New biomass derived carbon catalysts for biomass valorization

Due to diminishing petroleum reserves, unsteady market situation and the environmental concerns associated with utilization of fossil resources, the utilization of renewables for production of energy and chemicals (biorefining) has gained considerable attention. Biomass is the only sustainable source of organic compounds that has been proposed as petroleum equivalent for the production of fuels, chemicals and materials. In fact, it would not be wrong to say that the only viable answer to sustainably convene our future energy and material requirements remain with a bio-based economy with biomass based industries and products. This has prompted biomass valorization (biorefining) to become an important area of industrial research. While many disciplines of science are involved in the realization of this effort, catalysis and knowledge of chemical technology are considered to be particularly important to eventually render this dream to come true. Traditionally, the catalyst research for biomass conversion has been focused primarily on commercially available catalysts like zeolites, silica and various metals (Pt, Pd, Au, Ni) supported on zeolites, silica etc. Nevertheless, the main drawbacks of these catalysts are coupled with high material cost, low activity, limited reusability etc. – all facts that render them less attractive in industrial scale applications (poor activity for the price). Thus, there is a particular need to develop active, robust and cost efficient catalytic systems capable of converting complex biomass molecules. Saccharification, esterification, transesterification and acetylation are important chemical processes in the valorization chain of biomasses (and several biomass components) for production of platform chemicals, transportation fuels, food additives and materials. In the current work, various novel acidic carbons were synthesized from wastes generated from biodiesel and allied industries, and employed as catalysts in the aforementioned reactions. The structure and surface properties of the novel materials were investigated by XRD, XPS, elemental analysis, SEM, TEM, TPD and N2-physisorption techniques. The agro-industrial waste derived sulfonic acid functionalized novel carbons exhibit excellent catalytic activity in the aforementioned reactions and easily outperformed liquid H2SO4 and conventional solid acids (zeolites, ion-exchange resins etc). The experimental results indicated strong influence of catalyst pore-structure (pore size, pore-volume), concentration of –SO3H groups and surface properties in terms of the activity and selectivity of these catalysts. Here, a large pore catalyst with high –SO3H density exhibited the highest esterification and transesterification activity, and was successfully employed in biodiesel production from fatty acids and low grade acidic oils. Also, a catalyst decay model was proposed upon biodiesel production and could explain that the catalyst loses its activity mainly due to active site blocking by adsorption of impurities and by-products. The large pore sulfonated catalyst also exhibited good catalytic performance in the selective synthesis of triacetin via acetylation of glycerol with acetic anhydride and out-performed the best zeolite H-Y with respect to reusability. It also demonstrated equally good activity in acetylation of cellulose to soluble cellulose acetates, with the possibility to control cellulose acetate yield and quality (degree of substitution, DS) by a simple adjustment of reaction time and acetic anhydride concentration. In contrast, the small pore and highly functionalized catalysts obtained by hydrothermal method and from protein rich waste (Jatropha de-oiled waste cake, DOWC), were active and selective in the esterification of glycerol with fatty acids to monoglycerides and saccharification of cellulosic materials, respectively. The operational stability and reusability of the catalyst was found to depend on the stability of –SO3H function (leaching) as well as active site blocking due to adsorption of impurities during the reaction. Thus, our results corroborate the potential of DOWC derived sulfated mesoporous active carbons as efficient integrated solid acid catalysts for valorization of biomass to platform chemicals, biofuel, bio-additive, surfactants and celluloseesters.

Compilation of measurements from two interdisciplinary STAR-shaped surveys in the North Sea: The ZISCH - Dataset

The measurements were obtained during two North Sea wide STAR-shaped cruises during summer 1986 and winter 1987, which were performed to investigate the circulation induced transport and biologically induced pollutant transfer within the interdisciplinary research in the project "ZISCH - Zirkulation und Schadstoffumsatz in der Nordsee / Circulation and Contaminant Fluxes in the North Sea (1984-1989)". The inventory presents parameters measured on hydrodynamics, nutrient dynamics, ecosystem dynamics and pollutant dynamics in the pelagic and benthic realm. The research program had the objective of quantifying fluxes of major budgets, especially contaminants in the North Sea. In spring 1986, following the phytoplankton spring bloom, and in late winter 1987, at minimum primary production activity, the North Sea ecosystem was investigated on a station net covering the whole North Sea. The station net was shaped like a star. Sampling started in the centre, followed by the northwest section and moving counter clockwise around the North Sea following the residual currents. By this strategy, a time series was measured in the central North Sea and more synoptic data sets were obtained in the individual sections. Generally advection processes have to be considered when comparing the data from different stations. The entire sampling period lasted for more than six weeks in each cruise. Thus, a time-lag should be considered especially when comparing the data from the eastern and the western part of the central and northern North Sea, where samples were taken at the beginning and at the end of the campaign. The ZISCH investigations represented a qualitatively and quantitatively new approach to North Sea research in several respects. (1) The first simultaneous blanket coverage of all important biological, chemical and physical parameters in the entire North Sea ecosystem; (2) the first simultaneous measurements of major contaminants (metals and organohaline compounds) in the different ecosystem compartments; (3) simultaneous determinations of atmospheric inputs of momentum, energy and matter as important ecosystem boundary conditions; (4) performance of the complex measurement program during two seasons, namely the spring plankton bloom and the subsequent winter period of minimal biological activity; and (5) support of data analysis and interpretation by oceanographic and meteorological numerical models on the same scales.