Effect of polymerization conditions on o‐phenylenediamine and o‐phenetidine oxidative copolymers

A series of new o‐phenylenediamine (OPD)/o‐phenetidine (PHT) copolymers with partly phenazine‐like structures has been successfully synthesized at three polymerization temperatures by chemically oxidative polymerization in four different polymerization media. The molecular structures and properties of the resulting OPD/PHT polymers were investigated by IR, UV–vis and high‐resolution ¹H NMR spectroscopies, and DSC, in order to ascertain the effect of reaction temperature, comonomer ratio and acid medium. The copolymerization mechanism of OPD with PHT monomers has been proposed. It is found that the statistical OPD/PHT copolymer obtained at a temperature of 118 °C has a higher degree of polymerization than that obtained at 12–17 °C. The OPD content in the copolymers calculated from NMR spectroscopic analysis is higher than that in the feed OPD content, whereas the OPD content calculated from element analysis is slightly lower than the feed OPD content. It can be predicted that denitrogenation takes place in the OPD units during the polymerization process at OPD/PHT molar ratios of 90/10 and 100/0. These OPD/PHT copolymers exhibit a much better solubility than the OPD homopolymer, hence suggesting an incorporation of PHT units into the phenazine structure of the homopolymer. The thermal behavior of the copolymers was also studied. Copyright © 2004 Society of Chemical Industry     

Oil Spill Cleanup from Sea Water by Sorbent Materials

Three sorbents were compared in order to determine their potential for oil spill cleanup. Polypropylene nonwoven web, rice hull, and bagasse with two different particle sizes were evaluated in terms of oil sorption capacities and oil recovery efficiencies. Polypropylene can sorb almost 7 to 9 times its weight from different oils. Bagasse, 18 to 45 mesh size, follows polypropylene as the second sorbent in oil spill cleanup. Bagasse, 14 to 18 mesh size, and rice hull have comparable oil sorption capacities, which are lower than those of the two former sorbents. It was found that oil viscosity plays an important role in oil sorption by sorbents. All adsorbents used in this work could remove the oil from the surface of the water preferentially.     

Magnetic Resonance Visualisation of Flow and Pore Structure in Packed Beds with Low Aspect Ratio

Different NMR techniques were combined to obtain the structure and velocity information for a systematic investigation of fixed beds with low aspect ratio (tube diameter to particle diamter, d_t/d_p) in the range 1.4 to 32. The structure of the void space was determined for a variety of packed beds of glass beads or regular and irregular porous pellets by magnetic resonance imaging (MRI). Based on the images the radial distribution of the voids within the bed was obtained. Ordering effects were found even for non‐spherical and polydisperse particles, and a maximum of the fluid density near the tube wall was confirmed for all pellet geometries and sizes. By combining MRI with velocity encoding, velocity profiles and distributions of flow velocity components of a single fluid phase through packed beds have been acquired. The radial velocity distribution follows an oscillatory pattern which largely reflects the ordering of the particles, which can be accessed from the density distribution of the interparticle fluid. Maximum velocities of up to four times the average value were found to occur near the tube wall. This wall effect was observed for all but the smallest particles, where the aspect ratio was d_t/d_p = 32. Moreover, a visualisation of flow pattern in the presence of packed particles was achieved by using a tagging technique, and the stationary flow field could be identified for an experimental time of several hours.     

Highly Cooperative Tetrametallic Ruthenium-mu-Oxo-mu-Hydroxo Catalyst for the Alcohol Oxidation Reaction

The tetrametallic ruthenium-oxo-hydroxo-hydride complex {[(PCy(3))(CO)RuH](4)(mu(4)-O)(mu(3)-OH)(mu(2)-OH)} (1) was synthesized in two steps from the monomeric complex (PCy(3))(CO)RuHCl (2). The tetrameric complex 1 was found to be a highly effective catalyst for the transfer dehydrogenation of alcohols. Complex 1 showed a different catalytic activity pattern towards primary and secondary benzyl alcohols, as indicated by the Hammett correlation for the oxidation reaction of p-X-C(6)H(4)CH(2)OH (rho = -0.45) and p-X-C(6)H(4)CH(OH)CH(3) (rho = +0.22) (X = OMe, CH(3), H, Cl, CF(3)). Both a sigmoidal curve from the plot of initial rate vs [PhCH(OH)CH(3)] (K(0.5) = 0.34 M; Hill coefficient, n = 4.2+/-0.1) and the phosphine inhibition kinetics revealed the highly cooperative nature of the complex for the oxidation of secondary alcohols.     

Biofiltration of toluene in the absence and the presence of ethyl acetate under continuous and intermittent loading

BACKGROUND: Two peat biofilters were used for the removal of toluene from air for one year. One biofilter was fed with pure toluene and the other received 1:1 (by weight) ethyl acetate:toluene mixture. RESULTS: The biofilters were operated under continuous loading: the toluene inlet load (IL) at which 80% removal occurred was 116 g m^?3 h^?1 at 57 s gas residence time. Maximum elimination capacity of 360 g m^?3 h^?1 was obtained at an IL of 745 g m^?3 h^?1. The elimination of toluene was inhibited by the presence of ethyl acetate. Intermittent loading, with pollutants supplied for 16 h/day, 5 days/week, did not significantly affect the removal efficiency (RE). Biomass was fully activated in 2 h after night closures, but 6 h were required to recover RE after weekend closures. Live cell density remained relatively constant over the operational period, while the dead cell fraction increased. Finally, a 15 day starvation period was applied and operation then re‐started. Performance was restored with similar re‐acclimatization period to that after weekend closures, and a reduction in dead cell fraction was observed. CONCLUSION: This study demonstrates the capacity of the system to handle intermittent loading conditions that are common in industrial practices, including long‐term starvation. Copyright © 2008 Society of Chemical Industry     

Inhibition of sulfide on the simultaneous removal of nitrate and p‐cresol by a denitrifying sludge

BACKGROUND: Many industrial discharges, such as those generated from petrochemical refineries, contain large amounts of sulfurous, nitrogenous and organic contaminants. Denitrification has emerged as a suitable technology for the simultaneous removal of these pollutants in a single reactor unit; however, more evidence is demanded to clarify the limitations of denitrification on the simultaneous removal of sulfide and phenolic contaminants and to optimize the biological process. The aim of this study was to evaluate the capacity of a denitrifying sludge to simultaneously convert sulfide and p‐cresol via denitrification. RESULTS: Sulfide was the preferred electron donor over p‐cresol, imposing a 5 h lag phase (required for complete sulfide removal) on organotrophic denitrification. Addition of sulfide (20 mg S^2? L^?1) to p‐cresol‐amended denitrifying cultures also decreased the reduction rate of nitrate and nitrite, as well as the production rate of nitrogen gas. Nitrite reduction rate was the most affected step by sulfide, decreasing from 35 to 21 mg N (g VSS d)^?1. A synergistic inhibitory effect of nitrate and sulfide was also observed on nitrite reduction. Despite the effects of sulfide on the respiratory rates monitored, complete removal of nitrate, sulfide and p‐cresol could be achieved after 48 h of incubation. CONCLUSION: Our results suggest that simultaneous removal of sulfide and p‐cresol could be achieved in denitrifying reactors, but a large hydraulic residence time may be required to sustain an efficient process due to inhibitory effects of sulfide. Copyright © 2008 Society of Chemical Industry     

Photodegradation mechanism and stabilization of polyphenylene oxide and rigid‐rod polymers

Poly(2,4‐dimethyl‐1,4‐phenylene oxide) (PPO), poly(benzo[1,2‐d:5,4‐d′]bisoxazole‐2,6‐diyl‐1,4‐phenylene) (PBO) and poly(benzo[1,2‐d:4,5‐d′]bisthiazole‐2,6‐diyl‐1,4‐phenylene) (PBZT), which are polymers with extended conjugated structures, undergo a self‐sensitized photo‐induced electron‐transfer reaction. A second component is not required. This article presents many similar observations on these polymers when they are exposed to light and evidence to support the proposed photo‐induced electron‐transfer mechanism. Methods to stabilize these polymers against photo‐oxidation are also described. Workers investigating other conjugated polymeric systems may find the experimental methods, observations and polymer stabilization approaches discussed in this review useful. Copyright © 2005 Society of Chemical Industry     

Application of artificial neural networks to the analysis of two‐dimensional fluorescence spectra in recombinant E coli fermentation processes

A two‐dimensional (2D) spectrofluorometer was used to monitor various fermentation processes with recombinant E coli for the production of 5‐aminolevulinic acid (ALA). The whole fluorescence spectral data obtained during a process were analyzed using artificial neural networks, ie self‐organizing map (SOM) and feedforward backpropagation neural network (BPNN). The SOM‐based classification of the whole spectral data has made it possible to qualitatively associate some process parameters with the normalized weights and variances, and to select some useful combinations of excitation and emission wavelengths. Based on the classified fluorescence spectra a supervised BPNN algorithm was used to predict some of the process parameters. It was also shown that the BPNN models could elucidate some sections of the process's performance, eg forecasting the process's performance. Copyright © 2005 Society of Chemical Industry