THERMAL POWER MSc Academic Year 2010-2011




25 February 2011



ABSTRACT In the last few decades natural-fired power plants have increased in number due to the higher efficiency and allowed the great reduction in cost of electricity, although the natural gas price is still higher than the coal. For these reasons the combined cycle power plant using natural gas as fossil fuel is investigated in this report. An overview of all the different pollutants emitted by the power station is carried out and their harmful impacts on the surrounding environment are discussed. Moreover, it is established that the oxide of nitrogen is the main pollutant with most hazardous effects on the environment. However, in gas turbine technology many efforts have been already involved in the investigation of the NOx emission abatement treatment and all the different mitigation techniques are consolidated in the worldwide power plants installations. Therefore, the objective of this report is to study an innovative technology to reduce the carbon dioxide emissions related to the natural-fired combined cycle power plants. Furthermore, all the different post-combustion processes for CO2 capturing in power stations are discussed and the chemical absorption process results as the preferred technique involving carbon dioxide recovery systems. For this emission-mitigation technology, the fundamentals of the process, the chemical reactions and the main advantages are described. Beside, further technical information and cost estimation of the system are investigated and a comparison with reference to other types of power generation plants is carried out. Finally, the application of this technology for various industrial processes is discussed.

LIST OF CONTENTS INTRODUCTION 1 COMBINED CYCLE POWER PLAN 1 EMISSIONS FROM THE PROCESS AND ENVIRONMENTAL IMPACTS 3 CARBON DIOXIDE 4 POSSIBLE CONTROL TECHNIQUES 6 SELECTION OF THE TECHNOLOGY 8 6.1. Principle and description of the process 8 6.2. MEA and chemical reaction involved 10 6.3. Key issue of the process 11 7. TECHNO-ECONOMIC PERFORMANCE 11 8. SIMILAR PROCESS APPLICATIONS 13 8.1. Natural gas sweetening 14 8.2. Ammonia production 14 8.3. Cement production 14 8.4. Steel production 15 9. CONCLUSION 15 10. REFERENCES 16 APPENDIX A - Cost and performance data of CCGT 19 1. 2. 3. 4. 5. 6.



ABBREVIATIONS CCGT, Combined Cycle Gas Turbine; CCS, Carbon Capture and Storage; CO2, Carbon dioxide; CO, Carbon monoxide; GHG, Greenhouse Gases; HRSG, Heat Recovery Steam Generator; IEA, International Energy Agency; IGCC, Integrated Gasification Combined Cycle; IPCC, Inter-governmental Panel of Climate Change; LCE, Low Carbon Economy; MEA, Monoethanolamine; NGCC, Natural Gas Combined Cycle; NOx, Oxide of Nitrogen; PC, Pulverized Coal; PSA, Pressure Swing Absorption; SOx, Oxide of Sulphur; TSA, Temperature Swing Absorption; UHC, Unburned Hydrocarbon;

Note of the author: as established by SI the base unit for temperature is the thermodynamic temperature measured in Kelvin (K). However, in all the literature concerning MEA absorption process temperature is measured in degree Celsius (°C). As stated by National Institute of Standard and Technology, this latter unit is a derived unit in SI and so it can be used. On the basis of these considerations and for reasons of simplicity, the °C unit is used for the temperature in this report.



1. INTRODUCTION Nowadays, carbon dioxide emissions related to humans activities have reached such proportion that the natural cycle have now been modified. The best way to deal with that should be reach a low carbon economy based on a large scale energy process leading to a non fossil fuel energy source in which the minimal amount of greenhouse gas are emitted into the atmosphere [5]. Until when a LCE becomes available several actions can be implemented including reducing energy consumption while continuing country growth, diminishing the energy carbon content per unit of energy produced and controlling fossil fuel energy supplies to cope with decrease of fossil fuel reservoir and the augment in global energy demand. However the most effective climate change mitigation option could be capturing the carbon dioxide emitted by the man-made activity, such as industrial process and power plant [12]. Depending on the application there are number of different techniques available for the CO2 recovery system and [3] presents an overview of the different techniques. 2. COMBINED CYCLE POWER PLAN The combined cycle consists in two thermal cycles working at different temperatures within a single power station (see Figure 1). From the thermodynamic point of view, the heat discharged from the gas turbine cycle (Brayton cycle) at high temperature is recovered as a heat supply to the steam cycle (Rankine cycle) at low temperature. Because the gas turbine thermal efficiency is usually between 35% and 41%, less than half of the total energy used in the cycle is converted into electrical power. Therefore, the waste heat is recovered by means of a steam turbine set downstream the gas turbine increasing the performance of the power generation plants [14]. Moreover, the gas turbine and the steam turbine cycles are operating independently due to their different working fluids, respectively air and water vapour. The main objective of a combined cycle is to achieve higher total efficiency of the power plants compared to a simple cycle, in order to diminish the fuel consumption and hence the capital cost of the electricity per kWh. Thus, a modern CCGT can achieve an overall efficiency of 55% [7]. The main components of a CCGT power plant are illustrated in Figure 2 and described as follow [24]: 1. Compressor, in which the air is compressed and both pressure and temperature increase; 2. Combustor chamber, in which the fossil fuel is burned to produce energy and release to the working fluid; 3. Gas turbine, which drives the compressor and supplies the power for the electrical generator; 4. HRSG, where the heat released by the exhaust gases of the gas turbine increase the temperature of the pressurized water to produce steam; 5. Steam turbine, where the energy of the steam is converted into kinetic energy and then into electrical power; 6. Condenser, in which the remained steam is cooled and it condenses in feed water because that is continuously re-circulated through the system;



Figure 1 – Layout of combined cycle power plant. Source:







Figure 2 – Flow diagram of a Combined Cycle power plan Source:



3. EMISSIONS FROM THE PROCESS AND ENVIRONMENTAL IMPACTS In the power plants, the pollutants are formed mainly when the fossil fuel is burned in the combustion chamber to produce energy. Because of the environmental concerns and the increasing in cost of electricity, many efforts are put into developing new power plants able to produce electricity with lower emissions. The introduction by the governments of more severe regulations for the emissions leads to the request of estimating in details the emission in gas turbine exhaust. Thus, the power plants company should provide the detailed data of each pollutant generated inside the cycle. The typical range of pollutants concentration, the main sources and the most common mitigation techniques in the stationary gas turbine are reported in Table 1. The Oxide of Nitrogen is produced in large quantities at very high temperature in the primary zone of the burner. According to [21], the NOx can be divided in two categories depending on the way of formation: thermal NOx and organic NOx. The former pollutant is obtained by the oxidation of free nitrogen and air. It becomes directly dependent on the stoichiometric adiabatic flame mixture that represents the most important variable for characterizing NOx emissions. The latter pollutant is produced by the oxidation of organically bound nitrogen in the fuel. Moreover, the oxide of nitrogen emissions augment exponentially as the primary zone temperature, the resident time or the fuel-to-air ratio increases. The effects of the NOx emissions are extremely dangerous. On the one hand, NOx is the main cause of ozone depletion within the stratosphere. On the other hand, it increases the ozone concentration at ground level. The best way to reduce the NOx emissions should be burn inside the combustion chamber pure oxygen instead of air, but the production of electricity will become very expensive and this is not feasible for power generation stations. The Carbon Monoxide and the Unburned Hydrocarbon are formed by the incomplete or partial-incomplete combustion in the burner where the temperature is too low or the time available for the combustion process is not long enough. The emissions are considerable only at low power condition and during transient states. However, the NGCC tends to operate at design point conditions usually at 85% of the maximum power and with very short loading sequence leading to a significant low CO and UHC emissions. In addition, both CO and UHC are toxic and dangerous for the whole living creatures. CO is particularly harmful for the health of human being due to the reduction of the capability to carry oxygen by the red blood cell, which can cause headache or even death. The Oxide of Sulphur formation is mainly due to the presence of sulphur in air, fuel or injected water. Since the sulphur concentration in ambient air and in injected water is very low, this contribute to the SOx emissions is negligible. According to [21], the sulphur carried by the fuel is inevitably transformed in SOx and hence its content in the emissions become directly dependent on the quality of the fossil fuel, for example the residual fuel can reach 10-15% of SOx concentration in volume. The NGCC particularly exhibits lower SOx emissions due to the low concentration in the natural gas.



Table 1 – NGCC pollutants emissions, source and mitigation techniques. Source: [8,21]
POLLUTANT Carbon dioxide (CO2) Oxides of Nitrogen (NOx) Carbon Monoxide (CO) Unburned Hydrocarbon (UHC) Oxides of Sulphur (SOx) Particulate matter (C) TYPICAL CONCENTRATION 1 - 5 %vol SOURCES Oxidation of Fuel Carbon Oxidation of Atmospheric Nitrogen or Fuel-Bound Organic Nitrogen Incomplete oxidation of Fuel Carbon Incomplete oxidation of Fuel or Intermediates Oxidation of Fuel-Bound Organic Sulphur Inlet Ingestion, Fuel Ash, Hot-Gas-Path Attrition MITIGATION TECHNIQUES CCS Lean Head End Liner, Water or Steam Injection, Dry Low NOx Gas turbine's Combustor Design, Catalytic Reduction Gas turbine's Combustor Design

20 - 240 ppmv

5 - 330 ppmv

5 - 300 ppmv

Trace - 100 ppmv

Control Sulphur in Fuel

Trace - 25 ppmv

Fuel Composition

Moreover, the oxide of sulphur is produced both in the form of SO2 and SO3. Nevertheless, only 5% of the sulphur oxides consist in SO3, which combines with water vapour in the flue gases to form sulphuric acid. This acid becomes extremely toxic for the human being and corrosive for the creatures and items that come in contact with it. The particulates matter due to the combustion process consists almost in smoke, ash, erosion and corrosion products and ambient non-combustibles objects. The smokes, particularly, are considered as the visible part of filterable particulate matter, which must remains under control by the installation of a specific smoke-measuring emission unit. 4. CARBON DIOXIDE Carbon dioxide is the by-product of a complete and successful combustion process of a hydrocarbon fossil fuel, since the carbon molecules stored in them are emitted almost entirely as carbon dioxide. The simplified equation of a general combustion reaction and a combustion reaction with natural gas, which contains mainly methane (CH4), are shown respectively in equation (1) and (2).
!! !! + ! + ! 4 ∙ !! + 3,76 ∙ !! = ! ∙ !!! + ! 2 ∙ !! ! + ! + ! 4 ∙ 3,76 ∙ !! !!! + 2 ∙ !! + 3,76 ∙ !! = !!! + 2 ∙ !! ! + 7,52 ∙ !!

(1) (2)



It is worth noting that the concentration of carbon dioxide emission is proportional to the content of carbon in the fossil fuel. Therefore, the new NGCC can achieve a reduction by 40% in CO2 emission per KWh compared to the more conventional power plants burning coal [14]. Even if carbon dioxide is not considered as a toxic gas, it can be also dangerous for human health, since concentration of CO2 between 3% and 6% leads to headache and higher concentration can result in coma or even possible death. However, the main impact of CO2 emission is the contribution of anthropogenic emissions of GHG in the atmosphere, as shown in Figure 3a. As explained in [26], the presence of GHGs can affect the radiation going through the atmosphere and an augment in their concentration makes more radiation to be reflected to the Earth leading to a temperature raise of the Earth’s surface and hence the global warming. Since governments have signed Kyoto Protocol, the concerning about climate change and global warming is significantly grown [33]. For example the UK government has recently increased the aim of GHG reduction from 60% to 80% before 2050 and this issue proves the importance of environmental CO2 impact [35]. As published in [30], a specific database is introduced for several CO2 stationary sources, providing the distribution by process type. The power plants clearly represent the major contribute of the CO2 emissions in the atmosphere (see Figure 3b).



(a) (b)   Figure 3 – (a) Contribution of Anthropogenic Emissions of all Greenhouse Gases to the Enhanced Greenhouse Effect Since Industrial Times (measured in Watts/m2), Source: IPCC 1996; (b) Distribution of Carbon Dioxide emission sources by industry sector in 2000, Source: [27].  



5. POSSIBLE CONTROL TECHNIQUES The purpose of carbon capture and storage is to extract this pollutant from the flue gas stream and to obtain a nearly pure CO2 stream at high pressure for transport and injection in the underground sites. Particularly for power generation plants, CO2 recovery systems can reduce considerably the emissions into the atmosphere. However, the design of these emission abatement systems becomes significantly dependent on the CO2 capture efficiency and on the reduction in overall power plants efficiency due to the additional power required for the separation process (see Figure 4). On the one hands conventional technologies are able to capture approximately 90% of the CO2 produced. On the other hand a power station with CCS would require between 10% and 30% more energy comparing with a plant of equivalent power output without CCS, leading to increased fuel requirements and hence energy production cost [12]. As wide discussed in paragraph 4, the formation of carbon dioxide occurs inside the burner of the gas turbine during the combustion process. For this reason several techniques can be adopted in power stations to capture the CO2 inside the cycle instead of being emitted directly into the atmosphere. Three main emission-mitigation technologies are expected to be applied to capturing the CO2 generated by the combustion of natural gas in the worldwide industry. These are respectively: pre-combustion treatment, which consists first in the extraction and capture of carbon from the initial fuel and then the production of hydrogen; oxy-combustion, in which the mass flow entering in the process is oxygen instead of air and thus the exhaust gases are mainly CO2 and water; post-combustion treatment, where the carbon dioxide contained in the exhaust gas is extracted before being released into the atmosphere [12,8,3]. In this paper, the latter pathway is discussed in order to assess both the consolidated and innovative techniques and evaluate an effective comparison in terms of technical and economical impacts. Moreover, the main advantage of postcombustion treatment is that it can be implemented also on those power plants, which are already installed and in operation without any disruption during the electrical energy production [30]. The main objectives of CO2 emission-mitigation techniques are the production of a concentrated CO2 flow for storage reservoir and the releasing of flue gases with low CO2 content, containing mainly nitrogen, oxygen and water. Many efforts are carried out by industries and companies in order to achieve the maximum value of capture efficiency, lowering the cost of CO2 recovery system and the related augment in overall costs of the power plants. The different types of CO2 capture techniques currently used for industrial application can be divided as follows [34,3,12,16]: - absorption in solvents or in solids; - membrane separations; - cryogenics. The first type of techniques is the most largely adopted for industrial processes and it exploits essentially the reversible nature of the solvents. Therefore, the separation of carbon dioxide is achieved dissolving the pollutant contained in the exhaust gas using an appropriate solvent (absorption process). Then, the



decarbonated gas is released at the upper part of the vessel, whereas the CO2rich solvent passing through a regeneration process is recycled and it is sent back to the absorber. These techniques are usually based on a chemical or physical principle. In the former, the CO2 separation is achieved by a reversible chemical reaction and the regeneration is obtained by heating the solvent in order to break the chemical bond and release the CO2. In the latter, the absorption process is based mainly on the temperature difference between flue gases and solvent. In this case the regeneration process can be obtained by using two different principles: PSA regenerates the absorbent by pressure reduction, whereas TSA achieves the regeneration by increasing the temperature [34]. Moreover, the augment of CO2 partial pressure or the reduction in absorption temperature can lead to a higher performance of the recovery system. Nevertheless, this process is still at R&D stage due to the high cost of the CO2 recovery system [13]. Another technology is the so called Hybrid absorption that consists in a combined use of these two separation processes applying particular solvents and providing a good result in terms of CO2 recovery and emission abatement. In a slightly different scheme, a solid absorbent with high CO2 affinity, such as zeolites or activated charcoals, can be adopted as the sorbent in the separation process. In this technique the sorbent does not recirculate through the vessels because both the absorption and the regeneration steps are applied by cyclic variation in temperature or pressure. However, this absorption process has not yet reached the commercial stage [25]. Beside, CO2 separation from the flue gases can be achieved by means of membrane processes exploiting the selective permeation of the gas through specially manufactured materials. The gaseous mixture flow through the membrane is driven by a pressure difference across the membrane wall. Several types of membrane are currently investigated, such as polymer, mineral and composite. The numerous researchers are mainly focusing on two directions: the development of these new membrane materials and their integration in optimized processes; the development of a new type of membrane contactor, in which the membrane is associated with a solvent. Nevertheless, membranes for large-scale applications in power plant have not yet been introduced due to the low percentage of CO2 removed and the low partial pressure of CO2 in the flue gas, leading to higher energy penalties on the overall efficiency compared to a standard absorption process [10,28,2]. Cryogenic processes exploit the state changing of CO2 from gaseous to liquid by means of a series of compressions and cooling of flue gas stream. Even if several studies have been carried out to overcome the operating problems related to the formation of solid CO2, this technology appears highly penalized for post-combustion applications [31]. It is worth mentioning that the current capacity of all these technologies remains well below the real size necessary for installation on the largest CO2-emitting industry.



Emission of CO2 [kg/kWh]


  Figure 4 - Comparison of CO2 produced in power plants with CCS and without CCS stated by [12]

6. SELECTION OF THE TECHNOLOGY Several studies have shown that chemical absorption processes are largely the preferred techniques for CO2 capture systems. Nowadays all power plants with CCS have already applied MEA as the most wide used solvent for separation processes. Indeed, this solvent offers low energy cost and it can reach higher capture efficiency and selectivity compared with the other post-combustion CO2 recovery systems [22,35]. However, commercial alkanolamines react also with oxygen and other impurities present in post-combustion flue gases and these secondary reactions tend to degrade the solvent by forming non-regeneratable compounds extremely harmful to the capture installation. As Leci reported [17], monoethanolamine has been introduced since over 60 years for removal of various acid gases from natural gas streams. After the development of CCS, many studies are involved to increase the degradation resistance and corrosion resistance of this solvent. However, the MEA process is not yet considered as a fully mature technology, since the current technique must be improved to become cost-effective for application in post-combustion treatment at large scale. 6.1. Principle and description of the process As already mentioned in paragraph 3, post-combustion flue gasses contain large proportion of sulphur oxides and nitrogen oxides, as well as dust likely to degrade the solvent. Upstream from the CO2 capture system, the flue gases passing through SOx, NOx and dust elimination unit are cooled and the majority of the impurities are removed. At this stage the pressure of the exhaust gas is close to atmospheric and the temperature is between 40°C and 60°C. A



simplified flow diagram of a MEA absorption process is presented in Figure 5. The flue gases enter the bottom of the absorption column and rise upwards, whereas the CO2-lean solvent flows down from at the upper part of the system by gravity and comes into contact with the counter-current flow of exhaust gases involving the CO2 separation process. Therefore, the CO2 present in the flue gases diffuses through the solvent and it reacts chemically with the MEA. The gas-liquid exchange area inside the absorber is optimized in order to maximise the CO2 capture efficiency. Leaving the absorption zone the flue gases have lost about 90% of CO2 and continue rising through the absorber washing zone before being emitted into the atmosphere. In this zone the MEA solvent that is passed into the flue gases by vaporisation and mechanical drag is recovered by washing with water droplet. The solvent loaded with CO2 exits the absorption column from the bottom part and it is pumped into a heat exchanger where the CO2-lean solvent leaving the regenerator release heat. Afterwards the CO2-rich solvent passes into a regenerator vessel where it is heated to release CO2. At the bottom of the regenerator a boiler vaporizes some of the solvent to provide the heat energy required for the regeneration. This process is carried out at high temperature between 120°C and 140°C and relatively higher pressure between 0,1 and 0,3 MPa. Finally the CO2-lean solvent is pumped back to the absorption column via the heat exchanger to reduce the temperature until 50°C before injection into the absorber. Moreover, the CO2 released in the regenerator is usually compressed until a pressure of 10-20 MPa and dried for transport and storage. For particular transportation, such as ship and pipeline, the CO2 capture is compressed at 7 MPa and cooled at -55°C to provide its liquid state [3,15].

Figure 5 – Simplified diagram of an amine-based natural decarbonation unit [3]



6.2. MEA and chemical reaction involved An aqueous solution with 30% concentration of MEA is implemented in the post-combustion treatment allowing high absorption capacity and limiting solvent corrosion and deterioration. The chemical formula of MEA is shown in (3) [29], whereas the more complex chemical structure of various alkanolamines, generally called amines, is illustrated in Figure 6. H2N-CH2-CH2-OH (3) The amine function (NH2) of these compounds makes amines basic, allowing them to react with CO2. It is worth noting that different types of alkanolamines exhibit different reactivity with respect to CO2, since the nitrogen atom is bonded to single, double or triple carbon atoms. MEA is chosen for the absorption process rather than other amines owing to its high reactivity with CO2 together with its low molar mass (M = 61,08 g/mole), giving it a high CO2 absorption capacity per unit mass and limiting the flow rate of solvent applied in the process. Beside, other important advantages of MEA implementation are the relatively low cost of the solvent and the easiness of production [book]. Analysing the chemical reaction, the acidic CO2 in the flue gases is absorbed according to an acid-base reaction by the basic MEA as shown in (4):
! 2 !! !! !" !!! + !!! ↔ !! !! !" !!! +   !! !! !" !"#$!!



Carbon dioxide

Protonated MEA


This is a balanced reaction that can therefore be shifted in either direction by varying the process operating conditions. CO2 absorption is carried out at low temperature and it is an exothermic reaction realising heat. On the other direction of the reaction, MEA regeneration requires heat and it is achieved at high temperature [15].

Figure 6 – Chemical structure of some alkanolamines [3]



6.3. Key issue of the process The high energy consumption required to regenerate the solvent represents one of the major drawback of the chemical absorption process. This energy is divided between the following types of heat [4]: - sensible heat, which corresponds to the heat required to raise the solvent temperature from the absorption zone to the regeneration zone; - stripping heat, which is related to the energy required to vaporise some of the water contained in the solvent; - heat of reaction, which means the energy required to break the chemical bond formed between the CO2 and the MEA. Optimization of this operating cost is a critical aspect of the process and the minimum cost is reached when the concentration of the amines is approximately 50%. However a reduction in solvent regeneration rate causes a slightly increase in the total regeneration energy. Thus, in power plants application the common value corresponds to 30% of solvent concentration, as stated in paragraph 6.2. The efficiency of the absorption process is maintained at high level by MEA filtering, reclaiming and replacement and a common solvent consumption is between 0,2 and 1,6 kg/tonsCO2 [12]. In addition, the typical solvent losses are mainly caused by three different factors: - mechanical drag of vaporized solvent by the exhaust gas flow; - vaporization of the solvent in the flue gases; - solvent degradation and corrosion. The latter process is caused by irreversible damage to the MEA in the mixture and the built up degradation products becomes progressively less active for the CO2 separation and more corrosive for the installation. This phenomenon is reduced by a strictly corrosion control by means of limiting the excessive temperature in the regenerator and the addition of corrosion inhibitors. 7. TECHNO-ECONOMIC PERFORMANCE In principle, chemical absorption process for CCS applications can be applied broadly in large-scale industry. Nevertheless, few power generation stations, natural gas treatment plants and ammonia production facilities have already introduced this CO2 emission abatement treatment. The main reason is that the majority of power plants and industrial processes have typically low CO2 partial pressure in the flue gases, leading to more stringent condition for the CO2 capture process. According to [11], the CO2 capture cost tends to decrease when the exhaust gas from the process contains a pure and high partial pressure CO2 stream. Furthermore, the main parameters affecting the economic and technical installation of the CO2 recovery system are the following [12,1]: - flue gas flow rate and its CO2 content; - capture efficiency of the device; - increase of energy requirement; - CO2 purity at the end of the separation process; - solvent flow rate.



The main drawback of the CO2 capture system installation is the reduction both in the electric efficiency and in the specific work of the power station. As in chemical industry this negative effect can be overcome due to the high quality of the products, in the power generation this aspect represents a huge limit because the prince of electricity in the market is lower and it is more difficult to cope with the completion of other companies. In [8] the influence of CO2 removal system on the power generation plants was studied. As shown in Figure 7, the reduction in electric efficiency is higher compared to the reduction in specific work, leading to increase in fuel consumption and hence cost of electricity. It is interesting noting that also the liquefaction process of the carbon dioxide affects negatively the performance of the power plants. This further post-combustion treatment is usually applied in the circumstance in which the captured CO2 is not allowed to be storage the geological environment and hence its transport by ship or through pipeline is required. Since Inter-governmental Panel of Climate Change has published the cost and performance of new power plants with and without carbon dioxide removal in [12], a brief analysis of NGCC is carried out. Since many factors affect the techno-economic performance of power generations with CO2 capture system, Table A.1 (in Appendix A) describes several studies involved in the investigation of the natural-fired power plants in operation. The chemical absorption process with MEA is introduced in all of the studies and the overall performances are compared to. The CO2 recovery system is applied to the power generation leading to capture efficiency of the order of 85-90% and a CO2 emissions reduction of 83-88%. However, the reduction in net plant size and net plant efficiency correspond respectively to 13-15% and 6-10%. Moreover, the capital cost increases significantly by 64-100%, while the cost of electricity increase by 37-69%. The influence of the post-combustion process on the performance is studied in similar power plants in order to a better understanding and assessment of the costs impacts. Therefore, a brief comparison is carried out with reference to power generation representative both of consolidated technology, such as NGCC, and of emerging and innovative technology, including PC and IGCC. Table A.2 (in Appendix A) presents an overview of the overall performance and the CO2 capture cost of these power stations. The values are referred only to the capture process and do not include the cost of CO2 transport and storage. As the table shows, the NGCC is the process that suffers more the installation of CO2 recovery system both in the increase of capital cost and in the associated cost of CO2 avoided emissions. On the other hands, the overall efficiency with CO2 capturing remains higher in NGCC and the capture energy requirement is still lower compared to the other two types of power plant. Furthermore, other features need to be considered before being able to estimate the complete cost impacts of CO2 capture process and evaluating the specific circumstance under which the CO2 recovery system will be installed. It may be expected to investigate whether or not other emissions controls are already introduced in the power station. Moreover, it might be considered if the CO2 sequestration system is applied to an existing plant or it is designed for a new power plant [11,20].



57   ELECTRIC  EFFICINECY  [%]   55   53   51   49   47   45   300  



400   450   500   550   600   SPECIFIC  WORK  [kJ/kgair]  



Figure 7 – performance of combined cycle with and without CO2 removal and liquefaction [8].

According to [23], the high energy requirements for the regeneration process of the MEA solvent represents a strict limitation for the large-scale application. Thus, an optimization process is necessary in order to diminish the increase in energy demand and hence the rise of electricity cost. Even if the current cost of sequestration process remains about 55$/tons CO2, many efforts are involved to reduce this cost below 25$/tons CO2. In addition, recent studies shows that an overall investigation of the power plants offers considerable benefit in terms of environmental and cost effect. As stated in [18], the concept of ‘environomic’ (thermodynamic, economic and environmental) performance is introduced in order to highlight the wide problem concerning the CO2 capture system and the several parameters that has to be taken into account. 8. SIMILAR PROCESS APPLICATION Carbon dioxide capture systems have been applied broadly in industrial processes since over 70 years [15]. In the past years nevertheless the majority of CO2 was extracted cleaning the gases flow and then it was reemitted into the atmosphere, because restrictive and severe emission regulation policies and incentive by the governments were not applied yet. The continuous increase in carbon dioxide concentration in the atmosphere led to the application of severe emission regulation and hence the introduction of CO2 recovery systems with chemical solvents. Nowadays this established technology is broadly applied in several sectors of chemical industry [19]. In addition to power plants, there are worldwide large CO2-emitting factories in which CCS technology is usually performed at considerably lower costs involving the similar separation process mentioned in paragraph 7. However, the total reduction in CO2 emission remains much smaller compared to the volume of combustion-generated CO2



and a considerable benefit concerning the climate change problem has not reached yet. Current example of CO2 recovery systems from process streams are sweeting of natural gas, cement and steel production, oil refinery and production of hydrogen synthesis gas for the manufacture of ammonia, alcohols and synthetic liquid fuel [5]. 8.1. Natural gas sweetening Natural gas purification exhibits different level of carbon dioxide concentration depending of its source and for that reason different separation techniques, such as chemical and physical absorption and membranes, are applied in the industrial process. The emission abatement systems are commonly performed by chemical absorption process with various alkanolamines. For natural gas sweeting the absorption process takes place at higher pressure comparing with the process presented in paragraph 7. Thus a subsequent expansion before the regeneration column is required. As the CO2 concentration in natural gas rises, membrane systems are usually applied due to their competitive technology. Indeed they offer some advantages including lower capital cost, lower energy consumption and ease of installation energy [32]. 8.2. Ammonia production Carbon dioxide represents one of the main by-products of ammonia production and in modern industry the amount of CO2 produced is approximately 1,27 kgCO2/kgNH3. For this reason CO2 recovery system is a consolidated ongoing process during the ammonia production. However, the whole amount of CO2 capture is not available for transport and storage, since the ammonia industries are frequently connected with urea plants [12]. 8.3. Cement production Cement manufacturing is the second largest carbon dioxide emitting industry behind the power plants. The CO2 is released not only by the fossil fuel combustion but also during the production of lime from the calcium carbonate leading to CO2 emissions about 15% of the total amount of CO2 emissions in the world [30]. In principle, cement production allows introducing the established post-combustion technologies for CO2 capturing, since the CO2 concentration in the flue gases between 15-30% by volume is significantly higher than in the exhaust gas from power and heat production. Nevertheless, the chemical absorption technique has not been applied in the cement processes yet. Indeed, cement production manufacturing requires a large amount of fossil fuel to drive the high temperature and the high-energy reactions and also an additional steam generator for the regeneration process of the solvent used in the CO2 capturing. This aspect represents the main drawback of CCS installations in cement industry.



8.4. Steel production The steel and iron industry is established as the largest energy-consuming sector in the world manufacture. According to [30], the energy consumption reaches 10-15% of the total industrial energy consumption and the carbon dioxide emissions released into the atmosphere are approximately 6%. The steel and iron production offers many possibilities of carbon dioxide emission abatement, for example removing the CO2 from the blast furnace and recycling of CO-rich gas to the upper part of the device with a mixture of pure oxygen. Other novel processes for CO2 recovery have been investigated and they are currently at the R&D stage. CONCLUSION Among the various post-combustion CO2 capture pathways, the absorption process using chemical solvents currently represents the most established technique and hence it is considered the process preferably applied to the power plants in the short-term period. However the capture cost is still double that required for massive use and the capacity of the present CO2 recovery systems in terms of tonnes of CO2 captured per day is still well below the size of typical installations. Development of new solvents more competitive than the current ones, including potassium carbonate and sterically hindered amines, is clearly the challenge for CCS applications in the power station, which should lead to large-scale industrial implementation in the medium terms. Further studies are involved in the investigation of other techniques, such as membranes, absorption on solids, metal organic framework and cryogenics. They might become feasible for power stations in the long terms replacing the existing systems, being cost-effective and reducing the energy required. In conclusion, minimizing the energy required by the CCS system, together with improvements in capture efficiency will continue to be the principle objective for future technology development in order to reduce the overall environmental impacts and cost.



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APPENDIX A. Cost and performance data of CCGT Table A.1 - CO2 capture cost in natural-fired power plants using current technology [12].



Table A.2 - Summary of new plants performance and CO2 capture cost based on current technology [12].



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