This thesis investigated whether or not it is possible to generate and capture arynes under mechanochemical conditions. The investigation covered mechanochemical parameters, as well as parameters known to influence aryne generation in solution such as crown ether and CsF loading. Experiments were performed in steel vessels, each equipped with a single free moving steel ball in a shaker type mill. Different reactivities were probed, including nucleophilic addition, [4+2] Diels-Alder cycloaddition, [3+2] cycloaddition and Pd-catalyzed cyclotrimerization. Acquired crude product mixtures were analysed with NMR spectroscopy, and spectra were compared to reported spectra of reactants and expected products. The results showed generation and capturing of arynes to be possible under mechanochemical conditions with borylated, as well as non-borylated aryne precursors in moderate to good yields. Regioselectivity did not appear to differ from solvent conditions since only single regioisomers were observed. / Detta kandidatarbete undersökte möjligheten att generera och reagera aryner under mekanokemiska förhållanden. Undersökningen täcker mekanokemiska parametrar likaså parametrar som, sen tidigare, är kända för att påverka generering av aryner i lösning, exempelvis mängden tillsatt kron-eter och CsF. Experimenten utfördes i stålbehållare innehållandes en stålkula vardera som skakades med hjälp av en kvarn av skaktyp. Olika reaktiviteter utforskades, däribland nukleofil addition, [4+2] Diels-Alder cykloaddition, [3+2] cykloaddition och Pd-katalyserad cyklotrimerisering. Erhållna rå-lösningar analyserades med NMR-spektroskopi och erhållna spektran jämfördes därefter med tidigare rapporterade spektran av reaktanterna och de förväntade produkterna. Resultaten visade att generering av och reaktion med aryner är möjligt med både borylerade och icke-borylerade aryn-föregångare under mekanokemiska förhållanden. Regioselektiviteten hos reaktionerna under mekanokemiska förhållanden skilde sig inte från den regioselektivitet som tidigare observerats i lösning.

The goal of this work was to synthesize different dendritic architectures and evaluate the effect from the dendrons on the material properties. The work presented in this licentiate thesis, Synthesis and Characterization of Dendritic Architectures, is divided into major parts. The first part deals with the synthesis and characterization of two sets of dendritic porphyrins based on 2,2-bis(methylol)propionic acid (bis-MPA). The second part deals with the synthesis and characterization of a series of dendronized polymers based on bis-MPA. Both free-base and zinc containing dendritic porphyrins were synthesized up to the fifth generation utilizing the acetonide protected anhydride of bis-MPA. The resulting dendrimers were characterized by SEC, NMR, and MALDI-TOF. The dendrimers were found to be well-defined, virtually monodisperse, molecules up to the fourth generation. In the case of the fifth generation dendrimers, some structural defects were observed. The hydrodynamic volume (in THF) of these molecules was calculated using the rotational correlation time, and they were found to be more compact than the corresponding Fréchet-type dendrimers of the same generation. Macromonomers of the first and second generation were also synthesized utilizing the acetonide protected anhydride of bis-MPA and subsequently polymerized by atom transfer radical polymerization, using a system of N-propyl-2-pyridylmethanamine, Cu(I)Br, and Cu(I)Br2. This system resulted in well-controlled polymerizations with low polydispersity polymers. By adopting a divergent ‘graft-to’ approach, welldefined dendronized polymers with acetonide, hydroxyl, acetate, and hexadecyl functionality respectively, were obtained. The bulk properties of the dendronized polymers were investigated by differential scanning calorimetry, dynamic-mechanical measurements, and 1H-NMR selfdiffusion. It was found that that increasing the size of the pendant dendron increased the glass transition temperature of the materials. The degree of crystallization of the hexadecyl functional materials was found to decrease with dendron size, most likely due to the reduced flexibility of the backbone prohibiting effective crystallization. The dynamic mechanical measurements revealed that the behavior of the complex viscosity as a function of frequency was independent of functionality. The second and third generation materials were found to have a Newtonian plateau up to a frequency where they become shear-thinning. The fourth generation materials were found to be shearthinning in the frequency range. 1H-NMR self-diffusion measurements revealed that the shape of the acetonide functional dendronized polymers in solution was best described by using a rod-like or prolated ellipsoid model. / QC 20101216

The work was done in collaboration with Lantmännen's research foundation to produce a new and health-promoting bread. The dietary fiber beta-glucan was added to bread at a sufficiently high content to have positive health effects on blood cholesterol and blood sugar levels. The bread should also have a high sensory quality. In this project the effects of addition of beta-glucan on the theoretical GI (glycemic index) and GL (glycemic load) were investigated. An in vitro analysis was used, and the GL was calculated from the GI. These analyses were carried out on both freeze-dried bread and fresh bread containing different concentrations of beta-glucan. A sensory analysis was also done to see if there was any difference between the control bread and the bread containing the beta-glucan. The purpose of the work was to investigate how the theoretical GI value and the theoretical GL value are affected by two different preparations of beta-glucan (with concentration of 32% respectively 75% beta-glucan) in bread with end concentrations of 0.2 and 2.0 % beta-glucan of the total quantity of flour. The result indicates that there is significant effect on GI and GL of beta-glucan in wheat-based bread. Between the reference bread and the 0.2% bread of the freeze-dried bread, a significant difference was seen with a p-value of 0.048 in a paired t-test. It also was a significant difference between the reference bread and the 2.0% bread with a pvalue of 0.014 in a paired t-test. The GI values were calculated to 65 and 63 respectively for 0.2 and 2.0% beta glucan for the freeze-dried bread. The GI value for the fresh bread were calculated to 68 and 52 respectively for 0.2 and 2.0% beta glucan. The GL-values for the fresh-bread were calculated to 79 and 60 respectively for 0.2 and 2.0% beta glucan. The GL-values for the freeze-dried bread were calculated to 38 and 37 respectively for 0.2 and 2.0% beta glucan. A significant difference was seen between the reference bread and thefresh bread containing 2% added betaglucan (p-value = 0.002using t-test). The fresh bread with 0.2% added betaglucan had at about the same GI value as the reference bread and a significant difference could not be seen (p = 0.7642). In other studies, whole grain flour and a dietary fiber content of 15-45 g / serving have been shown to have an effect on the GI and GL values. The desired result is to have attenuated effects on blood sugar levels in the blood after food intake and thus be able to achieve prerequisites for blood sugar claims. To achieve the desired effect a whole-wheat flour should be used to raise the dietary fiber content and reduce the proportion of wheat flour and glucose available.

Using and finding applications from biomass is and will continue to be an important subject forresearch, and biomass from trees, has shown several outstanding aspects other than just for the pulpand paper applications. It is now, more than ever, time to find efficient uses for all the woodcomponents, in particular, the hemicelluloses. The hemicelluloses account for approximately onethirdof a dry composition of lignocellulosic wood biomasses. Of these hemicelluloses, xylan is themost abundant in many plants, particularly in hardwood. As for the Swedish forestry, xylan frombirch is considered as one of the most promising resources for the future.This thesis investigates the impact of acetylation of xylan on some properties such as solubility,thermal stability and film formation. Films were prepared using the non- and acetylated xylan withaddition of different plasticizers (glycerol, sorbitol and xylitol).Alkali-soluble birch xylan (ASX), obtained by ethanol/toluene extraction and sodium chloritedelignification of the wood sawdust followed by potassium hydroxide extraction of the obtainedholocellulose, and commercial xylan (CX) were acetylated to different degree of substitution withacetyl groups (DSAc), using acetic anhydride in dimethyl sulfoxide (DMSO) and 1-methylimidazole(NMI). Films were prepared by suspending non-acetylated xylan in water (H2O) and adding differentpercentages of plasticizers (20 and 40%) or by suspending acetylated xylan in chloroform (CHCl3).Characterizations of the non- and acetylated polymer (AcASX and AcCX) and films were conducted inorder to determine thermal and mechanical properties.CX and ASX presented different reactivity leading to different behaviour during acetylation and sodifferent DSAc. The thermal stability has been improved for both ASX and CX following the increase ofthe DSAc. Concerning film formation, ASX showed a great ability to form films through casting with orwithout plasticizers while it was impossible to obtain any films using only CX. For AcASX and AcCX thefilm formation using chloroform was depending on the DSAc and the dispersability in the solvent. Allthe films obtained have been mechanically and thermally tested. Best results for the mechanicaltests were obtained with 40% plasticizers with creation of a plastic behaviour and improvement ofthe flexibility. Thermally speaking, the thermal stability gained through acetylation of the samples islost by film casting, and use of plasticizers reduced the thermal stability as a new component wasadded to the composition. / Att använda och hitta tillämpningar från biomassa är och kommer att fortsätta att vara ett viktigtämne för forskning, och biomassa från träd har visat flera goda aspekter annat än bara för massaochpappersapplikationer. Det är hög tid att hitta effektiva användningar för alla träkomponenter, isynnerhet hemicelluloserna. Hemicelluloserna står för ungefär en tredjedel av en torrsammansättning av lignocellulosa. Av dessa hemicellulosor är xylan den vanligaste i många växter,särskilt i lövträ. När det gäller det svenska skogsbruket anses xylan från björk vara en av de mestlovande resurserna för framtiden.Denna avhandling undersöker effekterna av acetylering av xylan på vissa egenskaper, såsomlöslighet, termisk stabilitet och filmbildning. Filmer framställdes med användning av den icke-ochacetylerade xylanen med tillsats av olika mjukningsmedel (glycerol, sorbitol och xylitol).Alkalöslöslig björkxylan (ASX), erhållen genom etanol / toluenutvinning och natriumkloritfördelningav träsågspån följt av kaliumhydroxidutvinning av erhållen holocellulosa och kommersiell xylan (CX)acetylerades till olika grad av substitution med acetylgrupper (DSAc), med användning avättiksyraanhydrid i dimetylsulfoxid (DMSO) och 1-metylimidazol (NMI). Filmer framställdes genom attsuspendera icke-acetylerad xylan i vatten (H2O) och tillsätta olika procentdelar mjukningsmedel (20och 40%) eller genom att suspendera acetylerad xylan i kloroform (CHCI3). Karakteriseringar av denicke-och acetylerade polymeren (AcASX och AcCX) och filmer utfördes för bestämning av te rmiskaoch mekaniska egenskaper.CX och ASX presenterade olika reaktivitet vilket ledde till olika beteenden under acetylering och såolika DSAc. Den termiska stabiliteten har förbättrats för både ASX och CX efter ökningen av DSAc. Närdet gäller filmbildning uppvisade ASX en stor förmåga att bilda filmer genom gjutning med eller utanmjukningsmedel medan det var omöjligt att erhålla några filmer med endast CX. För AcASX och AcCXvar filmbildningen med användning av kloroform beroende av DSAc och dispergerbarheten ilösningsmedlet. Alla filmer som erhållits har testats mekaniskt och termiskt. Bästa resultat för demekaniska testerna erhölls med 40% mjukningsmedel med skapandet av ett plastiskt beteende ochförbättring av flexibiliteten. Termiskt sett förloras den termiska stabiliteten som erhållits genomacetylering av proverna genom filmgjutning, och användning av mjukningsmedel reducerade dentermiska stabiliteten som en ny komponent tillsattes till kompositionen.

The cleaning technology for exhaust air is an area under constant development. In collaboration with Ozone Tech Systems the project resulted in a lab scale test rig for air cleaning units. The test rig was designed primarily to investigate the mechanisms of an UV reactor as well as the life times of a hydrogen sulphide absorption bed and an activated carbon bed. The thesis consisted in the design of the system, the acquisition of units and the construction of the system followed by the modelling of the pollutant elimination in the UV reactor. Fluid dynamics of the process flow is neglected, while the light distribution is numerically calculated. Two separate pollutants were considered, one being volatile organic compounds represented by acetaldehyde, and the other being hydrogen sulphide, chosen due to their prevalence in exhausts. An experimental plan is developed to validate the model, find model parameters and finally to investigate process parameters in the UV reactor. / Luftföroreningar är ett mycket aktuellt problem, och tekniken för att rena luftströmmar är under ständig utveckling. I samarbete med Ozone Tech Systems designades och byggdes en testrigg för att undersöka olika luftreningsenheter. De primära målen var att undersöka mekanismerna i en UV reaktor samt livslängden för två lika packade bäddar; en absorptionsbädd för divätesulfid samt en adsorptionsbädd av aktiverat kol. Examensarbetet bestod av designmomentet, införskaffande av rätt enheter och konstruktionen av systemet. Även numerisk modellering av UV-reaktorn ingick i projektet, och denna gjordes med störst avseende på UV-ljusets fördelning i reaktorn medan flödesdynamiken försummades.Två olika föroreningar valdes p. g. a. deras frekventa förekomst i luftströmmar som ska renas; divätesulfid och flyktiga organiska ämnen (representerade här av acetaldehyd). Rapporten presenterar även en experimentell plan för att validera modellen, hitta modellens semiempiriska parametrar, samt till slut för att med hjälp av faktoriell design undersöka interaktionen mellan olika faktorer i UV-reaktorn.

As the mission to the decrease global warming and phase out highly pollutingenvironmental practices globally, regulations including Euro 6 and policies generated by theUnited Nations Framework Convention on Climate Change (UNFCCC) are pushing companiesto be more innovative when it comes to their energy sources. These regulations involve manyfactors related to the cleanliness of the fuel and produced emissions, for example, propertiesof the fuels such as sulfur content, ash content, water content, and resulting emission valuesof Carbon dioxide (CO2) and Nitrogen Oxides (NOx). Furthermore, Sweden has set achallenging target of a fossil-fuel-independent vehicle fleet by 2030 and no net greenhousegasemissions by 2050.One way to cut down on the polluting properties in the fuel, as well as weakening thedependence on fossil fuel based fuel includes utilizing higher blending ratios of biofuels in thetransport sector. This transition to biofuels comes with many challenges to the transportindustry due to higher concentrations of these new fuels leads to clogging of the filters in theengine, as well as, internal diesel injector deposits (IDIDs) that produce injector fouling. Thisclogging of the filters leads to lower performance by the engines which leads to higher repairtimes (uptime) and less time on the road to transport goods. The formation of these softparticles at the root of the clogging issue is a pivotal issue because the precise mechanismsbehind their formation are highly unknown. Scania, a leader in the Swedish automotiveindustry, is very interested in figuring out what mechanisms are the most influential in theformation of these particles in the engine. Understanding the key mechanisms would allowScania to make appropriate adjustments to the fuel or the engines to ensure more time onthe road and less maintenance.There are many conditions known to be possible causes of the formation of softparticles in engines such as water content, ash content, and temperature. After generatingsoft particles using a modified accelerated method, particles were analyzed using infraredtechnology (RTX-FTIR) and a Scanning Electric Microscope (SEM-EDX). Many differentexperiments were performed to be able to make a conclusion as to which mechanisms weremost influential including temperature, time, water, air, and oil. The combination of agingbiofuels (B100, B10, HVO) with metals, and water produced the largest amount of particlesfollowed by aging the biofuels with aged oil, metals, and water. Aging the fuels with aged oilincreased particles, meanwhile the addition of water prevented particle production possiblydue to additives. B100 produced the highest amount of particles when aged with Copper, B10with Brass, and HVO with Iron.

No description available.

The annual increase in waste car tires in addition to the enormous amount at present poses a major waste management problem as well as an environmental hazard. However, pyrolysis is emerging as a solution for waste tire management and a viable technology for material recycling and energy recovery that produces high energy liquid and gas products as well as char. The pyrolysis oil that is produced from this technology has the potential to be used as vehicle fuel but contains exceeding levels of sulfur and other impurities. This study investigates the upgrading and desulfurization of waste tire pyrolysis oil by reactive adsorption using a molybdenum modified zeolite and its desilicated form. The experiments were performed at 320 °C and a LHSV of 45-50 h-1 for approximately 45 min, and revealed that both desilication and Mo-modification resulted in the cracking of both gaseous and liquids compounds, reduction of TAN, denitrogenation, and deoxygenation. Desilication increased desulfurization while Mo-modification increased the EHI. The treatment was the most effective in the removal of oxygen, followed by nitrogen and sulfur. In conclusion, the treatment process is promising as a method for direct liquid upgrading but requires further research.

The study has been conducted in collaboration with Swestep AB, a Swedish company that specializes in the conversion of waste to valuable products via the KDV technology. The study explores the possibility of using cassava chips and cassava pulp as a potential feedstock in the production of synthetic diesel and compares the KDV method with fermentation, a conventional method of using cassava chips and cassava pulp in Thailand. To obtain the carbon yield, amount of product and system efficiency, a mass and energy balances were first performed on wood feedstock data provided by the company. The balances were thereafter used as a basis for a simulation analysis of the cassava feedstock. The diesel product yield is produced through a KDV 150 plant using 551kg/h of the different feedstock; wood, cassava chips and cassava pulp resulting in different amounts of diesel product 150 L/h, 116.79 L/h and 121.31 L/h, respectively. For cassava, the C yield in diesel is 0.41 while the C yield of ethanol production is 0.14, since C in the ethanol production is converted into other matters. Besides, the system efficiency of the KDV plant with different types of feedstock is around 0.84 because some parts of the KDV plant is self-supplied whereas the ethanol production plant (55% of system efficiency) is not. Economical evaluations of the KDV 5000 and ethanol production plant were performed. The KDV 5000 with cassava pulp as feedstock produces 31 ML/year and is feasible for investment in Thailand due to the low price of the feedstock which is driving the operation cost (15.167 baht/L or 0.46 USD/L). This is lower than the selling price (21.329 baht/L or 0.65 USD/L) whereas the KDV 5000 plant with cassava chips is not feasible. The KDV plant with cassava pulp as a feedstock will reach the breakeven point after running for 7 years. The ethanol production process with cassava chip as feedstock produces 49 M liter/year and has an operation cost of 19.693 baht/liter (0.6 USD/L) which is higher than the KDV plant due to the feedstock price. The selling price of ethanol is 23.11 baht/l (0.705 USD/L) which resulted in the process reaching the breakeven point after 14 years.

Sveriges riksdag har tagit fram 16 miljömål där ett av dem ämnar att minska övergödningen isvenska sjöar och vattendrag. Övergödning är bland annat ett resultat från näringsämnen somläckt från jordbruk. En lösning på övergödningsproblemet skulle kunna vara att samla upp deläckta näringsämnena och återföra dem till åkern. Detta skulle kunna göras med hjälp av biokolsom adsorbent och syftet med detta projekt är att undersöka dessa möjligheter samt biokoletsstruktur. Definitionen på biokol är att det är en heterogen kolliknande substans från hållbart framtagenbiomassa. Den ska även ha ett högt kolinnehåll och användas på ett sådant sätt att den binderupp kolet under en längre tid. Biokol framställs genom pyrolys eller förgasning under högtemperatur och syrefattiga förhållanden. Syftet med användande av biokol som adsorbent ärmöjligheten att kunna skapa ett kretslopp. Biokolet ska först verka som filter i avrinningsdikenvid åkermark för att sedan återföras, mättad med näringsämnen, tillbaka till åkermarken. Vid experimenten användes tre olika kol. Ett grillkol och två olika biokol. Strukturen på deolika kolen undersöktes med en BET-analys. Analysen av grillkolen gav ett orimligt svar menför de två biokolen gavs resultat som ansågs rimliga. Denna analys ger inte ett direkt värde påadsorptionsförmåga hos kolen utan behöver verifieras med ett experimentellt framtagetsamband mellan struktur och adsorptionsförmåga. Ett alternativ till BET-analysen är att göraen jodnummeranalys, som ger värden på adsorptionsförmåga för det undersökta ämnet. Denna analys utfördes inte praktiskt. Två lösningar med olika koncentrationer av Na3PO4 förbereddes och blandades underomrörning med de olika kolen. Två olika omrörningstider användes för att kunna undersökauppehållstidens betydelse. Efter omrörning filtrerades proverna för att få bort kol och de olikafiltraten genomgick en ICP-analys för undersökning av fosforinnehåll. Resultatet som framkomav denna analys var att filtraten hade en högre fosforhalt än vad de initiala lösningarna hade.Förklaringen till detta antas vara att biokolet redan innehöll fosforföreningar som Na3PO4 ut. Problemet med ICP-analysen var att den inte kunde detektera i vilken form fosforn var.Det gick heller inte att detektera kväve i ICP-analysen då luften runt omkringinstrumentet innehåller kväve vilken kontaminerar provet och detekteras i analysen. Enalternativ metod till ICP är att använda spektroskopi som dels kan detektera kväve men ävenolika former av fosfor- och kväveföreningar. Slutsatsen var att analys av biokols adsorptionsförmåga är att den är komplex. BET-analys ären bra metod för att visa struktur på kolen men jodnummer kan vara ett bättre alternativ för attdirekt hitta ett värde på kolets adsorptionsförmåga. För analys av lösningar fungerar ICP enbartför fosfor och därför skulle spektroskopi kunna vara ett bättre alternativ då det kan detekterakväve samt olika former av föreningar. / The aim of this project is to create a deeper understanding of biochar’s ability to adsorbnutrients. In the long run the aim is to find a way to use the most suitable structures of biocharfor a maximum adsorption of different kinds of nutrients. The objective of this project is tofind, through case studies and practical experiments, an effective method to examine andanalyze the structure of biochars and their ability to adsorb nitrates and phosphates. The conclusion of the project was that analysis of the biochar’s ability to adsorb is a complexmatter. The BET-analysis is a good method to find the structure of the biochar. However, iodinenumber analysis could be a better alternative to directly find a value on the biochar’s ability toadsorb. The ICP-analysis of the solutions only works for phosphor, therefore spectroscopywould be a better alternative since it also can detect nitrogen and the different compounds.