CN107108233B - 从发电系统和方法生产低压液态二氧化碳 - Google Patents
从发电系统和方法生产低压液态二氧化碳 Download PDFInfo
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- CN107108233B CN107108233B CN201580057985.4A CN201580057985A CN107108233B CN 107108233 B CN107108233 B CN 107108233B CN 201580057985 A CN201580057985 A CN 201580057985A CN 107108233 B CN107108233 B CN 107108233B
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Abstract
本公开涉及提供低压液态CO2流的系统和方法。特别地,本公开提供了以下系统和方法:其中高压CO2流(诸如,来自主要使用CO2作为工作流体的发电过程的再循环CO2流)可被分开以使得其一部分可被膨胀并用作热交换器中的冷却流以冷却高压CO2流的剩余部分,后者随后可被膨胀以形成低压CO2流,所述低压CO2流可为含有CO2蒸汽的混合形式。所述系统和方法可用于提供易于运输的液体形式的来自燃烧的净CO2。
Description
技术领域
本文所公开的主题涉及生产液态二氧化碳的系统和方法。具体而言,液态二氧化碳可为由在发电系统和方法(特别是使用二氧化碳作为工作流体的系统和方法)中生产的二氧化碳形成的低压二氧化碳流。
背景技术
碳捕获和封存(CCS)是生产二氧化碳(CO2)的任何系统或方法的关键考虑因素。这与通过燃烧化石燃料或其它含碳氢材料的发电特别相关。已提出若干能够实现CCS的发电方法。具有CCS的高效发电领域中的一篇出版物,Allam等人的第8,596,075号美国专利,提供了利用再循环CO2流在闭环氧-燃料燃烧系统中的理想效率。在这种系统中,CO2在高压下被捕获为相对纯的流。
目前关于CO2处理的建议通常需要在高压管线中作为100巴(10MPa)至250巴(25MPa)压力下的高密度超临界流体来输送。这种管线需要高资本支出。经管道输送的CO2被封存在地下地质层,诸如深层盐水层中,或者可用于经济价值,诸如用于提高采油率(EOR)。
将CO2用于EOR需要其在大面积富油地区上可用。这将需要广泛使用在整个地区延伸的管网。这在许多用途中,特别是在离岸油田中变得非常昂贵。因此,有用的是提供易于递送至离岸采油平台的液体形式的大量CO2(诸如由发电系统和方法所生产的)。如果CO2能够以液化形式提供,则可设想从发电设施收集的CO2的其他有益用途。
发明内容
本公开提供了可用于生产液态CO2的系统和方法。所公开的系统和方法可使用来自任何来源的CO2。然而,当与产生高压CO2流、特别是近环境温度的高压CO2流的系统和方法相关时,所述系统和方法可能是特别有利的。本发明的系统和方法的有利之处还在于可生产非常高纯度的液态CO2,特别是具有低水平的氧气、氮气和稀有气体(例如,氩气)。
在某些实施方式中,可用于生产液态CO2的CO2源可为发电系统(特别是氧燃料(oxyfuel)燃烧系统)和发电方法(更具体而言,使用CO2工作流体的燃烧方法)。可从其获得CO2流的发电系统和方法在以下文献中描述:第8,596,075号美国专利、第8,776,532号美国专利、第8,959,887号美国专利、第8,986,002号美国专利、第9,068,743美国专利、第2010/0300063号美国专利申请公开、第2012/0067054号美国专利申请公开、第2012/0237881号美国专利申请公开和第2013/0213049号美国专利申请公开,这些文件以其全部内容通过引用并入本文。
在一些实施方式中,本公开涉及生产低压液态二氧化碳(CO2)流的方法。该方法可包括提供压力为约60巴(6MPa)或更高、约100巴(10MPa)或更高或者在如本文另外公开的压力范围内的高压CO2流。所述方法还可包括分出(divide out)高压CO2流的一部分并使该部分膨胀以形成可用作制冷剂的冷却流。例如,所述冷却流可处于约-20℃或更低的温度或在本文另外公开的温度范围内。所述方法还可包括通过将高压CO2流与冷却流成热交换关系地通过热交换器来将高压CO2流冷却至约5℃或更低(优选约-10℃或更低)的温度。所述方法还可包括膨胀高压CO2流以形成压力低至约6巴(0.6MPa)的低压CO2流。所述方法还可包括使低压CO2流通过能有效地从其中分离蒸汽流并提供低压液态CO2流的分离器。
在另外的实施方式中,本公开涉及可用于生产低压液态二氧化碳(CO2)流的系统。在一些实施方式中,这样的系统可包括一个或多个适于提供高压CO2流的组件、一个或多个热交换器、一个或多个膨胀器(例如,阀)、一个或多个分离器以及一个或多个蒸馏器。在非限制性实例中,根据本公开的系统可包括:适于高压CO2流通过的管道;适于将高压CO2流分成冷却部分和主体流的分配器;适于膨胀和冷却高压CO2流的冷却部分的膨胀器;适于用经加温膨胀(warming expanded)和冷却的高压CO2流的冷却部分来冷却主体高压CO2流的热交换器;适于膨胀和冷却主体高压CO2流以形成两相低压CO2流的膨胀器;适于从两相低压CO2流中去除蒸汽部分的分离器;以及适于去除至少一部分非CO2组分并提供低压液态CO2流的蒸馏器。
在仍然其它实施方式中,本公开涉及从来自发电过程的高压CO2流生产低压液态二氧化碳(CO2)流的方法。在一些实施方式中,该方法可包括在约100巴(10MPa)或更高的压力和约400℃或更高的温度在氧气和再循环CO2流存在下在燃烧器中燃烧碳质或碳氢燃料,以形成包含CO2的燃烧器出口流。燃烧器出口流特别地可处于约200巴(20MPa)至约400巴(40MPa)的压力。燃烧器出口流特别可处于约800℃至约1,600℃的温度。所述方法还可包括在涡轮机中膨胀燃烧器出口流以发电并形成压力为约50巴(5MPa)或更低的包含CO2的涡轮机出口流。涡轮机出口流特别地可处于约20巴(2MPa)至约40巴(4MPa)的压力。所述方法还可包括在热交换器中冷却涡轮机出口流,热传递到加热再循环CO2流中。冷却可至约80℃或更低的温度,诸如近环境温度。所述方法还可包括用环境冷却装置进一步冷却涡轮机排气流并在分离器中分离冷凝水。所述方法还可包括将CO2从涡轮机出口压力泵压至约100巴(10MPa)或更高的压力以形成高压CO2流。特别地,高压CO2流可处于约100巴(10MPa)至约500巴(50MPa)或者约200巴(20MPa)至约400巴(40MPa)的压力。来自经冷却的涡轮机出口流的CO2可被压缩到第一压力,冷却以提高其密度,然后被泵压到上述范围内的第二较高压力。高压CO2流的一部分可在返回到燃烧器中之前被返回通过热交换器以用冷却涡轮机出口流加热。还可在压缩之后和通入燃烧器之前对所述流施加进一步加热,诸如用来自非涡轮机出口流的来源的进一步加热。高压CO2流的一部分(该部分可包含在燃烧中产生的任何净CO2)可被冷却至约5℃或更低的温度,例如在使用制冷剂的热交换器中。制冷剂可包括高压CO2流的一部分,其可以通过将该部分膨胀至约30巴(3MPa)或更低但高于CO2三相点压力的压力而被用作冷却部分。冷却部分可处于约0℃或更低或者约-20℃或更低的温度。在特定实施方式中,高压CO2流的冷却部分可被冷却至约-55℃至约0℃的温度。在热交换器中用CO2冷却部分冷却的高压CO2流的部分以被膨胀至低至约6巴(0.6MPa)的压力(优选始终保持高于CO2三相点压力的压力),以形成低压液态CO2流。特别地,经冷却的高压CO2流的部分可被膨胀至约30巴(3MPa)或更低但高于CO2三相点压力的压力。
如上所述的方法还可包括其它元件。例如,涡轮机出口流的冷却特别地可达到约70℃或更低或者约60℃或更低的温度。可使用一个热交换器或多个热交换器。例如,可使用节能热交换器,之后是冷水热交换器。在冷却之后,所述方法还可包括将包含CO2的涡轮机出口流通过一个或多个分离器以从其中去除至少水。此外,在所述泵压步骤之前,所述方法可包括将包含CO2的涡轮机出口流压缩至至多约80巴(8MPa)的压力(例如,约60巴(6MPa)至约80巴(8MPa)的压力)。此外,所述方法可包括提高包含CO2的涡轮机出口流的密度,诸如通过在冷水热交换器中冷却所述流。例如,密度可被提高到约600kg/m3或更大,约700kg/m3或更大,或约800kg/m3或更大。涡轮机出口流可在增加流密度之前压缩。
所述方法还可包括,在主体高压CO2流于热交换器中的所述冷却之后并于所述膨胀之前,使主体高压CO2流通过再沸器。再沸器可特别地与蒸馏器(例如,汽提塔)组合。因此,再沸器可向蒸馏器提供加热。
所述方法可包括对主体低压液态CO2流的进一步处理。例如,低压液态CO2流可为包含液相和汽相的两相材料。因此,所述方法可包括使低压液态CO2流通过能从其中有效分离蒸汽流的分离器。在一些实施方式中,蒸汽流可占通过分离器的低压液态CO2流的至多约8wt%(特别是,至多约4wt%或至多约6wt%)。在一些实施方式中,蒸汽流可包含约1wt%至约75wt%的CO2。在一些实施方式中,蒸汽流可包含约25wt%至约99wt%的N2、O2和氩(或其它惰性气体)的组合。所述方法还可包括将剩余的低压液态CO2流(例如,在从其中提取汽相之后)通过蒸馏器,诸如汽提塔(其可包括再沸器,如上所述)。
在蒸馏步骤之后,可将液态CO2提供至泵以将其压力增加到期望值。来自泵的冷排出流可被供应到再沸器上游的热交换器,以补充被膨胀以产生制冷剂的高压CO2的冷却负荷。加温(warmed)的制冷剂CO2和/或来自汽提蒸馏塔的塔顶流可被提供至压缩机,该压缩机以与高压CO2流所来源的系统相容的压力排出流。来自分离器的汽相流也可被提供至实施附加分离过程的系统。或者,汽相流可被排出。
根据本公开提供的低压液态CO2流特别地可仅具有非常低的氧浓度。在一些实施方式中,低压液态CO2流可具有不超过约25ppm的氧含量,特别是不超过约10ppm。低压液态CO2流也可以具有类似低浓度的惰性气体,诸如氮气和氩气。
作为非限制性实例,本公开可以涉及以下实施方式。这样的实施方式旨在说明整个公开内容的更广泛的性质。
在一些实施方式中,本公开可提供生产低压液态CO2流的方法。例如,该方法可包括:在约100巴(100MPa)或更高的压力和约400℃或更高的温度以及在再循环CO2流存在下在燃烧器中用氧气燃烧碳质或碳氢燃料,以形成包含CO2的燃烧器出口流;在涡轮机中膨胀燃烧器出口流以发电并形成压力为约50巴(5MPa)或更低的包含CO2的涡轮机出口流;在第一热交换器中冷却涡轮机出口流以形成经冷却的涡轮机出口流;将来自经冷却的涡轮机出口流的CO2泵压至约100巴(10MPa)或更高的压力以形成高压CO2流;将高压CO2流分为主体部分和冷却部分;膨胀高压CO2流的冷却部分以将其温度降低至约-20℃或更低;通过将高压CO2流的主体部分通过第二热交换器用经膨胀的高压CO2流的冷却部分来将高压CO2流的主体部分冷却至约5℃或更低的温度;并且将经冷却的高压CO2流的主体部分膨胀至约30巴(3MPa)或更低但高于CO2三相点压力的压力,从而形成低压液态CO2流。在另外的实施方式中,该方法可包括以下陈述中的一个或多个,这些陈述可以任何数量和任何组合而组合。此外,该方法可包括本文另外描述的任何其它元件。
燃烧器出口流可处于约200巴(20MPa)至约400巴(40MPa)的压力。
燃烧器出口流可处于约800℃至约1,600℃的温度。
包含CO2的涡轮机出口流可处于约20巴(2MPa)至约40巴(4MPa)的压力。
涡轮机出口流可在热交换器中冷却至约80℃或更低的温度。
所述方法还可包括使经冷却的包含CO2的涡轮机出口流通过一个或多个分离器以从其中去除至少水。
所述方法还可包括在热交换器中用涡轮机出口流加热氧气和再循环CO2流中的一种或两种。
高压CO2流可处于约200巴(20MPa)至约400巴(40MPa)的压力。
高压CO2流的主体部分可被冷却至约-55℃至约0℃的温度。
所述方法还可包括在高压CO2流的主体部分的冷却之后并且在高压CO2流的主体部分的膨胀之前,使高压CO2流的主体部分通过再沸器。
再沸器可在汽提塔中。
所述方法还可包括使低压液态CO2流通过能有效地从其中分离蒸汽流的分离器。
蒸汽流可占通过分离器的低压液态CO2流的至多约8wt%。
蒸汽流可包含约1wt%至约75wt%的CO2和约25wt%至约99wt%N2、O2和氩气中的一种或多种。
所述方法还可包括将剩余的低压液态CO2流通入汽提塔。
离开汽提塔的低压液态CO2流可具有不超过约25ppm的的氧含量。
所述方法可包括将低压液态CO2流泵压至至少约100巴(10MPa)的压力。
所述方法可包括将经泵压的液态CO2流输送到CO2管线。
所述方法还可包括将来自汽提塔的塔顶蒸汽与离开第二热交换器的高压CO2流的冷却部分相混合。
所述方法还可包括将来自汽提塔的塔顶蒸汽和离开第二热交换器的高压CO2流的冷却部分的混合物添加到经冷却的涡轮机出口流中。
在另外的示例性实施方式中,本公开可提供设置用于生产低压液态CO2流的系统。例如,所述系统可包括:分流器,其设置为将高压CO2流分成第一部分和第二部分;第一膨胀器,其被设置用于膨胀和冷却高压CO2流的第一部分;热交换器,其用于将高压CO2流的第二部分用离开膨胀器的经冷却的高压CO2流的第一部分冷却;以及第二膨胀器,其被设置用于膨胀经冷却的高压CO2流的第二部分以形成低压液态CO2流。在另外的实施方式中,这样的系统可包括以下陈述中的一个或多个,这些陈述可以以任何数量和任何组合而组合。此外,这种系统可包括本文另外描述的任何其它元件。
第一膨胀器可被设置用于将高压CO2流的第一部分冷却至约-20℃或更低的温度。
热交换器可被设置用于将高压CO2流的第二部分冷却至约5℃或更低的温度。
第二膨胀器可设置为将经冷却的高压CO2流的第二部分膨胀至约30巴(3MPa)或更低但高于CO2三相点压力的压力。
所述系统还可包括组合的汽提塔和再沸器。
汽提塔可连接在第二膨胀器的下游,并且再沸器可连接在热交换器的下游和第二膨胀器的上游。
所述系统还可包括位于第二膨胀器下游和汽提塔上游的液/汽分离器。
所述系统还可包括压缩机,其被设置用于接收来自热交换器的高压CO2流的第一部分。
所述系统还可包括:燃烧器,其被设置用于在约100巴(10MPa)或更高的压力和约400℃或更高的温度在再循环CO2流的存在下在燃烧器中燃烧碳质或碳氢燃料,以形成包含CO2的燃烧器出口流;涡轮机,其被设置用于膨胀燃烧器出口流以发电并形成包含CO2的涡轮机出口流;另外的热交换器(further heat exchanger),其被设置用于冷却涡轮机出口流;以及泵,其被设置用于从泵压来自经冷却的涡轮机出口流的CO2以形成高压CO2流。
所述发明包括以下实施方式,但不限于此。
实施方式1:生产低压液态二氧化碳(CO2)流的方法,所述方法包括:在约100巴(10MPa)或更高的压力和约400℃或更高的温度以及在再循环CO2流的存在下,在燃烧器中用氧气燃烧碳质或碳氢燃料以形成包含CO2的燃烧器出口流;在涡轮机中膨胀燃烧器出口流以发电并形成压力为约50巴(5MPa)或更低的包含CO2的涡轮机出口流;在第一热交换器中冷却涡轮机出口流以形成经冷却的涡轮机出口流;将来自经冷却的涡轮机出口流的CO2泵压至约100巴(10MPa)或更高的压力以形成高压CO2流;将高压CO2流分成主体部分和冷却部分;膨胀高压CO2流的冷却部分以将其温度降低至约-20℃或更低;通过使高压CO2流的主体部分通过第二热交换器用经膨胀的高压CO2流的冷却部分的第二热交换器将高压CO2流的主体部分冷却至约5℃或更低的温度;并将经冷却的高压CO2流的主体部分膨胀到约30巴(3MPa)或更低但高于CO2三相点压力的压力,以形成低压液态CO2流。
实施方式2:任何前述或后续实施方式的方法,其中燃烧器出口流处于约200巴(20MPa)至约400巴(40MPa)的压力。
实施方式3:任何前述或后续实施方式的方法,其中燃烧器出口流处于约800℃至约1,600℃的温度。
实施方式4:任何前述或后续实施方式的方法,其中包含CO2的涡轮机出口流处于约20巴(2MPa)至约40巴(4MPa)的压力。
实施方式5:任何前述或后续实施方式的方法,其中涡轮机出口流在热交换器中被冷却至约80℃或更低的温度。
实施方式6:任何前述或后续实施方式的方法,还包括使包含CO2的冷却涡轮机出口流通过一个或多个分离器以从其去除至少水。
实施方式7:任何前述或后续实施方式的方法,还包括在热交换器中用涡轮机出口流加热氧气和再循环CO2流中的一种或两种。
实施方式8:任何前述或后续实施方式的方法,其中高压CO2流处于约200巴(20MPa)至约400巴(40MPa)的压力。
实施方式9:任何前述或后续实施方式的方法,其中高压CO2流的主体部分被冷却至约-55℃至约0℃的温度。
实施方式10:任何前述或后续实施方式的方法,还包括在高压CO2流的主体部分的所述冷却之后和在高压CO2流的主体部分的所述膨胀之前,使高压CO2流的主体部分通过再沸器。
实施方式11:任何前述或后续实施方式的方法,其中再沸器在汽提塔中。
实施方式12:任何前述或后续实施方式的方法,还包括使低压液态CO2流通过能有效地从其中分离蒸汽流的分离器。
实施方式13:任何前述或后续实施方式的方法,其中蒸汽流占通过分离器的低压液态CO2流的至多约8wt%。
实施方式14:任何前述或后续实施方案的方法,其中蒸汽流包含约1wt%至约75wt%的CO2和约25wt%至约99wt%的N2、O2和氩气中的一种或多种。
实施方式15:任何前述或后续实施方式的方法,还包括将剩余的低压液态CO2流通入汽提塔。
实施方式16:任何前述或后续实施方式的方法,其中离开汽提塔的低压液态CO2流具有不超过约25ppm的氧含量。
实施方式17:任何前述或后续实施方式的方法,包括将低压液态CO2流泵压至至少约100巴(10MPa)的压力。
实施方式18:任何前述或后续实施方式的方法,包括将经泵压的液态CO2流输送到CO2管线。
实施方式19:任何前述或后续实施方式的方法,还包括将来自汽提塔的塔顶蒸汽与离开第二热交换器的高压CO2流的冷却部分相混合。
实施方式20:任何前述实施方式的方法,还包括将混合物加入到经冷却的涡轮机出口流中。
实施方式21:设置用于生产低压液态二氧化碳(CO2)流的系统,所述系统包括:分流器,其被设置用于将高压CO2流分成第一部分和第二部分;第一膨胀器,其被设置用于膨胀和冷却高压CO2流的第一部分;热交换器,其用于用离开膨胀器的经冷却的高压CO2流的第一部分来冷却高压CO2流的第二部分;以及第二膨胀器,其被设置用于使经冷却的高压CO2流的第二部分膨胀以形成低压液态CO2流。
实施方式22:任何前述或后续实施方式的系统,其中第一膨胀器被设置用于将高压CO2流的第一部分冷却至约-20℃或更低的温度。
实施方式23:任何前述或后续实施方式的系统,其中热交换器设置为将高压CO2流的第二部分冷却至约5℃或更低的温度。
实施方式24:任何前述或后续实施方式的系统,其中第二膨胀器设置为将经冷却的高压CO2流的第二部分膨胀至约30巴(3MPa)或更低但高于CO2三相点压力的压力。
实施方式25:任何前述或后续实施方式的系统,还包括组合的汽提塔和再沸器。
实施方式26:任何前述或后续实施方式的系统,其中汽提塔连接在第二膨胀器下游且其中再沸器连接在热交换器的下游和第二膨胀器的上游。
实施方式27:任何前述或后续实施方式的系统,还包括位于第二膨胀器下游和汽提塔上游的液/汽分离器。
实施方式28:任何前述或后续实施方式的系统,还包括设置为接收来自热交换器的高压CO2流的第一部分的压缩机。
实施方式29:任何前述实施方式的系统,还包括:燃烧器,其被设置用于在约100巴(10MPa)或更高的压力和约400℃或更高的温度以及在再循环CO2流的存在下在燃烧器中用氧气燃烧碳质或碳氢燃料,以形成包含CO2的燃烧器出口流;涡轮机,其被设置用于膨胀燃烧器出口流以发电并形成包含CO2的涡轮机出口流;另外的热交换器,其被设置用于冷却涡轮机出口流;以及泵,其被设置用于泵压来自经冷却的涡轮机出口流的CO2以形成高压CO2流。
通过阅读下面的详细描述以及下面将要简要描述的附图,本发明的这些和其它特征、方面和优点将变得显而易见。本发明包括上述实施方式中的两个、三个、四个或更多个的任何组合,以及本公开中阐述的任何两个、三个、四个或更多个特征或元件的组合,而不管这些特征或元件在本文的具体实施方式的描述中被明确地组合。除非上下文另有明确规定,本公开旨在整体地阅读,使得在其任何方面和实施方式中的任何本公开发明的任何可分离的特征或元件应被视为旨在可组合。
附图说明
现在将参考附图,其不一定按比例绘制,并且其中:
图1示出了根据本公开的实施方式的用于形成低压液态CO2流的系统的流程图;和
图2示出了根据本公开的实施方式的用于利用从发电过程取得的高压CO2流的一部分形成低压液态CO2流的系统的流程图。
具体实施方式
现在将在下文中参考其示例性实施方式更全面地描述本主题。描述这些示例性实施方式,使得本公开将是彻底和完整的,并且将向本领域技术人员充分传达主题的范围。实际上,主题可以以许多不同的形式实施,并且不应被解释为限于本文所阐述的实施方式;相反,提供这些实施方式使得本公开将满足适用的法律要求。如在说明书和所附权利要求中所使用,单数形式“一/一个/中(a或an)”、“所述/该(the)”包括复数指示物,上下文另有明确规定除外。
本公开涉及适用于生产低压液态二氧化碳(CO2)的系统和方法。所述系统和方法特别可适于引入包含非液态CO2(例如,气态CO2或超临界CO2)的流并将至少一部分非液态CO2转化为液态CO2。引入流可包括液态CO2部分;然而,引入流优选包含不超过约25wt%、不超过约10wt%、不超过约5wt%或不超过约2wt%的液态CO2。
根据本公开生产的液态CO2可在低压下生产,因为所生产的液态CO2的压力小于50巴(5MPa)但高于CO2三相点压力,以优选地避免固态CO2的大量形成。在一些实施方式中,所生产的液态CO2的压力可低至约6巴(0.6MPa)、特别是约30巴(3MPa)至约6巴(0.6MPa)、约25巴(2.5MPa)至约6巴(0.6MPa)或约15巴(1.5MPa)至约6巴(0.6MPa)。所产生的液态CO2的温度优选地在给定压力下的饱和温度的范围内。例如,温度可在约5℃至约-55℃、约-5℃至约-55℃或约-15℃至约-55℃的范围内。
根据本公开实施方式的生产液态CO2的方法通常可包括冷却和膨胀来自引入流的CO2。取决于引入流的来源,所述方法可包括一个或多个压缩步骤。在优选实施方式中,引入的CO2可处于约60巴(6MPa)或更高、约100巴(10MPa)或更高或约200巴(20MPa)或更高的压力。在其他实施方式中,引入的CO2的压力可处于约60巴(6MPa)至约400巴(40MPa)的范围内。引入的CO2的温度可高于10℃,或者可在约10℃至约40℃、约12℃至约35℃或约15℃至约30℃的范围内。在一些实施方式中,引入的CO2可处于约环境温度。
图1中示出了根据本公开的用于生产液态CO2的系统和方法的实施方式。如图所示,高压CO2流24可经由通过水冷却器50(根据高压CO2流的实际温度,其可为任选的)来冷却。然后使用分流器68(或设置用于分流的其它合适系统元件)将高压CO2流24分成第一部分和第二部分,以提供可被膨胀的高压CO2侧流57,诸如通过阀58或其他合适装置,以形成冷却CO2流56。剩余的高压CO2流62通过热交换器10,在那里其被冷却CO2流56冷却,后者作为CO2流33离开。离开热交换器10冷端的经冷却的高压CO2流51可处于约5℃或更低的温度、约0℃或更低、约-10℃或更低或者约-20℃或更低(例如,约5℃至约-40℃或约0℃至约-35℃)。经冷却的高压CO2流51可被膨胀以形成液态CO2流。如图1所示,经冷却的高压CO2流51首先通过再沸器52,再沸器52是图1中汽提塔53的一部分,从而为其中的蒸馏提供加热,这在下面进一步描述。因此通过再沸器可以是任选的。离开再沸器52的高压CO2流55被膨胀以形成处于上述范围内的温度和压力下的低压液态CO2流35。在图1中,流55通过阀48膨胀,但是可使用用于膨胀经压缩的CO2流的任何装置。例如,膨胀装置可为诸如涡轮机的工作生产系统,其降低入口和出口之间的CO2的焓,并进一步降低出口温度。
高压CO2流(例如,约60巴(6MPa)至约400巴(40MPa)范围内)膨胀以形成低压CO2流(例如,约30巴(3MPa)或大于CO2三相点压力的压力)可得到由具有与输入到阀(或其它膨胀装置)的CO2流相同的总焓的气和液混合物形成的两相产物流。离开阀(或者根据上文所述的示例性替代实施方式的涡轮机)的两相混合物的温度特别地可处于减压下的液体饱和温度。在图1中,离开阀58的流56和离开阀48的流35都可为两相流。离开阀48的两相低压CO2流35可通过分离器9以提供CO2蒸汽部分流49和CO2液态部分流36。
在其中输入高压CO2流来自氧燃烧发电系统的实施方式中,可从低压液态CO2流中分离的蒸汽部分将包含存在于氧源和燃料源(例如,天然气)中的大部分惰性气体(例如,氮气,过量的O2,和惰性气体,例如氩气)。作为非限制性实例,氧燃烧发电过程可用1%过量的氧气流进入燃烧器来实施,氧气流由近似99.5%的氧气和0.5%的氩气形成。得到的净CO2产物可包括2%浓度的O2和1%浓度的氩。
根据本发明,通过间接冷却装置将来自如上所例示的电力系统的CO2产物冷却至当通过阀膨胀至例如10巴(1MPa)的压力时的温度,这导致近似4%的闪蒸蒸汽(flashvapor)部分。在多个实施方式中,蒸汽部分可为总液态CO2流(例如,图1中的流35)的至多约6wt%、至多约5wt%或至多约4wt%。蒸汽流(例如,图1中的流49)可包含约1wt%至约75wt%的CO2和约25wt%至约99wt%的N2、O2和氩气(或其它惰性气体)的组合。在另外的实施方式中,蒸汽流可包含约60wt%或更多、约65wt%或更多或者约70wt%或更多的N2、O2和氩气(或其它惰性气体)的组合。闪蒸蒸汽部分(例如,图1中离开分离器9的流49)可被排放到大气中或被捕获。闪蒸蒸汽流的生产在其中输入CO2流来源于氧燃烧过程的实施方式中是有益的,因为蒸汽部分的去除将防止惰性氩气和/或氮气的积聚(其可存在于所燃烧的天然气和/或煤衍生燃料气中并且其可存在于源自低温空气分离随机设备的氧气流中)。为形成闪蒸蒸汽部分,有用的可以是在膨胀之前将高压CO2流(例如,图1中的流62)冷却至约-30℃或更低或者约-33℃或更低的温度。在其中输入高压CO2流来源于可能基本或完全不含惰性气体(和任选的氧气)的来源的实施方式中,可无需形成闪蒸蒸汽部分。在于氧-燃料发电生产过程中使用含有大量N2的天然气燃料的实施方案中,有用的可以是调节流51所被冷却到的温度,以确保去除流49中的主要N2以及O2和氩气,同时最少损失流49中的CO2。
优选地,来自输入CO2流的O2和氩气(和其它惰性气体)浓度的大部分在闪蒸蒸汽部分中被去除,使得CO2液态部分流(例如,图1中的流36)仅具有少量的N2、O2和氩气浓度-例如,约1wt%或更低、约0.5wt%或更低或者约0.2wt%或更低。可诸如通过使用蒸馏装置(例如,图1中的汽提塔53)从CO2液态部分流中脱除少量的N2、O2和氩气浓度。或者可替代图1所示,脱除部分可被装配在闪蒸分离器的下部。在利用汽提塔的实施方式中,可包括再沸器(如上所述的图1中的部件52)以从部分或全部的高压CO2流(例如,图1中的流51)中提取剩余的可用热。可改变这种加热以提供必要的液汽比,以降低净液态CO2产物(图1中的流54)中的氧浓度。净液态CO2流中的氧浓度可不超过约25ppm,不超过约20ppm,或不超过约10ppm。
在另外的实施方式中,可将产物液态CO2流54泵压到高压并在热交换器10(或在另外的热交换器中或通过另外的装置)中加热,以输送到CO2管线中。产物液态CO2流特别地可被泵压到约100巴(10MPa)至约250巴(25MPa)的压力。
返回到图1所示,离开汽提塔53的顶部产品63在需要时可被进一步降低压力,诸如在阀64中,然后与CO2流33合并。经合并的流可在压缩机34中被压缩以提供返回高压CO2流21,后者可例如与输入高压CO2流24合并或被添加到另外的含CO2流中(参见图2)。
前述用于形成低压液态CO2流的实施方式在经济上是理想的,因为净低压CO2流(例如,图1中的流35)中的约95wt%或更多、约96wt%或更多或约97wt%或更多的CO2可作为低压液态CO2流去除。在上述实施方式中,约1.5wt%至约2.5wt%的净CO2产物可与N2、O2和氩气合并流(例如,图1中的流49)一起排放到大气中,从而提供约97.5%至约98.5%的CO2去除效率。在其中上述方法与使用CO2作为工作流体的闭环电力系统联合执行的实施方式中,流49优选被排放到大气中,因为惰性组分的去除需要保持其分压和浓度尽可能低。任选地,流59在于阀60中减压之后可穿过热交换器10中的通道组,以在流59被排放之前提供用于冷却流62的额外制冷。
输入高压CO2流24的利用提供了向高压CO2流提供间接冷却的独特能力。如上述实施方式所述,间接冷却可通过在近环境温度分出高压CO2流的一部分,然后将该分出的高压CO2流的一部分膨胀至约-20℃或更低、约-30℃或更低或者约-40℃或更低(例如,近似-40℃至约-55℃)的温度。这可通过将高压CO2流24的压力降低至低于约20巴(2MPa)、低于约10巴(1MPa)或低于约8巴(0.8MPa)(例如,约20巴(2MPa)至约5巴(0.5MPa)或约12巴(1.2MPa)至约5巴(0.5MPa),特别是约5.55巴(0.555MPa))来实现。所得到的液加汽流(例如,图1中的流56)随后用于在热交换器中对主体高压CO2流进行间隔冷却。
当与利用CO2工作流体的发电方法结合使用时,本公开的系统和方法是特别有利的,诸如第8,596,075号美国专利,其公开内容通过引用整体并入本文。特别地,这种方法可使用膨胀高压再循环CO2流和由燃料燃烧产生的燃烧产物的混合物的高压/低压比涡轮机。可使用任何化石燃料,特别是碳质燃料。优选地,所述燃料是气体燃料;然而,非气体燃料不必被排除。非限制性实例包括天然气、压缩气体、燃料气体(例如,包括H2、CO、CH4、H2S和NH3中的一种或多种)和类似的可燃气体。还可使用固体燃料-例如煤、褐煤、石油焦炭、沥青等,同时加入必需的系统元件(诸如,使用部分氧化燃烧器或气化器来将固体或重质液态燃料转化为气体形式)。也可使用液态碳氢燃料。纯氧可用作燃烧过程中的氧化剂。热涡轮机排气用于部分预热高压再循环CO2流。再循环CO2流也使用源自CO2压缩机的压缩能的热来加热,如本文进一步所讨论的。所有燃料和燃烧产生的杂质(诸如硫化合物、NO、NO2、CO2、H2O、Hg等)都可被分离弃置而不排放到大气。包括CO2压缩系列(compression train),其包括确保最小增量功耗的高效单元。CO2压缩系列可特别地提供再循环CO2燃料压缩机流,后者可被部分再循环到燃烧器并部分作为输入高压CO2流而被导入液态CO2生产部件。
图2,例如示出了与如本文所述的元件组合的发电系统,以生产源自初级燃料(primary fuel)中的碳的净CO2产物,所述初级燃料为低压液态形式,其中氧含量在如本文所述的最小范围内。下面结合图2的实例描述了这种系统的实施方式。
CO2净产品总流量的大小可根据所用燃料的性质而变化。在利用天然气燃料的实施方式中,CO2净产品总流量可为再循环CO2燃料压缩机总流量的约2.5%至约4.5%(例如,约3.5%)。在利用典型的烟煤(例如,伊利诺斯州6号(Illinois No.6))的实施方式中,CO2净产品总流量可为再循环CO2燃料压缩机总流量的约5%至约7%(例如,约6%)。用于制冷的再循环CO2的量可在净CO2产物流量的约15wt%至约35wt%或约20wt%至约30wt%(例如约25wt%)的范围内。
在一些实施方式中,液化天然气(LNG)可以如第2013/0104525号美国专利公开所述的方式用作制冷源,该公开内容通过引用整体并入本文。在特定的实施方式中,LNG可被加热到接近CO2涡轮机排气冷凝温度的温度(例如,在约20巴(2MPa)至约40巴(4MPa)的压力下)。离开水分离器的涡轮机排气流可在干燥剂干燥器中干燥至低于约-50℃的露点,然后使用源自高压LNG的制冷进行液化,而后者又被加热。液态CO2现在可使用多级离心泵被泵压至约200巴(20MPa)至约400巴(40MPa)的压力。高压天然气的温度将通常在约-23℃(对于以约20巴(2MPa)离开节能热交换器的涡轮机排气)至约0℃(对于以约40巴(4MPa)离开节能热交换器的涡轮机排气)的范围内,使用这些压力下CO2饱和温度的5℃以内。这种冷的高压天然气可在膨胀之前用于预冷却处于约60巴(6MPa)至约400巴(40MPa)的高压CO2,以生产约6巴(0.6MPa)至约30巴(3MPa)的压力范围内的液态CO2。这种制冷可通过源自如上所述的高压CO2的膨胀的附加制冷来补充,以提供经冷却的净CO2产物的温度,该产物在膨胀至所需的液态CO2产物的压力时得到包含约50wt%至约80wt%的(O2+N2+Ar)的气体部分。其效果是显著减少必须再循环用于制冷的额外CO2的量。
实施例
通过以下实施例进一步说明本公开的实施方式,其被阐述以说明本公开的主题,而不应被解释为限制性的。下面描述组合发电系统及方法以及用于生产低压液态CO2的系统及方法的实施方式,如图2所示。
如图2所示,在压缩机44中将约40巴(4MPa)的天然气燃料流42(在本实例中为纯甲烷)压缩至约320巴(32MPa),以提供经压缩的天然气燃料流43,后者又进入燃烧室1,在这里其在经预热的氧化剂流38中燃烧,所述经预热的氧化剂流38包含约23wt%的氧气与约77wt%的稀释剂CO2的混合物。在所示实施方式中,总氧量包含比化学计量燃烧所需者多近似1wt%的氧气。燃烧产物在燃烧器1中用约304巴(30.4MPa)和约707℃的经加热的再循环CO2流37稀释。温度为约1153℃的燃烧器出口流39被通入涡轮机2的入口,所述涡轮机与发电机3和主CO2再循环压缩机4相连。
燃烧器出口流39在涡轮机2中被膨胀以提供约30巴(3MPa)和约747℃的涡轮机出口流45,后者又被通过节能热交换器15并被冷却至约56℃,作为经冷却的涡轮机出口流16离开。经冷却的涡轮机出口流16用冷却水在水冷却器7中进一步冷却到近环境温度(图2中的流17)。将经冷却的涡轮机出口流17通过分离器6,在这里液态水流18与气态CO2塔顶流19中分离,后者自身被分成分开的流(图2中的流22和20)。
气态CO2塔顶主体流22进入CO2再循环压缩机4,后者与中间冷却器5一起工作并将环境温度的气态CO2塔顶主体流22(来自涡轮机出口流45)从约28.2巴(2.82MPa)压缩至约63.5巴(6.35MPa)的压力-即经压缩的CO2流23。
气态CO2塔顶部分流20用于稀释由低温空气分离设备14产生的99.5%O2流28(其处于约28巴(2.8MPa)的压力)。合并的流20和28形成低压氧化剂流26,后者在带有中间冷却器12的压缩机11中被压缩至约320巴(32MPa)(流27)。高压氧化剂流27在节能热交换器中被加热,作为经预热的氧化剂流38(约304巴(30.4MPa)和约707℃)离开。
从加热高压再循环CO2流中提取110℃的第一侧流32,并在侧热交换器13中用热传递流体(作为流30进入侧热交换器并作为流29离开)加热至约154℃(图2中的流31),所述热传递流体从低温空气分离设备14中的空气压缩机去除压缩热。ASU具有大气空气进料40和排出到大气的废氮出口流41。
从加热高压再循环CO2流中提取约400℃的第二侧流61,并将其在涡轮机2中用于内部冷却。
处于约63.5巴(6.35MPa)和约51℃的经压缩的CO2流23在热交换器46中用冷却水冷却,以提供处于约17.5℃且密度约为820kg/m3的流47,所述流47在多级离心泵8中被泵压至约305巴(30.5MPa)的压力。泵排出流分为两部分。
来自泵排出流的高压再循环CO2流25通过节能热交换器15,并且用作从其获取第一测流和第二测流(如上所述)的流的作用。
来自泵排出流的流24包括源自天然气中的碳的净CO2产物流。流24优选可包括用于制冷的另外的CO2含量。另外的CO2含量可为再循环CO2的至多约50wt%、至多约40wt%或至多约30wt%。在一些实施方式中,另外的CO2含量可为再循环CO2的约5wt%至约45wt%,约10wt%至约40wt%或约15wt%至约35wt%。
将高压CO2流24在水冷却器50中冷却至近环境温度并分成两部分。高压CO2部分流57的压力在阀58中降低至约8.2巴(0.82MPa),以形成冷却CO2流56,其在约-45℃的温度是两相混合物。冷却CO2流56通过热交换器10,在那里其蒸发并加热至近环境温度,作为CO2流33离开。
高压净CO2产物流62直接通入热交换器10,在那里将其用冷却CO2流56冷却至约-38℃的温度,作为经冷却的高压净CO2产物流51离开。然后将该流通过在汽提塔53底部的小型再沸器52作为流55离开。该流在阀48中压力被降低至约10巴(1MPa),以形成两相净CO2产物流35,后者随后通过分离器9。
离开分离器9顶部的塔顶蒸汽流49包含两相净CO2产物流35流量的约4wt%,并且由约30wt%的CO2和约70wt%的O2和氩气的组合形成。塔顶蒸汽流49的压力在阀60中减小,然后被排放到大气(图2中的流59)。任选地,流59可在热交换器10中加热到接近环境温度,提供额外的制冷,然后进一步加热至高于环境温度,以使排气流上浮。
离开分离器9的液态CO2流36处于约10巴(1MPa)的压力,其包含两相净CO2产物流35流量的约96wt%。流36被进料到汽提塔53的顶部。
离开汽提塔53底部的是低压液态CO2产物流54,其包括由进料至电力系统的初级燃料中的碳产生的CO2。在所示实施方式中,流54的氧含量低于10ppm。
离开汽提塔53的顶部产物流63的压力在阀64中降低至约8巴(0.8MPa),并被添加到CO2流33中。合并的流33和63在压缩机34中被压缩至约28.5巴(2.85MPa)。在CO2压缩机34中压缩的排出流21与气态塔顶主体流22混合并在CO2压缩机4和泵8中被压缩回约305巴(30.5MPa)。
在上述实施例中,提供了具体值(例如,温度、压力和相对比率)以示出本公开的示例性实施方式的工作条件。这些值并不意味着限制本公开,并且应当理解,这些值可在本文另外公开的范围内变化,以根据本文提供的总体描述来实现进一步的工作实施。
受益于前述描述和相关附图中所呈现的教导,本主题所属领域的技术人员将会想到本公开主题的许多修改和其它实施方式。因此,应当理解,本公开不限于本文所述的具体实施方式,并且修改和其他实施方式旨在被包括在所附权利要求的范围内。尽管本文采用了具体的术语,但它们仅在通用和描述性意义上使用,而不是为了限制的目的。
Claims (20)
1.生产低压液态二氧化碳(CO2)流的方法,所述方法包括:
在约100巴(10MPa)或更高的压力和约400℃或更高的温度在再循环CO2流存在下在燃烧器中用氧气燃烧碳质或碳氢燃料以形成包含CO2的燃烧器出口流;
在涡轮机中膨胀燃烧器出口流以发电并形成压力为约50巴(5MPa)或更低的包含CO2的涡轮机出口流;
在第一热交换器中冷却涡轮机出口流以形成经冷却的涡轮机出口流;
将来自经冷却的涡轮机出口流的CO2泵压至约100巴(10MPa)或更高的压力以形成高压CO2流;
将高压CO2流分为主体部分和冷却部分;
将高压CO2流的冷却部分膨胀以将其温度降低至约-20℃或更低;
通过将高压CO2流的主体部分通过第二热交换器以用经膨胀的高压CO2流的冷却部分将高压CO2流的主体部分冷却至约5℃或更低的温度;和
将经冷却的高压CO2流的主体部分膨胀至约30巴(3MPa)或更低但高于CO2的三相点压力的压力,从而形成低压液态CO2流。
2.根据权利要求1所述的方法,其中燃烧器出口流处于约200巴(20MPa)至约400巴(40MPa)的压力。
3.根据权利要求1所述的方法,其中燃烧器出口流处于约800℃至约1,600℃的温度。
4.根据权利要求1所述的方法,其中包含CO2的涡轮机出口流处于约20巴(2MPa)至约40巴(4MPa)的压力。
5.根据权利要求1所述的方法,其中涡轮机出口流在热交换器中冷却至约80℃或更低的温度。
6.根据权利要求5所述的方法,还包括将经冷却的包含CO2的涡轮机出口流通过一个或多个分离器以从其中去除至少水。
7.根据权利要求1所述的方法,还包括在热交换器中用涡轮机出口流加热氧气和再循环CO2流中的一种或两种。
8.根据权利要求1所述的方法,其中高压CO2流处于约200巴(20MPa)至约400巴(40MPa)的压力。
9.根据权利要求1所述的方法,其中高压CO2流的主体部分被冷却至约-55℃至约0℃的温度。
10.根据权利要求1所述的方法,还包括在高压CO2流的主体部分的所述冷却之后并且在高压CO2流的主体部分的所述膨胀之前,使高压CO2流的主体部分通过再沸器。
11.根据权利要求10所述的方法,其中再沸器在汽提塔中。
12.根据权利要求1所述的方法,还包括将低压液态CO2流通过能从其中有效分离蒸汽流的分离器。
13.根据权利要求12所述的方法,其中蒸汽流占通过分离器的低压液态CO2流的至多约8wt%。
14.根据权利要求12所述的方法,其中蒸汽流包含约1wt%至约75wt%的CO2和约25wt%至约99wt%的N2、O2和氩中的一种或多种。
15.根据权利要求12所述的方法,还包括将剩余的低压液态CO2流通入汽提塔。
16.根据权利要求15的方法,其中离开汽提塔的低压液态CO2流的氧含量不多于25ppm。
17.根据权利要求15所述的方法,包括将低压液态CO2流泵压至至少100巴(10MPa)的压力。
18.根据权利要求17所述的方法,包括将经泵压的液态CO2流输送到CO2管线。
19.根据权利要求1所述的方法,还包括将来自汽提塔的塔顶蒸汽与离开第二热交换器的高压CO2流的冷却部分混合。
20.根据权利要求19所述的方法,还包括将混合物加入到经冷却的涡轮机出口流中。
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