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Upcoming biorefineries, such as lignin-first provide renewable aromatics containing unique aliphatic alcohols. In this context, a Cu-ZrO2 catalyzed hydrogen borrowing approach was established to yield tertiary amine from the lignin model monomer 3-(3,4-dimethoxyphenyl)-1-propanol and the actual lignin-derived monomers, (3-(4-hydroxyphenyl)-1-propanol and dihydroconiferyl alcohol), with dimethylamine. Various industrial metal catalysts were evaluated, resulting in nearly quantitative mass balances for most catalysts. Identified intermediates, side and reaction products were placed into a corresponding reaction network, supported by kinetic evolution experiments. Cu-ZrO2 was selected as most suitable catalyst combining high alcohol conversion with respectable aliphatic tertiary amine selectivity. Low pressure H2 was key for high catalyst activity and tertiary amine selectivity, mainly by hindering undesired reactant dimethylamine disproportionation and alcohol amidation. Besides dimethylamine model, diverse secondary amine reactants were tested with moderate to high tertiary amine yields. As most active catalytic site, highly dispersed Cu species in strong contact with ZrO2 is suggested. ToF-SIMS, N2 O chemisorption, TGA and XPS of spent Cu-ZrO2 revealed that imperfect amine product desorption and declining surface Cu lowered the catalytic activity upon catalyst reuse, while thermal reduction readily restored the initial activity and selectivity demonstrating catalyst reuse. ispartof: CHEMSUSCHEM vol:15 issue:19 ispartof: location:Germany status: published

5-hydroxymethylfurfural (HMF) is an important bio-derived platform molecule that is generally obtained from hexoses via acid-catalyzed dehydration. It can be effectively transformed into a variety of value-added derivatives, thus being an ideal candidate for fossil replacement. Both HMF oxidation and hydrogenation processes enable the synthesis of numerous chemicals, monomers for polymerization, and biofuel precursors. This Review summarizes the most recent advances in heterogeneous catalytic hydroconversion of HMF into valuable chemicals with strong focus on 2,5-bishydroxymethyl furan (BHMF), 2,5-bishydroxymethyltetrahydrofuran (BHMTHF), and 2,5-dimethyltetrahydrofuran (DMTHF). In addition, multifunctional catalytic systems that enable a tunable production of various HMF derived intermediates are discussed. Within this chemistry, the surprising impact of HMF purity on the catalytic performance, such as selectivity and activity, during its upgrading is highlighted. Lastly, the remaining challenges in the field of HMF hydroconversion to the mentioned chemicals are summarized and discussed, taking into account the knowledge gain of catalyst properties and feedstock purity.

Alternative biobased bisphenols from lignocellulosic biomass are not only favorable to reduce the environmental impact of current petroleum-derived plastics, but they can be simultaneously beneficial for health issues related to bisphenol A (BPA). Additionally, conventional BPA synthesis entails a large excess of unrecoverable homogeneous acid catalyst (e.g., HCl) or unrecyclable thermolabile sulfonated resins. In this report, zeolites are proposed as recoverable and thermally stable solid acids for the Bronsted-acid-catalyzed condensation between 4-methylguaiacol and formaldehyde to selectively produce renewable bisphenols. It is found that the Bronsted-acid-site density plays a pivotal role for catalyst performance. In particular, the cheap and environmentally friendly FAU 40 exhibits outstanding activity (turnover frequency of 496 h−1) and selectivity (>95 %), outperforming even the best benchmark catalyst. Additionally, the zeolite can be easily recycled without activity loss after regeneration by coke burn-off. The catalytic zeolite system also seems very promising for other lignin-derived alkylphenols, alkylguaiacols, and alkylsyringols.

The catalytic valorization of cellulose is currently subject of intense research. Isosorbide is among the most interesting products that can be formed from cellulose as it is a potential platform molecule and can be used for the synthesis of a wide range of pharmaceuticals, chemicals, and polymers. A promising direct route from cellulose to isosorbide is presented in this work. The strategy relies on a one-pot bifunctional catalytic concept, combining heteropoly acids, viz. H(4)SiW(12)O(40), and redox catalysts, viz. commercial Ru on carbon, under H(2) pressure. Starting from pure microcrystalline cellulose, a rapid conversion was observed, resulting in over 50% isosorbide yield. The robustness of the developed system is evidenced by the conversion of a range of impure cellulose pulps obtained by organosolv fractionation, with isosorbide yields up to 63%. Results were compared with other (ligno)cellulose feedstocks, highlighting the importance of fractionation and purification to increase reactivity and convertibility of the cellulose feedstock.

Lignocellulose represents a potential supply of sustainable feedstock for the production of biofuels and chemicals. There is, however, an important cost and efficiency challenge associated with the conversion of such lignocellulosics. Because its structure is complex and not prone to undergo chemical reactions very easily, chemical and mechanical pretreatments are usually necessary to be able to refine them into the compositional building blocks (carbohydrates and lignin) from which value-added platform molecules, such as glucose, ethylene glycol, 5-hydroxymethylfurfural, and levulinic acid, and biofuels, such as bioderived naphtha, kerosene, and diesel fractions, will be produced. Conventional (wet) methods are usually polluting, aggressive, and highly energy consuming, so any alternative activation procedure of the lignocellulose is highly recommended and anticipated in recent and future biomass research. Lignocellulosic plasma activation has emerged as an interesting (dry) treatment technique. In the long run, in particular, in times of fairly accessible renewable electricity, plasma may be considered as an alternative to conventional pretreatment methods, but current knowledge is too little and examples too few to guarantee that statement. This review therefore highlights recent knowledge, advancements, and shortcomings in the field of plasma treatment of cellulose and lignocellulose with regard to the (structural and chemical) effects and impact on the future of pretreatment methods.

Polylactic acid (PLA) is a very promising biodegradable, renewable, and biocompatible polymer. Aside from its production, its application field is also increasing, with use not only in commodity applications but also as durables and in biomedicine. In the current PLA production scheme, the most expensive part is not the polymerization itself but obtaining the building blocks lactic acid (LA) and lactide, the actual cyclic monomer for polymerization. Although the synthesis of LA and the polymerization have been studied systematically, reports of lactide synthesis are scarce. Most lactide synthesis methods are described in patent literature, and current energy-intensive, aselective industrial processes are based on archaic scientific literature. This Review, therefore, highlights new methods with a technical comparison and description of the different approaches. Water-removal methodologies are compared, as this is a crucial factor in PLA production. Apart from the synthesis of lactide, this Review also emphasizes the use of chemically produced racemic lactic acid (esters) as a starting point in the PLA production scheme. Stereochemically tailored PLA can be produced according to such a strategy, giving access to various polymer properties.

The reactive double bonds in conjugated vegetable oils are of high interest in industry. Traditionally, conjugated vegetable oils are added to paints, varnishes, and inks to improve their drying properties, while recently there is an increased interest in their use in the production of bioplastics. Besides the industrial applications, also food manufactures are interested in conjugated vegetable oils due to their various positive health effects. While the isomer type is less important for their industrial purposes, the beneficial health effects are mainly associated with the c9,t11, t10,c12 and t9,t11 CLA isomers. The production of CLA-enriched oils as additives in functional foods thus requires a high CLA isomer selectivity. Currently, CLAs are produced by conjugation of oils high in linoleic acid, for example soybean and safflower oil, using homogeneous bases. Although high CLA productivities and very high isomer selectivities are obtained, this process faces many ecological drawbacks. Moreover, CLA-enriched oils can not be produced directly with the homogeneous bases. Literature reports describe many catalytic processes to conjugate linoleic acid, linoleic acid methyl ester, and vegetable oils rich in linoleic acid: biocatalysts, for example enzymes and cells; metal catalysts, for example homogeneous metal complexes and heterogeneous catalysts; and photocatalysts. This Review discusses state-of-the-art catalytic processes in comparison with some new catalytic production routes. For each category of catalytic process, the CLA productivities and the CLA isomer selectivity are compared. Heterogeneous catalysis seems the most attractive approach for CLA production due to its easy recovery process, provided that the competing hydrogenation reaction is limited and the CLA production rate competes with the current homogeneous base catalysis. The most important criteria to obtain high CLA productivity and isomer selectivity are (1) absence of a hydrogen donor, (2) absence of catalyst acidity, (3) high metal dispersion, and (4) highly accessible pore architecture.

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.

While conjugated vegetable oils are currently used as additives in the drying agents of oils and paints, they are also attractive molecules for making bio-plastics. Moreover, conjugated oils will soon be accepted as nutritional additives for "functional food" products. While current manufacture of conjugated vegetable oils or conjugated linoleic acids (CLAs) uses a homogeneous base as isomerisation catalyst, a heterogeneous alternative is not available today. This contribution presents the direct production of CLAs over Ru supported on different zeolites, varying in topology (ZSM-5, BETA, Y), Si/Al ratio and countercation (H(+), Na(+), Cs(+)). Ru/Cs-USY, with a Si/Al ratio of 40, was identified as the most active and selective catalyst for isomerisation of methyl linoleate (cis-9,cis-12 (C18:2)) to CLA at 165 °C. Interestingly, no hydrogen pre-treatment of the catalyst or addition of hydrogen donors is required to achieve industrially relevant isomerisation productivities, namely, 0.7 g of CLA per litre of solvent per minute. Moreover, the biologically most active CLA isomers, namely, cis-9,trans-11, trans-10,cis-12 and trans-9,trans-11, were the main products, especially at low catalyst concentrations. Ex situ physicochemical characterisation with CO chemisorption, extended X-ray absorption fine structure measurements, transmission electron microscopy analysis, and temperature-programmed oxidation reveals the presence of highly dispersed RuO(2) species in Ru/Cs-USY(40).