CN104204157A - 生物燃料组合物 - Google Patents

生物燃料组合物 Download PDF

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CN104204157A
CN104204157A CN201380003836.0A CN201380003836A CN104204157A CN 104204157 A CN104204157 A CN 104204157A CN 201380003836 A CN201380003836 A CN 201380003836A CN 104204157 A CN104204157 A CN 104204157A
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叶夫根尼·瓦连京诺维奇·潘捷列夫
加林娜·维克托罗芙娜·潘捷列瓦
帕维尔·叶夫根尼耶维奇·潘捷列夫
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Abstract

本发明涉及用于柴油燃料的生物添加剂。要求保护基于石油产品的生物燃料组合物，包含基于缩醛和植物油的添加剂，其特征在于，该生物燃料组合物是按体积计98-60％的石油柴油燃料和按体积计2-40％的生物添加剂2的混合物。使用燃料组合物使得增加了燃烧过程的效率、增大了发动功率并减少了从发动机的排放。

Description

生物燃料组合物
技术领域
本发明涉及柴油燃料，并且可以作为发动机燃料用在国民经济中，与石油发动机燃料具有等效的物理和化学特性。
背景技术
目前为柴油发动机使用的燃料主要包括原油组分。对于柴油发动机需要高质量的燃料组成，包含生物来源的组分，这也满足在任何温度操作柴油燃料的质量要求。此外，燃料必须是环境无害的。目前，燃料中最常见的生物来源组分是油菜籽甲基醚，指定为RME(RU2393209)。RME以其本身或以与其他燃料的混合物使用。RME的缺点是其与柴油燃料差的混溶性，并且与传统柴油相比(EN590)，尤其是在低温下，其在低温下差的储存稳定性和差的性能。此外，它会导致发动机污染并增加氮氧化物(NOx)的排放。ITR生产有副产物(甘油)，当生产大量的产品时，这可能是个问题。类似地，也可以制备其他植物油的醚和脂肪酸甲基醚，俗称FAME(脂肪酸甲基醚)。这种FAME可以用于与油菜籽甲基醚相同的应用中，但它们对柴油燃料的质量也具有负面影响，特别是关于在低温下的性能，此外，在燃油中的使用它们增加了氮氧化物的排放。在某些情况下，FAME和RME导致更高的颗粒排放和当启动冷机时形成烟雾。
申请WO2001012581描述了用于生产用作生物柴油的甲基醚的方法，其中脂肪酸和甘油三酯的混合物在一个阶段中被醚化。在该方法中，在温度低于溶液的沸点时，形成了脂肪酸、甘油三酯、醇、酸催化剂和普通溶剂的溶液。以提供单相的量使用共溶剂(助溶剂，co-solvent)；然后保持所述溶液足够时间以提供酸催化的脂肪酸的醚化。在此之后，中和酸催化剂，并加入碱性催化剂用于甘油三酯的醚交换(transetherification)，最后，从溶液中回收醚。以这种方式，制得具有按重量计至少0.4％的甘油含量的含醚的生物燃料。
缺点是复杂性、多阶段过程和产品的高成本。
据了解，为了提高十六烷值，基于石油馏分和凝析气(gas condensate)的柴油燃料，包括为燃烧促进剂的添加剂，如有机硝酸盐。(美国专利号US4,473,378，C10L1/22，1984)
然而，这些添加剂并不保证提高夏季柴油燃料在低温下的起动性。此外，尾气含有大量的氮氧化物。在实践中已成功地证明在燃料中加入含氧化合物，如醇类和简单醚类。
WO81/00721描述了通过添加醇类、水、简单醚类和植物油改性的燃料混合物。使用甘油的这些简单醚类的目的是消除亲水性，并降低沸点至燃料组分的沸点的示意图所在的范围，并减少密度而同时保持十六烷值。
甘油的简单醚的缺点在于，当生产它们时，至多形成含11％的三醚的混合物。剩余量为单醚和二醚，由于仍然存在羟基，它们部分地溶于单独燃料组分中。
已知石油柴油燃料，以按重量计％含有添加剂：烷基(C3-C18)硝酸盐75-90，腐蚀组分(corrosion component)5-15，和蒸发范围120-2700S的烃馏分，上达至100。(专利RF2355732)。然而，柴油燃料包括昂贵的组分，这增加了成本，并且多步方法(multi-stage process)增加了氮氧化物的形成。
最接近于所要求的发明的是在I.S.Khusnutdinov等人的文章中描述的工作(Chemistry and Chemical Engineering,2009,Volume52,no.11,page119)“关于二乙氧基乙烷的研究1.1，作为柴油燃料的组分。”("Research1.1on diethoxyethane,as a component of diesel fuel.")
在此文件中，已经研究了二乙氧基乙烷与柴油和菜籽油的组合物1.1，并且已经与柴油燃料的GOST305-82的要求相比确定了它们的主要性能指标。
该溶液的缺点是二乙氧基乙烷和基于它的组合物的低十六烷值1.1，不超过46分，这不符合新的GOST R53605-2009的要求(EN14214:2003)。
发明内容
本发明的目的是提供一种包含生物添加剂的柴油燃料至石油柴油燃料，具有高十六烷值，其中，随着提高的柴油燃料的低温性能和起动性，阻碍了腐蚀过程，不用翻新发动机而使用，并具有生态可行的(ecologically-sound)排放，同时由于使用的组分尤其是添加剂(基于由国内自然资源、包括可再生的资源提供的低成本大吨位的可用产品)显著降低了成本。
本发明的技术结果是提供一种具有低成本和高产品产量的高品质柴油燃料，对应于当前GOST，以及高技术有效性的生产和广泛的资源基础。
使用燃料组合物使得在发动机运行期间增加了燃烧过程的效率、增加了发动机功率并降低了发动机加速时间。此外，该产品可以用于减少发动机的排放、提高在寒冷中的流动性并增加十六烷值。
通过生物燃料组合物实现了所述效果，该生物燃料组合物是石油柴油燃料(按体积计98-60％)和生物燃料(按体积计2-40％)的混合物，其中，反过来，由二乙基甲缩醛(dietilformal)(1.1二乙氧基甲烷)，(按体积计35-40％)和不饱和脂肪酸的甘油酯(按体积计65-60％)组成。任何植物油都可以用作甘油酯。
具体实施方式
众所周知，利用植物油测试柴油机的发动机。但植物油具有高粘度、高浇注点(pouring point)，并且因为这个原因，世界上通常使用甲基醚油。油的醚交换过程的部分占高达30％的成本，并且其中使用碱并形成了副产物。
当一起使用二乙基甲缩醛和不饱和脂肪酸的甘油酯(简单混合)时，提高了对生物柴油的欧洲标准EN14214中的11个指标。通过应用乙醇和甲醛缩合的已知方法(Himik.ru.化工百科全书(Himik.ru.ChemicalEncyclopedia))，并且通过甲醇从甲烷中得到甲醛(ru.wikipedia.org.甲醇，甲醛(ru.wikipedia.org.Methanol,formaldehyde))，二乙基甲缩醛-生物燃料可以容易地获自可再生能源生物乙醇和生物气。
以与不饱和脂肪酸的甘油酯(如植物油，以35-40％(按体积计)的量)的混合物使用二乙基甲缩醛，允许获得具有高十六烷值的生物燃料，其特征符合俄罗斯标准GOST R53605-2009、欧洲标准EN14214-2003和美国标准ASTMD6751。这样消除了对油与甲醇的醚交换的需要，醚交换占30％的成本，并消除处理副产物(甘油和废碱催化剂)的需要。
(生物燃料、乙醇和生物柴油的市场的市场研究，2012年5月18，Research Techart，第54页，(Marketing research of the market of biofuel,ethanol and biodiesel,May18,2012Research Techart,page54))。更好地利用植物再生原料一般对环境是有利的。
表1
生物柴油的一个重要参数是其保质期，这是非常小的而且受油中的高碘值和不饱和化合物的量的限制。当用二乙基甲缩醛稀释油时，碘值降低并且生物燃料变得更耐氧化、聚合过程，等。
在室温下混合组分，并在认证的实验室根据GOST进行分析。根据标准方法在可比较的条件下获得植物油的甲基醚。
与植物油混合的DEP浓度对生物柴油组合物的密度、粘度和碘值的影响示于表1。
表2
样品号 组合物配方 十六烷值，点
1 柴油燃料+20％(菜籽油+40％DEP) 54.0
2 柴油+30％(菜籽油+40％DEP) 54.0
3 柴油+40％(菜籽油+40％DEP) 54.0
4 柴油+20％油菜籽柴油 53.8
5 柴油+20％(棕榈油+40％DEP) 54.0
6 柴油+20％棕榈柴油 53.0
7 柴油EKTO+20％(葵花籽油+40％DEP) 53.8
8 柴油+20％葵花籽柴油 53.0
结论
1.对于二乙基甲缩醛的浓度等于按体积计30％和植物油的浓度等于按体积计70％，粘度的指标不符合标准，但碘值是令人满意的，除棕榈油和亚麻籽油之外，它们符合密度指标(0.900)。
2.对于二乙基甲缩醛的浓度等于35％和植物油的浓度等于65％，所有指标符合美国标准ASTMD6751，但对粘度(5.0)而言，它们不符合EN14214-欧洲标准和俄罗斯GOST R53605-2009。
3.对于二乙基甲缩醛的浓度等于40％和植物油的浓度等于60％，所有指标符合国际标准。
表2示出了甲基醚，DEP和油的混合物在生物柴油和柴油燃料的混合物的十六烷值上的比较。
结论
在发明人的实验中，油和二乙基甲缩醛的混合物总是具有稍微高于给定油的甲基醚的十六烷值。差异并不显著，但这使得可能主张油与甲醇的醚交换经济上并不可行，因为费用的部分占30％甚至更多的成本，形成了一些应处理掉的副产物(甘油和碱)。

Claims (3)

1.一种基于石油产品的生物燃料组合物，包含基于缩醛和植物油的添加剂，其特征在于，所述生物燃料组合物是按体积计98-60％的石油柴油燃料和按体积计2-40％的生物添加剂2的混合物。
2.根据权利要求1所述的基于石油产品的生物燃料组合物，其特征在于，所述生物添加剂包含按体积计35-40％的二乙基甲缩醛和按体积计60-65％的不饱和脂肪酸的甘油酯。
3.根据权利要求2所述的基于石油产品的生物燃料组合物，其特征在于，任何植物油用作不饱和脂肪酸的甘油酯。
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CN104204157B (zh) 2016-12-14
WO2014077731A1 (en) 2014-05-22

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