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

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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) | Viewed by 27245

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Special Issue Editor

Prof. Dr. Yong-Kul Lee

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Guest Editor

Advanced Catalysis Lab for Energy and Environment, Departent of Chemical Engineering, Dankook University, Yongin 16982, Korea
Interests: heterogeneous catalysis; design and synthesis of nanomaterials (metal chalcogenides); X-ray absorption spectroscopy (in situ XAFS measurements); DFT calculations
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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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12 pages, 2256 KiB

Open AccessArticle

Catalytic Activities of Noble Metal Phosphides for Hydrogenation and Hydrodesulfurization Reactions

by Yasuharu Kanda, Kota Kawanishi, Taiki Tsujino, Ahmad MFM Al-otaibi and Yoshio Uemichi

Catalysts 2018, 8(4), 160; https://doi.org/10.3390/catal8040160 - 17 Apr 2018

Cited by 22 | Viewed by 5473

Abstract

In this work, the development of a highly active noble metal phosphide (NM_XP_Y)-based hydrodesulfurization (HDS) catalyst with a high hydrogenating ability for heavy oils was studied. NM_XP_Y 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

(This article belongs to the Special Issue Recent Progress in Transition Metal Phosphide Catalysts for the Hydroprocessing of Petroleum or Biomass Feedstocks)

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10 pages, 1901 KiB

Open AccessFeature PaperArticle

A New Approach to Deep Desulfurization of Light Cycle Oil over Ni₂P Catalysts: Combined Selective Oxidation and Hydrotreating

by Gwang-Nam Yun, Kye-Syng Cho, Yong-Su Kim and Yong-Kul Lee

Catalysts 2018, 8(3), 102; https://doi.org/10.3390/catal8030102 - 01 Mar 2018

Cited by 11 | Viewed by 4407

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 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

(This article belongs to the Special Issue Recent Progress in Transition Metal Phosphide Catalysts for the Hydroprocessing of Petroleum or Biomass Feedstocks)

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3543 KiB

Open AccessArticle

Synergetic Effect of Ni₂P/SiO₂ and γ-Al₂O₃ Physical Mixture in Hydrodeoxygenation of Methyl Palmitate

by Ivan V. Shamanaev, Irina V. Deliy, Evgeny Yu. Gerasimov, Vera P. Pakharukova, Evgeny G. Kodenev, Pavel V. Aleksandrov and Galina A. Bukhtiyarova

Catalysts 2017, 7(11), 329; https://doi.org/10.3390/catal7110329 - 06 Nov 2017

Cited by 24 | Viewed by 6142

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 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

(This article belongs to the Special Issue Recent Progress in Transition Metal Phosphide Catalysts for the Hydroprocessing of Petroleum or Biomass Feedstocks)

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2718 KiB

Open AccessArticle

HDO of Methyl Palmitate over Silica-Supported Ni Phosphides: Insight into Ni/P Effect

by Irina V. Deliy, Ivan V. Shamanaev, Evgeny Yu. Gerasimov, Vera P. Pakharukova, Ilya V. Yakovlev, Olga B. Lapina, Pavel V. Aleksandrov and Galina A. Bukhtiyarova

Catalysts 2017, 7(10), 298; https://doi.org/10.3390/catal7100298 - 04 Oct 2017

Cited by 26 | Viewed by 4686

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) and ((NH₄)₂HPO₄) as a precursor. The Ni_xP_y/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, PO_x 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 PO_x 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 PO_x 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

(This article belongs to the Special Issue Recent Progress in Transition Metal Phosphide Catalysts for the Hydroprocessing of Petroleum or Biomass Feedstocks)

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Review

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22 pages, 3749 KiB

Open AccessEditor’s ChoiceReview

Platinum Group Metal Phosphides as Efficient Catalysts in Hydroprocessing and Syngas-Related Catalysis

by Luis Alvarado Rupflin, Chiara Boscagli and Stephan Andreas Schunk

Catalysts 2018, 8(3), 122; https://doi.org/10.3390/catal8030122 - 20 Mar 2018

Cited by 15 | Viewed by 5752

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, 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

(This article belongs to the Special Issue Recent Progress in Transition Metal Phosphide Catalysts for the Hydroprocessing of Petroleum or Biomass Feedstocks)

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