Catalyst Deactivation on a Two-Stroke Engine

With the legislative demands increasing on recreational vehicles and utility engined applications, the two-stroke engine is facing increasing pressure to meet these requirements. One method of achieving the required reduction is via the introduction of a catalytic converter. The catalytic converter not only has to deal with the characteristically higher CO and HC concentration, but also any oil which is added to lubricate the engine. In a conventional two-stroke engine with a total loss lubrication system, the oil is either scavenged straight out the exhaust port or is entrained, involved in combustion and is later exhausted. This oil can have a significant effect on the performance of the catalyst.
To investigate the oiling effect, three catalytic converters were aged using a 400cm₃ DI two-stroke engine. A finite level of oil was added to the inlet air of the engine to lubricate the internal workings. The oil flow rate is independent of the engine speed and load.

Three catalysts were aged for 50 hours, experiencing a constant space velocity and set engine conditions. The engine was fueled on petrol and later on propane to eliminate the effects, if any, of petrol additives on catalyst deactivation. The oiling rate was varied to investigated deactivation from oil contamination. Post-mortem analysis was performed on the three catalysts. This consisted of a controlled light-off test performed on a catalyst rig, during which period, temperatures were measured and recorded towere aged for 50 hours, experiencing a constant space velocity and set engine conditions. The engine was fueled on petrol and later on propane to eliminate the effects, if any, of petrol additives on catalyst deactivation. The oiling rate was varied to investigated deactivation from oil contamination. Post-mortem analysis was performed on the three catalysts. This consisted of a controlled light-off test performed on a catalyst rig, during which period, temperatures were measured and recorded to find out where deactivation of each catalyst was occurring. The recorded results were all analyzed and these showed that from the measured light-off temperatures the aged catalysts behaved similarly. However the pattern in the light-off was significantly different when the engine was fueled by propane as opposed to gasoline.

Inlet recirculation in automotive turbocharger centrifugal compressors

As the designers of modern automotive turbochargers strive to increase map width and lower the mass flow rate at which compressor surge occurs, the recirculating flows at the impeller inlet are becoming a much more relevant aerodynamic feature. Compressors with relatively large map widths tend to have very large recirculating regions at the inlet when operating close to surge; these regions greatly affect the expected performance of the compressor.

This study analyses the inlet recirculation region numerically using several modern automotive turbocharger centrifugal compressors. Using 3D Computational Fluid Dynamics (CFD) and a single passage model, the point at which the recirculating flow begins to develop and the rate at which it grows are investigated. All numerical modelling has been validated using measurements taken from hot gas stand tests for all compressor stages. The paper improves upon an existing correlation between the rate of development of the recirculating region and the compressor stage, which is supported by results from the numerical analysis.

Simultaneous biosorption of methylene blue and trivalent chromium onto olive stone

In this work, olive stone (OS) was utilized to investigate its capacity as biosorbent for methylene blue (MB) and Cr(III), which are usually present in textile industry effluents. Equilibrium and kinetic experiments were performed in batch experiments. The biosorption process followed pseudo-second-order kinetics. The equilibrium data were fitted with several models, but Langmuir and Sips models best reproduced the experimental results. Maximum biosorption capacities were 3.296 mg/g (0.0116 mmol/g) and 4.990 mg/g (0.0960 mmol/g) for MB and Cr(III), respectively. Several operation variables, such as
biosorbent mass, flow rate, and initial concentration on the removal of dye and metal, were evaluated in column system. The removal efficiency improved as OS mass increased and decreased when flow rate and initial concentration increased. Also, MB uptake was substantially decreased by increasing the initial concentration of Cr(III), ranging from 6.09 to 2.75 mg/g. These results show that the presence of Cr(III) significantly modifies the biosorption capacity of MB by the OS. These results suggest that OS is a potential low-cost food industry waste for textile industry wastewater treatment.

TAP Reactor Development and Application in the Kinetic Characterization of Catalysts for Heterogeneously Catalyzed Gas Phase Reactions

This manuscript describes the application and further development of the TAP technique in kinetic characterization of heterogeneous catalysis. The major application of TAP systems is to study mechanisms, kinetics and transport phenomena in heterogeneous catalysis, all of which is made possible by the sub-millisecond time resolution. Furthermore, the kinetic information obtained can be used to gain an insight into the mechanism occurring over the catalyst system. This is advantageous as heterogeneous catalysts with an improved efficiency can be developed as a result. TAP kinetic studies are carried out at low pressure (~1x10-7 mbar) and TAP pulses are sufficiently small (1013-1015 molecules) so as to maintain this low pressure. The use of a small number of molecules in comparison to the total number of active sites means the state of the catalyst remains relatively unchanged. The use of the low intensity pulses also makes the pressure gradient negligible and so allows the TAP reactor system to operate in the Knudsen Diffusion regime, where gas-gas reactions are eliminated. Hence only gas-catalyst reactions are investigated and, by the use of moment analysis of observed exit flow, rate constants of elementary steps of the reaction can be obtained.

In this manuscript, two attempts to further the TAP technique are reported. Firstly, the work undertaken at QUB to attempt to control the number of molecules of condensable reagents that can be pulsed during a TAP pulse experiment is disclosed. Secondly, a collaborative project with SAI Ltd Manchester is discussed in a separate chapter, where technical details and validation of a customised time of flight mass spectrometer (ToF MS) for the QUB TAP-1 system are reported. A collaborative project with Cardiff Catalysis Institute focusing on the study of CO oxidation over hopcalite catalysts is also reported. The analysis of the experimental results has provided an insight into the possible mechanism of the oxidation of CO over these catalysts. A correction function has also been derived which accounts for the adsorption of reactant molecules over inert materials that are used for the reactor packing in TAP experiments. This function was then applied to the selective reduction of O2 in a H2 rich ethene feed, so that more accurate TAP moment based analysis could be conducted.

Identification of human neutrophil defensins (HNPs1-3) in biopsies of squamous cell carcinomas of the human tongue

It has previously been reported that the a-defensins, found in the granules of polymorphonuclear leukocytes (neutrophils/ PMNs), are cytolytic for human tumour cells in vitro. Objective: To identify and quantify the a- defensins, HNP-1, HNP-2 and HNP-3 in healthy and tumour tissue from patients with oral squamous cell carcinoma using HPLC, mass spectrometry and amino acid sequencing. Methods: All patients (n=5) were diagnosed with oral squamous cell carcinoma of the tongue.Biopsy tissue from the site of the tumour (n=5) and a non-affected region of the tongue (n=5) was snap frozen and subsequently stored at -70 ºC until analysed. Peptides were extracted from the 10 tissue biopsies using acidified ethanol. Peptide extracts were separated by reverse-phase HPLC . All tumour and control tissue samples were individually analysed under identical conditions with a flow rate of l ml/min, ambient column temperature and absorbance detection at 214 and 280 nm. Fractions (1ml) were collected automatically. HPLC fractions were analysed by MALDI-MS using a linear time-of-flight Voyager DE-mass spectrometer (PerSeptive Biosystems, UK). Using this system the detection limit was 10 fmol. Peptides with molecular masses corresponding to those reported for the a-defensins were deemed of interest and were further subject to complete structural analysis by automated Edman degradation using an Applied Biosystems 491 Procise microsequencer. Results: MALDI-MS revealed a triad of peptides of molecular masses 3442 Da, 3371 Da and 3486 Da in both healthy and tumour tissue. Full length sequence data were obtained for the three a-defensins, unequivocally identifying their presence in both tumour and healthy tissue. Analysis of the MALDI-MS and sequence data indicated that the a-defensins were overexpressed (up to 12 fold) in tumour tissue. Conclusion: This study demonstrates the feasibility of screening tumour tissue for novel peptides/proteins using HPLC and MALDI-MS.The role of a-defensins in oral squamous cell carcinoma of the tongue requires further investigation.