CN111500328B - 一种甲醇燃料复合添加剂 - Google Patents

一种甲醇燃料复合添加剂 Download PDF

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CN111500328B
CN111500328B CN202010303074.8A CN202010303074A CN111500328B CN 111500328 B CN111500328 B CN 111500328B CN 202010303074 A CN202010303074 A CN 202010303074A CN 111500328 B CN111500328 B CN 111500328B
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李俊华
贺刚
李俊莉
沈燕宾
拓宏兵
王佳
张颖
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Shaanxi Chemical Research Institute Co ltd
Shaanxi Yanchang Petroleum Energy Technology Co ltd
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Abstract

本发明公开了一种甲醇燃料复合添加剂,其由以下质量百分比的原料组成:聚醚胺20%~35%、多胺甲基聚异丁烯苯酚11%~25%、双苯并三氮唑基双咪唑啉席夫碱0.6%~5.0%、2,6‑二叔丁基对甲酚0.1%~3.0%、单油酸甘油酯1.0%~8.0%、油酸二乙醇酰胺硼酸酯0.3%~3.0%、癸二酸二异辛酯0.5%~6.0%、其余为助溶剂。本发明甲醇燃料复合添加剂协同作用良好,在低剂量加入的情况下可有效改善甲醇燃料的清净性能、润滑性能、抗氧化性能、汽车油路系统金属的耐腐蚀性能以及橡胶的溶胀性能,并且制备工艺简单、原料易得、成本适中,环保性能良好。

Description

一种甲醇燃料复合添加剂
技术领域
本发明属于能源化工技术领域,具体涉及一种甲醇燃料复合添加剂。
背景技术
随着石油资源短缺和环境污染的问题日益突出,积极寻求和发展清洁替代能源已成为促进我国经济发展的关键课题。在众多的新能源燃料的开发研究中,甲醇燃料以其优异的性能作为一种新型环保燃料应运而生,是目前世界上可再生能源的发展重点。美国、欧盟、巴西等国家已经大规模使用甲醇燃料。目前,我国有关甲醇的相应的标准有GB/T 23510车用燃料甲醇、GB/T 23799车用甲醇汽油M85和各省相继推出的M15、M25、M30、M50等甲醇汽油地方标准,这些规范的标准体系建立意味着甲醇燃料的使用符合国家新能源政策大政方针;2019年3月,国家八部委61号文件《关于在部分地区开展甲醇汽车应用的指导意见》明确,鼓励推广应用甲醇汽车,甲醇燃料的推广步伐显著加快。
使用甲醇燃料最主要的优点在于:来源广泛,经济效益显著;辛烷值高、动力性好;含氧量高、燃烧充分、排放有害气体量少;燃油系统自洁、使用方便等,是理想的车用汽油替代品。但是甲醇燃料在使用过程中存在冷启动困难、橡胶溶胀、金属的腐蚀、相分离和气阻等问题。为解决上述问题,市场上推出了各类复合添加剂来改善甲醇燃料的使用性能,但其配方成分复杂(有的复合添加剂组分甚至达到20多种)、原料成本高,且产品质量良莠不齐,支撑关键性能的试验数据较少,给产品的使用和推广造成了诸多障碍。
发明内容
本发明的目的是提供一种制备工艺简单、原料易得、成本适中、环保性能良好的甲醇燃料复合添加剂,在低剂量加入的情况下,有效改善甲醇燃料的清净性能、润滑性能、抗氧化性能、汽车油路系统金属的耐腐蚀性能以及橡胶的溶胀性能。
为了达到上述目的,本发明所采用的甲醇燃料复合添加剂由下述质量百分比的原料组成:
Figure GDA0003120223920000021
上述甲醇燃料复合添加剂优选由下述质量百分配比的原料组成:
Figure GDA0003120223920000022
上述的聚醚胺是数均分子量分别为400、1000和2000的D系列产品按质量比为1:2~6:6~11的混合物,优选数均分子量分别为400、1000和2000的D系列产品按质量比为1:3~5:7~9的混合物。
上述双苯并三氮唑基双咪唑啉席夫碱的结构式如下所示:
Figure GDA0003120223920000023
其制备方法为:将4-羧基苯并三氮唑、二亚乙基三胺和硼酸按摩尔比为1:1.05~1.25:0.1~0.5,在180~200℃下加热搅拌反应4~6h,待脱出理论产出水的90%后降温,得苯并三氮唑基咪唑啉;将苯并三氮唑基咪唑啉和N-甲基丁二酰胺按摩尔比为2:1.00~1.15加入异丙醇中,在40℃搅拌条件下缓慢滴加冰醋酸,调节至体系的pH=4~6后,在80~110℃下反应2~4h,冷却至室温,过滤后重结晶得双苯并三氮唑基双咪唑啉席夫碱。
上述的助溶剂优选季戊四醇、乙二醇单丁醚、司盘80质量比为1:5~13:0.5~2.5的混合液,进一步优选季戊四醇、乙二醇单丁醚、司盘80质量比为1:6~10:1~2的混合液。
上述的多胺甲基聚异丁烯苯酚为聚异丁烯基苯酚与甲醛、多胺的缩合物。其中,聚异丁烯基苯酚为聚异丁烯与苯酚在路易斯酸催化作用下的加成产物,所述聚异丁烯的数均分子量为800~2400,优选聚异丁烯的数均分子量为900~1300。
本发明甲醇燃料复合添加剂的制备方法为:将双苯并三氮唑基双咪唑啉席夫碱和2,6-二叔丁基对甲酚加入助溶剂中,在35~40℃下搅拌分散至完全溶解;再依次加入聚醚胺、多胺甲基聚异丁烯苯酚、油酸二乙醇酰胺硼酸酯、单油酸甘油酯和癸二酸二异辛酯,搅拌均匀。
本发明的有益效果如下:
1、本发明的甲醇燃料复合添加剂中的聚醚胺和多胺甲基聚异丁烯苯酚为性能优良的油品清净剂,两者复配使用,可显著提高发动机油路系统的清净功能,其表面的活性成分既可使已产生的积炭松脱、细化,又可被吸附在燃油系统和燃烧室的金属表面,防止积炭生成;聚醚胺按数均分子量的高低进行搭配使用,从而使发动机不论在低负荷状态下,还是在高负荷工作状态下均能保持优良的清净性能,降低发动机油路系统机件的磨损,延长发动机的使用寿命。
2、本发明的甲醇燃料复合添加剂中的双苯并三氮唑基双咪唑啉席夫碱为优异的抗氧化剂和金属减活剂,其结构中的苯并三氮唑基以及亚胺基均能与金属原子形成共价键和配位键,在铜、碳钢、铝等金属表面的吸附能力增强。
3、本发明的甲醇燃料复合添加剂中的油酸二乙醇酰胺硼酸酯分子结构中含有酰胺基、硼酸基以及长碳链的烃基,因此具有显著的润滑和防腐蚀功能,且分散和增溶作用优良,与双苯并三氮唑基双咪唑啉席夫碱配合使用,可获得很好的铜腐蚀抑制效果,与单油酸甘油酯和癸二酸二异辛酯配合使用,抗摩作用增强。
4、本发明的甲醇燃料复合添加剂中的乙二醇单丁醚是优良的溶剂,能以任意比与醇类和水混溶,对石油烃具有高的稀释度,其与季戊四醇和司盘80作为助溶剂复合使用,可促使复合添加剂中各组分充分溶解,以保证产品的稳定性及相应的性能要求。
5、本发明的甲醇燃料复合添加剂各组分之间协同作用良好,原料易得、制备工艺简单、成本适中、燃烧效率高,环保性能良好。
具体实施方式
下面结合实施例对本发明进一步详细说明,但本发明的保护范围不仅限于这些实施例。
实施例1
以制备甲醇燃料复合添加剂1000g为例,其由下述原料组成:
Figure GDA0003120223920000041
本实施例中,聚醚胺选用数均分子量分别为400、1000和2000的D系列产品按质量比为1:2.5:6.5的混合物;多胺甲基聚异丁烯苯酚为聚异丁烯基苯酚与甲醛和多胺的缩合物,其中聚异丁烯基苯酚是数均分子量为950的聚异丁烯与苯酚在路易斯酸催化作用下的加成产物;助溶剂为季戊四醇、乙二醇单丁醚、司盘80质量比为1:5:1的混合液。
本实施例的甲醇燃料复合添加剂的制备方法为:将416g助溶剂加入反应器中,并加入19g双苯并三氮唑基双咪唑啉席夫碱和21g 2,6-二叔丁基对甲酚,在35~40℃下搅拌分散至完全溶解,再依次加入280g聚醚胺、180g多胺甲基聚异丁烯苯酚、18g油酸二乙醇酰胺硼酸酯、30g单油酸甘油酯和36g癸二酸二异辛酯,搅拌均匀。
实施例2
以制备甲醇燃料复合添加剂1000g为例,其由下述原料组成:
Figure GDA0003120223920000042
Figure GDA0003120223920000051
本实施例中,聚醚胺选用数均分子量分别为400、1000和2000的D系列产品按质量比为1:5:8的混合物;多胺甲基聚异丁烯苯酚为聚异丁烯基苯酚与甲醛和多胺的缩合物,其中聚异丁烯基苯酚是数均分子量为1300的聚异丁烯与苯酚在路易斯酸催化作用下的加成产物;助溶剂为季戊四醇、乙二醇单丁醚、司盘80质量比为1:10:1.5的混合液。
本实施例的甲醇燃料复合添加剂的制备方法与实施例1相同。
实施例3
以制备甲醇燃料复合添加剂1000g为例,其由下述原料组成:
Figure GDA0003120223920000052
本实施例中,聚醚胺选用数均分子量分别为400、1000和2000的D系列产品按质量比为1:6:7的混合物;多胺甲基聚异丁烯苯酚为聚异丁烯基苯酚与甲醛和多胺的缩合物,其中聚异丁烯基苯酚是数均分子量为800的聚异丁烯与苯酚在路易斯酸催化作用下的加成产物;助溶剂为季戊四醇、乙二醇单丁醚、司盘80质量比为1:9:0.5的混合液。
本实施例的甲醇燃料复合添加剂的制备方法与实施例1相同。
实施例4
以制备甲醇燃料复合添加剂1000g为例,其由下述原料组成:
Figure GDA0003120223920000061
本实施例中,聚醚胺选用数均分子量分别为400、1000和2000的D系列产品按质量比为1:2:10的混合物;多胺甲基聚异丁烯苯酚为聚异丁烯基苯酚与甲醛和多胺的缩合物,其中聚异丁烯基苯酚是数均分子量为1000的聚异丁烯与苯酚在路易斯酸催化作用下的加成产物;助溶剂为季戊四醇、乙二醇单丁醚、司盘80质量比为1:5:2.5的混合液。
本实施例的甲醇燃料复合添加剂的制备方法与实施例1相同。
实施例5
以制备甲醇燃料复合添加剂1000g为例,其由下述原料组成:
Figure GDA0003120223920000062
本实施例中,聚醚胺选用数均分子量分别为400、1000和2000的D系列产品按质量比为1:4:10的混合物;多胺甲基聚异丁烯苯酚为聚异丁烯基苯酚与甲醛和多胺的缩合物,其中聚异丁烯基苯酚是数均分子量为1100的聚异丁烯与苯酚在路易斯酸催化作用下的加成产物;助溶剂为季戊四醇、乙二醇单丁醚、司盘80质量比为1:5.5:2的混合液。
本实施例的甲醇燃料复合添加剂的制备方法与实施例1相同。
对比例1
将实施例1中的甲醇燃料复合添加剂中的聚醚胺替换为等量的市售聚醚胺(平均分子量为1000),其他成分及其用量与实施例1相同。
对比例2
将实施例2中的甲醇燃料复合添加剂中的聚醚胺替换为等量的市售聚醚胺(平均分子量为1000),其他成分及其用量与实施例2相同。
对比例3
将实施例3中的甲醇燃料复合添加剂中的双苯并三氮唑基双咪唑啉席夫碱替换为等量的市售苯并三氮唑,其他成分及其用量与实施例3相同。
对比例4
将实施例4中的甲醇燃料复合添加剂中的双苯并三氮唑基双咪唑啉席夫碱替换为等量的市售苯并三氮唑,其他成分及其用量与实施例4相同。
为了证明本发明的有益效果,发明人进行了性能评价试验,具体试验如下:
1、清净性能评价
试验参照《汽油清净剂评价汽油机进气阀沉积物模拟试验法》GB/T 37322-2019中的方法,对实施例1~5和对比例1、2中制备的甲醇燃料复合添加剂进行清净性试验,评定条件:待检油样为300mL甲醇汽油M15,沉积物收集器温度为180℃,复合添加剂加量为500mg/L,清净性能评定结果见表1。
表1复合添加剂的清净性能结果
复合添加剂 沉积物质量(mg/300mL) 沉积物下降率/%
空白 15.2 -
实施例1 0.9 94.08
实施例2 0.8 94.74
实施例3 0.6 96.05
实施例4 1.0 93.42
实施例5 0.8 94.74
对比例1 1.9 87.50
对比例2 3.9 74.34
由表1可知,在相同的试验条件下,本发明实施例1~5制备的甲醇燃料复合添加剂的沉积物质量较对比例1和2均低,沉积物下降率均在90%以上,且均达到《车用汽油清净剂》GB 19592-2019表1中不大于2.0mg/300mL的要求,这说明按数均分子量的高低进行搭配使用的聚醚胺和多胺甲基聚异丁烯苯酚复合使用,可使甲醇汽油M15燃烧更完全,燃油系统更清洁,汽车尾气中CH化合物、CO、NOx污染物的排放量大大降低,从而降低了机件磨损,延长了发动机使用寿命,减少了环境污染。
2、铜片腐蚀试验
试验参照《石油产品铜片腐蚀试验法》(GB/T 5096-2017)标准中9.3试管步骤-适用于多数液体产品的试验方法,对实施例1~5和对比例3、4中制备的甲醇燃料复合添加剂进行铜片腐蚀试验(复合添加剂加量为500mg/L),按9.4中的方法检查铜片;为强化实验,腐蚀介质为外加0.5%甲酸的M100甲醇燃料,试验结果见表2。
表2复合添加剂的缓蚀性能
Figure GDA0003120223920000081
由表2可知,在外加0.5%甲酸的M100甲醇燃料中,本发明实施例1~5制备的甲醇燃料复合添加剂对铜片的缓蚀性能均符合铜标准色板分级中1a的要求,较对比例3、4对铜片的缓蚀效果更优。
3、抗摩性能
试验参照《润滑油抗摩损性能的测定(四球法)》NB/SH/T 0189-2017和《润滑油摩擦系数测定法(四球法)》SH/T0762-2005中的方法,测定了复合添加剂在加量为500mg/L的M100甲醇燃料中的磨斑直径和摩擦系数,试验结果见表3。
表3复合添加剂的抗摩性能
复合添加剂 磨斑直径/μm 摩擦系数
实施例1 448.24 0.083
实施例2 410.37 0.079
实施例3 445.75 0.081
实施例4 402.98 0.067
实施例5 420.12 0.073
指标 ≤480 ≤0.12
由表3可知,本发明实施例1~5制备的甲醇燃料复合添加剂的磨斑直径、摩擦系数均满足指标要求,说明其在M100甲醇燃料中均具有良好的抗摩性能。

Claims (7)

1.一种甲醇燃料复合添加剂,其特征在于它由下述质量百分比的原料组成:
Figure FDA0003120223910000011
上述的聚醚胺是数均分子量分别为400、1000和2000的D系列产品按质量比为1:2~6:6~11的混合物;
上述的双苯并三氮唑基双咪唑啉席夫碱的结构式如下所示:
Figure FDA0003120223910000012
2.根据权利要求1所述的甲醇燃料复合添加剂,其特征在于它由下述质量百分比的原料组成:
Figure FDA0003120223910000013
3.根据权利要求1或2所述的甲醇燃料复合添加剂,其特征在于:所述的聚醚胺是数均分子量分别为400、1000和2000的D系列产品按质量比为1:3~5:7~9的混合物。
4.根据权利要求1或2所述的甲醇燃料复合添加剂,其特征在于:所述的助溶剂是季戊四醇、乙二醇单丁醚、司盘80质量比为1:5~13:0.5~2.5的混合液。
5.根据权利要求4所述的甲醇燃料复合添加剂,其特征在于:所述的助溶剂是季戊四醇、乙二醇单丁醚、司盘80质量比为1:6~10:1~2的混合液。
6.根据权利要求1或2所述的甲醇燃料复合添加剂,其特征在于:所述的多胺甲基聚异丁烯苯酚为聚异丁烯基苯酚与甲醛、多胺的缩合物,其中,聚异丁烯基苯酚为聚异丁烯与苯酚在路易斯酸催化作用下的加成产物,所述聚异丁烯的数均分子量为800~2400。
7.根据权利要求6所述的甲醇燃料复合添加剂,其特征在于:所述聚异丁烯的数均分子量为900~1300。
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