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

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1 Fast Pyrolysis Liquids to Biofuels: R&D at PNNL and IEA Bioenergy DOUG ELLIOTT Chemical and Biological Process Development Energy and Environment Directorate NORTHWEST WOOD ENERGY TEAM FORUM STEVENSON, WASHINGTON MAY 7,

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

3 The National Laboratory system May 9,

4 Powerful combination of core capabilities World-class technical staff State-of-the-art equipment Mission-ready facilities May 9,

5 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 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 May 9,

6 Expanding campus, growing capabilities May 9,

7 Bioproducts, Sciences and Engineering Laboratory Discovery in processes for biobased 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 May 9,

8 Pyrolytic Conversion of Biomass Mode Conditions Liquid Solid Gas Gasification ~ 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 :68 94 May 9,

9 Liquid Fuels from Biomass Bridgwater AV. Review of fast pyrolysis of biomass and product upgrading. Biomass and Bioenergy :68 94 May 9,

10 Systems for Biomass Fast Pyrolysis Venderbosch, RH, Prins W. Fast pyrolysis technology development. Biofpr : May 9,

11 Deliver technologies for gasoline, diesel and jet fuel that use today s infrastructure 11

12 Technical Approach and Strategy Liquefaction Develop an understanding of intermediate bio-oil quality and how to improve It Conceptually In field remove O as CO 2 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 H 2 O 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 May 9,

13 Pyrolysis and Upgrading Upgraded Oil Hydrotreat Fast pyrolysis bio-oil composition 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? May 9,

14 Hydrotreating of Pyrolysis Bio-oils fast pyrolyzer gas byproduct bio-oil H 2 hydrogen recycle and byproduct gas reforming light products 500 C 1-2 sec HT medium products char byproduct aqueous byproduct aqueous byproduct biomass HC heavy products May 9,

15 Fluidized-Bed Fast Pyrolysis System Secondary hopper FEED HOPPER Metered screw High speed screw Heated Nitrogen 1 kg/h 1.6s vapor residence time PUMP2 FLUIDIZED BED REACTOR PUMP1 Solids Collection Liquid Collection Gas Collection Cyclones PRODUCT TANK Hydrocarbon HX EXHAUST Wet Test Meter May 9, SPRAY TOWER Packing tower Coalescer #1 GC Dry ice trap Coalescer #2 Hydrocarbon quench circulation flow

16 Catalytic Upgrading at PNNL Two zone, continuous-flow, trickle-bed, bench-scale reactor 400 ml catalyst bed First zone: 140 C C Second zone: 350 C C sulfided catalyst ~200 ppm H 2 S in feed LHSV atm H m 3 H 2 /L bio-oil OBJECTIVE: To produce upgraded bio-oil for long periods of time (~ 60 days) May 9,

17 Stabilization in the Upgrading Process T < 200 C 0.5 LHSV 68 atm H m 3 H 2 /L bio-oil May 9, non-sulfided catalyst

18 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 May 9,

19 The Future: 100% Renewable Jet The hydroplane ran on 98% Bio-SPK and 2% renewable aromatics Jet A1 Spec Starting SPK Woody Pyrolysis Oil Aromatics Freeze Point ( o C) Flash Point ( o C) Density (g/ml) May 9,

20 8-Reactor Packed Bed System (1.4 cc) 1.4 cc 8-reactor packed bed system Typical LHSV range = h -1 (cc oil/cc catalyst-h) Typical flow rate = 0.24 cc/h per tube May 9,

21 Bio-oil Hydrotreating Catalyst Evaluation using various bio-oils Lab-scale hydrotreater I II Two stage reactor Two-stage reactor, 40 ml catalyst capacity, T< 450 o C, P < 15 MPa Typical LHSV range = h -1 (cc oil/cc catalyst-h) Maximum flowrate = 5 cc/h June 14,

22 Hydrotreating Catalyst Bed Design Challenge: Catalyst Lifetime Bio-oil gas H 2 Gas recycle/ reforming Ligno-cellulosic biomass FLUIDIZED BED REACTOR char Bio-oil Liquid recycle HT Ebullated Bed HC Gas recycle Diesel Jet Fuel Gasoline Fast Pyrolysis H 2 aqueous Hydrotreatment May 9,

23 Scaled-up Catalytic Hydrotreater 9-zone fixed-bed catalytic hydrotreater (20 L) Atmospheric distilling column for fuel fraction collection May 9,

24 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 May 9,

25 Distributed Pyrolysis and Centralized Bio-oil Processing Corn Stover P P P Refinery P P P Deoxygenate Biomass Pyrolysis Mixed Woods Stabilization Biocrude Other Refinery Processes Gasoline Diesel Jet Chemicals Holmgren, J. et al. UOP LLC, NPRA national meeting, San Diego, February May 9,

26 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 May 9,

27 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 May 9,

28 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 May 9,

29 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 May 9,

30 Task 34 Pyrolysis Approved Plan for 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 May 9,

31 Task 34 Approved Plan for 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 May 9,

32 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 May 9,

33 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) May 9,

34 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 May 9,

35 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 May 9,

36 CHP Integrated Pyrolysis Process Fortum with UPM & VTT integrated fast pyrolysis in Joensuu, Finland May 9,

37 BTG & BTG Bioliquids FAST PYROLYSIS PROCESS 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 2 5 kg/hr kg/hr 2 t/hr May 9,

38 EMPYRO: Pyrolysis demonstration plant, Hengelo

39 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 spraycondensor 22m 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 kw e May 9,

40 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 May 9,

41 Thank You! Acknowledgement: Bio-oil Production Miki Santosa LJ Rotness Todd Hart Dan Howe Hydroprocessing Gary Neuenschwander Mariefel Olarte LJ Rotness Huamin Wang Management John Holladay Corinne Drennan Rick Orth