STRUCTURE AND PROPERTIES OF SEQUENTIALLY POLYMERIZED PROPYLENE-B-[ETHYLENE-CO-PROPYLENE]-B-PROPYLENE COPOLYMERS

The structure and properties of presumed block copolymers of polypropylene (PP) with ethylene-propylene random copolymers (EPR), i.e., PP-EPR and PP-EPR-PP, have been investigated by viscometry, transmission electron microscopy, dynamic mechanical analysis, differential scanning calorimetry, gel permeation chromatography, wide-angle x-ray diffraction, and other techniques testing various mechanical properties. PP-EPR and PP-EPR-PP were synthesized using delta-TiCl3-Et2AlCl as a catalyst system. The results indicate that the intrinsic viscosity of these polymers increases with each block-building step, whereas the intrinsic viscosity of those prepared by chain transfer reaction (strong chain-transfer reagent hydrogen was introduced between block-building steps during polymerization) hardly changes with the reaction time. Compared with PP / EPR blends, PP-EPR-PP block copolymers have lower PP and polyethylene crystallinity, and lower melting and crystallization temperatures of crystalline EPR. Two relaxation peaks of PP and EPR appear in the dynamic spectra of blends. They merge into a very broad relaxation peak with block sequence products of the same composition, indicating good compatibility between PP and EPR in the presence of block copolymers. Varying the PP and EPR content affects the crystallinity, density, and morphological structure of the products, which in turn affects the tensile strength and elongation at break. Because of their superior mechanical properties, sequential polymerization products containing PP-EPR and PP-EPR-PP block copolymers may have potential as compatibilizing agents for isotactic polypropylene and polyethylene blends or as potential heat-resistant thermoplastic elastomers.

CHARACTERIZATION, MORPHOLOGY AND THERMAL-PROPERTIES OF ETHYLENE PROPYLENE BLOCK COPOLYMERS

Characterization, morphology and thermal properties of commercial ethylene-propylene block copolymers have been studied by C-13 nuclear magnetic resonance (n.m.r.) spectroscopy, differential scanning calorimetry (d.s.c.), dynamic mechanical analysis (d.m.a.) and scanning electron microscopy (SEM). The results obtained show that there exists some ethylene-propylene random copolymer in the block copolymers extractable by n-heptane. The possibility of forming PP-b-PE diblock copolymer is questionable on the basis of the effects of residual propene and the chain-transfer reaction in the sequential copolymerization. A difference in the thermal properties between commercial ethylene-propylene block copolymers and PP/PE blends was noticed, which cannot be used to identify PP-b-PE diblock copolymer. The multiphase structure has been confirmed by d.m.a. and SEM, with ethylene-propylene random copolymer and polyethylene forming the domains in the matrix of polypropylene.

Synergetic effect between NiO and Ni3V2O8 in propane oxidative dehydrogenation

The oxidative dehydrogenation (ODH) of propane was investigated on Ni-V-O catalysts in a wide range of vanadium contents (5-40%). The addition of a small amount of vanadium significantly increased the catalytic activity of NiO for oxidative dehydrogenation of propane to propene. The formation of propene has a good correlation with the coexistence of NiO and Ni3V2O8. This result strongly suggests that a synergetic effect exists between them in NiXV1-XOY (X = 0.95 to 0.6). The best results were obtained with a high Ni/V ratio (e.g. X = 0.95 to 0.85). The active sites and selective oxygen species are discussed. The influence of the catalyst preparation technique and the redox properties of the catalyst were also examined.

Dramatic liquid-phase dehydrogenation rate enhancements using gas-phase hydrogen acceptors

The dehydrogenation of 1,2,3,4-tetrahydrocarbazole (THCZ) to form carbazole (CZ) over supported palladium catalysts was examined in the presence of hydrogen acceptors. As expected, liquid hydrogen acceptors increased the rate of reaction but, importantly, gaseous hydrogen acceptors also have been used. Ethene, propene, and but-1-ene showed up to a fivefold increase in the rate of dehydrogenation. Moreover, compared with the analogous liquid systems, the gaseous alternatives are a potentially more economic method of enhancing the activity and provide a simpler workup. The mechanism for the increase in rate was examined by density functional theory calculations, which showed that the propene hydrogenation competes effectively with the back-hydrogenation of the intermediates formed during the THCZ dehydrogenation, resulting in a shift in the equilibrium toward to the formation of CZ. (C) 2007 Elsevier Inc. All rights reserved.

On the nature of the silver phases of Ag/Al2O3 catalysts for reactions involving nitric oxide

The nature of the silver phases of Ag/Al2O3 catalysts (prepared by silver nitrate impregnation followed by calcination) was investigated by X-ray diffractograms (XRD), transmission electron microscopy (TEM) and UV-VIS analyses and related to the activity of the corresponding materials for the oxidation of NO to NO2. The UV-VIS spectrum of the 1.2 wt.% Ag/Al2O3 exhibited essentially one band associated with Ag+ species and the NO2 yields measured over this material were negligible. A 10 wt.% Ag/Al2O3 material showed the presence of oxidic species of silver (as isolated Ag+ cations and silver aluminate), but the UV-VIS data also revealed the presence of some metallic silver. The activity for the NO oxidation to NO2 of this sample was moderate. The same 10% sample either reduced in H-2 or used for the C3H6-selective catalytic reduction (SCR) of NO showed a significantly larger proportion of silver metallic phases and these samples displayed a high activity for the formation of NO2. These data show that the structure and nature of the silver phases of Ag/Al2O3 catalysts can markedly change under reaction feed containing only a fraction of reducing agent (i.e. 500 ppm of propene) in net oxidizing conditions (2.5% O-2). The low activity for N-2 formation during the C3H6-SCR of NO (reported in an earlier study) over the high loading sample can. therefore, he related to the presence of metallic silver. which is yet a good catalyst for NO oxidation to NO2. The reverse observations apply for the oxide species observed over the low loading sample, which is a good SCR catalyst but do not oxidize NO to NO2. (C) 2002 Elsevier Science B.V. All rights reserved.

Selective catalytic reduction of O-2 with excess H-2 in the presence of C2H4 or C3H6

The selective reduction of molecular oxygen with excess H-2 in the presence of alkenes was achieved successfully for the first time: silver supported on alumina catalysts exhibited full conversion of O-2 at temperature as low as 50 degrees C, while the conversion of ethene or propene remained essentially zero up to 250 degrees C.

Activation of Alkanes by Gold-Modified Lanthanum Oxide

Functionalization of alkanes is much sought after for the production of fine and bulk chemicals. In particular, the oxidative activation of alkanes and their conversion to ethene and propene has been studied extensively, owing to the use of these alkenes in polymerization reactions. The greater reactivity of the products in comparison with the reactants has proven a major issue in this reaction as this can result in overoxidation, producing CO and CO2 and, therefore, reducing the alkene yield. Herein, the first application of supported gold catalysts for the direct activation of C2+ aliphatic alkanes with oxygen to form alkenes is demonstrated. This catalyst is particularly notable as it is highly active, selective to propene and ethene, and stable on stream over a 48 h period. Maintaining cationic gold is thought to be critical for the stability and this catalyst design provides the possibility of applying gold-based catalysts over a much wider temperature range than has been reported.

Asymmetric Carbon-Carbon Bond Forming Reactions Catalysed by Metal(II) Bis(oxazoline) Complexes Immobilized using Supported Ionic Liquids

A series of bis(oxazoline) metal(II) complexes has been supported on silica and carbon supports by non-covalent immobilisation using an ionic liquid. The catalytic performance of these solids was compared for the enantioselective Diels-Alder reaction between N-acryloyloxazolidinone and cyclopentadiene and the Mukaiyama-aldol reaction between methyl pyruvate and 1-methoxy-1-trimethylsilyloxy-propene. In both reactions the enantioselectivity was strongly influenced by the choice of support displaying enantioselectivies (ee values) up to 40% higher than those conducted under homogeneous reaction conditions.

Oxidative dehydrogenation of propane with N2O over Fe-ZSM-5 and Fe-SiO2: Influence of the iron species and acid sites

A series of iron containing zeolites with varying Si/Al ratios (11.5-140) and low iron content (similar to 0.9 wt.% Fe) have been synthesised by solid-state ion exchange with commercially available zeolites and tested, for the first time, in the oxidative dehydrogenation of propane (ODHP) with N2O. The samples were characterised by XRD, N-2-Adsorption, NH3-TPD and DR-UV-vis spectroscopy. The acidity of the Fe-ZSM-5 can be controlled by high temperature and steam treatments and Si/Al ratio. The selectivity and yield of propene were found to be the highest over Fe-ZSM-5 with low Al contents and reduced acidity. The initial propene yield over Fe-ZSM-5 was significantly higher than that of Fe-SiO2 since the presence of weak and/or medium acid sites together with oligonuclear iron species and iron oxides on the ZSM-5 are found to enhance the N2O activation. The coking of Fe-ZSM-5 catalysts could also be controlled by reduction of the surface acidity of ZSM-5 and by the use of O-2 in addition to N2O as the oxidant. Fe-ZSM-5 zeolites prepared with solid-state method have been shown to have comparable activity and better stability towards coking compared with Fe-ZSM-5 zeolites prepared by liquid ion exchange and hydrothermal synthesis methods. (C) 2012 Elsevier B.V. All rights reserved.

A spectroscopic study of the chemistry and reactivity of SO2 on Pt{111}: Reactions with O-2, CO and C3H6

The chemisorption and reactivity of SO2 on Pt{111} have been studied by HREELS, XPS, NEXAFS and temperature-programmed desorption. At 160 K SO2 adsorbs intact at high coverages, with eta(2) S-O coordination to the surface. On annealing to 270 K, NEXAFS indicates the SO2 molecular plane essentially perpendicular to the surface. Preadsorbed O-a reacts with SO2 to yield adsorbed SO4, identified as the key surface species responsible for SO2-promoted catalytic alkane oxidation. Coadsorbed CO or propene efficiently reduce SO2 overlayers to deposit S-a, and the implications of this for catalytic systems are discussed.

Critical role of water in the direct oxidation of CO and hydrocarbons in diesel exhaust after treatment catalysis

CO and C3H6 oxidation have been carried out in the absence and presence of water over a Pd/Al2O3catalyst. It is clear that water promotes CO and, as a consequence, C3H6oxidation takes place at muchlower temperatures compared with the dry feed. The significant increase in the catalyst’s activity withrespect to CO oxidation is not simply associated with changes in surface concentration as a result ofcompetitive adsorption effects. Utilising18O2as the reactant allows the pathways whereby the oxidationdue to gaseous dioxygen and where the water activates the CO and C3H6to be distinguished. In thepresence of water, the predominant pathway is via water activation with C16O2and C16O18O being themajor species formed and oxidation with dioxygen plays a secondary role. The importance of wateractivation is further supported by the significant decrease in its effect when using D2O versus H2O.

Design of an automated solar concentrator for the pyrolysis of scrap rubber

An automated solar reactor system was designed and built to carry out catalytic pyrolysis of scrap rubber tires at 550°C. To maximize solar energy concentration, a two degrees-of-freedom automated sun tracking system was developed and implemented. Both the azimuth and zenith angles were controlled via feedback from six photo-resistors positioned on a Fresnel lens. The pyrolysis of rubber tires was tested with the presence of two types of acidic catalysts, H-beta and H-USY. Additionally, a photoactive TiO<inf>2</inf> catalyst was used and the products were compared in terms of gas yields and composition. The catalysts were characterized by BET analysis and the pyrolysis gases and liquids were analyzed using GC-MS. The oil and gas yields were relatively high with the highest gas yield reaching 32.8% with H-beta catalyst while TiO<inf>2</inf> gave the same results as thermal pyrolysis without any catalyst. In the presence of zeolites, the dominant gasoline-like components in the gas were propene and cyclobutene. The TiO<inf>2</inf> and non-catalytic experiments produced a gas containing gasoline-like products of mainly isoprene (76.4% and 88.4% respectively). As for the liquids they were composed of numerous components spread over a wide distribution of C<inf>10</inf> to C<inf>29</inf> hydrocarbons of naphthalene and cyclohexane/ene derivatives.

Moving from Batch to Continuous Operation for the Liquid Phase Dehydrogenation of Tetrahydrocarbazole

Despite the numerous advantages of continuous processing, high-value chemical production is still dominated by batch techniques. In this paper, we investigate options for the continuous dehydrogenation of 1,2,3,4- tetrahydrocarbazole using a trickle bed reactor operating under realistic liquid velocities with and without the addition of a hydrogen acceptor. Here, a commercial 5 wt % Pd/Al₂O₃ catalyst was observed to slowly deactivate, hence proving unsuitable for continuous use. This deactivation was attributed to the strong adsorption of a byproduct on the surface of the support. Application of a base washing technique resolved this issue and a stable continuous reaction has been demonstrated. As was previously shown for the batch reaction, the addition of a hydrogen acceptor gas (propene) can increase the overall catalytic activity of the system.