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Catalyst Activity (catalyst + activity)
Selected AbstractsInfluence of supported vanadium catalyst on ethylene polymerization reactionsPOLYMER INTERNATIONAL, Issue 2 2008Sutapa Ghosh Abstract 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 [source] Kinetic Reaction Models for the Selective Reduction of NO by Methane over Multifunctional Zeolite-based Redox CatalystsCHEMICAL ENGINEERING & TECHNOLOGY (CET), Issue 12 2004T. Sowade Abstract Kinetic measurements of the selective catalytic reduction (SCR) of NO by methane were performed over CeO2/H-ZSM-5, In-ZSM-5, and CeO2/In-ZSM-5 catalysts. The parameter space covered NO, CH4, and O2 concentrations varying from 250 to 1000 ppm, from 500 to 2000 ppm, and from 0.5 to 10,vol.-%, respectively, space velocities between 5000 and 90000 h,1 and temperatures between 573 and 873 K depending on the catalyst activities. With CeO2/In-ZSM-5 an additional series of measurements was performed with moistened feed gas (0.5,10,vol.-% H2O). On the basis of a pseudo-homogeneous, one-dimensional fixed-bed reactor model, the data were fitted to a kinetic model that includes power rate laws for the reduction of NO and for the unselective total oxidation of methane. From analyses of isothermal data sets, almost all reaction orders were found to vary significantly with changing temperature, which indicates that the simple kinetic model cannot reflect the complex reaction mechanism correctly. Nevertheless, the data measured with In-ZSM-5 could be modeled with good accuracy over a wide range of reaction temperatures (150 K) while the accuracy was less satisfactory with the remaining data sets, in particular for data with the moist feed over CeO2/In-ZSM-5. With the latter catalyst it was not possible to represent the data measured in dry and in moist feed in a single model even upon confinement to fixed reaction temperatures. A comparison of the separate models established showed strong changes in the reaction orders in the presence of water, which occur apparently already at a very low water content (,,0.5,vol.-%). The kinetic parameters found are in agreement with earlier conclusions about the reaction mechanisms. With In-ZSM-5, both reaction orders and the activation energy show a rate-limiting influence of NO oxidation on the NO reduction path which is removed by the presence of the CeO2 promoter. A difference in the reaction mechanism over CeO2/In-ZSM-5 and CeO2/H-ZSM-5 is reflected in different kinetic parameters. The differences of the kinetic parameters between dry-feed and moist-feed models for CeO2/In-ZSM-5 reflect adsorption competition between the reactants and water. [source] Mono(aryloxido)Titanium(IV) Complexes and Their Application in the Selective Dimerization of EthyleneEUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 20 2009Jean-Benoit Cazaux Abstract We report on the synthesis of mono(aryloxido)titanium(IV) complexes of general formula {Ti[O(o -R)Ar]X3}, with X = OiPr, ArO = 2- tert -butyl-4-methylphenoxy and R = CMe3 (2a), CMe2Ph (2b) and CH2NMe2 (2c). Attempts to reach pure mono(aryloxido) complexes when R = CH2NMe(CH2Ph) (2d) or CH2N(CH2Ph)2 (2e) were unsuccessful. When R = CH2OMe, the analogous mononuclear complex was not obtained, and instead, a dinuclear complex [(2- tert -butyl-4-methyl-6-methoxymethylphenoxy) TiCl(OiPr)(,2 -OiPr)2TiCl(OiPr)2] (3) was formed. Complexes 2b and 3 were characterized by single-crystal X-ray diffraction. The former contains a tetrahedrally coordinated TiIV centre, whereas in the latter the aryloxido ligand behaves as a chelating,bridging ligand between the two, chemically very different metal centres that form two face-sharing octahedra. Different synthetic approaches starting from [Ti(OiPr)4] or [TiCl(OiPr)3] were evaluated and are discussed. The hemilabile behaviour of the aryloxido ligand resulting from reversible coordination of its side arm was studied by variable-temperature 1H NMR spectroscopy for 2c (R = CH2NMe2). Complexes 2a,d were contacted with ethylene and AlEt3 as cocatalyst. When activated with AlEt3 (3 equiv.) at 20 bar and 60 °C, complex 2c exhibits interesting activity (2100 g/gTi/h) for the selective dimerization of ethylene to 1-butene (92,% C4=; 99+% C4=1). Noticeable differences in catalyst activity were observed when the R group was modified. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2009) [source] Towards Long-Living Metathesis Catalysts by Tuning the N-Heterocyclic Carbene (NHC) Ligand on Trifluoroacetamide-Activated Boomerang Ru ComplexesEUROPEAN JOURNAL OF ORGANIC CHEMISTRY, Issue 25 2009Hervé Clavier Abstract The synthesis and characterization of three novel trifluoromethylamido-containing "boomerang" precatalysts bearing various N-heterocyclic carbene (NHC) ligands are reported. Comparative kinetic and stability studies show the significant effect of the NHC on the catalyst reaction profile. An investigation of the reaction scope for diverse metathesis transformations has allowed us to establish the influence of the NHC on catalyst activity, especially as a function of substrate steric bulk. The excellent stability of one of the novel precatalysts is disclosed, and allowed for its recovery at the end of catalytic reactions. Large-scale ring-closing metathesis, enyne-metathesis and cross-metathesis experiments have revealed the recoverability of the catalyst. ICP-MS analyses of the synthesized products reveal Ru contamination levels of less than 2.5 ppm.(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2009) [source] Electro-Oxidation of Methanol and Ethanol on Poly(3,4-Ethylenedioxythiophene) with Dispersed Pt, Pt + Sn, and Pt + Pb Particles,FUEL CELLS, Issue 1-2 2003S. Biallozor Abstract The influence of tin and lead additives on the catalytic activity of platinum particles dispersed on a poly(3,4-dioxyethylenethiophene) (PEDT) layer deposited on gold or steel towards anodic oxidation of methanol and ethanol was studied. It was found that these additives increase the rate of anodic oxidation of both alcohols. It was also found that the electro-catalytic properties of PEDT depend on the kind of support used for its deposition. The authors have shown that these additives (Pb and Sn) increase the rate of anodic oxidation of both alcohols on platinum deposited on PEDT, but tin was evidently more effective than lead. In the presence of Sn, the steady-state current density of methanol oxidation increases about 100 times, while Pb only promotes the platinum catalyst activity by about 2 times. In the authors opinion the most probable mechanism for the tin promotion effect seems to be a homogenous catalytic reaction with the participation of the Sn (IV) and Sn (II) ions as mediators. [source] Suzuki reaction of aryl chlorides using saturated N -heterocarbene ligandsHETEROATOM CHEMISTRY, Issue 7 2005Ismail Özdemir From readily available starting materials, six 1,3-dialkyl-imidazolinium bromides (2a,f) have been prepared and characterized by conventional spectroscopic methods and elemental analyses. The incorporation of saturated N -heterocyclic carbenes into palladium precatalysts gives high catalyst activity in the Suzuki coupling of deactivated aryl chloride substrates in aqueous media. The complexes were generated in the presence of Pd(OAc)2 by in situ deprotonation of 2a,f. © 2005 Wiley Periodicals, Inc. Heteroatom Chem 16:557,561, 2005; Published online in Wiley InterScience (www.interscience.wiley.com). DOI 10.1002/hc.20140 [source] DiPAMP's Big Brother "i- Pr-SMS-Phos" Exhibits Exceptional Features Enhancing Rhodium(I)-Catalyzed Hydrogenation of OlefinsADVANCED SYNTHESIS & CATALYSIS (PREVIOUSLY: JOURNAL FUER PRAKTISCHE CHEMIE), Issue 17 2009Michel Stephan Abstract Switching Knowles DiPAMP's {DiPAMP=1,2-bis[(o -anisyl)(phenyl)phosphino]- ethane} MeO groups with i- PrO ones led to the i- Pr-SMS-Phos {i- Pr-SMS-Phos=1,2-bis[(o -isoprop- oxyphenyl)(phenyl)phosphino]ethane} ligand which displayed a boosted catalyst activity coupled with an enhanced enantioselectivity in the rhodium(I)-catalyzed hydrogenation of a wide-range of representative olefinic substrates (dehydro-,-amido acids, itaconates, acrylates, enamides, enol acetates, ,,,-diarylethylenes, etc). The rhodium(I)-(i- Pr-SMS-Phos) catalytic profile was investigated revealing its structural attributes and robustness, and in contrast to the usual trend, 31P,NMR analysis revealed that its methyl (Z)-,-acetamidocinnamate (MAC) adduct consisted of a reversed diastereomeric ratio of 1.4:1 in favour of the most reactive diastereomer. [source] Palladium-Catalysed Telomerisation of Isoprene with Glycerol and Polyethylene Glycol: A Facile Route to New Terpene DerivativesADVANCED SYNTHESIS & CATALYSIS (PREVIOUSLY: JOURNAL FUER PRAKTISCHE CHEMIE), Issue 3 2009Alvaro Gordillo Abstract We present here the first example of the telomerisation of isoprene with glycerol and polyethylene glycol (PEG-200), opening a facile route to new terpene structures, based on a combination of renewable and petroleum-based feedstocks. The reaction is catalysed by a palladium-carbene complex. Significantly, this system gives >99% of linear monotelomer products. The factors that govern substrate conversion, dimerisation/telomerisation selectivity, and catalyst activity are studied and discussed. [source] Enhanced Hydrogenation Activity and Recycling of Cationic Rhodium Diphosphine Complexes through the Use of Highly Fluorous and Weakly-Coordinating Tetraphenylborate AnionsADVANCED SYNTHESIS & CATALYSIS (PREVIOUSLY: JOURNAL FUER PRAKTISCHE CHEMIE), Issue 5 2003Broeke, Joep van Abstract The effect of the nature of the anion on the performance of ionic rhodium catalysts has received little attention. Herein it is shown that the use of highly fluorous tetraphenylborate anions can enhance catalyst activity in both conventional and fluorous media. For hydrogenation catalysts of the type [Rh(COD)(dppb)][X] {COD=1,5- cis,cis -cyclooctadiene; dppb=1,4-bis(diphenylphosphino)butane; X=BF4, (1a), [BPh4], (1b), [B{C6H4(SiMe3)-4}4], (1c), [B{C6H3(CF3)2 -3,5}4], (1d), [B{C6H4(SiMe2CH2CH2C6F13)-4}4], (1e), [B{C6H4(C6F13)-4}4], (1f) and [B{C6H3(C6F13)2 -3,5}4], (1,g)} the activity towards the hydrogenation of 1-octene in acetone increased in the order 1c <1b <1e <1a <1d ~ 1f <1g with 1g being twice as active as the commonly applied 1a. Despite the fluorophilic character introduced by the substituted tetraarylborate anions, the presence of some perfluoroalkyl-substituents in the cation was still required for achieving high partition coefficients. Therefore, [Rh(COD)(Ar2PCH2CH2PAr2)][X] {Ar=C6H4(SiMe2CH2CH2C6F13)-4, X=[B{C6H3(C6F13)2 -3,5}4], (3f); Ar=C6H4(SiMe(CH2CH2C6F13)2)-4 and X=[B{C6H4(C6F13)-4}4], (2g)} were prepared, which were active in the hydrogenation of 1-octene, 2g even more so than 3f. Both these highly fluorous catalysts could be recycled with 99% efficiency through fluorous biphasic separation, whereas the corresponding BF4, complex of 2g (2a) did not show any affinity for the fluorous phase. [source] Selective Oxidation of Alcohols to Carbonyl Compounds and Carboxylic Acids with Platinum Group Metal CatalystsADVANCED SYNTHESIS & CATALYSIS (PREVIOUSLY: JOURNAL FUER PRAKTISCHE CHEMIE), Issue 4 2003Ross Anderson Abstract The use of platinum group metal (PGM) catalysts for the selective oxidation of various primary and secondary alcohols under mild conditions is described. High throughput screening (HTS) techniques have been used to identify trends in catalyst activity and product selectivity. Using air as oxidant and water as solvent 5% Pt, 1% Bi/C has been identified as an efficient catalyst for the transformation of 2-octanol to 2-octanone and 1-octanol to octanoic acid. To improve aldehyde selectivity the promotion of Pt/Al2O3 and Ru/C catalysts has been investigated. The use of H2O2 as oxidant has been demonstrated as a suitable alternative to air. [source] Preparation of ultra-high-molecular-weight polyethylene and its morphological study with a heterogeneous Ziegler,Natta catalystJOURNAL OF APPLIED POLYMER SCIENCE, Issue 6 2010G. H. Zohuri Abstract Ultra-high-molecular-weight polyethylene (PE) with viscosity-average molecular weight (Mv) of 3.1 × 106 to 5.2 × 106 was prepared with a heterogeneous Ziegler,Natta MgCl2 (ethoxide type)/TiCl4/triethylaluminum catalyst system under controlled conditions. The optimum activity of the catalyst was obtained at a [Al]/[Ti] molar ratio of 61 : 1 and a polymerization temperature of 60°C, whereas the activity of the catalyst increased with monomer pressure and decreased with hydrogen concentration. The titanium content of the catalyst was 2.4 wt %. The rate/time profile of the catalyst was a decay type with a short acceleration period. Mv of the PE obtained decreased with increasing hydrogen concentration and polymerization temperature. The effect of stirrer speeds from 100 to 400 rpm did not so much affect the catalyst activity; however, dramatic effects were observed on the morphology of the polymer particles obtained. A stirrer speed of 200 rpm produced PE with a uniform globulelike morphological growth on the polymer particles. The particle size distributions of the polymer samples were determined and were between 14 and 67 ,m. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010 [source] Spatial near-infrared imaging of hydroxyl band coverage on ceria-based catalystsAICHE JOURNAL, Issue 4 2006Farid Aiouache Abstract High-throughput near-infrared imaging was used to distinguish catalyst activity for low-temperature methane steam-reforming. Geminal hydroxyls of reduced ceria were depicted during methane reforming at 673 K. The changes in absorbance maps under various water partial pressures showed evidence of formate intermediate formations without redox exchanges. Higher resolution was observed in absorbance change images than that of thermal images obtained from catalyst surface self-emissions. The experimental results illustrated higher activity of pure rhodium catalyst than that of bimetallic ones, likely because of the high dispersion of rhodium on the catalyst support. Moreover, the reaction was accelerated when high surface area silica was added because more reduced sites were exposed. Our filter bandwidths limited our interest in band-shift distribution of geminal hydroxyl band during the reduction process. © 2005 American Institute of Chemical Engineers AIChE J, 2006 [source] Dryout phenomena in a three-phase fixed-bed reactorAICHE JOURNAL, Issue 1 2003Zhen-Min Cheng Understanding the mechanism of liquid-phase evaporation in a three-phase fixed-bed reactor is of practical importance, because the reaction heat is usually 7,10 times the vaporization heat of the liquid components. Evaporation, especially the liquid dryout, can largely influence the reactor performance and even safety. To predict the vanishing condition of the liquid phase, Raoult's law was applied as a preliminary approach, with the liquid vanishing temperature defined based on a liquid flow rate of zero. While providing correct trends, Raoult's law exhibits some limitation in explaining the temperature profile in the reactor. To comprehensively understand the whole process of liquid evaporation, a set of experiments on inlet temperature, catalyst activity, liquid flow rate, gas flow rate, and operation pressure were carried out. A liquid-region length-predicting equation is suggested based on these experiments and the principle of heat balance. [source] Ethylene/,-olefin copolymerization with bis(,-enaminoketonato) titanium complexes activated with modified methylaluminoxaneJOURNAL OF POLYMER SCIENCE (IN TWO SECTIONS), Issue 24 2005Li-Ming Tang Abstract Copolymerizations of ethylene with ,-olefins (i.e., 1-hexene, 1-octene, allylbenzene, and 4-phenyl-1-butene) using the bis(,-enaminoketonato) titanium complexes [(Ph)NC(R2)CHC(R1)O]2TiCl2 (1a: R1 = CF3, R2 = CH3; 1b: R1 = Ph, R2 = CF3; and 1c: R1 = t -Bu, R2 = CF3), activated with modified methylaluminoxane as a cocatalyst, have been investigated. The catalyst activity, comonomer incorporation, and molecular weight, and molecular weight distribution of the polymers produced can be controlled over a wide range by the variation of the catalyst structure, ,-olefin, and reaction parameters such as the comonomer feed concentration. The substituents R1 and R2 of the ligands affect considerably both the catalyst activity and comonomer incorporation. Precatalyst 1a exhibits high catalytic activity and produces high-molecular-weight copolymers with high ,-olefin insertion. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 6323,6330, 2005 [source] Polymerization of substituted acetylenes by various rhodium catalysts: Comparison of catalyst activity and effect of additivesJOURNAL OF POLYMER SCIENCE (IN TWO SECTIONS), Issue 19 2005Atsushi Nakazato Abstract This research deals with comparison of the activity of various Rh catalysts in the polymerization of monosubstituted acetylenes and the effect of various amines used in conjunction with [Rh(nbd)Cl]2 in the polymerization of phenylacetylene. A zwitterionic Rh complex, Rh+(nbd)[(,6 -C6H5)B,(C6H5)3] (3), was able to polymerize phenylacetylene (5a), t -butylacetylene (5b), N -propargylhexanamide (5c) and n -hexyl propiolate (5d), and displayed higher activity than the other catalysts examined, that is [Rh(nbd)Cl]2 (1), [Rh(cod)(O - o -cresol)]2 (2), and Rh-vinyl complex (4). Monomers 5a and 5c polymerized virtually quantitatively or in fair yields with all these catalysts, while monomer 5b was polymerizable only with catalyts 3 and 4. Monomer 5d did not polymerize in high yields with these Rh complexes. The catalytic activity tended to decrease in the order of 3 > 4 > 2 > 1. Although polymerization of 5a did not proceed at all in toluene with [Rh(nbd)Cl]2 alone, it smoothly polymerized in the presence of various amines as cocatalysts. The polymerization rate as well as the molecular weight of polymer depended on the basicity and steric bulkiness of amines. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 4530,4536, 2005 [source] Effects of methylaluminoxane immobilization on silica on the performance of zirconocene catalysts in propylene polymerizationJOURNAL OF POLYMER SCIENCE (IN TWO SECTIONS), Issue 13 2005Madri Smit Abstract Investigation of the characteristics and performance in propylene polymerization of silica-immobilized methylaluminoxane (MAO), in combination with a moderately and a highly isospecific zirconocene catalyst, has revealed that a simple impregnation of silica with MAO at ambient temperature is insufficient to obtain uniform distribution of MAO throughout the support particle. Homogeneous Al distribution throughout the support, giving increased catalyst activity, was achieved by a more rigorous impregnation of silica with MAO at elevated temperatures. The highest catalyst activities were obtained by precontacting the MAO with the zirconocene to generate the activated species before immobilization on silica. Polymer particle morphology was strongly dependent on the characteristics of the silica used for catalyst immobilization. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 2734-2748, 2005 [source] A new tetradentate ligand for atom transfer radical polymerizationJOURNAL OF POLYMER SCIENCE (IN TWO SECTIONS), Issue 14 2004Shijie Ding Abstract The properties of a ligand, including molecular structure and substituents, strongly affect the catalyst activity and control of the polymerization in atom transfer radical polymerization (ATRP). A new tetradentate ligand, N,N,-bis(pyridin-2-ylmethyl-3-hexoxo-3-oxopropyl)ethane-1,2-diamine (BPED) was synthesized and examined as the ligand of copper halide for ATRP of styrene (St), methyl acrylate (MA), and methyl methacrylate (MMA), and compared with other analogous linear tetrdendate ligands. The BPED ligand was found to significantly promote the activation reaction: the CuBr/BPED complex reacted with the initiators so fast that a large amount of Cu(II)Br2/BPED was produced and thus the polymerizations were slow for all the monomers. The reaction of CuCl/BPED with the initiator was also fast, but by reducing the catalyst concentration or adding CuCl2, the activation reaction could be slowed to establish the equilibrium of ATRP for a well-controlled living polymerization of MA. CuCl/BPED was found very active for the polymerization of MA. For example, 10 mol% of the catalyst relatively to the initiator was sufficient to mediate a living polymerization of MA. The CuCl/BPED, however, could not catalyze a living polymerization of MMA because the resulting CuCl2/BPED could not deactivate the growing radicals. The effects of the ligand structures on the catalysis of ATRP are also discussed. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 3553,3562, 2004 [source] Novel synthesis of polyethylene,poly(dimethylsiloxane) copolymers with a metallocene catalystJOURNAL OF POLYMER SCIENCE (IN TWO SECTIONS), Issue 10 2004Andrés E. Ciolino Abstract Polyethylene,poly(dimethylsiloxane) copolymers were synthesized in solution from an ethylene monomer and an ,-vinyl poly(dimethylsiloxane) (PDMS) macromonomer at 363 and 383 K with EtInd2ZrCl2/methylaluminoxane as a catalyst. The copolymers obtained were characterized with Fourier transform infrared spectroscopy, 1H and 13C NMR, size exclusion chromatography, and differential scanning calorimetry. The rheological properties of the molten polymers were determined under dynamic shear flow tests at small-amplitude oscillations, whereas the physical arrangement of the phase domains was analyzed with scanning electron microscopy (SEM)/energy dispersive X-ray (EDX). The analysis of the catalyst activity and the resulting polymers supported the idea of PDMS blocks or chains grafted to polyethylene. The changes in the rheological behavior and the changes in the Fourier transform infrared and NMR spectra were in agreement with this proposal. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 2462,2473, 2004 [source] Supported (nBuCp)2ZrCl2 Catalysts: Effects of Selected Lewis Acid Organotin Silica Surface Modifiers on Ethylene PolymerizationMACROMOLECULAR REACTION ENGINEERING, Issue 4 2008Muhammad N. Akhtar Abstract This study investigated the effects of several organotin silica surface modifiers on the ethylene polymerization performance of (nBuCp)2ZrCl2 -based supported catalysts in which MAO and metallocene were sequentially loaded. Each organotin compound acted as a spacer, increasing the catalyst activity. However, the catalyst activity and of the resulting polyethylenes varied as follows: Activity and fractional Sn+ charge: nBuSn(OH)2Cl,>,MeSnCl3,>,nBuSnCl3,>,Reference catalyst; and, : Reference catalyst,>,nBuSnCl3,>,MeSnCl3,>,nBuSn(OH)2Cl. The above catalyst activity rating was explained considering the influence of the Lewis acidity, that is, the fractional Sn+ charge of the organotin modifiers on the generation, concentration, and electron density at the active [(nBuCp)2ZrMe]+ cation. All the catalysts showed fairly stable kinetic profiles and produced narrow molecular weight distribution resins; 2.8,,,PDI,,,3. [source] Influence of supported vanadium catalyst on ethylene polymerization reactionsPOLYMER INTERNATIONAL, Issue 2 2008Sutapa Ghosh Abstract 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 [source] Rate equations for the fischer-tropsch reaction on a promoted iron catalystTHE CANADIAN JOURNAL OF CHEMICAL ENGINEERING, Issue 5 2001Montazer Rahmati Abstract Intrinsic rates for the Fischer-Tropsch synthesis reaction over a promoted iron catalyst fabricated at the Research Institute of the Petroleum Industry (RIPI) have been obtained in the temperature range of 290°C to 310°C, pressure range of 1500 to 2300 kPa, molar hydrogen to carbon monoxide ratio of 0.76 to 1.82, and a space velocity of 3300 h,1 under conditions of constant catalyst activity. To this end, the initial reaction rates have been measured at constant temperature (±1°C) in the absence of diffusion limitations, and power-law equations have been fitted in terms of the hydrogen and carbon monoxide partial pressures for the reaction rates. Des vitesses intrinsèques pour la réaction de synthèse de Fischer-Tropsch sur un catalyseur de fer activé fabriqué à l'Institut de recherche de l'industrie du pétrole (RIPI) ont été obtenues pour des températures entre 290°C et 310°C, des pressions entre 1500 et 2300 kPa, un rapport hydrogène molaire/oxyde de carbone entre 0.76 et 1.82 et une vitesse spatiale de 3300 h,1 avec une activité constante du catalyseur. À cette fin, les vitesses de réaction initiales ont été mesurées à température constante (±1°C) en l'absence de limitations par la diffusion, et des équations de loi de puissance ont été calées par rapport aux pressions partieiles de l'hydrogène et de l'oxyde de carbone pour les vitesses de réaction. [source] The Influence of Phosphane Ligands on the Versatility of Ruthenium,Indenylidene Complexes in MetathesisCHEMISTRY - A EUROPEAN JOURNAL, Issue 30 2010Julie Broggi Dr. Abstract The aim of the present study is to develop readily available and stable pre-catalysts that could be easily prepared on large scale from simple starting materials. Based on the hypothesis that substitution of classical PCy3 with phosphanes of varying electron-donating properties could be a straightforward manner to improve catalytic activity, a methodical study dealing with the effect of phosphane fine-tuning in ruthenium,indenylidene catalysts was performed. Challenged to establish how the electronic properties of para -substituted phosphane ligands translate into catalyst activity, the versatile behaviour of these new ruthenium,indenylidene complexes was investigated for a number of metathesis reactions. [source] Macrocyclic Cyclooctene-Supported AlCl,Salen Catalysts for Conjugated Addition Reactions: Effect of Linker and Support Structure on CatalysisCHEMISTRY - A EUROPEAN JOURNAL, Issue 5 2009Nandita Madhavan Dr. Abstract AlCl,salen (salen=N,N,-bis(salicylidene)ethylenediamine dianion) catalysts supported onto macrocyclic oligomeric cyclooctene through linkers of varying length and flexibility have been developed to demonstrate the importance of support architecture on catalyst activity. The role played by the support and the linkers in dictating catalyst activity was found to vary for reactions with contrasting mechanisms, such as the bimetallic cyanide and the monometallic indole addition reactions. While the flexible support significantly enhanced the cyanide addition reaction, most likely by improving salen,salen interactions in the transition state, it lowered the reaction rate for the monometallic indole reaction. For both reactions, significant increase in catalytic activity was observed for catalysts with the longest linkers. The effect of the flexible macrocyclic support on catalysis was further exemplified by the enhanced activity of the supported catalyst in comparison with its unsupported analogue for the conjugate addition of tetrazoles, which is known to be catalyzed by dimeric ,-oxo,salen catalysts. Our studies with the cyclooctene supported AlCl,salen catalysts provides significant insights for rationally designing highly efficient AlCl,salen catalysts for a diverse set of reactions. [source] Renewable H2 from Glycerol Steam Reforming: Effect of La2O3 and CeO2 Addition to Pt/Al2O3 catalysts.CHEMSUSCHEM CHEMISTRY AND SUSTAINABILITY, ENERGY & MATERIALS, Issue 5 2010Tiziano Montini Dr. Abstract Glycerol is the main byproduct of biodiesel production and its increased production volume derives from the increasing demand for biofuels. The conversion of glycerol to hydrogen-rich mixtures presents an attractive route towards sustainable biodiesel production. Here we explored the use of Pt/Al2O3 -based catalysts for the catalytic steam reforming of glycerol, evidencing the influence of La2O3 and CeO2 doping on the catalyst activity and selectivity. The addition of the latter metal oxides to a Pt/Al2O3 catalyst is found to significantly improve the glycerol steam reforming, with high H2 and CO2 selectivities. A good catalytic stability is achieved for the Pt/La2O3/Al2O3 system working at 350,°C, while the Pt/CeO2/Al2O3 catalyst sharply deactivates after 20,h under similar conditions. Studies carried out on fresh and exhausted catalysts reveal that both systems maintain high surface areas and high Pt dispersions. Therefore, the observed catalyst deactivation can be attributed to coke deposition on the active sites throughout the catalytic process and only marginally to Pt nanoparticle sintering. This work suggests that an appropriate support composition is mandatory for preparing high-performance Pt-based catalysts for the sustainable conversion of glycerol into syngas. [source] MCM-41 Bound Ruthenium Complex as Heterogeneous Catalyst for Hydrogenation I: Effect of Support, Ligand and Solvent on the Catalyst PerformanceCHINESE JOURNAL OF CHEMISTRY, Issue 7 2006Ying-Min Yu Abstract The functionalized MCM-41 mesoporous bound ruthenium complex was synthesized and characterized using elemental analysis, atomic absorption spectrophotometer, BET, XRD and FTIR. Hydrogenation of carbon dioxide to formic acid was investigated over these catalysts under supercritical CO2 condition. The effect of reactant gas partial pressure, supports, solvents and ligands on the synthesis of formic acid was studied. These factors could influence the catalyst activity, stability and reuse performance greatly and no byproduct was detected. These promising catalysts also offered the industrial advantages such as easy separation. [source] | ||||||||||||||||||||||||||||