화학공학소재연구정보센터
Clean Technology, Vol.23, No.1, 104-112, March, 2017
Ni-K2TixOy 촉매를 이용한 해조류 유래 수열 액화 원료의 수증기 개질 반응 연구
Steam Reforming of Hydrothermal Liquefaction Liquid from Macro Algae over Ni-K2TixOy Catalysts
E-mail:,
초록
해조류로부터 수열 액화 반응을 통해 생성된 원료를 이용하여 수소가스를 생산하기 위해 개질 반응용 상용화 촉매와 K2TixOy가 첨가된 니켈(Ni) 제조 촉매를 사용하여 반응온도에 따른 수증기 개질 반응을 수행하였다. 반응원료는 해조류 바이오매스를 503 K의 반응온도에서 2시간 동안 수열 액화를 통해 생성된 액화 원료를 사용하였으며, 상용화 촉매(FCR-4-02)와 제조 촉매(Ni/K2TixOy-Al2O3, Ni/K2TixOy-SiO2, Ni/K2TixOy-ZrO2/CeO2, Ni/K2TixOy-MgO) 및 반응온도에 따른 수증기 개질반응의 활성을 비교 연구하였다. 실험결과 제조 촉매 4종 모두 상용화 촉매와 비교하여 반응활성이 높게 나타나는 것이 확인되었으며, 제조 촉매의 지지체에 따라 생성되는 가스의 조성이 달라지는 것이 확인되었다. 특히, 산성이나 염기성을 띄는 Al2O3와 MgO의 지지체와 중성을 띄는 SiO2의 지지체에서는 CO가 선택적으로 높게 생성이 되었으며 환원성을 띄는 CeO2 를 포함하는 지지체에서는 수성가스 전환 반응이 일어나 CO2가 높게 생성됨을 보였다.
Hydrogen production via steam reforming of liquefaction liquid from marine algae over hydrothermal liquefaction was carried out at 873 ~ 1073 K with a commercial catalyst and Ni based K2TixOy added catalysts. Liquefaction liquid obtained by hydrothermal liquefaction (503 K, 2 h) was used as a reactant and comparison studies for catalytic activity over different catalysts (FCR-4-02, Ni/K2TixOy-Al2O3, Ni/K2TixOy-SiO2, Ni/K2TixOy-ZrO2/CeO2 and Ni/K2TixOy-MgO), reaction temperature were performed. Experimental results showed Ni/K2TixOy based catalysts (Ni/K2TixOy-Al2O3, Ni/K2TixOy-SiO2, Ni/K2TixOy-ZrO2/CeO2 and Ni/K2TixOy-MgO) have a higher activity than commercial catalyst (FCR-4-02) and In particular, a product composition was different depending on support materials. An acidic support (Al2O3) and a basic support (MgO) led to a higher selectivity for CO while a neutral support (SiO2) and a reducing support (ZrO2/CeO2) resulted in a higher CO2 selectivity due to water gas shift reaction.
  1. Goyal N, Pant KK, Gupta R, Int. J. Hydrog. Energy, 38(2), 921 (2013)
  2. Heracleous E, Int. J. Hydrog. Energy, 36(18), 11501 (2011)
  3. Maximiliano M, Guido WS, Francese C, Daniel M, Green Chem., 4, 414 (2002)
  4. Bridgwater AV, Biomass Bioenerg., 38, 68 (2012)
  5. Czernik S, Evans R, French R, Catal. Today, 129(3-4), 265 (2007)
  6. Christensen JM, Mortensen PM, Trane R, Jensen PA, Jensen AD, Appl. Catal. A: Gen., 366(1), 29 (2009)
  7. Raffelt K, Henrich E, Kogel A, Stahl R, Steinhardt J, Weirich F, Appl. Biochem. Biotechnol., 129, 153 (2006)
  8. Song CS, Catal. Today, 77(1-2), 17 (2002)
  9. Li DL, Atake I, Shishido T, Oumi Y, Sano T, Takehira K, J. Catal., 250(2), 299 (2007)
  10. Juan-Juan J, Roman-Martinez MC, Illan-Gomez MJ, Appl. Catal. A: Gen., 301(1), 9 (2006)
  11. Li BT, Kado S, Mukainakano Y, Miyazawa T, Miyao T, Naito S, Okumura K, Kunimori K, Tomishige K, J. Catal., 245(1), 144 (2007)
  12. Mukainakano Y, Li BT, Kado S, Miyazawa T, Okumura K, Miyao T, Naito S, Kunimori K, Tomishige K, Appl. Catal. A: Gen., 318, 252 (2007)
  13. Tomishige K, Asadullah M, Kunimori K, Catal. Surv. Asia., 7, 219 (2003)
  14. Remiro A, Valle B, Oar-Arteta L, Aguayo AT, Bilbao J, Gayubo AG, Int. J. Hydrog. Energy, 39(13), 6889 (2014)
  15. Zhang FB, Wang N, Yang L, Li M, Huang LH, Int. J. Hydrog. Energy, 39(32), 18688 (2014)
  16. Kechagiopoulos PN, Voutetakis SS, Lemonidou AA, Vasalos IA, Energy Fuels, 20(5), 2155 (2006)
  17. Matsumura Y, Nakamori T, Appl. Catal. A: Gen., 258(1), 107 (2004)
  18. Kan T, Xiong JX, Li XL, Ye TQ, Yuan LX, Torimoto Y, Yamamoto M, Li QX, Int. J. Hydrog. Energy, 35(2), 518 (2010)
  19. Davidian T, Guilhaume N, Iojoiu E, Provendier H, Mirodatos C, Appl. Catal. B: Environ., 73(1-2), 116 (2007)
  20. Domine ME, Iojoiu EE, Davidian T, Guilhaume N, Mirodatos C, Catal. Today, 133, 565 (2008)
  21. Song MK, Pham HD, Seon J, Woo HC, Renew. Sust. Energ. Rev., 50, 782 (2015)
  22. Andersson S, Wadsley AD, Nature, 187, 499 (1960)
  23. Kim T, Song KH, Yoon H, Chung JS, Int. J. Hydrog. Energy, 41(40), 17922 (2016)
  24. Lee SY, Lim H, Woo HC, Int. J. Hydrog. Energy, 39(31), 17645 (2014)
  25. Ping L, Qingli X, Ming Z, Lihong L, Suping Z, Yongjie Y, Chem. Eng. Technol., 12, 2021 (2010)
  26. Park YB, Lim H, Woo HC, Korean Chem. Eng. Res., 54(1), 94 (2016)
  27. Vizcaino AJ, Arena P, Baronetti G, Carrero A, Calles JA, Laborde MA, Amadeo N, Int. J. Hydrog. Energy, 33, 3489 (2007)
  28. Swartz SL, “Nano-Scale Water-Gas-Shift Catalysts,” DOE CRAFT Program (2003).
  29. Dong WS, Roh HS, Jun KW, Park SE, Oh YS, Appl. Catal. A: Gen., 226(1-2), 63 (2002)