Effect of alkali and alkaline earth metals on nitrogen release during temperature programmed pyrolysis of coal

Formation of HCN, NH₃, and N₂ during fixed-bed pyrolysis at 10K min⁻¹ has been studied using coal samples after partial demineralization followed by addition of metal hydroxides from aqueous systems. Without additives, NH₃ is the predominant product at ≤ 700°C, showing the two peaks in the formation rate profile, whereas N₂ is the only product at ≥ 800°C. The presence of NaOH, KOH and Ca(OH)₂ promotes considerable NH₃ formation between 450 and 600°C, but in contrast suppresses HCN formation in this region. The Ca shows the largest effect on both the promotion and suppression. It is likely that the NH₃ increased by Ca addition arises partly from HCN, but mainly from secondary reactions of tar-N. These hydroxides affect N₂ formation in quite different manners: the Na decreases the rate between 700 and 950°C, and the K changes it less significantly than the Na, but the Ca remarkably increases the rate in a low temperature region of 550–700°C. These different features are discussed in terms of solid-phase reactions of alkali metal carbonates with char-N and secondary decomposition reactions of tar-N on CaO particles. As a result, total conversion of coal-N to HCN, NH₃ and N₂ up to 1000°C increases in the sequence of Na < none < K < Ca.     

N.m.r. studies on the effect of water on the glass transition of polystyrene

These investigations are concerned with water-polymer interactions in polymer latices. It is known that water can act as a plasticizer for many solid polymers and cause a reduction in the glass transition temperature, T_g, of the amorphous regions. Experiments were carried out to determine whether pulsed n.m.r. techniques could be used to study the T_g of a polymer suspension and hence the influence of water and electrolyte on it. From T₁ and T₂ proton relaxation measurements as a function of temperature on polystyrene latex systems it was shown that the presence of water lowers the T_g of the polymer particles (by about 10°C), the effect being slightly greater in the presence of concentrated electrolyte. The extent of electrolyte penetration into the particles was deduced by studying relaxation as a function of particle diameter in latices containing paramagnetic Mn²⁺ ions. Using simple theories of relaxation and spin diffusion it was concluded that for all but the smallest particles electrolyte penetration is restricted to a very thin shell of the order of 1 nm. These conclusions were supported by the results of similar measurements on PTFE particles.     

Experimental Simulation of the Reactor Section of Fluid Cokers: Comparison of FCC and Fluid Coke Particles

The hydrodynamics of fluid cokers were studied in a pressurized fully cylindrical cold model of diameter 483 mm, geometrically and dynamically scaled down by a factor of ～20 from commercial units. Differential pressure fluctuations, voidage distributions, solids momentum flux distributions and steady state gas mixing behaviour in the reactor section are compared for the same operating conditions with two kinds of particles, FCC and fluid coke. The voidage distributions and core‐annular flow structures in the reactor section were similar enough that either FCC or fluid coke particles can be used for cold modelling of fluid cokers.     

Free-radical grafting of cellulose in N-methylmorpholine oxide: Water-soluble pam-g-cellulose copolymers

The homogeneous graft copolymerization of acrylamide (AM) onto cellulose initiated by t-butylperoxy-2-ethylhexanoate in a cellulose solvent, N-methylmorpholine oxide (NMMO), was investigated. The method afforded water-soluble PAM-g-cellulose copolymers in fair yields. The copolymers produced are of low molecular weight (50,000–100,000 M?_w). Little apparent homopolymerization was observed.     

Controlled coagulation of emulsion polymers

Coagulation of latex particles is most often carried out in the diffusion limited aggregation (DLA) regime where the time for coagulation to take place is on the millisecond timescale. This process produces aggregates of low density, irregular shape, and a broad particle size distributions. When the coagulation is carried out in the reaction limited aggregation (RLA) regime, a coagulation time of about 1–120 sec, the system can be controlled by mixing to yield dense, spheroidal aggregates with a very narrow particle size distribution. The important variables in the RLA process for butyl acrylate/methyl methacrylate (BA/MMA) latexes were found to be mixing intensity, latex copolymer composition, and coagulation temperature. Dried aggregates formed in the RLA process were found to have excellent powder flow properties and low dustiness.     

Fabrication and characterization of planar and channel polymer waveguides. III. Compositional distribution and solute loss in polymer thin films

For many microelectronic and optoelectronic applications, polymer thin films require the addition of small molecules. However, the thin‐film geometry and associated processing techniques will influence the final morphology and compositional distribution of the constituents. It is therefore important that these be examined directly rather than inferred from bulk measurements. As an example system, the concentration and distribution of Disperse Red 1 (DR1) molecules in poly(methyl methacrylate) thin films were examined. Ultraviolet visibility spectroscopy and dynamic secondary ion mass spectrometry indicate that the composition of the molecules decreased dramatically with thermal treatment of the film. The sublimation of the chromophore was observed to occur at temperatures well below the melting point of the small molecule and the glass transition of the pure polymer; this solute loss manifested itself in changes in the glass transition temperature of the film. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 2021–2024, 2002     

Studies on cocurrent gas-liquid flow in helically coiled tubes. II. Theory and experiments on turbulent mass transfer with and without chemical reaction

Pure carbon dioxide was absorbed into distilled water and sodium hydroxide solution, in cocurrent two phase annular flow in helically coiled tubes in order to measure physical and chemical mass transfer coefficients and interfacial areas. (k*_La) was correlated by the pressure drop in the test sections and interfacial areas were found to vary with the liquid phase energy dissipation. According to a new theory, (k*_L) has been shown to be a function of the root mean square vorticity near the interface. The root mean square vorticity has been related to the pressure drop, gas density, liquid flow rate and liquid velocity. The physical mass transfer coefficients theoretically predicted are in good agreement with experimental results.