Vol. 4, No.2 JOURNAL OF CHEMICAL INDUSTRY AND ENGINEERING (CHINA) 1989 A STUDY ON MASS TRANSFER IN PULSED SIEVE-PLATE EXTRACTION COLUMN Quan Yut(42_ #8), Fer Wervane (48 3%) aND WANG JIADING (3E 3% 38) Department of Chemical Engineering, Tsinghua University, Beijing, China) Abstract Mass transfer experiments have been carried out ina 40mm diameter pulsed sieve-plate extraction column. Both standard and “dispersion-coalescence™ type cartridges were tested with 30% TBP (kerosene as diluent)/ Nitric Acid/Water system. “Ture” volumetric mass transfer coefficient and backmixing parameters in contin- uous and dispersed phases were simultaneously evaluated from the steady state concentration profiles of both phases based on the stage backmixing model. Drop sizes and dispersed phase hold-up in the column were meas- show that the tured at the same time. Overall mass transfer coefficients were then calculated. The resul ‘mass transfer characteristics of pulsed sieve-plate extraction column can be predicted by the single turbulent circulating drop mechanism. 1. Introduction The investigation of mass transfer characteristics of liquid-liquid extraction process has been focussed on two aspects: (1) Theoretical analysis and experimental investigation of mass transfer inside and outside single drops: The mass transfer rates fo single drops have been extensively studied with different models established('-®, These works laid the foundation uous phase and the swarm of drops in an ex- for the analysis of mass transfer between the cont traction column. However, for the practical design, the relation between these models and the actual circumstances in extraction columns should be further explored. (2) Evaluation of volumetric mass transfer coefficient from measured solute concentration profiles: This method has been successfully developed by Smoot‘, Zilkowaskit”, Lei Xia et al. The steady state concentration profiles of two phases in pulsed sieve-plate columns were measured, from which, mass transfer and axial mixing parameters were estimated based on the diffusion model. Thus, “true” and “apparent” Height of Transfer Unit Hoc, Hocy can be cal culated. However, data of interphase mass transfer coefficient, Ky; in the pulsed sieve- plate column are still lacking, since the drop size and interfacial specific area in extractors are difficult to measure or correlate under the conditions of mass transfer operation, while the physical properties of solvent, drop size distributions and the flow behavior influence Received November 8, 1986, Journal of Chemical Industry and Engineering (Chinese Edition), 39{S], 522(1988), * Author to whom correspondence should be addressed,MASS TRANSFER IN EXTRACTION COLUMN 219 the mass transfer performance significantly. Work described in this paper concerns the mass transfer experiments in a pulsed sieve- plate column, from which the interphase mass transfer coefficients were estimated and the rela~ tionship between the mass transfer processes in actual extraction columns and the single drop mechanism was analyzed. ‘The comparison of two kinds of cartridge indicate the possible way of improving the performances of extraction columns. TL, Experiment The extraction column was constructed from hard glass tube of 40 mm inner diameter with an effective height of 1.12m", Two kinds of cartridges were adopted in the experiments: (1) standard cartridge; (2) “dispersion-coalescence” type cartridge. The liquid-liquid system tested is 30% Tributyl Phosphate (TBP) in kerosene as dispersed phase, and water as continuous phase. Nitric acid as solute is transferred from the continuous phase to dispersed phase. Eight pairs of samplers were arranged along the column. Samplers for aqueous phase were stainless steel needles. As to samplers for dispersed phase, an organic wetting polyethy!- ene cup was attached to the needle to get organic sample free from water. Mass transfer operation reached a steady state in about one hour after starting up of the column. Then, sampling operation was carried out and pure samples free from the other phase were obtained. Nitric acid concentrations were analyzed by alkalimetry. Flow rate of sampling was less than 0.5% of flow rate of two phases. The drop sizes were measured by photography. A camera equipped with extension lube was used, with an exposuse time 1/1000 s, The dispersed phase hold-up was estimated by volumetric replacement method. Il, Mathematical Model and Calculation Either the diffusion model or stage backmixing model could be used to described the mass transfer and axial mixing in extraction columns, while the latter was adopted in this work. In the stage backmixing model, as shown in Fig. 1, assuming constant model parameters and constant flow rates throughout the column, a material balance for steady state mass trans- given as follows: AW oxi (L42a)V oxi + (1+a)Voxins— Koca(xi— fol yi) )h=0 (1) (1+ B)V nyins— LF 28)V ny t AV yin +K ocala — fel yi) )h (2) where closed boundary conditions are assumed. With given composition of two feed streams fer operation in jth cell and model parameters (a,8,Koca, 2N simultancous equations can be solved to obtain sey). Comparison of these with a set of concentration profiles xjca15 Yiea (f= measured steady state concentration profiles xj.0a> (7 gives a maximum likelihood function: gyms) Vien (G= 1s ynty)220 IOURNAL OF CHEMICAL NDUSTRY AND ENGINEFRING (CHINA) Koot tn ~ Sen = (Ih oe ove ena} frrerer Ca¥ yeah Ve In { Cte Ve tnt (it a) Mp eves, { AV Pia a (xj fyb , ee ee oreo Cte Vex (rarer BV J [cis ave x aay, even | \c em TAK Mp | ah yt nr Kyca (ni Sef, Fig, 1 Schematic of stage backmixing model Flay K oa) DS Gehan een EDS (Vise aie)! (3) 4 i while the parameters (Kgca,a and f) could be obtained from measured concentration iable non-linear equa- profiles by the method of optimal parameter estimation for multi tions. A computation algorithm is proposed in coordnation with the need to process ex- perimental data for systems with non-linear phase equilibrium behavior. Parameters thus evaluated are in agreement with those from the algorithm proposed by Ricker and Kingt'®), but the computing time is considerably reduced as some reasonable simplifications have been made in our program, Calculated concentration profiles fit well to the measured ones (Fig. 2). The method of random error analysis indicates that the deviations of estimated parameters are 3% for Koca and S—10% for g and 8 while a deviation of 1.5% for measured profiles is imposed. The interfacial specific area g was calculated from the measured drop size distribution and hold-up of the dispersed phase: Dndi xs nd Slate Sad: Seay Then, the overall mass transfer coefficient K’., can be obtained as (4)MASS TRANSFER IN EXTRACTION COLUMN 221 mol/L 0 02 04 06 0.8 1.0 112 Fig. 2. Comparison of measured and calculated concentration profiles Af =25mm/|s; Ve=1.2mmjs; Vo=3.4 mm/s; © measured; —— calculated - Koca _m-Koca-dy Koy 3 (3) In order to describe the mass transfer process in a column with single drop model, the specified operating conditions should be considered, In a study of the mass transfer mechanism in a reciprocating sieve-plate column, Tojo & Miyanami™ pointed out that a drop with diameter smaller than the critical drop size d, can be considered as a stagnant drop. . d.=0.005/0/Ap (6) where er is the interfacial tension. According to this criterion, the critical size should be 0.36 mm for the present system. But in the operation region of the present work, drop sizes are in the range of 0.5—4.0 mm. Deduced from Hadamard’s flow pattern function and some experimental investigationst'*) , the laminar circulating mechanism generally occurs when drop Reynolds number Re<10. In this work, drop Re is larger than 30, drops showed dis- tortion and swing to various extents, that means the turbulent circulating pattern is dominating, In this case, Handlos-Baron equation!" is adopted bas = 1680 Fn Fhe) (asic. /S wie) m where 4, and B, are eigenvalues and coefficients of the Sturm-Liowville equation respec- tively, with 4, =2.88. The exponential terms C,=exp[ —A;uet/[128d(1 +4a/uc) I], decrease very rapidly for longer than one second of contact time. So a simplified turbulent circulating single drop mass transfer model Handlos-Baron model is given as222 JOURNAL OF CHEMICAL INDUSTRY AND ENGINEERING (CHINA) 7681 + s/c) (#) Correspondingly, Garner equationt*l is adopted as the mass transfer model for outside of drops. She= 50 +0,0085ReS (9) In the region of this investigation (Re =30—230), the values of Sie calculated from this equation are close to those from Higbie's surface penetration theory, She= (durd/De)'* (Go) and those from Su’s experimental study of single drop mass transfer in continuous phase. Overall coefficient can be calculated from the concept of additivity of resistances. 1 1,1 oo ha * minke on It is found that the resistance inside the drop is about ten times higher than outside the drop for the testing system of this work. IV. Results and Discussions 1. Mean drop size and dispersed phase hold-up Since the drop sizes of the dispersed phase in an extraction column are of random dis- tribution, the mean drop size is obtained from the statistics of a large number of drops. The negative films of photographs were enlarged to 20 times. Three to four hundred drops were counted and fed into a TI-S9 programmable calculator for calculation of the mean drop size. The intensity of pulsation has a significant influence on the mean drop size, as shown in Fig. 3. An emperical equation of correlation was obtained: dy:=7 85 x 107*(Af)-°" (12) e,| Fig. 3 Mean drop size d, versus 3 pulsation intensity (Af) x (standard cartridge) = 1 0-005 0.01 0.02 0.05 As, misMASS TRANSFER IN EXTRACTION COLUMN 223 The coefficient in this equation will vary with the physical properties of systems and/or the geometries of columns. Drop size decreases sharply with the increase of pulsation intensity while the dispersed phase hold-up increases with it. In consequence, interfacial specific area increases and the flooding flux decreases. Therefore, an appropriate pulsation intensity must be carefully chosen to adjust the mass transfer rate and throughout in a column according to the process requirement. To obtain the data of interfacial specific area, it is desirable to correlate the mean drop size with the dispersed phase hold-up. In the region of emulsion operation, based on the ex- pression given in literature!*®, the data of this investigation can be tentatively correlated as Fe 5 = 85.80.06)" + (aa) Numerical constants in this equation will vary with the physical properties of the system tested. 2. Mass transfer characteristics of pulsed sieve-plate column with standard cartridge In general, the mass transfer performance can be expressed in “apparent” or “true” . Ve height of transfer unit, Hoey Of Hoc. Apparent height of transfer unit Hcy represents the overall mass transfer achievement. The height of a column is calculated as H=Hocr-N ace (a) while Hoc» can be divided into two parts ". Hoce=HoctHoow (15) where Hyc=Ve/Kocas and Hoc.p is called diffusional height of transfer unit, which can also be approximately calculated from the bach ing parameters of two phases. With in- crease of pulsation intensity, the changes of overali volumetric mass transfer coefficient K ca and diffusional height of transfer unit H{ yc,» are illustrated in Figs. 4 and 5 respectively. With the increase of pulsation intensity, the interfacial specific area g and Ka in- crease, and H oc, decreases correspondingly. However, further increase of Af will increase the hold-up, and hence increase the frequency of collision and coalescence between drops, Thus the increase of interfacial specific area will approach an upper limit. On the other hand, higher pulsation intensity enhances axial backmixing, and Hoc,o/Hocp may be Fig. 4 Koco versus Af224 JOURNAL OF CHEMICAL INDUSTRY AND ENGINEERING (CHINA) Fig. 3 Hoc.o/Hoce versus Af Hoc,» / Hoc, P T.0% Af, m/s higher than 0.5 in some cases, which means more than 50% of the column height being used to compensate the backmixing in two phases. Because both Hycp and Koc a are influenced comprehensively by a number of factors, it is difficult to apply them directly to the analysis of mass transfer process or to the engineering design reliably. Therefore, the accurate evaluation or prediction of interphase mass transfer coefficient Ao) becomes an important subject in the extraction column research and development 3. Comparison of K oy evaluated from the concentration profiles and predicted from the single drop mass transfer model ” Thirty five sets of steady state concentration profiles of two phases were measured and fitted with stage backmixing model to obtain the interphase mass transfer coefficient Kop. The variation of Ko, with slip velocity is shown in Tig. 6. Valucs predicted from the single drop mass transfer model is also presented for comparison. % Koo x10°, m/s Fig. 6 Comparison of measured and predicted Kop © standard cartridge; VY “dispersion-coalescence” type cartridge; — predicted by turbulent circulating drop mass transfer modelMASS TRANSFER IN EXTRACTION COLUMN 225 It can be seen that: (1) Interphase mass transfer coefficient increases with the increase of drop size and slip velocity. This tendency is consistent with other work, such as the single drop mass transfer investigation by Zhangt*}, and the experimental data in reciprocating plate column by Tojo and Miyanamit, the data in asymmetric rotating disc contactor by Misek‘**, and the data in rotating disc contactor by Strand‘*, Johnson", Korchinsky"'”, Zhangt'*) and others, According to the single drop models with stagnant or laminar circulating flow pattern, Kis proportional to the molecular diffusion coefficient but inversely proportional to drop size. In industrial extractors, circulating and interfacial turbulence may occur at a low Reynolds number, The circumstances are quite different from free rising or falling drops in static fluid. Therefore, it is unreasonable to predict the mass transfer process in liquid- liquid extraction column from stagnant or laminar circulating models. @) In Handlos-Baron model for drops with turbulent circulating pattern, Ky is proportional to the drop velocity 1, which is in turn proportional to the drop size in prac- tical operating region of extraction columns. This is in consistent with the results of our investigation. However, mass transfer coefficients reported in literature for other types of extractors ©! are about 30-70% of those predicted by Handlos-Baron model, while our results are about 80—110% in the pulsed sieve-plate column. Higher interphase mass transfer coefficient in the present case may result from more intensive turbulence and pulsation movement of flow which enhances the circulation in drops. 4. Comparison of mass transfer characteristics of columns with dispersion-coalescence (D-C) type cartridge and standard cartridge A specially designed louver type coalescence plate was made of plexiglass to make them wettable by organic phase. The “D-C type cartridge” was constructed from placing the louver plate into each of the three stainless steel sieve plates. Both the flooding throughput and the mass transfer efficiency are improved with D-C type cartridge in comparison with those obtained with the “standard” one. In order to have a clear understanding of differ- ent effects on mass transfer with the different types of cartridge, some of the experimental re- sults are illustrated in Fig, 7. It can be seen from Fig. 7: (1) In the column with D—C cartridge, the spacing between plates was reduced to one half of that of the standard catridge, resulting the number of plates doubled in a column of the same height. Owing to the increase of hindrance of plates and the coalescence and re- tardation of the louver plates to organic drops, the dispersed phase hold-up with D-C car- ‘ridge is higher than that with standard cartridge in the whole operation range. This increases the contact time and interfacial area of mass transfer between the two phases. (2) Besides the properties of system tested, the drop size in the extractor depends on two other factors: energy input and cartridge geometry. When the pulsation intensity | is at low level, drops are relatively large and the effect of cartridge on drop size is dominant226 JOURNAL OF CHEMICAL INDUSTRY AND ENGINEERING (CHINA) Fig. 7. Comparison of mass transfer performances of column with D-C cartridge and standard cartridge A. D-C cartridge © standard cartridge Kocaxio?, st 0.0T Os 0.02 0.035 Af, m/s in the pulsed sieve-plate column, Therefore, the drop size with D-C cartridge is obviously larger than that with standard cartridge owing to the coalescence of drops under the plexiglass plate, Whereas under the high level of pulsation intensity, most of the drops are smaller than the hole size of plate. The effect of type of cartridge on drop size is far less than the effect of pulsation intensity, thus the drop sizes in a column with cither of the two types of cartridge do not show much difference. (3) It can be seen from the above discussion that the interfacial specific area with D-C cartridge is larger than that with standard cartridge in emulsion operation region, so doesMASS TRANSFER IN EXTRACTION COLUMN 227 the volumetric mass transfer coefficient. In addition, D-C cartridge is effective in reducing the backming in column.t*) (4 At the same slip velocity /,, the interphase mass transfer coefficients Ky» in columns with two kinds of cartridge are close to each other, in spite of the notable differences in hydrodynamics and geometry of these two kinds of cartridge. This result is significant in applying single drop models to designing columns with internals of different configurations. V. Conclusions 1. Interphase mass transfer coefficients Ko, have been evaluated by concentration profile method coupled with the measurement of drop size, drop size distribution and hold-up in the pulsed sieve-plate extraction column, In connection with single drop mass transfer, Kop can be predicted from the mass transfer model of turbulent circulating drop, and practically same results are obtained for two types of cartridge with different geometry and wetting property to the dispersed phase. It may be concluded that Kop is a more important basic parameter than the other parameters for the design of extraction columns. 2. For the testing system used in the present work, mean drop size in pulsed sieve plate column can be calculated by the following equation (under mass trausfer condition): d,=7.85 x 10-°(AF)-"" By incorporating with the dispersed phase hold-up, interfacial specific area can be calculated, With the gy evaluated from the single drop mass transfer models, the volumetric mass transfer coefficient, Koya, can be estimated. 3. More work should be done with ditterent testing system to prove further the conclus— ions obtained at present. Acknowledgment This research was supported by a grant from the National Natural Science Foundation of China. Nomenclature 4 pulse amplitude (peak to peak), m D iffusivity coefficient, m:/s d drop diameter, m das volume/sueface mean size, m i pulse frequency, s+ Ze) phase equilibrium function HocsHoce “ture” and “apparent” height of a transfer unit, based on continuous phase, m k height of a stage in backmixing model, m KocsKon interphase mass transfer coefficient, based on continuous or dispersed phase, m/s k mass transfer coefficient in individual phase, m/s m equilibrium distribution coefficient, m=dx/dv N number of stages in backmixing model Re Reynolds number, Re=V adsrpe/ne Sh Sherwood number, Sh=kds./D 1 velocity of drop, m/s228 JOURNAL OF CHEMICAL INDUSTRY AND ENGINEERING (CHINA) v superficial velocity, m/s x solute concentration in the continuous phase, mol/L. > solute concentration in the dispersed phase, mol/L 2 distance along the column height, m ab backflow ratio in continuous phase or dispersed phase 6 hold-up of dispersed phase Pp density, g/m* au viscosity, Pa-s subscripts c continuous phase D dispersed phase a drop R slip or relative velocity . 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