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Chapter 1

Introduction

Most of the Countries today face four basic interdependent challenges namely; increasing food prices, non-sustainable depletion of natural resources, Climate Change and Volatile Fuel Prices. Most of the Resources are scare and have alternate uses. For example, crops such as corn, sunflower etc. which are traditionally used as a food crop can also be used to obtain fuel as a substitute to fossil fuels. It is this conflict between food and fuel (food vs. fuel) that makes things complex.

Most of the non-renewable technologies are cheap but they cause large amount of Green House Gas (GHG) emissions. Most of the Renewable technologies on the other hand produce limited emissions but are expensive. The objective of every country is to try to achieve an optimum energy mix so as to reduce the GHG emissions and at the same time keep fuel and electricity prices within a competitive range. It is for this reason that high dependence on fossil fuel based technologies is expected to continue in the near future. As a result of increased research, renewable technologies are expected to become cheaper and they will be incorporated in the energy mix as and when they become competitive with fossil fuel based technologies. . Meanwhile, scientists have been looking into other options to reduce the overall CO2 emissions from fossil fuel utilization while keeping the cost per unit energy output lower than that of renewable sources at present. There are a large number of options being looked into such as improving energy efficiencies, switching to less carbon intensive technologies, nuclear energy, Carbon Capture and Storage (CCS) etc. Among these the most promising technology in terms of capacity of CO2 abatement is CCS. According to IPCCs Special Report on Carbon Dioxide Capture and Storage (2005), CCS has the potential to reduce overall mitigation costs and increase flexibility in achieving greenhouse gas emission reductions.

The various Carbon Capture Technologies available mainly fall into either one of these categories, namely; Pre Combustion Capture, Post Combustion Capture and Oxy-fuel Combustion [1]. Pre Combustion Capture is applied in the case of Gasification or Partial Oxidation. An inherent advantage associated with Pre Combustion Capture is that the gases are usually produced at a higher pressure and the CO2 concentration in the stream is higher than that of simple combustion [1]. As a result, the costs associated with capture are lower and the energy penalty to implement carbon capture is also lower than Post Combustion Capture [1]. Post Combustion Capture is employed in case of CO2 capture from flue gases of processes. Oxy-fuel capture technology is in demonstration phase. This technology aims at using pure Oxygen in the combustion process [2]. A portion of flue gases is recirculated to control the flame temperatures. As a result of Oxy-fuel combustion what is produced is a concentrated stream of CO2 and H2O. Broadly, there can be three possible pathways for CO2 storage [3]: 1. Geological and Oceanic: This includes both underground terrestrial and oceanic 0sequestration. 2. Chemical: This includes fixing of CO2 in industrial chemicals such as Methanol, urea, inorganic and organic carbonates etc. and CO2 use in Enhanced Oil Recovery (EOR). 3. Biological: This includes CO2 sequestration in both Terrestrial Biomass and Algae. Among these Geological Sequestration appears to have the maximum capacity for CO2 sequestration. At present, Chemical and Biological sequestration are viewed as means to accelerate the initial uptake of Geological Sequestration by generating additional revenues [4].

CO2 Storage Pathways

Geological and Oceanic

Chemical

Biological

Figure 1.1 Different CO2 Storage Pathways It is also important to note here that there are certain gaps in our understanding of Geological Sequestration. There are certain apprehensions among the scientific community regarding the side effects of Geological Sequestration such as induced seismic activity, contamination of underground water and possible leakages [5]. This knowledge gap is expected to fill as our practical experience with Geological Sequestration increases. Besides, Geological Sequestration is an expensive technology. Unless a Carbon Tax is levied there isnt any financial incentive for companies to go for Geological Sequestration. The other two pathways, i.e. Chemical and Biological, are expected to generate some additional revenue and alternate energy sources that can help increase the uptake of Geological Sequestration in its initial stages [4].

Chemical Storage basically aims at reuse of the CO2 to form industrial products. Different products have different lifetimes, for example if we use the CO2 to form urea then as and when the urea is put to use the CO2 would be released back into the atmosphere. Hence, people have been proposing some closed carbon loops in which the CO2 can be fixed to form a particular chemical and then when upon usage these chemical release CO2, the CO2 can be collected and pumped back into the loop to produce the same or an alternate chemical [6]. Another possible utilization route for CO2 can be to produce chemicals like carbonates which can fix the CO2 for a long period of time.

Biological Sequestration aims at sequestering CO2 by biological means such as in terrestrial biomass (Forests, Grasslands etc.) or oceanic biomass (Algae etc.). Terrestrial biomass, mainly due to their low rate of CO2 fixation, requires a larger area to sequester a unit weight of CO2. Chapter 2 looks into what are the processes that have a major share in anthropological CO2 emissions. It also looks into what are the different CO2 capture technologies available. Chapter 3 looks into the various industrial CO2 reuse options available. It also looks into their relative capacities for CO2 Storage. Chapter 4 looks into the relative potential of Terrestrial Biomass sequestration and Algae based sequestration by taking a 900 tonne per day Ammonia plant as case study. Chapter 5 enlists major conclusions from this study

Chapter 2

Major CO2 Sources and Capture technologies 2.1 Major CO2 Sources:

The major CO2 sources are Power Plants, Cement manufacturing plants and Refineries. A list of various CO2 sources and their relative share in total CO2 emissions is listed in Table 2.1: Table 2.1 Major CO2 emitting Processes and their share in total anthropogenic emissions as of 2005(Reprinted from [1])

An important characteristic of flue gas streams which affects the capture cost is its CO2 concentration. Higher the CO2 concentration lower is the capture cost [4]. Table 2.2 enlists various sources and their respective CO2 concentration.

Table 2.2 CO2 concentration in the flue gases from different sources (Source: [1]) CO2 Concentration (%) Source Power Station Flue Gas: Coal Fired Boiler Natural Gas Fired Boiler Natural Gas Combined Cycle Coal-Oxygen Combustion Power Station Pre-Combustion capture of CO2: Coal Gasification Fuel Gas Natural Gas Partial Oxidation Fuel Gas Blast Furnace Gas: Before Combustion After Combustion Cement Kiln Off-Gas Oil Refinery and Petrochemical Plant Fired Heaters 8 20 27 14-33 40 24 14 8 4 >80 (Approximate)

2.2

CO2 Capture Technologies

There are primarily three Carbon dioxide capture technologies:

Post Combustion Capture: This technique is employed when sequestering CO2 from diluted flue gases from combustion processes. The flue gasses are generally at low

pressures. The concentration of CO2 in the flue gasses generally ranges from about 4% (volume %) for natural gas fired plants to 14% (volume %) for pulverised coal fired plants [7]. The problem with dilute CO2 streams is that if we sequester them without first concentrating them with CO2, the gasses would occupy large volumes and since our storage capacity is limited, it would limit the maximum amount of CO 2 that we can store. Besides compressing dilute flue gas stream implies higher capture cost and an increase in energy penalty. Similarly, if the gases are at lower pressures the size of the equipment would have to be large implying an increase in costs [7]. Amine solutions (MEA, DEA etc.) are used to absorb CO2 from the flue gases. The Amine solution is later heated with the help of steam in order to regenerate the amine solution and get a highly concentrated CO2 stream. This regeneration process is highly energy intensive [7]. Figure 2.1 depicts this technology when applied to a Gas turbine combined cycle.

Figure 2.1 Gas turbine combined cycle with post-combustion capture of CO2 (Reprinted From [7])

Pre Combustion Capture: This technique involves partial oxidation/gasification of fossil fuels producing a stream which is predominantly CO, N2and H2. The CO is generally converted to CO2 in what is called a Shift Reactor. As a result the stream becomes highly concentrated in CO2 and is generally at high pressures implying lower equipment costs. It also allows use of Physical solvents rather than chemical solvents implying that a mere pressure reduction and slight heating is all that is necessary to regenerate the solvent. At present, this technology is already employed in various ammonia manufacturing and coal, petcoke gasification plants Figure 2.2 depicts the technology in a Coal fired IGCC plant.

Figure 2.2 Coal fired IGCC with pre-combustion capture of CO2 (Reprinted From [7]) Oxy-fuel Combustion: The dilution of the flue gas stream is primarily caused due to the large amount of N2 that comes from air. If oxygen is used instead of air, the flue gas will primarily consist of CO2, H20 and excess Oxygen. The flame temperature would be higher. In order to control the flame temperature a part of the flue gases is recycled. CO2 concentration in flue gases reaches up-to 80% [4] thereby making CO2 capture

economical. Another advantage associated with Oxy-fuel combustion is that NOx emissions are suppressed mainly due to the absence of nitrogen. A major disadvantage associated with Oxy-fuel combustion is that the generation of pure oxygen through an Air Separation Unit (ASU) is an expensive process both in terms of capital costs and operating costs [7].

Figure 2.3 Oxy-Fuel Capture based CCS (Reprinted From [2])

Tables 2.3 and 2.4 shows the energy penalties imposed as a result of Post Combustion and Pre Combustion capture. As is evident, the energy penalties imposed in the case of Post Combustion Capture are greater than that for Pre Combustion Capture.

Table 2.3 Post Combustion Capture penalty (Pulverized Coal Fired Power Plant) (Reprinted from [7])

Table 2.4 Pre Combustion Capture Penalty (Coal Fired IGCC Plant) (Reprinted from [7])

Chapter 3

Chemical Storage

3.1

Industrial use of CO2:

3.1.1 Differentiation between Captive and Non-Captive uses [4]

Captive uses refer to processes in which CO2 is an intermediate product in the process. For example, use of CO2 in Methanol and Urea manufacturing. Non Captive uses refer to processes whose demand of CO2 is to be met by an external source. Some people find this differentiation necessary because captive uses dont provide an opportunity to store CO2 that is being emitted by large sources such as Power Plants [4].

Figure 3.1 Annual US CO2 utilization (Captive + Non-Captive uses) in 1989 (Reprinted from [8])

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Figure 3.2 Approximate proportion of current CO2 demand by end use (Worldwide, non-Captive uses only) (Reprinted from [4])

Considering only the non-captive uses, the total demand for CO2 (reuse) amounts to 80 MMT /yr [4]. Enhanced Oil Recovery (EOR) accounts for nearly 50 MMT/yr of the total demand. Of this 50 MMT/yr about 40 MMT/yr is met by natural CO2 reservoirs [4]. This is because the cost of bulk CO2 in market is higher than what they have to incur by extracting CO2 from natural reservoirs. The price of bulk CO2 is expected to decrease on introduction of carbon tax [4]. As discussed earlier the CO2 sources may be divided in two broad categories based on the concentration of CO2 in the stream they produce. Sources such as Natural Gas processing plants, Fertiliser plants and IGCC plants produce a stream that is concentrated with CO 2. The bulk price of such streams varies in the range of US$ 15-19/tonne [4]. While, on the other hand sources such as Pulverized Coal Power Plants produce a stream that is diluted with nitrogen and is generally at low pressures. If it is assumed that the plant supplying this stream processes it to bring it at par with its concentrated counterpart, the cost of the stream would rise to be US$>50/tonne [4].

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Presently, it has been estimated that about 500 MMT/yr supply of the concentrated stream exits, while, an additional 18000 MMT/yr is supplied in the form of dilute stream [4].

3.1.2. Thermodynamic Stability of CO2: Table 3.1 enlists the Gibbs free energy of formation of CO2 and certain other carbon containing compounds. Such a table can help us to identify which product could be formed more easily from CO2. Table 3.1 Gibbs free energy of formation, G0 for CO2 and other chemicals (Reprinted from: [7])

An important inference which we can draw from the Table 3.1 is that CO2 is more stable than most of the other carbon containing compounds. Only organic carbonates (DMC) and inorganic carbonates (MgCO3 and CaCO3) are more stable than CO2.Hence an ideal choice for chemically storing CO2 would be to produce organic and inorganic carbonates which are relatively more stable than CO2. Another appealing characteristic of carbonates is that the transformation of CO2

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to carbonates is an exothermic process thereby any additional energy input by burning of fossil fuels to propel the conversion is avoided, hence ensuring maximum CO2 sequestration. Another important aspect of chemical storage of CO2 is that the chemicals should have substantial shelf life, for example polymers and inorganic carbonates. Chemical such as Urea and Methanol generally have a low shelf life. They are able to store the fixed CO 2 only for small durations. They release the fixed CO2 as soon as they are put to use. To produce chemicals less stable than CO2 we must ensure that the energy input that we give to facilitate the conversion must cause lesser emissions than what we fix. Smith and Thambimuthu [6] proposed a simple carbon free energy cycle for CO2 utilization (Figure 3.3).

Energy

CO2 Fuel Power Plant / Other CO2 Source

Non Fossil Energy

A CO2 based Secondary Energy Cycle

Synthesis

Electricity Chemicals (Typically having large shelf life)

CO2 Fuel Utilization Energy


Figure 3.3 A CO2 based secondary energy cycle (Source: [6]) 13

Such a cycle can be used to produce chemicals having higher Gibbs free energy than CO 2. For maximum net sequestration of CO2 the energy input to this process needs to be from a renewable source. This cycle essentially mimics the natural carbon cycle in the nature through which atmospheric CO2 is fixed by the means of photosynthesis. The only limitation to this cycle is in the case of production of chemical having low shelf life. In such a case, once the chemicals are put to use they would release the CO2 that had been sequestered during their manufacturing, while the CO2 sources, primarily Power Plants (as they are the largest CO2 emitters), would continue to emit CO2. Hence, until and unless the chemicals have large shelf life (as in the case of CO2 based polymers or carbonates) there wont be much contribution to net CO 2 sequestration.

In order to avoid the limitation associated with the cycle proposed by Smith and Thambimuthu some people [9, 10] have worked on what is called a Carbon neutral secondary energy cycle. They have proposed the use of CO2 to produce fuels such as Methane and Methanol as per reactions (1) and (2). In fact the recently proposed Methanol Economy is also based on similar concept. This energy needed for this conversiom is to be supplied from renewable sources. Figure 3.4 shows such a cycle. CO2 + 4H2 CH4 + 2H2O CO2 + 3H2 CH3OH + H2O Go298 = 113.6 kJ/mol Go298 = 3.9 kJ/mol

(3.1) (3.2)

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Figure 3.4 A comprehensive CO2 and secondary energy utilization strategy (Reprinted From [7])

3.1.3. CO2 reuse technologies: Some of the reuse technologies that are important in terms of their CO2 storage potential* are listed below:

Enhanced Oil Recovery (EOR): Overview: After the limit of primary production from a well is reached, EOR is used to further increase the oil yield by 7-23 % [4]. EOR requires CO2 at high pressures to be pumped into the oil well. At high pressures CO2 is miscible in Oil, resulting in oil swelling and reduction in its viscosity, thereby facilitating its recovery.

Please Note that we have discussed only non-captive uses of CO2 in this section 15

Technology Status: CO2 was first used in EOR in the early 1970s in Texas, USA. Hence, this technology can be considered as mature. CO2 Storage Potential: Site specific but typical value: 0.5 t CO2/barrel of Crude [4]. A study recently noted that at least 8 billion tonnes of CO2 could be sequestered in the US by using EOR [11]. CO2 Sources: EOR needs concentrated CO2 stream. Current demand of CO2 for EOR in USA is 50 MMT/yr, of which 40 MMT/yr is supplied via naturally occurring CO2 reservoirs (Price: US$ 15-19/tonne). Benefits: Increased Crude Oil recovery. Barriers: High CAPEX and OPEX costs and uncertainties over long term Oil prices are some of the barriers to large scale CO2 propelled EOR [4].

Urea yield boosting in case of Ammonia production from SMR: Overview: Natural Gas based Urea plants usually produce 5-10% surplus Ammonia. This excess Ammonia can be reacted with non-captive CO2 in order to boost the yield of Urea [4]. Technology Status: Urea manufacturing from Ammonia and CO2 is a mature technology with most of the Urea in the world being manufactured through this technology. CO2 Storage Potential: 0.73 t CO2/ tonne Urea. Typical Plant size: 100-400 tpd CO2 [4]. CO2 Sources: CO2 from reformer flue gases in an SMR plant can be used as a feedstock for Urea yield boosting [4].

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Benefits: Mainly because of the mature state of CO2 to Urea technology, it is one of the few technologies which can be used presently to generate revenue without much investment required in R&D. Barriers: The decision to convert Ammonia to Urea depends upon the relative prices of Ammonia and Urea. Though the fertiliser industry in India is regulated but worldwide there are countries where the volatility in prices of Ammonia and Urea poses the biggest barrier in implementation of this technology [4].

CO2 as a working fluid for Enhanced Geothermal Systems (EGS): Overview: In this technology supercritical CO2 is used as a heat transfer fluid. Technology Status: There are some Pilot plants are either in operation or development in Australia, USA and Germany[4]. CO2 Storage Potential: The storage potential is site specific. Typical Value: 24 t CO2 /day/ MWe [4] CO2 Sources: Dry concentrated CO2 stream is needed for enhanced EGS. Benefits: Minimised water usage. Barriers: Remains to be proved at a large scale. CO2 has lower specific heat than water, resulting in a higher flow rate requirement for same amount of heat transferred. Storage Capacity of CO2 varies to a large extent from site to site. There are also uncertainties regarding long term storage of CO2.

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Polymer processing: Overview: Traditionally, polymers have been made from petroleum derivatives such as ethylene, propylene etc. A new approach to polymer processing being looked into these days is to use CO2 along with traditional feedstocks. Polycarbonates are produced by combining CO2 with epoxides over a Zinc based catalyst system. The epoxide can be changed in order to affect the properties of the end product. Typical polycarbonates include PolyPropylene Carbonate (PPC) and Poly-Ethylene Carbonate (PEC). Technology Status: Novomer Ltd. has been operating a Pilot batch plant at Kodak Speciality Chemicals facility in Rochester, NY. They are also looking into developing a continuous plant in order to reduce production costs. The CO2 based polymers made by Novomer are being tested and they have been found to be comparable and sometimes even superior to traditional polymers [4]. CO2 Storage Potential: Typical Storage potention 0.5 t CO2/ tonne product [4] Benefits: High CO2 storage capacity and comparable (sometimes even superior) properties with respect to traditional petroleum based polymers are some of the advantages associated with CO2 based Polymers. Barriers: Technology still at demonstration phase. Since the Polycarbonates are aliphatic, they could degrade in as short a period as 6 months and release the CO2 that has been fixed during their manufacturing [4]. The cost of the final product needs to be lowered to make it competitive with traditional polymers.

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Inorganic Carbonate Mineralisation: Overview: For long term CO2 storage we can store it in the form of inorganic carbonates by reacting it with Alkali and Alkali-earth metal oxides that are normally found in naturally occurring silicate rocks such as serpentine, forsterite, periclase and olivine. This carbonation of oxides occurs naturally in nature but at a very slow pace. Presently, research is focussed on accelerating this rate. Besides silicate rocks, people have also been looking into using industrial waste streams. Calera Corporation has developed a process in which they contact flue gases with water and solid oxides in an absorber. Mineral Carbonates which precipitate out are separated and dewatered. Supplementary Cementitious materials (SCM), aggregate and other building related materials are produced by this process. They have also developed a novel low voltage technology known as Alkalinity Based on Low Energy(ABLE) to generate the required alkalinity [12]. Skyonic have also developed a technology which they call Skemine. Skymine technology also removes CO2 from industrial waste streams and produces solid carbonate and/or bicarbonates [13]. Technology Status: Calera Corporation is operating a continuous pilot scale plant in Moss Landing, California with a capacity of 5t/day of Supplementary Cementitious Material (SCM). Another demonstration plant is also under construction. Calera is also constructing a pilot plant based on its proprietary technology ABLE [4]. CO2 Storage Potential: 0.5 tonne CO2/ tonne Carbonate formed [4] CO2 Sources: Moderately concentrated stream of CO2 is required for this process.

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Benefits: Utilisation of waste stream, ability of the technology to work on moderately concentrated CO2 stream and the ability to capture other emissions such SO2 and heavy metals are some of the advantages of Caleras Process. Barriers: Not every silicate reserve can be used for this process. Environmental emissions caused by mining of Silicate materials. Carbonation Technology is still in research phase.

CO2 as a feedstock for liquid fuel production: Overview: CO2 is also being looked at as a future source of liquid fuels such as Methanol and Formic Acid. As can be seen from Table 3.1 some amount of energy would be needed to perform this conversion. These processes generally have low efficiencies; its for this reason that the energy input required for the process should come from a renewable source. Technology Status: Carbon Recycling International (CRI), Finland is developing a commercial plant to produce renewable methane from CO2. Another company Mantra Venture Group (Mantra), USA is in negotiations for building first commercial plant based on producing formic acid from CO2 [4]. CO2 Storage Potential: 1.375 t CO2/ t Methanol and 0.95 t CO2/ t Formic Acid. CO2 Sources: Concentrated CO2 stream is required. Benefits:

Methanol can be used as an energy carrier. The use of existing petroleum based infrastructure is a benefit of CO2 to liquid fuels approach.

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Barriers: Low efficiency and high capital costs. Most of the technologies are costlier than their petroleum based counterparts.

CO2 as a feedstock for Di-Methyl Carbonate (DMC): Overview: Traditionally, DMC has been manufactured from phosgene but amidst recent safety concerns over its use people have started looking at Carbon monoxide and Carbon dioxide as alternative feedstocks for DMC. DMC is primarily used as a solvent and motor fuel octane booster. CO2 Storage Potential: 0.5 t CO2/ t DMC. CO2 Sources: Concentrated CO2 stream is required. Benefits: Safety issues associated with phosgene can be avoided. Life Cycle Analysis (LCA) of DMC manufacturing process via phosgene and CO2 have shown that the phosgene route has an environment impact four times that of CO2 pathway [7]. Barriers: Low shelf life

CO2 use for Bauxite Residue Carbonation: Overview: Bauxite to Alumina conversion results in the formation of a highly alkaline (pH=13) bauxite residue slurry (red mud). Red mud is usually a mixture of minerals and some alkaline liquor (NaOH) from Bayer extraction process. This slurry is carbonated with the help of CO2 thereby reducing the pH to about 10 and making its disposal easier [4].

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Technology Status: Alcoa Ltd. has been operating a trial plant based upon this technology for the last seven years. Its patents over the technology have ended [4]. CO2 Storage Potential: The CO2 storage capacity of untreated Red Mud is approximately 35kg of CO2 /tonne of Red Mud (dry). If the residue is treated with sea water its storage capacity increase to 750 kg CO2 / tonne of Red Mud [4]. CO2 Sources: Concentrated CO2 stream is required. Benefits: Due to the process of carbonation the pH of the Red Mud drops from 13 to 10 which make its disposal easier and cheaper. Barriers: 3.1.3.1. Low Storage capacity.

Differentiation between processes based on their feedstock quality and the nature of CO2 storage:

Process Requiring Concentrated CO2 Stream

Enhanced Oil Recovery (EOR) Urea Yield Boosting Polymer Processing Bauxite Residue Carbonation Renewable Methanol Formic Acid Algae Cultivation Mineral Carbonation Terrestrial Biomass Sequestration

Process Requiring Dilute CO2 Stream

Figure 3.5 Segregation of various CO2 reuse technologies based on their CO2 feedstock stream (Source: [4])

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Figure 3.6 An overview of various CO2 reuse technologies (Reprinted from [4])

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3.1.4. Current and Future potential demand of potential CO2 uses: Table 3.2 Current and Future potential demand of potential CO2 uses (Reprinted from [4]):

Presently most of the CO2 demand is from EOR. A report recently published by Global CCS institute has projected the potential demand from emerging uses (discussed above) in the future. The data from the report is shown in Table 3.3. Processes such as Inorganic Mineralisation, CO2

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to liquid fuels (Methanol and Formic Acid) and Algae Cultivation are expected to contribute significantly to the demand for CO2 in the future. Table 3.3 Future potential CO2demand from emerging uses (Reprinted from [4]):

Considering the fact that Power Plants (dilute sources) are the major emitters of CO2 we may have to either enrich the flue gases in CO2 or shift to IGCC in order to produce a concentrated stream so that it may be utilised in EOR, CO2 to liquid process which are expected to have significant demand for CO2 in the future.

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Chapter 4

Biological Sequestration

4.1

Comparison between Terrestrial Biomass and Algal Sequestration:

As far as biological sequestration is concerned, the two pathways available are Terrestrial biomass storage and Algal cultivation. A simple calculation was performed to estimate the area that would be required to store all the CO2 emissions that resulted from a 900 tonne per day Ammonia manufacturing plant. This Ammonia plant uses Coal Gasification to produce the required hydrogen. The Ammonia plant was simulated in ASPEN PLUS and the CO2 emissions were estimated based on the material balance performed by ASPEN PLUS. Tables 4.1 and 4.2 show a brief summary of the calculations. For terrestrial sequestration Acacia plantation was specifically chosen as it had high growth rate [14].

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Table 4.1 CO2 storage by Terrestrial Biomass Sample Calculations for a Ammonia plant based on Coal (Lignite) gasification: Capacity of Ammonia Plant: 900 TPD Carbon-di-Oxide TPY Emissions: 600000 (Approximate) OR 1643.836 TPD Carbon Mass to be Sequestered: 163636.4 TPY OR 163.6364 ktC/yr A Total Carbon Uptake Increment (kt C) B Carbon Fraction of Dry Matter C Annual Biomass Increment (kt dm) C=(A/B) 327.27 D Annual Growth Rate [14] (t dm/ha) F Area of Biomass Stocks (kha) F=(C/D)

Acacia (Tropical Plantations)

163.64

0.5

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21.818182

The area required comes out to be equivalent to ~92 times the area of IIT Bombay.

A similar set of calculations were done for Algae. The results are shown in Table 4.2.

Table 4.2 CO2 Storage potential of Algae


Typical CO2 Fixation by Algae: Algal Growth Rate: Area Required to sequester all CO2 from this particular Plant: 1.8 tCO2/t dry algal biomass [15] 98 g/m2/day [15] 9318796 m2 OR 2302.72 acre

Assuming, that Algae is Harvested as soon as it achieves maturity:

The area required comes out to be equivalent to ~4 times the area of IIT Bombay.

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Conclusions

During the transition from fossil to renewable energy powered world, Carbon Capture and Storage (CCS) appears to have great potential to reduce the present level of emissions while at the same time keeping the energy costs within a competitive range.

The different technologies available for carbon capture were looked into and Pre Combustion capture appeared to be the most promising one.

Among the three possible pathways for CCS, Geological Sequestration appears to be the most promising one. But during its initial stages of deployment scientists are looking for means that could generate some additional revenues which could in turn accelerate the uptake of Geological Sequestration. The other two pathways, i.e. Chemical and Biological Storage, seem to do just that.

Enhanced Oil Recovery (EOR) has the largest share in CO2 reuse at present. But, at present, it meets about 80% of its requirement through natural CO2 reservoirs. Most of the other CO2 reuse technologies, expected to have significant demand for CO2 in future, are in either research or demonstration phase. Hence, in the near future EOR is expected to play a major role in storing CO2 while generating extra revenues. There are certain other technologies like inorganic carbonate mineralisation and CO2 conversion to liquid fuels (Methanol and Formic Acid) that are expected to have substantial demand for CO2 in the future. Based on the specifications of the CO2 feed stream (concentrated or diluted with N2) the different technologies were divided into two categories. Also, based on the nature of CO2 storage (permanent or temporary) the technologies were segregated. For temporary storage of CO2 people have proposed some closed cycles in which the CO2 is converted into liquid fuels with the help of some renewable form of energy. The CO2 formed during their use is again recycled to be converted into liquid fuels.

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Among the two Biological storage routes (i.e. Terrestrial Biomass and Algal Storage) available Algal storage seems to be more promising mainly because it requires ~25 times less area than what is required for Terrestrial Biomass sequestration. This is mainly because of the enormous growth rates of Algae.

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References

1. IPCC, 2005: IPCC Special Report on Carbon Dioxide Capture and Storage. Prepared by Working Group III of the Intergovernmental Panel on Climate Change [Metz, B., O. Davidson, H. C. de Coninck, M. Loos, and L. A. Meyer (eds.)]. Cambridge University Press, Cambridge, United Kingdom and New York, NY, USA, 442 pp*. 2. Scottish Carbon Capture and Storage, Oxy-Fuel Combustion Capture, http://www.geos.ed.ac.uk/sccs/capture/oxyfuel.html, April 10, 2012. 3. Muhs J. et al., A Summary of Opportunities, Challenges and Research NeedsAlgae Biofuels & Carbon Recycling , Utah State University, May 2009. 4. Global CCS Institute and Parsons Brinckerhoff, Accelerating the uptake of CCS: Industrial Use of Captured Carbon Dioxide, Global CCS Institute and Parsons Brinckerhoff, March 2011. 5. Katzer J et al., The Future of Coal, Massachusetts Institute of Technology, 2007. 6. Smith I.M. and Thambimuthu, K.V., Greenhouse gases, abatement and control: the role of coal, IEA Coal Research, Report No IEACR/39, 1991. 7. Thambimuthu K., Davision J. and Gupta M., CO2 Capture and Reuse, Workshop on Carbon Dioxide Capture and Storage, 31-49, 2002. 8. IEA Working Party on Fossil Fuels Task force on Zero Emissions Technology Strategy, Challenges for large-scale CO2 Utilization and Sequestration, IEA WPFF, March 2002. 9. Aresta, M, Perspective of carbon dioxide utilization in the synthesis of chemicals: Coupling chemistry and biotechnology, Advances in Chemical Conversions for Mitigating Carbon Dioxide, Elsevier Science B.V., 114, 65-76., 1998 10. Arakawa, H., Research and development on new synthetic routes for basic chemicals by catalytic hydrogenation of CO, Advances in Chemical Conversions for Mitigating Carbon Dioxide, Elsevier Science B.V., 114, 19-30, 1998 11. World Resources institute, CO2-Enhanced Oil Recovery, http://www.wri.org/publication/content/8355, April 10, 2012. 12. Calera Corporation, The Science: Carbonate Formation, http://calera.com/index.php/technology/the_science , April 10, 2012.

30 The Format of the reference is in accordance with the authors request.

13. Skyonic Limited, The Skymine Process, http://skyonic.com/skymine/ , April 10, 2012. 14. IPCCs Task Force on National Greenhouse Gas Inventories, Revised 1996 IPCC Guidelines for National Greenhouse Gas Inventories, 1996 15. Sun S. and Hobbs R., Power Plant Emissions to biofuels, Arizona Public Service, DEFC26-06NT42759, 2008.

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