Progress 01/01/14 to 12/31/18
Outputs
Target Audience:The production of liquid fuels via fast pyrolysis and electrocatalysis was targeted to research scientists, engineers, industrial partners, stakeholder groups, a 4H student group, and two groups of Detroit area youth that attended at summer camp at Michigan State University. Two presentations regarding pyrolysis were provided to high school students (71 total) from the Detroit area as part of PAAMEE (Preparing African American Males for Energy and Education) in June of 2018. The concepts of biomass deconstruction and pyrolysis were also presented to 4H students, mostly high schoolers, in July of 2018. One presentation was given at the 232nd Electrochemical Society meeting in 2017. Four presentations were given at the American Institute of Chemical Engineers annual conference in November of 2017 to an engineering and scientific audience. One presentation was presented at the American Society of Agricultural and Biological Engineers in July of 2018, again to an engineering and scientific audience. Finally, my graduate students routinely presented posters at local symposia and conferences at Michigan State University in 2018 to mixed audiences. Changes/Problems:
Nothing Reported
What opportunities for training and professional development has the project provided?One graduate student was advised to investigate the use of electrocatalysis to transform lignin model compounds to chemically reduced forms such as cyclohexanol. This student performed a variety of chemical reductions, more than tripling the slate of molecules that were previously investigated. She also upgraded lignin dimers using electrocatalysis, demonstrating this technology for molecules that better represent the lignin oligomers in actual bio-oil. She has also continued to develop a new method for catalyst preparation that will be universally adopted in our laboratory. This method is much less severe in terms of temperature and pressure than the previous method. She completed her dissertation in the summer of 2018. A second graduate student, funded by the EPA, has been working on whole bio-oil electroreduction. She is currently using electrocatalysis to upgrade pine wood bio-oil. Once completed, the mass and energy balance data collected will inform a life-cycle assessment that includes biomass processing by pyrolysis and electrocatalysis. A third graduate student is now formulating a kinetic model of electrocatalysis that will be useful for scaling up electrocatalysis to the bench and pilot levels. The model is being derived for phenol conversion into cyclohexanol. Several stoichiometric expressions, including those for hydrogen gas evolution, are included in this model. Completion of this activity is key for the design of bio-oil upgrading depots that use pyrolysis and electrocatalysis to deconstruct and upgrade biomass into a reliable, commoditized, fuel intermediate. How have the results been disseminated to communities of interest?Research results were disseminated to the scientific community at the AICHE conference in Minneapolis, MN, the ASABE conference in Detroit, MI, and the TCBiomass Conference in Chicago, IL. Two journal articles were also published during the reporting period to further information dissemination to the scientific community. What do you plan to do during the next reporting period to accomplish the goals?
Nothing Reported
Impacts
What was accomplished under these goals?
Biomass conversion to solid fuels and liquid fuels were the subjects of this past project. Solid fuel production from biomass was investigated to provide a renewable replacement for coal in power plants. Biomass torrefaction, a mild heat treatment that creates a renewable solid fuel with coal-like properties, was investigated as a pretreatment for making industrial chemicals and as a renewable competitor to wind energy. Unlike wind and solar sources of electricity, torrefied biomass is readily dispatchable to meet real-time demand. A demonstration trial involving about 300 tons of torrefied biomass was performed at the T.B. Simon Power Plant at Michigan State University (MSU). This trial was largely regarded as a success, though grinding energy was higher than that required for grinding coal. Biomass-to-liquids is an ongoing pursuit at Michigan State University, with an emphasis on deconstruction by fast pyrolysis followed by upgrading with electrocatalysis. Since the start of this project, an in-depth study of lignin-derived phenolics has led to an advanced understanding of how such molecules become saturated with hydrogen under the conditions present during electrocatalysis. Several lignin monomer studies have shown that electrocatalysis can cleave methoxy functional groups, saturate aromatic rings, and partially deoxygenate phenolics using different catalytic cathodes. The impact of this new knowledge should extend to raw pyrolysis bio-oils to result in a new pathway to make hydrocarbon replacements for fossil fuels. If successful, this potentially carbon-negative approach will couple renewable electricity with renewable biomass to make fuels and chemicals while reducing atmospheric carbon dioxide. Solid fuel creation by biomass torrefaction: 1. Survey biomass varieties (esp. forest biomass) and torrefaction operating conditions (temperature, residence time) to provide guidance for a nascent solid fuels industry In previous years of this project, mixed hardwoods were characterized prior to torrefaction in MSU's kilogram-scale torrefier. This sample was provided by Heat Transfer International, a company with interest in thermal conversion. A temperature of 263°C and a residence time of 10 minutes were found to optimize the energy yield of torrefaction, a value that is within the range provided in the literature. 2. Develop techniques to assess fuel properties such as grindability, dust formation and hydrophobicity that along with existing methods for higher heating value, bulk density and ultimate analysis will be used for comparison with coal A HGI (Hardgrove Grindability Index) mill was purchased by to assess the grindability of solid fuel products. Additionally, a water droplet immersion assay was developed to assess the hydrophobicity of torrefied wood briquettes and pellets. 3. Formulate a systems model to assess the economics and environmental impacts of decentralized torrefaction and densification on centralized electrical power generation In prior years of this project, our research team reported the effect of water content on the optimum torrefaction scale, i.e. processing capacity. More severe torrefaction can be justified at higher moisture contents owing to more torrefaction gas produced. As this gas is burned, more gas equates to more process heat, which is needed to remove larger amounts of water. My group also detailed the production of aromatic chemicals upon a sequence of torrefaction, pyrolysis, and heterogenous catalysis using ZSM5-type catalysts. Generally, torrefaction can be used as pyrolysis pretreatment if biomass costs are low (less than $58 per tonne). Higher biomass costs preclude torrefaction because mass loss negates the higher yields observed during subsequent pyrolysis. We also compared the use of torrefied biomass briquettes to wind energy supplemented with natural gas to make electricity. Natural gas is needed to supplement wind energy to overcome intermittency and to provide process heat. In terms of an energy analysis, torrefaction provides heat and power at greater energy return on investment (EROI) than does wind plus natural gas. Only at high wind velocities are wind turbines superior. Liquid fuel creation by biomass pyrolysis: 4. Survey biomass varieties and pyrolysis operating conditions to determine plant species and process parameters that yield favorable bio-oil characteristics and system economics Mixed pine wood bio-oil was obtained from BTG and has been used as a feedstock for electrocatalysis. Significant method development was necessary as this substrate tends to form foam and leave the cathode compartment. Also, dilution in water, necessary to scale down the experiments so that the available power supplies can reasonably complete an experiment, leads to unwanted phase separation to form an aqueous layer and pyrolytic lignin. Work with pine wood is ongoing and progress has been made towards its upgrading via electrocatalysis. In prior years of this project, the Saffron group participated with the Great Lakes Bioenergy Research Center to investigate the use of electrocatalysis to first deconstruct corn stover-derived lignin, and then reduce the products into fuels and chemicals. In this regard, we evaluated a number of model compounds that become saturated by hydrogen at mild conditions of 1 atm and 80°C. These bio-oils serve as feedstocks for electrocatalytic reduction. 5. Investigate ECH as a means of stabilizing model compounds and raw bio-oil and develop methods for characterizing the complex bio-oil intermediate Whole bio-oil electroreduction from pine wood was attempted during this reporting cycle. Several issues related to cell operation were encountered when using raw pine bio-oil as the sole substrate in the cathode compartment. First, the hydrogen gas formation occurred at an excessive rate, leading to foam formation and entrainment of bio-oil out of the cathode compartment and onto the upper walls of the glass cathode cylinder. Second, rupture of the Nafion 115 membrane occurs for reasons that are not fully understood. Somewhat high voltages may be responsible for concentrating migrating ions on the anode side of the membrane, leading to pinhole ruptures. Low electrolyte addition to the cathode may be necessary to reduce such voltages, though electrolyte recycle will be costly at full scale. Dilution of bio-oil in methanol has been attempted to reduce the run time needed for full saturation of carbon-carbon, carbon-oxygen, and aromatic pi bonds. Though ideal for solubilizing nearly all of bio-oil, and ideal for direct injection into GC/MS for analysis, methanol was found to migrate across the Nafion 115 membrane and into the anode compartment. New membrane materials are being investigated that are impermeable to methanol migration. 6. Assess hydroprocessing as a means of upgrading stabilized bio-oil to hydrocarbon fuels Dr. Saffron collaborated with a Chinese visiting scholar who developed a new hydroprocessing model for petroleum upgrading. This model is being extended to gauge the use of hydroprocessing for upgrading the post-electrocatalysis products. 7. Formulate a systems model to assess the economics and environmental impacts of decentralized pyrolysis and ECH on liquid fuel supply chains through centralized hydroprocessing The hydroprocessing model described in the previous objective is being embedded in a refinery model that also involves distillation, alcohol-to-olefins processing, and olefin oligomerization to form fuel-range hydrocarbons. This model has been formulated and is being alpha tested to identify and fix programming errors. In parallel, a manuscript has been drafted and is undergoing revisions as the simulation's descriptive capacity is improved.
Publications
- Type:
Journal Articles
Status:
Published
Year Published:
2018
Citation:
Bhalla, A.; Fasahati, P.; Particka, C.A.; Assad, A.E.; Stoklosa, R.J.; Bansal, N.; Semaan, R. Saffron, C.M.; Hodge, D.B.; Hegg, E.L. Integrated experimental and technoeconomic evaluation of two-stage Cu-catalyzed alkaline-oxidative pretreatment of hybrid poplar. Biotechnology for Biofuels. 2018. 11(143).
- Type:
Journal Articles
Status:
Published
Year Published:
2018
Citation:
Wu, Le; Liang, Xiaoqiang; Kang, Lixia; Liu, Yongzhong; Saffron, C.M. Hydrogen network optimization by integrating impurity distributions of a fluid catalytic cracker and hydrogenation kinetics. Journal of Cleaner Production. 2018. 542-552.
|
Progress 10/01/16 to 09/30/17
Outputs
Target Audience:The production of liquid fuels via fast pyrolysis and electrocatalysis was targeted to research scientists, engineers, industrial partners, stakeholder groups, a 4H student group, and two groups of Detroit Area youth that attended at summer camp at Michigan State University. Two presentations were given at the American Institute of Chemical Engineers annual conference in November of 2016 to an engineering and scientific audience. Two presentations and two posters were presented at the American Society of Agricultural and Biological Engineers in July of 2017, again to an engineering and scientific audience. One presentation was given to a stakeholder group at the Michigan Forest Biomass Conference in February of 2017. Finally, my graduate students routinely presented posters at local symposia and conferences at Michigan State University in 2017 to mixed audiences. Changes/Problems:
Nothing Reported
What opportunities for training and professional development has the project provided?One graduate student was advised to investigate the use of electrocatalysis to transform lignin model compounds to chemically reduced forms such as cyclohexanol. This student performed a variety of chemical reductions, more than tripling the slate of molecules that were previously investigated. She also upgraded lignin dimers using electrocatalysis, demonstrating this technology for molecules that better represent the lignin oligomers in actual bio-oil. She has also developed a new method for catalyst preparation that will be universally adopted in our laboratory. This method is much less severe in terms of temperature and pressure than the previous method. Her work was presented through numerous posters and at the AICHE conference in November of 2016. A second graduate student, funded by the EPA, has been working on whole bio-oil electroreduction. Her work has resulted in marked physicochemical changes in bio-oil in terms of color, clarity, and odor. Analyses of post-electrocatalysis samples are in progress and a better understanding of the transformations occurring are expected in coming months. A third graduate student provided the modeling results that were used to compare a pyrolysis-electrocatalysis bioenergy system to cellulosic ethanol. This student is now formulating a kinetic model of electrocatalysis that will be useful for scaling up electrocatalysis to the bench and pilot levels. How have the results been disseminated to communities of interest?Research results were disseminated to the scientific community at the AICHE conference in San Francisco, CA, the ASABE conference in Spokane, WA, and the Michigan Forest Biomass Conference in Grand Rapids, MI. Three journal articles were also published during the reporting period to further information dissemination to the scientific community. What do you plan to do during the next reporting period to accomplish the goals?Further electrocatalysis of model compounds and real lignin dimers will proceed to quantify product yields and energy input. This work will be extended to real lignin samples and raw bio-oils with the aim of creating higher-value fuels and chemical products. Analysis of post-electrocatalysis bio-oils is in-progress, which will lead to an advanced understanding of the possible transformations that are enabled by this technology. Kinetic modeling of electrocatalysis is underway, which is needed to better design such systems for larger-scale applications.
Impacts
What was accomplished under these goals?
Solid fuel creation by biomass torrefaction: 1. Survey biomass varieties (esp. forest biomass) and torrefaction operating conditions (temperature, residence time) to provide guidance for a nascent solid fuels industry Nothing to report. 2. Develop techniques to assess fuel properties such as grindability, dust formation and hydrophobicity that along with existing methods for higher heating value, bulk density and ultimate analysis will be used for comparison with coal Nothing to report. 3. Formulate a systems model to assess the economics and environmental impacts of decentralized torrefaction and densification on centralized electrical power generation Nothing to report. Liquid fuel creation by biomass pyrolysis: 4. Survey biomass varieties and pyrolysis operating conditions to determine plant species and process parameters that yield favorable bio-oil characteristics and system economics The Saffron group participates on a project through the Great Lakes Bioenergy Research Center that is investigating the use of electrocatalysis to first deconstruct corn stover-derived lignin, and then reduce the products into fuels and chemicals. In this regard, we have evaluated a number of model compounds that become saturated by hydrogen at mild conditions of 1 atm and 80°C. In addition to corn stover, hybrid poplar (NM6) has been subjected to pyrolysis to produce liquid bio-oils. These bio-oils serve as feedstocks for electrocatalytic reduction. 5. Investigate ECH as a means of stabilizing model compounds and raw bio-oil and develop methods for characterizing the complex bio-oil intermediate Much work has been accomplished in this regard during the previous year. Electrocatalytic hydrogenation was shown to reduce such monoaromatic molecules as phenol, guaiacol and syringol. Phenolic dimers, such as 4-phenoxyphenol, were also cleaved to ultimately form cyclohexanol. In this reporting period, actual lignin dimers have been cleaved to demonstrate this technology's ability to upgrade lignin-derived bio-oil. A new technique for making the catalytic cathodes used for saturating bio-oils was investigated. This technique requires only mild conditions and does not produce gaseous hydrochloric acid as a by-product, which is corrosive to metal containers. This technique of preparing cathodes could be implemented within small-scale pyrolysis depots, which is important for reducing costs in these facilities. Whole bio-oil, derived from poplar, was also subjected to electrocatalytic reduction. Generally, several compounds within bio-oil become saturated, in an analogous manner as was observed in our model compound studies. Data from these experiments will be used to inform energy analyses, technoeconomic analysis and life cycle assessment. In this reporting period, whole bio-oils were electrocatalytically reduced to create a liquid stream with a higher fuel value. 6. Assess hydroprocessing as a means of upgrading stabilized bio-oil to hydrocarbon fuels Nothing to report. 7. Formulate a systems model to assess the economics and environmental impacts of decentralized pyrolysis and ECH on liquid fuel supply chains through centralized hydroprocessing Most importantly, in this reporting period, we compared a bioenergy system that uses decentralized pyrolysis-electrocatalysis to cellulosic ethanol as described by NREL (Humbird et al. 2011). The energy comparison shows that coupling energy from renewable electricity to the energy in bio-oil will substantially increase the amount of energy delivered as liquid fuel when compared to cellulosic ethanol. Further, the pyrolysis-electrocatalysis bioenergy system generates biochar as a co-product, which sequesters carbon when land applied. This fuel system is potentially "carbon-negative" when using decentralized pyrolysis-electrocatalysis to create a fuel intermediate that is sent to existing petroleum refineries.
Publications
- Type:
Journal Articles
Status:
Published
Year Published:
2017
Citation:
Lam, C.H.; Das, S.; Erickson, N. C.; Hyzer, C.D.; Garedew, M.; Anderson, J.E.; Wallington, T.J.; Tamor, M.A.; Jackson, J.E.; Saffron, C.M. Towards sustainable hydrocarbon fuels with biomass fast pyrolysis oil and electrocatalytic upgrading. Sustainable Energy and Fuels. 2017. 1. 258-266.
http://pubs.rsc.org/en/content/articlepdf/2017/se/c6se00080k
- Type:
Journal Articles
Status:
Published
Year Published:
2017
Citation:
Safferman, S.I.; Smith, J.S.; Dong, Y.; Saffron, C.M.; Wallace, J.M.; Binkley, D.; Thomas, M.R.; Miller, S.A.; Bissel, E.; Booth, J.; Lenz, J. Resources from Wastes: Benefits and Complexity. Journal of Environmental Engineering. 2017. 143(11): 03117005. http://ascelibrary.org.proxy2.cl.msu.edu/doi/pdf/10.1061/%28ASCE%29EE.1943-7870.0001259
- Type:
Journal Articles
Status:
Published
Year Published:
2017
Citation:
Fasahati, P.; Saffron, C.M.; Woo, H.C. Liu, J.J. Potential of brown algae for sustainable electricity production through anaerobic digestion. Energy Conservation and Management. 2017. 135. 297-307. http://ac.els-cdn.com/S0196890416311797/1-s2.0-S0196890416311797-main.pdf?_tid=0b9434aa-e810-11e6-a831-00000aacb362&acdnat=1485906809_4fc041caa704f4e0d5dfc239591f3eee
|
Progress 10/01/15 to 09/30/16
Outputs
Target Audience:The production of liquid fuels via fast pyrolysis and electrocatalysis was targeted to research scientists, industrial partners and a 4H student group that visited Michigan State University in the summer of 2016. Several posters were given at the Great Lakes Bioenergy Research Center's Annual Meeting in May of 2016. Two presentations were given at the American Institute of Chemical Engineers annual conference in November of 2015 to a scientific audience. A presentation and poster were presented at the American Society of Agricultural and Biological Engineers in July of 2016, again to a scientific audience. My graduate students routinely presented posters at local symposia and conferences at Michigan State University in 2016 to mixed audiences. My research in bio-oil electrocatalysis was selected by an undergraduate senior design group for further development in the Fall semester of 2015 and again in Spring of 2016. These students learned how to perform electroreduction of organic molecules that make up pyrolysis bio-oils. Changes/Problems:
Nothing Reported
What opportunities for training and professional development has the project provided?What opportunities for training and professional development has the project provided? Four senior design students selected electrocatalysis as a means of creating renewable hydrocarbons for displacing fossil petroleum. These students operated a small voltaic cell reactor to produce stable bio-oil, characterized its products analytically, and assessed its performance by developing a governing equation that describes the key reaction and transport mechanisms that control yields and rates. A process model was also formulated by these students to compute the cost contribution to a model hydrocarbon fuel. Finally, their results were discussed in an oral presentation given at BE Showcase and in a written report. One graduate student was advised to investigate the use of electrocatalysis to transform lignin model compounds to chemically reduced forms such as cyclohexanol. This student performed a variety of chemical reductions, more than tripling the slate of molecules that were previously investigated. Her work was presented through numerous posters and at the AICHE conference in November of 2015. A second graduate student, funded by the EPA, has been working on whole bio-oil electroreduction. In this regard, she presented a poster at the ASABE meeting in June of 2016. How have the results been disseminated to communities of interest?Research results were disseminated to the scientific community at the AICHE conference in Salt Lake City and the ASABE conference in Orlando. Three journal articles were also published during the reporting period to further information dissemination to the scientific community. What do you plan to do during the next reporting period to accomplish the goals?Developing torrefied biomass pellets or briquettes that are stable during water immersion is the next phase of my research regarding solid fuel production. Different feedstocks, operating conditions, densification conditions and the use of binding agents will be explored to create stable, fungible solid fuels from biomass. Surface characterization will also be pursued to better understand why water infiltrates what should be a hydrophobic material. Further electrocatalysis of model compounds and real lignin dimers will proceed to quantify product yields and energy input. This work will be extended to real lignin samples with the goal of converting lignin into higher-value fuels and chemical products.
Impacts
What was accomplished under these goals?
OBJECTIVES: The goal of this project is to develop sustainable bioenergy systems that convert biomass into stationary fuels for electric power or hydrocarbon fuels for transportation using carbon, hydrogen and energy efficient strategies. Solid fuels production will consist of decentralized torrefaction and densification, followed by centralized combustion at existing coal-fired power facilities. Transportation fuels production will include each of the three major conversion processes, i.e. pyrolysis, electrocatalysis, and hydroprocessing, needed to convert biomass into fungible liquids. Mass and energy balance data will be collected during my proposed investigation, with the aim of informing technoeconomic and future life cycle models. Because the application of electrocatalysis is a relatively unstudied approach, the exploration of model compound conversion is included to better understand the results gained upon actual bio-oil stabilization. The new knowledge that is gained will reduce the risk associated with the ultimate scale up and commercialization of the proposed system. The proposed objectives are a first step towards de-risking commercial processes that will be deployed near the areas of biomass harvest and collection. Accomplishments are listed by objective below. Briefly, the Saffron lab's solid fuel research centers on developing a water resistant briquette or pellet. Hydrophobicity, energy density and grindability of the torrefied material are key properties that must meet benchmarks before adoption of this renewable option will become widespread. In addition to solid fuels, liquid fuel from biomass, using pyrolysis and electrocatalysis, is being investigated that could supply renewable feedstock to America's petroleum refineries. Electrocatalysis is used to saturate carbon-carbon and carbon-oxygen double bonds using electricity from wind and solar energy sources. Solid fuel creation by biomass torrefaction: 1. Survey biomass varieties (esp. forest biomass) and torrefaction operating conditions (temperature, residence time) to provide guidance for a nascent solid fuels industry Nothing to report. 2. Develop techniques to assess fuel properties such as grindability, dust formation and hydrophobicity that along with existing methods for higher heating value, bulk density and ultimate analysis will be used for comparison with coal A proposal in this regard was submitted to the USDA Foundational Program in the July of 2016. This proposal is under review at the time of this report. 3. Formulate a systems model to assess the economics and environmental impacts of decentralized torrefaction and densification on centralized electrical power generation Three journal articles related to torrefaction were published during this reporting period. The first article, by Chai and Saffron, reported the effect of water content on the optimum torrefaction scale, i.e. processing capacity. More severe torrefaction can be justified at higher moisture contents owing to more torrefaction gas produced. As this gas is burned, more gas equates to more process heat, which is needed to remove larger amounts of water. A second article detailed the production of aromatic chemicals upon a sequence of torrefaction, pyrolysis, and heterogenous catalysis using ZSM5-type catalysts. Generally, torrefaction can be used as pyrolysis pretreatment if biomass costs are low (less than $58 per tonne). Higher biomass costs preclude torrefaction because mass loss negates the higher yields observed during subsequent pyrolysis. A third article compares the use of torrefied biomass briquettes to wind energy supplemented with natural gas. Natural gas is needed to supplement wind energy to overcome intermittency and to provide process heat. In terms of an energy analysis, torrefaction provides heat and power at greater energy return on investment (EROI) than does wind plus natural gas. Only at high wind velocities are wind turbines superior. Liquid fuel creation by biomass pyrolysis: 4. Survey biomass varieties and pyrolysis operating conditions to determine plant species and process parameters that yield favorable bio-oil characteristics and system economics The Saffron group participates on a project through the Great Lakes Bioenergy Research Center that is investigating the use of electrocatalysis to first deconstruct corn stover-derived lignin, and then reduce the products into fuels and chemicals. In this regard, we have evaluated a number of model compounds that become saturated by hydrogen at mild conditions of 1 atm and 80°C. This work will be extended to additional biomass varieties in future experiments. 5. Investigate ECH as a means of stabilizing model compounds and raw bio-oil and develop methods for characterizing the complex bio-oil intermediate Much work has been accomplished in this regard during the previous year. Electrocatalytic hydrogenation was shown to reduce such monoaromatic molecules as phenol, guaiacol and syringol. Phenolic dimers, such as 4-phenoxyphenol, were also cleaved to ultimately form cyclohexanol. This cleavage bodes well for cleaving lignin dimers that are the products of fast pyrolysis. A larger suite of phenolic molecules was surveyed during this reporting period. As a general rule, electroreduction capably demethoxylates and de-aromatizes the phenolic constituents in biomass pyrolysis oils. The results from these trials have been used as inputs to a global bioenergy system model that clearly shows the benefit of using electroreduction as an energy upgrading step. Whole bio-oil, derived from poplar, was also subjected to electrocatalytic reduction. Generally, several compounds within bio-oil become saturated, in an analogous manner as was observed in our model compound studies. Data from these experiments will be used to inform energy analyses, technoeconomic analysis and life cycle assessment. 6. Assess hydroprocessing as a means of upgrading stabilized bio-oil to hydrocarbon fuels Nothing to report. 7. Formulate a systems model to assess the economics and environmental impacts of decentralized pyrolysis and ECH on liquid fuel supply chains through centralized hydroprocessing A mass and energy balance model has been devised to describe biomass conversion into liquid fuels using decentralized pyrolysis and electrocatalysis followed by centralized refinement into hydrocarbons. The renewable energy return on fossil energy invested exceeds 6:1 for this system, and may be higher pending the production strategy used for making hydrogen. The use of this process could double the amount of energy available as liquid fuel versus what can be made by yeast to make ethanol. The Saffron group is readying a submission in this regard and expects publication within the next reporting period.
Publications
- Type:
Journal Articles
Status:
Published
Year Published:
2016
Citation:
Parkhurst, K.M.; Saffron, C.M.; Miller, R.O. An energy analysis comparing biomass torrefaction in depots to wind with natural gas combustion for electricity generation. Applied Energy. 2016. 179. 171-181.
- Type:
Journal Articles
Status:
Published
Year Published:
2016
Citation:
Chai, L.; Saffron, C.M.; Yang, Y.; Zhang, Z.; Munro, R.W.; Kriegel, R.M. Integration of decentralized torrefaction with centralized catalytic pyrolysis to produce green aromatics from coffee grounds. Bioresource Technology. 2016. 201. 287-292.
- Type:
Journal Articles
Status:
Published
Year Published:
2016
Citation:
Chai, L.; Saffron, C.M. Comparing pelletization and torrefaction depots: Optimization of depot capacity and biomass moisture to determine the minimum production cost. Applied Energy. 2016. 163. 387-395.
|
Progress 10/01/14 to 09/30/15
Outputs
Target Audience:The production of liquid fuels via fast pyrolysis and electrocatalysis was targeted to research scientists, industrial partners and a 4H student group that visited Michigan State University in the summer of 2015. A presentation and several posters were given at the Great Lakes Bioenergy Research Center's annual retreat, and at the American Institute of Chemical Engineers annual conference. A summer research opportunity (SROP) student worked with graduate students in the laboratory. Solid fuels production was targeted to an undergraduate design group, who furthered a method for making biomass briquettes. The T.B. Simon Power Plant, at Michigan State University, was included in this project, with the goal of replacing coal with torrefied biomass. Changes/Problems:
Nothing Reported
What opportunities for training and professional development has the project provided?Three senior design students selected torrefaction as a means of creating renewable electrical power for MSU's power plant. These students operated a pilot-scale reactor to produce torrefied wood, operated a briquetting system, and assessed different binding agents for maintaining briquette integrity. A process model was formulated by these students to compute the cost contribution to electrical power generation. Finally, their results were discussed in an oral presentation given at BE Showcase and in a written report. One graduate student was advised to investigate the use of electrocatalysis to transform lignin model compounds to chemically reduced forms such as cyclohexanol. This student performed a variety of chemical reductions, more than tripling the slate of molecules that were previously investigated. Her work was presented through numerous posters and at the AICHE conference in November of 2014. A Ph.D. student finished his dissertation involving the conversion of biomass into aromatic chemicals. He studied the effects of torrefaction as a preprocessing step on aromatic yields after catalytic pyrolysis. He has accepted a post-doctoral position in my research group. How have the results been disseminated to communities of interest?Research results were disseminated to the scientific community at the at the TCS Symposium in Denver and the AICHE conference in Atlanta. Five journal articles were also published during the reporting period to further information dissemination to the scientific community. What do you plan to do during the next reporting period to accomplish the goals?Developing torrefied biomass pellets or briquettes that are stable during water immersion is the next phase of my research regarding solid fuel production. Different feedstocks, operating conditions, densification conditions and the use of binding agents will be explored to create stable, fungible solid fuels from biomass. Surface characterization will also be pursued to better understand why water infiltrates what should be a hydrophobic material. Further electrocatalysis of model compounds and real lignin dimers will proceed to quantify product yields and energy input. This work will be extended to real lignin samples with the goal of converting lignin into higher-value fuels and chemical products.
Impacts
What was accomplished under these goals?
Solid fuel creation by biomass torrefaction: 1. Survey biomass varieties (esp. forest biomass) and torrefaction operating conditions (temperature, residence time) to provide guidance for a nascent solid fuels industry Bench-scale biomass torrefaction is being routinely performed using a small reactor that maintains anoxic conditions while be externally heated in a furnace. Gram quantities of torrefied product are typically collected from this reaction vessel. Even smaller-scale torrefaction has been performed using a themogravimetric analyzer to collect sub-gram quantities of product. This technique is useful as a screening tool for quickly assessing the properties of torrefied products. 2. Develop techniques to assess fuel properties such as grindability, dust formation and hydrophobicity that along with existing methods for higher heating value, bulk density and ultimate analysis will be used for comparison with coal Higher heating value, bulk density and ultimate analysis are supported by the Saffron lab or other labs funded by AgBioResearch at MSU. The Hardgrove Grindability Index can now be measured at Michigan State to determine the ease of grinding torrefied biomass into smaller particulates. Water droplet and immersion assays were developed in 2015 to assess hydrophobicity of torrefied wood briquettes and pellets 3. Formulate a systems model to assess the economics and environmental impacts of decentralized torrefaction and densification on centralized electrical power generation A senior design project and two graduate research projects contributed to this model. The senior design project investigated the use of different binding agents for creating stable biomass briquettes and the cost of such binding agents was found to be significant. Conversely, torrefied biomass combustion for electricity outperforms wind turbines in areas of low wind velocity. This article is under review in the journal Applied Energy. Liquid fuel creation by biomass pyrolysis: 4. Survey biomass varieties and pyrolysis operating conditions to determine plant species and process parameters that yield favorable bio-oil characteristics and system economics Different biomass varieties were evaluated by catalytic fast pyrolysis for making aromatic chemicals. Those varieties that contain higher levels of carbon and lower levels of oxygen tend to produce greater amounts of aromatics. From this result, plant varieties for the manufacture of bio-terephthalic acid can be better selected, which has implications for making PETE beverage containers. 5. Investigate ECH as a means of stabilizing model compounds and raw bio-oil and develop methods for characterizing the complex bio-oil intermediate A larger suite of phenolic molecules was surveyed during this reporting period. As a general rule, electroreduction capably demethoxylates and de-aromatizes the phenolic constituents in biomass pyrolysis oils. The results from these trials have been used as inputs to a global bioenergy system model that clearly shows the benefit of using electroreduction as an energy upgrading step. 6. Assess hydroprocessing as a means of upgrading stabilized bio-oil to hydrocarbon fuels Nothing to report. 7. Formulate a systems model to assess the economics and environmental impacts of decentralized pyrolysis and ECH on liquid fuel supply chains through centralized hydroprocessing A mass and energy balance model has been devised to describe biomass conversion into liquid fuels using decentralized pyrolysis and electrocatalysis followed by centralized refinement into hydrocarbons. The renewable energy return on fossil energy invested exceeds 6:1 for this system, and may be higher pending the production strategy used for making hydrogen. The use of this process could double the amount of energy available as liquid fuel versus what can be made by yeast to make ethanol.
Publications
- Type:
Journal Articles
Status:
Published
Year Published:
2015
Citation:
Chen, R.; Rojas-Downing, M.M.; Zhong, Y.; Saffron, C.M.; Liao, W. Life cycle and economic assessment of anaerobic co-digestion of dairy manure and food waste. Industrial Biotechnology. 2015. 11(2): 127-139.
- Type:
Journal Articles
Status:
Published
Year Published:
2015
Citation:
Kelkar, S.; Saffron, C.M.; Andreassi, K.; Li, Z.; Murkute, A.; Miller, D.J.; Pinnavaia, T.J.; Kriegel, R.M. "A survey of catalysts for aromatics from fast pyrolysis of biomass." Applied Catalysis B: Environmental. 2015. 174. 85-95.
- Type:
Journal Articles
Status:
Published
Year Published:
2015
Citation:
Lam, C.H.; Lowe, C.B.; Li, Z.; Longe, K.N.; Rayburn, J.T.; Caldwell, M.A.; Houdek, C.E.; Maguire, J.B.; Saffron, C.M.; Miller, D.J.; Jackson, J.E. Electrocatalytic upgrading of model lignin monomers with Earth abundant metal electrodes. Green Chemistry. 2015. 17. 601-609.
- Type:
Journal Articles
Status:
Published
Year Published:
2015
Citation:
Okoroigwe, E.; Li, Z.; Kelkar, S.; Saffron, C.M.; Onyegegbu, S. Bio-oil yield potential of some tropical woody biomass. Journal of Energy in Southern Africa. 2015. 26(2): 33-41.
- Type:
Journal Articles
Status:
Published
Year Published:
2015
Citation:
Kelkar, S.; Saffron, C.M.; Chai, L; Bovee, J.; Stuecken, T.; Garedew, M.; Li, Z.; Kriegel, R.M. Pyrolysis of spent coffee grounds using a screw-conveyor reactor. Fuel Processing Technology. 2015. 137. 170-178.
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Progress 01/01/14 to 09/30/14
Outputs
Target Audience: The production of liquid fuels via fast pyrolysis and electrocatalysis was targeted to research scientists, industrial partners and 4H student groups that visited Michigan State University. Presentations were given at the Great Lakes Bioenergy Research Center’s annual retreat, at the American Society of Agricultural and Biological Engineering Annual Conference and at the Thermochemical Sciences Symposium. 4H studentsare routinelyengaged during a summer program in which they visit campus to learn about the methods used to convert biomass into fuels via thermal processes. Changes/Problems:
Nothing Reported
What opportunities for training and professional development has the project provided? Four senior design students selected torrefaction as a means of creating renewable electrical power for MSU’s power plant. These students operated a pilot-scale reactor to produce torrefied wood and constructed a briquetting system. A process model was formulated by these students to compute the cost contribution to electrical power generation. Finally, their results were discussed in an oral presentation given at BE Showcase and in a written report. One graduate student was advised to investigate the use of electrocatalysis to transform lignin model compounds to chemically reduced forms such as cyclohexanol. This student learned to construct and operate a divided voltaic cell for reducing such compounds as phenol, guaiacol and syringol. Her work was presented as a poster at the Great Lakes Bioenergy Research Center retreat and at the ASABE conference in Montreal. How have the results been disseminated to communities of interest? Research results were disseminated to the scientific community at the ASABE Annual Meeting in Montreal and again at the TCS Symposium in Denver. Two posters and two oral presentations were given at the ASABE annual meeting, while a presentation and poster were given at the TCS Symposium. Four journal articles were also published in 2014 to further information dissemination to the scientific community. What do you plan to do during the next reporting period to accomplish the goals? Developing torrefied biomass pellets or briquettes that are stable during water immersion is the next phase of my research regarding solid fuel production. Different feedstocks, operating conditions, densification conditions and the use of binding agents will be explored to create stable, fungible solid fuels from biomass. Surface characterization will also be pursued to better understand why water infiltrates what should be a hydrophobic material. Further electrocatalysis of model compounds and real lignin dimers will proceed to quantify product yields and energy input. This work will be extended to real lignin samples with the goal of converting lignin into higher-value fuels and chemical products. An economic model will be developed to estimate the costs associated with lignin valorization using this approach.
Impacts
What was accomplished under these goals?
Accomplishments are listed by objective below. Briefly, the Saffron lab’s solid fuel research centers on developing a water resistant briquette or pellet. Hydrophobicity, energy density and grindability of the torrefied material are key properties that must meet benchmarks before adoption of this renewable option will become widespread. In addition to solid fuels, liquid fuel from biomass, using pyrolysis and electrocatalysis, is being investigated that could supply renewable feedstock to America’s petroleum refineries. Electrocatalysis is used to saturate carbon-carbon and carbon-oxygen double bonds using electricity from wind and solar energy sources. Solid fuel creation by biomass torrefaction: 1. Survey biomass varieties (esp. forest biomass) and torrefaction operating conditions (temperature, residence time) to provide guidance for a nascent solid fuels industry A sample of mixed hardwoods was characterized prior to torrefaction in MSU’s kilogram-scale torrefier. This sample was provided by Heat Transfer International, a company with interest in thermal conversion. A temperature of 263°C and a residence time of 10 minutes were found to optimize the energy yield of torrefaction, a value that is within the range provided in the literature. 2. Develop techniques to assess fuel properties such as grindability, dust formation and hydrophobicity that along with existing methods for higher heating value, bulk density and ultimate analysis will be used for comparison with coal Higher heating value, bulk density and ultimate analysis are supported by the Saffron lab or other labs funded by AgBioResearch at MSU. Funds to purchase a HGI (Hardgrove Grindability Index) mill have been allotted to PI Saffron and the capability to assess grindability will be an expertise that Saffron’s lab can provide. Water droplet and immersion assays are being developed to assess hydrophobicity of torrefied wood briquettes and pellets. 3. Formulate a systems model to assess the economics and environmental impacts of decentralized torrefaction and densification on centralized electrical power generation The systems model for describing torrefaction is well underway in its development. An energy balance, starting from cultivation and ending after combustion at a power plant, has been constructed. Verification of this balance is currently being performed, and early predictions of the renewable energy return on fossil energy invested exceed 6:1. Liquid fuel creation by biomass pyrolysis: 4. Survey biomass varieties and pyrolysis operating conditions to determine plant species and process parameters that yield favorable bio-oil characteristics and system economics The Saffron group published a journal article in Biomass and Bioenergy that correlated feedstock and product properties using principal component analysis. Of the species sampled, pyrolysis products did not seem to align with taxonomic relatedness for the eight plant varieties considered. 5. Investigate ECH as a means of stabilizing model compounds and raw bio-oil and develop methods for characterizing the complex bio-oil intermediate Much work has been accomplished in this regard during the previous year. Electrocatalytic hydrogenation was shown to reduce such monoaromatic molecules as phenol, guaiacol and syringol. Phenolic dimers, such as 4-phenoxyphenol, were also cleaved to ultimately form cyclohexanol. This cleavage bodes well for cleaving lignin dimers that are the products of fast pyrolysis. 6. Assess hydroprocessing as a means of upgrading stabilized bio-oil to hydrocarbon fuels Nothing to report. 7. Formulate a systems model to assess the economics and environmental impacts of decentralized pyrolysis and ECH on liquid fuel supply chains through centralized hydroprocessing A mass and energy balance model has been devised to describe biomass conversion into liquid fuels using decentralized pyrolysis and electrocatalysis followed by centralized refinement into hydrocarbons. The renewable energy return on fossil energy invested exceeds 6:1 for this system, and may be higher pending the production strategy used for making hydrogen.
Publications
- Type:
Journal Articles
Status:
Published
Year Published:
2014
Citation:
Kelkar, S.; Li, Z.; Bovee, J.; Thelen, K.D.; Kriegel, R.; Saffron, C.M. Pyrolysis of North-American grass species: Effect of feedstock composition and taxonomy on pyrolysis products. Biomass and Bioenergy. 2014. 64. 152-161.
- Type:
Journal Articles
Status:
Published
Year Published:
2014
Citation:
Okoroigwe, E.C.; Saffron, C.M.; Kamdem, P.D. Characterization of palm kernel shell for materials reinforcement and water treatment. Journal of Chemical Engineering and Materials Science. 2014. 5(1). 1-6.
- Type:
Journal Articles
Status:
Published
Year Published:
2014
Citation:
Kelkar, S.; Saffron, C.M.; Li, Z.; Kim, S.-S.; Pinnavaia, T.J.; Miller, D.J.; Kriegel, R. Aromatics from biomass pyrolysis vapour using a bifunctional mesoporous catalyst. Green Chemistry. 2014. 16. 803-812.
- Type:
Journal Articles
Status:
Published
Year Published:
2014
Citation:
Li, Z.; Kelkar, S.; Raycraft, L.; Garedew, M.; Jackson, J.E.; Miller, D.J.; Saffron, C.M. A mild approach for bio-oil stabilization and upgrading: electrocatalytic hydrogenation using ruthenium supported on activated carbon cloth. Green Chemistry. 2014. 16, 844-852.
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