CN104937081A - 一种基于甘油的生物燃料的配方物、制备方法和用途 - Google Patents

一种基于甘油的生物燃料的配方物、制备方法和用途 Download PDF

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CN104937081A
CN104937081A CN201480003768.2A CN201480003768A CN104937081A CN 104937081 A CN104937081 A CN 104937081A CN 201480003768 A CN201480003768 A CN 201480003768A CN 104937081 A CN104937081 A CN 104937081A
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C·艾斯特维斯卡帕尼
N·贝亚里费里
J·卡斯泰尔斯波利亚特
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Abstract

本发明涉及一种新的生物燃料配方物，包含：粗甘油、甘油缩甲醛、任选地至少一种脂肪酸甘油缩甲醛酯和任选地至少一种脂肪酸甲酯。本发明还涉及所述生物燃料配方物的制备方法以及所述生物燃料配方物用于燃烧目的的用途。

Description

一种基于甘油的生物燃料的配方物、制备方法和用途
技术领域
本发明涉及生物燃料领域。具体而言，本发明涉及一种新的基于甘油的生物燃料，以及其制备方法和用途。
背景技术
世界已认识到迫切需要使经济增长脱离资源影响。具体而言，欧洲旨在增加工业竞争力并同时大幅度降低资源和能源的低效率。根本的原则是沿着价值链开发有条件实现的技术和解决方案以达到“事半功倍”。
已提出以下的目标：
1.到2030年，通过例如使热电联产、过程强化、新节能工艺的引入和过程循环中可再生能源的渐进引入相结合，将化石燃料能源强度从当前水平降低最高达30％。
2.到2030年，通过提高化学和物理转化率和/或使用具有得到证实的可持续性优势的二次和可再生原材料，将不可再生、初级原材料的强度从当前水平降低最高达20％。
将生物柴油合成中作为副产品获得的甘油用于燃烧的可能性是这些原则最相关之处，这是因为生物柴油和生物乙醇是当前市场上主要的生物燃料，另外因为并非所有的油原料都转化成了生物燃料，因此其生产是低效率的。共存的副产品甘油连同脂肪酸甲酯一起获得，脂肪酸甲酯是当前的汽车生物燃料。
为了燃烧在生物柴油合成(作为一种获得用于燃烧目的的可再生能源的方法)中作为副产品获得的甘油，已进行了许多尝试。然而，粗甘油显示不利的燃烧性质，并且不能在商用燃烧器中持续燃烧。
Agirre I等人"Glycerol acetals,kinetic study of the reactionbetween glycerol and formaldehyde",Biomass and Bioenergy,Pergamon,Amsterdam,NL,第35卷,第8期,第363-3642页，公开了一种由甘油和甲醛反应获得的组合物。该研究旨在确定使用离子树脂作催化剂的该反应的动力学参数。
Ruiz V R等人"Gold catalysts and solid catalysts for biomasstransformations:Valorization of glycerol and glycerol-water mixturesthrough formation of cyclic acetals",Journal of Catalysys,AcademicPress,Duluth,MN,US,第271卷,第2期,第351-357页，公开了一种由甘油和甲醛反应获得的组合物。在该文献中，该研究旨在发现新的催化体系(金催化剂)。
在这两篇文献中，所述的低转化必然导致产生含有大量(＞100ppm，基于化学计量)甲醛的组合物。因此，未反应的甲醛以甲醛或甲醛前体、三氧杂环己烷的形式存在于所述组合物中。甲醛的存在是绝对不希望的，这是因为本领域公知，甚至在低浓度，甲醛也是一种刺激性的物质，对于长期暴露于其中的人而言甚至是致癌的。
因此，虽然这些文献公开了包含甘油和可用作生物燃料成分的甘油缩甲醛的组合物，但是目前的工业标准却不能使用这种有毒的组合物(包含甲醛)，因为在目前的规章下官方不会批准这种产品。
所有这些问题均促使发明人开发一种新的生物燃料组合物，其与粗甘油相比具有改善的燃烧性能，能实现对于有效的和可再生的燃料的需求，且不含有毒成分，例如甲醛。
因此，本发明的目的是提供一种新的无毒的基于甘油的生物燃料配方物(formulation)，其解决了粗甘油在目前燃烧器中不能持续燃烧的问题。本发明的另一目的是提供一种制备所述生物燃料的方法。本发明的另一目的是展示本发明所述的生物燃料与粗甘油相比更好的燃烧性能。
发明内容
本发明涉及一种新的生物燃料配方物，包含：
A)粗甘油，其可通过市售生物柴油的生产方法获得，优选包含60-99％重量/重量的甘油、0-2％重量/重量的灰分(ash)、0-40％重量/重量的水和0-2％重量/重量的有机残余物，
B)甘油缩甲醛，其可通过使用合适的缩醛剂由甘油的缩醛化反应获得，
C)任选地，至少一种脂肪酸甘油缩甲醛酯，和
D)任选地，至少一种脂肪酸甲酯，
其特征在于，所述配方物不含甲醛。
在另一实施方案中，本发明涉及一种新的生物燃料配方物，其由以下物质组成：
A)粗甘油，其可通过市售生物柴油的生产方法获得，优选包含60-99％重量/重量的甘油、0-2％重量/重量的灰分、0-40％重量/重量的水和0-2％重量/重量的有机残余物，
B)甘油缩甲醛，其可通过使用合适的缩醛剂由甘油的缩醛化反应获得。
在另一实施方案中，本发明的生物燃料配方物包含以下物质或由以下物质组成：粗甘油、甘油缩甲醛和至少一种脂肪酸甘油缩甲醛酯。
在另一实施方案中，本发明的生物燃料配方物包含以下物质或由以下物质组成：粗甘油、甘油缩甲醛和至少一种脂肪酸甲酯。
在另一实施方案中，本发明的生物燃料配方物包含以下物质或由以下物质组成：粗甘油、甘油缩甲醛、至少一种脂肪酸甘油缩甲醛酯和至少一种脂肪酸甲酯。
优选地，所述生物燃料配方物包含以下质量比的四种组分A、B、C和D：10％至90％重量/重量的组分A、10％至90％重量/重量的组分B、0％至80％重量/重量的组分C和0％至80％重量/重量的组分D，基于全部组合物计。优选地，组分A的质量比为50％至90％重量/重量，组分B的质量比为10％至50％重量/重量，组分C的质量比为0％至40％重量/重量，并且组分D的质量比也为0％至40％重量/重量，基于全部组合物计。在一个具体的实施方案中，本发明的生物燃料包含70-90％重量/重量的粗甘油(成分A)、10-30％重量/重量的甘油缩甲醛(成分B)、0-20％重量/重量的脂肪酸甘油缩甲醛酯(成分C)和0-20％重量/重量的脂肪酸甲酯(成分D)，基于全部组合物计。
本发明的生物燃料可包含任选地一种或多种选自以下的添加剂：抗氧化剂、杀生物剂、螯合剂、去污剂、分散剂、溶剂、腐蚀抑制剂和氧化物抑制剂(oxide inhibitor)。
在另一实施方案中，本发明的生物燃料配方物包含以下物质或由以下物质组成：粗甘油、甘油缩甲醛、至少一种脂肪酸甘油缩甲醛酯和一种或多种上述添加剂。
在另一实施方案中，本发明的生物燃料配方物包含以下物质或由以下物质组成：粗甘油、甘油缩甲醛、至少一种脂肪酸甲酯和一种或多种上述添加剂。
在另一实施方案中，本发明的生物燃料配方物包含以下物质或由以下物质组成：粗甘油、甘油缩甲醛、至少一种脂肪酸甘油缩甲醛酯、至少一种脂肪酸甲酯和一种或多种上述添加剂。
生物柴油衍生的粗甘油是本领域技术人员公知的产品。其指的是甘油、水、灰分和有机残余物的混合物。其成分的不同比例形成不同等级的甘油，从粗甘油(通常包含80％重量/重量的甘油)到工业级甘油(通常包含高于98％重量/重量的甘油)。其可含有不同的水含量，其取决于原始甘油的等级和在配方物制备方法的任选的预处理步骤期间的干燥程度(见下文)。
甘油缩甲醛是甘油衍生物，其可通过缩醛化作用获得。在一个优选的实施方案中，甘油缩甲醛由粗甘油按照EP2049623中记载的方法获得，其公开内容在此以引证的方式纳入本说明书中。甘油缩甲醛是具有最低分子量的甘油缩醛。因此，与较高的同系物例如甘油乙缩醛或甘油丙醛相比，其表现出较高的蒸汽压、较低的沸点和较低的粘度。如下文所示，这些性质改善了粗甘油/甘油缩甲醛/脂肪酸甘油缩甲醛酯/脂肪酸甲酯混合物相对于单独的粗甘油的燃烧性能。
水含量是至关重要的，这是因为其不仅影响生物燃料组合物的热含量，还影响组合物的单位成本。在一个优选的实施方案中，粗甘油的水含量在0％和30％之间。
本发明还涉及一种用于制备本发明的生物燃料的方法。该方法包括混合粗甘油、甘油缩甲醛、脂肪酸甘油缩甲醛酯(如果存在)、脂肪酸甲酯(如果存在)和一种或多种任选的添加剂的步骤。优选地，该方法的温度在20℃和60℃之间，更优选在40℃左右。所述混合在配备有搅拌器的容器内进行，所述搅拌器提供足够的动力以使混合物完全均匀。所得混合物是稳定的。任选地进行预处理步骤。该预处理步骤包括过滤和任选地脱盐和水蒸发。
本发明还涉及本发明的生物燃料用于燃烧目的、优选工业燃烧的用途。
具体实施方式
实施例1：生物燃料的配方物
将含有2％有机残余物和7％灰分的粗甘油于60℃加热、过滤、并加入至混合容器中。随后，加入水含量低于5％的甘油缩甲醛。最后，加入脂肪酸甘油缩甲醛酯和脂肪酸甲酯，并将该混合物用机械搅拌器以380rpm的速率搅拌30分钟。
实施例2：燃烧性能的评估
为了评估本发明的生物燃料的燃烧性能，发明人于环境压力下在实验室的空气燃烧器中进行了数次实验。待评估的生物燃料在100℃下预热。
将50g待评估的生物燃料加入至不锈钢燃烧器中。将该生物燃料于100℃下预热，避免其成分的任何损失。用点火器点燃燃烧器。该实验测定燃料点燃燃烧器和持续、规则的燃烧直到燃烧完为止的能力。结果如表1所示：
表1：包含粗甘油、甘油缩甲醛、脂肪酸甲酯和脂肪酸甘油缩甲醛酯的12种组合物的燃烧性能。列2和3(从左数起)显示了粗甘油的甘油含量和水含量。将组合物预热至100℃，并用点火器点燃。
从表1所示的实验，可得出几个结论：
在含有72％重量/重量的甘油的组合物中，用于持续燃烧的甘油缩甲醛的浓度阈值是20％重量/重量(组合物1至6)。在具有较高甘油含量的组合物(组合物11)中，该阈值可降低至16％重量/重量。
水的影响似乎是关键的。例如，实验7和11表明，粗甘油的水含量增加2％实质上可抑制燃烧过程。实验5进一步证实水不利于燃烧质量。
组合物6为对照实验，其中使用了具有72％甘油含量的单纯的粗甘油。
脂肪酸甘油缩甲醛酯的影响是改善燃烧质量，如用组合物9和11获得的结果所示。
总之，粗甘油的燃烧性能可通过甘油缩甲醛的加入而得到极大的改善。增加的水浓度会降低燃烧质量。组合物中的水浓度越高，所需要的甘油缩甲醛的浓度越高，以保证适当的燃烧。组合物中脂肪酸甘油缩甲醛酯的存在利于燃烧过程，条件是存在足够的甘油缩甲醛浓度。

Claims (10)

1.生物燃料配方物，包含：
A)粗甘油，
B)甘油缩甲醛，
C)任选地，至少一种脂肪酸甘油缩甲醛酯，和
D)任选地，至少一种脂肪酸甲酯，
其特征在于，所述配方物不含甲醛。
2.根据权利要求1所述的生物燃料配方物，其中所述粗甘油包含：60-99％重量/重量的甘油、0-2％重量/重量的灰分、0-40％重量/重量的水和0-2％重量/重量的有机残余物。
3.根据权利要求1或2所述的生物燃料配方物，其中所述生物燃料配方物中的所述组分具有以下质量比：10％至90％重量/重量的组分A、10％至90％重量/重量的组分B、0％至80％重量/重量的组分C和0％至80％重量/重量的组分D，基于全部组合物计。
4.根据权利要求1或2所述的生物燃料配方物，其中所述生物燃料配方物中的所述组分具有以下质量比：50％至90％重量/重量的组分A、10％至50％重量/重量的组分B、0％至40％重量/重量的组分C和0％至40％重量/重量的组分D，基于全部组合物计。
5.根据权利要求1或2所述的生物燃料配方物，其中所述生物燃料配方物中的所述组分具有以下质量比：70％至90％重量/重量的组分A、10％至30％重量/重量的组分B、0％至20％重量/重量的组分C和0％至20％重量/重量的组分D，基于全部组合物计。
6.根据权利要求1至5中任一项所述的生物燃料配方物，还包括一种或多种选自以下的添加剂：抗氧化剂、杀生物剂、螯合剂、去污剂、分散剂、溶剂、腐蚀抑制剂和氧化物抑制剂。
7.制备权利要求1至6中任一项所述的生物燃料配方物的方法，包括混合粗甘油、甘油缩甲醛、至少一种脂肪酸甘油缩甲醛酯、至少一种脂肪酸甲酯和一种或多种任选的添加剂的步骤。
8.根据权利要求7所述的方法，其中所述方法的温度在20℃和60℃之间，更优选在约40℃。
9.根据权利要求7或8所述的方法，还包括预处理步骤，所述预处理步骤包括过滤和任选地脱盐和水蒸发。
10.权利要求1至6中任一项所述的生物燃料配方物用于燃烧目的的用途。
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