NTNU Fakultet for naturvitenskap og teknologi Norges teknisk-naturvitenskapelige Institutt for kjemisk prosessteknologi universitet FORDYPNINGSPROSJEKTER HØSTEN 2012 SPECIALIZATION PROJECTS AUTUMN 2012 TKP4510/TKP4511 KATALYSE (CATALYSIS) Coordinator: Edd Anders Blekkan If candidates wish to work on a specific task (e.g. defined by themselves or in collaboration with external laboratories or partners), please contact one of the professors. All the proposed projects are planned with a continuation of the same project for the master thesis. Project proposals from Professor Edd A. Blekkan: [email protected]1. Catalytic dehydrogenation of propane The catalytic dehydrogenation of propane is a very demanding process designed to overcome the thermodynamics of the main reaction (strongly endothermic and equilibrium limited). Furthermore the reaction conditions are such that coke formation is an important issue. We work on an alternative process concept, where the idea is to add some oxygen to the system, selectively burning approximately 50% of the hydrogen produced, thus providing in situ process heat, and at the same time removing some hydrogen and “pulling” the equilibrium conversion towards the product side. A key issue is finding a catalyst capable of burning only the hydrogen in a stream also containing reactive hydrocarbons. The project will involve experimental and theoretical investigations of the selective hydrogen combustion, investigating in detail a catalyst system for this demanding process. Key elements of the work are catalyst preparation and characterization, and activity and selectivity measurements in a dedicated experimental set-up. Co-supervisor: Andrey S. Volynkin 2. Catalytic hydrodeoxygenation of bio‐oils 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 CO 2 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, acidity, 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. Metal sulphides, commonly used for HDS, are less suited for this process, since they require fairly high sulphur concentrations if the feed in order to maintain activity. We
Transcript
1
NTNU Fakultet for naturvitenskap og teknologi Norges teknisk-naturvitenskapelige Institutt for kjemisk prosessteknologi universitet
Coordinator: Edd Anders Blekkan If candidates wish to work on a specific task (e.g. defined by themselves or in collaboration with external laboratories or partners), please contact one of the professors. All the proposed projects are planned with a continuation of the same project for the master thesis.
1.CatalyticdehydrogenationofpropaneThe catalytic dehydrogenation of propane is a very demanding process designed to overcome the thermodynamics of the main reaction (strongly endothermic and equilibrium limited). Furthermore the reaction conditions are such that coke formation is an important issue. We work on an alternative process concept, where the idea is to add some oxygen to the system, selectively burning approximately 50% of the hydrogen produced, thus providing in situ process heat, and at the same time removing some hydrogen and “pulling” the equilibrium conversion towards the product side. A key issue is finding a catalyst capable of burning only the hydrogen in a stream also containing reactive hydrocarbons. The project will involve experimental and theoretical investigations of the selective hydrogen combustion, investigating in detail a catalyst system for this demanding process. Key elements of the work are catalyst preparation and characterization, and activity and selectivity measurements in a dedicated experimental set-up. Co-supervisor: Andrey S. Volynkin
2.Catalytichydrodeoxygenationofbio‐oilsThe 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, acidity, 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. Metal sulphides, commonly used for HDS, are less suited for this process, since they require fairly high sulphur concentrations if the feed in order to maintain activity. We
2
are studying alternative catalysts such as metal phosphides, carbides and nitrides. The work is mainly experimental (catalyst synthesis and characterization, and catalytic experiments), supported by literature studies and theoretical considerations. Co-supervisor: Rune Lødeng, Sara Boullose Eiras, SINTEF
3.MicrocalorimetryAdsorption 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: Postdoc Eleni Patanou.
4.HotgascleaningBiomass 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 gas phase, 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)
5.NewcatalystsfortheFischer‐TropschsynthesisSynthetic crude produced from Fischer-Tropsch Synthesis (FTS) is an attractive alternative for the production of chemicals and transportation fuels. Modern Fischer-Tropsch (FT) technology focuses on maximizing the yield of long chain paraffins (waxes), which are then in turn hydrocracked to high quality diesel and other products. Slurry reactors, due to their excellent temperature control and ease of removing generated heat during the reaction, are widely believed to be superior for natural gas based FTS. But there are technical challenges linked to the application of this technology, in particular are the mechanical properties of the catalyst important. The goal of the project is therefore to develop FTS catalysts with improved mechanical properties, maintaining good activity and selectivity. Hydrothermal synthesis of α-alumina will be studied in order to get a better understanding of the effects on the physical and chemical support parameters. Hydrothermal synthesis of boehmite has shown interesting results indicating that hydrothermal treatment can alter the support acidity. Supports and catalyst will be prepared and characterized. In the second part of the project selected materials will be tested for the FTS.
6.Shortcontacttimereactionsoverkanthalgauzes.Catalyst gauzes applied industrially in short contact time reactions such as ammonia oxidation have traditionally been fabricated from pure metals or alloys (e.g. Pt and PtRh). Recent development at KA Rasmussen AS has enabled gauze fabrication from high temperature steel alloys, and deposition of catalyst support layers onto the steel. Hence, considerably less noble metal quantities may be required in the future, given that active nanoparticles can be successfully deposited and stabilized of such gauzed. The project explores different approaches to metal nanoparticle deposition on gauzes supplied by KA Rasmussen AS, and the resulting catalyst will be studied in oxidative dehydrogenation of lower alkanes. Supervisors: Prof. Edd Blekkan, Anders Holmen and Hilde J. Venvik.
7.Carbonnanotubes(CNT)forenhancedoilproductionfromshalesThe few last years there has been a significant development in production of oil and gas from shale resources, mainly in the US. Increased supply has resulted in a drop in the gas price in North America and predictions that USA will be self-supplied with oil in the future. The development has been accelerated by progress in two technology areas: horizontal drilling and fracking of the reservoir. During fracking with water at high pressure a so-called propant is added. A propant is a strong particle typically of alfa-alumina that helps keep the fracks (cracks) open. Now we are interested in developing propants with added functionality. With a composite material between CNT and the traditional propant, we have a possibility to introduce a reactant and/or catalyst directly into the reservoir during fracking for in situ upgrading of the resource. The project will comprise synthesis of the composite materials and characterize how these can incorporate a catalyst or reactant. A summer job at the Catalysis group is available. Supervisors: De Chen and Erling Rytter
8.Reactormodelforoxychlorinationofethyleneinfixedbedmulti‐tubularreactors.Oxychlorination of ethylene is one of the steps in a balanced process for production of vinyl chloride (VCM) the monomer for production of polyvinyl chloride (PVC) one of the world’s most widely produced thermoplastic. Chlorination of ethylene C2H4 + Cl2 => C2H4Cl2 (EDC) Thermal cracking of EDC C2H4Cl2 => HCl + VCM Oxychlorination of ethylene C2H4 + 2 HCl + ½ O2 => C2H4Cl2 Several types of reactor concepts can be used for the oxychlorination process. The reactor concept of interest for this modeling work consists of three multi-tubular reactors in series. Ethylene and HCl are fed to the first reactor while the oxygen is fed as air and distributed between the reactors. The heat of reaction is removed by raising steam on the shell side of the
4
reactors. The reaction temperature is controlled by the steam pressure. The aim of the project is to develop a two dimensional non-isothermal model that predict the impact of reactor parameters on temperature profiles and by-product formation. Rate expressions for the reactions, equations for heat and mass transfer and pressure drop parameters will be provided. Data from an industrial plant will be provided for evaluation of the model. Supervisors: Prof. De Chen, Prof. Hugo Jakobsen, Dr. Kumar Ranjan Rout and Terje Fuglerud
9.KineticstudyofoxychlorinationprocessCatalytic 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 K, La and Mg modified CuCl2 layer on alumina supports. The site reactivity will be studied by combined UV-Vis spectroscopy-MS and transient kinetic study on catalysts with different site density. The project will be performed at the catalysis group and be closely cooperated with INEOS. A summer job at the Catalysis group is available. Supervisor: Prof. De Chen
10.Investigationofmixedoxide‐basedammoniacombustioncatalystsIntroduction: Yara international ASA is the world’s leading chemical company that converts energy, natural minerals and nitrogen from the air into essential products for farmers and industrial customers. The main application is fertilizers, while industrial uses and environmental solutions are also important growth segments. To produce our products using the minimum of energy and having the lowest possible environmental impact, Yara has an pro-active Catalyst Technology Development Research Department, based in Yara Technology Centre in Porsgrunn. Aim: Determine chemical and structural changes in oxide catalysts exposed to the ammonia combustion reactive atmosphere Description: Mixed oxides with the perovskite structure ABO3, where A is a large cation, such as La, Gd or Sr, and B is a small cation such as Co, Fe, Mn, are of great interest as oxidation catalysts. One potential application for such catalysts, is as a replacement for the current platinum based catalyst for the selective oxidation or combustion of ammonia to NOx (NO + NO2), which is a key step in the commercial production of nitric acid. Cobalt based perovskites such as La1-XSrXCoO3 have been shown to be one of the more promising catalysts for selective ammonia oxidation. However, any catalyst replacing the current platinum-based catalyst must have a lifetime that at least matches that of the platinum catalyst. Perovskite-based ammonia combustion catalysts have shown very promising initial activities. However, they typically undergo a loss of activity and selectivity, after a period of weeks or months of operation. The project aims to determine the chemical and structural changes to a La0.7Sr0.3CoO3-based catalysts when it is exposed to the ammonia combustion environment. Analysis of the catalysts will involve electron microscopy and / or surface analysis. Electron microscopy could involve TEM or STEM (with EDS, CBED or SAD, EELS), or SEM (with EDS). Surface analysis could involve X-ray photoelectron spectroscopy (XPS) or Auger electron spectroscopy (AES or Scanning Auger Microprobe).
5
Exposure of the catalysts to ammonia combustion conditions will take place in a Yara reactor system, and physical characterisation of the fresh and exposed catalysts, using X-ray diffraction, Nitrogen or Krypton adsorption, and mercury porosimetry may also be carried out at Yara Technology Centre. The goal of the project is to identify chemical or structural changes to the catalyst that lead to the loss of performance. Name of Yara Co-supervisor: Marianne S. Grønvold Name of Academic supervisor at NTNU: De Chen
11.HydrogenproductionfrombiomassderivedcompoundsbysorptionenhancedreformingSorption 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. The present work will focus on the fundamental understanding of surface reactions involved in hydrogen production from biomass derived chemicals. The project involves catalysts synthesis and kinetic study of water gas shift reactions and steam reforming reactions in a fixed bed reactor. Supervisor: Prof. De Chen
12.SynthesisoffuelsfrombiomassderivedoxygenatesOxygenates, 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 Co-supervisor: Dr. Børre Børresen, STATOIL
13.One‐potconversionofbiomasstochemicalsonNi/ZnObasedcatalystsCatalytic 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 deal with synthesis, characterization and catalytic test of Ni/ZnO based catalysts. Supervisor: Prof. De Chen Co-supervisor: Dr. Børre Børresen, STATOIL
6
14.UnderstandingofchaingrowthinF‐TsynthesisbykineticstudyFischer-Tropsch synthesis is the key process in the production of liquid fuels from natural gas, coal and biomass. The reaction mechanism has long been the central research topic. However, the mechanism for the chain growth in the F-T synthesis is still in debate. The present work will deal with a steady-state isotopic transient kinetic analysis combining a detailed kinetic study at mediate CO pressures to elucidate the chain growth monomers. The project includes also the synthesis of Co nanoparticles with controlled size and shapes. The kinetic study will be performed on the resulted materials to gain a relationship between the properties and catalytic performance. Supervisor: Prof. De Chen, Prof. Anders Holmen Co-supervisors: Michael
15.AutothermaldryreformingofmethaneCombined total combustion and dry reforming will be studied in a fixed bed reactor. Ni-Co catalysts with different Ni/Co ratio will be synthesised and tested in the reaction. The operating conditions, particular the ratio of O2/CO2/CH4 will be studied as a function of activity, CO/H2 ratio and carbon formation. The catalytic combustion of methane will be focused in the project. Supervisor: Prof. De Chen, Prof. Anders Holmen
16.Fischer‐TropschcatalystsforjetfuelproductionDuring low temperature Fischer-Tropsch conversion of syngas using cobalt catalyst the conditions are normally tuned to optimize wax productions. The wax will further be upgraded to fuels, mainly diesel, and petrochemical feedstock by hydrocracking/-isomerization. Recently there has emerged an interest from the aviation industry in FT synthesis starting with gasification of biomass. For jetfuel few alternative fuels with low CO2 footprint exist, and fuel from FT synthesis has excellent properties for jet engines. However, the product slate of jetfuel is limited, and the present project is directed at optimizing the jetfuel fraction through modification of the FT catalyst. Attempts in the literature, e.g. by coating of FT catalyst with a zeotype layer, have shown low performance due to transport restrictions in the outer layer. Therefore, new approaches are needed. Prepared catalysts will be characterized by standard techniques like BET (porosity), TPR and chemisorption. Selected catalysts will then be tested during FT conditions. The work will be based on some initial promising tests already carried out. The work will be conducted in close cooperation with Statoil research centre at Rotvoll. Supervisors: Erling Rytter ([email protected]) and Magnus Rønning Co-advisors at Statoil: Sigrid Eri and Edvard Bergene
7
17.PhotocatalyticH2‐productionthroughphoto‐reformingofhydrocarbonsProducing 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 new efficient nanomaterials with tuneable bandgap, and also testing of the catalyst materials in photocatalytic reactions such as photoreforming of methanol, ethanol and glycerol. Supervisor/ co-advisors: Magnus Rønning/ Charitha Udani
18.Dopedcarbonnanostructuresasmetal‐freecatalystsDoped 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, XPS, 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. Supervisor/co-advisors: Professor Magnus Rønning/ Marthe Emelie Buan, Navaneethan Muthuswamy
19.CharacterisationofpromotedFischer‐TropschcatalystsIn situ characterisation methods are able to give information about catalysts and catalytic reactions at reaction conditions close to industrial processes. The Catalysis Group is using an increasing number of advanced in situ techniques for catalyst characterisation. The project deals with characterisation of Fischer-Tropsch catalysts at industrially relevant conditions in terms of pressure, temperature and feed composition. The work will include synthesis of promoted catalysts Re, Pt or Ni) and characterisation using in situ XRD, FT-IR and Raman spectroscopy in combination with Fischer-Tropsch synthesis. In addition, standard characterisation using chemisorption, XPS and BET will be performed. The project will be carried out in close collaboration with Statoil and SINTEF. Supervisor/ co-advisor: Magnus Rønning/ Georg Voss
20.InvestigationoftheYara58‐Y1nitrousoxidedecompositioncatalystIntroduction: Yara international ASA is the world’s leading chemical company that converts energy, natural minerals and nitrogen from the air into essential products for farmers and industrial customers. The main application is fertilizers, while industrial uses and
8
environmental solutions are also important growth segments. To produce our products using the minimum of energy and having the lowest possible environmental impact, Yara has an pro-active Catalyst Technology Development Research Department, based in Yara Technology Centre in Porsgrunn. Aim: Determine factors in raw material properties that affect the structure and performance of the derived catalyst. Description: Yara’s 58-Y1 catalyst is the leading commercial technology for decomposing the N2O by-product in the production of nitric acid. The catalyst consists of 2 mole % of an active phase, Co2AlO4, supported on cerium dioxide. The cerium oxide acts as a support phase that has little interaction with the active phase under the extreme process conditions of ammonia combustion (850oC, 1 to 15 bara pressure, and an oxidising gas containing 15% water vapour). It is observed that the source of the cerium oxide (the supplier, and grades by single suppliers) lead to catalysts with quite different levels of performance, in terms of activity and selectivity. It is proposed Co2AlO4 – CeO2 catalysts, derived from two grades of cerium oxide powder will be analysed. One grade will be a powder that produces a stable, high activity catalyst, and the other grade of cerium oxide will produce an unstable, low activity catalyst. Analysis of the cerium oxide powders and catalysts will involve electron microscopy and / or surface analysis. Electron microscopy could involve TEM or STEM (with EDS, CBED or SAD, EELS), or SEM (with EDS). Surface analysis could involve X-ray photoelectron spectroscopy (XPS) or Auger electron spectroscopy (AES or Scanning Auger Microprobe). Exposure of the catalysts to reaction conditions will take place in a Yara reactor system, and physical characterisation of the fresh and exposed catalysts, using X-ray diffraction, Nitrogen or Krypton adsorption, and mercury porosimetry may also be carried out at Yara Technology Centre. The goal of the project is to link properties of the cerium oxide to the performance of the final catalyst. Supervisor: Magnus Rønning Co-supervisor at Yara: David Waller
21.DirectandindirectsynthesisofDMEoveracidiccatalysts.Dimethyl ether (DME), CH3OCH3, is the simplest ether and a possible clean and economical fuel for the future, with the characteristics of 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. 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. At NTNU, we have successfully applied so-called microstructured reactors with integrated heat exchange to for the direct synthesis of DME over physical mixtures of a Cu-based methanol synthesis catalysts and an acidic (γ-alumina, HZSM5) methanol dehydration catalyst. The project aims at comparing the activity and stability of different dehydration catalysts in the direct synthesis to the dehydration alone, and includes characterization and testing of
9
catalysts in a high pressure experimental set-up. The project is part of a collaboration with SINTEF Materials and Chemistry. Supervisor: Prof. Hilde Venvik Co-advisors: Prof. Anders Holmen, Research Scientist Rune Myrstad (SINTEF), PhD student Farbod Dadgar.
22.MicrochannelmembranereactorforsmallscalehydrogenproductionMembrane 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. Supervisor: Hilde Venvik Co-advisor: Thijs Peters (SINTEF), PhD student Nicla Vicinanza, Post doc. Ingeborg-Helene Svenum.
23.InitialstagesofmetaldustingcorrosionMetal dusting is a high temperature corrosion phenomenon that 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
10
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. The project work will focus on alloys applied in so-called microstructured reactors (Inconel 800 series) for process intensification, and the particular issues associated with fabricating such reactors. The work will be carried out in collaboration with Karlsruhe Institute of Technology. Supervisor: Prof. Hilde Venvik Co-advisors: Research Scientist John Walmsley (SINTEF), PhD student Daham Gunawardana.
24.ProcessintensificationoftheFischer‐TropschsynthesisIn the Fischer-Tropsch (FT) synthesis, synthesis gas (H2+CO) can converted to liquid hydrocarbons, and the technology is currently applied in large-scale plants to produce fuels and oils from natural gas. Microstructured reactors are under development for process intensification, i.e. enhancement of productivity per mass or volume of the reactor, and such devices are considered particularly interesting for off-shore conversion (FPSO) of associated gas or conversion of biomass to fuels. At NTNU, we recently published very interesting results on FT synthesis over a Co-based catalyst in a microstructured reactor with integrated heat exchange. This project is a continued study, with emphasis on further investigations of this reaction environment in terms of pressure, temperature and synthesis gas composition. The project is part of a collaboration with SINTEF Materials and Chemistry. Supervisor: Prof. Hilde Venvik Co-advisors: Prof. Anders Holmen, Research Scientist Rune Myrstad (SINTEF), Research Scientist Sara Boullousa-Eiras (SINTEF).
25.AdsorptionofalkalinemetalsoncobaltsinglecrystalsurfacesCobalt 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
11
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.
Supervisor: Prof. Hilde J. Venvik Co-advisors: Prof. Anne Borg, Dept. of Physics (IFY), PhD student Marie Døvre Strømsheim, Dr. Bjørn Chr. Enger, IKP.
26.StudyoftheMechanismofFormationofCalciumNaphthenateDepositsbyIsothermalTitrationCalorimetry.Tetra-acid (also known as Arn) is a molecule present in petroleum crude oil at low concentration, typically the ppm level. This molecule can precipitate with calcium present in produced water 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. The goal of this project is to follow up the formation of calcium naphthenate deposits in an oil/water system using isothermal titration calorimetry (ITC). This technique allows to measure the heat of reaction associated to the formation of these deposits when Tetra-acid is put into contact with calcium. A robust procedure will be first developed to study this formation before determining the influence of different parameters. 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 and the supervisors will be Dr. Sébastien Simon and Pr. Johan Sjöblom.
27.DeterminationofMassofTetra‐AcidattheWater/OilInterfacebyCombiningLangmuirTroughwithQCMMeasurementsTetra-acid (also known as Arn) is a molecule present in petroleum crude oil at low concentration, typically the ppm level. This molecule can precipitate with calcium present in produced water 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 water-oil interface. This new technique is based on the combination of quart crystal microbalance and Langmuir-Schaefer deposition technique. The first part of the work has already allowed to determine the application range of this technique at the water-air interface. The goal of this subject is to transpose this technique for the water-oil interface. 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 and the supervisors will be Dr. Sébastien Simon and Pr. Johan Sjöblom.
13
28.Studyoftheefficiencyofcommercialandgreendemulsifiersonwaterremovalefficiency»Crude oil emulsions (w/o) are present during the oil production. If the water and salt are not removed from the oil, the facilities can suffer serious corrosion problems. Resolving emulsion processes slow down the global process and consume a costly amount of energy for the separation. Demulsifiers are chemicals that speed up this process. These chemicals cause coalescence and flocculation to the water droplets allowing to separate oil from water. The goal of this project is to study the effect of green demulsifiers and their mixtures on the water removal efficiency of crude oil emulsions using Low Field Nuclear Magnetic Resonance (LF-NMR) technique. This technique allows to determine the brine content in emulsions as well as the water droplet sizes. Different parameters will be studied to improve the demulsification efficiency. In particular the synergy existing between demulsifiers will be studied. This project is part of the Joint Industrial Program 1 project, sponsored by several central oil companies and chemical vendors. The work will be done at Ugelstad Laboratory, Department of Chemical Engineering and the supervisors will be PhD Student Albert Barrabino and Pr. Johan Sjöblom.
29.Preparationandcharacterizationofparticle‐stabilizedmodeloilemulsionsPhase inversion in crude oil production is a topic of high interest. The process is dependent on numerous parameters that are challenging to control. Thus, establishing these parameters may help to improve separation and transportation of the crude oils. Model oil emulsions stabilized by silica particles of different polarity represent potential for mimicking inversion behaviour of the crude oil systems. Catastrophic phase inversion can be achieved by increasing concentration of the dispersed phase or by applying a shear. The relationship between shear rate, droplet sizes and the time of droplet instability are important parameters to be established in this study. The project will be a part of the research project FACE at the Ugelstad Laboratory (NTNU), and the results will be of high interest for the industry partners in the project. Project goal: Prepare model oil emulsions stabilized by various particle types and investigate emulsion properties close to inversion point. Main project activities: Preparation of model oil emulsions stabilized by hydrophobic (Aerosil R972) and hydrophilic (Aerosil R7200) particles Establishing inversion point via conductivity measurements, droplet size measurements and stability tests Characterization of the emulsions at concentrations close to inversion point (may include rheology, SEM and NMR). Main supervisor: Prof Johan Sjöblom (NTNU)
Co-supervisor: Dr Galina Rodionova (NTNU)
30.NewPPDFormulations An experimental research investigation will be initiated to ascertain the mechanisms of wax inhibitors and to develop a standardized methodology for wax inhibitor formulating for PPD applications with dispersion technology. Per today a variety of wax inhibitors are available
14
from a variety of commercial vendors, but no systematic technique exists for formuling wax inhibitors to specific fluid compositions. It is known that generic wax inhibitors typically provide a single order of magnitude reduction in yield stress, while effectively tailored inhibitors can reduce yield stresses by up to 4 orders of magnitude. These activities influence with surfactant will be ascertained. A variety of instrumental techniques will be used to investigate paraffin inhibitor mechanisms, including: densitometry, rheometry, QCM, NMR, and AFM. Investigated mechanisms will include: surface adsorption, crystal modification, and steric stabilization. Polymer chemistries may include: alkyl esters, polyacrylates, and ethylene vinyl acetates. Supervisors: Johan Sjöblom and Kristofer Paso
31.Influenceofdispersednano‐crystalsonthenon‐NewtonianrheologyofparaffinicoilsDescription: A new predictive model will be developed to describe the influence of dispersed nano-crystals on the creeping flow of wax-gels, within an adhesive and cohesive breakage regime methodology of wax-gels in oil pipelines using a simple viscosity-based model. AFM nanosurf, profilometry, SEM, and S(T)EM will be used for morphological characterization of the dispersed systems. Rheometric experiments will corroborate the time and strain dependencies of the local stress tensor τZZ. The local rheology model will capture the complete mechanical response of gelled fluid samples, starting from initial yielding kinetics and ending with equilibrium flow properties. The influence of dispersed nano-crystals will be established by the mechanistic activity and will be corroborated to the morphological characterization. Measurements will be performed in controlled-stress as well as controlled-strain modes to investigate creeping deformation and forced breakage response to the morphology (AFM). In addition to waxes, the local rheology model may account for co-precipitated hydrate nano-crystals, emulsified water, and solid inorganics, as well as dispersed nano-crystal adhesion (AFM-contact mode). The complete local stress tensor τZZ provides a direct link between morphology (AFM), rheology and pipeline hydrodynamics.
Student Qualifications: Background studies in Chemical Engineering or Materials Science. Masters or Ph.D. studies at NTNU.
Usage of NTNU Nanolab: The following instruments will be used, based on availability: AFM nanosurf, Profilometer, SEM, and S(T)EM, AFM Veeco (contact mode)
32.Interfacialcharacterisationofgas‐liquidinterfacesrelatedtogasflotationinoffshoreproducedwatertreatmentProduced 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
15
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 how dissolved hydrocarbons (organic acids, phenols, etc.) and production chemicals influence 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 and Gisle Øye
33.Characterisationofliquid‐liquidinterfacesrelatedtooffshoreproducedwatertreatmentProduced 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. Break-up and coalesence of oil droplets depends on oil-water interfacial properties. Naphthenic acids are important in this respect, but less is known about basic crude oil components and their influence on interfacial properties. The aim of this project will be to study the time-dependent evolution of interfacial tension and interfacial rheology for model systems containing acidic and basic components. The measurement will be carried out using the pendant drop and oscillating pendant drop methods. The project is part of a research programme sponsored by ConocoPhillips, ENI Norge, Schlumberger Division MI EPCON, Statoil and Total. Supervisors: Bartłomiej Gaweł and Gisle Øye
34.InvestigationoflossofsurfactantbyadsorptionontoclaymineralsrelatedtoenhancedoilrecoverymethodsEnhanced oil recovery (EOR) is the final stage in the recovery of crude oil from reservoirs. Many oilfields at the Norwegian Continental Shelf are entering the tail production phase and it is crucial to implement EOR processes in order to avoid leaving large amounts of oil in the reservoirs. Surfactant flooding is a recognized EOR method that has been used commercially by oil companies for decades, while low salinity water flooding is still a novel method. Nowadays, 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. Most sandstone reservoirs contain considerable amounts of fine-grained clay (montmorillonite, illite, kaolinite, etc.) and these minerals can influence surfactant adsorption during the combined EOR process. Since low retention of surfactants in the reservoir is crucial for the method to be efficient and economically feasible, it is important to understand which parameters that can influence the extent of surfactant adsorption onto minerals. The aim of the project is to study adsorption of surfactants onto different types of clay.
16
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, Statoil and Unger Surfactants. Supervisors: Meysam Nourani and Gisle Øye
35.PartitioningofsurfactantsbetweenthewaterandoilphasesrelatedtoenhancedoilrecoverymethodsEnhanced oil recovery (EOR) is the final stage in the recovery of crude oil from reservoirs. Many oilfields at the Norwegian Continental Shelf are entering the tail production phase and it is crucial to implement EOR processes in order to avoid leaving large amounts of oil in the reservoirs. Surfactant flooding is a recognized EOR method that has been used commercially by oil companies for decades, while low salinity water flooding is still a novel method. Nowadays, 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 interfacial tension between oil and water is important for mobilisation of oil, and detailed understanding of factors influencing the partitioning of surfactants between the oil, water and interface is important for fundamental understanding and optimisation of the process. The task for the project is to determine partition coefficients of surfactants between water and oil phases at different pH and salinities. The optimal outcome would be a general model for explaining the phase behaviour of new surfactant/brine/oil systems. UV-Vis, surface tension and HPLC measurements can be used to determine surfactant concentrations. Exact liquid/liquid interfacial tensions will be measured by the spinning drop method. 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, Statoil and Unger Surfactants. Supervisors: Thomas Tichelkamp and Gisle Øye
36.DesignofSmartSuperparamagneticPolymerNanocompositesIn recent years, increasing use of wireless devices, for example, mobile phones, has caused threat to human health by emitting electromagnetic (EM) radiations . Therefore, the design of novel shielding nanomaterials is of significant importance which can suppress or adsorb the EM waves. The high level of shielding can not be obtained by using polymeric materials alone. Incorporating magnetic nanoparticles into polymer matrix can be very efficient in adsorbing radiations from electrical or magnetic sources. The fabrication of such magnetic polymer nanocomposites is very critical and challenging as it requires control over uniform dispersion of nanoparticles embedded in polymer matrix without any aggregation or clustering of nanoparticles in order to optimize the performance of materials. Such magnetic polymeric nanocomposites are also potentially useful for their applications in defense, missile-and space industries. Thus, the main aim of this project is to develop a new strategy to synthesize magnetic nanoparticles of tunable sizes in-situ in a polymer matrix to attain improved nanoparticle dispersion by balancing the competitive interaction between polymer-
17
nanoparticle and polymer-polymer. The surface effects of nanoparticles due to their shape and surface anisotropies on adsorption will also be investigated. The project will use experimental techniques available at the Ugelstad Laboratory as well as in the NTNU NanoLab.
This project is suitable for a highly motivated student who is particularly interested in the applications of nanomaterials in real world problems. The student will get good research exposure in nanomaterials synthesis and their characterization by microscopic and spectroscopic techniques.
Main Supervisor: Wilhelm Robert Glomm, IKP, e-mail: [email protected], Co-supervisor: Gurvinder Singh (IKP)
37.SynthesisandCharacterizationofChemicallyStableFeCoPtAlloyNanoparticlesMagnetic nanoparticles with superior magnetic properties including large permeability, large coercivity, and high saturation magnetization are attractive materials for a wide range of applications such as magnetic energy and data storage at room temperature, enhanced contrast agents for highly sensitive magnetic resonance imaging (MRI), catalyst, fuel cell, turbine engine components and magnetic bearings. However, the synthesis of monodisperse such magnetic nanoparticles is a challenging task due to their poor chemical stability, control over chemical composition, size and shape, and low blocking temperature. The aim of this project is to develop a novel chemical synthesis route that could overcome these above-mentioned drawbacks and form a general route for synthesizing various alloys nanoparticles with tunable compositions. The project will use experimental techniques available at the Ugelstad Laboratory as well as in the NTNU NanoLab.
Interested students will have the opportunity to learn nanoparticle synthesis, thin film by self-assembled nanoparticles and will achieve experience of various nano-characterization techniques.
Main Supervisor: Wilhelm Robert Glomm, IKP, e-mail: [email protected], Co-supervisor: Gurvinder Singh (IKP)
38.SmartnanoparticlesfortargeteddrugdeliveryCombining nanoparticles with pharmaceutically active compunds such as small drug molecules, peptides, enzymes and antibodies holds great promise in developing “smart” drug delivery vectors with superior performance and selectivity. The successful design of these new materials depends on an understanding of how the pharmaceutically active compound interacts with the nanomaterial, and to which extent the components exhibit emergent properties, i.e.; whether or not the nanoparticle construct has (desirable) properties not found in either the nanoparticle or pharmaceutical compund alone. In addition to carrying a pharmaceutically active compund, the nanoparticle core can act as a diagnostic tool; either optically (by using noble metal nanoparticles) or provide enhanced contrast in MRI measurements (by utilizing magnetic nanoparticles), or a combination thereof.
18
In this project, various nanoparticle vectors will be synthesized, and the properties will be screened based on stability in biological media, optical and/or magnetic properties, and, where applicable, functionality of the construct. The prospective nanoparticle constructs will be investigated using experimental techniques available at the Ugelstad Laboratory and at NTNU NanoLab. Main subject teacher: Wilhelm Glomm, IKP, e-mail: [email protected] , Co-supervisor: Sulalit Bandyopadhyay (IKP)
39.Introductiontomolecularsimulationofmulti.componentadsorptionatliquid‐liquidinterfaces.Surfactant stabilized liquid-liquid interfaces are prevalent in a myriad of industrial chemical processes encountered in the food, coatings, cosmetic, pharmaceutical, materials, and petroleum industries. Naturally, most processes of economic relevance involve complex interfaces composed of two or more surfactants. Consequently, mechanistic descriptions of the non-ideal thermodynamics, mass transfer, and electrochemical phenomena at the interfaces are particularly valuable for the design and operation of multiphase chemical processes. The introductory project is very applied: the student will be taught how to use molecular simulation software to simulate the adsorption of interfacially active crude oil components while learning the key concepts of molecular simulation as they progress. Relationships between adsorption and mass transfer within the scope of the overall process behavior will also be explored. Supervisor: Brian Grimes
40.Introductiontomodelinggravityseparationofemulsions:Applicationtocrudeoil‐waterseparationsGravity separation of crude oil and water emulsions is a key process encountered in the Norwegian (and global) petroleum industry. Particularly, the newer oil fields on the Norwegian continental shelf are so-called “heavy” crude oils, and emulsions containing this oil are difficult to separate. Therefore, there is a strong impetus to elucidate and understand the mechanisms of the gravity separation process both in terms of the emulsion droplet size distribution and the physicochemical properties of the phase interface. The introductory project is very applied: the student will be taught the numerical approach to solving a population balance equation for emulsion separation. Key elements of constructing and solving advanced chemical engineering models involving mass transfer and fluid dynamics will be explored. Supervisor: Brian Grimes
41.VLEfortheCO2‐amineofCO2‐carbonatesystemsThe purpose of the projects is to map various CO2 – amine/carbonate systems regarding VLE for CO2 and VLE in unloaded systems. The aim is to produce consistent sets of data for many amine concentrations and for the temperatures 25, 40, 60, 80, 100, and 120oC. There are three apparatuses, one low temperature apparatus for 25-80 oC, one high temperature apparatus for 80-120 oC and finally an ebulliometer for unloaded VLE. The data from these will form the basis for a consistent equilibrium model and the task will also include modelling of equilibrium using an e-UNIQUAC or e-NRTL model. These models are already programmed but will need adjustment to the system in question. In addition there will be parameter fitting using the PSO method that is already established. In this area we can have up to 3 simultaneous projects. The autumn project is planned continued to an MSc thesis, but not necessarily in the same area. Faglærer/Veiledere: Hallvard Svendsen/Ardi Hartono/Hanna Knuutila
42.KineticsandphysicalsolubilityinCO2‐absorbentsystemsWe have two kinetic apparatuses, one wetted wall column(WWC) and one string of discs(SDC). In addition we have a physical solubility apparatus. Mass transfer rates will be measured for both CO2 loaded and unloaded system to provide an experimental basis for developing kinetic models. These models can be based on simplified concentration based equilibrium models or activity based using the more rigorous e-UNIQUAC or e-NRTL. Solubility in addition to density and viscosity are necessary data for the kinetic modelling and will be measured. Solubility measurements are based on the so called N2O analogy. In this area we can have up to 2 simultaneous projects. The autumn project is planned continued to an MSc thesis, but not necessarily in the same area. Faglærer/Veiledere: Hanna Knuutila Hallvard Svendsen/Ardi Hartono
43.VLLE,Vapour‐Liquid‐LiquidequilibriumA new breed of absorbents is under development. The main feature is that they form two liquid phases when loaded with CO2, one which is high in CO2 and one low in CO2. We have a new VLLE apparatus established and two systems will be studied. The work will be combined with equilibrium modelling as for the VLE studies. The autumn project is planned continued to an MSc thesis, but not necessarily in the same area.
44.CO2absorption:CalorimetricmeasurementsOne of the most important properties of new absorbent systems for CO2 capture, are their thermal behaviour. We need to know the heat of reaction as function of temperature and CO2 content. Some system, in particular 2nd and 3rd generation solvents may undergo phase change. This we also need to understand and characterize fully. The measurements will take place in a calorimeter and involve liquid phase analysis. The thermal data will be analyzed using a rigorous thermodynamic model, either the extended UNIQUAC model or the eNRTL model. Faglærer/Veileder: Hallvard Svendsen/Anastasia Trollebø
45.DegradationmodellingTCM DA is now well underway with construction of the world's largest center for testing, verification and development of CCS technologies. The technology center is located at Mongstad, north of Bergen. The center will utilize flue gas from two sources: Mongstad refinery's catalytic cracker (RFCC) and Dong's heat and power plant (CHP). For more information see www.tcmda.com. Based on work done in our laboratories on degradation of amines, a degradation model has been developed in Matlab and fitted to data from lab scale experiments. The model is also implemented in ASPEN and can be used to predict degradation in an absorber column. We want to improve and expand the model. This will be mainly a modeling task but can be combined with Project 12 on experimental degradation. Faglærer/veileder: Hanna Knuutila /Hallvard Svendsen
46.MethodforcarbamateconstantdeterminationOne of the most difficult properties to measure for amine and amino acid systems is the carbamate constant. It can be obtained at low temperature using NMR, but for higher temperature rapid proton shift and reaction rates make it almost impossible. We have been trying to develop a wet chemical method based on a combination of gravimetric and titration analysis. This method needs to be further developed and validated. The work is partly experimental but will also involve equilibrium modeling. If of interest, and if necessary background is available, also molecular modeling may be used. The project will be combined with kinetics or equilibrium modeling for the MSc thesis. Faglærer/veileder: Hallvard Svendsen/Ardi Hartono
47.MeasurementsandmodelingofphysicalpropertiesofsolventsathighpressuresPhysical properties of the studied solvents are necessary for design and operation of the processes as well as for thermodynamic modeling. SINTEF/NTNU has recently built a capillary viscometer set-up suitable for measuring a kinematic viscosities of different fluids at temperatures from room temperature to about 150oC and pressures up to 15 MPa. In addition
21
an Anton Paar flow density meter is installed in the same set-up allowing measuring the densities at temperatures up to 120 oC. Planned activity:
- Measurements of solvents properties at different concentration, CO2 loading, temperature and pressure
- Modeling (fitting) of the measured properties
The activity may be eventually connected to the measurements and modeling of phase equilibria at high pressure. Supervisors: Hanna Knuutila/Inna Kim /Hallvard Svendsen
48.DegradationandcorrosionofabsorbentsystemsPost-combustion with reactive absorption is currently the most feasible technology for CO2 capture and can be applied also to existing plants. Alkanolamines are widely used as solvents for post-combustion CO2-capture because many of them react fast with CO2 and they have a high absorption capacity. One major problem using amines is amine degradation which causes additional operating costs related to solvent losses, corrosion of the process equipment, fouling, foaming and the potential effects that the degradation products may cause to the environment. This project work is to study the connection between degradation and corrosion. The work will be experimental. Degradation compounds will be identified using different analytical instruments, IC and GC-MS together with LC-MS. The task will be to try to see trends, possibly suggest mechanisms for some of the degradation products. If time allows, some modelling can be included. The autumn project is planned to continue to an MSc thesis, but not necessarily in the same area. Supervisors: Hanna Knuutila/ Hallvard Svendsen/Giorgos Fytianos
49.ModellingofammoniabasedCO2capturewithAspenPlus CO2 can be captured with ammonia. The main advantage is the possibility to strip CO2 from the solution at high pressures. The main disadvantage is the high volatility of ammonia due to which low temperatures in the absorber are required. The task for the autumn project is to build thermodynamic process model for ammonia based CO2 capture using simulation tool Aspen Plus. Here the main emphasis will be to validate the underlying thermodynamic models available in the Aspen Plus with experimental data from literature. The autumn project can continue to an MSc thesis. Supervisors: Hanna Knuutila/ Hallvard Svendsen/Magne Hillestad
50.DeterminationofthemechanismofthereactionbetweenCO2andalkanolamines. The reaction of CO2 with aqueous and non-aqueous alkanolamine solutions respectively has been a subject of research for many decades. Moreover it is still a topic that receives much attention as these solvents are likely to be applied in a/o CO2 capture and storage processes. The overall reaction equation for CO2 with primary and secondary amines is: CO2 + 2 R1R2NH = R1R2NCOO- + R1R2NH2
+ On the true reaction mechanism a long debate is going on in literature. Basically two mechanisms are proposed:
- the zwitterion mechanism, originally proposed by Danckwerts in 1970, - the termolecular mechanism, originally proposed by Falck da Silva early 2000.
Although there is a fundamental difference between these models from a chemical point of view, the resulting overall rate equations are almost identical! In this project it is aimed at revealing the real mechanism of the above mentioned reaction! From a thorough theoretical study the differences between the models have to be identified and translated into experiments to demonstrate experimentally the various assumptions and reaction paths. The study will start as a summer job at PROCEDE in Enschede, the Netherlands and the experiments will partly be carried out at the premises of PROCEDE (see www.procede.nl) and also partly as the autumn project at NTNU. This project can possibly be continued as a master thesis either at NTNU or PROCEDE. Supervision: prof. Geert Versteeg (NTNU and also in the Netherlands) and prof. Hallvard Svendsen (NTNU).
51.Developmentofadesulphurisationprocessthatis100%selectiveforH2S. In the past PROCEDE (see www.procede.nl) has developed a process that removes 100% selectively H2S from acidic gases, e.g. natural gas, refinery gas and biogas produced by digesters. The basic idea of the process is the direct reaction of H2S with Cu-ions in an aqueous copper sulphate solution: H2S + Cu2+ + SO4
2- = CuS (solid) + 2H+ + SO42- (1)
The solid CuS is removed from the solvent and upgraded to CuO with elemental sulphur as product:
23
CuS + 0.5 O2 = CuO + S (2) The copper oxide is fed to copper sulphate solution were the following reaction occurs: CuO + 2H+ + SO4
2- = Cu2+ + SO42- + H2O (3)
Overall it has been demonstrated that the H2S absorption, reaction (1), works excellent and H2S removal efficiencies of more than 99,99+% have been realized meanwhile maintaining 100% selectivity towards CO2. It also was concluded that it is very difficult to design a continuous process for the regeneration of the CuS (reactions (2) and (3) respectively). Therefore new process routes have been developed in order to arrive at a process that can regenerate the CuS in a continuous mode. A possible route could be the following reaction in an aqueous iron(III)sulphate solution: CuS (s) + 2Fe3+ + 3 SO4
2-= Cu2+ + Fe2+ + 3 SO42- + S(s)
(4) The Fe2+ can be oxidized again resulting in Fe3+. This oxidation can be carried out with (compressed) air: 2Fe2+ + 3 SO4
2- + 0.5 O2 + 2H+ = 2Fe3+ + 3 SO42- + H2O (5)
From literature is known that both reactions proceed at temperatures below 100 oC and, depending on the required oxygen level, at atmospheric to ambient pressures. In order to be able to design a continuously operated CuS regeneration process the kinetics of both reactions (4) and (5) have to be studied and determined. The study will start as a summer job at PROCEDE in Enschede, the Netherlands and the experiments will partly be carried out at the premises of PROCEDE (see www.procede.nl) and also partly as the autumn project at NTNU. This project can possibly be continued as a master thesis either at NTNU or PROCEDE. Supervision: prof. Geert Versteeg (NTNU and also in the Netherlands) and prof. Hallvard Svendsen (NTNU).
52.DeterminationofthemasstransferparameterskL,kGandaofstructuredpackings. At the premises of PROCEDE (see www.procede.nl) in Enschede, PROCEDE has design and constructed a pilot-plant for the study of CO2 capture processes. Another application of the pilot plant (ID=0.175 m and H=6 m) is the characterization of commercially available packing in terms of kL, kG and a. Usually the determination of these mass transfer parameters are carried out via absorption experiments with model systems like e.g.:
- SO2 and NaOH for kGa, - CO2 and NaOH for a, - O2 and water for kLa.
Of course many other model systems have been proposed in (open) literature. All these model systems have in common that only one mass transfer parameter is determined.
24
In this project it is aimed at developing experimental systems that can, at least, determine two mass transfer parameters. Examples, derived from the above mentioned model systems could be:
- SO2 and CO2 absorption in NaOH solutions for kGa and a simultaneously, - CO2 and O2 absorption in NaOH solutions for kLa and a simultaneously.
One might even think of absorbing the three gases at the same time! This means that special analytical techniques must be developed to monitor the concentrations of the various species in both gas and liquid phase and selectively! Moreover, it is known that aqueous amine solutions are also suitable as model system but these are not frequently used! Part of the project will be focussing on the applicability of these amine solutions. As the pilot-plant is also equipped with a regenerator section (stripper) the use of amine systems seems very attractive as the consumption of chemicals can be substantially reduced! The study will start as a summer job at PROCEDE in Enschede, the Netherlands and the experiments will fully be carried out at the premises of PROCEDE (see www.procede.nl) during the summer. The evaluation and interpretation part of the work can be done as the autumn project at NTNU. This project can possibly be continued as a master thesis at PROCEDE. Supervision: prof. Geert Versteeg (NTNU and also in the Netherlands) and prof. Hallvard Svendsen (NTNU).
53.Scaleupofadesulphurizationprocessthatis100%selectiveforH2S. A new process has been developed by PROCEDE (www.procede.nl) for the removal of H2S from gas streams: the Vitrisol® process. The Vitrisol® process is designed for operation at ambient pressures (e.g. removal of H2S from biogas) and is able to selectively remove H2S by precipitation with metal ions in an aqueous solution forming metal sulphides, without co-absorption of CO2. Currently two Vitrisol® plants are built in the Netherlands for the removal of H2S from biogas. The application of the Vitrisol® process is under scrutiny in the ISPT project called ‘Removal and recovery of sulphur components from natural gas.’ In this project, the Vitrisol® process is made applicable for stranded gas fields, and therefore should be able to handle elevated pressures and higher gas throughputs compared to ambient conditions (e.g. biogas purification). One of the aspects of scale up is the type of gas-liquid interaction (called flow regime) the downflow absorber should operate in. Possible flow regimes are e.g. trickle flow, pulse flow, spray flow. While many flow regime transition models exist, none of them succeed in predicting the transition for varying systems. Moreover, almost no information is known about the effect of solids on the trickle to pulse flow transition. Therefore experimental verification of the trickle to pulse flow transition is required.
25
Aim of this project is to investigate experimentally the trickle to pulse flow transition in a cold-flow absorber at ambient conditions, in the presence of solids. The effect of elevated pressure will be simulated by using gases with varying densities. Experimental data obtained can be used to create a tailor-made flow regime transition model for the Vitrisol® process. The study can start either as a summer job, or a master thesis at PROCEDE in Enschede, the Netherlands. Experiments will be carried out at the premises of PROCEDE (see www.procede.nl). When started as a summer job, this project can possibly be continued as a master thesis at PROCEDE. Supervision: prof. Geert Versteeg (NTNU and also in the Netherlands) and prof. Hallvard Svendsen (NTNU).
54.DevelopmentofanOsmoticMembranePressureActuator(OMPA)forEnhancedOil&GasRecoveryWater flowing into the wells in sub-sea oil and gas production will directly cause reduced production of oil and gas. This may especially be a problem in a horizontal and branched well; produced water in a branched well will intrude the oil and gas production in the other branched wells, which again will causereduced gas and oil recovery. The identification and shutting down the water production well is expensive for the subsea operation. In the OMPA-project an autonomous valve based on the principle of pressure retarded osmosis (PRO) is to be developed, for detection of water production in parts of an oil/gas producing well, and for operation of the valve, so that it will be able to close off the water producing zones in the well while other parts of the well continue to produce oil/gas. The main focus will be to develop a membrane that can withstand the harsh environmental conditions in a given well. This project is in collaboration with oil industry so the operation condition of OMPA is defined by industry based on a chosen will. Scope of work (SOW)
Currently, the method of preparation of osmosis membranes has been developed in the Memfo group. Thus the main work will focus on the membrane characterization and membrane performance test. The scope of work is listed below.
1. Membrane characterizations.
This work includes the measurement of thermal stability of membrane material by
DSC and TGA-MS and characterization of membrane surface morphologies by AFM
as well as the analysis membrane material structure by IR and NMR.
2. Testing of membranes in forward osmosis (FO) process
This work includes testing of membranes in FO process with different salts as draw
solution. The temperature effects on membrane performance will also be investigated.
3. Testing of membranes in pressure retarded osmosis (PRO) process
The work will be done in the new PRO rig, which can test the membrane up to 20bar
from room temperature to 60 °C. The generated pressure by the osmotic pressure
26
difference in feed solution and draw solution will be measured, which is the important
parameter for design the OMPA.
Co-supervisor: Dr Qiang Yu (NTNU)
55.Developmentofmembranematerialsforagas‐liquidmembranecontactorforCO2capturefromnaturalgasIn gas-liquid membrane contactors the advantages of both membrane technology and absorption processes are combined. The absorption liquid performs the selectivity of the system, while the membrane acts as a barrier between the gas and the liquid. In this project we want to develop membrane materials to be used in a gas-liquid membrane contactor for CO2 capture form natural gas. The demands for the material in a gas-liquid membrane contactor are high permeability, hydrophobicity, compatibility with the absorption liquid and mechanical strength, there is no need for membrane selectivity. Nanocomposites of high free volume polymers and nanoparticles (developed by Sintef Materials and Chemistry) are investigated as the membrane material. Scope of work (SOW)
1. In this project you will contribute to the membrane material development by testing the membrane in a membrane contactor set‐up built specifically for this project. Gas flow rate, liquid flow rate, temperature, absorption liquid concentration and pressure are variables that will be explored.
2. Study the mass transfer of CO2 from methane under various conditions in this CO2‐removal process.
3. Characterization of the membrane material before and after the membrane contactor experiments may also be included, applying FT‐IR (Fourier Transform Infrared Spectroscopy), optical tensiometry (contact angle measurements) and gas permeation tests.
If not all parts of SOW can be covered due to time constrictions, the work can be continued during spring 2014 in MSc-thesis work. This project will be a part of an ongoing work in a PhD-project on the same topic. The PhD-project is in collaboration with Sintef Materials and Chemistry, and industrial partners are Statoil, Petrobras, and Gassco. Co-supervisor: Karen Nessler Seglem, PhD-student ([email protected])
56.Fixed‐Site‐CarrierMembranesforCO2CapturefromCementIndustryCement is produced in virtually all countries globally and its manufacturing is the third largest energy consuming and carbon dioxide (CO2) emitting sector after the steel industry and the petrochemical industry. The cement industry contributes about 4-5% to global anthropogenic CO2 emissions and is estimated to cause about 2-3% of all CO2 emissions in Norway. 60-65% of carbon dioxide (CO2) from cement manufacturing is a byproduct of a chemical conversion process (calcination) used in the production of clinker, a component of cement, in which limestone (CaCO3) is converted to lime (CaO), the remainder CO2 is emission from the fuel used.
27
The cement manufacturing is a very intensive CO2 producing process and it emits 400-900 kg of CO2 for every 1000 kg of cement produced. As a result, the emerging climate change policies have the potential to place the industry at significant financial risk. Recently a new project has been started with Norcem for concept study and pre-engineering of CO2 capture at the test facility in Brevik where various CO2 capture technologies are to be verified. The FSC (fixed-site-carrier) membrane which has been developed in MEMFO group (IKP, NTNU) is planned to be tested with a flat sheet module. The membrane has shown promising performance test results for CO2 separation from flue gas from coal and gas power plant. However the flue gas from the cement factory in Brevik contains up to 20 percent CO2, a much higher percentage and possibly various contaminants from calcination. These will be the challenges for the FSC membrane together with the differences in temperature and pressure conditions. The scope of work of this project is as follows:
1. Review on cement production process with potential membrane CO2 capture concept: Cement production has multiple CO2 emission sources and the flue gas may contain various contaminants with process conditions different from power plants which may affect membrane performance. The existing cement production processes and the potential use of membrane for CO2 capture in the processes will be reviewed. The review will be useful for suggestion and evaluation of the potential cement production process alternatives with membrane CO2 capture concept for the Norcem project.
2. FSC membrane preparation and performance test: The FSC membranes based on the previous preparation parameters (polymer concentration, temperature, time, etc.) will be prepared and tested under flue gas conditions similar to Norcem Brevik cement production. If the performance needs to be improved for the cement industry conditions or if the physical (or mechanical) characteristics of the membrane needs to be changed for the spiral wound module development, membrane preparation parameters can be changed or new ideas (for example, additional coating of PDMS or use of different support, etc.) can be introduced and then tested too.
3. Review on spiral wound module design: The membrane module to be tested in Norcem Brevik is a plate and frame type for small pilot scale verification. Generally a spiral wound module is more feasible for further realistic commercialization. Basic mathematical models and description of transport phenomena in the spiral wound module, necessary design parameters will be reviewed for a potential spiral wound module design.
Co-supervisors: Dr. Taek-Joong Kim (SINTEF) and Dr. M. Washim Uddin (NTNU) Reserved: Mohammad Vahid Sarfaraz
57.PreparationofPVAm/PSfcompositehollowfibersforfluegasapplicationsThe only viable solution to reduce the greenhouse gas emission and to prevent climate change is to develop and implement carbon dioxide (CO2) capture and sequestration technologies. The intrinsic simplicity of a membrane separation process represents a unique advantage among other separation processes such as amine absorption because of relatively low energy consumption and lack of chemicals which may create an extra source of pollution Processing large volume of gases from industrial sources such as flue gas from power plants, requires a
large moptimum
The mabased opolymeand higof the bscale mScope oThe assbe focuoutside experimsealing The labside, wpolysulcollabor(SEM),Differenhollow solutionhollow for diffeCo-sup
58.HiCO2/CThis maof Newpartnerspressure(FSC) massignmtested. For flatsheet F40bar.
membrane arm solution d
Fig. 1
ain objectivon polysulfoer layer for Cgh CO2/N2 sbiggest mem
membrane mof Work (Ssignment reqused on diffe
(shell) sidmental work
of the moduboratory wo
with a selecfone hollowrative proje gas permeant parametefibers. Opt
n concentratfibres will
ferent gas mpervisors: D
ighPressCH4Separaster projec
w Membrans (Statoil, Ne testing omembranes
ment involve
t sheet geoSC membrHowever, t
rea with a mdue to the h
Example o
ve of the proone (PSf) fCO2 captureelectivity.
mbrane prodmodules.
OW) quires a lite
ferent coatinde coating k will be tule and gas
ork will conctive layer w fibers toect. The meation, IR spers will be timization otions, choicbe packed
mixtures suchDr. Marius
sureTestrationt will be a p
ne MaterialsNorway andf polyvinyl
s for CO2/Ces both liter
ometry, the anes showethe perform
minimal foohigh ratio of
of hollow fib
oject is to pfibers as poe from flue The project
ducers in the
erature studyng technique
and insidthe membraflow patter
nsist of coaof PVAm
o be coateembranes wectroscopy optimised
of the PVAce of solven
in modulesh as CO2/N2
Sandru (SI
tingofFix
part of activs) project. d Petrobras lamine/poly
CH4 separatrature/theor
recently ded a good smance at hi
ot print. Holf membrane
ber and holl
prepare androus suppogas. The pr
t involves ce world and
y and practies for thin f
de coating. ane modulerns inside mating PSf ho
m, possibly d will be
will be invesand possiblto obtain h
Am coating nt, coating ps and memb2, CO2/CH4.INTEF) an
xed‐site‐
vities in NaGThe projecBrasil) and
yvinylalcohotion relatedry and labor
developed cseparation pigher press
llow fibre me area per vo
low fiber pr
d test comprt and selecroject will dollaboration
d will be orie
ical experimfilms (0.5-2
Another e fabricatio
module. ollow fiber followed breceived f
stigated by ly other methighly permwill involv
procedure anbrane separ. nd Dr. Mar
‐carrierM
GaMa (Natut involves
d SINTEF. Tol (PVAm/
d to CO2 reratory work
carbon nanoperformanceure up to
membrane golume.
roduced at N
osite hollowctive polyvidocument hin with Air Pented towar
ments. The l2 microns) s
focus of on, packing
membraneby a protefrom Air Pscanning ethods.
meable and ve investigand drying prration prope
ria T. G. Gu
Membran
ural Gas Prbeside NTNThe project/PVA) blenemoval from. Flat sheet
otubes (CNe at moder80 bar and
geometry re
NTNU
w fiber meminylamine (igh CO2 perProducts, Urds developi
literature stusuch as dip the literatu
g density of
es, on shell ctive coatin
Products thrlectron mic
defect freeation of: porotocol. Theerties will b
utierrez (N
nesfor
ocessing byNU, two int will focus nd fixed-sitem natural gmembranes
NTs) reinforate pressure
d the influe
presents
mbranes (PVAm) rmeance
USA, one ing pilot
udy will coating, ure and f fibers,
or bore ng. The rough a
croscopy
e coated olymeric e coated
be tested
NTNU)
y the use ndustrial on high
e-carrier gas. The s will be
rced flat es up to ences of
28
29
process configuration have not been investigated-this should be further conducted in this project. The scope of this work (SOW) can be specified as follows: (1) Literature investigation of the use of spiral-wound modules for natural gas sweetening in
the market today; design of modules and types of materials. (2) High pressure testing of the pilot-scale flat-sheet membrane module up to 80bar. (3) Testing of different process configurations such as 3 sheets in parallel and in series, and
two stages in cascade related to retentate. (4) Characterizations of the FSC membrane structure and morphology using SEM and other
techniques. Co-supervisor: Dr. Xuezhong He (NTNU) and Dr. M. Washim Uddin (NTNU)
59.CharacterizationofagasliquidmembranecontactorforCO2captureNon dispersive gas-liquid contact with the help of a membrane is an efficient new technique in the field of contacting equipment for CO2 capture. A state of the art lab scale membrane contactor setup has recently been developed in the group. To validate the design, characterization of the setup especially the membrane cell is very important. The main task in this project is to evaluate a commercially available micro-porous PTFE membrane/ glass membrane as a non-dispersive and hydrophobic interface between (aqueous) liquid and (CO2 rich) gas phase at post combustion conditions. Experiments shall be conducted with pure CO2 and water, NaOH solution at various gas/liquid flowrates to estimate mass transfer resistance in each phase. Supervisor: Ass. Prof. Liyuan Deng, Co-supervisor: PhD-student Muhammad Saeed
60.DevelopmentofapartiallypyrolyzedhighporositygasseparationmembraneMembrane separation technology is attracting more attention in the recent years as an alternative purification method in air and natural gas industry. In the past two decades, extensive research has been carried out to get better gas separation performance. However, developing membranes with both high gas permeability and selectivity is still critical in gas separation industry. This project is to develop high free volume / high porosity membranes by introducing 3D structured supermolecules as pore precursors in the polymeric matrix, followed by a thermal treatment step to decompose the supermolecule and so create cavities in the polymeric matrix. This project has three tasks.
(1) Suitable candidate materials (both 3D structured supermolecule and the polymer matrix) identification based on literature studies;
(2) Pyrolysis condition optimization, including pyrolysis protocol, supermolecule decomposition temperature, soaking time, etc.
(3) Characterization of the membrane within FTIR, GPC, TGA, SEM etc.
Supervisor: Ass. Prof. Liyuan Deng, Co‐supervisor: PhD‐student Zhongde Dai
61.EvcorroIonic liqbecausecapacitydata of corrosivtransporILs andimportafound oflowingliquids under afor the pSuperv
Projec
62.SyFor ecotechnolmateriapossibleother cr
The corwill be series orepresen(disperstemperasolved avariable The medescribefree radthe desi(MWD)economdifferenimplemMWD tmodel. optimaland mo
valuationsiontestquids are ate of their disy and reasonCO2 in somveness of thrtation, and
d the containant for both on the test og state. As pfor pre-com
above mentipre-combus
visor: Ass. P
tproposal
ystematiconomic and ogies with i
al and energe equipmenriteria that in
re of a chemfurther dev
of functions nted by dession), distribature, catalyas an optimes are applie
ethod is to bed. The mo
dical polymeired molecu) in combin
mic objectivent ways of c
ment a methotogether wit Apply the l mixing connomer feed
nofionictttracting attestinctive pronable therm
me pure or mhese solventd operation oners, pipes, safety reasof the corros
part of the ‘Mmbustion COoned conditstion CO2 caProf. Liyua
lfromPro
cStagingenvironmenimproved my should be
nt volumes, anclude ener
mical plant ieloped and or basic opign functionbution of exyst dilution
mal control ped. The real
be applied ondel will be perization rea
ular weight dnation with ae function. R
calculating tod of calculth the entiremodel to finnfiguration,
d distribution
liquidsa
ention as a toperties suc
mal stability,mixtures of Its with regarof the ionic and processons and thesion of metaMCIL-CO2O2 capture),tions, whichapture. an Deng, C
fessorMa
inChemntal reasons
material and e utilized to areas, energrgy efficienc
s the reactoapplied wit
perations to ns on the voxtra feed podistribution
problem. Parlization is a
n a known sprogrammeaction wherdistributionan Review the MWD, ating the
e kinetic nd the , initiator n, heat
asCO2ab
type of efficch as neglig, with tailorILs are avairds to the stliquids are
sing equipmir successfu
als under ele2’ project (N the corrosih is more re
o-superviso
agneHille
micalReacs, it is of par
energy effiproduce va
gies etc. A scy will also
or. A methodth a publishform the de
olume path.ints, distrib
n and more. rameterizat
a staged proc
system wheed in Matlabre the objec
n
bsorbents
cient and grgible volatilirable structuilable in litetructural maless studied
ment made oul applicatioevated temp
Novel Membion propertiealistic to th
or: PhD-stu
estad:ma
ctorDesiramount imiciencies. Thaluable prodsimple critero be conside
d for systemed kinetic m
esired produ The design
bution of heaThe concepion of the dcess string o
ere the kinetb or Python.tive is to de
s,witha
reen CO2 caity, high COure and properature. Howaterials usedd. The corroof metallic mons. Howevperature andbrane contaes of variou
he process o
udent Zhon
agne.hilles
ignmportance to
he input facducts, with trion is spac
ered.
matic staginmodel. Reacucts. The ban functions aat transfer aptual reactodesign functof multifunc
tics and oth. Applicatioesign a react
focuson
apture absorO2 absorptioperty. Solubwever, data d for the stoosion rates bmaterials arer, few repo
d pressures iactor using ius ILs will boperation co
ngde Dai
stad@ntnu
develop prctors such athe use of lece-time-yiel
g of chemicctants pass tasic operatioare fluid miarea and coor design pro
tions and thectional unit
er phenomeon area can tor path tha
rbents on bility on the
orage, between re very orts are in ionic be tested nditions
u.no
rocess s raw east d, but
cal reactors through a ons are ixing olant oblem is e state s.
ena are be on a
at produces
30
31
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-advisor: PhD Student Paris Klimantos
63.DynamicmodellingandsimulationofaCO2captureplantWe will focus on dynamic modelling of a post-combustion capture plant based on an amine solution. The motivation is to evaluate the process design, control structure 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-adivor: PhD Student Nina Enaasen
64.ModellingandoptimizationofaGas‐to‐LiquidplantA 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. 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.
65.EnergyconsiderationsaroundanamineCO2captureplantAdding 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-advisors: Karl Anders Hoff (Sintef)
32
66.OffshoremethanolproductionOffshore production of methanol from natural gas on a FPSO unit has certain requirements with respect to size and weight in addition to safety compared to an onshore plant. In addition, cogeneration of power will be required. Information with respect to these requirements will be collected. A conceptual design of an offshore methanol plant needs to be generated, optimized and evaluated.
67.Offshoregas‐to‐liquidproductionOffshore production of Fischer-Tropsch liquids on a FPSO unit has certain requirements with respect to size and weight in addition to safety compared to an onshore plant. In addition, cogeneration of power may be required. Information with respect to these requirements will be collected. A conceptual design of an offshore GTL plant needs to be generated, optimized and evaluated.
69.Experimentalinvestigationofsingledropletbreakageinstirredtank.The work will consist in adjusting a high-speed camera setup to study the deformation and breakage of droplets in the range 20 micrometers to 1 mm under three turbulence dissipation rate levels ( in [0.5, 1.0, 1.5] [m2/s3]). The variables to study are the breakage frequency, b [1/s], the number of daughters, , and the daughter size distribution function hb [1/m]. The first step is to set up the data interpretation program in Matlab and make reasonable interpretations of the outcome of the breakage. To determine b we measure the inverse breakage time scale which is the time from initial droplet deformation until final breakage. Then, the number of daughter daroplets created by the breakage event must be counted, and finally the size distribution of the daughter droplets must be determined. It is of interest to study the standard deviations of these measurements, thus the reproducibility must be investigated. Each measurement must thus be reproduced at least 100-500 times to get suitable statistics. If time allow, the existing kernel functions should be fitted to the experimental data. Pending the quality of the fitting, it might be necessary to derive novel kernel functions. Co-supervisor: Jannike Solsvik This project is reserved for Reza Farzad.
ProjectproposalfromProfessorSigurdSkogestad:[email protected] more details about these projects see here: http://www.nt.ntnu.no/users/skoge/diplom/prosjekt13/
70.ValidationofPIDtuningrulesGrimholt and Skogestad (2012) have recently proposed a new way analyzing the optimality of tuning rules. This involves using Pareto-optimal curves portraying the optimal performance versus robustness for a given process. This has been done for the SIMC rules for several different processes. In the continuation of this project it is interesting to compare with other tuning rules (e.g. Ziegler-Nichols, Astrom, Tyreius-Luyben, and more). It is also interesting to take a deeper look at our criteria for optimality. That is, if it sufficiently covers the criteria of a "good" tuning. The work will be conducted with simulations in Matlab and Simulink. Co-supervisor: Chriss Grimholt
71.EnergystorageinadomesticwaterheaterIn order to discourage energy usage during periods of high consumption in the energy grid, it is easy to envision that the energy companies will increase the energy price during these times. In this project, we want to investigate the storing of energy in a domestic water heater such that we avoid energy usage during the high price period. As a solution, we want to find simple strategies (e.g. with simple feedback), and avoid complicated controllers as MPC. The work will be conducted with simulations in Matlab and Simulink. Co-supervisor: Chriss Grimholt
72.OilProductionOptimizationusingSelf‐OptimizingControlThe 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.
34
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
73.EconomicplantwidecontrolusingcommercialprocesssimulationsoftwareA systematic top-down procedure for the design of economic plantwide control system was developed by Skogestad in 2000. The word economic is used here to distinguish the Skogestad’s plantwide design procedure which is based on the steady state plant’s economic performance. The main objective of Skogestad’s procedure is to design a control structure for the complete plant that achieves safe and close to optimal economic performance based on simple control strategies e.g. constant setpoint policies. In this project we want to explore the possibility of automating the economic plantwide design procedure for various process flowsheets developed using commercial process simulators like Hysis or Unisim. The main focus of the project is to formulate an algorithmic procedure that will facilitate the control structure design for the engineers that use these process simulators for this purpose. A successful completion of the project requires: the development of the steady state and dynamic model of a generic chemical process (could be a process which consists of reactor, separator and recycle stream), design of the economic plantwide control (the steady state model is used here) and the evaluation of the performance of the designed control structure (the dynamic model is used here). Co-supervisor: Vladimiros Minasidis
74.DynamicoptimizationandcontrolofbatchcrystallizationprocessesBatch 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
35
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 (defined) disturbance (optimally invariant trajectory). Therefore, tracking this trajectory by a feedback controller will automatically produce optimal inputs for any sufficiently small disturbance. A crucial requirement in batch processes operation is to be able to meet all the constraints despite disturbances and model uncertainties. Thus, we would like to employ a model predictive controller (MPC) to track the optimally invariant trajectory. The motivation behind MPC is that it can intrinsically handle constraints and it is, therefore, well suited for batch operation. Furthermore, apart from feasibility, it also is important to be near the optimal solution even in face of unforeseen disturbances. For that matter, we will add an economical term in the MPC cost function which should automatically drive the system towards the optimal solution. Co-supervisor: Vinicius de Oliveira
75.ExpectedproblemswhenpairingonnegativeRGA‐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.
76.OptimaliseringogreguleringavCO2‐stripper(samarbeidmedStatoilKårstø)CO2-stripperen er en destillasjonskolonne der CO2 strippes fra etan. Bunnproduktet er rent etan, mens topp-produktet er en blanding av etan og CO2. Topp-produktet brukes som fyrgass i dampproduksjon noe som gir betydelig frihet i valg av toppsammensetning. Optimal toppsammensetning vil avhenge sterkt av føden. Betydelig variasjon i toppsammensetningen og potensiell nær azeotropisk blanding av etan og CO2 i toppen gjør prosessen ulineær og utfordrende å regulere.
36
Oppgaven består i: 1. Lage en dynamisk modell av en CO2-stripper 2. Finne optimal drift for ulike føder 3. Foreslå en reguleringsstruktur som muliggjør optimal drift (både basis- og overordnet regulering) 4. Implementere regulering ved bruk av PID-regulering og / eller MPC. Medveileder: Marius Govatsmark, Statoil Kårstø
77.Modellering,estimering,optimaliseringogreguleringavNPK‐prosessenMedveileder: Knut Wiig Mathisen, Yara NB. Studenten som velger denne oppgaven bør ha kunnskap om NPK-prosessen.
Projectproposalsfromprof.IIKristerForsman,processcontrolspecialistatPerstorpFor more details about these projects see here: http://www.nt.ntnu.no/users/skoge/diplom/prosjekt13/
78.CascadecontrolIn a traditional cascade loop, a disturbance in the slave control loop leads to a disturbance in the master loop which has an ”unnecessary” undershoot. This type of behavior is impossible to achieve without modifying the structure. Is there a modification of the structure that does not have this effect? A different question: Is it possible to quantify when cascade control should be used?
79.ImplementationofratiocontrolRatio control can be implemented in several different ways and the objective is to compare these. One issue is how we handle saturation, and another issue is how to handle nonlinearity caused by changes in the operating point.
80.VarianceminimizingcontrolIn applications, occasionally the control valve will saturate, i.e. go to 0% or 100%, in which case the controller is not active any more. Normally, this just means that we are facing a process design problem, and there is nothing to be done about the situation from a control point of view. However, in some applications it may be as important to reduce variations in the process variable as it is to keep its value close to the setpoint. To solve this compromise we may consider modifying the working setpoint slightly so that we get back into a controllable situation, but also monitor when we can start going back to the target setpoint.
84.SimgrowtA novelenvironnutrientset of ortime steHowevepracticaThe maintegratcreativestep and(ode45,
ndustrialare several p
rainingsipervisor: Ol
tproposal
evelopmestrin,Forrch.
rk componennd their effey measurablon and reguan be devel
ation. This ch.
ain goal of thlin, EGF anab, and the n
Supervisor:pervisors: N
mulationth(Systeml mathemati
nmental conts, proteins rdinary diffep, first ordeer, this methal implemenain goal of thtion methode combinatid Matlab's O, ode15s). T
controlcpossible cas
imulatorleg Pajalic,
lsfromAs
ent,analrskulin,H
nt analysis ct on their te, and these
ulation. Genloped from Ncircuits are v
he project id HRG stimnecessary tr
Associate Naresh D. J
nandnummbiological model t
nditions, hasand fat, thro
ferential equer Euler intehod for solvntation is nehis project i
d of the modon betweenODE time v
The project i
caseatPees, includin
rforform, Perstorp
sociatePr
ysisandHRGand
(NCA) is a target genese predictionnetically circNCA analyvery import
s to simulamulated netwraining to u
Professor NJ., PhD Can
mericalogy:appliethat predicts been develough the meuations. It wegration meving the diffeeded. is to optimizdel, using a n a constant variable solvis interestin
erstorpng distillatio
malinpro
rofessorNa
simulatiEGFstim
tool that prs (TG). Genns are usefulcuits that de
ysis and prottant for the
te various sworks. The use it will be
Nadav S. Bndidate, Pr
optimizatedmodels the growthloped durinetabolic pro
was implemeethod to solvfferential equ
ze the novel, time-
vers ng since it
on processes
ocess
adavS.B
ionsofgemulinetw
redicts the anerally, the al to understaescribe the atein protein understand
scenarios ofNCA is a re
e provided.
Bar rof. Lars Im
tionofaling)h of fish, gi
ng 2003-200ocesses of thented in Mave the differuations is v
s.
Bar:nadi.ba
eneregulworksinC
activity of tractivity of thand the effeactivation ainteraction
ing of cell r
f the NCA oeady-to-use
msland, Tek
dynamic
iven the feed09. The modhe body, anatlab code, urential equa
d type and del traces thd basically using a conations. ent, and a m
rcuits
n factors ot
sion of
n cancer
ackage
etic
of
he it is a stant
more
37
attemptmodel. optimizaquaculhealthy The canmore efdifferenapplied Main S
85.Mo(Syste
It was foEgyptiasimilar twas thatits fligh
In our laInstitutemodel thconvergreduce tleaves, abrain printerestidue to itturbulen
The maiin matladynamicto 3-D.
The bat implemecan be lstrategieMain SCo-sup
ts to give a pIf the progr
zed and madlture field, bfish feed.
ndidate will fficient, howntial equatio
modeling. Supervisor:
odelingaemsbiolo
found in 201an fruit bats ato the strategt the bat triet to the targe
ab (in coopee of Sciencehat estimate
ges to its targthe noise thaand other obrocesses the ing manner, ts non-linearnces, not the
in goal of thab) to the z- cs and the co
flight, contrented and silater integrates. upervisor: ervisor: Pro
practical, inram (the impde efficient,both in stud
learn how w to simulatons, a very i
Assoc. Pro
andsimuogy:Neur
0 (Science Mapply a sonagy used by c
es to reduce tet (which ca
eration with , and the U.S
es the x-y traget, and expat is reflectedbjects aroundsonar informstems from
r flight mane common ae
he project is axis as wellontrol system
rol and filterimulated in mted in Maste
Associate Pof. Lars Im
ndustrial, applementatio it will be o
dy fish devel
to make difte and develimportant as
ofessor Nad
ulationsoroscience
Magazine, Yar measuremcertain GPSthe sonar me
an be fruit or
Univ. of MaS. defence), ajectories of lored the strd from the sd the target)mation and f
m the fact thaeuvers (the berodynamics
to extend thl. It involvesm, extending
ring is a statmatlab, and er thesis, stu
Professor Namsland, Cybe
pplied solution of the moof a great valopment and
fferential eqlop models spect of any
dav S.Bar
ofbatflige).
Yovel et al. 2ment strategy. One of theeasurement r insect).
aryland, Wewe develop
f the bat's fligrategies it apsurroundings). We found filter the noiat the bats habat flies usins applied by
he model (ims modeling og it from 2-
te space modestimated udying the so
adav S. Barernetic
ion to a theoodel) could alue to the d design mo
quation solvusing ordin
y
ghtandso
2010) that y that is explanationnoise during
eizmann ped a dynamght as it pplies to s (trees, that the bat'
ise in a veryas to apply ang
y birds).
mplemented of the flight dimensions
del, using 145 reaonar effect a
r
oretical be
ore
vers nary
onarin3
ns g
mic
's
a specific flig
al time expeand the flight
3dimensi
ght control s
riments. Thet convergen
ions
system
e project ce
38
86.ThBiolog
Cell miggrows uproliferaeventua
We devgastrin, to diagnexplore aim is tomigratio
Projec
87.TeFluiTecreactor buildingconstruProduct We havpolymeproduct We havproduceis based
hesimulagy:Cance
gration is onuncontrollabation (the ce
ally a tumour
eloped a sima central ho
nose cancer talternative f
o simulate non to gastrin
tproposal
emperatuc is a small, concept calg blocks. Thct small-scation range is
ve currently er productiontion technol
ve one of a fer FluiTec. d on an opti
ationsoferresear
ne of the synly, the apopell's devisionr, tend also t
mplified dynormone whictypes. The mfeedback pa
numerous scen.
lsfromPro
uredistrhi-tech com
lled ContiPlhese reactorale productis in the 10 k
one studenn. This is thlogies.
four universOur installacal laser-inf
f adynamrch)
ndromes cautosis (cell's n and multipto migrate, s
namical modch is involvemodel is impathways that enarios that
ofessorHe
ibutionimpany locatlant. It is a Lr types are cions that cank tons per y
nt working inhe main rese
sity installatation is equiferential me
micmode
used by cancself destruct
plication) is asuch that the
del of the resed in stomacplemented in
can cause thcan be appl
einzPrei
nmilli‐reted in SwitzLego-like idcurrently tesn be placed
year.
n BASF moearch divisi
tions of the ipped with aeter to meas
lofcellm
cer. During ct mechanismaccelerated.e tumour spr
sponse of cech and intestn matlab. Whe cell to suied to chang
isig:heinz
eactor. zerland whodea in whichsted by the into contain
odelling theon of BASF
reactor, wha cutting edsure temper
migration
cancer develm) is suppres The defecti
reads faster.
ll migration tines cancerse wish te ex
uppress migrge the respon
z.preisig@
o is the innoh milli-reaclarge polymners and thu
se reactors F that looks
hich was prodge temperaatures along
n(System
lopment, thessed, cell ive cells, for
to the horms, deadly and
xtend the moration. The pnse of cell
@ntnu.no
ovator of a nctors are themer industrieus are mobi
in the contes into new
ovided by thature sensor g the axis o
ms
e cell
rming
mone d hard
odel and project
new e es to ile.
ext of
he which f the
39
40
reactor on 8 positions with only one fibre. The fibre is less than in the order of 0.2 mm and the reactor inside approx 6 mm. So we are talking very highly sophisticated reactor equipment with highly sophisticated measurement equipment. We shall aim at
Constructing a dynamic residence-time distribution experiment for research and felles lab.
Simulating the behaviour using CFD software Supervisor and daily contact: Heinz A Preisig 88.Residence‐timedistributioninvariousmixedsystems As part of the renewal of the felles lab, I am extending the scope of reactor-engineering related projects. In particular the concept of residence-time distribution is being one of the targets. We have built a flexible bench-scale experiment, which demonstrates the hydraulic behaviour of various different physical systems. We would now like to extend the scope of the experiment adding better sensors and extending to different “plants” like a series of tanks, static mixers or the like.... Supervisor and daily contact: Heinz A Preisig 89.Continuousdistillation We are nearly getting to finish the installation of a new distillation arrangement for the felles lab. New is essentially everything besides the centre column pieces: boiler, head, physical arrangement, a reflux pump, a flow measurement, control. What we like to do is to refurbish two columns with additional pumps to enable them running in continuous mode. The pump arrangement is new as we built the pumps ourselves from commercially available components. There are new mechanical ideas we also discuss to replace the commercial pump head with a new advanced design. Effort focus can vary from control, software to more engineering-type activities. Supervisor and daily contact: Heinz A Preisig 90.Colloidchemistryexperiment I got a suggestion for a new experiment and would like to build it. Supervisor and daily contact: Collaboration with colloid group 91.ChemicalEngineeringontologyforstandardreactortypes I am working on mapping chemical engineering into software, which is using a framework called ontology. These beasts are the formal representation of concepts and rules underlying the models. So it is a type of concise representation of chemical engineering here limited to standard hydraulic reactor types. This may extend to work with TetraPak's engineering division that builds the world's biggest dairy manufacturing processes. The project aims at enhancing and partially substituting the current chemical engineering simulator software. Supervisor and daily contact: Heinz A Preisig 92.Computer‐aidedmodellingWe are building on a new tool expanding on three previous generations of modelling tools. The objective of this project is to provide a high-level modelling tool generating code for existing software tools, such as gProms or other simulation environments. The software implements a step-wise approach to modelling as it is being taught in the Control Course and the Systems Engineering Course. It builds on a graph representation of the processes, adds the "chemistry". A "theory" module provides the basic descriptions, like the balance equations and, where appropriate alternative transfer descriptions and kinetic laws, material
41
descriptions and the like. The "theory" module is designed using a special tool, which implements a simple, tailored language. The project aims at enhancing and partially substituting the current chemical engineering simulator software. The project could be any combination of the following: - use the existing theory definition tool to include the main balances (mass, energy, momentum) - explore the possibilities of using the tool for distributed systems. - implement thermo component - expand to include entropy Recent publication: http://dx.doi.org/10.1016/j.compchemeng.2010.02.023 An excellent opportunity to learn more about modelling and if so desired, programming. Supervisor and daily contact: Heinz A Preisig 93.ControlandFelleslabrejuvenationWe have now completed the main effort of re-building the felles lab, but would like to extend further so as to make it more versatile and more flexible. There is also an ongoing discussion of extending the scope of the lab to other courses. Also the control lab shall be updated and augmented with a couple of experiments. Initial plans have been developed. We invite to help thinking about possible, interesting processes and their realisation. An excellent opportunity to learn about real-time programming, control and making experiments fool proof. Supervisor and daily contact: Heinz A Preisig 94.AutomaticSafetyandHazardAnalysisSafety and hazard analysis are done mostly in a systematic way, but based on mental models of the process. We would like to change this and use a model-based approach. Starting from a model of a continuous process, we have software that computes the possible things that may happen if the environment changes or faults occur. Since we can do this computation, this method could be used to study if indeed something could possibly happen, which is precisely what a safety and hazard analysis does. This type of analysis would give a systematic way of exploring the possible faults in a system, a subject of great interest to industry. Supervisor and daily contact: Heinz A Preisig 95.SimpleThermoServerThe Process Systems Engineering group is heavily involved in process modelling particularly distillation. Distillation models and associated material models are used at a high frequency.
The project is aiming at implementing a server that provides: Interface requesting material information over the net Generic distillation simulation, freely configurable running on the server
The material model software is running and we are using it in a variety of ways. We thought it would be fun and very useful to build a little user interface that enables the interactive use of what the core can generate. This could then be put on-line in the form of a web page, for example. We have a rather generic distillation column model that is quite generally parameterised, which could be augmented with an appropriate interface to make it usable on the web.
42
Such a system has been realised for Yara. A prototype sever exists and is currently operable for ammonia, nitric acid and urea production. The Matlab interface is already working and we are working on an interface to other computer languages such as Python. An interesting task would be to use an interface to gProms. Supervisors: Heinz A Preisig, Tore Haug-Warberg
96.OntimescalinginchemicalprocessesThe Process Systems Engineering group is heavily involved in process modelling. The objective is to generate a very general framework in which models for the process industry can be generated quickly and rapidly. Making time-scale assumptions is done very frequently in the modelling process. Mostly it is not really done explicitly, but just kind of happens. Examples are decision on how to model a heat transfer, for example using an overall heat transfer model is making a time-scale assumption about the distributed transfer system to be of negligible capacity. Similar assumptions appear all over the place and we would like to put this problem into a more systematic framework. The problem of getting measures for the relative dynamic of parallel fundamental transfer process is a common problem in chemical engineering. Probably best known are the “modules” such as the Thiele modules and dimensionless numbers. The derivation of such modules is very frequently based on “pseudo steady-state” assumptions, which in mathematical terms is a standard singular perturbation. The project should look into the literature and analyse the mechanism behind the derivation of the different modules and the like with the aim of deriving a generic understanding behind these measures. In the next stage we want to know if such measures are useful in deciding if or if not the underlying pseudo steady-state assumption can be made or not and if possible on how wrong one is if one does make the assumption dependent on the dynamics. Supervisor and daily contact: Heinz A Preisig
97.FrequencyAnalysisofDistillationCounter current processes show some very peculiar behaviours in the frequency domain. We have been analysing these behaviours in a couple of projects in the past: Ma, PhD on distributed models for tubular heat exchangers and the derivation of simple, but very accurate dynamic models. The findings have been verified in an experimental work done as a master thesis. Recently we found a similar behaviour in distillation columns, which we would like to explore some more. Currently a project is ongoing looking into what looks like a simple linear counter current process, which has a structure similar to a distillation. This work should be continued towards a true distillation model. The work has potential to uncover a new methodology for identifying the internal dynamics in columns. It is thinkable that experimental work to that extent is added using the new-to-be-build columns in the felles lab. Recent work: Puschke's diploma thesis available on request. Supervisor and daily contact: Heinz A Preisig
43
98.ProcessIdentificationusingWaveletsWavelets are mostly used in signal processing as a data reduction processing. A common application is image processing. We are using the same technology for process identification. Essentially we can using wavelets to get derivatives to relatively high order on different level of resolution. This enables us to do identification on a multi-scale a technique matching the current development of multi-scale processes reaching from nano to industrial size equipment. I have also the vision that these technologies will enter the control field heavily in the future as these processes must be controlled across the scales. Thus some kind of plant-wide multi-scale process control. Will introduce the student to multi-scale process modelling and wavelet methodologies. Supervisor and daily contact: Heinz A Preisig
99.DynamiskmodellavBOLIDENOddaellerdeleravanleggetforåkunneforutsehvordanvariasjoneriråstoffsammensetningpåvirkerproduksjonenfremoveritidBOLIDEN Odda er i dag et middels stort Zn smelteverk med en årsproduksjon på knappe 160 000 tonn over kai. Zn tas inn som et forurenset sinksulfid hvor svovelen fjernes og Zn oksideres ved forbrenning ved 930 °C eller ved høyt trykk og temperatur. Neste steg i prosessen består i å løse opp ZnO i en svovelsyreløsning. Her går også mesteparten av forurensingselementene i løsning. For å kunne produsere Zn elektrolytisk er det derfor påkrevd med flere rensetrinn for å fjerne alle forurensingselementene. Kontroll på pH og temperatur samt tilsats av Zn metall er en sentral del av renseprosessen. Etter at forurensingene er fjernet går sinksulfatoppløsningen til elektrolysehallen hvor en produsere Zn på katodene og H+ ioner på anodene. Sinksulfatoppløsningen som forlater elektrolysehallen er anriket på svovelsyre (H+ ioner), mens konsentrasjonen av Zn2+ ioner har gått ned. Denne løsningen pumpes så tilbake til det steget hvor en løser ZnO i prosessen, dermed øker sinkkonsentrasjonen i sinksulfatoppløsningen igjen. Kan det utvikles en modell som beskriver væskeflowen gjennom anleggets mange tanker og settlingsbasseng? Kan en bygge ut modellen til å si noe om hvordan konsentrasjon av ulike element endrer seg i de ulike prosessavsnittene i anlegget? Boliden Odda kan tilby sommerjobb i Odda for å sette seg inn i prosessen ved BO og få kartlagt pumpekapasitet, størrelsen på tanker og settlingsbassenger. En annen viktig bit er å få innblikk i de kjemiske analysene som utføres i de ulike prosessavsnittene. Veileder/Fagansvarlig: NTNU: Heinz A Preisig, Tore Haug-Warberg BOLIDEN: Steinar Jørstad Comment: This project can accomodate more than one student as there are also
interesting design and control issues to be considered. (Heinz Preisig)
100.ThermodynamicsofLNGusingtheGERGequationofstate.Equations of state based on Helmholtz energy are increasingly used for calculations (modelling and simulation) of industrial processes. The motivation for progress in this field is that a good numerical model of the mass and energy balances of the plant is very useful in all stages of plant design, operation, and safety analysis. The prime concern of such models are the mass and energy (heat) balances, but also the volumetric (flow) properties are of great interest as they allow for a combined fluid flow and thermodynamic calculation of heat exchangers, reactors, valves, pipes, etc. The aim of this project is to implement, test and make use of the “The GERG-2004 Wide-Range Equation of State for Natural Gases and Other Mixtures” which is the result of a large European research program on the accurate description of LNG mixtures for international energy trade (E.ON Ruhrgas, Germany; Enagás, Spain; Gasunie, The Netherlands; Gaz de France, France; Snam Rete Gas, Italy; and Statoil, Norway). Goal: Implement (with assistance of the supervisor) the GERG equation of state and make approriate (numerical) tests to verify thermodynamic consistency. Validate the implementation using experimental densities and vapor-liquid equilibria, possibly also speed of sound and enthalpies of vaporization. The student must be motivated to read up a little on equation of state theory and thermodynamic phase equilibrium in general. 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. Supervisor (NTNU): Ass. prof. Tore Haug-Warberg
101.Rigorousthermodynamicsofaplug‐flowreactormodelledinPythonThe understanding of, and training into, the art of mathematical modelling of chemical processes is a key issue for the Department of Chemical Engineering. For this reason the department has agreed to launch a new modelling course which aims at training students (third year) in basic modelling conceps AND in computer programming. This project is devoted the practical issues of getting a mathematical model to run on a computer such that it is useful for class-room teaching and student training. Goal: The language of choice is Python and the goal is to make a full implementation of a plug-flow reactor with rigorous thermodynamics (supplied by the supervisor). Parts of the code do already exist, but there is still work to be done in making a program that is suitable for teaching purposes. This means verification and validation, consolidating and documenting the code, breaking it into smaller modules, and finally to help making a piece of software that runs smoothly on Windows, Linux and Mac. Prior knowledge and experience: The student must have a fair background in computer programming, thermodynamics and numerical mathematics. Supervisor (NTNU): Ass. prof. Tore Haug-Warberg
45
102.Taylor‐expansionofthermodynamicequilibriumstatesarisingfromflashcalculations.Dynamic simulation is very important for start-up, control and optimization of all kinds of chemical processes . This need applies to the process industry world wide and is a driving force for developing better simulators. However, the CPU time can be prohibitive once thermodynamic models are taking into the modelling. This issue becomes especially important when multicomponent mixtures are needed in the simulation. Current equations of state have many parametters and are algebraically quite complex, which gives a high calculation load. One way to drastically reduce the CPU time is to make Taylor expansions of the equilibrium properties as they are calculated in the valves, separators, reactors, compressors, etc. This opens up for many clever things like running a thermodynamic model inside an MPC (model predictive control). Goal: The student shall derive and implement the thermodynamic equilibrium conditions for a flash-drum or a reactor. The output(s) of the unit operation shall next be differentiated with respect to the input and used to establish a multivariable Taylorexpansion around a freely chosen set-point. The derivatives that are needed will be supplied by a thermodynamic package developed at IKP, but the accuracy of the Taylor expansion and the reduction in CPU time must be documented by the student. If time allows there is also a possibilty to make a small dynamic simulator around two or three such linearized units, or to attempt higher order (n>1) Taylor expansions to see if there are any benefits compared to the rigorous model. The student must be motivated to read up a little on equation of state theory and thermodynamic phase equilibrium in general. 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. Supervisor (NTNU): Ass. prof. Tore Haug-Warberg
103.Jatrophaoilindevelopingcountries‐byinitiativeofIngeniørerUtenGrenser(http://www.iug.no/)ZERO - the Zero Emissions Resource Organisation - is an Oslo, Norway-based independent not-for-profit foundation working for zero emission solutions to the global climate challenge. Since 2007, they have been working with Kirkens Nødhjelp (the Norwegian Church Aid) to help local communities in Kenya to produce local bioenergy and thus becoming more self-suficcient. Currently, the project involves approximately 1000 farmers who have planted and harvest the hardy oil plant jatropha. The jatropha plant has a seed oil content of approximately 30%, can be harvested several times per year and can grow in very dry and unfavorable conditions. The oil can be used either neat in stoves and modified Diesel engines, or it can be used as a raw material for biodiesel production. Currently, some of the challenges are testing of oil quality with limited technological resources, and good yields during pressing of the seeds. Supervisor: Størker Moe
104.ExtractionofoilfromjatrophaseedpresscakeCurrently, there is a large amount of residual oil in the presscake after pressing, and increasing the yield is paramount for good performance and economy of the initiative. One alternative method is extraction with a low-viscosity nonpolar solvent, however, the choice of solvent is not straightforward due to the low technological level and lack of funds for building complex extraction plants.
The project will involve evaluating candidates for extraction medium and performing extractions in the laboratory to collect data on actual performance of the extraction medium. Also, other methods for increasing the pressing yield can be included in the work. Supervisor: Størker Moe
105.SimpleanalysismethodsforjatrophaoilqualityThe quality of the oil varies with harvesting conditions, and monitoring of oil quality is important for good performance. The main parameters to be monitored are acid content, phosphorus content and water content. The project will involve a literature study to find low-technology, probably wet chemistry based analysis procedures for appropriate analyses, testing these in the laboratory and comparing the results with more advanced anaylysis methods. Supervisor: Størker Moe
47
106.UseofmineralacidmixturesinconcentratedacidhydrolysisoflignocelluloseThe concentrated acid hydrolysis process has recently seen renewed interest after the development of acid recovery processes, due to its low processing temperature, high yields, low production of sugar degradation products and robustness towards raw material variation.
The most commonly used acid in concentrated acid hydrolysis for saccharification of lignocellulose is sulfuric acid. However, the use of sulfuric acid alone has a profound impact on the biomass, and combinations of sulfuric acid with other mineral acids like phosphoric acid are interesting modifications to the concentrated acid hydrolysis process.
The aim of the project will be to investigate the effect of different sulfuric acid/phosphoric acid mixtures on the saccharification process, by performing several hydrolysis experiments and quantifying sugar yields by HPLC. If the candidate is familiar with multivariate experimental planning, such methods should preferably be used in the design of the experimental matrix. Supervisor: Størker Moe
107.MethodforproducingcelluloseinsulationmatsBackground Cellulose based insulation materials represent a promising alternative to traditional insulation materials like glass fibres, rock wool and foams. Cellulose insulation has favorable product properties, is made of renewable and recyclable raw materials and is favorable with respect to health and worker safety during manufacture and installation. Wood based insulation mats are produced and applied in several European countries, however in Norway, the insulation material market is totally dominated by rock and glass based insulation mats. Now, an innovation project termed iWood has been initiated which aims at developing a new technology for producing virgin fibre based cellulose insulation products in Norway. The project is owned by Viken Skog and managed by PFI. Purpose of student work The purpose of the student work is to develop a laboratory technique for producing cellulose insulation mats and compare essential product properties with existing insulation materials. The student work will be a part of the iWood project and practical work will be carried out in cooperation with PFI personnel. Supervisors: Øyvind Weiby Gregersen, NTNU IKP, [email protected] Kai Toven, PFI, [email protected]
108.ApplicationofnanocellulosefibrilsinfibroussheetsforbarrierpropertycontrolObjective: Investigate the effects of varied amounts, qualities and structural organization of fibres and nanocellulose fibrils in tailor made sheets on material barrier properties relevant for food packaging applications Background: Packaging materials based on renewable fibres and fibrous components may replace oil-based environmentally problematic polymer packaging solutions if these offer similar properties and can be produced at reasonable cost. Polymers in food packaging are varied and versatile, flexible or rigid, transparent or opaque, thermosetting or thermoplastic, and cheap, but generate problems for the environment. Paper based packaging is characterized by low costs, good availability, low weight, printability and good mechanical strength. The disadvantage for a wider application in food packaging is their sensitivity to moisture. The potential of nanocellulose fibrils to reinforce the structure or smoothen the surface of fibrous sheets was shown in a number of studies (e.g. Mörseburg and Chinga-Carrasco, 2009). Effects of nanocellulose fibrils on barrier properties of paper have also been studied (Syverud and Stenius, 2009). Hult et al. (2010) reported for sheets coated with microfibrillar cellulose and shellac the oxygen transmission rate to decrease several logarithmic units and the water vapour transmission rate to correspond to high barrier in food packaging. This work aims at enhancing the understanding of relationships between the material properties of nanofibril - containing fibre networks and their suitability for food packaging applications. Suggested key activities: - Production and testing of tailored sheet structures composed of varying proportions and qualities of papermaking fibres and nanocellulose fibrils - Quality assessment through measurements of relevant paper strength and barrier properties with focus on water vapour transmission rate - Writing of project work report in English The research is mainly to be conducted at PFIs laboratories. Guidance and scientific supervision: - DSc Kathrin Mörseburg (senior research scientist, PFI) - professor Kristin Syverud (adjunct professor, NTNU, Department of Chemical Engineering Bio-refinery and fibre technology)
109.AlternativefireretardantsforcelluloseinsulationmaterialsBackground General challenges for cellulose insulation materials are low fire resistance and risk for mould contamination. Flame retardants are required, as cellulose based insulation is more prone to fire risk than conventional insulation products such as rock wool and glass wool. Today, most producers of cellulose-based insulation use boric acid based flame retardants. Boric acid based chemicals are however toxic, and may give adverse effects on reproducibility and fetus. Therefore, alternative flame retardants are needed. Ammonium polyphosphate is a non-toxic alternative but it has been speculated that phosphate based flame retardants may act as a nutrient for microbiological growth. Purpose of student work
49
The purpose of the student work is to review alternative flame retardants and test experimentally the risk for microbiological growth in virgin fibre based and recycled fibre based cellulose insulation materials with and without fire retardant additives. The student work will be a part of the iWood project and practical work will be carried out in cooperation with PFI personnel. Supervisors: Kristin Syverud, NTNU IKP, [email protected] Kai Toven, PFI, [email protected]
110.ExtractinghemicellulosesugarsfromwoodandwoodfibresBackground For cellulose fibre producers, extraction of hemicelluloses represents an interesting approach for producing co-products. Hemicelluloses are generally much less stable than the other wood components cellulose and lignin and are thus prone to degradation during chemical or thermal treatments. Hemicelluloses are heterogeneous polysaccharides (Dp 50 – 200) which can be extracted in both oligomeric and monomeric sugar form. Hemicelluloses can be extracted by different methods like for instance by hot water extraction. Purpose of student work The purpose of the student work is to optimize a technique for extracting hemicellulose sugars from wood chips and wood fibres with respect to separate a concentrated extract of hemicelluloses in mono-sugar form while minimizing the formation of toxic inhibitors. The student work will be a part of the iWood project and practical work will be carried out in cooperation with PFI personnel. Supervisors: Kristin Syverud, NTNU IKP, [email protected] Bård Helge Hoff, NTNU IK, [email protected] Kai Toven, PFI, [email protected]
