Synthesis, characterization and hydrotreating performance of supported tungsten phosphide catalysts

Supported tungsten phosphide catalysts were prepared by temperature-programmed reduction of their precursors (supported phospho-tungstate catalysts) in H₂ and characterized by X-ray diffraction (XRD), BET, temperature-programmed desorption of ammonia (NH₃-TPD) and X-ray photoelectron spectroscopy (XPS). The reduction-phosphiding processes of the precursors were investigated by thermogravimetry and differential thermal analysis (TG-DTA) and the suitable phosphiding temperatures were defined. The hydrodesulfurization (HDS) and hydrodenitrogenation (HDN) activities of the catalysts were tested by using thiophene, pyridine, dibenzothiophene, carbazole and diesel oil as the feedstock. The TiO₂, γ-Al₂O₃ supports and the Ni, Co promoters could remarkably increase and stabilize active W species on the catalyst surface. A suitable amount of Ni (3%–5%), Co (5%–7%) and V (1%–3%) could increase dispersivity of the W species and the BET surface area of the WP/γ-Al₂O₃ catalyst. The WP/γ-Al₂O₃ catalyst possesses much higher thiophene HDS and carbazole HDN activities and the WP/TiO₂ catalyst has much higher dibenzothiophene (DBT) HDS and pyridine HDN activities. The Ni, Co and V can obviously promote the HDS activity and inhibit the HDN activity of the WP/γ-Al₂O₃ catalyst. The G-Ni5 catalyst possesses a much higher diesel oil HDS activity than the sulphided industrial NiW/γ-Al₂O₃ catalyst. In general, a support or promoter in the WP/γ-Al₂O₃ catalyst which can increase the amount and dispersivity of the active W species can promote its HDS and HDN activities.     

金属氮化物/碳化物催化剂加氢性能研究进展

介绍了过渡金属氮化物/碳化物独特的晶体结构和电子性能及其与催化性能的内在联系。综述了过渡金属氮化物/碳化物在涉氢反应中催化加氢机理的研究进展,以及过渡金属氮化物/碳化物在加氢脱硫(HDS)、加氢脱氮(HDN)和其他涉氢反应中的应用。与传统的过渡金属硫化物催化剂相比,过渡金属氮化物/碳化物具有更加优异的氢吸附、活化和转移能力。     

Catalytic performances of platinum doped molybdenum carbide for simultaneous hydrodenitrogenation and hydrodesulfurization

The hydrotreating activity of molybdenum carbide doped with platinum (0.3 wt.%) was studied and compared to that of a pure, non-modified Mo₂C. 4,6-Dimethyldibenzothiophene (4,6-DMDBT, 300 ppm of S) and carbazole (100 ppm of N) were designated as model compounds and subjected to hydrodesufurization (HDS) and hydrodenitrogenation (HDN) processes either separately or simultaneously. In both cases the molybdenum carbide doped with platinum (Mo₂C-Pt) turns out to be more active than Mo₂C. The increase of the hydrotreating activity, owing to the presence of platinum in molybdenum carbide can be related to the raise of hydrogenation activity of the modified catalyst. The platinum modified molybdenum carbide was stable (displays a long lifetime) under HDN and HDS reaction conditions. The predominant reaction products are bicyclohexyl (BCH) for the HDN process or 3,3′-dimethylbiphenyl (3,3′-DMBPh) and methylcyclohexyltoluene (MCHT) for the HDS process, respectively.     

Decane reforming reaction over Pt,Ir, Pt-Ir and Pt-Ni bimetallic catalysts supported on Y-zeolite

Pt, Ir, Pt-Ir and Pt-Ni bimetallic catalysts supported on NaY- and HY-zeolite were examined as a catalyst for producing gasoline from n-decane via simultaneous reforming and cracking. The catalysts were prepared by calcining and reducing metal-ion-exchanged Y-zeolite with O₂ and H₂ at 300°C., respectively. Thus prepared catalysts were characterized by hydrogen chemisorption and temperature programmed desorption of ammonia. Pt-Ni/NaY and Pt-Ir/NaY bimetallic catalysts offered the improved activity maintenance compared to Pt/NaY monometallic catalyst. The catalysts supported on HY-zeolite showed higher selectivity toward C₅–C₇ and skeletal isomers of C₅–C₇- and C₈–C₁₀ than those of the catalysts supported on NaY-zeolite, which is a desired characteristic for increasing octane value of gasoline these days. However, deactivation with reaction time was much more pronounced on HY-zeolite-supported catalyst. When the catalyst was prcsulfided with H,S, the stability with time on stream was enhanced and the selectivity was quite different from that of the catalyst before presulfiding. The acidity of Y-zeolite and presulfiding of catalyst greatly influenced the activny, selectivity and stability of Pt, Ir, Pt-Ir and Pt-Ni bimetallic catalysts supported on Y-zeolite in n-decane reforming reaction.     

Nano-structured CeO2 supported Cu-Pd bimetallic catalysts for the oxygen-assisted water–gas-shift reaction

The present work focuses on the development of novel Cu-Pd bimetallic catalysts supported on nano-sized high-surface-area CeO₂ for the oxygen-assisted water–gas-shift (OWGS) reaction. High-surface-area CeO₂ was synthesized by urea gelation (UG) and template-assisted (TA) methods. The UG method offered CeO₂ with a BET surface area of about 215 m²/g, significantly higher than that of commercially available CeO₂. Cu and Pd were supported on CeO₂ synthesized by the UG and TA methods and their catalytic performance in the OWGS reaction was investigated systematically. Catalysts with about 30 wt% Cu and 1 wt% Pd were found to exhibit a maximum CO conversion close to 100%. The effect of metal loading method and the influence of CeO₂ support on the catalytic performance were also investigated. The results indicated that Cu and Pd loaded by incipient wetness impregnation (IWI) exhibited better performance than that prepared by deposition–precipitation (DP) method. The difference in the catalytic activity was related to the lower Cu surface concentration, better Cu–Ce and Pd–Ce interactions and improved reducibility of Cu and Pd in the IWI catalyst as determined by the X-ray photoelectron spectroscopy (XPS) and temperature-programmed reduction (TPR) studies. A direct relation between BET surface area of the CeO₂ support and CO conversion was also observed. The Cu-Pd bimetallic catalysts supported on high-surface-area CeO₂ synthesized by UG method exhibited at least two-fold higher CO conversion than the commercial CeO₂ or that obtained by TA method. The catalyst retains about 100% CO conversion even under extremely high H₂ concentration.     

Novel phosphorus-doped alumina-supported molybdenum and tungsten carbides: synthesis, characterization and hydrogenation properties

The effect of atomically dispersed phosphorus on Mo₂C- and WC-supported -Al₂O₃ has been studied. Phosphorus was introduced via molybdenum or tungsten heteropolyanions. Mo- and W-based heteropolyanions were used to synthesize supported materials. Propene and tetralin hydrogenation were used as molecular probe reactions to test the activity and selectivity of the alumina-supported molybdenum or tungsten carbides. The effect of phosphorus on the hydrogenation activity of materials was also considered. Catalysts were characterized by X-ray diffraction, transmission electron microscopy (TEM), energy-dispersive spectroscopy (EDS) and CO chemisorption. Phosphorus was found to increase significantly the activity of molybdenum and tungsten carbides. Supported molybdenum carbides are highly dispersed. Tungsten carbide particles are well dispersed with sizes ranging from 2 to 4 nm. To check the stability of carbides they were characterized after catalytic runs.     

Synthesis and characterization of P-modified mesoporous CoMo/HMS–Ti catalysts

A hexagonal mesoporous siliceous material with a wormhole framework structure incorporating Ti (HMS-Ti; Si/Ti atomic ratio of 40) was modified with variable amounts of phosphorous and used as support for CoMo phases. The catalysts were prepared by successive impregnation, with Mo being introduced first. The supports and catalysts were characterized by N₂ adsorption–desorption, High-resolution transmission electron microscopy, X-ray diffraction, FT-IR study of the framework vibrations, DRIFT spectra in the OH region, ¹H NMR, FT-IR spectra of adsorbed NO, micro-Raman spectroscopy and X-ray photoelectron spectroscopy. The catalysts were tested in the reaction of hydrodesulfurization (HDS) of dibenzothiophene (DBT) and their activity compared with that of a commercial P-containing CoMo/γ-Al₂O₃ catalyst. The physical and chemical characterization of the P-modified HMS–Ti substrates shows that the presence of P₂O₅ on the support surface does not change its mesoporous character, but modifies its surface properties. In addition, characterization data of the oxide catalysts show that phosphate favors the dispersion of the active phases and increases the population of octahedral Co²⁺ ions associated to Mo species. As a result, HDS activity was strongly enhanced upon P-loading, which reached a maximum of 0.64 wt%. This catalyst is 3.7 times more active than the commercial one and 2.4 times more active than its P-free counterpart. The highest activity of this catalyst was explained in terms of the specific electronic properties of its active phases and the largest Mo surface exposure on the support.     

Catalytic hydrogenolysis of CFC-12 (CC1<Subscript>2</Subscript>F<Subscript>2</Subscript>) over bimetallic palladium catalysts supported on activated carbon

Experiments were conducted for the hydrogenolysis of CFC-12 (CCl₂F₂) to CH₂F₂ over bimetallic palladium catalysts (Pd-Bi, Pd-Ru) supported on activated carbon. The characteristics of the bimetallic palladium catalysts were examined with ICP, XRD, TPD, TEM, and N₂ physisorption/H₂ chemisorption and the Pd-F formation was identified by XPS analysis. The catalytic activity of the bimetallic palladium catalyst (Pd-Bi/C, or Pd-Ru/C) was superior to that of the monometallic palladium catalyst. The bimetallic palladium catalysts showed much higher conversion rates (more than 99% of it was converted) than did the monometallic palladium catalyst (< 92%) and were deactivated to a lesser extent, even at high temperatures (>320 ‡C). The bimetallic components maintained the good dispersion of the Pd on the activated carbon support.     

煤焦油加氢裂化反应及其催化剂的研究

以煤焦油为原料,研究加氢裂化反应类型及反应产物油馏分的调制机理。以γ-Al2O3为载体,Mo、Ni为加氢活性组分,采用分步浸渍法制备负载型MoO3-NiO/γ-Al2O3加氢裂化催化剂。在高压反应釜上考察反应压力、反应温度对煤焦油加氢催化裂化反应的影响,比较了3种不同NiO质量分数的催化剂加氢活性,实验结果表明,NiO质量分数为3.68%的催化剂活性最好,并获得了低硫、低氮、低芳烃的反应产物油。     

Preparation, characterization, and catalytic properties of the Mo2C/SBA-15 catalysts

A series of Mo₂C/SBA-15 catalysts with different Mo contents were prepared by temperature-programmed carburization (TPC). The materials obtained and their oxide precursors (MoO₃/SBA-15) were characterized by Nitrogen adsorption-desorption isotherms, X-ray diffraction (XRD), and Fourier transform-infrared (FT-IR) spectroscopy. The activities of the catalysts for deep hydrodesulfurization (HDS) of thiophene were evaluated. The results of N₂ adsorption-desorption isotherms indicated that the surface area and pore diameter of the oxide precursors increase after carburization. The XRD patterns show that Mo₂C particles are highly dispersed in the SBA-15 ordered mesoporous. The test results show that Mo₂C/SBA-15 catalysts have an excellent performance for the deep HDS under the lower temperature region.     

Carbon-supported cobalt–iron catalysts for ammonia synthesis

The cobalt, iron and Co–Fe catalysts deposited on carbon were prepared, characterised (XRD, H₂ TPD) and studied in ammonia synthesis at 90 bar (H₂:N₂ = 3:1). Partly graphitised carbon material obtained via high temperature treatment (1900 °C) of commercial activated carbon was used as a support for the active metals (10 wt.%) and barium or potassium were used as promoters. XRD studies of unpromoted materials have shown that cobalt (5–20% in Co + Fe) dissolves in the iron phase (alloy formation); the average sizes of crystallites (20–30 nm) are roughly independent of the metal kind (Co, Fe, Co–Fe). The effect of Ba and that of K on the catalyst performance proved to be strongly dependent on the choice of an active phase (Co or Fe or Co–Fe). In the case of Co/C, the promotional effect of barium was extremely large. Furthermore, the Ba–Co/C system was found to be less inhibited by the ammonia product than Ba–Fe/C. At low temperature (400 °C) and at high conversion (8% NH₃ in the gas), the surface-based reaction rate (TOF) for Ba–Co/C is about six times higher than that for Ba–Fe/C.     

Preparation, interconversion and characterization of nanometer-sized molybdenum carbide catalysts

Nanometer-sized molybdenum carbide particles have been shown to have hydrogenation and other catalytic properties similar to those of the more-expensive noble metals. However, current preparation techniques for molybdenum carbide require the high-temperature reduction of unsupported molybdenum oxide in the presence of CH₄ and H₂. Although this method is effective, it yields particles of relatively large size, 11 nm. Different, simpler, synthesis procedures starting with ammonium heptamolybdate impregnated on carbon yield carbides of different stiochiometries. Particle sizes are in the 2–10 nm range, which are generally smaller than those previously obtained, and can be altered by changing the method of preparation. The focus of this work is to characterize the new procedures, specifically the bulk transitions of the new starting material to the different molybdenum carbides, using time-resolved X-ray diffraction, temperature-programmed reduction, and temperature-programmed desorption.     

K–V–Ca catalysts supported on porous alumina ceramic substrate for soot combustion: Preparation and characterization

The KCl, KNO₃, CaCl₂, Ca(NO₃)₂, V–Ca and K–V–Ca catalysts supported on alumina ceramic substrates have been prepared. X-ray diffraction and thermogravimetry/differential scanning calorimetry were used to characterize the catalysts, and their catalytic activities were evaluated by a soot oxidation reaction using the temperature-programmed reaction system. The catalytic activity of KNO₃ is higher than KCl, and the catalytic activity of Ca(NO₃)₂ is as much as that of CaCl₂. The catalyst containing a higher KNO₃ content exhibits CO₂ adsorption, whereas higher CaCl₂ and Ca(NO₃)₂ content can restrain the adsorption of CO₂. The K–V–Ca catalyst with a molar ratio of 6:1:1 had the lowest soot onset combustion temperature. The melting and oxidation–reduction of KNO₃, oxygen content of catalyst surface, and formation of some eutectic phase may be the key factors in improving catalytic activity of catalysts.     

Synthesis and characterization of massive molybdenum carbides and supported carbide-containing catalysts Mo2C/C prepared through mechanical activation

Procedures for the synthesis of massive molybdenum carbide by the mechanical activation of a mixture of MoO₃, commercial carbon, and Zn in air and the synthesis of the supported carbide-containing catalyst Mo₂C/C by the mechanical activation of commercial carbon impregnated with a 16% aqueous solution of ammonium paramolybdate in an inert atmosphere were developed for the first time. With the use of a set of physicochemical methods, the metal contents, particle sizes, specific surface areas, and phase compositions of the mechanically activated composites were determined. The structure of the carbide-containing supported catalyst was studied by electron microscopy, and its acidic properties were studied by the temperature-programmed desorption of ammonia; catalytic tests in the model reactions of dibenzothiophene (DBT) and alkane aromatization were performed. It was found that the Mo₂C/C catalyst exhibited high activity in these reactions: the conversion of DBT at a contact time of 3–6 h was 80–85%. The conversion of n-heptane at a contact time of 2 h was 31.2%, and 100% toluene was the reaction product. An increase in the contact time to 6 h led to a decrease in the conversion of n-heptane to 1.3%, and to 47% C₆-C₇ cycloalkanes were present in the reaction products. The results of this work are indicative of the high catalytic activity of the Mo₂C/C catalyst obtained by mechanical activation.     

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 cat-alysts 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 cat-alyst 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/γ-Al2O3.The introduction of NDC improved the sul-fidation degree of Mo by 21.8％ as compared to the CoMo/γ-Al2O3 catalyst,which was beneficial to form more active sites.The HDS conversion of the NDC supported catalysts are higher than CoMo/γ-Al2O3 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/γ-Al2O3 catalyst.     

Synthesis,characterization and catalytic methanation performance of modified kaolin-supported Ni-based catalysts

Kaolin as a raw material for mesoporous support was firstly modified by calcination, acid treatment, and then was used to prepare nickel catalysts. The amount of alumina which was activated in kaolin during thermal treatment and then leached out in the acid was different. XRD pattern of the kaolin calcined at 600℃ or 900℃ exhibited only the diffraction peaks for amorphous silica and quartz while that calcined at 1100℃ showed obvious peaks for γ-Al₂O₃. Therefore, the nickel-based catalysts exhibited different physic-chemical properties. Atmospheric syngas methanation over the catalysts clarified an activity order of CA-1100 > CA-900 > CA-1400 > CA-600 > KA ≈ 0 at temperatures of 350-650℃ and a space velocity of 120 L·g^-1·h^-1. Metallic nickel with small diameter which has medium interaction with the modified kaolin and is well dispersed on the support would have reasonably good activity and carbon-resistance for syngas methanation.     

Catalytic hydrodechlorination of hexachlorobenzene on carbon supported Pd-Ni bimetallic catalysts

The study of the catalytic activity of carbon supported Pd-Ni catalysts for the hydrodechlorination of hexachlorobenzene was carried out in the liquid phase. The degree of dechlorination was found proportional to the surface Pd concentration, which is enhanced by the segregation of this element at the surface of the bimetallic particles.

It is also shown that isolated Pd atoms located at the surface of Ni rich bimetallic particles are more active than those lying in larger ensembles.

Finally bimetallic Pd-Ni catalysts containing only between 20 and 50 Pd atom%, although less active than pure Pd, lead to 75% of useful compounds, i.e. benzene, mono and dichlorobenzene.     

Effect of the electronic properties of Mo sulfide phase on the hydrotreating activity of catalysts supported on Al2O3, Nb2O5 and Nb2O5/Al2O3

Activity in thiophene hydrodesulfurization (HDS) and in the three routes of 2,6-dimethylaniline (DMA) decomposition was examined on Mo sulfide catalysts supported on Al₂O₃, Nb₂O₅ and Nb₂O₅–Al₂O₃. Catalysts activity is enhanced when Mo phase is deposited on niobium-containing support. For HDS and for the hydrogenation route of DMA decomposition, the niobium-containing support strongly contributes to the catalyst activity whereas the activity of the Mo phase per Mo atom decreases with the increase of niobium amount in the support. By contrast, as for the DMA route, which leads to xylene formation (XYL), the activity of the Mo sulfide phase per Mo atom is strongly enhanced. The electronic properties of the MoS₂ phase were studied by means of IR spectroscopy of CO adsorption. Comparison of ν(CO/Mo) wavenumbers reveals an upward shift when Mo sulfide phase is deposited on Nb-containing support. The modification of the electronic properties of the sulfide phase is related to an interaction Mo–Nb either through the formation of a mixed Mo–Nb sulfide phase, or through the interaction MoS₂ slabs – support whose strength depends on the support acidity. Hence, the beneficial effect for xylene formation route is attributed to a decrease of the electron density of the Mo sulfide phase that should strengthen the DMA adsorption on the sulfide phase.     

Performances of mixed alcohols synthesis over potassium promoted molybdenum carbides

Molybdenum carbides, β-Mo₂C and α-MoC_1−X, promoted by K₂CO₃ were studied as catalysts for CO hydrogenation reactions at T = 573 K, P = 8.0 MPa, GHSV = 2000 h⁻¹, H₂/CO = 1.0. Unpromoted molybdenum carbides produced mainly light hydrocarbons under these conditions. Addition of K₂CO₃ as a promoter, however, both β-Mo₂C and α-MoC_1−X resulted in remarkable selectivity shift from hydrocarbons to alcohols. Moreover, the promoter of potassium enhanced the ability of chain propagation of β-Mo₂C and α-MoC_1−X with higher selectivity to C₂₊OH. Meanwhile, the investigation of the loadings of K₂CO₃ in β-Mo₂C and α-MoC_1−X revealed that the maximum of yield of alcohol was obtained at K/Mo (molar ratio) of 0.2 and 0.1, respectively. On K/β-Mo₂C catalysts, the distribution of hydrocarbons obeyed traditional linear A–S–F plot, while alcohols gave a unique linear A–S–F distribution with remarkable deviation of methanol compared with that of on β-Mo₂C catalyst. However, there was no significant difference between α-MoC_1−X and K/α-MoC_1−X catalysts about the distributions of alcohols and hydrocarbons; they both have similar linear A–S–F plots. Thus, the potassium promoter played a different role over β-Mo₂C and α-MoC_1−X catalysts upon the catalytic performance of mixed alcohols synthesis.     

Second row transition metal sulfides for the hydrotreatment of coal-derived naphtha I. Catalyst preparation, characterization and comparison of rate of simultaneous removal of total sulfur, nitrogen and oxygen

Naphtha derived from an Illinois No. 6 coal contains appreciable quantities of sulfur-, nitrogen- and oxygen-containing compounds. The hydrotreatment of this naphtha has been evaluated over unsupported transition metal sulfide catalysts of the second row in the Periodic Table. The catalysts were prepared by a room temperature precipitation reaction. Surface areas, crystalline phase and particle size distributions were determined by Brunauer-Emmet-Teller (BET), X-ray diffraction (XRD) and transmission electron microscopy (TEM), respectively. A comparison of average particle sizes calculated from these three techniques has enabled the understanding of the morphology of the transition metal sulfides. The catalysts exhibit a so-called volcano plot for the HDS of dibenzothiophene. Similar so-called volcano plots are also exhibited for the simultaneous hydrodesulfurization (HDS), hydrodenitrogenation (HDN) and the hydrodeoxygenation (HDO) of the coal-derived naphtha containing a mixture of heteroatoms. The order of reactivity of the transition metal catalysts is the same for all three of the processes. Ruthenium sulfide (RuS₂) is the most active catalyst for HDS, HDN and HDO of the coal-derived naphtha.