CN110408454B - 一种改善发动机动力的添加剂 - Google Patents

一种改善发动机动力的添加剂 Download PDF

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CN110408454B
CN110408454B CN201910672668.3A CN201910672668A CN110408454B CN 110408454 B CN110408454 B CN 110408454B CN 201910672668 A CN201910672668 A CN 201910672668A CN 110408454 B CN110408454 B CN 110408454B
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CN110408454A (zh
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钟亮
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Tianjin Sinopec Yuetai Technology Co ltd
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Abstract

本发明提供一种改善发动机动力的添加剂，以重量计，包括复配摩擦改进剂5‑15份，分散剂5‑10份，粘度调节剂1‑8份，抗氧剂5‑15份，表面活性剂2‑20份，其他0‑30份。本发明的添加剂在有效发挥耐磨抗磨作用的同时，还能够改善发动机的动力，提高燃油的燃烧效率。

Description

一种改善发动机动力的添加剂
技术领域
本发明涉及汽油添加剂技术领域，具体涉及一种在发挥摩擦润滑作用的同时能够改善发动机动力的添加剂。
背景技术
汽车发动机中90％以上的问题来源于磨损，改善摩擦磨损危害的添加剂是发动机添加剂的重要作用之一，也是添加剂研究开发的重要课题和方向，采用具有抗磨减磨作用的添加剂能够有效提高发动机的安全性、稳定性、耐久性和热安定性等性能。
改善摩擦的关键在于提高摩擦面或接触点之间的润滑，添加剂中采用的摩擦改进剂是调整润滑的主要物质，他们通常通过两种途径来发挥作用：一是通过表面基团的吸附、沉积等作用在金属表面形成润滑油膜，隔绝金属间的摩擦，二是通过化学渗透或表面化学反应在金属表面形成表面渗透层或表面保护膜层，以提高金属表面的耐磨性。这两条途径可能单独发挥作用，也可能协同进行，同时，这些吸附、沉积、反应、渗透等作用的发挥还受到众多复杂因素的影响，诸如金属表面情况、粘度、温度、转速、杂质、浓度等，因此添加剂润滑减磨效果也在实际应用中存在各类问题，也具有较大差异。
近年来随着对发动机性能要求的提高，对含有摩擦改进剂的添加剂种类也朝向多元化发展，按照摩擦改进剂的元素组成，大体分为以下几个类别：一是含硫、磷类化合物，这类化合物由于具有良好的极压抗磨作用而被广泛应用，但随着环保要求的提高，不含硫磷类添加剂的开发已经成为必然趋势；二是有机钼、铜等硫磷类有机化合物，这类化合物由于同时具有良好的抗氧化性能，在具有环保要求的汽油中具有广泛的应用，但由于其中含有易于沉积的金属元素，容易在发动机内形成积碳或附着物，对发动机的清洁不利；三是无机纳米颗粒，如纳米二氧化铈和二氧化硅等，这类粒子也容易沉积在发动机内部造成清洁困难，并且添加量有限，具有与基础油相容性差的难题；还有一些天然环保类化合物如酒石酸类、柠檬酸类、和苹果酸类等或其酯化改性化合物，但这类化合物的高温性能较差，并未在添加剂中得到普遍应用。
无论采用哪种摩擦改进剂，形成良好的摩擦润滑均会带来一定的粘度变化，并且这种粘度变化在发动机动力提升方面有着不利影响，燃油经济性和效率受到制约，例如目前普遍使用的二烷基二硫代磷酸锌(ZDDP)据信对燃料的综合经济效率具有有害影响。
发明内容
本发明的目的在于提供一种改善发动机动力的添加剂，在有效发挥耐磨抗磨作用的同时，还能够改善发动机的动力，提高燃油的燃烧效率。
发动机动力性能与燃油的燃烧性能密切相关，是发动机动力提升的关键因素之一，若添加剂能够提高燃油在发动机内的燃烧效率，则能够获得良好的动力改善效果。燃油通过喷嘴以雾化颗粒的形式进入气缸，点火后进行燃烧，燃烧的充分性受到雾化颗粒的大小和分布的影响，我们希望促使燃油喷雾颗粒向小粒径方向均匀分布，以使发动机将更多的燃烧热转化为输出功率。除了发动机及其喷嘴本身的设计及操作条件之外，燃油本身的性能决定了雾化颗粒的状态，燃油雾化颗粒的分布多受到喷嘴设计的影响，而颗粒尺寸则更多地与燃油粘度、表面张力等性质相关。摩擦改进剂、清净剂等外加剂的加入往往造成粘度不适当的升高以及表面张力增大，不利于雾化颗粒的细化，使得添加剂带来的在其他方面效能的提升难以与动力提升的需求获得平衡。一些添加剂中为提升燃油经济性，会在配方中加入助燃剂，如二茂铁类，但助燃剂一般通过提高燃油的辛烷值来提升动力效果，并且会降低火花塞功能，对发动机排气门、活塞和缸壁均产生损害，影响发动机的使用寿命。本案通过设计添加剂中摩擦改进剂及其他复配外加剂，通过改善燃油雾化颗粒状态有效提升发动机动力，并避免对发动机造成不利影响。
本发明的改善发动机动力的添加剂，以重量计，包括复配摩擦改进剂0.5-1.5份，分散剂5-10份，粘度调节剂1-8份，抗氧剂5-15份，表面活性剂2-20份，其他0-30份；所述复配摩擦改进剂由含氮硼酸酯化醚类抗磨剂、含氮受阻酚类抗磨剂、和硬脂酸表面改性高岭土复配而成；所述分散剂为亚氨基的氢被烷氧基、酰氧基或羟基取代的琥珀亚胺；所述粘度调节剂为氢化-苯乙烯-双烯聚合物；所述抗氧剂为萘胺化合物；所述表面活性剂为低分子线性醇醚。
上述添加剂能够直接应用于汽油，也可以优选的添加到基础溶剂之中制作复合添加剂成品，复合添加剂成品中所述基础溶剂的含量为50％-90％，基础溶剂选自C9-C12的直链烷烃，如正癸烷等。
所述复配摩擦改进剂中，含氮硼酸酯化醚类抗磨剂优选自硼酸酯化醚二胺，醚类抗磨剂防锈性能较佳，胺基团为含氮基团，能够形成较为稳定的分子间氢键，在摩擦界面之间形成较厚的吸附润滑膜，有效降低摩擦系数，经硼酸酯化后有效提高了醚类分子的高温稳定性，使抗磨剂能够良好适应发动机高温工作环境，但硼酸酯化基团易团聚和水解，需要复合其他外加剂改善分散性能。
所述复配摩擦改进剂中，含氮受阻酚类抗磨剂优选自噻二唑受阻酚抗磨剂，例如TH520和BTMT等，受阻酚类抗磨剂具有良好的抗氧效果，能够复配提高硼酸酯化醚类抗磨剂的高温稳定性，含氮基团噻二唑一方面具有良好的极压抗磨效果，有利于改善混合润滑和边界润滑状态，另一方面能够与硼酸酯化醚类抗磨剂中的含氮基团交联复配，提升协同作用。
所述复配摩擦改进剂中，硬脂酸表面改性高岭土为煅烧纳米高岭土经硬脂酸表面改性而得，改性后能够提高高岭土在体系中的相容性和分散性，高岭土为层状硅酸盐结构，具有良好的吸水性、吸附性和粘性，抗极压能力强，能够弥补含氮受阻酚类抗磨剂中含氮基团高剪切作用下抗极压能力的不足，并防止硼酸酯化基团的吸水团聚，高岭土颗粒通过沉积成膜作用改善界面润滑，不会与含氮基团形成竞争吸附的抵触影响，通过层状晶界滑移改善金属表面的微划痕，在磨损表面进行修复和保护，容易形成铺展并具有较高的承载能力，同时硬脂酸的表面改性有利于通过羧基交联反应形成化学反应膜进一步减小摩擦。
所述复配摩擦改进剂中，三个组分的协同复配能够提升摩擦润滑的工况适应能力，通过吸附、沉积、化学反应膜等多种机制，在发动机低速、高速等不同运转环境下发挥广泛平稳的摩擦改进效果。其中硬脂酸表面改性高岭土由于容易造成在发动机内部沉积，因此需要控制其添加比例，含氮硼酸酯化醚类抗磨剂、含氮受阻酚类抗磨剂、和硬脂酸表面改性高岭土三者的质量比优选为(48-60)：(8-10)：(0.1-0.3)。
所述琥珀亚胺类分散剂通过亚胺基团能够与摩擦改进剂中含氮基团良好相容分散，调整外加剂(摩擦改进剂)的分子间力，降低表面张力并细化喷射雾滴颗粒，该类分散剂为无灰分散剂，环境友好且高温耐受能力强，琥珀亚胺分子中亚氨基的氢被烷氧基、酰氧基或羟基取代，如N-羟基-琥珀酰亚胺、N-丙烯酰氧基琥珀亚胺等，具有平衡分散剂极性、调节体系分子间力的效果，改善雾化的同时还具有增氧助燃作用。
所述粘度调节剂为氢化-苯乙烯-双烯聚合物一般为典型的氢化-苯乙烯-丁二烯聚合物，优选10％甲苯溶液粘度≤800mpa.s，加氢度≥97％的聚合物。粘度调节剂能够平衡体系喷射雾化时的整体粘度，对聚合物的粘度控制能够有效防止局部粘度过大造成体系雾化颗粒增加的不利影响，避免喷射前粘度过低，同时避免摩擦过程中粘度的局部骤增。但氢化-苯乙烯-双烯聚合物可能导致沉积物和积碳水平增加，除控制添加量外，还需要复配其他外加剂降低沉积物和积碳的生成。
所述抗氧剂萘胺化合物具有较强的沉积物控制力，在低添加量情况下能够克服氢化-苯乙烯-双烯聚合物的不利影响，并与其具有良好的相容性，优选为N-苯基-α(β)-萘胺，是一种受阻酚类抗氧剂，与复配摩擦改进剂中含氮受阻酚类抗磨剂同时具有良好的复配协同作用，加强了体系抗磨和抗氧能力。
所述表面活性剂的分子量不大于1500，优选为乙二醇丁醚，低分子线性醇醚具有极低的表面张力，易于与含氮基团相容，能够使得体系整体的表面张力降低，从而在燃油自喷嘴喷射时，能够形成更为细小的雾化液滴，雾化颗粒的整体尺寸向小粒径方向移动，雾化后的燃油颗粒更易充分燃烧，产生更大的热能转化为功，发动机动力性能得到良好提升。
所述其他组分可以根据需要进行添加，包括防腐剂、防锈剂、破乳剂等。
本发明通过配方组分的选择和控制，在保障添加剂润滑抗磨作用的同时，能够通过细化燃油雾化颗粒有效提升发动机动力和燃油经济性，并避免对发动机的相关结构产生损害，防止沉积物、积碳等的生成，使发动机动力方面的提升与其他方面功效得到良好平衡。本发明添加剂不含金属，不含铅、硫、磷等环境污染物质，能够满足节能环保的普遍要求。
附图说明
构成本发明的一部分的附图用来提供对本发明的进一步理解，本发明的示意性实施例及其说明用于解释本发明，并不构成对本发明的不当限定。在附图中：
图1-2是不同添加剂含量下燃油粒度的分布图。
图3是添加剂在95#汽油中对发动机动力的改善效果图。
图4-5是添加剂分别在高低转速下对燃油经济性的改善效果图。
具体实施方式
为了更好的理解本发明，下面结合具体附图对本发明进行详细描述。
一、油品制备
本发明采用的各组成原料均能够通过市购获得，也可以采用已知的常规制备工艺自行制备获得。本发明的添加剂可以直接与燃油复合使用，也可以与基础油调和后作为添加剂油使用。按照重量比将各组分在15-30℃之间进行调和复配，首先将燃油或基础油进行恒温加热，然后加入分散剂、粘度调节剂和表面活性剂，充分搅拌20-30分钟达到均匀且粘度基本稳定后，再加入复配摩擦改进剂、抗氧剂和其他外加剂，再次充分搅拌20-30分钟，得到混合均匀的油品。与基础油调和后的添加机油在使用时加入燃油中，并以添加剂在燃油中的含量进行计算。制备油品中添加剂的组成在表1中列明。
实验组中添加剂在燃油中的含量以0ppm、500ppm、1000ppm三个规格加入，对照组中添加剂在燃油中的含量为1000ppm。燃油汽油选择通用的中石化92#和95#汽油进行实验。
表1
Figure BDA0002142226840000041
Figure BDA0002142226840000051
二、检测方法
摩擦性能采用SRV高温摩擦磨损试验机进行。冲程1mm，频率25Hz和50Hz每隔20min交替，时间2h，载荷300N，温度120℃。
采用CEC F-20-A-98方法，通过发动机台架试验测试添加不同添加剂的油品的积碳生成情况，发动机型号为ARR-1.6L80KW 4V FSI。
采用表面张力仪(型号:BH19-HARKE-CP)测定添加剂添加前后对油品表面张力的影响。
雾化实验采用PDA测试实验系统进行。试验用喷嘴采用电控顶针式单孔直喷喷嘴，喷嘴出口直径0.16mm。雾化实验过程中，喷嘴喷射脉冲的时间间隔为50ms,每次喷射脉冲时间为5ms。
采用GB18276-2017的方法对添加剂添加前后发动机的动力性能进行评价。另外，在发动机高低两个转速下，对添加剂添加前后燃油经济性进行对比。
三、检测结果
表2显示了添加剂不同汽油中摩擦性能影响。可以看出，在92#和95#汽油中，实验组添加剂均显示出良好的摩擦改作用，并且1000ppm量下相较于500ppm的添加量具有更好的抗磨减磨作用。在对照组中，相较于无添加剂的汽油，显示出一定的摩擦改进效果，但由于体系复配性和相容性略低，因此改进效果略差。其中对照A组效果最差，可能的原因是采用ZDDP代替硬脂酸表面改性煅烧纳米高岭土，因ZDDP也通过表面吸附作用于金属表面，与含氮硼酸酯化醚类抗磨剂和含氮受阻酚类抗磨剂产生竞争吸附，协同作用转化为拮抗作用，影响了复配效果的提升，另外，ZDDP不具有吸水能力，不能协同降低硼酸酯化醚类抗磨剂的水解，也影响到硼酸酯化醚类抗磨剂作用的发挥。
表2
Figure BDA0002142226840000052
Figure BDA0002142226840000061
不同添加剂在两种汽油中的积碳情况如表3所示。可以看出，添加剂的加入对发动机中积碳的形成具有一定的抑制作用。一方面可能由于汽油雾化性能的提升促进了燃烧的充分性，有助于减少积碳形成，另一方面萘胺化合物抗氧剂的加入起到了一定的抗沉积物形成作用，以及分散剂的合理复配减少了凝集颗粒的沉积，使得发动机内沉积物有所降低。
表3
Figure BDA0002142226840000062
添加剂添加前后油品表面张力的大小列于表4。可以看出实验组的添加剂能够有效降低燃油分子间的表面张力，这有助于燃油喷射时的雾化，使得雾化颗粒的直径降低，1000ppm添加量的表面张力相较于500ppm的添加量的降低作用更大。对照组中表面张力降低有限，其中对照A组降低效果基本与实验组相当，是由于除ZDDP外其他与实验组相同的组分也达到了降低分子内聚力的作用，对照B组和对照C组分别因粘度调节剂和分散剂的体系相容性降低，影响到分子间相互作用，表面张力降低有限。
表4
Figure BDA0002142226840000071
不同添加剂含量下燃油粒度的分布情况如图1和2所示。由图可以看出，随着添加剂含量的增加，燃油喷射出的雾化粒径向小尺寸方向集中，雾化颗粒得以有效细化，有助于发动机动力的提升以及燃油经济性的增加。
图3显示了添加剂在95#汽油中添加前后发动机动力的改善情况。可以看出实验组能够显著提升发动机的输出功率，从整体来看，发动机的动力能够提升1.2％-1.5％以上。
图4-5显示了添加剂分别在高低转速下对燃油经济性的影响。可以看出实验组能够有效降低在高低转速下发动机的燃油消耗率，平均节油率约为2.8％，而对照组对燃油消耗率的影响不明显。
以上所述仅为本发明的较佳实施例而已，并不用以限制本发明，凡在本发明的精神和原则之内，所作的任何修改、等同替换、改进等，均应包含在本发明的保护范围之内。

Claims (10)

1.一种改善发动机动力的添加剂，以重量计，包括复配摩擦改进剂0.5-1.5份，分散剂5-10份，粘度调节剂1-8份，抗氧剂5-15份，表面活性剂2-20份，其他0-30份；所述复配摩擦改进剂由含氮硼酸酯化醚类抗磨剂、含氮受阻酚类抗磨剂、和硬脂酸表面改性高岭土复配而成；所述分散剂为亚氨基的氢被烷氧基、酰氧基或羟基取代的琥珀亚胺；所述粘度调节剂为氢化苯乙烯-双烯聚合物；所述抗氧剂为萘胺化合物；所述表面活性剂为低分子线性醇醚。
2.根据权利要求1所述的改善发动机动力的添加剂，其特征在于，所述复配摩擦改进剂中，含氮硼酸酯化醚类抗磨剂为硼酸酯化醚二胺，含氮受阻酚类抗磨剂为噻二唑受阻酚抗磨剂，硬脂酸表面改性高岭土为硬脂酸表面改性煅烧纳米高岭土。
3.根据权利要求1所述的改善发动机动力的添加剂，其特征在于，所述复配摩擦改进剂中，含氮硼酸酯化醚类抗磨剂、含氮受阻酚类抗磨剂、和硬脂酸表面改性高岭土三者的质量比为（48-60）：（8-10）：（0.1-0.3）。
4.根据权利要求1所述的改善发动机动力的添加剂，其特征在于，所述分散剂为N-羟基-琥珀酰亚胺或N-丙烯酰氧基琥珀亚胺。
5.根据权利要求1所述的改善发动机动力的添加剂，其特征在于，所述粘度调节剂为氢化苯乙烯-丁二烯聚合物，10%甲苯溶液粘度≤800mpa·s，加氢度≥97%。
6.根据权利要求1所述的改善发动机动力的添加剂，其特征在于，所述抗氧剂萘胺化合物为N-苯基-α-萘胺或N-苯基-β-萘胺。
7.根据权利要求1所述的改善发动机动力的添加剂，其特征在于，所述表面活性剂的分子量不大于1500。
8.根据权利要求7所述的改善发动机动力的添加剂，其特征在于，所述表面活性剂为乙二醇丁醚。
9.根据权利要求1所述的改善发动机动力的添加剂，其特征在于，所述其他组分包括防腐剂、防锈剂、破乳剂。
10.根据权利要求1所述的改善发动机动力的添加剂，其特征在于，所述添加剂直接应用于汽油，或添加到基础溶剂之中制作复合添加剂成品，所述复合添加剂成品中所述基础溶剂的含量为50%-90%，基础溶剂选自C9-C12的直链烷烃。
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