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.

The U.S. Department of Energy (DOE) promotes the production of a range of liquid fuels and fuel blendstocks from lignocellulosic biomass feedstocks by funding fundamental and applied research that advances the state of technology in biomass collection, conversion, and sustainability. As part of its involvement in this program, the National Renewable Energy Laboratory (NREL) investigates the conceptual production economics of these fuels.Between 1999 and 2012, NREL conducted a campaign to quantify the economic implications associated with measured conversion performance for the biochemical production of cellulosic ethanol, with a formal program between 2007-2012 to set cost goals and to benchmark annual performance toward achieving these goals, namely the pilot-scale demonstration by 2012 of biochemical ethanol production at a price competitive with petroleum gasoline based on modeled assumptions for an "n th " plant biorefinery. This goal was successfully achieved through NREL's 2012 pilot plant demonstration runs, representing the culmination of NREL research focused specifically on cellulosic ethanol, and a benchmark for industry to leverage as it commercializes the technology. This important milestone also represented a transition toward a new Program focus on infrastructure-compatible hydrocarbon biofuel pathways, and the establishment of new research directions and cost goals across a number of potential conversion technologies.This report describes in detail one potential conversion process to hydrocarbon products by way of biological conversion of lignocellulosic-derived sugars. The pathway model leverages expertise established over time in core conversion and process integration research at NREL, while adding in new technology areas primarily for hydrocarbon production and associated processing logistics. The overarching process design converts biomass to a hydrocarbon intermediate, represented here as a free fatty acid, using dilute-acid pretreatment, enzymatic saccharification, and bioconversion. Ancillary areas-feed handling, hydrolysate conditioning, product recovery and upgrading (hydrotreating) to a final blendstock material, wastewater treatment, lignin combustion, and utilities-are also included in the design. Detailed material and energy balances and capital and operating costs for this baseline process are also documented.This benchmark case study techno-economic model provides a production cost for a cellulosic renewable diesel blendstock (RDB) that can be used as a baseline to assess its competitiveness and market potential. It can also be used to quantify the economic impact of individual conversion performance targets and prioritize these in terms of their potential to reduce cost. The analysis presented here also includes consideration of the life-cycle implications of the baseline process model, by tracking sustainability metrics for the modeled biorefinery, including greenhouse gas (GHG) emissions, fossil energy demand, and consumptive water use.Building on prior design reports for bioch...

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from the National Renewable Energy Laboratory (NREL) for helpful discussions, comments, and shared insights during the development of this report. We appreciate all of the help from Kathy Cisar for her technical editing and support in publishing this report. Finally, we thank Billie Christen from the NREL for her help in formatting this report and for developing the U.S. bioproduct facilities map.

Although the purchase price of cellulosic feedstocks is competitive with petroleum on an energy basis, the cost of lignocellulose conversion to ethanol using today's technology is high. Cost reductions can be pursued via either in-paradigm or new-paradigm innovation. As an example of new-paradigm innovation, consolidated bioprocessing using thermophilic bacteria combined with milling during fermentation (cotreatment) is analyzed. Acknowledging the nascent state of this approach, our analysis indicates potential for radically improved cost competitiveness and feasibility at smaller scale compared to current technology, arising from (a) R&D-driven advances (consolidated bioprocessing with cotreatment in lieu of thermochemical pretreatment and added fungal cellulase), and (b) configurational changes (fuel pellet coproduction instead of electricity, gas boiler(s) in lieu of a solid fuel boiler).

Pyrolysis offers a rapid and efficient means to depolymerize lignocellulosic biomass, resulting in gas, liquid, and solid products with varying yields and compositions depending on the process conditions. With respect to manufacture of "drop-in" liquid transportation fuels from biomass, a potential benefit from pyrolysis arises from the production of a liquid or vapor that could possibly be integrated into existing refinery infrastructure, thus offsetting the capital-intensive investment needed for a smaller scale, standalone biofuels production facility. However, pyrolysis typically yields a significant amount of reactive, oxygenated species including organic acids, aldehydes, ketones, and oxygenated aromatics. These oxygenated species present significant challenges that will undoubtedly require pre-processing of a pyrolysisderived stream before the pyrolysis oil can be integrated into the existing refinery infrastructure. Here we present a perspective of how the overall chemistry of pyrolysis products must be modified to ensure optimal integration in standard petroleum refineries, and we explore the various points of integration in the refinery infrastructure. In addition, we identify several research and development needs that will answer critical questions regarding the technical and economic feasibility of refinery integration of pyrolysis-derived products. † Electronic supplementary information (ESI) available. See

This study develops an approach to incentivize both higher extents of waste plastics reclamation and use of bio-based chemicals. In particular, reclaimed plastics (polyethylene terephthalate) and chemicals derivable from renewable resources are combined to create high-performance, long-lifetime composite materials with properties that exceed those of standard petroleum-based materials and that exhibit higher selling prices than reclaimed plastic. Analysis predicts that this approach results in reductions in energy input and greenhouse gas emissions relative to standard composites manufacturing today.