Biorefining Twin Transition: Digitalisation for Bio-based Chemicals/Materials - Discovery, Design and Optimisation

The article discusses the production of platform chemicals from various biological sources, including glycerol, lignin, cellulose, bio-oils, and sea products. It presents the results of catalytic and downstream processes involved in the conversion of these biomass-derived feedstocks. The experimental approaches are complemented by numerical descriptions, ranging from density functional theory (DFT) calculations to kinetic modellingof the experimental data. This multi-scale modelling approach helps to understand the underlying mechanisms and optimize the production of platform chemicals from renewable resources

Catalytic cracking of biomass-derived hydrocarbon tars or model compounds to form biobased benzene, toluene, and xylene isomer mixtures

The gasification of biomass is one of the most prominent technologies for the conversion of the raw material feedstock to polymers, useful chemical substances, and energy. The main engineering challenge during the processing of wastes is the presence of tars in gaseous reaction products, which could make this operation methodology unsuccessfully due to the blockage of separating particle filters, fuel line flow, and substantial transfer losses. Catalytic hydrocarbon cracking appears to be a promising developing approach for their optimal removal. However, it is still highly desirable to enhance the catalysts’ activity kinetics, selectivity, stability, resistance to (ir)­reversible coke deposition, and regeneration solutions. The purpose of this Review is to provide a comparative systematic evaluation of the various natural, synthetic, and hybrid ways to convert the model molecular compounds into benzene, toluene, xylene, (poly)­aromatics, syngas, and others. The recent scientific progress, including calcite, dolomite, lime, magnesite, olivine, char, nonmetallic activated carbons, supported alkali, noble, and transition metals, and (metal-promoted) zeolites, is presented. A special concentrated attention is paid to effectiveness, related to hydrogenation, peculiar pore structure, and formulations’ suitable acidity. The role of catalysis is described, recommendations for prospective catalyzed mechanisms are provided, and future technical feasibility is discussed as well

Wet torrefaction of biomass waste into levulinic acid and high-quality hydrochar using H-beta zeolite catalyst

Wet torrefaction (WT) is an effective pretreatment method of biomass waste for producing high-quality hydrochar and valuable liquid products. This study delves into how acid catalysts and reaction conditions in WT impact the resulting hydrochar’s surface characteristics and elemental composition, as well as the distribution of liquid products. The focus is on utilizing wood cellulose pulp residue (WCPR) as the feedstock with H-Beta zeolite catalyst in a nitrogen-rich environment. The WT process involves a temperature range of 180–260 °C, and reaction durations spanning 15–60 min. The findings reveal that WT conditions, including the catalyst for WCPR, significantly influence the hydrochar’s properties and liquid product distribution. With increasing temperature and reaction time, the hydrochar experiences changes, including increased carbon content and reduced oxygen content. The study identifies 260 °C and 30 min as the optimal temperature and time for levulinic acid production, achieving a remarkable selectivity of 62.8% with the H-Beta zeolite catalyst using H$_2$O/WCPR = 10. Various properties of the resulting hydrochar are assessed, including higher heating values (HHVs), decarbonization (DC), dehydrogenation (DH), deoxygenation (DO), enhancement factor, carbon enrichment, surface area, pore diameter, weight loss as well as solid, carbon, hydrogen, and energy yields. The WT + Beta_220 sample, processed at 220 °C for 30 min, exhibited the highest HHV at 30.3 MJ/kg and carbon content at 78.9% in hydrochar compared to various biomass types, with an enhancement factor of 1.51 and carbon enrichment of 1.63, while the sequence of element removal during WT prioritized as DO > DH > DC. Furthermore, it is worth highlighting that the most significant weight loss, increasing from 17.0 to 60.7%, was observed under the same WT conditions. Lastly, a comprehensive reaction pathway is proposed to elucidate the WT of WCPR with the presence of H-Beta zeolite catalyst under these optimized conditions

Catalytic wet torrefaction of biomass waste into bio-ethanol, levulinic acid, and high quality solid fuel

Creating a sustainable society hinges on efficient chemical and fuel production from renewable cellulosic biomass, necessitating the development of innovative transformation routes from cellulose. In this investigation, we unveil a pioneering chemocatalytic method, utilizing an H-ZSM-5 catalyst within a batch reactor under a nitrogen atmosphere, for the simultaneous one-pot generation of levulinic acid (LA) and/or ethanol during wet torrefaction (WT) of wood cellulose pulp residue (WCPR), yielding high-quality solid fuel. WT parameters include a temperature range of 180 to 260 °C, H$_2$O/WCPR = 10, and reaction durations of 15 to 60 min. Optimal conditions for bio-ethanol production are identified at 180 °C and 15 min, achieving an outstanding 89.8 % selectivity with H-ZSM-5 catalyst. Notably, 69.5 % LA formation occurs at 240 °C after 60 min. Hydrochar assessments include higher heating values (HHVs), decarbonization (DC), dehydrogenation (DH), deoxygenation (DO), enhancement factor, carbon enrichment, surface area, pore diameter, weight loss, and yields of solid, carbon, hydrogen, and energy. The highest carbon content of 76.7 % is attained at 260 °C for 60 min, resulting in an HHV of 29.0 MJ/kg, an enhancement factor of 1.44, and carbon enrichment of 1.59, with a sequence of element removal as DO > DH > DC. A proposed reaction pathway elucidates WT of WCPR with the H-ZSM-5 catalyst, emphasizing the direct cellulose conversion into hydroxyacetone and subsequent ethanol generation through C–C cleavage of hydroxyacetone. Through this research approach, both ethanol and LA can be produced efficiently from renewable cellulosic biomass, offering a novel pathway to reduce dependence on fossil resources

Wet torrefaction of biomass waste into high quality hydrochar and value-added liquid products using different zeolite catalysts

Wet torrefaction (WT) proves to be a highly efficient pretreatment method for biomass waste, resulting in the production of hydrochar and valuable liquid products. In this study, a groundbreaking chemocatalytic approach is introduced, employing various zeolite catalysts (H-ZSM-5, H-Beta, H–Y, H-USY, and H-Mordenite) in a batch reactor under a nitrogen atmosphere. This method enables the simultaneous one-pot production of levulinic acid (LA) and/or bio-ethanol during the WT process of wood cellulose pulp residue (WCPR), ultimately yielding high-quality solid fuel. The WT process involves at 220 and 260 °C, H$_2$O/WCPR = 10, and torrefaction time at 15, 30 and 60 min. The study identifies that at 220 °C and 15 min, as the optimal temperature and time, for bio-ethanol production, achieving a selectivity of 59.0 % with the H–Y catalyst, while the highest amount of bio-ethanol (75.6 %) was detected in presence of H-USY zeolite at 260 °C after 60 min. In addition, it was found the formation of relatively high amount of LA (62.0 %) at 220 °C after 60 min but using the H-ZSM-5 catalyst. For the WT + Mordenite sample (220 °C, 60 min), the highest carbon content of 71.5 % is achieved, resulting in the higher heating value (HHV) of 27.3 MJ/kg, an enhancement factor of 1.36, and carbon enrichment of 1.48, with the sequence of element removal during WT prioritized as DO > DH > DC and the weight loss of 68 %. Finally, the reaction mechanism was proposed to elucidate the formation of liquid products after WT of WCPR with participation of zeolite catalysts. The main pathway involving the direct conversion of cellulose into hydroxyacetone, followed by the subsequent generation of ethanol through the C–C cleavage of hydroxyacetone while LA formed via well-known route which includes cellulose hydrolysis to form glucose, conversion to 5-HMF and the subsequent transformation of 5-HMF into LA

Reaction microkinetic model of xylose dehydration to furfural over beta zeolite catalyst

In recent decades, there has been a growing interest in bio-refineries as a crucial element in transitioning to a low-carbon economy. One specific aspect of this interest is the conversion of carbohydrates into separate platform chemicals, such as furfural (FUR), which play a significant functional role in various daily life processes. This research paper focuses on investigating the use of a H-beta catalyst with SiO2/Al2O3 = 28 for producing furfural from xylose in water. Various conditions, such as temperature and initial solution concentration, are studied to determine their effect on FUR yield. The highest FUR yield (40 mol.%) is obtained when FUR is the only product species. We also report that about 90% yield from reaction with fresh catalyst can be achieved after catalyst regeneration. The activation energies for the reaction on the catalyst surface are found to be in the range of 38–75 kJ/mol. A mathematical kinetic model with three irreversible steps is derived to estimate the reaction sequence at 160, 180, and 200 °C. The model takes into account mechanisms such as adsorption, desorption, and transport (internal or external). Our results suggest that the H-beta catalyst shows high activity toward FUR yield and could be a promising alternative for mass-scale production of the latter

Wet torrefaction of biomass waste into value-added liquid product (5-HMF) and high quality solid fuel (hydrochar) in a nitrogen atmosphere

Wet torrefaction (WT) offers distinct advantages over other pretreatment methods for producing hydrochar, making it also a promising technology for converting biomass waste into value-added platform chemicals. In this research, we conducted a comprehensive investigation into the influence of reaction conditions on the WT process, evaluating its effects on the surface morphology and elemental composition of the resulting hydrochar, as well as on the formation of value-added liquid products, such as 5-hydroxymethylfurfural (5-HMF). During the course of our study, we utilized wood cellulose pulp residue (WCPR) as the feedstock and subjected it to WT in a nitrogen atmosphere. This process encompassed a temperature range of 180–260 °C, H$_2$O/WCPR ratios ranging from 10 to 25, and reaction durations spanning from 15 to 60 min. Our findings unequivocally revealed that the reaction conditions during the WT of WCPR significantly influence the properties of the resulting hydrochar and the distribution of liquid products. Elemental and proximate analyses showed that as the reaction temperature and time increased during the WT of WCPR, the hydrochar composition experienced significant changes, including an increase in carbon content and a reduction in oxygen content. At the same time, the distribution of the liquid product revealed that 220 °C was the optimal temperature for producing 5-HMF, achieving an impressive selectivity of 73.3 % without the need for a catalyst. In summary, our research has established the optimal conditions for WT of WCPR as follows: a temperature of 220 °C, a reaction time of 30 min, and an H$_2$O/WCPR ratio of 10. Various properties of the obtained hydrochar were thoroughly assessed, including the higher heating value (HHV), decarbonization, dehydrogenation, deoxygenation, enhancement factor, surface area, pore diameter, as well as solid, carbon, hydrogen, and energy yields. The highest carbon content, reaching 68.3 %, was achieved at 260 °C after 30 min of treatment, resulting in an HHV of 27,340 kJ/kg and an enhancement factor of 1.43. Finally, we have proposed a comprehensive reaction pathway to elucidate the WT of WCPR under these optimized conditions

Sulfuric Acid Leaching of Altered Ilmenite Using Thermal, Mechanical and Chemical Activation

The kinetics of the sulfuric acid leaching of altered ilmenite, mechanisms, and process intensification methods were studied. The effect of changing the chemical composition during grinding was determined. The content of ilmenite and pseudorutile decreased from 5.3% to 3.1% and from 90.2% to 63.1%, respectively. Rutile increased from 4.5% to 28.7%, while a pseudobrookite new phase appeared in the amount of 5.1% after 2 h of grinding. It was found that the modification of raw material by sulfuric acid led to the increase of the decomposition rate, and at the same time, decreased when the ore was utilized due to an increase of insoluble TiO2 content. Isothermal conditions were evaluated with H2SO4 concentration varying from 50 to 96%. The data obtained were described with the approximation of the contracting sphere model. It was shown for the first time that H2SO4 > 85 wt% causes a sharp constant decrease of titanium. Correlating these phenomena allows for the consideration of H2SO4·H2O as reagents, rather than H2SO4 molecules. It was experimentally proven that at a temperature above 190 °C, the Ti leaching degree dropped, which is explained by the formation of polymerized TiOSO4. Finally, it was shown that adding NaF reduced the activation energy to 45 kJ/mol