Liquid–Liquid Phase Equilibria for Quinary, Quaternary, and Ternary

Article Cite This: J. Chem. Eng. Data XXXX, XXX, XXX−XXX

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Liquid−Liquid Phase Equilibria for Quinary, Quaternary, and Ternary Systems {Water + Furfural + Acetic Acid + Cyclopentyl Methyl Ether + CaCl2}: Measurement, Effect of Salt ,and Comparative Study Hongxun Zhang*

J. Chem. Eng. Data Downloaded from pubs.acs.org by WASHINGTON UNIV on 08/08/18. For personal use only.

College of Chemistry, Chemical and Environmental Engineering, Henan University of Technology, Zhengzhou, Henan 450001, China ABSTRACT: Ternary liquid−liquid equilibria (LLE) data for water + furfural + cyclopentyl methyl ether (CPME) and quaternary LLE data for water + furfural + acetic acid + CPME were measured at T = 293.15, 303.15, and 313.15 K and atmosphere pressure (p ≈ 100.25 kPa). In addition, the LLE for the quinary system of {water + furfural + acetic acid + CPME + CaCl2} were determined at 303.15 K and atmosphere pressure to study salting effect on the quaternary system. Finally, based on researches of predecessors and our previous work, comparative study of various solvents including CPME, 2-methyltetrahydrofuran (2-MTHF), p-xylene, toluene, methyl iso-butyl carbinol (MIBC), tert-amyl methyl ether (TAME), and methyl tert-butyl ether(MTBE) was demonstrated.

1. INTRODUCTION Nowadays, people are paying more and more attention to renewable energy, circular economy, and cleaner production technical of chemicals. Furfural, which is one of the important industry chemicals, can be only obtained from renewable biomass and agricultural waste such as corncob, wheat straw, rice hull, bagasse, coconut shell, among others.1−4 As a key platform chemical, furfural is widely used in synthetic resins, synthetic fibers, synthetic rubber, and oil refining.5−7 Especially, higher requirement is put forward to the quality of furfural used in food, medicine, flavor, and pesticides.8,9 In current furfural manufacturing processes, there are three major shortcomings: low final furfural yield, a large amount of refractory wastewater, and high-energy consumption.10,11 Therefore, the current research on furfural production has focused on how to increase the yield, reduce waste emissions, and energy consumption. It is worth noting that biphasic process of furfural production has obvious advantage in yield and decreasing wastewater comparing to other methods.12,13 Many organic solvents like toluene, 1-butanol, cyclohexane, 2-methyltetrahydrofuran (2-MTHF), methyl iso-butyl carbinol (MIBC), and cyclopentyl methyl ether (CPME) have been used in the water−solvents biphasic system.14−16 Of the solvents, the overall furfural yield can be up to near 100% when water− CPME biphasic system is adopt under certain conditions.15 On the other hand, in order to reduce the energy consumption it is also the important thing to select suitable purification method of furfural. The crude furfural which comes from reactor often contains lots of water and some quantity of acetic acid. The acetic acid in the crude furfural cannot be neglected because its content is about one-quarter of furfural in mass fraction.17−19 Because an azeotrope with water is formed at 0.35 furfural mass fraction and there is low relative volatility between acetic acid and water, liquid extraction can be an economically attractive option.20 The quaternary or ternary liquid−liquid equilibria (LLE) data of some organic solvents © XXXX American Chemical Society

(such as p-xylene, toluene, MIBC, 2-MTHF, TAME, MBTE, and CPME, and so forth) with water, furfural, and/or acetic acid have been reported.21−24 We have reported the ternary LLE of {water + acetic acid + CPME}.25 In this work, quaternary and ternary LLE for CPME with water, furfural, and acetic acid were measured at T = 293.15, 303.15, and 313.15 K and p ≈ 100.25 kPa. To study the salting effect on the quaternary system mentioned above, the LLE for the quinary system of {water + furfural + acetic acid + CPME + CaCl2} was determined at 303.15 K and atmosphere pressure. Finally, a comparative study of the relevant solvents has been made in terms of physical properties and extraction capability.

2. EXPERIMENTAL SECTION 2.1. Materials. Furfural (CAS No. 98-01-1), acetic acid (CAS No. 64-19-7) with minimum mass fraction of 0.99 and 0.998, anhydrous calcium chloride (CAS No.10043-52-4) with purity of 0.999, and chromatographic grade isopropanol (CAS No. 67-63-0) as the internal standard were purchased from Sinopharm Chemical Reagent Co., Ltd. CPME (CAS No. 5614-37-9) with a mass fraction of 0.999 was supplied by Alfa Aesar Inc. Bidistilled water was prepared in our lab. Before the experiment, furfural was further distilled, and other chemicals were used without further purification. The purities, densities, and refractive index of all chemicals used in this work were checked and listed in Table 1 together with the values from the literature.26,27 The density (ρ) and refractive index (nD) were measured at T = 293.15 K and p = 100.25 kPa. A density instrument (Julabo VDM-300, made in Germany) which had a reported uncertainty of u = 1.0 kg·m−3 was used to measure the densities of the chemicals. An Abbé refractometer (2WAJ, Shanghai) was used to determine the refractive indexs in this Received: March 21, 2018 Accepted: July 24, 2018

A

DOI: 10.1021/acs.jced.8b00222 J. Chem. Eng. Data XXXX, XXX, XXX−XXX

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Table 1. Chemicals Used in This Work and Their Reported and Measured Gas Chromatograph (GC) Purities, Density (ρ), and Refractive Index (nD) Measured at 100.25 kPaa ρ/(kg·m−3) (T = 293.15 K)

purity (mass fraction) chemical name

supplier

minimum purity

water furfural acetic acid CPME

Sinopharm Sinopharm Alfa Aesar

0.99 0.998 0.999

b

nD (T = 293.15 K)

GC analysis

exptl.

litc

exptl

litc

0.9995 0.9985d 0.9983 0.9995

998.25 1159.16 1048.93 860.13

998.2 1159.4 1049.2 860e

1.3334 1.5259 1.3717 1.4187

1.3334 1.5261 1.3718 1.4189e

Standard uncertainty (u) are u(w, mass fraction) = 0.0005, u(ρ) = 1.0 kg·m−3, u(nD) = 0.0002, u(T) = 0.05 K, u(p) = 1.0 kPa. bStated by supplier. Taken from ref 26. dThe purity after distilled. eTaken from ref 27.

a c

Table 2. LLE Data in Mass Fraction, Distribution Coefficients, and Separation Factor for {Water (1) + Furfural (2) + CPME (3)} at T = 293.15, 303.15, and 313.15 K and p ≈ 100.25 kPaa water-rich phase(II)

solvent-rich phase(I)

T/K

w1

w2

w1

w2

Dfurfural

Sfurfural

293.15

0.9752 0.9678 0.9631 0.9571 0.9532 0.9509 0.9469 0.9422 0.9753 0.9677 0.9626 0.9569 0.9532 0.9505 0.9467 0.9416 0.9752 0.9676 0.9621 0.9562 0.9523 0.9495 0.9458 0.9408

0.0166 0.0244 0.0296 0.0359 0.0395 0.0419 0.0461 0.0505 0.0169 0.0251 0.0305 0.0365 0.0405 0.0433 0.0472 0.0521 0.0177 0.0256 0.0311 0.0372 0.0413 0.0441 0.0481 0.0539

0.0081 0.0103 0.0126 0.0153 0.0172 0.0201 0.0222 0.0259 0.0093 0.0123 0.0146 0.0181 0.0203 0.0236 0.0262 0.0306 0.0103 0.0135 0.0161 0.0199 0.0223 0.0256 0.0288 0.0337

0.1100 0.1923 0.2729 0.3658 0.4262 0.4812 0.5432 0.6315 0.1093 0.1895 0.2688 0.3587 0.4179 0.4705 0.5327 0.6201 0.1081 0.1876 0.2661 0.3551 0.4137 0.4658 0.5235 0.6123

6.66 7.88 9.22 10.19 10.79 11.48 11.78 12.51 6.47 7.55 8.81 9.83 10.32 10.87 11.29 11.90 6.11 7.33 8.56 9.55 10.02 10.56 10.88 11.36

790.76 740.52 704.71 637.40 597.96 543.31 502.59 454.91 678.25 593.98 581.06 519.55 484.51 437.63 407.80 366.24 578.24 525.24 511.30 458.67 427.76 391.76 357.42 317.13

303.15

313.15

Figure 1. LLE phase diagram for {water (1) + furfural (2) + CPME (3)} at T = 293.15, 303.15, and 313.15 K and p ≈ 100.25 kPa.

Figure 2. Comparison of the LLE tie-line data for {water + furfural + CPME} measured in this work to the literature data.22

a

Standard uncertainties u are u(T) = 0.05 K, u(p) = 1.0 kPa, u(wI1) = 0.0015, u(wI2) = 0.002, u(wI3) = 0.0008, u(wII1 ) = 0.001, u(wII2 ) = 0.0018, and u(wII3 ) = 0.001.

2.2.2. Procedure. Before the experiment, the mixed solution of furfural and acetic acid in a mass ratio of 4:1 and three different concentrations of calcium chloride aqueous solution was prepared. Then, furfural or the mixed solution of furfural and acetic acid, water or calcium chloride aqueous solution, and CPME was added to the jacketed glass cell at the designed mass fraction. The steps below were detailed in earlier work.28 2.2.3. Sample Analysis. Samples of the ternary and quaternary systems were analyzed using gas chromatography. Because the samples contained salt, the samples of the quinary system were analyzed in two steps: (1) all the component contents except salt were determined using gas chromatograph (GC-122) and (2) the salt content was measured by using argentimetry. The detailed conditions of analysis are as follows: thermal conductivity detector (TCD), bridge current = 120 mA; column, 2 m long and 2 mm inner diameter packed with

work. It had a standard uncertainty of u(nD) = 0.0002 reported by the refractometer manufacturer. 2.2. Apparatus and Procedure. 2.2.1. Apparatus. An electronic balance (AUY220, SHIMADZU) which had a reported standard uncertainty of ±0.0001 g was used to weigh mixures and some samples. A gas chromatograph (GC-122) equipped with a thermal conductivity detector (TCD) and a Parapak Q-S (80/100) column packing were used to analyze the components of the samples. The salt contents of samples were measured using an automatic potentiometric titractor (ZDJ-4A) which was equipped with a silver-ion selectiveelectrode (216 type) and a reference electrode (217 type). The ZDJ-4A had a resolution of 0.1 mV. Other apparatus such as a thermostatically controlled bath (501A type, Shanghai, China) with an accuracy of ±0.05 K and an approximately 50 cm3 jacketed glass cell were used in this work. B

DOI: 10.1021/acs.jced.8b00222 J. Chem. Eng. Data XXXX, XXX, XXX−XXX

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Table 3. LLE Data in Mass Fraction, Distribution Coefficients, and Separation Factor for {Water (1) + Furfural(2) + Acetic Acid (3) + CPME (4)} at T = 293.15, 303.15, and 313.15 K and p ≈ 100.25 kPaa water-rich phase

solvent-rich phase

T/K

w1

w2

w3

w1

w2

w3

Dfurfural

Dacetic acid

Sfurfural

Sacetic acid

293.15

0.9548 0.9341 0.9058 0.8928 0.8663 0.8504 0.8221 0.7948 0.7748 0.9518 0.9296 0.9022 0.8852 0.8567 0.8376 0.8059 0.7758 0.7532 0.9458 0.9216 0.8885 0.8695 0.8554 0.8348 0.8094 0.7718 0.7379

0.0175 0.0253 0.0364 0.0416 0.0486 0.0525 0.0597 0.0676 0.0733 0.0192 0.0277 0.0364 0.0437 0.0521 0.0578 0.0666 0.0751 0.0821 0.0211 0.0295 0.0405 0.0477 0.0541 0.0586 0.0678 0.0775 0.0867

0.0188 0.0305 0.0469 0.0540 0.0711 0.0824 0.1027 0.1212 0.1344 0.0208 0.0338 0.0517 0.0607 0.0784 0.0909 0.1131 0.1336 0.1482 0.0249 0.0404 0.0619 0.0727 0.0793 0.0941 0.1090 0.1358 0.1596

0.0115 0.0155 0.0214 0.0275 0.0368 0.0437 0.0545 0.0599 0.0673 0.0117 0.0157 0.0243 0.0301 0.0429 0.0532 0.0661 0.0699 0.0776 0.0121 0.0169 0.0260 0.0359 0.0452 0.0541 0.0669 0.0717 0.0795

0.0984 0.1590 0.2538 0.3176 0.3896 0.4361 0.4969 0.5451 0.5761 0.0935 0.1511 0.2412 0.3018 0.3701 0.4143 0.4721 0.5178 0.5473 0.0888 0.1435 0.2291 0.2867 0.3516 0.3936 0.4485 0.4919 0.5199

0.0085 0.0146 0.0236 0.0292 0.0394 0.0477 0.0605 0.0722 0.0805 0.0081 0.0139 0.0224 0.0273 0.0374 0.0448 0.0575 0.0686 0.0765 0.0077 0.0132 0.0213 0.0263 0.0305 0.0377 0.0455 0.0575 0.0678

5.62 6.28 6.97 7.63 8.02 8.31 8.32 8.06 7.86 4.87 5.45 6.63 6.91 7.10 7.17 7.09 6.89 6.67 4.21 4.86 5.66 6.01 6.50 6.72 6.62 6.35 6.00

0.45 0.48 0.50 0.54 0.55 0.58 0.59 0.60 0.60 0.39 0.41 0.43 0.45 0.48 0.49 0.51 0.51 0.52 0.31 0.33 0.34 0.36 0.38 0.40 0.42 0.42 0.42

466.84 378.74 295.13 247.86 188.71 161.65 125.55 106.99 90.48 396.16 322.98 246.02 203.10 141.86 112.85 86.43 76.52 64.70 328.96 265.27 193.31 145.57 122.99 103.64 80.03 68.32 55.66

37.54 28.85 21.30 17.56 13.05 11.27 8.89 7.90 6.90 31.68 24.35 16.09 13.23 9.53 7.76 6.20 5.70 5.01 24.17 17.82 11.76 8.76 7.28 6.18 5.05 4.56 3.94

303.15

313.15

a Standard uncertainties u are u(T) = 0.05 K, u(p) = 1.0 kPa, u(wI1) = 0.0012, u(wI2) = 0.0018, u(wI3) = 0.002, u(wI4) = 0.001, u(wII1 ) = 0.001, u(wII2 ) = 0.0015, u(wII3 ) = 0.0017, and u(wII4 ) = 0.0008.

Table 4. Coefficients (a, b), Linear Correlation Coefficient (R2), and Standard Deviation (SD) of the Othmer−Tobias Equation for {Water (1) + Furfural (2) + CPME (3)} at T = 293.15, 303.15, and 313.15 K and p ≈ 100.25 kPa T/K

a

b

R2

SD

293.15 303.15 313.15

9.2430 8.9964 8.3627

3.1212 3.0472 2.8545

0.9962 0.9960 0.9904

0.0579 0.0592 0.0919

Table 5. Coefficients (a, b), Linear Correlation Coefficient (R2), and Standard Deviation (SD) of the Othmer−Tobias Equation for {Water (1) + Furfural (2) + Acetic Acid (3) + CPME (4)} at T = 293.15, 303.15, and 313.15 K and p ≈ 100.25 kPa Figure 3. LLE phase diagram for {water (1) + furfural (2) + acetic acid (3) + CPME (4)} at T = 293.15, 303.15, and 313.15 K and p ≈ 100.25 kPa.

T/K

a

b

R2

SD

293.15 303.15 313.15

2.9860 3.2590 2.4712

1.6601 1.6911 1.6110

0.9981 0.9985 0.9925

0.0463 0.0432 0.0873

The potentiometric titration was used to determine the calcium chloride content of the samples. Specific steps are the following: step 1, weigh the samples and record their weight; step 2, dilute the samples with a certain amount of water, measure the content of chloride-ion by the automatic potentiometric titractor (ZDJ-4A), and meanwhile a blank titration must be done; step 3, calculate the calcium chloride content based on the chloride-ion content of the samples.

Parapak Q-S (80/100) mesh; oven temperature = 453.15 K, detector temperature = 493.15 K, and injector temperature = 473.15 K; carrier gas, hydrogen, flow rate = 0.8 cm3·s−1; and sample injection = 0.2 mm3. The internal standard and correction factor methods were used to analyze the compositions by using isopropanol as the internal standard. The peak separations were very clear under the chromatographic conditions. C

DOI: 10.1021/acs.jced.8b00222 J. Chem. Eng. Data XXXX, XXX, XXX−XXX

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reproducibility and repeatability measurements, the relative standard uncertainties in mass fraction of all compositions were calculated according to the “Evaluation of measurement data-Guide to the expression of uncertainty in measurement”.29

3. RESULT AND DISCUSSION 3.1. Experimental Data. The ternary LLE data for {water + furfural + CPME} at T = 293.15, 303.15, and 313.15 K and p ≈ 100.25 kPa is listed in Table 2. Figure 1 shows the LLE phase behavior of the ternary system at different temperatures. Männistö et al.22 have reported the LLE data of {CPME + furfural + water} between 298 and 343 K. Figure 2 shows a comparison of the LLE tie-line data between this work and the literature by Männistö et al. From Figure 2, it can be seen that the LLE tie-line diagrams at different temperatures of this work have a good consistency with the literature.22 The quaternary LLE data for {water + furfural + acetic acid + CPME} is listed in Table 3, and Figure 3 shows the LLE phase behavior of the quaternary systems at different temperatures. The extraction capability of a solvent can be measured by the distribution coefficient.The separation factor can be used to evaluate the selectivity of the solvent. The distribution coefficient (D) and the separation factor (S) are given by

Figure 4. Comparison of distribution coefficients for furfural when used different solvents.

Di =

Si =

wiI wiII

(1)

Di D1

(2)

where w represents the mass fraction of the componet, and the superscripts I and II represent the solvent-rich phase and water-rich phase, respectively. D1 represents the distribution coefficient of water. The distribution coefficient of furfural (Dfurfural) and separation factor (Sfurfural) for the ternary system are listed in the Table 2 together with LLE data. Table 3 lists the Dfurfural, Dacetic acid, Sfurfural, and Sacetic acid for the quaternary system at three temperatures. 3.2. Reliability of the LLE Data. The reliability of the experimental LLE tie-line data can be validated by the Othmer−Tobias30,31equation as

Figure 5. Comparison of separation factors for furfural when used different solvents.

I II ji 1 − wsolvent zyz jij 1 − wwater zyz z j zz = + lnjjj ln a b zz jj II j wI z solvent k { k wwater {

The uncertainties of this method are not more than 0.0035 in mass fraction. The determination of the composition of the each sample was carried out more than three times, and the average values were used as sample composition. On the basis on the

(3)

When Othmer−Tobias equation is used to evaluate the reliability of the tie-line data for the containing salt quinary system, it can be depicted as

Table 6. A Comparison of the Properties for CPME, MTBE, TAME, 2-HTMF, Toluene, p-Xylene, and MIBC properties CPMEa MTBEa TAME 2HTMFa toluene p-xylene MIBCf

boiling point [K]

enthalpy of vaporization (bp) [kJ·kg−1]

azeotropic point with water [K]

azeotrope with furfural

azeotrope with acetic acid

solubility of solvent in water [g/100 g]

solubility of water in solvent [g/100 g]

379.15 328.15 359.51b 353.15

289.66 341.98 337.67b 364.59

356.15 326.05 340.91c 362.15

no no no no

no no no no

1.1 (296.15K) 4.8 (296.15 K) 0.9096d 14 (296.15 K)

0.3 (296.15K) 1.5 (296.15 K) 0.7858d 4.4 (296.15 K)

383.78 411.50f 507.50

363.51 339.08f 414.07

357.25 366.15f 367.45

no yesg no

yes yesg no

0.0682e 0.0207e 1.729 (293.15K)

0.0532e 0.0553e 6.157 (293.15K)

a

Taken from ref 27. bTaken from ref 32. cCalculated by Aspen Plus using NRTL model. dTaken from ref 33 at T = 298.15 K and atmospheric pressure. eTaken from ref 34 at T = 303.15 K and p = 101.3 kPa. fTaken from ref 35. gTaken from ref 26. D

DOI: 10.1021/acs.jced.8b00222 J. Chem. Eng. Data XXXX, XXX, XXX−XXX

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Table 7. LLE Data in Mass Fraction for {Water (1) + Furfural (2) + Acetic Acid (3) + CPME (4) + CaCl2 (5)} at T = 303.15 K, p ≈ 100.25 kPa, and Different Initial Concentration of CaCl2a water-rich phase(II)

solvent-rich phase(I)

initial mass fraction of CaCl2

w1

w2

w3

w4

w5

w1

w2

w3

w4

0.0498

0.9152 0.8961 0.8753 0.8589 0.8478 0.8352 0.8259 0.8152 0.8040 0.8722 0.8554 0.8434 0.8322 0.8212 0.8125 0.8024 0.7933 0.7849 0.8276 0.8152 0.8054 0.7977 0.7862 0.7780 0.7715 0.7668 0.7596

0.0172 0.0257 0.0332 0.0389 0.0430 0.0484 0.0526 0.0569 0.0620 0.0155 0.0235 0.0291 0.0337 0.0379 0.0424 0.0457 0.0487 0.0522 0.0134 0.0201 0.0237 0.0282 0.0328 0.0365 0.0393 0.0434 0.0471

0.0125 0.0249 0.0393 0.0514 0.0595 0.0677 0.0733 0.0803 0.0863 0.0094 0.0195 0.0286 0.0359 0.0438 0.0487 0.0568 0.0636 0.0693 0.0078 0.0162 0.0237 0.0282 0.0361 0.0415 0.0462 0.0476 0.0520

0.0053 0.0055 0.0061 0.0061 0.0063 0.0062 0.0065 0.0066 0.0072 0.0033 0.0045 0.0039 0.0044 0.0046 0.0048 0.0049 0.0052 0.0052 0.0016 0.002 0.0028 0.0034 0.0038 0.0043 0.0044 0.0047 0.0047

0.0498 0.0478 0.0461 0.0447 0.0434 0.0425 0.0417 0.0410 0.0405 0.0996 0.0971 0.0950 0.0938 0.0925 0.0916 0.0902 0.0892 0.0884 0.1496 0.1465 0.1444 0.1425 0.1411 0.1397 0.1386 0.1375 0.1366

0.0107 0.0149 0.0209 0.0242 0.0278 0.0343 0.0373 0.0462 0.0529 0.0100 0.0144 0.0175 0.0219 0.0257 0.0284 0.0320 0.0358 0.0393 0.0093 0.0125 0.0147 0.0164 0.0187 0.0197 0.0226 0.0254 0.0289

0.1147 0.2013 0.2847 0.3355 0.3843 0.4398 0.4842 0.5342 0.5773 0.1224 0.2129 0.2782 0.3449 0.3953 0.4485 0.4916 0.5429 0.5859 0.1276 0.2289 0.2946 0.3511 0.4146 0.4659 0.5023 0.5512 0.5975

0.0077 0.0175 0.0316 0.0440 0.0527 0.0623 0.0708 0.0782 0.0825 0.0091 0.0217 0.0354 0.0466 0.0580 0.0657 0.0769 0.0861 0.0933 0.0111 0.0248 0.0378 0.0488 0.0594 0.0683 0.0793 0.0880 0.1016

0.8669 0.7663 0.6628 0.5963 0.5352 0.4636 0.4077 0.3414 0.2873 0.8584 0.7509 0.6688 0.5865 0.5210 0.4574 0.3995 0.3352 0.2815 0.8518 0.7337 0.6528 0.5836 0.5072 0.4461 0.3958 0.3354 0.2720

0.0997

0.1500

w5 4.4 3.4 2.6 2.0 1.6 1.4 1.2 4.3 2.5 1.2 9.1 7.1 5.5 4.4 3.2 2.1 1.1 3.9 1.6 1.3 1.0 8.1 6.0 3.9 2.4 1.3 5.2

× × × × × × × × × × × × × × × × × × × × × × × × × × ×

10−05 10−05 10−05 10−05 10−05 10−05 10−05 10−06 10−06 10−04 10−05 10−05 10−05 10−05 10−05 10−05 10−05 10−06 10−04 10−04 10−04 10−05 10−05 10−05 10−05 10−05 10−06

Standard uncertainties u are u(T) = 0.05 K, u(p) = 1.0 kPa, u(wI1) = 0.002, u(wI2) = 0.0015, u(wI3) = 0.0018, u(wI4) = 0.001, u(wI5) = 0.5 × 10−06, u(wII1 ) = 0.001, u(wII2 ) = 0.0012, u(wII3 ) = 0.0015, u(wII4 ) = 0.0008, and u(wII5 ) = 0.0035.

a

Table 8. Coefficients (c and d), Linear Correlation Coefficient (R2), and Standard Deviation (SD) of the Othmer−Tobias Equation for the Quinary {Water (1) + Furfural (2) + Acetic Acid (3) + CPME (4) + CaCl2 (5)} at T = 303.15 K, p ≈ 100.25 kPa, and Different Initial Mass Fraction of CaCl2 c

R2

d

SD

initial mass fraction of CaCl2

furfural

acetic acid

furfural

acetic acid

furfural

acetic acid

furfural

acetic acid

0.0497 0.9980 0.1500

31.6418 39.3603 38.0207

36.0118 42.8986 39.7642

−10.0903 −17.0358 −20.8387

−10.6770 −17.4981 −20.4360

0.9866 0.9918 0.9933

0.9465 0.9483 0.9695

0.0940 0.0724 0.0648

0.2028 0.1913 0.1375

II y ij 1 − wiI yz i zz = c + d lnjjj 1 − wsalt zzz lnjjj zz jj II j w I zz i k { k wsalt {

4. COMPARATIVE STUDY First, the effect of temperature on distribution coefficient and separation factor is studied. From Table 2 and Table 3, we can see that the distribution coefficient and separation factor of furfural and acetic acid increase with the decrease of temperature. When compared with Dfurfural and Sfurfural in the ternary system of {water + furfural + CPME}, the values of the Dfurfural and Sfurfural in the quaternary system drop a lot because of the addition of acetic acid. Second, the extraction capability and physical properties of different solvents are compared. Many solvents such as p-xylene, toluene, MIBC, 2-MTHF, TAME, MBTE, and CPME were used to extract furfural and/or acetic acid from water.21−24 To further evaluate the properties of the solvents mentioned above, a comparative study is conducted in terms of their distribution coefficients, separation factors, and physical properties. The distribution coefficients and separation factors of furfural when using different solvents are summarized in Figure 4

(4)

where the superscript I and II represent the solvent-rich phase and the water-rich phase, respectively; the subscript solvent represents CPME, subscript i represents solute furfural (i = 2) or acetic acid (i = 3), subscript salt represents calcium chloride; and a, b, c, and d are the coefficients of the Othmer− Tobias equation. Table 4 and Table 5 list the validation results of Othmer− Tobias equation for the ternary and quaternary systems, respectively. As shown in Table 4 and Table 5, all of the correlation factors (R2) are not less than 0.9823, and all of the standard deviations (SDs) are not more than 0.1269. The consistency of the ternary and quaternary experimental tie-line data is satisfactory. The consistency of the quinary system on the salt basis was evaluated by using eq 4. E

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because their structures are similar to furfural. It is worth noting that the distribution coefficients of toluene, p-xylene, and MIBC from the literaure24 are the values in low concentration of furfural. From Figure 5, it can be seen that the separation factor of furfural (Sfurfural) using p-xylene is close to that using toluene and significantly higher than that when using other solvents, and the order of Sfurfural using other solvents is CPME > TAME > MTBE > 2-MTHF > MIBC. The separation factor of solvent has a direct relation to its mutual solubility with water. In general, the lower the mutual solubility is, the larger the separation factor is. From Table 6, it can be seen easily that the mutual solubilities of p-xylene and toluene with water are far less than that of other solvents. However, from the Table 6 it is found that CPME has smaller enthalpy of vaporization than all the other solvents. It means that CPME would have the greatest energy-saving potential.28 The solvent, p-xylene, has a larger separation factor, however, it can form azeotropes with both furfural and acetic acid, respectively.35 That will create difficulties for subsequent separation processes such as distillation or azeotropic distillation. It is similar to p-xylene when using toluene as solvent because toluene can form azeotrope with acetic acid.35 Finally, salt-effect on the LLE of {water + furfural+ acetic acid+CPME} system has been studied. At T = 303.15 K and p ≈ 100.25 kPa, the LLE data for {water (1) + furfural (2) + acetic acid (3) + CPME (4) + CaCl2 (5)} with CaCl2 mass fraction in the initial saline solution of 0.0498, 0.0997, and 0.1500 was measured and listed in Table 7. The coefficients (c and d), linear correlation coefficient (R2), and standard deviation (SD) of the Othmer−Tobias equation for the quinary system are listed in Table 8. Table 9 lists the distribution coefficient and separation factor of the quinary system at different initial concentration of CaCl2. Figure 6 shows the LLE phase diagram of the quinary system on a salt-free basis. As shown in Figure 6, with the increase of CaCl2 initial mass fraction in the saline solution the contents of furfural and acetic acid in the water-rich phase decrease clearly, and the two-phase regions increase. From Table 9, it can be seen that Dfurfural, Dacetic acid, Sfurfural, and Sacetic acid show a marked increase with the increase of the initial concentration of CaCl2.

Table 9. Distribution Coefficients (D) and Separation Factor (S) of {Water (1) + Furfural (2) + Acetic Acid (3) + CPME (4) + CaCl2 (5)} at T = 303.15 K, p ≈ 100.25 kPa, and Different Initial Concentration of CaCl2 initial mass fraction of CaCl2 0.0498

0.0997

0.1500

Dwater

Dfurfural

Dacetic acid

Sfurfural

Saceitc acid

0.01 0.02 0.02 0.03 0.03 0.04 0.04 0.05 0.06 0.01 0.02 0.02 0.02 0.03 0.03 0.04 0.04 0.05 0.01 0.01 0.02 0.02 0.02 0.02 0.03 0.03 0.03

6.34 7.45 8.18 8.24 8.54 8.69 8.82 9.01 8.94 7.12 8.19 8.64 9.27 9.46 9.60 9.79 10.15 10.23 8.13 9.74 10.64 10.67 10.85 10.99 11.02 10.96 10.94

0.58 0.67 0.77 0.82 0.85 0.88 0.93 0.93 0.92 0.88 1.00 1.12 1.18 1.20 1.23 1.23 1.23 1.23 1.21 1.31 1.36 1.48 1.41 1.42 1.48 1.59 1.69

570.39 470.62 359.14 306.26 272.24 221.02 203.77 165.76 141.58 689.43 538.73 460.03 388.77 332.91 302.49 269.95 246.92 224.04 850.58 744.32 681.10 605.36 531.29 504.40 436.52 383.58 333.18

52.51 42.18 33.67 30.39 27.01 22.41 21.38 17.19 14.54 84.77 66.10 59.65 49.34 42.27 38.61 33.97 30.01 26.90 126.27 99.74 87.39 84.14 69.23 65.05 58.63 55.80 51.38

5. CONCLUSIONS The LLE data for the ternary {water + furfural + CPME} system, quaternary {water + furfural + acetic acid + CPME} system, and quinary {water + furfural + acetic acid + CPME + CaCl2} system were reported. The reliability of the LLE tieline data was evaluated by the Othmer−Tobias equation. The results indicate that the reliability of the experimental LLE data is acceptable. By the comparative study, the following conclusions are drawn: (1) it may be beneficial to extract furfural and/or acetic acid from water using CPME as solvent at a relatively low temperature; (2) p-xylene may not be a good solvent to extract furfural and acetic acid from water although it has a very high separation factor because it can form azeotropes with both furfural and acetic acid, respectively; (3) CPME may be the suitable solvent for separating furfural and acetic acid from water because it has a relatively high extraction efficiency and a lower enthalpy of vaporization; (4) the effect of the addition of CaCl2 to the quaternary {water + furfural + acetic acid + CPME} system is notable, the two-phase region, distribution coefficient, and separation factor increase with the increasing initial concentration of CaCl2.

Figure 6. LLE phase diagram on salt-free basis for {water (1) + furfural (2) + acetic acid (3) + CPME (4) + CaCl2 (5)} at T = 303.15 K, p ≈100.25 kPa, and different CaCl2 initial concentrations.

and Figure 5. As shown in Figure 4, the distribution coefficient of furfural (Dfurfural) using CPME is close to that using 2-MTHF and slightly above that using MTBE and TAME but is clearly higher than that when using p-xylene and MIBC as solvent. A larger distribution coefficient means the solvent extracts more solute from water. This phenomenon can be explained by the principle of “like dissolves like”. CPME, 2-MTHF, and toluene have larger distribution coefficient F

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AUTHOR INFORMATION

Corresponding Author

*E-mail: [email protected]. Tel: +86037167756725. Fax: +86037167756718. ORCID

Hongxun Zhang: 0000-0001-8916-9715 Notes

The author declares no competing financial interest.

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DOI: 10.1021/acs.jced.8b00222 J. Chem. Eng. Data XXXX, XXX, XXX−XXX