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Title: Aqueous Phase Reforming of Glycerol for Hydrogen Production Over Pt-Re Supported on Carbon

Abstract

Hydrogen production from the aqueous phase reforming of glycerol over several 3%Pt-Re/C catalysts (1-4.5% Re) has been studied in the absence and presence of base, and the results compared with a Re-free 3%Pt/C catalyst. Although the Pt/C catalyst is very selective toward the production of hydrogen, catalytic activity is low. Addition of Re significantly increases the conversion of glycerol, at some loss of hydrogen selectivity to light hydrocarbons and water-soluble oxygenates. Addition of 1%KOH to the feedstock increases the selectivity of the Pt-Re/C catalysts toward hydrogen, but selectivity toward aqueous phase oxygenates also increases except for 3%Pt-3%Re/C, where it remains constant. The increase in hydrogen selectivity with base addition arises primarily from reducing the selectivity toward methane and higher alkanes, products that consume H2. For comparison, KOH addition to the glycerol feed with the Re-free 3%Pt/C catalyst provides an increase in glycerol conversion but results in a decline in both H2 and alkanes relative to aqueous phase oxygenates. This indicates that alternative pathways have been enabled by base addition. The highest hydrogen productivity among the catalysts tested is achieved with a 3%Pt-3%Re/C catalyst with added KOH base, but this hydrogen productivity declines with time on stream. The observed product distributionsmore » as well as deactivation with base can be understood in terms of the different reaction pathways that become emphasized depending on catalyst composition and pH.« less

Authors:
; ; ; ; ; ; ;
Publication Date:
Research Org.:
Pacific Northwest National Lab. (PNNL), Richland, WA (United States)
Sponsoring Org.:
USDOE
OSTI Identifier:
992358
Report Number(s):
PNNL-SA-71141
Journal ID: ISSN 0926-3373; ACBEE3; EB4201000; TRN: US201022%%284
DOE Contract Number:
AC05-76RL01830
Resource Type:
Journal Article
Resource Relation:
Journal Name: Applied Catalysis. B, Environmental, 99(1-2):206-213; Journal Volume: 99; Journal Issue: 1-2
Country of Publication:
United States
Language:
English
Subject:
08 HYDROGEN; 03 NATURAL GAS; ALKANES; CARBON; CATALYSTS; DEACTIVATION; GLYCEROL; HYDROCARBONS; HYDROGEN; HYDROGEN PRODUCTION; METHANE; PRODUCTION; PRODUCTIVITY

Citation Formats

King, David L., Zhang, Liang, Xia, Guanguang, Karim, Ayman M., Heldebrant, David J., Wang, Xianqin, Peterson, Thomas H., and Wang, Yong. Aqueous Phase Reforming of Glycerol for Hydrogen Production Over Pt-Re Supported on Carbon. United States: N. p., 2010. Web. doi:10.1016/j.apcatb.2010.06.021.
King, David L., Zhang, Liang, Xia, Guanguang, Karim, Ayman M., Heldebrant, David J., Wang, Xianqin, Peterson, Thomas H., & Wang, Yong. Aqueous Phase Reforming of Glycerol for Hydrogen Production Over Pt-Re Supported on Carbon. United States. doi:10.1016/j.apcatb.2010.06.021.
King, David L., Zhang, Liang, Xia, Guanguang, Karim, Ayman M., Heldebrant, David J., Wang, Xianqin, Peterson, Thomas H., and Wang, Yong. 2010. "Aqueous Phase Reforming of Glycerol for Hydrogen Production Over Pt-Re Supported on Carbon". United States. doi:10.1016/j.apcatb.2010.06.021.
@article{osti_992358,
title = {Aqueous Phase Reforming of Glycerol for Hydrogen Production Over Pt-Re Supported on Carbon},
author = {King, David L. and Zhang, Liang and Xia, Guanguang and Karim, Ayman M. and Heldebrant, David J. and Wang, Xianqin and Peterson, Thomas H. and Wang, Yong},
abstractNote = {Hydrogen production from the aqueous phase reforming of glycerol over several 3%Pt-Re/C catalysts (1-4.5% Re) has been studied in the absence and presence of base, and the results compared with a Re-free 3%Pt/C catalyst. Although the Pt/C catalyst is very selective toward the production of hydrogen, catalytic activity is low. Addition of Re significantly increases the conversion of glycerol, at some loss of hydrogen selectivity to light hydrocarbons and water-soluble oxygenates. Addition of 1%KOH to the feedstock increases the selectivity of the Pt-Re/C catalysts toward hydrogen, but selectivity toward aqueous phase oxygenates also increases except for 3%Pt-3%Re/C, where it remains constant. The increase in hydrogen selectivity with base addition arises primarily from reducing the selectivity toward methane and higher alkanes, products that consume H2. For comparison, KOH addition to the glycerol feed with the Re-free 3%Pt/C catalyst provides an increase in glycerol conversion but results in a decline in both H2 and alkanes relative to aqueous phase oxygenates. This indicates that alternative pathways have been enabled by base addition. The highest hydrogen productivity among the catalysts tested is achieved with a 3%Pt-3%Re/C catalyst with added KOH base, but this hydrogen productivity declines with time on stream. The observed product distributions as well as deactivation with base can be understood in terms of the different reaction pathways that become emphasized depending on catalyst composition and pH.},
doi = {10.1016/j.apcatb.2010.06.021},
journal = {Applied Catalysis. B, Environmental, 99(1-2):206-213},
number = 1-2,
volume = 99,
place = {United States},
year = 2010,
month = 3
}
  • Gold particles supported on carbon and titania were explored as catalysts for oxidation of CO or glycerol by O{sub 2} at room temperature in liquid-phase water. Although Au/carbon catalysts were not active for vapor phase CO oxidation at room temperature, a turnover frequency of 5 s{sup -1} could be achieved with comparable CO concentration in aqueous solution containing 1 M NaOH. The turnover frequency on Au/carbon was a strong function of pH, decreasing by about a factor of 50 when the pH decreased from 14 to 0.3. Evidently, a catalytic oxidation route that was not available in the vapor phasemore » is enabled by operation in the liquid water at high pH. Since Au/titania is active for vapor phase CO oxidation, the role of water, and therefore hydroxyl concentration, is not as significant as that for Au/carbon. Hydrogen peroxide is also produced during CO oxidation over Au in liquid water and increasing the hydroxyl concentration enhances its formation rate. For glycerol oxidation to glyceric acid (C{sub 3}) and glycolic acid (C{sub 2}) with O{sub 2} (1-10 atm) at 308-333 K over supported Au particles, high pH is required for catalysis to occur. Similar to CO oxidation in liquid water, H{sub 2}O{sub 2} is also produced during glycerol oxidation at high pH. The formation of the C-C cleavage product glycolic acid is attributed to peroxide in the reaction.« less
  • In this paper we examine the feasibility of steam reforming the mixed oxygenate aqueous fraction derived from fast pyrolysis bio-oils. Catalysts selective towards hydrogen formation and resistant to carbon formation utilizing feeds with relatively low steam-to-carbon (S/C) ratios are desired. Rh (5 wt%), Pt (5 wt%), Ru (5 wt%), Ir (5 wt%), Ni (15 wt%), and Co (15 wt%) metals supported on MgAl2O4 were evaluated for catalytic performance at 500 °C and 1 atm using a complex feed mixture comprising acids, polyols, cycloalkanes, and phenolic compounds. The Rh catalyst was found to be the most active and resistant to carbonmore » formation. The Ni and Co catalysts were found to be more active than the other noble metal catalysts investigated (Pt, Ru, and Ir).« less
  • In this study we examine feasibility for steam reforming the mixed oxygenate aqueous fraction derived from mildly hydrotreated fast pyrolysis bio-oils. Catalysts selective towards hydrogen formation and resistant to carbon formation utilizing feeds with relatively low steam-to-carbon (S/C) ratios are desired. Rh (5 wt%), Pt (5 wt%), Ru (5 wt%), Ir (5 wt%), Ni (15 wt%), and Co (15 wt%) metals supported on MgAl 2O 4 were evaluated for catalytic performance at 500°C and 1 atm using a complex feed mixture comprising of acids, polyols, cycloalkanes, and phenolic compounds. The Rh catalyst was found to be the most active andmore » resistant to carbon formation. The Ni and Co catalysts were found to be more active than the other noble metal catalysts investigated (Pt, Ru, and Ir). However, Ni was found to form significantly more carbon (coke) on the catalyst surface. Furthermore, Co was found to be the most selective towards H 2 formation. Evaluating the effect of temperature on stability for the Rh catalyst we found that catalyst stability was best when operated at 500°C as compared to the higher temperatures investigated (700, 800°C). When operating at 700°C significantly more graphitic formation was observed on the spent catalyst surface. Operating at 800°C resulted in reactor plugging as a result of thermal decomposition of the reactants. Thus, a concept analogous to the petroleum industries’ use of a pre-reformer, operated at approximately 500°C for steam reforming of the heavier naphtha components, followed by a high temperature methane reforming operated in the 600-850°C temperature range, could be applied in the case of steam reforming biomass derived oxygenates. Moreover, stability evaluations were performed over the Rh, Ni, and Co catalysts at 500°C and 1 atm, under similar initial conversions, reveal the Co catalyst to be the most stable and selective towards H 2 production. Conversion and selectivity to CH 4 over Co remained relatively stable at approximately 80% and 1.2%, respectively. By contrast, the Rh and Ni catalysts CH 4 selectivity’s were approximately 7-8%. Thus suggesting that a Co type catalyst may be more suitable for the steam reforming of biomass derived oxygenates as compared to the more conventional Ni and Rh type steam reforming catalysts. However, deposition of carbon on the surface was observed. High resolution TEM on the spent catalysts revealed the formation of graphitic carbon on the Rh catalyst, and filamentous carbon formation was observed on both the Ni and Co catalysts, albeit less pronounced on Co. Thus there is certainly opportunity for improvement in Co catalyst design and/or with process optimization.« less