Éthanol cellulosique | EPFL Graph Search

L'éthanol cellulosique (ou ceetol) est un biocarburant de transport fabriqué à partir de déchets agricoles et ligneux, ainsi que d'arbres à croissance rapide. La paille de blé, la canne à sucre, le maïs, les déchets ligneux, le panic érigé et le peuplier constituent autant de sources potentielles. Les sous-produits végétaux servent à produire l'énergie requise pour la fabrication de l'éthanol cellulosique. Son potentiel de réduction des émissions de gaz à effet de serre est supérieur à celui de l'éthanol traditionnel fabriqué à partir de céréales. Comme l'éthanol traditionnel, l'éthanol cellulosique peut être ajouté à l'essence et utilisé dans tous les véhicules à essence d'aujourd'hui. La production d'éthanol cellulosique pourrait permettre de stimuler la croissance économique dans les régions rurales, d'ouvrir de nouveaux marchés aux agriculteurs et d'accroître l'usage de l'énergie renouvelable. La production d'éthanol se découpe en plusieurs étapes : rupture de la cellulose pour

Hydrothermally Stable Sulfonated Carbons as Solid Acid Catalysts for the Hydrolysis of Lignocellulose

David Ferdinand Scholz

The recycling of homogeneous acids imposes great challenges to the feasibility of lignocellulose hydrolysis processes. Although heterogeneous catalysts would offer a perspective to circumvent these challenges, conventional solid acids are instable under the hydrothermal conditions typical of hydrolysis processes. In this regard, acid functionalized carbons appear as auspicious alternatives due to the higher perseverance of carbon frameworks. The strong Brønsted acid sites in sulfonated carbons would be particularly well suited to catalyze the hydrolysis of cellulosic biomass. The utilization of these materials has so far been impeded by the controversy regarding the stability of sulfonic acid groups in carbons. Furthermore, it remains uncertain how the constraints imposed on the reaction system by the insolubility of lignocellulose influence the ability of solid acids to function as hydrolysis catalysts. This thesis shows that hydrothermally stable sulfonated carbons can be prepared by utilizing the structure-stability dependence of sulfonic acid groups in carbonaceous materials. The sulfonation of materials featuring a low degree of graphitization resulted in active solid Brønsted acid catalysts that however deactivated through the leaching of sulfonic acid groups. An in-depth physicochemical characterization of the catalysts paired with a systematic study of the stability of model sulfonic acids, revealed that the leaching-tendency is defined by substituent effects. Activating/deactivating substituents control the hydrothermal stability of aryl sulfonic acids by decreasing/increasing the tendency of the carbon-sulfur bond to undergo solvolysis. The presence of stabilizing and destabilizing substituents was found to be tunable by the temperature dependent decomposition of oxygen containing surface groups. Sulfonation of cellulose carbonized at 350°C resulted in a catalyst with 850 µmol g-1 hydrothermally (180 °C) stable sulfonic acid groups. Additionally, a hitherto unknown mode of deactivation was identified that proceeds by the ion-exchange of cationic impurities with protons of the active sites. This mode of deactivation can be fully overcome by implementing countermeasures to reverse or suppress ion-exchange processes. To tackle the limitations of homogeneous acids, the stable sulfonated carbons were used as catalysts in a semi-batch based lignocellulose hydrolysis process. It was found that the chemical recalcitrance and the insolubility of the substrate imposed strong limitations on the reaction with the catalyst and that soluble product formation occurred predominantly via auto-hydrolysis. The propensity of cellulose to undergo auto-hydrolysis could be enhanced by amorphizing its crystal structure through mechanical pretreatment in ball-mill. A heterogeneously catalyzed hydrolysis was achieved through mechanocatalytic processes facilitated by the concerted ball-milling (CBM) of the sulfonated carbon with the substrate. Sulfonic acid groups were pinpointed as active sites during the mechanocatalytic formation of soluble oligosaccharides. The secondary hydrolysis to monosaccharides in the semi-batch reactor was no longer constrained by the insolubility of the substrate. The combination of CBM pretreatment and hydrolysis in the semi-batch reactor was successfully extrapolated to the conversion of spruce fir wood to achieve yields in C5 and C6 derived products that are competitive with state-of-the-art diluted acid processes.

EPFL2019

Model-based scale-up of a continuously operated consolidated bioprocess based on a microbial consortium for the production of ethanol

David Béat Dempfle

This work demonstrated that consolidated bioprocessing is a promising concept for conversion of lignocellulose to ethanol at industrial scale. CBP offers great cost saving potential, is feasible to be operated continuously and may be scaled up due to extensive knowledge of the process from a chemical engineering point of view.Cost savings of up to 27.5% of the total costs compared to conventional bioethanol production from lignocellulose, as stated by a techno-economic assessment, make continuous CBP the strongest lever to reduce processing costs of lignocellulosic ethanol. A cost sensitivity analysis identified scale and yield as the main cost-pushers from a process point of view, whereas the price level of the plant location has the highest impact on the investment conditions.To prove the feasibility of continuous CBP, and therefore the mentioned cost savings, experiments with a maximum titer of 3.258±0.007 g/L, a productivity of 0.025 g/(Lh) and constant enzyme production over 750h were conducted. Furthermore, the continuous experiments showed that experiments with identical volumetric oxygen transfer rate k_L a, but different oxygen fluxes per membrane area, showed titer differences of ca. 80% (1.83 g/L vs 3.26 g/L) in favor of setups with the large membrane surface. A rigorous process model was developed for continuously operated CBP. 9 species were considered (oxygen, glucose, total concentration Trichoderma reesei, secondary mycelia concentration of T. reesei, enzymes, cellulose, cellobiose, yeast density and ethanol). 8 of these 9 species needed to be modelled spatially resolved to account properly for mass transfer limitations. The fungal biofilm thickness d_f was found to be a critical parameter with an optimum for every membrane configuration. Smaller d_f reduced the fungal biofilm volume and thus, the enzyme production and larger d_f increased the diffusion path length causing shortage in nutrient supply as well as lower enzyme concentrations in the bulk. The enzyme synthesis rate of the secondary mycelia was fitted by reducing it by ca. 40% (0.67 FPU/(mLd) vs 1.152 (FPU/(mL*d) compared to batch models.With the process model as centerpiece, a scale-up framework consisting of the model and a set of non-dimensional parameters was developed to scale CBP from 2.7L laboratory scale to 130L pilot scale. The majority of the non-dimensional parameters could be kept constant during scale-up as requested by the similarity paradigm. Necessary changes were simulated with the model. Again, the fungal biofilm thickness d_f proved to be a relevant parameter for scale-up considerations. In general, the relative loss of biofilm volume is compensated by longer residence times since the residence time has by far the least impact on the process economics.Finally, popular rate-controlled separation techniques were investigated regarding their potential with CBP, since they offer the potential to reduce yeast inhibition, to avoid separation limitations by the azeotrope and they are not bound to the vapor-liquid-equilibrium of highly diluted ethanol-water mixtures. However, most of the mechanisms fail to handle the solids of the fermentation broth. Pervaporation, being the most promising concept for in-situ product removal, would be a cost-saving alternative to distillation for batch operation, but is limited by an unfavorable vapor-liquid equilibrium due to low bulk concentrations during continuous operation.

EPFL2022

Developing structure-oriented models for enzymatic hydrolysis of lignocellulosic biomass

Jessica Charlène Rohrbach

With the unsustainable use of fossil fuels increasing strains on human institutions and ecosystems, the development of a renewable energy alternative is of paramount importance. Second generation biorefineries, based on the production of fuels and chemicals from lignocellulosic biomass, appear as attractive alternative to their non-renewable counterparts. Within the multiplicity of existing valorisation routes, enzymatic hydrolysis of lignocellulosic biomass into its constituent sugars has generated considerable interest, notably in the context of biofuels production. However, major hurdles stemming from the intricate structure of the lignocellulosic feedstocks still impede large-scale deployment of this process. The multiplicity of highly intertwined spatiotemporal factors impacting the enzymatic hydrolysis of lignocellulosic biomass represents a challenge to rationally design efficient hydrolysis process. Here, we propose a theory-based modelling framework relying on pore-diffusion and surface reaction to explore the effects of recognised bottlenecks on the enzymatic hydrolysis of lignocellulosic substrates. The model is based on a set of partial differential equations describing the evolution of the substrate morphology to investigate the interplay between experimental conditions and the physical characteristics of biomass particles as the reaction proceeds. The overall quantity of cellulase present in the hydrolysis mixture is carefully considered to investigate its interplay with the available accessible cellulose surface. Also, non-uniformity in terms of cellulose accessibility and cellulose digestibility are introduced in the model to weight their influence on observed hydrolysis rates. Finally, deactivation mechanisms are considered through unproductive adsorption of cellulases on both cellulose and lignin fractions, with the existence of such phenomena alleged to be critical in the efficiency of the hydrolysis process. Based on predictions of our model, we were able to confirm the critical role of cellulose accessibility, as defined by the combination of particle size, porosity and accessible cellulose surface, in dictating early reaction rates for a range of pretreated beech wood substrates. While high biomass loading should be favoured to improve enzyme penetration in the substrates, high enzyme loadings going beyond the initial number of cellulose adsorption appeared beneficial in notably two cases: (i) to promote internal diffusion in large particles and (ii) counteract undesired enzyme adsorption on lignin. For the latter, a relatively low increase in enzyme loading was sufficient to offset the resulting slowdown. We also showed that the existence of structural heterogeneities, and in particular non-uniform pore volume distribution within the lignocellulosic samples, contribute to the rate slowdown observed at later stage of the hydrolysis, while not explaining it in its entirety. Unproductive adsorption to cellulose, coupled to decrease in the cellulase efficiency at the cellulose surface, appeared as major contributor to the rate slowdown. Overall, we show how the use of a theory-based model can help decouple and evaluate the effects of key factors in the enzymatic hydrolysis of lignocellulosic biomass. As such, our model can help pave the way towards efficient integrated rational design strategies for enzyme process engineering for biomass conversion.

EPFL2021