Extraction of Gibberellic Acid from Aqueous Solution by Amberlite LA

Article pubs.acs.org/jced

Extraction of Gibberellic Acid from Aqueous Solution by Amberlite LA‑2 in Different Diluents Hasan Uslu* Engineering & Architecture Faculty, Chemical Engineering Department, Beykent University, Ayazağa, Iṡ tanbul, Turkey ABSTRACT: The (3S,3aS,4S,4aS,7S,9aR,9bR,12S)-7,12-dihydroxy-3-methyl-6-methylene-2-oxoperhydro-4a,7-methano9b,3-propenoazuleno[1,2-b]furan-4-carboxylic acid (Gibberellic acid (GA)) extraction from aqueous solution by Amberlite La-2 in different diluents (isoamyl alcohol, or octan-1-ol, or decan-1-ol) was studied. According to experimental results, some thermodynamic parameters such as distribution coefficients (KD), loading factors (Z), and extraction efficiency (E) were calculated. The best extraction efficiency, distribution coefficient, and loading factor were determined by isoamyl alcohol diluent at values of 98 %, 97, and 4.6, respectively. Besides, the linear solvation energy relationship (LSER) model regressed to experimental results with a regression coefficient (R square) of 0.98. The LSER model predicts results close to experimental data.

1. INTRODUCTION The fermentation method is the most chosen method for the production of carboxylic acids which are used in the medicine and food additive industries. These acids are produced approximately 8 % in mass, and they must be separate from aqueous solution. Distillation, precipitation,1 membrane,2,3 and adsorption4,5 methods have been used for separating many acids from aqueous and other media solutions, but nowadays the reactive extraction is the most promising method. Reactive extraction is getting attractive and more use in the separation process day by day. This method is based on the acid−amine complex formation. Besides, appropriate diluents should be used to decrease the viscosity of amine and solve between the complex of acid and amine after reactive extraction in the organic phase. Therefore, the chemical structure of used diluents is important. A change in polarity of organic diluents in the extractant can cause changes in complexation. Polar diluents give a high distribution coefficient. Therefore, polar diluents were studied to solve amine in this study. Recently, there have been many attractive studies in the literature about extraction of many carboxylic acids from aqueous solution by the separation method of reactive extraction. Tang et al.6 focused on reactive extraction of ibuprofen enantiomers from organic media to aqueous media by using hydroxypropylβ-cyclodextrin (HP-β-CD). The modeling and experimental data of extraction performance factors were investigated to obtain the optimal extraction conditions. Wasewar et al.7 investigated itaconic acid extraction by means of quaternary amine salt (Aliquat 336) diluted in ethyl acetate, toluene, hexane, and kerosene. The results were presented in the form of distribution coefficient, loading ratio, and equilibrium complexation constant. Wasewar and Shende8 reported equilibrium for the reactive extraction of caproic acid using tri-n-butyl phosphate in methyl isobutyl ketone and xylene. Martı et al.9 tested the separation of pyruvic acid © 2012 American Chemical Society

from aqueous solution using trioctylamine (TOA) or Alamine 336 in octan-1-ol or oleyl alcohol. Cascaval et al.10 focused on the effect of polarity of solvents on the reactive extraction of acetic acid with tri-n-octyl amine.

2. CHEMICALS AND METHODS 2.1. Chemicals. Amberlite La-2 which is a secondary amine and anion exchange extractant was purchased from Merck Co. (purity is greater than 99 %). Amberlite La-2 is a colorless liquid with molecular weight of 353.67 g·mol−1. GA (Merck, purity is greater than 99 % in mass fraction), isoamyl alcohol (Merck, purity is greater than 99 % in mass fraction), octan-1-ol (Merck, purity is greater than 99 % in mass fraction), and decan-1-ol (Merck, purity is greater than 99 % in mass fraction) were used without further purification. 2.2. Methods. The GA is produced by a fermentation method with fungi Gibberella f ujikuroi as 0.65 g·kg−1. This is the initial concentration of GA, and it is prepared with dissolving in distilled water (1.877·10−3 mol·kg−1). Eight constant concentrations of Amberlite La-2 were prepared by mixing diluents (isoamyl alcohol, octan-1-ol, decan-1-ol). Prepared concentrations of Amberlite La-2 are changed from 0.1 mol·kg−1 to 0.8 mol·kg−1 at 0.1 intervals. These (Amberlite La-2+diluents) mixtures help to find the optimum concentration of amine. Equal volumes of an aqueous GA and prepared organic solution of LA-2 were mixed in Erlenmeyer flasks. These prepared two-phase systems were shaken in a temperature-controlled Shaker at 50 rpm and 25 °C for 2 h. After equilibration, both phases were separated. Received: August 11, 2012 Accepted: November 9, 2012 Published: November 19, 2012 3685

dx.doi.org/10.1021/je300983b | J. Chem. Eng. Data 2012, 57, 3685−3689

Journal of Chemical & Engineering Data

Article

The amount of GA in the aqueous phase after extraction was analyzed by a UV spectrophotometer at 254 nm as explained by Holbrook et al.11 Determination of relative uncertainty in the aqueous phase was in 1 %. The deviation of amount of acid in both phases was 1 %. The solubilities of organic compounds used in this study in the aqueous phase were negligible.

3. RESULTS AND DISCUSSION The physical extraction and reactive extraction were studied in respect to distribution coefficient (D), loading factor (Z), and extraction efficiency (E). The values of distribution coefficient2 (D) are described by the ratio of the concentration of GA in the organic phase to the concentration of GA in the aqueous phase Corg D= Caq (1)

Figure 1. Equilibrium distribution of GA in the organic phase. Corg is the concentration of GA in the organic phase, and CLA‑2 is the concentration of Amberlite LA-2 in the organic phase: ⧫, isoamyl alcohol; □, octan-1-ol; ▲, decan-1-ol.

In eq 1, Corg is the concentration of gibberellic acid in the organic phase, and Caq is the concentration of gibberellic acid in the aqueous phase. The loading factor2 (Z) is described by the ratio of the concentration of acid in the organic phase and the concentration of amine in the organic phase. Z=

At low [Amberlite LA-2], D is directly proportional to [Amine]. According to the results of diluents in the distribution coefficient, they varied between 97.7 and 0.179. At an intermediate concentration of 0.4 mol·kg−1, Amberlite LA-2 has the highest value of distribution coefficients of 97.7, 8.4, and 3.4, and the extraction efficiency (E) is 97 %, 89 %, and 77 % for isoamyl alcohol, octan-1-ol, and decan-1-ol, respectively. These results may be explained by solvation power of diluents to Amberlite LA-2. This solvation power depends on its polarity, and also the polarity depends on the dielectric constant of diluents. In this work, used diluents (isoamyl alcohol, octan-1-ol, and decan1-ol) have values of dielectric constants of 15.3, 10.3, and 8.1, respectively. In a previous study,13 the extraction of GA by tricaprylmethylammonium chloride (TOMAC) in the same diluent (isoamyl alcohol or octan-1-ol or decan-1-ol) systems were studied. The highest distribution coefficients of the (TOMAC + (isoamyl alcohol, or octan-1-ol, or decan-1-ol)) were found as 3.81, 1.78, and 1.21, respectively. In this study, the highest distribution coefficients of the (Amberlite LA-2 + (isoamyl alcohol, or octan1-ol, or decan-1-ol)) ternary systems were found as 97.7, 8.4, and 3.4, respectively. The results showed that the Amberlite La-2 is a more suitable extractant than TOMAC with the same diluents. The values of extraction efficiencies of alcohols used in a previous study varied from 22 % to 79 %. In this study, the values of extraction efficiencies of the alcohols varied from 24 % to 97 %. Table 2 presents loading factor values for isoamyl alcohol, octan-1-ol, and decan-1-ol. As seen from Table 2 and clearly shown in Figure 2, Z values are gradually decreasing with an increase of concentration of Amberlite LA-2. Overloading is described as bigger than unity (>1). This shows that the complexes have more than one acid per amine. For systems with only one amine per complex, it can be seen that there is no effect of total amine concentration on the loading. In these experimental studies, overloading has been observed almost at all amine concentrations. This situation can be explained by formation of a complex between acid and amine. The loading factors for the used diluent in this study were observed to decrease from 0.766 to 7.14 with an increase of amine concentration from 0.1 mol·kg−1 to 0.8 mol·kg−1. The loading factor gives information about the overall complexation constant (KE) between acid and amine.

Corg C LA‐2

(2)

In eq 2, Corg is the concentration of gibberellic acid in the organic phase, and CLA‑2 is the concentration of amine in the organic phase. The efficiency of extraction, E, is expressed as ⎛ Caq ⎞ E = ⎜1 − ⎟ ·100 C initial ⎠ ⎝

(3)

In eq 3, Caq is the GA concentration present in the aqueous phase after the extraction, and Cinitial is the initial GA concentration present in the aqueous phase. E gives information on how much acid was removed from the aqueous phase to the organic phase after extraction. Table 1 and Figure 1 show results of physical extraction equilibrium. As seen from the results, the maximum extraction of GA is 0.12 mol·kg−1, and its efficiency is 6.3 %. Table 1. Results for Physical Extraction of GA at T = 298 Ka Corg −1

diluents

(mol·kg )·10

IAA OCT DEC

0.12 0.087 0.059

Caq 3

(mol·kg−1)·103

D

%E

1.757 1.79 1.818

0.068 0.048 0.032

6.3 4.6 3.1

Corg/mol·kg−1 is the concentration of GA acid in the organic phase; Caq/mol·kg−1 is the concentration of GA in the aqueous phase; D is the distribution coefficient; E is the extraction efficiency; IAA is the isoamyl alcohol; OCT is the octan-1-ol; and DEC is the decan-1-ol. a

Reactive extraction results for isoamyl alcohol, octan-1-ol, and decan-1-ol were presented in Table 2. As seen from Figure 2 and Table 2, when the amount of Amberlite LA-2 increases in the organic phase, the extraction power increases until a maximum of 0.4 mol·kg−1 at an intermediate amine concentration. After this concentration, the distribution coefficient (D) decreased. The reason for this behavior was explained in a previous article.12

Z = Caq − KE 1−Z 3686

(4)



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Table 2. Results for Reactive Extraction of GA at T = 298 Ka CLA‑2

Corg

diluents

mol·kg−1

mol·kg−1·103

D

Dmodel

Z

%E

KE

IAA

0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8

0.714 1.152 1.421 1.858 1.821 1.429 1.204 0.945 0.583 0.98 1.342 1.679 1.592 1.311 1.058 0.796 0.452 0.78 1.129 1.452 1.423 1.102 0.817 0.613

0.613 1.588 3.116 97.789 32.517 3.189 1.789 1.013 0.450 1.092 2.508 8.479 5.585 2.316 1.291 0.736 0.317 0.711 1.509 3.416 3.134 1.421 0.770 0.484

0.611 1.513 3.305 94.519 31.846 3.325 1.810 1.044 0.438 1.084 2.491 8.392 5.778 2.125 1.301 0.727 0.319 0.741 1.539 3.372 3.202 1.437 0.748 0.496

7.14 5.76 4.736 4.645 3.642 2.381 1.72 1.181 5.83 4.9 4.473 4.197 3.184 2.185 1.511 0.995 4.52 3.90 3.76 3.63 2.846 1.836 1.167 0.766

38.039 61.374 75.705 98.987 97.016 76.132 64.144 50.346 31.060 52.210 71.497 89.451 84.816 69.845 56.366 42.408 24.081 41.555 60.149 77.357 75.812 58.711 43.526 32.658

1.29

OCT

DEC

1.34

1.43

a CLA‑2/mol·kg−1 is the concentration of Amberlite LA-2 in the organic phase; Corg/mol·kg−1 is the concentration of GA in the organic phase; D is the distribution coefficient; Dmodel is the distribution coefficient calculated by the LSER model; E is the extraction efficiency; KE is the complexation constant; IAA is the isoamyl alcohol; OCT is the octan-1-ol; and DEC is the decan-1-ol.

Figure 3. Estimation of the equilibrium complexation constant (KE) for isoamyl alcohol. Caq/mol·kg−1 is the concentration of GA in the aqueous phase. Figure 2. Distribution of loading factor (Z). CLA‑2 is the concentration of Amberlite LA-2 in the organic phase: ⧫, isoamyl alcohol; □, octan-1-ol; ▲, decan-1-ol.

system in reactive extraction, a new LSER model was given by Bizek et al.14 The influence of solvent effects on a single solute is shown in eq 5, whereby XYZ resembles the property to be correlated.

According to eq 4, a plot of Z/1 − Z vs concentration of acid in the aqueous phase (Caq) gives the linear line, and the intercept is KE. Figures 3 to 5 show a plot of Z/1 − Z vs Caq, and KE values were presented in Table 2 for each diluent.

XYZ = (XYZ)0 + m(Vm/100) + s(π * + dδ) + aα + bβ (5)

where (XYZ)0 is a property relating to a standard process; π* is the dipole−dipole interaction; and δ is the dipole-induced dipole interaction. The solvatochromic parameter α term is of solvent HBD (hydrogen-bond donor) acidities. This explains the ability of the solvent to donate a proton from a solvent−solute hydrogen bond. The β term is of solvent HBA (hydrogen-bond acceptor) basicities. The β term is a measure of the solvent’s ability to accept a proton from a solute−solvent hydrogen bond. Vm is

4. LINEAR SOLVATION ENERGY RELATIONSHIP (LSER) MODEL APPLICATION Some properties of extraction according to hydrogen bond formation between acid and amine can be estimated by the linear solvation energy relationship mode (LSER) based on the solvatochromic approach. For the equilibrium of an amine/diluents/acid 3687



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presented in Table 2 as Dmodel. A new LSER equation was obtained. log D = 1.395 + 2.142(Vm /100) + (− 20.322)(π * + 0.δ) + 19.319α + (− 1.498)β

As seen from Table 2, the LSER model predicts results close to experimental data.

5. CONCLUSION Equilibrium experiments for physical extraction and reactive extraction of GA were performed in batch extraction systems with three different organic solvents (isoamyl alcohol, octan1-ol, and decan-1-ol). The experimental data for degree of physical extraction and reactive extraction were compared. 98 % of acid from aqueous solution was removed to the organic phase with LA-2 in isoamyl alcohol at intermediate concentration (0.4 mol·kg−1). The optimum LA-2 concentration has been determined to be 0.4 mol·kg−1. The overall complexation constants (KE) for each diluent were obtained by a graphical method. The LSER model showed results close to experimental data with R square of 0.98.

Figure 4. Estimation of equilibrium complexation constant (KE) for octan-1-ol. Caq/mol·kg−1 is the concentration of GA in the aqueous phase.

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AUTHOR INFORMATION

Corresponding Author

*E-mail: [email protected]. Phone: +90 212 444 1997-5247. Funding

Hasan Uslu would like to thank board of trustees of Beykent University for supplying chemicals and equipment. Figure 5. Estimation of equilibrium complexation constant (KE) for decan-1-ol. Caq/mol·kg−1 is the concentration of GA in the aqueous phase.

Notes

the solute volume. The coefficients s, d, a, and b include the solute properties that come from regression.15 The solvatochromic parameters were taken from the literature and presented in Table 3.15,16

(1) Schügerl, K. Integrating processing of biotechnology products. Biotechnol. Adv. 2000, 18, 581−599. (2) Tung, L. A.; King, C. J. Sorption and extraction of lactic and succinic acids at pH > pKa1. 1. Factors Governing Equilibria. Ind. Eng. Chem. Res. 1994, 33, 3217−3223. (3) Dai, Y; King, King, C. J. Selectivity between lactic acid and glucose during recovery of lactic acid with basic extractants and polymeric sorbents. Ind. End. Chem. Res. 1996, 35, 1215−1224. (4) Husson, S. M.; King, C. J. Multiple-acid equilibria in adsorption of carboxylic acids from dilute aqueous solution. Ind. Eng. Chem. Res. 1999, 38, 502−511. (5) Lee, E. G.; Moon, S. H.; Chang, Y. K. Lactic acid recovery using two-stage electrodialysis and its modelling. J. Membr. Sci. 1998, 145, 53−66. (6) Tang, K.; Cai, J.; Zhang, P. Equilibrium and Kinetics of Reactive Extraction of Ibuprofen Enantiomers from Organic Solution by Hydroxypropyl-β-cyclodextrin. Ind. Eng. Chem. Res. 2012, 51 (2), 964−971. (7) Wasewar, K. L.; Shende, D. Z.; Keshav, A. Reactive Extraction of Itaconic Acid Using Quaternary Amine Aliquat 336 in Ethyl Acetate, Toluene, Hexane, and Kerosene. Ind. Eng. Chem. Res. 2011, 50 (2), 1003−1011. (8) Wasewar, K. L.; Shende, D. Z. Equilibrium for the Reactive Extraction of Caproic Acid Using Tri-n-butyl Phosphate in Methyl Isobutyl Ketone and Xylene. J. Chem. Eng. Data 2011, 56 (8), 3318− 3322. (9) Marti, M. E.; Turker, G.; Doraiswamy, K. L. Equilibrium and Kinetic Studies on Reactive Extraction of Pyruvic Acid with Trioctylamine in 1-Octanol. Ind. Eng. Chem. Res. 2011, 50 (23), 13518−13525. (10) Caşcaval, D.; Kloetzer, L.; Galaction, A. I. Influence of Organic Phase Polarity on Interfacial Mechanism and Efficiency of Reactive

The authors declare no competing financial interest.

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Table 3. Solvatochromic Parameters15,16a Vm

Kamlet solvatochromic parameters diluents

π*

δ

β

α

cc·mol−1

IAA OCT DEC

0.40 0.40 0.40

0 0 0

0.84 0.81 0.81

0.84 0.77 0.72

109.4 157.7 191.8

a Vm is the solute volume; π* is the dipole−dipole interaction; δ is the dipole-induced−dipole interaction. The β term is of solvent HBA (hydrogen-bond acceptor) basicities. The α term is of solvent HBD (hydrogen-bond donor) acidities. IAA is the isoamyl alcohol; OCT is the octan-1-ol; and DEC is the decan-1-ol.

The LSER model regressed experimental data to predict distribution ceofficients (D) as eq 6 log D = log D0 + m(Vm/100) + s(π * + dδ) + aα + bβ (6)

In eq 6, the coefficients m, s, a, b, and d are determined from linear regression. The log D term is the intercept that comes from the regression of the experimental data. The distribution coefficients (D) of each diluent calculated from experimental results were used in the linear solvation energy relationship (LSER) model.13 LSER model results were 3688

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Extraction of Gibberellic Acid from Aqueous Solution by Amberlite LA

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