Tetrachloroethylene (PCE) is a contaminant that has been frequently detected in ground water, surface water, air and soil. Advanced reduction processes (ARP) make up a set of wastewater treatment technologies that have been proposed recently. This project has conducted research on degrading PCE with an ARP that combines dithionite and ultraviolet activation. The purpose of the project is to provide knowledge for the development of potential wastewater treatment technologies. Several control experiments (blank control, reagent control and UV control) were conducted to prove the feasibility of applying the dithionite/UV ARP to degrade PCE. ARP degradation of PCE was studied under different pH (5, 7, 8, 9) and light intensities (2, 4, 7.3 mW/cm2). The results showed that the fastest degradation was observed at pH 7 and that degradation becomes faster at higher light intensities. Combining dithionite and UV light resulted in a faster degradation of PCE than only using UV light to photolyze PCE.

This study explores alternative alkaline agents other than sodium carbonate for ASP process on reactive and non-reactive crude oil recovery at 55oC and 100oC. The alkalis studied were sodium metaborate, pH of 10-10.5, and a sodium silicate/borax mixture, pH of 11. Sodium metaborate showed very optimistic results similar to sodium carbonate studies. Sodium metaborate ASP floods recovered 97-99% of residual oil after waterflood in Berea sandstone at 55oC. The oil saturation in the core after the chemical flood was between 0.5-2%. Sodium metaborate ASP floods recovered 96% of the tertiary oil with a residual oil saturation of 2.6% in Bentheimer sandstone at 100oC. More importantly, the retention of surfactant was very low with the use of metaborate in Berea, Bentheimer and high clay content reservoir cores. 0.18 mg/g rock (68%) and 0.07 mg/g rock (30%) of surfactant was retained in Berea and Bentheimer respectively with the use of sodium metaborate. Sodium metaborate ASP floods recovered 96% and 98% of residual oil with a final oil saturation of 4.8% and 0.56% at 100oC and 55oC respectively in reservoir rock. The retention in reservoir core was 0.13 mg/g (48%) and 0.29 mg/g (80%) at 100oC and 55oC respectively. Sodium borax/metasilicate had a lower tertiary oil recovery due to higher surfactant retention in Berea sandstone. The ASP flood recovered 81% and 86% of tertiary oil at 100oC and 55oC respectively. The retention was 0.326 mg/g (97%) and 0.267 mg/g (98%). The last section involves treatment and reduction of reservoir cores containing clays and iron minerals. Reservoirs exist as anaerobic and reduced environments and these conditions must be emulated in laboratory experiments. Exposure of reservoir cores to aerobic conditions causes an oxidizing environment in the core leading to higher surfactant retention in the laboratory than the field. Dithionite was used to reduce reservoir cores and produce lower surfactant retention closer to field tests. Proper reduced conditions also improved oil recovery. Dithionite must be buffered with sodium bicarbonate to maintain the reducing power of dithionite. Dithionite oxidation by ferric iron and water causes hydroxyl ion consumption and pH decrease. The EH and iron concentration of the effluents must be monitored to determine the success of the core reduction. Effluent EH matching injected values and iron concentration close to the mineral solubility in brine should be used as benchmark for the success of core reduction / text

Die vorliegende Arbeit beschreibt die Etablierung einer neuen Methode zur Durchführung von Diffusionsmessungen innerhalb weniger Nanometer dicker Polyelektrolytmultischichten. An das Polykation PAH wurde der Fluorophor NBD gekoppelt. PAH-NBD kann im Rahmen des Beschichtungsprozesses an verschiedene Positionen des auf kolloidalen Teilchen adsorbierten PAH/PSS-Multifilms lokalisiert werden. Nach Dithionitzugabe wird die Fluoreszenz durch die ablaufende Reduktionsreaktion zwischen NBD und Dithionit gelöscht. Die Abnahme der Fluoreszenzintensität wird flowzytometrisch detektiert. Die Auswertung der Daten erfolgte auf der Grundlage verschiedener theoretischer Näherungslösungen für Subdiffusion, gekoppelt mit der Reaktionskinetik der Fluoreszenzlöschung. Die Ergebnisse sind nicht mit normaler Diffusion innerhalb der Schichten vereinbar. Vielmehr ergibt sich eine stark subdiffusive Transportcharakteristik des Dithionits innerhalb des Polyelektrolytmultifilms. Als Ursachen hierfür werden die Wechselwirkungen der Dithionitmoleküle mit den PAH-Molekülen sowie die unterschiedlichen Zugänglichkeiten der NBD-Moleküle für die diffundierenden Dithionitmoleküle durch ständige Konformationsänderungen der PAH-Moleküle angesehen. Hervorzuheben ist, dass erstmalig eine Technik etabliert wurde, mit welcher Diffusionsmessungen auf nanoskopischer Skala innerhalb von Polyelektrolytmultischichten durchgeführt werden können. Die subdiffusive Kinetik ist im Vergleich zu normaler Diffusion stark verzögert und ermöglicht dadurch einen länger anhaltenden Stofftransport, was für die Anwendung der Polyelektrolytmultischichten als Medikamententräger besonders vorteilhaft ist. Es wurde gezeigt, dass die Ladung der obersten Schicht des Polyelektrolytmultifilms einen erheblichen Einfluss auf die Qualität und die Struktur der Polyelektrolytmatrix, und das ebenfalls in tieferen Bereichen der Polyelektrolytmultischicht, hat.

The purpose of this work was to study polymer degradation mechanisms as well as ways to mitigate it. In the area of chemical stability, defined as divalent cation tolerance of acrylic polymers as hydrolysis increases, use of the n-vinyl pyrrolidone (NVP) monomer helps to preserve viscosity and tolerate higher calcium concentrations over those polymers without NVP. Also, ethylenediaminetetraacetate tetrasodium salt (EDTA-Na+4) is shown to sequester calcium ions at alkaline conditions (pH>10) and, in the case of lab-aged post-hydrolyzed poly(AM-co-AMPS), helps to retain full viscosity at all calcium concentrations when EDTA is present at a stoichiometric equivalence of calcium. Many discrepancies exist in the literature concerning the presence or absence of degradation under various field or laboratory conditions. Carbonate and bicarbonate, which are typically present in natural waters but often neglected in lab-prepared brines, prove to be a hidden variable in resolving why Shupe (1981) saw no loss in viscosity when sodium dithionite was added to polymer in the presence of oxygen (with bicarbonates) but others (Knight, 1973 and Levitt and Pope, 2008) observed severe degradation under similar conditions (but without bicarbonates). A commercial HPAM polymer (Flopaam 3630S) has been shown to be stable in the presence of ferrous iron in the absence of oxygen, clarifying an apparent discrepancy in the literature between the results of Yang and Treiber (1985) and Kheradmand (1987). Dissolved oxygen (DO) levels, and not redox potential (ORP) measurements, are often reported in polymer stability research on oxidative degradation. ORP is shown to be a better measure of the onset of degradation because oxygen is initially being consumed and may not appear until substantial degradation has occurred. Although generally believed to be a detriment to polymer stability in the field, aeration of iron-laden source water prior to hydration of polymer may be beneficial in certain cases where exposure to air in unavoidable. Also, a novel process of safely producing sodium dithionite in the field proves to perform better in terms of long-term polymer stability in anaerobic conditions than the traditional method of using a solution made from powder dithionite. Finally, a pre-sheared 5 million Dalton HPAM is successfully injected into a 3 mD carbonate reservoir core plug. Remarkably, permeability reduction factors remain at values close to unity. However, pressure data from ASP tertiary corefloods suggest that polymer is not feasible for field injections. / text

Die vorliegende Arbeit beschreibt die Etablierung einer neuen Methode zur Durchführung von Diffusionsmessungen innerhalb weniger Nanometer dicker Polyelektrolytmultischichten. An das Polykation PAH wurde der Fluorophor NBD gekoppelt. PAH-NBD kann im Rahmen des Beschichtungsprozesses an verschiedene Positionen des auf kolloidalen Teilchen adsorbierten PAH/PSS-Multifilms lokalisiert werden. Nach Dithionitzugabe wird die Fluoreszenz durch die ablaufende Reduktionsreaktion zwischen NBD und Dithionit gelöscht. Die Abnahme der Fluoreszenzintensität wird flowzytometrisch detektiert. Die Auswertung der Daten erfolgte auf der Grundlage verschiedener theoretischer Näherungslösungen für Subdiffusion, gekoppelt mit der Reaktionskinetik der Fluoreszenzlöschung. Die Ergebnisse sind nicht mit normaler Diffusion innerhalb der Schichten vereinbar. Vielmehr ergibt sich eine stark subdiffusive Transportcharakteristik des Dithionits innerhalb des Polyelektrolytmultifilms. Als Ursachen hierfür werden die Wechselwirkungen der Dithionitmoleküle mit den PAH-Molekülen sowie die unterschiedlichen Zugänglichkeiten der NBD-Moleküle für die diffundierenden Dithionitmoleküle durch ständige Konformationsänderungen der PAH-Moleküle angesehen. Hervorzuheben ist, dass erstmalig eine Technik etabliert wurde, mit welcher Diffusionsmessungen auf nanoskopischer Skala innerhalb von Polyelektrolytmultischichten durchgeführt werden können. Die subdiffusive Kinetik ist im Vergleich zu normaler Diffusion stark verzögert und ermöglicht dadurch einen länger anhaltenden Stofftransport, was für die Anwendung der Polyelektrolytmultischichten als Medikamententräger besonders vorteilhaft ist. Es wurde gezeigt, dass die Ladung der obersten Schicht des Polyelektrolytmultifilms einen erheblichen Einfluss auf die Qualität und die Struktur der Polyelektrolytmatrix, und das ebenfalls in tieferen Bereichen der Polyelektrolytmultischicht, hat.

Sodium dithionite (Na2S2O4) is a powerful reducing agent. It has therefore been suggested to be used as an additive in kraft pulping to improve the yield. However, sodium dithionite easily decomposes and it is thus important to determine the effect of different conditions. The aim of this thesis has been to investigate the thermal stability of sodium dithionite under anaerobic conditions using ATR-FTIR spectroscopy under different conditions, such as heating temperature, concentration of the solution, heating time and pH. The stability of sodium dithionite was found to decrease with increasing heating temperature, concentration of sodium dithionite, heating time and pH. Sodium dithionite was found to be relatively stable at moderate alkaline pH:s 11.5 and 12.5, while a rapid decrease in stability with time was noted at higher heating temperatures and concentrations of sodium dithionite. Based on this study on the thermal stability of sodium dithionite, the following conditions are suggested as the most promising, when adding sodium dithionite to the kraft cooking as an additive; pH 12.5, with 0.4 M concentration of the solution, at a heating temperature of 100 °C.

The three main components of wood, namely, cellulose, hemicellulose, and lignin, can be used in various areas. However, since lignin covalently crosslinks with wood polysaccharides creating networks that is an obstacle for extraction, direct extraction of different wood components in high yield is not an easy matter. One potential approach to overcome such obstacles is to treat the wood with specific enzymes that degrade the networks by specific catalysis. However, the structure of wood is so compact that the penetration of the wood fibers by large enzyme molecules is hindered. Thus, the pretreatment of wood prior to the application of enzymes is necessary, for “opening” the structure. One pretreatment method that was performed in this thesis is based on kraft pulping, which is a well-established and industrialized technique. For untreated wood, the wood fibers cannot be attacked by the enzymes. A relatively mild pretreatment was sufficient for wood polysaccharides hydrolyzed by a culture filtrate. A methanol-alkali mixture extraction was subsequently applied to the samples that were pretreated with two types of hemicellulases, Gamanase and Pulpzyme HC, respectively. The extraction yield increased after enzymatic treatment, and the polymers that were extracted from monocomponent enzyme-treated wood had a higher degree of polymerization. Experiments with in vitro prepared lignin polysaccharide networks suggested that the increased extraction was due to the enzymatic untying. However, the relatively large loss of hemicellulose, particularly including (galacto)glucomannan (GGM), represents a problem with this technique. To improve the carbohydrate yield, sodium borohydride (NaBH4), polysulfide and anthraquinone were used, which increased the yields from 76.6% to 89.6%, 81.3% and 80.0%, respectively, after extended impregnation (EI). The additives also increased the extraction yield from approximately 9 to 12% w/w wood. Gamanase treatment prior to the extraction increased the extraction yield to 14% w/w wood. Sodium dithionite (Na2S2O4) is an alternative reducing agent for the preservation of hemicelluloses because it is less expensive than metal hydrides and only contains sodium and sulfur, which will not introduce new elements to the recovery system. Moreover, Na2S2O4has the potential to be generated from black liquor. Na2S2O4 has some preservation effect on hemicelluloses, and the presence of Na2S2O4 also contributed to delignification. The extraction yield increased to approximately 15% w/w wood. Furthermore, Na2S2O4 has been applied in the kraft pulping process of spruce. The yield and viscosity increased, while the Klason lignin content and kappa number decreased, which represents a beneficial characteristic for kraft pulp. The brightness and tensile strength of the resulting sheets also improved. However, the direct addition of Na2S2O4 to white liquor led to greater reject content. This problem was solved by pre-impregnation with Na2S2O4 and/or mild steam explosion (STEX) prior to the kraft pulping process. Following Na2S2O4 pre-impregnation and mild STEX, the obtained kraft pulp had substantially better properties compared with the properties exhibited after direct addition of Na2S2O4 to the white liquor. The wood structure opening efficiency of mild STEX alone was also tested. The accessibility of the wood structure to enzymes was obtained even at very modest STEX conditions, according to a reducing sugar analysis, and was not observed in untreated wood chips, which were used as a reference. The mechanical effect of STEX appears to be of great importance at lower temperatures, and both chemical and mechanical effects occur at higher STEX temperatures. / <p>QC 20140903</p>

<p>The potential of using acid hydrogen peroxide under Fenton conditions to lower the electrical energy consumed during the production of Black spruce (Picea mariana) thermomechanical pulp (TMP) was investigated. The chemical system, which consisted of ferrous sulphate, hydrogen peroxide and optionally an enhancer (3,4-dimethoxybenzyl alcohol, ethylenediaminetetraacetic acid or oxalic acid/sodium oxalate), was evaluated as an inter-stage treatment where the primary refiner was used as a mixer. The produced TMPs were thoroughly characterised in order to explain the effect of the chemical system on fibre development and to be able to propose a mechanism for the impact on refining energy reduction. The possibility to improve the optical properties by washing, chelating and sodium dithionite or hydrogen peroxide bleaching the treated pulps was evaluated.</p><p> </p><p>The results obtained in a pilot plant trial show that it is possible to significantly reduce the comparative specific energy consumption by approximately 20% and 35% at a freeness value of 100 ml CSF or a tensile index of 45 Nm/g by using 1% and 2% hydrogen peroxide respectively. The energy reduction is obtained without any substantial change in the fractional composition of the pulp, though tear strength is slightly reduced, as are brightness and pulp yield. No major differences between the reference pulp and the chemically treated pulps were found with respect to fibre length, width or cross-sectional dimensions. However, the acid hydrogen peroxide-treated pulps tend to have more collapsed fibres, higher flexibility, a larger specific surface area and a lower coarseness value. The yield loss accompanying the treatment is mainly a consequence of degraded hemicelluloses. It was also found that the total charge of the chemically treated pulps is higher compared to the reference pulps, something that may have influenced the softening behaviour of the fibre wall.</p><p> </p><p>A washing or chelating procedure can reduce the metal ion content of the chemically treated TMPs considerably. The amount of iron can be further reduced to a level similar to that of untreated pulps by performing a reducing agent-assisted chelating stage (QY) with dithionite. The discoloration cannot, however, be completely eliminated. The brightness decrease of the treated pulps is thus not only caused by higher iron content in the pulp, but is also dependent on the type of iron compound and/or other coloured compounds connected with the acid hydrogen peroxide treatment. Oxidative bleaching with hydrogen peroxide (P) is more effective than reductive bleaching with sodium dithionite in regaining the brightness lost during the energy reductive treatment. Using a QY P sequence, a hydrogen peroxide charge of 3.8% was needed to reach an ISO brightness of 75% for the chemically treated pulps. The corresponding hydrogen peroxide charge for the untreated TMP reference was 2.5%.</p><p> </p><p>The radicals generated in the Fenton reaction will probably attack and weaken/soften the available outer fibre wall layers. This could facilitate fibre development and consequently lower the electrical energy demand for a certain degree of refinement.</p>

The potential of using acid hydrogen peroxide under Fenton conditions to lower the electrical energy consumed during the production of Black spruce (Picea mariana) thermomechanical pulp (TMP) was investigated. The chemical system, which consisted of ferrous sulphate, hydrogen peroxide and optionally an enhancer (3,4-dimethoxybenzyl alcohol, ethylenediaminetetraacetic acid or oxalic acid/sodium oxalate), was evaluated as an inter-stage treatment where the primary refiner was used as a mixer. The produced TMPs were thoroughly characterised in order to explain the effect of the chemical system on fibre development and to be able to propose a mechanism for the impact on refining energy reduction. The possibility to improve the optical properties by washing, chelating and sodium dithionite or hydrogen peroxide bleaching the treated pulps was evaluated.   The results obtained in a pilot plant trial show that it is possible to significantly reduce the comparative specific energy consumption by approximately 20% and 35% at a freeness value of 100 ml CSF or a tensile index of 45 Nm/g by using 1% and 2% hydrogen peroxide respectively. The energy reduction is obtained without any substantial change in the fractional composition of the pulp, though tear strength is slightly reduced, as are brightness and pulp yield. No major differences between the reference pulp and the chemically treated pulps were found with respect to fibre length, width or cross-sectional dimensions. However, the acid hydrogen peroxide-treated pulps tend to have more collapsed fibres, higher flexibility, a larger specific surface area and a lower coarseness value. The yield loss accompanying the treatment is mainly a consequence of degraded hemicelluloses. It was also found that the total charge of the chemically treated pulps is higher compared to the reference pulps, something that may have influenced the softening behaviour of the fibre wall.   A washing or chelating procedure can reduce the metal ion content of the chemically treated TMPs considerably. The amount of iron can be further reduced to a level similar to that of untreated pulps by performing a reducing agent-assisted chelating stage (QY) with dithionite. The discoloration cannot, however, be completely eliminated. The brightness decrease of the treated pulps is thus not only caused by higher iron content in the pulp, but is also dependent on the type of iron compound and/or other coloured compounds connected with the acid hydrogen peroxide treatment. Oxidative bleaching with hydrogen peroxide (P) is more effective than reductive bleaching with sodium dithionite in regaining the brightness lost during the energy reductive treatment. Using a QY P sequence, a hydrogen peroxide charge of 3.8% was needed to reach an ISO brightness of 75% for the chemically treated pulps. The corresponding hydrogen peroxide charge for the untreated TMP reference was 2.5%.   The radicals generated in the Fenton reaction will probably attack and weaken/soften the available outer fibre wall layers. This could facilitate fibre development and consequently lower the electrical energy demand for a certain degree of refinement.

A new class of treatment processes called Advanced Reduction Processes (ARP) has been proposed. The ARPs combine activation methods and reducing agents to form highly reactive reducing radicals that degrade oxidized contaminants. Batch screening experiments were conducted to identify effective ARP by applying several combinations of activation methods (ultraviolet light, ultrasound, electron beam, microwaves) and reducing agents (dithionite, sulfite, ferrous iron, sulfide) to degradation of five target contaminants (perchlorate, nitrate, perfluorooctanoic acid, 2,4 dichlorophenol, 1,2 dichloroethane) at 3 pH levels (2.4, 7.0, 11.2). These experiments identified the combination of sulfite activated by ultraviolet light produced by a low pressure mercury vapor lamp as an effective ARP. More detailed kinetic experiments were conducted with nitrate and perchlorate as target compounds and nitrate was found to degrade more rapidly than perchlorate. The effects of pH, sulfite concentration, and light intensity on perchlorate and nitrate degradation were investigated. The effectiveness of the sulfite/UV-L treatment process improved with increasing pH for both perchlorate and nitrate.