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Course on Carbon dioxide to Chemicals and Fuels PRESENTATION - FIVE 24 TH February 2014 On Line Course of NCCR ( Total Number of Projections for this Lecture.

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Presentation on theme: "Course on Carbon dioxide to Chemicals and Fuels PRESENTATION - FIVE 24 TH February 2014 On Line Course of NCCR ( Total Number of Projections for this Lecture."— Presentation transcript:

1 Course on Carbon dioxide to Chemicals and Fuels PRESENTATION - FIVE 24 TH February 2014 On Line Course of NCCR ( Total Number of Projections for this Lecture is 20) NCCR on Line L31

2 PHOTOELECTROREDUCTION OF CO 2 Principle An Example J.P. Collin & J.P. Sauvage, Coord. Chem. Rev. 93 (1989) 245 Appealing Approach! An important energy input contribution from light might be expected, thus diminishing electricity consumption

3 A study on photo-electro-reduction of CO 2 Possible Mechanistic Route By insitu-IR J, O‘M. Bockris & J. C. Wass, Mater Chem Phys, 22 (1989) 249 Photovoltomogram, λ= 560 nm (0.5 mW \cm 2 )

4 Metal islet catalysts deposited on a p-CdTe electrode in DMF-0.1 M TEAP/5% H20 MPc catalysts adsorbed on a p-CdTe electrode in DMF-0.1 M TEAP/5% H20 Product analysis results for CO2 reduction on phthalocyanine/p-CdTe J, O‘M. Bockris & J. C. Wass, Mater Chem Phys, 22 (1989) 249 Study on photo-electro-reduction of CO2

5 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 CO 2

6 Product analysis results Current-potential curves for crown ether catalysts added to the electrolyte for a p-CdTe electrode in DMF-0.1 M TEAP/S% H20 J, O‘M. Bockris & J. C. Wass, Mater Chem Phys, 22 (1989) 249 Study on photo-electro-reduction of CO 2

7 Catalytic shift (ΔE) times the CO faradaic efficiency for metal catalysts on p-CdTe as a function of M-O bond energy For metal-phthalocyanine catalysts on p- CdTe as a function of M-O bond energy ΔE values for CO production are linear Catalytic shift (ΔE) J, O‘M. Bockris & J. C. Wass Mater Chem Phys, 22 (1989) 249

8 For trinuclear carbonyl catalysts on p-CdTe as a function of M-C bond energy Catalytic shift (ΔE) J, O‘M. Bockris & J. C. Wass, Mater Chem Phys, 22 (1989) 249

9 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 CARBON MANAGEMENT

10 High cost of capturing, processing, & transporting anthropogenic CO 2 Incomplete understanding of reservoir processes Underdeveloped monitoring & verification technologies Unclear emissions trading regulations Potential conflicts of interest between sequestration & EOR or natural gas recovery Barriers to wider implementation CO 2 sequestration

11 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 Public Perception CO 2 Sequestration

12 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

13 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

14 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

15 WHAT HAS BEEN COVERED SO FAR The electronic structure of Carbon dioxide

16 CHEMICAL REDUCTION OF CARBONDIOXIDE ADDING HYDROGEN AND ELIMINATING WATER M. A. Scibioh & B. Viswanathan,Proc. Indn. Natl. Acad. Sci., 70 A (3),

17 Electrochemical Reduction of CO2 The possible electrochemical Reactions and the corresponding potentials E 0 Delta G 0 (Kcal/mol) H2O to H2(g)+ 0.5O2(g) CO2 + H2 to HCOOH 5.1 CO2 + H2O to HCOOH + 0.5O CO2 + H2 to CO + H2O 4.6 CO2 to CO + 0.5O CO2 + 3H2 to CH3OH + H2O ` -4.1 CO2 + 4H2 to CH3OH + 2 H2O CO2 + 2 H2O to CH3OH + 1.5O CO2 + 2 H2O to CH4 + 2 O

18 Table : Sector-wise contribution of CO2 emissions Sector Percent Contribution Land use and forestry 17 Industry 19 Residential and commercial 8 Buildings Transportation 13 Power 26 waste and waste water 3

19 Scheme.1.Chemical Transformations of CO2

20 (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. Barriers for Further Progress

21 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) M. Aulice Scibioh and V.R. Vijayaraghavan, J. Sci. Indus. Res., 1998, 57, M. Aulice Scibioh and B. Viswanathan, Proc. Indn. Natl. Acad.Sci., 70 A (3), 2004, M. Aulice Scibioh and B. Viswanathan, Editor. Satoshi Kaneco, Japan, Photo/ Electrochemistry and Photobiology for Environment,Energy and Fuel, 2002, 1- 46, ISBN: F. Bertilsson and H. T. Karlsson, Energy Convers. Mgmt Vol. 37,No. 12, pp , I. Omae, Catalysis Today 115 (2006) M. Gattrell, N. Gupta and A. Co, J. Electroanal Chem, 594, (2006), 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) P. G. Jessop, F. Jo, C-C Tai, Coordination Chemistry Reviews 248 (2004)

22 THE TOPIC THAT FOLLOWS IS DRY REFORMING OF CARBON DIOXIDE

23 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


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