Biomass is an important feedstock for the renewable production of fuels, chemicals, and energy. As of 2005, over 3% of the total energy consumption in the United States was supplied by biomass, and it recently surpassed hydroelectric energy as the largest domestic source of renewable energy. Similarly, the European Union received 66.1% of its renewable energy from biomass, which thus surpassed the total combined contribution from hydropower, wind power, geothermal energy, and solar power. In addition to energy, the production of chemicals from biomass is also essential; indeed, the only renewable source of liquid transportation fuels is currently obtained from biomass.

The Catalytic Valorization of Lignin for the Production of Renewable Chemicals

Pretreatment technologies for an efficient bioethanol production process based on enzymatic hydrolysis: A review

Background Lignin, nature’s dominant aromatic polymer, is found in most terrestrial plants in the approximate range of 15 to 40% dry weight and provides structural integrity. Traditionally, most large-scale industrial processes that use plant polysaccharides have burned lignin to generate the power needed to productively transform biomass. The advent of biorefineries that convert cellulosic biomass into liquid transportation fuels will generate substantially more lignin than necessary to power the operation, and therefore efforts are underway to transform it to value-added products. Production of biofuels from cellulosic biomass requires separation of large quantities of the aromatic polymer lignin. In planta genetic engineering, enhanced extraction methods, and a deeper understanding of the structure of lignin are yielding promising opportunities for efficient conversion of this renewable resource to carbon fibers, polymers, commodity chemicals, and fuels. [Credit: Oak Ridge National Laboratory, U.S. Department of Energy] Advances Bioengineering to modify lignin structure and/or incorporate atypical components has shown promise toward facilitating recovery and chemical transformation of lignin under biorefinery conditions. The flexibility in lignin monomer composition has proven useful for enhancing extraction efficiency. Both the mining of genetic variants in native populations of bioenergy crops and direct genetic manipulation of biosynthesis pathways have produced lignin feedstocks with unique properties for coproduct development. Advances in analytical chemistry and computational modeling detail the structure of the modified lignin and direct bioengineering strategies for targeted properties. Refinement of biomass pretreatment technologies has further facilitated lignin recovery and enables catalytic modifications for desired chemical and physical properties. Outlook Potential high-value products from isolated lignin include low-cost carbon fiber, engineering plastics and thermoplastic elastomers, polymeric foams and membranes, and a variety of fuels and chemicals all currently sourced from petroleum. These lignin coproducts must be low cost and perform as well as petroleum-derived counterparts. Each product stream has its own distinct challenges. Development of renewable lignin-based polymers requires improved processing technologies coupled to tailored bioenergy crops incorporating lignin with the desired chemical and physical properties. For fuels and chemicals, multiple strategies have emerged for lignin depolymerization and upgrading, including thermochemical treatments and homogeneous and heterogeneous catalysis. The multifunctional nature of lignin has historically yielded multiple product streams, which require extensive separation and purification procedures, but engineering plant feedstocks for greater structural homogeneity and tailored functionality reduces this challenge.

https://lifelong.unt.edu/sites/default/files/EmeritusCollege/Spring2015/Handouts/Lignin%20co-products.pdf

Lignin valorization: improving lignin processing in the biorefinery.

Lignocelluloses are often a major or sometimes the sole components of different waste streams from various industries, forestry, agriculture and municipalities. Hydrolysis of these materials is the first step for either digestion to biogas (methane) or fermentation to ethanol. However, enzymatic hydrolysis of lignocelluloses with no pretreatment is usually not so effective because of high stability of the materials to enzymatic or bacterial attacks. The present work is dedicated to reviewing the methods that have been studied for pretreatment of lignocellulosic wastes for conversion to ethanol or biogas. Effective parameters in pretreatment of lignocelluloses, such as crystallinity, accessible surface area, and protection by lignin and hemicellulose are described first. Then, several pretreatment methods are discussed and their effects on improvement in ethanol and/or biogas production are described. They include milling, irradiation, microwave, steam explosion, ammonia fiber explosion (AFEX), supercritical CO2 and its explosion, alkaline hydrolysis, liquid hot-water pretreatment, organosolv processes, wet oxidation, ozonolysis, dilute- and concentrated-acid hydrolyses, and biological pretreatments.

/pdf/pretreatment-of-lignocellulosic-wastes-to-improve-ethanol-zbwx58h962.pdf

Pretreatment of lignocellulosic wastes to improve ethanol and biogas production: a review.

This review gives a survey on the latest most representative developments and progress concerning ionic liquids, from their fundamental properties to their applications in catalytic processes. It also highlights their emerging use for biomass treatment and transformation.

Ionic liquids and catalysis: Recent progress from knowledge to applications

Lignin-based carbon fibers for composite fiber applications

Inhibition of cellulase, xylanase and β-glucosidase activities by softwood lignin preparations

Hydrogen bonding in lignin: a Fourier transform infrared model compound study.

Carbon fibers have been produced from hardwood lignin/synthetic polymer blend fibers. Hardwood kraft lignin was thermally blended with two recyclable polymers, poly(ethylene terephthalate) (PET) and polypropylene (PP). Both systems were easily spun into fibers. A thermostabilization step was utilized prior to carbonization to prevent fusion of individual fibers. For the lignin-based carbon fibers, careful control of heating rate was required. However, PET–lignin blend fibers can be thermostabilized under higher heating rates than the corresponding homofibers. Carbon fiber yield decreased with increasing incorporation of synthetic plastic. However, carbon fiber yield obtained for a 25% plastic blend fiber was still higher than that generally reported for petroleum pitch. Blend composition also affected surface morphology of the carbon fibers. Immiscible lignin–PP fibers resulted in a hollow and/or porous carbon fiber; whereas carbon fiber produced from miscible lignin–PET fibers have a smooth surface. Synthetic polymer blending also affected the mechanical properties of the fibers, especially MOE; lignin-based carbon fiber properties improved upon blending with PET.

Lignin-based Carbon Fibers: Effect of Synthetic Polymer Blending on Fiber Properties

Blends of poly(ethylene oxide) with organosolv lignin (Alcell) were prepared by thermal blending. Excellent fiber spinning was achieved over the entire blend ratio. The good thermal properties of the Alcell lignin arise from its unique chemical structure. HMQC 2D NMR analysis revealed the presence of alkoxyl chains at the Cα and Cγ positions of the Alcell lignin side chain structure acting as internal plasticizers and enhancing the thermal mobility of the lignin. The addition of a small amount of Alcell lignin to PEO resulted in an increase of the PEO crystalline domain size. However, both PEO crystallinity and crystalline domain size decreased with lignin incorporation beyond 25 wt %. A negative polymer−polymer interaction energy density “B” was calculated on the basis of the melting point depression of PEO and a negative deviation of Tg from the weighted average values observed. Good prediction of the Tg-composition behavior was obtained indicating the presence of favorable interactions between blend co...

Satoshi Kubo

Papers

Lignin-based carbon fibers for composite fiber applications

Inhibition of cellulase, xylanase and β-glucosidase activities by softwood lignin preparations

Hydrogen bonding in lignin: a Fourier transform infrared model compound study.

Lignin-based Carbon Fibers: Effect of Synthetic Polymer Blending on Fiber Properties

Poly(Ethylene Oxide)/Organosolv Lignin Blends: Relationship between Thermal Properties, Chemical Structure, and Blend Behavior