Quaternary and Quinary Liquid–Liquid Equilibria for Systems of

Article pubs.acs.org/jced

Quaternary and Quinary Liquid−Liquid Equilibria for Systems of Ethanol + Butanol + Octane + Nonane + Water at 298.15 K under Atmospheric Pressure Shenfeng Yuan, Jiafeng Liu, Hong Yin,* and Zhirong Chen Zhejiang Provincial Key Laboratory of Advanced Chemical Engineering Manufacture Technology, College of Chemical and Biological Engineering, Zhejiang University, Hangzhou 310027, China ABSTRACT: Liquid−liquid equilibrium (LLE) data for the quaternary systems of ethanol + butanol + octane + water and ethanol + butanol + nonane + water were obtained at 298.15 K under atmospheric pressure in this article. The nonrandom twoliquid (NRTL) equation was used to correlate the LLE data, and the two quaternary systems were used to regress the interaction parameters of the model. The obtained interaction parameters of NRTL model were used to predict the LLE of the quinary system ethanol + butanol + octane + nonane + water and was compared with the experimental values. The results showed that the calculated values coincided with the experimental data well, an indication that the NRTL model and the interaction parameters obtained from quaternary systems could be used to predict the LLE data of quinary system. The LLE data of the quinary system were also characterized by the distribution coefficient and the selectivity, and the results showed that the ethanol aqueous solution which contained about 40 wt % ethanol was suitable for separating butanol from the butanol−octane−nonane mixture.

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INTRODUCTION As a result of diminishing petroleum reserves, violent fluctuations of crude oil prices, increasingly stringent regulations for environmental protection purposes, and the global demand for a decreased dependence on petroleum for the production of fuels and chemicals in the past few years, Fischer−Tropsch (FT) synthesis1 has been considered as one of the most promising ways to produce ultraclean fuel at an economically feasible cost.2−4 The FT synthesis product spectrum is composed of a complicated multicomponent mixture of paraffins, olefins, alcohols, and aldehydes.2,5−7 The synthesis of alcohols under FT conditions is an attractive research target, and lots of relative research work8−11 has been done because alcohols can be used as fuels, fuel additives for octane or cetane enhancement, and as intermediates for high-value chemicals. However, there are lots of azeotropes between alkane and alcohol.12 Thus, research on the separation of alkane and alcohol is essential. Extraction is one of the feasible methods for separating alkane and alcohol, and ethanol aqueous solution is a potential extractant. In this article, the LLE for systems containing ethanol + butanol + octane + nonane + water was investigated. Skrzecz13 has reviewed the ternary LLE of alcohol + hydrocarbon + water systems including ethanol + water + octane, ethanol + water + nonane. In this article, LLE was performed at 298.15 K under atmospheric pressure for the quaternary system ethanol + water + butanol + octane and ethanol + water + butanol + nonane. The LLE data of the two quaternary systems were used to correlate the binary parameters of NRTL model. The obtained parameters were © 2017 American Chemical Society

used to predict the LLE of the quinary system ethanol + butanol + octane + nonane + water, and the calculated values were compared with the experimental data. The LLE data of the quinary system were also characterized by the distribution coefficient and the selectivity.

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EXPERIMENTAL SECTION Materials. Information about the chemicals is listed in Table 1. Ethanol (>0.995, Sinopharm), butanol (>0.995, Sinopharm), and nonane (>0.990, Aladdin) were used directly without any further purification. Octane (>0.98, Sinopharm) was purified by distillation. Distilled water was used in the experiments. Isoamyl alcohol (>0.985, Sinopharm) which was purified by distillation was used as the internal standard. The purity of organic materials was confirmed by gas chromatography. The moisture in the samples was measured by the Karl Fisher (KF) titration method (ANTING ZSD-1). Apparatus and Procedure. The apparatus used in the experiments was the same with the apparatus in the other works.14,15 The apparatus consisted of an 80 cm3 glass roundbottomed vessel with a thermostated water jacket and sample opening in each phase. The temperature was controlled by a super thermostatic water bath (AHYQ HH-501) with the accuracy of 0.01 K. A precision electronic balance (JINGHAI FA1004N) was used to ensure the accuracy of 0.1 mg. All of the experiments were done at 298.15 K under atmospheric pressure. First of all, each component was added Received: December 16, 2016 Accepted: March 20, 2017 Published: March 29, 2017 1487

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Table 1. Specifications of the Chemicals

a

chemical name

CAS No.

source

initial purity (mass fraction)

purification method

final purity (mass fraction)

ethanol butanol nonane octane isoamyl alcohol

64-17-5 71-36-3 111-84-2 111-65-9 123-51-3

Sinopharm Sinopharm Aladdin Sinopharm Sinopharm

>0.995 >0.995 >0.995 >0.98 >0.985

none none none distillation distillation

0.9996 0.9974 0.9975 0.9994 0.9993

analysis method GCa, GCa, GCa, GCa, GCa,

KFb KFb KFb KFb KFb

Gas chromatography. bKarl Fischer moisture meter.

Table 2. Experimental LLE Data (Mass Fraction) for the Quaternary System Ethanol (1) + Butanol (2) + Octane (3) + Water (5) at 298.15 K under Atmospheric Pressurea alkane-rich phase

a

water-rich phase

w1

w2

w3

w5

w1

w2

w3

w5

0.0390 0.0844 0.1313 0.0497 0.0399 0.0386 0.0450 0.0327 0.0259 0.0243 0.0397 0.0866 0.0293 0.0229 0.0199 0.0189 0.0191

0.4251 0.3965 0.3602 0.1371 0.0954 0.0814 0.3998 0.0775 0.0549 0.0422 0.3632 0.2810 0.0705 0.0465 0.0335 0.0265 0.0216

0.4825 0.4499 0.4146 0.8006 0.8566 0.8735 0.5046 0.8846 0.9160 0.9309 0.5598 0.5887 0.8962 0.9281 0.9448 0.9531 0.9579

0.0534 0.0691 0.0938 0.0126 0.0081 0.0065 0.0506 0.0053 0.0032 0.0026 0.0372 0.0437 0.0040 0.0025 0.0018 0.0014 0.0014

0.0623 0.1198 0.1787 0.2471 0.2823 0.3138 0.0766 0.2758 0.3118 0.3513 0.0849 0.1705 0.2547 0.2857 0.3288 0.3701 0.4080

0.0622 0.0683 0.1011 0.2954 0.3001 0.3071 0.0623 0.1900 0.1929 0.1950 0.0625 0.0865 0.1362 0.1386 0.1426 0.1408 0.1412

0.0003 0.0002 0.0012 0.0538 0.0601 0.0693 0.0002 0.0150 0.0168 0.0203 0.0007 0.0005 0.0046 0.0058 0.0080 0.0098 0.0139

0.8752 0.8116 0.7189 0.4037 0.3575 0.3098 0.8609 0.5192 0.4785 0.4334 0.8519 0.7425 0.6045 0.5699 0.5206 0.4793 0.4369

Standard uncertainties u are u(w) = 0.0005 and u(T) = 0.1 K.

Table 3. Experimental LLE Data (Mass Fraction) for the Quaternary System Ethanol (1) + Butanol (2) + Nonane (4) + Water (5) at 298.15 K under Atmospheric Pressurea alkane-rich phase

a

water-rich phase

w1

w2

w4

w5

w1

w2

w4

w5

0.0332 0.0307 0.0267 0.0273 0.0901 0.0264 0.0215 0.0194 0.0141 0.0173 0.0554 0.0188 0.0163 0.0130 0.0152 0.0147

0.1183 0.0898 0.0729 0.0616 0.3312 0.0793 0.0548 0.0416 0.0333 0.0272 0.1989 0.0483 0.0338 0.0259 0.0205 0.0170

0.8411 0.8727 0.8953 0.9071 0.5193 0.8903 0.9205 0.9367 0.9508 0.9539 0.7221 0.9305 0.9483 0.9596 0.9630 0.9672

0.0074 0.0068 0.0051 0.0040 0.0594 0.0041 0.0033 0.0023 0.0018 0.0016 0.0235 0.0025 0.0017 0.0015 0.0013 0.0011

0.2251 0.2537 0.2868 0.3134 0.1571 0.2393 0.2731 0.3091 0.3467 0.3842 0.1750 0.2617 0.2927 0.3214 0.3845 0.4138

0.3033 0.3058 0.3132 0.3141 0.0933 0.1888 0.1932 0.1959 0.1974 0.1972 0.1124 0.1393 0.1406 0.1406 0.1471 0.1432

0.0431 0.0420 0.0453 0.0513 0.0004 0.0097 0.0107 0.0117 0.0139 0.0173 0.0014 0.0036 0.0045 0.0051 0.0073 0.0096

0.4286 0.3985 0.3547 0.3213 0.7492 0.5622 0.5230 0.4833 0.4420 0.4013 0.7112 0.5954 0.5623 0.5330 0.4611 0.4334

Standard uncertainties u are u(w) = 0.0005 and u(T) = 0.1 K.

to the vessel at a known ratio by mass. The mixture was stirred intensively at least 1 h by a magnetic stirrer to ensure perfect mixing and then was left not less than 6 h to let the equilibrium established. Then, the phases were sampled from the vessel by a syringe carefully.

The organic components of the sample were analyzed by a gas chromatography (GC-920) equipped with a HT-1 capillary column (50 m × 0.32 mm × 0.5 μm), a flame-ionization detector (FID), and nitrogen as the carrier gas. The temperatures of the injector and the detector were maintained at 553.15K. The colmn temperature was programmed for an 1488

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Table 4. Default and Regressed NRTL Binary Interaction Parameters component i

ethanol

ethanol

ethanol

ethanol

butanol

butanol

butanol

octane

octane

nonane

component j

butanol

octane

nonane

water

octane

nonane

water

nonane

water

water

Aij Aji Bij Bji αij

0 0 363.8936 −851.603 0.3

−0.1431 −1.5735 723.2385 880.9203 0.47

0 0 2494.753 644.7904 0.35

−0.8009 3.4578 129.7941 −932.653 0.3

0 0 −129.684 655.4077 0.3

0 0 −55.1918 593.1893 0.3

−2.0405 13.1102 1200.656 329.6186 0.3

0 0 −68.8427 72.1715 0.3

−12.035 1.2166 4607.237 3560.649 0.2

0 0 1137.279 4363.77 0.2

In the process of data regression, the binary interaction parameters Aij, αij of all components and the Bij of octane and nonane were assigned by the default values in Aspen Plus software for simplifying the calculation process, while Bij of binary systems containing the other components were regressed by the software. The regression method19 used in the Aspen Plus software was based on the maximum likelihood principles. The BrittLuecke algorithm20 was used in the Aspen Plus to obtain the parameters. The default and regressed binary interaction parameters are listed in Table 4. Parity plots of experimental and calculated mass fractions of ethanol, butanol, octane, nonane, and water in the alkane-rich and water-rich phases at equilibrium of the two quaternary systems are presented in Figures 1 and 2. The root-mean-square error (RMSE) and the average absolute deviation (AAD)21 in mass fraction obtained using the NRTL model at 298.15 K of the two quaternary systems are shown in Table 5. The RMSE and AAD are defined as follows:

initial temperature of 333.15 K, held for 3.5 min, rising to 413.15 K at the rate of 20 K per min, and maintained for 2 min. The injection volume was 0.1 μL, and the split ratio was 50:1.

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RESULTS AND DISCUSSION Experimental Data. The experimental tie-line LLE data of the quaternary system ethanol + water + butanol + octane and

RMSE = Figure 1. Experimental and calculated mass fraction of quaternary system ethanol + butanol + octane + water using NRTL: ●, ethanol; △, butanol; ▼, octane; ○, water.

AAD =

1 N

1 N

∑ (wiexp − wical)2 i

∑ |wiexp − wical| i

(1)

(2)

where N is the number of data points and wi is the mass fraction of component i. It is shown in Figures 1 and 2 and Table 5 that the calculated values of NRTL model are in good agreement with the experimental data. Prediction of the Quinary System. The obtained interaction parameters of NRTL model were used to predict the LLE of the quinary system ethanol + butanol + octane + nonane + water and was compared with the experimental values which are listed in Table 6. The accuracy of the prediction was also assessed by the parity plots shown in Figure 3 and RMSE and AAD listed in Table 7. The results showed that the calculated values coincided with the experimental data well, an indication that the NRTL model and the interaction parameters obtained from quaternary systems could be used to predict the LLE data of quinary system. Distribution Coefficient and Selectivity. The LLE data of the quinary system were also characterized by the distribution coefficient (Di) and separation factor or selectivity (Si) which are given by

Figure 2. Experimental and calculated mass fraction of quaternary system ethanol + butanol + nonane + water using NRTL: ●, ethanol; △, butanol; ☆, nonane; ○, water.

ethanol + water + butanol + nonane are shown in Tables 2 and 3. All of the data are expressed in mass fraction. Data Correlation. The nonrandom two-liquid (NRTL) model of Renon and Prausnitz16 was used to correlate the tieline data. The model has been used by Santiago and Aznar17,18 to represent the LLE of several quaternary and quinary systems. The quaternary data were correlated using the Aspen Plus simulator to get the regressed binary interaction parameters of NRTL.

D1 =

D2 = 1489

E wbutanol R wbutanol

(3)

E E woctan e + wnonane R R woctan e + woctan e

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Table 5. RMSE and AAD in Mass Fraction for the Two Quaternary Systems ethanol

butanol

octane

water

phase

RMSE

AAD

RMSE

AAD

RMSE

AAD

RMSE

AAD

alkane-rich water-rich

0.0027 0.0037

0.0022 0.0028

0.0035 0.0211

0.0025 0.0144

0.0039 0.0052

0.0031 0.0024

0.0028 0.0190

0.0021 0.0119

phase

RMSE

AAD

RMSE

AAD

RMSE

AAD

RMSE

AAD

alkane-rich water-rich

0.0119 0.0067

0.0018 0.0049

0.0037 0.0100

0.0028 0.0066

0.0038 0.0078

0.0029 0.0063

0.0023 0.0070

0.0014 0.0055

ethanol

butanol

nonane

water

Table 6. Experimental LLE Data (Mass Fraction) for the Quinary System Ethanol (1) + Butanol (2) + Octane (3) + Nonane (4) + Water (5) at 298.15 K under Atmospheric Pressurea alkane-rich phase

a

water-rich phase

w1

w2

w3

w4

w5

w1

w2

w3

w4

w5

0.0264 0.0237 0.0223 0.0210 0.0248 0.0182 0.0211 0.0193 0.0194 0.0187 0.0195 0.0160 0.0186 0.0194 0.0140 0.0175 0.0180 0.0172 0.0175 0.0173 0.0077 0.0113 0.0151 0.0179 0.0160 0.0186 0.0188 0.0224 0.0220

0.0655 0.0482 0.0380 0.0304 0.0600 0.0400 0.0402 0.0371 0.0354 0.0333 0.0319 0.0287 0.0299 0.0300 0.0260 0.0251 0.0244 0.0225 0.0232 0.0196 0.0041 0.0095 0.0163 0.0234 0.0287 0.0299 0.0351 0.0443 0.0499

0.4470 0.4571 0.4624 0.4636 0.4544 0.4609 0.4661 0.4666 0.4676 0.4699 0.4651 0.4673 0.4673 0.4797 0.4660 0.4744 0.4726 0.4774 0.4719 0.4743 0.4897 0.4877 0.4890 0.4826 0.4673 0.4673 0.4623 0.4532 0.4302

0.4572 0.4683 0.4751 0.4836 0.4574 0.4791 0.4702 0.4752 0.4760 0.4764 0.4817 0.4865 0.4826 0.4700 0.4930 0.4819 0.4838 0.4818 0.4860 0.4878 0.4978 0.4909 0.4790 0.4751 0.4865 0.4826 0.4823 0.4780 0.4947

0.0039 0.0028 0.0022 0.0015 0.0033 0.0018 0.0024 0.0018 0.0017 0.0018 0.0018 0.0015 0.0017 0.0010 0.0010 0.0012 0.0011 0.0011 0.0014 0.0010 0.0007 0.0006 0.0006 0.0009 0.0015 0.0017 0.0014 0.0021 0.0031

0.2793 0.3176 0.3597 0.3944 0.2608 0.2918 0.2981 0.3096 0.3159 0.3212 0.3261 0.3426 0.3355 0.3454 0.3498 0.3601 0.3856 0.3844 0.3761 0.4252 0.3802 0.3651 0.3583 0.3446 0.3426 0.3355 0.3284 0.3190 0.3114

0.1936 0.1957 0.1980 0.1980 0.1379 0.1410 0.1394 0.1424 0.1424 0.1413 0.1405 0.1426 0.1410 0.1416 0.1418 0.1410 0.1488 0.1433 0.1405 0.1440 0.0318 0.0615 0.0896 0.1157 0.1426 0.1410 0.1643 0.1870 0.2080

0.0071 0.0084 0.0099 0.0119 0.0020 0.0030 0.0034 0.0035 0.0035 0.0037 0.0039 0.0040 0.0040 0.0043 0.0043 0.0046 0.0049 0.0055 0.0052 0.0068 0.0004 0.0004 0.0017 0.0023 0.0040 0.0040 0.0055 0.0077 0.0091

0.0055 0.0064 0.0077 0.0092 0.0015 0.0022 0.0032 0.0026 0.0025 0.0028 0.0029 0.0029 0.0030 0.0031 0.0032 0.0034 0.0036 0.0039 0.0039 0.0050 0.0002 0.0004 0.0012 0.0017 0.0029 0.0030 0.0043 0.0062 0.0080

0.5145 0.4719 0.4246 0.3865 0.5978 0.5620 0.5559 0.5419 0.5357 0.5310 0.5265 0.5079 0.5166 0.5055 0.5008 0.4910 0.4571 0.4630 0.4743 0.4190 0.5874 0.5726 0.5492 0.5357 0.5079 0.5166 0.4975 0.4801 0.4636

Standard uncertainties u are u(w) = 0.0005 and u(T) = 0.1 K.

S1/2 =

D1 D2

selectivity of butanol against alkanes (S1/2) increased first and then decreased with the increase of ethanol/(ethanol + water) mass ratio in the initial mixture. When the ethanol/(ethanol + water) mass ratio reached 0.40, the selectivity reached the highest value of 691. Therefore, the ethanol aqueous solution which contained about 40 wt % ethanol was suitable for separating butanol from the butanol−octane−nonane mixture.

(5)

where superscripts E and R refer to the extract (water-rich) phase and to the raffinate (alkane-rich) phase, respectively. The butanol and alkane distribution coefficients versus the ethanol/(ethanol + water) mass ratio in the condition that the mass ratio of (ethanol + water)−butanol−octane−nonane was 12:2:1:1 are shown in Figure 4. It was seen that both the distribution coefficients increased with the increase of ethanol/ (ethanol + water) mass ratio in the initial mixture. The selectivity of butanol against alkanes versus ethanol/ (ethanol + water) mass ratio in the condition that the mass ratio of (ethanol + water)−butanol−octane−nonane was 12:2:1:1 was shown in Figure 5. It was shown that the

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CONCLUSION The LLE experiments for the quaternary systems ethanol + water + butanol + octane and ethanol + water + butanol + nonane were performed for different overall composition at 298.15 K under atmospheric pressure. The quaternary experimental tie-line data were regressed using the NRTL model, and the binary interaction parameters were obtained. 1490

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Figure 4. Mass based distribution coefficients of butanol and alkane versus ethanol/(ethanol + water) mass ratio in the initial mixture: ▼, distribution coefficient of butanol (D1); △, distribution coefficient of alkanes (D2).

Figure 3. Experimental and calculated mass fraction of quinary system ethanol + butanol + octane + nonane + water using NRTL: ●, ethanol; △, butanol; ▼, octane; ☆, nonane; ○, water.

The obtained interaction parameters of the NRTL model were used to predict the LLE of the quinary system ethanol + butanol + octane + nonane + water and were compared with the experimental data. The results showed that the calculated values coincided with the experimental data well, an indication that the interaction parameters obtained from quaternary systems could be used to predict the LLE data of quinary system. The characterization of distribution coefficient and selectivity showed that the ethanol aqueous solution which contained about 40 wt % ethanol was suitable for separating butanol from the butanol−octane−nonane mixture. The successful prediction of the LLE of the quinary system ethanol + butanol + octane + nonane + water was of great significance for the further separation process simulation.

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Figure 5. Selectivity of butanol against alkane (S1/2) versus ethanol/ (ethanol + water) mass ratio in the initial mixture.

AUTHOR INFORMATION

nanotubes supported cobalt catalyst in Fischer−Tropsch synthesis. Appl. Catal., A 2009, 353, 193−202. (6) Ma, W.; Jacobs, G.; Sparks, D. E.; Gnanamani, M. K.; Pendyala, V. R. R.; Yen, C. H.; Klettlinger, J. L. S.; Tomsik, T. M.; Davis, B. H. Fischer−Tropsch synthesis: Support and cobalt cluster size effects on kinetics over Co/Al2O3 and Co/SiO2 catalysts. Fuel 2011, 90, 756− 765. (7) Huffman, G. P. Incorporation of catalytic dehydrogenation into Fischer−Tropsch synthesis of liquid fuels from coal to minimize carbon dioxide emissions. Fuel 2011, 90, 2671−2676. (8) Ishida, T.; Yanagihara, T.; Liu, X.; Ohashi, H.; Hamasaki, A.; Honma, T.; Oji, H.; Yokoyama, T.; Tokunaga, M. Synthesis of higher alcohols by Fischer−Tropsch synthesis over alkali metal-modified cobalt catalysts. Appl. Catal., A 2013, 458, 145−154. (9) Pei, Y.; Jian, S.; Chen, Y.; Wang, C. Synthesis of higher alcohols by the Fischer−Tropsch reaction over activated carbon supported CoCuMn catalysts. RSC Adv. 2015, 5, 76330−76336. (10) Tien-Thao, N.; Zahedi-Niaki, M. H.; Alamdari, H.; Kaliaguine, S. Effect of alkali additives over nanocrystalline Co-Cu-based perovskites as catalysts for higher-alcohol synthesis. J. Catal. 2007, 245, 348−357. (11) Yang, Y.; Wang, L.; Xiao, K.; Zhao, T.; Wang, H.; Zhong, L.; Sun, Y. Elucidation of reaction network of higher alcohol synthesis

Corresponding Author

*E-mail: [email protected]. ORCID

Jiafeng Liu: 0000-0001-6258-7896 Notes

The authors declare no competing financial interest.

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REFERENCES

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Table 7. RMSE and AAD in Mass Fraction for the Quinary System ethanol

butanol

octane

nonane

water

phase

RMSE

AAD

RMSE

AAD

RMSE

AAD

RMSE

AAD

RMSE

AAD

alkane-rich water-rich

0.0024 0.0056

0.0020 0.0048

0.0038 0.0125

0.0036 0.0119

0.0041 0.0010

0.0039 0.0008

0.0037 0.0029

0.0035 0.0026

0.0021 0.0117

0.0020 0.0104

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