Simulation of high pure alcohol preparation by distillation-adsorption-membrane separation coupling process

doi:10.16085/j.issn.1000-6613.2020-0850

Abstract

Abstract:

High pure alcohol is widely used in food, medicine, petrochemical, etc. The common method for the preparation of high concentration of alcohol is alcohol five-column distillation, but the traditional distillation process is often accompanied by high energy consumption and high cost. To solve the above problems, a new distillation-adsorption-membrane separation coupling process was proposed in this study to efficiently obtain high concentration alcohol from ethanol fermentation broth. Aspen Plus process simulation software was used to investigate the distillation-adsorption-membrane separation coupling process, and the sensitivity analysis tool was used to optimize the parameters of the distillation column. The results showed that the mass fraction of ethanol reached 99.2% and the ethanol recovery was 65.6% when the number of trays in the distillation column was 37, the reflux ratio was 9, the feeding position was the 35th tray, the adsorbent was natural zeolite and the membrane was separated by polyvinylidene fluoride pervaporation membrane. Compared with the traditional five-column distillation method, high pure alcohol can be obtained with low energy consumption and equipment cost. Meanwhile, the space utilization rate is also reduced. This study reveals that distillation-adsorption-membrane separation coupling process has a good industrial prospect.

Key words: process simulation, distillation, adsorption, membrane separation, high pure alcohol

摘要：

高纯度酒精广泛应用于食品、医药和石油化工等行业，国内外制备高纯度酒精的常用方法为酒精五塔精馏，但传统酒精精馏工艺往往伴随高能耗与高成本。为了解决上述问题，本文提出一种精馏-吸附-膜分离耦合新工艺，从乙醇发酵液中高效获得高纯度酒精。借助Aspen Plus流程模拟软件对精馏-吸附-膜分离耦合工艺进行研究，并用灵敏度分析工具对其精馏塔部分进行参数优化。结果表明，当精馏塔的塔板数为37、回流比为9、进料位置为第35块塔板、吸附剂采用天然沸石、膜分离用聚偏氟乙烯渗透汽化膜时，乙醇质量分数达到99.2%，乙醇回收率为65.6%。与传统五塔精馏方法相比不仅能获得高纯度酒精，而且能耗与设备成本相对较低，也充分提高了空间利用率，具有很好的工业前景。

关键词: 流程模拟, 精馏, 吸附, 膜分离, 高纯度酒精

CLC Number:

TQ214

LI Chunli, CHENG Yonghui, LI Hao. Simulation of high pure alcohol preparation by distillation-adsorption-membrane separation coupling process[J]. Chemical Industry and Engineering Progress, 2021, 40(3): 1354-1361.

李春利, 程永辉, 李浩. 精馏-吸附-膜分离耦合工艺制备高纯度酒精流程模拟[J]. 化工进展, 2021, 40(3): 1354-1361.

Figures/Tables 14

References 31

1	赵常红. 酒精厂工艺设计中的主要节能措施[J]. 工程技术研究, 2019, 18(4): 228-230.
	ZAHO C H. The main energy saving measures in the process design of distillery [J]. Engineering and Technological Research, 2019, 18(4): 228-230.
2	SHINNOSUKE O, JACEK A K, WILLIAM S J, et al. Ethanol purification with ozonation, activated carbon adsorption, and gas stripping[J].Separation and Purification Technology, 2015, 151(4): 165-171.
3	AZAM M, MOHAMMAD M, RASOOL P, et al. Ethanol purification using polyamide-carbon nanotube composite membranes[J]. Polymer Engineering & Science, 2014, 54(4): 961-968.
4	石会龙, 李成帅, 刘博文, 等. 异丁醇-乙醇-水三元体系精馏分离的模拟与优化[J]. 石油与天然气化工, 2018, 47(3): 44-48.
	SHI H L, LI C S, LIU B W, et al. Simulation and optimization of distillation separation of isobutanol-ethanol-water three-element system[J]. Chemical Engineering of Oil & Gas, 2018, 47(3): 44-48.
5	王洪海, 李春利, 方静. 加盐萃取精馏制取无水乙醇过程的模拟[J]. 石油化工, 2008, 37(3): 852-855.
	WANG H H, LI C L, FANG J. Simulation of salt extractive distillation for preparation of anhydrous ethanol [J]. Petrochemical Technology, 2008, 37(3): 852-855.
6	孙德芳, 邵旻, 周政, 等. 减压精馏法制备无水乙醇的研究[J]. 现代化工, 2010, 30(6): 74-77.
	SUN D F, SHAO M, ZHOU Z, et al. Study on production of anhydrous ethanol from vacuum distillation [J]. Modern Chemical Industry, 2010, 30(6):74-77.
7	YOSHISHIGE H, SYOICHI Y, TAKUYA K, et al. An efficient ethanol concentration process by vapor permeation through asymmetric polyimide membrane[J]. Journal of Membrane Science, 2000(177): 233-239.
8	杨座国, 许振良, 王学军. L-DBTA印迹中空纤维复合膜分离乙醇-水的研究[J]. 高分子材料科学与工程, 2006, 22(6): 220-224.
	YANG Z G, XU Z L, WANG X J. Study on the separation of ethanol/water using L-DBTA molecular imprinted composite membranes [J]. Polymer Materials Science & Engineering, 2006, 22(6): 220-224.
9	Al ASHEH S, BANAT F, Al LAGTAH N. Separation of ethanol water mixtures using mole cular sieves and biobased adsorbents[J].Chemical Engineering Research and Design, 2004, 82(A7): 855-864.
10	CHANG Hua, YUAN Xigang, TIAN Hua, et al. Experimental investigation and modeling of adsorption of water and ethanol on cornmeal in an ethanol water binary vapor system[J]. Chemical Engineering & Technology, 2006, 29(4): 454-461.
11	CHANG Hua, YUAN Xigang, TIAN Hua, et al. Experiment and prediction of breakthrough curves for packed bed adsorption of water vapor on cornmeal[J]. Chemical Engineering and Processing, 2006, 45(9): 747-754.
12	贾宪勇, 汪洋, 王悦伟. Aspen Plus软件在乙醇-水分离塔设计中的应用[J]. 天津化工, 2019, 33(2): 35-39.
	JIA X Y, WANG Y, WANG Y W. Application of Aspen Plus software in the design of ethanol-water separation column [J]. Tianjin Chemical Industry, 2019, 33(2): 35-39.
13	李沫林, 陈砺, 严宗诚. 燃料乙醇脱水工艺的研究与展望[J]. 食品工业科技, 2010, 31(5): 410-413.
	LI M L, CHEN L, YAN Z C. Study and prospect of dehydration processing of fuel ethanol [J]. Science and Technology of Food Industry, 2010, 31(5): 410-413.
14	邵昌哲, 陈钢, 侯仲轲. 含异戊醇、乙醇废水的精馏分离模拟分析[J]. 精细化工中间体, 2017, 47(6): 33-36, 69.
	SHAO C Z, CHEN G, HOU Z K. Simulation analysis of distillation for the separation of wastewater containing isoamyl alcohol and ethanol[J]. Fine Chemical Intermediates, 2017, 47(6): 33-36, 69.
15	石永胜, 王永飞, 杜娟. 精馏法处理高浓度有机废水研究进展[J]. 化工管理, 2015, 25: 212-213.
	SHI Y S, WANG Y F, DU J. Research progress of ordinary distillation treatment on high concentration organic wastewater[J]. Chemical Enterprise Management, 2015, 25: 212-213.
16	ROXANA A M, MICHAEL R D, MCELROY C R, et al. The role of surface functionality of sustainable mesoporous materials Starbon^® on the adsorption of toxic ammonia and sulphur gasses[J]. Sustainable Chemistry and Pharmacy, 2020(15): 1-9.
17	田俊英. 溶度积驱动循环模板法制备氧化铝空心球及其吸附性能[D]. 大连: 大连理工大学, 2018.
	TIAN J Y. Solubility product driven preparation of Al₂O₃ hollow microspheres base on recyclable template and their adsorption performances[D]. Dalian: Dalian University of Technology, 2018.
18	范方舟. 化学-生物氧化组合方法处理纤维素乙醇废水的研究[D]. 天津: 天津大学, 2016.
	FAN F Z. Chemical-biological oxidation process for treating cellulosic ethanol production wastewater[D]. Tianjin: Tianjin University, 2016.
19	刘帅. PDMS/PVDF复合膜制备及渗透蒸发分离水中酚的研究[D]. 哈尔滨: 哈尔滨工业大学, 2017.
	LIU S. Research on preparation of PDMS/PVDF composite membrane and pervaporation separation properties for phenol water[D]. Harbin: Harbin Institute of Technology, 2017.
20	张浅, 朱华旭, 唐志书, 等. 基于蒸气渗透膜技术的中药连翘含油水体中挥发油分离工艺研究[J]. 中国中药杂志, 2018, 43(8): 1642-1648.
	ZAHNG Q, ZHU H X, TANG Z S, et al. Study on essential oil separation from Forsythia suspensa oil-bearing water body based on vapor permeation membrane separation technology[J]. China Journal of Chinese Materia Medic, 2018, 43(8): 1642-1648.
21	BOTOND S, TRANG D T H, DANIEL F, et al. Modelling of hybrid method for VOC removal from process wastewater: distillation and hydrophilic pervaporation[J]. Periodica Polytechnica Chemical Engineering, 2020, 64(3): 364-370.
22	崔永芳, 凌德生, 赵蕴慧, 等. 用PVA/PAN复合膜分离乙醇水溶液[J]. 水处理技术, 1993, 19(5): 21-26.
	CUI Y F, LING D S, ZHAO Y H, et al. Aqueous ethanol was separated by PVA/PAN membrane [J]. Technology of Water Treatment, 1993, 19(5): 21-26.
23	孙兰义. 化工流程模拟实训: Aspen Plus[M]. 北京: 化学工业出版社, 2012: 181-300.
	SUN L Y. Chemical engineering process simulation using Aspen Plus[M]. Beijing: Chemical Industry Press, 2012: 181-300.
24	解娅男, 李复. 基于Aspen Plus的酸水汽提模拟[J]. 计算机与现代化, 2019(12): 78-82, 87.
	XIE Y N, LI F. Simulation of acid water extraction based on Aspen Plus [J]. Computer and Modernization, 2019(12): 78-82, 87.
25	甄宝勤. 吸附法脱除食用酒精中的甲醇和水分研究[J]. 化工时刊, 2004, 18(10): 50-51.
	ZHEN B Q. Study on removing methanol and water from edible alcohol with absorbent[J]. Chemical Industry Times, 2004, 18(10): 50-51.
26	中国科学院广州化学研究所. 用聚偏氟乙烯渗透汽化膜分离乙醇水溶液的方法: CN 99116274.9[P]. 1999-12-22.
	Guangzhou Institute of Chemistry, Chinese Academy of Sciences. Separation of aqueous ethanol solution by pervaporation membrane of polyvinylidene fluoride: CN 99116274.9[P]. 1999-12-22.
27	唐俏瑜, 王莉, 展侠, 等. 高选择性PDMS/PVDF复合膜渗透汽化分离乙醇/水混合物[J]. 膜科学与技术, 2011, 31(6): 1-5.
	TANG Q Y, WANG L, ZHAN X, et al. Highly selective PDMS/PVDF composite membrane pervaporation separation of ethanol/water mixture[J]. Membrane Science and Technology, 2011, 31(6): 1-5.
28	SHI T, CHUN W, YANG A, et al. Optimization and control of energy saving side-stream extractive distillation with heat integration for separating ethyl acetate-ethanol azeotrope[J]. Chemical Engineering Science, 2020, 215: 1-18.
29	YANG A, SUN S R, SHI T, et al. Energy-efficient extractive pressure-swing distillation for separating binary minimum azeotropic mixture dimethyl carbonate and ethanol[J]. Separation and Purification Technology, 2019, 229: 1-11.
30	李洪亮, 王战辉, 姚银娇. 膜分离法回收不凝气中乙醇/水蒸气的实验研究[J]. 郑州大学学报(工学版), 2012, 33(3): 91-94.
	LI H L, WANG Z H, YAO Y J. Experimental study on recovery of ethanol/vapour from non-condensable gas by membrane separation [J]. Journal of Zhengzhou University (Engineering Science), 2012, 33(3): 91-94.
31	VANKELECOM I F J, DEPRE D, BEUKELAER S D, et al. Influence of zeolites in PDMS membranes: pervaporation of water/alcohol mixtures[J]. The Journal of Chemical Physics, 1995, 99(35): 13193-13197.

组成	质量分数/%	密度/g·cm^-3	沸点/℃
水	89.70	1.00	100
乙醇	10.00	0.789	78.3
甲醇	0.10	0.792	64.7
乙酸乙酯	0.05	0.902	77
正丙醇	0.03	0.803	97.1
异丁醇	0.02	0.81	107.9
异戊醇	0.06	0.81	132.5
乙酸	0.02	1.05	117.9
辛酸	0.01	0.91	237
己酸	0.01	0.93	205.4

组成	质量分数/%	密度/g·cm^-3	沸点/℃
水	89.70	1.00	100
乙醇	10.00	0.789	78.3
甲醇	0.10	0.792	64.7
乙酸乙酯	0.05	0.902	77
正丙醇	0.03	0.803	97.1
异丁醇	0.02	0.81	107.9
异戊醇	0.06	0.81	132.5
乙酸	0.02	1.05	117.9
辛酸	0.01	0.91	237
己酸	0.01	0.93	205.4

项目	T1 (粗馏塔)	T2 (水洗塔)	T3 (精馏塔)	T4 (脱甲醇塔)	T5 (回收塔)
塔板数	25	50	67	51	50
进料位置	18	28	50	26	43
塔压降/kPa	13	20	60	30	30
加热模式	再沸器	直接蒸汽	直接蒸汽	再沸器	直接蒸汽
再沸比	0.385	0.134	0.521	0.400	1.090

项目	T1 (粗馏塔)	T2 (水洗塔)	T3 (精馏塔)	T4 (脱甲醇塔)	T5 (回收塔)
塔板数	25	50	67	51	50
进料位置	18	28	50	26	43
塔压降/kPa	13	20	60	30	30
加热模式	再沸器	直接蒸汽	直接蒸汽	再沸器	直接蒸汽
再沸比	0.385	0.134	0.521	0.400	1.090

精馏-吸附-膜分离耦合工艺	五塔精馏工艺
质量分数
水 0.22%	水 16.42%
乙醇 99.2%	乙醇 83.4%
甲醇 0.03%	甲醇 0.075%
乙酸乙酯 0.054%	乙酸乙酯 0
正丙醇 0	正丙醇 0.004%
异丁醇 0	异丁醇 0.0027%
乙酸 0	乙酸 0.007%
辛酸 0	辛酸 4.74×10^-8
己酸 0	己酸 1.88×10^-8
异戊醇 0	异戊醇 0.0081%
流量 132.254kg/h	流量 148.5kg/h