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Molybdenum carbide supported on activated carbon (β‐Mo2C/AC) has been tested as catalyst in the reductive catalytic fractionation (RCF) of lignocellulosic biomass both in batch and in Flow‐Through (FT) reaction systems. High phenolic monomer yields (34 wt.%) and selectivity to monomers with reduced side alkyl chains (up to 80 wt.%) could be achieved in batch in the presence of hydrogen. FT‐RCF were made with no hydrogen feed, thus via transfer hydrogenation from ethanol. Similar selectivity could be attained in FT‐RCF using high catalyst/biomass ratios (0.6) and high molybdenum loading (35 wt.%) in the catalyst, although selectivity decreased with lower catalyst/biomass ratios or molybdenum contents. Regardless of these parameters, high delignification of the lignocellulosic biomass and similar monomer yields were observed in the FT mode (13‐15 wt.%) while preserving the holocellulose fractions in the delignified pulp. FT‐RCF system outperforms the batch reaction mode in the absence of hydrogen, both in terms of activity and selectivity to reduced monomers that is attributed to the two‐step non‐equilibrium processes and the removal of diffusional limitations that occur in the FT mode. Even though some molybdenum leaching was detected, the catalytic performance could be maintained with negligible loss of activity or selectivity for 15 consecutive runs. [ABSTRACT FROM AUTHOR]

Two series of Ni and Co catalysts supported onto La-Al2O3 were prepared and the CO2 hydrogenation reactions investigated. The catalytic performance was evaluated in terms of the evolution with the reaction temperature of the CO2 conversion and product (CH4 and CO) yields, as well as specific activities (TOF) and apparent activation energies. CH4 was the favored product over both metals while the TOF for CH4 formation was about three times higher for Ni than Co at 240–265 °C. Metallic particle size effects were found, with the TOF for CH4 formation decreasing over both Ni and Co as the mean metallic size decreased. In contrast, the TOF for CO formation tended to increase at a decreasing particle size for the catalysts with the smallest Ni particle sizes. The apparent activation energies for Ni and Co were very similar and significantly decreased to values of 73–79 kJ/mol when the metallic dispersion increased. The catalysts were prepared using the all-in-one method, resulting in (poly)vinyl alcohol (PVA) being a key additive that allowed us to enhance the dispersion of Ni and Co to give very effective catalysts. This comparative study joins the few existing ones in the literature in which catalysts based on these metals operated under strictly the same reaction conditions. [ABSTRACT FROM AUTHOR]

Renewed interest in CO2 methanation is due to its role within the framework of the Power-to-Methane processes. While the use of nickel-based catalysts for CO2 methanation is well stablished, the support is being subjected to thorough research due to its complex effects. The objective of this work was the study of the influence of the support with a series of catalysts supported on alumina, ceria, ceria–zirconia, and titania. Catalysts' performance has been kinetically and spectroscopically evaluated over a wide range of temperatures (150–500 °C). The main results have shown remarkable differences among the catalysts as concerns Ni dispersion, metallic precursor reducibility, basic properties, and catalytic activity. Operando infrared spectroscopy measurements have evidenced the presence of almost the same type of adsorbed species during the course of the reaction, but with different relative intensities. The results indicate that using as support of Ni a reducible metal oxide that is capable of developing the basicity associated with medium-strength basic sites and a suitable balance between metallic sites and centers linked to the support leads to high CO2 methanation activity. In addition, the results obtained by operando FTIR spectroscopy suggest that CO2 methanation follows the formate pathway over the catalysts under consideration. [ABSTRACT FROM AUTHOR]

Microstructured reactors (MSRs) are especially indicated for highly demanding heterogeneous catalysis due to the small channel dimensions that minimize diffusional limitations and enhance mass and heat transport between the fluid and the catalyst. Herein, we present the fabrication protocol of the fused filament 3D printing of silicone monolithic microreactors based on a multichannel design. Microchannels of 200 to 800 µm in width and up to 20 mm in length were developed following the scaffold-removal procedure using acrylonitrile butadiene styrene (ABS) as the material for the 3D-printed scaffold fabrication, polydimethylsiloxane (PDMS) as the building material, and acetone as the ABS removing agent. The main printing parameters such as temperature and printing velocity were optimized in order to minimize the bridging effect and filament collapsing and intercrossing. Heterogeneous catalysts were incorporated into the microchannel walls during fabrication, thus avoiding further post-processing steps. The nanoparticulated catalyst was deposited on ABS scaffolds through dip coating and transferred to the microchannel walls during the PDMS pouring step and subsequent scaffold removal. Two different designs of the silicone monolithic microreactors were tested for four catalytic applications, namely liquid-phase 2-nitrophenol photohydrogenation and methylene blue photodegradation in aqueous media, lignin depolymerization in ethanol, and gas-phase CO2 hydrogenation, in order to investigate the microreactor performance under different reaction conditions (temperature and solvent) and establish the possible range of applications. [ABSTRACT FROM AUTHOR]

Lignocellulosic residues have the potential for obtaining high value-added products that could be better valorized if biorefinery strategies are adopted. The debarking of short-rotation crops yields important amounts of residues that are currently underexploited as low-grade fuel and could be a renewable source of phenolic compounds and other important phytochemicals. The isolation of these compounds can be carried out by different methods, but for attaining an integral valorization of barks, a preliminary extraction step for phytochemicals should be included. Using optimized extraction methods based on Soxhlet extraction can be effective for the isolation of phenolic compounds with antioxidant properties. In this study, poplar bark (Populus Salicaceae) was used to obtain a series of extracts using five different solvents in a sequential extraction of 24 h each in a Soxhlet extractor. Selected solvents were put in contact with the bark sample raffinate following an increasing order of polarity: n-hexane, dichloromethane, ethyl acetate, methanol, and water. The oily residues of the extracts obtained after each extraction were further subjected to flash chromatography, and the fractions obtained were characterized by gas chromatography coupled with mass spectrometry (GC–MS). The total phenolic content (TPC) was determined using the Folin–Ciocalteu method, and the antioxidant activity (AOA) of the samples was evaluated in their reaction with the free radical 2,2-Diphenyl-picrylhydrazyl (DPPH method). Polar solvents allowed for higher individual extraction yields, with overall extraction yields at around 23% (dry, ash-free basis). Different compounds were identified, including hydrolyzable tannins, phenolic monomers such as catechol and vanillin, pentoses and hexoses, and other organic compounds such as long-chain alkanes, alcohols, and carboxylic acids, among others. An excellent correlation was found between TPC and antioxidant activity for the samples analyzed. The fractions obtained using methanol showed the highest phenolic content (608 μg of gallic acid equivalent (GAE)/mg) and the greatest antioxidant activity. [ABSTRACT FROM AUTHOR]

Fruit and vegetable wastes derived from the agri-food industry are generated in large amounts and they can cause great environmental contamination because they have a high moisture content and microbial load. However, both their structural parts (stems, leaves, peels, pulps, seeds, and roots) and the residues resulting after the extraction of their juices are rich in different valuable compounds such as antioxidants, oils, fiber, fatty acids, isoprenoids, lipids, proteins, saponins, and phytoestrogens. Such bioactive compounds can be used as pharmaceutical excipients, food additives, or included in pharmaceutical formulations or food matrices for obtaining nutraceutical products and functional foods, respectively. The aim of this review is to present the most promising alternatives for the valorization of selected fruit and vegetable wastes, currently underexploited, as well as the challenges that may arise when considering the valorization of these wastes in the form of value-added bioactive products. This is exemplified through the revision of the opportunities offered by artichoke, cardoon, asparagus, and pomegranate, which generate large amounts of waste during their processing. A final section is devoted to present the emerging technologies that are being developed for an efficient extraction of bioactive compounds from vegetable matrices. [ABSTRACT FROM AUTHOR]

The biorefinery concept has been proposed as a route map to convert biomass into fuels and chemicals, maximizing economic and environmental benefits while minimizing pollution. A biorefinery strategy based on fast pyrolysis is proposed following a two-stage process, where biomass is first subjected to fast pyrolysis, optimized to collect up to 75% (per unit weight of biomass) of a liquid fraction called bio-oil. This bio-oil or its fractions can be upgraded in a second step to different chemicals, to a syngas and/or to energy. In particular, the catalytic steam reforming of the aqueous fraction of bio-oil obtained by fractionation with water is one of the most attractive possibilities for bio-oil upgrading, yielding a H2-rich syngas with low CO content. From the results obtained, it can be concluded that the best alternative for the catalytic steam reforming process is hydrogen production through further purification of the gas obtained. [ABSTRACT FROM AUTHOR]

In this work, the production of renewable hydrocarbons was explored by the means of waste cottonseed oil (WCSO) micropyrolysis at 500 °C. Catalytic upgrading of the pyrolysis vapors was studied using α-Al2O3, γ-Al2O3, Mo-Co/γ-Al2O3, and Mo-Ni/γ-Al2O3 catalysts. The oxygen removal efficiency was much lower in non-catalytic pyrolysis (18.0%), whilst γ-Al2O3 yielded a very high oxygen removal efficiency (91.8%), similar to that obtained with Mo-Co/γ-Al2O3 (92.8%) and higher than that attained with Mo-Ni/γ-Al2O3 (82.0%). Higher conversion yields into total renewable hydrocarbons were obtained with Mo-Co/γ-Al2O3 (61.9 wt.%) in comparison to Mo-Ni/γ-Al2O3 (46.6%). GC/MS analyses showed a relative chemical composition of 31.3, 86.4, and 92.6% of total renewable hydrocarbons and 58.7, 7.2, and 4.2% of oxygenated compounds for non-catalytic bio-oil (BOWCSO), BOMoNi and BOMoCo, respectively. The renewable hydrocarbons that were derived from BOMoNi and BOMoCo were mainly composed by olefins (35.3 and 33.4%), aromatics (31.4 and 28.9%), and paraffins (13.8 and 25.7%). The results revealed the catalysts' effectiveness in FFA decarbonylation and decarboxylation, as evidenced by significant changes in the van Krevelen space, with the lowest O/C ratio values for BOMoCo and BOMoNi (O/C = 0–0.10) in relation to the BOWCSO (O/C = 0.10–0.20), and by a decrease in the presence of oxygenated compounds in the catalytic bio-oils. [ABSTRACT FROM AUTHOR]

Ash behavior is a key operational aspect of industrial-scale power generation by means of biomass combustion. In this work, FactSageTM 6.4 software was used to develop and assess three models of wheat straw combustion in a vibrating grate-fired commercial boiler of 16 MWth, aiming to describe the inorganic elements release as well as fly ash melting behavior and composition. Simulations were carried out solving four consecutive calculation stages corresponding to the main plant sections. Chemical fractionation was adopted in order to distinguish between reactive, inert and partially reactive biomass fractions. The developed models allow take into account different levels of partial reactivity, values of the temperature for each sub-stage on the grate, and ways to apply entrained streams based on data from the elemental analyses of the fly ashes. To this end, two one-week experimental campaigns were conducted in the plant to carry out the sampling. It has been found that considering chemical fractionation is indispensable to describe the entrainment of solid particles in the gas stream. In addition, the best results are obtained by adopting a small reactivity (2%) of the inert fraction. As for fly ash composition, the concentrations of the major elements showed good agreement with the results from the chemical analyses. In the case of S and Cl, calculations revealed a match with gas cooling effects in the superheaters as well as an entrainment effect. The melting behavior together with the presence of KCl and K2SO4 condensates, point out at possible corrosion phenomena in walls at temperatures of 700–750 °C. [ABSTRACT FROM AUTHOR]

Lignocellulosic materials are promising alternatives to non-renewable fossil sources when producing aromatic compounds. Lignins from Populus salicaceae. Pinus radiata and Pinus pinaster from industrial wastes and biorefinery effluents were isolated and characterized. Lignin was depolymerized using homogenous (NaOH) and heterogeneous (Ni-, Cu- or Ni-Cu-hydrotalcites) base catalysis and catalytic hydrogenolysis using Ru/C. When homogeneous base catalyzed depolymerization (BCD) and Ru/C hydrogenolysis were combined on poplar lignin, the aromatics amount was ca. 11 wt.%. Monomer distributions changed depending on the feedstock and the reaction conditions. Aqueous NaOH produced cleavage of the alkyl side chain that was preserved when using modified hydrotalcite catalysts or Ru/C-catalyzed hydrogenolysis in ethanol. Depolymerization using hydrotalcite catalysts in ethanol produced monomers bearing carbonyl groups on the alkyl side chain. The analysis of the reaction mixtures was done by size exclusion chromatography (SEC) and diffusion ordered nuclear magnetic resonance spectroscopy (DOSY NMR). 31P NMR and heteronuclear single quantum coherence spectroscopy (HSQC) were also used in this study. The content in poly-(hydroxy)-aromatic ethers in the reaction mixtures decreased upon thermal treatments in ethanol. It was concluded that thermo-solvolysis is key in lignin depolymerization, and that the synergistic effect of Ni and Cu provided monomers with oxidized alkyl side chains. [ABSTRACT FROM AUTHOR]

Abstract Syngas production has been investigated via oxidative steam reforming of concentrated glycerol aqueous solutions (Steam-to-Carbon molar ratio = 4 and 6 vol% O 2 in N 2). Results obtained using different (bulk) bed materials (SiO 2 , SiC and γ-Al 2 O 3) were compared with results achieved while using a cobalt aluminate catalyst prepared by coprecipitation dispersed in each of those same bed fillers. The effects on conversion and gas production of the filler bed material, activation temperature (1023 K, 1073 K and 1123 K) and reaction temperature (823 K, 923 K and 1023 K) were studied, as well as the catalyst reuse (at 1023 K) to assess its performance after regeneration. High glycerol conversion levels (above 80%) were attained at 1023 K without the catalyst. The main gaseous products were H 2 , CO, CO 2 and CH 4. Using a bed of commercial γ-Al 2 O 3 , around 90% of the C fed into the reactor could be converted into gaseous products, yielding syngas with H 2 /CO molar ratio close to 1. In what concerns the use of the Co aluminate catalyst in the oxidative steam reforming of glycerol, very high overall conversion levels (above 90% in all cases) were achieved, as well as significantly higher H 2 /CO molar ratios (within the 2.0–2.5 range). The Co catalyst helped in effectively converting approximately 90% of the glycerol in the feed into product gases at temperatures as low as 823 K, and up to 94% of overall C conversion to gas could be achieved at 1023 K. Higher activation or reforming reaction temperatures did not improve the catalyst performance, the glycerol conversion or gas production. The catalyst could be effectively used during 20 h on stream in four consecutive reaction/regeneration cycles. Catalyst deactivation by encapsulating carbon caused drastic changes in the catalyst structure, which evolved into a core-shell configuration when deactivated. Upon regeneration by air oxidation and subsequent activation, the catalyst recovered its original structure and initial activity. These new insights allowed to propose the use of a pre-reforming step over relatively inexpensive bulk bed materials, where thermal decomposition of glycerol processes dominate followed by the catalytic oxidative steam reforming, to obtain high syngas production at moderate conditions (823 K). Highlights • γ-Al 2 O 3 , SiO 2 or SiC were effective in oxidative steam reforming. • A new Co spinel catalyst was tested and dramatically changed product selectivities. • The regeneration and reuse of the catalyst was successfully tested. • The catalyst maintained its activity upon 20 h on stream. • Co species migrated to the surface over the spinel structure acting as Co reservoir. [ABSTRACT FROM AUTHOR]

Reductive depolymerization of lignin-containing stillage (LA lignin) from 2nd generation bioethanol industrial plants have been studied over two different families of catalysts: conventional porous Ru catalysts supported on ZrO 2 or activated carbon, and 1-dimensional Ru catalysts supported on multi-walled carbon nanotubes (MWCNT). The lignin depolymerization degree using conventional porous catalysts resulted in values of 42 and 53%, for Ru/ZrO 2 and Ru/C, respectively. Strikingly, when using 1D-supported catalysts (Ru/MWCNT and Ru/ZrO 2 /MWCNT), the extent of lignin depolymerization measured by 1 H 13 C HSQC NMR, reached values of c.a. 80% of β-O-4 bond disappearance and a reduction of the average molecular weight from 3600 Da to ~ 1900 Da. The higher accessibility of the lignin agglomerates to the 1-D catalyst nanoparticles substantially improves the lignin depolymerization degree, which make this approach of great interest in the production of fine chemicals and fuel additives. [ABSTRACT FROM AUTHOR]

Molybdenum carbide supported on activated carbon (β-Mo 2 C/AC) has been tested as catalyst in the reductive catalytic fractionation (RCF) of lignocellulosic biomass both in batch and in Flow-Through (FT) reaction systems. High phenolic monomer yields (34 wt.%) and selectivity to monomers with reduced side alkyl chains (up to 80 wt.%) could be achieved in batch in the presence of hydrogen. FT-RCF were made with no hydrogen feed, thus via transfer hydrogenation from ethanol. Similar selectivity could be attained in FT-RCF using high catalyst/biomass ratios (0.6) and high molybdenum loading (35 wt.%) in the catalyst, although selectivity decreased with lower catalyst/biomass ratios or molybdenum contents. Regardless of these parameters, high delignification of the lignocellulosic biomass and similar monomer yields were observed in the FT mode (13-15 wt.%) while preserving the holocellulose fractions in the delignified pulp. FT-RCF system outperforms the batch reaction mode in the absence of hydrogen, both in terms of activity and selectivity to reduced monomers that is attributed to the two-step non-equilibrium processes and the removal of diffusional limitations that occur in the FT mode. Even though some molybdenum leaching was detected, the catalytic performance could be maintained with negligible loss of activity or selectivity for 15 consecutive runs., (© 2024 The Authors. ChemSusChem published by Wiley-VCH GmbH.)

IN THE PRESENT WORK, SEVERAL FATTY ACID METHYL ESTERS (FAME) HAVE BEEN SYNTHESIZED FROM VARIOUS FATTY ACID FEEDSTOCKS: used frying olive oil, pork fat, soybean, rapeseed, sunflower, and coconut. The oxidation stabilities of the biodiesel samples and of several blends have been measured simultaneously by both the Rancimat method, accepted by EN14112 standard, and the PetroOXY method, prEN16091 standard, with the aim of finding a correlation between both methodologies. Other biodiesel properties such as composition, cold filter plugging point (CFPP), flash point (FP), and kinematic viscosity have also been analyzed using standard methods in order to further characterize the biodiesel produced. In addition, the effect on the biodiesel properties of using 4-allyl-2,6-dimethoxyphenol and catechol as additives in biodiesel blends with rapeseed and with soybean has also been analyzed. The use of both antioxidants results in a considerable improvement in the oxidation stability of both types of biodiesel, especially using catechol. Adding catechol loads as low as 0.05% (m/m) in blends with soybean biodiesel and as low as 0.10% (m/m) in blends with rapeseed biodiesel is sufficient for the oxidation stabilities to comply with the restrictions established by the European EN14214 standard. An empirical linear equation is proposed to correlate the oxidation stability by the two methods, PetroOXY and Rancimat. It has been found that the presence of either catechol or 4-allyl-2,6-dimethoxyphenol as additives affects the correlation observed.