Calcination of calcium-based sorbents at pressure in a broad range of CO2 concentrations

11 figures, 3 tablesThe calcination reaction of two limestones and a dolomite with different porous structures was studied by thermogravimetric analysis. The effects of calcination temperature (1048-1173 K), particle size (0.4 2.0 mm), CO2 concentration (0 80%) and total pressure (0.1 1.5 MPa) were investigated. SEM analysis indicated the existence of two different particle calcination models depending on the sorbent type: a shrinking core model with a sharp limit between the uncalcined and calcined parts of the particle and a grain model with changing calcination conversion at the particle radial position. The appropriate reaction model was used to determine the calcination kinetic parameters of each sorbent. Chemical reaction and mass transport in the particle porous system were the main limiting factors of the calcination reaction at the experimental conditions. A Langmuir-Hinshelwood-type kinetic model using the Freundlich isotherm was proposed to account for the effect of the CO2 during sorbent calcination. This allowed us to predict the calcination conversion of very different sorbents in a broad range of CO2 partial pressures. Total pressure also inhibited the sorbent calcination. This fact was accounted for by an additional decrease in the molecular diffusion coefficient with increasing total pressure with respect to that indicated by Fuller's equation.This research was carried out with the financial support from the Comisión Interministerial de Ciencia y Tecnología (CICYT) (Project No. AMB 98-0883). The authors thank Dr. Diego Alvárez for his assistance with the SEM technique.Peer Reviewe

Effect of pressure on the behavior of copper-, iron-, and nickel-based oxygen carriers for chemical-looping combustion

8 pages, 8 figures, 2 tables.The combustion process integrated by coal gasification and chemical-looping combustion (CLC) could be used in power plants with a low energy penalty for CO2 capture. This work analyzes the main characteristics related to the CLC process necessary to use the syngas obtained in an integrated gasification combined cycle (IGCC) power plant. The kinetics of reduction with H2 and CO and oxidation with O2 of three high-reactivity oxygen carriers used in the CLC system have been determined in a thermogravimetric analyzer at atmospheric pressure. The iron- and nickel-based oxygen carriers were prepared by freeze-granulation, and the copper-based oxygen carrier was prepared by impregnation. The changing grain size model (CGSM) was used for the kinetic determination, assuming spherical grains for the freeze-granulated particles containing iron and nickel and a platelike geometry for the reacting surface of the copper-based impregnated particles. The dependence of the reaction rates on temperature was low, with the activation energy values varying from 14 to 33 kJ mol-1 for the reduction and 7 to 15 kJ mol-1 for the oxidation. The reaction order depended on the reacting gas and oxygen carrier, with values ranging from 0.25 to 1. However, an increase in the operating pressure for the IGCC + CLC system increases the thermal efficiency of the process, and the CO2 is recovered as a high pressure gas, decreasing the energy demand for further compression. The effect of pressure on the behavior of the oxygen carriers has been analyzed in a pressurized thermogravimetric analyzer at 1073 K and pressures up to 30 atm. It has been found that an increase in total pressure has a negative effect on the reaction rates of all the oxygen carriers. Moreover, the use of the CGSM with the kinetic parameters obtained at atmospheric pressure predicted higher reaction rates than those experimentally obtained at higher pressures, and therefore, the kinetic parameters necessary to design pressurized CLC plants must be determined at the operating pressure. © 2006 American Chemical Society.This work was carried out with financial support from the European Coal and Steel Community Project (7220-PR125) and the Spanish Ministry of Education and Science (Project CTQ 2004-04034). The authors thank Dr. Anders Lyngfelt and Dr. Tobias Mattisson for the preparation of the freeze-granulated particles.Peer Reviewe

The use of ilmenite as oxygen-carrier in a 500Wth Chemical-Looping Coal Combustion unit

12 pages, 13 figures, 6 tablesChemical-Looping Combustion, CLC, is a promising technology to capture CO2 at low cost in fossil-fuelled power plants. In CLC the oxygen from air is transferred to the fuel by a solid oxygen-carrier that circulates between two interconnected fluidized-bed reactors: the fuel- and the air-reactor. This work studies the CLC technology in a 500Wth facility fuelled with bituminous coal with ilmenite as oxygen-carrier. The effect of temperature and coal particle size on coal conversion and combustion efficiency was assessed. Char gasification and combustion of both gasification products and volatile matter were evaluated. At higher temperatures, gasification and combustion reactions are promoted. Carbon capture and combustion efficiencies grow with the temperature, with faster increase at temperatures higher than 910°C. The outgoing unburnt gases come from volatile matter that was not fully oxidized by ilmenite. Little CH4 was measured and there were neither hydrocarbons heavier than CH4 nor tars in the fuel-reactor outlet. At 870°C the char conversion was 15% and reached 82% at 950°C. The combustion efficiency in the fuel-reactor increased from 70% at 870°C to 95% at 950°C. The results show that ilmenite has good behavior as oxygen-carrier and that optimizing CLC with coal can lead to energy production with high CO2 capture.This work was partially supported by the European Commission, under the RFCS program (ECLAIR Project, Contract RFCP-CT-2008-0008), from Alstom Power Boilers and by the Spanish Ministry of Science and Innovation (Project ENE2010-19550). A. Cuadrat thanks CSIC for the JAE Pre. fellowship. Alberto Abad thanks to the Ministerio de Ciencia e Innovación for the financial support in the course of the I3 Program.Peer Reviewe

Characterization for disposal of Fe-based oxygen carriers from a CLC unit burning coal

Chemical Looping Combustion (CLC) is an emerging low cost CO2 capture technology for large scale power units. The oxygen needed for combustion is supplied by a solid oxygen carrier circulating between two reactors. Fe-based oxygen carriers have been proposed for CLC of coal due to their low cost. Some of them are minerals or industrial residues which can contain toxic trace elements. After its use, the oxygen carrier should be disposed in a landfill and therefore, the presence of soluble toxic elements in the oxygen carrier should be analyzed. In this study, lixiviation tests were carried out with three different Fe-based oxygen carriers used in coal CLC experiments in a continuous unit: ilmenite, a bauxite waste and an iron ore. All the spent oxygen carriers, except the bauxite waste, can be classified as a stable non-reactive hazardous waste and therefore can be disposed in a landfill for non-hazardous residues. An estimation of the amount of solid waste generated in the process based on the fly ash content of the coal and the oxygen carrier particle lifetime was made.The authors thank the Spanish Ministry for Science and Innovation (MICCIN) for the financial support via the ENE2011-26354 project. This work was also partially supported by FEDER funds. T. Mendiara thanks for the “Ramón y Cajal” post-doctoral contract awarded by the Ministry of Economy and Competitiveness.Peer reviewe

Prompt considerations on the design of chemical-looping combustion of coal from experimental tests

13 Figures, 5 TablesThe Chemical-Looping Combustion of coal in the reactor system has been proposed as an interesting option to process a solid fuel in a CLC system. In this process, a solid fuel is directly fed to the fuel reactor in a CLC system. Solid fuel pyrolysis, char gasification and oxidation of gaseous products by reaction with the oxygen-carrier are the main chemical processes happening in the fuel reactor. The aim of this study is to analyze the performance of ilmenite as oxygen-carrier for CLC of coal regarding to the conversion of gaseous products from char gasification. Successive reduction-oxidation cycles were carried out in a fluidized bed using bituminous coal char as reducing agent. The changes on chemical and physical properties of ilmenite particles were determined. An activation process of ilmenite through the redox cycles was evidenced which was justified by an increase of porosity. The results showed that the activation for ilmenite reduction reaction was completed after 7 redox cycles. However, the oxidation reaction rate was increasing still after 16 redox cycles because the porosity was not fully developed. The gasification reaction rate and the ilmenite reactivity were analyzed. The effect of ilmenite itself and the influence of the gasification agent, i.e. H2O, CO2 or H2O/CO2 mixtures, and temperature on the gasification rate were evaluated. Limited use of CO2 in the fluidizing gas was identified in order to maintain high gasification rates. Higher temperature improved the char gasification rate, mainly using steam as gasification agent, and the combustion efficiency of the gasification products. Nevertheless, the effect of temperature on the combustion efficiency was of lower relevance than that on the gasification rate. Finally, a theoretical approach was developed to easily evaluate the conversion of char in the fuel-reactor by gasification.This work was partially supported by the European Commission, under the RFCS program (ECLAIR Project, Contract RFCP-CT-2008-0008), from Alstom Power Boilers and by the Spanish Ministry of Science and Innovation (Project ENE2010- 19550). A. Cuadrat thanks CSIC for the JAE Pre. fellowship. Alberto Abad thanks to the Ministerio de Ciencia e Innovación for the financial support in the course of the I3 Program.Peer reviewe

Kinetic determination of a highly reactive impregnated Fe2O3/Al2O3 oxygen carrier for use in gas-fuelled chemical looping combustion

The objective of this work was to determine the kinetic parameters for reduction and oxidation reactions of a highly reactive Fe-based oxygen carrier for use in chemical looping combustion (CLC) of gaseous fuels containing CH4, CO and/or H2, e.g. natural gas, syngas and PSA-off gas. The oxygen carrier was prepared by impregnation of iron on alumina. The effect of both the temperature and gas concentration was analysed in a thermogravimetric analyser (TGA). The grain model with uniform conversion in the particle and reaction in grains following the shrinking core model (SCM) was used for kinetics determination. It was assumed that the reduction reactions were controlled by two different resistances: the reaction rate was controlled by chemical reaction in a first step, whereas the mechanism that controlled the reactions at higher conversion values was diffusion through the product layer around the grains. Furthermore, it was found that the reduction reaction mechanism was based on the interaction of Fe2O3 with Al2O3 in presence of the reacting gases to form FeAl2O4 as the only stable Fe-based phase. The reaction order values found for the reducing gases were 0.25, 0.3 and 0.6 for CH4, H2 and CO, respectively, and the activation energy took values of between 8 kJ mol-1 (for H2) and 66 kJ mol-1 (for CH4). With regard to oxidation kinetics, the reacting model assumed a reaction rate that was only controlled by chemical reaction. Values of 0.9 and 23 kJ mol-1 were found for reaction order and activation energy, respectively. Finally, the solids inventory needed in a CLC system was also estimated by considering kinetic parameters. The total solids inventory in the CLC unit took a minimum value of 150 kg MW-1 for CH4 combustion, which is a low value when compared to those of other Fe-based materials found in the literature.This paper is based on the work carried out within the framework of the SUCCESS project, funded by the European Commission under the seventh Framework Programme (Contract 608571). This research was supported by the Spanish Ministry of Science and Innovation (MICINN Project: ENE2011-26354) and by FEDER.Peer reviewe

Kinetic analysis of a Cu-based oxygen carrier: Relevance of temperature and oxygen partial pressure on reduction and oxidation reactions rates in Chemical Looping with Oxygen Uncoupling (CLOU)

The kinetic of reduction of CuO to Cu2O with N2+O2 mixtures and the oxidation of Cu2O to CuO with O2 of a Cu-based oxygen carrier for the CLOU process has been determined in a TGA. For kinetic determination, the O2 concentrations were varied between 0 and 9 vol.% for reduction, and between 21 and 1.5 vol.% for oxidation reactions; temperature was varied between 1148 and 1273 K for the reduction and between 1123 and 1273 K for the oxidation. The oxygen carrier showed high reactivity both in oxidation and reduction reactions. The nucleation and nuclei growth model with chemical reaction control properly described the evolution of solids conversion with time. The Langmuir-Hinshelwood model was able to describe the effect of oxygen concentration on reduction and oxidation rates. The reaction order was 0.5 for reduction and 1.2 for the oxidation. The kinetic constant activation energies were 270 kJ mol-1 for the reduction and 32 kJ mol-1 for the oxidation. The kinetic model was used to calculate the solids inventory needed in the fuel reactor for complete combustion of three different rank coals. It was possible to use a low oxygen carrier inventory in the fuel reactor (160 kg/MWth) to supply the oxygen required to full lignite combustion. However, to reach high CO2 capture efficiencies (³95%), oxygen carrier inventories in fuel reactor higher than 600 kg/MWth were needed with the lignite.This work was supported by the European Commission, under the RFCS program (ACCLAIM Project, Contract RFCP-CT-2012-00006), the Spanish Ministry of Science and Innovation (MICINN Project: ENE2011-26354) and the European Union FEDER Funds. I. Adánez-Rubio thanks CSIC for the JAE fellowship co-financed by the European Social Fund.Peer reviewe

Characterization of a limestone in a batch fluidized bed reactor for sulfur retention under oxy-fuel operating conditions

12 FiguresCO2 and SO2 are some of the main polluting gases emitted into atmosphere in combustion processes using fossil fuel for energy production. The former is one of the major contributors to build-up the greenhouse effect implicated in global climate change and the latter produces acid rain. Oxy-fuel combustion is a technology, which consists in burning the fuel with a mix of pure O2 and recirculated CO2. With this technology the CO2 concentration in the flue gas may be enriched up to 95%, becoming possible an easy CO2 recovery. In addition, oxy-fuel combustion in fluidized beds allows in situ desulfurization of combustion gases by supplying calcium based sorbent.In this work, the effect of the principal operation variables affecting the sulfation reaction rate in fluidized bed reactors (temperature, CO2 partial pressure, SO2 concentration and particle size) under typical oxy-fuel combustion conditions have been analyzed in a batch fluidized bed reactor using a limestone as sorbent. It has been observed that sulfur retention can be carried out by direct sulfation of the CaCO3 or by sulfation of the CaO (indirect sulfation) formed by CaCO3 calcination. Direct sulfation and indirect sulfation operating conditions depended on the temperature and CO2 partial pressure. The rate of direct sulfation rose with temperature and the rate of indirect sulfation for long reaction times decreased with temperature. An increase in the CO2 partial pressure had a negative influence on the sulfation conversion reached by the limestone due to a higher temperature was needed to work in conditions of indirect sulfation. Thus, it is expected that the optimum temperature for sulfur retention in oxy-fuel combustion in fluidized bed reactors be about 925-950°C. Sulfation reaction rate rose with decreasing sorbent particle size and increasing SO2 concentration.This research has been supported by Spanish Ministry of Science and Innovation (MICINN, Project: CTQ2008-05399/PPQ) and by FEDER. M. de las Obras-Loscertales thanks MICINN for the F.P.I. fellowship.Peer Reviewe

Performance of Cu- and Fe-based oxygen carriers in a 500 Wth CLC unit for sour gas combustion with high H2S content

Sour gas represents about 43% of the world's natural gas reserves. The sustainable use of this fossil fuel energy entails the application of CO2 Capture and Storage (CCS) technologies. The Chemical Looping Combustion (CLC) technology can join the exploitation of the energy potential of the sour gas and the CO2 capture process in a single step without the need of a sweetening pre-treatment unit. In this work, a total of 60 h of continuous operation with sour gas and H2S concentrations up to 15 vol% has been carried out in a 500 Wth CLC unit, from which 40 corresponded to a Cu-based oxygen carrier (Cu14γAl) and 20 to a Fe-based material (Fe20γAl). This is the first time that so high H2S concentrations are present in a fuel to be burnt in a CLC process. The Cu14γAl oxygen carrier seems to be not recommendable for the combustion of sour gas because, although all the H2S is burnt to SO2, copper sulfides were formed at all combustion conditions. In contrast, the Fe20γAl oxygen carrier presented an excellent behavior with no agglomeration problems and maintaining the reactivity of the fresh material. The sour gas (CH4, H2 and H2S) was completely burnt, and neither SO2 was released in the AR nor iron sulfides were formed at usual CLC operating conditions. These tests demonstrated the possibility to use sour gas in a CLC process with 100% CO2 capture without any SO2 emissions to the atmosphere.This work has been financed by Shell Global Solutions International B.V. within the frame of the agreement PT22648 signed between Shell Global Solutions International B.V. and Instituto de Carboquímica—Consejo Superior de Investigaciones Científicas (ICB—CSIC).Peer reviewe

Validation of a fuel reactor model for in-situ Gasification Chemical Looping Combustion

3 figures.-- Talk delivered in the IEA GHG, 3rd Oxyfuel Combustion Conference, Ponferrada (Spain), 6th -13th september 2013.The success of a Chemical-Looping Combustion (CLC) system for coal combustion is greatly affected by the performance of the fuel reactor. When coal is gasified in-situ in the fuel reactor, several parameters affect to the coal conversion, and hence to capture and combustion efficiencies. In this work a mathematical model for the fuel reactor is validated against experimental results obtained in a 100 kWth CLC unit when reactor temperature, solids circulation flow rate or solids inventory are varied. The validated model can be used to evaluate the relevance of operating conditions on process efficiency.This work was partialy supported by the European Commission, under the RFCS program (ECLAIR Project, Contract RFC-PP-07011), Alstom Power Boilers, and the Spanish Ministry for Science and Innovation via the ENE2010-19550 project.Peer reviewe