CN101058753A - 生物燃料的改进 - Google Patents

生物燃料的改进 Download PDF

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CN101058753A
CN101058753A CNA2007101044346A CN200710104434A CN101058753A CN 101058753 A CN101058753 A CN 101058753A CN A2007101044346 A CNA2007101044346 A CN A2007101044346A CN 200710104434 A CN200710104434 A CN 200710104434A CN 101058753 A CN101058753 A CN 101058753A
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A·C·苏特科斯奇
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Abstract

本发明涉及一种包含主要量的油和少量添加剂组合物的液体组合物，其中添加剂组合物包含BHQ和N，N’－二亚水杨基丙二胺，并且至少2重量％的所述油源自植物或动物。本发明还涉及防止或延迟液体组合物氧化的方法和添加剂在防止或延迟液体组合物氧化中的用途。

Description

生物燃料的改进
本发明涉及防止或延迟源自植物或动物的油的氧化。
源自植物或动物的油和脂肪越来越多地用作燃料，特别是用作石油衍生中间馏分燃料(例如柴油)的部分或完全替代品。通常，这种燃料称为“生物燃料”或“生物柴油”。生物燃料可以由许多来源衍生得到。其中最普遍的是从例如油菜籽、葵花籽等植物中提取的脂肪酸的烷基酯，往往是甲酯。这些类型的燃料往往称为FAME(脂肪酸甲酯)。
对环境的重视促进了这种燃料的使用，因为它们由可再生来源得到。还有一点是生物燃料燃烧所产生的污染比等同的石油衍生燃料要小。
但是，由于这种燃料由天然来源衍生得到，因此它们储存时往往会因氧化而恶化。
氧化问题对于石油衍生燃料虽不明显，但仍重要，并且公知在石油衍生油中使用抗氧化添加剂。所用的最普遍一类是芳基-胺类和酚类抗氧化剂，例如二苯胺、二烷基苯胺、BHT、BHQ、Irganox L118和Irganox L57。也使用酮类、磷基和糖酯抗氧化剂，例如2，4-壬二酮、二月桂基亚磷酸酯、三甲苯基磷酸酯和抗坏血酸棕榈酸酯。US2004/0139649 A1描述了BHT(2，4-二叔丁基羟基甲苯)用于提高生物柴油储存稳定性的用途。
已知金属钝化剂(MDA)用在燃料中，以使金属表面和溶解的金属钝化，并防止它们加速劣化。
本发明基于发现了一定已知抗氧化剂物质2，5-二叔丁基氢醌(BHQ)与一定MDA N，N’-二亚水杨基丙二胺(disalicylidene propylene diamine)的组合协同地提高了源自植物或动物的油的氧化稳定性。这是意外的，因为所观察的效应并没有扩展到其它类的已知抗氧化剂，并没有发现它们与MDA的组合同样表现出协同效果。
因此，根据第一方面，本发明提供了一种液体组合物，其包含主要量的油和少量的添加剂组合物，其中添加剂组合物包含BHQ和N，N’-二亚水杨基丙二胺，并且至少2重量％的油源自植物或动物。
根据第二方面，本发明提供了一种防止或延迟包含至少2重量％的源自植物或动物的油的液体组合物氧化的方法，该方法包括向该组合物中添加BHQ和N，N’-二亚水杨基丙二胺的组合。
根据第三方面，本发明提供了一种提高包含至少2重量％的源自植物或动物的油和BHQ的液体组合物的氧化稳定性的方法，该方法包括向该组合物中添加N，N’-二亚水杨基丙二胺。
根据第四方面，本发明提供了BHQ和N，N’-二亚水杨基丙二胺的组合用于防止或延迟液体组合物氧化的用途，其中液体组合物包含至少2重量％的源自植物或动物的油。
根据第五方面，本发明提供了N，N’-二亚水杨基丙二胺用于提高包含至少2重量％的源自植物或动物的油和BHQ的液体组合物氧化稳定性的用途。
如上讨论的，芳胺类物质，特别是二芳胺类物质和酚类物质是已知的石油衍生油的抗氧化剂。仍如上讨论的，已有建议BHT可有效地提高生物柴油的储存稳定性(US2004/0139649A1)。据广泛认为，烃燃料的氧化按自由基机理进行：
(i)反应开始于自由基生成：
                        RH→R·+H·
(ii)烃自由基(R·)接着可以与氧反应，生成过氧基，而过氧基接着能够与其它烃以永动方式反应：
                        R·+O2→ROO·
                      ROO·+RH→ROOH+R·
(iii)抗氧化剂(AH)能够为过氧基提供氢原子，该反应比过氧基与其它烃的反应更有利：
                      ROO·+AH→ROOH+A·
抗氧化剂(酚类或芳胺类)中芳基的存在使得所生成的抗氧化基(A·)由于共振而充分稳定，以致传播停止。
该机理也被广泛认为是由天然来源衍生的油氧化的过程。这种油的组分结构的特征在于存在或多或少的烯烃类不饱和键。与烯烃类不饱和键相邻的氢原子更容易移出，由此以上步骤(i)中的R·生成更容易。因此含有更高比例的烯键式不饱和物质和/或带多个烯烃类不饱和键的物质的油更容易氧化。例如，已有报道C18甲酯氧化的相对速率按递增顺序为：油酸(C18:1)、亚油酸(C18:2)、亚麻酸(C18:3)。
考虑以上概括的可接受的抗氧化机理，并不清楚为什么N，N’-二亚水杨基丙二胺会影响BHQ的效果。此外，并没有看到N，N’-二亚水杨基丙二胺与BHT的组合表现出相同效果，尽管BHT和BHQ结构相似。
现在将更详细地描述适合本发明所有方面的各种特征。
源自植物或动物的油
源自动物或植物的油的例子是油菜籽油、芫荽油、大豆油、棉籽油、葵花籽油、蓖麻油、橄榄油、花生油、玉米油、杏仁油、棕榈籽油、椰子油、芥子油、麻风果油(jatropha oil)、牛脂和鱼油。其它例子包括源自玉米、黄麻、芝麻、牛油树、花生蛋白的油和亚麻籽油，并且可以通过本领域已知方法衍生得到。油菜籽油是其中脂肪酸部分被甘油酯化的混合物，它可以大量获取，并且可以通过压榨油菜籽的简单方式得到。循环油，例如用过的厨房用油也适用。
作为脂肪酸的烷基酯，可以考虑下面的例如商用混合物：碘值为50-150，特别为90-125，具有12-22个碳原子的脂肪酸，例如月桂酸、肉豆蔻酸、棕榈酸、棕榈油酸、硬脂酸、油酸、反油酸、岩芹酸、蓖麻油酸、桐酸、亚油酸、亚麻酸、花生酸、鲟油酸、山嵛酸或芥子酸的乙酯、丙酯、丁酯和特别是甲酯。具有特别有利性质的混合物是主要包含，即包含至少50wt％具有16-22个碳原子和1、2或3个双键的脂肪酸甲酯的那些。优选的脂肪酸低级烷基酯是油酸、亚油酸、亚麻酸和芥子酸的甲酯。
所述类的商用混合物例如通过与低级脂族醇的酯交换而将动物和植物脂肪和油断裂和酯化得到。对于制备脂肪酸的烷基酯，有利的是开始于含有少量(低于20％)饱和酸且碘值小于130的脂肪和油。下面酯或油的混合物合适，例如油菜籽、葵花籽、芫荽、蓖麻、大豆、花生、棉籽、牛脂等。优选基于新一类油菜籽油的脂肪酸烷基酯，其中脂肪酸组分的大于80wt％由具有18个碳原子的不饱和脂肪酸衍生得到。
特别优选能够用作生物燃料的油。据认为生物燃料，即源自动物或植物的燃料燃烧时对环境的破坏小，并且由可再生来源得到。已有报道，燃烧时所形成的二氧化碳比等量石油馏分燃料，例如柴油燃料形成的要少，所形成的二氧化硫非常少。植物油的某些衍生物，例如通过用一元烷基醇皂化和再酯化得到的那些可以用作柴油燃料的替代品。
因此，生物燃料是能够用作燃料的、由植物或动物，或它们二者得到的油或其衍生物。
虽然许多上述油可以用作生物燃料，但优选植物油衍生物，其中特别优选的生物燃料是油菜籽油、棉籽油、大豆油、葵花籽油、橄榄油或棕榈油的烷基酯衍生物，特别优选油菜籽油甲酯。
当前，最普遍的是生物燃料与石油衍生油组合使用。本发明适用于生物燃料和石油衍生燃料的任意比的混合物。例如，至少重量5％，优选至少25重量％，更优选至少50重量％，例如至少95重量％的油可以衍生自植物或动物来源。
为避免疑问，本发明也适用于纯生物燃料。在其一种实施方案中，液体组合物包含几乎100重量％的源自植物或动物的油。
本发明的实际结果是可以处理特别容易因氧化而恶化的纯生物燃料和生物燃料含量高的燃料，以改善其保存时间。这都可能重要，无论生物燃料要以基本纯的形式使用，或在延长保存后要与石油衍生油混合。
处理速率
BHQ优选以基于液体重量10-1000ppm的量添加到液体组合物中。优选地，以基于液体重量10-500ppm，例如10-300ppm的量添加。
N，N’-二亚水杨基丙二胺与BHQ的比基于所用BHQ的重量优选为1∶50-1∶1，更优选为1∶50-1∶10，例如1∶35-1∶25。
氧化的防止或延迟
可以利用Rancimat Test(ISO 6886，pr EN 14112)测定包含源自植物或动物的油的液体组合物的氧化稳定性。该方法来源于食品工业[例如参见H.Prankl，“Oxidation Stability of fatty acid methyl esters”，第10届关于能源和工业用生物质的欧洲会议(10th European Conference on Biomassfor Energy and Industry)，1998年6月8-11日，Wurzburg]。在该测试中，在恒定温度(110℃)下老化液体样品，同时空气以10l/hr的速率通过该液体。用过的空气流通过充满蒸馏水的测量室。连续测定该测量室的导电率，并自动记录。随着液体氧化，挥发性有机酸生成，并被蒸馏水吸取。这增加了水的导电率。该氧化过程如此使得所测量的导电率逐渐升高后，再快速升高。快速升高之前的时间段称为“诱导段”，作为被测液体氧化稳定性的量度。有效抗氧化剂的存在会延长该诱导段。该Rancimat Test已采纳为鉴定生物柴油燃料的规范测试。
关于本发明第二和第三方面的方法和第四和第五方面的用途，液体组合物氧化的防止或延迟或其氧化稳定性的提高优选按利用Rancimat Test(ISO 6886)所测定的。也就是说，Rancimat Test测得诱导段比未经处理的液体组合物的诱导段有增加，这表明液体组合物的氧化得到防止或延迟，或其氧化稳定性得到提高。在第三和第五方面，未经处理的液体组合物对应于包含已含有BHQ的源自植物或动物的油的液体组合物。
现在仅通过实施例来描述本发明。
下表2示出了由Rancimat测试得到的结果。接受测试的是具有下表1所示规格且包含200ppm(按重量计)许多常用类型的抗氧化剂(包括BHQ)的生物燃料。使用相同抗氧化剂和10ppm(按重量计)MDA的组合，重复测试。为全面起见，也对只包含10ppm(按重量计)MDA的燃料进行测试。对基础燃料的5次测量的平均值是Rancimat诱导时间为5.83hr。表2报道了比该基础燃料值增加的诱导时间。
表1
  碘值   g I2/g生物燃料   66
  C16:0   质量％   4.59
  C16:1   质量％   0.21
  C18:0   质量％   1.58
  C18:1   质量％   56.04
  C18:2   质量％   19.88
  C18:3   质量％   10.39
  C20:0   质量％   -
  总饱和物   质量％   6.17
表2
  编号   添加剂 相比较基础燃料Rancimat诱导时间的增加值/小时
  1   MDA   0.72
  2   抗坏血酸棕榈酸酯   2.81
  3   抗坏血酸棕榈酸酯+MDA   2.72
  4   BHT   2.10
  5   BHT+MDA   2.93
  6   BHQ   4.28
  7   BHQ+MDA   10.72
MDA-N，N’-二亚水杨基丙二胺
BHT-2，4-二叔丁基羟基甲苯
BHQ-2，5-二叔丁基氢醌
从所得结果可以看到，MDA当单独使用时(实施例1)仅发挥了微小作用。MDA与抗坏血酸棕榈酸酯的组合(实施例2和3)所得的值比根据这两组分效果的简单加和所预计的值(0.72+2.81＝3.53)要小，这暗示着这种组合存在拮抗作用。MDA与BHT组合(实施例4和5)的效果非常接近于根据这两组分贡献的加和所预计的值(0.72+2.10＝2.82)，这表明既不存在协同作用，也不存在拮抗作用。相反，根据本发明使用BHQ的组合(实施例6和7)效果表现出明显的协同作用。该组合的效果值比根据这两组分贡献的简单加和所预计的值(0.72+4.28＝5.00，对比10.72)的2倍还多。

Claims (8)

1.一种包含主要量的油和少量添加剂组合物的液体组合物，其中添加剂组合物包含2，5-二叔丁基氢醌和N，N’-二亚水杨基丙二胺，并且至少2重量％的所述油源自植物或动物。
2.如权利要求1所述的液体组合物，其中至少5重量％，优选至少25重量％，更优选至少50重量％，例如至少95重量％的所述油源自植物或动物。
3.一种防止或延迟液体组合物氧化的方法，所述液体组合物包含至少2重量％源自植物或动物的油，所述方法包括向所述组合物中加入2，5-二叔丁基氢醌和N，N’-二亚水杨基丙二胺的组合。
4.一种提高液体组合物氧化稳定性的方法，所述液体组合物包含至少2重量％源自植物或动物的油和2，5-二叔丁基氢醌，所述方法包括向所述组合物中加入N，N’-二亚水杨基丙二胺。
5.如权利要求3或4所述的方法，其中液体组合物氧化的防止或延迟或其氧化稳定性的提高按利用Rancimat Test(ISO 6886)所测定的。
6.2，5-二叔丁基氢醌和N，N’-二亚水杨基丙二胺的组合在防止或延迟液体组合物氧化中的用途，其中所述液体组合物包含至少2重量％源自植物或动物的油。
7.N，N’-二亚水杨基丙二胺在提高液体组合物氧化稳定性中的用途，其中所述液体组合物包含至少2重量％源自植物或动物的油和2，5-二叔丁基氢醌。
8.如权利要求6或7所述的用途，其中液体组合物氧化的防止或延迟或其氧化稳定性的提高按利用Rancimat Test(ISO 6886)所测定的。
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