CN1629259A - 减少含有含氧物的中间馏分燃料中过氧化物的组合物和方法 - Google Patents

减少含有含氧物的中间馏分燃料中过氧化物的组合物和方法 Download PDF

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CN1629259A
CN1629259A CNA200410088374XA CN200410088374A CN1629259A CN 1629259 A CN1629259 A CN 1629259A CN A200410088374X A CNA200410088374X A CN A200410088374XA CN 200410088374 A CN200410088374 A CN 200410088374A CN 1629259 A CN1629259 A CN 1629259A
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S·D·施瓦布
J·J·本内特
A·A·阿拉迪
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Abstract

通过烃添加物与中间馏分燃料结合,减少中间馏分燃料中过氧化物形成或存在。特别地,将中间馏分燃料与一种或多种含氧物混合。烃添加物包括极性官能基团和官能基团β位的叔氢。结合添加物的中间馏分燃料、添加物自身和使用添加物的方法都可减缓燃料中过氧化物的形成或减少燃料中过氧化物的存在。过氧化物的减少可提高燃料系统弹性体的耐用性,增强燃料的稳定性和颜色的持久性,以及减少燃料沉积物的形成。

Description

减少含有含氧物的中间馏分燃料中过氧化物的组合物和方法
技术领域
本发明涉及包括将烃添加物与中间馏分燃料结合,以减少燃料中过氧化物形成或存在的组合物和方法。特别地,将中间馏分燃料与一种或多种含氧物(oxygenates)混合。烃添加物包括极性官能基团和官能基团β位的叔氢。添加物与中间馏分燃料结合减缓了过氧化物的形成和/或减少了过氧化物的存在,从而提高燃料系统弹性体的耐用性,例如弹性体是垫圈、胶管和封条,其暴露于燃料中的过氧化物中。烃添加物的其它优点包括增强燃料的稳定性和颜色的持久性,以及减少燃料中的沉积物。
背景技术
柴油发动机较之点火汽油发动机的公认优点是柴油发动机的高效率。柴油发动机的相对效率显著地超出点火汽油发动机,并可直接转化为燃料的节约以及燃烧副产物中的温室气体例如二氧化碳的降低。但是,其负面作用是,柴油发动机具有高的颗粒物和Nox散发的缺点。通过在柴油燃料中混有含氧物,可显著降低颗粒物。这些混入物能显著减少颗粒物的水平,并且不会显著增加Nox。不幸的是,混有柴油燃料的普通含氧物会加剧柴油燃料中过氧化物的形成。过氧化物对周围贮存容器和操作条件是一个严重问题,结果是造成柴油燃料系统老化。
而且现在倾向于使用极低硫的柴油燃料,极低硫的柴油燃料一般是指具有50ppm或更低的硫的燃料(″ULSD燃料″)。这种使用ULSD燃料的趋势会导致燃烧系统的实质改变,并同样显著地改变燃料的规格。许多工业化国家正在减少和/或已经减少他们强制的硫含量的最大规格。结果,符合新的规格配制的燃料的性能和操作面临新的关注。
一种对ULSD燃料的关注是去除硫化合物(一些硫化合物是有效的过氧化物清除剂和/或分解剂)会使过氧化物在这些燃料中产生。过氧化物潜在的增加对燃料系统有害,因为已知过氧化物会老化燃料系统的弹性体。因此,增加过氧化物会引起使用ULSD燃料的燃料系统的封条、垫圈和胶管出现故障。例如,参见Owen和Colev,汽车燃料参考书(Automotive Fuels Reference Book)第二版,1995,pp.520-523。这一问题潜在的严重性在1960和1970年代的喷气式发动机燃料中也有较好的证明,这些燃料中的高过氧化物含量与这些系统中燃料胶管、垫圈和封条的高损坏速度相关。参见E.g.,Fodor等人“喷气式发动机燃料中过氧化物的形成”, 能量和燃料(Energv and Fuels),1988,pp.729-34。
其它的关注是当过氧化物的水平上升时,燃料稳定性、颜色持久性和燃料沉积物增加。这些关注在Bacha和Lesnini,“柴油燃料在3000的热稳定性(Diesel Fuel Thermal Stability at 3000)”,液体燃料的稳定性和操作的第六次国际会议,Vancouver,加拿大,1997年10月13-17日;Vardi和Kraus,“Peroxide Formation in Low SulfurAutomotive Diesel Fuels”,SAE论文No.920826中有论述。
发明内容
通过烃添加物与燃料的结合,获得中间馏分燃料中过氧化物的形成或存在的减少。特定地,中间馏分燃料与一种或多种含氧物混合。烃添加物包括极性官能基团和官能基团β位的叔氢。结合添加物的中间馏分燃料、添加物自身和使用添加物的方法都可减缓燃料中过氧化物的形成或减少燃料中过氧化物的存在。过氧化物的减少可提高燃料系统弹性体的耐用性,增强燃料的稳定性和颜色的持久性,以及减少燃料沉积物的形成。
根据本文实施方案的燃料组合物,含有中间馏分燃料、含氧物和烃添加物,其中烃添加物含有极性官能基团和官能基团β位的叔氢。一种减少混有一种或多种含氧物的中间馏分燃料中过氧化物含量的方法,包括将中间馏分燃料与一种或多种含氧物混合;燃料与烃添加物结合,该烃添加物含有极性官能基团和官能基团β位的叔氢;其中和没有烃添加物的相同燃料比较,与燃料结合的烃添加物的量减少了燃料中过氧化物的量。
相信具有极性官能基团和官能基团β位的叔氢(质子氢)的烃添加物在贮存和操作温度下作为中间馏分燃料自由基陷阱。这些自由基陷阱俘获氧化的中间馏分燃料中的强自由基R*、OH*和R1-CH*-O-R2并阻断过氧化物的生成。未处理的氧化燃料可按如下过程产生过氧化物:
添加物分子上的极性官能基团可以是以下特征基团:醇、烷基酯、羧酸、酮、醛、胺、胺酯、硝基和亚硝酸酯化合物、硝酸酯、酚和其它官能基团,该官能基团或使其附着的烃分子β位的电子撤回,或能够使自由基共振离域。
烃添加物包括一类化合物,此类化合物在这些自由基可促进构成过氧化物形成的燃料自由基的链支化和增长步骤之前,用化学方法设置为初生态烷基(R*)和羟基(OH*)自由基的自由基陷阱。自由基猝灭反应由以下两个反应式表示:
其中R1和R2是碳链长度为C2-C30的不同烷基,在由任意官能基团组成的极性″X″官能基团的β位附加在自由基清除分子上,电子在自由基清除添加物分子的β位撤回。
在一个例子中,硝酸烷基酯作为自由基陷阱在低硫中间馏分燃料中抑制过氧化物的形成。
产物R1R2C*-CH2-ONO2具有稳定硝酸酯官能基团β位叔碳的自由基,硝酸酯官能团还可以进一步稳定经过硝酸酯官能基上共振离域的自由基。类似的自由基稳定反应式可写成添加物分子与其它上述列举的可作为自由基陷阱的官能基团。
本文利用的烃燃料通常由馏程为大约160℃至370℃的烃的混合物组成。此类燃料经常被称作“中间馏分燃料”,由于它们含有的成分在汽油之后蒸馏。此类燃料包括柴油燃料、生物柴油(biodiesel)和生物柴油-衍生燃料、燃烧器燃料(burner fuel)、煤油、瓦斯油(gas oil)、喷气式发动机燃料(jet fuel)和燃气涡轮发动机燃料。
在一个实施方案中,应用的中间馏分燃料是具有以下蒸馏分布特征的燃料:
    °F     ℃
    IBP     250-500     121-260
    10%     310-550     154-288
    50%     350-600     177-316
    90%     400-700     204-371
    EP     450-750     232-399
也可使用具有范围在30-60的清晰十六烷值(clear cetane number)(例如,缺乏任何十六烷改进剂(例如有机硝酸酯)时的十六烷值)的中间馏分燃料。在另一个例子中清晰十六烷值在40-50范围内。
通过在中间馏分燃料中混入含氧物,使得燃料氧含量在2-6%(8-15体积%),可以显著降低从中间馏分燃料燃烧系统释放出来的颗粒物。这些混合物能减少30-50%的颗粒物,同时不会显著增加NOx。可使用的含氧物包括:醚类,例如二甲醚(DME)、丁醚、戊醚、二正丁醚;甘醇二甲醚聚醚类,例如二甘醇甲醚(DGME)、三甘醇二甲醚、二甘醇二甲醚、1,2-二甲氧基乙烷(甘醇二甲醚)、Cetaner(96%甘醇二甲醚和4%二甲氧基甲烷的混合物)、乙二醇单叔丁基醚;乙二醇单正丁基醚;碳酸酯类,例如碳酸二甲酯和碳酸二乙酯;二乙酸酯类,例如乙二醇乙酸酯;缩醛类,例如二甲氧基甲烷(DMM或甲缩醛)、2-乙基己基乙酸酯;植物或动物油的酯,例如豆油脂肪酸甲酯,醇类,例如乙醇、甲醇、异丙醇、丁醇,酮,醛,羧酸及其酯,等等。
例如上述列举的酯可混入中间馏分燃料以减少中间馏分发动机中的微粒释放,所述柴油发动机在氧存在下有自氧化的倾向,形成过氧化物,如反应式1所示。
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                                [2]
                         [3]
                                                          [4]
                               [5]
[6]
纯的柴油燃料也有自氧化的倾向,并且由于燃料与氧反应形成过氧化物,会在贮存温度氧化老化。此类过氧化物的形成依赖于温度,在升高的温度下形成的速度更高。负载过氧化物的燃料造成危害贮存和操作的爆炸。在柴油燃料与含氧物混合以更高的速度形成过氧化物时,如反应式1-6所示,上述危险会进一步加剧。由于过氧化物形成的老化会成为周围贮存容器和操作条件(高至80℃)的严重问题。
例如中间馏分燃料(柴油、喷气式发动机燃料,等等)的烃中形成的过氧化物根据以下反应由氧夺取燃料分子的氢自由基开始。
                                                     [7]
                                                  [8]
                                                          [9]
                                                        [10]
                       [11]
通过过两个“热”自由基R*(烷基自由基)和OH*(羟基自由基)反应7-9开始并促进燃料过氧化物的形成。反应10和11表示烷基自由基R*如何引起过氧化物在燃料中产生。此类过氧化物在升高温度下的贮存过程中有热爆炸危险。因此,通过使用在本文初描述的烃添加物抵消两个“热”自由基R*和OH*,可有效地阻断燃料过氧化物自由基在环境温度下形成。
其它添加物也可包括在本文描述的燃料组合物中,条件是它们不会对不同于本文得到的过氧化物的含量或形成有不利影响。因此,可使用一种或多种此类组分组成作为腐蚀抑制剂、抗氧化剂、抗锈剂、去污剂和分散剂、燃料润滑添加剂、破乳剂、染料、惰性稀释剂、冷流改进剂、电导剂、金属减活化剂、稳定剂、止泡添加剂、去冰剂、生物杀灭剂、增香剂、减阻剂、助燃剂,例如,包括MMT(三羰基甲基环戊二烯基锰methylcyclopentadienyl manganese triacarbonyl)、含氧物和类似材料。这些添加剂也可组合成添加包使用。
硫化合物自身可减少燃料中过氧化物的量,所以目前的分析涉及低硫燃料。例如,含有有机硝酸酯助燃剂的极低硫燃料可具有小于大约100ppm的硫,或者小于大约50ppm的硫。更进一步可选择包括具有小于大约20ppm或小于大约10ppm的硫的燃料。
氧化中间馏分燃料中烃添加物的浓度可在相对宽的限度内变化,以便应用的量至少能足以减少存在或形成的过氧化物。处理率可根据燃料中混合的含氧物的类型和浓度变化。处理率也可根据与燃料结合的特定烃添加物变化。添加物的量为每百万份燃料100-5,000体积份添加物。在一个例子中,烃添加物与燃料以每百万份燃料500-2500体积份烃添加物的处理率结合。
保持氧化燃料中过氧化物的量小于大约8ppm,本文描述的有机烃添加物与氧化中间馏分燃料能获得(1)弹性体耐久性提高,(2)提高的燃料稳定性,(3)燃料沉积物的减少,和(4)提高的颜色持久性。
基于前面的分析,可以知道含有烃添加物的氧化中间馏分燃料中过氧化物的形成和/或存在(例如,过氧化物的量)减少了。当燃料长期贮存时,这对于延长与燃料接触的弹性材料的寿命是一个显著的优点。其它的优点包括提高燃料的稳定性、颜色的持久性和减少燃料中的沉积物。
期望根据行驶英里数、燃料燃烧的加仑数或服务的天数/年限,与不含所述烃添加物的燃料系统的弹性体耐久性比较,易受由暴露在燃料系统中过氧化物的老化影响的弹性体的稳定性因此可以延长或提高至少25%。在另一个实施方案中,与暴露在不含烃添加物的燃料的弹性体的耐久性比较,弹性体的耐久性延长或提高至少10%。
期望根据行驶英里数、燃料燃烧的加仑数或服务的天数/年限,与不含所述烃添加物的燃料的稳定性比较,中间馏分燃料的燃料稳定性因此可以延长或提高至少25%。在另一个实施方案中,与不含烃添加物的燃料的稳定性比较,燃料的稳定性延长或提高至少10%。
期望根据行驶英里数、燃料燃烧的加仑数或服务的天数/年限,与不含所述烃添加物的燃料的颜色持久性比较,燃料颜色的持久性因此可以延长或提高至少25%。在另一个实施方案中,期望与不含烃添加物的燃料的耐久性比较,燃料颜色的耐久性延长或提高至少10%。
期望根据行驶英里数、燃料燃烧的加仑数或服务的天数/年限,与不含所述烃添加物的燃料中燃料沉积物的量比较,燃料沉积物的形成或存在因此可以减少至少25%。在另一个实施方案中,与不含烃添加物的燃料中燃料沉积物的量比较,沉积物的量减少或延长至少10%。
应当理解在说明书或权利要求书的任何位置以单数或复数提到的反应物和组分的化学名称确认为它们在与另外的由化学名称或化学类型提到的物质(例如,基础燃料、溶剂,等等)接触之前存在的化学名称。不管什么化学变化、转化和/或反应,如果发生的话,得到的混合物或溶液或反应介质本身的变化、转化和/或反应是在按照本公开的条件下共同产生具体的反应物和/或组分的自然结果。因此,反应物和组分确定为共同进行期望的化学反应或形成想要的组合物(例如,添加浓缩物或添加的燃料混合物)的成分。还会认识到添加组分可加入或混入或各自与基础燃料混合和/或作为用于形成预先形成添加结合物和/或次结合物的组分。因此,虽然以下的权利要求以现在时态提到物质、组分和/或成分(″comprises″,″is″等),但是引用的物质、组分或成分是在其按照本公开内容第一次混入或与一种或多种其它物质、组分和/或成分混合之前存在的。实际上物质、组分或成分在这样混入或混合操作过程中或之后立刻经过化学反应或转化会失去其原始特性,到如此程度才能对本公开内容及其权利要求完全在精神上精确理解和领会。
在本说明书中多处,引用文献已制定为数字技术文件。所有这些引用文献如在这里全部阐明都清楚地并入本公开的内容中。
本发明在实施中允许有明显的变更。因此,上述描述不意在限制,和不应解释为将本发明限制到上文提到的特定范例。将意在概括的内容在随后的权利要求书中阐明并且其等价物在法律上被允许。
申请人不意在向公众贡献出任何公开的实施方案,对于范围而言,任何公开的改进或变更不应按照字义落入权利要求的范围,它们被认为是等同原则下本发明的一部分。

Claims (7)

1、一种降低混有一种或多种含氧物的中间馏分燃料中过氧化物的量的方法,该方法包括以下步骤:
提供混有一种或多种含氧物的中间馏分燃料;
将燃料与烃添加物结合,烃添加物含有极性官能基团和官能基团β位的叔氢;
其中和没有烃添加物的相同燃料比较,与燃料结合的烃添加物的量减少了燃料中过氧化物的含量。
2、一种燃料组合物,含有
中间馏分燃料;
含氧物;和
烃添加物,烃添加物含有极性官能基团和在官能团β位的叔氢。
3、一种含有含氧物的中间馏分燃料的烃添加物,该添加物含有极性官能基团和官能基团β位的叔氢。
4、一种提高中间馏分燃料系统弹性体耐用性的方法,包括以下步骤:
提供混有一种或多种含氧物的中间馏分燃料;
将燃料与烃添加物结合,该烃添加物含有极性官能基团和官能基团β位的叔氢;
其中和燃烧没有烃添加物的中间馏分燃料的中间馏分燃料系统中弹性体的稳定性比较,与燃料结合的烃添加物的量提高了中间馏分燃料系统弹性体的稳定性。
5、一种提高混有一种或多种含氧物的中间馏分燃料颜色耐久性的方法,包括以下步骤:
提供混有一种或多种含氧物的中间馏分燃料;
将燃料与烃添加物结合,烃添加物含有极性官能基团和官能基团β位的叔氢;
其中和没有烃添加物的混有一种或多种含氧物的中间馏分燃料的颜色耐久性比较,与燃料结合的烃添加物的量提高了中间馏分燃料的颜色耐久性。
6、一种提高混入一种或多种含氧物的中间馏分燃料稳定性的方法,包括以下步骤:
提供混入一种或多种含氧物的中间馏分燃料;
将燃料与烃添加物结合,该烃添加物含有极性官能基团和官能基团β位的叔氢;
其中和没有烃添加物的混有一种或多种含氧物的中间馏分燃料的燃料稳定性比较,与燃料结合的烃添加物的量提高了中间馏分燃料的燃料稳定性。
7、一种减少混有一种或多种含氧物的中间馏分燃料中燃料沉积物的方法,包括以下步骤:
提供混有一种或多种含氧物的中间馏分燃料;
将燃料与烃添加物结合,该烃添加物含有极性官能基团和官能基团β位的叔氢;
其中和没有烃添加物的混有一种或多种含氧物的中间馏分燃料中的燃料沉积物比较,与燃料结合的烃添加物的量减少了中间馏分燃料中的燃料沉积物。
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