Biomass derived 5-hydroxymethylfurfural (HMF) has emerged as an important platform chemical for the production of value added chemicals and liquid fuels that are currently obtained from petroleum.Although a significant amount of research has been performed over the past decade, the high production cost of HMF is still a bottleneck for its sustainable utilization for making other value added chemicals and fuels on a commercial scale. Among several factors, low product selectivity and high purification cost are major constraints. To address these drawbacks, HMF production methodology in recent years has been directed towards utilization of biphasic media for concurrent extraction of HMF into an organic phase immediately after its formation in the reactive phase. As a result, several dozens of journal and patent articles have appeared, demonstrating the benefit of biphasic media for effective HMF extraction. This review article summarizes the findings of the most recent research articles with critical discussion on the factors that enhance the performance of biphasic media. Particular emphasis has been given to the development of more effective extracting solvents and their beneficial effect in enhancing HMF yield and selectivity, improvement of partition coefficient, mechanistic role of the bi-functional acid catalysts and factors that control high HMF selectivity for solid catalysts.
Lignocellulosic biomass provides an attractive source of renewable carbon that can be sustainably converted into chemicals and fuels. Hydrodeoxygenation (HDO) processes have recently received considerable attention to upgrade biomass-derived feedstocks into liquid transportation fuels. The selection and design of HDO catalysts plays an important role to determine the success of the process. This review has been aimed to emphasize recent developments on HDO catalysts in effective transformations of biomass-derived platform molecules into hydrocarbon fuels with reduced oxygen content and improved H/C ratios. Liquid hydrocarbon fuels can be obtained by combining oxygen removal processes (e.g. dehydration, hydrogenation, hydrogenolysis, decarbonylation etc.) as well as by increasing the molecular weight via C-C coupling reactions (e.g. aldol condensation, ketonization, oligomerization, hydroxyalkylation etc.). Fundamentals and mechanistic aspects of the use of HDO catalysts in deoxygenation reactions will also be discussed.
Biomass is a promising feedstock for the next generation drop-in liquid fuels and renewable chemicals, and hence the development of economically viable technologies for the production of commodity and specialty chemicals from sustainable biomass have received significant attention in recent years.While biomass transformation into drop-in biofuels involves multiple processing steps in which biomass is first depolymerized and converted to furfurals (5hydroxymethylfurfural, furfural), catalytic upgrading of furfurals is the most important step in achieving end products of the desired fuel properties. Several research articles have been published in the past decade reporting homogeneous and heterogeneous catalytic processes for upgrading furfurals to relevant drop-in fuel candidates such as, 2,5-dimethylfuran (DMF), 2methylfuran (2-MF), 5-ethoxymethylfurfural (EMF), γ-valorolactone (GVL), ethyl levulinate and long chain hydrocarbon alkanes. Although process technologies for the production and upgrading of some of these fuel compounds have been reviewed, a concise overview on production methodologies for all relevant furan based fuel compounds, including long chain hydrocarbon alkanes, from furfurals is yet to be published. This review article is aimed atpresenting an up to date analysis of the reported catalytic technologies for upgrading furfurals into long chain hydrocarbons with special emphasis on the condensation reactions for producing high carbon chain precursors and catalytic systems for their subsequent deoxygenation to achieve high yield and selectivity in fuel grade hydrocarbons. The current state-of-the-art on upgrading furfurals to DMF, 2-MF and EMF are also analyzed.
We report a new and
robust strategy toward the development of high-performance
pressure sensitive adhesives (PSAs) from chemicals directly obtained
from raw biomass deconstruction. A particularly unique and translatable
aspect of this work was the use of a monomer obtained from real biomass,
as opposed to a model compound or lignin-mimic, to generate well-defined
and nanostructure-forming polymers. Herein, poplar wood depolymerization
followed by minimal purification steps (filtration and extraction)
produced two aromatic compounds, 4-propylsyringol and 4-propylguaiacol,
with high purity and yield. Efficient functionalization of those aromatic
compounds with either acrylate or methacrylate groups generated monomers
that could be easily polymerized by a scalable reversible addition–fragmentation
chain-transfer (RAFT) process to yield polymeric materials with high
glass transition temperatures and robust thermal stabilities, especially
relative to other potentially biobased alternatives. These lignin-derived
compounds were used as a major component in low-dispersity triblock
polymers composed of 4-propylsyringyl acrylate and n-butyl acrylate (also can be biobased). The resulting PSAs exhibited
excellent adhesion to stainless steel without the addition of any
tackifier or plasticizer. The 180° peel forces were up to 4 N
cm–1, and tack forces were up to 2.5 N cm–1, competitive with commercial Fisherbrand labeling tape and Scotch
Magic tape, demonstrating the practical significance of our biomass-derived
materials.
Multistage dissolution experiments of humins, obtained from fructose dehydration, were performed in various solvents to investigate the solubility and molecular structure using spectroscopic, chromatography and mass spectrometric techniques.
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