Joan G. Lynam Chemical & Materials Engineering Dept, Univ. of Nevada, Reno Boise State Mechanical and Biomedical Engineering Department Seminar October 30, 2015 Seminar Boise State Mechanical and Biomedical Engineering Department October 30, 2015 1 Biomass Carbon Cycle CO2 once stored in the biomass is returned to the atmosphere. Biomass absorbs CO2 through photosynthesis. CO2 CO2 Cellulosic ethanol C C The Energy Independence and Security Act of 2007 (EISA): Set goals to reduce fossil fuels and greenhouse gas (GHG) by increasing cellulosic ethanol use from 250 million gallons in 2011 to 16 billion by 2022 No cellulosic ethanol was produced in 2011 and 0.2 million gallons was produced in the first quarter of 2015 Seminar Boise State Mechanical and Biomedical Engineering Department October 30, 2015 2 Lignocellulosic Biomass Not Ionic Liquids Ionic Liquid – Glycerol Mixtures Rice hull pretreatment Loblolly pine pretreatment Characterization Recycling Diluted Ionic Liquid Conclusions/Future Work Seminar Boise State Mechanical and Biomedical Engineering Department October 30, 2015 3 Biorefinery Pretreatment Ionic Liquid Solvent Separation Ethanol Butanol Enzymatic Hydrolysis Fermentation Lignin Recycle Fuel Seminar Boise State Mechanical and Biomedical Engineering Department October 30, 2015 Chemicals 4 Biorefinery Pretreatment Ionic Liquid Solvent Separation Ethanol Butanol Enzymatic Hydrolysis Fermentation Lignin Recycle Fuel Seminar Boise State Mechanical and Biomedical Engineering Department October 30, 2015 Chemicals 5 p-hydroxyphenyl (H) guaiacyl (G), and syringyl (S) Lignin shields cellulose from use. Hemicelluloses are easiest to remove. Mannose and Xylose, hemicellulosic monomers of galactoglucomannan and arabinoglucuronoxylan https://www.detip.upc.edu/recerca/fotos-projectes/projecte1 Cellulose, Hemicellulose Lignin Outcome Biofuels, Polymers Pretreatment Platform Chemicals Separation Seminar Boise State Mechanical and Biomedical Engineering Department October 30, 2015 7 Seminar Boise State Mechanical and Biomedical Engineering Department October 30, 2015 8 ❶Molten salts – melting point < 100 ̊C Ionic Liquid Solvent ❷Large cation – ionic structure poorly coordinated ❸Extremely low vapor pressure (unlike VOCs) “green” ❹Can be recycled ❺Can dissolve lignin in lignocellulosic biomass! Seminar Boise State Mechanical and Biomedical Engineering Department October 30, 2015 9 Seminar Boise State Mechanical and Biomedical Engineering Department October 30, 2015 10 _ Cl can produce HCl gas if IL is decomposed S containing anions can produce SO2 gas if IL is decomposed F containing anions can produce HF if IL is decomposed Seminar Boise State Mechanical and Biomedical Engineering Department October 30, 2015 11 _ Seminar Boise State Mechanical and Biomedical Engineering Department October 30, 2015 _ 12 + - Or Seminar Boise State Mechanical and Biomedical Engineering Department October 30, 2015 13 These have high Kamlet-Taft ẞ values ẞ => ability to be hydrogen bond acceptor + + Kamlet-Taft ẞ values greater than 0.8 can dissolve cellulose Seminar Boise State Mechanical and Biomedical Engineering Department October 30, 2015 14 + - But they are costly! Or $$$$ Seminar Boise State Mechanical and Biomedical Engineering Department October 30, 2015 15 H2O Biomass precipitates out Seminar Boise State Mechanical and Biomedical Engineering Department October 30, 2015 16 $$$$ Seminar Boise State Mechanical and Biomedical Engineering Department October 30, 2015 17 Seminar Boise State Mechanical and Biomedical Engineering Department October 30, 2015 18 Seminar Boise State Mechanical and Biomedical Engineering Department October 30, 2015 19 Glycerol is a byproduct of biodiesel production and is about 18¢/kg (8¢/lb). Seminar Boise State Mechanical and Biomedical Engineering Department October 30, 2015 20 Biomass Pretreatment Procedure Biomass Ionic Liquid Hulls + Glycerol 110 ̊C or 140 ̊C 3 hours Orbital Shaker 200 RPM HPLC Glucose Xylose Pretreated Biomass Antisolvent Analysis of sugars Biomacromolecules Cellulase, Hemicellulase Recycle Precipitate Cellobiase, Na citrate buffer(4.8 pH) Seminar Boise State Mechanical and Biomedical Engineering Department October 30, 2015 Biomass Pretreatment Procedure Biomass Ionic Liquid Hulls + Glycerol 110 ̊C or 140 ̊C 3 hours Pretreated biomass rinsed, filtered and dried. to determine which have been liberated by the process from the biomass. Water Orbital HPLC Shaker Glucose 200 RPM Xylose Antisolvent Analysis of sugars Biomacromolecules Cellulase, Hemicellulase Recycle Precipitate Cellobiase, Na citrate buffer(4.8 pH) Seminar Boise State Mechanical and Biomedical Engineering Department October 30, 2015 Biomass Pretreatment Procedure Biomass Ionic Liquid Hulls + Glycerol 110 ̊C or 140 ̊C 3 hours Biomass is enzymatically hydrolyzed and HPLC used to determine glucose and hemicellulosic sugars liberated from the biomass. Water Orbital HPLC Shaker Glucose 200 RPM Xylose Antisolvent Analysis of sugars Biomacromolecules Cellulase, Hemicellulase Recycle Precipitate Cellobiase, Na citrate buffer(4.8 pH) Seminar Boise State Mechanical and Biomedical Engineering Department October 30, 2015 Biomass Pretreatment Procedure Biomass Ionic Liquid Hulls + Glycerol 110 ̊C or 140 ̊C 3 hours Glucose and xylose yields as a % of initial cellulose & hemicellulose sugar content used to determine pretreatment efficiency. Water Orbital HPLC Shaker Glucose 200 RPM Xylose Antisolvent Analysis of sugars Biomacromolecules Cellulase, Hemicellulase Recycle Precipitate Cellobiase, Na citrate buffer(4.8 pH) (Ran experiments in triplicate) Seminar Boise State Mechanical and Biomedical Engineering Department October 30, 2015 Yield Glucose = Glucose produced after enzymatic hydrolysis x 100% Glucose existing in cellulose in raw biomass The yields of glucose and hemicellulosic sugars were used to determine biomass pretreatment efficacy. Seminar Boise State Mechanical and Biomedical Engineering Department October 30, 2015 Enzymatic Hydrolysis 25 Must be generated to produce food Already removed from field to processing centers Rice hulls 1200 800 400 Ash(~21%) 0 Faostat 2013 Rice hulls are ~20% of the seed Seminar Boise State Mechanical and Biomedical Engineering Department October 30, 2015 26 Glucose yield as a percentage of cellulose in original biomass Seminar Boise State Mechanical and Biomedical Engineering Department October 30, 2015 Control is raw rice hulls 27 ẞ => ability to be hydrogen bond acceptor Control is raw rice hulls Also, EMIM Form has a higher lattice potential energy, so it is more tightly bonded to itself. Seminar Boise State Mechanical and Biomedical Engineering Department October 30, 2015 28 If 25% glycerol added Control is raw rice hulls Seminar Boise State Mechanical and Biomedical Engineering Department October 30, 2015 29 Xylose yield as a percentage of hemicellulose in original biomass Seminar Boise State Mechanical and Biomedical Engineering Department October 30, 2015 Control is raw rice hulls 30 If 25% glycerol added Control is raw rice hulls Seminar Boise State Mechanical and Biomedical Engineering Department October 30, 2015 31 Seminar Boise State Mechanical and Biomedical Engineering Department October 30, 2015 32 Seminar Boise State Mechanical and Biomedical Engineering Department October 30, 2015 33 If 50% glycerol added Seminar Boise State Mechanical and Biomedical Engineering Department October 30, 2015 34 Seminar Boise State Mechanical and Biomedical Engineering Department October 30, 2015 35 50% or 75% glycerol added Seminar Boise State Mechanical and Biomedical Engineering Department October 30, 2015 36 Loblolly Pine Second most common species of tree in the US Rapid growth Commercially Important for pulp and paper industry High in guaiacyl lignin 30% Seminar Boise State Mechanical and Biomedical Engineering Department October 30, 2015 recalcitrant Changed to 140 °C Pretreatment (Lignin’s Tg ) 37 Klason Lignin HPLC FTIR Seminar Boise State Mechanical and Biomedical Engineering Department October 30, 2015 38 EMIM Ac results Glucose yield as a percentage of cellulose in original biomass Seminar Boise State Mechanical and Biomedical Engineering Department October 30, 2015 39 12 x yield compared to raw pine Glucose yield as a percentage of cellulose in original biomass Seminar Boise State Mechanical and Biomedical Engineering Department October 30, 2015 40 15 x yield for raw pine Mannose/ xylose yield as a percentage of hemicellulose in original biomass Seminar Boise State Mechanical and Biomedical Engineering Department October 30, 2015 41 yield for 1315x xyield raw pine to compared raw pine Mannose/ xylose yield as a percentage of hemicellulose in original biomass Seminar Boise State Mechanical and Biomedical Engineering Department October 30, 2015 42 EMIM Form results Glucose yield as a percentage of cellulose in original biomass Seminar Boise State Mechanical and Biomedical Engineering Department October 30, 2015 43 18 x yield compared to raw pine Glucose yield as a percentage of cellulose in original biomass Seminar Boise State Mechanical and Biomedical Engineering Department October 30, 2015 44 Mannose/ xylose yield as a percentage of hemicellulose in original biomass Seminar Boise State Mechanical and Biomedical Engineering Department October 30, 2015 45 15 x yield compared to raw pine Mannose/ xylose yield as a percentage of hemicellulose in original biomass Seminar Boise State Mechanical and Biomedical Engineering Department October 30, 2015 46 FTIR-ATR shows: ❶ Pretreated pine has less lignin. ❷ Pretreated pine has more amorphous or type II cellulose. ❸ Material precipitated out of IL by ethanol is lignin rich. ❹ Enzymatically hydrolyzed pine has more lignin and less cellulose Seminar Boise State Mechanical and Biomedical Engineering Department October 30, 2015 Lignin Cellulose Lignin Cellulose Enzymatically Hydrolyzed Pine Lignin 47 35 Raw pine 30 25 % Klason 20 lignin in pretreated 15 sample EMIM form EMIM Ac 10 5 0 0% 25% 50% 75% %IL in IL-glycerol mixture Seminar Boise State Mechanical and Biomedical Engineering Department October 30, 2015 48 Raw loblolly pine Pine after pretreatment in 50% EMIM Form had pulpy “cotton – like” texture Seminar Boise State Mechanical and Biomedical Engineering Department October 30, 2015 49 Raw Loblolly 50% EMIM Form Glycerol Pretreated 75% EMIM Form EMIM Form: Lignin removed between wood cell walls (middle lamella) Seminar Boise State Mechanical and Biomedical Engineering Department October 30, 2015 50 Seminar Boise State Mechanical and Biomedical Engineering Department October 30, 2015 51 Why does EMIM Form with glycerol pretreatment work better than EMIM Ac with glycerol? Why does EMIM Form’s performance improve with glycerol dilution? Seminar Boise State Mechanical and Biomedical Engineering Department October 30, 2015 52 Why does EMIM Form with glycerol pretreatment work better than EMIM Acet with glycerol? Why does EMIM Form’s performance improve with glycerol dilution? To figure it out I investigated pH, viscosity, and density. Seminar Boise State Mechanical and Biomedical Engineering Department October 30, 2015 53 Higher pH solutions generally better at dissolving lignin Seminar Boise State Mechanical and Biomedical Engineering Department October 30, 2015 54 0 25 90 100 110 120 130 140 Temperature (° C) [C2mim][OAc] (EMIM Ac) mole fractions: (♦) 0 (all glycerol), (■) 0.153 (25% IL), (▲) 0.351 (50% IL), (●) 0.619 (75% IL), (○) 1.0 (all EMIM Ac) . Seminar Boise State Mechanical and Biomedical Engineering Department October 30, 2015 55 0 25 90 100 110 120 130 140 Temperature (° C) [C2mim][O2CH] (EMIM Form) mole fractions: (♦) 0 (all glycerol), (■) 0.164 (25% IL), (▲) 0.371 (50% IL), (●) 0.638 (75% IL), (○) 1.0 (all EMIM Form) . Seminar Boise State Mechanical and Biomedical Engineering Department October 30, 2015 56 Is higher viscosity requiring greater energy for mixing causing particle shearing or fragmentation? 0 25 90 100 110 120 130 140 Temperature (° C) [C2mim][O2CH] (EMIM Form) mole fractions: (♦) 0 (all glycerol), (■) 0.164 (25% IL), (▲) 0.371 (50% IL), (●) 0.638 (75% IL), (○) 1.0 (all EMIM Form) . Seminar Boise State Mechanical and Biomedical Engineering Department October 30, 2015 57 Less dense means greater volume per mole Seminar Boise State Mechanical and Biomedical Engineering Department October 30, 2015 58 EMIM Ac – small VmE EMIM Ac mole fractionEMIM EMIM Form – large, positive VmE Particularly at 140° C EMIM Form mole fraction Seminar Boise State Mechanical and Biomedical Engineering Department October 30, 2015 59 Dissociation of positive and negative ions VmE Disruption of hydrogen bonding network in molecular solvent VmE Anions may hydrogen bond with the molecular solvent VmE Molecules from molecular solvent may fit in the interstices of IL VmE EMIM Ac has smaller VmE and less positive VmE : effects & effects may counteract each other EMIM Form has larger VmE and positive VmE : Seminar Boise State Mechanical and Biomedical Engineering Department October 30, 2015 effects outweigh effects 60 Tighter structure Seminar Boise State Mechanical and Biomedical Engineering Department October 30, 2015 61 EMIM Form Seminar Boise State Mechanical and Biomedical Engineering Department October 30, 2015 62 Loose structure Seminar Boise State Mechanical and Biomedical Engineering Department October 30, 2015 63 Biorefinery Pretreatment Ionic Liquid Solvent Separation Ethanol Butanol Enzymatic Hydrolysis Fermentation Lignin Recycle Fuel Seminar Boise State Mechanical and Biomedical Engineering Department October 30, 2015 Chemicals 64 Biorefinery Pretreatment Ionic Liquid Solvent Separation Ethanol Butanol Enzymatic Hydrolysis Fermentation Lignin Recycle Fuel Seminar Boise State Mechanical and Biomedical Engineering Department October 30, 2015 Chemicals 65 Recycling Diluted Ionic Liquids Water Biomass has to be rinsed after ionic liquid pretreatment Water is an anti-solvent excluding biomass and diluting ionic liquid H2O Seminar Boise State Mechanical and Biomedical Engineering Department October 30, 2015 66 Recycling Diluted Ionic Liquids Water Biomass has to be rinsed after ionic liquid pretreatment Water is an anti-solvent excluding biomass and diluting ionic liquid H2O Ionic liquids are expensive and need to be recycled $$$$ Seminar Boise State Mechanical and Biomedical Engineering Department October 30, 2015 67 Seminar Boise State Mechanical and Biomedical Engineering Department October 30, 2015 Standard Distillation –Energy Intensive: High Temperature or Low Pressure Boiling point elevation with ions from ionic liquid Pervaporation – Vacuum Use Direct Contact Membrane Distillation (DCMD) - Ambient Pressure http://library.thinkquest.org/C006669/data/Chem/colligative.html Seminar Boise State Mechanical and Biomedical Engineering Department October 30, 2015 Direct Contact Membrane Distillation (DCMD) Uses lower temperatures (30 – 90 °C) so waste heat can be used Uses vapor pressure difference of the solution at different temperatures Ambient pressure Hydrophobic membrane – Ionic Liquid will not wet it. Water gas molecules will pass through hydrophobic membrane, but ionic liquid (salt) does not vaporize. Seminar Boise State Mechanical and Biomedical Engineering Department October 30, 2015 5% Ionic Liquid Feed at either 40 °C or 50 °C Water Distillate at 20 °C ∆T = 20 °C or 30 °C Flat-sheet Membrane with 78 cm2 of surface area Cross Flow Velocity of 0.12 m/s Run at least 45 minutes Seminar Boise State Mechanical and Biomedical Engineering Department October 30, 2015 Seminar Boise State Mechanical and Biomedical Engineering Department October 30, 2015 Ran until Feed was used up Seminar Boise State Mechanical and Biomedical Engineering Department October 30, 2015 Ran until Feed was used up Seminar Boise State Mechanical and Biomedical Engineering Department October 30, 2015 60 50 40 % IL Ran until Feed was used up 30 20 10 0 Time Able to concentrate ILs from 5 % to 50% Further concentration possible Seminar Boise State Mechanical and Biomedical Engineering Department October 30, 2015 Seminar Boise State Mechanical and Biomedical Engineering Department October 30, 2015 76 IL – Glycerol mixtures can be used to pretreat recalcitrant biomass for hydrolysis to glucose and hemicellulosic sugars Higher temperatures and more equal IL: Glycerol ratios may increase excess molar volume in the mixtures Higher molar volumes may increase lignin removal, enhancing sugar yields Diluted ionic liquids can be concentrated using direct contact membrane distillation Seminar Boise State Mechanical and Biomedical Engineering Department October 30, 2015 77 Optimize temperature, dissolutions times, and particle diameters Pretreat corn stover or other easier-todeconstruct biomass with IL - glycerol mixtures Investigate direct contact membrane distillation for IL-glycerol mixtures Seminar Boise State Mechanical and Biomedical Engineering Department October 30, 2015 78 This material is based upon work supported by the National Institute of Food and Agriculture, U.S. Department of Agriculture, under Agreement No. 2013-67011-21011 Seminar Boise State Mechanical and Biomedical Engineering Department October 30, 2015 Any opinions, findings, conclusions, or recommendations expressed in this publication are those of the author(s) and do not necessarily reflect the view of the U.S. Department of Agriculture. 79 This material is based upon work supported by the National Institute of Food and Agriculture, U.S. Department of Agriculture, under Agreement No. 2013-67011-21011 Seminar Boise State Mechanical and Biomedical Engineering Department October 30, 2015 Questions? 80 Seminar Boise State Mechanical and Biomedical Engineering Department October 30, 2015 81 Questions? Joan G Lynam Publications (all in peer-reviewed journals): 1. Joan G Lynam and Charles J Coronella, Glycerol as an ionic liquid co-solvent for pretreatment of rice hulls to enhance glucose and xylose yield, Bioresource Technology 2014. Volume 166: 471-478. 2. Joan G. Lynam, M. Toufiq Reza, Wei Yan, Charles J. Coronella*, Victor R. Vásquez, Hydrothermal carbonization of various lignocellulosic biomass. Biomass Conversion Biorefinery 2014 3. Lisha Yang, Ji Su, Sarah Carl, Joan G. Lynam, Xiaokun Yang, Hongfei Lin, Catalytic conversion of hemicellulosic biomass to lactic acid in pH neutral aqueous phase media, Applied Catalysis B Environmental 2015. Volume 162: 149-157. 4. M. Toufiq Reza*, Janet Andert, Benjamin Wirth, Daniela Busch, Judith Pielert, Joan G. Lynam, Jan Mumme 2014. Hydrothermal Carbonization of Biomass for Energy and Crop Production. Applied Bioenergy 2014. Volume 1: 11-29. 5. M. Toufiq Reza, Joan G. Lynam, M. Helal Uddin, and Charles J. Coronella, Engineered Pellets from Dry Torrefied and HTC Biochar Blends, Biomass and Bioenergy 2014. Volume: 63: 229-238. 6. M. Toufiq Reza, Wei Yan, M. Helal Uddin, Joan G. Lynam, S. Kent Hoekman, Charles J. Coronella*, and Victor R. Vásquez, Reaction Kinetics of Hydrothermal Carbonization of Loblolly Pine. Bioresour. Tech. 2013. Volume 139: 161-169. 7. M. Toufiq Reza, Joan G. Lynam, M. Helal Uddin, and Charles J. Coronella, Hydrothermal carbonization: Fate of Inorganics, Biomass and Bioenergy 2013. Volume 49: 86-94. 8. M. Helal Uddin, M. Toufiq Reza, Joan G. Lynam, and Charles J. Coronella, Effects of water recycling in hydrothermal carbonization of loblolly pine. Envir. Prog and Sust. Energy 2013. Volume 33: 1309-1315. 9. Joan G. Lynam, M. Toufiq Reza, Victor R. Vasquez, Charles J. Coronella*,. Pretreatment of rice hulls by ionic liquid dissolution. Bioresource Technology 2012. Volume 114: 629-636. 10. Joan G. Lynam, Charles J. Coronella*,, Mohammad T. Reza, and Victor R. Vasquez, Effect of Salt Addition on Hydrothermal Carbonization of Lignocellulosic Biomass. Fuel 2012. Volume 99: 271-273. 11. M. Toufiq Reza, Joan G. Lynam, Victor R. Vasquez and Charles J. Coronella*, 2012. Pelletization of biochar from hydrothermally carbonized wood. Environmental Progress & Sustainable Energy 2012. Volume 31: 12. Joan G. Lynam, M. Toufiq Reza, Victor R. Vasquez, Charles J. Coronella*, 2012. Effects of acetic acid and LiCl on lignocellulosic biomass. Bioresour. Tech. 2012. Volume 114: 629-636. 13. Prepared for submission to Biotechnology for Biofuels: Joan G Lynam and Charles J Coronella, Loblolly pine pretreatment by ionic liquid-glycerol mixtures, May 2015. Biomass Pretreatment using Ionic Liquid – Glycerol Mixtures Dissertation Defense May 7, 2015 82 Biomass Pretreatment using Ionic Liquid – Glycerol Mixtures Dissertation Defense May 7, 2015 83 Biomass Pretreatment using Ionic Liquid – Glycerol Mixtures Dissertation Defense May 7, 2015 84 Kamlet Taft beta The solvatochromic probe molecules 4-nitroanisole (1), 4-nitrophenol (2), and 2,6-diphenyl-4-[2,4,6triphenylpyridinio]phenolate inner salt (Reichardt’s Dye) (3) in uv-visible light. Biomass Pretreatment using Ionic Liquid – Glycerol Mixtures Dissertation Defense May 7, 2015 85 Biomass Pretreatment using Ionic Liquid – Glycerol Mixtures Dissertation Defense May 7, 2015 86 Biomass Pretreatment using Ionic Liquid – Glycerol Mixtures Dissertation Defense May 7, 2015 87 SI Figure 1 FTIR-ATR spectra for (top to bottom) washed raw loblolly pine, pine pretreated in 100% glycerol, pine pretreated in 25% EMIM Form-75% glycerol mixture, pine pretreated in 50% EMIM Form-50% glycerol mixture, and pine pretreated in 75% EMIM Form-25% glycerol mixture. Three spectra of a given condition were averaged for each line, and spectra were normalized using the 2300 cm-1 plateau baseline and the 1030 cm-1 peak, since it has lignin, cellulose, and hemicellulose components (Colom X, Carrillo F, Nogues F and Garriga P (2003) Structural analysis of photodegraded wood by means of FTIR spectroscopy. Polym. Degrad. Stabil. 80:543-549). Wavenumber 1160 corresponds to peak for cellulose type I and type II noticeably increases with higher IL % pretreatment (reduced lignin means higher cellulose concentration). Wavenumber 1262 corresponds to lignin guaiacyl methoxyl group. Peak decreases with higher IL % pretreatment. Wavenumber 1457 corresponds to lignin and xylan. Peak decreases with higher IL % pretreatment. Wavenumber 1510 corresponds to lignin. Peak decreases with higher IL % pretreatment. Wavenumber 896 corresponds to amorphous cellulose. Peak increases with higher IL % pretreatment. Biomass Pretreatment using Ionic Liquid – Glycerol Mixtures Dissertation Defense May 7, 2015 88 http://www.intechopen.com/books/sustainable-degradation-o lignocellulosic-biomass-techniques-applications-andcommercialization/hydrolysis-of-biomass-mediated-by-cellula for-the-production-of-sugars http://nptel.ac.in/courses/116102016/20 Swelling of cellulose fibres in Alkali solutions http://www.celignis.com/chemistry.php Biomass Pretreatment using Ionic Liquid – Glycerol Mixtures Dissertation Defense It must be clear that mercerization involves disruption of crystalline part of cellulose. For this to happen, alkali solutions of sufficiently high concentrations which can form alkali hydrates of such sizes which can enter the crystalline phase must be employed. Swelling occurs during mercerization but it is not the sufficient condition for mercerization to take place. May 7, 2015 89 Biomass Pretreatment using Ionic Liquid – Glycerol Mixtures Dissertation Defense May 7, 2015 90 (P+ a*n^2/V^2)(V-nb) = nRT (a) is attractive force, (b) is volume of exclusion Biomass Pretreatment using Ionic Liquid – Glycerol Mixtures Dissertation Defense May 7, 2015 91 Biomass Pretreatment using Ionic Liquid – Glycerol Mixtures Dissertation Defense May 7, 2015 92 Glycerol is a byproduct of biodiesel production and is about 18¢/kg (8¢/lb). Biomass Pretreatment using Ionic Liquid – Glycerol Mixtures Dissertation Defense May 7, 2015 93