STUDENT NAME: Muhammad Ali Qaiser STUDENT ID: 26561999

STUDENT EMAIL: maq1g13@soton COURSEWORK MODULE: SESM6021

COURSE MODULE SUB-UNIT SUPERVISOR COURSEWORK TYPE

Introduction to Energy Technologies Conversion and Storage of Electrochemical Energy Prof. Carlos Ponce de Leon / Prof. Richard Wills Individual Essay (1500 words)

Title: CO2 Capture Define the problem of carbon dioxide and describe the proposed existing technologies to convert it into useful fuel such as alcohols. Write a critical review and compare this technology with other possibilities. Author: Muhammad Ali Qaiser Key Words: Carbon Management | Carbon Conversion | Photocatalysis | Biofuel | Sequestration

Abstract: The essay seeks to establish evidential grounds for CO2 emissions as an urgent problem. It then goes on to compare novel solutions and pilot ideas that are being researched to convert this CO2 into useful products, primarily biofuels. It looks at the general principles involved in one particular technique designated as cyanobacterial photosynthesis and then explains the advantages and challenges encountered in this context. It also presents other experimental alternatives of CO2 utilisation for cursory comparison.

Introduction: Carbon dioxide emission is increasingly becoming an environmental concern. A vast majority of modern scientists concur that climate change is occurring due to rising emissions of greenhouse gases (Leshner, 2009) from manmade activities. The largest contributor in this regard is seen to be carbon dioxide, with proven heat-trapping properties. Its concentration in earths atmosphere has historically never been above 300 ppm1, but this level was surpassed in 1950 and now stands around 400 ppm (NASA Earth Team, 2013).

ppm is parts per million by mass

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STUDENT NAME: Muhammad Ali Qaiser STUDENT ID: 26561999

STUDENT EMAIL: maq1g13@soton COURSEWORK MODULE: SESM6021

According to Wilcox (2012), 30 Gt2 of CO2 are released annually by anthropogenic activities, of which 15 Gt are reabsorbed by natural sinks. The remainder represents an annual increase of 2 ppm CO2 in the atmosphere. Carbon dioxide is in most part produced by burning of fossil fuels3 for provision of energy to transport, electricity, industrial and residential sectors. Furthermore, a small proportion of this gas is also released as a by-product of certain manufacturing processes4. As correlation between climbing global temperatures and upward trend in CO2 exhaust are proven, it is obvious that active research is required for technologies that can scrub out this gas from flue and then dispose it. This subject area is referred formally to as Carbon Capture and Sequestration (CCS), and 16 large-scale solutions have been already been demonstrated and deployed around the world, storing potentially up to 36 million tonnes of CO2 per year (Global CCS Institute, 2012). One such example is the Sleipner project off the Norwegian coast, which stores 2,700 tonnes daily 1 km below the seabed. This essay will not critique the well-established processes used for CCS5. Instead, it will rather look at novel methods being researched for utilization of captured carbon in fates other than storage, such as conversion to organic compounds. This broadens the scope from sequestration to carbon management.

Literature Review: Carbon sequestration takes a variety of forms after CO2 capture ranging from chemical conversion to combustible reuse to storage. In comparing the various techniques, this essay will review as primary subject, the attractive possibility of CO2 conversion to alcohols, which can subsequently be used as chemical feedstock, source of renewable fuels and even beverages. An emerging technique for this is the use of microbial photoautotrophs i.e. a class of microorganisms including cyanobacteria and algae
2 3

Gt is giga-tonne, where 1 tonne = 1,000 kg Coal, oil, natural gas 4 Amongst others: Cement production, Iron extraction by blast furnace, Aluminium extraction by electrolysis 5 Pre-combustion, post-combustion and oxy-fuel for carbon extraction, and underground injection for storage in saline formations, depleted or unmineable seams

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STUDENT NAME: Muhammad Ali Qaiser STUDENT ID: 26561999

STUDENT EMAIL: maq1g13@soton COURSEWORK MODULE: SESM6021

that are capable of photosynthesis. According to Ducat et al. (2011), cyanobacteria are industrially feasible because of their ability to use sunlight as a free energy input, as well as responsiveness to genetic engineering. It is also noted that microbial photosynthesis permits more efficient solar collection than land plants by a factor of nearly 2 to 3. In combination with the principle that they can thrive in water and require inexpensive mineral inputs along with carbon dioxide, photoautotrophs therefore offer a high productivity-to-cost alternative which does not compete for land with higher crops producing food or fuel. Another interesting aspect of this technique is that the microbes can be induced to switch between production of lipids, proteins and glycogen by altering the environmental stresses; these include pond temperature and selection of mineral catalysts (Dismukes, et al., 2008). Although cyanobacteria do not naturally produce biofuels, they are receptive to genetic engineering of new pathways of biosynthesis. Recent studies in this regard have successfully demonstrated the production of organic fuels like butanol and fatty alcohols, after modification of strains such as Synechoccus elongatus (Oliver, et al., 2013). Alcohol may also be produced from CO2 in a more standard industrial and less biological manner by reduction6. It has been further demonstrated (Obert & Dave, 1999) that the yield of methanol produced by reduction is enhanced if inorganic catalysts are replaced by enzymes, and the reaction environment is provided in form of gel matrix (perhaps due to confinement of the reactants and increase of available surface area). In contrast to bacterial photosynthesis, a hint of alternative carbon utilization techniques being researched at industrial scale comes from the US government funded Industrial Carbon Capture and

Hydrogenation i.e. addition of H2

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STUDENT NAME: Muhammad Ali Qaiser STUDENT ID: 26561999

STUDENT EMAIL: maq1g13@soton COURSEWORK MODULE: SESM6021

Storage7 programme of the Department of Energy8 (Folger, 2013). This has resulted in the following pilot commercial processes: 1. Catalytic combination of CO2 and shale gas (ethane) into high-performance polymers (Novomer Inc., Massachusetts USA; see novomer.com) 2. Large-scale farming of Cassava starch plants for fermentation into ethanol, and backward integration of CO2 from this fermentation into algal ponds for further production of catalysed biofuels (Phycal LLC, Ohio USA; see phycal.com) 3. Retrofitting of emission plants with mineralisation kits, in order to scrub out CO2 for transformation into carbonate and bicarbonate salts through metal oxides termed sorbents. This carries the advantage of saleable products and eliminates the need for transport or pressurization of liquid/gaseous CO2 (Skyonic Corp., Texas USA; see skyonic.com) 4. Mineralization by aqueous precipitation of calcium carbonate cement, by combination of industrial CO2 flue with alkaline waste such as Ca(OH)2. The products can be sold to construction sector for manufacture of board materials (Calera Corp., California USA; see calera.com) Another very novel commercial idea for carbon dioxide management is the use of distributed absorbent network (National Academy of Sciences, 2003). This idea seems to the author a distinct future possibility, wherein is envisaged the routine use of CO2 absorbent membrane kits at consumer level. These kits would be fitted in exhaust pipes of home gas burners, cars and office heating systems. Saturated kits would be swapped for new ones at convenient intervals (such as time of refuelling), and an integrated supply chain service similar to municipal waste collection would be established to bring collected CO2 back to a central location for catalytic reduction.

7 8

ICCS US DOE

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STUDENT NAME: Muhammad Ali Qaiser STUDENT ID: 26561999

STUDENT EMAIL: maq1g13@soton COURSEWORK MODULE: SESM6021

In comparison, the more conventional uses of CO2 (National Academy of Sciences, 2001) comprise manufacture of urea (for fertilizers) and salicylic acid (for pharmaceuticals). Lastly, geological storage of liquefied or aqueous CO2 under ocean beds, depleted oil reserves or deep saline formations is also now a well-established process. The disadvantages of these conventional methods is that they are not suitable for all geographical locations, and incur energy expenditure in fulfilment (Herzog, 2013). Examples: Amongst the many possible photosynthetic and enzymatic conversion example processes studied, one in particular (Ducat, et al., 2011) is outlined below due to its representative nature.

INPUTS

INTERMEDIATE REACTIONS enzymes

OUTPUTS

Calvin Cycle
NADPH

C2H5OH

Figure 1 Cyanobacterial Carbon Fixation The above process depicts in a simplified manner the conversion of carbon dioxide to ethanol by cyanobacteria. However, the steps may be further broken down as follows: 1. Photons from sunlight are captured by thylakoid pigments and transferred to chlorphyll of photosystems within the bacteria 2. The photosystems (PS) use this energy to split water as: 2H2O O2 + 4H+ + 4e3. The free electrons are further excited through photon injection by PS, and are transported to Ferredoxin (Fd) complex for reduction of nicotineamide adenine dinucleotide phosphate Page 5 of 9

STUDENT NAME: Muhammad Ali Qaiser STUDENT ID: 26561999

STUDENT EMAIL: maq1g13@soton COURSEWORK MODULE: SESM6021

(NADP+) to NADPH; free protons (H+) produced by the PS participate in the above reduction process as well 4. Reduced NADP (or NADPH) takes part in a series of organic reactions originating from the Calvin Cycle, and mediated by externally added enzymes (such as decarboxylase and dehydrogenase) to finally produce ethanol The sequence above is summarized by a block diagram below.

Thylakoid Pigment

photons

Chloropyll

photons

Water Split eH+ Fd

PS

NADPH

NADP+

eH+

Plasmic Transport

Figure 2 Photosynthetic Reactions in Cyanobacteria What makes such synthesis so exciting is that the user can vary the final product (e.g. ethanol, glucose, lactate or butanol) by carefully controlling the following factors: a. Selection of added enzymes b. Variation of environmental stresses (amount of light, temperature or inhibiting salts) c. Genetic engineering of specific biosynthetic pathways Research experiments with cyanobacteria in the laboratory demonstrate a steady production of end product over a period of 3 weeks, after which it plateaus out due to toxic effect of the product itself (unless removed by user) (Oliver, et al., 2013).

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STUDENT NAME: Muhammad Ali Qaiser STUDENT ID: 26561999

STUDENT EMAIL: maq1g13@soton COURSEWORK MODULE: SESM6021

Product (g/L)

Time (days)

Figure 3 Photosynthetic Production Pattern in Lab Environment

Conclusion: The problem of CO2 emissions by anthropogenic activities, primarily fossil fuel combustion, is leading to a search for novel opportunities. While expensive processes such as geological storage are already being practised, new methods are continuously being explored to allow conversion of CO2 into useful products, notably biofuels such as ethanol. This not only leads one to claim that the use of biofuels is carbon neutral because its preparation consumes the carbon that it subsequently releases, but it also provides an answer to increasing regional government regulations that encourage carbon reduction (Ed Miliband MP (Secretary of State), 2009). The spectrum of carbon management is arguably broad and exciting, ranging from established industrial methods such as geological storage, EOR9, membrane separation and pre/post/oxy combustion capture to pilot ideas like photolytic conversion, enzymatic reduction, sorbent mineralisation and biomass crop management. While the dividends of such novel methods are yet to be confirmed, they do open up the scope of scientific endeavour into the domain of responsible engineering.

Enhanced Oil Recovery

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STUDENT NAME: Muhammad Ali Qaiser STUDENT ID: 26561999

STUDENT EMAIL: maq1g13@soton COURSEWORK MODULE: SESM6021

Specifically for biofuel synthesis from photoautotrophs, challenges such as toxicity tolerance, long reaction times and enzyme prices require resolution before the processes can be commercialized on large scale. On the brighter side though, these processes carry the very distinct advantage of requiring little artificial energy input, abundant availability of CO2 and little or no competition with land area for higher crops. (Total word count from Introduction to Conclusion = 1574)

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STUDENT NAME: Muhammad Ali Qaiser STUDENT ID: 26561999

STUDENT EMAIL: maq1g13@soton COURSEWORK MODULE: SESM6021

References
Dismukes, G. C. et al., 2008. Aquatic phototrophs: efficient alternatives to land-based crops for biofuels. Current Opinion in Biotechnology, Volume 19, pp. 235-240. Ducat, D. C., Way, J. C. & Silver, P. A., 2011. Engineering cyanobacteria to generate high-value products. Trends in Biotechnology, 29(2), pp. 95-103. Ed Miliband MP (Secretary of State), 2009. The UK Renewable Energy Strategy, London: Crown Copyright. Folger, P., 2013. Carbon Capture and Sequestration: Research, Development, and Demonstration at the U.S. DOE, www.crs.gov: Congressional Research Service (R42496). Global CCS Institute, 2012. The Global Status of CCS, Canberra: s.n. Herzog, H., 2013. Economics and Costs. [Online] Available at: http://sequestration.mit.edu/research/mitigation.html [Accessed 15 Oct 2013]. Leshner, A. I., 2009. Joint Statement of 18 Scientific Societies, Washington DC: American Association for the Advancement of Science. NASA Earth Team, 2013. Evidence. [Online] Available at: http://climate.nasa.gov/evidence/ [Accessed 10 Oct 2013]. National Academy of Sciences, 2001. Carbon Management: Implication for R&D in the Chemical Sciences and Technology, Washington DC: www.nap.edu. National Academy of Sciences, 2003. Novel Approaches to Carbon Management, Washington DC: www.nap.edu. Obert, R. & Dave, B. C., 1999. Enzymatic Conversion of Carbon Dioxide to Methanol: Enhanced Methanol Production in Silica Sol-Gel Matrices. American Chemical Society, 121(51), pp. 12192-12193. Oliver, J. W. K., Machado, L. M. P., Yoneda, H. & Atsumi, S., 2013. Cyanobacterial conversion of carbon dioxide to 2,3-butanediol. PNAS (Proceedings of National Academy of Sciences), 110(4), pp. 1249-1254. Wilcox, J., 2012. Carbon Capture. 1st ed. Stanford: Springer.

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