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Production of Drop-in Transportation Fuels via Combined Biomass Gasification-
Fischer-Tropsch Synthesis
Amit Gujar, Jong Baik, Nathaniel Garceau, Nazim Muradov and Ali T-Raissi
Florida Solar Energy CenterUniversity of Central Florida
29 September 2010
FESC 2010 Summit, Orlando
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Objectives & Approach
• Demonstrate, at pilot-scale, production of transporatation fuel from biomass feedstock
• Build a PDU-scale oxygen-blown gasifier capable of steady-state operation.
• Fabricate a multi-tube Fischer-Tropsch (FT) reactor capable of yielding 1L/8hr liquid hydrocarbon fuel
• Integrate, operate and optimize integrated combined biomass gasification and FT synthesis reactor.
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Introduction
Pine wood
pellets
Pine charcoal
pellets
Citrus pulp
pelletsDuckweedRiver
algae
Ash
Wood pellets, algae, citrus waste, etc.
water
fuel refining
F-T reactor
conditioner
scrubber
gasifier
O2
raw bio-fuel
diesel
gasoline
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Introduction
• Ideal biomass gasification reaction-
CH1.4O0.6 + 0.4 O2 0.7 CO + 0.3 CO2 + 0.6 H2 + 0.1 H2O
• Ideal Fischer-Tropsch (FT) synthesis reaction-
CO + 2 H2 -CH2- + H2O
Other reactions
CO+H2O------> CO2 + H2
C+CO2-----> 2CO
CO+3H2----->CH4 +H2O
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Gasification Reactor
/
SUS304
200psig cylinder
Biomass
(charcoal, wood
pellet etc.)
Glass fiber
insulation
Insulating riser
sleeve
Hearth zone
Grate/flow
diffuser
Ash collector
Cyclone
• 3.25” Hearth dia.
• 9” Internal dia. of the riser sleeve.
• 41 lt of biomass volume capacity.
• 200psig pressure rating.
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Results – Biomass Gasification (1)
Optimum [H2O]0/[O2]0 molar feed ratio appears to be in the range of 4-5.
Feed [H2O]
0/[O
2]0 ratio, -
0 1 2 3 4 5
H2/C
O &
CO
/CO
2 r
atios a
nd C
gasifie
d/C
com
buste
d,
-
0.0
0.2
0.4
0.6
0.8
1.0
1.2
1.4
1.6
1.8
H2/CO in syngas
Cgasified/Ccombusted
Linear fit to data
CO/CO2 in syngas
Small gasifier
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Results – Biomass Gasification (2)
High O2 mass flow rate leads to higher concentration of H2 & CO in the syngas as well as higher gasification rates.
Useful data for sizing the gasifier
Specie
s c
oncentr
ation,
%
0
20
40
60
80
100
Input oxygen mass flow rate, g/min
0 1 2 3 4 5 6
Gasific
ation r
ate
& s
yngas p
roduction r
ate
, g/m
in
0
2
4
6
8
10
12
Gasification rate
Syngas mass flow rate
Linear fit to data
[H2O]/[O2]= 2.25
H2
CO
CO2
CH4
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FT Reactor Design
• Twelve (12) 1” OD SS316 tubes
• 6 cartridge heaters
Cartridge heaters
Syngas from
gasifier
FT reactor
(1"OD SS316)
Copper spacers
Steam inlet
Steam outlet
Liquid fuel
to condenser
FT reactor / Heater
arrangement
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Results – FT Synthesis (1)
• Co catalyst tested at 250°C, 200 psig, 3,106 mL/gcat.hr
Elapsed time, hrs
0 10 20 30 40 50
Specie
s c
onvers
ion/s
ele
ctivity,
%
0
20
40
60
80
100
CO conversion
CH4 selectivity
CO2 selectivity
Fit to data
33% CO & balance H2 over 20% Co-SiO2
Gasoline range (C5-C10) 48.98 wt%
Kerosene/jet fuel range (C11-C12)
15.08
Diesel range (C13-C16) 21.10
Lube oil and wax range (C17-C26)
14.84
Space-time yield = 0.24 g/gcat.hr
H2 conversion
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Results – FT Synthesis (2)Scale up studies Temperature effect (H2:CO=2:1 & 450 mL/min
flow)
Temperature, oC
180 190 200 210 220
Specie
s c
onvers
ion/s
ele
ctivity,
%
0
20
40
60
80
100
H2 conversion
CO conversion
CH4 selectivity
CO2 selectivity
C2-C4 selectivity
Fit to data
Space-t
ime y
ield
, g/g
cat/
hr
0.00
0.02
0.04
0.06
0.08
0.10
0.12
STY
Nonlinear fit to STY data
• Increase in temperature leads to increase in conversions and space time yields of liquid product
CH4
CO2
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Results – FT Synthesis (3)Effect of space velocity at 220°C
Syngas flow rate, mL/min
400 500 600 700 800 900
Specie
s c
onvers
ion/s
ele
ctivity,
%
0
20
40
60
80
100
H2 conversion
CO conversion
CH4 selectivity
CO2 selectivity
C2-C4 selectivity
Space-t
ime y
ield
, S
TY
, g/g
cat.
/hr
0.10
0.11
0.12
0.13
0.14
0.15
STY
• Increasing the syngas flow rate eventually leads to increase in
methane light gas selectivity due to exothermicity of the reaction thus
leading to decrease in liquid yields.
CO2
CH4
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Results – FT Synthesis (4)
Increasing pressure helps but reaction does proceed at low pressures, as well (unlike Fe catalyst)
Total pressure, psig
40 60 80 100 120 140 160
Convers
ion/s
ele
ctivity,
%
0
20
40
60
80
100
H2 conversion
CO conversion
CH4 selectivity
CO2 selectivity
C2-C4 selectivity
40 60 80 100 120 140 160
Space-t
ime y
ield
, S
TY
, g/g
cat.
/hr
0.10
0.12
0.14
0.16
0.18
0.20
STY
CH4
CO2
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Results – FT Synthesis (5)
Decrease in the CH4 selectivity as CO2
concentration in the feed increases
CO2 concentration in syngas, %
0 10 20 30 40 50
Convers
ion/s
ele
ctivity,
%
0
20
40
60
80
100
H2 conversion
CO conversion
CH4 selectivity
C2-C4 selectivity
Space-t
ime y
ield
, S
TY
, g/g
cat.
/hr
0.06
0.08
0.10
0.12
0.14
STY
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Results – FT Synthesis (6)Effect of space velocity (230°C & H2:CO= 1:1)
Syngas flow rate, LPM
0.40 0.60 0.80 1.00 1.20
Convers
ion/s
ele
ctivity,
%
0
20
40
60
80
100
H2 conversion
CO conversion
CH4 selectivity
CO2 selectivity
C2-C4 selectivity
Space-t
ime y
ield
, S
TY
, g/g
cat.
/hr
0.05
0.10
0.15
0.20
0.25
STY
• Upto 50% more liquid yield per tube when H2:CO=1:1
H2
CO
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Summary of FT Tests
• Using Syngas of H2:CO=1:1 is preferable if the aim is to get maximum liquids out in a single pass mode.
• The use of syngas of H2:CO=2:1 is preferable if the aim is to have maximum utilization of the inlet gas.
• Presence of CO2 is helpfully in controlling the exothermicity of the reaction thus reducing the methane and light gas selectivity.
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Acknowledgement
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