3.4. (Continuous Electrodeionization) 3.4.1... 1950 Walter [Walter et al., 1955]. Walter 100%,,., 100%.,.,,. 1987 Millipore co.,. DOE (Deparatment of Energy) NASA..,, (Demi System). 3.4.2. (CEDI, Continuous Electrodeionization). 1987 (Milipore Corp.) Ionpure TM CDI (Continuous Deionization). CEDI, EDI, CDI American Society for Testing and
Materials'D-19 Committee on Water CEDI. CDI [Mike Henley, 1997].. U. S. Filter CDI TM 1986 Milipore. Milipore Ionpure [Giuffrida et al.,1986]. 1993 Eastern Enterprises Ionpure U. S. Filter 1000. Electropure Milipore 1984. Electropure HOH Water Technologies Milipore [Ultrapure Water, 1993 ; 1996] U.S. Filter Ionics E-Cell. 1991 Ionics. US Filter US Reissue Patent No. Re 35, 741. 10 US Filter Ionics..,,,. E-Cell US Filter Ionics 80 gpm 2000 gpm,,. E-Cell 50 %. 12.5 gpm. E-Cell Ailly 3 13,000 gpm Ionics 10 6,000 7,000 gpm. 1980. 1.
. 3.4.3, 3. 1,. Porous plug,, -,, -,.. (Ion-conducting spacer).,.
전기탈이온시스템의최적공정설계및개발 금속이온을포함하지않는상수및폐수 - 초순수제조공정개발 금속이온을포함하는상수및폐수 - 일차냉각수정화공정개발 - 도금폐수에서중금속회수공정개발 이온전도성스페이서의개발 이온교환수지 이온교환섬유 이온교환폴리우레탄 전기탈이온시스템의특성분석 - Flow cell 에의한전기전도도측정 - Porous-plug model - 이온전도성스페이서의흡착 - 평형연구.,,,.,. 3.4.4., Porous-plug. Porous plug model Spiegler, Yoest Willie.. 2 (1, a) (2, b). (3, c).. a, b, c 3 d, e [Spiegler et al., 1956].
1 2 3 d1 e1 d2 e2 d3 a b c 3 IRN 77, CIEPU [Yeon and Moon, 2003]. e(0.28) e(0.30) d(0.72) d(0.70) a(0.68) b(0.05) c(0.27) a(0.63) b(0.03) c(0.34) IRN77 CIEPU. IRN 77 0.68 fraction, 0.05, 0.27., actively conducting pathway, porous plug model b., b., b, actively conducting pathway
., porous plug model.,. chronopotentiometry conducting region nonconducting regtion.. [Yeon and Moon, 2000] Langmuir (isotherm). box.
.,,...,
( ), ( ),,,,,. I (C 2 -C 1 ),,, charge.,. ph, Freundlich Langmuir.
(Pore diffusion) (Film diffusion) (rate limiting step) [Rengaraj, Yeon, Moon, 2001; Glasstone, 1946]. [Yeon, Moon, 2003].,.,. U. S. Filter Ganzi (packing density) [Ganzi, 1991]. Cubic structure Hexagonal structure conductive path. Hexagonal structure. -.. ( ),. monopolar membrane, bipolar membrane.,
.,. 3.4.5. 1987 Milipore Ionpure CDI. 100 ( 2 3). 1950 (400 800 ) ( ). US Filter, Ionics, Electropure, E-Cell... Kedem (The Institutes for Applied Research, Ben-Gurion Unversity of the Negev) Polyolefin [Korngold, Aronov, Kedem, 1998]. (Reacted spacer). (functional group) (Coated spacer) [Messalem et al., 1998]. bromomethylated and aminated polysulfone. Gavach [Laktionov et al., 1999; Dejean et al., 1997; Dejean et al., 1998]. Institut Textile de France Emmanuel Dejean. 200 ( 5). 4. 0.5 1.0 meq/g.
(irradiation). (backbone polymer) (branched polymer)..., UV.. Co-60-30 k [ (gray): SI, 1 = 1 J/kg = 100
rad].. 0.6 1.2 meq/g. 1.5 meq/g..,...... (bead). (sheet). (400 800 )... [,,, 2001]. [,, 2001].. 1999-0072765,, 2 50 %. 65. (110 )
.. /. 5. 70%. -ray,,. UV. 6 UV. 4. UV,,. 2-..,. UV... UV 2.2 meq/g..,.,.,.
혼합기 적하깔데기 온도계 콘덴서 N2 가스 반응플라스크 OCN NCO TDI Stirring 30 min at 110 0 C NCO Dropping PPG below 110 0 C HO CH 2 CH O H n CH 3 Foaming Ion-exchanger (bead/powder) +surfactant+glycerine+water O TDI PPG O C NH O O NH-C-O-PPG-O-C-NH- R N C O H O Urethane H 2 C R' O NH-C-O-TDI-PPG-TDI O + R N C O H 2 110 o C R N C O C R' Isocyanate C O Allophanate NH O R H N C H N R' Disustituted Urea R O + R N C O R H N C N 110 o C Isocyanate Biuret C NH R R' O
BP coating UV-grafting polymerization Thermal reaction polymerization H 2 C CHCOOH (AAc) H 2 C CH SO 3 Na (SSS) CH 2 HOOCHC CH 2 H 2 C SO 3 Na CH 2 CH n CH 3 (Polypropylene) + UV UV Heat (80 C) CH 2 CH 2 C n CH 3 Cation exchange textile C O (BP) UV H 2 C CH CH 2 N(CH 3 ) 3 Cl (VBTAC) H 2 C C(CH 3 )COCH 2 CH 2 OH O (HEMA) CH 2 HOH 2 CH 2 COC(H 3 C)C CH 2 H 2 C CH 2 N(CH 3 ) 3 Cl CH 2 CH 2 C n CH 3 Anion exchange textile 7. UV. 5. UV CIET AIET Photo initiator 3 wt.% BP 5 wt.% BP Monomer Concentration 10 wt.% AAc, 5 ~25 wt.% SSS 30 wt.%hema, 25 wt.% VBTMC Solvent Distilled water Methanol/DMF(50:50vol%) Temperature (C) 80 Reaction time 4hr 6hr Abbreviations :BP = Benzophenone, AAc =Acrylic acid, SSS = Sodium styrenesulfonate, HEMA = 2-Hydroxyethyl methacrylate, VBTAC = vinylbenzyl trimetyl ammonium chloride DMF = Dimethylformamide
3.4.6. 1955 Walter, Weiser, Marek Argonne National Laboratory [Walters et al., 1955]. 8 (Reverse Osmosis, R/O). - 10 60 psig,,, 0.01 ppm, SDI 4, 0.1 ppm 80 % 1.0 ppm 90 % 1.0 ppm.,,,,,. (Tap Feed System) (R/O Feed System). 80 %. 90 % (Fouling) (chemical cleaning) - (R/O-CEDI system) [, 1998].
- 16.6M cm 5 s/cm,... 9.,..,. UF/EDR/RO/EDI UF/RO/EDI. 4.5 /hr, 11.3 /hr 22.7 /hr 3. ( 9). Florida Power & Light, Turkey Point 1, 2. 80 kw.
.,, 45 /hr. Grand Gulf 1991 11.3 /hr [, 1998]. OMEXELL plate leakage EDI ( 11). 50%,.,. 15,000 gpm,. CEM BM AEM CEM BM AEM CEM BM AEM Me + X - CATHODE H 2 OH - X - Me + CIXAIX OH - OH - OH - X - Me + X - Me + X - X - Me + CIXAIX CIXAIX O 2 Me + ANODE Feed Desalted solution Concentrate Institut für Chemische Verfahrens technik Eignberger. 12 Bipolar membrane 13.
Rinsing bath ph. 5 %. [Thate and Eigenberger, 2000]. Feed CEM CEM AEM CEM CEM AEM CEM CEM AEM CEM CEM AEM ANODE O 2 X - Me + X - Me + CIX X - X - Me + CIX X - H 2 X - X - X - X - Me + Me + CIX CIX CATHODE Acid Feed MeX concentrate Pure water ( 14)... ( )..,. 1987 Milipore Co. Edison U.S Filter (Make up Water)...
CMX CMX AMX CMX + OH - ->H 2 O OH - NO 3 OH - Co 2+ C D C Na 2 SO 4 Co 2+ -, NO 3 CIX AIX MIX. (Layered bed-cedi system). 11 (CIX) : (AIX) : (MIX) 1:1:1. ph 7 ph 3. CIX:AIX:MIX = 1:1:1. ph ph [Yeon, Rengaraj, Moon, 2000]., 98%.,. 10 ppm 98%,.. ph., sorption. RO 65%,,.
, 100%.,,,.,. 100%,.,.,,..,..,,.,. 10 mm leakage [Korngord, 1976],.,, sizing parameter actively conducting pathway. actively conducting surface area.. (Mixed bed-cedi) (Layered bed-cedi) (Mixed bed-cedi) (Layered bed-cedi). (Membrane fouling)
(Layered bed-cedi). 15. 60. ph 6.9 7.4. ph ph ph ph..,,... (CVCS) (VCT) [,, 2001].
12 15 1 13 16 4 5 9 10 2 3 6 8 7 11 14 1. 일차냉각수원수 2. 냉각장치 3. ph 조정 Tank 4. ph 조정용산 (Acid) Tank 5. ph 조정용염기 (Base) Tank 6. 정밀여과장치 7. 정밀여과농축액 ( 액상폐기물처리 ) 8. 정밀여과처리수 9. 전기탈이온 (EDI) 장치 10. EDI 농축액 Tank 11. 전극액 Tank 12. 전원공급장치 13. EDI 희석액 Tank 14. EDI 농축액 ( 액상폐기물처리 ) 15. 일차냉각수보충수 (make-up water) 16. EDI 처리수 ( 일차냉각수로재순환 ) BIIL(Bipolar interface inhibitory layer) 장착한전기탈이온스택 일차냉각수보충수일차냉각수보충수 RO/NF & EDI System RO/NF & EDI System D 전처리 노심초기 C VCT 원자로일차냉각수로원자로일차냉각수로재순환재순환 BIIL (Bipolar interface inhibitory layer) 장착하지않은전기탈이온스택 (Volume Control Tank) D 노심말기 전기투석 BIIL-EDI 원자로일차냉각수 C EDI 농축수 BRS (Boron Recovery System)
. 20 50 gpm. gpm [Auerswald, 1994].. 사용자 : Nebraska Public Power District 위치 : Cooper Nuclear Station, Nebraska 적용년도 : 1997 응용 : High purity water for boiler feed 유입수 : Well water 유입수질 : High in bacteria, high in barium & manganese, high bicarbonate, very high iron and high silica. High hardness, 750 ppm TDS 유출수질 : 18 megohm-cm resistivity 처리용량 : 60 gpm 적용기술 : Multimedia Filtration (MF), Activated Carbon Filtration, Degasification, Ultraviolet(UV), Ultrafiltration (UF), Reverse Osmosis (RO) 기술제공업체 : IONICS 사용자 : Florida Power and Light 위치 : Cutler Station, Florida 적용년도 : 1997 응용 : High purity water for boiler feed 유입수 : Well water 유입수질 : 300 ppm TDS 유출수질 : 10 megohm-cm resistivity 처리용량 : 50 gpm 적용기술 : Reverse Osmosis (RO), Electrodeionization(EDI) 기술제공업체 : IONICS 미국의남부캘리포니아 Edison 발전소 ( 1990년 Southern California Edison's Huntington Beach) 의여러곳에 US Filter에서 CDI 시스템을보충수처리시스템인순수처리시스템에적용하여매우좋은결과를얻었다고보고하고있다 1994년싱가폴의 Chartered Semiconductor Manufacturing에초순수공급을위한대단위 US Filter CDI 시스템을공급하여운전중에있다.
2 4. (Capital cost).,,.,,. 6. (Operating cost).. 1912 RO, NF, CEDI. CEDI Water Polishing. [Mike Henley, 1999].,,..
,.,.. 5, 5 5.,. 3.4.7. Auerswald, D. Regeneration without chemicals, Ultrapure water 11(3), 52-61 (1997). Dejean, E., Laktionov, E., Sandeaux, J., Sandeaux, R., Pourcelly, G., Gavach, C., Electrodeionization with ion-exchange textile for the production of high resistivity water: Influence of the nature of the textile, Desalination 114, 165-173 (1997). Dejean, E., Sandeaux, J., Sandeaux, R., Gavach, C., Water Demineralization by Electrodeionization with Ion-exchange Textile. Comparison with Conventional electrodialysis, Separation Science and Technology, 33(6), 801-818 (1998). Electropure lawsuit claims patent infringements, Ultrapure Water, 10(6), 10 (1993). Fournier, C., Rothenberg, B., Zoccolante, G., Impact of Proposed Pharmaceutical Water quality test revisions on system design, performance, and costs, pharmaceutical engineering, 15(6) (1995). Ganzi, G. C., Ionpure CDI Electrodeionization systems-new product and process- developments, in New Developments in Ion Exchange-Materials, Fundamentals, and applications, 317-322 (1991). Giuffrida, A.J.; Jha, A.D.; Ganzi, G.C., Electrodeionization apparatus, US Patent No. 4,632,745 (Dec. 30, 1986). Glasstone, A (Ed), Text Book of Physical Chemistry, Macmillan, Little Essex Street, London, (1946). HOH Water renamed Electropure, Ultrapure Water 13(6), 8 (1996). Henley, M., Market Overview: Ion exchange market shows slower growth, Ultrapure Water, July/August (1999). Henley, M., Technology Overview, CEDI gains ground as water treatment approach, Ultrapure
Water, October, 15-20 (1997). Korngold, E., Aronov, L., Kedem, O., Novel ion-exchange spacer for improving electrodialysis,. Reacted spacer, J. Memb. Sci. 138, 165-170 (1998). Laktionov, E., Dejean, E., Sandeaux, J., Sandeaux, R., Gavach, C., Production of High Resistivity water by Electrodialysis. Influence of Ion-exchange Textiles as Conducting spacers, Separation Science and Technology, 34(1) 69-84 (1999). Messalem, R., Mirsky, Y., Daltrophe, N., Saveliev, G., Kedem, O., Novel ion-exchange spacer for improving electrodialysis,. Coated spacer, J. Memb. Sci., 138, 171-180 (1998). Rengaraj, S., Yeon, K.-H., Moon, S.-H., Removal of Chromium from Water and Wastewater by Ion Exchange Resin, Journal of Hazardous Materials, 272(3), 1-15 (2001). Seong, J.-H., Yeon, K.-H., Choi, Y-H. and Moon, S.-H. A study on the characterization of an ion-exchange resin bed with metal solutions, The 3rd International symposium on Advanced Environmental Monitoring, K-JIST, 364-365 (2000). Spiegler, K. S., Yoest, R. L. and Wyllie, M. R. J., Discussions Faraday Soc., 21, 174 (1956). Thate, S. and Eigenberger, G. Continuous Electrodeionization(CEDI)- A Combination of electrodialysis and ion-exchange, in Advanced course on electro-membrane process (2000). Walter, W. R., Weiser, D. W., Marek, L. J., "Concentration of Radioactive Aqueous Wastes: Electromigration through Ion-exchange membranes, Industrial and Engineering Chemistry, 47, 61-67 (1955). Yeon, K.-H., Rengaraj, S. and Moon S.-H., Theory and Practice of Continuous Deionization in a Reactor Coolant System, The Korean Society of Clean Technology, B-11, 107-110 (2000). Yeon, K.-H., Rengaraj, S., Moon, S.-H., An electric resistance model for continuous electrodeionization, Theories and Applications of Chem. Eng., 6(1), 613-616 (2000).,,,, 1 (2001).,,, (Electrodeionization, EDI), 2001-52861.,, 1, : 2001-7122.,,, 1 (1998).,,, 1 (1998).