13 November 2006IAWS Meeting 2006 XD1 Has Thermo-chemical Conversion of Wood a Future ? by Xavier DEGLISE Emeritus Professor at University Henri Poincaré, Nancy 1 Has Thermo-chemical Conversion of Wood a Future ? by Xavier DEGLISE Emeritus Professor at University Henri Poincaré, Nancy 1 International Academy of Wood Science Meeting 2006

13 November 2006IAWS Meeting 2006 XD2 1. Introduction 2. Pyrolysis 3. Gasification 4. Carbonisation 5. Liquefaction 6. Conclusion

13 November 2006IAWS Meeting 2006 XD3 Forest Biomass represents 2230 MTOE/year (without deforestation) around 65% of 3365 MTOE in potential Renewable Energies. Biomass could fulfill 22 % of the actual world energy needs…and Wood is the major biomass!

13 November 2006IAWS Meeting 2006 XD4 But, there is a lot of issues for Forests! 1. Climate change 3. Nature oriented management Forest owner behavior Vulnerability and extremes 2. Increased demand; incl. bio energy New giants: Russia, China 4. Forestry in broader context of all land uses New services & functions: C sequestration

13 November 2006IAWS Meeting 2006 XD5 Forests resources are increasing vs time!: C sequestration European forest sector carbon balance 1950 –1999 (Nabuurs et al. 2003) Pg C y -1 = Petagram C / year =10 15 gram / year

13 November 2006IAWS Meeting 2006 XD6 In EU 25, still fellings remain rather stable, and the resource is growing fast! Net annual increment Fellings Mil. m 3 over bark Latest German inventory gave a net annual increment of 12 m 3.ha -1.y - 1

13 November 2006IAWS Meeting 2006 XD7 “Bio energy” will lead to an extra demand Value added will be very low …but the stove needs to burn Current oil price rise ~ 100 $ /ton CO 2 carbon tax Suitability of residue extraction from EU 25 forests

13 November 2006IAWS Meeting 2006 XD8 Extra Resource Wood Biomass ?

13 November 2006IAWS Meeting 2006 XD9 Source of ResidueType of Residue Forest operations Branches, needles, leaves, stumps, roots, low grade and decayed wood, slashings and sawdust Pulp industry, Sawmilling and planning Bark, sawdust, trimmings, split wood, planer shavings Plywood production Bark, core, sawdust, veneer clippings and waste, panel trim, sanderdust Particleboard production Bark, screening fines, panel trim, sawdust, sanderdust Wood Wastes Packing material, old wooden furniture, wooden building waste (demolition wood) Wood Residues

13 November 2006IAWS Meeting 2006 XD10 Estimated potential of Wood Residues in the World Overall quantity of WR * ~ 2,000 MT/y or ~ 650 MTOE/y to compare with Overall quantity of WR * ~ 2,000 MT/y or ~ 650 MTOE/y to compare with 7,000 MT/y of Forest biomass or MTOE/y 7,000 MT/y of Forest biomass or MTOE/y WR ~ 30% of potential Forest Biomass WR ~ 30% of potential Forest Biomass * Matti Parikka, Biomass and Bioenergy 27 (2004) 613–620

13 November 2006IAWS Meeting 2006 XD11 Wood Residues vs “Clean Wood” in France Wood Residues vs “Clean Wood” in France Overall quantity of WR: 16 MT / year to compare with Overall quantity of WR: 16 MT / year to compare with o ~ 23 MT / Year of processed wood (5 MT/y imported) o ~ 40 MT / Year of Wood biologically produced by the forest o ~ 20 MT / Year of Fuel Wood (estimated) with 80% domestic consumption WR represent an important source of Biomass (5.5 MTOE)…but is scattered! WR represent an important source of Biomass (5.5 MTOE)…but is scattered! WR corresponds only to 6% of the oil consumption (96 MT/y) WR corresponds only to 6% of the oil consumption (96 MT/y)

13 November 2006IAWS Meeting 2006 XD12 Biomass upgrading into Energy or Chemicals Co-combustion Bioprocesses Fuel cells Engine Turbine SNG DME H 2 Fischer Tropsch hydrocarbons Alcohols Methanol Ethanol Bio-fuel Direct Combustion Biomass Electricity Heat Gasification Pyrolysis Direct Liquefaction N/A ?

13 November 2006IAWS Meeting 2006 XD13 Overview of “Wood thermal Processes” (Co) combustionGasification Pyrolysis Wood Upgrading treatment CH 3 OH, C n H m, H 2 Direct heating Indirect Heating Synthesis/cleaning Atmospheric or pressurized O 2, air, H 2 O Bio-fuels Direct Liquefaction syngas H 2 O, critical conditions, Hydro liquefaction (H 2 ) High Pressure Liquid biomass Heavy bio-oil slow fast, flash Heat and Electricity Flue gas Engine or Turbine char oil gas Charcoal

13 November 2006IAWS Meeting 2006 XD14 Operating conditions of the thermal processes Thermal ProcessTemperatureAtmosphereProductsMean overall Yield Combustion> 900°CO 2 (air)CO 2 + H 2 O + N 2 + ashes to be treated ~ 65 % Pyrolysis< 500°CInert gas or Low pressure char + tars + gas, which proportions are related to the pyrolysis parameters ~ 45 % Gasification by Fast pyrolysis > 700°CInert gas or Low pressure Mainly gas (CO, H 2, CH4, C 2 H 4 …) with low quantity of char used ~ 75 % Gasification> 800°CAir or H 2 O vapour Gas (H 2, CO, CO 2, CH 4, N 2 ) + ashes to be treated % Liquefaction by Fast Pyrolysis < 550°CLow pressureHigh viscosity liquid (phenols)~ 75 % Direct Liquefaction 300°C- 350°C Slurry in water CO High pressure High viscosity liquid (phenols) non soluble in water ~ 80 %

13 November 2006IAWS Meeting 2006 XD15 1. Introduction 2. Pyrolysis 3. Gasification 4. Carbonisation 5. Liquefaction 6. Conclusion

13 November 2006IAWS Meeting 2006 XD16 Pyrolysis is the Key Reaction of all the thermal Processes Pyrolysis GasificationCombustionLiquefaction Charcoal making Heated Wood WOOD Cutting or Grinding Drying

13 November 2006IAWS Meeting 2006 XD17 Mechanism of the pyrolysis Mechanism of the pyrolysis

13 November 2006IAWS Meeting 2006 XD18 Operating conditions of the pyrolysis process PAH

13 November 2006IAWS Meeting 2006 XD19 To lower the PAH’s Naphtalene, Anthracene, Pyrene, Benzopyrene …… which are formed during the pyrolysis step of the thermal conversion, it is compulsory: to decrease the Residence Time to increase the Temperature when it is possible!

13 November 2006IAWS Meeting 2006 XD20 1. Introduction 2. Pyrolysis 3. Gasification 4. Carbonisation 5. Liquefaction 6. Conclusion

13 November 2006IAWS Meeting 2006 XD21 Possible applications of the Product Gas co-combustion in a coal power plant co-combustion in a coal power plant co-combustion in a natural gas power plant without modifications at the burners co-combustion in a natural gas power plant without modifications at the burners production of electric energy in a gas turbine production of electric energy in a gas turbine production of electric energy in a gas engine production of electric energy in a gas engine production of electric energy in a fuel cell production of electric energy in a fuel cell as synthesis gas in the chemical industry as synthesis gas in the chemical industry as reduction gas in the steel industry as reduction gas in the steel industry for direct reduction of iron ore for direct reduction of iron ore for production of Synthetic Natural Gas by methanation for production of Synthetic Natural Gas by methanation for production of Liquid Fuels by Fischer-Tropsch for production of Liquid Fuels by Fischer-Tropsch

13 November 2006IAWS Meeting 2006 XD22 Main Reactions Wood (Pyrolysis) C slightly endothermic Wood (Pyrolysis) C slightly endothermic C + O 2  CO 2 (ΔH 0 = -391,6 kJ mol-1) exothermic C + O 2  CO 2 (ΔH 0 = -391,6 kJ mol-1) exothermic C + H 2 O  CO+H 2 (ΔH 0 = + 131,79 kJ mol-1) endothermic C + H 2 O  CO+H 2 (ΔH 0 = + 131,79 kJ mol-1) endothermic C + CO 2  2 CO (ΔH 0 = + 179,3 kJ mol-1) endothermic C + CO 2  2 CO (ΔH 0 = + 179,3 kJ mol-1) endothermic CO + H 2 O  CO 2 + H 2 (ΔH 0 = - 47,49 kJ mol-1) slightly exothermic CO + H 2 O  CO 2 + H 2 (ΔH 0 = - 47,49 kJ mol-1) slightly exothermic C + 2H 2  CH 4 (ΔH 0 = - 22 kJ mol-1) slightly exothermic C + 2H 2  CH 4 (ΔH 0 = - 22 kJ mol-1) slightly exothermic With the operating parameters (Pressure, Temperature) it is possible to select a gas containing more Syngas (CO+H 2 ) or more SNG (CH 4 ) With the operating parameters (Pressure, Temperature) it is possible to select a gas containing more Syngas (CO+H 2 ) or more SNG (CH 4 )

13 November 2006IAWS Meeting 2006 XD23 Main kinds of Reactors for Gasification Updraft and Downdraft reactors have been developed since ~ They produce a low BTU Gas (~ 6000 KJ/m3) with tars. Actually the new systems use mainly fluidized beds and circulating fluidized beds….but they are often too complicated energy output < energy in put!

Problems with Tars! Tar content (g/Nm 3 dry gas) in the fuel gas Güssing EC project

Circulating Fluidized Bed

Advantages of Gasification by fast Pyrolysis in a Circulating Fluidized Bed System product gas nearly free of nitrogen calorific value higher than 13 MJ/Nm³ very low tar content due to steam gasification gas quality is independent of water content in biomass feed now, the apparatus are compact……not enough! a wide range of feedstock can be gasified possibility to use a catalyst as bed material (regeneration of catalyst in combustion zone) to influence the gas composition and gasification kinetic in a more positive way But sometimes energy output < energy input!

Circulating Fluidized Beds Example: FERCO (Battelle) Numerous systems have been developed since 1980: - KUNII - FERCO - Our (TNEE) - RENET (Güssing) - ………….

13 November 2006IAWS Meeting 2006 XD28 We have an old expertise in wood gasification in dual fluidized bed pyrolysis, until the pilot scale A pilot with a capacity of 500Kg/H pine barks was operating in a pulp mill in 1984/1985. Its power was around 2 MW and it produces a medium BTU Gas (HHV around KJ/m 3)

13 November 2006IAWS Meeting 2006 XD29

20 Years later….always the same process developed in the RENET Biomass Power Station, Güssing, Austria (Schematic layout)

Photos of the RENET Pilot which start in Austria in 2001

Circulating Fluidized Bed with CO 2 Absorber

13 November 2006IAWS Meeting 2006 XD33 Complete Syngas Process Gasifier Combustor Heat Exchangers Steam Dried Biomass Air Water treatment & steam production unit Fly Ash removal Bottom Ash Extraction Catalyst heat carrier Shift Reactor Wet scrubber Synthesis Gas compression Flue Gas CO 2 elimination

13 November 2006IAWS Meeting 2006 XD34 Optimum Capacity of Gasification Processes 10t/h could be a great maximum for RW

13 November 2006IAWS Meeting 2006 XD35 To solve the problem of capacity, it is necessary to have a pre-treatment process producing a char from different kinds of biomass, which could be then transformed at a larger scale. To solve the problem of capacity, it is necessary to have a pre-treatment process producing a char from different kinds of biomass, which could be then transformed at a larger scale. Such a system is proposed for the production of Hydrogen from Biomass Such a system is proposed for the production of Hydrogen from Biomass The Philosophy of this two step process could be adapted, as the optimum input feed of the gasification must be over 10T/H The Philosophy of this two step process could be adapted, as the optimum input feed of the gasification must be over 10T/H

13 November 2006IAWS Meeting 2006 XD36 1. Introduction 2. Pyrolysis 3. Gasification 4. Carbonisation 5. Liquefaction 6. Conclusion

13 November 2006IAWS Meeting 2006 XD37 Van KREVELEN Diagram giving the elementary Composition and yield of Charcoal vs carbonization temperature It is possible to select which kind of Char you want: high Carbon content high Yield ……………….. Porosity depends on the heating Rate

13 November 2006IAWS Meeting 2006 XD38 Low temperature Pyrolysis for Wood Residues “The Chartherm Process”

13 November 2006IAWS Meeting 2006 XD39

13 November 2006IAWS Meeting 2006 XD40 1. Introduction 2. Pyrolysis 3. Gasification 4. Carbonisation 5. Liquefaction 6. Conclusion

13 November 2006IAWS Meeting 2006 XD41 1. Introduction 2. Pyrolysis 3. Gasification 4. Carbonisation 5. Liquefaction 6. Conclusion Liquid fuels from Syngas Liquid fuels from Pyrolysis

13 November 2006IAWS Meeting 2006 XD42 For hydrocarbons the main Reaction of Fischer Tropsch Synthesis: n CO + (m/2 +n) H 2 = C n H m + nH 2 0 Catalyst (metal oxides) This process is used in RSA, its name is SASOL, producing around 15 Mio T/y of liquid fuel The relative proportion of CO and H 2 vary as a function of what you want: gas or diesel With Syngas we can produce Hydrocarbons or Methanol CO+2H 2 = CH 3 OH For methanol the main reaction is:

energy efficiency from tree-to-barrel: 44% light products: 11%, power: 14% overall energetic efficiency: about 69% Biomass-derived Fischer-Tropsch diesel production

Stepwise gasification to bio-diesel production

13 November 2006IAWS Meeting 2006 XD45 1. Introduction 2. Pyrolysis 3. Gasification 4. Carbonisation 5. Liquefaction 6. Conclusion Liquid fuels from Syngas Liquid fuels from Pyrolysis

13 November 2006IAWS Meeting 2006 XD46 Wood Liquefaction via Fast Pyrolysis

13 November 2006IAWS Meeting 2006 XD47 Wood Liquefaction via Fast Pyrolysis Bubbling fluid bed reactor with electrostatic precipitator Circulating fluid bed reactor

13 November 2006IAWS Meeting 2006 XD48 Wood Liquefaction via Fast Pyrolysis Product Yield vs temperature

13 November 2006IAWS Meeting 2006 XD49 Bio-oil from fast Pyrolysis  The crude pyrolysis liquid or bio-oil is dark brown and approximates to biomass in elemental composition.  Ready substitution for conventional fuels in many stationary applications such as boilers, engines, turbines  Heating value of 17 MJ/kg at 25% wt. water, is about 40% that of fuel oil / diesel  Does not mix with hydrocarbon fuels  Not as stable as fossil fuels

13 November 2006IAWS Meeting 2006 XD50 Direct Hydrothermal Liquefaction Direct hydrothermal liquefaction involves converting Wood to an oily liquid (crude oil), in a pressurized reactor with CO The reaction was: CO + wood product = CO 2 + reduced wood Wood react with CO, (in fact H 2 coming from a shift reaction, CO+H 2 O = CO 2 +H 2 ) in water at elevated temperatures ( °C) with sufficient pressure to maintain the water primarily in the liquid phase (12-20 MPa) for residence times up to 30 minutes.

13 November 2006IAWS Meeting 2006 XD51 Direct Hydrothermal Liquefaction (continued) The overall approx. stoichiometry is: 100 Kg wood + 1 mol CO = 2.2 mol CO mol H 2 O + 55 Kg of non vapor product. oil yield was 33% of dry wood feed with a rather high energy content, giving a high energy yield, around 65% of the HHV of wood. Hydrothermal treatment is based on early work performed by the Bureau of Mines Albany Laboratory in the 1970s.

13 November 2006IAWS Meeting 2006 XD52

13 November 2006IAWS Meeting 2006 XD53 1. Introduction 2. Pyrolysis 3. Gasification 4. Carbonisation 5. Liquefaction 6. Conclusion

13 November 2006IAWS Meeting 2006 XD54 Actually, all the thermo-chemical processes are not able to convert wood into liquid fuels. The main problems are: The main problems are:  Capacity of the plant in relationship with the input feed  How to use different sources of dry biomass (residues from forest and wood industries, treated wood, wastes…)  What to do with the by-products of the different steps of the conversions (gas, liquid or solid)  Energy efficiency

13 November 2006IAWS Meeting 2006 XD55 Idea ? Charcoal Treated Wood wastes Untreated Wood Wastes Primary Processing Recovered wood from Forest Operations Thinnings…. Dry urban Wastes Paper, cardboard Charcoal Gasification CO + H 2 SNG Methanol Bio-diesel (FT) Hydrocarbons (FT) Pyrolysis

13 November 2006IAWS Meeting 2006 XD56 Questions?