Thijs Ennaert

Influence of bio-based solvents on the catalytic reductive fractionation of birch wood

Reductive catalytic fractionation constitutes a promising approach to separate lignocellulose into a solid carbohydrate pulp and a stable liquid lignin oil. The process is able to extract and convert most of the lignin into soluble mono-, di- and oligomers, while retaining most of the carbohydrates in the pulp. This contribution studies the impact of the solvent choice on both pulp retention and delignification efficiency. Several bio-derivable solvents with varying properties were therefore tested in the Pd/C-catalyzed reductive liquid processing of birch wood. Though a high solvent polarity favors delignification, a too polar solvent like water causes significant solubilization of carbohydrates. A new empirical descriptor, denoted as ‘lignin-first delignification efficiency’ (LFDE), is introduced as a measure of efficient wood processing into soluble lignin derivatives and solid sugar pulp. Of all tested solvents, methanol and ethylene glycol showed the highest LFDE values, and these values could be increased by increasing both reaction time and temperature. Moreover, substantial differences regarding the process characteristics and analyzed product fractions between these two different solvents were discussed extensively. Most striking is the impact of the solvent on the pulp macrostructure, with methanol yielding a pulp composed of aggregated fiber cells, whereas the ethylene glycol pulp comprises nicely separated fiber cells.

The importance of pretreatment and feedstock purity in the reductive splitting of (ligno)cellulose by metal supported USY zeolite

Reductive hydrolysis of cellulose to hexitols is a promising technology to valorize cellulose streams. Several catalytic systems have been reported to successfully process commercially available purified cellulose powders according to this technology. Ruthenium-loaded USY zeolites in the presence of minute amounts of HCl previously showed very high hexitol yields. This contribution first investigates into more detail the impact of several cellulose accessibility-related properties like cellulose crystallinity, particle size and degree of polymerization on the conversion rate and hexitol selectivity. Therefore, a series of commercial cellulose samples and several mechano- and chemotreated ones were processed with the Ru/H-USY–HCl catalytic system under standard hot liquid water conditions. The results reveal that the polymerization degree has a large impact on both the conversion rate and selectivity, but its impact fades for DPs lower than 200. From then on, the dominant parameters are the particle size and crystallinity. A second part addresses the influence of cellulose purity. Therefore, organosolv pulps of three lignocellulosic substrates (wheat straw, spruce and birch wood), optionally followed by a bleaching procedure, were processed under the same catalytic circumstances. Here factors like residual lignin content and acid buffer capacity appeared crucial, pointing to the necessity of a dedicated delignification and purification procedure step in order to form the most reactive cellulose feedstock for hexitol production. Complete removal of non-glucosic components is not required since processing of ethanol organosolv birch cellulose and bleached ethanol organosolv wheat straw cellulose, both containing about 6 wt% of lignin and minor contents of ashes and proteins, showed a similar hexitol yield, viz. 34–39%, to that derived from pure microcrystalline cellulose.

Compositional and structural feedstock requirements of a liquid phase cellulose-to-naphtha process in a carbon- and hydrogen-neutral biorefinery context

Processing raw (ligno)cellulosic feedstock into renewable light naphtha alkanes could lead to a gradual replacement of fossil feedstock for the production of chemicals, materials and fuels. The production of drop-in alkanes is a preferable short term strategy because of its practical implementation and integration in existing infrastructure and processes. A handful of promising cellulose-to-alkane biorefinery initiatives were recently reported, both processing in gas and liquid phase. This contribution presents a detailed study of the two-liquid phase hydrodeoxygenation of cellulose to n-hexane under relatively mild circumstances, proceeding through the recently communicated HMF route, in presence of a soluble acid and Ru/C metal catalyst. Two main points were addressed here: (i) the importance (or not) of the lignocellulose pretreatment and purification to the alkane yield, and (ii) the renewability of the consumed hydrogen in the process. A systematic study of the effect of cellulose purity, crystallinity, degree of polymerization and particle size (surface area) on the light naphtha yield was performed to tackle the first part. As fibrous cellulose with large particles was the most favourable feedstock with regard to alkane yield and as the presence of hemicellulose and lignin impurities had no effect on the cellulose-to-naphtha conversion, costly mechanical and purification steps are redundant to the process, in contrast to their notable importance in other cellulose valorisation processes (e.g. to glucose, sorbitol, isosorbide and acids). The second point regarding sustainable hydrogen supply is discussed in detail by calculating hydrogen and carbon mass and energy balances of the chemical conversions, assuming selected scenarios among others to recuperate the hydrogen by steam-reforming of waste streams (like gaseous C<6 hydrocarbons and aqueous polyol fractions) and (partial) aromatization of the C6 fraction into benzene. The study shows potential to integrate the liquid phase cellulose-to-naptha (LPCtoN) technology into a self-sufficient biorefinery, in which the chemical processes may run without consumption of external (non-renewable) hydrogen, carbon and energy, except for solar light.

Reductive splitting of hemicellulose with stable ruthenium-loaded USY zeolites

Reductive catalytic splitting to sugar alcohols is a promising technology to valorize (hemi)cellulosic feedstock. This contribution focuses on the conversion of arabinoxylan (AX), a common hemicellulose polymer, to pentitols like xylitol and arabitol in the presence of ruthenium-loaded H-USY zeolites. Both acid and metal sites on the catalyst play a crucial role in the bifunctional catalytic mechanism. Overall, the reaction mechanism involves hydrolysis of AX into shorter (less reactive) xylan oligomer intermediates (XOs), which are in turn hydrolysed into sugar monomers. The first step occurs fast in hot liquid water, but the second step which is rate limiting, requires acid catalysis. Literature has reported successful XO hydrolysis with soluble acids. However, USY zeolites, being non-corrosive instead of the former, are able to hydrolyse XOs more efficiently, likely due to their strong mesopore adsorption capacity. Once formed, the monomeric sugars should be hydrogenated on the metal sites as fast as possible, as otherwise undesired competitive acid catalysed side-reactions will occur. While another catalyst like Ru on carbon can also be used in the one-pot approach close proximity of the two sites, e.g. in the pores of the USY zeolite, is beneficial for the pentitol selectivity, as long as they are well harmonised. After searching for the ideal dual site balance, exceptionally high pentitol yields up to 90 mol% were achieved after only 5 h of reaction. Comparison with earlier reported cellulose reactions shows a narrowing of the ideal acid-to-metal range, besides a shift to lower ratios. Initial regeneration studies show a stable Ru/USY catalytic system able to perform multiple reaction runs with retention of activity and selectivity.

Unconventional Pretreatment of Lignocellulose with Low-Temperature Plasma

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.

Conversion of biomass to chemicals: The catalytic role of zeolites

Abstract Since the mid-20th century zeolites have been successfully applied in oil refining and petrochemistry, owing to the strong Bronsted acidity of their protonated form in a porous crystalline matrix. Yet, concerns about the excessive use of fossil fuels force researchers to develop processes for the production of fuels and chemicals from CO2-neutral feedstocks such as biomass, considered as the alternative and sustainable source of carbon for the production of future bio-derived chemicals. With their success in refinery and petrochemistry, there is increasing interest in the use of zeolites in biomass processing, and this has already resulted in the gradual entrance of zeolites in the conversion of biomass feedstocks. Many interesting biomass conversions have been demonstrated today using the unique acid and redox chemistry of zeolites. However, there are disadvantages inherent to the biomass conversion that need to be overcome before zeolite chemistry can play as important a role in the conversion of biomass as in the conversion of fossil feedstocks. These disadvantages include unstable products and complex conversion network schemes, the stability of zeolites in often polar (condensed) media and active site accessibility of large biomolecules. This chapter presents the major organic compounds in biomass feedstock and provides an overview of the numerous chemical reactions with these chemicals using zeolites in the bulk and fine chemistry. Developments and future challenges in the area are summarized.