CN102686695B - 选择制冷剂-润滑剂组合的方法 - Google Patents

选择制冷剂-润滑剂组合的方法 Download PDF

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CN102686695B
CN102686695B CN201080059823.1A CN201080059823A CN102686695B CN 102686695 B CN102686695 B CN 102686695B CN 201080059823 A CN201080059823 A CN 201080059823A CN 102686695 B CN102686695 B CN 102686695B
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B·L·范霍恩
P·波内特
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Abstract

本发明提供了选择制冷剂润滑剂组合以用于热传递循环***中的方法并且提供了用于运行所述热传递***的方法。更确切地说，本发明提供了用来选择制冷剂润滑剂组合以用于热传递循环***中的方法，其中在该热传递循环的较低温度下该制冷剂与润滑剂是易混溶的并且在该热传递循环的较高温度下该制冷剂与润滑剂是相分离的并且使得该组合的密度相转移温度低于该热传递循环的较高运行温度。

Description

选择制冷剂-润滑剂组合的方法
发明领域
本发明涉及用于选择制冷剂润滑剂组合以用于热传递循环***中的方法并且提供了用于运行所述热传递***的方法。更确切地说，本发明涉及用来选择制冷剂润滑剂组合以用于热传递循环***中的方法，其中在该热传递循环的较低温度下该制冷剂与润滑剂是易混溶的并且在该热传递循环的较高温度下该制冷剂与润滑剂是相分离的并且使得该组合的密度相（density phase）转化温度低于该热传递循环的较高运行温度。
发明概述
在热传递***、例如蒸气压缩制冷***中制冷剂与润滑剂之间的易混溶性对于决定此类***的性能是重要的。在许多情况下，优选的是在所有运行条件下润滑剂与制冷剂之间的易混溶性，以便确保足够的润滑、润滑剂在该***中的充分循环、并且在关键的***部件中维持有效的热传递。然而，许多制冷剂润滑剂组合在高温下展现出相分离。已经发现了一种选择制冷剂润滑剂组合的方法，该方法使用此类相分离的制冷剂润滑剂组合，这些组合还展现了密度相转化的特性。在低于“相转化温度”的温度下，富含润滑剂的相不及富含制冷剂的相致密，而在高于“相转化温度”的温度下，富含制冷剂的相不及富含润滑剂的相致密。一种特定的组合从一个更致密的相转向另一个、并且由此从一个顶部相转向另一个相时的温度是相转化温度。
本发明的一个实施方案是选择热传递***中的制冷剂润滑剂组合的方法，该***包括但不限于制冷蒸气压缩型***，该***结合了至少一种制冷剂以及至少一种润滑剂。在本发明的一个进一步的实施方案中，该选择制冷剂润滑剂组合的方法是选择一个较低的运行温度范围，此时该制冷剂和润滑剂形成一个单相，并且选择一个较高运行温度范围，此时该制冷剂和润滑剂分离成富含制冷剂的相以及富含润滑剂的相。在一个进一步的实施方案中，该制冷剂-润滑剂相转化温度是在该较低运行温度范围与该较高运行温度范围之间。在传统的制冷蒸气压缩***中，例如在制冷或空气调节***中，这样的较低和较高运行温度可以分别是蒸发器排出物温度和压缩机排出物温度。
本发明的选择制冷剂润滑剂组合的温度将促进热传递***中的有效的油返回并且有助于维持有效的性能。例如，在具有制冷蒸气压缩循环的蒸发器中，制冷剂与润滑剂之间的不混溶性可能导致油测井（oil logging）以及过量的油累积，这可能使该蒸发器对热传递绝缘，从而降低***效率。如果该润滑剂与制冷剂是易混溶的，则润滑剂趋向于从蒸发器穿过并返回至压缩机。因此，本发明的一个优选实施方案是该制冷剂润滑剂组合在该热传递***的较低温度下是易混溶的以便使油测井最小化。
另一个问题是在热传递***的接收器或储存器中收集油的潜力。典型地，如果润滑剂与制冷剂是不混溶的，则一个富含润滑剂的相可能漂浮在接收器或储存器中的更致密的富含制冷剂的相的表面上，这使得该富含润滑剂的相高于了用于返回至压缩机的抽吸线。这可能导致润滑剂在这些储存器中聚集并且润滑剂随后从压缩机中排出，这可能导致压缩机零件的润滑不充分，从而导致过度磨损和过早失效。如果此类储存器或接收器的温度充分高于该制冷剂-润滑剂组合的相转化温度，则富含润滑剂的相将沉到底部并且被收集而回到压缩机中，由此确保了有效的油返回。如果此类储存器或接收器中的温度是等于或接近该制冷剂-润滑剂组合的相转化温度，则富含润滑剂的相以及富含制冷剂的相可以形成具有长凝固时间的稳定乳液或混合物，再次允许有效的油返回。本发明的一个实施方案是，该相转化点是在该***的较高与较低运行温度之间并且优选地接近或低于该接收器或储存器的温度，这样使得在该接收器或储存器中不形成一个富含润滑剂的上层相。
制冷剂与润滑剂的易混溶行为在热传递***的压缩机中是非常重要的，其中润滑作用对于正确的运行和维持设备寿命而言是重要的。如果溶解的制冷剂使润滑剂的粘度降低太多，则在压缩机中可能存在不充分的润滑，从而导致过度磨损和过早失效。另一个问题是溢流起点的问题，其中压缩机储槽在关闭后有制冷剂溢流。在启动过程中，制冷剂的存在可能减小润滑剂粘度，从而导致不足够的压缩机润滑作用。这对于不混溶的制冷剂/润滑剂***尤其是个问题，此时在压缩机储槽中可以形成两个层，其中制冷剂层在底部。润滑剂正常情况下被抽入压缩机轴承中的抽出点是在底部。在本发明的一个优选实施方案中，压缩机中的温度高于该相转化温度，由此限制了制冷剂使润滑剂在压缩机储槽中移位的机会，这将辅助润滑作用并且避免许多溢流起点的问题。在一个单独的实施方案中，在空转时期中压缩机中的温度是使得制冷剂与润滑剂是混溶的。
虽然不打算限制本发明的范围，但本发明的制冷剂包括含有以下各项的组合物：氢氟烷（HFC）、氢氟烯烃（HFO）、氯氟烃（HCFO）、氯氟烃（HCFC）、烃（HC）、二氧化碳、氨、二甲醚、和/或它们的混合物。优选地，该制冷剂包含一种氢氟烯烃。更优选地，该制冷剂包含一种氟化的C3至C6烯烃，更优选一种氟化的C3至C4烯烃，甚至更优选一种三、四、或五氟丙烯，并且甚至更优选一种三氟丙烯、四氟丙烯、和/或它们的混合物。示例性的三氟丙烯包括3,3,3-三氟丙烯（HFO-1243zf）。示例性的四氟丙烯包括2,3,3,3-四氟丙烯（HFO-1234yf）和1,3,3,3-四氟丙烯（HFO-1234ze）。1,3,3,3-四氟丙烯（HFO-1234ze）可以包括顺式异构体、反式异构体、以及它们的混合物；优选地1,3,3,3-四氟丙烯主要是反式异构体。
示例性的HFC包括但不限于：二氟甲烷（HFC-32）、1-氟代乙烷（HFC-161）、1,1-二氟乙烷（HFC-152a）、1,2-二氟乙烷（HFC-152）、1,1,1-三氟乙烷（HFC-143a）、1,1,2-三氟乙烷（HFC-143）、1,1,1,2-四氟乙烷（HFC-134a）、1,1,2,2-四氟乙烷（HFC-134）、1,1,1,2,2-五氟乙烷（HFC-125）、1,1,1,3,3-五氟丙烷（HFC-245fa）、1,1,2,2,3-五氟丙烷（HFC-245ca）、1,1,1,2,3-五氟丙烷（HFC-245eb）、1,1,1,3,3,3-六氟丙烷（HFC-236fa）、1,1,1,2,3,3,3-七氟丙烷（HFC-227ea）、1,1,1,3,3-五氟丁烷（HFC-365mfc）、1,1,1,2,3,4,4,5,5,5-十氟丙烷（HFC-4310）、以及它们的混合物。
示例性的烃包括但不限于：丙烷、丁烷、异丁烷、丙烯、以及它们的混合物。示例性的氯氟烃包括但不限于：HCFC-22、HCFC-123、以及它们的混合物。示例性的HCFO包括但不限于：1-氯-3,3,3-三氟丙烯（HCFO-1233zd）、优选反式异构体，2-氯-3,3,3-三氟丙烯（HCFO-1233xf），和/或它们的混合物。
虽然不打算以任何方式限制本发明的范围，但是本发明的润滑剂包括但不限于：聚亚烷基二醇（PAG）、多元醇酯（POE）、聚乙烯基醚（PVE）、聚乙二醇类、聚亚烷基乙二醇酯、烷基苯、矿物油、聚α烯烃、和/或它们的混合物。PAG油优选是由两个或更多氧化丙烯基团组成的均聚物或共聚物。PAG油可以是“未封端的”、“单端封端的”、或“双端封端的”。商业PAG油的实例包括但不限于：ND-8、Castrol PAG 46、Castrol PAG 100、CastrolPAG 150、Daphne Hermetic PAG PL、Daphne Hermetic PAG PR。商业POE油的实例包括但不限于：Emkarate POE RL 32H、Emkarate POE RL 68H、Copeland Ultra 22CC、Copeland Ultra 32CC。该润滑油的优选粘度是从约10至约200厘沱。
在本发明的范围之内的制冷剂/润滑剂组合的实例包括：
HFO-1234yf/PAG
HFO-1234yf/POE
HFO-1234yf/PVE
HFO-1234ze/PAG
HFO-1234ze/POE
HFO-1234ze/PVE
HFO-1243zf/PAG
HFO-1243zf/POE
HFO-1243zf/PVE
已认可的是在同一族内的润滑剂（例如PAG）的化学组成可以不相同。因此，从一种润滑剂到下一种，其混溶行为以及转化温度可以不相同，甚至在与同一种制冷剂组合时。因此，本发明的冷却方法的运行温度可以根据制冷剂和润滑剂的特定组合而改变。本领域技术人员将能够确定一种特定组成的相转化温度。
包括制冷、空调、以及液体骤冷在内的热传递***的运行为：一部分的循环是处于较低的运行温度范围内并且另一部分的循环是处于较高的运行温度范围内。这些较高和较低的温度范围将取决于特定的应用。例如，用于低温制冷的运行温度可以与用于汽车空气调节或用于水冷却器的不相同。优选地，该较高的运行温度范围是从约+15°C至约+90°C、更优选从约+30°C至约+70°C。优选地，该较低的运行温度范围是从约+25°C至约-60°C、更优选从约+15°C至约-30°C。例如，一个低压液体冷却器可以在从-10°C至+10°C的蒸发器温度以及从约+30°C至+55°C的冷凝器温度下运行。例如，一个空气调节器、例如汽车AC，能以4°C的蒸发温度和40°C的冷凝温度运行。对于制冷，该较低的运行温度范围可以取决于特定的应用。例如，对于制冷而言一些典型的应用温度包括：冷冻机（例如冰淇淋）：-15°F+/-2°F（-26°C+/-1.1°C）；低温：0°F+/-2°F（-18°C+/-1.1°C）；中温：38°F+/-2°F（3.3°C+/-1.1°C）。这些实例仅提供信息的并且不打算以任何方式限制本发明的范围。在本发明的范围之内可以采用其他的运行温度和运行温度范围。
这些组合物还包含添加剂，如染料、粘度改性剂、抗发泡剂、腐蚀抑制剂、稳定剂、增容剂、抗氧化剂、降凝剂、纳米颗粒、火焰抑制剂以及它们的混合物。
本发明的另一个实施方案是用一种制冷剂-润滑剂组合来运行一种热传递***的方法。在一个实施方案中，该热传递***的一个部分是以较低的运行温度范围运行，此时制冷剂和润滑剂形成了一个单相。该热传递***的另一个部分是以较高的运行温度范围运行，此时制冷剂和润滑剂分离成为一个富含制冷剂的相和一个富含润滑剂的相。在本发明的这个实施方案中，该热传递***是在以下情况下运行：该制冷剂/润滑剂组合的密度相转化温度是在该较高的与较低的运行温度之间。
实例1
向一个带刻度的压力容器中加入近似相等部分的HFO-1234yf和一种商业PAG润滑剂（Castrol PAG 46）。将这些组分混合并允许其在环境温度下静置到平衡。在环境温度（约20°C）下，该混合物进行相分离，其中一个富含润滑剂的液相漂浮在一个富含制冷剂的液相上。为了将混合物的温度降低到低于环境，将该压力容器置于一个恒温制冷机或冷冻器中并冷却到达到平衡。在8°C下该混合物是易混溶的，仅显示一个单一液相。在-20°C下该混合物是易混溶的，仅具有一个单一液相。
为了将该混合物的温度升高至高于环境，然后将该带刻度的压力容器放在一个恒温浴中并分阶段地从25°C加热至50°C、允许其在每个阶段达到平衡，并周期性地观察容器的内含物。该混合物包含两个液相。在30°C下，这两个相非常难以区分。在35°C下，这两个相仍然难以区分，但一个液体的、富含制冷剂的相漂浮在一个更加富含润滑剂的相的上方。在40°C以及更高温度下，该样品的富含制冷剂的相的部分增加并且这两个相更容易区分。
将该带刻度的压力容器从该恒温浴中取出并允许其冷却。在该容器冷却时，观察到该富含制冷剂的相沉到容器底部。
这个实例显示，HFO-1234yf与Castrol PAG 46的组合在从8°C-20°C是易混溶的、而在+20°C及以上是不混溶的，密度相转变温度是约+30°C。
实例2
使用实例1的制冷剂/润滑剂组合可以允许一种蒸气压缩空气调节***，其中该制冷剂是HFO-1234yf并且润滑剂是Castrol PAG 46。该较低的运行温度范围可以是从大约+8°C至大约-20°C，而该较高的运行温度范围可以是从大约30°C及以上。该空气调节***可以根据本发明来运行，其中将蒸发器温度维持在4°C+/-2°C，并将冷凝温度维持在大约40°C。使用这些运行条件，该制冷剂和润滑剂在空气调节***中的最冷条件下是易混溶的，而在该较高的运行温度下，制冷剂和润滑剂将是不混溶的，但此时富含制冷剂的相是较不致密的。

Claims (4)

1.一种选择制冷剂润滑剂组合以用于蒸气压缩热传递***中的方法，该方法包括：
a.确定一个蒸气压缩热传递***的一个较低的蒸发器排出物运行温度范围；
b.确定该蒸气压缩热传递***的一个较高的压缩机排出物运行温度范围；并且
c.选择一个第一浓度的一种四氟丙烯制冷剂，该制冷剂是选自：2,3,3,3-四氟丙烯(HFO-1234yf)、1,3,3,3-四氟丙烯(HFO-1234ze)、或它们的混合物；以及一个第二浓度的一种润滑剂，该润滑剂是选自：聚亚烷基二醇(PAG)，其中所述制冷剂和所述润滑剂在-60℃至+25℃的所述较低的运行温度范围的一个第一温度下是易混溶的并形成单相，并且在+15℃至+90℃的所述较高的运行温度范围内的一个第二温度下产生了具有一个富含制冷剂的相以及一个富含润滑剂的相的一个流体***，其条件是所述第二温度是高于所述第一温度，其中在所述第二温度下该富含润滑剂的相是相对于该富含制冷剂的相而言更致密的，其中相转化温度低于压缩机运行温度。
2.如权利要求1所述的方法，其中所述较高的运行温度范围是+30℃至+70℃，并且所述较低的运行温度范围是-30℃至+15℃。
3.如权利要求1所述的方法，其中所述流体***进一步包含选自下组的一种或多种添加剂，该组由以下各项组成：染料、粘度改性剂、抗发泡剂、腐蚀抑制剂、稳定剂、增容剂、抗氧化剂、降凝剂、纳米颗粒、火焰抑制剂以及它们的混合物。
4.一种将制冷剂和润滑剂引入蒸气压缩热传递装置***中的方法，该方法包括：
a.提供一个蒸气压缩热传递装置，该装置包括一个热传递回路、具有一个进口侧和一个出口侧的一个压缩机、一个制冷剂和润滑剂储存器，其中所述储存器与该压缩机的进口侧并且与所述热传递回路是流体连通的，并且所述热传递回路与该压缩机的所述出口侧是流体连通的；
b.确定该蒸气压缩制冷装置的较低的压缩机进口侧运行温度范围；
c.确定该蒸气压缩制冷装置的较高的压缩机出口侧运行温度范围；
d.选择一个第一浓度的一种四氟丙烯制冷剂，该制冷剂是选自：2,3,3,3-四氟丙烯(HFO-1234yf)、1,3,3,3-四氟丙烯(HFO-1234ze)、或它们的混合物；并且选择一个第二浓度的一种润滑剂，该润滑剂是选自：聚亚烷基二醇(PAG)，其中所述制冷剂和所述润滑剂在-60℃至+25℃的所述较低的运行温度范围的一个第一温度下是易混溶的并形成单相，并且在+15℃至+90℃的所述较高的运行温度范围内的一个第二温度下产生了具有一个富含制冷剂的相以及一个富含润滑剂的相的一个流体***，其条件是所述第二温度是高于所述第一温度，其中在所述第二温度下该富含润滑剂的相是相对于该富含制冷剂的相而言更致密的，其中相转化温度低于压缩机运行温度；并且
e.将所述制冷剂和润滑剂引入该蒸气压缩热传递装置。
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US9481820B2 (en) 2016-11-01
CA2785854A1 (en) 2011-07-07
US9890312B2 (en) 2018-02-13
EP2519599A4 (en) 2017-05-03
JP6141019B2 (ja) 2017-06-07
ES2957896T3 (es) 2024-01-29
EP2519599A1 (en) 2012-11-07
US20120272668A1 (en) 2012-11-01
MX2012007563A (es) 2012-07-25
MX345853B (es) 2017-02-17
US20170029680A1 (en) 2017-02-02
MX360657B (es) 2018-11-12
WO2011082003A1 (en) 2011-07-07
JP2013515838A (ja) 2013-05-09
CA2785854C (en) 2017-11-28
EP2519599B1 (en) 2023-08-23

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