CN102639683A - 功能性流体组合物 - Google Patents

功能性流体组合物 Download PDF

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CN102639683A
CN102639683A CN2010800499382A CN201080049938A CN102639683A CN 102639683 A CN102639683 A CN 102639683A CN 2010800499382 A CN2010800499382 A CN 2010800499382A CN 201080049938 A CN201080049938 A CN 201080049938A CN 102639683 A CN102639683 A CN 102639683A
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CN102639683B (zh
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J·M·史密瑟斯
D·J·韦德洛克
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Shell Internationale Research Maatschappij BV
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Abstract

本发明提供一种功能性流体组合物，其包含：环烷类光亮油基油；和费-托衍生基油，其中所述功能性流体组合物的粘度指数(按ASTM D2270)大于95。

Description

功能性流体组合物
技术领域
本发明涉及一种功能性流体组合物，特别是在持续高负荷条件下操作的发动机如船用柴油机和发电用途中用作润滑组合物的功能性流体组合物。更特别地，本发明涉及在船用柴油机中用作船用汽缸油的功能性流体。
需要注意的是，虽然在下文中针对特别用作船用汽缸油的功能性流体描述了本发明，但本发明无论如何不限于这种船用汽缸油；本发明可以同等地用作用于其它用途的润滑组合物。
背景技术
由于船用柴油机是通常在高温高压下在接近满负荷条件下长期连续运转，因此在船用柴油机中应用的船用汽缸油承受特别高的应力。
船用汽缸油是所谓的“全损”组合物，和它们的目的是在汽缸内衬和活塞环之间提供强的油膜。如果在高的操作温度和压力下油膜破裂，则汽缸内壁将会承受粘附磨损(称作“齿轮咬磨”)。
除了在汽缸内衬和活塞环之间提供强的油膜外，通常配制船用汽缸油以提供好的氧化和热稳定性、水破乳性、防腐和好的消泡性能。
本发明的目的是提供替代的功能性流体组合物，特别是替代的船用汽缸油配制物。
发明内容
为此，本发明提供一种功能性流体组合物，其包含：
-环烷类光亮油基油；和
-费-托衍生基油，
其中所述功能性流体组合物的粘度指数(按ASTM D 2270)大于95。
按照本发明已经令人惊奇地发现，环烷类光亮油基油可在功能性流体如船用汽缸油中应用，同时获得理想的VI、氧化稳定性和耐磨性。虽然在过去已经建议在汽缸油中应用链烷类光亮油基油，但鉴于其弱的油膜和差的氧化稳定性性能，现在使用环烷类光亮油基油可能被认为是不合适的；在下文的对比例4中例举了环烷类光亮油基汽缸油的差的氧化稳定性性能。
在这方面，要注意的是，最近出版的WO 2007/003623 A1公开了一种在低速柴油机中使用的汽缸油配制物，其包含：
(i)包含在100℃下粘度为8-25mm2/s的链烷类基油组分、及矿物衍生渣油和脱沥青油组分的光亮油基油共混物；
(ii)链烷类基油组分或雾状链烷类基油组分；和
(iii)一种或多种选自如下的添加剂：分散剂、过碱性清净剂、耐磨剂、降摩擦剂、粘度改进剂、粘度增稠剂、金属钝化剂、酸性螯合剂和抗氧化剂。但在WO 2007/003623 A1中没有建议环烷类光亮油基油。
对于在本发明的功能性流体组合物中应用的环烷类光亮油基油没有特别限制。通常，环烷类光亮油基油为来自通过炼油工艺由环烷类矿物原油原料(通常TAN(总酸值，ASTM D 664)值大于0.5mg KOH/g的矿物原油原料是环烷类的，而小于0.5mg KOH/g的是链烷类的)获得的环烷类减压渣油的渣油基油；在环烷类光亮油基油的制备过程中没有脱蜡步骤(相对于其中需要脱蜡步骤的链烷类基油的制备)。矿物衍生的光亮油基油是公知的，和在“Lubricant base oil and waxprocessing”,Avilino Sequeira,Jr.,Marcel Dekker,Inc,New York,1994,ISBN 0-8247-9256-4,28-35页中更详细地进行了描述。优选地，当按本发明应用时，环烷类光亮油基油的初沸点(按ASTM D 2887的真实沸点)大于380℃，优选大于400℃，更优选大于420℃。另外，环烷类光亮油基油的芳族原子含量CA(按ASTM D 3238)优选低于2wt%(对于链烷类基油，该值通常高于2wt%)。
环烷类光亮油基油的商购来源包括由Ergon PetroleumSpecialties(Jackson,Mississippi,USA)以商品名“HypreneV150BS”商购的那些。
优选地，环烷类光亮油基油的倾点低于-9℃，优选低于-12℃(按ASTM D 5950)。
此外，优选的是环烷类光亮油基油的粘度指数(按ASTM D 2270)小于97，优选小于95，更优选小于90，甚至更优选小于85。
对于在本发明的功能性流体组合物中应用的费-托衍生基油没有特别限制。
费-托衍生基油是本领域中已知的。术语“费-托衍生”指所述基油是费-托法的合成产品或衍生自费-托法的合成产品。费-托衍生基油也可以称为GTL(气至液)基油。在本发明的功能性流体组合物中可以方便地用作基油的合适的费-托衍生基油为例如在如下专利中公开的那些：EP 0776 959、EP 0668 342、WO97/21788、WO 00/15736、WO00/14188、WO 00/14187、WO 00/14183、WO 00/14179、WO 00/08115、WO 99/41332、EP 1 029 029、WO 01/18156和WO 01/57166。
按照本发明中的费-托衍生基油在100℃下的运动粘度(按ASTM D445)通常为2.0-25.0cSt。按照本发明，费-托衍生基油在100℃下的运动粘度优选为至少3.0cSt(按ASTM D 445)，优选为至少4.0cSt和更优选为至少7.0cSt。当基油包含两种或更多种基油的共混物时，优选的是基油对该运动粘度的总贡献亦为所指出的(在2.0-25.0cSt之间等)。
除了环烷类光亮油基油和费-托衍生基油外，本发明的功能性流体组合物还可以另外包含一种或多种其它矿物油和/或一种或多种合成油的混合物。矿物油包括液态石油和链烷、环烷或混合的链烷/环烷类溶剂处理或酸处理的矿物润滑油，其可以通过加氢精制和/或脱蜡进一步精制。
在本发明的功能性流体组合物中应用的合适的附加基油为第I-III类矿物基油、第IV类聚α-烯烃(PAO)和它们的混合物。
在本发明中，“第I类”、“第II类”、“第III类”和“第IV类”基油指按照美国石油协会(API)针对I、II、III和IV类的定义的润滑油基油。这些API分类在API出版物1509,第15版，附录E，2002年4月中进行了定义。
合成油包括烃油如烯烃低聚物(包括聚α-烯烃基油；PAO)、二元酸酯、多元醇酯、聚亚烷基二醇(PAG)、烷基萘和脱蜡的蜡质异构体。可以方便地应用由Shell Group以名称“Shell XHVI”(商标)出售的合成烃基油。
以功能性流体组合物的总重量计，在本发明的功能性流体组合物中结合的基油(即环烷类光亮油基油、费-托衍生基油和任意的附加基油)的总量优选为60-99.9wt%，更优选为70-98wt%，和最优选为80-96wt%。
如上所述，本发明的功能性流体组合物的粘度指数(按ASTM D2270)大于95，优选大于100。
另外优选的是组合物的总碱数(TBN)值(按ASTM D 4739)大于35且小于75mg KOH/g，优选为45-70mg KOH/g。
本发明的功能性流体组合物可以进一步包含一种或多种添加剂如抗氧化剂、耐磨剂、分散剂(优选无灰的)、清净剂、极压添加剂、摩擦调节剂、金属钝化剂、防腐剂、破乳剂、消泡剂、密封相容剂和添加剂稀释剂基油等。
因为本领域技术人员熟悉上述和其它添加剂，因此这里不再进一步详细讨论。这些添加剂的具体实例例如在Kirk-Othmer的Encyclopedia of Chemical Technology，第三版，第14卷，477-526页中有述。
本发明的功能性流体组合物可以方便地通过混合一种或多种添加剂和基油来制备。
以功能性流体组合物的总重量计，上述添加剂的存在量通常为0.01-35.0wt%，优选为0.05-25.0wt%，和更优选为1.0-20.0wt%。
优选地，本发明的功能性流体组合物包含小于1.0wt%的聚异丁烯(PIB)，优选小于0.5wt%。还优选的是以组合物的总重量计，功能性流体组合物包含至少20wt%的环烷类光亮油基油，优选为至少25wt%，更优选为至少30wt%。另外优选的是润滑组合物包含小于5.0wt%的除一种或多种清净剂以外的任何其它添加剂。
本发明的功能性流体组合物优选为船用汽缸油。
在另一方面，本发明提供本发明的功能性流体组合物改进抗氧化性能(具体按ASTM D 2272)的用途。
参考如下实施例描述本发明，所述实施例不以任何方式限制本发明的范围。
实施例
功能性流体组合物
配制了在船用柴油机中用作SAE 50船用汽缸油(符合2009年1月修订的所谓的SAE J300规格，SAE代表汽车工程师学会)的各种功能性流体组合物。
表1给出了所应用的基油的性能。表2给出了所测试的配制完成的船用汽缸油组合物的组成和性能；组分的含量以组合物的总重量计按wt%给出。
所有测试的船用汽缸油组合物均包含基油混合物与添加剂包(在所有的测试组合物中添加剂包均相同)的组合。
“添加剂包”是船用汽缸油的特殊性能包，和包含各种性能添加剂的组合，所述添加剂包括防锈剂、分散剂、破乳剂和过碱性清净剂。
“基油1”为环烷类光亮油基油。基油1由例如中国石油(Karamay，中国)以商品名“Karamay BS”商购获得。
“基油2”为在100℃下运动粘度(ASTM D445)为约3cSt(1cSt对应于1mm2/s)的费-托衍生基油(“GTL 3”)。GTL 3可以通过WO2004/07647中描述的方法或类似方法方便地制备，其中的教导在这里作为参考引入。
“基油3”为在100℃下运动粘度(ASTM D445)为约4cSt的费-托衍生基油(“GTL 4”)。
“基油4”为在100℃下运动粘度(ASTM D445)为约8cSt的费-托衍生基油(“GTL 8”)。
这些GTL4和GTL8基油可以例如WO 02/070631中描述的方法或类似方法方便地制备，其中的教导在这里作为参考引入。
“基油5”和“基油6”为可商购的第I类矿物源基油。基油5和6由Shell Base oils(Shell Centre,London,UK)分别以商品名“HVI 130”和“HVI 650”出售。
“基油7”为可商购的聚丁烯(PIB)基油，以商品名“Indopol H-7”由INEOS Oligomers(Lavera,法国)获得。
实施例1-3和对比例1的组合物应用传统的润滑剂共混过程混合基油与添加剂包获得。
Figure BDA00001601792300071
Figure BDA00001601792300081
氧化稳定性
为了验证本发明组合物的氧化性能，按ASTM D 2272的工业标准RPVOT测试(在150℃下)进行氧化稳定性测量。测得值(以分钟表示)在下表3中给出。
磨损性能
为了验证本发明组合物的耐磨性能，按IP-239-4的工业标准四球磨损测试进行磨损测量(负载60kg，时间60分钟；速度1500rpm；温度75℃)。按IP-239-4测得的磨痕(以mm表示)在下表3中给出。
表3
讨论
从表1-3可以看出，按照本发明令人惊奇地发现，可以应用具有合适VI(即大于95)和运动粘度的环烷类光亮油基油配制船用汽缸油。
另外，从表3可以看出，本发明的组合物在氧化稳定性方面甚至胜过基于常用矿物衍生基油的船用汽缸油(对比例1-2，其含有与实施例1-3的配方相同的添加剂包)，同时获得理想的耐磨性能。
另外，在氧化稳定性和耐磨性能方面，本发明的实施例还胜过仅基于环烷类光亮油基油的船用汽缸油(对比例4，其含有与实施例1-3的配方相同的添加剂包，但不含费-托衍生基油)。另外，对比例4不具有高于95的理想VI值。

Claims (10)

1.一种功能性流体组合物，其包含：
环烷类光亮油基油；和
费-托衍生基油，
其中所述功能性流体组合物的粘度指数(按ASTM D 2270)大于95。
2.权利要求1的功能性流体组合物，其中所述环烷类光亮油基油的倾点低于-9℃，优选低于-12℃(按ASTM D 5950)。
3.权利要求1或2的功能性流体组合物，其中所述环烷类光亮油基油的粘度指数(按ASTM D 2270)低于97，优选低于95，更优选低于90，甚至更优选低于85。
4.权利要求1-3任一项的功能性流体组合物，其中所述费-托衍生基油在100℃下的运动粘度大于7.0cSt。
5.权利要求1-4任一项的功能性流体组合物，其具有大于100的粘度指数。
6.权利要求1-5任一项的功能性流体组合物，其总碱数(TBN)值(按ASTM D 4739)大于35且小于75mg KOH/g，优选为45-70mg KOH/g。
7.权利要求1-6任一项的功能性流体组合物，其包含小于1.0wt%的聚异丁烯(PIB)，优选小于0.5wt%。
8.权利要求1-7任一项的功能性流体组合物，其包含以组合物的总重量计至少20wt%的环烷类光亮油基油，优选为至少25wt%，更优选为至少30wt%。
9.权利要求1-8任一项的功能性流体组合物，其为船用汽缸油。
10.权利要求1-9任一项的功能性流体组合物提高抗氧化性(具体按ASTM D 2272)的用途。
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