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