1. t TNO Environment, Energy and Process Innovation Crude oil from biomass with the HTU ® process Example of an Early Stage Technology Jaap Koppejan EMIMENT workshop, 8-9 03 2004, Riga

2. t 8 March 2004 EMINENT 2 HTU = crude oil from biomass

3. t 8 March 2004 EMINENT 3 What is HTU ? Conditions: 300 – 350°C; 120 - 180 bar reaction time 5 - 20 minutes liquid water Feedstocks:All types of biomass, domestic, agricultural and industrial residues, wood Also wet feedstocks, no drying required Chemistry:Oxygen removed as Carbon Dioxide Products 45% Biocrude (%w on feedstock, dry basis) 25% Gas (> 90% CO 2 ) 20% H 2 O 10% dissolved organics (e.g., acetic acid, methanol) Thermal efficiency: 70 - 90 %

4. t 8 March 2004 EMINENT 4 HTU ® Product characteristics Biocrude- Heavy organic liquid - Solidifies at 80 °C - Not miscible with water - Oxygen content 10 - 18 %w - H/C ratio = 1.1 - LHV 30 -35 MJ/kg Applications Biocrude: (co)combustion in coal- and oil- fired power stations After hydrogenation: - premium diesel fuel; kerosene - lubrication oils - chemicals feedstock (cracker)

5. t 8 March 2004 EMINENT 5 Perspectives for energy from biomass 19902040 Energy demand3501000 Delivered by: Fossil fuels255480 Renewables80>400 Hydropower2050 Wind-70 Solar-130 Biomass Biomass60>200 (Shell scenario)

6. t 8 March 2004 EMINENT 6 Global potential for energy from biomass Energy farming on 10 9 ha land area @ 15 ton(db)/ha.year 250 EJ/yr Biomass residues (Forestry, wheat, rice, sugar cane, corn,etc. 70 EJ/yr

7. t 8 March 2004 EMINENT 7 Suitable feedstocks for HTU in Europe Agricultural / Industrial Residues200 Million tons/a (db) (Source: Eurec agency, 1996) Short-term niches for HTU: - Olive Oil Industry3 - 5 Million tons/a (db) - Organic household waste26 ktons/a (db) per (from centralized waste separation) 250,000 inhabitants - Residues from sugar and beer production.

8. t 8 March 2004 EMINENT 8 Agricultural and industrial residues4,000 Mt/a (db) (Source: “Renewable Energy; sources for (approx. 70 EJ/a) fuels and electricity”, 1993) Future organic household waste 800 Mt/a (db) (own tentative estimate) Short-term niches for HTU: - Organic household waste - Bagasse (> 100 Mtons/a) - Forestry residues from existing plantations - Coir dust Suitable feedstocks for HTU worldwide

9. t 8 March 2004 EMINENT 9 Development of HTU 1982 – 1988Process R&D, Shell Laboratory, Amsterdam 1994 – 1997Technical-Economic evaluation of HTU technology 1997 – 2000Process development project 2002 – 2004Final process development 2006 – 2007First commercial demonstration 2009HTU diesel commercially available

10. t 8 March 2004 EMINENT 10 Technology Development Path ( S - curve) Scientific Base / Explanatory Process Scouting Techn./Econ. Feasibility Process Development Commercial Prototype HTU diesel commercially available Next S- curve Improved scientific base 2006-2007 2004-2005 2000-2002 1983 2008-2009

11. t 8 March 2004 EMINENT 11 HTU pilot plant at TNO Feed 100 kg/h (wet) Biocrude product 8 kg/h

12. t 8 March 2004 EMINENT 12 Block scheme of HTU pilot plant Biomass 10-20 kg/hr (db) High pressure pump Preheater / Re actor 1 Reactor 2Cooler Gas /liquid separator CO 2 Condensor Pressure reducer 1 bar biocrude/ water collection storage gases 330 °C 180 bar storage Cooler CO 2

13. t 8 March 2004 EMINENT 13 Thermal efficiency Definition:  th = (HHV of biocrude output) * 100 % (HHV of feed) + (HHV from external fuel) For present process design:  th = 55.62 * 100% = 74.9 % 72.98 + 1.3 (Theoretical maximum for this case is 78.6 %)

14. t 8 March 2004 EMINENT 14 Upgrading of biocrude by HDO Principle of catalytic Hydrodeoxygenation has been demonstrated Upgrading cost compensated by higher product value Diesel fraction has excellent ignition properties Potential applications: Transport fuel Kerosine Fuel in high-efficient gas turbine Feedstock for chemicals (via ethylene cracker) Etc.

15. t 8 March 2004 EMINENT 15 HDO process scheme Biocrude Hydrogen HDO reactor system Fractionator (from HTU) electricity NH 3, H 2 S C 1 -C 4 gas H2OH2O Kerosine Gas oil >370°C residue To refininery pool Air transport Diesel fuel for Road transport Lubricating oil; chemical feedstock Naphtha Separator section Recycle gas compressor

16. t 8 March 2004 0 1 2 3 4 5 6 7 8 0123 Feedstock price, $/GJ Biocrude cost, $/GJ First Plant Coal (2 $/GJ) / Crude Oil (12 $/bbl) Replacement Future plant 0 + 40 $ per ton CO 2 avoided energy farmingBiomass residues - 20 + 20 + 60 Production costs of biocrude and costs of avoiding one ton of CO 2

17. t 8 March 2004 EMINENT 17 0 2 4 6 8 10 -20123 Biomass HTU Feedstock Price, $/GJ Total Product Cost, $/GJ First Plant Premium Diesel, assumed crude oil =25 $/bbl Future plant Biomass residuesenergy farming Production costs of HTU diesel

18. t 8 March 2004 EMINENT 18 HTU ® R&D topics Most essential items: Pressurizing feedstock Continuous integrated operation of pilot plant Important items Heating – up feedstock Oil/water separation Product properties / applications Effluent treatment Design data: Phase equilibria Physical properties, esp. at reactor/separator conditions

19. t 8 March 2004 EMINENT 19 Process Development Work in autoclaves, 10 ml, 1 liter, 2 liter Testing of feedstocks and process conditions Continuous pilot plant capacity 20 kg/hour (dry basis) commissioning 1 July 1999 first product prepared: 24 November 1999 24 h run with verge grass feb 2004 3 weeks run planned march 2004

20. t 8 March 2004 EMINENT 20 Results of first development phase Pilot plant construction completed Pilot plant operation: - process principles verified - most initial problems solved - 200 kg biocrude produced Pressurizing of feedstock successfully proven with commercial prototype pump Data on thermodynamics and phase equilibria obtained; model operational Waste water treatment routes defined Product: various applications explored Process design and cost estimation completed Fundamental research to start: NWO – Japan project.

21. t 8 March 2004 EMINENT 21 Commercial HTU demonstration plant Location:Large new waste incinerator in Amsterdam, synergy for O&M, wastewater treatment, etc. Input: Roadside grass 7 ton/h of feedstock, 3 t/h on dry basis Output:1,4 t/h biocrude (incl ash) Capital investment 17 M€, startup 2006-2007

22. t 8 March 2004 EMINENT 22 Commercial HTU plant