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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

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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

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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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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