Special Issue "Recent Progress in Transition Metal Phosphide Catalysts for the Hydroprocessing of Petroleum or Biomass Feedstocks"

A special issue of Catalysts (ISSN 2073-4344). This special issue belongs to the section "Biomass Catalysis".

Deadline for manuscript submissions: closed (28 February 2018)

Special Issue Editor

Guest Editor
Prof. Dr. Yong-Kul Lee

Dankook University, Yongin 16982, Korea
Website | E-Mail
Interests: heterogeneous catalysis; hydrotreating; hydrodesulfurization; hydrodeoxygenation; metal phosphide; metal chalcogenides; EXAFS; in situ spectroscopy

Special Issue Information

Dear Colleagues,

The transition metal phosphides, as a new class of hydro-processing catalysts, have shown excellent activity in hydrogenation (HYD), hydrodesulfurization (HDS), and hydrodenitrogenation (HDN) of petroleum feedstocks. More recently, metal phosphides have been effectively exploited in hydrodeoxygenation (HDO) for the upgrading of biomass feedstocks. Particular attention has been devoted to the preparation of more active and stable phosphides, since most of the catalytic properties that make the active phosphides strongly depend on the preparation method and pretreatment conditions. Moreover, the challenging aspects of the reaction mechanisms over the phosphides and the nature of active sites are still open for research. This Special Issue covers recent progress of transition metal phosphides, ranging from basic research and characterization to industrial applications. The Guest Editor hopes that the topics covered in this Special Issue will convey the expanding potential of phosphide catalysts and will be of interest for those active in the field.

I look forward to receiving original contributions or review papers.

Prof. Dr. Yong-Kul Lee
Guest Editor

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Keywords

  • Transition metal phosphide
  • Hydrotreating
  • Hydroprocessing
  • Hydrodesulfurization
  • Hydrodenitrogenation
  • Hydrodeoxygenation

Published Papers (5 papers)

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Research

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Open AccessArticle Catalytic Activities of Noble Metal Phosphides for Hydrogenation and Hydrodesulfurization Reactions
Catalysts 2018, 8(4), 160; https://doi.org/10.3390/catal8040160
Received: 27 February 2018 / Revised: 12 April 2018 / Accepted: 12 April 2018 / Published: 17 April 2018
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Abstract
In this work, the development of a highly active noble metal phosphide (NMXPY)-based hydrodesulfurization (HDS) catalyst with a high hydrogenating ability for heavy oils was studied. NMXPY catalysts were obtained by reduction of P-added noble metals
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In this work, the development of a highly active noble metal phosphide (NMXPY)-based hydrodesulfurization (HDS) catalyst with a high hydrogenating ability for heavy oils was studied. NMXPY catalysts were obtained by reduction of P-added noble metals (NM-P, NM: Rh, Pd, Ru) supported on SiO2. The order of activities for the hydrogenation of biphenyl was Rh-P > NiMoS > Pd-P > Ru-P. This order was almost the same as that of the catalytic activities for the HDS of dibenzothiophene. In the HDS of 4,6-dimethyldibenzothiophene (4,6-DMDBT), the HDS activity of the Rh-P catalyst increased with increasing reaction temperature, but the maximum HDS activity for the NiMoS catalyst was observed at 270 °C. The Rh-P catalyst yielded fully hydrogenated products with high selectivity compared with the NiMoS catalyst. Furthermore, XRD analysis of the spent Rh-P catalysts revealed that the Rh2P phase possessed high sulfur tolerance and resistance to sintering. Full article
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Open AccessFeature PaperArticle A New Approach to Deep Desulfurization of Light Cycle Oil over Ni2P Catalysts: Combined Selective Oxidation and Hydrotreating
Catalysts 2018, 8(3), 102; https://doi.org/10.3390/catal8030102
Received: 15 January 2018 / Revised: 21 February 2018 / Accepted: 27 February 2018 / Published: 1 March 2018
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Abstract
Amphiphilic phosphotungstic acid (A-PTA) and Ni2P/SBA-15 catalysts were prepared to apply for selective oxidation of refractory sulfur compounds in light cycle oils and hydrotreating of the oxidized S compounds, respectively. Physical properties of the catalyst samples were analyzed by BET, CO
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Amphiphilic phosphotungstic acid (A-PTA) and Ni2P/SBA-15 catalysts were prepared to apply for selective oxidation of refractory sulfur compounds in light cycle oils and hydrotreating of the oxidized S compounds, respectively. Physical properties of the catalyst samples were analyzed by BET, CO uptake chemisorption, and TEM. Structural properties for the supported Ni2P catalysts were analyzed by X-ray diffraction (XRD) and extended X-ray absorption fine structure (XAFS) spectroscopy. The selective oxidation of S compounds in the LCO feed was conducted in a batch reactor at H2O2/S ratio of 10, atmospheric pressure and 353 K and then the products were fed to a continuous flow fixed-bed reactor for hydrotreating at 623 K, 3.0 MPa, and LHSV’s of 0.5–2.0 h−1. A-PTA catalyst showed a high oxidation conversion of 95% for a real LCO feed. The following hydrotreating led to a hydrodesulfurization (HDS) conversion of 99.6% and a hydrodenitrogenation (HDN) conversion of 94.7% over Ni2P/SBA-15, which were much higher than those of direct hydrotreating results which gave an HDS conversion of 63.5% and an HDN conversion of 17.5% based on the same LHSV of 2.0 h−1. It was revealed that the reduction in refractory nitrogen compounds after oxidative treatment contributed to the increase of the following HDS activity. Full article
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Open AccessArticle Synergetic Effect of Ni2P/SiO2 and γ-Al2O3 Physical Mixture in Hydrodeoxygenation of Methyl Palmitate
Catalysts 2017, 7(11), 329; https://doi.org/10.3390/catal7110329
Received: 9 October 2017 / Revised: 26 October 2017 / Accepted: 31 October 2017 / Published: 6 November 2017
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Abstract
The Ni2P/SiO2 catalyst, which was prepared by in situ temperature-programmed reduction and in the mixture with the inert (SiC, SiO2) or acidic (γ-Al2O3) material was studied in methyl palmitate hydrodeoxygenation (HDO). Methyl palmitate HDO
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The Ni2P/SiO2 catalyst, which was prepared by in situ temperature-programmed reduction and in the mixture with the inert (SiC, SiO2) or acidic (γ-Al2O3) material was studied in methyl palmitate hydrodeoxygenation (HDO). Methyl palmitate HDO was carried out at temperatures of 270–330 °C, H2/feed volume ratio of 600 Nm3/m3, and H2 pressure of 3.0 MPa. Ni2P/SiO2 catalyst, diluted with γ-Al2O3 showed a higher activity than Ni2P/SiO2 catalyst diluted with SiC or SiO2. The conversion of methyl palmitate increased significantly in the presence of γ-Al2O3 most probably due to the acceleration of the acid-catalyzed reaction of ester hydrolysis. The synergism of Ni2P/SiO2 and γ-Al2O3 in methyl palmitate HDO can be explained by the cooperation of the metal sites of Ni2P/SiO2 and the acid sites of γ-Al2O3 in consecutive metal-catalyzed and acid-catalyzed reactions of HDO. The obtained results let us conclude that the balancing of metal and acid sites plays an important role in the development of the efficient catalyst for the HDO of fatty acid esters over supported phosphide catalysts. Full article
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Open AccessArticle HDO of Methyl Palmitate over Silica-Supported Ni Phosphides: Insight into Ni/P Effect
Catalysts 2017, 7(10), 298; https://doi.org/10.3390/catal7100298
Received: 30 July 2017 / Revised: 19 September 2017 / Accepted: 30 September 2017 / Published: 4 October 2017
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Abstract
Two sets of silica-supported nickel phosphide catalysts with a nickel content of about 2.5 and 10 wt % and Ni/P molar ratio 2/1, 1/1 and 1/2 in each set, were prepared by way of a temperature-programmed reduction method using (Ni(CH3COO)2
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Two sets of silica-supported nickel phosphide catalysts with a nickel content of about 2.5 and 10 wt % and Ni/P molar ratio 2/1, 1/1 and 1/2 in each set, were prepared by way of a temperature-programmed reduction method using (Ni(CH3COO)2) and ((NH4)2HPO4) as a precursor. The NixPy/SiO2 catalysts were characterized using chemical analysis N2 physisorption, XRD, TEM, 31P MAS NMR. Methyl palmitate hydrodeoxygenation (HDO) was performed in a trickle-bed reactor at 3 MPa and 290 °C with LHSV ranging from 0.3 to 16 h−1. The Ni/P ratio was found to affect the nickel phosphide phase composition, POx groups content and catalytic properties in methyl palmitate HDO with the TOF increased along with a decline of Ni/P ratio and a growth of POx groups’ content. Taking into account the possible routes of methyl palmitate conversion (metal-catalyzed hydrogenolysis or acid-catalyzed hydrolysis), we proposed that the enhancement of acid POx groups’ content with the Ni/P ratio decrease provides an enhancement of the rate of methyl palmitate conversion through the acceleration of acid-catalyzed hydrolysis. Full article
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Review

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Open AccessReview Platinum Group Metal Phosphides as Efficient Catalysts in Hydroprocessing and Syngas-Related Catalysis
Catalysts 2018, 8(3), 122; https://doi.org/10.3390/catal8030122
Received: 23 February 2018 / Revised: 12 March 2018 / Accepted: 13 March 2018 / Published: 20 March 2018
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Abstract
Platinum group metal phosphides are reviewed as catalytic materials for hydroprocessing and syngas-related catalysis. Starting from synthetic procedures leading to highly disperse nano-particular compounds, their properties in the applications are discussed and compared with relevant benchmarks, if available. Regarding their mode of action,
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Platinum group metal phosphides are reviewed as catalytic materials for hydroprocessing and syngas-related catalysis. Starting from synthetic procedures leading to highly disperse nano-particular compounds, their properties in the applications are discussed and compared with relevant benchmarks, if available. Regarding their mode of action, two confronting mechanistic scenarios are presented: (i) a cooperative scenario in which catalytic sites of different functionalities are active in hydroprocessing and (ii) single site catalysis, which appears to be the relevant mode of action in syngas-related catalysis and which occurs over “frustrated” active sites. Full article
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