Exergy analysis on combustion and energy conversion processes

When we consider exergy analysis on combustion and thermodynamic processes, we introduce another concept against energy analysis, which is supported by an evaluation of its temperature level. When a higher temperature energy than that an ambient level is taken into consideration, it can be put for some domestic or industrial purpose. A medium temperature energy of 30–60 °C is used for domestic heating, and a high temperature of 200 °C and above is suitable for power generation or process heating. Therefore, we study exergy concept supported by temperature level. When we discuss power generation, a high temperature energy of 1500 °C and above in combined cycle has a higher conversion efficiency than that of 500–600 °C in steam cycle. If we try to apply high temperature air combustion, a preheated air temperature of 1000 °C and above can be produced by exhaust heat recovery from stack gas, which has been developed as a new technology of energy conservation. In this study, the authors present an exergy analysis on combustion and energy conversion processes, which is based on the above-mentioned concept of exergy and energy supported by temperature level. When we discuss high temperature air combustion in furnace, this process shows a higher performance than that of the ambient air combustion. Furthermore, when we discuss the power generation and heat pump processes, the minimum ambient temperature would already be known for each season, and the conversion performance can be estimated by the maximum operating temperature in their cycles. So, the authors attempt to calculate the exergy and energy values for combustion, power generation and heat pump processes.     

Reactivity study on a novel hydrogen fueled chemical-looping combustion

In this paper the reactivity study on hydrogen fueled chemical-looping combustion, which is capable of making breakthrough in simultaneous contribution to the efficient use of energy and being environmentally benign, has been carried out by a thermogravimetric analyzer (TGA) and a fixed bed reactor. The hydrogen fueled chemical-looping combustion in the new gas turbine cycle consists of two successive reactions: hydrogen fuel is reacted with metal oxide (reduction of metal oxide), instead of air or pure oxygen, and then the reduced metal is successively oxidized by air. Here, we have developed looping materials based on the integration of NiO, as solid reactants, with a composite metal oxide of NiAl₂O₄, as a binder, leading to a significant role in improving reaction rate, conversion, and regenerability in cyclic reaction in this combustor, compared with the other materials. These promising results indicated that this novel hydrogen fueled chemical-looping combustion is expected to be an effective use of hydrogen energy in power generation.     

Gasification inhibition in chemical-looping combustion with solid fuels

Chemical-looping combustion (CLC) is a novel technology that can be used to meet growing demands on energy production without CO₂ emissions. The CLC process includes two reactors, an air and a fuel reactor. Between these two reactors oxygen is transported by an oxygen carrier, which most often is a metal oxide. This arrangement prevents mixing of N₂ from the air with CO₂ from the combustion giving combustion gases that consist almost entirely of CO₂ and H₂O. The technique reduces the energy penalty that normally arises from the separation of CO₂ from other flue gases, hence, CLC could make capture of CO₂ cheaper. For the application of CLC to solid fuels, the char remaining after devolatilization will react indirectly with the oxygen carrier via steam gasification. It has been suggested that H₂, and possibly CO, has an inhibiting effect on steam gasification in CLC. In this work experiments were conducted to investigate this effect. The experiments were conducted in a laboratory fluidized-bed reactor that was operating cyclically with alternating oxidation and reduction periods. Two different oxygen carriers were used as well as an inert sand bed. During the reducing period varying concentrations of CO or H₂ were used together with steam while the oxidation was conducted with 10% O₂ in N₂. The temperature was constant at 970 °C for all experiments. The results show that CO does not directly inhibit the gasification whereas the partial pressure of H₂ had a significant influence on fuel conversion. The results also suggest that dissociative hydrogen adsorption is the predominant hydrogen inhibition mechanism under the laboratory conditions, thus explaining why char conversion is much faster in a bed of oxygen carrying material, compared to an inert sand bed.     

A novel gas turbine cycle with hydrogen-fueled chemical-looping combustion

In this paper we have proposed a novel gas turbine cycle with hydrogen-fueled chemical-looping combustion, and the system study on two hydrogen-fueled power plants, the new gas turbine cycle and an advanced gas turbine cycle with H₂/O₂ combustion, has been investigated with the aid of exergy principle (EUD methodology). The hydrogen fueled chemical-looping combustion in the new gas turbine cycle consists of two successive reactions: hydrogen fuel is reacted with metal oxide (reduction of metal oxide), and then instead of air or pure oxygen, the reduced metal is successively oxidized by the saturated air. As a result, the new hydrogen-fueled gas turbine cycle has a breakthrough performance, with at least about 12 percentage-point higher efficiency compared to the gas turbine cycle with H₂/O₂ combustion, and will be environmentally superior due to complete elimination of NO_x formation. The promising results obtained here indicated that this novel gas turbine cycle with hydrogen-fueled chemical looping combustion could make a breakthrough in efficient use of hydrogen energy in power plants.     

Exergy analysis of self-ignition combustion synthesis for producing rare-earth-based hydrogen storage alloy

A new production system for rare-earth-based hydrogen storage alloys is proposed. We applied self-ignition combustion synthesis (SICS) utilizing hydrogenation heat of metallic calcium. The required primary energy and total exergy loss (EXL) for the production of 1 kg of LaNi₅ alloy with the proposed and conventional systems were evaluated. The results revealed that the production of raw materials accounted for more than 90% of the total EXL in both systems. Specifically, the use of calcium had decisive effects on the total EXL of the system for producing LaNi₅ alloy. The proposed system reduced the total EXL by 14.6 MJ/kg-LaNi₅ as compared with the conventional system. The SICS was remarkably exergy-saving because the heating temperature was decreased by utilizing the hydrogenation heat of calcium and the product absorbed hydrogen without an activation treatment.     

Exergy analysis of solid-oxide fuel-cell (SOFC) systems

The exergy concept has been used to analyze two methane-fueled SOFC systems. The systems include preheating of fuel and air, reforming of methane to hydrogen, and combustion of the remaining fuel in an afterburner. An iterative computer program using a sequential-modular approach was developed and used for the analyses. Simulation of an SOFC system with external reforming yielded first-law and second-law efficiencies of 58 and 56%, respectively, with 600% theoretical air. Heat released from the afterburner was used to reform methane, vaporize water, and preheat air and fuel. When these heat requirements were satisfied, the exhaust-gas temperature was so low that it could only be used for heating rooms or water. Because of heat requirements in the system, fuel utilization (FU) in the FC was limited to 75%. The remaining fuel was used for preheating and reforming. Reduced excess air led to reduced heat requirements and the possibility of a higher FU in the FC. Irreversibilities were also reduced and efficiencies increased. Recycling fuel and water vapor from the FC resulted in first-law and second-law efficiencies of 75.5 and 73%, respectively, with 600% theoretical air, vaporization of water was avoided and the FU was greater.     

Exergy analysis and experimental study of heat pump systems

Exergy analysis of heat pump—air conditioner systems has been carried out. The irreversibilities due to heat transfer and friction have been considered. The coefficient of performance based on the first law of thermodynamics as a function of various parameters, their optimum values, and the efficiency and coefficient of performance based on exergy analysis have been derived. Based on the exergy analysis, a simulation program has been developed to simulate and evaluate experimental systems. The simulation of a domestic heat pump—air conditioner of 959 W nominal power (Matsushita room air conditioner model CS-XG28M) is then carried out using experimental data. It is found that COP based on the first law varies from 7.40 to 3.85 and the exergy efficiency from 0.37 to 0.25 both a decreasing function of heating or cooling load. The exergy destructions in various components are determined for further study and improvement of its performance.     

Exergy analysis of lithium bromide/water absorption systems

Exergy analysis of a single-effect lithium bromide/water absorption system for cooling and heating applications is presented in this paper. Exergy loss, enthalpy, entropy, temperature, mass flow rate and heat rate in each component of the system are evaluated. From the results obtained it can be concluded that the condenser and evaporator heat loads and exergy losses are less than those of the generator and absorber. This is due to the heat of mixing in the solution, which is not present in pure fluids. Furthermore, a simulation program is written and used for the determination of the coefficient of performance (COP) and exergetic efficiency of the absorption system under different operating conditions. The results show that the cooling and heating COP of the system increase slightly when increasing the heat source temperature. However, the exergetic efficiency of the system decreases when increasing the heat source temperature for both cooling and heating applications.     

A chemical intercooling gas turbine cycle with chemical-looping combustion

A novel methanol-based power system with Chemical-Looping Combustion (CLC) is proposed in this paper. CLC system is a promising approach to greatly decrease the energy penalty for CO₂ removal, where iron oxides circulate between two reactors and an inherent CO₂ separation occurs. The combustion process of CLC systems mainly include two steps: a reduction reaction of iron oxides, where the fuel is not mixed with air and the thermal energy for the endothermic reaction is supplied by the intercooling heat of the compressor of the gas turbine, and an oxidation reaction of iron oxides, where the compressed air is heated by the iron oxides. On the basis of the system's integration of cascade utilization of chemical energy of methanol and thermal energy, the thermal efficiency of this novel cycle is expected to be 56.8% with 90% of CO₂ recovery, 10.2 percentage points higher than a combined cycle (CC) with the same CO₂ capture. The promising results obtained here indicate that this novel thermal cycle is a promising approach to accomplish the efficient utilization of chemical energy of methanol without a decrease in thermal efficiency for CO₂ removal.     

Modeling of the chemical-looping combustion of methane using a Cu-based oxygen-carrier

A mathematical model for a bubbling fluidized bed has been developed to simulate the performance of the fuel-reactor in chemical-looping combustion (CLC) systems. This model considers both the fluid dynamic of the fluidized bed and freeboard and the kinetics of reduction of the oxygen-carrier, here CuO impregnated on alumina. The main outputs of the model are the conversion of the carrier and the gas composition at the reactor exit, the axial profiles of gas concentrations and the fluid dynamical structure of the reactor. The model was validated using measurements when burning CH₄ in a 10 kW_th prototype using a Cu-based oxygen-carrier. The influence of the circulation rate of solids, the load of fuel gas, the reactor temperature and size of the oxygen-carrier particles were analyzed. Combustion efficiencies predicted by the model showed a good agreement with measurements. Having validated the model, the implications for designing and optimizing a fuel-reactor were as follows. The inventory of solids for a high conversion of the fuel was sensitive to the reactor’s temperature, the solids’ circulation rate and the extent to which the solids entering to the reactor had been regenerated. The optimal ratio of oxygen-carrier to fuel was found to be 1.7–4 for the Cu-based oxygen-carrier used here. In this range, the inventory of solids to obtain a combustion efficiency of 99.9% at 1073 K was less than 130 kg/MW_th. In addition, the model’s results were very sensitive to the resistance to gas diffusing between the emulsion and bubble phases in the bed, to the decay of solids’ concentration in the freeboard and to the efficiency contact between gas and solids in the freeboard. Thus, a simplified model, ignoring any restriction to gas and solids contacting each other, will under-predict the inventory of solids by a factor of 2–10.     

Evaluation of reaction mechanism of coal-metal oxide interactions in chemical-looping combustion

The knowledge of reaction mechanism is very important in designing reactors for chemical-looping combustion (CLC) of coal. Recent CLC studies have considered the more technically difficult problem of reactions between abundant solid fuels (i.e. coal and waste streams) and solid metal oxides. A definitive reaction mechanism has not been reported for CLC reaction of solid fuels. It has often been assumed that the solid/solid reaction is slow and therefore requires that reactions be conducted at temperatures high enough to gasify the solid fuel, or decompose the metal oxide. In contrast, data presented in this paper demonstrates that solid/solid reactions can be completed at much lower temperatures, with rates that are technically useful as long as adequate fuel/metal oxide contact is achieved. Density functional theory (DFT) simulations as well as experimental techniques such as thermo-gravimetric analysis (TGA), flow reactor studies, in situ X-ray photo electron spectroscopy (XPS), in situ X-ray diffraction (XRD) and scanning electron microscopy (SEM) are used to evaluate how the proximal interaction between solid phases proceeds. The data indicate that carbon induces the Cu-O bond breaking process to initiate the combustion of carbon at temperatures significantly lower than the spontaneous decomposition temperature of CuO, and the type of reducing medium in the vicinity of the metal oxide influences the temperature at which the oxygen release from the metal oxide takes place. Surface melting of Cu and wetting of carbon may contribute to the solid-solid contacts necessary for the reaction.     

Pressurized chemical-looping combustion of coal with an iron ore-based oxygen carrier

Chemical-looping combustion (CLC) is a new combustion technology with inherent separation of CO₂. Most of the previous investigations on CLC of solid fuels were conducted under atmospheric pressure. A pressurized CLC combined cycle (PCLC-CC) system is proposed as a promising coal combustion technology with potential higher system efficiency, higher fuel conversion, and lower cost for CO₂ sequestration. In this study pressurized CLC of coal with Companhia Valedo Rio Doce (CVRD) iron ore was investigated in a laboratory fixed bed reactor. CVRD iron ore particles were exposed alternately to reduction by 0.4 g of Chinese Xuzhou bituminous coal gasified with 87.2% steam/N₂ mixture and oxidation with 5% O₂ in N₂ at 970 °C. The operating pressure was varied between 0.1 MPa and 0.6 MPa. First, control experiments of steam coal gasification over quartz sand were performed. H₂ and CO₂ are the major components of the gasification products, and the operating pressure influences the gas composition. Higher concentrations of CO₂ and lower fractions of CO, CH₄, and H₂ during the reduction process with CVRD iron ore was achieved under higher pressures. The effects of pressure on the coal gasification rate in the presence of the oxygen carrier were different for pyrolysis and char gasification. The pressurized condition suppresses the initial coal pyrolysis process while it also enhances coal char gasification and reduction with iron ore in steam, and thus improves the overall reaction rate of CLC. The oxidation rates and variation of oxygen carrier conversion are higher at elevated pressures reflecting higher reduction level in the previous reduction period. Scanning electron microscope and energy-dispersive X-ray spectroscopy (SEM-EDX) analyses show that particles become porous after experiments but maintain structure and size after several cycles. Agglomeration was not observed in this study. An EDX analysis demonstrates that there is very little coal ash deposited on the oxygen carrier particles but no appreciable crystalline phases change as verified by X-ray diffraction (XRD) analysis. Overall, the limited pressurized CLC experiments carried out in the present work suggest that PCLC of coal is promising and further investigations are necessary.     

Kinetic and thermodynamic analysis of iron oxide reduction by graphite for CO2 mitigation in chemical-looping combustion

Chemical-looping combustion (CLC) provides a platform to generate energy streams while mitigating CO₂ using iron oxide as a carrier of oxygen. Through the reduction process, iron oxide experiences phase transformation to ultimately produce metallic iron. To understand iron oxide reduction characteristics and optimally design the fuel reactor, kinetic and thermodynamic analyses were proposed, utilizing graphite. This study aims to evaluate the reduction behavior under the non-isothermal process of various mixture ratios of hematite and graphite via thermogravimetric analysis with simultaneously evaluating evolved gases using a Fourier transform infrared spectrometer. The Coats-Redfern model was employed to approximate the kinetic and thermodynamic parameters which assessed the different reaction mechanisms together with the distributed activation energy model (DAEM). The results revealed that the hematite-to-graphite ratio of 4:1 had the highest reduction degree and had three distinct peaks representing three iron oxide reduction phases. The zero-order reaction mechanism agreed with the experimental results compared with other reaction models. The thermodynamic analysis showed an overall endothermic spontaneous reaction for the three phases which signified the direct reduction of the iron oxides. The DAEM result validated a stepwise reduction of iron oxides to metallic iron. The study aids the optimal design of the CLC fuel reactor for enhanced system performance.     

Reactivity study on oxygen carriers for solar-hybrid chemical-looping combustion of di-methyl ether

A power cycle with the solar-hybrid chemical-looping combustion can simultaneously provide a new insight for treating with the problem of large energy penalty for CO₂ capture in the energy system and achieve the efficient utilization of the mid-temperature solar thermal energy. Experiments were implemented on a thermo-gravimetrical reactor with di-methyl ether (DME) as fuel to identify suitable looping material for this system. Oxygen carriers, with Fe₂O₃, NiO, and CoO as solid reactants and Al₂O₃, MgAl₂O₄, and YSZ as binders, were prepared by dissolution method. Compared with Fe₂O₃ and NiO, CoO has higher reactivity in the research temperature range of 673–773 K, and the suitable reduction temperature of CoO with DME is around 723 K. Carbon deposition in the reduction process of DME with CoO/CoAl₂O₄ can be completely suppressed by adding water vapor to the gaseous reactant, and the optimal range of H₂O/DEM is around 1.5–2.0. Scanning electron microscopy was used to characterize the morphological features of the fresh and the cycling used oxygen carriers. For CoO/YSZ, big grains formed after cyclic reactions, but no apparent change was found for CoO/CoAl₂O₄. The findings of this paper provide a promising looping material candidate for the solar-hybrid chemical-looping combustion.     

Comparison of carbon capture IGCC with pre-combustion decarbonisation and with chemical-looping combustion

Carbon capture from conventional power cycles is accompanied by a significant loss of efficiency. One process concept with a potential for better performance is chemical-looping combustion (CLC). CLC uses a metal oxide to oxidize the fuel, and the reduced metal is then re-oxidized in a second reactor with air. The combustion products CO₂ and water remain unmixed with nitrogen, thereby avoiding the need for energy intensive air separation. In this paper, the performance of various configurations of CLC used in integrated gasification combined cycle power plants (CLC-IGCC) are analyzed and compared to a conventional IGCC design with pre-combustion carbon capture by physical absorption. The analysis is based on process simulation using Aspen Plus and GateCycle. Key design parameters are varied, and the results are interpreted using exergy analysis. The CLC-IGCC offers the advantages of higher plant efficiency and more complete carbon capture. The efficiency is very sensitive to changes in the gas turbine inlet temperature for both the CLC and the conventional IGCC designs. The development of oxygen carrier particles with a high thermal stability is therefore crucial for capitalizing on the potential efficiency advantage of CLC.     

Exergy analysis of hydrogen/diesel combustion in a dual fuel engine using three-dimensional model

In the present study, the energy and exergy analysis were carried out for a Deutz dual fuel (diesel + hydrogen) engine at different gas fuel-air ratios (ø_H2 = 0.3, 0.4, 0.5, 0.6, 0.7, and 0.8) and constant diesel fuel amount (6.48 mg/cycle). The energy analysis was performed during a closed cycle by using a three-dimensional CFD code and combustion modeling was carried out by Extend Coherent Flame Model- Three Zone model (ECFM-3Z). For the exergy analysis, an in-house computational code is developed, which uses the results of the energy analysis at different fuel-air ratios. The cylinder pressure results for natural gas/diesel fuelled engine are verified with the experimental data in the literature, which shows a good agreement. This verification gives confidence in the model prediction for hydrogen- fuelled case. With crank position at different gas fuel-air ratios, various rate and cumulative exergy components are identified and calculated separately. It is found that as gas fuel-air ratio increases from 0.3 to 0.8, the exergy efficiency decreases from 43.7% to 34.5%. Furthermore, the value of irreversibility decreases from 29.8% to 26.6% of the mixture fuels chemical exergies. These values are in good agreement with data in the literature for dual fuel engines.     

Exergy analysis for stationary flow systems with several heat exchange temperatures

A thermodynamic theory of exergy analysis for a stationary flow system having several heat inputs and outputs at different temperature levels is presented. As a new result a relevant reference temperature of the surroundings is derived for each case. Also a general formula which combines exergy analysis with a modified Carnot efficiency is derived. The results are illustrated by numerical examples for mechanical multi-circuit heat pump cycles, for a Brayton process and for an absorption heat pump.     

Exergy and reliability analysis of wind turbine systems: A case study

The present study undertakes an exergy and reliability analysis of wind turbine systems and applies to a local one in Turkey: the exergy performance and reliability of the small wind turbine generator have been evaluated in a demonstration (1.5 kW) in Solar Energy Institute of Ege University (latitude 38.24 N, longitude 27.50 E), Izmir, Turkey. In order to extract the maximum possible power, it is important that the blades of small wind turbines start rotating at the lowest possible wind speed. The starting performance of a three-bladed, 3 m diameter horizontal axis wind turbine was measured in field tests. The average technical availability, real availability, capacity factor and exergy efficiency value have been analyzed from September 2002 to November 2003 and they are found to be 94.20%, 51.67%, 11.58%, and 0–48.72%, respectively. The reliability analysis has also been done for the small wind turbine generator. The failure rate is high to an extent of 2.28×10⁻⁴ h⁻¹ and the factor of reliability is found to be 0.37 at 4380 h. If failure rate can be decreased, not only this system but also other wind turbine systems of real availability, capacity factor and exergy efficiency will be improved.     

Exergy analysis and optimisation of waste heat recovery systems for cement plants

In the last decades, heat recovery systems have received much attention due to the increase in fuel cost and the increase in environmental issues. In this study, different heat recovery systems for a cement plant are compared in terms of electricity generation and exergy analysis. The heat sources are available in high temperature (HT) and low temperature (LT). For the HT section a dual pressure Rankine cycle, a simple dual pressure Organic Rankine Cycle (ORC) and a regenerative dual pressure ORC are compared. Also, for the LT section, a simple ORC is compared with transcritical carbon dioxide cycle. To find the best system, an optimisation algorithm is applied to all proposed cycles. The results show that for the HT section, regenerative ORC has the highest exergy efficiency and has the capability of producing nearly 7?MW electricity for a cement factory with the capacity of 3400 ton per day. The main reason for this is introducing the regenerative heat exchanger to the cycle. For the LT section, ORC showed a better performance than the CO₂ cycle. It is worth mentioning that the generated power in this section is far lower than that of the HT section and is equal to nearly 300?kW.     

Exergy efficiency calculation of energy intensive systems

An innovative method for the exergy efficiency calculation of a complex energy-intensive system with arbitrary structures is described in this paper. The method is based on a novel general equation to calculate the total system exergy efficiency, and on an exergy flow graph proposed by the authors. This approach allows a user to obtain not only the exergy efficiency of the total system, but also to show the relationship between the exergy efficiency of an individual element and that of the whole system. An example employing the method to the thermodynamic exergy analysis of a power plant is provided.