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1.8 Atomic H/C ratio 1.6 1.4 1.2 1.0 0.8 0.6 0.4 0.2 0
Anthracite Increased Heating Value Coal Lignite Lignin Peat Wood Biomass Cellulose
0.2
0.6
0.8
Gr (kJ/mol)
50
100
150
200
BUT: catalyst does not exist! (s) CO2, CH4 and C300 250 more stable at low temperature
350
Temperature (C)
Gasification in a CHO-diagram
0.0 1.0
0.2
0.8
Mol % H
0.6
0.4
0.6
Mol % C CO CO2
0.2
CH 4
0.8
0.0 1.00
Mol % O
2000
tio ra
1500
1227C
1000
927C carbon boundary temperature
Product gas
Gasifier
total =
Gasification efficiency
90 88 86 overall efficiency 84 82 80 78 76 74 72 70 68 66 64 62 60 0.0 0.2 0.4 0.6 0.8 chemical efficiency
C H/ gh hi io rat C H/ w lo io rat
low H /C ra tio high H/C r atio carbon boundary low H/C ratio temperature high H/C 927C ratio low H/C ratio high H/C 1227C ratio
Intermediate conclusions
Fuels with high O/C ratio have relatively high chemical exergy ( = 1.12-1.14 for biomass, 1.05 for solid carbon) ch, fuel = LHV fuel and therefore lower gasification efficiency Fuels with high O/C ratio are over-oxidized at practical gasification temperatures (1200-1500 K)
Biomass torrefaction
1.8 Atomic H/C ratio 1.6 1.4 1.2 1.0 0.8 0.6 0.4
1. 2. 3. Thermo of gasification Biomass torrefaction TW as a gasifier fuel Increased Heating Value Anthracite Coal Lignite Lignin Peat Wood Biomass Cellulose
0.2 0
0.2
0.6
0.8
Torrefaction experiments
Thermo balance (TGA):
reaction kinetics
0.80 0.75 0.70 0.65 0.60 0.55 0.50 0.45 1000 1500 2000 2500 3000 3500 4000 4500
straw
xylan
5000
150 5500
Time (s)
Temperature (C)
0.85
beech willow
270
larch beech willow
0.80 0.75 0.70 0.65 0.60 0.55 0.50 0.45 1000 1500 2000 2500 3000 3500 4000 4500
straw
190 170
xylan
5000
150 5500
Time (s)
Temperature (C)
0.85
O
H2CO
OH
Hemicellulose
OH
OH
O
O-Ac
O
O-Ac
OH
OH
OH
O
OH
O
OH
O
O-Ac
Highly reactive
Cellulose
Hardly reactive
Lignin
Only sidechains
Composition hemicelluloses
4-O methyl glucuronoarabinoxylan (wt%) <1 <1 <1 <1 1-5 80-90 5-15 80-90% 5-15% 15-30 1-5 60-70 1-5 15-30 <1 1-5
C B A time
Reactor
heater
heater
Temp controller
Flow Pressure Temp Tracing inlet 10-50 ml/min Atmospheric 230-300 C 120 C
Condensable volatiles
acetic acid water furfural formic acid hydroxy acetone methanol phenol
14.0%
lactic acid
10.0%
8.0%
6.0%
4.0%
2.0%
0.0%
230C (50 min.) 250C (30 min.) 270C (15 min.) 280C (10 min.) 300C (10 min.)
willow
Non-condensable volatiles
carbon dioxide carbon monoxide
6.0%
5.0%
4.0%
3.0%
2.0%
1.0%
0.0%
230C (50 min.) 250C (30 min.) 270C (15 min.) 280C (10 min.) 300C (10 min.)
willow
21000
20500
20000
19500
19000
18500
18000 220
230
240
250
270
280
290
300
Energy yield
105% Lower heating value retained in solid product [%]
larch
100%
95%
90%
85%
80%
75%
70% 220
230
240
250
270
280
290
300
Low ash, sulphur and nitrogen content Increased energy density: 18 to 21 MJ/kg Reduced moisture content: 10 % to < 2 % Ratio of volatiles/FC: 80/20 to 60/40 Reduced hemi-cellulose: 20-30% < 5 % Friable Cheaper to transport
storage
Demonstration of TW (co-) gasification in entrained flow gasifiers EF pilot plant For stand-alone torrefaction:
Catalytic combustion of volatiles
1. 2. 3. F-T fuels from biomass Biomass torrefaction TW as a gasifier fuel
at ECN; Buggenum?
Techno-economic analysis of torrefactionaided gasification (stand-alone, integrated) versus direct wood gasification