Advanced

 Clean  Coal  Technologies:  Chemical  

Looping  

 
36th  Annual  VCEA  Conference  and  Expo  
 
Andrew  Tong    
Department  of  Chemical  and  Biomolecular  Engineering  
The  Ohio  State  University  
 
May  19th,  2015  
Kingsport,  TN  
 Large-­‐Scale  CCS  Projects  
40  
•  60  total  CCS  projects    
–  15  less  than  2012  report  
–  Decline  in  CCS  due  mostly  to  
United  States  
Europe  –  no  large-­‐scale  CCS  
30  
Africa  
opera4on  an4cipated  un4l  
2018-­‐2020  
South  America  
•  21  CCS  ac4ve  projects:  
Other  Asia   under  construc4on  or  in  
20  
Middle  East  
opera4on  
–  40  MMTPY  CO2  capture  
Australia  
–  14  ac4ve  CCS  projects  
Canada   located  in  North  America  
10  
•  3  addi4onal  projects  to  
China  
receive  final  investment  for  
Europe  
construc4on  an  opera4on  in  
2014  
0  
•  United  States  leading  in  CCS  
Planning   Construc4on   Opera4on   projects  
 Statoil/Shell  860  MW  NG  Power  Plant,  Draugen,  Norway  

CO2  Capture  with  

Exis4ng  
Technologies:  
Large  steam  
requirement;  
Large  footprint;  
Low  CO2  
regenera4on                    
pressure;  
 ~30%  CO2  capture  
penalty.  

Jose  D.  Figueroa,NETL,  OSU  Seminar  2010.  

Original  Source:  Jon  Gibbins  et  al,  Capture  Ready  Fossil  Fuel  Plants:  
Defini[ons,  Technology  Op[ons  and  Economics,  2006  
CO2  Capture  from  Fossil  Energy  –  Technological  
Solu[ons  

Source: José D. Figueroa, National Energy Technology Laboratory (NETL), USDOE

 Economics  of  OSU  Chemical  Looping  Process    
Enhancer  Gas  
Recycle  Fan
Base   MEA   CDCL  
Water CO2
compressor
Plant   Plant   Plant  
CO2
FGD
H2O
Sequestration Coal  Feed,  kg/h 185,759 256,652 205,358  

CO2+H2O
Spent  Air Particulate  
CO2  Capture  Efficiency,  % 0 90 96.5  
FGD Stack
Removal
ID  
Fan
Net  Power  Output,  MWe 550 550 550  
Fly  Ash   and   Carrier  
Particle  Fines
Net  Plant  HHV  Heat  Rate,   9,165   12,663   10,084  
Fe2O3
kJ/kWh  (Btu/kWh) (8,687) (12,002) (9,558)  
Coal Coal  Prep. Reducer
Electricity
Net  Plant  HHV  Efficiency,  
Existing   equipment   39.3 28.5 35.6  
for  repowering   case
Combustor
%
FeO/Fe
Steam HP IP LP
Carrier   Particle   Cost  of  Electricity,  $/
Makeup  (Fe2O3) 80.96   132.56   102.67  
Water
Steam  Cycle
MWh
Air
Increase  in  Cost  of  
Existing   equipment   ID   Cooling   Existing   equipment   -­‐   63.7   26.8  
for  repowering   case Fan
Pump
Tower for  repowering   case Electricity,  %  

•  Retrofit  to  conven4onal  coal  combus4on  process  

•  CDCL  replaces  exis4ng  PC  boiler  
–  Addi4onal  equipment  for  CO2  compression  and  transporta4on  required  
•  Techno-­‐Economic  analysis  performed  comparing  CDCL  to  Base  Plant  with  no  CO2  
capture  and  90%  CO2  capture  via  post-­‐combus4on  MEA  process  
  Process  Concept  

CxHyOz Hot Spent

Air/H2

Fe2O3 Fe

CO2 + H2O Air/H2O

Sequestration

Reducer:  Coal  +  Fe2O3    →    Fe/FeO  +  CO2  +  H2O                        (endothermic)   CL   Process   reduces   exergy   loss   by  
Oxidizer:  Air/H2O  +  Fe/FeO    →    Fe2O3  +  Spent  Air/H2  (exothermic)   recupera4ng   the   low   grade   heat  
while   producing   a   larger   amount   of  
Overall:  Coal  +  Air    →    CO  +  H O  +  Spent  Air                            (exothermic)   high  grade  heat  
2 2
Reducer    Opera4on  
 Modes  of  Chemical  Looping  Reactor  Systems  
 Mode-­‐1    Mode-­‐2  
 

Reducer Mode 1 Mode 2

Bubbling,
Moving packed,
turbulent, fast
Operation Regime or multistage
fluidized, or
fluidized bed
spouted bed

Gas Solid Contacting

Mixed/Cocurrent Countercurrent
Moving  Bed       Pattern
       Reducer  
Subsequent Hydrogen
No Yes
Production
CO2    
H2O     CO2,  H2O     Particle size, µm 100-600 1000-3000
Fluidized  Bed      
Reducer gas velocity*, m/s <0.4 >1.0
       Reducer  

Fuel  
Fuel  

Chalmers  University  CLC  System   OSU  CLC  System  

Thomas,  T.,  L.-­‐S.  Fan,  P.  Gupta,  and  L.  G.  Velazquez-­‐Vargas,  “Combus[on  Looping  Using  Composite  Oxygen  Carriers”  U.S.  Patent  No.  7,767,191  (2010)  
Chemical  Looping  Reactor  Opera[on  
Phase  Diagram  –  Thermodynamic  Restric[ons  

Shaded  area  is  not  

reducer  opera[on    
zone  

Opera[ng  Equa[on  for  Moving  Bed  Reducer  

Oxygen  Carrier  Development  
 Oxygen  Carrier  Selec[on  For  CLC  
Temperature#(°C)#

500# 600# 700# 800# 900# 1000# 1100# 1200# 1300#

0#
0.21#atm#O2#

?50# 0.05#atm#O2#
O2#+#4Mn3O4#=#6Mn2O3#

O2+2Cu2O=4CuO# O2#+#6MnO#=#2Mn3O4#
?100#
O2#+#4Fe3O4#=#6Fe2O3#

O2+4Cu=2Cu2O#
?150#

?200#
ΔG#(kj/mol)#

O2+2Ni#=#2NiO#
99.5%CO2/0.5%CO#

?250#

?300#
O2+.5CaS=.5CaSO4#
O2#+#2Fe#=#2FeO#
?350#
20H2:80H2O# O2#+#6FeO#=#2Fe3O4#

O2#+#4Fe3O4#=#6Fe2O3# O2#+#6FeO#=#2Fe3O4# O2#+#2Fe#=#2FeO#

?400# 65H2:#45H2O#
O2+2Ni#=#2NiO# O2+.5CaS=.5CaSO4# O2#+#6MnO#=#2Mn3O4#
O2#+#4Mn3O4#=#6Mn2O3# O2+2Cu2O=4CuO# O2+4Cu=2Cu2O#
20H2:80H2O# 65H2:#45H2O# 1H2:99H2O#
0.21#atm#O2# 0.05#atm#O2# 99.5%CO2/0.5%CO#
?450#
Pellet  Reac[on  Mechanism  –  Ionic  Diffusion  
for  Unsupported  Iron

12
 Cyclic  Redox  of  Pure  Fe2O3    with    Hydrogen    
   

Cyclic  Redox  of  Composite  Fe2O3  with  Hydrogen  

100 Cycle Pellet Reactivity

100 Cycle Pellet Strength

450

400

350

300

Force  (N)
250

200

150

100

50

Fresh
10  C ycles
100  C ycles
Coal  Direct  Chemical  Looping  (CDCL)  
25  kWth  Sub-­‐Pilot  Demonstra4ons  
CDCL  OSU  Moving  Bed  Reactor  Configura[on  
Reducer  (Sec[on  A)  
 25  kWth  Sub-­‐Pilot  Demonstra[on  
Fuel   Fuel  Flow   Fuel  
Type   Enhancer  
Feedstock   (lb/hr)   Conversion  
Coal  volatile   CH4   0.1-­‐0.4   H2   99.80%  
Lignite   0.7-­‐2.0   CO2/H2O   94.90%  
Coal  char     Metallurgical  
0.05-­‐3   CO2/H2O   50-­‐97.30%  
Coke  
Sub-­‐
0.05-­‐7   CO2/H2O   60  –  99+%  
Bituminous    
Coal    
Bituminous   0.05-­‐3   CO2/H2O   70  –  95%  
Anthracite   0.2-­‐0.7   CO2/H2O   95.50%  
Biomass   Wood  pellets   0.1   CO2   75  –  99%  

•  Combined  >680hours  of  opera4onal  

experience  
•  Successful  results  for  all  coal  
feedstock  tested  
 
 200+  Sub-­‐Pilot  Con[nuous  Run  -­‐  Sample  Results  
Once-­‐Through  Reducer  Carbon  Conversion  Profile   Reducer  Gas  Concentra[on  Profile  
100% 100% 5%
90% 99%

Concentration CO, CH4, O2 (%)

80% 98%
CO2   4%
Carbon Conversion (%)

Concentration CO2 (%)

70% 97% CO2
60% 96% CO 3%
50% 95% CH4
40% 94% 2%
30% 93%
20% 92% CH4   1%
10% 91% CO  
0% 90% 0%
10 30 50 70 90 110 130 0 50 100 150 200
Time of reaction (min) Time (min)

Combustor  Gas  Concentra[on  Profile  

0.5
•  Con[nuous  steady    >90%  carbon  conversion  

Concentration (%) CO, CH4, CO2

10 0.45
from  reducer  throughout  all  solid  fuel  loading   0.4
(5-­‐  25kWth)  
Concentration (%) O2

8 0.35
•  <0.25%  CO  and  CH4  in  reducer  outlet  =  full  fuel   0.3
conversion  to  CO2/H2O   6
CO2
0.25

•  <0.1%  CO,  CO2,  and  CH4  in  combustor  =   4 O2 0.2

negligible  carbon  carry  over,  nearly  100%   CO

CH4
0.15
0.1
carbon  capture   2
0.05
  0 0
2 4 6 8 10 12 14 16 18
Time (min)
SCL  Pilot  Demonstra4on  Unit  
 OSU  Syngas  Chemical  Looping  Process  
Fe  2O
  3    
Depleted   Main  reac[ons:    
CO2  &  Steam   Air    

Reducer:  CxHyOz  +  Fe2O3  →  CO2  +  H2O  +  Fe  

Oxidizer:  Fe  +  H2O  →  Fe3O4  +  H2  +  Q  
Reducer  

Combustor:  Fe3O4  +  O2  →  Fe2O3  +  Q  

CHEMICAL  LOOPING  
Total:  CxHyOz  +  H2O  +  O2  →  CO2  +  H2  +  Q  

Combustor  
Syngas    Fuel  

   
Fe  /  FeO

H2  &  Steam  
General  Observa[ons:  
 
•   High  fuel  conversion  
Oxidizer  

•   Near  100%  in-­‐situ  CO2  capture  

•   High  purity  H2  genera4on  
Air   •   High  oxygen  carrier  conversion  
Steam   •   Low  solid  circula4on  rate  

Fe3O4  
25  kWth  SCL  Sub-­‐Pilot  Unit  
 25  kWth  SCL  Sub-­‐Pilot  Demonstra[on  
Reducer  Gas  Profile  –  3  Day  Demonstra[on   Reducer  Profile  –  Methane  Test  

Oxidizer  Gas  Profile–  3  Day  Demonstra[on   Reducer  Profile  -­‐  Simulated  NCCC  Air-­‐Blown  Gasifier  Feed  

•  Con4nuous  ~99.99%  syngas  and  methane  conversion  achieved  

•  Con4nuous  hydrogen  produc4on  >99.99%  purity  
•  >360hrs  sub-­‐pilot  opera4ons  without  opera4onal  issues  
 SCL  Pilot  Unit  Development  
•  Objec4ve:  Design,  construct,  and  demonstrate  a  SCL   Depleted$Air/Par:cle$Recovery$
pilot  unit  
–  Opera4ng  Condi4ons   Fe2O3$
•  High  Temperature:  850-­‐1050°C  
•  High  Pressure:  10  atm  
–  Design   Fe2O3$
•  Moving  bed  reducer  and  oxidizer  reactors  
•  Non-­‐mechanical  process  design  
•  Pressure  vessel  design  standards  (ASME  Sect.  8  Div.  I)   H2O/CO2$

Reducer'
–  Process  Control  
•  Instrumenta4on  requirements  
•  Process  safety  interlocks  
•  Automated  process  control  philosophy   Syngas$

–  Opera4ons  
Fe/FeO$
•  Real  syngas  feed  performance  results  
•  Long  term  opera4on  experience  
•  High  purity  H2  genera4on   H2$

Oxidizer'
•  High  syngas  conversion  
•  Project  Team  
–  Babcock  &  Wilcox  Power  Genera[on  Group,  Inc.  (B&W  
PGG):  Design  Engineering   H2O$
–  Louis  Perry  &  Associates  (LPA):  Balance  of  Plant  

Combustor'
–  The  Perry  Group  Ltd.  (PGL):  Construc4on  Management  
Fe3O4$
–  Par[culate  Solid  Research,  Inc.  (PSRI):  Cold  model  study  
–  CONSOL  Energy,  Inc.:  Techno-­‐economic  analysis  
–  Clear  Skies  Consul[ng  LLC:  Project  Management   Air$
OSU  SCL  250  kWth-­‐  3MWth  High  Pressure  Pilot  Unit  
Opera[on  for  Hydrogen  Genera[on  
Chemical  Looping  Par4al  
Oxida4on  (CLPO)  
 The  OSU  CTS  Chemical  Looping  Process:  Mass  and  Energy  Balance  
Natural
pre-heat Syngas  Specifica[ons  
T  =  600  C  
Gas
5.6 kg/hr
1 2 H2/CO  =  2.06  
Coal (PRB)
15 oC
4
CO2  (  v/v)  =  10  %  
10 bar
15.592 kg/hr Steam
3
 Syngas  (  dry  basis  v/v)  =  84.8  %  
Pre-­‐condi[oning   1 kmol/hr
600C
Fe2O3
Carbon  Capture  :  90.2  %  
T  =  1180  C  
Material  &Energy  Balance  Table   Fe2O3/C  =  0.756  

1   2   3   4   5   6   7   S2   S1  
S1

T  (  C)   25   600   600   15   700   1180   25   864   1180  

Reducer

~ 10 bar
P  (bar)     29   29   11   1.01   11   10   1.01   10   10  
Mass  
kg/hr   5.615   5615   18.01   0   69.24   59.59   0   0   0  
Mole  Flow  kmol/hr   Syngas  
CH4   0.35   0.35  
H2O   1   0.08  
CO2   0.12  
N2   1.89   1.89   S2
O2   0.51   0.001  

Solid   592.6   603.5  

COAL   15.5   2.6   Spent-air
ASH   1.27   6

CO2    emissions  <  10%  

Combustor
~ 10 bar

Coal (PRB)
pre-heat
15 oC
7 Air
10 bar
5 10 bar
1.113 kg/hr
Pre-­‐condi[oning   T  =  700  C   69.74 kg/hr
Economic Analysis
Case  Descrip[on Technology  Status Reference
MBL-­‐1 Reference   from  DOE/NETL  (341/101514)  coal   Conven[onal NETL  MBL  Report
feedstock  without  CO2  capture
MBL-­‐2 Reference   from  DOE/NETL  (341/101514)  coal   Conven[onal NETL  MBL  Report
feedstock  with  CO2  capture
OSU-­‐1 OSU  CLG  –  2  reactor  system  –coal  only Advanced N/A
OSU-­‐2 OSU  CLG  –  2  reactor  system  –coal  and  natural  gas Advanced N/A

2.00

1.78
1.75

Methanol Required Selling Price ($/gal)

1.64

1.48
1.50
1.41
  Case
  MBL-­‐1 MBL-­‐2 OSU-­‐1 OSU-­‐2 1.25 Capital Costs
Required  Selling   1.18
1.23
0.81
Fixed Costs

Price  ($/ton,   495.2 535.5 425.1 446.6 1.00

0.89
Variable Costs
Electricity Cost
2011$) NG Costs
Required  Selling   0.75
Coal Cost
Price  ($/Gal,   1.64 1.78 1.41 1.48 0.09
2011$) 0.50 0.05
0.11
0.14 0.14 0.10
0.06
0.09 0.09
0.25 0.03 0.05 0.14 0.29

0.21 0.21 0.18

0.10
0.00
MBL-1 MBL-2 OSU-1 OSU-2
 OSU  Chemical  Looping  Technology  Plaporm
Feedstock      

Driver  

Applica[ons  and  Products  

Coal   Chemical  Looping   CO2  Capture/Emission  
Combus4on  (CLC)   Control  
Natural  Gas  
  Electricity/heat  
Oil  
•   Retrofit  to  PC  
Petcoke   Chemical  Looping   •   New  Plant  
Gasifica4on  (CLG)   •   Combined  Cycle  
Biomass   •   SOFC  
 
Waste   Hydrogen  
Carbona4on-­‐  Calcina4on  
Syngas   Reac4on  (CCR)   CLG  Syngas  
F-­‐T  light     Liquid  fuel  
hydrocarbon   •  F-­‐T  Synthesis  
Calcium  Looping  Process   •  CO2  Hydrogena4on  
……   (CLP)   •  Olefins  to  Liquid  Fuel  
    Chemicals  
•  Olefins  
Direct  Chemical  Synthesis   •  Ammonia  
(with  Bio2Electric)    
   

Combus[on   Looping   Using   Composite  

Oxygen   Carriers,   T.   Thomas,   L-­‐S   Fan   P.  
Looping Gupta  and  L.Vargas,  U.S.  Provisional  Patent  
Particle Series   No.   11/010,648   (2004),   U.   S.   Patent  
Developme 7,767,191.  
nt
 Concluding  Remarks  
•  Chemical  Looping  embodies  all  elements  of  par[cle  
science  and  technology  -­‐  par[cle  synthesis,  reac[vity  
and  mechanical  proper[es,  flow  stability  and  contact  
mechanics,  gas-­‐solid  reac[on  engineering…  
•  OSU  processes  characterized  by  the  moving  bed    
reducer  configura[on  are  compact  in  design  and  high  
efficiency  in  opera[on.  Success  achieved  in  the  
opera[on  of  200+  hour  con[nuous  sub-­‐pilot  CDCL  run  
using  coal  and  progress  made  in  the  on-­‐going  Syngas  
Chemical  Looping  pilot  demonstra[on  reflect  the  
likelihood  of  commercializa[on  of  these  technologies  
in  the  near  future.  
 Acknowledgements  
•  U.S.  Department  of  Energy    (USDOE):  Na4onal  Energy  Technology  Laboratory  
(NETL),  Advanced  Projects  Research  Agency  –  Energy  (ARPA-­‐E)  
•  Ohio  Coal  Development  Office  (OCDO)  of  the  Ohio  Air  Quality  Development  
Authority  (OAQDA)    
•  Industrial  Collaborators  (Babcock  &  Wilcox,  Par4culate  Solids  Research  Inc.,  
CONSOL,  Air  Products,  Shell,  Clear  Skies)    
•  Na4onal  Carbon  Capture  Center  (NCCC)  
•  Fellow  graduate  students  and  research  associates  
•  Professor  L.-­‐S.  Fan  
•  This  material  is  based  upon  work  supported  by  the  Department  of  Energy    under  
Award  Number  DE-­‐FE0009761  and  DE-­‐FE0023915