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