Wet oxidation of recalcitrant lignin waters: Experimental and kinetic studies

The dissertation is based on four articles dealing with recalcitrant lignin water purification. Lignin, a complicated substance and recalcitrant to most treatment technologies, inhibits seriously pulp and paper industry waste management. Therefore, lignin is studied, using WO as a process method for its degradation. A special attention is paid to the improvement in biodegradability and the reduction of lignin content, since they have special importance for any following biological treatment. In most cases wet oxidation is not used as a complete ' mineralization method but as a pre treatment in order to eliminate toxic components and to reduce the high level of organics produced. The combination of wet oxidation with a biological treatment can be a good option due to its effectiveness and its relatively low technology cost. The literature part gives an overview of Advanced Oxidation Processes (AOPs). A hot oxidation process, wet oxidation (WO), is investigated in detail and is the AOP process used in the research. The background and main principles of wet oxidation, its industrial applications, the combination of wet oxidation with other water treatment technologies, principal reactions in WO, and key aspects of modelling and reaction kinetics are presented. There is also given a wood composition and lignin characterization (chemical composition, structure and origin), lignin containing waters, lignin degradation and reuse possibilities, and purification practices for lignin containing waters. The aim of the research was to investigate the effect of the operating conditions of WO, such as temperature, partial pressure of oxygen, pH and initial concentration of wastewater, on the efficiency, and to enhance the process and estimate optimal conditions for WO of recalcitrant lignin waters. Two different waters are studied (a lignin water model solution and debarking water from paper industry) to give as appropriate conditions as possible. Due to the great importance of re using and minimizing the residues of industries, further research is carried out using residual ash of an Estonian power plant as a catalyst in wet oxidation of lignin-containing water. Developing a kinetic model that includes in the prediction such parameters as TOC gives the opportunity to estimate the amount of emerging inorganic substances (degradation rate of waste) and not only the decrease of COD and BOD. The degradation target compound, lignin is included into the model through its COD value (CODligning). Such a kinetic model can be valuable in developing WO treatment processes for lignin containing waters, or other wastewaters containing one or more target compounds. In the first article, wet oxidation of "pure" lignin water was investigated as a model case with the aim of degrading lignin and enhancing water biodegradability. The experiments were performed at various temperatures (110 -190°C), partial oxygen pressures (0.5 -1.5 MPa) and pH (5, 9 and 12). The experiments showed that increasing the temperature notably improved the processes efficiency. 75% lignin reduction was detected at the lowest temperature tested and lignin removal improved to 100% at 190°C. The effect of temperature on the COD removal rate was lower, but clearly detectable. 53% of organics were oxidized at 190°C. The effect of pH occurred mostly on lignin removal. Increasing the pH enhanced the lignin removal efficiency from 60% to nearly 100%. A good biodegradability ratio (over 0.5) was generally achieved. The aim of the second article was to develop a mathematical model for "pure" lignin wet oxidation using lumped characteristics of water (COD, BOD, TOC) and lignin concentration. The model agreed well with the experimental data (R2 = 0.93 at pH 5 and 12) and concentration changes during wet oxidation followed adequately the experimental results. The model also showed correctly the trend of biodegradability (BOD/COD) changes. In the third article, the purpose of the research was to estimate optimal conditions for wet oxidation (WO) of debarking water from the paper industry. The WO experiments were' performed at various temperatures, partial oxygen pressures and pH. The experiments showed that lignin degradation and organics removal are affected remarkably by temperature and pH. 78-97% lignin reduction was detected at different WO conditions. Initial pH 12 caused faster removal of tannins/lignin content; but initial pH 5 was more effective for removal of total organics, represented by COD and TOC. Most of the decrease in organic substances concentrations occurred in the first 60 minutes. The aim of the fourth article was to compare the behaviour of two reaction kinetic models, based on experiments of wet oxidation of industrial debarking water under different conditions. The simpler model took into account only the changes in COD, BOD and TOC; the advanced model was similar to the model used in the second article. Comparing the results of the models, the second model was found to be more suitable for describing the kinetics of wet oxidation of debarking water. The significance of the reactions involved was compared on the basis of the model: for instance, lignin degraded first to other chemically oxidizable compounds rather than directly to biodegradable products. Catalytic wet oxidation of lignin containing waters is briefly presented at the end of the dissertation. Two completely different catalysts were used: a commercial Pt catalyst and waste power plant ash. CWO showed good performance using 1 g/L of residual ash gave lignin removal of 86% and COD removal of 39% at 150°C (a lower temperature and pressure than with WO). It was noted that the ash catalyst caused a remarkable removal rate for lignin degradation already during the pre heating for `zero' time, 58% of lignin was degraded. In general, wet oxidation is not recommended for use as a complete mineralization method, but as a pre treatment phase to eliminate toxic or difficultly biodegradable components and to reduce the high level of organics. Biological treatment is an appropriate post treatment method since easily biodegradable organic matter remains after the WO process. The combination of wet oxidation with subsequent biological treatment can be an effective option for the treatment of lignin containing waters.

Measurement and Improvement of Wet Paper Web Strength

Various strength properties of paper are measured to tell how well it resists breaks in a paper machine or in printing presses. The most often measured properties are dry tensile strength and dry tear strength. However, in many situations where paper breaks, it is not dry. For example, in web breaks after the wet pressing the dry matter content can be around 45%. Thus, wet-web strength is often a more critical paper property than dry strength. Both wet and dry strength properties of the samples were measured with a L&W tensile tester. Originally this device was not designed for the measurement of the wet web tensile strength, thus a new procedure to handle the wet samples was developed. The method was tested with Pine Kraft (never dried). The effect of different strength additives on the wet-web and dry paper tensile strength was studied. The polymers used in this experiment were aqueous solution of a cationic polyamidoamine-epichlorohydrin resin (PAE), cationic hydrophilised polyisocyanate and cationic polyvinylamine (PVAm). From all three used chemicals only Cationic PAE considerably increased the wet web strength. However it was noticed that at constant solids content all chemicals decreased the wet web tensile strength. So, since all chemicals enhanced solid content it can be concluded that they work as drainage aids, not as wet web strength additives. From all chemicals only PVAm increased the dry strength and two other chemicals even decreased the strength. As chemicals were used in strong diluted forms and were injected into the pulp slurry, not on the surface of the papersheets, changes in samples densities did not happen. Also it has to be noted that all these chemicals are mainly used to improve the wet strength after the drying of the web.

The Effects of Some Furnish and Paper Structure Related Factors on Wet Web Tensile and Relaxation Characteristics

The objective of this thesis was to identify the effects of different factors on the tension and tension relaxation of wet paper web after high-speed straining. The study was motivated by the plausible connection between wet web mechanical properties and wet web runnability on paper machines shown by previous studies. The mechanical properties of wet paper were examined using a fast tensile test rig with a strain rate of 1000%/s. Most of the tests were carried out with laboratory handsheets, but samples from a pilot paper machine were also used. The tension relaxation of paper was evaluated as the tension remaining after 0.475 s of relaxation (residual tension). The tensile and relaxation properties of wet webs were found to be strongly dependent on the quality and amount of fines. With low fines content, the tensile strength and residual tension of wet paper was mainly determined by the mechanical interactions between fibres at their contact points. As the fines strengthen the mechanical interaction in the network, the fibre properties also become important. Fibre deformations caused by the mechanical treatment of pulp were shown to reduce the mechanical properties of both dry and wet paper. However, the effect was significantly higher for wet paper. An increase of filler content from 10% to 25% greatly reduced the tensile strength of dry paper, but did not significantly impair wet web tensile strength or residual tension. Increased filler content in wet web was shown to increase the dryness of the wet web after the press section, which partly compensates for the reduction of fibrous material in the web. It is also presumable that fillers increase entanglement friction between fibres, which is beneficial for wet web strength. Different contaminants present in white water during sheet formation resulted in lowered surface tension and increased dryness after wet pressing. The addition of different contaminants reduced the tensile strength of the dry paper. The reduction of dry paper tensile strength could not be explained by the reduced surface tension, but rather on the tendency of different contaminants to interfere with the inter-fibre bonding. Additionally, wet web strength was not affected by the changes in the surface tension of white water or possible changes in the hydrophilicity of fibres caused by the addition of different contaminants. The spraying of different polymers on wet paper before wet pressing had a significant effect on both dry and wet web tensile strength, whereas wet web elastic modulus and residual tension were basically not affected. We suggest that the increase of dry and wet paper strength could be affected by the molecular level interactions between these chemicals and fibres. The most significant increases in dry and wet paper strength were achieved with a dual application of anionic and cationic polymers. Furthermore, selectively adding papermaking chemicals to different fibre fractions (as opposed to adding chemicals to the whole pulp) improved the wet web mechanical properties and the drainage of the pulp suspension.

Charta öfver Åland

1 kartta : käsinvär. ; 41,5 x 71,5 cm, lehti 46 x 74,7 cm.

Vårt land, vårt land

Laulusolisti ilmoittaa nimensä alkukuulutuksessa; kuulutus epäselvä.

På flykt i eget land : internflyktingar i Sverige under stora nordiska kriget

År 1721 stod bondhustrun Lisbeta Mickelsdotter från Pyhäjoki framför prästen i Piteå socken och redogjorde för sina upplevelser under det hemska året 1714 då ryssarna inföll i Österbotten och alla som bara kunde begav sig på flykt. Lisbeta är bara en av de tiotusentals flyktingar som under det stora nordiska kriget 1700–1721 flydde från såväl Östersjöprovinserna men framför allt från Finland till tryggheten i Sverige. I avhandlingen skildras vilka som flydde, varifrån och vart. Man kan tala om en elitens flykt där ämbetsmän och präster sökte sig västerut enligt de direktiv som Karl XII gett om att civilbefolkningen skulle söka sig bakom den egna armén. Det förekom också en bondeflykt från framför allt Österbotten och Åland. Det här var områden som p.g.a. strategiska skäl förhärjades av ryssarna. För många fanns det inget annat alternativ än att fly, antingen ut i de djupa skogarna eller västerut till Sverige. En delorsak till flykten var den order som Karl XII gett. Ryssarna föregicks av ett rykte som hade sin bakgrund i den propaganda som de svenska myndigheterna i decennier hade bedrivit. Ryssarna sågs som en grym fiende. När ämbetsverk och magistrat började packa ihop sina arkiv för en överflyttning till Sverige skedde det i smyg för att inte förorsaka oro bland den övriga befolkningen. Paniken låg hela tiden på lur och det faktum att myndigheterna gav sig av ledde till, att när ryssarna verkligen plötsligt dök upp i socknen var det många som valde att hals över huvud ge sig iväg. För att hjälpa flyktingarna ekonomiskt samlades det till förmån för flyktingarna kollekt över hela det svenska väldet. I Stockholm tillsatte myndigheterna en flyktingkommission som fick till uppgift att bland flyktingarna fördela de medel som hade samlats in. Huvudprincipen var att ju mer man hade förlorat desto större understöd skulle man få. Det var viktigt att ståndssamhället bevarades. Utanför de grupper som skulle hjälpas lämnades bl.a. köpmän och hantverkare som förväntades kunna fortsätta sin verksamhet i Sverige, gamla och orkeslösa som skulle beredas rum på fattighus samt unga och friska som skulle försörja sig genom arbete. Eftersom det var svårt att finna en försörjning och då många tvingades livnära sig genom att tigga tvingades flyktingkommissionen också ge en slant till personer som enligt kommissionens instruktion skulle lämnas utan hjälp. Det är ändå tveksamt om de små summor det stora flertalet fick egentligen hade någon betydelse för dem. Man kan konstatera att många hade det oerhört svårt under sin tid i Sverige. För mitt arbete har det viktigaste källmaterialet varit de förteckningar som flyktingkommissionen gjorde över vem som fått understöd och hur mycket som utbetalades. Av de här uppgifterna har jag byggt upp en databas med över 13 000 identifierade flyktingar. Jag har utgående från bl.a. uppgiften om identifierade individer kunnat fastställa att antalet finska flyktingar uppgick till åtminstone 30 000 personer, vilket motsvarade närmare en tiondedel av befolkningen i Finland. Efter fredsslutet 1721 återvände de flesta hem. I Österbotten möttes då en del av en överraskning då de fann att någon främmande person hade övertagit deras hemman. Det förekom under slutet av 1710-talet en inflyttning från de österbottniska finskspråkiga inlandssocknarna till de svenskspråkiga kustsocknarna. Det är ändå uppenbart att de finskspråkiga snart assimilerade sig och helt uppgick i den svenskspråkiga majoriteten.

Berättelse om Åland

Author: Samuel Ehrenmalm.

Beskrifning öfver Åland : af Fredric Wilhelm Radloff, med. doct. och provincial-medicus på Åland.

Dedicated to: Hans Maj:t Konungen.