Charles E. Wyman

Lignin Valorization: Improving Lignin Processing in the Biorefinery

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. The Lignin Landscape Lignin is a chemically complex polymer that lends woody plants and trees their rigidity. Humans have traditionally either left it intact to lend rigidity to their own wooden constructs, or burned it to generate heat and sometimes power. With the advent of major biorefining operations to convert cellulosic biomass into ethanol and other liquid fuels, researchers are now exploring how to transform the associated leftover lignin into more diverse and valuable products. Ragauskas et al. (10.1126/science.1246843) review recent developments in this area, ranging from genetic engineering approaches that tune lignin properties at the source, to chemical processing techniques directed toward extracting lignin in the biorefinery and transforming it into high-performance plastics and a variety of bulk and fine chemicals. Research and development activities directed toward commercial production of cellulosic ethanol have created the opportunity to dramatically increase the transformation of lignin to value-added products. Here, we highlight recent advances in this lignin valorization effort. Discovery of genetic variants in native populations of bioenergy crops and direct manipulation of biosynthesis pathways have produced lignin feedstocks with favorable properties for recovery and downstream conversion. Advances in analytical chemistry and computational modeling detail the structure of the modified lignin and direct bioengineering strategies for future targeted properties. Refinement of biomass pretreatment technologies has further facilitated lignin recovery, and this coupled with genetic engineering will enable new uses for this biopolymer, including low-cost carbon fibers, engineered plastics and thermoplastic elastomers, polymeric foams, fungible fuels, and commodity chemicals.

How biotech can transform biofuels

For cellulosic ethanol to become a reality, biotechnological solutions should focus on optimizing the conversion of biomass to sugars.

Fuel ethanol from cellulosic biomass.

Ethanol produced from cellulosic biomass is examined as a large-scale transportation fuel. Desirable features include ethanols fuel properties as well as benefits with respect to urban air quality, global climate change, balance of trade, and energy security. Energy balance, feedstock supply, and environmental impact considerations are not seen as significant barriers to the widespread use of fuel ethanol derived from cellulosic biomass. Conversion economics is the key obstacle to be overcome. In light of past progress and future prospects for research-driven improvements, a cost-competitive process appears possible in a decade.

Handbook on bioethanol : production and utilization

Table of Ethanol production from lignocellulosic biomass: overview Strategic, economic, and environmental issues for transportation fuels Performance of ethanol as a transportation fuel Bioethanol market forces Environmental impacts of bioethanol Biomass feedstock resources and composition Hemicellulases: diversity and applications Cellulases: structure, function, and applications Biocatalyst development for bioethanol production from hydrolysates Pretreatment of biomass Cellulase production Cellulose bioconversion technology Hemicellulose conversion to ethanol Advanced process options for bioethanol production Ethanol from corn: technology and economics Integrated bioprocess development for bioethanol production Review of pilot plant programs for bioethanol conversion Methods for the chemical analysis of biomass process streams

Physical and chemical characterizations of corn stover and poplar solids resulting from leading pretreatment technologies.

In order to investigate changes in substrate chemical and physical features after pretreatment, several characterizations were performed on untreated (UT) corn stover and poplar and their solids resulting pretreatments by ammonia fiber expansion (AFEX), ammonia recycled percolation (ARP), controlled pH, dilute acid, flowthrough, lime, and SO(2) technologies. In addition to measuring the chemical compositions including acetyl content, physical attributes determined were biomass crystallinity, cellulose degree of polymerization, cellulase adsorption capacity of pretreated solids and enzymatically extracted lignin, copper number, FT-IR responses, scanning electron microscopy (SEM) visualizations, and surface atomic composition by electron spectroscopy of chemical analysis (ESCA). Lime pretreatment removed the most acetyl groups from both corn stover and poplar, while AFEX removed the least. Low pH pretreatments depolymerized cellulose and enhanced biomass crystallinity much more than higher pH approaches. Lime pretreated corn stover solids and flowthrough pretreated poplar solids had the highest cellulase adsorption capacity, while dilute acid pretreated corn stover solids and controlled pH pretreated poplar solids had the least. Furthermore, enzymatically extracted AFEX lignin preparations for both corn stover and poplar had the lowest cellulase adsorption capacity. ESCA results showed that SO(2) pretreated solids had the highest surface O/C ratio for poplar, but for corn stover, the highest value was observed for dilute acid pretreatment with a Parr reactor. Although dependent on pretreatment and substrate, FT-IR data showed that along with changes in cross linking and chemical changes, pretreatments may also decrystallize cellulose and change the ratio of crystalline cellulose polymorphs (Ialpha/Ibeta).

ETHANOL FROM LIGNOCELLULOSIC BIOMASS: TECHNOLOGY, ECONOMICS, AND OPPORTUNITIES

Abstract Production of ethanol from agriculutural and forestry residues, municipal solid waste, energy crops, and other forms of lignocellulosic biomass could improve energy security, reduce trade deficits, decrease urban air pollution, and contribute little, if any, net carbon dioxide accumulation to the atmosphere. Dilute acid can open up the biomass structure for subsequent processing. The simultaneous saccharification and fermentation (SSF) process is favored for producing ethanol from the major fraction of lignocellulosic biomass, cellulose, because of its low cost potential. Technology has also been developed for converting the second largest biomass fraction, hemicellulose, into ethanol. The remaining fraction, containing mostly lignin, can be burned as boiler fuel to power the conversion process and generate extra electricity to export. Developments in conversion technology have reduced the projected gate price of ethanol from about US

Lignin content in natural Populus variants affects sugar release

0.95/liter (US

Xylooligomers are strong inhibitors of cellulose hydrolysis by enzymes

3.60/gallon) in 1980 to only about US

Enzymatic hydrolysis of cellulosic biomass

0.32/liter (US

REVIEW: CONTINUOUS HYDROLYSIS AND FERMENTATION FOR CELLULOSIC ETHANOL PRODUCTION

1.22/gallon) in 1994. Technical targets have been identified to bring the selling price down to about US