A conventional exhaust gas after treatment system (EATS) for the Euro VI legislation contains four different catalyst. The first two (particulate filter system) remove particulates and the last two (SCR system) remove nitrogen oxides (NOx). The particulate filter system also optimizes the gas composition with respect to nitrogen monoxide (NO) and nitrogen dioxide (NO2). The performance of the SCR system has a strong dependency on the NO:NO2 ratio as the so called selective catalytic reduction (SCR) reaction is kinetically favored at a NO:NO2 ratio of 1:1. The diesel oxidation catalyst (DOC) is placed first in the EATS. Due to this placement, the DOC is subjected to a rough environment, e.g. high temperatures and oil/fuel impurities that with time will affect its performance, i.e. the catalyst ages. In this master thesis, the aging of the DOC has been empirically correlated to thermal load and sulfur exposure. The study shows that it is possible to predict how the NO oxidation performance decays as a function of thermal and sulfur exposure. The empirical relation was fitted against two aging cycles and validated against an additional four. The results show that the loss of catalytic activity can to a large extent be explained by the cycle it has been used on. / Ett konventionellt efterbehandlingssystem för Euro VI-standarden innehåller fyra olika katalysatorer. De första två rensar (partikelfiltersystemet) från partiklar och de två sista (SCR-systemet) tar bort kväveoxider (NOx). Partikelfiltersystemet reglerar även gassammansättningen med avseende på kvävemonoxid (NO) och kvävedioxid (NO2). Prestandan för SCR-systemet har ett starkt beroende på NO:NO2-förhållandet där ett förhållande på 1:1 är kinetiskt gynnat för den så kallade SCR-reaktionen (eng: Selective Catalytic Reduction). Oxidationskatalysatorn (DOC) sitter som ett första steg i efterbehandlingen. Placeringen medför att katalysatorn finns i en tuff miljö där den till exempel utsätts för hög temperatur och olje/bränsleföroreningar som över tiden påverkar dess prestanda. Detta brukar kallas att DOC:n åldras. I detta examensarbete har åldrandet av DOC:n korrelerats empiriskt till termisk belastning och svavelexponering. Studien visar att det är möjligt att förutsäga hur NO-oxidationsprestandan avtar som en funktion av termisk last och svavelexponering. Det empiriska modellen anpassades till två åldringscykler och validerades emot ytterligare fyra cykler. Resultaten visar att den kvarvarande katalytiska aktiviteten i stor utsträckning kan förklaras genom vilken cykel den har körts på.

Mankind has to provide a sustainable alternative to its energy related problems. Bioenergy is considered as one of the potential renewable energy resources and as a result bioenergy market is also expected to grow dramatically in future. However, logistic issues are of serious concern while considering biomass as an alternative to fossil fuel. It can be improved by introducing pretreated wood pellet. The main objective of this thesis is to address thermochemical behaviour of steam exploded pretreated biomass. Additionally, process aspects of torrefaction were also considered in this thesis. Steam explosion (SE) was performed in a laboratory scale reactor using Salix wood chips. Afterwards, fuel and thermochemical aspects of SE residue were investigated. It was found that Steam explosion pretreatment improved both fuel and pellet quality. Pyrolysis of SE residue reveals that alerted biomass composition significantly affects its pyrolysis behaviour. Contribution from depolymerized components (hemicellulose, cellulose and lignin) of biomass was observed explicitly during pyrolysis. When devolatilization experiment was performed on pellet produced from SE residue, effect of those altered components was observed. In summary, pretreated biomass fuel characteristics is significantly different in comparison with untreated biomass. On the other hand, Process efficiency of torrefaction was found to be governed by the choice of appropriate operating conditions and the type of biomass. / QC 20120110

The purpose of this project was the modeling, optimization and prediction of a hybrid system composed of a fuel cell, a dc-dc converter and a supercapacitor in series. Lab tests were performed for each device to understand their behavior, and then each one was modeled using software (Simulink). The validation of the model was done by comparing its results with measured data; finally the model was used for the optimization and the prediction of the hybrid system

Europeiska Unionen presenterade den 8 juni 2020 sin vätgasstrategi i syfte för att minska koldioxidutsläppen. Det unionen vill uppnå med sin vätgasstrategi är att uttnytja konceptet Power-to-X där elektricitet omvandlas till energi. Om elektricitetkällan kommer från förnyelsebar energi kommer grön vätgas produceras. Problemet med vätgas idag är lagring, transport och hanteringstrukturen för ämnet men vätgas kan lagras i flertal applikationer. En av de mest lovande lagringsalternativen är ammoniak som bildas när vätgas med kvävgas reagerar med varandra via ammoniaksyntes. Eftersom vätgasproduktionen idag använder fossila bränslen kommer även dess applikation göra det, men med grön vätgas kommer dess applikation även att bli grön. Idag står ammoniakproduktion för 2 % av fossilbränsleanvändning globalt och frigör mer än 400 miljoner ton CO2 årligen. Dessa utsläpp skulle försvinna om produktionen av ammoniak gjordes med Power-to-X konceptet. Syftet med detta examensarbete är att undersöka förutsättningarna ur ett ekonomiskt, tekniskt och säkerhetsmässigt hållbart Power-to-X koncept i form av en Grön Ammoniakanläggning i Norra Sverige. Det innebär att processer för en ammoniakproduktion skall analyseras ur ett teknisk synvinkel där fokus på funktion mot grön ammoniak är i fokus. Den ekonomiska synvinkeln innebär vad kapitalkostnaden (CAPEX) blir för anläggningen samt driftkostnaden (OPEX) som processen får. Arbetet innehåller först en analys av de processer som krävs för att kunna producera ammoniak. Därefter en analys över möjliga tekniker för dessa processer, hur väl de fungerar mot grön ammoniak och vilka antaganden som är i detta arbete. Anläggningen skulle vara storskalig vilket innebär en produktion på 500 ton NH3 $/dag. Det är även antaget en kontinuerlig eltillförsel samt att elnät redan är tillgänglig. Detta gav att vätgasproduktionen gjordes med en PEM-elektrolys, där kvävgas fås från kryogen destillation och ammoniak produceras med HB-processen. Resultatet visades att anläggningens CAPEX och OPEX blev 2 820 MSEK respektive 1 272 MSEK/år. Den dominerande faktorn för kapitalkostnaden var för vätgasproduktion som utgjorde 60 % av CAPEX. Den höga kostnaden för PEM-elektrolys är dels för att utvecklingen av processen inte är fullbordad, där utvecklingen för tekniken skulle kunna ge en stor kostnadsreducering. Det elbehov som anläggningen kräver är 1,6 TWh och och utgör en påverkan på OPEX är 55,4 %. Den process som kräver mest energi är vätgasproduktionen vilket omfattar 94 % av hela anläggningens totala elbehov. En stor anledning till de dyra driftkostnaderna är elpriset. I detta arbete valdes elpriset till ett medelvärde för SE1 i Sverige under en 10 års period. I ett verkligt scenario hade vätgasproduktionen kunnat optimeras för uppnå billigare drift.

The kraft process is a complex system with many variables, and though the process is fairly well understood, there is still much we do not know.      This thesis examines some aspects of the kraft process that could prove to be of interest for the pulp and paper industry, specifically, the impact of wood chip impregnation and of the chemical structure of xylan on spruce kraft pulp. The intent is to suggest modifications to the kraft process as it is used today.      The effect of wood chip impregnation varies with the prevalent conditions, and increases the effect of the subsequent kraft cook. Longer impregnation at a lower temperature was found to increase screened pulp yield, reduce shives content, make it possible to reach a certain kappa number at a lower H-factor, and make it possible to reach a certain kappa number at a lower total alkali consumption.      Xylan has previously been found to have a strength-enhancing effect on pulp, and the chemical structure of the xylan in question was found to be the main strength-enhancing factor. For spruce xylan, the structure that provides the largest increase in strength is not the same as the structure that increases the yield the most. Removing xylan was determined to have a negative impact on pulp strength.      Xylan extracted from agro waste can be used as an additive to increase pulp strength. This could be viable, especially when combined with the production of green plastics from hemicelluloses extracted from the agro waste.      A suggested configuration of a future pulp mill is presented, incorporating the following modifications to the now standard kraft cooking system: impregnation at a lower temperature for a longer time; extracting xylan-enriched black liquor at an early stage of the impregnation or cook, and adding this liquor at a late stage of the cook; terminating the cook at a higher kappa number; increasing oxygen delignification to compensate for the increased kappa number at the end of the cook, keeping the kappa number constant going into the bleaching plant; and adding agro-waste xylan during oxygen delignification. / <p>QC 20150525</p>

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.