Sustainable Materials: Production Methods and End-of-life Strategies

All three natural polymers of biomass and the monomer platforms derived from them present multiple avenues to develop products from specialty to bulk markets, which could serve as entry points into the industry for bio based sustainable materials. However, several roadblocks still exist in the pathway of technology development of these materials due to challenges related to cost-competitiveness, scalability, performance and sustainability. This review outlines these major technical challenges as four key checkpoints (cost-competitive, scalability, sustainability, performance) to be addressed for successful market entry of a new sustainable material

Organic Solvent Effects in Biomass Conversion Reactions

Transforming lignocellulosic biomass into fuels and chemicals has been intensely studied in recent years. A large amount of work has been dedicated to finding suitable solvent systems, which can improve the transformation of biomass into value-added chemicals. These efforts have been undertaken based on numerous research results that have shown that organic solvents can improve both conversion and selectivity of biomass to platform molecules. We present an overview of these organic solvent effects, which are harnessed in biomass conversion processes, including conversion of biomass to sugars, conversion of sugars to furanic compounds, and production of lignin monomers. A special emphasis is placed on comparing the solvent effects on conversion and product selectivity in water with those in organic solvents while discussing the origins of the differences that arise. We have categorized results as benefiting from two major types of effects: solvent effects on solubility of biomass components including cellulose and lignin and solvent effects on chemical thermodynamics including those affecting reactants, intermediates, products, and/or catalysts. Finally, the challenges of using organic solvents in industrial processes are discussed from the perspective of solvent cost, solvent stability, and solvent safety. We suggest that a holistic view of solvent effects, the mechanistic elucidation of these effects, and the careful consideration of the challenges associated with solvent use could assist researchers in choosing and designing improved solvent systems for targeted biomass conversion processes

Introduction to High Pressure CO2 and H2O Technologies in Sustainable Biomass Processing

Biomass is an attractive source of renewable carbon-based fuels and chemicals and their production is envisaged within the framework of integrated biorefineries. Multiple research efforts to make biorefineries more economically competitive and sustainable are ongoing. In this context the use of high-pressure CO2 and CO2/H2O mixtures for biomass conversion is especially attractive. These mixtures are cheap, renewable, environmentally benign and allow tuning of various processing parameters by varying temperature, pressure and CO2 loading. This chapter presents a broad introduction of the principal processes and conversion routes being considered within biorefineries, and how high-pressure CO2 and CO2/H2O mixtures could help address certain challenges associated with biomass conversion. Some of the principle advantages associated with high-pressure CO2 and CO2/H2O mixtures that we highlight here are their abilities to act as green substitutes for unsustainable solvents, to enhance acid-catalysed reaction rates by in situ carbonic acid formation, to reduce mass transfer-limitations, and to increase access to substrates and catalysts. We discuss these advantages in the context of the trade-offs associated with implementing large-scale high-pressure systems including safety concerns and increased capital costs. With this introduction, we highlight both the principal benefits and challenges associated with the use of high-pressure CO2 and CO2/H2O mixtures, which are further detailed in subsequent chapters

The influence of interunit carbon–carbon linkages during lignin upgrading

The cleavage of β-O-4 linkages in lignin can generate monomers with a phenyl propane structure that can easily be upgraded into valuable hydrocarbon biofuels and renewable aromatic chemicals. High-yield lignin monomer production from extracted (or technical) lignin that is produced in a practical way could facilitate the productivity and profitability of biomass conversion processes. However, interunit carbon–carbon (C–C) linkages present in native lignin or formed during lignin condensation in biomass pretreatments dramatically reduce lignin monomer yields. Here, we present a perspective on biological and chemical strategies that have been successfully used to reduce the formation of C–C linkages in native or technical lignin. We analyze the mechanisms involved in these strategies and offer our views on improving the quality of technical lignin resulting from biomass conversion in order to achieve high-yield lignin monomer production

Engineering of ecological niches to create stable artificial consortia for complex biotransformations

The design of controllable artificial microbial consortia has attracted considerable interest in recent years to capitalize on the inherent advantages in comparison to monocultures such as the distribution of the metabolic burden by division of labor, the modularity and the ability to convert complex substrates. One promising approach to control the consortia composition, function and stability is the provision of defined ecological niches fitted to the specific needs of the consortium members. In this review, we discuss recent examples for the creation of metabolic niches by biological engineering of resource partitioning and syntrophic interactions. Moreover, we introduce a complementing process engineering approach to provide defined spatial niches with differing abiotic conditions (e.g. O2, T, light) in stirred tank reactors harboring biofilms. This enables the co-cultivation of microorganisms with non-overlapping abiotic requirements and the control of the strain ratio in consortia characterized by substrate competition

Improving Heterogeneous Catalyst Stability for Liquid-phase Biomass Conversion and Reforming

Biomass is a possible renewable alternative to fossil carbon sources. Today, many bio-resources can be converted to direct substitutes or suitable alternatives to fossil-based fuels and chemicals. However, catalyst deactivation under the harsh, often liquid-phase reaction conditions required for biomass treatment is a major obstacle to developing processes that can compete with the petrochemical industry. This review presents recently developed strategies to limit reversible and irreversible catalyst deactivation such as metal sintering and leaching, metal poisoning and support collapse. Methods aiming to increase catalyst lifetime include passivation of low-stability atoms by overcoating, creation of microenvironments hostile to poisons, improvement of metal stability, or reduction of deactivation by process engineering

Densely Packed, Ultra Small SnO Nanoparticles for Enhanced Activity and Selectivity in Electrochemical CO2 Reduction

Controlling the selectivity in electrochemical CO2 reduction is an unsolved challenge. While tin (Sn) has emerged as a promising non‐precious catalyst for CO2 electroreduction, most Sn‐based catalysts produce formate as the major product, which is less desirable than CO in terms of separation and further use. Tin monoxide (SnO) nanoparticles supported on carbon black were synthesized and assembled and their application in CO2 reduction was studied. Remarkably high selectivity and partial current densities for CO formation were obtained using these SnO nanoparticles compared to other Sn catalysts. The high activity is attributed to the ultra‐small size of the nanoparticles (2.6 nm), while the high selectivity is attributed to a local pH effect arising from the dense packing of nanoparticles in the conductive carbon black matrix

Slowing the Kinetics of Alumina Sol-Gel Chemistry for Controlled Catalyst Overcoating and Improved Catalyst Stability and Selectivity

Catalyst overcoating is an emerging approach to engineer surface functionalities on supported metal catalyst and improve catalyst selectivity and durability. Alumina deposition on high surface area material by sol–gel chemistry is traditionally difficult to control due to the fast hydrolysis kinetics of aluminum‐alkoxide precursors. Here, sol–gel chemistry methods are adapted to slow down these kinetics and deposit nanometer‐scale alumina overcoats. The alumina overcoats are comparable in conformality and thickness control to overcoats prepared by atomic layer deposition even on high surface area substrates. The strategy relies on regulating the hydrolysis/condensation kinetics of Al(sBuO)3 by either adding a chelating agent or using nonhydrolytic sol–gel chemistry. These two approaches produce overcoats with similar chemical properties but distinct physical textures. With chelation chemistry, a mild method compatible with supported base metal catalysts, a conformal yet porous overcoat leads to a highly sintering‐resistant Cu catalyst for liquid‐phase furfural hydrogenation. With the nonhydrolytic sol–gel route, a denser Al2O3 overcoat can be deposited to create a high density of Lewis acid–metal interface sites over Pt on mesoporous silica. The resulting material has a substantially increased hydrodeoxygenation activity for the conversion of lignin‐derived 4‐propylguaiacol into propylcyclohexane with up to 87% selectivity

Dual Valorization of Lignin as a Versatile and Renewable Matrix for Enzyme Immobilization and (Flow) Bioprocess Engineering

Lignin has emerged as an attractive alternative in the search for more eco-friendly and less costly materials for enzyme immobi- lization. In this work, the terephthalic aldehyde-stabilization of lignin is carried out during its extraction to develop a series of functionalized lignins with a range of reactive groups (epoxy, amine, aldehyde, metal chelates). This expands the immobiliza- tion to a pool of enzymes (carboxylase, dehydrogenase, trans- aminase) by different binding chemistries, affording immobiliza- tion yields of 64–100%. As a proof of concept, a ω- transaminase reversibly immobilized on polyethyleneimine- lignin is integrated in a packed-bed reactor. The stability of the immobilized biocatalyst is tested in continuous-flow deamina- tion reactions and maintains the same conversion for 100 cycles. These results outperform previous stability tests carried out with the enzyme covalently immobilized on methacrylic resins, with the advantage that the reversibility of the immobilized enzyme allows recycling and reuse of lignin beyond the enzyme inactivation. Additionally, an in-line system also based on lignin is added into the downstream process to separate the reaction products by catch-and-release. These results demonstrate a fully closed-loop sustainable flow- biocatalytic system based exclusively on lignin

A mild biomass pretreatment using gamma-valerolactone for concentrated sugar production

Here we report that gamma-valerolactone (GVL), a biomass-derived solvent, can be used to facilitate the mild pretreatment of lignocellulosic biomass. An 80% GVL, 20% water solvent system was used to pretreat hardwood at the mild temperature of 120 degrees C with an acid loading of 75 mM H2SO4. Up to 80% of original lignin was removed with 96-99% of original cellulose retained in the pretreated substrates. The use of a mild temperature and low acid concentrations caused negligible degradation of sugars. Up to 99% of the original glucan and 96% of the original xylan could be recovered after pretreatment. The pretreated substrate was quantitatively converted to sugars (99% and 100% total glucose and xylose yield) with an enzyme loading of 15 FPU g(-1) glucan. These digestibilities were three times higher than those obtained when using other organic solvents such as tetrahydrofuran or ethanol, and 20 times higher than when pure water was used during pretreatment. Over 99.5% of GVL could be recovered by liquid-CO2 extraction of the pretreated slurries while removing less than 1% of the sugars. This approach produced pretreatment slurries that could easily undergo high-solids (30% w/v) enzymatic hydrolysis without any substrate washing or drying. We obtained glucose and xylose yields of up to 90% and 97%, respectively, and generated sugar streams with sugar concentrations up to 182 g L-1