CN101213274B - 包含聚甲醛二烷基醚的生物柴油燃料混合物 - Google Patents

包含聚甲醛二烷基醚的生物柴油燃料混合物 Download PDF

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CN101213274B
CN101213274B CN2006800237044A CN200680023704A CN101213274B CN 101213274 B CN101213274 B CN 101213274B CN 2006800237044 A CN2006800237044 A CN 2006800237044A CN 200680023704 A CN200680023704 A CN 200680023704A CN 101213274 B CN101213274 B CN 101213274B
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G-D·特贝恩
H·舍林
E·施特勒费尔
R·平科斯
A·豪纳特
M·艾尔曼
J·卡尔
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Abstract

本发明涉及一种十六烷值＞40的生物柴油燃料混合物，其包含a)1～100％重量的生物柴油，b)0～98.9％重量的化石源柴油，c)0.1～20％重量的式RO(CH2O)nR的聚氧亚烷基二烷基醚，其中R为具有1～10个碳原子的烷基，和n＝2～10，以及d)0～5％重量的其它添加剂。

Description

包含聚甲醛二烷基醚的生物柴油燃料混合物
本发明涉及一种包含聚甲醛二烷基醚的生物柴油燃料混合物。
许多年来，工业上一直努力识别非化石源的可替代的能源，并且还努力使得所谓的可再生原料具有可利用性。后者包括植物油(即脂肪酸酯)，典型的是甘油三酯，它们一般归为可生物降解的且对环境是无害的能源。油菜籽可认为是该类植物油的原型。通常，该类油包含许多种酸的甘油酯(所述酸可随着植物油的类型和来源而改变)，以及如果合适的话额外地包含磷酸甘油酯。该类油可通过已知的方法获得。植物油可通过酯交换获得烷基酯，例如连接在甘油酯上的脂肪酸的甲基酯。
FR-A 2 492 402描述了一种包含一种或多种通式R1-COOR2的动物或植物源的脂肪酸酯的燃料组合物，其中R1是具有5～23个碳原子的基本上线性的饱和或不饱和脂族基团，以及R2是具有1～12个碳原子的线性或支化的饱和或不饱和脂族基团。该类燃料组合物描述适合用于柴油机，因为它们具有大约相当于常规柴油燃料的十六烷值的十六烷值，所述的常规柴油燃料由矿物油获得。
生物柴油作为可再生燃料的主要优点是净CO2排放降低。而且，硫氧化物、颗粒物和一氧化碳的废气排放也降低。与此相比，氮氧化物排放可能轻微增加，因而可推定：当生物柴油燃烧时所释放的CO2量(大约2.4吨/吨生物柴油)可被生长的植物再次吸收掉，而由所述植物继而获得用于生物柴油的植物油，因此净CO2的输出接近0。生物柴油基本上也是无硫的(与在常规化石柴油燃料中高达350ppm的硫相比，生物柴油的硫含量为0～0.0024ppm)。尽管纯生物柴油的NOx排放比化石源柴油的那些平均高6％，但是不存在硫使得能够采用使用常规化石柴油不能采用的用于降低NOx的技术。存在于生物柴油中的氧化物改善了燃烧和排放分布，以使得与化石柴油燃料相比，形成约低20％的一氧化碳。生物柴油的颗粒物排放也明显更低，且比常规化石柴油低40％或更多。生物柴油的生物降解性与化石柴油相比有很大增加。
生物柴油的能含量是化石柴油的92％，以至于大约1.1L的生物柴油可替代1L的化石柴油燃料。
而且，欧洲柴油规格较大地关注更高的十六烷值，同时硫和聚芳族烃的含量也要降低。
已知柴油燃料的十六烷值可通过混合线性醚而增加。此外，燃料的低温性能得以改进且稀释降低芳族烃和硫的含量。醚对于排放也具有积极作用。高十六烷值导致烃和一氧化碳的更低排放。醚中高的氧含量额外地导致废气中烟灰颗粒物的减少。
EP-A 1 070 755公开了一种具有＞40的十六烷值并且由典型的柴油切取馏分和1～20％体积的聚甲醛二烷基醚组成的柴油燃料混合物。添加聚甲醛二烷基醚将十六烷值由48升至63～100之间。
本发明的目的是提供一种具有高十六烷值和良好的排放分布的基于生物柴油的柴油燃料混合物。
该目的通过具有＞40的十六烷值的生物柴油燃料混合物得以实现，所述混合物包含
a)1～100％重量的生物柴油，
b)0～98.9％重量的化石源柴油，
c)0.1～20％重量的下式的聚氧亚烷基二烷基醚
RO(CH2O)nR
其中R为具有1～10个碳原子的烷基，和n＝2～10，以及
d)0～5％重量的其它添加剂。
作为组分a)，本发明的生物柴油燃料混合物包含1～100％重量，通常为5～90％重量，优选5～50％重量和更优选10～50％重量的生物柴油。生物柴油在40℃通常具有1.9～6.5cSt、优选3.5～5.0cSt的粘度，硫含量不大于0.05％重量，优选不大于0.01％重量，十六烷值至少为40，优选至少49，以及酸值至多0.80mg KOH/g，优选至多0.50mg KOH/g。生物柴油通常由通式R1-COOR2的脂肪酸酯组成，其中R1是具有5～23个碳原子的基本上线性的饱和或不饱和脂族基团，以及R2是具有1～12个碳原子的线性或支化的饱和或不饱和脂族基团。存在于生物柴油中的脂肪酸酯优选衍生自在R1基团中具有11～23个碳原子的线性的饱和或不饱和脂肪酸R1COOH，尤其衍生自饱和脂肪酸，如月桂酸、肉豆蔻酸、棕榈酸、硬脂酸、花生酸、二十二烷酸和二十四烷酸，单烯属不饱和脂肪酸，如月桂烯酸、肉豆蔻脑酸、棕榈油酸、油酸、顺式9-二十碳烯酸和顺式13-二十二碳烯酸，还有二-或多烯属不饱和脂肪酸，如亚油酸和亚麻酸。存在于生物柴油中的脂肪酸酯的脂肪酸可由植物或动物脂肪获得。植物脂肪是例如油菜籽油、向日葵油、椰子油、玉米油、棉籽油、大豆油和花生油。合适的动物源脂肪是例如猪肉脂肪或牛脂。
存在于生物柴油中的酯的醇组分优选选自甲醇、乙醇、正丙醇、异丙醇、正丁醇、异丁醇、2-乙基己醇或十二烷醇。脂肪酸酯优选可由存在于植物或动物源的天然脂肪的甘油酯通过与醇R2OH的酯交换反应获得。
作为组分b)，本发明的生物柴油燃料混合物包含化石源的常规柴油。柴油代表矿物油的中间馏出物的高沸点部分。典型的柴油切取馏分具有150～380℃、优选200～350℃的沸点并具有在15℃下为0.76～0.935g/ml的密度。
作为组分c)，本发明的生物柴油燃料混合物包含0.1～20％重量、通常为1～20％重量、优选3～11％重量、更优选4～11％重量的聚甲醛二烷基醚。这些中，优选聚甲醛二甲基醚和聚甲醛二乙基醚。还优选具有n＝3、4或5个氧亚甲基单元的聚甲醛二烷基醚，还有其混合物。特别优选具有3、4或5个氧亚甲基单元的聚甲醛二甲基醚及其混合物。特别优选具有n＝3或4个氧亚甲基单元的聚甲醛二甲基醚及其混合物；尤其优选四(氧亚甲基)二甲基醚(n＝4)。
本发明还提供聚甲醛二烷基醚在含有至少1％重量生物柴油的生物柴油燃料混合物中作为添加剂用于增加十六烷值的应用。
如EP-A 1 070 755所述，聚甲醛二烷基醚c)可通过在酸性催化剂存在下由合适的醇(优选甲醇)与甲醛的反应制备。
制备特别适于作为生物柴油燃料添加剂c)的聚甲醛二甲基醚(尤其是其中n＝3和4(三聚体、四聚体)的聚甲醛二甲基醚)的特别有利的方法是由甲缩醛(n＝1)和三
Figure 2006800237044_0
烷开始。将这些物质进料至反应器中并在酸性催化剂存在下进行反应，通过甲缩醛、三烷和/或催化剂引入到反应混合物中的水量基于反应混合物为＜1％重量。
在甲缩醛与三
Figure 2006800237044_2
烷生成聚甲醛二甲基醚的反应中，没有作为副产物的水形成。该反应通常在50～200℃、优选90～150℃的温度和1～20巴、优选2～10巴的压力下进行。甲缩醛：三
Figure 2006800237044_3
烷的摩尔比通常为0.1～10，优选0.5～5。
酸性催化剂可以是均相或非均相酸性催化剂。合适的酸性催化剂是无机酸，如基本上无水的硫酸，磺酸如三氟甲基磺酸和对甲苯磺酸，杂多酸，酸性离子交换树脂，沸石，硅铝酸盐，二氧化硅，氧化铝，二氧化钛和二氧化锆。为了增加它们的酸强度，氧化催化剂可掺杂硫酸根或磷酸根，其掺杂量通常为0.05～10％重量。反应可在搅拌釜反应器(CSTR)或管状反应器中进行。当使用非均相催化剂时，优选固定床反应器。当使用固定床反应器时，产物混合物可随后与阴离子交换树脂接触以获得基本上无酸的产物混合物。
通过甲缩醛和三
Figure 2006800237044_4
烷以及通过催化剂引入的水量基于由甲缩醛、三
Figure 2006800237044_5
烷和催化剂组成的反应混合物总计为＜1％重量，优选＜0.5％重量，更优选＜0.2％重量，尤其是＜0.1％重量。为此目的，使用基本上无水的三烷和甲缩醛，且如果合适的话，也相应地限制通过催化剂引入的水量。在水的存在下通过水解由已经形成的聚甲醛二甲醚形成的半缩醛(单醚)或聚甲醛二醇具有与聚甲醛二甲基醚相当的沸点，这使得从这些副产物中取出聚甲醛二甲基醚变得复杂。
为了以受控的方式获得其中n＝3和n＝4(三聚体、四聚体)的聚甲醛二甲基醚，将包含三聚体和四聚体的部分从甲缩醛与三
Figure 2006800237044_7
烷的反应的产物混合物中取出，并将未转化的甲缩醛、三
Figure 2006800237044_8
烷和n＜3的聚甲醛二甲基醚循环至酸催化的反应中。在另一个根据本发明的方法的实施方案中，额外地也将n＞4的聚甲醛二甲基醚循环至反应中。作为循环的结果，获得特别大量的三聚体和四聚体。
在特别优选的实施方案中，包含甲缩醛的第一部分，包含二聚体(n＝2)和三烷的第二部分，包含三聚体和四聚体(n＝3、4)的第三部分以及包含五聚体和更高同系物(n＞4)的第四部分可由甲缩醛与三
Figure 2006800237044_10
烷的酸催化反应的产物混合物获得。在上下文中尤其优选在三个顺序连接的蒸馏塔中取出甲缩醛与三
Figure 2006800237044_11
烷的酸催化反应的产物混合物，其中在一个蒸馏塔中由反应的产物混合物中取出第一部分，在第二个蒸馏塔中由剩余的混合物中取出第二部分，并在第三个蒸馏塔中将剩余混合物分离成第三部分和第四部分。在该分离中，第一蒸馏塔可例如在0.5～1.5巴的压力下操作，第二蒸馏塔例如在0.05～1巴的压力下操作和第三蒸馏塔例如在0.001～0.5巴的压力下操作。优选将第一和第二部分循环至反应中，更优选还额外地将第四部分循环至反应中。
当使用均相催化剂，例如无机酸或磺酸时，该催化剂保留在第四部分中并将其循环至酸性催化反应中。
乙缩醛(还包括用于本文中的聚甲醛二烷基醚)在酸性条件下解离是公知常识。生物柴油具有通常为至少0.1mg KOH/g且至多0.8mg KOH/g(根据US标准)或至多0.5mg KOH/g(根据DIN 51606)的酸值。作为在储存或消耗过程中水含量增加的结果，所述酸值可进一步在脂肪酸酯向脂肪酸转化的化学平衡中作为移动的结果而升高。生物柴油的酸性性质导致预计聚甲醛二烷基醚在生物柴油中将会不稳定并将会被解离成甲醛和甲醇。然而，已经令人吃惊地发现不存在这种情形，尽管生物柴油具有酸性性质，但聚甲醛二甲基醚在生物柴油和生物柴油/柴油混合物中完全稳定。
作为组分d)，本发明的生物柴油燃料混合物可包含0～5％重量、优选0～1％重量的其它添加剂。典型的其它添加剂是可以通常以至多1％重量存在的十六烷值改进剂。
本发明的生物柴油燃料混合物具有＞40、通常＞45、优选＞50、更优选＞52的十六烷值。
优选的本发明生物柴油混合物包含
a)5～90％重量的生物柴油
b)6～92％重量的化石源柴油
c)3～11％重量的聚甲醛二烷基醚
d)0～1％重量的十六烷值改进剂。
本发明将通过下面的实施例进行详细说明。
实施例
实施例1：
在25℃下搅拌150g的生物柴油(connediesel
Figure 2006800237044_12
CD 99，酸值＝0.12mgKOH/g)和20g的四聚甲醛二甲基醚H3CO(CH2O)4CH3。H3CO(CH2O)4CH3的含量以规则的间隔通过气相色谱法进行测定。在整个12天的实验期间，没有检测到H3CO(CH2O)4CH3含量的降低。
实施例2：
在25℃下搅拌150g的柴油和20g的四聚甲醛二甲基醚H3CO(CH2O)4CH3。H3CO(CH2O)4CH3的含量以规则的间隔通过气相色谱法进行测定。在整个12天的实验期间，没有检测到H3CO(CH2O)4CH3含量的降低。

Claims (6)

1.一种十六烷值＞40的生物柴油燃料混合物，其包含
a)5～90％重量的生物柴油，
b)0～98.9％重量的化石源柴油，
c)1～20％重量的下式的聚氧亚烷基二烷基醚
RO(CH2O)nR
其中R为具有1～10个碳原子的烷基，和n＝2～10，以及d)0～5％重量的其它添加剂，
其中所述生物柴油燃料混合物的所有组分的百分含量之和为100％重量。
2.根据权利要求1的生物柴油燃料混合物，其包含作为组分c)的具有3、4或5个氧亚甲基单元的聚甲醛二烷基醚或其混合物。
3.根据权利要求1的生物柴油燃料混合物，其包含作为组分c)的聚甲醛二甲基醚。
4.根据权利要求1的生物柴油燃料混合物，其包含
a)5～90％重量的生物柴油
b)6～92％重量的化石源柴油
c)3～11％重量的聚氧亚烷基二烷基醚
d)0～1％重量的十六烷值改进剂。
5.根据权利要求1的生物柴油燃料混合物，其十六烷值＞45。
6.下述通式的聚甲醛二烷基醚在具有至少1％重量的生物柴油的生物柴油燃料混合物中作为添加剂用于增加十六烷值的应用
RO(CH2O)nR
其中R为具有1～10个碳原子的烷基，和n＝2～10。
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