Graduation date: 1993

Bibliography: leaves 279-293. / xxxiv, 323 leaves : ill. ; 30 cm. / Title page, contents and abstract only. The complete thesis in print form is available from the University Library. / Temperature-programmed Pyrolysis experiments employing Bowmans and Lochiel low-rank coal and treated Bowmans coals, were conducted to investigate the sulphur transformations during pyrolysis. / Thesis (Ph.D.)--University of Adelaide, Dept. of Chemical Engineering, 2000

Bibliography: leaves 279-293. Temperature-programmed Pyrolysis experiments employing Bowmans and Lochiel low-rank coal and treated Bowmans coals, were conducted to investigate the sulphur transformations during pyrolysis.

Yes / A simulation was conducted using Aspen HYSYS® software for an industrial scale condensate stabilization unit and the results of the product composition from the simulation were compared with the plant data. The results were also compared to the results obtained using PRO/II software. It was found that the simulation is closely matched with the plant data and in particular for medium range hydrocarbons. The effects of four process conditions, i.e. feed flow rate, temperature, pressure and reboiler temperature on the product Reid Vapour Pressure (RVP) and sulphur content were also studied. The operating conditions which gave rise to the production of off-specification condensate were found. It was found that at a column pressure of 8.5 barg and reboiler temperature of 180°C, the condensate is successfully stabilised to a RVP of 60.6 kPa (8.78 psia). It is also found that as compared to the other parameters the reboiler temperature is the most influential parameter control the product properties. Among the all sulphur contents in the feed, nP-Mercaptan played a dominant role for the finishing product in terms of sulphur contents.

Yes / A simulation was conducted using Aspen HYSYS® software for an industrial scale condensate stabilization unit and the results of the product composition from the simulation were compared with the plant data. The results were also compared to the results obtained using PRO/II software. The results show that the simulation is in good agreement with the plant data, especially for medium range hydrocarbons. For hydrocarbons lighter than C5, the simulation results over predict the plant data while for hydrocarbons heavier than C9 this trend is reversed. The influences of steam temperature and pressure, as well as feed conditions (flow rate, temperature and pressure) for the product specification (RVP and sulphur content) were also investigated. It was reported that the operating conditions gave rise to the production of off-specification condensate and it was also found that the unit could be utilized within 40–110% of its normal throughput without altering equipment sizing and by the operating parameters.

<p>The aim of this project is to investigate the possibilities of minimizing the sulphur content in Kraft lignin. Kraft lignin contains about 1.5 to 3% sulphur. The sulphur is believed to be present in lignin as inorganic sulphur, as elemental sulphur, as adsorbed polysulphide and/or as organically bound sulphur. For the determination of these different types of sulphur components, different approaches and methods were used. For the determination of inorganic sulphur, lignin was washed with water at pH 6 and pH 2 and the wash waters were analysed with ion chromatography (IC). For the determination of total sulphur content in the lignin, two methods were used; Schöniger combustion followed by ion chromatography (IC) and wet digestion followed by inductively coupled plasma (ICP). The elemental sulphur content in water-extracted lignin was determined after n-pentane extraction. ICP analysis was performed on the washed lignin.</p><p>Calcium present in the lignin may bind polysulphides and thus be a source of the observed sulphur. The lignin was thus ion-exchanged to remove any calcium. To further investigate how the sulphur content in lignin can be decreased, two different types of reactions were performed on lignin; oxidation and reduction. The oxidation reactions were made in sodium hydroxide with oxygen at different temperatures and time on both original and water-extracted lignin. The reduction reactions were made on water-extracted lignin with Raney nickel in three different solvent systems: methanol: water, acetone: water and sodium hydroxide.</p><p> </p><p>The original lignin contained 2.6% sulphur as determined by ICP. Washing lowered the content to 1.85% sulphur. By n-pentane extraction the elemental sulphur was lowered to a level of 1.82% sulphur, which was considered to be organically bound sulphur. Neither the ion exchange nor the oxidation lowered the sulphur content significantly.</p><p> </p><p>The reduction reactions successfully the organically bound sulphur from 1.82% to a level of 0.54%.</p><p> </p><p>The relative distribution of the sulphur content in the studied softwood lignin was as follows: about 29% as inorganic sulphur, about 1% as elemental sulphur and approximately 70% as organically bound sulphur, of which 49% could be removed by Raney nickel.</p>

The aim of this project is to investigate the possibilities of minimizing the sulphur content in Kraft lignin. Kraft lignin contains about 1.5 to 3% sulphur. The sulphur is believed to be present in lignin as inorganic sulphur, as elemental sulphur, as adsorbed polysulphide and/or as organically bound sulphur. For the determination of these different types of sulphur components, different approaches and methods were used. For the determination of inorganic sulphur, lignin was washed with water at pH 6 and pH 2 and the wash waters were analysed with ion chromatography (IC). For the determination of total sulphur content in the lignin, two methods were used; Schöniger combustion followed by ion chromatography (IC) and wet digestion followed by inductively coupled plasma (ICP). The elemental sulphur content in water-extracted lignin was determined after n-pentane extraction. ICP analysis was performed on the washed lignin. Calcium present in the lignin may bind polysulphides and thus be a source of the observed sulphur. The lignin was thus ion-exchanged to remove any calcium. To further investigate how the sulphur content in lignin can be decreased, two different types of reactions were performed on lignin; oxidation and reduction. The oxidation reactions were made in sodium hydroxide with oxygen at different temperatures and time on both original and water-extracted lignin. The reduction reactions were made on water-extracted lignin with Raney nickel in three different solvent systems: methanol: water, acetone: water and sodium hydroxide.   The original lignin contained 2.6% sulphur as determined by ICP. Washing lowered the content to 1.85% sulphur. By n-pentane extraction the elemental sulphur was lowered to a level of 1.82% sulphur, which was considered to be organically bound sulphur. Neither the ion exchange nor the oxidation lowered the sulphur content significantly.   The reduction reactions successfully the organically bound sulphur from 1.82% to a level of 0.54%.   The relative distribution of the sulphur content in the studied softwood lignin was as follows: about 29% as inorganic sulphur, about 1% as elemental sulphur and approximately 70% as organically bound sulphur, of which 49% could be removed by Raney nickel.

The reaction of sulfate with six podzolic horizons of the Southern Laurentians (Quebec) was investigated using batch reaction techniques. It was demonstrated that sulfate sorption increased with decreasing solution pH to a maximum sorption capacity at around pH 4.0; below this pH retention decreased. This drop in sorption capacity was related to the partial dissolution of Al surface coatings. Indeed, the amount of native sulfate and the maximum sorption during the experiment were positively correlated (R$ sp2$ = 0.982, 0.800) with the oxalate extractable Al content of these forested soils. In all six horizons, the increase in sulfate sorption as a function of equilibrium sulfate concentration was best described by the Gunary equation. Kinetic experiments showed the presence of two major stages in both sorption and desorption reactions with an initial quick change (first 6 h) in solution concentration being followed by a second step where the reactions between sulfate and the soil matrix were much slower. The time-dependence of these reactions emphasized the appropriateness of kinetic equation in describing field situations. Moreover, kinetics studies performed under highly acidic conditions demonstrated that the amount of sulfate sorbed decreased with time after an initial sorption step due to the partial dissolution of Al surface materials. Thermodynamic calculations further suggested the subsequent precipitation of jurbanite. It was then concluded that surface dissolution and mineral formation should be considered in the interpretation of results obtained from experiments aimed at determining the effect of pH on sulfate retention.

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