Immobilization and activation of vanadium(III) and titanium(III) single‐site catalysts for ethylene polymerization using MgCl2‐based supports

Significant increases in the activity of vanadium(III) amidinate catalysts for ethylene polymerization have been obtained by immobilization on a MgCl₂‐based support prepared by reaction of AlEt₃ with a MgCl₂/ethanol adduct. Catalyst immobilization and activation on this type of support prevents the rapid decay in activity observed under homogeneous polymerization conditions with unsupported catalysts. Stable polymerization activity is also observed with analogous titanium(III) complexes. Polyethylene with narrow molecular weight distribution and spherical particle morphology is obtained without reactor fouling. Copyright © 2005 Society of Chemical Industry     

N.m.r. line shape-relaxation correlation analysis of bitumen and oil sands

The first results of the analysis of bitumen and oil sands using the recently developed n.m.r. spingrouping technique are presented. The n.m.r. relaxation experiments were carried out on bitumen, and on natural and dried oil sands samples. The results indicate that the spin-grouping can resolve and quantify several components of the samples studied. The bitumen and bitumen fraction of the oil sands are resolved according to their spin-spin relaxation times into three major groups: solid-like (rigid), solid-like (mobile) and semi-liquid. The water in the oil sands exists in two different environments. Tentatively one environment is assigned to be the bridges between the sand grains, while the other is assigned to be the clay surface. One can conclude that with spin grouping of complex mixtures the decomposition (in which components are resolved according to their dynamic state) is possible. The accuracy of such resolution is of the order of a few per cent.     

Steric requirements for coal swelling by amine bases

A set of six coals ranging in rank from lignite to hvA bituminous was swollen with a series of alkyl-substituted pyridines and a smaller set of 4-alkylanilines. The size and branching of the alkyl groups was varied and the effect of this variation on the dissolution of the amines in the coal and the resulting coal swelling was measured volumetrically. In a few cases, substituents which hindered the amine nitrogen were studied. The lignite and subbituminous coal have a much higher tolerance to branched, bulky groups than do the bituminous coals. The presence of tertiary groups in a solute strongly inhibits their dissolution in bituminous coals. Bituminous coals behave as if extensive parallel packing of structures occurs. Often, they can accept very large planar groups but have a low capacity for branched groups.     

Kinetics of hydantoin formation

The reaction of lignite in a slagging gasifier produces reactants which in turn form 5,5-dimethylhydantoin (DMH) as a major constituent in the condensate water. Variations in plant operating conditions made it impossible to accurately study the kinetics of formation of DMH in the actual gasifier water, and thus a model system was chosen. The reaction of acetone cyanohydrin in the presence of excess ammonium carbonate at concentrations approaching those obtained in the condensate water were studied at 50,70, and 90 °C. Secondorder kinetics were obeyed, and the pseudo second-order rate constants at the respective temperatures were 1.86, 3.6, and 4.62 dm³ mol^{? 1} h^{? 1}. Independent variation of the concentration of either acetone, cyanide, ammonia or carbonate gave results consistent with the interpretation that the formation of DMH is first order in all reactants: rate of formation of DMH = k[acetone][HCN][NH₃][CO₂]. The pseudo second-order rate constant is a complex rate constant including several rapid equilibria. A mechanism consistent with the kinetic data is presented.     

Effect of polymerization conditions on the melt rheological properties of vinyl chloride–vinyl acetate copolymers

Mathematical models have been developed which predict the composition, molecular weight, and melt rheological properties for vinyl chloride/vinyl acetate copolymers of inherent viscosity range 0.4–0.7 dL/g and bound vinyl acetate levels of 3.8–17.4%. The effect of polymer long chain branching on the viscous/elastic moduli ratio is discussed as well as the comparison of Tinius–Olsen melt index measurements vs. mechanical spectrometer results. The reactivity ratio for vinyl chloride/vinyl acetate comonomer pairs was remeasured and found to be significantly different from literature values.     

Particle structure of PVC based on cellulosic suspension system. III. Effect of monomer refluxing

The effects of monomer refluxing on both resin properties and reactor fouling of suspension PVC have been studied in a laboratory-scale 14-L reactor. Process control equations were developed which related the particle properties to the reflux condenser operation by controlling the parameters of (1) the time at which refluxing is begun and (2) the rate profile of heat removal from the condenser. An operating envelope has been developed for laboratory scale operations which optimizes the cycle time of polymerization while minimizing the adverse effects on particle properties. These operating conditions may have application to production scale operations when the proper scaling factors are employed.     

Contacting modes and behaviour classification of gas—solid and other two-phase suspensions

An attempt is made to extend schemes for classifying the behaviour of gas—solid contacting modes and other two-phase systems. The regime diagram approach of Reh (1971) is modified and extended to cover the operating regions of common reactors and contactors where a gas flows upwards through a bed of solids including fixed and moving packed beds, conventional fluidized beds, circulating beds, spouted beds, and pneumatically conveyed suspensions. New boundaries are proposed between groups A and B and between groups B and D of the Geldart (1972, 1973) powder classification scheme. These boundaries reflect more recent data and allow the classification scheme to be used for gases other than air and for temperatures and pressures other than atmospheric.     

Clinical psychologists reflect on the usefulness of various components of graduate training.

Graduates of clinical training programs were surveyed to determine the degree to which they have found various graduate school experiences useful in their professional work. Samples of academic clinical psychologists and practicing clinical psychologists reported time allocation and preference for various professional activities, perceived usefulness of various theoretical orientations, and the influence on their current professional work of 19 different graduate training topics. Results suggest that where differences exist, academic clinical psychologists are generally more satisfied with Boulder-model-inspired scientific training than are clinical practitioners. (PsycINFO Database Record (c) 2010 APA, all rights reserved)     

Experimental abatement data of underflow baffles for removal of floatables in the CSOs of the Greater Montréal (Canada) area.

Underflow baffles have gained in popularity over the years as a viable mean to intercept floatables in Combined Sewer Overflows (CSOs). This choice was mainly justified by the extremely low capital cost (CAPEX) and operational cost (OPEX) of this solution, although the efficiency of underflow baffles has never been clearly proven. The only similar application to underflow baffles are scum boards in grit chambers and clarifier. However, the flow conditions at CSOs vary considerably from those in grit chambers and clarifier. For this reason, review of the behavior of floatables in a rapid flow is paramount. Only then can comprehensive design criteria for underflow baffles and overflow chambers be suggested. Pilot scale tests, performed in a 17 metres long basin at various flowrates, had already shown that a critical horizontal velocity for floatables (Vcr) may develop in the overflow chambers. In this follow up study, the fate of intercepted floatables was investigated. It appears from this latest data that permanent capture of floatables decreases rapidly with an increase in the horizontal velocity of the flow, no matter what the baffle depth. Baffle depth increases capture at lower velocities (0.17 m/s) but become irrelevant at higher velocities (0.61 m/s). This data suggests that capture efficiency of existing underflow baffles in overflow chambers can be, at best, very low whenever the horizontal velocity increases above 0.30 m/s or 1 ft/s.     

Synthesis,characterization and ion exchange properties of zirconium(IV) tungstoiodophosphate,a new cation exchanger

Zirconium(IV) tungstoiodophosphate has been synthesized under a variety of conditions. The most chemically and thermally stable sample is prepared by adding a mixture of aqueous solutions of 0·5 mol L⁻¹ sodium tungstate, potassium iodate and 1 mol L⁻¹ orthophosphoric acid to aqueous solution of 0·1 mol L⁻¹ zirconium(IV) oxychloride. Its ion exchange capacity for Na⁺ and K⁺ was found to be 2·20 and 2·35 meq g⁻¹ dry exchanger, respectively. The material has been characterized on the basis of chemical composition, pH titration, Fourier transform infrared spectroscopy (FTIR) and thermogravimetric analysis. The effect on the exchange capacity of drying the exchanger at different temperatures has been studied. The analytical importance of the material has been established by quantitative separation of Pb²⁺ from other metal ions.