CN105008499A - 发电和从甲烷水合物中回收甲烷 - Google Patents

发电和从甲烷水合物中回收甲烷 Download PDF

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CN105008499A
CN105008499A CN201480012535.9A CN201480012535A CN105008499A CN 105008499 A CN105008499 A CN 105008499A CN 201480012535 A CN201480012535 A CN 201480012535A CN 105008499 A CN105008499 A CN 105008499A
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methane
gaseous mixture
nitrogen
methane hydrate
hydrate
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S·K·达努卡
M·W·伊顿
R·A·亨廷顿
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ExxonMobil Upstream Research Co
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Abstract

本发明涉及一种系统和方法，其用于发电和从甲烷水合物中回收甲烷。该系统包括配置成发电的低排放的发电装置，其中来自该低排放的发电装置的废气提供包括氮气和二氧化碳的气体混合物。该系统还包括甲烷回收系统，其配置成通过将来自该气体混合物的氮气和二氧化碳注入到甲烷水合物中以从甲烷水合物中回收甲烷。

Description

发电和从甲烷水合物中回收甲烷
交叉参考的相关申请
本申请要求2013年3月8日提交的，名称为“发电和从甲烷水合物中回收甲烷”的美国专利申请61/775168的优先权，其全部内容在此通过引入并入本申请。
发明领域
本发明总体涉及发电和从甲烷水合物中回收甲烷的整合。更具体的，本发明涉及经由发电装置发电和使用来自该发电装置的废气从甲烷水合物中回收甲烷的系统和方法。
发明背景
本节介绍了可能与本发明的示例性实施方案有关的本领域各个方面。这样的讨论据信有助于提供框架来促进更好的理解本发明的具体方面。因此，应当理解本节应当以这样的方式解读，并且不必然是对现有技术的承认。
目前大体积的甲烷以甲烷水合物的形式包含在永久冻土区域中。在许多情况中，令人期望的是可以从甲烷水合物中回收甲烷。已经开发了用于从甲烷水合物中回收甲烷的几种技术。根据一种技术，甲烷是经由热激励从甲烷水合物中回收的。这可以通过管线将高温水注入水合物层中来完成。另外一种技术包括经由减压使用真空装置从甲烷水合物中分离甲烷。另外，另一种技术包括使用抑制剂从甲烷水合物中分离甲烷，该抑制剂导致该甲烷水合物变得不稳定。
Lee等人的美国专利No.7988750描述了一种通过将含有氮气和二氧化碳气体的气体混合物加入到甲烷水合物中以从甲烷水合物中回收甲烷的方法。具体的，该甲烷水合物内的甲烷与该气体混合物反应，并且该气体混合物取代甲烷水合物中的甲烷，因此释放了甲烷。此外，该含有氮气和二氧化碳的气体混合物可以是获自工厂的烟道气。但是，该烟道气可以包括氮气和二氧化碳之外的气体组分，例如水，硫和多种其它气体组分。因此，可以使用清洁设备来在烟道气注入到甲烷水合物之前，从烟道气中除去额外的气体组分，来保护环境。在一些情况中，从烟道气中除去气体组分导致了运行成本明显升高，因此使得从甲烷水合物中回收甲烷是不太合算的。
一种常规气体涡轮发动机经常具有涡轮压缩机，其通过轴杆机械连接到膨胀涡轮上。该涡轮压缩机可以用于压缩由涡轮压缩机引入的空气流。该压缩空气然后送到燃烧器。在该燃烧器中，注入燃料并且点燃来产生连续火焰。来自该火焰的高压废气流入膨胀涡轮，其在该废气膨胀时产生了来自其的机械能。该机械能通过轴杆转移到涡轮压缩机，被用于为空气压缩供能。另外的机械能是在用于压缩吸入空气的量上产生的，并且收集用于其它目的，例如用于发电。该火焰温度会超过燃烧器罐的冶金极限，因此经常使用过量空气来提供冷却。但是，这种排列会产生更高量的污染物例如氮氧化物(NOx)。
因为诸多原因，从废气中捕集二氧化碳用于其它用途会是有问题的。例如在常规燃气涡轮机的废气中存在着低浓度的二氧化碳，并且必须处理非常大体积的气体。该废气也可以处于相对低的压力例如在约1050千帕(kPa)，和相对高的温度例如约425摄氏度(℃)到约700℃。此外，该废气可以包含大量氧气，其会干扰CO2的提取或使用。最后，该废气可以是由来自冷却的水饱和的，这会增加CO2提取系统中再沸器的负担。
在燃烧器内(例如与燃气涡轮机整合的燃烧器)燃料的燃烧可以通过监控离开膨胀机的废气温度来控制，因为对于现有的仪器来说，燃烧器中的温度通常是过高的。在满负荷时，典型的燃气涡轮机调整了引入到许多燃烧器中的燃料的量，来达到期望的燃烧气体或者废气温度。
但是，当目标是从废气中捕集二氧化碳(CO2)时，控制引入到燃烧器中的氧化剂的量也会是令人期望的。目前的二氧化碳捕集技术由于多种原因而是昂贵的。例如废气中二氧化碳的低压力和低浓度。但是，二氧化碳浓度可以通过将燃烧方法在基本上化学计量比条件下运行而从约4％明显增加到大于10％。此外，一部分的废气可以作为稀释剂再循环到燃烧器，来代替空气来冷却燃烧产物。
增强的废气可以通过其它系统来捕集使用，例如直接从燃气涡轮机排气中捕集。但是如果燃气涡轮机是由分开的来源来供给氧化剂，则可以更有效的压缩该燃气涡轮机的涡轮压缩机中的废气，并且将该压缩气体作为冷却剂再循环到燃烧器，然后在再循环流的控制过程中捕集高压渗流。许多研究已经调查了将一部分的废气再循环到燃烧器的理念。
例如Earnest的美国专利No.4271664公开了一种具有废气再循环的涡轮发动机。该发动机具有在开环Brayton循环上运行的主功率涡轮机。供给到主功率涡轮机的空气是通过闭路Rankine循环的涡轮机独立驱动的压缩机来供给的，其导出了来自Brayton涡轮机的废气的热能。在部分负荷运行过程中，将一部分的该废气再循环入压缩机入口中。但是，没有公开再循环废气另外的用途。
发明内容
本发明的一种示例性实施方案提供一种用于发电和从甲烷水合物中回收甲烷的系统。该系统包括配置成发电的低排放的发电装置，其中来自该低排放的发电装置的废气提供包括氮气和二氧化碳的气体混合物。该系统还包括甲烷回收系统，其配置成通过将来自该气体混合物的氮气和二氧化碳注入到甲烷水合物中以从甲烷水合物中回收甲烷。
另一示例性实施方案提供一种用于发电和从甲烷水合物中回收甲烷的方法。该方法包括经由低排放的发电装置发电，其中来自该低排放的发电装置的废气提供包括氮气和二氧化碳的气体混合物。该方法还包括通过将来自该气体混合物的氮气和二氧化碳注入到甲烷水合物中以从甲烷水合物中回收甲烷。
另一示例性实施方案提供一种用于从甲烷水合物中回收甲烷的系统，其使用来自组合的循环发电装置的气体混合物。该系统包括膨胀涡轮，其配置通过从离开燃烧器的气体混合物提取能量来提供机械能，其中该气体混合物包括氮气和二氧化碳。该系统还包括热回收蒸汽发生器(HRSG)，其配置成通过用来自膨胀涡轮的该气体混合物加热锅炉来产生蒸汽，蒸汽涡轮，其配置成通过提取HRSG产生的蒸汽的能量来提供机械能，和发电机，其配置成由膨胀涡轮和蒸汽涡轮提供的机械能来发电。该系统进一步包括分离系统，其配置成将二氧化碳与该气体混合物中的甲烷分离，和甲烷回收系统，其配置成通过将来自该气体混合物的氮气和二氧化碳注入到甲烷水合物中以从甲烷水合物中回收甲烷。从该甲烷水合物回收的甲烷的至少一部分作为燃料流入该燃烧器中。
附图说明
本发明的优点通过参考下面的详细说明和附图而更好理解，在其中：
图1是发电和从甲烷水合物中回收甲烷的开采区图示；
图2是组合的循环发电装置的过程流程图，其可以用于发电和产生包括氮气(N2)和二氧化碳(CO2)的稀释剂气体混合物；
图3是将低排放发电与由甲烷水合物中回收甲烷相整合的系统的过程流程图；
图4是显示了作为温度、压力和氮气摩尔分数函数的N2/CO2水合物地岩层曲线的图；
图5是将低排放发电与由甲烷水合物回收甲烷相整合的另一系统的过程流程图；
图6是用于从甲烷水合物地岩层中回收甲烷的管线构造的透视图；
图7是用于从甲烷水合物地岩层中回收甲烷的另一管线构造的透视图；和
图8是用于发电和由甲烷水合物中回收甲烷的方法的过程流程图。
具体实施方式
在下面的具体实施方式部分，描述了本发明的具体实施方案。但是，下面的说明对于具体实施方案或者本发明的具体用途来说处于特定的程度，其目的仅仅是用于示例性目的和简单提供对于示例性实施方案的说明。因此，本发明不限于此处所述的具体实施方案，而是包括了落入附加的权利要求真实的主旨和范围内全部的选项，改变和等价物。
在开始时为了便于提及，阐述了用于本申请的某些术语和它们在本文上下文中所用的含义。此处所用术语不限于此处所定义的程度，它应当给予所属领域技术人员已经给出的最宽定义，即，该术语如至少一个印刷的公开文献或者公布的专利所反映的。此外，本发明不受限于此处所示的术语的使用，因为起到了相同或类似目的全部等价物，同义词，新发展和术语或技术被认为处于本发明权利要求的范围内。
“组合的循环发电装置”通常是开放Brayton循环和Rankine循环的组合。组合的循环发电装置典型的使用蒸汽和燃气涡轮机二者来发电，但除了水和蒸汽之外的其它工作流体也可以用于Rankine循环中。该组合的循环气体/蒸汽发电装置通常具有比仅仅气体或蒸汽设备更高的能量转化效率。组合的循环设备的效率可以高达较低加热值(LHV)的50％-60％。较高的组合的循环效率是由燃气涡轮机与蒸汽涡轮的组合的协同使用来产生的。典型的，组合的循环发电装置使用了来自燃气涡轮机排气的热量来使水沸腾产生蒸汽。典型的组合的循环设备中的锅炉可以称作热回收蒸汽发生器(HRSG)。产生的蒸汽被用于为组合的循环设备中的蒸汽涡轮供能。该燃气涡轮机和蒸汽涡轮可以用于分别为独立的发电机供能，或者可选择的，该蒸汽涡轮可以与燃气涡轮机组合来经由共用的驱动杆共同驱动单个发电机。
本文使用的“压缩机”包括任何类型的设备，其设计来增加流体或工作流体的压力，和包括任何一种类型的或者组合的类似或者不同类型的压缩设备。压缩机也可以包括与压缩机相连的辅助设备例如发动机，和驱动系统等。该压缩机可以使用一个或多个压缩级，例如串联的。示例性压缩机可以包括但不限于主动置换类似的，例如诸如往复式和旋转式压缩机，和动态类型的例如诸如离心的和轴流压缩机。例如压缩机可以是处于燃气涡轮机发动机中的第一级，如此处进一步详细讨论的。
本文使用的“冷却”宽泛的表示使物质的温度和/或内部能量下降和/或降低例如任何合适的量。冷却可以包括温度下降至少约1摄氏度(℃)，至少约5℃，至少约10℃，至少约15℃，至少约25℃，至少约50℃，至少约100℃和/或类似温度。冷却可以使用任何合适的冷源例如产生蒸汽，热水加热，冷却水，空气，制冷剂，其它工艺流(整合)及其组合。一种或多种冷却源可以组合和/或级联来达到期望的出口温度。该冷却步骤可以使用冷却单元，其具有任何合适的装置和/或设备。根据一种实施方案，冷却可以包括间接热交换，例如与一种或多种热交换器的热交换。热交换器可以包括任何合适的设计，例如壳管式，板框式，逆流，同流，延伸的表面和/或类似物。在该选项中，冷却可以使用蒸发性(汽化热)冷却和/或直接热交换，例如直接喷入工艺流中的液体。
“低温”指的是约-50℃或更低的温度。
“稀释剂”是用于降低供入燃气涡轮机中来燃烧燃料的氧化剂浓度的气体。该稀释剂可以是过量的氮气，二氧化碳，燃烧废气或者任何数目的其它气体。在实施方案中，稀释剂也可以提供来冷却燃烧器。
“当量比”指的是燃料与进入燃烧器的氧气的质量比，除以当所述比率是化学计量比时的燃料与氧气的质量比。燃料和氧气理想的燃烧来形成二氧化碳和水时的当量比是1。过贫混合物(例如具有比燃料多的氧气)将提供当量比小于1，而过于富含的混合物(例如具有比氧气多的燃料)将提供当量比大于1。
“示例性”在此专门用于表示“充当例子、情况或者说明”。此处描述为“示例性的”任何实施方案不解释为优先于或者优越于其它实施方案。
“地岩层”是任何有限的地下区域。该地岩层可以包含一个或多个含烃层，一个或多个非含烃层，过负荷的和/或不足负荷的任何地下地质地岩层。“过负荷”和/或“不足负荷”是在所关注的地岩层之上或之下的地质材料。
“燃料”包括可以用氧化剂燃烧来为燃气涡轮机供能的任何数目的烃。这样的烃可以包括天然气，经处理的天然气，煤油，汽油或者任何数目的其它天然或合成烃。在一种实施方案中，将来自油田的天然气净化和用于为涡轮机供能。在另一实施方案中，重整气体例如在蒸汽重整方法中加工烃产生的重整气体可以用于为涡轮机供能。
术语“气体”是与“蒸气”可互换使用的，并且定义为处于气态的物质或者物质的混合物，其有别于液态或固态。同样，术语“液体”表示处于液态的物质或者物质的混合物，其有别于气态或固态。
“燃气涡轮机发动机”以Brayton循环运行。如果废气排出到大气中，则被称作开放Brayton循环，而废气的再循环产生了封闭的Brayton循环。本文使用的“燃气涡轮机”典型的包括压缩机区，许多燃烧器，和膨胀涡轮区。该压缩机可以用于压缩氧化剂，其与燃料混合和经过通道送到燃烧器。该燃料和氧化剂的混合物然后点燃来产生热的燃烧气体。该燃烧气体经过通道送到膨胀涡轮区，其提取该燃烧气体的能量，用于为压缩机供能，以及产生有用的功来为负荷供能。在这里所讨论的实施方案中，氧化剂可以通过外部压缩机提供到燃烧器，其可以或者可以不机械连接到燃气涡轮发动机的轴杆。此外在实施方案中，该压缩机区可以用于压缩稀释剂例如再循环的废气，其可以作为冷却剂供给到燃烧器。
“热交换器”宽泛的表示任何这样的装置，其能够将热从一种介质传递到另一介质，并且包括具体的任何的结构，例如通常称作热交换器的装置。热交换器包括“直接热交换器”和“间接热交换器”。因此，热交换器可以是板框式，壳管式，螺旋式，发夹式，核式，核罐式，双管式或者任何其它类型的已知的热交换器。“热交换器”也可以指的是任何柱，塔，单元或者其它排列，其用于使得一种或多种流送过其中，和来影响制冷剂的一个或多个管线，和一种或多种供料流之间的直接或间接热交换。
“热回收蒸汽发生器”或“HRSG”是热交换器或者锅炉，其回收了来自热气流的热量。它产生了蒸汽，其可以用于加工中或者用于驱动蒸汽涡轮。HRSG的一种普通应用是组合的循环发电装置，这里来自燃气涡轮机的热废气被供给到HRSG来产生蒸汽，其依次驱动了蒸汽涡轮。这种组合比单独的燃气涡轮机或者蒸汽涡轮更有效的产生了电。
本文使用的“水合物”是由主体化合物(其形成了基本骨架)和客体化合物(其通过分子间相互作用例如氢键，范德华力等保持在主体骨架中)构成的复合物。水合物也可以称作主体-客体络合物，内含化合物和加成物。本文使用的“插合物”、“插合物水合物”和“水合物”是可互换的术语，其用于表示具有由作为主化合物的水构成的基本框架的水合物。水合物是一种结晶固体，其看起来像冰，并且在“水合物地岩层成分”周围形成水分子笼形结构。
“水合物地岩层成分”指的是石油流体中的化合物或者分子，包括天然气，其在高压和/或降低的温度时形成水合物。示例性的水合物地岩层成分包括但不限于烃例如甲烷，乙烷，丙烷，丁烷，新戊烷，乙烯，丙烯，异丁烯，环丙烷，环丁烷，环戊烷，环己烷和苯等。水合物地岩层成分还可以包括非烃物质例如氧气，氮气，硫化氢，二氧化碳，二氧化硫和氯等。根据此处所述的实施方案，由甲烷形成的水合物被称作“甲烷水合物”。甲烷水合物可以经常出现在永久冻土区中例如诸如北极地区。
“烃”是一种有机化合物，其主要包括元素氢和碳，虽然也会存在少量的氮，硫，氧，金属或者任何数目的其它元素。本文使用的烃通常指的是粗天然气中存在的组分例如CH4，C2H2，C2H4，C2H6，C3异构体，C4异构体，苯等。
“天然气”指的是一种多组分气体，其获自原油井或者地下带有气体的地岩层。天然气的组成和压力可以变化很大。一种典型的天然气体流包含甲烷(CH4)作为主要组分，即，大于50mol％的该天然气体流是甲烷。该天然气体流还可以包含乙烷(C2H6)，较高分子量烃(例如C3-C20烃)，一种或多种酸性气体(例如二氧化碳或者硫化氢)或者其任意组合。该天然气也可以包含少量污染物例如水，氮气，硫化铁，蜡，原油或者其任意组合。该天然气流可以在用于实施方案之前充分净化，来除去可以充当毒物的化合物。
“氧化剂”是这样的气体混合物，其可以流入燃气涡轮发动机的燃烧器中来燃烧燃料。本文使用的氧化剂可以是氧，其混合有任何数目的其它气体作为稀释剂，包括二氧化碳(CO2)，氮气(N2)，空气，燃烧废气等。除了氧之外，充当氧化剂的其它气体可以存在于该氧化剂混合物中，包括臭氧，过氧化氢，NOx等。
“压力”是由气体在体积壁上单位面积所施加的力。压力可以表示为磅/平方英寸(psi)。“大气压”指的是空气的局部压力。“绝对压力”(psia)指的是大气压(在标准条件为14.7psia)加上表压(psig)的总和。“表压”(psig)指的是通过表所测量的压力，其仅仅表示超过局部大气压的压力(即，表压0psig对应于14.7psia的绝对压力)。术语“蒸气压力”具有通常的热力学含义。对于在给定压力的封闭系统中的纯组分来说，该组分蒸气压力基本上等于该系统总压力。
术语“永久冻土”指的是长期的冻土，即，天然存在的材料，其长期持续处于低于0℃的温度。这样的冻土层被专门基于温度来命名。它的部分或者全部湿气可以是未冷冻的，这取决于水的化学组成或者通过毛细管力的冷冻点下降。但是大部分永久冻土是通过冰来固结的。除了水之外，永久冻土可以存储任何数目的其它物质。例如永久冻土可以存储水合物形式的甲烷和/或二氧化碳。永久冻土形成和存在于平均每年空气温度是0℃或更低处的气候中。这样的气候通常的特征是漫长寒冷的冬天和短的相对干燥的凉爽的夏天。因此永久冻土遍布于北极、亚北极区和南极。
“基本上”当用于表示材料的量或者其具体特征时，指的是足以提供该材料或特征意图提供的效果的量。可允许的准确的背离度在一些情况中会取决于具体上下文。
概述
此处所述的实施方案提供将低排放的发电与从甲烷水合物中回收甲烷相整合的系统和方法。根据这样的实施方案，包括N2和CO2的气体混合物由低排放的发电装置在发电过程中产生。该气体混合物被用于例如回收在永久冻土区域中的甲烷水合物中截留的甲烷。在一些实施方案中，所回收的甲烷然后作为燃料用于低排放的发电装置，因此提供整合的发电和甲烷回收系统。
用于发电和从甲烷水合物回收甲烷的系统
图1是用于发电和从甲烷水合物中回收甲烷的开采区100的图示。在各种实施方案中，开采区100位于永久冻土区域中，例如诸如北极或者亚北极。开采区100包括低排放的发电装置102，其是与甲烷回收系统104整合的。
该低排放的发电装置102可以是半封闭的Brayton循环发电装置，或者包括半封闭的Brayton循环和Rankine循环二者的组合的循环发电装置。如果该低排放的发电装置102是组合的循环发电装置，则来自半封闭的Brayton循环的膨胀涡轮的排出流可以用于沸腾热回收蒸汽发生器(HRSG)中的水或者其它传热流体，所述水或者其它传热流体可以用于为Rankine循环发电装置供能。在该Rankine循环发电装置中，蒸汽或者其它蒸气可以用于驱动涡轮机和产生更多的电。
根据此处所述的实施方案，来自低排放的发电装置102的废气提供气体混合物，其主要包括N2和CO2。来自该低排放的发电装置102的气体混合物被提供到甲烷回收系统104，如箭头106所示。
甲烷回收系统104包括注入系统，用于将该气体混合物注入甲烷水合物地岩层108中，如箭头110所示。在各种实施方案中，将该气体混合物注入甲烷水合物地岩层108中导致甲烷从甲烷水合物中释放。具体的，该气体混合物中的二氧化碳替换了甲烷水合物内的甲烷。另外，该气体混合物内的氮气通过增加甲烷水合物的温度而有助于甲烷从甲烷水合物中释放。然后所释放的甲烷流回甲烷回收系统104，如箭头112所示。
在一些实施方案中，甲烷回收系统104还包括分离系统，用于将该气体混合物分离成二氧化碳流和氮气流。然后该二氧化碳流和氮气流可以分别注入到甲烷水合物地岩层108中。
经由甲烷回收系统104回收的甲烷可以包括一些量的杂质，例如来自甲烷水合物地岩层108或者周围的永久冻土的土壤或者水。所以，该甲烷可以流到分离设施114，如箭头116所示。分离设施114可以除去甲烷的杂质和将杂质送到另一目的地例如尾矿池，如箭头118所示。净化的甲烷然后可以作为最终的甲烷产品卸下，如箭头120所示。
在各种实施方案中，一部分的净化的甲烷可以从分离设施114送到低排放的发电装置102，如箭头122所示。然后该甲烷可以作为燃料，用于低排放的发电装置102的燃气涡轮发动机。此外在一些实施方案中，经由甲烷回收系统104回收的甲烷是基本纯净的，并且可以作为燃料，无需在分离设施114中净化而用于低排放的发电装置102的燃气涡轮发动机。在这样的实施方案中，所回收的甲烷可以从甲烷回收系统104直接流到低排放的发电装置102，如箭头124所示。
图1的框图并非意图表示开采区100是包括图1所示的全部组分。此外，开采区100可以包括图1未示出的任何数目的另外的组分，这取决于具体实施方案的细节。
图2是组合的循环发电装置200的过程流程图，其可以用于发电202和产生包括N2和CO2的稀释剂气体混合物。在各种实施方案中，该组合的循环发电装置200是在开采区100中作为低排放的发电装置102来使用的。此外，在各种实施方案中，该组合的循环发电装置200包括半封闭的Brayton循环(其包括例如膨胀涡轮206)和Rankine循环(其包括例如HRSG 208)。
在该组合的循环发电装置200内，氧化剂210和燃料气体212被送到燃烧器214中进行燃烧。压缩的稀释剂流216也被供给到燃烧器214来降低燃料气体212和氧化剂210的总量，这使得燃烧过程在接近于化学计量比条件运行，而不会使燃烧器214或膨胀涡轮206过热。结果，降低了燃烧过程产生的O2和CO的量，并且离开该燃烧器的热废气218主要包括CO2、H2O和N2，还有一些痕量气体例如CO和NOx。
氧化剂210和燃料气体212的压力可以例如使用压缩机来增加，促使该压力匹配压缩的稀释剂流216在燃烧器214处的注入压力。来自燃烧器214的热废气218流到膨胀涡轮206，使用热废气218的能量来旋转轴杆220。轴杆220将机械能提供到压缩机涡轮机224，完成Brayton循环。轴杆220还可以将机械能提供到发电机222来发电202。发电机222可以从膨胀涡轮206直接耦合到轴杆220上，或者可以通过齿轮箱、离合器或者其它装置耦合到轴杆220上。
热废气218从膨胀涡轮206流到HRSG 208。该HRSG 208可以用来自热废气218的能量使得水流224沸腾来产生蒸汽226。产生的蒸汽226可以用于驱动蒸汽涡轮228和旋转轴杆230。在离开蒸汽涡轮228后，所形成的低压蒸汽232可以冷却和冷凝，作为水流224供给HRSG 208。
来自蒸汽涡轮228的轴杆230可以将机械能提供到发电机234来发电202，或者可以用于为其它装置例如压缩机供能。发电机234可以从蒸汽涡轮228直接耦合到轴杆230上，或者可以通过齿轮箱，离合器或者其它装置耦合到轴杆230上。此外，在图2所示的实施方案中，膨胀涡轮206和蒸汽涡轮228耦合来分开发电机222和234。但是，应当理解膨胀涡轮206和蒸汽涡轮228也可以直接或间接耦合到一个共用发电机上。
离开HRSG 208的热气体流236流到冷却器238。冷却器238冷却了热气体流236，使得燃烧方法中形成的水蒸气冷凝出来，使得它作为分别的水流240除去。在除去水流240后，冷却的气体混合物242被提供到压缩机244进行压缩，然后将该压缩的稀释剂流216供给到燃烧器214来帮助冷却该燃烧器214。热气体流236作为稀释剂流216再循环部分的封闭了组合的循环发电装置200中的Brayton循环，产生了半封闭的Brayton循环。
当燃料气体212和氧化剂210连续供入组合的循环发电装置200来保持燃烧时，连续除去一部分246的稀释剂流216。稀释剂流216可以主要包括N2和CO2。根据此处所述的实施方案，离开组合的循环发电装置200的稀释剂流216被用于从甲烷水合物中回收甲烷，如此处进一步讨论的。
图2的过程流程图并非意图表示组合的循环发电装置200包括图2所示的全部组分。此外，该组合的循环发电装置200可以包括图2未示出的任何数目的另外的组分，这取决于具体实施方案的细节。
图3是系统300的过程流程图，其用于将低排放的发电与从甲烷水合物回收甲烷相整合。在各种实施方案中，系统300是在开采区100中作为低排放的发电装置102和甲烷回收系统104来使用的。系统300提供低排放的发电，其使用组合的循环发电装置，该设备包括半封闭的Brayton循环(其使用燃气涡轮发动机302)和Rankine循环(其使用HRSG 304)。另外，该系统300通过使用来自组合的循环发电装置的废气从甲烷水合物中释放甲烷，而提供从甲烷水合物中回收甲烷。
如图3所示，空气306和燃料气体308供给到燃烧器310中以在半封闭Brayton循环中燃烧。虽然空气306在图3所示的实施方案中用作氧化剂，但是应当理解任何其它合适类型的氧化剂也可以与系统300一起使用。
压缩的稀释剂流312也供给到燃烧器310来降低用于燃烧方法的空气306和燃料气体308的总量。这可以使得燃烧方法在接近于化学计量比的条件运行，而不过热。结果，降低了在燃烧方法中产生的O2和CO的量，并且离开燃烧器的热废气314主要包括CO2、H2O、和N2，还有一些痕量的气体。
空气306和燃料气体308的压力可以例如使用压缩机增加，来促使该压力匹配压缩的稀释剂流312在燃烧器310处的注入压力。例如根据图3所示的实施方案，空气306是在空气压缩机316内压缩的。另外，空气压缩机316可以包括一个或多个压缩级，和可以包括一个或多个中间冷却器来降低级间空气温度。此外，当包括大于一级的压缩时，单级可以或者可以不配置在共用外壳中或者通过共用轴杆或者其它驱动装置来驱动。该压缩的空气306然后供入燃烧器310中进行燃烧。
来自燃烧器310的热废气314流到燃气涡轮发动机302的膨胀涡轮322，其使用热废气314的能量来旋转轴杆324。轴杆324将机械能提供到发电机326来发电328。发电机326可以从膨胀涡轮322直接耦合到轴杆324上，或者可以通过齿轮箱，离合器或者其它装置耦合到轴杆324上。
热废气314从膨胀涡轮322流到组合的循环发电装置的Rankine循环内的HRSG 304。HRSG 304用来自热废气314的能量使水流330沸腾来产生蒸汽332。在各种实施方案中，产生的蒸汽332被用于驱动蒸汽涡轮，利用蒸汽332的能量来旋转轴杆。该轴杆可以将机械能提供到发电机来产生另外的电。
离开HRSG 304的热气体流334流到废气再循环(EGR)鼓风机336。该EGR鼓风机336压缩该热气体流334和将所形成的压缩的气体流338供入EGR冷却器340中。EGR冷却器340冷却该压缩的气体流338，产生稀释剂流342。冷却该热气体流334还会冷凝出水，干燥该稀释剂流342。
稀释剂流342然后供入压缩机344中。压缩机344压缩了稀释剂流342，产生压缩的稀释剂流312。在图3所示的实施方案中，压缩机344耦合到轴杆324上，并且轴杆324旋转提供的机械能被用于驱动压缩机344。
压缩的稀释剂流312从压缩机344供给到燃烧器310，来帮助冷却燃烧器310。热气体流334作为压缩的稀释剂流312的再循环部分的封闭了组合的循环发电装置中的Brayton循环，产生半封闭的Brayton循环。
当空气306和燃料气体308连续供给到燃烧器310来保持燃烧方法时，连续除去至少一部分的压缩的稀释剂流312。例如一部分的稀释剂流312可以作为主要包括N2和CO2的气体混合物346来除去。
根据此处所述的实施方案，气体混合物346可以在它燃烧后从燃烧器310中抽出，并且用于驱动膨胀涡轮322。例如该气体混合物346可以以约2206千帕(kPa)和427℃从膨胀涡轮322中抽出。该气体混合物346然后使用冷却器348冷却，和任选的用于在HRSG 304内产生蒸汽332。
在气体混合物346已经在冷却器348内冷却后，气体混合物346流入甲烷回收系统350。甲烷回收系统350包括注入系统，用于将该气体混合物346注入甲烷水合物地岩层中。当气体混合物346注入甲烷水合物地岩层时，该气体混合物346使得甲烷352从甲烷水合物中释放，并且经由甲烷回收系统350回收。
具体的，在一些实施方案中，将该气体混合物346以这样的压力注入甲烷水合物地岩层中，该压力低于该气体混合物346的水合物地岩层压力。在这样的实施方案中，因为气体混合物346具有比甲烷更高的水合物地岩层压力，因此该气体混合物346增加了甲烷水合物的温度，这使得甲烷352从甲烷水合物中逸出。在其它实施方案中，气体混合物346是以这样的压力注入甲烷水合物地岩层中，该压力高于气体混合物346的水合物地岩层压力。在这样的实施方案中，因为二氧化碳具有比甲烷低的水合物地岩层压力，因此气体混合物346内的二氧化碳优先代替甲烷水合物中的甲烷352，这使得甲烷352与甲烷水合物地岩层分离。
所释放的甲烷352然后经由甲烷回收系统350泵送到地面。在各种实施方案中，甲烷352是作为最终的甲烷产品从系统300中开发的。此外，在一些实施方案中，至少一部分的甲烷352作为燃料气体308用于燃气涡轮发动机302。
图3的过程流程图并非意图表示系统300是包括图3所示的全部组分。此外，系统300可以包括图3未示出的任何数目的另外的组分，这取决于具体实施方案的细节。
在各种实施方案中，离开图3的系统300的组合的循环发电装置的气体混合物346包括约89％的氮气和11％的二氧化碳。在一些情况中，期望的是在气体混合物346注入甲烷水合物地岩层中之前，调整该气体混合物中氮气与二氧化碳的比率，如涉及图4所讨论的。
图4是显示了作为温度，压力和氮气摩尔分数的N2/CO2水合物地岩层曲线的图400。图400的x轴402代表摄氏度温度(℃)，其中温度值是-20℃到15℃。图400的y轴404代表磅/平方英寸的绝对压力(psia)，其中压力值是0psi(0kPa)-5000psi(34474kPa)。
图4所示的每个水合物地岩层曲线代表气体混合物346在具体氮气摩尔分数时的水合物地岩层特性。氮气摩尔分数是气体混合物346中氮气的摩尔除以气体混合物346中氮气和二氧化碳的摩尔总和，即，该气体的总摩尔。水合物地岩层曲线406代表氮气摩尔分数为0.9。水合物地岩层曲线408代表氮气摩尔分数为0.8。水合物地岩层曲线410代表氮气摩尔分数为0.7。水合物地岩层曲线412代表氮气摩尔分数为0.6。水合物地岩层曲线414代表氮气摩尔分数为0.5。水合物地岩层曲线416代表氮气摩尔分数为0.4。水合物地岩层曲线418代表氮气摩尔分数为0.3。水合物地岩层曲线420代表氮气摩尔分数为0.2。水合物地岩层曲线422代表氮气摩尔分数为0.1，和水合物地岩层曲线424代表氮气摩尔分数为0。通过对比，水合物地岩层曲线426代表纯甲烷。
如图4所示，调整气体混合物346的氮气摩尔分数允许调整气体混合物346的水合物地岩层特性，这与甲烷的水合物地岩层特性形成对比。氮气的水合物地岩层压力高于甲烷的水合物地岩层压力，而二氧化碳的水合物地岩层压力低于甲烷的水合物地岩层压力。此外，对于气体混合物346的水合物地岩层压力来说，高于或低于甲烷的水合物地岩层压力是令人期望的，这取决于具体实施方案的细节。所以，气体混合物346的氮气摩尔分数可以基于期望的气体混合物346的水合物地岩层压力来增加或者降低。
图5是将低排放的发电与从甲烷水合物回收甲烷相整合的另一系统500的过程流程图。相同的附图标记如涉及图3的系统300所述。图5的系统500类似于图3的系统300。但是，根据图5的系统500，将气体混合物346中的二氧化碳和氮气分别注入甲烷水合物地岩层中。
根据图5的系统500，在气体混合物346已经在冷却器348中冷却后，该气体混合物346流入分离系统502中。分离系统502将气体混合物346中的二氧化碳504与氮气506分离。在一些实施方案中，分离系统502经由CO2分离工艺，例如诸如胺分离方法或者碳酸钾分离工艺来完成这样的分离。
然后二氧化碳504和氮气506可以作为分开的流流入甲烷回收系统350中。甲烷回收系统350可以包括注入系统，用于分别将二氧化碳504和氮气506注入甲烷水合物地岩层中，或者可以混合两种流504和506到目标浓度。在二氧化碳504和氮气506注入甲烷水合物地岩层时，二氧化碳504和氮气506使得甲烷352从甲烷水合物中释放和经由甲烷回收系统350回收。具体的，因为氮气具有比甲烷更高的水合物地岩层压力，因此氮气506增加了甲烷水合物的温度，使得甲烷352更容易的从甲烷水合物中逸出。另外，因为二氧化碳具有比甲烷低的水合物地岩层压力，因此二氧化碳504优先取代甲烷水合物中的甲烷352，这使得甲烷352与甲烷水合物分离。
图5的过程流程图并非意图表示系统500是包括图5所示的全部组分。此外，系统500可以包括图5未示出的任何数目的另外的组件，这取决于具体实施方案的细节。
图6是管线构造600的透视图，其用于从甲烷水合物地岩层中回收甲烷。管线构造600包括注入管线602，用于将二氧化碳和氮气注入甲烷水合物地岩层中，如箭头604所示。管线构造600还包括生产管线606，用于从甲烷水合物中回收甲烷，如箭头608所示。根据图6所示的实施方案，注入管线602和生产管线606在北到南和东到西二者运行。
在一些实施方案中，经由注入管线602将二氧化碳和氮气注入甲烷水合物地岩层中引起了甲烷水合物地岩层中的甲烷释放。所释放的甲烷然后在生产管线606的方向上移动，如箭头610所示，并且经由生产管线606回收。
图7是用于从甲烷水合物地岩层中回收甲烷的另一管线构造700的透视图。管线构造700包括注入管线702，用于将二氧化碳和氮气注入甲烷水合物地岩层中，如箭头704所示。管线构造700还包括生产管线706，用于从甲烷水合物中回收甲烷，如箭头708所示。根据图7所示的实施方案，注入管线702和生产管线706每个包括多个分支，其在北到南和东到西二者运行。
当二氧化碳和氮气经由注入管线702注入甲烷水合物地岩层中时，二氧化碳和氮气可以移动通过甲烷水合物地岩层，如箭头710所示。这会引起甲烷水合物地岩层中的甲烷释放。所释放的甲烷然后可以在生产管线706的方向上移动，如箭头712所示，并且经由生产管线706回收。
图6和7的图示并非意图表示图6和7所示的管线构造600和700仅仅是此处所述的实施方案中可以使用的管线构造。而是根据此处所述的实施方案，可以使用任何合适类型的管线构造，其提供来将分布甲烷水合物地岩层中的氮气和二氧化碳和从甲烷水合物地岩层中回收甲烷。例如在一些实施方案中，图6和7的管线构造600和700每个包括两个注入管线602和702，用于将二氧化碳和氮气分别注入甲烷水合物地岩层中。
用于发电和从甲烷水合物回收甲烷的方法
图8是方法800的一个过程流程图，用于发电和从甲烷水合物中回收甲烷。方法800可以通过涉及图2、3和5所述的任何一个的系统200，300或500来执行。此外，方法800可以通过涉及图2、3和5所述的系统200，300或500的任何变体来执行，或者通过能够将发电与从甲烷水合物中回收甲烷相整合的任何合适的可选择的系统来执行。此外，方法800可以在包括甲烷水合物地岩层的永久冻土环境例如诸如北极、亚北极地区或者南极来进行。
方法800开始于块802，在此处经由低排放的发电装置来发电。来自该低排放的发电装置的废气提供包括氮气和二氧化碳的气体混合物。
在各种实施方案中，经由该低排放的发电装置发电包括经由燃气涡轮发动机的膨胀涡轮，使用在气体混合物于燃烧器中燃烧后，从该气体混合物提取的能量来提供机械能，并且经由发电机使用由该膨胀涡轮提供的机械能来发电。此外，在各种实施方案中，经由该低排放的发电装置发电还包括经由HRSG，通过用来自膨胀涡轮的排出流加热锅炉来产生蒸汽，经由蒸汽涡轮，使用从HRSG产生的蒸汽提取的能量来提供机械能，和经由发电机，使用蒸汽涡轮提供的机械能来发电。在一些实施方案中，使用一个共用发电机，由膨胀涡轮和蒸汽涡轮提供的机械能来发电，而在其它实施方案中，使用分别的发电机。
在块804处，甲烷是通过将来自该气体混合物的氮气和二氧化碳注入甲烷水合物中以从甲烷水合物回收的。在一些实施方案中，该气体混合物被分离成二氧化碳和氮气，并且二氧化碳和氮气分别注入甲烷水合物中。在其它实施方案中，该气体混合物注入甲烷水合物中，并且没有从该气体混合物的二氧化碳中分离氮气。在一些情况中，在将该气体混合物注入甲烷水合物之前，调整该气体混合物中氮气与二氧化碳的比率。例如可以调整该气体混合物的氮气摩尔分数，如涉及图4所讨论的。
在一些实施方案中，至少一部分的回收的甲烷是作为燃料用于该低排放的发电装置的燃烧器的。此外在一些实施方案中，回收的甲烷是经由分离设施净化，来除去与甲烷一起回收自甲烷水合物的任何杂质。这样的杂质可以包括来自例如甲烷水合物的水或者来自周围永久冻土的土壤。
图8的过程流程图并非意图表示方法800的步骤是以任何具体次序进行的，或者在每种情况中包括方法800的全部步骤。此外，任何数目的另外的步骤可以包括在方法800内，这取决于具体实施方案的细节。例如在一些实施方案中，该气体混合物中的氮气和二氧化碳是在注入甲烷水合物中之前冷却。这可以防止氮气和二氧化碳通过接触来熔融所述甲烷水合物。

Claims (25)

1.一种用于发电和从甲烷水合物中回收甲烷的系统，其包含：
配置成发电的低排放的发电装置，其中来自该低排放的发电装置的废气提供包含氮气和二氧化碳的气体混合物；和
甲烷回收系统，其配置成通过将来自该气体混合物的氮气和二氧化碳注入到甲烷水合物中以从甲烷水合物中回收甲烷。
2.权利要求1的系统，其包括二氧化碳分离系统，该二氧化碳分离系统配置成将氮气与所述气体混合物中的二氧化碳分离。
3.权利要求2的系统，其中该甲烷回收系统配置成通过将二氧化碳和氮气分别注入到甲烷水合物中以从甲烷水合物中回收甲烷。
4.权利要求1或2中任一项的系统，其中该甲烷回收系统配置成在不将氮气与所述气体混合物中的二氧化碳分离的情况下通过将包含二氧化碳和氮气的气体混合物注入到甲烷水合物中以从甲烷水合物中回收甲烷。
5.权利要求1、2或4中任一项的系统，其中该甲烷回收系统配置成在将该气体混合物注入甲烷水合物中之前，调整该气体混合物中氮气与二氧化碳的比率。
6.权利要求1、2、4或5中任一项的系统，其中该低排放的发电装置包含：
膨胀涡轮，其配置成在该气体混合物在燃烧器中燃烧之后，通过提取来自该气体混合物的能量来提供机械能；和
发电机，其配置成由该膨胀涡轮提供的机械能来发电。
7.权利要求6的系统，其中从该甲烷水合物回收的甲烷的至少一部分作为燃料流入该燃烧器中。
8.权利要求1、2或者4-6中任一项的系统，其中该低排放的发电装置包含组合的循环发电装置。
9.权利要求8的系统，其中该组合的循环发电装置包含：
膨胀涡轮，其配置成在该气体混合物在燃烧器中燃烧之后，通过提取来自该气体混合物的能量来提供机械能；
热回收蒸汽发生器(HRSG)，其配置成通过用来自膨胀涡轮的排出流加热锅炉来产生蒸汽；
蒸汽涡轮，其配置成通过从HRSG产生的蒸汽提取能量来提供机械能；和
发电机，其配置成由膨胀涡轮和蒸汽涡轮提供的机械能来发电。
10.权利要求9的系统，其中从该甲烷水合物回收的甲烷的至少一部分作为燃料流入该燃烧器中。
11.权利要求1、2、4-6或者8中任一项的系统，其中一部分的该气体混合物再循环到该低排放的发电装置。
12.权利要求1、2、4-6、8或11中任一项的系统，其包含用于在将来自该气体混合物的二氧化碳和氮气注入甲烷水合物中之前冷却该气体混合物的冷却器。
13.权利要求1、2、4-6、8、11或12中任一项的系统，其中该低排放的发电装置配置成以基本上化学计量比平衡的条件来运行，其中至少一部分的该废气再循环到该低排放的发电装置。
14.一种用于发电和从甲烷水合物中回收甲烷的方法，其包括：
经由低排放的发电装置发电，其中来自该低排放的发电装置的废气提供包含氮气和二氧化碳的气体混合物；和
通过将来自该气体混合物的氮气和二氧化碳注入到甲烷水合物中以从甲烷水合物中回收甲烷。
15.权利要求14的方法，其包括：
将该气体混合物分离成二氧化碳和氮气；和
将该二氧化碳和氮气分别注入甲烷水合物中。
16.权利要求14或15中任一项的方法，其包括在不将二氧化碳与该气体混合物中的氮气分离的情况下将该气体混合物注入甲烷水合物中。
17.权利要求16的方法，其包括在将该气体混合物注入甲烷水合物中之前，调整该气体混合物中氮气与二氧化碳的比率。
18.权利要求14-16中任一项的方法，其中经由该低排放的发电装置发电包括：
在该气体混合物在燃烧器中燃烧后，经由膨胀涡轮使用提取自该气体混合物的能量来提供机械能；和
经由发电机，使用该膨胀涡轮提供的机械能来发电。
19.权利要求18的方法，其包括将从甲烷水合物回收的甲烷的至少一部分作为燃料流入该燃烧器中。
20.权利要求14-16或18中任一项的方法，其中经由该低排放的发电装置发电包括：
在该气体混合物在燃烧器中燃烧后，经由膨胀涡轮使用提取自该气体混合物的能量来提供机械能；和
经由热回收蒸汽发生器(HRSG)，通过用来自该膨胀涡轮的排出流加热锅炉来产生蒸汽；
经由蒸汽涡轮，使用从HRSG产生的蒸汽提取的能量来提供机械能；和
经由发电机，使用由膨胀涡轮和蒸汽涡轮提供的机械能来发电。
21.权利要求20的方法，其包括将从甲烷水合物回收的甲烷的至少一部分作为燃料流入该燃烧器中。
22.权利要求14-16、18或20中任一项的方法，其中通过将来自该气体混合物的氮气和二氧化碳注入到甲烷水合物中以从甲烷水合物中回收甲烷包括：
通过将该甲烷水合物与氮气接触来升高该甲烷水合物的温度；和
通过将该甲烷水合物与二氧化碳接触以从该甲烷水合物解离甲烷，其中该二氧化碳替换了该甲烷水合物中的甲烷。
23.权利要求14-16、18、20或22中任一项的方法，其包括从回收自甲烷水合物的甲烷中除去杂质。
24.一种用于使用来自组合的循环发电装置的气体混合物从甲烷水合物中回收甲烷的系统，其包含：
膨胀涡轮，其配置成通过从离开燃烧器的气体混合物提取能量来提供机械能，其中该气体混合物包含氮气和二氧化碳；
热回收蒸汽发生器(HRSG)，其配置成通过用来自膨胀涡轮的气体混合物加热锅炉来产生蒸汽；
蒸汽涡轮，其配置成通过从HRSG产生的蒸汽提取能量来提供机械能；
发电机，其配置成由膨胀涡轮和蒸汽涡轮提供的机械能来发电；
分离系统，其配置成从该气体混合物的甲烷中分离二氧化碳；和
甲烷回收系统，其配置成通过将来自该气体混合物的氮气和二氧化碳注入到甲烷水合物中以从甲烷水合物中回收甲烷，其中从该甲烷水合物回收的甲烷的至少一部分作为燃料流入该燃烧器中。
25.权利要求24的系统，其中该膨胀涡轮配置成以基本上化学计量比平衡的条件来运行，其中将至少一部分的该气体混合物再循环到燃烧器。
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