Jatkuvatoimisen natriumhypokloriittireaktorin mallinnus

Natriumhypokloriittia voidaan valmistaa kloorista ja lipeästä jatkuvatoimisessa absorberissa. Tässä työssä tutkittiin kokeellisesti, miten kaasun ja nesteen virtausnopeudet vaikuttavat täytekappalekolonnin tulvimiseen ja painehäviöön, kuinka nopeasti kloori absorboituu lipeään ja kuinka suuri hypokloriittiliuoksen kierrätys tarvitaan, ettei hypokloriitti ala hajota. Lisäksi luotiin matemaattinen malli, jolla voidaan mitoittaa jatkuvatoiminen vastavirtaperiaatteella toimiva natriumhypokloriittireaktori. Kloori–lipeäsysteemin havaittiin tulvivan suuremmilla virtausnopeuksilla kuin ilma–vesisysteemin. Tosin osa kloorista absorboituu jo ennen täytekappalekerrosta, minkä vuoksi kaasun todellinen virtausnopeus täytekappalekerroksen alaosassa on pienempi kuin mitattu arvo. Kolonnin painehäviö nousee erittäin jyrkästi tulvimispisteen läheisyydessä. Koska kloori absorboituu lähes täydellisesti ja vain kolonnin alaosa tulvii, voidaan kolonnia painehäviön kannalta operoida lähellä tulvimispistettä. Sekä mallinnuksen että koetulosten perusteella yli 99,99 % kloorista absorboituu koeolosuhteissa kahden metrin täytekappalekerroksessa. Nopea absorptio johtuu erittäin nopeasta, irreversiibelistä kloorin reaktiosta ja prosessille tyypillisestä natriumhydroksidikonversion rajoittamisesta alle 94 %:iin. Jotta varmistetaan, ettei hypokloriitti ala hajota, valmista hypokloriittiliuosta täytyy kierrättää kolonniin vähintään noin 4-kertainen määrä tuoreen lipeän syöttömäärän nähden.

Model-based study of a chemical-looping combustion process

Chemical-looping combustion (CLC) is a novel combustion technology with inherent separation of the greenhouse gas CO2. The technique typically employs a dual fluidized bed system where a metal oxide is used as a solid oxygen carrier that transfers the oxygen from combustion air to the fuel. The oxygen carrier is looping between the air reactor, where it is oxidized by the air, and the fuel reactor, where it is reduced by the fuel. Hence, air is not mixed with the fuel, and outgoing CO2 does not become diluted by the nitrogen, which gives a possibility to collect the CO2 from the flue gases after the water vapor is condensed. CLC is being proposed as a promising and energy efficient carbon capture technology, since it can achieve both an increase in power station efficiency simultaneously with low energy penalty from the carbon capture. The outcome of a comprehensive literature study concerning the current status of CLC development is presented in this thesis. Also, a steady state model of the CLC process, based on the conservation equations of mass and energy, was developed. The model was used to determine the process conditions and to calculate the reactor dimensions of a 100 MWth CLC system with bunsenite (NiO) as oxygen carrier and methane (CH4) as fuel. This study has been made in Oxygen Carriers and Their Industrial Applications research project (2008 – 2011), funded by the Tekes – Functional Material program. I would like to acknowledge Tekes and participating companies for funding and all project partners for good and comfortable cooperation.

Passiiviset turvallisuusjärjestelmät tulevaisuuden kiehutusvesireaktorilaitoksissa

Kandidaatintyössä on esitelty passiivisten turvallisuusjärjestelmien hyödyntämistä seuraavan sukupolven kiehutusvesireaktorilaitoksissa.

Novel Robot Solutions for Carrying out Field Joint Welding and Machining in the Assembly of the Vacuum Vessel of ITER

It is necessary to use highly specialized robots in ITER (International Thermonuclear Experimental Reactor) both in the manufacturing and maintenance of the reactor due to a demanding environment. The sectors of the ITER vacuum vessel (VV) require more stringent tolerances than normally expected for the size of the structure involved. VV consists of nine sectors that are to be welded together. The vacuum vessel has a toroidal chamber structure. The task of the designed robot is to carry the welding apparatus along a path with a stringent tolerance during the assembly operation. In addition to the initial vacuum vessel assembly, after a limited running period, sectors need to be replaced for repair. Mechanisms with closed-loop kinematic chains are used in the design of robots in this work. One version is a purely parallel manipulator and another is a hybrid manipulator where the parallel and serial structures are combined. Traditional industrial robots that generally have the links actuated in series are inherently not very rigid and have poor dynamic performance in high speed and high dynamic loading conditions. Compared with open chain manipulators, parallel manipulators have high stiffness, high accuracy and a high force/torque capacity in a reduced workspace. Parallel manipulators have a mechanical architecture where all of the links are connected to the base and to the end-effector of the robot. The purpose of this thesis is to develop special parallel robots for the assembly, machining and repairing of the VV of the ITER. The process of the assembly and machining of the vacuum vessel needs a special robot. By studying the structure of the vacuum vessel, two novel parallel robots were designed and built; they have six and ten degrees of freedom driven by hydraulic cylinders and electrical servo motors. Kinematic models for the proposed robots were defined and two prototypes built. Experiments for machine cutting and laser welding with the 6-DOF robot were carried out. It was demonstrated that the parallel robots are capable of holding all necessary machining tools and welding end-effectors in all positions accurately and stably inside the vacuum vessel sector. The kinematic models appeared to be complex especially in the case of the 10-DOF robot because of its redundant structure. Multibody dynamics simulations were carried out, ensuring sufficient stiffness during the robot motion. The entire design and testing processes of the robots appeared to be complex tasks due to the high specialization of the manufacturing technology needed in the ITER reactor, while the results demonstrate the applicability of the proposed solutions quite well. The results offer not only devices but also a methodology for the assembly and repair of ITER by means of parallel robots.

Potentials of process intensification in the Finnish petrochemical industry

This research was motivated by the need to examine the potential application areas of process intensification technologies in Neste Oil Oyj. According to the company’s interest membrane reactor technology was chosen and applicability of this technology in refining industry was investigated. Moreover, Neste Oil suggested a project which is related to the CO2 capture from FCC unit flue gas stream. The flowrate of the flue gas is 180t/h and consist of approximately 14% by volume CO2. Membrane based absorption process (membrane contactor) was chosen as a potential technique to model CO2 capture from fluid catalytic cracking (FCC) unit effluent. In the design of membrane contactor, a mathematical model was developed to describe CO2 absorption from a gas mixture using monoethanole amine (MEA) aqueous solution. According to the results of literature survey, in the hollow fiber contactor for laminar flow conditions approximately 99 % percent of CO2 can be removed by using a 20 cm in length polyvinylidene fluoride (PDVF) membrane. Furthermore, the design of whole process was performed by using PRO/II simulation software and the CO2 removal efficiency of the whole process obtained as 97 %. The technical and economical comparisons among existing MEA absorption processes were performed to determine the advantages and disadvantages of membrane contactor technology.

Suunnitellun alas- ja ylösajon todennäköisyysperustainen riskianalyysi ydinvoimalaitokselle

Työssä tehtiin ydinvoimalaitoksen suunnitellun alas- ja ylösajon todennäköisyysperus-tainen riskianalyysi. Suunnitellun alasajon analyysi sisälsi Teollisuuden Voima Oyj:n käyttämän vanhan PRA-mallin päivityksen ja laajentamisen. Ylösajon analyysiä varten kehitettiin kokonaan uusi malli. Diplomityöselostuksen alussa on yleinen katsaus luotettavuustekniikan käsitteisiin, pe-rusperiaatteisiin ja työkaluihin. Sitten on esitelty laitostekniikkaa tärkeimpien alas- ja ylösajoihin osallistuvien järjestelmien osalta. Myös normaalit alas- ja ylösajotoimenpi-teet on kuvattu. Yleisen teoriaosuuden jälkeen on keskitytty uusien mallien muodosta-miseen. Työssä käytetyt oletukset ja arviot on esitelty perusteluineen. Uudet tapahtuma- ja vikapuut sekä niiden perusteella lasketut sydänvaurioriskit johtopäätöksineen on käy-ty läpi selostuksen lopussa. Alkutapahtumataajuuksien määrittäminen tehtiin vikapuiden avulla, joissa huomioitiin komponenttivikojen, inhimillisten virheiden ja ulkoisten tekijöiden vaikutus. Aiemmin alkutapahtumat oli määritetty pääasiassa käyttöhistorian perusteella. Uusi määrittelytapa antaa eri vikaantumistapojen välille paremman kuvan niiden keskinäisestä merkitykses-tä sekä paremman päivitettävyyden laitosmuutosten yhteydessä. Mallien avulla voidaan laskea alas- ja ylösajon merkitys kokonaissydänvauriotaajuuteen entistä yksityiskohtaisemmin. Tuloksia voidaan myös hyödyntää laitosten vikatilanteis-sa, kun vertaillaan jatketun käytön ja mahdollisten korjaustöiden vaatiman alas- ja ylösajon riskejä. Uusien mallien antamat tulokset laskivat vain hieman kokonaissydän-vauriotaajuutta, mutta merkittävästi alasajon vaikutusta siihen. Ylösajosta aiheutuva riskinlisä oli noin puolet alasajon riskistä.

Kevytvesilaitosten reaktoripainesäiliöiden säteilyhaurastuminen

Työssä käydään läpi säteilyhaurastumisilmiöitä ja niistä johtuvia vaikutuksia kevytvesilaitosten reaktoripainesäiliöille

Model based study of a calcium oxide looping process for post-combustion carbon dioxide capture

Calcium oxide looping is a carbon dioxide sequestration technique that utilizes the partially reversible reaction between limestone and carbon dioxide in two interconnected fluidised beds, carbonator and calciner. Flue gases from a combustor are fed into the carbonator where calcium oxide reacts with carbon dioxide within the gases at a temperature of 650 ºC. Calcium oxide is transformed into calcium carbonate which is circulated into the regenerative calciner, where calcium carbonate is returned into calcium oxide and a stream of pure carbon dioxide at a higher temperature of 950 ºC. Calcium oxide looping has proved to have a low impact on the overall process efficiency and would be easily retrofitted into existing power plants. This master’s thesis is done in participation to an EU funded project CaOling as a part of the Lappeenranta University of Technology deliverable, reactor modelling and scale-up tools. Thesis concentrates in creating the first model frame and finding the physically relevant phenomena governing the process.

Reaktoreiden termisen tehon laskennan epävarmuuksien kartoitus

Diplomityössä selvitettiin Fortum Power and Heat Oy:n Loviisan VVER-440 painevesireaktorilaitosten termisen tehon laskentaan liittyviä epävarmuuksia. Laitoksen turvallisuusteknisissä käyttöehdoissa (TTKE) määrätään reaktorin suurimmaksi sallituksi lämpötehoksi 1500 MW. Tähän perustuen haluttiin selvittää nykyiseen RT1 laskentaan liittyvät epävarmuudet tarkastamalla nykyinen laskenta ja siinä käytetyt termohydrauliset laskentasovitteet. Työn alussa selostetaan lyhyesti Loviisan voimalaitoksen toimintaperiaate, jonka jälkeen esitellään laskentaan osallistuvat prosessimittaukset ja niihin liittyvät epävarmuustekijät. Mittauksille määritettiin epävarmuudet käyttäen hyödyksi komponenttivalmistajien tietoja sekä laitoksen kalibrointitodistuksia ja näiden lisäksi laskettiin standardin mukainen virhe virtauslaipoille. Edellä mainittujen virheiden perusteella voitiin laskea tehon epävarmuudet yksittäiselle höyrystimelle, josta edelleen varianssien summamenetelmällä saatiin reaktorin termiselle teholle 0,78 %:n epävarmuus 95 % luottamustasolla. Laskettua tehon epävarmuutta verrattiin Monte Carlo -menetelmällä suoritettuun tarkistuslaskentaan, jolla termisen tehon epävarmuudeksi saatiin 0,53 %, luottamustason ollessa 95 %. Työssä tarkasteltiin keskiarvotuksen vaikutusta mittausdataan. Näissä tarkasteluissa havaittiin pinnansäädöstä aiheutuva reaktoritehon huojunta, joka oli työn merkittävin havainto.

CFD Simulation of Two-phase and Three-phase Flows in Internal-loop Airlift

Airlift reactors are pneumatically agitated reactors that have been widely used in chemical, petrochemical, and bioprocess industries, such as fermentation and wastewater treatment. Computational Fluid Dynamics (CFD) has become more popular approach for design, scale-up and performance evaluation of such reactors. In the present work numerical simulations for internal-loop airlift reactors were performed using the transient Eulerian model with CFD package, ANSYS Fluent 12.1. The turbulence in the liquid phase is described using κ- ε the model. Global hydrodynamic parameters like gas holdup, gas velocity and liquid velocity have been investigated for a range of superficial gas velocities, both with 2D and 3D simulations. Moreover, the study of geometry and scale influence on the reactor have been considered. The results suggest that both, geometry and scale have significant effects on the hydrodynamic parameters, which may have substantial effects on the reactor performance. Grid refinement and time-step size effect have been discussed. Numerical calculations with gas-liquid-solid three-phase flow system have been carried out to investigate the effect of solid loading, solid particle size and solid density on the hydrodynamic characteristics of internal loop airlift reactor with different superficial gas velocities. It was observed that averaged gas holdup is significantly decreased with increasing slurry concentration. Simulations show that the riser gas holdup decreases with increase in solid particle diameter. In addition, it was found that the averaged solid holdup increases in the riser section with the increase of solid density. These produced results reveal that CFD have excellent potential to simulate two-phase and three-phase flow system.

Kinetic modeling of mechanisms of industrially important organic reactions in gas and liquid phase

This dissertation is based on 5 articles which deal with reaction mechanisms of the following selected industrially important organic reactions: 1. dehydrocyclization of n-butylbenzene to produce naphthalene 2. dehydrocyclization of 1-(p-tolyl)-2-methylbutane (MB) to produce 2,6-dimethylnaphthalene 3. esterification of neopentyl glycol (NPG) with different carboxylic acids to produce monoesters 4. skeletal isomerization of 1-pentene to produce 2-methyl-1-butene and 2-methyl-2-butene The results of initial- and integral-rate experiments of n-butylbenzene dehydrocyclization over selfmade chromia/alumina catalyst were applied when investigating reaction 2. Reaction 2 was performed using commercial chromia/alumina of different acidity, platina on silica and vanadium/calcium/alumina as catalysts. On all catalysts used for the dehydrocyclization, major reactions were fragmentation of MB and 1-(p-tolyl)-2-methylbutenes (MBes), dehydrogenation of MB, double bond transfer, hydrogenation and 1,6-cyclization of MBes. Minor reactions were 1,5-cyclization of MBes and methyl group fragmentation of 1,6- cyclization products. Esterification reactions of NPG were performed using three different carboxylic acids: propionic, isobutyric and 2-ethylhexanoic acid. Commercial heterogeneous gellular (Dowex 50WX2), macroreticular (Amberlyst 15) type resins and homogeneous para-toluene sulfonic acid were used as catalysts. At first NPG reacted with carboxylic acids to form corresponding monoester and water. Then monoester esterified with carboxylic acid to form corresponding diester. In disproportionation reaction two monoester molecules formed NPG and corresponding diester. All these three reactions can attain equilibrium. Concerning esterification, water was removed from the reactor in order to prevent backward reaction. Skeletal isomerization experiments of 1-pentene were performed over HZSM-22 catalyst. Isomerization reactions of three different kind were detected: double bond, cis-trans and skeletal isomerization. Minor side reaction were dimerization and fragmentation. Monomolecular and bimolecular reaction mechanisms for skeletal isomerization explained experimental results almost equally well. Pseudohomogeneous kinetic parameters of reactions 1 and 2 were estimated by usual least squares fitting. Concerning reactions 3 and 4 kinetic parameters were estimated by the leastsquares method, but also the possible cross-correlation and identifiability of parameters were determined using Markov chain Monte Carlo (MCMC) method. Finally using MCMC method, the estimation of model parameters and predictions were performed according to the Bayesian paradigm. According to the fitting results suggested reaction mechanisms explained experimental results rather well. When the possible cross-correlation and identifiability of parameters (Reactions 3 and 4) were determined using MCMC method, the parameters identified well, and no pathological cross-correlation could be seen between any parameter pair.

Simulation of hydrogen peroxide direct synthesis in a microreactor

A set of models in Aspen plus was built to simulate the direct synthesis process of hydrogen peroxide in a micro-reactor system. This process model can be used to carry out material balance calculation under various experimental conditions. Three thermodynamic property methods were compared by calculating gas solubility and Uniquac-RK method was finally selected for process model. Two different operation modes with corresponding operation conditions were proposed as the starting point of future experiments. Simulations for these two modes were carried out to get the information of material streams. Moreover, some hydrodynamic parameters such as gas/liquid superficial velocity, gas holdup were also calculated with improved process model. These parameters proved the proposed experimental conditions reasonable to some extent. The influence of operation conditions including temperature, pressure and circulation ratio was analyzed for the first operation mode, where pure oxygen was fed into dissolving tank and hydrogen-carbon dioxide mixture was fed into microreactor directly. The preferred operation conditions for the system are low temperature (2°C) and high pressure (30 bar) in dissolving tank. High circulation ratio might be good in the sense that more oxygen could be dissolved and fed into reactor for reactions, but meanwhile hydrodynamics of microreactor should be considered. Furthermore, more operation conditions of reactor gas/liquid feeds in both of two operation modes were proposed to provide guidance for future experiment design and corresponding hydrodynamic parameters were also calculated. Finally, safety issue was considered from thermodynamic point of view and there is no explosion danger at given experimental plan since the released reaction heat will not cause solvent vaporization inside the microchannels. The improvement of process model still needs further study based on the future experimental results.

Development of chemical looping combustion process

Chemical looping combustion (CLC) provides a promising technology to help cut carbon dioxide emissions. CLC is based on separated oxidation and reduction processes. Oxygen carrier, which is made from metal and supporting material, is in continuous recirculation between the air and fuel reactors. The CLC process does not require separation unit for carbon dioxide. The fuel reactor can produce an almost pure carbon dioxide feed which decrease costs of carbon capture and storage (CCS). The CLC method is one of the most promising ones for energy efficient carbon capture. A large amount of literature was examined for this study and from it the most promising methods and designs were chosen. These methods and designs were combined as reactor system design which was then sized during the making of this thesis. Sizing was done with a mathematical model that was further improved during the study.