Biorefining: Engineering, Science, and Economics
Michael R. LadischPurdue University
September 12, 2018Montevideo, Uruguay
Academia Nacional Ingenieria, Uruguay2018 CAETS, Montevideo, Uruguay
National Academy of Engineering, US
National Academy of Engineering, Uruguay
Purdue UniversityCollege of EngineeringCollege of Agriculture
Acknowledgements
Grand Challenges
Water Energy
Food
Society
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Make solar energy economicalProvide energy from fusion
Develop carbon sequestration methodsManage the nitrogen cycle
Provide access to clean waterRestore and improve urban infrastructure
Advance health informaticsEngineer better medicines
Prevent nuclear terrorSecure cyberspace
Enhance virtual realityAdvance personalized learning
Engineer the tools of scientific discoveryReverse engineer the brain
The Grand Challenges for Engineering
Engineering for the Future,The Third Global Grand
Challenges Summit, July, 2017
Atmospheric greenhouse gas concentrations, global temperatures, and risks to human populations are all increasing, stated Ding
• Extreme weather and climate events
• Failure to mitigate and adapt to climate change
• Large-scale loss of biodiversity and collapse of ecosystems
• Large-scale natural disasters
• Anthropogenic environmental damage and disasters
GLOBAL CLIMATE CHANGE AND SUSTAINABLE CITIES
Engineering for the Future,The Third Global Grand
Challenges Summit, July, 2017
America’s Energy Future: Technology Opportunities,
Risks, and TradeoffsJuly 2009
October 2008 Est. September, 2009
http://www.nationalacademies.org/energy
May 20, 2009 June 15, 2009
Basic Concerns/Motivations
● Environmental concerns emanating from the burning of fossil fuels with inadequate accounting for the serious externalities involved.
● National security concerns emanating from our falling production of petroleum, our dependence on fragile supply chains, the vulnerability of our electrical grid and transportation sector, and nuclear safety and proliferation.
● Economic competitiveness in the face of volatile prices for energy supplies and uncertainties that surround the various supply chains.
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National Academies, 2009
AEF “Global” Conclusion
The only way to meet the concerns identified given our initial conditions is to embark on a sustained effort to transform the manner in which we produce and consume energy.
Transforming the Energy Sector
The AEF committee carefully considered some of the critical technological options (including their costs and limitations) that might be deployed in pursuing a transformation of the energy sector that would meet the identified economic, environmental and national security concerns.
4National Academies, 2009
Economics: Oil Price Trends are Uncertain$ / Bbl – EIA International Energy Outlook
Oil Prices Fluctuate
http://www.macrotrends.net/1369/crude-oil-price-history-chart
CPI Correlates to Oil Prices
http://www.macrotrends.net/1373/oil-prices-vs-the-cpi-historical-chart
Energy Consumption in other Countries is Increasing (in Quadrillion Btu)
Renaissance in US Oil Production
Global Energy Sources (and Consumption) are Increasing
Pearl Gas-to-Liquid Plant, Qatar
Fossil: Oil, Coal, Gas
RenewablesHydro Nuclear
World Energy Council, 2013
TPES = total primary energy supplyMtoe = millions of tons of oil equivalentRenewables = wind, solar, PV, biomass“Negajoule” = energy saved
Global CO2 Emissions are Increasing
Scripps Institute: http://www.climatecentral.org/gallery/graphics/keeling_curve
Keeling Curve
The Wall Street Journal, 5/22/17
Future of Liquid Transportation Fuels?
Two Approaches to Reduce Liquid Fuels Emissions
Engine Technology More miles with less fuel
More fuel with less carbon –advanced low carbon biofuels
Cellulosic materials: low carbon and with long term sustainability. Combined with efficient biofuel engines, emission reductions result.
Shaver, 2014, Kakosimos, 2016; Allen, 2015
Biorefining18
sustainable processing of biomass into bio-based products:
food feed chemicals materials
and bioenergy:biofuels power and/or heat
IEA Bioenergy Task 42 on Biorefineries, 2017https://www.iea-bioenergy.task42-biorefineries.com/en/ieabiorefinery.htm Houghton, Weatherwax, Ferrell, DOE SCE 0095, 2006
Agricultural Residues: Collection and storage must be efficient
with permission, Shinners, 2009
US Corn Stover 1 to 2 tons (dry basis)/acre 300 million tons / year stover
Some Residue left on groundCorn
Brazil Sugar Cane 7 to 10 tons (dry basis)/acre; Green residue: 3 tons /acre 300 million tons / year bagasse
Unica Report, 2010
Corn Stover - stalks
Sugarcane and bagasse
Iowa Cornstover Collection Study, 2008-2012 20
Biomass Program Overview, Poet / DSM 2008-2012
Corn Cobs: Large scale harvest and storage
Yinbu Qu, Shandong U., 12/4/2008
200,000 tons / year in the Yucheng area - China
Global Agriculture = Water
Irrigation = 70% of global fresh water consumptionResearch: drought tolerance or submergence (water) tolerance
Nitrogen (Fertilizer) via Haber – Bosch Process (uses 3% of global gas production)118 million metric tonnes / yr ($100 Bn / yr) ammoniaResearch: nitrogen fixing crops (plants and soils)
PhosphorousBioavailable orthophosphate; only 30 % of amount applied is actually used by plants (reacts with soils)Research: increase efficiency of phosphorous use and delivery of fertilizer
Holistic Approach: Research: Precision Agriculture, Phenotyping, Genotyping, Stacked Traits
Jez et al, Science, 353, 6305, 1241, 2016; Farinas, 2016; Plaut, 2015
Requires Large Amounts of Water (Rainfall and Irrigation)Fertilizer, biotechnology (traits of productive crops)
SOIL HEALTH PRACTICES (Sequester Carbon)Crop Rotation Biosolids Application
No Till Rotational Grazing
National AcademiesLand Management Practices for CO2 Removal…, 2018
Soil Carbon Sequestration
2-3 times more carbon in soil than in atmospheric (Stocker et al., 2013)
1.4 billion metric tonnes (G + C) can be stored annually agricultural soils
80% of potential G + C could be reached at $100 / ton CO2(Smith et al., 2008)
But soil organic carbon will only increase over a finite period until new equilibrium occurs
National AcademiesLand Management Practices for CO2 Removal…, 2018
Gen 2 Second Generation (Cellulosic) Biofuels
Major sources of uncertainty for cellulosic biofuels:Future oil prices,Feedstock costs and availability by region,Conversion costs and efficiencies,Environmental impacts,Government policy.
The combination of all of these uncertainties makes analysis of biofuels impacts highly uncertain.Current condition of the financial markets causes difficult conditions for cellulosic biofuel investment
Tyner, 2013
David Dayton, NREL, IEA, 2007
1. Biochemical vs Chemical Conversion
Composition of Lignocellulosic Biomass
Glucan44%
Xylan17%
Lignin32%
Acetyl groups3%
Ash2%
Extractive2%
Hardwood composition
Similar CompositionsCorn residueSugar Cane BagasseSwitch grassHardwoods
Lignin under-utilizedInhibits hydrolysisProtects structural
carbohydrates
Ko, Kim, 2014
Biochemical Conversion of Cellulose
6 Combustion orGasification
54321
CO2
Co-products
Pretreatment Hydrolysis FermentationFeedstockPreparation
Feedstock
Catalysts
EnzymesMicrobes
(Yeast, Bacteria)
Separations
Fuel, Chemicals
ResidueEnergy
Aqueous based, microbial/protein catalysts, mild conditions
2. PretreatmentPretreatment disrupts biomass for better enzyme access
Approximately 18% of total cost
Mosier et al., 2005
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Feedstock preprocessing needed for operability
Liquefy (from slurry) if possible Minimize addition of chemicalsSimplify pumps / pumping Understand inhibition / inhibitors
Minimize hydrolysis during liquefaction (minimizes enzyme)Chose microorganism wisely
Modeling of liquefaction of lignocellulosic biomass (to start in 2018)
Pictures of corn stover at 22% weight of solids / volume of water
Ladisch, Kim, Ximenes 2009; Ximenes et al 2010,2011; Cuhna, 2014; Ladisch, Wassgren, Mosier, Sharma, et al 2017
Addition of BSA to Enzyme High Yield at Lower Enzyme Loading and High Severity
BSA Added
No BSA Added
No Pretreatment
Cellic Ctec2 of 5 FPU (8 mg protein)/g glucan, pH 4.8, in 50 mM citrate buffer, 50°C, 200 rpm for 168 hrs. Equivalent to 3.5 mg/g total solids prior to pretreatment
Kim et al, 2014
32Diluting Enzyme with Non Catalytic Protein Increases Yield
As specific activity decreases, conversion increases
Cellulase loading fixed at 1.8 FPU / g glucan, equivalent to 1.3 FPU / g pretreated solids
Kim et al, 2014
Pretreatment and Cost Effective Enzymes are KeyPretreatment:
- makes substrate susceptible- decreases enzyme usage (increases yield)- releases enzyme inhibitors (increases enzyme usage)
xylo-oligosaccharidesphenols, tannic acids
- may form fermentation inhibitorsacetic acidaldehydes (fufural)phenols
Science led to strategies for managing inhibition due to lignin. Engineering reduced enzyme requirement (and cost) by 5X.
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Biorefining: Common DenominatorsBiomass derived sugars (glucose, xylose) are a key intermediate
Major Current Products: Ethanol, biodiesel, aviation biofuelsAmino acids (food, nutritional and animal supplements)Enzymes (detergents, biocatalysts)
Some moderate volume chemicals being scaled upMainly organic acids, glycerolLactic acid (polylactate)Glycerol derived from biodiesel co-product, sugars
Many small volume / high value candidates (precursor molecules)on pathway to commercialization
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Ethanol, Glycerol, Sorbitol35
B-P Criteria of 9 / 9 (i.e., renewable with documentable commercial potential)
Sorbitol: 500,000 tons / yr.; major use is as sweetner and food additive
Glycerol: (converted to products mainly via catalytic routes )Hydrogenolysis to ethylene glycol, propylene glycol, acetol, lactic acid
Dehydration to hydroxypropionaldehyde and acrolein
Being researched for biochemical conversion to 1,3 propanediol (PDO, Dupont SeronaTM ). Glucose is a feedstock for 1,3 PDO fermentation.
Ethanol: 15.8 billion gal per year in 2017; may be converted to ethylene
Chemistry, chemical catalysis, and biochemical technology for bioproductmanufacture in processes that require hydrogen may evolve using biological approaches (living microbial catalysts) in the future.
Bozell and Petersen, Green Chem., 2010, 12, 539-554.
Sustainability: Industrial Biology / BiotechnologyBiobased Products 50 million tons / yr worldwide
US Economic activity of $353 billion / yr (2.2 % of GDP ) – major growth potential
Industrialization of Biology, NAS 2015
Not yet Commercial Commercial
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ConclusionsSustainability, Food, Energy:
inter-dependent – and dependent on - agriculture.
Factors that impact food, energy, and chemicals production are:
1. Land 2. Seeds 3. Productivity 4. Energy 5. Technology
The chemical and energy enterprises are needed to provide production tools to agriculture, either in the field or in the plant.
Distribution of resources / population tipping point are unknowns.
Economics: the driver