Coal steam Coal IGCC Coal IGCC cycle no GE no Shell no capture capture capture

Coal post Coal post Coal IGCC Coal IGCC Coal Gas no combustion combustion GE capture Shell oxyfuel capture Fluor MHI capture

Gas post Gas post Gas pre- Gas combustion combustion combustion oxyfuel Fluor MHI

Figure 3.6 Thermal efficiencies of power plants with and without CO2 capture, % LHV-basis (Source data: Davison 2005, IEA GHG 2004, IEA

a. The efficiencies are based on a standard set of plant design criteria (IEA GHG, 2004).

b. The coal steam cycle plants, including the post-combustion capture and oxy-fuel plants, are based on ultra-supercritical steam (29MPa, 600C superheat, 620C reheat). The IGCC and natural gas pre- and post-combustion capture plants are based on GE 9FA gas turbine combined cycles. The natural gas oxy-fuel plant is based on a CO2 recycle gas turbine, as shown in Figure 3.10, with different operating pressures and temperatures but similar mechanical design criteria to that of the 9FA.

c. Data are presented for two types of post-combustion capture solvent: MEA (Fluor plant designs) and KS-1 (MHI plant designs). The solvent desorption heat consumptions are 3.2 and 2.7 MJ/kgCO2 captured respectively for the coal plants and 3.7 and 2.7 MJ kg-1 for the natural gas plants.

d. Data are presented for IGCC plants based on two types of gasifier: the Shell dry feed/heat recovery boiler type and the GE (formerly Texaco) slurry feed water quench type.

e. The natural gas pre-combustion capture plant is based on partial oxidation using oxygen.

f. The oxy-fuel plants include cryogenic removal of some of the impurities from the CO2 during compression. Electricity consumption for oxygen production by cryogenic distillation of air is 200 kWh/ tO2 at atmospheric pressure for the coal plant and 320 kWh/ tO2 at 40 bar for the natural gas plant. Oxygen production in the IGCC and natural gas pre-combustion capture plants is partially integrated with the gas turbine compressor, so comparable data cannot be provided for these plants.

g. The percentage CO2 capture is 85-90% for all plants except the natural gas oxy-fuel plant which has an inherently higher percentage capture of 97%. 2 Effluents

As a result of decomposition of amines, effluents will be created, particularly ammonia and heat-stable salts. Rao and Rubin (2002) have estimated these emissions for an MEA-based process based on limited data. In such processes, heat stable salts (solvent decomposition products, corrosion products etc.) are removed from the solution in a reclaimer and a waste stream is created and is disposed of using normal HSE (Health, Safety and Environmental) practices. In some cases, these reclaimer bottoms may be classified as a hazardous waste, requiring special handling (Rao and Rubin, 2002). Also a particle filter and carbon filter is normally installed in the solvent circuit to remove byproducts. Finally, some solvent material will be lost to the environment through evaporation and carry over in the absorber, which is accounted for in the solvent consumption. It is expected that acid gases other than CO2, which are still present in the flue gas (SOx and NO2) will also be absorbed in the solution. This will lower the concentration of these components further and even the net emissions in some cases depending on the amount of additional energy use for CO2 capture (see Tables 3.4 and 3.5). As SO2-removal prior to CO2-removal is very likely in coal-fired plants, this will lead to the production of a waste or byproduct stream containing gypsum and water from the FGD unit.

3.3.3 Emerging technologies Other absorption process

Various novel solvents are being investigated, with the object of achieving a reduced energy consumption for solvent regeneration (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).

Besides novel solvents, novel process designs are also currently becoming available (Leites et al. 2003). Research is also being carried out to improve upon the existing practices and packing types (Aroonwilas et al., 2003). Another area of research is to increase the concentration levels of aqueous MEA solution used in absorption systems as this tends to reduce the size of equipment used in capture plants (Aboudheir et al., 2003). Methods to prevent oxidative degradation of MEA by de-oxygenation of the solvent solutions are also being investigated (Chakravarti et al., 2001). In addition to this, the catalytic removal of oxygen in flue gases from coal firing has been suggested (Nsakala et al., 2001) to enable operation with promising solvents sensitive to oxygen.

Coal post Coal post comb. Fluor comb. MHI

Coal IGCC Coal IGCC Coal oxyfuel Gas post Gas post Gas pre- Gas oxyfuel GE Shell comb. Fluor comb. MHI combustion

H CO2 compression and purification

■ O2 production and power plant impacts

CH Fuel gas processing and related impacts

CO2 separation

Figure 3.7 Percentage increase in fuel use per kWh of electricity due to CO2 capture, compared to the same plant without capture (Source data:

Davison, 2005; IEA GHG, 2004; IEA GHG, 2003; IEA GHG, 2000b; Dillon et al., 2005).

a. The increase in fuel required to produce a kWh of electricity is calculated by comparing the same type of plant with and without capture. The increase in fuel consumption depends on the type of baseline plant without capture. For example, the increase in energy consumption for a GE IGCC plant with capture compared to a coal steam cycle baseline plant without capture would be 40% as opposed to the lower value shown in the figure that was calculated relative to the same type of baseline plant without capture.

b. The direct energy consumptions for CO2 separation are lower for pre-combustion capture than for post-combustion capture, because CO2 is removed from a more concentrated, higher pressure gas, so a physical rather than a chemical solvent can be used.

c. The 'Fuel gas processing and related impacts' category for IGCC includes shift conversion of the fuel gas and the effects on the gas turbine combined cycle of removal of CO2 from the fuel gas and use of hydrogen as a fuel instead of syngas. For natural gas pre-combustion capture this category also includes partial oxidation/steam reforming of the natural gas.

d. The energy consumption for CO2 compression is lower in pre-combustion capture than in post-combustion capture because some of the CO2 leaves the separation unit at elevated pressure.

e. The energy consumption for CO2 compression in the oxy-fuel processes depends on the composition of the extracted product, namely 75% by volume in the coal-fired plant and 93% by volume in the gas fired plant. Impurities are cryogenically removed from the CO2 during compression, to give a final CO2 purity of 96% by volume. The energy consumption of the cryogenic CO2 separation unit is included in the CO2 compression power consumption.

f. The 'Oxygen production and power plant impacts' category for oxy-fuel processes includes the power consumption for oxygen production and the impacts of CO2 capture on the rest of the power plant, that is excluding CO2 compression and purification. In the coal-fired oxy-fuel plant, the efficiency of the rest of the power plant increases slightly, for example due to the absence of a flue gas desulphurization (FGD) unit. The efficiency of the rest of the gas fired oxy-fuel plant decreases because of the change of working fluid in the power cycle from air to recycled flue gas. Adsorption process

In the adsorption process for flue gas CO2 recovery, molecular sieves or activated carbons are used in adsorbing CO2. Desorbing CO2 is then done by the pressure swing operation (PSA) or temperature swing operation (TSA). Most applications are associated with pressure swing adsorption (Ishibashi et al., 1999 and Yokoyama, 2003). Much less attention has been focused on CO2 removal via temperature swing adsorption, as this technique is less attractive compared to PSA due to the longer cycle times needed to heat up the bed of solid particles during sorbent regeneration. For bulk separations at large scales, it is also essential to limit the length of the unused bed and therefore opt for faster cycle times.

Adsorption processes have been employed for CO2 removal from synthesis gas for hydrogen production (see Section It has not yet reached a commercial stage for CO2 recovery from flue gases. The following main R&D activities have been conducted:

• Study of CO2 removal from flue gas of a thermal power plant by physical adsorption (Ishibashi et al., 1999);

• Study of CO2 removal from flue gas of a thermal power plant by a combined system with pressure swing adsorption and a super cold separator (Takamura et al., 1999);

• Pilot tests on the recovery of CO2 from a coal and oil fired power plant, using pressure temperature swing adsorption (PTSA) and an X-type zeolite as an adsorbent (Yokoyama, 2003).

Pilot test results of coal-fired flue gas CO2 recovery by adsorption processes show that the energy consumption for capture (blowers and vacuum pumps) has improved from the original 708 kWh/tCO2 to 560 kWh/tCO2. An energy consumption of 560 kWh/tCO2 is equivalent to a loss corresponding to 21% of the energy output of the power plant. Recovered CO2 purity is about 99.0% by volume using two stages of a PSA and PTSA system (Ishibashi et al., 1999).

It can be concluded that based on mathematical models and data from pilot-scale experimental installations, the design of a full-scale industrial adsorption process might be feasible. A serious drawback of all adsorptive methods is the necessity to treat the gaseous feed before CO2 separation in an adsorber. Operation at high temperature with other sorbents (see Section can circumvent this requirement (Sircar and Golden, 2001). In many cases gases have to be also cooled and dried, which limits the attractiveness of PSA, TSA or ESA (electric swing adsorption) vis-à-vis capture by chemical absorption described in previous sections. The development of a new generation of materials that would efficiently adsorb CO2 will undoubtedly enhance the competitiveness of adsorptive separation in a flue gas application. Membranes

Membrane processes are used commercially for CO2 removal from natural gas at high pressure and at high CO2 concentration (see Section 3.2.2). In flue gases, the low CO2 partial pressure difference provides a low driving force for gas separation. The removal of carbon dioxide using commercially available polymeric gas separation membranes results in higher energy penalties on the power generation efficiency compared to a standard chemical absorption process (Herzog et al., 1991, Van der Sluijs et al., 1992 and Feron, 1994). Also, the maximum percentage of CO2 removed is lower than for a standard chemical absorption processes. Improvements can be made if more selective membranes become available, such as facilitated membranes, described below.

The membrane option currently receiving the most attention is a hybrid membrane - absorbent (or solvent) system. These systems are being developed for flue gas CO2 recovery. Membrane/solvent systems employ membranes to provide a very high surface area to volume ratio for mass exchange between a gas stream and a solvent resulting in a very compact system. This results in a membrane contactor system in which the membrane forms a gas permeable barrier between a liquid and a gaseous phase. In general, the membrane is not involved in the separation process. In the case of porous membranes, gaseous components diffuse through the pores and are absorbed by the liquid; in cases of non-porous membranes they dissolve in the membrane and diffuse through the membrane. The contact surface area between gas and liquid phase is maintained by the membrane and is independent of the gas and liquid flow rate. The selectivity of the partition is primarily determined by the absorbent (solvent). Absorption in the liquid phase is determined either by physical partition or by a chemical reaction.

The advantages of membrane/solvent systems are avoidance of operational problems occurring in conventional solvent absorption systems (see Section where gas and liquid flows are in direct contact. Operational problems avoided include foaming, flooding entrainment and channelling, and result in the free choice of the gas and liquid flow rates and a fixed interface for mass transfer in the membrane/solvent system. Furthermore, the use of compact membranes result in smaller equipment sizes with capital cost reductions. The choice of a suitable combination of solvent and membrane material is very important. The material characteristics should be such that the transfer of solvent through the membrane is avoided at operating pressure gradients of typically 50-100 kPa, while the transfer of gas is not hindered. The overall process configuration in terms of unit operations would be very similar to a conventional chemical absorption/desorption process (see Figure 3.4). Membrane/solvent systems can be both used in the absorption as well as in the desorption step. Feron and Jansen (2002) and Falk-Pedersen et al. (1999) give examples of suitable membrane/solvent systems.

Research and development efforts have also been reported in the area of facilitated transport membranes. Facilitated transport membranes rely on the formation of complexes or reversible chemical reactions of components present in a gas stream with compounds present in the membrane. These complexes or reaction products are then transported through the membrane. Although solution and diffusion still play a role in the transport mechanism, the essential element is the specific chemical interaction of a gas component with a compound in the membrane, the so-called carrier. Like other pressure driven membrane processes, the driving force for the separation comes from a difference in partial pressure of the component to be transported. An important class of facilitated transport membranes is the so-called supported liquid membrane in which the carrier is dissolved into a liquid contained in a membrane. For CO2 separations, carbonates, amines and molten salt hydrates have been suggested as carriers (Feron, 1992). Porous membranes and ion-exchange membranes have been employed as the support. Until now, supported liquid membranes have only been studied on a laboratory scale. Practical problems associated with supported liquid membranes are membrane stability and liquid volatility. Furthermore, the selectivity for a gas decreases with increasing partial pressure on the feed side. This is a result of saturation of the carrier in the liquid. Also, as the total feed pressure is increased, the permeation of unwanted components is increased. This also results in a decrease in selectivity. Finally, selectivity is also reduced by a reduction in membrane thickness. Recent development work has focused on the following technological options that are applicable to both CO2/N2 and CO2/H2 separations:

• Amine-containing membranes (Teramoto et al., 1996);

• Membranes containing potassium carbonate polymer gel membranes (Okabe et al., 2003);

• Membranes containing potassium carbonate-glycerol

• Dendrimer-containing membranes

(Kovvali and Sirkar, 2001).

• Poly-electrolyte membranes (Quinn and Laciak, 1997);

Facilitated transport membranes and other membranes can also be used in a preconcentration step prior to the liquefaction of CO2 (Mano et al., 2003). Solid sorbents

There are post-combustion systems being proposed that make use of regenerable solid sorbents to remove CO2 at relatively high temperatures. The use of high temperatures in the CO2 separation step has the potential to reduce efficiency penalties with respect to wet-absorption methods. In principle, they all follow the scheme shown in Figure 3.2a, where the combustion flue gas is put in contact with the sorbent in a suitable reactor to allow the gas-solid reaction of CO2 with the sorbent (usually the carbonation of a metal oxide). The solid can be easily separated from the gas stream and sent for regeneration in a different reactor. Instead of moving the solids, the reactor can also be switched between sorption and regeneration modes of operation in a batch wise, cyclic operation. One key component for the development of these systems is obviously the sorbent itself, that has to have good CO2 absorption capacity and chemical and mechanical stability for long periods of operation in repeated cycles. In general, sorbent performance and cost are critical issues in all post-combustion systems, and more elaborate sorbent materials are usually more expensive and will have to demonstrate outstanding performance compared with existing commercial alternatives such as those described in 3.3.2.

Solid sorbents being investigated for large-scale CO2 capture purposes are sodium and potassium oxides and carbonates (to produce bicarbonate), usually supported on a solid substrate (Hoffman et al., 2002; Green et al., 2002). Also, high temperature Li-based and CaO-based sorbents are suitable candidates. The use of lithium-containing compounds (lithium, lithium-zirconia and lithium-silica oxides) in a carbonation-calcination cycle, was first investigated in Japan (Nakagawa and Ohashi, 1998). The reported performance of these sorbents is very good, with very high reactivity in a wide range of temperatures below 700°C, rapid regeneration at higher temperatures and durability in repeated capture-regeneration cycles. This is essential because lithium is an intrinsically expensive material.

The use of CaO as a regenerable CO2 sorbent has been proposed in several processes dating back to the 19th century. The carbonation reaction of CaO to separate CO2 from hot gases (T > 600°C) is very fast and the regeneration of the sorbent by calcining the CaCO3 into CaO and pure CO2 is favoured at T > 900°C (at a partial pressure of CO2 of 0.1 MPa). The basic separation principle using this carbonation-calcination cycle was successfully tested in a pilot plant (40 tonne d-1) for the development of the Acceptor Coal Gasification Process (Curran et al., 1967) using two interconnected fluidized beds. The use of the above cycle for a post-combustion system was first proposed by Shimizu et al. (1999) and involved the regeneration of the sorbent in a fluidized bed, firing part of the fuel with O2/CO2 mixtures (see also Section 3.4.2). The effective capture of CO2 by CaO has been demonstrated in a small pilot fluidized bed (Abanades et al., 2004a). Other combustion cycles incorporating capture of CO2 with CaO that might not need O2 are being developed, including one that works at high pressures with simultaneous capture of CO2 and SO2 (Wang et al., 2004). One weak point in all these processes is that natural sorbents (limestones and dolomites) deactivate rapidly, and a large make-up flow of sorbent (of the order of the mass flow of fuel entering the plant) is required to maintain the activity in the capture-regeneration loop (Abanades et al., 2004b). Although the deactivated sorbent may find application in the cement industry and the sorbent cost is low, a range of methods to enhance the activity of Ca-based CO2 sorbents are being pursued by several groups around the world. 3.3.4 Status and outlook

Virtually all the energy we use today from carbon-containing fuels is obtained by directly burning fuels in air. This is despite many decades of exploring promising and more efficient alternative energy conversion cycles that rely on other fuel processing steps prior to fuel combustion or avoiding direct fuel combustion (see pre-combustion capture - Section 3.5). In particular, combustion-based systems are still the competitive choice for operators aiming at large-scale production of electricity and heat from fossil fuels, even under more demanding environmental regulations, because these processes are reliable and well proven in delivering electricity and heat at prices that often set a benchmark for these services. In addition, there is a continued effort to raise the energy conversion efficiencies of these systems through advanced materials and component development. This will allow these systems to operate at higher temperature and higher efficiency.

As was noted in Section 3.1, the main systems of reference for post-combustion capture are the present installed capacity of coal and natural gas power plants, with a total of 970 GWe subcritical steam and 155 GW of supercritical/ultra-supercritical steam-based pulverized coal fired plants, 339 GW of natural gas combined cycle, 333 GWe natural gas steam-electric power plants and 17 GWe of coal-fired, circulating, fluidized-bed combustion (CFBC) power plants. An additional capacity of 454 GWe of oil-based power plant, with a significant proportion of these operating in an air-firing mode is also noted (IEA WEO, 2004 and IEA CCC, 2005). Current projections indicate that the generation efficiency of commercial, pulverized coal fired power plants based on ultra-supercritical steam cycles would exceed 50% lower heating value (LHV) over the next decade (IEA, 2004), which will be higher than efficiencies of between 36 and 45% reported for current subcritical and supercritical steam-based plants without capture (see Section 3.7). Similarly, natural gas fired combined cycles are expected to have efficiencies of 65% by 2020 (IEA GHG, 2002b) and up from current efficiencies between 55 and 58% (see Section 3.7). In a future carbon-constrained world, these independent and ongoing developments in power cycle efficiencies will result in lower CO2-emissions per kWh produced and hence a lower loss in overall cycle efficiency when post-combustion capture is applied.

There are proven post-combustion CO2 capture technologies based on absorption processes that are commercially available at present . They produce CO2 from flue gases in coal and gas-fired installations for food/beverage applications and chemicals production in capacity ranges between 6 and 800 tCO2 d-1. They require scale up to 20-50 times that of current unit capacities for deployment in large-scale power plants in the 500 MWe capacity range (see Section 3.3.2). The inherent limitations of currently available absorption technologies when applied to post-combustion capture systems are well known and their impact on system cost can be estimated relatively accurately for a given application (see Section 3.7). Hence, with the dominant role played by air- blown energy conversion processes in the global energy infrastructure, the availability of post-combustion capture systems is important if CO2 capture and storage becomes a viable climate change mitigation strategy.

The intense development efforts on novel solvents for improved performance and reduced energy consumption during regeneration, as well as process designs incorporating new contacting devices such as hybrid membrane-absorbent systems, solid adsorbents and high temperature regenerable sorbents, may lead to the use of more energy efficient postcombustion capture systems. However, all these novel concepts still need to prove their lower costs and reliability of operation on a commercial scale. The same considerations also apply to other advanced CO2 capture concepts with oxy-fuel combustion or pre-combustion capture reviewed in the following sections of this chapter. It is generally not yet clear which of these emerging technologies, if any, will succeed as the dominant commercial technology for energy systems incorporating CO2 capture.

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