Partitioning of Substrate within Aqueous Micelle Systems by Using Dead-End and Cross Flow Membrane Filtrations

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1 Available online at Procedia Engineering 33 (212 ) 7 77 IEE 11 Partitioning of ubstrate within Aqueous icelle ystems by Using Dead-End and Cross Flow embrane Filtrations hamed. Djennad a, Djafer Benachour b, and Reinhard. chomäcker c* a University of ostaganem, B. P.3, ostaganem 27, Algeria, b University of etif, Faculty of echnology, etif 19, Algeria, c echnische Universität Berlin, Fakultät II Institut für Chemie, Germany Abstract he partition coefficients of different solutes as Itaconic acid ( IA), dimethyl itaconate (DI), diethyl itaconate (DEI) and dibuthyl itaconate (DBI) between water and micelles of riton X-1 are determined by the two methods of separation namely Cross Flow Filtration and Dead-End Filtration by using a membrane that rejects the micelles and lets passing the molecules of solute. Partition coefficient of the solute between the aqueous phase and micelle aggregate was determined by titration and HPLC methods. he results obtained are discussed in our researcher s group and compared to others made with theoretical data reported from simulation. he effect of the different concentrations of solutes and transmembrane pressures have been investigated using a commercial membrane Nadir C5 (CO = 5 kda). 211 Published by Elsevier Ltd. election and/or peer-review under responsibility of IEE 11 Open access under CC BY-NC-ND license. Keywords; icelle-enhanced Ultrafiltration, rejection of micelles, partition coefficient in micelles, modelling of distribution of partitioning coefficient. * Corresponding author. el: Fax: address: schomaecker@tu-berlin.de Published by Elsevier Ltd. doi:1.116/j.proeng Open access under CC BY-NC-ND license.

2 hamed. Djennad et al. / Procedia Engineering 33 ( 212 ) Nomenclature K [-] Partition coefficient X [-] olar fraction of solute in micelles X [-] olar fraction of solute in water CC [mol./l] Critical micelle concentration of surfactant C [mol./l] Initial concentration of micelles in volume V V [L] Initial volume of solution n n n [mol.] [mol.] [mo.] oles of solute in water oles of solute in initial volume of solution oles of surfactant in total volume (V) n [mol.] oles of water in initial volume of solution VP [L] Volume of permeate VR [L] Volume of retentate R urfactant concentration in retentate P urfactant concentration in permeate Rmembr. [mm] Radius of the membrane P [bar] ransmembrane pressure C C C Concentration of solute in micelle phase Concentration of solute in aqueous phase Concentration of solute in initial volume of solution V Concentration of surfactant in initial volume of solution Concentration of surfactant in micelle phase Concentration of surfactant in aqueous phase R [%] Rejection of solute in permeate or in retentate R [%] Rejection of micelles G [kj/mol] Free energy of the system

3 72 hamed. Djennad et al. / Procedia Engineering 33 ( 212 ) Introduction urfactant solutions which solubilise hydrophobic compounds in aqueous solution have been studied over many years. As a consequent, the partitioning of solutes in these micelle systems is determined in order to evaluate the fraction dissolved in the surfactant. In many cases, the coefficient is not easy to determine by such a technique and depends to several parameters. One of these proposed methods to separate the solute from the retained aggregates is called micelle-enhanced ultrafiltration (EUF) [1-4]. A simple scheme of the commercial technologies Dead-End Filtration and Cross flow Filtration used in this work is reported in Fig 1. In the present study, partition coefficients of different solutes as Itaconic acid (IA), dimethyl itaconate (DI), diethyl itaconate (DEI) and dibuthyl itaconate (DBI) between water and micelles of riton X-1 are determined by the two methods of separation namely Cross flow and Dead-End Filtration by using a membrane that rejects the micelles and lets passing the molecules of solute. he values of the partition coefficients are compared to those obtained by a mathematical model presented by a collaborated group [5]. 2. Experimental 2.1. aterials and methods Itaconic acid (IA) was purchased from Aldrich, dimethyl itaconate (DI) was obtained from Fluka, diethyl itaconate (DEI) and dibuthyl itaconate (DBI) were supplied by CI Europe nv and riton X-1 was from igma- Aldrich. oluene, 2-propanol, acetonitrile and water grade for HPLC were purchassed from Carl Roth GmbH + Co. KG. All the concentrations were performed spectrophotometrically using an UVIKON 81 spectrophotometer from KONRON Instrument GmbH ( = 276 nm, = 25 C) and two HPLCs apparatus Dionex GmbH with Chromeleon chromatography software (detector UV-Vis with = 21/27nm; flux =,7 ml/min; P =13/15 bar; Injection volume = 1 µl and 6% ACN & 4% H 2 O) and P58 LPG high-pressure quaternary gradient pump and

4 hamed. Djennad et al. / Procedia Engineering 33 ( 212 ) RP-HPLC Agilent 11 from h&pagilent (Pumpe G1311A), Entgaser G1379A, Autosampler G1313A, Diodenarraydetektor G1315A, hermostat G1316A with = 21/27nm; flux =2, ml/min; P =15/16 bar; Injection volume = 1 µl and 8% ACN & 2% H 2 O). For the two methods a column of 12 RP 18-5 µ at 25 C was used. he permeate was filtrated under different pressures across a membrane at 25 C using an ultrafiltration (UF) unit consisting of a cell (stirrer speed 7 U/min) from Bioengineering AG (ald, chweiz). he assay were fed with a pressure produced by an HPLC pump 64 (Knauer, Germany) and a second pump from Ismatec, A Unit of IDEX-Corporation (BVP-Z). In addition, the fed solution across the same membrane was performed by using a Dead-End Filtration process mode Berghof Laborprodukte GmbH (Niederdruckzelle GN 1-4). he membrane used in this work was from icrodyn Nadir C-eries, CO 5 kda with a pure water flux > 25 L/(m 2 *h) and a test solute of Dextran 1 (1%). he diameters of this membrane were 67 mm and 76 mm for Dead-End Filtration and Cross Flow-Filtration, respectively. A solution of,1 g solute (IA, DI, DEI or DBI) + 1 g riton X-1 + 1L H 2 O was filtrated across the membrane at different pressures,6;,8; 1,; 1,2 bar. wo different methods were used to calculate the partition coefficients (titration and HPLC). In contrast to the titration method, the different concentrations of initial solution permeate and retentate measured by HPLC were more precise. 3. Results and discussion he partition coefficient can be written as follows X X X K = (1) ( 1 fex) n ( 1 f ) n + n = (2) ex he following terms are defined as X f n ex = fex n + n (3) n f ex = (4) n n = V ( C CC ) (5)

5 74 hamed. Djennad et al. / Procedia Engineering 33 ( 212 ) 7 77 As can be seen in able 1, the partition coefficient is merely independent of the choice of the filtration technique. It seems that the solute depends strongly to the nature of its bonds in aqueous and micelle phases. he influence of the hydrophobicity of the solute on the partitioning coefficient was reported in Figures 2-3. As is seen in these figures, K has an exponential form and depends clearly with the hydrophobic compounds in the micelle systems, from itaconic acid (IA) to dibuthyl itaconate acid (DBI). As a result, more hydrophobic solutes are strongly bound to micelle molecules relating to the rejection in ultrafiltration. In addition, the variation of the transmembrane pressure has no influence on the variation of partitioning coefficient. he plot of the partition coefficient calculated from both experiment and simulation is shown in Figure 4. o compare the simulated values of K with our data, the following protocol has been considered: Variation of the different concentrations a) f ( C ) C = athematical equation b) K f ( C ) for [ ] = athematical equation C c) C = f ( C ); C = f ( C ); C = f ( C ); C = f ( C ) athematical equations d) R = f ( K ); R f ( K ) = athematical equations Final mathematical model Variation of the free energy a) ΔG = R ln K b) ΔG = f ( ) n R CH 3 a) 3.3.tudy of the micelle solutions b) study of the added chemical components c) effect of ph d) shapes of micelles and their implication

6 hamed. Djennad et al. / Procedia Engineering 33 ( 212 ) Repeat the same experiments with different solutes and surfactants able 1. Partition coefficients of Dead-End and Cross Flow Filtrations Dead-End Filtration Cross Flow Filtration olute K ave K ave IA DI DIE DBI K ave : Average value of the partition coefficient DEF : Dead End Filtartion CFF : Cross Flow Filtration

7 76 hamed. Djennad et al. / Procedia Engineering 33 ( 212 ) 7 77 Kexp: Experimenta K Ksim: imulated K 4. Conclusions Partition coefficient of micelle system was investigated by increasing the hydrophobicity of the solute and varying the concentration of surfactant and solute. he choice of Dead-End and Cross Flow Filtrations and the variation of transmembrane pressure had no influence on the partitioning coefficient. icelle enhanced ultrafiltration is a good method used in this work to separate permeate with the solute. Also, the rejection of surfactant was quite high. he comparison of our results with those simulated was in agreement.

8 hamed. Djennad et al. / Procedia Engineering 33 ( 212 ) Acknowledgments I would like to express my gratitude to the echnical University of Berlin for financially supporting this work. I wish to express my sincere gratitude to Prof. Dr. R. chomäcker, Head of Reaction Engineering Group at U Berlin. References [1] camehorn J. F.,. D. Christian, R.. Ellington, urfactant-based eparation Processes, Dekker, New York (1989) [2] Keskinler B., U. Danis, A. Cakici, G. Akay, ep. ci. echnol., 32 (1997), 1999 [3] chwarze., R. chomäcker, Chem. Ing. ech. 78 (26), 7, 931 [4] chwarze.,. Djennad, A. Rost,. Buggert,. Arlt, R. chomäcker, Chem. Ing. ech. 78 (26), 9, 1277 [5] Buggert., L. okrushina, I. mirnova, R. chomäcker,.artl, Chem. Eng. echnol. 29 (26), 5, 567