Progress 12/01/08 to 11/30/13
Outputs
Target Audience: For solid fuels from plant biomass, Michigan power companies, small and large equipment manufacturers and biomass suppliers were targeted for interest in the torrefaction work group. Torrefaction mass and energy yields as well as preliminary process and systems economics were disseminated to the group. As much as possible, information regarding the thermochemical conversion of biomass was provided to diverse audiences, student groups, business leaders and academic peers. Several presentations regarding biomass-to-liquid fuels were given at local and national conferences to audiences comprised of chemical companies, petroleum companies and general attendees. During the reporting period, fast pyrolysis to produce bio-oil that is stabilized by electrocatalysis within regional processing depots was introduced as a bioenergy system. The broad use of thermochemical approaches for bioenergy production was also shared with 4H students and high school students from disadvantaged urban areas. A new bioenergy curriculum, comprised of three new courses, was developed at Michigan State University (MSU). CSS 467, “Biomass Feedstock Production,” is jointly taught by the Department of Plant, Soil and Microbial Sciences, the Department of Forestry and the Department of Biosystems Engineering at MSU. Agronomic and forestry cultivation and harvesting practices are thoroughly described in this course. CHE 468, “Biomass Conversion Engineering,” introduces students to such subjects as enzymatic hydrolysis, fermentation and gasification. This course is administered by the Department of Chemical Engineering and the Department of Biosystems Engineering. BE 469, “Sustainable Bioenergy Systems” is also administered by Biosystems Engineering and Chemical Engineering departments. BE 469 is a capstone course in which students perform system-wide economic analyses and life cycle assessments for selected biomass varieties and conversion processes. Students present their progress every two weeks and provide midterm and final project reports. A total of 36 students were enrolled in the Spring 2013 offering of BE 469, evidence that the bioenergy curriculum has garnered stakeholder interest. Changes/Problems:
Nothing Reported
What opportunities for training and professional development has the project provided? A new bioenergy curriculum, comprised of three new courses, was developed at Michigan State University (MSU). CSS 467, “Biomass Feedstock Production,” is jointly taught by the Department of Plant, Soil and Microbial Sciences, the Department of Forestry and the Department of Biosystems Engineering at MSU. Agronomic and forestry cultivation and harvesting practices are thoroughly described in this course. CHE 468, “Biomass Conversion Engineering,” introduces students to such subjects as enzymatic hydrolysis, fermentation and gasification. This course is administered by the Department of Chemical Engineering and the Department of Biosystems Engineering. BE 469, “Sustainable Bioenergy Systems” is also administered by Biosystems Engineering and Chemical Engineering departments. BE 469 is a capstone course in which students perform system-wide economic analyses and life cycle assessments for selected biomass varieties and conversion processes. Students present their progress every two weeks and provide midterm and final project reports. A total of 36 students were enrolled in the Spring 2013 offering of BE 469, evidence that the bioenergy curriculum has garnered stakeholder interest. Further,oneMaster's student andtwo Doctoral studentshave received their degrees during this period.Each student was trained to work in both dry and wet labs using such techniques as: GC/MS, LC/MS, thermogravimetric analysis, Karl-Fischer titration, bomb calorimetry and scanning electron microscopy, X-ray photoelectron spectroscopy and X-ray diffraction. Further, students were trained to use a kilogram per hour pyrolysis reactor for producing bio-oil, biochar and combustible gas. How have the results been disseminated to communities of interest? Results have been disseminated through publication of journal articles, conference presentations, presentations to local and state stakeholders, and lectures to 4H and high school students. Dr. Saffron’s work is exhibited on the Department of Biosystems Engineering’s website. Recently, he discussed torrefaction to produce solid fuels on Fox 47 News, a televised news source. What do you plan to do during the next reporting period to accomplish the goals?
Nothing Reported
Impacts
What was accomplished under these goals?
Objective 1. Investigate, by experiment, the importance of mass and heat transport versus chemical kinetics in defining the rate and extent of fast pyrolysis of biomass. A lab containing the tools necessary to understand the mechanisms occurring in pyrolysis has been equipped. Currently this lab has a CDS Analytical Pyroprobe connected to a GC/MS, a LC/MS, a thermogravimetric analyzer with differential scanning calorimetry and a kilogram-scale screw conveyor pyrolysis reactor. The screw-conveyor reactor has been optimized for bio-oil production for poplar DN34 and a proprietary processing waste stream. Though a rate model for describing conversion in the MSU screw conveyor reactor has not yet been formulated, models by Di Blasi et al. and Babu et al. have been extensively reviewed. Future work will be proceed to model pyrolysis in terms of the fundamental mechanisms that control product distribution. Objective 2. Investigate, by experiment, the effect of various reducing gases on the yield and composition of bio-oil produced by the fast pyrolysis of biomass. The use of methane gas was investigated as a source of reducing equivalents due to the abundance of domestic natural gas. Unfortunately, the results of methane activation during preliminary catalysis trials were not encouraging. Methane addition to benzaldehyde was found not to occur in significant amounts over several trial catalysts. For this reason, the use of methane as a reducing gas has been temporarily discontinued. An attempt will be made to publish the unsuccessful results of these trials. Objective 3. Investigate, by experiment, the reaction pathways that define the co- or downstream catalysis of pyrolysis gas formed in an atmosphere of reducing gas. Instead of the use of methane as a reducing gas, the catalytic cracking of pyrolysis gas over HZSM5 catalyst was examined. As expected, aromatic and alkane hydrocarbon yields increased when HZSM5 was used as a shape selective catalyst. Yields were further improved by adjusting its aluminum to silicon ratio and through addition of mesopores into the catalyst matrix. An article was recently accepted by the journal “Green Chemistry” describing the use of this catalyst to upgrade the products of biomass pyrolysis. Objective 4. Formulate a scale-up criterion upon demonstrating the fast pyrolysis process at the large bench scale. As of yet, no simple scale-up criterion has been devised, though scaling in a screw-conveyor reactor will be limited by heat transfer from the outer wall through the reactor annulus. This may limit the flow rate that can be achieved in a screw-conveyor, or extruder, type of pyrolysis reactor. For this reason, it is likely that pyrolysis by this method might only be supported in small-scale, regional pyrolysis depots. After completion of the mathematical model detailed by Objective 1, the search for a scaling criterion will continue. Objective 5. Construct economic models of the pyrolysis process using combinations of reducing gas and pyrolysis as demonstrated in Objectives 1 through 4. An economic model to describe pyrolysis, in tandem with electrocatalysis and hydroprocessing is currently well underway. A model for pyrolysis followed by solid catalysis has also been derived, though results from this model are more likely to support green plastic production than liquid fuels. Hydrocarbon fuels at less than $3.00 per gallon will be competitive with gasoline in today’s market. Currently, an extensive study of hydroprocessing strategies is underway and a process model for fuel finishing is being constructed.
Publications
- Type:
Journal Articles
Status:
Published
Year Published:
2013
Citation:
1. Stoklosa, R.J.; Velez, J.; Kelkar, S.; Saffron, C.M.; Thies, M.C.; Hodge, D.B. Correlating Lignin Structural Features to Phase Partitioning Behavior in a Novel Aqueous Fractionation of Softwood Kraft Black Liquor. Green Chemistry. 2013. In press.
- Type:
Journal Articles
Status:
Published
Year Published:
2012
Citation:
2. Li, Z.; Garedew, M.; Lam, C.H.; Jackson, J.E.; Miller, D.J.; Saffron, C.M. Mild electrocatalytic hydrogenation and hydrodeoxygenation of bio-oil derived phenolic compounds using ruthenium Supported on activated carbon cloth Green Chemistry. 2012. 14, 2540-2549.
http://pubs.rsc.org.proxy2.cl.msu.edu/en/content/articlepdf/2012/gc/c2gc35552c?page=search
- Type:
Journal Articles
Status:
Published
Year Published:
2012
Citation:
3. Li, Z.; Kelkar, S.; Lam, C.H.; Luczek, K.; Jackson, J.E.; Miller, D.J.; Saffron, C.M. Aqueous electrocatalytic hydrogenation of furfural to furfuryl alcohol and 2-methylfuran using a sacrificial anode. Electrochimica Acta. 2012. 64, 87-93.
http://ac.els-cdn.com/S0013468611019438/1-s2.0-S0013468611019438-main.pdf?_tid=afbb8b1efda1b2c4cdf47df11fbaa8b8&acdnat=1338251470_239fccad1d6d922e33fdbf9fad073281
- Type:
Journal Articles
Status:
Published
Year Published:
2012
Citation:
4. Thelen, K.D.; Gao, J.; Hoben, J.; Qian, L.; Saffron, C.M.; Withers, K. A spreadsheet-based model for teaching the agronomic, economic and environmental aspects of bioenergy cropping systems. Computers and Electronics in Agriculture. 2012. 85, 157-163.
http://ac.els-cdn.com/S0168169912001093/1-s2.0-S0168169912001093-main.pdf?_tid=7d1e7537b84a0628964eb91451c38a36&acdnat=1338559862_f808457763ae5ed2e494f007fd2050a5
- Type:
Journal Articles
Status:
Published
Year Published:
2012
Citation:
5. Okoroigwe, E.C.; Li, Z.; Onyegegbu, S.O.; Saffron, C.M. Maximizing the energy potential of palm kernel shell by pyrolytic conversion to biofuel. Proceedings of the Fourth International Renewable Energy Congress. Peer reviewed. 2012.
http://www.irec.cmerp.net/files/Proceedings.pdf
6. Okoroigwe, E.C.; Saffron, C.M. Determination of the bioenergy potential of palm kernel shell by physicochemical characterization. Nigerian Journal of Technology. 2012. 31, 329-335.
http://www.nijotech.com/index.php/nijotech/article/view/561/513#
7. Okoroigwe, E.; Li, Z.; Stuecken, T.; Saffron, C.M.; Onyegegbu, S. Pyrolysis of Gmelina arborea wood for bio-oil/biochar production: Physical and chemical characterization of the products. Journal of Applied Sciences. 2012. 12(4), 369-374.
http://scialert.net/qredirect.php?doi=jas.2012.369.374&linkid=pdf
8. Li, M.; Foster, C.; Kelkar, S.; Pu, Y.; Holmes, D.; Ragauskas, A.; Saffron, C.M.; Hodge, D.B. Structural characterization of alkaline hydrogen peroxide pretreated grasses exhibiting diverse lignin phenotypes. Biotechnology for Biofuels. 2012. 5(38).
http://www.biotechnologyforbiofuels.com/content/pdf/1754-6834-5-38.pdf
9. Leistritz, F.L.; Hodur, N.M.; Senechal, D.M.; Stowers, M.D.; McCalla, D.; and Saffron, C.M. Use of agricultural residue feedstock in North Dakota biorefineries. Journal of Agribusiness. 2009, 27, 17-32.
http://ageconsearch.umn.edu/bitstream/90655/2/JAB%2cSpr-Fall09%2c%2302%2cpp17-32.pdf
10. Safferman, S.; Liao, W.; and Saffron, C.M. Engineering the bioeconomy. Journal of Environmental Engineering-ASCE. 2009, 135, 1085.
http://scitation.aip.org.proxy2.cl.msu.edu/getpdf/servlet/GetPDFServlet?filetype=pdf&id=JOEEDU000135000011001085000001&idtype=cvips&prog=normal
- Type:
Journal Articles
Status:
Published
Year Published:
2012
Citation:
6. Okoroigwe, E.C.; Saffron, C.M. Determination of the bioenergy potential of palm kernel shell by physicochemical characterization. Nigerian Journal of Technology. 2012. 31, 329-335.
http://www.nijotech.com/index.php/nijotech/article/view/561/513#
- Type:
Journal Articles
Status:
Published
Year Published:
2012
Citation:
7. Okoroigwe, E.; Li, Z.; Stuecken, T.; Saffron, C.M.; Onyegegbu, S. Pyrolysis of Gmelina arborea wood for bio-oil/biochar production: Physical and chemical characterization of the products. Journal of Applied Sciences. 2012. 12(4), 369-374.
http://scialert.net/qredirect.php?doi=jas.2012.369.374&linkid=pdf
- Type:
Journal Articles
Status:
Published
Year Published:
2012
Citation:
8. Li, M.; Foster, C.; Kelkar, S.; Pu, Y.; Holmes, D.; Ragauskas, A.; Saffron, C.M.; Hodge, D.B. Structural characterization of alkaline hydrogen peroxide pretreated grasses exhibiting diverse lignin phenotypes. Biotechnology for Biofuels. 2012. 5(38).
http://www.biotechnologyforbiofuels.com/content/pdf/1754-6834-5-38.pdf
- Type:
Journal Articles
Status:
Published
Year Published:
2009
Citation:
9. Leistritz, F.L.; Hodur, N.M.; Senechal, D.M.; Stowers, M.D.; McCalla, D.; and Saffron, C.M. Use of agricultural residue feedstock in North Dakota biorefineries. Journal of Agribusiness. 2009, 27, 17-32.
http://ageconsearch.umn.edu/bitstream/90655/2/JAB%2cSpr-Fall09%2c%2302%2cpp17-32.pdf
- Type:
Journal Articles
Status:
Published
Year Published:
2009
Citation:
10. Safferman, S.; Liao, W.; and Saffron, C.M. Engineering the bioeconomy. Journal of Environmental Engineering-ASCE. 2009, 135, 1085.
http://scitation.aip.org.proxy2.cl.msu.edu/getpdf/servlet/GetPDFServlet?filetype=pdf&id=JOEEDU000135000011001085000001&idtype=cvips&prog=normal
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Progress 01/01/12 to 12/31/12
Outputs
OUTPUTS: The 2012 reporting period is the fifth full year of this project titled, "Thermochemical Conversion of Woody Biomass to Fuels and Chemicals." As with previous years, biomass fast pyrolysis, bio-oil upgrading and torrefaction were the focus of research and development. Biomass fast pyrolysis involves the heating of plant biomass in the absence of oxygen at short vapor residence times and temperatures between 400C and 600C. Torrefaction occurs at lower temperatures, 200C to 400C and longer residence times. Both forest and agricultural biomass varieties were considered as feedstocks for thermal conversion. At the pilot scale, several different biomass feedstocks were pyrolyzed using a screw-conveyor reactor at Michigan State University, including poplar and a waste product from an industrial partner. Bio-oil yields in excess of 60% along with biochar yields of 20% were observed on a mass basis. Higher bio-oil yields were achieved in 2012 than in 2011 because an electrostatic precipitator that was placed in line with the non-condensed gas to collect bio-oil aerosols. A flame calorimeter that followed the electrostatic precipitator determined that approximately 50% of the energy needed to perform pyrolysis can be recovered from the non-condensed gas. At the analytical scale, a pyroprobe in tandem with gas chromatography-mass spectrometry continues to be used to characterize the product distribution after pyrolysis using only milligram quantities of biomass. The composition of the pyrolysis gas in the products has been related to the composition of the feedstock using multivariate analysis, an approach that has significant ramifications for feedstock selection. A statistical correlation analysis was used to relate the feedstock composition to the product composition. The use of electrocatalysis as a method for stabilizing the bio-oil product of pyrolysis was examined in 2012. Electrocatalysis uses electricity from the local power grid to reduce the reactivity and corrosiveness of bio-oil so that it can be transported in metal tanks and pipes to petroleum refineries for further upgrading. Pyrolysis followed by electrocatalysis is a novel coupling of these technologies that may enable the decentralization of future bioenergy systems. PARTICIPANTS: During this reporting period, my student Mr. Zhenglong Li received his Ph.D. regarding the use of electrocatalysis to stabilize bio-oil. Mr. Jon Bovee has been assessing different native grass feedstocks for bioenergy potential via pyrolysis. Mr. Shantanu Kelkar has been developing catalysts for valuable products formation. Ms. Mahlet Garedew has been developing a new methodology for mapping the reaction pathways of pyrolysis. TARGET AUDIENCES: Industrial collaborations involving biomass thermochemical conversion have been pursued. Continued outreach to communities and engagement with industry will proceed in 2013. PROJECT MODIFICATIONS: Nothing significant to report during this reporting period.
Impacts
The overall impact of this research program is to displace fossil sources of energy and chemicals with renewable sources. The production of hydrocarbon liquid fuels requires a carbonaceous feedstock. Terrestrial plants, such as grasses and trees, offer a substrate for conversion by pyrolysis to liquids, and ultimately hydrocarbon fuels upon catalytic upgrading. During 2012, the use of terrestrial plants was examined for liquid fuel production at two scales, the analytical scale using milligram quantities of biomass and the pilot scale using kilogram quantities. As bio-oil is reactively unstable, progress was made in bio-oil upgrading using approaches that are not dependent upon gaseous sources of molecular hydrogen, but instead use electricity such as electrocatalysis. Additionally, several Midwestern grass varieties were analyzed by the py-GC/MS system and the results were compared to biomass composition using multivariate analysis. These results will facilitate the selection of plant species for conversion into liquid fuels. In addition to outcomes generated at the analytical-scale, significant results were obtained from a pilot-scale screw-conveyor reactor. A waste material from an industrial partner was found capable of producing bio-oil yields greater than 60% when our electrostatic precipitator was used to collect aerosols. Further investigation of poplar pyrolysis (additional clones), native grass varieties, and corn stover are planned for 2013. Seven different presentations were given at conferences and in front of community groups in 2012. The first titled, "Torrefaction of Poplar and Short-rotation Coppiced Willow," was presented as the Hanover seminar in Forestry at Michigan State University. A second presentation titled, "Fundamentals of Torrefaction" was given at the Agriculture and Agribusiness Institute in front of Extension educators. A third presentation titled, "Value Addition to Local Biomass Processing Depots by Upgrading e-AFEX Lignin Using Pyrolysis and Electrocatalysis," was presented at the Great Lakes Bioenergy Research Center's annual retreat. A fourth presentation titled, "Thermochemical Conversion of Biomass" was given to summer students from urban schools at an event sponsored by Michigan State's Diversity Programs Office. This same presentation was given to a group of students at a 4H event on Michigan State's campus. A fifth presentation titled, "Biomass Thermochemical Conversion R&D Efforts at MSU" was presented at Aston University in England. A sixth presentation titled, "Pyrolysis of North-American Grass Species: Effect of Feedstock Composition and Location" was provided at the SunGrant Conference in New Orleans. Finally, a seventh presentation was given at the United Nations 67th Anniversary Commemoration titled "Thermochemical Processes for Biomass Conversion to Bioenergy." This last presentation was read by Prof. Ajit Srivastava. As much as possible, information regarding the thermochemical conversion of biomass was provided to diverse audiences, student groups, business leaders and academic peers.
Publications
- Li, Z.; Garedew, M.; Lam, C.H.; Jackson, J.E.; Miller, D.J.; Saffron, C.M. "Mild Electrocatalytic Hydrogenation and Hydrodeoxygenation of Bio-oil Derived Phenolic Compounds using Ruthenium Supported on Activated Carbon Cloth" Green Chemistry. 2012. 14, 2540-2549.
- Li, Z.; Kelkar, S.; Lam, C.H.; Luczek, K.; Jackson, J.E.; Miller, D.J.; Saffron, C.M. "Aqueous electrocatalytic hydrogenation of furfural to furfuryl alcohol and 2-methylfuran using a sacrificial anode." Electrochimica Acta. 2012. 64, 87-93.
- Thelen, K.D.; Gao, J.; Hoben, J.; Qian, L.; Saffron, C.M.; Withers, K. "A spreadsheet-based model for teaching the agronomic, economic and environmental aspects of bioenergy cropping systems." Computers and Electronics in Agriculture. 2012. 85, 157-163.
- Okoroigwe, E.; Li, Z.; Stuecken, T.; Saffron, C.M.; Onyegegbu, S. "Pyrolysis of Gmelina arborea wood for bio-oil/biochar production: Physical and chemical characterization of the products." Journal of Applied Sciences. 2012. 12(4), 369-374.
- Li, M.; Foster, C.; Kelkar, S.; Pu, Y.; Holmes, D.; Ragauskas, A.; Saffron, C.M.; Hodge, D.B. "Structural characterization of alkaline hydrogen peroxide pretreated grasses exhibiting diverse lignin phenotypes." Biotechnology for Biofuels. 2012. Accepted for publication in January of 2012. 5(38).
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Progress 01/01/11 to 12/31/11
Outputs
OUTPUTS: The 2011 reporting period is the fourth full year of this project titled, "Thermochemical Conversion of Woody Biomass to Fuels and Chemicals." During this year, biomass fast pyrolysis and torrefaction were the focus of research and development. Biomass fast pyrolysis involves the heating of plant biomass in the absence of oxygen at short vapor residence times and temperatures between 400C and 600C. Torrefaction occurs at lower temperatures, 200C to 400C and longer residence times. Both forest and agricultural biomass varieties were considered as feedstocks for thermal conversion. At the pilot scale, poplar was pyrolyzed using a screw-conveyor reactor at Michigan State University. Bio-oil yields in excess of 55% along with biochar yields of 20% were observed on a mass basis. Higher bio-oil yields are expected after an electrostatic precipitator is placed in line with the non-condensed gas to collect bio-oil aerosols. A flame calorimeter was constructed in 2011 to measure the energy content of the non-condensed gas from pyrolysis and a full energy balance with this reactor system is expected in 2012. At the analytical scale, a pyroprobe in tandem with gas chromatography-mass spectrometry has been used to characterize the product distribution after pyrolysis using only milligram quantities of biomass. The composition of the pyrolysis gas in the products has been related to the composition of the feedstock using multivariate analysis, an approach that has significant ramifications for feedstock selection. In addition to pyrolysis, hypothetical supply chains based on poplar or willow grown in plantation were examined when torrefaction was implemented at decentralized regional centers to produce feedstock for electrical power generation. These results have been compiled for the Department of Energy in a report titled, "Forestry Biofuel Statewide Collaboration Center: Task B2. Analyze the Economic and Logistics Performances of Woody Biomass Harvesting, Forwarding, and Processing Systems from Natural Forest Stands and Energy Plantations in Michigan." PARTICIPANTS: Nothing significant to report during this reporting period. TARGET AUDIENCES: Industrial collaborations involving biomass thermochemical conversion have been pursued. Continued outreach to communities and engagement with industry will proceed in 2012. PROJECT MODIFICATIONS: Nothing significant to report during this reporting period.
Impacts
The overall impact of this research program is to displace fossil sources of energy and chemicals with renewable sources. The production of hydrocarbon liquid fuels requires a carbonaceous feedstock. Terrestrial plants, such as grasses and trees, offer a substrate for conversion by pyrolysis to liquids, and ultimately hydrocarbon fuels upon catalytic upgrading. During 2011, the use of terrestrial plants was examined for liquid fuel production at two scales, the analytical scale using milligram quantities of biomass and the pilot scale using kilogram quantities. As bio-oil is reactively unstable, progress was made in bio-oil upgrading using approaches that are not dependent upon gaseous sources of molecular hydrogen. Additionally, several Midwestern grass varieties were analyzed by the py-GC/MS system and the results were compared to biomass composition using multivariate analysis. These results will facilitate the selection of plant species for conversion into liquid fuels. In addition to outcomes generated at the analytical-scale, significant results were obtained from a pilot-scale screw-conveyor reactor. Poplar DN34 was investigated for its potential to produce bio-oil and biochar. Poplar was identified in the Billion-ton Study Update as a significant plantation crop. Bio-oil yields in excess of 55% were obtained without the use of an electrostatic precipitator to collect aerosols. Further investigation of poplar pyrolysis with an in-line electrostatic precipitator is planned for 2012. Two presentations were given at conferences in 2011. The first titled, "Thermochemical Conversion of Palm Kernel Shell (PKS) to Bio-energy," was presented at American Society of Mechanical Engineers 5th International Conference on Energy Sustainability and 9th Fuel Cell Science, Engineering and Technology Conference in Washington D.C. The second titled, "Aqueous Phase Hydrogenation and Hydrodeoxygenation of Bio-Oil Model Compounds Under Mild Temperature and Pressure" was presented at the AICHE Annual meeting in Minneapolis.
Publications
- A report was compiled for the Department of Energy that contained a subsection describing the regional deployment of torrefaction. The report is titled, "Forestry Biofuel Statewide Collaboration Center: Task B2. Analyze the Economic and Logistics Performances of Woody Biomass Harvesting, Forwarding, and Processing Systems from Natural Forest Stands and Energy Plantations in Michigan." This report will be publicly available in 2012.
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Progress 01/01/10 to 12/31/10
Outputs
OUTPUTS: The 2010 reporting period is the third full year of this project titled, "Thermochemical Conversion of Woody Biomass to Fuels and Chemicals." Of the thermochemical conversion technologies, gasification, torrefaction and pyrolysis, biomass fast pyrolysis was the focus of research. Biomass fast pyrolysis involves the heating of plant biomass in the absence of oxygen at short vapor residence times and temperatures between 400C and 600C. Forest and agricultural biomass varieties were considered as feedstocks for thermal conversion. Forest feedstocks native to Michigan as well as those native to equatorial regions, especially Nigeria, were assessed during 2010. Agricultural feedstocks, primarily grass species native to the Midwest, were also considered as sources of carbon for biofuels production. Both agricultural and forest feedstocks were examined at two process scales to gain an understanding of how different mechanisms are functions of reactor size. At the analytical scale, a pyroprobe in tandem with gas chromatography-mass spectrometry has been used to characterize the product distribution after pyrolysis using only milligram quantities of biomass. A new methodology for assessing catalyst activity and deactivation kinetics was developed to screen catalyst-biomass combinations. Several strong acid catalysts have shown potential for upgrading pyrolysis products to fuels and chemicals. At the pilot scale, several biomass varieties from Nigeria were converted in a screw-conveyor reactor into bio-oil, bio-char and combustible gas. These generalized products were characterized by bomb calorimetry, py-GC/MS and ultimate analysis. New stabilization strategies, that do not require the production of molecular hydrogen, are being investigated for producing a drop-in replacement for crude oil within the existing petroleum industry. The vision for these strategies includes eventual deployment in farm or forest cooperatives that will densify biomass all the while creating jobs in rural communities. As for information dissemination, five presentations and five posters were given at meetings, conferences, and invited lectures during 2010. Three presentations focused on biomass fast pyrolysis, while two described additional thermal approaches known as torrefaction and gasification. PARTICIPANTS: Nothing significant to report during this reporting period. TARGET AUDIENCES: Industrial collaborations involving biomass thermochemical conversion have been pursued. Continued outreach to communities and engagement with industry will proceed in 2011. PROJECT MODIFICATIONS: Nothing significant to report during this reporting period.
Impacts
The overall impact of this research program is to displace fossil sources of energy and chemicals with renewable sources. The production of hydrocarbon liquid fuels requires a carbonaceous feedstock. Terrestrial plants, such as grasses and trees, offer a substrate for conversion by pyrolysis to liquids, and ultimately hydrocarbon fuels upon catalytic upgrading. During 2010, the use of terrestrial plants was examined for liquid fuel production at two scales, the analytical scale using milligram quantities of biomass and the pilot scale using kilogram quantities. At the analytical-scale, a pyroprobe in tandem with a GC/MS (py-GC/MS) has been used to assess catalyst activities for various biomass-catalyst combinations. Several biomass-catalyst combinations have shown potential for liquid fuel production, though carbonaceous coke formation is significant. Coke formation leads to catalyst encapsulation and ultimately deactivation. Mechanisms of pyrolysis are also being investigated at the analytical scale to enhance existing models to more accurately describe pyrolysis. Several Midwestern grass varieties were analyzed by the py-GC/MS system and the pyrograms were compared using multivariate analysis. It was determined that less than ten analytical peak responses were needed to describe much of the variability in pyrolysis products between eight different Midwestern grass species. This result will facilitate the improvement of existing pyrolysis models which tend toward generalized reaction schemes. In addition to outcomes generated at the analytical-scale, significant results were obtained from a pilot-scale screw-conveyor reactor. Eight different Nigerian biomass varieties were converted to bio-oil and bio-char to gather mass and energy balance information. Bio-oil yields as high as 71% (mass basis) were measured during these trials. Additionally, several equatorial biomass varieties exhibited promising heating values upon bomb calorimetry, a result which will benefit rural energy production in economically challenged regions. Several presentations and posters were provided at conferences, meetings and invited lectures. A presentation and two posters were given at the Thermal and Catalytic Sciences Conference at Iowa State University in September of 2010. Presentations were also given at the Great Lakes Bioenergy Research Center Annual Retreat in South Bend, IN; the Northeast Region SunGrant Initiative Annual Meeting in Syracuse, NY; and the Waste to Energy Summit in East Lansing, MI.
Publications
- Leistritz F.L.; Hodur N.M.; Senechal D.M.; Stowers M.D.; McCalla, D.; Saffron C.M. "Use of agricultural residue feedstock in North Dakota biorefineries." Journal of Agribusiness. 2009. 27, 17-32.
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Progress 01/01/09 to 12/31/09
Outputs
OUTPUTS: The 2009 reporting period is the second full year of this project titled, "Thermochemical Conversion of Woody Biomass to Fuels and Chemicals." During 2009, a small pilot-scale pyrolysis reactor was made operational and the chemical composition of the resulting product liquid has been characterized. A screw-conveyor reactor was designed as a study reactor to investigate the governing mechanisms of pyrolysis. Reactors of this type may also be deployable in regional biomass processing centers located near to biomass collection. Both mixed-wood sawdust and switchgrass have been processed by this reactor during the reporting period. Reactor modifications are being made to improve biomass feed characteristics and char collection as intermittent flow and char blockage currently limit operation. In addition to pilot-scale pyrolysis, analytical-scale pyrolysis has been used to examine the potential of various biomass feedstocks for producing fuels and chemicals. Milligram quantities of biomass have been pyrolyzed in a CDS Analytical Pyroprobe that is connected in series to a gas chromatograph-mass spectrometer. Hundreds of compounds have been identified in the pyrolysis gas, including: aldehydes, furans, ketones, organic acids, and phenolics. Solid catalysts have been screened along with biomass varieties using analytical pyrolysis to measure the potential for converting the oxygenated organic compounds in pyrolysis gas to compounds with reduced oxygen content. Modifications of this analytical approach are proceeding to develop a method with improved scalability. Information about biomass conversion using pyrolysis was reported in a presentation given at the Michigan Agri-Energy Conference titled, "Biomass Fast Pyrolysis." PARTICIPANTS: Christopher M. Saffron, PI Shantanu Kelkar, Doctoral Student Zhenglong Li, Doctoral Student TARGET AUDIENCES: Industrial collaborations involving biomass thermochemical conversion have been pursued. Continued outreach to communities and engagement with industry will proceed in 2010. PROJECT MODIFICATIONS: No project modifications to report during this period.
Impacts
The overall impact of this research program is to displace fossil sources of energy and chemicals with renewable sources. The construction of a pilot-scale reactor that is capable of processing kilogram quantities of plant biomass was needed to provide significant quantities of product liquid for analysis. This reactor will be used to develop a scaling criterion to de-risk the adoption of this technology. Data collected upon performing analytical-scale pyrolysis has also de-risked adoption, as different biomass varieties produce different levels of organic acids upon pyrolysis. Decreased acidity is desired, as the tanks and pipes that store and transport the liquid product of pyrolysis are made of steel alloys which are subject to corrosion. Biomass varieties that result in desirable compositions upon pyrolysis will be selected for scale-up to the pilot-scale reactor for further examination during the next fiscal year. Several biomass-catalyst combinations have exhibited potential for producing liquid fuels and value-added chemicals. Implementation of pyrolysis and supporting technologies could displace a fraction of the petroleum currently used by the U.S. and provide energy independence and security.
Publications
- Kelkar, S.; Vossler, K.; Teravest, M.; Bughrara, S.; Kamdem, P.; Saffron, C.M. "Quantification and screening of acetic acid production for selected biomass varieties using Py-GC/MS." ASABE Annual Conference. Reno, NV. 2009.
- Kelkar, S.; Vossler, K.; Saffron, C.M. "Quantification of acetic acid levels in Michigan tree species by pyroprobe-GC/MS and comparison of results with acid hydrolysis-HPLC." TCBiomass Conference. Chicago, IL. 2009.
- Li, Z.; Okoroigwe, E.; Kelkar, S.; Stuecken, T.; Saffron, C.M. "Bio-oil production using a screw-conveyor reactor and characterization via GC/MS." TCBiomass Conference. Chicago, IL. 2009.
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