Korean Chemical Engineering Research

The Korean Institute of Chemical Engineers (한국화학공학회)
권호 표지
DOI QR코드

DOI QR Code

Hydrolysis Reaction of NaBH4 using Unsupported Co-B, Co-P-B Catalyst

비담지 Co-B, Co-P-B 촉매를 이용한 NaBH4 가수분해 반응

  • Oh, Sung-June (Department of Chemical Engineering, Sunchon National University) ;
  • Jung, Hyeon-Seong (Department of Chemical Engineering, Sunchon National University) ;
  • Jeong, Jae-Jin (Department of Chemical Engineering, Sunchon National University) ;
  • Na, Il-Chai (CNL Energy Co.) ;
  • Ahn, Ho-Geun (Department of Chemical Engineering, Sunchon National University) ;
  • Park, Kwon-Pil (Department of Chemical Engineering, Sunchon National University)
  • Received : 2014.08.14
  • Accepted : 2014.09.04
  • Published : 2015.02.01
Download PDF
⟨ Previous Next ⟩

Abstract

Sodium borohydride, $NaBH_4$, shows a number of advantages as hydrogen source for portable proton exchange membrane fuel cells(PEMFCs). Properties of $NaBH_4$ hydrolysis reaction using unsupported Co-B, Co-P-B catalyst were studied. BET surface area of catalyst, yield of hydrogen, effect of $NaBH_4$ concentration and durability of catalyst were measured. The BET surface area of unsupported Co-B catalyst was $75.7m^2/g$ and this value was 18 times higher than that of FeCrAlloy supported Co-B catalyst. The hydrogen yield of $NaBH_4$ hydrolysis reaction by unsupported catalysts using 20~25 wt% $NaBH_4$ solution was 97.6~98.5% in batch reactor. The hydrogen yield decrease to 95.3~97.0% as the concentration of $NaBH_4$ solution increase to 30 wt%. The loss of unsupported catalyst was less than that of FeCrAlloy supported catalyst during $NaBH_4$ hydrolysis reaction and the loss increased with increasing of $NaBH_4$ concentration. In continuous reactor, hydrogen yield of $NaBH_4$ hydrolysis was 90% using 1.2 g of unsupported Co-P-B catalyst with $3{\ell}/min$ hydrogen generation rate.

휴대용 고분자전해질 연료전지의 수소발생용으로써 $NaBH_4$는 많은 장점을 갖고 있다. 본 연구에서는 비담지 Co-B, Co-P-B 촉매의 $NaBH_4$ 가수분해 특성에 대해 연구하였다. 촉매의 BET 표면적, 수소 수율, $NaBH_4$ 농도 영향, 촉매 내구성 등을 실험하였다. 비담지 Co-B 촉매의 BET 표면적은 $75.7m^2/g$으로 FeCrAlloy에 담지한 Co-B 촉매에 비해 BET 면적이 18배 높았다. 회분식 반응기에서 비담지 촉매들은 $NaBH_4$ 20~25 wt% 사용조건에서 97.6~98.5%의 높은 수소 수율을 보였다. $NaBH_4$ 농도가 30 wt%로 증가하면서 수소수율은 95.3~97.0%로 감소하였다. 비담지 촉매의 촉매 손실율은 FeCrAlloy에 담지 촉매에 비해 낮았으며, $NaBH_4$ 농도가 증가하면서 촉매 손실율도 증가하였다. 연속 반응기에서 1.2 g 비담지 Co-P-B 촉매를 사용해서 약 $3{\ell}/min$ 발생속도로 가수분해 반응하여 90%의 수소 수율을 얻었다.

Keywords

References

  1. Aneesh C. Gangal, Raju Edla, Kartik Iyer, Rajesh Biniwale, Manvendra Vashistha and Pratibha Sharma, "Effect of Zeolites on Thermal Decomposition of Ammonia Borane," Int. J. Hydrog. Energy, 37, 3712-3718(2012). https://doi.org/10.1016/j.ijhydene.2011.04.011
  2. Fernandes, R., Patel, N., Miotello, A. and Filippi, M., "Studies on Catalytic Behavior of Co-Ni-B in Hydrogen Production by Hydrolysis of $NaBH_4$," J. Mol. Catal. A-Chem., 298, 1-6(2009). https://doi.org/10.1016/j.molcata.2008.09.014
  3. Fernandes, R., Patel, N., Miotello, A., Jaiswal, R. and Korthari, D. C., "Stability, Durability, and Reusability Studies on Transition Metal-doped Co-B Alloy Catalysts for Hydrogen Production," Int. J. Hydrog. Energy, 36, 13379-13391(2011). https://doi.org/10.1016/j.ijhydene.2011.08.021
  4. Fernandes, R., Patel, N. and Miotello, A., "Hydrogen Generation by Hydrolysis of Alkaline $NaBH_4$ Solution with Cr-promoted Co-B Amorphous Catalyst," Appl. Catal. B: Environ., 92, 68-74(2009). https://doi.org/10.1016/j.apcatb.2009.07.019
  5. Fernandes, R., Patel, N. and Miotello, A., "Efficient Catalytic Properties of Co-Ni-P-B Catalyst Powders for Hydrogen Generation by Hydrolysis of Alkaline Solution of $NaBH_4$," Int. J. Hydrog. Energy, 34, 2893-2900(2009). https://doi.org/10.1016/j.ijhydene.2009.02.007
  6. Moon, G. Y., Lee, S. S., Yang, G. R. and Song, K. H., "Effects of Organic Acid Catalysts on the Hydrogen Generation from $NaBH_4$," Korean J. Chem. Eng., 27(2), 474-479(2010). https://doi.org/10.1007/s11814-010-0072-3
  7. Demirci, U. B. and Garin, F., "Ru-based Bimetallic Alloys for Hydrogen Generation by Hydrolysis of Sodium Tetrahydroborate," J. Alloy. Compd., 463, 107-111(2008). https://doi.org/10.1016/j.jallcom.2007.08.077
  8. Ye, W., Zhang, H., Xu, D., Ma, L. and Yi, B., "Hydrogen Generation Utilizing Alkaline Sodium Borohydride Solution and Supported Cobalt Catalyst," J. Power Sources, 164, 544-548(2007). https://doi.org/10.1016/j.jpowsour.2006.09.114
  9. Simagina, V. I., Netskina, O. V., Komova, O. V., Odegova, G. V., Kochubei, D. I. and Ishchenko, A. V., "Activity of Rh/$TiO_2$ Catalysts in $NaBH_4$ Hydrolysis: The Effect of the Interaction Between $RhCl_3$ and the Anatase Surface During Heat Treatment," Kinet. Catal., 49(4), 568-573(2008). https://doi.org/10.1134/S0023158408040174
  10. Simagina, V. I., Storozhenko, P. A., Netskina, O. V., Komova, O. V., Odegova, G. V., Samoilenko, T. Yu. and Gentsler, A. G., "Effect of the Nature of the Active Component and Support on the Activity of Catalysts for the Hydrolysis of Sodium Borohydride," Kinet. Catal., 48(1), 168-175(2007). https://doi.org/10.1134/S0023158407010223
  11. Demirci, U. B. and Garin, F., "Promoted Sulphated-zirconia Catalysed Hydrolysis of Sodium Tetrahydroborate," Catal. Commun., 9(6), 1167-1172(2008). https://doi.org/10.1016/j.catcom.2007.10.028
  12. Chen, Y. and Kim, H., "Ni/Ag/Silica Nanocomposite Catalysts for Hydrogen Generation from Hydrolysis of $NaBH_4$ Solution," Mater. Lett., 62, 1451-1454(2008). https://doi.org/10.1016/j.matlet.2007.08.084
  13. Hwang, B. C., Jo, J. Y., Sin, S. J., Choi, D. K., Nam, S. W. and Park, K. P., "Study on the Hydrogen Yield of $NaBH_4$ Hydrolysis Reaction," Korean Chem. Eng. Res., 49(5), 516-520(2011). https://doi.org/10.9713/kcer.2011.49.5.516
  14. Hwang, B. C., Jo, A. R., Sin, S. J., Choi, D. K., Nam, S. W. and Park, K. P., "$NaBH_4$ Hydrolysis Reaction Using Co-P-B Catalyst Supported on FeCrAlloy," Korean Chem. Eng. Res., 51(1), 35-41(2013). https://doi.org/10.9713/kcer.2013.51.1.35
  15. Kim, S. J., Lee, J. Y., Kong, K. Y., Jung, C. R. Min, I. G., Lee, S. Y., Kim, H. J., Nam, S. W. and Lim, T. H., "Hydrogen Generation System Using Sodium Borohydride for Operation of a 400W-scale Polymer Electrolyte Fuel Cell Stack," J. Power Sources, 170, 412-418(2007). https://doi.org/10.1016/j.jpowsour.2007.03.083

Cited by

  1. 고농도 NaBH4 수용액에서 비담지 촉매의 가수분해 반응 특성 vol.54, pp.5, 2015, https://doi.org/10.9713/kcer.2016.54.5.587
  2. 활성탄 담지 Co-B/C, Co-P-B/C 촉매를 이용한 NaBH4 가수분해 반응 vol.56, pp.5, 2015, https://doi.org/10.9713/kcer.2018.56.5.641
  3. 바닷물을 이용한 NaBH4 가수분해에 의한 수소발생 vol.57, pp.6, 2015, https://doi.org/10.9713/kcer.2019.57.6.758