제올라이트 4A 분리막을 이용한 물/메탄올, 물/부탄올 혼합물의 투과증발 특성 연구: 실험 및 모형 = Pervaporation of binary Water/Methanol and Water/Butanol Mixtures through Zeolite 4A Membranes: Experiments and Modeling

국문 초록 (Abstract)

본 연구에서는 (주)파인텍에서 제조한 제올라이트 4A 분리막을 이용하여 물/메탄올, 물/부탄올 혼합물의 투과증발 실험을 수행하였다. 분리막을 투과한 기체분자들은 액체질소트랩을 이용하여 포집하였으며, 기체크로마토그래피(TCD)를 이용하여 혼합물의 조성을 분석하였다. 실험을 통해 물과 메탄올(분리계수 최대 250 이상), 물과 부탄올(분리계수 최대 1,500 이상)의 혼합물에서 선택적으로 물을 분리하는 것을 확인하였다. GMS (generalized Maxwell Stefan) 이론을 적용하여 2성분 계의 투과증발 거동을 모사하였으며, 상수추정을 통하여 제올라이트 비지지체의 흡착상수 및 확산상수를 구하였다. 제올라이트 4A 분리막의 경우 기공의 크기가 물보다는 크고, 메탄올, 부탄올 보다는 작기 때문에, 알코올로부터 물을 분리시키는 공정에 적용시킬 수 있다. 바이오 에탄올 분리, 부탄올 분리, 막반응기, 하이브리드 반응-탈수 공정 등에 적용할 수 있을 것으로 사료된다.

다국어 초록 (Multilingual Abstract)

In this study, pervaporation performances of water/methanol and water/butanol mixture were evaluated using zeolite 4A membranes manufacutred by FINETECH by experimental works and numerical modeling. Permeation and separation characteristics, such as flux and separation factor, were analyzed by gas chromatography (TCD) and liquid nitrogen traps. Experiments have shown that water is selectively separated from a mixture of water and methanol (separation factor up to approximately 250) and water and butanol (separation factor up to approximately 1,500). Generalized Maxwell Stefan (GMS) theory was implemented to predict pervaporation behaviors of water/alcohol mixtures and diffusional coefficients of zeolite layer were obtained through parameter estimation using MATLAB Ⓡ optimization toolbox. Since the pore size of zeolite 4A are much larger than kinetic diameter of water molecules and smaller than those of methanol and butanol, zeolite 4A membranes can be applied to in situ water removal process such as membrane reactors or hybrid reaction-dehydration process.

참고문헌 (Reference)

1 이용택, "에틸아세테이트 생산 공정의 탈수를 위한 NaY 제올라이트 분리막 투과증발" 한국화학공학회 43 (43): 366-370, 2005

2 R. Rautenbach, "The separation potential of pervaporation : Part 1. discussion of transport equations and comparison with reverse osmosis" 25 : 1-, 1985

3 F. Kapteijn, "The generalized Maxwell-Stefan model for diffusional in zeolites : sorbate molecules with different saturation loadings" 55 : 2923-, 2000

4 Y. Morigami, "The first large-scale pervaporation plant using tubular-type module with zeolite NaA membrane" 25 : 251-, 2001

5 R. C. Reid, "The Properties of Gases and Liquids" McGraw-Hill 1977

6 R. Krishna, "The Maxwell-Stefan description of mass transport across zeolite membranes" 57 : 155-, 1995

7 H. Kita, "Synthesis of a zeolite NaA membrane for pervaporation of water/organic liquid mixtures" 14 : 206-, 1995

8 R. C. Binning, "Separation of liquid mixtures by permeation" 53 : 45-, 1961

9 S. Y. Li, "Separation of 1-butanol by pervaporation using a novel tri-layer PDMS composite membrane" 363 : 287-, 2010

10 W. Won, "Pervaporation with chitosan membranes : separation of dimethylcarbonate/methanol/water mixtures" 209 : 493-, 2002

11 Y. M. Lee, "Pervaporation of organic liquid mixtures through polymer membranes" 13 : 3-, 1989

12 Y. K. Hong, "Pervaporation characteristics of aqueous isopropanol solution using tubular type PDMS/ceramic composite membrane" 36 : 524-, 1998

13 L. Gongping, "Pervaporation Separation of Butanol-Water Mixtures Using Polydimethylsiloxane/Ceramic Composite Membrane" 19 : 40-, 2011

14 F. Kapteijn, "Permeation and separation of light hydrocarbons through a silicalite-1 membrane Application of the generalized Maxwell-Stefan equations" 57 : 145-, 1995

15 Q. Liu, "Organics/water separation by pervaporation with a zeolite membrane" 117 : 163-, 1996

16 A. Kasik, "Organic solvent pervaporation properties of MOF-5 membranes" 121 : 38-, 2014

17 C. C. Pereira, "New insights in the removal of diluted volatile organic compounds from dilute aqueous solution by pervaporation process" 138 : 227-, 1998

18 D. Hofmann, "Molecular modelling of pervaporation separation of binary mixtures with polymeric membranes" 144 : 145-, 1998

19 The Membrane Society of Korea, "Membrane separation – basic"

20 H. Renon, "Local composition in thermodynamic excess functions for liquid mixtures" 14 : 135-, 1968

21 P. Aptel, "Liquid transport through membranes prepared by grafting of polar monomers onto poly(tetrafluoroethylene)films. I. Some fractionations of liquid mixtures by pervaporation" 16 : 1061-, 1972

22 E. A. Mason, "Gas transport in porous media : the dusty-gas model" Elsevier Science Ltd 30-50, 1983

23 P. Uchytil, "Gas permeation in ceramic membranes Part 1. Theory and testing of ceramic membranes" 97 : 139-, 1994

24 A. J. Burggraaf, "Fundamentals of inorganic membrane, science and technology, 1996" Elsevier 35-66, 2009

25 T. C. Bowen, "Fundamentals and applications of pervaporation through zeolite membranes" 245 : 1-, 2004

26 A. S. Michales, "Conditioned polyethylene as a permselective membrane. Separation of isomeric xylenes" 1 : 14-, 1962

27 A. Tuchlenski, "An experimental study of combined gas phase and surface diffusion in porous glass" 140 : 165-, 1998

28 "ASPEN DATABANK"