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130 IPCC Special Report on Carbon dioxide Capture and Storage frame are predicting efficiencies above 50% (IEA, 2004) for plants using ultra-supercritical steam conditions. An increase in efficiency of more than 5% can therefore be expected for future oxy-fuel capture systems based on coal firing that could potentially match the best efficiencies realisable today for pulverized coal-fired plants without CO2 capture. Similarly, natural gas fired combined cycles will have efficiencies of 65% in 2020 (IEA GHG, 2000b and up from current efficiencies between 55 and 58%), which will enable plant efficiencies for natural gas fired oxy-fuel cycles with CO2 capture above 50%. The energy penalty for producing oxygen is by far the most important cause for reduced efficiency in an oxy-fuel cycle compared to a conventional power plant. Partial oxidation CxHy + x/2O2 ↔ xCO + (y/2)H2 ∆H –ve (2) This is followed by the ‘shift’ reaction to convert CO to CO2 by the addition of steam (reaction 3): Water Gas Shift Reaction CO + H2O ↔ CO2 + H2 ∆H -41 kJ mol-1 (3) Current technology development envisages very high efficiency separation of NOx, SOx, and Hg, as part of the CO2 compression and purification system. Improved separation efficiencies of these contaminants are possible based on further process and heat integration in the power cycle. Finally, the CO2 is removed from the CO2/H2 mixture. The concentration of CO2 in the input to the CO2/H2 separation stage can be in the range 15-60% (dry basis) and the total pressure is typically 2-7 MPa. The separated CO2 is then available for storage. Current cryogenic oxygen technology is showing continuing cost reduction based on improved compressor efficiencies, more efficient process equipment and larger scale plants. The new high temperature oxygen membrane could significantly improve power generation efficiency and reduce capital cost. It is possible to envisage two applications of pre-combustion capture. The first is in producing a fuel (hydrogen) that is essentially carbon-free. Although the product H2 does not need to be absolutely pure and may contain low levels of methane, CO or CO2, the lower the level of carbon-containing compounds, the greater the reduction in CO2 emissions. The H2 fuel may also contain inert diluents, such as nitrogen (when air is typically used for partial oxidation), depending on the production process and can be fired in a range of heaters, boilers, gas turbines or fuel cells. Future oxy-fuel demonstration plants could be based on retrofits to existing equipment such as process heaters and boilers, in order to minimize development costs and achieve early market entry. In this respect, power systems of reference for oxy-fuel combustion capture are mainly the steam-based pulverized coal and natural gas fired plants that currently represent up to 1468 GWe, or 40% (IEA WEO, 2004) of the existing global infrastructure (see also Section 3.1.2.3). Several demonstration units may be expected within the next few years particularly in Europe, USA, Canada and Australia where active research initiatives are currently underway. As these developments proceed and the technologies achieve market penetration they may become competitive relative to alternate options based on pre- and post-combustion CO2 capture. A significant incentive to the development of oxy-fuel combustion technology, as well as for pre- and post-combustion capture technologies, is the introduction of environmental requirements and/or fiscal incentives to promote CO2 capture and storage. Secondly, pre-combustion capture can be used to reduce the carbon content of fuels, with the excess carbon (usually removed as CO2) being made available for storage. For example, when using a low H:C ratio fuel such as coal it is possible to gasify the coal and to convert the syngas to liquid Fischer-Tropsch fuels and chemicals which have a higher H:C ratio than coal. In this section, we consider both of these applications. 3.5 Pre-combustion capture systems 3.5.1 Introduction A pre-combustion capture process typically comprises a first stage of reaction producing a mixture of hydrogen and carbon monoxide (syngas) from a primary fuel. The two main routes are to add steam (reaction 1), in which case the process is called ‘steam reforming’, or oxygen (reaction 2) to the primary fuel. In the latter case, the process is often called ‘partial oxidation’ when applied to gaseous and liquid fuels and ‘gasification’ when applied to a solid fuel, but the principles are the same. Steam reforming CxHy + xH2O ↔ xCO + (x+y/2)H2 ∆H +ve (1) This section reports on technologies for the production of H2 with CO2 capture that already exist and those that are currently emerging. It also describes enabling technologies that need to be developed to enhance the pre-combustion capture systems for power, hydrogen or synfuels and chemicals production or combination of all three. 3.5.2 Existing technologies Steam reforming is the dominant technology for hydrogen production today and the largest single train plants produce up to 480 tH2 d-1. The primary energy source is often natural gas, Then the process is referred to as steam methane reforming (SMR), but can also be other light hydrocarbons, such as naphtha. The process begins with the removal of sulphur compounds from the feed, since these are poisons to the current nickel-based catalyst and then steam is added. The reforming reaction (1), which is endothermic, takes place over a catalyst at high temperature (800°C-900°C). Heat is supplied to the reactor tubes by burning part of the fuel (secondary fuel). The reformed gas is cooled in a waste heat boiler which generates the steam needed for the reactions and passed into the CO shift system. Shift reactors in one or two stages are used to convert most of the CO in the syngas to CO2 (Reaction 3, which is exothermic). 3.5.2.1 Steam reforming of gas and light hydrocarbonsPDF Image | CARBON DIOXIDE CAPTURE AND STORAGE
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