Modeling for the Recovery of Organic Acid by Bipolar Membrane Electrodialysis

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1 Korean Chem. Eng. Res., Vol. 44, No. 5, October, 26, pp m n ˆ i m l i Çm z p edš l s op ek 34 (26 3o 31p r, 26 6o 2p }ˆ) Modeling for the Recovery of Organic cid by ipolar Membrane Electrodialysis Sang-Hun Kim and yung-chul Lee Department of Chemical System Engineering, Hongik University, 34, Shinan-ri, Jochiwon, Yeongigun, Chungnam , Korea (Received 31 March 26; accepted 2 June 26) k h l l o mp o p p p 2e l rp p r Œ p pn l m. o p k r p n mp, o p, p ph p r l r m. o mp rp o p r lp k, ql Na pmp p ˆ pl. e ˆp pm p l rp p m. e l o p, p ph p ep e p m q p m. bstract This paper studied the recovery of organic acid from organic acid salt by using bipolar membrane electrodialysis. cetic acid and lactic acid was used as for organic acid. Organic acid concentration, sodium hydroxide concentration and ph values were measured at various current density. Organic acid salt was effectively converted to organic acid and sodium hydroxide. ased on the experimental results, mathematical models were developed, in which time changes in ion balance were considered. Model predictions of organic acid concentration, sodium hydroxide concentration and ph values were in good agreement with the experimental data. Key words: Organic cid, cetic cid, Lactic cid, ipolar Membrane Electrodialysis (EDM), Modeling 1. l l kl r m p eˆ o l rp p n l v p. k t o p p p p p e, pk, q, q o p mll n lv p [1. o p eqp 4Í j q. o p acetic acid(1,8, T/y), lactic acid(9, T/y), citric acid(725, T/y), gluconic acid (45, T/y) [2. lrp l p o p p, r,, rr l rl p p lv. l p llv o mp p p eˆ l l v p n p. sp o } l n p l King Paul[3, aniel[4 erglund [5p rk n p t n l m. p rr p l o solvent pn, p p eˆ rrp v To whom correspondence should be addressed. bclee@hongik.ac.kr p. l r Œ p pn l o p p rk p. r Œ p pm p ro pn l pmp eˆp f nk tl sq r v p pm p rr, p rp. r Œ rp kl o p k rl o p l n l vp np tp p tp f o p p np., r Œ p p rr r r q~ k eˆ p r l l n rp rp. p r Œ (EDM, electrodialysis with bipolar membrane) p kpm ppm p ˆmn r Œ rl p l H pm OH pmp p p p p rp [6. p p k/ppm p n ˆp p rn o pp l v l l p [7. p r Œ p rp microfiltration(mf) sp r Œ (ED, electrodialysis) p r} rl r mp n. Roux-de almann [8 Cheryan [9 p l q p p r} r 476

2 l l p. p r Œ l o rl m p t tn r, okp, ph p p [1, 11. ph o p pml m p t l pl l n. l l p kpm p 2e s p p r Œ q pn l o rs e p mp p l p p p p l m p t tn p ph m p r p n q m. 2. m r Œ q shahi Chemicall rq SV-7 typep n mp q p Fig. 1. p p o p p strom p NEOSEPT P-1p n m o p o shahi Chemical p dž CIFLEX K-51S p n m. dˆp o 2ep m p o rp 5 cm 2p r~ dˆl o rp.1 m 2 m. k p Žp n m p p d p d džžp n m. p r Œ rp, m, r k p p p 1.5 Ln PVC l l e q rp ˆ m. kp.3 M Na 2 SO 4 (Daejung Chemicals & Metals Co.) nkp ph 2 sr l n mp, kl ~p r o kp 3 L/minp pr e. o e p l k ph, r, l o p p k. p o l k r p r 1~2 /m 2 e e p v m. o p k (Duksan Chemical Co.) r (Duksan Chemical Co.)p ˆ l e m. l p o m p 1M mp NaOH(Duksan Chemical Co.) l ph 6.8 sr l sl nkp m o EDMl p o l 477 nkp sr m. m l p p.3 M sr m. m p 1.5 L/min p pr ov m. q l rkp rksr (shahi MP-18-14) pn l mp, r r (Kikusui PD35-5L, -35V 5) n l m. e p s l p 1Í NaOH nk.35í HCl(Samchen Chemical Industries)nk v r m. o p r r o C(acid compartment)m C(base compartment)l p phm r r p ph meter(istek, Japan)m conductivity meter(oakton PC51) pn l pr p r l mp, k~p p p r o p ko p r l m. rkp v e l e p s m., Cl p o p 1 p e } l.2 M NaOH nkp rrl p r m, Cl p NaOHp 1 p e } l.2 M HCl nkp rrl p r m. 3. m 3-1. l l l 2 i EDMm k p r Œ p mp p p l p o l n. Fig. 2m p dˆp kpm p p l 2e lp ˆ m. Cl mp Cl m nkp. l l r t p p l l p r l Cl H pmp C l OH pmp. Cl ph p mp p, Cl Cl kpm p lm kpm p p l p OH pm l m. Cl p rr v Cl m rr v. p o p l o mp o p mj l phjm r Œ l vp p p l p pm v p p Fig. 1. Schematic diagram of experimental set up (I: current, C: conductivity, Q: flux, ph: ph value, T: temperature, U i : inner (stack)voltage, U o : outer(applied)voltage). Fig. 2. Principle of EDM for the conversion of organic acid salts - example of a sodium salts. Korean Chem. Eng. Res., Vol. 44, No. 5, October, 26

3 478 Ëp ~ m p r p l p p v kp pm v p l p l p p. p pm p pm ˆ q p pm p tn pq. r m p. p pms p pp nkp phm l p r. ph r Œ sp nrl m p t q pq p. k p k p n l rp pm. p pm r k p m m p sqp l l p m p. k p pm acetate pm H pmp. [ Hc K [ H [ c (1) cetate pm k m r~ (2)e. l V r~ p. Formular weight Hc V [ Hc c [ (2) k p (3)e p. F Hc [ Hc [ c _ k p ep (4)e. l K mol/lp p 5. [ H [ c K [ Hc p p [Hcl r p v vel p (5)e p. [ H [ c F Hc c K [ k p acetate p acetate pp α 1, α 2 p (6)e. α 1 [ c F Hc K [ H K (3) (4) (5) (6a) Fig. 3. Fractional ionization and ph for acetic acid and lactic acid l m Fig. 4 p n o pp p. (4)ep p p l j (7)ep. K n H ( t)n c ( t) V ( t)n Hc ( t), pm p p p p ˆ p. J H M M J OH J H CEM CEM J Na Cm Cl p pm p p p ˆ p. dn Hc dn H ( t) ( t) M J dt dt H dn OH ( t) M CEM J OH J H dt J H CEM (7) (8) (9-a) (9-b) Na pmp H pm l r p k p. p p l r p p ˆ p. α 2 [ Hc F Hc [ H [ H K (6b) p ep phl e Fig. 3 p. Fig. 3p k r p pm pp ˆ p. pm pp K l v. l k K mol/l p r p K mol/lp. Fig. 3l m p k r p ph v l pm pp v. l k p ph 4.72l r~ p 1/2p pm, r p ph 3.86l r~ p 1/2p pm., r ph l ~ r p pmpp k p pmp p k p. p p o p e l ph p p p m p. o44 o5 26 1k Fig. 4. Schematic drawing of the fluxes and reactions considered for the model establishment.

4 EDMl p o l 479 n H ( t) n Hc ( t) n OH t (1) l rp r p l r.2ip. e l p ep p p ˆ p. C ( t) C ( t) (11-a) (11-b) l V (t) V at, V (t) V at p. a p p l pqp phm n H ( t) n Hc ( t) rt V ( t) n Na ( t) V ( t) ( ) n Na ( t) rt Cl p l p H pmp p l ph p. ph p o l v v p. e p q p p p. Fig. 5 k e l r m e l Cl p k p e p l m p e l k p rp v p lt pp e (11-a)ep q p p p., r v k p v pp rp v p lt p. p p Fig. 6l ˆ l. Fig. 7 p Cl NaOHp e p k p p ˆ po Cl p Na pmp kpm p p k p p l r~rp NaOHp k p. Fig. 8p k e l r m e l Cl p ph e p l m p e p v l ph p p p p p Na pmp kp m p Cyp p l acetate pmp H pm l k p p, p l p H pmp p l r~rp H pmp v n H ( t) n H, n c n Hc t ( ) n c, t ( t) rt e( t) h t n Na ( ) n Hc, et ( ) et ( ) ( ) (12-a) (12-b) (12-c) l e(t) e l k p p, h(t) kpm p H pmp p. (12)ep (7)el p p e(t)l r p p. et ( ) gt ( ) gt ( ) 2 ± 4n c, [ n Na ( t) rt h( t) l gt ( ) K V ( t) n H, n Na ( t) rt n c, h(t) e l p pp p e. (13) p. h(t) (pi q) It 2 (14) ht ( ) l pm q r m e l f , p. k k p p (9)e p pm p(a)l p p. Fig. 5. Concentration of acetic acid in the acid compartment for acetic acid experiment. n c, n α (15-a) n Hc, n n c, (15-b) (13), (14), (15)ep (12)el p l n H ( t) p ph e p p ˆ pl. n ph H ( t) log ( t) V 4. m (16) p r Œ l p o p p p kk o r ep l. ep pn l Cm Cl e r l ph, o NaOHp plp, e p p k. p Fig. 6. Concentration velocity as current density. Korean Chem. Eng. Res., Vol. 44, No. 5, October, 26

5 48 Ëp ~ Fig. 7. Concentration of sodium ion in the base compartment for acetic acid experiment. Fig. 9. Concentration of lactic acid in the acid compartment for lactic acid experiment. Fig. 8. ph value in the acid compartment for acetic acid experiment. Fig. 1. Concentration of sodium ion in the base compartment for lactic acid experiment. ppp lt p p., r v l ph p p r v l p l p p pl ppp lt p p. l m p p }pl p e p v l php pl, p (6-a)el m p H pmp v p m pp p p. v p acetate pmp k p r l e H pmp v l ph p. Fig. 9, 1, 11p Fig. 5, 7, 8 p s l r p rneˆ e p p. k p p v pp, e p q p p p. p l ph o l p r l k r p ph m. Fig. 12 k r p ph p p Fig. 12l m p r p ph p k p o44 o5 26 1k Fig. 11. ph value in the acid compartment for lactic acid experiment.

6 Fig. 12. ph value in the acid compartment at 2 /m 2. Fig. 13. Concentration of acid in the acid compartment at 2 /m 2. EDMl p o l 481 p, po r p K p mol/lp k p 4 K mol/l ƒ pm pp ƒv p p 5. p e l ph p p m pp, (16)ep p q p p k pl. Fig pr r p s l Cm Cl p p m NaOHp e p k r p n p v p pp lt p. p p Cp ph p 6.8 p l k r p pm pp 1l l Na pmp p p. k r p l m p p lt p. 5. l p r Œ l p o l rp l. p edšl p kpm p n 2e l p r Œ q n l o m p o p e p m. o p k r p n mp, p e l e m el p e l m ph tep k. p n p l rep m, m ph m p r p m. r l p m k r p p l llv e p m q p p pl. l 24 p l vo l p lp pl. k C : concentration [N F : formular weight I : current density [/m 2 J : flux [kg/m 2 h K : equilibrium constant [mol/l n : mol t : time [h V : volume [L Fig. 14. Concentration of sodium ion in the base compartment at 2 /m 2. g zm : acid compartment : base compartment M : bipolar membrane CEM : cation exchange membrane H : hydrogen ion c : acetate ion Na : sodium ion Hc : acetic acid Korean Chem. Eng. Res., Vol. 44, No. 5, October, 26

7 482 Ëp ~ y 1. Kirk, R. E. and Othmer, D. F., in H. G. Mary(Ed), Encyclopedia of Chemical Technology, (J. Wiley & Sons, New York, 3rd edn), 21, (1983). 2. Sicard, P.-J., io-industries: La Nouvelle Donne, Infochimie Magazine, 415, 68-72(2). 3. King, J. C. and Paul,., Process for Sorption Solute Recovery, US Patent No. 4,67,155(1987). 4. aniel,. M., Recovery of Carboxylic cid from Organic Solutions that Contains an mine and an Extraction Enhancer, US Patent No. 5,78,276(1998). 5. erglund, K.., Elankovan, P. and Glassner, D.., Carboxylic cid Purification and Crystallization Process, US Patent No. 5,34,15(1991). 6. Kang, M. S., Water-splitting Phenomena and pplications in Ion-exchange Membranes, Ph.D Thesis, GIST, Gwangju(23). 7. Kemperman,. J.., Handbook on ipolar Membrane Technology, Twente Univ. Press, Enschede(2). 8. Carrere, H., laszkow, H. and Roux-de almann, H., Modelling of the Clarification of Lactic cid Fermentation roths by Cross Flow Microfiltration, J. Membr. Sci., 186(2), (21). 9. ailly, M., Roux-de almann, H., imar, P., Lutin, F. and Cheryan, M., Production Processes of Fermented Organic cids Targeted round Membrane Operations: Design of the Concentration Step by Conventional Electrodialysis, J. Membr. Sci., 191(1-2), (21). 1. Strathmann, H., Krol, J. J., Rapp, H. J. and Eigenberger, G., Limiting Current Density and Water Dissociation in ipolar Membranes, J. Membr. Sci., 125(2), (1997). 11. Gineste, J. L., Pourcelly, G., Lorrain, Y., Perrin, F. and Gavach, C., nalysis of Factors Limiting the use of ipolar Membranes: Simplified Model to Determine Trends, J. Membr. Sci., 112(2), (1996). 12. Paula, J. M., Satish, J. P. and Shih, P. T., Competitive nion Transport in Desalting of Mixtures of Organic cids by atch Electrodialysis, J. Membr. Sci., 141(1), 75-89(1998). 13. Roux-de almann, H., ailly, M., Lutin, F. and imar, P., Modelling of the Conversion of Weak Organic cids by ipolar Membrane Electrodialysis, Desalination, 149(1-3), (22). 14. Lee, E. G., Moon, S. H., Chang, Y. K., Yoo, I. K. and Chang, H. N., Lactic cid Recovery Using two-stage Electrodialysis and Its Modelling, J. Membr. Sci., 145(1), 53-66(1998). 15. Lee,. C. and Kim, S. H., Separation of Succinic cid from Organic cid Mixture Using Electrodialysis, Korean Chem. Eng. Res., 43(2), (25). o44 o5 26 1k

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