고온석탄가스에서 아연계 탈황제에 의한 H<SUB>2</SUB>S의 제거

이태진; 박노국; 김장희; 김기석; 박영우; 이창근

HWAHAK KONGHAK, Vol.34, No.4, 435-442, August, 1996

Export Citation

고온석탄가스에서 아연계 탈황제에 의한 H₂S의 제거

Re- moval of H₂S by Zinc-Based Sorbents from High Temperature Coal-Derived Gases

이태진, 박노국, 김장희, 김기석, 박영우, 이창근

초록

복합금속산화물인 zinc ferrite와 zinc titanate 탈황제를 사용하여 석탄가스에서 H₂S의 제거 가능성을 연구하였다. 고온가스에 함유한 H₂S와 탈황제의 반응에 있어서 최적반응온도를 찾기 위해서 500-750℃ 범위에서 조사하였으며, 실험결과 zinc ferrite와 zinc titanate의 H₂S제거 효율은 각각 550℃와 650℃에서 최적조건을 나타내었다. 또한 SEM과 BET분석을 통해서도 최적온도에 대한 입자의 특징을 확인할 수 있었다. 황하-재생의 연속반응 10-cycle 실험은 탈황제의 연속적인 사용가능성을 평가하기 위해서 충전층 반응기에서 수행하였으며 표본시료에 대한 BET표면적, XRD, SEM 등의 분석도 같이 수행하였다. 황화-재생반응의 cycle이 반복되는 동안 zinc ferrite는 탈황제의 화학적 변형으로 인해서 황수용 능력이 증가하는 특이한 결과가 나타났으며, zinc titanate는 연속적인 cycle에서 거의 일정한 황수용 능력을 보였다.

Removal of H₂S by mixed-metal oxides was studied experimentally to demonstrate the potential use of zinc ferrite and zinc titanate as a sorbent in high temperature desulfuri- zation of coal gas. To find optimal temperature, the reactions of sorbents with a hot gas con- taining H₂S were investigated over a temperature range of 500-750℃. The experimental results showed that optimal H₂S removal efficiency of zinc ferrite and zinc titanate sorbents was obtained at 550℃ and 650℃ respectively, and SEM and BET analyses were in accord with this feature. Ten cycles of sulfidation and regeneration were sequentially conducted in the packed-bed reactor to determine the long-term performance of the sorbents. A series of characterizations were also performed sample including BET surface area, XRD, and SEM. Zinc ferrite sorbent exhibited a significant rise in sulfur capacity during the repeated cycles of absorption and regeneration due to the chemical transformations of the sorbent, while zinc ti- tanate sorbent showed nearly constant sulfur capacity with the successive cycle operation.

Keywords:H₂S Removal;Zinc Ferrite;Zinc Titanate;Absorption and Regeneration

[References]

이인철, 진경태, 손재익, "미국의 청정석탄 활용기술현황," 제 3회 신, 재생에너지기술 개발 및 동향에 관한 세미나, 한국에너지기술연구소, 12-1 (1990)
박영성, 이태진, "석탄가스화 복합발전용 고온건식탈황기술 개발(I)," 한국전력공사 기술연구원 보고서, p. 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, Vol. 1, p. 337-350 (1994)
Grindley T, Everitt CE, "Absorption of Hydrogen Sulfide by Zinc Ferrite in the Temperature Range 315 to 538℃," Proceeding of the Coal-Fired Power Systems 94 - Advances in IGCC and PFBC Review Meeting, DOE/METC 94/1008, Vol. 1, p. 431-443 (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/METC93/6131, p. 315-325 (1993)
Sa LN, Focht GD, Ranade PV, Harrison DP, Chem. Eng. Sci., 44(2), 215 (1989)
Haldipur GB, "KRW Process Development Coal Gasi-fication Hot-Gas Cleanup," Proceedings of the Seventh Annual Gasification and Gas Stream Cleanup Systems Contractors' Review Meeting, DOE/METC87/66079, Vol. 2, p. 668-677 (1992)
Wu JC, Robin AM, Kassman JS, "Integration and Testing of Hot Gas Desulfurization and Entrained Flow Gasification for Power Generation Systems," Proceedings of the Ninth Annual Gasification and Gas Stream Cleanup Systems Contractors' Review Meeting, DOE/METC89/6106, Vol. 1 (1989)
Robin AM, Jung DY, Kassman JS, Leininger TF, Wolfenbarger JK, Yang PP, "Integration and Testing of Hot Desulfurization and Entrained Flow Gasification for Power Generation Systems," Proceedings of the Twelfth Annual Gasification and Gas Stream Cleanup Systems Contractors' Review Meeting, DOE/METC92/6128, Vol. 1, p. 95-104 (1992)
Gupta RP, Gangwal SK, "Fluidizable Zinc Titanate Materials with High Chemical Reactivity and Attrition Resistance," U.S. Patent, No. 5,254,516 (1993)
Campbell WM, O'Donnell JJ, Katta S, Grindley T, Delzer G, Khare G, "Desulfurization of Hot Fuel Gas with Z-Sorb-III Sorbent," Proceedings of the Coal-Fired Power Systems 93 - Advances in IGCC and PFBC Review Meeting, DOE/METC 93/6131, p. 179-190 (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 R, "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/METC93/6131, p. 146-157 (1993)
Ayala RE, Gal E, Gupta RP, "Testing 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, p. 136-145 (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 Desulfurization 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)
Woods MC, Leese KE, Gangwal SK, Harrison DP, Jothimurugesan K, "Reaction Kinetics and Simulation Models for Novel High Temperature Desulfurization Sorbents," Final Report to DOE/METC, DOE/MC/24160-2671 (1989)

[Referenced By]

[1] 이인철, 진경태, 손재익, "미국의 청정석탄 활용기술현황," 제 3회 신, 재생에너지기술 개발 및 동향에 관한 세미나, 한국에너지기술연구소, 12-1 (1990)

[2] 박영성, 이태진, "석탄가스화 복합발전용 고온건식탈황기술 개발(I)," 한국전력공사 기술연구원 보고서, p. 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, Vol. 1, p. 337-350 (1994)

[4] Grindley T, Everitt CE, "Absorption of Hydrogen Sulfide by Zinc Ferrite in the Temperature Range 315 to 538℃," Proceeding of the Coal-Fired Power Systems 94 - Advances in IGCC and PFBC Review Meeting, DOE/METC 94/1008, Vol. 1, p. 431-443 (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/METC93/6131, p. 315-325 (1993)

[6] Sa LN, Focht GD, Ranade PV, Harrison DP, Chem. Eng. Sci., 44(2), 215 (1989)

[7] Haldipur GB, "KRW Process Development Coal Gasi-fication Hot-Gas Cleanup," Proceedings of the Seventh Annual Gasification and Gas Stream Cleanup Systems Contractors' Review Meeting, DOE/METC87/66079, Vol. 2, p. 668-677 (1992)

[8] Wu JC, Robin AM, Kassman JS, "Integration and Testing of Hot Gas Desulfurization and Entrained Flow Gasification for Power Generation Systems," Proceedings of the Ninth Annual Gasification and Gas Stream Cleanup Systems Contractors' Review Meeting, DOE/METC89/6106, Vol. 1 (1989)

[9] Robin AM, Jung DY, Kassman JS, Leininger TF, Wolfenbarger JK, Yang PP, "Integration and Testing of Hot Desulfurization and Entrained Flow Gasification for Power Generation Systems," Proceedings of the Twelfth Annual Gasification and Gas Stream Cleanup Systems Contractors' Review Meeting, DOE/METC92/6128, Vol. 1, p. 95-104 (1992)

[10] Gupta RP, Gangwal SK, "Fluidizable Zinc Titanate Materials with High Chemical Reactivity and Attrition Resistance," U.S. Patent, No. 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-Sorb-III Sorbent," Proceedings of the Coal-Fired Power Systems 93 - Advances in IGCC and PFBC Review Meeting, DOE/METC 93/6131, p. 179-190 (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 R, "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/METC93/6131, p. 146-157 (1993)

[14] Ayala RE, Gal E, Gupta RP, "Testing 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, p. 136-145 (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 Desulfurization 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] Woods MC, Leese KE, Gangwal SK, Harrison DP, Jothimurugesan K, "Reaction Kinetics and Simulation Models for Novel High Temperature Desulfurization Sorbents," Final Report to DOE/METC, DOE/MC/24160-2671 (1989)