Reactor and Catalyst Development

for Fischer-Tropsch Synthesis

APPLICABLE TO SMALL SCALE WOOD

PROCESSING PLANTS IN NEW ZEALAND

CHRIS PENNIALL
DR CHRIS WILLIAMSON
DR AARON MARSHALL
PROF. SHUSHENG PANG
 Objectives

Make biomass based Fischer-Tropsch

work in New Zealand!

Plant configuration Reactor/Catalyst

development
 Plant Configuration

Think outside biomass supply vs. economy of scale squeeze

Advantages

Sawmill Integration
Heat Sink

Existing wood supply

chain

Electricity requirement
-Once through process

Sized on requirement,
F-T not on compromise!!!
 Modelling 3 scenarios

Scenario 1 Scenario 2 Scenario 3

Meet all on peak mill Meet off peak mill No Electrical Generation
electricity requirements electricity requirements

Meet heat requirements Meet heat requirements Meet heat requirements

Maximise FT production Maximise FT production Maximise FT production

Wood Gasifier Wood Gasifier Wood Gasifier
45 MW 43 MW 29 MW

Cleaning Boiler Cleaning Boiler Cleaning Boiler

& F-T & F-T & F-T

Gas Gas Steam 7.8 MW

Steam 7.8 MW Steam 7.8 MW
FT Engine FT Engine Drying 9.7 MW FT
Drying 10 MW Drying 6.7 MW
4.9 MW 4.9 MW 3.2 MW
Power Power
1.4 MW 0.36 MW
 Modelling - Methodology

Sawmill energy
model workbook

Input/Output Chemical HYSYS model Economic

workbook Equilibrium workbook
model workbook
 Modelling - Results

Scenario 1 Scenario 2 Scenario 3

Meet all on peak mill Meet off peak mill No Electricity Generation
electricity requirements electricity requirements

Capital Cost Capital Cost Capital Cost

$NZ 36 M $NZ 33 M $NZ 19 M

Breakeven Breakeven Breakeven

FT Crude Cost FT Crude Cost FT Crude Cost
$US 147 bbl $US 154 bbl $US 199 bbl

Production rate Production rate Production rate

74 bbl/day 75 bbl/day 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 Catalyst development

High performance i.e. good catalyst Suitable for reactor choice

utilisation and conversion

Favourable for maximum

Easily Scalable production from once through process

Suitable for smaller scale

 Microchannel Reactor

What is it? Reactor with channels of

dimensions between 0.1-5mm

Advantages

Heat and mass transfer rates Effectively a small fixed bed reactor
orders of magnitude higher than
traditional reactors

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
0.2mm 316ss shim
Wire cut channels 0.3mm x
50 per shim
-Repeatable
-Scalable

-Aluminium foil gasketing

-25mm hardened tool steel top and
bottom plates with cartridge heaters
 Trial Rig
T1 Heaters

Reactor
N2 Vent

P2
T2 T4 Micro GC

H2
P1

F Cooling
T3
64% H2 Flow meter
Collection pot
32% CO
4% N2
 Microchannel reactor washcoats

Neat cobalt nitrate Cobalt on titania Combustion synthesis

-Simple -More traditional -Expect tighter

-Easy to add solution -Expect less deactivation distribution of crystal size
-Repeatable

-Potentially wasteful of -Questionable -Questionable

cobalt repeatability repeatability
-Deactivation
 Results - Conversion

10
Conversion (g product/g catalyst/hr)

4
240
3
210
2
225 Temperature ( oC)
1
240
0
Cobalt Cobalt on Combustion Fixed bed
titania synthesis
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
 Results - Deactivation

Comparison between conversion of first and last 240oC run

60

50

40
Deactivation (%)

30

20

10

0
Cobalt Cobalt on titania Combustion synthesis Fixed bed
 Methodology Liquids analysis
0.08
Development of method
and standards in GC
0.07

0.06
Fraction of total product Wt %

0.05

0.04

0.03

0.02

0.01

0
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
Carbon number
 Methodology Liquids analysis
0.08

0.07

Wn/n = (1-)2n-1
0.06
Fraction of total product Wt %

0.05

0.04

0.03

0.02

0.01

0
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
Carbon number
 Methodology Liquids analysis

0
0 5 10 15 20 25 30 35 40 45
-0.5

-1

-1.5
Log(Wn/n)
-2
Log(Wn/n)

-2.5

-3

-3.5

-4

-4.5

-5
Carbon number (n)
 Results Liquids analysis

0.95
Values of for various catalysts over temperature range

0.9

0.85
Selectivity ()

0.8
240
225
0.75 210
240

0.7

0.65

0.6
Cobalt Cobalt on titania Combustion synthesis Fixed bed
 Results Liquids analysis
90 90
80
Cobalt 80
Cobalt on titania
70 70
Yield (wt%)

Yield (wt%)
60 60
50 50
40 C20+ 40 C20+
30 30
C5-C19 C5-C19
20 20
10 10
0 0
240 225 210 240 240 225 210 240
Temperature (oC) Temperature (oC)

Combustion synthesis Fixed bed

90 90
80 80
70 70
Yield (wt%)

Yield (wt%)
60 60
50 50
40 C20+ 40 C20+
30 30
C5-C19 C5-C19
20 20
10 10
0 0
240 225 210 240 240 225 210 240
Temperature (oC) Temperature (oC)
 Results SEM analysis

Cobalt
washcoat
 Results SEM analysis

Cobalt
washcoat
 Results SEM analysis

Cbalt
washcoat
 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 Michael Sandridge

Dr Aaron Marshall Woei-Lean Saw

Prof. Shusheng Pang Rest of the technical staff

Foundation for Research, Science and Technology

And Thank You

for Listening!!