CN106010454A - 基于1,3,3,3-四氟丙烯的组合物 - Google Patents

基于1,3,3,3-四氟丙烯的组合物 Download PDF

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CN106010454A
CN106010454A CN201610365469.4A CN201610365469A CN106010454A CN 106010454 A CN106010454 A CN 106010454A CN 201610365469 A CN201610365469 A CN 201610365469A CN 106010454 A CN106010454 A CN 106010454A
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W.雷切德
B.布桑德
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Abstract

本申请涉及基于1,3,3,3‑四氟丙烯的组合物。本申请的主题是包含基于多元醇酯(POE)或PVE的润滑剂以及含有1~99重量%的反式‑1,3,3,3‑四氟丙烯(反式‑HFO‑1234ze)和1~99重量%的1,1,1,3‑四氟乙烷的制冷剂F的组合物。本申请的主题还为所述组合物在制冷、空气调节以及热泵中的用途。

Description

基于1,3,3,3-四氟丙烯的组合物
本申请是中国发明申请(发明名称:基于1,3,3,3-四氟丙烯的组合物,申请日:2011年9月16日;申请号:201110274542.4)的分案申请。
技术领域
本发明涉及能够用于制冷、空气调节和热泵的含有反式-1,3,3,3-四氟丙烯和1,1,1,3-四氟乙烷以及至少一种润滑剂的组合物。
背景技术
在蒙特利尔讨论了由损耗大气臭氧层的物质所引起的问题,其中签署了强制减少氯氟烃(CFC)的制造和使用的议定书。该议定书已经成为这样的修正案的主题,所述修正案要求放弃CFC并且将规定扩展至其它产品,包括氢氯氟烃(HCFC)。
制冷工业和空调工业已经在这些制冷剂的替代方面进行了大量投入,因此氢氟烃(HFC)已经上市。
在机动车工业中,许多国家中出售的车辆的空调系统已经由氯氟烃(CFC-12)制冷剂变为对臭氧层的危害较小的氢氟烃(1,1,1,2-四氟乙烷:HFC-134a)制冷剂。然而,从由京都议定书所设定的目标的观点来看,HFC-134a(GWP=1430)被认为具有高的发热能力(heating power)。制冷剂对温室效应的贡献通过标准即GWP(全球变暖潜势)量化,其通过将二氧化碳作为基准值1来概括发热能力。
氢氟烯烃(HFO)具有低的发热能力并因而满足由京都议定书所设定的目标。文献JP 4-110388公开了氢氟丙烯作为传热剂。
在工业领域中,最通常使用的制冷机基于通过液态制冷剂的蒸发的冷却。在气化后,制冷剂被压缩,然后冷却以回到液态并从而继续该循环。
所用的制冷压缩机为往复式、涡旋式、离心式或螺杆式的。通常,为了减少移动部件的磨损和发热、完成它们的密封性并使它们不被腐蚀,压缩机的内部润滑是必需的。
除了良好的传热剂性能外,为了使制冷剂在商业上被接受,其特别地必须表现出热稳定性以及与润滑剂的相容性。具体地,高度期望制冷剂与压缩机中所用的润滑剂相容,所述压缩机存在于大部分制冷系统中。对于制冷系统的实施和效率而言,制冷剂与润滑剂的这种组合是重要的;特别地,在整个工作温度范围内,润滑剂应当在制冷剂中是充分可溶的或可溶混的。
因此,已经开发聚亚烷基二醇(PAG)作为机动车空调中的HFC-134a的润滑剂。
在文献WO 2004/037913的实施例2中已经描述了1,1,3,3,3-五氟丙烯和1,3,3,3-四氟丙烯与润滑剂的溶混性的测试。在实施例3中还已描述了与聚亚烷基二醇的相容性测试。但是,这些测试没有详细说明1,3,3,3-四氟丙烯异构体的性质。
而且,文献WO 2005/108522公开了反式-1,3,3,3-四氟丙烯和1,1,1,3-四氟乙烷的共沸组合物。
就在最近,2,3,3,3-四氟丙烯被选择作为机动车空调中的制冷剂用于代替HFC-134a。
发明内容
本申请人现已开发可用于制冷、空气调节和热泵的制冷剂和润滑剂的配对。
本发明涉及:
1.组合物,包含制冷剂F和至少一种基于多元醇酯(POE)或PVE的润滑剂,所述制冷剂F含有1~99重量%的反式-1,3,3,3-四氟丙烯(反式-HFO-1234ze)和1~99重量%的1,1,1,3-四氟乙烷。
2.条目1的组合物,特征在于所述制冷剂F包含5~95重量%的反式-1,3,3,3-四氟丙烯(反式-HFO-1234ze)和5~95重量%的1,1,1,3-四氟乙烷。
3.条目1或2的组合物,特征在于所述制冷剂F包含30~91重量%的反式-1,3,3,3-四氟丙烯(反式-HFO-1234ze)和9~70重量%的1,1,1,3-四氟乙烷。
4.条目1-3中任一项的组合物,特征在于所述POE是由具有新戊基骨架的多元醇例如新戊二醇、三羟甲基丙烷、季戊四醇和二季戊四醇得到的。
5.条目1-4中任一项的组合物,特征在于所述POE是由含有2~15个碳原子的线型或支化羧酸得到的。
6.条目1-5中任一项的组合物,特征在于所述POE占该组合物的10~50重量%。
7.条目1-6中任一项的组合物在制冷、空气调节和热泵中的用途。
具体实施方式
因此,本申请的主题是包含含有1~99重量%的反式-1,3,3,3-四氟丙烯(反式-HFO-1234ze)和1~99重量%的1,1,1,3-四氟乙烷的制冷剂F、以及至少一种基于多元醇酯(POE)或聚乙烯基醚(PVE)的润滑剂的组合物。
优选地,根据本发明的组合物包含含有5~95重量%的反式-1,3,3,3-四氟丙烯(反式-HFO-1234ze)和5~95重量%的1,1,1,3-四氟乙烷的制冷剂F、以及至少一种基于多元醇酯(POE)或聚乙烯基醚(PVE)的润滑剂。
特别优选的组合物包含含有30~91重量%的反式-1,3,3,3-四氟丙烯(反式-HFO-1234ze)和9~70重量%的1,1,1,3-四氟乙烷的制冷剂F、以及至少一种基于多元醇酯(POE)或聚乙烯基醚(PVE)的润滑剂。
制冷剂F还可包含其它氢氟烃。
流体F具有比反式-HFO-1234ze更有效的优点,且此外,该制冷剂在POE或PVE的存在下的稳定性高于反式-HFO-1234ze在PAG的存在下的稳定性。
多元醇酯通过多元醇(含有至少两个羟基-OH的醇)与单官能或多官能羧酸或者与单官能羧酸的混合物的反应获得。除去在该反应期间所形成的水,以防止逆反应(即水解)。
根据本发明,优选的多元醇为具有新戊基骨架的那些,例如新戊二醇、三羟甲基丙烷、季戊四醇和二季戊四醇;季戊四醇是优选的多元醇。
所述羧酸可含有2~15个碳原子,碳骨架可为线型或支化的。可特别提及正戊酸、正己酸、正庚酸、正辛酸、2-乙基己酸、2,2-二甲基戊酸、3,5,5-三甲基己酸、己二酸和丁二酸、以及它们的混合物。
一些醇官能团未被酯化,但它们的比例保持为低的。因此,POE可包含0~5相对摩尔%的CH2-OH单元,相对于-CH2-O-(C=O)-单元。
优选的POE润滑剂为在40℃下具有1~1000厘斯(cSt)、优选10~200cSt、且有利地30~80cSt的粘度的那些。
聚乙烯基醚(PVE)油优选为以下两种单元的共聚物:
该油的性质(特别是粘度、制冷剂的溶解度、以及与制冷剂的溶混性)可通过改变m/n比以及m+n之和调节。优选的PVE油是具有50~95重量%的单元1的那些。
根据本发明的一个优选实施方式,润滑剂占所述组合物的10~50重量%(包括端点)。
制冷剂F还可含有添加剂例如有气味的化合物。
本发明的主题还为上述组合物在以下中的用途:制冷,特别是家庭或商业制冷、冷藏室、食品工业、加工工业、冷藏运输(卡车、船);空气调节,特别是家庭、商业或工业空气调节,其中所用的设备为冷却器或直接膨胀设备;和热泵,特别是中等温度热泵和高温热泵。
由于根据本发明的组合物的滑移温度低,其可用于带有干膨胀式蒸发器的装置和带有在泛滥式系统中操作的蒸发器的装置两者。
实验部分
热稳定性试验根据标准ASHRAE 97-2007:“sealed glass tube method totest the chemical stability of materials for use within refrigerant systems”进行。
测试条件如下:
将润滑剂引入42.2ml玻璃管中。然后,将该管在真空下抽空并然后向其中加入制冷剂F。然后,将该管焊接以使其关闭并将其置于200℃烘箱中14天。
在该测试结尾,进行多种分析:
-收取气相以通过气体色谱法分析:主要杂质通过GC/MS(与质谱法联用的气体色谱法)鉴别。来自制冷剂F的杂质与来自润滑剂的杂质可由此合并;
-分析润滑剂:颜色(通过光谱色度法,Labomat DR Lange LICO220 ModelMLG131)、含水量(通过Karl Fischer电量分析法,Mettler DL37)和酸值(通过采用0.01N甲醇(methanolic)氢氧化钾定量测定)。
测试三种商业润滑剂:PAG ND8油、POE Ze-GLES RB68油、及PVEFVC 68D油。
注意到,在POE或PVE的存在下,反式-HFO-1234ze改善润滑剂的稳定性。此外,在POE的存在下,制冷剂的稳定性也得到改善。
应用
使用所讨论的混合物的系统的热力学性能
计算工具
使用RK-Soave方程式计算混合物的密度、焓、熵以及液汽平衡数据。该方程式的使用需要知道所讨论的混合物中所用纯物质的性质以及对于各二元组合的相互作用的系数。
对于各纯物质所必需的数据为:
沸点、临界压力和临界温度、随着温度从沸点至临界点变化的压力曲线、随温度变化的饱和液体和饱和蒸汽的密度。
HFC的数据公开在ASHRAE Handbook 2005 chapter 20中,而且也可在Refrop(NIST开发的用于计算制冷剂性质的软件)下得到。
HFO的温度-压力曲线数据通过静态法测量。临界压力和温度使用由Setaram销售的C80热量计测量。随温度变化的在饱和状态下的密度通过由école des Mines de Paris[French Engineering School]的实验室开发的振动管密度计技术测量。
二元相互作用系数:
RK-Soave方程式使用二元相互作用系数来表示混合物中各产品的行为。该系数根据实验的液汽平衡数据计算。
用于液汽平衡测量的技术是静态分析池法。平衡池包括蓝宝石管,且装配有两个Rolsitm电磁取样器。其浸在低温恒温浴(Huber HS40)中。使用通过在变速下旋转的磁场驱动的磁力搅拌加速达到平衡。通过使用热导计(TCD)的气体色谱法(HP5890系列II)进行样品分析。
HFC-134a/反式-HFO-1234ze
对于20℃的等温线,进行HFC-134a/反式-HFO-1234ze二元组合的液汽平衡测量。
压缩系统
考虑装配有蒸发器、冷凝器、液体-蒸汽换热器(内部换热器)、螺杆式压缩机和压力调节器的压缩系统。
该系统采用15℃的过热和在冷凝器出口和蒸发器出口之间的内部换热器工作。
压缩机的等熵效率取决于压缩比。该效率根据以下方程式计算:
对于螺杆式压缩机,等熵效率方程式(1)的常数a、b、c、d和e根据在“Handbook of air conditioning and refrigeration,page 11.52”中公布的标准数据计算。
性能系数(COP)定义为系统所提供的有效功率除以系统所提供或消耗的功率。
洛伦茨性能系数(COPLorenz)是参比性能系数。其取决于温度且用于比较各种制冷剂的COP。
洛伦茨性能系数定义如下:
(温度T的单位为K)
在调节的空气以及制冷的情况中的洛伦茨COP:
在加热的情况中的洛伦茨COP:
对于各组合物,洛伦茨循环的性能系数作为相应温度的函数计算。
%COP/COPLorenz是系统的COP相对于相应的洛伦茨循环的COP的比。
在冷却模式中的结果
在冷却模式中,压缩系统在-5℃的蒸发温度和50℃的冷凝温度之间工作。
各组合物的成分(HFC-134a、反式-HFO-1234ze)的值以重量百分比给出。
在加热模式中的结果
在加热模式中,压缩系统在-5℃的蒸发温度和50℃的冷凝温度之间工作。
各组合物的成分(HFC-134a、反式-HFO-1234ze)的值以重量百分比给出。

Claims (6)

1.组合物,包含制冷剂F和在40℃下具有1~1000厘斯(cSt)的粘度的至少一种基于多元醇酯(POE)的润滑剂,所述制冷剂F含有1~99重量%的反式-1,3,3,3-四氟丙烯(反式-HFO-1234ze)和1~99重量%的1,1,1,3-四氟乙烷。
2.权利要求1的组合物,特征在于所述制冷剂F包含5~95重量%的反式-1,3,3,3-四氟丙烯(反式-HFO-1234ze)和5~95重量%的1,1,1,3-四氟乙烷。
3.权利要求1或2的组合物,特征在于所述制冷剂F包含30~91重量%的反式-1,3,3,3-四氟丙烯(反式-HFO-1234ze)和9~70重量%的1,1,1,3-四氟乙烷。
4.权利要求1-3中任一项的组合物,特征在于所述POE在40℃下具有20~300厘斯的粘度。
5.权利要求1-4中任一项的组合物,特征在于所述POE占该组合物的10~50重量%。
6.权利要求1-5中任一项的组合物在制冷、空气调节和热泵中的用途。
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