Design and characterisation of a close-concentric annular reactor for kinetic studies at high temperatures

A novel annular reactor for kinetic studies at high temperature and flow conditions has been designed to keep eccentricity tolerances below 10%. In a previous work, we have shown that it is very important to keep such low eccentricity values in order to collect reliable kinetic data from this type of reactors. As proposed in this study, a modified reactor with the use of a spacer could guarantee an annular duct with low levels of eccentricity. Manufacturing tolerances or deformation effects giving rise to eccentricity can be significantly minimised when using this apparatus. The reactor has been both experimentally and theoretically characterised. Carbon monoxide oxidation was used as a model reaction under mass-transfer limited conditions revealing an eccentricity of ∼5%. With such small eccentricity levels, a concentric annular form can be assumed in the reactor analysis. Simple 1D or 2D models can therefore be inexpensively used in the evaluation of the kinetic data. Also, prior to the design of the annular reactor, a numerical investigation was carried out to clarify the effects of eccentricity, physical properties of the carrier gas and the annular aspect ratio on mass-transfer limitations. Contrary to expectations, a considerable increase in the fuel mass-diffusivity by carrier gas substitution did not change the mass-transfer rates for cases when eccentricity and aspect ratios were high.     

Thermal stability of metal-supported catalysts for reduction of cold-start emissions in a wood-fired domestic boiler

The aim of the present work is to develop a catalyst based on a mixture of manganese oxides and platinum supported on a metallic monolith for abatement of emissions from wood combustion, particularly during the cold-start phase. The activity and the thermal stability of the catalysts have been studied in the laboratory, before performing tests in a wood-stove. The effect of the hydrothermal treatment at 900°C on the adherence of the washcoat onto a metallic substrate was studied using scanning electronic microscope. It revealed well-adhering washcoat onto the metallic support due to the growth of the alumina whiskers during the treatment. The influence of the amount of washcoat, as well as the influence of the concentration of manganese oxides in it (Mn: 5 to 20 mol%/Al₂O₃) on the activity of fresh and hydrothermally-treated catalysts were studied. The activity tests were carried out using a mixture of carbon monoxide, naphthalene and methane in the presence of air, steam and carbon dioxide to resemble the flue gases from wood combustion. On the fresh catalysts, containing the same total amount of manganese, a high concentration of manganese oxides in the washcoat favoured the oxidation of carbon monoxide and naphthalene, whereas a lower concentration of manganese oxides in the washcoat gave higher activity for the oxidation of methane. An increased total amount of manganese oxides in the catalysts, which had the same amount of washcoat, resulted in an increase in activity for the oxidation of the three combustibles. After thermal treatment at 900°C for 270 h in steam, most of the manganese oxide catalysts were activated for the oxidation of carbon monoxide and naphthalene while only being slightly deactivated for the oxidation of methane. The addition of manganese oxides in the washcoat, however, lowers the temperature of the γ- to -alumina phase transformation. Platinum (0.5 mol%) was added to the manganese oxide (10 mol%) catalyst to improve its activity. A platinum catalyst was also tested for comparison. The platinum and the mixed catalysts showed similar activity for the oxidation of carbon monoxide and naphthalene, while the mixed catalysts were more active for the oxidation of methane. A similarly mixed MnO_x–Pt (10–0.5 mol%) catalyst supported on Al₂O₃ stabilised with 3% lanthanum, but at larger scale, was tested in a wood-stove. The possibility of pre-heating the catalyst during the start-up phase was studied. The tests revealed a strong decrease of the carbon monoxide and unburned hydrocarbons emissions during the start-up phase when the catalyst was pre-heated with hot air compared with no pre-heating or no catalyst.     

Conversion and in situ FTIR studies of direct NO decomposition over Cu-ZSM5

Copper ion-exchanged zeolites ZSM5 with SiO₂:Al₂O₃ molar ratios 33 and 53 have been subjected to activity tests for direct decomposition of NO (2000 ppm, GHSV 560–5400 h⁻¹). In situ infrared measurements were used to follow the reaction and surface and gas phase compositions. IR studies were also done in excess oxygen with rapid NO₂ formation in the gas phase.

A high level of overexchange of copper in the zeolite in combination with a low concentration of acid sites, concurrent with a high SiO₂:Al₂O₃ ratio, enhances the conversion of NO. A vibrational band at 1631 cm⁻¹ is observed below the light-off temperature and interpreted as a bridged nitrato group bound to Cu²⁺–O–Cu²⁺ dimers. This band disappears above the light-off temperature but the intensity below this temperature correlates with the catalytic activity. We interpret that these bridge bound nitrato groups act as siteblockers on the active sites for NO conversion and that a tentative reaction intermediate, N₂O₃, also binds in a bridge configuration to the same Cu²⁺–O–Cu²⁺ dimers.

A second nitrato group with unidentate coordination and vibrational bands at 1598/1575 cm⁻¹ probes isolated copper ions.

A third infrared band at 2130 cm⁻¹ confirms previous observations of -ions bound to the zeolite. We conclude that these species are coordinated to deprotonated and negatively charged sites on the zeolite and that these sites for adsorption are blocked by Cu²⁺ ion-exchange. The 2130 cm⁻¹ species appear to have no role in direct NO decomposition but the adsorption sites are crucial for the stability of the zeolite and intimately related to ion mobility in the lattice.

Prolonged immersion of the zeolite in dilute solutions of copper ions improves the catalyst performance by copper hydroxylation leading to enhanced formation of the above dimers.

A high SiO₂:Al₂O₃ ratio leads to more stable catalysts, particularly in combination with a modest overexchange of copper ions. Excessive amounts of copper escalates the deactivation of the Cu-ZSM5 catalyst through the migration and sintering of cupric oxide crystallites.     

The feasibility of a coal gasifier combined with a high-temperature fuel cell

The purpose of the study presented in this paper was to find out the feasibility of integrating a 50 MW fuel cell system, fed by gas from a coal gasifier, with an existing network for distribution of heat and power. The work presented is the results of the technical evaluation of a 50 MW coal fired high-temperature fuel cell power plant. The overall system can be divided into four subsystems including: coal gasification, gas cleaning, power generation and heat recovery.

The final system, a entrained flow gasifier combined with standard low-temperature gas cleanup and SOFC, resulted in an overall electrical efficiency of about 47%, and an overall efficiency close to 85%.     

Catalytic cracking of tar in biomass pyrolysis gas in the presence of calcined dolomite

The possibility of decreasing the content of tar in the fuel gas obtained by biomass pyrolysis has been studied. Catalytic cracking of the tar in presence of dolomite was used. Dolomite showed a high catalytic activity. The overall effect of the dolomite is to increase the gas yield by decreasing the tar yield. The dolomite and the steam used seem to affect the amount of naphthalene produced. By adjusting both the amounts of catalyst and steam, we were able to decrease significantly naphthalene (13 mg/kg dry substance biomass) and amount of tar (164 mg/kg dry substance biomass).     

The combined dewatering and liquid phase hydrogenolysis of raw peat using carbon monoxide

Raw peat, as received from the bog, was treated with carbon monoxide in batch autoclave at initial cold pressures comprising between 5.5 and 8.3 MPa and reaction temperatures ranging from 275° to 350°C. Potassium carbonate was added as a would-be catalyst for the shift reactions and its role has been found to be negligible in the presence of moderately humified peat with a relatively high ash content (8.1 wt. %).As a consequence of the above described treatment the organic matter in peat underwent significant changes losing its colloidal structure thus facilitating the separation between the resulting aqueous phase and the organic products. The latter appear as a sort of bitumen which is formed in quantities ranging from 25% to 60% (weight percentage relative to the maf peat initially present). Typical compositions (weight percentages) of the bitumen obtained are: C, 80%; H, 9%; O, 7%; N, 2% and S, 0.1%.     

Repeat abortion: a comparative study

In a study of 404 women (simple random sample) 20-29 years of age, 201 women (group A) applying for abortion and 203 women (group B) continuing their pregnancies were given a questionnaire and were also interviewed. The aim of the study was to describe women applying for repeat abortion and to compare them with women having their first abortion and with women continuing their pregnancies. Variables measured were socio-economic, psychological and social problems, relationship with the partner, earlier pregnancies, how the present pregnancy was experienced and decision-making. For presentation of the results, the data have been divided into four subgroups: pregnant women applying for their first abortion (A1, n = 137), women applying for repeat abortion (A2, n = 64), women continuing their pregnancies who have never applied for abortion (B1, n = 142), and women continuing their pregnancies who had previously applied for one or more abortions (B2, n = 58). Women who had had previous abortion/abortions had experienced more psychological problems during their lifetime than the other groups studied. They had more contact with the social welfare service and evaluated their relationship with the partner as less harmonious than women having a first abortion, also in comparison with women continuing their pregnancies with no earlier applications for abortion. Women who have had previous abortion/abortions seem to have a need for special attention. This involves not only being provided with efficient and acceptable contraception, but also with social and psychological support based on the experiences of the women.     

Total oxidation catalysts based on manganese or copper oxides and platinum or palladium II: Activity, hydrothermal stability and sulphur resistance

Deactivation of catalysts based on either manganese oxides, copper oxides, platinum, palladium or combinations of these metal oxides and noble metals supported on γ-alumina was studied. The activity of the catalysts for the oxidation of carbon monoxide, naphthalene and methane, in a mixture resembling the flue gases from wood combustion, was measured before and after exposure of the catalysts either to a temperature of 900°C in the presence of steam or to sulphur dioxide. Most of the mixed catalysts were more resistant to hydrothermal and sulphur treatments than the catalysts with a single active component. After the hydrothermal treatment the activity of the MnO_x catalyst was enhanced. When Pt is combined with MnO_x or CuO_x, the loss of activity of Pt was decreased during the hydrothermal treatment. Also, the hydrotreated mixed MnO_x–Pd and CuO_x–Pd catalysts were more active than the treated Pd catalyst for the oxidation of methane. After sulphur treatment, the activities of the mixed MnO_x–Pt (Pt: 0.05 mol%), MnO_x–Pd and CuO_x–Pd catalysts were improved for the oxidation of carbon monoxide and naphthalene. Among the catalysts studied, the MnO_x–Pt, CuO_x–Pt and CuO_x–Pd catalysts, with a metal oxide and a noble metal loading of 10 and 0.1 mol%/γ-alumina, respectively, had the best combination of activity, thermal stability and resistance to sulphur treatment.     

Total oxidation catalysts based on manganese or copper oxides and platinum or palladium I: Characterisation

Temperature-programmed reduction (TPR), oxidation (TPO), Raman spectroscopy, X-ray photoelectron spectroscopy (XPS) and X-ray diffraction (XRD) were used to characterise catalysts based on manganese oxides, copper oxides or one of them mixed with platinum or palladium-supported on γ-alumina. The catalysts were characterised before and after they had been exposed either to high temperature in the presence of steam or to sulphur dioxide. Raman spectroscopy, XRD, XPS and TPR performed on the fresh samples of MnO_x, mixed MnO_x–Pt and MnO_x–Pd revealed the presence of a mixture of manganese oxides, particularly Mn₂O₃. In the fresh mixed MnO_x–Pd and CuO_x–Pd samples, Pd catalysed the reduction of both MnO_x and CuO_x, whereas Pt only catalysed the reduction of MnO_x. After hydrothermal treatment at 900°C of the MnO_x, mixed MnO_x–Pt and MnO_x–Pd samples, there was a formation of new manganese oxide phase, Mn₃O₄ detected by Raman spectroscopy. TPR revealed increasing interaction between the metal oxides and the noble metals in the hydrothermally treated mixed MnO_x–Pd and CuO_x–Pd samples, and also the appearance of interaction in the treated mixed CuO_x–Pt sample. The sulphur adsorbed in all the MnO_x samples formed sulphate, which was more difficult to reduce than the oxides. Also, the reduction temperature of sulphates was lowered when noble metals are present.