Course on Carbon dioxide to Chemicals
and Fuels
PRESENTATION - FIVE
24TH February 2014
On Line Course of NCCR
(Total Number of Projections for this Lecture is 20)
NCCR on Line L3
1
PHOTOELECTROREDUCTION OF CO2
Appealing Approach!
An important energy input contribution from light might be
expected, thus diminishing electricity consumption
Principle
An Example
J.P. Collin & J.P. Sauvage, Coord. Chem. Rev. 93 (1989) 245
A study on photo-electro-reduction of CO2
Possible Mechanistic Route
By insitu-IR
Photovoltomogram, λ= 560 nm (0.5 mW \cm2)
J, O‘M. Bockris & J. C. Wass, Mater Chem Phys, 22 (1989) 249
Study on photo-electro-reduction of CO2
J, O‘M. Bockris & J. C. Wass, Mater Chem Phys, 22 (1989) 249
Metal islet catalysts deposited on a p-CdTe
electrode in DMF-0.1 M TEAP/5% H20
Product analysis results for CO2 reduction on phthalocyanine/p-CdTe
MPc catalysts adsorbed on a p-CdTe electrode
in DMF-0.1 M TEAP/5% H20
Study on Photo-electro-reduction of CO2
Current-potential curves for trinuclear carbonyl catalysts
adsorbed on a p-CdTe electrode in DMF-0.1 M TEAP/5%
H20.
Product analysis results for CO2 reduction on carbonyl/p-CdTc
Iron carbonyl is the best among the three carbonyls studied
J, O‘M. Bockris & J. C. Wass, Mater Chem Phys, 22 (1989) 249
Study on photo-electro-reduction of CO2
Current-potential curves for crown ether
Product analysis results
catalysts added to the electrolyte for a p-CdTe
J, O‘M. Bockris & J. C. Wass, Mater Chem
electrode in DMF-0.1 M TEAP/S% H20
Phys, 22 (1989) 249
Catalytic shift (ΔE)
Catalytic shift (ΔE) times the CO faradaic
efficiency for metal catalysts on p-CdTe as a
function of M-O bond energy
ΔE values for CO production are linear
For metal-phthalocyanine catalysts on pCdTe
as a function of M-O bond energy
J, O‘M. Bockris & J. C. Wass
Mater Chem Phys, 22 (1989) 249
Catalytic shift (ΔE)
J, O‘M. Bockris & J. C. Wass, Mater Chem Phys, 22 (1989) 249
For trinuclear carbonyl catalysts on p-CdTe
as a function of M-C bond energy
CARBON MANAGEMENT
• Fertilization of open waters to increase primary
production &
hence to absorb more carbon in fixed form
• Disposal of captured carbon dioxide directly
into oceanic waters
• Injection of captured CO2 into sub-seabed
geological formations
CO2 sequestration
Barriers to wider implementation
• High cost of capturing, processing, &
transporting anthropogenic CO2
• Incomplete understanding of reservoir
processes
• Underdeveloped monitoring & verification
technologies
• Unclear emissions trading regulations
• Potential conflicts of interest between
sequestration & EOR or natural gas recovery
CO2 Sequestration
Public Perception
The technology is in its infancy and unproven
• The technology is too costly
• Not enough is known about the long-term storage of
CO2
• The capture and storage of CO2 are seen as being
energy intensive
• The option presents an enormous engineering and
infrastructure challenge
• It is not a long-term solution
Barriers can only be overcome by research and design
& effective demonstration of the technology
Perceptions: Large-Scale CO2 Utilization &
Sequestration
• Two big challenges
– Reducing costs
– Developing storage Reservoirs
• Utilization scores on these two challenges but
opportunities are limited
• Utilization will play a major role in initial
sequestration
• Utilization will play a minor role for long term large
scale sequestration
UTILIZATION
• Opportunities
– Help economics
– Estimates storage issues
Why large scale use of CO2 such a challenge?
– Market sizes
– Transportation costs
– Product life times
– Energy considerations
TRANSPORTATION COSTS
• Many production sources
• CO2 expensive to transport well in small
quantities.
• Use sources of opportunities (process by products
natural wells)
• Example –US 1997 capacity for liquid CO2
– 9.7 million metric tons
– 93 plants
– Largest 900 metric tons/day
– Average 300 metric tons /day
WHAT HAS BEEN COVERED SO FAR
The electronic structure of Carbon dioxide
M. A. Scibioh & B. Viswanathan,Proc. Indn. Natl. Acad. Sci., 70 A
(3), 2004.407-462
CHEMICAL REDUCTION OF
CARBONDIOXIDE
ADDING HYDROGEN AND ELIMINATING WATER
Electrochemical Reduction of CO2
The possible electrochemical Reactions and the corresponding
potentials
H2O to
H2(g)+ 0.5O2(g)
CO2 + H2 to HCOOH
CO2 + H2O to HCOOH + 0.5O2
CO2 + H2 to CO + H2O
CO2 to CO + 0.5O2
CO2 + 3H2 to CH3OH + H2O `
CO2 + 4H2 to CH3OH + 2 H2O
CO2 + 2 H2O to CH3OH + 1.5O2
CO2 + 2 H2O to CH4 + 2 O2
E0
1.23
1.34
1.33
1.20
1.06
Delta G0 (Kcal/mol)
56.7
5.1
61.8
4.6
61.3
-4.1
-31.3
166
195
Table : Sector-wise contribution of CO2 emissions
Sector
Percent Contribution
Land use and forestry
17
Industry
Residential and commercial
Buildings
Transportation
Power
waste and waste water
19
8
13
26
3
Scheme.1.Chemical Transformations of CO2
Barriers for Further Progress
(1) the magnitude of environmental consequences,
(2) the economic costs of these consequences,
(3) options available that could help avoid or diminish the
damage to our environment and the economy
(4) the environmental and economic consequences for each
of these options
(5) an estimate of cost for developing the technology to
implement these options
and (6) a complete energy balance which accounts for energy
demanding steps and their costs.
Suggested Some References
1. A Beher, Carbon Dioxide Activation by Metal Complexes VCH, Weinheim (1988)
2. Catalytic Activation of Carbon Dioxide (ACS Symp Ser) (1988) 363
3. M. Aulice Scibioh and V.R. Vijayaraghavan, J. Sci. Indus. Res., 1998, 57, 111-123.
4. M. Aulice Scibioh and B. Viswanathan, Proc. Indn. Natl. Acad.Sci., 70 A (3), 2004, 407-462
5. M. Aulice Scibioh and B. Viswanathan, Editor. Satoshi Kaneco, Japan, Photo/ Electrochemistry
and Photobiology for Environment,Energy and Fuel, 2002, 1- 46, ISBN: 81-7736-101-5.
6. F. Bertilsson and H. T. Karlsson, Energy Convers. Mgmt Vol. 37,No. 12, pp. 1725-1731, 1996
7. I. Omae, Catalysis Today 115 (2006) 3352
8. M. Gattrell, N. Gupta and A. Co, J. Electroanal Chem, 594, (2006),1-19.
9. Enzymatic and Model Carboxylation and Reduction Reaction for Carbon Dixoide Utilization
(NATO ASF Ser C 314 (1990)
10. Electrochemical and Electrocatalytic Reaction of Carbon Dioxide (Eds B P Sullivan, K Krist and
H E Guard) Elsevier Amsterdam (1993)
11. M M Halmann Chemical Fixation of Carbon Dixoide CRC Boca Raton (1993) D Walther Coord
Chem Rev 79 (1987) 135.
12. P. G. Jessop, F. Jo, C-C Tai, Coordination Chemistry Reviews 248 (2004) 2425-2442
THE TOPIC THAT FOLLOWS IS
DRY REFORMING OF CARBON
DIOXIDE
Topics in Reforming of Carbon dioxide
(1) what is this reaction and why this reaction?
(2)what are the concurrent possible reactions?
(3) The basic thermodynamics of the reaction
(4) Catalyst systems that have been studied.
(5) The rationale for the selection of catalysts