A comparative simulation study of power generation plants involving chemical looping combustion systems

This work presents a simulation study on both energy and economics of power generation plants with inherent CO₂ capture based on chemical looping combustion technologies. Combustion systems considered include a conventional chemical looping system and two extended three-reactor alternatives (exCLC and CLC3) for simultaneous hydrogen production. The power generation cycles include a combined cycle with steam injected gas turbines, a humid air turbine cycle and a simple steam cycle. Two oxygen carriers are considered in our study, iron and nickel. We further analyze the effect of the pressure reaction and the turbine inlet temperature on the plant efficiency. Results show that plant efficiencies as high as 54% are achieved by the chemical looping based systems with competitive costs. That value is well above the efficiency of 46% obtained by a conventional natural gas combined cycle system under the same conditions and simulation assumptions.     

Syngas combustion in a 500 Wth Chemical-Looping Combustion system using an impregnated Cu-based oxygen carrier

Chemical-Looping Combustion (CLC) is an emerging technology for CO₂ capture because separation of this gas from the other flue gas components is inherent to the process and thus no energy is expended for the separation. For its use with coal as fuel in power plants, a process integrated by coal gasification and CLC would have important advantages for CO₂ capture. This paper presents the combustion results obtained with a Cu-based oxygen carrier in a continuous operation CLC plant (500 Wth) using syngas as fuel. For comparison purposes pure H₂ and CO were also used. Tests were performed at two temperatures (1073 and 1153 K), different solid circulation rates and power inputs. Full syngas combustion was reached at 1073 K working at f higher than 1.5. The syngas composition had small effect on the combustion efficiency. This result seems to indicate that the water gas shift reaction acts as an intermediate step in the global combustion reaction of the syngas. The results obtained after 40 h of operation showed that the copper-based oxygen carrier prepared by impregnation could be used in a CLC plant for syngas combustion without operational problems such as carbon deposition, attrition, or agglomeration.     

Comparative assessment of coal fired IGCC systems with CO2 capture using physical absorption,membrane reactors and chemical looping

The integrated gasification combined cycle (IGCC) as an efficient power generation technology with lowest specific carbon dioxide emissions among coal power plants is a very good candidate for CO₂ capture resulting in low energy penalties and minimised CO₂ avoidance costs. In this paper, the techno-economic characteristics of four different capture technologies, which are built upon a conventional reference case, are studied using the chemical process simulation package “ECLIPSE”. The technology options considered are: physical absorption, water gas shift reactor membranes and two chemical looping combustion cycles (CLC), which employ single and double stage reactors. The latter system was devised to achieve a more balanced distribution of temperatures across the reactors and to counteract hot spots which lead to the agglomeration and the sintering of oxygen carriers. Despite the lowest efficiency loss among the studied systems, the economic performance of the double stage CLC was outperformed by systems employing physical absorption and water gas shift reactor membranes. Slightly higher efficiencies and lower costs were associated with systems with integrated air separation units. The estimation of the overall capital costs was carried out using a bottom-up approach. Finally, the CO₂ avoidance costs of individual technologies were calculated based on the techno-economic data.     

Syngas combustion in a chemical-looping combustion system using an impregnated Ni-based oxygen carrier

Chemical-looping combustion (CLC) has emerged as a promising option for CO₂ capture because this gas is inherently separated from the other flue gas components and thus no energy is expended for the separation. This technology would have some advantages if it could be adapted for its use with coal as fuel. In this sense, a process integrated by coal gasification and CLC could be used in power plants with low energy penalty for CO₂ capture. This work presents the results obtained in the combustion of syngas as fuel with a Ni-based oxygen carrier prepared by impregnation in a CLC plant under continuous operation. The effect on the oxygen carrier behaviour and the combustion efficiency of several operating conditions was determined in the continuous CLC plant. High combustion efficiencies (～99%), close to the values limited by thermodynamics, were reached at oxygen carrier-to-fuel ratios higher than 5. The temperature in the FR had a significant influence, although high efficiencies were obtained even at 1073 K. The syngas composition had small effect on the combustion, obtaining high and similar efficiencies with syngas fuels of different composition, even in the presence of high CO concentrations. The low reactivity of the oxygen carrier with CO seemed to indicate that the water gas shift reaction acts as an intermediate step in the global reaction of the syngas in a continuous CLC plant. Neither agglomeration nor carbon deposition problems were detected during 50 h of continuous operation in the prototype. The obtained results showed that the impregnated Ni-based oxygen carrier could be used in a CLC plant for the combustion of syngas produced in an integrated gasification combined cycle (IGCC).     

Chemical-looping combustion in a 300 W continuously operating reactor system using a manganese-based oxygen carrier

Chemical-looping combustion (CLC) is a method for the combustion of fuel gas with inherent separation of carbon dioxide. This technique involves the use of two interconnected reactors. A solid oxygen carrier reacts with the oxygen in air in the air reactor and is then transferred to the fuel reactor, where the fuel gas is oxidized to carbon dioxide and water by the oxygen carrier. Fuel gas and air are never mixed and pure CO₂ can easily be obtained from the flue gas exit. The oxygen carrier is recycled between both reactors in a regenerative process. This paper presents the results from a continuously operating laboratory CLC unit, consisting of two interconnected fluidized beds. The feasibility of the use of a manganese-based oxygen carrier supported on magnesium stabilized zirconia was tested in this work. Natural gas or syngas was used as fuel in the fuel reactor. Fuel flow and air flow was varied, the thermal power was between 100 and 300 W, and the air ratio was between 1.1 and 5.0. Tests were performed at four temperatures: 1073, 1123, 1173 and 1223 K. The prototype was successfully operated at all conditions with no signs of agglomeration or deactivation of the oxygen carrier. The same particles were used during 70 h of combustion and the mass loss was 0.038% per hour, although the main quantity was lost in the first hour of operation. In the combustion tests with natural gas, methane was detected in the exit flue gases, while CO and H₂ were maintained at low concentrations. Higher temperature or lower fuel flows increases the combustion efficiency, which ranged from 0.88 to 0.99. On the other hand, the combustion of syngas was complete for all experimental conditions, with no CO or H₂ present in the gas from the fuel reactor.     

Auto-thermal chemical looping combustion of sulphur with Fe2O3 oxygen carriers for sulphuric acid production: Thermodynamics

Chemical looping is a novel fuel conversion and material separation technology. It can be applied to obtain sulphur through selective oxidation of H₂S. Further, chemical looping combustion (CLC) of sulphur can generate SO₂ with a high concentration without NO_x formation. The high SO₂ concentration is adjustable and facilitates large-scale H₂SO₄ production. In this study, we examined the thermodynamics of the CLC of sulphur for H₂SO₄ production, which has not been reported previously. We analyzed the effects of reactor temperature and sulphur to Fe₂O₃ oxygen carrier (OC) ratios on sulphur allotrope transformations and on the distributions of reaction products. Moreover, the reactors were operated auto-thermally. Based on this design, we examined the effects of fuel reactor (FR) and air reactor temperatures on the minimum recirculation of the OC, as well as the gas and solid products and heat released from the air reactor. Our results showed that the CLC of sulphur with Fe₂O₃ OC could occur through an auto-thermal process. The FR in a sulphur CLC system should be operated over a temperature range of 800–950°C, with an Fe₂O₃ OC recirculation between 45 and 143 kg/kg_S(s). Furthermore, when the FR was operated in the auto-thermal mode, we achieved 100% SO₂ conversion. The findings of this study may be applied to reactor design for large-scale H₂SO₄ production through CLC of sulphur.     

Numerical simulation and experimental verification of chemical reactions for SCR DeNOx

Selective catalytic reduction (SCR) is a major commercial technology for NO _x removal in power plants. There are a lot of complex chemical reactions in SCR reactors, and it is of great significance to understand the internal process of chemical reactions for SCR DeNO _x and study the impact of various factors on NO _x removal efficiency. In this paper, the impact of reaction temperature, ammonia-nitrogen molar ratio and resident time in the catalyst bed layer on NO _x removal efficiency were studied by simulation of chemical reactions. Then calculated results were compared with catalyst activity test data in a power plant, which proved that the simulated results were accurate. As a result, the reaction conditions were optimized in order to get the best removal efficiency of NO, so that we can provide a reference for optimal running of SCR in power plants.     

A process for generating power from the oxidation of coal in supercritical water

A theoretical study of power generation from oxidation of coal by supercritical water oxidation (SCWO) is presented. Two versions of SCWO power plant are compared to two of the most efficient conventional power plant processes: pulverised coal power plants and pressurised fluidised bed power plant. The effects of steam pressure and temperature on produced (W_p), consumed (W_c) and net work (W_N) are calculated in order to compare the efficiency of these power plants for the same steam conditions. Enthalpies have been calculated using residual enthalpies by Peng-Robinson equation of state. Calculated results show that net work in SCWO power plant is 5% higher than in other power plants, due to the fact that no air surplus is necessary for complete combustion and because steam is produced by direct heating. Energetic efficiency of SCWO increases more quickly with temperature than for the other power plants. The effect of steam pressure is different: until 30 MPa power plant efficiencies increase more quickly in SCWO power plants than in conventional plants, but when steam pressures increases beyond 30 MPa, efficiencies decrease in SCWO power plants.     

Gas leakage measurements in a cold model of an interconnected fluidized bed for chemical-looping combustion

In chemical-looping combustion (CLC) a gaseous fuel is burnt with inherent separation of the greenhouse gas carbon dioxide. The oxygen is transported from the combustion air to the fuel by means of metal oxide particles acting as oxygen carriers. A CLC system can be designed similar to a circulating fluidized bed, but with the addition of a bubbling fluidized bed on the return side. Thus, the system consists of a riser (fast fluidized bed) acting as the air reactor. This is connected to a cyclone, where the particles and the gas from the air reactor are separated. The particles fall down into a second fluidized bed, the fuel reactor, and are via a fluidized pot-seal transported back into the riser. The gas leaving the air reactor consists of nitrogen and unreacted oxygen, while the reaction products, carbon dioxide and water, come out from the fuel reactor. The water can easily be condensed and removed, and the remaining carbon dioxide can be liquefied for subsequent sequestration.The gas leakage between the reactors must be minimized to prevent the carbon dioxide from being diluted with nitrogen, or to prevent carbon dioxide from leaking to the air reactor decreasing the efficiency of carbon dioxide capture. In this system, the possible gas leakages are: (i) from the fuel reactor to the cyclone and to the pot-seal, (ii) from the cyclone down to the fuel reactor, (iii) from the pot-seal to the fuel reactor. These gas leakages were investigated in a scaled cold model. A typical leakage from the fuel reactor was 2%, i.e. a CO₂ capture efficiency of 98%. No leakage was detected from the cyclone to the fuel reactor. Thus, all product gas from the air reactor leaves the system from the cyclone. A typical leakage from the pot-seal into the fuel reactor was 6%, which corresponds to 0.3% of the total air added to the system, and would give a dilution of the CO₂ produced by approximately 6% air. However, this gas leakage can be avoided by using steam, instead of air, to fluidize the whole, or part of, the pot-seal. The disadvantages of diluting the CO₂ are likely to motivate the use of steam.     

Catalytic steam reforming of model biogas

Catalytic steam reforming of a model biogas (CH₄/CO₂ = 60/40) is investigated to produce H₂-rich synthesis gas. Gas engines benefit from synthesis gas fuel in terms of higher efficiency and lower NO_x production when compared to raw biogas or CH₄. The process is realized in a fixed bed reactor with a Ni-based catalyst on CaO/Al₂O₃ support. To optimize the performance, the reactor temperature and the amount of excess steam are varied. The experimental results are compared to the theoretical values from thermodynamic calculation and the main trends of CH₄ conversion and H₂ yield are analyzed and verified. Finally, optimal reactor temperature is pointed out and a range of potential steam to methane ratios is presented. The experimental results will be applied to design a steam reformer at an existing anaerobic biomass fermentation plant in Strem, Austria.     

Multiphase CFD Modeling for a Chemical Looping Combustion Process (Fuel Reactor)

There are growing concerns about increasing emissions of greenhouse gases and a looming global warming crisis. CO₂ is a greenhouse gas that affects the climate of the earth. Fossil fuel consumption is the major source of anthropogenic CO₂ emissions. Chemical looping combustion (CLC) has been suggested as an energy‐efficient method for the capture of carbon dioxide from combustion. A chemical‐looping combustion system consists of a fuel reactor and an air reactor. The air reactor consists of a conventional circulating fluidized bed and the fuel reactor is a bubbling fluidized bed. The basic principle involves avoiding direct contact of air and fuel during the combustion. The oxygen is transferred by the oxygen carrier from the air to the fuel. The water in combustion products can be easily removed by condensation and pure carbon dioxide is obtained without any loss of energy for separation. With the improvement of numerical methods and more advanced hardware technology, the time required to run CFD (computational fluid dynamic) codes is decreasing. Hence, multiphase CFD‐based models for dealing with complex gas‐solid hydrodynamics and chemical reactions are becoming more accessible. To date, there are no reports in the literature concerning mathematical modeling of chemical‐looping combustion using FLUENT. In this work, the reaction kinetics models of the (CaSO₄ + H₂) fuel reactor is developed by means of the commercial code FLUENT. The effects of particle diameter, gas flow rate and bed temperature on chemical looping combustion performance are also studied. The results show that the high bed temperature, low gas flow rate and small particle size could enhance the CLC performance.     

Comparison of nickel- and iron-based oxygen carriers in chemical looping combustion for CO2 capture in power generation

In chemical looping combustion (CLC), a solid oxygen carrier circulates between two fluidised bed reactors and transports oxygen from the combustion air to the fuel; thus, the fuel is not mixed with air and an inherent CO₂ separation occurs. In this paper, CLC is integrated in a natural gas fired combined cycle (NGCC). In this system, nickel- and iron-based oxygen carriers are compared regarding the system's electrical and exergy efficiencies. Furthermore, the feasibility of CLC in two interconnected pressurised fluidised bed reactors (IPFBR) is studied for both oxygen carriers. The hypothetical layout plus dimensions of the IPFBR is presented for a capacity of 800 MW input of natural gas. Finally, top-firing is proposed as an option to overcome the apparent limitation in operating temperature of the reactor equipment and/or the oxygen carriers. The results indicate that there is no significant difference in the system's efficiency if both oxygen carriers could operate at the same temperature. However, CLC seems easier to be technically realised in an IPFBR with a nickel-based oxygen carrier.     

Effect of air separation unit integration on integrated gasification combined cycle performance and NO<Subscript>x</Subscript> emission characteristics

Thermodynamic simulation method is developed and applied to analyze the performance and the NO_x emission characteristics of the IGCC (Integrated Gasification Combined Cycle) power plants coupled with ASU (Air Separation Unit). Simulations on IGCC power plants are made through combining the chemical process models for coal gasification and gas clean-up and the thermodynamic combined cycle model with NO_x prediction capability. With coal as feedstock of IGCC, the present study investigates and compares the power output, the overall efficiency and the NO_x emission characteristics of various IGCC plants at different ASU integration conditions in order to give the design criteria for efficient and environmental friendly IGCC configuration.     

基于双级燃料反应器的污泥化学链燃烧特性

化学链燃烧技术是一种可以实现CO₂内分离的新型燃烧技术。本文利用基于双级燃料反应器的新型化学链燃烧反应系统,以赤铁矿为载氧体,对污泥的化学链燃烧进行实验研究,系统连续稳定运行8h,考察燃料反应器温度（800～900℃）、污泥进料量（300～600g/h）对污泥化学链燃烧性能的影响。结果表明,稳定运行过程中,床料大部分位于一级燃料反应器,下降管高度保持稳定;双级燃料反应器的设计极大提高了污泥碳转化率,随温度的增加,碳转化率和碳捕集效率逐渐升高,且额外耗氧量始终低于10%;随着污泥进料量增加,碳转化率和CO₂体积分数逐渐降低。对两级燃料反应器内载氧体进行XRD分析,结果显示,还原后的载氧体在空气反应器再生后进入二级燃料反应器,和一级燃料反应器相比,具有更多的Fe₂O₃成分,保证其具有更高的反应活性。     

Comparison of hydrodynamic and mass transfer performances of an emulsion loop-venturi reactor in cocurrent downflow and upflow configurations

Hydrodynamic parameters (gas-induced flow rate and gas hold-up) and mass transfer characteristics (k_La, k_L and a) have been investigated in a gas–liquid reactor denoted “Emulsair” in which the distributor is an emulsion-venturi and the gas phase is self-aspired by action of the kinetic energy of the liquid phase at the venturi throat. Two configurations, respectively cocurrent downflow and cocurrent upflow were compared. A chemical method involving the dispersion of a CO₂–air mixture in a monoethanolamine (MEA) aqueous solution was used to measure mass transfer parameters. Experimental results showed that only the homogeneous bubbling regime prevailed in the upward configuration, while an annular regime could also be observed for cocurrent downflow at low liquid flow rate. Gas-induced flow rate and gas hold-up were usually smaller for cocurrent upflow, both at constant liquid flow rate and specific power input. The same stood for mass transfer properties. Conversely, specific power requirements were lower at constant liquid flow rate and mass transfer characteristics were enhanced at constant gas-induced flow rate for cocurrent upflow. A comparison with other gas–liquid contacting devices showed that the Emulsair reactor is a versatile tool avoiding the presence of mechanically moving parts when high and quickly adaptable dissolved gas supply is required. The cocurrent upflow configuration can be preferred when high gas flow rates are desired because the evolutions of gas-induced flow rate and mass transfer characteristics exhibit a stronger dependence on specific power input in the homogeneous bubbling regime for this configuration.     

Ni载体整体煤气化链式燃烧联合循环性能

本文将具有分离CO₂的链式燃烧技术与整体煤气化联合循环(IGCC)技术结合,构成整体煤气化链式燃烧联合循环系统,对系统性能进行了模拟研究。结果表明,采用德士古气化工艺、空气反应器出口温度1200℃,NiO/NiAl₂O₄作载氧体,压气机压比17、补燃后透平初温(TIT)1350℃、冷却空气量12％时,系统净效率39.61% HHV（41.55%LHV）,CO₂排放量126 g·kW^-1·h^-1。补燃温度1350℃,空气反应器温度由1000℃升高到1200℃,CO₂的回收率提高约23％,系统效率由40.3%降低到39.61％;补燃温度由1200℃提高到1500℃,系统净效率由37.4%增加到40.8%,CO₂的排放量从3g·kW^-1·h^-1增加到202 g·kW^-1·h^-1;补燃温度一定,压比增大,系统比功减小,CO₂排放量增加,效率先增大后减小,存在最佳压比.     

Capital costs and energy considerations of different alternative stripper configurations for post combustion CO2 capture

Capturing and storing the greenhouse gas carbon dioxide produced by power plants and chemical production plants before it is emitted to the atmosphere will play a major role in mitigation climate change. Among the different technologies, aqueous amine absorption/stripping is a promising one. In this study, five different configurations for aqueous absorption/stripping have been compared with regards to capital investment and energy consumption. The process simulations are made with the use of Unisim Design and ProTreat, while for the cost calculations, data from Turton et al. (2009) and Sinnott and Towler (2009) are used.We cannot identify one single configuration to be the optimum always for all situations, as it depends on many parameters like energy and material costs, interest rate, plant complexity, etc. With the assumption and estimated parameters in this study we find that vapor recompression configuration is the best configuration because it has the lowest total capture cost and CO₂ avoided cost. In addition, the plant complexity does not increase very much compared to the benchmark. The split-stream configuration with cooling of semi-lean amine is the second best. However, this configuration increases the investment cost and plant complexity significantly.The effect of heat integration between the compression section and the stripper is also considered. We can reduce heat requirement by heat integration, but since the inlet temperature to the compressors become higher, the compression efficiency will decrease and compression work will increase. In addition, the capital cost and the complexity of the plant will increase. Because of the higher inlet temperature the water content of produced CO₂ is higher and consequently the corrosion problems is more serious in pipes and equipment for compression and injection section.     

Process synthesis and economics of combined biomethanol and CHP energy production derived from biomass wastes

BACKGROUND: This paper reports on process synthesis and economics of combined methanol and CHP (combined heat and power) energy production from crude biooil, waste glycerol produced in biodiesel factories and biomass wastes using integrated reactor design for hydrogen rich syngas. This new process consists of three process steps: (a) pyrolysis of organic waste material to produce biooil, char and pyrogas; (b) steam assisted hydrogasification of the crude glycerol wastes, biooil mixed with pyrogas for hydrogen rich gas; and (c) a low temperature methanol synthesis process. The H₂‐rich gas remaining after methanol synthesis is recycled back to the pyrolysis reactor, the catalytic hydro‐gasification process and the heat recovery steam generator (HRSG). RESULTS: The breakeven price of the Hbiomethanol process yields positive net financial NPV and IRR above 600 USD per tonne. The total capital cost for a small‐scale methanol plant of capacity 2 tonne h^?1 combined with a cogeneration plant of capacity 2 MWe power is estimated to be 170.5 million USD. CONCLUSION: Recycling gas allows the methanol synthesis reactor to perform at a relatively lower pressure than conventionally while the plant still maintains a high methanol yield. The integrated hydrogasification reactor and energy recovery design process minimizes heat loss and increases the process thermal efficiency. The Hbiomethanol process can convert any condensed carbonaceous material and liquid wastes, to produce methanol and CHP. Copyright © 2012 Society of Chemical Industry     

Methane dry reformer by application of chemical looping combustion via Mn-based oxygen carrier for heat supplying and carbon dioxide providing

In this study, the production of H₂ utilizing chemical looping combustion (CLC) in a methane dry reformer assisted by H₂ perm-selective membranes in a CLC-DRM configuration has been investigated. CLC via employment of a Mn-based oxygen carrier generates large amounts of heat in addition to providing CO₂ as the raw material for the dry reforming (DR) reaction. The main advantage of the CLC-DRM configuration is the simultaneous capturing and consuming of CO₂ as a greenhouse gas for H₂ production.A steady state one dimensional heterogeneous catalytic reaction model is applied to analyze the performance and applicability of the proposed CLC-DRM configuration. Simulation results show that CH₄ is completely consumed in the fuel reactor (FR) of the CLC-DRM and pure CO₂ is captured by condensation of H₂O. Also, CH₄ conversion and H₂ yield reach 73.46% and 1.459 respectively at the outlet of the DR side in the CLC-DRM. Additionally, 4562 kmol h⁻¹ H₂ is produced in the DR side of the CLC-DRM.Finally, results indicate that by increasing the FR feed temperature up to 880 K, CH₄ conversion and H₂ production are enhanced to 81.15% and 4790 kmol h⁻¹ respectively.     

The use of iron oxide as oxygen carrier in a chemical-looping reactor

Chemical-looping combustion (CLC) is a method for the combustion of fuel gas with inherent separation of carbon dioxide. This technique involves the use of two interconnected reactors, an air reactor and a fuel reactor. The oxygen demanded in the fuel combustion is supplied by a solid oxygen carrier, which circulates between both reactors. Fuel gas and air are never mixed and pure CO₂ can be obtained from the flue gas exit. This paper presents the results from the use of an iron-based oxygen-carrier in a continuously operating laboratory CLC unit, consisting of two interconnected fluidized beds. Natural gas or syngas was used as fuel, and the thermal power was between 100 and 300 W. Tests were performed at four temperatures: 1073, 1123, 1173 and 1223 K. The prototype was successfully operated for all tests and stable conditions were maintained during the combustion. The same particles were used during 60 h of hot fluidization conditions, whereof 40 h with combustion. The combustion efficiency of syngas was high, about 99% for all experimental conditions. However, in the combustion tests with natural gas, there was unconverted methane in the exit flue gases. Higher temperature and lower fuel flows increase the combustion efficiency, which ranged between 70% and 94% at 1123 K. No signs of agglomeration or mass loss were detected, and the crushing strength of the oxygen carrier particles did not change significantly. Complementary experiments in a batch fluidized bed were made to compare the reactivity of the oxygen carrier particles before and after the 40 h of operation, but the reactivity of the particles was not affected significantly.