Chemical Looping Technology and CO2 Capture
Transcript of Chemical Looping Technology and CO2 Capture
Chemical Looping Technology and CO2 Capture
L. S. FanDepartment of Chemical and Biomolecular
Engineering The Ohio State University
Columbus, Ohio 43210
by
May 3, 2011
Chemical Looping for Hydrogen Production or Combustion
CO2
CxHy
Metal
Oxide
H2O
Metal
H2O
H2
3
Chemical Looping for Fossil Fuel Conversions
Two typical types of looping reaction systems
Oxygen Carrier (Type I)
Me/MeO, MeS/MeSO4
CO2 Carrier (Type II)
MeO/MeCO3
“1st Meeting of High Temperature Solids Looping Cycle
Network”, Oviedo, Spain, September 15-17 (2009).
“1st International Conference on Chemical
Looping”, Lyon, France, March 17-19 (2010).
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Historical Development of Chemical Looping Technologiesfor Fossil Energy Conversions
TechnologiesLane Process and
Messerschmitt Process
Lewis and
Gilliland ProcessIGT HYGAS Process
CO2 Acceptor
Process
Time Early Twentieth Century 1950s 1970s 1970s
Looping Media Fe/FeO/Fe3O4 Cu2O/CuO FeO/Fe3O4 CaO/CaCO3
Reactor Design Fixed bed Fluidized bed Staged fluidized bed Fluidized bed
Lane Process
Lewis and Gilliland Process
IGT Process
CO2 Acceptor Process
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IGT Steam Iron HYGAS Process
MO=> M M=> MO
Gas Conversion (%) 65 45
Solid inlet 80% Fe3O4- 20% FeO 95% FeO- 5% Fe
Temperature (oC) 900 900
Reactor Fluid Bed Fluid Bed
– Poor solid phase conversions: Used only about 25% oxygen
capacity of the particles.
– Low gas phase conversions:
– Used iron ore: Low reaction rates
– Only about 40% efficient
– The process not geared towards making pure CO2
Poor Thermo
CO2 Capture from Fossil Energy – Technological Solutions
Source: José D. Figueroa, National Energy Technology Laboratory (NETL), USDOE
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ε ≈ 1
Partial oxidation
/Gasification
ε = 0.88
H2 + CO
407.7 kJ
358.9 kJ
0 Heat Loss
48.8 kJ Exergy Loss
Water Gas Shift
H2 +CO2
393.4 kJ
322.9 kJ
ε = 0.82
ε = 0.89
Fe
514.8 kJ
456.4 kJFe3O4 @1023K
(0.395 mol)
107.1 kJ
71.9 kJ
ε = 0.669
14.3 kJ Heat Loss
36 kJ Exergy Loss
H2 + Fe3O4
485.5 + 107.1 kJ
396.9 +71.9 kJ
ε = 0.82
Carbon
407.7 kJ/mol
407.7 kJ/mol
23.2 kJ Exergy Loss77.8 kJ thermal
energy @ 380 K
12.41kJ Exergy
ε = 0.16
Partial oxidation
I
II
Substance
Enthalpy of degradation
Exergy
Exergy Rate (ε)
Energy/Exery Loss
Additional Energy Input
Final Product
ε ≈ 1
Partial oxidation
/Gasification
ε = 0.88
H2 + CO
407.7 kJ
358.9 kJ
0 Heat Loss
48.8 kJ Exergy Loss
Water Gas Shift
H2 +CO2
393.4 kJ
322.9 kJ
ε = 0.82
ε = 0.89
Fe
514.8 kJ
456.4 kJFe3O4 @1023K
(0.395 mol)
107.1 kJ
71.9 kJ
ε = 0.669
14.3 kJ Heat Loss
36 kJ Exergy Loss
H2 + Fe3O4
485.5 + 107.1 kJ
396.9 +71.9 kJ
ε = 0.82
Carbon
407.7 kJ/mol
407.7 kJ/mol
23.2 kJ Exergy Loss77.8 kJ thermal
energy @ 380 K
12.41kJ Exergy
ε = 0.16
Partial oxidation
I
II
Substance
Enthalpy of degradation
Exergy
Exergy Rate (ε)
Energy/Exery Loss
Additional Energy Input
Final Product
I. Contional Process
Exergetic Efficiency
322.9/407.7 = 79.2%
II. Chemcial Looping Process
Exergetic Efficiency
396.9/(407.7 + 12.41)=94.5%
Exergy Analysis on Hydrogen Production
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Chalmers University of Technology Gaseous Fuel CLC
Photo Courtesy of Professor Anders Lyngfelt
Up to 99% gaseous fuel conversion; Satisfactory (Ni) particle performance;
Solids inventory: 100 – 200 kg/MWth; Solids circulation rate: 4 kg/s·MWth
9State-of-the-art
OSU Syngas Chemical Looping Process
BFW
To Steam
Turbine
Coal
Candle
FilterHot Gas
Cleanup
Sulfur
Byproduct
2000 psi CO2 (with
H2S, Hg, HCl)
Steam
H2 (450 PSI)
Hot Spent Air
O2
N2
Compressor
Gas Turbine Generator
Fe3O4
Fe
Air Oxidation
Fe2O3
Fuel
ReactorH2
ReactorBFW
Fly
Ash
Hot
Syngas
Raw
Syngas
Compressor
Air
Makeup
Purge
Air
Thomas, T., L.-S. Fan, P. Gupta, and L. G. Velazquez-Vargas, “Combustion Looping Using Composite Oxygen Carriers” U.S. Patent No. 7,767,191 (priority date 2003).
Zone 2
Enhancing Gas Fe
Coal/biomass
Fe2O3CO2/H2O
Discussions on Alternative Coal Direct Chemical Looping Reducer
Zone 1
Thomas, T., L.-S. Fan, P. Gupta, and L. G. Velazquez-Vargas, “Combustion Looping Using Composite Oxygen Carriers” U.S. Patent No. 7,767,191 (priority date 2003)
Fan, L.-S., P. Gupta, L.G. Velazquez-Vargas, “Systems and Methods of Converting Fuels” WO 2007/082089 (2006)
Zone 1
Zone 2
Zone 3
Zone 4
Coal/biomass
Particle Fixed Bed Tests
Bench Scale Tests
Time
Sca
le
Sub-Pilot SCL
Integrated Tests
0
5
10
15
20
25
30
35
40
45
50
0 5 10 15 20 25 30 35
Axil Position (inch)
So
lid
Co
nv
ers
ion
(%
)
0
10
20
30
40
50
60
70
80
90
100
Gas C
on
vers
ion
s (
%)
Solid H2 COParticle Reactivity Confirmed
Maximum Operating Temperature Determined
Reactor Performance Confirmed
Syngas Chemical Looping Process Development
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Chemical Looping Reactor Design
FeOy
FeOx
CO/H2
CO2/H2O
(x>y)
FeOy CO/H2
(x>y)
FeOx CO2/H2O
Fluidized BedMoving Bed
FeOy CO/H2
(X>Y)
FeOx CO2/H2O
Fluidized Bed Moving Bed
Moving Bed – The Selected Reactor Type
FeOy
FeOx
CO/H2
CO2/H2O
(X>Y)
Fluidized Bed v.s. Moving Bed
Maximum Solid Conversion
Gas Velocity
Particle Size
11.11%
> Umfv
Small
50.00%
< Umfv
Large
Fluidized Bed v.s. Moving Bed
Maximum Solid Conversion
Gas Velocity
Particle Size
11.11%
> Umfv
Small
50.00%
< Umfv
Large
Maximum Solid Conversion
Gas Velocity
Particle Size
11.11%
> Umfv
Small
50.00%
< Umfv
Large
1.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)
PC
O2/P
CO
Fe2O3
Fe3O4
FeO
Fe
1.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)
PC
O2/P
CO
Fe2O3
Fe3O4
FeO
Fe
Fluidized Bed
Moving Bed
(x>y)
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Coal/
O2
Particulateremoval
H2S Removal
F-Treactor
Productseparation
Liquid Fuel
Gas
Phase
HRSG
H2
H2/CO = 0,5
H2 /CO=2
Gas
ifie
r
Syngas Chemical Looping in CTL Applications – I
Fuel
Rea
ctor
H2
Rea
ctor
CO2
Air
N2
N2
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Syngas Chemical Looping in CTL Applications – II
Steam
from F-T
Biomass
and F-T
byproduct
MeOx
H2 rich gas
MeOy (y < x)
MeOz
(y<z≤x)Air (Optional)
F-T and
Product Upgrade
CO2
H2O
Sequestrable CO2
H2O
Liquid Fuel
Product
Byproduct to
Reactor 1
H2O
(Cooling)
Steam to
Reactor 2
Reac
tor 3
Reac
tor 1
Reac
tor 2
Steam
from F-T
Biomass
and F-T
byproduct
MeOx
H2 rich gas
MeOy (y < x)
MeOz
(y<z≤x)Air (Optional)
F-T and
Product Upgrade
CO2
H2O
Sequestrable CO2
H2O
Liquid Fuel
Product
Byproduct to
Reactor 1
H2O
(Cooling)
Steam to
Reactor 2
Reac
tor 3
Reac
tor 1
Reac
tor 2
3H2 + CO2 -(CH2)- + 2H2O
C + H2O/O2 H2 + CO2/Heat
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Chemical Looping Integrated with Fuel Cell – I
2H2 + O2 2H2O + Electricity
C + H2O/O2 H2 + CO2/Heat
Re
ac
tor 1Biomass
Sequestrable
CO2 and H2O
MeOx
An
od
e
Cath
od
e
H2 rich gasS
OF
C
Steam rich exhaust to Reactor 2
Compressed Air
Oxygen lean air
to Reactor 3
Oxygen lean air
from SOFC
cathode (Optional)
Re
ac
tor 3
Electric
Power
MeOy (y < x)MeOy (y < x)
MeOz
(y<z≤x)
Re
ac
tor 2
Re
ac
tor 1Biomass
Sequestrable
CO2 and H2O
MeOx
An
od
e
Cath
od
e
H2 rich gasS
OF
C
Steam rich exhaust to Reactor 2
Compressed Air
Oxygen lean air
to Reactor 3
Oxygen lean air
from SOFC
cathode (Optional)
Re
ac
tor 3
Electric
Power
MeOy (y < x)MeOy (y < x)
MeOz
(y<z≤x)
Re
ac
tor 2
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Single Loop High Density CFB System (Kirbas et al., 2007)
Two Loop High Density CFB System (Kulah et al., 2008)
Kirbas G, Kim SW, Bi X, Lim J, Grace JR. Radial Distribution of Local Concentration Weighted Particle Velocities in High Density Circulating Fluidized Beds. Paper presented at: The 12th International Conference on Fluidization - New Horizons in Fluidization Engineering; May 13-17, 2007; Vancouver, Canada.
Kulah G, Song X, Bi HT, Lim CJ, Grace JR. A NOVEL SYSTEM FOR MEASURING SOLIDS DISPERSION IN CIRCULATING FLUIDIZED BEDS. Paper presented at: 9th International Conference on Circulating Fluidized Beds; May, 13 – 16, 2008; Hamburg, Germany.
Circulating Fluidized Bed Systems
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Particle Type Ni Cu Fe
Type of Data
Lab
Scale
CFB 120
kW
Lab
Scale CFB 10kW Lab Scale
CFB
300W
Moving Bed -H2
25 kW
Particle Type
NiO/
MgAl2O4
NiO/
MgAl2O4
CuO/
Al2O3 CuO/Al2O3
Fe2O3/
MgAl2O4
Fe2O3/
Al2O3 Composite Fe2O3
Air Flow Rate @1000 MWth and 10% Excess (mol/s) 11784 1309
Volumetric Air Flow Rate at 1 atm and 900 ºC (m3/s) 1134 126
Particle Circulation Rate @ 1000 MWth (kg/s) 4000 10000 3000 6000 8000 10000 800
Reducer Solids Inventory (tonne) 230 160 70total
2100
500 12001500 Total
Oxidizer Solids Inventory (tonne) 390 80 390 n/a 350
Medium Particle Size (μm) 153 120 300 200 153 151 2000
Particle Density (g/cm3) 1.9 5 2.5 2.5 4.1 2.15 2.5
Ut (m/s) 2 0.8 2 1.2 1.1 0.6 11
Uc (m/s) 4 4.8 4.9 4.2 4.8 3.6 4
Use (m/s) 6 6.7 7.5 6.1 6.9 4.9 9.7
Typical Riser Superficial Gas Velocity (m/s) 7.00 12
Bed Area Turbulent Section (if Required) at 1 atm (m2) 231.47 25.18
Bed Area Required for Riser Section at 1 atm (m2) 162.03 10.49
Corresponding Riser Diameter (m) 14.37 3.66
Solids Flux at 1 atm (kg/m2s) 24.69 61.72 18.52 37.03 49.37 61.72 76.23
Number of Beds Needed given 8 m ID Riser 3.23 <1
Number of Beds Needed given 1.5 m ID Riser 91.73 5.94
Ug for a Single 1.5 m ID Riser at 1 atm (m/s) 642.14 71.29
Ug for a Single 8 m ID riser at 1 atm (m/s) 22.58 2.5 (Ug < Ut; N/A)
Required Pressure for a Single 1.5m ID Riser (atm) 91.73 10.00
Solids Flux for a Single 1.5 m ID Riser (kg/m2s) 2264.69 5661.71 1699 3397.03 4529.37 5661.71 452.88
Required Pressure for a Single 8 m ID Riser (atm) 3.23Ug < Ut; N/A
Solids Flux for a Single 8 m ID Riser (kg/m2s) 79.62 199.04 59.71 119.43 159.24 199.04
4000 – 10000 kg/s or 14,000 – 36,000 ton/hour
< 3,000 ton/hour
Oxygen Carrier Selection
Primary Metal Fe Ni Cu Mn Co
Potential Supports Al2O3, TiO2, MgO, Bentonite, SiO2, etc
Cost + – – ~ –
Oxygen Capacity1(wt %) 30 21 20 253 21
Thermodynamics for
CLC
+ ~ + + +
Kinetics/Reactivity2 – + + + –
Melting Points + ~ – + +
Strength + – ~ ~ ~
Environmental& Health ~ – – ~ –
Hydrogen Production + – – – –
1. Maximum theoretical oxygen carrying capacity; 2. Reactivity with CH4; 3. Mn3O4 is the highest oxidation state based on thermodynamics, although not thermodynamically favorable, Mn is assumed to be the lowest oxidation state
Recyclability of Commercial Fe2O3
20
Performance of Composite Fe2O3
0
50
100
150
200
250
300
350
400
450
Fresh
10 Cycles
100 Cycles
Forc
e (N
)
100 Cycle Pellet Reactivity
100 Cycle Pellet Strength
21
Pellet Reaction Mechanism – Ionic
Diffusion for Unsupported Iron
22
Partially oxidized Fe with support Pt mapping
Pt Epoxy Resin PtPellet bulk phase
Pellet Reaction Mechanism – Ionic
Diffusion for Supported Iron
Structures of Iron Oxide
NaCl Type
oxygen close-packed
cubic pattern
iron occupy all
octahedral interstices
inverse Spinel Type
FeO Fe3O4
octahedral interstices
1/2 occupation rate
tetrahedral interstices
1/8 occupation rate
Role of Support – Oxidation of Fe and Fe/TiO2Simulation
Energy barrier for O2- can be reduced after support addition
Oxygen anion transfer in Wüstite and Ilemnite
Number of cycles
2 3 4 5 6 8 20 30 40 50 60 801 10 100
Wt
% C
O2 c
ap
ture
(g
-CO
2 / g
-so
rben
t)
0
10
20
30
40
50
60
70
80
90
PCCa
LCa
Li4SiO4b
PbOc
CaO (microns)d
dolomitee
Theoretical capacity
Comparisons with other HT sorbents
(acurrent work; bToshiba Corpn., cKato et al, 1999; dBarker, 1973; eHarrison et al, 2001, dBarker, 1974)
Atomic Investigation of CO2 Adsorption on CaO
(100)
(110)
(111)
:O :Ca : C
Relaxed adsorption images of CO2
molecule on CaO surfaces
Adsorption energy of CO2 molecules on various CaO surfaces
Surface (100) (110) (111)
Adsorption energy
(eV)
-0.90 -2.12 -0.71
Simulation:Vienna Ab-Initio Simulation Package (VASP)
Surface structure: semi-infinite model
extremely stable configuration may prohibit a further transformation of the intermediate
(CaO·CO2) into the calcium carbonate
Front View Side View
Microscopic
XRD spectra of the sintered sorbents (a) sintered (b) hydrated
800˚C 900˚C 1000˚C 1100˚C 1200˚C 1300˚C
Before 0.139 0.107 0.097 0.088 0.149 0.113
After 0.263 0.234 0.249 0.249 0.235 0.26
The main peak breadth (FWHM) of the sorbents before/after hydration
800˚C 900˚C
1000˚
C
1100˚
C
1200˚
C
1300˚
C
Before
hydration
(111) 19.17 18.70 17.15 18.44 18.12 17.35
(200) 50.82 54.55 51.81 51.55 52.66 50.60
(220) 30.02 26.75 31.04 30.00 29.22 32.05
After
hydration
(111) 20.87 19.84 19.87 22.16 20.36 20.45
(200) 51.19 55.87 53.84 55.40 56.18 55.17
(220) 27.94 24.29 26.29 22.44 23.46 24.38
The intensity of the first three planes on the CaO
surface of various sorbents before and after hydration
fraction of (111) and (100) increase! (110) decrease!
OSU CCR Process
CARBONATOR
CALCINER
HYDRATOR
BOILER
50.3249 48.31 48.71
47.67 47.549.18
46.8948.35
46.6248.44
47.17 46.545.62
44.0545.05
43.713y = -0.316x + 50.085
R² = 0.7591
0
10
20
30
40
50
60
1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17
% C
aptu
re c
apac
ity
Cycle number
Hydrated sample capture capacity
before hydration (Calcined)
After hydration
OSU CCR Process
CCR Process Demonstration
Calcium Looping Sub-pilot Unit for Hydrogen production
Comparison Among Gaseous Chemical Looping, Direct Coal Chemical Looping and Traditional Coal to Hydrogen/Electricity Processes
Assumptions used are similar to those adopted by the USDOE baseline studies.
33
My Graduate Students and Research Associates
Zhenchao Sun
S. Rao
William Wang
Songgeng Li
Andrew Tong
Nihar Phalak
Siwei Luo
Yao Wang
Niranjani Deshpande
Ted Thomas
Himanshu Gupta
Puneet Gupta
Alissa Park
Mahesh Iyer
Luis Velazquez-Vargas
Bartev Boghos Sakadjian
Danny Wong
Fanxing Li
Shwetha Ramkumar
Liang Zeng
FuChen Yu
Deepak Sridhar
Ray Kim
Fei Wang
34
Government Agencies and Industrial Corporations
• U. S. Department of Energy
• Ohio Coal Development Office
• U. S. Department of Defense
•Clear Skies
•Noblis/Metritek
•CONSOL Energy
•PSRI
•AEP
•Duke Energy
•Babcock & Wilcox
•Air Products
•Shell
•CRI/Criterion
•First Energy
•Carmeuse Lime and Stone
•LittleFord Day
•Southern Company