Improving the competitiveness of electrolytic Zinc process by chemical reaction engineering approach

This doctoral thesis describes the development work performed on the leachand purification sections in the electrolytic zinc plant in Kokkola to increase the efficiency in these two stages, and thus the competitiveness of the plant. Since metallic zinc is a typical bulk product, the improvement of the competitiveness of a plant was mostly an issue of decreasing unit costs. The problems in the leaching were low recovery of valuable metals from raw materials, and that the available technology offered complicated and expensive processes to overcome this problem. In the purification, the main problem was consumption of zinc powder - up to four to six times the stoichiometric demand. This reduced the capacity of the plant as this zinc is re-circulated through the electrolysis, which is the absolute bottleneck in a zinc plant. Low selectivity gave low-grade and low-value precipitates for further processing to metallic copper, cadmium, cobalt and nickel. Knowledge of the underlying chemistry was poor and process interruptions causing losses of zinc production were frequent. Studies on leaching comprised the kinetics of ferrite leaching and jarosite precipitation, as well as the stability of jarosite in acidic plant solutions. A breakthrough came with the finding that jarosite could precipitate under conditions where ferrite would leach satisfactorily. Based on this discovery, a one-step process for the treatment of ferrite was developed. In the plant, the new process almost doubled the recovery of zinc from ferrite in the same equipment as the two-step jarosite process was operated in at that time. In a later expansion of the plant, investment savings were substantial compared to other technologies available. In the solution purification, the key finding was that Co, Ni, and Cu formed specific arsenides in the “hot arsenic zinc dust” step. This was utilized for the development of a three-step purification stage based on fluidized bed technology in all three steps, i.e. removal of Cu, Co and Cd. Both precipitation rates and selectivity increased, which strongly decreased the zinc powder consumption through a substantially suppressed hydrogen gas evolution. Better selectivity improved the value of the precipitates: cadmium, which caused environmental problems in the copper smelter, was reduced from 1-3% reported normally down to 0.05 %, and a cobalt cake with 15 % Co was easily produced in laboratory experiments in the cobalt removal. The zinc powder consumption in the plant for a solution containing Cu, Co, Ni and Cd (1000, 25, 30 and 350 mg/l, respectively), was around 1.8 g/l; i.e. only 1.4 times the stoichiometric demand – or, about 60% saving in powder consumption. Two processes for direct leaching of the concentrate under atmospheric conditions were developed, one of which was implemented in the Kokkola zinc plant. Compared to the existing pressure leach technology, savings were obtained mostly in investment. The scientific basis for the most important processes and process improvements is given in the doctoral thesis. This includes mathematical modeling and thermodynamic evaluation of experimental results and hypotheses developed. Five of the processes developed in this research and development program were implemented in the plant and are still operated. Even though these processes were developed with the focus on the plant in Kokkola, they can also be implemented at low cost in most of the zinc plants globally, and have thus a great significance in the development of the electrolytic zinc process in general.

Review of water electrolysis technologies and design of renewable hydrogen production systems

An electric system based on renewable energy faces challenges concerning the storage and utilization of energy due to the intermittent and seasonal nature of renewable energy sources. Wind and solar photovoltaic power productions are variable and difficult to predict, and thus electricity storage will be needed in the case of basic power production. Hydrogen’s energetic potential lies in its ability and versatility to store chemical energy, to serve as an energy carrier and as feedstock for various industries. Hydrogen is also used e.g. in the production of biofuels. The amount of energy produced during hydrogen combustion is higher than any other fuel’s on a mass basis with a higher-heating-value of 39.4 kWh/kg. However, even though hydrogen is the most abundant element in the universe, on Earth most hydrogen exists in molecular forms such as water. Therefore, hydrogen must be produced and there are various methods to do so. Today, the majority hydrogen comes from fossil fuels, mainly from steam methane reforming, and only about 4 % of global hydrogen comes from water electrolysis. Combination of electrolytic production of hydrogen from water and supply of renewable energy is attracting more interest due to the sustainability and the increased flexibility of the resulting energy system. The preferred option for intermittent hydrogen storage is pressurization in tanks since at ambient conditions the volumetric energy density of hydrogen is low, and pressurized tanks are efficient and affordable when the cycling rate is high. Pressurized hydrogen enables energy storage in larger capacities compared to battery technologies and additionally the energy can be stored for longer periods of time, on a time scale of months. In this thesis, the thermodynamics and electrochemistry associated with water electrolysis are described. The main water electrolysis technologies are presented with state-of-the-art specifications. Finally, a Power-to-Hydrogen infrastructure design for Lappeenranta University of Technology is presented. Laboratory setup for water electrolysis is specified and factors affecting its commissioning in Finland are presented.

On site measurements of DC link electrolytic capacitor bank of frequency converter using constant DC magnetization of the motor

Preventive maintenance of frequency converters has been based on pre-planned replace-ment of wearing or ageing components. Exchange intervals follow component life-time expectations which are based on empirical knowledge or schedules defined by manufac-turer. However, the lifetime of a component can vary significantly, because drives are used in very different operating environments and applications. The main objective of the research was to provide information on methods, i.e. how in-verter's operating condition can be measured reliably under field conditions. At first, the research focused on critical components such as current transducers, IGBTs and DC link capacitor bank, because these aging have already been identified. Of these, the DC link capacitor measurement method was selected for closer examination. With this method, the total capacitance and its total series resistance can be measured. The suitability of the measuring procedure was estimated on the basis of practical measurements. The research was made by using so called triangulation method, including a literature review, simulations and practical measurements. Based on the results, the new measu-rement method seems suitable with some reservations to practical measurements. How-ever, the measuring method should be further developed in order to improve its reliability.

Haja-asutusalueiden sakokaivolietteiden kalkkistabilointi ja hyötykäyttö maataloudessa

In the sparsely populated areas of Finland there are approximately 350 000 households and 450 000 leisure time residences outside sewer networks. According to the Finnish domestic wastewater act outside sewer networks, the Finnish Government is reducing the environmental load of domestic wastewaters by the year 2017. The law is aimed at restricting the quality of sludge from domestic wastewater purification systems. The wastewater purification systems are complex systems, which often include sedimentation basins. The sedimentation basins remove most of the nutrients from the domestic wastewaters. The Finnish Government has decided that sedimentation basin sludge must be treated before reusing. One possibility is to stabilise domestic sludge with slaked lime and to reuse treated sludge in agriculture. According to this master’s thesis lime stabilisation can be done in sedimentation basins or in decanting tanks. Decanting tanks must be under 100 m3. Dosage of stabilisation is 8,5 kg/m3 of lime. If you are treading sludge that is highly hydrous, you need 13,5 kg/m3 of lime. In stabilisation lime and sludge must be thoroughly mixed. Mixed sludge must be in sedimentation basin at least two hours. If there is evidence that sludge contains salmonella or if it’s decanting tank stabilisation time is 48 hours. Sludge must be mixed at least once during the longer stabilisation time. Lime destroys Esherichia coli and enterococcus concentrations below accepted level. Lime also destroys Salmonella bacterium. After treating, sludge’s can be distributed over a field. You can safely spread lime treated domestic sludge’s about 40 m3/ha. Lime stabilisation can also be used to treat separately and collectively collected domestic wastewaters.

Kunnan ympäristönsuojelumääräykset case Kotka

Ympäristönsuojelulain (86/2000) 19 §:n nojalla kunnilla voi olla ympäristönsuojelumääräykset. Määräysten antaminen on kunnille vapaaehtoista. Määräysten tulee olla ympäristönsuojelulain täytäntöönpanon kannalta tarpeellisia, kunnan paikallisista olosuhteista johtuvia kuntaa tai sen osaa koskevia yleisiä määräyksiä. Määräykset antaa kunnanvaltuusto. Ympäristönsuojelumääräyksillä on muuta lainsäädäntöä täydentävä, ei korvaava asema. Tämän työn tavoitteena oli laatia Kotkan kaupungille ehdotus kunnan ympäristönsuojelumääräyksiksi. Työn teoriaosassaon selvitetty kunnan ympäristönsuojelumääräysten oikeudelliset lähtökohdat ja suhde muuhun lainsäädäntöön. Tulososassa on selvitetty mitä toimintoja Kotkassa tulisi säännellä kunnan ympäristönsuojelumääräyksin. Työn toimeksiantajan kannalta oleellisimmat tulokset on esitetty työn liiteosassa. Ehdotuksen määräykset koskevat jätevesien käsittelyä, lumenkaatopaikkojen aiheuttamia ympäristöhaittoja, pölyn torjuntaa, tilapäisen melun torjuntaa, öljysäiliöiden tarkastamista ja käytöstä poistamista sekä hevosten pidon ympäristövaikutuksia. Ympäristönsuojelumääräysten voimaantulon myötä osa ympäristönsuojeluviranomaisen antamista suosituksista saa sitovan vaikutuksen. Ympäristönsuojelumääräykset osaltaan selventävät ympäristönsuojeluviranomaisen mahdollisuuksia puuttua eri toimintojen ympäristövaikutuksiin ennakolta.

Analysis of the voltage source inverter with small DC-link capacitor

IIn electric drives, frequency converters are used to generatefor the electric motor the AC voltage with variable frequency and amplitude. When considering the annual sale of drives in values of money and units sold, the use of low-performance drives appears to be in predominant. These drives have tobe very cost effective to manufacture and use, while they are also expected to fulfill the harmonic distortion standards. One of the objectives has also been to extend the lifetime of the frequency converter. In a traditional frequency converter, a relatively large electrolytic DC-link capacitor is used. Electrolytic capacitors are large, heavy and rather expensive components. In many cases, the lifetime of the electrolytic capacitor is the main factor limiting the lifetime of the frequency converter. To overcome the problem, the electrolytic capacitor is replaced with a metallized polypropylene film capacitor (MPPF). The MPPF has improved properties when compared to the electrolytic capacitor. By replacing the electrolytic capacitor with a film capacitor the energy storage of the DC-linkwill be decreased. Thus, the instantaneous power supplied to the motor correlates with the instantaneous power taken from the network. This yields a continuousDC-link current fed by the diode rectifier bridge. As a consequence, the line current harmonics clearly decrease. Because of the decreased energy storage, the DC-link voltage fluctuates. This sets additional conditions to the controllers of the frequency converter to compensate the fluctuation from the supplied motor phase voltages. In this work three-phase and single-phase frequency converters with small DC-link capacitor are analyzed. The evaluation is obtained with simulations and laboratory measurements.

Titanyylisulfaatin elektrolyyttisen pelkistyslaitoksen esisuunnitelma

Työssä esisuunniteltiin Kemira Pigments Oy:lle uusi titanyylisulfaatin elektrolyyttinen pelkistyslaitos. Suurin syy uuden laitoksen suunnitteluun oli nykyisen laitoksen aiheuttamat korkeat H2SO4-pitoisuudet pelkistyslaitoksen läheisyydessä. Työn kirjallisuusosassa käsitellään elektrolyysilaitteiston suunnitteluun liittyviä seikkoja ja esitellään titanyylisulfaatin elektrolyyttiseen pelkistykseen liittyvää tutkimustietoa. Ennen uuden laitoksen suunnittelua suoritettiin nykyisellä pelkistyslaitoksella koeajoja, joiden tarkoituksena oli antaa lähtötiedot uuden laitoksen suunnittelulle. Koeajot osoittivat mm., että pelkistys on edullisinta suorittaa alhaisella virrantiheydellä n. 300…400 A/m2 ja vesilaimennuksen avulla anolyytin H2SO4-pitoisuus saadaan säädettyä tasolle, jossa titaani ei saostu. Kärynpoistoyhteisiin asennettujen pesuvesisuuttimien avulla saatiin titaanin saostuminen kärynpoistokanaviin estettyä. Uudesta titanyylisulfaatin elektrolyyttisestä pelkistyslaitoksesta laadittiin mm. seuraavat dokumentit: prosessin virtauskaavio ja ainevirtakenttä, PI-kaavio, layout-kuvat laitoksesta ja sen sijoituksesta sekä rakennepiirros elektrolyysialtaasta. Hankkeelle tehtiin kustannusarvio tarkkuudella ±20 %, jonka loppusummaksi saatiin 1 489 000 €. Laitoksen vuotuisten käyttökustannuksien arvioitiin olevan n. 105 000 €. Investoinnista aiheutuvien vuotuisten annuiteettikustannusten arvioitiin olevan n. 237 000 € 16,3 % korolla.

Mekanisoidun hitsauksen käyttö ydinvoimalaitoksella

Diplomityössä päätavoitteena oli selvittää kuinka mekanisointia voitaisiin hyödyntää Fortum Power & Heat Oy:n Loviisan voimalaitoksen hitsauksissa. Työn osatavoitteisiin kuului mm. tutkia saadaanko mekanisoinnin käytön seurauksena parannettua laatua pienennettyä säteilyannoksia tai kustannuksia. Käytännön esimerkkinä oli pääkiertopumpun pesän tiivistepinnan korjaushitsaus. Teoriaosuus käsittelee nykyaikaisia hitsausmenetelmiä sekä hitsauksen mekanisoinnista ja automatisoinnista saatavia etuja. Käytännön osuudessa käytiin läpi Loviisan voimalaitoksen mekanisoidun hitsauksen historia ja hitsauksen nykytila ja tulevaisuus. Tulevaisuuden tarkastelussa kartoitettiin kohteita missä mekanisoinnin käytöstä saataisiin hyötyä ja mietittiin miten kyseinen kohteen mekanisointi voitaisiin toteuttaa. Tarkastelujen perusteella Loviisan voimalaitokselta löytyi kolme kohdetta, jossa hitsauksen mekanisointi olisi järkevä toteuttaa tavoitteiden puitteissa. Mekanisoitavissa olevat kohteet olivat putkiston hitsaus, suurien säiliöiden vuorauksien hitsaus ja suurien tiivistepintojen pinnoitushitsaus. Pääkiertopumpun pesän tiivistepinnan hitsaukselle löydettiin kolme laitteistovaihtoehtoa, joiden pohjalta lopullinen päätös voidaan tehdä.

ADVANCED NUMERICAL METHODS FOR SIMULATING MICROBUBBLE IN AN AERATED MIXING TANK

Fluid mixing in mechanically agitated tanks is one of the major unit operations in many industries. Bubbly flows have been of interest among researchers in physics, medicine, chemistry and technology over the centuries. The aim of this thesis is to use advanced numerical methods for simulating microbubble in an aerated mixing tank. Main components of the mixing tank are a cylindrical vessel, a rotating Rushton turbine and the air nozzle. The objective of Computational Fluid Dynamics (CFD) is to predict fluid flow, heat transfer, mass transfer and chemical reactions. The CFD simulations of a turbulent bubbly flow are carried out in a cylindrical mixing tank using large eddy simulation (LES) and volume of fluid (VOF) method. The Rushton turbine induced flow is modeled by using a sliding mesh method. Numerical results are used to describe the bubbly flows in highly complex liquid flow. Some of the experimental works related to turbulent bubbly flow in a mixing tank are briefly reported. Numerical simulations are needed to complete and interpret the results of the experimental work. Information given by numerical simulations has a major role in designing and scaling-up mixing tanks. The results of this work have been reported in the following scientific articles: ·Honkanen M., Koohestany A., Hatunen T., Saarenrinne P., Zamankhan P., Large eddy simulations and PIV experiments of a two-phase air-water mixer, in Proceedings of ASME Fluids Engineering Summer Conference (2005). ·Honkanen M., Koohestany A., Hatunen T., Saarenrinne P., Zamankhan P., Dynamical States of Bubbling in an Aerated Stirring Tank, submitted to J. Computational Physics.

Syöttövesisäiliöiden pinnanheilahteluiden hallinta Loviisan voimalaitoksella

Tässä työssä tarkastellaan syöttövesisäiliöiden käyttäytymistä Loviisan voimalaitoksella. Työssä käydään läpi laitoksen kaikki pääjärjestelmät primääri- ja sekundääripuolelta. Lisäksi selvitetään myös säiliöiden käyttäytymiseen liittyvät apujärjestelmät niiltä osin kuin tarpeellista. Työn pääpaino laitosesittelyn jälkeen siirtyy täysin syöttövesisäiliömallin luomiseen ja simulointeihin. Työssä on tutkittu useita esille tulleita ideoita syöttövesisäiliöiden pinnanheilahdusten minimoimiseksi. Säiliömallin luominen ja simuloinnit on suoritettu APROS-voimalaitossimulaattorilla. Työssä on alustavasti tarkasteltu kaikki pinnanheilahdusten hallintaideat. Mahdolliset jatkotutkimukset ja parannustyöt aloitetaan tämän työn pohjalta. Työn aikana saatiin paljon uutta tietoa syöttövesisäiliöiden käyttäytymisestä. Tätä tietoa pystytään hyödyntämään käytössä, prosessisuunnittelussa ja koulutussimulaattoria päivitettäessä.

Jätevedenpuhdistamon toiminnan optimointi

Schauman Wood Oy Pelloksen tehtaat on Euroopan suurin havuvanerin valmistaja. Tehtailla tukkien haudonnassa ja kuorien kuivaamisessa syntyvät jätevedet sekä sosiaalijätevedet puhdistetaan omassa biologisessa puhdistamossa. Puhdistamo rakennettiin alun perin aktiivilietelaitokseksi ja muutettiin kuormituksen kasvaessa vuonna 2002 kantoaineprosessiksi. Puhdistamolle laskettiin ensin optimaalinen kuormitus, jonka perusteella kuormitusta ryhdyttiin nostamaan. Tavoitteena oli saavuttaa virtaaman nostolla ja ajomallien muutoksilla tilavuuskuorma 1-3 kgBOD/m3•d. Kun tulovirtaamaa oli saatu nostettua riittävästi, tehtiin laskeutuskokeita laskeutuskemikaalin optimimäärän selvittämiseksi. Koeajojakson lopuksi pidettiin kolmen viikon tehotarkkailujakso, jolloin kokeiltiin puhdistamon ajoa erilaisilla kemikaalimäärillä. Näin saatiin selville tasemielessä tietyn puumäärän aiheuttama kuormitus puhdistamolle. Jätevedenpuhdistamon tulovirtaama saatiin nostettua tasolle 300- 350 m³/d, jolloin tilaavuuskuormaksi tuli 1,68 kgBOD/m3•d. Kolmen viikon tehotarkkailujakson aikana saatiin selvitettyä optimikemikaaliannostus sekä laskettua kolmesta eri vaihtoehdosta taloudellisesti kannattavin ajomalli. Puhdistusreduktioiden, puhdistamon toimivuuden ja taloudellisuuden kannalta paras vaihtoehto oli laskeutuskemikaalin ja polymeerin yhteiskäyttö.

Dimensioning DC-voltage capacitor for a DC-distribution system and dynamic analysis

Technical analysis of Low Voltage Direct Current (LVDC) distribution systems shows that in LVDC transmission the customer voltage quality is higher. One of the problems in LVDC distribution networks that converters both ends of the DC line are required. Because of the converters produce not pure DC voltage, but some fluctuations as well, the huge electrolytic capacitors are required to reduce voltage distortions in the DC-side. This thesis master’s thesis is focused on calculating required DC-link capacitance for LVDC transmission and estimation of the influence of different parameters on the voltage quality. The goal is to investigate the methods of the DC-link capacitance estimation and location in the transmission line.

Vaahdonestokemikaalin syöttötapahtuman tehostamisen vaikutus märkäosan toimintaan

An improved defoamer dosage procedure and a more efficient dosing point to the approach system were studied in this thesis. Their influence on paper machine wet end operations was investigated. The improved defoamer dosing procedure was examined at UMP-Kymmene Tervasaari PM8. Air content and its controlling methods at the paper machine were studied in the literature survey. Also the influence of dissolved gases and entrained air in the papermaking furnish were introduced. Feeding methods – a TrumpJet chemical mixer and traditional feeding devices – were reviewed. The defoamer’s functioning methods were studied. The influence of the use of defoamers was estimated based on the main selected wet end operations. In the experimental part, defoamer mixing with a traditional feeding method and two improved mixing stages were compared based on the air content profiles in PM8’s approach system. The reference dosage procedure was PM8’s old dosing system. The first dosage procedure in the comparison involved two TrumpJet chemical mixers installed on the bottom wire trays. The second element of comparison involved the improvement brought by a third TrumpJet chemical mixer installed on the top wire tray. This second comparison of the efficient defoamer feeding concept was made at a higher production speed of PM8. The air content control situation was also studied at the higher production speed. In addition the connection between the defoamer and air content was observed and a mill-scale system was studied. The economical benefits of the new dosing procedure were also reviewed. Air content profiles of short circulation were measured in the reference situation and the two comparison points of the study. These air content measurements proved the main gas load is introduced to PM8's paper furnish from the white water tray. Thick stock air content was not essential when the air volume flow was considered. The improved defoamer dosing procedure made lower dosage amounts possible. Compared with the traditional feeding system, the new defoamer feeding concept made only few direct improvements to the wet end operations and the produced paper itself. The lower defoamer need was noticed to have a positive influence on hydrophobic sizing and paper defects. The surfaces of the white water tanks and the operation of pumps were assessed based on the density variations of the suspension. The temperature in the white water silo was stated to have a significant influence on the air content measured in the first centrifugal cleaning stage.

Epäpuhtauksien poistaminen prosessivesistä

Kemira Chemicals Oy in Äetsä produces sodium chlorate as its main product. It is produced with electrolysis in electrolyte cells. During the manufacturing process impurities, out of which the largest one is iron, accumulate in the cells. These impurities are removed in cell wash with hydrochloric acid liquid, after which the wash water is precipitated with sodium hydroxide and sodium carbonate, and filtered with filter press. After the treatment the wash water is recycled back to the manufacturing process. The aim of this thesis was primarily to improve the treatment of wash water in order to remove the impurities with low costs. This would result in more impurity-free water and in sufficient capacity of impurity removal. The second aim was to maintain the chromium in the treated wash water because it forms a diaphragm of chromium hydroxide to cathode which prevents the flow of anions to cathode. The literature part investigates properties, use and manufacturing of sodium chlorate, electrolyte cell and its wash technique, and impurities of wash water. The beginning of the applied part investigates alternatives of separation methods which could be used to improve the treatment of wash water. In the experiments an optimum pH for the precipitation of wash water was determined, and a research of the use of sodium hydroxide, sodium carbonate, calcium hydroxide and calcium chloride as a precipitant was carried out. Also a suitable flocculant and a filter cloth for the treatment of wash water were determined. Finally, process changes were introduced, partly by applying the current equipment, and the costs and savings were calculated.

Elektrolyyttinen nanopinnoitus

Diplomityö on osa Savonia-amk:n hallinnoimaa ENC- pinnoitushanketta, jossa tutkitaan uuden teknologian elektrolyyttisiä kromi (III) -nanopinnoitteita. Tavoitteena oli selvittää uudella menetelmällä saavutettavat parannukset pinnoitteiden mekaanisiin ominaisuuksiin. Työ toteutettiin rakentamalla pinnoitustutkimuksen toimintaympäristö osaksi Savo-nia-amk:n materiaalitekniikan laboratorioita sekä tutkimalla eri koe- ja sovelluspinnoitteiden mekaanisia ominaisuuksia eri pinnoitusparametreilla. Työssä tutkittiin, miten nanopartikkelit sekä erilaiset pinnoitusparametrit vaikuttavat kromipinnoitteiden rakenteeseen sekä mekaaniseen suorituskykyyn.