Liquid–Liquid Equilibrium Measurements for the Ternary System of

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Liquid−Liquid Equilibrium Measurements for the Ternary System of Water/2,3-Butanediol/4-Methyl-2-pentanol at Various Temperatures Joon-Hyuk Yim,† Kwang Woo Park,† Jong Sung Lim,*,† and Kyu Yong Choi‡ †

Department of Chemical and Biomolecular Engineering, Sogang University, Seoul, 121-742, Korea Department of Chemical and Biomolecular Engineering, University of Maryland, College Park, Maryland 20742, United States

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‡

ABSTRACT: Liquid−liquid equilibrium (LLE) of a ternary mixture of water, 2,3-butanediol, and 4-methyl-2-pentanol has been measured at three different temperatures (298.2, 308.2, and 318.2 K) under atmospheric pressure. The experimentally measured solubility and tieline data for the two-phase system were used to construct a ternary phase diagram at each temperature. With the experimental data, the distribution coefficients and separation factors were also calculated and Othmer− Tobias and Hand plots were used to verify the consistency of the measured data. The universal quasichemical (UNIQUAC) and nonrandom-two liquid (NRTL) models were used for the LLE, and the rootmean-square deviation values between the calculated and experimental data were less than 1.21% by the UNIQUAC model and less than 1.96% by the NRTL model, indicating that both model calculations provide excellent agreement with the experimentally measured LLE data in the present study. liquid−liquid extraction,15,16 reactive extraction17,18 and salting-out extraction.19 Among these, liquid−liquid extraction (solvent extraction) at low temperatures is considered as one of the most promising technologies because of its cost effectiveness and low-energy consumption.20−22 Liquid−liquid equilibrium (LLE) data are essential in designing a productive and efficient solvent extraction. Also, a proper solvent plays a key role because the solvent being used dictates the efficiency of separation and the overall process economy. To this purpose, various solvents have been studied for the recovery of the 2,3-BDO and water mixture.23−29 Birajdar et al.30 report that C4−C6 alcohols are potentially effective for the extraction of 2,3-BDO. 4-Methyl-2pentanol has been chosen in the current study as a solvent for the extraction of 2,3-BDO. In this work, to provide a database for the potential liquid− liquid extraction process using 4-methyl-2-pentanol as a solvent, isobaric LLE data of the water/2,3-BDO/4-methyl-2pentanol system have been measured at temperatures from 298.2 to 318.2 K. LLE data for this ternary system are not available in the literature. To verify the LLE data, Othmer− Tobias31 and Hand32 plots were used. Also, for each temperature, both the separation factors and the distribution coefficients were evaluated using the LLE data. Nonrandom two-liquid (NRTL)33 and universal quasichemical (UNIQUAC)34 models were used for correlating the experimental LLE data.

1. INTRODUCTION With a rapid progress in biotechnology, the production of biobased chemicals and materials using renewable resources has been the topic of worldwide research in recent years. Among numerous well-known biobased products, 2,3butanediol (2,3-BDO)1 is one of the most well-known and industrially important bulk chemicals. The first commercial scale biological processes of 2,3-BDO was developed during World War II, and there has been a renewed interest in recent years in developing advanced industrial biotechnology.2,3 Bacillus polymyxa, Klebsiella pneumoniae, Klebsiellaoxytoca, Bacillus subtilis, and Serratiamarcescens have been reported as 2,3-BDO producing strains.4−7 2,3-BDO is widely used in industry. For example, it is used to make solvents, antifreeze solutions, and plasticizers.6−9 2,3-BDO is also used in various intermediates such as methyl ethyl ketone (MEK) (a liquid fuel additive), 1,3-butadiene as a monomer for synthetic rubbers, and acetoin and diacetyl (precursors of polyurethanes), etc.2,10,11 Biotechnology for the microbial production of 2,3-BDO has progressed quite significantly in recent years using fermentation techniques.2 However, the biggest obstacle in commercializing microbial 2,3-BDO is the recovery cost of 2,3-BDO from fermentation broth associated with its high boiling point (177 °C at atmospheric pressure) and strong affinity with water. Also, the concentration of 2,3-BDO in fermentation broth is low, making the separation of 2,3-BDO by traditional distillation very difficult and costly. To solve the 2,3-BDO recovery problem, various alternative separation processes have been proposed, including reactive-distillation,12 membrane filtration,3,13 stream stripping,7 alcohol precipitation,14 © XXXX American Chemical Society

Received: April 3, 2019 Accepted: August 22, 2019

A

DOI: 10.1021/acs.jced.9b00290 J. Chem. Eng. Data XXXX, XXX, XXX−XXX

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2. EXPERIMENTAL SECTION 2.1. Materials. All chemicals used in this work were used as supplied and their purity data are listed in Table 1. Gas chromatography (GC) was used to assess the purity of pure components used in our experiments. The water used in this study was of HPLC grade.

cell of 80 mL in volume. To keep the cell temperature constant during the measurement period, a constant temperature water bath-circulator (RW3025, Lab Co. Korea) was used, and the cell temperature measured by an RTD sensor inserted in the cell was controlled within ±0.1 K of accuracy from the desired temperature set points. The standard uncertainty of temperature (u(T)) was 0.1 K. A precision balance (Precisa 1212 M) was used to measure the mass of the sample mixtures. The uncertainty of the precision balance is ±0.0001 g. A gas chromatograph (Young-Lin YL6100 GC, Korea) equipped with a thermal conductivity detector (TCD) and a Porapak Q column were used for the sample analysis. The temperatures of injector and detector were fixed at 523.15 K. The oven temperature was 473.15 K and the injection volume of the sample was 1 μL. Helium gas (purity, 0.999999 in mass fraction; flow rate, 30 mL/min) was used as a carrier gas. Ethanol which shows good solubility properties for three components was used as internal standard. Binodal point was determined by observing the cloud point that appears when the single phase mixture separates to two phases, The microburet having ±10−2 mL accuracy was used to titrate the mixtures of (water/4-methyl-2-pentanol) with 2,3BDO until the cloud point was reached. To obtain the solubility data in the water-rich phase, the water/2,3-BDO mixture was titrated with 4-methyl-2-pentanol until the clean solution became turbid. For the solubility data in the solventrich phase, a clear mixture of (4-methyl-2-pentanol/2,3-BDO)

Table 1. Suppliers and Mass Fraction of Materials component

CAS No.

suppliers

water

7732-18-5

levo-2,3butanediolb 4-methyl-2pentanol

24347-58-8

Daejung Co. (Korea) Sejinci Co. (Korea) Sejinci Co. (Korea)

108-11-2

mass fraction

analysis method

>0.999

GCa

>0.980

GCa

>0.990

GCa

a

Gas chromatograph. bStructure of levo-2,-3-butanediol:

2.2. Experimental Apparatus and Procedure. To measure LLE data, we used a water-jacketed glass equilibrium

Table 2. Binodal Solubility Curve Data (in Mass Fraction) for Water (1) + 2,3-Butanediol (2) + 4-Methyl-2-pentanol (3) System at T = 298.2, 308.2, and 318.2 Ka under Atmospheric Pressure titrated with water w1

w2

titrated with 2,3-butandiol w3

w1

w2

0.0557 0.0653 0.0772 0.0875 0.0966 0.1126 0.1340 0.2075

0.0000 0.0293 0.0816 0.1270 0.1668 0.2001 0.2273 0.3017

0.9443 0.9054 0.8412 0.7855 0.7366 0.6873 0.6387 0.4908

0.2389 0.2844 0.3214 0.3583 0.3838 0.4186 0.4532 0.4919

0.0622 0.0775 0.0904 0.1040 0.1220 0.1375 0.1529 0.1846 0.2075

0.0000 0.0567 0.1076 0.1491 0.1840 0.2142 0.2403 0.2697 0.3017

0.9378 0.8658 0.8020 0.7469 0.6941 0.6482 0.6068 0.5457 0.4908

0.2130 0.2487 0.2842 0.3077 0.3299 0.3639 0.4023 0.4406

298.2 K 0.3247 0.3464 0.3632 0.3676 0.3727 0.3816 0.3897 0.3934 308.2 K 0.2927 0.3153 0.3364 0.3496 0.3590 0.3733 0.3858 0.3927

0.0673 0.0706 0.0905 0.1102 0.1252 0.1420 0.1632 0.1900

0.0000 0.0557 0.1097 0.1489 0.1832 0.2122 0.2358 0.2657

0.9327 0.8737 0.7998 0.7409 0.6916 0.6458 0.6010 0.5443

0.2198 0.2537 0.3014 0.3437 0.3887 0.4330 0.4646 0.5119

318.2 K 0.2876 0.3102 0.3315 0.3438 0.3530 0.3621 0.3663 0.3695

titrated with 4-methyl-2-pentanol w3

w1

w2

w3

0.4364 0.3692 0.3154 0.2741 0.2435 0.1998 0.1572 0.1148

0.5743 0.6371 0.7019 0.7783 0.8213 0.8694 0.9233 0.9845

0.3714 0.3295 0.2723 0.2013 0.1593 0.1124 0.0597 0.0000

0.0543 0.0334 0.0258 0.0204 0.0194 0.0182 0.0170 0.0155

0.4942 0.4360 0.3793 0.3427 0.3111 0.2628 0.2119 0.1668

0.5203 0.5692 0.6300 0.6983 0.7746 0.8182 0.8669 0.9218 0.9842

0.3869 0.3759 0.3328 0.2766 0.2046 0.1621 0.1145 0.0609 0.0000

0.0928 0.0549 0.0371 0.0251 0.0208 0.0197 0.0186 0.0173 0.0158

0.4926 0.4360 0.3671 0.3125 0.2583 0.2049 0.1690 0.1186

0.6262 0.5614 0.6975 0.7565 0.8209 0.8696 0.9246 0.9869

0.3288 0.3684 0.2746 0.2234 0.1616 0.1141 0.0607 0.0000

0.0450 0.0703 0.0279 0.0201 0.0175 0.0162 0.0148 0.0131

a

The standard uncertainty of temperature is u(T) = 0.1 K. The overall standard uncertainty of solubility data is u(w) = 0.005 in mass fraction. B

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Table 3. LLE Data (in Mass Fraction) for Water(1) + 2,3-Butanediol (2) + 4-Methyl-2-pentanol (3) System at T = 298.2, 308.2, and 318.2 Ka under Atmospheric Pressure water-rich phase b

4-methyl-2-pentanol-rich phase b

w1

u(w1)

w2

u(w2)

0.6852 0.7173 0.7374 0.7609 0.7847 0.8024 0.8469 0.8702

0.0022 0.0021 0.0021 0.0020 0.0003 0.0010 0.0005 0.0005

0.2916 0.2617 0.2437 0.2195 0.1974 0.1788 0.1362 0.1122

0.0020 0.0029 0.0016 0.0005 0.0003 0.0008 0.0007 0.0000

0.6669 0.6902 0.7406 0.8103 0.8553 0.9190

0.0008 0.0028 0.0015 0.0014 0.0009 0.0013

0.3034 0.2809 0.2385 0.1718 0.1295 0.0661

0.0001 0.0006 0.0021 0.0016 0.0008 0.0007

0.6502 0.6723 0.6919 0.7089 0.7468 0.8122 0.8595 0.8784

0.0024 0.0014 0.0069 0.0009 0.0024 0.0007 0.0060 0.0012

0.3107 0.2942 0.2792 0.2653 0.2324 0.1689 0.1222 0.1047

0.0014 0.0014 0.0051 0.0012 0.0021 0.0012 0.0050 0.0013

w1

u(w1)b

w2

u(w2)b

0.1049 0.0940 0.0888 0.0862 0.0802 0.0770 0.0684 0.0657

0.0012 0.0027 0.0005 0.0029 0.0027 0.0003 0.0013 0.0015

0.1589 0.1336 0.1167 0.0988 0.0871 0.0753 0.0515 0.0389

0.0003 0.0008 0.0020 0.0000 0.0051 0.0005 0.0009 0.0002

0.1220 0.1130 0.0988 0.0752 0.0724 0.0534

0.0006 0.0006 0.0016 0.0006 0.0018 0.0009

0.1983 0.1770 0.1337 0.0834 0.0580 0.0263

0.0016 0.0024 0.0008 0.0007 0.0003 0.0002

0.1514 0.1346 0.1165 0.1193 0.0955 0.0808 0.0685 0.0666

0.0009 0.0017 0.0012 0.0023 0.0028 0.0006 0.0029 0.0000

0.2368 0.2153 0.1927 0.1815 0.1455 0.0965 0.0636 0.0506

0.0006 0.0016 0.0013 0.0027 0.0005 0.0002 0.0000 0.0005

298.2 K

308.2 K

318.2 K

a The standard uncertainty of temperature, u(T) = 0.1 K. bThe standard uncertainties of water (u(w1)) and 2,3-BDO (u(w2)) in mass fraction. All “0.0000” are rounded off values to the fourth decimal place.

was titrated with water until the mixture became turbid. To warrant the accuracy of the measurements, this procedure was repeated at least three times. The obtained binodal solubility data are reported in Table 2. To obtain the tie-line data in the phase diagram, the samples of water/2,3-BDO/4-methyl-2-pentanol mixtures are prepared such that the mixture composition lies inside the binodal curve (two-phase region). Experimentally, about 50 g of the prepared ternary mixture is placed in the water-jacketed glass equilibrium cell. The ternary mixture sample is stirred continuously for 3 h at 550 rpm using a magnetic stirring bar. Then the well mixed sample is left in the cell for more than 12 h to equilibrate. After the sample mixture is completely separated to organic solvent-rich (upper) and water-rich (lower) phases, samples taken from each phase are analyzed by GC to determine the composition. The results of compositional analysis are shown in Table 3 with the standard uncertainties of water (u(w1)) and 2,3-BDO (u(w2)) in mass fraction that were determined using the NIST35 and GUM36 protocols. Detailed explanations for the calculation of u(w) can be found elsewhere.37 In Table 3, the standard uncertainties of each composition (u(w)) were listed point by point, and the overall average value was 0.0014.

ln γi =

∑j xjGjiτji ∑k xkGki

∑

+

j

ÄÅ ÉÑ ÅÅ ∑k xkτkjGkj ÑÑÑ ÅÅ ÑÑ ÅÅτij − Ñ ∑k xkGkj ÑÑÑ ∑k xkGkj ÅÅÅ Ç Ö xjGij

(1)

where the subscripts i, j, and k denote the chemical species, xi is the mole fraction of species i and τij, τji, τkj, Gij, Gji, and Gkj are the adjustable binary parameters. These parameters are calculated using the following equations: Gij = exp( −αijτij) τij = aij +

bij T

and

Gii = 1

+ eij ln T

(2)

(3)

αij = αji = cij

(4)

where aij, bij, cij, and eij are the NRTL binary parameters and T is the temperature in K. The nonrandomness parameters (αij and αji) were set to 0.3. 3.2. UNIQUAC. The activity coefficient of component i (γi) in the UNIQUAC model is given as ln γi = li −

Vi xi

∑ xjlj + ln

ij j + qijjj1 − jj k

3. MODELING To correlate our experimental data, we used the NRTL31 and UNIQUAC32 thermodynamic models. 3.1. NRTL. The activity coefficient of component i (γi) in the NRTL model is given as follows:

j

∑ j

Vi F z + qi ln i 2 xi Vi

yz z − ln ∑ Fjτji zzz zz ∑k Fkτkj j { Fjτij

(5)

Where τij, τji, τkj, li, and lj indicate the adjustable parameters and z is the coordination number (set to 10). Fi, Fj, and Fk are the van der Waals surface areas and Vi is the volume fractions C

DOI: 10.1021/acs.jced.9b00290 J. Chem. Eng. Data XXXX, XXX, XXX−XXX

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of component i. The UNIQUAC model parameters are calculated as follows: z li = (ri − qi) − (ri − 1) (6) 2 τij = aij + bij /T + cij ln T + dijT

(7)

xr Vi = i i ∑ rx i i

(8)

Fi =

The measured data were plotted in triangular phase diagrams along with the calculation results by NRTL and UNIQUAC models. The ternary phase diagrams are shown in Figures 2, 3, and 4 for each measurement temperature. All

xiqi ∑ xiqi

(9)

where aij, bij, cij, and dij are the binary interaction parameters. ri is the volume parameter and qi is the surface area parameter, which are listed in Table 4. The ri and qi are calculated using the Bondi group contribution method.38 Table 4. van der Waals Volume Parameters r and Surface Parameters q for the UNIQUAC Models component

r

q

water 2,3-butanediol 4-methyl-2-pentanol

0.92 3.76 4.80

1.40 3.32 4.12

Figure 2. LLE data (mass fraction) for the ternary systems water + 2,3-butanediol + 4-methyl-2-pentanol at T = 298.2 K; , experimental solubility curve; ●●, experimental tie-line data; ☆---☆, calculated NRTL data; △---△, calculated UNIQUAC data.

4. RESULTS AND DISCUSSION In our LLE study of water/2,3-BDO/4-methyl-2-pentanol system, the LLE measurements were made at three different temperatures (298.2, 308.2, and 318.2 K) under atmospheric pressure. Tables 2 and 3 show the resulting binodal solubility and LLE data, respectively. To verify our binodal solubility data, we compared graphically our data with that from the literature39−41 for the 4-methyl-2-pentanol + water binary system in Figure 1. As can be seen in this figure, our data showed a similar trend with the literature data except for those from Ginnings et al. which were reported at 1938.40 Figure 3. LLE data (mass fraction) for the ternary systems water + 2,3-butanediol + 4-methyl-2-pentanol at T = 308.2 K; , experimental solubility curve; ●●, experimental tie-line data; ☆---☆, calculated NRTL data; △---△, calculated UNIQUAC data.

these phase diagrams indicate that the water/2,3-BDO/4methyl-2-pentanol system shows the phase behavior of type I where two completely miscible liquid pairs of 2,3-BDO/water and 2,3-BDO/4-methyl-2-pentanol, and one partially miscible liquid pair of (4-methyl-2-pentanol/water) are present. Tie-line data were verified using the Othmer−Tobias31 and Hand32 correlations presented in eq 10 and eq 11, respectively. ÅÄÅ ÑÉ ÅÄÅ ÑÉ ÅÅ 1 − w3I ÑÑÑ ÅÅ 1 − w1II ÑÑÑ Å Ñ Å ÑÑ lnÅÅ Ñ = a + b lnÅÅ ÅÅ w3I ÑÑÑ ÅÅ w1II ÑÑÑ (10) ÅÇ ÑÖ Ç Ö ÄÅ I ÉÑ ÄÅ II ÉÑ ÅÅ w ÑÑ ÅÅ w ÑÑ lnÅÅÅÅ 2I ÑÑÑÑ = c + d lnÅÅÅÅ 2II ÑÑÑÑ ÅÅ w3 ÑÑ ÅÅ w1 ÑÑ (11) ÅÇ ÑÖ Ç Ö

Figure 1. Solubility diagram of water in 4-methyl-2-pentanol for comparison of our experimental data and literature data: (red ●) this study (at 298.2, 308.2, and 318.2 K), (blue ■) Stephenson et al. (at 293.15, 303.15, 313.45, 323.15, and 333.25 K),39 (green ◆) Ginnings et al. (at 293.15, 298.15, and 303.15 K),40 (yellow ▲) Crittenden et al. (at 298.15 K)41

Here, w is the mass fraction, superscript I represents the 4methyl-2-pentanol-rich phase, and II represents the water-rich phase. The subscripts 1, 2, and 3 represent water, 2,3-BDO, D

DOI: 10.1021/acs.jced.9b00290 J. Chem. Eng. Data XXXX, XXX, XXX−XXX

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D2 vs W2II plots show excellent linearity. The regression coefficient values (R2) listed in Table 5 are all larger than 0.9905 indicating excellent consistency of the data correlations. Table 5. Constants of the Othmer−Tobias Equation and Hand Equation for the Water + 2,3-Butanediol + 4-Methyl2-pentanol System (R2: Regression Coefficient) Othmer−Tobias Correlation

Figure 4. LLE data (mass fraction) for the ternary systems water + 2,3-butanediol + 4-methyl-2-pentanol at T = 318.2 K; , experimental solubility curve; ●●, experimental tie-line data; ☆---☆, calculated NRTL data; △---△, calculated UNIQUAC data.

Hand Correlation

T/K

a

b

R2

c

d

R2

298.2 308.2 318.2

1.0125 1.0415 0.8761

0.3119 0.1580 −0.1525

0.9933 0.9948 0.9905

0.7552 0.7892 0.7442

0.3248 0.2207 0.0136

0.9987 0.9966 0.9968

To evaluate the potential of 4-methyl-2-pentanol as a solvent for extracting 2,3-BDO from aqueous solution, a distribution coefficient (D) and selectivity (S) are needed. They are defined as follows:

and 4-methyl-2-pentanol, respectively. These correlation results are plotted in Figure 5, and the distribution coefficients

D2 = S=

w2I w2II

(12)

w2I /w2II w1I/w1II

(13)

where superscript I indicates the 4-methyl-2-pentanol-rich phase, II represents the water-rich phase, and subscripts 1 and 2 refer to water and 2,3-BDO, respectively. As shown in the Table 6, although the distribution coefficients (D) are smaller than 1.0, the selectivities (S) of this solvent are much higher than 1.0 (3.27−6.84) in the temperature range investigated. Table 6. Distribution Coefficients of 2,3-Butanediol (D2) and Separation Factors (S) of Water + 2,3-Butanediol + 4Methyl-2-pentanol System at Different Temperatures T/K

wII2

D2a

Sb

298.2

0.2916 0.2617 0.2437 0.2195 0.1974 0.1788 0.1362 0.1122 0.3034 0.2809 0.2385 0.1718 0.1295 0.0661 0.3107 0.2942 0.2792 0.2653 0.2324 0.1689 0.1222 0.1047

0.54 0.51 0.48 0.45 0.44 0.42 0.38 0.35 0.65 0.63 0.56 0.49 0.45 0.4 0.76 0.73 0.69 0.68 0.63 0.57 0.52 0.48

3.56 3.9 3.98 3.97 4.32 4.39 4.68 4.59 3.57 3.85 4.2 5.23 5.29 6.84 3.27 3.65 4.1 4.07 4.9 5.74 6.53 6.37

308.2

318.2

Figure 5. (a) Othmer−Tobias plot for the water + 2,3-butanediol + 4methyl-2-pentanol system. (b) Hand plot for the water + 2,3butanediol + 4-methyl-2-pentanol system; ○, 298.2 K; △, 308.2 K; □, 318.2 K. Superscript I represents the 4-methyl-2-pentanol-rich phase, and II represents the water-rich phase. w1, w2, and w3 are the mass fractions of water, 2,3-BDO, and 4-methyl-2-pentanol, respectively.

a

Distribution coefficients of 2,3-butanediol (D2 = wI2/wII2 ). bSeparation factors (S = (wI2/wII2 )/(wI1/wII1 )).

E

DOI: 10.1021/acs.jced.9b00290 J. Chem. Eng. Data XXXX, XXX, XXX−XXX

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This result implies that 4-methyl-2-pentanol is a very effective solvent for extracting 2,3-BDO from the aqueous solution. In Figure 6, D2 values are plotted against wII2 . Note that the distribution coefficients for 2,3-BDO increase with temper-

Table 8. Parameters of the UNIQUAC Models (τij) for the Water (1) + 2,3-Butanediol (2) + 4-Methyl-2-pentanol (3) System and RMSD Values at T = 298.2, 308.2, and 318.2 K under Atmospheric Pressure τija

T/K 298.2 308.2 318.2

τ12 τ21 τ12 τ21 τ12 τ21

= = = = = =

2045.14 −36.6308 1123.38 76.0314 1200.00 113.758

τ13 τ31 τ13 τ31 τ13 τ31

= = = = = =

RMSD

−211.514 −129.947 −220.271 −152.08 −238.567 −139.963

τ23 τ32 τ23 τ32 τ23 τ32

= = = = = =

−2911.45 2200.11 −528.116 1337.71 −385.315 1433.99

0.0081 0.0110 0.0121

a τij = exp(−εij)/RT. τij is a UNIQUAC model binary interaction parameter (dimensionless).

RMSD values, the agreement between the experimental data and the model is very satisfactory. Therefore, we can conclude that the experimental LLE data obtained in this study have been successfully correlated with both models. The binary parameters calculated from these two models could be used in simulating and designing the extraction processes for the system investigated in this work.

Figure 6. Distribution coefficients (D2) plotted against the mass fraction of 2,3-BDO in water-rich phase (wII2 ) for water + 2,3butandiol + 4-methyl-2-pentanol system at different temperatures: ●, 298.2 K; ◇, 308.2 K; ▲, 318.2 K.

5. CONCLUSIONS We have investigated the feasibility and effectiveness of 4methyl-2-pentanol as an extracting solvent. The LLE data of water/2,3-BDO/4-methyl-2-pentanol system was obtained at three different temperatures, 298.2, 308.2, and 318.2 K under atmospheric pressure. For this temperature range, the separation factors of 4-methyl-2-pentanol for 2,3-BDO were found to be greater than 3.2 (4.58 in average). This signifies that 4-methyl-2-pentanol is a very effective extracting solvent for 2,3-BDO from fermented aqueous solution. The measured LLE data were verified by the Othmer−Tobias plot and Hand plot. The regression coefficients (R2) were larger than 0.9905, indicating a good consistency of the data obtained in our experimental study. The NRTL and UNIQUAC models also showed excellent correlations with the experimental data with a RMSD less than 0.0196 and 0.0121, respectively.

ature and the concentration of 2,3-BDO in the water-rich phase (wII2 ). Thus, we can conclude that the temperature and wII2 have positive effects on the distribution coefficients of 2,3BDO. On the other hand, as shown in Table 6, as the mass fraction of 2,3-BDO in the water-rich phase (wII2 ) decreases, the separation factor (S) increases. To verify the fidelity of data fitting with the NRTL and UNIQUAC models in predicting the LLE, we calculated the root-mean-square deviations (RMSD) using following equation. É1/2 ÅÄÅ 3 exp cal 2 Ñ ÅÅ ∑i = 1 ∑2j = 1 ∑nk = 1 (xijk − xijk ) ÑÑÑÑ ÅÅ ÑÑ RMSD = ÅÅ ÑÑ ÅÅ 6n ÅÅÇ ÑÑÑÖ (14) For each model, Tables 7 and 8 present the calculated binary parameters and RMSD values at each temperature. The RMSD

■

AUTHOR INFORMATION

Corresponding Author

Table 7. Parameters of the NRTL Models (τij) for the Water (1) + 2,3-Butanediol (2) + 4-Methyl-2-pentanol (3) System and RMSD Values at T = 298.2, 308.2, and 318.2 K under Atmospheric Pressure

*Tel.: +82 02 7058918. E-mail: [email protected].

τija

The authors declare no competing financial interest.

T/K 298.2 308.2 318.2

τ12 τ21 τ12 τ21 τ12 τ21

= = = = = =

−9523.64 946.735 −8452.42 833.195 −8628.96 841.26

τ13 τ31 τ13 τ31 τ13 τ31

= = = = = =

−9523.64 946.735 −8452.42 833.195 −8628.96 841.26

ORCID

Jong Sung Lim: 0000-0002-1826-6216 Notes

RMSD τ23 τ32 τ23 τ32 τ23 τ32

= = = = = =

−9523.64 946.735 −8452.42 833.195 −8628.96 841.26

■

0.0115

ACKNOWLEDGMENTS This study was supported by Basic Science Research Program through the National Research Foundation of Korea (NRF) funded by the Ministry of Education (NRF2016R1D1A1B01013707). This research was also supported by C1 Gas Refinery Program through the National Research Foundation of Korea (NRF) funded by the Ministry of Science, ICT & Future Planning (NRF2017M3D3A1A01037006-2).

0.0177 0.0196

τij = (gij − gjj)/RT. τij is a NRTL model binary interaction parameter (dimensionless). a

■

values are less than 0.0196 for the NRTL models and those for the UNIQUAC model are less than 0.0121. Looking at the binary parameters in the Tables 7 and 8, we observe that there is no relation between the temperature and the parameter values. Generally, if the correlation result shows less than 5% in

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DOI: 10.1021/acs.jced.9b00290 J. Chem. Eng. Data XXXX, XXX, XXX−XXX