Al-modified yolk-shell silica particle-supported NiMo catalysts for ultradeep hydrodesulfurization of dibenzothiophene and 4,6-dimethyldibenzothiophene:Efficient accessibility of active sites and suitable acidity

Yolk-shell SiO2 particles(YP)with center-radial meso-channels were fabricated through a simple and effective method.Al-containing YP-supported NiMo catalysts with different Al amounts(NiMo/AYP-x,x=Si/Al molar proportion)were prepared and dibenzothiophene(DBT)and 4,6-dimethyl-dibenzothiophene(4,6-DMDBT)were employed as the probes to evaluate the hydrodesulfurization(HDS)catalytic performance.The as-prepared AYP-x carriers and corresponding catalysts were characterized by some advanced characterizations to obtain deeper correlations between physicochemical properties and the HDS performance.The average pore sizes of series AYP-x supports are above 6.0 nm,which favors the mass transfer of organic sulfides.The cavity between the yolk and the shell is beneficial for the enrichment of S-containing compounds and the accessibility between reactants and active metals.Aluminum embedded into the silica framework could facilitate the formation of Lewis(L)and Brønsted(B)acid sites and adjust the metal-support interaction(MSI).Among all the as-synthesized catalysts,NiMo/AYP-20 catalyst shows the highest HDS activities.The improved HDS activity of NiMo/AYP-20 catalyst is attributed to the perfect combination of excellent structural properties of the yolk-shell mesoporous silica,enhanced acidity,moderate MSI,and good accessibility/dispersion of active components.

Combined Promoting Effects of Specific Organic Functional Groups and Alumina Surface Characteristics for the Design of a Highly Efficient NiMo/Al_(2)O_(3) Hydrodesulfurization Catalyst

To prepare a highly efficient NiMo/Al_(2)O_(3) hydrodesulfurization catalyst,the combined effects of specific organic functional groups and alumina surface characteristics were investigated.First,the correlation between the surface characteristics of four different alumina and the existing Mo species states was established.It was found that the Mo equilibrium adsorption capacity can be used as a specific descriptor to quantitatively evaluate the changes in surface characteristics of different alumina.A lower Mo equilibrium adsorption capacity for alumina means weaker metal-support interaction and the loaded Mo species are easier to transform into MoS2.However,the Mo-O-Al bonds still exist at the metal-support interface.The introduction of cationic surfactant hecadecyl trimethyl ammonium bromide(CTAB)can further improve Mo species dispersion through electrostatic attraction with Mo anions and interaction of its alkyl chain with the alumina surface;meanwhile,the introduction of ethylenediamine tetraacetic acid(EDTA)can complex with Ni ions to enhance the Ni-promoting effect on Mo.Therefore,the NiMo catalyst designed using alumina with lower Mo equilibrium adsorption capacity and the simultaneous addition of EDTA and CTAB exhibits the highest hydrodesulfurization activity for 4,6-dimethyl dibenzothiophene because of its proper metal-support interaction and more well-dispersed Ni-Mo-S active phases.

Active phase morphology engineering of NiMo/Al2O3 through La introduction for boosting hydrodesulfurization of 4,6-DMDBT

Herein,we designed and constructed a mesoporous LaAlOx via a solvent evaporation induced self-assembly protocol.The structure and physicochemical property of the corresponding NiMo supported catalyst was analyzed by a set of characterizations,and its catalytic activity was investigated for hydrodesulfurization(HDS)of 4,6-dimethyldibenzothiophene.It has confirmed that the incorporation of La profoundly facilitate the generation of“Type II”NiMoS phase by weakening the interaction of Mo–O–Al leakage and promoting the sulfidation of both Ni and Mo oxides as well as changing the morphology of Ni promoted MoS2 slabs,thereafter boosting the HDS performance substantially.The finding here may contribute to the fundamental understanding of structure-activity in ultra-deep desulfurization and inspire the advancement of highly-efficient HDS catalyst in future.

Tuning active sites in MoS_(2)-based catalysts via H_(2)O_(2)etching to enhance hydrodesulfurization performance

A H_(2)O_(2)etching strategy was adopted to introduce coordinatively unsaturated sites(CUS)on MoS_(2)-based catalysts for dibenzothiophene(DBT)hydrodesulfurization(HDS).The CUS concentrations on MoS_(2) slabs were finely regulated by changing the concentrations of H_(2)O_(2)solution.With the increasing H_(2)O_(2)concentrations(0.1–0.3 mol/L),The CUS concentrations on MoS_(2) slabs increased gradually.However,the high-concentration H_(2)O_(2)etching(0.5 mol/L)increased the MoOxSy and MoO_(3) contents on MoS_(2) slabs compared to etching with the H_(2)O_(2)concentration of 0.3 mol/L,which led to the less CUS concentration in the sulfided Mo–H-0.5 catalyst than in the sulfided Mo–H-0.3 catalyst.A microstructure-activity correlation indicated that the CUS introduced by H_(2)O_(2)etching on MoS_(2) slabs significantly enhanced DBT HDS.Different Co loadings were further introduced into Mo–H-0.3,which had the most CUS concentration,and the corresponding 0.2-CoMo catalyst with the highest CoMoS content(3.853 wt%)exhibited the highest reaction rate constant of 6.95×10^(−6)mol g^(−1)s^(−1)among these CoMo catalysts.

Optimization of dendritic TS-1/Silica micro–mesoporous composites for efficient hydrodesulfurization of dibenzothiophene and 4,6-dimethyldibenzothiophene

A novel composite material(TD)composed of TS-1 microcrystalline and dendritic mesoporous silica nanospheres(DMSNs)was successfully prepared.The TD composite material had open pore structure and large specific surface area,which was conducive to the mass transfer of reactants and products.The Ti element in TS-1 could be used as an electron assistant,and the spillover d-electrons were conducive to the improvement of the sulfidation and dispersion of MoS_(2),thereby forming more type II MoS_(2) active phases.The incorporation of Ti could bring more Brønsted(B)and Lewis(L)acid,which was conducive to the hydrogenation pathway(HYD)selectivity(41.2%)of dibenzothiophene(DBT)hydrodesulfurization(HDS)and isomerization(ISO)route selectivity(21.9%)of 4,6-dimethyldibenzothiophene(4,6-DMDBT)HDS,thus improve the HDS activity of DBT and 4,6-DMDBT.NiMo/TD-70(Aging temperature=70℃)had the best HDS activities of DBT(99.0%)and 4,6-DMDBT(93.7%)due to its large open pore structure,good acidity,suitable metal-support interaction(MSI)and perfect dispersion of the metallic active sites.

Highly Active Sulfided NiPMo Hydrodesulfurization Catalyst Prepared from Keggin-type Phosphomolybdic Acid

A highly active sulfided NiPMo/MCM-41(NiPMo-S/M41)hydrodesulfurization(HDS)catalyst was successfully synthesized using Keggin-type phosphomolybdic acid as the phosphorus and molybdenum source and thioacetamide as the sulfur source.The supported catalysts NiPMo/M41,Ni_(2)P-Mo/M41,and Ni_(2)P/M41 were also prepared to investigate the effects of Mo,S,and the Keggin structure on the HDS performance.The HDS activities of NiPMo/M41 and NiPMo-S/M41 toward dibenzothiophene were much higher than that of Ni_(2)P-Mo/M41,demonstrating that the active phases in the Keggin-structured catalysts were significantly superior to the Mo-modified Ni_(2)P phase.The HDS activities of the catalysts followed the order NiPMo-S/M41(96.7%)>NiPMo/M41(89.9%)>Ni_(2)P-Mo/M41(53.5%)>Ni_(2)P/M41(48.9%).For Ni_(2)P/M41,Ni_(2)P-Mo/M41,and NiPMo/M41,cyclohexylbenzene(CHB)was formed in low concentrations(<21.0%),indicating that direct desulfurization was the favored reaction route and that this did not change for Keggin-structured NiPMo/M41.By contrast,the CHB selectivity of NiPMo-S/M41 increased to 44.6%,much higher than that of NiPMo/M41(17.6%),demonstrating that sulfidation enhanced the hydrogenation ability,which was ascribed to a metal-acid synergistic effect.

Ni-_2P-MoS_2/γ-Al_2O_3 Catalyst for Deep Hydrodesulfurization via the Hydrogenation Reaction Pathway

A series of highly active Ni2P-Mo S2/γ-Al2O3 catalysts were prepared and characterized, the catalytic performance of which was evaluated through hydrodesulfurization of dibenzothiophene. The result indicated that when the amount of Ni2 P was 4%, the catalyst showed a relatively high activity to provide a reliable reference for the hydrodesulfurization pathway in comparison with the conventional Ni Mo and Ni Mo P catalysts. The physicochemical properties of the catalysts were correlated with their catalytic activity and selectivity on hydrodesulfurization. The stacking number of active Mo S2 phases was important for influencing the hydrogenation activity.

NiMo/Al_2O_3 catalyst containing nano-sized zeolite Y for deep hydrodesulfurization and hydrodenitrogenation of diesel

Two mixed-matrix NiMo/Al2O3 catalysts containing nano-and micro-sized zeolite Y have been prepared to explore the size effect of zeolite Y particle on the hydrodesulfurization（HDS）and hydrodenitrogenation（HDN）activities of fluid catalytic cracking（FCC）diesel.They were characterized by SEM,BET,XRD,H2-TPR,NH3-TPD and HRTEM.The results show that the catalyst containing nano-sized zeolite Y possesses larger average pore diameter,higher pore volume,weaker and lesser acid sites,more easily reducible metal phases,shorter MoS2 slabs and more slab layers than the catalyst containing micro-sized zeolite Y.The catalysts were also evaluated with a high-pressure fixed-bed reactor using real FCC diesel as feed.The results display that the catalyst containing nano-sized zeolite Y bears higher HDS and HDN activities and exhibits higher relative rate constant for the removal of total sulfur or nitrogen than the one containing micro-sized zeolite.

Ni_2P/ZrO_2-SBA-15 Dibenzothiophene Hydrodesulfurization Catalysts: Preparation,Characterization and Evaluation

Ni_2P/ZrO_2-SBA-15 catalysts with different zirconium n-propoxide/SBA-15 mass ratios were synthesized to evaluate their dibenzothiophene hydrodesulfurization catalytic activity. Effect of ZrO_2 introduction was investigated. Supports and catalysts were characterized by BET,XRD,^(29)SiNMR,XPS and FTIR. The results indicated that zirconium was incorporated into SBA-15 in the forms of [(–O–)_2 Si(–O–Zr)_2 ] and/or [(–O–)_3 Si–O–Zr],and that the SBA-15 framework structure was maintained after incorporation of ZrO_2. With zirconium content increasing,ZrO_2 was transformed from amorphous phase to tetragonal phase. Zirconium incorporation into SBA-15 supports could facilitate to form more dispersed Ni_2P active phase. There might be some interaction occurring between the P and Zr species. In addition to Ni_2P,another kind of active phase,ZrP,was formed,which might exhibit a better HDS activity than Ni_2P. It was observed that at a temperature of 280 °C,pressure of 3.0 MPa,WHSV of 6.5 h^(-1) and H_2 to oil ratio of 450,the Ni_2P/Zr-SBA(1.5) catalyst,where 1.5 represents zirconium n-propoxide/SBA-15 mass ratio,showed the highest DBT conversion,which was 86.6%,almost 35% higher than that of the Ni_2P/Zr-SBA(0) catalyst.

The tuning of pore structures and acidity for Zn/Al layered double hydroxides:The application on selective hydrodesulfurization for FCC gasoline

Co–Mo catalysts applied on the hydrodesulfurization（HDS） for FCC gasoline were prepared with Zn–Al layered double hydroxides（LDHs） to improve their performances,and the effects of pore structures and acidity on HDS performances were studied in detail. A series of Zn–Al/LDHs samples with different pore structures and acidities are synthesized on the bases of co-precipitation of OH-,CO2-,Al3＋,and Zn2＋. The neutralization p H is a main factor to affect the pore structures and acidity of Zn–Al/LDHs,and a series of Zn–Al/LDHs with different pore structures and acidities are obtained. Based on the representative samples with different specific surface areas（SBET） and acidities,three Co Mo/LDHs catalysts were prepared,and their HDS performances were compared with traditional Co Mo/Al2O3 catalysts. The results indicated that catalysts prepared with high SBETpossessed high HDS activity,and Br？nsted acid sites could reduce the thiol content in the product to some extent. All the three catalysts prepared with LDHs displayed little lower HDS activity but higher selectivity than Co Mo/Al2O3,and could restrain the reactions of re-combination between olefin and H2 S which could be due to the existence of Br？nsted acid sites.

The effect of chelating agent on hydrodesulfurization reaction of ordered mesoporous alumina supported Ni Mo catalysts

In this paper,ordered mesoporous alumina(OMA)support with the high surface area(328 m^(2)g^(-1))and the large pore volume 0.74(cm^(3)·g^(-1))was synthesized by homogeneous precipitation method.And the influence of EDTA on the physical and chemical properties of the modified catalysts was also studied.The characteristic results showed that the addition of EDTA could adjust the metal-support interaction and improved the acidity of the corresponding catalyst.Combined with the catalytic performance results,the EDTA-modified Ni Mo E(1.0)/OMA catalyst displays the highest DBT hydrodesulfurization conversion(97.7%).

Effects of pore size,mesostructure and aluminum modification on FDU-12 supported NiMo catalysts for hydrodesulfurization

A series of NiMo/FDU-12 catalysts with tunable pore diameters and mesostructures have been controllably synthesized by adjusting the synthetic hydrothermal temperature and applied for the hydrodesulfurization of dibenzothiophene and its derivative.The state-of-the-art electron tomography revealed that the pore sizes of FDU-12 supports were enlarged with the increase in the hydrothermal temperature and the mesostructures were transformed from ordered cage-type pores to locally disordered channels.Meanwhile,the MoS2 morphology altered from small straight bar to semibending arc to spherical shape and finally to larger straight bar with the change of support structures.Among them,FDU-12 hydrothermally treated at 150℃possessed appropriate pore diameter and connected pore structure and was favorable for the formation of highly active MoS2 with curved morphology;thus,its corresponding catalyst exhibited the best HDS activity.Furthermore,it was indicated that the isomerization pathway could be significantly improved for HDS of 4,6-dimethyldibenzothiophene after the addition of aluminum,which was expected to be applied to the removal of the macromolecular sulfur compounds.Our study sheds lights on the relationship between support effect,active sites morphology and HDS performance,and also provides a guidance for the development of highly active HDS catalysts.

Synthesis, characterization and hydrodesulfurization activity of silica-dispersed NiMoW trimetallic catalysts

Silica-dispersed NiMoW trimetallic hydrodesulfurization catalysts were prepared by deposition-precipitation method. For comparative pur- poses, bulk NiMoW trimetallic catalysts were obtained by co-precipitation. Silica was employed to disperse active metals for full utilization of active components and silica-dispersed NiMoW catalyst had high active metal content. BET analysis showed that silica-dispersed NiMoW trimetallic catalysts had a high surface area （165.1 m2/g） and pore volume （0.27 ml/g）. Transmission electron microscopy results proved that active components were well dispersed. Hydrodesulfurization activity of silica-dispersed NiMoW catalysts was much higher than that of comparative catalysts and up to twice greater than those of commercial NiMo alumina-supported systems per gram of catalyst.

The surface properties of aluminated meso–macroporous silica and its catalytic performance as hydrodesulfurization catalyst support

Aluminated mesoporous silica was prepared by multiple post-grafting of alumina onto uniform mesoporous SiO2 ,which was assembled from monodisperse SiO2 microspheres.Hydrodesulfurization（HDS）catalyst was prepared by loading Ni and Mo active components onto the aluminated uniform mesoporous SiO2 ,and its HDS catalytic performance was evaluated using hydrodesulfurization of dibenzothiophene as the probe reaction at 300℃ and 6.0 MPa in a tubular reactor.The samples were characterized by N2 physisorption,scanning electronic microscopy,Fourier transform infrared spectrum,X-ray diffraction（XRD）,temperature-programmed desorption of ammonia（NH3-TPD）,^27Al nuclear magnetic resonance（^27Al-NMR）and high-resolution transmission electron microscopy（HRTEM）.The results showed that the Si–OH group content of SiO2 was mainly dependent on the pretreatment conditions and had significant influence on the activity of the Ni Mo catalyst.The surface properties of the aluminated SiO2 varied with the Al2O3-grafting cycles.Generally after four cycles of grafting,the aluminated SiO2 behaved like amorphous alumina.In addition,plotting of activity of Ni Mo catalysts supported on aluminated meso–macroporous silica materials against the Al2O3-grafting cycle yields a volcano curve.

Novel NiMo Catalysts Supported on Sol-Gel Nanosized HY Zeolite-Alumina Composites for Hydrodesulfurization of Diesel

Composite materials(AZ-x) were prepared by mixing the nanosized HY zeolite and γ-Al_2 O_3 using the sol-gel mixing method and were employed as the support for NiMo catalysts(NiMo/AZ-x). These composites and catalysts were characterized by XRD, BET, TPD, TPR, HRTEM and FT-IR spectroscopy. Compared with the NiMo catalyst supported onγ-Al_2 O_3(NiMo/γ-Al_2 O_3), these NiMo/AZ-x catalysts show higher activity in the hydrodesulfurization(HDS) of FCC diesel,and the HDS activity increases with an increasing HY mass content in the composites, provided that the HY mass fraction does not exceed 20%. Compared with γ-Al_2 O_3, the introduction of nanosized HY zeolite can improve the porous structure of the composites,which can benefit the mass transfer of the reactant molecules. Furthermore,the nanosized HY zeolite in the composites can modify their surface properties which would increase the ratio of metal species to be transformed into reducible phase in low temperature region and modify the morphology of the MoS2 phases to form more multi-stacked MoS_2 active phases with increased dispersion of edges and corners of Mo atoms.

Preparation, characterization and hydrodesulfurization performances of Co-Ni_2P/SBA-15 catalysts

A series of Co-Ni_2P/SBA-15 catalysts with various Co contents, Ni_2P contents and P/Ni molar ratios were prepared by impregnating nickel nitrate, diammonium hydrogen phosphate, and then cobalt nitrate into SBA-15 support followed by temperature-programmed reduction in a H_2 flow. The catalyst structure was characterized by X-ray diffraction （XRD）, high resolution-transmission electron microscopy （HR-TEM） and N_2 adsorption-desorption techniques and their catalytic performance of the hydrodesulfurization （HDS） of dibenzothiophene （DBT） was evaluated. The effects of Co contents, Ni_2P contents and P/Ni molar ratios on the catalyst structure and HDS of DBT over the Co-Ni_2P/SBA- 15 catalyst were investigated. The results indicated that the mesoporous structure was mainly maintained and the nickel phosphides were well dispersed in all of the characterized catalysts. The 4Co-25Ni_2P/SBA-15 （P/Ni = 0.8） catalyst with the Co and Ni_2P contents of 4 wt% and 25 wt%, respectively, and the P/Ni molar ratio of 0.8 showed the highest catalytic performance for HDS of DBT. Under the reaction conditions of 380 ℃ and 3.0 MPa, the DBT conversion can reach 99.62%. The HDS of DBT proceeded mainly via the direct desulfurization （DDS） pathway with biphenyl （BP） as the dominant product on all of the catalysts and the BP selectivity was slightly enhanced after the introduction of Co promoters.

Study on the mechanism of hydrodesulfurization of tetrahydrothiophene catalyzed by nickel phosphide

Hydrodesulfurization(HDS)reaction can significantly reduce the viscosity and sulfur content of heavy oil,while the HDS reaction mechanism of tetrahydrothiophene as the main sulfide in heavy oil is still unclear.The HDS experiment of tetrahydrothiophene catalyzed by nickel phosphide(Ni_(2)P)is carried out at 200-300°C.The results indicate that the H_(2)S production under the catalysis of Ni_(2)P increases obviously within 200-250°C.The main gas products of HDS reaction are butane,butene and H_(2)S.Meanwhile,the mechanism of tetrahydrothiophene catalyzed by Ni_(2)P is analyzed based on Density Functional Theory(DFT).It is revealed that the adsorption model is most stable when tetrahydrothiophene is vertically adsorbed on the V-Ni-Hcp1 site of Ni_(2)P(001).The C-S bond is elongated and the C-C bond is shortened after adsorption.Hydrogenation(HYD)is the most possible reaction route of tetrahydrothiophene on Ni_(2)P(001)surface.There are two routes with the lowest activation energy,which are C_(4)H_(8)S→C_(4)H_(8)SH^(*)→C_(4)H_(9)SH^(*)→C_(4)H_(10)+H_(2)S and C_(4)H_(8)S→C_(4)H9S^(*)→C_(4)H_(9)^(*)+SH^(*)→C_(4)H_(10)+H_(2)S.Butane and H_(2)S are produced in the reaction,corresponding to the experimental results.This study provides a basis for understanding of the HDS mechanism of tetrahydrothiophene catalyzed by Ni_(2)P.

Synthesis of alumina-nitrogen-doped carbon support for CoMo catalysts in hydrodesulfurization process

More stringent environmental legislation imposes severe requirements to reduce the sulfur content in diesel to ultra-low levels with high efficient catalysts.In this paper,a series of CoMo/NDC@alumina catalysts were synthesized by combination of the chemical vapor deposition of nitrogen-doped carbon(NDC)using 1,10-phenanthroline and co-impregnation of Mo and Co active components.The optimal catalyst with additive of 25%1,10-phenanthroline was screened by a series of property characterization and the hydrodesulfrization(HDS)active test.The amount of“CoMoS”active phase of the optimal CoMo/C3 catalyst increased 5.3%as compared with the CoMo/c-Al_(2)O_(3).The introduction of NDC improved the sulfidation degree of Mo by 21.8%as compared to the CoMo/c-Al_(2)O_(3) catalyst,which was beneficial to form more active sites.The HDS conversion of the NDC supported catalysts are higher than CoMo/c-Al_(2)O_(3) whether for the dibenzothiophene(DBT)or 4,6-dimethyl dibenzothiophene(4,6-DMDBT).Further hydroprocessing evaluation with Dagang diesel revealed that the CoMo/C3 catalyst possessed higher HDS property and the removal rate of DBTs in the diesel increased by 4%–11%as compared to the CoMo/c-Al_(2)O_(3) catalyst.

Coupling non-isothermal trickle-bed reactor with catalyst pellet models to understand the reaction and diffusion in gas oil hydrodesulfurization

In this work,a trickle-bed reactor coupled with catalyst pellet model is employed to understand the effects of the temperature and catalyst pellet structures on the reaction-diffusion behaviors in gas oil hydrodesulfurization(HDS).The non-isothermal reactor model is determined to be reasonable due to non-negligible temperature variation caused by the reaction heat.The reaction rate along the reactor is mainly dominated by the temperature,and the sulfur concentration gradient in the catalyst pellet decreases gradually along the reactor,leading to the increased internal effectiveness factor.For the fixed catalyst bed volume,there exists a compromise between the catalyst reaction rate and effectiveness factor.Under commonly studied catalyst pellet size of 0.8-3 mm and porosity of 0.4-0.8,an optimization of the temperature and catalyst pellet structures is carried out,and the optimized outlet sulfur content decreases to 7.6 wppm better than the commercial level at 0.96 mm of the catalyst pellet size and 0.40 of the catalyst porosity.

Hierarchically porous Beta/SBA-16 with different silica-alumina ratios and the hydrodesulfurization performances of DBT and 4,6-DMDBT

Hierarchically porous Beta/SBA-16(BS)composite materials,combining the characteristics of the acidity from the Beta zeolite and the three-dimensional structure from SBA-16,were synthesized successfully through a two-step in-situ assembly hydrothermal crystallization method.A series of Ni Mo catalysts supported on BS with different silica-alumina ratios were prepared.The supports and the corresponding catalysts were characterized by XRD,N_(2) physisorption,^(27)Al MAS NMR,TEM,pyridine-FTIR,Raman,XPS and HRTEM.The activities of series catalysts were evaluated by the hydrodesulfurization(HDS)performances of dibenzothiophene(DBT)and 4,6-dimethyldibenzothiophene(4,6-DMDBT).It was found that the Beta crystallites were embedded into SBA-16 through silanols accompanied by dealumination on the T3-T9 sites of Beta crystallites.Ni Mo/BS-3 with a silica-alumina ratio of 100 exhibited the highest DBT and 4,6-DMDBT HDS activities at the WHSV value of 10 h^(-1),with the conversions of 95.9%and 86.9%respectively,due to the synergistic effects of the suitable specific surface areas,the relatively large pore size,appropriate acidity,the relatively high sulfidation degree,moderate dispersity and good stacking degree of Mo S;active phases.