Computationsl modelling of dimethyl ether separation and steam reforming in fluidized bed reactors

This study presents a computational fluid dynamic (CFD) study of Dimethyl Ether (DME) gas adsorptive separation and steam reforming (DME-SR) in a large scale Circulating Fluidized Bed (CFB) reactor. The CFD model is based on Eulerian-Eulerian dispersed flow and solved using commercial software (ANSYS FLUENT). Hydrogen is currently receiving increasing interest as an alternative source of clean energy and has high potential applications, including the transportation sector and power generation. Computational fluid dynamic (CFD) modelling has attracted considerable recognition in the engineering sector consequently leading to using it as a tool for process design and optimisation in many industrial processes. In most cases, these processes are difficult or expensive to conduct in lab scale experiments. The CFD provides a cost effective methodology to gain detailed information up to the microscopic level. The main objectives in this project are to: (i) develop a predictive model using ANSYS FLUENT (CFD) commercial code to simulate the flow hydrodynamics, mass transfer, reactions and heat transfer in a large scale dual fluidized bed system for combined gas separation and steam reforming processes (ii) implement a suitable adsorption models in the CFD code, through a user defined function, to predict selective separation of a gas from a mixture (iii) develop a model for dimethyl ether steam reforming (DME-SR) to predict hydrogen production (iv) carry out detailed parametric analysis in order to establish ideal operating conditions for future industrial application. The project has originated from a real industrial case problem in collaboration with the industrial partner Dow Corning (UK) and jointly funded by the Engineering and Physical Research Council (UK) and Dow Corning. The research examined gas separation by adsorption in a bubbling bed, as part of a dual fluidized bed system. The adsorption process was simulated based on the kinetics derived from the experimental data produced as part of a separate PhD project completed under the same fund. The kinetic model was incorporated in FLUENT CFD tool as a pseudo-first order rate equation; some of the parameters for the pseudo-first order kinetics were obtained using MATLAB. The modelling of the DME adsorption in the designed bubbling bed was performed for the first time in this project and highlights the novelty in the investigations. The simulation results were analysed to provide understanding of the flow hydrodynamic, reactor design and optimum operating condition for efficient separation. Bubbling bed validation by estimation of bed expansion and the solid and gas distribution from simulation agreed well with trends seen in the literatures. Parametric analysis on the adsorption process demonstrated that increasing fluidizing velocity reduced adsorption of DME. This is as a result of reduction in the gas residence time which appears to have much effect compared to the solid residence time. The removal efficiency of DME from the bed was found to be more than 88%. Simulation of the DME-SR in FLUENT CFD was conducted using selected kinetics from literature and implemented in the model using an in-house developed user defined function. The validation of the kinetics was achieved by simulating a case to replicate an experimental study of a laboratory scale bubbling bed by Vicente et al [1]. Good agreement was achieved for the validation of the models, which was then applied in the DME-SR in the large scale riser section of the dual fluidized bed system. This is the first study to use the selected DME-SR kinetics in a circulating fluidized bed (CFB) system and for the geometry size proposed for the project. As a result, the simulation produced the first detailed data on the spatial variation and final gas product in such an industrial scale fluidized bed system. The simulation results provided insight in the flow hydrodynamic, reactor design and optimum operating condition. The solid and gas distribution in the CFB was observed to show good agreement with literatures. The parametric analysis showed that the increase in temperature and steam to DME molar ratio increased the production of hydrogen due to the increased DME conversions, whereas the increase in the space velocity has been found to have an adverse effect. Increasing temperature between 200 oC to 350 oC increased DME conversion from 47% to 99% while hydrogen yield increased substantially from 11% to 100%. The CO2 selectivity decreased from 100% to 91% due to the water gas shift reaction favouring CO at higher temperatures. The higher conversions observed as the temperature increased was reflected on the quantity of unreacted DME and methanol concentrations in the product gas, where both decreased to very low values of 0.27 mol% and 0.46 mol% respectively at 350 °C. Increasing the steam to DME molar ratio from 4 to 7.68 increased the DME conversion from 69% to 87%, while the hydrogen yield increased from 40% to 59%. The CO2 selectivity decreased from 100% to 97%. The decrease in the space velocity from 37104 ml/g/h to 15394 ml/g/h increased the DME conversion from 87% to 100% while increasing the hydrogen yield from 59% to 87%. The parametric analysis suggests an operating condition for maximum hydrogen yield is in the region of 300 oC temperatures and Steam/DME molar ratio of 5. The analysis of the industrial sponsor’s case for the given flow and composition of the gas to be treated suggests that 88% of DME can be adsorbed from the bubbling and consequently producing 224.4t/y of hydrogen in the riser section of the dual fluidized bed system. The process also produces 1458.4t/y of CO2 and 127.9t/y of CO as part of the product gas. The developed models and parametric analysis carried out in this study provided essential guideline for future design of DME-SR at industrial level and in particular this work has been of tremendous importance for the industrial collaborator in order to draw conclusions and plan for future potential implementation of the process at an industrial scale.

Synthetic strategies to nanostructured photocatalysts for CO2 reduction to solar fuels and chemicals

Artificial photosynthesis represents one of the great scientific challenges of the 21st century, offering the possibility of clean energy through water photolysis and renewable chemicals through CO2 utilisation as a sustainable feedstock. Catalysis will undoubtedly play a key role in delivering technologies able to meet these goals, mediating solar energy via excited generate charge carriers to selectively activate molecular bonds under ambient conditions. This review describes recent synthetic approaches adopted to engineer nanostructured photocatalytic materials for efficient light harnessing, charge separation and the photoreduction of CO2 to higher hydrocarbons such as methane, methanol and even olefins.

The characterisation of clean metal surfaces

The most perfectly structured metal surface observed in practice is that of a field evaporated field-ion microscope specimen. This surface has been characterised by adopting various optical analogue techniques. Hence a relationship has been determined between the structure of a single plane on the surface of a field-ion emitter and the geometry of a binary zone plate. By relating the known focussing properties of such a zone plate to those obtained from the projected images of such planes in a field-ion micrograph, it is possible to extract new information regarding the local magnification of the image. Further to this, it has been shown that the entire system of planes comprising the field-ion imaging surface may be regarded as a moire pattern formed between over-lapping zone plates. The properties of such moire zone plates are first established in an analysis of the moire pattern formed between zone plates on a flat surface. When these ideas are applied to the field-ion image it becomes possible to deduce further information regarding the precise topography of the emitter. It has also become possible to simulate differently proJected field-ion images by overlapping suitably aberrated zone plates. Low-energy ion bombardment is an essential preliminary to much surface research as a means of producing chemically clean surfaces. Hence it is important to know the nature and distribution of the resultant lattice damage, and the extent to which it may be removed by annealing. The field-ion microscope has been used to investigate such damage because its characterisation lies on the atomic scale. The present study is concerned with the in situ sputtering of tungsten emitters using helium, neon, argon and xenon ions with energies in the range 100eV to 1keV, together with observations of the effect of annealing. The relevance of these results to surface cleaning schedules is discussed.

Enhanced renewable energy adoption for sustainable development in India:interpretive structural modeling approach

Poverty alleviation and social upliftment of rural India is closely linked with the availability and use of energy for development. At the same time, sustainable supply of clean and affordable renewable energy sources is required if development is to be sustainable, so that it does not cause any environmental problems. The purpose of this paper is to determine the key variables of renewable energy implementation for sustainable development, on which the top management should focus. In this paper, an interpretive structural modeling (ISM) - based approach has been employed to model the implementation variables of renewable energy for sustainable development. These variables have been categorized under ‘enablers’ that help to increase the implementation of renewable energy for sustainable development. A major finding of this research is that public awareness regarding renewable energy for sustainable development is a very significant enabler. In this paper, an interpretation of variables of renewable energy for sustainable development in terms of their driving and dependence powers has been examined. For better results, top management should focus on improving the high-driving power enablers such as leadership, strategic planning, public awareness, top management support, availability of finance, government support, and support from interest groups.

Fast x-ray spectroscopy study of ethene on clean and SO4 precovered Pt{111}

The adsorption and decomposition of ethylene over a Pt{111} single crystalsurface has been investigated by fast x-ray spectroscopy. At 100 K ethene displays precursor-mediated adsorption kinetics, adopting a single environment with a saturation C2H4 coverage of 0.25 ML and binding energy of 283.2 eV. Thermal decomposition proceeds above 240 K via dehydrogenation to ethylidyne with an activation barrier of 57±3 kJ mol−1 and preexponential factor ν=1×1010±0.5 s−1. Site-blocking by preadsorbed SO4 reduces the saturation ethene coverage but induces a new, less reactive π-bonded ethene species centered around 283.9 eV, which in turn decomposes to ethylidyne at 350 K.