CN101283162A - 用于orc过程的工质、orc过程和orc装置 - Google Patents
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Abstract
本发明涉及在热电联产的热ORC过程中实现能量转换的工质。具体而言,所用热源为热水。所用工质为部分或全氟化烃和/或部分或全氟化聚醚和/或部分或全氟化酮。在本发明的一个实施方案中,所用工质为1,1,1,3,3-五氟丁烷和分子量为340、101.3kPa下沸点为57℃的氟化聚醚的组合。
Description
本发明涉及用于在热电联产的热循环过程中实现能量转换的ORC过程的工质、涉及ORC过程并涉及实施ORC过程的装置。
ORC(organic Rankine cycle,有机朗肯循环)过程为以WilliamRankine的名字命名的热力学循环。ORC装置将热能转化为电流。在热ORC过程中,适宜工质的选择使得温差可以桥接和利用。这类设备用来由废热温度高于150℃的玻璃生产装置、水泥窑、炼钢炉及其他工艺的废热生成电能。地热、太阳热或来自废物焚化、生物质和其他液体或固体燃料的废热的利用或者汽轮机与废热利用的联合操作同样可以通过ORC过程实现。
地热可直接利用或转化为电能。地热向电能的转化已变得越来越重要。现在通常使用采用有机工质(ORC工质)进行操作的蒸汽动力过程。采用有机工质的这类系统由蒸发器、涡轮机、冷凝器和进给泵等主要部件及附随的控制和调节元件组成。工质的选择应使其热力学性质与存在的热源相匹配。优选使用在较低温度下蒸发的工质。
地热以温度为例如约180℃的热水形式用作热源。较低温度的热水同样可用作热源,在这种情况下必须选择蒸发温度适当低的工质。
工质经热源预热、然后过热、最后在涡轮机中减压,随着其进行,工质通过轴驱动发电机发电。其后,工质再经由进给泵冷凝和压缩并再循环进预热器中。
为保证操作的经济可行性,对工质有特定的要求。具体而言,工质的选择应考虑热源的热焓。
工质应无毒且没有任何消耗臭氧的潜能。此外,其应尽可能不易燃且在高温下仍具有适当低的压力。工质应具有高的热和化学稳定性。由于工质用在通常由金属部件组成的闭合回路中,对所用金属的反应性和腐蚀性问题同样是工质选择中的重要方面。
为限制涡轮机的造价,已发现高分子量工质的使用是有利的。由于其较低的速度,在最大涡轮机转速下,重分子的可利用的动能可在很大程度上为一个涡轮机叶片环或仅几个涡轮机叶片环所消耗。就较轻因而较易于流动的流体来说,需要采购更昂贵的较大型涡轮机或两级涡轮机以获得高转速,或需要结合其他传动装置。
已使用的适宜工质的实例包括烃如戊烷或卤代烃如三氟甲烷、四氟甲烷、五氟丙烷(EP 0066439,US 6880344)。使用纯烃情况下的显著不利在于其爆炸性。
本发明的目的是提供一种满足所述要求的用于能量回收、特别是用于利用温度至高约200℃、优选至高约180℃的热源的工质。
本发明的另一目的是提供一种满足所述要求的用于能量回收、特别是用于利用温度至高约200℃、优选至高约180℃的热源的方法。
本发明的又一目的是提供一种实施ORC过程的装置。
本发明的这些以及其他目的依靠包含至少一种选自部分或全氟化烃如四氟乙烷(特别是1,1,1,2-四氟乙烷)、五氟丙烷(特别是1,1,1,3,3-五氟丙烷)、六氟丙烷、七氟丙烷(特别是1,1,1,2,3,3,3-七氟丙烷)、五氟丁烷(特别是1,1,1,3,3-五氟丁烷)、六氟丁烷、七氟丁烷、十氟戊烷、全氟戊烷、全氟己烷的化合物或其混合物和/或至少一种选自部分或全氟化聚醚和/或部分或全氟化酮的化合物的工质;通过用于能量回收、优选用于利用温度至高约200℃、优选至高约180℃的热源的ORC过程,其中使用包含至少一种选自部分或全氟化烃如四氟乙烷(特别是1,1,1,2-四氟乙烷)、五氟丙烷(特别是1,1,1,3,3-五氟丙烷)、六氟丙烷、七氟丙烷(特别是1,1,1,2,3,3,3-七氟丙烷)、五氟丁烷(特别是1,1,1,3,3-五氟丁烷)、六氟丁烷、七氟丁烷、十氟戊烷、全氟戊烷、全氟己烷的化合物或其混合物和/或至少一种选自部分或全氟化聚醚和/或部分或全氟化酮的化合物的工质;和通过包括本发明的ORC工质的装置实现。
下面对ORC工质加以详细描述。下面详细描述的ORC工质的优选实施方案也是使用其的ORC过程和包含其的装置的优选实施方案。
上述氟化烃与上述氟化聚醚和/或酮的混合物同样可用作ORC过程的工质,并优选用作本发明的工质。本发明的工质选自为数众多的适宜化合物或这些化合物的混合物以便所用工质的沸点低于热源的温度,从而使工质可以蒸发而无任何大的技术复杂性。混合物的组成优选选择为使得形成共沸或基本共沸的混合物。
所用工质在所关心的温度范围内是稳定的并具有良好的热力学性质。
适宜的全氟化聚醚描述于例如WO 02/38718中。这些全氟化聚醚基本上由碳、氟和氧原子组成并包含至少两个、优选三个C-O-C醚键或若干满足该定义的化合物的混合物。通常,全氟聚醚中的氧原子只存在于C-O-C醚键内。全氟聚醚的分子量通常为约200或以上。其分子量通常低于约1500。如果所述聚醚为若干物质的混合物,则所述分子量为重均分子量。101.3kPa下全氟聚醚的沸点通常高于或等于40℃。101.3kPa下全氟聚醚的沸点通常低于或等于约200℃。由于制备的原因,这些全氟聚醚常为单个物质的混合物。
25℃下全氟聚醚的运动粘度通常低于或等于1cSt(厘沲)。25℃下的运动粘度通常为至少0.3cSt。
实例包括:
在本发明的优选实施方案中,所用部分氟化烃特别是为1,1,1,3,3-五氟丁烷(HFC-365mfc)、1,1,1,2-四氟乙烷(HFC 134a)、1,1,1,3,3-五氟丙烷(HFC 245fa)或其相互混合物。
聚醚与氟化烃的混合物同样是本发明范围内的适宜工质。
所用氟化酮为具有通式R-C(O)-R’的部分或全氟化酮,其中R和R’为部分或全氟化取代基,其可相同或不同,优选氟化烷基。但R也可为直链或支链烷基。含优选1-6个碳原子的氟化烷基同样可为直链或支链的,在这种情况下不超过两个氟原子可为氢所替代。R优选全氟异丙基,R’优选三氟甲基或五氟乙基。在一个实施方案中,所用部分氟化的酮为具有上述通式的化合物,其中R为直链或支链烷基,优选甲基,R’的定义同上。酮与氟化烃的混合物同样是适宜的。这些氟化酮的制备描述于EP 1261398中。适宜的酮的沸点在0℃-约150℃范围内,优选0℃-约110℃范围内,特别是0℃-约75℃范围内。
在一个优选的实施方案中,使用选自CF3C(O)CF(CF3)2、CF3CF2C(O)CF(CF3)2、CH3C(O)CF2CF2H、CH3C(O)CF2CFHCF3的氟化酮。在另一优选的实施方案中,酮与部分或全氟化烃联合用作工质。具体而言,使用包含HFC-365mfc和至少一种选自上述酮的化合物(优选CF3C(O)CF(CF3)2)或由HFC-365mfc和至少一种选自上述酮的化合物(优选CF3C(O)CF(CF3)2)组成的混合物。
优选的实施方案涉及包含一种或多种氢氟碳化合物与一种或多种(部分和/或全)氟化醚和/或一种或多种(部分和/或全)氟化酮的混合物。特别优选包含1,1,1,3,3-五氟丁烷(HFC-365mfc)和/或1,1,1,3,3-五氟丙烷(HFC 245fa)的这类混合物作为氢氟碳化合物。
WO 02/38718中所述的组合物特别适宜作为本发明的工质。
在其中所述的组合物中,氢氟烷与全氟聚醚的重量比通常高于或等于5∶95,常高于或等于10∶90,优选高于或等于25∶75。氢氟烷与全氟聚醚的重量比通常低于或等于95∶5,常低于或等于90∶10,优选低于或等于85∶15。
描述于WO 02/38718中由HFC-365mfc和特别是全氟聚醚GALDENHT55、GALDENHT70或FOMBLINPFS1形成的二元共沸混合物或假共沸混合物为可用作本发明的ORC工质的适宜混合物的实例。
HFC-365mfc与氢氟醚或HFC-365mfc与全氟己烷或HFC-365mfc与全氟戊烷或HFC-365mfc与十氟戊烷的混合物同样是优选的工质,特别是对于使用地热水作为热源的能量转换。混合比可不同,例如为50/50、40/60或65/35。优选混合比的选择使得形成共沸或基本共沸的混合物。
本发明的工质可特别用于始于温度约50-180℃的热源的能量转换。其特别适合于地热以热水的形式向电能的转换。利用其他热源如太阳热或来自垃圾焚化、生物质或者其他液体或固体燃料的废热的能量转换也同样可以想到。适宜的生物质包括例如来自植物的生物质或来自畜牧业的粪便。
同样,可按本发明转换例如来自工业生产过程的废热。在本发明的另一实施方案中,转换在用于热电联产的装置或设备中进行,例如在公共热/电站中。
上述工质适于冷却光电电池以增强太阳能的转换。由此吸收的热能可例如按本发明用以转化为其他电能。这里,冷却可单独进行,例如通过法兰式安装的结构元件,但也可通过将光电电池直接浸入工质中进行(浸没冷却)。
此外,可应用本发明的工质在工作机器或加工机器如分散的工作或加工机器(特别是例如在其中太阳能被转换为机械能的独立泵)中直接使用热源。在本文中,术语“分散的”特别是指工作或加工机器基本上按本发明供以来自自然发生于工作或加工机器所在位置或为工作或加工机器的需要人工生成的热源的能量。
多个工艺阶段的组合,例如以次级循环的形式,可使设备的效率得到提高。各个次级循环中使用的工质可相同或不同。在这种情况下,循环过程的各个次级循环的废热在各情况下被送到下一过程或下一阶段。在使用不同工质的情况下,工质可选择为使其随温度的变化有不同的蒸汽压,且蒸汽压应各在最佳范围内。这类次级回路串联的结果是在各阶段后存在为例如加热目的传输热能的可能性。
在一个实施方案中,热水经深泵(depth pump)传输到设备中。在这里,热释放给预热器和蒸发器中的工质。工质在所谓的次级回路中循环,在次级回路中,当通过进给泵增大压力后,工质流过预热器和蒸发器。过热蒸汽在涡轮机中减压并通过轴驱动发电机发电。减压不在冷凝曲线上方进行,而是总保持在湿蒸汽范围外。经减压的流体因此仍是过热的,此热必须在工质冷凝和返回预热器之前被移除。被移除的热可例如用来加热房间。
包含本发明的ORC工质、适于实施本发明的ORC过程的装置也是本发明的主题。这类装置原则上是已知的。其通常包括加热ORC工质的设备(如蒸发器,任选的预热器和/或过热器)、与发电机相连以产生电流的涡轮机和ORC工质的耗热器(冷凝器)。
图1给出了按本发明的装置的简图。其包括蒸发器E、经由在其中ORC工质被压缩的泵P与蒸发器和耗热器HC相连的管线1。通过管线1,液体ORC工质自耗热器HC输送到蒸发器E。蒸发器E通过管线2与涡轮机T相连。通过管线2,ORC工质以蒸汽形式输送到涡轮机T中。涡轮机T与产生电能的发电机G相连。涡轮机T通过管线3与耗热器HC相连。通过管线3离开涡轮机的蒸汽在耗热器HC中冷凝。蒸发器E可通过相应的热源如地热水、生物质等加热。本发明的装置包含上述ORC工质之一。耗热器HC中生成的热可例如用来加热房间。
下面用实施例对本发明加以说明。
实施例1:
ORC过程始于外部供热,经由预热器和蒸发器。
Claims (12)
1.用于ORC过程的工质,其包含以下成分或由以下成分组成:至少一种选自部分或全氟化烃的化合物和/或至少一种选自部分或全氟化聚醚的化合物和/或至少一种选自部分或全氟化酮的化合物或这些化合物的相互混合物。
2.权利要求1的用于ORC过程的工质,其中所述部分或全氟化烃为至少一种选自四氟乙烷、特别是1,1,1,3-四氟乙烷,五氟丙烷、特别是1,1,1,3,3-五氟丙烷,六氟丙烷,七氟丙烷、特别是1,1,1,2,3,3,3-七氟丙烷,五氟丁烷、特别是1,1,1,3,3-五氟丁烷,六氟丁烷,七氟丁烷,十氟戊烷,全氟戊烷,全氟己烷的化合物或其混合物。
3.权利要求2的工质,其还包含至少一种部分或全氟化聚醚。
4.权利要求1-3中任一项的工质,其中所述部分或全氟化聚醚在101.3kPa下的沸点高于或等于40℃。
5.权利要求1-4中任一项的工质,其中所述部分或全氟化醚在101.3kPa下的沸点等于或低于约200℃。
6.权利要求1-5中任一项的工质,其包含1,1,1,3,3-五氟丁烷和至少一种全氟化聚醚的混合物或由1,1,1,3,3-五氟丁烷和至少一种全氟化聚醚的混合物组成。
7.权利要求1-6中任一项的工质,其中所述至少一种全氟化聚醚在101.3kPa下的沸点为约57℃。
8.权利要求1的工质,其中所述部分或全氟化酮选自具有通式R-C(O)-R’的化合物,其中R为烷基,优选甲基,或者直链或支链的氟化C1-C6烷基,其中不超过两个氟原子可为氢所替代,R’为直链或支链的氟化C1-C6烷基,其中不超过两个氟原子可为氢所替代。
9.权利要求1和8的工质,其中所述氟化酮选自CF3C(O)CF(CF3)2、CF3CF2C(O)CF(CF3)2、CH3C(O)CF2CF2H、CH3C(O)CF2CFHCF3。
10.权利要求9的工质,其包含1,1,1,3,3-五氟丁烷和CF3C(O)CF(CF3)2的混合物或由1,1,1,3,3-五氟丁烷和CF3C(O)CF(CF3)2的混合物组成。
11.用于将热转化为电能的ORC过程,其中使用权利要求1-10中任一项的ORC工质作为ORC工质。
12.用于实施ORC过程的装置,其包括权利要求1-10中任一项的ORC工质。
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EP05019969A EP1764487A1 (de) | 2005-09-19 | 2005-09-19 | Arbeitsfluid für einen ORC-Prozess |
EP05019969.4 | 2005-09-19 | ||
US60/790,738 | 2006-04-10 |
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EP (2) | EP1764487A1 (zh) |
JP (1) | JP2009508978A (zh) |
KR (1) | KR20080045716A (zh) |
CN (1) | CN101283162A (zh) |
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2006
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CN103154447A (zh) * | 2010-08-26 | 2013-06-12 | 伊戈尔·阿纳托列维奇·列文科 | 用于转化能、增加焓并提高压缩系数的方法 |
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EP1929129A1 (en) | 2008-06-11 |
ZA200802273B (en) | 2010-05-26 |
WO2007033958A1 (en) | 2007-03-29 |
US8245512B2 (en) | 2012-08-21 |
JP2009508978A (ja) | 2009-03-05 |
US20090056333A1 (en) | 2009-03-05 |
RU2008115437A (ru) | 2009-10-27 |
KR20080045716A (ko) | 2008-05-23 |
US20110162366A1 (en) | 2011-07-07 |
EP1764487A1 (de) | 2007-03-21 |
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