CN102471671A - 传热方法 - Google Patents
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Abstract
本发明涉及制冷剂在有机兰金循环体系中的用途,所述制冷剂包含至少一种由式(I)R1CH=CHR2表示的具有至少4个碳原子的氢氟烯烃,其中R1和R2独立地表示用至少一个氟原子取代的、任选地用至少一个氯原子取代的、具有1-6个碳原子的烷基。
Description
本发明涉及借助于包含氢氟烯烃的组合物的能量转化方法。更具体地,本发明涉及包含氢氟烯烃的组合物在有机兰金循环体系中的用途。
随着能量价格的持续提高,对于能量的使用和回收的优化存在增长的需要。而且,用于提高对减少二氧化碳排放的需要的意识的活动显示出能量回收的重要性。
能量回收的原理是将未使用的能量转化为电。流体如气体的膨胀将动能转化为机械能。因此,涡轮机通过如下产生电:利用膨胀现象驱动轮子并产生电。
兰金循环构成用于由液态水/蒸汽产生能量的在工业水平上的基本循环。其由以下阶段组成:(i)加热;(ii)在恒温下进行蒸发直至达到饱和;(iii)等熵膨胀(理想情况);(iv)在恒温下冷凝;和(v)等熵压缩。
兰金循环可应用于其它热力学体系,尤其是使用除蒸汽外的流体的热力学体系。有机兰金循环使得可利用这些其它流体的性能。
在蒙特利尔商议了由损耗大气臭氧层(具有臭氧损耗潜势,ODP)的物质导致的问题,在蒙特利尔签署了要求减少氯氟烃(CFC)的制造和使用的议定书。已经对该议定书进行了修正,要求放弃CFC并且扩展至对其它产品的控制。
氢氟烃(HFC)已经代替CFC和/或氢氯氟烃(HCFC)。
因此,已经提出1,1,3,3,3-五氟丙烷(HFC-245fa)作为用于有机兰金循环体系的流体,其中在140°F-300°F(60-149℃)的温度下对HFC-245fa进行加热(WO 2006/113902)。
文献WO 2005/085398公开了多氟化醚和多氟化酮的用途,它们作为在HFC-245fa的临界温度(154℃)或高于该临界温度,用于将热能转化为机械能(尤其是用于有机兰金循环体系)的流体。
采用这些多氟化醚或酮所遇到的问题是在冷凝器处的低压,从而促进空气渗透到装置中。湿气和氧气在装置中的存在导致机械部件的腐蚀和破坏。
本申请人现已发现:包含氢氟烯烃的组合物非常特别地适合作为用于在有机兰金循环体系(尤其是在60-150℃的低温下操作的体系)中的能量转化的流体。而且,这些组合物具有可忽略的ODP和低于现有流体的GWP(全球增温潜势)。这些混合物还具有高于150℃的临界温度,因此可在较高的温度下在有机兰金循环体系中使用。
流体对于温室效应的贡献由标准GWP量化,所述GWP概括升温效应,其以二氧化碳作为参考值1。
有机兰金循环体系在一个或多个级中使用称为制冷剂的流体操作。
本发明涉及使用涡轮机系统的能量转化方法,所述涡轮机系统具有至少一个相继包括如下步骤的级:制冷剂的蒸发步骤、在涡轮机中的膨胀步骤、在内交换器中的去过热(降温,desuperheating)步骤、所述流体的冷凝步骤、以及在泵中的液体压缩步骤,特征在于所述制冷剂包含至少一种由式(I)R1CH=CHR2表示的具有至少4个碳原子的氢氟烯烃,其中R1和R2独立地表示用至少一个氟原子取代的、任选地用至少一个氯原子取代的、具有1-6个碳原子的烷基。
优选地,所述氢氟烯烃的至少一个烷基被氟原子完全取代。
优选地,制冷剂的冷凝温度大于或等于空气或天然冷源(湖泊或水流)的环境温度,取决于季节和地理位置,所述环境温度通常为-40℃~50℃。
优选地,制冷剂的蒸发温度为60-150℃、且有利地为80℃-150℃。
作为特别有利的式(I)的氢氟烯烃,我们可特别提及1,1,1,4,4,4-六氟丁-2-烯、1,1,1,4,4,5,5,5-八氟戊-2-烯、1,1,1,4-四氟丁-2-烯、1,1,1,4,4-五氟丁-2-烯、1,1,4-三氟丁-2-烯、1,1,1-三氟丁-2-烯、4-氯-1,1,1-三氟丁-2-烯、4-氯-4,4-二氟丁-2-烯。
优选的式(I)的氢氟烯烃可为顺式或反式、或者两者的混合。
除了式(I)的氢氟烯烃外,制冷剂可包含至少一种选自氢氟烃、烃、(氢)氟醚、氢氯氟丙烯、氢氟丙烯、醚、醇、甲酸甲酯、二氧化碳和反式-1,2-二氯乙烯的化合物。
作为氢氟烃,我们可特别提及1,1,1,3,3-五氟丁烷、1,1,1,2-四氟乙烷、五氟乙烷、1,1,1,3,3-五氟丙烷、1,1,1,2,3-五氟丙烷、1,1,1,2,2-五氟丙烷、1,1,1,3,3,3-六氟丙烷、1,1,2,2,3-五氟丙烷、1,1,1,3,3-五氟丁烷、1,1,1,2,2,3,4,5,5,5-十氟戊烷和1,1,1,2,3,3,3-七氟丙烷。
优选具有至少三个碳原子的烃。尤其优选具有5个碳原子的烃如戊烷、异戊烷、环戊烷。
优选的氢氯氟丙烯为2-氯-3,3,3-三氟丙-1-烯和1-氯-3,3,3-三氟丙-1-烯,尤其是反式-1-氯-3,3,3-三氟丙-1-烯。
优选的氢氟醚为具有3-6个碳原子的那些。
作为氢氟醚,我们可特别提及七氟甲氧基丙烷、九氟甲氧基丁烷和九氟乙氧基丁烷。氢氟醚可以若干种同分异构形式利用,例如1,1,1,2,2,3,3,4,4-九氟-乙氧基丁烷、1,1,1,2,3,3-六氟-2-(三氟甲基)-3-乙氧基丁烷、1,1,1,2,2,3,3,4,4-九氟-甲氧基丁烷、1,1,1,2,3,3-六氟-2-(三氟甲基)-3-甲氧基丁烷和1,1,1,2,2,3,3-七氟甲氧基丙烷。
优选的氢氟丙烯为三氟丙烯如1,1,1-三氟丙烯、四氟丙烯如2,3,3,3-四氟丙烯(HFO-1234yf)和1,3,3,3-四氟丙烯(顺式和/或反式的)。
醚可选自二甲醚、二乙醚、二甲氧基甲烷或二丙氧基甲烷。
醇可选自乙醇、异丙醇、丁醇和异丁醇。
优选地,制冷剂包含至少一种式(I)的氢氟烯烃和至少一种氢氟烃。所述氢氟烃有利地选自1,1,1,3,3-五氟丁烷和1,1,1,3,3-五氟丙烷。
1,1,1,4,4,4-六氟丁-2-烯或1,1,1,4,4,5,5,5-八氟-戊-2-烯与甲酸甲酯、戊烷、异戊烷、环戊烷或反式-1,2-二氯乙烯的共沸组合物也可为合适的。
优选地,制冷剂包含至少10重量%的式(I)的氢氟烯烃。
根据本发明的一个实施方案,制冷剂包含:40-100重量%的1,1,1,4,4,4-六氟丁-2-烯;以及0-60重量%的至少一种选自戊烷、异戊烷、环戊烷和反式-1,2-二氯乙烯的化合物。
作为特别优选的制冷剂,我们可提及包含60-100重量%的1,1,1,4,4,4-六氟丁-2-烯和0-40重量%的环戊烷、戊烷、异戊烷或反式-1,2-二氯乙烯的那些。
本发明中所用的制冷剂可包含氢氟烯烃的稳定剂。相对于流体的总组成,该稳定剂占至多5重量%。
作为稳定剂,我们可特别提及:硝基甲烷;抗坏血酸;对苯二甲酸;唑,例如甲苯并三唑(tolutriazole)或苯并三唑;酚化合物,例如生育酚、对苯二酚、叔丁基对苯二酚、2,6-二-叔丁基-4-甲基苯酚;环氧化物(烷基环氧化物(任选地被氟化或全氟化)、或者烯基或芳族环氧化物),例如正丁基缩水甘油醚、己二醇二缩水甘油醚、烯丙基缩水甘油醚、丁基苯基缩水甘油醚;亚磷酸酯;磷酸酯;膦酸酯;硫醇;和内酯。
根据本发明的方法中所用的制冷剂可包含润滑剂,例如矿物油、烷基苯、聚α烯烃、聚亚烷基二醇、多元醇酯和聚乙烯基醚。与制冷剂一起使用的润滑剂可包含用于改善流体的导热性以及流体与润滑剂的相容性的纳米颗粒。作为纳米颗粒,我们可特别提及Al2O3或TiO2的颗粒。
与制冷剂一起使用的润滑剂可包含沸石型减湿剂。沸石吸收水,这防止腐蚀和性能劣化。
实验部分
Evap:蒸发器,
Cond:冷凝器,
Temp:温度,
P:压力,
效率:其为由涡轮机提供的功率与供给至体系的有用高温功率之比。
下面给出在蒸发器处的温度保持为11.7℃且冷凝器处的温度为149℃的能量转化循环中的操作条件下的制冷剂性能。
涡轮机的等熵效率:100%
C:异戊烷
D:TDCE
F:戊烷
G:1,1,1,4,4,4-六氟丁-2-烯
PFE-PFIPK(全氟乙基全氟异丙基酮)
MPFBE(甲基全氟丁基醚)
结果表明:对于PEE-PFIPK和MPFBE这两种产品,在冷凝器处的压力低,这促进空气渗透到装置中。
Claims (10)
1.采用涡轮机系统的能量转化方法,所述涡轮机系统具有至少一个相继包括如下步骤的级:制冷剂的蒸发步骤、在涡轮机中的膨胀步骤、在内交换器中的去过热步骤、所述流体的冷凝步骤、以及在泵中的液体压缩步骤,特征在于所述制冷剂包含至少一种由式(I)R1CH=CHR2表示的具有至少4个碳原子的氢氟烯烃,其中R1和r2独立地表示用至少一个氟原子取代的、任选地用至少一个氯原子取代的、具有1-6个碳原子的烷基。
2.权利要求1的方法,特征在于蒸发温度为60-150℃、优选80-150℃。
3.权利要求1或2的方法,特征在于所述制冷剂进一步包含至少一种选自氢氟烃、烃、(氢)氟醚、氢氯氟丙烯、氢氟丙烯、醚、甲酸甲酯、二氧化碳和反式-1,2-二氯乙烯的化合物。
4.权利要求1-3中任一项的方法,特征在于所述制冷剂包含至少一种选自1,1,3,3,3-五氟丙烷和1,1,3,3,3-五氟丁烷的氢氟烃。
5.权利要求1-4中任一项的方法,特征在于所述制冷剂包含至少一种选自戊烷、异戊烷和环戊烷的氢氟烃。
6.权利要求1-5中任一项的方法,特征在于所述制冷剂包含40-100重量%的1,1,1,4,4,4-六氟丁-2-烯、以及0-60重量%的至少一种选自戊烷、异戊烷、环戊烷和反式-1,2-二氯乙烯的化合物。
7.权利要求1-6中任一项的方法,特征在于所述制冷剂包含60-100重量%的1,1,1,4,4,4-六氟丁-2-烯、以及0-40重量%的环戊烷、戊烷、异戊烷或反式-1,2-二氯乙烯。
8.权利要求1-7中任一项的方法,特征在于所述制冷剂包含稳定剂。
9.权利要求1-8中任一项的方法,特征在于所述制冷剂包含润滑剂。
10.权利要求9的方法,特征在于所述润滑剂为聚亚烷基二醇、多元醇酯或聚乙烯基醚。
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FR0955267A FR2948679B1 (fr) | 2009-07-28 | 2009-07-28 | Procede de transfert de chaleur |
PCT/FR2010/051283 WO2011015738A1 (fr) | 2009-07-28 | 2010-06-23 | Procede de transfert de chaleur |
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CN104047649A (zh) * | 2013-03-15 | 2014-09-17 | 霍尼韦尔国际公司 | 用于高温热传递应用的稳定化的hfo和hcfo组合物 |
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US10443912B2 (en) | 2013-10-25 | 2019-10-15 | Mitsubishi Heavy Industries Thermal Systems, Ltd. | Refrigerant circulation device, method for circulating refrigerant and acid suppression method |
US10465959B2 (en) | 2013-10-25 | 2019-11-05 | Mitsubishi Heavy Industries Thermal Systems, Ltd. | Refrigerant circulation device, method for circulating refrigerant and method for suppressing isomerization |
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EP3444315A1 (fr) | 2019-02-20 |
EP2459668B1 (fr) | 2018-09-05 |
US20120117991A1 (en) | 2012-05-17 |
PL2459668T3 (pl) | 2018-11-30 |
US20160115827A1 (en) | 2016-04-28 |
JP6138194B2 (ja) | 2017-05-31 |
JP2013500374A (ja) | 2013-01-07 |
CN102471671B (zh) | 2016-05-04 |
ES2689455T3 (es) | 2018-11-14 |
FR2948679B1 (fr) | 2011-08-19 |
EP2459668A1 (fr) | 2012-06-06 |
US9279074B2 (en) | 2016-03-08 |
WO2011015738A1 (fr) | 2011-02-10 |
FR2948679A1 (fr) | 2011-02-04 |
US10704428B2 (en) | 2020-07-07 |
US20180320560A1 (en) | 2018-11-08 |
JP2015158361A (ja) | 2015-09-03 |
US10036285B2 (en) | 2018-07-31 |
JP6071552B2 (ja) | 2017-02-01 |
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