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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.

The synthesis of novel, renewable lignin-based protective films with anticorrosive properties is presented in this work. Thermosetting films are prepared by means of tandem UV-initiated thiol-yne "click" synthesis and Claisen rearrangement strategy. These films contain high lignin loading, 46-61%, originating from a nickel-catalyzed birch wood reductive catalytic fractionation (RCF) process. Lignin fractions with varying monomer content are compared before resins preparation, namely a mixture of monomers and oligomers without fractionation, or after fractionation via extraction and membrane separation. This study aims to determine if the separation of lignin monomers and oligomers is necessary for the application as a thermosetting resin. The resulting films exhibit remarkable adhesion to a metal surface and excellent solvent resistance, even after exposure to a corrosive environment. Moreover, those films show superior barrier properties, studied with odd random phase electrochemical impedance spectroscopy (ORP EIS). After 21 days of exposure, the examined films still show impressive high corrosion protection with the low-frequency impedance approximate to 10(10) omega cm(2) and capacitive behavior. This work demonstrates an interesting proof-of-concept where laborious, costly, and energy-intensive separation of the depolymerized lignin mixture of monomers and oligomers is not necessary for the successful resin synthesis with excellent properties using the applied synthetic strategy.

Every twig and splinter used Plant-based production of commodity chemicals faces steep competition from fossil resources, which are often cheaper and easier to partition. Sustainable use of renewable resources requires strategies for converting complex and recalcitrant biomolecules into streams of chemicals with extraordinary efficiency. Liao et al. developed a biorefinery concept in which wood is eventually fully converted into useful chemicals: phenol, propylene, pulp amenable to ethanol production, and phenolic oligomers that can be incorporated into ink production (see the Perspective by Zhang). A life-cycle assessment and techno-economic analysis highlight the efficiency of the process and reveal the potential for such biorefinery strategies to contribute to sustainable chemicals markets. Science , this issue p. 1385 ; see also p. 1305

Depolymerization of cellulose is often used as a (pre)treatment protocol within the catalytic valorization strategies of cellulose. Typical depolymerization protocols yield polymerization degrees above 70 anhydroglucose units (AGU). However, shorter cellulose fibers are of interest in the search for accessible dietary fiber additives or renewable materials with distinct mechanical properties (bio-composites). In this work, short-polymer microcrystalline celluloses (SMCC) with an average polymerization degree between 29 and 70 AGU were produced with material yields of 95 % and above by combining a planetary ball mill pretreatment with mild acid hydrolysis. By first decreasing the levelling-off degree of polymerization (LODP) with an intensive ball mill treatment, a mild acid hydrolysis protocol was sufficient to ensure high yields of SMCC. Furthermore, the desired polymerization degree could be obtained by tuning the process parameters.

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.

© 2018, The Author(s), under exclusive licence to Springer Nature Limited. There is an urgent need to address environmental problems caused by our transportation systems, which include the reduction of associated CO2 emissions. In the short term, renewable drop-in fuels are ideal, as they allow a direct integration into the existing infrastructure. However, preferably they would perform better than current alternatives (for example, bioethanol) and be synthesized in a more efficient way. Here we demonstrate the production of biogasoline with a direct upstream integration into processes in existing petrorefinery facilities that targets the 10% bio-based carbon in accordance with the current European Union directives (for 2020) for biofuels. To achieve this goal, we show the valorization of (hemi)cellulose pulp into light naphtha using a two-phase (H2O:organic) catalytic slurry process. A C5–C6 alkane stream, enriched with bio-derived carbon and compatible with further downstream petrorefinery operations for (bio)gasoline production, is automatically obtained by utilizing fossil light straight run naphtha as the organic phase. The ease of integration pleads for a joint petro/bio effort to gradually produce bio-enriched gasolines, wherein the chemical compounds of the bio-derived fraction are indistinguishable from those in current high-quality gasoline compositions. ispartof: Nature Energy vol:3 issue:11 pages:969-977 status: published

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.

Lignin is the main cause of lignocellulosic biomass recalcitrance to industrial enzymatic hydrolysis. By partially replacing the traditional lignin monomers by alternative ones, lignin extractability can be enhanced. To design a lignin that is easier to degrade under alkaline conditions, curcumin (diferuloylmethane) was produced in the model plant Arabidopsis thaliana via simultaneous expression of the turmeric (Curcuma longa) genes DIKETIDE-CoA SYNTHASE (DCS) and CURCUMIN SYNTHASE 2 (CURS2). The transgenic plants produced a plethora of curcumin- and phenylpentanoid-derived compounds with no negative impact on growth. Catalytic hydrogenolysis gave evidence that both curcumin and phenylpentanoids were incorporated into the lignifying cell wall, thereby significantly increasing saccharification efficiency after alkaline pretreatment of the transgenic lines by 14–24% as compared with the wild type. These results demonstrate that non-native monomers can be synthesized and incorporated into the lignin polymer in plants to enhance their biomass processing efficiency. A study introduces curcumin biosynthesis in Arabidopsis by expressing the turmeric genes DIKETIDE-CoA SYNTHASE and CURCUMIN SYNTHASE 2, and the monomers curcumin and phenylpentanoids were successfully incorporated into the lignin cell wall to enhance biomass processing.

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...

Lignin is the main cause of lignocellulosic biomass recalcitrance to industrial enzymatic hydrolysis. By partially replacing the traditional lignin monomers by alternative ones, lignin extractability can be enhanced. To design a lignin that is easier to degrade under alkaline conditions, curcumin (diferuloylmethane) was produced in the model plant Arabidopsis thaliana via simultaneous expression of the turmeric (Curcuma longa) genes DIKETIDE-CoA SYNTHASE (DCS) and CURCUMIN SYNTHASE 2 (CURS2). The transgenic plants produced a plethora of curcumin- and phenylpentanoid-derived compounds with no negative impact on growth. Catalytic hydrogenolysis gave evidence that both curcumin and phenylpentanoids were incorporated into the lignifying cell wall, thereby significantly increasing saccharification efficiency after alkaline pretreatment of the transgenic lines by 14-24% as compared with the wild type. These results demonstrate that non-native monomers can be synthesized and incorporated into the lignin polymer in plants to enhance their biomass processing efficiency.

Linear, branched and cyclic alkanes are important intermediates and end products of the chemical industry and are nowadays mainly obtained from fossil resources. In search for alternatives, biomass feedstocks are often presented as a renewable carbon source for the production of fuels, chemicals and materials. However, providing a complete market for all these applications seems unrealistic due to both financial and logistic issues. Despite the very large scale of current alkane-based fuel applications, biomass definitely has the potential to offer a partial solution to the fuel business. For the smaller market of chemicals and materials, a transition to biomass as main carbon source is more realistic and even probably unavoidable in the long term. The appropriate use and further development of integrated chemo- and biotechnological (catalytic) process strategies will be crucial to successfully accomplish this petro-to-bio feedstock transition. Furthermore, a selection of the most promising technologies from the available chemo- and biocatalytic tool box is presented. New opportunities will certainly arise when multidisciplinary approaches are further explored in the future. In an attempt to select the most appropriate biomass sources for each specific alkane-based application, a diagram inspired by van Krevelen is applied, taking into account both the C-number and the relative functionality of the product molecules.

Valorization of lignin is essential for the economics of future lignocellulosic biorefineries. Lignin is converted into novel polymer building blocks through four steps: catalytic hydroprocessing of softwood to form 4-alkylguaiacols, their conversion into 4-alkylcyclohexanols, followed by dehydrogenation to form cyclohexanones, and Baeyer-Villiger oxidation to give caprolactones. The formation of alkylated cyclohexanols is one of the most difficult steps in the series. A liquid-phase process in the presence of nickel on CeO2 or ZrO2 catalysts is demonstrated herein to give the highest cyclohexanol yields. The catalytic reaction with 4-alkylguaiacols follows two parallel pathways with comparable rates: 1) ring hydrogenation with the formation of the corresponding alkylated 2-methoxycyclohexanol, and 2) demethoxylation to form 4-alkylphenol. Although subsequent phenol to cyclohexanol conversion is fast, the rate is limited for the removal of the methoxy group from 2-methoxycyclohexanol. Overall, this last reaction is the rate-limiting step and requires a sufficient temperature (> 250 degrees C) to overcome the energy barrier. Substrate reactivity (with respect to the type of alkyl chain) and details of the catalyst properties (nickel loading and nickel particle size) on the reaction rates are reported in detail for the Ni/CeO2 catalyst. The best Ni/CeO2 catalyst reaches 4-alkylcyclohexanol yields over 80 %, is even able to convert real softwood-derived guaiacol mixtures and can be reused in subsequent experiments. A proof of principle of the projected cascade conversion of lignocellulose feedstock entirely into caprolactone is demonstrated by using Cu/ZrO2 for the dehydrogenation step to produce the resultant cyclohexanones (approximate to 80%) and tin-containing beta zeolite to form 4-alkyl-e-caprolactones in high yields, according to a Baeyer-Villiger-type oxidation with H2O2.

Comprehensive HT-GC × GC FID/MS enables reliable detection and quantification of RCF lignin monomers, dimers and, trimers.