New insights into the chemical activation of lignins and tannins using K₂CO₃—a combined thermoanalytical and structural study

Engineering of activated carbons (ACs) through chemical activation of organic precursors has been extensively studied for a wide variety of biopolymers, biomasses, wastes and other fossil-based precursors. Despite huge efforts to engineer evermore performant and sustainable ACs, “searching-for-the-best-recipe” type of studies are more the rule than the exception in the published literature. Emerging AC applications related to energy and gas storage require strict control of the AC properties and a better understanding of the fundamentals underlying their engineering. In this study, we provide new insights into the K2CO3 chemical activation of plant-based polyphenols—lignins and tannins—through careful thermoanalytical and structural analyses. We showed for the the first time that the reactivity of polyphenols during K2CO3 chemical activation depends remarkably on their purity and structural properties, such as their content of inorganics, OH functionalities and average molecular weight. We also found that the burn-off level is proportional to the K2CO3/lignin impregnation ratio (IR), but only within a certain range—high impregnation ratios are not needed, unlike often reported in the literature. Furthermore, we showed for the first time that the K2CO3 chemical activation of different carbon surfaces from lignins and tannins can be modelled using simple global solid-state decomposition kinetics. The identified activation energies lay in the range of values reported for heterogenous gas-carbon surface gasification reactions (O2-C, H2O-C, or CO2-C) in which the decomposition of C(O) surface complexes is the common rate-limiting step.</p

Recycling of Superbase-Based Ionic Liquid Solvents for the Production of Textile-Grade Regenerated Cellulose Fibers in the Lyocell Process

This article has a correction concerning the authors: We regret that there is an error with the author list in our original article. The authors Jussi Helminen, Paulus Hyväri, and Ilkka Kilpeläinen, all with the Department of Chemistry, University of Helsinki, P.O. Box 55, FI-00014 Helsinki, Finland, were mistakenly omitted. The author list should be as shown above in this Addition and Correction. DOI 10.1021/acssuschemeng.0c07773Ioncell is a Lyocell based technology for the production of manmade cellulose fibers. This technology exploits the intrinsic dissolution power of superbase-based ionic liquids (ILs) toward cellulose and the ability to form spinnable cellulose solutions. The regenerated fibers are produced via a dry-jet wet spinning process in which the cellulose filaments are stretched in an air gap before regenerating in an aqueous coagulation medium. For the commercialization of this process, it is essential to demonstrate the quantitative recovery of the solvent from the coagulation bath without impairing its solvation power. This study reports on the spinnability and recyclability of the IL 7-methyl-1,5,7-triazabicyclo[4.4.0]dec-5-enium acetate ([mTBDH][OAc]) over five cycles in comparison to 1,5-diaza-bicyclo[4.3.0]non-5-enium acetate ([DBNH][OAc]). The aqueous IL solutions were recovered from the coagulation bath by successive thermal treatments under reduced pressure. Accordingly, the recycled ILs were utilized to dissolve 13 wt % cellulose pulp in each cycle without the addition of make-up IL. While using [mTBDH][OAc], the pulp was completely dissolved and processed into easily spinnable cellulose solutions during all five cycles, whereas the ability to dissolve pulp was completely lost after the first recovery cycle when using [DBNH][OAc]. The composition of the recovered ILs and extent of side-products generated in the adopted process was analyzed in detail. This includes characterization of the rheological properties of the solutions as well as the macromolecular and mechanical properties of the regenerated fibers. In addition, we review the toxicity of both solvents using Vibrio fischeri bacteria. Finally, the spun fibers from all [mTBDH][OAc] spinning trials were combined to produce a demonstration dress (Paju), designed and sewn by Marimekko Design House in Finland.Peer reviewe

The Metaverse: Survey, Trends, Novel Pipeline Ecosystem & Future Directions

The Metaverse offers a second world beyond reality, where boundaries are non-existent, and possibilities are endless through engagement and immersive experiences using the virtual reality (VR) technology. Many disciplines can benefit from the advancement of the Metaverse when accurately developed, including the fields of technology, gaming, education, art, and culture. Nevertheless, developing the Metaverse environment to its full potential is an ambiguous task that needs proper guidance and directions. Existing surveys on the Metaverse focus only on a specific aspect and discipline of the Metaverse and lack a holistic view of the entire process. To this end, a more holistic, multi-disciplinary, in-depth, and academic and industry-oriented review is required to provide a thorough study of the Metaverse development pipeline. To address these issues, we present in this survey a novel multi-layered pipeline ecosystem composed of (1) the Metaverse computing, networking, communications and hardware infrastructure, (2) environment digitization, and (3) user interactions. For every layer, we discuss the components that detail the steps of its development. Also, for each of these components, we examine the impact of a set of enabling technologies and empowering domains (e.g., Artificial Intelligence, Security & Privacy, Blockchain, Business, Ethics, and Social) on its advancement. In addition, we explain the importance of these technologies to support decentralization, interoperability, user experiences, interactions, and monetization. Our presented study highlights the existing challenges for each component, followed by research directions and potential solutions. To the best of our knowledge, this survey is the most comprehensive and allows users, scholars, and entrepreneurs to get an in-depth understanding of the Metaverse ecosystem to find their opportunities and potentials for contribution

Effets du CO2 sur la pyro-gazéification de la biomasse dans des conditions de chauffe lente et de chauffe rapide

The present work deals about the effects of CO2 enriched atmospheres on biomass pyrolysis and char gasification reactions in High Heating Rate (HHR) and Low Heating Rate (LHR) conditions, at the biomass particle level. In the first part, we studied the effects of CO2 on the high temperature fast pyrolysis reaction and evaluate its effects on the pyrolysis rate, on the gas yield as well as on the char properties including chemical composition, texture and reactivity at 850°C. We focused also on the effects of CO2 on the HHR-char gasification reaction when injected as a co-reactant with steam. We studied the mixed atmosphere gasification reaction in CO2 and H2O for different atmosphere compositions. Finally, we imagined a hypothetical case of a pure CO2 operating gasifier. The case of a pure CO2 pyrogasification process was tackled experimentally and theoretically by numerical modelling with aim to provide pyrolysis and gasification characteristic reaction times, and to understand the unfolding of the global CO2 pyro-gasification reaction. In the second part, we were interested on the issue of LHR-char gasification in the presence of CO2 with two principal objectives: on one hand, providing reactivity data for practical gasification operations and on the other hand, understanding the gasification reaction mechanisms (in CO2, H2O and their mixtures) at the level of the char basic structural units (BSU). We examined the influence of particle size on the single atmosphere gasification in CO2 and H2O using the Thiele modulus approach. We also studied the effects of temperature and particle size on the char gasification in mixed atmosphere of CO2 and steam at 900°C. We also had a focus on the issue of cyclic atmosphere gasification and studied the effects of a prior CO2 gasification on the char reactivity towards H2O and vice versa. To further understand the char gasification mechanisms in single and mixed atmospheres of CO2 and H2O, we opted to monitor the evolution of the chemical, structural and textural char properties along the gasification in CO2, H2O and their mixtures. Deep char characterization were performed on small LHR-char particles partially gasified at 20%, 50% and 70% of conversion in CO2, H2O and their mixtures. These characterisations are of high interest as they shed light on the unfolding of the gasification reaction in CO2, H2O and their mixtures.La présente étude porte sur les effets de CO2 sur la pyrolyse de la biomasse et la gazéification de chars dans des conditions de chauffe lente et de chauffe rapide. Dans la première partie de ce travail, nous avons étudié les effets du CO2 sur la réaction de pyrolyse rapide à haute température et évalué ses effets sur la vitesse de pyrolyse, sur le rendement de gaz ainsi que sur les propriétés du char. Nous avons aussi étudié la réaction de gazéification en atmosphère mixte en présence de CO2 et de H2O. Enfin, nous avons imaginé le cas hypothétique d’un gazogène au CO2 pur. Le cas d’une pyro-gazéification sous CO2 pur a été abordé au niveau de la particule de biomasse, expérimentalement et théoriquement par la modélisation numérique avec l’objectif de fournir des temps caractéristiques de pyrolyse et de gazéification, et de comprendre le déroulement de la pyro-gazéification sous CO2. Dans la deuxième partie, nous nous sommes intéressés à la question de la gazéification des chars obtenus par chauffe lente, en présence de CO2 avec deux objectifs principaux : d’une part, de fournir des données de réactivité dans des conditions opératoires de réacteurs de gazéification et d’autre part, de comprendre les mécanismes de réaction de gazéification sous CO2, H2O et leurs mélanges. Nous avons examiné l’influence de la taille des particules sur la vitesse de gazéification sous des atmosphères simples de CO2 et H2O en utilisant une approche basée sur le module de Thiele. Nous avons également étudié les effets de la température et de la taille des particules sur la gazéification du char sous atmosphères mixtes contenant CO2 et H2O à 900°C. Nous avons également abordé la question des atmosphères cycliques en examinant l’effet de la gazéification du char sous CO2 sur sa réactivité à H2O et vice versa. Pour mieux comprendre les mécanismes de gazéification dans des atmosphères simples et mixtes de CO2 et H2O, nous avons suivi l’évolution de la texture, de la structure et de la chimie de surface du char le long de la gazéification sous CO2, H2O et leurs mélanges. Des caractérisations chimiques, texturales et structurales ont été ainsi effectuées sur des particules de char partiellement gazéifiés à 20%, 50% et 70% de conversion sous CO2, H2O et leurs mélanges. Ces caractérisations conduisent à une meilleure compréhension du déroulement de la réaction de gazéification

Controlling the Molecular Weight of Lignosulfonates by an Alkaline Oxidative Treatment at Moderate Temperatures and Atmospheric Pressure: A Size-Exclusion and Reverse-Phase Chromatography Study

The molecular weights of lignosulfonates (LSs) are modified by a rather simple process involving an alkaline oxidative treatment at moderate temperatures (70–90 °C) and atmospheric pressure. Starting from LSs with an average molecular weight of 90,000 Da, and using such a treatment, one can prepare controlled molecular weight LSs in the range of 30,000 to 3500 Da based on the average mass molecular weight. The LS depolymerisation was monitored via reverse-phase and size-exclusion chromatography. It has been shown that the combination of O2, H2O2 and Cu as a catalyst in alkaline conditions at 80 °C induces a high LS depolymerisation. The depolymerisation was systemically accompanied by a vanillin production, the yields of which reached 1.4 wt % (weight percentage on LS raw basis) in such conditions. Also, the average molecular weight and vanillin concentration were correlated and depended linearly on the temperature and reaction duration

Sustainable biodegradable coffee grounds filler and its effect on the hydrophobicity, mechanical and thermal properties of biodegradable PBAT composites

International audiencePoly(butylene adipate-co-terephthalate) (PBAT) and coffee grounds (CG) wastes are biodegradable materials. The high cost of PBAT restricts its marketability; the lignocellulosic CG were used as a reinforcing agent for PBAT. Thus, the present work focuses mainly on the preparation and characterization of bio-based PBAT composites filled with CG bio-additives with affordable cost, and with potential use in a variety of eco-friendly fields such as packaging, biomedical devices, and composting. The PBAT polymer was melt blended with various contents of CG powder using twin screw extrusion. The compatibility and dispersion state of investigated biocomposites in presence or absence of PEG as plasticizer were investigated by using scanning electron microscopy (SEM) and X-ray diffraction (XRD). The effect of the addition of PEG on PBAT/CG was characterized by differential scanning calorimetry (DSC), tensile properties, contact angle measurements, and thermogravimetric analysis. The chemical interaction between hydroxyl groups of CG particles and PEG plasticizer was achieved by these techniques. A pyrolysis kinetic model was proposed to identify the kinetic parameters of the thermal degradation of PBAT and CG powder

La nature du carbone déposé à la suite de la réaction de craquage du méthane sur un char de biomasse chargé en nickel

International audienceThe catalytic properties of raw biomass chars and Ni-loaded biomass chars prepared at a high-heating-rate were assessed in the methane decomposition reaction. The raw chars exhibited a moderated catalytic activity in methane cracking while the Ni-loaded chars showed a catalytic activity 10 times higher than the raw chars. The deposited carbon was a highly ordered one as evidenced by XRD, Raman analysis and oxygen reactivity tests. The activation energy in the combustion reaction was estimated to be 300 kJ/mol. These results indicate that biomass char can be an effective low-cost and active support for metal impregnation to be used in catalytic cracking of hydrocarbons for hydrogen production.Les propriétés catalytiques des chars de biomasse, dopés ou non au nickel et préparés par pyrolyze rapide à haute température, ont été évalués dans la réaction de décomposition du méthane. Les chars non dopés présentent une activité catalytique modérée dans la réaction de craquage du méthane, tandis que ceux dopés en nickel ont montré une activité catalytique 10 fois plus élevée. Le carbone déposé sur le char dopé était très ordonné, comme en témoignent les analyses DRX et Raman ainsi que les tests de réactivité à l’oxygène. L′énergie d'activation de la réaction de combustion a été estimée à 300 kJ/mol. Ces résultats indiquent que le char de biomasse représente un support catalytique à faible coût et efficace pour l'imprégnation de métaux utilisé dans le craquage catalytique d'hydrocarbures pour la production d'hydrogène

Quantitative Raman spectroscopy for the Ioncell (TM) process. Part 1 : comparison of univariate and multivariate calibration methods for the quantification of water and protic ionic liquid components

We investigate in this paper the potential of Raman spectroscopy for the quantification of protic ionic liquid components (acid and base) and water, in ionic liquid/water mixtures, taking 1.5-Diazabicyclo[4.3.0]non-5-enium acetate ([DBNH][OAc]) as a case study. We show that the combination of Raman spectroscopy and chemometrics is quite successful for the quantitative analysis of the ionic liquid components and water in mixtures over wide concentration ranges. The finding of the present work suggest that Raman spectroscopy should be considered more universally for the in-line monitoring and control of processes involving ionic liquid/H2O mixtures.Peer reviewe

Biomass Chars: The Effects of Pyrolysis Conditions on Their Morphology, Structure, Chemical Properties and Reactivity

International audienceSolid char is a product of biomass pyrolysis. It contains a high proportion of carbon, and lower contents of H, O and minerals. This char can have different valorization pathways such as combustion for heat and power, gasification for Syngas production, activation for adsorption applications, or use as a soil amendment. The optimal recovery pathway of the char depends highly on its physical and chemical characteristics. In this study, different chars were prepared from beech wood particles under various pyrolysis operating conditions in an entrained flow reactor (500-1400 degrees C). Their structural, morphological, surface chemistry properties, as well as their chemical compositions, were determined using different analytical techniques, including elementary analysis, Scanning Electronic Microscopy (SEM) coupled with an energy dispersive X-ray spectrometer (EDX), Fourier Transform Infra-Red spectroscopy (FTIR), and Raman Spectroscopy. The biomass char reactivity was evaluated in air using thermogravimetric analysis (TGA). The yield, chemical composition, surface chemistry, structure, morphology and reactivity of the chars were highly affected by the pyrolysis temperature. In addition, some of these properties related to the char structure and chemical composition were found to be correlated to the char reactivity