Combustion characteristics of coal in a mixture of oxygen and recycled flue gas

The combustion of coal in a mixture of pure O₂ and recycled flue gas is one variant of a novel combustion approach called oxy-fuel combustion. With the absence of N₂, this approach leads to a flue gas stream highly enriched in CO₂. For many applications, this flue gas stream can then be compressed and sequestered without further separation. As a result, oxy-fuel combustion is an attractive way to capture CO₂ produced from fossil fuel combustion. When coal is burned in this O₂ and CO₂ rich environment, its combustion characteristics can be very different from conventional air-fired combustion. In CETC-O, a vertical combustor research facility has been used in the past years to investigate the combustion characteristics of several different coals with this variant of oxy-fuel combustion. This included flame stability, emissions of NO_x, SO_x and trace elements, heat transfer, in-furnace flame profiles and flue gas compositions. This paper will report some of the major findings obtained from these research activities.     

CO2 capture using oxygen enhanced combustion strategies for natural gas power plants

This paper describes a series of experiments conducted with natural gas in air and in mixtures of oxygen and recycled flue gas, termed O₂/CO₂ recycle combustion. The objective is to enrich the flue gas with CO₂ to facilitate its capture and sequestration. Detailed measurements of gas composition, flame temperature and heat flux profiles were taken inside CANMET's 0.3 MWth down-fired vertical combustor fitted with a proprietary pilot scale burner. Flue gas composition was continuously monitored. The effects of burner operation, including swirling of secondary stream and air staging, on flame characteristics and NO_x emissions were also studied. The results of this work indicate that oxy-gas combustion techniques based on O₂/CO₂ combustion with flue gas recycle offer excellent potential for retrofit to conventional boilers for CO₂ emission abatement. Other benefits of the technology include considerable reduction and even elimination of NO_x emissions, improved plant efficiency due to lower gas volume and better operational flexibility.     

CO2 sequestration from coal fired power plants

The paper takes into consideration a new approach for CO₂ capture and transport, based on the formation of solid CO₂ hydrates.Carbon dioxide sequestration from power plants can take advantage of the properties of gas hydrates. The formation and decomposition of hydrates from various N₂-CO₂ mixtures has been studied experimentally in a 2 l reactor, to determine the CO₂ separation in terms of hydrate composition and residual CO₂ content in the reacted gas.Carbon dioxide acts as a co-former for the production of hydrates containing nitrogen, besides CO₂. The mixed hydrates that are obtained are less stable than simple CO₂ hydrates. When CO₂ content in the flue gas is higher than 30% by volume, the hydrates formed at 5 MPa are sufficiently concentrated (about 70% CO₂) and carbon dioxide reduction in the reacted gas is acceptable.The application of a process based on hydrate formation could be especially interesting (for CO₂ capture and transport) when connected to an oxy-coal combustion process; in this case the CO₂ content in the flue gas is very high and the hydrate formation is greatly facilitated.     

Simulation of turbulent combustion and NO formation in a swirl combustor

A presumed probability density function (PDF) model for temperature fluctuation is proposed and formulated in this paper. It incorporates a two-step reaction mechanism for propane combustion and the thermal and prompt NO formation mechanisms. The present model, together with a new algebraic Reynolds stress model (ASM), is employed to simulate the turbulent combustion and NO formation in a swirl combustor. The calculated propane, carbon monoxide, and carbon dioxide concentrations agree with the measurement. The calculated gas temperature and oxygen and NO concentrations are in general agreement with the measured data. The simulated results show that NO forms mainly in the upstream region of the combustor. The flue gas recirculation effectively abates the nitrogen oxides (NO_x) emission in the combustor.     

Separation of carbon dioxide from flue emissions using Endex principles

In an Endex reactor endothermic and exothermic reactions are directly thermally coupled and kinetically matched to achieve intrinsic thermal stability, efficient conversion, autothermal operation, and minimal heat losses. Applied to the problem of in-line carbon dioxide separation from flue gas, Endex principles hold out the promise of effecting a CO₂-capture technology of unprecedented economic viability. In this work we describe an Endex Calcium Looping reactor, in which heat released by chemisorption of carbon dioxide onto calcium oxide is used directly to drive the reverse reaction, yielding a pure stream of CO₂ for compression and geosequestration. In this initial study we model the proposed reactor as a continuous-flow dynamical system in the well-stirred limit, compute the steady states and analyse their stability properties over the operating parameter space, flag potential design and operational challenges, and suggest an optimum regime for effective operation.     

Progress in carbon dioxide capture and separation research for gasification-based power generation point sources

The purpose of the present work is to investigate novel approaches, materials, and molecules for the abatement of carbon dioxide (CO₂) at the pre-combustion stage of gasification-based power generation point sources. The capture/separation step for CO₂ from large point sources is a critical one with respect to the technical feasibility and cost of the overall carbon sequestration scenario. For large point sources, such as those found in power generation, the carbon dioxide capture techniques being investigated by the Office of Research and Development of the National Energy Technology Laboratory possess the potential for improved efficiency and reduced costs as compared to more conventional technologies. The investigated techniques can have wide applications, but the present research is focused on the capture/separation of carbon dioxide from fuel gas (pre-combustion gas) from processes such as the Integrated Gasification Combined Cycle (IGCC) process. For such applications, novel concepts are being developed in wet scrubbing with physical sorption, chemical sorption with solid sorbents, and separation by membranes. In one concept, a wet scrubbing technique is being investigated that uses a physical solvent process to remove CO₂ from fuel gas of an IGCC system at elevated temperature and pressure. The need to define an “ideal” solvent has led to the study of the solubility and mass transfer properties of various solvents. Pertaining to another separation technology, fabrication techniques and mechanistic studies for membranes separating CO₂ from the fuel gas produced by coal gasification are also being performed. Membranes that consist of CO₂-philic ionic liquids encapsulated into a polymeric substrate have been investigated for permeability and selectivity. Finally, processes based on dry, regenerable sorbents are additional techniques for CO₂ capture from fuel gas. An overview of these novel techniques is presented along with a research progress status of technologies related to membranes and physical solvents.     

Combination of Sorption-Enhanced Steam Methane Reforming and Electricity Generation by MCFC: Concept and Numerical Simulation Analysis

Abstract

Reformed gas made by the steam methane reforming(SMR) process is used as fuel feed to MCFC, but it is not as good as pure hydrogen due to the presence of CO₂ and CO. The sorption-enhanced steam methane reforming(SE-SMR) process can reduce CO₂ and CO to a low level and produce high purity hydrogen. Considering the merits of similar operating temperatures (about 500°C) and carbon dioxide recycle, a novel concept of a six-step sorption-enhanced steam methane reforming (SE-SMR) combined with electricity generation by molten carbonate fuel cell (MCFC) is proposed. In the present paper, a cycle of the SE-SMR process, which include the steps of reaction/adsorption, depressurization, gas purges (nitrogen and reformed gas, respectively), and pressurization with reformed gas, is modeled and analyzed. The process stream in the SE-SMR process is used as anode feed in MCFC. According to the result of numerical simulation, a fuel cell grade hydrogen product (above 80% purity) at the SE-SMR temperature of 450°C can be obtained. A carbon dioxide recycle mechanism is developed for cathode feed of MCFC from flue gas by burning with excess air to achieve a proper CO₂/air ratio (about 30:70). The novel electricity generation system, which can operate at lower energy consumption and high purity hydrogen feed is helpful for the MCFC'S performance and life time.     

Critical review of strategies for CO2 delivery to large-scale microalgae cultures

Microalgae have great, yet relatively untapped potential as a highly productive crop for the production of animal and aquaculture feed, biofuels, and nutraceutical products. Compared to conventional terrestrial crops they have a very fast growth rate and can be produced on non-arable land. During microalgae cultivation, carbon dioxide (CO₂) is supplied as the carbon source for photosynthesising microalgae. There are a number of potential CO₂ supplies including air, flue gas and purified CO₂. In addition, several strategies have been applied to the delivery of CO₂ to microalgae production systems, including directly bubbling CO₂-rich gas, microbubbles, porous membrane spargers and non-porous membrane contactors. This article provides a comparative analysis of the different CO₂ supply and delivery strategies and how they relate to each other.     

Modeling of oxy-fuel combustion for a western Canadian sub-bituminous coal

The motivation of this research is to develop practical oxy-coal combustion techniques in order to facilitate the conversion of coal-fired utility power plants so as to recover a CO₂ rich flue gas stream for use and/or sequestration. The objective of this study is to ascertain the applicability and accuracy of a modeling tool to assist with future pilot scale oxy-fuel combustion experiments and burner scale-up studies. Two modes of oxy-coal combustion, O₂ enriched air (OEA) and recycled flue gas (RFG), were experimentally tested in a 0.3 MW_th pilot-scale combustor using a western Canadian sub-bituminous coal. The computational fluid dynamic tool was utilized to model the combustion, heat transfer and pollutant formation characteristics of these test cases and to examine the impact due to changes in the combustion medium, burner swirl and burner configuration. The model provided insights for the observed variation in NO_x production among the test cases: the dramatic increase in the OEA mode, the drop at higher burner swirl settings and the surprisingly small reduction in the RFG mode. Overall the model results compared well with measured data in all test cases and established confidence in using the model to explore new design concepts for oxy-coal combustion.     

Preliminary analysis of process flow sheet modifications for energy efficient CO2 capture from flue gases using chemical absorption

The energy penalty associated with solvent based capture of CO₂ from power station flue gases can be reduced by incorporating process flow sheet modifications into the standard process. A review of modifications suggested in the open and patent literature identified several options, primarily intended for use in the gas processing industry. It was not immediately clear whether these options would have the same benefits when applied to CO₂ capture from near atmospheric pressure combustion flue gases. Process flow sheet modifications, including split flow, rich split, vapour recompression, and inter-stage cooling, were therefore modelled using a commercial rate-based simulation package. The models were completed for a Queensland (Australia) based pilot plant running on 30% MEA as the solvent. The preliminary modelling results showed considerable benefits in reducing the energy penalty of capturing CO₂ from combustion flue gases. Further work will focus on optimising and validating the most relevant process flow sheet modifications in a pilot plant.     

Multiphase CFD-based models for chemical looping combustion process: Fuel reactor modeling

Chemical looping combustion (CLC) is a flameless two-step fuel combustion that produces a pure CO₂ stream, ready for compression and sequestration. The process is composed of two interconnected fluidized bed reactors. The air reactor which is a conventional circulating fluidized bed and the fuel reactor which is a bubbling fluidized bed. The basic principle is to avoid the direct contact of air and fuel during the combustion by introducing a highly-reactive metal particle, referred to as oxygen carrier, to transport oxygen from the air to the fuel. In the process, the products from combustion are kept separated from the rest of the flue gases namely nitrogen and excess oxygen. This process eliminates the energy intensive step to separate the CO₂ from nitrogen-rich flue gas that reduce the thermal efficiency.Fundamental knowledge of multiphase reactive fluid dynamic behavior of the gas-solid flow is essential for the optimization and operation of a chemical looping combustor.Our recent thorough literature review shows that multiphase CFD-based models have not been adapted to chemical looping combustion processes in the open literature. In this study, we have developed the reaction kinetics model of the fuel reactor and implemented the kinetic model into a multiphase hydrodynamic model, MFIX, developed earlier at the National Energy Technology Laboratory. Simulated fuel reactor flows revealed high weight fraction of unburned methane fuel in the flue gas along with CO₂ and H₂O. This behavior implies high fuel loss at the exit of the reactor and indicates the necessity to increase the residence time, say by decreasing the fuel flow rate, or to recirculate the unburned methane after condensing and removing CO₂.     

Understanding the performance of membrane for direct air capture of CO2

Direct air capture (DAC) of CO₂ is becoming increasingly important for reducing greenhouse gas concentrations in the atmosphere. However, the cost and energy requirements associated with DAC make it less economically feasible than carbon capture from flue gases. While various methods like solid sorbents and gas–liquid absorption have been explored for DAC, membrane processes have only recently been investigated. The objective of this study is to examine the separation performance of a membrane unit for capturing CO₂ from ambient air. The performance of a membrane depends on several factors, including the composition of the feed gas, pressure ratio, material selectivity, and membrane area. The single-stage separation process with the co-current flow and constant permeability flux model is evaluated using a commercial module integrated with a process simulator to separate a binary mixture of carbon dioxide and nitrogen to assess the sensitivity of selectivity on purity and recovery of CO₂ in permeate, and power requirement. Additionally, three levels of CO₂ reduction from the feed stream to the retentate stream (25%, 50%, and 75%) are studied. A trade-off between purity and recovery factor is observed, and achieving high purity in permeate requires high concentration in the retentate.     

Design and operation of pilot plant for CO2 capture from IGCC flue gases by combined cryogenic and hydrate method

This project is a trial conducted under contract with CO₂CRC, Australia of a new CO₂ capture technology that can be applied to integrated gasification combined cycle power plants and other industrial gasification facilities. The technology is based on combination of two low temperature processes, namely cryogenic condensation and the formation of hydrates, to remove CO₂ from the gas stream. The first stage of this technology is condensation at −55 °C where CO₂ concentration is expected to be reduced by up to 75 mol%. Remaining CO₂ is captured in the form of solid hydrate at about 1 °C reducing CO₂ concentration down to 7 mol% using hydrate promoters. This integrated cryogenic condensation and CO₂ hydrate capture technology hold promise for greater reduction of CO₂ emissions at lower cost and energy demand. Overall, the process produced gas with a hydrogen content better than 90 mol%. The concentrated CO₂ stream was produced with 95-97 mol% purity in liquid form at high pressure and is available for re-use or sequestration. The enhancement of carbon dioxide hydrate formation and separation in the presence of new hydrate promoter is also discussed. A laboratory scale flow system for the continuous production of condensed CO₂ and carbon dioxide hydrates is also described and operational details are identified.     

Carbon deposition characteristics and regenerative ability of oxygen carrier particles for chemical-looping combustion

For gaseous fuel combustion with inherent CO₂ capture and low NO_x emission, chemical-looping combustion (CLC) may yield great advantages for the savings of energy to CO₂ separation and suppressing the effect on the environment. In a chemical-looping combustor, fuel is oxidized by metal oxide medium (oxygen carrier particle) in a reduction reactor. Reduced particles are transported to the oxidation reactor and oxidized by air and recycled to the reduction reactor. The fuel and the air are never mixed, and the gases from the reduction reactor, CO₂ and H₂O, leave the system as separate streams. The H₂O can be easily separated by condensation and pure CO₂ is obtained without any loss of energy for separation. In this study, NiO based particles are examined from the viewpoints of reaction kinetics, carbon deposition, and cyclic use (regenerative ability). The purpose of this study is to find appropriate reaction conditions to avoid carbon deposition and achieve high reaction rate (e.g., temperature and maximum carbon deposition-free conversion) and to certify regenerative ability of NiO/bentonite particles. In this study, 5.04% methane was used as fuel and air was used as oxidation gas. The carbon deposition characteristics, reduction kinetics and regenerative ability of oxygen carrier particles were examined by TGA (Thermal Gravimetrical Analyzer).     

CFD modelling of oxy-coal combustion in an entrained flow reactor

Oxy-fuel combustion is seen as one of the major options for CO₂ capture for both new and existing coal fired power stations. Coal is burned with a mixture of oxygen and recycled flue gas to obtain a rich CO₂ stream ready for sequestration. Computational fluid dynamics (CFD) tests for coal combustion under different O₂/CO₂ (21-35% vol O₂) atmospheres in an entrained flow reactor (EFR) were carried out using three coals of different volatile matter content. The temperature profiles, burning rates, burnout and concentration of major species, such as O₂, CO₂, CO, were predicted and compared with an air reference case. A decrease in gas temperature and burning rate was observed for 21% O₂/79% CO₂ environment in comparison to the air reference case due to the difference in gas properties between N₂ and CO₂. Experimental coal burnouts obtained in the EFR, were used to test the accuracy of the CFD model. The numerical results showed a decrease in coal burnout when N₂ was replaced by CO₂ for the same oxygen concentration (21%), but an improvement in the O₂/CO₂ atmosphere for an oxygen concentration higher than 30%. The numerical results for oxy-coal combustion were in good agreement with the experimental results.     

Preparation and adsorption properties of polyethylenimine containing fibrous adsorbent for carbon dioxide capture

We successfully prepared a novel fibrous adsorbent for carbon dioxide (CO₂) capture by coating polyethylenimine (PEI) on a glass fiber matrix, using epoxy resin (EP) as crosslinking agent. The physicochemical properties of the fibrous adsorbents were characterized in terms of Fourier transform infrared spectrometry and thermogravimetric analysis. Factors that affected the adsorption capacity of the fibrous adsorbent were studied, including the crosslinking agent dosage, coating weight, moisture, adsorption temperature, and CO₂ concentration of the simulated flue gas. The experimental results indicate that the properly crosslinked fibrous adsorbent had a high thermal stability at about 280°C. With a PEI/EP ratio of 10:1, a maximum adsorption capacity of 276.96 mg of CO₂/g of PEI was obtained at 30°C. Moisture had a promoting influence on the adsorption of CO₂ from flue gas. The CO₂ adsorption capacity of the fibrous adsorbent in the presence of moisture could be 19 times higher than that in dry conditions. The fibrous adsorbent could be completely regenerated at 120°C. The CO₂ adsorption capacity of the regenerated fibrous adsorbent was almost the same as that of the fresh adsorbent. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Efficient electrochemical synthesis of 2-arylsuccinic acids from CO2 and aryl-substituted alkenes with nickel as the cathode

A simple and efficient electrochemical route was developed by using non-noble metal nickel as the cathode and aluminum or magnesium as an anode for the synthesis of 2-arylsuccinic acids from carbon dioxide and aryl-substituted alkenes. The electrochemical dicarboxylation of aryl-substituted alkenes and carbon dioxide could be smoothly carried out in an undivided cell containing n-Bu₄NBr-DMF electrolyte with a constant current under 4 MPa pressure of CO₂ at room temperature in the absence of additional catalysts, and the corresponding 2-arylsuccinic acids were afforded in moderate to good yields (50-87%) and high selectivity (98%). The influence of some key factors (such as electrode materials, supporting electrolyte, substrate concentration, current density and CO₂ pressure) on the results of the electrochemical synthesis was investigated, and the electrochemical reaction mechanism was also briefly discussed.     

Coal combustion characteristics in a circulating fast fluidized bed

The effect of coal size (0.73–1.03 mm), excess air ratio (1.0–1.4), operating bed temperature (750–900‡C), coal feeding rate (1–3 kg/h), and coal recycle rate (20–40 kg/h) on combustion efficiency, temperature profiles along the bed height and flue gas composition have been determined in a bubbling and circulating fluidized bed combustor (7.8 cm-ID x 2.6 m-high). Combustion efficiency increases with increasing excess air ratio and operating bed temperature and it decreases with increasing particle size in the bubbling and circulating fluidzing beds. In general, temperature profiles and combustion efficiency are more uniform and higher in a circulating bed than those in bubbling bed. Combustion efficiency also increases with increasing recycle rate of unburned coal in the circulating bed. The ratio of CO/CO₂ of flue gas decreases with increasing bed temperature and excess air ratio, whereas the ratio of O₂(CO + CO₂) decreases with bed temperature in both bubbling and circulating fluidized beds.     

Spirulina platensis Culture with Flue Gas Feeding as a Cyanobacteria‐Based Carbon Sequestration Option

The scientific community is currently examining potential approaches in order to reduce the anthropical contributions to global warming. One approach is carbon capture and its storage, i.e., capturing CO₂ at its source and storing it indefinitely to avoid its release into the atmosphere. Conversion of CO₂ by microalgae or cyanobacteria is a sequestration option. Here, the application of an air‐lift reactor to flue gas treatment using cyanobacteria for the absorption of CO₂ was investigated, with the simultaneous abatement of NO_x. A Spirulina platensis culture was fed with CO₂ and NO_x, simulating a flue gas. The preliminary test yielded positive indications on the process feasibility, both in terms of cell productivity (86.8 mg L^–1d^–1) and CO₂ abatement (229 mg d^–1). Opportune dosages of flue gas used in fed‐batch test achieved a high abatement of CO₂ (407 mg d^–1), 90.0 % removal of NO_x, and a biomass production of 188.7 mg L^–1d^–1.     

The use of carbonic anhydrase to accelerate carbon dioxide capture processes

The chemical absorption of CO₂ into a monoethanolamine solvent is currently the most widely accepted commercial approach to carbon dioxide capture. However, the subsequent desorption of CO₂ from the solvents is extremely energy intensive. Alternative solvents are more energy efficient, but their slow reaction kinetics in the CO₂ absorption step limits application. The use of a carbonic anhydrase (CA) enzyme as a reaction promoter can potentially overcome this obstacle. Native, engineered and artificial CA enzymes have been investigated for this application. Immobilization of the enzyme within the gas absorber or in a membrane format can increase enzyme stability and avoid thermal denaturation in the stripper. However, immobilization is only effective if the mass transfer of carbon dioxide through the liquid phase to reach the immobilization substrate does not become rate controlling. Further research should also consider the process economics of large‐scale enzyme production and the long‐term performance of the enzyme under real flue gas conditions. © 2014 Society of Chemical Industry