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International Academy of Wood Science Meeting 2006. Has Thermo-chemical Conversion of Wood a Future ? by Xavier DEGLISE Emeritus Professor at University Henri Poincaré, Nancy 1. Introduction Pyrolysis Gasification Carbonisation Liquefaction Conclusion. - PowerPoint PPT Presentation
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13 November 200613 November 2006 IAWS Meeting 2006 XDIAWS Meeting 2006 XD 11
Has Thermo-chemical Conversion of Wood
a Future ?
by Xavier DEGLISE
Emeritus Professor at University Henri Poincaré, Nancy 1Emeritus 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 1Emeritus Professor at University Henri Poincaré, Nancy 1
International Academy of Wood Science Meeting 2006
13 November 200613 November 2006 IAWS Meeting 2006 XDIAWS Meeting 2006 XD 22
1. Introduction
2. Pyrolysis
3. Gasification
4. Carbonisation
5. Liquefaction
6. Conclusion
13 November 200613 November 2006 IAWS Meeting 2006 XDIAWS Meeting 2006 XD 33
Forest Biomass represents 2230 MTOE/year (without deforestation) Forest Biomass represents 2230 MTOE/year (without deforestation) around 65% of 3365 MTOE in potential Renewable Energies. Biomass around 65% of 3365 MTOE in potential Renewable Energies. Biomass could fulfill 22 % of the actual world energy needs…and Wood is the could fulfill 22 % of the actual world energy needs…and Wood is the major biomass!major biomass!
13 November 200613 November 2006 IAWS Meeting 2006 XDIAWS Meeting 2006 XD 44
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 sequestratio
n
13 November 200613 November 2006 IAWS Meeting 2006 XDIAWS Meeting 2006 XD 55
Forests resources are increasing vs time!: C
sequestration
-0,030
0,020
0,070
0,120
0,170
1950 1955 1960 1965 1970 1975 1980 1985 1990 1995
Co
mp
on
en
ts o
f th
e t
ota
l fo
res
t s
ec
tor
sin
k (
Pg
C y
-1)
Tree Biomass
Coarse woody debris
Forest floor
Mineral soil
Wood Products
Total
European forest sector carbon balance 1950 –1999 (Nabuurs et al. 2003) Pg C y-1= Petagram C / year =1015 gram / year
13 November 200613 November 2006 IAWS Meeting 2006 XDIAWS Meeting 2006 XD 66
In EU 25, still fellings remain rather stable, In EU 25, still fellings remain rather stable, and the resource is growing fast!and the resource is growing fast!
0
100
200
300
400
500
600
700
800
1950 1960 1970 1980 1990 2000
Net annual increment
Fellings
Mil. m3 over bark
Latest German inventory gave a net
annual increment of 12 m3.ha-1.y-1
13 November 200613 November 2006 IAWS Meeting 2006 XDIAWS Meeting 2006 XD 77
““Bio energy” will lead to anBio energy” will lead to an extra extra
demanddemand
Value added will be very low
…but the stove needs to burn
Current oil price rise
~ 100 $ /ton CO2 carbon tax
Suitability of residue extraction
from EU 25 forests
13 November 200613 November 2006 IAWS Meeting 2006 XDIAWS Meeting 2006 XD 88
Extra Resource Wood Biomass ?Extra Resource Wood Biomass ?
13 November 200613 November 2006 IAWS Meeting 2006 XDIAWS Meeting 2006 XD 99
Source of Residue Type 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 ResiduesWood Residues
13 November 200613 November 2006 IAWS Meeting 2006 XDIAWS Meeting 2006 XD 1010
Estimated potential of Wood ResiduesEstimated potential of Wood Residuesin the Worldin the World
Overall quantity of WR * Overall quantity of WR * ~~ 2,000 MT/y or 2,000 MT/y or ~~ 650 MTOE/y to compare with 650 MTOE/y to compare with
7,000 MT/y of Forest biomass or 2 230 7,000 MT/y of Forest biomass or 2 230 MTOE/yMTOE/y
WR WR ~ 30% of potential Forest Biomass~ 30% of potential Forest Biomass
* Matti Parikka, Biomass and Bioenergy 27 (2004) 613–620
13 November 200613 November 2006 IAWS Meeting 2006 XDIAWS Meeting 2006 XD 1111
Wood Residues vs “Clean Wood”Wood Residues vs “Clean Wood”in Francein France
Overall quantity of WR: 16 MT / year to compare Overall quantity of WR: 16 MT / year to compare withwith
o ~ ~ 23 MT / Year of processed wood (5 MT/y imported) 23 MT / Year of processed wood (5 MT/y imported)
o ~ ~ 40 MT / Year of Wood biologically produced by the 40 MT / Year of Wood biologically produced by the forestforest
o ~ ~ 20 MT / Year of Fuel Wood (estimated) with 80% 20 MT / Year of Fuel Wood (estimated) with 80% domestic consumptiondomestic consumption
WR represent an important source of Biomass (5.5 WR represent an important source of Biomass (5.5 MTOE)…but is scattered!MTOE)…but is scattered!
WR corresponds only to 6% of the oil consumption WR corresponds only to 6% of the oil consumption (96 MT/y)(96 MT/y)
13 November 200613 November 2006 IAWS Meeting 2006 XDIAWS Meeting 2006 XD 1212
Biomass upgrading into Energy or Chemicals
Co-combustion
Bioprocesses
Fuel cells
EngineTurbine
SNGDMEH2
Fischer Tropschhydrocarbons
Alcohols
Methanol
Ethanol
Bio-fuel
DirectCombustion
Biomass
ElectricityHeat
GasificationPyrolysis
DirectLiquefaction
N/A ?
N/A ?
13 November 200613 November 2006 IAWS Meeting 2006 XDIAWS Meeting 2006 XD 1313
Overview of “Wood thermal Processes”Overview of “Wood thermal Processes”
(Co) combustion GasificationPyrolysis
Wood
Upgrading treatment
CH3OH, CnHm, H2
Direct heating
IndirectHeating
Synthesis/cleaning
Atmospheric or pressurizedO2, air, H2O
Bio-fuels
Direct Liquefaction
syngas
H2O, critical conditions,Hydro liquefaction (H2)
High Pressure
Liquid biomassHeavy bio-oil
slowfast, flash
Heat and Electricity
Flue gas
Engine or Turbine
charoilgas
Charcoal
13 November 200613 November 2006 IAWS Meeting 2006 XDIAWS Meeting 2006 XD 1414
Operating conditions of the thermal Operating conditions of the thermal processesprocesses
Thermal Process
Temperature Atmosphere Products Mean overall Yield
Combustion > 900°C O2 (air) CO2 + H2O + N2
+ ashes to be treated~ 65 %
Pyrolysis < 500°C Inert gas orLow
pressure
char + tars + gas, which proportions are related to the pyrolysis parameters
~ 45 %
Gasification by Fast
pyrolysis
> 700°C Inert gas orLow
pressure
Mainly gas (CO, H2, CH4, C2H4 …) with low quantity
of char used
~ 75 %
Gasification > 800°C Air or H2O vapour
Gas (H2, CO, CO2, CH4, N2) + ashes to be treated
50-60 %
Liquefaction by Fast
Pyrolysis
< 550°C Low pressure
High viscosity liquid (phenols)
~ 75 %
Direct Liquefaction
300°C- 350°CSlurry in water
CO High pressure
High viscosity liquid (phenols) non soluble in
water
~ 80 %
13 November 200613 November 2006 IAWS Meeting 2006 XDIAWS Meeting 2006 XD 1515
1. Introduction
2. Pyrolysis
3. Gasification
4. Carbonisation
5. Liquefaction
6. Conclusion
13 November 200613 November 2006 IAWS Meeting 2006 XDIAWS Meeting 2006 XD 1616
Pyrolysis is the Key Reaction of Pyrolysis is the Key Reaction of allall the thermal Processes the thermal Processes
Pyrolysis
Gasification Liquefaction Charcoal makingCombustion Heated Wood
WOOD
Cutting or Grinding
Drying
13 November 200613 November 2006 IAWS Meeting 2006 XDIAWS Meeting 2006 XD 1717
Mechanism of the pyrolysisMechanism of the pyrolysis
HO LO C ELLULO SE
high T
depolymerization
high T
depolymerization
LIG NIN
fragmentation,decarbonylation(C O),dehydration(H 2O)
transglicos ilation
low T
low T
C har, H 2O,C O, C O 2
C har, C O , CO 2
ac ids, acetol,furfural, lac tons,hydroxyacetaldehyde
levoglucosan and sugars
phenols ,methoxyphenols(guaiacols),dimethoxyphenols(syringols)
C arbonylcompounds,furans, phenols ,C O, C O 2
Primary degradation Sec ondary degradation
Sec ondary degradation
Sec ondary degradation
13 November 200613 November 2006 IAWS Meeting 2006 XDIAWS Meeting 2006 XD 1818
Operating conditions of the pyrolysis Operating conditions of the pyrolysis processprocess
PAH
13 November 200613 November 2006 IAWS Meeting 2006 XDIAWS Meeting 2006 XD 1919
To lower the PAH’sTo 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 200613 November 2006 IAWS Meeting 2006 XDIAWS Meeting 2006 XD 2020
1. Introduction
2. Pyrolysis
3. Gasification
4. Carbonisation
5. Liquefaction
6. Conclusion
13 November 200613 November 2006 IAWS Meeting 2006 XDIAWS Meeting 2006 XD 2121
Possible applications of the Product Possible applications of the Product
GasGas co-combustion in a coal power plant co-combustion in a coal power plant co-combustion in a natural gas power plant without co-combustion in a natural gas power plant without
modifications at the burners 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 for production of Synthetic Natural Gas by
methanation methanation for production of Liquid Fuels by Fischer-Tropsch for production of Liquid Fuels by Fischer-Tropsch
13 November 200613 November 2006 IAWS Meeting 2006 XDIAWS Meeting 2006 XD 2222
Main ReactionsMain Reactions Wood (Pyrolysis) C slightly endothermicWood (Pyrolysis) C slightly endothermic
C + OC + O22 CO CO22 ( (ΔΔHH00= -391,6 kJ mol-1) exothermic= -391,6 kJ mol-1) exothermic
C + HC + H22O O CO+H CO+H22 ( (ΔΔHH00 = + 131,79 kJ mol-1) endothermic = + 131,79 kJ mol-1) endothermic
C + COC + CO22 2 CO ( 2 CO (ΔΔHH00 = + 179,3 kJ mol-1) endothermic = + 179,3 kJ mol-1) endothermic
CO + HCO + H22O O CO CO22 + H + H2 2 ((ΔΔHH00 = - 47,49 kJ mol-1) slightly = - 47,49 kJ mol-1) slightly exothermic exothermic
C + 2HC + 2H22 CH CH44 ( (ΔΔHH00= - 22 kJ mol-1) slightly exothermic = - 22 kJ mol-1) slightly exothermic
With the operating parameters (Pressure, Temperature) it is With the operating parameters (Pressure, Temperature) it is possible to select a gas containing more Syngas (CO+Hpossible to select a gas containing more Syngas (CO+H22) or ) or more SNG (CHmore SNG (CH44))
13 November 200613 November 2006 IAWS Meeting 2006 XDIAWS Meeting 2006 XD 2323
Main kinds of Reactors for Gasification
Updraft and Downdraft reactors have been developed since ~ 1930.
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!
0 5 10 15 20
vapeur/ catalyseur
vapeur/ olivine
vapeur/ quartz
air/ quartz
Tar content (g/Nm3 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 developedsince 1980:- KUNII- FERCO- Our (TNEE)- RENET (Güssing)- ………….
13 November 200613 November 2006 IAWS Meeting 2006 XDIAWS Meeting 2006 XD 2828
We have an old expertise in wood gasification in dual fluidized bed pyrolysis, until the pilot scaleA pilot with a capacity of 500Kg/H pine barks was operating in a pulp mill in 1984/1985.Its power was around 2 MWand it produces a medium BTU Gas (HHV around 16000 KJ/m3)
bois
gaz de pyrolyse recyclé (300 - 400°C)
lit en pyrolyse( ~ 800°C)
char + caloporteur
lit transporté de combustion(950°C)
caloporteur (950°C)
fumées (950°C)
cyclone dépoussièreur
gaz de pyrolyse(850°C)
13 November 200613 November 2006 IAWS Meeting 2006 XDIAWS Meeting 2006 XD 2929
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 CO2 Absorber
13 November 200613 November 2006 IAWS Meeting 2006 XDIAWS Meeting 2006 XD 3333
Complete Syngas Complete Syngas ProcessProcess
GasifierCombustor
Heat Exchangers
Steam Dried Biomass
Air
Water treatment &steam production unit
Fly Ashremoval
Bottom AshExtraction
Catalyst heat
carrier
ShiftReactor
Wet scrubber
SynthesisGas
Gas compression
Flue Gas CO2
elimination
13 November 200613 November 2006 IAWS Meeting 2006 XDIAWS Meeting 2006 XD 3434
Pressurised fl uidised
Bed
Circulating Fluidised
Bed
Fluidised Bed
Downdraf t
Updraf t
1 MW 10 MW 100 MW 1000 MW1 kW 10 kW 100 kW
0,2 kg/ h 2 kg/ h 20 kg/ h 200 kg/ h 2 t/ h 20 t/ h 200 t/ h
Optimum Capacity of Gasification Processes
10t/h could be a great maximum for RW
13 November 200613 November 2006 IAWS Meeting 2006 XDIAWS Meeting 2006 XD 3535
To solve the problem of capacity, it is necessary To solve the problem of capacity, it is necessary to have a pre-treatment process producing a to have a pre-treatment process producing a char from different kinds of biomass, which char from different kinds of biomass, which could be then transformed at a larger scale.could be then transformed at a larger scale.
Such a system is proposed for the production of Such a system is proposed for the production of Hydrogen from BiomassHydrogen from Biomass
The Philosophy of this two step process could be The Philosophy of this two step process could be adapted, as the optimum input feed of the adapted, as the optimum input feed of the gasification must be over 10T/Hgasification must be over 10T/H
13 November 200613 November 2006 IAWS Meeting 2006 XDIAWS Meeting 2006 XD 3636
1. Introduction
2. Pyrolysis
3. Gasification
4. Carbonisation
5. Liquefaction
6. Conclusion
13 November 200613 November 2006 IAWS Meeting 2006 XDIAWS Meeting 2006 XD 3737
cellulose
00,2 0,4 0,6
rapport O/C0,8
pétroles
rapport H/C
1,5asphaltesbitumes
charbons
1000 °C (26,5 %)800 °C (26,7 %)
600 °C ( 31 %)
500 °C (33 %)
400 °C (37,8 %)
300 °C (51,4 %)
200 °C (91,8 %)
(rendement de production en % de la masse anhydre)
lignine
230 °C1
0,5
bois
charbons
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 200613 November 2006 IAWS Meeting 2006 XDIAWS Meeting 2006 XD 3838
Low temperature Pyrolysis for Wood Low temperature Pyrolysis for Wood Residues Residues “The Chartherm Process”“The Chartherm Process”
13 November 200613 November 2006 IAWS Meeting 2006 XDIAWS Meeting 2006 XD 3939
13 November 200613 November 2006 IAWS Meeting 2006 XDIAWS Meeting 2006 XD 4040
1. Introduction
2. Pyrolysis
3. Gasification
4. Carbonisation
5. Liquefaction
6. Conclusion
13 November 200613 November 2006 IAWS Meeting 2006 XDIAWS Meeting 2006 XD 4141
1. Introduction
2. Pyrolysis
3. Gasification
4. Carbonisation
5. Liquefaction
6. Conclusion
Liquid fuels from Syngas
Liquid fuels from Pyrolysis
13 November 200613 November 2006 IAWS Meeting 2006 XDIAWS Meeting 2006 XD 4242
For hydrocarbons the main Reactionof Fischer Tropsch Synthesis:
n CO + (m/2 +n) H2 = CnHm + nH20Catalyst (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 H2 vary as a function of what you want: gas or diesel
With Syngas we can produce Hydrocarbons or Methanol
CO+2H2 = CH3OH
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 200613 November 2006 IAWS Meeting 2006 XDIAWS Meeting 2006 XD 4545
1. Introduction
2. Pyrolysis
3. Gasification
4. Carbonisation
5. Liquefaction
6. Conclusion
Liquid fuels from Syngas
Liquid fuels from Pyrolysis
13 November 200613 November 2006 IAWS Meeting 2006 XDIAWS Meeting 2006 XD 4646
Wood Liquefaction via Fast Pyrolysis
13 November 200613 November 2006 IAWS Meeting 2006 XDIAWS Meeting 2006 XD 4747
Wood Liquefaction via Fast Pyrolysis
Bubbling fluid bed reactor with electrostatic precipitator
Circulating fluid bed reactor
13 November 200613 November 2006 IAWS Meeting 2006 XDIAWS Meeting 2006 XD 4848
Wood Liquefaction via Fast PyrolysisProduct Yield vs temperature
13 November 200613 November 2006 IAWS Meeting 2006 XDIAWS Meeting 2006 XD 4949
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 200613 November 2006 IAWS Meeting 2006 XDIAWS Meeting 2006 XD 5050
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 = CO2 + reduced wood
Wood react with CO, (in fact H2 coming from a shift reaction, CO+H2O = CO2+H2) in water at elevated temperatures (300-350°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 200613 November 2006 IAWS Meeting 2006 XDIAWS Meeting 2006 XD 5151
Direct Hydrothermal Liquefaction (continued)
The overall approx. stoichiometry is:
100 Kg wood + 1 mol CO = 2.2 mol CO2 + 1 mol H2O + 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 200613 November 2006 IAWS Meeting 2006 XDIAWS Meeting 2006 XD 5252
13 November 200613 November 2006 IAWS Meeting 2006 XDIAWS Meeting 2006 XD 5353
1. Introduction
2. Pyrolysis
3. Gasification
4. Carbonisation
5. Liquefaction
6. Conclusion
13 November 200613 November 2006 IAWS Meeting 2006 XDIAWS Meeting 2006 XD 5454
Actually, all the thermo-chemical processes are Actually, all the thermo-chemical processes are not able to convert wood into liquid fuels.not able to convert wood into liquid fuels.
The main problems are:The main problems are:
Capacity of the plant in relationship with the Capacity of the plant in relationship with the input feedinput feed
How to use different sources of dry biomass How to use different sources of dry biomass (residues from forest and wood industries, (residues from forest and wood industries, treated wood, wastes…)treated wood, wastes…)
What to do with the by-products of the different What to do with the by-products of the different steps of the conversions (gas, liquid or solid)steps of the conversions (gas, liquid or solid)
Energy efficiencyEnergy efficiency
13 November 200613 November 2006 IAWS Meeting 2006 XDIAWS Meeting 2006 XD 5555
Idea ?Idea ?
CharcoalTreated Wood wastes
Untreated Wood WastesPrimary Processing
Recovered wood from Forest Operations
Thinnings….
Dry urban WastesPaper, cardboard
Charcoal
Charcoal
Charcoal
Gasification
CO + H2
SNG
Methanol
Bio-diesel (FT)
Hydrocarbons(FT)
Pyrolysis
13 November 200613 November 2006 IAWS Meeting 2006 XDIAWS Meeting 2006 XD 5656
Questions?Questions?