Pretreatment Technology Evaluation
Pretreatment Technology Evaluation
In general, pretreatment processes produce a solid pretreated biomass residue that is more amenable to enzymatic hydrolysis by cellulases and related enzymes than native biomass. Many pretreatment approaches, such as dilute acid and steam/pressurized hot water based methods, seek to achieve this by hydrolyzing a significant amount of the hemicellulose fraction of biomass and recovering the resulting soluble monomeric and/or oligomeric sugars. Other pretreatment processes, such as alkaline-based methods, are generally more effective at solubilizing a greater fraction of lignin while leaving behind much of the hemicellulose in an insoluble, polymeric form. Most pretreatment approaches do not hydrolyze significant amounts of the cellulose fraction of biomass, but enable more efficient enzymatic hydrolysis of the cellulose by removal of the surrounding hemicellulose and/or lignin along with modification of the cellulose microfibril structure.
Numerous pretreatment approaches have been investigated at many laboratories, universities, and industrial locations over the past 25 years. In the past, it has been difficult to compare the performance and economics of these various approaches due to difference in feedstocks tested, chemical analysis methods, and data reporting methodologies. Recently, a group of pretreatment researchers across North America have begun to collaborate to investigate different pretreatment approaches on a common basis to allow meaningful comparison. These researchers have formed the Biomass Refining Consortium for Applied Fundamentals and Innovation (CAFI) to advance the efficacy and knowledge base of pretreatment technologies. Current participating institutions in the Biomass Refining CAFI are Auburn University (Y.Y. Lee), University of British Columbia (Jack Saddler), Dartmouth College (Charles Wyman), University of Hawaii (Michael Antal), Michigan State University (Bruce Dale), National Renewable Energy Laboratory [NREL] (Rick Elander), Purdue University (Michael Ladisch), University of Sherbrooke (Esteban Chornet), and Texas A&M University (Mark Holtzapple).
As an active member of the Biomass Refining CAFI, NREL is generating and supplying data on dilute acid pretreatment and the hot wash process to on-going CAFI projects via its ongoing US DOE Biomass Program projects. In addition, NREL is providing several support activities to CAFI projects, including common feedstock supply and analysis, common enzyme supply and analysis, process engineering model development, and training to students of the CAFI institutions. NREL is using pretreatment process information being generated by the Biomass Refining CAFI and other pretreatment researchers to evaluate and ultimately select the most attractive pretreatment approaches for both near term technology platforms (i.e. Enzyme Sugar Platform Project) and for longer term advanced technology platforms. Such evaluation and selection activities are typically made in collaboration with recognized experts in an open, review meeting setting.
Dilute Acid Pretreatment
Biomass Program researchers have been actively developing and demonstrating various dilute acid pretreatment approaches, primarily utilizing sulfuric acid, for more than 15 years. Current work in this area is primarily in support of the Enzyme Sugar Platform Project involving the use of pilot scale pretreatment reactors in the Process Development Unit. Technical goals in this effort are to improve the enzymatic digestibility of cellulose that remains in the pretreated solids by achieving near-complete solubilization of the hemicellulose fraction with resulting high yields of soluble sugars from the hemicellulose. Process economics dictate that such processes be operated at high solids loading to reduce steam demands and produce high concentration streams for subsequent bioconversion and recovery steps of the process.
Hot Wash Process
A variation of dilute acid pretreatment, which may be applicable to other pretreatment processes, involves a high temperature separation and washing of the pretreated solids. It is believed that such a processing step prevents re-precipitation of lignin and/or xylan that may have been solubilized under pretreatment conditions back upon the pretreated solids. This re-precipitation can negatively affect the subsequent enzymatic hydrolysis of the pretreated solids due to the presence of this lignin.
Initial work on this process concept employed a continuously flowing percolation reactor system using extremely dilute sulfuric acid (~0.1% w/v). This process resulted in high yields of recovered xylose oligomers and monomers (>95% of theoretical) and produced significantly more reactive pretreated solids in subsequent enzymatic hydrolysis operations using a hardwood feedstock. In order to minimize required liquid volumes, a hybrid process that employs a batch or high-solids plug-flow pretreatment followed directly by a hot separation and washing of the pretreated solids is being investigated. Pilot scale equipment to operate such a process at the pilot scale is currently being installed in the Process Development Unit.
For Further Reading
Dilute Acid Pretreatment
Schell, D.J., Farmer, J., Newman, N, Dowe, N., McMillan, J.D. (2002). "Dilute Sulfuric Acid Pretreatment of Corn Stover in a Pilot-Scale Reactor: Influence of Compositional Variability." Presented at AIChE 2002 Annual Meeting, Indianapolis, IN, November 3-8, 2002.
Schell, D.J., Farmer, J., Newman, N., McMillan, J.D. (2002). "Dilute Sulfuric Acid Pretreatment of Corn Stover in a Pilot-Scale Reactor: Investigation of Yields, Kinetics, and Solids Enzymatic Digestibilities." (PDF 296 KB) Presented at the 24th Symposium on Biotechnology for Fuels and Chemicals, Gatlinburg, TN, April 28-May 1, 2002.
Tucker, M.P., Farmer, J.D., Keller, F.A., Schell, D.J. (1998). "Comparison of Yellow Poplar Pretreatment Between NREL Digester and Sunds Hydrolyzer." Applied Biochemistry and Biotechnology. 70-72, 25-35.
Hot Wash Process
Washing Away Bioprocessing Cost (Pressurized Hot Wash fact sheet) (PDF 739 KB)
Nagle, N., Elander, R., Newman, M., Rohrback, B., Ruiz, R., Torget, R. (2002). "Efficacy of a Hot Wash Process for Pretreated Yellow Poplar to Enhance Bioethanol Production." Biotechnology Progress. 18, 734-738.
Nagle, N., Torget, R., Newman, M., Rohrback, B., Ruiz, R., Elander, R. (2002). "Aqueous Hot Water Extraction for Enhanced Fractionation of Pretreated Biomass." Presented at AIChE 2002 Annual Meeting, Indianapolis, IN, November 3-8, 2002.
Elander, R., Nagle, N., Torget, R. (2001). "Examining the Potential for Solid Waste and Energy Reduction in Thermochemical Dilute Sulfuric Acid Processes for Biobased Products and Bioethanol Production." Presented at AIChE 2001 Annual Meeting, Reno, NV, November 4-9, 2001.
Torget, R., (2001). "Aqueous Fractionation of Biomass Based on Novel Carbohydrate Hydrolysis Kinetics." U.S. Patent 6,228,177.
Torget, R., Hatzis, C., Hayward, T.K., Hsu, T., Philippidis, G.P. (1996). "Optimization of Reverse-Flow, Two-Temperature, Dilute-Acid Pretreatment to Enhance Biomass Conversion to Ethanol." Applied Biochemistry and Biotechnology. 57-58, 85-101
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