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Experimental study of the supercritical water reforming of glycerol without the addition of a catalyst

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  • Gutiérrez Ortiz, F.J.
  • Serrera, A.
  • Galera, S.
  • Ollero, P.

Abstract

Hydrogen production from the supercritical water reforming of glycerol was studied in a tubular reactor without adding a catalyst. Experiments were carried out at a pressure of 240bar, temperatures of 750–850°C, and glycerol feed concentrations of 5–30wt.%. Likewise, the residence time was changed from 12 to 160s, by handling the feed flow-rate. The dry gas is mainly consisted of H2, CO2, CO, CH4. In addition, small concentrations of glycerol were measured in the liquid phase analysis, but barely traces of others like glycolaldehyde, glyceraldehyde, dihydroxyacetone and lactic acid were detected. Thus, two probable reaction pathways are discussed, which makes it possible to explain the experimental results by using a method applicable to other similar processes. The results showed that the glycerol conversion was almost complete, except at the highest glycerol feed concentration, in which the conversion was of 88%. Hydrogen yields from 2 to 4molH2/molglycerol were obtained at high and low glycerol feed concentrations, respectively, when operating at high temperature and residence time. Besides, it was verified the catalytic effect of the reactor material (Inconel 625) from the trend of the gas product yields with time and the structured carbon nanotubes encountered. The catalytic activity of the reactor material was decreasing to reach a steady state after a few tens of operating hours. This study illustrates that the reforming of glycerol using supercritical water without added catalyst is feasible to achieve a high-yield hydrogen production, and it encourages to continue the research line, to obtain a process economically interesting.

Suggested Citation

  • Gutiérrez Ortiz, F.J. & Serrera, A. & Galera, S. & Ollero, P., 2013. "Experimental study of the supercritical water reforming of glycerol without the addition of a catalyst," Energy, Elsevier, vol. 56(C), pages 193-206.
    • Handle: RePEc:eee:energy:v:56:y:2013:i:c:p:193-206
    DOI: 10.1016/j.energy.2013.04.046
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    3. Serrera, A. & Gutiérrez Ortiz, F.J. & Ollero, P., 2014. "Syngas methanation from the supercritical water reforming of glycerol," Energy, Elsevier, vol. 76(C), pages 584-592.
    4. Zhang, Fengming & Xu, Chunyan & Zhang, Yong & Chen, Shouyan & Chen, Guifang & Ma, Chunyuan, 2014. "Experimental study on the operating characteristics of an inner preheating transpiring wall reactor for supercritical water oxidation: Temperature profiles and product properties," Energy, Elsevier, vol. 66(C), pages 577-587.
    5. Schwengber, Carine Aline & Alves, Helton José & Schaffner, Rodolfo Andrade & da Silva, Fernando Alves & Sequinel, Rodrigo & Bach, Vanessa Rossato & Ferracin, Ricardo José, 2016. "Overview of glycerol reforming for hydrogen production," Renewable and Sustainable Energy Reviews, Elsevier, vol. 58(C), pages 259-266.
    6. Ojani, Reza & Hasheminejad, Ehteram & Raoof, Jahan Bakhsh, 2015. "Direct growth of 3D flower-like Pt nanostructures by a template-free electrochemical route as an efficient electrocatalyst for methanol oxidation reaction," Energy, Elsevier, vol. 90(P1), pages 1122-1131.
    7. Mohsin Raza & Abrar Inayat & Basim Abu-Jdayil, 2021. "Crude Glycerol as a Potential Feedstock for Future Energy via Thermochemical Conversion Processes: A Review," Sustainability, MDPI, vol. 13(22), pages 1-27, November.
    8. Florentina Maxim & Iuliana Poenaru & Elena Ecaterina Toma & Giuseppe Stefan Stoian & Florina Teodorescu & Cristian Hornoiu & Speranta Tanasescu, 2021. "Functional Materials for Waste-to-Energy Processes in Supercritical Water," Energies, MDPI, vol. 14(21), pages 1-23, November.
    9. Gutiérrez Ortiz, F.J. & Campanario, F.J. & Aguilera, P.G. & Ollero, P., 2015. "Hydrogen production from supercritical water reforming of glycerol over Ni/Al2O3–SiO2 catalyst," Energy, Elsevier, vol. 84(C), pages 634-642.
    10. Xu, Jialing & Rong, Siqi & Sun, Jingli & Peng, Zhiyong & Jin, Hui & Guo, Liejin & Zhang, Xiang & Zhou, Teng, 2022. "Optimal design of non-isothermal supercritical water gasification reactor: From biomass to hydrogen," Energy, Elsevier, vol. 244(PB).
    11. Silva, Joel M. & Soria, M.A. & Madeira, Luis M., 2015. "Challenges and strategies for optimization of glycerol steam reforming process," Renewable and Sustainable Energy Reviews, Elsevier, vol. 42(C), pages 1187-1213.
    12. Knez, Ž. & Markočič, E. & Leitgeb, M. & Primožič, M. & Knez Hrnčič, M. & Škerget, M., 2014. "Industrial applications of supercritical fluids: A review," Energy, Elsevier, vol. 77(C), pages 235-243.
    13. Gutiérrez Ortiz, F.J. & Campanario, F.J. & Aguilera, P.G. & Ollero, P., 2016. "Supercritical water reforming of glycerol: Performance of Ru and Ni catalysts on Al2O3 support," Energy, Elsevier, vol. 96(C), pages 561-568.
    14. Ju, Jianfeng & Chen, Xi & Shi, Yujun & Wu, Donghui & Hua, Ping, 2013. "A novel TiO2 nanofiber supported PdAg catalyst for methanol electro-oxidation," Energy, Elsevier, vol. 59(C), pages 478-483.

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