4.7 Review

Recent advances in the unsupported catalysts for the hydrodesulfurization of fuel

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Article Engineering, Chemical

Co-processing of hydrodeoxygenation and hydrodesulfurization of phenol and dibenzothiophene with NiMo/Al2O3-ZrO2 and NiMo/TiO2-ZrO2 catalysts

Jesus Andres Tavizon Pozos et al.

Summary: The study found that NiMo/TiO2-ZrO2 exhibited higher activity in the co-processing reaction of phenol and DBT compared to NiMo/Al2O3-ZrO2, indicating more active sites and lower competition. Both catalysts showed similar functionalities, but the competition levels varied due to the availability of the highly active NiMoS phase.

INTERNATIONAL JOURNAL OF CHEMICAL REACTOR ENGINEERING (2022)

Article Chemistry, Applied

High-performance NiMoS hydrodesulfurization catalysts by one-pot hydrothermal synthesis using Ni(acac)2 for sulfur-free liquid fuels

Antony Rajendran et al.

Summary: The study attempted a straightforward hydrothermal synthesis of NiMoS active phases loaded on SBA-15. Characterization of the catalysts revealed that the one-pot synthesis promoted the generation of dispersed MoS2 layers, leading to improved catalytic activity and ultra-deep sulfur removal in dibenzothiophene hydrodesulfurization.

FUEL PROCESSING TECHNOLOGY (2022)

Article Chemistry, Applied

The catalytic hydrodesulfurization performance and mechanism of hierarchically porous iron-based catalyst for coal liquefaction oil

Xiongchao Lin et al.

Summary: Hierarchically porous iron-based catalysts were prepared using carbon microsphere as a template via impregnation and coprecipitation methods. The catalysts exhibited high dispersion of nano-size particles with large surface area. The mixed-valence and vacancy as active sites in the catalysts, along with the nitrogen doping, improved desulphurization activity by offering more active sites and lowering the C-S bond strength. The hierarchical pore structure facilitated hydrogen and sulfur-containing molecules adsorption, leading to high efficiency and selectivity on sulfur removal.

FUEL PROCESSING TECHNOLOGY (2022)

Article Chemistry, Physical

Insights into the intrinsic kinetics for efficient hydrodesulfurization of 4,6-dimethyldibenzothiophene over mesoporous CoMoS2/ZSM-5

Lu Qi et al.

Summary: The intrinsic kinetics of the hydrodesulfurization of 4,6-DMDBT was studied using CoMoS2/MZSM-5 catalyst and compared to CoMoS2/γ-Al2O3 catalyst. A kinetic model considering direct desulfurization and two hydrogenation pathways was established. The rate constants of reactions on CoMoS2/MZSM-5 were higher than those on CoMoS2/γ-Al2O3. Activation energies played a critical role in the reaction rates, and sulfur vacancies were found to facilitate the reaction.

JOURNAL OF CATALYSIS (2022)

Article Chemistry, Applied

Deep hydrodesulfurization of 4,6-dimethydibenzothiophene over CoMoS/TiO2 catalysts: Impact of the TiO2 treatment

Teddy Roy et al.

Summary: Mesostructured titania as a support for the CoMoS active phase enhances HDS activity and DDS selectivity, with temperature treatment significantly affecting catalyst activity. Higher activities are obtained after treatment at 380 degrees C, correlating with higher specific surface area and a semicrystalline anatase framework in the mesostructured TiO2 material.

CATALYSIS TODAY (2021)

Article Chemistry, Applied

Effects of Fe species on promoting the dibenzothiophene hydrodesulfurization over the Pt/γ-Al2O3 catalysts

Juan Liu et al.

Summary: Adding Fe to Pt catalyst can significantly improve sulfur tolerance, promote the reduction of Pt oxides, enhance the dispersion of Pt nanoparticles, and increase the affinity to sulfur, making Fe a favorable additive for hydrodesulfurization.

CATALYSIS TODAY (2021)

Article Chemistry, Physical

Effect of Lanthanum Doping on the reactivity of unsupported CoMoS2 catalysts

Carolina Valdes et al.

Summary: In this study, catalytic systems based on La-doping were developed to improve the activity and performance of CoMoS2 hydrodesulfurization catalysts. The La-doped catalysts showed enhanced catalytic activity compared to undoped CoMoS2, with the major reaction pathway being direct desulfurization.

APPLIED CATALYSIS A-GENERAL (2021)

Article Chemistry, Physical

Rational design of ionic V-MOF with confined Mo species for highly efficient oxidative desulfurization

Shuo Wang et al.

Summary: By adjusting the valence state of metal units, this study successfully generated active species within ionic metal-organic frameworks, which is crucial for the rational design of efficient ionic MOFs.

APPLIED CATALYSIS B-ENVIRONMENTAL (2021)

Article Chemistry, Physical

Template-free, facile synthesis of nickel promoted multi-walled MoS2 & nano-bricks containing hierarchical MoS2 nanotubes from the bulk NiMo oxide

Ramesh Kumar Chowdari et al.

Summary: The low-temperature and template-free synthesis method was developed to prepare MoS2 nanotubes by sulfidation of bulk NiMo oxide. The in-situ sulfided catalyst showed outstanding activity in the hydrodesulfurization of dibenzothiophene (DBT), significantly increasing the initial reaction rate. Mathematical expression (RKC equation) was derived to correlate the size of the regular hexagonal MoS2 nanoparticles with its activity.

APPLIED CATALYSIS B-ENVIRONMENTAL (2021)

Article Biotechnology & Applied Microbiology

Performance and characteristic of a haloalkaliphilic bio-desulfurizing system using Thioalkalivibrio verustus D301 for efficient removal of H2S

Tingzhen Mu et al.

Summary: This study developed a bio-desulfurizing system based on a sulfur-oxidizing bacterium under haloalkaliphilic conditions, demonstrating optimal performance under specific sulfide load and ORP values, as well as revealing spatial and temporal heterogeneity in the bioreactor. The study also emphasized the key role of operating conditions in shaping sulfur particle morphology and highlighted the efficiency of gravity settling for particle harvesting. The findings provide valuable insights for the design and optimization of industrial bio-desulfurizing equipment in the future.

BIOCHEMICAL ENGINEERING JOURNAL (2021)

Article Engineering, Environmental

Carbon nanotube-incorporated alumina as a support for MoNi catalysts for the efficient hydrodesulfurization of thiophenes

Tawfik A. Saleh

Summary: The study showed that adding carbon nanotubes to the alumina support enhances the catalytic activity for the hydrodesulfurization reaction of dibenzothiophene in fuels, with the AlCNTMoNi catalyst demonstrating better performance and stability compared to AlMoNi.

CHEMICAL ENGINEERING JOURNAL (2021)

Article Engineering, Environmental

Facile synthesis of few-layer MoS2 nanosheets with different morphologies supported on Al-TUD-1 for efficient hydrodesulfurization of dibenzothiophene and 4,6-dimethyldibenzothiophene

Chengkun Xiao et al.

Summary: Low-cost pure aluminum-based Al-TUD-1 mesoporous materials were successfully synthesized and modified with Citric acid to form NiMo/AT catalysts for DBT and 4,6-DMDBT HDS reactions. The NiMoCA(2)/AT catalyst showed superior performance with improved HDS activity and selectivity, achieving maximal efficiency and TOF values at WHSV of 10 h-1.

CHEMICAL ENGINEERING JOURNAL (2021)

Article Chemistry, Physical

New approach to unsupported ReS2 nanorod catalyst for upgrading of heavy crude oil using methane as hydrogen source

Zohal Safaei Mahmoudabadi et al.

Summary: Highly active ReS2 nanocatalysts were prepared and applied in upgrading heavy crude oil, showing significant catalytic activities. RSM technique was used to investigate the effects of temperature, pressure, and dosage of catalyst on reaction performance, with optimal conditions yielding highest HDS activity. Additionally, the influence of ReS2 nanorods catalyst on HDN of heavy crude oil was studied, revealing highest efficiency under specific conditions.

INTERNATIONAL JOURNAL OF HYDROGEN ENERGY (2021)

Article Energy & Fuels

Migration and Rearrangement of Fe-Zn Species in the Preparation of Fe-Zn Bimetallic Catalysts and Their Effects on the Hydrodesulfurization Reactivity

Xinyue Zhang et al.

Summary: The addition of urea changed the distribution of Fe-Zn bimetallic catalysts, resulting in a significant increase in the Fe/Zn atomic ratio on the catalyst surface, which enhanced the catalytic activity, especially the HDS activity.

ENERGY & FUELS (2021)

Article Chemistry, Applied

Effect of the titanium incorporation method on the morphology and HDS activity of supported ternary Ni-Mo-W/SBA-16 catalysts

M. O. Alonso-Perez et al.

Summary: A series of trimetallic Ni-Mo-W catalysts supported on cubic mesoporous silica modified with Ti were prepared to study the effect of Ti incorporation method on the physical and chemical properties. The catalysts prepared by sol-gel method demonstrated to be more effective toward sulfur removal from dibenzothiophene compared to the catalyst modified by post-synthesis method.

MICROPOROUS AND MESOPOROUS MATERIALS (2021)

Article Energy & Fuels

Low-temperature catalytic oxidative desulfurization by two-phase system with O-bridged diiron perfluorophthalocyanine

Ze Fang et al.

Summary: An environmentally friendly desulfurization technology was developed using a biomimetic catalytic system, ethanol and water solvent, achieving a high removal rate of dibenzothiophene. The research provides a new idea for the design of efficient, energy-saving, and environmentally friendly desulfurization systems.
Article Energy & Fuels

An experimental study of Ni-Mo adsorbent for reactive adsorption desulfurization of spent tire pyrolysis oil modelled using n-hexane and thiophene

Qian Zhang et al.

Summary: Using a co-precipitated nickel-molybdenum (NiMo) adsorbent for the reactive adsorption desulfurization (RADS) of model spent tire pyrolysis oil, it was found that under mild reaction conditions of 300 degrees C, 1 MPa, and 108 H:S molar ratio, a sulfur removal percentage of 99.9% was achieved. Ni and Mo played cooperative and multifunctional roles in the RADS process, acting first as sulfur acceptors and then as active centers for hydrodesulfurization (HDS).
Article Chemistry, Applied

Unraveling the molecular-level structures and distribution of refractory sulfur compounds during residue hydrotreating process

Jiamin Zhao et al.

Summary: The study revealed that volatile PASHs are present in lower quantities in the products of residue hydrotreating process, while the major refractory sulfur compounds are identified as S1 class compounds. Furthermore, collision-induced dissociation experiments showed that the key refractory PASHs have a structure of alkyl (C2)-substituted DBT.

FUEL PROCESSING TECHNOLOGY (2021)

Article Energy & Fuels

Enhanced catalytic activity of ultrasmall NiMoW trimetallic nanocatalyst for hydrodesulfurization of fuels

Rupesh Singh et al.

Summary: The research demonstrates that NiMoW trimetallic catalysts exhibit higher activity in hydrodesulfurization due to synergistic effect, which involves partial substitution of Mo by W during synthesis, as well as the use of ultrasmall size catalysts.
Review Engineering, Chemical

Review on Hydrodesulfurization over Zeolite-Based Catalysts

Tian-You Cui et al.

Summary: Zeolite-based HDS catalysts play a crucial role in alleviating the removal of refractory sulfur compounds through isomerization and cracking abilities. These catalysts can improve HDS efficiency and reduce coke formation, leading to better selectivity in the process.

INDUSTRIAL & ENGINEERING CHEMISTRY RESEARCH (2021)

Article Chemistry, Physical

Hybrid CoMoS - polyaniline nanowires catalysts for hydrodesulfurisation applications

Sourav Ghosh et al.

Summary: The catalytic performances of promoted CoMoS catalysts were greatly improved by structuring the active phase using self-assembled PANI nanowires, followed by the addition of cobalt acetylacetonate on oxidic or sulfided Mo-based hybrids. The highest rate constants normalized by mol of (MoS2)(edges+corner) in the hydrodesulfurization of 3-methylthiophene were obtained when Co(acac)(2) was deposited on a MoS3/PANI hybrid precursor. The normalized HDS rate constants for the different samples increased with the Co/Moedges+corner atomic ratios, with an optimum observed for HDS/HYD selectivity in the same ratio.

APPLIED CATALYSIS A-GENERAL (2021)

Article Chemistry, Multidisciplinary

Oxidative desulfurization of refinery diesel pool fractions using LaVO4 photocatalyst

Iqrash Shafiq et al.

Summary: Oxidative desulfurization (ODS) is an effective method for removing organosulfur compounds at mild conditions without the need for costly hydrogen. In this study, a pure LaVO4 photocatalyst was prepared and found to exhibit excellent visible-light-driven deep oxidative desulfurization performance. The photocatalyst showed great potential for desulfurization of various petroleum refinery diesel pool fractions, with a possible mechanism proposed and recyclability discussed.

JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY (2021)

Article Engineering, Environmental

Modification of ZSM-5 mesoporosity and application as catalyst support in hydrodesulfurization of dibenzothiophene: Experimental and DFT studies

Mustapha Umar et al.

Summary: The study investigated the hydrodesulfurization efficiency of NiMoS supported on modified H-ZSM-5, with focus on desilication and its impact on the catalysts' performance. Results showed that desilication improved mesoporosity and surface area of H-ZSM-5, leading to higher HDS performance of the catalysts. The experimental findings were in good correlation with DFT simulation on the direct desulfurization pathway.

JOURNAL OF ENVIRONMENTAL CHEMICAL ENGINEERING (2021)

Article Chemistry, Multidisciplinary

Carbon nitride used as a reactive template to prepare mesoporous molybdenum sulfide and nitride

Daria Ryaboshapka et al.

Summary: Carbon nitride C3N4 has been used as a sacrificial template to prepare inorganic materials with hierarchical pore structure, impregnated with ammonium heptamolybdate. Treatment with specific reactive gas mixtures allows mesoporous molybdenum sulfide and molybdenum nitride materials to be obtained, showing advantageous catalytic properties, especially in thiophene hydrodesulfurization (HDS) and electrochemical hydrogen evolution reaction (HER). The highest rates in both reactions were observed for partially sulfidized Mo2N solid.

RSC ADVANCES (2021)

Article Chemistry, Physical

Lamellar flower-like porous MoS2 as an efficient cocatalyst to boost photocatalytic hydrogen evolution of CdS

Lei Su et al.

Summary: The photocatalytic H-2 evolution activity of CdS was significantly enhanced by fabricating a unique porous MoS2 cocatalyst with a lamellar structure. The enhanced activity of the porous MoS2/CdS composite was attributed to the distinctive cocatalyst structure, including coexisting spherical porous and lamellar structures, as well as a heterojunction structure between MoS2 and CdS. The heterojunction structure accelerated the transfer of photo-induced electrons, leading to improved visible-light utilization and potential enhancement of H-2 evolution activities in other photocatalysts.

CATALYSIS SCIENCE & TECHNOLOGY (2021)

Article Chemistry, Physical

New insight into the support effect on HDS catalysts: evidence for the role of Mo-support interaction on the MoS2 slab morphology

Elizabeth Dominguez Garcia et al.

APPLIED CATALYSIS B-ENVIRONMENTAL (2020)

Article Materials Science, Multidisciplinary

Structural and magnetic properties of MgFe2O4 powders synthesized by solution combustion method: the effect of fuel type

P. Heidari et al.

JOURNAL OF MATERIALS RESEARCH AND TECHNOLOGY-JMR&T (2020)

Article Chemistry, Physical

Novel NiMoW-clay hybrid catalyst for highly efficient hydrodesulfurization reaction

Youlin Liu et al.

CATALYSIS COMMUNICATIONS (2020)

Article Chemistry, Applied

Thiophene HDS on La-Modified CoMo/Al2O3 Sulfided Catalysts. Effect of Rare-Earth Content

J. Escobar et al.

TOPICS IN CATALYSIS (2020)

Article Materials Science, Multidisciplinary

Facile ambient pressure propylene carbonate solution synthesis of highly divided CoMoS solids

Santiago Palencia-Ruiz et al.

MATERIALS LETTERS (2020)

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Deactivation study of unsupported nano MoS2 catalyst

Haiping Zhang et al.

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Advanced Hydrodesulfurization Catalysts: A Review of Design and Synthesis

Abdulkadir Tanimu et al.

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Article Green & Sustainable Science & Technology

The effect of calcination temperature on the activity of hydrodesulfurization catalysts supported on mesoporous activated carbon

Umar Cheche Abubakar et al.

JOURNAL OF CLEANER PRODUCTION (2019)

Article Engineering, Chemical

Microwave sodium roasting (MWSR) spent HDS catalysts for recovery Mo and in situ sulfur fixation

Xiaolei Ye et al.

JOURNAL OF THE TAIWAN INSTITUTE OF CHEMICAL ENGINEERS (2019)

Article Chemistry, Physical

Study on the modification of unsupported hydrodesulfurization catalysts by the ZSM-5 zeolite nanoclusters

Chengwu Dong et al.

APPLIED CATALYSIS A-GENERAL (2019)

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Hydrodesulfurization activity of Ni-containing unsupported Ga(x)WS2 catalysts

T. A. Zepeda et al.

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Effect of Particle Size on the Deep HDS Properties of Ni2P Catalysts

Peter J. Topalian et al.

JOURNAL OF PHYSICAL CHEMISTRY C (2019)

Article Chemistry, Physical

Morphology-performance relation of (Co)MoS2 catalysts in the hydrodesulfurization of FCC gasoline

Cen Zhang et al.

APPLIED CATALYSIS A-GENERAL (2018)

Article Chemistry, Physical

The Effects of Chelating Agents on CoMo/TiO2-Al2O3 Hydrodesulfurization Catalysts

Liancheng Bing et al.

CATALYSIS LETTERS (2018)

Article Engineering, Chemical

Controlling dispersion and morphology of MoS2 nanospheres by hydrothermal method using SiO2 as template

Zhenwei Zhang et al.

CHINESE JOURNAL OF CHEMICAL ENGINEERING (2018)

Article Energy & Fuels

Hydrodesulfurization of Thiophene on Activated Carbon Fiber Supported NiMo Catalysts

Yogendra Nath Prajapati et al.

ENERGY & FUELS (2018)

Article Green & Sustainable Science & Technology

Simultaneous adsorptive desulfurization of diesel fuel over bimetallic nanoparticles loaded on activated carbon

Tawfik A. Saleh

JOURNAL OF CLEANER PRODUCTION (2018)

Article Chemistry, Physical

Synthesis of molybdenum cobalt nanocatalysts supported on carbon for hydrodesulfurization of liquid fuels

Tawfik A. Saleh et al.

JOURNAL OF MOLECULAR LIQUIDS (2018)

Article Nanoscience & Nanotechnology

Fabrication of 3D Porous Hierarchical NiMoS Flowerlike Architectures for Hydrodesulfurization Applications

Wenjing Song et al.

ACS APPLIED NANO MATERIALS (2018)

Review Chemistry, Physical

Hydrodesulfurization catalysts based on carbon nanostructures: A review

Zeinab Hajjar et al.

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HDS of dibenzothiophene with CoMoS2 synthesized using elemental sulfur

Jacob Sollner et al.

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Naphtha HDS over Co-Mo/Graphene catalyst synthesized through the spray pyrolysis technique

Zeinab Hajjar et al.

JOURNAL OF ANALYTICAL AND APPLIED PYROLYSIS (2017)

Article Engineering, Environmental

Effects of bimetallic Ce/Fe nanoparticles on the desulfurization of thiophenes using activated carbon

Gaddafi I. Danmaliki et al.

CHEMICAL ENGINEERING JOURNAL (2017)

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Effect of NiMo phases on the hydrodesulfurization activities of dibenzothiophene

Huan Liu et al.

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Hamidreza Arandiyan et al.

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HDS performance of NiMo catalysts supported on nanostructured materials containing titania

Julio Cesar Morales-Ortuno et al.

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Study for the production of ultra-low sulfur gas oils on a highly loaded NiMoW catalyst

Changlong Yin et al.

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High-activity MgO-supported CoMo hydrodesulfurization catalysts prepared by non-aqueous impregnation

Ludek Kaluza et al.

APPLIED CATALYSIS B-ENVIRONMENTAL (2015)

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Understanding of the effect of synthesis temperature on the crystallization and activity of nano-MoS2 catalyst

Haiping Zhang et al.

APPLIED CATALYSIS B-ENVIRONMENTAL (2015)

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Hydrothermal synthesis of nanocrystalline H[Fe, Al]ZSM-5 zeolites for conversion of methanol to gasoline

Jianqing Li et al.

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Zirconia-silica based mesoporous desulfurization adsorbents

Jessica M. Palomino et al.

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Cotton-templated fabrication of hierarchical SnO2 mesoporous microtubes as the anode material of lithium ion battery

Xiangyang Zhou et al.

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From core-shell MoSx/ZnS to open fullerene-like MoS2 nanoparticles

Elodie Blanco et al.

JOURNAL OF MATERIALS CHEMISTRY A (2014)

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Comparative Activity of Ni-W and Co-Mo Sulfides Using Transition Metal Oxides as Precursors in HDS Reaction of DBT

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Effect of Ti loading on the HDS and HDN activity of KLGO on NiMo/TiSBA-15 catalysts

Kapil K. Soni et al.

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Hierarchically ordered meso/macroporous γ-alumina for enhanced hydrodesulfurization performance

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Essential role of citric acid in preparation of efficient NiW/Al2O3 HDS catalysts

Huifeng Li et al.

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Z. Ismagilov et al.

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Synthesis, Characterization, and Thiophene Hydrodesulfurization Activity of Novel Macroporous and Mesomacroporous Carbon

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Hydrodesulphurisation activity of CoMo catalyst supported on multi wall carbon nanotube: sulphur species study

Payman Khorami et al.

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Unsupported NiMoW sulfide catalysts for hydrodesulfurization of dibenzothiophene by thermal decomposition of thiosalts

Yanjiao Yi et al.

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Electron microscopy investigation of the microstructure of unsupported Ni-Mo-W sulfide

B. S. Zhang et al.

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Synthetic Fabrication of Nanoscale MoS2-Based Transition Metal Sulfides

Shutao Wang et al.

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Trimetallic NiMoW unsupported catalysts for HDS

A. Olivas et al.

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Hai Fan et al.

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HDS of benzothiophene and dihydrobenzothiophene over sulfided Mo/γ-Al2O3

Huamin Wang et al.

APPLIED CATALYSIS A-GENERAL (2008)

Article Chemistry, Physical

Hydrodesulfurization of thiophene on carbon nanofiber supported Co/Ni/Mo catalysts

Zhixin Yu et al.

APPLIED CATALYSIS B-ENVIRONMENTAL (2008)

Article Chemistry, Applied

Solution synthesis of the unsupported Ni-W sulfide hydrotreating catalysts

Zhang Le et al.

CATALYSIS TODAY (2008)

Article Chemistry, Physical

Solution synthesis of unsupported Ni-W-S hydrotreating catalysts

Le Zhang et al.

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Article Materials Science, Multidisciplinary

Shape-control of nano-ZnO by changing the solvent

Zhengping Fu et al.

MATERIALS LETTERS (2007)

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The role of Co-Mo-S type structures in hydrotreating catalysts

Henrik Topsoe

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States of carbon nanotube supported Mo-based HDS catalysts

Hongyan Shang et al.

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Effect of sulfidation on Mo-W-Ni trimetallic catalysts in the HDS of DBT

Y Gochi et al.

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Solution syntheses of unsupported Co(Ni)-Mo-S hydrotreating catalysts

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Porous MoS2 synthesized by ultrasonic spray pyrolysis

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CATALYSIS TODAY (2003)

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Hydrothermal synthesis of MoS2 nanowires

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Atomic-scale structure of Co-Mo-S nanoclusters in hydrotreating catalysts

JV Lauritsen et al.

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Sol-gel and ultrafine particle formation via dielectric tuning of inorganic salt-alcohol-water solutions

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