Decreasing the degree of polymerization of microcrystalline cellulose by mechanical impact and acid hydrolysis.

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.

Engineering Curcumin Biosynthesis in Poplar Affects Lignification and Biomass Yield.

Lignocellulosic biomass is recalcitrant toward deconstruction into simple sugars mainly due to the presence of lignin. By engineering plants to partially replace traditional lignin monomers with alternative ones, lignin degradability and extractability can be enhanced. Previously, the alternative monomer curcumin has been successfully produced and incorporated into lignified cell walls of Arabidopsis by the heterologous expression of DIKETIDE-CoA SYNTHASE (DCS) and CURCUMIN SYNTHASE2 (CURS2). The resulting transgenic plants did not suffer from yield penalties and had an increased saccharification yield after alkaline pretreatment. Here, we translated this strategy into the bio-energy crop poplar. Via the heterologous expression of DCS and CURS2 under the control of the secondary cell wall CELLULOSE SYNTHASE A8-B promoter (ProCesA8-B), curcumin was also produced and incorporated into the lignified cell walls of poplar. ProCesA8-B:DCS_CURS2 transgenic poplars, however, suffered from shoot-tip necrosis and yield penalties. Compared to that of the wild-type (WT), the wood of transgenic poplars had 21% less cellulose, 28% more matrix polysaccharides, 23% more lignin and a significantly altered lignin composition. More specifically, ProCesA8-B:DCS_CURS2 lignin had a reduced syringyl/guaiacyl unit (S/G) ratio, an increased frequency of p-hydroxyphenyl (H) units, a decreased frequency of p-hydroxybenzoates and a higher fraction of phenylcoumaran units. Without, or with alkaline or hot water pretreatment, the saccharification efficiency of the transgenic lines was equal to that of the WT. These differences in (growth) phenotype illustrate that translational research in crops is essential to assess the value of an engineering strategy for applications. Further fine-tuning of this research strategy (e.g., by using more specific promoters or by translating this strategy to other crops such as maize) might lead to transgenic bio-energy crops with cell walls more amenable to deconstruction without settling in yield.

Low molecular weight and highly functional RCF lignin products as a full bisphenol a replacer in bio-based epoxy resins.

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.

A sustainable wood biorefinery for low-carbon footprint chemicals production.

The profitability and sustainability of future biorefineries are dependent on efficient feedstock use. Therefore, it is essential to valorize lignin when using wood. We have developed an integrated biorefinery that converts 78 weight % (wt %) of birch into xylochemicals. Reductive catalytic fractionation of the wood produces a carbohydrate pulp amenable to bioethanol production and a lignin oil. After extraction of the lignin oil, the crude, unseparated mixture of phenolic monomers is catalytically funneled into 20 wt % of phenol and 9 wt % of propylene (on the basis of lignin weight) by gas-phase hydroprocessing and dealkylation; the residual phenolic oligomers (30 wt %) are used in printing ink as replacements for controversial para-nonylphenol. A techno-economic analysis predicts an economically competitive production process, and a life-cycle assessment estimates a lower carbon dioxide footprint relative to that of fossil-based production.

Introducing curcumin biosynthesis in Arabidopsis enhances lignocellulosic biomass processing.

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.

Functionalised heterogeneous catalysts for sustainable biomass valorisation.

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.

Alkane production from biomass: chemo-, bio- and integrated catalytic approaches.

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.

Selective nickel-catalyzed conversion of model and lignin-derived phenolic compounds to cyclohexanone-based polymer building blocks.

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 °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 (≈80 %) and tin-containing beta zeolite to form 4-alkyl-ε-caprolactones in high yields, according to a Baeyer-Villiger-type oxidation with H2 O2 .