CN1914292A - 有机兰金循环流体 - Google Patents

有机兰金循环流体 Download PDF

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CN1914292A
CN1914292A CNA2005800038332A CN200580003833A CN1914292A CN 1914292 A CN1914292 A CN 1914292A CN A2005800038332 A CNA2005800038332 A CN A2005800038332A CN 200580003833 A CN200580003833 A CN 200580003833A CN 1914292 A CN1914292 A CN 1914292A
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steam
heat
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J·J·布拉斯兹
U·J·荣松
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Raytheon Technologies Corp
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K5/00—Heat-transfer, heat-exchange or heat-storage materials, e.g. refrigerants; Materials for the production of heat or cold by chemical reactions other than by combustion
    • C09K5/02—Materials undergoing a change of physical state when used
    • C09K5/04—Materials undergoing a change of physical state when used the change of state being from liquid to vapour or vice versa
    • C09K5/041—Materials undergoing a change of physical state when used the change of state being from liquid to vapour or vice versa for compression-type refrigeration systems
    • C09K5/044—Materials undergoing a change of physical state when used the change of state being from liquid to vapour or vice versa for compression-type refrigeration systems comprising halogenated compounds
    • C09K5/045—Materials undergoing a change of physical state when used the change of state being from liquid to vapour or vice versa for compression-type refrigeration systems comprising halogenated compounds containing only fluorine as halogen
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    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K5/00—Heat-transfer, heat-exchange or heat-storage materials, e.g. refrigerants; Materials for the production of heat or cold by chemical reactions other than by combustion
    • C09K5/02—Materials undergoing a change of physical state when used
    • C09K5/04—Materials undergoing a change of physical state when used the change of state being from liquid to vapour or vice versa
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    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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    • C09K5/00—Heat-transfer, heat-exchange or heat-storage materials, e.g. refrigerants; Materials for the production of heat or cold by chemical reactions other than by combustion
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
    • F01K—STEAM ENGINE PLANTS; STEAM ACCUMULATORS; ENGINE PLANTS NOT OTHERWISE PROVIDED FOR; ENGINES USING SPECIAL WORKING FLUIDS OR CYCLES
    • F01K25/00—Plants or engines characterised by use of special working fluids, not otherwise provided for; Plants operating in closed cycles and not otherwise provided for
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
    • F01K—STEAM ENGINE PLANTS; STEAM ACCUMULATORS; ENGINE PLANTS NOT OTHERWISE PROVIDED FOR; ENGINES USING SPECIAL WORKING FLUIDS OR CYCLES
    • F01K25/00—Plants or engines characterised by use of special working fluids, not otherwise provided for; Plants operating in closed cycles and not otherwise provided for
    • F01K25/08—Plants or engines characterised by use of special working fluids, not otherwise provided for; Plants operating in closed cycles and not otherwise provided for using special vapours
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2205/00—Aspects relating to compounds used in compression type refrigeration systems
    • C09K2205/10—Components
    • C09K2205/108—Aldehydes or ketones

Abstract

一种操作有机兰金循环系统的方法，其中将液体制冷剂循环到蒸发器，在该蒸发器中将热量引入到该制冷剂中以使其转变成蒸气。该蒸气随后经过涡轮机，所获得的冷却的蒸气随后经过冷凝器，以使得该蒸气冷凝成液体。该制冷剂是CF3CF2C(O)CF(CF3) 2，(CF3) 2CFC(O)CF(CF3) 2，CF3 (CF2) 2C(O)CF(CF3) 2，CF3 (CF2) 3C(O)CF(CG3) 2，CF3 (CF2) 5C(O)CF3，CF3CF2C(O)CF2CF2CF3，CF3C(O)CF(CF3) 2中的一种。

Description

有机兰金循环流体
背景技术
本发明总体上涉及有机兰金循环系统，尤其涉及所述系统中的改进工作流体的用途。
公知的封闭式兰金循环包括用于蒸发动力流体的锅炉或蒸发器，从该锅炉供应蒸气以便驱动发电机或其它负载的涡轮机，用于使得来自该涡轮机的排出蒸气冷凝的冷凝器，以及用于使得冷凝的流体再循环到该锅炉的装置，例如泵。美国专利3,393,515说明和描述了这种系统。
这些兰金循环系统通常用于发电，发出的电力可供应给配电系统或电网，用于国内的民用和商用。在这些系统内所使用的动力流体通常是水，其中涡轮机由蒸气来驱动。供应给锅炉的热源可以是任何形式的化石燃料，例如油、煤、天然气或核能。在这些系统中涡轮机设计成在较高的压力和温度下工作，并且其制造和使用成本较高。
有机兰金循环(ORC)是用制冷剂(有机流体)代替水/蒸气作为工作流体的蒸气动力循环。功能上它类似于蒸气循环发电机：一种增加冷凝液体制冷剂压力的泵。通过从涡轮机或发动机废气中提取废热，将该液体在蒸发器/锅炉中蒸发。高压制冷剂蒸气在涡轮机中膨胀而产生电力。离开涡轮机的低压蒸气在流回泵进行重循环之前被冷却。
由于制冷剂具有某些特性，在发电ORC体系中使用具有确凿可靠性和性能记录的商购空调和制冷设备花费会非常高。
用于发电的兰金循环按照下面的四步顺序进行：
1.用泵升高绝热压力
2.在预热器，蒸发器和过热器中等压加热
3.在涡轮机中绝热膨胀
4.在冷凝器中等压热消耗
有机兰金循环中的主要热力学不可逆性是由于蒸发器中废热流和沸腾的制冷剂间温度的巨大温差造成的。废热流温度越高，此不可逆性就变得越大。在较高温度下能沸腾的有机流体具有降低废热流和有机兰金循环工作流体间温差的能力，从而可以获得更高的热力学ORC循环效率。流体可在高至临界温度的温度下沸腾，在该临界温度以上不沸腾。因此，具有较高临界温度的流体能获得更高的ORC循环效率。过去就已建议使用具有高临界温度的含氯流体作为ORC流体。例如R114，R113，R11，R141b和R123比R245fa的临界温度高，因而实质上获得的热效率就更高。然而，这些流体可燃和/或有毒，破坏臭氧层和/或具有显著的全球变暖影响。它们已经被禁用(CFC’s)或很快将会被禁用(HCFC’s)，因此将不能用于未来的ORC生产。
发明概述
因此本发明的目的是克服上述的现有技术问题。
本发明的另一目的是提供新的改进的有机兰金循环工作流体。
本发明的另一目的是提供能在较低压力和较低涡轮机机速下工作的有机兰金循环工作流体。
本发明的又一目的是提供具有高临界温度且环境友好的有机循环工作流体。
本发明的再一目的是提供在使用中经济实用且环境友好的兰金循环系统。
已经发现，最近作为灭火流体引入市场的一种有机流体具有作为有机兰金循环系统中的工作流体或制冷剂的独特用途。优选的流体实例是酮CF3CF2C(O)CF(CF3)2，其临界温度高于最可接受的现有技术流体R245fa。此流体具有零臭氧层潜力和零全球变暖潜力，因此是环境友好的。
在典型有机兰金循环系统中使用此流体和等效酮可以是有利的，如在该系统中用泵将液体制冷剂循环到蒸发器，在该蒸发器中将热量引入到该制冷剂中以使其转变成蒸气，该蒸气随后先经过多个喷嘴，然后经过涡轮机。所获得的冷却的蒸气随后经过冷凝器，以使得该蒸气冷凝成液体。在本发明中，制冷剂可以是CF3CF2C(O)CF(CF3)2，(CF3)2CFC(O)CF(CF3)2，CF3(CF2)2C(O)CF(CF3)2，CF3(CF2)3C(O)CF(CG3)2，CF3(CF2)5C(O)CF3，CF3CF2C(O)CF2CF2CF3，CF3C(O)CF(CF3)2，全氟环己酮和其混和物中的任何一种。
附图的简要说明
通过结合所附附图并且参照以下的本发明详细描述，可以进一步理解发明的这些目的，其中
图1是根据本发明的有机兰金循环系统的示意图。
图2是R245fa和CF3CF2C(O)CF(CF3)2的对比TS图表。
图3说明使用245fa利用370℃显废热源的ORC。
图4说明使用CF3CF2C(O)CF(CF3)2利用370℃显废热源的ORC。
图5是说明本发明第二实施方案的有机兰金循环系统的示意图。
发明详述
参照图1，所示的典型兰金循环系统10包括蒸发器/锅炉12和冷凝器14，它们分别接收和分配热量。这些组件执行的功能与在传统空调和制冷系统中使用的蒸气压缩循环中的功能相似。因此，这些热交换组件在有机兰金循环应用中使用时可以进行微小改变。兰金循环包括发电涡轮机16，其通过该系统中的动力流体来驱动并且进而驱动产生电力的发电机18，以及增加离开冷凝器的液体压力的电消耗泵20。
在操作时，蒸发器，其通常是输入大量热量的锅炉，将动力流体蒸发，所述动力流体是本发明的新型制冷剂，该蒸气随后经过涡轮机为其提供动力。一旦离开涡轮机，低压蒸气就经过冷凝器18，在该冷凝器中借助与冷却介质的热交换关系，蒸气被冷凝。随后，如图所示，冷凝的液体通过泵22循环到蒸发器，从而完成循环。
图2显示R245fa和CF3CF2C(O)CF(CF3)2的对比TS图表。应注意CF3CF2C(O)CF(CF3)2的临界温度较高。
图3显示使用R245fa利用被冷却到93℃(B点)的370℃显废热源(A点)的有机兰金循环。R245fa有机兰金循环的过程包括将涡轮机中的工作流体膨胀，和因此产生的电力，从状态点1进行到点2。在冷凝器中脱过热(2->3)和冷凝(3->4)，从而排到周围环境中去。用泵增大压力(4->5)，利用废热在制冷剂锅炉中预热(5->6)和蒸发(6->1)，且所述废热从入口温度A被冷却到出口温度B。
图4显示使用CF3CF2C(O)CF(CF3)2利用相同废热流的有机兰金循环。由于如图1所示CF3CF2C(O)CF(CF3)2的临界温度高于R245fa的事实，R245fa比CF3CF2C(O)CF(CF3)2的热转化不可逆性-面积AB561A-略大。这就使得与R245fa相比，CF3CF2C(O)CF(CF3)2的热动力兰金循环效率更高。
CF3CF2C(O)CF(CF3)2的状态点2处的涡轮机出口温度高于R245fa。这使得可以用水加热器代替部分冷凝器，并且以CHP(组合热电)模式运行有机兰金循环，如图5所示。为了用R245fa获得相同的CHP功能，需要更高的涡轮机出口温度，使设计复杂化并导致更高的最初成本。
尽管参照如附图所示的最佳实施方式，对本发明进行了具体地说明和描述，但是本领域的普通技术人员应当理解，在不脱离如权利要求所限定的本发明的精神和范围的情况下，可以进行各种细节的改变。
权利要求书
(按照条约第19条的修改)
1、一种操作有机兰金循环系统的方法，其中将液体制冷剂循环到蒸发器，在该蒸发器中将热量引入到该制冷剂中以使其转变成蒸气，该蒸气随后经过涡轮机，所获得的冷却的蒸气随后经过冷凝器，便使得该蒸气冷凝成液体；其中所述制冷剂是CF3CF2C(O)CF(CF3)2。
2、一种操作有机兰金循环系统的方法，其中将液体制冷剂循环到蒸发器，在该蒸发器中将热量引入到该制冷剂中以使其转变成蒸气，该蒸气随后经过涡轮机，所获得的冷却的蒸气随后经过冷凝器，以使得该蒸气冷凝成液体；其中所述制冷剂选自下组：CF3CF2C(O)CF(CF3)2，(CF3)2CFC(O)CF(CF3)2，CF3(CF2)2C(O)CF(CF3)2，CF3(CF2)3C(O)CF(CG3)2，CF3(CF2)5C(O)CF3，CF3CF2C(O)CF2CF2CF3，CF3C(O)CF(CF3)2。
3、一种操作有机兰金循环系统的方法，其中泵用于将液体制冷剂循环到蒸发器，在该蒸发器中将热量引入到该制冷剂中以使其转变成蒸气，该蒸气随后首先经过多个喷嘴，然后经过涡轮机，所获得的冷却的蒸气随后经过冷凝器，以使得该蒸气冷凝成液体；其中将热量引入到该制冷剂中的步骤是用从发动机中提取废热的方法，并且所述制冷剂是CF3CF2C(O)CF(CF3)2。
4、(删除)
5、如权利要求13所述的方法，其中从所述内燃机中提取热量的步骤是通过从离开所述内燃机的废气中提取热量来实现的。
6、如权利要求13所述的方法，其中从内燃机中提取热量的步骤是通过从在所述内燃机中流动的冷却剂中提取热量来实现的。
7、一种操作有机兰金循环系统的方法，其中泵用于将液体制冷剂循环到蒸发器，在该蒸发器中将热量引入到该制冷剂中以使其转变成蒸气，该蒸气随后首先经过多个喷嘴，然后经过涡轮机，所获得的冷却的蒸气随后经过冷凝器，以使得该蒸气冷凝成液体；其中将热量引入到该制冷剂中的步骤是用从发动机中提取废热的方法，并且所述制冷剂是选自CF3CF2C(O)CF(CF3)2，(CF3)2CFC(O)CF(CF3)2，CF3(CF2)2C(O)CF(CF3)2，CF3(CF2)3C(O)CF(CG3)2，CF3(CF2)5C(O)CF3，CF3CF2C(O)CF2CF2CF3，CF3C(O)CF(CF3)2，全氟环己酮和其混和物组成的组中的至少一种。
8、如权利要求7所述的方法，其中所述发动机是内燃机。
9、(删除)
10、(删除)
11、一种操作有机兰金循环系统的方法，其中将液体制冷剂循环到蒸发器，在该蒸发器中将热量引入到该制冷剂中以使其转变成蒸气，该蒸气随后经过涡轮机，所获得的冷却的蒸气随后经过冷凝器，以使得该蒸气冷凝成液体；其中所述制冷剂是CF3CF2C(O)CF(CF3)2，且所述冷凝器进一步包括利用从所述涡轮机获得的废热产生热水的水加热器。
12、一种操作有机兰金循环系统的方法，其中将液体制冷剂循环到蒸发器，在该蒸发器中将从内燃机吸取的热量引入到该制冷剂中以使其转变成蒸气，该蒸气随后经过涡轮机，所获得的冷却的蒸气随后经过冷凝器，以使得该蒸气冷凝成液体；其中所述制冷剂是CF3CF2C(O)CF(CF3)2。
13、一种操作有机兰金循环系统的方法，其中将液体制冷剂循环到蒸发器，在该蒸发器中将从内燃机吸取的热量引入到该制冷剂中以使其转变成蒸气，该蒸气随后经过涡轮机，所获得的冷却的蒸气随后经过冷凝器，以使得该蒸气冷凝成液体；其中所述制冷剂选自下组：CF3CF2C(O)CF(CF3)2，(CF3)2CFC(O)CF(CF3)2，CF3(CF2)2C(O)CF(CF3)2，CF3(CF2)3C(O)CF(CG3)2，CF3(CF2)5C(O)CF3，CF3CF2C(O)CF2CF2CF3，CF3C(O)CF(CF3)2。

Claims (11)

1、一种操作有机兰金循环系统的方法，其中将液体制冷剂循环到蒸发器，在该蒸发器中将热量引入*到该制冷剂中以使其转变成蒸气，该蒸气随后经过涡轮机，所获得的冷却的蒸气随后经过冷凝器，以使得该蒸气冷凝成液体；其中所述制冷剂是CF3CF2C(O)CF(CF3)2。
2、一种操作有机兰金循环系统的方法，其中将液体制冷剂循环到蒸发器，在该蒸发器中将热量引入到该制冷剂中以使其转变成蒸气，该蒸气随后经过涡轮机，所获得的冷却的蒸气随后经过冷凝器，以使得该蒸气冷凝成液体；其中所述制冷剂选自下组：CF3CF2C(O)CF(CF3)2，(CF3)2CFC(O)CF(CF3)2，CF3(CF2)2C(O)CF(CF3)2，CF3(CF2)3C(O)CF(CG3)2，CF3(CF2)5C(O)CF3，CF3CF2C(O)CF2CF2CF3，CF3C(O)CF(CF3)2。
3、一种操作有机兰金循环系统的方法，其中泵用于将液体制冷剂循环到蒸发器，在该蒸发器中将热量引入到该制冷剂中以使其转变成蒸气，该蒸气随后首先经过多个喷嘴，然后经过涡轮机，所获得的冷却的蒸气随后经过冷凝器，以便使得该蒸气冷凝成液体；其中将热量引入到该制冷剂中的步骤是用从发动机中提取废热的方法，并且所述制冷剂是CF3CF2C(O)CF(CF3)2。
4、如权利要求1所述的方法，其中所述发动机是内燃机。
5、如权利要求2所述的方法，其中从所述内燃机中提取热量的步骤是通过从离开所述内燃机的废气中提取热量来实现的。
6、如权利要求2所述的方法，其中从内燃机中提取热量的步骤是通过从在所述内燃机中流动的冷却剂中提取热量来实现的。
7、一种操作有机兰金循环系统的方法，其中泵用于将液体制冷剂循环到蒸发器，在该蒸发器中将热量引入到该制冷剂中以使其转变成蒸气，该蒸气随后首先经过多个喷嘴，然后经过涡轮机，所获得的冷却的蒸气随后经过冷凝器，以使得该蒸气冷凝成液体；其中将热量引入到该制冷剂中的步骤是从发动机中提取废热，并且所述制冷剂是选自CF3CF2C(O)CF(CF3)2，(CF3)2CFC(O)CF(CF3)2，CF3(CF2)2C(O)CF(CF3)2，CF3(CF2)3C(O)CF(CG3)2，CF3(CF2)5C(O)CF3，CF3CF2C(O)CF2CF2CF3，CF3C(O)CF(CF3)2，全氟环己酮和其混和物组成的组中的至少一种。
8、如权利要求7所述的方法，其中所述发动机是内燃机。
9、如权利要求6所述的方法，其中从所述内燃机中提取热量的步骤是通过从离开所述内燃机的废气中提取热量来实现的。
10、权利要求6所述的方法，其中从内燃机中提取热量的步骤是通过从在所述内燃机中流动的冷却剂中提取热量来实现的。
11、一种操作有机兰金循环系统的方法，其中将液体制冷剂循环到蒸发器，在该蒸发器中将热量引入到该制冷剂中以使其转变成蒸气，该蒸气随后经过涡轮机，所获得的冷却的蒸气随后经过冷凝器，以便使得该蒸气冷凝成液体；其中所述制冷剂是CF3CF2C(O)CF(CF3)2，且所述冷凝器进一步包括利用从所述涡轮机获得的废热产生热水的水加热器。
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CN102619581A (zh) 2012-08-01
US20050166607A1 (en) 2005-08-04
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