CN105695007B - 一种含摩擦改进剂节省燃油的汽油清净剂及其制备方法 - Google Patents

一种含摩擦改进剂节省燃油的汽油清净剂及其制备方法 Download PDF

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CN105695007B
CN105695007B CN201610109327.1A CN201610109327A CN105695007B CN 105695007 B CN105695007 B CN 105695007B CN 201610109327 A CN201610109327 A CN 201610109327A CN 105695007 B CN105695007 B CN 105695007B
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friction improver
fuel oil
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赫常山
王宜献
肖颖
蔡德华
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Beijing Refined Scholar's Clariant Petrochemical Complex Co Ltd
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Abstract

本发明公开了一种含摩擦改进剂节省燃油的汽油清净剂及其制备方法，所述含摩擦改进剂节省燃油的汽油清净剂由下述质量百分比的原料组成：清净剂20‑70％、分散剂5‑15％、辛烷值提高剂5‑15％、摩擦改进剂2.5‑7.5％、抗氧剂0.1‑0.8％、防锈剂0.1‑4.5％、破乳剂0.01‑1％、稀释剂10‑50％、余量为载体油。本发明除在喷油嘴、进排气阀和燃烧室等部位具有高效清净性能，还具备对喷油嘴、活塞上部和活塞一环、二环有良好的润滑性能和节省燃油的功效。

Description

一种含摩擦改进剂节省燃油的汽油清净剂及其制备方法
技术领域
本发明涉及一种燃油添加剂，具体涉及一种含摩擦改进剂节省燃油的汽油清净剂及其制备方法。
背景技术
汽油添加剂是为了弥补汽油在某些性质上的缺陷和赋予汽油一些新的优良特性而在汽油中重新加入的功能性物质，由多种有机分子、抗氧、防腐等多种材料组成，具有提升动力、清除积炭、清洁油路、节省燃油、防锈等多种功效。
汽车发动机运转时，喷油嘴温度在100℃左右，进气阀温度在200-300℃之间。在这样的温度下，汽油中的不稳定成份，极易产生氧化缩合反应，生成胶质和积碳，沉积在喷油嘴、进气阀、活塞顶部燃烧室壁上，尤其是高增压发动机和使用燃油直喷技术的发动机更容易产生积碳，而处于发动机活塞上部以及接近顶部的活塞环，由于润滑条件恶劣，得不到良好的润滑，使摩擦磨损增大；作为燃料的汽油，不但要具备好的燃烧性能，还应具有一定的润滑性能，以便对需要润滑的活塞顶部和活塞一环、二环提供润滑，借助燃油对发动机内部提供润滑是一种新的方法和手段，它要求此种物质在提供必要的润滑的同时还能够安全的燃烧而不影响发动机正常运行。把脂肪酸酯等类物质添加于汽油中，能够起到这种作用。
本发明根据现在车用汽油高环保的质量要求和汽油在发动机燃烧工作中出现的胶质、积碳以及活塞上部和活塞环润滑条件恶劣等问题，提供了一种既能保持整个燃油油路及喷油嘴、进排气阀、燃烧室清洁，又对活塞上部、活塞一环、二环、喷油嘴提供润滑保护的复合汽油添加剂。
发明内容
本发明一种含摩擦改进剂节省燃油的汽油清净剂，其含有摩擦改进剂、抗氧剂、防锈剂、破乳剂、清净剂等多种添加剂，是一种多功能复合燃油添加剂，因此各添加剂之间需要充分地溶解分散，使得调配的产品在储存和使用的过程中一直处于稳定的状态，因此还要加入一定量的溶剂油和载体油确保分散均匀，获得稳定的体系。
为实现上述目的，本发明采用下述技术方案
一种含摩擦改进剂节省燃油的汽油清净剂，由下述质量百分比的原料组成：清净剂20-70％、分散剂5-15％、辛烷值提高剂5-15％、摩擦改进剂2.5-7.5％、抗氧剂0.1-0.8％、防锈剂0.1-4.5％、破乳剂0.01-1％、稀释剂10-50％、余量为载体油。
优选地，所述的清净剂为曼尼希碱、聚醚胺中的一种或其混合物。
优选地，所述的分散剂为聚异丁烯基丁二酰亚胺或硼化聚异丁烯丁二酰亚胺。
优选地，所述的辛烷值提高剂为乙基叔丁基醚。
优选地，所述的摩擦改进剂可以为N,N-二(十二)烷基二硫代氨基甲酸钼，也可以采用市售的路博润Powerzol9525A。
优选地，所述的抗氧剂为4,4'-二辛基二苯胺和/或4,4'-二甲基二苯胺。
更优选地，所述的抗氧剂由40-60wt％4,4'-二辛基二苯胺和40-60wt％4,4'-二甲基二苯胺组成。
优选地，所述的防锈剂为十二烯基丁二酸半酯或十二烯基丁二酸。
优选地，所述的破乳剂为二甲基硅油或聚醚类破乳剂DL32。
优选地，所述的稀释剂可以为环保脱芳烃溶剂，也可以为碳酸二甲酯。
优选地，所述的载体油为聚烷撑二醇或壬二酸二(2-乙基己基)酯，聚烷撑二醇可以采用陶氏化学OSP68。
优选地，一种含摩擦改进剂节省燃油的汽油清净剂，由下述质量百分比的原料组成：曼尼希碱25-55％、硼化聚异丁烯丁二酰亚胺3-10％、乙基叔丁基醚6-10％、N,N-二(十二)烷基二硫代氨基甲酸钼3-5.5％、抗氧剂0.3-0.5％、十二烯基丁二酸1.5-3％、二甲基硅油0.05-0.2％、碳酸二甲酯10-20％、余量为壬二酸二(2-乙基己基)酯；
所述的抗氧剂由40-60wt％4,4'-二辛基二苯胺和40-60wt％4,4'-二甲基二苯胺组成。
本发明还提供了上述含摩擦改进剂节省燃油的汽油清净剂的制备方法，包括以下步骤
(1)将载体油、稀释剂、清净剂、分散剂依次加入反应釜中边搅拌边加热至55±5℃，搅拌0.5h混合均匀；
(2)加入摩擦改进剂、抗氧剂、防锈剂、破乳剂，保温搅拌0.5h混合均匀；
(3)降温至40℃，加入辛烷值提高剂，搅拌1小时，经5μm过滤器过滤后放出即得产品。
本发明添加剂各组分之间、主剂和各组分之间均不起化学反应，化学、物理性质稳定，储存方便。
本发明添加剂的应用是将添加剂按1000-2000ppm加入到汽油中稍加搅拌即可，亦可在汽车加油前按比例直接加入汽车燃油箱内再加注燃油则自然冲击混合均匀使用。
本发明添加剂中以特定结构的曼尼希碱为主剂，优选各组成原料，使燃油系统整个油路、喷油嘴和进气阀等温度相对低的部位清洁，同时使燃烧室、排气阀、活塞头部和缸套上部等高温区域保持清洁而没有任何沉积物产生。本发明添加剂与以往的汽油清净剂技术相比较，除在喷油嘴、进排气阀和燃烧室等部位具有高效清净性能，还具备对喷油嘴、活塞上部和活塞一环、二环有良好的润滑性能和节省燃油的功效。
附图说明
为了更清楚地说明本发明实施例或现有技术中的技术方案，下面将对实施例或现有技术描述中所需要使用的附图作简单地介绍，显而易见地，下面描述中的附图仅仅是本发明的一些实施例，对于本领域普通技术人员来讲，在不付出创造性劳动的前提下，还可以根据这些附图获得其他的附图。
图1为未使用含摩擦改进剂节省燃油的汽油清净剂拍出的照片；
图2为使用含摩擦改进剂节省燃油的汽油清净剂拍出的照片。
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：
曼尼希碱，合成方法如下：将0.1mol的对叔丁基苯酚与120ml的甲苯加入釜内，加入0.4g的对甲苯磺酸，搅拌均匀，通过加料口加入多烯多胺于釜内，通入氮气，升温至80℃，加入多聚甲醛，继续升温至120-130℃，反应3h，保持此温度，待分水器不再分水后，反应完成后，静置1h，用50-60℃热水将有机层洗涤5次，经滤机过滤后进行减压分离杂质既得曼尼希碱。
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。
乙基叔丁基醚，CAS号：637-92-3。
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。
4,4'-二辛基二苯胺，CAS号：101-67-7。
4,4'-二甲基二苯胺，CAS号：620-93-9。
十二烯基丁二酸，CAS号：29658-97-7。
二甲基硅油，CAS号：63148-62-9。
碳酸二甲酯，CAS号：108481-44-3。
壬二酸二(2-乙基己基)酯，CAS号：103-24-2。
实施例1-4
按表1中原料配比并按下述方法制备含摩擦改进剂节省燃油的汽油清净剂。
(1)将载体油、稀释剂、清净剂、分散剂依次加入反应釜中边搅拌边加热至55℃，搅拌0.5h混合均匀；
(2)加入摩擦改进剂、抗氧剂、防锈剂、破乳剂，保温搅拌0.5h混合均匀；
(3)降温至40℃，加入辛烷值提高剂，搅拌1小时，经5μm过滤器过滤后放出即得产品。
表1：实施例1-4的原料配比表
实施例5
含摩擦改进剂节省燃油的汽油清净剂原料(质量百分比)：曼尼希碱40％、硼化聚异丁烯丁二酰亚胺7％、乙基叔丁基醚8％、N,N-二(十二)烷基二硫代氨基甲酸钼4.5％、抗氧剂0.4％、十二烯基丁二酸2.2％、二甲基硅油0.1％、碳酸二甲酯15％、余量为壬二酸二(2-乙基己基)酯。
所述的抗氧剂由50wt％4,4'-二辛基二苯胺和50wt％4,4'-二甲基二苯胺搅拌混合均匀得到。
含摩擦改进剂节省燃油的汽油清净剂制备：
(1)将壬二酸二(2-乙基己基)酯、碳酸二甲酯、曼尼希碱、硼化聚异丁烯丁二酰亚胺依次加入反应调和釜中加热至55℃，400转/分搅拌0.5h混合均匀；
(2)加入N,N-二(十二)烷基二硫代氨基甲酸钼、抗氧剂、十二烯基丁二酸、二甲基硅油，温度为55℃，400转/分搅拌0.5h混合均匀；
(3)降温至40℃，加入乙基叔丁基醚，400转/分搅拌1小时，经5μm过滤器过滤。得到实施例5的含摩擦改进剂节省燃油的汽油清净剂。
实施例6
按实施例5的方法制备含摩擦改进剂节省燃油的汽油清净剂，区别仅仅在于：所述的抗氧剂仅为4,4'-二辛基二苯胺。得到实施例6的含摩擦改进剂节省燃油的汽油清净剂。
实施例7
按实施例5的方法制备含摩擦改进剂节省燃油的汽油清净剂，区别仅仅在于：所述的抗氧剂仅为4,4'-二甲基二苯胺。得到实施例7的含摩擦改进剂节省燃油的汽油清净剂。
测试例1
将以上实施例1-7制备的含摩擦改进剂节省燃油的汽油清净剂采用不同的实验室模拟试验方法对清净性进行评定。
1、SDT斑点分散试验
将发动机油泥5g与100g500N基础油、150mg各实施例添加剂在150℃下一齐搅拌1小时，然后趁热用2ml的移液管移取少许混合液滴在直径9cm的定性滤纸上，在室温(25℃)下扩散24小时后，测定油泥扩散圈直径与油扩散圈直径的比值，即SDT值，SDT值越大，说明添加剂的分散性能越好，测试数据如下表2。
表2：斑点分散试验结果表
试验油样 SDT值
实施例1 0.58
实施例2 0.61
实施例3 0.56
实施例4 0.67
实施例5 0.69
实施例6 0.66
实施例7 0.64
2、进气阀积碳模拟试验
利用曲轴箱模拟试验仪的加热板将倾斜的铝板加热并恒温在330±10℃，将含300mg实施例1-7制备的含摩擦改进剂节省燃油的汽油清净剂的200g汽油装在底部带流量计的玻璃容器内，以5mg/min的流速连续地滴落在铝板表面上，通过测定铝片上积炭的多少和漆膜颜色来定性地评价汽油清净剂对积炭生成的抑制能力，该方法可有效模拟积炭在进气阀部位产生的倾向。测试数据如下表3。
表3：进气阀积碳模拟试验结果表
两项模拟试验结果显示本发明添加剂对燃油油路、喷油嘴、燃烧室等清洁效果明显，能有效抑制进气阀、燃烧室等积碳的生成，提高燃油燃烧效率。
比较实施例5与实施例6-7，实施例5(4,4'-二辛基二苯胺和4,4'-二甲基二苯胺复配)清净性能明显优于实施例6-7(4,4'-二辛基二苯胺和4,4'-二甲基二苯胺中单一原料)。
测试例2
通过行车试验对本发明添加剂效果进一步进行验证。
行车试验
1、试验设备：工业内窥镜。
2、试验样品配比：汽油添加剂的配比按实施例4中的配比。汽油添加剂与基础汽油的体积比为1：800。
3、试验方法：
使用汽油添加剂前，采用工业内窥镜观察车辆进气阀沉积物，并拍照，结果如图1所示；加入实施例4汽油添加剂正常行驶三箱油后，再采用工业内窥镜观察车辆进气阀沉积物，并拍照，结果如图2所示。通过对比使用汽油添加剂清洗前后的进气阀沉积物照片，定性评价汽油添加剂对燃油系统沉积物的清洗效果。
4、试验结果：
未使用含摩擦改进剂节省燃油的汽油清净剂拍出的照片(见图1)显示：活塞顶部、活塞环、缸壁、进气阀阀座被沉积物覆盖，布满积碳，呈黑色；使用含摩擦改进剂节省燃油的汽油清净剂拍出的照片(见图2)显示：活塞顶部、活塞环、缸壁和进气阀阀杆基本没有沉积物，露出金属光泽，进气阀阀座只残存少量沉积物。通过对比照片发现使用本发明的汽油添加剂，能有效清除燃烧系统中已产生的沉积物，有利于提高燃料的经济性、降低汽车尾气排放、提高车辆驱动性能。
测试例3
对实施例1-3制备的含摩擦改进剂节省燃油的汽油清净剂进行节油效果验证。
为了保证行车试验结果的普遍性，试验使用了两种经常跑相同路段的车型，多次使用本发明添加剂进行试验。
试验车辆：
奥迪A6 1.8T，车龄8年，经常跑北京--唐山往返。
现代悦动1.6L，车龄3年，经常跑北京--天津往返。
数据记录：奥迪A6 1.8T满油箱70L,现代悦动满油箱52L,两台车均不带油耗表，每次出车前将油箱加满，返回后再次将油箱加满，补加油数量即为此次往返烧油升数；
试验使用实施例4配方，仍按1:800配比，每部车共试验了4次，对比油耗为使用本发明添加剂前平均油耗数。
试验统计数据见表4。
表4：节油率测试结果表单位：％
车辆 奥迪A6 现代悦动
实施例1 15.28 13.10
实施例2 15.31 13.13
实施例3 15.16 13.02
实施例4 15.44 13.21
实施例5 15.63 13.38
实施例6 15.36 13.12
实施例7 15.30 13.07
以上模拟试验和行车试验结果说明本发明汽油清净剂优选各组成原料，发挥各自优点，辅以防锈、抗氧化和破乳添加剂，可以有效清洗燃油系统，保持发动机燃油系统清洁；引入可对活塞顶环进行润滑的摩擦改进剂，大大减少了活塞头部和气缸的摩擦阻力，有效节省燃油，提升动力，减少排放。
比较实施例5与实施例6-7，实施例5(4,4'-二辛基二苯胺和4,4'-二甲基二苯胺复配)节油率明显优于实施例6-7(4,4'-二辛基二苯胺和4,4'-二甲基二苯胺中单一原料)。

Claims (4)

1.一种含摩擦改进剂节省燃油的汽油清净剂，其特征在于，由下述质量百分比的原料组成：清净剂20-70％、分散剂5-15％、辛烷值提高剂5-15％、摩擦改进剂2.5-7.5％、抗氧剂0.1-0.8％、防锈剂0.1-4.5％、破乳剂0.01-1％、稀释剂10-50％、余量为载体油；
所述的清净剂为曼尼希碱、聚醚胺中的一种或其混合物；
所述的分散剂为聚异丁烯基丁二酰亚胺或硼化聚异丁烯丁二酰亚胺；
所述的辛烷值提高剂为乙基叔丁基醚；
所述的抗氧剂由40-60wt％4,4'-二辛基二苯胺和40-60wt％4,4'-二甲基二苯胺组成。
2.如权利要求1所述的含摩擦改进剂节省燃油的汽油清净剂，其特征在于，所述的防锈剂为十二烯基丁二酸半酯或十二烯基丁二酸。
3.如权利要求1所述的含摩擦改进剂节省燃油的汽油清净剂，其特征在于，所述的破乳剂为二甲基硅油或聚醚类破乳剂，所述的载体油为聚烷撑二醇或壬二酸二(2-乙基己基)酯。
4.如权利要求1-3中任一项所述的含摩擦改进剂节省燃油的汽油清净剂的制备方法，包括以下步骤：
(1)将载体油、稀释剂、清净剂、分散剂依次加入反应釜中边搅拌边加热至55±5℃，搅拌0.5h混合均匀；
(2)加入摩擦改进剂、抗氧剂、防锈剂、破乳剂，保温搅拌0.5h混合均匀；
(3)降温至40℃，加入辛烷值提高剂，搅拌1小时，经5μm过滤器过滤后放出即得产品。
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