Measurement and correlation of liquid-liquid equilibrium data for o-cresol-m-xylene-ethylene glycol

doi:10.11949/0438-1157.20200181

Abstract

Abstract:

Ethylene glycol can selectively extract phenols from oils containing aromatic hydrocarbon components. To provide fundamental data to help developing new processes for extracting and separating phenols from coking phenolic oil by ethylene glycol, a simplified design method was adopted due to the complicated components of coking phenolic oil, that was o-cresol and m-xylene chosen as typical substances of phenolic compounds and aromatics based on existing phase equilibrium data, respectively. The ternary liquid-liquid equilibrium data of the o-cresol-m-xylene-ethylene glycol system were measured at 303.15, 313.15 and 323.15 K under atmospheric pressure. The reliability of the liquid-liquid equilibrium data at different temperatures was verified by Othmer-Tobias, Hand as well as Bachman equations. All of squares of correlation coefficients were greater than 0.99, which indicates the reliability of the measured experimental data was good. The experimental data were correlated by both NRTL and UNIQUAC models. The binary interaction energy parameters at different temperatures were obtained by data regression. As a result, the phase equilibrium data were calculated and compared with the experimental data. The root-mean-square deviations (RMSD) were less than 1.8%, indicating that NRTL and UNIQUAC models can successfully describe the phase equilibrium behavior of the system.

Key words: extraction, phase equilibria, o-cresol, ethylene glycol, m-xylene, thermodynamics

摘要：

乙二醇可从含芳烃组分油品中选择性萃取酚类，为支撑焦化含酚油中的酚类化合物萃取分离新工艺开发，针对其组分特点，在现有相平衡数据基础上选定代表物，利用液液平衡釜法测出常压下303.15、313.15和323.15 K时邻甲酚-间二甲苯-乙二醇体系液液相平衡数据，并利用Othmer-Tobias方程、Hand方程、Bachman方程分别进行实验数据可靠性检验，其线性相关系数的平方均大于0.99。同时分别用NRTL和UNIQUAC活度系数模型对实验数据进行关联，回归得到不同温度下的模型参数，模型计算值与实验数据对比后发现其均方根偏差小于1.8%，说明NRTL和UNIQUAC模型均可较好地描述该三元体系相平衡行为。

关键词: 萃取, 相平衡, 邻甲酚, 乙二醇, 间二甲苯, 热力学

CLC Number:

TQ 028.3

Li HE, Xiong ZOU, Haotian YE, Xiangqin LI, Hongguang DONG. Measurement and correlation of liquid-liquid equilibrium data for o-cresol-m-xylene-ethylene glycol[J]. CIESC Journal, 2020, 71(7): 2993-2999.

何莉, 邹雄, 叶昊天, 李香琴, 董宏光. 邻甲酚-间二甲苯-乙二醇液液平衡数据的测定与关联[J]. 化工学报, 2020, 71(7): 2993-2999.

Figures/Tables 8

References 33

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T/K	Raffinate phase			Extraction phase			D	S
T/K	w₁	w₂	w₃	w₁	w₂	w₃	D	S
303.15	0.9852	0.0140	0.0008	0.0241	0.0874	0.8885	6.24	255.21
	0.9473	0.0504	0.0022	0.0548	0.2165	0.7287	4.30	74.26
	0.9175	0.0786	0.0039	0.0862	0.3168	0.5969	4.03	42.90
	0.8903	0.1018	0.0079	0.1129	0.3416	0.5455	3.36	26.46
	0.8574	0.1293	0.0133	0.1468	0.3651	0.4881	2.82	16.49
	0.8272	0.1512	0.0215	0.2005	0.3909	0.4086	2.59	10.67
	0.7614	0.2010	0.0376	0.2888	0.4103	0.3009	2.04	5.38
	0.7143	0.2331	0.0526	0.3399	0.4151	0.2451	1.78	3.74
313.15	0.9752	0.0246	0.0002	0.0315	0.0953	0.8732	3.87	119.93
	0.9315	0.0668	0.0017	0.0607	0.2215	0.7177	3.32	50.89
	0.9095	0.0850	0.0055	0.0994	0.3052	0.5954	3.59	32.85
	0.8763	0.1154	0.0083	0.1176	0.3335	0.5489	2.89	21.53
	0.8473	0.1373	0.0154	0.1509	0.3583	0.4908	2.61	14.65
	0.8120	0.1655	0.0225	0.2127	0.3770	0.4104	2.28	8.70
	0.7386	0.2137	0.0478	0.3019	0.3979	0.3002	1.86	4.56
	0.6991	0.2403	0.0607	0.3514	0.4017	0.2470	1.67	3.33
323.15	0.9689	0.0305	0.0006	0.0324	0.0940	0.8735	3.08	92.16
	0.9168	0.0809	0.0024	0.0640	0.2221	0.7140	2.75	39.33
	0.8785	0.1115	0.0100	0.1069	0.2926	0.6006	2.62	21.57
	0.8493	0.1355	0.0152	0.1255	0.3248	0.5498	2.40	16.22
	0.8172	0.1529	0.0298	0.1606	0.3461	0.4933	2.26	11.52
	0.7755	0.1853	0.0392	0.2255	0.3797	0.3948	2.05	7.05
	0.7202	0.2215	0.0583	0.3071	0.3907	0.3023	1.76	4.14
	0.6782	0.2477	0.0741	0.3592	0.3921	0.2487	1.58	2.99

T/K	Raffinate phase			Extraction phase			D	S
T/K	w₁	w₂	w₃	w₁	w₂	w₃	D	S
303.15	0.9852	0.0140	0.0008	0.0241	0.0874	0.8885	6.24	255.21
	0.9473	0.0504	0.0022	0.0548	0.2165	0.7287	4.30	74.26
	0.9175	0.0786	0.0039	0.0862	0.3168	0.5969	4.03	42.90
	0.8903	0.1018	0.0079	0.1129	0.3416	0.5455	3.36	26.46
	0.8574	0.1293	0.0133	0.1468	0.3651	0.4881	2.82	16.49
	0.8272	0.1512	0.0215	0.2005	0.3909	0.4086	2.59	10.67
	0.7614	0.2010	0.0376	0.2888	0.4103	0.3009	2.04	5.38
	0.7143	0.2331	0.0526	0.3399	0.4151	0.2451	1.78	3.74
313.15	0.9752	0.0246	0.0002	0.0315	0.0953	0.8732	3.87	119.93
	0.9315	0.0668	0.0017	0.0607	0.2215	0.7177	3.32	50.89
	0.9095	0.0850	0.0055	0.0994	0.3052	0.5954	3.59	32.85
	0.8763	0.1154	0.0083	0.1176	0.3335	0.5489	2.89	21.53
	0.8473	0.1373	0.0154	0.1509	0.3583	0.4908	2.61	14.65
	0.8120	0.1655	0.0225	0.2127	0.3770	0.4104	2.28	8.70
	0.7386	0.2137	0.0478	0.3019	0.3979	0.3002	1.86	4.56
	0.6991	0.2403	0.0607	0.3514	0.4017	0.2470	1.67	3.33
323.15	0.9689	0.0305	0.0006	0.0324	0.0940	0.8735	3.08	92.16
	0.9168	0.0809	0.0024	0.0640	0.2221	0.7140	2.75	39.33
	0.8785	0.1115	0.0100	0.1069	0.2926	0.6006	2.62	21.57
	0.8493	0.1355	0.0152	0.1255	0.3248	0.5498	2.40	16.22
	0.8172	0.1529	0.0298	0.1606	0.3461	0.4933	2.26	11.52
	0.7755	0.1853	0.0392	0.2255	0.3797	0.3948	2.05	7.05
	0.7202	0.2215	0.0583	0.3071	0.3907	0.3023	1.76	4.14
	0.6782	0.2477	0.0741	0.3592	0.3921	0.2487	1.58	2.99

T/K	Othmer-Tobias			Hand			Bachman
T/K	A	B	R²	p	q	R²	m	n	R²
303.15	1.9097	0.9707	0.9919	1.4979	0.9023	0.9958	–0.1580	1.1542	0.9991
313.15	1.9441	1.0660	0.9927	1.5678	1.0181	0.9913	–0.1710	1.1587	0.9987
323.15	1.8288	1.1228	0.9909	1.5236	1.0951	0.9983	–0.1928	1.1648	0.9963

T/K	Othmer-Tobias			Hand			Bachman
T/K	A	B	R²	p	q	R²	m	n	R²
303.15	1.9097	0.9707	0.9919	1.4979	0.9023	0.9958	–0.1580	1.1542	0.9991
313.15	1.9441	1.0660	0.9927	1.5678	1.0181	0.9913	–0.1710	1.1587	0.9987
323.15	1.8288	1.1228	0.9909	1.5236	1.0951	0.9983	–0.1928	1.1648	0.9963

T/K	i-j	NRTL			RMSD/%	UNIQUAC		RMSD/%
T/K	i-j	(g_ij-g_ii)/(J·mol^-1)	(g_ji-g_jj)/(J·mol^-1)	α_ij	RMSD/%	(u_ij-u_ii)/(J·mol^-1)	(u_ji-u_jj)/(J·mol^-1)	RMSD/%
303.15	1-2	–1992.11	2130.65	0.3	0.988	–3110.95	1641.63	1.132
	1-3	14801.29	9584.97	0.3		–7382.30	–1093.76
	2-3	–603.83	–3173.88	0.47		1492.72	–1575.74
313.15	1-2	–3591.05	2500.81	0.3	1.150	–2147.94	1278.70	1.031
	1-3	16835.85	9471.36	0.3		–38966.86	–831.95
	2-3	–126.26	–4554.05	0.47		1879.11	–2308.78
323.15	1-2	–3619.17	1718.88	0.3	1.728	–2006.43	1259.56	1.579
	1-3	14632.64	9405.78	0.3		–34919.17	–872.03
	2-3	–306.42	–4220.63	0.47		2038.69	–2885.14