I rapporten framgår det en termodynamisk analys för reverse water gas shift med att sammanmata etanol för att undvika det långsammaste steget i reaktionen för att producera högre alkoholer. Ifrån ett termodynamiskt perspektiv, verkar det möjligt att utgå ifrån reverse water gas shift för att producera högre alkoholer vid 100 bar med en temperatur på 300C . Reaktionen är exotermisk, vilket gynnas av det låga temperaturer och det rekommenderas höga tryck p.g.a. en mol kontraktion. Jämviktshalterna var låga, det föreslås att ta bort vatten ifrån jämvikten.  I den matematiska modellen utgick det ifrån en kedja-reaktion för att producera högre alkoholer med reverse water gas shift i processförhållanden på 10–200 bar. I modellen utfördes en senstivty-analysis för jämvikten på tryck och vattenborttagning. Genom att ta bort vatten ifrån jämvikten låg CO2 utbytet kring 95% vid 200 bar även vid låga tryck som 10 bar. Inom CO2 hydrering till högre alkoholer är det begränsat med data och reaktionsmekanismen bakom reaktionen är inte riktigt förstådd. Experimentella försök krävs för att få en mer ökad förståelse. I modellen beskrevs CO2 hydrering och resterande reaktioner som en funktion av en sigmoid. Inom litteraturstudien kom det fram till att det fanns ingen kommersiell tillgänglig membran förtillfället för att ta bort vatten inom krävande process förhållanden. Tekniken ser dock lovande ut. / In this work, a thermodynamic analysis for CO2 hydrogenation by co-feeding ethanol to higher alcohols was performed with the HSC software package. The results suggested a high pressure and a low temperature for the reaction. However, it yielded low equilibrium compositions for the higher alcohols even at a high pressure of 100 bar at 300C . Increasing the equilibrium compositions for the higher alcohols can be done by removing water.  A mathematical model was used to analyse the rate-limiting step in a process for the production of higher alcohols from CO2.  In this process, reverse water gas shift (RWGS) reaction was used to convert CO2 to CO, subsequently, the obtained CO reacts with ethanol and hydrogen to produce higher alcohols directly. The mathematical model was developed in MATLAB to simulate how the reaction could behave by feeding CO2, H2 and ethanol at different pressures ranging from 10-200 bars. The water removal effect on the equilibrium is measured in terms of CO2   conversion by achieving 95% for removing water.  The results indicated that the process can be used to convert CO2 to higher alcohols and at a lower pressure. The limiting factor for CO2 hydrogenation is the reaction mechanism, it’s an urgent problem for the development of the catalysts. In this model it was assumed to be a logistic function. The conversion of CO2 into higher alcohols is an important problem that is required to be addressed by more experimental verifications to understand the mechanism. The literature review shows that there is no available membrane for removal of water for the process currently, due to the harsh process conditions, mainly because of the membrane stability. However, membrane technology is a promising method for separation of water/organic mixtures that can be studied further in the future.

Rexcell Tissue & Airlaid AB is a producer of paper products such as coloured tissue, where it is important to manufacture a product that does not release any colour during usage. To prevent colour bleeding, a fixative is added during the paper dyeing process. However, excessive fixative can cause issues to the papermaking process due to its charge. Currently, charge measurements on the water flow are used to detect fixative overdose, but a more precise method is desired. This study explores using FTIR spectroscopy and existing charge measurements (PCD and Z-potential) to analyse process water for different dye types (Red, Black, Green). The ATR-FTIR technique shows that fixative is detectable only at higher concentrations than present in the water. By reducing the process water to measurable fixative levels, concentration determination is possible using IR peaks associated with the amine bond. Comparing concentration values with charge values, a good agreement is observed for two dye types, but the green whitewater shows discrepancies. This could be due to the charged dye molecules influencing the fixative spectrum, affecting concentration determination. The study suggests using an ATR crystal allowing multiple reflections to enhance the fixative signal for accurate concentration measurement. Further investigation is needed to understand the impact of coloured molecules on fixative properties and the FTIR spectrum. In summary, it is feasible to determine fixative concentration in whitewater using FTIR-ATR, but refining the methodology is essential for reliable results

Transformers are electrical devices used in practice to increase or decrease voltages. Transformers are of various sizes and used mainly in power distribution. To provide cooling and insulation, transformer oils are used together with cellulose that acts as a solid insulation. The most common type of transformer oil is mineral oil and is a product derived from the refining of crude oil. Its low cost and good compatibility with cellulose are two factors that have led to its predominant position as the common transformer oil. There are also synthetic ester based transformer oils, and following an increased interest in environmentally friendly products, transformer oils made from natural esters such as sunflower, soybean and rapeseed. Mineral oil is not biodegradable and is deemed as hazardous waste. The ester based oils are biodegradable and promoted as a more environmentally friendly alternative to mineral oil. In this thesis, the possibility of re-refining used mineral transformer oil is assessed from a financial perspective in the form of a business case and an LCA study has been done to compare the environmental impacts between ester based transformer oils and mineral based transformer oil. The results from the LCA study showed that from a cradle-to-gate perspective, mineral oil has a lower environmental impact than ester-based transformer oils. The re-refining of used mineral transformer oil further reduces the environmental impact. The results from the business case showed that a small scale re-refining facility is financially feasible but highly dependent on the supply and demand of used transformer oil. It is recommended to pursue further studies before making any decision. There is lack of data regarding the re-refining market in Eastern Europe and the accuracy of the LCA study can be further improved by having emissions data from re-refining used mineral transformer oil. / Transformatorer är elektriska komponenter som tillämpas vid spänningsregleringar. Dessa transformatorer har olika storlekar och används i eldistribution. Transformatorolja tillsammans med cellulosa används som elektrisk isolering och kylning av transformatorer. Den vanligaste typen av transformatorolja är mineralolja och är en produkt som erhålls vid raffinering av råolja. Dess låga kostnad och goda kompatibilitet med cellulosa är två faktorer som har lett till dess dominerande ställning. Det finns också syntetisk esterbaserad transformatorolja och efter ett ökat intresse för miljövänliga produkter så tillverkas även transformatoroljor av naturliga estrar så som solros, soja och raps. Mineralolja är inte nedbrytbar och anses vara farligt avfall. De esterbaserade oljorna är nedbrytbara och anses vara ett mer miljövänligt alternativ till mineralolja. I denna rapport utvärderades möjligheten till att återraffinera använd mineralolja ur ett ekonomiskt perspektiv i form av en affärsplan och en LCA-studie där esterbaserad olja och mineralolja har jämförts ur ett miljöperspektiv. Resultaten från LCA-studien visade att mineralolja från ett ”cradle-to-gate” perspektiv har en lägre miljöpåverkan än esterbaserade transformatoroljor. Återraffinering av använd mineralolja minskar dess miljöpåverkan ytterligare. Resultatet från affärsplanen visade att en småskalig återraffineringsanläggning är ekonomiskt hållbar men samtidigt väldigt beroende av utbud respektive efterfrågan på använd mineralolja. Det rekommenderas att göra en djupare analys innan man fattar ett beslut. Det finns brist på information med avseende på återraffineringsmarknaden i Östeuropa. Noggrannheten på LCA-studien kan förbättras ytterligare genom att emissionsdata från en återraffineringsanläggning är tillgänglig.

Uganda is well endowed with economic quantities of salt evident in the interstitial brines and evaporite deposits of Lake Katwe, a closed saline lake located in the western branch of the great East African rift valley. Currently, rudimentally methods of salt mining based on solar evaporation of brine continue to be used for salt extraction at the lake. These have proved to be hazardous and unsustainable to the salt miners and the environment. In this work, literature concerning the occurrence of salt and the most common available technologies for salt extraction is documented. Field studies were undertaken to characterize the salt lake deposit and to devise strategies of improving salt mining and extraction from the salt lake raw materials. The mineral salt raw materials (brines and evaporites) were characterized to determine their physical, chemical, mineralogical, and morphological composition through field and laboratory analyses. In addition, laboratory extraction techniques were undertaken to evaluate possibilities of future sustainable salt extraction from the lake deposit. Also, PHREEQC simulations using Pitzer models were carried out to determine the present saturation state of the lake brine and to estimate which salts and the order in which they precipitate from the brine upon concentration by evaporation. Results reveal that the raw materials from the salt lake contain substantial amounts of salt which can be commercialized for optimum production. The brines are highly alkaline and rich in Na+, K+, Cl-, SO42-, CO32-, and HCO3-. Moreover, they contain trace amounts of Mg2+, Ca2+, Br-, and F-. The lake is hydro-chemically of a carbonate type with the brines showing an intermediate transition between Na-Cl and Na-HCO3 water types. The evaporites are composed of halite mixed with other salts such as hanksite, burkeite, trona etc, with their composition varying considerably within the same grades. The laboratory extraction experiments indicate that various types of economic salts such as thenardite, anhydrite, mirabilite, burkeite, hanksite, gypsum, trona, halite, nahcolite, soda ash, and thermonatrite precipitate from the brine of Lake Katwe. The salts crystallize in the order following the sequence starting with sulfates, followed by chlorides and carbonates, respectively. Moreover, thermodynamic modeling in PHREEQC accurately predicted the solubility and sequence of the salt precipitation from the lake brine. Understanding the sequence of salt precipitation from the brine helps to control its evolution during concentration and hence, will lead to an improved operating design scheme of the current extraction processes. The work providesinformation towards future mineral salt exploitation from the salt lake. / <p>QC 20131129</p>

In the time line of world industrial age, the most important era begins in the late 18th century when the use of fossil fuels was growing intensively. This approach has continued and developed up to the 20th century. Besides, this trend has had side effects like polluting environment. Air pollution is one of the critical issues nowadays that stems from using hydrocarbon fuels. One type of the problematic compounds in polluting air is nitrogen oxides that can be produced in combustion process from engines and industrial plants. Different solutions have been suggested to remove air polluting compounds. One method for removing nitrogen oxides is using the mechanism of Selective Catalytic Reduction in silencer of engines. This method has become practical in trucks’ engines. Therefore, research on SCR chemistry is important for improving the usage of this method in removing nitrogen oxides. SCR has its own problems when used in trucks. One of the problems is formation of white clumps on pipe wall of silencers using SCR which can cause back pressure in the engines and costs a lot to remove them from engines.  This report evaluates the effect of alternative fuels on SCR chemistry .Different parameters affecting deposit formation are studied and evaluated. Ethanol is one of the controversial fuels used in engines and acetic acid is one its byproducts. Also, urea and its by products are important materials in SCR chemistry, too. Consequently, the first part of the report studies the influence of acetic acid and Ferrite steel, one of the usual steels in silencers of engines, on urea, biuret and cyanuric acid decomposition. The instruments used in the first part include TGA-DSC (Thermo Gravimetric Analysis-Differential Scanning Calorimetric) which is connected to FTIR (Fourier Transform Infrared Spectroscopy).In the second part of the report, the effect of diesel exhaust and ethanol exhaust on cyanuric acid evaporation rate is evaluated. Cyanuric acid is the main compound forming deposit in silencers. The instrument used in the second part is TGA. The third part consists surveying effect of Adblue, aqueous solution of urea, and additivised Adblue, surfactant added Adblue to improve its efficiency, in a patented rig that is scaled down of a silencer of truck. The most important result for the first part includes the effect of Ferrite steel treated with acetic acid that accelerated the decomposition of cyanuric acid. This result can be investigated more in order to be used in silencers to accelerate the decomposition rate of clumps formed. In the second part, it is found out that cyanuric acid evaporates faster under ethanol exhaust than diesel exhaust. The third part’s results shows that in the current assembly of pipes in the rig, Additivised Adblue loses its improved efficiency which is an interesting result for engine welding in order to avoid this type of connection in engines.

This project aims to evaluate the technical feasibility of an absorption process for carbon capture and storage (CCS). Currently, the CCS process commonly used in the industry is energy and cost-intensive, making its large-scale development a difficult task. The process under evaluation in this project is labeled as an intensified CCS process as it is more energy-efficient, theoretically, compared to the current standard process. The intensified process is based on absorption with aqueous K2CO3/KHCO3 followed by cristallization of KHCO3. The project aims to show the technical feasibility of two parts of the intensified process, the cooling crystallization in the reactor and the regeneration of carbon dioxide through calcination. The cooling crystallization was conducted at different cooling rates for two different solution compositions, while the calcination was conducted the same for all tests. Microscopic images were utilized to examine the relationship between cooling rates, solution composition, crystal size, and clustering. Thermogravimetric analysis was used to simulate the calcination and to analyze the crystals' decomposition and purity. The report concludes that none clustered selective crystallization of potassium bicarbonate and the total regeneration of carbon dioxide through calcination were achieved. A conclusive correlation between cooling rates and crystal yields could not be proven. And the relationship between crystal size and cooling rates substantially deviated from what was expected. Based on the results the intensified process is deemed technically feasible. / Syftet med detta projekt är att utvärdera den tekniska genomförbarheten av en “carbon capture and storage” (CCS) absorptionsprocess. CCS-processen som nuvarande förekommer i industrin är både energi- och kostnadskrävande, detta förhindrar möjligheten till vidare uppskalning. Processen som utvärderas i detta projekt kallas för en intensifierad CCS-process vilket innebär att den är teoretiskt mer energieffektiv jämfört med nuvarande standardprocess. Den intensifierade processen är baserad på absorption med en K2CO3/KHCO3 vattenlösning följt av en kristallisation av KHCO3. Projektet ämnar att visa den tekniska genomförbarheten av specifikt två delar av den intensifierade processen, kylningskristalliseringen i reaktorn samt regenereringen av koldioxid genom kalcinering. Kylningskristalliseringen genomfördes med olika kylningshastigheter för två olika lösningskompositioner medan kalcineringen utfördes likadant för samtliga tester. Mikroskopiska bilder nyttjades för att undersöka förhållandet mellan kylningshastigheten, lösningens sammansättning, kristallstorlek och kristallkluster. Termogravimetrisk analys användes för att efterlikna kalcineringen samt analysera kristallernas sönderdelning och renhet. Rapporten fastställer att selektiv kristallisering av kaliumbikarbonat uppnåddes utan signifikant kluster. En definitiv korrelation mellan kylningshastighet och kristallutbyte kunde ej påvisas. Förhållandet mellan kristallstorlek och kylningshastighet avvek betydande från vad som förväntades. Baserat på resultaten bedömdes den intensifierade processen vara tekniskt genomförbar.

The effects of global warming are well understood. In order to combat this, society must move towards net zero emissions of green house gases, where carbon dioxide (CO2) plays a key role. In several IPCC climate scenarios that meet the Paris agreement, negative emission technologies that effectively remove CO2 from the atmosphere are included. Of several different technologies, bioenergy with carbon capture and storage (BECCS) is one of the most mature. This technology utilises an absorption-desorption process where CO2 is solved in liquid, producing a rich solvent, and later desorbed, resulting in pure CO2. There are, however, still challenges to implement this technology on a large scale, and one such issue is the monitoring of process streams to gain control over process conditions and system parameters.  In this project, the absorption solvent in BECCS processes were mimicked in order to determine if FTIR spectroscopy could be used to produce process parameters that are accurate, sensitive and robust. Accuracy and sensitivity are defined as the ability to correctly predict the presence and amount of species of interest in the absorption liquid. Robustness on the other hand is defined as the ability to produce precise measurements in the presence of pollutants. To evaluate how accurate and sensitive the measurements are, two different numerical models were developed and calibrated using prepared samples mimicking an absorption solvent. One model was solely based on the least square method, whereas the other was based on principal component analysis (PCA). These models were then tested on clean validation samples, as well as pilot plant samples from Stockholm Exergi, in a case study. An analysis of FTIR spectra from simulated absorption liquids showed that it could distinguish between the species of interest. Furthermore, the spectra showed that pollutants did not impact the readings in a major way. The results showed that both models produced accurate predictions of process parameters.

Sandvik Materials Technology tillverkar varje år cirka 230 000 ton stål varav en stor del är rostfritt stål. För att sänka kolhalten i stålet används en AOD-konverter där en kombination av syrgas och inertgas blåses in stålet för att avlägsna kol som kolmonoxid. Vissa duplexa rostfria stålsorter är trögfärskade vilket lätt leder till att konvertern blir flaskhalsen i stålverket. Syftet med arbetet är att undersöka och kartlägga parametrar som påverkar färskningstiden för trögfärskade duplexa stålsorter. Tiden i konvertern kan variera kraftigt mellan olika charger och det finns därför en ekonomisk drivkraft i att förkorta färskningstiden. Kolfärskningen i AOD-konvertern bygger på drivkraften hos kol att reagera med syre. Genom att använda blåssteg med ökande andel inertgas kan partialtrycket av CO-gas i stålet sänkas vilket gynnar oxidationen av kol. Vid färskning av rostfria stål som innehåller höga halter krom oxideras både kol och krom på grund av hög affinitet för syre. En liten slaggvolym kan anses som gynnsamt för färskningen då en mindre mängd kromspineller kan bindas till slaggen. Parametrarna har undersökts genom statistik från historiska charger samt genom ytterligare provtagningar under färskningsförloppet. De parametrar som undersökts är ståltemperatur, tid i överföringsskänk, mängd justeringar, antal dysor och gasflöde, operatör, stålsammansättning och slaggens inverkan. Det är ett stort antal parametrar som påverkar färskningen och det är svårt att avgöra vilken eller vilka som påverkar mest. Utifrån resultatet kan det ses att de undersökta parametrarna påverkar resultatet på olika sätt; en hög temperatur in i konvertern är gynnsam lika som en kort tid i överföringsskänken och en stålsammansättning nära riktvärdet. Många av parametrarna är dessutom beroende av varandra så som att stålsammansättningen påverkas av justeringarna och temperaturen påverkas av tiden i överföringsskänken. Slaggens inverkan på färskningen studerades utifrån typen och mängden slaggbildare. Resultaten visar att kromspineller bildas i slaggen oberoende av vilken slaggbildare som används. För chargen med slaggbildare 1 var det tydligt att det fanns fri kalciumoxid i slaggen vilket tyder på att slaggen är mättad på kalciumoxid. En mättad slagg kan leda till bildandet av en större mängd spineller vilket kan leda till en längre färskningstid. När slaggbildartillsatsen förändrades och tillsattes under steg 2 visar resultatet att 5/10 charger når en kolhalt under riktvärdet vid prov 54. Slutsatser som kan dras är att det är viktigt att fokusera på de parametrar som har en stor påverkan på färskningstiden men samtidigt är möjliga att påverka. Det kan vara att använda fler dysor och på så sätt öka gasflödet, minska slaggvolymen eller undvika att stålet förvaras långa tider i överföringsskänken.

Since their introduction by Sony in 1990, lithium-ion batteries (LIBs) have acquired a sizable market share. They have the best energy densities, a high open circuit voltage, a low self-discharge rate, no memory effect, and a slow loss of charge when not in use. These properties make them the most popular rechargeable batteries for portable gadgets, electric vehicles and aerospace applications.  They do, however, pose major safety issues since the electrolytes are made up of fluorinated salts dissolved in volatile organic solvents, the former being meta-stable at ambient temperature and the latter being flammable a with high vapour pressure. Thus, there is an urge to develop thermally and electrochemically stable non-fluorinated electrolytes to improve the safety and performance of batteries. Electrolytes based on ionic liquids (ILs) in general offer a range of suitable advantages including low volatility and high thermal and electrochemical stabilities,and can additionally be made fluorine-free. In general, their physicochemical properties are determined by the interactions between the cations and anions, which are controlled by the chemical functionalities present, with vast freedom in structural design to reduce these interactions and enhance also the ion mobilities.  In this study, favoring from of “structural design” three different families of fluorine-free ionic liquids-based electrolytes are designed and created. These families of ILs comprising n- tetrabutylphosphonium, imidazolium, pyridinium based cations and pyridine, pyrazine and ether functionalized salicylate-based anions. The structures and purity of these new ILs are characterized by using multinuclear NMR, FTIR and mass spectrometry. Several features and properties of the novel electrolytes are investigated; thermogravimetric analysis, differential scanning calorimetry, ionic conductivity and electrochemical stability. These studies are further complemented by using PFG NMR diffusometry to understand the possible interaction mechanisms between the oppositely charged ions within the electrolytes, and especially, the influence of Li+ addition in the IL-based electrolytes.

Calcination is important for modern society as we know it since products from the reaction is used inseveral industries. Calcination is a chemical reaction where a solid particle, e.g., limestone, is exposedto high temperature which causes volatile impurities to be released from the particle.One of the main challenges with lime production is the mere scale of commercial production. Ensuringgood calcination and high-quality lime in laboratory scale is relatively easy, whereas commercial limekilns produce 100 – 800 tons lime each day, causing the conditions to be much more challenging. Theenvironment inside a lime kiln is extreme, with temperatures exceeding 1200°C, and a moving stonebed makes measurements difficult to perform. To obtain information about the calcination processand the extreme environment that arises in commercial lime kilns, companies and researchers havedeveloped simulation programmes to evaluate how changes in ambient condition affect the calcinationprocess.In this project, a shrinking core model has been used to simulate calcination of limestone with variedgeometry and size in different ambient condition. A transient model was used to simulate the heatingphases before and after the calcination phase. The results obtain from the simulation are compared tomeasured data obtain by others.There are many similarities between the measured data and the simulation, a reoccurringphenomenon is that the transit model, during the pre-heating, heats the limestone faster compared tothe measured data. However, in one case, the transient model is slower. A reason for this may be thatthe transient model does not account for morphological effects, as they are included in the heattransfer coefficient instead, such as the thermal conductivity coefficient and specific heat transfercoefficient. The post heating phase, after the reaction phase, required further work.The simulation with the Shrinking core model shows that a cylindrical geometry requires longercalcination duration, or a higher ambient temperature compared to a spherical geometry, even if bothgeometries have same material properties and radius. The factor with the most influence uponcalcination time is the ambient temperature in combination with reaction temperature. A highercarbon dioxide pressure, above atmospheric CO2 partial pressure, has relatively small effect comparedto a low ambient temperature, less than 1000°C.