Den pågående elektrifieringen av transport och samhälle kräver utveckling av nya metoder för återvinning av batterier. Hydrometallurgi som fokuserar på selektiv kristallisation av metaller är ett intressant alternativ för dessa ändamål. Dessa system kan studeras genom modellering och simulering. Många matematiska modeller finns tillgängliga för att beskriva de olika involverade processerna i kristallisationen av metaller. Dessa processer inkluderar övermättnad, nukleation, kristalltillväxt och aggregation. Denna rapport sammanställer ett antal av de tillgängliga matematiska modellerna och presenterar ett numeriskt tillvägagångssätt för modellering av den tidsberoende nummerdensiteten av partiklar genom en populationsbalansekvation. Populationsbalansen kan lösas med olika metoder såsom momentmetoden och metoden av viktade residualer. Här löses ekvationen genom diskretisering. Diskretisering av den inre koordinaten i ett flertal längdintervall möjliggör simulering av partikel-storleksfördelningen som en funktion av tid. Det numeriska tillvägagångssättet applicerades på bariumsulfatutfällning i en perfekt blandad satsreaktor och två- och tre-dimensionella T-mixer-system, såväl som en perfekt blandad satsreaktor för förträngningskristallisation av nickelsulfat med groddning. Den simulerade storleksfördelningens placering visade sig ha bra överenstämmelse med experimentell data vid låga Reynolds-tal. Här undersöktes även påverkan av en mängd parametrar såsom diskretisering, aggregation och magnituden av diffusion. Aggregation hade en märkbar inverkan på välblandade system. Inverkan av aggregation i diffusions-kontrollerade system med kort retentionstid var låg. Diffusionsmagnituden hade liten påverkan på den normaliserade distributionen men större på det totala antalet partiklar. / The currently ongoing electrification of society and transport necessitates the development of novel methods for battery recycling. Hydrometallurgy with a focus on selective metal crystallisation is an interesting prospect to these ends. The resource recovery systems of interest can be studied through simulation where many mathematical models are available to describe the varying processes involved. These processes include supersaturation generation, nucleation, growth and aggregation. This work compiles some of these mathematical models and presents a numerical approach for the modelling of the time-dependent particle number density with a population balance equation. The population balance equation can be solved using a variety of different methods such as method of moments and method of weighted residuals. Here, the balance equation was solved by discretisation. Discretising the inner coordinate (crystal length) into a number of length intervals allows for the particle size distribution to be modelled as a function of time for various crystallisation systems. The framework was successfully applied to barium sulphate precipitation in a perfectly mixed batch reactor and two- and three-dimensional T-mixer systems, as well as a seeded perfectly mixed nickel sulphate anti-solvent crystallisation system. The simulated size distribution showed promising similarity to experimental data at low Reynolds number. The influence of a variety of parameters such as aggregation and magnitude of diffusion was investigated. Aggregation had a significant impact on well-mixed systems increasing with retention time. The impact of aggregation on diffusion-controlled systems with low retention time was low. The magnitude of diffusion had little impact on the particle size distribution of the crystal population but a large impact on the total number of crystals.

Koldioxidutsläpp (CO2) från energiproduktionsindustrin och transportsektorn globalt påverkar miljön negativt. Länder har enats om att minska utsläppen för att nå målet om en genomsnittlig temperaturökning på 1,5 °C till 2030. Trots detta förväntas de globala utsläppen av CO2 från fossila bränslen och industriella processer vara cirka 40 Gton per år fram till 2100. För att dra nytta av CO2-utsläppen och skapa värdefulla produkter med negativa utsläpp är mineralkarbonatisering en önskvärd process. Denna process innebär att CO2 och mineraler löses upp i en alkalisk lösning och bildar stabila produkter. Faktorer som partikelstorlek hos mineralerna och CO2-lösningshastigheten påverkar mineralkarbonatiseringens hastighet. Experiment utfördes med en batchreaktor från Paebbl AB och en matematisk modell utvecklades i Matlab. Resultaten jämfördes för olika partikelstorlekar i tre motståndsfall. Större partikelstorlek hos olivin visade sig öka tiden för total konvertering, oavsett motståndstyp. De modellerade motstånden beskrev inte tillräckligt processen och indikerade att alla tre motstånd har en samtidig och enhetlig effekt på olivinmineralisering, utöver eventuella begränsningar som föroreningar och biprodukter. Mineraliseringsexperiment med 20 μm partiklar under en timme gav 34,4% omvandling, medan 10 μm partiklar under två timmar gav 46,7% omvandling. En inledande undersökning av massöverföringsbegränsningar visade att CO2-lösningshastigheten inte är den begränsande faktorn, utan lägre omrörningshastigheter och beteendet hos (CO2 + olivin)-systemet behöver ytterligare studeras. Framtida forskning bör fokusera på att lösa dessa begränsningar. / Carbon dioxide (CO2) emissions from the energy production industry and the transportation sector globally negatively affect the environment. A prominent example is the interconnection of carbon with the greenhouse effect. Countries have agreed to mitigate their emissions and try to fulfill the target of 1.5 oC average temperature increase by 2030, but in order to do so the global emissions of CO2 from fossil fuels and industrial processes will still lead up to the astonishing amount of 40 Gtons of CO2 each year until 2100.  It is apparent that processes that try to take advantage of the emitted CO2 creating valuable products with negative emissions are highly desired. One of these is mineral carbonation, where CO2 and minerals dissolve in an alkaline solution and form stable products. Many factors affect the rate at which mineral carbonation happens. The effect of the particle size of the mineral in the process will be investigated, along the CO2 dissolution rate through the overall gas-liquid mass transfer coefficient (kLa), in order to get a better understanding of the process. Experiments were conducted with a batch reactor provided by Paebbl AB and a mathematical model was developed in Matlab. The experimental and numerical results, in regards to the particle size, were then compared for the cases of three resistances. This model can be developed further for use in a continuous mineralization process. The results revealed that increasing the particle size of olivine leads to a significant increase in the time required for total conversion, irrespective of the resistance type. The modelled resistances were found to inadequately describe the process, suggesting a simultaneous and uniform effect of all three resistances on olivine mineralization, in addition to the effect of other possible limitations such as impurities and by-products. Mineralization experiments with 20μm particles and a duration of 1 hour led to 34.4% conversion, whereas experiments with 10μm particles and a duration of 2 hours resulted in 46.7% conversion. Finally, the initial investigation of the mass transfer limitations in a system of CO2 and water led to an average kLa coefficient of 191 h-1, suggesting that the CO2 dissolution rate is not the limiting factor. However, the impact of lower stirring rates remains unexplored due to the absence of appropriate instrumentation and the behaviour of the (CO2 + olivine) system should also be studied. Future research should aim to address these limitations.

As the world population keeps increasing, ammonia-based fertilizers like urea are essential to provide food security. However, the current fertilizer industry is based on fossil fuel feedstock (mainly natural gas), making the production process CO2 emission-intensive. More specifically, besides the CO2 emitted during the process, the CO2 captured in urea is also released into the atmosphere after the fertilizer is applied to agricultural soils. Thus, positioning the fertilizer industry among the top four industrial emitters globally. Hence, in order to meet the target of limiting global warming to 1.5 ºC and achieve net-zero emissions by 2050, it is necessary to strengthen the carbon mitigation efforts in the current fertilizer industry. This can be achieved in different ways, such as using renewable biofuels and implementing technologies that can lead to zero/negative CO2 emissions. For that reason, the present study presents pathways to achieve a more environmentally friendly fertilizer production process. An overall analysis is performed if negative emissions can be achieved by replacing different fractions of natural gas (used as both feedstock and fuel) with biogas and biomethane and by capturing and storing the CO2 emitted from the process using chemical solvents as activated MDEA and MEA. The results obtained from the study revealed that negative emissions in fertilizer plant can be achieved by retrofitting an existing ammonia plant with a MEA based CO2 capture system (with a carbon capture rate of 90%) for the SMR burner flue gas, and by introducing 50% of biogas in the feedstock (alongside Natural gas), and 75% of biogas in the SMR burner fuel (alongside Natural gas). This initial approach would result in net negative emissions from urea's production and application and require approximately 0.5 kg of biogas per kg of urea produced in this case. Furthermore, the equivalent energy intensity for the negative emission urea plant would be 0.32% and 3.37% lower compared to the fossil fuel-based case without/with CCS, respectively. Ultimately, it is even possible to produce approximately 6% more urea product by replacing a particular fraction of natural gas with biogas. The reason for this increased production is due to the surplus of carbon dioxide by the introduction of biogas. It can be used along with the ammonia product going to storage in the fossil fuel-based case, where there was not enough CO2 to keep the feedstock molar ratio at the urea plant's inlet.

In today’s pulp and paper industry the Kraft process is the most common method for pulp production. This method uses sodium based chemicals (white liquor) in the cooking process to remove lignin from the wood chips and create pulp. The remains from this process is called black liquor and is being sent to a recycling system for the purpose of recovering the cooking chemicals. Evaporation of black liquor is a big part of this recycling, and the evaporation plant consists of many different tanks that stores black liquor. At Smurfit Kappa Piteå a model has previously been created for the purpose of production planning. In this work the opportunity to add a part that simulates how the liquor stock in the chemical recovery system will change based on the planned production was investigated. This was done by estimating the amount of dry black liquor in the tanks through inflows and outflows. A formula for the produced black liquor was also developed. The results showed that simulating tank levels separately was difficult as data was lacking in some key areas. The final model is therefore a simplified version that estimates the total amount of dry black liquor in the evaporation plant. It simulates the black liquor buffer based on the planed production and how it will change over five days. This could be done with an error smaller than 6%, compared to measurements from sensors in the black liquor tanks. Attempts were also made to create similar models for the rest of the chemical recovery system. It was concluded that information about the inflow of green and white liquor has to be further investigated in order to implement these in the production planning model.

Arbetet studerade skillnaderna mellan en användning av kalciumhydroxid samtnatriumhydroxid som pH-reglerande kemikalie i en kemisk vattenreningsanläggning.Samt dess påverkan på filtreringssteg som sandfilter, aktivkol filtrering samt jonbytarfiltrering. Det behandlade hur reningsgraden påverkas sett till metallreduktion av;krom, nickel, koppar och zink. Hur slammängderna är i förhållande tillvarandramellan de olika pH-reglernade kemikalierna och slutligen hur filtreringsstegenpåverkas beroende på vilken pH-reglerande kemikalie som doserats. Resultatet förarbetet har visat på att reningsgraden minskar vid användning av natriumhydroxidsom pH-reglerande kemikalie vilket besvarar en del av syftet samt frågeställningenmed arbetet. Ytterligare har resultatet påvisat att de efterkommande filtreringsstegensom i en eventuell framtid kan implementeras leder till en reducering avmetallhalterna i vattnet, vanligen gick reduceringen inte att statistiskt säkerställa mentendenser på en reducering påvisades. Även de erhållna slammängdernareducerades vid användning av natriumhydroxid som pH-reglerande kemikalie vilketvar ett förväntat resultat sett till hypotes och litteratur. Ytterligare minskadeturbiditeten för klarfasproverna vid en natriumhydroxiddosering i förhållande till enkalciumhydroxiddosering. Arbetets resultat har således påvisat den goda möjlighetenatt ersätta den manuella doseringen av solid kalciumhydroxid som pH-reglerandekemikalie emot en automatisk dosering av natriumhydroxid erhållen i vätskeform. / This work studied the differences between the use of calcium hydroxide and sodiumhydroxide as a pH-regulating chemical in a chemical water treatment plant. As wellas its impact on filtration steps such as sand filter, activated carbon filtration and ionexchange filtration. It dealt with how the degree of purification is affected in terms ofmetal reduction of; chromium, nickel, copper and zinc. How the sludge amounts arein relation to each other between the different pH-regulated chemicals and finallyhow the filtration steps are affected depending on which pH-regulating chemical hasbeen dosed. The results for the work have shown that the degree of purificationdecreases when using sodium hydroxide as a pH-regulating chemical, whichanswers part of the purpose and the question of the work. Furthermore, the resultshave shown that the subsequent filtration steps that can be implemented in thepossible future lead to a reduction of the metal contents in the water, usually thereduction could not be statistically confirmed but tendencies of a reduction wereshown. The amounts of sludge obtained were also reduced by using sodiumhydroxide as a pH-regulating chemical, which was an expected result in terms ofhypothesis and literature. Furthermore, the turbidity of the clear phase samplesdecreased at a sodium hydroxide dosage relative to a calcium hydroxide dosage.The results of the work have thus demonstrated the good possibility of replacing themanual dosing of solid calcium hydroxide as a pH-regulating chemical with anautomatic dosing of sodium hydroxide obtained in liquid form.

Cellulose nanofibrils (CNF) is a renewable material with unique strength properties. A difficulty in CNF production is that CNF suspensions contain large amounts of water. If CNF suspension volume can be decreased by dewatering facilitated by centrifugation, then transportation costs and storage costs can be reduced. The aim of this thesis is to investigate the impact various parameters have on CNF centrifugation dewatering and identify optimal conditions for maximal water removal. A laboratory study was conducted using four materials; 2.0 w% enzymatically treated CNF (CNF1), 1.9 w% carboxymethylated CNF (CNF2) and two commercial samples (1.9 w% CNFA and 1.8 w% CNFB). The main method was analytical centrifugation up to 2330 g. Parameters tested were initial concentration before centrifugation, temperature, NaCl addition, pH, and applied solid compressive pressure (g-force and surface weight). In addition to centrifugation experiments the four materials were characterized with laser diffraction, UV-vis absorption, Dynamic light scattering, and dry weight measurements. Analysis of the experimental data collected show that increase in initial concentration give a higher final concentration, but less water is removed. Furthermore, temperature changes have no effect on separation of CNF and water. At an applied solid compressive pressure of 3 kPa and initial concentration at 1.5 w% the concentrations 5.5 w%, 1.5 w%, 4.0 w%, and 4.3 w% can be reach for CNF1, CNF2, CNFA, and CNFB respectively. After extrapolation of polynomial functions fitted to experimental data an applied solid compressive pressure of 22 kPa and initial concentration at 1:5 w%, the concentrations 9.1 w%, 1.5 w%, 6.9 w%, and 7.9 w% are predicted for CNF1, CNF2, CNFA, and CNFB respectively. The thickening of CNF suspensions achieved and predicted in this thesis implies possibilities for large amounts of water removal, e.g. the water content in a CNF1 suspension is reduced from 65.7 litres/kg CNF to 10.0 litres/kg CNF at the solid compressive pressure 22 kPa. The concentrations at 22 kPa are determined by extrapolation from experimental data <3 kPa solid compressive pressure. The carboxymethylated CNF2 can not be dewatered unless it is diluted or if salt or pH is adjusted. This is directly correlated to the electrostatic forces in the suspension and the Debye length. Addition of salt or lowered pH also eliminate any concentration gradients in diluted and centrifuged CNF2 suspensions. / Cellulosa nanofibriller (CNF) är ett förnybart material med unika styrkeegenskaper. En svårighet med produktion av CNF är att CNF suspensioner innehåller stora mängder vatten. Om volymerna av CNF suspensioner kan minskas med avvattning genom centrifugering, då kan transport- och lagerkostnader sänkas. Målet med det här examensarbetet är att undersöka vilken inverkan olika parametrar har på CNF-avvattning genom centrifugering och identifiera optimala förhållanden för maximalt avlägsnande av vatten. En laboratoriestudie utfördes på fyra olika material. De fyra materialen är 2 w% enzymatiskt behandlad CNF (CNF1), 1.9 w% karboxymetylerad CNF (CNF2) och två kommersiella prover (1.9 w% CNFA och 1.8 w% CNFB). Den huvudsakliga metoden var analytisk centrifugering upp till maximalt 2330 g. De testade parametrarna var initial koncentration innan centrifugering, temperatur, NaCl tillsats, pH, och applicerat fast kompressionstryck (g-kraft och ytvikt). Förutom centrifugeringsexperimenten så karaktäriserades the fyra mmaterialen med laser diffraktion, UV-vis absorption, dynamisk ljusspridning och vägningar av torrhalt. Analys av den experimentella data som insamlats visar att en ökad initial koncentration ger en högre slutkoncnentration, men mindre vatten kan bortföras. Temperaturförändringar har ingen effekt på separation av CNF och vatten. Vid ett applicerat fast kompressibelt tryck på 3 kPa och en initial koncentration 1.5 w% kan koncentrationerna 5.5 w%, 1.5 w%, 4.0 w%, och 4.3 w% nås för CNF1, CNF2, CNFA, och CNFB. Efter extrapolering av polynoma funktioner passad till experimentell data förutspås att koncentrationerna 9.1 w%, 1.5 w%, 6.9 w%, och 7.9 w% kan nås för CNF1, CNF2, CNFA, and CNFB vid 22 kPa och en initial koncentration på 1.5 w%. Förtjockningen av CNF suspensioner som kan, eller förutspås kunna nås genom centrifugering i det här examensarbetet innebär att det är möjligt att avlägsna stora mängder vatten, till exempel kan vatteninnehållet i CNF1 minskas från 65.7 liter/kg CNF till 10.0 liter/kg CNF vid 22 kPa fast kompressionstryck. Koncentrationerna vid 22 kPa fast kompressionstryck är extrapolerade från exprimentell data <3 kPa fast kompressionstryck. Den karboy- metylerade CNF2 kan inte avvattnas om den inte späds ut eller om salt eller pH justeras. Detta är direkt kopplat till de elektrostatiska krafterna i suspensionen och Debye längden. Tillsats av salt eller sänkt pH eliminerar också de koncentrationsgradienter som kan förekomma i utspädda centrifugerade CNF2 suspensioner.

With the continuing transition to renewable inherently intermittent energy sources like solar- and wind power, electrical energy storage will become progressively more important to manage energy production and demand. A key technology in this area is Li-ion batteries. To operate these batteries efficiently, there is a need for monitoring of the current battery state, including parameters such as state of charge and state of health, to ensure that adequate safety and performance is maintained. Furthermore, such monitoring is a step towards the possibility of the optimization of battery usage such as to maximize battery lifetime and/or return on investment. Unfortunately, possible online measurements during actual operation of a lithium-ion battery are typically limited to current, voltage and possibly temperature, meaning that direct measurement of battery status is not feasible. To overcome this, battery modeling and various regression methods may be used. Several of the most common regression algorithms suggested for estimation of battery state of charge and state of health are based on Kalman filtering. While these methods have shown great promise, there currently exist no thorough analysis of the impact of so-called filter tuning on the effectiveness of these algorithms in Li-ion battery monitoring applications, particularly for state of health estimation. In addition, the effects of only adjusting the cell capacity model parameter for aging effects, a relatively common approach in the literature, on overall state of health estimation accuracy is also in need of investigation. In this work, two different Kalman filtering methods intended for state of charge estimation: the extended Kalman filter and the extended adaptive Kalman filter, as well as three intended for state of health estimation: the dual extended Kalman filer, the enhanced state vector extended Kalman filer, and the single weight dual extended Kalman filer, are compared from accuracy, performance, filter tuning and practical usability standpoints. All algorithms were used with the same simple one resistor-capacitor equivalent circuit battery model. The Li-ion battery data used for battery model development and simulations of filtering algorithm performance was the “Randomized Battery Usage Data Set” obtained from the NASA Prognostics Center of Excellence.  It is found that both state of charge estimators perform similarly in terms of accuracy of state of charge estimation with regards to reference values, easily outperforming the common Coulomb counting approach in terms of precision, robustness and flexibility. The adaptive filter, while computationally more demanding, required less tuning of filter parameters relative to the extended Kalman filter to achieve comparable performance and might therefore be advantageous from a robustness and usability perspective. Amongst the state of health estimators, the enhanced state vector approach was found to be most robust to initialization and was also least taxing computationally. The single weight filter could be made to achieve comparable results with careful, if time consuming, filter tuning. The full dual extended Kalman filter has the advantage of estimating not only the cell capacity but also the internal resistance parameters. This comes at the price of slow performance and time consuming filter tuning, involving 17 parameters. It is however shown that long-term state of health estimation is superior using this approach, likely due to the online adjustment of internal resistance parameters. This allows the dual extended Kalman filter to accurately estimate the SoH over a full test representing more than a full conventional battery lifetime. The viability of only adjusting the capacity in online monitoring approaches therefore appears questionable. Overall the importance of filter tuning is found to be substantial, especially for cases of very uncertain starting battery states and characteristics.

This thesis builds around the idea of a biofuel production process that is comprised of biomass production, biomass gasification, gas cleaning, and fuel production. In this work, we specifically looked into H2S removal as a part of cleaning the producer gas and flocculation of microalgae which is involved in the harvesting of microalgae after biomass production. One of the impurities to remove from the producer gas is hydrogen sulfide which can be removed by using a packed bed of zinc oxide. Despite the regular use, it was only recently shown that during reaction with H2S, nano-size particles of ZnO exhibit void formation and outward growth. In this work, a micro-scale model was introduced to describe the void formation and outward growth. On the macro-scale, the simulations captured pore clogging of pellets due to the outward growth. The pore clogging prevents the full conversion of pellets and consequently leads to shorter breakthrough times of beds. The second problem investigated here deals with the flocculation of microalgae. Microalgae is produced in relatively low concentrations in the incubator liquid medium and during the harvesting, the concentration is increased to an acceptable level. The harvesting process includes a flocculation followed by a filtration or centrifuge unit. During flocculation, microalgae are stimulated to aggregate and form clusters. The experiments showed that the mean size of clusters formed during flocculation increases with time to a maximum and then starts decreasing, resulting in an overshoot in the mean size profile. The size of clusters influence the efficiency of the afterward filtration or centrifuge, thus it is of interest to carefully track the size evolution of clusters, making the studying of overshoot a crucial research topic. In this work, the possible mechanisms behind this overshoot were investigated. / <p>QC 20170330</p>

The combustion of fossil fuels has for a long time been a problem from an environmental and sustainability point of view, especially when it comes to the emissions of atmospheric carbon dioxide. The environmental concern has for instance shifted the attention towards finding new sustainable alternatives for producing chemicals and fuels, as a substitute to today’s dependence on fossil based crude oil. Catalytic Fast Pyrolysis of biomass is an excellent way to produce valuable chemicals and fuels using renewable resources. However, the process has some drawbacks, for example rapid deactivation of catalysts due to coke formation. Little is known about the characteristics of the formation of catalytic coke from pyrolysis processes, which should be a vital concern in future industrial processes. This thesis is dedicated to investigate the chemical coke characteristics found on zeolitic catalysts. Four zeolites of the type ZSM-5 were chosen for this thesis to deduce any chemical differences in the coke: HZSM-5, Fe/ZSM-5, Ni/ZSM-5, and Fe-Ni/ZSM-5. The coke were characterized by TGA, GC/MS, and FTIR. The results show that Fe/ZSM-5 produced the highest amount of coke compared to the other zeolites, where HZSM-5 had the lowest amount of coke formation. The coke consisted mainly of aromatic and cyclic hydrocarbons, dominated by polycyclic aromatic hydrocarbons. The content of ketones and alcohols in the coke found on HZSM-5 was higher compared to the metal-doped zeolites, while the formation of naphthalenes was lower. The FTIR results also show that coke was mainly comprised of aromatic hydrocarbons. However, traces of alkanes and alkenes reveal that the coke may have a greater variety than the GC/MS analysis suggests. The results show interesting features when metals are introduced to the zeolitic structure, at least when it comes to coke formation. The metal-doping of zeolites certainly seems to alter the chemistry of the catalytic reactions, compared to the parent zeolite. The differences in the chemical characteristics found in the coke are certainly interesting, and it could mean that the chemistry of the bio-oil also varies depending on the metals chosen for the ZSM-5. The new properties that metals introduce to the parent catalyst may open up new possibilities in industrial catalytic processes, and allow industries to take more advantage of the great benefits that biomass has to offer. / Förbränning av fossila bränslen har under lång tid utgjort ett problem ur miljö- och hållbarhetssynpunkt, i synnerhet gällande utsläppen av koldioxid. En större miljömedvetenhet har gett upphov till sökandet efter nya råvaror för att framställa bränslen och kemikalier, utan att förlita sig på fossil råolja. Katalytisk pyrolys av biomassa är ett utmärkt sätt att framställa värdefulla kemikalier från förnybara källor. Processen står dock inför en del tekniska utmaningar, bland annat en snabb deaktivering av använda katalysatorer genom koksning. Målet med detta examensarbete är att undersöka den kemiska sammansättningen av koks, som bildats på zeolitkatalysatorerna. Mer specifikt, att försöka undersöka huruvida den kemiska sammansättningen av koks skiljer sig mellan katalysatorn HZSM-5 och metalldopad HZSM-5. Fyra katalysatorer valdes för detta examensarbete, nämligen HZSM-5, Fe/ZSM-5, Ni/ZSM-5 och Fe-Ni/ZSM-5. Kokset har analyserats genom termogravimetrisk analys (TGA), gaskromatograf kopplad med en masspektrometer (GC/MS), samt Fourier-transform-infraröd-spektroskopi (FTIR). Resultaten visar att Fe/ZSM-5 bildade en större mängd koks jämfört med de andra zeoliterna, varpå HZSM-5 hade lägst halt koks. Utöver detta bestod kokset till största del av aromatiska- och cykliska kolväten, speciellt polycykliska aromatiska kolväten. Innehållet av ketoner och alkoholer i kokset var störst för HZSM-5, medan bildandet av naftalenföreningar ökade för de metalldopade zeoliterna. FTIR-analysen gav även upphov till signaler som är signifikanta för både alkaner och alkener. Därför kan det innebära att kokset innehar en större kemisk variation än vad GC/MS-analysen påvisade. Resultaten visar intressanta egenskaper hos metallmodifierade zeoliter, i synnerhet gällande koksbildning. Det verkar som att de metalldopade zeoliterna påverkar de katalytiska reaktionerna som sker i katalysatorn, jämfört med den obehandlade katalysatorn. Skillnaderna i den kemiska sammansättningen hos kokset för de olika katalysatorerna är definitivt intressant och kan indikera att det även kan föreligga skillnader i den kemiska sammansättningen hos bio-olja, beroende på vilken metall ZSM-5 har behandlas med. De nya egenskaperna som metaller bidrar med till ZSM-5 kan öppna upp nya möjligheter i industriella katalytiska processer, vilket även kan medföra att industrier bättre kan ta tillvara på de fantastiska egenskaper biomassa innehar.

Vid produktion av biodiesel produceras även råglycerol (10 vikt%) som biprodukt och utbudet av råglycerol har ökat över de senaste åren till följd av att biodieselproduktionen ökat. Marknadsvärdet för råglycerol är lågt, men det är en utmärkt föregångare till att producera mervärdesprodukter för exempelvis läkemedelsindustrin, kemikalieindustrin eller kosmetika. Genom att reformera glycerol till mervärdesprodukter ökar konkurrenskraftigheten för biodiesel och värdekedjans ekonomiska hållbarhet. Elektrokemisk reformering av glycerol är en lovande metod för att producera dess mervärdesprodukter, eftersom processen är justerbar och miljövänlig. En ytterligare fördel är att vätgas kan samproduceras med mervärdesprodukterna genom denna metod och energikonsumtionen för att producera vätgas genom denna metod är ungefär hälften av vad som krävs vid vattenelektrolys. Denna studie utvärderar hur masstransport påverkar selektiviteten och prestandan för elektrokemisk oxidation av glycerol, genom att utföra elektrokemiska experiment, karaktärisera processens katalysator och analysera produkter som produceras.  Den experimentella uppställningen innefattar en roterande diskelektrod med ett elektrodepositerat lager av Pd, på ett Ni-substrat, i varierande tjocklek. Elektroden undersöks i elektrolyter bestående av varierande koncentration av NaOH (1, 0.5 och 0.25 M) och 0.5 M glycerol vid 25 oC. Systemet konstrueras även som modell i Comsol Multiphysics 6.0 för att simulera experiment. Resultaten visar att masstransport av glycerol begränsar systemet genom att orsaka deaktiveringen av katalysatorn. Vid de lägre NaOH koncentrationerna begränsar även masstransport av OH- reaktionshastigheten genom att miljön omgärdande elektroden blir mindre oxidativ. Slutligen visas att reaktionsmekanismen vid alla tjocklekar av katalysatorn utgörs av två parallella reaktionsvägar. En ökande tjocklek hos katalysatorn ökar selektiviteten mot den ena reaktionsvägen framför den andra, samt ökar antal oxidationssteg som åstadkoms vid reaktionen. / Biodiesel production gives rise to 10 wt% crude glycerol as a byproduct, which is becoming increasingly available on the market owing to the increased biodiesel production over the last few years. Crude glycerol has a low market value, but it is an excellent precursor to producing value added products for the pharmaceutical industry, chemical industry or cosmetics to mention a few. By producing value added products with biodiesel derived glycerol, the ability of biodiesel to compete with fossil fuels is improved and its economical sustainability is promoted. One of the most promising methods to convert glycerol into its value added products is electrochemical reforming, as it poses high tunability and is an environmentally friendly process. Additionally, the process produces hydrogen concurrently and halves the energy consumption compared to producing hydrogen from water electrolysis. This study evaluates the impact of mass transport in the glycerol electrooxidation reaction (GEOR), as a parameter that can be used to finetune product selectivity and optimise the system performance. To do so, the study employs electrochemical experiments, catalyst characterisation and product analysis. The experimental setup consists of a rotating disk electrode (RDE) cell with electrodeposited Pd on Ni substrate at varying thicknesses, operating in 1, 0.5, 0.25 M NaOH and 0.5 M glycerol electrolyte at 25 oC. Additionally, the system is modelled in Comsol Multiphysics 6.0 which is used to perform simulations. It is found that mass transport of glycerol is limiting the system by causing the deactivation of the catalyst. At lower NaOH bulk concentrations for the thicker electrodes, the mass transport of OH- also limits the reaction rate by causing the formation of a locally less oxidative environment. Finally, it is found that all electrodes pose dual reaction mechanisms. Increasing the electrode thickness promotes one reaction mechanism over the other as well as it increases the number of oxidation steps achieved in the reaction.