Chemical Looping Gasification for Hydrogen Enhanced Syngas Production with In‐Situ CO2
Capture
August 10, 2015
2015 DOE Gasification Systems Workshop
L.‐S. FanDepartment of Chemical and Biomolecular Engineering
The Ohio State University
Why Syngas ?
Syngas(CO + H2)
Natural Gas
Coal
Biomass
Other Feedstocks:Flash Gas, pet cokes,Liquid oil residue…….
F‐T Processed(Gas To Liquids)
• Naptha,• Jet Fuels,• Disel,• Gasoline,• Lubes,• Waxes….
Methanol(Oxygenates)
• Gasoline,• Acetic Acid,• Formaldehyde,• Dimethyl Ether,• Olefins,• Ethanol,• Syn‐LPG……
Hydrogen • Hydrogen (fuel), • Ammonia,• Urea, • Fertilizers, • Chemicals…….Power Generation, Fuel Cells ……
CH4 or other Carbonaceous
Fuels
CO2 + H2O H2 + Flue Gas
reduction calcinationoxidation carbonation
Oxygen Carrier (Type I) CO2 Carrier (Type II)
CO2 Rich HeatSteam/Air
CO2 Lean CO2
Chemical Looping Systems withCO2 Generation or Separation
Me/MeS
MeO/MeSO4
MeCO3
MeO
Fan, L.-S. Chemical Looping Systems for Fossil Energy Conversions. Wiley, 2010.Ramkumar, S., Fan, L.-S. Energy & Fuels. 2010. 24, 4408.
Chemical Looping Systems withNon-CO2 Generation
CH4 or other Carbonaceous
Fuels
CH4 or other Carbonaceous
Fuels
Syngas CO + H2 Chemicals
Solar Energy/Nuclear Energy
H2O H2 + O2
chemical looping chemical loopingchemical looping
Chueh, W. C., Falter, C., Abbott, M., Scipio, D., Furler, P., Haile, S.M., Steinfeld, A. Science. 2010. 330(6012), 1797.Fan, L.-S., Zeng, L., Luo, S. AIChE Journal. 2015. 61(1), 2.
5
Block Flow DiagramsDOE/NETL Baseline Configuration Case 1
Coal Drying and Preparation
Shell Quench Gasifier
Elevated Pressure ASU
Wet Scrubbing Water Gas Shift MercuryRemoval
Acid Gas Removal Rectisol
Claus Plant Sulfur Product
Combustion TurbineAmbient Air
Steam Turbine
HRSG
Methanol Synthesis
Heat Recovered from Methanol
Synthesis
Tail and Purge Gas to Boiler
CO2
Vent
AmbientAir
Exhaust Gas to Stack
Crude Methanol Product
Natural Gas
Wet Coal
Sour WaterSolid
Waste
Sour Water System
Sour Gas Bypass
Raw Syngas
DryCoal
O2
Recycle Gas
Sour Syngas
Low Temperature Gas Cooling
Acid Gas
Sweet Syngas
Flash Gas
Sour Gas
DOE Baseline AnalysisCase 1: Coal‐to‐Crude‐Methanol without CCS
To Waste Water
Treatment
6
Block Flow DiagramsDOE/NETL Baseline Configuration Case 2
Combustion TurbineAmbient Air
Steam Turbine
HRSG
Heat Recovered from Methanol
Synthesis
CO2
Product
Natural Gas
Fluor Econamine Post‐Combustion CO2 Capture
CO2
Product
Exhaust Gasto Stack
Coal Drying and Preparation
Shell Quench Gasifier
Elevated Pressure ASU
Wet Scrubbing Water Gas Shift MercuryRemoval
Acid Gas Removal Rectisol
Claus Plant Sulfur Product
Methanol Synthesis
Tail & Purge Gas to Boiler
AmbientAir
Crude Methanol Product
Wet Coal
Sour WaterSolid
Waste
Sour Water System
Sour Gas Bypass
Raw Syngas
DryCoal
O2
Recycle Gas
Sour Syngas
Low Temperature Gas Cooling
Acid Gas
Sweet Syngas
Flash Gas
Sour Gas
To Waste Water
Treatment
CO2
Compressor
CO2
Compressor
DOE Baseline AnalysisCase 2: Coal‐to‐Crude‐Methanol with CCS
Ambient Air
OSUReducer
Coal
Low Temp Cooling&
Mercury Removal
Acid GasRemoval(Rectisol)
SweetSyngas
CO2Compressor
CO2Product
MethanolSynthesis
CrudeMethanolProduct
Tail Gas fromMethanolSynthesis toSteam ProductionSour Water
System
SourWater
ClausPlant
AcidGas
Sour Gas SulfurProduct
StrippedWaterFlash Gas
OSU Oxidizer
Coal Gasification for Methanol Production:OSU Process
N2
Sour Syngas
Oxidized OC
Reduced OC
Steam
Master title
Economic AnalysesMethanol Required Selling Price
0.21 0.21 0.18 0.10
0.03 0.05 0.290.14
0.11
0.09 0.09 0.06
0.05
0.14 0.14 0.10
0.09
1.181.23
0.89
0.81
0.00
0.25
0.50
0.75
1.00
1.25
1.50
1.75
2.00
MBL-1 MBL-2 OSU-1 OSU-2
Met
hano
l Req
uire
d Se
lling
Pric
e ($
/gal
)
Capital CostsFixed CostsVariable CostsElectricity CostNG CostsCoal Cost
1.641.78
1.41
1.48
Zones of Metal Oxides for Chemical Looping
A: Combustion
B: Syngas Production
C: Inert
Standard Gibbs Free Energy of R
eactions (kJ/molO2)
Temperature (oC)
Zone A: They can work as oxygen carriers for both CLFO and CLPO. (NiO, CuO, CoO, Fe2O3, and Fe3O4, etc.)
Zone B: They are able to work as oxygen carriers for CLPO but not for CLFO (CeO2, FeO, etc.)
Zone C: They cannot be used as oxygen carriers and are considered as inert materials. (Cr2O3 and SiO2, etc.)
Transition Zone: They are considered as possible CLPO materials with a significant amount of H2O generated. (SnO2, etc.) Recent research focus on Complex Metal Oxides
FeOy
FeOx
CO/H2
CO2/H2O
Fluidized Bed Moving Bed1.E-01
1.E+00
1.E+01
1.E+02
1.E+03
1.E+04
1.E+05
1.E+06
1.E+07
200 400 600 800 1000
Temperature (C)
PCO
2/PC
O
Fe2O3
Fe3O4
FeO
Fe1.E-01
1.E+00
1.E+01
1.E+02
1.E+03
1.E+04
1.E+05
1.E+06
1.E+07
200 400 600 800 1000
Temperature (C)
PCO
2/PC
O
Fe2O3
Fe3O4
FeO
Fe
Fluidized Bed
Moving Bed
(x>y)
Reducer Design Concept
Fluidized Bed V.S. Moving Bed
CH4
CO + H2
CO + H2
CH4
(x>y)
FeOy
• Coal mixed with Oxygen Carrier particles• Tests performed:
• Methane to syngas• Sub‐bituminous and Bituminous coal• Coal to syngas• Co‐injection of methane• Co‐injection of methane and steam
Bench Moving Bed Reducer
• Coal gasification – Coal gasification with OC confirmed – Observed both devolatilization and char
gasification– Achieved 30 – 34% of OC conversion
(FeO)– Proved that OC is capable of converting
CO2 to CO– Justifies further moving bed studies
Experimental Studies – Fixed Bed TestsTest Apparatus
Outlet Gas Results – coal as fuel
Enhancing gas 1L/min
30% CO2, 70% N2
1.6 g Illinois #6 coal mixed with 20 g fully oxidized O.C. @ 1050˚C
Outlet gas
CO
CO2
CH4
H2
Coal to Syngas ‐ Bench Scale Moving Bed Tests
0%
10%
20%
30%
40%
50%
60%
70%
0 20 40 60 80
Concen
tration (Dry)
Time (min)
PRB CoalCO
H2
CO2
CH4
100% Conversion 85% Syngas Purity
Condition: Coal: 4g/minOxygen Carrier: 20g/min
Reducer
Oxidizer C
ombustor
Depleted Air
AirFe3O4
Fe/FeO
Fe2O3
Fuel
CO2
Steam
Hydrogen
Counter-current: Full Combustion
Main Reactions
Reducer: CO+H2+Fe2O3CO2+H2O+Fe/FeO
OxidizerFe/FeO+H2OFe3O4+H2
CombustorFe3O4+O2Fe2O3
Overall ReactionCO+H2+H2O+O2CO2+H2O+H2
0
20
40
60
80
100
8:52:48 AM 10:19:12 AM 11:45:36 AM 1:12:00 PM
Concen
tration (%
)
H2
CO
0
20
40
60
80
100
1:33:36 PM 2:09:36 PM 2:45:36 PM 3:21:36 PM
Concen
tration (%
)
H2
CO
CO2
> 99% CO2 purity generated
>99.99% hydrogen purity at steady state
Li, F., Zeng, L., Velazquez-Vargas, L.G., Yoscovits, Z., Fan, L.-S. AIChE Journal. 2010. 56(8), 2186. Tong, A., Sridhar, D., Sun, Z., Kim, H.R., Zeng, L., Wang, F., Wang, D., Kathe, M.V., Luo, S., Sun,
Y., Fan, L.-S. Fuel. 2013. 103. 495.
OSU Chemical Looping Hydrogen Production Process
Concluding Remarks• From theoretical (thermodynamics and kinetics),
experimental (bench and sub‐pilot), and economic (third party) evidence, the OSU chemical looping gasification technology using coal, shale gas, and/or biomass as feedstock to produce, in one step without the use of molecular oxygen from air separation, to produce a high purity syngas at H2:CO at 2:1 for direct application to generate chemicals and liquid fuels downstream can potentially revolutionize the energy and chemical industries in short years.
• The studies from the concluded DOE Phase 1 project activities with independent economic assessment by WorleyParsons have ascertained the technical soundness, process viability and economic attractiveness of these OSU technologies and prepared for further process scale‐up efforts.
Concluding Remarks (continued)
• The experience from the on‐going high pressure pilot demonstration of H2production at NCCC for the OSU Syngas chemical looping technology can accelerate the gasification commercialization process.
Acknowledgements
National Energy Technology Laboratory: Thismaterial is based upon work supported by theDepartment of Energy under Award NumbersDE‐FE0023915 and DE‐FE0012136
Ohio Coal Development Office (OCDO)of the Ohio Development ServicesAgency (ODSA)
This presentation was prepared as an account of work sponsored by an agency of the United States Government. Neither the UnitedStates Government nor any agency thereof, nor any of their employees, makes any warranty, express or implied, or assumes any legalliability or responsibilities for the accuracy, completeness, or usefulness of any information, apparatus, product, or process disclosed, orrepresents that its use would not infringe privately owned rights. Reference herein to any specific commercial product, process, or serviceby trade name, trademark, manufacturer, or otherwise does not necessarily constitute or imply its endorsement, recommendation, orfavoring by the United States Government or any agency thereof. The views and opinions of the authors expressed herein do notnecessarily state or reflect those of United States Government or any thereof.
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