Preparation of Vanadium Phosphate Catalysts from VOPO4 · 2H2O: Effect of Microwave Irradiation on Morphology and Catalytic Property

The present work addresses the influence of microwave irradiation on undoped and doped vanadium phosphate catalysts. These catalysts were prepared via VOPO₄ · 2H₂O. The catalyst’s precursors‚ VOHPO₄ · 0.5H₂O were subjected to microwave irradiation and comparison was made with the conventional heating. The interaction of these complex materials with microwave and the addition of several doponts (Nb, Bi, Co, Mo) provide interesting improvements in catalyst preparation found to be a faster, develop higher surface area, higher activity and selectivity for the oxidation of n-butane to maleic anhydride. All the catalysts were characterized by using a combination of powder XRD, H₂-TPR, BET surface area and SEM.     

Influence of Rare-Earth and Bimetallic Promoters on Various VPO Catalysts for Partial Oxidation of n-Butane

Vanadium phosphorous oxide (VPO) catalyst was prepared using dihydrate method and tested for the potential use in selective oxidation of n-butane to maleic anhydride. The catalysts were doped by La, Ce and combined components Ce + Co and Ce + Bi through impregnation. The effect of promoters on catalyst morphology and the development of acid and redox sites were studied through XRD, BET, SEM, H₂-TPR and TPRn reaction of n-butane/He. Addition of rare-earth element to VPO formulation and drying of catalyst precursor by microwave irradiation increased the fall width at half maximum (FWHM) and reduced the crystallite size of the Vanadyl hydrogen phosphate hemihydrate (VOHPO₄ · 1/2 H₂O, VHP) precursor phase and thus led to the production of final catalysts with larger surface area. The Ce doped VPO catalyst which, assisted by the microwave heating method, exhibited the highest surface area. Moreover, the addition of promoters significantly increased catalyst activity and selectivity as compared to undoped VPO catalyst in the oxidation reaction of n-butane. The H₂-TPR and TPRn reaction profiles showed that the highest amount of active oxygen species, i.e., the V⁴⁺–O^? pair, was removed from the bimetallic (Ce + Bi) promoted catalyst. This pair is responsible for n-butane activation. Furthermore, based on catalytic test results, it was demonstrated that the catalyst promoted with Ce and Bi (VPOD1) was the most active and selective catalyst among the produced catalysts with 52% reaction yield. This suggests that the rare earth metal promoted vanadium phosphate catalyst is a promising method to improve the catalytic properties of VPO for the partial oxidation of n-butane to maleic anhydride.     

Preparation of vanadium phosphate catalyst precursors using a high pressure method

The preparation of vanadium phosphate catalysts is known to be an important factor in determining their performance for the oxidation of butane to maleic anhydride. In this paper the preparation of catalyst precursors from V₂O₅ and H₃PO₄ using both aqueous hydrochloric acid and isobutanol as reducing agents are evaluated. In particular, the preparation of materials at higher temperatures using an autoclave method is described and compared with the materials prepared using the typical reflux methodology. The materials were characterised using a combination of powder XRD, BET surface area measurement, laser Raman spectroscopy and scanning electron microscopy. With the reflux method (1 bar pressure) both methods lead to the formation of VOHPO₄·0.5H₂O. The aqueous hydrochloric acid method leads to the formation of VO(H₂PO₄)₂ as a minor impurity that is readily removed by water extraction. The high temperature autoclave route gives significant differences. The aqueous hydrochloric acid route surprisingly does not give V⁴⁺ phases but gives a mixture of hydrated VOPO₄·xH₂O phases. In contrast the isobutanol method at higher temperature and pressure gave VOHPO₄·0.5H₂O as expected. However, for both methods the use of the higher temperature and higher pressure led to lower surface area materials being formed and consequently this will limit the usefulness of this methodology with these reducing agents.     

n-butane oxidation to maleic anhydride: effect of Co and Fe addition by the method of incipient wetness on vanadium phosphate catalysts prepared by the aqueous HC1 method

The effect of the addition of Co²⁺ and Fe³⁺ on the catalytic performance and structure of vanadium phosphate catalysts is described and discussed. The catalyst precursor VOHPO₄.0.5H₂O was prepared using the aqueous HC1 route and Co²⁺ and Fe³⁺ were incorporated using the incipient wetness method. Addition of Co²⁺ improves the selectivity to maleic anhydride, but is found to decrease the specific activity for the formation of maleic anhydride, whereas the addition of Fe³⁺ increases the specific activity up to a maximum level at ca. 2 mol% Fe. The effects are not due to changes in the specific surface area of the final catalyst, which remains 6.5 ±0.5 m² g^–1 for all the catalysts studied. Part of the effect is due to the formation of VOPO₄ phases in the catalyst precursor due to the method of addition of the Co²⁺ or Fe³⁺ and this is both related to the effect of the oxidation potential of the additive cation and to the pH of the impregnating solution. It is apparent that the use of the incipient wetness method for the addition of promoter compounds should be used with care for the VPO system at variance with the direct incorporation of the promoter during the preparation of the VOHPO₄.0.5H₂O precursor.     

Influence of supported vanadium catalyst on ethylene polymerization reactions

BACKGROUND: In the research area of homogeneous Ziegler–Natta olefin polymerization, classic vanadium catalyst systems have shown a number of favourable performances. These catalysts are useful for (i) the preparation of high molecular weight polymers with narrow molecular weight distributions, (ii) the preparation of ethylene/R‐olefin copolymers with high R‐olefin incorporation and (iii) the preparation of syndiotactic polypropylenes. In view of the above merits of vanadium‐based catalysts for polymerization reactions, the development of well‐defined single‐site vanadium catalysts for polymerization reactions is presently an extremely important industrial goal. The main aim of this work was the synthesis and characterization of a heterogeneous low‐coordinate non‐metallocene (phenyl)imido vanadium catalyst, V(NAr)Cl₃, and its utility for ethylene polymerization. RESULTS: Imido vanadium complex V(NAr)Cl₃ was synthesized and immobilized onto a series of inorganic supports: SiO₂, methylaluminoxane (MAO)‐modified SiO₂ (4.5 and 23 wt% Al/SiO₂), SiO₂? Al₂O₃, MgCl₂, MCM‐41 and MgO. Metal contents on the supported catalysts determined by X‐ray fluorescence spectroscopy remained between 0.050 and 0.100 mmol V g^?1 support. Thermal stability of the catalysts was determined by differential scanning calorimetry (DSC). Characterization of polyethylene was done by gel permeation chromatography and DSC. All catalyst systems were found to be active in ethylene polymerization in the presence of MAO or triisobutylaluminium/MAO mixture (Al/V = 1000). Catalyst activity was found to depend on the support nature, being between 7.5 and 80.0 kg PE (mol V)^?1 h^?1. Finally, all catalyst systems were found to be reusable for up to three cycles. CONCLUSION: Best results were observed in the case of silica as support. Acid or basic supports afforded less active systems. In situ immobilization led to higher catalyst activity. The resulting polyethylenes in all experiments had ultrahigh molecular weight. Finally, this work explains the synthesis and characterization of reusable supported novel vanadium catalysts, which are useful in the synthesis of very high molecular weight ethylene polymers. Copyright © 2007 Society of Chemical Industry     

Preparation of La-Mn-O Perovskite Catalyst by Microwave Irradiation Method and its Application to Methane Combustion

La-Mn-O perovskite catalyst was successfully prepared by microwave irradiation processing using only several minutes for heat treatment, and characterized by XRD, SEM, XPS, H₂-TPR and O₂-TPD. The catalyst by microwave irradiation processing with 6 min, mainly non-stoichiometric excess oxygen LaMnO_3.15 phase, shows excellent catalytic performance. Compared with the sample prepared by conventional method, it possesses relative higher surface area, the increase in Mn⁴⁺ and oxygen vacancy content and the enhancement in the mobility of lattice oxygen which play an important part in the methane combustion.     

The Synthesis of Three-Dimensional CeO2 and Their Catalytic Activities for CO Oxidation

This article reports a novel preparation of three-dimensional (3D) CeO₂ originating from crystalline cerium formate by a surfactant-free route using H₂O, ethanol and ethylene glycol as solvents. The sea urchin shaped 3D CeO₂ gave rise to micro/nanocomposite structures with high BET surface area up to 234 m² g^?1. The 3D structure improved the reducibility of surface CeO₂ due to the increased oxygen vacancy. Both 3D CeO₂ and 5 wt% CuO loaded on 3D CeO₂ exhibit high catalytic activities for CO conversion.     

Effect of the preparation conditions of carbon-supported Pt catalyst on PEMFC performance

Carbon-supported Pt catalysts were prepared using NaBH₄ as a reducing agent in either ethylene glycol or water for use as a cathode catalyst in PEMFCs (polymer electrolyte membrane fuel cells). Aqueous NaBH₄ solution was used to reduce Pt precursor and to produce the Pt-W catalyst, while Pt-E and Pt-E-base catalysts were synthesized using NaBH₄ in ethylene glycol for the reduction of Pt. Compared to Pt-W catalyst, Pt-E and Pt-E-base catalysts have higher Pt dispersion and larger EAS (electrochemically active surface area) due to the stabilizing effect of ethylene glycolic NaBH₄ solution on Pt particles. In addition, increasing pH of the preparation solution improved the Pt dispersion (Pt-E-base). In unit cell tests the performance of Pt catalysts decreased in the following order: Pt-E-base > Pt-E > Pt-commercial > Pt-W. Higher metal dispersion and larger EAS are believed to be responsible for the superior performance of Pt-E catalysts, particularly Pt-E-base, compared to other catalysts.     

A REACTION-EXTRACTION-REGENERATION SYSTEM FOR HIGHLY SELECTIVE OXIDATION OF BENZENE TO PHENOL

The reaction-extraction-regeneration system for the liquid-phase oxidation of benzene to phenol in the benzene-water-oxygen system was investigated. Phenol was extracted in the extractor to reduce the concentration of phenol in the benzene phase. As vanadium catalyst was oxidized to inactive species after the oxidation reaction, the regenerator was installed in the system to reduce the oxidation state of vanadium catalyst from V⁴⁺ or VO²⁺ to the active V³⁺ under H₂ flow. The effects of various operating parameters including concentration of VCl₃ catalyst, O₂ and H₂ flow rates, benzene bubble size, pH, surface area of Pt regeneration catalyst, the metal species, and amount of ascorbic acid were investigated. Ascorbic acid was employed as a reducing agent for helping reduce the V⁴⁺ form to the active form and therefore improving the activity of vanadium catalyst. VCl₃ catalyst concentration of 10 mol/m³ with pH of 3–4 in the reactor and Pt surface area of 0.05 m² in the regenerator showed optimal conditions for the system.     

Spherical mesocellular silica foams: a superior support for hydrodesulfurization of fluid catalytic cracking diesel

High surface area aluminum containing spherical mesocellular silica foams (SMCFs) with ultra-large pore volume and 3D pore size were successfully synthesized through a simple hydrothermal route, and the as-synthesized aluminum containing SMCFs (Al-SMCFs) was applied as the support of NiMo-base catalyst for the hydrodesulfurization (HDS) of fluid catalytic cracking (FCC) diesel. The as-synthesized supports and corresponding catalysts were characterized by powder small X-ray diffraction, nitrogen physisorption, scanning electron microscopy, transmission electron microscopy (TEM), inductively coupled plasma optical emission spectroscopy, and temperature-programmed reduction with H₂. The characterization results showed that, compared with other prepared catalysts (NiMo/Al-SBA-15 and NiMo/Al-KIT-6), the NiMo/Al-SMCFs catalyst possessed the most optimal physicochemical parameters, i.e., ultra-large 3D pore size (42.0 nm), high surface area (330.1 m²·g^?1), and ultra-large pore volume (1.96 cm³·g^?1), resulting in the formation of more homogeneous distribution of octahedral Mo active species and good mass transfer performance. Consequently, the NiMo/Al-SMCFs catalyst displayed the outstanding HDS performance (98.8%) of FCC diesel, confirming that the Al-SMCFs may be a type of promising candidate for oil hydrotreating.     

Microwave Synthesized Mesoporous Vanadium-MFI Catalysts for Epoxidation of Styrene Using Molecular Oxygen

Carbon templated mesoporous vanadium MFI catalysts with different Si/V ratios were successfully synthesized using microwave irradiation. X-ray diffraction studies revealed the formation of more crystalline MFI structures. SEM and TEM imaging also showed well ordered zeolite single crystals having mesoporosity. The N₂ sorption isotherm showed the formation of bimodal mesoporous zeolites. FT-IR studies showed absorbance around 970 cm^?1 corresponding to Si–O–V stretching vibration and the UV–Vis studies revealed strong peaks in the range of 230–340 nm which is related to the presence of tetrahedral V⁵⁺ state. The catalytic activity of the microwave synthesized catalysts was evaluated for epoxidation of styrene using molecular oxygen. The catalysts exhibited 20–40% styrene conversion with 60–75% epoxide selectivity. With increasing Vanadium content, the conversion as well as the selectivity was observed to increase. The catalyst could be recycled for three cycles without a loss in activity.     

How the Yield of Maleic Anhydride in n-Butane Oxidation,Using VPO Catalysts,was Improved Over the Years

Key patents for the oxidation of n-butane to maleic anhydride (MA) using V/P mixed metal oxides (VPO) have been analyzed to evidence the important parameters needed to optimize the catalytic behaviour. The important aspects for the optimization of the catalyst performance are the preparation of the precursor (VO)HPO₄·0.5H₂0, its activation to form the active catalyst VO₂P₂O₇ and a small amount of VOPO₄, the methodology of the addition of promoters, and the shaping of the catalyst. Even small, sustainable improvements in the MA yield (>1 %) achieved by improved, modified or optimized catalysts are significant on an industrial scale with the world production of MA being a respectable 2.7 Million tons/year. Although substantial improvements in MA yield have been achieved industrially over the past 40 years by improving the VPO catalyst composition and by optimizing process operations; the MA process remains, as practiced today, one of the least efficient industrial selective oxidation processes. Therefore, a huge incentive exists in the field to improve the MA catalyst and process, which led us to search for clues towards this end by analyzing the pertinent patent literature, as reported here.     

Rapid synthesis of cellulose triacetate from cotton cellulose and its effect on specific surface area and particle size distribution

A highly rapid process is described for the preparation of cellulose triacetate and its effect on particle size and surface area of the product. The process involves microwave-assisted rapid synthesis of cellulose triacetate with very low amount of acetic anhydride (10–15% of acetic anhydride is used in conventional methods) in the presence of iodine as a catalyst using a designed reaction vessel. The technique used is simple and rapid; it is also characterized by a high conversion ratio (yield 100%). A small amount of iodine (115 and 230 mg, 1.15 and 2.3% of cellulose weight) was found to be effective in the production of cellulose triacetate using 25, 30 to 40 mL acetic anhydride for 10 g cellulose under microwave irradiation for 2–4 min. The production of cellulose triacetate and the degree of substitution were confirmed by FTIR, Raman, ¹H NMR, and thermogravimetric analysis. The optimal reaction condition was discovered to be 3 min microwave radiation and 30 mL acetic anhydride in the presence of 230 mg iodine for 10 g cellulose. The effects of the amount of acetic anhydride, and amount of catalyst and reaction time on the specific surface area, pore volume, mean pore diameter, and particle size distribution were investigated. The highest surface area obtained was 39.63 m²/g. The specific surface area and particle size distribution are highly dependent on the amount of acetic anhydride and I₂ catalyst. About 10% of the synthesized cellulose acetate showed particle size less than 200 nm.     

The effect of the duration of n-butane/air pretreatment on the morphology and reactivity of (VO)2P2O7 catalysts

Three vanadium pyrophosphate catalysts have been prepared by calcining vanadium hydrogen phosphate hemihydrate (VOHPO₄0.5H₂O, prepared in an organic medium) for different lengths of time (40, 100 and 132 h) in a n-butane (0.75%)/air mixture at 473 K. The catalysts were designated VPO40, VPO100 and VPO132. Increasing the duration of reaction with n-butane/air mixture led to an increase in the total surface area from 21.3 m²g^–1 (VPO40) to 24.9 m²g^–1(VPO100) and to 27.0 m²g^–1(VPO132). It also led to the complete removal of the VOPO₄ phase from catalysts VPO100 and VPO132, this VOPO₄ phase having seen as a minor component of catalyst VPO40. Scanning electron microscopy showed that longer periods of pretreatment in the n-butane/air mixture produced catalysts with increasing amounts of a characteristic rosette-type of agglomerate. Temperature-programmed reduction with H₂ resulted in the removal of 11 monolayers equivalent of oxygen from all three of these catalysts at a peak maximum temperature of 1000 K with the development of a second reduction peak at 1100 K which increases with increasing time of n-butane/air pretreatment. The morphology produced by extended pretreatment in the n-butane/air mixture at 673 K is therefore predisposed to reaction with H₂ (and probably with n-butane). Apparently paradoxically, increasing the duration of n-butane/air pretreatment results in catalysts which on temperature-programmed desorption desorb less oxygen.     

Comparison of Ethylene Glycol Steam Reforming Over Pt and NiPt Catalysts on Various Supports

Steam reforming of ethylene glycol (EG) was studied on Pt and NiPt catalysts supported on γ-Al₂O₃, TiO₂, and carbon. On all supports bimetallic NiPt catalysts show higher activity for H₂ production than the corresponding Pt catalysts as predicted from model surface science studies. The kinetic trends are similar for all catalysts (Pt and NiPt) with the H₂ production rate being zero-order and fractional order with respect to water and ethylene glycol, respectively. Slight differences in selectivity to minor products are observed depending both on active metal and support. On γ-Al₂O₃, NiPt shows higher H₂ and less alkane formation than Pt. TiO₂ supported catalysts show increased water-gas shift activity but also increased selectivity to alkane precursors. NiPt/C is identified as an active and selective catalyst for EG reforming.     

Vanadium oxide catalysts on structured microfiber supports for the selective oxidation of hydrogen sulfide

Vanadium(V) oxide catalysts for the selective oxidation of hydrogen sulfide to sulfur on a nonporous glass-fiber support with a surface layer of a porous secondary support (SiO₂) are studied. The catalysts are obtained by means of pulsed surface thermosynthesis. Such catalysts are shown to have high activity and acceptable selectivity in the industrially important region of temperatures below 200°C. A glass-fiber catalyst containing vanadium oxide (10.3 wt % of vanadium) in particular ensures the complete conversion of H₂S at a temperature of 175°C and a reaction mixture hourly space velocity (RMHSV) of 1 cm³/(g_cat s) with a sulfur yield of 67%; this is at least 1.35 times higher than for the traditional iron oxide catalyst. Using a structured glass-fiber woven support effectively minimizes diffusion resistance and greatly simplifies the scaleup of processes based on such catalysts. Such catalysts can be used for the cleansing of tail gases from Claus units and in other processes based on the selective oxidation of H₂S.     

Vanadyl formate VO(HCOO)2·H2O as a precursor for preparing nanoscale vanadium sesquioxide V2O3

Vanadyl formate monohydrate VO(HCOO)₂·H₂O has been synthesized by a facile two-stage method. The chemical and structural identity of the synthesized compound has been confirmed by X-ray diffraction, thermogravimetry, vibrational and absorption spectroscopy. It was established that during heating in water and ethylene glycol, VO(HCOO)₂·H₂O leads to vanadyl hydroxide VO(OH)₂ and vanadyl glycolate VO(OCH₂CH₂O) being formed. When heated in air or in helium at 300 °C and higher, VO(HCOO)₂·H₂O transforms into vanadium pentoxide or sesquioxide, respectively. VO(HCOO)₂·H₂O was used as a precursor for the synthesis of nanoscale vanadium sesquioxide (with an average particle size of 50 nm), which is stable under the normal conditions and is characterized by a lower metal-insulator transition temperature than the microsized (bulk) compound. The effect of transition temperature reduction for nanoscale vanadium sesquioxide agrees with the lower value of its unit cell volume (V = 296.74 Å³) as compared with that for bulk V₂O₃ (297.7 Å³). The main factor affecting the V₂O₃ particle size is the annealing temperature of precursor in inert atmosphere.     

Tetrahydrofuran polymerization initiated by heteropolyacid in the presence of ethylene oxide: Reaction behavior of water and glycol

The reaction behavior of water and low molecular weight glycol in tetrahydrofuran polymerization initiated by H₃PW₁₂O₄₀ in the presence of ethylene oxide has been studied. A lot of water was used in the hydrolysis reaction of ethylene oxide at the early stage of the polymerization and transformed into ethylene glycol (EG), which was consumed subsequently through a chain transfer reaction. EG was more reactive both than 1,4‐butylene glycol and hexamethylene glycol toward propagating species, and the reaction rate constants at 0°C were determined by GC to be 0.142, 8.83 × 10⁻², and 5.53 × 10⁻² L · mol⁻¹s⁻¹, respectively. The molecular weight of the product can be predicted by an equation based upon conversion of polymerization and the concentrations of molecular weight controller and H₃PW₁₂O₄₀. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 74: 1821–1826, 1999     

Synthesis and activity of zirconocene catalysts supported on silica-type sol-gel carrier for ethylene polymerization

Summary Synthesis and activity of bis(cyclopentadienyl)zirconium dichloride catalyst supported on unconventional silica-type material obtained in sol-gel process and activated by organoaluminium co-catalyst were studied. The effect of support modification conditions (thermal dehydration and/or modification by organoaluminium compound) and a type of co-catalyst on an activity of the catalytic system in ethylene polymerization and properties of resulting polymers were investigated and compared with results obtained earlier for vanadium catalysts supported on mentioned sol-gel carrier. The most appropriate method of the sol-gel silica-type support preparation is thermal pre-treating (200°C) followed by modification with AlEt₂Cl. Metallocene catalyst supported on such sol-gel product and activated by MAO appeared to be most active among studied systems. Studied Cp₂ZrCl₂/MAO supported on silica-type sol-gel carrier allow to obtain polyethylene (at 50°C polymerization temperature) with yield up to 30·10⁶ g/(mol_Zr·h), molecular weight below 300 000 and MWD=2−4. Received: 4 September 2000/Revised version: 3 January 2001/Accepted: 3 January 2001     

Direct conversion of cellulose into polyols or H2 over Pt/Na(H)-ZSM-5

The direct conversion of cellulose into polyols such as ethylene glycol and propylene glycol was examined over Pt catalysts supported on H-ZSM-5 with different SiO₂/Al₂O₃ molar ratios. The Pt dispersion, determined by CO chemisorption and transmission electron microscopy (TEM), as well as the surface acid concentration measured by the temperature-programmed desorption of ammonia (NH₃-TPD), increased with decreasing SiO₂/Al₂O₃ molar ratio for Pt/H-ZSM-5. The total yield of the polyols, i.e., sorbitol, manitol, ethylene glycol and propylene glycol, generally increased with increasing Pt dispersion in Pt/H-ZSM-5. The one-pot aqueous-phase reforming of cellulose into H₂ was also examined over the same catalysts. The Pt catalyst supported on H-ZSM-5 with a moderate SiO₂/Al₂O₃ molar ratio and a large external surface area showed the highest H₂ production rate. The Pt dispersion, surface acidity, external surface area and surface hydrophilicity appear to affect the catalytic activity for this reaction.