蒸汽渗透技术在燃料乙醇生产中的应用研究进展

doi:10.16085/j.issn.1000-6613.2019-1458

摘要/Abstract

摘要：

蒸汽渗透作为一种新型膜分离技术，可有效解决生物燃料乙醇生产中发酵产物浓度低、能源消耗量大、污染环境等诸多瓶颈问题。与渗透蒸发相比，蒸汽渗透技术具有分离性能好、进料清洁、能量损耗低、操作弹性大等优点，在燃料乙醇生产领域具备更广阔的应用前景。本文在比较渗透蒸发和气体分离技术的基础上，简述了蒸汽渗透过程的机理和特点。介绍了优先透水膜和优先透醇膜两类应用于燃料乙醇生产不同阶段的蒸汽渗透膜和这两类膜材料当前的研究进展，重点阐述了有机/无机杂化膜在成膜方法、杂化材料选择等方面的最新成果。回顾了蒸汽渗透在乙醇脱水方面的工业应用成果，指出该技术在发酵原位分离乙醇和替代精馏工艺方面所具有的优势，探讨了与固态发酵技术相结合进行一次相变生产燃料乙醇工艺实现的可能性，并提出未来亟待研究和解决的问题，为蒸汽渗透技术在燃料乙醇生产领域大规模发展提供参考。

关键词: 蒸汽渗透, 渗透蒸发, 生物燃料, 乙醇, 膜, 固态发酵

Abstract:

As an emerging membrane separation technology, vapor permeation could effectively resolve the bottlenecks such as low fermentation yield, large energy consumption and environmental pollution problem in the production of biofuel ethanol. Compared with pervaporation, vapor permeation has the advantages in separation performance, feeding cleanliness, energy saving and operation flexibility, which make it own a broader application prospect in the field of fuel ethanol production. On the basis of comparing with pervaporation and gas separation technology, the mechanism and characteristics of vapor permeation are described. In this paper, the materials and research progress of two kinds of membrane applied in different stages of fuel ethanol production, namely ethanol perm-selective membrane and water perm-selective membrane, are introduced. The novel researches of mixed matrix membrane in preparation methods and hybrid particle material selection are presented in detail. The paper reviews the industrial application of vapor permeation in the ethanol dehydration. The technology coupled with in-situ ethanol recovery and alternative distillation process are demonstrated. The possibility of vapor permeation combined with advanced solid state fermentation as once phase change method to produce biofuel ethanol is discussed. The problems that required to be studied and solved in the future are put forward to provide reference for the further application of vapor permeation technology in biofuel ethanol production.

Key words: vapor permeation, pervaporation, biofuel, ethanol, membrane, solid-state fermentation

中图分类号:

TQ028.8

李洪深, 李十中. 蒸汽渗透技术在燃料乙醇生产中的应用研究进展[J]. 化工进展, 2020, 39(5): 1620-1631.

Hongshen LI, Shizhong LI. Advances in research and application of vapor permeation for biofuel ethanol production[J]. Chemical Industry and Engineering Progress, 2020, 39(5): 1620-1631.

参考文献

1	SEMENCENKO V V, MOJOVIC L V, PETROVIC S D, et al. Recent trends in bioethanol production[J]. Hemijska Industrija, 2011, 65(2): 103-114.
2	PROSKURINA S, JUNGINGER M, HEINIMO J, et al. Global biomass trade for energy—Part 2: production and trade streams of wood pellets, liquid biofuels, charcoal, industrial roundwood and emerging energy biomass[J]. Biofuels Bioproducts & Biorefining-Biofpr, 2019, 13(2): 371-387.
3	ZABED H, SAHU J N, SUELY A, et al. Bioethanol production from renewable sources: current perspectives and technological progress[J]. Renewable & Sustainable Energy Reviews, 2017, 71: 475-501.
4	岳国君, 武国庆, 郝小明. 我国燃料乙醇生产技术的现状与展望[J]. 化学进展, 2007,19(7/8): 1084-1090.
4	YUE G J, WU G Q, HAO X M. The status quo and prospects of fuel ethanol process technology in China[J]. Progress in Chemistry, 2007, 19(7/8):1084-1090.
5	SANCHEZ O J, CARDONA C A. Trends in biotechnological production of fuel ethanol from different feedstocks[J]. Bioresource Technology, 2008, 99(13): 5270-5295.
6	韩冰, 王莉, 李十中, 等. 先进固体发酵技术(ASSF)生产甜高粱乙醇[J]. 生物工程学报, 2010, 26(7): 966-973.
6	HAN B, WANG L, LI S Z, et al. Ethanol production from sweet sorghum stalks by advanced solid state fermentation (ASSF) technology[J]. Chinese Journal of Biotechnology, 2010, 26(7): 966-973.
7	LI S Z, LI G M, ZHANG L, et al. A demonstration study of ethanol production from sweet sorghum stems with advanced solid state fermentation technology[J]. Applied Energy, 2013, 102: 260-265.
8	VANE L M. Review: Membrane materials for the removal of water from industrial solvents by pervaporation and vapor permeation[J]. Journal of Chemical Technology and Biotechnology, 2019, 94(2): 343-365.
9	陈镇, 秦培勇, 陈翠仙. 渗透汽化和蒸汽渗透技术的研究、应用现状及发展[J]. 膜科学与技术, 2003, 23(4): 103-109.
9	CHEN Z, QIN P Y, CHEN C X, Research, application situation and development of pervaporation and vapor permeation technology[J]. Membrane Science and Technology, 2003, 23(4): 103-109.
10	VANE L M, ALVAREZ F R. Effect of membrane and process characteristics on cost and energy usage for separating alcohol-water mixtures using a hybrid vapor stripping-vapor permeation process[J]. Journal of Chemical Technology and Biotechnology, 2015, 90(8): 1380-1390.
11	URAGAMI T, MORIKAWA T, OKUNO H. Characteristics of permeation and separation of aqueous alcohol-solutions through hydrophobic polymer membranes[J]. Polymer, 1989, 30(6): 1117-1122.
12	GORRI D, IBANEZ R, ORTIZ I. Comparative study of the separation of methanol-methyl acetate mixtures by pervaporation and vapor permeation using a commercial membrane[J]. Journal of Membrane Science, 2006, 280(1/2): 582-593.
13	SUEMATSU H, KIMURA S, NITTA T. Cost estimation of pervaporation and vapor permeation membrane separation systems for ethanol-water mixtures[J]. Kagaku Kogaku Ronbunshu, 1998, 24(6): 881-887.
14	王保国, 马明林. 高分子致密膜内渗透现象的同一性研究[J]. 化工学报, 2006, 57(1): 1-5.
14	WANG B G, MA M L. Permeation behaviors consistency in polymeric homogenous dense membranes[J]. Journal of Chemical Industry and Engineering (China), 2006, 57(1): 1-5.
15	SCHAETZEL P, VAUCLAIR C, NGUYEN Q T, et al. A simplified solution-diffusion theory in pervaporation: the total solvent volume fraction model[J]. Journal of Membrane Science, 2004, 244(1/2): 117-127.
16	WIJMANS J G, BAKER R W. The solution-diffusion model : a review[J]. Journal of Membrane Science, 1995, 107(1/2): 1-21.
17	由涛, 陈龙祥, 李波, 等. 渗透汽化传质模型的研究进展[J]. 化工进展, 2009, 28(7): 1109-1114.
17	YOU T, CHEN L X, LI B, et al. Research progress of mass transfer models for pervaporation[J]. Chemical Industry and Engineering Progress, 2009, 28(7): 1109-1114.
18	HUANG R Y M. Pervaporation membrane separation processes[M]. Amsterdan: Elsevier Publishers, 1991.
19	BETTEN B, VERHOEF A, VEEN H M VAN, et al. Pervaporation of binary water-alcohol and methanol-alcohol mixtures through microporous methylated silica membranes: Maxwell-Stefan modeling[J]. Computers & Chemical Engineering, 2010, 34(11): 1775-1788.
20	KUBACZKA A, KAMINSKI W, MARSZALEK J. Predicting mass fluxes in the pervaporation process using Maxwell-Stefan diffusion coefficients[J]. Journal of Membrane Science, 2018, 546: 111-119.
21	YE P, ZHANG Y, WU H, et al. Mass transfer simulation on pervaporation dehydration of ethanol through hollow fiber NaA zeolite membranes[J]. AIChE Journal, 2016, 62(7): 2468-2478.
22	LIU L, KENTISH S E. Pervaporation performance of crosslinked PVA membranes in the vicinity of the glass transition temperature[J]. Journal of Membrane Science, 2018, 553: 63-69.
23	DUDEK G, STRZELEWICZ A, TURCZYN R, et al. The study of ethanol/water vapors permeation through sulfuric acid cross-linked chitosan magnetic membranes[J]. Separation Science and Technology, 2014, 49(11): 1761-1767.
24	DUDEK G, GNUS M, STRZELEWICZ A, et al. Permeation of ethanol and water vapors through chitosan membranes with ferroferric oxide particles cross-linked by glutaraldehyde and sulfuric(Ⅵ) acid[J]. Separation Science and Technology, 2016, 51(15/16): 2649-2656.
25	HUA D, CHUNG T S, SHI G M, et al. Teflon AF2400/Ultem composite hollow fiber membranes for alcohol dehydration by high-temperature vapor permeation[J]. AIChE Journal, 2016, 62(5): 1747-1757.
26	MAKERTIHARTHA I G B N, DHARMAWIJAYA P T, WENTEN I G. Recent advances on bioethanol dehydration using zeolite membrane[C]//WARIS A, SHIN B, KONDO M, et al. 1st International Conference on Energy Sciences. Indonesia: Journal of Physics, 2017: 877-884.
27	RANGNEKAR N, MITTAL N, ELYASSI B, et al. Zeolite membranes : a review and comparison with mofs[J]. Chemical Society Reviews, 2015, 44(20): 7128-7154.
28	OKAMOTO K, KITA H, HORII K, et al. Zeolite NaA membrane: preparation, single-gas permeation, and pervaporation and vapor permeation of water/organic liquid mixtures[J]. Industrial & Engineering Chemistry Research, 2001, 40(1): 163-175.
29	NGOC T M, MAN T M, PHONG M T, et al. Fabrication of tubular ceramic-supported malic acid cross-linked poly(vinyl alcohol)/rice husk ash-silica nanocomposite membranes for ethanol dehydration by pervaporation[J]. Korean Journal of Chemical Engineering, 2019, 36(4): 584-590.
30	CHENG X X, PAN F S, WANG M R, et al. Hybrid membranes for pervaporation separations[J]. Journal of Membrane Science, 2017, 541: 329-346.
31	HUANG Z, GUAN H M, TAN W L, et al. Pervaporation study of aqueous ethanol solution through zeolite-incorporated multilayer poly(vinyl alcohol) membranes: effect of zeolites[J]. Journal of Membrane Science, 2006, 276(1/2): 260-271.
32	YU L, ZENG C, WANG C, et al. In situ impregnation gelation hydrothermal crystallization synthesis of hollow fiber zeolite NaA membrane[J]. Microporous and Mesoporous Materials, 2017, 244: 278-283.
33	SHIRAZI Y, TOFIGHY M A, MOHAMMADI T. Synthesis and characterization of carbon nanotubes/poly vinyl alcohol nanocomposite membranes for dehydration of isopropanol[J]. Journal of Membrane Science, 2011, 378(1/2): 551-561.
34	WANG M R, PAN F S, YANG L X, et al. Graphene oxide quantum dots incorporated nanocomposite membranes with high water flux for pervaporative dehydration[J]. Journal of Membrane Science, 2018, 563: 903-913.
35	DUDEK G, GNUS M, STRZELEWICZ A, et al. The influence of metal oxides on the separation properties of hybrid alginate membranes[J]. Separation Science and Technology, 2018, 53(8): 1178-1190.
36	VANE L M. A review of pervaporation for product recovery from biomass fermentation processes[J]. Journal of Chemical Technology and Biotechnology, 2005, 80(6): 603-629.
37	MOHAMMADI T, AROUJALIAN A, BAKHSHI A. Pervaporation of dilute alcoholic mixtures using pdms membrane[J]. Chemical Engineering Science, 2005, 60(7): 1875-1880.
38	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.
38	TANG Q Y, WANG L, ZHAN X, et al. Pervaporation of ethanol /water mixtures by PDMS /PVDF composite membranes with high permeability[J]. Membrane Science and Technology, 2011, 31(6): 1-5.
39	ZHAN X, LI J D, HUANG J Q, et al. Pervaporation properties of PDMS membranes cured with different cross-linking reagents for ethanol concentration from aqueous solutions[J]. Chinese Journal of Polymer Science, 2009, 27(4): 533-542.
40	PARK H B, KAMCEV J, ROBESON L M, et al. Maximizing the right stuff: the trade-off between membrane permeability and selectivity[J]. Science, 2017, 356(6343): 10.
41	LAN Y, YAN N, WANG W. Polydimethylsiloxane (PDMS) membrane filled with biochar core-shell particles for removing ethanol from water[J]. Bioresources, 2017, 12(3): 6591-6606.
42	LAN Y, YAN N, WANG W. Application of pdms pervaporation membranes filled with tree bark biochar for ethanol/water separation[J]. RSC Advances, 2016, 6(53): 47637-47645.
43	SUN D, LI B B, XU Z L. Pervaporation of ethanol/water mixture by organophilic nano-silica filled pdms composite membranes[J]. Desalination, 2013, 322: 159-166.
44	LI Q, CHENG L, SHEN J, et al. Improved ethanol recovery through mixed-matrix membrane with hydrophobic MAF-6 as filler[J]. Separation and Purification Technology, 2017, 178: 105-112.
45	CHEN X, PING Z H, LONG Y C. Separation properties of alcohol-water mixture through silicalite-i-filled silicone rubber membranes by pervaporation[J]. Journal of Applied Polymer Science, 1998, 67(4): 629-636.
46	LIU J, CHEN J X, ZHAN X, et al. Preparation and characterization of ZSM-5/PDMS hybrid pervaporation membranes: laboratory results and pilot-scale performance[J]. Separation and Purification Technology, 2015, 150: 257-267.
47	LIU G P, XIANGLI F J, WEI W, et al. Improved performance of PDMS/ceramic composite pervaporation membranes by ZSM-5 homogeneously dispersed in PDMS via a surface graft/coating approach[J]. Chemical Engineering Journal, 2011, 174(2/3): 495-503.
48	ZHAN X, LU J, XU H, et al. Enhanced pervaporation performance of PDMS membranes based on nano-sized octa (trimethoxysilyl)ethyl -poss as macro-crosslinker[J]. Applied Surface Science, 2019, 473: 785-798.
49	卞锐, 米文强, 赵靓, 等. 乙醇脱水3种膜-蒸馏耦合工艺[J]. 化工进展, 2011, 30(s2): 158-161.
49	BIAN R, MI W Q, ZHAO L, et al. Three kinds of membrane-distillation hybrid process for water-ethanol seperation[J]. Chemical Industry and Engineering Progress, 2011, 30(s2): 158-161.
50	SANDER U, JANSSEN H. Industrial application of vapor permeation[J]. Journal of Membrane Science, 1991, 61: 113-129.
51	GOZAN M, SETIAWAN M S, LISCHER K. Purification simulation with vapor permeation and distillation-adsorption in bioethanol plant[J]. Makara Journal of Technology, 2017, 21(1): 43-48.
52	胡子益, 李洪波, 谭宇鑫, 等. 微波合成的NaA型分子筛膜在乙醇脱水中试及3万吨/年工业示范装置的蒸汽渗透性能研究[J]. 化工进展, 2016, 35(s2): 438-442.
52	HU Z Y, LI H B, TAN Y X, et al. Microwave synthesis type NaA zeolite membrane for ethanol dehydration on vapor permeation study of experiment facility and 30000 tons per year industrial demostration unit[J]. Chemical Industry and Engineering Progress, 2016, 35(s2): 438-442.
53	MORIGAMI Y, KONDO M, ABE J, et al. The first large-scale pervaporation plant using tubular-type module with zeolite NaA membrane[J]. Separation and Purification Technology, 2001, 25(1/2/3): 251-260.
54	陈翠仙, 李继定, 潘健, 等. 我国渗透汽化技术的工业化应用[J]. 膜科学与技术, 2007, 27(5): 1-4.
54	CHEN C X, LI J D, PAN J, et al. Industrial application of pervaporation membrane technology in China[J]. Membrane Science and Technology. 2007, 27(5): 1-4.
55	WALSH P K, LIU C P, FINDLEY M E, et al. Ethanol separation from water in a two-stage adsorption process [J]. Biotech. Bioeng. Symp., 1983, 13: 629-647.
56	李云. 乙醇发酵蒸汽渗透耦合过程硅橡胶膜内多组分渗透机理研究[D]. 北京: 北京化工大学, 2012.
56	LI Y. The transport research through PDMS membrane during the continuous ethanol fermentation- vapor permeation process[D]. Beijing: Beijing University of Chemical Technology, 2012.
57	GAYKAWAD S S, RUTZE D N, WIELEN L A M VAN DER, et al. Vapour permeation for ethanol recovery from fermentation off-gas[J]. Biochemical Engineering Journal, 2017, 124: 54-63.
58	GAYKAWAD S S, WIELEN L A M VAN DER, STRAATHOF A J J. Effects of yeast-originating polymeric compounds on ethanol pervaporation[J]. Bioresource Technology, 2012, 116: 9-14.
59	O'BRIEN D J, ROTH L H, MCALOON A J. Ethanol production by continuous fermentation-pervaporation: a preliminary economic analysis[J]. Journal of Membrane Science, 2000, 166(1): 105-111.
60	DI LUCCIO M, BORGES C P, ALVES T L M. Economic analysis of ethanol and fructose production by selective fermentation coupled to pervaporation: effect of membrane costs on process economics[J]. Desalination, 2002, 147(1/2/3): 161-166.
61	SI Z, SHAN H, HU S, et al. Recovery of ethanol via vapor phase by polydimethylsiloxane membrane with excellent performance[J]. Chemical Engineering Research & Design, 2018, 136: 324-333.
62	SUN W, JIA W, XIA C J, et al. Study of in situ ethanol recovery via vapor permeation from fermentation[J]. Journal of Membrane Science, 2017, 530: 192-200.
63	董丹丹, 赵黛青, 廖翠萍, 等. 生物基燃料乙醇生产工艺的能耗分析与节能技术综述[J]. 化工进展, 2007, 26(11): 1596-1601.
63	DONG D D, ZHAO D Q, LIAO C P, et al. Energy consumption of fuel ethanol production and review of energy-saving technologies[J]. Chemical Industry and Engineering Progress, 2007, 26(11): 1596-1601.
64	KHALID A, ASLAM M, QYYUM M A, et al. Membrane separation processes for dehydration of bioethanol from fermentation broths: recent developments, challenges, and prospects[J]. Renewable & Sustainable Energy Reviews, 2019, 105: 427-443.
65	HUANG Y. Biosep: a new ethanol recovery technology for small scale rural production of ethanol from biomass[C]//2006 National Meeting of the American Institute of Chemical Engineers. San Francisco, CA. 2006.
66	VANE L M, NAMBOODIRI V V, BOWEN T C. Hydrophobic zeolite-silicone rubber mixed matrix membranes for ethanol-water separation: effect of zeolite and silicone component selection on pervaporation performance[J]. Journal of Membrane Science, 2008, 308(1/2): 230-241.
67	岳国君, 董红星, 刘文信, 等. 燃料乙醇工艺的化学工程分析[J]. 化工进展, 2011, 30(1): 144-149.
67	YUE G J, DONG H X, LIU W X, et al. Chemical engineering analysis of fuel ethanol process[J]. Chemical Industry and Engineering Progress, 2011, 30(1): 144-149.
68	GUERRERO L, CASTILLA S, COBO M. Advances in ethanol reforming for the production of hydrogen[J]. Quimica Nova, 2014, 37(5): 850-856.
69	NI M, LEUNG D Y C, LEUNG M K H. A review on reforming bio-ethanol for hydrogen production[J]. International Journal of Hydrogen Energy, 2007, 32(15): 3238-3247.

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