The Challenge World of Carbon Dioxide and CCS (Carbon Capture
Carbon Capture, Storage and Utilization
Shik Chi Edman TSANG [email protected]
Inorganic Chemistry Laboratory University of Oxford
Contents for This Seminar 1
•Why do we need CCS? •The magnitude of CCS
2
Key Challenges of CCS
3 4
New CCS materials 5
Carbon Recycle and Utilization 6. Summary and Outlook
1. Why do we need CCS ?
Business as usual -total final consumption
Source: Shell 2006
Global carbon pools and fluxes. Modified from Lal (2008)
River Thames Picture
River Thames= 3 x 1015g H2O Lock Ness = 7.4 x 1015g H2O
(10 times p.a.) (3 times p.a.)
2. The magnitude of CCS
The concept is to store carbon permanently and safely on the ground at large scale. The storage needs to be maintained and the responsibility for keeping the carbon out of the mobile carbon pool for a long time.
Amine Scrubbing for CO2 Capture
Amine scrubbing has been used to separate carbon dioxide (CO2) from natural gas and hydrogen since 1930. It is a robust technology and is ready to be tested and used on a larger scale for CO2 capture from coal-fired power plants. Gary T. Rochelle, et al. Science, 325, 1652 (2009)
1. Inorganic Physisorbents Adsorbents a. Zeolites b. Activated carbons 2.Chemisorbents a. Metal-based adsorbents b. Hydrotalcite-like compounds 3. Organic and Organic– Inorganic Hybrid Adsorbents Amines physically adsorbed on oxide supports; covalently tethered to oxide supports; on solid organic materials 4. Metal–Organic Frameworks: An Emerging Class of Materials 5. Ionic liquids
Precipitation-sublimation method:
SiCl4 diluted in pentane + NH3 (g) SixNy Hz (MSIN-X)
Figure 1. (a) Typical TEM image of MSIN-673. (b) Nitrogen sorption isotherms for MSIN-673 and its pore size distribution centred at 2.3 nm (insert).
Table 2 CO2 capture capacities of different materials at 1 bar but various temperatures Samples
Capacity (mmol g-1)
Qst (kJ mol-1) Ref.
298 K
373 K
MSIN-673
2.6
2.3
68.1
This work
AC
2.1
0.7
36.7
This work
Zeolite 13X
3.9
n.d.
34.4
Cu-BTC
4.7
0.5
30.0
MSIN-700
821
0.61
59.7
Figure 4. Cyclic tests of CO2 and N2 adsorptions on MSIN-673 at ambient temperature and pressure.
Synthesis of mesoporous Carbon nitrides
Scheme 1. For preparation of Mesoporous carbon nitride
Vinnu. A. Adv. Funct. Mater. 2008, 18, 816.
CO2 Utilisations
Yu, Curcic, Gabriel, Tsang ChemSusChem. (2008), 1, 893.
The Chemical Fixation of Carbon H2
epoxides
polyols: sugars / glycerol
cyclic carbonates
CO / H2
CO2 / H2
Yu, Curcic, Gabriel, Morganstewart, Tsang, J. Phys. Chem. A, DOI: 10.1021/jp906365g
Carbon Recycle (CO2 to Fuels) Making a liquid fuel from CO2 will give us exciting opportunity to recycle the greenhouse gas to make the fuel that runs our engines, producing energy, and provides the basic chemical building blocks that run our industries.
(1) Catalytic fixing of CO2 + renewable H2 to hydrocarbons (2) Catalytic fixing of CO2 + renewable H2 to methanol
(3) Photocatalytic fixing of CO2 + renewable carriers to hydrocarbons/alcohols
Table 1. Catalytic activity comparison of different ZnO mixed with copper in the synthesis of methanol though the hydrogenation of CO2 Note: The reaction condition was fixed at 280 oC and 4.5MPa (CO2/H2 volume ratio = 1:2.18) with 0.3g catalysts (Cu/ZnO/Al 2O3 weight ratio = 1/1/1) in a tube micro-reactor. The detailed calculations of methanol selectivity and carbon conversion were list in supporting information.
CO2 + 3H2 = CH3OH + H2O Catalyst
CO2 Conversion/%
CH3OH Selectivity/%
Rod ZnO/Cu/Al2O3
15.3
39.1
Plate ZnO/Cu/Al2O3
12.0
71.6
catalytic interface:
Tsang et al., Angew Chem, 2011, doi: 10.1002/anie.201007108.
Yu, Leung, Tsang, J. Am. Chem. Soc., 129(20) (2007), 6360 – 6361
6. Summary and Outlook
•CCS can offer possible way to reduce CO2 emission and has the potential to offset years of accumulative CO2 from atmosphere
•Cost of CCS must be reduced (new chemistry, new materials, novel engineering and separation) •Lessons learned from small or large field projects will help deployment of CCS •Ambient CCS should be addressed •Recycling of carbon and utilization are more ideal than storage
•Educate people to be more energy conscious
Acknowledgements
Abdullah Khan, Hongwei Yang, Dr Kerry Yu , Dr Connie Yeung, Dr Adam Kong, Dr. Valarie Caps, Dr Eric Yu, Dr Nick Cailuo, Dr William Oduro, Karaked Tedsree, Dr Nadia Acerbia (Oxford Chem)
Tong Li, Dr. Paul Bagot, Prof. Angus Kirkland , Prof. George Smith (Oxford Materials) Drs Peter Bishop, Bene Thiebaut, James Cookson, David Thompsett , Janet Fischer and Paul Collier (Johnson Matthey) Dr Stan Glounski (Cardiff Univ.) Professor R Burch, Professor Chris Hardacre (QUB Univ.) Professor Heyong He, Prof. Xueqing Gong (Shanghai, China)
Shik Chi Edman TSANG [email protected]
Inorganic Chemistry Laboratory University of Oxford
Contents for This Seminar 1
•Why do we need CCS? •The magnitude of CCS
2
Key Challenges of CCS
3 4
New CCS materials 5
Carbon Recycle and Utilization 6. Summary and Outlook
1. Why do we need CCS ?
Business as usual -total final consumption
Source: Shell 2006
Global carbon pools and fluxes. Modified from Lal (2008)
River Thames Picture
River Thames= 3 x 1015g H2O Lock Ness = 7.4 x 1015g H2O
(10 times p.a.) (3 times p.a.)
2. The magnitude of CCS
The concept is to store carbon permanently and safely on the ground at large scale. The storage needs to be maintained and the responsibility for keeping the carbon out of the mobile carbon pool for a long time.
Amine Scrubbing for CO2 Capture
Amine scrubbing has been used to separate carbon dioxide (CO2) from natural gas and hydrogen since 1930. It is a robust technology and is ready to be tested and used on a larger scale for CO2 capture from coal-fired power plants. Gary T. Rochelle, et al. Science, 325, 1652 (2009)
1. Inorganic Physisorbents Adsorbents a. Zeolites b. Activated carbons 2.Chemisorbents a. Metal-based adsorbents b. Hydrotalcite-like compounds 3. Organic and Organic– Inorganic Hybrid Adsorbents Amines physically adsorbed on oxide supports; covalently tethered to oxide supports; on solid organic materials 4. Metal–Organic Frameworks: An Emerging Class of Materials 5. Ionic liquids
Precipitation-sublimation method:
SiCl4 diluted in pentane + NH3 (g) SixNy Hz (MSIN-X)
Figure 1. (a) Typical TEM image of MSIN-673. (b) Nitrogen sorption isotherms for MSIN-673 and its pore size distribution centred at 2.3 nm (insert).
Table 2 CO2 capture capacities of different materials at 1 bar but various temperatures Samples
Capacity (mmol g-1)
Qst (kJ mol-1) Ref.
298 K
373 K
MSIN-673
2.6
2.3
68.1
This work
AC
2.1
0.7
36.7
This work
Zeolite 13X
3.9
n.d.
34.4
Cu-BTC
4.7
0.5
30.0
MSIN-700
821
0.61
59.7
Figure 4. Cyclic tests of CO2 and N2 adsorptions on MSIN-673 at ambient temperature and pressure.
Synthesis of mesoporous Carbon nitrides
Scheme 1. For preparation of Mesoporous carbon nitride
Vinnu. A. Adv. Funct. Mater. 2008, 18, 816.
CO2 Utilisations
Yu, Curcic, Gabriel, Tsang ChemSusChem. (2008), 1, 893.
The Chemical Fixation of Carbon H2
epoxides
polyols: sugars / glycerol
cyclic carbonates
CO / H2
CO2 / H2
Yu, Curcic, Gabriel, Morganstewart, Tsang, J. Phys. Chem. A, DOI: 10.1021/jp906365g
Carbon Recycle (CO2 to Fuels) Making a liquid fuel from CO2 will give us exciting opportunity to recycle the greenhouse gas to make the fuel that runs our engines, producing energy, and provides the basic chemical building blocks that run our industries.
(1) Catalytic fixing of CO2 + renewable H2 to hydrocarbons (2) Catalytic fixing of CO2 + renewable H2 to methanol
(3) Photocatalytic fixing of CO2 + renewable carriers to hydrocarbons/alcohols
Table 1. Catalytic activity comparison of different ZnO mixed with copper in the synthesis of methanol though the hydrogenation of CO2 Note: The reaction condition was fixed at 280 oC and 4.5MPa (CO2/H2 volume ratio = 1:2.18) with 0.3g catalysts (Cu/ZnO/Al 2O3 weight ratio = 1/1/1) in a tube micro-reactor. The detailed calculations of methanol selectivity and carbon conversion were list in supporting information.
CO2 + 3H2 = CH3OH + H2O Catalyst
CO2 Conversion/%
CH3OH Selectivity/%
Rod ZnO/Cu/Al2O3
15.3
39.1
Plate ZnO/Cu/Al2O3
12.0
71.6
catalytic interface:
Tsang et al., Angew Chem, 2011, doi: 10.1002/anie.201007108.
Yu, Leung, Tsang, J. Am. Chem. Soc., 129(20) (2007), 6360 – 6361
6. Summary and Outlook
•CCS can offer possible way to reduce CO2 emission and has the potential to offset years of accumulative CO2 from atmosphere
•Cost of CCS must be reduced (new chemistry, new materials, novel engineering and separation) •Lessons learned from small or large field projects will help deployment of CCS •Ambient CCS should be addressed •Recycling of carbon and utilization are more ideal than storage
•Educate people to be more energy conscious
Acknowledgements
Abdullah Khan, Hongwei Yang, Dr Kerry Yu , Dr Connie Yeung, Dr Adam Kong, Dr. Valarie Caps, Dr Eric Yu, Dr Nick Cailuo, Dr William Oduro, Karaked Tedsree, Dr Nadia Acerbia (Oxford Chem)
Tong Li, Dr. Paul Bagot, Prof. Angus Kirkland , Prof. George Smith (Oxford Materials) Drs Peter Bishop, Bene Thiebaut, James Cookson, David Thompsett , Janet Fischer and Paul Collier (Johnson Matthey) Dr Stan Glounski (Cardiff Univ.) Professor R Burch, Professor Chris Hardacre (QUB Univ.) Professor Heyong He, Prof. Xueqing Gong (Shanghai, China)
