Mild hydrotreating over NiMo/sepiolite catalyst

Summary In order to introduce an alternative catalyst for hydrotreating (HDT) reaction a study of NiMo supported on natural sepiolite catalysts is presented. The sepiolite catalyst has been prepared in this laboratory and a NiMo/Al₂O₃ commercial catalyst is used as a reference. The textural properties of the materials and their catalytic activity in hydrotreating (HDT) and hydrodesulfuration (HDS) using a FCC feed at 400-475°C and 50 MPa total pressure, have been evaluated. The support of the commercial catalyst is alumina containing mesopores. The sepiolite support is a hydrated magnesium phylosilicate containing micropores but with an open structure that confers the possibility to use it as a catalyst. The hydrotreating conversion (wt.% HDT) is defined here as the net hydrotreating conversion into products boiling below 380°C. For the commercial catalyst the wt.% HDT was only 5% higher than for the catalyst supported on sepiolite and the product selectivity was very similar. HDS conversion was 20% lower for the sepiolite supported catalyst. Taking into account these results the sepiolite is a suitable support of HDS catalysts.     

Influence of the activation temperature on structural and textural properties of NiMo/Al2O3 hydrodesulfurization catalysts

Investigations of a commercial NiMo/Al₂O₃ hydrodesulfurization (HDS) catalyst are directed towards optimization of the activation procedure of HDS catalyst concerning active phase formation and thermal stability. Structural and textural data obtained with XRD, IR-FTIR, XPS and LTNA reveal that the optimal temperature for the formation of active species on the catalyst surface and an appropriate pore structure is 300°C.     

TiO2柱撑海泡石负载Ni2P的噻吩加氢脱硫性能

以氢氧化镍为镍源, 亚磷酸为磷源, TiO₂柱撑海泡石(Ti-Sep)为载体, 采用浸渍法制备了含磷化镍前驱体的样品, 然后采用程序升温还原法制备了Ni质量分数(w)为5%-25%的Ni₂P/Ti-Sep催化剂, 并考察了其噻吩加氢脱硫性能. 采用X射线衍射(XRD)、N₂吸附-脱附、热重分析(TGA)、透射电子显微镜(TEM)和傅里叶变换红外(FTIR)光谱对催化剂样品进行了表征. 结果表明, 海泡石经TiO₂柱撑之后层间距增大, 比表面积和孔容都明显变大, 热稳定性增强, 活性组分Ni₂P能很好地分散在海泡石层间及表面, 并且没有破坏海泡石的层状结构. 上述原因导致Ni₂P/Ti-Sep催化剂的噻吩加氢脱硫活性明显优于Ni₂P/Na-Sep(NaCl改性海泡石)和Ni₂P/HCl-Sep(HCl改性海泡石)催化剂. 当Ni负载量为15% (w)时, Ni₂P/Ti-Sep催化剂具有最好的噻吩加氢脱硫性能; 在反应温度为400℃时, 噻吩转化率达100%.     

Comparing the hydrodesulfurization reaction of thiophene on γ-Al2O3 supported CoMo, NiMo and NiW sulfide catalysts

The thiophene hydrodesulfurization (HDS) reaction on γ-Al₂O₃ supported CoMo, NiMo and NiW sulfide catalysts was compared in order to gain insight into the promoter effect on direct desulfurization (DDS) and hydrogenation (HYD) pathways. Ni-promoted Mo (or W) sulfide catalysts favor the hydrogen transfer reactions relative to CoMo sulfide catalyst, which facilitates the direct route instead. This different performance and also the dependence of the apparent Arrhenius parameters with the catalyst formulation were attributed to the major participation of Mo (or W) edge for the Ni-containing catalysts and S edge for CoMo sulfide catalyst upon the thiophene-HDS reaction.     

Mono- and heterometallic carbonyl precursor based RuMo/Al2O3 catalysts: hydrodesulfurization activity and temperature programmed studies

The effects of preparation process and starting material on hydrodesulfurization (HDS) activity of alumina supported ruthenium, molybdenum and ruthenium–molybdenum hydrotreating catalysts were investigated. Conventional impregnation method and gradual gas phase adsorption were compared as a preparation route. The HDS tests showed that controlled gas phase deposition is advantageous in the preparation of the monometallic catalyst systems. The most promising HDS activity was achieved with the RuMo/Al₂O₃ catalyst prepared from binuclear organometallic complex. This suggests that the direct ruthenium–molybdenum bond in the structure of the catalyst precursor favors the formation of highly active surface phase. The oxidation and reduction behavior of the catalysts was studied by oxygen pulse chemisorption (PCO) and temperature programmed reduction (TPR). A clear relationship was observed between the method of preparation and the reactivity of the surface species.     

Kinetic behavior of benzene hydrogenation and thiophene hydrogenolysis on sulfide Ni-Mo/Al2O3 catalyst

Summary An unsteady-state kinetic model of both benzene hydrogenation (HDA) and thiophene hydrogenolysis (HDS) on a sulfide hydrotreating catalyst Ni-Mo/Al₂O₃ has been developed. The model adequately describes experimental data obtained at the pressure 2 MPa, temperature 573 K and at various contact times and ratios of benzene/thiophene. The model is based on the assumption that the catalyst surface contains only one type of active sites, i.e., Ni atoms in the sulfide bimetallic species, which are responsible for both hydrogenolysis and hydrogenation reactions.     

Investigation of the HDS kinetics of dibenzotiophene and its derivatives in real gas oil ??

Summary The hydrodesulfurization (HDS) of dibenzothiophene (DBT), 4-methyl-dibenzothiophene (4 M-DBT), 4,6-dimethyldibenzothiophene (4,6 DM-DBT) and 4,6-diethyldibenzothiophene (4,6 DE-DBT) as real gas oil components on NiMo/Al₂O₃ catalyst was investigated. On the basis of the first order rate constants of HDS of the individual sulfur compounds calculated by both integral and differential evaluations the reactivities of the investigated compounds decreased in the order DBT >> 4 M-DBT > 4,6 DE-DBT ? 4,6 DM-DBT. Additionally, results showed that product inhibition during HDS does not take place.     

不同磷含量对NiMoP/Al2O3加氢处理催化剂的影响

采用NiMoP浸渍液浸渍载体γ Al₂O₃制备了不同磷含量的NiMoP/Al₂O₃加氢处理催化剂。为了研究磷对该系列催化剂活性相结构的影响,用二苯并噻吩（DBT）和喹啉为模型化合物,考察了催化剂的加氢脱硫（HDS）和加氢脱氮（HDN）性能。结果表明,添加适当的磷能够提高催化剂的HDS和HDN活性,但是高含量的磷能显著的降低催化剂的催化性能。通过对催化剂进行XRD和HRTEM表征发现,添加磷能够增加MoS2的堆积层数以及Ⅱ型“Ni-Mo-S”相的相对含量,这是因为在制备过程中添加磷降低了活性组分与载体之间的相互作用。     

镍钼杂多酸制备NiMo/γ-Al2O3催化剂及硼、钴或镍改性氧化铝的影响（英文）

A hydrotreating NiMo/γ-Al2O3 catalyst(12 wt% Mo and 1.1 wt% Ni) was prepared by impregnation of the support with the Anderson-type heteropolyoxomolybdate(NH4)4Ni(OH)6Mo6O18.Before impregnation of the support,it was modified with an aqueous solution of H3BO3,Co(NO3)2,or Ni(NO3)2.The catalysts were investigated using N2 adsorption,O2 chemisorption,X-ray diffraction,UV-Vis spectroscopy,Fourier transform infrared spectroscopy,temperature-programmed reduction,temperature-programmed desorption,and X-ray photoelectron spectroscopy.The addition of Co,Ni,or B influenced the Al2O3 phase composition and gave increased catalytic activity for 1-benzothiophene hydrodesulfurization(HDS).X-ray photoelectron spectroscopy confirmed that the prior loading of Ni,Co or B increased the degree of sulfidation of the NiMo/γ-Al2O3 catalysts.The highest HDS activity was observed with the NiMo/γ-Al2O3 catalyst with prior loaded Ni.     

Influence of Pd-Ce interaction and chlorine ion on hydrodesulfurization reaction: The activity and sulfur tolerance of the Pd-Ceo2/Al2O3 catalyst

CeO₂ promoted palladium catalysts supported on Al₂O₃ were prepared using the impregnation (IM) and the deposition-precipitation (DP) methods. The activities and sulfur tolerance of the catalysts for hydrodesulfurization (HDS) were detected with thiophene HDS as probe reaction. H₂ adsorption, XRD, FTIR, NH₃-TPD, XPS were used to characterize the catalysts. The Pd-CeO₂/Al₂O₃ (IM) catalyst was highly active for the HDS reaction, and it had much stronger sulfur tolerance than the Pd/Al₂O₃ catalyst. Pd-CeO₂/Al₂O₃ (DP) showed excellent sulfur tolerance while its initial activity decreased. It was observed that with the chlorine bridge, the interfacial structure of Pd-Cl⁻¹-Ce³⁺ was responsible for the high activity of the Pd-CeO₂/Al₂O₃ (IM) catalyst, at the same time the interaction of Pd with Ce was weakened by Cl₋₁ ions. The enhanced sulfur tolerance over the Pd-CeO₂/Al₂O₃ (IM) catalyst was attributed to the weakened Pd-S bond caused by the competitive adsorption of H₂S on Ce³⁺ ions. As to the Pd-CeO₂/Al₂O₃ (DP) catalyst, a strong interaction of Pd with Ce put Pd at an electron-deficient state, the creation of sulfided palladium was therefore inhibited.     

助剂Ni与载体的相互作用及其对NiMo/γ-Al_2O_3催化剂加氢脱硫性能的影响

以γ-Al_2O_3为载体,制备了一系列不同NiO负载量的NiMo/γ-Al_2O_3催化剂,利用XRD、~(27)Al-MAS NMR、Py-FTIR和HRTEM等技术对其进行了表征;在高压微反装置对该系列催化剂的加氢脱硫性能进行了评价,研究了助剂Ni与载体γ-Al_2O_3中不饱和铝间的相互作用及其对催化剂活性相结构形貌和催化活性的影响。结果表明,助剂Ni优先作用于γ-Al_2O_3表面的四配位不饱和铝原子位置;随着NiO负载量的增加,硫化态NiMo/γ-Al_2O_3催化剂中MoS_2活性相的长度变短、堆垛层数增加。Ni的引入能明显提高NiMo/γ-Al_2O_3催化剂的加氢脱硫活性,但其加氢选择性则有所降低。     

Improvement of the Mo/TiO2-Al2O3 Catalyst by the Control of the Sol-Gel Synthesis

Traditional hydrotreating catalysts are constituted by molybdenum deposited on Al₂O₃ promoted by nickel and phosphorous. Several studies have shown that TiO₂-Al₂O₃ mixed oxides are excellent supports for the active phases. Results concerning the preparation, characterization and testing of molybdenum catalyst supported on titania-alumina are presented. The support was prepared by sol-gel route using titanium and aluminum isopropoxides, the titanium one chelated with acetylacetone (acac) to promote similar hydrolysis ratio for both the alcoxides. The effect of nominal molar ratio [Ti]/[Ti+Al] on the microstructural features of nanometric particles was analyzed by X-Ray Diffraction, N₂ Adsorption Isotherms and Transmission Electron Microscopy. The catalytic activity of Mo impregnated supports was evaluated using the thiophene hydrodesulfurization at different temperatures and atmospheric pressure. The pores size distribution curve moves from the micropores to the mesopores by increasing the Ti contents, allowing the fine tuning of average size from 2.5 to 6 nm. Maximal (367 m²·g^?1) and minimal (127 m²·g^?1) surface area were found for support containing [Ti]/[Ti+Al] ratio equal to 0.1 and 1, respectively. The good mesopore texture of alumina-titania support with [Ti]/[Ti+Al] molar ratio between 0.3 and 0.5 was found particularly valuable for the preparation of well dispersed MoS₂ active phase, leading to HDS catalyst with somewhat higher activity than that prepared using a commercial alumina support.     

镍磷物质的量比对负载型Ni2P/MCM-41催化剂结构及加氢脱硫性能的影响

以MCM-41为载体,采用一种简捷、温和法制备了负载型Ni₂P/MCM-41催化剂。用H₂程序升温还原(H₂-TPR)、X射线衍射(XRD)、N₂吸附比表面积测定(BET)和X射线光电子能谱(XPS)分析对催化剂进行了表征。以1%(质量分数)二苯并噻吩(DBT)的十氢萘溶液为原料,在连续固定床反应装置上,研究了初始Ni/P物质的量比对催化剂HDS活性的影响,并考察了催化剂的稳定性。结果表明,初始Ni/P物质的量比为1/2和1/3的前驱体,在390 ℃下还原时得到单一的Ni₂P相。初始Ni/P物质的量为1/2时,得到的催化剂活性最好。在反应温度340 ℃、压力3.0 MPa、氢/油体积比500、质量空速2.0 h^-1时,DBT的转化率接近100%。     

Co调变MoS2催化剂的作用本质及其FCC汽油选择性加氢脱硫机理

采用含硫前驱体四硫代钼酸铵直接构建MoS₂催化剂,通过调变Co/Mo原子比深入认识Co调变MoS₂催化剂的作用本质及其FCC汽油选择性加氢脱硫机理。借助XRD、HRTEM、XPS、H₂-TPR和Py-FTIR表征发现,Co/Mo原子比能够影响催化剂的活性相微观结构组成,从而影响催化剂的加氢脱硫活性和选择性。当Co/Mo（atomic ratio）<0.2时,助剂Co原子倾向于占据MoS₂相的边角位而形成CoMoS活性相,明显提高了催化剂的加氢脱硫活性;当0.2 < Co/Mo（atomic ratio） < 0.6时,助剂Co在催化剂表面形成适量的Co₉S₈相,其产生的溢流氢能提高硫化物的脱除活性而对烯烃饱和活性的影响较小;当Co/Mo（atomic ratio）>0.6时,过量的Co会形成大颗粒的Co₉S₈相,阻碍硫化物和烯烃与催化剂活性中心的接触,从而降低催化剂的活性和选择性。     

Effect of calcination temperature on the properties of industrial V2O5-TiO2 (anatase) catalysts in methanol oxidation

The properties of the catalysts for partial oxidation of o-xylene depend on the structure of the supported vanadium sites. The structure itself is strongly dependent on the calcination temperature of the catalyst at which thermal deposition of the metal oxide on the oxide support takes place. We have investigated the effect of calcination temperature on the activity and selectivity of industrial V₂O₅-TiO₂ (anatase) supported catalysts designed for partial oxidation of o-xylene in their application to methanol oxidation.This revised version was published online in December 2005 with corrections to the Cover Date.     

Preparation and characterization of highly dispersed V2O5/SiO2prepared by a CVD method

Highly dispersed V₂O₅/SiO₂(CVD catalyst) was prepared by the reaction of vaporized VO(OPrⁱ)₃ with silica at 293 K, whose process was followed by an IR technique. The rate of propylene photooxidation increased with an increase in V₂O₅ loading for CVD catalysts, but leveled off for impregnated ones. The CVD catalysts were characterized by XAFS and photoluminescence spectroscopy.     

Egyptian heavy vacuum gas oil hydrotreating over Co-Mo/CNT and Co-Mo/γ-Al_2O_3 catalysts

The catalytic activity of CoMoS /CNT towards the Egyptian heavy vacuum gas oil hydrotreating was studied. The delivered CNT was functionalized with 6 mol /L HNO_3. The CNT were loaded with 12% MoO_3( by weight) and 0.7 Co /Mo atomic ratio with impregnation methods. The γ-Al_2O_3 catalyst was also prepared by impregnation method to compare both catalysts activities.The analysis tools such XRD,Raman spectroscopy,TEM,and BET were used to characterize the catalysts. The autoclave reactor was used to operate the hydrotreating experiments. The hydrotreating reactions were tested at various operating conditions of temperature 325-375 ℃,pressure 2-6 MPa,time 2-6 h,and catalyst /oil ratio( by weight) of 1 ∶75,1 ∶33 and 1 ∶10. The results revealed that the CoMoS /CNT was highly efficient for the hydrotreating more than the CoMoS /γ-Al_2O_3. Also, the hydrodesulfurization( HDS) increased with increasing catalyst /oil ratio. Additionally,results showed that the optimum condition was temperature 350℃,pressure 4 MPa,catalyst /oil ratio of 1 ∶75 for 2 h. Furthermore,even at low CoMoS /CNT catalyst /oil ratio of 1 ∶75,an acceptable HDS of 77.1% was achieved.     

Tungsten/Alumina Catalysts: Effect of H3PW12O40 Countercation on Surface Properties and Hydrodesulfurization Activity

H₃PW₁₂O₄₀ heteropoly acid (HPW₁₂) and its Co, Fe, Ni salts supported on alumina have been used to model hydrodesulfurization catalysts of different activity. All catalysts revealed a promoting effect of the countercation in thiophene hydrodesulfurization, that of the nickel cation being the highest. The catalysts were characterized by measurements of surface area, HDS activity, TPR, FTIR, and DR spectra. IR spectra confirmed an effect of the countercation on the phase composition of the supported heteropoly compounds. 12-Tungstoaluminate heteropoly anions and coordinately unsaturated anions of HPW₁₂ were detected in the IR spectra of the catalysts. The hydrotreating activity of the catalysts was proportional to the amount of hydrogen consumed in the range 20–500°C during TPR.     

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.     

Catalytic combustion of chlorobenzene over V2O5/TiO2 catalysts prepared by the precipitation-deposition method

Catalytic combustion of chlorobenzene over supported vanadium oxides has been investigated. TiO₂ was prepared by the sol-gel method from titanium isopropoxide. The supported vanadium oxide catalysts have been prepared by precipitation-deposition and impregnation method and characterized by XRD, FT-Raman and TPR. In the VO_x/TiO₂catalysts prepared using the impregnation method, when vanadium loading reaches 3 wt.%, the activity shows a maximum. However, in the VO_x/TiO₂catalysts prepared by precipitation-deposition, when vanadium loading reaches 7 wt.%, the activity shows a maximum. This result suggests that the precipitation-deposition can yield a higher metal loading on the support and a high dispersion compared to the impregnation method. This revised version was published online in August 2006 with corrections to the Cover Date.