Enhancing the capacity of oxygen carriers for selective oxidations through phase cooperation: Bismuth oxide and ceria-zirconia

Interfacing selective catalysts with oxygen carriers enhances capacity without affecting the surface chemistry, simplifying the design of selective oxygen carriers.</p

Modelling rates of gasification of a char particle in chemical looping combustion

Rates of gasification of lignite char were compared when gasification with CO2 was undertaken in a fluidised bed of either (i) an active Fe-based oxygen carrier used for chemical looping or (ii) inert sand. The kinetics of the gasification were found to be significantly faster in the presence of the oxygen carrier, especially at temperatures above 1123 K. An analytical solution assuming pseudo-binary diffusion of species was developed to account for external and internal mass transfer and for the effect of the looping agent. The model also included the effects of the evolution of the pore structure at different conversions. The results are compared with a full numerical model using the Stefan-Maxwell equations. Excellent agreement was observed between the rates predicted by the two models and those observed experimentally at T ≤ 1123 K. At 1173 K, the pseudo-binary model predicted slightly higher rates than the full numerical solution. It was found that a significant share of the error of the predicted rates with the analytical solution was caused by an underestimation of intraparticle diffusional resistance rather than by assuming a pseudo-binary system external to the particle. Both models suggested that the presence of Fe2O3 led to an increase in the rate of gasification because of the rapid oxidation of CO by the oxygen carrier to CO2. This resulted in the removal of CO and maintained a higher mole fraction of CO2 in the mixture of gas around the particle of char, i.e. within the mass transfer boundary layer surrounding the particle. This effect was most prominent at ~20% conversion when (i) the surface area for reaction was a maximum and (ii) because of the accompanying increase in porosity, intraparticle resistance to gas mass transfer within the particle of char had fallen, compared with that in the initial particle.EPSRCThis is the author accepted manuscript. The final version is now available at http://www.sciencedirect.com/science/article/pii/S1540748914003150

Using an experimentally-determined model of the evolution of pore structure for the calcination of cycled limestones

A pseudo-steady state model of reaction and diffusion has been constructed to model the non-isothermal calcination of limestone particles which have been subjected to a history of cycling between the calcined and carbonated states. This typically occurs when using Ca-based materials for removing CO$_{2}$ from the flue gas of plants such as a power station, cement plant and steel factory in certain schemes for carbon capture and storage. The model uses a Cylindrical Pore Interpolation Model to describe the intraparticle mass transfer of CO$_{2}$ through the pores of the material coupled with an experimentally-determined function, $\textit{f(X)}$, describing the pore evolution as a function of the conversion of the CaCO$_{3}$ present to CaO. The intrinsic rate of calcination was taken to be first order in concentration driving force. External to the limestone particle, the Stefan-Maxwell equations were used to describe the diffusion of CO$_{2}$ away from the particle and into the particulate phase of the fluidised bed. The equation of energy was used to allow for the enthalpy of the reaction. In order to validate the use of the $\textit{f(X)}$ function, the theoretical predictions were compared with experiments conducted to measure the rates and extent of conversion, at various temperature and different particle sizes, of Purbeck and Compostilla limestones that had been previously cycled between the carbonated and fully-calcined state. Excellent agreement between experiment and theory was obtained, and the model using the $\textit{f(X)}$ approach predicted the conversion of particles of various sizes well at temperatures different to that at which the function was derived, thus indicating that the $\textit{f(X)}$ solely dependent on the evolution of the morphology of the particle

Modelling reaction and diffusion in a wax-filled hollow cylindrical pellet of Fischer Tropsch catalyst

Previous modelling of fixed-bed, Fischer-Tropsch (FT) reactors has demonstrated the advantages relative to spherical pellets of using cylindrical and shaped pellets to provide improved transport attributes under conditions relevant to industrial operation. However, mass transport models have focussed on the investigation of transport within pellets with spherical symmetry, whilst detailed investigations of more complex shapes have not been undertaken. Here, a pseudo-isothermal, steady-state, two-dimensional model was investigated for catalyst pellets of cylindrical form, both solid and hollow. A cobalt-based catalyst was considered at conditions where the rate of condensable hydrocarbon generation is large enough to result in the accumulation of liquid hydrocarbons in the pores of a catalyst. It was found that effectiveness factors were bounded by those of sphere and slab above and below Thiele moduli of ~0.75 and ~1.15, respectively, for the conditions examined, with the effectiveness factors exceeding those of both sphere and slab models between these moduli. Here, comparisons were made on the basis of the characteristic diffusion length, the catalyst particle’s volume divided by its external surface area. However, values of the FT chain growth parameter, α, between these values of Thiele modulus were lower than both those of sphere and slab geometry, and thus under these conditions hollow cylinders gave the greatest methane selectivity

Kinetics of oxygen uncoupling of a copper based oxygen carrier

Here, an oxygen carrier consisting of 60 wt% CuO supported on a mixture of Al_2O_ 3 and CaO (23 wt% and 17 wt% respectively) was synthesised by wet-mixing powdered CuO, Al(OH)_3 and Ca(OH)_2, followed by calcination at 1000⁰C. Its suitability for chemical looping with oxygen uncoupling (CLOU) was investigated. After 25 repeated redox cycles in either a thermogravimetric analyser (TGA) or a laboratory-scale fluidised bed, (with 5 vol% H_2 in N_2 as the fuel, and air as the oxidant) no significant change in either the oxygen uncoupling capacity or the overall oxygen availability of the carrier was found. In the TGA, it was found that the rate of oxygen release from the material was controlled by intrinsic chemical kinetics and external transfer of mass from the surface of the particles to the bulk gas. By modelling the various resistances, values of the rate constant for the decomposition were obtained. The activation energy of the reaction was found to be 59.7 kJ/mol (with a standard error of 5.6 kJ/mol) and the corresponding pre-exponential factor was 632 m^3/mol/s. The local rate of conversion within a particle was assumed to occur either (i) by homogeneous chemical reaction, or (ii) in uniform, non-porous grains, each reacting as a kinetically-controlled shrinking core. Upon cross validation against a batch fluidised bed experiment, the homogeneous reaction mode l was found to be more plausible. By accurately accounting for the various artefacts (e.g. mass transfer resistances) present in both TGA and Fluidised bed experiments, it was possible to extract a consistent set of kinetic parameters which reproduced the rates of oxygen release in both experiments.This work is supported by the Engineering and Physical Sciences Research Council (EPSRC grant EP/I010912/1) and The Cambridge Commonwealth, European & International Trust as well as Selwyn College, University of Cambridge. The authors would also like to thank Mohammad Ismail for the XRD analysis and Zlatko Saracevic for the nitrogen adsorption analysis.This is the final version of the article. It first appeared from Elsevier via http://dx.doi.org/10.1016/j.apenergy.2015.10.00

Limitations on Fluid Grid Sizing for Using Volume-Averaged Fluid Equations in Discrete Element Models of Fluidized Beds

Bubbling and slugging fluidization were simulated in 3D cylindrical fluidized beds using a discrete element model with computational fluid dynamics (DEM-CFD). A CFD grid was used in which the volume of all fluid cells was equal. Ninety simulations were conducted with different fluid grid cell lengths in the vertical (dz) and radial (dr) directions to determine at what fluid grid sizes, as compared to the particle diameter (dp), the volume-averaged fluid equations broke down and the predictions became physically unrealistic. Simulations were compared with experimental results for time-averaged particle velocities as well as frequencies of pressure oscillations and bubble eruptions. The theoretical predictions matched experimental results most accurately when dz = 3-4 dp, with physically unrealistic predictions produced from grids with lower dz. Within the valid range of dz, variations of dr did not have a significant effect on the results.CMB acknowledges the Gates Cambridge Trust for funding his research.This is the author accepted manuscript. The final version is available from ACS via http://dx.doi.org/10.1021/acs.iecr.5b0318

High selectivity epoxidation of ethylene in chemical looping setup

We describe the remarkable performance of a new catalyst for the chemical looping (CL-) epoxidation of ethylene, performed at atmospheric pressure and without any promoters added to either the catalyst or the feed gas. To undertake the CL-epoxidation of ethylene, silver was used as the catalyst, supported on either the perovskite SrFeO3 or Ce-modified SrFeO3. Here, the oxygen for the reaction is supplied to the silver catalyst from the active solid support, not from the gas stream. When the support has been reduced and depleted of oxygen, it is regenerated in a separate step with air, which makes the process cyclic and closes a chemical loop. Thus, there is no need to co-feed gaseous oxygen along with the ethylene feed, an important improvement in safety. Two methods were used to synthesise Ce-modified materials, employing either (i) the mechanical mixing of powdered CeO2 and the solid precursors of the perovskite, or (ii) the impregnation of a solution of cerium nitrate into solid particles of SrFeO3. In both cases, the materials were calcined to produce a mixture of CeO2 and SrFeO3. Both CeO2-SrFeO3 materials surpassed the unmodified SrFeO3 for CL-epoxidation. For the CeO2-SrFeO3 prepared by mechanical mixing, the production of ethylene oxide was stable over 15 cycles, giving 60% selectivity at 10% conversion of C2H4. In contrast, the material prepared by impregnation gave up to 85% selectivity but only in the first cycle of reduction, with the performance degrading over subsequent cycles. The reported results are better than the 50% selectivity achieved for the classical epoxidation using pure silver as the catalyst and feeds of gaseous ethylene and oxygen, without reaction promoters

The role of the Boudouard and water–gas shift reactions in the methanation of CO or CO<inf>2</inf> over Ni/γ-Al<inf>2</inf>O<inf>3</inf> catalyst

The Boudouard and the water–gas shift reactions were studied at different temperatures between 453 and 490 K over a Ni/γ-Al$_2$O$_3$ catalyst in a Carberry batch reactor using various mixtures of CO, H$_2$ and CO$_2$. The activity of the Boudouard reaction was found to be low, compared to the water–gas shift reaction, and diminished over time, suggesting that the temperature was too low for significant activity after an initiation period of CO adsorption. Furthermore, the rate of the Boudouard reaction has been reported to decrease in the presence of H$_2$O and H$_2$. The water–gas shift reaction was found to be the main reaction responsible for the production of CO$_2$ in a mixture of CO, H$_2$ and H$_2$O in the batch reactor. The ratio of the total amount of CO consumed to the total amount of CO$_2$ produced showed that the catalyst was also active towards hydrogenation, where the rate of the hydrogenation reaction was very much faster than the water–gas shift reaction. The resulting ratio of $\textit{p}$$_{H_2}$ to $\textit{p}$$_{CO}$ was found to be extremely low, probably leading to the production of long-chain hydrocarbons. The stoichiometry of the overall reaction was such that for every mole of CO$_2$ produced, 1.5 mol of CO was consumed in the batch reactor. Kinetic studies were performed in the batch reactor. An Eley-Rideal mechanism was found to provide a good agreement with the experimental results over a wide range of partial pressures of steam and CO.JYL was funded by the Cambridge International Scholarship Scheme. The Cambridge Philosophical Society, the Lundgren Research Award and Corpus Christi College are also gratefully thanked for contributing to the support of his PhD studies. We are grateful for the assistance of Dr A.P.E. York, Johnson Matthey Technology Centre, Sonning Common, Reading RG4 9NH, United Kingdom, for his valuable input to this research.This is the author accepted manuscript. The final version is available from Elsevier via http://dx.doi.org/10.1016/j.ces.2016.06.04

Sensitivity of chemical-looping combustion to particle reaction kinetics

A simple simulation for chemical-looping combustion (CLC) is discussed: two, coupled fluidised reactors with steady circulation of particles of oxygen carrier between them. In particular, the sensitivity of CLC to different particle kinetics is investigated. The results show that the system is relatively insensitive to different kinetics when the mean residence time of particles in each reactor is greater than the time taken for them to react completely.This is the final published version. It first appeared at http://www.sciencedirect.com/science/article/pii/S0009250916302779

Use of a Chemical-Looping Reaction to Determine the Residence Time Distribution of Solids in a Circulating Fluidized Bed

The residence time distribution (RTD) of solids in various sections of a circulating fluidized bed (CFB) is of great importance for design and operation but is often difficult to determine experimentally. A noninvasive method is described, for which the RTD was derived from temporal measurements of the temperature following the initiation of a chemical-looping reaction. To demonstrate the method, a CuO-based oxygen carrier was used in a small-scale CFB, and measurements were made in the fuel reactor, operated as a bubbling fluidized bed. The measurements were fitted to the tanks-in-series model, modified to account for heat losses from the reactor. There was excellent agreement between the model and the experiment. Limitations and further improvements of the method are discussed, also with respect to larger reactors.This work is supported by the Engineering and Physical Sciences Research Council (EPSRC Grant EP/I010912/1).This is the final version of the article. It first appeared from Wiley via http://dx.doi.org/10.1002/ente.20160014