TY - JOUR
T1 - Upgrading of pyrolysis bio-oil using nickel phosphide catalysts
AU - Koike, Natsume
AU - Hosokai, Sou
AU - Takagaki, Atsushi
AU - Nishimura, Shun
AU - Kikuchi, Ryuji
AU - Ebitani, Kohki
AU - Suzuki, Yoshizo
AU - Oyama, S. Ted
N1 - Funding Information:
This work was supported by Development of Next-generation Technology for Strategic Utilization of Biomass Energy of New Energy and Industrial Technology Development Organization (NEDO), Japan and a Grant-in-Aid for Scientific Research (B) (no. 26289301 ) of JSPS , Japan. STO received support from the National Science Foundation under grant CHE-1361842 and the U.S. Department of Energy under grant DE-FG02-96ER14669 .
Funding Information:
The catalyst precursors were prepared at Japan Gas Company Catalysts and Chemicals (JG-CCC) and kindly supplied by Y. Shirahama, S. Yabe. The TEM pictures in this work were taken in Research Hub for Advanced Nano Characterization, The University of Tokyo, supported by the Ministry of Education, Culture, Sports, Science, and Technology (MEXT), Japan. The authors thank Dr. Akio Miyazato (Nano-center, JAIST) for his help in FT-ICR MS experiments.
Publisher Copyright:
© 2015 Elsevier Inc.
PY - 2016/1/1
Y1 - 2016/1/1
N2 - Pyrolysis bio-oil is a promising source of liquid fuels, but requires upgrading to remove excess oxygen and produce a satisfactory fuel oil. Nickel phosphide has been shown to be an active composition for hydrodeoxygenation (HDO) of bio-oil model compounds. In this study, nickel phosphide catalysts were used for direct upgrading of an actual pyrolysis bio-oil derived from cedar chips. The activity of Ni2P deposited on an amorphous SiO2 support for HDO was first verified using the model compound, 2-methyltetrahydrofuran (2-MTHF), at the temperature of the pyrolysis oil treatment of 350°C. The Ni2P/SiO2 catalyst showed high activity for 2-MTHF hydrodeoxygenation under atmospheric pressure hydrogen with low cracking activity. Fast pyrolysis and catalytic upgrading were conducted sequentially using a laboratory-scale, two-stage system consisting of a fluidized bed pyrolyzer and a fluidized bed catalytic reactor both operating at 0.1 MPa, with a hydrogen partial pressure of 0.06 MPa. It was found that the Ni2P/SiO2 catalyst was moderately effective in upgrading the biomass pyrolysis vapors and producing a refined bio-oil with decreased oxygen content. The moderate deoxygenation of the bio-oil was confirmed by elemental analysis and Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS) analysis. Gas chromatography-mass spectrometry (GC-MS) analysis showed that the treated bio-oil mainly consisted of phenolic compounds, and the MS spectra before and after upgrading suggested that reactions including hydrodeoxygenation, hydrogenation, decarbonylation, and hydrolysis occurred during the upgrading. Furthermore, Ni2P supported on ZSM-5 zeolite eliminated oxygen in the bio-oil with smaller reduction in the oil yield than Ni2P supported on SiO2. The deoxygenation activity of the nickel phosphide catalysts was higher than that of conventional catalysts such as Ni/SiO2, Pd/C and an FCC-catalyst.
AB - Pyrolysis bio-oil is a promising source of liquid fuels, but requires upgrading to remove excess oxygen and produce a satisfactory fuel oil. Nickel phosphide has been shown to be an active composition for hydrodeoxygenation (HDO) of bio-oil model compounds. In this study, nickel phosphide catalysts were used for direct upgrading of an actual pyrolysis bio-oil derived from cedar chips. The activity of Ni2P deposited on an amorphous SiO2 support for HDO was first verified using the model compound, 2-methyltetrahydrofuran (2-MTHF), at the temperature of the pyrolysis oil treatment of 350°C. The Ni2P/SiO2 catalyst showed high activity for 2-MTHF hydrodeoxygenation under atmospheric pressure hydrogen with low cracking activity. Fast pyrolysis and catalytic upgrading were conducted sequentially using a laboratory-scale, two-stage system consisting of a fluidized bed pyrolyzer and a fluidized bed catalytic reactor both operating at 0.1 MPa, with a hydrogen partial pressure of 0.06 MPa. It was found that the Ni2P/SiO2 catalyst was moderately effective in upgrading the biomass pyrolysis vapors and producing a refined bio-oil with decreased oxygen content. The moderate deoxygenation of the bio-oil was confirmed by elemental analysis and Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS) analysis. Gas chromatography-mass spectrometry (GC-MS) analysis showed that the treated bio-oil mainly consisted of phenolic compounds, and the MS spectra before and after upgrading suggested that reactions including hydrodeoxygenation, hydrogenation, decarbonylation, and hydrolysis occurred during the upgrading. Furthermore, Ni2P supported on ZSM-5 zeolite eliminated oxygen in the bio-oil with smaller reduction in the oil yield than Ni2P supported on SiO2. The deoxygenation activity of the nickel phosphide catalysts was higher than that of conventional catalysts such as Ni/SiO2, Pd/C and an FCC-catalyst.
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U2 - 10.1016/j.jcat.2015.10.022
DO - 10.1016/j.jcat.2015.10.022
M3 - Article
AN - SCOPUS:84947968235
SN - 0021-9517
VL - 333
SP - 115
EP - 126
JO - Journal of Catalysis
JF - Journal of Catalysis
ER -