Adsorption Materials and Processes for Carbon Capture from Gas-Fired Power Plants – AMPGas - presentation by Enzo Mangano in the Natural Gas CCS session at the UKCCSRC Cardiff Biannual Meeting, 10-11 September 2014

1. University of Edinburgh , School of Engineering, Edinburgh
SCCS – Scottish Carbon Capture and Storage Centre
Adsorption Materials and Processes for Carbon Capture from Gas-Fired Power Plants – AMPGas
E. Mangano1, E. Shiko1, A. Greenaway3, A. Gibson2, A. Gromov2, M. M. Lozinska3, H. Ahn1, M. C. Ferrari1, H. Yiu4, E. Campbell2, P. A. Wright3, S. Brandani1
1 University of Edinburgh, School of Engineering;
2 University of Edinburgh, School of Chemistry;
3 University of St. Andrews;
4 Heriot-Watt University
EPSRC: EP/J02077X/1
s.brandani@ed.ac.uk

2. AMPGas Project 2
Partners:
The University of Edinburgh (Coordinator)
University of St. Andrews
Heriot-Watt University
Industrial Partner:
Howden Group Ltd
Other industrial contributions:
Chemviron Carbon; Purolite; Thomas Swan and UOP CCS and Industry – Cardiff Biannual Meeting, 10 – 11 Sept. 2014

3. AMPGas Project 3
Aims:
•
Apply a range of experimental techniques to determine equilibrium and kinetic properties of nanoporous materials, which are being developed for CO2 capture from dilute streams;
•
Predict the performance of an integrated adsorption process based on rapid thermal swing;
•
Demonstrate the proposed process using a bench scale rotary wheel adsorber.
Materials:
Thanks to the expertise of the partners different materials can be tested:
Zeolites (St. Andrews University)
Amine-containing MOFs (St. Andrews University)
Amine-based Silicas (Heriot-Watt University & St. Andrews University)
Amine-containing Carbon and Carbon Nanotubes (University of Edinburgh)
CCS and Industry – Cardiff Biannual Meeting, 10 – 11 Sept. 2014

4. Adsorbents: the challenges 4
Tailoring novel adsorbents for CO2 separation from dilute streams:
Physisorption (optimised zeolites)
Chemisorption (amine-based adsorbents )
•
Structures
•
Cation types
•
Cation distribution
•
Hydrophilicity
•
Supporting material
•
Pore size/volume
•
Amine groups
•
Synthesis process
•
Chemical and thermal stability
•
Behaviour in presence of water CCS and Industry – Cardiff Biannual Meeting, 10 – 11 Sept. 2014

5. Cation Gating Zeolites: Flexible, highly selective adsorbents 5
Zeolites containing double 8 membered rings, such as:
ECR-18
Have been shown to exhibit excellent CO2/N2 selectivity due to a cation gating mechanism: CCS and Industry – Cardiff Biannual Meeting, 10 – 11 Sept. 2014
-

6. Reducing hydrophilicity of Cation Gating zeolites 6
Improving performance of zeolitic materials by implementing an hydrophobic shell with long alkyl chain functionalised silanes
SiCl3
Hydrophilic zeolite, deactivated by water
Hydrophobic zeolite, retains high CO2 capacity CCS and Industry – Cardiff Biannual Meeting, 10 – 11 Sept. 2014
Details on the experimental results on the hydrophobic materials can be found in the poster of Dr. Eleni Shiko

7. Functionalization of Carbon Materials 7
Functionalization of carbon nanotubes with basic amine moieties
MWCNT/agarose aerogel produced by lyophilisation
•
Carbon nanotubes can be functionalized for selective carbon capture
•
Functionalized CNTs can be utilised to create 3D structures with high specific surface area
•
Can be heated ohmically for cyclic regeneration of the adsorbent CCS and Industry – Cardiff Biannual Meeting, 10 – 11 Sept. 2014

8. Material Preparation
Three main types of material prepared:
1. CNTs grafted with a basic amino functionalities
2.
Activated carbon grafted with amino functionalities
3.A physical impregnation of amino groups to the surface
of two different types of porous carbon
8
Amine
Grafted carbon nanotubes (CNT-CO-NHR)
Amine grafted porous carbon
Amine impregnated porous carbon (various loadings)
EDA
√
√
√
DETA
√
-
√
TETA
√
√
√
PEI (MW600)
√
√
√
PEI (MW10000)
√
√
√
PEI (MW750000)
√
-
-
Linear Triethylenetetramine (TETA): CCS and Industry – Cardiff Biannual Meeting, 10 – 11 Sept. 2014

9. Physical impregnation of amine onto porous carbons
N2 isotherms at 77 K at various weight loadings of TETA:
(A) Microporous activated carbon (AC) (B) Mesoporous activated carbon (MC) 9
0
100
200
300
400
500
0
0.2
0.4
0.6
0.8
1
Volume/ cc g-1
P/P0
AC
AC-TETA-10
AC-TETA-30
AC-TETA-50
AC-TETA-70
0
100
200
300
400
500
600
700
0
0.2
0.4
0.6
0.8
1
Volume/ cc g-1
P/P0
MC10
MC10-TETA-10
MC10-TETA-30
MC10-TETA-50
MC10-TETA-70
Surface Area [m2 /g]
Pore Volume [cc/g]
AC
MC
AC
MC
Raw
1280
849
0.74
1.09
TETA-10
972
525
0.52
0.77
TETA-30
220
281
0.11
0.47
TETA-50
23.9
166
0.02
0.31
TETA-70
1.10
95.6
0.01
0.19
TETA-X: X= Percentage weight loading of amine CCS and Industry – Cardiff Biannual Meeting, 10 – 11 Sept. 2014

10. Thermal gravimetric analysis (TGA) 10
00.10.20.30.40.50.60.70.80.910246810 q/ mmols g-1 Time/ hours35 °C50 °C75 °C90 °C00.050.10.150.20.250.301234 q/ mmols g-1 Time/ hours35 °C50 °C75 °C
A C
Functionalised
A C CCS and Industry – Cardiff Biannual Meeting, 10 – 11 Sept. 2014
T, °C
ΔHADS, kJ mol-1
ΔHDES, kJ mol-1
AC
35
-28.0
26.2
50
-27.8
26.3
75
-28.5
28.6
35
-97.4
98.0
AC-TETA-50
50
-88.9
88.7
75
-90.9
90.7
90
-90.5
91.1
MC-TETA-30
75
-87.8
85.7
MC-TETA-50
75
-91.2
91.3
MC-PEI600-100
75
-92.5
92.4
27 kJ mol-1
90 kJ mol-1
PCO2 = 0.1 bar

11. Ranking of CO2 capacity for selected carbon materials (UoE) 11
0
0.2
0.4
0.6
0.8
1
1.2
1.4
1.6
1.8
q [mol/kg]
35 °C
50 °C
62 °C
75 °C
90 °C
PCO2 = 0.1 atm
AC (Calgon-SRD10061)
AC-TETA-10
AC-TETA-30
AC-TETA-50
AC-TETA-75
MC10-TETA-50
MC10-TETA-75
MC10-TETA-85
AC-microporous activated carbon;
MC- mesoporous activated carbon;
Benchmark: Commercial AC (Calgon) CCS and Industry – Cardiff Biannual Meeting, 10 – 11 Sept. 2014

12. Ranking of CO2 capacity for Zeolites (UoStA)
T = 35 °C; PCO2 = 0.1 atm CCS and Industry – Cardiff Biannual Meeting, 10 – 11 Sept. 2014

13. 13
Breakthrough experiment on Li - Rho
Ptot = 1 atm
T = 35 °C
YCO2 = 0 .05
YCH4 = 0.4
Carrier gas: He CCS and Industry – Cardiff Biannual Meeting, 10 – 11 Sept. 2014
CO2/CH4 selectivity

14. Breakthrough experiments on Paulingite 14
Ptot = 1 atm
YCO2 = YN2 = 0.3 in He
Evidence of structural change
Adsorption CCS and Industry – Cardiff Biannual Meeting, 10 – 11 Sept. 2014
CO2/N2 selectivity

15. ZLC kinetic experiments on Na-Rho – 1% CO2
R2/D = 167 min
1 % experiment BELOW 10% !!!
Evidence of structural change CCS and Industry – Cardiff Biannual Meeting, 10 – 11 Sept. 2014 15

16. Rotary Wheel Adsorber for carbon capture – Advantages
16
•
Can treat large volumes of gas
•
Lower capital cost (no multiple columns, piping , valves, etc…)
•
Efficient heat integration
•
Low pressure drop
•
Can perform rapid temperature swings
•
Thermal cycles of few minutes: 10 times faster than traditional TSA in fixed bed
•
Significant reduction of the size of the capture plant
Due to very low concentration of CO2 thermal swing adsorption is required for rapid regeneration of the adsorbent. A properly designed rotary wheel adsorber: CCS and Industry – Cardiff Biannual Meeting, 10 – 11 Sept. 2014

17. Bench scale Rotary Wheel Adsorber for carbon capture
17
•
12-columns rotary system
•
Each column is detachable and can be independently tested
•
Up to 24 thermocouples (2 per column)
•
Large amount of data to be sent in real time
•
Max. rotational speed 1 rpm
•
Regeneration using electrical heating elements
•
One of the first LiFi communication on moving elements
•
Real time computer for data acquisition and control of the system CCS and Industry – Cardiff Biannual Meeting, 10 – 11 Sept. 2014
Rotating part
Stationary part
Stationary part

18. RWA concept - system control
18
Slip rings for H-E
60 W AC motor 0 - 1 rpm
NI – CRIO real time computer
MFC
Gas
D-P transducers
LED ring
TC data + position
LiFi receiver CCS and Industry – Cardiff Biannual Meeting, 10 – 11 Sept. 2014

19. 19
Real rotary system CCS and Industry – Cardiff Biannual Meeting, 10 – 11 Sept. 2014

20. Complete modelNon- Isothermal: 1TNon- Isothermal: 2TNon- Isothermal: 3TIsothermalNo Pressure dropPressure dropNo Film resistanceFilm resistanceNoMacroporeMacroporeLDFMacroporeDiffusionMicroporeLDFMicroporeDiffusionMicroporeEquilibriumDusty Gas ModelMS-Surface diffusionComplete diffusion
Adsorption model hierarchy 20
Now including also Ideal Adsorption Solution Theory methods for multicomponent adsorption
Dr. Daniel Friedrich CCS and Industry – Cardiff Biannual Meeting, 10 – 11 Sept. 2014

21. General adsorption cycle simulator 21
Feed Pressurisation
Adsorption
Evacuation
PE
Purge
PE
Column 2
Column 1
Adsorption systems
•
Multiple adsorption columns
•
Connected by splitters, mixers, valves and tanks
•
Series of cycle steps: pressurisation, feed, purge, …
Extend column simulation to general adsorption cycles
•
Modular system with different units: adsorption columns, valves, splitters, tanks, ...
•
Arbitrary number and connection of the units
•
Simulate different cycle configurations by time events, e.g. switching of valves
Dr. Daniel Friedrich CCS and Industry – Cardiff Biannual Meeting, 10 – 11 Sept. 2014

22. Buffer unit for unibed approach 22
•
All columns cycle through the same steps
•
Steps with interaction between two columns
•
Output of one column is input of the other column
•
Add a buffer unit for each interaction pair
•
Data in buffer unit is half a cycle out of date
•
Same result at Cyclic Steady State
•
Order of magnitude faster
Dr. Daniel Friedrich CCS and Industry – Cardiff Biannual Meeting, 10 – 11 Sept. 2014

23. 23
Preliminary simulations
TRI-PE-MCM-41
P = 0.05 bar
Adapting Cysim cycle simulator for the simulation of a base case study:
Adsorbent : TRI-PE-MCM-41(Y. Belmabkhout, et al., 2010)
Feed: 5% CO2 in N2
Adsorption time: 1 min 35 °C
Heating time: 3 min
F = 200 cc/min CCS and Industry – Cardiff Biannual Meeting, 10 – 11 Sept. 2014

24. 24
Preliminary simulations CCS and Industry – Cardiff Biannual Meeting, 10 – 11 Sept. 2014

25. LiFi – how does it work? 25
Time
Intensity
1
1
1
1
0
0
0
0
0
On
Off
Spectrum:
•
Unregulated (free)
•
Huge
•
Safe Existing Infrastructure Inexpensive devices
Prof. Harald Haas, Dr. Stefan Videv CCS and Industry – Cardiff Biannual Meeting, 10 – 11 Sept. 2014

26. Recent ‘hero’ demonstrations 26
3.5 Gbps from single color LED at 5 mW 1.1 Gbps at 10 m at 5 mW
5 mW
Prof. Harald Haas, Dr. Stefan Videv CCS and Industry – Cardiff Biannual Meeting, 10 – 11 Sept. 2014

27. Conclusions
•
Several materials have been developed and tested using different techniques (ZLC, TGA, Breakthrough)
•
Some of the amine-based carbons show a clear chemisorption process
•
Some of the zeolitic frameworks show evidence of structural modification associated to the presence of CO2
•
A novel bench scale rotary wheel adsorber has bee designed and is being built at the UoE
•
CySim is being modified to predict the performance of the bench scale prototype
•
A novel LiFi communication system (one of the first on moving elements) is being developed for the data acquisition in the RWA CCS and Industry – Cardiff Biannual Meeting, 10 – 11 Sept. 2014 27

28. Acknowledgments 28
We would like to acknowledge the financial support of: UK CCS Research Centre in carrying out this work. The UKCCSRC is funded by the EPSRC as part of the RCUK Energy Programme. EPSRC for funding the AMPGas project (EP/J02077X/1) CCS and Industry – Cardiff Biannual Meeting, 10 – 11 Sept. 2014