Local mass transport effects in the FM01 laboratory electrolyser

A number of patterns of segmented line electrodes have been manufactured using copper printed circuit board technology. These segmented electrodes have been used to investigate local mass transport effects in ICI's FM01-LC parallel plate electrolyser. It is shown that in the absence of a turbulence promoter the current distribution is uneven. Along the direction of electrolyte flow, a tertiary current distribution is observed. In addition, close to the cell entrance, an uneven current distribution occurs perpendicular to the direction of electrolyte flow; this reflects the design of the electrolyte distributor. With a turbulence promoter the current distribution is more even and the entry effects are much reduced. The turbulence promoter can, however, impose its own pattern on the current distribution perpendicular to the flow.     

Studies of three-dimensional electrodes in the FMO1-LC laboratory electrolyser

A FMO1-LC parallel plate, laboratory electrochemical reactor has been modified by the incorporation of stationary, flow-by, three-dimensional electrodes which fill an electrolyte compartment. The performance of several electrode configurations including stacked nets, stacked expanded metal grids and a metal foam (all nickel) is compared by (i) determining the limiting currents for a mass transport controlled reaction, the reduction of ferricyanide in 1 m KOH and (ii) measuring the limiting currents for a kinetically controlled reaction, the oxidation of alcohols in aqueous base. It is shown that the combination of the data may be used to estimate the mass transfer coefficient, _L, and the specific electrode area, A _e, separately. It is also confirmed that the use of three dimensional electrodes leads to an increase in cell current by a factor up to one hundred. Finally, it is also shown that the FM01-LC reactor fitted with a nickel foam anode allows a convenient laboratory conversion of alcohols to carboxylic acids; these reactions are of synthetic interest but their application has previously been restricted by the low rate of conversion at planar nickel anodes.Nomenclature A _e electrode area per unit electrode volume (m²m^–3) - c bulk concentration of reactant (mol m^–3) - E electrode potential vs SCE (V) - E _1/2 half wave potential (V) - F Faraday constant (96 485 C mol^–1) - I current (A) - IL limiting current (A) - j _L limiting current density (A m^–2) - _L mass transfer coefficient (m s^–1) - n number of electrons transferred - p empirical constant in Equation 2 - P pressure drop over reactor (Pa) - R resistance between the tip of the Luggin capillary and the electrode surface () - q velocity exponent in Equation 2 - (interstitial) linear flow rate of electrolyte (ms^–1) - V _e volume of electrode (m³)     

Evaluation of carbon electrodes and electrosynthesis of coumestan and catecholamine derivatives in the FM01-LC electrolyser

This work extends the range of electrodes and conditions under which the FM01-LC reactor has been used in a laboratory environment and evaluates the performance of carbon electrodes. Reticulated vitreous carbon (RVC) has been used to provide a stable, inert, three-dimensional electrode surface for organic electrosynthesis; its performance is compared to that of nickel mesh for the oxidation of catechol to o-quinone. This product was then reacted in situ with (i) 4-hydroxycoumarin and (ii) 1,3-dimethylbarbituric acid to produce, respectively, coumestan and catecholamine, products of synthetic interest. In mass transport experiments using hydroquinone oxidation as a model reaction, performance was similar to nickel electrodes, but Sherwood numbers were reduced by about 5–10% when carbon electrodes were used. The best-performing RVC electrode, however, showed poorer behaviour than its nickel counterpart. Yields for the production of coumestan and catecholamine were approximately 45% and 25%, respectively, although this was mostly due to extraction problems, since current efficiencies were both in the region of 65–70%. The electrode material, rather than the fluid flow behaviour, leads to a reduction in overall cell efficiency; this is confirmed by studies which show a film forming on the surface of the electrode.     

The application of flow dispersion models to the FM01-LC laboratory filter-press reactor

The flow distribution in the rectangular channel of a laboratory filter-press electrochemical reactor was evaluated using three flow models namely: (a) axial dispersion, (b) sum of two phases and (c) fast and stagnant zones. In the case of the axial-dispersion model, several methods have been used to calculate the Peclet number; the moment method, the non-linear least-squares and the Laplace transform technique. Several boundary conditions, involving different physical and experimental assumptions of the flow were used to solve the partial differential equation that describes the flow behaviour. A total of nine expressions to examine flow dispersion has been used. The comparison of experimental and predicted response signals was made by evaluating the root mean squared error. A data fit in real time has been found to be a better choice as solutions based on the evaluation of moments are prone to error due the overweight of the signal at long times. Data fitting in the Laplace plane is very accurate but it does not guarantee a good fit in real time. Models based on the sum of a fast and a slow or stagnant phase resulted in solutions having very low values of the extension of the slow and stagnant phases, the assumption of a single phase with some degree of dispersion was considered more appropriate.     

Numerical simulation of mass transport in a filter press type electrochemical reactor FM01-LC: Comparison of predicted and experimental mass transfer coefficient

This paper studies flow characteristics and their effect on local mass transfer rate to a flat plate electrode in a FM01-LC electrochemical reactor. 3D reactor simulations under limiting current and turbulent flow conditions were performed using potassium ferro-ferricyanide electrochemical system with sodium sulfate as supporting electrolyte. The model consists of mass-transport equations coupled to hydrodynamic solution obtained from Reynolds-averaged Navier–Stokes equations using standard k–? turbulence model, where the average velocity field, the turbulence level given by the eddy kinetic energy and the turbulent viscosity of the hydrodynamic calculation were used to evaluate the convection, turbulent diffusion and the concentration wall function. The turbulent mass diffusivity was evaluated by Kays–Crawford equation using heat and mass transfer analogies, while wall functions, for mass transport, were adapted from Launder–Spalding equations. Simulation results describe main flow properties, concentration profiles throughout the entire volume of the reactor and local diffusion flux over the electrode. Overall mass transfer coefficients estimated by simulation, without fitting parameters, agree closely with experimental coefficients determined from limiting current measurements (1.85% average error) for Re between 187 and 1407.     

Prediction of mass transport profiles in a laboratory filter-press electrolyser by computational fluid dynamics modelling

A commercial computational fluid dynamics code (Fluent) has been used to analyze the performance of a unit cell laboratory; the filter-press reactor (FM01-LC) operating with characteristic linear flow velocities between 0.024 m s⁻¹ and 0.110 m s⁻¹. The electrolyte flow through the reactor channel was numerically simulated using a finite volume approach to the solution of the Navier-Stokes equations. The flow patterns in the reactor were obtained and the mean linear electrolyte velocity was evaluated and substituted into a general mass transport correlation to calculate the mass transport coefficients. In the region of 150 < Re < 550, mass transport coefficients were obtained with a relative error between 5% and 29% respect to the experimental k_m values. The differences between theoretical and experimental values are discussed.     

Electrochemical incineration of indigo textile dye in filter-press-type FM01-LC electrochemical cell using BDD electrodes

This work shows results obtained in the incineration of 1 mM indigo textile dye (536 ppm COD) in 0.05 M NaCl aqueous media (which resembles a denim laundry industrial wastewater). Microelectrolysis and macroelectrolysis studies indicated that oxidation of indigo dye was carried out via hydroxyl radicals (OH) formed by water oxidation on the BDD surface, instead of active chlorine as usually occurs by using DSA. Electrolyses in a FM01-LC reactor was performed at Reynolds between 1600 < Re < 18300, and a fixed current density of 5.3 and 15 mA cm⁻². The experimental set-up achieved 100% efficiency in color removal, indigo mineralization and current efficiency. Estimated energy consumption, at Re = 12892 and J = 5.3 mA cm⁻², was 9 kWh m⁻³. Experimental data revealed that hydrodynamic conditions do not influence either the indigo degradation rate or the current efficiencies; therefore indigo degradation must involve a complex mechanism.     

Electrochemical incineration of p-cresol and o-cresol in the filter-press-type FM01-LC electrochemical cell using BDD electrodes in sulfate media at pH 0

This work shows a comparative study of the incineration of 2-mM p-cresol and o-cresol in 1 M-H₂SO₄ in aqueous media. Microelectrolysis studies indicated that both the p-cresol and o-cresol oxidation were carried out via hydroxyl radicals (OH) formed by water oxidation in the boron-doped diamonds (BDD)-H₂O-H₂SO₄-p-cresol and o-cresol interface. In both cases, the potential and current density ranges, where great amounts of OH are formed, were between 2.3 V ≤ E ≤ 2.75 V versus SHE and J = 10 mA cm⁻². Electrolyses in an undivided FM01-LC reactor were performed at different Reynolds values 27,129 ≤ Re ≤ 42,631, and at J = 10 mA cm⁻². For p-cresol and o-cresol, the rate of degradation was slow, however it increases slightly as a function of the Re, indicating that the oxidation involves a complex pathway; current efficiency also rises as a function of the Re. For p-cresol, the mineralization at Re = 42,631 reached 90%, with 71% current efficiency and an energy consumption of 7.84 kWh m⁻³; whereas o-cresol was mineralized to 84%, with 67% current efficiency and an energy consumption of 6.56 kWh m⁻³. The results obtained in this work demonstrated that o-cresol is more recalcitrant than p-cresol.     

Design of a new FM01-LC reactor in parallel plate configuration using numerical simulation and experimental validation with residence time distribution (RTD)

The goal of this work was to develop new geometry design of inlet and outlet distributors of the FM01-LC in parallel plate configuration using Computational Fluid Dynamics (CFD). The new distributor geometry was experimentally evaluated with RTD experimental curves using the stimulus-response technique and approximated with axial dispersion model (ADM), plug dispersion exchange model (PDEM) and by solving the hydrodynamic (Reynolds average Navier–Stokes equation for low Reynolds number, RANS-LRN) and mass transport (convection–diffusion equation in transient and turbulent regimen) equations using computational fluid dynamics (F-tracer RTD method). Two sets of RTD experiments (common and new inlet and outlet distributors) in FM01-LC reactors with channel thickness of 0.011 m were carried out. The volumetric flows (Q) employed were from 0.5 to 3.5 L min⁻¹ (U₀ = 0.02-0.15 m s⁻¹). The new FM01-LC reactor had a more homogeneous velocity field in the entire reaction zone, as shown by axial dispersion values lower than those obtained with the common FM01-LC, at different Reynolds numbers. The RTD curves obtained with Comsol Multiphysics 4.3a are in agreement with RTD experimental curves, but deviations are observed at Reynolds numbers greater than “5991”.     

Analysis and interpretation of residence time distribution experimental curves in FM01-LC reactor using axial dispersion and plug dispersion exchange models with closed-closed boundary conditions

The liquid phase mixing flow pattern at low (20 < Re < 120) and intermediate liquid flow rate (120 < Re < 400) was studied by means of residence time distribution (RTD) experimental curve in an up-flow Filter Press electrochemical reactor (FM01-LC) bench scale. For this purpose, a plastic turbulence promoter was used with stainless-steel and platinised titanium structural meshes as electrodes in channel configuration. To visualize and determine the mixing flow pattern in the liquid phase, the stimulus-response technique was employed using dextran blue (D_M = 1.058 × 10⁻¹¹ m² s⁻¹, 25 °C, in water) as model tracer. A theoretical analysis and approximation RTD experimental curves with axial dispersion model (ADM) and plug dispersion exchange model (PDE), with “closed-closed vessel” boundary conditions were used in order to establish a better approximation of the axial dispersion, stagnant zones, channelling and by-pass (preference flow) effects present at low and intermediate Re. RTD curves show that the liquid flow pattern in the FM01-LC deviates considerably from axial dispersion model at low Re, where the FM01-LC exhibits large channelling, stagnant zones, and dead zone. The PDE model represents fairly this deviation from ideal flow (less dead zone).     

Advanced laboratory electrolyser for production of pure hydrogen

A laboratory scale diaphragmless water electrolyser has been developed for the production of pure hydrogen at a pressure of up to 140 kPa by electrolysis of a KOH solution. Porous electrodes with a nickel catalyst and a copper cover layer serve as cathodes, and nickel sheets as anodes. Modular construction of the electrolyser permits simple combination of its cells into larger units. Thus, up to 20 cells with disc-shaped electrodes of 7 cm in diameter were connected in series and provided with electrolyte manifolds and automatic pressure and electrolyte level control devices. The dimensions of the electrolyte manifolds were optimized on the basis of calculations of parasitic currents. A good agreement between the calculated and measured current efficiencies was found at various cell numbers and total currents.     

Simulation of velocity profiles in a laboratory electrolyser using computational fluid dynamics

A commercial CFD code, Fluent, has been used to analyse the design of a filter-press reactor operating with characteristic linear flow velocities between 0.024 and 0.192 m s⁻¹. Electrolyte flow through the reactor channel was numerically calculated using a finite volume approach to solve the Navier-Stokes equations. The length of the channel was divided into 7 sections corresponding to distances of 0, 0.01, 0.04, 0.08, 0.12, 0.14 and 0.15 m from the electrode edge nearest to the inlet. The depth of the channel was divided into three planes parallel to the channel bottom. For each channel section, a velocity profile was obtained at each depth together with the average velocity in each plane. The flow predictions show that the flow development, as the electrolyte passes through the cell, is strongly affected by the manifold causing strong vortex structures at the entrance and exit of the channel. Although the flow disturbances are a function of the flow rate, they gradually disappear downstream along the channel length. Simulated velocity profiles are considered for the typical current density range used in the FM01-LC reactor.     

A computational laboratory on the role of mass transport contributions in electrochemical systems: Copper deposition

This paper presents a computational laboratory that describes the ionic transport of chemical species in an electrochemical process. The system is modeled in 1D using a kinetic model type Butler–Volmer coupled with mass balance equations, i.e. Nernst–Planck formalism. This laboratory is intended to be a practical learning tool to study the deposition of chemical species, e.g. Cu²⁺, subject to the typical mass transfer mechanisms, i.e. diffusion, migration and convection. Sensitivity analyses are used to analyze the effect of each mass transport phenomena over the process reaction rate. The material showed in this paper is a section (laboratory) of two third-year courses in the Nanotechnology and Chemical Engineering undergraduate programs at the University of Waterloo. The pedagogical goals, learning experiences and students’ comments of this laboratory are presented in this work.     

Flow field in the rotating electrolyser

The fluid velocity field in the rotating electrolyser has been computed for a variety of conditions. It is shown that there is strong coupling between the orthogonal velocity components, the volumetric flowrate and the angular velocity. Reversing radial and tangential flows are predicted, particularly in the entry region, which agrees with laser-Doppler measurements previously reported. Outside the entry region (r/a25) there is good agreement between experimental and theoretical profiles, which approach the predictions of first order theory within 15% for reasonable flowrates, making design studies of the electrolyser simple.     

CFD evaluation of internal manifold effects on mass transport distribution in a laboratory filter-press flow cell

The internal manifold geometry strongly influences the flow distribution inside an electrochemical reactor. The mass transport coefficient is a function of the flow pattern and is a key parameter in successful electrochemical reactor design and scale-up. In this work, a commercial computational flow dynamics (CFD) package was used to describe the flow pattern in the FM01-LC reactor at controlled volumetric flow rates (corresponding to mean linear flow velocities past the electrode surface between 0.024 and 0.11 m s^?1). Numerical Re numbers were obtained for each local flow velocity at different positions in the reactor channel. From a known mass transport correlation (based on dimensionless groups, i.e. Sh, Re, Sc), numerical k _m values were obtained (in the range 200 < Re < 1,000) at different positions in the reactor channel. Computed k _m numbers are compared against experimental values. This computational approach could be useful in reactor design or selection since it facilitates a fast, preliminary reactor flow and mass transport characterisation without experimental electrochemical measurements.     

大规模异养发酵培养小球藻USTB-01研究

采用异养小球藻USTB-01,分别在50、500 L和5 000 L发酵罐逐级放大进行异养发酵培养的优化控制研究.结果表明,随着小球藻异养培养过程中生物量的增大,按照3个不同阶段逐渐加大葡萄糖和硝酸钾(C/N质量比为20:1)分别作为碳源和氮源的流加量.可以大幅度提高小球藻USTB-O1的生长速度.72 h内,分别在50、500 L和5 000 L发酵罐进行异养发酵培养小球藻USTB-01过程中,都获得了质量浓度40 g/L以上的藻细胞干重,在培养物中保持低浓度的葡萄糖和硝酸钾在支持小球藻快速生长方面发挥了重要作用.无论在培养规模,还是在最终培养获得的藻生物量上,均取得了非常重要的研究进展.     

Voltammetry in the presence of ultrasound: mass transport effects

The voltammetry of various well-defined systems in acetonitrile solution has been studied using both micro and macroelectrodes in the presence of power ultrasound. A simple model is established which quantifies the mass transport observed under these conditions; this assumes that the effect of ultrasound is to promote mixing within the bulk of the solution up to within a certain distance of the electrode surface. Thus the ultrasound serves to thin the diffusion layer which would exist at the corresponding electrode under silent conditions. The relative enhancement of transport limited currents by ultrasound is dependent on the size of the electrode; for micrometre-sized electrodes the steady state limiting current observed tends to that predicted under silent conditions whereas for large electrodes a thin, steady-state diffusion layer is seen with a thickness which is power dependent. In addition to steady-state experiments, a.c. impedance measurements and potentials steps are used to verify the model proposed.Author to whom corresponding should be sent.     

Electro-organic reactions. Part 60[1]. The electro-oxidative conversion at laboratory scale of a lignosulfonate into vanillin in an FM01 filter press flow reactor: preparative and mechanistic aspects

The electrochemical conversion of a spruce lignosulfonate into vanillin, at nickel anodes, was explored in previously unobtainable detail. A flow reactor (FM01), in a rig that permitted considerable variation of electrolysis conditions, allowed up to 150 g to be electrolysed at up to12 A at a variety of electrode configurations. Samples taken during electrolysis gave detailed reaction profiles. The electrolyser operated at 145 °C/500 kPa/3 M NaOH and yields of vanillin were similar to those obtained industrially using chemical oxidants (about 5–7% w/w). Vanillin production was favoured by low current density and low initial concentration of lignosulfonate. Vanillin, alone, was consumed in a 2.7 F process under the above conditions. Historically, yields in chemical and electrochemical conversions of lignins into vanillin do not exceed 10%; the results herein explain this apparent limit as equilibrium between formation of vanillin, its concomitant oxidative destruction and further condensation of lignins.     

Estimation of concentration-dependent diffusion coefficient in drying process from the space-averaged concentration versus time with experimental data

The estimation of a concentration-dependent diffusion coefficient in a drying process is known as an inverse coefficient problem. The solution is sought wherein the space-average concentration is known as function of time (mass loss monitoring). The problem is stated as the minimization of a functional and gradient-based algorithms are used to solve it. Many numerical and experimental examples that demonstrate the effectiveness of the proposed approach are presented. Thin slab drying was carried out in an isothermal drying chamber built in our laboratory. The diffusion coefficients of fructose obtained with the present method are compared with existing literature results.     

Multiphase mass transport with partitioning and inter-phase transport in porous media

We derive the effective mass-transfer coefficient between two fluid phases in a porous medium, one of which is flowing and the other is immobile. A passive tracer is advected by the flowing phase, becomes partitioned at the fluid-fluid interface and diffuses in the immobile phase. We use traditional volume-averaging methods to obtain a unit-cell boundary-value problem for the calculation of the effective mass-transfer coefficient. The problem is controlled by the Peclet number of the flowing phase, by a second dimensionless parameter that captures diffusion and partition in the two phases and by the geometrical properties of the porous medium.We derive asymptotic results for the scaling of the mass-transfer coefficient under various limiting conditions. Then, we use numerical methods that solve for the flow velocity field under Stokes flow conditions, and for the transport problem. The numerical results verify the asymptotic scaling expressions and provide estimates of the coefficient for a number of special cases. In particular, we find that when the immobile phase is wetting the solid (in the form of films), the mass transfer coefficient is larger than in the non-wetting case (where the phase is distributed in the form of blobs). Shape factors for practical applications are also obtained.