Mass Transfer Studies in Stirred AirLift Reactor

In the present work, water and three phase compositions of Solka-Floc, a cellulose fiber for simulating the biomass in bacteria, yeast, and fungal fermentation were studied in a 1.4?m³ stirred airlift reactor. The fractional dispersed phase holdup and the overall volumetric mass transfer coefficients were measured. The dispersed phase riser gas holdup and overall volumetric mass transfer coefficients both increased with increasing riser superficial dispersed phase velocity (0.02–0.1?ms^?1) and agitator speed in the range of 0–5?rs^?1. An increase in the Solka-Floc concentration (1–3% w/v) was found to reduce ?_GR and K _L a _L . Empirical correlations have been developed for fractional dispersed phase gas holdup and overall volumetric mass transfer coefficients.     

On mass transfer effect due to electrolytically evolved gas

Based on the Ibl penetration model mass transfer equations for gas-evolving electrodes were derived and compared to the effect of forced convection. Experimental studies were conducted in a rectangular flow channel with the working electrode facing downward. The variables were linear bubble velocity, linear electrolyte velocity, nature of the gas and electrode position. Up to bubble velocities (U_x) of 2 and 6 cm s⁻¹ for O₂ and H₂ gases respectively, the thickness of the Nernst diffusion layer (δ_av) was described well by the equation δ_av = [Dd_eL/(U_x)_av]^1/3. Intermediate slopes between − 1/3 and − 1 were observed for O₂ bubble velocities between 2 and 6 cm s⁻¹. A theoretical derivation suggests that in the absence of bubble coalescence, the mass transfer effect due to laminar flow induced by electrolytically evolved gas exceeds that due to forced external laminar flow for all practical channel designs.     

EFFECTS OF GEOMETRY ON HYDRODYNAMICS IN EXTERNAL-LOOP AIRLIFT REACTORS

Experimental investigations were carried out in model external-loop airlift reactors. Two reactors of laboratory scale (riser liquid height ranged between 1.16-1.56 m, riser diameter 0.03 m, A_D/A_R ratio between 0.111-1,000, total liquid volume V_T = (1.189-2.446).10^-3m³) and pilot-plant scale (riser liquid height of 4.4 and 4.7 m, respectively, riser diameter 0.200 m, A_D/A_R ratio of 0.1225 and 0.040 m, total liquid volume, V_T = (0.144-0.170) m³) were used.

The influences of reactor geometry characterized by some parameter as: A_D/A_R ratio, liquid height in riser and downcomer and liquid height in gas separator, together with the amount of introduced air, on the basic hydrodynamic design parameters: gas holdup and liquid circulation velocity were analysed.

The influence of gas sparger design on gas holdup and liquid velocity was found to be negligible.

The experimental liquid circulation velocity was correlated using a simplified form of the energy balance in airlift reactors, valid for external-loop airlift reactors with almost complete phase separation at the top.

An original dimensionless correlation for gas holdup prediction involving superficial velocities of gas and liquid, cross sectional areas, dispersion height, riser diameter, as well as Froude number, was obtained.     

MASS TRANSFER AND PHASE HOLDUP CHARACTERISTICS IN THREE-PHASE FLUIDIZED BEDS

The effects of liquid surface tension (42.6 ∼ 72,4 mN/m) and viscosity (1 ∼214mPa • sⁿ), liquid (0.01 ∼0.12m/s) and gas (0.01 ∼0.20m/s) velocities and particle sizes (1 — 8 mm) on phase holdup and mass transfer coefficient ( k_La) have been determined in a 0.142 m-I.D. × 2.0 m-high Plexiglas column. The gas phase holdup increases with liquid velocity, and the rate of increase in gas phase holdup sharply increases with gas velocity in the bed of surfactant solutions. In the beds of 1.0 and 1.7 mm glass beads, the bed contraction occurs whereas in the beds of 2.3 mm glass beads the bed contraction does not occur with an aqueous soltuion of ethanol (σ = 50.4 mN/m). The value of k_La increases with decreasing surface tension (σ ) but it decreases exponentially with increasing liquid viscosity in continuous bubble columns and three-phase fluidized beds. In three-phase fluidized beds with surfactant solutions, k_La increases with gas and liquid velocities and particle size. In three-phase fluidized beds of viscous or surfactant soltuions, k_L,a can be estimated in terms of the energy dissipation rate based on the isotropic turbulence theory and a flow regime map is proposed based on the drift flux theory.     

油性微乳液的循环气升式反应器的流体力学和传质性能研究简

This study reports an experimental investigation on hydrodynamics and mass transfer characteristics in a 15.6x10-3 m3 external loop airlift reactor for oil-in-water micro-emulsions with oil to water volume ratio （φ） rang- ing from 3% to 7% （by volume）. For comparative purposes, experiments were also carried out with water. Increase in φ of micro-emulsion systems results in an increment in the gas holdup and a decrease in the volumetric gas-liquid oxygen transfer coefficient and liquid circulation velocity, attributed to the escalation in the viscosity of mi- cro-emulsions. The gas holdup and volumetric mass transfer coefficient for micro-emulsion systems are signifi- cantly higher than that of water system. Two correlations are developed to predict the gas holdup and oxygen trans- fer coefficient     

水力喷射-空气旋流器用于湿法烟气脱硫及其传质机理

在一种新型高效的气液传质设备--水力喷射-空气旋流器(WSA)中,以Ca(OH)₂料浆为吸收剂进行了模拟烟气湿法脱硫的实验研究。结果表明:脱硫率随进口气速增加而增加;随液体喷射速度增加先增加,增加到一定程度后几乎不变;随烟气中SO₂的进口浓度增加而减小,存在一适宜的Ca(OH)₂浓度和回流比。在气体流量24～72 m³·h^-1、循环液体量0.4～0.8 m³·h^-1、料浆中Ca(OH)₂浓度7500 g·m^-3时,对SO₂浓度为1891～6373 mg·m^-3的烟气进行湿法脱硫,脱硫率达88.9%～97.7%,且WSA的旋流气体和喷射液体在湿法脱硫中具有自清洁能力,未发现内部结垢和喷孔堵塞现象。总体积传质系数K_Ga、有效相界面积a均随进口气速u_G增大而增大,而总传质系数K_G随u_G增加变化较小;当液体喷射速度 u_L≤0.26 m·s^-1时,K_Ga和K_G随u_L增加快速增大,之后增加缓慢,而a随u_L几乎线性增加,K_Ga和K_G随吸收剂中Ca(OH)₂浓度c_L增加有一最大值。结合实验数据拟合得到了相关的经验公式,这些关联式能较好地预测WSA的湿法脱硫传质性能。气体旋流场强度对总体积传质系数K_Ga和有效相界面积a起支配作用,脱硫传质过程同时受气膜和液膜阻力控制,但以液膜控制为主。     

Influences of top clearance and liquid throughput on the performances of an external loop airlift slurry reactor integrated mixing and separation

A new developed external loop airlift slurry reactor, which was integrated with gas–liquid–solid three-phase mixing, mass transfer, and liquid–solid separation simultaneously, was deemed to be a promising slurry reactor due to its prominent advantages such as achieving continuous separation of clear liquid from slurry and cyclic utilization of solid particles without any extra energy, energy-saving, and intrinsic safety design. The principal operating parameters, including gas separator volume, handling capacity, and superficial gas velocity, are systematically investigated here to promote the capabilities of mixing, mass transfer, and yield in the pilot external loop airlift slurry reactor. The influences of top clearance and throughput of the clear liquid on flow regime and gas holdup in the riser, liquid circulating velocity, and volumetric mass transfer coefficient with a typical high solid holdup and free of particles are examined experimentally. It was found that increasing the gas separator volume could promote the liquid circulating velocity by about 14.0% at most. Increasing the handling capacity of the clear liquid from 0.9 m~3·h~(-1) to 3.0 m~3·h~(-1) not only could increase the output without any adverse consequences, but also could enhance the liquid circulating velocity as much as 97.3%. Typical operating conditions investigated here can provide some necessary data and guidelines for this new external loop airlift slurry reactor to upgrade its performances.     

Effect of electro-chemical properties of sodium salts of various anions on their diffusional parameters in symmetrical cellulose acetate membranes

A relation was obtained between electro-chemical properties of sodium salts (NaCl, NaBr, and Na₂SO₄), and the thermodynamic property of permeability in symmetrical cellulose acetate membranes, the distribution coefficient K and the kinetic property, the overall diffusion coefficients D. K and D were obtained by the method we proposed using measured unsteady- and steady-state dialysis data. The K values increase with the increase of water content and are in the range of 10⁻² for sodium halides and 10⁻³ for Na₂SO₄. D is found to increase with the increase of the solute concentration, and the extrapolated values of D to zero concentration D⁽⁰⁾ are obtained as 0.015–0.03 μm²/s and increase with the increase of water content in the membrane. D can be divided into the concentration independent diffusion coefficients in the dense part of the membrane D_d and in the porous D_p, applying a two-part (perfect or dense and imperfect or porous) model of the membrane. Contrary to D_d, D_p increases with the increase of W_w and can be correlated as D_p,c = _d exp (γ × W_w). It is shown that the averaged D_d, _D increases with the increase of the quantity of the ionic mobility u of the solutes at infinite dilution divided by valence, and that the parameter γ increases with the increase of the ionic mobility u. The value of K increases slightly with the increase of water content and decreases with the increase of the Flory—Huggins parameter χ. The Flory—Huggins parameter χ is calculated from the measured values of distribution coefficients and data obtained from the literature. And it was found that the gradient of linear decrease of χ (λ_cation) depends on equivalent ionic conductivity of anion of salt, λ_an.     

Interaction between Pt and MoO3 dispersed over alumina

Pt–xMo/γ-Al₂O₃ catalysts of different molybdenum loading (2–20 wt.%) and with 1 wt.% of platinum were prepared by successive wet impregnation after intermediate calcination. The structure, morphology and surface were characterized by various methods. The DRS results indicate the presence of octahedral Mo⁶⁺ and tetrahedral Mo⁶⁺ phases. It also evidences the presence of polymeric MoO_x species, responsible for the formation of a well dispersed surface sublayer and bulk MoO₃ crystalline phase. XPS results after reduction and passivation of the 1Pt and 1Pt2Mo revealed the presence of residual chlorine, in the form of surface species such as [Pt(OH)_xCl_y]_s and [PtO_xCl_y]_sfavoring the formation of well dispersed platinum particles. The TPD and FTIR results are consistent with the existence of new active sites of Pt in the presence of molybdenum loading. For low Mo content there is a H₂ spillover effect. These results confirm the decoration model of Pt encapsulation by partially reduced Mo species as well as H₂ storage and backspillover due to the generation of a bronze compound.     

带波纹隔板的平板式光生物反应器流动特性

在传统平板式光生物反应器中加入波纹形隔板,以其导流作用强化液体循环和气液传质,建立了新型带波纹隔板的平板式光生物反应器. 利用计算流体动力学(CFD)模拟及实验考察了该反应器的流动与传质特性及其影响因素. 结果表明,CFD模拟结果与实验测量值吻合良好,液体在上升区和下降区之间形成了良好的循环,随通气比增加,液相速度、平均气含率和溶氧体积传质系数均近似线性增加. 单位体积能量输入与平均液相体积传质系数之间有良好的线性关系. 综合各相关参数得到优化结构为：下降区/上升区截面积为1.62,隔板顶端到液面的距离为260 mm,隔板底端到反应器底部的距离为20 mm.     

AFeO3 (A=La, Nd, Sm) and LaFe1−xMgxO3 perovskites as methane combustion and CO oxidation catalysts: structural, redox and catalytic properties

Catalytic methane combustion and CO oxidation were investigated over AFeO₃ (A=La, Nd, Sm) and LaFe_1−xMg_xO₃ (x=0.1, 0.2, 0.3, 0.4, 0.5) perovskites prepared by citrate method and calcined at 1073 K. The catalysts were characterized by X-ray diffraction (XRD). Redox properties and the content of Fe⁴⁺ were derived from temperature programmed reduction (TPR). Specific surface areas (SA) of perovskites were in 2.3–9.7 m² g⁻¹ range. XRD analysis showed that LaFeO₃, NdFeO₃, SmFeO₃ and LaFe_1−xMg_xO₃ (x·0.3) are single phase perovskite-type oxides. Traces of La₂O₃, in addition to the perovskite phase, were detected in the LaFe_1−xMg_xO₃ catalysts with x=0.4 and 0.5. TPR gave evidence of the presence in AFeO₃ of a very small fraction of Fe⁴⁺ which reduces to Fe³⁺. The fraction of Fe⁴⁺ in the LaFe_1−xMg_xO₃ samples increased with increasing magnesium content up to x=0.2, then it remained nearly constant. Catalytic activity tests showed that all samples gave methane and CO complete conversion with 100% selectivity to CO₂ below 973 and 773 K, respectively. For the AFeO₃ materials the order of activity towards methane combustion is La>Nd>Sm, whereas the activity, per unit SA, of the LaFe_1−xMg_xO₃ catalysts decreases with the amount of Mg at least for the catalysts showing a single perovskite phase (x=0.3). Concerning the CO oxidation, the order of activity for the AFeO₃ materials is Nd>La>Sm, while the activity (per unit SA) of the LaFe_1−xMg_xO₃ catalysts decreases at high magnesium content.     

微通道内单乙醇胺水溶液吸收CO2/N2混合气的传质特性

采用高速摄像仪对400 μm×400 μm T形微通道内单乙醇胺（MEA）水溶液吸收混合气中CO₂过程的气液两相流及传质特性进行了实验研究,微通道内的压力降采用压力传感器进行测量。考察了弹状流型下气液两相流量及MEA浓度对压力降、比表面积和传质性能的影响。结果表明,当MEA浓度不变,气液两相流量增大时,压力降、比表面积、传质系数、体积传质系数和增强因子均增大,并逐渐趋于恒定。当气液流量不变,MEA浓度增大时,压力降、传质系数、体积传质系数和增强因子增大,但比表面积减小。实验条件下,压力降范围为2.00~5.23 kPa,化学吸收过程的传质系数范围为7.74×10^-4~2.97×10^-3 m·s^-1。对于伴有快速化学反应的传质过程,以Sherwood数、Reynolds数、Schmidt数及增强因子为变量建立了体积传质系数的预测关联式,平均偏差为5.09%,具有良好的预测性能。     

气升式外环流反应器的体积传质系数

以Higbie的渗透理论和Kolmogoroff的湍流理论为基础,提出了计算液体旋涡在气液相界面暴露时间的方法,并建立了预测体积传质系数的模型方程。在不同管径比下的外环流反应器中,对空气 水体系测定了操作气速对体积传质系数、循环液速和气含率的影响。将体积传质系数与表观气速和下降管与上升管的面积比按幂函数进行关联,其预测值和试验值符合较好。     

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, p H 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 p H 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 p H, the gas holdup variation was negligible, while the liquid-side volumetric mass transfer coefficient at the p H value of 6 was higher than that at the p H = 3. At a constant p H 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.     

PHASE HOLDUPS AND LIQUID-LIQUID EXTRACTION IN THREE PHASE FLUIDIZED BEDS

Effects of the continuous phase velocity (0.01-0.08 m/s(, the dispersed phase velocity (0.0-0.04 m/s) and particle size (1.0-3.0 mm) on the individual phase holdups and the mass transfer coefficient have been determined in two (liquid-liquid) and three (liquid-liquid-solid) phase fluidized beds.

In the beds, the dispersed phase holdup increased with dispersed phase velocity but it decreased with continuous phase velocity. Whereas the continuous phase holdup decreased with dispersed phase velocity but it increased with continuous phase velocity. The bed porosity increased with both the dispersed and continuous phase velocities in the beds of 1.7 and 3.0 mm particles. In addition, the continuous phase holdup decreased with the presence of solid particles in the bed, however, the dispersed phase holdup was not affected by the presence of the particles.

The overall mass transfer coefficients in the continuous and dispersed phases increased with increasing fluid velocities but it decreased with the bed height.

The continuous phase holdup and mass transfer coefficient data have been correlated with the operating variables and the dimensionless groups.     

Sulfuric acid formation over ammonium sulfate loaded V2O5–WO3/TiO2 catalysts by DeNOx reaction with NOx

Operating the SCR DeNO_x reactor at temperatures below 200 °C results in a considerable saving in operating costs. Plant experience shows that on the catalysts in these second generation DeNO_x plants, even for flue gases with SO₂ concentration below 10 mg/m³, over 1–2 years operating time sizeable quantities of ammonium sulfates accumulate. Ammonium sulfates deposited on V₂O₅–WO₃/TiO₂ catalysts react with NO_x to nitrogen and sulfuric acid. Second-order rate constants of this reaction for temperatures of 170 °C have been derived. It could be shown that the sulfuric acid formed on the catalyst is displaced by water vapour and desorbs resulting in gas phase concentrations of up to 6.5 mg acid/m³ flue gas. Plant equipment downstream of the ammonium sulfate containing low temperature DeNO_x catalysts has to be protected against the corrosive action of the sulfuric acid in the flue gases leaving the DeNO_x reactor.     

CO2在正戊醇中的溶解度和体积传质系数

基于等体积饱和法搭建了气体在液体中溶解度与体积传质系数的实验测量系统,该实验系统温度、压力、溶解度、体积传质系数的扩展不确定度分别为0.02 K、0.01%、2%、4%。利用该实验系统测量了温度为323～343 K、压力为0.9～5.0 MPa范围内CO₂在正戊醇中的溶解度和体积传质系数。CO₂在正戊醇中的摩尔分数随着压力的升高而升高,在温度为323 K时,压力从2.5 MPa升高到3.2 MPa,溶解度升高26%。CO₂在正戊醇中的摩尔分数随着温度的升高而减小,在压力为0.9 MPa时,温度从323 K升高为343 K,溶解度降低26%。升高温度和压力都有利于提高体积传质系数,当温度和初始压力分别由323 K、1.1 MPa升高至343 K、5.0 MPa时,CO₂在正戊醇中的体积传质系数由0.0089 s^-1升高至 0.0175 s^-1。     

Palladium-substituted lanthanum cuprates: application to automotive exhaust purification

A series of palladium-substituted La₂CuO₄, corresponding to the formula La₂Cu_{1 −x}Pd_xO₄ (x = 0−0.2) were prepared by metal nitrate decomposition in a polyacrylamide gel. This method allows an easy incorporation of palladium in the mixed-oxides, which are formed at moderate temperature with rather high specific areas (13–17 m²/g). The partial substitution of copper for palladium allows a strong improvement of the three-way catalytic activity, in particular for NO reduction. The light-off temperatures for the conversions of CO, NO and C₃H₆ decreased markedly when increasing the palladium content, the activity of catalysts La₂Cu_0.9Pd_0.1O₄ and La₂Cu_0.8Pd_0.2O₄ being comparable to that of a Pt-Rh/CeO₂–Al₂O₃ catalyst for NO reduction, and higher for CO and C₃H₆ oxidation.

All the La₂Cu_{1 − x} Pd_xO₄ catalysts are activated under reacting conditions. This activation corresponds to the destruction of the mixed-oxide structure, with formation of reduced Pd⁰ ions atomically dispersed, surrounded by Cu⁺ and Cu²⁺ species on a lanthanum oxycarbonate matrix. This high dispersion state of the two transition metals in various oxidation states is supposed to originate from the initial La₂Cu_{1 −x}Pd_xO₄ structure.     

Preparation and characterization of inexpensive heterogeneous catalysts for air pollution control: Two case studies

Relatively inexpensive heterogeneous catalysts for two reactions of great importance in air pollution control, NO reduction and VOC combustion, were prepared and characterized. Apart from their common practical goal and the frequent need for simultaneous removal of air pollutants, these reactions share a similar redox mechanism, in which the formulation of more effective catalysts requires an enhancement of oxygen transfer.

For NO reduction, supported catalysts were prepared by adding a metal (Cu, Co, K) using ion exchange (IE) and incipient wetness impregnation (IWI) to chars obtained from pyrolysis of a subbituminous coal. The effects of pyrolysis temperature, between 550 and 1000 °C, on selected catalyst characteristics (e.g., BET surface area, XRD spectrum, support reactivity in O₂) are reported. For IE catalysts, the surface area increased in the presence of the metals while the opposite occurred for IWI catalysts. For the Co-IE catalysts, the highest surface area was obtained at 700 °C. The XRD results showed that, except for Cu (which exhibited sharp Cu⁰ peaks), the catalysts may be highly dispersed (or amorphous) on the carbon surface. For the C–O₂ reaction the order of (re)activity was K  Co > Cu for IE catalysts and K > Cu > Co for IWI catalysts. For NO reduction the orders were K > Co > Cu (IE catalysts) and Cu > Co > K (IWI catalysts). In all cases the catalytic (re)activity for NO reduction was lower than that exhibited for the C–O₂ reaction. The K-IE and Cu-IWI catalysts appeared to be the most promising ones, although further improvements in catalytic activity will be desirable. Some surprising results regarding CO and CO₂ selectivity are also reported, especially for Co catalysts.

In VOC combustion, the effect of the nature of ion B (Fe and Ni) on the partial substitution of ion A (Ca for La) in ABO₃ perovskites (e.g., LaFeO₃ and LaNiO₃) and on their catalytic activity was studied. The perovskite-type oxides were characterized by means of surface area measurements, XRD, temperature-programmed desorption (TPD) and temperature-programmed reduction (TPR). The effect of partial substitution of La³⁺ by Ca²⁺ was more significant for the La_1−xCa_xFeO₃ perovskites. In this case, the electronic perturbation is compensated by an oxidation state increase of part of Fe³⁺ to Fe⁴⁺. The TPD results revealed that, at higher substitution levels, oxygen vacancies are also formed to preserve electroneutrality. For the La_1−xCa_xNiO₃ perovskites, the characterization results showed no evidence of large differences in electronic properties as calcium substitution increases. The La_1−xCa_xNiO₃ perovskites exhibited lower activity than the simple LaNiO₃ perovskite, whereas for the La_1−xCa_xFeO₃ substituted perovskites the most active catalyst (exhibiting the lowest ignition temperature) was obtained at the highest substitution level, La_0.6Ca_0.4FeO₃.

The performance of both groups of catalysts is briefly discussed in terms of redox processes, in which the interplay between oxygen transfer and electron transfer requires further elucidation for the improvement of catalytic activity.