LIQUID-LIQUID EQUILIBRIUM AND KINETICS OF ETHANOLIC EXTRACTION OF SOYBEAN OIL USING ETHYL ACETATE AS CO-SOLVENT

Dagostin, João L. A.; Carpiné, Danielle; Santos, Paulo R. S. dos; Corazza, Marcos L.

doi:10.1590/0104-6632.20180352s20160175

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Brazilian Journal of Chemical Engineering

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CBTermo-2015 • Braz. J. Chem. Eng. 35 (2) • Apr-Jun 2018 • https://doi.org/10.1590/0104-6632.20180352s20160175 copy

LIQUID-LIQUID EQUILIBRIUM AND KINETICS OF ETHANOLIC EXTRACTION OF SOYBEAN OIL USING ETHYL ACETATE AS CO-SOLVENT

Authorship SCIMAGO INSTITUTIONS RANKINGS

Abstract

This work reports a new set of experimental data for the liquid-liquid equilibrium (LLE) of the system (soybean oil + ethyl acetate + anhydrous ethanol) and the kinetics of crude oil extraction from soybean flakes using anhydrous ethanol + ethyl acetate mixtures. Data for the LLE binodal were measured at 298.15, 313.15 and 333.15K by the cloud point method and tie-lines were obtained at 298.15 and 313.15 K. LLE data were successfully modeled using the NRTL model. Batch extractions were performed at 298.15, 313.15 and 328.15 K at a fixed (4:1) solvent to soybean flake mass ratio and two concentration of ethyl acetate (5% and 10%) in ethanol. Higher temperatures increased the solubility of the system and improved the extraction yields. In addition, higher ethyl acetate ratios in anhydrous ethanol led to an increase in the total amount of crude oil extracted when operating at 298.15 and 313.15 K. At 328.15 K, no improvement in extractions was verified when 5% and 10% of ethyl acetate were used in the ethanol. A mass transfer model based on Fick’s Law was applied to describe the extraction kinetics, presenting an average relative deviation of ± 5.11%, in terms of extraction yield.

Keywords:
Liquid-liquid equilibrium; extraction; kinetics; soybean oil; ethanol

298.15 K			313.15 K			333.15 K
w₁	w₂	w₃	w₁	w₂	w₃	w₁	w₂	w₃
0.0495	0.0000	0.9505	0.0796	0.0000	0.9204	0.1951	0.0000	0.8049
0.0738	0.0787	0.8475	0.1007	0.0385	0.8608	0.2104	0.0061	0.7836
0.1020	0.1146	0.7834	0.1137	0.0573	0.8290	0.2250	0.0116	0.7635
0.1228	0.1322	0.7450	0.1290	0.0720	0.7989	0.2434	0.0162	0.7404
0.1495	0.1508	0.6997	0.1516	0.0881	0.7602	0.2662	0.0194	0.7144
0.1764	0.1642	0.6594	0.1822	0.1039	0.7139	0.3021	0.0222	0.6757
0.2088	0.1740	0.6172	0.2024	0.1097	0.6878	0.4023	0.0233	0.5744
0.2357	0.1775	0.5867	0.2165	0.1126	0.6709	0.4550	0.0187	0.5263
0.2689	0.1784	0.5527	0.2557	0.1181	0.6262	0.4947	0.0173	0.4881
0.3046	0.1764	0.5190	0.2901	0.1193	0.5906	0.5136	0.0147	0.4718
0.3355	0.1734	0.4911	0.3271	0.1172	0.5557	0.5539	0.0107	0.4354
0.3582	0.1706	0.4713	0.3578	0.1148	0.5274	0.5776	0.0072	0.4151
0.3960	0.1674	0.4366	0.3905	0.1118	0.4976	0.5963	0.0043	0.3994
0.4213	0.1659	0.4128	0.4171	0.1101	0.4727	0.6205	0.0000	0.3795
0.4420	0.1630	0.3950	0.4664	0.1036	0.4299
0.4642	0.1593	0.3764	0.4944	0.0999	0.4057
0.4976	0.1534	0.3490	0.5229	0.0961	0.3810
0.5223	0.1482	0.3295	0.5486	0.0911	0.3603
0.5573	0.1396	0.3031	0.5887	0.0820	0.3293
0.6008	0.1266	0.2725	0.6238	0.0719	0.3043
0.6439	0.1118	0.2443	0.6568	0.0618	0.2814
0.6924	0.0924	0.2152	0.6902	0.0503	0.2595
0.7355	0.0731	0.1914	0.7227	0.0369	0.2404
0.7867	0.0477	0.1655	0.7542	0.0240	0.2218
0.8243	0.0284	0.1473	0.7756	0.0153	0.2091
0.8740	0.0000	0.1260	0.8040	0.0000	0.1960

Ethanol rich phase (I)			Oil rich phase (II)
w₁	w₂	w₃	w₁	w₂	w₃
*T = 298.15 K*
0.0761	0.0570	0.8669	0.8078	0.0118	0.1805
0.1025	0.0900	0.8075	0.7583	0.0442	0.1975
0.1036	0.0929	0.8035	0.7452	0.0531	0.2017
0.1372	0.1334	0.7295	0.6813	0.0865	0.2322
0.1923	0.1590	0.6487	0.6124	0.1142	0.2734
*T = 313.15 K*
0.1267	0.0436	0.8297	0.7345	0.0183	0.2473
0.1658	0.0867	0.7475	0.6611	0.0488	0.2902
0.2259	0.1177	0.6564	0.5708	0.0777	0.3515

i-j	A_ij / K	A_ji / K	B_ij	B_ji	a _ij
1-2	-303.67	210.10	-412.58	359.70	0.2
1-3^* * Values used from Dagostin et al. (2015a)	3774.80	44.50	-1289.43	491.26	0.4544
2-3	1087.68	-137.62	-595.93	206.80	0.2
RMSDx100	0.097

T (K)	Solvent	^a a C∞ is the equilibrium concentration. , ^b b goil and gs correspond to the units (grams) of crude soybean oil and soybean flakes, respectively. (g_oil g_s^-1)	k^c c parameter k for MTKM corresponds to D/L2from Equation (7), for L = 0.110 mm. (min^-1)	R²	AARD (%)	RMSE^b b goil and gs correspond to the units (grams) of crude soybean oil and soybean flakes, respectively. (g_oil g_s^-1)
298.15	EtOH^d d Dagostin et al. (2015b).	0.1491 ± 0.0014	0.0745 ± 0.0037	0.9827	3.13	0.005
	Et5A	0.1822 ± 0.0030	0.0403 ± 0.0031	0.9743	5.36	0.007
	Et10A	0.2105 ± 0.0041	0.0345 ± 0.0030	0.9678	7.11	0.010
313.15	EtOH^d	0.2142 ± 0.0021	0.0495 ± 0.0023	0.9801	4.50	0.008
	Et5A	0.2374 ± 0.0025	0.0433 ± 0.0023	0.9864	3.72	0.007
	Et10A	0.2410 ± 0.0064	0.0520 ± 0.0070	0.9593	7.36	0.012
328.15	EtOH^d d Dagostin et al. (2015b).	0.2505 ± 0.0025	0.0633 ± 0.0035	0.9659	4.63	0.011
	Et5A	0.2440 ± 0.0038	0.0999 ± 0.0084	0.9666	4.83	0.010
	Et10A	0.2459 ± 0.0043	0.1202 ± 0.0126	0.9278	5.38	0.013

Solvent	Temperature (K)	K	ΔHº (kJ mol^-1)	ΔSº (J mol^-1K^-1)	ΔGº (kJ mol^-1)	R²
EtOH	298.15	1.40	95.01 ± 16.92	320.02 ± 54.14	-0.41	0.969
	313.15	5.15			-5.21
	328.15	47.26			-11.61
Et5A	298.15	2.48	58.02 ± 16.86	203.56 ± 53.95	-2.67	0.922
	313.15	12.90			-5.72
	328.15	20.68			-9.79
Et10A	298.15	4.65	45.78 ± 11.75	167.30 ± 37.63	-4.10	0.938
	313.15	16.28			-6.61
	328.15	24.84			-9.96

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[1] *Corresponding author: Dr. Marcos L. Corazza, Department of Chemical Engineering, Federal University of Paraná, PO Box 19011 Polytechnic Center, Curitiba 81531-980, PR, Brazil. Email: corazza@ufpr.br; Telephone: + 55-41-33613190