Öljynjalostamon vetyverkon PINCH-analyysi

Tässä diplomityössä on tarkasteltu Porvoon öljynjalostamon vetyverkkoa ja pohdittu keinoja, joilla vedyn käyttöä jalostamolla voitaisiin tehostaan sekä polttokaasuverkkoon menevän vedyn määrä pienentää. Tarkastelun lähtökohtana toimii vetytaseen pohjalta laadittu vetypinch-analyysi. Kirjallisuusosassa on esitelty jalostamon vetyverkkoon kuuluvat yksiköt sekä käsitelty lyhyesti niiden toimintaa. Lisäksi on käsitelty vetypinch-analyysin periaate, sekä kuinka todelliset prosessirajoitteet voidaan huomioida sitä toteutettaessa. Kirjallisuusosan lopussa on esitetty miten vetyverkon vaiheittainen optimointi etenee. Työn soveltavassa osassa laadittiin vetyverkon virtauskaavio, jolla saatiin luotua kattava käsitys jalostamon vedynjakelusta. Virtauskaaviosta tehtiin yksinkertaistettu versio, jonka perusteella laadittiin vetytase. Vetytaseen pohjalta suoritettiin vetypinch-analyysi, jonka mukaan jalostamolla tuotettiin tasehetkellä ylimäärin vetyä. Vedyn käytön tehostamiseksi jalostamolla tulee rikkivedyn talteenottoyksikkö 2:n polttokaasuvirta pyrkiä minimoimaan tai hyödyntämään. Lisäksi virtausmittareiden mitoituspisteiden molekyylimassat tulisi muuttaa vastaamaan paremmin nykyistä ajotilannetta, sekä seurata niitä jatkossa säännöllisesti. Myös vetypitoisuutta mittaavien online-analysaattoreiden kalibroinnista tulee huolehtia, ja ottaa riittävästi kenttänäytteitä vetyverkosta. On huomattava, että öljynjalostamon vedyn tuotannon minimointi ei ole aina automaattisesti taloudellisin ratkaisu. Joissain tapauksissa vedyn osapaineen nostaminen vetyä kuluttavan yksikön reaktorissa voi lisätä yksikön tuottavuutta niin paljon, että se kompensoi lisääntyneestä vedyn tuotannosta aiheutuvat kustannukset.

Electrochemical Treatment of Wastewaters

Electrocoagulation is a process in which wastewater is treated under electrical current. Coagulant is formed during the process through the metal anode dissolution to respective ions which react with hydroxyl ions released in cathode. These metal hydroxides form complexes with pollutant ions. Pollutants are removed among metal hydroxide precipitates. This study was concentrated on describing chemistry and device structures in which electrochemical treatment operations are based on. Studied pollutants were nitrogen compounds, sulphate, trivalent and pentavalent arsenic, heavy metals, phosphate, fluoride, chloride, and bromide. In experimental part, removal of ammonium, nitrate, and sulphate during electrochemical treatment was studied separately. Main objective of this study was to find suitable metal plate material for ammonium, nitrate, and sulphate removal, respectively. Also other parameters such as pH of solution, concentration of pollutant and sodium chloride, and current density were optimized. According to this study the most suitable material for ammonium and sulphate removal by electrochemical treatment was stainless steel. Respectively, iron was the optimum material for nitrate removal. Rise in the pH of solution at the final stage of electrochemical treatment of ammonium, nitrate, and sulphate was detected. Conductivities of solutions decreased during ammonium removal in electrochemical processes. When nitrate and sulphate were removed electrochemically conductivities of solutions increased. Concentrations of residual metals in electrochemically treated solutions were not significant. Based on this study electrochemical treatment processes are recommended to be used in treatment of industrial wastewaters. Treatment conditions should be optimized for each wastewater matrix.

Finnish cleantech SMEs in China: Challenges and solutions

The rapid economic growth in China has resulted in environmental challenges ranging from air pollution to water-related issues. Thus supporting clean technology, or cleantech, that encompasses industries that focus on alternative energy, pollution and recycling, power supplies and conservation has become one of the focal points in the Chinese economic policy for the next decade. Simultaneously, the Finnish government has initiated programs to support the internationalisation of domestic cleantech companies in an attempt to spiral the industry into one of the pillars of Finnish economic growth. This study concentrates on the conjunction of these two themes and studies the challenges faced by Finnish cleantech SMEs in the Chinese market. Consequently, the study answers the following sub questions: 1. What human and financial resource-based challenges do Finnish cleantech SMEs face in the Chinese market and what are their solutions? 2. What knowledge-based challenges do Finnish cleantech SMEs face in the Chinese market and how can these difficulties be resolved? 3. What network-based challenges do Finnish cleantech SMEs face in the Chinese market, how do they relate to the resource- and knowledge-based challenges, and how can these difficulties be resolved? This qualitative study is conducted by analysing four semi structured interviews collected from four Finnish SMEs that operate in China. The findings of the study indicate that in human resources the most important challenges are related to the hiring and retaining of employees. In contrast to extant academic literature results distinguish salary and social status as the main solutions to this challenge. Regarding financial resources it is discovered that cleantech companies enjoy a benign business environment in China and benefit from the Chinese government’s support for cleantech industry. Challenges related to knowledge resources can be grouped into categories with the most interesting knowledge flows being the stream of local market knowledge into to the foreign parent company and the outward flow of manufacturing and business practice information into the target venture. The challenge related to the first flow is gathering relevant information and the main solutions are clustering at the foreign location and hiring knowledge prior to internationalisation. Regarding the second flow the main challenge is related to intellectual property rights and the most interesting solution is the purposeful transformation of explicit knowledge into tacit knowledge. Finally, it is discovered that networks, called guanxi in China, greatly affect the business processes. Within the guanxi system there is the concept of face which was found to affect employee propensity to stay as well as, as a novel academic result, employees’ knowledge sharing intention.

Mäskin sisältämän ligniinin modifiointi PCD-hapetuksella

Teoriaosassa tutkittiin mäskin muodostumista oluentuotantoprosessissa, ligniiniä ja sen pilkkoutumista hapetuksella, eri kehittyneitä hapetusmenetelmiä ja hapetuksella saatavia potentiaalisia pääkomponentteja. Kehittyneissä hapetusmenetelmissä keskityttiin pääasiassa pulssitettuun koronapurkaukseen perustuvaan PCD-menetelmään (Pulsed Corona Discharge). Tutkittavana pääkomponenttina toimi glyoksyylihappo. Työn kokeellisessa osassa tutkittiin mäskistä erotetun ligniinin pilkkoutumista PCD-hapetuksella. Tässä menetelmässä hapetus perustuu sähköpurkauksen aikana syntyvien hydroksyyliradikaalien ja otsonin muodostumiseen, jotka voivat toimia hapettimina. Kokeissa käytettiin oluentuotannosta saatua mäskiä, josta ligniiniä liuotettiin natriumhydroksidi-vesi-liuoksen avulla uuttamalla.. Tämän jälkeen liuosta käsiteltiin PCD laitteistossa. PCD-käsiteltyä tuotetta analysoitiin mittaamalla ligniinin ja aldehydien pitoisuudet siitä spektrofotometrin avulla. Työn tarkoituksena on tutkia PCD hapetusmenetelmän soveltuvuutta mäskin sisältämän ligniinin muokkaamiseen siten, että siitä syntyvää tuotetta voitaisiin käyttää jossakin muussa sovelluksessa, kuten esimerkiksi lääkkeiden raaka-aineena lääketeollisuudessa. PCD hapetusmenetelmä on koronasähköpurkauksiin perustuva laite, jota käytetään pääasiassa vedenpuhdistuksessa hajoittamaan haitallisia orgaanisia yhdisteitä. Tämän työn perusteella ligniiniä hajosi, aldehydejä muodostui ja hapetusnäytteiden pH laski hapetusajan kasvaessa. Tämä viittasi vahvasti glyoksyylihapon muodostumiseen PCD-laitteistossa.

Modelling of potentiometric ion sensors

Potentiometric ion sensors are a very important subgroup of electrochemical sensors, very attractive for practical applications due to their small size, portability, low-energy consumption, relatively low cost and not changing the sample composition. They are investigated by the researchers from many fields of science. The continuous development of this field creates the necessity for a detailed description of sensor response and the electrochemical processes important in the practical applications of ion sensors. The aim of this thesis is to present the existing models available for the description of potentiometric ion sensors as well as their applicability and limitations. This includes the description of the diffusion potential occurring at the reference electrodes. The wide range of existing models, from most idealised phase boundary models to most general models, including migration, is discussed. This work concentrates on the advanced modelling of ion sensors, namely the Nernst-Planck-Poisson (NPP) model, which is the most general of the presented models, therefore the most widely applicable. It allows the modelling of the transport processes occurring in ion sensors and generating the potentiometric response. Details of the solution of the NPP model (including the numerical methods used) are shown. The comparisons between NPP and the more idealized models are presented. The applicability of the model to describe the formation of diffusion potential in reference electrode, the lower detection limit of both ion-exchanger and neutral carrier electrodes and the effect of the complexation in the membrane are discussed. The model was applied for the description of both types of electrodes, i.e. with the inner filling solution and solidcontact electrodes. The NPP model allows the electrochemical methods other than potentiometry to be described. Application of this model in Electrochemical Impedance Spectroscopy is discussed and a possible use in chrono-potentiometry is indicated. By combining the NPP model with evolutionary algorithms, namely Hierarchical Genetic Strategy (HGS), a novel method allowing the facilitation of the design of ion sensors was created. It is described in detail in this thesis and its possible applications in the field of ion sensors are indicated. Finally, some interesting effects occurring in the ion sensors (i.e. overshot response and influence of anionic sites) as well as the possible applications of NPP in biochemistry are described.

Circular Spectropolarimetric Studies of DQ White Dwarfs

This thesis summarizes studies of a class of white dwarfs (WDs) called DQ WDs. White dwarfs are the remnants of ordinary stars like our Sun that have run out of nuclear fuel. WDs are classified according to the composition of their atmosphere and DQ WDs have an atmosphere made of helium and carbon. The carbon comes in either atomic or molecular form and in some cases the strong spectral absorption features cover the entire optical wavelength region. The research presented here utilizes spectropolarimetry, which is an observational technique that combines spectroscopy and polarization. Separately these allow to study the composition of a target and the inhomogeneous distribution of matter in the target. Put together they form a powerful tool to probe the physical properties in the atmosphere of a star. It is espacially good for detecting magnetic fields. The papers in this thesis describe efforts to do a survey of DQ white dwarfs with spectropolarimetry in order to search for magnetic fields in them. Paper I describes the discovery of a new magnetic cool DQ white dwarf, GJ841B. Initial modeling of molecular features on DQ WDs showed inconsistencies with observations. The first possible solution to this problem was stellar spots on these WDs. To investigate the matter, two DQ WDs were monitored for photometric variability that could arise from the presence of such spots. Paper II summarizes this short campaign and reports the negative results. Paper III reports observations of the rest of the objects in our survey. The paper includes the discovery of polarization from another cool DQ white dwarf, bringing the total of known magnetic cool DQs to three. Unfortunately the model used in this thesis cannot, in its present state, be used to model these objects nor are the observations of high enough spectroscopic resolution to do so.

Säilöntämenetelmien parantaminen höyryvoimaprosessissa

Lahti Energia Oy:n kivihiiltä polttavan Kymijärvi I voimalaitoksen vuotuiset käyttötunnit ovat vähentyneet. Syy vähennykseen on ollut uuden kaasutusvoimalaitoksen käyttöönotto vuonna 2012, jolloin vanhan voimalaitoksen käytölle ei ole ollut tarvetta kesäkuukausina. Seisonta-aikana voimalaitoksen höyryvoimaprosessi tulee säilöä. Säilönnällä tarkoitetaan toimenpiteitä, joilla estetään korroosio-olosuhteiden syntyminen voimalaitoksen laitteisiin. Säilöntätavasta riippuen estetään joko hapen tai kosteuden esiintyminen. Tässä diplomityössä tutkitaan eri säilöntämenetelmien ominaisuuksia tavoitteena löytää sopivin vaihtoehto vanhalle kivihiilivoimalaitokselle. Työssä perehdytään teorian kautta kolmeen menetelmään voimalaitoksen kattilan säilönnässä. Typpi- ja märkäsäilönnässä estetään hapen ja kuivailmasäilönnässä kosteuden esiintyminen. Työssä on myös tutkittu kattilan säilöntämenetelmien vaikutuksia muihin laitteistoihin ja järjestelmiin. Tuloksien perusteella voidaan todeta, että kuivailmasäilöntä on toimivin ratkaisu voimalaitoksen viimeisille käyttövuosille. Voimalaitoksen jäädessä varavoimalaitokseksi on typpisäilöntä kustannustehokkain vaihtoehto.

Projektien resurssien hallinnan parantaminen Loviisan voimalaitoksella

Työn tavoitteena oli löytää NCC:n (Nuclear Competence Center) toimintaympäristöön sopivat resurssien hallinnan ratkaisumallit työkaluineen. Tarkoituksena oli saada näkemys siitä mitä tulisi tehdä, jotta projektien resurssien hallintaa pystyttäisiin parantamaan. Työssä käydään läpi resurssisuunnittelua ja resurssien hallintaa kokonaisvaltaisesti. Tärkein keskittymisalue on kuitenkin resurssien hallinta moniprojektiympäristössä. Työssä on haastateltu projektipäälliköitä ja muita resurssiongelmien kanssa tekemisissä olevia, jotta saadaan kuva siitä, mikä resurssien hallinnan nykytilanne on ja miten sitä halutaan kehittää. Haastatteluiden pohjalta on tehty ehdotuksia resurssien hallinnan toteuttamiseksi. Tuloksista tärkeimmäksi voisi todeta sen, että resurssien hallinnan parantaminen ei ole helppoa ja se tulee vaatimaan monia toimintatapamuutoksia. Lisäksi tällä hetkellä resurssien hallintaa ei luultavasti ole mahdollista toteuttaa valmisohjelman avulla, joten ainakin toistaiseksi olisi järkevintä toteuttaa resurssien hallinta Excel-ratkaisun avulla.

How to take advantage of ORCID in institutional repositories

Workshop at Open Repositories 2014, Helsinki, Finland, June 9-13, 2014

Kestomagnetoidun roottorin mekaniikkasuunnittelu ja -analysointi

Työssä kehitettiin suurnopeuskäyttöön soveltuva kestomagnetoitu roottori olemassa olevan induktiokoneen staattorirunkoon. Kehitystyön tarkoituksena oli selvittää roottorin mekaaniset raja-arvot, kuten maksimi kehänopeus. Samalla otettiin kantaa myös tarvittaviin analysointi- ja mitoitusmenetelmiin. Maksimi kehänopeuden, laakeroinnin ja roottorin skaalattavuuden selvittäminen edellytti myös tarkkaa materiaaliselvitystä ja optimointia. Tästä syystä työn aikana tehtiin tiivistä yhteistyötä materiaalitoimittajien kanssa. Työn tuloksena syntyi uusi menetelmä toteuttaa radiaalisen magneettivuon luova kestomagneettiroottori 200 m/s kehänopeudelle. Suunniteltua roottoriratkaisua käytetään testausroottorina, jolla selvitetään valmistuksen, kokoonpanon ja sähkötehon rajoitteet käytännössä. Suunnittelutyö edellyttikin jatkuvaa iterointia sähkösuunnittelun ja roottorin osien valmistajien kanssa, jotta löydettiin paras kompromissiratkaisu roottorin prototyyppiin. Tämän seurauksena saatiin luotua varsin tarkat suunnittelu- ja analysointiraja-arvot kestomagneettiroottorin tuotteistettavia versioita varten.

Co-creating value with customers as a new approach of entering new market

Global trends associated with development of information technology, globalization, industrial and economic changes are influencing on company and customer domains and thus transforming company-customer relationship. The company centric paradigm with a strong product focus shifts to a customer oriented one with a strong emphasis on customer collaboration. As a result, the customer role changes from a passive observer to an active player. Moreover, global trends contribute to transformation of competitive environment making it tougher and simplifying an access to resources previously considered as unique. All that factors push the companies towards cooperation with customers in order to identify unarticulated needs and finding the best possible solution to existing customer problems. The Master’s Thesis is done for Outotec (Lappeenranta) which considers extension of dewatering business in Russian coal market. Research aims to identify key features of coal preparation and dewatering of fine coal and tailings in Russian preparation plants; analyze the state of Russian coal market and evaluate market potential for Outotec dewatering solutions. The study has a qualitative nature and implements an action research methodology that involves both creation of knowledge and introduction of changes into the system. The base for taking actions is formed by theoretical framework that targets on describing company - customer interaction and has selected co-creation as the most appropriate method of customer involvement. The integration of co-creation approach into an action research cycle allows not only fulfilling the research objectives but also facilitates organizational learning and intraorganizational collaboration, assists in establishing customer contacts and making the first steps into the market, bringing new joint projects to the company and opening real business opportunities.

Advanced analysis and design methods for preparative chromatographic separation processes

Preparative liquid chromatography is one of the most selective separation techniques in the fine chemical, pharmaceutical, and food industries. Several process concepts have been developed and applied for improving the performance of classical batch chromatography. The most powerful approaches include various single-column recycling schemes, counter-current and cross-current multi-column setups, and hybrid processes where chromatography is coupled with other unit operations such as crystallization, chemical reactor, and/or solvent removal unit. To fully utilize the potential of stand-alone and integrated chromatographic processes, efficient methods for selecting the best process alternative as well as optimal operating conditions are needed. In this thesis, a unified method is developed for analysis and design of the following singlecolumn fixed bed processes and corresponding cross-current schemes: (1) batch chromatography, (2) batch chromatography with an integrated solvent removal unit, (3) mixed-recycle steady state recycling chromatography (SSR), and (4) mixed-recycle steady state recycling chromatography with solvent removal from fresh feed, recycle fraction, or column feed (SSR–SR). The method is based on the equilibrium theory of chromatography with an assumption of negligible mass transfer resistance and axial dispersion. The design criteria are given in general, dimensionless form that is formally analogous to that applied widely in the so called triangle theory of counter-current multi-column chromatography. Analytical design equations are derived for binary systems that follow competitive Langmuir adsorption isotherm model. For this purpose, the existing analytic solution of the ideal model of chromatography for binary Langmuir mixtures is completed by deriving missing explicit equations for the height and location of the pure first component shock in the case of a small feed pulse. It is thus shown that the entire chromatographic cycle at the column outlet can be expressed in closed-form. The developed design method allows predicting the feasible range of operating parameters that lead to desired product purities. It can be applied for the calculation of first estimates of optimal operating conditions, the analysis of process robustness, and the early-stage evaluation of different process alternatives. The design method is utilized to analyse the possibility to enhance the performance of conventional SSR chromatography by integrating it with a solvent removal unit. It is shown that the amount of fresh feed processed during a chromatographic cycle and thus the productivity of SSR process can be improved by removing solvent. The maximum solvent removal capacity depends on the location of the solvent removal unit and the physical solvent removal constraints, such as solubility, viscosity, and/or osmotic pressure limits. Usually, the most flexible option is to remove solvent from the column feed. Applicability of the equilibrium design for real, non-ideal separation problems is evaluated by means of numerical simulations. Due to assumption of infinite column efficiency, the developed design method is most applicable for high performance systems where thermodynamic effects are predominant, while significant deviations are observed under highly non-ideal conditions. The findings based on the equilibrium theory are applied to develop a shortcut approach for the design of chromatographic separation processes under strongly non-ideal conditions with significant dispersive effects. The method is based on a simple procedure applied to a single conventional chromatogram. Applicability of the approach for the design of batch and counter-current simulated moving bed processes is evaluated with case studies. It is shown that the shortcut approach works the better the higher the column efficiency and the lower the purity constraints are.

Functional cellulose microspheres for pharmaceutical applications

Dissolving cellulose is the first main step in preparing novel cellulosicmaterials. Since cellulosic fibres cannot be easily dissolved in water-based solvents, fibres were pretreated with ethanol-acid solution prior to the dissolution. Solubility and changes on the surface of the fibres were studied with microscopy and capillary viscometry. After the treatment, the cellulose fibres were soluble in alkaline urea-water solvent. The nature of this viscous solution was studied rheologically. Cellulose microspheres were prepared by extruding the alkaline cellulose solution through the needle into an acidic medium. By altering the temperature and acidity of the mediumit was possible to adjust the specific surface area and pore sizes of themicrospheres. A typical skin-core structure was found in all samples. Microspheres were oxidised in order to introduce anionic carboxylic acid groups (AGs). Anionic microspheres are more hydrophilic; their water-uptake increased 25 times after oxidation and they could swell almost to their original state (88%) after drying and shrinking. Swelling was studied in simulated physiological environments, corresponding to stomach acid and intestines (pH 1.2-7.4). Oxidised microspheres were used as a drug carriers. They demonstrated a highmass uniformity, which would enable their use for personalised dosing among different patients, including children. The drug was solidified in microspheres in amorphous form. This enhanced solubility and could be used for more challenging drugs with poor solubility. The pores of themicrospheres also remained open after the drug was loaded and they were dried. Regardless of the swelling, the drug was released at a constant rate in all environments.

Readout architectures for hybrid pixel detector readout chips

The original contribution of this thesis to knowledge are novel digital readout architectures for hybrid pixel readout chips. The thesis presents asynchronous bus-based architecture, a data-node based column architecture and a network-based pixel matrix architecture for data transportation. It is shown that the data-node architecture achieves readout efficiency 99% with half the output rate as a bus-based system. The network-based solution avoids “broken” columns due to some manufacturing errors, and it distributes internal data traffic more evenly across the pixel matrix than column-based architectures. An improvement of > 10% to the efficiency is achieved with uniform and non-uniform hit occupancies. Architectural design has been done using transaction level modeling (TLM) and sequential high-level design techniques for reducing the design and simulation time. It has been possible to simulate tens of column and full chip architectures using the high-level techniques. A decrease of > 10 in run-time is observed using these techniques compared to register transfer level (RTL) design technique. Reduction of 50% for lines-of-code (LoC) for the high-level models compared to the RTL description has been achieved. Two architectures are then demonstrated in two hybrid pixel readout chips. The first chip, Timepix3 has been designed for the Medipix3 collaboration. According to the measurements, it consumes < 1 W/cm^2. It also delivers up to 40 Mhits/s/cm^2 with 10-bit time-over-threshold (ToT) and 18-bit time-of-arrival (ToA) of 1.5625 ns. The chip uses a token-arbitrated, asynchronous two-phase handshake column bus for internal data transfer. It has also been successfully used in a multi-chip particle tracking telescope. The second chip, VeloPix, is a readout chip being designed for the upgrade of Vertex Locator (VELO) of the LHCb experiment at CERN. Based on the simulations, it consumes < 1.5 W/cm^2 while delivering up to 320 Mpackets/s/cm^2, each packet containing up to 8 pixels. VeloPix uses a node-based data fabric for achieving throughput of 13.3 Mpackets/s from the column to the EoC. By combining Monte Carlo physics data with high-level simulations, it has been demonstrated that the architecture meets requirements of the VELO (260 Mpackets/s/cm^2 with efficiency of 99%).

Enzymatic Synthesis, Recovery, and Purification of Ethyl β-ᴅ-glucopyranoside

A method to synthesize ethyl β-ᴅ-glucopyranoside (BEG) was searched. Feasibility of different ion exchange resins was examined to purify the product from the synthetic binary solution of BEG and glucose. The target was to produce at least 50 grams of 99 % pure BEG with a scaled up process. Another target was to transfer the batch process into steady-state recycle chromatography process (SSR). BEG was synthesized enzymatically with reverse hydrolysis utilizing β-glucosidase as a catalyst. 65 % of glucose reacted with ethanol into BEG during the synthesis. Different ion exchanger based resins were examined to separate BEG from glucose. Based on batch chromatography experiments the best adsorbent was chosen between styrene based strong acid cation exchange resins (SAC) and acryl based weak acid cation exchange resins (WAC). CA10GC WAC resin in Na+ form was chosen for the further separation studies. To produce greater amounts of the product the batch process was scaled up. The adsorption isotherms for the components were linear. The target purity was possible to reach already in batch without recycle with flowrate and injection size small enough. 99 % pure product was produced with scaled-up batch process. Batch process was transferred to SSR process utilizing the data from design pulse chromatograms and Matlab simulations. The optimal operating conditions for the system were determined. Batch and SSR separation results were compared and by using SSR 98 % pure products were gained with 40 % higher productivity and 40 % lower eluent consumption compared to batch process producing as pure products.