Modeling of Gold Cyanidation

The chemistry of gold dissolution in alkaline cyanide solution has continually received attention and new rate equations expressing the gold leaching are still developed. The effect of leaching parameters on gold gold cyanidation is studied in this work in order to optimize the leaching process. A gold leaching model, based on the well-known shrinking-core model, is presented in this work. It is proposed that the reaction takes place at the reacting particle surface which is continuously reduced as the reaction proceeds. The model parameters are estimated by comparing experimental data and simulations. The experimental data used in this work was obtained from Ling et al. (1996) and de Andrade Lima and Hodouin (2005). Two different rate equations, where the unreacted amount of gold is considered in one equation, are investigated. In this work, it is presented that the reaction at the surface is the rate controlling step since there is no internal diffusion limitation. The model considering the effect of non-reacting gold shows that the reaction orders are consistent with the experimental observations reported by Ling et al. (1996) and de Andrade Lima and Hodouin (2005). However, it should be noted that the model obtained in this work is based on assumptions of no side reactions, no solid-liquid mass transfer resistances and no effect from temperature.

Modeling reaction kinetics and mass transfer in ozonation in water solutions

This dissertation is based on four articles dealing with modeling of ozonation. The literature part of this considers some models for hydrodynamics in bubble column simulation. A literature review of methods for obtaining mass transfer coefficients is presented. The methods presented to obtain mass transfer are general models and can be applied to any gas-liquid system. Ozonation reaction models and methods for obtaining stoichiometric coefficients and reaction rate coefficients for ozonation reactions are discussed in the final section of the literature part. In the first article, ozone gas-liquid mass transfer into water in a bubble column was investigated for different pH values. A more general method for estimation of mass transfer and Henry’s coefficient was developed from the Beltrán method. The ozone volumetric mass transfer coefficient and the Henry’s coefficient were determined simultaneously by parameter estimation using a nonlinear optimization method. A minor dependence of the Henry’s law constant on pH was detected at the pH range 4 - 9. In the second article, a new method using the axial dispersion model for estimation of ozone self-decomposition kinetics in a semi-batch bubble column reactor was developed. The reaction rate coefficients for literature equations of ozone decomposition and the gas phase dispersion coefficient were estimated and compared with the literature data. The reaction order in the pH range 7-10 with respect to ozone 1.12 and 0.51 the hydroxyl ion were obtained, which is in good agreement with literature. The model parameters were determined by parameter estimation using a nonlinear optimization method. Sensitivity analysis was conducted using object function method to obtain information about the reliability and identifiability of the estimated parameters. In the third article, the reaction rate coefficients and the stoichiometric coefficients in the reaction of ozone with the model component p-nitrophenol were estimated at low pH of water using nonlinear optimization. A novel method for estimation of multireaction model parameters in ozonation was developed. In this method the concentration of unknown intermediate compounds is presented as a residual COD (chemical oxygen demand) calculated from the measured COD and the theoretical COD for the known species. The decomposition rate of p-nitrophenol on the pathway producing hydroquinone was found to be about two times faster than the p-nitrophenol decomposition rate on the pathway producing 4- nitrocatechol. In the fourth article, the reaction kinetics of p-nitrophenol ozonation was studied in a bubble column at pH 2. Using the new reaction kinetic model presented in the previous article, the reaction kinetic parameters, rate coefficients, and stoichiometric coefficients as well as the mass transfer coefficient were estimated with nonlinear estimation. The decomposition rate of pnitrophenol was found to be equal both on the pathway producing hydroquinone and on the path way producing 4-nitrocathecol. Comparison of the rate coefficients with the case at initial pH 5 indicates that the p-nitrophenol degradation producing 4- nitrocathecol is more selective towards molecular ozone than the reaction producing hydroquinone. The identifiability and reliability of the estimated parameters were analyzed with the Marcov chain Monte Carlo (MCMC) method. @All rights reserved. No part of the publication may be reproduced, stored in a retrieval system, or transmitted, in any form or by any means, electronic, mechanical, photocopying, recording, or otherwise, without the prior permission of the author.

Statistical Inversion Theory in X-ray Tomography

In this thesis the X-ray tomography is discussed from the Bayesian statistical viewpoint. The unknown parameters are assumed random variables and as opposite to traditional methods the solution is obtained as a large sample of the distribution of all possible solutions. As an introduction to tomography an inversion formula for Radon transform is presented on a plane. The vastly used filtered backprojection algorithm is derived. The traditional regularization methods are presented sufficiently to ground the Bayesian approach. The measurements are foton counts at the detector pixels. Thus the assumption of a Poisson distributed measurement error is justified. Often the error is assumed Gaussian, altough the electronic noise caused by the measurement device can change the error structure. The assumption of Gaussian measurement error is discussed. In the thesis the use of different prior distributions in X-ray tomography is discussed. Especially in severely ill-posed problems the use of a suitable prior is the main part of the whole solution process. In the empirical part the presented prior distributions are tested using simulated measurements. The effect of different prior distributions produce are shown in the empirical part of the thesis. The use of prior is shown obligatory in case of severely ill-posed problem.

Error Modeling and Accuracy Analysis of a Novel Mobile Hybrid Parallel Robot

Over the last decades, calibration techniques have been widely used to improve the accuracy of robots and machine tools since they only involve software modification instead of changing the design and manufacture of the hardware. Traditionally, there are four steps are required for a calibration, i.e. error modeling, measurement, parameter identification and compensation. The objective of this thesis is to propose a method for the kinematics analysis and error modeling of a newly developed hybrid redundant robot IWR (Intersector Welding Robot), which possesses ten degrees of freedom (DOF) where 6-DOF in parallel and additional 4-DOF in serial. In this article, the problem of kinematics modeling and error modeling of the proposed IWR robot are discussed. Based on the vector arithmetic method, the kinematics model and the sensitivity model of the end-effector subject to the structure parameters is derived and analyzed. The relations between the pose (position and orientation) accuracy and manufacturing tolerances, actuation errors, and connection errors are formulated. Computer simulation is performed to examine the validity and effectiveness of the proposed method.

Gamma spectrometry and gamma and X-ray tomography of nuclear fuel

The purpose of gamma spectrometry and gamma and X-ray tomography of nuclear fuel is to determine both radionuclide concentration and integrity and deformation of nuclear fuel. The aims of this thesis have been to find out the basics of gamma spectrometry and tomography of nuclear fuel, to find out the operational mechanisms of gamma spectrometry and tomography equipment of nuclear fuel, and to identify problems that relate to these measurement techniques. In gamma spectrometry of nuclear fuel the gamma-ray flux emitted from unstable isotopes is measured using high-resolution gamma-ray spectroscopy. The production of unstable isotopes correlates with various physical fuel parameters. In gamma emission tomography the gamma-ray spectrum of irradiated nuclear fuel is recorded for several projections. In X-ray transmission tomography of nuclear fuel a radiation source emits a beam and the intensity, attenuated by the nuclear fuel, is registered by the detectors placed opposite. When gamma emission or X-ray transmission measurements are combined with tomographic image reconstruction methods, it is possible to create sectional images of the interior of nuclear fuel. MODHERATO is a computer code that simulates the operation of radioscopic or tomographic devices and it is used to predict and optimise the performance of imaging systems. Related to the X-ray tomography, MODHERATO simulations have been performed by the author. Gamma spectrometry and gamma and X-ray tomography are promising non-destructive examination methods for understanding fuel behaviour under normal, transient and accident conditions.

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.

Laitosmittaukset turbiinilaitoksen suorituskyvyn seurantaan ydinvoimalaitoksen vuosihuoltojen yhteydessä

Työssä kehitettiin höyryvoimalaitosprosessin tilan seurantaan laitosmittausrutiini, jolla tarkastellaan erityisesti turbiinilaitoksen suorituskykyä ennen ja jälkeen vuosihuoltojen. Laitosmittaukset on kehitetty Teollisuuden Voima Oyj:n Olkiluodon ydinvoimalaitosyksikköjen OL1 ja OL2 tarpeisiin. Mittauksilla saadaan tietoa vuosihuollon kokonaisvaikutuksista prosessiin eli muuttuiko mikään vuosihuollon aikana ja mitkä syyt johtivat muutokseen. Lisäksi säännöllisillä mittauksilla tavoitellaan pitkän aikavälin referenssitietoa prosessin tilasta. Esimerkkimittaukset tehtiin kevään 2008 vuosihuolloissa, R108 ja R208. Työssä on esitetty mittausten suorittaminen, tulosten laskenta ja tarkastelu sekä raportointi. Luotu mittausrutiini pohjautuu höyryturbiinien ja lämmönsiirtimien vastaanottokokeita käsitteleviin standardeihin sekä laitosten viimeisimpiin prosessimuutosten yhteydessä toteutettuihin suorituskykymittauksiin. Laitosmittauksista tehtiin vastaanottokokeita kevyemmät ja yksinkertaisemmat mittaustapahtumat, joilla saadaan kuitenkin riittävän luotettavaa tietoa. Tunnuslukuja, joita ei käytettävissä olevien mittatietojen avulla saatu suoraan selville tai laskettua massa- ja energiataseilla, määritettiin stationaarisen tilan mallinnusohjelmalla TEMPO:lla. Esimerkkimittaukset sujuivat hyvin ja saadut tulokset antoivat kaivattua lisätietoa vuosihuollon vaikutuksesta prosessiin. Generaattorin bruttoteho aleni OL1:llä ja pysyi ennallaan OL2:lla. OL1:n tehon aleneminen selittyi syöttöveden virtausmäärän vähenemisellä, johon vaikutti virtausmittalaitteen lähettimen vaihto. OL2:lla ei havaittu turbiiniprosessissa muutoksia, mutta lauhduttimien suorituskyky parani. Lauhduttimien suorituskyvyn paraneminen ilmeni asteisuuksien pienentymisenä, johon vaikuttivat puhdistaminen ja ilmavuotojen väheneminen.

Kaksoislaatuisesta rakenneputkesta hitsatun X-liitoksen kestävyys ja muodonmuutoskyky

Rautaruukki Oyj:n uusi Ruukki double grade S420MH/S355J2H -rakenneputki yhdistää putkilajien S420MH ja S355J2H ominaisuudet. Eurocode 3:n suunnitteluohjeiden mukaan Ruukki double graden käyttöön on sovellettava lujuusluokan S420 mukaista hitsien mitoitusta ja rakenneputkiliitosten staattista mitoituskestävyyttä alentavaa varmuuskerrointa, kun halutaan hyödyntää lujuusluokan S420 ominaisuudet Ruukki double gradea käytettäessä. Tässä työssä tutkittiin S420-lujuusluokkaa vastaavien suunnittelumääräysten soveltamistarvetta Ruukki double grade -rakenneputken käyttöön. Työn tavoitteena oli arvioida Ruukki double grade -rakenneputkesta hitsaamalla valmistetun X-liitoksen kestävyyden ja muodonmuutoskyvyn riittävyys, kun hitsit mitoitettiin S355-lujuusluokkaa vastaavien Eurocode 3:n suunnitteluohjeiden mukaisesti. X-liitosten kestävyyttä ja muodonmuutoskykyä tutkittiin kokeellisesti -40 C lämpötilassa suoritettujen laboratoriokokeiden avulla sekä analyyttisen laskennan ja elementtimenetelmän keinoin. Kestävyyden riittävyyttä arvioitiin vertaamalla laboratoriokokeista saatuja liitosten kestävyyksiä Eurocode 3:n ja myötöviivateorian mukaisiin kestävyyksiin. Elementtimenetelmän ja laboratoriokokeen pohjalta piirrettyjä liitoksen voima-siirtymäkuvaajia vertailtiin keskenään, kun elementtimalli analysoitiin eri materiaalimalleilla. Lisäksi verrattiin elementtimallin voima-venymäkuvaajia liitoksen venymäliuskan arvoihin. Kaikki koesarjan S355-lujuusluokan mukaisilla hitsin a-mitoilla valmistetut liitokset täyttivät kestävyydelle ja muodonmuutoskyvylle asetetut vaatimukset. Täten tämän koesarjan perusteella ei ollut tarpeellista soveltaa S420-lujuusluokan mukaista hitsien mitoitusta ja staattista mitoituskestävyyttä alentavaa varmuuslukua Ruukki double grade -rakenneputkeen. Elementtimenetelmästä ja laboratoriokokeesta saadut liitoksen voima-siirtymäkuvaajat vastasivat hyvin toisiaan. Sen sijaan elementtimallin voima-venymä-kuvaajat eivät vastanneet venymäliuskojen mittausdataa kovin hyvin.

Modeling of electrolyte sorption – from phase equilibria to dynamic separation systems

In this thesis, general approach is devised to model electrolyte sorption from aqueous solutions on solid materials. Electrolyte sorption is often considered as unwanted phenomenon in ion exchange and its potential as an independent separation method has not been fully explored. The solid sorbents studied here are porous and non-porous organic or inorganic materials with or without specific functional groups attached on the solid matrix. Accordingly, the sorption mechanisms include physical adsorption, chemisorption on the functional groups and partition restricted by electrostatic or steric factors. The model is tested in four Cases Studies dealing with chelating adsorption of transition metal mixtures, physical adsorption of metal and metalloid complexes from chloride solutions, size exclusion of electrolytes in nano-porous materials and electrolyte exclusion of electrolyte/non-electrolyte mixtures. The model parameters are estimated using experimental data from equilibrium and batch kinetic measurements, and they are used to simulate actual single-column fixed-bed separations. Phase equilibrium between the solution and solid phases is described using thermodynamic Gibbs-Donnan model and various adsorption models depending on the properties of the sorbent. The 3-dimensional thermodynamic approach is used for volume sorption in gel-type ion exchangers and in nano-porous adsorbents, and satisfactory correlation is obtained provided that both mixing and exclusion effects are adequately taken into account. 2-Dimensional surface adsorption models are successfully applied to physical adsorption of complex species and to chelating adsorption of transition metal salts. In the latter case, comparison is also made with complex formation models. Results of the mass transport studies show that uptake rates even in a competitive high-affinity system can be described by constant diffusion coefficients, when the adsorbent structure and the phase equilibrium conditions are adequately included in the model. Furthermore, a simplified solution based on the linear driving force approximation and the shrinking-core model is developed for very non-linear adsorption systems. In each Case Study, the actual separation is carried out batch-wise in fixed-beds and the experimental data are simulated/correlated using the parameters derived from equilibrium and kinetic data. Good agreement between the calculated and experimental break-through curves is usually obtained indicating that the proposed approach is useful in systems, which at first sight are very different. For example, the important improvement in copper separation from concentrated zinc sulfate solution at elevated temperatures can be correctly predicted by the model. In some cases, however, re-adjustment of model parameters is needed due to e.g. high solution viscosity.

Epälineaaristen regressiomenetelmien vertaaminen robottikäden otemallinnuksessa

Tässä työssä verrattiin monikerrosperseptronin, radiaalikantafunktioverkon, tukivektoriregression ja relevanssivektoriregression soveltuvuutta robottikäden otemallinnukseen. Menetelmille ohjelmoitiin koeympäristö Matlabiin, jossa mallit koestettiin kolmiulotteisella kappaledatalla. Koejärjestely sisälsi kaksi vaihetta. Kokeiden ensimmäisessä vaiheessa menetelmille haettiin sopivat parametrit ja toisessa vaiheessa menetelmät koestettiin. Kokeilla kerättiin dataa menetelmien keskinäiseen vertailuun. Vertailussa huomioitiin laskentanopeus, koulutusaika ja tarkkuus. Tukivektoriregressio löydettiin potentiaaliseksi vaihtoehdoksi mallintamiseen. Tukivektoriregression koetuloksia analysoitiin muita menetelmiä enemmän hyvien koetulosten takia.

Test Campaign Parameter Editor for a Graphical TTCN-3 Development Environment

This paper presents the design for a graphical parameter editor for Testing and Test Control Notation 3 (TTCN-3) test suites. This work was done in the context of OpenTTCN IDE, a TTCN-3 development environment built on top of the Eclipse platform. The design presented relies on an additional parameter editing tab added to the launch configurations for test campaigns. This parameter editing tab shows the list of editable parameters and allows opening editing components for the different parameters. Each TTCN-3 primitive type will have a specific editing component providing tools to ease modification of values of that type.

Synthesis of percarboxylic acids in microreactor

Percarboxylic acids are commonly used as disinfection and bleaching agents in textile, paper, and fine chemical industries. All of these applications are based on the oxidative potential of these compounds. In spite of high interest in these chemicals, they are unstable and explosive chemicals, which increase the risk of synthesis processes and transportation. Therefore, the safety criteria in the production process should be considered. Microreactors represent a technology that efficiently utilizes safety advantages resulting from small scale. Therefore, microreactor technology was used in the synthesis of peracetic acid and performic acid. These percarboxylic acids were produced at different temperatures, residence times and catalyst i.e. sulfuric acid concentrations. Both synthesis reactions seemed to be rather fast because with performic acid equilibrium was reached in 4 min at 313 K and with peracetic acid in 10 min at 343 K. In addition, the experimental results were used to study the kinetics of the formation of performic acid and peracetic acid. The advantages of the microreactors in this study were the efficient temperature control even in very exothermic reaction and good mixing due to the short diffusion distances. Therefore, reaction rates were determined with high accuracy. Three different models were considered in order to estimate the kinetic parameters such as reaction rate constants and activation energies. From these three models, the laminar flow model with radial velocity distribution gave most precise parameters. However, sulfuric acid creates many drawbacks in this synthesis process. Therefore, a ´´greener´´ way to use heterogeneous catalyst in the synthesis of performic acid in microreactor was studied. The cation exchange resin, Dowex 50 Wx8, presented very high activity and a long life time in this reaction. In the presence of this catalyst, the equilibrium was reached in 120 second at 313 K which indicates a rather fast reaction. In addition, the safety advantages of microreactors were investigated in this study. Four different conventional methods were used. Production of peracetic acid was used as a test case, and the safety of one conventional batch process was compared with an on-site continuous microprocess. It was found that the conventional methods for the analysis of process safety might not be reliable and adequate for radically novel technology, such as microreactors. This is understandable because the conventional methods are partly based on experience, which is very limited in connection with totally novel technology. Therefore, one checklist-based method was developed to study the safety of intensified and novel processes at the early stage of process development. The checklist was formulated using the concept of layers of protection for a chemical process. The traditional and three intensified processes of hydrogen peroxide synthesis were selected as test cases. With these real cases, it was shown that several positive and negative effects on safety can be detected in process intensification. The general claim that safety is always improved by process intensification was questioned.

Design and characterization of large area position sensitive radiation detectors

Planar, large area, position sensitive silicon detectors are widely utilized in high energy physics research and in medical, computed tomography (CT). This thesis describes author's research work relating to development of such detector components. The key motivation and objective for the research work has been the development of novel, position sensitive detectors improving the performance of the instruments they are intended for. Silicon strip detectors are the key components of barrel-shaped tracking instruments which are typically the innermost structures of high energy physics experimental stations. Particle colliders such as the former LEP collider or present LHC produce particle collisions and the silicon strip detector based trackers locate the trajectories of particles emanating from such collisions. Medical CT has become a regular part of everyday medical care in all developed countries. CT scanning enables x-ray imaging of all parts of the human body with an outstanding structural resolution and contrast. Brain, chest and abdomen slice images with a resolution of 0.5 mm are possible and latest CT machines are able to image whole human heart between heart beats. The two application areas are presented shortly and the radiation detection properties of planar silicon detectors are discussed. Fabrication methods and preamplifier electronics of the planar detectors are presented. Designs of the developed, large area silicon detectors are presented and measurement results of the key operating parameters are discussed. Static and dynamic performance of the developed silicon strip detectors are shown to be very satisfactory for experimental physics applications. Results relating to the developed, novel CT detector chips are found to be very promising for further development and all key performance goals are met.

Novel Methods for Error Modeling and Parameter Identification of a Redundant Serial-Parallel Hybrid Robot

To obtain the desirable accuracy of a robot, there are two techniques available. The first option would be to make the robot match the nominal mathematic model. In other words, the manufacturing and assembling tolerances of every part would be extremely tight so that all of the various parameters would match the “design” or “nominal” values as closely as possible. This method can satisfy most of the accuracy requirements， but the cost would increase dramatically as the accuracy requirement increases. Alternatively, a more cost-effective solution is to build a manipulator with relaxed manufacturing and assembling tolerances. By modifying the mathematical model in the controller, the actual errors of the robot can be compensated. This is the essence of robot calibration. Simply put, robot calibration is the process of defining an appropriate error model and then identifying the various parameter errors that make the error model match the robot as closely as possible. This work focuses on kinematic calibration of a 10 degree-of-freedom (DOF) redundant serial-parallel hybrid robot. The robot consists of a 4-DOF serial mechanism and a 6-DOF hexapod parallel manipulator. The redundant 4-DOF serial structure is used to enlarge workspace and the 6-DOF hexapod manipulator is used to provide high load capabilities and stiffness for the whole structure. The main objective of the study is to develop a suitable calibration method to improve the accuracy of the redundant serial-parallel hybrid robot. To this end, a Denavit–Hartenberg (DH) hybrid error model and a Product-of-Exponential (POE) error model are developed for error modeling of the proposed robot. Furthermore, two kinds of global optimization methods, i.e. the differential-evolution (DE) algorithm and the Markov Chain Monte Carlo (MCMC) algorithm, are employed to identify the parameter errors of the derived error model. A measurement method based on a 3-2-1 wire-based pose estimation system is proposed and implemented in a Solidworks environment to simulate the real experimental validations. Numerical simulations and Solidworks prototype-model validations are carried out on the hybrid robot to verify the effectiveness, accuracy and robustness of the calibration algorithms.