CN116855295A - 柴油机油组合物及其制备方法和应用 - Google Patents

柴油机油组合物及其制备方法和应用 Download PDF

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CN116855295A
CN116855295A CN202210314272.3A CN202210314272A CN116855295A CN 116855295 A CN116855295 A CN 116855295A CN 202210314272 A CN202210314272 A CN 202210314272A CN 116855295 A CN116855295 A CN 116855295A
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oil composition
diesel engine
antioxidant
diesel
engine oil
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林志鹏
郑金花
潘威
杨慧青
王靖宇
鞠媛媛
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China Petroleum and Chemical Corp
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Abstract

本发明提供一种柴油机油组合物及其制备方法和应用,通过特定的清净剂(磺酸盐、硫化烷基酚盐和石油磺酸盐)、特定的分散剂(双丁二酰亚胺以及任选地单丁二酰亚胺、高分子丁二酰亚胺、硼化聚异丁烯基丁二酰亚胺、聚异丁烯基丁二酰亚胺中的一种或多种)以及特定的抗氧抗腐剂(二异辛基二硫代磷酸锌盐和硫磷仲醇基锌盐中至少一种)的配合使用,使得所提供的组合物同时具有优异的烟炱分散性和水分离性。

Description

柴油机油组合物及其制备方法和应用
技术领域
本发明涉及润滑油技术领域,具体涉及一种柴油机油组合物及其制备方法和应用。
背景技术
烟炱是柴油发动机润滑油中最常见的不溶物之一,其产生原因主要是由于燃烧不良及燃烧室发生窜气,滑油中烟炱过多会导致柴油机运行效率降低、燃油消耗量增加;烟炱和沉积物聚集,有时伴有水污染,会形成油泥;抗磨添加剂被烟炱吸收导致抗磨性下降,导致发动机部件磨损;分散剂被吸收,清净分散能力降低;在有水存在情况下,烟炱容易被滤器的纤维吸收从而堵塞油路及滤器;烟炱会加剧润滑油的氧化;烟炱会导致润滑油粘度增加。柴油机油良好的分散剂体系性能使烟炱颗粒分散在润滑油体系中防止其聚集,对延长柴油机油使用寿命,保护发动机零部件起着重要作用。一般来说,分散剂加剂量越高,烟炱分散性越好,但随着清洁分散剂这类表面活性剂的增加,油品的水分离性能会变差。船用柴油发动机由于长期在海洋环境运行,难免会受到水污染,需要通过油水分离机不定期对在用润滑油进行水分离操作,故船用柴油发动机润滑油要求具有良好的水分离性能。
文献CN201710969292.3公开了一种柴油机油组合物及其制备方法,其包含苯并三唑衍生物、高分子丁二酰亚胺无灰分散剂、单丁二酰亚胺无灰分散剂、磺酸钙清净剂、硫化烷基酚钙清净剂、烷基化二苯胺型抗氧剂、屏蔽酚型抗氧剂、分散型OCP黏度指数改进剂和润滑油基础。
CN 110016380 A公开了一种柴油机油组合物,包含适量金属清净剂、无灰分散剂、抗氧抗腐剂、复合抗氧剂、复合减摩剂、黏度指数改进剂、降凝剂和余量基础油。
CN 110713859 A也公开了一种柴油机油组合物,以该柴油机油组合物总重量为基准,该柴油机油组合物包括:质量含量为2.0%~8.0%的金属清净剂;质量含量为3.0%~10.0%的无灰分散剂;质量含量为0.3%~2.5%的抗氧抗腐剂;质量含量为0.3%~2.0%的复合抗氧剂;质量含量为0.2%~2.0%的复合减摩剂;质量含量为3.0%~14.0%的黏度指数改进剂;质量含量为0.2%~0.8%的降凝剂;质量含量为72.0%~90.0%的基础油。
现有技术中虽然已存在诸多类型的柴油机油组合物,但现有柴油机油组合物仍存在烟炱分散性和水分离性不能同时达到较好技术水平的技术缺陷。
发明内容
鉴于上述现有技术中存在的问题,本发明的目的之一在于提供一种柴油机油组合物,通过特定的清净剂、特定的分散剂以及特定的抗氧抗腐剂的配合使用,使得所提供的组合物同时具有优异的烟炱分散性和水分离性。
本发明的目的之二在于提供一种与目的之一相对应的柴油机油组合物的制备方法。
本发明的目的之三在于提供一种与上述目的相对应的柴油机油组合物的应用。
为实现上述目的之一,本发明采取的技术方案如下:
一种柴油机油组合物,其或其原料以重量份数计包括下述组分:
其中,所述清净剂包括磺酸盐、硫化烷基酚盐和石油磺酸盐,优选由磺酸盐、硫化烷基酚盐和石油磺酸盐组成,更优选由合成磺酸钙、硫化烷基酚钙和石油磺酸钙组成;
所述分散剂包括双丁二酰亚胺以及任选地单丁二酰亚胺、高分子丁二酰亚胺、硼化聚异丁烯基丁二酰亚胺、聚异丁烯基丁二酰亚胺中的一种或多种,优选为双丁二酰亚胺;以及
所述抗氧抗腐剂选自二异辛基二硫代磷酸锌盐和硫磷仲醇基锌盐中至少一种。
在本发明的一些优选的实施方式中,所述柴油机油组合物或其原料以重量份数计包括:
在本发明的一些优选的实施方式中,所述柴油机油组合物或其原料以重量百分数计包括:
在本发明的一些优选的实施方式中,所述抗氧抗腐剂与所述基础油的质量比为0.008~0.02。
在本发明的一些优选的实施方式中,所述辅助抗氧剂选自胺型抗氧剂、屏蔽酚抗氧剂、氨基甲酸盐类抗氧剂中的至少一种。
根据本发明,市售的胺型抗氧剂、屏蔽酚抗氧剂、氨基甲酸盐类抗氧剂均可用于本发明并获得相当的技术效果,因此,本发明并不意欲对胺型抗氧剂、屏蔽酚抗氧剂、氨基甲酸盐类抗氧剂的具体种类进行限制。
在本发明的一些优选的实施方式中,所述降凝剂选自聚α烯烃、烷基萘、聚甲基苯烯酸脂中的至少一种,优选地,所述聚α烯烃选自平均分子量为50000~150000的聚α烯烃中的至少一种;所述烷基萘选自C60~C66烷基萘中的至少一种。
根据本发明,市售的聚α烯烃、烷基萘、聚甲基苯烯酸脂均可用于本发明并获得相当的技术效果,因此,本发明并不意欲对聚α烯烃、烷基萘、聚甲基苯烯酸脂的具体种类进行限制。
在本发明的一些优选的实施方式中,所述抗泡剂选自复合抗泡剂和甲基硅油中的至少一种。
根据本发明,市售的复合抗泡剂和甲基硅油均可用于本发明并获得相当的技术效果,因此,本发明并不意欲对复合抗泡剂和甲基硅油的具体种类进行限制。
在本发明的一些优选的实施方式中,所述基础油包括Ⅰ类基础油和Ⅱ类基础油,其中,所述Ⅰ类基础油和所述Ⅱ类基础油的质量比为(2~4):1。
根据本发明,Ⅰ类基础油和Ⅱ类基础油为本领域公知的产品,本发明中Ⅰ类基础油和Ⅱ类基础油适用本领域中Ⅰ类基础油和Ⅱ类基础油的广义定义所限定的那些。
在本发明的一些优选的实施方式中,所述柴油机油组合物中磷含量不大于1200ppm,钙含量不大于6000ppm,氮含量不小于200ppm且不大于1400ppm,优选地,所述柴油机油组合物中磷含量不大于1000ppm,钙含量不大于5500ppm,氮含量不小于400ppm且不大于1200ppm,优选地,所述柴油机油组合物中磷含量不大于800ppm,钙含量不大于5000ppm,氮含量不小于600ppm且不大于1000ppm。
根据本发明,柴油机油组合物中的氮含量主要来源于分散剂及部分抗氧剂,氮含量的下限值是由分散剂及部分抗氧剂的添加量决定的。
为实现上述目的之二,本发明采取的技术方案如下:
一种上述实施方式中任一项所述的柴油机油组合物的制备方法,包括:在50℃~70℃的温度范围内混合所述清净剂、所述分散剂、所述抗氧抗腐剂、所述辅助抗氧剂、所述降凝剂、所述抗泡剂和所述基础油,得到所述柴油机油组合物。
在本发明的一些优选的实施方式中,所述混合在搅拌的条件下进行,所述搅拌的转速为300rpm~500rpm;所述搅拌的时间为10min~240min,优选为30min~120min,更优选为50min~100min。
为实现上述目的之三,本发明采取的技术方案如下:
一种上述实施方式中任一项所述的的柴油机油组合物或上述实施方式中任一项所述的制备方法制得的柴油机油组合物作为润滑油的应用,尤其是在作为陆用及船用四冲程大功率柴油发动机的曲轴箱及气缸的润滑油的应用。
本发明的有益效果至少在于以下几个方面:
其一,本发明所提供的柴油机油组合物原料易得,制备方法简单,成本低,性价比高,在具备良好的高温清净型、抗氧性的基础上,同时具备良好的分散性及分水性。
其二,本发明所提供的柴油机油组合物基于上述提及的优异性能,能够有效保护陆用及船用四冲程大功率柴油发动机的曲轴箱及气缸零部件,且本发明所提供的柴油机油组合物使用寿命长。
具体实施方式
以下通过实施例对本发明进行详细说明,但本发明的保护范围并不限于下述说明。
实施例中未注明具体条件者,按照常规条件或制造商建议的条件进行。所用试剂或仪器未注明生产厂商者,均为可以通过市购途径获得的常规产品。
下述实施方式中,柴油机油烟炱分散性测试仪的型号为L-5型,其测试原理是柴油在烟炱发生器中燃烧生成烟炱、废气和水蒸气,这些燃烧后的物质被不断的吸收到盛有油品的吸收瓶内,烟炱与样品在瓶中得到充分混合,溢出的气体经三级过滤后进入吸引器排空。当通入烟炱的初期(抑制期),被测油样中的烟炱以单独的小颗粒状存在,不会引起粘度的快速变化,粘度呈现缓慢增加的趋势,瓶中负压也在缓慢上升。分散性的好与差,取决于样品在抑制期内坚持的时间长短,也就是承载烟炱数量的能力。当烟炱粒子增加到一定程度时,就会发生积聚,形成胶状的网状结构,引起粘度的激增,进入吸收烟炱的末期(锐变期),样品对烟炱的分散作用失效,由烟炱凝聚的胶状物堵塞了吸收瓶的通道(相当于发动机过滤器被堵,油压下降),瓶内负压急剧增加,当压力达到试验机设定的极限负压时,试验自动停止。累计通入烟炱的时间,即为油品的分散性衰变期。
实施例1~9和对比例1~5
将表1-表3中所示的各组分在60℃温度下搅拌1小时,之后采用柴油机油烟炱分散性测试仪(自建方法)评价油品的烟炱分散性,其中,衰变期越长,表示油品的烟炱分散性越好,反之越差;采用分水性试验(SH/T 0619)评价油品的分水性,其中,水层越大,乳化层越小表明油品分水性越好,反之越差。检测结果见表4。
表1
表2
表3
表4
应当注意的是,以上所述的实施例仅用于解释本发明,并不构成对本发明的任何限制。通过参照典型实施例对本发明进行了描述,但应当理解为其中所用的词语为描述性和解释性词汇,而不是限定性词汇。可以按规定在本发明权利要求的范围内对本发明作出修改,以及在不背离本发明的范围和精神内对本发明进行修订。尽管其中描述的本发明涉及特定的方法、材料和实施例,但是并不意味着本发明限于其中公开的特定例,相反,本发明可扩展至其他所有具有相同功能的方法和应用。

Claims (10)

1.一种柴油机油组合物,其或其原料以重量份数计包括下述组分:
其中,所述清净剂包括磺酸盐、硫化烷基酚盐和石油磺酸盐,优选由磺酸盐、硫化烷基酚盐和石油磺酸盐组成,更优选由合成磺酸钙、硫化烷基酚钙和石油磺酸钙组成;
所述分散剂包括双丁二酰亚胺以及任选地单丁二酰亚胺、高分子丁二酰亚胺、硼化聚异丁烯基丁二酰亚胺、聚异丁烯基丁二酰亚胺中的一种或多种,优选为双丁二酰亚胺;以及
所述抗氧抗腐剂选自二异辛基二硫代磷酸锌盐和硫磷仲醇基锌盐中至少一种。
2.根据权利要求1所述的柴油机油组合物,其特征在于,所述抗氧抗腐剂与所述基础油的质量比为0.008~0.02。
3.根据权利要求1或2所述的柴油机油组合物,其特征在于,所述辅助抗氧剂选自胺型抗氧剂、屏蔽酚抗氧剂、氨基甲酸盐类抗氧剂中的至少一种。
4.根据权利要求1-3中任一项所述的柴油机油组合物,其特征在于,所述降凝剂选自聚α烯烃、烷基萘、聚甲基苯烯酸脂中的至少一种,优选地,所述聚α烯烃选自平均分子量为50000~150000的聚α烯烃中的至少一种;所述烷基萘选自C60~C66烷基萘中的至少一种。
5.根据权利要求1-4中任一项所述的柴油机油组合物,其特征在于,所述抗泡剂选自复合抗泡剂和甲基硅油中的至少一种。
6.根据权利要求1-5中任一项所述的柴油机油组合物,其特征在于,所述基础油包括Ⅰ类基础油和Ⅱ类基础油,其中,所述Ⅰ类基础油和所述Ⅱ类基础油的质量比为(2~4):1。
7.根据权利要求1-6中任一项所述的柴油机油组合物,其特征在于,所述柴油机油组合物中磷含量不大于1200ppm,钙含量不大于6000ppm,氮含量不小于200ppm且不大于1400ppm,优选地,所述柴油机油组合物中磷含量不大于1000ppm,钙含量不大于5500ppm,氮含量不小于400ppm且不大于1200ppm,优选地,所述柴油机油组合物中磷含量不大于800ppm,钙含量不大于5000ppm,氮含量不小于600ppm且不大于1000ppm。
8.一种权利要求1-7中任一项所述的柴油机油组合物的制备方法,包括:在50℃~70℃的温度范围内混合所述清净剂、所述分散剂、所述抗氧抗腐剂、所述辅助抗氧剂、所述降凝剂、所述抗泡剂和所述基础油,得到所述柴油机油组合物。
9.根据权利要求8所述的制备方法,其特征在于,所述混合在搅拌的条件下进行,所述搅拌的转速为300rpm~500rpm;所述搅拌的时间为10min~240min,优选为30min~120min,更优选为50min~100min。
10.一种权利要求1-7中任一项所述的柴油机油组合物或根据权利要求8或9所述的制备方法制得的柴油机油组合物作为润滑油的应用,尤其是在作为陆用及船用四冲程大功率柴油发动机的曲轴箱及气缸的润滑油的应用。
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Publication number Priority date Publication date Assignee Title
CN1523086A (zh) * 2003-02-20 2004-08-25 中国石油天然气股份有限公司 一种适用于ⅲ类基础油的发动机润滑油组合物
CN111500349A (zh) * 2020-05-27 2020-08-07 中国石油化工股份有限公司 船用柴油机用油组合物、制备方法及其用途
CN112143542A (zh) * 2020-09-30 2020-12-29 新乡市瑞丰新材料股份有限公司 一种柴油机油复合剂及制备方法

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1523086A (zh) * 2003-02-20 2004-08-25 中国石油天然气股份有限公司 一种适用于ⅲ类基础油的发动机润滑油组合物
CN111500349A (zh) * 2020-05-27 2020-08-07 中国石油化工股份有限公司 船用柴油机用油组合物、制备方法及其用途
CN112143542A (zh) * 2020-09-30 2020-12-29 新乡市瑞丰新材料股份有限公司 一种柴油机油复合剂及制备方法

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