Different efficiency toward the biomimetic aerobic oxidation of benzyl alcohol in microchannel and bubble column reactors: Hydrodynamic characteristics and gas–liquid mass transfer

The selective aerobic oxidation of benzyl alcohol to benzaldehyde has attracted considerable attention because benzaldehyde is a high value-added product. The rate of this typical gas–liquid reaction is significantly affected by mass transfer. In this study, CoTPP-mediated(CoTPP: cobalt(II) mesotetraphenylporphyrin) selective benzyl alcohol oxidation with oxygen was conducted in a membrane microchannel(MMC) reactor and a bubble column(BC) reactor, respectively. We observed that 83% benzyl alcohol was converted within 6.5 min in the MMC reactor, but only less than 10% benzyl alcohol was converted in the BC reactor. Hydrodynamic characteristics and gas–liquid mass transfer performances were compared for the MMC and BC reactors. The MMC reactor was assumed to be a plug flow reactor,and the dimensionless variance was 0.29. Compared to the BC reactor, the gas–liquid mass transfer was intensified significantly in MMC reactor. It could be ascribed to the high gas holdup(2.9 times higher than that of BC reactor), liquid film mass transfer coefficient(8.2 times higher than that of BC reactor), and mass transfer coefficient per unit interfacial area(3.8 times higher than that of BC reactor). Moreover,the Hatta number for the MMC reactor reached up to 0.61, which was about 15 times higher than that of the BC reactor. The computational fluid dynamics calculations for mass fractions in both liquid and gas phases were consistent with the experimental data.

Analysis and Measurement of Mass Transfer in Airlift Loop Reactors

Inter-phase mass transfer is important to the design and performance of airlift loop reactors for either chemical or biochemical applications, and a good measurement technique is crucial for studying mass transfer in multiphase systems. According to the model of macro-scale mass transfer in airlift loop reactors, it was proved that the airlift loop reactor can be regarded as a continuous stirred tank reactor for measuring mass transfer coefficient. The calculated mass transfer coefficient on such a basis is different from the volumetric mass transfer coefficient in the macro-scale model and the difference is discussed. To describe the time delay of the probe response to the change of oxygen concentration in the liquid phase, a model taking into account the time constant of response is es-tablished. Sensitivity analysis shows that this model can be used to measure the volumetric mass transfer coefficient. Applying this model to the measurement of volumetric mass transfer coefficient in the loop reactor, results that co-incide with the turbulence theory in the literate were obtained.

A convenient method for measuring gas-liquid volumetric mass transfer coefficient in micro reactors

The research on gas-liquid multiphase reactions using micro reactors is becoming increasingly widespread, given their excellent mass transfer performance. Establishing an accurate and reliable method to measure the gas-liquid mass transfer performance of micro reactors is crucial for evaluating and optimizing the design of micro reactor structure. In this paper, the physical absorption method of aqueous solution-CO_(2) and the chemical absorption method of sodium carbonate solution-CO_(2) were proposed. By analyzing the chemical reaction equilibrium during the absorption process, the relationship between the mass transfer of CO_(2) and the solubility of hydroxide ions in the solution was established, and the total gas-liquid mass transfer coefficient was immediately obtained by measuring the p H value. The corresponding testing platform and process have been established based on the characteristics of the proposed method to ensure fast and accurate measurement. In addition, the chemical absorption method takes into account temperature factors that were not previously considered. The volumetric mass transfer coefficient measured by these two methods is in the same range as those measured by other methods using the same microchannel structure in previous literature. The methods have the advantages of low equipment cost, faster measurement speed, and simpler procedures, which can facilitate its wide application to the evaluation of the mass transfer performance and hence can guide the structure optimization of microchannel reactors.

Experimental Study on the Hydrodynamics and Mass Transfer Characteristics of Airlift Loop Reactors (ALR)

The promoting effect of ultrasonic wave on the hydrodynamics and mass transfer characteristics of the airlift loop reactor was studied. The effect of the airlift reactor and ultrasonic wave on the reactor’s gas holdup, liquid circulation velocity, mixing time and overall volumetric mass transfer coefficient respectively with and without the presence of ultrasonic wave is empathetically examined and compared. The experiment has proven that the incorporation of ultrasonic wave has no effect on the gas holdup but has the tendency to gradually decrease the liquid circulation velocity and increase the overall volumetric mass transfer coefficient; the effect on the mixing time is relatively complex. At low gas velocity, low powered ultrasonic wave promotes the radial mixing of fluid; with the increase of ultrasonic power, ultrasonic vibration obstructs the radial mixing of fluid. Therefore, there exists an optimal ultrasonic power. Moreover, the effect of ultrasonic wave on the mixing time gradually decreases with the increase of the superficial gas velocity. Correlations were also proposed for the hydrodynamics and mass transfer characteristics of the reactor.

A Comprehensive Review of the Influence of Heat Exchange Tubes on Hydrodynamic,Heat,and Mass Transfer in Bubble and Slurry Bubble

Bubble and slurry bubble column reactors(BCRs/SBCRs)are used for various chemical,biochemical,and petro-chemical applications.They have several operational and maintenance advantages,including excellent heat and mass transfer rates,simplicity,and low operating and maintenance cost.Typically,a catalyst is present in addition to biochemical processes where microorganisms are used to produce industrially valuable bio-products.Since most applications involve complicated gas-liquid,gas-liquid-solid,and exothermic processes,the BCR/SBCR must be equipped with heat-exchanging tubes to dissipate heat and control the reactor’s overall performance.In this review,past and very recent experimental and numerical investigations on such systems are critically dis-cussed.Furthermore,gaps to befilled and critical aspects still requiring investigation are identified.

Experimental determination of gas holdup and volumetric mass transfer coefficient in a jet bubbling reactor

The hydrodynamics and mass transfer characteristics of a lab-scale jet bubbling reactor(JBR)including the gas holdup,volumetric mass transfer coefficient and specific interfacial area were assessed experimentally investigating the influence of temperature,pH and superficial gas velocity.The reactor diameter and height were 11 and 30 cm,respectively.It was equipped with a single sparger,operating at atmospheric pressure,20 and 40℃,and two pH values of 3 and 6.The height of the liquid was 23 cm,while the superficial gas velocity changed within 0.010-0.040 m·s^(-1)range.Experiments were conducted with pure oxygen as the gas phase and saturated lime solution as the liquid phase.The liquid-side volumetric mass transfer coefficient was determined under unsteady-state oxygen absorption in a saturated lime solution.The gas holdup was calculated based on the liquid height change,while the specific interfacial area was obtained by a physical method based on the bubble size distribution(BSD)in different superficial gas velocities.The results indicated that at the same temperature but different pH,the gas holdup variation was negligible,while the liquid-side volumetric mass transfer coefficient at the pH value of 6 was higher than that at the pH=3.At a constant pH but different temperatures,the gas holdup and the liquid-side volumetric mass transfer coefficients at 40℃were higher than that of the same at 20℃.A reasonable and appropriate estimation of the liquid-side volumetric mass transfer coefficient(kla)in a pilot-scale JBR was provided which can be applied to the design and scale-up of JBRs.

Hydrodynamics and Mass Transfer in a Modified Three-phase Airlift Loop Reactor

A modified internal-loop airlif reactor （MIALR） with a continuous slurry phase was studied to investigate the local hydrodynamic characteristics, including gas holdup, bubble size, bubble rise velocity and local mass transfer properties. Based on the analysis of geometrical construction and fluid properties of gas and slurry, MIALR was divided into six flow regions. In these flow regions, the local hydrodynamic characteristics were investigated over a wide range of operating variables. Furthermore, a new method was developed to measure the dissolved oxygen concentration. The volumetric mass-transfer coefficient in six flow regions was also calculated for comparison.

Modeling of mass transfer characteristics of bubble column reactor with surfactant present

Danckwert’s method was used to determine the specific interfacial area, a, and the individual mass transfer coefficient, kL, during absorption of CO2 in a bubble column with an anionic surfactant in the carbonate-bicarbonate buffer solution and NaAsO2 as catalyst, the presence of which decreases the specific interfacial area and the individual mass transfer coefficient. The specific interfacial area and the individual mass transfer coefficient increase with increasing su- perficial gas velocity. The specific interfacial area decreases whereas the individual mass transfer coefficient increases with increasing temperature. The results of experiments were used to determine the dependence of a, kL, and kLa on the surface tension, the temperature of the absorption phase, and the superficial velocity of the gas. The calculated results from the correlation were found to be within 10% deviation from the actual experimental results.

Transfer Characteristics in Mechanically Stirred Airlift Loop Reactors with or without Static Mixers

The mechanically stirred internal loop airlift reactors equipped with or without static mixers are devised for intensification of gas-liquid mass transfer rate. The influences of superficial gas velocity, agitation or static mixers on gas hold-up, mixing time, liquid circulating velocity and volumetric mass transfer coefficient have been investigated with tap water and carboxymethyl cellulose (CMC) aqueous solution. The experimental results indicate that mechanical agitation is more efficacious than static mixer in highly viscous media for improving mass transfer in airlift reactors. The empirical correlation of volumetric mass transfer coefficient with apparent viscosity, and energy consumption for mechanical agitation and aeration is developed.

Bubble size fractal dimension,gas holdup,and mass transfer in a bubble column with dual internals

As the scale of residual oil treatment increases and cleaner production improves in China,slurry bubble column reactors face many challenges and opportunities for residual oil hydrogenation technology.The internals development is critical to adapt the long-term stable operation.In this paper,the volumetric mass transfer coefficient,gas holdup and bubble size in a gas-liquid up-flow column are studied with two kinds of internals.The gas holdup and volumetric mass transfer coefficient increase by 120% and 42% when the fractal dimension of bubbles increases from 0.56 to 2.56,respectively.The enhanced mass transfer processing may improve the coke suppression ability in the slurry reactor for residual oil treatment.The results can be useful for the exploration of reacting conditions,scale-up strategies,and oil adaptability.This work is valuable for the design of reactor systems and technological processes.

HYSTERESIS OF GAS-LIQUID MASS TRANSFER IN A TRICKLE BED REACTOR

1 INTRODUCTIONTrickle bed reactors are widely used in the process industry,particularly in petroleumhydroprocessing operations,and have been extensively studied by chemical engineers.In atrickle bed reactor,the gas and liquid flow cocurrently down through the packed bedand undergo chemical reactions.However,there exist multiple hydrodynamic stateswhich correspond to either uniform or,in most cases,nonuniform radial distributionof the gas and liquid flows in the packed section.Moreover,the hydrodynamic state

CORRELATION BETWEEN HYSTERESIS OF GAS-LIQUID MASS TRANSFER AND LIQUID DISTRIBUTION IN A TRICKLE BED

The hysteresis of gas-liquid mass transfer rate and the corresponding radial liquiddistribution in a trickle bed reactor are measured to provide evidence for the correlation between thesetwo behaviors.Experimental results indicate that the hysteresis of gas-liquid mass transfer originatesfrom the nonuniformity of the hydrodynamic state of gas-liquid flow and the radial maldistributionof local kgia corresponds very well to the radial maldistribution of liquid flow in the bed.The localliquid flow rate is also found to be nonuniform in the azimuthal direction.In view of maldistributedliquid flow even in the pulsing flow regime,the conventional plug flow model seems oversimplifiedfor describing the behavior of a trickle bed.

FLOW BEHAVIOR AND MASS TRANSFER IN THREE-PHASE EXTERNAL-LOOP AIRLIFT REACTORS WITH LARGE PARTICLES

The flow behavior and mass transfer in a three-phase external-loop airlift reactor can be improved by adding large particles. The mass transfer and liquid dispersion behavior for a three-phase external-loop reactor with large particles are studied in terms of the effect of the diameter and loading of the large particles on the liquid dispersion coefficient and mass transfer coefficient, The results showed that increasing the diameter or loading of the large particles tend to decrease dispersion and intensify mass transfer, and that an increase in the diameter of the large particles remarkably decreases the particle loop rate, while the effect of fine particles is much less notable.

Investigation of extraction fraction in confined impinging jet reactors for tri-butyl-phosphate extracting butyric acid process

The extraction fraction E and overall volumetric mass transfer coefficient kka of TBP extracting butyric acid pro- cess in confined impinging jet reactors （CIJR） with two jets were investigated. The main variables tested were the concentration of tri-butyl-phosphate （TBP） and butyric acid, the impinging velocity V, the impinging velocityratio of two phases Vorg/Vaq, the nozzle inner diameter di and the distance L between the jet axes and the top wall of the impinging chamber. The results showed that E and kLa increase with an increase of the impinging velocity V, the concentration ofTBP Corg, and the impinging velocity ratio Vor/Vaq. However, E and kta decrease with an increase of the inner diameter d1 from 1 to 2 mm, the concentration of butyric acid Caq from 0.5% （v/v） to 2% （v/v）. The factor L ranging from 3 to 11 mm has a negligible effect on E and kLa. A correlation on these variables and kLa was proposed based on the experimental data. These results indicated good mass transfer oerformance of CIJR in the extraction operation.

Numerical Study on the Effects of Contraction Ratio in a Two-Phase Flow Injection Nozzle

The Euler-Euler numerical method was used to investigate the effects of contraction ratio on twophase flow mixing with mass transfer in the flow injection nozzle. The geometric shape of the nozzle was modified to improve carbonation efficiency. A gas inlet hole was created to increase the flow mixing of CO2 with water. A nozzle throat was also introduced to increase the gas dissolution by increasing flow rates. Various contraction ratios of nozzle throat, inlet gas and liquid velocities, and gas bubble sizes were employed to determine their effects on gas hold-up, gas concentration, and mass transfer coefficient. Results revealed that the flow injection nozzle with high contraction ratios improved carbonation because of high gas hold-up. Gas concentration was directly related to contraction ratio and gas flow velocities. Carbonation reduced when high liquid velocities and large gas bubbles were employed because of inefficient flow mixing. This study indicated that flow injection nozzle with large contraction ratios were suitable for carbonation because of their ability to increase gas hold-up, gas concentration, and mass transfer coefficient.

Coupled Transport Phenomena in Corrugated Photocatalytic Reactors

Corrugated reactors are known for their use in applications requiring UV-exposure, whereby media flowing within the corrugated channel react with a photo-active catalyst impregnated on the surface （i.e. TiO2）. The performance in these systems is dependent on catalyst properties and reactivity for a given light source, in conjunc-tion with the coupled transport of reactants within the media and photons falling incident to the catalyst surface. Experimental and computational analyses of local mass transfer and radiation pattems for a broad range of corrugation angles, depths, and non-idealities introduced during manufacture （i.e. fold curvature） are thus integrated to the design and optimization of these systems. This work explores techniques for determining incident energy distribu-tions on the surface of corrugated reactor geometries with non-ideal cross-sectional profiles, and the local and overall mass transfer rates obtained using computational fluid dynamics and experimental analysis. By examining the reaction kinetics for the photo-degradation of 4-chlorophenol over a TiO2 catalyst, the effects of surface area, energy incidence with photon recapture, and local mass transfer on overall reactor performance are presented to highlight ootimization concerns for these tvoes of reactors.

Intensification of Deep Hydrodesulfurization Through a Two-stage Combination of Monolith and Trickle Bed Reactors

Deep hydrodesulfurization （HDS） is an important process to produce high quality liquid fuels with ultra-low sul- fur. Process intensification for deep HDS could be implemented by developing new active catalysts and/or new types of reactors. In this work, the kinetics of dibenzothiophene （DBT） hydrodesulfurization over Ni-P/SBA-15/ cordierite catalyst was investigated at 340-380 ℃ and 3.0-5.0 MPa. The first-order reaction model with respect to both DBT and H2 was used to fit the kinetics data in a batch recycle operation system. It is found that both the activation energy and rate constant over the Ni-P monolithic catalyst under our operating conditions are close to those over conventionally used HDS catalysts. Comparative performance studies of two types of reactors, i.e., trickle bed reactor and monolithic reactor, were performed based on reactor modeling and simulation. The results indicate that the productivity of the monolithic reactor is 3 times higher than that of the trickle bed reactor on a catalyst weight basis since effective utilization of the catalyst is higher in the monolithic reactor, but the volumetric productivity of the monolithic reactor is lower for HDS of DBT. Based on simulation results, a two- reactor-in-series configuration for hydrodesulfurization is proposed, in which a monolithic reactor is followed by a tickled bed reactor so as to attain intensified performance of the system converting fuel oil of different sulfur-containing compounds. It is illustrated that the two reactor scheme outperforms the trickle bed reactor both on reactor volume and catalyst mass bases while the content of sulfur is reduced from 200 μg·g-1 to about 10 μ·g-1.

Overview of Fischer-Tropsch Synthesis in Slurry Reactors

A brief review of Fischer-Tropsch synthesis specially in slurry reactors is presented, covering reaction kinetics, activity and selectivity of catalysts, product distribution, effects of process parameters, mass transfer and solubility of gas. Some important aspects of further research are proposed for improving both theories and production.

Mass Transfer Characteristics of H_2 and CO in Mimicked F-T Slurry Bubble Column Reactor

The equilibrium solubilities,volumetric gas-liquid mass transfer coefficients kLa of H_2 and CO were measured as functions of temperature(298―513 K),pressure(1―3 MPa),superficial gas velocity(0.5―3 cm/s) and solid volume fraction(5%―25%) in liquid paraffin/iron-based catalyst slurry bubble column reactor.The volumetric mass transfer coefficients kLa were obtained by measuring the dissolution rate of H_2 and CO.The influences of the operation conditions,such as pressure,temperature,superficial gas velocity and catalyst concentration on kLa,were investigated.Two empirical correlations were proposed to predict kLa values of H_2 and CO in liquid paraffin/solid particles slurry bubble column reactor.The results showed that the equilibrium solubilities of H-2 and CO increased with an increasing temperature and pressure,and the solubility of CO was greater than that for H_2.It was found that the equilibrium solubility can be expressed by Henry's law.The volumetric mass transfer coefficients of H_2 and CO were of the same order of magnitude,and increased with the increase of pressure,temperature and superficial gas velocity.The presence of solid particles decreased kLa values of both H_2 and CO.

Mass transfer in the absorption of SO_2 and NO_x using aqueous euchlorine scrubbing solution

Attempts have been made to generate euchlorine gas by chlorate-chloride process and to utilize it further to clean up SO2 and NOx from the flue gas in a lab scale bubbling reactor. Preliminary experiments were carded out to determine the gas and liquid phase mass transfer coefficients and their correlation equations have been established. Simultaneous removal of SO2 and NOx from the simulated flue gas using aqueous euchlorine scrubbing solution has been investigated. Euchlorine oxidized NO into NO2 completely and the later subsequently absorbed into the scrubbing solution in the form of nitrate. SO2 removal efficiency around 100% and NOx removal efficiency around 72% were achieved under optimal conditions. Mass balance has been confirmed by analyzing the sulfate, nitrate, euchlorine and chloride ion using ion chromatograph/auto-titrator and comparing it with their corresponding calculated values.