稳态产生。
在另外的实施方式中，使氢气流120保持较高温度用于混合以及在燃烧器220b内进行燃烧可以是期望的。可以通过与热排出气体流122或蒸汽流128或128′、系统200内其它压缩机(例如压缩机201、210或220a)中的一个产生的热或HRSG 126的交叉交换来加热流120。优选的是足以提高燃烧器220b内燃烧效率的温度。在一个实施方式中，氢气流120在进入燃烧器220b时可以为约50摄氏度(℃)至约500℃。
燃烧器220b可以是标准的燃烧器或可以是定制的或改进的燃烧器。可使用的燃烧器类型的实例包括部分氧化(POX)燃烧器、扩散燃烧器(diffusion burners)、贫燃预混(lean-premix)燃烧器和点火燃烧器。要注意的是，每个燃烧器类型可以要求一些改进以与可获得的燃料流一起工作。在扩散火焰燃烧器(或″燃烧装置″)中，燃料与氧化剂混合并同时在主燃烧区燃烧。扩散燃烧器产生接近化学计量的燃料/空气混合物区域，在此区域温度非常高。在预混合燃烧器中，燃料和空气在初始阶段被完全混合，形成均匀、贫燃、未燃烧的燃料/空气混合物，其被送至发生燃烧反应的第二阶段。目前贫燃预混燃烧器因为较低的火焰温度在燃气轮机中常用，其产生较低的NOx排放。在点火燃烧器中，热点火引导确保在其周围的贫燃料氧化剂混合物保持稳定燃烧。这些点火燃烧器通常被用于航空发动机和用于其本身不能保持稳定燃烧的燃料。
PSR实例
为了进一步阐明PSR系统102的实施方式，在下面表1中给出了图1-2中示出的实施方式的计算的热和材料平衡的一些示例性的流。该示例性变压重整装置系统102作为在再生步骤和重整步骤之间交替的两个圆柱形反应器进行操作。如所示，单元204反映反应器容器当前处于再生步骤中，而单元206反映反应器容器当前处于重整步骤中。反应器的内部尺寸为直径11ft(3.4M)，长度4ft(1.2M)。反应器的圆柱轴定位于垂直方位，并且当向上流时进行重整；当向下流时进行再生。填料由400孔/in2(62孔/cm2)蜂窝状单块组成，所述蜂窝状单块的堆积密度为50lb/ft3(0.8g/cc)。填料的底部70％包括重整催化剂。总循环长度为30秒；15秒为再生步骤，15秒为重整步骤。在重整步骤的最后，包括简短的蒸汽吹扫。
重整单元206以1760kgmoles/hr的速率进料甲烷106，并且伴随以4494kgmoles/hr速率进料蒸汽108，这代表3,600hr-1的重整ClGHSV。合成气(重整油)211以表1中示出的速率产生，并且在高温和低温变换阶段212变换以产生变换的产物213。通过使用活化的MDEA溶剂系统进行吸收，完成分离，这在纯化流116中产生1647kgmoles/hr的CO2，和在表1中示出的富含氢气燃料流120。
富含氢气燃料的26％在PSR再生步骤中使用(经由流216)和74％被消耗并经由表1上示出的流120’送至燃气轮机104。燃气轮机104按以下运行：空气压缩至12.6atm.abs.和384℃；10,100BTU/kWh(10655kJ/kWh)的加热速度；921lb/sec(418kg/s)的轮机流量；和126MW的净能量输出136。
空气压缩机201将新鲜空气110a提供给PSR再生系统，如在表1中所示。该空气与压缩机210压缩的再循环烟道气结合，并作为流202进料到PSR再生步骤。再生排气208(在再循环除去前)在表1中示出。冷却PSR流出物208的非再循环部分以除去水，产生在表1上示出的N2产物。
表1
(3600hr-1 ClGHSV下的PSR)
Figure BPA00001231709500121
图4是利用反应器单元的用于低排放发电和烃采收的集成系统的图解。系统400包括反应器单元402，其被配置为利用空气流410a、烃燃料流406和蒸汽流408来产生二氧化碳(CO2)流416和主要包含氢气和氮气的混合产物流420。该系统400可进一步包括：提高采收率法采油油藏418，以接收二氧化碳流416并任选地采出烃流417；和压力保持油藏414，其任选地采出烃流415。在一些实施方式中，也提供燃气轮机单元404，其利用空气流410b和混合产物流420以产生能量436和包括蒸汽和氮气的气态排出流422，其可被导向热回收单元426，所述热回收单元被配置为利用水424以冷却气态排出流422来形成主要包含氮气的冷却的排出流430，产生至少一单位的蒸汽428用于蒸汽发生器432中以产生能量434。
在一些可选的实施方式中，至少一部分冷却的排出流430可被进一步分离以增加氮气浓度，并且该氮气可被重新导向至空气流410b，用作燃气电轮机(gas power turbine)中的稀释剂，或经由管线430″送至压力保持油藏414。另外，至少一部分流428可被重新导向以经由流428′与蒸汽流408组合。在又一可选的实施方式中，空气流410b可被集成入燃气轮机404的空气压缩机压缩。
图5图解了利用类似图4所示的反应器单元的用于低排放发电和烃采收的集成系统的示意图。因此，可参考图4最好地理解图5。系统500是系统400的可选的示例性实施方式，并且包括入口空气压缩机502和压缩的入口流504，其中入口流504被引入反应器单元402。反应器单元402产生包含一氧化碳、二氧化碳、氮气和氢气的合成气流505，其可被供应给水煤气变换反应器510以将至少一部分一氧化碳转化为二氧化碳来形成主要包含二氧化碳、氮气和氢气的变换流511，其可被送至分离器512，分离器512将尽可能多的二氧化碳分离为流416，以产生具有基本是氢气和氮气的混合产物流420。分离器512可以是溶剂基吸收/再生系统例如胺或物理溶剂系统。燃气轮机404包括集成空气压缩机514a、燃烧器514b和膨胀器514c。然后，混合产物流420可以与来自集成压缩机514a的高压空气混合并且燃烧(预混合或其他布置，如上所述)以形成燃烧产物流520，其然后经由膨胀器514c膨胀。任选地，压缩空气可从进口压缩机514a经由流515到入口流504。
在一个示例性可选的实施方式中，集成压缩机514a与压缩机502相同，并且高压空气504的一部分在反应器单元中使用，而其余的在燃烧器514b中使用。另外，任选地，系统500可包括热交换器506，其被配置为利用来自合成气流505的热量形成任选的蒸汽流508以形成轻微冷却的合成气流507。任选的蒸汽流508可被加入到蒸汽流428或428′或与蒸汽流408一起使用。
图6是操作利用类似图4-5所示的自热重整单元的用于低排放发电和烃采收的集成系统的方法的示例性流程图。因此，可参考图4-5最好地理解图6。方法600包括利用反应器单元402产生包含一氧化碳、二氧化碳、氮气和氢气的合成气流505的步骤602；在水煤气变换反应器510中，将至少一部分一氧化碳转化为二氧化碳以形成变换流511的步骤604；将二氧化碳与变换流511分离以产生基本是二氧化碳的流416和主要包含氮气和氢气的混合产物流420的步骤606；在燃气轮机404中，产生能量436和包含氮气和蒸汽的气态排出流422的步骤608，其中燃气轮机404被配置为使用主要包含氮气和氢气的混合产物流420作为燃料；将氮气与蒸汽分离以至少产生气态氮气流430的步骤610；将至少一部分气态氮气流430″注入压力保持油藏414的步骤612；和从压力保持油藏414经由流415采出烃的步骤614。
在一个示例性可选的实施方式中，该方法可进一步包括将至少一部分分离的二氧化碳流416注入提高采收率法采油油藏418的步骤616；和从提高采收率法采油油藏418经由流417采出烃的步骤618。另外，方法600可包括将至少一部分从提高采收率法采油油藏418采出的烃417再循环到反应器单元402的步骤619；和将至少一部分从压力保持油藏414采出的烃415再循环到反应器单元402的步骤615。
分离步骤606也可分离流511中存在的任何硫化氢(H2S)以从混合产物流420将其移出，并且从而在流416中包括H2S。然后，流416可被进一步加工以将H2S转化为硫，或注入油藏417，以分离或用于提高采收率法采油。
在方法600的另一实施方式中，空气410a在专用空气压缩机502中压缩(或从燃气轮机空气压缩机514a中引出)并连同甲烷406和蒸汽408一起送至反应器单元402。调节空气速率以满足反应器402中的放热和吸热反应之间的热平衡。空气504中的氮气作为惰性气体通过重整装置402(和变换反应器510)并最后作为送去发电的氢气流420中的可接受的(甚至优选的)燃料稀释剂。在变换反应器510之后进行分离步骤606，以移出CO2416；不移出惰性氮气，并且其作为送至燃气轮机404的H2燃料的稀释剂。来自燃气轮机404的烟道气(例如，排出气422)由氮气和蒸汽组成，并且根据需要进行干燥，然后在石油采出操作中应用(例如油藏414和/或418)。注意，油藏414和418可具有与前面讨论的油藏114和118相同或相似的性质。
在一个示例性可选的实施方式中，反应器单元402可以是以下反应器的一个：放热部分氧化反应器，其中烃燃料流406是含碳烃燃料流，或吸热蒸汽重整反应器，其中烃燃料流406是天然气燃料流。在一个示例性系统中，烃的部分氧化重整的理想方程可以为：CnHmOp+x(O2+3.76N2)+(2n-2x-p)H2O＝nCO2+(2n-2x-p+m/2)H2+3.76N2
其中x是氧气与燃料的摩尔比。该比率可用于确定1)转化碳至二氧化碳所需水的量，2)氢气收率(以摩尔计)，3)产物流中氢气的浓度(单位为mol％)，和4)反应的热量。当x＝0时，方程简化为吸热蒸汽重整反应；当x＝12.5时，方程为部分氧化燃烧反应。空气进料流410a中含有的氧气与燃料进料流406中碳(烃中)的摩尔比(例如″x″的值)可以为大约0.45∶1到0.85∶1，或大约0.6∶1到0.7∶1。
在一个示例性实施方式中，燃料进料流406可包含一种或多种另外的气体组分，其选自具有两个或更多个碳原子的较重的烃(下文称为C2+烃)、二氧化碳、氮气和一氧化碳。
在公开的系统400和500以及方法600的一些实例中，蒸汽408与引入反应器402中的烃燃料流406中碳(烃中)的摩尔比为至多大约3∶1，或至多大约2.5∶1。例如，蒸汽408与烃燃料流406中碳(烃中)的摩尔比在0∶1到3∶1的范围内，优选在0.3∶1到3∶1的范围内，更具体地在1∶1到2.5∶1的范围内。蒸汽与碳的摩尔比基于燃料进料流中烃中的碳，其不包括燃料进料流中存在的任何二氧化碳和/或一氧化碳中的碳。当蒸汽存在于工艺流中时，mole％基于讨论中的流的总湿摩尔流速(total wet molar flow rate)的％。任选地，空气进料流也包括蒸汽。例如，空气进料流41oa中的蒸汽的量为至多10mole％，特别地至多1mole％。
任选地，引入反应器402的烃燃料流406包括氢气。在烃燃料流406中存在氢气可能是有利的，这是因为氢气可促进用空气进料流410a中含有的氧点燃烃燃料流406。例如，燃料进料流中氢气的量可以在大约0至大约20mole％的范围内，或大约2至大约18mole％的范围内。
在公开的系统400和500以及方法600的又一示例性实施方式中，在大约350℃到大约700℃或大约400℃到大约650℃或大约425℃到大约620℃范围内的温度下，将烃燃料流406引入反应器402。烃燃料流406可以与流408、428′、505、504、422的任意一个或多个或一些其他的流交叉交换。然而，如果在大约600℃以上温度将烃燃料流406引入反应器，那么可优选使用外部加热器(没有示出)升高烃燃料流406的温度。空气进料流410a或504可被相似地加热。
在公开的系统400和500以及方法600的一些示例性实施方式中，烃燃料流406可通过将包含烃原料和蒸汽的预重整进料流通过包含预重整催化剂的预重整装置(未显示)产生，以获得包含甲烷、氢气、一氧化碳、二氧化碳和蒸汽的烃燃料流406。如果需要，可增加烃燃料流中的氢气含量。这可通过多步预重整、通过使用高的预重整装置进口温度或通过将氢气再循环到燃料进料流来实现。烃燃料流406的烃原料可选自天然气、液化石油气(LPG)和各种石油馏分(例如石脑油)。另外，包含氢化器和脱硫装置的脱硫单元可设置在反应器402和预重整装置(如果存在的话)的上游，以从烃原料(例如天然气、LPG或石油馏分)除去含硫化合物。
在公开的系统400和500以及方法600的实施方式中，反应器402是气动反应器。在一个示例性实施方式中，空气进料流410a或504在多级空气压缩机502中压缩，所述多级空气压缩机例如具有4到8级，优选6级的压缩机。可选地，空气可由集成压缩机514a压缩并送至增压压缩机502，进行额外的压缩，然后进入反应器402。变换转换器510可以是含有变换催化剂的单一变换反应器，或者其可包含含有高温变换催化剂的高温变换反应器和含有低温变换催化剂的低温变换反应器。
在进一步的实施方式中，适当的CO2分离单元512包括使用膜将氢气流与浓缩二氧化碳流分离的单元，或包含使用物理或化学吸收溶剂的CO2吸收器和CO2解吸塔的单元。在一个示例性实施方式中，二氧化碳流416可包含至少大约98％的干基的CO2，剩余的大多数是氢气。在一些情况中，混合产物流420可包含痕量氧化碳(CO和CO2)和甲烷，例如以摩尔计小于500ppm。
在进一步的实施方式中，二氧化碳流416被脱水以减少其水含量，以便脱水的CO2流在二氧化碳流416的运输压力下具有大约-1℃的露点，从而确保液体(水)将不会冷凝出该流。例如，二氧化碳流416可在大约20至大约60barg的压力下脱水。适当地，在抽吸分离鼓中，减少二氧化碳流416的水含量。然后，二氧化碳流416可被压缩，并且压缩的CO2流通过至少一个脱水床(由例如分子筛或硅胶形成)或通过乙二醇脱水单元(例如，三甘醇脱水单元)以进一步减少水含量。
优选地，脱水二氧化碳流416被压缩，并递送到管道以转移至油田或气田的接收设备，在那里二氧化碳流416被用作油或天然气油藏418中的注入气体。二氧化碳流416可被进一步压缩至高于油田或气田的提高采收率法采油油藏418的压力，然后注入该油藏。注入的CO2移动烃朝向相关的生产井以增强从那里采收烃。
本发明的方法的优点是合成气流505和因此氢气流420具有比较高的氮气含量。因此，氢气可被氮气充分地地稀释，这不需要用额外的水稀释氢气流420，以便控制燃气轮机404的排气422中的NOx水平。例如，排出气(尾气)中NOx的水平可小于大约60ppm，或小于大约25ppm。在另一个实例中，氢气流420可包含按体积计大约35％到大约65％的氢气，更优选地按体积计45％到60％的氢气，例如按体积计48％到52％的氢气。
在公开的系统400和500以及方法600的进一步示例性实施方式中，热回收单元426是热量回收和蒸汽发生器单元(HRSG)，其产生和过加热额外的蒸汽用于蒸汽轮机432和系统400和500的其他地方。因此，HRSG 426能够产生高压(HP)蒸汽、中压(MP)蒸汽和低压(LP)蒸汽，并且能够过加热这些蒸汽流。HRSG 426也能够再加热作为排出流从多级蒸汽轮机432的高压级产生的中压蒸汽。例如，在HRSG 426中产生的过热的高压蒸汽的压力范围为大约80到大约200barg，并且温度范围为大约450℃到大约600℃。过热的中压蒸汽可例如在压力范围为大约25到大约50barg和温度范围为大约300℃到大约400℃的情况下，在HRSG 426中产生。此外，过热的低压蒸汽可例如在压力范围为大约2到大约10barg和温度范围为大约200℃到大约300℃的情况下，在HRSG 426中产生。在另一个可选的实施方式中，HRSG 426中的热量回收可在升高的压力下进行。在这样的方法中，气态排出流422的量可明显减少并且水在较高温度下凝结出来；这使得除去水更容易完成并且在较高温度可获得冷凝热，这比发电434或脱盐(未示出)更有价值。
在本发明的一个示例性实施方式中，冷却的排出气430从HRSG426经由管线430′再循环到进口空气流410b的任一个或两个并经由管线430″注入压力保持油藏414。在任一种情况下，该流可能要求额外的净化或干燥，类似于上述关于二氧化碳流416的方法。流430″也可在注入之前经由压缩机加压。流430″也可在注入之前进一步处理以除去痕量氧气。
图7是利用类似图4-5所示的反应器单元的用于低排放发电和烃采收的集成系统的可选实施方式的图解。因此，可参考图4-5最好地理解图7。系统700包括空气分离单元711，其被配置为产生基本是氮气的流712和基本是氧气的流713；反应器单元702，其被配置为利用基本是氧气的流713、烃燃料流706和蒸汽流708来产生二氧化碳(CO2)流716和氢气流720，其中二氧化碳流716可被导向提高采收率法采油油藏718，用于烃采收作业，例如烃流717的采出。氮气流712可被用于经由管线712′稀释氢气流720，或可导向压力保持油藏714，用于烃采收作业，例如烃流715的采出。
在一些实施方式中，也提供燃气轮机单元704，其利用空气流710b和氢气流720产生能量736和气态排出流722，其可被导向热回收单元726，所述热回收单元726被配置为使用水724冷却气态排出流722，以形成冷却的排出流730和产生至少一单位蒸汽728，用于蒸汽发生器732中以产生能量734。在另外的可选实施方式中，一些氮气可用于稀释经由管线712″进入燃气轮机704的空气流710b。在一些可选的实施方式中，至少一部分蒸汽728可经由流728′重新导向以与蒸汽流708组合。在又一可选的实施方式中，空气流710b可被集成入燃气轮机704的压缩机压缩。
图8图解了利用类似图7所示的反应器单元的用于低排放发电和烃采收的集成系统的示意图。因此，可参考图7最好地理解图8。系统800是系统700的可选的示例性实施方式，并且包括入口空气压缩机802以产生进料给ASU711的压缩空气流803；和独立压缩机804以压缩氮气流712。反应器单元702产生包含一氧化碳、二氧化碳和氢气的合成气流805，其被供应给水煤气变换反应器810以将至少一部分一氧化碳转化为二氧化碳，形成主要包含二氧化碳和氢气的变换流811，然后将其送至分离器812，分离器812将尽可能多的二氧化碳分离为流716，以产生氢气流720。燃气轮机704包括集成压缩机814a、燃烧器814b和膨胀器814c。然后，氢气流720可以与来自集成压缩机814a的高压空气混合并燃烧(预混合或其他布置，如上所述)以形成燃烧产物流820，其然后经由膨胀器814c膨胀。任选地，压缩空气可从进口压缩机814a经由流815到入口流804。
在一个示例性可选的实施方式中，集成压缩机814a与压缩机802相同，并且高压空气803的一部分在反应器单元702中使用，而其余的在燃烧器814b中使用。另外，任选地，系统800可包括热交换器806，其被配置为利用来自合成气流805的热量形成任选的蒸汽流508以形成轻微冷却的合成气流807。任选的蒸汽流808可被加入到蒸汽流728或728′或与蒸汽流708一起使用。如同反应器402一样，反应器702可以被配置以在放热部分氧化反应中操作，其中烃燃料流706是含碳烃，或在吸热蒸汽重整反应中操作，其中烃燃料流706是天然气燃料流。
图9是操作利用类似图7-8所示的反应器单元的用于低排放发电和烃采收的集成系统的可选方法的示例性流程图。因此，可参考图7-8最好地理解图9。方法900包括在空气分离单元711中分离空气的步骤902，所述空气分离单元711被配置为产生基本是氮气的流712和基本是氧气的流713；使用反应器单元702产生包含一氧化碳、二氧化碳和氢气的合成气流805的步骤904，所述反应器单元702被配置为利用基本是氧气的流713、烃燃料流706和蒸汽流708；在水煤气变换反应器810中，将至少一部分一氧化碳转化为二氧化碳以形成变换流811的步骤906；将变换流811分离成二氧化碳流716和氢气流720的步骤908；将至少一部分分离的二氧化碳流注入提高采收率法采油油藏的步骤910；和从提高采收率法采油油藏718采出烃的步骤912。
另外，任选地，方法900可包括在燃气轮机704中产生能量736的步骤914，其中燃气轮机704被配置为利用至少一部分氢气流720作为燃料；将至少一部分基本是氮气的流712注入压力保持油藏714的步骤916；从压力保持油藏714采出烃的步骤916。在进一步可选的实施方式中，任选地，方法900可包括将至少一部分从提高采收率法采油油藏718采出的烃经由管线717再循环到反应器单元702的步骤913；和将至少一部分从压力保持油藏714采出的烃经由管线715再循环到反应器单元702的步骤919。
在公开的系统700和800以及方法900中的一些实施方式中，空气710a被压缩以进料给空气分离单元(ASU)711，所述空气分离单元可以是低温单元。为了有效运行ASU711，空气进料压力的范围可以为大约6到大约10barg。氮气产物流712可以被泵压或经压缩机804压缩至产物氮气进入的石油采出操作需要的压力。氧产物流713可被泵压或压缩至注入反应器单元702需要的压力。调节进入反应器单元702的氧气进料速率以满足反应器中放热反应和吸热反应之间的热平衡。
另外地和任选地，反应器重整步骤904优选在供应燃料给燃气轮机704需要的压力下进行(一般地，高于燃气轮机燃烧压力大约50到大约200psig)。来自重整步骤的产物是包含CO、H2、CO2、H2O和少量其他成分的合成气混合物805。在热交换器806(在一些实施方式中，其可以是与HRSG 726相同的单元)中任选的热采收蒸汽发生以在蒸汽轮机(一个或多个)732中进行额外的发电和任选的H2O加入后，对流807进行变换以将大多数CO转换为CO2(产生更多氢气)，并且进行分离步骤908以移出CO2。分离可经由传统的酸气洗涤或如上所述的任何其他有效方法进行。根据石油采出操作的需要(如上所述)，移出的CO2716被调节，并输送以进行分离或注入提高采收率法采油油藏718中。
氢气流720被用于发电736。氢气720可用于任何发电循环中，但是有利地用作燃气轮机发电系统704的进料，更有利地用作组合循环燃气轮机发电系统的进料。在反应器热回蒸汽发生器726或组合循环燃气轮机发电系统704中产生的蒸汽728的一些部分可被用作反应器进料蒸汽708。在又一可选的实施方式中，至少一部分氮气712′可被用于稀释氢气720，然后将氢气用作燃气轮机系统704中的燃料。
在系统700和800以及方法900的特定实施方式中，空气分离单元(一个或多个)(ASU)711可基于低温分离或使用分子筛的分离。在基于低温的ASU的氧纯度谱的低端是对于高纯度氮气产生优化的ASU设计，这产生低于大约70％的氧气纯度。该流可含有大于20％的氮气水平。在该谱的另一端是对于高纯度氧气产生优化的ASU设计，其中甚至氩气也与氧气分离，这产生接近100％的氧气纯度。
在本公开的一些实施方式中，ASU 711是用于将氮气712和氧气713与空气分离的低温过程。与ASU 711相关的成本一般取决于需要的产品纯度。与产生95％纯度的氧气的ASU相比，产生99.5％纯度的氧气需要明显增加资金和马力。因此，在反应器中使用的氧气的纯度应该基于合成气流805的规格进行限定。如果需要高纯度流，那么可能需要高纯度氧气。
也可以考虑燃料杂质。一般而言，应当只考虑产生可满足EOR规格的副产物的燃料，或处于足够高的经济优势以使去除它们的加工装备可被认为是适当的燃料。
在氩气市场存在的情况下，ASU 711中用于其分离的额外成本、能量和复杂性可以认为是适当的。
虽然本发明可能有各种改进和可选形式，但以上讨论的示例性实施方式仅以实例的方式被显示。然而，还应该理解本发明并不意欲限于本文公开的特定实施方式。事实上，本发明包括落入所附权利要求的真正精神和范围内的所有替代方式、改进和等同物。

Claims (4)

1.集成系统，包括：
变压重整单元，其被配置为利用空气流、天然气流和蒸汽流以产生主要包含氮气的再生流和包含一氧化碳、二氧化碳和氢气的合成气流；
压力保持油藏，其接收至少一部分所述主要包含氮气的再生流；
水煤气变换反应器，其被配置为将至少一部分所述一氧化碳转化为二氧化碳；
分离单元，其被配置为将所述合成气流分离成二氧化碳流和氢气流；
提高采收率法采油油藏，其接收至少一部分所述二氧化碳流；
从所述压力保持油藏采出的第一采出流，其中至少一部分所述第一采出流与所述天然气流组合；和
从所述提高采收率法采油油藏采出的第二采出流，其中至少一部分所述第二采出流与所述天然气流组合。
2.权利要求1所述的系统，进一步包括燃气轮机，所述燃气轮机被配置为利用所述氢气流以产生能量和气态排出流。
3.权利要求2所述的系统，进一步包括热回收单元，所述热回收单元被配置为接收和冷却所述气态排出流，产生至少一单位的热能，并且产生至少一体积的水和冷却的气流，其中所述热能被用于产生蒸汽。
4.权利要求3所述的系统，其中所述蒸汽以选自下列的方式应用：1)在蒸汽轮机中产生蒸汽能量，2)再循环到所述变压重整单元，和3)它们的任意组合。
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US20110000671A1 (en) 2011-01-06
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WO2009121008A2 (en) 2009-10-01
MY153097A (en) 2014-12-31
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