CN102171309A - 传热流体 - Google Patents

传热流体 Download PDF

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CN102171309A
CN102171309A CN2009801389067A CN200980138906A CN102171309A CN 102171309 A CN102171309 A CN 102171309A CN 2009801389067 A CN2009801389067 A CN 2009801389067A CN 200980138906 A CN200980138906 A CN 200980138906A CN 102171309 A CN102171309 A CN 102171309A
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c2h4f2
tetrafluoeopropene
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methylene fluoride
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威萨姆.雷切德
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Arkema France SA
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Abstract

本发明涉及包含四氟丙烯的组合物，更具体地涉及包含60～90重量％的2，3，3，3-四氟丙烯和10～40重量％的至少一种选自二氟乙烷和二氟甲烷的化合物的组合物，其可用作传热流体。

Description

传热流体
本发明涉及包含氢氟烯烃的组合物和它们作为传热流体、发泡剂、溶剂和气溶胶的用途。
由减少大气臭氧层(ODP：臭氧损耗潜势)的物质所造成的问题在蒙特利尔(Montreal)得到处理，在那里签署了强制减少氯氟烃(CFC)的制造和使用的协议。该协议已为修改的主体，其强制放弃CFC并将所述规定延伸到其它产品，在所述产品中有氢氯氟烃(HCFC)。
制冷工业和空调工业已经在这些制冷剂流体的替代物方面进行了大量的投资，和该投资的产品是氢氟烃(HFC)的商业化。
用作膨胀剂(expandant)或溶剂的(氢)氯氟烃也已经被HFC所替代。
在汽车工业中，在许多国家销售的车辆的空调系统已经从氯氟烃(CFC-12)制冷剂流体转换为对臭氧层损害较少的氢氟烃(1，1，1，2-四氟乙烷：HFC-134a)。然而，考虑到京都议定书(Kyoto Protocol)设定的目标，HFC-134a(GWP＝1300)被认为具有高的变暖潜势。流体对温室效应的贡献是通过标准GWP(全球变暖潜势)量化的，其通过以二氧化碳作为参考值1指出变暖潜势。
无毒、不可燃和具有非常低GWP的二氧化碳已经被提出作为空调系统的制冷剂流体来作为HFC-134a的替代物。然而，二氧化碳的使用带来许多缺点，特别是与其作为现有装置和技术中的制冷剂流体使用的非常高的压力有关。
而且，由44重量％的五氟乙烷、52重量％的三氟乙烷和4重量％的HFC-134a组成的混合物R-404A被广泛用作超级商店(超级市场)和冷冻运输中的制冷剂流体。然而，这种混合物具有3900的GWP。由52重量％的HFC-134a、25重量％的五氟乙烷和23重量％的二氟甲烷组成的混合物R-407C被用作空调和热泵中的传热流体。然而，这种混合物具有1800的GWP。
文献JP 4110388描述了其中m和n代表1～5(包括端点)的整数且m+n＝6的式C3HmFn的氢氟丙烯，特别是四氟丙烯和三氟丙烯作为传热流体的用途。
文献WO 2004/037913公开了包含至少一种具有三个或四个碳原子的含氟链烯、更具体地五氟丙烯和四氟丙烯的组合物(优选具有不超过150的GWP)作为传热流体的用途。
文献WO 2005/105947教导了向四氟丙烯、优选1，3，3，3-四氟丙烯添加助发泡剂如二氟甲烷、五氟乙烷、四氟乙烷、二氟乙烷、七氟丙烷、六氟丙烷、五氟丙烷、五氟丁烷、水或二氧化碳。
文献WO 2006/094303公开了含有7.4重量％的2，3，3，3-四氟丙烯(1234yf)和92.6重量％的二氟甲烷(HFC-32)的共沸组合物。该文献同样地公开了含有91重量％的2，3，3，3-四氟丙烯和9重量％的二氟乙烷(HFC-152a)的共沸组合物。
现在申请人开发了含有氢氟丙烯的组合物，其可用作传热流体，不具有上述缺点并且同时具有零ODP与比现有传热流体如R-404A或R-407C或R22(氯二氟甲烷)低的GWP。
根据本发明的组合物特征在于它们包含60重量％～90重量％的2，3，3，3-四氟丙烯和10重量％～40重量％的至少一种选自二氟乙烷和二氟甲烷的化合物。
根据本发明的第一实施方式，所述组合物包含60重量％～79重量％的2，3，3，3-四氟丙烯和21重量％～40重量％的选自二氟乙烷和二氟甲烷的化合物。
根据该第一实施方式的组合物优选包含60重量％～70重量％的2，3，3，3-四氟丙烯和30重量％～40重量％的选自二氟乙烷和二氟甲烷的化合物。
有利地，根据该第一实施方式的组合物包含60重量％～65重量％的2，3，3，3-四氟丙烯和35重量％～40重量％的选自二氟乙烷和二氟甲烷的化合物。
根据该第一实施方式的特别优选的组合物包含2，3，3，3-四氟丙烯和二氟甲烷。
有利地，这些组合物基本上含有2，3，3，3-四氟丙烯和二氟甲烷。
根据本发明的第二实施方式，所述组合物包含60重量％～90重量％的2，3，3，3-四氟丙烯和10重量％～40重量％的由二氯甲烷和二氟乙烷组成的混合物。
根据该第二实施方式的优选组合物包含60重量％～80重量％的2，3，3，3-四氟丙烯和20重量％～40重量％的由二氟甲烷和二氟乙烷组成的混合物。
根据该第二实施方式的有利地优选的组合物包含60重量％～75重量％的2，3，3，3-四氟丙烯和25重量％～40重量％的由二氟甲烷和二氟乙烷组成的混合物。
特别优选的组合物包含60重量％～80重量％的2，3，3，3-四氟丙烯及5重量％～35重量％的二氟甲烷和5重量％～35重量％的二氟乙烷。
关注的组合物是基本上包含或含有60重量％～80重量％的2，3，3，3-四氟丙烯及10重量％～30重量％的二氟甲烷和10重量％～30重量％的二氟乙烷的那些。
根据本发明的组合物可包含用于2，3，3，3-四氟丙烯的稳定剂。所述稳定剂占相对于总组合物的不超过5重量％。
稳定剂更具体地包括硝基甲烷，抗坏血酸，对苯二甲酸，唑如甲苯三唑或苯并三唑，酚类化合物如生育酚、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、任选地氟化或全氟化，或者链烯基或芳族环氧化物)如正丁基缩水甘油醚、己二醇二缩水甘油醚、烯丙基缩水甘油醚和丁基苯基缩水甘油醚，亚磷酸酯，磷酸酯，膦酸酯，硫醇和内酯。
根据本发明的组合物可包含润滑剂如矿物油、烷基苯、聚亚烷基二醇和聚乙烯基醚。
根据本发明的组合物适于替代在现有系统中的制冷中的R-404A和/或空调和热泵中的R-407C。它们也可适于替代采用级联压缩方式的制冷系统中的R-404A，其中用根据本发明的组合物运行至少一个阶段。特别关注的用于现有系统中的R-404A的替代物的组合物的实例包括基本上包含或含有60重量％的2，3，3，3-四氟丙烯和40重量％的二氟甲烷；70重量％的2，3，3，3-四氟丙烯和30重量％的二氟甲烷；以及60重量％的2，3，3，3-四氟丙烯、30重量％的二氟甲烷和10重量％的二氟乙烷的那些。
特别关注的用于以级联压缩方式运行的系统中的R-404A的替代物的组合物的实例包括基本上包含或含有60重量％的2，3，3，3-四氟丙烯和40重量％的二氟乙烷；70重量％的2，3，3，3-四氟丙烯和30重量％的二氟乙烷；以及75重量％的2，3，3，3-四氟丙烯、20重量％的二氟甲烷和5重量％的二氟乙烷的那些。
根据本发明的组合物也可用作例如热泵中的R-407C的替代物。
特别关注的用于现有系统中的R-407C的替代物的组合物的实例包括基本上包含或含有60重量％的2，3，3，3-四氟丙烯和40重量％的二氟甲烷；70重量％的2，3，3，3-四氟丙烯和30重量％的二氟甲烷；60重量％的2，3，3，3-四氟丙烯、30重量％的二氟甲烷和10重量％的二氟乙烷；以及70重量％的2，3，3，3-四氟丙烯、25重量％的二氟甲烷和5重量％的二氟乙烷的那些。
而且，根据本发明的组合物可用作发泡剂、气溶胶和溶剂。
实验部分
在制冷运行条件下的根据本发明的组合物的性能数据在表1中给出。各组合物的组分(1234yf、32和152a)的值以重量百分比给出。
对于R-404A，在下列运行条件下，标称运行压力为18巴，体积容量为1500kJ/m3且COP为1.8：
蒸发温度：-20℃
冷凝温度：40℃
压缩机入口温度：-5℃
过冷液温度：33℃
压缩机的等熵产率(效率，yield)：70％
BP：蒸发器的压力
HP：冷凝器的压力
比：压缩比
T压缩机出口：压缩机出口的温度
COP：性能系数-为了制冷的目的定义为系统提供的有效冷却功率，作为系统提供或消耗的功率的比例。
CAP：体积容量(kJ/m3)
％CAP或COP是混合物的CAP或COP值相对于R-404A的同样值的比。
表1
在热泵和空调的运行条件下根据本发明的组合物的性能数据在表2中给出。各组合物的组分(1234yf、32和152a)的值以重量百分比给出。
对于R-407C，在下列运行条件下，标称运行压力为34巴，体积容量为1461kJ/m3且COP为2.1。
蒸发温度：-5℃
冷凝温度：70℃
压缩机入口温度：5℃
过冷液温度：65℃
压缩机的等熵产率(效率)：70％
BP：蒸发器的压力
HP：冷凝器的压力
比：压缩比
T压缩机出口：压缩机出口的温度
COP：性能系数-为了热泵的目的定义为系统提供的有效加热功率，作为系统提供或消耗的功率的比例。
CAP：体积容量(kJ/m3)
％CAP或COP是混合物的CAP或COP值相对于R-407C的同一值的比。
表2
Figure BDA0000053443600000052
Figure BDA0000053443600000061

Claims (8)

1.组合物，其包含60重量％～90重量％的2，3，3，3-四氟丙烯和10重量％～40重量％的至少一种选自二氟乙烷和二氟甲烷的化合物。
2.权利要求1的组合物，特征在于其包含60重量％～79重量％的2，3，3，3-四氟丙烯和21重量％～40重量％的选自二氟乙烷和二氟甲烷的化合物。
3.权利要求1和2任一项的组合物，特征在于其包含60重量％～70重量％的2，3，3，3-四氟丙烯和30重量％～40重量％的选自二氟乙烷和二氟甲烷的化合物。
4.权利要求1的组合物，特征在于其包含60重量％～80重量％的2，3，3，3-四氟丙烯和20重量％～40重量％的由二氟甲烷和二氟乙烷组成的混合物。
5.权利要求1的组合物，特征在于其包含60重量％～80重量％的2，3，3，3-四氟丙烯及5重量％～35重量％的二氟甲烷和5重量％～35重量％的二氟乙烷。
6.权利要求1或5的组合物，特征在于其包含60重量％～80重量％的2，3，3，3-四氟丙烯及10重量％～30重量％的二氟甲烷和10重量％～30重量％的二氟乙烷。
7.包括前述权利要求中任一项的组合物的传热流体。
8.权利要求1～6中任一项的组合物，特征在于其用作制冷中的R-404A和/或热泵或空调中的R-407C的替代物。
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CN104603228A (zh) * 2012-09-04 2015-05-06 大金工业株式会社 含有2,3,3,3-四氟丙烯的混合制冷剂的填充方法
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CN104603228B (zh) * 2012-09-04 2018-04-06 大金工业株式会社 含有2,3,3,3‑四氟丙烯的混合制冷剂的填充方法
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CN113383060B (zh) * 2019-02-14 2023-02-21 出光兴产株式会社 冷冻机用组合物
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US20170145276A1 (en) 2017-05-25
US20160025394A1 (en) 2016-01-28
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US9599381B2 (en) 2017-03-21
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JP2019052317A (ja) 2019-04-04
US20110186772A1 (en) 2011-08-04
FR2936807A1 (fr) 2010-04-09
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JP2021066889A (ja) 2021-04-30
EP2586842A2 (fr) 2013-05-01
US20190203094A1 (en) 2019-07-04
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TW201026835A (en) 2010-07-16

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