CN105695056B - 一种低灰分、长寿命、环保城市燃气发动机用油 - Google Patents
一种低灰分、长寿命、环保城市燃气发动机用油 Download PDFInfo
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Abstract
本发明公开了一种低灰分、长寿命、环保城市燃气发动机用油,由下述重量份的原料组成:复配剂5‑20份、聚甲基丙烯酸酯5‑10份、酚酯型无灰抗氧剂0.1‑1份、4,4'‑二辛基二苯胺0.1‑1份、有机钼0.005‑0.02份、抗泡剂0.002‑0.005份、噻二唑0.1‑0.5份、150N基础油15‑25份、500N基础油20‑30份、聚α‑烯烃20‑30份、偏苯三酸酯20‑30份、光亮油20‑30份。本发明优化了油品的组成,采用不同种类的清净剂、无灰分散剂、抗氧剂、基础油等既能够保证在使用中不形成过多的灰分,也能够满足进排气系统的润滑要求,具有持续的中和能力,产生的少量积炭较松软,易于清除,极大地提高活塞清净性,在热氧化条件下,润滑油粘度增长小,减少了硝化倾向,延长了换油周期。
Description
技术领域
本发明涉及发动机润滑油领域,具体涉及一种低灰分、长寿命、环保城市燃气发动机用油。
背景技术
石油能源现在依然是世界各国采用的主要能源,但是燃油发动机的尾气排放造成的大气污染非常的严重,特别是在城市交通拥堵的情况下,停停开开造成了更严重的污染,极端的条件下也是形成雾霾的重要原因之一。大气污染中,50%以上的一氧化碳、氮氧化合物、烃类有机挥发物来自于汽车尾气的排放。与液体燃料相比,气体燃料的优势在于能够大幅度地降低燃料成本,减少汽车尾气排放所造成的污染,被称为清洁燃料。燃气发动机与燃油发动机的主要不同在于燃气发动机在工作时温度更高,容易生成更多的氮氧化合物、润滑油容易硝化,润滑油使用周期变短;气体燃料对发动机的润滑、冷却效果差,导致进排气阀磨损和阀座塌陷;高灰分在活塞顶和气缸内形成的沉积物产生积碳,致使火花塞污染造成提前点火,汽缸壁与活塞环之间的磨损加大;因此要求燃气发动机使用的润滑油比燃油发动机使用的润滑油具有更高的热氧化安定性和清净分散性能。
本发明根据燃气发动机的特点和实际工作环境,通过对燃气发动机油配方的筛选,提供了一种能够解决现有技术出现的不足问题并在热氧化安定性、清净性、抗硝化性、高温润滑性、高温抗氧性、延长换油周期等方面,满足实际使用需要的燃气发动机油。
发明内容
本发明技术路线首先对基础油进行考察,以控制成焦成漆的倾向、抗氧化安定性和热稳定性等高温指标,在基础油确定后,进行筛选主剂,以在清净分散性能方面、灰分控制上得到最佳效果,以确定最终方案。
基础油的选择:燃气发动机的工况,要求基础油高温稳定性、氧化安定性性能优良,为了保证满足使用条件,高、低粘度基础油都各选了一种二类油与一种合成油搭配,相互互补,达到最佳组合。基础油性能见表1。
表1:基础油性能数据表
项目 | 偏苯三酸酯 | 500N | PAO-4 | 150N | 120BS光亮油 |
粘度100℃ | 10.2 | 10.57 | 4.1 | 5.15 | 21 |
粘度指数 | 120 | 95 | 132 | 110 | 91 |
闪点 | 276 | 248 | 227 | 218 | 260 |
倾点 | -35 | -27 | -30 | -19 | -10 |
蒸发损失% | 0.54 | 3.5 | 8.6 | 8.89 | 1.21 |
表2:基础油1-3的配比表 单位:%
基础油 | 基础油1 | 基础油2 | 基础油3 |
150N | 45 | 20 | |
PAO-4 | 45 | 25 | |
500N | 50 | 25 | |
偏苯三酸酯 | 50 | 25 | |
120BS | 5 | 5 | 5 |
表3:基础油1-3氧化安定性数据表
项目 | 基础油1 | 基础油2 | 基础油3 |
旋转氧弹试验/min | 21 | 23 | 25 |
表4:基础油1-3成焦成漆数据表
通过对以上成焦成漆倾向和抗氧化数据的分析,二类油与二种合成油相互搭配使用,在抗氧化和成焦成漆方面,能够取得比较满意的效果。因此确定基础油3为最终选择。
添加剂的选择:市售复合添加剂A、市售复合添加剂B、单剂。
单剂的选择:虽然燃气发动机油没有统一的分类,但是依据燃气发动机油的特性要求,对产品的硫酸盐灰分、碱值和磷含量,特别是燃气中腐蚀气体的存在能够对发动机产生很大的的负面影响。硫酸盐灰分主要来源于清净分散剂,用以保护进排气阀系,中和产生的酸性气体。如果灰分过低,酸性气体会对进排气阀系产生腐蚀和烧蚀,使气门关闭不严,甚至阀座变形;灰分过高,会产生提前点火、活塞环粘环等现象。燃气发动机油的配方应该具有良好的清净分散性,使产生的沉积物不坚硬,易于分散,适当的碱值,以中和酸性气体,适当的硫酸盐灰分,以保护进排气阀系,优异的氧化安定性和热稳定性,以满足高温工作环境的需要。单剂性能见表4。
表5:单剂性能数据表
表6:单剂1-3清净分散剂的组成表 单位:克
将单剂1-3分别以上述配方用量,调制1000克,加温溶解、搅拌均匀后检验。
表7:单剂复配后碱值与硫酸盐灰分数据表
项目 | 复配剂1 | 复配剂2 | 复配剂3 |
总碱値mgKOH/g-1 | 6.7 | 6.5 | 5.1 |
硫酸盐灰分% | 0.78 | 0.67 | 0.54 |
表8:单剂1-3成焦成漆试验数据表
通过以上数据我们发现,采用不同高碱值的钙盐与中碱值的钙盐复配,样品的硫酸盐灰分高、碱值大、形成的积碳坚硬;采用中碱值钙盐与中低碱值镁盐复配,硫酸盐灰分适中、碱值符合要求、形成的积碳较松软,易于清除,符合燃气发动机对碱值与硫酸盐灰分的要求,因此复配剂1为最终选择。
表9:复配剂与市售复合剂对比
表10:复配单剂与复合剂A、B碱值与硫酸盐灰分数据表
项目 | 复配单剂 | 复合剂A | 复合剂B |
总碱値mgKOH/g-1 | 5.1 | 5.89 | 7.21 |
硫酸盐灰分% | 0.54 | 0.65 | 0.83 |
表11:复配单剂与复合剂A、B成焦成漆试验数据表
通过以上数据可以看出,复合剂在加入量大于单剂的情况下,与单剂指标相当,从产品质量和经济性上考虑,选用单剂。
本发明目的是通过如下技术方案实现的:
一种低灰分、长寿命、环保城市燃气发动机用油,由下述重量份的原料组成:复配剂5-20份、聚甲基丙烯酸酯5-10份、酚酯型无灰抗氧剂0.1-1份、4,4'-二辛基二苯胺0.1-1份、有机钼0.005-0.02份、抗泡剂0.002-0.005份、噻二唑0.1-0.5份、150N基础油15-25份、500N基础油20-30份、聚α-烯烃20-30份、偏苯三酸酯20-30份、光亮油20-30份。
优选地,所述的复配剂由下述质量百分比的原料组成:中碱値环烷酸镁10-15%、低碱値环烷酸镁10-15%、聚异丁烯丁二酰亚胺25-35%、环烷酸酯10-15%、余量为中碱值水杨酸钙。
优选地,所述的复配剂由下述质量百分比的原料组成:烷基苯磺酸钙20-40%、硫化烷基酚钙20-40%,余量为硼化聚异丁烯丁二酰亚胺。
优选地,所述的聚甲基丙烯酸酯可以为聚甲基丙烯酸酯(10C)、聚甲基丙烯酸酯(12C),也可以采用专利申请号:201410753667.9中实施例1的方法制备聚甲基丙烯酸酯。
优选地,所述的酚酯型无灰抗氧剂为硫代二乙撑双[3-(3,5-二叔丁基-4-羟基苯基)丙酸酯]和/或己二醇双[3-(3,5-二叔丁基-4-羟基苯基)丙酸酯]。
更优选地,所述的酚酯型无灰抗氧剂由40-60wt%硫代二乙撑双[3-(3,5-二叔丁基-4-羟基苯基)丙酸酯]和40-60wt%己二醇双[3-(3,5-二叔丁基-4-羟基苯基)丙酸酯]组成。
优选地,所述的有机钼为二异辛基二硫代氨基甲酸钼、N,N-二(2-乙基己基)二硫代三环氨基甲酸钼、N,N-二(2-乙基己基)二硫代氨基甲酸钼、N-环己基N-十三烷基二硫代氨基甲酸钼、N,N-二(十二)烷基二硫代氨基甲酸钼、N,N-二烷(芳基)二硫代氨基甲酸钼、N-苄基N-辛基二硫代氨基甲酸钼、N-辛基N-十八烷基硫代氨基甲酸钼中的一种或几种混合物。
优选地,所述的抗泡剂为硅油;更优选地,所述硅油为二甲基硅油,可以采用市售的道康宁硅油PMX-200抗泡剂。
优选地,所述的聚α-烯烃,可采用专利申请号:02817015.6中实施例1的方法制备,也可以采用市售的PAO4和/或PAO8的聚α烯烃基础油。
优选地,所述的偏苯三酸酯为偏苯三酸三壬酯、三异癸醇偏苯三酸酯、十三烷醇偏苯三酸酯、偏苯三酸三-正丁基酯、偏苯三酸三正己酯、偏苯三酸三辛酯中一种或多种的混合物。
优选地,所述的光亮油为120BS光亮油和/或150BS光亮油。
优选地,一种低灰分、长寿命、环保城市燃气发动机用油,由下述重量份的原料组成:硼化聚异丁烯丁二酰亚胺4-6份、烷基苯磺酸钙3-5份、硫化烷基酚钙3-5份、聚甲基丙烯酸酯6-8份、4,4'-二辛基二苯胺0.3-0.5份、硫代二乙撑双[3-(3,5-二叔丁基-4-羟基苯基)丙酸酯]0.3-0.5份、己二醇双[3-(3,5-二叔丁基-4-羟基苯基)丙酸酯]0.3-0.5份、N,N-二(十二)烷基二硫代氨基甲酸钼0.005-0.015份、二甲基硅油0.002-0.005份、聚α-烯烃20-30份、噻二唑0.1-0.3份、150N基础油15-25份、偏苯三酸三壬酯20-30份、150BS光亮油3-7份、500N基础油20-30份。
本发明的有益效果是,优化了油品的组成,采用不同种类的清净剂、无灰分散剂、抗氧剂、基础油等既能够保证在使用中不形成过多的灰分,也能够满足进排气系统的润滑要求,具有持续的中和能力,产生的少量积炭较松软,易于清除,极大地提高活塞清净性,有效地控制低温油泥的形成,减少在发动机活塞上部和活塞第一、第二环槽上积碳的形成,保护机件表面的光滑;抑制酸性物质的产生,在热氧化条件下,润滑油粘度增长小,减少了硝化倾向,延长了换油周期。
具体实施方式
下面结合实施例对本发明做进一步的说明,以下所述,仅是对本发明的较佳实施例而已,并非对本发明做其他形式的限制,任何熟悉本专业的技术人员可能利用上述揭示的技术内容加以变更为同等变化的等效实施例。凡是未脱离本发明方案内容,依据本发明的技术实质对以下实施例所做的任何简单修改或等同变化,均落在本发明的保护范围内。
实施例4-6中各原料介绍:
硼化聚异丁烯丁二酰亚胺,合成方法参照万烈雄,冯洁泳,骆新平《硼化无灰分散剂的研制及应用》,润滑油,2001,其结构式如下:
其中,R为分子量为1000的聚异丁烯,R'=H。
烷基苯磺酸钙采用专利申请号:200810011923.1中实施例1的方法制备。
硫化烷基酚钙采用专利申请号:201210389112.1中实施例1的方法制备。
聚甲基丙烯酸酯,采用专利申请号:201410753667.9中实施例1的方法制备聚甲基丙烯酸酯。
4,4'-二辛基二苯胺,CAS号:101-67-7。
硫代二乙撑双[3-(3,5-二叔丁基-4-羟基苯基)丙酸酯],CAS号:41484-35-9。
己二醇双[3-(3,5-二叔丁基-4-羟基苯基)丙酸酯],CAS号:35074-77-2。
有机钼采用N,N-二(十二)烷基二硫代氨基甲酸钼,其结构式如下:其结构式如下:
其中R为直链十二烷基。
抗泡剂采用二甲基硅油,CAS号,63148-62-9。
聚α-烯烃,采用专利申请号:02817015.6中实施例1的方法制备。
噻二唑,CAS号:289-06-5
150N基础油,采用苏州禾森特种油品有限公司提供的150N基础油,,其理化指标如下:运动粘度(40℃)32.6mm2/s,运动粘度(100℃)5.66mm2/s,闪点(开口)238℃,倾点-30℃。
偏苯三酸酯采用偏苯三酸三壬酯,CAS号:35415-27-1。
光亮油采用150BS光亮油,采用苏州赛帕汉特种油品有限公司提供的500N基础油,其理化指标如下:运动粘度(40℃)565.3mm2/s,运动粘度(100℃)31.40mm2/s,闪点(开口)290.2℃,倾点-20℃。
500N基础油,采用苏州赛帕汉特种油品有限公司提供的500N基础油,其理化指标如下:运动粘度(40℃)96.66mm2/s,运动粘度(100℃)10.93mm2/s,闪点(开口)252.1℃,倾点-28℃。
实施例1-3
按表12中的原料配比,并按下述方法制备低灰分、长寿命、环保城市燃气发动机用油。
将基础油按比例混合均匀。将混合均匀的基础油的50%加入釜内,搅拌升温至50℃,加入聚甲基丙烯酸酯(12C),搅拌0.5h;将聚甲基丙烯酸酯(10C)用10%的混合基础油稀释后加入釜内,搅拌升温至50℃,搅拌1.5h;将中碱值水杨酸钙、中碱値环烷酸镁、低碱値环烷酸镁、高分子量聚异丁烯丁二酰亚胺、环烷酸酯,用10%混合基础油稀释后加入釜内,升温至65℃,通过搅拌和静态混合器进行充分的混合,时间1.5h;加入酚酯型无灰抗氧剂、4,4'-二辛基二苯胺、噻二唑,通过搅拌和静态混合器进行充分的混合,时间0.5h;以上过程均在0.1MPa氮气保护下进行,放掉氮气,在-0.06MPa的条件下脱气0.1h;加入30%混合基础油,温度降至45℃,放掉负压,加入有机钼、复合抗泡剂,通过搅拌和静态混合器进行充分的混合,时间0.5h;通过5μm的过滤器放出。
表12:实施例1-3原料配比表 单位:重量份
原料组成 | 实施例1 | 实施例2 | 实施例3 |
中碱值水杨酸钙 | 3 | 4 | 4.5 |
中碱値环烷酸镁 | 3 | 1.5 | 1.5 |
低碱値环烷酸镁 | 1 | 1.5 | 2 |
高分子量聚异丁烯丁二酰亚胺 | 4 | 3.5 | 3 |
环烷酸酯 | 2 | 1.5 | 1 |
聚甲基丙烯酸酯(10C) | 7.5 | 6.5 | 7 |
聚甲基丙烯酸酯(12C) | 1.0 | 0.8 | 0.6 |
酚酯型无灰抗氧剂 | 0.7 | 0.5 | 0.3 |
4,4'-二辛基二苯胺 | 0.7 | 0.5 | 0.3 |
有机钼 | 0.03 | 0.01 | 0.005 |
复合抗泡剂 | 40ppm | 40ppm | 40ppm |
噻二唑 | 0.2 | 0.2 | 0.2 |
混合基础油 | 100 | 100 | 100 |
实施例4
低灰分、长寿命、环保城市燃气发动机用油原料(重量份):烷基苯磺酸钙3.6份、硫化烷基酚钙3.6份,硼化聚异丁烯丁二酰亚胺4.8份、聚甲基丙烯酸酯7份、酚酯型无灰抗氧剂0.8份、4,4'-二辛基二苯胺0.4份;N,N-二(十二)烷基二硫代氨基甲酸钼0.01份;二甲基硅油0.003份;噻二唑0.2份;150N基础油20份、500N基础油25份、聚α-烯烃25份、偏苯三酸三壬酯25份、150BS光亮油5份。
所述的酚酯型无灰抗氧剂由50wt%硫代二乙撑双[3-(3,5-二叔丁基-4-羟基苯基)丙酸酯]和50wt%己二醇双[3-(3,5-二叔丁基-4-羟基苯基)丙酸酯]搅拌混合均匀得到。
低灰分、长寿命、环保城市燃气发动机用油制备:将150N基础油、500N基础油、聚α-烯烃、偏苯三酸三壬酯、150BS光亮油400转/分搅拌混合均匀,得到混合基础油;将混合基础油总重量二分之一的混合基础油(即混合基础油总重量的一半)加入调和釜中,400转/分搅拌,并升温至50℃,加入聚甲基丙烯酸酯,400转/分搅拌0.5h;将烷基苯磺酸钙、硫化烷基酚钙,硼化聚异丁烯丁二酰亚胺加入调和釜中,升温至65℃,400转/分搅拌1.5h;加入酚酯型无灰抗氧剂、4,4'-二辛基二苯胺、噻二唑,400转/分搅拌0.5h;以上过程均在0.1MPa氮气保护下进行,放掉氮气,在-0.06MPa的条件下脱气0.1h;加入剩余二分之一混合基础油,温度降至45℃,放掉负压,加入N,N-二(十二)烷基二硫代氨基甲酸钼、二甲基硅油,400转/分搅拌0.5h;通过5μm的过滤器放出。得到实施例4的低灰分、长寿命、环保城市燃气发动机用油。
实施例5
按实施例4的方法制备低灰分、长寿命、环保城市燃气发动机用油,区别仅仅在于:所述的酚酯型无灰抗氧剂仅为硫代二乙撑双[3-(3,5-二叔丁基-4-羟基苯基)丙酸酯]。得到实施例5的低灰分、长寿命、环保城市燃气发动机用油。
实施例6
按实施例4的方法制备低灰分、长寿命、环保城市燃气发动机用油,区别仅仅在于:所述的酚酯型无灰抗氧剂仅为己二醇双[3-(3,5-二叔丁基-4-羟基苯基)丙酸酯]。得到实施例6的低灰分、长寿命、环保城市燃气发动机用油。
测试例1
对实施例1-3制备的低灰分、长寿命、环保城市燃气发动机用油进行性能测试,结果见表13。
表13:实施例1-3理化分析数据表
测试例2
对实施例1-6制备的低灰分、长寿命、环保城市燃气发动机用油进行成焦成漆清净性能测试,测试参数:曲轴箱试验板温310℃、油温150℃时间为6h,具体结果见表14。
表14:实施例1-6成焦成漆数据表
项目 | 评级 | 焦重/mg |
实施例1 | 2.5 | 28.9 |
实施例2 | 2.5 | 21.5 |
实施例3 | 3.0 | 25.2 |
实施例4 | 2.0 | 20.6 |
实施例5 | 3.0 | 27.4 |
实施例6 | 3.5 | 35.6 |
比较实施例4与实施例5-6,实施例4(硫代二乙撑双[3-(3,5-二叔丁基-4-羟基苯基)丙酸酯]和己二醇双[3-(3,5-二叔丁基-4-羟基苯基)丙酸酯]复配)成焦成漆清净性能明显优于实施例5-6(硫代二乙撑双[3-(3,5-二叔丁基-4-羟基苯基)丙酸酯]和己二醇双[3-(3,5-二叔丁基-4-羟基苯基)丙酸酯]中单一原料)。
测试例3
对实施例1-6制备的低灰分、长寿命、环保城市燃气发动机用油进行氧化安定性测试,实验根据SH/T 0193-2008润滑油氧化安定性的测定-旋转氧弹法检测,氧化时间越长则抗氧性越好。具体结果见表15。
表15:实施例1-6氧化安定性数据表
项目 | 旋转氧弹试验/min |
实施例1 | 271 |
实施例2 | 260 |
实施例3 | 265 |
实施例4 | 285 |
实施例5 | 260 |
实施例6 | 255 |
比较实施例4与实施例5-6,实施例4(硫代二乙撑双[3-(3,5-二叔丁基-4-羟基苯基)丙酸酯]和己二醇双[3-(3,5-二叔丁基-4-羟基苯基)丙酸酯]复配)抗氧性能明显优于实施例5-6(硫代二乙撑双[3-(3,5-二叔丁基-4-羟基苯基)丙酸酯]和己二醇双[3-(3,5-二叔丁基-4-羟基苯基)丙酸酯]中单一原料)。
Claims (4)
1.一种低灰分、长寿命、环保城市燃气发动机用油,其特征在于,由下述重量份的原料组成:复配剂5-20份、聚甲基丙烯酸酯5-10份、酚酯型无灰抗氧剂0.1-1份、4,4'-二辛基二苯胺0.1-1份、有机钼0.005-0.02份、抗泡剂0.002-0.005份、噻二唑0.1-0.5份、150N基础油15-25份、500N基础油20-30份、聚α-烯烃20-30份、偏苯三酸酯20-30份、光亮油20-30份;所述的复配剂由下述质量百分比的原料组成:中碱値环烷酸镁10-15%、低碱値环烷酸镁10-15%、聚异丁烯丁二酰亚胺25-35%、环烷酸酯10-15%、余量为中碱值水杨酸钙,所述的光亮油为120BS光亮油。
2.如权利要求1所述的低灰分、长寿命、环保城市燃气发动机用油,其特征在于,所述的酚酯型无灰抗氧剂为硫代二乙撑双[3-(3,5-二叔丁基-4-羟基苯基)丙酸酯]和/或己二醇双[3-(3,5-二叔丁基-4-羟基苯基)丙酸酯]。
3.如权利要求2所述的低灰分、长寿命、环保城市燃气发动机用油,其特征在于,所述的酚酯型无灰抗氧剂由40-60wt%硫代二乙撑双[3-(3,5-二叔丁基-4-羟基苯基)丙酸酯]和40-60wt%己二醇双[3-(3,5-二叔丁基-4-羟基苯基)丙酸酯]组成。
4.如权利要求1所述的低灰分、长寿命、环保城市燃气发动机用油,其特征在于,所述的有机钼为二异辛基二硫代氨基甲酸钼、N,N-二(2-乙基己基)二硫代三环氨基甲酸钼、N,N-二(2-乙基己基)二硫代氨基甲酸钼、N-环己基N-十三烷基二硫代氨基甲酸钼、N,N-二(十二)烷基二硫代氨基甲酸钼、N,N-二烷(芳基)二硫代氨基甲酸钼、N-苄基N-辛基二硫代氨基甲酸钼、N-辛基N-十八烷基硫代氨基甲酸钼中的一种或几种混合物。
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CN101395256A (zh) * | 2006-03-22 | 2009-03-25 | 新日本石油株式会社 | 低灰分机油组合物 |
CN102971406A (zh) * | 2010-04-12 | 2013-03-13 | 卢布里佐尔公司 | 食品级压缩机润滑剂 |
CN102041141A (zh) * | 2010-05-05 | 2011-05-04 | 无锡惠源包装有限公司 | 一种燃气汽车发动机油复合添加剂及发动机油 |
CN102690709A (zh) * | 2011-03-24 | 2012-09-26 | 中国石油化工股份有限公司 | 一种燃气发动机润滑油组合物 |
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