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+,PSFBO4PD&OWJSPO&OH _ Original Paper IUUQTEPJPSH,4&& *44/F*44/ Monoethanolamine t szsm5 MS13X CO 2 y m Adsorption of CO 2 on Monoethanol Amine-Impregnated ZSM5 and MS13X Sung-Woo Choi x s vw}s} Department of Environmental Science and Engineering, Keimyung University (Received February 7, 2017; Revised March 23, 2017; Accepted May 12, 2017) Abstract : Adsorption experiments of carbon dioxide were performed on ZSM5 and Molecular Sieve 13X (MS13X) impregnated with Monoethanol Amine (MEA). Adsorption efficiency of CO 2 was investigated in a U type packed column with GC/TCD. The adsorption capacities of adsorbents are estimated in the temperature range of 30-80. The modified adsorbents was characterized by BET surface area, N 2 adsorption/desorption isotherms, X-ray diffraction and FT-IR. Surface analysis results showed that the impregnation method did not affect the crystallinity of any adsorbents. BET surface area of the MS13X impregnated amine decreased to 19.945 m 2 /g from 718.335 m 2 /g. These reults showed that amine molecules were filled with the pore volume in MS13X, as a results restricting access of nitrogen into the pores. The MEA modified MS13X showed improvement in CO 2 adsorption capacity over the ZSM5 impregnated with MEA. The MS13X-MEA showed the highest adsorption capacity due to physical adsorption and chemical adsorption by amino-group content. This results also showed that adsorption capacity of MS13X-MEA increases with the temperature range of 60-80 compared with pristine MS13X. Key Words : Adsorption, CO 2 Capture, ZSM5, Molecular Sieve 13X, Impregnation, MEA. Monoethanolamine (MEA) j jzsm5 Molecular Sieve 13X (MS13X) ¼j m p lj º. m p n U jgc/tcd j º. pp в30~80 p ³ faj º. } mùph d kbet, N 2 p, XRD, FT-IR j º. h j Ùp lk j ÙMS13X BETh718.335 m 2 /g 19.945 m 2 /g q j º. ²MS13X j a pjj²ä º. MS13X-MEA²ZSM5-MEA k m p ³ } n a ²p mj p jä Ùº. jms13x-meam p ³ MS13X k60~80 Ð Ð aú º.. p, m g, ZSM5, Molecular Sieve 13X, j, MEA 1. IPCC (intergovernmental panel on climate change)² mq jccs (carbon capture and storage) ngpp j º. 1) p pbb ºe, pîj p¼j Ð kø º. 2~4) 100 Ña mp g k Ðp a³jp¼j a j jº. d²m Ða mp Ø p a Ð j º. Park î 5) d m jm p l kjda j p ³ a ²ää j º. m p p k Ð ² m p ³ a ºj º. 6) ôña zmp g j k ²pmj p j jº. mj p aj k j jm p n ¼ º. ¼h monoethanolamine (MEA), ethylenediamine (EDA), polyethylenimine (PEI) î í m, d î j j² j dp² j Ð j² a º. 7) d d h } mj mp ³ } j ² a kø º. Lee î 8) ZSM5l d PEI j j m p ³ 1.7 a d 13X MEA j j m p a ² kj º. 9) j Hong î 10) d 13X MEA piperazine Corresponding author E-mail: swchoi@kmu.ac.kr Tel: 053-580-5245 Fax: 053-580-5385

326 +,PSFBO4PD&OWJSPO&OH (PZ) j º jm d j j d Ð a ô p ³ q j p Ð 50 PZj da 1.8, MEAaj Ù d²20p ³ ajºj º. jjadhav î 11) } mj d 13X m p ³ } j, mj p º j º. m mj p p j jº. d p e akøp e ² jº. jò pðj Õ, Õ ô º Ð j º. ô ²MEA j jp j Ò l Õj p j º. p ²ZSM5 MS13Xj j n m p n h d j º. Fig. 1. %JBHSBN PG UIF FYQFSJNFOUBM TFUVQ B $0 C / D NBTTGMPXDPOUSPMMFSENJYJOHDIBNCFSFUFNQFSB UVSF DPOUSPMMFS G GVSOBDF H BETPSCFOU JO 6UVCF I ($5$% J 1$ 2. jzsm5 (ACROS, Belgium) Molecular sieve 13X (Fisher Chemical, U.K) h j ZSM5²SiO2/Al2O3a400~570 d Ål Molecular sieve 13X SiO2/Al2O3² 2.6~3.0 º. mj pj Ð99% MEA (JUNSEI, J.P)jj Xu î 12) j º. 15jº» 15 e nj Ù» 70, 16 eò Õ n j º. Õ je Õ Ð 70 j j nx² j o mj º. j30 wt% j (g) j j (wt%) = 100 p (g) + (g) j º. CO 2 p fa k Ùph p l j º. CO 2 p l GC-TCD (HP6890, Hewlett Packard, U.S.A)jFig. 1 º. lùco 2a в15%j, 30, 60, jj70 º 80 p lj º. ÙU l j 10 mm, ²200 mm º. j MFC (mass flow meter) j cylinder CO 2 10 cm 3 /min j º. m Ù 30 m, 0.32 mm j Þ 3 µm GS-Carbonplot (U.S.A) j º. j GC-TCD Õ 185 injector Ð 150 detector Ðj, oven в35 j j º. Autosorb-iQ & Quadrasorb SI (Quantachrome. U.S.A) jp faj h, j j º. MEAa j Ù p ZSM5-MEA MS13X-MEA² o jj k343k Ð 18 e jn j p d j º. º j k XRD (x-ray diffractometer)² D/max- 2500 (Rigaku, J.P) jbpj Ù j d d j kft-ir (Fouier transform infrared spectroscopy)frontier(perkinelmer, U.S.A) j º. 3. 3.1. MEA j jzsm5 MS13X d d MEA j j ZSM5 MS13X d Fig. 2 º. d l p в30, 60, 80 j Ð d d j º. C o² m Ð C²t ep n m Ð º. Fig. 2(a)MEA j jzsm5² 4 ¼ d a Ø Ð 30 d e 5.2 mp n a º. ²ZSM5 p jä p Ða p ³º. ô p Ð aa 30 p ³d e º. 60 80 ² d e Ñ Ò j p n a º. Fig. 2(b) MEA a j Ø MS13X 2.7 4.6 ¼ d a ØZSM5jd k º. MEAaj ØZSM5 MS13X² jd d amp ³aÑ Journal of KSEE Vol.39, No.6 June, 2017

+,PSFBO4PD&OWJSPO&OH.POPFUIBOPMBNJOF j j;4..49 $0 p d 327 B ;4. C.49 D ;4..&" E.49.&" Fig. 2. 5IF CSFBLUISPVHI DVSWFT PG $0 BETPSCFE CZ UZQF PG BETPSCFOTUT BU EJGGFSFOU BETPSQUJPO UFNQFSBUVSF º. Fig. 2(c)² 30 wt% MEAa j Ù ZSM5 bp Ð d k p MEAaj Ø ZSM5 k jñ p ² k º. Lee î 7) ô PEI j j ZSM5a j jzsm5 k mp ³ ² jº. ²MEA j nzsm5 hq p l p h j ²sitea mj p d e p ³ q Ùä Ùº. Fig. 2(d)²30 wt% MEA j jms13x p Ð 10 ¼ d a Ø30, 60, 80 p n aú º. ²MS13X-MEA k m mj p ³ aø 80 Ð mp ³ aú º. m º zº. 2RNH 2 + CO 2 RNHCOO - + + RNH 3 RNHCOO - - + H 2O RNH 2 + HCO 3 3.2. MEA j jzsm5 MS13X p ZSM5 MS13X CO 2 p MEA 30 wt% j j ZSM5 MS13X CO 2 p Fig. 3 º. Î CO 2 p á ª Z Þœ à œ ß j õ m p í(g) Q² a(ml/min), C i C oø²co 2 Ð(ppm), t² e(sec) jº. ZSM5 CO 2 pp 0.5 g ¼30 21.1 mg, 60 17.4 mg, 80 16.7 mg pa i p º. ZSM5-MEA30 18.1 mg, 60 16.8 mg, 80 16.4 mg k ZSM5 j MEA j jð j p p e ² k º. Lee î 8) ZSM5 PEI (polyethylenimine) j jôm pfaj º. ²PEIaj Ù ZSM5a ZSM5 k m p ¼jm jm 39 6m 2017 6

328 +,PSFBO4PD&OWJSPO&OH B ;4. C.49 Fig. 3. $PNQBSJTPO PG UPUBM BNPVOU PG $0 BETPSCFE POUP BETPSCFOUT BOE.&"JNQSFHOBUFE BETPSCFOUT º j ²PEI mj p jº j º. ² j ²È ²j SiO 2/Al 2O 3 Ùº. dpfrantz î 13) ôd Si/Al a m p n a º j º. ÙZSM5² a400 Ð kk mp n q Ùä bùº. MS13X CO 2 p 30 19.93 mg, 60 19.4 mg, 80 15.7 mg ZSM5j k Þp e CO 2 p ² Ñj º. MEA j jms13x CO 2 p 30 34.2 mg, 60 35.9 mg, 80 37.6 mg MS13X kco 2 p 2 p Ð ô ² º. ²j ÙMEAaMS13X hn ³ p ³ aùäbùº. dpp h j MEA j j j j p kppe m Ø MEA² p Ñh dk ºj º. 9) dpchatti î 14) d j j ímgj z j jº j º. } mù p m e Ò jº j 2 mol 1 mol m a w²º. ² l ja³l Ù d ä bùº.» j j pchatti î 14) a l jº p l º º. ² amj p jº²a j p l º n l kj j a ä Ùº. 3.3. MEA EDA j MCM41 h j Ùph d p n p j k BET, XRD, FT-IR j º. Table 1 p hj º. ZSM5 230 m 2 /g Lee î 8) j ZSM5 271~328 m 2 /g Frantz î 13) jj h º. ZSM5-MEA h 88 m 2 /g3q jä º. ² ZSM5 MEAaj Ø l jíq j º. Lee î 8) j ZSM5 m jn aq jº j º. j ZSM5-MEA aj jð jmp n ä Ùº. jxu î 15) β- d MEA j jh574 m 2 /g 15 m 2 /g j² 0.230 cm 3 /g 0.074 cm 3 /g q j, Hong î 10) Chatti î 14) ² d13x 30 wt% MEA 50 w t% MEA j j hbb613.5 m 2 /g, 386.4 m 2 /g 0.4 m 2 /g, 14.9 m 2 /g q j j² bb 0.2935 cm 3 /g, 0.2335 cm 3 /g 3.19 10-4 cm 3 /g, 0.0441 cm 3 /g q j ºj º. ²MEA j n MS13X h718.335 m 2 /g 19.945 m 2 /g j² Table 1. 4VSGBDF BSFB BOE QPSF WPMVNF PG UIF QSFQBSFE BE TPSCFOUT YRF" YRF"F84 FR W FR WF84 58SR ƒqfhpfƒpf x r!" %%!% $% " &&!" I ƒp w xp hx r $! # && Journal of KSEE Vol.39, No.6 June, 2017

+,PSFBO4PD&OWJSPO&OH.POPFUIBOPMBNJOF j j;4..49 $0 p d 329 f YRF" g FR W Fig. 4. G fi ƒ t yip ƒ t yt spƒx qfi ƒgpy fyif84tx ƒpryf pifi ƒgpy 0.360 cm 3 /g 0.099 cm 3 /g q jk j k º. dp Bezerra î, 9) Hong î 10) Chatti î 15) j aj hj² q jºj ²MEAa jø p kj j º. ZSM5 MS13X ZSM5-MEA MS13X-MEA N 2 î p Fig. 4 º. Þ pþ P/P oa0.1 0.8 m IUPAC ô Ilî º. ²bp l Bezerra î 9) Hong î 10) j º. jfrantz î 13) ZSM5 j m p N 2 p ajº H3l ² p km j º j º. ZSM5 MS13X } mùpxrd Fig. 5 º. Frantz î 12) ô ZSM5 XRD j 2θ s 7.9, 8.9, 23.13, 23.8 24.8 ºj Ð7.9, 8.7, 23.04, 23.89, 24.37 j ld XRD eº. dpzsm5ms13x MEA j n XRD j e j ²È ² j MEA j jð j d k jm k ²ºj º. 13) jhong î 10) j30 wt%, 50 wt%, 70 wt% aj ô XRD j qðaºj ²j aa d jq Ùº j º. ZSM5 MS13X j ÙpFT-IR Fig. 6 º. ZSM5 MS13X950~1,060 cm -1 Si-O ¼hj a º. MEA j j 1,515~1,651 cm -1 N-H 2 ìa Ø j m j Hong î, 10) Pham î 16) jp ìd a º. Bezerra î 9) ô ² 1,200 1,700 cm -1 º j º. Hong î 10) 3,278 cm -1 O-H alcoholj a 2,934~2,874 cm -1 C-H stretchj a1,648~1,581 f YRF" g FR W Fig. 5. WQ7 f pƒy q ƒt typ fi ƒgpy fyi fxtyptx ƒpryf pi fi ƒgpy ¼jm jm 39 6m 2017 6

330 +,PSFBO4PD&OWJSPO&OH B ;4. C.49 Fig. 6. '5*3TQFDUSBPGQSJTUJOFBETPSCFOUBOEBNJOFJNQSFHOBUFEBETPSCFOU cm -1 N-Hj a Ø º j MEA j aj ô FT-IR j a ajº j º. Frantz î 13) ô ZSM5450, 790, 1,080 1,220 cm -1 SiO 4 d ìa 1220 cm -1 ZSM5dº j 550~ 450 cm -1 p ìa ZSM5l d d j º. Acknowledgement ²2016 Ð ¼j kø º. References 4. ² m pk¼h MEA ZSM5 MS13X j j m p l hj º z º., m p l ZSM5 ZSM5-MEA² j nams13x²j Ù MS13X-MEA p 2 aj²ä º. dpms13x-mea mp30 34.2 mg, 60 35.9 mg, 80 37.6 mgð a ô e aj² k p j º. ß, BET h ÞpÞj n í MS13X²718.335 m 2 /g MEA j n 19.945 m 2 /g j j 0.360 cm 3 /g 0.099 cm 3 /g q j º. XRD FT-IR ² l ZSM5 MS13X j e j Ùp d j a Ø º. MS13X MEA j jp a m p n60-80 p Ð Ðnmp j º. ² nco 2 p } m Ùä ¼Ùº. 1. IPCC, IPCC special report on carbon dioxide capture and storage, Cambridge University Press, New York, pp. 105~ 178(2005). 2. Feng, B., An, H. and Tan, E., Screening of CO 2 adsorbing materials for zero emission power generation systems, Energy and Fuel., 21, 426~434(2007). 3. Wang, X. P., Jun J. J., Cheng, J., Hao, Z. P. and Xu, Z. P., High-temperature adsorption of carbon dioxide on mixed oxides derived from hydrotalcite-like compounds, Environ. Sci. Technol., 42, 614~618(2008). 4. Belmabkhout, Y., Serna-Guerrero, R. and Abdelhamid Sayari, A., Adsorption of CO 2 from dry gases on MCM41 silica at ambient temperature and high pressure. 1: pure CO 2 adsorption, Chem. Eng. Sci., 64(17), 3721~3728(2009). 5. Park, I. G., Hong, M. S., Kim, B. S. and Kang, H. G., Ambient CO 2 adsorption and regeneration performance of zeolite and activated carbon, J. Korean Soc. Environ. Eng., 35 (5), 307~311(2013). 6. Chena, C., Sona, W. J., Youb, K. S., Ahnb, J. W. and Ahna, W. S., Carbon dioxide capture using amine-impregnated HMS having textural mesoporosity, Chem. Eng. J., 161, 46~52(2010). 7. Brandani, F. and Ruthven, D. M., The effect of water on the adsorption of CO 2 and C 3H 8 on type X zeolites, Ind. Eng. Chem. Res., 43(26), 8339~8344(2004). 8. Lee, C. H., Hyeon, D. H., Jung, H., Chung, W., Jo, D. H., Shin, D. K. and Kim, S. H., Effects of pore structure and PEI impregnation on carbon dioxide adsorption by ZSM-5 zeolites, J. Ind. Eng. Chem., 23, 251~256(2015). Journal of KSEE Vol.39, No.6 June, 2017

+,PSFBO4PD&OWJSPO&OH.POPFUIBOPMBNJOF j j;4..49 $0 p d 331 9. Bezerra, D. P., Silva, F. W. M., Moura, P. A. S., Sousa, A. G. S., Vieira, R. S., Castellon, E. R. and Azevedo, D. C. S., CO 2 adsorption in amine-grafted zeolite 13X, App. Surf. Sci., 314, 314~321(2014). 10. Hong, M. S., Pankaj, S., Jung, Y. H., Park, S. Y., Park, S. J. and Baek, I. H., Separation of carbon dioxide using pelletized zeolite adsorbent with amine impregnation, Korean Chem. Eng. Res., 50(2), 244~250(2012). 11. Jadhav, P. D., Chatti, R. V., Biniwale, B., Labhsetwar, N. K., Devotta, S. and Rayalu, S. S., Monoethanol amine modified zeolite 13X for CO 2 adsorption at different temperatures, Energy and Fuel., 21, 3555~3559(2007). 12. Xu, X., Song, C., Andresen, J, M., Miller, B, G. and Scaroni, A, W., Preparation and characterization of novel CO 2 molecular basket adsorbents based on polymer-modified mesoporous melecular sieve MCM-41, Micro & Meso. Mat., 62, 29~45(2003). 13. Frantz, T. S., Ruiz, W. A., Rosa, C. A. and Mortola, V. B., Synthesis of ZSM-5 with high sodium content for CO 2 adsorption, Micro. and Meso. Mat., 222, 2009~2017(2016). 14 Chatti, R., Ransiwal, A. K., Thote, J. A., Kumar, V., Jadhav, P., Lokhande, S. K., Biniwale, R. B., Labhsetwar, N. K. and Rayalu, S. S., Amine loaded zeolites for carbon dioxide capture: Amine loading and adsorption studies, Micro. and Meso. Mat., 121, 84~89(2009). 15. Xu, X., Zhao, X., Sun. L. and Liu. X., Adsorption separation of carbon dioxide, methane and nitrogen on monoethanol amine modified β-zeolite, J. Natu. Chem., 18, 167~172(2009). 16. Pham, T. H., Lee, B. K. and Kim, J. T., Novel improvement of CO 2 adsorption capacity and selectivity by ethylenediaminemodified nano zeolite, J. Tai. Ins. Chem. Eng., 66, 239~248 (2016). ¼jm jm 39 6m 2017 6