CN101796171A - 与生物燃料相容的用于柴油发动机中的润滑组合物 - Google Patents
与生物燃料相容的用于柴油发动机中的润滑组合物 Download PDFInfo
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Abstract
本发明提供一种与生物燃料相容的用于柴油发动机中的润滑组合物,所述润滑组合物包含属于API基油分类第III类和/或第II类的基油、0.5-5质量%的酚类抗氧化剂和0.5-5质量%的胺基抗氧化剂,抗氧化剂的总含量为至少2质量%。
Description
技术领域
本发明涉及用于利用生物燃料的柴油发动机中的润滑组合物。
背景技术
近些年来,由于降低全球环境中CO2的贡献,积极利用由植物衍生和通过生物质技术生产的燃料存在越来越大的动力。然而,在组成上它们不一定与现有的化石燃料相似,因此可以预期生物燃料可能产生许多问题。在内燃机中使用的润滑油领域内,在技术方面进行了许多研究,以应对这些问题。
在主要用于汽油发动机领域的醇燃料的情况下,不能避免与水进行混合,并且与汽油的情况下相比,发动机部件受到更大的磨损。由此,已经提出了这些问题的解决方案。参见日本特许公开专利5-70786(1993)。
在一些情况下,用于机动车辆中的柴油发动机中的生物燃料通过植物油甲酯化生产,在欧洲的法国、德国和意大利主要用菜籽油或葵花籽油作为它们的原料,和在美国主要用大豆油作为它们的原料。在许多情况下,这些燃料通过在轻油中混合约20%进行使用。
当使用这些生物柴油燃料时,必须牢记有关这些生物柴油燃料的几点。它们的一些方面仅从燃料的角度来看需要进行改进,这是因为它们的粘度和倾点太高,和它们由于衍生自植物油而含有许多不饱和脂肪酸因而易于发生氧化。此外,这些生物柴油燃料可能直接与可食用植物油竞争,因此它们不如上述作为汽油替代品的醇燃料研究得那么多,所以很少尝试改进与生物柴油燃料相关联的润滑油。
在上述柴油发动机中,因为使用了生物柴油燃料与轻油的混合物,观察到的现象是生物柴油燃料的未燃部分与润滑油混合,促进了润滑油的老化。这导致难以长期稳定使用润滑油。
本发明人发现即使在与生物柴油燃料混合之后也能够通过在润滑油组合物中组合不同种类的抗氧化剂即酚类抗氧化剂和胺基抗氧化剂,来抑制润滑油老化和特别是润滑油清净剂性能的劣化。
发明内容
为此,本发明提供与生物燃料相容的用于柴油发动机中的润滑组合物,所述润滑组合物包含属于API基油分类第III类和/或第II类的基油、0.5-5质量%的酚类抗氧化剂和0.5-5质量%的胺基抗氧化剂,抗氧化剂的总含量为至少2质量%。
根据本发明,即使生物柴油燃料在润滑油中混合之后,也可能通过一起使用不同种类的抗氧化剂即酚类抗氧化剂和胺基抗氧化剂来抑制清净剂性能的快速劣化和润滑油的加速老化,和因此可能在长时间内稳定使用润滑油。
如上所述,机动车辆的柴油发动机中使用的轻燃料油和生物柴油具有多种明显的区别,和根据文献(Kagaku Kogyo Nippo[TheChemical Daily]在2002-04-25出版的“New biomass liquid fuels for the21st century”,该文献的教导经此引用并入本文),它们可以概述为表1中所示的区别。
表1
生物柴油 | 轻油 | |
倾点(℃) | -5.5 | -11.5 |
运动粘度(mm2/s) | 5.6 | 3.0 |
闪点(℃) | 135-145 | 88 |
硫含量(%) | 0.0001 | 0.2 |
碳(%) | 77.1-77.9 | 87.2 |
氢(%) | 11.7-11.8 | 12.8 |
氧(%) | 11.1-11.2 | 0 |
由表1明显看出,在上述方面中,生物柴油与轻油明显不同的是组分氧原子的含量。此外,据信由于它们含有源自不饱和脂肪酸的双键,因此燃烧反应本身不同。
另外,可以提及的是,在物理性质方面,闪点比轻油高,和它们更易于蒸发。当作为燃料供应至发动机时,反应可能在完全燃烧过程中在基本过程中停止,和未反应部分将通常与润滑油混合或未燃组分本身将与润滑油混合,导致润滑油中形成污泥和通过氧化加速润滑油的老化。
考虑到这些事实,当仅使用轻油作为燃料时,润滑油的特征将在于在甚至比暴露于高温更为苛刻的条件下进行使用。
对于本发明的基油,可能使用任意适合的矿物油或合成油,和通常可能单独或以混合物形式使用属于API(美国石油学会)基油分类的第III类和第II类的基油。
这些第III类和第II类基油包括例如:通过对由原油常压蒸馏获得的润滑油馏分进行高度加氢精制获得的链烷烃矿物油,通过Isodewax方法(该方法脱蜡并用异链烷烃取代通过脱蜡方法生产的蜡)精制的基油,通过Mobil蜡异构化方法精制的基油,和通过费-托方法合成之后溶剂脱蜡或催化剂脱蜡的所谓的GTL(天然气制合成油)基油。它们还包括根据NAD(National Advertising Division)的规则可以称为“合成油”的那些,NAD负责美国的广告裁定。
酚类抗氧化剂和胺基抗氧化剂一起共混在这些基油中。
作为这些酚类抗氧化剂的实例,可以提及的有:2,6-二-叔-丁基苯酚,2,6-二-叔-丁基-p-甲酚,2,6-二-叔-丁基-4-乙基苯酚,2,2′-亚甲基双(4-甲基-6-叔-丁基苯酚),2,2′-亚甲基双(4-乙基-6-叔-丁基苯酚),4,4′-双(2,6-二-叔-丁基苯酚),4,4′-硫代双(6-叔-丁基-o-甲酚),和3-(4-羟基-3,5-二-叔-丁基-苯基)丙酸的烷基醇酯例如3-(4-羟基-3,5-二-叔-丁基-苯基)丙酸的6甲基庚醇酯。
此外,作为这些胺基抗氧化剂的实例,可以提及的有:二苯胺,p,p′-二辛基二苯胺,p,p′-二壬基二苯胺,p,p′-二(十二烷基)二苯胺,苯基-α-萘胺,p-辛基苯基-α-萘胺,p-壬基苯基-α-萘胺和p-十二烷基苯基-α-萘胺,和它们的混合物。
上述二苯胺的一个优选实例是二苯胺,其是N-苯基苯胺和2,4,4-三甲基戊烯的反应产物。
上述酚类抗氧化剂的量为润滑油组合物总量的0.5-5.0质量%,和优选为0.5-2质量%。
上述胺基抗氧化剂的量为润滑油组合物总量的0.5-5.0质量%,和优选为0.5-2质量%。
对于上述酚类抗氧化剂和胺基抗氧化剂,如果含量小于0.5质量%,则氧化稳定性下降,这是不希望的,和如果它超过5质量%,则活塞清净性下降,这通常也是不希望的。
酚类抗氧化剂和胺基抗氧化剂分别以上述量进行使用,但是同时还要求两种抗氧化剂的总量不小于2质量%。如果二者的总量小于该值,则将得不到预期的效果。
还可以向该润滑油组合物中按需加入适合的分散剂、极压剂、清净剂、粘度指数改进剂和其它添加剂。
在另一方面,本发明提供操作柴油发动机的方法,包括用本发明的润滑组合物润滑柴油发动机,和使用生物燃料作为燃料,所述生物燃料优选衍生自菜籽油。
实施例
生物柴油燃料(BDF)是衍生自菜籽油的甲基酯,和制备该生物柴油燃料使之具有表2中显示的性质。
表2
项目 | 测试方法 | 单位 | 特征(数值) |
密度:振动法(15℃) | JIS K-2249 | g/cm3 | 0.883 |
闪点:PMCC方法 | JIS K-2265 | ℃ | 155 |
运动粘度:30℃ | JIS K-2283 | mm2/s | 5.51 |
十六烷值 | JIS K-2280 | 53.0 |
以下组分材料用于制备本发明实施方案的实施例和对比例。
(1)基油:属于API第III类的矿物油
(2)酚类抗氧化剂:3-(4-羟基-3,5-二-叔-丁基-苯基)丙酸的6甲基庚醇酯
(3)胺基抗氧化剂:二苯胺,为N-苯基苯胺和2,4,4-三甲基戊烯的反应产物
(4)添加剂包:含分散剂、ZnDTP和清净剂的添加剂。
实施例1-4,对比例1-6
利用上述组分材料,根据表3和4制备实施例1-4和对比例1-6的润滑油组合物。
上述对比例6是机动车辆中使用的含有JASO(Engine OilStandards Implementation Panel)DH-2级别柴油燃烧发动机油的组合物。
在每种情况下,共混的各组分的量以质量%表示。
测试
为了观察实施例1-4和对比例1-6的润滑油组合物的性能,在280℃下,在针对100质量%的每种润滑油组合物加入5质量%的生物柴油燃料的负载条件下,进行热管测试(根据JPI-5S-55-99;日本石油学会用于测定高温沉积物的标准测试)。
对热管测试的评价分为0-10,0.5作为最小单位,7和7以上设定为合格。
测试结果
结果显示在表3和4中。
表3
实施例1 | 实施例2 | 实施例3 | 实施例4 | |
基油 | 86 | 85 | 85.5 | 82 |
酚类抗氧化剂 | 1.0 | 1.5 | 1.5 | 2.0 |
胺基抗氧化剂 | 1.0 | 1.5 | 1.0 | 4.0 |
添加剂包 | 12 | 12 | 12 | 12 |
总计 | 100 | 100 | 100 | 100 |
混合的BDF | 5 | 5 | 5 | 5 |
热管评分 | 7.0 | 7.0 | 7.0 | 7.5 |
表4
对比例1 | 对比例2 | 对比例3 | 对比例4 | 对比例5 | 对比例6 | |
基油 | 88 | 85.5 | 84.5 | 85.5 | 86.5 | 88 |
酚类抗氧化剂 | 2.5 | 0.5 | ||||
胺基抗氧化剂 | 2.5 | 3.5 | 1.0 |
对比例1 | 对比例2 | 对比例3 | 对比例4 | 对比例5 | 对比例6 | |
添加剂包 | 12 | 12 | 12 | 12 | 12 | 12 |
总计 | 100 | 100 | 100 | 100 | 100 | 100 |
混合的BDF | 5 | 5 | 5 | 5 | 5 | |
热管评分 | 1.0 | 2.0 | 5.0 | 3.0 | 2.5 | 7.0 |
评价
当一起使用酚类抗氧化剂和胺基抗氧化剂(如实施例1-4中所示)、各自的量不小于1质量%和总量不小于2质量%时,在所有情况下,在热管测试中均获得7或更高的评价,很明显这些润滑油组合物在与生物燃料混合后不易老化。
在对比例1的情况下没有添加抗氧化剂,和热管评分不好,为1.0。对比例2仅使用2.5质量%的胺基抗氧化剂,虽然总量超过2质量%,但是热管评分不好,为2.0。对比例3中加入了比对比例2更多的胺基抗氧化剂,但是热管评分仅上升至5.0。对比例4仅使用2.5质量%的酚类抗氧化剂,虽然总量超过2质量%,但是热管评分不好,为3.0。对比例5一起使用了两种抗氧化剂,但是总量小于2质量%和因此热管评分不好,为2.5。因此对于对比例1-5任一个来说,均没有获得令人满意的效果。
对比例6没有混合生物燃料,和即使没有使用酚类抗氧化剂或胺基抗氧化剂,热管评分也为7.0,因此它可以视为获得了令人满意的效果。
Claims (7)
1.一种与生物燃料相容的用于柴油发动机中的润滑组合物,所述润滑组合物包含属于API基油分类第III类和/或第II类的基油、0.5-5质量%的酚类抗氧化剂和0.5-5质量%的胺基抗氧化剂,抗氧化剂的总含量为至少2质量%。
2.权利要求1的润滑组合物,其中所述酚类抗氧化剂是3-(4-羟基-3,5-二-叔-丁基-苯基)丙酸的6-甲基庚醇酯。
3.权利要求1或2的润滑组合物,其中所述胺基抗氧化剂是二苯胺,该二苯胺为N-苯基苯胺和2,4,4-三甲基戊烯的反应产物。
4.权利要求1-3任一项的润滑组合物,其中柴油发动机中使用的生物燃料衍生自菜籽油。
5.权利要求1-4任一项的润滑组合物在柴油发动机中的用途。
6.权利要求5的用途,其中在柴油发动机中使用生物燃料,优选衍生自菜籽油的生物燃料。
7.一种操作柴油发动机的方法,包括用权利要求1-4任一项的润滑组合物润滑柴油发动机,和使用生物燃料作为燃料,所述生物燃料优选衍生自菜籽油。
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US7960322B2 (en) * | 2007-10-26 | 2011-06-14 | Chevron Oronite Company Llc | Lubricating oil compositions comprising a biodiesel fuel and an antioxidant |
CA2766063A1 (en) | 2009-06-26 | 2010-12-29 | The Lubrizol Corporation | Engine oil formulations for biodiesel fuels |
BR112012002608A2 (pt) * | 2009-08-05 | 2016-03-29 | Basf Se | composição lubrificante, e, método para melhorar o desempenho de uma composição lubrificante. |
JP2017039841A (ja) * | 2015-08-19 | 2017-02-23 | コスモ石油ルブリカンツ株式会社 | 内燃機関用潤滑油組成物 |
CA3047284A1 (en) | 2016-12-27 | 2018-07-05 | The Lubrizol Corporation | Lubricating composition with alkylated naphthylamine |
EP3562921B1 (en) | 2016-12-27 | 2022-04-27 | The Lubrizol Corporation | Lubricating composition including n-alkylated dianiline |
WO2018156304A1 (en) | 2017-02-21 | 2018-08-30 | Exxonmobil Research And Engineering Company | Lubricating oil compositions and methods of use thereof |
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EP2179011B1 (en) | 2018-06-27 |
US20130102509A1 (en) | 2013-04-25 |
BRPI0814579B1 (pt) | 2018-03-27 |
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