CN111944591B - 一种萘胺抗氧剂的燃气机润滑油及其制备方法 - Google Patents
一种萘胺抗氧剂的燃气机润滑油及其制备方法 Download PDFInfo
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Abstract
本发明公开了一种萘胺抗氧剂的燃气机润滑油及其制备方法,该萘胺抗氧剂的燃气机润滑油,由下述组分按质量份数计组成:抗氧剂1.5‑2.5份、清净剂1‑6份、抗磨剂0.2‑3份、分散剂1‑12份、粘指剂0.1‑17份、降凝剂0.01‑4份、消泡剂0.003‑0.004份、基础油75.3‑83.7份;其中,所述抗氧剂为萘胺与二烷基二硫代磷酸锌按质量份数比(0.5~2):(1~1.5)混合而成;所述清净剂为磺酸钙与磺酸镁按质量份数比(0.5~4):(0.5~2)混合而成。本发明的萘胺抗氧剂的燃气机润滑油提升了油品高温抗氧化性能,使油品具有更长的使用寿命,从而延长燃气机油换油里程。
Description
技术领域
本发明属于燃气机润滑油的技术领域,具体涉及一种萘胺抗氧剂的燃气机润滑油及其制备方法。
背景技术
大多数重负荷燃气发动机是基于柴油发动机改造成火花塞点燃式,燃气机相比柴油机燃烧温度更高,更苛刻的氧化作用导致油泥和粘度增加,要求燃气机油比柴机油抗氧性能更好;燃气没有重组分,因此燃气机没有烟炱生成;燃气更干,而润滑油灰分能够减少阀系磨损,但是灰分的沉积物会导致早燃,因此必须优化灰分限值。燃气机油与柴油机油各项性能对比见表1。
表1燃气机油与柴油机油各项性能对比
油品性能 | 柴油机油 | 燃气机油 |
分散性(烟炱) | ++ | + |
抗磨性 | ++ | ++ |
抗氧化 | + | ++ |
清净性(沉积物) | ++ | ++ |
目前市场上应用的燃气机油产品主要有柴油机/燃气机通用机油以及燃气机专用机油两类,见表2。
表2燃气机油产品分类
现有技术中,申请号CN201510659138.7名为《一种燃气动力式天然气压缩机润滑油组合物》的发明专利公开了一种由Ⅱ类矿物基础油调和的线型粘指剂燃气机油,采用氨基硫代酯抗氧剂,没有采用萘胺抗氧剂。申请号CN201910066866.5名为《一种长寿命天然气发动机油及其制备方法》的发明专利公开了一种抗氧剂为硫磷仲醇基锌盐和硫磷双辛基碱性锌盐,采用Ⅲ类基础油调和的燃气机油。
燃气机燃烧温度相比柴油机高,所以在高温抗氧化性方面要求比柴油机油要苛刻,导致换油里程很难做到6万公里以上,国内主机厂已应用的燃气机油产品及保养间隔见表3。
表3国内主机厂燃气机油产品
主机厂 | 燃气机型号 | 换油里程/万公里 | 燃气机油规格 |
主机厂1 | MT13、MT07 | 3-5 | MAN3271、MAN3477 |
主机厂2 | X14N | 6 | CES20092 |
主机厂3 | YCK13N、YCK15N | 5 | CES20092 |
主机厂4 | WP13NG、WP10NG | 6 | 无规格 |
由此可知,燃气机油换油里程最长想要超过现有产品达到10万公里,需要在现有的CES20092燃气机油规格基础上进行补强。
发明内容
本发明的目的就是为了解决上述背景技术存在的不足,提供一种萘胺抗氧剂的燃气机润滑油及其制备方法。
为实现上述目的,本发明采用的技术方案是:一种萘胺抗氧剂的燃气机润滑油,由下述组分按质量份数计组成:
其中,所述抗氧剂为萘胺与二烷基二硫代磷酸锌按质量份数比(0.5~2):(1~1.5)混合而成;
所述清净剂为磺酸钙与磺酸镁按质量份数比(0.5~4):(0.5~2)混合而成。
上述技术方案中,所述二烷基二硫代磷酸锌的分子结构式如下:
式中,R=CnH2n+1,n=5-15。
上述技术方案中,磺酸钙的分子结构式如下:
式中,R=CnH2n+1,n=5-15。
上述技术方案中,磺酸镁的分子结构式如下:
式中,R=CnH2n+1,n=5-15。
上述技术方案中,所述抗磨剂选自二烷基二硫代氨基甲酸锌;所述二烷基二硫代氨基甲酸锌的分子结构式如下:
式中,R=CnH2n+1,n=5-15。
上述技术方案中,所述分散剂选自聚异丁烯丁二酰亚胺;所述聚异丁烯丁二酰亚胺的分子结构式如下:
式中,R=CnH2n+1,n=50-100,m=5-10。
上述技术方案中,所述粘指剂选自异戊二烯苯乙烯星型共聚物;所述异戊二烯苯乙烯星型共聚物的分子结构式如下:
式中,m=100-500,n=100-500。
上述技术方案中,所述降凝剂选自聚甲基丙烯酸酯;所述聚甲基丙烯酸酯的分子结构式如下:
式中,R=CnH2n+1,n=10-20。
上述技术方案中,所述消泡剂选自聚二甲基硅油;所述聚二甲基硅油的分子结构式如下:
式中,n=100-200。
上述技术方案中,所述基础油为III类石蜡基合成基础油,具体为由粘度8cSt250N和粘度6cSt 150N两种粘度的III类石蜡基合成基础油组成。
本发明还提供一种上述萘胺抗氧剂的燃气机润滑油的制备方法,包括如下步骤:
1)按照配方比例依次加入分散剂、抗氧剂、清净剂、抗磨剂,最后加入消泡剂持续搅拌,搅拌温度为60-65℃,搅拌时间为1-3h,得到产物a;
2)将基础油加入调和釜中,开始搅拌升温至60-65℃并保持此温度,加入粘指剂、降凝剂,继续搅拌反应,搅拌速度为70-80r/min,搅拌时间为1-3h,得到产物b;
3)最后将产物a加到产物b中,持续搅拌反应,搅拌温度为60-65℃,搅拌时间为1-3h,即可。
最佳实施方式的,所述步骤1)中,搅拌温度为62℃,搅拌时间为2h;所述步骤2)中,搅拌速度为77.5r/min,搅拌时间为2h;所述步骤3)中,搅拌温度为62℃,搅拌时间为2h。
与现有技术相比,具有如下有益效果:
其一,本发明的萘胺抗氧剂的燃气机润滑油根据不同类型抗氧剂的特点酚类:捕捉自由基(带游离电子的小基团),130℃以下性能好;胺类:捕捉自由基,高温150℃以上性能好;ZDDP:分解过氧化物,高温下性能好,但分解产物有沉淀,采用ZDDP(二烷基二硫代磷酸锌)+抗氧化性能更优的萘胺组合,提升油品高温抗氧化性能,ZDDP抗磨性能相比抗氧化性能更为显著,而萘胺在高温下稳定性更好,抗氧作用优于ZDDP。
其二,本发明的萘胺抗氧剂的燃气机润滑油采用磺酸钙与磺酸镁复配清净剂技术,镁盐相对钙盐分子量低(镁相对原子质量24,钙相对原子质量40),单位质量的镁盐能够提供更多的TBN,能够使油品具有更长的使用寿命;另外,镁盐的碱值保持能力相比钙盐要好,相比目前现有市场上主要以磺酸钙为主的清净剂,对于油品使用寿命的保证性更好。
其三,本发明的萘胺抗氧剂的燃气机润滑油通过在满足CumminsCES20092规格产品基础上补加抗氧剂,更换新型清净剂,提升基础油等级,从技术角度延长燃气机油换油里程。目前国内、国外主机厂已发布的燃气机油配方换油里程最长为6万公里,与现有的燃气机油配方相比,本发明的萘胺抗氧剂的燃气机润滑油满足国Ⅵ排放标准,能够显著延长换油里程,能够为用户节省保养时间、费用,同时提升了公司产品的竞争力。
附图说明
图1为实施例2与现有产品的COP氧化试验的测试结果示意图;
图2为实施例2的硝化值、氧化值含量及变化的结果示意图;
图3为实施例2的TAN、TBN含量及变化的结果示意图;
图4为实施例2的KV100变化趋势的结果示意图;
图5为实施例2的磨损元素Fe含量及变化的结果示意图;
具体实施方式
下面结合具体实施例对本发明作进一步的详细说明,便于清楚地了解本发明,但它们不对本发明构成限定。
本发明实施例1-5的萘胺抗氧剂的燃气机润滑油,由下述组分按质量份数计组成,具体配方如表4所示。
表4实施例1-5配方表
本发明的萘胺抗氧剂的燃气机润滑油制备方法包括如下步骤:
1)按照配方比例依次加入分散剂、抗氧剂、清净剂、抗磨剂,最后加入消泡剂持续搅拌,搅拌温度为60-65℃,搅拌时间为1-3h,得到产物a;
2)将基础油加入调和釜中,开始搅拌升温至60-65℃并保持此温度,加入粘指剂、降凝剂,继续搅拌反应,搅拌速度为70-80r/min,搅拌时间为1-3h,得到产物b;
3)最后将产物a加到产物b中,持续搅拌反应,搅拌温度为60-65℃,搅拌时间为1-3h,即可。
效果例1
对上述实施例1-5与对比例进行理化指标测试,测试结果如下表5所示,由表5可知,实施例1~5的各项理化指标均能够满足CES20092标准限值要求;其中,实施例2的低温冷启动粘度、高温高剪切粘度、蒸发损失等指标在实施例中是性能最优的;实施例2与对比例相比,运动粘度略高能够保证油膜厚度,采用钙镁复配清净剂总碱值较高对实现长换油里程有帮助,硫、磷含量控制更严格,能够降低机油对燃气机搭载的三元催化器的影响,灰分较低对燃气机活塞清净性以及缸套-活塞环磨损有利。
表5理化指标测试结果
效果例2
选取效果例1中理化性能最好的实施例2进行下步的台架试验验证。
(1)COP氧化台架试验
通过CES20092 COP氧化台架试验验证,COP氧化试验的测试结果见图1,其中红外峰面积变化发生的时间、红外峰高度变化发生的时间、铅含量变化发生的时间三项指标越大越好,红外峰面积变化率、红外峰高度变化率、铅含量变化率三项指标越小越好,本发明的产品整体结果超越现有的CES20092产品约15-20%。本发明与现有产品(CES20092)COP氧化台架试验数据对比见表6。
表6 COP氧化台架试验数据对比
典型指标 | CES 20092产品 | 实施例2 |
红外峰面积变化发生的时间,Hrs | 230 | 250 |
红外峰高度变化发生的时间,Hrs | 230 | 275 |
铅含量变化发生的时间,Hrs | 230 | 250 |
红外峰面积变化率,Unit/Hrs | 26 | 19 |
红外峰高度变化率,Unit/Hrs | 0.6 | 0.5 |
铅含量变化率,ppm/Hrs | 1.8 | 1.3 |
(2)可靠性台架试验验证:
根据东风可靠性(全速全负荷)台架试验机油监测数据,本发明产品氧化值、硝化值增长整体水平较低,TBN衰减、TAN增加幅度较少,测试结果见图2~图5。从图2~图5的测试结果可以看出,本发明产品能够满足CES20092规格要求,能够通过东风300小时可靠性台架试验考核,而且本专利产品在理化指标、COP氧化试验中的性能表现均优于现有产品。
综上所述,本发明产品为实现长换油里程所采用的抗氧剂在ZDDP基础之上增加抗氧化性能更优的萘胺,从CES20092标准规定的COP氧化试验结果以及东风DGI 13台架试验结果分析,本发明产品在油品抗氧化性方面优于CES20092规格的现有燃气机油产品。采用磺酸钙、磺酸镁复配清净剂技术,镁盐相对钙盐低(镁相对原子质量24,钙相对原子质量40),单位质量的镁盐能够提供更多的TBN,另外镁盐的碱值保持能力相比钙盐要好,从东风DGI 13台架试验过程中TBN、TAN的变化趋势情况也得到了验证,相比目前现有市场上主要以磺酸钙为主的清净剂,对于油品使用寿命的保证性更好。
以上,仅为本发明的具体实施方式,应当指出,其余未详细说明的为现有技术,任何熟悉本领域的技术人员在本发明所揭露的技术范围内,可轻易想到的变化或替换,都应涵盖在本发明的保护范围之内。
Claims (3)
1.一种萘胺抗氧剂的燃气机润滑油,其特征在于:由下述组分按质量份数计组成:
其中,所述抗氧剂为萘胺与二烷基二硫代磷酸锌按质量份数比1.25:1.25混合而成;
所述清净剂为磺酸钙与磺酸镁按质量份数比1.3:0.7混合而成;
所述抗磨剂选自二烷基二硫代氨基甲酸锌;所述二烷基二硫代氨基甲酸锌的分子结构式如下:
式中,R=CnH2n+1,n=5-15;
所述消泡剂选自聚二甲基硅油;所述聚二甲基硅油的分子结构式如下:
式中,n=100-200;
所述二烷基二硫代磷酸锌的分子结构式如下:
式中,R=CnH2n+1,n=5-15;
所述分散剂选自聚异丁烯丁二酰亚胺;所述聚异丁烯丁二酰亚胺的分子结构式如下:
式中,R=CnH2n+1,n=50-100,m=5-10;
所述粘指剂选自异戊二烯苯乙烯星型共聚物;所述异戊二烯苯乙烯星型共聚物的分子结构式如下:
式中,m=100-500,n=100-500;
所述降凝剂选自聚甲基丙烯酸酯;所述聚甲基丙烯酸酯的分子结构式如下:
式中,R=CnH2n+1,n=10-20;
所述基础油为石蜡基合成油,由粘度8cSt 250N和粘度6cSt 150N两种粘度的III类石蜡基合成基础油组成;
所述萘胺抗氧剂的燃气机润滑油由如下方法制备而成:
1)按照配方比例依次加入分散剂、抗氧剂、清净剂、抗磨剂,最后加入消泡剂持续搅拌,搅拌温度为60-65℃,搅拌时间为1-3h,得到产物a;
2)将基础油加入调和釜中,开始搅拌升温至60-65℃并保持此温度,加入粘指剂、降凝剂,继续搅拌反应,搅拌速度为70-80r/min,搅拌时间为1-3h,得到产物b;
3)最后将产物a加到产物b中,持续搅拌反应,搅拌温度为60-65℃,搅拌时间为1-3h,即可;
所述萘胺抗氧剂的燃气机润滑油的粘度等级为10W40,100℃运动粘度为14.83mm2/s,40℃运动粘度为104.5mm2/s,粘度指数为150,在-20℃的低温冷启动粘度为4019mPa.s,在150℃的高温高剪切粘度为4.38mPa.s,蒸发损失NOACK为3.85%,总碱值为8.0mgKOH/g,硫含量为0.29%,磷含量为720mg/kg,硫酸盐灰分为0.75%。
2.一种权利要求1所述萘胺抗氧剂的燃气机润滑油的制备方法,其特征在于:包括如下步骤:
1)按照配方比例依次加入分散剂、抗氧剂、清净剂、抗磨剂,最后加入消泡剂持续搅拌,搅拌温度为60-65℃,搅拌时间为1-3h,得到产物a;
2)将基础油加入调和釜中,开始搅拌升温至60-65℃并保持此温度,加入粘指剂、降凝剂,继续搅拌反应,搅拌速度为70-80r/min,搅拌时间为1-3h,得到产物b;
3)最后将产物a加到产物b中,持续搅拌反应,搅拌温度为60-65℃,搅拌时间为1-3h,即可。
3.根据权利要求2所述的萘胺抗氧剂的燃气机润滑油的制备方法,其特征在于:所述步骤1)中,搅拌温度为62℃,搅拌时间为2h;所述步骤2)中,搅拌速度为77.5r/min,搅拌时间为2h;所述步骤3)中,搅拌温度为62℃,搅拌时间为2h。
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