CN1295306C - 用于减少燃烧室中形成沉积物的燃料组合物添加剂 - Google Patents
用于减少燃烧室中形成沉积物的燃料组合物添加剂 Download PDFInfo
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- CN1295306C CN1295306C CNB031586856A CN03158685A CN1295306C CN 1295306 C CN1295306 C CN 1295306C CN B031586856 A CNB031586856 A CN B031586856A CN 03158685 A CN03158685 A CN 03158685A CN 1295306 C CN1295306 C CN 1295306C
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- propylamine
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Abstract
本发明提供了一种使用用于易燃燃料的摩擦改良剂来减少发动机燃烧室中沉积物形成的方法。摩擦改良剂通过将饱和羧酸和烷基化胺或烷氧基化胺混合制得。选择特定的摩擦改良剂可提供稳定的添加剂浓缩液以进行制备,在不增加消耗经添加剂浓缩液改性的燃料的燃烧发动机IVD沉积的发生率的情况下,以显著的降低CCD。
Description
此申请为2002年4月24日申请的申请号为10/128,529的待审申请的部分连续申请。
发明背景
本发明涉及用于燃料,特别是用于内燃机汽油的磨擦调节添加剂。本发明还涉及控制,即减少或消除发动机的燃烧室中的沉积物并同时能增强燃料经济性的新方法。
几年以来,人们在用于控制(防止或减少)点火式内燃机的燃料送入系统中的沉积物形成的添加剂方面进行大量的工作。特别是,可有效控制燃料喷射器沉积物、进气阀沉积物和燃烧室沉积物的添加剂代表了该领域中大量添加剂研究的焦点,并且,尽管进行了上述努力,仍需要作进一步的改进。
PFI和DIG发动机发生与燃料相关的沉积物问题的主要区域是喷射器、进气阀和燃烧室。此外,气阀结构、燃料泵之间的支动机摩擦导致了燃料消耗增加。在DIG发动机工艺中特别是在高压泵(高至1500psi排出量)中存在着与摩擦有关的耐用性问题,由于汽油本身不够润滑,可导致高压泵发生故障。因此,在石油工业中存在着这样的需求,即,生产出一种均适用于PFI和DIG发动机的,并可应对上文提到的发动机沉积物和摩擦力要求的燃料。
如McLean的美国专利号6,277,158中一定程度所讨论的,汽油和其它燃料的性能可以通过使用添加剂工艺进行改进。例如,已经使用了清洁剂以抑制进料系统沉积物的形成,由此可增加发动机的清洁度和性能。调节的要求需要导入低硫燃料,已知该燃料的润滑性差,因此,更需要关注燃料泵和喷射器的耐用性。已知硫本身并不是润滑改良剂。然而,公知通过深度氢化除去硫也能不经意地除去燃料中的天然润滑组分,如芳香族化合物、羧酸和酯类。不幸的是,否则除非以非常高的浓度将其加入到燃料中商业可获得的汽油清洁剂和分散剂几乎没有减少摩擦的性能。这些高清洁剂浓度常常可以达到其中无害作用如CCD变得无法接受的水平。
有人建议,可以向汽油中加入独立地摩擦改良剂以通过降低发动机沉积物而增加燃料的节省。燃料摩擦改良剂也可用于保护高压燃料泵和喷射器,诸如那些DIG发动机中发现的部件发现于全世界都在呼唤迅速减少燃料中的硫含量,这将甚至进一步加剧上述损耗问题。在为联合清洁剂/摩擦调节添加剂包选择适宜的组分时,保证清洁剂和摩擦改性性能的之间的平衡等是非常重要的。理想的,摩擦改良剂不会不利的影响清洁剂的沉积物控制功能。此外添加剂包不会不利的影响发动机性能。例如,添加剂不能加剧阀门粘性或导致其它降低性能的问题。为了适于化学使用,摩擦调节添加剂也必须通过所有针对汽油性能添加剂的无害测试。这通常是商业可得摩擦调节添加剂的最大障碍。无害测试包括1)与汽油和其它汽油中可能存在的添加剂在一定温度范围中具有相容性,2)不会增加IVD和CCD,3)在低温下没有阀门粘性,并且4)不会腐蚀燃料系统、汽缸、和曲轴箱。开发符合上述所有标准的添加剂是具有挑战性的。
多数现有的燃料摩擦改良剂是天然产物(得自植物或动物的)脂肪酸的衍射物,只有很少的纯净的合成产物。例如,WO 01/72930A2描述了描述了一种用于向上部汽缸壁和贮油槽中传递燃料衍生的摩擦改良剂,从而使上部汽缸/环和阀门润滑的机械方案摩擦改良剂与燃料清洁分散剂如聚醚胺(PEAs)、聚异丁烯胺(PIBAs)、曼尼希碱和琥珀酰亚胺一起进行包。WO’930确定了燃料摩擦改性的现有技术,参考资料包括美国专利号2,252,889、4,185,594、4,208,190、4,204,481以及4,428,182,这些都描述了在柴油机燃料中使用燃料改良剂。上述专利所涵盖的化学品包括脂肪酸酯、不饱和二聚脂肪酸、脂肪伯胺、二乙醇胺的脂肪酰胺以及长链脂族单羧酸。其它特定提到的专利美国专利号4,427,562,其公开了一种烷氧基烷基伯胺与羧酸反应得到或通过有适宜的甲酸酯的氨解而制备的润滑油和燃料摩擦改良剂,同样特定提及的还有美国专利号4,729,769。
美国专利号4,729,769公开了一种用于汽油组合物的得自C6-C20脂肪酸酯,诸如椰子油;以及单-或二-羟基烃基胺,诸如二乙醇胺的反应产物的用后汽化器清洁剂的汽油汽化器清洁剂。在专利'769中的添加剂被描述为可用于任一汽油中,包括含铅和含甲基环戊二烯基三羰基锰(MMT)的汽油。记载于专利′769的燃料可含有其它必要的添加剂,诸如防冻剂,以及腐蚀抑制剂。
美国专利号5,858,029描述了用于燃料和润滑剂的减少磨擦的添加剂,其涉及醚伯胺与氢羧酸的反应产物提供了可减少燃料和润滑剂磨擦的羟基酰胺。记载了摩擦改良剂的其它专利包括美国专利4,617,026(三元醇的单羧酸酯、甘油单油酸酯作为燃料和润滑剂摩擦改良剂);4,789,493、4,808,196和4,867,752(脂肪酸甲酰胺的应用);4,280,916(脂肪酸酰胺的应用);4,406,803(在润滑剂中的烷烃1,2-二醇用以改进燃料经济性的应用);以及4,512,903(从单或多元羟基取代脂族单羧酸和胺所得到的酰胺的应用)。美国专利6,328,771公开了由某种羧酸与含有杂环芳香胺的组分反应得到的含有润滑促进盐组合物的燃料组合物。EP0798364公开了含有羧酸和脂族胺的盐或由羧酸和脂族胺的脱水缩合而获得的酰胺的内燃机燃料添加剂。
EP 0 869 163 A1描述了一种通过使用乙氧基化胺减少发动机磨擦的方法。此外,美国专利4,086,172(作为润滑剂抗氧剂的油溶羟基胺,诸如“ETHOMEEN18-12TM”分子式C18H37N-(CH2CH2OH)2);4,129,508(作为破乳剂琥珀酸或酸酐与聚亚烷基二醇或单醚有机碱金属、烷基化胺的反应产物作为破乳剂);4,231,883;4,409,000和4,836,829都教导了羟基胺在燃料和润滑剂中的各种。
美国专利号6,277,158记载了在汽油供应中现行的实施方法,通常先将燃料添加剂预混合到碳氢化合物溶剂基质的浓缩液中,然后,在交给顾客前,将浓缩液注射到用于灌注油箱的汽油管子中。为了促进浓缩液注射到汽油中,浓缩液以低粘度的均匀液体的形式存在是很重要的。
摩擦改良剂可作为单独的添加剂也可以与清洁分散剂包相结合添加到汽油中,清洁分散剂包对燃料的相容性作了充分的配制,可以让发动机顺利的运作。此外,汽油的清洁剂/摩擦调节添加剂浓缩液可所有提高燃料节省、控制燃烧室沉积物和减少磨擦的需要。此外,满足浓缩液还必须在所有可能储存的温度下保持稳定,不能不利地影响成品汽油和使用该汽油的发动机的运行和性能,特别是不会导致IVD或CCD问题的增加。
发明概述
本发明提供了一种减少发动机内CCD形成的方法。本方法使用发动机的磨擦改良剂来实现,摩擦改良剂通过将饱和支链或直链羧酸与一种胺,诸如氨或烷基化胺或烷氧基化胺相混合来进行制备。
如此文中所使用的,术语“烷基化”通常是指它可以单烷基化或多烷基化(诸如“二烷基化”)。与摩擦改良剂一起使用的,上下文中使用的术语“胺”通常是指氨、单胺、或多胺(诸如“二胺”)。
在一优选的方面,摩擦改良剂含有单或二烷基化胺的支链饱和羧酸盐。在另一个优选的方面,摩擦改良剂含有烷基胺异硬脂酸盐。还应该认识到,摩擦改良剂和任一清洁剂软包并不一定是同一种物质。
如此文中所使用的,术语“烷氧基化”或“烷氧基”通常是指单烷氧基化、或多烷氧基化(诸如“二烷氧基化”)。与磨擦改良剂混合使用的,上下文中的术语“胺”通常是指单胺、或多胺(诸如“二胺”)。在一优选的方面,摩擦改良剂含有含有单或二烷基化胺的支链饱和羧酸盐。在另一个优选的方面,摩擦改良剂含有烷氧基胺异硬脂酸盐或醚胺异硬脂盐。
如此文中所使用的,术语“烷氧基化胺”和“醚胺”指伯、仲、叔胺,其中含有至(a)一个-OR型烷氧基,其中的R是C1-C28的脂族碳氢化合物,或含有(b)一个R-O-R'型醚基,其中的R和R'各自独立地为C1-C28脂族碳氢化合物。
当配制到发动机燃料中时,本发明的摩擦改良剂以可使发动机在耗油时显著减少燃烧室中的沉积物的有效量包括在其中。
在一个特别优选的方面,本发明利用一种用于燃烧内燃机燃料的添加剂浓缩液,该浓缩液含有(重量以浓缩液的总重量为计):
(a)0.2至50%的摩擦改良剂,其中含有氨或单或二烷基化胺的支链或直链饱和羧酸盐,其优选的是液体,或者可在室温或常压下可被溶液化;
(b)40至99.8%的清洁剂包,主要含有清洁剂和载体混合物;以及
(c)0至80%的溶剂。
在本发明的一个实施例中,其中的摩擦改良剂是正丁胺异硬脂酸盐或其支链饱和异构体,或者它们的混合物。在另一个实施例中,摩擦改良剂是通过将异癸氧基丙胺与异硬脂酸混合而形成的。同样的,摩擦改良剂(燃烧时)可以是无灰或产灰的,在优选的实施方式中是无灰的。
一方面,氨或烷基化胺或烷氧基化胺的支链或直链饱和羧酸盐,与清洁剂软包相结合的这种特别的选择,可以提供一种稳定的添加剂浓缩液以配制成可有效的获得显著的摩擦减少效果的摩擦改良剂,并且,由此,在不引起CCD增加的情况下使燃料节省得到了提高。在另一个方面,通过本发明,CCD显著的降低。
此处令人惊讶和意想不到的是,可以在不对IVD和/或燃料节省产生有害影响的情况下降低CCD。
在一优选的具体实施方式中,如本文中所定义的摩擦改良剂包括各自具有不同脂肪酸基团的各种单胺盐的混合物,其中的脂肪酸基团的主链长度各不相同,并有不同程度的支链取代。这样的摩擦改良剂的混合物可以进一步的降低添加剂组份的熔点,这样可使得摩擦调节组份更易于成为液体。优选的摩擦改良剂是在至少约-20℃至约+35℃温度范围内的液体。
人们发现,包含或烷基化胺或烷氧基化胺的支链或直链饱和羧酸盐的改良剂可以提供所有上述优点,而对比化合物,诸如正丁胺油酸盐这样的,特别是当与清洁剂合用时,会产生不希望的IVD发生率增加。虽然不被任何理论所束缚,但仍然假设,当使用被含摩擦改良剂和清洁剂的添加剂浓缩液改良后的燃料时,在本发明摩擦改良剂组份中提供饱和脂肪酸不会干扰寻找所需的CCD控制机理的,同时可分别得到所需的摩擦改性功能与CCD的降低。
本发明具体实施方式的实施中,用作摩擦改良剂的烷基化胺或烷氧基化胺的支链饱和羧酸盐脂肪酸基部分的聚亚烷基链的结构性支链化,被发现对于增加饱和摩擦调节添加剂化合物保持液态的可能性,并在正常操作温度下易于与燃料混合的性质是重要的。然而,如果希望或需要帮助固体形式的摩擦改良剂的增溶,增溶剂也可以包括在其中,诸如,直链饱和的羧酸,例如碳氢化合物溶剂,诸如醇类或有机酸,所以尽管增溶剂并不是重要的必须条件,但是也不能排除在本发明范围以外。
进而,本发明也直接涉及在控制汽油发动机内CCD和IVD沉积物的同时提高燃料效率的方法。在另一个实施方式中,本发明的物质组合物以零件市场或“首选”燃料添加剂组合物的形式被提供。
优选实施方式的详细说明
发明直接涉及通过向发动机在投入一种摩擦改良剂来降低发动机中CCD的具体实施方式,摩擦改良剂是通过将饱和直线型,或优选支链羧酸与氨或烷基化胺或烷氧基化胺反应、混合或联合而得到。示例性的方面,摩擦改良剂是通过将(i)饱和羧酸,与(ii)单烷基化单胺、或二烷基化单胺、(iii)单烷氧基化单胺、(iv)二烷氧基化单胺,或它们的任一二胺或多胺的类似物或其组合或混合物反应、混合而制得的。在一优选的方面,在制备摩擦改良剂中使用的饱和的支链脂肪酸是异硬脂酸。
当此摩擦改良剂与用于在带进气阀的发动机中燃烧的燃料的清洁剂包相结合使用时,可同时提供显著的性能改进效果与燃料节省的改进,并且在不增加IVD的情况下降低了CCD。例如,被本发明研究人发现的烷基化或烷氧基化单胺的饱和与支链或直线行羧酸盐,可显示特别优良的促进汽油燃料节省的性质,通过以下方式实现,例如,1)降低发动机上部汽缸壁的润滑油薄膜的边缘摩擦系数,并且2)当与清洁剂或沉积物抑制剂结合使用时,将IVD和CCD降低至低于单独使用沉积物抑制剂时的水平。它们也可展现优良的破乳能力。
摩擦改良剂
在一优选的具体实施方式中,本发明所使用的摩擦改良剂含有氨或单烷基化、二烷基化胺、多烷基化胺或单烷氧基化胺、二烷氧基化胺或烷氧基化胺的饱和支链或直线型单、二元或多元羧酸盐。在一较为优选的具体实施方式中,包括了饱和羧酸主链的支链化,以增加其在常温下与燃料的兼容性。
特别明确的,此文中所使用的羧酸非限制性地包括,2-乙基己酸、月桂酸、棕榈酸、硬脂酸、癸酸,十二烷酸、十一烷酸、肉豆蔻酸、癸酸、己酸、辛酸、甲基缬草酸、二缬草酸,以及异构体和它们的混合物。此外,其他本文可用的羧酸可以是烷基呈环状的烷基酸,其在这里被称为环状羧酸。
此外,本发明所使用的羧酸可以是单羧酸、二羧酸、多羧酸或者它们的混合物。
适宜的烷基化胺或烷氧基化胺的支链或直链饱和羧酸盐的非限制性结构式为如下的结构式I:
其中的R2和R3各自独立地代表烷基基团,优选C1-C6烷基基团,较为优选的是甲基;j是1至20,优选1至5;符号-(CH2)x-其中的x是4至20,条件是,每个R3将A处主链碳原子上的氢取代,且A处任一主链碳原子上连接的R3基团不超过两个;R4、R5和R6各自独立地代表烃基基团,诸如烷基或烷氧基、或氢原子;且q是1、2或3,且z和y各自独立地是0或1,其条件是,当z和y分别为0时q是3,当z或y中的一个是1另一个是0时q是2,当z和y分别为1时q是1。在一个具体实施方式中,A或R2可各自独立地是环状。
在一进一步的具体实施方式中,结构I中每一R4和R5各自独立地代表脂族C1-C8烷基或烷氧基基团,该基团可以是直链、环状、支链、未取代或取代的,其条件是,任一种分枝或取代基都不能使其与改性的燃料组合物不相容。在一特别的具体实施方式中,R4和R5各自独立地表示非羟基化的、脂族C1-C8烷基或烷氧基基团。在一个优选的方面,结构I中的R2和R3各自独立地代表脂族C1-C6烷基基团,该基团可以是直链的、支链的、环状的、未取代的和取代的,其条件是,任一种分枝或取代基都不能使其与改性的燃料组合物不相容。此处使用的环状胺的一个例子是哌啶。
作为本发明摩擦改良剂的氨或烷基化胺或烷氧基化胺的支链或直线型饱和羧酸盐可以通过以下方法制备,例如,将摩尔比约为1∶1的(i)支链或直线型饱和羧酸,或者它们的混合物和(ii)单-和/或二烷基化或烷氧基化单胺,和/或单-和/或二-烷基化或烷氧基化多胺混合后,在温度范围25℃至75℃下搅拌至温度不再发生变化。
此文中所定义的具有不同主链长度和各种支链化程度的摩擦改良剂的混合物可有利的用作摩擦改良剂。该类混合物可进一步的降低添加剂组分的熔点,从而可以使磨擦改性组分更易于以液体的形式存在。
同样的,结构I的磨擦改良剂的烷基化胺部分可以是,例如,单烷基化单胺,诸如正-丁基胺,或二烷基化单胺,诸如二-正-丁基胺。
同样的,结构I的磨擦改良剂的烷氧基化胺部分可以是,例如,
异己氧基丙胺
2-乙己氧基丙胺
辛/癸氧基丙胺
异癸氧基丙胺
异十二烷氧基丙胺
异十三烷氧基丙胺
C12-15烷氧基丙胺
异癸氧基丙基-1,3-二氨基丙烷
异十二烷氧基丙基-1,3-二氨基丙烷
异十三烷氧基丙基1,3-二氨基丙烷
异己氧基丙胺
2-乙基己氧基丙胺
辛/癸氧基丙胺
异癸氧基丙胺
异丙氧基丙胺
十四烷氧基丙胺
十二烷/十四烷氧基丙胺
十四烷/十二烷氧基丙胺
十八烷/十六烷氧丙胺
作为示例性的摩擦改良剂组分(a),其中的正-丁基胺异硬脂酸盐的通式是:(CH3)2CH(CH2)14C(O)O-+NH3C4H9。
正-丁胺异硬脂酸盐及其支链异构体都可用作磨擦改良剂。一种示例性的非限制性的结构性的表达式为以下的结构II:
上文所述的正-丁胺异硬脂酸盐,可以通过以下方法制得:以1∶1的摩尔比例混合正-丁胺和异硬脂酸后,在25℃至75℃温度范围内搅拌直至温度不再发生变化。
另一个例子是异癸氧基丙胺异硬脂酸盐。另一些例子是异硬脂酸铵和硬脂酸铵。
在成品汽油中的磨擦改良剂的处置浓度通常是可以实现改进性能并降低CCD效果,如本文中所说的提高燃料节省等等的量。例如,处置浓度为至少约5PTB(磅/一千桶),更优选的是至少约50PTB的摩擦改良剂可用于汽油中。
摩擦改良剂组分(a)可以以烷基化物烷氧基化胺支链饱和羧酸盐的相对纯的形式存在,或者任选的,以碘值低于10的其它支链羧酸烷基化胺或烷氧基化胺的其它支链羧酸盐共存的形式存在,只要碘值不会不利的影响本文中所定义的所需的添加剂性能。
汽油性能添加剂(GPA)包
传统的GPA包通常包括清洁剂包,清洁剂包中主要含有清洁剂和载体混合物,其主要目的是使发动机中的组分不产生沉积物。GPA包中的其它的组分典型的包括腐蚀抑制剂、破乳剂、抗氧化剂和溶剂,在某些情况下,向GPA包中加入标记物以便标识。由此,清洁剂包典型的加入到燃料添加剂浓缩液中作为GPA包的一部分,但这并不是必须的。
清洁剂(沉积物抑制剂)包
本文所述的添加剂浓缩液的具体实施方式中的清洁剂包组分中所使用的清洁剂或沉积物抑制剂可包括任一适宜的商业可得的清洁剂或沉积物抑制剂。用于汽油的沉积物抑制剂通常指作为清洁剂或分散剂的成分是公知的且可使用多种化合物。这些例子包括曼尼希碱、聚亚烷基胺聚亚烷琥珀酰亚胺,其中的聚亚烷基团典型的具有600至2000的平均分子量,优选800至1400;以及聚醚胺。优选用于本发明添加剂浓缩液的清洁剂是曼尼希碱清洁剂。
适用于本发明的曼尼希碱清洁剂包括高分子量的烷基-取代的羟基芳香化合物、醛类和胺的反应产物。用于制备本发明曼尼希反应产物的烷基-取代的羟基芳香化合物、醛类和胺可以是任一本领域公知并使用的化合物。
用于本发明的适宜的曼尼希清洁剂包括那些美国专利4,231,759、5,514,190、5,634,951、5,697,988中教导的清洁剂。5,725,612和5,876,468中所公开的内容在此引入作为参考。适宜的曼尼希碱清洁剂还包括,例如,HiTEC4995和HiTEC6410清洁剂,它们可从美国弗吉尼亚州Richmond的Ethyl公司处得到。
本发明的燃料组合物可进一步的含有选自曼尼希清洁剂、聚醚胺清洁剂、聚异丁烯清洁剂、琥珀酰亚胺清洁剂和咪唑啉清洁剂的材料。
载体
在一优选的实施方式中,清洁剂优选的与载体或导入助剂一起使用。载体典型的为一种载体液。这种载体可以是各种类型的,诸如,例如,液体聚-α-烯烃低聚物、矿物油、液体聚(氧化烯)化合物、聚链烷以及相似的液体载体。也可以使用所述载体中两种或多种的混合物。
可任选的溶剂
在其它方面,如有需要的话,添加剂浓缩液的运动粘度可以通过加入溶剂来调节(降低)。为了实现这一目的,可向浓缩液中加入溶剂,诸如芳烃类溶剂或醇类。这样的例子包括甲苯、二甲苯、四氢呋喃、异丙醇、异丁基甲醇、正-丁醇、以及石油碳氢化合物溶剂,诸如石油脑溶剂等。
燃料组合物
本发明的燃料组合物中除了上文所述的沉积结垢控制添加剂之外,可含有补充添加剂。所述补充添加剂包括分散剂/清洁剂、抗氧化剂、载体液、金属减活剂、染料、标记物、腐蚀抑制剂、杀生物剂、抗静电剂、减阻剂、破乳剂、乳化剂、dehazers、防冻添加剂、防爆添加剂、辛烷增强剂、防止阀座后退添加剂、润滑添加剂、表面活性剂和助燃剂。特别优选的补充添加剂包括甲基环戊二烯基三羰基锰,也即MMT,或者含-猛的汽油添加剂。
在另一方面,本发明提供了一种燃料组合物,其含有易燃燃料以及50至2500ppm重量的添加剂组合,该添加剂组合中含有如上所述的组分(a)、(b)以及任选的溶剂(c)。
本发明燃料组合物中使用的易燃燃料通常是指可用于内燃机的作为燃料的石油碳氢化合物,例如,汽油。这些燃料典型的含有不同类型的碳氢化合物的混合物,包括直链和支链石蜡、烯烃、芳香和环烷碳氢化合物、以及其它适宜点燃汽油发动机的液体。
上述组合物以几种级别提供,诸如无铅和含铅汽油,并且典型的通过常用的精炼和混合步骤诸如直馏、热裂解、加氢裂化、催化裂解和不同的改进操作得自石油原油。汽油可定义为最初沸点在20至60℃之间,最终沸点在150至230℃之间液态碳氢化合物或氧合碳氢化合物的混合物,其中所说沸点例如是由ASTM D86蒸馏法所测定的。汽油可含有其它的可燃物如醇类,例如甲醇或乙醇。
配制本发明中的燃料组合物所用的易燃燃料优选含有任一适宜用于汽油发动机作业的可燃燃料诸如含铅或无铅车用汽油,也叫新配方汽油,其典型的既含有可在汽油沸腾温度内沸腾的碳氢化合物也含有可溶于燃料的氧合混合剂(“氧合”),诸如醇、醚和其它适宜的含氧有机化合物。优选的,燃料是在汽油沸腾温度内沸腾的碳氢化合物的混合物。此燃料可由直链或支链石蜡、环烷烃、烯烃、芳香碳氢化合物或任一它们的混合物组成。汽油可得自直馏石油脑、聚合汽油、天然汽油或着从在80°至约450下沸腾的催化改造原料中衍生而来。汽油的辛烷值没有严格的要求,任一常用的汽油都可用于实践本发明。
适用于本发明的氧合物包括甲醇、乙醇、异丙醇、正-丁醇、C1至C5混合醇、甲基-叔丁醚、叔戊基-甲基醚、乙基-叔丁醚以及混合醚。在使用时,氧合物可正常的在基质燃料中以低于约85%体积的量存在,优选的,在全部燃料中所提供的氧含量在约0.5至约5%体积。
配制本发明优选的燃料所使用的添加剂可单独或以各种亚-混合体的形式混合到基质燃料中。
本发明的摩擦调节添加剂可通常用于耗用液体燃料的内燃机,特别的,是碳化了的、电控喷射(PFI)的,并且是直接注入汽油(DIG)的点火式汽油发动机。本发明优选的具体实施方式包括控制发动机沉积结垢的方法。通过将本文所述的a)点火式燃料和b)沉积结垢抑制剂软包/磨擦调节剂导入到发动机燃料组合物并分散其中而实现此目的。
实施例
本发明的实践和优点将通过以下实施例进行证明,这些实施例用于进行说明而非限定。
测试样本的制备
作为以下实施例的目的,对几种不同的摩擦改良剂进行测试,分别以5%5W30 GF-3测试油的溶液用于边界磨擦测定,或者与清洁剂HiTEC6421结合用于序号VI-B燃料节省发动机测试及IVD和CCD测定。HiTEC6421汽油性能添加剂(GPA)可从美国弗吉尼亚Richmond的Ethyl公司中商业购得。对于如下所述的序列VI-B发动机燃料节省测试,制备摩擦改良剂/GPA结合体以含有(a)50PTB摩擦改良剂和(b)80.9PTB的HiTEC6421GPA作为清洁剂的来源。
本发明中摩擦改性(FM)添加剂的例子是Century 1101V的正-丁胺盐Century 1101V是衍生自植物油的支链饱和脂肪酸的混合物。这种盐称为FM-1。本发明中盐的第二个例子(FM-2)是Century 1101P的正-丁胺盐,Century 1101P是衍生自松油的支链饱和脂肪酸的混合物。本发明盐的第三个例子是FM-3,是正-丁胺盐异硬脂酸。同样可用于本发明酸的是氢化动物源的脂肪酸和/或低聚物而得到的物质。作为比较,正-丁胺油酸盐,本发明范围以外的化合物,以相同的重量%比例代替正-丁胺异硬脂酸盐,以证实本发明CCD控制优越性。支链饱和脂肪酸的混合物以通用产品名Century 1101从Arizona Chemical购得。
对照实施例FM-4是单不饱和油酸铵/亚油酸铵混合物(分别为37%和46%其余为硬脂酸)。这些可以CenturyMO-5N从Arizona Chemical购得。
在Ford 2.3L发动机上根据ASTM操作的修订版进行CCD的测定,用以比较FM-1、FM-2和FM-3添加剂。测量含80.9PTB的曼尼希清洁剂(以及载体液)的燃料HiTEC6421GPA分别与50PTB的摩擦改良剂FM-1、50PTBFM-2和FM-3一起燃烧产生的CCD水平。所得结果概括于表1中。
表1
添加剂配制品 | 燃烧室沉积结垢(CCD)mg |
曼尼希 清洁剂(A) | 1613 |
(A)+FM-1(本发明) | 1443 |
(A)+FM-2(本发明) | 1460 |
(A)+FM-3(本发明) | 1416 |
(A)+FM-4(比较) | 1721 |
结果在表1中进行阐明,其显示,与含有不饱和添加剂(FM-4)和相同类型的清洁剂相的燃料组合物相比,含有饱和羧酸(FM1、FM-2和FM-3)正-丁胺盐清洁剂的燃料组合物明显显示了更为优秀的CCD控制和沉积结垢减少。
本发明同时指出,本发明中的正-丁胺异硬脂酸盐和现有技术中的正-丁胺油酸盐的功能都是用作汽油摩擦改良剂,但是使用含有清洁剂和正-丁胺异硬脂酸盐的燃料添加剂可得使CCD的发生率减少,而使用含有清洁剂与正-丁胺油酸酯的混合体的燃料添加剂导致不希望的CCD发生率的增加。
可以理解,对于以化学名表示的在说明书或权利要求书中任何地方出现的的反应物和组份不管其是单数还是复数应当在其与其他用化学名或化学类型(如碱性燃料、溶剂等)表示的物质接触前进行确认。无论何种化学改变、转换和/或反应,如果发生在所得混合物或溶液或反应介质中,诸如改变、转换和/或反应是将特定的反应物和/或组份放置在以本发明公开的内容为依据的条件下发生的自然反应。由此,反应物和组份应当被视为用于一起进行所需化学反应(诸如曼尼希冷凝反应)或用于形成所需的化合物(诸如添加剂浓缩液或添加的燃料混合物)的成分。同样的,需要认识到的是,添加剂组份可加入或混入或与碱性燃料本身单独混合和/或作为用于预形成的添加剂混合体和/或亚-混合体的组份。相应的,尽管下文中的权利要求可涉及到物质、组份和/或成分以现在时(“comprises”、“is”等)表示,意思是物质、组份或成分如同就在其首次与一种或多种其他的本发明公开的物质、组份和/或成分混合之前存在着。在所述的混合操作中,通过化学反应或变化,这些物质、组份或成分可丧失其原始等同性的事实,对于精确的理解和掌握本发明和权利要求是完全不重要的东西。
此处所使用的术语“燃料-可溶的”或“汽油-可溶的”表示,所讨论的物质在20℃下在碱性燃料中是充分可溶的,其中的碱性然料经选择用于达到至少可使物质发挥其作用的最低浓度。优选的,物质可具有在碱性燃料中比此更大的实际的溶解度。然而,物质不需要在所有部分都能溶于碱性溶液中。
在本说明书多处地方,给出了一系美国专利的参考。所有这些引用的文件都清楚的全部包括在此说明书公开物中,如同在此处已清楚的阐明。
本发明在实践中是易于进行多种变化的。因此,前述说明书并不用于限制、也并不能认为是要将本发明限制在上文中特别的示例之中。进而,本发明意在涵盖内容充分阐述在以下权利要求书及法律意义上许可的等同物之中。
Claims (31)
1.用于减少带有燃烧室的内燃机中的燃烧室中形成沉积物的方法,所述方法包括在所述内燃机中燃烧一种含有碳氢化合物燃料和摩擦改良剂的燃料组合物,其中的摩擦改良剂通过将一种胺与饱和羧酸相混合而制得,由此,所述发动机中燃烧室沉积物与在所述发动机中燃烧不含所述摩擦改良剂的燃料组合物的燃烧室沉积物相比有所减少。
2.权利要求1的方法,其中的胺选自氨、烷基胺和烷氧基胺。
3.权利要求1的方法,其中的饱和羧酸是支链化的。
4.权利要求1的方法,其中的饱和羧酸是直线型的。
6.权利要求1的方法,其中的胺选自单烷氧基化胺和多元烷氧基化胺。
7.权利要求1的方法,其中的胺选自单醚胺和聚醚胺。
8.权利要求1的方法,其中的胺选自单烷氧基化单胺和二烷氧基化单胺。
9.权利要求1的方法,其中的胺选自单烷氧基化二胺和二烷氧基化多胺。
10.权利要求1的方法,其中的胺选自多烷氧基化物二胺。
11.权利要求1的方法,其中的胺选自多烷氧基化物多胺。
12.权利要求5的方法,如果有R4、R5和R6,它们以饱和脂族烃基的形式存在。
13.权利要求1的方法,其中的羧酸选自异硬脂酸、2-乙基己酸、月桂酸、棕榈酸、硬脂酸、癸酸、十二烷酸、十一烷酸、肉豆蔻酸、癸酸、己酸、辛酸、甲基缬草酸、二甲基缬草酸以及它们的异构体和混合物。
14.权利要求1的方法,其中的羧酸是支链或环状羧酸。
15.权利要求1的方法,其中的羧酸选自单羧酸、二元羧酸和多元羧酸。
16.权利要求1的方法,其中的胺选自异己氧基丙胺;2-乙基己氧基丙胺;辛/癸氧基丙胺;异癸氧基丙胺;异十二烷氧基丙胺;异十三烷氧基丙胺;C12-15烷氧基丙胺;异癸氧基丙基-1,3-二氨基丙烷;异十二烷氧基丙基-1,3-二氨基丙烷;异十三烷氧基丙基1,3-二氨基丙烷;异己氧基丙胺;2-乙基己氧基丙基胺;辛/癸氧基丙胺;异癸氧基丙胺;异丙氧基丙胺;十四烷氧基丙胺;十二/十四烷氧基丙胺;十四/十二烷氧基丙胺;十八/十六烷氧基丙胺;十四烷氧基丙基-1,3-二氨基丙烷;以及C12-C15烷氧基丙基-1,3-二氨基丙烷。
17.权利要求1的方法,其中的胺是氨。
18.权利要求1的方法,其中的胺对羧酸的摩尔比约为1∶1。
19.权利要求1的方法,其中的胺选自单烷基化胺和多烷基化胺。
20.权利要求1的方法,其中的胺选自单烷基化单胺和二烷基化物单胺。
21.权利要求1的方法,其中的胺选自单烷基化二胺和二烷基化多胺。
22.权利要求1的方法,其中的胺选自多烷基化二胺。
23.权利要求1的方法,其中的胺选自多烷基化多胺。
24.权利要求1的方法,其中的胺是环型胺。
25.权利要求1的方法,其中的燃料组合物进一步含有选自曼尼希清洁剂、聚醚胺清洁剂、聚异丁烯清洁剂、琥珀酰亚胺清洁剂以及咪唑啉清洁剂的物质。
26.权利要求1的方法,其中的燃料组合物进一步含有一种或多种补充添加剂,选自分散剂、清洁剂、抗氧化剂、载体液、金属减活剂、染料、标记物、腐蚀抑制剂、杀生物剂、抗静电剂、减阻剂、破乳剂、乳化剂、消浊剂、防冻添加剂、辛烷增高剂、防爆添加剂、防止阀座后退添加剂、润滑添加剂、表面活性剂和助燃剂。
27.权利要求1的方法,其中的燃料组合物进一步含有甲基环戊二烯基三羰基锰。
28.权利要求1的方法,其中的燃料组合物进一步含有足够量的氧合燃料组合物的一种或多种氧合剂,选自甲醇、乙醇、异丙醇、正-丁醇、混合C1至C5醇、甲基-叔丁醚、叔戊基-甲基醚、乙基-叔丁基醚以及混合醚。
29.权利要求1的方法,其中的燃料组合物进一步的含有选自载体液、多元醇、矿物油和聚α-烯烃的物质。
30.一种燃烧如权利要求1所定义的燃料组合物的发动机。
31.权利要求1的方法,其中的饱和羧酸包括氢化动物-源的脂肪酸或低聚物所得的物质。
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US10/397,772 US7402185B2 (en) | 2002-04-24 | 2003-03-26 | Additives for fuel compositions to reduce formation of combustion chamber deposits |
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EP (1) | EP1462506A1 (zh) |
JP (1) | JP2004292788A (zh) |
KR (1) | KR100533490B1 (zh) |
CN (1) | CN1295306C (zh) |
AU (1) | AU2003231597A1 (zh) |
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JP2004292788A (ja) | 2004-10-21 |
CA2436197A1 (en) | 2004-09-26 |
EP1462506A1 (en) | 2004-09-29 |
SG110063A1 (en) | 2005-04-28 |
US7402185B2 (en) | 2008-07-22 |
KR100533490B1 (ko) | 2005-12-06 |
CN1534083A (zh) | 2004-10-06 |
KR20040086089A (ko) | 2004-10-08 |
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US20040010966A1 (en) | 2004-01-22 |
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