甲醇-甲醛-聚甲氧基二甲醚三元体系汽液平衡

doi:10.11949/0438-1157.20190440

摘要/Abstract

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

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

中图分类号:

TQ 031.1

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.

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.

图/表 8

参考文献 30

1	李振光, 袁建团. 中国柴油需求趋势分析[J]. 国际石油经济, 2015, 23(9): 88-93.
	Li Z G, Yuan J G. China s diesel demand[J]. International Petroleum Economics, 2015, 23(9): 88-93.
2	石华. 我国石油对外依存度首破60%[J]. 石油库与加油站, 2016, 25(1): 25.
	Shi H. China s oil external dependence first broke 60%[J]. Oil Depot and Gas Station, 2016, 25(1): 25.
3	焦瑞. 如何认识我国原油对外依存度逐年攀升[J]. 炼油技术与工程, 2017， (4): 45.
	Jiao R. How to understand China s crude oil dependence increasing year by year[J]. Refining Technology and Engineering, 2017, (4): 45.
4	钱伯章. 到2020年柴油需求将超过汽油[J]. 润滑油与燃料, 2014, (z1): 34.
	Qian B Z. Demand for diesel will exceed demand for gasoline by 2020[J]. Lube and Fuel, 2014, (z1): 34.
5	李俊涛. 添加剂对柴油质量影响的研究[D]. 武汉: 武汉工程大学, 2016.
	Li J T. Study on the effect of additives on diesel oil quality[D]. Wuhan: Wuhan Institute of Technology, 2016.
6	王志, 刘浩业, 张俊, 等. 聚甲氧基二甲醚与柴油混合燃料的燃烧与排放特性[J]. 汽车安全与节能学报, 2015, 6(2): 191-197.
	Wang Z, Liu H Y, Zhang J, et al. Combustion and emission characteristics of diesel engines fuelled by polyoxymethylene dimethyl ethers (PODE_n)[J]. Journal of Automotive Safety and Energy, 2015, 6(2): 191-197.
7	Pellegrini L, Marchionna M, Patrini R, et al. Combustion behaviour and emission performance of neat and blended polyoxymethylene dimethyl ethers in a light-duty diesel engine[R]. SAETechnical Paper, 2012.
8	Pellegrini L, Marchionna M, Patrini R, et al. Emission performance of neat and blended polyoxymethylene dimethyl ethers in an old light-duty diesel car[R]. SAETechnical Paper, 2013.
9	张信伟, 李杰, 倪向前, 等. 聚甲氧基二甲醚合成技术的产业化进展[J]. 化工进展, 2016, 35(7): 2293-2298.
	Zhang X W, Li J, Ni X Q, et al. Industrialization progress of polyoxymethylene dimethyl ethers synthesis technology[J]. Chemical Industry and Engineering Progress, 2016, 35(7): 2293-2298.
10	杨丰科, 王俊伟. 柴油添加剂聚甲氧基二甲醚的合成研究进展[J]. 应用化工, 2012, 41(10): 1803-1806.
	Yang F K, Wang J W. Progress on the synthesis of polyoxymethylene dimethyl ethers as component of tailored diesel fuel[J]. Applied Chemical Industry, 2012, 41(10): 1803-1806.
11	史高峰, 陈英赞, 陈学福, 等. 聚甲氧基二甲醚研究进展[J]. 天然气化工, 2012, 37(2): 74-78.
	Shi G F, Chen Y Z, Chen X F, et al. Research progress in polyoxymethylene dimethyl ethers[J]. Natural Gas Chemical Industry, 2012, 37(2): 74-78.
12	张建强, 唐斌, 刘殿华, 等. 聚甲氧基二甲醚合成研究现状[J]. 煤化工, 2013, (1): 41-43.
	Zhang J Q, Tang B, Liu D H, et al. Research progress of polyoxymethylene dimethyl ethers synthesis[J]. Coal Chemical Industry, 2013, (1): 41-43.
13	Burger J, Siegert M, Ströfer E, et al. Poly (oxymethylene) dimethyl ethers as components of tailored diesel fuel: properties, synthesis and purification concepts[J]. Fuel, 2010, 89(11): 3315-3319.
14	Burger J, Ströfer E, Hasse H. Chemical equilibrium and reaction kinetics of the heterogeneously catalyzed formation of poly(oxymethylene) dimethyl ethers from methylal and trioxane[J]. Industrial & Engineering Chemistry Research, 2012, 51(39): 12751-12761.
15	Burger J, Hasse H. Multi-objective optimization using reduced models in conceptual design of a fuel additive production process[J]. Chemical Engineering Science, 2013, 99: 118-126.
16	Burger J, Ströfer E, Hasse H. Production process for diesel fuel components polyoxymethylene dimethyl ethers from methane-based products by hierarchical optimization with varying model depth[J]. Chemical Engineering Research and Design, 2013, 91(12): 2648-2662.
17	孙兰义. 化工过程流程模拟实训: Aspen Plus教程[M]. 北京: 化学工业出版社, 2012.
	Sun L Y. Chemical Process Process Simulation Training: Aspen Plus Tutorial[M]. Beijing: Chemical Industry Press, 2012.
18	张治山, 杨超龙. Aspen Plus在化工中的应用[J]. 广东化工, 2012, 39(3): 77-78.
	Zhang Z S, Yang C L. Application of Aspen Plus in chemical engineering[J]. Guangdong Chemical Industry, 2012, 39(3): 77-78.
19	More R K, Bulasara V K, Uppaluri R, et al. Optimization of crude distillation system using Aspen Plus: effect of binary feed selection on grass-root design[J]. Chemical Engineering Research & Design, 2010, 88(2): 121-134.
20	Ramzan N, Ashraf A, Naveed S, et al. Simulation of hybrid biomass gasification using Aspen plus: a comparative performance analysis for food, municipal solid and poultry waste[J]. Biomass & Bioenergy, 2011, 35(9): 3962-3969.
21	Doherty W, Reynolds A, Kennedy D. Computer simulation of a biomass gasification-solid oxide fuel cell power system using Aspen Plus[J]. Energy, 2010, 35(12): 4545-4555.
22	周怀申, 韩世钧. 一种新的循环法汽液平衡釜——改进的Rose釜[J]. 化学工程, 1980, (5): 23-26.
	Zhou H S, Han S J. A new kind of vapor liquid balance kettle of circulating method — improved Rose kettle[J]. Chemical Engineering(China), 1980, (5): 23-26.
23	朱云庆.醋酸物系相平衡研究[D]. 青岛: 中国石油大学, 2008.
	Zhu Y Q. Study on phase equilibrium of acetic acid[D]. Qingdao: China University of Petroleum, 2008.
24	任海鸥, 周金波, 李长明, 等. 常压下叔丁醇-水-乙二醇体系汽液平衡测定与关联[J]. 化学工程, 2017, 45(9): 35-38.
	Ren H O, Zhou J B, Li C M, et al. Determination and correlation of vapor - liquid equilibrium of tert-butanol - water - glycol system under atmospheric pressure[J]. Chemical Engineering(China), 2017, 45(9): 35-38.
25	周航. 乙醇-丙酸乙酯-对二甲苯等压汽液相平衡研究[D]. 天津: 天津大学, 2017.
	Zhou H. Study on vapor-liquid equilibrium of ethanol-ethyl propionate -p-xylene at constant pressure[D]. Tianjin: Tianjin University, 2017.
26	曹玲, 徐威震, 李学琴, 等. 甲醇+碳酸二甲酯+二乙二醇三元物系等压汽液平衡数据的测定与关联[J]. 石油化工, 2017, 46(9): 74-79.
	Cao L, Xu W Z, Li X Q, et al. Isobaric vapor-liquid equilibrium for methanol+dimethyl carbonate+ diethylene glycol system[J]. Petrochemical Technology, 2017, 46(9): 74-79.
27	Nagahama K. VLE measurements at elevated pressures for process development [J]. Fluid Phase Equilibria, 1996, 116(1): 361-372.
28	Fornari R E, Alessi P, Kikic I. High-pressure fluid-phase equilibria: experimental methods and systems investigated(1978—1987)[J]. Fluid Phase Equilibria, 1990, 57: 1-33.
29	Dohrn R, Brunner G. High-pressure fluid-phase equilibria: experimental methods and systems investigated (1988—1993) [J]. Fluid Phase Equilibria, 1995, 106(1): 213-282.
30	王琦. 双循环加压汽液相平衡装置的建立与校核[J]. 石油学报, 1988, 4(2): 50-56.
	Wang Q. Establishment and verification of double cycle pressurized vapor liquid phase balance device[J]. Acta Petroleum Sinica, 1988, 4(2): 50-56.

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