NREL is a national laboratory of the U.S. Department of Energy, Office of Energy Efficiency and Renewable Energy, operated by the Alliance for Sustainable Energy, LLC.

Advanced Liquid Biofuels Developments in the USA

James D. (Jim) McMillan, Ph.D.

Bioenergy Australia 2016 Conference

Brisbane, Queensland, Australia

November 15, 2016

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Synopsis

• US remains world’s largest producer, producing over 50 B L ethanol and 6 B L diesel biofuels o 10% ethanol “blend wall” fracturing

o Momentum for higher blends building

• Science and technology continues to advance o Many routes and bio/catalysts

improving, increasing efficiency, reducing production costs

• Commercialization of cellulosic ethanol operations progressing o e.g., DuPont, POET-DSM and QCCP

• Paris COP21 agreement reflects growing consensus to address/mitigate climate change.

• Oil prices remain too low for most advanced biofuels to be economical o Many technology developers/ producers

are halting biofuels RD&D, redirecting efforts to higher value non-fuel products

o Abengoa, INEOS plants idled & for sale o Norway out of Task 39 (oil price impact)

• Production of cellulosic and advanced biofuels lags RFS2 targets; obligated volumes lowered for 2014-2016

• Bioenergy held to higher standard than other technologies. Concerns about: o Carbon neutrality, food vs. fuel, etc.

• Other challenges o Polarized administration and congress o No value/price on reducing carbon emissions

despite mounting global warming – Atmospheric CO2 > 400 ppm – Great barrier reef dying (bleaching) – 2016 on track to be hottest year yet

Positive Negative 2015-2016: Exciting but Challenging Times

* RFS2 = Renewable Fuel Standard

* RFS2 = Renewable Fuel Standard

* RD&D = Research, Development and Demonstration

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Outline

•Current drivers, energy landscape and production levels

•Cellulosic biofuels options, challenges and progress •Thermochemical, biochemical and hybrid routes

o2012 NREL biochemical cellulosic ethanol demonstration •Process relevant performance data that’s in the public domain

• Illustrates the power of sustained, focused, well-funded R&D

•Emerging Adv. Biofuels Technologies & New Initiatives

•Summary and outlook

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Promote use of domestic and

renewable (sustainable)

energy resources

Create a new bio-industry, foster science & engineering, and create new

jobs

Reduce carbon emissions from energy and fuel production and

consumption

Reduce

dependence on non-

renewable petroleum

supplies

The use of renewable biomass as as a feedstock for producing fuels and chemicals supports United States national priorities

Biofuels Support National Priorities

5 | Bioenergy Technologies Office

The Challenge and Opportunity in the USA

Biofuels could displace 30% of liquid transportation fuels by 2030

THE OPPORTUNITY

More than 1 billion tons of biomass could be sustainably produced in the U.S.

1 Billion tons of biomass could displace 30% of U.S. petroleum use by 2030 and reduce annual GHG emissions by 400 million tons

THE CHALLENGE

More than $1 billion is spent every three days on U.S. crude oil imports

Transportation sector accounts for 67% of petroleum consumption and 26% of GHG emissions in the U.S.

Biomass resources can help mitigate petroleum dependence and GHG emissions

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Transport Fuel is a Big Part of U.S. Energy Mix

Source: Lawrence Livermore National Laboratory, 2016. (https://flowcharts.llnl.gov)

U.S. Energy Use in 2015 (97.5 Quads) (Quadrillion Btu)

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U.S. Fuel Ethanol Production Capacity (2015)

2/29/16, 10:40 AMU.S. Fuel Ethano l Plant Product ion Capacity

Page 1 of 1ht tps: / /www.eia.gov/petroleum/ethanolcapacity/ index. c fm

U.S. Nameplate Fuel Ethanol Plant Production Capacity as of January 1,2015

PADDistrict

Numberof Plants

2015Nameplate Capacity

2014Nameplate Capacity

(MMgal/year) (mb/d) (MMgal/year) (mb/d)

PADD 1 5 464 30 260 17

PADD 2 173 13,151 858 12,504 816

PADD 3 5 442 29 442 29

PADD 4 5 190 12 190 12

PADD 5 7 510 33 285 19

U.S.Total 195 14,757 962 13,681 893

Nameplate Capacity: volume of denatured fuel ethanol that can be producedduring a period of 12 months under normal operating conditions

Source: Form EIA-819M Monthly Oxygenate Report

Petroleum & Other Liquids

U.S. Fuel Ethanol Plant Production CapacityRelease Date: June 23, 2015 | Next Release Date: June 2016

Previous Issues

Year: 2015 Go

This is the fifth release of U.S. Energy Information Administration data on fuel ethanol production capacity. EIA first reported fuel

ethanol production capacities as of January 1, 2011 on November 29, 2011. This new report contains production capacity data for all

operating U.S. fuel ethanol production plants as of January 1, 2015.

Detailed nameplate and maximum sustainable capacities of fuel ethanol plants by Petroleum Administration for Defense District (PAD

District) are available in XLS.

Source: US EIA. https://www.eia.gov/petroleum/ethanolcapacity/index.cfm

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US Commercial Ethanol Production Plants

Source: Renewable Fuels Association (RFA), 2016: http://www.ethanolrfa.org/resources/biorefinery-locations/

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U.S. Diesel Biofuels Production 2003-2013

Sources: National Biodiesel Board (NBB) and EIA Annual Energy Outlook 2014 (AEO 2014), NBB: http://www.biodiesel.org/production/production-statistics

AEO: Table 11. Petroleum and Other Liquids Supply and Disposition http://www.eia.gov/forecasts/aeo/tables_ref.cfm

Biodiesel (FAME & HEFA) production levels reached 1.2 - 1.8 and 1.4 billion gallons in 2013 and 2014, respectively, with NBB estimates much higher than EIA’s.

Annual production levels highly constrained feedstock supply. Need alternative

feedstocks to enable major growth

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Cellulosic Biofuels Options, Challenges and Progress

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Thermochem

Cellulosic Biofuels Technology Routes Biochem, Thermochem & Hybrid Approaches

Product Recovery/

Purification, Storage &

Distribution

Feedstock Supply

Logistics, Preparation & Handling

Syngas Fermentation

Aqueous Phase

Reforming

Biomass Sugars Hydrolysate

Conditioning / Detoxification

Pretreatment & Enzymatic Hydrolysis/

Saccharification

Biomass Sugar

Fermentation

Biochem

Syngas Cleanup &

Conditioning/ Tar Reforming

Thermochemical Synthesis Gas Production/ Gasification

Syngas Catalytic

Upgrading/ Product

Synthesis

Gasification

Bio-oil Stabilization

Pyrolysis Bio-oil

Upgrading To Fuel

Pyrolysis

Hybrid

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Biochemical Conversion Flow Diagram

Pretreatment Conditioning

Co- fermentation

of C5 & C6 Sugars

Product Recovery Products

By-products

Enzyme Production

Enzymatic Hydrolysis

Residue Processing

Simultaneous Saccharification and Co fermentation

Ethanol Yields

Ethanol Concentration

Xylose Yield Xylose Degradation

Reactor Costs Solids Loading

Sugar Losses

Glucose Yield

Solids Loading (titer)

Feedstock Variation

Feedstock Quality Enzyme Cost

Rate Hydrolyzate Toxicity

Feedstock Cost

How can research reduce cost?

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Technical Barriers – Biochemical 1. Plant cell wall recalcitrance

Deconstruct secondary cell wall sugar-based polymers to fermentable sugars (and lignin?) at high yield and low cost (low energy and other inputs)

2. Carbohydrate heterogeneity Ferment all biomass sugars to ethanol at high yield, i.e., both hexoses (glucose, galactose, fructose and mannose) and pentoses (arabinose and xylose)

3. Process integration and scale up Cost effectively test/qualify process options; close mass balance; demonstrate process robustness, scalability

Design-Expert® Software

Ethanol Yield

X1 = B: Conditioning X2 = D: Strain

Actual FactorsA: Hydrolysate Strenght = 65.00C: Added Glucose = 100

Neutralization

Ov erliming S.c. D5A

Broin S.c.

Z. m. 8b

P.s.

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USA’s CE Development Timeline (40+ Years!) 1970s – Oil shocks spur search for renewable liquid fuels supply

1990s – Sugars cofermenting microbes developed (ethanol)

2000s – Hydrolytic enzyme cost reduced 10-20-fold

2006 – US admits it’s addicted to oil; aggressively funds cellulosic ethanol (CE) Integrated BioRefineries (IBRs)

2010s – Scaled up commercial production begins…

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Cellulosic Ethanol Development Timeline (2) 1970s – Oil shocks spur search for renewable fuel supply

1990s – Sugars cofermenting microbes developed (ethanol)

2000s – Hydrolytic enzyme cost reduced 10-20-fold;

2006 – US admits it’s addicted to oil; aggressively funds cellulosic ethanol (CE) Integrated BioRefineries (IBRs)

2010s – Scaled up commercial production begins… 2012

- NREL pilots BC (and TC) CE processes, achieving performance consistent with a modeled production cost of US $2.15/gallon

Operating conditions for NREL’s BC pilot CE demonstration – Feedstock: Corn stover (i.e., the agricultural residue after harvesting the corn grain)

– Pretreatment: 160°C, 10 minutes, ~0.35% (w/w) H2SO4 acid in aqueous reaction, in some cases after first applying an NaOH alkaline washing “deacetylation” step

– Enzymatic hydrolysis: Novozymes CTec2 cellulase, 20% total solids loading (~12% insoluble solids), 50°C, pH 4.8-5.2 controlled with NH4OH

– Fermentation: DuPont’s cofermenting Zymomonas mobilis A7, 33°C, pH 5.8 controlled with NH4OH, 10% (v/v) inoculum (~0.5 g/L initial cell density, dry basis)

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g/L

) Glucose

Xylose

Arabinose

Ethanol

Pilot Process - SHF Concentration Data

Enzyme: Ctec2 loaded at 19 mg cellulase/g cellulose; substantially lower w/ Ctec3

24 0 0 48 72 24 48

Enzymatic Hydrolysis Fermentation

Time (h)

SHF mode ≥ 1000 L scale

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2007$ p

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gallo

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Conversion Feedstock

$3.85 $3.64

$3.57 $3.18

$2.77 $2.56

$2.15

$4.27

$5.33

$6.90

$9.16

Bench Scale - Enzymes

Scale Up Pretreatment

Scale Up Enz Sacch/Ferm

History of CE Technology Improvement

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Commercial CE Plants (partial list)

COMPANY LOCATIONCELLULOSICFEEDSTOCK

TECHNOLOGYPLATFORM

SIZE(MGY)

Abengoa Hugoton,Kansas,USAAg.residues,energycrops

Biochem 23

Chemtex Crescentino,ItalyWheatstraw,

ArundodonaxBiochem 20

DuPont Nevada,Iowa,USA Cornstover Biochem 25

Enerkem*Edmonton,Alberta,Canada

Municipalsolidwaste

Thermochem 10

Fiberight Blairstown,Iowa,USAMunicipalsolidwaste

Biochem 6

GranBioSãoMigueldosCampos,Alagoas,Brazil

Sugarcanebagasse

Biochem 20

IneosBioVeraBeach,Florida,USA

Municipalsolidwaste

TC-BCHybrid 8

POET-DSM Emmetsburg,Iowa,USA Cornstover Biochem 20

QuadCountyCornProcessors

Glava,Iowa,USA Cornkernelfiber Biochem 2

Raízen(Iogen)Piracicaba,SãoPaulo,Brazil

Sugarcanebagasse

Biochem 10

Total 144113

*Markettargetisethanolalbeitneartermfocusismethanol;MeOHàEtOHinprogress.

Emerging Technologies & New Initiatives

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Emerging Technologies & New Initiatives

• Current RD&D focused on “drop-in” infrastructure compatible biofuels; higher ethanol blends also in the mix

• Science and process technology are improving, but economics remain challenging given market conditions

•Highlight developments: • Pyrolysis oil coprocessing in

petroleum refineries (Ensyn)

• Gasification + Fischer-Tropsch synthesis (Fulcrum)

• Combined optimization of advanced fuels and advanced engines (USDOE’s Co-optima initiative)

Schematic of Petrobras’ demo-scale FCC unit. Source: A.R. Pinho et al. Fuel 188 (2017)

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Refinery Co-processing Pathway Advancing

Source: A.R. Pinho et al. Fuel 188 (2017) 462–473

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Co-Optimization of Fuels and Engines

• better fuels. better vehicles. sooner.

Crosscutting project tackling fuel and engine innovation to co-optimize performance, maximize transport efficiency.

Advancing R&D to: • Bring affordable, scalable advanced

biofuels and advanced engine solutions to market more quickly

• Improve fuel economy 15%–20% beyond targets of BAU R&D efforts

• Reduce petroleum use, achieve massive cost savings annually via improved fuel economy

• Dramatically decrease transport sector pollutants and GHG emissions

Co-Optimization of Fuels and Engines

Draws on collaborative expertise of two DOE research offices, nine national

laboratories, and numerous industry and academic partners.

http://energy.gov/eere/bioenergy/co-optimization-fuels-engines

Summary and Outlook

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Commercialization Status

Cellulosic Ethanol oAbengoa, DuPont, INEOS Bio and POET-DSM

progressing CE plant start ups; production remains well below design capacity oDuPont seeks to license to China and Macedonia; no

licenses yet but agreements in place to enable this o Technology robustness and economic viability remain to be fully

demonstrated for ag. residue and woody feedstocks

o Corn ethanol dry mills now implementing production of CE from corn fiber (cellulosic fraction of DDGs)

FAME and Renewable Diesel oVO, FOG-based FAME and HEFA production growing

however volumes constrained by feedstock supply

Other advanced routes also progressing but performance info proprietary, not public) o Syngas fermentation (e.g., LanzaTech)

oGasification + Fisher-Tropsch (e.g., Fulcrum)

o Pyrolysis + Refinery Coprocessing (e.g., Ensyn)

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Situation and Outlook

• Terrestrial and aquatic biomass remains our only renewable source of carbon; it can also be carbon neutral or carbon sequestering.

• CE technologies progress shows power of sustained, focused R&D, with multiple feedstock x conversion process options now being commercialized o Sugar platform approaches dominate but hybrid and

thermochemical gasification routes also progressing

o Economics challenged by low oil price & policy uncertainty

o Market success needed to re-frame biofuels’ image and demonstrate that advanced biofuels “can be done right”

• Commercialization of drop-in hydrocarbon biofuels at earlier stage, with TC routes now predominant

• Supportive policies like U.S.’s RFS2 and CARB LCFS are key to expanding advanced biofuels deployment - Needed to ensure a market and foster investment

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More Information

• National Renewable Energy Laboratory www.nrel.gov

• USDOE’s Bioenergy Technologies Office (BETO) http://www1.eere.energy.gov/bioenergy/

• USDOE BETO Peer Reviews (2011, 2013, 2015) www.energy.gov/eere/bioenergy/2015-project-peer-review

• USDOE-USDA Biomass R&D Initiative www.biomassboard.gov

• Alternative Fuels Data Center www.afdc.doe.gov

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Thanks for Your Attention! Questions?

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Funding: US DOE EERE BioEnergy Technologies Office (BETO)

Data: NREL’s Biochemical Cellulosic Ethanol Demonstration Project Team (Daniel Schell et al.)

Refinery Coprocessing: NREL’s Helena Chum & Michael Talmadge

Acknowledgments