Hydrodesulfurization Reaction Research Articles

Unveiling the degradation mechanism of cathodic MoS2/C electrocatalysts for PEMWE applications

Molybdenum dichalcogenides (MoS2) are promising non-noble alternatives to replace platinum (Pt) for Hydrogen Evolution Reaction (HER) electrocatalysis in Proton Exchange Membrane Water Electrolyzers (PEMWE). The knowledge acquired on this class of catalyst for hydrodesulfurization (HDS) reactions has enabled significant advances in designing active MoS2 for HER. However, the stability of MoS2 in the dynamic operating conditions of a PEMWE coupled to renewable energy sources is often overlooked in the literature and is the focus of the present work. Herein, using nano slabs of 2H MoS2 supported on high surface area carbon, we dynamically monitored Mo dissolution trends both under HER conditions and at more anodic potentials to mimic start-ups and shut-downs of a PEMWE device. We report minimal Mo dissolution under HER conditions but it continuously increased with higher electrode potentials. In particular, Mo dissolution peaked during the irreversible oxidation from Mo(IV) to Mo(VI) starting at E = 0.7 VRHE which in turn fully annihilates HER activity. Since no change in Mo and S surface composition was observed, the decline in HER activity was attributed to the continuous exfoliation of the 2D MoS2 stacked layers induced by oxidation/dissolution of Mo. Additionally, our findings indicate that Mo cations can redeposit onto the cathode catalytic layer, forming a Mo blue film primarily composed of Mo(VI) species. This redeposition hampers HER performance by blocking catalytic sites and diminishing the catalyst's overall efficiency. These insights demonstrate the need to avoid excursions above E = 0.6 VRHE for the safe use of MoS2 cathode catalyst in PEMWE.

Enhancing Ultradeep Hydrodesulfurization of Coker Diesel through Adsorptive Predenitrogenation.

The petroleum refining industry places significant challenge in the production of ultralow-sulfur diesel (ULSD) from various middle distillates with high nitrogen concentration in an energy-efficient and cost-effective way to meet strict environmental regulations as coexisting nitrogen compounds significantly inhibit the ultradeep hydrodesulfurization (HDS). Among all of the approaches reported in the literature for this challenge, a combination of adsorptive denitrogenation (ADN) and HDS has attracted great attention. This study focuses on ultradeep HDS of coker diesel (CD) through a synergistic approach combining ADN over a carbon-based adsorbent and the current HDS process. The study found that the predenitrogenation significantly enhanced the HDS reactivity of CD and greatly reduced the start of run temperature for producing ULSD by even 20 °C, depending on the denitrogenation depth. It results in dominantly decreasing energy and H2 consumption in the HDS process, and increasing the lifetime of the catalyst. Furthermore, the predenitrogenation prior to HDS significantly improved the quality of the hydrodesulfurized product by decreasing aromatic content and density, increasing the cetane index, and improving the color and stability of the product as the HDS process for producing ULSD can be conducted at a much lower temperature. The study demonstrated the combination of ADN and HDS for producing ULSD from CD on a pilot unit scale, and the advantages and disadvantages of this combination were discussed in comparison with the conventional HDS process. In addition, it was found that there is a good linear relationship between the logarithm of the product sulfur concentration and the HDS reaction temperature, which can be used conveniently to predict the start-of-run temperature to achieve different sulfur levels.

Insights into the Effect of a Microwave Field on the Properties of Modified γ-Alumina: A DFT Study

γ-Alumina is often used as a support for hydrodesulfurization catalysts due to its excellent performance. During the catalytic reaction, the strong surface acidity of γ-alumina can induce a strong interaction between the active phase and the support. The reaction activity of the catalyst can be affected by changing the present mode of the active phase on the surface of the support. The (110) crystal plane, acting as the strongest acidity plane of γ-alumina, was selected for modification. The supports modified with boron and phosphorus were successfully constructed, and the acid strengths were quantified by simulating the adsorption of the relevant probe molecules: pyridine in correlation with surface electronic properties via density functional theory. The surface adsorption energy calculation shows that the boron-modified surface is able to moderately reduce the adsorption capacity of alumina, while that of the surface modified by phosphorus is found to be enhanced over the sites of a tetrahedral coordination structure; however, at the other unsaturated Al sites, this is obviously reduced. The results of introducing electric fields imply that applying horizontal electric fields changes the surface acidity of alumina under the premise of a stable structure. With the enhancement of the horizontal electric fields, the adsorption capacity of tetra-coordination sites on the original surface gradually decreases, while those of the others gradually increases. However, for the boron-modified surface, introducing horizontal electric fields can reduce the adsorption capacity of all sites. Hence, microwave-electric-field-assisted modification of B further reduces the surface acidity of alumina, making it beneficial for deep hydrodesulfurization reactions.

Al2O3 Concentration Effect on Deep Hydrodesulfurization of 4,6-Dimethyldibenzothiophene over NiWS/Al2O3-ZrO2 Catalysts.

The Al2O3 concentration effect over NiWS/Al x Zr100-x catalysts was investigated for deep hydrodesulfurization (HDS) of 4,6-dimethyldibenzothiophene (4,6-DMDBT). The sol-gel method changed the wt % Al2O3 concentrations used to synthesize the Al x Zr100-x supports. The NiWS/Al x Zr100-x catalysts were prepared with ammonium metatungstate hydrate and nickel(II) nitrate hexahydrate by sequential incipient impregnation, calcination, and H2S/H2 activation. The catalytic evaluation data fit a pseudo-first-order trend in the 4,6-DMDBT HDS reactions. In the oxide phase, the catalysts presented Ni and W species in tetrahedral (td) and octahedral (oh) coordination, with the oh species prevailing as a function of the Al2O3 amount. The lower amount of Al2O3 can facilitate the "Type II" NiWS phase formation by weakening the interaction of the W-O-Al bond and promoting W and Ni species sulfidation. In the sulfide phase, catalysts with (oh) coordination and surface WO X species promote the formation of WS2 and NiWS species during the catalyst activation step. This species favors the reaction yield, where the hydrogenation route is predominant, with the highest initial reaction rate using the NiWS/Al25Zr75 catalyst. A direct correlation was found between high hydrogenation/hydrogenolysis ratio values and low Al2O3 concentrations.

Synthesis, characterization, and performance evaluation of unsupported tetrametallic CoMoMnAl and CoMoZnAl catalysts for selective hydrodesulfurization (HDS)

New formulations of unsupported tetrametallic catalysts derived from layered double hydroxides (LDH) compounds were synthesized by a constant pH coprecipitation method, characterized, and evaluated in the selective hydrodesulfurization (HDS) of thiophene in the presence of cyclohexene. The layered double hydroxides were prepared using terephthalate (C8H8O2)2- as the interlayer anion with nominal aluminum molar fraction of 0.5, and nominal cobalt to MII (M = Zn or Mn) ratios of 0.2, 0.4 and 0.6. Molybdenum introduction in the LDH precursor was accomplished by an ion exchange process using the heptamolybdate anion. The calcined Mn samples showed a higher surface area than those obtained from Zn. The sulfidation was carried out in situ with a heating ramp up to 673 K and the catalysts were evaluated in a tubular flow reactor. The catalytic evaluation of Zn and Mn-based materials for simultaneous thiophene HDS and cyclohexene hydrogenation (HYD) was conducted at 573 K and 20 bar. The results show that the Zn-based unsupported catalysts synthesized here exhibited higher selectivity for the HDS reaction than an industrial one.

Hydrodesulfurization of methanethiol over Co-promoted MoS2 model catalysts

The process of hydrodesulfurization is one of the most important heterogeneous catalytic reactions in industry as it helps with reducing global SOx emissions by selectively removing the sulfur contaminants from commercial fuel. In this work, we successfully combine high-pressure scanning tunneling microscopy and reaction modeling using density functional theory to observe the hydrodesulfurization of methanethiol (CH3SH) on the Co-substituted S edges of a Co-promoted MoS2 model catalyst in situ at near-industrial conditions and investigate the plausible reaction pathways. The active sites on the Co-substituted S edges show a time-varying atomic structure influenced by the hydrodesulfurization reaction rate. The involvement of the edge Co site allows for the C-S bond scission to occur at appreciable rates, and is the critical step in the hydrodesulfurization of CH3SH. The atomic structures of the S-edge active sites from our reaction models match excellently with those observed in situ in the experiments.

Sulfured FeMo carbides and nitrides catalysts upgrade extra heavy crude oil quality

In the context of the energy transition scenario, effective sulfur management is crucial. Enhancing the quality of extra heavy crude oil (EHCO) through catalytic processes, specifically hydrotreatment, is essential for reducing pollutant emissions like SOx into the atmosphere. Traditional hydrotreatment, utilizing MoS2-based catalysts typically on Al2O3 support, faces challenges with EHCO due to its elevated S and N content, which hampers catalyst efficiency. Metal carbides and nitrides exhibit promising electronic structures that confer resistance to deactivation in the presence of heteroatoms. This study compares the catalytic performances of Fe-promoted Mo sulfides, carbides, and nitrides (FeMoS(C,N)) in the thiophene hydrodesulfurization (HDS) reaction, serving as a model molecule for sulfur removal. Subsequently, we investigate the upgrading of a Venezuelan EHCO in terms of pollutant reduction, API gravity, and feedstock aromaticity. Catalysts were prepared from oxide precursors, varying the (Fe/(Fe+Mo)) atomic ratios (x = 0.00, 0.10, 0.33, 0.50, and 1.00), employing a temperature-programmed reaction protocol. Catalytic upgrading of EHCO was conducted in a stirred batch reactor, and the results were compared with a commercial CoMo-based catalyst. FeMoC(N) outperformed the commercial catalyst in sulfur removal. The elemental composition and nitrogen content of the feed remained constant; however, the sulfur content of asphaltenes decreased. Furthermore, the API gravity of crude oil increased when employing FeMoS and FeMoN catalysts, except with FeMoC, possibly linked to dealkylation reactions and the enrichment of lighter fractions with alkanes. FeMoN increased asphaltene aromaticity, while FeMoC decreased it. These results highlight the promise of FeMoC(N) as catalysts for HDS and upgrading heavy feedstocks.

Enhancing simultaneous hydrodesulfurization and hydrodenitrogenation reactions: Kinetic modeling of stacked NiMoP and CoMoP catalysts beds

Stringent environmental regulations require reducing fuel sulfur content for adequate operation of vehicle emission control systems. Deep hydrodesulfurization (HDS) removes over 99 % of sulfur compounds, including the less reactive ones like 4,6-dimethyldibenzothiophene (4,6-DMDBT). However, HDS kinetics is inhibited by compounds like H2S, nitrogenous compounds, and aromatics. This article delves into kinetic modeling of concurrent hydrodesulfurization (HDS) of 4,6-DMDBT and hydrodenitrogenation (HDN) of quinoline (Q) reactions. It explored the use of stacked beds of CoMoP and NiMoP catalysts in two configurations. The effects of temperature and weight hourly space velocity (WHSV) on conversions and product yields were investigated. Higher reaction temperatures, in addition to the expected increase of 4,6-DMDBT and quinoline overall conversions, also led to an increased in hydrogenation selectivity. Kinetic models were developed for these reactions and catalysts, and kinetic parameters were estimated using a hybrid numerical procedure. The configuration where CoMoP was the first catalyst to encounter the reaction feedstock exhibited higher conversions for both reactions. The apparent activation energies for 4,6-DMDBT HDS were 99 and 41 kJ mol−1 for NiMoP and CoMoP, respectively while for HDN, values of 62 and 68 kJ mol−1 were estimated. For the adsorption enthalpy of nitrogenous compounds, values of −59 and −40 kJ mol−1 were observed for NiMoP and CoMoP, respectively.

Flower-like hierarchical TS-1/Al2O3 composite supported NiMo catalysts for efficient hydrodesulfurization of dibenzothiophenes

Flower-like Al2O3 materials were successfully incorporated by TS-1 nanocrystals to synthesize Flower-like TS-1-Al2O3 (FTA) micro-mesoporous composite by a facile nano self-assembly method. FTA supported NiMo bimetallic catalysts (NiMo/FTA) were further constructed and applied to the hydrodesulfurization (HDS) reactions for dibenzothiophene (DBT) and 4,6-dimethyldibenzothiophene (4,6-DMDBT). FTA composites were constructed from flower-like pore structures stacked with nanosheets, which are conducive to the even load and dispersion of active species and the diffusion of macromolecular sulfur-containing compounds with relatively low resistance. The fabrication of TS-1 nanocrystals effectively enhanced the acidic sites, regulated the metal-support interaction, which could increase the stacking layer of MoS2 slabs, and producing more NiMoS-II type active phase. NiMo/FTA-10 presented the excellent HDS conversion of DBT (99.3 %) and 4,6-DMDBT (93.2 %) at 10 h−1, the highest reaction rate constant (2.6 × 10-7 mol g−1 s−1) and turnover frequency values (6.7 × 10-4 s−1) for 4,6-DMDBT HDS reaction. Compared to the direct desulfurization route (DDS), hydrogenation route (HYD) and isomerization route (ISO) can effectively eliminate the steric hindrance of 4,6-DMDBT, which is more conducive to the HDS reaction.

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.

Optimizing the Incorporation Modes of TiO2 in TiO2-Al2O3 Composites for Enhancing Hydrodesulfurization Performance of Corresponding NiMoP-Supported Catalysts

TiO2-Al2O3 supports with different incorporation methods of titania were synthesized via three methods: impregnation (TA-I), co-precipitation (TA-CP), and co-precipitation–hydrothermal treatment (TA-HT). And the NiMoP catalysts prepared on the corresponding supports were evaluated for hydrodesulfurization (HDS) reactions. The results demonstrated that the Ti atoms in TA-I are attached to alumina through hydroxyl groups, while the Ti atoms in TA-CP and TA-HT can be dispersed in the alumina skeleton. Variations in the incorporation modes of TiO2 affect the support properties, consequently influencing the nature of the active metal on the supports. The Ti atoms dispersed in the Al2O3 skeleton allow an increase in the basic hydroxyl groups. Meanwhile, TiO2 in TA-CP and TA-HT can absorb hydrogen molecules and be partially reduced. Furthermore, metal species supported on the TA-CP and TA-HT are more easily reduced and better dispersed. For the NiMoP catalysts prepared with TA-CP and TA-HT, the Ti element promotes the sulfidation degree of Mo, besides shortening the average (Ni)MoS2 slab. The catalysts prepared with TA-CP exhibited superior activity for 4,6-DMDBT hydrodesulfurization. This can be ascribed not only to the relatively high sulfidation degree of Mo and proportion of the NiMoS active phase but also to the well-dispersed (Ni)MoS2 slabs. Moreover, the Ti4+ ions dispersed in the Al2O3 skeleton can be partially reduced to act as electron donors, enhancing the metallic character of the S layers in MoS2, which facilitates the improvement of the hydrogenation desulfurization activity.

Suppression of inactive sites in NiMo@amorphous alumina catalysts for hydrodesulfurization reaction: Effect of Ga doping

Hydrodesulfurization (HDS) reaction activity depends on the formation of active NiMoS (completely sulfided multilayer type 2 sites) and inactive NiAl2O4/NixSy phases on the catalyst surface. These inactive phases not only itself inactive for the reaction but also hinder the formation of active NiMoS phases. In addition, the formation of strong Mo-O-Al bonds also lowers the reducibility of the catalyst, suggesting lesser catalytic activity (type 1 sites, partially sulfided single-layer sites). To this end, we report the formation of NiMo/Ga doped amorphous alumina (A-Al2O3) catalysts prepared by the colloidal synthesis method. A-Al2O3 was chosen as a support because it has lower surface energy, better physicochemical properties, and enhanced acidic sites than the crystalline alumina phase, which favours the formation of type 2 sites or weak metal-support interaction (completely sulfided multilayer NiMoS sites). Further, the Ga doping in A-Al2O3 support substitute the tetrahedral Al sites and form GaAl2O4 phases by reducing NiAl2O4 inactive sites, and the free Ni decorate the edges of MoS2 to form HDS active NiMoS sites. Therefore, NiMo/Ga doped A-Al2O3 catalyst (at 1 wt% Ga loading) reported enhanced HDS catalytic activity (25%), HDS reaction rate constant (kHDS-2.15 times) and turn over frequency (TOF-1.3 times) than the conventional NiMo/γ-Al2O3 catalysts.

N-octyltrimethylammonium bromide-assisted self-assembly of CoMo precursors to prepare CoMoS/Al2O3 catalysts for highly selective hydrodesulfurization of thiophene

A novel (C11H26N)2Co(MoS4)2 complex was prepared via the n-octyltrimethylammonium bromide-assisted self-assembly of CoMo precursors for the selective hydrodesulfurization (HDS) of thiophene. The complex was generated by the interaction between the negatively charged CoMo compound and the positively charged n-octyltrimethylammonium ions. Then positively charged bimolecular layers were formed owing to van der Waals forces between the C11H26N+ and the complex, and they were anchored on the negatively charged γ-Al2O3. Compared with CoMoS/γ-Al2O3 catalysts prepared by impregnation, the optimal CoMoN-0.3/γ-Al2O3 catalyst exhibited better performance for selective HDS due to the enhanced Mo dispersion, the close contact between Co and Mo, and the increased amount of CoMoS phases on γ-Al2O3. Among these catalysts, the optimal CoMoN-0.3/γ-Al2O3 catalyst with the highest concentration of CoMoS phases exhibited the highest HDS reaction rate constant of 6.95 × 10-6 mol·g−1·s−1 and the best selective factor of 26.1 for the selective HDS of thiophene with 1-hexene.

Insights into the hydrodesulfurization reaction mechanisms catalyzed by different K-promoted MoS2 edge sites

The K-promoted MoS2 active phase structure and its catalytic mechanism in the hydrodesulfurization reaction were investigated through the density functional theory calculations. On the basis of the calculations, the sulfur vacancy formation mechanism and the direct desulfurization of thiophene were systematically explored, and the structure–activity relationship was also discussed in detail. In the sulfur vacancy generation process, it could be found that the formation of sulfur vacancies was more favorable over the sulfur-rich edges, such as K-promoted S-edge with 100 % S coverage. In addition, the K-promoted S-edge was more preferable for the C-S bond scissions compared with the K-promoted M−edge. Furthermore, potassium atoms could prevent the adsorptions of toluene and 2-butene adsorptions, in order to reduce the excessive hydrogenation saturation of olefins and monocyclic aromatics, which would be beneficial for the octane rating maintenance during the production process of gasoline.

Controlled construction of Co3S4@CoMoS yolk-shell sphere for efficient hydrodesulfurization promoted by hydrogen spillover effect

A yolk-shell structured Co3S4@CoMoS catalyst was prepared through Oswald ripening method and subsequently used for hydrodesulfurization (HDS) reaction. The shells, constructed from Co-promoted MoS2 nanosheets, possess abundant active sites and facilitate the adsorption of reactants through the development of pore channels. The MoS2 sheets are arranged in a staggered and convoluted manner, creating numerous defect sites. The shorter MoS2 slabs provide a wide distribution of reactive sites, ensuring efficient reactions. The Co3S4 species within the inner core acts as an auxiliary active phase, inducing the hydrogen spillover effect in the HDS system. This facilitates the transfer of active hydrogen species to the CoMoS shell, where both CoMoS and Co3S4 phases synergistically enhance the HDS reaction. The Co3S4@CoMoS catalyst achieved up to 99.2% dibenzothiophene (DBT) conversion and 94.9% 4,6-dimethyldibenzothiophene conversion at the lower dosage (30 mg). The structure-activity relationships between active phase and HDS activity were investigated via in-situ infrared spectroscopy and other characterizations as well as density functional theory calculations.

Non-equilibrium electronic structure of Fe-based bulk catalysts: Dual-channel electron transfer behavior among Fe, Zn, and P species and its impact on hydrodesulfurization reaction pathway

Regulation of electronic structure of metal active phase for catalysts has been known as efficient in promoting its catalytic activity; however, manipulating the activity of catalysts via controllable metal active phase electronic structure is still challenging. A non-equilibrium electronic structure Fe-based bulk catalyst has been developed via controllably adding P species, where the non-equilibrium electronic structure of Fe species is formed through the electron transfer from the Zn species through the P electronic channel. As a result, the catalytic activity of the modified Fe-based bulk catalysts has increased by 24.4–50.4%. Meanwhile, the sulfurization degree (SD) of the modified Fe-based bulk catalysts has increased by 5.6–25.9%. In addition, the HDS reaction rate constant (kHDS) has increased by about 2.0 times, and the DDS reaction rate constant (kDDS) has increased by about 2.4 times. The P modifying can regulate the directional transfer of unpaired free electrons between Fe and Zn species to form a more non-equilibrium electronic structure of Fe species, which can reduce the energy barrier of the C–S bond adsorbed on the P-modified Fe-based bulk catalysts. Importantly, the P species can be used as an active site to adsorb S-containing compounds in the modified Fe-based bulk catalysts, which is conducive to generating more coordinatively unsaturated sites (CUSs). The former can promote the formation of the more non-equilibrium electronic structure of Fe species, and the latter can adjust the adsorption active site of S-containing on the catalyst surface. Therefore, an electron transfer channel is formed among Fe, Zn, and P species, and another one is formed among Fe, P, and S-containing compounds, which form a dual-channel electron transfer behavior. Furthermore, the specific surface area, total pore volume, and reducibility of the modified Fe-based bulk catalysts have also shown varying degrees of improvement via the controllable addition of P species.

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.

АКТИВНОСТЬ НИКЕЛЬ-МОЛИБДЕНОВОГО КАТАЛИЗАТОРА, РЕГЕНЕРИРОВАННОГО МЕТОДОМ СВЕРХКРИТИЧЕСКОЙ ФЛЮИДНОЙ ЭКСТРАКЦИИ

The activity of selective hydrogenation catalyst samples after supercritical fluid extraction regeneration at a temperature of 473 K and a pressure of 20 MPa with pure supercritical carbon dioxide and modified with hexane and ethanol was evaluated. The selectivity and chemical activity of the nickel-molybdenum catalyst LD-145 was determined on a model substance by the rate of the chemical reaction of hydrodesulfurization of the substance with the formation of dibenzotifene and the hydrogenation reaction of the substance with the formation of naphthalene in a flow-through experimental setup. The qualitative composition of the hydronisate was determined by gas-liquid chromatography on a Kristall-2000 chromatograph. The activity in the target reaction of naphthalene hydrogenation of the deactivated catalyst was 41.3%; catalyst regenerated with pure supercritical carbon dioxide - 43.4%; sample regenerated with a mixture of supercritical carbon dioxide + ethanol - 45.5%; and the sample regenerated with a mixture of supercritical carbon dioxide + hexane - 57%. Thus, the highest hydrogenation capacity was achieved on the sample regenerated with modified supercritical carbon dioxide hexane. Thus, the test results indicate an increase in the catalytic activity of catalyst samples that were regenerated by the supercritical fluid extraction method. It has been established that both the hydrogenating and hydrodesulfurizing functions of the catalyst can be restored. The level of recovery of the target hydrogenating activity of the catalyst achieved in this work is 57%. The level of recovery of catalytic activity of the spent catalyst samples can be improved by optimizing the conditions of supercritical fluid extraction process, more successful selection of the physical and chemical nature of the extractant and possibly earlier abandonment of the method of oxidative regeneration of the investigated catalyst during its operation.

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.

Liquid-phase adsorption of nitrogen compounds from model diesel fuel on activated carbons

One of the great challenges in deep hydrodesulfurization (HDS) to produce ultra-low-sulfur diesel (ULSD) is the coexisting heterocyclic nitrogen-containing compounds in middle distillates, which significantly inhibit the HDS reactions. This study investigates various activated carbon (AC) samples for selectively removing nitrogen compounds from a model diesel fuel through adsorption. The physical and chemical properties of the AC samples were characterized using low-temperature N2 adsorption–desorption, SEM–EDS, and FT-IR to explore their impact on the adsorption performance. The results indicate that the adsorption performance is influenced not only by the surface area and by the number of oxygen-containing functional groups on the surface but also by the pore diameter distribution. Among all AC samples tested, AC-W exhibited the highest adsorption capacity, achieving a nitrogen removal rate of 97.8% with the addition of 10 wt.% of AC-W. The adsorption capacity was approximately 24.0 mg-N/g-A at a nitrogen equilibrium concentration of 200 ppmw. The adsorption isotherms for total nitrogen and individual nitrogen compounds in the fuel over AC can be described well by the Freundlich isotherm model. An approach for improving the ADN performance of AC is discussed based on the findings in this study.