Design of an Integrated CSP-Calcium Looping for Uninterrupted Power Production Through Energy storage.

SOlar Calcium looping integRAtion for Thermo-Chemical Energy Storage
SOlar Calcium looping integRAtion for Thermo-Chemical Energy
Storage
Design of an Integrated CSP-Calcium
Looping for Uninterrupted Power
Production Through Energy Storage
21st Conference on Process Integration for
Energy Saving and Pollution Reduction - PRES
2018, 25-29 August 2018, Prague, Czech
Republic
Evgenios Karasavvas, Kyriakos Panopoulos,
Simira Papadopoulou, Spyros Voutetakis
Chemical Process and Energy Resources Institute
(CPERI), Centre for Research and Technology – Hellas
(CERTH), 57001 Thermi-Thessaloniki, Greece

100 MW
Work
Power
System
Power
System
Time horizon=12 hrs
Concentrating Solar Power (CSP) plant – Thermochemical Energy Storage (TCES)
PRES 2018 25-29 August 2018
PRAGUE, CZECH REPUBLIC
Exothermic
Endothermic
CaO (s) + CO2 (g) → CaCO3 (s)CaCO3 (s) → CaO (s) + CO2 (g)

SOCRATCES Project – Description
PRES 2018 25-29 August 2018
• Ca-Looping (CaL)-Concentrating Solar
Power (CSP) plant
• Most promising technology for
thermochemical energy storage (TCES)
Solar driven
calcination
reaction
Highly
exothermic
carbonation
reaction
T~650-1000
oC
Reactants/
Products
stored at
ambient
temperatures
High energy
density of
CaO/CaCO3
~3226 MJ/m3
Low price (<10
€/tn),
Abundant,
Harmlessness
of natural
CaCO3
Pilot-scale
plant
erection
(10 kWth)
Molten salts
CaCO3 (s) ↔ CaO (s) + CO2
(g)

System Integration: Carbonation/Calcination
PRES 2018 25-29 August 2018
Presentation Outline
• The scope of the study
• Process description of a conceptual CSP-CaL integration scheme
• Calcination Process Flow Diagram for Thermochemical Energy
Storage (TCES) and Power Production
• Carbonation Process Flow Diagram for Power Production
• Calciner - Carbonator Integration Scheme
• Calcination section simulations results
• Carbonation section simulations results
• Conclusions

PRES 2018 25-29 August 2018
Conceptual CSP-CaL integration scheme
▪ Use of solar energy to heat CO2 (>1000 oC) / accomplish calcination / preheat solids
▪ Surplus CO2 to exploit excess thermal energy → power production through Rankine cycle
during daylight / Brayton or Rankine cycle during the night
Heat
Exchanger
Network
Calciner Carbonator
CaO
Storage
Water
Rankine
Cycle
Heat
Exchanger
Network
CO2
Storage
CaCO3/
CaO
Storage
Compression Expansion
Brayton or
Rankine Cycle
Q
CaO (s)
CO2 (g)
CO2 (g)
CO2 (g)
CaO (s)
CaCO3
(s)
CO2 (g)
CO2 (g)
CaCO3 (s)
CO2
CaO
CaCO3
CaCO3 (S)→CaO (s) + CO2 (g)
ΔΗrxn = +178 kJ/mol
CaO (s) + CO2 (g)→CaCO3 (s)
ΔΗrxn = -178 kJ/mol
Calciner side| Energy input| Energy production
12 hours the day
Carbonator side| Energy production
12 hours the night
CaO (s), T=200-700 o
C
Tcarb=875 o
C
Pcarb=1-7 bar
Tcalc=950 o
C
Pcalc=1 bar

Calcination: Thermochemical Energy Storage (TCES) & Power Production in the day
PRES 2018 25-29 August 2018
CaCO3
Storage
CO2
Storage
Turbine
Rankine
Compressor
S-03
S-04
S-06
S-01
S-07
S-20
S-21
S-22
S-19
S-02
S-05
Compressor
1
S-14S-13S-12S-10S-09
S-08
Compressor
2
Compressor
3
S-15 S-16 S-17 S-18
S-11
Cooler2 IntCool1 IntCool2 IntCool3
HXA
Evaporator
Solar
HX Calciner
Pump
Condenser
Cooler1
CaCO3/
CaO
CO2
H20
Insulated
CaO
Storage
TCO2=? [1000,1050,1100] oC
• A design based on a volumetric gas (CO2) solar receiver
• CO2 heated up above 1000 oC to preheat solids / accomplish calcination
• Large amounts of hot CO2 recirculates → Exploitation (Rankine) → Power production
• CO2 through a three stage compression and intercoolings to store. (75 bar / Ambient Temp.)
• Storage of produced solids (CaO/CaCO3) at an insulated storage vessel
• Parametric analysis of CO2 receiver temperature

Carbonation: Power Production in the night
PRES 2018 25-29 August 2018
• Stored solids (CaO/CaCO3) are conveyed to carbonator
• Compressed CO2 after expansion, is pumped through a HX network to carbonator
• Two CO2 alternative routes after carbonator, depending on the carbonation pressure
• Use of ORC to exploit low enthalpy stream (S-08, ~200 oC)
• Parametric analysis of Carbonation pressure and CaO storage temperature
Turbine
Compressor
CaCO3
/CaO
Storage
S-01
S-16
S-03
S-05a
S-06
S-07
S-08
S-10
S-11 S-12 S-13 S-14
S-17
Turbine
Rankine

S-24
S-21 S-22
S-23
S-04b
S-02
CO2
Storage
Insulated
CaO
Storage
Condenser
Pump
Evaporator
Turbine
Brayton
S-04a
S-05b
S-15
S-19
S-09
ORC
HXD HXE HXG
HXI
Carbonator
HXF
CO2
CaO/CaCO3
H20
S-18
S-20
CO2 alternative
routes
TCaCO3=? [200,500,690] oC
Pcarb=? [1,3,5,7] bar

Modelling methodology and model assumptions
PRES 2018 25-29 August 2018
Calcination Assumptions Values Carbonator Assumptions Values
Net solar flux in solar HX (Qinput) (MWth) 100 - -
Thermal losses in calciner (%)
Calciner Temperature (oC)
Calciner pressure (bar)
Ambient Temperature (oC)
CaCO3 conversion (%)
max Rankine temperature (oC)
max Rankine Pressure (bar)
min temperature approach for GG, GS, GL HX (oC)
Intercoolings in CO2 storage compression
Intercoolings in CO2 cycle compression
CO2 storage conditions (bar, ambient)
Daylight hours (h)
Isentropic efficiencies (compression/expansion)
Organic Rankine Cycle (ORC) efficiency (%)
5
950
1
25
97
600
75
50, 25, 25
3
1
75
12
0.89
-
Thermal losses in carbonator (%)
Carbonator temperature (oC)
Carbonator pressure (bar)
Ambient temperature (oC)
CaO conversion (%)
Brayton outlet pressure (bar)
-
-
-
Night hours (h)
0
875
1,3,5,7
25
50
1 bar
-
50, 25, 25
-
1
-
12
0.89
15
, ,12 12
100 12
net day net night
global
W hr W hr
hr

 + 
=

Global plant efficiency
, 1 2 3
,
100
turb rank comp comp comp comp pump
net day
W W W W W W
W
− − − − −
=
, ,mainnet night turb turb ORC compressorW W W W W= + + −

Turbine
Compressor
CaCO3
/CaO
Storage
S-01
S-16
S-03
S-05a
S-06
S-07
S-08
S-10
S-11 S-12 S-13 S-14
S-17
Turbine
Rankine

S-24
S-21 S-22
S-23
S-04b
S-02
CO2
Storage
Insulated
CaO
Storage
Condenser
Pump
Evaporator
Turbine
Brayton
S-04a
S-05b
S-15
S-19
S-09
ORC
HXD HXE HXG
HXI
Carbonator
HXF
S-18
S-20
Calciner – Carbonator Integration Scheme
PRES 2018 25-29 August 2018
CaCO3
Storage
CO2
Storage
Turbine
Rankine
Compressor
S-03
S-04
S-06
S-01
S-07
S-20
S-21
S-22
S-19
S-02
S-05
Compressor
1
S-14S-13S-12S-10S-09
S-08
Compressor
2
Compressor
3
S-15 S-16 S-17 S-18
S-11
Cooler2 IntCool1 IntCool2 IntCool3
HXA
Evaporator
Solar
HX Calciner
Pump
Condenser
Cooler1
CaCO3/
CaO
CO2
H20
Insulated
CaO
Storage

Calcination section scenarios results (1)
PRES 2018 25-29 August 2018
• Maximum solids throughput of 9.3 kg/s ~ 558 kg/min
• Significant decrease of CO2/Solids mass rate with CO2 temperature (78/1 → 8.5/1)
• Calcination Net Work of a range of 25-30 MW
• Decrease of CO2 recycle with CO2 temperature (91 → 81 kg/s)
• Decrease of Rankine H20 flowrate with temperature (26 → 22 kg/s)
30.77 27.9 25
90.95 85.87
81.30
25.74 23.68 21.66
0.75 3.18 6.04
1.16
4.91
9.32
0.00
10.00
20.00
30.00
40.00
50.00
60.00
70.00
80.00
90.00
1000 1050 1100
Work(MW),MassFlow(Kg/s)
Temperature (o
C)
Wnet (MW) FCO2,recycle (Kg/s) FH20 (Kg/s) CaCO3 (kg/s) CaCO3/CaO (kg/s)
CO2/Solids =78/1
CO2/Solids =17/1
CO2/Solids =8.5/1
Parametric analysis of CO2 solar receiver temperature
FCO2,recycle (kg/s) FH2O (kg/s) CaCO3 (kg/s) CaCO3 / CaO (kg/s)

PRES 2018 25-29 August 2018
• Dramatic increase of calcination contribution (1 → 10 MW) and solids preheating
(1 → 9 MW) with CO2 inlet temperature
• Considerable decrease of Rankine input energy (90 → 76 MW) with CO2 inlet temperature
90.2 83 75.89
1.26 5.43 10.42
1.12 4.57
9
7.42 7 4.69
0%
10%
20%
30%
40%
50%
60%
70%
80%
90%
100%
Tcalc_1000 Tcalc_1050 Tcalc_1100
%Distribution
CO2 inlet temperature oC
Distribution of input energy in different sections
Rankine exchanger (MW) Calcination (MW) Solids preheat (MW) Other (MW)

PRES 2018 25-29 August 2018
Parametric analysis of CO2 solar receiver temperature
• Great difference in the energy produced vs. the energy consumed
30.77
27.9
25
33.31
30.64
28.02
2.22 2.12 2.04
0.03 0.12 0.240.04 0.15 0.290.03 0.15
0.270.22 0.2 0.19
0.00
5.00
10.00
15.00
20.00
25.00
30.00
35.00
1000 1050 1100
DistributionofIndividualWork(MW)
Temperature (o
C)
Wnet (MW) Wturb,Rank (MW) Compressor (MW) Compressor 1 (MW)
Compressor 2 (MW) Compressor 3 (MW) Pump (MW)

Carbonation operation scenarios results (1)
PRES 2018 25-29 August 2018
• Carbonation net work of a range of 0.45-5.75 MW
• Increase of net work with CaO storage temperature, CO2 receiver temperature
and carbonator pressure
4.27 4.47 4.56
4.98 5.15 5.22
3.64
5.48 5.68 5.75
0.00
1.00
2.00
3.00
4.00
5.00
6.00
7.00
Pcarb=1 bar Pcarb=3.2 bar Pcarb=5 bar Pcarb=7 bar
Network(MW)
Carbonation pressure (bar)
Carbonation net work from Calcination with Treceiver=1100 oC
TCaO_200 oC TCaO_500 oC TCaO_690 oC Linear (TCaO_690 oC)oC oC oC oC)

PRES 2018 25-29 August 2018
29.3 29.5 29.630.0 30.2 30.228.6
30.5 30.7 30.8
0.00
5.00
10.00
15.00
20.00
25.00
30.00
35.00
Pcarb=1 bar Pcarb=3.2 bar Pcarb=5 bar Pcarb=7 bar
Globalefficiency(%)
carbonation pressure (oC)
Global efficiency of process from calcination with Treceiver=1100 oC
TCaO_200 oC
TCaO_500 oC
TCaO_690 oC
oC
oC
oC
• Slight increase of the global efficiency with the carbonation pressure and CaO
storage temperature
• For fixed CO2 solar receiver temperature → range of efficiency: 28.6-30.8%

PRES 2018 25-29 August 2018
• Generally, contribution of carbonation on the global efficiency increases
significantly with calcination temperature (1.45-18.70 %)
Carbonation contribution on the total produced work for three CO2 receiver temperatures
2.25
97.75
TCO2, Reveiver=1,000 oC
9.69
90.31
TCO2, Receiver=1,050 oC
18.50
81.50
TCO2, Receiver=1,100 oC
Pcarb = 5 bar
TCaO = 690 oC

Conclusions
PRES 2018 25-29 August 2018
• Assuming a 100 MW solar input flux → Power can be produced both in day (calcination)
and night (carbonation)
• Power generation in carbonation examined only by using two alternatives ways (CO2
Brayton cycle or/and Rankine cycle)
• Total heat uptake in the calciner is achieved solely if CO2 is used as the heat transfer fluid
• The majority of the power is produced due to the surplus hot CO2 at calcination section
• Global efficiency is slightly favored by high carbonation pressure and high CaO
storage temperature and slightly reduced with CO2 receiver temperature
• CO2 receiver temperature has a great impact on global performance:
➢ If CO2 temperature increases (1000 →1100 οC) CO2/solids (mass) → DECREASE (78/1 → 8.5/1)
Global efficiency (%) → DECREASE (31.5 → 30.7)
Carbonation contribution (%) → INCREASE (1.45 → 18.70)

This Project has received funding from European Commission by means of Horizon 2020,
the EU Framework Programme for Research & Innovation, under Grant Agreement no.727348.
Thanks for your attention!
Any Questions?
Contact details:
Evgenios Karasavvas: ekarasav@cperi.certh.gr
Kyriakos Panopoulos: panopoulos@certh.gr
Useful links :
https://socratces.eu/
https://www.certh.gr/root.en.aspx

Design of an Integrated CSP-Calcium Looping for Uninterrupted Power Production Through Energy storage.

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Design of an Integrated CSP-Calcium Looping for Uninterrupted Power Production Through Energy storage.