CN107835849A - 具有改善十六烷值和润滑性能的柴油组合物 - Google Patents
具有改善十六烷值和润滑性能的柴油组合物 Download PDFInfo
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- C—CHEMISTRY; METALLURGY
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Abstract
本发明的目的是一种新型柴油组合物,其包含柴油燃料和从0.01至0.8体积%的甘油缩醛或缩酮。与已知的柴油组合物相比,这种新型柴油组合物显示出更高的十六烷值和更好的润滑性能。
Description
发明领域
本发明涉及一种新型柴油组合物,其含有特定低量的甘油缩酮或缩醛作为改善柴油组合物的十六烷值和润滑性能的添加剂。
发明背景
十六烷值或CN是柴油燃料燃烧速度的指标。
十六烷值是燃料点火延迟的反函数,并且燃料燃烧期间喷射开始与第一可识别压力之间的时间段增加。在特定的柴油机中,十六烷较高的燃料与十六烷较低的燃料相比,点火延迟时间较短。
简而言之,在压缩设置(例如柴油机)中,十六烷值越高,燃料就越容易燃烧。因此,较高的十六烷值燃料通常会使发动机更平稳、更安静地运转。
一般来说,CN值为从40到55时,柴油机运行良好。具有较高十六烷值的燃料具有较短的点火延迟时间,其为燃料燃烧过程提供更多的时间。因此,柴油机的十六烷值燃料越高则会更高速、有效地运转。
在欧洲,柴油十六烷值在1994年设置为最低38,在2000年设置为40。目前在欧盟、冰岛、挪威和瑞士销售的柴油标准在EN 590中设定,最低十六烷指数为46,并且最低十六烷值为51。优质柒油燃料的十六烷值可高达60。
在北美,大多数州采用ASTM D975作为其柴油燃料标准,并且最低十六烷值设置为40,而典型值在42-45的范围内。根据供应商的不同,优质柴油可能有或没有更高的十六烷值。优质柴油通常使用添加剂来改善CN和润滑性能,使用清洁剂清洁燃料喷射器,并根据地理和季节性需求将积碳、水分散剂和其他添加剂降到最低。加州柴油燃料的最低十六烷值为53。根据德克萨斯州低排放柴油(TxLED)计划,110个县的柴油燃料必须具有48或更大的十六烷值,否则必须使用经过批准的替代方案或符合指定的替代限值。
源自植物油源的生物柴油记录为十六烷值范围为46至52,并且基于动物脂肪的生物柴油十六烷值范围为56至60。二甲醚是一种潜在的柴油燃料,因为它具有高的十六烷等级(55-60),并且可作为生物燃料生产。
精确测量出十六烷值是相当困难的,因为它要求在标准测试条件下,在称为合作燃料研究(CFR)的稀有柴油发动机中燃烧燃料。CFR发动机的操作者使用手轮来增加发动机的压缩比(和气缸内的峰值压力),直到燃料喷射与燃烧之间的时间为2.407毫秒。
然后通过确定十六烷(十六碳烷)和异辛烷(2,2,4,4,6,8,8-七甲基壬烷)的哪种混合物将导致相同的点火延迟来计算所得的十六烷值。
测量十六烷值的行业标准是ASTM D-613(ISO 5165)。
提高十六烷值的常用添加剂是硝酸烷基酯,主要是硝酸2-乙基己酯和过氧化二叔丁基。硝酸2-乙基己酯被列为环境危险品,其对水生生物有毒并具有长期持续的影响,如果吞咽或吸入具有急性毒性,并且接触皮肤会产生有害影响。二叔丁基过氧化物有急性水生毒性、慢性水生毒性和生殖细胞致突变性。
CN是决定柴油燃料质量的重要因素,但不是唯一的因素;柴油质量的其他测量包括(但不限于)能量含量、密度、润滑性能、冷流性质和硫含量。
润滑性能是减少摩擦和/或润滑剂磨损的措施。
物质的润滑性能不是物质性质,并且不能直接测量。进行测试以量化特定系统的润滑剂性能。这通常是通过确定给定的磨损物体在给定的时间量内对表面造成磨损的多少来完成的。还规定了其他因素,如表面大小、温度和压力。对于具有相同粘度的两种流体来说,导致较小磨斑的流体被认为具有较高的润滑性能。由于此因,润滑性能也被称为物质的抗磨损性能。
在现代柴油机中,燃料是发动机润滑过程的一部分。柴油燃料自然含有提供润滑性能的化合物,但是由于许多国家(例如美国和欧盟)的法规,必须在燃料被销售之前从燃料中除去硫,并且加氢处理柴油燃料以除去硫也可去除提供润滑性能的化合物。没有添加生物柴油的新配方柴油燃料具有较低的润滑性能并需要润滑性能改进添加剂以防止发动机过度磨损。
已经建立了一种通过使用HFRR方法(ISO 12156-1标准)的合适的柴油燃料润滑标准:测试柴油燃料后获得的HFRR磨斑直径(WSD)必须低于460μm,以确保该燃料具有足够的润滑性能。必要时,添加添加剂可以很容易地恢复更好的润滑性能。但是,这些添加剂必须单独或在掺入多功能配方后具有良好的物理和化学稳定性。它们还必须与燃料中可能存在的其他添加剂完全相容,如流动改进剂、防沉蜡添加剂、清洁剂等。
为了验证这种物理和化学相容性,并确保每种添加剂在与多功能配方或燃料本身混合后保持其全部效率,则不进行危害测试。
已经提出了许多类型的添加剂以改善柴油的润滑性能。因此已经将抗磨损添加剂加入到柴油燃料中,其中一些在润滑油领域是已知的,例如脂肪酸酯和不饱和脂肪酸二聚体、脂肪胺、脂肪酸酯、二乙醇胺和长链脂族一元羧酸,如在美国专利2,252,889、4,185,594、4,204,481、4,208,190和4,428,182中所述。这些添加剂大多数具有足够的润滑能力,但浓度非常高,并且这在经济上非常不利于购买。US7789918公开了一种用于低硫柴油的润滑性能改进剂组合物,其包含0.1-10%重量的衍生自腰果壳油液(CNSL酯)的酯衍生物。WO0136568、EP 1230328、JP 2003 5149537描述了涉及添加剂混合物的发明,该添加剂混合物包含a)二羧酸或其衍生物与长链脂肪族胺反应后形成的反应产物b)天然脂肪酸酯,c)用于改善燃料的润滑性能并改善发动机耐磨性的所述添加剂混合物的用途,此外还涉及含有所述添加剂混合物的燃料和润滑剂组合物。
描述使用低硫柴油添加剂用途的几个其他专利是WO 03/020851、WO 96/23855、WO98/04656和FR 2772 784 A。
在US2003/0163949中提出,使用大量的甘油缩醛和其醚作为添加剂或用作汽油的配制基料,并导致颗粒排放的显著减少。当暴露于氧气中时,醚倾向于形成不稳定的过氧化物。乙基、异丁基、乙基叔丁基和乙基叔戊基醚在这方面特别危险。
本发明的目的之一是提出一种改进的柴油组合物。特别是,本发明的目的在于提供一种十六烷值更高的组合物,该组合物也具有更好的润滑性能。
本发明的另一个目的是提出一种在较低剂量下产生有效作用的十六烷增效剂(booster)和/或润滑性能改进剂。
本发明的另一个目的是提出至少部分来源于双资源的十六烷增效剂和/或润滑性能改进剂。
发明概述
因此,本发明提出了一种柴油组合物,其包含至少一种柴油燃料和0.01至0.8体积%的至少一种下式I的化合物:
其中
R1和R2,彼此独立地,在下组中选择,该组由以下各项组成:直链或支链C1-C12烷基、C4-C12环烷基或芳基;
R3是H、直链或支链烷基、环烷基或-C(=O)R4基团,其中R4是直链或支链C1-C4烷基或C5-C6环烷基。
本发明还提出使用至少一种根据所有可能的实施例及其组合的上述式I化合物来提高柴油组合物的十六烷值、柴油组合物的润滑性能或柒油组合物的十六烷值和润滑性能。
具体实施方式
本发明的柴油组合物包含至少一种柴油燃料和从0.01至0.8体积%的至少一种下式I的化合物:
其中
R1和R2,彼此独立地,在下组中选择,该组由以下各项组成:直链或支链C1-C12烷基、C4-C12环烷基或芳基;
R3是H、直链或支链烷基、环烷基或-C(=O)R4基团,其中R4是直链或支链C1-C4烷基或C5-C6环烷基。
“0.01-0.8体积%”应理解为该量基于柴油组合物的总体积。
在一个优选实施例中,R1和R2彼此独立地在下组中选择,该组由以下各项组成:甲基、乙基、异丙基、正丙基、异丁基、正丁基、叔丁基、正戊基、环戊基、环己基或苯基。
有利地是,在上式I中,R3是H或-C(=O)R4基团,其中R4是甲基、乙基、异丙基、正丙基、异丁基、正丁基或叔丁基。更优选地R3是H。
一个优选的实施例是当R1和R2是甲基并且R3是H时。在这种情况下,该化合物是例如在名称Clean Multi、SL191或Solketal下可商购的。该化合物可以在众所周知的经典条件下通过在甘油与丙酮之间的反应来合成。
在另一个实施例中,R1是甲基,R2是异丁基且R3是H。在这种情况下,该化合物是例如在名称Clean Plus或Film下可商购的。该化合物可以在众所周知的经典条件下通过在甘油与甲基-异丁基酮之间的反应来合成。
在第三个实施例中,R1是甲基、R2是苯基、R3是H。在这种情况下,该化合物是例如在名称Film HB下可商购的。该化合物可以在众所周知的经典条件下通过在甘油与苯乙酮之间的反应来合成。
另一种可能性是使R1和R2是甲基并且R3是一C(=O)R4基团,其中R4是甲基。在这种情况下,该化合物是例如在名称ACT下可商购的。该化合物可以在众所周知的经典条件下通过Solketal与乙酸烷基酯的酯基转移来合成。
在甘油三酸酯的酯基转移期间,可以作为副产物从生物柴油生产获得甘油。
本发明的式I化合物在应用中具有非常好的性能,低气味且对人体或环境无毒性。另外,因其具有高燃点,使用它们不会引起安全问题。它们是柒油应用中现有十六烷和润滑性能改进剂的可持续替代品,因为它们符合可持续性的三大支柱(经济、环境和社会)。
当两种或更多种式I化合物的共混物用于根据本发明的柴油组合物中时,也是一种有利的实施例。该共混物优选地包含Clean Multi和Clean Plus,重量比约为30∶70至70∶30,甚至更优选为50∶50。另一种有利的共混物包含Clean Plus和ACT,其重量比约为30∶70至70∶30,甚至更优选为60∶40。
在根据本发明的柴油组合物中,特别优选使式I化合物的存在量为柴油组合物总体积的0.05-0.5%。
柴油燃料可以包含石油来源的柴油燃料或源自植物油的烷基酯的混合物。
本发明还提出使用至少一种根据所有可能的实施例及其组合的上述式I化合物来提高柴油组合物的十六烷值、柴油组合物的润滑性能或柴油组合物的十六烷值和润滑性能。
将上述式I化合物引入到汽油和/或植物油酯的混合物中,致使相对于不含所述产物的燃料来说,柴油机燃料可以提高十六烷值和润滑性能。
以下实例以非限制性方式说明本发明。
附图说明
图1至图3相当于十三烷值测量图,作为三种不同柴油燃料添加的SL191的量的函数。这些图涉及实例1至3。
图4、图5和图6分别是润滑性能、十六烷值和硫含量测量图,其作为添加到实例4中描述的柴油燃料中的SL191的量的函数。
实例
测量方法
对于下面的实例,根据下表I所示的标准测量了参数。
表I-测量方法
测试与结果
在添加了Augeo SL191或其他Augeo成分和合理的搅拌时间(大约十分钟)以均化该溶液之后,对包括生物柴油在内的不同类型的柴油的十六烷值和润滑性能结果进行了测量。
实例1:Gazole Biofree EN590
Gazole Biofree EN590也被称为EN590 B0,它是一种超低硫柴油,不含生物成分(生物柴油或FAME=脂肪酸甲酯)。它是一种全球性的交易(traded cut),主要在欧洲市场上销售。下表II列出了其主要规格。
表II
实例1
以下面所示的浓度添加Augeo SL191,并根据已经提到的标准测量十六烷值。下表III列出了所得的结果。
表III
该实例的图表如图1所示。
实例1bis
按下面所示的浓度加入Augeo膜(式I,其中R1是甲基,R2是异丁基,R3是H),并且按照已经提到的标准测定了十六烷值。下面的表IIIbis列出了所得的结果。
表IIIbis
实例1ter
以下面所示的浓度加入Augeo膜HB(式I,其中R1是甲基,R2是苯基,R3是H),并按照已经提到的标准测定十六烷值。下面的表IIIter列出了所得的结果。
表IIIter
实例2:Gazole Biofree US
这种类型的柴油规格在ASTM D975 ULSD中被提及,并且它也没有FAME含量。十六烷值规格最低为40。
以下面所示的浓度添加Augeo SL191,并根据已经提到的标准测量十六烷值。下面的表IV列出了所得的结果。
表IV
这个实例的图表如图2所示。
实例3:生物柴油
生物柴油也被称为FAME、脂肪酸甲酯,并且其规格在标准EN ISO 14214中提及。
以下面所示的浓度添加Augeo SL191,并根据已经提到的标准测量十六烷值。下面的表V列出了所得的结果。
表V
这个实例的图表如图3所示。
实例4:超低硫柴油
这种柴油要求是超低硫含量,并且具体值取决于地区。在美国,限度为15ppm,而在欧洲是10ppm(如EN590所示)。下面的表VI示出了在使用Augeo SL191作为添加剂的情况下,获得这种柴油的结果。
表VI
这个实例的图表如图4、图5和图6所示。
以上结果表明,正如所提出的那样,在非常低的用量下,式I的组分不仅能够改善市场上可得到的不同类型柴油商品的十六烷值,还能改善润滑性能。
Claims (14)
1.一种包含至少一种柴油燃料和从0.01至0.8体积%的至少一种下式I的化合物的柴油组合物:
其中
R1和R2,彼此独立地,在下组中选择,该组由以下各项组成:直链或支链C1-C12烷基、C4-C12环烷基或芳基;
R3是H、直链或支链烷基、环烷基或-C(=O)R4基团,其中R4是直链或支链C1-C4烷基或C5-C6环烷基。
2.根据权利要求1所述的柴油料组合物,其中R1和R2彼此独立地在下组中选择,该组由以下各项组成:甲基、乙基、异丙基、正丙基、异丁基、正丁基、叔丁基、正戊基、环戊基、环己基或苯基。
3.根据权利要求1或2所述的柴油组合物,其中R3是H或-C(=O)R4基团,其中R4是甲基、乙基、异丙基、正丙基、异丁基、正丁基或叔丁基。
4.根据权利要求1至3中任一项所述的柴油组合物,其中R1和R2是甲基并且R3是H。
5.根据权利要求1至3中任一项所述的柴油组合物,其中R1是甲基、R2是异丁基并且R3是H。
6.根据权利要求1至3中任一项所述的柴油组合物,其中R1是甲基、R2是苯基并且R3是H。
7.根据权利要求1至3中任一项所述的柴油组合物,其中R1和R2是甲基并且R3是-C(=O)R4基团,其中R4是甲基。
8.根据权利要求1至7中任一项所述的柴油组合物,其包含两种或更多种具有式I的化合物的共混物。
9.根据权利要求1或2所述的柴油组合物,其中该式I化合物以该柴油组合物总体积的0.05至0.5体积%的量存在。
10.根据权利要求1至4中任一项所述的柴油组合物,其中所述柴油燃料包含石油来源的柴油燃料。
11.根据权利要求1至4中任一项所述的柴油组合物,其中所述柴油燃料包含植物油来源的烷基酯的混合物。
12.至少一种具有下式I的化合物:
其中
R1和R2,彼此独立地,在下组中选择,该组由以下各项组成:直链或支链C1-C12烷基、C4-C12环烷基或芳基;
R3是H、直链或支链烷基、环烷基或-C(=O)R4基团,其中R4是直链或支链烷基或环烷基;
用于提高柴油组合物的十六烷值的用途。
13.至少一种具有下式I的化合物:
其中
R1和R2,彼此独立地,在下组中选择,该组由以下各项组成:直链或支链C1-C12烷基、C4-C12环烷基或芳基;
R3是H、直链或支链烷基、环烷基或-C(=O)R4基团,其中R4是直链或支链烷基或环烷基;
用于提高柴油组合物的润滑性能的用途。
14.至少一种具有下式I的化合物:
其中
R1和R2,彼此独立地,在下组中选择,该组由以下各项组成:直链或支链C1-C12烷基、C4-C12环烷基或芳基;
R3是H、直链或支链烷基、环烷基或-C(=O)R4基团,其中R4是直链或支链烷基或环烷基;
用于提高柴油组合物的十六烷值和润滑性能的用途。
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EP3320058A1 (en) | 2018-05-16 |
UY36769A (es) | 2017-01-31 |
US11072753B2 (en) | 2021-07-27 |
BR112017027944B8 (pt) | 2023-04-18 |
BR112017027944A2 (pt) | 2018-08-28 |
BR112017027944B1 (pt) | 2021-12-07 |
US20180258356A1 (en) | 2018-09-13 |
WO2017006141A1 (en) | 2017-01-12 |
ES2738002T3 (es) | 2020-01-17 |
EP3320058B1 (en) | 2019-04-24 |
AR105273A1 (es) | 2017-09-20 |
WO2017006167A1 (en) | 2017-01-12 |
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