人工肝生物反应器中溶解氧浓度动态分布的模型与数值分析

研究了人工肝生物反应器的结构特点,并在对反应器内部液体流动与气液传质规律进行分析的基础上,结合反应器的实际需要,建立了基于一维轴向扩散模型的人工肝专用生物反应器溶解氧浓度动态分布的数学机理模型. 利用有限差分方法对模型离散化求解,得到了流动速度、氧传质系数及细胞耗氧速率对反应器内部溶解氧浓度分布的影响规律. 通过对模型数值解的分析得到了特定条件下反应器内的优化参数为液体流速0.55 mm/s,传质系数0.31 s-1,扩散系数0.02 mm2/s. 最后,通过仿真数据与实测实验的对比验证了该模型的正确性,其平均误差在±5%以内. 本模型的建立在理论上验证了该专用生物反应器可以提供稳定且均匀的溶解氧浓度分布,同时也为下一代新型反应器的优化设计提供了参考数据和理论依据.     

A New Mechanism of the Selective Photodegradation of Antibiotics in the Catalytic System Containing TiO2 and the Inorganic Cations

The mechanism of sulfisoxazole (SFF) selective removal by photocatalysis in the presence of titanium (IV) oxide (TiO₂) and iron (III) chloride (FeCl₃) was explained and the kinetics and degradation pathways of SFF and other antibiotics were compared. The effects of selected inorganic ions, oxygen conditions, pH, sorption processes and formation of coordination compounds on the photocatalytic process in the presence of TiO₂ were also determined. The Fe³⁺ compounds added to the irradiated sulfonamide (SN) solution underwent surface sorption on TiO₂ particles and act as acceptors of excited electrons. Most likely, the SFF degradation is also intensified by organic radicals or cation organic radicals. These radicals can be initially generated by reaction with electron holes, hydroxyl radicals and as a result of electron transfer mediated by iron ions and then participate in propagation processes. The high sensitivity of SFF to decomposition caused by organic radicals is associated with the steric effect and the high bond polarity of the amide substituent.     

Photocatalytic degradation of model organic pollutants on an immobilized particulate TiO2 layer: Roles of adsorption processes and mechanistic complexity

The kinetics of photocatalytic degradation of four different model organic compounds, formic acid (FA), oxalic acid (OA), 4-chlorophenol (4-CP) and the herbicide monuron (3-(4-chlorophenyl)-1,1-dimethylurea) in a self-constructed batch-mode plate photoreactor with a thin flow of contaminated aqueous solution circulating over an illuminated particulate layer of TiO₂ P25 (Degussa) was compared. Both OA and FA were adsorbed on TiO₂ surface; their mineralization, induced by direct transfer of photogenerated holes, proceeded in a single step, without observable intermediates, following approximately zero order kinetics. Numerical simulations were performed using a newly proposed kinetic model based on the photostationary state assumption. The model allowed an explanation of the observed reaction order as well as the comparison of independent with competitive adsorption of organic compound and oxygen on the photocatalyst surface, yielding a better fit for the case of competition. 4-CP and monuron, which were not adsorbed under the conditions used, were degraded through the action of photogenerated hydroxyl radicals. Their degradation proceeded with lower photoefficiency than for the adsorbed compounds (FA and OA). While the mineralization of both 4-CP and monuron followed zero order kinetics, their degradation was close to first order. The different reaction orders were consistently explained using the photostationary state approach.     

Photocatalytic degradation of oxalic acid on a semiconductive layer of n-TiO2 particles in a batch plate reactor. Part III: Rate determining steps and nonsteady diffusion model for oxygen transport

The effect of oxygen concentration on the photocatalytic degradation rate of oxalic acid on a fixed layer of TiO₂ particles in a batch mode plate photoreactor was investigated at various light intensities. The regions where the photocatalytical decomposition rate is controlled by the flux of oxygen, photons, or both, were identified. For low oxygen concentration (0–0.15 mol m^–3) and photon flux intensity in the range from 10 to 24 × 10^–5 einstein m^–2 s^–1 the experimentally determined photocatalytical decomposition rate was in agreement with that theoretically calculated assuming the process to be controlled by the limiting flux of oxygen to the TiO₂ surface. At higher concentrations of oxygen (0.15–0.94 mol m^–3) the rate of photocatalysis was controlled simultaneously by both the flux of oxygen and photons. The influence of the oxygen concentration decreased with decreasing photon flux. For low photon flux intensities (3.5 × 10^–5 einstein m^–2 s^–1), the reaction rate was controlled by the photon flux. The concentration profile of oxygen in the diffusion layer along the reactor plate was calculated and showed a significant decrease in oxygen concentration on the TiO₂ surface.     

Effect of oxidisable substrates on the photoelectrocatalytic properties of thermally grown and particulate TiO<Subscript>2</Subscript> layers

The photoelectrochemical properties of titanium dioxide layers, prepared by thermal oxidation of titanium at 500–750 °C, were compared with those of layers of particulate (Degussa) P25, especially for oxidation of oxalic acid. The thermally formed oxide layers had rutile structures with a particle size of about 100 nm. Values of incident photon-to-current conversion efficiencies increased with rutile layer thickness and reached a maximum at about 1 μm. Photocurrents for particulate TiO₂ layers were about one order lower than those for thermal layers, due to the poor contact among individual particles, resulting in high electric resistance of the whole layer. The presence of oxalic acid had no effect on the photocurrent of thermal TiO₂ layers, while in the case of porous particulate layers, the photocurrent increased strongly, due to oxalate adsorption and subsequent enhanced oxidation rate with photogenerated holes. For oxalic acid concentrations ≤10⁻³ M, the photocurrent decayed due to mass transfer limitations, resulting in oxalate depletion in the porous particulate layer.     

IMPORTANCE OF DISPERSED SOLIDS IN BUBBLES FOR EXOTHERMIC REACTIONS IN FLUIDIZED BEDS

Ignition of activated carbon particles were measured in a vertical tube reactor of 4 cm ID, where single particles fell consecutively through a gas mixture containing oxygen.

A two dimensional fluidized bed reactor 24 cm wide, 51 cm high and 2.5 cm in thickness was used for visual observation through a wide front window 24 cm × 35 cm covered with a silica glass plate 1 cm thick. Activated carbon particles were fluidized incipientiy by air, and a gas mixture containing oxygen was injected upwards into the bed through a nozzle positioned 5 cm above the distributor, forming single bubbles intermittently.

It was observed that carbon particles dispersed in rising bubbles were ignited abruptly at emulsion phase temperatures above 550°C. Experimental findings from the fluidized bed were compared with those from the tube reactor, suggesting that the igniting conditions for particles dispersed in bubbles are nearly the same as for single particles falling in the tube reactor.     

IMPORTANCE OF DISPERSED SOLIDS IN BUBBLES FOR EXOTHERMIC REACTIONS IN FLUIDIZED BEDS

Ignition of activated carbon particles were measured in a vertical tube reactor of 4 cm ID, where single particles fell consecutively through a gas mixture containing oxygen.

A two dimensional fluidized bed reactor 24 cm wide, 51 cm high and 2.5 cm in thickness was used for visual observation through a wide front window 24 cm × 35 cm covered with a silica glass plate 1 cm thick. Activated carbon particles were fluidized incipientiy by air, and a gas mixture containing oxygen was injected upwards into the bed through a nozzle positioned 5 cm above the distributor, forming single bubbles intermittently.

It was observed that carbon particles dispersed in rising bubbles were ignited abruptly at emulsion phase temperatures above 550°C. Experimental findings from the fluidized bed were compared with those from the tube reactor, suggesting that the igniting conditions for particles dispersed in bubbles are nearly the same as for single particles falling in the tube reactor.     

Kinetics of the electrochemical oxidation of organic compounds at BDD anodes: modelling of surface reactions

This paper presents the results of a numerical study of the kinetics of electrochemical oxidation of different organic substances at boron doped diamond (BDD). It is well established that oxidation of organics at BDD anodes takes place in the potential region of oxygen evolution, through reaction steps in which OH radicals are involved: these radicals can react with organic compounds to give more oxidised substances, or with water to give oxygen. Because of the high reactivity of OH radicals these reactions are confined to a thin film adjacent to the electrode surface. A mathematical model was implemented, which accounts for chemical and electrochemical reactions, as well as for the transport phenomena involved in the process: the parameters of the model were derived from experimental data. The model allowed calculation of the trend with time of reactant concentration, reaction intermediates and oxidisable agents: their space profiles in the reactor were also obtained. The numerical predictions of the model were compared with experimental results obtained from galvanostatic electrolyses of different organic compounds: (a) 2,4,6-trihydroxy-1,3,5 triazine also known as cyanuric acid (CA), which is well known to be refractory to oxidation with OH; (b) atrazine (ATR) the most oxidisable precursor of CA, and (c) phenol which is considered as an OH scavenger because of its high reactivity. The agreement between experimental and model predicted data was good in all the examined conditions.     

FORMATION OF MAGNETITE FINE PARTICLES BY CHEMICAL ABSORPTION INTO AQUEOUS SUSPENSIONS OF FERROUS HYDROXIDE

The formation of magnetite particles by oxidation of aqueous suspensions of Fe(OH)₂ with dissolved oxygen has been found to be composed of (I) the formation step of ferric hydroxo-complex by oxidation of FeOH' ion in the liquid film around the gas bubble, and (ii) the formation step of magnetite by the coprecipitation of FeOH⁺ and ferric hydroxo-complex in the thin layer adjacent to the Fe(OH)₂ particle in the bulk of suspension medium. The oxidation reaction rate can be expressed apparently by zero-order with respect to the content of total Fe(II) and by first-order with respect to the concentration of dissolved oxygen up to the fractional oxidation of 0.9.Only octahedral particles whose size ranges from O.14μm to 0.20 μmare formed so long as the oxidation reaction finishes within 50 min. When the reaction completion time becomes longer than about 90 min, almost particles are of cubic shape with a mean size of about 0.20 fim.     

Electrochemically assisted photocatalytic degradation of oxalic acid on particulate TiO2 film in a batch mode plate photoreactor

Electrochemically assisted photocatalytic degradation of oxalic acid was studied in a batch mode plate photoreactor composed of particulate TiO₂ film immobilized on Ti metal plate (Ti/TiO₂ electrode) and Pt wires immersed in a flowing film of aqueous solution (Pt counter electrode). The degradation rate of oxalic acid was followed as a function of the potential of the Ti/TiO₂ electrode, the oxygen concentration and the light intensity. The presence of oxalic acid caused an increase in the measured photocurrent by one order of magnitude which is due to its reaction with photogenerated holes. The degradation rate increased with increasing potential up to 0.5 V vs SCE, then the increase was more gradual. Electrochemically assisted photocatalytic degradation of oxalic acid also proceeded in the absence of oxygen. The photogenerated electrons caused hydrogen evolution (low oxygen concentration) or predominantely oxygen reduction (high oxygen concentration) on the Pt counter electrode.     

Enhancement of oxygen mass transfer rate in the presence of nanosized particles

Absorption of gases into a liquid is essentially important for two- or three-phase reactions, because the diffusion of a sparingly soluble gas, like oxygen, across a gas-liquid interface generally limits the reaction rates. Using a third, dispersed phase, the mass transfer rate could be significantly increased. The question arises how the absorption rate can be described in the presence of very fine, nanometer size particles or droplets. Its mathematical model should take into account the specific properties of the nanoparticles, e.g. the Brownian motion of particles, its effect on the diffusion of the bulk phase molecules, the mass transfer rate into the nanoparticles, its dependency on the particle size, etc. The mass transfer rate of oxygen, in the presence of nanometer size, organic droplets, has been investigated both experimentally, using organic submicron n-hexadecane droplets, and theoretically. The effect of the Brownian motion of the nanoparticles as well as its effect on the diffusivity in the nanofluid has been discussed. Accordingly, the enhanced diffusion coefficient, due to the convective motion of the continuous liquid phase induced by the moving particles, has been predicted and its effect on the mass transfer enhancement has been calculated using both homogeneous and heterogeneous mathematical models. The predicted data were compared to the measured ones.     

CexZr1 − xO2 mixed oxides applied to minimize the bromate formation in the catalytic ozonation of a filtered water

Several Ce_xZr_1 − xO₂ mixed oxides were prepared and used as catalysts to investigate the minimization of BrO₃⁻ formation in the ozonation of a filtered water containing Br⁻ in a batch reactor. The Ce_xZr_1 − xO₂ mixed oxides showed good performance in reducing BrO₃⁻ formation and removing organic compounds. The Ce_0.75Zr_0.25O₂ oxide exhibited the highest efficiency, and 53% BrO₃⁻ was reduced after 20 min reaction. The mixed oxides accelerated the decomposition of the dissolved O₃ into OH radicals, and the competitive reaction between organic compounds and Br⁻ with OH radicals was found to occur in the ozonation reaction.     

直接甲醇燃料电池阴极水的传输特性

利用COMSOL Multiphysics软件对直接甲醇燃料电池（DMFC）阴极模型进行计算,获得压力、速度、水、氧气和液态饱和度分布情况,研究扩散层在不同物理参数（如厚度、孔隙率、孔径大小和亲憎水性）下电池阴极水和氧气的传输情况,进一步建立扩散层孔隙率梯度的数学模型,研究扩散层孔隙率梯度以及支撑层参数对直接甲醇燃料电池性能和物质传输的影响。结果表明,扩散层具有大孔隙率、薄扩散层时均有利于氧气传质,可以使电池性能提高;扩散层孔隙率梯度的存在可以减轻氧气传输阻力,提高电池性能。     

II. Electrodeposition/removal of nickel in a spouted electrochemical reactor

An investigation is presented of nickel electrodeposition from acidic solutions in a cylindrical spouted electrochemical reactor. The effects of solution pH, temperature, and applied current on nickel removal/recovery rate, current efficiency, and corrosion rate of deposited nickel on the cathodic particles were explored under galvanostatic operation. Nitrogen sparging was used to decrease the dissolved oxygen concentration in the electrolyte in order to reduce the nickel corrosion rate, thereby increasing the nickel electrowinning rate and current efficiency. A numerical model of electrodeposition, including corrosion and mass transfer in the particulate cathode moving bed, is presented that describes the behavior of the experimental net nickel electrodeposition data quite well.     

Removal of aqueous Fe2+ using MnO2–clinoptilolite in a batch slurry reactor: Catalyst synthesis,characterization and modeling of catalytic behavior

An Iranian clinoptilolite has been modified with MnO₂ for the catalytic removal of Fe²⁺ cations from water in a batch slurry reactor. The modified zeolite was subjected to FESEM, XRD, WDX, XRF and specific surface area analysis. A correlation for the intrinsic catalytic reaction rate incorporating both Fe²⁺ and dissolved oxygen concentration as a function of reaction temperature has been presented. The effect of the modified zeolite aggregate particle size on the iron removal kinetics has been investigated. It was shown that for particles larger than 150 μm, diffusion through the mesopores of the zeolite aggregate is rate controlling. The effective diffusion coefficient through the particles at RT has been calculated as 2.3 × 10^?6 cm² s^?1. It is shown that liquid phase molecular diffusion within the mesopores is the dominating mass transfer mechanism.     

Development of microbubble aerator for waste water treatment using aerobic activated sludge

In large-scale waste water treatment plants, the aerobic biochemical reactor is the most important process, where the oxygen supply into the microorganisms often limits the overall waste water treatment rate. On the other hand, several kinds of microbubble distributors have been developed to enrich the oxygen dissolution in water. Therefore, the application of microbubbles for a waste water treatment system was investigated in this study.The oxygen absorption performance of typical microbubble generators was compared with typical bubble generators. To evaluate each bubble generator, the liquid-phase volumetric oxygen transfer coefficient, gas hold-up and power consumption per unit liquid volume were measured in a bubble column attached to each bubble generator. All the microbubble generators allowed the oxygen to dissolve faster than the typical aerators. The spiral liquid flow type microbubble generator had the highest oxygen transfer coefficient even at a low air flow rate although it used more energy than the typical distributors.To improve an industrial waste water treatment system, a novel aeration system utilizing a spiral liquid flow type microbubble generator was proposed in this study. The present system has some advantages such as compact size, portability and fast oxygen dissolution rate. To ensure the performance for organic waste water treatment, the effects of the aeration rate, dissolved oxygen concentration and device properties on the specific consumption rate of model organic waste were investigated. For the novel aeration system, the most suitable conditions to treat organic waste were found.     

装配水平筛板的气升式反应器中气液传质特性的数值模拟

利用Turbulent–Lehr组合模型对装配水平筛板的气升式反应器进行了计算流体力学(CFD)模拟,研究水平筛板对气含率、气泡直径、体积传质系数(kLa)和气液流速的影响。结果表明,筛板对气相的囤积作用和对液相的阻碍作用增加了反应器的整体气含率。筛板对气相的二次均布作用减弱了筛板和液面之间区域的气泡聚并过程,筛板筛孔对气泡的破碎作用产生了大量小于初始直径的气泡,增加了气泡比表面积(a);筛板对液相的阻碍作用提高了筛板附近的气–液相流动速度差,从而提高了该区域的液膜传质系数(kL),强化了反应器内的气液传质效果。     

PEMFC阴极扩散层结构特性对水淹影响的数值分析

建立质子交换膜燃料电池一维两相传递模型,通过达西定律和菲克定律的联立求解得到扩散层中的液体饱和度和氧气浓度分布。考察扩散层特性参数孔隙率、厚度、接触角、渗透率对阴极水淹的影响,结果表明扩散层表面憎水将有助于液态水移出,但当达到憎水条件后,增大接触角对液态水传输和氧气传质的影响逐渐变小。憎水条件下孔隙率和厚度对液态水传输的影响不是很明显,但孔隙率增大和扩散层厚度减小均有利于氧气传质,实际应用中孔隙率增大的同时,厚度也要适当增大,极限电流密度相差不大。模型计算结果与文献中不同PTFE含量条件下实验的Tafel斜率和极限电流密度比较,吻合较好。     

New insights into the influence of activated carbon surface oxygen groups on H2O2 decomposition and oxidation of pre-adsorbed volatile organic compounds

In this study, the influence of the surface oxygen groups of activated carbons (ACs) on the decomposition of H₂O₂ and the consequent OH radicals generation is investigated. The oxidation of pre-adsorbed volatile organic compounds by H₂O₂ is also studied. Four ACs, with low percentage of inorganic matter (<0.2%), similar textural properties but differing in their surface oxygen content were evaluated. The surface oxygen groups of the ACs were characterised by using appropriate characterisation techniques (temperature programmed desorption and X-ray photoelectron spectroscopy). The kinetic curves of H₂O₂ decomposition were very similar for all the ACs. However, different profiles in the production of OH radicals were observed. OH radicals generation seemed to be promoted by low surface oxygen contents. Oxidation of two volatile organic compounds (VOCs) of different polarity, methyl ethyl ketone (MEK) and toluene, pre-adsorbed onto the ACs was finally investigated. H₂O₂ was used as oxidising agent. Both VOCs presented similar maximum oxidation rates, around 70%, in spite of their different hydrophobicity. Some evidences are provided supporting that oxidation of pre-adsorbed VOCs can take place in the inner pore structure of the ACs.     

高温液态水中甜高粱渣半纤维素水解及其机理

为了回收甜高粱渣中的半纤维素衍生糖并了解其水解机理,在自行设计的Flowthrough反应器中对甜高粱渣进行了高温液态水水解,分别考察了不同反应温度和反应液流量下水解液中产物的生成情况。研究表明,相对葡萄糖和阿拉伯糖而言,木糖的生成受反应温度和反应液流量影响更大。温度高于195 ℃时糖降解加剧,总木糖浓度不断降低;低流量（5 ml?min-1）条件下生成的木糖不能被及时排出而进一步降解。通过产物分析可知,甜高粱渣半纤维素中含有典型的O-乙酰基-4-O-甲基葡萄糖醛酸基阿拉伯糖基木聚糖结构,木糖、葡萄糖、阿拉伯糖、各种低聚糖、乙酸和葡萄糖醛酸等是半纤维素水解的直接产物,糠醛和5-羟甲基糠醛等是糖类的降解产物, 甲酸等小分子酸是它们的进一步降解产物。