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SUPERGEN - WORK PACKAGE 3

MATHEMATICAL MODELLING WORKSHOP


14 Tuesday March 2006
University of Sheffield

Mathematical Modelling of Biomass Pyrolysis and


Gasification in Lab-
Lab-scale Packed-
Packed-bed Systems

SUWIC SuperGen Research Team: Dr Yao Bin Yang,


Dr Changkook Ryu, Dr David Poole, Paul Gilbert, Adela Khor,
Professor Vida Sharifi,
Sharifi Professor Jim Swithenbank

SUWIC, Sheffield University


Pyrolysis of Wood

Reactor:
Pyrolyser Inner diameter: 12 cm
Condensers Furnace Height: 32.5cm
Controller
Wood Samples:
Nitrogen cubes 20x20mm, 200g
Data Logger/ PC
Gas purge: Nitrogen: 2l/min
Liquid Traps
o
Heating rate: 10 C/min.
Pyrolysis of Wood

Two types of model used:


two-stage parallel reaction model (Janse et al. [23] and Blasi [24] )
to predict final product yield
Pyrolysis of Wood
FG model to predict product compositions
Table 4. Kinetic parameters and precursor pool size (yields) for main species for wood pellets in the FG model (after Jong et al. [3])

Yield per
Precursor pool
precurs
identifier A (s-1) E/R (K) σ/R (K) or pool
per evolved
wt% (daf)
species
1-CO2 5.2×1011 18,300 900 0.95
2-CO2 5.2×1011 20,500 500 3.10
3-CO2 2.8×1012 24,830 900 0.90
1-CO 5.2×1011 20,300 500 1.90
2-CO 6.5×1012 26,300 3200 3.05
3-CO 2.8×1012 35,930 3300 1.80
1-H2O 5.2×1011 19,900 1200 11.94
2-H2O 4.4×1012 26,000 2500 3.0
1-CH4 6.5×1011 19,200 800 0.05
2-CH4 6.5×1011 22,500 800 0.6
3-CH4 3.1×1012 27,700 2100 0.6
1-H2* 3.1×1012 30,700 2100 0.1
1-tar 5.2×1011 20,500 500 38
1-C2H4 2.8×1012 25,930 800 0.2
1-CH3OH 5.2×1011 17,800 800 0.40
2-CH3OH 2.3×1011 21,030 700 0.39
* Assumed in this
1-CH2O 5.2×10
work
11 18,400 500 1.20
Pyrolysis of Wood
The Furnace
Temperature profile Local heating rate profile
r /r 0 =
0
700 18 0.85
0.76
600 0.33

Local heating rate, ºC/min


0.61
Programmed wall T 16
0.47
500 0.47
Temperature, °C

0.33
400 14 0
Predicted T at the centre 0 (measured) 0.61
300
12 0.76
200 0.85
Measured T at the centre
100 10

0
0 1000 2000 3000 4000 5000 6000 8
Time, sec
1000 1500 2000 2500 3000 3500
Time, sec
Pyrolysis of Wood
Comparison between model prediction and experiments
for the yields of final products
50

Tar
40

Gas
Yield, wt%

30

Char

20

10
300 400 500 600 700 800
Final tem perature, ºC
Pyrolysis of Wood

Packed-bed compared to TGA test

120

100

80
M/M0x100%

Packed-bed
60 pyrolyser
(predicted)
TGA
40
test

20

0
0 1000 2000 3000 4000 5000

Time, sec
Pyrolysis of Wood

Gas compositions

18 Wood Temperature, ºC
1000
70 1500
160 2000
250 2500
340 3000
430 3500
520 4000
610 4500
700 5000
700
16
16 50
CO2
14 CO 14 CO

Gas composition, vol %


40
Gas composition, vol %

12 12
10
CO2 CO2 30
10
CO
8 8 20
CH4 CH4
6 CH4 6
H2 10
4 H2 4
C2H4 H2 0
2 2 C2H4
C2H4
C2H6
0 0 -10
1000 2000 3000 4000 5000
100 200 300 400 500 600 700
-2
Time, sec
Temperature, ºC

FG model Measurement
Pyrolysis of Wood

Some preliminary conclusions from the pyrolysis modelling

Secondary reactions (tar cracking) becomes important for real (large-


scale) system, different from TGA data; Modelling experiences with
different biomass or its derived fuels show different tar cracking abilities
, suspected to related to mineral content in the fuel.

FG model requires refining and improvements, especially the ability to


predict the final product yields. FG-biomass model newly developed
at Advanced Fuel Research, USA, will be tested and assessed.

Thanks Miss N Anh Phan for carrying out the wood pyrolysis tests
Conceptual Modelling Study on
Pyrolysis Tube with Emphasis on
Tar Cracking
Pyrolysis Tube & Tar Cracking

Nitrogen Gases
Tar

Biomass
feed Char

Heated wall 500∘C - 800∘C


Pyrolysis Tube & Tar Cracking

The Model

Gases
k1 Gases
k4
Biomass k2
Tar
k5
k3 Char

Char

Ki =Ai exp(-
exp(-Ei/RT) (i=1,2,3,4,5)
Pyrolysis Tube & Tar Cracking
o
Wall at 700 C
200 1000
180 Solid T
Gas T 800
160
140

Temperature, K
600
120 Hot char layer
mass %

100 400
80
200
60 Fixed carbon
40
0
20 Volatile matter
Moisture
0 -200
0 100 200 300 400 500 600 700
Tube length, mm
Pyrolysis Tube & Tar Cracking
o
Wall at 700 C
50

H2O
40
Tar
30
Vol %

20

H2
CO
10 CH4
CO2
0
0 100 200 300 400 500 600 700

Tube length, mm
Pyrolysis Tube & Tar Cracking

Tar concentration (vol


(vol%)
vol%)
at tube exit
Wall Temperature Tube-length Tube Length
500mm 800mm
o
500 C 36.4% 33.5%

600oC 25.7% 15.8%

700oC 18.0% 1.07%

800oC 7.1% 0.4% (4000ppm)


Pyrolysis and Gasification

Sub-
Sub-Conclusions

Hot char layer can reduce tar significantly in the pyrolysis process;

Further cracking of tar can be achieved by steam gasification, to 1/8


of that from pyrolysis with nitrogen;

Problem with tube steam gasification – char gasification rate is too low
to match the pyrolysis rate and an additional/separate char gasifier
reactor is required.
THANKS