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The implementation of flow-through (FT) systems in the lignin-first approach can be a strategic tool for increasing the proficiency of biorefineries. Herein, the reductive catalytic fractionation (RCF) of waste beech wood sawdust (BWS) was conducted in an FT system using Ni on a nitrogen-doped carbon catalyst (35Ni/NDC) in pellet shape and MeOH and MeTHF as solvents. Lignin extraction was maximized in the first 4 h of time on stream (TOS), yielding maximum cumulative monomers of 247 mg gKL−1 using MeOH as solvent, extraction temperature of 235 °C, and reduction temperature of 225 °C. Importantly, the catalyst was used for two cycles and total time on stream (TOS) of 14 h without losing initial activity. These findings show that FT systems represent a promising solution for applications in lignin-first biorefineries.

Basic carbocatalyst made of simple natural precursors using environmentally friendly processes are eagerly required for a wide range of chemical processes. This work is devoted to a carbocatalyst with base functionality from of soybean flour as a nitrogen-rich carbon source. This metal-free basic carbocatalyst showed a density of basic sites of 0.165 mmol g-1 as quantified via CO2-TPD. The activity of the prepared basic carbons was successfully confirmed in two industrially important base-catalyzed reactions of green chemistry, namely, ring-opening polymerization (ROP) of ɛ-caprolactone and transesterification of isosorbide with dimethyl carbonate. Utilizing the prepared basic carbon in ROP reaction of ɛ-caprolactone, gave a white polymer with high molecular weight (MW = 30000 g mol-1), which is comparable to industrial products. Moreover, a yield of 79% of isosorbide bismethyl carbonate was obtained using the prepared basic carbon in isosorbide transesterification with dimethyl carbonate at 493 K for 6 hours

For the transition towards greener biorefineries with reduced waste, valorization of lignin to drop‐in chemicals instead of their combustion for energy purposes is a key issue for future processes. In this context, lignin should be extracted from lignocellulosic biomass (LCB) and fragmented into smaller units, followed by catalytic funneling to fine chemicals. In this review, we report on the classical approaches for lignin valorization from LCB: thermal treatments, solvolytic valorization, acid‐catalyzed process, and base‐catalyzed process. We also provide the reader with the modern approach of lignin valorization that led to an integrated LCB biorefinery. The performance of different solid catalysts in lignin‐first approach via reductive or oxidative catalytic fractionation at different conditions is discussed in detail.

Continuous-flow sorbitol dehydration in liquid water was performed on β zeolite (Si/Al molar ratio = 75) with conversion of 94 and 83 mol % isosorbide yield. This efficiency is due to the three-dimension pore architecture, high specific surface area (520 m2 g–1), and Brønsted acid sites of 69 μmol g–1. The pore size of β zeolite (6.6 × 6.7 Å2) is slightly larger than the cross section of sorbitol and isosorbide and enables an efficient diffusion of the reactant and product to/from the pores. Operation in continuous flow allows rapid dehydration of sorbitol to 1,4-sorbitan, after which the latter got converted to isosorbide. The high yield of isosorbide is attributed to the continuous removal of the formed products from the catalyst surface. Finally, direct isosorbide production from aqueous glucose solution via hydrogenation on Ni catalyst supported on nitrogen-doped carbon, followed by dehydration of the formed sorbitol to isosorbide, was pioneered.

Isosorbide is one of the most interesting cellulosic-derived molecules with great potential to be implemented in wide range of products that shaping our daily life. This minireview describes the recent developments in the production of isosorbide from sorbitol in batch and continuous flow systems under hydrothermal conditions using solid acid catalysts. Moreover, we are summarizing the current hurdles and challenges that facing the synthesis of isosorbide from cellulosic biomass in continuous flow process using solid acid catalysts, as well as the scaling up of this process into pilot level, which will lead to an established industrial process with high sustainability metrics.

Biorefinery seeks to utilize biomass waste streams as a source of chemical precursors with which to feed the chemical industry. This goal seeks to replace petroleum as the main feedstock,} however this task requires the development of efficient catalysts capable of transforming substances derived from biomass into useful chemical products. In this study{,} we demonstrate that a highly-active iridium complex can be solid-supported and used as a low-temperature catalyst for both the decomposition of formic acid (FA) to produce hydrogen{,} and as a hydrogenation catalyst to produce vanillyl alcohol (VA) and 2-methoxy-4-methylphenol (MMP) from vanillin (V); a lignin-derived feedstock. These hydrogenation products are promising precursors for epoxy resins and thus demonstrate an approach for their production without the need for petroleum. In contrast to other catalysts that require temperatures exceeding 100 °C{,} here we accomplish this at a temperature of

Sodium lignosulfonate (LS) was valorized to low molecular weight (Mw) fractions by combining solvothermal (SF) and catalytic hydrogenolysis/hydrogenation fragmentation (SHF) in continuous flow system. This achieved in either alcohol/water (EtOH2O or MeOH/H2O) as a solvent and Ni on nitrogen-doped carbon as a catalyst. The tunability according to temperature of both SF and catalytic SHF of LS has been separately investigated at 150°C, 200°C and 250°C. In SF, the minimal Mw was 2994 g mol-1 at 250°C with a dispersity (Đ) of 5.3 using MeOH/H2O. In catalytic SHF using MeOH/water, extremely low Mw was found (433 mg gLS-1) with Đ of 1.2 combined with 34 mg gLS-1. The monomer yield was improved to 42 mg gLS-1 using dual catalytic beds. These results is a direct evident that lignin is an unstable polymer at elevated temperature and could be efficiently deconstructed in hydrothermal conditions with and without catalyst.

Hydrogenation reactions in water at elevated temperatures are challenging for heterogeneous catalysts. Thus, we present a simple, cheap, scalable, and sustainable approach for synthesizing an efficient and stable Ni catalyst supported on highly porous nitrogen-doped carbon (NDC) in pellet form. The performance of this catalyst was evaluated in the aqueous-phase hydrogenation of lignocellulosic biomass-derived compounds, i.e., glucose (Glu), xylose (Xyl), and vanillin (V), using a continuous-flow system. The as-prepared 35 wt% Ni on NDC catalyst exhibited a high catalytic performance in all three aqueous-phase hydrogenation reactions, i.e., the conversion of Glu, Xyl, and V was 96.3 mol%, 85 mol%, and 100 mol% and the yield of sorbitol (Sor), xylitol (Xyt), and 2-methoxy-4-methylphenol (MMP) was 82 mol%, 62 mol%, and 100 mol%, respectively. This high activity was attributed to the high specific surface area of NDC and mainly to the heterojunction effects stabilizing and adjusting the homogenously and highly dispersed Ni nanoparticles (ANi = 20 m2 g−1) on the surface of NDC. Changing the electron density in the nickel nanoparticles allows the high performance of the catalyst for a long time on stream (40 h) with minimized Ni leaching and without the loss in catalytic performance.

Waste lignocellulosic biomass is sustainable and an alternative feedstock to fossil resources. Among the lignocellulosic derived compounds, 2,5-dimethylfuran (DMF) is a promising building block for chemicals, e.g., p-xylene, and a valuable biofuel. DMF can be obtained from 5-hydroxymethylfurfural (HMF) via catalytic deoxygenation using non-noble metals such as Ni in the presence of H2. Herein, we present the synthesis of DMF from HMF using 35 wt.% Ni on nitrogen-doped carbon pellets (35Ni/NDC) as a catalyst in a continuous flow system. The conversion of HMF to DMF was studied at different hydrogen pressures, reaction temperatures, and space times. At the best reaction conditions, i.e., 423 K, 8.0 MPa, and space time 6.4 kgNi h kgHMF&minus, 1, the 35Ni/NDC catalyst exhibited high catalytic activity with HMF conversion of 99 mol% and 80 mol% of DMF. These findings can potentially contribute to the transition toward the production of sustainable fine chemicals and liquid transportation fuels.

The continuous flow synthesis of p-xylene (pXL) via Diels–Alder cycloaddition of lignocellulosic biomass-derivable 2,5-dimethylfuran (DMF) and acrylic acid (AA) was performed over different type of zeolites, i.e. Beta, ZSM-5 and Y. Among the tested zeolites, Beta zeolite showed an optimum catalytic performance in pXL synthesis from DMF and AA. In this context, Beta zeolite with a Si/Al molar ratio of 150 which is abbreviated as Beta(150), resulted in complete DMF conversion with a pXL yield of 83% and by-product 2,5-dimethylbenzoic acid (DMBA) with a yield of 17%, at 473 K in 10.1 min residence time (τ), with excess AA (0.7 M). This high catalytic activity is attributed to the high specific surface area of 1180 m2 g−1 with a three-dimensional porous architecture with a pore diameter of 6.6 × 6.7 A and an acid site density above 40 μmol g−1. The utilized Beta(150) showed a very stable performance up to 10 h time on stream with minor deactivation after 8 h of TOS, while the pXL yield remained above 70%. The original catalytic performance of Beta(150) in the conversion of DMF to pXL was restored by applying a regeneration step for the spent catalyst, which is simple in continuous flow reactors. Finally, this sustainable continuous flow process enables an efficient and selective pXL production from DMF and AA as a dienophile at lower reaction temperature (473 K) and shorter residence time (τ = 10.1 min) in comparison to a batch fashion.

The removal of hydrophobic polymer films from surfaces is one of the top priorities of modern conservation science. Nanostructured fluids containing water, good solvents for polymers, either immiscible or partially miscible with water, and surfactants have been used in the last decade to achieve controlled removal. The dewetting of the polymer film is often an essential step to achieve efficient removal; however, the role of the surfactant throughout the process is yet to be fully understood. We report on the dewetting of a methacrylate/acrylate copolymer film induced by a ternary mixture of water, propylene carbonate (PC) and C9-11E6, a nonionic alcohol ethoxylate surfactant. The fluid microstructure was characterised through small angle X-ray scattering and the interactions between the film and water, water/PC and water/PC/C9-11E6, were monitored through confocal laser-scanning microscopy (CLSM) and analised both from a thermodynamic and a kinetic point of view. The presence of a surfactant is a prerequisite to induce dewetting of μm-thick films at room temperature, but it is not a thermodynamic driver. The amphiphile lowers the interfacial energy between the phases and favors the loss of adhesion of the polymer on glass, decreasing, in turn, the activation energy barrier, which can be overcome by the thermal fluctuations of polymer film stability, initiating the dewetting process.