Hydrodesulfurization Efficiency Research Articles

Comparison between Conventional and Metakaolin bi-functional Catalyst in the Hydrodesulfurization Operation

The present study investigates hydrodesulfurization (HDS) of gas oil with 9300 ppm (0.93 wt%) sulfur supplied from Al-Dura Refinery by using an economic catalyst prepared from raw mineral (kaolin clay) cemented by alumina as composite support alumina meta-kaolin (AMK). Characterization of the prepared catalyst was achieved by using Energy Dispersive X-Ray Analysis (EDAX), scanning electron microscopy (SEM), BET surface area, pore volume , Bulk density, X-ray diffraction analysis (XRD) and Fourier-transform infrared spectroscopy (FTIR). AMK was modified as a bifunctional catalyst with active metal (Co and Mo). The hydrodesulfurization (HDS) efficiency was evaluated and compared with the traditional catalyst (CoMo-Al2O3) in a hydrotreating reaction carried out in one stage reactor at temperature 375 oC, pressure 40 bar, LHSV 1hr-1, and H2/HC ratio 200 vol. ratio. 62.2% and 90% of hydrodesulfurization efficiency were achieved for prepared catalyst (CoMo-AMK) and commercial CoMo-Al2O3 respectively at the same operating conditions.

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

Low-cost pure aluminum-based Al-TUD-1 mesoporous materials (AT) were successfully synthesized and the corresponding NiMo/AT catalysts were modified with Citric acid (CA), which were utilized for dibenzothiophene (DBT) and 4,6-dimethyldibenzothiophene (4,6-DMDBT) hydrodesulfurization (HDS) reactions. CA could effectively modulate the acidity and metal-support-interaction (MSI) of NiMoCA(x)/AT catalysts, which were in favor of generating more MoS2 active species with higher sulfurization degree and higher dispersion degree. The morphology of the MoS2 active phase of NiMoCA(x)/AT catalysts was changed after the addition of CA. The NiMoCA(2)/AT catalyst showed the higher B/L ratio and higher S-edge/M-edge ratio, which was conducive to the isomerization (ISO) route selectivity (81%) of 4,6-DMDBT HDS, thus resulting the improvement of HDS activity of the NiMoCA(2)/AT catalyst. The NiMoCA(2)/AT exhibited the maximal DBT and 4,6-DMDBT HDS efficiency of 99.0% and 95.5% as well as maximal kHDS and TOF values of 4,6-DMDBT HDS (13.4 × 10−4 mol⋅g−1⋅h−1, 4.7 h−1) among other series NiMoCA(x)/AT catalysts and reference commercial NiMo/Al2O3 catalyst at the Weight hour space velocity (WHSV) of 10 h−1.

Insights into the effect of solvent on dibenzothiophene hydrodesulfurization

The hydrodesulfurization (HDS) of dibenzothiophene (DBT) over a NiMo/Al-SBA-15 catalyst was performed in different solvent systems and the results showed that the solvent selection had a great impact on the TOF values and the reaction networks. The phase equilibrium experiments, and the PRO/II stimulation ascribed the solvent effects as the partial evaporation of DBT and the large diffusion resistance in the gas-liquid-solid reaction. The density functional theory (DFT) simulation and the GC–MS results attributed the solvent effects to the competitive adsorption of H2, DBT, and the solvent molecules on the active sites. Hydrogen donations of decalin and tetralin were found to have negligible contributions to the HDS processes, while the corresponding dehydrogenation process of decalin and tetralin would produce naphthalene and the other polycyclic aromatic compounds, consequently leading to the lower HDS efficiencies. Furthermore, the internal diffusion effectiveness factors (η) were calculated, and the results demonstrated that the HDS of DBT in the p-xylene and tetralin solvent systems were limited by the surface-reactions, while that in the DBT-cyclohexane system was limited by the intraparticle diffusion.

Catalytic activity of synthesized 2D MoS2/graphene nanohybrids for the hydrodesulfurization of SRLGO: experimental and DFT study.

Hydrodesulfurization (HDS) of straight run light gas oil (SRLGO) using novel highly active two-dimensional (2D) MoS2/graphene (G) nanohybrid catalysts is a precursor technology for the production of clean heavy fuel. The aim of this research is the synthesis of 2D MoS2/G nanohybrid catalysts by use of exfoliation method from commercial bulky MoS2 and graphite using hydrothermal ball milling system, which is a low-cost, high-yield, and scalable method. These nanohybrid catalysts were characterized by XRD, Raman spectroscopy, XPS, SEM, TEM, STEM, ICP, BET surface, TPR, and TPD techniques. Also, catalytic activities of 2D MoS2/G nanohybrid catalysts were evaluated under different operating conditions such as temperature, pressure, LHSV, and H2/Feed (SRLGO) ratio in the HDS reaction. The conversion of the HDS of SRLGO with 14000 ppm sulfur showed a considerably higher activity of 2D MoS2/G nanohybrid catalyst (99.95% HDS efficiency) compared with the Co-Mo/γAl2O3 as a commercial catalyst (90% HDS efficiency) in the operation condition (340 °C, 40 bars, LHSV: 1 h-1and H2/oil: 600 NL L-1) which is economically valuable. Using density functional theory calculations, the detailed mechanism of the HDS process over MoS2/G catalyst was explored. It was found that sulfur coverage on the Mo edge of MoS2 plays an important role in the hydrogenation of sulfur components.

Tailoring NiMoS active phases with high hydrodesulfurization activity through facilely synthesized supports with tunable mesostructure and morphology

Nanoscaled mesoporous silicas (NMS) with tunable mesostructure and morphology were successfully fabricated using a simple modified-Stöber synthesis system. The Al modified NMS-x materials with highly ordered mesostructures were used as supports to prepare hydrodesulfurization (HDS) catalysts NiMo/Al-NMS-x. The characteristics and activity test results revealed that the dispersion and morphology of NiMoS active phases were modulated on various supports, and TOF values showed dependence on the stacking degrees and dispersion of MoS2 slabs. Moreover, diffusion properties reflected that a support with larger pore size and 3D mesochannel would alleviate restrictive diffusion. Compared to other catalysts, NiMo/Al-NMS-7 with 3D cubic mesochannel and sphere-like shape exhibited the highest catalytic activity, i.e., HDS efficiency (95%, WHSV = 20 h−1), TOF (4.8 ± 0.32 h−1), rate constant (1.4 × 10-3 mol·g−1·h−1) and De (12.8 × 106 cm2·s−1), which would be derived from the preferable diffusion performance of guest-species, especially the better dispersion and suitable stacks of active phases.

Hydrotreating atmospheric gasoil and co-processing with rapeseed oil using supported Ni-Mo and Co-Mo carbide catalysts

Sulfur-free Mo carbide catalysts supported on Al2O3 and TiO2 have shown good activity during the co-processing of middle distillates with vegetable oils in prior studies. However, their hydrotreating activity is low compared with that of conventional hydrotreating catalysts. To increase the hydrotreating effectiveness, promoter metals, such as Ni or Co, can be added. This paper describes an extensive study on the use of four sulfur-free Ni-Mo and Co-Mo carbide catalysts (supported on Al2O3 and TiO2) for the hydrotreatment of atmospheric gasoil (AGO) and co-processing with rapeseed oil (RSO). The tests were conducted in a fixed bed reactor unit at 330–350 °C, 5.5 MPa, a weigh hourly space velocity (WHSV) = 1–2 h−1, and AGO/RSO of 100/0, 95/5, 90/10, and 75/25 wt.%. Analogous to conventional hydrotreatment catalysts, adding the promotor metals significantly increased the product quality and the hydrodesulfurisation and hydrodenitrogenation efficiencies at higher temperatures or at lower WHSVs. In the case of RSO co-processing, all the tested catalysts promoted the hydrodeoxygenation pathway instead of (hydro)decarboxylation/decarbonylation with an insignificant decrease in the hydrodesulfurization efficiency at lower AGO/RSO ratios. Therefore, our results suggest that promoting Mo carbide catalysts with Ni or Co significantly improves their catalytic properties, making them more competitive with conventional hydrotreating catalysts.

Experimental and theoretical study of microwave enhanced catalytic hydrodesulfurization of thiophene in a continuous-flow reactor

Hydrodesulfurization (HDS) of thiophene, as a gasoline model oil, over an industrial Ni-Mo/Al2O3 catalyst was investigated in a continuous system under microwave irradiation. The HDS efficiency was much higher (5%–14%) under microwave irradiation than conventional heating. It was proved that the reaction was enhanced by both microwave thermal and non-thermal effects. Microwave selective heating caused hot spots inside the catalyst, thus improved the reaction rate. From the analysis of the non-thermal effect, the molecular collisions were significantly increased under microwave irradiation. However, instead of being reduced, the apparent activation energy increased. This may be due to the microwave treatment hindering the adsorption though upright S-bind (η1) and enhancing the parallel adsorption (η5), both adsorptions were considered to favor to the direct desulfurization route and the hydrogenation route respectively. Therefore, the HDS process was considered to proceed along the hydrogenation route under microwave irradiation.

Sulfur free supported MoCx and MoNx catalysts for the hydrotreatment of atmospheric gasoil and its blends with rapeseed oil

Generally, the commercial catalysts for hydrotreatment in refineries are supported sulfide transition-metal-based catalysts. However, the co-processing of vegetable oils reduces their hydrodesulfurization (HDS) efficiency by leaching sulfur from the active sites of the catalyst. The present work reports the use of six sulfur-free MoCx and MoNx catalysts (supporter with Al2O3, TiO2 or ZrO2) for the hydrotreatment of atmospheric gasoil (AGO) and co-processing of rapeseed oil (RSO – 5, 10 and 25 wt%). The screening tests were carried out in a fixed bed reactor at industrial operating conditions (330–350 °C, 5.5 MPa, WHSV = 1–2 h−1). Higher reaction temperatures and lower WHSV had a positive effect on catalyst activity and product quality. In case of co-processing, the hydrodeoxygenation reaction mechanism was found to be dominant, producing n-C16 and n-C18 n-alkanes at all AGO/RSO ratios used. Overall, our results suggest that alumina supported catalysts are the most promising materials, exhibiting a combination of excellent stability, high activity and no negative effects on HDS efficiency during AGO/RSO co-processing.

Synthesis of mesoporous γ-Al2O3 by using cellulose nanofiber as template for hydrodesulfurization of dibenzothiophene

Mesoporous γ-Al2O3 materials with different channel properties were successfully synthesised by using cellulose nanofiber (CNF) as template. The corresponding NiMo catalysts were prepared and further evaluated in the hydrodesulfurization (HDS) of dibenzothiophene (DBT). The as-synthesised γ-Al2O3 supports and NiMo catalysts were characterized by XRD, nitrogen adsorption-desorption, H2-TPR, Raman, SEM, TEM, XPS and HRTEM techniques. The NiMo/MA-7 catalyst displayed the highest DBT conversion at all liquid hourly space velocities (LHSVs). At high LHSV of 150 h−1, DBT HDS efficiency over NiMo/MA-7 (∼30%) is about six times than that of the comparison catalyst NiMo/MA-0 (5%) without CNF addition. This outstanding performance attributed to synergistic effects of open mesoporous structure, appropriate dispersion and stacking morphology of active metals, and the suitable MSI (metal-support-interaction). In addition, the products distributions of all catalysts in the HDS of DBT were investigated, and it is found that HYD/DDS ratio was promoted after using CNF as template agent.

Influence of Support Acidity on the HDS Performance over β-SBA-16 and Al-SBA-16 Substrates: A Combined Experimental and Theoretical Study

A novel composite material β-SBA-16 is successfully synthesized and utilized as the support for the development of hydrodesulfurization (HDS) catalyst. The supports and the corresponding catalysts were characterized by a variety of techniques involving X-ray diffraction, N2 physisorption, 27Al NMR, Raman, pyridine IR, X-ray photoelectron spectra, and high-resolution transmission electron microscopy. The activity evaluation results displayed that the NiMo/β-SBA-16 catalyst possessed the highest dibenzothiophene HDS efficiency of 97.3% at weight hourly space velocity of 20 h–1 compared with the catalysts supported on the Al-modified SBA-16 and the conventional Al2O3. Furthermore, the HDS efficiency of NiMo/β-SBA-16 is almost 1.5 times that of the other two catalysts at 150 h–1, which was considered to be closely linked to the acidic properties of the supports. Correspondingly, the results of pyridine IR exhibited that NiMo/β-SBA-16 possessed larger amounts of total acidity and higher B/L acidities ratio. Fu...

The development of catalysts and their stacking technology for diesel ultra-deep hydrosulfurization

The CoMo type and NiMo type catalysts with high amounts of Bronsted (B) acid sites, referred to as FHUDS-5 and FHUDS-6 respectively, were investigated for their hydrogenation performances including alkylation, hydrodesulfurization (HDS), and hydrodenitrogenation (HDN). The results demonstrated that, as hydroprocessing different diesel feedstocks, appropriate types of catalyst or their stacking system should be considered to achieve optimal HDS performance. As processing the feedstock with high sulfur content but low contents of nitrogen and aromatics, the CoMo type FHUDS-5 exhibited the highest HDS efficiency. On the other hand, the NiMo type catalyst FHUDS-6 presented the highest HDS and HDN efficiency as processing the feedstock with high amounts of nitrogen and aromatics. As processing the feedstock with medium contents of nitrogen and aromatics, the catalysts stacking system of FHUDS-6/FHUDS-5 presented the highest HDS efficiency due to their synergistic effects. The commercial applications for these hydroprocessing catalysts for the ultra-deep HDS on diesel at different refinery plants were also reported.

Study on Hydrodesulfurization of a Mixture of Middle Distillates

This study aimed to investigate the feasibility of hydrodesulfurization (HDS) of a mixture of crude oil fractions (e.g., naphtha, kerosene, and gas oil) all in one time in a single reactor loaded with $$\hbox {NiCoMo}/\hbox {Al}_{2}\hbox {O}_{3}$$ under various operating parameters such as temperature $$(310{-}370\,^{\circ }\hbox {C})$$ , pressure (40–55 bars), weight hour space velocity $$(1.2\hbox {--}3.6\, \hbox {h}^{-1})$$ , and hydrogen-to-hydrocarbon ratio (150–300 vol/vol). Experimental results showed that temperature and pressure have positive effects on process performance while weight hour space velocity gives a different trend. Optimum operating conditions (i.e., $$350 \,^{\circ }\hbox {C}$$ , $$50\,\hbox {bars}, 1.2\,\hbox {h}^{-1}$$ , and 200 vol/vol) with the theoretical and experimental values of HDS efficiency of 95.4 and 95.8%, respectively, were estimated using advance statistical software DESIGN-EXPERT 10.0.6.0. Reaction products were fractionated and analyzed for comparing with products of the conventional HDS method. An approximate evaluation of the proposed system indicated a 60% reduction in fixed capital cost compared to that for conventional hydrotreatment system. The experimental analysis revealed the feasibility of the proposed method.

Study on novel scheme for hydrodesulfurization of middle distillates using different types of catalyst

This study aimed to investigate the hydrodesulfurization (HDS) of a mixture of crude oil fractions (e.g., naphtha, kerosene, and gas oil) all in one time in a single reactor under various operating parameters such as temperature (T = 310–370 °C), pressure (P = 40–55 bar), weight hour space velocity (WHSV = 1.2–3.6 h−1), hydrogen-to- hydrocarbon ratio (150–300 vol/vol), and type of catalysts (di-metallic and tri-metallic). Experimental results showed that temperature and pressure have positive effects on process performance while weight hour space velocity gives a different trend. Results indicated that HDS efficiency was 95.8% at optimized operating parameters T = 350 °C, P = 50 bars, WHSV = 1.2 h−1, and (H2/HC) ratio = 200 vol/vol. and with NiCoMo/γ-Al2O3 catalyst which offered a higher HDS efficiency compared with other types of catalysts used. Kinetic analysis revealed that a pseudo-first order rate law is well expressing the HDS reaction of the operating system for all types of catalysts. Estimation of rate parameters over each type of catalyst was also presented. Study of mass transfer limitations revealed that surface reaction is the rate controlling step. Feasibility of the proposed technique may offer a large reduction in fixed and operating costs of the HDS unit in a modern petroleum refinery.

Effects of Ga- and P-modified USY-based NiMoS catalysts on ultra-deep hydrodesulfurization for FCC diesels

USY zeolites have been modified by incorporation of gallium, phosphorus and a combination of gallium and phosphorus by wetness impregnation method using gallium nitrate and ammounium phosphate diabasic, and the corresponding NiMo supported hydrodesulfurization (HDS) catalysts have been prepared for HDS of an inferior FCC diesel. The individual physical-chemical properties of the modified USY zeolites and the series NiMo supported catalysts were characterized using XRD, N2-adsorption-desorption(BET), NH3-TPD, Py-FTIR, H2-TPR, HRTEM and XPS methods, and their catalytic performances for an inferior FCC diesel HDS were assessed. The results show that both gallium and phosphorus modification can modulate the acid property of USY zeolite and weaken the interaction between the active metal and the supports, thus enhancing the degree of sulfidation and the dispersion of Mo species that are beneficial for the HDS of highly refractory organosulfur compounds. The highest HDS and HDN efficiencies of 99.7% and 99.6%, respectively, were observed over the catalyst containing the PGaUSY zeolite. More importantly, gallium modification of the USY zeolite promotes the hydrodesulfurization of all organosulfur compounds, and especially 4,6-DMDBT, in the FCC diesel and phosphorus modification of the USY zeolite promotes the hydrodesulfurization of most organosulfur compounds except for 4,6-DMDBT in the FCC diesel.

Diesel Ultradeep Hydrodesulfurization over Trimetallic WMoNi Catalysts by a Liquid-Phase Preparation Method in a Slurry Bed Reactor

A series of Ni–Mo–W slurry catalysts were prepared by a novel complete liquid-phase method and tested for diesel ultradeep hydrodesulfurization (HDS) in a slurry bed reactor. Results showed that Ni–Mo–W catalysts prepared by this novel method exhibited a relatively high HDS efficiency, reaching approximately 96%. Characterization results showed that a suitable amount of W was beneficial for the dispersion of MoS2 species and the production of small particles. Meanwhile, the catalysts incorporating a suitable amount of W had a shorter slab length and more stacking number of MS2, which would enhance the HDS activity. It was also found that HDS efficiency was closely related to (Ni + Mo + W)/(Ti + Al) atomic ratios on the catalyst surface. The incorporation of a suitable amount of W was beneficial for the HDS reproduction, and the best catalytic performance was obtained when the Ni/W atomic ratio was 1:0.5.

Hydro-upgrading Performance of Fluid Catalytic Cracking Diesel over Different Crystal Forms of Alumina-Supported CoMo Catalysts

A series of CoMo/Al2O3 catalysts was prepared using different crystal forms of alumina (including γ-Al2O3, δ-Al2O3, θ-Al2O3, and α-Al2O3) as supports for the hydrodesulfurization (HDS) and hydrodenitrogenation (HDN) of fluid catalytic cracking diesel. The physicochemical properties of the supports and the corresponding catalyst were analyzed by various characterization methods. The results showed that δ-Al2O3 possessed a moderate surface area, a concentrated pore size distribution, and less surface hydroxyl groups. The CoMo/δ-Al2O3 catalyst exhibited the highest HDS and HDN efficiencies, 98.4 and 96.1%, respectively. This could be attributed to its reduced metal–support interaction, moderate stacking morphology, and highest sulfidation degree of active phases. The HDS and HDN efficiencies of the catalysts followed the order of CoMo/α-Al2O3 (87.3 and 72.2%) < CoMo/γ-Al2O3 (94.8 and 87.9%) < CoMo/θ-Al2O3 (96.2 and 90.1%) < CoMo/δ-Al2O3 (98.4 and 96.1%).

Post Synthesis of Aluminum Modified Mesoporous TUD-1 Materials and Their Application for FCC Diesel Hydrodesulfurization Catalysts

Post-synthesis methods are a promising technology and have received much attention. In this paper, a series of post-synthesis aluminum modified TUD-1 (PAT) materials with different Al contents were successfully prepared by using aluminum isopropoxide to be Al sources, then the as-synthesized materials were adopted as support additives mixed with commercial γ-Al2O3 to prepare hydrodesulfurization (HDS) catalysts for FCC diesel. The supports and catalysts were analyzed using N2 adsorption-desorption, XRD, SEM, Py-IR, ICP, 27Al MAS NMR, UV-vis, H2-TPR and HRTEM techniques. The results of Py-IR and 27Al MAS NMR indicated that the addition of Al species could bring Lewis (L) and Brönsted (B) sites into Si-TUD-1, and that the material of PAT-3 had the highest total acidity sites and Brönsted acid sites among the series PAT composites. The HRTEM technique showed that, compared to the traditional catalyst NiMo/γ-Al2O3, the sulfided catalyst NiMo/APAT-3 had a relatively short length (3.2 nm) and suitable stacking number (2.5) of MoS2 slabs. The HDS efficiencies of all the catalysts were tested in a fixed bed micro-reactor with FCC diesel as feedstock. The catalytic results confirmed that the catalyst NiMo/APAT-3 possessed the highest HDS efficiency (97.0%), due to synergistic effects of advantageous properties such as higher acidity, moderate MSI, and relatively short length of the MoS2 slabs.

Experimental Study on Catalyst Deactivation by Nitrogen Compounds in a Hydroprocessing Reactor

The present work was devoted to study the effect of nitrogen compounds on hydrodesulfurization (HDS) activity of straight-run heavy naphtha loaded with thiophene, as a sulfiding model, onto a commercial \(\hbox {CoMo/Al}_{2}\hbox {O}_{3}\) in a fixed bed reactor. Parameter evaluation of ideal flow behavior in the reactor revealed that a catalyst bed packed with a particle diameter \(\,=\,316 \,\upmu \hbox {m}\) helps to eliminate wall, poor wetting and back-mixing effects. Results showed that sulfur removal would be enhanced by increasing temperature, and pressure, while liquid flow rate gives a different trend. The effect of nitrogen compounds on reaction rate constant was investigated (at temperature 320–380\(^{\circ }\hbox {C}\), pressure 30 bar, particle diameter \(316 \,\upmu \hbox {m}\), and \(\hbox {WHSV}= 2.5\,\hbox {h}^{-1}\)) with different concentrations of carbazole and pyridine, and a mixture with equal weight proportions of them. The experimental results were fitted to a first-order kinetics with correlation coefficients higher than 0.98. The experimental results confirmed that addition of nitrogen compounds does not affect the order of HDS reaction. Hydrodesulfurization efficiency was decreased from 93.4 to 73.3, 66.5, and 63.3% as the concentration of carbazole, pyridine, and a mixture of them increased from 0 to 100 ppmw, respectively. As observed from experimental results, the inhibiting effect of nitrogen compounds on HDS activity increased as the nitrogen concentration increased. The inhibition behavior was found to be highly nonlinear.

Hierarchically Structured Porous Silica Spheres by Microemulsion/Vesicle Templating for Hydrodesulfurization of Fluid Catalytic Cracking Diesel

A series of hierarchically structured porous silica sphere (HSPSS) materials are successfully fabricated by a facile, one‐step microemulsion/vesicle bimodal method in a multicomponent microemulsion system of P123/n‐butanol/1,3,5‐trimethylbenzene/KCl/H2O (surfactant/cosurfactant/oil/salt/water). The pore structures of the obtained HSPSS products consist of mesocellular foam and mesostructured vesicles. In contrast to the traditional porous silica materials the new structures combine two separate, distinct mesophases with different‐sized mesovoids in a single porous sphere. Moreover, the proportion of every mesophase in obtained HSPSS can be easily adjusted by tuning the initially added amount of n‐butanol or KCl in this multicomponent microemulsion system. When the molar ratio of KCl/tetraethoxysilane is 2.15, the obtained HSPSS material is turned into uniform mesostructured vesicle silica spheres, which consist of many small diameter vesicle particles. The hydrodesulfurization (HDS) activity of fluid catalytic cracking diesel over the HSPSS was tested. HSPSS‐0.75‐1.43 catalyst support with multiple mesoporous structures shows the highest HDS efficiency (98.5%) among all the studied catalysts.

Synthesis of mesoporous silica material with ultra-large pore sizes and the HDS performance of dibenzothiophene

Ultra-large mesoporous silica materials using different micelle expanders including hexane, cyclohexane, 1,3,5-triisopropylbenzene and 1,3,5-triethylbenzene, have been successfully synthesized by the template of polymer surfactant of P123 (Aldrich, EO20PO70EO20). Among all the used micelle expanders, highly ordered cubic mesoporous silica material (SBA-16@hexane) with ultra-large pore size was obtained by using hexane. All the obtained samples were well characterized by small-angle X-ray scattering (SAXS), transmission electron microscopy (TEM), nitrogen adsorption–desorption, UV–vis diffuse reflectance spectroscopy (DRS), H2-TPR, pyridine-FTIR, 27Al MAS NMR, GC–MS and Raman. The synthesis mechanism was also proposed. Compared with the conventional SBA-16 (6.31 nm) synthesized taking polymer surfactant of F127 (propylene oxide block copolymer) as the template, the as-synthesized SBA-16@hexane had a pore diameter of 15.1 nm with a highly ordered mesostructure, which was the largest one among all the reported pore sizes of SBA-16 materials. The corresponding hydrodesulfurization (HDS) catalysts of NiMo/Al-SBA-16@hexane, NiMo/γ-Al2O3, and NiMo/Al-SBA-16 were prepared by using different supports respectively, furthermore, their HDS performances were evaluated adopting dibenzothiophene (DBT) as the probe reactant. The DBT HDS efficiencies over these catalysts followed the order: NiMo/Al-SBA-16@hexane > NiMo/γ-Al2O3 > NiMo/Al-SBA-16. The high activity of NiMo/Al-SBA-16@hexane can be attributed to the superior diffusivity of the novel support of SBA-16@hexane with ultra-large pore size.