Review

Review
Utilization of Micromixers for Extraction Processes
By Kurt Benz, Klaus-Peter Jckel, Klaus-Jrgen Regenauer, Jrg Schiewe, Klaus Drese, Wolfgang Ehrfeld, Volker Hessel, and Holger Lwe* The aim of the investigation was to evaluate the extraction performance of a mixer settler set-up for miniplant technology using static micromixers as an alternative to conventional stirring apparatuses. A comprehensive experimental study was conducted at BASF AG to broaden the technology base for the extraction unit operation which is well established for miniplants in order to be utilized for microplant systems. The work proved that micromixers, or micromixer arrays, are highly efficient apparatuses for extraction purposes. The extraction efficiency was found to be a function of volume flow, which could be explained in light of the volume flow dependence of the mean droplet size and, hence, the specific surface area of the dispersions intermediately formed. At optimal flow conditions, one practical mixer settler stage was found to yield one theoretical plate for most systems investigated.

1 Introduction
Extraction is an important unit operation in chemical technology. In most cases it includes two steps: the formation of a dispersion and subsequent phase separation. A range of different apparatuses including mixer settler cascades, counter-current-, sieve plate-, packed-, pulsed- and rotating disc extraction columns are utilized in chemical production. In miniplants, BASF exclusively employs mixer settler cascades for reasons of scale-up simplification. The main parameters governing extraction processes are mass transport across the phase boundary, interfacial kinetics and mass transport phenomena within the bulk phase. Since mass transport by diffusion from one phase into the other is greatly facilitated by a large specific surface area, efficient dispersion is an indispensable prerequisite to achieve total phase saturation, characterized by thermodynamic equilibrium. The specific surface area itself is inversely related to the droplet size of the disperse phase. Recently, micromixers have been utilized for the generation of emulsions as well as for gas liquid dispersions and creams [13]. Investigating a silicon oil/water model system, it was found that micromixers produce emulsions with micrometer-sized droplets showing a remarkably narrow density distribution. Depending on the flow rate, droplet diameters of 60 down to 20 lm were measured [1] which correspond to extremely large specific surface areas of 50,000 to 160,000 m2/m3, respectively. Hence, mass transport by diffusion should be completed within milliseconds due to the large surface to volume ratio and the short diffusional length. These considerations and the fact that mixer settler configurations are preferably utilized for miniplant technology motivated the evaluation of the feasibility of using these micromixers for extraction purposes in a mixer settler
[*] K. Benz, K.-P. Jckel, K.-J. Regenauer, BASF AG, 67056 Ludwigshafen, Germany; J. Schiewe, K. Drese, W. Ehrfeld, V. Hessel, H. Lwe, Institut fr Mikrotechnik Mainz GmbH, Carl-Zeiss-Str. 18-20, 55129 Mainz, Germany.

configuration. In continuously operated miniplants, typical volume flows of 0.13 L/h are utilized. The reactor volume normally ranges between 0.1 and 10 L. Using micromixers with 30300 microchannels, volume flows of the same order of magnitude can be realized, and hence, qualify these devices to be used in miniplants. Furthermore, these micromixers are designed to be operated at pressures up to 30 bar. Besides the technically valuable features of micromixers, i.e., their small physical size, high mixing performance and modular design, their low price compared to standard stirring apparatuses also motivated the following investigations.

2 Experimental
All experiments characterizing the extraction efficiency of micromixers were performed in a mixer settler flow configuration using micromixers in combination with standard miniplant settler systems (Fig. 1). Two types of static

Figure 1. Photograph of the experimental setup comprising feed lines, filters, pressure sensors, micromixer and 150 mL settler.

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Review micromixers developed at IMM GmbH were utilized for different volume throughputs. For low and medium total volume flow rates of up to 1.6 L/h a micromixer utilizing the multilamination principle was used comprising 30 interdigital microchannels of 40 lm width (Fig. 2) [1,4]. To maintain a continuous flow without pulsation, piston pumps (Labotron) were used comprising two pistons, allowing a maximum volume flow of 1 L/h at a maximum pressure of 50 bar. The different physical properties of aqueous and organic phase in some cases resulted in a pressure difference of the feed flows. Although, at high flow rates pressure differences of up to 4 bar were formed across the microstructure, damage of the mixing element was never observed. For all other experiments at higher total flow rates of up to 6400 mL/h, a micromixer array was employed comprising 300 microchannels arranged in 10 parallel segments of equal microstructure as described above for the micromixer (Fig. 3) [1,4]. For flow rates above 1 L/h, two flow controlled gear pumps (Ismatec) were employed. To prevent clogging in all experiments, 7 lm pore filters (Nupro) were inserted into the feed lines to the micromixing devices. Initial experiments were carried out using a minisettler with a 15 mL internal volume (Fig. 4A). Since at total volume flow rates over 400 mL/h the capacity of this minisettler was exceeded, in all following experiments reported in section 3 the smallest standard miniplant settler available at BASF with 150 mL volume was used (Fig. 4B, C). All chemicals used were of highest purity. The volumetric flow ratio of extract phase and raffinate phase for all

Figure 4. Settler: A) minisettler of 15 mL volume, B) settler of 150 mL volume, and C) settler of 150 mL volume with heating jacket.

experiments was set to one. During the course of the extraction experiments the volume flows were increased stepwise each time by a factor of 2 starting at 100 mL/h when using the micromixer and 400 mL/h when using the micromixer array. After reaching the highest flow rates (800 mL/h and 3,200 mL/ h when using the micromixer and the micromixer array, respectively), the experiment was continued, now successively decreasing the volume flows to check for hysteresis effects. The amount of the extracted compound in the extract and raffinate was determined by gas chromatography. Experiments to establish the Nernst partition coefficient k were carried out for all model systems in a 1 L separation funnel by shaking for 250 min and analysis of the extracted compound in both phases.

3 Results and Discussion

In order to evaluate the efficiency of micromixers for extraction processes in a miniplant mixer settler set-up, various experiments were conducted investigating four different model systems as compiled in Tab. 1. The first three model systems shown in Tab. 1 are recommended standard systems of the European Federation of Chemical Engineering (EFCE) [5] whereas system 4 is an application example of BASF. All systems considerably differ in their interfacial tension (Dr, see Tab. 1). System 1, water (acetone)/toluene having the highest Dr of 33 mN/m, poses high demands on the mixing efficiency, whereas system 3, water (succinic acid)/n-butanol of low Dr readily forms an emulsion that is difficult to break. In all experiments, no difficulties were encountered concerning phase separation. The observation of alternating plugs of equal
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Figure 2. Photographs of a 30 channel static micromixer.

Figure 3. Photographs of a 300 channel micromixer array.

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Review volume of the two phases in the outlet tube right behind the micromixing devices indicated immediate and complete phase separation, even for system 3 having the smallest Dr of 1.7 mN/m.
Table 1. Model systems used to evaluate the extraction efficiency of micromixers. Raffinate phase water water water water Component acetone (10 wt%) acetone (10 wt%) succinic acid (5 wt%) dl-pantolactone (10 wt%) Extract phase toluene n-butyl acetate n-butanol methyl-isobutylketone Dr* [mN/m] 33.0 14.0 1.7 Table 2. Results of the experimental determination of thermodynamic partition coefficients for all systems. Model system 1) 2) 3) 4) Water Water Water Water Partition coefficient Experiment Literature value [5] (acetone, 10 wt%)/ toluene 0.83 0.82 (acetone, 10 wt%)/ butyl acetate 0.96 0.96 (succinic acid, 5 wt%)/ butanol 1.23 1.23 (pantolactone, 10 wt%)/ MiBK* 1.18

*MiBK: methyl-isobutyl-ketone

1) 2) 3) 4)

*interfacial tension

rates of extract phase and raffinate phase was set accordingly. A ratio of one resulted in almost equal quantities of the extracted component in both phases, thus, minimizing the analytical effort for quantification.

Prior to the investigation of the phase partition of the extracted compound as a function of the volume throughput, the thermodynamic partition coefficient was measured for each system in a long-term experiment (250 min) and compared to literature values. The results are listed in Tab. 2. As can be seen from Tab. 2 excellent agreement of experimental and literature values was found indicating the validity of the experimental method used. Since the Nernst coefficients of all systems are close to one, the ratio of flow

3.1 Results Utilizing One Micromixer Fig. 5A shows the phase partition values obtained for system 1, water (acetone)/toluene as a function of the total volume flow. The phase partition was calculated as the quotient of the acetone concentration in the extract and raffinate phases (determined as weight percent). At flow rates above 800 mL/h, conditions close to thermodynamic equilib-

Figure 5. Phase partition as a function of volume flow using a 30 channel static micromixer: A) system 1, water (acetone)/toluene, B) system 3, water (succinic acid)/n-butanol, C) system 4, water (dl-pantolactone)/methyl-isobutylketone and D) comparison of the results in terms of extraction efficiency (in % of the thermodynamic partition coefficient) as a function of volume flow using a 30 channel static micromixer: a system 1, water (acetone)/toluene, b system 3, water (succinic acid)/n-butanol, and c water (dl-pantolactone)/methyl-isobutylketone. The solid horizontal lines indicate thermodynamic equilibrium. Chem. Eng. Technol. 24 (2001) 1, WILEY-VCH Verlag GmbH, D-69469 Weinheim, 2001 0930-7516/01/0101-0013 $ 17.50+.50/0

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Review rium were reached. Since the internal volume of the micromixer is on the order of 14 lL (volume of the mixing chamber), residence times are less than 0.25 s (0.2 mL/h). Despite these extremely short residence times, nearly 100 % extraction efficiency could be established (thermodynamic equilibrium was reached). Fig. 5B shows a similar result for system 3, water (succinic acid)/n-butanol. The shape of the phase partition curves for both model systems can be explained qualitatively in light of an increase in specific surface area at higher flow rates. Assuming that the diffusion (diffusion coefficient D) from a sphere of radius r into a well-stirred volume is a complex function of time t [6] described by two parameters:   c Dt kVE f 2 ; VR c0 r (1)
Figure 7. Dependence of the droplet diameter of silicon oil in water emulsions on the volume flow. Short-term stable silicon oil/water emulsions were generated using a 30 channel micromixer at a ratio of feed flows of 1:1.

with k being the partition coefficient and VE/VR the ratio of extract to raffinate volume, which was set to one. In this function, only the first parameter Dt/r2 is time dependent. Fig. 6 shows a plot of the calculated extraction efficiency for succinic acid which is in good agreement with the experiments (Fig. 5D, curve b) for volume flows larger than 200 mL/h.

Figure 6. Extraction efficiency calculated assuming the diffusion coefficient of succinic acid, a phase ratio of 1:1 and the effective radius being a function of the total flow rate similar to the droplet size dependence shown in Fig. 7 (characterized by a Pade fit with an exponent of 3).

Since the residence time t is inversely related to the volume flow, one would expect maximum extraction efficiency at low flow rates. However, the droplet diameter 2r, as a measure of diffusional length, decreases with increasing flow rate. Recent investigations employing micromixers to generate short-term stable silicon oil in water emulsions without adding emulsifiers revealed that, depending on the total flow rate, oil droplets with mean diameters of 60 down to 20 lm were formed [1]. Fig. 7 shows an almost linear decrease of the droplet size in the range of 300 and 1200 mL/h at a feed flow ratio of one. Substitution of r into Eq. (1) by 1/t results in a positive correlation of extraction efficiency and flow rate as experimentally found.

Furthermore, it is expected that at very high flow rates the droplet size approaches a minimum value, and hence, the diffusional length is not further decreased (as assumed for the calculations, the dependence of droplet radius on the flow rates was simulated using a Pade fit with an exponent of 3). As a result, the extraction efficiency reaches a maximum value at high flow rates as depicted in Fig. 6. In this case, the extraction efficiency has a maximum at intermediate to high flow rates and decreases again at very high flow rates, a behavior which was found for systems 1 and 3 (see Fig. 5A and B). On the other hand, at very low flow rates the extraction efficiency is expected to increase again due to the prolonged residence time. Experiments discussed in the following paragraph experimentally confirm this finding (see Fig. 9B). The extrapolation to zero flow rate in theory should result in 100 % extraction efficiency. Investigating system number 4, water (pantolactone)/ methyl-isobutylketone, an extraction efficiency of only 90 % was found for almost all flow rates with a decreasing trend at higher flow rates (Fig. 5C). Since system 4 is not a model system, the influence of interfacial kinetics on the extraction behavior is not known. In this case an interpretation based on theoretical considerations of mass transport only was considered to be invalid. In Fig. 5D, three systems extracting different compounds are compared in terms of extraction efficiency. Whereas systems 1 and 3 show more than 95 % efficiency at flow rates above 800 mL/h, system 4 does not reach thermodynamic equilibrium. In addition, a remarkable difference in extraction efficiency at low flow rates was found for acetone (system 1) and succinic acid (system 3). Since both substances differ in their diffusion constants by a factor of two (1*109 m2/s for acetone, and 0.5*109 m2/s for succinic acid), a contribution of mass transport by diffusion within the

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Review settler was expected. Therefore, a set of experiments was conducted in a quiescent solution using a 150 mL settler. The settler was chosen instead of a separation funnel in order to retain the geometry of the experimental set-up. 42 %. Therefore, the results in terms of extraction efficiency obtained for the systems including acetone as the compound extracted have to be reconsidered in the light of the mass transport contribution in the settler. Especially, the low flow rate values for system 1 are too high and the difference of system 1 and system 3 is actually much less. Hence, both systems containing acetone (system 1 and 2) are less applicable to characterize the extraction efficiency of the micromixer. As a consequence all further experiments were conducted, only using systems 3 and 4, water (succinic acid)/ butanol and water (pantolactone)/methyl-isobutylketone, respectively.

3.2 Contribution of Diffusional Mass Transport within the Settler At flow rates of 200 and 400 mL/h residence times in the settler of 45 and 22.5 min, respectively, have to be taken into account. Fig. 8A shows that investigating system 2, water (acetone)/butyl acetate an extraction efficiency of more than 85 % was reached even after 30 min, thus, considerably contributing to the overall extraction efficiency of the mixer settler arrangement. System 3, water (succinic acid)/butanol, however, shows only a 12 % extraction after 30 min. (Fig. 8B), hence, being a more suitable system to characterize the extraction efficiency of the micromixer. Therefore, data from system 2 have not been included in the analysis of the extraction efficiency. Fig. 8C and D show a 24 h run for system 1, water (acetone)/ toluene, and system 4, water (pantolactone)/methyl-isobutylketone. In case of acetone being the compound extracted, thermodynamic equilibrium is achieved after 24 h, whereas pantolactone (system 4) even after 24 h was only extracted to

3.3 Results Utilizing Two Micromixers in Series The volume flow rate in miniplants in most cases is not a free variable and has to be tailored to meet the specific process conditions. Hence, if the extraction efficiency at a particular flow rate is not optimal, cascades of more than one mixer stage are usually applied. Thus, further experiments were dedicated to elucidate the enhancement of extraction efficiency when using two micromixers in series at low flow rates. For system 3, water (succinic acid)/butanol, 100 % extraction efficiency was reached at 200 mL/h, a flow rate where one micromixer is not sufficient to establish thermodynamic equilibrium.

Figure 8. Phase partition as a function of time when contacting 75 mL aqueous phase and 75 mL organic phase in a 150 mL settler: A) system 2, water (acetone)/n-butyl acetate, B) system 3, water (succinic acid)/n-butanol, C) system 1, water (acetone)/toluene, and D) water (dl-pantolactone)/methyl-isobutylketone. The solid horizontal lines indicate thermodynamic equilibrium. Chem. Eng. Technol. 24 (2001) 1, WILEY-VCH Verlag GmbH, D-69469 Weinheim, 2001 0930-7516/01/0101-0015 $ 17.50+.50/0

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Figure 9. Phase partition as a function of volume flow using a 300 channel micromixer array: A) system 3, water (succinic acid)/ n-butanol, and B) water (dl-pantolactone)/methyl-i-butylketone. The solid horizontal lines indicate thermodynamic equilibrium.

3.4 Results Utilizing One Micromixer Array For high volume flow rates up to 6400 mL/h a micromixer array in combination with a 150 mL settler was utilized. Fig. 9A and B show the results for succinic acid (system 3) and pantolactone (system 4) extraction, respectively. The phase partition curve for succinic acid shows qualitatively the same behavior as discussed for the 30 channel micromixer, and thermodynamic equilibrium is reached at a volume flow rate of 6400 mL/h. This result is consistent with the data obtained in previous experiments using the micromixer. Since the number of microchannels of the micromixer array is ten times higher than the number of microchannels of the single mixer, similar linear velocities of the fluids in the channels and hence similar sheer forces are to be expected theoretically at a ten times higher volume flow. However, the pressure drop influence of the feed channels also has to be taken into account resulting in a factor less than ten. Indeed, previous experiments have shown that at a similar pressure drop six to eight times higher flow rates are obtained. From Figs. 5B and 9A the maxima of the phase partition were found to be at 800 mL/h and 6400 mL/h, respectively, with a factor of eight difference. This stands in good accordance to the previous observations. The phase partition as a function of volume flow for system 4, water (pantolactone)/methyl-isobutylketone, qualitatively shows similar behavior as found for succinic acid extraction, though not reproducing the data obtained when using the single micromixer (Fig. 5C) at comparable flow rates (200800 mL/h). In contrast to the trend of the extraction curve reported in Section 3.1, 96 % extraction efficiency was achieved when using the micromixer array at a maximum flow rate of 6400 mL/h. These trend differences are not yet understood and are subject to future investigations.

a hundred milliseconds. Fast extraction employing microdevices that utilize a nondispersive principle was reported in the literature [7,8]. Microchannel contactors with partial overlap [7] have shown efficient phenol extraction from aqueous solution into octanol with short contact times below one second. Future investigations will focus on a direct comparison of disperse and nondisperse operation, i.e., micromixers and microchannel contactors as well as membrane contactors. In all micromixer experiments using different systems for extraction, efficiency is a function of the volume flow rate which could be interpreted based on mass transfer considerations. At optimal flow rates, in most cases thermodynamic equilibrium was reached in only one mixer settler stage. In cases were equilibrium was not achieved (low volume flow), 100% efficiency could be established using two micromixers in series. The practical range of flow rates (2001600 mL/h) can be extended to volume flows of 6400 mL/h when using a micromixer array without loss of extraction efficiency. Furthermore, because of their low costs of approximately 20% of standard 0.25 L stirring reactors, it is a technically and economically sound alternative to state of the art extraction devices.

Acknowledgments
The authors like to acknowledge the valuable support concerning the experimental work by Klaus Eckrich and Volker Schwuchow, BASF AG.
Received: July 11, 2000 [CET 1217]

References 4 Conclusions
The micromixers employed proved to be highly efficient for extraction purposes. Due to very high specific interfacial areas of the dispersed system formed, extraction is completed within 16
WILEY-VCH Verlag GmbH, D-69469 Weinheim, 2001 [1] [2] Haverkamp, V., Ehrfeld, W., Gebauer, K., Hessel, V., Lwe, H., Richter, T., Wille, Ch., Fresenius J. Anal. Chem. 364 (1999) pp. 617624. Hessel, V., Ehrfeld, W., Golbig, K., Haverkamp, V., Lwe, H., Richter, T., Proceedings of 2nd International Conference on Microreaction Technology, Topical Conference Reprints, AIChE, New Orleans, February 1998, pp. 259266.

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[3] [4] [5] [6] Hessel, V., Ehrfeld, W., Haverkamp, V., Lwe, H., Schiewe, J., in: Mller, R.H., ed., Dispersion Techniques for Laboratory and Industrial Production, Apothekerverlag Stuttgart, in press. Ehrfeld, W., Golbig, K., Hessel, V., Lwe, H., Richter, T., Ind.Eng. Res. 38 (1999) pp. 10751082. Misek, T., Berger, R., Schrter, J., Standard Test Systems for Liquid Extraction, European Federation of Chemical Engineering, EFCE Publications Series No. 46, 2nd Edition, 1985. Crank, J., The mathematics of diffusion, 2nd Edition, Clarendon Press, Oxford 1975. [7] Shaw, J., Turner, C., Miller, B., Robins, I., Kingston, J., Harper, M., Proceedings of 2nd International Conference on Microreaction Technology, Topical Conference Reprints, AIChE, New Orleans, February 1998, pp. 267271. TeGrotenhuis, W. E., Cameron, R. J., Butcher, M. G., Martin, P. M., Wegeng, R. S., Proceedings of 2nd International Conference on Microreaction Technology, Topical Conference Reprints, AIChE, New Orleans, February 1998, pp. 335339.

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