Photo‐Fenton Remediation of Wastewaters Containing Silicones: Experimental Study and Neural Network Modeling

The present work is aimed at the investigation of the photo‐Fenton technology with regard to the remediation of diluted aqueous emulsions containing an aminosilicone polymer, in a bench‐scale photochemical reactor. The experimental results show a strong interaction between temperature, light, Fe(II) and H₂O₂ concentrations on the degradation process, which generates substances that might be readily biodegradable and/or a solid phase that is easily separated by simple mechanical operations. The neural network technique is an effective, simple approach to successfully modeling the photo‐Fenton degradation system, in which thermal and photochemical reactions and related phenomena (such as solid precipitation) take place. The model might therefore be useful in process optimization, as well as in the design and scaleup of photochemical reactors for industrial application.     

Prediction via Neural Networks of the Residual Hydrogen Peroxide used in Photo‐Fenton Processes for Effluent Treatment

This communication proposes the use of neural networks in the prediction of residual concentrations of hydrogen peroxide from the treatment of effluents through Advanced Oxidative Processes (AOP's), in particular, the photo‐Fenton process. To verify the efficiency of the oxidative process, the Chemical Oxygen Demand (COD) parameter, the values of which may be modified by the presence of oxidizing agents such as residual hydrogen peroxide, is frequently taken in account. The analysis of the H₂O₂ interference was performed by spectrophotometry at 450 nm wavelength, via the monitoring of the reaction of ammonia with metavanadate. The results of the hydrogen peroxide residual concentration were modeled via a feedforward neural network, with the correlation coefficients between actual and predicted values above 0.96, indicating good prediction capacity.     

Modeling of Kinetic Expressions for the Reduction of NOx by Hydrogen in Oxygen‐Rich Exhausts Using a Gradient‐Free Loop Reactor

The reduction of NO_x by hydrogen under lean conditions is investigated in a gradient‐free loop reactor. Using this computer‐controlled reactor, the reaction rates can be measured under exact isothermal conditions. Systematic variation of the input concentrations of hydrogen, nitric oxide, oxygen as well as reaction temperature provides a complete data set of reaction rates for the given reaction system. A number of kinetic rate expressions were evaluated for their ability to fit the experimental data by using toolboxes of MATLAB. The temperature influence on reaction rate constants and adsorption equilibrium constants were correlated simultaneously using Arrhenius and van’t Hoff equations, respectively. The kinetic rate expression based on a Langmuir‐Hinshelwood‐type model describes the data and the model can be improved by introducing a correction term in square root of hydrogen partial pressure over the range of conditions investigated.     

Advanced Oxidative Removal of Nitric Oxide from Flue Gas by Homogeneous Photo‐Fenton in a Photochemical Reactor

In this work, advanced oxidation removal of nitric oxide (NO) from flue gas by homogeneous Photo‐Fenton was investigated in a photochemical reactor and the effects of several influencing factors on NO removal were evaluated. The gas‐liquid reaction products were determined. The reaction pathways of NO removal are also preliminarily discussed. It was found that with the increase of Fe²⁺ concentration, NO removal efficiency first increased and then decreased. Increasing H₂O₂ concentration and UV radiation intensity greatly increased NO removal efficiency, but the growth rates gradually became smaller. NO removal efficiency greatly reduced with the increase of gas flow and NO concentration, and only slightly decreased with the increase of solution temperature, but significantly increased with the increase of initial solution pH value. The main anion product in the liquid phase was NO₃^–. With respect to removal of NO using homogeneous Photo‐Fenton, ·OH oxidation was the main reaction pathway, and H₂O₂ oxidation was the secondary reaction pathway.     

Rapid Pyrolysis of Wheat Straw in a Bench‐Scale Circulating Fluidized‐Bed Downer Reactor

The effects of acid washing treatment on the pyrolysis product distribution and product properties were investigated in a bench‐scale circulating fluidized‐bed (CFB) downer reactor with wheat straw as feedstock. The acid treatment not only removes most of the inorganic species present in the biomass but also alters the distribution of the remaining organic constituents. It was found that the removal of the inorganic species increases the yield of liquid product and reduces char formation and gas yield. CO and CO₂ are the dominant components in the gaseous product, accounting for over 90 %. The concentration of CO in the gaseous product increases after acid treatment, while the CO₂ concentration decreases. The oxygen and water contents in the liquid product are decreased on acid treatment, leading to a relatively high heating value and viscosity. More volatiles can be found in the char derived from the acid‐treated wheat straw than from the raw wheat straw. This may suggest that a longer residence time is needed for pyrolysis of the acid‐treated wheat straw in order to obtain the maximal yield of volatile matter.     

Performance and Economic Assessment of the Treatment of Phenol with TiO2 Photocatalysis,Photo‐Fenton,Biological Aerated Filter,and Wetland Reactors

The performance and economic cost of the removal of phenol with TiO₂ photocatalysis, photo‐Fenton reactions, biological aerated filter (BAF), and constructed wetland (CW) reactors has been studied. The BAF achieved complete removal with a maximum phenol concentration of 200 mg·L^?1. The BAF‐CW combination provided a phenol‐free effluent with a maximum phenol concentration of 650 mg·L^?1. In both cases, a complete detoxification of the treated water was achieved at the concentrations studied. The efficiency of TiO₂ photocatalysis was limited to concentrations below 50 mg L^?1 to minimize removal reduction and toxicity of the intermediates. Photo‐Fenton was more efficient, but also more expensive because of the high cost of H₂O₂. The photo‐Fenton‐BAF combination is proposed to be the most suitable one.     

Study of the Characteristics of Methanol Synthesis in a Recirculation Slurry Reactor – A Novel Three‐Phase Synthesis Reactor

A process feasibility analysis on the liquid phase methanol synthesis (LPMeOH^TM) process was performed in a recirculation slurry reactor (RSR). In the three‐phase RSR system, a fine catalyst is slurried in the paraffin and this catalyst slurry is continuously recirculated through the nozzle from the slurry sector to the entrained sector by a pump. The syngas is fed concurrently with the downward flow of slurry to form the methanol product. A laboratory scale mini‐pilot plant version of a recirculation slurry reactor system was successfully designed and built to carry out process engineering research, and in addition, an identical cold model was built to measure the mass transfer coefficient in the recirculation slurry reactor. The effects of operating conditions, including temperature, pressure, gas flow rate and catalyst slurry recirculation flow rate on the productivity of methanol were studied. This experimental data helps the scale‐up and commercialization of the methanol synthesis process in recirculation slurry reactors.     

Heat Transfer Characteristics of CO2 Desorption from N‐Methyldiethanolamine Solution in a Microchannel Reactor

The heat transfer performance and energy consumption of CO₂ desorption from rich N‐methyldiethanolamine (MDEA) solution were determined experimentally in a straight microchannel reactor. Nucleate boiling was found to be the dominant heat transfer mechanism in this experiment. The heat transfer coefficients were strongly dependent on the heat flux. The solution flow rate was the most influential factor on the heat flux, followed by desorption temperature, MDEA concentration, and CO₂ loading. In addition, an empirical correlation was proposed to predict the experimental heat transfer coefficients.     

Membrane‐Aerated Biofilm Reactor Behaviors for the Treatment of High‐Strength Ammonium Industrial Wastewater

A single‐tube membrane‐aerated biofilm reactor (MABR) was used to investigate the effect of the reaction time, reaction temperature, pH value, C/N ratio, and sludge concentration on the removal rates of the NO_x^–‐N and COD in high‐strength ammonium industrial water by supplying oxygen during the batch experiment. The homogeneous mathematical model is developed to predict their transient responses using Monod kinetics with dual substrate limitation. The model incorporates mass transport by convection and diffusion in the surrounding liquid contained inside the interconnected pores and channels within the biofilm. Transport and kinetic parameters are estimated from experiments and the model successfully predicts concentration measurements in some of the sets of experiments.     

Modeling the kinetics of a photochemical water treatment process by means of artificial neural networks

We have investigated the kinetics of the degradation of 2,4-dimethyl aniline (2,4-xylidine), chosen as a model pollutant, by the photochemically enhanced Fenton reaction. This process, which may be efficiently applied to the treatment of industrial waste waters, involves a series of complex reactions leading eventually to the mineralization of the organic pollutant. A model based on artificial neural networks has been developed for fitting the experimental data obtained in a laboratory batch reactor. The model can describe the evolution of the pollutant concentration during irradiation time under various conditions. It has been used for simulating the behavior of the reaction system in sensitivity studies aimed at optimizing the amounts of reactants employed in the process — an iron(II) salt and hydrogen peroxide. The results show that the process is much more sensitive to the iron(II) salt concentration than to the hydrogen peroxide concentration, a favorable condition in terms of economic feasibility.     

The Fabrication of Nano-Particles in Aqueous Solution From Oxyfluoride Glass Ceramics by Thermal Induction and Corrosion Treatment

An innovative route is reported to fabricate nano-particles in aqueous solution from oxyfluoride glass by the thermal induction and corrosion treatment in this letter. The investigations of X-ray diffraction and transmission electron microscope based on nano-particles in glass ceramics (GCs) and aqueous solution indicate that the nano-particles formed in glass matrix during the thermal induction process are released to aqueous solution and their structure, shape and luminescent properties in glass host can be kept. Owing to the designable composition of the nano-particles during glass preparation process, the method is a novel way to obtain nano-particles in aqueous solution from GCs.     

Model‐Aided Design of a Three‐Phase Gas‐Lift Reactor for Oxidation Accompanied by Catalyst Reversible Deactivation

A mathematical model of a three‐phase gas‐lift reactor (GLR) is developed to aid the design of a target reactor for simultaneous substrate catalytic oxidation in riser and a deactivated reactivation catalyst in the downcomer section of the multifunctional reactor. In the GLR model, the hydrodynamics of a real GLR and the kinetics of glucose oxidation by air over a palladium catalyst are incorporated. The GLR model searches for the optimal geometry of the target reactor. With regard to the GLR optimal geometry, the reactor productivity is maximal for given input operational conditions. An algorithm of the GLR model is presented together with simulation results of the target GLR and with insight into the parametric sensitivity of the model. Effects of the reaction components concentrations and the gas‐phase superficial velocity on the location of the target reactor optimal geometry and on the reactor productivity are discussed.     

Input Multiplicity Analysis in a Non‐Isothermal CSTR for Acid‐Catalyzed Hydrolysis of Acetic Anhydride

Multiplicity analysis gives practical guidance for process design to eliminate difficult operating regions associated with input and output multiplicities. Continuous stirred tank reactors (CSTRs) present challenging operational problems due to complex behavior such as input and output multiplicities, ignition/extinction, parametric sensitivity, and nonlinear oscillations. In the absence of a unified mathematical theory for representing various nonlinear system characteristics, the present study was aimed at understanding the dynamic behavior of CSTRs by means of experiments and to link the experimental data to theoretical considerations for further detection and elimination of operating problems. Theoretical modeling and analysis of a non‐isothermal CSTR with acid‐catalyzed hydrolysis of an acetic anhydride system for input multiplicity are discussed. Theoretical modeling of a non‐isothermal CSTR using a root‐finding technique was carried out for predicting steady‐state temperatures. Alternatively, a mathematical model for a non‐isothermal CSTR using unsteady‐state mass and energy balance equations is proposed. Computer‐based simulation was carried out using a program developed in MATLAB for final transient temperature and time‐temperature data of the CSTR system under investigation. The results of a theoretical analysis conducted for confirming the existence of input multiplicity in non‐isothermal CSTRs with acid‐catalyzed hydrolysis of acetic anhydride were compared with experimental investigations for validation.     

CFD Modeling of a Carbonation Reactor with a K‐Based Dry Sorbent for CO2 Capture

A 2D CFD simulation of the carbonation reactor is carried out to evaluate the performance of potassium‐based dry sorbent during the CO₂ capture process. A multiscale drag coefficient model is incorporated into the two‐fluid model to take the effects of clusters into account. The influence of several parameters on CO₂ removal is investigated. The results indicate that increasing the reactor height and reducing the gas velocity can lengthen the residence time of particles and enhance the CO₂ removal. The operating pressure has a significant influence on the performance of solid sorbents. A higher pressure will decrease the CO₂ removal efficiency.     

Two‐Dimensional Model for Oxidative Coupling of Methane in a Packed‐Bed Membrane Reactor

A two‐dimensional (2D) model of a packed‐bed membrane reactor was developed to describe ethylene production by oxidative coupling of methane (OCM). The model covers all relevant energy and mass transport processes in the reactor and allows a more precise prediction of the temperature and conversion patterns. It is demonstrated that the fast OCM reaction leads to oxygen depletion in the vicinity of the membrane, causing strong radial concentration gradients in the bed. Further results indicate that the detailed 2D model can provide more accurate predictions of experimental data than the simplified one.     

内循环生物流化床处理N、P废水的试验研究

采用内循环生物流化床系统,通过控制曝气时间和溶解氧浓度,能同时脱氮除磷.含氮、磷进水COD为352～1 048 mg/L,总氮(TN)为46.9～76.4 mg/L, 总磷(TP)在5.8～14.4 mg/L时,COD 、总氮(TN)、总磷(TP)去除率分别为92%、80%、93%,出水可达到国家二级排放标准.     

Study of Hydrodynamics,Mixing and Gas‐Liquid Mass Transfer in a Split‐Rectangular Airlift Reactor

Global hydrodynamic characteristics, liquid mixing and gas‐liquid mass transfer for a 63 L split‐rectangular airlift reactor were studied. Correlations for gas holdup and overall liquid circulation velocity were derived for the air‐water system as a function of the specific power input; these were compared to data and correlations for reactor volumes between 4.7 L and 4600 L. A partial recirculation of small bubbles in the riser was observed when U_gr > 0.03 m/s, which was attributed to the use of a single‐orifice nozzle as the gas phase distributor. The dimensionless mixing time and the overall axial dispersion coefficient were nearly constant for the range of gas flow rates studied. However, values of K_L/d_B were greater than those reported in previous studies and this is caused by the partial recirculation of the gas phase in the riser. While scale effects remain slight, the use of a gas distributor favouring this partial recirculation seems adequate for mass transfer in split‐rectangular airlift reactors.     

超高交联树脂对水溶液中山梨酸的吸附研究

研究了NDA-150超高交联吸附树脂对水溶液中山梨酸的静态吸附行为,探讨了pH值、温度、盐度以及乙醇的含量等因素对山梨酸在NDA-150树脂上吸附的影响。实验结果表明,该树脂对山梨酸的吸附能力明显优于CHA-111和XAD-4树脂,树脂的表面极性和微孔结构在吸附过程中起决定作用。吸附的最佳pH值为3,降低温度有利于吸附,NaCl的存在有利于吸附,乙醇的质量分数大于1%时,吸附量会显著降低。