C02 to compression

Figure 3.9 Principle flow scheme of the advanced zero emission power plant cycle. Advanced zero emission power plant The advanced zero emission power plant (or AZEP as outlined in Figure 3.9; Griffin et al., 2003) is an indirect heating gas turbine cycle that incorporates a high-temperature oxygen transport membrane, operating at about 800°C -1000°C (see Section This process uses a standard air-based gas turbine in a combined cycle arrangement. Three process steps take place in a reactor system that replaces the combustion chamber of a standard gas turbine: 1) separation of oxygen from hot air using the membrane and transport to the combustion section; 2) combustion and 3) heat exchange from the combustion products to the compressed air.

A net efficiency for advanced zero emission power cycle of around 49-50% LHV is claimed including CO2 compression for transport. In order to get full advantage of the potential of the most advanced gas turbines, which have inlet temperatures of 1300°C-1400°C, an afterburner fired with natural gas in air may be added behind the reactor system. The efficiency then climbs up to 52% but now 15% of the CO2 generated by combustion is released at the stack and is not captured.

3.4.3 Oxy-fuel direct heating - gas turbine cycle

Oxy-fuel combustion takes place in a pressurized CO2-rich recirculating stream in a modified gas turbine. The hot gas is expanded in the turbine producing power. The turbine exhaust is cooled to provide heat for a steam cycle and water vapour is condensed by further cooling. The CO2-rich gas is compressed in the compressor section. The net CO2-rich combustion product is removed from the system. Only natural gas, light hydrocarbons and syngas (CO + H2) can be used as fuel. Cycle description and performance Figure 3.10 shows how a gas turbine can be adapted to run with oxy-fuel firing using CO2 as a working fluid. Exhaust gas leaving the heat recovery steam generator is cooled to condense water. The net CO2 product is removed and the remaining gas is recycled to the compressor. Suitable fuels are natural gas, light to medium hydrocarbons or (H2 + CO) syngas, which could be derived from coal. The use of CO2 as the working fluid in the turbine will necessitate a complete redesign of the gas turbine (see Section A recent study (Dillon et al., 2005) gives an overall efficiency including CO2 compression of 45%.

Two typical variants of this configuration are the so-called Matiant and Graz cycles (Mathieu, 2003; Jericha et al, 2003). The Matiant cycle uses CO2 as the working fluid, and consists of features like intercooled compressor and turbine reheat. The exhaust gas is preheating the recycled CO2 in a heat exchanger. The CO2 generated in combustion is extracted from the cycle behind the compressor. The net overall LHV efficiency is expected to be 45-47% and can increase above 50% in a combined cycle configuration similar to that shown in Figure 3.10. The Graz cycle consists of an integrated gas turbine and steam turbine cycle. A net LHV efficiency of above 50% has been calculated for this cycle (Jericha et al., 2003).

A recent comprehensive review of gas turbine cycles with CO2 capture provides efficiencies of different cycles on a common basis (Kvamsdal et al., 2004). The CO ./oxy-fuel gas turbine

In existing gas turbines the molecular weight of the gases in the compressor and turbine are close to that of air (28.8). In the case of oxy-fuel combustion with CO2-recycle the compressor fluid molecular weight is about 43 and about 40 in the turbine. The change in working fluid from air to a CO2-rich gas results in a number of changes in properties that are of importance for the design of the compressor, combustor and the hot gas path including the turbine:

• The specific heat ratio is lower than air resulting in a lower temperature change on adiabatic compression or expansion. An oxy-fuel gas turbine in a combined cycle has a higher optimal pressure ratio, typically 30 to 35 compared to 15

Pressurized oxygen


Pressurized oxygen


C02to compression >

Figure 3.10 Principle of the oxy-fuel gas turbine combined cycle. Exhaust gas is recycled, compressed and used in the combustion chamber to control the temperature entering the turbine.

C02to compression >

about 90% recycle

Figure 3.10 Principle of the oxy-fuel gas turbine combined cycle. Exhaust gas is recycled, compressed and used in the combustion chamber to control the temperature entering the turbine.

to 18 used with air in a combined cycle system. With the highest turbine inlet temperature consistent with material limitations, the rather high-pressure ratio results in an exhaust gas temperature of about 600°C, which is optimal for the steam cycle.

These changes in the fundamental properties of the working fluid will have a significant impact on gas turbine components, requiring completely new designs of compressors, combustors (to account for aerodynamic changes and acoustic feedbacks) and hot gas path (O2 partial pressure must be low in oxy-fuel systems but it is also important to avoid reducing conditions for the materials of the turbine or the change to materials allowing much lower O2 partial pressures).

3.4.4 Oxy-fuel direct heating - steam turbine cycle

In an oxy-fuel steam turbine cycle, water is pressurized as a liquid and is then evaporated, heated by the direct injection and combustion of a fuel with pure oxygen and expanded in a turbine. Most of the water in the low pressure turbine exhaust gas is cooled and condensed, prior to pumping back to a high pressure while the CO2 produced from combustion is removed and compressed for pipeline transport. A variant of this cycle in which the heat is provided by burning natural gas fuel in-situ with pure oxygen was proposed by Yantovskii et al. (1992).

The direct combustion of fuel and oxygen has been practised for many years in the metallurgical and glass industries where burners operate at near stoichiometric conditions with flame temperatures of up to 3500°C. A water quenched H2/O2 burner capable of producing 60 tonne h-1, 6 MPa super heated steam was demonstrated in the mid-1980s (Ramsaier et al., 1985). A

recent development by Clean Energy Systems incorporating these concepts where a mixture of 90 % by volume superheated steam and 10% CO2 is produced at high temperature and pressure to power conventional or advanced steam turbines is shown in Figure 3.11. The steam is condensed in a low-pressure condenser and recycled, while CO2 is extracted from the condenser, purified and compressed. (Anderson et al., 2003 and Marin et al, 2003).

Plants of this type require a clean gaseous or liquid fuel and will operate at 20 to 50 MPa pressure. The steam plus CO2 generator is very compact. Control systems must be very precise as start-up and increase to full flow in a preheated plant can take place in less than 2 seconds. Precise control of this very rapid start was demonstrated (Ramsaier et al., 1985) in a 60 tonne steam h-1 unit. The Clean Energy Systems studies claim efficiencies as high as 55% with CO2 capture depending on the process conditions used.

The Clean Energy Systems technology can be initially applied with current steam turbines (565°C inlet temperature). The main technical issue is clearly the design of the steam turbines which could be used at inlet temperatures up to 1300°C by applying technology similar to that used in the hot path of gas turbines. The combustor itself (the 'gas generator') is adapted from existing rocket engine technology. In 2000, Clean Energy Systems proved the concept with a 110 kW pilot project conducted at the University of California Davis. A 20 MW thermal gas generator was successfully operated in a test run of the order of a few minutes in early 2003. A zero emissions demonstration plant (up to 6 MW electrical) is now on-line. US Department of Energy's National Energy Technology Laboratory designed the reheater (Richards, 2003) and NASA tested it in 2002. Much more technology development and demonstration

Figure 3.11 Principle of the Clean Energy Systems cycle. The combustion of the fuel and oxygen is cooled by injection of liquid-water, which is recycled in the process.

is needed on this proposed power cycle, but it shows significant potential for low capital cost and high efficiency.

3.4.5 Techniques and improvements in oxygen production

Oxygen is the key requirement for any oxy-fuel combustion system. It is also a key technology for pre-combustion CO2 capture (see Section 3.5). In the next paragraphs, existing large-scale O2 production methods are described first, followed by emerging concepts aimed at reducing the energy consumption and cost. Cryogenic oxygen production

The very large quantities of oxygen required for CO2 capture using the techniques of oxy-fuel combustion and pre-combustion de-carbonization can only be economically produced, at present, by using the established process of oxygen separation from air by distillation at cryogenic temperatures (Latimer, 1967). This is a technology that has been practiced for over 100 years.

In a typical cryogenic air separation plant (Castle, 1991; Figure 3.12), air is compressed to a pressure of 0.5 to 0.6 MPa and purified to remove water, CO2, N2O and trace hydrocarbons which could accumulate to dangerous levels in oxygen-rich parts of the plant, such as the reboiler condenser. Two or more switching fixed bed adsorbers are used, which can be regenerated by either temperature or pressure swing, using in each case, a low pressure waste nitrogen stream. The air is cooled against returning products (oxygen and nitrogen) in a battery of aluminium plate-fin heat exchangers and separated into pure oxygen and nitrogen fractions in a double distillation column, which uses aluminium packing.

Oxygen can be pumped as liquid and delivered as a high-pressure gas at up to 10 MPa. Pumped oxygen plants have largely replaced the oxygen gas compression systems. They have virtually identical power consumptions but in a pumped cycle, a high-pressure air booster compressor provides a means of efficiently vaporizing and heating the liquid oxygen stream to ambient temperature. Current plant sizes range up to 3500 tO2 d-1 and larger single train plants are being designed. Typical power consumption for the delivery of 95% O2 at low pressure (0.17 MPa, a typical pressure for an oxy-fuel application) is 200 to 240 kWh/tO2. There are numerous process cycle variations particularly for the production of oxygen at less than 97.5% purity which have been developed to reduce power and capital cost. Note that adsorption and polymeric membrane methods of air separation are only economic for small oxygen production rates. High temperature oxygen ion transport membranes Ceramic mixed metal oxides have been developed which exhibit simultaneous oxygen ion and electron conduction at

Figure 3.12a Oxygen production by distillation of liquid air.

Figure 3.12b A 3000 t day-1 oxygen plant (Courtesy of Air Products).

temperatures above 500°C and preferably above 700°C (Skinner and Kilner 2003; Bouwmeester and Van Laar, 2002; Dyer et al., 2000; Bredesen et al., 2004). Typical crystal structures which exhibit these properties include the perovskites and the brownmillerites. The selectivity of these materials for oxygen is infinite. The oxygen permeability is primarily controlled by the oxygen ion vacancies in the metal oxide lattice. A difference in oxygen partial pressure across the membrane will cause oxygen molecules to ionize on the ceramic surface and pass into the crystal structure while simultaneously on the permeate side of the membrane, the oxygen ions give up their electrons and leave the ceramic in the region of lower activity. The electron conduction path is through the metal ions in the lattice. Unlike conventional membranes, the flux through the ceramic is a function of the partial pressure ratio. In the technical literature, the engineered structures of these ceramic mixed metal oxides are referred to as ion transport membranes, ITM or oxygen transport membranes, OTM.

The oxygen transport membrane can be fabricated in the form of plain tubes or as hollow fins on a central collector tube (Armstrong et al., 2002). The finned elements are then mounted in tube sheets within a pressure vessel with high-pressure air flowing over the fins. There are several new concepts that have been proposed for using oxygen transport membranes in power cycles with CO2 capture. A prime example of an oxy-fuel gas turbine cycle that incorporates an oxygen transport membrane for oxygen production is the advanced zero emission power plant described in Section Another example is found in Sundnes (1998).

Development status

Oxygen transport membrane systems for oxygen production are currently in the early stages of development by at least two consortia receiving research funding from the US Department of Energy and the European Commission. The concept has now reached the pilot plant stage and projected cost, manufacturing procedures and performance targets for full size systems have been evaluated. Systems capable of large-scale production are projected to be available after industrial demonstration in about 7 years time (Armstrong et al., 2002).

3.4.6 Chemical looping combustion

Originally proposed by Richter and Knoche (1983) and with subsequent significant contributions by Ishida and Jin (1994), the main idea of chemical looping combustion is to split combustion of a hydrocarbon or carbonaceous fuel into separate oxidation and reduction reactions by introducing a suitable metal oxide as an oxygen carrier to circulate between two reactors (Figure 3.13). Separation of oxygen from air is accomplished by fixing the oxygen as a metal oxide. No air separation plant is required. The reaction between fuel and oxygen is accomplished in a second reactor by the release of oxygen from the metal oxide in a reducing atmosphere caused by the presence of a hydrocarbon or carbonaceous fuel. The recycle rate of the solid material between the two reactors and the average solids residence time in each reactor, control the heat balance and the temperature levels in each reactor. The effect of having combustion in two reactors compared to conventional combustion in a single stage is that the CO2 is not diluted with nitrogen gas, but is almost pure after separation from water, without requiring any extra energy demand and costly external equipment for CO2 separation.

Possible metal oxides are some oxides of common transitionstate metals, such as iron, nickel, copper and manganese (Zafar et al., 2005). The metal/metal oxide may be present in various forms, but most studies so far have assumed the use of particles with diameter 100-500 |im. In order to move particles between the two reactors, the particles are fluidized. This method also ensures efficient heat and mass transfer between the gases and the particles. A critical issue is the long-term mechanical and chemical stability of the particles that have to undergo repeated cycles of oxidation and reduction, to minimize the make-up requirement. When a chemical looping cycle is used in a gas turbine cycle, the mechanical strength for crushing and the filtration system is important to avoid damaging carry-over to the turbine.

The temperature in the reactors, according to available information in the literature, may be in the range 800°C-

Figure 3.13 The chemical looping combustion principle in a gas turbine cycle.

1200°C. NO formation at these typical operating temperatures will always be low. The fuel conversion in the reduction reactor may not be complete, but it is likely (Cho et al., 2002) that the concentrations of methane and CO when burning natural gas are very small. In order to avoid deposit of carbon in the reduction reactor, it is necessary to use some steam together with the fuel.

The chemical looping principle may be applied either in a gas turbine cycle with pressurized oxidation and reduction reactors, or in a steam turbine cycle with atmospheric pressure in the reactors. In the case of a gas turbine cycle, the oxidation reactor replaces the combustion chamber of a conventional gas turbine. The exothermic oxidation reaction provides heat for increasing the air temperature entering the downstream expansion turbine. In addition, the reduction reactor exit stream may also be expanded in a turbine together with steam production for power generation. The cooled low pressure CO2 stream will then be compressed to pipeline pressure. Another option is to generate steam using heat transfer surfaces in the oxidation reactor. Current circulating fluidized bed combustion technology operating at atmospheric pressure in both the oxidation and reduction stages necessitates the use of a steam turbine cycle for power generation. Using natural gas as fuel in a chemical looping combustion cycle which supplies a gas turbine combined cycle power plant and delivering CO2 at atmospheric pressure, the potential for natural gas fuel-to-electricity conversion efficiency is estimated to be in the range 45-50% (Brandvoll and Bolland, 2004). Work on chemical looping combustion is currently in the pilot plant and materials research stage.

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