A P P L I C A B L E T O S M A L L S C A L E W O O D P R O C E S S I N G P L A N T S I N N E W Z E A L A N D
C H R I S P E N N I A L L
D R C H R I S W I L L I A M S O N
D R A A R O N M A R S H A L L
P R O F . S H U S H E N G P A N G
Reactor and Catalyst Development for Fischer-Tropsch Synthesis
Objectives
Make biomass based Fischer-Tropschwork in New Zealand!
Plant configuration Reactor/Catalyst development
Plant Configuration
Think outside biomass supply vs. economy of scale squeeze
Sawmill Integration
F-T
Advantages
•Heat Sink
•Existing wood supply
chain
•Electricity requirement
-Once through process
Sized on requirement, not on compromise!!!
Modelling – 3 scenarios
Scenario 1 Scenario 2 Scenario 3
•Meet all on peak mill
electricity requirements
•Meet heat requirements
•Maximise FT production
•Meet off peak mill
electricity requirements
•Meet heat requirements
•Maximise FT production
•No Electrical Generation
•Meet heat requirements
•Maximise FT production
GasifierWood
45 MW
BoilerCleaning& F-T
GasEngineFT
4.9 MWPower
1.4 MW
Steam 7.8 MW
Drying 10 MW
GasifierWood
43 MW
BoilerCleaning& F-T
GasEngineFT
4.9 MWPower
0.36 MW
Steam 7.8 MW
Drying 9.7 MW
GasifierWood
29 MW
BoilerCleaning& F-T
FT
3.2 MW
Steam 7.8 MW
Drying 6.7 MW
Modelling - Methodology
Sawmill energy model workbook
Input/Output workbook
Chemical Equilibrium
model workbook
HYSYS model Economic workbook
Modelling - Results
Scenario 1 Scenario 2 Scenario 3
•Meet all on peak mill
electricity requirements
Capital Cost
$NZ 36 M
Breakeven
FT Crude Cost
$US 147 bbl
Production rate
74 bbl/day
•Meet off peak mill
electricity requirements
Capital Cost
$NZ 33 M
Breakeven
FT Crude Cost
$US 154 bbl
Production rate
75 bbl/day
•No Electricity Generation
Capital Cost
$NZ 19 M
Breakeven
FT Crude Cost
$US 199 bbl
Production rate
49 bbl/day
-Based on wood cost of $10 odt, for $40 odt fuel price is $209 for Scenario 1-Assumed error of +/- 25% for capital cost estimation
Modelling Conclusions
The breakeven prices for the FT crude are similar to peak oil prices of recent years
Scenario 1 and 2 are a better solution due to lower product production costs as well as protection
from electricity price volatility
All scenarios are very sensitive to capital cost variations
Catalyst and Reactor Development
Reactor Selection
High performance i.e. good catalyst utilisation and conversion
Easily Scalable
Catalyst development
Suitable for smaller scale
Suitable for reactor choice
Favourable α for maximum
production from once through process
Microchannel Reactor
What is it? Reactor with channels of dimensions between 0.1-5mm
Advantages
Heat and mass transfer rates orders of magnitude higher than
traditional reactors
Effectively a small fixed bed reactor
Easily scalable – number up rather than scale up
Very suitable to small scale once through process
Microchannel Reactor
Reactor Design What we made
Manufacturability
-No exotic materials-No specialised manufacturing
techniques
-Repeatable-Scalable
0.2mm 316ss shimWire cut channels 0.3mm x
50 per shim
-Aluminium foil gasketing-25mm hardened tool steel top and
bottom plates with cartridge heaters
Trial Rig
Micro GC
64% H2
32% CO
4% N2
F
T2
T1
T4
N2
H2
Flow meter
P1
P2
T3Cooling
VentReactor
Collection pot
Heaters
Microchannel reactor washcoats
Neat cobalt nitrate Cobalt on titania Combustion synthesis
-Simple-Easy to add solution-Repeatable
-Potentially wasteful of cobalt-Deactivation
-More traditional-Expect less deactivation
-Questionable repeatability
-Expect tighter distribution of crystal size
-Questionable repeatability
Results - Conversion
240
225
210
240
0
1
2
3
4
5
6
7
8
9
10
Cobalt Cobalt on titania
Combustion synthesis
Fixed bed
240 9.7 3.6 3.3 0.24
225 2.7 1.4 0.84 0.077
210 1.4 0.75 0.67 0.04
240 4.6 2.4 2.29 0.14
Temperature (oC)
Co
nv
er
sio
n (
g p
ro
du
ct/
g c
ata
lys
t/h
r)
Results - Deactivation
0
10
20
30
40
50
60
Cobalt Cobalt on titania Combustion synthesis Fixed bed
De
ac
tiv
ati
on
(%
)
Comparison between conversion of first and last 240oC run
Methodology – Liquids analysis
0
0.01
0.02
0.03
0.04
0.05
0.06
0.07
0.08
1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30
Frac
tio
n o
f to
tal p
rod
uct
Wt
%
Carbon number
Development of method and standards in GC
Methodology – Liquids analysis
0
0.01
0.02
0.03
0.04
0.05
0.06
0.07
0.08
1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40
Frac
tio
n o
f to
tal p
rod
uct
Wt
%
Carbon number
Wn/n = (1-α)2αn-1
Methodology – Liquids analysis
Log(Wn/n)
-5
-4.5
-4
-3.5
-3
-2.5
-2
-1.5
-1
-0.5
0
0 5 10 15 20 25 30 35 40 45
Lo
g(W
n/n
)
Carbon number (n)
Results – Liquids analysis
0.6
0.65
0.7
0.75
0.8
0.85
0.9
0.95
Cobalt Cobalt on titania Combustion synthesis Fixed bed
Se
lec
tiv
ity
(α
)
240
225
210
240
Values of α for various catalysts over temperature range
Results – Liquids analysis
0
10
20
30
40
50
60
70
80
90
240 225 210 240
Yie
ld (
wt%
)
Temperature (oC)
C20+
C5-C19
0
10
20
30
40
50
60
70
80
90
240 225 210 240
Yie
ld (
wt%
)
Temperature (oC)
C20+
C5-C19
0
10
20
30
40
50
60
70
80
90
240 225 210 240
Yie
ld (
wt%
)
Temperature (oC)
C20+
C5-C19
0
10
20
30
40
50
60
70
80
90
240 225 210 240
Yie
ld (
wt%
)
Temperature (oC)
C20+
C5-C19
Cobalt Cobalt on titania
Combustion synthesis Fixed bed
Results – SEM analysis
Cobalt washcoat
Results – SEM analysis
Cobalt washcoat
Results – SEM analysis
Cbaltwashcoat
Results – SEM analysis
Cobalt washcoat
Combustion synthesis method
Where to from here?
Further SEM analysis
Further testing
-Longer runs-More conditions
-Select conditions for optimisation of small scale FT i.e. pressure effects
Modelling of microchannel reactor
Stretch goal – incorporate FT rig with lab gasifier
Acknowledgments
Dr Chris Williamson
Dr Aaron Marshall
Prof. Shusheng Pang
Michael Sandridge
Woei-Lean Saw
Rest of the technical staff
Foundation for Research, Science and Technology
And Thank You for Listening!!
