INTEGRATED CHEMICAL LOOPING AIR SEPARATION (ICLAS) · INTEGRATED CHEMICAL LOOPING AIR SEPARATION...
Transcript of INTEGRATED CHEMICAL LOOPING AIR SEPARATION (ICLAS) · INTEGRATED CHEMICAL LOOPING AIR SEPARATION...
INTEGRATED CHEMICAL LOOPING AIR SEPARATION (ICLAS)
Research and Development activities at the University of Newcastle
Terry Wall, Kalpit Shah, Hui Song and Behdad Moghtaderi*Presented by Rohan Stanger*
Chemical Engineering, School of Engineering, Faculty of Engineering and Built Environment, The University of Newcastle, Callaghan NSW 2308, Australia
Outline• Oxygen production technologies• Chemical Looping Air Separation Concept• Process simulation results• Experimental (TGA) results• Design, fabrication, commissioning and modelling of 5
kWth –hot and 500 kWth cold flow rigs
Current and emerging drivers for oxygen production for oxy-fuel
Technology Technology providers• ASU• PSA/VPSA• ITM/OTM
Membranes• SOFC/Electrolysis• Chemical air
separation methods (CASM)
• Airgas • Air Liquide• Air Products & Chemicals • The Linde Group, AGA
AB, BOC (formerly LindeAG)
• Praxair • CRYOTEC Anlagenbau
GmbH
Methods Energy Req.
Purities (vol%)
Technology Status Advantages Disadvantages
CASU 120-165kwh/ t of O2
High MatureLarge scale production
High energy consumption
Adsorption 100-145kwh/ t of O2
High Semi-matureSmall to medium scale production
Scale up and energy
Polymer membraneHigh (100-145 kwh/ t
of O2)
Low (~40%) Semi-mature Scale up, energy and membrane costsIon transport
membrane (ITM or OTM)
High
(99%)Developing
Moltox 40% lower than CASU
High Developing Lowenergy requirement
CorrosiveDu Motay ,Brin and
Mallat process40% lower than CASU
Medium Out dated
CAR and process of TDA
20-40% lower than
CASUHigh Developing Energy effective
Carbonation of ceramics, cyclic stability of oxygen carriers, difficult to maintain partial pressure and temperature in the reactor, scale up??
CLAS40-80%
lower than CASU
High DevelopingEnergy effective
Status of Oxygen production processes
Universities/Research groups engaged in CASM Research
1. Eltron Research, Inc. (Sorbent development)2. TDA Research, Inc. (FBC-ceramic oxygen carriers)3. The BOC Group, Inc. (Fixed bed-ceramic oxygen carriers)4. Alstom Power Plant Laboratories (pilot plant study) 5. Western Research Institute, USA. (Fixed bed-ceramic oxygen
carriers)6. The University of Utah, USA. (FBC-ceramic oxygen carriers)7. The University of Newcastle, Australia (FB/FBC-metal oxides)8. Tsinughua University, China (Metal oxides)9. Energy Concepts Co. and Air product (Solvent development)
Development and testing of new solvents, sorbents, oxygen carriers and efficient reactor and process design
On-going R&D in CASM
Challenges in CASM• Corrosion related problems with Moltox process utilizing
molten salt solution of mixed alkali metal nitrates andnitrates.
• Sorbent and oxygen carriers reaction with flue gas and itsimpurities
• Sorbent and oxygen carriers long term stability, lowtemperature operation, lower price and preparation costs
• Efficient reactor design and process to maintain uniformtemperature and partial pressure profiles in the reactor
• Effective heat integration of the process
Chemical looping air separation (CLAS) – concept
OxidationMex Oy-2 (S) + O2 (g) Mex Oy (S)
ReductionMex Oy (S) Mex Oy-2 (S) + O2 (g)
Air
Energy
Reduced AirN2 +O2
SteamOr CO2
O2+ Steam or CO2
0.01
0.1
10 500 1000 1500 2000
Equil
ibrium
Parti
al Pr
essu
re of
O2
Temperature (C)
MnO/MnO2
MnO2/Mn2O3
Mn2O3/Mn3O4
Pb/PbO
PbO/PbO2
Pb3O4/PbO2
Fe3O4/Fe2O3
Pd/PdO
PdO/PdO2
Pd/PdO2
CrO2/Cr2O3
Os/OsO2
CaO2/CaO
CuO/Cu2O
Co3O4/CoO
Partial Pressure Requirement
Thermodynamic modelling –identification of suitable oxy. carriersStudy on 20 different elements from periodic table(i.e. K,Ca,Ce, Cr, Mn, Fe, Co, Ni, Cu, Zn, Ru, Rh, Pd, Pt, Cd, Re, Os, Ir, Pb, Bi) with their different oxidation states (Total >40 metal oxide systems studied)
Steam/CO2 requirement in reduction reactor
Typical calculation basis:1Kg air (OR) = 1Kg CO2 (RR)
MnO2/Mn2O3
1. IBS or IGS, 2. Reduction reactor, 3. Oxidation reactor, 4. Air Blower, 5. Condensor, 6. Oxy-furnace, 7. Steam drum, 8. Flue gas cleaning and CO2 processing Unit (CPU)
1 2 3
5
7
6
4
8
Coalor NG
Coal
Steam at 560oC
CO2 for storage
Steam to turbine
Impurities
Flue gasCO2 + H2O
O2+ CO2+H2O H2O
Air
Me
MeO
O2
+CO2
Red. Air
Recycled CO2
at 380oCCoalor NG
Essential:• High heat recovery (80-95%)• High conversion (>90%)• Lower O2 partial pressure
(+/- 5% than EPP)
Process simulations for Oxy-fuel – Isothermal CLAS integration
1.E-11
1.E-10
1.E-09
1.E-08
1.E-07
1.E-06
1.E-05
1.E-04
1.E-03
1.E-02
1.E-01
1.E+00
1.E+01
1.E+02
1.E+03
1.E-071.E-061.E-051.E-041.E-031.E-021.E-011.E+001.E+011.E+021.E+031.E+041.E+051.E+061.E+071.E+081.E+091.E+101.E+111.E+121.E+131.E+141.E+15
0 500 1000 1500 2000
Stea
m re
quire
men
t (kg
/kg o
f air)
Temperature (C)
Steam/CO2 req. PO2
Equilbrium Partial Pressure of Oxygen (%
)
Oxygen production cost
O2% in product stream
Process simulations for Oxy-fuel– Isothermal CLAS integration
0%2%4%6%8%10%12%14%16%18%20%
0123456789
10
880 900 920 940 960 980 1000 1020 1040
O2 production (kg) CO2 req. (kg) Operating cost ($/ tonne of O2) O2% in recycle gas
Temperature (C)
Oxy-fuel process needs 22 wt.% O2through burners !!!
Option (1) to provide desired O2concentration
1. Solar/Electric heater/IBS/IGS, 2. Reduction reactor, 3. Oxidation reactor, 4. Air Blower, 6. Steam drum, 7. Flue gas cleaning and CO2 processing Unit (CPU), 8. Condensor
2 3
6
5
4
7
Coal
Recycled CO2 at 380oC (39%)
CO2 for storage
Steam to turbine
Impurities
Flue gas
Air
Me
MeO
Red. Air
1
O2 = 10%CO2 = 35%H2O = 55%
Steam at 560oC (61%)
8H2O
O2 = 22%CO2 =78%Use steam with RFG in the fuel
reactor to increase O2 concentration !!!
1. Solar/Electric heater/IBS/IGS, 2. Reduction reactor, 3. Oxidation reactor, 4. Air Blower, 6. Steam drum, 7. Flue gas cleaning and CO2 processing Unit (CPU), 8. CASU/ membrane/PSA/VPSA
2 3
6
5
4
7
Coal
Recycled CO2 at 380oC
CO2 for storage
Steam to turbine
Impurities
Flue gas
O2 = 22%CO2 =78%
Air
Me
MeO
Red. Air
1
O2 =10%CO2 = 90%
8 O2 (100%)
Option (2) to provide desired O2concentration
Use hybrid CLAS/CASUsystem!!!
Isothermal ICLAS Design 1 (Direct/Indirect NG)
Air*
RC* RC*CH4 CH4
Combustors
Reduction Reactor (RR)Oxidation Reactor (OR)Better
heat transfer
AirX
Red. AirX Red. Air **
(CO2 + O2)**
Flue gas forcleaning
CH4
X at 200-300oC* at 600-700oC** at 900oC
CH4
Tmin TminTmax Tmax
T**
Height of reactors OR RR
IICLASRA**
CO2+O2**
HE1
HE2
RA @ 45oC
Air @ 35oC Air @ 600-700oCto IICLAS
Recycled flue gas@ 350oC
Recycled flue gas@ 600-700oC to IICLAS
CO2+O2 at@ 360oC
Effective Integrationto get highest recovery
UON reactor design: Isothermal-CLAS for oxygen production
Improved actual partial pressure of O2 !!!!!!!
1. Solar/Electric heater/IBS/IGS/IOFF/IOFFH, 2. Reduction reactor, 3. Oxidation reactor, 4. Air Blower
2 3
4
Red. Air
1
Delta T(Betn two bed) = 100-300oC
Oxidation = XoCReduction = X+(100-300oC)
O2 +Recycled CO2/steam
1
Recycled CO2/steam from oxy-fuel thermal power plant
0%10%20%30%40%50%60%70%80%90%100%
0
1
2
3
4
5
6
7
427
437
447
457
467
867
877
887
897
1017
1027 86
787
788
789
790
791
792
7
Operating cost O2 % in product stream
MnO2/Mn2O3 Mn2O3/Mn3O4 CuO/Cu2O CoO/Co3O4
OxidationTemp. oC 327 727 797897
Redcution Temperature oC
O2
$/to
nne
of O
2
O2% in the product stream
Temperature Swing CLAS
Option (3) to provide desired O2concentration
ESP Flue Gas Cleaning
CondensationCompressionPurification
HE
TransportStorageCO2/H2O
CO2/SOx/NOx/O2/H2O
CO2/SOx/NOx/O2/H2O+ PM
Steam turbine
CO2 + O2
COAL
CO2
H2O
Vent
( ) y
CLASMeO
Me
AIR
N21 2 3 4
??
Process simulations for Oxy-fuel– Effect of flue gas impurities
0
20
40
60
80
100
0 500 1000 1500 2000Co
mpo
siti
on o
f Cu
base
d ox
ygen
ca
rrie
rs (m
ol %
)Temperature (C)
CuOCu2OCuCO3Cu(OH)2
CuOCu2OCuCO3
Cu(OH)2
0
20
40
60
80
100
0 500 1000 1500 2000
Com
posi
tion
of C
u ba
sed
oxyg
en
carr
iers
(mol
%)
Temperature (C)
CuOCu2OCuCO3Cu(OH)2
CuOCu2OCuCO3
Cu(OH)2
0
20
40
60
80
100
0 500 1000 1500 2000
Com
posi
tion
of C
u ba
sed
oxyg
en
carr
iers
(mol
%)
Temperature (C)
CuOCu2OCu(OH)2CuCO3CuSCu2SCuSO4Cu2SO4(CuO)(CuSO4)CuSO4(H2O)Cu
CuOCu2OCu(OH)2
CuCO3
CuSCu2SCuSO4
Cu2SO4
(CuO)(CuSO4)(CuSO4) (H2O)Cu
0
20
40
60
80
100
0 500 1000 1500 2000
Com
posi
tion
of C
u ba
sed
oxyg
en
carr
iers
(mol
%)
Temperature (C)
CuOCu2OCu(OH)2CuCO3CuSCu2SCuSO4Cu2SO4(CuO)(CuSO4)CuSO4(H2O)Cu
CuOCu2OCu(OH)2
CuCO3
CuSCu2SCuSO4
Cu2SO4
(CuO)(CuSO4)(CuSO4) (H2O)Cu
0
20
40
60
80
100
0 500 1000 1500 2000
Com
posi
tion
of C
u ba
sed
oxyg
en
carr
iers
(mol
%)
Temperature (C)
CuOCu2OCu(OH)2CuCO3CuSCu2SCuSO4Cu2SO4(CuO)(CuSO4)CuSO4(H2O)Cu
CuOCu2OCu(OH)2
CuCO3
CuSCu2SCuSO4
Cu2SO4
(CuO)(CuSO4)(CuSO4) (H2O)Cu
(a) (b)
(c)
(d) (e)
Pure steamPure CO2
Wet
DryImpure
CuO/Cu2O
Sulphate formation
Above 900oC no sulphate Formation and thereforeno contamination of Oxygen carriers !!!
The designed ICLAS will be more efficient than CAR/TDA process as contamination is avoided.
Material preparation and characterization
Oxygen
carriers
Active metal
oxide content
(wt. %)
Density of
particle
(kg/m3)
Crushing
strength
(N)
Crystalline phase
CuO/SiO2 47.7 2900 1.2 ± 0.3 CuO, SiO2
Mn2O3/SiO2 32.43100 1.5 ± 0.4 Mn2O3, Mn3O4,
Mn7SiO12
Co3O4/SiO2 21.8 4000 2.6 ± 0.3 Co3O4, Co2SiO4
CuO/Al2O3 25.8 4100 0.9 ± 0.2 CuO, CuAl2O4
Mn2O3/Al2O3 21.6 3800 1.7 ± 0.5 Mn2O3, Mn3O4, Al2O3
Co3O4/Al2O3 26.5 4700 3.5 ± 0.5 Co3O4, Co2AlO4, Al2O3
Characterization of the fresh oxygen carriers
• Prepared by dry impregnation method• Sintered at 950oC for 6 hours • Typical particle size in the range of 106-125 μm were
sieved for further reactivity studies.
Experimental – Reactivity and selectivity study
Good enough for fluidization
CuO/SiO2 - 41 cycle/ 1200 min operation
0 200 400 600 800 1000 120094
96
98
100
102
Weig
ht V
ariat
ion (%
)
Time / min
0.00.71.42.12.83.5
T1 T2 T3 T1 T2 T3
Al2O3
T1 T2 T3
Mass
chan
ge / w
t%
Temperature / oC
SiO2
T1 T2 T3 T1 T2 T3 T1 T2 T3
CuO-Red CuO-Oxd Mn2O3-Red Mn2O3-Oxd Co3O4-Red Co3O4-Oxd
CuO/SiO2 found best !!!
T = 700-900oC
TGA results
0 3 6 9 12 150.0
0.2
0.4
0.6
0.8
1.0
800oC825oC850oC875oC900oC975oCO
xyge
n D
esor
ptio
n C
onve
rsio
n
Time (min)
Oxidation
0.0 0.2 0.4 0.6 0.8 1.00.0
0.2
0.4
0.6
0.8
1.0
800oC 900oC 925oC 950oC 975oC
Oxy
gen
Sor
ptio
n C
onve
rsio
n
Time (min)
(a)
Reduction
Kinetic model development
SEM images of CuO/SiO2
Fresh
After 1200 minoperation
Sintering !!!
SEM images of Cu-Mg-O/SiO2
Fresh After 1200 minoperation
Cu: Mg = 7:3
Cu: Mg = 1:1
Addition of Mg provide stability and reduce clustering!!!
Stability improved with Mg additionto CuO-SiO2
0 6 12 18 24 30 36 42-2
0
2
4
6
8
10
12 C49S C18S CMS9-1 CMS4-1 CMS7-3 CMS1-1
Loss
of O
TC (%
)
Cycle num
Spray dried oxygen carrier testing is ongoing at UoN.Dry impregnation is easy and cost effective method compare to spray drying.
Therefore, comparison will be made in terms of performance improvement gain!!
Design of the 5 kW bench scale unit of CLAS
Oxi RedReactor Inner Dia m 0.5000 0.6250Height (Assumed) m 0.95 0.45Reactor Outer Dia (thk =12 mm) m 0.5120 0.6370Common riser Inner Dia m 0.24Height (Assumed including reducer) m 4.87Riser Outer Dia m 0.2520
Total volume m3 0.406685 0.137988 Calculation boxTotal Height (Assumed) 6.02 0.45
Oxi RedType Temperature K 300 300Inlet (a) m 0.240 Pressure Pa 101325 101325D m 0.480 Operating pressure Pa 101325 101325b m 0.096 Stiochiometric Air flow rate L/min 20000.00 2000.00De m 0.240 m3/s 0.33333 0.03333S m 0.240 Densty of air at 25 C kg/m3 1.18452 1.18452h m 0.72 Stio. Air flow rate at 25 C kg/s 0.39484 0.03948H m 1.92 Densty of air at operating temp kg/m3 1.17662 1.17662B m 0.18 m3/s 0.3356 0.0336
kg/s 0.39484 0.03948Excess air % 0.0 0.0
3. LS 1 and 2 dimensions Total air at operating temp m3/s 0.33557 0.03356
Inlet dia m 0.180000 Total air at 25 C L/min 20000.0 2000.0Outlet Dia m 0.180000 Oxygen avilable g/s 90.8133 9.0813Height m 0.450 Solid circulation rate g/s 812.155 81.215Slit (base on the ratio from hot rig) m 0.125 Solid circulation rate with binders (active : 50%) g/s 1624.309 162.431
Kg/s 1.624 0.162m3/s 0.0004641 0.0000464kg/hr 5847.513 584.751
Solid velocity in Reactor m/s 0.002365 0.000151
Residence time in Reactor s 401.728 2973.319Solid velocity in Riser m/s 0.0102638
Pressure in the system Pa 101325 325 Residence time in Riser s 474.580Temperature in the system K 300.00 125 Total Residence time s 876.309Avg. Density (assumed) kg/m3 3500.00 15
Void fraction (assumed) 0.60 0.60
Flow rate Gas velocity in Reactor m/s 2.85 0.18Red reactor L/min 2000.00 Gas velocity in Riser m/s 12.37Oxi reactor L/min 20000.00 Massflux (Reactor) Kg/m2s 8.28 0.53
Solid Inventory Massflux (Riser) Kg/m2s 35.92
Red reactor Kg 150
Oxi reactor Kg 150 2. LS calculationsLS Kg 50
Cross sectional area m2 0.032
Volume (double) m3 0.029
OC weight g 50000.000
OC density kg/m3 3500.000
Gas velocities Oxi Red Voidage 0.600
Gas velocity in Reactor m/s 2.85 0.18 (Look Gildart chart for different PS and density , for the oxidation reactor it should be between 1-3, and fo OC volume m3 0.023810
Gas velocity in Riser m/s 12.37 Surplus volume in the loop seal m3 0.005350
System calculation
Total solid holdup in the system 18.1% (< 15-20 based on Literature) 3. Total system volume calculationsPressure drop calculations Oxi RedTotal head loss Pa 9205 3171 Total solid in the system 0.11428571
Input pressure required Pa 110530 104496 (Blower can provide around 125000 Pa) Total volume including LS and downcomer 0.631216
Total solid holdup in the system 18.1%
4. System Pressure Drop calculationsReactor volume m3 0.1864375 0.13798828Solid inventory in each reactor g 150000 150000
m3 0.04285714 0.04285714initial voidageSurplus volume in reactor m3 0.14358036 0.09513114Pressure Drop Calculations Air Reactor Fuel ReactorHeight of the bed m 0.218 0.140Voidage ( e= 0.4 for Umf zone) (here assumed) 0.60 0.60Static head loss for solid Pa 2999.23567 1919.51083Static head loss gas Pa 539.598397 345.342974Solid velocity m/s 0.002365 0.000151Frcition factor 9553.77712 149277.768Frictional head loss (Ronald et.al 1989) for riser Pa 3036.1411
Misc. system loss (LS+ Cyclone + bend + pipe + valves) (con% 40.0000 40.0000Total head loss Pa 9205 3171Input pressure required Pa 110530 104496
Stio. Air flow rate at Operating temp
Inputs
Results
Demonstration unit design calculations
1. Reactor diemensions
1. Reactor Calculations2. Cyclone diemensions
HE
In house design code
Commissioning activities finished early July 2013 !!! Experiments are ongoing. Results will be published soon.
Design and modelling of the 500 kW demo scale unit of CLAS (Cold flow model)
Commissioning of 500 kW cold flow model
Experiments are ongoing to derive the hydrodynamics based scaling equations !!!
Ongoing activities at UONStudy with spray dried oxygen carriersBench scale experiments in 5 kWth rigHydrodynamics study at demonstration scale (500 kWth) rigDetailed Process modelling of ICLAS-oxyfuel 250MWe
Journal publications• Kalpit Shah, Behdad Moghtaderi, Jafar Zanganeh and Terry Wall. Integration options for novel
chemical looping air separation (ICLAS) process for oxygen production in oxy-fuel coal fired power plants, Fuel 2013 (Accepted article in press: Uncorrected proof).
• Kalpit Shah, Behdad Moghtaderi, and Terry Wall. Effect of flue gas impurities on the performance of a chemical looping based air separation process for oxy-fuel combustion, Fuel 103 (2013), pp 932-942.
• Kalpit Shah, Behdad Moghtaderi, and Terry Wall. Selection of Suitable Oxygen Carriers for Chemical Looping Air Separation: A Thermodynamic Approach. Enrgy and Fuels 26 (4) (2012), pp2038-2045.
Thank you