Determination and correlation of vapor-liquid equilibrium for polyoxymethylene dimethyl ether system

doi:10.11949/0438-1157.20191346

Abstract

Abstract:

The vapor-liquid equilibrium data of the PODE₂-PODE₃ binary system was determined by the modified Rose vapor-liquid equilibrium reactor under normal pressure conditions. The thermodynamic consistency test was carried out on the measured experimental data, and the results showed that the measured vapor-liquid equilibrium could pass the thermodynamic consistency test. The Aspen Plus v8.8 simulation software was used to correlate the NRTL, Wilson, and UNIQUAC activity coefficient models respectively, and the corresponding binary interaction parameters are obtained through regression. By comparison, the average absolute deviations of the temperature and vapor phase composition between the fitted and experimental values are not more than 0.37 K and 0.0044, respectively, indicating that the fitted results of the three models are in good agreement with the experimental data, and the deviations are all within a reasonable range. This work adds basic data for distillation to the chemical database, and also lays the foundation for further research on distillation design and engineering design with PODE₂ and PODE₃ systems.

Key words: vapor-liquid equilibrium, rectification data, polyoxymethylene dimethyl ether, diesel addictive, correlation

摘要：

通过改进的Rose汽液平衡釜在常压条件下测定了PODE₂-PODE₃二元体系的汽液平衡数据，对所测得的实验数据进行热力学一致性检验，结果表明所测汽液平衡可通过热力学一致性检验。使用Aspen Plus v8.8 模拟软件，分别对NRTL、Wilson、UNIQUAC活度系数模型进行关联，通过回归得到对应的二元交互作用参数，并将三种模型拟合所得到的汽液平衡数据与实验所得的数据相对比，得到拟合值与实验值的温度和气相组成的平均绝对偏差均不大于0.37 K和0.0044，表明3种模型的拟合结果与实验数据吻合均较好，偏差均在合理范围内。这些工作为化工数据库增添了精馏的基础数据，也为含PODE₂和PODE₃体系的精馏设计与工程设计的进一步深入研究奠定了基础。

关键词: 汽液平衡, 精馏数据, 聚甲醛二甲醚, 柴油添加剂, 关联

CLC Number:

O 642.42

Zhuodong SONG, Zuoyi ZHANG, Xuelong PAN, Yunfang WANG. Determination and correlation of vapor-liquid equilibrium for polyoxymethylene dimethyl ether system[J]. CIESC Journal, 2020, 71(S1): 1-6.

宋卓栋, 张作毅, 潘学龙, 王云芳. 聚甲醛二甲醚体系汽液平衡数据的测定与关联[J]. 化工学报, 2020, 71(S1): 1-6.

Figures/Tables 5

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色谱条件	操作参数	色谱条件	操作参数
检测器	氢离子火焰检测器	分流比	150∶1
色谱柱型号	PONA(30 m×0.32 mm×0.5 μm)	氮气流速/(ml/min)	25
柱温	初始温度60℃，保持1 min，然后以10℃/min的速率升温到220℃，保持5 min	氢气流速/(ml/min) 空气流速/(ml/min)	25 250
进样口温度/℃	200	进样量/μl	0.2
检测器温度/℃	220

色谱条件	操作参数	色谱条件	操作参数
检测器	氢离子火焰检测器	分流比	150∶1
色谱柱型号	PONA(30 m×0.32 mm×0.5 μm)	氮气流速/(ml/min)	25
柱温	初始温度60℃，保持1 min，然后以10℃/min的速率升温到220℃，保持5 min	氢气流速/(ml/min) 空气流速/(ml/min)	25 250
进样口温度/℃	200	进样量/μl	0.2
检测器温度/℃	220

序号	T_exp/K	x_1,exp	y_1,exp	γ₁	γ₂	NRTL		Wilson		UNIQUAC
序号	T_exp/K	x_1,exp	y_1,exp	γ₁	γ₂	ΔT^①/K	Δy₁^②	ΔT^①/K	Δy₁^②	ΔT^①/K	Δy₁^②
1	429.05	0.0000	0.0000	1.0906	1.0000	0.00	0.0000	0.00	0.0000	0.00	0.0000
2	422.62	0.0640	0.2322	1.0865	1.0000	0.56	0.0021	0.56	0.0021	0.53	0.0027
3	417.89	0.1064	0.3555	1.0840	1.0000	0.30	0.0027	0.31	0.0031	0.28	0.0024
4	414.03	0.1481	0.4377	1.0817	1.0001	0.51	0.0106	0.54	0.0098	0.51	0.0105
5	413.02	0.1699	0.4811	1.0806	1.0002	0.17	0.0099	0.13	0.0090	0.15	0.0097
6	409.12	0.2139	0.5566	1.0782	1.0003	0.31	0.0102	0.37	0.0090	0.35	0.0096
7	406.46	0.2558	0.6179	1.0760	1.0004	0.08	0.0086	0.15	0.0073	0.13	0.0080
8	403.55	0.2879	0.6634	1.0742	1.0005	0.78	0.0032	0.87	0.0019	0.84	0.0026
9	402.71	0.3077	0.6873	1.0730	1.0006	0.45	0.0010	0.53	0.0001	0.51	0.0005
10	401.46	0.3404	0.7095	1.0711	1.0008	0.14	0.0112	0.05	0.0101	0.07	0.0108
11	399.20	0.3704	0.7393	1.0692	1.0012	0.37	0.0087	0.46	0.0078	0.44	0.0085
12	395.79	0.4468	0.7991	1.0638	1.0018	0.02	0.0056	0.05	0.0053	0.03	0.0060
13	393.77	0.4894	0.8271	1.0603	1.0042	0.05	0.0037	0.10	0.0037	0.08	0.0044
14	392.58	0.5185	0.8439	1.0577	1.0064	0.00	0.0028	0.03	0.0030	0.01	0.0037
15	390.09	0.5745	0.8682	1.0522	1.0084	0.24	0.0055	0.24	0.0061	0.22	0.0067
16	388.13	0.6296	0.8966	1.0461	1.0138	0.21	0.0056	0.17	0.0065	0.15	0.0071
17	386.85	0.6596	0.9022	1.0424	1.0219	0.45	0.0053	0.39	0.0064	0.38	0.0069
18	385.36	0.7021	0.9244	1.0369	1.0280	0.55	0.0024	0.47	0.0013	0.46	0.0008
19	384.33	0.7407	0.9360	1.0315	1.0526	0.43	0.0021	0.34	0.0010	0.33	0.0006
20	382.64	0.7871	0.9504	1.0247	1.0748	0.77	0.0032	0.66	0.0023	0.66	0.0020
21	382.09	0.8148	0.9571	1.0205	1.0922	0.59	0.0025	0.48	0.0018	0.49	0.0015
22	380.78	0.8513	0.9670	1.0150	1.1215	0.91	0.0030	0.81	0.0025	0.82	0.0024
23	380.02	0.8859	0.9755	1.0100	1.1582	0.80	0.0030	0.72	0.0028	0.73	0.0027
24	379.13	0.9229	0.9859	1.0053	1.2111	0.78	0.0044	0.72	0.0045	0.73	0.0044
25	378.64	0.9674	0.9922	1.0011	1.3022	0.27	0.0001	0.24	0.0004	0.25	0.0003
26	378.48	0.9781	0.9942	1.0005	1.3304	0.18	0.0004	0.17	0.0002	0.17	0.0003
27	378.15	1.0000	1.0000	1.0000	1.4003	0.00	0.0000	0.00	0.0000	0.00	0.0000
最大绝对偏差						0.91	0.0112	0.87	0.0101	0.84	0.0108
平均绝对偏差						0.37	0.0044	0.35	0.0040	0.35	0.0043

序号	T_exp/K	x_1,exp	y_1,exp	γ₁	γ₂	NRTL		Wilson		UNIQUAC
序号	T_exp/K	x_1,exp	y_1,exp	γ₁	γ₂	ΔT^①/K	Δy₁^②	ΔT^①/K	Δy₁^②	ΔT^①/K	Δy₁^②
1	429.05	0.0000	0.0000	1.0906	1.0000	0.00	0.0000	0.00	0.0000	0.00	0.0000
2	422.62	0.0640	0.2322	1.0865	1.0000	0.56	0.0021	0.56	0.0021	0.53	0.0027
3	417.89	0.1064	0.3555	1.0840	1.0000	0.30	0.0027	0.31	0.0031	0.28	0.0024
4	414.03	0.1481	0.4377	1.0817	1.0001	0.51	0.0106	0.54	0.0098	0.51	0.0105
5	413.02	0.1699	0.4811	1.0806	1.0002	0.17	0.0099	0.13	0.0090	0.15	0.0097
6	409.12	0.2139	0.5566	1.0782	1.0003	0.31	0.0102	0.37	0.0090	0.35	0.0096
7	406.46	0.2558	0.6179	1.0760	1.0004	0.08	0.0086	0.15	0.0073	0.13	0.0080
8	403.55	0.2879	0.6634	1.0742	1.0005	0.78	0.0032	0.87	0.0019	0.84	0.0026
9	402.71	0.3077	0.6873	1.0730	1.0006	0.45	0.0010	0.53	0.0001	0.51	0.0005
10	401.46	0.3404	0.7095	1.0711	1.0008	0.14	0.0112	0.05	0.0101	0.07	0.0108
11	399.20	0.3704	0.7393	1.0692	1.0012	0.37	0.0087	0.46	0.0078	0.44	0.0085
12	395.79	0.4468	0.7991	1.0638	1.0018	0.02	0.0056	0.05	0.0053	0.03	0.0060
13	393.77	0.4894	0.8271	1.0603	1.0042	0.05	0.0037	0.10	0.0037	0.08	0.0044
14	392.58	0.5185	0.8439	1.0577	1.0064	0.00	0.0028	0.03	0.0030	0.01	0.0037
15	390.09	0.5745	0.8682	1.0522	1.0084	0.24	0.0055	0.24	0.0061	0.22	0.0067
16	388.13	0.6296	0.8966	1.0461	1.0138	0.21	0.0056	0.17	0.0065	0.15	0.0071
17	386.85	0.6596	0.9022	1.0424	1.0219	0.45	0.0053	0.39	0.0064	0.38	0.0069
18	385.36	0.7021	0.9244	1.0369	1.0280	0.55	0.0024	0.47	0.0013	0.46	0.0008
19	384.33	0.7407	0.9360	1.0315	1.0526	0.43	0.0021	0.34	0.0010	0.33	0.0006
20	382.64	0.7871	0.9504	1.0247	1.0748	0.77	0.0032	0.66	0.0023	0.66	0.0020
21	382.09	0.8148	0.9571	1.0205	1.0922	0.59	0.0025	0.48	0.0018	0.49	0.0015
22	380.78	0.8513	0.9670	1.0150	1.1215	0.91	0.0030	0.81	0.0025	0.82	0.0024
23	380.02	0.8859	0.9755	1.0100	1.1582	0.80	0.0030	0.72	0.0028	0.73	0.0027
24	379.13	0.9229	0.9859	1.0053	1.2111	0.78	0.0044	0.72	0.0045	0.73	0.0044
25	378.64	0.9674	0.9922	1.0011	1.3022	0.27	0.0001	0.24	0.0004	0.25	0.0003
26	378.48	0.9781	0.9942	1.0005	1.3304	0.18	0.0004	0.17	0.0002	0.17	0.0003
27	378.15	1.0000	1.0000	1.0000	1.4003	0.00	0.0000	0.00	0.0000	0.00	0.0000
最大绝对偏差						0.91	0.0112	0.87	0.0101	0.84	0.0108
平均绝对偏差						0.37	0.0044	0.35	0.0040	0.35	0.0043

物质	A	B	C	D	E	F	T_min/K	T_max/K
PODE₂	19.28571	2124.74	104.2	0	0	0	310.00	380.00
PODE₃	75.1949	8042.31	46.13	7.41	0	0	313.83	429.05