Evaluation of Ion-Exchange and Adsorbent Resins for the

Aug 20, 2010 - AgroParisTech and INRA, UMR 1145 Ingénierie Procédés Aliments, 1 aVenue des Olympiades,. F-91300 Massy, France. Batch isotherm ...
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Ind. Eng. Chem. Res. 2010, 49, 9248–9257

Evaluation of Ion-Exchange and Adsorbent Resins for the Detoxification of Beet Distillery Effluents Claire Fargues,* Richard Lewandowski, and Marie-Laure Lameloise AgroParisTech and INRA, UMR 1145 Inge´nierie Proce´de´s Aliments, 1 aVenue des Olympiades, F-91300 Massy, France

Batch isotherm experiments were carried out to select the best chromatographic supports for the purification of beet distillery condensates with the aim of recovering fermentable water. Adsorption parameters of four inhibitory solutes of the condensates chosen as targets were obtained, leading to the selection of a weak anion-exchanger and a polystyrenic resin. These results were further used for the chromatographic scaleup. Dynamic adsorption experiments run on both resins with a synthetic mixture of the four target solutes showed the presence of competition for the adsorption. The extended Langmuir model was then found to be applicable for a first estimation of the solute breakthrough. The treatment efficiencies of the two supports were confirmed with an industrial condensate, indicating components in the effluent that were not considered did not significantly affect the adsorption of the main compounds. Eventually, a combination of the two complementary resins was proposed for complete effluent detoxification. 1. Introduction Like many fermentation industries, beet distillery plants require large quantities of water, especially for the dilution of fermentation musts (8 L of water per liter of alcohol produced), and generate an equivalent volume of final effluent. As further development is expected in the coming years with an increasing demand for biofuel, improving the management of the effluents produced is a necessity. Condensates generated by stillage evaporation have a chemical oxygen demand (COD) of up to 10 g of O2 L-1 depending on the plants. They are usually sent to stabilization ponds, where a few months’ retention time is required before land-spreading. This is a costly practice constrained by restrictive rules. Recycling the condensates at the fermentation stage is thus an effective way to simultaneously decrease wastewater production and water consumption, and it would also contribute to the preservation of local groundwater resources.1 It has been shown, however, that purification of this effluent is necessary before recycling, as it contains toxic compounds released from the raw materials or formed during the alcohol production stage.2 Because of their major inhibitory power, acetic acid (aa), butanoic acid (ba), furfural (f), and 2-phenethyl alcohol (phol) were chosen as targets among nine well-identified and -quantified inhibitory compounds. They are known to affect microbial metabolism,3,4 and their inhibitory power has been assessed in single-compound solutions through batch fermentation tests.5 It was shown that acetic acid is inhibitory because of its high concentration in the condensates more than because of its intrinsic inhibitory power. On the contrary, more dilute compounds such as longer carboxylic acids or furfural appear to be very inhibitory even at small concentrations. Moreover, synergic effects were noticed for mixtures of several inhibitors. Therefore, it appears imperative to remove as much of the inhibitory solutes as possible to ensure safe recycling of the condensates at the fermentation stage. Similar compounds are likely to appear in hemicellulosic hydrolyzates (from storn cover, softwood, sugar cane bagasse, * To whom correspondence should be addressed. Address: AgroParisTech, UMR 1145 Ge´nie Industriel Alimentaire, 1 av des Olympiades, F-91300 Massy, France. Tel.: +33 (0)1 69 93 50 95. Fax: +33 (0)1 69 93 50 44. E-mail: [email protected].

etc.) rich in sugars such as xylose, which makes them suitable feedstocks for the production of ethanol or other valuable chemicals by fermentation. Their detoxification is therefore of major concern, and ion exchange, adsorption (activated carbon or polymeric adsorbents), and combined treatment procedures have already been investigated.6-12 Through these studies, it appears that carboxylic acids and acetic acid in particular are well retained by weak or strong anion exchangers.7-9 This is in agreement with the fact that, for ionized or highly polar solutes, ion exchange represents a commonly used method; furthermore, ion-exchange supports can be reused and regenerated easily, especially weak ion exchangers, which, in addition, show higher exchange capacities than strong ion exchangers.13 Phenol and furan derivatives in hydrolyzates seem to be better adsorbed on hydrophobic polymeric adsorbents than on activated carbon.7,12 This confirms more fundamental studies showing that polymeric adsorbents, and polystyrenic adsorbents in particular, are efficient for the adsorption of phenolic and other aromatic molecules.14-16 In addition, because of their greater mechanical strength and feasible regeneration under mild conditions, synthetic porous polymeric adsorbents are an attractive alternative to activated carbons for efficiently removing or recovering the organic compounds contained in chemical and industrial effluents. Most of the time, the previously cited studies evaluated treatment efficiency through the subsequent hydrolyzate fermentability, and as such, they neither differentiated the influence of each inhibitory solute nor provided fundamental results such as equilibrium adsorption data of single compounds on the supports tested. Extrapolation to other effluents with similar solutes is therefore difficult. In the present study, two adsorbents and two anion exchangers produced by Rohm and Haas Co. (Dow Chemical Company, Midland, MI) were compared with respect to their retention capacities for the four target inhibitory molecules of the condensates to be treated (Table 1,17). Amberlite XAD4 and Amberlite XAD7HP adsorbents were chosen for their potential retention of the aromatic and/or low-polarity compounds. The polystyrene DVB matrix of XAD4 is known to have an excellent selectivity toward aromatic solutes, including furfural,1,14,15,18-20 as a result of specific π-π interactions.21 Moreover, its char-

10.1021/ie100330y  2010 American Chemical Society Published on Web 08/20/2010

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Table 1. Physicochemical Characteristics of the Solutes under Study

Table 2. Physical Properties of the Resins resins XAD4 XAD7HP A26 OH A21 a

matrix styrenic acrylate styrenic styrenic

MRa MRa MRa MRa

functional groups

average diameter (µm)

surface area (m2 gdry-1)

exchange capacity (equiv L-1)

quaternary amine tertiary amine; pKa ≈ 9

490-690 560-710 560-700 490-690

>750 >380 30 35

nonpolar polar >0.8 >1.3

bed porosity ε

Fapp (g L-1)

0.61

292.4

0.64b

273b

MR ) macroreticular. b Free-base form.

acteristic pore size distribution (average pore size ) 5 nm) makes it an excellent adsorbent for organic substances of relatively low molecular weight such as those in the condensates to be treated.22 XAD7HP resin is a nonionic aliphatic acrylic polymer with a more hydrophilic structure than XAD4.19 It is expected to be less efficient for the retention of the aromatic target compounds, but because of its more polar matrix, it could represent a good compromise with a possible retention of the polar carboxylic acids that have to be eliminated as well. Concerning the carboxylic acids, both strong and weak basic anion exchangers could be good candidates for the retention of these acids.23-25 Therefore, both exchanger types with a hydrophobic polystyrene matrix were tested (Amberlyst A26 OH and Amberlyst A21). Despite their grafting, they are expected to have affinity also for the aromatic solutes because of their phenyl rings. The best chromatographic resin(s) for this particular application were selected through batch isotherm experiments. Two complementary supports were identified, and the retention results obtained were further used for the chromatographic scaleup. Dynamic adsorption experiments were then run on both resins with a synthetic mixture of the four target solutes and an industrial condensate, to check the equilibrium capacities under competitive conditions. A treatment procedure was finally proposed to achieve complete detoxification of this effluent. 2. Material and Methods 2.1. Chromatographic Supports and Organic Solutes. The supports were purchased from Rohm and Haas Co. (Dow Chemical Company, Midland, MI) (Table 2): Amberlite XAD4 and Amberlite XAD7HP are particularly expected to retain rather nonpolar compounds, as already mentioned. They are based on a polystyrene (nonpolar) matrix and a polyacrylic ester (polar) matrix, respectively. Both adsorbents were purified before use by removing the residual monomers with ethanol

and were then further washed several times with deionized water. Amberlyst A26 OH and Amberlyst A21 are polystyrenic and anionic resins which are strong and weak respectively. Prior to being used, they were washed with deionized water several times to remove inorganic impurities and conditioned with 1 M NaOH. They were finally rinsed with deionized water. A21 is thus under free base form, whereas A26 OH amine groups are positively ionized, regardless of the pH. All chemical products were of analytical grade (purity > 99%). Butanoic acid, furfural, and 2-phenethyl alcohol were purchased from Sigma-Aldrich (Saint-Quentin Fallavier, France), and acetic acid was obtained from Fisher Scientific Labosi (Elancourt, France). For chromatographic experiments, a synthetic mixture was prepared in accordance with the average composition of distillery condensates.5 An industrial condensate, provided by a French beet distillery, was also eventually studied (Table 3). 2.2. Analytical Methods. For the study of single-solute retention through batch experiments, the initial and final concentrations of each solute were measured after calibration by UV spectroscopy (V-550 spectrophotometer, Jasco, Paris, France) at a wavelength adapted to the particular molecule. To avoid a pH effect on the UV-absorption response of the carboxylic acids, all standards and samples were acidified at pH 2, by addition of 0.1% (v/v) 4.5 M sulfuric acid. Concerning the column experiments on synthetic mixtures or industrial condensates, samples taken at the column outlet were analyzed by high-performance liquid chromatography (HPLC) with an equipment including a 465 automatic HPLC injector autosampler (Bio Tek Instruments, Inc., Winooski, VT), an Aminex HPX 87 H column (7.8-mm i.d., 300-mm length, from Bio-Rad, Marnes La Coquette, France) maintained at 35 °C, and a Gilson 307 injection pump. For the detection of fa, aa, pra, ba, pa, ha, f, and phol, a Waters 996 photodiode array detector was used at wavelengths of 207 nm for the acids and

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Table 3. Compositions of Synthetic and Industrial Mixtures

a

industrial condensatea

synthetic solution

compound, abbreviation

beet distillery condensates: concentration range5 (mg L-1)

mg L-1

mmol L-1

formic acid, fa acetic acid, aa propanoic acid, pra butanoic acid, ba pentanoic acid, pa hexanoic acid, ha furfural, f 2-phenethyl alcohol, phol 2,3-butanediol, bdiol

20-120 900-2500 80-120 50-200 10-70 100 44

>100 30 38 38 12 2

a Vbi corresponds to a leakage of 10% of CFeed i and includes porous and extracolumn volumes.

Figure 10. Breakthrough curves of target solutes in a synthetic mixture on A21 (one experiment: BV ) 16.2 cm3, Q ) 4.2 BV h-1).

ticomponent adsorption.31-33 The decreasing section of its excess peak concentration occurs simultaneously with the acetic acid breakthrough. As the two types of molecules probably do not compete for the same retention sites, a salting-out effect might explain the rejection of the poorly sorbed apolar phol by the highly polar and concentrated acetic acid during exchange on this resin. In the synthetic mixture, the concentration of acetic acid is twice that in the industrial condensate. The spreading of a sorption front is known to be controlled by the shape of the corresponding equilibrium isotherm.34,35 Because of the favorable isotherm shape for this acid and its higher concentration in the synthetic mixture, its breakthrough appears steeper, which could explain the higher concentration effect observed for the displaced 2-phenethyl alcohol. It can also be observed in Figures 10 and 11 that the breakthrough curve is much steeper for acetic acid than for butanoic acid. In the case of acetic acid, the isotherm curvature is noteworthy from 0 to CFeed, leading to a clear compressive wave and breakthrough. With a concentration

10 times smaller (CFeed < 3 mM), ba exhibits an adsorption isotherm that could be considered linear, corresponding to a much broader shape of the breakthrough curve. Table 7 shows good retention for all of the acids in the industrial condensate, with Vbi values of over 30 BV; formic acid does not even break through in the time of the experiment. As for XAD4, a competition model is essential for a good evaluation of the solute retention (Table 6b), as the VSCi estimations are very far from the experimental VSEi values. The major competitive effects seem to be between acetic and butanoic acids, the most retained compounds of the condensates on this resin. However, for both the synthetic and industrial effluents, the extended Langmuir model leads to an inversion of the calculated breakthroughs relative to the experimental values, with acetic acid appearing to be more retained than butanoic acid: the model underestimates the influence of other molecules on the acetic acid retention and overestimates this influence on butanoic acid. Improvement of the model fit would probably be obtained by adjustment of the Ki equilibrium constants of both acids: in that case, Kba should be increased, and Kaa should be decreased. The shift appears to be higher in the case of the industrial condensate. For acetic acid, it can be assumed that other carboxylic acids not considered in the model hinder its adsorption, particularly formic and propanoic acids, whose concentrations in the effluent are significant (Table 3). Additional acids such as 2-butenoic, isovaleric, 2-methylbutanoic, and octanoic acids, in particular, were detected in a previous study2 and could also affect both the butanoic and acetic acid retentions.

Figure 11. Breakthrough curves of solutes in industrial condensate on A21 (two experiments: BVa ) 14.4 cm3, Qa ) 4.1 BVa h-1; BVb ) 15.2 cm3, Qb ) 4.2 BVb h-1).

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Table 8. Solute Breakthrough Volumes and Concentrations in the A21 Outlet during XAD4-A21 Combination Experiments cycle 1

cycle 2

CFeed i Vbi Cplateau i Cplateau i/ Vbi Cplateau i Cplateau i/ (mg L-1) (BV) (mg L-1) CFeed i(%) (BV) (mg L-1) CFeed i(%) acetic acid furfural

980 9

16 17

120 9

12.2 100

18 17

20 4

2.0 44.4

To estimate the industrial condensate treatment on this anionexchange resin, a fermentation test was performed on the first 35 BV of effluent obtained. An inhibition of 1.5% arose which was very small compared to the inhibition of the untreated condensate (about 20%). This residual inhibition might be due to the neutral molecules still remaining in the treated condensate. From these results, we see that it is necessary in any case to take the competitive effects into account for a correct prediction of the breakthrough of the solutes in question, particularly for the major interacting solutes: acetic and butanoic acids on A21 and furfural and 2-phenethyl alcohol on XAD4. 3.2.3. Combination of XAD4 and A21. For complete purification of the distillery condensate, A21 should be associated in series with XAD4 (Figure 1). Actually, it was observed that XAD4 not only adsorbs the aromatic solutes in the condensate well, but also adsorbs butanoic acid, whose breakthrough volume is over 20 BV. During that period, the XAD4 effluent is free of this acid, which is the major competing solute for the acetic acid retention on the A21 support. An enhanced retention of acetic acid on A21 is then expected when introduced after the XAD4 column, compared to the results obtained with A21 alone. As XAD4 and A21 columns are connected in series, management of the global treatment process would be simplified if the regeneration and rinsing steps occurred simultaneously for both resins. For the design of this combination, attention was focused on furfural retention on XAD4 and acetic acid retention on A21, as those molecules cannot be eliminated by the complementary support. If not desired in the purified condensate, retention of those molecules on the appropriate support should be total during the time of the treatment. As already seen, breakthrough of furfural on XAD4 occurs after 44 BV and its VSEi is about 64 BV. In the case of the resin combination, with BV1 ) 14.6 cm3 for XAD4 (Table 4), the treated condensate volume could then be around 0.95 L. This column would then need regeneration and rinsing steps. Concerning the A21 column, the acetic acid breakthrough occurs much sooner, at 30 BV, and its VSEi is 38 BV, or 0.56 L for a similar resin volume, with a 40% smaller value than the furfural one on XAD4. Therefore, a volume of A21 resin twice that of XAD4 was used (BV2, Table 4). The acetic acid VSE value on A21 would then correspond to a feed volume of 1.06 L, close to that of the furfural on XAD4 column. The condensate volume that could be treated through this pattern would then correspond to 23(BV1 + BV2) or about 68 BV1. To check the assumptions made and verify the breakthroughs of both solutes, a greater volume of the industrial condensate was loaded on the combined XAD4 and A21 columns [1.8 L corresponding to about 42(BV1 + BV2) or 120BV1]. As already mentioned, two successive adsorption-regeneration cycles were performed. During these experiments, neither propanoic and butanoic acids nor 2-phenethyl alcohol appeared in the A21 outlet (Table 8). They were completely eliminated from the industrial condensate. As expected, acetic acid and furfural were the “limiting solutes” (Figures 12 and 13, respectively). They appeared in the effluent after 17 BV, or 0.72 L of condensate feed, sooner than predicted. As the condensate first flowed

Figure 12. Acetic acid breakthrough during successive treatment experiments using XAD4 and A21 in combination (BV ) BV1 + BV2 ) 42.5 cm3, Q ) 1.12 cm3 min-1).

Figure 13. Furfural breakthrough during successive treatment experiments using XAD4 and A21 in combination (BV ) BV1 + BV2 ) 42.5 cm3, Q ) 1.12 cm3 min-1). Table 9. Capacities and Regeneration Efficiencies for the Solutes during XAD4-A21 Combination Experiments average q (mmol g-1) CFeed i q *Langmuir regeneration compound (mmol L-1) cycle 1 cycle 2 (mmol g-1) efficiency (%) aa ba f phol

16.4 1.90 0.094 0.16

3.37 >0.417 0.016 >0.064

3.56 >0.417 0.027 >0.064

4.59 1.02 0.023 0.265

70-82 71-75 50 40

through the XAD4 resin before reaching A21 column, dispersion effects probably spread the breakthrough curve of acetic acid, corresponding to a similar spread of its concentration at the inlet of the A21 column and leading to a premature breakthrough. However, the aa and f concentrations in the effluent were much reduced, especially during the second cycle, for which the average concentrations of acetic acid and furfural in the 40 BV of treated condensate reached 10 and 2 mg L-1, respectively (i.e., only 1% and 25%, respectively, of their initial concentrations). Capacities for all the solutes through this coupling were calculated by integration of the breakthrough curves and compared to the capacities calculated by the Langmuir equation (eq 1) on the most efficient column, namely, aa and ba retentions attributed to the A21 column and phol and f retentions attributed to the XAD4 column. The results obtained are reported in Table 9. They show that the absence of ba and phol at the outlet of the columns is normal, as the theoretical q*Langmuir capacity is far above the quantity injected during the experiment for those solutes. Concerning aa and f, as already mentioned, the results were better during cycle 2, with an increased capacity. The capacity for furfural was close to the theoretical Langmuir value

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on XAD4. For acetic acid, it was still smaller, probably because of the competition of other acids as previously discussed. Improvement of the capacities from the first to the second cycle is probably due to the improvement of the resin packing after the first regeneration stage. Actually, regeneration leads to an expansion followed by shrinking of the resin bed when subjected consecutively to the regeneration solution (ethanol or NaOH), water, and acid condensate. This improved the hydraulics in the bed, reducing dead volumes. The regeneration efficiencies of both supports were also evaluated from the ratio of the recovered compounds in the regeneration and rinse fractions to the adsorbed quantity (Table 9). It showed an incomplete recovery, especially for neutral molecules, confirming the difficulty of regenerating the adsorbent support in particular. This step should be adjusted for the optimization of the continuous process. Eventually, the efficiency of that treatment process for effluent detoxification appeared satisfactory, as the fermentation test run on the 40 BV of effluent obtained showed no inhibition. Issues of water savings through this treatment and of the disposal of the ultimate effluents have also been considered. Regarding the anion exchanger A21, a preliminary study was conducted in the laboratory with a similar condensate on a similar resin.36 Fresh water consumption could further be evaluated: The volume of water used for the optimized regeneration and rinsing steps was about 6 BV. Given that the volume of condensates treated with A21 resin before needing regeneration was about 35 BV and considering that the entirety of that volume could be sent to the fermentation step as dilution water, we conclude that anion-exchange treatment alone would lead to an 83% water savings. Regarding the remaining regeneration liquor, several possibilities are currently being investigated for its disposal. The simplest one consists of recycling it to the stillage’s concentration stage. It was checked that the introduction of this basic liquor did not significantly change the conditions in the evaporator. Sodium acetate and hydroxide (the main components of the liquor) are then recovered with the dry matter used as fertilizer; for better agronomic valorisation, KOH should be used as regenerant instead of NaOH. 4. Conclusions By associating a polystyrenic adsorbent support and a weakbase ion-exchanger resin, the purification of industrial beetdistillery condensate was achieved. Scaleup of the process requires the equilibrium adsorption data for each of the solutes, as well as a model taking competitive effects into account. Therefore, adsorption isotherms for each of the four major inhibitory compounds chosen as targets were measured separately on several chromatographic resins, allowing for the choice of the most efficient chromatographic combination. According to these experiments, it appeared that the apolar and macroporous polystyrenic XAD4 support was very efficient for the adsorption of the aromatic solutes (furfural and 2-phenethyl alcohol) because of the π-π interactions that occur. This support also allowed, to a lesser extent, other apolar solutes such as butanoic acid to be retained. For the elimination of the smallest acids (formic, acetic, and+or propanoic acids), use of an anionexchanger resin was necessary, with a weak one based on a polystyrenic matrix giving the best results. On the other hand, this resin was inefficient for the retention of the aromatic inhibitory compounds investigated, as its apolar and aromatic skeleton was mostly hidden by the grafted tertiary amine groups.

When favorable adsorption was observed, the isotherms could be modeled according to a Langmuir equation. The breakthrough volumes obtained for the target compounds during dynamic experiments with mixtures showed that an extended Langmuir model gave a good prediction of the retention efficiency, especially in the case of industrial effluent. The prediction of the retention of acetic acid would probably be improved by considering the influence of additional acids present in the condensate at significant concentrations. Establishment of complementary isotherms for formic and propanoic acids in particular would then be beneficial. Concerning condensate purification, use of the adsorbent XAD4 column alone did not lead to a sufficient detoxification level because of the acetic acid still remaining in the effluent produced. An A21 column gave better results, but did not retain the aromatic inhibitory compounds (furfural and 2-phenethyl alcohol). Recycling of this effluent at the fermentation stage could then lead, with time, to an accumulation of those unassimilated molecules in the fermentation broth and to a likely strong inhibition of yeast growth after a while. The combination of the two supports, therefore, appears to be appropriate for the complete purification of beet distillery condensates. An A21 resin volume twice that of XAD4 adsorbent was used to achieve simultaneous regenerations. For one XAD4 bed volume (and consecutively, two A21 bed volumes), an equivalent of 120 BV of effluent could be treated. The condensate treated in that way did not show any residual inhibition. Eventually, the isotherm results established in this study could serve similar applications: guiding the choice of the resin and allowing a first evaluation of the resin bed volumes to be implemented for the treatment of distillery effluents containing mainly those solutes. Acknowledgment The authors gratefully acknowledge the Rohm and Haas Co. (Dow Chemical Company, Midland, MI) for providing all of the resins used in this study free of charge. Nomenclature BV ) resin bed volume in column (L) C0i ) initial concentration of solute i in the solution (batch experiments) (mol L-1) CFeed i ) concentration of solute i in the solution at the column inlet (mol L-1) Ci ) concentration of solute i in the solution (mol L-1) C*i ) concentration of solute i in the solution, in equilibrium with q*i (mol L-1) i ) solute i (subscript) Inh ) inhibition of fermentation (%) Ki ) equilibrium constant for sorption of solute i (L mol-1) KOW ) octanol/water partition coefficient m ) dry weight of resin in the batch (g) mC ) dry weight of resin in the column (g) Q ) column feed volumetric flow rate (cm3 min-1 or BV h-1) q*i,n ) theoretical resin capacity for solute i in a mixture of n solutes (mol g-1 dry resin) q*i ) adsorbed amount of solute i in the resin phase (i.e., resin capacity) in equilibrium with C*i (mol g-1 dry resin) qsi ) maximum adsorbed amount of solute i (mol g-1 dry resin) ts ) mean residence time of a tracer (i.e., total void time) (s) Vbi ) breakthrough volume, when Ci ) 10% of CFeed i (L) Ve ) extracolumn dead volume (L) Vp ) void volume in the resin bed (L)

Ind. Eng. Chem. Res., Vol. 49, No. 19, 2010 VS ) stoichiometric breakthrough volume or mass center of the breakthrough (L) VSCCi ) theoretical stoichiometric breakthrough volume for solute i taking competitive effects into account (L) VSCi ) theoretical stoichiometric breakthrough volume for solute i without competitive effects (L) VSEi ) experimental stoichiometric breakthrough volume for solute i (L) ε ) global bed porosity Fapp ) apparent density of the resin bed (g L-1) Compounds aa ) acetic acid ba ) butanoic acid bdiol ) 2,3-butanediol f ) furfural fa ) formic acid ha ) hexanoic acid pa ) pentanoic acid phol ) 2-phenethyl alcohol pra ) propanoic acid

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ReceiVed for reView February 11, 2010 ReVised manuscript receiVed July 5, 2010 Accepted July 5, 2010 IE100330Y