CN110121586A - 用于电力生产和集成的氢气生产的系统和方法 - Google Patents

用于电力生产和集成的氢气生产的系统和方法 Download PDF

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CN110121586A
CN110121586A CN201780078537.1A CN201780078537A CN110121586A CN 110121586 A CN110121586 A CN 110121586A CN 201780078537 A CN201780078537 A CN 201780078537A CN 110121586 A CN110121586 A CN 110121586A
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hydrogen
power generation
heat exchanger
gas
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CN110121586B (zh
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R·J·奥勒姆
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8 Rivers Capital LLC
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8 Rivers Capital LLC
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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D53/00Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/02Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography
    • B01D53/04Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography with stationary adsorbents
    • B01D53/047Pressure swing adsorption
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J7/00Apparatus for generating gases
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • C01B3/34Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents
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    • C01B3/34Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents
    • C01B3/38Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents using catalysts
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    • C10K3/00Modifying the chemical composition of combustible gases containing carbon monoxide to produce an improved fuel, e.g. one of different calorific value, which may be free from carbon monoxide
    • C10K3/02Modifying the chemical composition of combustible gases containing carbon monoxide to produce an improved fuel, e.g. one of different calorific value, which may be free from carbon monoxide by catalytic treatment
    • C10K3/04Modifying the chemical composition of combustible gases containing carbon monoxide to produce an improved fuel, e.g. one of different calorific value, which may be free from carbon monoxide by catalytic treatment reducing the carbon monoxide content, e.g. water-gas shift [WGS]
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    • F02COMBUSTION ENGINES; HOT-GAS OR COMBUSTION-PRODUCT ENGINE PLANTS
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    • F02C3/20Gas-turbine plants characterised by the use of combustion products as the working fluid using a special fuel, oxidant, or dilution fluid to generate the combustion products
    • F02C3/22Gas-turbine plants characterised by the use of combustion products as the working fluid using a special fuel, oxidant, or dilution fluid to generate the combustion products the fuel or oxidant being gaseous at standard temperature and pressure
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    • F02C3/00Gas-turbine plants characterised by the use of combustion products as the working fluid
    • F02C3/20Gas-turbine plants characterised by the use of combustion products as the working fluid using a special fuel, oxidant, or dilution fluid to generate the combustion products
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    • F02C3/28Gas-turbine plants characterised by the use of combustion products as the working fluid using a special fuel, oxidant, or dilution fluid to generate the combustion products the fuel or oxidant being solid or pulverulent, e.g. in slurry or suspension using a separate gas producer for gasifying the fuel before combustion
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    • F02C3/00Gas-turbine plants characterised by the use of combustion products as the working fluid
    • F02C3/34Gas-turbine plants characterised by the use of combustion products as the working fluid with recycling of part of the working fluid, i.e. semi-closed cycles with combustion products in the closed part of the cycle
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Abstract

本公开涉及可用于电力生产的系统和方法。特别是,利用CO2作为工作流体的包括第一燃烧室(102)和涡轮机(103)的电力生产循环可以被配置用于在另外的氢气生产单元中同时生产氢气。有利的是,由电力生产和氢气生产中的燃烧产生的基本上所有的碳都以二氧化碳的形式被捕获。此外,所生产的氢气(任选地与从空气分离单元接收的氮气(160)混合)可以作为燃料输入燃气轮机联合循环单元中以在其中用于额外的电力生产而没有任何大气CO2排放。

Description

用于电力生产和集成的氢气生产的系统和方法
技术领域
本公开提供了电力生产系统和方法,其中利用CO2循环流体的电力生产循环可以被配置用于同时生产氢气。
背景技术
长期以来,氢气(如用于燃料电池中)由于它与储存能源之间来回的清洁转化而被认为是一种理想的能源。举例来说,使用燃料电池,有利地连同高容量蓄电池一起,氢气可以用作用于电动车辆推进的燃料。有利的是,使用氢气作为燃料可以消除CO2、NOx、CO以及烃排放并且因此显著减少空气污染。然而,实现以氢气为基础的世界经济的任何途径都将需要非常大的氢气生产能力。此外,这样的氢气生产方法将需要能够同时实现低氢气生产成本以及捕获接近100%的源自于所利用的化石燃料的CO2
氢气用作燃料源也可以有益于减少或消除与更常规的电力生产过程相关的二氧化碳排放。举例来说,可以将氢气用氮气和/或蒸汽稀释并且用作燃气轮机联合循环发电系统中的燃料。
燃气轮机联合循环发电系统是全世界范围内发电的主要来源,这是因为它们能够在低热值(LHV)基础上以60%范围内的效率从天然气生产电力。尽管具有理想的效率,但是这样的系统仍然存在问题,这是因为燃料中的碳会作为二氧化碳被排放到大气中。为了克服这个问题,有可能使用CO2代替空气作为工作流体来操作燃气轮机,这是通过将涡轮机排放CO2气体在冷却和去除产品CO2之后再循环到燃气轮机压缩机区段的入口来实现的。这也存在问题,这是因为燃料必须在纯氧中燃烧以仅产生CO2和水作为燃烧产物,并且这需要添加空气分离设备,这会造成对工艺效率的消耗。常常使用化学和/或物理溶剂洗涤处理来处理燃气轮机排气以去除CO2;然而,这样的处理可以提供混合的结果并且由于增加了排气处理系统和维护的成本而再次降低工艺效率。如上文所述,有可能通过利用氢气作为燃气轮机中的燃料来消除碳排放;然而,这种方法需要优先提供而没有相关的CO2产生的一致的氢源。由于使用氢气作为燃料源的可取性,因此仍然需要以低成本提供氢燃料而基本上不向大气排放CO2的手段。
发明内容
本公开涉及将电力生产和氢气生产组合的系统和方法。具体来说,电力生产(例如电力)和氢气生产可以通过烃燃料的燃烧同时实现。更具体来说,可以使烃燃料燃烧以提供包括氢气和/或被转化成氢气的燃烧产物。此外,可以在基本上零碳排放的情况下生产氢气,并且所述氢气可以用作用于电力生产的燃料。
在一些实施方案中,本公开还可以涉及利用氧气在催化反应和/或非催化反应中部分氧化烃燃料来产生氢气(H2)和一氧化碳(CO)的系统和方法。举例来说,可以使用部分氧化非催化反应器(POX)或催化自热反应器(ATR)。在烃燃料的部分氧化之后可以使用气体加热重整器(GHR)以与POX反应器或ATR反应器串联或并联模式,通过利用POX反应器系统和/或ATR反应器系统中的排气显热以为在GHR中发生的吸热催化蒸汽加天然气重整反应提供热量来产生另外的H2和CO(即合成气)。
在一个或多个实施方案中,本发明的系统和方法可以利用在制氢设备中产生的余热(例如在低于400℃的温度水平下)以为所述电力生产系统和方法提供额外的热量输入。这种增加的热量可以有益于帮助实现高发电效率。
在其他实施方案中,本公开包括向H2+CO合成气产生反应器提供使燃料流(例如天然气)和蒸汽进料流中的一个或这两者过热所需的热量。这可以例如使用源自于来自电力生产系统和方法的涡轮机排出流的热量来实现。
在另外的实施方案中,本发明的系统和方法可以利用变压吸附(PSA)系统从冷却的粗制氢气流中分离纯的高压氢气。这可以例如在通过与蒸汽进行催化变换反应将CO转化成H2之后实现。
在另外的实施方案中,本公开可以提供用于制氢设备的燃料中存在的基本上所有的碳的回收。举例来说,这可以通过压缩来自PSA的废气并且使用它作为用于电力生产循环系统和方法的燃料气体的一部分来实现,其中从冷却的涡轮机排气流中回收CO2
如果需要的话,用于电力生产循环系统和方法中的氧气的一部分或全部可以从低温空气分离设备或具有低压空气进料的氧离子传输膜(ITM)氧-燃料燃烧室供应。制氢设备可以利用高达105巴的压力的高压气态氧气流作为POX和/或ATR的进料,从而从PSA产生高达95巴的基本上纯的H2。供应高压氧的低温空气分离设备对于提供氧气可以是特别有用的。
此外,如果需要的话,可以使用第二燃料氧燃烧室来加热燃气轮机排气以为制氢设备燃料、氧气以及蒸汽进料流中的任何一个或多个提供预热。可以向它供应涡轮机排出压力的气态氧气流,但是这优先地可以在O2燃烧器喷射系统中用CO2稀释以控制绝热火焰温度。第二替代方案是使用被供给预热的低压空气的ITM燃烧室,使用与燃气轮机排气共混的预热的天然气流来预热涡轮机排气,其将与扩散氧气一起燃烧并且为合成气反应器的天然气流和蒸汽进料流提供必要的过热。
在一个或多个实施方案中,本公开可以提供一种电力生产系统或单元,其可以被配置用于同时进行电力生产和氢气生产。具体来说,所述系统可以包括:燃烧室;涡轮机;回热式热交换器;水分离器;压缩机;以及集成的氢气生产系统或单元。
在一个或多个实施方案中,本公开可以提供一种用于电力生产的方法。具体来说,所述方法可以包括以下:
在第一燃烧室中将含碳燃料在再循环的CO2流存在下在燃烧压力下用氧化剂燃烧以提供包括CO2的燃烧产物流;
使所述燃烧产物流在涡轮机中膨胀以产生电力并且形成包括CO2的涡轮机排出流;
在回热式热交换器中冷却所述包括CO2的涡轮机排出流;
将CO2与所述涡轮机排出流的任何另外的组分分离以提供再循环的CO2流;
将所述再循环的CO2流压缩到基本上燃烧压力;
从所述再循环的CO2流中去除源自于烃或含碳燃料中碳的燃烧的CO2
将所述压缩的再循环CO2流在所述回热式热交换器中用从所述涡轮机排气流中提取的热量和/或以低于约400℃的温度水平供应的外部热量加热;
使任选预热的含碳燃料(以及任选的氧气和/或蒸汽)通过POX或ATR,任选地随后通过GHR以形成合成气流,所述合成气流特别可以包含H2和CO;
将所述合成气冷却以产生高压蒸汽;
使所述合成气通过一个或多个催化变换反应器,有效地将CO和H2O转化成H2和CO2
从所述合成气流中分离H2;以及
在从所述合成气流中分离H2之后将剩余的燃料气体通到第一燃烧室和第二燃烧室中的一个或这两者中。
在上述方法中,应当了解的是,并非所有所述步骤都必须在每一个可能的实施方案中进行。相反,上述步骤中的一个或多个可以是任选的,并且本领域技术人员在了解本公开的情况下将能够识别可以在单独的实施方案中进行的步骤的各种可能组合。
除了上述之外,本发明公开的系统和方法还可以关于另外的要素和配置进一步限定。举例来说,以下任何一个或多个可以适用。
氢气生产可以具体地使用至少两个反应器进行,如部分氧化反应器和气体加热重整器反应器。
用于合成气生产的烃进料流和/或蒸汽进料流的高温加热可以利用源自于电力生产循环的热量。具体来说,所述热量可以源自于电力生产循环涡轮机排气的至少一部分。
可以在多床变压吸收单元中将氢气与一种或多种废物组分分离。
与氢气分离的一种或多种废物组分可以被压缩并且用作电力生产循环中燃料的一部分。
源自于在氢气生产系统和方法中用作燃料进料的烃燃料的基本上所有的碳可以作为高压CO2流被回收,所述高压CO2流可以适合于引入到CO2管线中。
从制氢设备中排出的基本上所有的低温热量(即高于环境温度,但是约400℃或更低的温度的热量)可以被回收用于电力生产循环中的热量输入。
在一个或多个实施方案中,本公开可以提供来自燃料(例如来自天然气)的氢气生产、源自于燃料中的碳的基本上所有CO2的捕获以及电力系统与氢气生产之间高效热量集成的集成。优选的是,这样的集成可以实现以高效率(例如>60%LHV)从燃料生产电力,其中向大气的CO2排放接近零并且电力成本基本上类似于由不提供部分或完全CO2捕获的当前工艺产生的成本。
在一些实施方案中,本公开可以提供一种用于电力生产的系统,所述系统包括:电力生产单元,其被配置用于连续压缩、加热、膨胀、冷却以及再循环CO2工作流体而没有CO2的大气排放;氢气生产系统或单元,其包括被配置成形成合成气流的部分氧化燃烧室和被配置成从所述合成气流中分离H2的分离器;以及燃气轮机联合循环单元,其被配置成接收和燃烧来自所述氢气生产系统或单元的H2
在一些实施方案中,本公开涉及一种电力生产方法和集成的H2生产方法,其包括:
在燃烧室中将气体燃料在升高的压力下在再循环的加热了的CO2存在下用基本上纯的O2燃烧以形成燃烧产物流;
使所述燃烧产物流在涡轮机中膨胀到更低的压力以产生轴功率并且形成涡轮机排气流;
将所述涡轮机排气流在回热式热交换器中冷却以形成冷却的涡轮机排气流,同时加热再循环的CO2流以形成所述再循环的加热了的CO2
任选地从外部来源将低于约400℃的温度水平的热量添加到所述再循环的CO2流中;
从所述冷却的涡轮机排气流中分离冷凝水以提供所述再循环的CO2流;以及
将所述再循环的CO2流压缩到适用于输入到所述燃烧室中的压力;
其中以下条件中的一个或多个适用:
利用从所述涡轮机排气流传递的热量加热向H2合成设备反应器供给的烃或含碳燃料流和蒸汽流中的一个或这两者;
增加涡轮机燃烧室燃料入口流量和涡轮机入口温度以提供来自涡轮机的额外功率加上预热制氢设备合成反应器的烃或含碳燃料和蒸汽进料所需的热量并且其中涡轮机入口温度与独立的CO2动力循环中的回热式热交换器基本上相同;
将低于约400℃的温度水平的来自H2合成设备的余热从所述H2合成设备传递到所述再循环的CO2流;
在一个或多个CO催化变换反应器中将CO转化成H2之后,在H2合成设备中从总不纯H2产物流中分离氢气,继而冷却到接近环境温度并且去除液态水;
将在H2合成设备中分离H2之后剩余的废燃料气体压缩到适用于输入到所述燃烧室中的压力;
在多个阶段中进行所述H2合成设备中的H2分离;
H2合成设备中的H2分离包括中间CO2去除和催化CO变换转化成H2
利用第二燃烧室,所述第二燃烧室使用基本上纯的氧气和燃料气体加上涡轮机排气的至少一部分以提供预热制氢设备合成反应器的烃或含碳燃料和蒸汽进料所需的热量的至少一部分;
提供低于约400℃的温度的加热了的加压水和/或蒸汽流并且将来自H2合成设备的余热输送到再循环的CO2流;
将从H2合成设备产生的H2与N2和/或蒸汽组合以产生适用于在燃气轮机中燃烧以生产电力的燃料气体。
在一个或多个实施方案中,本公开可以特别提供一种用于组合的电力生产和氢气生产的系统,所述系统包括:电力生产单元,其中使加压的二氧化碳膨胀以用于电力生产;氢气生产单元,其中将烃燃料部分氧化以产生合成气,从所述合成气中分离氢气;以及一个或多个流动部件,其被配置用于使一个或多个流在所述电力生产单元与所述氢气生产单元之间通过。
在另外的实施方案中,所述用于组合的电力生产和氢气生产的系统可以关于以下语句中的任何一个或多个进一步限定,其可以任何顺序和数量组合。
所述电力生产单元可以包括:燃烧室,其被配置成接收烃燃料和氧气并且输出至少包含加压的二氧化碳的加热流;涡轮机,其被配置成接收和膨胀来自所述燃烧室的包含加压的二氧化碳的加热流以生产电力并且形成包含膨胀的二氧化碳的加热流;回热式热交换器,其被配置成接收包含膨胀的二氧化碳的加热流并且形成包含二氧化碳的冷却流;分离器,其被配置成接收来自所述回热式热交换器的包含二氧化碳的冷却流并且提供二氧化碳流;以及压缩机,其被配置成接收来自所述分离器的二氧化碳流并且压缩所述二氧化碳。
所述氢气生产单元可以包括:部分氧化燃烧室,其被配置成接收氧气和烃燃料的一部分并且输出合成气;重整器,其与所述部分氧化燃烧室处于流体连通并且被配置成接收来自所述部分氧化燃烧室的合成气并且接收烃燃料的一部分;变换反应器,其与所述重整器处于流体连通;变换流热交换器,其与所述变换反应器处于流体连通;分离器,其与所述变换流热交换器处于流体连通;以及变压吸附单元,其与所述分离器处于流体连通;其中所述变压吸附单元被配置成输出基本上纯的氢气流。
可以从通过变换流热交换器的烃燃料管线向部分氧化燃烧室和重整器提供烃燃料。
烃燃料管线可以通过补充热交换器,补充热交换器被配置成接收和冷却离开电力生产单元的涡轮机的包含膨胀的二氧化碳的加热流。
所述系统还可以包括水管线,水管线可以被配置用于将水通到重整器中。
所述水管线可以通过变换流热交换器。
所述水管线可以通过补充热交换器,补充热交换器被配置成接收和冷却离开电力生产单元的涡轮机的包含膨胀的二氧化碳的加热流。
所述变压吸附单元可以被配置成输出与基本上纯的氢气流分离的废物流,其中所述废物流包含一氧化碳、二氧化碳、氢气、甲烷、氩气以及氮气中的一种或多种。
被配置用于使一个或多个流在电力生产单元与氢气生产单元之间通过的一个或多个流动部件可以包括用于使废物流的至少一部分从变压吸附单元通到电力生产单元的燃烧室的管线。
电力生产单元还可以包括附加热交换器,其被配置成将基本上纯的二氧化碳流相对于来自电力生产单元的一个或多个压缩流加热。
所述附加热交换器可以进一步被配置成将基本上纯的二氧化碳流相对于来自氢气生产单元的流加热。
在一个或多个实施方案中,本公开可以特别提供一种用于组合的电力生产和氢气生产的方法,所述方法包括:在电力生产单元中进行电力生产,所述电力生产包括:在第一燃烧室中将第一烃燃料在再循环的CO2流存在下在燃烧压力下用氧化剂燃烧以提供包括CO2的燃烧产物流;使所述包括CO2的燃烧产物流在涡轮机中膨胀以生产电力并且形成包括CO2的涡轮机排出流;在回热式热交换器中冷却所述包括CO2的涡轮机排出流;将CO2与所述涡轮机排出流的任何另外的组分分离以提供包含再循环的CO2的流;将所述包含再循环的CO2的流压缩到基本上燃烧压力;将所述压缩的再循环的CO2流在所述回热式热交换器中用从所述涡轮机排气流中取出的热量加热以提供包含再循环的CO2的加热流;以及将所述包含再循环的CO2的加热流通到第一燃烧室中;以及在氢气生产单元中进行氢气生产,所述氢气生产包括:使第二烃燃料流通过部分氧化反应器以形成合成气流;以及处理所述合成气以提供基本上纯的氢气流和包含至少一氧化碳的废物流。
在另外的实施方案中,所述用于组合的电力生产和氢气生产的方法可以关于以下语句中的任何一个或多个进一步限定,其可以任何顺序和数量组合。
所述方法还可以包括将至少一氧化碳从所述废物流通到第一燃烧室中。
处理所述合成气可以包括使所述合成气通过重整器,所述重整器还被配置成接收第二烃燃料气流和加热水流。
通过部分氧化反应器的第二烃燃料流、由重整器接收的第二烃燃料流以及由重整器接收的加热水流中的一个或多个可以在补充热交换器中利用从包括CO2的涡轮机排出流传递的热量来加热。
处理所述合成气可以包括使来自重整器的重整合成气通过变换反应器,继而通过变换流热交换器。
可以经由通过变换流热交换器的烃燃料管线将烃燃料流提供到部分氧化燃烧室和重整器中的一个或这两者中。
重整器中接收的加热水流可以经由通过变换流热交换器的水管线提供。
所述方法还可以包括使离开变换流热交换器的流通过水分离器以去除水并且形成包括氢气和杂质的粗制氢气流。
所述方法还可以包括使粗制氢气流通过变压吸附单元,所述变压吸附单元输出基本上纯的氢气和废物流。
可以将废物流压缩到适用于输入到电力生产单元的燃烧室中的压力,然后通到电力生产单元的燃烧室中。
所述电力生产单元可以包括附加热交换器,其将再循环CO2流相对于来自电力生产单元的一个或多个压缩流加热。
所述方法还可以包括使来自氢气生产单元的加热流通过附加热交换器以使得来自氢气生产单元的热量被传递到再循环CO2流。
从氢气生产单元传递到再循环CO2流的热量可以在低于约400℃的温度水平。
可以使包括CO2的涡轮机排出流的至少一部分与第一烃燃料和氧气流一起通过第二燃烧室以使得第一烃燃料燃烧以向包括CO2的涡轮机排出流的至少一部分提供额外的热量。
向包括CO2的涡轮机排出流的至少一部分提供的额外热量的至少一部分可以向氢气生产单元中的一个或多个流提供。
所述方法还可以包括在与电力生产单元分开的燃气轮机中进行电力生产,其中使基本上纯的氢气的至少一部分在所述燃气轮机中燃烧以生产电力。
在一个或多个实施方案中,本公开还可以提供一种用于电力生产的系统,所述系统包括:电力生产单元,其被配置用于连续压缩、加热、膨胀、冷却以及再循环CO2工作流体而没有CO2的大气排放;氢气生产单元,其包括被配置成形成合成气流的部分氧化燃烧室和被配置成处理所述合成气以形成基本上纯的氢气流和废物流的一个或多个另外的部件;以及燃气轮机联合循环单元,其被配置成接收和燃烧来自所述氢气生产单元的基本上纯的氢气的至少一部分。
附图说明
已经由此在上文大体上描述了本公开,现在将参考附图,所述附图不一定是按比例绘制的并且在所述附图中:
图1是使用CO2工作流体并且包括低温制氧设备的示例性电力生产系统和方法的流程图;
图2是包括用于与如图1中所示的电力生产系统和方法集成的元件的氢气生产设施的流程图;并且
图3是图示了组合系统的流程图,其中将来自空气分离单元的氮气和来自氢气产生单元的氢气输入到燃气轮机联合循环单元中。
具体实施方式
现在将在下文中参考本发明的主题的示例性实施方案更充分地描述本发明的主题。描述这些示例性实施方案以使得本公开将是全面的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,所述主题可以许多不同的形式实施并且不应当被解释为限于本文所述的实施方案;相反,提供这些实施方案以使得本公开将满足适用的法律要求。除非上下文另外明确规定,否则如本说明书和所附权利要求中所用的单数形式“a/an(一)”、“所述”包括复数指代对象。
本公开提供了其中同时实现电力生产和氢气生产的系统和方法。已经进行了先前的努力以提供电力和氢气的同时生产,并且来自这些先前的努力的一个或多个元件可以被集成到本发明公开的系统和方法中。举例来说,Allam等的美国专利号6,534,551描述了以下各项的组合:1)烃燃料气体与蒸汽和/或氧气的反应;以及2)利用压缩的氧化剂气体的电力系统,其中使用燃烧室产物燃烧燃料气体,从而通过功膨胀生产电力,并且其中使用膨胀的燃烧产物气体使用于氢气合成反应中的蒸汽过热,并且其中通过由燃烧产物气体的膨胀产生的电力的至少一部分驱动氧气生产单元。Allam等的美国专利号6,534,551的公开内容以引用的方式并入本文。
在一个或多个实施方案中,本发明的系统和方法可以有利地提供氢气生产与电力生产的组合而捕获基本上所有所产生的碳,特别是基本上所有所产生的CO2。所述组合可以是具有适合于实现氢气和电力的同时生产的元件组合的单一系统。在一些实施方案中,氢气生产系统或单元可以在适当的元件交叉的情况下与电力生产系统或单元并行操作以使这两个系统或单元作为单一集成系统运行。本公开因此可以涉及一种制氢设备,并且应当了解的是,这样的制氢设备指的是形成本文所用的氢气生产系统或单元所需的元件的组合。
根据本公开有用的电力生产循环可以包括其中在工作流中使用CO2(特别是超临界CO2或sCO2)的任何系统和方法。作为非限制性实例,以引用的方式并入本文的Allam等的美国专利号8,596,075描述了一种系统和方法,其中将再循环CO2流直接加热并且用于电力生产。确切地说,将再循环CO2流在高温和高压下提供,提供到其中使含碳燃料在氧气中燃烧的燃烧室中,在涡轮机中膨胀以生产电力,在热交换器中冷却,纯化以去除水和任何其他杂质,加压,使用取自涡轮机排气的热量再加热,并且再次通到燃烧室中以重复所述循环。这样的系统和方法是有益的,这是因为所有燃料和燃烧产生的杂质、过量的CO2以及水都作为气态或超临界流体、液体或固体(例如灰分)被去除,并且任何流的大气排放几乎为零。所述系统和方法经由例如在再循环CO2流已经被再加压之后并且在燃烧之前使用低温度水平(即低于500℃)热量输入来实现高效率(即除了从涡轮机排气流回收的热量之外还向再循环CO2流添加的低温度水平热量)。应当了解的是,在本文提到电力生产循环时,表示利用CO2工作流体以及本文和所并入的文献中所述的元件和方法步骤的组合的电力生产循环。
根据本公开有用的电力生产循环可以包括比上述更多的步骤或更少的步骤并且一般可以包括其中使高压再循环CO2流膨胀以用于进行电力生产并且再次再循环以用于进一步电力生产的任何循环。如本文所用的高压再循环CO2流可以具有至少100巴(10MPa)、至少200巴(20MPa)或至少300巴(30MPa)的压力。在所有情况下,压力的上限可以由在实施根据本公开的系统和/或方法时可用设备的限度决定。在一些实施方案中,高压再循环CO2流可以具有约100巴(10MPa)至约500巴(50MPa)、约150巴至约450巴(45MPa)或约200巴(20MPa)至约400巴(40MPa)的压力。因此,在本文提到高压再循环CO2流时,可以是处于上述范围内的压力的CO2流。这样的压力也适用于提到本文所述的其他高压流,如包含CO2的高压工作流。燃烧可以在约400℃或更高、约500℃或更高、约600℃或更高、约800℃或更高或约1000℃或更高的温度下进行。在所有情况下,温度的上限可以由在实施根据本公开的系统和/或方法时可用设备的限度决定。在一些实施方案中,在与再循环CO2混合之后第一燃烧室出口温度可以是约400℃至约1,500℃、约500℃至约1200℃或约600℃至约1000℃。
在一些实施方案中,如上文所述的电力生产循环与氢气生产设施的集成可以利用由制氢设备产生的多余的低温度水平热量以提高电力生产的效率。举例来说,可以在涡轮机排气流中使蒸汽和烃进料过热而增加电力生产系统和方法中的涡轮机功率输出。此外,制氢设备可以与电力生产循环集成以使得基本上所有源自于制氢设备或系统中的烃燃料进料中存在的碳的CO2被捕获并且任选地与从电力生产循环设备或系统中捕获的CO2组合。所述集成系统捕获高达100%的由电力设备和制氢设备这两者产生的CO2而向大气中的排放为零。
根据本公开使用的氢气生产设备可以包括已知适用于现有氢气生产设备中的任何种类的元件。举例来说,氢气生产设备可以包括两级反应器系统,其包括第一级反应器,所述第一级反应器使用氧气并且任选地在另外使用蒸汽的情况下对烃的部分氧化将烃进料转化成CO+H2气体。在一些实施方案中,可以在约1300℃至约1500℃的出口温度下在约30巴至约150巴的典型压力下用纯氧对天然气进料进行这样的部分氧化(POX)。自热重整器(ATR)可以在部分氧化燃烧器之后添加蒸汽和过量的烃,一般是天然气,以使得高温气体然后可以通过催化剂床,其中发生后续的蒸汽-烃重整反应,从而产生另外的H2+CO并且将气体混合物在约30巴至约150巴的压力下冷却到约1000℃至约1100℃的出口温度。第二级反应器可以包括蒸汽/烃催化重整器,其中使用来自这两个反应器的总H2+CO气体产物(例如在约1000℃或更高的温度下)提供管中具有催化剂的对流加热的壳侧流中重整反应的吸热。任选地,这两个反应器可以串联或并联模式操作。有利的配置使用具有从容器顶部处的单个管板悬挂的填充催化剂的开口管的立式气体加热重整器(GHR),其中产物H2+CO离开重整器管并且在GHR的基部与来自POX反应器或ATR的产物气体混合,并且总产物H2+CO流通过壳侧并且通常从约1050℃冷却到550℃至800℃。
双反应器配置的优势在于来自烃进料的H2+CO的产率达到最大,并且在反应中形成的所有CO2都被容纳在高压系统内。将产物CO+H2气体在产生蒸汽的废热锅炉(WHB)中进一步冷却,并且另一个优势在于该蒸汽量仅足以向两个H2+CO反应器提供所需的蒸汽流量而仅有少量过量流量。所述系统没有大量的副产物蒸汽产生。
为了产生氢气,使在约240℃至约290℃的典型温度下离开WHB并且通常含有约20%至约40%(摩尔)蒸汽的H2+CO产物通过一个或多个催化变换转化器,其中CO与蒸汽反应以产生CO2和额外的H2。整个H2生产过程顺序的反应示于下文中(使用CH4作为烃):
CH4+1/2O2→CO+2H2 部分氧化
CH4+2O2→CO2+2H2O 热量产生
CH4+H2O→CO+3H2 重整
CH4+CO2→2CO+2H2 重整
CO+H2O→CO2+H2 CO变换
将通过CO变换反应器的总CO+H2产物冷却,并且随着气体冷却和蒸汽冷凝,一般在约290℃或更低的温度水平释放大量的热量。该热量并不是在单一温度水平释放的,而是在低至接近环境温度的温度范围内释放的。该热量释放的一部分可以用于预热锅炉给水,但是存在大量过量,其处于低温度水平并且仅可在一定温度范围内获得。
在两个反应器中H2+CO产生的效率可以通过将烃和蒸汽进料预热到通常约400℃至约550℃并且优选地约500℃至约550℃来显著提高。这优选地使用外部热源进行,这是因为这些温度水平的余热在H2+CO产生反应器和WHB内不可获得。
随后使冷却的富含H2的气流通过冷却器(例如环境冷却器),其中去除冷凝水。然后将气流通到分离器中,其中可以分离出基本上纯的氢气。举例来说,可以使气流通过常规的多床变压吸附器,其通常分离约85%至约90%(摩尔)的氢气作为纯流,所述纯流通常具有约10ppm至约50ppm的总杂质并且具有通常约1巴至约2巴的从进料到产物H2的压降。粗制H2进料流中的所有杂质都被分离为废燃料气流,所述废物流可以包含诸如H2、CO、CO2、CH4、N2、氩气以及少量气相H2O的组分的任何组合。压力通常是约1.1巴至约1.5巴。该废气通常具有总烃反应器烃进料低热值(LHV)的约20%,因此它的有效使用对于H2生产的总体经济性是有利的。所述废气含有作为CO2+CO的所有来自总烃进料的碳并且在管线高压下作为纯CO2回收该碳对于满足气候变化排放目标同样是有利的。
高压双反应器氢气产生系统与利用CO2工作流的电力生产循环的集成可以实现多种益处。来自电力生产循环的涡轮机排气通常在约700℃至约800℃的范围内。可以在单独的热交换器中利用涡轮机排气流的一部分将两个反应器的蒸汽和烃进料预热到约500℃至约550℃的范围。这仅需要增加涡轮机燃烧室中燃烧的燃料以提供所需的额外热量。这增加了涡轮机入口温度和流速并且提供了来自涡轮机的显著的额外功率输出。蒸汽和烃或含碳燃料可以被加热到约400℃至约550℃的典型温度,同时涡轮机排气可以在进入回热式热交换器中之前被冷却到约700℃至约800℃的典型温度。
作为替代布置,可以设置第二燃烧室以预热涡轮机排气流的至少一部分以输送预热在两级反应器系统中产生合成气所需的燃料和蒸汽所需的热量。一个燃烧室布置使用用CO2稀释的包含基本上纯的O2的氧化剂以产生含有20摩尔%至30摩尔%的O2的氧化剂来燃烧燃料。第二燃烧室布置使用O2离子传输膜反应器,其将源自于预热的低压空气流的基本上纯的O2扩散到涡轮机排气的至少一部分中,已经向所述涡轮机排气中添加了受控制的一部分燃料以使得温度根据制氢设备预热负荷的需要而升高。
来自PSA的废气可以被压缩到通常约200巴至约400巴并且与进料烃混合并且非常有效地用作电力生产循环中的燃料气体。另一个优势是来自烃反应器进料的碳可以作为CO2在电力生产循环系统内捕获。另一个优势是废气的大质量流量,这是因为它具有通常约50%至约70%(摩尔)的高CO+CO2含量,这增加了额外的涡轮机功率。或者,可以将来自PSA的废气压缩到第一PSA的入口压力,可以在许多已知工艺之一中去除CO2,并且可以将CO2贫化的气流送到第二PSA中以分离更多的H2以添加到总H2产物流中。任选地,可以将废气在节能器热交换器中预热,可以添加蒸汽,并且可以在另外的催化CO变换反应器中产生更多的H2。然后可以将气体在节能器热交换器中冷却,之后在第二PSA中处理以分离更多的H2
可从冷却H2+CO流获得的大量低品位热量理想地适用于提供可以添加到电力生产循环中的低温度水平热量以增加从涡轮机排气回收的热量并且因此实现高效率。确切地说,来自冷却H2+CO流的“低品位”热量可以处于约200℃至约400℃、约220℃至约350℃,特别是约240℃至约290℃的温度水平。根据H2输出,这可以使得电力生产循环制氧设备主空气压缩机是常规的中间冷却压缩机,而不是在电力生产循环中具有显著的寄生功率降低的绝热单元。它还将导致更低的热CO2压缩机流量而进一步降低寄生功率。在如上所述的温度范围内(并且低至接近环境)的这种余热的可用性适合于在类似的温度范围内加热高压再循环CO2的侧流。所限定的集成系统同样适用于利用常规的低温氧气生产加上氧-燃料燃烧室的电力生产循环系统或利用氧离子燃烧室的系统。
在下文中关于各个附图描述根据本公开的集成电力生产和氢气生产。具体来说,图1图示了具有低温制氧设备并且使用天然气燃料的电力生产循环系统。尽管在下文中关于对应于一个示例性实施方案的操作参数描述了所述系统,但是应当了解的是,所述电力生产循环可以如本文另外所限定。此外,所述电力生产循环可以包括如以下文献中另外描述的元件和/或操作参数:Palmer等的美国专利号9,068,743;Allam等的美国专利号9,062,608;Palmer等的美国专利号8,986,002;Allam等的美国专利号8,959,887;Palmer等的美国专利号8,869,889;Allam等的美国专利号8,776,532;以及Allam等的美国专利号8,596,075,这些文献的公开内容以引用的方式并入本文。
在一个或多个实施方案中,根据本公开的电力生产循环可以被配置成使得包含CO2的工作流体至少经由压缩、加热、膨胀以及冷却的阶段重复循环。特别是,经由这些步骤中的至少一些,CO2可以是超临界的,尽管在一些实施方案中,它可以在超临界状态与液态和/或气态之间转变。在各种实施方案中,可以提高效率的电力生产循环可以包括以下步骤的组合:
·在再循环的CO2流存在下将含碳燃料用氧化剂燃烧以在至少约500℃或至少约700℃(例如约500℃至约2000℃或约600℃至约1500℃)的温度和至少约100巴(10MPa)或至少约200巴(20MPa)(例如约100巴(10MPa)至约500巴(50MPa)或约150巴(15MPa)至约400巴(40MPa))的压力下提供燃烧产物流;
·使高压再循环CO2流(例如在如上所述的压力下)在涡轮机中膨胀以用于电力生产;
·在回热式热交换器中冷却高温再循环CO2流(例如在如上所述的压力下),特别是涡轮机排出流;
·在回热式热交换器和环境冷却器中冷凝一种或多种燃烧产物(例如水),所述燃烧产物特别存在于已经膨胀和冷却的燃烧产物流中;
·将水和/或另外的物质与CO2分离以形成再循环的CO2流;
·将再循环的CO2流压缩到高压(例如,如上所述的压力),任选地在具有中间冷却的多个阶段中进行以增加流密度;
·在回热式热交换器中加热压缩的再循环CO2流,特别是相对于冷却涡轮机排气流进行加热;以及
·任选地除了从冷却涡轮机排气流回收的热量之外,还向再循环的CO2流中添加热量,所述热量来自另外的来源,如取自如本文所述的氢气生产系统或单元的低品位热量。
更具体地转向图1,举例说明了适用于与氢气生产单元组合的电力生产单元。应当了解的是,电力生产单元意图包括在一起操作时有效用于电力生产的单个部件的组合并且因而,意图与电力生产系统具有相同的含义。同样,应当了解的是,氢气生产单元意图包括在一起操作时有效用于氢气生产的单个部件的组合并且因而,意图与氢气生产系统具有相同的含义。尽管关于具体的操作参数描述了所举例说明的电力生产单元,但是应当了解的是,所述电力生产单元可以在与本文的整体公开内容一致的参数范围内操作。在图1中举例说明的电力生产单元中,在热交换器101中加热到715℃的304巴的CO2流107进入燃烧室102,在燃烧室中它与源自于甲烷流112的燃烧产物混合,所述燃烧产物在由电动机106驱动的压缩机105中被压缩到305巴(251℃),所述燃烧产物在氧化剂流108中燃烧,所述氧化剂流108具有约25摩尔%的氧气和约75摩尔%的CO2的组成并且已经在热交换器101中被加热到715℃。所得的混合流110在1150℃和300巴下进入涡轮机103中并且膨胀到30巴和725℃,作为流109离开并且在发电机104中发电。30巴的流在热交换器101中冷却并且将热量传递给高压CO2流并且在65℃作为流113离开。它在直接接触水冷却器115中进一步冷却,所述直接接触水冷却器115具有填充区段114和包括泵116和间接水冷式热交换器117的循环水区段,所述循环水区段将水流119、120以及121引导到填充区段的顶部。从水冷却器115的基部去除由CH4燃烧产生的过量液态水,即流118。离开冷却器115顶部的冷却的基本上纯的CO2流122分成多个流。基本上纯的CO2流122的第一部分123被分成被抽出用于输出或其他用途的净CO2产物流161和稀释剂流163。在优选的实施方案中,稀释剂流163在29巴下与燃烧室氧气流150共混以形成含有25%(摩尔)氧气的燃烧室氧化剂流151。冷却的基本上纯的CO2的主要部分124进入两级中间冷却CO2压缩机(具有第一压缩机级159、中间冷却器160以及第二压缩机级125),其中将它压缩到67.5巴,作为流162离开。离开冷却器115的CO2流是基本上纯的,这是因为它包含少于3摩尔%、少于2摩尔%、少于1摩尔%、少于0.5摩尔%、少于0.1摩尔%或少于0.01摩尔%的杂质。
电力生产循环需要以低于400℃的温度水平向高压CO2流提供大量另外产生的热量。在该举例说明的实施方案中,所述热量源自于提供压缩热的两个来源。第一个来源是来自空气压缩机140的5.6巴和226℃的绝热压缩的低温制氧设备进料空气流142,所述空气压缩机140由电动机141驱动压缩空气流139。第二来源是29.3巴的CO2流135,其在135℃的温度下取自热交换器101并且在压缩机136中绝热压缩以产生226℃的流137。使这两个流通过附加热交换器134,在其中它们向从直接取自多级泵129的排出流130分流的304巴的CO2流131提供附加热量。来自附加热交换器134的附加热量将CO2的温度从流131中的50℃升高到流133中的221℃。冷却的CO2流138和CO2再循环压缩机排出流162组合形成总CO2流127,将其在冷却水热交换器126中冷却以产生在19.7℃的CO2再循环流128。将该高密度CO2液体流在多级泵129中压缩到305巴。50℃的排出流130分成进入回热式热交换器101中的主要部分132和次要流131,所述次要流131在热交换器134中相对于冷却绝热压缩流137和142加热到221℃,从而产生如上所述的流133。流133在热交换器101中与高压CO2流的主要部分132重新结合。以这种方式,向再循环CO2流提供附加热量(即除了从涡轮机排出流109回收的热量之外)以实现高水平的操作效率。侧流179可以取自高压CO2流的主要部分132并且作为涡轮机叶片冷却流被引导到涡轮机103。
56℃的冷却空气流143进入低温空气分离系统中。这包括空气净化单元144,所述空气净化单元144具有直接接触空气冷却器、水冷却器以及切换式双床热再生吸附单元,所述切换式双床热再生吸附单元输送5.6巴和12℃的干燥无CO2空气流。该空气的一部分(流145)在由电动机178驱动的压缩机146中被压缩到70巴,并且空气流148和147进入泵送的液氧循环空气分离低温系统149中。来自空气分离器的产物是废氮气流160和30巴的产物氧气流150,所述产物氧气流150与离开直接接触CO2冷却器115的CO2流的冷却部分(稀释剂流163)共混以产生氧化剂流151。将其在CO2/O2压缩机组中压缩到304巴。确切地说,将氧化剂流151在由电动机153驱动的压缩机152中压缩,从而作为流155离开,将所述流155在中间冷却器154中冷却,从而作为流156离开,将所述流156在泵157中进一步压缩。将所得的压缩的氧化剂流158在热交换器101中加热到715℃,从而作为流108离开以进入燃烧室102中。
电力生产循环需要单独的低温空气分离器设备以产生氧气。这必须在被预热到通常超过700℃并且用CO2稀释的情况下以约20摩尔%至约30摩尔%的受控浓度输送到燃烧室中,这一般涉及单独的O2/CO2压缩机组或可选的具有显著高功耗的更复杂的低温空气分离设备。CH4燃料111在高压压缩机105中被压缩到305巴,如上文所述。
制氢设备与电力生产循环系统的集成(在举例说明的实施方案中以天然气为燃料)示于图2中。所述系统具有部分氧化(POX)反应器201,其具有270℃的99.5%纯O2的进料流221和500℃的天然气流246,这两者都处于85巴压力。POX反应器201提供1446℃的产物H2+CO流222(可以任选地通过添加饱和蒸汽流223将其骤冷和冷却到1350℃),所述产物H2+CO流222进入气体加热的重整器反应器202的基部203。产物H2+CO流222与离开开口的填充催化剂的管204中的每一个的重整的H2+CO产物流混合,并且总产物CO+H2流向上通过壳侧,从而为吸热重整反应提供热量并且作为在600℃的流224离开。所述管在热端处在操作温度和压差下自由地向下膨胀并且因此,管壁中的应力可忽略不计。所述管加上任何暴露的金属零件是由诸如693的合金制造的,其可以抵抗由沉积碳的鲍氏反应(Boudouard reaction)所引起的金属尘化腐蚀。此外,可以通过用氧化铝涂布来进一步保护金属表面。
流224经由通过废热锅炉236冷却并且在320℃作为产物气流254离开。产物气流254通过串联的两个填充催化剂的CO变换反应器207和208。出口流226和228进入变换流热回收热交换器209和210中,其中热量用于锅炉给水预热和天然气流预热。确切地说,离开CO变换反应器207的流226通过变换流热交换器209,从而作为流227离开以进入CO变换反应器208中。离开CO变换反应器208的流228通过变换流热交换器210,之后通过水冷却器235以作为流229离开。将锅炉给水流256和257分别在变换流热交换器210和209中加热以提供加热的水流258。将天然气流241和242分别在变换流热交换器210和209中加热以提供290℃的天然气流243。锅炉给水流258分成废热锅炉进料流260和在290℃的大量过量流259,所述大量过量流259在热交换器134(参见图1)中冷却到60℃,从而将它的热量释放到电力生产循环再循环高压CO2流131-133的一部分(示于图1中)。
离开热交换器210的粗制H2流271(其含有基本上所有源自于烃或含碳进料中的碳燃烧的CO2以及水蒸气和少量CO、CH4、N2和Ar)在水冷却器235中冷却到接近环境。在分离器212中将冷凝水从流229中分离。离开分离器212的水流262和离开热交换器134的冷却水流253进入水处理单元214,其产生纯化水255和过量水流261。纯化水255充当锅炉给水流并且在泵213中被泵送到约87巴压力。离开泵213的加压锅炉给水流256进入热交换器210中。
废热锅炉进料流260在废热锅炉236中被加热,从而作为饱和蒸汽流249离开,所述饱和蒸汽流249分成蒸汽流250和骤冷流223。饱和蒸汽流250和预热的天然气流243都在290℃进入补充热交换器237中,其中它们相对于流247被加热到500℃,所述流247对应于图1中的流109,即涡轮机排气流。出口流248在约725℃进入回热式热交换器101(在图1的电力生产单元中)。在这种情况下,升高图1的电力生产单元中涡轮机103的入口温度以提供在热交换器237中传递的所需热量并且增加涡轮机功率输出。补充热交换器237因此被配置成向饱和蒸汽流250和天然气流243提供补充加热,所述补充加热由来自电力生产单元的流提供。
离开热交换器237的热天然气流244分流以向POX反应器201提供作为在500℃流246的进料和向GHR 202提供作为流245的进料,所述流245与蒸汽流251混合以形成总GHR进料流252。在这种情况下,供给到GHR反应器202中的蒸汽流251提供6:1的蒸汽与碳的比率(在GHR反应器进料中与氢结合的碳)。该高比率允许80巴的H2+CO生产压力而在总产物H2+CO流224中具有低量的未转化的甲烷。
离开水分离器212的粗制氢气产物流230通入多床变压吸附单元215中,所述多床变压吸附单元215产生具有50ppm的杂质水平的基本上纯的H2产物流239,其包含流230中存在的氢气的88%。基本上纯的H2产物流因此可以包含少于500ppm的杂质、少于250ppm的杂质、少于100ppm的杂质或少于75ppm的杂质(例如低至0的杂质)。含有所有CO2加上各种含量的CO、H2、CH4、氩气、N2以及痕量的水蒸气的1.2巴压力的废物流232在由电动机219驱动的压缩机216中被压缩到30巴以作为流238离开。排出流238在冷却器217中冷却到接近环境并且作为入口流111(参见图1)的一部分添加到电力生产系统天然气压缩机105(参见图1)中。320巴的压缩机排出流112(参见图1)向电力生产单元燃烧室102(参见图1)提供进料。85巴的天然气进料流241也可以由单独的天然气压缩机级产生,所述单独的天然气压缩机级将是来自图1的压缩机105的一部分。
性能
操作246,151Nm3/hr的氢气生产单元与生产290.3MW电力的电力生产循环系统(这两者都具有纯CH4或天然气进料)的集成给出了以下计算的性能数据。
在74巴的压力下以50ppm的总杂质水平生产H2
来自所述集成系统的电力生产=234.23MW。
用于氢气生产的CH4=92,851.2Nm3/hr(等于923.2Mw)。
用于电力生产的CH4=43,773.9Nm3/hr(等于435.2Mw)。
作为CO2的源自于制氢设备和发电设备的CH4进料的碳的回收率是100%。
来自集成系统的CO2产量是6,437.1MT/D。
在150巴的压力下产生CO2
在如本文所述的系统和方法中,在燃烧室中使用基本上纯的氧气可以具有提供大量基本上纯的氮气的附带益处。所述氮气可以在相对高的压力下直接从空气分离单元提供,所述空气分离单元可以与电力生产单元附连以提供必要的基本上纯的氧气流。可以将该氮气的至少一部分与可以如本文所述生产的氢气共混。最终结果是H2+N2燃料气体,其适用于常规的燃气轮机联合循环发电系统中。这在图3中举例说明,其中将来自空气分离单元的氮气160(参见图1)和来自氢气生产设施的氢气239(参见图2)输入燃气轮机联合循环单元300中。
所述H2+N2燃料气体可以用于任何燃气轮机联合循环发电系统中。可以根据需要改动已知的系统以移除、停用或以其他方式放弃使用原本将为去除CO2所需的元件。可以根据本公开利用的已知的燃气轮机联合循环发电系统描述于Wichmann等的美国专利号8,726,628、Rogers等的美国专利号8,671,688、Benz等的美国专利号8,375,723、Lilley等的美国专利号7,950,239、Eroglu等的美国专利号7,908,842、Inage等的美国专利号7,611,676、Benz等的美国专利号7,574,855、Schutz的US 7,089,727、Uematsu等的美国专利号6,966,171以及Smith的美国专利号6,474,069中,这些文献的公开内容以引用的方式并入本文。
相对于燃气轮机联合循环系统的常规操作,本公开提供的系统的组合提供了明显的优势,其中由燃烧电力系统提供氢气和氮气,其中使烃燃料燃烧而基本上没有CO2的大气排放。特别是,本发明的系统组合可以消除燃气轮机中通常所需的天然气燃料并且替换为在燃烧时没有CO2产生的燃料。因而,在一些实施方案中,本公开提供了以下各项的组合:1)基于氧气的氢气生产单元;2)捕获基本上所有所产生的CO2的发电单元;以及提供额外发电的常规燃气轮机联合循环发电单元。如本文所述的组合系统可以提供惊人高的效率、低成本发电以及约100%的CO2捕获。因此,结果是一种迄今未知的方式,其用于从天然气燃烧提供电力生产而有约100%的CO2捕获并且操作成本等于或低于不提供100%CO2捕获的已知电力生产方法。
所述系统组合可以通过多种方式实现。在一些实施方案中,现有的联合循环发电站可以被转换以消除所有的CO2排放并且同时增加发电能力。这样的转换可以包括添加本文所述的用于使用CO2循环流体生产电力和生产H2+N2燃料气体的另外的系统部件。
性能
如上文所述的组合系统的性能计算可以基于GE PG9371(FB)燃气轮机热电联产系统,其被适配成在iso条件下生产432.25Mw电力。考虑到天然气燃烧电力生产单元与100%CO2捕获、H2生产、N2生产以及燃气轮机中H2+N2燃料气体的燃烧的组合,根据本公开的实施方案的计算值提供于下文中。
来自所述组合系统的总净电力产量是697Mw。
燃气轮机的燃料被假设为50%H2+50%N2(摩尔)。
总甲烷进料量是1,368.6Mw(LHV)。
所需的氧气是4979MT/天。
在150巴的压力下产生的CO2是6,437Mt/天。
总效率是50.9%(基于LHV)。
本发明公开的主题的许多修改方案和其他实施方案将由已经获益于上述说明和相关附图中所呈现的教导的本主题所属领域的技术人员所想到。因此,应当了解的是,本公开不限于本文所述的具体实施方案并且修改方案和其他实施方案意图被包括在所附权利要求的范围内。尽管在本文使用了特定的术语,但它们仅在一般的和描述性的意义上而不是为了限制的目的被使用。

Claims (29)

1.一种用于组合的电力生产和氢气生产的系统,所述系统包括:
电力生产单元,其中加压的二氧化碳膨胀以用于电力生产;
氢气生产单元,其中烃燃料被部分氧化以产生合成气,从所述合成气中分离氢气;以及
一个或多个流动部件,其被配置用于使一个或多个流在所述电力生产单元与所述氢气生产单元之间通过。
2.如权利要求1所述的系统,其中所述电力生产单元包括:
燃烧室,其被配置成接收烃燃料和氧气并且输出包含至少所述加压的二氧化碳的加热流;
涡轮机,其被配置成接收和膨胀来自所述燃烧室的包含所述加压的二氧化碳的所述加热流以生产所述电力并且形成包含膨胀的二氧化碳的加热流;
回热式热交换器,其被配置成接收包含所述膨胀的二氧化碳的所述加热流并且形成包含二氧化碳的冷却流;
分离器,其被配置成接收来自所述回热式热交换器的包含所述二氧化碳的所述冷却流并且提供所述二氧化碳流;以及
压缩机,其被配置成接收来自所述分离器的所述二氧化碳流并且压缩所述二氧化碳。
3.如权利要求2所述的系统,其中所述氢气生产单元包括:
部分氧化燃烧室,其被配置成接收氧气和所述烃燃料的一部分并且输出所述合成气;
重整器,其与所述部分氧化燃烧室处于流体连通并且被配置成接收来自所述部分氧化燃烧室的所述合成气并且接收所述烃燃料的一部分;
变换反应器,其与所述重整器处于流体连通;
变换流热交换器,其与所述变换反应器处于流体连通;
分离器,其与所述变换流热交换器处于流体连通;以及
变压吸附单元,其与所述分离器处于流体连通;
其中所述变压吸附单元被配置成输出基本上纯的氢气流。
4.如权利要求3所述的系统,其中由通过所述变换流热交换器的烃燃料管线向所述部分氧化燃烧室和所述重整器提供所述烃燃料。
5.如权利要求3所述的系统,其中所述烃燃料管线通过补充热交换器,所述补充热交换器被配置成接收和冷却离开所述电力生产单元的涡轮机的包含所述膨胀的二氧化碳的所述加热流。
6.如权利要求3所述的系统,所述系统还包括水管线,所述水管线被配置用于将水通到所述重整器。
7.如权利要求6所述的系统,其中所述水管线通过所述变换流热交换器。
8.如权利要求6所述的系统,其中所述水管线通过补充热交换器,所述补充热交换器被配置成接收和冷却离开所述电力生产单元的涡轮机的包含所述膨胀的二氧化碳的所述加热流。
9.如权利要求3所述的系统,其中所述变压吸附单元被配置成输出与所述基本上纯的氢气流分离的废物流,其中所述废物流包含一氧化碳、二氧化碳、氢气、甲烷、氩气以及氮气中的一种或多种。
10.如权利要求9所述的系统,其中所述被配置用于使一个或多个流在所述电力生产单元与所述氢气生产单元之间通过的一个或多个流动部件包括用于将所述废物流的至少一部分从所述变压吸附单元通到所述电力生产单元的燃烧室中的管线。
11.如权利要求3所述的系统,其中所述电力生产单元还包括附加热交换器,所述附加热交换器被配置成将基本上纯的二氧化碳流相对于来自所述电力生产单元的一个或多个压缩流加热。
12.如权利要求11所述的系统,其中所述附加热交换器进一步被配置成将所述基本上纯的二氧化碳流相对于来自所述氢气生产单元的流加热。
13.一种用于组合的电力生产和氢气生产的方法,所述方法包括:
在电力生产单元中进行电力生产,所述电力生产包括:
在第一燃烧室中将第一烃燃料在再循环的CO2流存在下在燃烧压力下用氧化剂燃烧以提供包含CO2的燃烧产物流;
使所述包含CO2的燃烧产物流在涡轮机中膨胀以生产电力并且形成包含CO2的涡轮机排出流;
在回热式热交换器中冷却所述包含CO2的涡轮机排出流;
将CO2与所述涡轮机排出流的任何另外的组分分离以提供包含再循环的CO2的流;
将所述包含再循环的CO2的流压缩到基本上所述燃烧压力;
将压缩的再循环的CO2流在所述回热式热交换器中用从所述涡轮机排气流中取出的热量加热以提供包含所述再循环的CO2的加热流;以及
将所述包含所述再循环的CO2的加热流通到所述第一燃烧室中;以及
在氢气生产单元中进行氢气生产,所述氢气生产包括:
使第二烃燃料流通过部分氧化反应器以形成合成气流;以及
处理所述合成气以提供基本上纯的氢气的流和包含至少一氧化碳的废物流。
14.如权利要求13所述的方法,所述方法还包括将至少所述一氧化碳从所述废物流通到所述第一燃烧室。
15.如权利要求13所述的方法,其中处理所述合成气包括使所述合成气通过重整器,所述重整器还被配置成接收第二烃燃料气流和加热水流。
16.如权利要求15所述的方法,其中将通过所述部分氧化反应器的第二烃燃料流、由所述重整器接收的第二烃燃料流以及由所述重整器接收的加热水流中的一个或多个在补充热交换器中利用从所述包含CO2的涡轮机排出流传递的热量加热。
17.如权利要求15所述的方法,其中处理所述合成气包括使来自所述重整器的重整合成气通过变换反应器,继而通过变换流热交换器。
18.如权利要求17所述的方法,其中经由通过所述变换流热交换器的烃燃料管线将所述烃燃料流提供到所述部分氧化燃烧室和所述重整器中的一个或这两者。
19.如权利要求17所述的方法,其中经由通过所述变换流热交换器的水管线提供在所述重整器中接收的所述加热水流。
20.如权利要求17所述的方法,所述方法还包括使离开所述变换流热交换器的流通过水分离器以去除水并且形成包括氢气和杂质的粗制氢气流。
21.如权利要求20所述的方法,所述方法还包括使所述粗制氢气流通过变压吸附单元,所述变压吸附单元输出所述基本上纯的氢气和所述废物流。
22.如权利要求13所述的方法,其中将所述废物流压缩到适用于输入到所述电力生产单元的燃烧室中的压力,然后通到所述电力生产单元的燃烧室中。
23.如权利要求13所述的方法,其中所述电力生产单元还包括附加热交换器,所述附加热交换器将所述再循环CO2流相对于来自所述电力生产单元的一个或多个压缩流加热。
24.如权利要求23所述的方法,所述方法还包括使来自所述氢气生产单元的加热流通过所述附加热交换器以使得来自所述氢气生产单元的热量被传递到所述再循环CO2流。
25.如权利要求24所述的方法,其中从所述氢气生产单元传递到所述再循环CO2流的热量处于低于约400℃的温度水平。
26.如权利要求13所述的方法,其中使所述包含CO2的涡轮机排出流的至少一部分与所述第一烃燃料和氧气的流一起通过第二燃烧室以使得所述第一烃燃料燃烧以向所述包含CO2的涡轮机排出流的至少一部分提供额外的热量。
27.如权利要求26所述的方法,其中使得向所述包含CO2的涡轮机排出流的至少一部分提供的额外热量的至少一部分向所述氢气生产单元中的一个或多个流提供。
28.如权利要求13所述的方法,所述方法还包括在与所述电力生产单元分开的燃气轮机中进行电力生产,其中使所述基本上纯的氢气的至少一部分在所述燃气轮机中燃烧以生产电力。
29.一种用于电力生产的系统,所述系统包括:
电力生产单元,其被配置用于连续压缩、加热、膨胀、冷却以及再循环CO2工作流体而没有CO2的大气排放;
氢气生产单元,其包括被配置成形成合成气流的部分氧化燃烧室和被配置成处理所述合成气以形成基本上纯的氢气的流和废物流的一个或多个另外的部件;以及
燃气轮机联合循环单元,其被配置成接收和燃烧所述来自所述氢气生产单元的基本上纯的氢气的至少一部分。
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