CO_(2)capture costs of chemical looping combustion of biomass:A comparison of natural and synthetic oxygen carrier

Chemical looping combustion has the potential to be an efficient and low-cost technology capable of contributing to the reduction of the atmospheric concentration of CO_(2) in order to reach the 1.5/2°C goal and mitigate climate change.In this process,a metal oxide is used as oxygen carrier in a dual fluidized bed to generate clean CO_(2) via combustion of biomass.Most commonly,natural ores or synthetic materials are used as oxygen carrier whereas both must meet special requirements for the conversion of solid fuels.Synthetic oxygen carriers are characterized by higher reactivity at the expense of higher costs versus the lower-cost natural ores.To determine the viability of both possibilities,a techno-economic comparison of a synthetic material based on manganese,iron,and copper to the natural ore ilmenite was conducted.The synthetic oxygen carrier was characterized and tested in a pilot plant,where high combustion efficiencies up to 98.4%and carbon capture rates up to 98.5%were reached.The techno-economic assessment resulted in CO_(2) capture costs of 75 and 40€/tCO_(2) for the synthetic and natural ore route respectively,whereas a sensitivity analysis showed the high impact of production costs and attrition rates of the synthetic material.The synthetic oxygen carrier could break even with the natural ore in case of lower production costs and attrition rates,which could be reached by adapting the production process and recycling material.By comparison to state-of-the-art technologies,it is demonstrated that both routes are viable and the capture cost of CO_(2) could be reduced by implementing the chemical looping combustion technology.

Application of Fe_2O_3/Al_2O_3 Composite Particles as Oxygen Carrier of Chemical Looping Combustion

Chemical looping combustion （CLC） of carbonaceous compounds has been proposed, in the past decade, as an efficient method for CO2 capture without cost of extra energy penalties. The technique involves the use of a metal oxide as an oxygen carrier that transfers oxygen from combustion air to fuels. The combustion is carried out in a two-step process： in the fuel reactor, the fuel is oxidized by a metal oxide, and in the air reactor, the reduced metal is oxidized back to the original phase. The use of iron oxide as an oxygen carrier has been investigated in this article. Particles composed of 80 wt% Fe2O3, together with Al2O3 as binder, have been prepared by impregnation methods. X-ray diffraction （XRD） analysis reveals that Fe2O3 does not interact with the Al2O3 binder after multi-cycles. The reactivity of the oxygen carrier particles has been studied in twenty-cycle reduction-oxidation tests in a thermal gravimetrical analysis （TGA） reactor. The components in the outlet gas have been analyzed. It has been observed that about 85% of CH4 converted to CO2 and H2O during most of the reduction periods. The oxygen carrier has kept quite a high reactivity in the twenty-cycle reactions. In the first twenty reaction cycles, the reaction rates became slightly higher with the number of cyclic reactions increasing, which was confirmed by the scanning electron microscopy （SEM） test results. The SEM analysis revealed that the pore size inside the particle had been enlarged by the thermal stress during the reaction, which was favorable for diffusion of the gaseous reactants into the particles. The experimental results suggested that the Fe2O3/Al2O3 oxygen carrier was a promising candidate for a CLC system.

Petroleum coke conversion behavior in catalyst-assisted chemical looping combustion

Efficiently using petroleum coke as fuel and reducing carbon emission meanwhile have become attractive in oil processing industry.The paper is focused on the application of Chemical Looping Combustion(CLC)with petroleum coke,with the purpose of investigating its combustion performance and effects of potassium.Some experiments were performed in a laboratory scale fluidized bed facility with a natural manganese-based oxygen carrier.Experimental results indicated that the coke conversion is very sensitive to reaction temperature.The pre sent natural manganese-based oxygen carrier decorated by K has little effect on the improvement of coke conversion.XRD,SEM-EDX,and H2-TPR were adopted to characterize the reacted oxygen carrier samples.After being decorated by K,the oxygen carrier's capacity of transferring oxygen was decrea sed.A calcination temperature above the melting point of K2 CO3(891℃)shows better oxygen transfer reactivity in comparison to the one calcined at a lower temperature.The natural oxygen carrier used in the work has a high content of Si,which can easily react with K to form K(FeSi2 O6).Further,irrespective of reaction temperature,the coke conversion can be significantly enhanced by decorating the coke with K,with a demonstration of remarkably shorter reaction time,faster average coke gasification rate and higher average carbon conversion rate.

Experimental and mechanistic study on chemical looping combustion of caking coal

Under high-temperature batch fluidized bed conditions and by employing juye coal as the raw material,the present study determined the effects of the bed material,temperature,OC/C ratio,steam flow and oxygen carrier cycle on the chemical looping combustion of coal.In addition,the variations taking place in the surface functional groups of coal under different reaction times were investigated,and the variations achieved by the gas released under the pyrolysis and combustion of Juye coal were analyzed.As revealed from the results,the carbon conversion ratio and rate were elevated significantly,and the volume fraction of the outlet CO_(2)remained more than 92%under the oxygen carriers.The optimized reaction conditions to achieve the chemical looping combustion of Juye coal consisted of a temperature of 900℃,an OC/C ratio of 2,as well as a steam flow rate of 0.5 g·min^(-1).When the coal was undergoing the chemical looping combustion,volatiles primarily originated from the pyrolysis of aliphatic-CH_(3)and-CH_(2),and CO and H_(2)were largely generated from the gasification of aromatic carbon.In the CLC process,H_(2)O and CO_(2)began to separate out at 270℃,CH4 and tar began to precipitate at 370℃,and the amount of CO_(2)was continuously elevated with the rise of the temperature.

Effects of operating pressure on the key parameters of coal direct chemical looping combustion

Techno-economic development of chemical looping combustion （CLC） process has been one of the most pursued research areas of the present decade due to its ability to reduce carbon foot print during utilization of coal to generate energy. Based on a 2D computational fluid dynamics model, the present work provides a computational approach to study the effect of operating pressure--a key parameter in designing of CLC reactors, on optimum operating conditions. The effects of operating pressure have been examined in terms of reactors temperature, percentage of fuel conversion and purity of carbon dioxide in fuel reactor exhaust. The simulated results show qualitative agreement with the trends obtained by other investigators during experimental studies.

Migration of sulfur in in-situ gasification chemical looping combustion of Beisu coal with iron-and copper-based oxygen carriers

Chemical looping combustion(CLC)is an energy conversion technology with high efficiency and inherent separation of CO_(2).The existence of sulfur in coal may affect the CO_(2) purity and the performance of oxygen carrier due to the interactions between sulfur contaminants and oxygen carrier.The migration of sulfur in Beisu coal during the in-situ gasification chemical looping combustion(i G-CLC)process using two oxygen carriers(iron ore and Cu O/Si O_(2))was investigated respectively.The thermodynamic analysis results showed the formation of metal sulfides was thermodynamically favored at low temperatures and low oxygen excess coefficients,while they were obviously inhibited and the production of SO_(2) was significantly promoted with an increase in temperature and oxygen excess coefficient.Moreover,part of sulfur was captured and fixed in the forms of alkali/alkaline earth metal sulfate due to the high amount of alkali/alkaline earth metal oxides in the coal ash or/and oxygen carrier.The experimental results showed that the sulfur in coal mainly released in the form of SO_(2),and the sulfur conversion efficiency(XS)in the reduction stage were 51.04%and 48.24%when using iron ore and Cu O/Si O_(2) respectively.The existence of metal sulfides was observed in the reduced oxygen carriers.The values of XSin the reoxidation process reached 3.80%and 7.64%when using iron ore and Cu O/Si O_(2) respectively.The residue and accumulation of sulfur were also found on the surfaces of two oxygen carriers.

Cycle performance of Cu-based oxygen carrier based on a chemical-looping combustion process

The cycle life of oxygen carrier（OC） is crucial to the practical applications of chemical looping combustion（CLC）. Cycle performance of Cu/SiO2 prepared with a mechanical mixing method was evaluated based on a CLC process characterized with an added methane steam reforming step. The Cu/SiO2 exhibited high redox reactivity in the initial cycles, while the performance degraded with cycle number. Through characterization of the degraded Cu/SiO2, the performance degradation was mainly caused by the secondary particles＇ fragmentation and the fine particles＇ local agglomeration, which worsened the distribution and diffusion of the reactive gases in the packed bed. A regeneration method of the degraded OC based on re-granulation has been proposed, and its mechanism has been illustrated. With this method, the performance of the degraded OC through 420 redox cycles was recovered to a level close to the initial one.

Investigation of the redox performance of pyrite cinder calcined at different temperature in chemical looping combustion

As an industrial solid waste,pyrite cinder exhibited excellent reactivity and cycle stability in chemical looping combustion.Prior to the experiment,oxygen carriers often experienced a high temperature calcination process to stabilize the physico-chemical properties,which presented significant influence on the redox performance of oxygen carriers.However,the effect of calcination temperature on the cyclic reaction performance of pyrite cinder has not been studied in detail.In this work,the effect of calcination temperature on the redox activity and attrition characteristic of pyrite cinder were studied in a fluidizedbed reactor using CH_(4) as fuel.A series of pyrite cinder samples were prepared by controlling the calcination temperature.The redox activity and attrition rate of the obtained pyrite cinder samples were investigated deeply.The results showed that calcination temperature displayed significant impact on the redox performance of pyrite cinder.Considering CH_(4) conversion(80%–85%)and attrition resistance,the pyrite cinder calcined at 1050℃ presented excellent redox properties.In the whole experiment process,the CO_(2) selectivity of the pyrite cinder samples were not affected by the calcination temperature and were still close to 100%.The results can provide reference for optimizing the calcination temperature of pyrite cinder during chemical looping process.

Numerical simulation of solid circulation mechanism and gas flow paths in a chemical looping combustion system

To study the gas-solid flow characteristics in a chemical looping combustion system integrated with a moving bed air reactor,a 3D full-loop numerical model was established using the Eulerian-Eulerian approach integrated with the kinetic theory of granular flow.The solid circulation mechanism and gas leakage performance were studied in detail.The simulation results showed that in the start-up process,the solid circulation rate first increased to approximately 5 kg/s and then dropped to approximately 1.2 kg/s;this observation was related to the dynamic control of the pressure distribution.In this system,the gas leakage between the inertial separator,upper air reactor,and lower air reactor was restrained by adjusting the pressure difference,thus obtaining optimal gas flow paths.When the pressures at the outlets of the inertial separator,upper air reactor,and lower air were 7.4,11.0,and 14.6 kPa,respectively,the gas leakage ratio was less than 1%in the system.

Reactivity Investigation on Iron-Titanium Oxides for a Moving Bed Chemical Looping Combustion Implementation

Ilmenite-type natural ore which is constituted mainly of iron-titanium oxide is an interesting candidate as an oxygen carrier in chemical looping combustion (CLC) process. Its reactivity was investigated using methane as reducing gas and air as oxidizing gas. Experiments were carried out in a coupled thermogravimetric–thermo differential analyzer (TGA-DTA). When temperature increases from 700℃ to 1000℃, the reaction rate increases by 50 times while the oxygen transfer capacity passes from 1.8% to 12%. TG-DT analyses showed that the overall mass loss due to ilmenite reduction reached at most 12%. It corresponds to 87% of theoretical mass loss due to the transformation of Fe2TiO5 into Fe and TiO2. It is established that the reduction for the iron-titanium oxides occurs in two steps: Fe2TiO5→ FeTiO3→ Fe + TiO2. The titanium reduction from the state TiO2 to the stage Ti3O5 was observed as well. This behavior is supported by XRD analysis. Subsequent oxidation of the reduced mineral led to recover the starting oxide. The stability of iron-titanium oxides was established over 35 looping cycles of oxidation-reduction, with an increase of 5% of oxygen transfer capacity and reactivity in the first 5 cycles and after that, ilmenite reactivity remained constant. At high temperatures, catalytic effect of ilmenite on methane decomposition leading to carbon deposition is observed. The deposited carbon participates in the reactivity of the oxide.

Numerical and experimental analysis for simulating fuel reactor in chemical looping combustor system

The greenhouse problem has a significant effect on our communities such as,health and climate.Carbon dioxide is one of the main gases that cause global warming.Therefore,CO2 capture techniques have been the focus of attention these days.The chemical looping combustion technique adopted the air reactor and fuel reactor to recycle heat energy.This study presents a numerical and experimental investigation on a fuel reactor in chemical looping combustor(CLC)system.The present numerical model is introduced by the kinetic theory of granular flow and coupled with gas–solid flow with chemical reactions to simulate the combustion of solids in the CLC.The k–εturbulent model was used to model the gas phase and the particle phase.The developed model simplify the prediction of flow patterns,particle velocities,gas velocities,and composition profiles of gas products and the distribution of heterogeneous reaction rates under the same operating conditions.The predicted and experimental results were compared according to the basis of determination coefficient(R2).In addition the results showed that there is a good agreement between the predicted and experimental data.The value of(R2)for CO,CO2 and CH4 was 0.959,0.925 and 0.969 respectively.This shows that the present model is a promising simulation for solid particle combustion and gives the power direction for the design and optimization of the CLC systems.

Performance analysis of an O_2/ CO_2 power plant based on chemical looping air separation

The process of an O2//CO2 power plant based on chemical looping air separation （CLAS） is modeled using the Aspen Plus software. The operating parameters and power consumption of the CLAS unit are analyzed. The CLAS system, thermal power generation system and flue gas cooling and compression unit （CCU） are coupled and optimized, and the temperature and flow of the flue gas extraction are determined. The results indicate that the net plant efficiency of CLAS O2/CO2 power plant is 39.2%, which is only 3.54% lower than that of the conventional power plants without carbon capture. However, the O2/CO2 power plant based on cryogenic air separation technology brings 8% to 10% decrease in the net plant efficiency. By optimizations, the net plant efficiency increases by 1.65%. The energy consumption of the CCU accounts for 59.7% and the pump accounts for 27.1%. The oxygen concentration from the chemical looping air separation unit is 12.2%.

ACCESSING HIGH THERMAL EFFICIENCY POWER GENERATION USING FLUID PHASE CHEMICAL LOOPING

In order to burn a hydrocarbon fuel efficiently using conventional cycles,very high temperatures are required.Chemical looping combustion（CLC）offers an alternative cycle for large scale power production.In CLC a carrier molecule is used to transport oxygen between two redox reactions,one where the carrier is oxidised and another where it is reduced by reaction with a fuel.Separation of the oxygen carrier from fuel ash can be aided by means of phase difference and this is a key advantage of fluid phase CLC where the carrier medium proposed is sodium,potassium or zinc.The principle exploited in fluid phase CLC is the recirculation of both energy and entropy.High thermal efficiencies,circa 75% at 35 bar are theoretically achievable taking into account component efficiencies,with separation of nitrogen and carbon dioxide,in combination with the water shift gas reaction,as an inherent part of the cycle if air is used as the oxygen source.

Off-design performance of a chemical looping combustion (CLC) combined cycle:effects of ambient temperature

The present work investigates the influence of ambient temperature on the steady-state off-design thermodynamic performance of a chemical looping combustion(CLC) combined cycle.A sensitivity analysis of the CLC reactor system was conducted,which shows that the parameters that influence the temperatures of the CLC reactors most are the flow rate and temperature of air entering the air reactor.For the ambient temperature variation,three off-design control strategies have been assumed and compared:1) without any Inlet Guide Vane(IGV) control,2) IGV control to maintain air reactor temperature and 3) IGV control to maintain constant fuel reactor temperature,aside from fuel flow rate adjusting.Results indicate that,compared with the conventional combined cycle,due to the requirement of pressure balance at outlet of the two CLC reactors,CLC combined cycle shows completely different off-design thermodynamic characteristics regardless of the control strategy adopted.For the first control strategy,temperatures of the two CLC reactors both rise obviously as ambient temperature increases.IGV control adopted by the second and the third strategy has the effect to maintain one of the two reactors' temperatures at design condition when ambient temperature is above design point.Compare with the second strategy,the third would induce more severe decrease of efficiency and output power of the CLC combined cycle.

Chemical looping combustion of coal in interconnected fluidized beds

Chemical looping combustion is the indirect combustion by use of oxygen carrier. It can be used for CO2 capture in power generating processes. In this paper, chemical looping combustion of coal in interconnected fluidized beds with inherent separation of CO2 is proposed. It consists of a high velocity fluidized bed as an air reactor in which oxygen carrier is oxidized, a cyclone, and a bubbling fluidized bed as a fuel reactor in which oxygen carrier is reduced by direct and indirect reactions with coal. The air reactor is connected to the fuel reactor through the cyclone. To raise the high carbon conversion efficiency and separate oxygen carrier particle from ash, coal slurry instead of coal particle is introduced into the bottom of the bubbling fluidized bed. Coal gasification and the reduction of oxygen carrier with the water gas take place simultaneously in the fuel reactor. The flue gas from the fuel reactor is CO2 and water. Almost pure CO2 could be obtained after the condensation of water. The reduced oxygen carrier is then returned back to the air reactor, where it is oxidized with air. Thermodynamics analysis indicates that NiO/Ni oxygen carrier is the optimal one for chemical looping combustion of coal. Simulation of the processes for chemical looping combustion of coal, including coal gasification and reduction of oxygen carrier, is carried out with Aspen Plus software. The effects of air reactor temperature, fuel reactor temperature, and ratio of water to coal on the composition of fuel gas, recirculation of oxygen carrier particles, etc., are discussed. Some useful results are achieved. The suitable temperature of air reactor should be between 1050–1150°C and the optimal temperature of the fuel reactor be between 900–950°C.

Mature versus emerging technologies for CO2 capture in power plants： Key open issues in post-combustion amine scrubbing and in chemical looping combustion

Carbon capture and storage （CCS） have acquired an increasing importance in the debate on global wanning as a mean to decrease the environmental impact of energy conversion technologies, by capturing the CO2 produced from the use of fossil fuels in electricity generation and industrial processes. In this respect, post-combustion systems have received great attention as a possible near-term CO2 capture technology that can be retrofitted to existing power plants. This capture technology is, however, energy-intensive and results in large equipment sizes because of the large volumes of the flue gas to be treated. To cope with the demerits of other CCS technologies, the chemical looping combustion （CLC） process has been recently considered as a solution for CO2 separation. It is typically referred to as a technology without energy penalty. Indeed, in CLC the fuel and the combustion air are never mixed and the gases from the oxidation of the fuel （i.e., CO2 and H2O） leave the system as a separate stream and can be separated by condensation of H2O without any loss of energy. The key issue for the CLC process is to find a suitable oxygen carrier, which provides the fuel with the activated oxygen needed for combustion. The aim of this work is to explore the feasibility of using perovskites as oxygen carriers in CLC and to consider the possible advantages with respect to the scrubbing process with amines, a mature post-combustion technology for CO2 separation.

Sulfur evolution in chemical looping combustion of coal with MnFe_2O_4 oxygen carrier

Chemical looping combustion （CLC） of coal has gained increasing attention as a novel combustion technology for its advantages in CO2 capture. Sulfur evolution from coal causes great harm from either the CLC operational or environmental perspective. In this research, a combined MnFe2O4 oxygen carrier （OC） was synthesized and its reaction with a typical Chinese high sulfur coal, Liuzhi （LZ） bituminous coal, was performed in a thermogravimetric analyzer （TGA）-Fourier transform infrared （FT-IR） spectrometer. Evolution of sulfur species during reaction of LZ coal with MnFeaO40C was systematically investigated through experimental means combined with thermodynamic simulation. TGA-FTIR analysis of the LZ reaction with MnFe2O4 indicated MnFe2O4 exhibited the desired superior reactivity compared to the single reference oxides Mn304 or Fe203, and SO2 produced was mainly related to oxidization of H2S by MnFe2O4. Experimental analysis of the LZ coal reaction with MnFe2O4, including X-ray diffraction and X-ray photoelectron spectroscopy analysis, verified that the main reduced counterparts of MnFe2O4 were Fe304 and MnO, in good agreement with the related thermodynamic simulation. The obtained MnO was beneficial to stabilize the reduced MnFe2O4 and avoid serious sintering, although the oxygen in MnO was not fully utilized. Meanwhile, most sulfur present in LZ coal was converted to solid MnS during LZ reaction with MnFe2O4, which was further oxidized to MnSO4. Finally, the formation of both MnS and such manganese silicates as Mn2SiO4 and MnSiO3 should be addressed to ensure the full regeneration of the reduced MnFe2O4.

Release characteristics of mercury in chemical looping combustion of bituminous coal

This study evaluated the release characteristics of mercury from bituminous coal in chemical looping combustion(CLC)using Australian iron ore as the oxygen carrier in a fixed bed reactor.The effects of several parameters,such as temperature in the fuel reactor(FR)and air reactor(AR),gasification medium in the FR,and reaction atmosphere in the AR,on mercury release characteristics,were investigated.The mercury speciation and release amount in the FR and AR under different conditions were further explored.The results indicate that most of the mercury in coal was released in the FR,while the rest of it was released in the AR.Hg0 was found to be the major species in the released mercury.The results also indicate that a higher temperature in the FR led to an increase in the total mercury release amount and a decrease in Hg0 proportion.However,a higher temperature in the AR resulted in a decrease in the total mercury release amount and Hg 0 proportion.The increase in the H2O/CO2 ratio of gasification mediums in the FR was beneficial for the increase in the total mercury release amount and Hg 0 proportion.A higher O2 concentration in reaction atmosphere in AR had a negligible effect on the total mercury release amount,but a positive effect on Hg0 oxidization.

Performance and kinetics of iron-based oxygen carriers reduced by carbon monoxide for chemical looping combustion

Chemical looping combustion is a promising technology for energy conversion due to its low-carbon, high-efficiency, and environmental-friendly feature. A vital issue for CLC process is the development of oxygen carrier, since it must have sufficient reactivity. The mechanism and kinetics of CO reduction on iron-based oxygen carriers namely pure Fe2O3 and Fe2O3 supported by alumina （Fe2O3/Al2O3） were investigated using thermo-gravimetric analysis. Fe2O3/Al2O3 showed better reactivity over bare Fe2O3 toward CO reduction. This was well supported by the observed higher rate constant for FezO3/Al2O3 over pure Fe2O3 with respective activation energy of 41.1±2.0 and 33.3±0.8 kJ. mol^-1. The proposed models were compared via statistical approach comprising Akaike information criterion with correction coupled with F-test. The phase-boundary reaction and diffusion control models approximated to 95% confidence level along with scanning electron microscopy results; revealed the promis- ing reduction reactions of pure Fe203 and Fe2O3/Al2O3. The boosting recital of iron-based oxygen carrier support toward efficient chemical looping combustion could be explained accurately through the present study.

Chemical looping combustion: A new low-dioxin energy conversion technology

Dioxin production is a worldwide concern because of its persistence and carcinogenic,teratogenic, and mutagenic effects. The pyrolysis-chemical looping combustion process of disposing solid waste is an alternative to traditional solid waste incineration developed to reduce the dioxin production. Based on the equilibrium composition of the Deacon reaction,pyrolysis gas oxidized by seven common oxygen carriers, namely, Cu O, Ni O, Ca SO4, Co O,Fe2O3, Mn3O4, and Fe Ti O3, is studied and compared with the pyrolysis gas directly combusted by air. The result shows that the activity of the Deacon reaction for oxygen carriers is lower than that for air. For four typical oxygen carriers（Cu O, Ni O, Fe2O3, and Fe Ti O3）, the influences of temperature, pressure, gas composition, and tar on the Deacon reaction are discussed in detail. According to these simulation results, the dioxin production in China, Europe, the United States, and Japan is predicted for solid waste disposal by the pyrolysis-chemical looping combustion process. Thermodynamic analysis results in this paper show that chemical looping combustion can reduce dioxin production in the disposal of solid waste.