CN1041110C - 润滑剂组合物 - Google Patents

润滑剂组合物 Download PDF

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Publication number
CN1041110C
CN1041110C CN94194656A CN94194656A CN1041110C CN 1041110 C CN1041110 C CN 1041110C CN 94194656 A CN94194656 A CN 94194656A CN 94194656 A CN94194656 A CN 94194656A CN 1041110 C CN1041110 C CN 1041110C
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China
Prior art keywords
compressor
lubricant
lubricant compositions
foam density
additive
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Expired - Fee Related
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CN94194656A
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CN1139450A (zh
Inventor
B·D·格雷格
A·M·史密夫
A·施沃劳
M·M·奥布赖恩
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Castrol Ltd
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Castrol Ltd
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Priority claimed from GB939322887A external-priority patent/GB9322887D0/en
Priority claimed from GB9415118A external-priority patent/GB9415118D0/en
Application filed by Castrol Ltd filed Critical Castrol Ltd
Publication of CN1139450A publication Critical patent/CN1139450A/zh
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    • C10M169/00—Lubricating compositions characterised by containing as components a mixture of at least two types of ingredient selected from base-materials, thickeners or additives, covered by the preceding groups, each of these compounds being essential
    • C10M169/04—Mixtures of base-materials and additives
    • C10M169/041—Mixtures of base-materials and additives the additives being macromolecular compounds only
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    • C10M105/08—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound containing oxygen
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    • C10M171/008—Lubricant compositions compatible with refrigerants
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F04—POSITIVE - DISPLACEMENT MACHINES FOR LIQUIDS; PUMPS FOR LIQUIDS OR ELASTIC FLUIDS
    • F04B—POSITIVE-DISPLACEMENT MACHINES FOR LIQUIDS; PUMPS
    • F04B39/00—Component parts, details, or accessories, of pumps or pumping systems specially adapted for elastic fluids, not otherwise provided for in, or of interest apart from, groups F04B25/00 - F04B37/00
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    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25B—REFRIGERATION MACHINES, PLANTS OR SYSTEMS; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS
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Abstract

一种用于至少有一台压缩机并使用卤化碳工作液体如R134a的致冷系统中的润滑剂组合物，它包含合成多元醇酯润滑剂和其量足够提高泡沫密度和控制蒸汽放出的硅氧烷。

Description

润滑剂组合物
本发明涉及致冷压缩机的润滑。
近些年来，由于环境保护的压力，已使用损害性不大的碳氟化合物如1，1，1，2-四氟乙烷来代替使用如含氯氟烃的传统致冷气体。这一变化还要求所用润滑剂随工作液体而变化，因为原来使用的润滑剂如烷基苯和矿物油与工作液体如1，1，1，2-四氟乙烷不是充分溶混的。因此一直在研制新的润滑剂。尤其是，合成多元醇酯润滑剂用于新的工作液体已显示出令人满意的结果。
然而，润滑剂这种变化的本身也产生了一些问题。尤其是，发现碳氟化合物工作液体/合成酯润滑剂体系在某些压缩机操作的情况下是成问题的，因为牵涉到从润滑油中释放过量的而且不可控制的致冷剂蒸汽，引起蒸汽溢流，从而妨碍了润滑剂有效地循环。体系中因缺乏适当的润滑可导致很高的磨损率和/或压缩机故障。
这样一种情况例如在启动压缩机时可能发生，而且在例如多台压缩机系统操作过程中也会出现，因为此时压力差会对一台或多台压缩机内的润滑剂/致冷剂的平衡造成影响。
当然，这样一些问题能通过压缩机系统的设计得到克服，致使所述的溢流不出现，但是，当现存的压缩机仍具有很长的可能使用期时，采取这样方式是不经济而费钱的。
本发明寻求通过能持续使用现存压缩机来克服这些问题，没有必要对系统进行结构改进。
根据本发明，提供一种供致冷体系使用的润滑剂组合物，它包括合成多元醇酯润滑剂和泡沫密度增长添加剂，所述致冷体系至少具有一台压缩机并使用卤化碳工作液体，要使所述添加剂存在量足以增加泡沫密度和控制蒸汽从压缩机或者从一台或多台压缩机中放出。
优选泡沫密度增长添加剂是硅氧烷，其平均分子量在200-13000范围内。
已知在致冷流体系统中含有某种硅氧烷这一事实本身并不是新的。美国专利3,792,755描述了在压缩机操作过程中使用泡沫剂，该泡沫剂被认为是能使噪声减弱的溶于甲苯中的有机硅氧烷。然而，该文献还是涉及使用传统的工作液体和润滑剂。此外，在该文献范围内，还存在着有关控制发泡量以防泡沫进入压缩室损坏压缩机的公认利害关系。现已提出硅氧烷聚合物在致冷系统中作抗泡沫剂使用，例如见美国专利5,021,179。这一点是不足为奇的，因为硅氧烷聚合物以前已在各种用途中被作为抗泡沫剂使用过。
由此令人惊奇的是发现了，按照本发明，使用硅氧烷能克服以前报道过的问题，借助于增加泡沫密度并控制致冷气体在压缩机操作变化过程中例如启动或压缩机内润滑剂/致冷剂平衡受到影响的其它情况下放出，由此获得克服可能的故障或磨损问题而使现存压缩机能继续在新的工作液体/润滑剂体系下得到使用的方法。
可以理解能增加泡沫密度致使能控制蒸汽放出的其它添加剂也能使用，例如卤代脂族聚酯如Fluorad FC 430，一种由3M，Bracknell买到的氟代脂族聚酯和某些有机聚合物，如从Monsanto买到的PC 1244。
合成多元醇酯润滑剂，尽管不是必须但适合地包括分子量大于250的酯，优选为脂族单羧酸与至少有三个羟基的醇形成的酯，这种醇，如季戊四醇和/或二季戊四醇。这类酯已被描述于欧洲专利说明书468729中。
多元醇酯润滑剂可以是单独使用的润滑剂，或以与其它合成的和/或矿物基润滑剂的混合物形式存在，这取决于所用的致冷工作液体和体系中优先使用的润滑剂。
卤化碳工作液体优选是环境可接受的碳氟化合物如1，1，1，2-四氟乙烷(称为HFC 134a或R 134a)，尽管本发明也可使用早期的且现在不大接受的含氯工作液体如R12(二氯二氟甲烷)。本发明也适用于“Retrofill”情况即以前所用润滑剂是例如烷基苯或矿物油，所用工作液体选自R12、R22、R502或R511的情况。这样的使用描述在上述参考过的欧洲专利说明书468729中。另外新的可接受的致冷剂如R404a也可以使用。
作为泡沫密度增长添加剂使用的硅氧烷适合具有平均分子量为200-1300，尽管实际选择的硅氧烷取决于在所用润滑剂时需要的溶解度。优选分子量平均值为236-5000。硅氧烷也可用其粘度来限定而且硅氧烷在25℃下粘度范围为0.65-1000厘泊，优选使用的1-100厘泊取决于使用的润滑剂和工作液体。
现已发现按本发明使用的合适硅氧烷是称作200/5CS的硅氧烷，平均分子量为680，可从Dow Corning(Reading，Berkshire)得到。
存在的泡沫密度增长添加剂的量必须足够提高泡沫密度和控制蒸汽在致冷系统内从压缩机，或从一台或多台压缩机中放出。尽管可以理解对特定用途来说优选浓度可由所属技术领域的技术人员来测定，但是优选添加剂的浓度按润滑剂重量超过150ppm，最好大于200ppm.为了保证添加剂仍与致冷剂溶混，最好添加剂使用量不超过1200ppm.优选润滑剂含有按添加剂体积计低于0.1％。
可将具有能克服启动溢流问题的具体优点的本发明润滑剂组合物用于例如用油泵加润滑剂的单-压缩机。此外，当操作多-压缩机系统时，最好使用润滑剂以排除不想要的致冷剂溢流作用，该溢流作用是由于例如向压缩机供应与溶解致冷剂一起的润滑剂的过程中产生的，该致冷剂含量很高。这种情况是作为供应润滑剂过程中高的压差的结果产生的，或作为必须供应附加液体致冷剂以冷却压缩机的结果产生的。
就半-密封压缩机而言，发现本发明是特别有效的，通常这种压缩机被用于多-压缩机装置中并且与涉及设备输送的操作有关，此时操作条件的极限值会加重溢流问题。
下列非限制性实施例就A〕压缩机的启动和B〕多台压缩机的操作而论，用来说明本发明。
A)压缩机的启动
试验程序
按下列程序试验具有和没有添加剂硅氧烷的润滑剂组合物：
一种常规的Carrier Thinline“用夹子夹上去的(clip-on)”容易冷却单元被安置在露天中并按插入冰水混合物中(在0℃下)的供应空气温度传感器的“调制模式”操作。调节温度给定值至大约0℃以保证压缩机连续操作。采用调制模式限制空吸以保证供应空气温度保持恒定并避免压缩机过分加热相当数量的可进入压缩机的液体致冷剂。这一点导致压缩机的“结冰”，原因在于液体致冷剂蒸发的冷却效果。该程序被用于人工产生“溢流开始”的情况，此时压缩机油槽盛有大约等比例的润滑剂和液体致冷剂。
在试验程序中，一旦有充足的冰珠形成，压缩机即停止而旁路阀打开使液体致冷剂由冷凝器流入油槽。在适当的“保温时间”后压缩机重新起动并按调制模式再次运转。监测首次数分钟操作过程中的实际油压(油槽和油泵出口间的压差)。
实施例AI(对比)
完成上述试验程序是使用R12作工作液体并使用标准矿物油润滑剂(由Sun Oil公司作为Napthenic ISO VG32买到的)。完成两次运转且结果列于图1中，该图表示油压在整个启动期都在可接受的水平上。
实施例AII(对比)
采用作工作液体的R134a和多元醇酯润滑剂一起并从Castrol作为Castrol ICEMATIC SW20买到重复试验程序。
往润滑剂中加入120ppm的Dow Corning硅氧烷“200/5CS”运转1和2的结果列于图2中。由图可见对于运转1油压在整个启动期维持不能接受的低水平上，而对于运转2，压力在达到适当水平之前就下降了。
实施例AIII
重复实施例2的试验程序但使用240ppm的硅氧烷“200/5CS”。运转1和2的结果列于图3中。可以看到在两种情况下起始低油压迅速达到可接受的水平因此在启动期间维持了适当的润滑作用。
B)多台压缩机操作
在图示于附图4中的超级市场致冷系统条件下使用本发明的润滑剂组合物。
示于图4中的系统包括6台Prestcold PL300/10040压缩机1、2、3、4、5和6，与单一排放管线7连接形成构造系统的单冷凝器。6台压缩机中，1、2和3与高吸引压力管线8连接，压缩机4、5和6与低吸引压力管线9连接。
6台压缩机的共用润滑系统包括排放管线7中冷凝器上游的油分离器10，油从这里经浮动式液面阀流入油收集储存器11，其标称压力保持在高于3巴的高吸收压力1巴的压力下。储存器11中的润滑剂由此在4巴的压力和环境温度下为致冷剂(例如R22)所饱和，过量的致冷剂蒸发经压力安全阀12进入高吸引压力管线8。每台压缩机1、2、3、4、5和6都装有浮动式液面阀14、15、16、17、18、19，当需要向压缩机供油时可从储存器11供给。对于压缩机1、2、和3来说，油是由4巴下的储存器11加至3巴下的压缩机油槽中，而对于压缩机4、5和6来说，油是从4巴下的储存器11加至与1巴的低吸引压力管线连接的压缩机油槽中。
在低温下(低于负20℃)采用常规合成多元醇酯润滑剂(从Castrol作为Castrol ICEMATIC SW 32买到的)操作时，压缩机4、5和6有润滑作用不够的缺点。
常规的环烷油润滑剂可用本发明的一种润滑剂，多元醇酯，含240ppm的硅氧烷200/5CS来代替。
通常系统是在低至-25℃的低温下操作，不显示压缩机润滑作用不足的迹象。

Claims (8)

1.一种用于至少有一台压缩机并使用卤化碳工作液体的致冷系统的润滑剂组合物，其特征在于该组合物包含合成多元醇酯润滑剂和泡沫密度增长添加剂，其中，该合成多元醇酯的分子量大于250；泡沫密度增长添加剂的量为150ppm-1200ppm的范围(以润滑剂重量计)，以提高泡沫密度和控制蒸汽从该压缩机或数台压缩机之一中放出。
2.按权利要求1的润滑剂组合物，其中泡沫密度增长添加剂是硅氧烷。
3.按权利要求2的润滑剂组合物，其中硅氧烷的平均分子量在200-13000范围内。
4.按权利要求1的润滑剂组合物，其中泡沫密度增长添加剂是卤代脂族聚酯。
5.按权利要求1的润滑剂组合物，其中该多元醇酯为脂族单羧酸与至少具有三个羟基的醇所形成的酯。
6.权利要求1-5中任一项的润滑剂组合物于有至少一台的半-密封压缩机的致冷系统中的用途。
7.按权利要求1-5中任一项的润滑剂组合物于采用1，1，1，2-四氟乙烷作工作液体的致冷系统中的用途。
8.按权利要求1-5中任一项的润滑剂组合物于用油泵润滑压缩机的致冷系统中的用途。
CN94194656A 1993-11-06 1994-11-04 润滑剂组合物 Expired - Fee Related CN1041110C (zh)

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CN1139450A (zh) 1997-01-01
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EP0726930A1 (en) 1996-08-21
EP0726930B1 (en) 1999-01-20
AU8065594A (en) 1995-05-23

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