Multinuclear and Multidimensional NMR Tools for Characterisation of Bio-oils produced from BSG

在过去十年中燃料消耗的增加已经引入了生物质作为绿色和更可持续的能源形式的利用。使用生物质是发展可持续和绿色能源平台的一个可能解决办法。啤酒糟（BSG）是啤酒酿造过程中的主要副产品之一。它主要由长而坚韧的碳水化合物和木质素链组成，因此，这限制了废料的进一步利用。然而，这种链可以通过破坏性加热或热解分解成粘稠的焦油状油。这种生物油是一种复杂的混合物，不仅含有烷烃和烯烃，而且含有含氧物质，如醇、醛、羧酸、愈创木酚和水。生物油作为燃料的直接使用受到这些物质存在的限制：它通常太酸并且含有太多的水。因此，了解这些生物油的化学成分至关重要，更重要的是量化含氧物质将深入了解需要什么样的升级过程。核磁共振（NMR）是一种广泛使用的非破坏性/非侵入性分析工具，给出关于样品中存在的化学物质的定量信息。然而，生物油是几十种甚至几百种不同化合物的混合物，分析这种复杂的混合物并不简单。在这个项目中，我们将使油与只与含氧基团联合收割机的化学物质反应，并用NMR活性核（如氟和磷）标记它们。该方法允许直接定量，甚至鉴定油样品中的有害含氧物质。将开发定量核磁共振协议，允许快速，精确的表征油样，并可能在核磁共振软件或作为独立的软件包实施。多维技术，如扩散NMR，可以应用于获得关于油样的附加信息，将NMR光谱中发现的化学信息与物理信息，如分子量相结合。可以扩展可用的衍生化合物的集合，以在NMR光谱中实现更好的分辨率或选择性地与油样品中的其他官能团反应。

An increase in fuel consumption over the last decade has introduced the utilisation of biomass as a green and more sustainable form of energy. The use of biomass is one possible solution for the development of sustainable and green energy platforms. Brewers' Spent Grain (BSG) is one of the major by-products of the brewing process. It consists mostly of long, tough carbohydrate and lignin chains, thus, this the further use of the waste materiallimited. However, such chains can be broken down by destructive heating, or pyrolysis, into a thick, tar-like oil. This bio-oil is a complex mixture containing not only alkanes and alkenes but also, oxygen-containing species such as alcohols, aldehydes, carboxylic acids, guaiacols, and water. The direct use of bio-oil as a fuel is limited by the presence of these species: it is typically, too acidic and contains too much water.Therefore, the understanding of the chemical composition of these bio-oils is crucial, and more importantly quantifying the oxygen-containing species will give the insight as to what upgrading process is required. Nuclear Magnetic Resonance (NMR) is a widely used non-destructive/non- invasive analytical tool, giving quantitative information about the chemical species present in a sample. Bio-oils, however, are mixtures of many dozens, if not hundreds, of different compounds and the analysis of such complex mixtures is not simple.In this project, we will react the oils with chemicals that will combine only with the oxygen-containing groups and label them with NMR-active nuclei such as fluorine and phosphorus. This method allows for the direct quantification and even identification of the detrimental oxygen-containing species in the oil samples. Quantitative NMR protocols will be developed, allowing for rapid, precise characterisation of oil samples and may be implemented on NMR software or as standalone packages. Multidimensional techniques, such as diffusion NMR, can be applied to obtain additional information about the oil samples, coupling the chemical information found in an NMR spectrum with physical information, such as molecular weight. The set of available derivatising compounds can be expanded, either to achieve better resolution in the NMR spectra or to selectively react with other functional groups in the oil samples.