Kinetic study on degradation of gaseous acetone over thin-film TiO2 photocatalyst in a continuous flow system

The effects of mixing condition by baffles, inlet concentration and face velocity on the photocatalytic degradation (PCD) of gaseous acetone over thin-film TiO₂ have been examined in a continuous flow system. The PCD rate increased upon installing baffles at a low inlet concentration and a high face velocity.     

Power consumption and gas—liquid dispersion in turbulently agitated vessels with vertical dual-array tubular coil baffles

In this work vertical dual-array tubular coil baffles arranged in groups of four, six or eight were investigated and the results compared with those from four planar baffles. The baffle coefficients for a single phase, along with the power consumption and gas hold-up in the gas-liquid phase of a system with the various baffle configurations for single and triple Rushton turbines are presented. Measurements were carried out using a dish-bottom vessel with an inner diameter of 0.29 m. Two ambient-temperature media were used as the liquid phase, namely, tap water and a 0.5 M Na₂SO₄ aqueous solution, representing coalescent and non-coalescent liquids, respectively. The results of the single-phase experiment revealed the coil baffles to have lower power numbers; when the baffle coefficient is ≥ 0.12, the mixing efficiency is the same as that for four planar baffles. The power consumption experiment using the gas-liquid phase showed that installing coil baffles prevented a large power draw in all types of media. In addition, the power draw characteristics are affected by the media. It was found that, because of the low K_B number, flooding occurred more readily with coil baffles than with planar baffles. Gas-liquid dispersion experiments in an air-water system indicated that, at a low gas flow-rate, the gas hold-up values of the coil baffles were almost 60 % higher than those of the conventional four baffles. However, this phenomenon was not observed in the Na₂SO₄ aqueous solution because of the existence of dead zones in viscous liquids. Finally, all the data from the power consumption and gas hold-up experiments on the gas-liquid phase were correlated.     

Evaluation of O2 and CO2 transfer coefficients in a locally integrated tubular hollow fiber bioreactor

We have studied the transfer coefficients for O₂ transport to and CO₂ removal from a model cell-free system using microporous hydrophobic hollow fibers axially placed along a tubular bioreactor for ethanol production with immobilized yeast in the shell. In this locally integrated bioreactor, O₂ and CO₂ transfer rates depend strongly on the shell side liquid flow rate; O₂ flow rate in the fiber bore influences O₂ transport only at very low flow rates. Diffusion of CO₂ does not affect O₂ transport. Local and overall O₂ and CO₂ transfer coefficients have been determined for a wide range of Reynolds Numbers. The efficiency of such transfers has been demonstrated for alcohol fermentation.     

Gas permeability of combined membrane systems with mobile liquid carrier

Gas transfer in a membrane system called a selective membrane valve (SMV) is studied. The SMV is a system consisting of two mobile gas phases, one mobile liquid phase, and two membranes acting as interfaces between gas and liquid. Such a membrane system has supplementary variable parameters and is designated for the separation of multicomponent gas mixtures. System permeability for individual gases (CO₂, O₂, and H₂) and its dependence on a flow rate of a liquid phase are studied. Time dependences of the non-steady state transfer of CO₂ through the immobile layer of chemisorbent (aqueous K₂CO₃ solution) at its different concentrations are studied for the first time. Two theoretical models are developed: the model of gas transfer through a selective membrane valve system with a mobile liquid absorbent (in the absence of chemical interaction) and the model of a non-steady-state transfer of CO₂ through the immobile layer of aqueous potassium carbonate solution. The first model makes it possible to determine gas-to-liquid diffusion coefficients; the second model permits us to plot kinetic permeability curves and to calculate system permeability with allowance for the CO₂ transfer accompanied by reversible chemical reaction with the carrier. The model dependences agree well with the experimental data.     

The effect of the physical properties of the liquid phase on the gas-liquid mass transfer coefficient in two- and three-phase agitated systems

The results of studies concerning two- and three-phase systems in an agitated vessel are presented. The aim of our research was to investigate the effect of the physical properties of the liquid phase on the value of the volumetric gas-liquid mass transfer coefficient in mechanically agitated gas-liquid and gas-solid-liquid systems. Our experimental studies were conducted in a vessel with an internal diameter of 0.288 m. The flat bottom vessel, equipped with four baffles, was filled with liquid up to a height equal to the inner diameter. The liquid volume was 0.02 m³. Three high-speed impellers of a diameter equal to 0.33 of the vessel diameter were used: Rushton turbine (RT), Smith turbine (CD 6), or A 315 impeller. The measurements were carried out in coalescing and non-coalescing systems. Distilled water and aqueous solutions of an electrolyte (sodium chloride) of two different concentrations were used as the liquid phase. The gas phase was air. In the three-phase system, particles of sea sand were used as solid phase. The measurements were conducted at five different gas-flow rates and three particle loadings. Volumetric gas-liquid mass transfer coefficients were measured using the dynamic method. The presence and concentration of an electrolyte strongly affected the value of the gas-liquid mass transfer coefficient in both two- and three-phase systems. For all agitators used, significantly higher k _l a coefficient values were obtained in the 0.4 kmol m⁻³ and 0.8 kmol m⁻³ aqueous NaCl solutions compared with the data for a coalescing system (with distilled water as the liquid phase). The k _l a coefficient did not exhibit a linear relationship with the electrolyte concentration. An increase in the sodium chloride concentration from 0.4 kmol m⁻³ to 0.8 kmol m⁻³ caused a considerable decrease in the volumetric mass transfer coefficient in both the two-phase and three-phase systems. It was concluded that the mass transfer processes improved at a certain concentration of ions; however, above this concentration no further increase in k _l a could be achieved.     

膜供氧催化氧化处理太空舱冷凝废水研究

采用膜供氧催化氧化反应器处理太空舱冷凝废水。以乙醇为目标污染物,研究了膜供氧催化氧化反应器对其的处理效果,并考察了催化反应对膜传质模型的影响。结果表明,随着停留时间的增加,乙醇的去除率增大,中间产物乙酸的生成率减少。当废水流量为0.5mL·min-1,气室压力为2kPa时,乙醇的去除率可达86.1%,其中81.4%完全氧化,4.7%转化成乙酸。基于传质模型对实验结果分析表明,催化反应有利于提高膜供氧总传质系数,当流量为0.5mL·min-1时,与无催化反应条件相比,氧总传质系数提高11.8倍。停留时间的增加也有利于提高膜供氧传质系数。结果表明,膜供氧催化氧化反应器可高效降解冷凝废水中的乙醇,在太空舱冷凝废水处理中有潜在的应用价值。     

Influence of the eluent composition on column efficiency in reversed-phase high-performance liquid chromatography

Summary The dependence of column efficiency on the eluent (MeOH/H₂O) composition in a reversed-phase liquid chromatography system within a wide concentration range has been systematically examined. It is shown that when the intracolumn effect of mass transfer and diffusion is the main factor controlling band broadening the column efficiency decreases with the increase of the viscosity of the MeOH/H₂O mixture; on the other hand, when the extra-column effect is the main factor an increase in the viscosity of the eluents will help in improving column efficiency. The column efficiency is also related to the properties of the sample.     

Heat transfer in a jacketed agitated vessel equipped with multistage impellers

In this work, heat transfer via the cylindrical part of the jacket in an agitated vessel has been investigated. Heat transfer coefficients were determined using the transient method based on measuring the temperature dependency of the liquid batch on time. A multistage impeller made of two impellers was used in a cylindrical vessel with dished bottom. The lower impeller was a curved blade turbine with the diameter of d = 100 mm and the upper impeller was either a pitched three-blade or pitched four-blade impeller with the diameter of d₁ = 67 mm. Three different impeller clearances in a multistage configuration, H₃/d₁ = 1, 1.5, and 2, were used in our measurements. The vessel was equipped with two baffles. Experimental results were evaluated using the Euler’s method and nonlinear regression procedure in the Matlab® software and they are summarized in form of Nusselt number correlations describing their dependency on the Reynolds number.     

Comparison ofE a values obtained by thermal analysis with energy of ‘charge-transfer’ spectra for potassium and silver permanganates

The activation energy,E _a taken from the thermal decomposition of KMnO₄ and AgMnO₄ was compared with the energy of the longest wavelength O→Mn ‘charge transfer’ (CT) transition. TheE _a and CT correlation was found in these systems. However, such relationship can be valid when in the dissociation process the electron transfer is assumed to be the rate determining step. Thus, the permanganates as well as the previously studied chromates, are positive examples showing that in some cases, the energies derived from both methods can be comparable.     

Hydrodynamic and mass transfer studies in an external-loop air-lift bioreactor for immobilized animal cell culture

Air-lift bioreactors containing suspended or immobilized animal cells have been used for the production of a variety of high-value biologicals. In the bioprocessing industry, there is a need to study and quantify the relationships between bioreactor-system properties such as mixing, flow, mass transfer, and cell processes. In the present study, the performance of a 1-L external-loop air-lift bioreactor was investigated by studying gas-liquid oxygen transfer, mixing time, liquid velocity and gas hold-up at various aeration rates. These studies were performed over a range (0-25%) of loadings of small (500-800 μm) calcium alginate beads to investigate the effect of using various concentrations of cell immobilization matrices on the physical properties of the system. At an aeration rate of 0.5 vvm, the mixing time was decreased by 50%, from 75 s at 0% bead loading to 38 s at 10% bead loading. A minimum liquid velocity of 10 cm/s was required to keep the alginate beads in suspension. As bead loading increased, flow within the reactor went from turbulent conditions to the transition zone. At all bead loadings tested, the gas hold-up increased by only 2% with an increase in aeration rate from 0.1 to 1.0 vvm, regardless of whether the total reactor volume (i.e., liquid and beads) or the liquid volume was used in calculating the hold-up. A mathematical correlation was developed for expressing the dependence of the volumetric mass-transfer coefficient, k₁a, on aeration rate (vvm) and microbead loading. With this equation it was possible to predict, within 20%, the k₁a knowing the gas-flow rate and the volume percentage of microbeads present in the bioreactor. A theoretical study was also performed to calculate the oxygen transfer from the bulk liquid to the center of microcapsules containing animal cells using experimental k₁a data. The results suggest that whereas there is no oxygen limitation at 10 to 15% microcapsule loading, there is a potential mass-transfer problem at 25% loading if the bioreactor is operated at an aeration rate of less than 1.06 vvm.     

Photoelectrochemistry of p-type Cu2O semiconductor electrode in ionic liquid

We investigated the photoelectrochemical characteristics and photo-stability of Cu₂O layered on a copper plate using a hydrophobic ionic liquid. Our findings revealed that Cu₂O is stable under white light irradiation, provided water is removed from the electrolyte. Methyl viologen derivative, a well-established electron acceptor, was introduced to the ionic liquid electrolyte, allowing the photo-induced electron transfer reaction at the Cu₂O/electrolyte interface to be characterized. The methyl viologen derivative exhibited two distinct redox reactions at −0.56 V and −0.98 V vs. Ag/AgCl, clearly indicating that no dimer formation or co-proportionation reaction occurred. The excessive photocurrents being continuously generated resulted from a viable photo-induced electron transfer reaction from the Cu₂O to the acceptor. However, in contrast, the reduction of the Cu₂O by water in the aqueous solution causes this electron transfer to be inhibited. We further demonstrate that these findings are vital to understanding the role of the Cu₂O and its photoelectrochemical applications.     

Semiclassical calculation of energy transfer in polyatomic molecules. VIII. Theory for atom + non-linear triatom

The theory for collision of an atom with a non-linear triatomic molecule is presented and the He + H₂O system considered as an example. It is shown that both anharmonic and Coriolis coupling are important for the energy transfer. Seventeen rate constants for vibrational transitions in H₂O are calculated in the temperature range 300–2000 K.     

Raman studies of molten salt hydrates: the beryllium and aluminium nitrate-water systems

Raman spectra of the liquid systems Be(NO₃)₂ · 20H₂O, Be(NO₃)₂ · 4H₂O, Al(NO₃)₃·20H₂O, and Al(NO₃)₃ · 9H₂O have been recorded. The spectra are analysed in terms of vibrational modes arising from water, the nitrate ion, the aquated metal ions and hydrolysis products. For the concentrated beryllium system, though not for the aluminium system, the spectra suggest a significant degree of proton transfer from [Be(OH₂)₄]²⁺ to NO₃^?. Solvent-separated metal-nitrate ion pairs appear to be present in all the systems studied.     

UF6 plasma chemistry reconstitution experiments using high-temperature fluorine

Prior results indicate techniques have been developed for fluid mechanical confinement of high-temperature uranium hexafluoride (UF₆) plasma for long test times while simultaneously minimizing uranium compound deposition on the walls. Follow-on investigations were conducted to demonstrate a UF₆/argon injection, separation, and reconstitution system for use with rf-heated uranium plasma confinement experiments applicable to UF₆ plasma core reactors. A static fluorine batch-type regeneration test reactor and a flowing preheated fluorine/UF₆ regeneration system were developed for converting all the nonvolatile uranium compound exhaust products back to pure UF₆ using a single reactant. Pure fluorine preheat temperatures up to 1000 K resulted in on-line regeneration efficiencies up to about 90%; static batch-type experiments resulted in 100% regeneration efficiencies but required significantly longer residence times. A custom-built, ruggedized time-of-flight (T.O.F.) mass spectrometer, sampling, and data acquisition system permitted on-line quantitative measurements of the UF₆ concentrations down to 30 ppm at various sections of the exhaust system; this system proved operational after long-time exposure to corrosive UF₆ and other uranium halides.     

A Comparison of Primary and Secondary Hydrogen Abstraction from Organophosphates by Hydroxyl Radical

To compare the effect of primary and secondary C? H bonds on hydrogen?atom abstraction by hydroxyl radical, rate constants for the reactions of OH radicals with trimethyl phosphate [TMPO, (CH₃O)₃P(O)] and triethyl phosphate [TEPO, (CH₃CH₂O)₃P(O)] have been calculated using the semiclassical flux–flux autocorrelation function (SCFFAF) method and compared with experimental measurements over the temperature range 250–350 K. SCFFAF specifies that structures be obtained at the CCSD/6?31++G** level of chemical theory and the height of the activation barrier be determined using an energy extrapolation, here a variant of the G2MP2 method. Dynamics are generated in the SCFFAF method from forces computed with a transfer Hamiltonian, which provides information about the curvature of the potential energy surface in the neighborhood of the transition state (TS), as well as the required internal forces. The temperature?dependent reaction rate constants are calculated for the various possible abstraction pathways, primary hydrogen atom abstraction in the case of TMPO, and primary and secondary in the case of TEPO. Since two energetically favorable parent structures for each system are included in the model, the activation energy is calculated with respect to the conformer that connects to a given TS and the total rate constant at a given temperature is Boltzmann weighted with respect to the parent conformer. The computed temperature?dependent rate curves are consistent with published experimental data in both magnitude and temperature dependence. © 2013 Wiley Periodicals, Inc. Int J Chem Kinet 45: 187–201, 2013     

Obtaining calcium carbonate in a multiphase system by the use of new rotating disc precipitation reactor

Rotating disc reactor (RDR) was constructed to conduct gas–liquid–solid reactions with controlled reagent transfer from gaseous to liquid phase. The concept is based on continuous formation of thin liquid films at a surface of rotating discs where the mass transfer proceed in diffusion–convective way. The reactor was employed to run precipitation reaction of CaCO₃ via carbon dioxide absorption in lime slurry. During each reaction pH changes and Ca²⁺ concentration in time were measured. Disc rotations and gas flows were changed during the experiment and their influence on the obtained CaCO₃ powders has been examined and fully discussed.     

TiO2/Cu2O/Pt复合空心微球的制备及其光催化性能

以锐钛矿相TiO₂溶胶为基底,采用沉淀法和液相沉积法制备了TiO₂/Cu₂O/Pt复合空心微球,通过改变n₍Ti⁴⁺)∶n_Cu2+和H₂Pt Cl₆·6H₂O溶液的加入量对TiO₂的形貌和结构进行调控,采用不同的方法对不同样品的物相及结构、微观形貌和光学性能进行了对比分析。分析结果表明,复合材料中Pt与Cu₂O的引入产生协同效应,不仅在一定程度上阻止了电子-空穴的复合,还降低了禁带宽度,在可见光区域光吸收明显增强。与TiO₂、Cu₂O和TiO₂/Cu₂O光催化剂相比较,TiO₂/Cu₂O/Pt降解有机污染物的能力显著增强,首次光照120 min可降解93%的甲基橙(MO)溶液,4次循环后降解率为71%,具有良好的光催化...     

TiO2/Cu2O/Pt复合空心微球的制备及其光催化性能

以锐钛矿相TiO₂溶胶为基底,采用沉淀法和液相沉积法制备了TiO₂/Cu₂O/Pt复合空心微球,通过改变n_Ti⁴⁺∶ n_Cu²⁺和H₂PtCl₆·6 H₂O溶液的加入量对TiO₂的形貌和结构进行调控,采用不同的方法对不同样品的物相及结构、微观形貌和光学性能进行了对比分析。分析结果表明,复合材料中Pt与Cu₂O的引入产生协同效应,不仅在一定程度上阻止了电子-空穴的复合,还降低了禁带宽度,在可见光区域光吸收明显增强。与TiO₂、Cu₂O和TiO₂/Cu₂O光催化剂相比较,TiO₂/Cu₂O/Pt降解有机污染物的能力显著增强,首次光照120 min可降解93%的甲基橙(MO)溶液,4次循环后降解率为71%,具有良好的光催化稳定性能。     

Vibrational energy transfer in hydrogen liquid and its isotopes

The transfer of vibrational energy (V-V) from H₂ to isotopic impurities (HD or D₂) has been studied in the liquid state, between 15 and 30 K. The subsequent relaxation (V-T) of the excited impurity by the H₂ liquid host has also been measured and contrasted with the vibrational relaxation behaviour of pure H₂ and D₂ liquids. The isothermal density dependence of both V-V and V-T transfer has been investigated in the fluid state at 30 K. High density relaxation rates are also compared to our data in the pure gases and to other available gas phase results. Measurements in the solid, near the triple point temperature, are equally reported for each process studied.     

Combination of nanofluid and inserts for heat transfer enhancement

Improving heat transfer is a critical subject for energy conservation systems which directly affects economic efficiency of these systems. There are active and passive methods which can be employed to enhance the rate of heat transfer without reducing the general efficiency of the energy conservation systems. Among these methods, passive techniques are more cost-effective and reliable in comparison with active ones as they have no moving parts. To achieve further improvements in heat transfer performances, some researchers combined passive techniques. This article performs a review of the literature on the area of heat transfer improvement employing a combination of nanofluid and inserts. Inserts are baffles, twisted tape, vortex generators, and wire coil inserts. The progress made and the current challenges for each combined system are discussed, and some conclusions and suggestions are made for future research.