Anomalous Capillary Pressure, Stress, and Stability of Solids-Coated Bubbles

A two-dimensional theoretical model for solids-coated, or "armored," bubbles shows how the armor can support a liquid-vapor interface of reduced or reversed curvature between the particles, giving the bubble zero or even negative capillary pressure. The inward capillary force pulling the particles into the center of the bubble are balanced by large contact forces between the particles in the armor. Thus the bubble is stabilized against dissolution of gas into surrounding liquid, which otherwise would rapidly collapse the bubble. The stresses between particles in such cases are large and could drive sintering of the particles into a rigid framework. Earlier work on solids-coated bubbles assumed that solids can freely enter or leave the bubble surface as the bubble shrinks or expands. In such a case, armored bubbles would not be stable to gas dissolution into surrounding liquid. A new free-energy analysis, however, suggests that a shrunken bubble would not spontaneously expel a solid particle from its armor to relieve stress and allow the bubble to shrink further. Implications and limitations of the theory are discussed. Copyright 1999 Academic Press.     

Mist separation and sonochemiluminescence under pulsed ultrasound

Differences in the amount of water-mist separation and the intensity of luminol chemiluminescence for pulsed and continuous-wave (CW) ultrasound at 135 kHz have been investigated. The amount of mist generated is estimated using the cooling rate of a copper plate sprayed with the mist. For pulsed operation with an appropriate duty cycle, the cooling rate and the cooling rate per input power to the transducer are higher by 4 and 12 times compared to CW operation, respectively. This is due to the amplitude of the pulsed ultrasound being higher than that for CW ultrasound. Relatively low power pulsed operation can successfully produce both a higher sonochemiluminescence (SCL) intensity and cooling rate than those for CW ultrasound. The sonochemical reaction for pulsed ultrasound occurs at the same input power threshold as that for mist separation, whereas for CW ultrasound, the former threshold is lower than the latter. A higher number of large bubbles is produced with CW ultrasound than that with pulsed ultrasound. To achieve a sound pressure amplitude sufficient for mist separation near the surface of a liquid, it is necessary to expel these bubbles by changing the sound field from resonant standing waves to progressive waves that give rise to capillary waves on the liquid surface.     

Experimental analysis of the hydrodynamics of a three-phase system in a vessel with two impellers

Results of experimental analysis concerning gas hold-up and average residence time of gas bubbles in a three-phase gas-solid-liquid system produced in a baffled, double-impeller vessel are presented. Measurements were carried out in a vessel with the internal diameter of 0.288 m. Two different double-impeller configurations were used for agitation: Rushton turbine (lower) — A 315 (upper) and Rushton turbine (lower) — HE 3 (upper). Upper impellers differed in the fluid pumping mode. Coalescing and non-coalescing systems were tested. Liquid phases were distilled water (coalescing system) and aqueous solutions of NaCl (non-coalescing systems). The ability of gas bubbles to coalesce in the liquid was described using parameter Y. Dispersed phases were air and particles of sea sand. The experiments were conducted at seven different gas flow rates and two particle loadings. Effects of the ability of gas bubbles to coalesce (liquid phase properties), operating parameters (superficial gas velocity, impeller speed, solids loadings), and of the type of the impeller configuration on the investigated parameters were determined. The results were approximated mathematically. For both impeller configurations tested, significantly higher gas hold-up values were obtained in the non-coalescing gas-solid-liquid systems compared to the coalescing one. Out of the tested impeller systems, the RT-A 315 configuration proved to have better performance ensuring good gas dispersion in the liquid in the three-phase systems.     

Agitation of a gas-solid-liquid system in a vessel with high-speed impeller and vertical tubular coil

Experimental results of gas hold-up, power consumption and residence time of gas bubbles in a gas-solid-liquid system produced in an agitated vessel equipped with a high-speed impeller and a vertical tubular coil are presented in this paper. Critical agitator speed, needed for the dispersion of gas bubbles and solid particles in liquid were also identified. The studies were carried out in an agitated vessel of the inner diameter D = 0.634 m and the working liquid volume of about 0.2 m³. A tubular coil of the diameter of 0.7D, consisting of 24 vertical tubes of the diameter of 0.016D, was located inside the flat-bottomed vessel. The agitated vessel was equipped with a Rushton turbine with six blades or an A 315 impeller with four blades. Both impellers had diameter, d, equal to 0.33D. The vessel was filled with liquid up to the height H = D. In this study, air and particles of sea sand with the mean diameter of 335 μm and the concentration of up to 3.0 mass % were dispersed in distilled water as the liquid phase. The measurements were carried out within the turbulent regime of the fluid flow in the agitated vessel. Results of the measurements were processed graphically and mathematically. Lower values of the critical agitator speed, n _JSG, needed for simultaneous dispersion of gas bubbles and particles with the solids concentration from 0.5 mass % to 2 mass %, were obtained for the vessel equipped with the A 315 impeller. Higher values of the specific power consumption were reached for the vessel with the Rushton turbine. Higher values of the gas hold-up and residence time of the gas bubbles in the fluid were obtained for the system equipped with the Rushton turbine. Results of the gas hold-up as a function of the specific power consumption, superficial gas velocity and solids concentration were approximated with good accuracy using Eq. (5).     

Long-term study of an intermittent air sparged MBR for synthetic wastewater treatment

Membrane bioreactors (MBR) combine biological processes with membrane filtration. Advantages of MBR in municipal wastewater treatment include high effluent quality and reduced space requirements. Steady operation of membrane plants requires careful management of membrane fouling. Even though it might be impossible to prevent, fouling can be limited by techniques such as gas sparging. The injection of gas bubbles increases the shear stress and removes fouling material from the membrane surface. Most cited literature on air sparging refers to short-term experiments, often times in bench scale. The aim of this study was therefore long-term investigations in pilot plant scale of a 70 L reactor fed with glucose-based synthetic wastewater. The main focus was on enhancing permeate flux by air sparging. The results showed that using air sparging significantly increased the permeate flux was doubled even over several weeks. The findings were interpreted using the dimensionless fouling and shear stress number. The fouling resistance was found to decrease significantly with air injection ratios between 0.4 and 0.5. When air sparging was applied after a period without air sparging, the shear stress number doubled. This increase in shear led to a reduction of the fouling number by approximately 30%. During several weeks air sparging only a slow fouling number increase was. In contrast to that after air sparging was ceased, an exponential increase of the fouling number was observed.     

Highly selective ethylbenzene production through alkylation of dilute ethylene with gas phase-liquid phase benzene and transalkylation feed

A novel industrial process was designed for the highly selective production of ethylbenzene.It comprised of a reactor vessel,vapor phase ethylene feed stream,benzene and transalkylation feed stream.Especially the product stream containing ethylbenzene was used to heat the reactor vessel,which consisted of an alkylation section,an upper heat exchange section,and a bottom heat exchange section.In such a novel reactor,vapor phase benzene and liquid phase benzene were coexisted due to the heat produced by isothermal reaction between the upper heat exchange section and the bottom heat exchange section.The process was demonstrated by the thermodynamic analysis and experimental results.In fact,during the 1010 hour-life-test of gas phase ethene with gas phase-liquid phase benzene alkylation reaction,the ethene conversion was above 95%,and the ethylbenzene selectivity was above 83% (only benzene feed) and even higher than 99% (benzene plus transalkylation feed).At the same time,the xylene content in the ethylbenzene was less than 100 ppm when the reaction was carried out under the reaction conditions of 140-185℃ of temperature,1.6-2.1 MPa of pressure,3.0-5.5 of benzene/ethylene mole ratio,4-6 v% of transalkylation feed/(benzene+transalkylation feed),0.19-0.27 h-1 of ethene space velocity,and 1000 g of 3998 catalyst loaded.Thus,compared with the conventional ethylbenzene synthesis route,the transalkylation reactor could be omitted in this novel Industrial process.     

High selective ethylbenzene obtainment through alkylation of dilute ethene with gas phase-liquid phase benzene and transalkylation feed

A novel industrial process was designed for the highly selective production of ethylbenzene. It comprised of a reactor vessel, vapor phase ethylene feed stream, benzene and transalkylation feed stream. Especially the product stream containing ethylbenzene was used to heat the reactor vessel, which consisted of an alkylation section, an upper heat exchange section, and a bottom heat exchange section. In such a novel reactor, vapor phase benzene and liquid phase benzene were coexisted due to the heat produced by isothermal reaction between the upper heat exchange section and the bottom heat exchange section. The process was demonstrated by the thermodynamic analysis and experimental results. In fact, during the 1010 hour-life-test of gas phase ethene with gas phase-liquid phase benzene alkylation reaction, the ethene conversion was above 95%, and the ethylbenzene selectivity was above 83% (only benzene feed) and even higher than 99% (benzene plus transalkylation feed). At the same time, the xylene content in the ethylbenzene was less than 100 ppm when the reaction was carried out under the reaction conditions of 140–185 °C of temperature, 1.6–2.1 MPa of pressure, 3.0–5.5 of benzene/ethylene mole ratio, 4–6 v% of transalkylation feed/(benzene+transalkylation feed), 0.19–0.27 h^?1 of ethene space velocity, and 1000 g of 3998 catalyst loaded. Thus, compared with the conventional ethylbenzene synthesis route, the transalkylation reactor could be omitted in this novel industrial process.     

Nanobubbles at the interface between water and a hydrophobic solid

A very thin layer (5-80 nm) of gas phase, consisting of discrete bubbles with only about 40 000 molecules, is quite stable at the interface between a hydrophobic solid and water. We prepare this gas phase from either ambient air or from CO(2)(g) through a solvent exchange method reported previously. In this work, we examine the interface using attenuated total internal reflection infrared spectroscopy. The presence of rotational fine structure in the spectrum of CO(2) and D(2)O proves that molecules are present in the gas phase at the interface. The air bubbles are stable for more than 4 days, whereas the CO(2) bubbles are only stable for 1-2 h. We determine the average gas pressure inside the CO(2) bubbles from the IR spectrum in two ways: from the width of the rotational fine structure (P(gas) < 2 atm) and from the intensity in the IR spectrum (P(gas) = 1.1 +/- 0.4 atm). The small difference in gas pressure between the bubbles and the ambient (1 atm) is consistent with the long lifetime. The dimensions and curvature of a set of individual bubbles was determined by atomic force microscopy. The pressures of individual bubbles calculated from the measured curvature using the Laplace equation fall into the range P(gas) = 1.0-1.7 atm, which is concordant with the average pressure measured from the IR spectrum. We believe that the difference in stability of the CO(2) bubbles and the air bubbles is due to a combination of the much lower pressure of CO(2) in the atmosphere and the greater solubility of CO(2) in water, compared to N(2) and O(2). As expected, smaller bubbles have a shorter average lifetime than larger bubbles, and the average pressure and the curvature of individual bubbles decreases with time. Surface plasmon resonance measurements provide supporting evidence that the film is in the gas state: the thin film has a lower refractive index than water, and there are few common contaminants that satisfy this condition. Interfacial gas bubbles are not ubiquitous on hydrophobic solids: bubble-free and bubble-decorated hydrophobic interfaces can be routinely prepared.     

Development of a sparging chamber for field radon analysis

Radon-222 has become a widely used tracer of submarine groundwater discharge. However, remote field studies are often limited by the need to pump water to a spray chamber which degasses dissolved radon for subsequent analysis in the gaseous phase. We develop here a new method of degassing dissolved ²²²Rn, utilizing a stream of bubbles driven by the internal air pump of a commercial radon analyzer to achieve air:water partitioning equilibrium, eliminating the need to pump water. This system utilizes a sparging chamber, comprised of a slotted vertically-oriented pipe with bubbles produced in the bottom. A non-slotted section of the pipe at the top of the chamber forms a sealed headspace, allowing air to be circulated in a closed loop between the sparging chamber and a radon-in-air monitor. We found that such a sparging chamber needs to allow bubbles to rise through at least 45 cm of water column to function at equal efficiency as the standard protocol of the spray chamber. Under our optimized configuration, the sparging chamber operates as efficiently as the standard protocol at measuring dissolved ²²²Rn activities when encountering increasing ²²²Rn activities, and offers even greater gas exchange efficiency when dissolved ²²²Rn activities decrease. The sparging chamber offers a more field-friendly alternative to measuring ²²²Rn activities, as it eliminates the need to maintain a submersible pump throughout the measurement and it offers increased temporal resolution when variable ²²²Rn activities are expected.     

Local hydrodynamic investigation of the aeration in a submerged hollow fibre membranes cassette

The better understanding of the effective air distribution inside a membrane cassette is a particular challenge in submerged membrane bioreactor. The present study is the first one that investigates the hydrodynamics of the coarse bubbles flow inside a hollow fibre membranes cassette. The experimental investigations were carried out in a reactor equipped with commercial modules from ZENON ZeeWeed^® 500d. A bi-optical probe was used to measure the bubble size, the bubble velocity and the gas hold-up at different locations between the modules and for three different gas flow rates. These local measurements gave significant information about the lateral distribution of the air and its evolution with the height on the surface of the membrane modules, which can impact on the filtration performance and are the first step to an optimisation of the aeration system and module geometry.     

Direct partial oxidation of methane to methanol： Reaction zones and role of catalyst location

Direct partial oxidation of methane to methanol was investigated in a specially designed reactor. Methanol yield of about 7%-8% was obtained in gas phase partial oxidation. It was proposed that the reactor could be divided into three reaction zones, namely pre-reaction zone, fierce reaction zone, and post-reaction zone, when the temperature was high enough to initiate a reaction. The oxidation of methane proceeded and was completed mostly in the fierce reaction zone. When the reactant mixture entered the post-reaction zone, only a small amount of produced methanol would bring about secondary reactions, because molecular oxygen had been exhausted in the fierce reaction zone. A catalyst, if necessary, should be placed either in the pre-reaction zone, to initiate a partial oxidation reaction at a lower temperature, or in the fierce reaction zone to control the homogeneous free radical reaction.     

Current status of membraneless water electrolysis cells

Commercial water electrolysis cells require a resistive, ion-permeable, gas-impermeable separator membrane between the electrodes to stop the hydrogen bubbles from mixing with the oxygen bubbles and vice versa. This work reviews the current status of ‘membraneless’ water electrolysis cells that safely avoid need for such a separator membrane. Three different approaches have been used to realize such cells. In the first approach, laminar flow within a microfluidic reaction chamber has been used to entrain the hydrogen and oxygen gas bubbles in separate, parallel streams that do not mix. In the second approach, closely-spaced porous electrodes have had liquid electrolyte divergently pumped through them to sweep the produced hydrogen and oxygen bubbles to different locations. In the most recent, promising approach, gas diffusion electrodes have been used to directly extract gas as it is produced, thereby avoiding discernible bubble formation and eliminating the need for a separator membrane to keep the gases separate.     

Three-Dimensionally Integrated Micro-solution Plasma: Numerical Feasibility Study and Practical Applications

This paper describes effects of design parameters for a three-dimensionally integrated micro-solution plasma (3D IMSP) reactor, which generates a large amount of microplasma in gas bubbles flowing with a liquid medium through a porous dielectric material. Electric fields in gas bubbles are calculated by solving Maxwell’s equations under the electro-quasi-static approximation. The calculated electric fields in the bubbles can be high enough for igniting electrical discharge in the bubbles even if the bubbles are surrounded by electrically conductive liquid. We show importance of higher permittivity of a dielectric-reactor tube and a higher voltage-rise rate for obtaining higher electric fields in the bubbles. Using a proto type 3D IMSP reactor, we demonstrate synthesis of gold nanoparticles and decomposition of methylene blue molecules in aqueous solution.     

Atmospheric-pressure microplasma in dielectrophoresis-driven bubbles for optical emission spectroscopy

The manipulation of bubbles and the ignition of microplasma within a 200 nL bubble at atmospheric pressure and in an inert silicone oil environment were achieved. Driven by dielectrophoresis (DEP), bubble generation, transportation, mixing, splitting, and expelling were demonstrated. This process facilitated the preparation of various bubbles with tuneable gas compositions. Different gas bubbles, including air, argon (Ar), helium (He), and Ar/He mixtures, were manipulated and ignited to the plasma state by dielectric barrier discharge (DBD) within a 50 μm-high gap between parallel plates. Moving and splitting the atmospheric-pressure microplasma in different gas bubbles were achieved by DEP. The excited light of the microplasma was recorded by an optical spectrometer for the optical emission spectroscopy (OES) analyses. The characteristic peaks of air, Ar, and He were observed in the DEP-driven microplasma. With the capability to manipulate bubbles and microplasma, this platform could be used for gas analyses in the future.     

基于晶格氧的甲烷化学链重整制合成气

利用氧载体中的晶格氧代替分子氧进行的甲烷化学链重整制合成气,是一种新颖的甲烷制合成气技术,具有较高经济效益和环境效应。它具有省却纯氧设备、能自热、合适的氢碳比、有用的副产物以及过程易于工业化等优点,因此受到国内外研究者的普遍关注。本文介绍了化学链重整技术的基本原理及其特点;重点总结了用于甲烷化学链重整的单金属氧载体和复合金属氧载体的研究进展;同时,探讨了几种具有典型代表的甲烷化学链重整反应装置,并指出串行流化床反应器是实现化学链重整技术工业化最有效的装置;最后对化学链重整技术的拓展应用以及与其他技术交叉运用等发展趋势进行了展望。     

Enhancement of sonochemical reaction rate by addition of micrometer-sized air bubbles

The sonochemical reaction rate has been enhanced by the introduction of tiny air bubbles. The bubbles including micrometer-sized ones are produced by method of atomization and are introduced into aqueous luminol solution under 141-kHz sonication in order to investigate the enhancement of sonochemical reaction rate by introduction of tiny bubbles through the intensity measurement of sonochemiluminescence (SCL). It is shown that the introduction of tiny bubbles under sonication accomplishes the large SCL intensity compared to the cases of sonication only and liquid flow under sonication. It is also shown that it is important to adjust the configuration of tiny-bubble addition to the sound field. Through the investigations on the intensity and the spatial pattern of luminol-SCL, it has been clarified that tiny bubbles added into the sonicated liquid not only cause the liquid flow but also increase the number of collapsing bubbles active for sonochemical reaction. It is also shown that the tiny-bubble addition enhances the reaction rate of KI oxidation under sonication. Therefore, the present method of introduction of tiny bubbles is effective for enhancement of sonochemical reaction rate.     

Micropumping of liquid by directional growth and selective venting of gas bubbles

We introduce a new mechanism to pump liquid in microchannels based on the directional growth and displacement of gas bubbles in conjunction with the non-directional and selective removal of the bubbles. A majority of the existing bubble-driven micropumps employs boiling despite the unfavorable scaling of energy consumption for miniaturization because the vapor bubbles can be easily removed by condensation. Other gas generation methods are rarely suitable for micropumping applications because it is difficult to remove the gas bubbles promptly from a pump loop. In order to eradicate this limitation, the rapid removal of insoluble gas bubbles without liquid leakage is achieved with hydrophobic nanopores, allowing the use of virtually any kind of bubbles. In this paper, electrolysis and gas injection are demonstrated as two distinctively different gas sources. The proposed mechanism is first proved by circulating water in a looped microchannel. Using H(2) and O(2) gas bubbles continuously generated by electrolysis, a prototype device with a looped channel shows a volumetric flow rate of 4.5-13.5 nL s(-1) with a direct current (DC) power input of 2-85 mW. A similar device with an open-ended microchannel gives a maximum flow rate of approximately 65 nL s(-1) and a maximum pressure head of approximately 195 Pa with 14 mW input. The electrolytic-bubble-driven micropump operates with a 10-100 times higher power efficiency than its thermal-bubble-driven counterparts and exhibits better controllability. The pumping mechanism is then implemented by injecting nitrogen gas bubbles to demonstrate the flexibility of bubble sources, which would allow one to choose them for specific needs (e.g., energy efficiency, thermal sensitivity, biocompatibility, and adjustable flow rate), making the proposed mechanism attractive for many applications including micro total analysis systems (microTAS) and micro fuel cells.     

Modeling and Simulation of Liquid Phase Propylene Polymerizations in Industrial Loop Reactors

Liquid phase tubular loop polymerization reactors are widely used in the polyolefin industries because of their capabilities to promote high mixing of reactants in the reaction vessel and to allow for high heat transfer rates with the cooling jacket due to their high aspect ratio. Previous works on this subject focused on the modeling of the polymerization system, but only a few compared their results with real industrial data. A literature review about the propylene production in loop reactors shows that the validation of a distributed model with actual industrial data is yet to be presented. A distributed mathematical model is presented for industrial liquid phase loop polypropylene reactors and validated with actual industrial data for the first time. The model is able to represent the dynamic trajectories of production rates, MFI and XS values during grade transitions within the experimental accuracy. The model indicates that the polymer quality can change significantly along the reactor train and that manipulation of feed flow rates can be successfully used for production of more homogeneous polymer products.     

Evolution of instrumentation for the study of gas-phase ion/ion chemistry via mass spectrometry

The scope of gas-phase ion/ion chemistry accessible to mass spectrometry is largely defined by the available tools. Due to the development of novel instrumentation, a wide range of reaction phenomenologies has been noted, many of which have been studied extensively and exploited for analytical applications. This perspective presents the development of mass spectrometry-based instrumentation for the study of the gas-phase ion/ion chemistry in which at least one of the reactants is multiply charged. The instrument evolution is presented within the context of three essential elements required for any ion/ion reaction study: the ionization source(s), the reaction vessel or environment, and the mass analyzer. Ionization source arrangements have included source combinations that allow for reactions between multiply charged ions of one polarity and singly charged ions of opposite polarity, arrangements that enable the study of reactions of multiply charged ions of opposite polarity and, most recently, arrangements that allow for ion formation from more than two ion sources. Gas-phase ion/ion reaction studies have been performed at near atmospheric pressure in flow reactor designs and within electrodynamic ion traps operated in the mTorr range. With ion trap as a reaction vessel, ionization and reaction processes can be independently optimized and ion/ion reactions can be implemented within the context of MSn experiments. Spatial separation of the reaction vessel from the mass analyzer allows for the use of any form of mass analysis in conjunction with ion/ion reactions. Time-of-flight mass analysis, for example, has provided significant improvements in mass analysis figures of merit relative to mass filters and ion traps.     

固定床反应器参数灵敏性与失控分析

本文采用邻二甲苯氧化的复合反应动力学模型分析了固定床反应器的参数灵敏性和失控行为,并与该反应的简单反应动力学模型的研究结果作了比较,发现二者间有显著的差别。本文还考察了固定床反应器对冷却介质流量和进口温度的灵敏性,发现反应器对冷却介质流量和进口温度的发迹极其敏感。因此对于强放热反应过程,考虑反应器对冷却介质的流量和进口温度的参数灵敏性对反应器的设计和控制是必要的。