CN109694769A - 一种可生物降解的船用发动机润滑油 - Google Patents

一种可生物降解的船用发动机润滑油 Download PDF

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CN109694769A
CN109694769A CN201710991696.2A CN201710991696A CN109694769A CN 109694769 A CN109694769 A CN 109694769A CN 201710991696 A CN201710991696 A CN 201710991696A CN 109694769 A CN109694769 A CN 109694769A
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oil
base oil
lubricating oil
marine engine
parts
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张翠侦
许海龙
马莉莉
齐邦峰
徐岩峰
秦一鸣
田义斌
朱长申
郭莎莎
朱玉龙
焦祖凯
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China National Offshore Oil Corp CNOOC
CNOOC Research Institute of Refining and Petrochemicals Beijing Co Ltd
CNOOC Qingdao Heavy Oil Processing Engineering Technology Research Center Co Ltd
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China National Offshore Oil Corp CNOOC
CNOOC Research Institute of Refining and Petrochemicals Beijing Co Ltd
CNOOC Qingdao Heavy Oil Processing Engineering Technology Research Center Co Ltd
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Abstract

本发明涉及一种可生物降解船用发动机润滑油，主要解决目前所用的船用润滑油的生物降解性。该船用发动机润滑油由复合基础油、复合添加剂及其他添加剂组成，其中，复合基础油50～95份，复合添加剂5～25份，其他添加剂0.01～1份。本发明采用生物降解性25～75份的海洋油加氢基础油、生物降解性接近100％的改性地沟油和合成油及环境友好型添加剂，以平衡经济性和可生物降解性的关系，提供一种经济性和可生物降解性均较好的船用发动机润滑油。

Description

一种可生物降解的船用发动机润滑油
技术领域
本发明涉及一种可生物降解的船用发动机润滑油。
背景技术
摩擦、磨损是机械设备运转过程中普遍发生的自然现象，也是造成材料、设备破坏和失效的重要原因。据统计，全世界生产能源的1/3～1/2损失在摩擦磨损上。随着润滑油的广泛应用，润滑油通过各种途径进入生态环境中，给生态环境造成严重污染。目前，全世界使用的润滑油中，除一部分由机械运转正常消耗掉或部分回收利用外，在装拆、灌注、机械运转过程中仍有4％～10％的润滑油流入生态环境。据统计，目前每年约有500万～1000万吨油基化学品进入生物圈，严重污染陆地植被和江河湖泊的生态平衡。经研究表明，传统的润滑油大多数以矿物油作为基础油，然而矿物油在自然环境中生物降解能力很差，容易在环境中集聚并对生态环境造成污染。
随着人们环保意识的不断增强和环保法规的日趋完善，矿物油基础油正面临着严峻的挑战。与此相适应，环境友好型润滑油应运而生。随着船运行业的发展，世界远洋船只数量及吨位在不断增长，船用内燃机油的需求量也不断提高。以石油产品为主要燃料的船舶发动机所产生的排放物对当前环境造成很大的破坏，尤其是船舶通行量大、交通密集的海域，其排放量更为惊人。为了减少环境的污染，制定了一系列海洋环保法规，如防止船舶污染国际公约、防止船舶大气污染细则等。随着环保等新法规的陆续出台，船舶制造业从降低排放的角度不断改进发动机设计，要求船用内燃机油具有低灰分、低金属含量、高碱值保持性等特点，然而现有的船用发动机油已无法满足上述要求。
专利CN 103710071 A公开了一种合成环保型船用内燃机油及其制备方法，其以Ⅱ类基础油、Ⅲ类基础油、合成烃基础油、合成酯基础油中的任意一种为原料与油溶性聚烷撑二醇复配，通过加入复合添加剂、黏度指数改进剂调和得到船用内燃机油，其环境友好性表明，该样品的生物降解率比常规船用内燃机油提高30～90％。
综上所述，以合成型基础油调和，所得的船用内燃机油生物降解性较好，但所用成本较高，经济性较差；以矿物型基础油调和，所得的船用内燃机油生物降解性较差。因此，开发具有良好经济性和生物可降解性的船用发动机润滑油以降低对环境的影响已经成为产品配制的驱动力。
发明内容
本发明为了弥补现有技术的不足，提供了一种经济性和可生物降解性均较好的船用发动机润滑油。
本发明所提供的船用发动机润滑油由复合基础油、复合添加剂及其他添加剂组成，按质量分数计算，各组成及质量份数如下：
复合基础油 50～95份
复合添加剂 5～25份
其他添加剂 0.01～1份。
其中，所述复合基础油的用量优选范围可为80.0～93.0份，具体可为84.2份或90.18份。
所述复合添加剂的用量优选范围可为8～20份，具体可为15.6份或9.8份。
所述其他添加剂的用量优选范围可为0.015～0.08份，具体可为0.02份。
所述复合基础油由合成型基础油和矿物型基础油组成，其中，合成型基础油与矿物型基础油的质量比可为0.3-1：2-7，具体可为1:4、1:2.8或0.37:7。
所述合成型基础油可为下述一种或几种的混合物：聚α烯烃、合成酯类基础油、和改性地沟油，具体可为季戊四醇合成酯基础油。
所述改性地沟油为地沟油经过白土和活性炭混合物的吸附及碱洗后过滤所得到。
所述矿物型基础油可为Ⅱ类基础油、Ⅲ类基础油、HVI150BS光亮油和环烷基基础油中的一种或几种，优选Ⅱ类基础油，具体可为HVI150BS光亮油、Ⅱ类基础油500N和环烷基润滑油基础油。
所述Ⅱ类石蜡基基础油、Ⅲ类石蜡基基础油可使用海洋馏分油经加氢精制得到。
所述HVI150BS光亮油的指标为色度不大于1.0，闪点不低于270℃、100℃运动黏度28-34mm2/s，酸值不大于0.3mgKOH/g，黏度指数大于80。
所述Ⅱ类基础油500N指标为：色度不大于2.0，闪点不低于260℃，100℃运动黏度为9.3-12.5mm2/s，酸值不大于0.3mgKOH/g，黏度指数不小于90。
所述环烷基润滑油基础油指标为：闪点不低于230℃，100℃运动黏度为15.0-20.0mm2/s，酸值不大于0.5mgKOH/g。
所述复合添加剂由清净分散剂和抗氧剂组成。其中，清净分散剂与抗氧剂的质量比可为8-16：0.5-1.5。
所述清净分散剂可选自下述至少一种：磺酸盐、硫化烷基酚盐、双丁二酰亚胺和有机物改性的丁二酰亚胺，具体可为质量比为1.8:1的高碱值合成磺酸钙和双丁二酰亚胺的混合物。
所述抗氧剂可选自下述至少一种：2,6-二叔丁基对甲酚、二烷基二苯胺、2,6-二叔丁基酚和亚乙基双酚。
所述其他添加剂由抗泡剂和破乳剂组成。其中，抗泡剂与破乳剂的质量比依次可为0.5-1.5：180-220。
所述抗泡剂可选自甲基硅油或丙烯酸酯、非硅抗泡剂中的至少一种。
所述破乳剂可选自胺与环氧乙烷缩合物或聚醚类高分子化合物中的至少一种。
本发明采用生物降解性约为70％的海洋油加氢基础油、生物降解性接近100％的改性地沟油和合成油及环境友好型添加剂，以平衡经济性和可生物降解性的关系，提供一种经济性和可生物降解性均较好的船用发动机润滑油。
具体实施方式
下面通过具体实施例对本发明进行说明，但本发明并不局限于此。
下述实施例中所使用的实验方法如无特殊说明，均为常规方法；下述实施例中所用的试剂、材料等，如无特殊说明，均可从商业途径得到。
实施例1
一种可生物降解船用发动机润滑油，按质量份数计算，其原料的组成及含量如下：
复合基础油84.2份
复合添加剂15.6份
其他添加剂0.02份
所述的复合基础油，是由季戊四醇合成酯基础油和Ⅱ类基础油500N组成，其质量比为1:4；
所述的复合添加剂包括清净分散剂、抗氧剂，其中清净分散剂为14.8份，为高碱值合成磺酸钙和双丁二酰亚胺，其质量比为1.8:1；抗氧剂为二烷基二苯胺，为0.8份；
所述的其他添加剂包括抗泡剂和抗乳化剂，其中抗泡剂为丙烯酸酯，所占份数为0.0001份；抗乳化剂为聚多元醇烷基醚，所占份数为0.0199份。
上述一种可生物降解船用发动机润滑油的制备方法，步骤如下：
按份数计算，在常温下将16.95分季戊四醇合成酯基础油加入到67.25份的Ⅱ类基础油500N中，升温至60℃，在搅拌的条件下，依次加入9.51份高碱值合成磺酸钙和5.29份双丁二酰亚胺、0.8份二烷基二苯胺，搅拌均匀后，再依次加入0.0001份丙烯酸酯和0.0199份聚多元醇烷基醚，并搅拌均匀。然后在60℃下继续搅拌0.5小时即得到可生物降解船用发动机润滑油。
实施例2
一种可生物降解船用发动机润滑油，按质量分数计算，其原料的组成及含量如下：
复合基础油84.2份
复合添加剂15.6份
其他添加剂0.02份
所述的复合基础油是由改性地沟油、Ⅱ类基础油500N和HVI150BS组成，其质量比为0.37:6:1；
所述的复合添加剂包括清净分散剂、抗氧剂，其中清净分散剂为14.8份，为高碱值合成磺酸钙和双丁二酰亚胺，其质量比为2:1；抗氧剂为二烷基二苯胺，为0.8份；
所述的其他添加剂包括抗泡剂和抗乳化剂，其中抗泡剂为丙烯酸酯，所占份数为0.0001份；抗乳化剂为聚多元醇烷基醚，所占份数为0.0199份。
上述一种可生物降解船用发动机润滑油的制备方法，步骤如下：
按分数计算，在常温下将4.38份改性地沟油和11.72份HVI150BS依次加入到72.2份的Ⅱ类基础油500N中，升温至60℃，在搅拌的条件下，依次加入9.87份高碱值合成磺酸钙和4.93双丁二酰亚胺、0.8份二烷基二苯胺，搅拌均匀后，再依次加入0.0001份丙烯酸酯和0.0199份聚多元醇烷基醚，并搅拌均匀。然后在60℃下继续搅拌0.5小时即得到可生物降解船用发动机润滑油。
实施例3
一种可生物降解船用发动机润滑油，按质量分数计算，其原料的组成及含量如下：
复合基础油90.18份
复合添加剂9.8份
其他添加剂0.02份
所述的复合基础油，是由聚α烯烃和Ⅱ类基础油500N组成，其质量比为1:2.78；
所述的复合添加剂包括清净分散剂、抗氧剂，其中清净分散剂为9.0份，为高碱硫化烷基酚钙和有机物改性的丁二亚酰胺，其质量比为1:1；抗氧剂为亚乙基双酚，为0.6份；
所述的其他添加剂包括抗泡剂和抗乳化剂，其中抗泡剂为丙烯酸酯，所占份数为0.0001份；抗乳化剂为聚多元醇烷基醚，所占份数为0.0199份。
上述一种可生物降解船用发动机润滑油的制备方法，步骤如下：
按分数计算，在常温下将23.86分聚α烯烃加入到66.32份的Ⅱ类基础油500N中，升温至60℃，在搅拌的条件下，依次加入4.5份高碱值合成磺酸钙和4.5份双丁二酰亚胺、0.6份亚乙基双酚，搅拌均匀后，再依次加入0.0001份丙烯酸酯和0.0199份聚多元醇烷基醚，并搅拌均匀。然后在60℃下继续搅拌0.5小时即得到可生物降解船用发动机润滑油。
对上述各实施例中所得可分解船用发动机润滑油进行性能检测，结果如下表所示。
由上表可知，在满足船用油的常规指标的前提下，本发明船用发动机润滑油生物降解性可达84.3％～95.5％，远优于市场上船用油的生物降解性。

Claims (10)

1.一种润滑油，由复合基础油、复合添加剂及其他添加剂组成，按质量分数计算，各组成及质量份数如下：
复合基础油50～95份
复合添加剂5～25份
其他添加剂0.01～1份。
2.根据权利要求1所述的润滑油，其特征在于：所述复合基础油由合成型基础油和矿物型基础油组成。
3.根据权利要求2所述的润滑油，其特征在于：合成型基础油与矿物型基础油的质量比为0.3-1：2-7。
4.根据权利要求2或3所述的润滑油，其特征在于：
所述合成型基础油为下述一种或几种的混合物：聚α烯烃、合成酯类基础油和改性地沟油；
所述矿物型基础油为Ⅱ类基础油、Ⅲ类基础油、HVI150BS光亮油和环烷基润滑油基础油中的一种或几种。
5.根据权利要求1-4中任一项所述的润滑油，其特征在于：所述复合添加剂由清净分散剂和抗氧剂组成。
6.根据权利要求5所述的润滑油，其特征在于：清净分散剂与抗氧剂的质量比为8-16：0.5-1.5；
所述清净分散剂选自下述至少一种：磺酸盐、硫化烷基酚盐、双丁二酰亚胺和有机物改性的丁二酰亚胺；
所述抗氧剂选自下述至少一种：2,6-二叔丁基对甲酚、二烷基二苯胺、2,6-二叔丁基酚和亚乙基双酚。
7.根据权利要求1-6中任一项所述的润滑油，其特征在于：所述其他添加剂由抗泡剂和破乳剂组成。
8.根据权利要求7所述的船用发动机润滑油，其特征在于：抗泡剂与破乳剂的质量比依次为0.5-1.5：180-220；
所述抗泡剂选自甲基硅油或丙烯酸酯、非硅抗泡剂中的至少一种；
所述破乳剂选自胺与环氧乙烷缩合物或聚醚类高分子化合物中的至少一种。
9.权利要求1-8中任一项所述的润滑油为船用发动机润滑油。
10.权利要求1-8中任一项所述的润滑油在船用发动机中的应用。
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