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Re‐engineering the Integrated Biorefinery:A materials approach to in situ biofuel upgrading
Jillian L. GoldfarbDepartment of Biological & Environmental Engineering
College of Agriculture and Life Sciences
Cornell University
Motivating Research Needs
Biomass
ThermochemicalConversion
BiochemicalConversion
Product UpgradingBiofuels Bioproducts
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Our Approach: Focus on Materials
Integrated Biorefinery
Chemicals
Fuels
Energy
Materials
Upgrading Biorefinery Materials
Post‐processing of biochar and biofuels
• “Activation” of biochar (chemical, physical) to open pores, increase surface area
• Catalytic upgrading of condensable and non‐condensable species
Pre‐processing of biomass
• Pre‐treatment (i.e. supercritical extraction, solvation) materials, changing biomass structure and content to change fuels
• Integrate heterogeneous materials during treatment to make multi‐functional materials
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Biochar Upgrading (Post‐Processing)
Pistachio Nutshells
Bio‐oil, Pyrolysis Gas Pistachio Biochar
Activated carbon
Electrochemical Cell
Bio‐oil, Pyrolysis Gas
Pyrolysis
Activation
J.L. Goldfarb, G. Dou, M. Salari, M.W. Grinstaff. “Biomass-Based Fuels and Activated Carbon Electrode Materials: An Integrated Approach to Green Energy Systems.” ACS Sustainable Chemistry & Engineering. 2017. 5, 3046-3054.
Physical and Chemical Activation
2.1
2.2
2.3
2.4
2.5
2.6
2.7
2.8
500 600 700
Ave
rage
Po
re D
iam
ete
r (n
m)
Activation Temperature (ºC)
KOH Activated
Large Particle
Small Particle
2.1
2.2
2.3
2.4
2.5
2.6
2.7
2.8
700 800 900
Ave
rage
Po
re D
iam
ete
r (n
m)
Activation Temperature (ºC)
CO2 Activated
Large Particle
Small Particle
KOH 500°C Small Particles CO2 700°C Small Particles
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Biomass Based Carbons “By Design”
Isıtan, S., S. Ceylan, Y. Topcu, C. Hintz, J. Tefft*, T. Chellappa, J. Guo and J.L. Goldfarb. “Product Quality Optimization in an Integrated Biorefinery: Conversion of Pistachio Nutshell Biomass to Biofuels and Activated Biochars via Pyrolysis.” Energy Conversion & Management.
2016. 127, 576‐588.
Activated Biochars for Water Treatment
Goldfarb, J.L., L. Buessing, E. Gunn, M. Lever*, A. Billias*, E. Casoliba, A. Schievano, F. Adani. “Novel Integrated Biorefinery for Olive Mill Waste Management: Utilization of Secondary Waste for Water Treatment.” ACS Sustainable Chemistry & Engineering.
2017. 5, 876-884.
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in situ Biofuel Upgrading: Biotemplating
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FeCl3
FeCl3 FeCl3
FeCl3
FeCl3 NaBH4
NaBH4
NaBH4
NaBH4 NaBH4
NaBH4
NaBH4
FeCl3
Xue, J., G. Dou, E. Ziade, J.L. Goldfarb. “Integrating Sustainable Biofuel and Silver Nanomaterial Production for in situ Upgrading of Cellulosic Biomass Pyrolysis.” Energy Conversion & Management. 2017. 142, 143-252.
Enhancing Pyrolyis Gas with AgNO3
H2 CH4 C2H2 C2H4 C2H6 CO2
m/z = 2 m/z = 16 m/z = 26 m/z = 27 m/z = 30 m/z = 44Raw Cellulose 4.509E-03 2.180E-03 2.017E-04 6.477E-04 1.519E-04 4.235E-03Ag Cellulose 1.324E-02 2.238E-03 2.332E-04 6.402E-04 2.186E-04 5.274E-03Rel Change: 193.7% 2.7% 15.6% -1.2% 43.9% 24.5%Raw Corn 5.366E-03 1.817E-03 1.423E-04 6.087E-04 1.747E-04 3.445E-03Ag Corn 1.271E-02 2.228E-03 1.457E-04 5.157E-04 2.544E-04 5.741E-03Rel Change: 136.9% 22.6% 2.4% -15.3% 45.6% 66.6%
Integrated MS Area
Xue, J., G. Dou, E. Ziade, J.L. Goldfarb. “Integrating Sustainable Biofuel and Silver Nanomaterial Production for in situ Upgrading of Cellulosic Biomass Pyrolysis.” Energy Conversion & Management. 2017. 142, 143-252.
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Increasing Bio‐oil Target Compounds
Xue, J., G. Dou, E. Ziade, J.L. Goldfarb. “Integrating Sustainable Biofuel and Silver Nanomaterial Production for in situ Upgrading of Cellulosic Biomass Pyrolysis.” Energy Conversion & Management. 2017. 142, 143-252.
Biotemplating Nanomaterials
Silver nanospherestemplated on corn husk
Iron oxide nanoparticles templated on banana stalk
Silver nanowires templated on cellulose
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Re‐engineering the Biorefinery
By taking a materials‐based, holistic approach to using biomass for energy and environmental applications, we can:• Manipulate bio‐oil and gas yields and properties:
• Incorporate secondary fuel recovery during biochar upgrading
• Improve yield of hydrogen and methane in pyrolysis gas• Increase furfurals (esp. 5‐HMF) in condensable biofuels
• Simultaneously fabricate materials from char systems:• Activated carbons “by design” (tuning surface area, surface
functional groups)• Heterogeneous clay‐biochar materials for improved
adsorbents, soil nutrient sequestration/fertilizer release• Bio‐template nanomaterials using reducing properties of
biomass
Laboratory Capabilities
Goldfarb Research Laboratory
• Furnaces and reactors for torrefaction, pyrolysis and hydrothermal carbonization
• Thermogravimetric Analyzer – Differential Scanning Calorimeter (proximate analysis, reactivity)
• Residual mass spectrometer (online gas analysis)
• Gas chromatograph‐mass spectrometer (condensable fuel and organics analysis)
• Inductively coupled plasma mass spectrometer (inorganics/heavy metals analysis)
• UV‐Vis spectrophotometer (contaminant uptake studies)
• Physi‐ and chemisorption surface area analyzer (surface areas, porosity, catalyst active site characterization)
Cornell Pyrolysis Kiln
• 120 lb/hour, up to 600°C kiln
• Designed and built by Full Circle Biochar (CA)
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Acknowledgements
A portion of this material is based upon work supported by the National Science Foundation under Grants NSF CBET‐1505718 and NSF CBET‐1127774
Graduate Students:Li Buessing, M.S. 2012Ana Celaya, M.S. 2013Chloe Hintz, M.S. 2014Junjie Xue, Ph.D. 2016Anna Newman, M.S. 2016Cole Ashman, M.Eng. 2017Giulia Ischia, M.S. 2018Silvia DelBianco, M.S. 2018Lihui Gao, Ph.D. (2019)
Post‐Docs:Thiago ChellappaGuolan DouCarol Johnson
Undergraduates:Melissa Lever, B.S. 2013Alex Billias, B.S. 2015Chitanya Gopu, B.S. 2017Ami Vyas, B.S. 2017Noah Bernays, B.S. 2018
Collaborators:Prof. Selim CeylanProf. Luca FioriProf. Mark GrinstaffProf. Emily RyanProf. Pirooz VakiliDr. Maryam SalariDr. Maurizio Volpe