Modeling of a continuous photocatalytic reactor for isovaleraldehyde oxidation: Effect of different operating parameters and chemical degradation pathway

An investigation of isovaleraldehyde (ISOV) photocatalytic oxidation was conducted at initial concentrations ranging from 25 to 150 mg/m³ and different relative humidities (5–90% RH) in order to characterize the process performances close to indoor air conditions. Experiments were carried out in two different reactors: cylinder and flat-plate photoreactor (planar reactor) at different air gap (20–60 mm) and gas residence times (0.67–5.0 s). A plug flow reactor system was developed in order to perform kinetic studies of (i) isovaleraldehyde removal, (ii) selectivity of CO₂, (iii) by-products formation and removal. It appears that ISOV removal efficiencies increased with lower inlet concentrations, lower air gap and higher gas residence times.     

Synthesis of Mn3O4/N-doped graphene hybrid and its improved electrochemical performance for lithium-ion batteries

Mn₃O₄/N-doped graphene (Mn₃O₄/NG) hybrids were synthesized by a simple one-pot hydrothermal process. The scanning electron microscopy (SEM), transition electron microscopy (TEM), X-ray powder diffraction (XRD), Thermogravimetric analysis (TG), Raman Spectroscopy and X-ray photoelectron spectroscopy (XPS) were used to characterize the microstructure, crystallinity and compositions. It is demonstrated that Mn₃O₄ nanoparticles are high-dispersely anchored onto the individual graphene nanosheets, and also found that, in contrast with pure Mn₃O₄ obtained without graphene added, the introduction of graphene effectively restricts the growth of Mn₃O₄ nanoparticles. Simultaneously, the anchored well-dispersed Mn₃O₄ nanoparticles also play a role as spacers in preventing the restacking of graphene sheets and producing abundant nanoscale porous channels. Hence, it is well anticipated that the accessibility and reactivity of electrolyte molecules with Mn₃O₄/NG electrode are highly improved during the electrochemical process. As the anode material for lithium ion batteries, the Mn₃O₄/NG hybrid electrode displays an outstanding reversible capacity of 1208.4 mAh g⁻¹ after 150 cycles at a current density of 88 mA g⁻¹, even still retained 284 mAh g⁻¹ at a high current density of 4400 mA g⁻¹ after 10 cycles, indicating the superior capacity retention, which is better than those of bare Mn₃O₄, and most other Mn₃O₄/C hybrids in reported literatures. Finally, the superior performance can be ascribed to the uniformly distribution of ultrafine Mn₃O₄ nanoparticles, successful nitrogen doping of graphene and favorable structures of the composites.     

Application of electrochemical oxidation for treatment of industrial wastewater — the influence of reactor hydrodynamics on direct and mediated processes

The influence of kinetic and hydrodynamic factors in electrochemical reactors used in the removal of pollutants from industrial wastewater is shown, distinguishing between the two main types of reactions, namely direct and mediated electro‐oxidation. The effect of stirring during treatment of four different types of wastewater is reported. Whilst for direct electro‐oxidation of pollutants, the influence of agitation on the performance of the reactor can be easily predicted from a mass transfer correlation, its effect during electro‐oxidation mediated in the homogeneous phase by a redox couple is not straightforward. The Hatta number can be a useful criterion to apply to electrochemical reactors performing mediated oxidation of compounds (in analogy to gas–liquid reactions), so as to define whether the reaction occurs in the bulk of the reactor or near the electrode, and thus can be affected differently by stirring. The hydrodynamic conditions in the reactor for treatment of industrial wastewater can affect the differential selectivity of the removal of pollutants and this can be used for optimising the performance of the reactor with respect to a target pollutant. Copyright © 2006 Society of Chemical Industry     

Optimal design and operation of an industrial three phase reactor for the oxidation of phenol

Among several treatment methods catalytic wet air oxidation (CWAO) treatment is considered as a useful and powerful method for removing phenol from waste waters. In this work, mathematical model of a trickle bed reactor (TBR) undergoing CWAO of phenol is developed and the best kinetic parameters of the relevant reaction are estimated based on experimental data (from the literature) using parameter estimation technique. The validated model is then utilized for further simulation and optimization of the process. Finally, the TBR is scaled up to predict the behavior of CWAO of phenol in industrial reactors. The optimal operating conditions based on maximum conversion and minimum cost in addition to the optimal distribution of the catalyst bed is considered in scaling up and the optimal ratio of the reactor length to reactor diameter is calculated with taking into account the hydrodynamic factors (radial and axial concentration and temperature distribution).     

Effects of porosity on the electrochemical oxidation performance of Ti4O7 electrode materials

Ti₄O₇ is a kind of conductive ceramic material with a high electrical conductivity and excellent electrochemical performance, rendering it a potential candidate for electrode applications. Here, for the first time, we report the successful preparation of Ti₄O₇ electrodes with different porosities by adding a pore-forming agent. The results showed that the as-prepared Ti₄O₇ electrodes contained both mesoporous and macroporous structures. In addition, with an increase in the porosity of the electrodes, the electrochemical oxidation degradation of high-concentration methyl orange (MO) solution first increased, until reaching a critical point, and then decreased. The Ti₄O₇ electrode with a porosity of 34.9% and an electrical conductivity of 336.1 S cm^-1 exhibited the highest electrochemical oxidation ability. The electrochemical oxidation rate constants for MO and chemical oxygen demand (COD) of the porous Ti₄O₇ electrode were 1.7 times those of the dense Ti₄O₇ electrode. Compared to commercial stainless steel, graphite, and Ti/RuO₂ electrodes, the Ti₄O₇ porous electrode showed superior electrochemical oxidation performance under the same experimental conditions. The result of this study provide new directions for the application of Ti₄O₇ electrode materials.     

Catalytic membrane structure influence on the pressure effects in an interfacial contactor catalytic membrane reactor applied to wet air oxidation

This paper deals with the influence of catalytic membrane structure on the way the gas pressure affects the efficiency of a catalytic membrane reactor (CMR). The CMR is an interfacial contactor, used for wet air oxidation, formic acid solution and air being fed separately from both sides of the catalytic membrane. The gas overpressure can shift the gas–liquid interface into the membrane wall, closer to the catalytic zone, and therefore greatly increase the reaction rate. It has been confirmed that this was not an oxygen partial pressure effect. When compared to a conventional slurry reactor, the contactor CMR showed a reaction rate more than three times higher.     

Effect of synthesis temperature on the phase structure,morphology and electrochemical performance of Ti3C2 as an anode material for Li-ion batteries

Ti₃C₂, the most widely studied MXene, was successfully synthesised by etching Al layers from Ti₃AlC₂ in HF solution. Given its distinct 2D layered structure, Ti₃C₂ is a promising anode material in Li-ion batteries because of its efficient ion transport, available large surface areas for improved ion adsorption and fast surface redox reactions. Herein, the effects of synthesis temperature on the phase structure, morphology and electrochemical performance were investigated. The materials synthesised at different temperatures were characterised by using X-ray diffraction, scanning electron microscopy and transmission electron microscopy. Optimal etching occurred at 100?°C, and the synthesised Ti₃C₂ exhibited smooth surface and large layer space. The synthesised Ti₃C₂, as anode material for Li-ion batteries, can accommodate more Li⁺ than those of others, and it exhibits the most ideal electrochemical performance.     

The effects of residual chlorine on the behaviour of platinum group metals for oxidation of different hydrocarbons

The oxidation of a mixture of four hydrocarbons and carbon monoxide has been studied over alumina-supported palladium, platinum and rhodium catalysts made using chloride precursor salts. The order of the light-off temperatures for the hydrocarbons is the same for each metal (1-hexene, toluene, benzene and finally iso-octane) but the separation between each and their occurrence relative to carbon monoxide varies. The absolute values, especially for iso-octane, are strongly dependent on the pretreatment procedure. Exposure to H₂/H₂O in the place of O₂ gives much higher activity. Activation can also be achieved by repeated runs with the reactant mixture. Chlorobenzene is produced in small amounts during experiments using partially activated catalysts especially with rhodium. Other reasons for believing that the development of activity is at least partly associated with the removal of chlorine are discussed.     

Effect of different adhesive protocols on bond strength between composite resins for indirect use and repair materials

Abstract

The aim of this work is to evaluate the effect of different adhesive protocols on the bond strength (SBS) of composite resin for indirect use to repairs of bulk-fill or conventional nanoparticulated composites. Forty-eight cylindrical specimens of composite resin for indirect use were prepared, aged, and randomly divided into four groups (n?=?12), a control group without any adhesion protocol, and three experimental groups: Silane?+?Scotch Bond Multipurpose adhesive (S?+?SBMP), Tetric N Bond Universal (TBU), and Single Bond Universal (SBU). The treated surfaces were restored using two different composite resins: Filtek Bulk-Fill or Filtek Z350XT. Then, the specimens were submitted to the SBS test, and the resultant data were analyzed with ANOVA on ranks test and Tukey’s test (α?=?0.05). There were no significant differences between the two types of resins used as repair material. For both resins, the groups treated with S?+?SBMP obtained the highest values (p?<?0.001). Groups TBU and SBU did not have statistically significant differences between them. Pre-treatment with a silane coupling agent and a layer of a hydrophobic adhesive can improve the bond strength of repairs performed on a composite resin for indirect use.     

有机废水电化学氧化阳极材料的研究进展

阳极材料是电化学氧化法处理有机废水的关键.综述了贵金属电极、碳素电极、钛基金属氧化物电极和合成掺硼金刚石(BDD)薄层电极在内的常用阳极材料的性能,并对有机废水电化学氧化阳极材料的发展趋向进行了展望.     

Electrochemical oxidation of organic pollutants in water at metal oxide electrodes: A simple theoretical model including direct and indirect oxidation processes at the anodic surface

The electrochemical oxidation of organics in water at metal oxide electrodes was investigated with the aim to discuss the correlations between the instantaneous current efficiency ICE and operative conditions by considering both the hypothesis of a direct oxidation process and of an indirect process mediated by adsorbed hydroxyl radicals or chemisorbed “oxygen”, in order to explicit the main differences expected between these cases. Thus, a simple theoretical model was discussed, as an extension of previous studies of Comnnellis and co-workers which were focused on indirect oxidation paths [C. Comninellis, Electrochim. Acta 39 (1994) 1857; O. Simond, V. Schaller, Ch. Comninellis, Electrochim. Acta, 42 (1997) 2009], concerning both the cases of mass transfer control and oxidation reaction control and mixed kinetic regimes. A very good agreement, between theoretical predictions and experimental data pertaining to the electrochemical oxidation of oxalic and formic acid at IrO₂–Ta₂O₅, was observed.     

A structured test reactor for the evaporation of methanol on the basis of a catalytic combustion

The kinetics of the catalytic deep oxidation of methanol was studied in stacked segments of a turbulence insert (SSTIs) coated with Pt/γ-Al₂O₃ and Pt/zeolite catalysts. These geometries, which are termed a structured test reactor in the heading, are intended to replace plane expanded metal discs (PEMDs) used in the so-called catalytic burner at Research Centre Jülich, up to the present. The catalytic burner performs the low-pollution combustion inter alia of the anode exhaust gases of the fuel cell. SSTIs coated with Pt/γ-Al₂O₃ showed different kinetics for differential conversions as a function of temperature. At low reaction temperatures (100–130°C) ignition kinetics with a very high activation energy of 60.3 kJ/mol was found. In the further course of the reaction, the kinetically controlled reaction with an activation energy of 48.5 kJ/mol was observed. In the range of non-differential conversions, the activation energy decreased significantly, which suggests a limitation of the reaction process by mass transport phenomena. Compared to the PEMDs, clearly higher reaction rates were observed, which enable a reduction of the catalyst mass. This as well as the spatial structure of the SSTIs make it possible to achieve a reduction in volume and weight and thus improved dynamics in constructing a novel catalytic burner. The SSTIs coated with Pt/zeolite showed perceptibly lower reaction rates than the Pt/γ-Al₂O₃ substrates and could thus not compete with the PEMDs.     

Study on the uniformity of water film in a transpiring wall reactor for supercritical water oxidation

A three-dimensional computational fluid dynamic model of a transpiring wall reactor for supercritical water oxidation has been built to optimize the uniformity of water film. Results show that the temperature and species distributions at the nozzle outlet deviate from the reactor centre. The inner wall of the porous tube near the transpiring water injection tube displays low temperatures, while high temperatures are recorded far from the injection tube. The circumferential temperature distribution on the inner wall of the porous tube is uneven. This phenomenon is due to the uneven injection of the transpiring water, leading to the uneven protection of the water film and local overheating of the porous wall. The injection velocity of the transpiring water significantly decreases when the number of injection tubes is increased, and the circumferential velocity and temperature distributions on the porous wall gradually become even. Moreover, high pressure drops across the porous wall at low porosities are useful for the uniform injection of the transpiring water. This characteristic is also conducive to obtaining a more uniform water film protection.     

The pyrolysis of natural gas: A study of carbon deposition and the suitability of reactor materials

This study of methane pyrolysis was designed to look at carbon deposition on the internal reactor and wafer surface during CH₄ pyrolysis. The rate of carbon deposition on the internal reactor surfaces could be reduced with: lower methane/oxygen ratios, shorter residence times, and lower temperatures. The type of carbon formed appeared to have a significant effect on the pyrolysis process. Pyrolytic carbon with a lower order structure produces a higher selectivity for carbon formation compared to carbon with a higher order structure. Form a process perspective, there are two obvious means of addressing this: deposited carbon could be regularly removed; and/or pyrolysis conditions are selected that produce carbon with a higher order structure. From the results, it is very clear that any development of a commercial process for natural gas pyrolysis in ceramic reactor systems would have to carefully address the selection of reactor material. © 2018 American Institute of Chemical Engineers AIChE J, 65: 1035–1046, 2019     

Simulation and thermodynamic analysis of an integrated process with H2 membrane CPO reactor for pure H2 production

A one-dimensional steady-state heterogeneous model has been used to simulate the H₂ membrane reactor. The simulation work is the basis for the thermodynamic analysis of the integrated pure H₂ production process. The simulation and analysis also provide a quantitative tool for insight into and understanding the process.The simulation and thermodynamic analysis results indicate that increasing the inlet ratio H₂O/CH₄ cannot enhance the pure H₂ production rate. With increasing the inlet ratio H₂O/CH₄, the overall exergy efficiency of the process decreases, because a large amount of energy is required to obtain the steam.When the geometric parameters of membrane reactor and inlet temperature are given, there is a maximum feeding rate of methane for the integrated process. The pure hydrogen production rate increases with the inlet methane rate increasing, while the overall exergy efficiency decreases as inlet methane rate increases.For the same inlet rate of methane, operating the process at higher inlet temperature increases hydrogen production rate. Whereas, the overall exergy efficiency is lowered.Three suggestions are discussed to improve the overall exergy efficiency. All of them require more equipment investment. There will be an optimal point to balance equipment investment, pure hydrogen production rate and overall exergy efficiency. To find the optimum, thermo-economic analysis will be helpful.     

Simulations of the effect of hydrodynamic conditions and properties of membranes on the catalytic performance of a fluidized-bed membrane reactor for partial oxidation of methane

In a fluidized-bed membrane reactor the selectivity of separation can be controlled by influencing the hydrodynamics of the fluidized bed. In this reactor type, with the mass transport limitation between bubbles and the emulsion phase, even with the non-selective membranes, high selectivity of separation can be achieved. This opens the possibility for applications of membrane reactors for reaction systems for which selective membranes do not exist, e.g. when Knudsen-type membranes or form-selective separation can not be applied. This paper is aimed at explaining the interaction between the selectivity of separation and the hydrodynamics of the fluidized bed by means of simulations that were performed for a fluidized-bed membrane reactor for catalytic partial oxidation of methane.     

Scale influence on the hydrodynamics of an internal loop airlift reactor

The overall circulation velocity, the overall riser and downcomer gas hold-ups and the effect of reactor scale on a two-phase circulation regimes were studied in this work in three airlift reactors of different scale. The measurements were carried out in airlift reactor with internal loops (IALRs) with a working volume of 10.5, 32 and 200 l at the range of temperatures 18–21 °C, under atmospheric pressure. Air and water were used as gas and liquid media. The three reactors were of similar geometry, the ratio between riser and downcomer cross-sectional areas, the aspect ratio of the column and the shape of the column bottom were taken as similarity criteria. In order to determine the linear circulation velocities, the magnetic tracer method was used. The riser and the downcomer were studied separately. Based on gas hold-up in both the riser and the downcomer, two regimes (homogeneous bubble (HMG) and heterogeneous churn-turbulent (HTG)) of the two-phase flow were observed. These were defined by Daniels [Chem. Eng. 70 (1995)] and described using the correlation proposed by Chisti [Airlift Bioreactors, Elsevier, London, 1989]. The average of the liquid circulation velocities increased with increasing reactor scale for the same superficial gas velocity. The overall circulation velocity was modelled on the basis of the momentum balance proposed in paper [Chem. Eng. Sci. 52 (1997) 25]. The parameters of both the correlation and the model tend to be constant for larger reactor scales. The value of the driving force (_R−_D) was found to be important only for lower values of gas flow rate, because at higher values, the circulation velocity seemed to be governed only by friction in the reactor vessel.     

Comparison of the performance of a direct-contact bubble reactor and an indirectly heated tubular reactor for solar-aided methane dry reforming employing molten salt

A theoretical approach is presented for the comparison of two different atmospheric pressure reactors—a direct-contact bubble reactor (DCBR) and an indirectly heated tubular reactor (IHTR)—to evaluate the reactor performance in terms of heat transfer and available catalytic active surface area. The model considers the catalytic endothermic reactions of methane dry reforming that proceeds in both reactors by employing molten salts at elevated temperatures (700–900 °C) in the absence of catalyst deactivation effects. The methane conversion process is simulated for a single reactor using both a reaction kinetics model and a heat transfer model. A well-tested reaction kinetics model, which showed an acceptable agreement with the empirical observations, was implemented to describe the methane dry reforming. In DCBR, the heat is internally transferred by direct contact with the three phases of the system: the reactant gas bubbles, the heat carrier molten salts and the solid catalyst (Ni-Al₂O₃). In contrast, the supplied heat in the conventional shell-and-tube heat exchanger of the IHTR is transferred across an intervening wall. The results suggest a combination system of DCBR and IHTR would be a suitable configuration for process intensification associated with higher thermal efficiency and cost reduction.     

厌氧氨氧化反应器的启动及其脱氮性能研究

采用添加多层多孔板的升流式厌氧污泥床接种混合污泥,于78 d内成功启动厌氧氨氧化反应器。第75天,反应器对NH4+-N和NO2--N的去除率达95%以上,容积氮去除负荷达0.525 kg/(m3·d)。启动后,快速提高进水基质浓度,反应器出现抑制现象,且抑制前后三氮之比具有显著变化。运行后期,底部出现红棕色污泥。与普通的升流式厌氧污泥床相比,其具有喷动床效应及水利筛分作用,有利于颗粒污泥的形成。