Review Paper - CCS

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02638762/06/$30.00+0.00 # 2006 Institution of Chemical Engineers Trans IChemE, Part A, September 2006 Chemical Engineering Research and Design, 84(A9): 739 763
REVIEW PAPER
CO2 CAPTURE AND STORAGE Closing the Knowing Doing Gap

R. STEENEVELDT , B. BERGER and T. A. TORP
Statoil ASA, Research & Technology Development, Rotvoll, Norway
he capture and storage of CO2 is gaining attention as an option for limiting CO2 emissions from the use of fossil fuels. CO2 capture is premised on the safe long-term storage of CO2 in geological formations. Naturally occurring CO2 is used for enhanced oil recovery in the USA, Trinidad, Turkey, Hungary, Brazil and Croatia. Industrially produced CO2 has been used for enhanced oil recovery at the Rangely eld in Colorado, USA since 1986 and at the Weyburn eld in Saskatchewan, Canada since 2000. Large-scale CO2 storage in geological formations to avoid CO2 emissions was rst undertaken offshore in Norway in 1996 and onshore in Algeria in 2004. CO2 delivered for EOR in the USA averaged around USD 11/tonne CO2 during the 1990s. The cost of CO2 capture from low concentration industrial sources varies with a number of factors, but will certainly be very much higher than the recovery of naturally-occurring CO2. Adequate knowledge exists in the oil and gas industry for the application of CO2 capture and storage. Widespread implementation of fully-integrated CO2 value chains will nonetheless depend on achieving public acceptance and regulatory approval for CO2 storage, cost reduction for CO2 capture and sufcient economic incentives for the key actors involved. This article discusses the most important research directions for CO2 capture and storage projects that have been initiated around the world. The adequacy of economic incentives will strongly inuence how quickly producers and users of fossil fuels are able to close the knowing-doing gap for CO2 capture and storage. Keywords: carbon dioxide capture; carbon dioxide storage; carbon dioxide transport; carbon dioxide value chain; carbon dioxide capture costs.
INTRODUCTION The worlds dependence on fossil fuels for the satisfaction of primary energy needs is at odds with growing atmospheric emissions of CO2 from the combustion of hydrocarbons. Given their high energy density and availability, fossil fuels are likely to continue to provide more than 80% of total world energy requirements for the coming decades, with especially coal and natural gas asserting their positions in the fuel mix by providing 38% and 30%, respectively of electricity demand in 2030 (IEA, 2004a). On a global basis, coal accounted for 24% of primary energy consumption in 2004, oil for 34%, natural gas for 21%, nuclear for 5%, large hydropower for 6% and renewable accounting for approximately 10% (BP, 2005) Power generation comprises the largest source of CO2 emissions (see Figure 1) (IEA GHG, 2002b). Flue or stack gases from this sector are usually at atmospheric pressure with the CO2 concentration varying between 3% (vol.) for natural gas red plants and 14% for oil and coal
Correspondence to: Ms R. Steeneveldt, Statoil ASA, Research & Technology Development, Arkitekt Ebbellsvei 10, Rotvoll, N-7005, Norway. E-mail: rosst@statoil.com
red boilers. In addition to fossil fuel based heat and power production, large stationary sources of CO2 emissions include natural gas sweetening, hydrogen production for ammonia and ethylene oxide, oil reneries, iron and steel production facilities, cement and limestone manufacturing plants. The transportation sector contributed 18% of global CO2 emissions in 2001 (Ibid). A viable CO2 value chain could provide the foundation for reducing emissions from the transportation sector through the production of hydrogen from fossil fuels. While the CO2 content of emissions from ammonia, ethylene oxide and renery reformers is typically above 95% (dry volume basis), iron and steel, cement and limestone production results in atmospheric emissions with a CO2 content of 20% or higher (Sheinbaum and Ozawa, 1998). Figure 2 shows that large-scale commercial applications of CO2 separation technology have typically been from streams where the partial pressure of CO2 is relatively high. Some newer concepts for power production focus on producing a pressurized and/or concentrated stream of CO2 so as to reduce the energy required for separation. Where systems for CO2 transport and storage are tolerant of contaminants like SOx, NOx and Hg, potentially costly investments in ue gas clean-up may be circumvented by co-storage of these components with the CO2. 739
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STEENEVELDT et al. plant (IPCC, 2005). Senior et al. (2004) provide an overview of the cost distribution, reproduced in Table 1. For example, Kvamsdal et al. (2005b) reported 67 USD/tonne5 total costs of CO2 capture from a 860 MW power plant, whereof 54 USD/tonne was the cost of capture and 13 USD/tonne the transport cost for a 150 km pipeline. There is remaining uncertainty about the application of the London (Dumping) Convention and the OSPAR Convention (Oslo Paris Convention), to CO2 storage offshore in geologic formations. Clarication may require intergovernmental negotiations. Public acceptance and endorsement of CO2 storage is an important premise for CCS. Apart from sizeable research funding only the Netherlands6 and Norway have in place legislation that provide some incentive for CO2 capture and storage (see Lee et al., 2005). Consequently, research on CO2 capture aims at technology development for reduced capital and operating costs, while research on CO2 storage aims at technology development for monitoring and verifying the safety of CO2 injection. The main research directions for CO2 storage and capture are depicted in Figure 3. A comprehensive review of the extensive literature on CO2 capture and storage is not the intent of this paper. The objectives of this paper are to: (1) give an overview of the most important CO2 capture technologies, (2) examine the status of the most important CCS projects that have been initiated worldwide, (3) briey examine the remaining development challenges of the main capture technologies, and (4) discuss some of the challenges for realizing a global CO2 value chain.7 Some scholars have argued that, like with systems for SOx removal, the cost of building and operating CO2 capture systems should be reduced over time through cumulative learning and technological progress (e.g., Alic et al., 2003; McDonald and Schrattenholzer, 2001; Riahia et al., 2004; Rubin et al., 2004a,b; Rao et al., 2003). As will be discussed in the remainder of this paper, there are numerous technical routes to CO2 capture at different stages of maturity. The cumulative learning contention rests on the assumption that there is effective learning across technology platformsan assumption that is debatable where there is a proliferation of approaches. The biggest factor likely to inuence the implementation of CCS is government support (both in terms of size and perceived predictability). SEPARATING CO2: EXISTING TECHNOLOGY In the petrochemical industry, CO2 is separated from other gaseous components using both physical and chemical absorbents. Large scale CO2 separation units in operation today focus on the removal of unwanted CO2 at high partial pressure. The recovery of CO2 from ue gas
5 6
Figure 1. Global CO2 emissions in 2001 (IEA).
Improved energy efciency, fuel switching (e.g., from coal to natural gas) and the capture and storage of CO2 are strategies for climate change mitigation that reconcile the continued use of fossil fuels with goals to reduce CO2 emission related to meeting global energy needs.1 This article focuses on CO2 capture and storage (CCS). The major components of a CCS value chain include capture (i.e., separation and compression to supercritical state) transport and storage (including measurement, monitoring and verication of safe operations). The large scale applications of CO2 that have been identied are the use of CO2 for enhanced oil recovery (EOR2), and for enhanced coal bed methane (ECBM3). The costs of CCS based on fossil fuels depends on a number of variables and considerations (see for example Bock et al., 2003; Rubin and Rao, 2003), including the cost of fuel, the technology characteristics of the power or industrial plant, the scale of the capture plant, the percentage CO2 captured, the characteristics of the storage site and the required transportation distance. CO2 capture from high pressure, high CO2 concentration streams can potentially be performed at lower cost than from exhaust gases from power production. In general, for CO2 capture and storage from power station ue gas, the cost of CO2 separation and compression dominates the CO2 costs, making up 50 80% of total specic CO2 costs across the value chain4: The application of capture technology would add about 0.18 0.034 USD/kWh to the cost of electricity from a pulverized coal power plant, 0.09 0.22 USD/kWh to the cost for electricity from an integrated gasication combined cycle coal power plant, and 1.2 2.4 USD/kWh from natural gas combined cycle power
Increased use of renewable energies and nuclear energy may also contribute to reducing CO2 emissions associated with meeting energy needs.
2 Enhanced oil recovery (EOR) is the term used for those techniques that are put into effect for altering the original properties of the oil to improve recovery from a producing eld. Enhanced oil recovery restores reservoir pressure and improves uid ow. The three major types of enhanced oil recovery approaches are chemical ooding, miscible displacement (CO2 injection or hydrocarbon injection) and thermal recovery (steamood or in situ combustion). Enhanced oil recovery is also called improved oil recovery or tertiary recovery. 3 Enhanced coal bed methane (ECBM) is the term used for techniques that increase the recovery of methane from unmineable (uneconomic) coal seamsCO2 is selectively adsorbed into the pore volume displacing the methane. 4 The cost of modications required to implement CO2 injection for EOR may in some cases prove to be substantial. 1
Assume 1 1 USD.
The Electricity Act that came into force on 1 July 2003, suggests that a tax exemption worth approximately 25 40 million in the rst year and increasing every year by between 2530 million will be established to support renewable energy, energy efciency and climate neutral electricity, including CO2 capture and storage.
7 While the potential fuel efciency achievable with fuel cells (SOFC; MCFC) are promising, the limited scale envisioned for fuel cells (10 50 MW) will limit the application of this technology for centralized power production. For this reason, research on fuel cells has been excluded from this review.
Trans IChemE, Part A, Chemical Engineering Research and Design, 2006, 84(A9): 739 763
CO2 CAPTURE AND STORAGE
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Figure 2. Partial pressure of CO2 from the most important CO2 producing stationary processes.
Table 1. Overview of indicative costs of elements in a CO2 capture and storage value chain. USD/tonne CO2 Capture and compression Transport Storage 590 020 212 Common cost drivers Volume of CO2 Location Specic cost drivers CO2 partial pressure in source Existing infrastructure Transport distance Existing infrastructure Storage capacity Monitoring requirements
is performed on a limited scale at a small number of plants around the world (IEA GHG, 2004). Physical solvents commonly in commercial use include methanol, dimethyl ethers of polyethylene glycol, propylene carbonate, and potassium carbonates (Astarita, 1983). Conceivable commercially available alternatives are selective polymeric membranes and cryogenic separation. The factors inuencing the choice of separation technology are the partial pressure of the CO2 in the feedstream, sensitivity of the method to other impurities or trace components, CO2 recovery, capital and operating costs and environmental impacts (waste or by-product production). For separating CO2 from ue gas with very low CO2 partial pressure in a large stream of mostly non-condensable gases, absorption processes using chemical solvents offer distinct advantages over the alternatives: lower energy use and costs, higher capture efciency and better selectivity. The application of selective membranes8 and cryogenic separation is economic for streams having both high feed
8 The trade-off between purity and recovery typically experienced with solution-diffusion membranes, makes it costly to achieve both high CO2 purity and high CO2 recovery.
concentration of CO2 and high pressure and low concentrations of other acidic components, like H2S. Despite the observation that examples of the small-scale commercial application of CO2 absorption from ue gas can be found around the world,9 the treatment of power plant ue gas for CO2 storage represents a scale-up challenge: The capacity of CO2 capture from ue gas for the supply of CO2 to the food and beverage industries ranges from 6 to 800 tonnes/day CO2 (Herzog, 1999; IEA, 2004b). Since a 500 MWe pulverized coal power plant emits approximately 10 12 k tonnes/day, and a natural gas combined cycle plant approximately 4 k tonne/day, this implies scale-up of 20 50 times (Riemer and Ormerod, 1995; IEA GHG 2000b). With absorber diameters of up to 15 meters considered feasible, single train CO2 recovery plant capacities of up to 8000 tonnes/day are believed achievable, depending on the inlet ue gas CO2 concentration. Larger plants could be designed with multiple absorbers that share a common stripper (Reddy et al., 2003; Roberts, 2002).
9 Fluors Bellingham 330 tonne per day CO2 capture plant is largest commercial plant based on turbine ue gas.
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Figure 3. Main research directions for CCS.
RESEARCH ON CCS There is signicant spending on CCS research and development around the world and in particularly in the EU, in the USA (DOEs Carbon Mitigation Program), Canada, Australia Japan and Norway. More than USD 80 million excluding the matching contributions from industry participants and other research institutions has been directed at CCS research under the EUs framework 5 and 6 programmes (McKee, 2002). The DOEs Carbon Mitigation Program had an annual budget of USD 46 million in 2005, with projections of a baseline funding requirement of USD 30 million per year until 2020. The IEAs Greenhouse Gas Program was established in 1991, providing an early marketplace for ideas and research on CCS. The recently released IPCC10 Special Report on Carbon Dioxide Capture and Storage (http://www.ipcc.ch/ activity/srccs/index.htm) knits together the diverse threads of research on CCS, presenting the results of 15 years of international research effort. Table 2 below lists a selection of the completed and ongoing international research projects on CCS. In addition there are pilot facilities at Karst, Norway, Osaka, Japan (Buller et al., 2004) and at the Boundary Dam power station, Saskatchewan, Canada with a capacity of 48 tonnes CO2 per day (Wilson et al., 2004). The CO2 capture pilot plant with the largest design capacity to date, of 24 tonnes CO2 per day, was opened at Esbjerg, Denmark in March 2006. An explicit goal for all ongoing research on CCS is the demonstration of new technology at pilot and semi-commercial scales.
point. All of the capture and storage pathways require energy, which implies that processes with CO2 capture produce more CO2/kWh or CO2/product (than equivalent reference plants without capture). For most analyses, the system boundaries are drawn such that energy involved in exploration/mining, energy for the production and transport of fossil fuels, the energy required to produce and transport important capture components like, e.g., amines for post-combustion and energy required for the disposal of waste is excluded from the analysis. A discussion of system boundaries can be found in Haefeli et al. (2004). Lombardi (2005) found the emissions associated with construction and dismantling of capture plants to be negligible relative to that of the central combustion processes. The CO2 emissions directly associated with capture, compression, transport and injection for storage or enhanced oil recovery are most often included. From a CO2 accounting perspective, both the direct and indirect CO2 emissions are important,11 as well as the estimated leakage from storage (see e.g., Ha-Duong and Keith, 2003). Implicit to the observation that there are additional CO2 emissions associated with all concepts, the CO2 avoided i.e., both the direct and indirect CO2 emissions from a reference plant (without capture) less CO2 emissions from a given plant with capture is often used in the literature. A discussion of methodological issues for calculating CO2 costs can be found in Melien (2005).
NEAR TERM IMPLEMENTATION OF CO2 CAPTURE FROM POWER PRODUCTION CO2 CAPTURE: PATHWAYS TO LOW EMISSIONS HEAT AND POWER The three main pathways to CO2 capture and storage are shown in Figure 4. CO2 is separated from the other components to optimize CO2 compression to the dense phase, for cost-effective transport and injection at the storage site and to meet the purity requirements at the injection
10 Intergovernmental Panel on Climate Change: http://www.ipcc.ch/ activity/srccs/index.htm.
In addition to the CO2 storage projects (discussed below) that are projected to come on-stream in the near future, there are three announced plans for realizing large-scale CO2 capture (and storage) from power production. These are BPs ambitious Decarbonised Fuel project in the UK, Vattenfalls 30 MWth oxyfuel pilot plant in Germany (Vattenfall, 2005) and CESs potential 50 MWe pilot in the Netherlands: BP and partners, Royal Dutch/Shell,
11
Associated with import of electricity or (other products) for example.

Table 2. Selection of international projects on CSS. Project CANMET Energy Technology Centre (CETC) SACS GESTCO ICBM GEODISC CCP 1 (http:// www.co2captureproject.com/ index.htm) RECOPOL US DOE Carbon Sequestration Program NGCAS NASCENT Total project funding (Million) Focus areas R&D Oxyfuel Combustion for CO2 Storage in Saline Aquifers: Sleipner Case CO2 storage potential in Europe Enhanced Coal Bed Methane, coal elds in Europe Storage Entire CCS value chain Economic comparisons of alternatives Enhanced Coal Bed Methane in Poland CCS CO2 storage Natural analogues in Europe for CO2 storage Timeframe 1994 19972002 19992002 20002003 19992002 20002005 20012004 20012020 20022005 20012004
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Capture/storage Capture Storage CO2 storage in coal seams CCS A eld injection trial of CO2 into a coal seam in Poland CCS CO2 storage in an offshore depleted oil eld Studying natural accumulations of CO2 in geological formations CO2 storage CCS
4.5 million US 3.76 Million Unknown 10 million Aust Dollars 28 million Dollars 3.5 million 30 million US per year 0.6 million 3.3 million
NACS CRUST CCP 2 (http:// www.co2captureproject.com/ index.htm) EU CASTOR (http://www.co2castor.com) CO2sink EU CO2GEONET CO2STORE (Norway and European Commission)
1.5 million 12 million
15.8 million
8.7 million 6 million 2.5 million
EU ISCC ENCAP (http:// www.encapco2.org/) EU HYPOGEN, Dynamis US DOE FutureGen ARC Enhanced Coal-Bed Methane Recovery Project (Canada, United States and United Kingdom) Frio Project (United States and Australia) ITC CO2 Capture with Chemical Solvents (Canada and United States) IEA GHG Weyburn CO2 Monitoring and Storage Project, Research project Weyburn II CO2 Storage Project (United States, Canada, and Japan)
2.9 million 22.2 million 1 billion US 3.4 million Canadian $
Demonstration of CO2 storage in depleted hydrocarbon reservoirs Continue the development of new technologies to reduce the cost of CO2 separation, capture, and geologic storage Novel solvents, Contacting Membranes, Advanced Process Development, 1 t/h CO2 capture Pilot plant at Esbjerg Ketzin CO2 injection project Network of excellence Follow-up to the Sleipner project, monitoring to track CO2 migration, focus on geochemistry and dissolution processes CO2 capture using solid sorbents Precombustion CO2 capture
20022005 20052007
20042008
CCS
20042009 20042009 20032006
Storage Storage Storage
20042007 20042009 20062015 20022012
Capture Capture Capture CO2 capture from coal and storage Storage
CO2 injection into deep coal beds
Demonstrate CO2 sequestration in an on-shore underground saline formation Demonstrate CO2 capture using chemical solvents 27 million USD CO2 for enhanced oil recovery
Storage Storage Storage
ConocoPhillips and Scottish & Southern Energy PLC have announced plans for a large-scale CO2 capture and storage project, envisioned to come on-stream in 2009 (http:// www.bp.com). The chosen route is the production of
hydrogen from natural gas. The hydrogen will fuel 350 MW from Scotlands Peterhead power station while 1.3 million tonnes of captured CO2 will be transported by an existing pipeline and injected for enhanced oil recovery and
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Figure 4. Main CO2 capture routes (from CCP12).
deep geological storage in the Miller Field.13 Vattenfall of Sweden (http://www.vattenfall.com) has announced plans to build a 30 MWth lignite-based plant using oxyfuel technology. The pilot plant is expected to come on-stream in 2008 and will provide the design basis for scale-up of the technology to 600 MWe. Although a solution for the CO2 has not been made known, oxyfuel boiler technology allows the recovery of high concentration CO2 Clean Energy Systems (CES) (http://www.cleanenergysystems.com) and SEQ Nederland, B. V. have entered into an agreement for engineering services for a 50 MW power plant to be built in the Netherlands, where the carbon dioxide captured from the plant will be used for enhanced gas recovery. By avoiding harmful atmospheric emissions, the proposed project could qualify for governmental support as a climate neutral combustion technology, under current Dutch law (see footnote 6). THE CONTENDING TECHNOLOGIES: POST-COMBUSTION CO2 CAPTURE The main routes for CO2 capture are depicted in Figure 4. The generic combustion reaction for hydrocarbon fuel can be written as equation (1) below where f is the molar ratio of air required in excess of stoichiometric oxygen required. n Cm Hn F m (O2 3:77 N2 ) 4 n n mCO2 H2 O (F 1) m O2 ! 2 4 n F m 3:77 N2 (1) 4
12 CCP: CO2 Capture Project: Carbon Capture Project, see http:// www.co2captureproject.org. 13 Injecting the carbon dioxide into the Miller Field reservoir more than three kilometres under the seabed could extend the life of the eld by about 20 years and enable additional production of about 40 million barrels of oil that are not currently recoverable.
The large amounts of excess air required for combustion control in current boiler and gas turbine technology result in a dilute CO2 stream that also has signicant oxygen content. Chemical absorption processes employ the reversible nature of the reaction of an aqueous alkali solvent with an acid gas. MEA (monoethanolamine), MDEA (methyldiethanolamine) and DEA (diethanolamine) are currently the main chemical solvents of interest for acid gas treatment. The process technology for acid gas removal from natural gas was developed during the 1920s (Herzog, 1999). For MEA, the fundamental reaction for the process is: ! C2 H4 OHNH2 H2 O CO2 C2 H4OHNH3 HCO3 The reaction proceeds to the right at low temperature 251008C allowing absorption from the gas stream. The solvent can be regenerated, and the CO2 recovered as a concentrated stream, by heating the solvent solution into the temperature range of 1001508C to reverse the absorption chemistry (Aboudheir et al., 2003). The economic amount of CO2 removal for post-combustion is between 80% and 95% CO2. Kvamsdal et al. (2005b) found that there was an efciency gain in lowering the CO2 capture from 90% to 75%, but found a sharp increase in capital costs for 95% capture. There are three main technology suppliers (see Table 3). From the process ow diagram shown in Figure 5, incoming gas is cooled, and enters the CO2 absorber where CO2 is taken up by the solvent at temperatures typically between 40 and 808C. The top section of the column is used as a water wash to prevent solvent carry-over and to correct the water balance. The rich solvent is pumped to the top of the stripper where the solvent is regenerated at about 1001408C, at around 60 kPa (g) (Barchas and Davis, 1992; Roberts et al., 2004). While many of the constituent elements of the amine scrubbing process consists of widely-known technology, the development of inhibitors and their application to

Table 3. Comparison of established suppliers of MEA scrubbing technology. Abb Lummus Kerr McGee Solvent used Solvent Replacement Cost (USD/tonne CO2) Source of CO2 Commercial experience 1520 wt% aqueous MEA (Monoethanolamine) inhibitor Coal The largest capacity delivered is 800 tonnes/day of CO2 utilizing two parallel trains Fluor (Econamine FG Plus) 30 wt% aqueous solution MEA 2.3 Natural gas Many plants worldwide recovering up to 330 tonnes/day of CO2 in a single train for use in beverage and urea production
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Mitsubishi Heavy Industries/ KEPCO (KS-1 Process) KS-1 2.28 Natural gas First commercial plant at 200 tonnes/day CO2 recovery from a ue gas stream has been operating in Malaysia since 1999 for urea production
Figure 5. Typical owsheet for CO2 capture using MEA.
cost-effectively prevent degradation and corrosion is a key area of technology know-how. Apart from the concerns for the purity of the CO2 at the point of use, the impurities in the ue gas are also important for the overall design and cost of the CO2 removal plant (Herzog et al., 1991). The relatively high oxygen content of ue gas represents a particular challenge for amine absorption due to degradation of amine by the oxygen. Solutions of MEA that are partly degraded are aggressive at high concentrations, causing high rates of corrosion, degradation of column internals and other elements (including lters) and reaction with other components in the gas. Flue gas from combustion will usually contain acidic components NO2 and SOx, hydrogen sulde (H2S), HCl, arsenic, and mercury. MEA removes nearly all of the SO2 and some of the NO2 but very little NO and
N2O.14 NO2 is usually less than 10% of overall NOx content in ue gas (Chapel et al., 1999, 2001). The acidic components react with the amine to form stable salts that reduce the absorption capacity, accumulate in the solution and cannot be regenerated by heating in the stripper. This represents a loss of solvent from the system and increases the solution viscosity undesirably. The elimination of heat stable salts results in operating costs for reclaiming the solvent and for handling the waste stream of sulphate and nitrate salts. MEA is typically recovered from the heat
14 The authors are not aware of research that has examined the effects of the other impurities on MEA absorption. Like with NOx and SOx, HCl also reacts with MEA to form heat stable salts. Remaining work in the EU project CASTOR will aim to better understand the formation of heat stable salts and the effect of ue gas impurities on absorption efciency and cost.
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Table 4. Energy requirements for post-combustion CO2 capture (leading technologies). Natural Gas Derived Flue Gas (GJ/tonne CO2) Coal Derived Flue Gas (GJ/tonne CO2) 45% (Pulverized Bituminous Coal 600 MW) 0.4 0.040.1 0.060.11 Specic power consumption will decrease with decreasing pressure ratio Average MW of coal-derived ue gas is higher (values from Bolland and Undrum, 2003) Lower circulating vol required for higher concentration CO2 in ue gas (values from IPCC, 2005; pg 117) Equivalent power from LP steam extraction (from Bolland and Undrum, 2003) Comment
Fuel Efciency without CO2 capture Captured CO2 Compression to 100 bar (g) Blower (overcome pressure drop in absorber) Pumps
58% (Combined Cycle, 0.04 bar condenser pressure 400 MW) 0.4 0.1 0.34 0.210.33
Sub Total Power Regeneration Heat (Equivalent Power) Fuel Efciency (%) with CO2 capture
Power: 0.711.07 2.7 3.3 (0.620.76) 47 50%
Power: 0.510.61 2.73.3 (0.620.76) 3436%
stable salts through reaction with soda ash (Reddy et al., 2003; Kvamsdal et al., 2005b). In addition to the solvent degradation, other gaseous components also affect the driving force for CO2 absorption, an effect that becomes more pronounced at elevated pressures (De Koeijer and Solbraa, 2004). The limits on SO2 and NO2 concentration in the ue gas being treated for CO2 removal by MEA absorption are recommended to be in the range from 10 to 50 ppmv. Amine tolerance levels are reported to be 90 ppm O2, 10 ppm SO2 and 20 ppm NOx (at 6% excess oxygen) (IEA, 2004b). At these values solvent degradation is not eliminated, but simply reduced to an acceptable rate (Heggum et al., 2005). Fly ash and soot removal is also important to prevent both foaming in the absorber and further reactions with the solvent. Post combustion treatment is costly and energy-intensive because of the large volume of gas to be treated, the low partial pressure of CO2 in the ue gas, the presence of contaminants that may be detrimental to the solvent and the energy demand associated with solvent regeneration. MEA has a high heat of absorption (which needs to be supplied in the regeneration step), the absorption of CO2 is modest and concentrations much greater than 20 30% result in corrosion problems. The energy requirements for post-combustion CO2 capture are summarized in Table 4. Extraction of LP steam from the steam turbine, instead of increasing the fuel demand gives 2 3% gain in fuel efciency (Bolland and Undrum, 2003; Kvamsdal et al., 2005b). Compression of CO2 to export pressure and the regeneration heat for the amine solution are the largest consumers of energy. In addition to increased fuel costs, operating costs for post combustion plants are incurred by replacing consumed solvent (0.2 1.6 kg/CO2 tonne) and the use of chemicals for the removal of decomposition products (e.g., 0.03 0.13 kg NaOH, 0.03 0.06 kg activated carbon/tonne CO2) (IPCC, 2005). Improvements that have already been identied could potentially reduce the energy requirements for post-combustion capture from the research efforts aimed at overcoming the weaknesses of the predominant approaches for post-combustion CO2 removal are outlined in Figure 6.
IMPROVED ABSORPTION An overview of existing solvents is given in Table 4. Sterically hindered amines have more favourable reaction stoichiometry, such that the theoretical capacity is higher than MEA, and lower heat of absorption/regeneration. Examples of sterically hindered amines are 2-amin-2methyl-1-propanol (AMP), and the proprietary solvents marketed by Mitsubishi Heavy Industries, KS-1, KS-2 and KS-3 (White et al., 2003). A large research effort is being directed at improved solvents to improve the CO2 loading, reduce the energy requirement for solvent circulation and regeneration and to overcome solvent degradation (Chakma, 1995; Chakma and Tontiwachwuthikul, 1999; Mimura et al., 1999; Zheng et al., 2003; Cullinane and Rochelle, 2003; Leites, 1998; Erga et al., 1995; Aresta and Dibenedetto, 2003; Bai and Yeh, 1997; Chakravarti et al., 2001; Mimura et al., 1995; Mimura et al., 2003). Improving the activated potassium carbonate process has been investigated using piperazine (e.g., Cullinane and Rochelle, 2003; Bishnoi and Rochelle, 2002). There is evidence that the capture process efciency can be substantially improved by careful design of a mixture of solvents (Melien, 2005; White et al., 2003). While current suppliers of technology, ABB Lummus, Fluor and Mitsubishi/ Kansai Electric Power Company (KEPCO) are pursuing research on improved solvents, there is ongoing research around the world including at the Tokyo Electric Power Company, TNO,15 in the Netherlands and at Praxair, Table 5 gives an overview of some of the amine-based solvents under development. Even though improved amines, e.g., can save regeneration operating costs, they may have slower reaction kinetics and thus require longer gasliquid contact time in the absorber. The design of improved contacting equipment that additionally overcomes the known operational problems with packed columns (ooding, channelling, entrainment and foaming) is thus another area where improvements are needed. Improved
15 TNO is a contract research and specialist consultancy with its corporate centre in Delft, The Netherlands, see http://www.tno.nl.
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Figure 6. Post-combustion research directions.
Table 5. CO2 solvents under development. Absorbent Licensor Fluor-Daniel Ecoamine ABB Lummus-Global Mitsubishi TNO (future) University of Regina Praxair CANSOLVw Absorbent MEA additives MEA KS-1, KS3 CORAL PSR Amine Blends CANSOLVw
packing, (e.g., Aroonwilas et al., 2003; Kvamsdal et al., 2005b) and the use of contacting membranes (e.g., Sybe Grnvold et al., 2005; Feron and Jansen, 2002; Feron, 1992, 1994; Falk-Pedersen et al., 1999) has been investigated. DeMontigny et al. (2005) found signicantly higher mass transfer coefcients for polymeric contactors as compared to structured packing. While membrane systems potentially have a smaller footprint and lower weight than conventional systems (Herzog and Falk-Pedersen, 2001), their modular nature implies that economy-of-scale benets for very large scale CO2 capture plants are likely to be very modest or non-existent. The combination of chemical absorption and selective membranes has also been suggested, so as to perform absorption and desorption in a single unit, see Mano et al. (2003) and Okabe et al. (2003). The combination of polymeric microporous membranes and DEA has been investigated by Bao and Trachtenberg (2005). The use of the carbonic anhydrase to catalyse and accelerate CO2 absorption and desorption forms the basis of the start-up company Carbozyme Inc.16 Other avenues that have been investigated are increased concentration of solvent (Aboudheir et al., 2003), so as to reduce circulation rates and thus energy requirements for regeneration, removal of oxygen, so as to enable the use of solvents that are intolerant of oxygen (Nsakala et al., 2003). Ammonia has been proposed as an alternative to amines and can be employed to capture all three major acid gases (SO2, NOx, CO2) in addition to any Hg, HCl and HF, which may exist in the ue gas of coal combustors
16
(Huang et al., 2002; Yeh and Bai, 1999; Yeh et al., 2002). Since SO2, NOx and Hg emissions must comply with given limits, a single process to capture all acidic and toxic gases is expected to reduce the total cost and complexity of emission control systems. Unlike the MEA process, ammonia is not expected to have absorbent degradation problems that are caused by sulphur dioxide and oxygen in ue gas, is not expected to cause equipment corrosion and could potentially reduce the energy requirements for CO2 capture. Recently, Powerspan Corp.,17 reported the application of ammonia for simultaneous reduction of SO2, NOx and mercury and announced the start-up of a pilot plant for testing the novel emission control concept that includes CO2 removal in 2006. In addition to the absorption processes using ammonia as a regenerative solvent, CO2 capture for the production of fertilizer has also been investigated. Split ow, where a portion of the side draw from the absorber is fed to the stripper, bringing the operating line of the absorber parallel to the equilibrium line and so improving the thermodynamic efciency (and thus lower reboiler duty) of the absorber has been suggested (Reddy et al., 2003). Kvamsdal et al. (2005b) found that at low CO2 loading and the correspondingly low regeneration temperature, a split ow regime gives no appreciable decrease in reboiler duty solid sorbents for CO2 have also been investigated (Abanades et al., 2004; Green et al., 2002). The purity of CO2 from post-combustion capture is typically 99.9% (vol.) (Sander and Mariz, 1992). However, CO2 derived from combustion gases may contain sulphur oxides, nitrogen oxides, several different low molecular weight hydrocarbons, carbon monoxide, and mercury. The concentrations of these impurities may vary greatly in individual processes; also, the variety of possible CO2 sources is responsible for a large number of potential impurities in the produced CO2. POWER BLOCK/CAPTURE INTEGRATION Energy requirements can be reduced by pursuing energy integration between the CO2 capture plant and the power plant. The recirculation of ue gas is the most
17
http://www.carbozyme.us/.
http://www.powerspancorp.com.
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STEENEVELDT et al. NEW TURBINE CYCLES Applying new turbine cycles to produce ue gas with higher CO2 content may avoid some of the challenges for post-combustion CO2 capture. For example, the Combicap concept (Lynghjem et al., 2004) comprises two gas turbines that are interconnected by a CO2 separation system and an integrated combustor-heat exchange system (see Figure 7). Combicap aims at producing a ue gas stream with a higher CO2 partial pressure. By recirculating the ue gas stream from the main gas turbine, a novel semi-closed top cycle is proposed employing a working uid of mostly N2 (approximately 85%) and CO2 (approximately 10%). The CO2 concentration is limited by the oxygen required in the combustor for complete combustion. Gas exiting the CO2 removal unit needs to be heated up to the hot gas temperature of the helper gas turbine unit. This required heat may be provided by heat exchange, without adding CO2 to the gas, or by supplementary ring that will lead to some additional CO2 in the exhaust gases if natural gas is burned. Increasing the CO2 partial pressure (.1.5 bar), potentially lowers the cost of CO2 capture by, e.g., polymer membrane systems. The use of novel, xed site carrier membranes where an amine group and other cross-linking agents (e.g., Fl) are incorporated into the structure of a polymer membrane for CO2 capture from ue gases has been investigated. (e.g., Hagg and Lind brathen, 2005). The Combicap concept exhibits relatively high overall fuel efciency (approximately 50%) due to the high temperature at the turbine inlet and has low formation of NOx since the combustor receives both fresh
studied integration option (Bolland and Sther, 1992). Combinations of the aforementioned measures have also been evaluated: For example Mimura et al. (1997) have investigated the combination of new solvent technology and integration of the steam requirements for the CO2 stripper with the power plant, and found that the energy penalty for CO2 capture and compression can potentially be lowered to 10 11% for natural gas and 15% for conventional coal. Chinn et al. (2004) proposed engineering options for reducing the costs of amine-based CO2-capture from the ue gas of a 400 MW natural gas combined cycle power, potentially bringing the costs of CO2 capture to around 35 USD/tonne. These potential improvements included depressurization of the lean solvent and vapour compression; elimination of contact coolers before the absorber, the use of structured packing, direct integration of the stripper and Heat Recovery Steam Generator and recycle of a portion of the ue gas to increase the CO2 feed concentration to the absorber. It has been argued that post combustion CO2 capture affords power producers greater operational exibility to respond to short term market signals than those alternatives that require integration between the power block and the capture plant (e.g., Gibbins et al., 2005). This may be valuable in terms of uctuations in both the prices of CO2 quota and electricity and in overcoming the barrier that potential mismatches in timing between the life of power plants and CO2 required for enhanced oil recovery may present. Typically, operational exibility comes at a cost (e.g., increased capital cost) that must be weighed against the uncertain value of the future benets.
Figure 7. The Combicap# cycle (Lyngheim et al., 2004).
CO2 CAPTURE AND STORAGE air and recycled ue gas. The advantages of the increased CO2 partial pressure and modest temperature for CO2 separation are partially offset by the increased complexity and higher degree of integration of the process. Humid air turbine (HAT) cycles have been proposed as a means of reducing the costs of power generation and CO2 removal (e.g., Rao and Day, 1996). A typical HAT cycle uses a high pressure ratio gas turbine, composed of a high pressure inter-cooled shaft and a low pressure power shaft. The high pressure air from the compressor is cooled and then humidied in an air saturator. The humidied air is heated in a heat recovery section that uses the turbine exhaust before entering the turbine combustor. Arguments for HAT cycles are that the added cost of a more expensive gas turbine, the air saturator and the increased number of heat exchangers is offset by elimination of the heat recovery steam generator (HRSG) steam cycle. An alternate approach to removing CO2 from the ue gas is to use oxygen for combustion instead of air. To maintain thermal conditions in the combustion zone and prevent overheating of the furnace liner materials, some of the ue gas would be recycled to the furnace. Using oxygen instead of air opens up new possibilities for increased combustion efciencies. Trace impurities exit with the CO2 stream and where these can be stored with the CO2 could result in overall lower emissions abatement costs. The oxyfuel pathway to CO2 capture and storage is discussed in the following section. THE CONTENDING TECHNOLOGIES: OXYFUEL ALTERNATIVES FOR CO2 CAPTURE Since nitrogen is the highest concentration component in the ue gas from power stations, removal of nitrogen in oxyfuel processes (also called pre-combustion denitrogenation) simplies downstream CO2 separation. One of the earliest investigations of oxyfuel CO2 capture was by Holt and Lindeberg (1988), who suggest oxygen ring instead of air and recirculation of CO2 and H2O as the working uid in a partially closed turbine cycle. Air separation precedes combustion so that the combustion products are chiey CO2, and water with small amounts of other acid gases (e.g., SOx, NOx), possible impurities such as HCl and Hg derived from the fuel used, and inert gas components, such as nitrogen, argon and oxygen either derived from the
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oxygen feed, the fuel stream or air leakage into the system. Oxyfuel concepts for both natural gas and coal feedstock have been proposed Croiset and Thambimuthu (2000) and Tan et al. (2002), and holds potential for more efcient NOx, SO2, particulate, trace element and moisture removal since the gas volume that has to be treated for ue gas purication is much reduced. Another challenge for the oxyfuel route is the relatively low purity CO2 produced. The research directions for oxyfuel technology are given in Figure 8. Combustion temperatures in oxyfuel processes are controlled by recycling a portion of the ue gas, steam or water back to the combustion chamber. Because of the higher heat capacity of carbon dioxide a reduced inert gas/O2 ratio is typically required (approaching 2.5 : 1 instead of 4 : 1 for air) (Chatel-Pelage et al., 2003; Tan et al., 2002). The net ue gas, after cooling to condense the water vapour, contains 80 98% CO2 depending on the fuel used and the particular type of oxyfuel process. The recycled ue gas may either be CO2 or H2O. Oxyfuel alternatives potentially allow for 100% CO2 capture, although a small amount of CO2 (around approximately 4 g/kWh) will not be recovered from oxyfuel cycles using water condensers. The advantages of oxyfuel can be offset by the cost of O2/N2 separation, the high oxygen demand and the efciency penalty incurred by ue gas recirculation. For oxyfuel boilers air leakage into the system undermines the extra capital and power associated with high purity oxygen and lowering the oxygen purity from 99.5% to 95% will signicantly reduce the power consumption. While the amount of excess air (largely determined by variations in air/fuel distribution between burners in multi-burner installations) of 15 20% excess air is normally required in pulverized coal combustion boilers to ensure adequate burnout, 10 20% excess oxygen is required for oxyfuel boilers. With signicant air in-leakage, inert gas removal to achieve the desired CO2 purity is required. In general, fuel efciency decreases with increasing oxygen and CO2 purity. A promising potential application of oxyfuel technology that has been reported (Wilkinson et al., 2003b) is the retrot of power plant boilers and a range of renery heaters in the Grangemouth renery complex in Scotland. The conversion of gas and oil red heaters to an oxy-fuel boiler required minor burner modications (a new O2 injection system and a new ue gas recycle line with a separate
Figure 8. Oxyfuel research directions.
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STEENEVELDT et al. expanded to 40 bar in a steam turbine. The hot gas from the HRSG is further expanded in a low pressure turbine before being nally cooled in a condenser. The condensed water and CO2 are separated in the condenser. The CO2 stream is compressed (with intercooling) before it is mixed into the combustor, as an inert gas for the control of the combustor exit temperature. The water collected from the condenser is preheated in the CO2 compression intercoolers, before it is pressurised for steam generation. Excess water, as well as some of the CO2, formed in the combustion is removed from the cycle (Jericha et al., 2003). In addition to the lowering the overall fuel efciency, recirculation of a H2O/CO2 cooling/mixing medium requires the development of turbo-machinery capable of using CO2/H2O mixtures as the working uid at high temperatures and pressures. The practical design of condensers for good heat recovery from the working uid (with relatively high concentration of non-condensable gases) is another important challenge. The development of gas turbines capable of operating with very high temperatures will potentially improve the efciency of oxyfuel cycles. Relatively low fuel efciency is reported for all of the oxyfuel alternatives (Bolland et al., 2005; IEA GHG, 2004). CHEMICAL LOOPING COMBUSTION Chemical Looping combustion, proposed by Richter and Knoche in 1983, divides combustion into intermediate oxidation and reduction reactions that are performed separately with a solid oxygen carrier circulating between the separated sections. Oxides of iron, copper, chrome, manganese and nickel have been investigated (Lyngfelt et al., 2001; Brandvoll and Bolland, 2004; Zafer et al., 2005; Ishida and Jin, 1994; Cho et al., 2002; Jin et al., 1999; Ishida et al., 1999, 2002). The major components of a chemical looping process are: solid oxygen carriers; a chemical looping system; fuel and air supplies; heat utilization/recovery and CO2 capture. Although there are various ways to perform CLC, a uidized-bed combustion system has some advantages over other alternatives, e.g., good heat transfer and effective transport of the solid oxygen carriers between the two reactors. At the present stage of development, the mechanical stability and chemical reactivity over many cycles are the main development issues for this process. OXYGEN MEMBRANES Conventional methods of oxygen production, i.e., cryogenic separation (99.99% O2) and vacuum pressure swing adsportion (90 94% O2) consume about 200 kWh/tonne O2. The largest single train air separation unit can produce approximately 3500 tons per day (TPD) of oxygen, a quantity sufcient to support an oxy-fuel power plant having roughly 200 MWe output. Larger single train units (.5000 TPD) seem possible and to offer some modest improvement in economy-of-scale. (Wilkinson et al., 2003a). A less energy intensive (and thus potentially more cost effective) alternative that has been pursued is the use of oxygen transport membranes to produce pure oxygen from air (e.g. Asen, 2001). Three different allianceslead by Air Products (e.g., Carolan et al., 2001), Praxair and the AZEP alliance (Grifn et al., 2003) have been working
blower) that could potentially yield increased boiler thermal efciency due to the recycle of hot gas. In general, modications to a coal red boiler are more complex (Allam et al., 2004; Croiset et al., 2000). The CO2 concentration in the ue gas in the Grangemouth case increased to 60%. Impurities (SOx, NOx) and gases (excess O2, N2, Argon) representing about 10% of the stream are separated from CO2 at low temperature (2558C). After cooling, compression and drying of the separated or non-recycled ue gas, the product for sequestration comprises 96% CO2.18 Production of ultra-pure CO2 for storage would be possible by adding distillation steps to the separation process. Theoretical studies have concentrated on the retrot option, however, there are advantages in applying oxyfuel technology to modern ultra-supercritical boilers since their increased efciency reduces the oxygen demand per unit of generated electricity and therefore the cost end efciency penalty of O2/CO2 recycle combustion. OXYFUEL TURBINE CYCLES The AZEP concept (Sundnes, 1998; Sundkvist, 2005; Grifn et al., 2003), involves the integration of a ceramic membrane in the combustor. The ceramic membrane allows transport of oxygen and heat, such that the combustion products, chiey CO2 and H2O are expanded in one turbine, while the heated oxygen-depleted air drives the main combined cycle gas turbine. The optimum operating window for the membrane is such that the turbine inlet temperature is lower than most of the advanced gas turbines, resulting in lower efciencies.19 Several novel turbine cycles using water, CO2 or a mixture of H2O/CO2 as the working uid have been proposed in the literature (e.g., Mathieu, 2003). Table 6 contains a broad comparison of the main oxyfuel cycles. The Clean Energy Systems (CES) process is a variant of the watercycle (H2O recycle) and the Graz cycles (77% H2O and 23% CO2 recycle). A combustor is red with a mixture of recycled high pressure water/steam, fresh oxygen and natural gas or synthesis gas. The combustion is performed at essentially stoichiometric conditions to produce steam and CO2 at high temperature and pressure that powers a turbine. The turbine exhaust is used for water/steam heating and is reheated to above 13708C by combustion of additional gas. The remaining turbine sections may have intermediate feed water heaters before the exhaust stream (approximately 90% H2O, 10% CO2) enters a partial condenser and then a condenser/CO2 recovery section. CES commissioned a 20 MWth gas generator at the Kimberlina power plant, California in May 2005. Considerable effort will be required to further develop the gas generator and the ultra high pressure/temperature turbines required for a full-scale commercial process. The Graz-cycle consists of a high pressure (40 bara) combustor, which is fed with natural gas, oxygen, CO2 and steam. The combustor exit stream, at 13288C, is expanded in a high pressure turbine. The turbine exit stream is cooled in a heat recovery steam generator (HRSG), where high-pressure steam is produced (174 bar, 5608C) and then
18 19
In addition to 2% N2, 1% Argon and approximately 1% O2 and SO2.
Supplementary ring allows higher turbine inlet temperatures and higher efciency at the cost of lower CO2 capture.

Table 6. Comparison of the main oxyfuel alternatives. Cycle efciency (from Kvamsdal et al., 2005a) 51 Technical development challenges
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Main feature AZEP Mixed Conducting Membranes for O2/N2 separation integrated with Combustor and Gas Turbine; Largescale (.45 MW) much longer term
Technology developer(s) Consortium: Norsk Hydro Alstom, Siemens, Borsig, Ulster Univ, PSI, Lund Technical Univ, Areva
Working uid Air
Graz
Water
Chemical looping combustion
3 Turbines (2 High, 1 Low Pressure), Steam Cycle, Recycle of CO2 and steam 2 Turbines (High and Low Pressure), Two combustors, Recycle of Heated Water Combustion occurs in reducing atmosphere (oxygen present as metal oxide) Circulate metal oxide between combustion and oxidizing sections/ reactors
Prof Jericha from Technical Univeristy of Graz Clean Energy Systems (CES) Consortium in CCP: BP, Alstom Boilers, Chalmers University, CSIC (Spain), ENI
77% H2O, 23% CO2 90% H2O, 10% CO2@ 808C Air as uidizing medium
43
44
51
Membrane (O2 Flux, Mechanical Strength and Stability, Scaleup), Ceramic Sealing at High Temperature, High Temperature Heat Exchange, Combustor Design Turbine integration with reactor Integrated Steam/Gas Turbine NonCondensable gases in Condenser Integrated Steam/Gas Turbine NonCondensable gases in Condenser Metal Attrition Fine Dust to Turbine Turbine integration with reactor
on the development of oxygen transport membranes. The advanced zero emission power concept (AZEP) entails the integration of an oxygen conducting membrane with conventional power turbines (Sundkvist et al., 2005; Moller et al., 2005). Robinson et al. (2004) report that theoretical studies show that the incorporation of an oxygen transport membrane into steam methane reforming improves hydrogen yield and lowers CO2 and NOx emissions. These dense membranes consist of complex crystalline structures, allowing oxygen ions to diffuse in the direction of decreasing oxygen partial pressure given an adequate electronic conductivity that allows the counter migration of electrons.20 At low temperatures, the ionic conductivity of the ceramic material is often too low so that the transport process requires high temperatures, i.e., .7008C, making it attractive to combine these membranes with exothermic processes/reactions (Skinner and Kilner, 2003; Bouwmeester and Van Der Haar, 2002; Dyer et al., 2000; Bredesen et al., 2004). In addition to achieving adequate oxygen ux, mechanical and compositional stability over repeated thermal and oxygen concentration cycles, preventing fouling/coking, achieving a high surface area/ volume design and module fabrication for large-scale applications are very serious development and commercialization challenges for these types of membranes.
20 Oxygen separation occurs as O2 molecules diffuse to the membrane surface, followed by dissociation into oxide ions, ions are transported through the membrane by sequentially occupying the oxygen ion vacancies and recombine on the other side of the membrane, liberating electrons. The ion transport is counterbalanced by a ow of electrons in the opposite direction. The driving force is the difference in the oxygen partial pressure between the permeate and retentate sides of the membrane. Since the transport mechanism is based on ion transport and not molecular sieving, the selectivity of the membranes is innite as long as there are no cracks or other surface imperfections.
THE CONTENDING TECHNOLOGIES: PRE-COMBUSTION CO2 CAPTURE The pre-combustion route is premised on the production of synthesis gas, CO2 removal and combustion of hydrogen. Hydrogen is produced from a variety of feedstock including natural gas, naphtha, heavy oils or coal in processes that convert the hydrocarbon source into synthesis gas. The production of synthesis gas comprises the reforming, partial oxidation and water gas shift reactions: Cx Hy X H2 O , xCO (x y=2) H2 Cx Hy x=2O2 , xCO y=2H2 CO H2 O , CO2 H2 Different synthesis gas technologies have different approaches to the supply/removal of the heat of reaction and for the supply of oxygen and steam, implying different ways of combining or coupling the reforming and partial oxidation reactions. The shift reactions convert the CO to CO2 and increase the hydrogen yield. For coal and heavy oils various forms of gasication form the main synthesis gas production technology. Pre-combustion CO2 capture based on coal is termed integrated gasication combined cycle (IGCC). The two predominant synthesis gas technologies from natural gas are steam methane reforming (SMR) and autothermal reforming (ATR). SMR introduced in the 1930s is by far the most common process. The current upper limit for the capacity of single trains SMR plants is around 480 tonnes/day hydrogen, and hydrogen is recovered at high pressure using pressure swing absorption. A SMR unit consists of Ni-alloy tubes lled with catalyst, which are heated externally by burners. The ATR is a large refractory-lined vessel with a burner and catalyst
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STEENEVELDT et al. the high cost of an air separation unit). For CO2 capture, oxygen-red, high pressure systemsresulting in higher CO2 partial pressuresmay be preferred, but given that nitrogen is required for combustion in the hydrogen turbine, airred systems may be economic for natural gas red systems. INTEGRATED GASIFICATION COMBINED CYCLE (IGCC) Worldwide there are more than 400 gasiers in operation that do not generate electricity, but produce synthesis gas and various other by-products of high rank coal and residual oil gasication. In these facilities, CO2 is separated after the gasication stage. CO2 capture costs for IGCC plants are among the lowest reported, see Table 7. The synthesis gas or hydrogen are used as a fuel or for chemical raw material, e.g., for liquid fuel manufacturing or ammonia synthesis. Bracht et al. (1997) report the economic potential of novel shift reactor and IGCC concept. There are a number of gasication technology suppliers, among them General Electric (acquired from ChevronTexaco), Shell, Foster Wheeler, E-GAS (ConocoPhillips and Fluor alliance) and Mitsubishi Heavy Industries (McDaniel and Hornick, 2002). A comparison of gasication technologies can be found in Zheng and Furinsky (2005) and Rosenberg et al. (2005). Despite the worldwide commercial use and acceptance of gasication processes and combined cycle power systems, the integration of a coal gasication with a combined cycle power block to produce electricity as a primary output is relatively new, and has been demonstrated at only a handful of facilities around the world (see Table 8 for an overview). The commercial gasication processes believed most suited for near-term IGCC applications using coal or petroleum coke feedstock are the General Electric, ConocoPhillips, and Shell entrained-ow gasiers. Each of these technologies is currently deployed at an operating commercial IGCC facility (see Table 8). HYDROGEN TURBINE The hydrogen turbine is the unit that is common for all pre-combustion technologies for all fuels. Pure hydrogen presents several complex challenges for ame stability due to its very high ame speed when premixed, and its high
bed. The partial combustion of natural gas with oxygen and steam occurs in the burner, and the reactants equilibrate in the catalyst bed to form synthesis gas. The addition of steam is required to prevent coking and and soot formation (Wilkinson and Clarke, 2002). The production of hydrogen from fossil fuels is energy intensive, and about 20 25% of the energy is irreversibly dissipated during the conversion (see Corradetti and Desideri, 2004; Ertesvag et al., 2005). Typically the product stream from the shift reactors has a CO2 concentration of CO2 in the range 15 60% (dry basis) and the total pressure is typically 2 7 MPa, which enables more efcient CO2 separation (by e.g., amine absorption or physical absorbents like Selexol). Using amine absorption to recover the CO2 followed by a PSA (Sircar and Golden, 2001) unit for hydrogen recovery, the efciency penalty for the CO2 capture unit in a natural gas red large SMR plant is around 3% at 88% capture (IEA GHG, 1996). CO2 capture is already commonly used in the production of ammonia and urea. The main research directions for pre-combustion CO2 capture are shown in Figure 9. A key aspect for all synthesis gas technologies is whether the oxidization agent is pure oxygen or air. In addition to the cost of the air separation unit, the compression of air and oxygen requires substantial power, comprising the largest parasitic load on a reformer or integrated gasication facility. The integration between the reforming and turbine units can improve thermal efciencies: For example, air extracted from the gas turbine air compressor can be mixed with the products from the pre-reformer and preheated against exhaust gas before entering the reformer and steam generated from the waste heat from reforming is used in the steam turbine. For IGCC units, the high partial pressure of the CO2 allows the use of physical solvents (e.g., Selexol). Cryogenic separation (e.g., Fluors CO2LDSepw) is another alternative. The parasitic load from air separation can be reduced by extracting a portion of the air from the compressor of the gas turbine to feed the air separation unit. However, because of reliability problems associated with 100% integration found at several demonstration IGCC facilities, current industry thinking in the US is that about 50% integration is the recommended maximum (Rosenberg et al., 2005). For air-blown systems, the introduction of nitrogen markedly increases equipment sizes (this must be traded off against
Figure 9. Pre-combustion research directions.

Table 7. Cost comparisons of the main technology options. Reference Parsons, 2002, 508 MW NG NETL, 2002, 379 MW NG IEA GHG, 2004, MEA, 776 MW NG Melien, 2005, 392 MW NG Rubin et al., 2005, 507 MW NG Rubin et al., 2005, 507 MW NG Fuel cost ($/kg) Estimated cost of CO2 avoided USD/tonne Estimated capital cost (USD/kW) 0.949 0.875 1.844 1.09 1.099 0.733 2.09 2.228 1.48 1.48 1.83 2.35 4.061 3.102
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Estimated capital (USD/kW) 1099 911 938 1261 909 909 1059 1941 837 647 2219 1943 1894 1936 1857
Post-combustion natural gas combined cycle 2.82 74 3.55 45 3 41 2.96 57 4.44 49 4.44 68 Post-combustion pulverized coal sub-critical boilers Simbeck, 2001, 294 MW 0.98 45 Alstom et al., 2001, 255 MW 96% capture 1.3 73 Chen et al., 2003, 140 MW 1.2 56 Chen et al., 2003, 282 MW 1.2 48 Post-combustion pulverized coal super and ultracritical boilers Parsons, 2002b, 329 MW PC 1.29 51 Parsons, 2002b, ultracritical boiler, 367 MW PC 1.29 49 IEA GHG, 2004, MEA, 666 MW PC 1.5 29 Rubin et al., 2005, 492 MW PC 1.25 40 Oxyfuel boiler Dillon et al., 2005, 532 MW 1.5 27 Oxyfuel natural gas cycle Dillon et al., 2005, 440 MW 3 47 Pre-combustion NG combined cycle Jacobs, 2003, 392 MW NG 3.52 68.4 Melien, 2005, 358 MW NG 2.96 76 IGCC GE oxygen-red, bituminous coal Simbeck, 2002, 455 MW BC 0.98 22 IEA GHG, 2003, 730 BC 1.5 16 Rubin et al., 2005, 492 BC 1.25 20 Melien, 2005, 699 MW BC 0.3 14.5 Melien, 2005, 424 MW 2.96 34.4
1.329 2.151 4.682 2.749 6.8 1.47
1034 1076 2067 1495 1748 1919 1089
temperatures when non-premixed. The high ame temperatures resulting from hydrogen combustion are attenuated by the addition of nitrogen and/or steam. General Electrics (GE) IGCC group has utilized fuels with H2 contents between 8% and 62% and fuels having up to 95% H2 have been used in GE turbines in process plants. General Electric reports having completed feasibility testing for 100% H2 fuel to dene the entire combustion map that shows that ratios of 50/50 H2/N2 can produce very low NOx as well as provide enhanced output in a modern IGCC gas turbine. The rate of NOx generation varies exponentially with ame temperature and linearly with the amount of time that the gases are exposed to the ame zone. NOx emissions can be reduced either with a conventional, diffusion-based combustor with nitrogen and/or steam dilution, or with a dry low emissions (DLE) premixed combustion system. At present, only dilution based on diffusion is commercially available for hydrogen-rich combustion and increases in hydrogen content increase the required amount of dilution gases. Although steam is the more effective of the two diluents, steam dilution results in higher metal temperatures of
the hot-gas components that can reduce equipment lifetimes if ring temperaturesand thereby also engine efciency are not reduced. Moreover, steam extraction has a direct negative impact on the energy efciency of a combined cycle. So, nitrogen is generally preferred over steam for dilution, but for high hydrogen content, the large volumetric ow to the combustor presents a design challenge. Modications to the combustors and fuel mixing system are the principal requirements when converting a natural gas turbine to burn hydrogen-rich fuels. Although hydrogen has almost three times more energy by mass than natural gas, by volume the energy density is much lower. As a result, hydrogen fuelled gas turbines will require larger delivery piping, manifold, valves and nozzle sizes than natural gas-burning engines currently need. Compressing hydrogen to a greater operating pressure than natural gas, to increase its volumetric energy density, would mitigate the increased size requirements for delivery equipment. The ammability range of hydrogen is quite large compared to other fuels, so that the fuel/air ratio can be throttled for much leaner combustion.
Table 8. Overview of existing IGCC facilities (after Rosenberg et al., 2005). Wabash Power Station Gasier technology Location Gas turbine Fuel feedstock Thermal efciency (HHV) Conoco Phillips Indiana, USA GE MS 7001FA Bituminous coke/ Petroleum coke 39.7 Polk Power Station GE Energy Florida, USA GE MS 7001FA Bituminous coke/ Petroleum coke 37.4 Willem Alexander Shell Buggenum, Netherlands Siemens V 94.2 Bituminous coke/ Petroleum coke 41.4 Puertollano Preno (Uhde/Krupp) Spain Siemens V 94.2 Bituminous coke/ Petroleum coke 41.5 Negishi GE Energy Japan MHI 701F Asphalt Unknown
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STEENEVELDT et al. accumulations varies over a wide range: the CO2 content of gas produced from the Jackson Dome in the USA can be as low as 65%, while the McElmo Dome (USA) produces 98 99% CO2. The CO2 purity requirements for ECBM and storage only (i.e., no hydrocarbon production) are believed to be less stringent than those for EOR. For EOR, components like N2 and O2 below 300 and 50 ppm levels respectively may be required, although for the SACROC EOR project in the USA (for example), a maximum content of 4 mol% N2 is specied. Since immiscible components may increase the minimum miscible pressure in the reservoir and thus decrease the efciency of CO2 injection, the total concentration of components immiscible with oil (CH4, Ar, N2 and H2) is important and the effect of the immiscible components is likely to be assessed for each EOR project. Oxygen present in the gas stream may cause precipitation reactions and reduce the permeability of the reservoir, or react exothermally with oil and cause overheating at the injection point. Particulates pose the danger of pore blockage near the injection well thereby reducing reservoir permeability. Acidic compounds, such as H2S, COS, CO, SO2 and NOx are corrosive and will be reproduced with the recovered hydrocarbons, affecting the choice of materials and potentially increasing the downstream processing required. Sulphur components may also downgrade produced hydrocarbons by increasing their sulphur content. Where water-alternating-gas (WAG) technology is the EOR strategy adopted, the CO2 stream will come into contact with water at the top of the well. To prevent hydrate formation, heating of the CO2 above 158C may be required. The composition of the gas to EOR will, in other words, have important implications for the modications that are required at the injection point and for investments in the downstream oil and gas processing equipment. RELATIVE POSITION OF THE MAIN CONTENDERS Haines et al. (2004) present a methodology for screening and comparing different processes for CO2 capture. Reported costs of CO2 capture are packed with technological and economic assumptions. Numerous comparisons of options for CO2 capture are to be found in the literature: Parsons (2002a,b), Bolland (2002), Singh et al. (2003), Haines et al. (2004), Kvamsdal et al. (2005b), Steinberg et al. (1984). The recent IPCC report on CCS (IPCC, 2005) contains a thorough review of a number of technology comparisons that have been performed. Table 7 presents a selection of the reported costs in the literature. For comparisons between different approaches to CO2 capture to be meaningful, the competing methods must be based on shared assumptions about plant size, feedstock quality, product quality, CO2 delivered (purity, temperature and pressure), and the quality of available utilities (e.g., cooling water temperature). For natural gas red systems, technoeconomic studies show that the fuel price has the largest impact on the production cost of electricity, making the fuel efciency of new concepts the most important selection criterion (e.g., Moller et al., 2005). Theoretical fuel efciency achievable on paper can in turn be based on optimistic assumptions about, e.g., turbine inlet temperatures, turbine efciencies, steam levels achievable in Heat Recovery Steam Generators, lowest pressure achievable in condensers
Although hydrogen combustion turbines are not presently commercially produced, there appears to be no major technical barriers for gas turbines burning gases with hydrogen contents up to roughly 70%. While immediate efciency gains could be obtained using hydrogen in place of natural gas, these would likely be offset by NOx control considerations, such as a lean fuel/air mixture to limit the combustion temperature. Since efciency and power roughly can be considered equal between these fuels, the most signicant gain from converting to hydrogen fuelled gas turbines is its nearly completely clean emissions prole. Todd and Battista (2001) have reported combustion trials assuming the modication of an existing GE frame 9F turbine. Steam injection was selected as the method of limiting NOx production. An alternative to steam injection is to use inlet fogging techniques (e.g., Van de Burgt, 2004). Such techniques are increasingly used in commercial operation to increase turbine output (up to 20%), to reduce heat rate, to improve turbine efciency and to reduce NOx emissions. These systems inject only of the order of 1% H2O by weight in a ne spray upstream of the compressor. Wotzak et al. (2005), report on the suitability for hydrogen utilization of the GE Frame 5002C and 6001B gas turbines at the BP Prudhoe Bay Facility. All the three big suppliers (GE, Siemens and Alstom) communicate a general interest in developing low emission and high-efciency hydrogen combustion. This is also manifested through their participation in big research projects such as ENCAP (EU) and FutureGEN (USA). ADVANCED OPTIONS Many novel pre-combustion concepts or improvements have been published (see for example Middleton et al., 2002; Holt et al., 2003; Jordal et al., 2003). A few of them are mentioned here. The sorption enhanced reaction process (SER) combines catalytic shift conversion (of carbon monoxide and steam to hydrogen and carbon dioxide) with a high temperature CO2 adsorption system using a mixture of solid catalyst and adsorbent (e.g. Hufton et al., 1999; Hufton et al., 2005; Liang et al., 2004). The conversion and CO2 removal steps are carried out in a multi-bed pressure swing adsorption unit which is regenerated using low pressure steam which is subsequently condensed to leave a relatively pure CO2 stream. The removal of hydrogen in dehydrogenation and synthesis gas reactions with membranes has been widely studied. Two different approaches have been investigated: Integration of a membrane into the reformer and integration of a membrane into the high temperature shift reactor. Product removal may occur by H2 permeation through a Pd-alloy or composite Pd-ceramic membrane or a ceramic porous membrane. The permeation of the sweep gas onto the feed (i.e., retentate) side also contributes to increasing the conversion. CO2 PURITY REQUIREMENTS The CO2 purity requirements for the whole CCS chain are being formulated. For CO2 capture for enhanced oil recovery (EOR), experience from existing large-scale EOR can be drawn upon (Stevens et al., 2001) The CO2 concentration of gas produced from CO2-rich geological
CO2 CAPTURE AND STORAGE and heat exchangers that cannot be built using current material technology (e.g., assuming that high temperature heat exchange with synthesis gas is possible even in the operational areas where metal dusting21 is known to occur). Technology choice implies a trade-off between fuel efciency, other operating expenses like maintenance or plant availability and capital costs. Internal consistent comparisons do not necessarily result in credible costs for CO2 capture and storage: conventions or published methods (e.g., Turton et al., 2003) for preparing cost estimates may differ from in-house standards for doing economic analysis that include assumptions about fuel and capital costs (including the economic life of the plant, on-stream factors, weighted average cost of capital, ination effects, interest charges during construction, taxation, commissioning costs and contingency elements). In addition to other sitespecic details like labour costs and weatherization costs associated with temperature or other extremes, methods for assessing costs often reect a rms orientation toward risk. For this reason, published costs are often not transferable across organizational boundaries. THE CONTENDING TECHNOLOGIES: NOVEL METHODS OF CO2 CAPTURE Given the glaring disadvantages of the conventional methods, there is room for novel methods that can bring about a step-change in efciency of CO2 capture. In addition to the commercially available separation techniques, the number of different concepts for separating CO2 is limited only by the creativity of the scientists and engineers who are set to work on the problem. Among the novel concepts, not described in detail here, but that have been forwarded is: biological CO2 xation with algae (algae convert CO2 to organic material) and formation of CO2 hydrates. An air-lift bioreactor with variablebut up to 95%CO2 removal is reported by Vunjak-Novakovic et al. (2005). This technology is the basis for the venture start-up GreenFuel Technologies Corporation, which has also announced that a larger eld trial of the bioreactor for the combined removal of CO2 and NOx.22 The use of dry regenerable sorbents has also been investigated. The CO2 is chemically absorbed by the sorbent and is then subsequently released in a second step to produce a concentrated stream of CO2 at which point the sorbent is regenerated and recycled. Sorbents such as sodium carbonate, calcium oxide and lithium silicates/zeolites have been investigated (Kato et al., 2001; Abanades, 2002; Abanades et al., 2004a,b; Klara and Srivastava, 2002; Hoffman et al., 2002; Kimura et al., 2005). Solid supports impregnated with amines have also been suggested (Contarini et al., 2002). While the carbonation of CaO to CaCO3 involves the separation of CO2 above 6008C, and regeneration at 9008C, temperatures of about 301008C are used to regenerate amine impregnated solids. Reactor systems that have been suggested for this type of process include xed bed reactors, moving bed reactors and uidized bed reactors. The main challenges for solid absorbents (e.g. Abanades
21 Boudard reaction: 2CO ! C CO2. One of the mechanisms that lead to the disintegration of metals. The critical temperature range is 4008008C and the relative concentrations of CO2/CO determining the reaction rate. 22
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et al., 2004a; Abanades et al., 2004b; Green et al., 2002) on a large scale are the costs of solids handling and dust elimination equipment, the cyclic absorption capacity and mechanical strength of the absorbent. Electric swing adsorption, involving the adsorption of CO2 on a charged carbon substrate and high-temperature polymer (solution-diffusion) membranes have also been proposed (e.g., Van der Sluijs et al., 1992). A further possibility for solid fuel ring is described by Alstom (Grifn et al., 2003)a high temperature carbonate loop is proposed in which calcined limestone is used to remove CO2 from oxygen rich ue gases. Limestone circulates between a high temperature calcinerthat produces free lime and CO2 for subsequent processing and disposaland a high temperature region of the furnace where CO2 is absorbed. CO2 TRANSPORT The transport of CO2 by land-based pipelines is a wellestablished practice worldwide: For example, 50 million tonnes/year of CO2 are transported in pipelines that extend over more than 2500 km in western USA, mostly carrying CO2 from natural sources to enhanced oil recovery projects (IEA GHG, 2002a; West, 1974). The Cortez pipeline is the largest example, with a diameter of 30 in and a capacity of 12.2 Mt CO2/year. The CO2 for this pipeline is produced from the McElmo eld, operated by Kinder Morgan, which contains 97 mole% of pure CO2. Before the CO2 is pumped down the pipeline, it is cleaned, dehydrated and compressed to supercritical pressure (145 bar). The use of pumps to transport supercritical CO2, rather than compressors for gas phase transport, reduces operating costs signicantly. In 2007, the rst long distance (150 km) offshore CO2 pipeline will be commissioned as part of the Snhvit LNG project. The most widely used operating pressure is between 7.4 and about 21 MPa, although the design pressure is obviously dependent on the desired delivery conditions, the transportation length and the composition of the gas to be transported. Above 7.4 MPa, CO2 exists as a single dense phase over a wide range of temperatures. The solubility of water in CO2 (to determine the percentage free water) and corrosion rates are important considerations for establishing the material specication for a CO2 pipeline. Water solubility in CO2 is given in Heggum et al. (2005). Existing practice for inhibiting hydrate formation and preventing excessive corrosion rates for carbon steel is to reduce the water content to ppm-levels using either molecular sieves, glycol (MEG/TEG) or alumina desiccants. The requirement for CO2 pipelines, used for EOR in the USA, is maximum 600 ppm water (Heggum et al., 2005). While accurate estimations of the water solubility is key to determining the corresponding corrosion rates and thus the dehydration/corrosion inhibition requirement, the solubility of water in CO2 is inuenced by the concentration of other components (e.g., hydrocarbons, N2) (Skovholt, 1993). The presence of hydrocarbons tends to lower the water solubility, as do decreasing temperatures. For deep water pipelines, the static head contributes to increased pressure and increased water solubility, and therefore tends to prevent the formation of free water. At the LNG plant at Hammerfest in Norway, CO2 will be removed
http://www.greenfuelonline.com.
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STEENEVELDT et al. geological formations for CO2 storage are depleted oil and gas reservoirs, deeply buried saline aquifers and uneconomic coal seams (Buller et al., 2004; Heinrich et al., 2003). A review of geological storage of CO2 can be found in Benson (2005). Depleted oil and gas reservoirs have the advantages of being proven traps; having wellknown reservoir geology and of having infrastructures that can readily be adapted for CO2 transport and injection. Nevertheless, relatively few hydrocarbon reservoirs are currently depleted or near depletion, so that the timing of CO2 storage will depend on reservoir availability (Beecy and Kuuskraa, 2005). Deep saline aquifers that could be used for long term CO2 storage are innumerable: In both casesdepleted reservoirs and saline aquifersmuch of the injected gas will eventually dissolve in the formation water, while some may react with the minerals to form carbonate precipitates. Rough IEA (2004b) estimates of how much CO2 could be stored in the various geological options are .15 Giga tonnes in unminable coal seams, 920 Giga tonnes in depleted oil and gas elds and 400 10 000 Giga tonnes in deep saline aquifers. Table 9 below lists the large-scale CO2 injection projects worldwide. CO2 STORAGE AT SLEIPNER, IN SALAH AND SNHVIT Motivated by the offshore CO2 tax imposed by the Norwegian government, currently at around 54 USD per tonne, since 1996 about 1 million tonnes per year of CO2 have been separated from the natural gas and stored in a saline aquifer (the Utsira formation) at the Sleipner eld. A special feature of the eld is the high carbon dioxide content. Initial gas produced from the main eld contains about 9 mole% CO2 which must be reduced to an average of 3 mole% to meet customer specications (Baklid et al., 1996; Hansen et al., 2005). The CO2 is stripped from the well-stream using an activated MDEA absorption process. The amine plant, which weighs about 9000 tonnes and is 35 m high, cost NOK 2 billion (about USD 300 million) in 1996, see Figure 10. Once the CO2 has been captured, its pressure is boosted by four compressors to 80 bara prior to being transferred to the Sleipner A platform for injecting into the base of the saline aquifer (Hansen et al., 2005). The cost of CO2 storage by this method has been estimated to be close to 15 USD per tonne CO2 (Torp, 2004). To predict the migration path of the injected CO2 and the storage capacity of a reservoir, the appraisal of the reservoir geometry and the presence of faults must be conducted over a range of scales. In addition, the construction of simplied geological models based on all the available data may be need to supplement reservoir simulation. As CO2 is buoyant
Table 9. List of present and near future CO2 storage. Year 1996 2000 2004 2004 2006 2009 Location Sleipner, Norway Weyburn, Canada In Salah, Algeria K12B Snhvit Gorgon, Australia Project CO2 injection rate (million tonnes/year) type 1 1.2 1.3 0.2 0.7 3.3 Storage EOR Storage Storage Storage Storage Operator Statoil EnCana BP Gaz de France Statoil Chevron
from the natural gas prior to the LNG liquefaction unit. The drying requirement for CO2 pipeline transporting the captured CO2 to the Tubaen formation, is 50 ppm water, which is the engineering practice for transportation of natural gas (Heggum et al., 2005; Maldal and Tappel, 2004). An important area of future research is to improve understanding of the inuence of the impurity concentration on thermo-physical properties such as critical pressure and temperature, mixing properties and how changing CO2 gas properties affect the design and operating parameters of the compression equipment. Transport scenarios for CO2 have been reported by Skovholt (1993) and Svensson et al. (2004): For long distance, offshore transport of CO2 an alternate approach to pipelines is a logistics chain consisting of CO2 liquefaction and intermediate storage facilities, ships, loading and unloading systems. It has been proposed that liquid CO2 is transported at a temperature of 2508C and a pressure of 7 to 8 bars. Large-scale liquefaction of CO2 is best achieved in an open cycle, using the CO2 feed as the refrigerant where the refrigeration is partly or fully provided by the feed gas itself. The liquefaction process includes compression, cooling and expansion to the liquid product specication. In addition volatile gases and water are removed (in gas scrubbers and an adsorption gas drier). The process delivers CO2 at 6.5 bara and 2528C to the storage tanks, with power consumption of about 110 kWh/tonne liquid CO2 (Barrio et al., 2004). Ships have the advantage of introducing exibility in the CO2 value chain, allowing collection of concentrated CO2 from various sources at volumes below the critical size for pipeline transportation. Even though Yara International and the Anthony Veder Group routinely transport CO2 by ship for the North-European market, the ships currently in service are too small for large-scale ship-based transport of CO2: Yara charters three ships carrying 9001200 tonnes of CO2 (1000 and 1500 m3, at a transport pressure of about 14 to 20 bara) While ships of up to 10 000 to 30 000 m3 with the exibility to also transport LPG have been studied, the carrying capacity will be inuenced by harbour conditions, volumes and distances (Berger et al., 2004). Ship-based transport would require liquefaction plants and intermediate storage at each loading site (Lekva et al., 2005). If an onshore CO2 hub were to be introduced, intermediate storage facilities matching the incoming amounts of liqueed CO2 would also be needed. Care must be taken to avoid dry-ice formation in the process plant, storage and when loading and unloading. In the dense phase, CO2 is pumped to a pressure sufcient to avoid phase transition during transfer and further to the injection pressure required. The total costs of ship-based transport are calculated to 23 31 USD/tonne for volumes larger than 2 million tonnes/year and distances limited to the North Sea (Berger et al., 2004). CO2 STORAGE: PROJECT AND GEOLOGICAL TIMESCALES Geological storage of CO2 in the earths upper crust is a naturally occurring phenomenon. Carbon dioxide from biological activity, volcanic activity, and chemical reactions is found underground either as dissolved/precipitated carbonate minerals, or in supercritical form. Candidate
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Figure 10. CO2 injection at the Sleipner Field.
(in both gaseous and uid phases) it will tend to rise to the top of the repository reservoir. Assessment of the depth to the top of the reservoir is therefore a basic prerequisite of CO2 storage, allowing a rst order estimate of short-term storage capacity, and the assessment of likely migration pathways (Buller et al., 2004). The detection of possible reservoir compartmentalization and/or the potential for fault-related leakage is also important. The presence of reservoir compartmentalization could lead to a rapid increase in formation pressures with time as uid ow between compartments is inhibited. The identication of small-scale faulting requires seismic data of adequate resolution (Ibid). The migration of CO2 in the Utsira Formation has been monitored using 4D23 seismic. A baseline survey was shot prior to injection in 1994, and repeat surveys have so far been acquired in 1999, 2001, 2002 and 2004. The 2004 seismic survey revealed that (after the injection of approximately 7 million tonnes) the area of the supercritical CO2 plume was about 2 km2 with a maximum lateral migration from the injection point of 1.5 km to the northeast (Hansen et al., 2005; Arts et al., 2004). Very long term geo-modelling of the Utsira aquifer suggests that most of the CO2 will eventually dissolve in the formation water: ow simulation models, calibrated with the 4D seismic data, have been used to predict the CO2 behaviour in the Utsira Formation, over periods of hundreds to thousands of years. The results of these models predict that, following accumulation beneath the rock cap seal for a few years after the injection has ceased, the CO2 will spread laterally on top of the brine column with migration routes controlled by the topography of the Utsira Formation/cap rock interface. It has been suggested that the area size of the free CO2 plume may reach its maximum size after a few hundred years, and most of the CO2 will have dissolved into the aquifer after between 5000 and 50 000 years (Hansen et al., 2005). The non-porous mineral volume composition of the Utsira formation is mainly quartz (76%), K-feldspar (7%), plagioclase (3%), mica (5%) and calcite (7%). Long-term (10 000 year perspective) numerical modelling of the reactivity of the CO2 in the aquifer indicates that only minor dissolution of the calcite occurs: the total volume of minerals undergoes little change and the overall porosity is unaffected over time (Audigane et al., 2005; Hansen et al., 2005).
23
At depths below 800 m, the properties of supercritical CO2 (including its high density) potentially provide for the efcient usage of the pores in the sedimentary rocks (Benson, 2005). Carbon dioxide can remain trapped underground through a number of mechanisms: trapping below the cap rock; retention as an immobile phase trapped in the free pore volume of the storage formation (also called residual gas saturation); dissolution in the uids present; and/or adsorption onto organic matter in coal and shale (Benson, 2005; White et al., 2003). Additionally, it may be trapped by reacting with the minerals in the storage formation and cap rock to produce carbonate minerals. By avoiding deteriorated wells, or open fractures or faults, injected CO2 will be retained for very long periods of time.24 The Sleipner case has yielded considerable insight which has been worked into a Best Practice Manual for CO2 storage by the SACS and CO2STORE25 projects. BP, the Algerian National oil and gas company, Sonatrach, and Statoil are participants in the In Salah gas project, comprising eight gas elds in the central Saharan region of the country (Riddiford et al., 2004). Like at Sleipner, naturally occurring CO2 must be removed from the produced gas to meet market specications. Adequate seal integrity, storage potential, good reservoir properties and a suitable reservoir pressure were the main criteria for identifying a good CO2 storage solution for the project. In addition, placement of the CO2 must be such that it is retained within the aquifer zone and is not reproduced with hydrocarbons during the life of the eld. There is no CO2 tax in Algeria and storage of CO2 is being done for environmental considerations only. Starting in 2004, approximately 1.2 million tonnes per year CO2 has been removed, compressed and in this case injected at a depth of 1800 m into an aquifer section at a remote corner of the Krechba gas eld. Maldal and Tappel (2004) describe the planned CO2 injection at the Snhvit eld. A schematic of the CO2 compression and injection system is shown in Figure 11. Starting in autumn 2006, CO2 injection will occur at the north-western part of the Snhvit eld, into the Tubaen formation, CO2 injection at Snhvit will extend knowledge of CO2 storage in offshore aquifers since there are important differences between the Utsira and Tubaen formations (see Table 10). Similarly to the CO2 injection into the Utsira formation, 4D seismic will be employed at Snhvit to monitor the CO2 injection. To provide a broader base of data, one of the gas producers could be deepened and used as a monitoring well for the injection if deemed necessary. In addition to the existing and planned CO2 storage projects, experience with CO2 ooding for EOR is relevant for storage: Hypotheses about the interaction of CO2 with other components (hydrocarbons, nitrogen and H2S) may be tested against existing data from EOR projects. In addition, monitoring techniques and safe practice encompassing proper operator training, maintenance procedures, pressure monitoring, reliable gas detection systems, emergency shutdown procedures and other safety systems relevant for EOR
24 As discussed previously, detailed seismic mapping can be used to identify fractures and faults.
Data along the three geometric dimensions plus time-interval data.
The aim of the CO2STORE is to prepare the ground for widespread underground storage of CO2 in aquifers. CO2STORE is a research project with 19 participants from industry and research institutes, partly funded by the European Union.
25
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STEENEVELDT et al.
Figure 11. Schematic of CO2 injection at Snhvit after Maldal and Tappel, 2004.
Table 10. Comparison of salient features of utsira and tubaen formations. Depth (m) Utsira (CO2 from Sleipner) Tubaen (CO2 from Snhvit) 800 1000 24002600 Porosity 35 40% 10 16% Permeability 18 Darcy 130880 mDarcy Gas cap No Minor Gas Cap
can be adapted for CO2 storage. In this regard, experience from the acid gas projects in Canada can also be exploited (Bachu and Gunter, 2005). Evidence from the Sleipner, Weyburn, and In Salah projects, indicates that it is feasible to store CO2 in geological formations. Chevron is proposing to remove CO2 from produced gas at the Gorgon eld, containing approximately 14% CO2 off Western Australia. The CO2 will be injected into the Dupuy Formation at Barrow Island (Oen, 2003, cited in IPCC, 2005). In the Netherlands, CO2 is being injected at pilot scale into the almost depleted K12-B offshore gas eld (van der Meer et al., 2005, cited in IPCC, 2005).
REALIZING THE VALUE CHAIN: OPPORTUNITIES AND CHALLENGES FOR VALUE CREATION Trials with the use of CO2 for producing incremental oil began as early as the 1950s (Holm and OBrien, 1971) and the large-scale injection of CO2 into subsurface geological formations was rst undertaken in Texas, USA, in the early 1970s, for EOR as a response to the rst oil price shock. Miscible CO2 ooding has become an increasingly important enhanced oil recovery technique in the USA for recovering residual or bypassed oil. At present there are 71 active CO2 EOR projects in the USA (Oil and Gas Journal, 2004) and approximately 12 operations outside of the USA.
The majority of these projects are clustered in the Permian Basin, located in west Texas and the adjoining area of south-eastern New Mexico and account for approximately 4% (206 000 barrels/day) of the total USA oil production in 2004 (Oil and Gas Journal, EOR Survey, April 12 2004). Approximately 30 million tonnes per year CO2 are injected for EOR worldwide (Oil and Gas Journal EOR survey, April 12 2004). The largest EOR injection rates exceed 10 ktonne/day, the typical emission rate of a 500 MW coal-based power station (Herzog, 1999). With CO2 EOR, the CO2 content of the produced gas changes from 1 to 5% vol at the start and goes beyond 80% towards the end of the project life. The extensive history of CO2 injection in the USA and experience from other countries (including Turkey and Trinidad) indicates that this technology can increase oil recovery by 7 15% for land-based elds as compared with water ooding alone: Holt et al. (2005) surveyed a selection of real eld projects worldwide and concluded that CO2 injection yielded, on average26 incremental oil recoveries above 12% and 17% of the original oil in place for sandstone and carbonate reservoirs, respectively. In a report issued by the Norwegian Petroleum Directorate27 (http://www.npd.no) in 2004, reservoir characteristics (including the spacing of wells) in Norway dictate lower incremental oil recovery (3 7%) for offshore elds. Accurate predictions of the EOR potential for a given eld can however only be assessed through extensive reservoir modelling using a numerical reservoir simulator and a detailed reservoir model. Prices of delivered CO2 to the Permian Basin typically vary between 9 18 USD/ tonne, following movement in oil prices and averaged
26 The CO2 oods included in SINTEF Petroleum Researchs database with 115 CO2 injection projects. 27 http://www.npd.no/Norsk/Produkter og tjenester/Publikasjoner/ Oversikt sokkelpublikasjoner/Rapport_CO2_2004.htm.
CO2 CAPTURE AND STORAGE around USD 11/tonne for pure, high pressure CO2 during the 1990s (Stevens et al., 2001). The production of CO2 with the hydrocarbons is an important issue, since typically more than 50% and up to 67% of the injected CO2 returns with the produced oil (Bondor, 1992) and is usually separated and re-injected into the reservoir. The remainder is trapped in the oil reservoir either by dissolution in reservoir oil that it is not produced and in reservoir pore space unconnected to the ow path for the producing wells.28 The Great Plains Synfuel Plant, near Beulah, North Dakota, gasies 16 326 metric tons per day of lignite coal into 3.5 million standard cubic metres per day of combustible syngas, and close to 7 million standard cubic metres of CO2. A part of the CO2 is captured at high pressure by a physical solvent based on methanol. The captured CO2 is compressed and 2.7 million standard cubic meters per day are piped over a 325 km distance to the Weyburn, Saskatchewan, oil eld, where the CO2 is used for EOR (Perry and Eliason, 2004). Statoil and partners have carried out studies to see if the Tampen offshore area in the North Sea (North of Sleipner) can benet from the use of CO2. A thorough evaluation consisting of reservoir simulation, an assessing the needed platform modications, transportation of CO2 andnot leastin accessing the best CO2-sources for a total need of 5 million tonnes per year (Agustsson and Grinestaff, 2004). Holt et al. (2005) examined the potential for CO2 based EOR in the North Sea, where 67.2 million tonnes of CO2 are injected annually over 40 years and reported that an average potential increase of 7.9% in hydrocarbon pore volume (HCPV). The value (purchase price) of CO2 delivered to export terminals that feeds CO2 into the transportation infrastructure was estimated to be between 7.9 and 12.8 USD/ tonne. When this is compared to the cost of CO2 capture from industrial ue gasses (e.g., a low estimate of 25 USD/ tonne) and transportation from point sources to the export terminals (e.g., 4 USD/tonne), it is evident that the use of CO2 for EOR can cover only a fraction of the total costs associated with CO2 capture, transport and storage.
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CO2 from power generation identied at present stands out as having greater inherent potential for substantially lowering the costs of CO2 capture in the next decade. The challenges for chemical engineering are many: to portray technology choice in the context of entire life-cycles, to improve focus on the fundamentals of molecules, materials and naturally-occurring mechanisms (e.g., photosynthesis) for enhanced process design and increased exploration of hybrid processes (e.g., integrated separation and reaction) that combine the attractive aspects of conventionally discrete unit operations for improved energy and exergy efciency. The increasing number of storage projects worldwide provides a basis for improved strategies for the mitigation and management of risk associated with deep geological storage. The use of CO2 for EOR can cover only a fraction of the total costs associated with CO2 capture from power production, transport and storage. Apart from technical advance, legislation and regulatory changes will be the stronger drivers for closing the knowing-doing gap for CO2 capture and storage. REFERENCES
Abanades, J.C., 2002, The maximum capture efciency of CO2 using carbonation/calcination cycle of CaO/CaCO3, Chem Eng J, 90: 303. Abanades, J.C., Anthony, E.J., Alvarez, D., Lu, D.Y. and Salvador, C., 2004a, Capture of CO2 from combustion gases in a uidised bed of CaO, AIChE J, 50(7): 16141622. Abanades, J.C., Rubin, E.S. and Anthony, E.J., 2004b, Sorbent cost and performance in CO2 capture systems, Ind Eng Chem Res., 43: 34623466. Aboudheir A., Tontiwachwuthikul, P., Chakma, A. and Idem, R., 2003, Kinetics of the reactive absorption of carbon dioxide in high CO2loaded, concentrated aqueous monoethanolamine solutions, Chem Eng Sci, 58: 51955210. Agustsson, H. and Grinestaff, G.H., 2004, A study of IOR by CO2 injection in the Gullfaks Field, Offshore Norway, SPE/DOE Fourteenth Symposium on Improved Oil Recovery, Tulsa, Oklahoma, USA, SPE 89338, 1 14. Alic, J.A., Mowery, D.C. and Rubin, E.S., 2003, U.S. technology and innovation policies, Lessons for Climate Change. Pew Center on Global Climate Change, Arlington, VA, November. Allam, C., McDonald, J., White, V., Stein, V.E. and Simmonds, M., 2004, Oxyfuel conversion of renery process equipment utilising ue gas recycle for CO2 capture, Proceedings of the 7th International Conference on Greenhouse Gas Control Technologies, Volume 1, Peer-Reviewed Papers and Plenary Presentations, Vancouver, BC, September 59, 2004. Alstom Power Inc., ABB Lummus Global Inc., Alstom Power Environmental Systems and American Electric Power, 2001, Engineering feasibility and economics of CO2 capture on and existing coal-red power plant. Report no. PPL-01CT-09 to Ohio Department of Development, Columbus, OH and US Department of Energy. Aresta, M.A. and Dibenedetto, A., 2003, New amines for the reversible absorption of carbon dioxide from gas mixtures, Greenhouse Gas Control Technologies, Proceedings of the 6th International Conference on Greenhouse Gas Control Technologies (GHGT-6), 14 Oct. 2002, Kyoto, Japan, J. Gale and Y. Kaya (eds). Elsevier Science Ltd, Oxford, UK, 15991602. Aroonwilas, A., Chakma, A., Tontiwachwuthikul, P. and Veawab, A., 2003, Mathematical modeling of mass-transfer and hydrodynamics in CO2 absorbers packed with structured packings, Chem Eng Sci, 58: 40374053. Arts, R., Chadwick, A. and Eiken, O., 2004, Recent time lapse seismic data show no indication of leakage at the Sleipner CO2-injection site, Proceedings of the 7th International Conference on Greenhouse Gas Control Technologies (GHGT-7), September 59, 2004, Vancouver, Canada. Volume I, Peer Reviewed Papers and Overviews, Elsevier Science, Oxford, UK. Asen I.K, 2001,. Process for generating power and/or heat comprising a mixed conducting membrane reactor, United States Patent, Patent No. US6,237,339 B1, 29 May 2001. Astarita, G., Savage, D.W. and Bisio, A., 1983, Removal of Carbon Dioxide, Gas Treating with Chemical Solvents (Wiley, New York, USA).
CONCLUSIONS The fundamentals of combustion and separation processes suggest that the capture of high purity, high concentration CO2 from fossil fuels requires energy. Improved energy efciency and fuel switching are thus clearly superior strategies for curtailing CO2 emissions, although these strategies do not actively capture CO2 from being the concern of a few specialists with strong convictions about man-made impacts on the earth, the substantial commitment of public resources to CCS R&D has contributed to establishing research on carbon dioxide capture and storage as part of the mainstream. CO2 capture is premised on the safe long-term storage of CO2 in geological formations. There is sufcient industry-wide know-how for realizing CO2 capture from dilute stationary sources of CO2, but poor economics prevents this knowledge from being put into practice. None of the major pathways for capturing
28 In the absence of an approach for CO2 capture from the transportation sector, CO2 (captured from the power sector) for enhanced oil recovery may lead to a net increase in global CO2 emissions, and arguments for the use of CO2 for EOR for limiting CO2 emissions should be moderated with the consequences of increased oil production.
760
STEENEVELDT et al.
Carolan, M.F., Dyer, P.N., Minford, E., Barton, T.F., Peterson, D.R., Sammells, A.F., Butt, D.L., Cutler, R.A. and Taylor, D.M., 2001, Development of the high pressure ITM syngas process, Proceedings of the 6th Natural Gas Conversion Symposium, Alaska, 1722 June. Chakma, A. and Tontiwachwuthikul, P., 1999, Designer solvents for energy efcient CO2 separation from ue gas streams, in Riemer, P., Eliasson, B. and Wokaun, A. (eds). Greenhouse Gas Control Technologies, 35 42 (Elsevier Science, Ltd., UK) Chakma, A., 1995, An energy efcient mixed solvent for the separation of CO2, Energy Conversion and Management, 36(69): 427430. Chakravarti, S., Gupta, A. and Hunek, B., 2001, Advanced technology for the capture of carbon dioxide from ue gases, Presented at First National Conference on Carbon Sequestration, May 1517, 2001, Washington, DC. Chapel, D.G., Mariz, C. and Ernest, J., 1999, Recovery of CO2 from ue gases, commercial trends, Paper No. 340 at the Annual Meeting of the Canadian Society of Chemical Engineering, Saskatoon, Canada, October. Chapel, D., Ernest, J. and Mariz C., 2001, Recovery of CO2 from ue gases, First National Conference on Carbon Sequestration, Washington, DC, May 1417. Chatel-Pelage, F., Ovidiu, M., Carty, R., Philo, G., Farzan, H. and Vecci, S., 2003, A pilot scale demonstration of oxy-fuel combustion with ue gas recirculation in a pulverised coal-red boiler, Proceedings 28th International Technical Conference on Coal Utilization & Fuel Systems, Clearwater, Florida, March 1013. Chen, C., Rao, A.B. and Rubin, E.S., 2003, Comparative assessment of CO2 capture options for existing coal-red power plants, presented at the Second National Conference on Carbon Sequestration, Alexandria, VA, USA, 58 May. Chinn, D., Eimer, D. and Hurst, P., 2004, CO2 capture project, post combustion Best Integrated Technology (BIT) overview, Third National Conference on Carbon Capture and Sequestration, National Energy Technology Laboratory/DOE, May 2004. Cho, P., Mattisson, T. and Lyngfelt, A., 2002, Reactivity of iron oxide with methane in a laboratory uidised bedapplication of chemical-looping combustion, 7th International Conference on Circulating Fluidised Beds, Niagara Falls, Ontario, May 57, 2002, 599606. Contarini, S., Barbini, M., Del Piero, G., Gambarotta, G., Mazzamurro, G., Riocci, M. and Zappelli, P., 2002, Solid sorbents for the reversible capture of carbon dioxide, 6 IEA Greenhouse Gas Technology Conference, Kyoto. Corradetti, A. and Desideri, V., 2005, Analysis of gas-steam combined cycles with natural gas reforming and CO2 capture, Journal of Engineering for Gas Turbines and Power, 127: 545552. Croiset, E. and Thambimuthu, K., 2000, Coal combustion in O2/CO2 mixtures compared to air, Canadian Journal of Chemical Engineering, 78: 402 407. Croiset, E., Thambimuthu, K. and Palmer, A., 2000, Coal combustion in O2/CO2 mixtures compared with air, The Canadian Journal of Chemical Engineering, 78: 402407. Cullinane, J.T. and Rochelle, G.T., 2003, Carbon dioxide absorption with aqueous potassium carbonate promoted by piperazine, Gale, J. and Kaya, Y. (eds). Greenhouse Gas Control Technologies, Vol. II, 16031606 (Elsevier Science, UK). Davison, J.E., 2005, CO2 capture and storage and the IEA Greenhouse Gas R&D Programme, Workshop on CO2 issues, Middelfart, Denmark, 24 May, IEA Greenhouse Gas R&D Programme, Cheltenham, UK. De Koeijer, G. and Solbraa, E., 2004, High pressure gas sweetening with amines for reducing CO2 emissions, Proceedings of GHGT-7, Vancouver, Canada, http://uregina.ca/ghgt7/PDF/papers/nonpeer/267.pdf. DeMontigny, Tontiwachwuthikul, P. and Chakma, A., 2005, Comparing the absorption performance of packed columns and membrane contactors, Ind Eng Chem Res, 44 (15): 57265732. Dillon, D.J., Panesar, R.S., Wall, R.A., Allam, R.J., White, V., Gibbins, J. and Haines, M.R., 2005, Oxy-combustion processes for CO2 capture from advanced supercritical PF and NGCC power plant, in Rubin, E.S., Keith, D.W. and Gilboy, C.F. (eds). Proceedings of 7th International Conference on Greenhouse Gas Control Technologies, Volume I: Peer Reviewed Papers and Overviews, Elsevier Science, Oxford, UK (in press). Dyer, P.N., Richards, R.E., Russek, S.L. and Taylor, D.M., 2000, Ion transport membrane technology for oxygen separation and syngas production, Solid State Ionics, 134: 2133. Eimer, D., 2005, Post-combustion CO2 separation technology summary, in Thomas, D.C. (ed.). Carbon Dioxide Capture for Storage in Deep Geologic Formations Results from the CO2 Capture Project, Capture and Separation of Carbon Dioxide from Combustion Sources. Volume 1, 9197 (Elsevier).
Audigane, P., Gaus, I., Pruess, K. and Xu T., 2005, Reactive transport modelling using TOUGHREACT for the long term CO2 storage at Sleipner, North Sea. Fourth Annual Conference on Carbon Capture and Sequestration DOE/NETL, May 2 5, 2005. Bachu, S. and Gunter, W., 2005, Overview of acid gas injection in western Canada. In Rubin, E.S., Keith, D.W. and Gilboy, C.F., (eds). Proceedings of 7th International Conference on Greenhouse Gas Control Technologies. Volume I: Peer Reviewed Papers and Overviews, Elsevier Science, Oxford, UK (in press). Bai, H. and Yeh, A.C., 1997, Removal of CO2 greenhouse gas by ammonia scrubbing, Ind Eng Chem Res, 36(6): 24902493. Baklid, A., Korbl, R, Owren, G., 1996, Sleipner vest CO2 disposal, CO2 injection into a shallow underground aquifer, SPE Annual Technical Conference and Exhibition, Denver, Colorado, USA, SPE 36600, 1996, 269 277. Barchas, R. and Davis, R., 1992, The Kerr-McGee/ABB Lummus Crest technology for the recovery of CO2 from stack gases, Energy Conversion and Management, 33(58): 333340. Barrio, M., Aspelund, A., Weydahl, T., Sandvik, T.E., Wongraven, L.R., Krogstad, H., Henningsen, R., Mlnvik, M. and Eide, S.I., 2004, Ship based transport of CO2, in Rubin, E.S., Keith, D.W. and Gilboy, C.F. (eds). Proceedings of 7th International Conference on Greenhouse Gas Control Technologies. Volume I: Peer Reviewed Papers and Overviews, Elsevier Science, Oxford, UK. Bao, L. and Trachtenberg, M., 2005, Modelling CO2-facilitated transport across a diethanolamine liquid membrane, Chem Eng Sci, 60: 68686875. Beecy, D.J. and Kuuskraa, V.A., 2005, Basic strategies for linking CO2 enhanced oil recovery and storage of CO2 emissions, in Rubin, E.S., Keith, D.W. and Gilboy, C.F. (eds). Proceedings of the 7th International Conference on Greenhouse Gas Control Technologies (GHGT-7), September 59, 2004, Vancouver, Canada. Volume I: Peer Reviewed Papers and Overviews, Elsevier Science, Oxford, UK. Berger, B., Karstad, O. and Haugen, H.A., 2004, Creating a large-scale CO2 infrastructure for enhanced oil recovery, in Proceedings of GHGT-7, Vancouver, Canada, http://uregina.ca/ghgt7/PDF/papers/ peer/108.pdf. Benson, S.M., 2005, Overview of geologic storage of CO2, in Thomas, D.C. and Benson, S. (eds). Capture and Separation of Carbon Dioxide from Combustion Sources, Volume 2 (Elsevier Science, Oxford, UK). Bishnoi, S. and Rochelle, G.T., 2002, Absorption of carbon dioxide in aqueous piperazine/methyldiethanolamine, AIChE J, 48(12): 27882801. Bock, B., Rhudy, R., Herzog, H., Klett, M., Davison, J., De la Torre Ugarte, D. and Simbeck, 2003, Economic evaluation of CO2 storage and sink options, DOE Research Report DE-FC26-00NT40937, U.S. Department of Energy, Pittsburgh Energy Technology Center, Pittsburgh, PA, USA. Bolland, O., 2002, Gaskraftverk med CO2-handtagning. Studie av alternative teknologier, SINTEF Energiforskning AS, Report nr. TR A5693, Trondheim, Norway. ISBN Nr, 82-594-2358-8 (In Norwegian). Bolland, O. and Undrum, H., 2003, A novel methodology for comparing CO2 capture options for natural gas-red combined cycle plants, Advances in Environmental Research, 7: 901 911. Bolland, O. and Sther, S., 1992, New concepts for natural gas red power plants which simplify the recovery of carbon dioxide, Energy Conversion Management, 33(58): 467475. Bolland, O., Kvamsdal H.M. and Boden, J.C., 2005, A comparison of the efciencies of the oxy-fuel power cycles water-cycle, graz-cycle and matiant-cycle, in Thomas, D.C. (ed.). Carbon Dioxide Capture for Storage in Deep Geologic Formations Results from the CO2 Capture Project, Capture and Separation of Carbon Dioxide from Combustion Sources. Volume 1; 499511 (Elsevier). Bondor, P.L., 1992, Applications of carbon dioxide in enhanced oil recovery, Energy Conversion and Management, 33(5): 579 586. Bouwmeester, H.J.M. and Van Der Haar, L.M., 2002, Oxygen permeation through mixed-conducting perovskite oxide membranes, Ceramic Transactions, 127: 4957. BP, 2005, BP Statistical Review of World Energy, http://www.bp.com. Brandvoll, . and Bolland, O., 2004, Inherent CO2 capture using chemical looping combustion in a natural gas red power cycle, ASME Paper No. GT-2002-30129, ASME Journal of Engineering for Gas Turbines and Power, 126: 316 321. Bredesen, R., Jordal, K. and Bolland, O., 2004, High-temperature membranes in power generation with CO2 capture, Journal of Chemical Engineering and Processing, 43: 1129 1158. Buller, A.T., Karstad, O. and De Koeijer, G., 2004, Carbon dioxide capture storage and utilization,. Statoil Research & Technology Memoir No. 5, Statoil Research Centre, 7005 Trondheim, Norway.

Erga, O., Juliussen, O. and Lidal, H., 1995, Carbon dioxide recovery by means of aqueous amines, Energy Conversion and Management, 36(69): 387 392. Ertesrag, I.S., Kvamstal, H.M. and Bolland, O., 2005, Exergy analysis of a gas-turbine combined-cycle power plant with precombustion CO2 capture, Energy, 30: 5 39. Falk-Pedersen, O., Dannstrom, H., Grnvold, M., Stuksrud, and Rnning, O., 1999, Gas treatment using membrane gas/liquid contractors, in Eliasson, B., Riemer, P. and Wokaun, A (eds). Greenhouse Gas Control Technologies, 115120 (Elsevier Science, Ltd., UK). Feron, P.H.M and Jansen, A.E., 2002, CO2 separation with polyolen membrane contactors and dedicated absorption liquids, Performances and prospects, Separation and Purication Technology, 27(3): 231242. Feron, P.H.M., 1992, Carbon dioxide capture, The characterisation of gas separation/removal membrane systems applied to the treatment of ue gases arising from power plant generation using fossil fuel, IEA/92/08, IEA Greenhouse Gas R&D programme, Cheltenham, UK. Feron, P.H.M., 1994, Membranes for carbon dioxide recovery from power plants. in Paul, J. and Pradier C.M. (eds). Carbon Dioxide Chemistry: Environmental Issues, 236 249 (The Royal Society of Chemistry, Cambridge, UK). Gibbins, J., Crane, R.I., Lambropoulos, D., Booth, C., Roberts, C.A. and Lord, M., 2005, Maximising the effectiveness of post-combustion CO2 capture systems, in Rubin, E.S., Keith, D.W. and Gilboy, C.F. (eds). Proceedings of the 7th International Conference on Greenhouse Gas Control Technologies. Volume, I: Peer Reviewed Papers and Overviews, Elsevier Science, Oxford, UK (in press). Green, D.A., Turk, B.S., Gupta, R.P., Portzer, J.W., McMichael, W.J. and Harrison, D.P., 2002, Capture of carbon dioxide from ue gas using regenerable sorbents, 19th Annual International Pittsburgh Coal Conference, September 2327, Pittsburgh, Pennsylvania, USA. Grifn, T., Sundkvist, S.G., Aasen, K. and Bruun, T., 2003, Advanced zero emissions gas turbine power plant, ASME Turbo Expo Conference, paper# GT-2003-38120, Atlanta, USA. Ha-Duong, M. and Keith, D.W., 2003, Carbon storage, the economic efciency of storing CO2 in leaky reservoirs, Clean Techn Environ Policy, 5: 181 189. Haefeli Su, Bosi, M. and Philibert, C., 2004 Carbon dioxide capture and storage issuesaccounting and baselines under the United Nations Framework Convention on climate change (UNFCC), IEA Information Paper, IEA, Paris. Hagg, M. and Lindbrathen, A, 2005, CO2 capture from natural gas red power plants by using membrane technology, Ind Eng Chem Res, 44: 76687675. Haines, M.R, Skinner, G.F. and Maunder, A.D., 2004, Rapid assessment of novel CO2 capturing power plants, in Rubin, E.S., Keith, D.W. and Gilboy, G.F. (eds). Proceedings of the 7th International Conference on Greenhouse Gas Control Technologies. Volume I: Peer Reviewed Papers and Overviews, Elsevier Science, Oxford, UK (in press). Hansen, H., Eiken, A. and Aasum, T.A., 2005, Tracing the path of carbon dioxide from a gas-condensate reservoir, through an amine plant and back into a subsurface acquifer, SPE-96742-PP. Heggum, G., Weydahl, T., Mo, R., Mlnvik, M. and Austegaard, A., 2005, CO2 Conditioning and Transportation, in Thomas, D.C. (ed.). Carbon Dioxide Capture for Storage in Deep Geologic Formations Results from the CO2 Capture Project, Vol. 2, 923936 (Elsevier). Heinrich, J., Herzog, H. and Reiner, D., 2003, Environmental assessment of geologic storage of CO2, Presented at the Second National Conference on Carbon Sequestration, Washington, DC, May 5 8, 2003. Herzog, H.J., 1999, The economics of CO2 capture, Proceedings of the Fourth International Conference on Greenhouse Gas Control Technologies, in Eliasson, B., Riemer, P. and Wokaun, A. (eds). 30 August 2 September 1998, Interlaken, Switzerland, Elsevier Science Ltd., Oxford, UK, 101 106. Herzog, H., Golomb, D. and Zemba, S., 1991, Feasibility, modelling and economics of sequestering power plant CO2 emissions in the deep ocean, Environmental Progress, 10(1): 6474. Herzog, H. and Falk-Pedersen, O., 2001, The Kvaerner membrane contactor, lessons from a case study in how to reduce capture cost, Proceedings Fifth International Conference on Greenhouse Gas Technologies, GHGT 5, Cairns, Australia. Hoffman, J.S., Fauth, D.J. and Pennline, H.W., 2002, Development of novel dry regenerable sorbents for CO2 capture. 19th Annual International Pittsburgh Coal Conference, September 2327, Pittsburgh, Pennsylvania, USA. Holm, L.W. and O Brien, L.J., 1971, Carbon dioxide tests at the Mead-Strawn eld, Journal of Petroleum Technology, April 1971, SPE 3103, pp. 431 432.
761
Holt, N., Booras, G and Todd, D, 2003, Summary of recent IGCC studies of CO2 for sequestration, Proceedings of Gasication Technologies Conference, October 1215, San Francisco, http://www.gasication.org. Holt, T. and Lindeberg, E., 1988, Miljvennlig gasskraft kombinert med kt oljeutvinning- en forstudie, I KU report no. 34.2776, 00/01/88 Trondheim, Norway. Holt, T., Lindeberg, E., Vassenden, F. and Wessel-Berg, D., 2005, A largescale infrastructure model for CO2 disposal and EOReconomic and capacity potential in the North Sea. Proceedings of the 7th International Conference on Greenhouse Gas Control Technologies (GHGT-7), September 59, 2004, Vancouver, Canada. Volume I: Peer Reviewed Papers and Overviews, Elsevier Science, Oxford, UK (in press). Huang, H., Chang, S.G. and Dorchak, T., 2002, A method to regenerate ammonia for the capture of carbon dioxide; Energy Fuels, 16(4): 904910. Hufton, J.R., Allam, R.J., Chiang, R., Middleton, R.P. Weist, E.L. and White, V., 2005, Development of a process for CO2 capture from gas turbines using a sorption enhanced water gas shift reactor system, in Rubin, E.S., Keith, D.W. and Gilboy, C.F. (eds). Proceedings of 7th International Conference on Greenhouse Gas Control Technologies, Volume I: Peer Reviewed Papers and Overviews, Elsevier Science. Hufton, J.R., Mayorga, S. and Sircar, S. 1999, Sorption enhanced reaction process for hydrogen production, AIChE J, 45: 248254. International Energy Agency (IEA), 2004a, IEA World Energy Outlook 2004, International Energy Agency, Paris France. International Energy Agency (IEA), 2004b, Prospects for CO2 Capture and Storage, ISBN 92-64-10881-5. (IEA) GHG, 1996, De-carbonisation of fossil fuels, Report PH2/2, March 1996, IEA GreenhouseGas R&D Programme, Cheltenham, UK. (IEA) GHG, 2000b, Leading options for the capture of CO2 emissions at power stations, report PH3/14, Feb. 2000, IEA Greenhouse Gas R&D Programme, Cheltenham, UK. (IEA) GHG, 2002a, Transmission of CO2 and energy, report PH4/6, March 2002, IEA GreenhouseGas R&D Programme, Cheltenham, UK. (IEA) GHG, 2002b, Opportunities for early application of CO2 sequestration technologies, report PH4/10, Sept. 2002, IEA Greenhouse Gas R&D Programme, Cheltenham, UK. (IEA) GHG, 2003, Potential for improvements in gasication combined cycle power generation with CO2 Capture, report PH4/19, IEA Greenhouse Gas R&D Programme, Cheltenham, UK. (IEA) GHG, 2004, Improvements in power generation with post-combustion capture of CO2, report PH4/33, Nov. 2004, IEA Greenhouse Gas R&D Programme, Cheltenham, UK. IPCC 2005, IPCC Special report on carbon dioxide capture and storage, Chapter 3, http://www.ipcc.ch/activity/srccs/index.htm. Ishida, M. and Jin, H., 1994, A new advanced power-generation system using chemical-looping combustion, Energy, 19(4): 415 422. Ishida, M., Yamamoto, M. and Sioto, Y., 1999, Experimental works on innovative chemical-looping combustor, Proceedings of ECOS99, International Conference on Efciency, Cost, Optimization, Simulation and Environmental Aspects of Energy Systems, 306 310, June 810, Tokyo, Japan. Ishida, M., Yamamoto, M. and Ohba, T., 2002, Experimental results of chemical looping combustion with NiO/NiAl2O4 particle circulation at 12008C, Energy Conversion and Management, 43: 14691478. Jin, H., Okamoto, T. and Ishida, M., 1999, Development of a novel chemical-looping combustion, synthesis of a solid looping material of NiO/NiAl2O4, Ind Eng Chem Res, 38: 126 132. Jacobs, 2003, Standardized PCDC, Jacobs Consultancy Nederland BV, Report Number 63891-00, CO2 Capture Project Team, Washington DC, USA. Jericha, H., Gottlich, E., Sanz, W. and Heitmeir, W.F., 2003, Design optimisation of the Graz cycle power plant, ASME Turbo Expo Conference, paper GT-2003-38120, Atlanta, USA. Jordal, K., Bredesen, R., Kvamsdal H.M. and Bolland, O., 2003, Integration of H2-separating membrane technology in gas turbine processes for CO2 sequestration, in Kyoto, Japan, in Gale, J. and Kaya, Y. (eds). Proceedings of the 6th International Conference on Greenhouse Gas Control Technologies (GHGT-6), Vol. 1, 135 140, 1 4 Oct. 2002, Elsevier Science Ltd, Oxford, UK. Kato, M., Yoshikawa, S. and Nakagawa, K., 2001, Carbon dioxide absorption by lithium ortosilicate in a wide range of temperature and carbon dioxide concentration, J of Materials Science Letters, 21: 485 487. Kimura, S., Adachi, M., Noda, R. and Horio, M., 2005, Particle design and evaluation of dry CO2 recovery sorbent with a liquid holding capability, Chem Eng Sci, 60: 40614071.
762
STEENEVELDT et al.
carbon dioxide recovery and steam system in power plant, Energy Conversion and Management, 36(69): 397400. Mimura, T., Nojo, T., Iijima, M., Yoshiyama, T. and Tanaka, H., 2003, Recent developments in ue gas CO2 recovery technology. Greenhouse Gas Control Technologies, in Gale, J. and Kaya, Y. (eds). Proceedings of the 6th International Conference on Greenhouse Gas Control Technologies (GHGT-6), 1 4 Oct., 2002, Kyoto, Japan (Elsevier Science Ltd, Oxford, UK). Moller, B. F., Torrison, T. and Assadi, M., 2005, AZEP gas turbine combined cycle power plantsthermo-economic analysis, Proceedings of ECOS 2005, Trondheim, Norway, June 2022, Vol. 2, 819 826. NETL, 2002, Advanced fossil power systems comparison study, Final report prepared for NETL by E.L. Parsons (NETL, Morgantown, WV), W.W. Shelton and J.L. Lyons (EG&G Technical Services, Inc., Morgantown, WV), December. Nsakala, N., Liljedahl, G., Marion, J., Bozzuto, C., Andrus, H. and Chamberland, R., 2003, Greenhouse gas emissions control by oxygen ring in circulating uidised bed boilers. Presented at the Second Annual National Conference on Carbon Sequestration, Alexandria, VA, USA May 58. Oil and Gas Journal, Suvery of EOR Projects, April 12, 2004. Okabe, K., Matsumija, N., Mano, H. and Teramoto, M., 2003, Development of CO2 separation membranes (1) Facilitated transport membrane, in Gale J. and Kaya Y. (eds). Greenhouse Gas Control Technologies, 15551558 (Elsevier Science, Ltd., UK). Parsons Infrastructure and Technology Group, Inc., 2002a, Hydrogen Production Facilities: Plant Performance and Cost Comparisons, Final Report, prepared for the National Energy Technology Laboratory, US DOE, March. Parsons Infrastructure & Technology Group, Inc., 2002b, Updated Cost and Performanc Estimates for Fossil Fuel Power Plants with CO2 Removal. Report under Contract No. DE-AM26-99FT40465 to U.S.DOE/NETL, Pittsburgh, PA, and EPRI, Palo Alto, CA., December. Perry, M. and Eliason, D., 2004, CO2 recovery and sequestration at Dakota Gasication Company. (http://gasication.org). Rao, A.B. and Rubin, E.S., 2002, A technical, economic, and environmental assessment of aminebased CO2 capture technology for power plant greenhouse gas control, Environmental Science and Technology, 36: 44674475. Rao, A.B., Rubin, E.S. and Morgan, M., 2003, Evaluation of potential cost reductions from improved CO2 capture systems, 2nd Annual Conference on Carbon Sequestration, Alexandria, VA, USA, 58 May, U.S. Department of Energy, NETL, Pittsburgh, PA. Rao, A.D. and Day W., 1996, Mitigation of greenhouse gases from gas turbine power plants, Energy Conversion Management, 37(68): 909914. Reddy, S., Scherfus, J., Freguia, S. and Roberts, C., 2003, Fluors Econamine FG PlusSM technologyan enhanced amine-based CO2 capture process, 2nd Annual Conference on Carbon Sequestration, Alexandria, VA, USA, 5 8 May, U.S. Department of Energy, National Energy Technology Laboratory, Pittsburgh, PA. Riahia, K., Rubin, E.S., Taylor, M.R., Schrattenholzer, L. and Hounshell, D., 2004, Technological learning for carbon capture and sequestration technologies, Energy Economics, 26: 539 564. Richter, H.J. and Knoche, K, 1983, Reversibility of combustion processes, efciency and costingsecond law analysis of processes, ACS Symposium Series, 235: 7185. Riddiford, F., Wright, A., Bishop, C., Espie, T. and Tourqu A., 2004, Monitoring geological storage, the In Salah gas CO2 storage project, Paper available at http://uregina.ca/ghgt7/PDF/papers/nonpeer/529.pdf. Riemer, P W F and Ormerod, W.G., 1995, International perspectives and the results of carbon dioxide capture disposal and utilisation studies, Energy Conversion and Management, 36(69): 813818. Roberts, C., 2002, Presentation at DTI CO2 Capture and Storage Seminar, May 2002. Roberts, CA, Gibbins, J., Panesar, R. and Kelsall, G., 2004, Potential for improvement in power generation with post-combustion capture of CO2, in Proceedings of GHGT-7, September 59, Vancouver, Canada, paper 510. Robinson, S., Aasland, S. and Chen, J., 2004, The application of oxygen transport membranes for syngas or hydrogen production, Presentation for the Spring AIChE Meeting, April 26, 2004, Session T9008. Rosenberg, W.G, Alpern, D.W. and Walker, M.R., 2005, Deploying IGCC In this Decade with 3Party Convenant Financing, Volume 1, May 2005 revision (John F Kennedy School of Government, Harvard University). Rubin, E.S. and Rao, A.B., 2003, Uncertainties in CO2 capture and sequestration costs, Greenhouse Gas Control Technologies, in Gale, J. and Kaya, Y. (eds). Proceedings of the 6th International Conference on
Klara, S.M. and Srivastava, R.D., 2002, US DOE integrated collaborative technology development program for CO2 separation and capture, Environmental Progress, 21(4): 247 253. Kreutz, T., Williams, R., Chiesa, P. and Consonni, S., 2005, Co-production of hydrogen, electricity and CO2 from coal with commercially ready technology. Part, B., Economic analysis, International Journal of Hydrogen Energy, 30(7): 769784. Kvamsdal, H., Maurstad, O., Jordal, K. and Bolland, O., 2005a, Benchmarking of gas-turbine cycles with CO2 capture, in Rubin, E.S., Keith, D.W. and Gilboy, C.F. (eds). Proceedings of 7th International Conference on Greenhouse Gas Control Technologies, Volume I: Peer Reviewed Papers and Overviews, Elsevier Science, 2005 (in press). Kvamsdal, H, Mejdell, T, Steineke, F, Weydahl, T, Aspelund, A, Hoff, K.A., Skouras, S. and Barrio, M., 2005b, Tjeldbergodden power/methanol CO2 reduction efforts, SP2 CO2 capture and transport, SINTEF Techical Report, Sintef Energy Research Trondheim, ISBN 82-594-2762-1. Lee, A., Christensen, D., Cappelen, F., Hartog, J., Thompson, A., Johns, G., Senior, B. and Akhurst, M., 2005, Policies and incentives developments in CO2 capture and storage technology, a focused survey by the CO2 capture project, in Thomas, D.C (ed.). Carbon Dioxide Capture for Storage in Deep Geologic Formations Results from the CO2 Capture Project, Capture and Separation of Carbon Dioxide from Combustion Sources. Volume 1; 3149 (Elsevier). Lekva, H., Karstad, O., Berger, B. and Sundset, T., 2005, CO2 from problem to business opportunity? in Proceedings of ECOS Conference, 2005, Trondheim. Leites, I.L., 1998, The thermodynamics of CO2 solubility in mixtures monoethanolamine with organic solvents and water and commercial experience of energy saving gas purication technology, Energy Conversion and Management, 39: 16651674. Liang, Y., Harrison, D.P., Gupta, R.P., Green, D.A. and McMichael, W.J., 2004, Carbon dioxide capture using dry sodium-based sorbents, Energy & Fuels, 18: 569 575. Lombardi, L., 2005, Life cycle assessment (LCA) and exergetic life cycle assessment (ELCA) of a semi-closed gas turbine cycle with CO2 chemical absorption, Energy Conversion & Management, 42(2001): 101 114. Lowe, C., Francuz, V. and Behrens, C., 2003, Hydrogen membrane selection for a water gas shift reactor, Second DoE Annual Conference on Carbon Sequestration, May, Arlington, VA. Lyngfelt, A., Leckner, B. and Mattisson, T, 2001, A uidized-bed combustion process with inherent CO2 separation; application of chemicallooping combustion, Chem Eng Sci, 56: 31013113. Lynghjem, A., Jakobsen, J, Kobro, H, Lund, A. and Gjerset, M., 2004, The Combicap cycle-efcient combined cycle power plants with CO2 capture, presented at the 2nd Trondheim Conference on CO2 Capture, Transport and Storage, Trondheim, Norway, October 25 25. Maldal, T. and Tappel, I. M, 2004, CO2 underground storage for Snhvit gas eld development, Energy 29: 14031411. Mano, H., Kazama, S. and Haraya, K., 2003, Development of CO2 separation membranes (1) Polymer membrane, in Gale J. and Kaya Y. (eds). Greenhouse Gas Control Technologies, 15511554 (Elsevier Science, Ltd., UK). Mathieu, P., 2003, Mitigation of CO2 emissions using low and near zero CO2 emission power plants. Clean air, International Journal on Energy for a Clean Environment, 4: 116. McDonald, A. and Schrattenholzer, L., 2001, Learning rates for energy technologies, Energy Policy, 29: 255261. McKee, B., 2002, Solutions for the 21st century. Zero emission technologies for fossil fuels, International Energy Agency Working Party on Fossil Fuels. Melien, T., 2005, CCP. Final cost estimation and economics common economic model team summary report. in Thomas, D.C. (ed.). Carbon Dioxice Capture for Storage in Deep Geologic FormationsResutls from the CO2 Capture Project, Capture and Separation of Carbon Dioxide from Combustion Souces. Volume 1, 4787 (Elsevier). Middleton, P., Solgaard-Andersen, H., and Rostrup-Nielsen, T., 2002, Hydrogen production with CO2 capture using membrane reactors. 14th World Hydrogen Energy Conference, June 914, Montreal, Canada. Mimura, T., Satsumi, S., Iijima, M. and Mitsuoka, S., 1999, Development on energy saving technology for ue gas carbon dioxide recovery by the chemical absorption method and steam system in power plant. Greenhouse Gas Control Technologies, Riemer, P., Eliasson, B. and Wokaun, A. (eds) (Elsevier, UK) pp 7176. Mimura, T., Simayoshi, H., Suda, T., Iijima, M. and Mitsuoka, S., 1997, Development of energy saving technology for ue gas carbon dioxide recovery in power plant by chemical absorption method and steam system, Energy Conversion and Management, 38: S57S62. Mimura, T., Shimojo, S., Suda, T., Iijima, M. and Mitsuoka, S., 1995, Research and development on energy saving technology for ue gas

Greenhouse Gas Control Technologies (GHGT-6), 14 Oct. 2002, Kyoto, Japan (Elsevier Science Ltd, Oxford, UK). Rubin, E.S., Rao, A.B. and Chen, C., 2005, Comparative assessments of fossil fuel power plants with CO2 capture and storage, Proceedings of 7th International Conference on Greenhouse Gas Control Technologies, Volume 1: Peer-Reviewed Papers and Overviews, Rubin, E.S., Keith D.W. and Gilboy C.F. (eds). (Elsevier Science, Oxford, UK) (in press). Rubin, E.S., Yeh, S. Hounshell, D.A. and Taylor, M.R., 2004a, Experience curves for power plant emission control technologies, International Journal of Energy Technology and Policy, 2(1/2): 5268. Rubin, E.S., Hounshell, D.A., Yeh, S., Taylor, M., Schrattenholzer, L., Riahi, K., Barreto, L. and Rao, S., 2004b, The effect of government actions on environmental technology innovation, applications to the integrated assessment of carbon sequestration technologies, Final Report of Award No. DE-FG02-00ER63037 from Carnegie Mellon University, Pittsburgh, PA to Ofce of Biological and Environmental Research, U.S. Department of Energy, Germantown, MD, January, 153 p. Sander, M.T. and Mariz, C.L. 1992, The Fluor Danielw EconamineTM FG process, past experience and present day focus, Energy Conversion Management, 33(58): 341 348. Senior, B., Adams Espie, T. and Wright, I., 2004, Investigation of how capture and storage could evolve as a large scale CO2 mitigation option, Proceedings of the7th International Conference on Greenhouse Gas Control Technologies (GHGT-7), September 59, 2004. Paper available at http://uregina.ca/ghgt7/PDF/papers/peer/462.pdf. Sheinbaum, C. and Ozawa, L., 1998, Energy use and CO2 emissions for Mexicos cement industry, Energy, 23(8): 725732. Simbeck, D.R., 2001, World Gasication Survey, Industrial trends and developments. Paper presented at the Gasication Technology Conference, San Francisco, CA, USA, October. (www.gasication.org). Simbeck, D.R., 2002, New Power Plant CO2 mitigation costs (SFA Pacic, Inc., California, USA). Singh, D., Croiset, E., Douglas, P.L. and Douglas, M.A., 2003, Technoeconomic study of CO2 capture from an existing coal-red power plant, MEA scrubbing vs. O2/CO2 recycle combustion, Energy Conversion and Management, 44: 30733091. Sircar, S., and Golden, C.M.A., 2001, PSA process for removal of bulk carbon dioxide from a wet hightemperature gas, US Patent no. 6322612. Skinner, S.J. and Kilner, J.A. 2003, Oxygen ion conductors, Materials Today, 6(3): 30 37. Skovholt, O., 1993, CO2 transportation system, Energy Conversion Management, 34: 10951103. Steinberg, M., Cheng, H.C. and Horn, F., 1984, A systems study for the removal, recovery and disposal of carbon dioxide from fossil fuel power plants in the US, prepared for United States Department of Energy, Ofce of Energy Research, Ofce of Basic Energy Sciences, Carbon Dioxide Research Division, Washington, D.C. 20545. DOE/ CH/000162. DE85 004499. Under Contract No. DE-AC0276CH00016. Stevens, S.H., Pearce, J.M., and Rigg, A.A.J., 2001, Natural analogues for geologic storage of CO2, an integrated global research program. First National Conference on Carbon Sequestration U.S. Department of Energy National Energy Technology Laboratory, May 15 17, 2001, Washington, DC. Sybe Grnvold M., Falk-Pedersen, O., Imai, N. and Ishida, K., 2005, KPS membrane contactor modlule combined with Kansai/MHI advanced solvent, KS-1 for CO2 Separation from Combustion Flue Gases, Carbon Dioxide Capture for Storage in Deep Geologic Formations- Resutls from the CO2 Capture Project. Capture and Separation of Carbon Dioxide from Combustion Souces. Volume 1, 137155 (Elsevier). Sundnes, A., 1998, Process for generating power and/or heat comprising a mixed conducting membrane reactor, International Patent number WO98/55394, Dec 1998. Sundkvist, S.G., Klang, A., Sjodin, M., Wilhelmsen, K., Asen, K., Tintinelli, A., McCahey, S. and Ye, H, 2005, AZEP gas turbine combined cycle power plantsthermal optimisation and LCA analysis, in Wilson, M., Morris, T., Gale, J. and Thambimuthu, K. (eds). Proceedings of 7th International Conference on Greenhouse. Gas Control Technologies. Volume II, Papers, Posters and Panel Discussion (Elsevier Science, Oxford, UK) (in press). Svensson, R., Odernberger, M., Johhsson, F. and Stromberg L, 2004, Transportation systems for CO2- application to carbon capture and storage, Energy Conversion and Management, 45: 23432353. Tan, Y., Douglas, M.A., Croiset, E. and Thambimuthu, K.V, 2002, CO2 capture using oxygen enhanced combustion strategies for natural gas power plants, Fuel, 81: 1007 1016.
763
Todd, D.M. and Battista, R.A., 2001, Demonstrated applicability of hydrogen fuel for gas turbines, 4th European Gasication Conference, 11 13 April, Noordwijk, Netherlands. Torp, T.A., 2004, Underground CO2 storage one of possible mitigation options? OSPAR Workshop, Trondheim, 25 Oct 2004, Impact of Placement of CO2 in the Maritime Area. Turton, R., Bailie, R.C., Whiting, W.B. and Shaeiwitz, J.A., 2003, Analysis, Synthesis and Design of Chemical Processes, 2nd Edition (Prentice Hall). Van der Sluijs, J.P, Hendriks, C.A. and Blok, K. 1992, Feasibility of polymer membranes for carbon dioxide recovery from ue gases, Energy Conversion Management, 33(58): 429436. Van de Burgt, W., 2004, Tophat, a smart way to get over 60% efciency in a simple cycle, Modern Power Systems, August 2004, 1922. Vattenfall Commits to CCS Plant, Power In Europe, 23 May 2005. Vunjak-Novakovic, G., Kim, Y., Wu, X., Berzin, I. and Merchuk, J.C., 2005, Air-lift bioreactors for algal growth on ue gas: Mathematical Modelling and Pilot Plant Studies, Ind Eng Chem Res, 44(16): 6154 6163. West, J.M., 1974, Design and operation of a supercritical CO2 pipelinecompression system, SACROC unit, Scurry County, Texas, Society of Petroleum Engineers Permian Basin Oil and Gas Recovery Conference, paper SPE 4804. White, C.M., Strazisar, B.R., Granite, E.J., Hoffman, J.S. and Pennline, H.W., 2003, Separation and capture of CO2 from large stationary sources and sequestration in geological formationscoalbeds and deep saline aquifers. Journal Air and Waste Management, 53: 645 715. Wilkinson, M.B. and Clarke, S.C., 2002, Hydrogen fuel production, advanced syngas technology screening study, 14th World Hydrogen Energy Conference, June 914, 2002, Montreal, Canada. Wilkinson, M.B., Simmonds, M., Allam, R.J. and White, V. 2003a, Oxyfuel conversion of heaters and boilers for CO2 capture, 2nd Annual Conf on Carbon Sequestration, Virginia (USA), May 2003. Wilkinson, M.B., Boden, J.C., Gilmartin, T., Ward, C., Cross, D.A., Allam, R.J. and Ivens, N.W., 2003b, CO2 capture from oil renery process heaters through oxyfuel combustion, Greenhouse Gas Control Technologies, Proc. of the 6th International Conference on Greenhouse Gas Control Technologies (GHGT-6), 1 4 Oct 2002, Kyoto, Japan, Gale, J. and Kaya, Y. (eds). Elsevier Science Ltd, Oxford, UK, 69 74. Wilson, M., Tontiwachwuthikul, P., Chakma, A., Idem, R., Veawab, A., Aroonwilas, A., Gelowitz, D., Barrie, J. and Mariz, C., 2004, Test results from a CO2 extraction pilot plant at boundary dam coal-red power station, Energy, 29: 12591267. Wotzak, G.P., Shilling, N.Z., Simons, G. and Yackly, K.A., 2005, An evaluation of conversion of gas turbines to hydrogen fuel, in Thomas, D.C. (ed.) Carbon Dioxide for Storage in Deep Geologic FormationsResults from the CO2 Capture Project. Volume 1 Capture and Separation of Carbon Dioxide from Combustion Sources. Yeh A.C. and Bai, H., 1999, Comparison of ammonia and monoethanolamine solvents to reduce CO2 greenhouse gas emissions, Sc. Total Environment, 228: 121 133. Yeh, J.T., Pennline, H.W. and Resnik, K.P., 2002, Aqua ammonia process for simulatenous reduction of CO2, SO2, NOx, Presented at the 19th Annual International Pittsburgh Coal Conference, Pittsburg, PA. Zafar, Q., Mattisson, T. and Gevert, B., 2005, Integrated hydrogen and power production with CO2 capture using chemical-looping reformingredox reactivity of particles of CuO, Mn2O3, NiO, and Fe2O3 using SiO2 as a support, Industrial and Engineering Chemistry Research, 44(10): 34853496. Zheng, X.Y., Diao, Y.F., He, B.S., Chen, C.H., Xu, X.C. and Feng, W., 2003, Carbon dioxide recovery from ue gases by ammonia scrubbing. Greenhouse Gas Control Technologies, Proc. of the 6th International Conference on Greenhouse Gas Control Technologies (GHGT-6), 14 Oct. 2002, Kyoto, Japan, Gale, J. and Kaya, Y. (eds). Elsevier Science Ltd, Oxford, UK, 193 200. Zheng, L. and Furinsky, E., 2005, Comparison of Shell, Texaco, BGL, and KRW gasiers as part of IGCC plant computer simulations, Energy Conversion and Management, 46(1112): 17671779.
ACKNOWLEDGEMENT
Valuable recommendations on literature sources and comments on earlier drafts were received from Gelein de Koeijer. The manuscript was received 9 November 2005 and accepted for publication after revision 13 February 2006.

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CO2 CAPTURE AND STORAGE Closing the Knowing Doing Gap

Figure 1. Global CO2 emissions in 2001 (IEA).

CO2 CAPTURE AND STORAGE

Figure 3. Main research directions for CCS.

Associated with import of electricity or (other products) for example.

CO2 CAPTURE AND STORAGE

1.5 million 12 million

8.7 million 6 million 2.5 million

2.9 million 22.2 million 1 billion US 3.4 million Canadian $

20042009 20042009 20032006

Storage Storage Storage

20042007 20042009 20062015 20022012

CO2 injection into deep coal beds

Storage Storage Storage

Figure 4. Main CO2 capture routes (from CCP12).

CO2 CAPTURE AND STORAGE

Figure 5. Typical owsheet for CO2 capture using MEA.

Power: 0.711.07 2.7 3.3 (0.620.76) 47 50%

Power: 0.510.61 2.73.3 (0.620.76) 3436%

CO2 CAPTURE AND STORAGE

Figure 6. Post-combustion research directions.

Figure 7. The Combicap# cycle (Lyngheim et al., 2004).

Figure 8. Oxyfuel research directions.

In addition to 2% N2, 1% Argon and approximately 1% O2 and SO2.

CO2 CAPTURE AND STORAGE

Working uid Air

Chemical looping combustion

Figure 9. Pre-combustion research directions.

CO2 CAPTURE AND STORAGE

1.329 2.151 4.682 2.749 6.8 1.47

1034 1076 2067 1495 1748 1919 1089

CO2 CAPTURE AND STORAGE

Figure 10. CO2 injection at the Sleipner Field.

Data along the three geometric dimensions plus time-interval data.

CO2 CAPTURE AND STORAGE

CO2 CAPTURE AND STORAGE

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Power: 0.711.07 2.7 3.3 (0.620.76) 47 50%

Power: 0.510.61 2.73.3 (0.620.76) 3436%