아연-티타늄 복합산화물 탈황제의 제조 및 반응특성 연구

김기석; 박노국; 이태진

Journal of the Korean Industrial and Engineering Chemistry, Vol.8, No.1, 122-131, February, 1997

Export Citation

아연-티타늄 복합산화물 탈황제의 제조 및 반응특성 연구

A Study on Preparation and Reactivity of Zinc Titanate Sorbents for H₂S Removal

김기석, 박노국, 이태진

초록

아연-티타늄 복합금속산화물 탈황제를 제조하여 석탄가스중의 H₂S를 제거하는 고온탈황성능을 연구하였다. H₂S 흡수에 의한 탈황제의 황화반응실험을 충전층 관형 흐름반응기를 사용하여 550∼750℃ 범위에서 수행한 결과 탈황율과 아연성분의 손실측면에서 650℃가 최적 황화반응 온도임이 밝혀졌다. SEM 분석에 의해서 650℃에서의 황화반응과 750℃에서의 재생반응에 따른 탈황제 입자의 구조변화를 관찰하였다. 탈황성능의 지속성과 탈황제 내구성을 평가하기 위하여 연속적인 황화-재생 cycle 반응실험을 수행하였으며 10번째 cycle 이후에 수거반 탈황제 시료의 특성을 BET, XRD, SEM/EDX에 의해서 분석하였다. 아연-티타늄 복합 산화물 탈황제는 연속적인 황화-재생 cycle 동안에 거의 일정한 탈황성능을 나타내었다.

Zinc titanate sorbents for H₂S removal were prepared and their reactivities were studied for high temperature desulfurization of coal gas. Sulfidation of zinc titanates by H₂S sorption was conducted in a packed-bed tubular flow reactor at the temperature range of 550∼750℃, and the results reveal that 650℃ was the optimal sulfidation temperature with respect to desulfurization efficiency and zinc loss. The structural change of sorbent particle was investigated by SEM analysis for the forbents sulfided at 650℃ and subsequently regenerated at 750℃. The stability of desulfurization capability as well as the mechanical stability of the zinc titanates was studied by means of the successive cycles of sulfidation-regeneration of sorbents, and the sorbent samples taken after the 10th cycle were characterized using BET, XRD, and SEM/EDX analyses. Zinc titanate sorbents exhibited nearly constant desulfurization capability in the successive cycle operation.

[References]

이인철, 진경태, 손재익, "미국의 청정 석탄활용 기술현황," 제 3회 신·재생에너지기술개발 및 동향에 관한 세미나, 한국에너지기술연구소, 12-1 (1990)
박영성, 이태진, "석탄가스화 복합발전용 고온건식탈황기술 개발(Ⅰ)," 한국전력공사기술연구원 보고서, 1 (1994)
Hepworth MT, Ben-Silmane R, "Hot Coal Gas Desulfurization with Manganese-Based Sorbents," Proceeding of the Coal-Fired Power Systems 94-Advances in IGCC and PFBC Review Meeting, DOE/METC 94/1008, 1, 337 (1994)
Grindley T, Everitt CE, "Absorption of Hydrogen Sulfide by Zinc Ferrite in the Temperature Range 315 to 538 ℃," Proceedings of the Coal-Fired Power Systems 94-Advances in IGCC and PFBC Review Meeting, DOE/METC 94/1008, 1, 431 (1994)
Mei JS, Gasper-Galvin LD, Everitt CE, Katta S, "Fixed-Bed Testing of a Molybdenum-Promoted Zinc Titanate Sorbent for Hot Gas Desulfurization," Proceedings of the Coal-Fired Power Systems 93-Advances in IGCC and PFBC Review Meeting, DOE/METC 93/6131, 315 (1993)
Sa LN, Focht GD, Ranade PV, Harrision DP, Chem. Eng. Sci., 44, 215 (1989)
Haldipur GB, "KRW Process Development Coal Gasification Hot-Gas Cleanup," Proceedings of the Seventh Annual Gasification and Gas Stream Cleanup Systems Contractors' Review Meeting, DOE/METC 87/66079, 2, 668 (1992)
Wu JC, Robin AM, Kassman JS, "Integration and Testing of Hot Gas Desulfurization and Engrained Flow Gasification for Power Generation Systems," Proceedings of the Nineth Annual Gasification and Gas Stream Cleanup Systems Contractors' Review MEeting, DOE/METC 89/6106, 1 (1989)
Robin AM, Jung DY, Kassman JS, Leininger TF, Wolfenbarger JK, Yang PP, "Integration and Testing of Hot Gas Desulfurization and Entrained Flow Gasification for Power Generation Systems," Proceedings of the Twelfth Annual Gasification and Gas Stream Cleanup Systems Contractors' Review Meeting, DOE/METC 92/6128, 1, 95 (1992)
Gupta RP, Gangwal SK, "Fluidizable Zinc Titanate Materials with High Chemical Reactivity and Attrition Resistance," U.S. Patent, 5,254,516 (1993)
Campbell WM, O'Donnell JJ, Katta S, Grindley T, Delzer G, Khare G, "Desulfurization of Hot Fuel Gas with Z-SorbIII Sorbent," Proceedings of the Coal-Fired Power Systems 93-Advances in IGCC and PFBC Review Meeting, DOE/METC 93/6131, 179 (1993)
Gupta RP, Gangwal SK, "High-Temperature, High-Pressure Testing of Zinc Titanate in a Bench-Scale Fluidized-Bed Reactor for 100 Cycles," Topical Report to DOE/METC, Contract No. DE-AC21-88MC25006, June (1993)
Gangwal SK, Gupta RP, "Enhanced Durability of High-Temperature Desulfurization Sorbents for Fluidized-Bed Applications," Proceedings of the Coal-Fired Power Systems 93-Advances in IGCC and PFBC Review Meeting, DOE/METC 93/6131, 136 (1993)
Ayala RE, Gal E, Gupta RP, "Texting of Zinc Titanate Desulfurization Sorbents for Moving-Bed Applications," Proceedings of the Coal-Fired Power Systems 93-Advances in IGCC and PFBC Review Meeting, DOE/METC 93/6131, 136 (1993)
Gupta RP, Gangwal SK, "Enhanced Durability of High-Temperature Desulfurization Sorbents for Fluidized-Bed Applications," Topical Report to METC, Contract No. DE-AC21-88MC25006, November (1992)
Ayala RE, "Enhanced Durability of High-Temperature Desulurization Sorbents for Moving-Bed Applications Option 2 Program : Development and Testing of Zinc Titanate Sorbents," Topical Report to METC, Contract No. DE-AC21-88MC25003, April (1992)
지평삼, "석탄가스화 복합발전 기술개발 (Ⅰ)," 한국전력공사기술연구원보고서, KRC-92G-J11, 170 (1994)
Gangwal SK, private communications

[Referenced By]

[1] 이인철, 진경태, 손재익, "미국의 청정 석탄활용 기술현황," 제 3회 신·재생에너지기술개발 및 동향에 관한 세미나, 한국에너지기술연구소, 12-1 (1990)

[2] 박영성, 이태진, "석탄가스화 복합발전용 고온건식탈황기술 개발(Ⅰ)," 한국전력공사기술연구원 보고서, 1 (1994)

[3] Hepworth MT, Ben-Silmane R, "Hot Coal Gas Desulfurization with Manganese-Based Sorbents," Proceeding of the Coal-Fired Power Systems 94-Advances in IGCC and PFBC Review Meeting, DOE/METC 94/1008, 1, 337 (1994)

[4] Grindley T, Everitt CE, "Absorption of Hydrogen Sulfide by Zinc Ferrite in the Temperature Range 315 to 538 ℃," Proceedings of the Coal-Fired Power Systems 94-Advances in IGCC and PFBC Review Meeting, DOE/METC 94/1008, 1, 431 (1994)

[5] Mei JS, Gasper-Galvin LD, Everitt CE, Katta S, "Fixed-Bed Testing of a Molybdenum-Promoted Zinc Titanate Sorbent for Hot Gas Desulfurization," Proceedings of the Coal-Fired Power Systems 93-Advances in IGCC and PFBC Review Meeting, DOE/METC 93/6131, 315 (1993)

[6] Sa LN, Focht GD, Ranade PV, Harrision DP, Chem. Eng. Sci., 44, 215 (1989)

[7] Haldipur GB, "KRW Process Development Coal Gasification Hot-Gas Cleanup," Proceedings of the Seventh Annual Gasification and Gas Stream Cleanup Systems Contractors' Review Meeting, DOE/METC 87/66079, 2, 668 (1992)

[8] Wu JC, Robin AM, Kassman JS, "Integration and Testing of Hot Gas Desulfurization and Engrained Flow Gasification for Power Generation Systems," Proceedings of the Nineth Annual Gasification and Gas Stream Cleanup Systems Contractors' Review MEeting, DOE/METC 89/6106, 1 (1989)

[9] Robin AM, Jung DY, Kassman JS, Leininger TF, Wolfenbarger JK, Yang PP, "Integration and Testing of Hot Gas Desulfurization and Entrained Flow Gasification for Power Generation Systems," Proceedings of the Twelfth Annual Gasification and Gas Stream Cleanup Systems Contractors' Review Meeting, DOE/METC 92/6128, 1, 95 (1992)

[10] Gupta RP, Gangwal SK, "Fluidizable Zinc Titanate Materials with High Chemical Reactivity and Attrition Resistance," U.S. Patent, 5,254,516 (1993)

[11] Campbell WM, O'Donnell JJ, Katta S, Grindley T, Delzer G, Khare G, "Desulfurization of Hot Fuel Gas with Z-SorbIII Sorbent," Proceedings of the Coal-Fired Power Systems 93-Advances in IGCC and PFBC Review Meeting, DOE/METC 93/6131, 179 (1993)

[12] Gupta RP, Gangwal SK, "High-Temperature, High-Pressure Testing of Zinc Titanate in a Bench-Scale Fluidized-Bed Reactor for 100 Cycles," Topical Report to DOE/METC, Contract No. DE-AC21-88MC25006, June (1993)

[13] Gangwal SK, Gupta RP, "Enhanced Durability of High-Temperature Desulfurization Sorbents for Fluidized-Bed Applications," Proceedings of the Coal-Fired Power Systems 93-Advances in IGCC and PFBC Review Meeting, DOE/METC 93/6131, 136 (1993)

[14] Ayala RE, Gal E, Gupta RP, "Texting of Zinc Titanate Desulfurization Sorbents for Moving-Bed Applications," Proceedings of the Coal-Fired Power Systems 93-Advances in IGCC and PFBC Review Meeting, DOE/METC 93/6131, 136 (1993)

[15] Gupta RP, Gangwal SK, "Enhanced Durability of High-Temperature Desulfurization Sorbents for Fluidized-Bed Applications," Topical Report to METC, Contract No. DE-AC21-88MC25006, November (1992)

[16] Ayala RE, "Enhanced Durability of High-Temperature Desulurization Sorbents for Moving-Bed Applications Option 2 Program : Development and Testing of Zinc Titanate Sorbents," Topical Report to METC, Contract No. DE-AC21-88MC25003, April (1992)

[17] 지평삼, "석탄가스화 복합발전 기술개발 (Ⅰ)," 한국전력공사기술연구원보고서, KRC-92G-J11, 170 (1994)

[18] Gangwal SK, private communications