나노세공 분자체를 이용한 천연가스 연료로부터 황 화합물의 선택적 흡착

김훈성; 정종국; 이석희; 천재기; 문명준; 우희철; Hoon-Sung Kim; Jong-Kook Chung; Seok-Hee Lee; Jae-Kee Cheon; Myung-Joon Moon; Hee-Chul Woo

Clean Technology, Vol.13, No.1, 64-71, March, 2007

Export Citation

나노세공 분자체를 이용한 천연가스 연료로부터 황 화합물의 선택적 흡착

Selective Adsorption of Sulfur compounds from Natural Gas Fuel Using Nanoporous Molecular Sieves

김훈성, 정종국, 이석희 , 천재기 , 문명준, 우희철 ^†

부경대학교 응용화학공학부, 608-739 부산시 남구 용당동 산 100

Hoon-Sung Kim, Jong-Kook Chung, Seok-Hee Lee , Jae-Kee Cheon , Myung-Joon Moon, and Hee-Chul Woo^†

Division of Applied Chemical Engineering, Pukyong National University, San 100, Yongdang-dong, Nam-gu, Busan 608-739, Korea

E-mail:

초록

천연가스로부터 유기 황 화합물인 THT 와 TBM의 제거를 위한 적합한 흡착제의 선정이 수행되었다. 황화합물에 대한 포화 흡착량은 Na-Y, Na-ZSM-5, Na,K-ET(A)S-10, Na-모더나이트, Na,K-클리놉틸올라이트, Ti/MCM-41, Ti/SBA-15이 포함되어진 나노세공 물질 및 무정형 티타노실리케이트에 대하여 펄스 흡착 방법에 의해 측정되었다. 측정되어진 물질들 중 Na-Y 와 Na,K-ET(A)S-10 제올라이트에서 THT 와 TBM에 높은 흡착 용량을 보였다. Na,K-ET(A)S-10에서의 THT에 대한 포화 흡착량은 효율적인 흡착제로 잘 알려진 Na-Y 제올라이트와 비슷하였다. Na,K-ET(A)S-10에서의 THT 와 TBM의 흡착량과 흡착능은 Na,K-ET(A)S-10의 결정성이 좋을수록 증가하였다. 모사되어진 천연가스를 이용한 파과 평가로부터 THT 와 TBM 사이의 경쟁적 흡착에 관한 연구에서 Na,K-ET(A)S-10은 THT에 선택적으로 흡착하는 것으로 나타났다. Na,K-ET(A)S-10의 THT에 대한 파과 용량은 1.19 mmol/g 이었다. 이러한 결과들은 Na,K-ET(A)S-10 과 Na,K-ETAS-10의 높은 흡착 성능이 제올라이트 구조의 넓은 기공 성질과 유기 황 화합물과의 강한 정전기적 상호작용을 지닌 제올라이트 구조 속의 높게 교환되어진 양이온에 기인하는 것으로 보인진다.

The selection of a suitable adsorbent for removing organic sulfur compounds tetrahydrothiophene (THT) and t-butylmercaptan (TBM) from natural gas has been carried out. The saturation adsorption capacity for the sulfur compounds were determined by pulse adsorption method for a group of nanoporous materials, including Na-Y, Na-ZSM-5, Na,K-ET(A)S-10, Na-Mordenite, Na,K-Clinoptilolite, Ti/MCM-41, Ti/SBA-15 and amorphous titanosilicates. Among the materials tested, Na-Y and Na,K-ET(A)S-10 zeolites showed high adsorptive capacities for THT and TBM. The saturation capacity for THT on Na,K-ETS-10 was comparable with that on Na-Y zeolite, which is well known as an effective adsorbent. The capacity and adsorptivity for THT and TBM on Na,K-ETAS-10 were improved by an increase in crystallinity of Na,K-ETAS-10. An investigation of the competitive adsorption between THT and TBM from the breakthrough test using a simulated natural gas indicates that Na,K-ETS-10 selectively adsorbs THT. The breakthrough capacity for THT on Na,K-ETS-10 was 1.19 mmol/g. The results show that the high adsorption performance of Na,K-ETS-10 and Na,K-ETAS-10 is due to the highly exchanged cations in the zeolitic structure which exhibit the strong electrostatic interactions with organic sulfur compounds and their wide pore nature.

Keywords:흡착제;천연가스;유기 황 화합물;탈황;제올라이트;연료전지

[References]

Haile SM, Acta Mater., 51, 5981 (2003)
Rojey A, Thoma M, Jullian S, U.S. Patent NO., 5,803,953 (1998)
Bonville LJ, Degeorge CL, Foley PF, Garow JR, Lesieur R, Preston JL, Szydlowski DF, U.S. Patent NO., 6,159,256 (2000)
Ma XL, Sun L, Song CS, Catal. Today, 77(1-2), 107 (2002)
Wakita H, Ono Y, Tachiband Y, Hosalca M, U.S. Patent No., 6,579,347 B1 (2003)
Titley CW, Wieninger PH, U.S. Patent NO., 6,582,624 B2 (2003)
Satokawa S, Kobayashi Y, Fujiki H, Appl. Catal. B: Environ., 56(1-2), 51 (2005)
Wakita H, Tachibana Y, Hosaka M, Microporous Mesoporous Mater., 46, 237 (2001)
Chen YX, Jiang Y, Li WZ, Jin RC, Tang SZ, Hu WB, Catal. Today, 50(1), 39 (1999)
Choi M, Heo W, Kleitz F, Ryoo R, Chem. Commun., 12, 1340 (2003)
Chaudhari K, Das TK, Chandwadkar AJ, Sivasanker S, J. Catal., 186(1), 81 (1999)
Satokawa S, Itabashi K, Microporous Mater., 8, 49 (1997)
Kuznicki SM, Thrush KA, U.S. Patent No., 5,244,650 (1993)
Webb PA, Orr C, Analytical methods in fine particle technology, Micromeritics Instrument Corporation, Norcross, GA USA, 1997, pp. 53-153
Felix SP, Savill-Jowitt C, Brown DR, Thermochim. Acta, 433(1-2), 59 (2005)
Chon H, Catalysis an Introduction, 2nd ed, Hanrimwon, Seoul, 1992, pp. 370-374
Kim WJ, Kim YS, J. Korean Ind. Eng. Chem., 9(1), 33 (1998)
Rocha J, Anderson MW, Eur. J. Inorg. Chem., 801 (2000)
Philippou A, Rocha J, Anderson MW, Catal. Lett., 57(3), 151 (1999)
Thompson RW, in Karge, H.G., and Weitkamp, J., Eds., Molecular Sieves Science and Technology, Vol.1, Springer-Verlag, Berlin Heidelberg, 1-33 (1998)

[Referenced By]

[Related Articles]

[1] Haile SM, Acta Mater., 51, 5981 (2003)

[2] Rojey A, Thoma M, Jullian S, U.S. Patent NO., 5,803,953 (1998)

[3] Bonville LJ, Degeorge CL, Foley PF, Garow JR, Lesieur R, Preston JL, Szydlowski DF, U.S. Patent NO., 6,159,256 (2000)

[4] Ma XL, Sun L, Song CS, Catal. Today, 77(1-2), 107 (2002)

[5] Wakita H, Ono Y, Tachiband Y, Hosalca M, U.S. Patent No., 6,579,347 B1 (2003)

[6] Titley CW, Wieninger PH, U.S. Patent NO., 6,582,624 B2 (2003)

[7] Satokawa S, Kobayashi Y, Fujiki H, Appl. Catal. B: Environ., 56(1-2), 51 (2005)

[8] Wakita H, Tachibana Y, Hosaka M, Microporous Mesoporous Mater., 46, 237 (2001)

[9] Chen YX, Jiang Y, Li WZ, Jin RC, Tang SZ, Hu WB, Catal. Today, 50(1), 39 (1999)

[10] Choi M, Heo W, Kleitz F, Ryoo R, Chem. Commun., 12, 1340 (2003)

[11] Chaudhari K, Das TK, Chandwadkar AJ, Sivasanker S, J. Catal., 186(1), 81 (1999)

[12] Satokawa S, Itabashi K, Microporous Mater., 8, 49 (1997)

[13] Kuznicki SM, Thrush KA, U.S. Patent No., 5,244,650 (1993)

[14] Webb PA, Orr C, Analytical methods in fine particle technology, Micromeritics Instrument Corporation, Norcross, GA USA, 1997, pp. 53-153

[15] Felix SP, Savill-Jowitt C, Brown DR, Thermochim. Acta, 433(1-2), 59 (2005)

[16] Chon H, Catalysis an Introduction, 2nd ed, Hanrimwon, Seoul, 1992, pp. 370-374

[17] Kim WJ, Kim YS, J. Korean Ind. Eng. Chem., 9(1), 33 (1998)

[18] Rocha J, Anderson MW, Eur. J. Inorg. Chem., 801 (2000)

[19] Philippou A, Rocha J, Anderson MW, Catal. Lett., 57(3), 151 (1999)

[20] Thompson RW, in Karge, H.G., and Weitkamp, J., Eds., Molecular Sieves Science and Technology, Vol.1, Springer-Verlag, Berlin Heidelberg, 1-33 (1998)