CN101747996A - 改进油组合物的方法 - Google Patents
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Abstract
一种改善含有从植物或动物材料中衍生的脂肪酸烷基酯的油的低温性质的方法,其中至少5%脂肪酸烷基酯衍生自C16-C22饱和脂肪酸。该方法包括至少一部分所述油与聚亚烷基多胺或同时带有聚亚烷基亚胺取代基和至少一个伯胺基团的咪唑啉反应。
Description
本申请涉及一种对从植物或动物材料获得的油的低温性能进行改进的方法。
越来越多的由植物或动物获得的油被作为燃料应用,特别是,作为石油衍生的中间馏分燃料如柴油的部分或全部替代品。一般来说,上述燃料被认为“生物燃料”或“生物柴油”。生物燃料可由很多来源获得。其中最常见的是由植物比如油菜籽、葵花籽等中提取的脂肪酸的烷基酯,通常是甲基酯。这种类型的燃料通常被称为FAME(fatty acid methyl ester,脂肪酸甲酯)。
存在环境上的驱动力以鼓励使用此类燃料,因为其来自可再生资源。同时,也存在着燃烧时生物燃料产生的污染比相当量的石油衍生燃料少的迹象。
由植物或动物材料获得的燃料油含有这样的组分,例如正链烷酸甲酯,所述组分在低温下易于沉淀为大的、片状的晶体,或者形成球状的蜡并因此形成凝胶的结构,这样会导致燃料失去流动性。燃料仍然能够流动的最低温度即为倾点。
随着燃料温度的降低并达到倾点,通过管线和泵来运输燃料的难度增大。此外,在温度高于倾点时,晶体的蜡容易堵塞燃料管线、滤网和过滤器。本领域对这些问题已经有了充分的了解,已经提出了多种添加剂,其中很多已经被商用,来降低燃料油的倾点,包括用于从石油中和从植物或动物材料中获得的燃料油。类似的,还提出了其他添加剂并且商用用于减小形成的蜡的晶体的尺寸和改变其形状。由于不容易堵塞过滤器,因此期望尺寸更小的晶体。特定的添加剂可以阻止蜡结晶成片晶的倾向,代之以形成针状的形态。与片晶相比,所获得的针相对更容易通过过滤器;或者在过滤器上生成多孔的晶体层。这些添加剂还可以使晶体蜡在燃料中保持悬浮状态,减缓了沉降并因此帮助阻止堵塞。
由植物或动物材料获得的油的低温性质很大程度上是由油中饱和脂肪酸的含量、特别是存在的C16-C22饱和脂肪酸的比例决定的。最成问题的是上述酸的甲酯和乙酯。在脂肪酸酯混合物中的物质结晶出来的温度或之下对上述油进行运输和操作时很困难的。含有很少量饱和脂肪酸酯的油有时可以通过传统添加剂处理成功改善其低温性质。但是,已经发现传统的添加剂对含有甚至相对低含量的特别是衍生自棕榈酸和硬脂酸的酯的油没有作用。
尽管存在上述这些问题,仍需要利用由植物或动物材料获得的含有C16-C22饱和脂肪酸的油。这是由于这些油是由相对便宜和丰富的资源获得。本发明提供了一种这些油在低温下运输和操作问题的解决方法。
根据本发明,提供了一种改善由植物或动物材料获得的含有脂肪酸烷基酯的油的低温性质的方法,其中至少5重量%的脂肪酸烷基酯为C16-C22饱和脂肪酸的酯,该方法包括将至少一部分油与至少一种具有3个或更多个氮原子的化合物反应,其中至少一个氮原子以伯胺的形式存在;其中至少一种具有3个或更多个氮原子的化合物含有聚亚烷基多胺或咪唑啉化合物,其带有聚亚烷基亚胺取代基和至少一个伯胺基团。
在本发明的上下文中,关于油的低温性质的改善可包括对倾点、浊点、冷滤堵塞点(CFPP)或其他操作性测试中的改善中的一项或多项。本领域技术人员熟知合适的测试。优选低温性质的改善包括对倾点和/或对CFPP的改善。
不希望受到任何理论限制,应认为对各种类型的使得低温性能变差的脂肪酸酯的混合物进行酰胺化,提供了可有效改善含有大量这些酯的油的低温性质的“添加剂”。该“添加剂”是通过将含有3个或更多氮原子的化合物直接与含有成问题的饱和脂肪酸衍生的酯原位反应制得的。如本领域所熟知的,例如甲酯和胺形成酰胺的反应是很容易进行的。
与具有3个或更多个氮原子的化合物反应的油的比例优选为以油重量计0.05-10重量%,更为优选为0.05-2重量%,例如0.05-1重量%。
一旦油与具有3个或更多个氮原子的化合物反应后,可以独立的使用,例如,作为纯生物燃料,或以任何比例与石油衍生油混合使用。
在一个优选实施方式中,使用了至少一种额外的脂肪酸。优选使用脂肪酸的混合物,例如,由植物或动物材料获得的脂肪酸的混合物。所述至少一种的脂肪酸与油和至少一种具有3个或更多个氮原子的化合物一同反应,或者加入油中。所述至少一种脂肪酸和所述至少一种具有3个或更多个氮原子的化合物可按任意顺序加入油中。
通过使用至少一种脂肪酸,可更进一步改善由植物或动物材料获得的含有至少5重量%的衍生自C16-C22饱和脂肪酸酯的脂肪酸烷基酯的油的低温性质。
所期待的是具有3个或更多个氮原子的化合物中的一个(或多个,如果存在的话)伯胺基团与脂肪酸烷基酯反应以形成酰胺。如上所述,该反应是有利的,并且可以通过温和的加热来促进。化合物上其他的氮原子可为,例如,仲胺或叔胺。由上述胺基团生成的酰胺较不优选,因此认为其在脂肪酸烷基酯存在下保持不反应。目前认为加入脂肪酸会促进一个或多个其他氮原子生产盐。
下面将详细描述本发明的各种性质。
脂肪酸烷基酯的混合物
脂肪酸烷基酯混合物中至少5重量%衍生自C16-C22饱和脂肪酸。优选至少10%,更为优选至少20%,更为优选至少30%的脂肪酸烷基酯混合物衍生自C16-C22饱和脂肪酸。优选为甲酯或乙酯,特别是甲酯。
在一个优选实施方式中,衍生自C16-C22饱和脂肪酸的脂肪酸烷基酯包括棕榈酸甲酯、硬脂酸甲酯,或者其混合物。
优选衍生自C16-C22饱和脂肪酸的脂肪酸烷基酯的混合物的量不超过60重量%。脂肪酸酯混合物中剩余物的大部分优选包括衍生自不饱和脂肪酸的那些。
合适的材料的非限定性例子包括棕榈油甲酯(PME)、豆油甲酯(SME)和菜籽油甲酯(RME)。还适合的有由不同来源获得的材料的混合物,例如,PME和菜籽油甲酯(RME)的混合物或类似的混合物。
具有3个或更多个氮原子的化合物
与油反应的化合物具有至少3个氮原子。这些氮原子中的至少一个以伯胺的形式存在。
在一个实施方式中,具有3个或更多个氮原子的化合物为(i)聚亚烷基多胺。
合适的为那些包含通过亚烷基桥连接的胺氮的物质,其中胺氮可为伯、仲和/或叔,前提是至少一个胺氮为伯胺基团。多胺可为直链,其中所有的胺基团均为伯或仲基团,或者可含有环状或支化部分或者两者均含有,在该情形下,也存在叔胺基团,再次地,前提是至少一个胺氮为伯胺基团。在一个分子之内亚烷基基团可为相同或不同。优选亚乙基或亚丙基,最为优选亚乙基。
合适的聚亚烷基多胺的非限定性例子包括二亚乙基三胺(DETA)、三亚乙基四胺(TETA)、四亚乙基五胺(TEPA)、五亚乙基六胺(PEHA)和类似的同系物。通常具有5个或更多个氮原子的聚亚烷基多胺优于具有4个或更少个氮原子的聚亚烷基多胺。
聚亚烷基多胺的混合物也是合适的。如本领域所知,可以容易的得到这些材料,并且这些材料含有各种尺寸的聚亚烷基多胺。其通常被称为PAM。其可通过组分中每分子含有的平均氮原子数来定义,该平均氮原子数优选每分子5-8.5,更有优选6.8-8,例如6.8-7.5个氮。较重的材料,所谓的HPAM,也是合适的,比如含有每分子平均7和8个,以及任选的9个氮原子的多胺的胺混合物。
在另一个实施方式中,具有3个或更多个氮原子的化合物为:(ii)同时带有聚亚烷基亚胺取代基和至少一个伯胺基团的咪唑啉化合物。该化合物可通过例如将脂肪酸或脂肪酸(例如硬脂酸或棕榈酸)的甲酯与聚亚烷基多胺,比如TETA、TEPA、PEHA、PAM和类似物反应制得。
脂肪酸
优选的脂肪酸为具有16-20个碳原子的不饱和脂肪酸。特别优选C18不饱和酸,比如油酸、亚油酸和亚麻酸。所述酸可作为纯组分使用,但优选使用由植物或动物材料获得的脂肪酸的混合物。例如由油菜籽油、妥尔油、芫荽油、大豆油、棉籽油、向日葵油、蓖麻油、橄榄油、花生油、玉米油、杏仁油、棕榈仁油、椰子油、芥末籽油、麻风树油、牛脂和鱼油获得的脂肪酸的混合物。更多的例子包括由玉米、黄麻、芝麻、牛油树果、花生和亚麻籽油衍生的油,并且可以由现有技术中已知的方法由此衍生。具有高C18不饱和脂肪酸比例的油是合适的,也就是超过50重量%的C18不饱和脂肪酸,优选超过70%或85重量%。由妥尔油和菜籽油得到的脂肪酸是特别合适的。
在本发明中可使用一种或多种共添加剂。合适的共添加剂为本领域中所熟知的那些能够有效提高燃料油低温性质的添加剂,以及能够改善油的其他性质的添加剂,比如润滑添加剂、抗氧化剂、分散剂、去垢剂及类似物。
在一个优选实施方式中,可使用乙烯聚合物作为共添加剂。下面将给出乙烯共聚物的例子。
乙烯聚合物
每个聚合物可为均聚物或乙烯与其他不饱和单体的共聚物。
优选的共聚单体为不饱和酯或醚单体,同时更为优选酯单体。优选的乙烯不饱和酯共聚物除了具有由乙烯衍生的单元外,还具有下式的单元:
-CR3R4-CHR5-
其中R3代表氢或甲基,R4代表COOR6,其中R6代表具有1-12个,优选1-9个碳原子的烷基,其为直链的,或者如果具有3个或更多个碳原子时,其为支化的,或者R4代表OOCR7,其中R7代表R6或H,并且R5代表H或COOR6。
它们可含有乙烯和乙烯类不饱和酯的共聚物,或者其衍生物。一个例子为乙烯和饱和醇与不饱和羧酸生成的酯的共聚物,但优选酯为不饱和醇与饱和酸形成的酯。乙烯-乙烯酯共聚物是有益的,优选乙烯-醋酸乙烯酯、乙烯-丙酸乙烯酯、乙烯-己酸乙烯酯、乙烯-2-乙基己酸乙烯酯、乙烯-辛酸乙烯酯或乙烯-vinyl versatate的共聚物。优选地,共聚物含有5-40重量%的乙烯酯,更为优选10-35重量%的乙烯酯。也可使用两种共聚物的混合物,例如在美国专利No.3,961,916中公开的。共聚物的Mn优选为1000-10000。如果需要,共聚物可含有衍生自额外的共聚单体的单元,例如三元共聚物、四元共聚物或更高的共聚物,例如其中额外的共聚单体为异丁烯或二异丁烯或另外的不饱和酯。
其他合适的共聚单体包括烃单体,比如丙烯、正-和异-丁烯、1-己烯、1-辛烯、甲基-1-戊烯乙烯基环己烷和现有技术中已知的多种α烯烃,比如1-癸烯、1-十二烯、1-十四烯、1-十六烷和1-十八烯及其混合物。
以下通过实施例描述本发明。
实施例1
将具有C16-C22饱和物含量为6.2重量%的菜籽油甲酯(RME)与量为0.125重量%的四亚乙基五胺反应。反应在氮气保护下于140℃进行4小时。未处理的RME的倾点为-12℃。在与TEPA的反应完成后,倾点减低到-42℃。
实施例2
将1-2摩尔的二亚乙基三胺与1摩尔的硬脂酸通过在二甲苯中回流在160℃反应。反应结束后,通过真空蒸馏去除过量的胺和溶剂。1-氨基乙基-2-十七烷基-咪唑啉作为产品获得。将具有C16-C22饱和物含量为14.6重量%的豆油甲酯(SME)与量为0.5重量%的咪唑啉反应。反应在氮气保护下于150℃进行4小时。向SME中加入0.6重量%的乙烯醋酸乙烯酯(EVA)共聚物,测得的倾点为-42℃。作为对比,包括0.6%的EVA共聚物的未反应的SME的倾点为-6℃。
实施例3
按照与实施例2相同的比例及反应条件将三亚乙基四胺与硬脂酸反应。1-(N-氨基乙基-氨基乙基)-2-十七烷基-咪唑啉作为产品获得。将含有C16-C22饱和物含量为14.6重量%的豆油甲酯(SME)与量为0.5重量%的咪唑啉反应。反应在氮气保护下于150℃进行4小时。向SME中加入0.6重量%的乙烯醋酸乙烯酯(EVA)共聚物,测得的倾点为-51℃。作为对比,包括0.6%的EVA共聚物的未反应的SME的倾点为-6℃。
Claims (9)
1.一种改善含有衍生自植物或动物材料的脂肪酸烷基酯的油的低温性质的方法,其中至少5%的脂肪酸烷基酯衍生自C16-C22饱和脂肪酸,该方法包括将至少一部分所述油与至少一种具有3个或更多个氮原子的化合物反应,所述氮原子中的至少一个以伯胺基团的形式存在;其中所述至少一种具有3个或更多个氮原子的化合物含有聚亚烷基多胺或同时带有聚亚烷基亚胺取代基和至少一个伯胺基团的咪唑啉化合物。
2.如权利要求1所述的方法,其中所述聚亚烷基多胺具有5个或更多个氮原子。
3.如权利要求1所述的方法,其中所述咪唑啉化合物是通过将脂肪酸或脂肪酸的甲酯与聚亚烷基多胺反应制得的。
4.如前述权利要求中任一项所述的方法,其中与具有3个或更多个氮原子的化合物反应的部分油为油的0.05-20重量%。
5.如前述权利要求中任一项所述的方法,其中所述含有衍生自植物或动物材料的脂肪酸烷基酯的油基本由甲酯或乙酯、优选甲酯组成。
6.如前述权利要求中任一项所述的方法,其中所述衍生自C16-C22饱和脂肪酸的脂肪酸烷基酯的至少5重量%由棕榈酸甲酯、硬脂酸甲酯,或者其混合物构成。
7.如前述权利要求中任一项所述的方法,其中至少一种脂肪酸与油以及至少一种具有3个或更多个氮原子的化合物一起反应,或者将其加入油中。
8.如权利要求6所述的方法,其中所述至少一种脂肪酸含有衍生自植物或动物材料的脂肪酸的混合物,优选具有超过50重量%的C18不饱和脂肪酸的混合物。
9.如前述权利要求中任一项所述的方法,其进一步包括向油中加入乙烯聚合物。
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