Article pubs.acs.org/jced
Equilibrium and Thermodynamic Studies on Reactive Extraction of Nicotinic Acid Using a Biocompatible Extraction System Dipaloy Datta,† B. V. Babu,‡ and Sushil Kumar*,§ †
Department of Chemical Engineering, Malaviya National Institute of Technology, Jaipur, Rajasthan 302017, India Computer Science & Engineering, Graphic Era University, Dehradun, Uttarakhand 248002, India § Department of Chemical Engineering, Motilal Nehru National Institute of Technology, Allahabad, Uttar Pradesh 211004, India ‡
ABSTRACT: The separation of organic compounds using reactive extraction (combination of extractant + solvent system) has a great potential in the near future but limits its application in the extractive fermentation system because of the toxicity of solvents. Here, a study is performed for the recovery of nicotinic acid using a biocompatible system comprising a tertiary amine, tri-ndodecylamine (TDDA), a high molecular weight modifier, oleyl alcohol, and an inert diluent, n-dodecane. At first, the effect of oleyl alcohol (modifier or active solvent) is studied at fixed TDDA concentration (0.1 v/v) with ndodecane. Oleyl alcohol (increased from 0.06 to 0.62 w/w) enhanced the extraction efficiency significantly (from 15.46% to 67.25%). To have a control over the physical properties of the extraction system, further extraction studies are performed using TDDA (9.94 × 10−5 to 4.91 × 10−4 mol·kg−1) dissolving it in n-dodecane and oleyl alcohol mixture maintained at a ratio of 2:1 w/w, and varying nicotinic acid concentration from 0.022 to 0.122 mol·kg−1. The highest distribution of acid is observed to be 1.87 with 4.91 × 10−4 mol·kg−1 of TDDA at 0.057 mol·kg−1 acid concentration and at 301 K. To deduce the extraction mechanism, the stoichiometric coefficient of complex formation (m), and equilibrium constant are determined. The temperature (varied between 301 and 333 K) effect is studied on the distribution coefficient, and used to determine thermodynamic parameters (ΔHo = −133.63 kJ·mol−1; ΔSo = −414.69 J·mol−1·K−1).
1. INTRODUCTION There is a tremendous demand for chemicals which could be synthesized by using biomass or renewable resources. Chemical industries are constantly looking for environmental benign routes to produce biofuel and biochemicals which are in high demand in the world market.1,2 Many carboxylic acids are produced by microorganisms but the challenge lies in their production by a fermentation path using renewable carbon sources such as feed stock.3 Nicotinic acid is such a kind of an organic acid which can be produced by nitrilase enzymes in a bioreactor.4 The acid plays a major role in DNA repair and helps in the formation of steroid hormones in the adrenal gland. The deficiency of this acid in the human body may lead to pellagra, and reduces metabolism activity causing a decrease in tolerance to cold.5−7 The separation of carboxylic acids from the fermentation medium which contains a very low amount of acid is a difficult step and limits the overall recovery. When the acid molecules are continuously generated in the fermentor then the pH of the broth goes down which inhibits the growth of the microorganisms. This leads to a low yield and productivity of acid. Researchers have tried several recovery methods to get a concentrated solution of organic acids, but application of these methods has been restricted because of their inherent shortcomings.8−12 These disadvantages could be overcome by using extractive fermentation in which the acid level in the © 2017 American Chemical Society
broth can be maintained constantly separating the product, that is, acid. It has been observed that normally the solvents used in the recovery process have a toxicity which may be harmful to the microorganisms to a certain degree. This is a major concern and becomes more dominant when the in situ technique of separation is used. The toxicity of solvents at the molecular level which depends on the solubility of solvent in the aqueous phase is comparatively less damaging than the phase level toxicity.13−15 A parameter, log Pa which is the logarithm of the distribution of the solvent between 1-octanol and water, is defined to denote the degree of toxicity. For toxic solvents the value of log Pa is less than 4, and for nontoxic solvents its value is generally greater than 6.16,17 To reduce the toxicity of the extracting medium, a nontoxic solvent or a mixture of a toxic one with a nontoxic one may be chosen to give an extracting system which will not inhibit the growth of the microbes used for the production of acid. Further addition of an immiscible and biocompatible solvent to the medium, which will capture any toxic compound present in the aqueous medium, may also reduce the toxic effect of the solvent.18 Literature is available with the equilibrium as well as kinetic studies for the reactive extraction of pyridine carboxylic Received: May 19, 2017 Accepted: August 29, 2017 Published: September 11, 2017 3431
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acids.19−27 Researchers have investigated the effect of several parameters of the system such as composition of the phases, type of diluents and extractants, type of acids, pH of the aqueous phase, temperature of the recovery system, etc. on the distribution of carboxylic acids. Here, in the current work, separation of nicotinic acid from a dilute solution of water is studied using a biocompatible system comprising an extractant, tri-n-dodecylamine (TDDA) dissolved in a diluent, n-dodecane (log Pa = 6.628) and, an active solvent, oleyl alcohol (log Pa = 7.6929).
3. RESULTS AND DISCUSSION The study on the extraction of nicotinic acid from its dilute aqueous solution was done by using a combination of a tertiary amine extractant, tri-n-dodecylamine (TDDA), an inert diluent, n-dodecane, and an active diluent or a modifier, oleyl alcohol. The equilibrium study showed that the solubility of extracted acid molecules increased in the organic phase because of the presence of modifier (oleyl alcohol). The addition of modifier (from 0.06 to 0.62 w/w) in the organic phase enhanced the recovery of nicotinic acid as depicted from Figure 1. The oleyl
2. EXPERIMENTAL SECTION 2.1. Chemicals. Nicotinic acid with purity of 0.995 w/w) was procured from Himedia, India. Tri-n-dodecylamine of 0.95 w/w purity was obtained from Fluka, USA. Oleyl alcohol (0.98 w/w of purity) and n-dodecane (0.98 w/w) were purchased from Spectrochem, India. Sodium hydroxide (0.98 w/w purity; Merck, India) solution was prepared freshly in water to determine the equilibrium concentration of acid with phenolphthalein (pH range of 8.2 to 10.0, CDH, India) as an indicator for titration. All the aqueous solutions were prepared using distilled water. 2.2. Method. The required amount of nicotinic acid was solubilized in distilled water to prepare four different concentrations varying from 0.022 to 0.122 mol·kg−1. The organic solvent phase was prepared by using tri-n-dodecylamine (TDDA: 9.94 × 10−5 to 4.91 × 10−4 mol·kg−1) dissolved in solvents such as n-dodecane and oleyl alcohol. Twenty milliliters of aqueous solution of acid was made in contact with same volume of organic phase in 100 mL conical flask to conduct the equilibrium experiments. These were placed in a water bath shaker (REMI Laboratories, India) fixed at constant temperature (301 K). The shaker was set at 100 rpm, and 6 h of time was given for the equilibrium to achieve. After that, the samples were kept for 2 h to have a distinct separation of phases. The quantity of nicotinic acid in the water phase at equilibrium was measured by titration with a NaOH solution of 0.01 N. The acid content in the organic solvent phase was determined by considering an exact mass balance (Corg = Cin − Caq) and negligible change in the volume of each phase. The equilibrium experiments and chemical analysis were repeated twice for some data points, and their mean values were used for the calculation purpose. The organic solvents like TDDA, ndodecane and oleyl alcohol, used in the present study are poorly miscible in water, and hence their effect of solubility was not accounted in the calculation of distribution coefficient (KD), degree of extraction (%E), and loading ratio (Z) as shown by eqs 1, 2, and 3, respectively. m KD = ̅ HNc mHNc (1) E=
m̅ HNc KD = × 100 m in 1 + KD
(2)
Z=
m̅ HNc m̅ NR3 ,in
(3)
Figure 1. Influence of modifier (oleyl alcohol) in the mixture of ndodecane + oleyl alcohol + TDDA (0.1 v/v) on degree of extraction at 301 K.
alcohol affected the extraction efficiency significantly when used with 0.1 v/v TDDA and n-dodecane. Since, the oleyl alcohol is viscous as compared to n-dodecane, a mixture of n-dodecane and oleyl alcohol was used in the ratio of 2:1 w/w to carry out further experiments. The equilibrium data for the reactive extraction of nicotinic acid are shown as isotherms in Figure 2 at varying concentrations of TDDA (9.94 × 10−5 to 4.91 × 10−4 mol·kg−1) with n-dodecane and oleyl alcohol maintained at 2:1 w/w. Using the experimental data, the values of KD, E, and Z are calculated and given in Table 1. It can be seen that, with the increase in the concentration of TDDA, their values increased. Also, the initial concentration of nicotinic acid affected the extraction efficiency, and their values notably decreased with an increase from 0.022 to 0.122 mol·kg−1. Different concentrations of TDDA were used to understand the effect of initial concentration of acid on the extraction efficiency. The effect of acid concentration on the degree of extraction is more significant with lower concentration of TDDA (limiting reagent). 3.1. Chemical Extraction Model (Chemodel). When the chemical interactions between the components present in both phases forming the acid−extractant complex are assumed to be stronger than the physical interactions in the system, then the extraction mechanism at equilibrium can be modeled successfully by proposing the formation of various stoichiometric complexes of acid and extractant in the extracting phase. The series of stoichiometric reactions occurring in the process may be described by the mass action law, and can be referred to as the chemical modeling (Chemodel) . Considering, m
where m̅ HNC and mHNc are equilibrium acid concentrations in the solvent and water phase, respectively; mHNc,in and m̅ NR3,in are the initial acid concentration in the aqueous phase and the initial extractant (TDDA) concentration in the organic solvent phase, respectively. 3432
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where the species concentrations are denoted by braces, the organic-phase species are marked with an overbar, and Kmn represents the corresponding equilibrium constant. It is also assumed that the extraction of acid by solvent alone (such as n-dodecane and oleyl alcohol) is negligible, there is no acid-dimers formed in the organic phase, and no water molecules are coextracted along with the acid molecules. Further, the dissociation of nicotinic acid molecule takes place by eq 6. The undissociated acid in the aqueous phase [HNc] can be found out using the relationships as given in eq 7 to 9, where mHNc is the total initial concentration of acid and Ka (= 1.78 × 10−5 for nicotinic acid at 298 K)30 is the dissociation constant for eq 6. HNc ↔ H+ + Nc− [H+][Nc−] [HNc]
(7)
mHNc = [HNc] + [Nc−]
(8)
Ka = Figure 2. Equilibrium isotherms of nicotinic acid for different concentrations of TDDA dissolved in n-dodecane + oleyl alcohol (2:1 w/w). Symbols: ■, 9.94 × 10−5 mol·kg−1; ∗, 1.97 × 10−4 mol· kg−1; ▲, 2.96 × 10−4 mol·kg−1; ▼, 4.91 × 10−4 mol·kg−1.
[HNc] =
K mn =
KD =
(4)
[(NR3)n (HNc)m ] [HNc]m [NR3]n
mHNc (1 + K a /[H+])
(9)
Therefore, the overall distribution coefficient (KD) may be given by eq 10 where m̅ HNc is the total nicotinic acid concentration in the organic phase at equilibrium.
molecules of acid (HNc) are interacting with n molecules of extractant (NR3) to form various (m:n) complexes at equilibrium, the following eqs (eqs 4 and 5) may be used to explain the process at equilibrium. mHNc + n NR3 ↔ (NR3)n (HNc)m
(6)
[(NR3)n (HNc)m ] m̅ HNc =m mHNc mHNc
(10)
Substituting the values of [(NR3)n (HNc)] from eq 5, and mHNc from eq 9 in eq 10 will give following eq 11.
(5)
Table 1. Equilibrium Results for the Extraction of Nicotinic Acid Using TDDA Dissolved in n-Dodecane/Oleyl Alcohol (2:1 w/ w) at a Temperature of 301 Ka m̅ NR3,in mol·kg−1 9.94 × 10−5
1.97 × 10−4
2.96 × 10−4
4.91 × 10−4
mHNc,in
mHNc
mol·kg−1 0.022 0.042 0.057 0.091 0.122 0.022 0.042 0.057 0.091 0.122 0.022 0.042 0.057 0.091 0.122 0.022 0.042 0.057 0.091 0.122
mol·kg−1 0.014 0.026 0.035 0.058 0.087 0.011 0.020 0.027 0.048 0.076 0.009 0.017 0.024 0.042 0.068 0.008 0.015 0.020 0.035 0.058
m̅ HNc mol·kg−1 0.008 0.016 0.022 0.034 0.036 0.011 0.022 0.030 0.044 0.047 0.013 0.025 0.033 0.050 0.055 0.014 0.027 0.037 0.056 0.065
KD
E
Z
pH
(−) 0.58 0.63 0.64 0.58 0.41 1.02 1.12 1.13 0.91 0.62 1.46 1.40 1.39 1.18 0.81 1.77 1.84 1.87 1.62 1.12
(%) 36.84 38.56 39.06 36.74 29.22 50.38 52.74 52.99 47.65 38.17 59.40 58.41 58.21 54.19 44.68 63.91 64.79 65.18 61.83 52.82
(−) 0.104 0.208 0.287 0.430 0.459 0.072 0.143 0.196 0.281 0.302 0.056 0.106 0.143 0.212 0.235 0.036 0.070 0.096 0.146 0.167
(−) 3.31 3.17 3.11 3.00 2.91 3.36 3.23 3.17 3.04 2.94 3.41 3.26 3.19 3.07 2.96 3.43 3.30 3.23 3.11 3.00
a
Relative standard uncertainties in molalities, ur(mHNc) = 0.1; standard uncertainties in temperature u(T) = 0.58 K; standard uncertainties in pH, u(pH) = 0.006. 3433
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Article
KD(1 + K a /[H+])m m−1 mmHNc [ m NR3]n
(11)
where m̅ NR3 is the free extractant concentration in the organic phase and determined as, m̅ NR3 = m̅ NR3 ,in −n[(HNc)(NR3)n ] = m̅ NR3 ,in −KDnmHNc /m
(12)
Putting the value of m̅ NR3 from eq 12 in eq 11 will lead to eq 13. m ⎞n mHNc n − 1 ⎛ KD = mKE⎜m̅ NR3,in − KDn HNc ⎟ ⎝ m ⎠ (1 + K a /[H+])m
(13)
For n = 1, eq 13 is used to determine the values of equilibrium extraction constant (Km1) and the stoichiometry (m) of the extraction reaction. The error between the experimental and predicted values of KD was minimized using the following objective function, root-mean-square deviation (rmsd). ⎡ ∑ (K exp − D rmsd = ⎢ ⎢⎣ N
Figure 3. Estimation of (1:1) nicotinic acid−TDDA equilibrium constant (K11) using eq 15 with different concentrations of TDDA in n-dodecane/oleyl alcohol (2:1 w/w). Symbols: ■, 9.94 × 10−5 mol· kg−1; ∗, 1.97 × 10−4 mol·kg−1; ▲, 2.96 × 10−4 mol·kg−1; ▼, 4.91 × 10−4 mol·kg−1.30
1/2 KDmodel)2 ⎤
⎥ ⎥⎦
(14)
where N is the number of data points. Again, the values of loading ratio, Z (given by eq 3) may also be utilized to determine the equilibrium constant and type of interactions between nicotinic acid and TDDA. The parameter Z gives an idea about the extraction ability of the extractant, that is, the strength of the acid−base interaction in the solvent phase. When the organic phase is not highly concentrated by the acid molecules, that is, at a relatively low loading of acid on the extractant (Z < 0.5, as values of Z are found in between 0.036 and 0.459), 1:1 acid−extractant complex formation may be assumed.31 Therefore, an equation relating Z and the equilibrium constant (K11 for m = 1 and n = 1) may be given as eq 15.
Z = K11[HNc] 1−Z
Table 2. Values of Equilibrium Constants (Km1 and K11) and Number of Reacting Acid:Extractant Molecules (m:n) for the Reactive Extraction of Nicotinic Acid (0.022 to 0.122 mol· kg−1) with TDDA Dissolved in n-Dodecane and Oleyl Alcohol (2:1 w/w) m̅ NR3,in mol·kg−1 9.94 1.97 2.96 4.91
(15)
× × × ×
−5
10 10−4 10−4 10−4
m
n
Km1 (using eq 13)
K11 (using eq 15) −1
(−)
(−)
(−)
kg mol
1.15 1.01 0.98 0.96
1 1 1 1
15.69 8.84 6.62 4.68
10.79 6.71 5.30 4.02
R2 (−) 0.982 0.964 0.965 0.967
percentage removal of nicotinic acid for all concentrations of TDDA. The increase in the thermal energy interferes in the interactions of acid and TDDA molecules which leads to the decrease of extraction capacity of the extractant. For a temperature of 333 K, extraction efficiency slightly increased due to the increased interactions between TDDA and acid (0.122 mol·kg−1) molecules. However, an improved separation of the phases is observed. The trend in the degree of extraction with temperature is in agreement with the results obtained by Keshav et al.29 Their study was focused on the extraction of monocarboxylic acids using Aliquat 336 as extractant and oleyl alcohol as an active diluent. From the thermodynamic point of view, the molecules of acid in the organic phase are more ordered as they exist as a complex. Thus, acid transfer from the aqueous phase as solvates to the organic phase increases the order and reduces the entropy. Generally the transfer of compounds from the aqueous phase to the organic phase is accompanied by a decrease in entropy. 3.3. Estimation of ΔHo and ΔSo. The thermodynamic analysis was performed by determining the standard enthalpy (ΔHo) and entropy (ΔSo) from the temperature study data. The Km1 values are estimated at temperatures of 301, 308, 313, 323, and 333 K for the separation of nicotinic acid using TDDA in n-dodecane/oleyl alcohol (2:1 w/w). Equation 13 was used
The calculated values of Z/(1 − Z) against [HNc] were plotted and fitted by a straight line passing through the origin giving the values of K11 from the slope (Figure 3). The estimated values of m and Km1 using eq 13, and K11 using eq 15 are given in Table 2. The m values determined are found to be near about 1 (0.96 to 1.15) with different TDDA concentrations indicating mainly a 1:1 type of complexes is formed in the organic phase. Small deviations in the values of m, depicts that there may be the possibility of little physical extraction of nicotinic acid molecules by diluents as well. Since the initial concentration of nicotinic acid used in the current study was not high (0.022 to 0.122 mol·kg−1) as compared to the TDDA concentration (9.94 × 10−5 to 4.91 × 10−4 mol· kg−1), the value of Z was found to be less than 0.5 (Table 1) which also validates the possible presence of 1:1 complexes of acid and TDDA in the organic phase. 3.2. Effect of Temperature. The study was also performed to see the effect of temperature on the extraction−equilibrium of nicotinic acid with TDDA (9.94 × 10−5 to 4.91 × 10−4 mol· kg−1) dissolved in n-dodecane/oleyl alcohol (2:1 w/w). The temperature was changed from 301 to 333 K, and the results are plotted in terms of extraction efficiency (Figure 4). The increase in the temperature had shown a negative effect on the 3434
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The negative value of ΔHo (−133.63 kJ mol−1) showed that the extraction process is exothermic. Similarly, the decrease in ΔSo (−414.69 J·mol−1·K−1) depicted that the process is stabilized, reducing the randomness of the system.
4. CONCLUSIONS The equilibrium and thermodynamic study for the recovery of nicotinic acid using TDDA as extractant, n-dodecane as inert diluent, and oleyl alcohol as modifier had been done extensively in this paper. Oleyl alcohol with n-dodecane showed a prominent effect on the distribution of acid between the phases. A highest distribution of acid was found to be 1.84 with TDDA (4.91 × 10−4 mol·kg−1) in n-dodecane + oleyl alcohol (2:1 w/w) at lower acid concentration of 0.022 mol·kg−1 and at 301 K. The reaction stoichiometry (m), overall (Km1), and individual (K11) equilibrium constants were determined which confirmed mainly 1:1 type of complex formation in the organic phase. From the temperature effect (301 to 333 K) study, it may be inferred that the interaction of different molecules is ordered with exothermicity. TDDA with a mixture of nontoxic diluents like n-dodecane and oleyl alcohol could be used as a biocompatible mixture for the recovery of nicotinic acid in in situ extractive fermentation.
Figure 4. Influence of temperature on extraction of nicotinic acid with different concentrations of TDDA in n-dodecane/oleyl alcohol (2:1 w/w). Symbols: ■, 9.94 × 10−5 mol·kg−1; ∗ 1.97 × 10−4 mol·kg−1; ▲, 2.96 × 10−4 mol·kg−1; ▼, 4.91 × 10−4 mol·kg−1. Relative standard uncertainties in molalities, ur(mHNc) = 0.1; standard uncertainties in temperature u(T) = 0.58 K; standard uncertainties in pH, u(pH) = 0.006.
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AUTHOR INFORMATION
Corresponding Author
*E-mail:
[email protected].
with n = 1 to determine the values of Km1 (36.93 at 301 K, 12.92 at 308 K, 2.12 at 313 K, 1.27 at 323 K, and 3.46 at 333 K). It may be seen that there is a decrease in the values of Km1 up to a temperature of 323 K but a sudden increase in Km1 is observed at 333 K. Therefore, in the calculation of change in standard enthalpy and entropy Km1 values at 301, 308, 313, and 323 K were considered. In the temperature range studied it was assumed that the change in enthalpy and entropy remains ΔH o ΔS o constant. The Vant’ Hoff equation (ln KE = − RT + R ) was used, and the data of ln Km1 was plotted against 1/T. This plot was fitted with a straight line, and from the slope and intercept the change in standard enthalpy and entropy of the reactive extraction reaction was determined, respectively (Figure 5).
ORCID
Dipaloy Datta: 0000-0002-2048-9064 Sushil Kumar: 0000-0001-7114-4579 Funding
Department of Science and Technology (DST), India, for funding a research project under Fast track scheme for Young Scientist, SR/FTP/ETA-25/2011, Reactive Extraction of Nicotinic- and Isonicotinic Acids from Aqueous Solution (PI: Dr. Sushil Kumar, MNNIT, Allahabad, India). Notes
The authors declare no competing financial interest.
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Figure 5. Determination of apparent enthalpy and entropy for the extraction of nicotinic acid with TDDA in n-dodecane/oleyl alcohol (2:1 w/w). R2 = 0.922. 3435
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DOI: 10.1021/acs.jced.7b00457 J. Chem. Eng. Data 2017, 62, 3431−3436
