CN105462636B - 一种低硫柴油添加剂及其制作工艺 - Google Patents

一种低硫柴油添加剂及其制作工艺 Download PDF

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CN105462636B
CN105462636B CN201511001734.2A CN201511001734A CN105462636B CN 105462636 B CN105462636 B CN 105462636B CN 201511001734 A CN201511001734 A CN 201511001734A CN 105462636 B CN105462636 B CN 105462636B
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丁以钿
刘五连
游子扬
丁宏
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Ding Yidian
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FUZHOU DONGYE ENERGY TECHNOLOGY Co Ltd
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Abstract

本发明涉及一种低硫柴油添加剂及其制作工艺,一种低硫柴油添加剂,以重量比计,生物柴油40~45份、甘油硬脂酸酯3~8份、硬脂酸乙酯2~5份、油酸酰胺9~15份、增溶剂20~24份、清洁剂6~10份、抗氧剂5‑8份;所述低硫柴油添加剂的制备方法,它包括以下步骤:先向反应容器中加入生物柴油以及增溶剂,加热搅拌之后加入甘油硬脂酸酯、硬脂酸乙酯以及油酸酰胺,再加入清洁剂和抗氧剂搅拌混合,之后过滤即的低硫柴油添加剂,本发明的优点在于:本发明的低硫柴油添加剂能够与柴油良好互溶、能够明显提高柴油的润滑性能;还具有抗氧化能力和清净分散性能。

Description

一种低硫柴油添加剂及其制作工艺
技术领域
本发明涉及添加剂领域,特别涉及一种低硫柴油添加剂及其制作工艺。
背景技术
柴油是一种石油炼制产品,在世界各国燃料结构中均占有较高的份额,已成为重要的动力燃料。随着世界范围内车辆柴油化趋势加快,未来柴油的需求量也会愈来愈大,但是柴油燃烧后排出的废气对环境的危害也日趋严重。如废气中的二氧化硫、氮氧化物不仅形成城市及周边地区的酸雨,还严重地破坏地球的臭氧层,颗粒物(PM)中含有多种被国际研究机构列为可能致癌的物质,同时颗粒物是造成雾霾的罪魁祸首。研究表明柴油硫含量对汽车污染物排放影响很大,特别是对氮氧化物和PM的产生有明显的促进作用,因此,为了保护环境,柴油的低硫化受到世界各国的普遍关注,柴油含硫低意味着柴油品质高,芳烃和极性物质含量降低。由于低硫柴油普遍采用较苛刻的加氢工艺,含氧、含氮化合物减少,造成柴油的润滑性能降低,并容易造成汽车喷油泵及内燃机活塞的磨损,降低了其使用寿命。
为了改善低硫柴油的的润滑性许多研究者致力于低硫柴油润滑剂的研究,发现一些醇醚类化合物、胺类化合物、酯类化合物、羧酸类化合物均能提高低硫柴油的润滑性。生物柴油其主要成分为脂肪酸甲酯,因此一些研究者直接往低硫柴油中加入生物柴油,发现生物柴油能够改善低硫柴油的润滑性,同时也能提高低硫柴油的燃烧率,另外,有机颗粒物的排放量也减少了。但是,因为生物柴油与低硫柴油的互溶性不够好,如往低硫柴油中加入低硫柴油量的50%的生物柴油,需要不断的大力机械搅拌,才能使二者完全的互溶,因此,如果想直接利用生物柴油来改善低硫柴油的润滑性,一方面使用起来不方便,另一方面如果二者互溶的不够,对低硫柴油的润滑性改善力度不大,也不能有效的提高低硫柴油的燃烧率。因此有必要发明出一种与低硫柴油具有良好互溶性、能够提高低硫柴油的润滑性能以及提高柴油燃烧效率的低硫柴油添加剂。
发明内容
本发明的目的在于提供一种与低硫柴油具有良好互溶性、能够提高低硫柴油的润滑性能以及提高柴油燃烧效率的低硫柴油添加剂及其制作工艺。
本发明的目的通过如下技术方案实现:
一种低硫柴油添加剂,以重量比计,生物柴油40~45份、甘油硬脂酸酯3~8份、硬脂酸乙酯2~5份、油酸酰胺9~15份、增溶剂20~24份、清洁剂6~10份、抗氧剂5-8份;
该低硫柴油添加剂是润滑剂、增溶剂、抗氧剂、清净剂的混合,使得该添加剂具备多种性能,不仅能够改善低硫柴油的润滑性、提高柴油的燃烧率;同时能够减少有机颗粒物的排放,减少对环境的污染。另外,它还能有效的防止积碳的产生,它是一种高效的低硫柴油添加剂。
其中,每百份增溶剂中含,40-45份山梨醇酐硬脂酸酯、35-45份聚环氧乙烷山梨糖醇单硬脂酸酯、15-20份山梨醇酐单油酸酯;山梨醇酐硬脂酸酯、聚环氧乙烷山梨糖醇单硬脂酸酯以及山梨醇酐单油酸酯均属于非离子表面活性剂,它们的混合能够使该低硫柴油添加剂与低硫柴油完全互溶,且仅需稍微搅拌就能使该添加剂与低硫柴油互溶。另外,本发明的发明人分别单独使用山梨醇酐硬脂酸酯、聚环氧乙烷山梨糖醇单硬脂酸酯以及山梨醇酐单油酸酯来作为增溶剂,发现它们单独使用的效果均没有它们三者结合所产生的效果好;并且发明人尝试了这三种非离子表面活性剂的不同混合比例,结果得到上述配方的效果最佳。
每百份清洁剂中含,15-25份咪唑啉、75-85份T151A聚异丁烯基丁二酰亚胺。T151A聚异丁烯基丁二酰亚具有良好的清净性和低温油泥分散性,可抑制发动机活塞上积炭和氧化膜的生成,该产品不含氯。适用于调制柴油机油、调制环保型内燃机油。咪唑啉具有净洗性,它在酸性和碱性介质中均稳定,可同阴、阳、非离子表面活性剂相伍。咪唑啉与聚异丁烯基丁二酰亚胺相配合能够有效的改善低硫柴油的清净性,另外,咪唑啉还可以由一些环烷酸咪唑啉代替,但是咪唑啉相比环烷酸咪唑啉而言,更简单更易得。
所述的抗氧剂为对,对-二异辛基二苯胺与2,6-二叔丁基-4-甲基苯酚的混合,其中每百份抗氧剂中含,45-55份对,对-二异辛基二苯胺、45-55份2,6-二叔丁基-4-甲基苯酚。
所述的低硫柴油添加剂,以重量比计,生物柴油43份、甘油硬脂酸酯5份、硬脂酸乙酯4份、油酸酰胺12份、增溶剂22份、清洁剂7份、抗氧剂7份;
其中,每百份增溶剂中含,42份山梨醇酐硬脂酸酯、40份聚环氧乙烷山梨糖醇单硬脂酸酯、18份山梨醇酐单油酸酯;
每百份清洁剂中含,20份咪唑啉、80份T151A聚异丁烯基丁二酰亚胺。
所述的低硫柴油添加剂,每百份抗氧剂中含,50份对,对-二异辛基二苯胺、50份2,6-二叔丁基-4-甲基苯酚。
所述的低硫柴油添加剂,其添加量为100-250mg/kg柴油。
所述低硫柴油添加剂的制备方法,它包括以下步骤:
先向反应容器中加入生物柴油以及增溶剂,边搅拌边缓慢加热使温度升至90-95℃,再在90-95℃条件下搅拌0.5-1h后,将温度降至55-65℃并恒定在55-65℃范围内,然后加入甘油硬脂酸酯、硬脂酸乙酯以及油酸酰胺,搅拌1-1.5h使原料充分互溶;再加入清洁剂,搅拌25-35min;最后加入抗氧剂,搅拌1-1.5h后,得混合溶液;将混合溶液冷却静置至室温后,经过滤得到透明澄清的柴油添加剂;其中,以上所述步骤中涉及搅拌的,搅拌速度控制在800~1400r/min范围内。
较之现有技术而言,本发明的优点在于:1)本发明制得的低硫柴油添加剂能够与柴油良好互溶,只需稍微搅拌或震荡便可互溶,无需长时间不断搅拌;2)该低硫柴油添加剂能够明显提高柴油的润滑性能;3)该低硫柴油添加剂不仅能够提高柴油的燃烧率,而且还具有抗氧化能力和清净分散性能,对胶质等极性化合物和细小颗粒具有很强的吸附和捕捉能力,可阻止其进一步氧化、聚集,从而减少柴油中氧化沉渣的产生。4)本发明的添加剂还具有其他功能,如改善柴油的铜片腐蚀性,减少柴油发动机尾气的排放,是一种环境友好型添加剂。
具体实施方式
下面结合实施例对本发明内容进行详细说明:
实施例一:低硫柴油添加剂的制备方法,它包括以下步骤:以重量比计,
先向反应容器中加入40份生物柴油以及20份增溶剂,其中,每百份增溶剂中含,40份山梨醇酐硬脂酸酯、45份聚环氧乙烷山梨糖醇单硬脂酸酯、15份山梨醇酐单油酸酯,边搅拌边缓慢加热使温度升至90℃,再在90℃条件下搅拌0.5h后,将温度降至55℃并恒定在55℃范围内;
然后加入8份甘油硬脂酸酯、2份硬脂酸乙酯以及15份油酸酰胺,搅拌1h使原料充分互溶;再加入10份清洁剂,搅拌25min,其中,每百份清洁剂中含,15份咪唑啉、85份T151A聚异丁烯基丁二酰亚胺;
最后加入5份抗氧剂,其中,每百份抗氧剂中含,45份对,对-二异辛基二苯胺、55份2,6-二叔丁基-4-甲基苯酚,搅拌1h后,得混合溶液。将混合溶液冷却静置至室温后,经过滤得到透明澄清的柴油添加剂。其中,以上所述步骤中涉及搅拌的,搅拌速度控制在800r/min范围内。
实施例二:低硫柴油添加剂的制备方法,它包括以下步骤:以重量比计,
先向反应容器中加入43份生物柴油以及22份增溶剂,其中,每百份增溶剂中含,42份山梨醇酐硬脂酸酯、40份聚环氧乙烷山梨糖醇单硬脂酸酯、18份山梨醇酐单油酸酯,边搅拌边缓慢加热使温度升至92℃,再在92℃条件下搅拌0.8h后,将温度降至60℃并恒定在60℃范围内;
然后加入5份甘油硬脂酸酯4份硬脂酸乙酯以及12份油酸酰胺,搅拌1.2h使原料充分互溶;再加入7份清洁剂,搅拌30min,其中,每百份清洁剂中含,20份咪唑啉、80份T151A聚异丁烯基丁二酰亚胺;
最后加入7份抗氧剂,其中,每百份抗氧剂中含,50份对,对-二异辛基二苯胺、50份2,6-二叔丁基-4-甲基苯酚,搅拌1.2h后,得混合溶液。将混合溶液冷却静置至室温后,经过滤得到透明澄清的柴油添加剂。其中,以上所述步骤中涉及搅拌的,搅拌速度控制在1200r/min范围内。
实施例三:低硫柴油添加剂的制备方法,它包括以下步骤:以重量比计,
先向反应容器中加入42份生物柴油以及23份增溶剂,其中,每百份增溶剂中含,43份山梨醇酐硬脂酸酯、38份聚环氧乙烷山梨糖醇单硬脂酸酯、19份山梨醇酐单油酸酯,边搅拌边缓慢加热使温度升至92℃,再在92℃条件下搅拌0.8h后,将温度降至60℃并恒定在60℃范围内;
然后加入6份甘油硬脂酸酯3份硬脂酸乙酯以及12份油酸酰胺,搅拌1.2h使原料充分互溶;再加入8份清洁剂,搅拌30min,其中,每百份清洁剂中含,18份咪唑啉、82份T151A聚异丁烯基丁二酰亚胺;
最后加入6份抗氧剂,其中每百份抗氧剂中含,47份对,对-二异辛基二苯胺、53份2,6-二叔丁基-4-甲基苯酚,搅拌1.2h后,得混合溶液。将混合溶液冷却静置至室温后,经过滤得到透明澄清的柴油添加剂。其中,以上所述步骤中涉及搅拌的,搅拌速度控制在1200r/min范围内。
实施例四:低硫柴油添加剂的制备方法,它包括以下步骤:以重量比计,
先向反应容器中加入44份生物柴油以及21份增溶剂,其中,每百份增溶剂中含,44份山梨醇酐硬脂酸酯、40份聚环氧乙烷山梨糖醇单硬脂酸酯、16份山梨醇酐单油酸酯,边搅拌边缓慢加热使温度升至92℃,再在92℃条件下搅拌0.8h后,将温度降至60℃并恒定在60℃范围内;
然后加入6份甘油硬脂酸酯4份硬脂酸乙酯以及11份油酸酰胺,搅拌1.2h使原料充分互溶;再加入7份清洁剂,搅拌30min,其中,每百份清洁剂中含,22份咪唑啉、78份T151A聚异丁烯基丁二酰亚胺;
最后加入7份抗氧剂,其中每百份抗氧剂中含,48份对,对-二异辛基二苯胺、52份2,6-二叔丁基-4-甲基苯酚,搅拌1.2h后,得混合溶液。将混合溶液冷却静置至室温后,经过滤得到透明澄清的柴油添加剂。其中,以上所述步骤中涉及搅拌的,搅拌速度控制在1200r/min范围内。
实施例五:低硫柴油添加剂的制备方法,它包括以下步骤:以重量比计,
先向反应容器中加入45份生物柴油以及24份增溶剂,其中,每百份增溶剂中含,45份山梨醇酐硬脂酸酯、35份聚环氧乙烷山梨糖醇单硬脂酸酯、20份山梨醇酐单油酸酯,边搅拌边缓慢加热使温度升至95℃,再在95℃条件下搅拌1h后,将温度降至65℃并恒定在65℃范围内;
然后加入3份甘油硬脂酸酯、5份硬脂酸乙酯以及9份油酸酰胺,搅拌1.5h使原料充分互溶;再加入6份清洁剂,搅拌35min,其中,每百份清洁剂中含,15份咪唑啉、85份T151A聚异丁烯基丁二酰亚胺;
最后加入8份抗氧剂,每百份抗氧剂中含,55份对,对-二异辛基二苯胺、45份2,6-二叔丁基-4-甲基苯酚,搅拌1.5h后,得混合溶液,将混合溶液冷却静置至室温后,经过滤得到透明澄清的柴油添加剂,其中,以上所述步骤中涉及搅拌的,搅拌速度控制在1400r/min范围内。
实施例六:选用柴油A,对实施例一所得的低硫柴油添加剂进行加剂前后的磨斑直径测试。所采用的方法为SH/T0765法测定,主要测定条件:添加量为100mg/kg,柴油油样体积:2.0±0.2(ml),冲程1.0±0.1(mm),频率50±1(Hz),液体温度60±2(℃),应用载荷200±1(g),试验时间75±0.1(min),测定润滑性磨斑直径,单位微米,实验结果见表2;
实施例七:选用低硫柴油B,对实施例一所得的低硫柴油添加剂进行加剂前后的磨斑直径测试,试验方法和测试条件同上,添加量为100mg/kg,实验结果见表2;
实施例八:选用柴油A,对实施例二所得的低硫柴油添加剂进行加剂前后的磨斑直径测试,试验方法和测试条件同上,添加量为150mg/kg,实验结果见表2;
实施例九:选用低硫柴油B,对实施例二所得的低硫柴油添加剂进行加剂前后的磨斑直径测试,试验方法和测试条件同上,添加量为150mg/kg,实验结果见表2;
实施例十:选用柴油A,对实施例三所得的低硫柴油添加剂进行加剂前后的磨斑直径测试,试验方法和测试条件同上,添加量为175mg/kg,实验结果见表2;
实施例十一:选用低硫柴油B,对实施例三所得的低硫柴油添加剂进行加剂前后的磨斑直径测试,试验方法和测试条件同上,添加量为175mg/kg,,实验结果见表2;
实施例十二:选用柴油A,对实施例四所得的低硫柴油添加剂进行加剂前后的磨斑直径测试,试验方法和测试条件同上,添加量为200mg/kg,实验结果见表2;
实施例十三:选用低硫柴油B,对实施例四所得的低硫柴油添加剂进行加剂前后的磨斑直径测试,试验方法和测试条件同上,添加量为200mg/kg,实验结果见表2;
实施例十四:选用柴油A,对实施例五所得的低硫柴油添加剂进行加剂前后的磨斑直径测试,试验方法和测试条件同上,添加量为250mg/kg,实验结果见表2;
实施例十五:选用低硫柴油B,对实施例五所得的低硫柴油添加剂进行加剂前后的磨斑直径测试,试验方法和测试条件同上,添加量为250mg/kg,实验结果见表2;
实施例十六:选用低硫柴油B,对实施例一所得的低硫柴油添加剂进行加剂前后的磨斑直径测试,试验方法和测试条件同上,添加量为120mg/kg,实验结果见表2;
实施例十七:选用低硫柴油B,对实施例一所得的低硫柴油添加剂进行加剂前后的磨斑直径测试,试验方法和测试条件同上,添加量为150mg/kg,实验结果见表2;
实施例十八:选用低硫柴油B,对实施例一所得的低硫柴油添加剂进行加剂前后的磨斑直径测试,试验方法和测试条件同上,添加量为175mg/kg,实验结果见表2;
实施例十九:选用低硫柴油B,对实施例一所得的低硫柴油添加剂进行加剂前后的磨斑直径测试,试验方法和测试条件同上,添加量为200mg/kg,实验结果见表2;
实施例二十:选用低硫柴油B,对实施例一所得的低硫柴油添加剂进行加剂前后的磨斑直径测试,试验方法和测试条件同上,添加量为250mg/kg,实验结果见表2;
其中A柴油和B柴油的一些理化性能见表1。
表1本发明试验所用柴油A和低硫柴油B的理化性能
表2本发明的柴油添加剂对柴油A和低硫柴油B润滑性的改善
从表2的试验结果可知:本发明的低硫柴油添加剂可以比较明显的改善低硫柴油的润滑性能。
实施例二十一至实施例二十五:低硫柴油添加剂对低硫柴油B氧化安定性的效果测试:
《馏分燃料油氧化安定性测定法(加速法)SHT0175-2004》概要:将已过滤的350ml试样装人氧化管中,通入氧气,速率为50ml/min,在95℃下氧化16h,然后将氧化后的试样冷却至室温,过滤,得到可滤出不溶物。用三合剂把粘附性不溶物从氧化管壁和通氧管壁上洗下来,把三合剂蒸发除去,得到粘附性不溶物。可滤出不溶物的量和粘附性不溶物的量之和为总不溶物的量,以mg/100ml表示。实验结果件表3
表3低硫柴油添加剂对低硫柴油B氧化安定性的效果
从表3的试验结果可知:本发明的低硫柴油添加剂可以比较明显的改善低硫柴油的氧化沉渣,提高了低硫柴油的抗氧化性能。
实施例二十六至实施例三十:添加剂对柴油清净性的效果测试:《SHT0764-2005柴油机喷嘴结焦试验方法(XUD-9法)》概要:试验在XUD-9柴油发动机试验台架上完成,将流量检查合格的清洁喷嘴装配到柴油发动机上,在方法要求的工况下,发动机运转10个小时。然后测量喷嘴在试验前后的空气流量变化,得到柴油对喷嘴的结焦性能的好坏。以0.1mm针阀升程时4个喷油嘴的空气流量损失率的平均值表示。实验结果件表4
表4低硫柴油添加剂对低硫柴油B清净性的效果试验
试验结果说明本发明的低硫柴油添加剂可以比较明显的改善低硫柴油对喷嘴的空气流量损失率,提高低硫柴油的清净性能。
实施例三十一至实施例三十五:低硫柴油添加剂与低硫柴油B互溶性的评价将实施例一至实施例五所得的低硫柴油添加剂分别与低硫柴油B在常温下进行搅拌混溶,测试其互溶澄清,所需的搅拌互溶时间,其中搅拌速度为400r/min。另外,设置对比例5,对比例5所用的与低硫柴油B混溶的添加剂为该低硫柴油添加剂配方中的生物柴油,测试的实验结果见表5:
表5低硫柴油添加剂与低硫柴油B的互溶效果评价
试验结果说明本发明的低硫柴油添加剂可以与低硫柴油B良好的互溶,且互溶性明显好于生物柴油。
另外发明人对实施例一至实施例五所得的低硫柴油添加剂还进行了铜片腐蚀试验,发现本发明的低硫柴油添加剂能改善柴油的铜片腐蚀性。

Claims (6)

1.一种低硫柴油添加剂,其特征在于:以重量比计,生物柴油40~45份、甘油硬脂酸酯3~8份、硬脂酸乙酯2~5份、油酸酰胺9~15份、增溶剂20~24份、清洁剂6~10份、抗氧剂5-8份;
其中,每百份增溶剂中含40-45份山梨醇酐硬脂酸酯、35-45份聚环氧乙烷山梨糖醇单硬脂酸酯、15-20份山梨醇酐单油酸酯;
每百份清洁剂中含15-25份咪唑啉、75-85份T151A聚异丁烯基丁二酰亚胺。
2.根据权利要求1所述的低硫柴油添加剂,其特征在于:所述的抗氧剂为对,对-二异辛基二苯胺与2,6-二叔丁基-4-甲基苯酚的混合,其中每百份抗氧剂中含45-55份对,对-二异辛基二苯胺、45-55份2,6-二叔丁基-4-甲基苯酚。
3.根据权利要求1所述的低硫柴油添加剂,其特征在于:以重量比计,生物柴油43份、甘油硬脂酸酯5份、硬脂酸乙酯4份、油酸酰胺12份、增溶剂22份、清洁剂7份、抗氧剂7份;
其中,每百份增溶剂中含42份山梨醇酐硬脂酸酯、40份聚环氧乙烷山梨糖醇单硬脂酸酯、18份山梨醇酐单油酸酯;
每百份清洁剂中含20份咪唑啉、80份T151A聚异丁烯基丁二酰亚。
4.根据权利要求3所述的低硫柴油添加剂,其特征在于:每百份抗氧剂中含50份对,对-二异辛基二苯胺、50份2,6-二叔丁基-4-甲基苯酚。
5.根据权利要求1所述的低硫柴油添加剂,其特征在于:其添加量为100-250mg/kg柴油。
6.根据权利要求1所述的低硫柴油添加剂的制备方法,其特征在于:它包括以下步骤:
先向反应容器中加入生物柴油以及增溶剂,边搅拌边缓慢加热使温度升至90-95℃,再在90-95℃条件下搅拌0.5-1h后,将温度降至55-65℃并恒定在55-65℃范围内;然后加入甘油硬脂酸酯、硬脂酸乙酯以及油酸酰胺,搅拌1-1.5h使原料充分互溶;再加入清洁剂,搅拌25-35min;最后加入抗氧剂,搅拌1-1.5h后,得混合溶液;将混合溶液冷却静置至室温后,经过滤得到透明澄清的柴油添加剂;其中,以上所述步骤中涉及搅拌的,搅拌速度控制在800~1400r/min范围内。
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