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There is an environmental concern regarding the use of petroleum-based lubricants, which are generally toxic and nonbiodegradable. Biobased lubricants, such as vegetable oils, are the alternative: they show excellent lubricity, are readily biodegradable and nontoxic. However, a major disadvantage of using vegetable oils in lubricant applications is their lack of thermo-oxidative stability, which can be improved by antioxidant additives. Here, we propose the use of lignin-based additives in biolubricant formulations to improve this feature, based on lignin’s known antioxidant properties. To ensure a stable dispersion in vegetable oil, lignin was partially esterified. Antioxidant properties of lignin before and after palmitoylation were demonstrated in a 2,2-diphenyl-1-picrylhydrazyl (DPPH) assay. Four different lignin-based fractions, commercial Protobind P1000 soda lignin from straw, solvolytically fractionated Protobind P1000 lignin and two lignin fractions from reductively catalyzed fractionation (RCF) of native birch wood, were tested in biolubricant formulations with castor oil as base oil. Those lignin fractions exhibited excellent performance compared to butylated hydroxytoluene (BHT), a commonly used petroleum-based antioxidant. Formulations of modified lignin in castor oil possess improved thermo-oxidative stability, as illustrated by their increased oxidation induction time. Additionally, rheological and tribological tests demonstrate similar, or in some cases improved, lubricating properties compared to castor oil. This study showcases the successful incorporation of lignin-based antioxidants in biolubricant formulations, tackling the major disadvantage of vegetable oils as environment-friendly lubricants.

Herein, we present a full lignocellulose-to-chemicals valorization chain, wherein low molecular weight and highly functional lignin oligomers, obtained from reductive catalytic fractionation (RCF) of pine wood, were used to fully replace bisphenol A (BPA) for synthesizing bio-based epoxy resins.

Efficient transformation of biomass to value-added chemicals and high-energy density fuels is pivotal for a more sustainable economy and carbon-neutral society. In this framework, developing potential cascade chemical processes using functionalised heterogeneous catalysts is essential because of their versatile roles towards viable biomass valorisation. Advances in materials science and catalysis have provided several innovative strategies for the design of new appealing catalytic materials with well-defined structures and special characteristics. Promising catalytic materials that have paved the way for exciting scientific breakthroughs in biomass upgrading are carbon materials, metal-organic frameworks, solid phase ionic liquids, and magnetic iron oxides. These fascinating catalysts offer unique possibilities to accommodate adequate amounts of acid-base and redox functional species, hence enabling various biomass conversion reactions in a one-pot way. This review therefore aims to provide a comprehensive account of the most significant advances in the development of functionalised heterogeneous catalysts for efficient biomass upgrading. In addition, this review highlights important progress ensued in tailoring the immobilisation of desirable functional groups on particular sites of the above-listed materials, while critically discussing the role of consequent properties on cascade reactions as well as on other vital processes within the bio-refinery. Current challenges and future opportunities towards a rational design of novel functionalised heterogeneous catalysts for sustainable biomass valorisation are also emphasized. ispartof: Chemical Society Reviews vol:47 issue:22 pages:8349-8402 ispartof: location:England status: published

In the last 5 years, reductive catalytic fractionation of lignocellulose biomass has emerged as a promising biorefinery concept that combines biomass fractionation with the preservation of chemical functionality in its products. Although significant efforts have been made in optimizing this technology on lab scale, the implementation on a larger (pilot) scale is still in its infancy. In our own search for the scale-up potential of this technology, we faced several fundamental and technical research questions that, to this day, remain unanswered. These fundamental questions are related to four main aspects of RCF, the lignocellulose feedstock, the operating pressure, the redox catalyst, and the solvent. In order to inspire future multidisciplinary research in the RCF community, these scale-up challenges are presented and discussed via multiple angles combining chemical process hurdles with more technical aspects, such as reactor design and process consequences.

One of the foremost challenges in lignocellulose conversion encompasses the integration of effective lignin valorization in current carbohydrate-oriented biorefinery schemes. Catalytic reductive fractionation (CRF) of lignocellulose offers a technology to simultaneously produce lignin-derived platform chemicals and a carbohydrate-enriched pulp via the combined action of lignin solvolysis and metal-catalyzed hydrogenolysis. Herein, the solvent (composition) plays a crucial role. In this contribution, we study the influence of alcohol/water mixtures by processing poplar sawdust in varying MeOH/water and EtOH/water blends. The results show particular effects that strongly depend on the applied water concentration. Low water concentrations enhance the removal of lignin from the biomass, while the majority of the carbohydrates are left untouched (scenario A). Contrarily, high water concentrations favor the solubilization of both hemicellulose and lignin, resulting in a more pure cellulosic residue (scenario B)...

Recent lignin-first catalytic lignocellulosic biorefineries produce large quantities of two potential platform chemicals, 4-n-propylguaiacol (PG) and 4-n-propylsyringol. Because conversion into 4-n-propylcyclohexanol (PCol), a precursor for novel polymer building blocks, presents a promising valorization route, reductive demethoxylation of PG was examined here in the liquid-phase over three commercial hydrogenation catalysts, viz. 5 wt % Ru/C, 5 wt % Pd/C and 65 wt % Ni/SiO2–Al2O3, at elevated temperatures ranging from 200 to 300 °C under hydrogen atmosphere. Kinetic profiles suggest two parallel conversion pathways: Pathway I involves PG hydrogenation to 4-n-propyl-2-methoxycyclohexanol (PMCol), followed by its demethoxylation to PCol, whereas Pathway II constitutes PG hydrodemethoxylation to 4-n-propylphenol (PPh), followed by its hydrogenation into PCol. The slowest step in the catalytic formation of PCol is the reductive methoxy removal from PMCol. Moreover, under the applied reaction conditions, PCol...

Reductive catalytic fractionation of lignocellulose is a promising “lignin-first” biorefinery strategy wherein lignin is solvolytically extracted from the cell wall matrix and simultaneously disassembled, resulting in a stable lignin oil and a solid carbohydrate-rich residue. Herein, we report on the different influence of acidic (H3PO4) and alkaline (NaOH) additives on the Pd/C-catalyzed reductive processing of poplar wood in methanol (MeOH). It was found that the addition of small quantities of H3PO4 results in three rather than two product streams, since under acidic conditions both delignification and alcoholysis of hemicellulose are promoted, leaving behind a cellulose-rich pulp. The simultaneous acid-catalyzed fractionation of the carbohydrates into separate cellulose and hemicellulose streams provides opportunities for more efficient downstream conversion, as processing parameters can be tailored to the needs of both streams. Alkaline conditions, on the other hand, also enhance delignification, but...