촉진수송 분리 막을 이용한 올레핀/파라핀 혼합물로부터 올레핀 분리에 관한 연구
- 발행기관 고려대학교
- 발행년도 2007
- 학위수여년월 2007. 2
- 학위명 석사
- 학과 대학원 화공생명공학과 화공생명공학전공
- 식별자(기타) DL:000018551446
- 서지제어번호 000045358292
초록/요약
본 연구에서는 촉진수송 분리막을 이용하여 ethylene/ethane, propylene/propane, isoprene/n-pentane과 같은 C2, C3, C5의 이성분계 올레핀/파라핀을 분리하였다. 우선 촉진 수송 분리막에 사용된 전해질로 imdazolium, morpholinium, piperidinium 및 pyrrolidinium을 기본으로 여러 작용기를 반응시킨 zwitterionic compound를 이용하여 사용하였다. 제조된 분리막들은 zwitterionic의 작용기, 은염의 종류, 그리고 zwitterionic compound의 종류에 따라 각기 다른 분리성능을 나타내었다. 또한, 촉진수송 분리막에 사용된 고분자 전해질로는 SO3H기를 가진 sulfonated poly(ether ether ketone)(SPEEK)을 사용하였는데, SPEEK는 제조 방법에 따라 다양한 Degree of Sulfonation(DS)을 나타내는 것을 1H NMR spectroscopy를 사용하여 확인할 수 있었다. SPEEK의 농도를 변화시켜 제조된 막은 각각 다른 두께로 코팅됨을 SEM으로 확인하였고, 이 막들을 이용하여 ethylene/ethane, propylene /propane의 혼합물 분리를 수행하였다. 그 결과 ethylene과 propylene은 SPEEK의 농도에 따라 200~500의 선택도를 보여주었고, 투과도는 5~50GPU값을 보여주었다. 또한 은염의 종류에 따라서도 각기 다른 분리성능을 나타내었다. Isoprene /n-pentane 분리실험에서는 Polysulfone(PSf) Hollow fiber에 SEEEK로 코팅한 Liquid-liquid membrane contactor를 이용하였다. Hollow fiber contactor 실험에서는 AgNO3 수용액을 흡착 용액으로 사용하였다. Isoprene/n-pentane 분리 실험 결과, 장시간 동안 (≥100h) 막의 성능이 유지됨으로써 뛰어난 성능을 보여주었으며, 높은 선택도를 나타내었다.
more초록/요약
This research has been performed to develop new support materials for silver-based olefin/paraffin separation membranes. The target olefin/paraffin mixtures were ethylene/ethane, propylene/propane and isoprene/n-pentane which require energy-intensive cryogenic distillation system in the conventional process. Imidazolium, morpholinium, piperidinium and pyrrolidinium based zwitterionic compounds have been synthesized and used as supports for the facililated transport membranes. The performance of prepared silver-ziwtterionc composit membrane for the separation of olefin/paraffin have been affected by the zwitterion structure, functional group of the zwitterion and the anion of silver salt. Also, the composite membranes containing sulfonated poly(ether ether)ketone (SPEEK)-AgNO3 layers on top of polyester supports were prepared and tested for the separation of olefin from paraffin. The SPEEK-AgNO3 membrans showed good selectivity for ethylene over ethane, propylene over propane and isoprene over n-pentane. Anion of siver salt, concentration of SPEEK solution in MeOH and DS of SPEEK affected the selectivity and the flux of the membrane. The separation of isoprene form n-pentane mixtures was also carried out using hallow fiber membranes containing SPEEK layers on top of PSf supports in a liquid-liquid membrane contactor system. Any significant deterioration in the membrane performance was not observed after 100 h operation, suggesting a possible application of these SPEEK-coated PSf hollow fibers to the separtion of real C5 mixtures.
more목차
CONTENTS
Abstract
List of Figures
List of Tables
CHAPTER Ⅰ. INTRODUCTION
1.1 Background of Olefin Separation
1.2 Research Trends of Olefin Separation
1.3 Research States
CHAPTER Ⅱ. THEORETICAL CONSIDERATION
2.1 Membrane
2.2 Reversible π-Complexation
2.3 Facilitated Transport Membrane
2.4 Ionic Liquids
CHAPTER Ⅲ. EXPERIMENTAL
3.1 Materials
3.2 Synthesis of Zwitterionic Silver Complex
3.3 Synthesis of Sulfonated Poly(ether ether ketone)
3.4 Preparation of Facilitated Transport Membranes
3.5 Preparation of Hollow Fiber Membrane Module
CHAPTER Ⅳ. RESULTS AND DISCUSSION
4.1 Performance of Zwitterionic Silver Complex Membranes
4.2 Performance of SPEEK Silver Complex Membrane
4.3 Performance of Liquid-liquid Membrane Contactor
CHAPTER Ⅴ. CONCLUSION
REFERENCES
List of Figures
Figure 2.1. π-bone complexation between olefin and Ag+
Figure 2.2. Facilitated transport membrane.
Figure 3.1. (a) Photograph of zwitterionic silver complex membrane, (b) Phtograph of membrane cell
Figure 3.2. (a) Photograph, (b) Schematic diagram of membrane moduleapparatus
Figure 3.3. SEM picture of a composite membrane with various concentrationSPEEK top layer on the polyester
Figure 3.4. (SEM picture of 5wt% SPEEK top layer on the Hollow fiber
Figure 3.5. (a) Polysulfone hollow fiber membrane module, (b) Schematicdiagram of membrane module apparatus
Figure 4.1. Effect of various zwitterionic silver complex membrane
Figure 4.2. Effect of PVIS silver complex membrane
Figure 4.3. Effects of the DS by reaction condition
Figure 4.4. (a)Nomenclature of the aromatic protons for SPEEK repeat unit,(b)1H NMR spectra of SPEEK (dissolved in DMSO)
Figure 4.5 Effect of various concentration SPEEK silver complex membrane
Figure 4.6 Effect of various concentration SPEEK silver complex membrane
Figure 4.7 Effect of various silver salts for SPEEK silver complex membrane
Figure 4.8 Effect of liquid-liquid membrane contactor
Figure 4.9 Effcet of concentration of aqueous AgNO3 solution
List of Tables
Table 1.1. The Scale and Process of Commercial process for separating isoprene from C5 Fraction.
Table 2.1. Phenomenological equations.
Table 2.2. Membrane processes and driving forces
Table 2.3. Classification of membrane separation process
Table 2.4. Promotion Energy and Electron Affinity Data of Various Metals
Table 3.1. Structural formula of Zwittrerionic and SPEEK
Table 3.2. The analysis condition of gas chromatography
Table 3.3. Characterization of microporous polyester membrane
Table 3.4. Thickness of various concentration SPEEK
Table 3.5. Characterization of polysulfone hollow fiber membrane
