Contamination of surface and ground water from industrial wastes and anthropogenic activities represents one of the greatest challenges to the sustainable development of human society. Heterogeneous photocatalysis, a kind of advanced oxidation process characterized by the production of highly oxidative hydroxyl radicals, is a relatively novel subject with tremendous potential in water treatment applications.     The purpose of this research was first to develop feasible hydroxyl radical detection methods, which can be used to evaluate efficiency of photocatalytic process, and second to prepare immobilized TiO2 films with high photocatalytic activities by the sol gel method.     The feasibility of Indigo carmine and phthalic hydrazide as OH-radical probes was investigated. The organic dye Indigo carmine absorbs visual light strongly at 610 nm and its destruction can be monitored conveniently in a spectrophotometer. Results showed that both ·OH and HO2· can bleach Indigo carmine, and the bleaching yield of ·OH was pH independent. The photocatalytic dye bleaching in black light UV illuminated Degussa P25 TiO2 aerated suspensions was then investigated. A strong pH dependency of the bleaching yield was found.  This implies that the quantum yield of OH radical at pH 3 is one fourth compared to that at pH 10. The reaction of the OH radical with phthalic hydrazide will form strongly chemiluminescent 3-hydroxyphthalic hydrazide. Using the more specific phthalic hydrazide as OH radical probe, an even stronger pH dependent quantum yield of OH radical was found. At pH 10 the quantum yield reached the same magnitude as that obtained by using Indigo carmine, whereas the quantum yields at acidic pH were close to zero. However it was found that the addition of phosphate and fluoride anions can substantially enhance the OH radical yield at acidic pH by blocking the adsorption of phthalic hydrazide onto the TiO2 surfaces. Hence the adsorption of phthalic hydrazide to TiO2 is an important factor to consider when this method is used.     Photocatalytic TiO2 films coated on metal plates were prepared by a sol gel method using titanium isopropoxide as TiO2 precursor and isopropanol as solvent. The photocatalytic activity of the obtained films was evaluated by bleaching of indigo carmine at pH 9 under black light UV irradiation. The effect of the molar ratio of isopropanol, water and hydrochloric acid to titanium isopropoxide was studied. It was also shown that the activities of TiO2 films are considerably influenced by calcination temperature, coating cycles and the supporting materials. / Förorening av yt- och grundvatten från industrier och humana aktiviteter utgör en av de största utmaningarna för en hållbar utveckling av det mänskliga samhället. Heterogen fotokatalys, en slags avancerad oxidations process som kännetecknas av att starkt oxidativa hydroxylradikaler produceras, är en relativt ny teknik med stor potential för vattenrening.     Ett syfte med detta licentiatarbete var först att utveckla och genomföra olika metoder för att detektera bildningen av hydroxylradikaler såväl i laboratoriet som i tekniska miljöer. Det andra syftet med arbetet var att syntetisera immobiliserade TiO2 filmer med hög fotokatalytisk effektivitet med en sol-gel metod.     Möjligheten att använda indigokarmin och ftalhydrazid som OH-radikalprob undersöktes. Det organiska färgämnet indigokarmin absorberar synligt ljus starkt vid 610 nm vilket gör att dess nedbrytning lätt kan följas i en spektrofotometer. Resultaten av gammaradiolys visade att båda •OH och HO2• kan bleka indigokarmin och att den blekning som härrör från •OH var oberoende av pH. Fotokatalytisk blekning av indigokarmin med blacklight UV bestrålning av  Degussa P25 TiO2 suspensioner undersöktes sedan. Ett starkt pH-beroende av blekningsutbytet erhölls vilket tolkas som att kvantutbytet av OH-radikaler vid pH 3 är en fjärdedel jämfört med det vid pH 10.     När ftalhydrazid reagerar med OH-radikaler bildas starkt kemiluminiscent 3-hydroxy-ftalhydrazid. Med denna  specifika OH-radikalprob, erhölls ett ännu starkare pH beroende. Vid pH 10 var kvantutbytet i paritet med det som erhölls med indigokarmin, medan kvantutbytet vid lågt pH var nära noll. Tillsats av fosfat-  och fluoridjoner visade sig avsevärt öka OH-radikalutbytet vid lågt pH-värde genom att blockera adsorption av ftalhydrazid på TiO2 ytorna. Adsorptionen av ftalhydrazid på TiO2 är således en viktig faktor när denna metod används.     Fotokatalytiskt verksamma TiO2-filmer på metallplattor framställdes med sol-gel metoden med titan-isopropoxide som TiO2-prekursor och isopropanol som lösningsmedel. Den fotokatalytiska aktiviteten av TiO2-belagda plattor utvärderades genom blekning av indigokarmin vid pH 9 under blacklight UV-bestrålning. Effekten av olika proportioner mellan isopropanol, vatten och saltsyra till titan isopropoxide undersöktes. Det visade sig att denfotokatalytiska aktiviteten av TiO2-plattorna i hög grad påverkades av kalcineringstemperatur, beläggningscykler och materialet i plattorna.

This project was a cooperation between the division of Chemical Technology at KTH, Cortus Energy and Haldor Topsoe A/S. The goal was to build up a totally new setup for converting and deoxygenate pyrolysis bio-oil, in order to increase the performance of Cortus Energy’s WoodRoll process. Therefore an iron based catalyst from Haldor Topsoe was used. The building up of the new setup with all reactors and the control panel was a complicated and time-consuming work. This led to an only short time slot for performing experiments, which means that more work needs to be done to get more valuable results. The most important success of this project was to get all the knowledge about the system and to make everything (the whole experimental setup) running properly. However, the sampling system needs to be improved before making further experiments. The experiments which have been done show promising results and that the iron based catalyst was working well for converting the bio-oil. During the two hour long experiment there were not shown any indications of deactivation, when looking at the gas compositions, but the results from temperature programmed oxidation (TPO) show carbon deposition on the catalyst and the BET surface also shows a slight decrease in surface area.

Polypeptides are becoming an important component of the antibiotic therapeutics. The production demand of therapeutic polypeptides is increasing and there is a significant interest in developing more efficient production processes. In pharmaceutical industries, polypeptides are produced as a crude mixture. Reverse phase high performance liquid chromatography (RP HPLC) is used as a typical separation technique to purify the target polypeptide from other impurities. Currently organic modifier gradients are used to elute product peptides separately from impurities. In this work, we add a second, simultaneous counter-ion gradient, in the hope of increasing separation performance and call it double gradient reverse phase chromatography. A general procedure of the model-based optimization of a polypeptide crude mixture purification process was followed to evaluate the effects of the double gradients on industrial chromatographic process. The target polypeptide elution profile was modeled with a bi-Langmuir adsorption equilibrium isotherm. The isotherm parameters of the target polypeptide were estimated by the inverse method. The model parameters of the impurities were regressed from experimental data. The variations of the isotherm parameters with the modifier concentration and counter-ion concentration were taken into account of the adsorption model. After model calibration and validation by comparison with suitable experimental data, Pareto optimization of the process were carried out to analyze the differences between single gradient chromatography and double gradient chromatography. It was observed that the additional linear gradient of counter-ion concentration did not improve the separation process. Conclusively we were able to demonstrate the concept of double gradient reverse phase chromatography within limited time and possible least experimental efforts.

Cement is produced in three main steps: grinding of a mixture of raw materials, sintering of the raw meal to form clinker, and grinding and mixing of clinker, gypsum and additives to make cement. Slag from steel manufacturing can be used to replace some of the raw material, but since slag is a carrier of some unwanted compounds, problems arise. Excess sulphur circulating in the system during clinker production can cause various problems such as clogging. In this report, the circulation of sulphur and other volatile compounds as well as the composition of gaseous and solid materials in the cyclone tower has been studied using old data from 2014 and new measurements. No sulphuric gases were found in the cyclones, so it was concluded that most of the sulphur condenses at the bypass at the inlet to the cyclone closest to the kiln. Condensation is assumed to occur early in the pre-heating tower because of air leaking in. Sulphur balances from 2014 and 2020 showed that usage of slag increases the amount of sulphur that circulates in the system and that the critical amount has been exceeded as of the measurements taken 2020. It is recommended that further measurements are performed, such as qualitative analysis of the solid material to distinguish the different sulphuric compounds, as well as more experiments with varied parameters such as the amount of slag and kiln fuel used.

Silver and palladium can be found in the so called palladium-ceramics which comes from catalyst production. These valuable metals needs to be recovered from these wastes in order to further increase both the environmental and economic sustainability of our society. This material has also been suspected of causing some problems at Boliden’s smelter Rönnskär during the silver smelting. Unfortunately due to the nature of massive economics at work in precious metal production there has not been much published work around this subject. Therefore this works seeks to increase the understanding of how this waste affects the A-slag in the precious metal production at Rönnskär.   This work takes a look at how certain fluxes and temperatures affects the slag and metal phases, as well as how increasing the addition of the palladium-ceramic affects the melt. It does so by making screening tests with a basic setup of slag from the process, silver granules and additions of coke and sodium carbonate at different temperatures.   The results show that using a reducing environment by adding coke does increase the recovery of the precious metals. Increasing the temperature of the melt also shows an improvement in the recovery of the precious metals.  Furthermore the basis to an alternative way of using this material, consisting of smelting it together with silver and fluxing materials has been suggested in this work in order to eliminate the possible problems it causes in the current process. / Silver och palladium kan finnas i materialet som kallas katalysatormassa som kommer från framställningen av katalysatorer. Dessa värdefulla metaller måste återvinnas från detta avfall för att öka hållbarheten i vårt samhälle både miljömässigt och ekonomiskt. Materialet har också varit en möjlig orsak till problem vid silversmältningen på Bolidens smältverk, Rönnskär. Tyvärr på grund av den enorma ekonomin kring ädelmetaller och deras produktion har det inte publicerats många artiklar om detta ämne. Därför försöker detta arbete att öka förståelsen av hur detta avfall påverkar A-slaggen hos ädelmetallframställningen på Rönnskär.   Detta arbete undersöker på hur olika flussmedel och temperaturer påverkar slaggen och metallfasen, samt hur en ökad mängd katalysatormassa påverkar smältan. Det görs genom att göra flera testsmältor med en bas med slagg från processen, silvergranuler samt tillsatser av koks eller natriumkarbonat vid olika temperaturer.   Resultaten visar att användandet av en reducerande miljö genom tillsättningen av koks ökar återvinningen av ädelmetallerna. En ökad temperatur på smältan har också visat på en ökad återvinning. Utöver detta så har grunden till ett alternativt sätt att använda sig av materialet tagits fram. Detta alternativ består av att smälta materialet tillsammans med silver och flussmedel och har tagits fram för att undvika möjliga problem i befintlig process.

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.