Kinetic and hydraulic studies in high-rate biological filters

Most published work on either low- or high-rate biological filters covers one of three topics: kinetics, microbiology/ecology or hydraulics. These areas have been re-examined together for high-rate filters in order to further integrate them and enable appropriate utilization of low-rate filter experience.

Chemical kinetic investigation of a commercial batch reactor process

The aim of this investigation was to study the chemical reactions occurring during the batchwise production of a butylated melamine-formaldehyde resin, in order to optimise the efficiency and economics of the batch processes. The batch process models are largely empirical in nature as the reaction mechanism is unknown. The process chemistry and the commercial manufacturing method are described. A small scale system was established in glass and the ability to produce laboratory resins with the required quality was demonstrated, simulating the full scale plant. During further experiments the chemical reactions of methylolation, condensation and butylation were studied. The important process stages were identified and studied separately. The effects of variation of certain process parameters on the chemical reactions were also studied. A published model of methylolation was modified and used to simulate the methylolation stage. A major result of this project was the development of an indirect method for studying the condensation and butylation reactions occurring during the dehydration and acid reaction stages, as direct quantitative methods were not available. A mass balance method was devised for this purpose and used to collect experimental data. The reaction scheme was verified using this data. The reactions stages were simulated using an empirical model. This has revealed new information regarding the mechanism and kinetics of the reactions. Laboratory results were shown to be comparable with plant scale results. This work has improved the understanding of the batch process, which can be used to improve product consistency. Future work has been identified and recommended to produce an optimum process and plant design to reduce the batch time.

Kinetic study on thermal decomposition of woods in oxidative environment

The purpose of this work is to gain knowledge on kinetics of biomass decomposition under oxidative atmospheres, mainly examining effect of heating rate on different biomass species. Two sets of experiments are carried out: the first set of experiments is thermal decomposition of four different wood particles, namely aspens, birch, oak and pine under an oxidative atmosphere and analysis with TGA; and the second set is to use large size samples of wood under different heat fluxes in a purpose-built furnace, where the temperature distribution, mass loss and ignition characteristics are recorded and analyzed by a data post-processing system. The experimental data is then used to develop a two-step reactions kinetic scheme with low and high temperature regions while the activation energy for the reactions of the species under different heating rates is calculated. It is found that the activation energy of the second stage reaction for the species with similar constituent fractions tends to converge to a similar value under the high heating rate.

Kinetic studies of the metathesis of 1-hexene using Re2O7/γ-Al2O3 and the synthesis and metathesis of oxazolines

The kinetics of the metathesis of 1-hexene using Re2O7/-Al_2O_3 as the catalyst were investigated under a variety of conditions. The experiments were carried out under high vacuum conditions. The product solutions were characterised by gas liquid chromatography and mass spectroscopy. The initial kinetics of the metathesis of 1-hexene showed that the reaction was first order in the weight of the catalyst and second order in the concentration of 1-hexene. A kinetic scheme which correlated the experimental data with the metallocarbene chain mechanism postulated by Herisson and Chauvin and the kinetics of the reaction was explained using a model based on the Langmuir-Hinshelwood theory. The low conversion of 1-hexene to its products is due to termination reactions which most likely occur by the decomposition of the metallocyclobutane intermediate to produce a cyclopropane derivative and an inactive centre. The optimum temperature for the metathesis of 1-hexene over Re_2O_7/-Al2O3 is 45oC and above this temperature, the rate of metathesis decreases rapidly. Co-catalysts alter the active sites for metathesis so that the catalyst is more selective to the metathesis of 1-hexene. However, the regeneration of metathesis activity is much worse for promoted catalysts than for the unpromoted. The synthesis and metathesis of 4,4-dimethyl-2-allowbreak (9-decenyl)-1,3-oxazoline and 4,4-dimethyl-2-allowbreak (3-pentenyl)-1,3-oxazoline was attempted and the products were analysed by thin layer chromatography, infra-red, 13C and 1H nmr and mass spectroscopy. Obtaining the oxazolines in a good yield with high purity was difficult and consequently metathesis of the impure products did not occur.

A comparison between static and kinetic visual attention as a means of detecting age-related deterioration of the visual system and driving performance

A critical review of previous research revealed that visual attention tests, such as the Useful Field of View (UFOV) test, provided the best means of detecting age-related changes to the visual system that could potentially increase crash risk. However, the question was raised as to whether the UFOV, which was regarded as a static visual attention test, could be improved by inclusion of kinetic targets that more closely represent the driving task. A computer program was written to provide more information about the derivation of UFOV test scores. Although this investigation succeeded in providing new information, some of the commercially protected UFOV test procedures still remain unknown. Two kinetic visual attention tests (DRTS1 and 2), developed at Aston University to investigate inclusion of kinetic targets in visual attention tests, were introduced. The UFOV was found to be more repeatable than either of the kinetic visual attention tests and learning effects or age did not influence these findings. Determinants of static and kinetic visual attention were explored. Increasing target eccentricity led to reduced performance on the UFOV and DRTS1 tests. The DRTS2 was not affected by eccentricity but this may have been due to the style of presentation of its targets. This might also have explained why only the DRTS2 showed laterality effects (i.e. better performance to targets presented on the left hand side of the road). Radial location, explored using the UFOV test, showed that subjects responded best to targets positioned to the horizontal meridian. Distraction had opposite effects on static and kinetic visual attention. While UFOV test performance declined with distraction, DRTS1 performance increased. Previous research had shown that this striking difference was to be expected. Whereas the detection of static targets is attenuated in the presence of distracting stimuli, distracting stimuli that move in a structured flow field enhances the detection of moving targets. Subjects reacted more slowly to kinetic compared to static targets, longitudinal motion compared to angular motion and to increased self-motion. However, the effects of longitudinal motion, angular motion, self-motion and even target eccentricity were caused by target edge speed variations arising because of optic flow field effects. The UFOV test was more able to detect age-related changes to the visual system than were either of the kinetic visual attention tests. The driving samples investigated were too limited to draw firm conclusions. Nevertheless, the results presented showed that neither the DRTS2 nor the UFOV tests were powerful tools for the identification of drivers prone to crashes or poor driving performance.

Pryolytic and kinetic study of Chlorella Vulgaris under isothermal and non-isothermal conditions

Algae are a new potential biomass for energy production but there is limited information on their pyrolysis and kinetics. The main aim of this thesis is to investigate the pyrolytic behaviour and kinetics of Chlorella vulgaris, a green microalga. Under pyrolysis conditions, these microalgae show their comparable capabilities to terrestrial biomass for energy and chemicals production. Also, the evidence from a preliminary pyrolysis by the intermediate pilot-scale reactor supports the applicability of these microalgae in the existing pyrolysis reactor. Thermal decomposition of Chlorella vulgaris occurs in a wide range of temperature (200-550°C) with multi-step reactions. To evaluate the kinetic parameters of their pyrolysis process, two approaches which are isothermal and non-isothermal experiments are applied in this work. New developed Pyrolysis-Mass Spectrometry (Py-MS) technique has the potential for isothermal measurements with a short run time and small sample size requirement. The equipment and procedure are assessed by the kinetic evaluation of thermal decomposition of polyethylene and lignocellulosic derived materials (cellulose, hemicellulose, and lignin). In the case of non-isothermal experiment, Thermogravimetry- Mass Spectrometry (TG-MS) technique is used in this work. Evolved gas analysis provides the information on the evolution of volatiles and these data lead to a multi-component model. Triplet kinetic values (apparent activation energy, pre-exponential factor, and apparent reaction order) from isothermal experiment are 57 (kJ/mol), 5.32 (logA, min-1), 1.21-1.45; 9 (kJ/mol), 1.75 (logA, min-1), 1.45 and 40 (kJ/mol), 3.88 (logA, min-1), 1.45- 1.15 for low, middle and high temperature region, respectively. The kinetic parameters from non-isothermal experiment are varied depending on the different fractions in algal biomass when the range of apparent activation energies are 73-207 (kJ/mol); pre-exponential factor are 5-16 (logA, min-1); and apparent reaction orders are 1.32–2.00. The kinetic procedures reported in this thesis are able to be applied to other kinds of biomass and algae for future works.

Anisotropic model of kinetic roughening:he strong-coupling regime

We study the strong coupling (SC) limit of the anisotropic Kardar-Parisi-Zhang (KPZ) model. A systematic mapping of the continuum model to its lattice equivalent shows that in the SC limit, anisotropic perturbations destroy all spatial correlations but retain a temporal scaling which shows a remarkable crossover along one of the two spatial directions, the choice of direction depending on the relative strength of anisotropicity. The results agree with exact numerics and are expected to settle the long-standing SC problem of a KPZ model in the infinite range limit. © 2007 The American Physical Society.

Dimethylsulfoxide oxidizes glutathione in vitro and in human erythrocytes:kinetic analysis by 1H NMR

The interaction of dimethylsulfoxide (Me2SO) with glutathione was investigated under non-equilibrium conditions in solution using 1H NMR and in intact erythrocytes using 1H spin-echo NMR. In solution the reaction was observed to follow second-order kinetics (Rate = k1[glutathione][Me2SO]) at 300 K pH 7.4, ksol = 4.7 × 10-5 mol -1 L1 s-1. In intact erythrocytes the rate constant for the cellular environment, kcell, was found to be slightly larger at 8.1 × 10-5 mol-1 L1 s-1. Furthermore, the reaction of Me2SO with erythrocyte glutathione showed a biphasic dependence on the Me2SO concentration, with little oxidation of glutathione occurring until the Me2SO concentration exceeded 0.5 mol L-1. The results suggest that at lower concentrations, Me2SO can be effectively removed, most probably by reaction with glutathione, which is regenerated by glutathione reductase, although preferential reaction with other cellular components (e.g., membrane or cellular thiols) cannot be ruled out. Thus the concentrations of Me2SO that are commonly used in cryopreservation of mammalian cells (∼1.4 mol L-1) can cause oxidation of intracellular glutathione.

Kinetic modeling studies of heterogeneously catalyzed biodiesel synthesis reactions

The heterogeneously catalyzed transesterification reaction for the production of biodiesel from triglycerides was investigated for reaction mechanism and kinetic constants. Three elementary reaction mechanisms Eley-Rideal (ER), Langmuir-Hinshelwood-Hougen-Watson (LHHW), and Hattori with assumptions, such as quasi-steady-state conditions for the surface species and methanol adsorption, and surface reactions as the rate-determining steps were applied to predict the catalyst surface coverage and the bulk concentration using a multiscale simulation framework. The rate expression based on methanol adsorption as the rate limiting in LHHW elementary mechanism has been found to be statistically the most reliable representation of the experimental data using hydrotalcite catalyst with different formulations. © 2011 American Chemical Society.

Kinetic study of the pyrolysis of miscanthus and its acid hydrolysis residue by thermogravimetric analysis

The kinetic parameters of the pyrolysis of miscanthus and its acid hydrolysis residue (AHR) were determined using thermogravimetric analysis (TGA). The AHR was produced at the University of Limerick by treating miscanthus with 5 wt.% sulphuric acid at 175 °C as representative of a lignocellulosic acid hydrolysis product. For the TGA experiments, 3 to 6 g of sample, milled and sieved to a particle size below 250 μm, were placed in the TGA ceramic crucible. The experiments were carried out under non-isothermal conditions heating the samples from 50 to 900 °C at heating rates of 2.5, 5, 10, 17 and 25 °C/min. The activation energy (EA) of the decomposition process was determined from the TGA data by differential analysis (Friedman) and three isoconversional methods of integral analysis (Kissinger–Akahira–Sunose, Ozawa–Flynn–Wall, Vyazovkin). The activation energy ranged from 129 to 156 kJ/mol for miscanthus and from 200 to 376 kJ/mol for AHR increasing with increasing conversion. The reaction model was selected using the non-linear least squares method and the pre-exponential factor was calculated from the Arrhenius approximation. The results showed that the best fitting reaction model was the third order reaction for both feedstocks. The pre-exponential factor was in the range of 5.6 × 1010 to 3.9 × 10+ 13 min− 1 for miscanthus and 2.1 × 1016 to 7.7 × 1025 min− 1 for AHR.

Labeled EF-Tus for rapid kinetic studies of pretranslocation complex formation

The universally conserved translation elongation factor EF-Tu delivers aminoacyl(aa)-tRNA in the form of an aa-tRNA·EF-Tu·GTP ternary complex (TC) to the ribosome where it binds to the cognate mRNA codon within the ribosomal A-site, leading to formation of a pretranslocation (PRE) complex. Here we describe preparation of QSY9 and Cy5 derivatives of the variant E348C-EF-Tu that are functional in translation elongation. Together with fluorophore derivatives of aa-tRNA and of ribosomal protein L11, located within the GTPase associated center (GAC), these labeled EF-Tus allow development of two new FRET assays that permit the dynamics of distance changes between EF-Tu and both L11 (Tu-L11 assay) and aa-tRNA (Tu-tRNA assay) to be determined during the decoding process. We use these assays to examine: (i) the relative rates of EF-Tu movement away from the GAC and from aa-tRNA during decoding, (ii) the effects of the misreading-inducing antibiotics streptomycin and paromomycin on tRNA selection at the A-site, and (iii) how strengthening the binding of aa-tRNA to EF-Tu affects the rate of EF-Tu movement away from L11 on the ribosome. These FRET assays have the potential to be adapted for high throughput screening of ribosomal antibiotics.

Isopeptidase activity of human transglutaminase 2:disconnection from transamidation and characterization by kinetic parameters

Transglutaminase 2 (TG2) is a multifunctional protein with diverse catalytic activities and biological roles. Its best studied function is the Ca2+-dependent transamidase activity leading to formation of γ-glutamyl-ε-lysine isopeptide crosslinks between proteins or γ-glutamyl-amine derivatives. TG2 has a poorly studied isopeptidase activity cleaving these bonds. We have developed and characterised TG2 mutants which are significantly deficient in transamidase activity while have normal or increased isopeptidase activity (W332F) and vice versa (W278F). The W332F mutation led to significant changes of both the Km and the Vmax kinetic parameters of the isopeptidase reaction of TG2 while its calcium and GTP sensitivity was similar to the wild type enzyme. The W278F mutation resulted in six times elevated amine incorporating transamidase activity demonstrating the regulatory significance of W278 and W332 in TG2 and that mutations can change opposed activities located at the same active site. The further application of our results in cellular systems may help to understand TG2 -driven physiological and pathological processes better and lead to novel therapeutic approaches where an increased amount of cross-linked proteins correlates with the manifestation of degenerative disorders.