Hydrodesulfurization Catalysts Research Articles

Mechanism of highly efficient oil removal from spent hydrodesulfurization catalysts by ultrasound-assisted surfactant cleaning methods

The removal of crude oil from spent hydrodesulfurization catalysts constitutes the preliminary stage in the recovery process of valuable metals. However, the traditional roasting method for the removal exhibits massive limitations. In view of this, the present study used an ultrasound-assisted surfactant cleaning method to remove crude oil from spent hydrodesulfurization catalysts, which demonstrated effectiveness. Furthermore, the study investigated the mechanism governing the process with calculation and experiments, so as to provide a comprehensive understanding of the cleaning method’s efficacy. The surfactant selection was predicated on the performance in the IFT test, with SDBS and TX-100 finally being chosen. Subsequent calculations and analysis were then conducted to elucidate their frontier molecular orbitals, electrostatic potential, and polarity. It has been found that both SDBS and TX-100 possess the smallest LUMO-HOMO energy gap (ΔE), registering at 4.91 eV and 4.80 eV, respectively, and presenting the highest interfacial reactivity. The hydrophilic structure in the surfactant regulates the wettability of the oil-water interface, and the long-chain alkanes have excellent non-polar properties that promote the dissolution of crude oil. The ultrasonic-assisted process further improves the interface properties and enhances the oil removal effect. Surprisingly, the crude oil residue was reduced to 0.25% under optimal conditions. The final phase entailed the techno-economic evaluation of the entire process, revealing that, in comparison to the roasting method, this process saves $0.38 per kilogram of spent HDS catalyst, with the advantages of operational simplicity and emission-free. Generally, this study shed new light on the realization of efficient oil removal, with the salience of green, sustainable, and economical.

The regulatory role of cysteine in active phase construction of polyoxometalate-based hydrodesulfurization catalysts: Reduction, chelation, and dispersion

Polyoxometalate-based hydrodesulfurization (HDS) catalysts were modified using cysteine to construct efficient CoMoS active phase. Cysteine, characterized by chelating (–COOH, –NH2) and reducing (−SH) groups, assumed a triple role in catalyst synthesis, including reduction, chelation, and dispersion. Cysteine pre-reduced polyoxometalates to heteropoly blue, significantly increasing the catalyst sulfidation. The increased nucleophilicity of heteropoly blue enhanced their attraction to Co2+ ions, intensifying the Co-Mo bimetallic synergy. The formation of Co-chelate species delayed Co sulfidation, allowing for the concurrent sulfidation of both Co and Mo species and promoting the generation of the CoMoS active phase. Carbonaceous deposits from the high-temperature carbonization of cysteine weakened the metal-support interaction, facilitating the dispersion of the active phase. The S-CoPMo12-Cys/Al2O3 catalyst demonstrated high activity in the HDS reaction of dibenzothiophene, showcasing their potential for advanced HDS reaction.

MOF-derived CoP/C catalyst for efficient dibenzothiophene hydrodesulfurization

The design of an active and sulfur-resistant catalyst for dibenzothiophene (DBT) hydrodesulfurization (HDS) in crude oil purification is highly desirable but remains a grand challenge. Here, two carbon-supported cobalt phosphide catalysts Co2P/C and CoP/C, and a reference sample Co/C are successfully synthesized using a metal–organic-frameworks (MOFs) precursor. A P/Co ratio dependence on crystal phases is found, leading to the formation of two pure-phase cobalt phosphide catalysts CoP/C and Co2P/C. Catalyst evaluation in HDS of DBT shows that the CoP/C catalyst exhibits a higher activity and stability than Co2P/C and Co/C, giving a 93.7 % DBT conversion with 100 h stability under 3 MPa and 380 ◦C. Moreover, a 67.4 % biphenyl yield characterizes the dominance of the direct desulfurization (DDS) pathway. The obtained catalytic performance over the CoP/C catalyst is also superior to the published cobalt phosphide catalysts. Multiple characterization techniques co-evidence that the copious specific surface area, efficient electron transport from Co to P, high thermal stability of Co nanoparticles (NPs), and strong sulfur resistance account for the enhanced catalytic performance of CoP/C. The findings of this report suggest that phosphorus-modified cobalt over the carbon support can act as a promising catalyst for the HDS of DBT.

Hydrodesulfurization Catalysts from Aluminium-Containing Waste

AbstractA possibility of using aluminum hydroxide, a product of processing of the adsorbent that lost its sorption activity in purification of a polyethylene solution cyclohexane, was demonstrated in the synthesis of aluminum kaolin borate supports for hydrodesulfurization catalysis in oil refining. The influence of typical impurities V, Ti and Na in the composition of the spent adsorbent on the physicochemical and catalytic properties of supports and catalysts was determined. Alumina-kaolin-borate catalyst carriers with the Ti content of approx. 0.2% have been prepared by atomic layer deposition (ALD) of TiCl4 onto the granules. A positive effect of molecular layering with TiO2 has been revealed by temperature programmed reduction and oxidation in combination with hydrodesulphurization activity testing. Graphical Abstract

Hydrodesulfurization of Dibenzothiophene: A Machine Learning Approach.

The hydrodesulfurization (HDS) process is widely used in the industry to eliminate sulfur compounds from fuels. However, removing dibenzothiophene (DBT) and its derivatives is a challenge. Here, the key aspects that affect the efficiency of catalysts in the HDS of DBT were investigated using machine learning (ML) algorithms. The conversion of DBT and selectivity was estimated by applying Lasso, Ridge, and Random Forest regression techniques. For the estimation of conversion of DBT, Random Forest and Lasso offer adequate predictions. At the same time, regularized regressions have similar outcomes, which are suitable for selectivity estimations. According to the regression coefficient, the structural parameters are essential predictors for selectivity, highlighting the pore size, and slab length. These properties can connect with aspects like the availability of active sites. The insights gained through ML techniques about the HDS catalysts agree with the interpretations of previous experimental reports.

Heavy oil atmospheric residue: HDS performance and life test using ARDS catalysts system

The objective of this study is to evaluate the catalyst by introducing atmospheric residue of heavy crude (H-AR) that secures full comprehensive characteristics and converts into a petroleum product, namely low sulfur fuel oil (LSFO). Furthermore, to estimate the catalyst’s lifespan under hydroprocessing conditions by monitoring its deactivation rate and maintaining consistent sulfur in LSFO products through gradual increases in reaction temperature. Prior to the hydrotreating test, the heavy crude oil underwent desalting, dewatering, and atmospheric distillation to obtained atmospheric residue (H-AR, i.e., 350°C+) for use as feedstock. The pilot plant employed a catalyst system comprising both hydrodemetallization (HDM) and hydrodesulfurization (HDS) catalysts, distributed across two fixed-bed reactors. The results showed the lifespan approximately 3.0 months as a function of time-on-stream (TOS). The H-AR feed, with its high sulfur, metals, asphaltenes, and micro carbon residue (MCR) content, poses several challenges including carbon deposition at start of run (SOR). The observed deactivation rate is attributing to the feedstock’s poor quality and its impact associated deposition of coke and metals (V and Ni) deposition with TOS.

Synergistic effect between CoSx and MoS2 at the micrometer scale: Considerable promotion of the hydrodesulfurization of DBT

The future implementation of ultralow sulfur fuel regulations requires researchers to have an excellent understanding of the mechanism of the synergistic effect between the Co(Ni) and (Mo)W sulfides in supported Co(Ni)Mo(W)S hydrodesulfurization (HDS) catalysts. This synergistic effect occurs when the distance between two metals is on the mm or nm scale. To investigate the promotion of HDS on the µm scale, a series of Co and Mo multilayer flake catalysts with a thickness of 1 mm were prepared by laminate molding. The distance between CoSx and MoS2 in these specially structured catalysts was adjustable on the µm scale by controlling the order and quality of the catalyst powder. The results for the HDS of dibenzothiophene (DBT) demonstrate that there is an obvious synergistic effect between CoSx and MoS2 on the µm scale. The results of pyridine IR spectroscopy indicate that this synergy is due to CoSx and MoS2 synergistically generating more coordinatively unsaturated sites (CUSs) and -SH active sites at the μm scale, thus increasing the HDS activity. Moreover, the catalyst activity increases as the distance between CoSx and MoS2 decreases, and the fact that the feed comes into contact with CoSx first greatly improves the activity.

Boosting ultra-deep hydrodesulfurization of diesel by tuning sulfidation degree of metals on NiMo/AlOOH catalyst

By using a room-temperature discharge-based sulphurization (RT-DS) process, we efficiently tune sulfidation degree of metal on γ-AlOOH-supported NiMo catalyst via simply changing feedstock amount for preparing catalysts, thus preparing a NiMoS/AOH-4 catalyst for hydrodesulfurization (HDS) of diesel. NiMoS/AOH-4 shows an excellent HDS performance, with S content of diesel being reduced from 18000 μg g−1 to 3 μg g−1 and without catalytic efficiency decrease after 1000 h reaction. Moreover, NiMoS/AOH-4 shows higher rate constant, higher turnover frequency but lower activation energy in HDS reaction, as compared with those on widely reported catalysts. The excellent HDS performance of NiMoS/AOH-4 is resulted from the appropriate sulfidation degree of Mo, which creates more abundant catalytic active Ni-Mo-S phases. RT-DS process for preparing NiMoS/AOH-4 proceeds in Ar at room temperature and atmospheric pressure, without using H2S and heating. This makes RT-DS process suitable for large-scale industrial applications to fabricate more efficient HDS catalysts.

Fabrication of well-structured NiMo hydrodesulfurization catalysts using electropositive Mo-based nanoparticles

Using electropositive Mo-based nanoparticles (Mo-NPs) as precursor could realize the resulting catalyst with more uniform, shorter, higher layered, better Ni-promoted, and stable MoS2 slabs, thus holding excellent HDS performance.

Probing the Effect of Environments on the Stability of Ni2P Nanoparticle Electrocatalysts

Ni2P has been shown to be an effective catalyst for the hydrogen evolution reaction (HER), making it a promising replacement for Pt which is the current state of the art HER catalyst.1,2 H2 is a clean-energy critical fuel and chemical highlighted by the US Department of Energy’s “Hydrogen Shot,” which seeks to reduce “the cost of carbon-neutral hydrogen by 80% to $1 per 1 kg in 1 decade, highlighting the key role of hydrogen in implementing carbon-neutral solutions.”3 Ni2P is also a good or promising catalyst for other reactions, such as alcohol oxidation, hydrodesulfurization,4,5 nitrate reduction, and oxygen evolution reaction.6 However, Ni2P and other TMPs are susceptible to oxidation, which can lead to catalyst degradation and loss in certain conditions.7,8 Stability is an important part of catalysis, especially for achieving the goals of the Hydrogen Shot. Therefore, it is important to understand complex degradation mechanisms in order to better understand structure-activity relationships in these materials. In the present work, in situ Ni K-edge X-ray absorption spectroscopy (XAS) and ex situ P Kα and Kβ X-ray emission spectroscopy (XES) couple together to understand the degradation of Ni2P and show the effects of electrolyte pH, ligands, and air on Ni2P nanoparticles.5 nm Ni2P nanoparticles were synthesized by heating NiCl2 and tris(diethylamino)phosphine in oleylamine. The nanoparticles were drop cast onto carbon fiber paper electrodes and Si wafers or Au-coated wafers for P Kα and Kβ XES. Oleylamine ligands are removed by thermal annealing. Electrochemical experiments were conducted with a three-electrode cell using carbon fiber paper or Au-coated wafers deposited with Ni2P nanoparticles as working electrode, Ag/AgCl calibrated to the H2 redox couple as reference electrode, and graphite rod as counter electrode. P Kα and Kβ XES experiments were conducted inside a N2 glovebox to prevent unintentional air oxidation. Transmission-mode Ni K-edge XAS was conducted on a benchtop spectrometer.Upon exposure to air, as-synthesized Ni2P nanoparticles were studied via P Kα and Kβ XES. Results showed that the phosphide species converted to phosphate with analysis of intermediates well fit by a simple two-phase mixture. Phosphide:phosphate ratios were quantified using linear combination analysis, providing a powerful tool to analyze P speciation on various samples in an inert environment and with minimal loss of material, both advantages of this system over 31P magic angle spinning solid state nuclear magnetic resonance spectroscopy and X-ray photoelectron spectroscopy. Continued work looks at analyzing the effects of the ligand environment on the stability of nanoparticles in electrolytes spanning from acidic to basic pH. We hypothesize that ligands will significantly stabilize the nanoparticles against corrosion and that without ligands Ni2P readily converts to a nickel phosphate species upon exposure to electrolyte.References(1) Popczun, E. J.; McKone, J. R.; Read, C. G.; Biacchi, A. J.; Wiltrout, A. M.; Lewis, N. S.; Schaak, R. E. Nanostructured Nickel Phosphide as an Electrocatalyst for the Hydrogen Evolution Reaction. J. Am. Chem. Soc. 2013, 135 (25), 9267–9270. https://doi.org/10.1021/ja403440e.(2) Liu, P.; Rodriguez, J. A. Catalysts for Hydrogen Evolution from the [NiFe] Hydrogenase to the Ni2P(001) Surface: The Importance of Ensemble Effect. J. Am. Chem. Soc. 2005, 127 (42), 14871–14878. https://doi.org/10.1021/ja0540019.(3) Bullock, M.; More, K. Basic Energy Sciences Roundtable: Foundational Science for Carbon-Neutral Hydrogen Technologies (Report); DOESC Office of Basic Energy Sciences, 2022. https://doi.org/10.2172/1834317.(4) Layan Savithra, G. H.; Muthuswamy, E.; Bowker, R. H.; Carrillo, B. A.; Bussell, M. E.; Brock, S. L. Rational Design of Nickel Phosphide Hydrodesulfurization Catalysts: Controlling Particle Size and Preventing Sintering. Chem. Mater. 2013, 25 (6), 825–833. https://doi.org/10.1021/cm302680j.(5) Rodriguez, J. A.; Kim, J.-Y.; Hanson, J. C.; Sawhill, S. J.; Bussell, M. E. Physical and Chemical Properties of MoP, Ni2P, and MoNiP Hydrodesulfurization Catalysts: Time-Resolved X-Ray Diffraction, Density Functional, and Hydrodesulfurization Activity Studies. J. Phys. Chem. B 2003, 107 (26), 6276–6285. https://doi.org/10.1021/jp022639q.(6) Menezes, P. W.; Indra, A.; Das, C.; Walter, C.; Göbel, C.; Gutkin, V.; Schmeiβer, D.; Driess, M. Uncovering the Nature of Active Species of Nickel Phosphide Catalysts in High-Performance Electrochemical Overall Water Splitting. ACS Catal. 2017, 7 (1), 103–109. https://doi.org/10.1021/acscatal.6b02666.(7) Ha, D.-H.; Han, B.; Risch, M.; Giordano, L.; Yao, K. P. C.; Karayaylali, P.; Shao-Horn, Y. Activity and Stability of Cobalt Phosphides for Hydrogen Evolution upon Water Splitting. Nano Energy 2016, 29, 37–45. https://doi.org/10.1016/j.nanoen.2016.04.034.(8) Parra-Puerto, A.; Ng, K. L.; Fahy, K.; Goode, A. E.; Ryan, M. P.; Kucernak, A. Supported Transition Metal Phosphides: Activity Survey for HER, ORR, OER, and Corrosion Resistance in Acid and Alkaline Electrolytes. ACS Catal. 2019, 11515–11529. https://doi.org/10.1021/acscatal.9b03359.

Enhancing Mo leaching efficiency from spent catalyst via Fenton-like oxidation process: A comprehensive investigation of leaching effects, mechanism and environmental impacts

Spent hydrodesulfurization (HDS) catalyst contains considerable amounts of Mo, Ni and V, is an important secondary resource for these valuable metals. Direct acid solution leaching method exhibits poor separation effect from catalyst carrier for Mo due to greater stability of MoS2. This study explored Mo leaching efficiencies from spent HDS catalyst by Fenton-like oxidation systems (H2O2 and K2S2O8), which were frequently employed in the wastewater treatment. To further improve Mo leaching efficiency, nano zero-valent iron (nZVFe) was used to activate H2O2/K2S2O8 and produce more free radicals (·OH and ·SO4-). Approximate 96.0 % and 93.3 % of Mo were leached from spent HDS catalyst in nZVFe + H2O2 + H2SO4 and nZVFe + K2S2O8 + H2SO4 systems under optimal experimental conditions, increased by 16.2 % and 8.2 % than normal H2O2 (79.8 %) and K2S2O8 (85.1 %) system without nZVFe. The leaching process of Mo in both nZVFe + H2O2 + H2SO4 and nZVFe + K2S2O8 + H2SO4 systems conformed to the shrinkage core model. Kinetic analysis and molecular calculation demonstrated the leaching process of Mo in nZVFe + H2O2 + H2SO4 system was driven by chemical reaction and solid film diffusion, and the leaching and oxidation reactions of MoS2 occurred simultaneously. However, the leaching process of Mo in nZVFe + K2S2O8 + H2SO4 system was driven only by chemical reaction, solid MoS2 was firstly dissolved into Mo4+ by H+, and then oxidized into Mo6+ by ·SO4-. The economic and environmental impacts evaluation indicated that the separation of Mo from spent HDS catalysts by nZVFe + H2O2 + H2SO4 was assigned as a better choice than normal H2O2 and K2S2O8 system without nZVFe due to higher leaching efficiency and lower cost.

Monodisperse dendritic micro-mesoporous composite self-assembled with tiny TS-1 seeds as efficient catalysts for hydrodesulfurization of dibenzothiophenes

Novel TS-1/dendritic mesoporous silica nanoparticles (TS-1/DMSNs, TD) micro-mesoporous composites with different morphology were prepared for NiMo catalysts (NiMo/TD-TEA). Series catalysts were tested in dibenzothiophene (DBT) and 4,6-dimethyldibenzothiophene (4,6-DMDBT) hydrodesulfurization (HDS) reactions in a fix-bed reactor. TS-1 were uniformly compounded with mesoporous materials in the form of Si-O-Ti bonds, which did not affect the typical dendritic morphology. The introduction of TEA could inhibit the growth of support particles, and modulate the acidity and the metal-support interaction (MSI) of catalysts. Optimized NiMo/TD-TEA catalyst showed the optimal DBT (98.0 %) and 4,6-DMDBT (92.3 %) desulfurization rate as well as the excellent hydrogenation (HYD) selectivity for DBT and 4,6-DMDBT HDS with the optimal reaction rate constant (12.2 mol·g−1·h−1, 6.7 mol·g−1·h−1) and turnover frequency (2.3 h−1, 1.4 h−1). By correlating to the catalyst acidity–activity and active phase–activity, the activity and selectivity were not only depended on the presence of Brønsted (B) acid and the total acid content but also associated with the dispersion and morphology of MoS2 slabs.

In situ synthesis of mesoporous NiS2-MoS2 sphere-flower hybrid for hydrodesulfurization of thiophene and 4,6-dimethyl-dibenzothiophene

A series of new NiS2-MoS2-x (x = 0–0.5) sphere-flower hybrids with different Ni/Mo molar ratios, synthesized via a one-pot hydrothermal method, were used as catalysts for hydrodesulfurization (HDS) of thiophene (TP) and 4,6-dimethyl-dibenzothiophene (4,6-DMDBT). The characterizations show that the microstructure of MoS2, including the size of MoS2 nano-flowers, the length of MoS2 slabs, and the number of defects, was regulated by changing Ni/Mo ratios. Increasing the Ni/Mo ratio in the NiS2-MoS2-x catalysts significantly boosts their HDS activity, with the optimum ratio being 0.2. In addition, the NiS2-MoS2-0.2 catalyst exhibits the best direct desulfurization performance, which is associated with the minimum ratio of average slab length (Lav) to average stacking number (Nav) as well as the highest concentration of Ni-promoted Mo sites and sulfur vacancies. Moreover, Ni-containing NiS2-MoS2-x catalysts, characterized by a highly stable sphere-flower configuration, exhibit superior structural stability and catalytic durability than the Ni-free NiS2-MoS2-0 catalyst.

The organic–inorganic dual anchoring strategy based on organic chelators and lacunary polyoxometalates for the preparation of efficient CoWS hydrodesulfurization catalysts

Designing catalysts with bimetallic intimate synergistic effects to enhance catalytic activity has always been a focused problem for hydrodesulfurization (HDS) systems. Efficient HDS catalysts with abundant CoWS active phases were prepared through novel organic–inorganic ligand dual anchoring strategy based on the organic chelating agents and lacunary polyoxometalates (POMs). Citric acid (CA) chelating agent and Co2+ promoter are pre-coordinated in the impregnating solution, the trivacant Keggin [SiW9O34]10- (SiW9) POMs attract the promoter through the nucleophilic oxygen groups at the vacant sites to form the CA-Co@SiW9 “sandwich-like” structure, which allows the organic chelator-promoter-active center to be intimate interaction in a single molecule, thus achieving atomic-scale Co-W proximity on the precursor. In the subsequent sulfidation process, CA delayed the reduction temperature of cobalt species, enabling more Co promoter to be anchored at the edge sites of WS2 clusters to form abundant CoWS active phases, which fully exerted the bimetallic intimate synergism in the HDS reaction. Furthermore, the carbon deposits generated from CA carbonation acted as secondary support weakening the interaction of active metals with Al2O3 support and increasing the sulfidation degree as well as the dispersion of active metals. As a result, the S-Co(CA)W/Al2O3 catalyst achieves a remarkable turnover frequencies (TOF) value of 1.24 × 10-3 s−1 in HDS reaction of dibenzothiophene (DBT). This dual anchoring method based on POMs inorganic ligand and organic chelator ligand provides a new idea for designing novel HDS catalysts.

The superior HDS catalyst derived from a new Waugh Co-Mo polyoxometalate via cationic substitution

In this paper, the Waugh Co-Mo polyoxometalate (POM) (NH4)6[CoMo9O32] was prepared and cationic substituted to increase the Co/Mo ratio to 0.44 with Mo and Co atoms in a new Waugh Co-Mo POM molecule. The method was verified by X-ray diffraction, X-ray fluorescence, and infrared spectroscopy. Then, two series of Co-Mo hydrodesulfurization (HDS) catalysts were prepared using the Waugh Co-Mo POMs and traditional precursors, respectively. The HDS evaluation results showed the activities of catalysts prepared from the new Waugh Co-Mo POM is higher than the reference catalysts. For the catalyst prepared from the new Waugh Co-Mo POM, the cationic substitution provides a higher Co/Mo ratio and atomic-level proximity between Mo and Co atoms, leading to shorter and less stacked MoS2 nano-particles and more exposure of unsaturated edges and corner sites. In addition, a weak interaction between the new Waugh Co-Mo POM and Al2O3 leads to more CoMoS active phases. Catalysts prepared from the new Waugh Co-Mo POM showed excellent HDS performance, demonstrating the new Waugh Co-Mo POM is a superior precursor to construct the efficient HDS catalyst.

Modifying the active phase structure of Ni2P/Al2O3 by Ga introduction for improved hydrodesulfurization of diesel

Modifying the structure of active phase is an effective protocol to improve the catalytic activity of hydrodesulfurization (HDS) catalyst. Here, a variety of mesoporous GaAlOx supports with various Ga doping amount were synthesized by a facile hydrothermal strategy. The corresponding Ni2P supported catalysts were fabricated via a conventional impregnation and temperature-programmed reduction method, and their catalytic performances for 4,6-DMDBT HDS were examined. The experimental analyses show that the introduction of Ga substantially influences the geometric and electrical structure of Ni2P active phase on Ni2P/GaAlOx catalysts. The metal-support interaction is effectively abated with the elevation of Ga doping amount, thereby increasing the d-electron density of Ni species and boosting the pre-hydrogenation (HYD) route, thereupon enhancing the HDS performances of corresponding Ni2P/GaAlOx catalysts. Therein, Ni2P/GaAlOx-0.50 exhibits the highest activity with 70.1% 4,6-DMDBT conversion because of the optimal morphology and percentage of active phase, as well as distinguished redox and acid property. Further increasing the Ga loading, however, inhibits the HDS activity of Ni2P/GaAlOx-1.0 catalyst due to the decrease in the fraction and dispersion of active phases. Therefore, this work may shine light on the understanding of structure–activity of HDS catalyst and thereafter the preparation of HDS catalysts with high efficiency in future.

Effect of Zirconium modified Y zeolite via in situ synthesis and its regulation on the formation of excellent NiW catalyst for ultra-deep hydrodesulfurization of 4,6-DMDBT

Alternative support materials, such as Y zeolite, have been introduced to overcome the challenges associated with industrial alumina-supported hydrodesulfurization (HDS) catalysts. However, to improve catalytic activity while avoiding excessive hydrocarbon cracking, the properties of Y zeolite, including acidity, should be modulated. Herein, Zr-modified Y zeolite was prepared via in-situ synthesis, and the corresponding NiW catalyst was obtained by impregnating hybrid zeolite-alumina supports with metal precursors. The catalytic performance was tested using 4,6-dimethyldibenzothiophene (4,6-DMDBT) as an HDS probe. The position of the Zr species in the zeolites depended on the modification methods. The ZrHY zeolite prepared by impregnation mainly formed non-framework ZrO2 on the surface of zeolite, whereas the HZrY zeolite via in-situ synthesis exhibited Zr species dispersed in the zeolitic framework. Zr species in the zeolitic framework not only enhanced the acidities of the zeolite and hybrid-support (HZrY-Al2O3), but also regulated the interaction of active metals and hybrid support, which significantly enhancing the catalytic activity of the catalyst. Among the four investigated catalysts, the turnover frequency (TOF) and reaction rate constant (k) of 4,6-DMDBT HDS over NiW/HZrYA catalyst were higher efficient than those of other catalysts, and their isomerization selectivity was improved, reducing hydrogen consumption. This enhanced efficiency was attributed to the NiW/HZrYA catalyst having more suitable acid sites, a greater degree of active metals sulfidation, more NiWS phase, superior isomerization performance, and a higher matching degree between hydrogenation and hydrolysis activity. These findings are great meaning for design the ultra-deep low hydrogen consumption HDS catalysts.

Design of active phase structure with high activity and stability in residue hydrotreating reactions

The catalyst with well-dispersed (Ni)MoS2 active phase characteristic of short slab length and low stacking numbers was designed by strengthening metal-support interaction (MSI) and metal dispersion, which displayed high activity and long-term stability in real-life residue hydrodesulfurization (HDS) reactions. Furthermore, the impacts of pseudo-boehmite and catalyst calcination temperature on surface properties were thoroughly investigated. Mo equilibrium adsorption method, Al27 NMR, XRD, Raman, UV–Vis DRS, and H2-TPR characterization showed that the hydroxyl groups concentration and tetrahedral cation vacancies increased upon reducing the pseudo-boehmite extrudates calcination temperature. Increasing calcination temperature of the catalysts further strengthened MSI, resulted in well-dispersed Mo species with enhanced MSI. Therefore, well-dispersed (Ni)MoS2 active phase was acquired on novel designed catalyst. XPS coupled with HRTEM indicated that the more potential active sites, less propensity for active phase evolution and gradual increase in sulfidation degree with processing time contributed to the high HDS performance of the designed active phase. This work can deepen our understanding toward evolution pattern of active phase during residue HDS catalysts, and give guidance for developing high performance catalyst by strengthening MSI and enhancing metal dispersion.

High-efficiency recycling of Mo and Ni from spent HDS catalysts: Enhanced oxidation with O2-rich roasting and selective separation with organic acid leaching- complexation extraction

Spent petroleum refining catalyst is regarded as the important secondary resource for valuable metals. However, common recycling strategies, including soda roasting, acid and alkaline solutions leaching and chemically precipitation, produced large quantities of high salinity wastewater. This study proposed an efficient method to recovery of Mo and Ni from the spent hydrodesulfurization (HDS) catalyst via O2-rich roasting and organic acid leaching with the advantage of less salinity wastewater production. The transformation of Mo(IV) into soluble Mo(VI) was enhanced by O2-rich atmosphere roasting, and 98.64% of Mo(IV) was oxidized at 650 ℃ for 2 h in atmosphere containing 30% of O2. The oxidation process of Mo(IV) was agreed with the shrinkage pore model, and regulated by surface reaction and internal diffusion. 97.97% of Mo(VI) was leached from roasted product by oxalic acid, separated with complexation extraction agent of Ala-TBP and recovered as (NH4)8Mo10O34 and (NH4)2Mo3O10 by evaporative crystallization. Ni was leached out from spent catalyst with 1 mol/L acetic acid, and precipitated as NiC2O4 with oxalic acid. 95.92% of Mo and 96.77% of Ni were recovered from spent HDS catalyst with this recycling route. This study provided a high-efficient and eco-friendly method to recovery of valuable metals from spent catalyst.

The Influence of Metal–Support Interactions on the Performance of Ni-MoS2/Al2O3 Catalysts for Dibenzothiophene Hydrodesulfurization

In this present work, a new kind of sulfurized hydrodesulfurization catalyst was synthesized via the hydrothermal treatment of MoS2, NiCO3·2Ni(OH)2·4H2O, and Al2O3 precursors, followed by annealing under a H2 atmosphere, which does not require a sulfurization process compared to traditional preparation methods. The influence of the annealing temperature and the type of Al2O3 precursor on the interactions between MoS2 and Al2O3 were studied using X-ray fluorescence spectroscopy, X-ray diffraction, N2 adsorption–desorption, Raman spectroscopy, X-ray photoelectron spectroscopy, and high-resolution transmission electron microscopy. The results indicated an increase in the number of stacked layers of the MoS2 catalyst, accompanied by a decrease in the degree of decoration of Ni atoms onto MoS2 nanoslabs, as a result of the strengthened MoS2–Al2O3 interaction. Subsequently, the efficiency of hydrodesulfurization (HDS) was evaluated using dibenzothiophene as a representative reactant, while establishing a correlation between the structure of the catalyst and its performance. The catalysts, using pseudo-boehmite as the precursor and calcined at 500 °C, synthesized by calcining pseudo-boehmite as the precursor for Al2O3 at a temperature of 500 °C and possessing suitable metal–support interactions, exhibited a reduced number of MoS2 stacking layers and lateral dimensions, along with an optimal decoration degree of Ni atoms, thereby resulting in the highest level of HDS activity.