Vapor-liquid equilibrium for methanol-formaldehyde-polyoxymethylene dimethyl ethers ternary system

doi:10.11949/0438-1157.20190440

Abstract

Abstract:

Polyoxymethylene dimethyl ether (PODE_n) is a kind of compound with high oxygen content，which is developing to be a high quality diesel additive in recent years.At a constant pressure of 101.3 kPa, the vapor-liquid equilibrium data of methanol-formaldehyde-PODE₂ ternary system was determined using the improved vapor-liquid equilibrium double cycle Rose kettle.Based on maximum-likelihood method，the measured ternary vapor-liquid equilibrium data were correlated by NRTL, Wilson， and UNIQUAC activity coefficient model with Aspen Plus software.And the corresponding binary interaction parameters and simulated calculation values of the three models are obtained respectively. By comparing the calculation value of three models with experimental value, the average absolute deviation in boiling point and vapor-phase composition were determined，which were less than 1.10 K， 0.0250 and 0.0240， respectively.The correlation results of the three models are applicable to the system, and the obtained binary interaction parameters can be applied to the distillation design of the methanol-formaldehyde-PODE₂ ternary system, laying a data foundation for the industrial separation optimization of the related matter system.

Key words: methanol, formaldehyde, PODE₂, vapor-liquid equilibrium, thermodynamic model

摘要：

聚甲氧基二甲醚(PODE_n)是一种含氧量较高的化合物，近年来更是发展为一种优质的柴油添加剂。在101.3 kPa恒定压力下，使用改进的汽液平衡双循环Rose釜测定了甲醇-甲醛-PODE₂三元体系汽液平衡数据。运用最大似然原理，在Aspen Plus软件中，分别采用NRTL、Wilson以及UNIQUAC三种活度系数模型对测定的三元汽液平衡数据进行回归，分别得到三个模型所对应的二元交互参数以及模拟计算值。通过对比模拟值与实验值，得到温度和气相组成的平均绝对偏差，分别小于1.10 K、0.0250和0.0240。三个模型的关联结果均适用于此体系，得到的二元交互参数能够应用于甲醇-甲醛-PODE₂三元体系的精馏设计，为相关物系的工业分离优化奠定了数据基础。

关键词: 甲醇, 甲醛, PODE₂, 汽液平衡, 热力学模型

CLC Number:

TQ 031.1

Pan LI, Hui KONG, Zhuodong SONG, Zuoyi ZHANG, Yunfang WANG. Vapor-liquid equilibrium for methanol-formaldehyde-polyoxymethylene dimethyl ethers ternary system[J]. CIESC Journal, 2020, 71(S1): 7-14.

李攀, 孔慧, 宋卓栋, 张作毅, 王云芳. 甲醇-甲醛-聚甲氧基二甲醚三元体系汽液平衡[J]. 化工学报, 2020, 71(S1): 7-14.

Figures/Tables 8

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仪器名称	规格型号	生产厂家
改进的Rose釜	玻璃制双循环	北京玻璃仪器加工厂
精密温度计	1/20	北京玻璃研究院
电子分析天平	AL204	METTLER TOLEDO(上海)有限公司
气相色谱仪	安捷伦GC7890A	美国安捷伦
均相反应器	KLJX-12A	烟台科立化工设备有限公司
电压调节器	TDGC₃-500W	上海征西电气科技有限公司
烘箱	DHG-9053A	上海浦东荣丰科学仪器有限公司

仪器名称	规格型号	生产厂家
改进的Rose釜	玻璃制双循环	北京玻璃仪器加工厂
精密温度计	1/20	北京玻璃研究院
电子分析天平	AL204	METTLER TOLEDO(上海)有限公司
气相色谱仪	安捷伦GC7890A	美国安捷伦
均相反应器	KLJX-12A	烟台科立化工设备有限公司
电压调节器	TDGC₃-500W	上海征西电气科技有限公司
烘箱	DHG-9053A	上海浦东荣丰科学仪器有限公司

试剂名称	规格	标牌纯度/%（质量）	生产厂家	GC纯度/%（质量）
甲醇	分析纯	≥99.5	国药集团	99.81
PODE₁	分析纯	≥99.7	国药集团	99.83
PODE₂	—	—	自制	99.49
多聚甲醛	—	—	自制	99.43

试剂名称	规格	标牌纯度/%（质量）	生产厂家	GC纯度/%（质量）
甲醇	分析纯	≥99.5	国药集团	99.81
PODE₁	分析纯	≥99.7	国药集团	99.83
PODE₂	—	—	自制	99.49
多聚甲醛	—	—	自制	99.43

No.	T_exp/K	x_1,exp	x_2,exp	y_1,exp	y_2,exp	T_est/K	y_1,est	y_2,est	ΔT/K	Δy₁	Δy₂
1	368.79	0.0305	0.9441	0.0619	0.9031	368.77	0.0532	0.9171	-0.03	-0.0088	0.0140
2	366.99	0.0425	0.9327	0.0996	0.8694	367.37	0.0778	0.8966	0.38	-0.0219	0.0272
3	365.83	0.0548	0.9200	0.1308	0.8400	366.02	0.1024	0.8739	0.20	-0.0284	0.0339
4	364.33	0.0689	0.9035	0.1623	0.8102	364.92	0.1262	0.8502	0.59	-0.0361	0.0399
5	362.00	0.0846	0.8900	0.2015	0.7748	362.56	0.1673	0.8127	0.56	-0.0342	0.0379
6	360.43	0.0985	0.8746	0.2358	0.7413	361.10	0.1936	0.7857	0.67	-0.0421	0.0444
7	359.54	0.1070	0.8654	0.2543	0.7227	360.21	0.2100	0.7690	0.67	-0.0443	0.0464
8	357.36	0.1350	0.8372	0.2937	0.6846	357.28	0.2683	0.7116	-0.08	-0.0255	0.0269
9	355.44	0.1548	0.8167	0.3330	0.6479	355.22	0.3103	0.6704	-0.22	-0.0226	0.0224
10	352.66	0.1959	0.7752	0.3934	0.5875	351.99	0.3797	0.6004	-0.67	-0.0137	0.0129
11	351.32	0.2143	0.7589	0.4264	0.5567	350.30	0.4164	0.5657	-1.01	-0.0100	0.0090
12	350.62	0.2237	0.7474	0.4416	0.5429	349.71	0.4319	0.5509	-0.91	-0.0097	0.0080
13	350.16	0.2338	0.7373	0.4529	0.5312	349.18	0.4444	0.5381	-0.98	-0.0086	0.0069
14	348.16	0.2699	0.7023	0.4931	0.4925	347.07	0.4945	0.4894	-1.10	0.0014	-0.0030
15	347.44	0.2881	0.6852	0.5087	0.4763	346.30	0.5132	0.4705	-1.14	0.0045	-0.0058
16	346.45	0.3197	0.6542	0.5328	0.4533	345.11	0.5467	0.4381	-1.34	0.0139	-0.0152
17	369.39	0.0279	0.9420	0.0476	0.9003	368.91	0.0439	0.9162	-0.48	-0.0037	0.0160
18	368.79	0.0388	0.9280	0.0657	0.8867	368.37	0.0587	0.9015	-0.42	-0.0070	0.0148
19	367.37	0.0511	0.9110	0.0959	0.8565	367.63	0.0733	0.8839	0.27	-0.0226	0.0273
20	364.11	0.0824	0.8754	0.1618	0.7934	365.28	0.1194	0.8405	1.17	-0.0424	0.0471
21	362.15	0.1054	0.8515	0.2048	0.7549	363.33	0.1585	0.8046	1.17	-0.0463	0.0498
22	359.54	0.1348	0.8219	0.2652	0.7016	360.11	0.2214	0.7476	0.57	-0.0438	0.0460
23	357.24	0.1613	0.7949	0.3156	0.6531	357.62	0.2700	0.6986	0.38	-0.0456	0.0455
24	356.03	0.1815	0.7759	0.3449	0.6257	355.95	0.3084	0.6621	-0.08	-0.0365	0.0365
25	354.74	0.2000	0.7558	0.3694	0.5984	354.66	0.3346	0.6335	-0.08	-0.0349	0.0351
26	353.86	0.2137	0.7419	0.3885	0.5837	353.64	0.3608	0.6094	-0.23	-0.0278	0.0257