Fast Pyrolysis Liquids to Biofuels: R&D at PNNL and IEA Bioenergy DOUG ELLIOTT

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Chemical and Biological Process Development Energy and Environment Directorate

NORTHWEST WOOD ENERGY TEAM FORUM STEVENSON, WASHINGTON MAY 7, 2014

Outline

Introduction to PNNL Research in fast pyrolysis and bio-oil upgrading at PNNL Status of process development within IEA Bioenergy countries

The National Laboratory system

May 9, 2014 3

Powerful combination of core capabilities

May 9, 2014 4

• World-class technical staff • State-of-the-art equipment • Mission-ready facilities

PNNL – FY2013 at a Glance

$936M operating budget 4,300 scientists, engineers and non-technical staff 2,000+ users & visiting scientists 1,168 peer-reviewed papers 85 U.S. and foreign patents; 264 invention disclosures

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Among top 1% in publications and citations in:

Biology and Biochemistry Chemistry Clinical Medicine Engineering Environment and Ecology Geosciences Materials Science Microbiology Molecular Biology & Genetics Physics

Expanding campus, growing capabilities

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Bioproducts, Sciences and Engineering Laboratory

Discovery in processes for bio-based product manufacture

High-pressure catalytic reactor rooms Development and engineering of fungal fermentations Synthesis and preparation of catalysts and feedstocks Catalysis research laboratory Analytical chemistry

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Pyrolytic Conversion of Biomass

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Mode Conditions Liquid Solid Gas

Gasification ~750-900°C 5% 10% char 85%

Fast ~500°C, short hot vapor residence time ~1 s

75% 12% char 13%

Intermediate ~500°C, hot vapor residence time ~10-30 s

50% in two phases

25% char 25%

Carbonization (slow)

~400°C, long vapor residence hours/days

30% in two phases

35% char 35%

Torrefaction (slow)

~290°C, solids residence time ~10-60 min

0% unless condensed, then up to 5%

80% solid 20%

Bridgwater AV. Review of fast pyrolysis of biomass and product upgrading. Biomass and Bioenergy 2012 38:68–94

Liquid Fuels from Biomass

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Bridgwater AV. Review of fast pyrolysis of biomass and product upgrading. Biomass and Bioenergy 2012 38:68–94

Systems for Biomass Fast Pyrolysis

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Venderbosch, RH, Prins W. Fast pyrolysis technology development. Biofpr 2010 4:178–208.

“Deliver technologies for gasoline, diesel and jet fuel that use today’s infrastructure”

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Technical Approach and Strategy

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Liquefaction Develop an understanding of intermediate bio-oil quality and how to improve It Conceptually—

In field remove O as CO2

Yield versus quality trade-offs Pathways

Fast Pyrolysis Catalytic Pyrolysis Hydropyrolysis Hydrothermal Liquefaction Catalytic Liquefaction Mixed oxygenates

Upgrading Reduce process intensity, improve fit for purpose (fuels of choice) Improve catalyst life and activity Conceptually—

Remove O as H2O Retain carbon yield in final product

Pathways HDO (remove O) Ketonization/condensation (improve C yield) Cracking (improve quality)

Lack of understanding of fundamental reactions and species

Pyrolysis and Upgrading

The Opportunity with Fast Pyrolysis High bio-oil yield with relatively low capital cost

Low quality with high volatile content containing acids, carbonyls and unsaturation Improved robust catalysts for upgrading thermally unstable oils HDO yield is consistent at 0.4g product/g bio-oil (due to O loss) Can we improve the quantity and quality of the jet and diesel fraction?

Fast pyrolysis bio-oil composition

Hydrotreat

Upgraded Oil

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Hydrotreating of Pyrolysis Bio-oils

fast pyrolyzer

500°C 1-2 sec

HC

light products

medium products

heavy products

hydrogen recycle and byproduct gas reforming

char byproduct

H2

biomass

HT

aqueous byproduct

gas byproduct

aqueous byproduct

bio-oil

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Fluidized-Bed Fast Pyrolysis System

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FEED HOPPER

Wet Test Meter

EXHAUST

Hydrocarbon HX

PRODUCT TANK

SP

RA

Y TOW

ER

FLUID

IZED

BE

D

RE

AC

TOR

P

UM

P1

PU

MP

2

Coalescer #2

Secondary hopper

High speed screw

Metered screw

Heated Nitrogen

Cyclones

Packing tow

er

Coalescer #1

Dry ice trap

Solids Collection Liquid Collection Gas Collection

GC

Hydrocarbon quench circulation flow

• 1 kg/h • 1.6s vapor

residence time

Catalytic Upgrading at PNNL

Two zone, continuous-flow, trickle-bed, bench-scale reactor

• 400 ml catalyst bed

• First zone: 140°C - 250°C

• Second zone: 350°C - 410°C

• sulfided catalyst

• ~200 ppm H2S in feed

• 0.1 -- 1.5 LHSV

• 75 -- 150 atm H2

• 1-10 m3 H2/L bio-oil

OBJECTIVE: To produce upgraded bio-oil for long periods of time (~ 60 days) May 9, 2014 16

Stabilization in the Upgrading Process

• T < 200°C

• 0.5 LHSV

• 68 atm H2

• 1-10 m3 H2/L bio-oil

• non-sulfided catalyst May 9, 2014 17

Performance over 1440 hours

Extended lifetime testing complete Expanded operating conditions evaluated Higher yield and lower oxygen content in cases Long-term catalyst defunctionalization present

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The Future: 100% Renewable Jet

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The hydroplane ran on 98% Bio-SPK and 2% renewable aromatics Jet A1

Spec Starting

SPK Woody Pyrolysis Oil

Aromatics Freeze Point (oC) -47 -63 -53 Flash Point (oC) 39 42 52 Density (g/mL) 0.775 0.753 0.863

8-Reactor Packed Bed System (1.4 cc)

1.4 cc 8-reactor packed bed system Typical LHSV range = 0.1 – 0.2 h-1 (cc oil/cc catalyst-h) Typical flow rate = 0.24 cc/h per tube

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Bio-oil Hydrotreating Catalyst Evaluation using various bio-oils

Two stage reactor

Lab-scale hydrotreater

Two-stage reactor, 40 ml catalyst capacity, T< 450 oC, P < 15 MPa

I

II

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Typical LHSV range = 0.1 – 0.24 h-1 (cc oil/cc catalyst-h) Maximum flowrate = 5 cc/h

Hydrotreating Catalyst Bed Design

Challenge: Catalyst Lifetime

Fast Pyrolysis Hydrotreatment

char Ligno-cellulosic biomass

gas

aqueous

FLUID

IZED

BE

D

RE

AC

TOR

Diesel Jet Fuel Gasoline

H2

Bio-oil

Gas

recy

cle

Ebul

late

d Be

d

Liqu

id re

cycl

e

Gas recycle/ reforming

H2

HC

HT

Bio-oil

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Scaled-up Catalytic Hydrotreater

9-zone fixed-bed catalytic hydrotreater (20 L) Atmospheric distilling column for fuel fraction collection

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UOP Integrated Biorefinery Demo Kapolei, Oahu, Hawaii

$25 M DOE funded with equal industrial cost share Integrated pyrolysis (RTP), bio-oil preparation (Upgrader I) and hydroprocessing (Upgrader II) 1 t/d = 4 bpd

gasoline diesel jet fuel

construction mid-2011 to 2015

operations 2012 and 2015 detailed life cycle assessment and growth potential

commercialization plan = 4 RTP units and 1 upgrading unit to produce 50 million gallons of fuels annually

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Distributed Pyrolysis and Centralized Bio-oil Processing

Holmgren, J. et al. UOP LLC, NPRA national meeting, San Diego, February 2008.

Stabilization Pyrolysis Biomass

Mixed Woods Mixed Woods

Corn Stover Corn Stover

Deoxygenate

Gasoline Diesel Jet Chemicals

Other Refinery

Processes

Biocrude

Refin

ery

P P

P P

P P

Refin

ery

P P

P P

P P

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IEA Bioenergy is an international collaboration set up in 1978 by the International Energy Agency (IEA) as one of “Implementing Agreements” within IEA’s Energy Technology Network

www.ieabioenergy.com

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IEA Bioenergy Tasks

The work of IEA Bioenergy is structured in a number

of Tasks, which have well defined objectives, budgets, and time frames.

Their activities include:

• Coordination of national RD&D programs,

information exchange and joint projects • Task meetings, study tours and workshops • Publications, reports, newsletters, websites • Networking with industrial and other stakeholders

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23 Contracting Parties

• Australia • Austria • Belgium • Brazil • Canada • Croatia • Denmark • European Commission • Finland • France • Germany • Ireland

• Italy • Japan • Korea • Netherlands • New Zealand • Norway • South Africa • Sweden • Switzerland • United Kingdom • United States

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10 Tasks in three areas

• Feedstock Forest and agricultural products, MSW and recovered fuels

• Conversion Combustion, gasification, pyrolysis, anaerobic digestion, fermentation, biorefineries

• Integrating Research Issues GHG balances, socioeconomic drivers, international trade, systems analysis

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Task 34 Pyrolysis Approved Plan for 2013-2015

Objective: To facilitate commercialization of biomass fast pyrolysis, -- maximize liquid product yield and quality -- produce renewable fuel oil and transportation fuels

Priority Topics

Review of Bio-oil Applications Bio-oil Standardization Support Round Robin for Method Validation TEAs of Biomass Pyrolysis Application Technologies

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Task 34 Approved Plan for 2013-2015

Task Participants National Team Leaders

U.S.A. – Doug Elliott, Pacific Northwest National Laboratory Germany – Dietrich Meier, Thünen Institute of Wood Research Netherlands – Bert van de Beld, BTG BV Finland – Anja Oasmaa, VTT -- Technical Research Centre of Finland U.K. – Tony Bridgwater, Aston University Bioenergy Research Group Sweden – Magnus Marklund, Energy Technology Centre

USA is Operating Agent Contracting Parties

U.S.A. – Department of Energy, Bioenergy Technologies Office Germany – Federal Ministry of Food, Agriculture and Consumer Protection Netherlands – NL Agency Finland – TEKES, Agency for Technology and Innovation U.K. – Department of Energy and Climate Change Sweden – Swedish Energy Agency

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Project Plan

Review of Bio-oil Applications Near-term emphasis Market size, resource size, property impacts Deliverable—journal article (update Oasmaa, Gust, Peacocke et al.)

Bio-oil Standardization Support implementation of standard methods

CEN ASTM REACH

Deliverable—Improved MSDS

Round Robin Bio-oil production with standardized feedstock and centralized analysis Deliverable—journal article publication of evaluation of results

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Project Plan, cont.

Technoeconomic assessments Evaluate various biomass pyrolysis application routes Deliverable--TEA to be published by TBD

Proposed Inter-task collaborations

TEA of bio-oil combustion to compare to solid biomass combustion (Task 32) TEA of bio-oil gasification to compare to solid biomass gasification (Task 33) Use TEAs to develop LCAs (Task 38) Development of operations database (Task 39, 33, ExCo) Evaluation of a pyrolysis-based biorefinery (Task 42)

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Continuing Task Activities

Round Robin on bio-oil production 15 participants will provide bio-oil products for centralized analysis

IEA Bioenergy web database Data input for pyrolysis plants will be generated

Collaboration on LCA of biomass liquefaction processes LCA being prepared and will be reviewed by Task 38

Planned participation with Task 42 meeting in Hamburg in June Comparison of biomass and bio-oil gasification continues

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A commercial application …

Savon Voima Oyj, Local energy production and distribution company in North Savo region, Finland. Has built a bio-oil compatible district heating plant in Iisalmi, Finland.

Stand-by hot water for the district heating grid. Municipal and industrial buildings as well as private houses.

Fortum (with UPM & VTT) Integrated fast pyrolysis plant in Joensuu, Finland Has signed a commercial supply contract for pyrolysis oil

Fuel delivery will start in the beginning of 2014.

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CHP Integrated Pyrolysis Process

Fortum with UPM & VTT integrated fast pyrolysis in Joensuu, Finland

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2 – 5 kg/hr 100 – 200 kg/hr 2 t/hr

Development of ‘rotating cone’ fast pyrolysis process; BTG Bioliquids has been established in 2007 to commercialize the technology; Pilot plant and bench-scale pyrolysis unit available in BTG lab

BTG & BTG Bioliquids FAST PYROLYSIS PROCESS

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EMPYRO: Pyrolysis demonstration plant, Hengelo

Basic plant configuration: Single reactor Pyrolysis gas and flue gas afterburning at 850 °C Integrated combustor/boiler External sand cooler Single-stage, low temperature, oil spray-

condensor

Basic data of the plant: Capacity = 5 t dry biomass/hr Oil Production = 3.2 t/hr Steam production = 2.5 MW Electricity production = 700 kWe

22m

EMPYRO: Pyrolysis demonstration plant, Hengelo

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Closing Thoughts

Biomass conversion to liquid fuels via pyrolytic processes and catalytic hydroprocessing continues in development Need to match end goal (fuel type and processing size) with conversion technology and, where possible, biomass type Catalysis plays a key role in improving quality of products Significant advances in upgrading catalysts

Long term stable operation even with the lowest grade bio-oils Allow researchers to focus on deactivation

Moving forward Improvements in catalyst life and activity Reducing risk refinery integration opportunities Scale-up is underway

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Thank You! Acknowledgement:

Hydroprocessing Gary Neuenschwander Mariefel Olarte LJ Rotness Huamin Wang

Bio-oil Production Miki Santosa LJ Rotness Todd Hart Dan Howe

Management John Holladay Corinne Drennan Rick Orth