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TRANSCRIPT
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Carbon Composite Adsorbents for Post Combustion CO2 Capture
ENERGY FLAGSHIP
Presenter: Yonggang Jin Research Team: Shi Su, Yonggang Jin, Ramesh Thiruvenkatachari, Jun Bae, Xinxiang Yu
HiPerCap EU-Australia workshop, Melbourne, 25-27 March 2015
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Lab Scale Study – Carbon Fibre Composites
Carbon Fibre (s) and Phenolic
resin binding material
Slurry or Paste
Vacuum Moulded to
honeycomb structure
Drying at 50-60ºC and
Curing at 130-150ºC
Carbonised with inert gas at
650-850ºC to pyrolize the resin
Activation at 650-950ºC to
achieve pore characteristics
Carbon Fibre (s) and Phenolic
resin binding material
Slurry or Paste
Vacuum Moulded to
honeycomb structure
Drying at 50-60ºC and
Curing at 130-150ºC
Carbonised with inert gas at
650-850ºC to pyrolize the resin
Activation at 650-950ºC to
achieve pore characteristics
Fabricated (HMCFC)
Length: 80mm, Dia: 30mm, Number of Channels: 17,
Microscopic morphology
Molding equipment
3 processing furnaces
Breakthrough Test Rig with Lab Scale Adsorption Chamber Adsorbent Characterisation
Adsorbent Testing Equipments
Fabrication and Testing of Lab Size Honeycomb Carbon Fibre Composite Monoliths
CSIRO carbon composite adsorbents for PCC 2 |
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Solid Carbon Sorbent CO2 Capture Technology • Based on honeycomb carbon composite monoliths
Enable CO2 capture with low pressure drop
Potentially low energy consumption for adsorbent regeneration
• Lower heat capacity of solid adsorbents than liquid solvents
• Physisorption - lower heat of CO2 adsorption
• Utilisation of flue gas waste heat for CO2 desorption
Tolerant to moisture, SOx and NOx • Avoid flue gas pre-treatment prior to CO2 capture; this is important as
there are no FGD and SCR DeNOx facilities at coal fired power plants in Australia
CSIRO carbon composite adsorbents for PCC 3 |
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Evolutionary Journey
CSIRO carbon composite adsorbents for PCC 4 |
Lab scale CO2 capture
(2006-2008)
Large scale CO2 capture with regeneration (2009-2011)
• Proof-of-Concept • Capture studies using
simulated flue gas
CO2 capture site trials
(2011-2014)
• CO2 capture combined with thermal and vacuum regeneration
• To evaluate CO2 capture and regeneration under real flue gas conditions
Lab scale studies Development of next generation carbon composite adsorbents (2010 – present)
Lab scale study New regeneration process with enhanced heat transfer (2011 – present)
NEXT
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Large Scale Capture-Regeneration Studies
CF composites
CSIRO carbon composite adsorbents for PCC 5 |
Large size adsorbent (Ø 123 mm)
Lab size adsorbent (Ø 30mm)
Large scale CO2 capture-regeneration unit
• Two 2 meter long columns • Repetitive capture & regeneration capability • Thermal and vacuum swing regeneration
CO2 adsorption Isotherms at 25 oC
• 11.7 wt % at 760 mmHg • 3.5 wt % at 114 mmHg (15% CO2)
Large scale moulding unit for composite fabrication
R. Thiruvenkatachari, S. Su et al., International Journal of Greenhouse Gas Control, 2013, 13, 191-200.
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CSIRO carbon composite adsorbents for PCC 6 |
Summary of Large Scale Study Results
Adsorption Breakthrough Profile Showing CO2 capture at Real Time
• CO2 capture carried out at ambient temperature and pressure • Simulated flue gas consisting of 13% CO2, 5.5% O2 and balance N2 • CO2 adsorption efficiency > 97% from adsorption breakthrough
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00:00:00 00:14:24 00:28:48 00:43:12 00:57:36 01:12:00 01:26:24
Co
lum
n T
emp
era
ture
, C
an
d G
as
Flo
w R
ate
, S
LM
Ga
s C
on
c.,
%
Time, h:m:s
CO2 Conc O2 Conc
Gas Flow Rate Bottom Temp
Top Temp
R. Thiruvenkatachari et al., International Journal of Greenhouse Gas Control, 2013, 13, 191-200.
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CSIRO carbon composite adsorbents for PCC 7 |
Thermal and Vacuum Regeneration Vacuum Regeneration
• Residual CO2 inside column after thermal regeneration
• Vacuum regeneration alone is ineffective • Heating is essential to desorb CO2 • Combined thermal and vacuum regeneration
with pure product purge is most effective • Very high purity of recovered CO2 • CO2 recovery > 95%
Individual Thermal Regeneration
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0:00:00 0:14:24 0:28:48 0:43:12 0:57:36 1:12:00 1:26:24
Des
orb
ed g
as v
ol,
L
Gas
co
nc,
%
Time, h:m:s
CO2
Gas Vol
Desorbed Gas Out
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Co
lum
n P
ress
ure
, K
pa
CO
2C
on
c, %
Time, hr:min:sec
CO2
Pressure
Vacuum Only
without Heating
Vacuum Stop
Start Heat
Combined Thermal and Vacuum Regeneration
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Des
orb
ed g
as v
olu
me,
L
Des
orb
ed C
O2
con
c.,
%
Time, h:m:s
CO2 Conc
Gas Vol
Volume of CO2 by Thermal Regeneration
Volume of CO2 by Vacuum Regeneration
R. Thiruvenkatachari, S. Su et al., International Journal of Greenhouse Gas Control, 2013, 13, 191-200.
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CSIRO carbon composite adsorbents for PCC 8 |
Site Trials of Prototype CO2 Capture Unit
• Objective – to evaluate the stability of honeycomb CF composite monolithic adsorbents
using the real flue gas at Vales Point Power Station – to test the effect of real flue gas characteristics on the operation and
performance of the CO2 capture unit
• Site installation, commissioning and testing
Opening of real flue gas to test
unit for first time at Vales Point
Power Station
Fully commissioned solid sorbent prototype
unit at Vales Point power Station Individual sensors to measure
SOx, NOx, CO and CO2 for
accurate measurement
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CSIRO carbon composite adsorbents for PCC 9 |
Site trial testing involving two main scenarios
– CO2 capture performance with flue gas pre-treatment
– CO2 capture performance without flue gas pre-treatment
Process methodology adopted for site trials
Performance of carbon composite solid adsorbents evaluated:
– Stability of adsorbents to real flue gas evaluated from over 200 tests
– CO2 removal performance
– Solid sorbent performance to removal of other gases apart from CO2
Site Trials of Prototype CO2 Capture Unit (continued)
Flue gas IN
Caustic Scrubber System for Flue gas
Pre-treatment
Adsorption/ Gas capture
CO2 FlushingThermal & Vacuum Swing Regeneration
CO2 Recovered from Fluegas
Recovered CO2 for FlushingFlue gas without Pre-treatment
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CSIRO carbon composite adsorbents for PCC 10 |
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07:12 15:33 23:54 32:15 40:36 48:58
Gas
Co
nce
ntr
atio
n, p
pm
CO
2C
on
cen
trat
ion
, %
Time, m:s
CO2 SO2 (ppm)NO (ppm) NO2 (ppm)CO2 vol% SO2 ppmv
NO ppmv NO2 ppmv
Results of Site Trials
Adsorption & desorption: flue gas with pretreatment
pretreatment
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CSIRO carbon composite adsorbents for PCC 11 |
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00:00 03:57 07:53 11:50 15:47 19:44 23:40
Ga
s C
on
cetr
ati
on
, pp
m
CO
2C
on
cen
tra
tio
n, %
Time, m:s
CO2 vol% SO2 ppmvNO ppmv NO2 ppmv
SO2NO2NO
CO2
Results of Site Trials (continued)
Adsorption & desorption: flue gas without pretreatment
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CSIRO carbon composite adsorbents for PCC 12 |
Results of Site Trials (continued)
Excellent stability to real flue gas over 200 site tests – CO2 adsorption efficiency consistently over 98% – CO2 desorption efficiency between 90-95%.
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0102030405060708090
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CO
2 D
eso
rpti
on
Eff
icie
ncy
, %
CO
2 A
dso
rpti
on
Eff
icie
ncy
, %
Run Number
Adsorption
Desorption
Adsorbent stability
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Development of New-Generation Carbon Composite Adsorbents
Objective Enhance CO2 adsorption capacity (smaller footprint, lower capital and
operating costs)
Lower the cost of adsorbents using local biomass waste and brown coals
New-generation carbon composite adsorbents • Carbon nanotube (CNT) modified carbon composite monoliths
• Biomass derived carbon composites (HiPerCap WP2)
CSIRO carbon composite adsorbents for PCC 13 |
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CNT Composites - Source of CNTs
• CPD &CCI are home made, Com the commercial product
CSIRO carbon composite adsorbents for PCC 14 |
CPD CCI Com
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Preparation of CNT Composite Adsorbents
CSIRO carbon composite adsorbents for PCC 15 |
Prepared CNT composite monolith Schematic of composite preparation procedures
CF/CNT/Resin/MC/H2O
Mix Mould
Curing 150 oC 1hr
Carbonisation 650 oC 1hr (N2)
CO2 activation950 oC 15minCO2 adsorption
Characterisation
The current preparation method (physical activation with CO2) is simpler and more economic than chemical activation (e.g. with KOH) and functionalisation with basic groups
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SEM Morphology
Morphology and macropore size distributions of CNT composites
16 | CSIRO carbon composite adsorbents for PCC
Morphology of activated phenolic resin
Y. Jin, S. Hawkins, C. Huynh, S. Su, Energy Environ. Sci., 2013, 6, 2591-2596.
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0 100 200 300 400 500 600 700 8000.0
0.5
1.0
1.5
2.0
2.5
3.0
3.5
CO
2 a
dso
rbe
d (
mm
ol g
-1)
Pressure (mmHg)
CNT composite (Com-15)
CF composite
resin alone derived carbon
0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.00.0
0.1
0.2
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0.4
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0.6
0.7
0.8
Po
re s
ize
dis
trib
utio
n (
cm
3 g
-1 n
m-1)
Pore size (nm)
CNT composite (CCI-15)
CF composite
resin alone derived carbon
Comparisons of CNT and CF composites
CSIRO carbon composite adsorbents for PCC 17 |
CNT composites exhibit much higher CO2 adsorption capacities • CO2 uptake: 15.9 wt% at 25
oC and 1 bar, and 5.2 wt% at 25 oC and 0.15 bar
• Up to 30% increase in CO2 adsorption capacity at 25 oC and 1 bar
• Over 45% increase in CO2 adsorption capacity at 25 oC and low CO2 pressures (0.15 bar)
CO2 uptake at 25 oC Narrow micropore size distributions
Y. Jin, S. Hawkins, C. Huynh, S. Su, Energy Environ. Sci., 2013, 6, 2591-2596.
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Adsorption Selectivity & Kinetics
CSIRO carbon composite adsorbents for PCC 18 |
0 100 200 300 400 500 600 700 8000
1
2
3
4
5
CO2-273K
CO2-298K
N2-273K
Am
ou
nt
ad
so
rbe
d (
mm
ol g
-1)
Absolute pressure (mmHg)
N2-298K
CO2 & N2 uptake adsorption Isotherms at 0 and 25 oC
Rates of CO2 adsorption at 25 oC
and 25 mmHg
• CO2/N2 selectivity: 32.6 at 273 K and 19.8 at 298 K • Fast adsorption kinetics observed in the CNT composites
Y. Jin, S. Hawkins, C. Huynh, S. Su, Energy Environ. Sci., 2013, 6, 2591-2596.
0 50 100 150 200 250 3000
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resin alone derived carbon (Res-60)
CNT composite (Com-15)
Ad
so
rptio
n c
om
ple
ted
(%
)Time (s)
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Conclusions
• Porous carbon composite monoliths show great promise in post-combustion CO2 capture.
• Site trials demonstrate the excellent stability of the carbon composite adsorbent towards real flue gas.
• New-generation CNT carbon composite adsorbents exhibit significantly enhanced CO2 uptake particularly under low CO2 pressures, which is of more relevance for flue gas applications.
CSIRO carbon composite adsorbents for PCC 19 |
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Acknowledgements
• Funding supports from:
Coal Innovation NSW for the site trials of prototype CO2 capture unit at the Vales Point power station
ANLEC R&D for the development of CF/CNT composites
CSIRO
• Site support from Delta Electricity
CSIRO carbon composite adsorbents for PCC 20 |
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ENERGY FLAGSHIP
Thank you Dr Shi Su Senior Principal Research Scientist Team Leader Phone: 07 3327 4679 Email: [email protected] Web: www.csiro.au