Niall R. McGlashan

Producing Hydrogen and Power Using Chemical Looping Combustion and Water-Gas Shift

A cycle capable of generating both hydrogen and power with ‘inherent’ carbon capture is proposed and evaluated. The cycle uses chemical looping combustion (CLC) to perform the primary energy release from a hydrocarbon, producing an exhaust of CO. This CO is mixed with steam and converted to H2 and CO2 using the water-gas shift reaction (WGSR). Chemical looping uses two reactions with a re-circulating oxygen carrier to oxidise hydrocarbons. The resulting oxidation and reduction stages are preformed in separate reactors — the oxidiser and reducer respectively, and this partitioning facilitates CO2 capture. In addition, by careful selection of the oxygen carrier, the equilibrium temperature of both redox reactions can be reduced to values below the current industry standard metallurgical limit for gas turbines. This means that the irreversibility associated with the combustion process can be reduced significantly, leading to a system of enhanced overall efficiency. The choice of oxygen carrier also affects the ratio of CO vs. CO2 in the reducer’s flue gas, with some metal oxide reduction reactions generating almost pure CO. This last feature is desirable if the maximum H2 production is to be achieved using the WGSR reaction. Process flow diagrams of one possible embodiment using a zinc based oxygen carrier are presented. To generate power, the chemical looping system is operated as part of a gas turbine cycle, combined with a bottoming steam cycle to maximise efficiency. The WGSR supplies heat to the bottoming steam cycle, as well as helping to raise the steam necessary to complete the reaction. A mass and energy balance of the chemical looping system, the WGSR reactor, steam bottoming cycle and balance of plant, is presented and discussed. The results of this analysis show that the overall efficiency of the complete cycle is dependant on the operating pressure in the oxidiser, and under optimum conditions, exceeds 75%.Copyright

Chemical Looping Combustion Using the Direct Combustion of Liquid Metal in a Gas Turbine Based Cycle

A combined cycle gas-turbine generating power and hydrogen is proposed and evaluated. The cycle embodies chemical looping combustion (CLC) and uses a Na based oxygen carrier. In operation, a stoichiometric excess of liquid Na is injected directly into the combustion chamber of a gas-turbine cycle, where it is burnt in compressed O 2 produced in an external air separation unit (ASU). The resulting combustion chamber exit stream consists of hot Na vapor and this is expanded in a turbine. Liquid Na 2 O oxide is also generated in the combustion process but this can be separated, readily, from the Na vapor and collects in a pool at the bottom of the reactor. To regenerate liquid Na from Na 2 O, and hence complete the chemical loop, a reduction reactor (the reducer) is fed with three streams: the hot Na 2 O from the oxidizer, the Na vapor (plus some entrained wetness) exiting a Na-turbine, and a stream of solid fuel, which is assumed to be pure carbon for simplicity. The sensible heat content of the liquid Na 2 O and latent and sensible heat of the Na vapor provide the heat necessary to drive the endothermic reduction reaction and ensure the reducer is externally adiabatic. The exit gas from the reducer consists of almost pure CO, which can be used to generate byproduct H 2 using the water-gas shift reaction. A mass and energy balance of the system is conducted assuming reactions reach equilibrium. The analysis allows for losses associated with turbomachinery; heat exchangers are assumed to operate with a finite approach temperature. However, pressure losses in equipment and pipework are assumed negligible-a reasonable assumption for this type of analysis that will still yield meaningful data. The analysis confirms that the combustion chamber exit temperature is limited by both first and second law considerations to a value suitable for a practical gas-turbine. The analysis also shows that the overall efficiency of the cycle, under optimum conditions and taking into account the work necessary to drive the ASU, can exceed 75%.

Carbon Capture and Reduced Irreversibility Combustion Using Chemical Looping

Power generation traditionally depends on combustion to ‘release’ the energy contained in fuels. Combustion is, however, an irreversible process and typically accounts for a quarter to a third of the lost work generation in power producing systems. The source of this irreversibility is the large departure from chemical equilibrium that occurs during the combustion of hydrocarbons. Chemical looping combustion (CLC) is a technology initially proposed as a means to reduce the lost work generation in combustion equipment. However, renewed interest has been shown in the technology since it also facilitates carbon capture. CLC works by replacing conventional “oxy-fuel” combustion with a two-step process. In the first, a suitable oxygen carrier (typically a metal) is oxidised using air. This results in an oxygen depleted air stream and a stream of metal oxide. The latter is then reduced in the second reaction step using a hydrocarbon fuel. The products of this second step are a stream of reduced metal, which is returned to the oxidation reaction, and a stream of CO2 and H2 O that can be separated easily. The thermodynamic benefits of CLC stem from the fact that the oxygen carrier is recirculated and can thus be chosen with a reasonable degree of freedom. This enables the chemistry to be optimised to reduce the lost work generation in the two reactors – the reactions can then be operated much closer to chemical equilibrium. It is widely accepted in the literature that a key issue in CLC is identifying the most effective oxygen carrier. However, most previous work appears to consider systems in which a solid phase metallic oxygen carrier is recirculated between two fluidised bed reactors. In the current paper, we explore the possibility of using liquid or gas phase reactions in the two reaction steps since it is hypothesised that these might be compatible with a wider range of fuels including coal. The paper, however, starts by reviewing the existing literature on CLC and the basic thermodynamics of a conceptual CLC power plant. The thermodynamic analysis is extended to include a general method for calculating the lost work generation in a given chemical reactor. Finally, this method is applied to the oxidation reaction of a proposed CLC reaction scheme.Copyright