High purity H2 by sorption-enhanced chemical looping reforming of waste cooking oil in a packed bed reactor.

High purity hydrogen (>95%) was produced at 600 degrees C and 1 atm by steam reforming of waste cooking oil at a molar steam to carbon ratio of 4 using chemical looping, a process that features redox cycles of a Ni catalyst with the in-situ carbonation/calcination of a CO(2) sorbent (dolomite) in a packed bed reactor under alternated feedstreams of fuel-steam and air. The fuel and steam conversion were higher with the sorbent present than without it. Initially, the dolomite carbonation was very efficient (100%), and 98% purity hydrogen was produced, but the carbonation decreased to around 56% with a purity of 95% respectively in the following cycles. Reduction of the nickel catalyst occurred alongside steam reforming, water gas shift and carbonation, with H(2) produced continuously under fuel-steam feeds. Catalyst and CO(2)-sorbent regeneration was observed, and long periods of autothermal operation within each cycle were demonstrated

High hydrogen yield and purity from palm empty fruit bunch and pine pyrolysis oils

The benefits of CO 2 sorption enhanced steam reforming using calcined dolomite were demonstrated for the production of hydrogen from highly oxygenated pyrolysis oils of the agricultural waste palm empty fruit bunches (PEFB) and pine wood. At 1 atm in a down-flow packed bed reactor at 600 °C, the best molar steam to carbon ratios were between 2 and 3 using a Ni catalyst. After incorporating steam-activated calcined dolomite as the CO 2 sorbent in the reactor bed, the H 2 yield from the moisture free PEFB oil increased from 9.5 to 10.4 wt.% while that of the pine oil increased from 9.9 to 13.9 wt.%. The hydrogen purity also rose from 68 to 96% and from 54 to 87% for the PEFB and pine oils respectively, demonstrating very substantial sorption enhancement effects

In situ X-ray diffraction of CaO based CO2 sorbents

In situ X-ray diffraction coupled with Rietveld refinement has been used to study CO2 capture by CaO, Ca(OH)2 and partially hydrated CaO, as a function of temperature. Phase quantification by Rietveld refinement was performed to monitor the conversion to CaCO3 and the results were compared to those derived using thermogravimetric analysis (TGA). It was found that Ca(OH)2 converted directly to 100% CaCO3 without the formation of a CaO intermediate, at ca. 600 °C. Both pure CaO and partially hydrated CaO (33.6 wt% Ca(OH)2) reached the same capture capacity, containing approximately 65 wt% CaCO3 at 800 °C. It was possible to provide direct evidence of the capture mechanism. The stresses in the Ca(OH)2 phase of the partially hydrated CaO were found to be more than 20 times higher than its strength, leading to disintegration and the generation of nano-sized crystallites. The crystallite size determined using diffraction (75 × 16 nm) was in good agreement with the average crystallite size observed using TEM (of 83 × 16 nm). Electron diffraction patterns confirmed coexistence of CaO and Ca(OH)2. The analysis provides an explanation of the enhanced capture/disintegration observed in CaO in the presence of steam

Production of hydrogen by unmixed steam reforming of methane

Unmixed steam reforming is an alternative method of catalytic steam reforming that uses separate air and fuel–steam feeds, producing a reformate high in H2 content using a single reactor and a variety of fuels. It claims insensitivity to carbon formation and can operate autothermally. The high H2 content is achieved by in situ N2 separation from the air using an oxygen transfer material (OTM), and by CO2 capture using a solid sorbent. The OTM and CO2 sorbent are regenerated during the fuel–steam feed and the air feed, respectively, within the same reactor. This paper describes the steps taken to choose a suitable CO2-sorbent material for this process when using methane fuel with the help of microreactor tests, and the study of the carbonation efficiency and regeneration ability of the materials tested. Elemental balances from bench scale experiments using the best OTM in the absence of the CO2 sorbent allow identifying the sequence of the chemical reaction mechanism. The effect of reactor temperature between 600 and on the process outputs is investigated. Temperatures of 600 and under the fuel–steam feed were each found to offer a different set of desirable outputs. Two stages during the fuel–steam feed were characterised by a different set of global reactions, an initial stage where the OTM is reduced directly by methane, and indirectly by hydrogen produced by methane thermal decomposition, in the second stage, steam reforming takes over once sufficient OTM has been reduced. The implications of these stages on the process desirable outputs such as efficiency of reactants conversion, reformate gas quality, and transient effects are discussed

Molecular Dynamics Study of Crystal Plasticity during Nanoindentation in Ni Nanowires

Molecular dynamics simulations were performed to gain fundamental insight into crystal plasticity, and its size effects in nanowires deformed by spherical indentation. This work focused on-oriented single-crystal, defect-free Ni nanowires of cylindrical shape with diameters of 12 and 30 nm. The indentation of thin films was also comparatively studied to characterize the influence of free surfaces in the emission and absorption of lattice dislocations in single-crystal Ni. All of the simulations were conducted at 300 K by using a virtual spherical indenter of 18 nm in diameter with a displacement rate of1 ms1. No significant effect of sample size was observed on the elastic response and mean contact pressure at yield point in both thin films and nanowires. In the plastic regime, a constant hardness of 21 GPa was found in thin films for penetration depths larger than 0.8 nm, irrespective of variations in film thickness. The major finding of this work is that the hardness of the nanowires decreases as the sample diameter decreases, causing important softening effects in the smaller nanowire during indentation. The interactions of prismatic loops and dislocations, which are emitted beneath the contact tip, with free boundaries are shown to be the main factor for the size dependence of hardness in single-crystal Ni nanowires during indentation

Grain Growth Behavior at Absolute Zero during Nanocrystalline Metal Indentation

The authors show using atomistic simulations that stress-driven grain growth can be obtained in the athermal limit during nanocrystalline aluminum indentation. They find that the grain growth results from rotation of nanograins and propagation of shear bands. Together, these mechanisms are shown to lead to the unstable migration of grain boundaries via process of coupled motion. An analytical model is used to explain this behavior based on the atomic-level shear stress acting on the interfaces during the shear band propagation. This study sheds light on the atomic mechanism at play during the abnormal grain coarsening observed at low temperature in nanocrystalline metal

Kinetics study and modelling of steam methane reforming process over a NiO/Al2O3 catalyst in an adiabatic packed bed reactor

Kinetic rate data for steam methane reforming (SMR) coupled with water gas shift (WGS) over an 18 wt. % NiO/α-Al2O3 catalyst are presented in the temperature range of 300-700 °C at 1 bar. The experiments were performed in a plug flow reactor under the conditions of diffusion limitations and away from the equilibrium conditions. The kinetic model was implemented in a one-dimensional heterogeneous mathematical model of catalytic packed bed reactor, developed on gPROMS model builder 4.1.0®. The mathematical model of SMR process was simulated, and the model was validated by comparing the results with the experimental values. The simulation results were in excellent agreement with the experimental results. The effect of various operating parameters such as temperature, pressure and steam to carbon ratio on fuel and water conversion (%), H2 yield (wt. % of CH4) and H2 purity was modelled and compared with the equilibrium values

Hydrogen production by sorption-enhanced steam reforming of glycerol

Catalytic steam reforming of glycerol for H(2) production has been evaluated experimentally in a continuous flow fixed-bed reactor. The experiments were carried out under atmospheric pressure within a temperature range of 400-700 degrees C. A commercial Ni-based catalyst and a dolomite sorbent were used for the steam reforming reactions and in situ CO(2) removal. The product gases were measured by on-line gas analysers. The results show that H(2) productivity is greatly increased with increasing temperature and the formation of methane by-product becomes negligible above 500 degrees C. The results suggest an optimal temperature of approximately 500 degrees C for the glycerol steam reforming with in situ CO(2) removal using calcined dolomite as the sorbent, at which the CO(2) breakthrough time is longest and the H(2) purity is highest. The shrinking core model and the 1D-diffusion model describe well the CO(2) removal under the conditions of this work

Chemical equilibrium analysis of hydrogen production from shale gas using sorption enhanced chemical looping steam reforming

Detailed chemical equilibrium analysis based on minimisation of Gibbs Energy is conducted to illustrate the benefits of integrating sorption enhancement (SE) and chemical looping (CL) together with the conventional catalytic steam reforming (C-SR) process for hydrogen production from a typical shale gas feedstock. CaO(S) was chosen as the CO2 sorbent and Ni/NiO is the oxygen transfer material (OTM) doubling as steam reforming catalyst. Up to 49 % and 52 % rise in H2 yield and purity respectively were achieved with SE-CLSR with a lower enthalpy change compared to C-SR at S:C 3 and 800 K. A minimum energy of 159 kJ was required to produce 1 mole of H2 at S:C 3 and 800 K in C-SR process, this significantly dropped to 34 kJ/mol of produced H2 in the CaO(S) /NiO system at same operating condition without regeneration of the sorbent, when the energy of regenerating the sorbent at 1170 K was included, the enthalpy rose to 92 kJ/mol H2, i.e., significantly lower than the Ca-free system. The presence of inert bed materials in the reactor bed such as catalyst support or degraded CO2 sorbent introduced a very substantial heating burden to bring these materials from reforming temperature to sorbent regeneration temperature or to Ni oxidation temperature. The choice of S:C ratio in conditions of excess steam represents a compromise between the higher H2 yield and purity and lower risk of coking, balanced by the increased enthalpy cost of raising excess steam

Electromagnetic analysis of arbitrarily shaped pinched carpets

We derive the expressions for the anisotropic heterogeneous tensors of permittivity and perme- ability associated with two-dimensional and three-dimensional carpets of an arbitrary shape. In the former case, we map a segment onto smooth curves whereas in the latter case we map a non convex region of the plane onto smooth surfaces. Importantly, these carpets display no singularity of the permeability and permeability tensor components, and this may lead to some broadband cloaking.Comment: 6 pages, 6 figures, Current Status of Manuscript: 19Apr10 26May10-Sent on appeal;report rcvd 29Dec09 13Apr10-Ed. decision and/or ref. comments to author;response rcvd 04Dec09 21Dec09-Ed. decision and/or ref. comments to author;response rcvd 01Dec09-Transferred from PRL to PRA 18Aug09 30Nov09-Ed.decision and/or ref. comments to author;response rcvd 14Aug09 - Correspondence sent to autho