A catalytic lignocellulose biorefinery process is presented, valorizing both polysaccharide and lignin components into a handful of chemicals. To that end, birch sawdust is efficiently delignified through simultaneous solvolysis and catalytic hydrogenolysis in the presence of a Ru on carbon catalyst (Ru/C) in methanol under a H-2 atmosphere at elevated temperature, resulting in a carbohydrate pulp and a lignin oil. The lignin oil yields above 50% of phenolic monomers (mainly 4-n-propylguaiacol and 4-n-propylsyringol) and about 20% of a set of phenolic dimers, relative to the original lignin content, next to phenolic oligomers. The structural features of the lignin monomers, dimers and oligomers were identified by a combination of GC/MS, GPC and 2D HSQC NMR techniques, showing interesting functionalities for forthcoming polymer applications. The effect of several key parameters like temperature, reaction time, wood particle size, reactor loading, catalyst reusability and the influence of solvent and gas were examined in view of the phenolic product yield, the degree of delignification and the sugar retention as a first assessment of the techno-economic feasibility of this biorefinery process. The separated carbohydrate pulp contains up to 92% of the initial polysaccharides, with a nearly quantitative retention of cellulose. Pulp valorization was demonstrated by its chemocatalytic conversion to sugar polyols, showing the multiple use of Ru/C, initially applied in the hydrogenolysis process. Various lignocellulosic substrates, including genetically modified lines of Arabidopsis thaliana, were finally processed in the hydrogenolytic biorefinery, indicating lignocellulose rich in syringyl-type lignin, as found in hardwoods, as the ideal feedstock for the production of chemicals
The objective of the paper is to establish a comprehensive resource-based life cycle impact assessment (LCIA) method which is scientifically sound and that enables to assess all kinds of resources that are deprived from the natural ecosystem, all quantified on one single scale, free of weighting factors. The method is based on the exergy concept. Consistent exergy data on fossils, nuclear and metal ores, minerals, air, water, land occupation, and renewable energy sources were elaborated, with well defined system boundaries. Based on these data, the method quantifies the exergy "taken away" from natural ecosystems, and is thus called the cumulative exergy extraction from the natural environment (CEENE). The acquired data set was coupled with a state-of-the art life cycle inventory database, ecoinvent. In this way, the method is able to quantitatively distinguish eight categories of resources withdrawn from the natural environment: renewable resources, fossil fuels, nuclear energy, metal ores, minerals, water resources, land resources, and atmospheric resources. Third, the CEENE method is illustrated for a number of products that are available in ecoinvent, and results are compared with common resource oriented LCIA methods. The application to the materials in the ecoinvent database showed that fossil resources and land use are of particular importance with regard to the total CEENE score, although the other resource categories may also be significant.
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