Progress 09/01/13 to 08/31/15
Outputs
Target Audience:The target audience was those professionals involved in researching and implementing biomass pretreatment.This includes a number of groups. One such group is fellow USDA NIFA AFRI project directors to whom I gave a presentation in August 2105.A second group of suchprofessionals reached include the readers of the journals Bioresource Technology, Chemical Engineering Journal, and Biomass Conversion and Biorefinery. The target audience includes attendees of the American Institute of Chemical Engineers (AIChE) Annual 2013, 2014, and 2015 meetings. Any AIChE member is also part of the target audience, since my five recorded presentations at the Annual meetingsare available on the AIChE website for viewing. In addition, the Biochemistry Department of Univ. of Nevada, Reno was reached through my presentationsat their Biofuels club in 2013, 2014, and 2015. Participants in the Process Integration and Carbon Efficiency Bioenergy Technologies Office Workshop of 2014in Denver, CO also were reached. Changes/Problems:Major additions to the original approach to the project were 1) characterization of the ionic liquid-glycerol solutions to determine why they enhanced yields and 2) creation of a novel ionic liquid - water separation technique that can use low temparature waste heat. What opportunities for training and professional development has the project provided?The project provided many opportunities for training and professional development. The main result of these opportunities was the completion of my Ph.D and dissertation. With the fellowship, I was able to choose my own creative work and achieve an outcome for my research that provides a green method for biomass deconstruction that could be used in the field. Other training and professional development opportunities the project provided included the following: Completing courses inBiochemistry, Mathematical Modeling, Teaching College Chemistry, and Environmental Law, achieving an"A" in each course. I learned much about plant physiology, how to model systems, and teaching techniques, thus having a change in knowledge. Interacting with Dr. Coronella, my mentor, I experienced a change in knowledge concerning how research should be conducted and prioritized. Presenting at the American Institute of Chemical Engineers (AIChE) Annual 2013, 2014, and 2015 meetings and experiencing other presentations there increased my expertise in biomass. Presenting for the Biochemistry Department of Univ. of Nevada, Reno. Presenting for the USDA NIFA AFRI Fellows in Washington and experiencing other presentations there increased my knowledge in biomass. Presenting seminars to the undergraduate and graduate students of the Chemical Engineering Department of the Univ. of Nevada, Reno. Participating in the Process Integration and Carbon Efficiency Bioenergy Technologies Office Workshop in Denver, CO, learning the new directions that biomass research is taking. Recruiting and mentoring volunteer undergraduates in my research. One of the undergraduates I mentored has co-authored a manuscript with me. Mentoring master's level graduate students, influencing them to change their actions toward more ethical or productive directions. Lecturing in the Process Control class at Univ. of Nevada, Reno. How have the results been disseminated to communities of interest?The results of my research have been disseminated through peer-reviewed journal articles. I also have presented my work at AIChE, the Biochemistry department and the Chemical Engineering department at UNR and the USDA NIFA AFRI Fellows meeting. What do you plan to do during the next reporting period to accomplish the goals?
Nothing Reported
Impacts
What was accomplished under these goals?
I accomplished a means to deconstruct rice hulls, loblolly pine, and corn stover using ionic liquid-glycerol mixtures. The carbohydrate portion, amenable to hydrolysis for fermentation to biofuels, was able to be separated from the protective lignin using theseenvironmentally-friendly solvents. As a inexpensive and safediluent, glycerol additionimproved the glucose yield in some cases.This less-hazardous, low temperature, and ambient pressure method could possibly be used in the field to acheive separation. Because of this USDA-NIFA-AFRI fellowship work, a change in knowledge has been facilitated in the biomass research community. During thefirst year of my USDA AFRI NIFA fellowship, I developed a method to deconstruct rice hulls. Over a million tons of this secondary agricultural residue is generated in the United States each year at central processing facilities. Using ionic liquids (salts molten at room temperature) and glycerol, a biodiesel by-product, I removed the lignin barrier from the hulls so that the biomass could be converted to glucose and other sugars. Glucose yield using this process was more than 30 times that for rice hulls that were not pretreated. A peer-reviewed journal article reported this work (Lynam, J.G., Coronella, C.J. 2014. Glycerol as an ionic liquid co-solvent for pretreatment of rice hulls to enhance glucose and xylose yield. Bioresour.Technol., 166, 471-478. DOI:10.1016/j.biortech.2014.05.086). If the low temperature/ low pressure process I developed is implemented to produce biofuels, it could enhance the economic viability of farm operations, since rice hulls are an underutilized agricultural residue that could be used as a sustainable resource. Beyond the United States, if rice hulls are used to produce biofuels, rather than burned in the open field for disposal, less fossil fuel would be used, so that climate change would be mitigated. During thesecond year of my USDA AFRI NIFA fellowship, Iinvestigated using the two ionic liquids 1-ethyl-3-methylimidazolium formate ([C2mim][O2CH]) and 1-ethyl-3-methylimidazolium acetate ([C2mim][OAc]) with glycerolto pretreat loblolly pine at 140 °C. With pretreatment, glucose yield from enzymatic hydrolysis was improved from 2% for raw pine up to 43%, while yields of mannose/xylose combined improved from 4% up to 77%. Pine pretreated with a 50% [C2mim][O2CH]-50% glycerol mixture exhibited a pulp-like structure, likely formed from removal of the lignin that binds cell walls together. Using this 50% mixture of [C2mim][O2CH] and glycerol for pretreatment gave a slightly lower glucose yield than a 75% mixture of [C2mim][O2CH] and glycerol, but gave a mannose/xylose yield twice as high. Klason lignin and Fourier transform infrared spectroscopy (FTIR) analysis indicated that [C2mim][O2CH] - glycerol pretreatment preferentially dissolves lignin. FTIR analysis also suggested increased amorphous cellulose content with this pretreatment. Using the anti-solvent ethanol, a lignin-rich substance was precipitated from the solvent mixtures. This research resulted in a peer-reviewed journal article (Loblolly pine pretreatment by ionic liquid-glycerol mixtures, Biomass Conv. Bioref.2015, Joan G. Lynam & Charles J. Coronella, DOI 10.1007/s13399-015-0183-5). Ionic liquids need to be recycled for re-use to improve economic feasibility and reduce waste treatment. I was able to recycle the ionic liquid solvents without loss of efficacy. However, water or other anti-solvents must be added to the ionic liquids to rinse or precipitate out biomacromolecules. Boiling off water can be used to regenerate the solvents. I wanted to use a lower temperature / ambient pressure means of separating water from ionic liquid. I came up with the idea of using membrane distillation for this separation. I found that this method using hydrophobic membranes was effective in removing water from ionic liquids, and filed a provisional patent application on it. A peer-reviewed journal article on this process is under review at Chemical Engineering Journal. Finally, I used these ionic liquid - glycerol mixtures on corn stover. I found that more than 90% of the glucose could be hydrolyzed from pretreatments using 25% ionic liquid - 75% glycerol solutions for 145 C pretreatments. A manuscript reporting these results is in preparation.
Publications
- Type:
Journal Articles
Status:
Published
Year Published:
2015
Citation:
Loblolly pine pretreatment by ionic liquid-glycerol mixtures,Biomass Conv. Bioref.2015,Joan G. Lynam & Charles J. Coronella, DOI 10.1007/s13399-015-0183-5.
- Type:
Journal Articles
Status:
Under Review
Year Published:
2016
Citation:
Under review by Chemical Engineering Journal: Joan G. Lynam, Genica I. Chow, Charles J. Coronella, and Sage R. Hiibel (Civil and Environmental Engineering Dept), Ionic Liquid and Water Separation by Membrane Distillation.
- Type:
Journal Articles
Status:
Other
Year Published:
2016
Citation:
Corn stover pretreatment by ionic liquid-glycerol mixtures, Joan G. Lynam, Genica I. Chow, Philip Hyland, Charles J. Coronella, in preparation.
- Type:
Conference Papers and Presentations
Status:
Submitted
Year Published:
2015
Citation:
Hydrothermal Carbonization of Different Biomass Types,Joan G. Lynam, M. Toufiq Reza, Wei Yan, Victor R. Vasquez and Charles J. Coronella, Presentation, ID# 413452 (password: 191015) Submitted to 2015 INTERNATIONAL CONGRESS ON ENERGY, 2015 Annual Meeting AIChE, Salt Lake City.
- Type:
Conference Papers and Presentations
Status:
Submitted
Year Published:
2015
Citation:
Dissolution of Lignin in Recalcitrant Biomass Using Ionic Liquid - Glycerol Mixtures, Joan G. Lynam and Charles J. Coronella,Presentation, ID# 413455 (password: 362311) Submitted to 2015 INTERNATIONAL CONGRESS ON ENERGY, 2015 Annual Meeting AIChE, Salt Lake City.
- Type:
Theses/Dissertations
Status:
Published
Year Published:
2015
Citation:
J.G. Lynam, Biomass Pretreatment using Ionic Liquid and Glycerol Mixtures, Chemical and Materials Engineering, University of Nevada, Reno, Reno, NV, USA, 2015.
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Progress 09/01/13 to 08/31/14
Outputs
Target Audience: The target audience during this reporting period is those professionals involved in researching and implementing biomass pretreatment. These professionals reached include the readers of the journal Bioresource Technology and the attendees of the American Institute of Chemical Engineers (AIChE) Annual 2014 meeting. Any AIChE member is also part of the target audience, since my recorded presentation at the Annual meeting is available on the AIChE website for viewing. In addition, the Biochemistry Department of Univ. of Nevada, Reno was reached through my presentation at their Biofuels club. Participants in the Process Integration and Carbon Efficiency Bioenergy Technologies Office Workshop in Denver, CO also were reached. Changes/Problems:
Nothing Reported
What opportunities for training and professional development has the project provided? 2. The other goal is the professional development of the Project Director. The project provided the following opportunities for training and professional development: 2.1 Training Activities: I completed graduate level courses in Biochemistry, Mathematical Modeling, and Teaching College Chemistry, achieving an "A" in each course. I learned much about plant physiology, how to model systems, and teaching techniques, thus having a change in knowledge. Also, through interacting with Dr. Coronella, my mentor, I experienced a change in knowledge concerning how research should be conducted and prioritized. 2.2 Professional Development: I presented at the American Institute of Chemical Engineers (AIChE) Annual 2014 meeting and for the Biochemistry Department of Univ. of Nevada, Reno. Experiencing other presentations there increased my knowledge in biomass pretreatment and modeling. I participated in the Process Integration and Carbon Efficiency Bioenergy Technologies Office Workshop in Denver, CO, learning the new directions that biomass research is taking. I also mentored undergraduates and master's level graduate students, influencing them to change their actions toward more ethical or productive directions. How have the results been disseminated to communities of interest?
Nothing Reported
What do you plan to do during the next reporting period to accomplish the goals? During the next reporting period, I plan to research loblolly pine pretreatment with IL-glycerol mixtures, characterizing the biomacromolecules precipitated from the mixture more thoroughly, as well as the glucose and other sugars produced by enzymatic hydrolysis.
Impacts
What was accomplished under these goals?
During the past year of my USDA AFRI NIFA fellowship, I developed a method to deconstruct rice hulls. Over a million tons of this secondary agricultural residue is generated in the United States each year at central processing facilities. Using ionic liquids (salts molten at room temperature) and glycerol, a biodiesel by-product, I removed the lignin barrier from the hulls so that the biomass could be converted to glucose and other sugars. Glucose yield using this process was more than 30 times that for rice hulls that were not pretreated. If the low temperature/ low pressure process I developed is implemented to produce biofuels, it could enhance the economic viability of farm operations, since rice hulls are an underutilized agricultural residue that could be used as a sustainable resource. Beyond the United States, if rice hulls are used to produce biofuels, rather than burned in the open field for disposal, less fossil fuel would be used, so that climate change would be mitigated. Long term Goal and Supporting Objectives: 1. The long term goal is to develop an environmentally-friendly, economically-feasible method to deconstruct non-food forest products and agricultural residues into cellulose, hemicellulose, lignin, and ash. Once separated, these components can be converted to valuable fuels and chemicals using available technology, while stimulating rural economies that possess biomass resources. 1.1 Major activities completed / experiments conducted: The chemicals/ biomass/ disposables required were ordered. The equipment obtained was modified for experimental setup. The Ionic Liquids (ILs) chosen were 1-ethyl-3-methylimidazolium acetate (EMIM Ac), 1-ethyl-3-methylimidazolium formate (EMIM Form), 1,3-dimethylimidazolium dimethylphosphate (DMIM DMP), and 1-ethyl-3-methylimidazolium diethylphosphate (EMIM DEP). Experimental cosolvents were varied to determine an optimum cosolvent. Glycerol was chosen as the most effective low-cost solvent. IL/ glycerol pretreatment of rice hull samples were performed at 110 °C for 3 hours using pure ILs, pure glycerol, 25:75, 50:50, and 75:25 mass ratios of IL: co-solvent. Each run was triplicated. 1.2 Data collected: Each residue was enzymatically hydrolyzed to find glucose and xylose yields using an HPLC. Mass yields and solvent recovery after filtration were measured. In addition, viscosity measurements of some IL-glycerol mixtures were made. 1.3 Summary statistics and discussion of results: Enzymatic hydrolysis of untreated rice hulls or rice hulls pretreated with glycerol, DMIM DMP, or EMIM DEP at 110 °C for 3 hours does not produce glucose or xylose. Pure EMIM Ac pretreatment is quite successful in preparing rice hulls for enzymatic hydrolysis, but when diluted with glycerol it loses its efficacy. EMIM Form pretreatment results in high sugar yields after subsequent enzymatic hydrolysis, even when diluted to a concentration of 25% with glycerol. A half and half mixture of EMIM Form with glycerol produced a better glucose yield than pure EMIM Form. Diluting EMIM Form with glycerol improved solvent recovery. Glucose yield increased with mass removal by pretreatment. The enhancements realized with an EMIM Form – glycerol pretreatments are partially due to lowered viscosity. 1.4 Key outcomes or other accomplishments realized: Rice hulls, a widely-available secondary agricultural residue, can be pretreated with EMIM Form-glycerol mixtures prior to enzymatic hydrolysis to enhance glucose and xylose yields. Since the high cost of ILs is a deterrent to commercial deployment at present, the key outcome is that glycerol, at about $0.18/Kg, is a suitable IL cosolvent for at least one IL. Using an EMIM Form – glycerol mixture for rice hull pretreatment could be a practical step in conversion of this recalcitrant biomass to biofuel. Because of this study (Lynam JG and Coronella CJ (2014) Glycerol as an ionic liquid co-solvent for pretreatment of rice hulls to enhance glucose and xylose yield. Bioresour.Technol. 166:471-478) a change in knowledge has been facilitated in the biomass research community.
Publications
- Type:
Journal Articles
Status:
Published
Year Published:
2014
Citation:
Lynam, J.G., Coronella, C.J. 2014. Glycerol as an ionic liquid co-solvent for pretreatment of rice hulls to enhance glucose and xylose yield. Bioresour.Technol., 166, 471-478. DOI:10.1016/j.biortech.2014.05.086
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