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

Multitechnique characterization of six technical lignins including nuclear magnetic resonance and size exclusion chromatography studies.

Mineral CO2 sequestration, i.e., carbonation of alkaline silicate Ca/Mg minerals, analogous to natural weathering processes, is a possible technology for the reduction of carbon dioxide emissions to the atmosphere. In this paper, alkaline Ca-rich industrial residues are presented as a possible feedstock for mineral CO2 sequestration. These materials are cheap, available near large point sources of CO2, and tend to react relatively rapidly with CO2 due to their chemical instability. Ground steel slag was carbonated in aqueous suspensions to study its reaction mechanisms. Process variables, such as particle size, temperature, carbon dioxide pressure, and reaction time, were systematically varied, and their influence on the carbonation rate was investigated. The maximum carbonation degree reached was 74% of the Ca content in 30 min at 19 bar CO2 pressure, 100 degrees C, and a particle size of <38 microm. The two most important factors determining the reaction rate are particle size (<2 mm to <38 microm) and reaction temperature (25-225 degrees C). The carbonation reaction was found to occur in two steps: (1) leaching of calcium from the steel slag particles into the solution; (2) precipitation of calcite on the surface of these particles. The first step and, more in particular, the diffusion of calcium through the solid matrix toward the surface appeared to be the rate-determining reaction step. The Ca diffusion was found to be hindered by the formation of a CaCO3-coating and a Ca-depleted silicate zone during the carbonation process. Research on further enhancement of the reaction rate, which would contribute to the development of a cost-effective CO2-sequestration process, should focus particularly on this mechanism.

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