Carbon materials and catalytic wet air oxidation of organic pollutants in wastewater

The use of carbon materials as catalytic support or direct catalyst in catalytic wet air oxidation (WAO) of organic pollutants is reviewed. The discussion covers important engineering aspects including the characterisation, activity and stability of carbon catalysts, process performance, reaction kinetics and reactor modelling. Recommendations for further research in catalytic WAO are outlined.     

Simulation of packed bed reactors using lattice Boltzmann methods

Lattice Boltzmann (LB) methods are used to simulate hydrodynamics, reaction and subsequent mass transfer in a disordered packed bed of catalyst particles at sub-pore length-scales. In contrast to previous studies, a variety of modifications are introduced in the LB method enabling particle Pe numbers up to 10⁸, and hence realistic values of diffusivity, to be accessed. These include decoupling the hydrodynamics from mass transfer and the use of a rest fraction in the LB formulation of mass transfer. In addition the mass transfer simulations are modified to permit spatially varying values of diffusivity, essential to differentiate between intra- and inter-particle diffusivity (D_intra and D_inter, respectively). The simulation method is applied to both a disordered and ordered 2D packing for a range of Pe (15.6-1557.8) and Re (0.16-1.56) numbers, as well as various ratios of D_intra/D_inter (0-1), whilst simulating an esterfication reaction catalyzed by an ion-exchange resin. The value of D_intra is found to have limited effect, whilst reducing Pe number results in a considerable increase in overall conversion. The simulation method is then applied to a 3D lattice for which experimental conversion data is available. This experimental data is straddled by the simulation case of D_intra=0 and D_intra=D_inter, as expected.     

Kinetics of fluidised bed melt granulation III: Tracer studies

Previous work (Proceedings of World Congress on Particle Technology, Sydney 2002, 629-636.) has shown that granule breakage occurs during fluidised bed melt granulation (FBMG) and should not be neglected when it comes to addressing granulation kinetics. In the current work, we have developed and verified tracer experiments in FBMG, in an attempt to decouple the influence of granule size and age on breakage kinetics. The tracer data during granulation shows that granule breakage is occurring at a much slower rate than aggregation, while the breakage-only tracer experiments reveal the breakage selection rate to be independent of size at an approximate value of . The observations allow us to deduce that the aggregation rate for smaller granules is actually faster than larger ones during granulation.     

External-loop fluidized bed airlift bioreactor (EFBAB) for the cometabolic biotransformation of 4-chlorophenol (4-cp) in the presence of phenol

The advantages from a 4-l external-loop inversed fluidized bed airlift bioreactor (EIFBAB) reported by Loh and Liu [2001. Chemical Engineering Science 56, 6171-6176] was synergized with preferential adsorption by granular activated carbon (GAC) for the enhanced cometabolic biotransformation of 4-chlorophenol (4-cp) in the presence of phenol as a growth substrate. This was achieved by incorporating a GAC fluidized bed in the lower part of the riser with the gas sparger relocated above this fluidized bed to avoid the presence of a 3-phase flow in the fluidized bed consequently providing larger gas holdup. Expanded polystyrene beads (EPS) were used as the supporting matrix for immobilizing Pseudomonas putida ATCC 49451, in the downcomer of the bioreactor. The hydrodynamics of the bioreactor system was characterized by studying the effect of the extent of valve opening, under cell-free condition, on gas holdup and liquid circulation velocity at different gas velocities and solids loading (EPS and GAC). The experimental data for gas holdup were modeled using power law correlations, while a Langmuir-Hinshelwood kinetics model was used for the liquid circulation velocity. The bioreactor was tested for batch cometabolic biotransformation of 4-cp in the presence of phenol at various concentration ratios of phenol and 4-cp (ranging from phenol: 4-cp to phenol: 4-cp) at 9% EPS loading and 2.8% (10 g) GAC loading. The 4-cp and phenol biotransformations were achieved successfully in the bioreactor system, which ascertained the feasibility of the bioreactor. Biotransformation of high 4-cp and phenol concentrations, which was oxygen limited, was also effectively achieved by increasing the gas holdup in the riser. This was possible in the current EFBAB system because of the synergistic effect of the GAC fluidized bed, the globe valve and cell immobilization by EPS.     

Uncertainties in the simulation of catalytic distillation process: A systematic grid refinement study

Computational fluid dynamics (CFD) methods are gradually finding applications in the simulation of distillation processes. In the discretization of the governing differential equations for the mass- and the energy-balance, finite volume method (FVM) is commonly employed. Upwind differencing scheme (UDS) and central differencing scheme (CDS) are most commonly employed in FVM to approximate the values of the variables on the control volume faces. The problems that arise while using these approximation methods are discussed here. These may be overcome by using a bounded linear deferred correction scheme (LDC). When solutions on more than one grid sizes are available, and the order of the numerical scheme is known, the exact solution may be predicted by using Richardson extrapolation technique. If the order is unknown, then the order of the scheme may be determined from grid refinement studies. However, for the determined order of the scheme to be meaningful, sufficiently fine grids must be used for these studies.     

Fluidization with hot compressed water in micro-reactors

In this paper the concept of micro-fluidized beds is introduced. A cylindrical quartz reactor with an internal diameter of only 1 mm is used for process conditions up to and 244 bar. In this way, fast, safe, and inherently cheap experimentation is provided. The process that prompted the present work on miniaturization is gasification of biomass and waste streams in hot compressed water (SCWG). Therefore, water is used as fluidizing agent. Properties of the micro-fluid bed such as the minimum fluidization velocity (U_mf), the minimum bubbling velocity (U_mb), bed expansion, and identification of the fluidization regime are investigated by visual inspection. It is shown that the micro-fluid bed requires a minimum of twelve particles per reactor diameter in order to mimic homogeneous fluidization at large scale. It is not possible to create bubbling fluidization in the cylindrical micro-fluid beds used. Instead, slugging fluidization is observed for aggregative conditions. Conical shaped micro-reactors are proposed for improved simulation of the bubbling regime. Measured values of U_mf and U_mb are compared with predictions of dedicated 2D and 3D discrete particle models (DPM) and (semi)-empirical relations. The agreement between the measurements and the model predictions is good and the model supports the concept and development of micro-fluid beds.     

Assessment of a redox alkaline/iron-chelate absorption process for the removal of dilute hydrogen sulfide in air emissions

The oxidative absorption of hydrogen sulfide (H₂S) into a solution of ferric chelate of trans-1,2- diaminocyclohexanetetraacetate (CDTA) was studied in a counter-current laboratory column randomly packed with 15 mm plastic Ralu rings. The present investigation takes concern about the Kraft pulping situation where dilute H₂S concentrations are omnipresent in large-volume gas effluents. A fractional two-level factorial approach was instigated to determine the significance of six operating variables, namely the solution's alkalinity (pH; 8.5-10.5), the liquid mass flow rate (L;1.73-), the solution's ionic strength (I_C;0.01-), the gas mass flow rate (G;0.19-), the inlet H₂S concentration (C_H2S,0;70-430 ppm) and the initial ferric CDTA concentration (C_Fe,0;100 -). Initially, a Plackett-Burman design matrix of seven duplicated experiments revealed that pH is the leading factor controlling the H₂S conversion rate while the ionic strength and ferric CDTA concentration effects remained negligible within the factorial domain. Surface response analysis based on 11 duplicated factorial experiments plus 10 central composite trials revealed that the H₂S conversion significantly increases with liquid flow rate but decreases with growing H₂S load up. Further examination about the influence of ferric CDTA on H₂S absorption rate was set up over a broader concentration range (C_Fe,0;0- at pH of 9.5 and 10.5. It showed good potential at as H₂S conversion increased by a significant 25% for both pH values in comparison to pure alkaline solutions containing no ferric CDTA.     

Electrochemical study of a hydrogen diffusion anode-membrane assembly for membrane electrolysis

The membrane electrode assembly (MEA) studied was constituted with a gas diffusion electrode (E-TEK) impregnated with Nafion^® solution which was assembled with a Nafion^® 117 cation exchange membrane under heat and pressure. The MEA was used as anode in a membrane electrolysis (ME) cell with the objective to regenerate HCl and NaOH from NaCl. Current efficiency for hydrogen oxidation was determined and its value is 100%, which indicates that the only reaction occurring at the anode is the oxidation of hydrogen. Current-potential curves, recorded in different conditions, showed a linear variation in the range 0-3000 A m⁻² when hydrochloric acid concentration is below 2 mol dm⁻³. In this case, the overvoltage was shown to be mainly due to the ohmic drop in the membrane and in the layer where Nafion^® impregnation was performed. MEA overvoltage necessary to reach 3000 A m⁻² current density was about 0.12 V. For high HCl concentration (6-8 mol dm⁻³), the MEA overvoltage increased sharply with current density due to the adsorption of chloride anions on platinum catalyst.     

Thermal properties and morphology of a poly(vinyl alcohol)/silica nanocomposite prepared with a self‐assembled monolayer technique

A poly(vinyl alcohol) (PVA)/silica (SiO₂) nanocomposite was prepared with a novel self‐assembled monolayer technique, and its morphology and thermal properties were studied with different material characterization instruments. The treated SiO₂ nanoparticles were dispersed in the PVA matrix homogeneously, and the thermal properties of the nanocomposite were markedly improved in comparison with those of pure PVA. Under the same isothermal heating conditions, the decomposition of the nanocomposite was delayed significantly in comparison with that of PVA. The thermal degradation of the nanocomposite was a two‐step reaction, including the degradation of the side chain and main chain. The products of side‐chain degradation were mainly carboxylic acid, whereas main‐chain degradation primarily produced carbon dioxide and low‐molecular‐weight conjugated polyene. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 96: 1436–1442, 2005     

Photoinduced Polymerization in the Wall of Hollow Capsules

Summary: Novel light‐sensitive hollow capsules were fabricated from the small molecule 3‐sulfopropylacrylate potassium (SPA) and poly(allylamine hydrochloride) (PAH). With UV irradiation, SPA could be photopolymerized in the wall of hollow capsules. After photopolymerization the capsule size and surfaces showed pronounced differences. The capsules became much more rigid as indicated by an increase in the modulus of more than a factor of 5.

CLSM image of SPA/PAH hollow capsule emission at 554 nm, from rhodamine B after photopolymerization.