Metal Retention Experiments for the Design of Soil-Mix Technology Permeable Reactive Barriers

Soil-mix technology is effective for the construction of permeable reactive barriers (PRBs) for in situ groundwater treatment. The objective of this study was to perform initial experiments for the design of soil-mix technology PRBs according to (i) sorption isotherm, (ii) reaction kinetics and (iii) mass balance of the contaminants. The four tested reactive systems were: (i) a granular zeolite (clinoptilolite-GZ), (ii) a granular organoclay (GO), (iii) a 1:1-mixture GZ and model sandy clayey soil and (iv) a 1:1:1-mixture of GZ, GO and model soil. The laboratory experiments consisted of batch tests (volume 900mL and sorbent mass 18g) with a multimetal solution of Pb, Cu, Zn, Cd and Ni. For the adsorption experiment, the initial concentrations ranged from 0.01 to 0.5mM (2.5 to 30mg/L). The maximum metal retention was measured in a batch test (300mg/L for each metal, volume 900mL, sorbent mass 90-4.5g). The reactive material efficiency order was found to be GZ>GZ-soil mix>GZ-soil-GO mix>GO. Langmuir isotherms modelled the adsorption, even in presence of a mixed cations solution. Adsorption was energetically favourable and spontaneous in all cases. Metals were removed according to the second order reaction kinetics; GZ and the 1:1-mix were very similar. The maximum retention capacity was 0.1-0.2mmol/g for Pb in the presence of clinoptilolite; for Cu, Zn, Cd and Ni, it was below 0.05mmol/g for the four reactive systems. Mixing granular zeolite, organoclay and model soil increased the chemisorption. Providing that GZ is reactive enough for the specific conditions, GZ can be mixed to obtain the required sorption. Granular clinoptilolite addition to soil is recommended for PRBs for metal contaminated groundwater. The laboratory experiments consisted of batch tests with a multimetal solution of Pb, Cu, Zn, Cd and Ni. The four reactive materials chosen were granular zeolite, clinoptilolite and model sandy clayey soil, granular organoclay and a mix of clinoptilolite, model soil and organoclay. The reactive material efficiency order was found to be granular clinoptilolite>clinoptilolite-soil mix>clinoptilolite-soil-organoclay mix>granular organoclay. © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

The influence of stacks on flow patterns and stratification associated with natural ventilation

We investigate the steady state natural ventilation of an enclosed space in which vent A, located at height hA above the floor, is connected to a vertical stack with a termination at height H, while the second vent, B, at height hB above the floor, connects directly to the exterior. We first examine the flow regimes which develop with a distributed source of heating at the base of the space. If hBhB>hA, then two different flow regimes may develop. Either (i) there is inflow through vent B and outflow through vent A, or (ii) the flow reverses, with inflow down the stack into vent A and outflow through vent B. With inflow through vent A, the internal temperature and ventilation rate depend on the relative height of the two vents, A and B, while with inflow through vent B, they depend on the height of vent B relative to the height of the termination of the stack H. With a point source of heating, a similar transition occurs, with a unique flow regime when vent B is lower than vent A, and two possible regimes with vent B higher than vent A. In general, with a point source of buoyancy, each steady state is characterised by a two-layer density stratification. Depending on the relative heights of the two vents, in the case of outflow through vent A connected to the stack, the interface between these layers may lie above, at the same level as or below vent A, leading to discharge of either pure upper layer, a mixture of upper and lower layer, or pure lower layer fluid. In the case of inflow through vent A connected to the stack, the interface always lies below the outflow vent B. Also, in this case, if the inflow vent A lies above the interface, then the lower layer becomes of intermediate density between the upper layer and the external fluid, whereas if the interface lies above the inflow vent A, then the lower layer is composed purely of external fluid. We develop expressions to predict the transitions between these flow regimes, in terms of the heights and areas of the two vents and the stack, and we successfully test these with new laboratory experiments. We conclude with a discussion of the implications of our results for real buildings.

Experiments and Lagrangian simulations on the formation of droplets in continuous mode

Experimental and computational studies on the dynamics of millimeter-scale cylindrical liquid jets are presented. The influences of the modulation amplitude and the nozzle geometry on jet behavior have been considered. Laser Doppler anemometry (LDA) was used in order to extract the velocity field of a jet along its length, and to determine the velocity modulation amplitude. Jet shapes and breakup dynamics were observed via shadowgraph imaging. Aqueous solutions of glycerol were used for these experiments. Results were compared with Lagrangian finite-element simulations with good quantitative agreement. © 2011 The American Physical Society.

Experiments and Lagrangian simulations on the formation of droplets in drop-on-demand mode

The creation and evolution of millimeter-sized droplets of a Newtonian liquid generated on demand by the action of pressure pulses were studied experimentally and simulated numerically. The velocity response within a model, large-scale printhead was recorded by laser Doppler anemometry, and the waveform was used in Lagrangian finite-element simulations as an input. Droplet shapes and positions were observed by shadowgraphy and compared with their numerically obtained analogues. © 2011 American Physical Society.

Kinetics of the chemical looping oxidation of H2 by a co-precipitated mixture of CuO and Al2O3

Chemical-looping combustion (CLC) has the inherent property of separating CO2 from flue gases. Instead of air, it uses an oxygen-carrier, usually in the form of a metal oxide, to provide oxygen for combustion. When used for the combustion of gaseous fuels, such as natural gas, or synthesis gas from the gasification of coal, the technique gives a stream of CO2 which, on an industrial scale, would be sufficiently pure for geological sequestration. An important issue is the form of the metal oxide, since it must retain its reactivity through many cycles of complete reduction and oxidation. Here, we report on the rates of oxidation of one constituent of synthesis gas, H2, by co-precipitated mixtures of CuO+Al2O3 using a laboratory-scale fluidised bed. To minimise the influence of external mass transfer, and also of errors in the measurement of [H2], particles sized to 355-500μm were used at low [H2], with the temperature ranging from 450 to 900°C. Under such conditions, the reaction was slow enough for meaningful measurements of the intrinsic kinetics to be made. The reaction was found to be first order with respect to H2. Above ∼800°C, the reaction of CuO was fast and conformed to the shrinking core mechanism, proceeding via the intermediate, Cu2O, in: 2CuO+H2→Cu2O+H2O, ΔH1073 K0=- 116.8 kJ/mol; Cu2O+H2→2Cu+H2O, ΔH1073 K0-80.9 kJ/mol. After oxidation of the products Cu and Cu2O back to CuO, the kinetics in subsequent cycles of chemical looping oxidation of H2 could be approximated by those in the first. Interestingly, the carrier was found to react at temperatures as low as 300°C. The influence of the number of cycles of reduction and oxidation is explored. Comparisons are drawn with previous work using reduction by CO. Finally, these results indicate that the kinetics of reaction of the oxygen carrier with gasifier synthesis gases is very much faster than rates of gasification of the original fuel. © 2010 The Institution of Chemical Engineers.