NTNU Fakultet for naturvitenskap og teknologi Norges teknisk-naturvitenskapelige Institutt for kjemisk prosessteknologi universitet

Suggestions for masther thesis 2013

at Department of Chemical Engineering Fagområder/-groups: 1: Katalyse / Catalysis Group 2: Kolloid- og polymerkjemi / Colloid- and Polymer Chemistry Group 3: Miljø- og reaktorteknologi / Environmental Engineering and Reactor Technology Group 4: Prosess-systemteknikk / Process Systems Engineering Group 5: Bioraffinering og fiberteknologi / Biorefining and fibre technology I:/ikp/3 UNDERV /Masteroppgaver2013/Samleliste Masteroppgaveforslag 2013

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Katalyse/Catalysis Group

EAB: Professor Edd A. Blekkan

EAB-1: Hydrocarbon pyrolysis Pyrolysis is a possible route to methane upgrading, and high yields of C2 compounds can be obtained if the reaction conditions are carefully controlled. The best conditions involve very high temperatures and very short residence times. The chemistry involved is complex, and involves free radical reactions. In this project the pyrolysis of methane or other compounds (e.g. biofuel relevant model compounds) will be studied experimentally, using a dedicated setup. Co-supervisor: Torbjørn Gjervan EAB-2: Catalytic dehydrogenation of propane by carbon supported metal

catalysts Use of nanostructured carbons (including carbon nanofibres and carbon nanotubes) as support for metal catalysts is an important area of research that can improve understanding of catalytic processes. One of those processes is dehydrogenation of light hydrocarbons. This project will involve an investigation of dehydrogenation of propane using platinum-based catalysts (prepared using the colloidal method or other methods), deposited on nanostuctured carbons. Key elements of the work are catalyst preparation and characterization, and activity and selectivity measurements in a dedicated experimental set-up, exploring the effect of the carbon structure and Pt loading and particle size on the catalytic properties. Reservert for Eirik Østbye Pedersen EAB-3: Hydrotreating of bio-oils over Mo-based catalysts The production of liquid fuels from biomass is a key feature of a future renewable energy system. Bio-oils can be produced by biomass pyrolysis, and would in principle not contribute to anthropogenic CO2 when combusted since they are part of a natural biological cycle. A main issue is the high content of oxygen in bio-oils (up to 50%) This is undesirable due to a low energy content (low heating value), thermal and chemical instability, poor miscibility with other fuels and a tendency to polymerize and form “gums” or particles. Therefore, the removal of the oxygen is necessary to allow the practical use of these oils. The hydrodeoxygenation (HDO) of oils is a hydrotreating process using hydrogen gas at high pressure. We study new catalysts for this process. Molybdenum-based materials have been shown to have interesting properties, and in this project different forms of Mo-based systems will be explored (carbides, nitrides or phosphides). The work is mainly experimental (catalyst synthesis and characterization, and catalytic experiments), supported by literature studies and theoretical considerations. Co-supervisor: Sara Boullosa Eiras Reservert for Sindre Asphaug EAB-4: Microcalorimetry Adsorption microcalorimetry involves the direct measurement of the heat of adsorption of a gas adsorbing on a heterogeneous catalyst while recording an adsorption isotherm, giving a direct measure of the adsorption enthalpy as a function of surface coverage. This information is very useful when comparing catalysts or adsorbents, or modelling catalytic reactions. In this project a dedicated apparatus consisting of a m microcalorimeter connected to a volumetric chemisorption apparatus will be used for the characterization of heterogeneous catalysts, in collaboration with other projects in the catalysis group. The catalysts of interest can be cobalt- or iron-based Fischer-Tropsch catalysts, Pt-based catalysts or other catalytic systems (acidic, basic or other metal-based systems). The project is best suited for a careful experimentalist. Co-supervisor: Jia Yang. EAB-5: Hot gas cleaning Biomass gasification and subsequent fuel synthesis is an interesting route to 2nd generation biofuels. Biomass contains a range of elements that to some extent occur in the gasphase, most prominently sulfur and alkali, but a range of other elements can be found in the syngas. Many of these species must be

removed in order to protect the catalysts used downstream. However, in order to optimize such processes with respect to thermal efficiency, it is desirable to clean the syngas at as high a temperature as possible, to avoid cooling and reheating the gas. Hot gas cleaning is a particular challenge, and new adsorbent materials that can adsorb undesired species at relatively high temperatures must be developed. This project deals with development of new materials for this purpose, and experimental work studying the adsorption properties. Initially, a new adsorption apparatus must be completed and tested and calibrated. Suitable candidate materials must be identified based on literature and theoretical studies, and finally adsorption studies will be done. Co-supervisor: Svatopluk Chytil (SINTEF) DC: Professor De Chen

DC-1: Kinetic study of oxychlorination process Catalytic oxychlorination of ethylene with hydrochloric acid and oxygen is the important industrial process to produce 1,2-dichloroethane, which can be converted into vinyl chloride by cracking process. Supported CuCl2 catalyst often used as oxychlorination catalysts. The present work focuses on the catalyst preparation and characterization of CuCl2 layer on alumina supports. The site reactivity will be studied by combined UV-Vis spectroscopy-MS and transient kinetic study on catalyst with different site density. Supervisor: Prof. De Chen Co-supervisor: Dr. Jun Zhu DC-2: Hydrogen production from biomass derived compounds by sorption enhanced reforming Sorption enhanced reforming (SER) is a promising process to overcome the thermodynamic constrains and to reach one-step hydrogen production with high purity and yield from biomass derived compounds. The CO2 high temperature acceptors and catalysts are installed together in the reactor. We have long worked on nearly pure hydrogen production by SER from biomass derived ethanol, glycerol, crude glycerol, sorbitol, glucose, synthesis gas from biomass gasification and crude biomass. There has been an excellent record of project and master projects on this topic, where four students worked on the topic, and each has at least one publication on high ranked journals based on their work. The present work will focus on the hydrogen production from bio-oils, which can be produced by fast pyrolysis of biomass. The project involves catalysts and sorbents synthesis and test in as fixed bed reactor using probe molecules such as acetic acid, acetone and aromatics. DC-3: Synthesis of fuels from biomass derived oxygenates Oxygenates, such as ethylene glycol and propanediol, can be directly produced by hydrogenolysis of wood biomass in a high yield. The present work focus on catalytic conversion of such oxygenates to biofuels via dehydration, hydrogenation and aldol condensation in one-stage on multifunctional catalysts. Supported Cu and Au catalysts will be synthesized, characterized and tested in a high pressure fixed-bed reactor. Supervisor: Prof. De Chen DC-4: One-pot conversion of biomass to chemicals Catalytic processes for conversion of biomass to transportation fuels have gained an increasing attention in sustainable energy production. The biomass can be converted to fuels via three platforms, such as fast pylolysis (bio-oil as intermediate), hydrolysis (sugars as intermediates) and gasification (synthesis gas as intimidates). Recently it has been reported that biomass can be directly converted to polyols, such as ethylene glycol and propanediol. Those polyols can be converted to gasoline and diesels via hydrogenolysis, aldol condensation and hydrogenation reactions on multifunctional catalysts. The project will review the different reaction routes from biomass to fuels. The process will be designed in HYSYS and evaluated in terms of product yields and energy efficiency based on reported values. This project is cooperated together with STATOIL and a summer job is available. Co-supervisor: Dr. Børre Børresen, STATOIL

MR: Professor Magnus Rønning

MR-1: Correlation of catalyst morphology with attrition resistance and

catalytic activity of Fischer-Tropsch catalysts Supported cobalt catalysts are widely studied and applied for conversion of synthesis gas in low temperature Fischer-Tropsch synthesis. The master work will include synthesis, characterisation and testing of FT catalysts. Particular focus will be given to investigation of correlations between catalyst morphology and catalyst attrition as well as catalyst performance. The project will be carried out at Statoil Research Centre and NTNU. Co-advisors: Erling Rytter/Sigrid Eri (Statoil) The project is reserved for Thomas Haukli Fiske MR-2: Photocatalytic H2-production through photo-reforming of hydrocarbons Producing hydrogen from photoreforming of hydrocarbons is an emerging field within renewable energy research. Photocatalysts that can operate at ambient temperature without producing harmful by-products are ideal as environmentally sound catalysts. For such systems to be considered in large-scale applications, photocatalytic systems that are able to operate effectively and efficiently in a continuous flow reactor must be established. The project involves synthesis and characterisation of efficient materials for photocatalysis and testing of the catalyst materials in photocatalytic reactions. Co-advisor: Charitha Udani MR-3: Doped carbon nanostructures as metal-free catalysts Doped nanocarbons represent a new class of metal-free catalyst for several potential catalytic applications, including the oxygen reduction reaction, oxidative dehydrogenation of light alkanes and advanced oxidation processes. The active sites in the metal-free catalysts are strongly embedded into the host matrix. The N-doped carbon nanofibres (N-CNF) show many properties that are markedly different from those of undoped counterparts. The N-CNF will be synthesized by chemical vapour deposition from a growth catalyst under a mixture of nitrogen-containing hydrocarbons. The emphasis will be put on synthesis method and characterisation of catalytic activity. The materials will be analysed by a wide range of characterisation techniques such as BET, TGA, XRD, Raman and STEM. The work is part of a project funded by EU-FP7 (FREECATS) and is a collaboration with academic and industrial partners from several European countries. Co-advisors: Marthe Emelie Buan, Navaneethan Muthuswamy

HJV: Førsteamanuensis Hilde J. Venvik

HJV-1: Bifunctional catalyst for the direct DME synthesis. Dimethyl ether (DME), CH3OCH3, is the simplest ether and a possible clean and economical fuel for the future, with characteristics as a sulphur free diesel fuel with low particulate emissions and high cetane number. The properties of DME are similar to those of LPG and it can hence be used for power generation as well as residential heating and cooking. DME is currently produced in a two-step process; a methanol synthesis step followed by the methanol dehydration reaction. In order to use DME as a fuel, it must be produced at low cost in large quantities. The catalytic dehydration of methanol is carried out over an acidic catalyst, and the cost of producing DME from methanol is influenced by price and availability of methanol. DME production from syngas is thermodynamically more favourable than from methanol and the direct DME synthesis should thus be more economic, provided a suitable catalyst is identified and combined with the appropriate reactor technology. The project includes the synthesis, characterization and testing of catalysts for the direct DME synthesis, for which a state-of-the art experimental set-up has been built. A next step would be comparing the functionality of the bifunctional catalyst in the direct synthesis from synthesis gas to that in the methanol synthesis and methanol dehydration by kinetic investigations. The project is part of a collaboration with SINTEF Materials and Chemistry. Co-advisors: Prof. Anders Holmen, Research Scientist Rune Myrstad (SINTEF), PhD student Farbod Dadgar.

HJV-2: Microchannel membrane reactor for small scale hydrogen production

Membrane reactors combine separation and reaction in a single step. The yield of a product may also be increased by its extraction through the membrane if the reaction is equilibrium limited. Palladium based membranes are 100 % selective to hydrogen and hence suited for reactions that produce hydrogen, such as steam reforming of methanol methane, or the water-gas shift (WGS) reaction. A possible application is miniaturized production of hydrogen for fuel cells, as an alternative to batteries. Promising results were recently obtained by integration of thin (<5µm) Pd membranes developed and patented by SINTEF Materials and Chemistry into a microchannel geometry. We recently showed that the membrane’s permeability under pure hydrogen as well as its sensitivity to carbon monoxide (CO) could be changed (reduced) through a particular heat treatment, and this has important implications for their applicability. The microchannel configuration is particularly suited for investigations of these phenomena. The topic involves investigation of the effect of relevant co-molecules such as CO, CO2, H2O, CH4, and CH3OH in the membrane microchannel configuration through experiments and modelling, as well at characterization of surface species present on the membrane during and after permeation experiments. A next step could be to approach methane steam reforming conditions. The work will be carried out in collaboration with SINTEF Materials and Chemistry in Oslo. Co-advisor: Thijs Peters (SINTEF), PhD student Nicla Vicinanza, Post doc. Ingeborg-Helene Svenum. HJV-3: Initial stages of metal dusting corrosion Metal dusting corrosion constitutes a problem in the conversion of natural gas to fuels and chemicals because it causes a gradual breakdown of alloy surfaces into fine, dust-like particles. It is a result of unwanted carbon formation on the inner surface of process equipment, and occurs where metals and alloys are exposed to a gaseous atmosphere with low oxygen/steam partial pressure at elevated temperature (300 ºC and up). This is typical for the production of synthesis gas from methane. Metal dusting carries significant cost, since precautions need to be taken to avoid catastrophic events in industrial processes characterized by explosive and/or poisonous gaseous mixtures under high pressure and temperature. The progress of metal dusting in the alloy matrix once carbide phases have formed has been well studied and documented. The initial stage of metal dusting is, however, analogous to the carbon formation on catalysts used in the production of synthesis gas, but less described. Carbon formation on catalysts is essentially kinetically controlled, particularly facile on Ni, Co and Fe, and has been widely studied. Fe and Ni are common constituents of alloys with good temperature resistance; hence their stability in the alloy matrix is critical for metal dusting. The overall objective of this study is to obtain better understanding of the initial stages in metal dusting corrosion, i.e. the initiation of the carbon formation. This is done by preparing different surface oxides of a representative alloy, which is then exposed to high carbon activity gas atmosphere at high temperature. This is combined with advanced characterization before and after the exposure in order to find a relationship between the structure and composition of the alloy surface and its propensity to form solid carbon. Co-advisors:, Research Scientist John Walmsley (SINTEF), PhD student Daham Gunawardana.

HJV-4: Adsorption of alkaline metals on cobalt single crystal surfaces Cobalt based catalysts are important in converting synthesis gas (CO + H2) derived from natural gas, coal or (non-food) biomass into liquid fuels through the Fischer-Tropsch-synthesis. Small amounts of alkali metals present in the reactant mixture have, however, been found to affect the activity and selectivity of the catalyst. This is typically the case if the feedstock is biomass, since these elements may exist in biomolecules. In the commercial application, the cobalt is dispersed as small particles on a porous support, but investigations of well ordered single crystal surfaces under controlled atmosphere may provide insight to the adsorption and reaction phenomena on a molecular scale that may explain the observations made under realistic conditions.

The project concerns atomic scale experimental investigations of ordered cobalt surfaces through application of scanning tunnelling microscopy (STM) as well as other relevant techniques (XPS - x-ray photoelectron spectroscopy and , LEED – low energy electron diffraction, etc.). Small amounts of alkalis (Na, K) will be deposited on the cobalt surface in order to determine typical adsorption sites and structures. Thereafter, the effect of alkali deposits on other, Fischer-Tropsch relevant, phenomena may be studied, for example CO adsorption and Co-restructuring. The figure shows a 20 nm x 15 nm STM image published by the supervisors on how a Co(11-20) surface was restructured into a new, ordered arrangement upon CO

adsorption. The project is offered in a collaboration between Dept. of Chemical Engineering (IKP), and Dept. of physics (IFY), and is well suited for students specializing in Nanotechnology for materials, energy and environment as well as Catalysis/Chemical Engineering, with and interest in experimental investigations. The laboratories are available at the abovementioned departments. Co-advisors: Prof. Anne Borg, Dept. of Physics (IFY), Dr. Lars Erik Walle, IFY, Dr. Bjørn Chr. Enger, IKP.

Kolloid- og polymerkjemi/Colloid- and Polymer Chemistry JOHS: Professor Johan Sjöblom JOHS-1: Study of the mechanism of demulsification of petroleum crude oil

emulsions by demulsifiers Asphaltenes are the most polar molecules present in petroleum in which they are present in concentrations that can be as high as tens of percents. They are responsible for the formation of stable emulsions created at different points in the oil production chain. These emulsions need to be broken and the water removed. This is generally done by adding demulsifiers i.e. cocktails of chemicals during the production. This master project aims to better understand the oil-water separation mechanism by demulsifiers. In order to do that, the interfacial rheology properties of mixed films of asphaltenes and demulsifiers will be determined by two different techniques: the shear interfacial rheology and the dilational interfacial rheology and their results compared.

This project is a part of the Joint Industrial Program 1 project, a project sponsored by several central oil companies and chemical vendors. The work will be done at Ugelstad Laboratory, Department of Chemical Engineering. Co-supervisor Dr. Sébastien Simon JOHS-2: Study of aggregation of Tetra-acid and its interactions with crude

oil indigenous surfactants and inhibitors by Isothermal Titration Calorimetry

Tetra-acid (also known as Arn) is a molecule present in petroleum crude oil at low concentration, typically the ppm level, which can precipitate in presence of calcium to form deposits. These deposits have an impact on oil production and can even lead to costly shut-down. That is why it is important to determine the formation mechanism of these deposits. Recently it has been demonstrated that Arn can be present in crude oil but this des not always lead to the formation of deposit. One of the possible explanations is that this formation could be inhibited by other crude oil components. That is why, in this project, we propose to study the aggregation of Arn and its interactions with other crude oil components and inhibitors using isothermal titration calorimetry (ITC) by measuring the heat of reaction associated to these two phenomena.

This project is a part of the Joint Industrial Program 2 project, a project sponsored by several central oil companies and chemical vendors. The work will be done at Ugelstad Laboratory, Department of Chemical Engineering. Co-supervisor Sébastien Simon. Reserved for Ezequiel Orlandi JOHS-2: Determination of Mass of Tetra-Acid at the Liquid/Liquid

Interface by Combining Langmuir Trough with QCM Measurements

Tetra-acid (also known as Arn) is a molecule present in petroleum crude oil at low concentration, typically the ppm level, which can precipitate in presence of calcium to form deposits. These deposits have an impact on oil production and can even lead to costly shut-down. In order to understand the formation mechanism of these deposits, a new analytical method is currently being developed which aims to accurately determine the mass of tetra-acid at the oil-water interface. This new technique is based on the combination of quart crystal microbalance and Langmuir-Schaefer apparatuses.

This project is a part of the Joint Industrial Program 2 project, a project sponsored by several central oil companies and chemical vendors. The work will be done at Ugelstad Laboratory, Department of Chemical Engineering. Co-supervisor Dr. Sébastien Simon Reserved for Hanne Aleksandersen GØ: Professor Gisle Øye

GØ-1: Characterisation of gas-liquid interfaces related to offshore produced water treatment - the effect of pH Produced water (PW) is water co-produced with oil and gas during petroleum production. Currently, the amount of PW on the Norwegian Continental Shelf is around 140 million m3 per year, which is approximately the same amount as for the oil produced. The water content will continue to increase as the fields mature. PW streams contain pollutants like dispersed oil and solids, as well as dissolved organics and gas. These constituents must be separated from the PW streams in order to comply with environmental regulations if the water is to be discharge to sea, or to achieve sufficient quality for reinjection of the water into the reservoir. Gas flotation, i.e. attachment of oil and particles to gas bubbles, is a common method for removing dispersed oil and solids from the PW strems. The interfacial properties of water-gas and oil-gas interfaces will largely determine the efficiency of this method. The aim of this project will be to study changes in the interfacial tension between produced water and gas bubbles at short time scales. The interfacial tension measurements will be carried out utilising a maximum bubble pressure tensiometer. The project is part of a research programme sponsored by ConocoPhillips, ENI Norge, Schlumberger Division MI EPCON, Statoil and Total. Supervisors: Mona Eftekhardadkhan, Bartlomiej Gawel and Gisle Øye Reserved for Kaja Neeb Kløcker GØ-2: Characterisation of gas-liquid interfaces related to offshore

produced water treatment – the effect of pH Produced water (PW) is water co-produced with oil and gas during petroleum production. Currently, the amount of PW on the Norwegian Continental Shelf is around 140 million m3 per year, which is approximately the same amount as for the oil produced. The water content will continue to increase as the fields mature. PW streams contain pollutants like dispersed oil and solids, as well as dissolved organics and gas. These constituents must be separated from the PW streams in order to comply with environmental regulations if the water is to be discharge to sea, or to achieve sufficient quality for reinjection of the water into the reservoir. Gas flotation, i.e. attachment of oil and particles to gas bubbles, is a common method for removing dispersed oil and solids from the PW strems. The interfacial properties of water-gas and oil-gas interfaces will largely determine the efficiency of this method. The aim of this project will be to study changes in the interfacial tension between produced water and gas bubbles at short time scales. The interfacial tension measurements will be carried out utilising a maximum bubble pressure tensiometer. The project is part of a research programme sponsored by ConocoPhillips, ENI Norge, Schlumberger Division MI EPCON, Statoil and Total. Supervisors: Mona Eftekhardadkhan, Bartlomiej Gawel Reserved for Helle Hofstad Trapnes GØ-3: Characterisation of gas-liquid interfaces related to offshore

produced water treatment – interfacial activity of model components Produced water (PW) is water co-produced with oil and gas during petroleum production. Currently, the amount of PW on the Norwegian Continental Shelf is around 140 million m3 per year, which is approximately the same amount as for the oil produced. The water content will continue to increase as the fields mature. PW streams contain pollutants like dispersed oil and solids, as well as dissolved organics and gas. These constituents must be separated from the PW streams in order to comply with environmental regulations if the water is to be discharge to sea, or to achieve sufficient quality for reinjection of the water

into the reservoir. Gas flotation, i.e. attachment of oil and particles to gas bubbles, is a common method for removing dispersed oil and solids from the PW streams. The interfacial properties of water-gas and oil-gas interfaces will largely determine the efficiency of this method. The aim of this project will be to study changes in the interfacial tension between produced water and gas bubbles at short time scales. The interfacial tension measurements will be carried out utilising a maximum bubble pressure tensiometer. The project is part of a research programme sponsored by ConocoPhillips, ENI Norge, Schlumberger Division MI EPCON, Statoil and Total. Supervisors: Mona Eftekhardadkhan, Bartlomiej Gawel Reserved for Solveig Hodneland GØ-4: Characterisation of liquid-liquid interfaces related to offshore produced

water treatment - interfacial activity of model Components Produced water (PW) is water co-produced with oil and gas during petroleum production. Currently, the amount of PW on the Norwegian Continental Shelf is around 140 million m3 per year, which is approximately the same amount as for the oil produced. The water content will continue to increase as the fields mature. PW streams contain pollutants like dispersed oil and solids, as well as dissolved organics and gas. These constituents must be separated from the PW streams in order to comply with environmental regulations if the water is to be discharge to sea, or to achieve sufficient quality for reinjection of the water into the reservoir. Efficient separation of emulsions depends on the interfactial properties at oil-water interfaces. The aim of this project will be to study the time-dependent evolution of interfacial tension and interfacial rheology for various model systems. The measurement will be carried out using the pendant drop and oscillating pendant drop methods. Supervisor: Bartlomiej Gawel the project is part of a research programme sponsored by ConocoPhillips, ENI Norge, Schlumberger Division MI EPCON, Statoil and Total. Reserved for Omar Olhaye GØ-5: Investigation of interfacial tension of surfactants in low

salinity water for enhanced oil recovery applications Enhanced oil recovery (EOR) is the final stage in the recovery of crude oil from reservoirs. As many oilfields at the Norwegian Continental Shelf are entering the tail production phase, it is crucial to implement EOR processes in order to avoid extreme waste of valuable natural resources by leaving large amounts of oil in the reservoirs. Surfactant flooding is a well-known EOR technique that has been used worldwide for decades, while low salinity water flooding is a newer technique which only has been used in single-well tests. Currently, combined surfactant and low salinity water flooding is considered by the industry to be an interesting EOR approach as an alternative to the stand-alone techniques. The presence of surfactants in low salinity water can reduce the capillary forces trapping oil in the reservoir, while the low salinity water offers advantages such as improved surfactant solubility, reduced retention of surfactants in the reservoir and consequently less use of chemicals. The aim of this project is to carry out a screening study in order to indentify surfactants that will give low interfacial tension under relevant salinity and pH ranges. The interfacial tension measurements will be carried out utilising a spinning drop tensiometer. The project is part of a research programme carried out in collaboration with Department of Petroleum Engineering and SINTEF Petroleum, and is sponsored by Det Norske Oljeselskap, GDF SUEZ, Lundin Norge and Statoil. Supervisor: Thomas Tichelkamp Reserved for Yen Vu GØ-6: Investigation of loss of surfactants during enhanced oil recovery

applications - adsorption of surfactants onto clay materials Enhanced oil recovery (EOR) is the final stage in the recovery of crude oil from reservoirs. As many oilfields at the Norwegian Continental Shelf are entering the tail production phase, it is crucial to implement EOR processes in order to avoid extreme waste of valuable natural resources by leaving large

amounts of oil in the reservoirs. Surfactant flooding is a well-known EOR technique that has been used worldwide for decades, while low salinity water flooding is a newer technique which only has been used in single-well tests. Currently, combined surfactant and low salinity water flooding is considered by the industry to be an interesting EOR approach as an alternative to the stand-alone techniques. Low retention of surfactants in the reservoir is cruicial for the method to be efficient and economically feasibable. The aim of the project is to study the effect type of surfactant, pH, salinity and ionic composition will have on adsorption of surfactants onto kaolinite. The project is part of a research programme carried out in collaboration with Department of Petroleum Engineering and SINTEF Petroleum, and is sponsored by Det Norske Oljeselskap, GDF SUEZ, Lundin Norge and Statoil. Supervisor: Meysam Nourani Reserved for Eivind Joo Behrens GØ-7: Oil spill response – wettability alterations of shoreline surfaces Development of new and flexible oil spill response systems are required in order to prevent or minimize the environmental impact of oil spill accidents. One aspect of such systems is to have efficient shoreline clean-up operations that can collect as much of the stranded oil as possible and prevent it from remobilization into the sea. Better understanding of the interactions between shoreline surfaces and the spilled oil will facilitate the development of efficient clean-up operations and enhanced restoration rates of the polluted shorelines. The aim of this project is to investigate how the chemical composition of a (model) shoreline surface and different crude oils affect the interactions between the two phases, and how this influence wettability alterations. The interactions will be studied by the Quartz Crystal Microbalance technique, while the wettability alterations will be investigated by contact angle measurements. The project is carried out in collaboration with SINTEF Marine Environmental Technology Supervisor: Umer Farooq Student: Jostein Kjemperud WRG: Førsteamanuensis Wilhelm R. Glomm WRG-1: Synthesis of Hybrid Nanoparticles for Biocatalysis

Background Nanomaterials research has recently made tremendous progress with the wet chemical synthesis of new heterostructured nanoparticles with a topologically defined distribution of their composition, broadly referred to as hybrid nanoparticles (HNPs). For example, hybrid metallic/magnetic nanoparticles represent an important class of nanomaterials because of their unique properties and applications in drug delivery, multimodal imaging, recoverable catalysis, therapy in biomedicine. Several synthesis approaches have been investigated in recent few years for constructing HNPs; however, the detailed understanding of the underlying mechanism, control over the size of individual components (i.e., chemical composition), and type of crystalline/amorphous layer incorporation to nanoparticle to grow another component, etc. are not extensively explored. The proposed project will develop a facile strategy to address aforementioned issues, and will use seeds of different sizes made from either crystalline iron oxide or iron particle coated with a thin layer of amorphous layer for the direct nucleation, and growth of the Ag or Au nanodomains on the seed nanoparticle surfaces. The size and number of Ag/Au in each hybrid particle can be varied by controlling the reaction time and concentration of the different precursor. The plasmonic and magnetic responses of these different types of hybrid nanoparticles will also be evaluated. The project will use experimental techniques available at the Ugelstad Laboratory (UV-vis spectroscopy, Malvern Zetasizer Nano ZS) as well as in the NTNU NanoLab (Schlenk line, STEM). Co-supervisor: Gurvinder Singh (IKP), Bård Helge Hoff (IKJ)

WRG-1: Karakterisering av alkydemulsjoner Bakgrunn Grundig karakterisering av overgangen fra alkydkontinuerlig til vannkontinuerlige emulsjoner er av svært stor betydning for formuleringer i dekorativ overflatebehandlinger. Med utgangspunkt i prosjektoppgaven med samme tema, vil det i masteroppgaven være relevant å se på emulgeringsforløpet for ulike formuleringer der effekten av røreverk, surfaktantsammensetning, alkydtype og vanndosering. Emulsjonene vil bli karakterisert med hjelp av NIR, konduktivitetsmålinger, e-crit og viskositetsmålinger, for å bestemme parametre som inversjonspunkt, dråpestørrelsesfordeling og emulsjonsstabilitet. Co-supervisor: Tina Helland, Stian Engebretsen (JOTUN) Reservered for Martine Lefsaker

Prosess-systemteknikk/Process Systems Engineering SiS: Professor Sigurd Skogestad SIS-1: Optimal operation of parallel systems In order to use the available energy resources optimally, it is often necessary to recover as much heat as possible from a process. This can often be done using a self-optimizing control structure. The idea of self-optimizing control is to achieve near-optimal control by keeping certain variables or variable combinations constant. For heat exchanger networks with parallel branches, we have developed a simple polynomial variable combination which we are considering for a patent application. The objective for this work is to further study the method by considering specific applications, for example, a process stream which is heated using the heat from different batch processes. The main task is to set up a model of the process and to implement the polynomial variable combinations. Matlab and Simulink will be used for simulations Co-supervisor: Jophannes Jäschke (postdoc) SIS-2: Modelling and control of a Bio diesel plant The task is to develop a model for a Bio diesel plant. The project tasks are 1. a literature review on bio diesel, 2. setting up a steady state model 3. Simulation and optimization of the model 4. Design of a control structure. Co-supervisor: Jophannes Jäschke (postdoc) SIS-3: Modelling, control and optimization of multiphase Heat exchangers This project is motivated by our difficulties in optimizing LNG (liquefied natural gas) processes, but also other (simpler) processes may considered. Optimizing LNG processes is very difficult due to phase change in the heat exchangers and due to mixed refrigerants, which have very non-linear behaviour. Moreover, tight integration and small temperature differences between the streams make the problem numerically challenging. However, in order to find good control structures, it is necessary to design a model such that it can be used in an optimization software. The task for this project is to model and optimize a multistream/multiphase heat exchanger using e.g. a new disjunct programming approach, as is described in Kamath et al. http://onlinelibrary.wiley.com/doi/10.1002/aic.12565/pdf This project requires good math skills and the ability to work independently. Although the project is not an easy one, it can be a very rewarding one, because the first task is to reproduce the results in the paper by Kamath et al. The main focus of the project is on the modeling and simulation. In a follow-up master project, the focus will be on using the model for control structure design or extending it to mixed refrigerants. The simulations will be done in the modeling languages ampl or GAMS. Co-supervisor: Jophannes Jäschke (postdoc) SIS-4: Control strategies for divided wall (Petlyuk) columns Divided wall columns offer large potential savings in energy and capital costs, but control remains a difficult issue. The task is test by dynamic simulations alternative control structures. The objective is to find a simple and robust structure, for example, based on a combination of temperature loops and outer composition loops. The project will start by testing some proposals recently made in our group (Dwivedi, Halvorsen, Skogestad) and comparing with other suggestions (e.g., Luyben). For simulation of the column one may use Matlab or Unisim/Hysys.

SIS-5: Control structure design for a sequence of distillation columns A good control structure has to optimally adapt to changing product prices in order to run the process as profitably as possible. The task of this project is to design control structures for a sequence of distillation columns. The project consists of modelling the Distillation columns in a modelling language like ampl and to use the sensitivity features of the software IPOPT to extract information needed to design a good control structure. This is a follow-up work of a well-going existing project and requires good skills with programming languages e.g. matlab/ampl.

SIS-6: Temperature control for exothermic CSTR Controlling the temperature in an exothermic chemical reactor poses a challenge, since the process itself is both non-linear and unstable. In many cases the process has a time delay, because the cooling is effectuated by a cooling water flow, the influence of which takes some time to reach the reactor solution. This is the case regardless of whether the heat exchanger is placed inside the reactor, or in an exterior circulation loop the reactor. These three factors (non-linearity, instability, delay) alone make this control problem quite a challenging one. In addition we have process variations that require the control to be robust. We study continuous stirred reactors. Within the Perstorp group there are several reactors of this type. A project plan may look as follows. The scope can be reduced if there is not enough time available: Verify the mass and heat balances, and linearize this model around a generic equilibrium. Investigate which simple PID controller tuning methods that are available for this type of

linear processes. If there are none, then suggest one Match the parameters in the suggested tuning method with the physical parameters of the process. Quantify fundamental limitations on control performance. Can normal operations data be used to estimate the kinetics parameters k0 and Ea? Will a non-linear controller structure significantly improve achievable control

performance? For more information see: http://www.nt.ntnu.no/users/skoge/diplom/prosjekt12/ Co-supervisor: Krister Forsman, Perstorp AB SIS-7: Evaluation of SIMC PID-rule. We have recently tested the optimality of the SIMC PI-rule and found it to be surprisingly good (see reference below). Actually, this work was done as part of a project by Chriss Grimholt in 2010. We now would like to extended the work to PID control, that is, we want to compare the SIMC PID-rule and compare it with the optimal PID-controller. Tasks 1. Define basis for comparison (measures for performance, robustness and input usage) 2. Find optimal controller for a range of processes and compare with best PI/PID controller. Co-supervisor: Chriss Grimholt (PhD student) SIS-8: Optimal PI-Control and Verification of the SIMC Tuning Rule Proceedings IFAC conference on Advances in PID control (PID'12), Brescia, Italy, 28-30 March 2012. http://www.nt.ntnu.no/users/skoge/publications/2012/grimholt-pi/ Co-supervisor Chriss Grimholt SIS-9: Performance and Robustness of Smith Predictor Controller. We want to test the performance and robustness of a Smith Predictor controller for processes with large time delays, by comparing it with PI and PID control. The performance is obviously better if the time delay is known, but it is claimed that it performs poorly if the time delay varies. For example, how does the Smith Predictor perform if the time delay is reduced to zero, or if the time delay is doubled (which are changes that are easily handled using a PI controller)? SIS-10: Finding the active constraints regions The idea of self optimizing control is to achieve a near optimal operation by keeping some

"magic" controlled variables constant using the available degrees of freedom. For a given optimal nominal point all the constraints that are active are perfect candidates for self optimizing controlled variables so ideally we would like to keep them constant at their constraints but the major problem is that the set of the active constraints may change when the process is disturbed. The main idea of this project is to develop an online algorithm that will be able to predict the changes in the active constraint set as a function of disturbances. As a case study any Matlab or Hysys/Unisim process model can be used. Co-supervisr: Minasidis Vladimiros (PhD student) SIS-11: Optimization of processes using “self-optimizing” variables This project is motivated by our difficulties in optimizing LNG (liquefied natural gas) processes, but also other (simpler) processes may considered. Steady-state simulation and optimization of LNG processes is difficult because of tight integration and small temperature differences between the streams. For example, the UniSim has large problems in converging when trying to optimize the operation of a given network. One possibility is to let Matlab do the optimization and UniSim the simulation. The focus in this project is on finding the best variables to specify in UniSim. Another approach is to use dynamic simulation for finding the steady-state solution. Also in this case the selection of good “self-optimizing” variables is critical. Co-supervisor: Vladimiros L. Minasidis (PhD student) SIS-12: Dynamic back-off for control of active constraints To operate processes safely generally there are constraints which have to be observed. A typical examples for a safety constraint is the maximum allowable temperature in a reactor. Exceeding this constraint can lead to serious consequences, e.g. explosions. At the same time, it often happens that the plant profit is maximised when a variable is at this constraint. Therefore it is desirable to operate the process as close to the constraint as possible. In practice, we will always have to back off a little bit from the constraint, because we want to make sure that we do not violate it, even if the the process conditions vary. At the same time, we want to minimize the back-off, because it causes economic loss. The goal of this project is to study how the back-off can be adapted to dynamically changing operating conditions. The principal idea is to impose large back-off when the variable value changes fast, and little back-off when the variable changes slowly or not at all. The student should like to work with matlab and have some knowledge about simulation of differential equations. The tasks are

Literature review Set up a small dynamic model Find a law which dynamically adapts the back-off to the rate of change in the variable Simulate a batch reaction process as a case study or a pH process

Co-supervisor: Jophannes Jäschke, postdoc SIS-13: Flexible/optimal steady-state backoff for unconstrained variables to avoid infeasibility To operate processes safely generally there are constraints which have to be observed. A typical examples for a safety constraint is the maximum allowable temperature in a reactor. Exceeding this constraint can lead to serious consequences, e.g. explosions. Variables which are unconstrained under a certain set of operating conditions may reach a constraint under other conditions. To remain truly optimal in both operating conditions, the control structure has to be changed. In practice, however, one would like to keep the control structure simple and to use one control structure for all operating conditions.

This project involves investigating under what circumstances a control structure can be found, which may not be truly optimal, but which does not have to be adapted to changing constraints. We will consider the case of a linear plant and a quadratic objective function. The student should like to work with matlab or some other programming language and have some knowledge in linear algebra Tasks:

Literature review Set up small examples and find control policies, which give an acceptable loss Derive theoretic results about how much loss has to be accepted when using a single control

structure for all operating conditions Co-supervisor: Jophannes Jäschke, postdoc SIS-14: Studies on modelling and control of distillation columns (in cooperation with Statoil/Gassco at Kårstø). Several projects possible. Need to be further discussed with Marius Govatsmark at Statoil Kårstø. SIS-15: Expected problems when pairing on negative RGA-elements The basis for this project is that it is not clear what happens if one pairs on a negative RGA. This will be a mix between simulation (in Simulink) and theory. Background: Pairing on a negative steady-state RGA-element may give good decentralized control performance, but there are potential risks. First, note that if one pairs on a negative RGA, then one cannot tune the controllers using independent designs (where each loop is tuned separately with the other loops in manual), because one would get instability when all loops are closed. Second, consider sequential loop closing, which is probably more common practise. In this case, pairing on a negative RGA is claimed to result in instability, and the objective of this work is to study this in more detail. SIS-16: Oil Production Optimization using Self-Optimizing The petroleum fields are usually optimized on several time horizons. On the long time horizon, typically ranging from one year to the reservoirs lifetime, decisions are related to the physical development of the field. That is, which production units should be commissioned, where should they be placed, and when should they be operational. On the medium time horizon, the planning revolves around maximizing the oil and gas extraction from the field within the bounds of the long time scale strategies. On this horizon, commissioning of new wells and their location, as well as the use of artificial lift technology, are important topics. Operational production planning occurs on the short time horizon, ranging from weeks to days, and is also known as real-time production optimization (RTPO). The objective is to maximize the daily production rates considering down-hole effects like coning, and production limitations like pipeline and downstream water handling capacity. Usually the RTPO problem is solved once a day under the assumption that the well conditions remains fairly constant. However, between each iteration of RTPO, the down-hole condition may change resulting in a suboptimal operation. In this project we will use a simple steady state model that consists of a four well cluster connected to a separator with one pipeline. The objective is to maximize oil production while satisfying the production constraints.

The goal of this project is to find good control variables (CV) such that, by using feedback, we can keep the production close-to optimum despite disturbances in down-hole conditions (e.g. gas oil ratio). We will find different CV by using well know methods like the null space method and exact local method, but we will also use newer concepts J\"aschke's optimal split of parallel units (by using marginal cost). We will also investigate changes in active constraints and how the control structure changes between the different constraint regions. Co-supervisor: Chriss Grimholt SIS-17: Optimal Temperature Control of rooms for Minimum Energy Cost

At any given time, the energy production is expected to cover the energy demand. Due to increasing energy consumption and larger usage of weather dependent generation like wind- and solar-power, managing this production-consumption gap is becoming a important research topic. One possible solution would be to reduce the fluctuations in the energy consumption by shifting the consumption from peak loads to more beneficial periods. Field tests in the USA have demonstrated that optimization of domestic energy consumption can significantly reduce load peaks. This can be achieved by manipulating the energy price according to demand information and weather forecasts. Electricity consumers are encouraged to consume electricity more prudently in order to minimize their electric bill. In such a scenario, the adaptation of the energy consumption by the final consumer is essential to the success of the approach. In this project we will focus on optimizing the energy cost of room heating by storing energy (e.g. in the floor or in a water heater) when energy prices are low, and use this energy when energy prices are high. Assuming that we have predictions for the future energy price and weather, we will compare model predictive control (MPC) with simpler feedback control strategies. The goal will be to find a simple setpoint switching strategy such that we minimize the energy cost without breaking constraints. We will extend the concept of self-optimizing to find a measurement combination which invariant at the optimum switching time despite disturbances such as price, outdoor temperature, and air venting. Co-supervisor: Chriss Grimholt SIS-18: Closed-loop optimal control of batch crystallization processes Batch crystallization is well established in the industry for the small-scale production of fine chemicals and pharmaceuticals industries as a purification and separation technique. Generally, chemical reaction steps take place in liquids while the final product is, in many cases, solids. Often, the solid product is obtained by crystallization. Many physical properties of the products are strongly linked to their size and shape. For instance, surface structure and reactivity varies with crystallography orientation. The production of crystalline material with a desired size distribution is a big challenge in industrial crystallization. In batch cooling crystallizers the fact that solubility depends on temperature is exploited to reach given specifications. The goal of this project is to use dynamic optimization techniques to obtain temperature profiles that minimizes the mass of nucleated (undesired) crystal in a batch cooling crystallization process. For this purpose we will use population balance models available on the literature and we propose applying simple single and multiple shooting methods for dynamic optimization. Once the optimal temperature profile is available an important question still remains: How do we implement it in practice in a simple and reliable way? For this we will seek simple feedback control structures that yield near optimal batches despite disturbances and implementation errors. To deal with disturbances, the main idea will be to find a combination of variables whose optimal trajectory is insensitive to the disturbance. Therefore, tracking this trajectory by a feedback controller will automatically produce optimal inputs for any sufficiently small disturbance. Finally, to minimize the effect of implementation errors in the optimal solution we will find the best (in

some to-be-defined-sense) transformation for the time domain variable. Such transformation should produce a warped time variable that better measures the evolution of the batch. Co-supervisor: Vinicius de Oliveira

Four master project proposals on slug control Spring 2013

Supervisor: Sigurd Skogestad, Dept. of Chemical Engineering, NTNU Co-supervisor: Esmaeil Jahanshahi We have for many years worked with modeling, simulations (Olga) and experiments for avoid slug flow in offshore installations. This is an interesting problem with a large economic potential for increased production. Slug-1: Nonlinear Control Strategies for Anti-Slug Control Supervisor cybernetics: Morten Hovd The motivation of this project is using nonlinear control techniques for improved stabilization of the offshore production facilities (pipeline-riser systems) compared to linear controllers. Dynamics of pipeline-riser systems with severe-slugging flow condition is highly nonlinear. Therefore, it is expected to improve the control and increase the controllability region of the system by using nonlinear control techniques. One example is using top-side pressure measurement for stabilization of the system. This measurement shows controllability problems found by frequency-domain controllability analysis of the linearized model. In addition, we could not be able to stabilize the system with this measurement by means of linear controllers. However, improved results have been achieved by using a high-gain observer and state-feedback. Moreover, the non-linear controllers are able to bring the system from an unstable condition to stable condition. It could be beneficial to explore other nonlinear control strategies for anti-slug control. The following control strategies might be tested:

a. Nonlinear observer-based controller b. Sliding mode controller c. Feedback linearization d. Lyapunov redesign e. Back-stepping

… and any good solution that you come across during the project. Slug-2: Online PID Tuning for Unstable Processes: Application to Anti- Slug Control PID controllers are still the most widely used controllers in the industry; in particular satisfactory results have been achieved in anti-slug control by the PID controller. However, this requires online re-adjusting the controller gain to counteract the nonlinearity of the system, because the slugging flow is a highly nonlinear phenomenon. Most of the online PID tuning rules are for stable first-order plus time-delay systems, while slug flow constitutes two unstable complex conjugate poles. This project involves following tasks:

a. Closed-loop identification of the unstable system (set-point change, relay feedback) b. Designing a stabilizing controller for the identified model by using IMC, LQR or H-inf c. Approximating the controller by the closest PID controller. d. Testing the resulting PID controller on OLGA model and experiments. e. Formulating simple PID tuning rules for similar unstable processes.

Slug-3: Simplified first principle model for severe-slugging flow in S- Shaped risers Supervisor process and energy department: Ole Jørgen Nydal

There have been a lot of research for modeling and control of L-shaped risers, and always we assume that behavior of the S-riser is not very different from the L-shaped ones. However, an S-riser has two bends and dynamics of the system are slightly different. We aim to investigate differences in behavior of two types of risers. We could use the model for L-shaped risers for S-shaped risers, otherwise we can extend the model for L-shaped risers by adding one more artificial valve for the second bend.

a. Simulating S-riser in OLGA (one OLGA case for S-riser exists) b. Extending the simplified model for L-riser to S-riser c. Comparing the results from OLGA and simple model d. Comparing results from the S-shaped riser to results from L-shaped riser model e. Verifying the simplified model by experiments on the S-riser in multi-phase flow lab f. Controllability analysis of the resulting simplified model. g. Control simulations using the simplified model and OLGA.

Slug 1- Robust control solutions for stabilizing flow from the reservoir: S-Riser

experiments Supervisor process and energy department: Ole Jørgen Nydal

a. Stabilizing control experiments using bottom pressure (buffer tank). b. Control using top pressure combined with density. c. Testing online PID tuning rules on S-riser experiments. d. Investigating effect of control valve dynamics (comparing slow valve and fast valve) e. Control simulations using LedaFlow and OLGA. (optional)

TH-W: Associate Professor Tore Haug-Warberg

TH-W-1: The PC-SAFT equation of state is designed to model complex mixtures of gases, liquids and long chain molecules. Background: The Perturbed Chain Statistical Association Fluid Theory (PC-SAFT) is a quite recent equation of state which is capable of modelling mixtures of hydrocarbons with varying lengths of the carbon chains. The model is capable of predicting multiphase equilibrium as well as thermo physical properties. It has been in use for approximately 10 years but there are some persistent issues about the model structure that makes it non-obvious how the dervatives should be calculated. The model exists in several flavours and it is not straightforward to jugde which modifactions are minor changes and which are not. E.g. in the original form it is an implicit model which must be solved at every iteration of the phase equilibrium calculation. This is not very practical and it is the aim of this project to do a couple of implementations and testings to gain some experience with the model – both theoretically and practically. Goal: The task will be to establish analytical thermodynamic derivatives of the model, implement it into an in-house tool called NeqSim and test model predictions on various glycol based equilibrium systems. The derivatives shall not be strictly tied up to NeqSim (Statoil) but shall be delivered on a form that makes other implementations possible such as RGrad (NTNU). Prior knowledge and experience: The student must show an interest in computer programming and numerical mathematics, and must have a fair background in physical chemistry and thermodynamics. Co-supervisorS: Geir Arne Evjen (Statoil) and Even Solbraa (Statoil) NS-B: Førsteamanuensis Nadi Skjøndal-Bar NS-B-1: Dynamical Modelling of the factors influencing appeting and feed intake in

fish Appetite and feed intake have a major impact on fish behavior and growth (Fernø et al. 1995, Lokkeborg and Fernø, 1999, Føre et al. 2009). The behavior of fish is mostly affected by the response to food, and more specifically, by the level of appetite. The mechanisms behind appetite regulation in fish are

investigated by several groups worldwide, yet no attempt has ever been made to integrate the knowledge in a systematic manner. To better understand feeding behavior and what regulates growth performance, we need to understand appetite in more detail. Goals: �By using an integrated (system) approach we wish to understand the combined effects of many endocrine factors on appetite and feed intake. Furthermore, it should be possible to rank (prioritize) the influence of these factors on appetite such that future research can be channeled towards the factors with the largest impact �Understand the role of known endocrine factors in the overall effect on appetite. �Understand how the various factors linked together, how do they affect each other in addition to their individual effect on appetite. Methodology: Framework: the model should be designed in Mathwork Simulink (available for NTNU students), but can be modelled by other measures, such as CellDesigner or by sets of differential equations. The complexity of the system is large and so is the number of components. However, to compensate for the complexity, the model will be designed is phases. The first Phase is to form a simple model of appetite regulation, mostly based on quantitative information available today in the literature. The number of variables expected is 4-10, and will be the variable that are known to have the largest effect on appetite and feed intake. Response (appetite) will be studied as the function of changes in the variables. The second Phase will increase the complexity by incorporating several other variables, also quantifiable. Response will be examine here as well. The Third phase will include all the other know variables, some of themhave unknow quantities, and estimate their influence on the appetite. Some simple analysis is recommended, such as sensitivity analysis to parameters and variables. Requirements: Basic knoweldge on modelling and simulations, either matlab or CellDesigner. Completed Years 1-4 in engineering. NS-B-2: Development, analysis and simulations of gene regulatory circuits

of Gastrin, Forskulin, HRG and EGF stimuli networks in Cancer research.

Network component analysis (NCA) is a tool that predicts the activity of transcription factors (TF) and their effect on their target genes (TG), given a known network topology and microarray expression data. The activity of the TFs is not directly measureable, and this prediction is useful to understand the cascade effect of gene activation and regulation. It was show recently that genetical circuits that identify the cascade chain reaction of gene activation and supression, can be developed from NCA analysis and protein protein interaction topology information. This circuits are very important for the understanding of cell signaling and regulation in cancer research. The main goal of the project is to first construct and then study regulation of genetic circuits using NCA and simulink/matlab, of one or more of the network stimulated by Gastrin, Forskulin, EGF and HRG. The gene circuits can be contructed in Matlab Simulink or CellDesigner. Analysis and simulations of these circuits will then be conducted to identify feedback /feedforward elements in the network. Metodology: Framework: the circuits should be designed in Mathwork Simulink (available for NTNU students), but can be modelled by other measures, such as CellDesigner or by sets of differential equations. NCA simulations should be conducted to create a matrix of TF temporal activity P. Matlab NCA/gene circuits toolbox developed by systems group will be applied to identify and contruct the circuits. Later, analysis of this circuits will be conducted ot identify feedback/forward elements in the network and generate hypothesese for tesing in the laboratory. Lab work will not be required and is not part of this project. Basic knowledge in NCA, Linear algebra, and engineering mathematics is required. Co-supervisor: Naresh Doni Jayavelu

Miljø- og reaktorteknologi/Environmental Engineering and Reactor Technology Group Reaktor Technology HAJ Professor Hugo Atle Jakobsen HAJ-1: Masteroppgave reservert for Kristian Selvaag: A multidimensional combined multifluid-PBE model for fluidized bed reactors: Application to SE-SMR In the reactor modeling group we have long time experience in modeling the steam methane reforming (SMR) process as operated both in packed bed and fluidized bed reactors. Similarly, the environmental friendly sorption enhanced – steam methane reforming (SE-SMR) process has been modeled in a similar manner. In a recent PhD study it has been observed that the pellet weight distribution of the sorbent particles might introduce a particle segregation effect which makes the heavy sorbents sink to the bottom and the lighter catalyst pellets will concentrate on the top. A way of avoiding this problem might be to design a single pellet with both the sorbent and catalyst properties. In this project the impacts of the segregation phenomena, the makeup of active sorbents as the sorbents deactivates, the crushing of solids due to the particle-particle and particle wall collisions, etc on the chemical conversion and hydrogen production will be studied. In the first phase of the project a brief literature study will be performed to establish the combined multifluid-population balance modeling framework with suitable closures and kernels for the important phenomena as occurring in these fluidized bed reactors. In a second phase, the established dynamic model should be solved in 2D (one space coordinate and one property coordinate) by use of the least squares method as implemented in matlab. In the last part of the work, the model will be re-implemented in another programming language and extended to multiple spatial dimensions. The latter part is necessary as the solution of the multifluid model constituting the Navier-Stokes equations and the continuity for each phase is computationally demanding. By use of this model several effects should be elucidated; is the reactor operated in a dynamic of steady-state mode, are the weight segregation phenomena important, how to perform the sorbent makeup in an optimal manner, etc HS: Professor Hallvard F. Svendsen Relatet to CO2-capture: HS-1: Kinetics and modelling in CO2-amine systems

Faglærer/Veiledere: Hallvard Svendsen/Hanna Knuutila/Juliana Monteiro The project is reserved for Hammad Majeed

HS-2: VLE for the CO2-amine systems Faglærer/Veiledere: Hallvard Svendsen/Hanna Knuutila/Ardi Hartono etc. The project is reserved for Mandana Amiri

HS-3: VLLE for amine systems

Faglærer/Veiledere: Hallvard Svendsen/Hanna Knuutila/Ardi Hartono etc. The project is reserved for Kristine B Foss

HS-4: Physical properties of amine systems Faglærer/Veiledere: Hallvard Svendsen/Hanna Knuutila/Ardi Hartono etc. The project is reserved for Birgit Johansen

HS-5: Modeling of degradation processes.

Faglærer/Veiledere: Hallvard Svendsen,Hanna Knuutila The project is reserved for Thea Brodtkorp

HS-6: Corrosion in degradet systems Supervisors: Hallvard Svendsen The project is reserved for Ebenezer Hayfron-Benjamin

HS-7: Degradation in amine system (CO2 capture)

Faglærere/Supervisors: Hallvard Svendsen/Hanna Knuutila The project is reserved for Maren Johansen, Dept of Chemistry NTNU

HS-8: Modeling of adsorber dehydrator Kårstø

Faglærere/Supervisors: Hallvard Svendsen/Hanna Knuutila/NN Statoil The project is reserved for Nicola Stewart

HS-9: Degradation in circulating loop

Faglærere/Supervisors: Hallvard Svendsen/Hanna Knuutila, NN Statoil The project is reserved for Mahla Rashidian

HS-10: Procede 1

Faglærere/Supervisors: Geert Versteeg/Hallvard Svendsen/Hanna Knuutila The project is reserved for Kristine Snarvold

HS-11: Procede 2 Faglærere/Supervisors: Geert Versteeg/Hallvard Svendsen/Hanna Knuutila The project is reserved for Usman Shoukat

HS-12: Procede 3

Faglærere/Supervisors: Geert Versteeg/Hallvard Svendsen/Hanna Knuutila The project is reserved for Muhammad Awais

MH: Professor Magne Hillestad MH-1: The effect of operational parameters in a methanol plant Statoil’s methanol plant at Tjeldbergodden converts natural gas to methanol. The plant consists of an air-separation-unit (ASU), syngas production, methanol synthesis and raw methanol distillation. This project will focus on the methanol synthesis loop but also the syngas production is of interest. There are a number of operational parameters that is of interest to look at, such as recycle ratio, syngas composition (makeup gas), temperature and pressure. The effect of these parameters will change with the catalyst activity. It is of interest to study the effect of different parameters at different catalyst activities (combination of activity and effectiveness factor). The synthesis loop can be modelled in Hysys, UniSim or Matlab with a published kinetic model. The continuation of this work for a master thesis will focus on new designs of the methanol synthesis.

MH-2: Systematic Staging in Chemical Reactor Design For economic and environmental reasons, it is of paramount importance to develop process technologies with improved material and energy efficiencies. The input factors such as raw material and energy should be utilized to produce valuable products, with the use of least possible equipment volumes, areas, energies etc. A simple criterion is space-time-yield, but other criteria that include energy efficiency will also be considered.

The core of a chemical plant is the reactor. A method for systematic staging of chemical reactors will be further developed and applied with a published kinetic model. Reactants pass through a series of functions or basic operations to form the desired products. The basic operations are represented by design functions on the volume path. The design functions are fluid mixing (dispersion), distribution of extra feed points, distribution of heat transfer area and coolant temperature, catalyst dilution distribution and more. The conceptual reactor design problem is solved as an optimal control problem. Parameterization of the design functions and the state variables are applied. The realization is a staged process string of multifunctional units. The method is to be applied on a known system where the kinetics and other phenomena are described. The model will be programmed in Matlab or Python. Application area can be on a free radical polymerization reaction where the objective is to design a reactor path that produces the desired molecular weight distribution (MWD) in combination with an economic objective function. Review different ways of calculating the MWD, implement a method of calculating the MWD together with the entire kinetic model. Apply the model to find the optimal mixing configuration, initiator and monomer feed distribution, heat transfer area and coolant temperature distribution in order to produce a desired MWD most cost effective way. Part of this will be suitable for a project work and may be continued for master thesis. Co-adivor: PhD Student Paris Klimantos MH-3: Dynamic modelling and simulation of a CO2 capture plant We will focus on dynamic modelling of a post-combustion capture plant based on an amine solution. The motivation is to evaluate the process design and operational philosophy of the plant. By dynamic simulation we will analyse how the plant is able to handle large load changes, start-up and shutdown procedures, flue gas composition changes, etc. Based on the simulations the design and operational procedures, including process control are to be evaluated and if necessary improved. The model of the absorber may be modelled as plug flow both for gas and liquid. Co-advisor: PhD Student Nina Enaasen MH-4: Modelling and optimization of a Gas-to-Liquid plant A GTL plant consists of syngas production, Fischer-Tropsch (FT) synthesis, and FT products upgrading. Different technologies have been developed for syngas production unit such as steam methane reforming

(SMR), autothermal reforming (ATR), gas-heated reforming and combinations thereof. In the FT unit the syngas is converted to liquid fuels on an iron or cobolt catalysts. There exist different reactor configurations for FT units, such as slurry bubble column and fixed bed reactor. Modelling of the GTL plant can be made in Hysys, Unisim or other systems. Model the FT unit will be by introducing a known kinetic model such as one given by Iglesia et al1. Compare different process configurations of syngas production in a GTL plant; perform a pinch analysis for optimal heat integration of the plant and make simple cost estimations for process evaluation. Co-advisor: PhD Student Paris Klimantos MH-5: Energy considerations around an amine CO2 capture plant Adding a CO2 capture plant to a power plant will introduce a penalty up to 30%. A post combustion CO2 capture plant will consist of an absorption column, a stripper, heat exchangers, a blower, pumps, CO2 compression. The most energy requirement is the steam for stripper. The aim of this project is to find the suitable solvent and operating condition and best configuration to reduce the energy consumption for a post combustion capturing plant. This project has three main tasks. The tasks are as follows: Solvent investigation and comparison for CO2 capture The irreversibility in capturing plant and the effect of it on energy consumption Compare different alternative configuration for capture plant In addition to analytical models, the capturer plant can be modelled in UniSim, Hysys or Aspen plus. Co-advisor: Karl Anders Hoff (Sintef) MH-6: Evaluation of a North Sea oil platform using exergy analysis The typical power consumption at a Norwegian continental shelf platform is around 10 MW to several 100 MW. Most platforms generate their own power with gas turbines and diesel engines. In 2008, gas turbines and diesel engines on oil platforms were responsible for 21 % of Norway’s total CO2 emissions [1]. Reduction in power consumption at the continental shelf is therefore an important challenge. There is a need for a tool to evaluate the performance of such offshore platforms. CO2 per produced oil is often used. However, different platforms have different operating conditions. Exergy efficiency is an alternative performance parameter where operating conditions are taken into account. Also, by doing an exergy analysis, one can indicate potentials for reduction in power consumption throughout the process. A HYSYS model of the oil and gas processes of an offshore oil platform shall be established, based on historical data provided by Statoil. An exergy analysis shall be performed, giving the exergy efficiency and indicating irreversibility in the process. [1] Statistics Norway, Statistisk Sentralbyrå. Emissions of greenhouse gases. 1990-2008*. http://www.ssb.no/emner/01/04/10/klimagassn/ [29.04.10]. Co-advisor: PhD student Mari Voldsund (Kjemi) Reserved for Jonas Kaasa MH-7: Gas-liquid model for SO2 The regenerable Elsorb Process is an eco-friendly buffer system for SO2 recovery from gas streams. The technology has been developed at NTNU in cooperation with SINTEF mainly for gases less than 5000 ppm SO2. Other industry sectors such as metallurgy, with richer off-gases, can also apply the technology, but needs some process modifications depending on the SO2 partial pressure.

1 E. Iglesia, S.C. Reyes, S.L. Soled, Reaction-Transport Models and the Design of Fischer-Tropsch Catalysts, Exxon Research and Engineering Company, Annandale, New Jersy, in: E.R. Becker, C.J. Pereira (Eds.), Computer-aided design of catalysts, New York 1993, pp. 199-257

The buffer system consists of an aqueous solution of Na2HPO4, NaH2PO4 and Na2SO4 formed from solvent degradation and SO3 in the feed gas. The off-gas is contacted by the absorption liquid to give a SO2 loaded solution, which is regenerated by evaporation (temperature/concentration shift) or steam stripping (temperature shift). The optimal regeneration method and buffer composition has to be evaluated to match the process conditions. An optimal gas treatment process requires reliable GLE data for the buffer solution to match the feed gas conditions and the required cleaned gas quality. The energy consumption for solvent regeneration is closely connected to the loaded buffer composition and must be minimized. A GLE model for the buffer should include the buffer composition and temperature. GLE data for some buffer compositions and temperature are available for model tuning. Co-advisors: Prof. em. Olav Erga and Olav Juliussen (SINTEF). MH-8: Online State Estimation of Gas Pipelines The following text is suggested by Gassco: Gassco har nylig tatt i bruk et nytt system for sanntidsovervåkning av rørmodellene vi opererer. Vår nye sanntidsstrømningsmodell kjører på kontrol mode "Maximum Likelihood State Estimation" beskrevet i vedlagt paper. En modell for lekkasjedeteksjon basert på volumbalanse skal teoretisk kjøre på kontrol mode trykk for å ha best mulig sensitivitet på deteksjonen. I tillegg er det kjent at tuning av en sanntidsmodell kan påvirke sensitivitet for lekkasjedeteksjon til modellen. Det er av interesse for Gassco å se i hvor stor grad denne sensitiviteten påvirkes for en gitt rørmodell basert på: Hvilken kontroll mode som kjøres? Hvilke tuningsalgoritmer som er i bruk Hvilken instrumenteringen modellen har? Demping basert på lengden av tuningssløyfene? Lengden på akkumuleringsperiodene til volumbalansen? Er det mulig å gi anbefalinger til bruken av modellen for å optimalisere lekkasjesesitivitet? Er det forslag til forbedring av algoritmer eventuelt en guidelines til bestemmelse av parametre som forbedrer sensitiviteten spesielt ved kjøring av MLSE mode? The topic is reserved: Nils Arne Susort. MH-9: Modeling and model identification of an equilibrium amine system Co-supervisors: Hallvard Svendsen and Diego Pinto The topic is reserved: Hilde Ekrheim Membrane Research Group - Membrane competence and/or polymeric chemistry background needed M-BH Professor May-Britt Hägg

M-BH-1: Preparation of PVAm/PSf composite hollow fibers for flue gas applications Processing large volume of gases from industrial sources requires a large membrane area with a minimal foot print. Hollow fibre membrane geometry represents optimum solution due to the high ratio of membrane area per volume.

The assignment requires a literature study and practical experiments. The literature study will investigate different coating techniques for thin films such as dip coating. The laboratory work will consist of PSf hollow fiber membrane coating with a selective layer of PVAm, possibly followed by a protective coating. The polysulfone hollow fibers to be coated are available from Air Products. The membranes will be investigated by scanning electron microscopy (SEM), gas permeation (before and after coating), IR spectroscopy and possibly other methods. Different parameters will be optimised to obtain highly permeable and defect free coated hollow fibers. Recommended protective coating may also be tried and tested. Optimization of the PVAm coating: polymeric solution concentration, choice of solvent, coating procedure and drying protocol. The coated hollow fibres will be packed in modules and membrane separation properties will be tested for different gas mixtures such as CO2/N2,

CO2/CH4. Co-supervisor: Dr. Maria Teresa Guzman Gutierrez M-BH-2: Testing and optimization of PVAm/PVA blend membranes at high pressure This project will focus on the testing and optimizing of polyvinylamine/polyvinylalcohol (PVAm/PVA) blend membrane for natural gas sweetening at high pressures. The objective of this project is to improve the target membrane to be more resistant at high pressures (up to 80bar) without the loss of the CO2 separation efficiency. Carbon nanotubes (CNTs) are considered as the nano-fillers in making the PVAm/PVA blend based nanocomposite membranes. Supported hollow fiber membranes will be prepared and is to be tested for high pressure natural gas sweetening. The scope of this work can be specified as follows: (1) Permeation test of the CNT-blend hollow fiber membranes or with other nanoparticles at high pressures

(10bar, 20bar, 40bar, 60bar, 80bar). The membranes will be prepared in various conditions with various thicknesses. The tests will be performed in an advanced high pressure pilot scale rig with an automatic operation monitoring and controlling system. The hollow fibers will be made available – spinning is not part of the project.

(2) Optimization of the membrane preparation conditions based on the membrane separation performance at high pressures. The effects of cross-linking procedure, support membrane, membrane thickness will be investigated and the optimized membrane preparation condition determined.

(3) Characterizations of the blend membranes using SEM and other techniques. Co-supervisor: Dr. Xuezhong He M-BH-3: Forward osmosis membrane study on high temperature and crude oil systems - Osmotic membrane pressure actuator (OMPA) This project will be part of a collaboration with Statoil, and is a complete new way for looking at increased oil recovery from existing wells. Inflow control device is a technology for controlling the inflow of gas, oil and water from the reservoir to the wells. Inflow control devices have become increasingly important as measures of improving production and reservoir management. The focus of this study is autonomous inflow control technology for choking of water in gas-condensate wells. The technology uses the principle of osmosis to actuate a valve and is termed; Osmotic membrane pressure actuator (OMPA). The technology is proved to work in a low pressure and low temperature environment using fresh water, crude oils and different osmotic agents. The FO membrane used at Telemark University College and Statoil were cellulose acetate and polyimide membranes. The property of the cellulose acetate membranes does not meet the requirements of high temperature conditions in the well and even though the polyimide material can withstand up to 300oC initial testing revealed that the selective layer loosened from the support at higher temperatures. A screening of membranes to be used in OMPA was executed in 2010. It was found that a commercial available forward osmosis membrane with the properties to withstand high temperatures does not exist. Scope of work (SOW) The proposed project will be a follow up of a MSc-thesis performed spring 2011. The main part of Task 1 and 2 have therefore already been done, but some additional information for these two tasks will also be needed. The focus will therefor be on Tasks 3 and 4. The project will be performed in collaboration with Statoil.

The SOW is listed below in prioritized order. Task 4 may be considered as additional work.

1. A literature study on materials that can withstand temperatures up to 200oC to be used for membrane development will be given together with a strategy on how to prepare the membrane. Other properties like potential durabilities and characteristics should be identified.

2. Membrane specifications for the group of selected materials will be identified using the well conditions from a specific field. An overview of potential challenges as e.g. fouling that must be solved to satisfy the functional requirements will be given along with recommendations on how this can be done. Other important characteristics that must be taken into account is the ability of a thinfilm selective layer to attach to the support at high temperature and the retention properties. The final membrane can potentially be a composite membrane consisting of an inorganic support coated with a thin film selective layer, a composite of two polymers, or an asymmetric membrane of one type of polymer. The various alternatives should be discussed.

3. Laboratory Testing of membranes to measure the properties of forward osmosis membranes will take place at the laboratory facilities at NTNU. The pore size, water flux, retention will be measured for commercial alternatives, likewise measurement of thermal stability (Tg) using DSC. The initial testing/characterizing of the membranes will be done in a RO cell – this is a usual way of doing the first scanning of materials.

4. Initial preparation/synthesis of new membranes that can withstand the conditions in a reservoir, i.e. temperatures up to 200 °C, pressure up to 200 bar and the chemical environment (condensate, saline reservoir water, H2S, organic acids etc.) will be recommended. The membrane should be able to provide reversibility, acceptable resistance against fouling, have a long lifetime and high integrity.

Co-supervisor: Dr Qiang Yu LD: Associate Professor Liyuan Deng LD-1: Synthesis and optimization of PVA nanocomposite membrane in membrane contactor This project will focus on the synthesis and optimizing of polyvinylalcohol (PVA) nanocomposite membrane in membrane contactor using water based absorbent for CO2 capture. The objective of this project is to improve the CO2 separation efficiency of the target membrane without the loss of its mechanical properties in water. Nano-sized biofibers, carbon nano-tubes (CNTs) or nanoparticles are considered as the nano-fillers. The functions of the nano fibers in this membrane include the reinforcement of the membrane mechanical properties and the improvement of the membrane swelling capacity and hence CO2 separation efficiency. The scope of this work can be specified as follows: (4) Optimization of the crosslinking conditions of PVA mixed with nanofibers based on the swelling

capacity and mechanical strength of the PVA. Orthogonal experimental design will be used. (5) Synthesis the nanocomposite membrane with optimized PVA nanocomposite as selective layer. The

optimization of the support membrane and top layer thicknesses are included, which is based on the results of their permeation test.

(6) Permeation test of the membranes. The tests will be performed in a humidified CO2 gas separation

system with automatic operation monitoring and controlling system. (7) Characterizations of the PVA nanocomposite membranes using SEM and XRD This project may contribute significantly to the success of a green process for CO2 capture. Creativity in this project is highly appreciated. Reserved for Anne Maupillier

Crystallization J-PA: Associate Professor Jens-Petter Andreassen J-PA-1: Crystal growth of calcium carbonate–growth rate determination and method evaluation The size of carbonate particles and the accompanying depletion of supersaturation in the liquids associated with the off-shore production of natural gas in domestic fields like “Snøhvit” and “Ormen Lange”, are determined by the crystal growth rate. The assignment is to determine the growth kinetics of aragonite, the high temperature polymorph of calcium carbonate in water/glycol mixtures at different temperatures. A method of seeded batch experiments should be used based on both freshly made and dried seed material. The former seeding approach has previously been used for the other polymorphs of calcium carbonate, and the applicability of using dry seeds should be tested against previous data. Co-supervisor: Ralf beck Reserved for Charlotte Aanonsen J-PA-2: Scaling of calcium carbonate on a heat exchanger surface and the effect on

heat transfer. When producing natural gas, calcium ions originating from the reservoir fluids and carbon dioxide from the gas phase can react to form calcium carbonate, either as particles in the bulk liquid or as surface scaling on the process equipment onshore. The calcium carbonate scale acts as an insulator on heat exchange equipment, and frequent shut-downs are required to remove this scale. Scaling is therefore a major challenge in many parts of the industry and the control or prevention of this phenomenon represents a huge economic and environmental advantage. Scaling versus bulk precipitation will be studied in a set-up with continuous addition of reactants at constant composition conditions. The morphology and growth rate of the scale should be determined at different heat exchanger temperatures, supersaturations and contents of ethylene glycol. Co-supervisor: Margrethe Nergaard Reserved for Ketil Hyllestad

Bioraffinering og fiberteknologi/Biorefining and Fibre Technology ØWG: Professor Øyvind Weiby Gregersen ØWG-1: In plane hygroexpansivity of board The project main objective is to investigate the furnish components’ hygroexpansivities on the dimensional stability of machine produced board. The student will start the project with literature review and laboratory studies. The laboratory work will include the following, where applicable:

1. The MD and CD hygroexpansivities of different furnishes (TMP, Chemical pulp and Broke) at different anisotropy level. The effects from freely and restrained drying will also be investigated.

2. The effect of mill chemical pulp fines and TMP fines on hygroexpansivity 3. Construct multilayer board using dynamic sheet former and investigate the effects of layered fibre

orientation anisotropy on board hygroexpansivity when the board is freely and restrained dried. 4. Measure the curl tendency of the paperboard when subjected to a change in moisture content and

compare to modelling of curl behaviour using a laminate model. A full scale machine trial will be conducted during the thesis work to compare the laboratory results with the dimensional stability of the machine produced board. The thesis work will be carried out in Iggesund Workington mill, Cumbria, United Kingdom. Iggesund Workington mill will cover both accommodation and transportation cost for the thesis student throughout the duration of the thesis work.

Supervisor at Iggesund Workington: PhD Collin Hii