1-甲基萘-正癸烷-1-十四烯-环丁砜体系液液相平衡数据测定及关联

doi:10.11949/0438-1157.20190608

摘要/Abstract

摘要：

采用溶剂萃取分离催化裂化柴油中的芳烃是催化裂化柴油改质一条有效的途径。测定了常压下323.15、333.15和343.15 K时1-甲基萘-正癸烷-1-十四烯-环丁砜体系的液液相平衡数据，得到该体系的三元相图，1-甲基萘对非芳烃的选择性系数保持在2~55之间，说明环丁砜溶剂萃取分离1-甲基萘是可行的。采用Hand方程和Othmer-Tobias方程对相平衡数据进行关联，相关性系数均大于0.99，表明相平衡数据具有较好的一致性。利用NRTL方程进行关联，获得二元交互作用参数，NRTL模型计算值与实验值的均方根偏差很小，说明NRTL模型适合该体系的液液相平衡。

关键词: 1-甲基萘, 环丁砜, 萃取, 相平衡, 模型

Abstract:

Separation of aromatic hydrocarbons in catalytically cracked diesel by solvent extraction is an effective way to reform catalytic diesel. Liquid-liquid equilibrium data provides basic data and theoretical guidance for the simulation, design and optimization of solvent-extracted aromatics process. The liquid-liquid equilibrium data of 1-methylnaphthalene-n-decane-1-tetradecene-sulfolane system at 323.15, 333.15 and 343.15 K were determined at atmospheric pressure. The ternary phase diagram of this system was obtained. The correlation coefficient of Hand equation and Othmer-Tobias equation was over 0.99, which indicated that the phase equilibrium data have good consistency. The binary interaction parameters were obtained by correlation with NRTL equation, the root mean square deviation between the calculated value and the experimental value was small, indicating that the NRTL model was suitable for the system. The selectivity coefficient of 1-methylnaphthalene to non-aromatic hydrocarbons was maintained between 2 and 55, it showed good separation performance.

Key words: 1-methylnaphthalene, sulfolane, extraction, phase equilibrium, model

中图分类号:

TQ 028.4

丁立群, 袁晓冰, 刘昌见. 1-甲基萘-正癸烷-1-十四烯-环丁砜体系液液相平衡数据测定及关联[J]. 化工学报, 2019, 70(10): 3899-3905.

Liqun DING, Xiaobing YUAN, Changjian LIU. Measurement and correlation of liquid-liquid equilibrium data for 1-methylnaphthalene-n-decane-1-tetradecene-sulfolane system[J]. CIESC Journal, 2019, 70(10): 3899-3905.

图/表 8

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T/K	Extraction phase mass fraction				Raffinate phase mass fraction
T/K	x ₁	x ₂	x ₃	x ₄	x ₁	x ₂	x ₃	x ₄
323.15	0	0.0084	0.0026	0.9890	0.0000	0.7409	0.2490	0.0101
	0.1367	0.0107	0.003	0.8496	0.1584	0.6184	0.2098	0.0134
	0.2311	0.0154	0.0051	0.7490	0.2530	0.5395	0.1885	0.0211
	0.3196	0.0238	0.0075	0.6491	0.3325	0.4763	0.1607	0.0305
	0.3861	0.0309	0.0098	0.5732	0.3961	0.4177	0.1405	0.0457
	0.4191	0.0409	0.0130	0.5270	0.4284	0.3886	0.1311	0.0519
	0.4466	0.0429	0.0139	0.4966	0.4474	0.3694	0.1246	0.0585
	0.4662	0.0549	0.0175	0.4615	0.4710	0.3393	0.1150	0.0747
	0.4905	0.0600	0.0200	0.4294	0.4956	0.3109	0.1048	0.0887
	0.5059	0.0695	0.0229	0.4015	0.5090	0.2915	0.0985	0.1009
	0.5270	0.0935	0.0311	0.3503	0.5318	0.2533	0.0870	0.1279
333.15	0	0.0063	0.0020	0.9916	0.0000	0.7338	0.2545	0.0116
	0.1346	0.0111	0.0032	0.8510	0.1558	0.6076	0.2183	0.0183
	0.2384	0.0194	0.0060	0.7362	0.2598	0.5242	0.1859	0.0301
	0.3229	0.0303	0.0095	0.6373	0.3409	0.4608	0.1591	0.0393
	0.3892	0.0377	0.0122	0.5609	0.4053	0.3973	0.1431	0.0543
	0.4144	0.0409	0.0130	0.5317	0.4295	0.3744	0.1304	0.0657
	0.4414	0.0492	0.0159	0.4934	0.4567	0.3441	0.1212	0.0781
	0.4654	0.0632	0.0200	0.4514	0.4774	0.3166	0.1133	0.0928
	0.4879	0.0676	0.0227	0.4218	0.4974	0.2896	0.1025	0.1104
	0.5052	0.0758	0.0260	0.3929	0.5196	0.2526	0.0917	0.1360
343.15	0	0.0097	0.0032	0.9872	0.0000	0.7169	0.2622	0.0209
	0.1377	0.0152	0.0046	0.8426	0.1571	0.5915	0.2260	0.0254
	0.2380	0.0200	0.0063	0.7357	0.2726	0.5048	0.1903	0.0324
	0.3191	0.0288	0.0086	0.6436	0.3443	0.4390	0.1634	0.0534
	0.3779	0.0426	0.0135	0.5660	0.4066	0.3821	0.1380	0.0733
	0.4141	0.0476	0.0146	0.5237	0.4379	0.3576	0.1286	0.0759
	0.4411	0.0546	0.0176	0.4867	0.4485	0.3397	0.1243	0.0875
	0.4676	0.0647	0.0201	0.4477	0.4890	0.2891	0.1041	0.1178
	0.4853	0.0741	0.0237	0.4169	0.5029	0.2483	0.0887	0.1600

T/K	Extraction phase mass fraction				Raffinate phase mass fraction
T/K	x ₁	x ₂	x ₃	x ₄	x ₁	x ₂	x ₃	x ₄
323.15	0	0.0084	0.0026	0.9890	0.0000	0.7409	0.2490	0.0101
	0.1367	0.0107	0.003	0.8496	0.1584	0.6184	0.2098	0.0134
	0.2311	0.0154	0.0051	0.7490	0.2530	0.5395	0.1885	0.0211
	0.3196	0.0238	0.0075	0.6491	0.3325	0.4763	0.1607	0.0305
	0.3861	0.0309	0.0098	0.5732	0.3961	0.4177	0.1405	0.0457
	0.4191	0.0409	0.0130	0.5270	0.4284	0.3886	0.1311	0.0519
	0.4466	0.0429	0.0139	0.4966	0.4474	0.3694	0.1246	0.0585
	0.4662	0.0549	0.0175	0.4615	0.4710	0.3393	0.1150	0.0747
	0.4905	0.0600	0.0200	0.4294	0.4956	0.3109	0.1048	0.0887
	0.5059	0.0695	0.0229	0.4015	0.5090	0.2915	0.0985	0.1009
	0.5270	0.0935	0.0311	0.3503	0.5318	0.2533	0.0870	0.1279
333.15	0	0.0063	0.0020	0.9916	0.0000	0.7338	0.2545	0.0116
	0.1346	0.0111	0.0032	0.8510	0.1558	0.6076	0.2183	0.0183
	0.2384	0.0194	0.0060	0.7362	0.2598	0.5242	0.1859	0.0301
	0.3229	0.0303	0.0095	0.6373	0.3409	0.4608	0.1591	0.0393
	0.3892	0.0377	0.0122	0.5609	0.4053	0.3973	0.1431	0.0543
	0.4144	0.0409	0.0130	0.5317	0.4295	0.3744	0.1304	0.0657
	0.4414	0.0492	0.0159	0.4934	0.4567	0.3441	0.1212	0.0781
	0.4654	0.0632	0.0200	0.4514	0.4774	0.3166	0.1133	0.0928
	0.4879	0.0676	0.0227	0.4218	0.4974	0.2896	0.1025	0.1104
	0.5052	0.0758	0.0260	0.3929	0.5196	0.2526	0.0917	0.1360
343.15	0	0.0097	0.0032	0.9872	0.0000	0.7169	0.2622	0.0209
	0.1377	0.0152	0.0046	0.8426	0.1571	0.5915	0.2260	0.0254
	0.2380	0.0200	0.0063	0.7357	0.2726	0.5048	0.1903	0.0324
	0.3191	0.0288	0.0086	0.6436	0.3443	0.4390	0.1634	0.0534
	0.3779	0.0426	0.0135	0.5660	0.4066	0.3821	0.1380	0.0733
	0.4141	0.0476	0.0146	0.5237	0.4379	0.3576	0.1286	0.0759
	0.4411	0.0546	0.0176	0.4867	0.4485	0.3397	0.1243	0.0875
	0.4676	0.0647	0.0201	0.4477	0.4890	0.2891	0.1041	0.1178
	0.4853	0.0741	0.0237	0.4169	0.5029	0.2483	0.0887	0.1600

Equation	T/K	a	b	R ²
Hand	323.15	1.0690	-0.0164	0.9988
	333.15	1.0251	-0.0430	0.9972
	343.15	0.9888	-0.0747	0.9950
Othmer-Tobias	323.15	1.0536	-0.0514	0.9986
	333.15	1.0074	-0.1225	0.9952
	343.15	0.9727	-0.1945	0.9962

Equation	T/K	a	b	R ²
Hand	323.15	1.0690	-0.0164	0.9988
	333.15	1.0251	-0.0430	0.9972
	343.15	0.9888	-0.0747	0.9950
Othmer-Tobias	323.15	1.0536	-0.0514	0.9986
	333.15	1.0074	-0.1225	0.9952
	343.15	0.9727	-0.1945	0.9962

T/K	i-j	τ_ij	τ_ji	RMSD/%
323.15	1-2	-1487.6913	-962.7367	1.3078
	1-3	52.7779	325.8851
	1-4	1049.2092	933.2794
	2-3	-463.8312	-830.7214
	2-4	1064.3781	-556.1436
	3-4	228.9103	248.0372
333.15	1-2	1193.3190	907.1869	0.5903
	1-3	786.0292	633.6361
	1-4	1058.4150	1453.7198
	2-3	-390.0223	1123.4691
	2-4	1002.3103	1919.1338
	3-4	307.7043	393.2229
343.15	1-2	735.8845	907.1869	0.8121
	1-3	725.5387	641.2457
	1-4	854.3041	1341.8531
	2-3	-254.5185	1151.4601
	2-4	1050.7952	1790.4588
	3-4	368.0254	448.5593