Article Cite This: J. Chem. Eng. Data XXXX, XXX, XXX-XXX
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L(+)-tartaric Acid Separations Using Aliquat 336 in n‑Heptane, Kerosene, and 1‑Octanol at 300 ± 1 K Hariom Sharma,# Karnail Singh,# Kailas L. Wasewar,*,† and Kanti Kumar Athankar† #
Department of Chemical Engineering, Shiv Nadar University, Noida, 201314, India Advance Separation and Analytical Laboratory (ASAL), Department of Chemical Engineering, Visvesvaraya National Institute of Technology (VNIT), Nagpur, MH 440010, India
†
ABSTRACT: In the present study, extraction equilibria experiments for water + L(+)-tartaric acid + extractant/diluents were carried out at T = 300 ± 1 K for concentrations of L(+)-tartaric acid (0.1 to 1.0 mol·kg−1) and Aliquat 336 (0.22 to 0.88 mol·kg−1) in various diluents (n-heptane, kerosene, n-octanol). The equilibrium results were discussed in terms of the overall equilibrium complexation constant (KE(1:1)), loading ratio (z), extraction efficiency (E%), distribution coefficient (KD), dimerization coefficient (D), and partition coefficient (P). Kerosene + 0.88 (mol·kg−1) Aliquat 336 was found to be a favorable solvent with 50% extraction efficiency for the reactive extraction of L(+)-tartaric acid, whereas, 32.14% for n-heptane + 0.88 (mol·kg−1) Aliquat 336, and 22.22% for 1octanol + 0.88 (mol·kg−1) Aliquat 336. 1:1 acid−amine complex was proposed for all the diluents with no overloading, that is, z < 0.5. A higher chemical extraction was observed in nonpolar diluents: n-heptane and kerosene. Further, equilibrium results were fitted with relative basicity and mass action law model and it was found that the relative basicity model predicted the results better than the mass action law for reactive extraction of L(+)-tartaric acid.
1. INTRODUCTION L(+)-tartaric acid is a white crystalline dicarboxylic acid. Its molecular structure exists in its mirror image D(−) tartaric acid, L(+)-tartaric acid.1 Naturally it occurs in various fruits particularly tamarinds, grapes, oranges, and banana.2,3 Vital derivatives of tartaric acid, including its salts (antimony potassium tartrate, potassium bitartrate, potassium sodium tartrate), are used in viniculture, pharmaceutical, and the food industries. It has wide application in the manufacture of carbonated beverages, effervescent drugs, and in the textile industry as a calico printing for controlling the liberation of chlorine from bleach powder.4 The conventional process has few complications during the separation of tartaric acid from fermentation broth. Natural sources such as tartrate, tartar, and lees are precipitated with milk of lime, in the form of calcium tartrate. Calcium tartrate can be recovered from the mother liquor by filtration and converted to tartaric acid by the addition of sulfuric acid. Almost 50% of the production cost required is for separations and purification.5,6 An enormous amount of calcium sulfate sludge is generated as waste. Hence, it is thought desirable to look toward alternative techniques.7 Various methods, for instance, precipitation,8 adsorption,9−13 ion exchange,14 electrodialysis,15,16 and direct distillation17 have been successfully employed for the separation of carboxylic acid, but reactive extraction is widely accepted rather than the above-mentioned techniques. Reactive extraction is easy to operate, requires less energy, and results in a higher yield of © XXXX American Chemical Society
substrate, etc., less than 10% (w/w) acid was found in this source.18−20 The extractant−diluent system was employed for the extraction of acid in the reactive extraction. In general extractants are categorized in three types: (i) amines, (ii) hydrocarbon and oxygen bearing extractants, and (iii) organophosphorous compounds. Primary amines are observed to be tremendously hydrophilic at room temperature, whereas thirdphase formation at the interface was observed in the case of secondary amines, which creates complications in phase separation.21 Tertiary amines are quite good rather than primary and secondary amines.22 Six or more carbon atoms per chain are available in tertiary amines which contributes to a proficient recovery of carboxylic acids.21 Most of the works in the literature were focused on using tertiary amine in the extraction for acid recovery. Since, tertiary amines are expensive and their use in a large scale unit could have a huge cost impact on the unit. Because of this, other extractants, for instance organophosphorous compounds or quaternary amines, have been used for the separation of carboxylic acids.23 An additional merit of quaternary amines are they could extract the acid under both acidic and basic conditions.24 Some work, for instance Jung et al. (1996),25 Marinova et al. (2004),26 Uslu (2007),27 and Inci et al. (2011),28 has been reported on the reactive extraction of tartaric acid as depicted in Received: December 28, 2016 Accepted: October 19, 2017
A
DOI: 10.1021/acs.jced.6b01070 J. Chem. Eng. Data XXXX, XXX, XXX−XXX
Journal of Chemical & Engineering Data
Article
Table 1. Extractant/Diluent System for the Recovery of L(+)-tartaric Acid by Reactive Extraction extractant
TOA 70% TBP 30% Aliquat 336 30% TOA 15% Aliquat 336 + 15% TOA 15% Aliquat 336 30% Aliquat 336 + 40% TBP 15% TOA + 15% TBP 15% TOA Alamine 336
diluent
xylene 30% dodecane 70% 1-decanol 70% 1-decanol 70% 1-decanol 15% 1-decanol + 70% dodecane 30% dodecane 70% dodecane 15% 1-decanol + 70% dodecane hexane
acid concentration (initial) (mol·kg−1)
(mol·kg−1)
0.008−1.0 4.728 4.728
0.05−1.0
0.347
cyclohexane
toluene
MIBK
butan-1-ol
MIBK + hexane
0.347
toluene + MIBK
hexane + toluene
Amberlite LA-2
cyclohexane
extractant concentration
0.77
isooctane
B
1.736 1.449 1.049 0.736 0.422 1.736 1.449 1.049 0.736 0.422 1.736 1.449 1.049 0.736 0.422 1.736 1.449 1.049 0.736 0.422 1.736 1.449 1.049 0.736 0.422 1.702 1.396 1.055 0.661 0.378 1.702 1.396 1.055 0.661 0.378 1.702 1.396 1.055 0.661 0.378 0.19 0.37 0.56 0.74 0.93 0.19 0.37 0.56 0.74
KD
0.002 0.27 0.39 50.55 0.22 1.33 0.46 13.14 15.52 14.77 4.77 2.07 0.50 19.35 14.04 12.35 1.11 0.38 23.79 9.21 8.11 4.01 0.70 48.57 37.56 33.70 20.69 3.13 42.38 37.56 27.92 19.35 4.09 42.38 23.79 6.54 3.39 0.61 85.75 42.25 22.13 5.80 1.28 20.69 11.39 6.89 2.73 0.62 0.13 0.50 1.29 2.13 5.16 0.16 0.55 1.16 2.49
E
KE
%
(kg mol−1)
0.18 21.22 28.31 98.06 100.00 18.07 57.13 31.68 92.93 93.95 93.66 82.42 67.44 33.43 94.81 93.08 92.51 52.45 27.38 95.97 90.20 88.76 79.83 41.21 97.98 97.41 97.12 95.39 75.79 97.69 97.41 96.54 94.81 80.12 97.69 95.97 86.74 77.23 37.75 98.85 97.41 95.68 85.30 56.20 95.39 91.93 87.32 73.20 38.33 11.18 33.29 56.32 68.02 83.76 13.91 35.50 53.64 71.36
ref
0.14
25 26
8.74 10.58 4.62 2.78 1.28 11.13 9.37 11.67 1.76 0.93 13.92 6.57 8.09 5.49 2.19 27.50 23.34 31.03 26.60 6.33 25.77 24.17 26.48 23.59 8.23
27
28
DOI: 10.1021/acs.jced.6b01070 J. Chem. Eng. Data XXXX, XXX, XXX−XXX
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Table 1. continued extractant
acid concentration (initial)
diluent
extractant concentration
(mol·kg−1)
KD
(mol·kg−1) 0.93 0.19 0.37 0.56 0.74 0.93 0.19 0.37 0.56 0.74 0.93 0.19 0.37 0.56 0.74 0.93
MIBK
1-octanol
hexane
5.13 0.10 0.48 1.14 3.47 10.66 0.55 0.16 0.48 1.12 2.79 0.13 0.50 1.02 2.18 4.49
E
KE
%
(kg mol−1)
ref
83.67 8.75 32.49 53.16 77.61 91.43 14.01 32.19 52.87 73.58 84.84 11.07 33.09 50.55 68.58 81.78
Table 2. Chemical Used in the Present Study (Sample Description Table) chemical name
molecular formula
L(+)-tartaric acid n-heptane kerosene 1-octanol Aliquat 336 NaOH oxylic acid
HO2CCH(OH)CH(OH)CO2H C7H16
2,3-dihydroxybutanedioic acid heptane
IUPAC name
CH3(CH2)7OH C25H54ClN NaOH C2H2O4
octan-1-ol N-Methyl-N,N,N-trioctylammonium chloride sodium hydroxide ethane-1,2-dioic acid
source
CAS No.
assay (%)
Avra Synthesis Pvt. Ltd., India Merck, India Local vendor Merck, India Spectrochem India SD Fine-Chem Ltd. India SD Fine-Chem Ltd. India
87-69-4 142-82-5
98 98
111-87-5 5137-55-3 1310-73-2 144-62-7
98 80 99 99
Table 3. Physicochemical Properties45−47 of Acid, Extractants, and Solvents Chosen for the Present Studya at 298 K solvent L(+)-tartaric acid n-heptane kerosene 1-octanol Aliquat 336
MW (kg mol−1)
MS
BP (K)
MP (K)
Swater (kg·L−1)
ρ (kg·m−3)
RI
μ Pa·s
ε
ST (N·m−1)
P
DM (D)
0.150
C4H6O6
399.3
441
1.33
1760
1.46
NA
NA
NA
NA
NA
0.100
C6H13CH3 NA CH3(CH2)7OH C25H54NCl
371 420 195 498
182 200 257 293
insoluble insoluble 0.00046 0.01
679.5 840 824 884
1.39 1.44 1.42 1.46
0.386 0.001 0.007 1.500
1.92 1.80 3.40 NA
0.0201 0.0275 0.0276 NA
0.012 ∼0 0.537 NA
0.0 ∼0 1.76 NA
0.130 0.404
a Abbreviations: MW, molecular weight; MS, molecular structure; BP, boiling point; MP, melting point; Swater, solubility in water at 298 K; ρ, density of pure liquid; RI, refractive index; μ, viscosity; ε, dielectric constant; ST, surface tension; P, polarity index; DM, dipole moment; NA, not available
Table 1, while Arslanoglu et al. (2010)13 reported 9.58% removal of tartaric acid at room temperature using single walled carbon nanotubes (SWCNT) as a adsorbent. Hence, it is thought desirable to carry out exhaustive research in the process development for the reactive extraction of tartaric acid. In the present work, equilibrium studies on L(+)-tartaric acid recovery using Aliquat 336 blended with n-heptane, kerosene, and 1-octanol was studied. To date, Aliquat 336 with n-heptane, kerosene, and 1-octanol was not chosen for the extraction of tartaric acid. The equilibrium results are reported in terms of the overall equilibrium complexation constant (KE(1:1)), loading ratio (z), extraction efficiency (E%), distribution coefficient (KD), dimerization coefficient (D), and partition coefficient (P). Furthermore, revival of solvent, extraction mechanism, and water coextraction phenomena were also discussed.
2. MATERIALS AND METHODS 2.1. Materials. L(+)-tartaric acid (0.98 mass fraction) was obtained from Avra Synthesis Pvt. Ltd., India. Aliquat 336, used as an extractant, procured from Spectrochem India, is a combination of C8−C10 (quaternary amine) with an assay of 0.80 mass faction, and a molecular weight and density of 0.404 kg/mol and 884 kg/m3, respectively. n-Heptane and 1-octanol were obtained from Merck, India, with purity >0.98 mass fraction, whereas kerosene was obtained from the local market. n-Heptane, kerosene, and 1-octanol were used as provided. LR grade sodium hydroxide procured from SD Fine Chem Ltd. India, was employed for titration (Table 2). Oxalic acid (mass fraction of 0.99) was applied for the standardization of the sodium hydroxide and phenolphthalein indicator. The initial concentrations of aqueous solutions of L(+)-tartaric acid and Aliquat 336 as 0.1 to 1.0 (mol·kg−1), 3 to 15% (w/w), and 0.22, C
DOI: 10.1021/acs.jced.6b01070 J. Chem. Eng. Data XXXX, XXX, XXX−XXX
Journal of Chemical & Engineering Data
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Table 4. Physical Equilibrium of L(+)-Tartaric Acid with Organic Solvents at 101325 Pa and 300 ± 1 Ka [HA]o (mol·kg−1)
[HA]aq (mol·kg−1)
[HA]org (mol·kg−1)
0.11 0.25 0.51 0.80 1.01
0.102 0.245 0.498 0.762 0.989
0.004 0.005 0.002 0.038 0.019
0.11 0.25 0.51 0.80 1.01
0.109 0.237 0.500 0.805 1.004
0.001 0.015 0.004 0.012 0.016
0.11 0.25 0.51 0.80 1.01
0.098 0.235 0.478 0.784 0.980
0.004 0.015 0.022 0.016 0.040
KD
solvent = n-heptane 0.040 0.019 0.004 0.050 0.020 solvent = kerosene 0.009 0.064 0.008 0.015 0.016 solvent = 1-octanol 0.041 0.063 0.046 0.020 0.041
KD(avg)
E (%)
Eavg (%)
P
D
0.027
3.88 1.89 0.38 4.72 1.92
2.558
0.028
1.256
0.022
0.87 6.00 0.78 1.51 1.58
2.148
0.045
8.089
0.042
3.92 5.92 4.35 2.00 3.92
4.022
0.041
2.533
Standard uncertainties u are u(T)=1 K, u([HA])=0.01 mol·kg−1., u(p)=1 kPa. Notation: [HA], L(+)-tartaric acid concentration; KD, distribution coefficient; E(%), extraction efficiency; P, partition coefficient; D, dimerization constant. a
Figure 1. Equilibrium isotherm of reactive extraction of L(+)-tartaric acid with various concentration of Aliquat 336 in n-heptane, kerosene, and 1octanol: (a) 0.22 mol·kg−1, (b) 0.44 mol·kg−1, (c) 0.66 mol·kg−1, (d) 0.88 mol·kg−1.
0.44, 0.66, and 0.88 mol·kg−1 were used, respectively. In the fermentation process, the concentration of L(+)-tartaric acid was found to be greater than 1 mol·kg−1.25 Table 3 represents the physicochemical characteristics of the chemicals employed in this work.
2.2. Method. A 1:1 volume ratio of aqueous and organic solutions in a 100 mL Erlenmeyer flask was shaken in a water bath shaker (model, RSB-12; REMI, Mumbai) until equilibrium was attained (6 h) at 190 rpm, T = 300 ≈ 1 K, and 101325 Pa. Further, the equilibrium mixture was kept for segregation of both phases for a minimum of 2 h at 300 K. The pH of the D
DOI: 10.1021/acs.jced.6b01070 J. Chem. Eng. Data XXXX, XXX, XXX−XXX
Journal of Chemical & Engineering Data
Article
Table 5. Chemical Equilibrium of Aqueous Solution of L(+)-Tartaric Acid with Aliquat 336 + n-Heptane at 101325 Pa and 300 ± 1 Ka [R4N+Cl−] −1
[HA]o
[HA]aq
E KD(avg)
(%)
z
pHo
pKb
(kg mol )
(kg mol )
(kg mol )
(kg mol−1)
0.22
0.11 0.25 0.51 0.80 1.01 0.11 0.25 0.51 0.80 1.01 0.11 0.25 0.51 0.80 1.01 0.11 0.25 0.51 0.80 1.01
0.098 0.219 0.442 0.698 0.891 0.083 0.192 0.415 0.679 0.857 0.087 0.189 0.400 0.638 0.804 0.072 0.189 0.370 0.619 0.808
0.008 0.034 0.064 0.102 0.117 0.023 0.060 0.091 0.121 0.151 0.019 0.064 0.106 0.162 0.204 0.034 0.064 0.136 0.181 0.200
0.08 0.16 0.15 0.15 0.13 0.27 0.31 0.22 0.18 0.18 0.22 0.34 0.26 0.25 0.25 0.47 0.34 0.37 0.29 0.25
0.134
7.14 13.43 12.69 12.74 11.61 21.43 23.88 17.91 15.09 14.98 17.86 25.37 20.90 20.28 20.22 32.14 25.37 26.87 22.64 19.85
0.03 0.15 0.29 0.46 0.53 0.05 0.14 0.21 0.27 0.34 0.03 0.10 0.16 0.25 0.31 0.04 0.07 0.16 0.21 0.23
3.2 3.1 2.9 2.6 2.5 3.2 3.1 2.9 2.6 2.5 3.2 3.1 2.9 2.7 2.5 3.2 3.1 2.9 2.7 2.5
6.4 6.2 5.9 5.5 5.3 6.4 6.3 6.0 5.6 5.3 6.4 6.3 6 5.6 5.4 6.5 6.3 6 5.7 5.4
0.36 0.83 0.93 1.24 1.28 0.65 0.83 0.62 0.56 0.61 0.34 0.57 0.48 0.51 0.56 0.57 0.42 0.50 0.42 0.37
0.93
1.19
0.92
0.65
0.59
0.65
0.49
0.53
0.49
0.46
0.40
0.45
0.344
−1
KE(1:1)RBM
KD
0.264
−1
KE(1:1)MAL
(mol·kg )
0.232
−1
KE(1:1)exp(avg)
(mol·kg )
0.88
−1
KE(1:1)exp
(mol·kg )
0.66
−1
[HA]org
(mol·kg )
0.44
−1
Standard uncertainties u are u(T) = 1 K, 3u([HA]) = 0.01 mol·kg−1, u([R4N+Cl−]) = 0.01 mol·kg−1, u(pH) = 0.01; u(p) = 1 kPa; solvent = Aliquat 336 + n-heptane. Notation: R4N+Cl−], concentration of the Aliquat 336; [HA], L(+)-tartaric acid concentration; KD, distribution coefficient; E(%), extraction efficiency; z, loading ratio; KE, equilibrium constant. a
Table 6. Chemical Equilibrium of Aqueous Solution of L(+)-Tartaric Acid with Aliquat 336 + Kerosene at 101325 Pa and 300 ± 1 Ka [R4N+Cl−]
[HA]o
[HA]aq
[HA]org
KE(1:1)exp
KE(1:1)exp(avg)
KE(1:1)MAL
KE(1:1)RBM
(mol·kg−1)
(mol·kg−1)
(mol·kg−1)
(mol·kg−1)
KD
KD(avg)
(%)
z
pHo
pKb
(kg mol−1)
(kg mol−1)
(kg mol−1)
(kg mol−1)
0.22
0.11 0.25 0.51 0.80 1.01 0.11 0.25 0.51 0.80 1.01 0.11 0.25 0.51 0.80 1.01 0.11 0.25 0.51 0.80 1.01
0.075 0.223 0.445 0.717 0.921 0.072 0.200 0.408 0.657 0.853 0.068 0.196 0.385 0.657 0.800 0.057 0.185 0.377 0.604 0.758
0.030 0.029 0.055 0.100 0.099 0.034 0.052 0.096 0.160 0.167 0.046 0.056 0.090 0.160 0.207 0.057 0.053 0.098 0.213 0.249
0.39 0.13 0.12 0.14 0.11 0.47 0.26 0.24 0.24 0.20 0.68 0.28 0.23 0.24 0.26 1.01 0.28 0.26 0.35 0.33
0.178
28.31 11.62 10.94 12.24 9.73 31.90 20.61 19.14 19.63 16.39 40.42 22.11 18.97 19.63 20.56 50.35 22.14 20.56 26.10 24.68
0.14 0.13 0.25 0.45 0.45 0.08 0.12 0.22 0.36 0.38 0.07 0.08 0.14 0.24 0.31 0.07 0.06 0.11 0.25 0.29
3.2 3.1 2.9 2.6 2.5 3.2 3.1 2.9 2.6 2.5 3.2 3.1 2.9 2.7 2.5 3.2 3.1 2.9 2.7 2.5
6.4 6.2 5.9 5.5 5.3 6.4 6.3 6.0 5.6 5.3 6.4 6.3 6 5.6 5.4 6.5 6.3 6 5.7 5.4
2.08 0.69 0.74 1.16 0.89 1.15 0.67 0.69 0.87 0.72 1.10 0.47 0.41 0.49 0.57 1.25 0.35 0.34 0.54 0.53
1.11
0.95
1.03
0.82
0.75
0.65
0.61
0.52
0.58
0.60
0.50
0.45
0.44
0.66
0.88
E
0.282
0.338
0.446
a Standard uncertainties u are u(T) = 1 K, u([HA]) = 0.01 mol·kg−1, u([R4N+Cl−]) = 0.01 mol·kg−1, u(pH) = 0.01; u(p) = 1 kPa; solvent = Aliquat 336 + kerosene. [R4N+Cl−], concentration of the Aliquat 336; [HA], L(+)-tartaric acid concentration; KD, distribution coefficient; E(%), extraction efficiency; z, loading ratio; KE, equilibrium constant.
aqueous phase pH at equilibrium being greater than the aqueous phase pH at the initial time. Equation 1 was employed for the quantification of pH of L(+)-tartaric acid solution.
aqueous phase (prior and later extraction) was quantified by digital pH meter procured from Arm Field Instrument Lab, India. A pH between 2.6 to 3.2 of an aqueous solution of L(+)tartaric acid was used for this study. Usually, the extraction of L(+)-tartaric acid depends on the pH of the system; that is, the
pH = − 0.742[HA]aq + 3.286 E
(1) DOI: 10.1021/acs.jced.6b01070 J. Chem. Eng. Data XXXX, XXX, XXX−XXX
Journal of Chemical & Engineering Data
Article
Table 7. Chemical Equilibrium of Aqueous Solution of L(+)-Tartaric Acid with Aliquat 336 + 1-Octanol at 101325 Pa and 300 ± 1 Ka [R4N+Cl−] −1
[HA]o
[HA]aq
E KD(avg)
(%)
z
pHo
pKb
(kg mol )
(kg mol )
(kg mol )
(kg mol−1)
0.22
0.11 0.25 0.51 0.80 1.01 0.11 0.25 0.51 0.80 1.01 0.11 0.25 0.51 0.80 1.01 0.11 0.25 0.51 0.80 1.01
0.094 0.223 0.454 0.713 0.940 0.086 0.209 0.436 0.713 0.929 0.079 0.216 0.428 0.666 0.900 0.076 0.194 0.403 0.648 0.864
0.004 0.015 0.014 0.033 0.036 0.011 0.029 0.032 0.033 0.047 0.018 0.022 0.040 0.080 0.076 0.022 0.044 0.065 0.098 0.112
0.04 0.07 0.03 0.05 0.04 0.13 0.14 0.07 0.05 0.05 0.23 0.10 0.09 0.12 0.08 0.29 0.22 0.16 0.15 0.13
0.046
3.70 6.22 3.08 4.45 3.69 11.11 12.27 6.92 4.45 4.80 18.52 9.24 8.46 10.72 7.75 22.22 18.32 13.85 13.14 11.44
0.02 0.07 0.07 0.15 0.16 0.02 0.07 0.07 0.08 0.11 0.03 0.03 0.06 0.12 0.11 0.02 0.05 0.07 0.11 0.13
3.2 3.1 2.9 2.6 2.5 3.2 3.1 2.9 2.6 2.5 3.2 3.1 2.9 2.7 2.5 3.2 3.1 2.9 2.7 2.5
6.4 6.2 5.9 5.5 5.3 6.4 6.3 6.0 5.6 5.3 6.4 6.3 6 5.6 5.4 6.5 6.3 6 5.7 5.4
0.18 0.32 0.15 0.25 0.21 0.29 0.34 0.18 0.11 0.13 0.35 0.16 0.15 0.21 0.14 0.34 0.27 0.20 0.20 0.17
0.22
0.22
0.22
0.21
0.13
0.21
0.20
0.16
0.19
0.23
0.18
0.23
0.190
−1
KE(1:1)RBM
KD
0.124
−1
KE(1:1)MAL
(mol·kg )
0.088
−1
KE(1:1)exp(avg)
(mol·kg )
0.88
−1
KE(1:1)exp
(mol·kg )
0.66
−1
[HA]org
(mol·kg )
0.44
−1
Standard uncertainties u are u(T) = 1 K, u([HA]) = 0.01 mol·kg−1, u([R4N+Cl−]) = 0.01 mol·kg−1, u(pH) = 0.01; u(p) = 1 kPa; solvent = Aliquat 336 + 1-octanol. [R4N+Cl−], concentration of the Aliquat 336; [HA], L(+)-tartaric acid concentration; KD, distribution coefficient; E(%), extraction efficiency; z, loading ratio; KE, equilibrium constant. a
Figure 2. Linear plot of [HA]aq and z/(1 − z) with various concentrations of Aliquat 336: (a) 0.22 mol·kg−1, (b) 0.44 mol·kg−1, (c) 0.66 mol·kg−1, (d) 0.88 mol·kg−1.
F
DOI: 10.1021/acs.jced.6b01070 J. Chem. Eng. Data XXXX, XXX, XXX−XXX
Journal of Chemical & Engineering Data
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The organic phase was removed for volume measurement, and the aqueous phase was collected by a 5 mL glass syringe. The concentration of acid was measured by titration using fresh and standardized NaOH. The equivalent acid concentration in the organic phase was evaluated by mass balance. An experimental uncertainty was calculated according to the National Institute of Standard and Technology (NIST) norms.29 Hence, few experiments were replicants and the results were obtained within ≈ 2%. For physical equilibrium the organic phase was nheptane, kerosene, and 1-octanol, while for chemical equilibrium, 10 to 40% (v/v) Aliquat 336 was taken in diluents as the organic phase.
3. RESULTS AND DISCUSSION 3.1. Physical Extraction. n-Heptane (nonpolar), kerosene (nonpolar), and 1-octanol (polar) was used for physical Figure 4. Water coextraction data of L(+)-tartaric acid with Aliquat 336 in n-heptane, kerosene, and 1-octanol.
HA org
P=
HA aq
(5)
(iii). Dimerization of the acid in the organic phase:
2HA org ↔ HA 2,org D=
(6)
[HA]2,org 2 [HA]org
(7)
The entire distribution coefficient for physical extraction Kdiluent D can be expressed as KDdiluent = =
[HA]org,total [HA]aq.total
=
[HA]org + 2[HA]2 [HA]aq + [A−]
P + 2P 2D[HA]aq ⎛ ⎜1 + ⎝
K HA ⎞ ⎟ H+aq ⎠
(8)
Equation 8 can be rearranged as ⎛ K ⎞ ⎟ = P + 2P 2D[HA]aq KDdiluent⎜⎜1 + HA H+aq ⎟⎠ ⎝
Figure 3. L(+)-tartaric acid−Aliquat 336 complex structures in organic phase (n:1): (i) 1:1; (ii) 2:1; (iii) 3:1.
In eq 9, [Haq ] may be disregarded and [KHA] ≈ 0 since concentrations of L(+) acid are quite low. P and D can be obtained by the linear curve of KDdiluent vs [HA]aq. Extraction efficiency, E%, is evaluated by eq 10:
extraction of L(+)-tartaric acid. It was executed by the following steps:21 (i). Ionization of the acid in an aqueous solution
E% =
Ka
HA aq ↔ H+ + A‐
(2)
[H+][A−] = [HA]aq
(3)
KHA
(9)
+
KDdiluent × 100 (1 + KDdiluent)
(10)
The partition and dimerization coefficients were calculated by the regression of experimental data and are tabulated in Table 4. KD values for L(+)-tartaric acid by diluents alone was found in the range of 0.004−0.019, 0.001−0.016, and 0.004−0.040 for n-heptane, kerosene, and 1-octanol, respectively. 1-Octanol was a more appropriate diluent rather than n-heptane and kerosene, on account of the higher distributions. n-Heptane, kerosene, and 1-octanol results reveal strong solute−diluent interaction by the polar diluents: 1-octanol as compared to relatively very less polar kerosene and nonpolar n-heptane. Inci et al. (2011)28
where pKHA1 = 3.01 and pKHA2 = 4.38 stands for ionization constants.25 (ii). Partition of the un-ionized acid between binary phases (aqueous and organic): HA aq ↔ HA org (4) G
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Table 8. Water Coextraction Results of Aqueous Solutions of L(+)-Tartaric Acid + Aliquat 336 + Solvent System at 101 325 Pa and 300 ± 1 Ka n-heptane
L(+)-tartaric acid Vin
[HA]o
Vorg
Vaq
1-octanol Vorg
WCE (%)
1.01 0.11 0.25 0.51 0.80
10 10 10 10 10
10.31 10.27 10.65 10.22 10.31
9.69 9.73 9.35 9.78 9.69
3.1 2.7 6.5 2.2 3.1
1.01 1.01 0.11 0.25 0.51
10 10 10 10 10
10.36 10.40 10.30 10.26 10.11
9.64 9.60 9.70 9.74 9.89
3.6 4.0 3.0 2.6 1.1
0.80 1.01 1.01 0.11 0.25
10 10 10 10 10
10.10 10.07 10.14 10.16 10.20
9.90 9.93 9.86 9.84 9.80
1.0 0.7 1.4 1.6 2.0
Vaq
0.00 mol·kg−1 [R4N+Cl−] 10.34 9.66 10.32 9.68 10.11 9.89 10.33 9.67 10.34 9.66 0.44 mol·kg−1 [R4N+Cl−] 10.23 9.77 10.38 9.62 10.29 9.71 10.13 9.87 10.34 9.66 0.88 mol·kg−1 [R4N+Cl−] 10.30 9.70 10.19 9.81 10.12 9.88 10.08 9.92 10.33 9.67
kerosene WCE (%)
Vorg
Vaq
WCE (%)
3.4 3.2 1.1 3.3 3.4
10.43 10.17 10.36 10.28 10.21
9.57 9.83 9.64 9.72 9.79
4.3 1.7 3.6 2.8 2.1
2.3 3.8 2.9 1.3 3.4
10.08 10.19 10.22 10.30 10.12
9.92 9.81 9.78 9.70 9.88
0.8 1.9 2.2 3.0 1.2
3.0 1.9 1.2 0.8 3.3
10.09 10.16 10.19 10.20 10.03
9.91 9.84 9.81 9.80 9.97
0.9 1.6 1.9 2.0 0.3
a Standard uncertainties u are u(T) = 1 K, u([HA]) = 0.01 mol·kg−1, u([R4N+Cl−]) = 0.01 mol·kg−1, u(Vin) = 0.5 mL; Aliquat 336+Solvents. Notation: [R4N+Cl−], concentration of the Aliquat 336; [HA]o, initial concentration of L(+)-tartaric acid; Vin, initial volume of aqueous phase; Vaq, volume of aqueous phase at equilibrium after phase separation; Vorg, volume of organic phase at equilibrium after phase separation; % WCE, percentage of water coextraction.
Table 9. Model Parameters for Relative Basicity Modela +
−
−1
[R4N Cl ] (mol·kg ) 0.22 0.44 0.66 0.88 0.22 0.44 0.66 0.88 0.22 0.44 0.66 0.88
C1
n-Heptane + Aliquat 336 −0.39 0.09 −0.12 0.13 Kerosene + Aliquat 336 0.12 0.09 0.17 0.13 1-Octanol + Aliquat 336 0.002 0.373 0.193 0.235
requires a high flow rate of solvent resulting in further dilution of the target acid. Hence, reactive components are imperative to effectuate the above-discussed criterion. 3.2. Chemical Equilibrium. In general, a low KD was observed for the pure diluents; hence, an extractant was suggested for enhancement of KD. The concentration range of Aliquat 336 of 10−40% (v/v) 0.22−0.88 (mol·kg−1) was employed in n-heptane, kerosene, and 1-octanol. Because of the higher viscosity of Aliquat 336, a third phase formation may form during extraction; hence, a lower concentration of Aliquat 336 was preferred in the present study. Both forms of acid, ionized and un-ionized, can be extracted using Aliquat 336.24 Equation 11 was employed to evaluate the distribution coefficient of L(+)-tartaric acid accompanied by Aliquat 336.
log(C2P) 0.78 −0.38 −0.05 −0.63 −0.26 −0.38 −0.62 −0.65 −0.671 −1.523 −1.144 −1.166
KD(A−) =
[R 4N+Cl−:A−]org [HA]aq + [A−]aq
KD(HA) =
[R 4N+Cl−:HA]org [HA]aq + [A−]aq (11)
Notation: [R4N+Cl−], concentration of the Aliquat 336; C1 and log(C2P), relative basicity model parameters.
a
Hence, the entire KD can be expressed as KD = KD(A−) + KD(HA)
reported the distribution coefficient of L(+)-tartaric acid as 0.04 in hexane and 0.09 in octanol for 0.71 mol·L−1, an initial concentration of acid. L(+)-tartaric acid has a low relative volatility and high affinity toward water, which renders it arduous to detach. The hydrophobic nature of L(+)-tartaric acid toward these organic diluents results in a low distribution coefficient of less than 1. Solvation by benefactor bonds and equilibrium solubility seems to be the main factor for the removal of acid when diluents were used alone. The variation of the distribution ratio in different diluents for the same acid emphasizes the importance of solvation for extraction of the carboxylic acid, since the key objective of extraction (greater KD and selectivity) was not fullfilled by diluents alone. Furthermore, low extraction with conventional diluents
(12)
In aqueous and organic solution, L(+)-tartaric acid exists in ionized and dimerized forms. Since the experiments were performed at low pH 2.5−3.3 which is less than the average pKa (3.7) of acid (pKa1 = 3.01; pKa2 = 4.38), it is envisaged that acid ionization is insignificant.25 Consequently, merely the unionized L(+)-tartaric acid and L(+)-tartaric acid−Aliquat 336 complex are supposed to exist in the aqueous and organic solutions, respectively. The reactive extraction is governed by the chemical reaction involving L(+)-tartaric acid and Aliquat 336. Figure 1(a−d) and Tables 5−7 illustrate the reactive extraction of L(+)-tartaric acid with Aliquat 336 (0.22−0.88 mol·kg−1 (10−40%)) in nheptane, kerosene, and 1-octanol. A third phase formation was H
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3.2.2. Consequence of Diluent and Aliquat 336 on KD. To improve the physiochemical characteristics of extractant and solvation of the acid−extractant complex, an organic diluent can be obligatory. The KD value is subjected to the nature of the diluent and concentration of extractant in the solvent phase.21 Usually, a polar solvent should ameliorate the extracting ability of the nonpolar amine by providing solvation of acid−amine complexes. For a dormant diluent, the KD might be proportional to the concentration of the extractant. Aliquat 336 is extremely viscous, consequently diluents are used with it to mitigate its viscosity and to enhance its physiochemical characteristics. In Tables 5−7, the average KD values were found to be increased from 0.13 to 0.34 in the case of n-heptane and 0.022 to 0.47 in kerosene, respectively, whereas, average KD values of acid were found to be increased from 0.04 to 0.19 in 1-octanol. Therefore, it was observed that the KD values of L(+)-tartaric acid for Aliquat 336 + n-heptane and Aliquat 336 + kerosene are far better than those for Aliquat 336 + 1-octanol. Inci et al. (2011)28 studied the extraction of tartaric acid and concluded that inert diluents give a higher chemical extraction rather than polar diluents with Amberlite LA-2. Polar diluents have been shown to be more appropriate diluents than inert because of the higher distributions.23 On the other hand in the present study, the reactive extraction of L(+)tartaric acid with Aliquat 336 did not have such an effect. Hence, it can be concluded that the polarity of the diluent is not significant in the reactive extraction of L(+)-tartaric acid by Aliquat 336. A merit of 1-octanol is the clear phase separation obtained that is not found with n-heptane and kerosene. 3.2.3. Chemical Equilibria Mechanism and Equilibrium Complex. Chemical extraction executed through a complexation reaction between L(+)-tartaric acid ([HA]) and Aliquat 336 ([R4N+Cl−]), render 1:1 ([R4N+Cl−:HA]), 2:1 ([R4N+Cl−: (HA)2]), and n:1 ([R4N+Cl−:(HA)n]) acid−Aliquat 336 complexes is represented by the following reactions:31 K1:1
[HA]aq + [R 4N+Cl−]org ←→ [R 4N+Cl−:HA]org
Figure 5. Parity plot of reactive extraction of L(+)-tartaric acid: (a) mass action law model; (b) relative basicity model.
(13)
K 2:1
[HA]aq + [R 4N+Cl−:HA]org ←→ [R 4N+Cl−:(HA)2 ]org (14)
not encountered with assorted diluents excluding at very high concentrations of Aliquat 336 and L(+)-tartaric acid in nheptane and kerosene, whereas in 1-octanol accompanied by Aliquat 336, KD was not substantially enhanced. Consequently, chemical extraction is quite excellent compared to physical extraction. 3.2.1. Consequence of L(+)-Tartaric Acid Concentration on KD. In Tables 5−7, KD values were observed to be much larger than those of the pure diluents indicating that chemical extraction is a far better technique than physical extraction. In the extraction, Aliquat 336 accompanied the chosen diluents, and the unit Vorg/Vaq ratio KD is either moderately influenced by the L(+)-tartaric acid concentration or is exorbitant at lower concentrations 0.1 (mol·kg−1) of L(+)-tartaric acid. The quantity of Aliquat 336 is prohibitive for the acid−amine reaction at higher concentrations of L(+)-tartaric acid. The experimental results of the lactic acid recovery using a tertiary amine had absolutely a reverse trend. Alamine 336 (15 and 50%) with oleyl alcohol was employed for the separation of lactic acid, and KD was found to decline from 10.5 to 0.5 and 13 to 4 with increasing lactic acid concentration from 10 to 100 g· L−1.30 Consequently, it can be an effective extract acid prevailing in the fermentation broth over tertiary amine.
[HA]aq + [R 4N+Cl‐: (HA)n − 1]org K n−1
←→ ⎯ [R 4N+Cl−:(HA)n ]org
(15)
Equilibrium complexation constant for eqs 13−15 can be expressed as KE(n:1) =
[R 4N+Cl−:(HA)n ]org n [R 4N+Cl−]org [HA]aq
(16)
Loading ratio, z is the ratio of concentration of carboxylic acid and extractant in organic phase: z=
[HA]org [R 4N+Cl−]1:org
(17)
Extractability of the acid and its aqueous concentration are the key factor for the magnitude of z. In the organic phase, the loading ratio is accountable for the stoichiometry of the overall reaction. In the present study, the organic phase is less concentrated hence loading ratios are Aliquat 336 + n-heptane > Aliquat 336 + 1-octanol. Thus, the lowest value was found with Aliquat 336 + 1-octanol. The ability of solvation of the acid−amine complex was found in the order Aliquat 336 + kerosene > Aliquat 336 + n-heptane > Aliquat 336 + 1octanol. The difference among KE(1:1) signifies solvation by the diluent and is a key factor in the reactive extraction of acid. Dormant diluents (alkanes) offer quite little KD of the acid into the diluent phase. Figure 3(i) shows the (1:1) L(+)-tartaric acid−Aliquat 336 complex for low acid concentration. L(+)-tartaric acid concentration in the aqueous phase is the key factor for the formation of (2:1) and (3:1) complexes.32 Congestion occurred due to the succeeding L(+)-tartaric acid molecule hydrogenbonding to the L(+)-tartaric acid that is previously involved in the (1:1) complex as shown in Figure 3(ii). The (3:1) complexes are established with an enormous loading ratio in which a third L(+)-tartaric acid is hydrogen-bonded to the second L(+)-tartaric acid of the (2:1) complex as revealed in Figure 3(iii). Usually a (1:1) complex was observed in the present study. 3.2.4. Consequence of Dielectric Constant of Diluents on Extraction. Various perspectives have been made to enumerate the influence of diluents on the (1:1) complexation. The nature of the diluent is the key factor for partition and self-association constants. The influence of the diluent on partition and selfassociation constants was explained by the distinct interactions between Aliquat 336 and the diluents. The Hildebrand solubility parameter was recommended to evaluate the solvation of the complex by the diluent.33 The acid distribution and solubility parameters follow the order as alkane < ethers < O
DOI: 10.1021/acs.jced.6b01070 J. Chem. Eng. Data XXXX, XXX, XXX−XXX
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ORCID
influence the extraction of carboxylic acid. The aforesaid factors can be correlated by eq 19: log KE(1:1) = [C1(pK b − pK a) + log(C2P)]
Kailas L. Wasewar: 0000-0001-7453-6308 Kanti Kumar Athankar: 0000-0002-7158-3210
(19)
Notes
The authors declare no competing financial interest.
In reactive extraction, the equilibria of carboxylic acid with the extractant−diluent system can be theorized by eq 19. KE(1:1) describes the ascendancy of extraction of the acid through the solvating power of the complex, complex of the ion pair, and hydrogen-bond association. Furthermore, pKb is the relative basicity of the extractant amalgam of HCl, excluding the nature of the solute. If the basicity of the extractant blend is relative to that of the solute, it can represent the nature of the extractant, diluents, and solute and also represent a special association, for instance, solvating power.35 KE(1:1) values C1 and C2 are shown in Tables 5−7 and Table 9, respectively. Figure 5 panels a and b show that an excellent fit was obtained and all the results are within ±5% except for a few points. Hence, the relative basicity model validates the experimental values of KE(1:1) and can be used to illustrate the reactive extraction of L(+)-tartaric acid with Aliquat 336 accompanied by chosen diluents. 3.2.7. Comparative Study. Table 10 depicts the present results of the reactive extraction of L(+)-tartaric acid with Aliquat 336 in n-heptane, 1-octanol, and kerosene as compared to the reactive extraction of other carboxylic acids, namely, lactic acid,36 propionic acid,37−40 levulinic acid,41,42 gallic acid,43 and glutaric acid44 using Aliquat 336 in various diluents. The results were compared for values of distribution coefficient and extraction efficiency. It can be seen that L(+)-tartaric acid has the lowest KD, and for E% the order is gallic acid < glutaric acid < lactic acid < propionic acid < levulinic acid < L(+)-tartaric. The results show that more L(+)-tartaric acid can be extracted with up to a certain concentration of Aliquat 336 in the chosen diluents.
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(1) Haskins, W. T.; Hudson, C. S. Improvements in the Preparation of L-Tartaric Acid from Racemic Tartaric Acid Through Resolution by a Substituted Benzimidazole Base. J. Am. Chem. Soc. 1939, 61, 1266− 1268. (2) DeBolt, S.; Cook, D. R.; Ford, C. M. L-Tartaric Acid Synthesis from Vitamin C in Higher Plants. Proc. Natl. Acad. Sci. U. S. A. 2006, 103, 5608−5613. (3) Willaert, R.; De Vuyst, L. Continuous Production of L(+)Tartaric Acid from Cis-Epoxysuccinate Using a Membrane Recycle Reactor. Appl. Microbiol. Biotechnol. 2006, 71, 155−163. (4) Gusler, G. M.; Browne, T. E.; Cohen, C. Sorption of Organic Acids from Aqueous Solution onto Polymeric Resins. Ind. Eng. Chem. Res. 1993, 32, 2727−2735. (5) Chaudhuri, J. B.; Phyle, D. L. Emulsion Liquid Membrane Extraction of Organic Acids.1. A Theoretical Model for Lactic Acid Extraction With Emulsion Swelling. Chem. Eng. Sci. 1992, 47, 41−48. (6) Eyal, A. M.; Bressler, E. Industrial Separation of Carboxylic Acid and Amino Acids by Liquid Membranes: Applicability, Process Considerations and Potential Advantages. Biotechnol. Bioeng. 1993, 41, 287−295. (7) Shreve, R. N.; Brink, J. A. Chemical Process Industries; McGrawHill: New York, 1977. (8) King, C. J.; Starr, J. Recovery of carboxylic acids from water by precipitation from organic solutions. US Patent 5,104,492, 1990. (9) Dai, Y.; King, C. J. Selectivity Between Lactic Acid and Glucose During Recovery of Lactic Acid With Basic Extractants and Polymeric Sorbents. Ind. Eng. Chem. Res. 1996, 35, 1215−1224. (10) Pazouki, M.; Panda, T. Recovery of Citric Acid-A Review. Bioprocess Eng. 1998, 19, 435−439. (11) Han, S. W.; Joo, S. W.; Ha, T. H.; Kim, Y.; Kim, K. Adsorption Characteristics of Anthraquinone-2-Carboxylic Acid on Gold. J. Phys. Chem. B 2000, 104, 11987−11995. (12) Paik, W. K.; Han, S.; Shin, W.; Kim, Y. Adsorption of Carboxylic Acids on Gold by Anodic Reaction. Langmuir 2003, 19, 4211−4216. (13) Arslanoglu, O. N.; Inci, I.; Bayazit, S. S. Purification of Biotechnological Carboxylic Acids with an Adsorption Method Using Single-Walled Carbon Nanotubes. J. Chem. Eng. Data 2010, 55, 5663− 5668. (14) Cao, X.; Yun, H. S.; Koo, Y. M. Recovery of L-(+)-Lactic Acid by Anion Exchange Resin Amberlite IRA-4000. Biochem. Eng. J. 2002, 11, 189−196. (15) Lee, E. G.; Moon, S. H.; Chang, Y. K.; Yoo, I. K.; Chang, H. N. Lactic Acid Recovery Using Two Stage Electrodialysis and its Modelling. J. Membr. Sci. 1998, 145, 53−66. (16) Wang, Z.; Luo, Y.; Yu, P. Recovery of Organic Acids from Waste Salt Solutions Derived from the Manufacture of Cyclohexanone by Electrodialysis. J. Membr. Sci. 2006, 280, 134−137. (17) Luque, R.; Lin, C. S. K.; Du, C.; Macquarrie, D. J.; Koutinas, A.; Wang, R.; Webb, C.; Clark, J. H. Chemical Transformations of Succinic Acid Recovered from Fermentation Broths by a Novel Direct Vacuum Distillation-Crystallisation Method. Green Chem. 2009, 11, 193−200. (18) Tamada, J. A.; King, C. J. Extraction of Carboxylic Acids With Amine Extractants, (3) Effect of Temperature, Water coextraction and Process Considerations. Ind. Eng. Chem. Res. 1990, 29, 1333−1338. (19) Jung, M.; Schierbaum, B.; Vogel, H. Extraction of Carboxylic Acids from Aqueous Solutions with the Extractant System Alcohol/ Tri-n-Alkylamines. Chem. Eng. Technol. 2000, 23, 70−74. (20) Wasewar, K. L.; Heesink, A. B. M.; Versteeg, G. F.; Pangarkar, V. G. Equilibria and Kinetics for Reactive Extraction of Lactic Acid
4. CONCLUSIONS Reactive extraction of L(+)-tartaric acid using Aliquat 336 in nheptane, kerosene, and 1-octanol was studied. The results are expressed in terms of the distribution coefficient, extraction efficiency, loading ratio, and overall equilibrium complexation constant. The physical extraction was found to have a very low extraction efficiency and distribution coefficient. Extraction efficiency was found in the range of 0.38−4.72% for n-heptane, 0.78−6.0% for sunflower oil, and 2.0−5.92% for 1-octanol, whereas, the average extraction efficiency was 11.52−25.37 for n-heptane, 14.57−28.76 for kerosene, and 4.23−15.79 for 1octanol with 0.22 to 0.88 mol·kg−1 of Aliquat 336, respectively. Consequently, kerosene with Aliquat 336 showed a higher extraction efficiency for the reactive extraction of L(+)-tartaric acid. The distribution coefficient was found to be in the order kerosene + Aliquat 336 > n-heptane + Aliquat 336 > 1-decanol + Aliquat 336. Since z < 0.5, a surcharge was not attained and the (1:1) acid/amine complex was assumed to be formed. Also, the water coextraction was studied, and it was found to be not more than 6%. The relative basicity model gives a better prediction than the mass action law for the reactive extraction of L(+)-tartaric acid with Aliquat 336 in the diluents used.
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REFERENCES
AUTHOR INFORMATION
Corresponding Author
*E-mail: k_wasewar@rediffmail.com. Tel.: +91-712-2801561. Fax: +91-712-2801565. P
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