Operating experience with chemical looping combustion in a 120 kW dual circulating fluidized bed (DCFB) unit

This study presents first operating experience with a 120 kW chemical looping pilot rig. The dual circulating fluidized bed reactor system and its auxiliary units are discussed. Two different oxygen carriers, i.e. ilmenite, which is a natural iron titanium ore, and a designed Ni-based particle, are tested in the CLC unit. The pilot rig is fueled with H₂, CO and CH₄ respectively at a fuel power of 65–145 kW. High solids circulation, very low solids residence time and low solids inventory are observed during operation. Owing to the scalability of the design concept, these characteristics should be quite similar to those of commercial CLC power plants. Ilmenite shows a high potential for the combustion of H₂-rich gases (e.g. from coal gasification with steam). The H₂ conversion is quite high but there is still a high potential for further improvement. The Ni-based oxygen carrier achieves the thermodynamic maximum H₂ and CO conversion and also very high CH₄ conversion. A variation of the air/fuel ratio and the reaction temperature indicates that the Ni/NiO ratio of the particle has an influence on the performance of the chemical looping combustor. Generally, low solids conversion in air and fuel reactors is observed in almost any conditions. Despite a very low H₂O/CH₄ molar ratio, no carbon formation is observed.     

Cold DeNOx development for oxyfuel power plants

Flue gas purification is a necessary method to avoid emission of sour gases like SO_x and NO_x into the environment. Another important aspect is the zero CO₂ emission from coal-fired power plants. Oxyfuel technology is one of the processes to reach this goal. LINDE KCA Dresden in cooperation with Vattenfall Europe is operating a pilot plant producing liquefied CO₂. Product specification and material requirements make flue gas purification for the removal of SO_x and NO_x unavoidable. The new oxyfuel technologies offer new process conditions for flue gas purification which are not available at atmospheric conditions.At Linde laboratories, catalytic and non-catalytic DeNOx and DeSOx processes have been screened for oxyfuel application. After first feasibility studies, laboratory experiments and economic evaluations, it was decided to develop a process based on wet scrubber systems to remove NO_x from flue gas, simultaneously producing ammonia nitrites which can be thermally decomposed into nitrogen in a second step. After demonstration of the single process steps on laboratory scale, a pilot scrubber was erected and commissioned in 2010 at Schwarze Pumpe Oxyfuel Pilot Plant. In September 2010, the successful completion of the pilot tests demonstrated the NO_x removal efficiency of this technology. The data from the pilot plant tests have been used to finalise a kinetic model describing the NO_x absorption behaviour regarding NO_x removal rate and nitrite selectivity for demonstration of plant scale up. This DeNOx-process is now marketed under the name “LICONOX”.     

Multi-stage chemical looping combustion (CLC) for combined cycles with CO2 capture

This paper presents application of the chemical looping combustion (CLC) method in natural gas-fired combined cycles for power generation with CO₂ capture. A CLC combined cycle consisting of single CLC-reactor system, an air turbine, a CO₂-turbine and a steam cycle has been designated as the base-case cycle. The base-case cycle can achieve net plant efficiency of about 52% at an oxidation temperature of 1200 °C. In order to achieve a reasonable efficiency at lower oxidation temperatures, reheat is introduced into the air turbine by employing multi CLC-reactors. The results show that the single reheat CLC-combined cycle can achieve net plant efficiency of above 51% at oxidation temperature of 1000 °C and above 53% at the oxidation temperature of 1200 °C including CO₂ compression to 110 bar. The double reheat cycle results in marginal efficiency improvement as compared to the single reheat cycle. The CLC-cycles are also compared with a conventional combined cycle with and without post-combustion capture in amine solution. All the CLC-cycles show higher net plant efficiencies with close to 100% CO₂ capture as compared to a conventional combined cycle with post-combustion capture, which is very promising.     

Exergoeconomic and exergoenvironmental analyses of a combined cycle power plant with chemical looping technology

CO₂ capture and storage from energy conversion systems is one option for reducing power plant CO₂ emissions to the atmosphere and for limiting the impact of fossil-fuel use on climate change. Among existing technologies, chemical looping combustion (CLC), an oxy-fuel approach, appears to be one of the most promising techniques, providing straightforward CO₂ capture with low energy requirements.This paper provides an evaluation of CLC technology from an economic and environmental perspective by comparing it with to a reference plant, a combined cycle power plant that includes no CO₂ capture. Two exergy-based methods, the exergoeconomic and the exergoenvironmental analyses, are used to determine the economic and environmental impacts, respectively. The applied methods facilitate the iterative optimization of energy conversion systems and lead towards the improvement of the effectiveness of the overall plant while decreasing the cost and the environmental impact of the generated product. For the plant with CLC, a high increase in the cost of electricity is observed, while at the same time the environmental impact decreases.     

Design and off-design analyses of a pre-combustion CO2 capture process in a natural gas combined cycle power plant

In this study, a cycle designed for capturing the greenhouse gas CO₂ in a natural gas combined cycle power plant has been analyzed. The process is a pre-combustion CO₂ capture cycle utilizing reforming of natural gas and removal of the carbon in the fuel prior to combustion in the gas turbine. The power cycle consists of a H₂-fired gas turbine and a triple pressure steam cycle. Nitrogen is used as fuel diluent and steam is injected into the flame for additional NO_x control. The heat recovery steam generator includes pre-heating for the various process streams. The pre-combustion cycle consists of an air-blown auto-thermal reformer, water–gas shift reactors, an amine absorption system to separate out the CO₂, as well as a CO₂ compression block. Included in the thermodynamic analysis are design calculations, as well as steady-state off-design calculations. Even though the aim is to operate a plant, as the one in this study, at full load there is also a need to be able to operate at part load, meaning off-design analysis is important. A reference case which excludes the pre-combustion cycle and only consists of the power cycle without CO₂ capture was analyzed at both design and off-design conditions for comparison. A high degree of process integration is present in the cycle studied. This can be advantageous from an efficiency stand-point but the complexity of the plant increases. The part load calculations is one way of investigating how flexible the plant is to off-design conditions. In the analysis performed, part load behavior is rather good with efficiency reductions from base load operation comparable to the reference combined cycle plant.     

Demonstrations of coal-fired oxy-fuel technology for carbon capture and storage and issues with commercial deployment

As one of the three major carbon capture technologies associated with carbon capture and storage (CCS), oxy-fuel technology is currently undergoing rapid development with a number of international demonstration projects of scale 10–30 MW_e having commenced and units with a scale of 250–300 MW_e emerging in the progression towards commercialisation. Industrial scale testing of coal combustion and burners is also being conducted by technology vendors.The paper details the current international status of the technology; the contributions of current demonstrations; and a roadmap for commercial deployment.At its current state of maturity oxy-fuel technology may be considered semi-commercial, in that even if a unit was economically viable and could be provided by a vendor, the generator and vendor would need to share the technical risk. This is because guarantees could not at present be provided for operating characteristics associated with mature technologies such as reliability, emissions, ramp rate and spray control. This is due to the maturity of the technology associated with the capability of vendors and associated design and operational uncertainties, associated with a lack of plant experience at scale.The projected development of oxy-fuel technology for first-generation plant is provided, using an ASU for oxygen supply, standard furnace designs with externally recirculated flue gas, and limited thermal integration of the ASU and compression plant with the power plant. Potential features of second generation technology are listed.Listed issues delaying deployment indicate that market, economic, legal and issues of public acceptance are more significant than technical barriers.     

Exergy analysis as a tool for the integration of very complex energy systems: The case of carbonation/calcination CO2 systems in existing coal power plants

A common characteristic of carbon capture and storage systems is the important energy consumption associated with the CO₂ capture process. This important drawback can be solved with the analysis, synthesis and optimization of this type of energy systems. The second law of thermodynamics has proved to be an essential tool in power and chemical plant optimization. The exergy analysis method has demonstrated good results in the synthesis of complex systems and efficiency improvements in energy applications.In this paper, a synthesis of pinch analysis and second law analysis is used to show the optimum window design of the integration of a calcium looping cycle into an existing coal power plant for CO₂ capture. Results demonstrate that exergy analysis is an essential aid to reduce energy penalties in CO₂ capture energy systems. In particular, for the case of carbonation/calcination CO₂ systems integrated in existing coal power plants, almost 40% of the additional exergy consumption is available in the form of heat. Accordingly, the efficiency of the capture cycle depends strongly on the possibility of using this heat to produce extra steam (live, reheat and medium pressure) to generate extra power at steam turbine. The synthesis of pinch and second law analysis could reduce the additional coal consumption due to CO₂ capture 2.5 times, from 217 to 85 MW.     

Integration of post-combustion capture and storage into a pulverized coal-fired power plant

Post-combustion CO₂ capture and storage (CCS) presents a promising strategy to capture, compress, transport and store CO₂ from a high volume–low pressure flue gas stream emitted from a fossil fuel-fired power plant. This work undertakes the simulation of CO₂ capture and compression integration into an 800 MW_e supercritical coal-fired power plant using chemical process simulators. The focus is not only on the simulation of full load of flue gas stream into the CO₂ capture and compression, but also, on the impact of a partial load. The result reveals that the energy penalty of a low capture efficiency, for example, at 50% capture efficiency with 10% flue gas load is higher than for 90% flue gas load at the equivalent capture efficiency by about 440 kWh_e/tonne CO₂. The study also addresses the effect of CO₂ capture performance by different coal ranks. It is found that lignite pulverized coal (PC)-fired power plant has a higher energy requirement than subbituminous and bituminous PC-fired power plants by 40.1 and 98.6 MW_e, respectively. In addition to the investigation of energy requirement, other significant parameters including energy penalty, plant efficiency, amine flow rate and extracted steam flow rate, are also presented. The study reveals that operating at partial load, for example at half load with 90% CO₂ capture efficiency, as compared with full load, reduces the energy penalty, plant efficiency drop, amine flow rate and extracted steam flow rate by 9.9%, 24.4%, 50.0% and 49.9%, respectively. In addition, the effect of steam extracted from different locations from a series of steam turbine with the objective to achieve the lowest possible energy penalty is evaluated. The simulation shows that a low extracted steam pressure from a series of steam turbines, for example at 300 kPa, minimizes the energy penalty by up to 25.3%.     

Derivation of correlations to evaluate the impact of retrofitted post-combustion CO2 capture processes on steam power plant performance

When integrating a post-combustion CO₂ capture process and CO₂ compression into a steam power plant, the three interface quantities heat, electricity and cooling duty must be satisfied by the power plant, leading to a loss in net efficiency. The heat duty shows to be the largest contributor to the overall net efficiency penalty of the power plant. Additional energy penalty results from the cooling and electric power duty of the capture and compression units.In this work, the dependency of the energy penalty on the quantity and quality of the heat duty is analyzed and quantified for a state-of-the-art hard coal fired power plant. Furthermore, the energy penalty attributed to the additional cooling and power duty is quantified. As a result correlations are provided which enable to predict the impact of the heat, cooling and electricity duty of post-combustion CO₂ capture processes on the net output of a steam power plant in a holistic approach.     

Integration of CO2 capture unit using single- and blended-amines into supercritical coal-fired power plants: Implications for emission and energy management

This work provides the essential information and approaches for integration of carbon dioxide (CO₂) capture units into power plants, particularly the supercritical type, so that energy utilization and CO₂ emissions can be well managed in the subject power plants. An in-house model, developed at the University of Regina, Canada, was successfully used for simulating a 500 MW supercritical coal-fired power plant with a post-combustion CO₂ capture unit. The simulations enabled sensitivity and parametric study of the net efficiency of the power plant, the coal consumption rate, and the amounts of CO₂ captured and avoided. The parameters of interest include CO₂ capture efficiency, type of coal, flue gas delivery scheme, type of amine used in the capture unit, and steam pressure supplied to the capture unit for solvent regeneration. The results show that the advancement of MEA-based CO₂ capture units through uses of blended monoethanolamine–methyldiethanolamine (MEA–MDEA) and split flow configuration can potentially make the integration of power plant and CO₂ capture unit less energy intensive. Despite the increase in energy penalty, it may be worth capturing CO₂ at a higher efficiency to achieve greater CO₂ emissions avoided. The flue gas delivery scheme and the steam pressure drawn from the power plant to the CO₂ capture unit should be considered for process integration.     

Purification of oxyfuel-derived CO2

Oxyfuel combustion in a pulverised fuel coal-fired power station produces a raw CO₂ product containing contaminants such as water vapour plus oxygen, nitrogen and argon derived from the excess oxygen for combustion, impurities in the oxygen used, and any air leakage into the system. There are also acid gases present, such as SO₃, SO₂, HCl and NO_x produced as byproducts of combustion. At GHGT8 (White and Allam, 2006) we presented reactions that gave a path-way for SO₂ to be removed as H₂SO₄ and NO and NO₂ to be removed as HNO₃. In this paper we present initial results from the OxyCoal-UK project in which these reactions are being studied experimentally to provide the important reaction kinetic information that is so far missing from the literature. This experimental work is being carried out at Imperial College London with synthetic flue gas and then using actual flue gas via a sidestream at Doosan Babcock's 160 kW coal-fired oxyfuel rig. The results produced support the theory that SO_x and NO_x components can be removed during compression of raw oxyfuel-derived CO₂ and therefore, for emissions control and CO₂ product purity, traditional FGD and deNO_x systems should not be required in an oxyfuel-fired coal power plant.     

Effective retrofitting of post-combustion CO2 capture to coal-fired power plants and insensitivity of CO2 abatement costs to base plant efficiency

Existing coal-fired power plants were not designed to be retrofitted with carbon dioxide post-combustion capture (PCC) and have tended to be disregarded as suitable candidates for carbon capture and storage on the grounds that such a retrofit would be uneconomical. Low plant efficiency and poor performance with capture compared to new-build projects are often cited as critical barriers to capture retrofit. Steam turbine retrofit solutions are presented that can achieve effective thermodynamic integration between a post-combustion CO₂ capture plant and associated CO₂ compressors and the steam cycle of an existing retrofitted unit for a wide range of initial steam turbine designs. The relative merits of these capture retrofit integration options with respect to flexibility of the capture system and solvent upgradability will be discussed. Provided that effective capture system integration can be achieved, it can be shown that the abatement costs (or cost per tonne of CO₂ to justify capture) for retrofitting existing units is independent of the initial plant efficiency. This then means that a greater number of existing power plants are potentially suitable for successful retrofits of post-combustion capture to reduce power sector emissions. Such a wider choice of retrofit sites would also give greater scope to exploit favourable site-specific conditions for CCS, such as ready access to geological storage.     

Designing a supercritical steam cycle to integrate the energy requirements of CO2 amine scrubbing

Absorption by chemical solvents combined with CO₂ long-term storage appears to offer interesting and commercial applicable CO₂ capture technology. However one of the main disadvantages is related to the large quantities of heat required to regenerate the amine solvent that means an important power plant efficiency penalty. Different studies have analyzed alternatives to reduce the heat duty on the reboiler and the thermal integration requirements on existing power cycles. In these studies integration principles have been well set up, but there is a lack of information about how to achieve an integrated design and the thermal balances of the modified cycle flowsheet. This paper proposes and provides details about a set of modifications of a supercritical steam cycle to overcome the energy requirements through energetic integration with the aim of reducing the efficiency and power output penalty associated with CO₂ capture process. Modifications include a new designed low-pressure heater flowsheet to take advantage of the CO₂ compression cooling for postcombustion systems and integration of amine reboiler into a steam cycle. It has been carried out several simulations in order to obtain power plant performance depending on sorbent regeneration requirements.     

Comparison of data-based methods for monitoring of air leakages into oxyfuel power plants

Air leakages compromise the CO₂ capture rate and auxiliary power consumption of oxyfuel power plants. Constructive measures can significantly improve the leakage rate in newly built plants. However, the mitigation of increasing leakage rates during the plant lifetime is crucial for high plant efficiency. In this paper, we apply three statistical methods on experimental process data gathered in an air leakage test in Vattenfall's Oxyfuel Pilot Plant in Schwarze Pumpe, Germany. The performance of the methods in identifying increasing leakage rates and localizing the leakage source is investigated. It was found that all three methods can identify and localize even small increases of the leakage rate. A combination of all three methods allows taking advantage of the individual features of each method. Additional installation of CO₂, O₂, H₂O, and SO₂ measurements in the oxidizer can considerably enhance localization performance. Finally, it is shown that the results can be transferred to commercial-scale oxyfuel pilot plants by generating training data with thermodynamic plant models.     

Long-term coal gasification-based power plants with near-zero emissions. Part A: Zecomix cycle

These two part papers analyse three plant configurations for high efficiency, near-zero emissions power generation from coal, suitable for long-term installations. In the first part the Zecomix cycle, a novel power plant based on various innovative processes, is presented. Zecomix plant is based on a coal hydrogasification process, using recycled steam and hydrogen as gasifying agents, to produce a CH₄ rich syngas. Methane is then converted to an H₂/H₂O based syngas and CO₂ is captured, by reacting in two carbonator reactors with CaO-based solid sorbent. CaCO₃ produced in carbonators is thermally regenerated in a calciner. The synthetic fuel is burned with oxygen in a semi-closed high temperature steam cycle, with a supercritical heat recovery.The paper presents a detailed analysis of the thermodynamic aspects of the process, with the scope of assessing its potential performance in terms of efficiency and emissions. Main operating parameters of the chemical island (e.g. hydrogasifier and calciner pressure, steam flow rates to carbonators, syngas recycle fraction) and of the power island (e.g. pressure ratio, turbine inlet temperature and reheat pressure) were varied in order to evaluate their effect on plant performance and to optimize the process. Critical issues are specifically discussed: the calcination process, the calcium oxide utilization in carbonators, the cooling requirement of the high temperature turbine, the presence of incondensable species in the steam cycle. An accurate performance estimation is therefore developed by considering advanced components, as an evolution of today's technology, excluding unproven devices whose feasibility cannot be anticipated.Depending on sorbent utilization, a net plant efficiency of 44–47% with a virtually complete carbon capture was obtained, a very interesting result with respect to other proposed coal-fired power plants with carbon capture. The high complexity of the chemical island and the importance of a good sorbent performance should be however taken into account for a fair comparison with other plant concepts. Further experimental investigations are mandatory to demonstrate the technical and economical feasibility of the Zecomix plant.     

CO2 capture from combined cycles integrated with Molten Carbonate Fuel Cells

In this paper Molten Carbonate Fuel Cells (MCFCs) are considered for their potential application in carbon dioxide separation when integrated into natural gas fired combined cycles. The MCFC performs on the anode side an electrochemical oxidation of natural gas by means of CO₃^2? ions which, as far as carbon capture is concerned, results in a twofold advantage: the cell removes CO₂ fed at the cathode to promote carbonate ion transport across the electrolyte and any dilution of the oxidized products is avoided.The MCFC can be “retrofitted” into a combined cycle, giving the opportunity to remove most of the CO₂ contained in the gas turbine exhaust gases before they enter the heat recovery steam generator (HRSG), and allowing to exploit the heat recovery steam cycle in an efficient “hybrid” fuel cell + steam turbine configuration. The carbon dioxide can be easily recovered from the cell anode exhaust after combustion with pure oxygen (supplied by an air separation unit) of the residual fuel, cooling of the combustion products in the HRSG and water separation. The resulting power cycle has the potential to keep the overall cycle electrical efficiency approximately unchanged with respect to the original combined cycle, while separating 80% of the CO₂ otherwise vented and limiting the size of the fuel cell, which contributes to about 17% of the total power output so that most of the power capacity relies on conventional low cost turbo-machinery. The calculated specific energy for CO₂ avoided is about 4 times lower than average values for conventional post-combustion capture technology. A sensitivity analysis shows that positive results hold also changing significantly a number of MCFC and plant design parameters.     

Evaluation of different CHP options for refinery integration in the context of a low carbon future

This study presents a comparison of different concepts for delivering combined heat and power (CHP) to a refinery in Norway. A reference case of producing high pressure steam from natural gas in boilers and electricity in a combined cycle power plant, is compared to a: (1) natural gas fueled CHP without any CO₂ capture; (2) hydrogen fueled CHP with hydrogen produced from steam methane reforming (SMR); (3) hydrogen fueled CHP with hydrogen produced from autothermal reforming (ATR); and finally (4) natural gas fueled CHP with postcombustion CO₂ removal. The options are compared on the basis of first law efficiency, emissions of CO₂ and a simplified cash flow evaluation. Results show that in terms of efficiency the standard natural gas fueled CHP performs better than the reference case as well as the options with carbon capture. The low carbon options in turn offer lower emissions of greenhouse gases while maintaining the same efficiency as the reference case. The cash flow analysis shows that for any option, a certain mix of prices is required to produce a positive cash flow. As expected, the relationship between natural gas price and electricity price affects all options. Also the value of heat and CO₂ emissions plays an important role.     

Oxygen supply for oxyfuel CO2 capture

This paper presents the results of a study to develop Air Products’ air separation unit (ASU) offerings for oxyfuel coal CO₂ capture projects. A scalable “reference plant” concept is described to match particular sizes of power generation equipment, taking into account factors such as safety, reliability, operating flexibility, efficiency, and low capital cost. We describe the selection of a process cycle to exploit the low purity requirements, as well as the options for compression machinery and drivers as the scale of the plant increases and the sizes of referenced equipment limit the possibilities. We also explore integration with other elements of the system, such as preheating condensate or heating and expanding pressurised nitrogen. In addition, we consider how the ASU affects the flexibility of the oxyfuel system and discuss how its power consumption can be reduced during periods of high power demand. Finally, the advantages and disadvantages of different execution strategies for air separation unit projects are discussed, as well as alternative commercial models for the supply of oxygen.     

Exergetic Potential of Fuels: The Case of a SOFC-Based Power Plant

Abstract

The method of exergy analysis is presented for a SOFC power plant involving external steam reforming and fed by methane and ethanol. The optimal operation parameters of the integrated SOFC plant are specified after minimizing the existing energy and exergy losses. A comparison of methane and ethanol as appropriate fuels for a SOFC-based power plant is provided in terms of exergetic efficiency assuming the minimum allowable (for carbon-free operation) reforming factors for both cases. Then, a parametric analysis provides guidelines for practical design. It is concluded that the exergy calculations pinpoint the losses accurately and that the exergy analysis gives a better insight into the system's process.     

Chemical-looping combustion using syngas as fuel

Chemical-looping combustion (CLC) is a combustion technology where an oxygen carrier is used to transfer oxygen from the combustion air to the fuel, avoiding direct contact between air and fuel. Thus, CO₂ and H₂O are inherently separated from the rest of the flue gases and the carbon dioxide can be obtained in a pure form without the use of an energy intensive air separation unit. The paper presents results from a 3-year project devoted to developing the CLC technology for use with syngas from coal gasification. The project has focused on: (i) the development of oxygen carrier particles, (ii) establishing a reactor design and feasible operating conditions and (iii) construction and operation of a continuously working hot reactor. Approximately, 300 different oxygen carriers based on oxides of the metals Ni, Fe, Mn and Cu were investigated with respect to parameters, which are important in a CLC system, and from these investigations, several particles were found to possess suitable qualities as oxygen carriers. Several cold-model prototypes of CLC based on interconnected fluidized bed reactors were tested, and from these tests a hot prototype CLC reactor system was constructed and operated successfully using three carriers based on Ni, Fe and Mn developed within the project. The particles were used for 30–70 h with combustion, but were circulated under hot conditions for 60–150 h.