Gasifier fuels

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

0.4 Atomic O/C ratio

0.6

0.8

Which fuel can be converted to gas with the highest efficiency?

A. Solid Carbon, because it has the highest calorific value B. Cellulose, because it requires less oxygen C. It does not matter D. I dont know

Reaction Gibss function Gr

C6(H2O)5 + H2O = 6 CO + 6 H2
150 100 50 0

Gr (kJ/mol)

-50 -100 -150 -200 -250 -300 -350 -400

50

100

150

200

BUT: catalyst does not exist! (s) CO2, CH4 and C300 250 more stable at low temperature

350

Scientist dream: kinetic pathway to synthesis gas

Temperature (C)

Gasification in a CHO-diagram
0.0 1.0

0.2

0.8

Mol % H
0.6

0.4

0.6

coal lignite peat biomass

1500 K 1100 K 1000 K 0.4 900 K 700 K

Mol % C CO CO2
0.2

CH 4
0.8

1.0 0.00 0.25 H2O 0.50 0.75

0.0 1.00

Mol % O

Gasification at carbon boundary

2500
low C H/ tio ra h hig C H/

Gasification temperature (C)

2000

tio ra

1500

1227C

1000
927C carbon boundary temperature

500 0.0 0.2 0.4 0.6 0.8

Thermodynamic efficiency of gasifiers

Fuel, ch = 18000-39000 kJ/kg Oxygen, ch = 124 kJ/kg

Product gas

Gasifier

Steam, ch = 527 kJ/kg ph = 92 kJ/kg

total =

m , gas ( ch , gas + ph , gas ) m ,oxygen ch ,oxygen m , fuel ch, fuel

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

Thermodynamic efficiency (%)

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

carbon boundary temperature 927C 1227C

Atomic O/C ratio of fuel

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 needs to be upgraded!!

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

Torrefaction (at 250-300C) Torrefied Wood

0.2 0

0.2

0.4 Atomic O/C ratio

0.6

0.8

Torrefaction experiments
Thermo balance (TGA):
reaction kinetics

Small scale oven: Feed Product 2 Product 1

Volatiles steam acetic acid methanol CO2, CO other organics product recovery product analysis mass and energy balances

Weight loss kinetics (250C)

1.00 0.95 0.90
larch cellulose

290 270 250 230 210 190 170

Relative weight (-)

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

Weight loss kinetics (270C)

1.00 0.95 0.90 290
cellulose

270
larch beech willow

Relative weight (-)

0.80 0.75 0.70 0.65 0.60 0.55 0.50 0.45 1000 1500 2000 2500 3000 3500 4000 4500

250 230 210

straw

190 170
xylan

5000

150 5500

Time (s)

Temperature (C)

0.85

Torrefaction Reactivity (at 250-300C)

COOH

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

Deciduous vs. coniferous wood

Composition
Polymer Lignin (wt%) Cellulose (wt%) Hemicelulloses (wt%) 4-O methyl glucuronoxylan (wt%) Glucomannan (wt%) Galactoglucomannan (wt%) Arabinogalactan (wt%) Other galactose polysaccharides (wt%) Pectin (wt%) Deciduous 18-25 40-44 15-35 Conifer 25-35 40-44 20-32

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

Kinetic model (for willow)

Di Blasi & Lanzetta, 1997 KV1 A KB Hemi-cellulose decomposition (Ea = 76 kJ/mol) V1 B KV2 KC V2 C

Cellulose decomposition (Ea = 152 kJ/mol)

Relative rates 250C 300C 1 5.5 0.025 0.52

Required residence time

0.9 0.8 0.7 0.6 120 0.5 100 0.4 80 0.3 60 0.2 0.1 0 230 240 250 260 270 280 290 300 40 20 0 200 180 160 140

Reaction time [min]

Relative weight [-]

C B A time

Torrefaction temperature [C]

Set-up for product analysis

Argon Pressure controller Mass flow controller

Reactor

heater

heater

Temp controller
Flow Pressure Temp Tracing inlet 10-50 ml/min Atmospheric 230-300 C 120 C

Gasbag Cooling Cooling Cold trap

Tracing outlet 180 C

Condensable volatiles
acetic acid water furfural formic acid hydroxy acetone methanol phenol

14.0%

lactic acid

12.0% Condensable volatile yield (wt%)

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%

Non-condensable volatile yield (wt%)

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

LHV of solid product

21500 Lower heating value of solid product [kJ/kg dry]
brown green larch willow 10 minutes 15 minutes

21000

20500

30 minutes 50 minutes 60 minutes

20000

19500

19000

18500

18000 220

230

240

250

260 Temperature (C)

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

260 Temperature (C)

270

280

290

300

Torrefied wood as a gasifier fuel

Attractive Gasification Properties

1. 2. 3. F-T fuels from biomass Biomass torrefaction TW as a gasifier fuel

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

50-85% less electricity for size reduction

Densification from 400 kg/m3 to pellets > 800 kg/m3 possible

Actions for future development

Construction & demonstration of continuous torrefaction reactors airless drying unit in Sneek

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