CN1526005B - 燃料组合物 - Google Patents

燃料组合物 Download PDF

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CN1526005B
CN1526005B CN018218369A CN01821836A CN1526005B CN 1526005 B CN1526005 B CN 1526005B CN 018218369 A CN018218369 A CN 018218369A CN 01821836 A CN01821836 A CN 01821836A CN 1526005 B CN1526005 B CN 1526005B
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fuel composition
fuel
volume
composition
additive
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CN1526005A (zh
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F·邦加特
W·霍奇森
A·雷
J·雷德
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02 diesel engine Europe Ltd
BASF Personal Care and Nutrition GmbH
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Cognis Deutschland GmbH and Co KG
AAE Technologies International PLC
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Abstract

本发明描述了一种燃料组合物，其基本上没有烷氧基化化合物且基本上没有具有至少6个C原子的长链烷基醇，且包含至少95％体积烃基燃料和0.1-5％体积的式(I)的添加剂；R-CO-NR1R2(I)，其中R是具有6-21个C原子的饱和或不饱和、线性或支化烷基基团；且R1和R2可相同或不同，分别表示具有1-4原子的羟基烷基基团。

Description

燃料组合物
本发明涉及包含链烷醇酰胺作为添加剂的柴油/醇混合物。
本发明另外涉及一种用于制备柴油/醇混合物的方法和所选各个组分作为增溶剂用于含醇柴油燃料的用途。
表面活性剂作为添加剂用于燃料的用途是长期已知的。因此，例如，英国专利GB 2 21 72 29描述了一种包含4 8体积份乙氧基化醇，3-8份月桂酸二乙醇酰胺，3-8份油酸二乙醇酰胺和1.5-4份乙氧基化油酸的添加剂。这种组合物适用作使水溶解在燃料中并因此减少腐蚀的添加剂。但在例如短链醇代替水用作燃料的混合相时出现问题。为此，WO98/17745描述了一种包含25％体积二乙醇酰胺，50％体积乙氧基化醇和25％体积的7mol乙氧基化的C14脂肪酸的替代组合物。该添加剂用于提高醇在乙醇中的溶解度，这最终导致CO2和CO和NOx排放的下降。
过去，缺点在于，必须使用许多单独的物质以获得所需作用。过去，需要通过使用尽可能简单的经济添加剂来实现乙醇在燃料，优选在柴油中的溶解，以由此获得燃料燃烧的气态反应产物，尤其是NOx和CO或CO2的明显下降。
本申请的一个目的是解决上述问题。
现已惊人地发现，乙醇在燃料，优选在柴油中的充分溶解可以通过使用所选各个组分而实现。
根据本发明的第一方面，我们提供了一种燃料组合物，它基本上没有烷氧基化化合物且基本上没有具有至少6个C原子的长链烷基醇，并包含至少95％体积烃基燃料和0.1-5％体积的式(I)添加剂；
R-CO-NR1R2  (I)
其中R是具有6-21个C原子的饱和或不饱和、线性或支化烷基基团；和
R1和R2可相同或不同，分别表示具有1-4个C原子的羟烷基基团。
在本申请的范围中，燃料理解为是指其自由燃烧能转化成机械功的所有的供能操作材料。这些包括所有种类的在室温和大气压下为液体的发动机和航空燃料。例如用于小汽车或卡车发动机的发动机燃料通常包含烃，如汽油级分或更高沸点矿物油级分。柴油燃料得自裂解的粗柴油或得自在褐煤或硬煤的低温碳化时得到的焦油。常规产物的密度在0.83和0.88g/cm3之间，沸点在170和360℃之间且闪点在70和100℃之间。优选地，根据本发明的燃料包含柴油或由柴油组成。它们还包括所谓的生物柴油，即脂肪酸甲酯，优选菜籽油脂肪酸的甲酯。
根据本发明的燃料的区别特征在于，它们仅包含选自式(I)化合物的单一组分并因此无需不同的各个物质的昂贵和复杂的混合物。特别排除的是从已有技术，如以上引用的WO 98/17745中得知的烷氧基化化合物和长链烷基醇。
优选选择添加剂组分，使得其HLB值低于12。该值计算如下：
HLB＝亲水链的分子体积×20/总分子体积。
在本发明的另一方面，以上描述的燃料组合物可包括一种烃基燃料，该燃料包括一定量的氧合剂，如一种或多种醇。这种醇优选为C1-C6链烷醇，如丙醇，丁醇或乙醇，和其异构体。最优选的醇是乙醇。在这种组合物中，醇的存在量可以是该组合物体积的1-10％。
按照本发明的燃料组合物可通过将燃料添加剂与燃料/乙醇混合物混合而制成。优选的燃料组合物是其中燃料如石油柴油与添加剂的体积比(v/v)范围是1000∶0.5-1000∶50，和优选1000∶1-1000∶50的那些。
本发明的一个优选的实施方案是一种由88-98.9％体积柴油，1-10％体积醇，如乙醇，和0.1-2％体积根据以上描述的添加剂组成的燃料组合物。
根据本发明的添加剂的应用使得有可能以一种经济的方式制备出燃料与醇，如乙醇，优选石油柴油与乙醇的混合物。优选地，将最大0.5-2.0％体积的添加剂加入柴油/乙醇混合物。也可存在水。特别优选使用优选包含低于0.5％体积水的基本上无水的乙醇。另外，总燃料组合物优选为无水的，即水含量应该低于0.2％体积，优选低于0.1％体积。
本发明的另一方面涉及一种由90-98.5％体积柴油，1-8％体积醇，如乙醇，和0.5-2％体积的式I的添加剂组成的燃料组合物。
对于燃料，乙醇可由化石燃料原料或通过衍生自谷物或其它生物燃料材料的糖的发酵而制成。因此，适用于本发明燃料组合物的乙醇可以是衍生自淀粉基糖的酵母或细菌发酵的燃料级乙醇。这种淀粉基糖可从谷类、甘蔗、木薯淀粉和糖用甜菜中提取。或者，燃料级乙醇可通过已知的稀和/或浓酸和/或例如来自废工业源(包括，市政固体废物，废纸，纸泥，锯屑的纤维素部分)的特殊生物燃料的酶水解而制成。生物燃料也可从包括例如稻壳和造纸厂污泥的农业废物收集物。
适用于本发明的燃料级乙醇可不含或仅包含污染物水平的水。应该指出，包含例如乙醇的燃料可包含痕量水。因此，例如，无水乙醇一般包含最高0.5％w/w水。因此，以下提及的无水燃料组合物应该理解为一种基本上没有水，但可包含例如最高0.5％w/w水的组合物。或者，适用于本发明的燃料级乙醇可包含较高量的水，最高5％w/w(含水乙醇)。
乙醇与柴油燃料的结合使用以前产生问题，其中乙醇/柴油燃料混合物不理想地分离成两个不同的相，尤其是当存在水时，并使得所得混合物不适用作可燃燃料。本发明燃料添加剂的应用使得含水乙醇能够令人满意地与常规柴油燃料共混而没有形成两相。按照本发明共混的燃料级乙醇的应用向总体燃料组合物提供理想的燃烧特性；如改进的燃料稳定性，较低烟和特殊物质，较低CO和NOx排放，改进的抗爆性质，和/或改进的抗冷冻特性。
本发明添加剂的存在保证燃料组合物形成一种持续稳定的匀质组合物并同时产生单层，其结果导致较好的更完全的燃烧，减少污染和增加每加仑的英里数。
由于共混燃料的结果，尤其是醇基燃料，能够以较冷的装料更精确地燃烧，减少通常可归因于发动机性能降低的来自醛过酸和过氧化物反应的甲酸铁。
我们进一步提供一种运转内燃机的方法，包括使用本发明的燃料组合物。
特别优选使用优选包含低于0.5％体积水的基本上无水的乙醇。另外，总燃料组合物优选为无水的，即水含量应该低于0.2％体积，优选低于0.1％体积。
国际专利申请No.WO99/35215(Wenzel)描述了一种用于可燃燃料的添加剂，包括氮源如脲。尽管该添加剂据说减少NOx，但该组合物非常复杂且包括许多成分，包括：水溶性醇，C6-C12醇，C6-C18乙氧基化醇，C10-C24脂肪酸，和氮源。
现已惊人地发现，本发明的燃料组合物在与含氮化合物如脲结合时可包含非常低的燃料∶添加剂比率。
因此根据本发明，我们提供了一种上述的燃料组合物和氮源。
氮化合物可选自氨，肼，烷基肼，二烷基肼，脲，乙醇胺，单烷基乙醇胺，和二烷基乙醇胺，其中烷基独立地选自甲基，乙基，正丙基或异丙基。脲是优选的。氮化合物可以是无水化合物或含水化合物，如水溶液，且可以是最高5％w/w水溶液。
根据本发明的另一特点，我们提供了一种将氮化合物在燃料组合物中增溶的方法，其包括混合以上描述的烃燃料组合物和氮化合物。本发明的方法可任选地包括加入水，正如以上所述。
我们也提供了氮化合物在制造本发明这一方面的燃料组合物中的用途。我们尤其提供了脲在制造本发明燃料组合物中的用途。
在本发明这一方面的燃料组合物中，氮化合物可通过掺入到燃料添加剂中而加入或可单独加入。另外，氮化合物可作为水溶液加入。
本发明的燃料组合物也可任选地包含十六烷值促进剂，其量是基于混合物体积的0.1％v/v-1.0％v/v。如果十六烷值促进剂包括在本发明的燃料组合物中，它可作为本发明燃料添加剂的一部分而加入或可单独加入。
适用于该混合物的十六烷值促进剂选自：硝酸-2-乙基己酯，过氧化叔丁基，二甘醇甲基醚，环己醇，和其混合物。十六烷值促进剂在混合物中的存在量取决于特定柴油燃料的十六烷值和存在于特定燃料组合物中的乙醇的量。一般，柴油燃料十六烷值越低，则十六烷值促进剂的量越高，类似地，因为乙醇通常用作十六烷抑制剂，所以乙醇在溶液中的浓度越高，则该混合物中需要越多的十六烷值促进剂。
本发明的燃料添加剂的优点尤其在于，它们比已有技术添加剂更有效地产生微乳液。因此，它们能够用烃燃料，如柴油/乙醇，甚至在水的存在下更有效地生产稳定的、透明和匀质溶液。因此，根据本发明的另一特点，我们提供了一种上述的燃料组合物，它任选地包括一定量的水，且其中燃料由基本上稳定的、透明和基本上均相的溶液组成。
另外，本发明的燃料添加剂或燃料组合物也可任选地包括反乳化剂，其量基于混合物体积计低于5％v/v和优选低于1％v/v。
添加剂的作用要理解为它们具有增溶作用。因此，还要求保护该燃料添加剂作为增溶剂用于含乙醇的柴油燃料的用途。
根据本发明的另一方面，我们提供了一种式I的化合物在制造以上描述的燃料组合物中的用途。
根据本发明的另一方面，以上描述的燃料组合物包含其主要部分是生物柴油的柴油。
式(I)的化合物是酰胺，其可通过羟烷基胺和羧酸之间的已知反应而得到。这种链烷醇酰胺和其性质例如描述于Handbook ofSurfactants(表面活性剂手册)，M.R.Porter，Chapman和Hall，1991，页数135-139。所引用的出版物的公开内容也是本申请的一部分。由于合成，除了式(I)的化合物，在商业使用的产品中通常存在副产物，优选游离的羟基胺。根据本发明的教导，可以存在根据DGF H-VI 4b测定的基于添加剂量计最高5％体积的游离胺。另外，少量的游离脂肪酸可由于生产结果而存在于添加剂中。根据DGF H-VI 4a测定的其量基于添加剂计不超过1％体积。式(I)的化合物由申请人以商品名出售。
其中基团R1和R2是相同的并表示羟基烷基基团、优选乙基基团的那些式(I)化合物是尤其优选的。另外，有利的是如果基团R具有11-21个C原子。油酸二乙醇酰胺(R这时对应于具有17个C原子的单不饱和烷基基团)作为添加剂的应用是尤其优选的。式(I)的化合物可以纯形式或作为不同的异构体的混合物使用。后者在优选使用的工业级中是常见的。在此，例如，存在包含过量油酸二乙醇酰胺和式(I)的其它化合物的异构体混合物，式(I)中R1和R2分别表示羟基烷基基团，且R表示具有11-13个C原子的烷基基团。
添加剂的作用要理解为它们具有增溶作用。因此，还要求保护根据式(I)的化合物作为增溶剂用于含乙醇的柴油燃料的用途。
因此我们进一步提供了式I的化合物在制造上述燃料组合物中的用途。
本发明现仅通过实施例描述。
实施例1
根据本发明的添加剂的作用根据EN 116：1997通过冷滤堵塞点试验(CFPP)而测试。
根据该试验方法，为此将含添加剂的燃料逐步冷却至-30C，在每种情况下在1℃温度间隔下取样并在2kPa减压下吸过标准化过滤器装置。所述温度值因此对应于燃料在给定时间内不能再流过过滤器装置时的温度。对于根据本发明的化合物，它们所增溶的乙醇和柴油的共混物具有类似于没有添加剂的柴油的CFPP值。
实施例2
在用于增溶含水乙醇(7.7％v/v)与柴油(92.3％v/v)的燃料共混物时，对油酸二乙醇酰胺和其组成属现有技术的添加剂的增溶效率进行比较。
现有技术添加剂包含25％v/v二乙醇酰胺，50％v/v乙氧基化醇和25％v/v用7摩尔EO乙氧基化的C14脂肪酸。实验上，所制成的乙醇/柴油共混物包含以体积确定的含量最高0.6％v/v的水和产生透明的稳定溶液所需量的添加剂。
将增溶比率，即现有技术添加剂的体积除以本发明添加剂的体积相对水含量作图(参见图1)。
结果证实链烷醇酰胺尤其在低水浓度下明显更加有效。

Claims (24)

1.一种燃料组合物，其基本上没有烷氧基化化合物且基本上没有具有至少6个C原子的长链烷基醇，并包含至少95％体积的包括柴油的烃基燃料和0.1-5％体积式(I)的添加剂；
R-CO-NR1R2(I)
其中R是具有6-21个C原子的饱和或不饱和、线性或支化烷基基团；和
R1和R2可相同或不同，分别表示具有1-4个C原子的羟基烷基基团，特征在于该燃料组合物含有不超过0.5％w/w的水。
2.根据权利要求1的燃料组合物，特征在于所述燃料包含1-10体积％的氧合剂，该氧合剂为含有低于0.5体积％水的基本无水的乙醇。
3.根据权利要求1的燃料组合物，特征在于所述基团R1和R2是相同的且分别表示羟基烷基基团。
4.根据权利要求3的燃料组合物，特征在于所述基团R1和R2是相同的且分别表示羟基乙基基团。
5.根据权利要求1的燃料组合物，特征在于所述基团R具有11-21个C原子。
6.根据权利要求1的燃料组合物，特征在于所述式I的化合物是油酸二乙醇酰胺。
7.根据权利要求1的燃料组合物，特征在于所述添加剂组分的HLB值低于12。
8.根据权利要求1的燃料组合物，特征在于燃料与添加剂的体积比(v/v)范围是1000∶0.5-1000∶50。
9.根据权利要求1的燃料组合物，特征在于燃料与添加剂的体积比(v/v)范围是1000∶1-1000∶50。
10.根据权利要求1的燃料组合物，特征在于该燃料组合物由85-98.9％体积柴油、1-10％体积醇和0.1-5％体积式I的添加剂组成。
11.根据权利要求1的燃料组合物，特征在于该燃料组合物由89-94.5％体积柴油、5-8％体积醇和0.5-3％体积添加剂组成。
12.根据权利要求1的燃料组合物，特征在于所述柴油包括石油柴油。
13.根据权利要求1的燃料组合物，特征在于所述柴油包括生物柴油。
14.根据权利要求1的燃料组合物，特征在于水含量低于0.2体积％。
15.根据权利要求1的燃料组合物，特征在于该组合物包含附加的氮源，且所述氮源选自氨、肼、烷基肼、二烷基肼、脲、乙醇胺、单烷基乙醇胺和二烷基乙醇胺，其中烷基独立地选自甲基、乙基、正丙基或异丙基。
16.根据权利要求1的燃料组合物，特征在于该组合物还包含十六烷值促进剂，其量基于混合物体积计为0.1％v/v-1.0％v/v。
17.根据权利要求16的燃料组合物，特征在于所述十六烷值促进剂选自硝酸-2-乙基己酯、过氧化叔丁基、二甘醇甲基醚、环己醇和它们的混合物。
18.根据权利要求1的燃料组合物，特征在于所述燃料由稳定的、透明和均相的溶液组成。
19.根据权利要求1的燃料组合物，特征在于该组合物包括其量低于5％v/v的反乳化剂。
20.根据权利要求1的燃料组合物，特征在于R是具有6-21个C原子的线性或支化不饱和的烷基基团。
21.一种增溶燃料组合物中的氮源的方法，包括混合根据权利要求1的烃燃料组合物和氨源，特征在于所述氮源选自氨、肼、烷基肼、二烷基肼、脲、乙醇胺、单烷基乙醇胺和二烷基乙醇胺，其中烷基独立地选自甲基、乙基、正丙基或异丙基。
22.一种用于制备根据权利要求1的燃料组合物的方法，其包括将其量为0.1-5％体积的添加剂与柴油混合并将该混合物喷溅共混成透明的稳定燃料。
23.式(I)的化合物作为增溶剂用于含无水的醇的柴油燃料的用途。
24.一种运行内燃机的方法，包括使用根据权利要求1的燃料组合物。
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GB0027274D0 (en) 2000-12-27
WO2002038707A2 (en) 2002-05-16
WO2002038707A3 (en) 2003-01-30
JP4216591B2 (ja) 2009-01-28
CA2433464C (en) 2008-08-12
ATE327302T1 (de) 2006-06-15
HK1059797A1 (en) 2004-07-16
MXPA03004053A (es) 2005-04-11
US20040040202A1 (en) 2004-03-04
BR0115205A (pt) 2004-02-03
EP1334171B8 (en) 2006-08-23
JP2004520453A (ja) 2004-07-08
AU2002223787B2 (en) 2006-08-03
DE60119964T8 (de) 2007-05-31

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