Flow field investigation in a photocatalytic reactor for air treatment (Photo-CREC-air)

The aerodynamic behavior of a photocatalytic reactor for air treatment, Photo-CREC-air, with demonstrated high quantum efficiency performance, is examined using CFX-5.7.1. Photo-CREC-air consists of a venturi section that features low pressure drop and uniform illumination of the photocatalyst, resulting in high oxidation quantum efficiencies. The numerical simulations allowed the identification of several design issues in the original Photo-CREC-air unit, which include extensive boundary layer separation close to the photocatalyst support and regions of flow recirculation that render ca. 77% of the support surface area inactive. The simulations reveal that this issue could be addressed by replacing the wire-mesh basket sidewalls with perforated plates. This modification causes an increase in the pressure drop downstream of the support and achieves significant uniformization of the mass flow and air-photocatalyst contact time distributions.A modified Photo-CREC-air design is also presented and studied using CFX-5.7.1. This modified design is envisaged with the objective of improving UV-irradiation uniformity, an issue that is not completely addressed in the original design due to the shape of the windows and divergent section. CFD simulations reveal that, although the flow field is uniform, mass flow and contact time distributions are not. Nonetheless, this problem is addressed by increasing the pressure drop downstream of the support through the addition of a region modeled as a perforated plate. The simulations reveal that the mass flow and contact time distributions are significantly uniformized once this modification is implemented.     

Mass transfer measurements and modeling in a microchannel photocatalytic reactor

The main objective of this paper was to evaluate the influence of mass transfer on the photocatalytic efficiency at a low flow rate in the order of several mL per hour. Several continuous flow microchannel reactors have been used to study the degradation of salicylic acid (SA) taken as a model pollutant. The photocatalytic degradation of salicylic acid, under UV illumination of 1.5 mW cm⁻², was assessed from the outlet concentration measured by liquid chromatography HPLC. It was shown that the degradation of SA by UV was limited by mass transfer. Numerical simulations have allowed establishing a relationship of the Sherwood number valuable for all the microchannel geometries. Computational fluid dynamics with Comsol Multiphysics is useful for predicting the degradation yield for a given geometry of the microreactor. The best representation of the experimental data is obtained by introducing a kinetic law taking into account mass transfer limitation.     

Scaling-up from first principles of a photocatalytic reactor for air pollution remediation

A proposal for scaling-up photocatalytic reactors is described and applied to catalytic walls coated with a thin layer of titanium dioxide and irradiated with near UV radiation. The method is exclusively based on the fundamentals of chemical reaction engineering and radiative transfer theory, without the use of adjustable parameters in going from the laboratory information to a pilot scale apparatus. Mathematical modeling has been utilized. From kinetic information obtained in experiments performed in a flat plate of , operating at steady state in a continuous, well-mixed reactor with recycle, predictions for a continuous flow, multi-annular reactor having a catalytic surface of agree very well with the validation tests. Thus, the achieved scale-up implies a change in size, shape, configuration and operating conditions of both employed reactors. Requirements to apply satisfactorily the proposed methodology are reported in detail. The root mean square error in the verification of conversion predictions for the larger scale photocatalytic reactor when compared with experimental data is less than 5.6%.     

Radiation absorption and degradation of an azo dye in a hybrid photocatalytic reactor

Results are presented for the photocatalytic degradation of an azo dye, reactive blue 69, in a novel hybrid photocatalytic reactor, illuminated by solar radiation and artificial light, under different experimental conditions. A radiative transfer model, based on the P1 approximation, is proposed to evaluate the distribution of local volumetric rate of photons absorption (LVRPA) in the reaction space of the hybrid photocatalytic reactor. This radiation transfer model, together with a first order kinetic model, is used to fit the experimental results. The model correlates well with the experiments, and values for an apparent first order kinetic constant for the degradation of RB69 are obtained. The proposed radiative transfer model (P1 approximation) is simple enough to allow for an analytical solution, yet complex enough to take into account scattering of radiation in all directions and to all orders. Simulations show a distribution of LVRPA that varies smoothly at small catalyst concentration, and is very quickly attenuated for high concentrations. Around of 70% of photons supplied by both illumination sources to the hybrid photocatalytic reactor are absorbed by the catalyst. The experimental results show the decolorization degree increases as catalyst concentration increase. In relation to mineralization process, the removal of total organic carbon is nearly complete after 5 hours irradiation. This indicates that not only the azo bond breakage is carried out, but also that the intermediate species are mineralized. The apparent kinetic constant has a dependence on catalyst concentration which is described by an adsorption model. Addition of oxygen by means of an air diffuser proves to be beneficial to the process.     

The degradation of an azo dye in a batch slurry photocatalytic reactor

The photocatalytic degradation of a commercial azo-reactive textile dye, Remazol Red F-3B, has been investigated in a batch slurry reactor using semiconductor catalysts like, ZnO and TiO₂, and two UV sources emitting mainly at 254 and 365 nm. Non-irradiated catalysts and non-catalyzed UV irradiation have negligible effect on the dye degradation. Initial pH, dye concentration, light power and catalyst loading as well as the catalyst type and UV wavelength are considered as process variables. The results showed that decolorization and TOC removal efficiencies of ZnO are higher under 365 nm UV. On the other hand, when two photocatalysts are compared, the decolorization performance of ZnO is higher than TiO₂ under 365 nm UV_, while TiO₂ performs better under 254 nm UV. Furthermore, from the TOC removal point, TiO₂ performs better than ZnO irrespective of the UV wavelength. TiO₂ irradiated under 254 nm UV degrades successfully both benzene and naphthalene derivatives.     

Photo-catalytic degradation of air borne pollutants apparent quantum efficiencies in a novel photo-CREC-air reactor

This study describes photo-conversion in a novel Photo-CREC-Air reactor. Experiments were developed using three model pollutants and two commercial TiO₂ photo-catalysts: Degussa P25 and Hombikat UV-100. Apparent quantum efficiencies were evaluated on the basis of the following: (a) 90% of pollutant converted in CO₂, (b) initial photo-conversion rates. It was observed that in a significant number of runs the apparent quantum efficiencies were in excess to 100% and this strongly suggests a radical chain reaction mechanism for the photo-conversion process.     

Non-isothermal lipase-catalyzed kinetic resolution in a packed bed reactor: Modeling, simulation and miniplant studies

A rigorous model is developed for the exothermic kinetic resolution of 1-methoxy-2-propanol with vinyl acetate catalyzed by immobilized Candida antarctica lipase B in a packed bed reactor. The non-isothermal two-dimensional heterogeneous model takes into account the coupled mass and energy balances, the uneven flow distribution and irreversible ping-pong bi-bi kinetics with competitive substrate inhibition by both enantiomers. This model is based on kinetic parameters, which were estimated in earlier work. The model simulation is validated with experimental results obtained in a fully automated modular miniplant and is shown to be capable of predicting the key parameters needed for process design of a kinetic resolution, the enantiomeric excess and the extent of conversion at a given superficial velocity.     

Carbonaceous-TiO2 nanomaterials for photocatalytic degradation of pollutants: A review

Semiconductor photocatalysis is one of most appealing and attractive technologies, which has been directly utilized to harvest solar energy for energy and environmental applications. Titanium dioxide (TiO₂) has been proved to be leading semiconductor photocatalyst for the degradation of pollutants. However, it suffers from low photocatalytic activity under visible light activation because of its intrinsic wide band gap. Various strategies have been developed to enhance TiO₂ efficiency in the visible light region. Among them TiO₂ modification with carbonaceous nanomaterials is very effective route for excellent photocatalytic activity. This critical review aims to present recent progress in the design and synthesis of carbonaceous-TiO₂ photocatalysts, covering carbon doping, activated carbon, fullerenes, carbon nanotubes and graphene. Moreover, proposed mechanisms of enhancement, effect of synthesis routes, demonstrations of performance and applications reported in literature are reviewed. Ongoing challenges and possible new directions are outlined.     

Optimisation of degradation conditions of 1,8-diazabicyclo[5.4.0]undec-7-ene in water and reaction kinetics analysis using a cocurrent downflow contactor photocatalytic reactor

The photocatalytic degradation of 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU, a non-biodegradable nitrogenous organic compound) in water was optimised under UV radiation using titanium dioxide photocatalyst. The reactor used was a pilot scale cocurrent downflow contactor photocatalytic reactor (CDCPR), a system offering very high mass transfer efficiency. The effect of photocatalyst loading, initial substrate concentration, temperature, pH, and different combinations of UV, O₂, H₂O₂ and TiO₂ on the photocatalytic oxidation of DBU was investigated. The TiO₂ photocatalyst used was Degussa VP Aeroperl P25/20, a granulated form of Degussa P-25, recently developed to ameliorate downstream catalyst separation problems. The CDCPR was fitted with an internally and vertically mounted 1.0 kW UV lamp. The reactions were carried out at 40–60 °C and 1 barg, with the reactor being operated in closed loop recycle mode and suspended photocatalyst being re-circulated. Optimisation of reaction conditions using a combination of TiO₂, UV radiation and O₂ gave the most rapid degradation and mineralisation of the DBU in comparison with other processes. Under optimised conditions, 100% degradation of DBU was achieved in 45 min, with a quantum yield of 7.39, using a 1 kW lamp, 0.5 g/dm³ TiO₂, 100 mg/dm³ DBU, 1 barg, 50 °C and pH of 3.17. Investigating the reaction pathway and its modelling showed a first order dependency, incorporating the effect of first intermediates of degradation. The activation energy was found to be 54.68 kJ mol⁻¹ showing a significant influence of temperature on the photocatalytic degradation of DBU.     

Simulation of turbulent combustion and NO formation in a swirl combustor

A presumed probability density function (PDF) model for temperature fluctuation is proposed and formulated in this paper. It incorporates a two-step reaction mechanism for propane combustion and the thermal and prompt NO formation mechanisms. The present model, together with a new algebraic Reynolds stress model (ASM), is employed to simulate the turbulent combustion and NO formation in a swirl combustor. The calculated propane, carbon monoxide, and carbon dioxide concentrations agree with the measurement. The calculated gas temperature and oxygen and NO concentrations are in general agreement with the measured data. The simulated results show that NO forms mainly in the upstream region of the combustor. The flue gas recirculation effectively abates the nitrogen oxides (NO_x) emission in the combustor.     

Photocatalytic degradation of gaseous perchloroethylene in continuous flow reactors: Rate enhancement by chlorine radicals

The degradation of perchloroethylene (PCE) by UV/TiO₂ photocatalysis in gas phase was studied. The degradation efficiency has been compared in different continuous flow reactors: a photocatalytic tangential reactor (PTR) where the air flows tangentially over the catalytic medium and two photocatalytic filtering reactors (PFR) where the air flows through the porous catalytic medium. The degradation rate shows a linear dependence with the concentration of pollutants (up to 350 mg PCE/N m³) for the PTR, but the degradation was negligible for the PFR. The degradation rate was enhanced by accelerating the chlorine radicals’ formation (by adding HCl in catalytic quantity in the air flow or by PCE over-heating). In these conditions, the oxidation rate constant of PCE in the PFR was about five times higher than that in the PTR, although the mass of catalyst involved in the PFR was about 10 times lower and the contact time was about a 1000 times shorter than that of the PTR. Thus, the catalyst is globally more efficiently used in the PFR, as the mass transfer is not limiting. As a result, a degradation mechanism of PCE, involving the generation of free chlorine radicals, as the first limiting step, has been confirmed.     

Comparison of different reactor types for low temperature Fischer-Tropsch synthesis: A simulation study

The commercially established slurry bubble column and fixed-bed reactors for low temperature Fischer-Tropsch synthesis were compared with novel micro- and monolith-reactors by mathematical modeling. Special attention was paid to the influence of catalytic activity on the reactor efficiency and the losses by mass and heat transfer resistances. The simulation results show that a micro-structured reactor exhibits the highest productivity per unit of catalyst volume followed by slurry bubble column reactor and monolith reactor. The fixed-bed reactor that was assumed to operate in the trickle-flow regime has a particularly low catalyst specific productivity due to severe mass transfer resistances. However, caused by a very low ratio of catalyst and reactor volume the micro-reactor has only a similarly low productivity per unit of reactor volume as the fixed-bed reactor. In contrast, the reactor specific productivity of slurry bubble column reactor and monolith reactor is up to one order of magnitude higher.     

Simulation of algae growth in a bench scale internal loop airlift reactor

The growth of red marine alga Porphyridium sp. cultivated in an internal loop airlift (ALR) photobioreactor was simulated. The model proposed integrates a dynamic formulation of the kinetics of photosynthesis, photoinhibition, and the fluid dynamics of the ALR, including shear stress effects on the kinetics of growth. The kinetic parameters obtained previously for a system under defined light/dark cycles were used, and satisfactory agreement was found. The maintenance term was modified to take into account the detrimental effects of shear stress in the bioreactor on the rate of growth. A hybrid method for approximate solution of the equations is proposed. The conditions of gas flow rate and illuminance required for positive growth were found. This is the first mathematical model that predicts the effect of gas flow rate, column height, column diameter, and cross-sectional areas on the productivity of a photosynthetic process in an airlift bioreactor. Extrapolations done using the model indicate the possibility of predicting the optimal diameter for an assembly of ALR photobioreactors.     

Radiation absorption and rate constants for carbaryl photocatalytic degradation in a solar collector

We discuss an analytical model for the evaluation of radiation absorption in a tubular photocatalytic reactor. The model has no adjustable parameters and takes into account scattering in all directions. We compare the results of this model with those of Monte Carlo (MC) simulations and of a Lambert–Beer (LB) approximation, for a reactor illuminated by a parabolic solar concentrator. A good correspondence is found with the MC simulations. In particular, the model displays the correct saturation behavior of absorption for large catalyst particle concentrations, which is not obtained with the LB approximation. We have carried out experiments for the degradation of carbaryl in a solar parabolic collector (PC). The model is used to calculate the rate constant for this degradation from the experimental data. The theoretical model predictions reproduce well, the trends observed in the experiments.     

Simulation and energy consumption analysis of a propane plus recovery plant from natural gas

This paper deals with the investigation of a cryogenic plant for the recovery of propane plus compounds from natural gas. The commercially available software ASPEN Plus® has been used to simulate the process, and to investigate the effect of the main operating variables on the efficiency of propane plus recovery and on the energy required by the various pieces of equipment of the plant. With respect to the base case considered, the optimized plant allows to reduce the heat required up to 25%; besides, the refrigeration required can be reduced up to 60%, without significantly affecting the propane plus recovery.     

Parametric analysis of Fischer‐tropsch synthesis in a catalytic microchannel reactor

Fischer‐Tropsch synthesis (FTS) involves highly exothermic conversion of syngas to a wide range of hydrocarbons, but demands isothermal conditions due to the strong dependence of product distribution on temperature. Running FTS in microchannel reactors is promising, as the sub‐millimeter dimensions can lead to significant intensification that inherently favors robust temperature control. This study involves computer‐based FTS simulations in a heat‐exchange integrated microchannel network composed of horizontal groups of square‐shaped cooling and wall‐coated, catalytic reaction channels. Effects of material type and thickness of the wall separating the channels, side length of the cooling channel, coolant flow rate, and channel wall texture on reaction temperature are investigated. Use of thicker walls with high thermal conductivities and micro‐baffles on the catalytic reaction channel wall favor near‐isothermal conditions. Response of reaction temperature against coolant flow rate is significant. Using cooling channels with smaller side lengths, however, is shown to be insufficient for temperature control. © 2011 American Institute of Chemical Engineers AIChE J, 2012     

CFD analysis of turbulence in a baffled stirred tank, a three-compartment model

Three-compartment model was used to study non-homogeneity of mixing in a fully baffled stirred tank. Multiple reference frame (MRF) technique was used for calculations. Calculations were performed to study the effects of agitator speed, impeller diameter, baffle width and distance of impeller from bottom of the tank on turbulent flow field. Three different zones of the vessel, that were a small zone near the impeller, another zone around the baffles, and a relatively large zone far from the impeller and baffles, named circulation zone, were investigated. Boundaries of these zones were determined using two different methods. The first method used gradient of energy dissipation rate while the other method used cumulative energy dissipation rate to determine the zone boundaries. Zone boundaries determined by both methods were comparable. The turbulent kinetic energy dissipation rate gradient was the preferred method due to its simplicity. Turbulent kinetic energy dissipation rate increased with agitator speed in all zones. Both turbulent kinetic energy dissipation rate and turbulent kinetic energy showed considerable change with impeller diameter at impeller zone, while no remarkable change was observed at baffle and circulation zones. Three-compartment model parameters, impeller and baffle energy dissipation ratios λ_i, λ_b, impeller and baffle volume ratios μ_i, μ_b and impeller and baffle exchange flow rates Q_i, Q_b were obtained from CFD simulations. Impeller energy dissipation ratio, impeller exchange flow rate and baffle exchange flow rate increased while baffle volume ratio decreased with agitation rate and impeller diameter. Baffle energy dissipation ratio and impeller volume ratio showed no considerable change with agitation rate and impeller diameter.     

Simulation of energy consumption in electrochemical grinding of hard-to-machine materials

The paper presents results of the simulation of the effect of some significant factors on energy consumption and specific energy consumption for electrochemical grinding and mechanical grinding of three hard-to-machine materials (sintered carbides B40, titanium alloy Ti6Al4V and steel 18G2A). The investigation has been carried out on models of energy consumption and specific energy consumption for electrochemical and mechanical grinding performed by the grinding wheel face. The results have shown that within the range of parameters and machining conditions employed, mechanical grinding of hard-to-machine materials is characterized by higher energy consumption than electrochemical grinding.     

Modeling and validation of a photocatalytic oxidation reactor for indoor environment applications

Modern building ventilation design must take into account the health, safety and comfort of the occupants, as well as energy consumption and the environment. The system needs to protect occupants against chemical contaminants from numerous internal sources—office equipment, furniture, building materials, appliances, as well as intentional release. A promising technology which has great potential in this respect is UV photocatalytic oxidation (UV-PCO). Designing a UV-PCO system for a building requires full understanding of its performance, which strongly depends on the UV intensity field, types and concentration levels of reactants, oxygen and moisture levels, temperature, reflectance of duct surfaces, system configuration, orientation, air stream characteristics like temperature, humidity, air velocity and mixing, just to mention a few.This paper reports the development of a mathematical model for predicting the performance of a honeycomb monolith PCO reactor used in building mechanical ventilation systems. The model is validated by comparing its prediction with experimental data and with the prediction made by an existing model. The influence of several kinetic parameters such as airflow rate, pollutant inlet concentration, light intensity, humidity and catalyst deactivation has been investigated. The developed model can be used as a practical tool to simulate and optimize a UV-PCO system for application in building mechanical ventilation system.