Temperature Effect on the Retention Behavior of Sugars and Organic Acids on poly (4-vinylpyridine) Resin

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1 Korean Chem. Eng. Res., Vol. 44, No. 1, February, 2006, pp PVP 분리수지에서온도에따른당과유기산의체류특성변화 smçmp *Ç l p, *r l p}e n 253 ( o 14p r, o 11p }ˆ) Temperature Effect on the Retention Behavior of Sugars and Organic Acids on poly (4-vinylpyridine) Resin Jin-Il Kim, Chong-Ho Lee* and Yoon-Mo Koo Department of Biological Engineering,G*ERC for Advanced Bioseparation Technology, Inha University, 253, Younghyun-dong, Nam-gu, Incheon , Korea (Received 14 November 2005; accepted 11 December 2005) k e l edšp f PVP vl, p e m r, k p o p n l m l ~ e p r kk k. d e p n l e p m l ~ e kk, v kk. PVP v p rp l n v k el m p p r lv p m, m l p ˆ v kk. l, PVP vl o p nl m., o l r r p kk o l 35 o C, 65 o C m l r l p p m. p m l p SMB(simulated moving bed)m p Š rl pn pp p Ž. h Abstract This study was performed to understand temperature effect on retention behavior of fructose and glucose as sugars and lactic acid and acetic acid as organic acids on poly (4-vinylpyridine) resin. The pulse tests were performed to understand temperature effect on retention time of sugars and the results were not shown large change. As it was able to predict with PVP resin not to be used for sugar separation generally, the results were shown poor resolution for separation of sugars and temperature effect on the resolution change of sugars also was not large. On the other hand, in the case of organic acids on PVP resin, the pulse tests were shown temperature effect on the retention behavior was very large. So, the frontal analyses were performed to understand quantitative adsorption behavior of organic acids at 35 and 65 o C. These adsorption characteristics of organic acids with PVP resin system can be used to preparative chromatographic process such as SMB (simulated moving bed). Key words: Poly(4-vinylpyridine) Resin, Fructose, Glucose, Acetic Acid, Lactic Acid 1. e p nv vp r pp ep kk p., p ep q e dšl r p } np p p. v, ep d m p p k v p e p p [1, 2]. p ep p rp Š p p rr rp l n p To whom correspondence should be addressed. ymkoo@inha.ac.kr [3, 4]., pr m ov p ep rl Š rp sll p v r p o t n. Wankat [9], Rempel [10, 11] Wang [12]l p m l l l l. p Š r l pl sl s p ˆp k v ppp p, n p p lp p [12]. p e p poly(4-vinylpyridine) v l, p r k p o l m l 35

2 36 vpëps Ë o ~ p p m. p kk o, pr p e d tp l, d e p m ~ e p kk k., o p m l ~ e p m l 35 o Cm 65 o Cp m ol r p l r rp m ep l l kk k h e p f, Samchun Pure Chemical. Co., Ltdl p m. o p k r p n m, Sigma Chemical Co.l p l n m. v poly(4-vinylpyridine) v n m. qˆp p p 30.6 cm, 1.0 cmp p v p ACE Glass Incorporated l n m. p p n 3 v Milliporep Milli Q systemp ll n m. LAUDA p RC 6 CS n l p m e l sr l e p m. n p n Shimadzu p LC-10AD, Waters p Waters 410 Refractometer l n m. rp o e Blue dextranp Sigma Chemical Co. l, NaClp Samchun Pure Chemical. Co., Ltdl p l n m. n e m p p l m ~r l e l n m m l ~ p kk q p 40, 50, 60 o C p m ol, o p 35, 45, 55, 65 o Cp m ol d e p m, p, 300 g/lp, r k p 30 g/lp d tp l e p m. m p l p r kk o 35 o Cm 65 o Cp m l o p r p ee l m ep r rp p m. rl e (q) (1)el p p e mp m [8]. T U s ( ) = v = = 1 ε e 1 ε ε p K e q + d ( 1 ε p )ρ s c + ε t ( 1 )ε p 3. y k l p e p ~ e l m p m p o l 40, 50, 60 o Cp m ol e p m, Fig. 1, 2l PVP vl p d tp ˆ l. PVP v pm vpv, p rp n n v k l p l v kp p m p e p m [10-12]., Table 1l p p p p ~ e p o p m, pl l PVP vp p ˆ p lpp p m., PVP v l m l p ~ p p p m. Fig. 1. Temperature effect on pulse experiments of fructose. L RT (4) (5) = Q i + 1 Q i + ( V F V O )( C i + 1 C i ) V a (1) (1)ep lp qm cp Scatchard plotp Langmuir isothermp m. q --- = bq + bq s C ac q = bc (2) (3) rp o l Blue dextran(m.w. 2,000,000) 1 g/lm NaCl (M.W. 58.5) 1 Mp n m. pq, pq p (4), (5)ep l m [5]. o44 o k Fig. 2. Temperature effect on pulse experiments of glucose.

3 PVP vl m l o p ~ 37 Table 1. Temperature effect on retention volume of fructose, glucose, acetic acid and lactic acid and porosity of PVP. Temperature ( o C) Retention volume (ml) Fructose Glucose Temperature ( o C) Retention Volume (ml) Acetic acid Lactic acid Porosity Total Inter-particle Intra-particle Fig. 3. Temperature effect on pulse experiments of acetic acid. Fig. 4. Temperature effect on pulse experiments of lactic acid. PVP vl o ~ e p 35, 45, 55, 65 o Cp m ol d tpp e p m. Fig. 3, 4l pl Š p ˆ l. Fig. 3, 4l p PVP vl p m l ~ e p p m. o l d e p m PVP vp, pq, pq p Table 1l r k. r l p v kpp p p l., m l o p ~ e p p l p p k p k pl. 35 o Cl 65 o C m v l ~ e p 35 o C tp r p k 38Í, k p k 54Íp p mv, pq, pq p v p p p., ~ e p m l p p. 35 o Cm 65 o C, m l e r p Fig. 5, 6. (a)m (b) 35 o Cm 65 o Cl p k r p r ˆ l, (c)m (d) r p lp p q, q/cp p Scatchard plotp l Langmuir isothermp m. Table 2l pl ˆ l. 35 o C tp l, k p Langmuir isotherm a 15.28Í, b 27.94Í m, r a 13.03Í, b 11.29Í m. p, m l p o p p pl. e l p p PVP v l o p p m l p m. pl po PVP v pm p p v p p phl p p p p l [10-12]. r k p p p l p, e m p p ph, p p ˆ p pl [7]. v, p php pv k l PVP v l l ˆ pv k. p PVP vl o p p p p. 4. m e p PVP vm o p ~ l m p m p kk q m. PVP vl m l p ~ p p v k p m, p l p p m. p p rp l jp pm vm PVP v p pl p p. pl, PVP vl m l o p ~ p m., m srp l tl k r p l pn p. l Thermally-assisted SMB SMB rp pn, SMBp zonep l m sr l e p l t l n p p p., PVP v l m l p o p p SMBm p Š rl pn p Ž [6, 9]. Korean Chem. Eng. Res., Vol. 44, No. 1, February, 2006

4 38 vpëps Ë o Fig. 5. Frontal analyses of acetic acid at 35 and 65 o C. (a), (b): results of frontal analyses at each temperature. (c), (d): Scatchard plot to estimate the Langmuir isotherm. Fig. 6. Frontal analyses of lactic acid at 35 and 65 o C. (a), (b): results of frontal analyses at each temperature. (c), (d): Scatchard plot to estimate the Langmuir isotherm. o44 o k

5 PVP vl m l o p ~ 39 Table 2. Temperature effect on the Langmuir isotherm parameter a, b for acetic acid and lactic acid l q p r l (ERC)p vop k md. ε T ε p U s : total porosity k : external void fraction (between particles) : intraparticle void fraction (within a particle) : velocity of solute in the column T : temperature [ o C] v : interstitial fluid velocity [m/min] ρ s : structural solid density [kg/m 3 ] q : amount of solute adsorbed [kg/kg adsorbent] c : solute concentration of fluid [kg/m 3 ] L : column length [cm] K d : fraction of interparticle volume species can penetrate C i : solute concentration of fluid during the ith step in frontal analysis [g/l] Q i : amount of solute adsorbed after the ith step in frontal analysis [g/l solid volume] V F : retention volume of the inflection point of the ith breakthrough curve in frontal analysis [ml] V o : column void volume [ml] : volume of adsorbent in the column [ml] V a Temperature ( o C) Langmuir Acetic acid a isotherm b Lactic acid a b y 1. Guichon, G., Golshan-Shirazi, S. and Jaulmes, A., Computer Simulation of the Propagation of a Large-Concentration Band in Liquid Chromatography, Anal. Chem., 60(18), (1988). 2. Saska, M., Clarke, S. J., Wu, M. D. and Iqbal, K., Glucose- Fructose Equilibria on Dowex Monosphere 99 CA Resin under Overloaded Conditions, J. Chromatogr. A., 590(2), (1992). 3. Ruthven, D. M. and Ching, C. B., Counter-Current and Simulated Counter-Current Adsorption Separation Processes, Chem. Eng. Sci., 44(2), (1989). 4. Guiochon, G., Preparative Liquid Chromatography, J. Chromatogr. A., 965(1-2), (2002). 5. Wankat, P. C., Rate-Controlled Separations, Glasgow, London (1994). 6. Migliorini, C., Wendinger, M. and Mazzotti, M., Temperature Gradient Operation of a Simulated Moving Bed Unit, Ind. Eng. Chem. Res., 40(12), (2001). 7. Lee, H.-J., Xie, Y., Koo, Y.-M. and Wang, N.-H. L., Separation of Lactic Acid from Acetic Acid Using a Four-Zone SMB, Biotechnol. Prog., 20(1), (2004). 8. Gorges, G., Sadroddin, G. S. and Antia, M. K., Fundamentals of Preparative and Nonlinear Chromatography, Academic Press, New York(1994). 9. Kim, J.-K., Abunsser, N., Wankat, P. C., Stawarz, A. and Koo, Y.-M., Thermally Assisted Simulated Moving Bed Systems, Adsorption, 11(1), (2005). 10. Chanda, M., Mcgarvey, C. and Rempel, G. L., Sorption of Aqueous Sulfur Dioxide on Polybenzimidazole and Poly(4-vinyl pyridine), Reactive Polymers, 10(1), 79-87(1989). 11. Chanda, M., O Driscoll, K. F. and Rempel, G. L., Sorption of Phenolics onto Cross-Linked Poly(4-vinyl pyridine), Reactive Polymers, 1(4), (1983). 12. Hritzko, B. J., Ortiz-Vega, M. J. and Wang, N.-H., Adsorption of [N-(Phosphonomethyl)imino]diacetic Acid and Iminodiacetic Acid on Poly(4-vinylpyridine), Ind. Eng. Chem. Res., 38(7), (1999). Korean Chem. Eng. Res., Vol. 44, No. 1, February, 2006

Purification of Fructooligosaccharides Using Simulated Moving Bed Chromatography

Korean Chem. Eng. Res., Vol. 43, No. 6, December, 2005, pp. 715-721 Simulated Moving Bed 크로마토그래피를이용한프럭토올리고당의정제 j mp * l p, *r l 402-701 p}e n 253 (2005 9o 30p r, 2005 11o 24p }ˆ) Purification of Fructooligosaccharides