Carbon dioxide evolution from snow-covered agricultural ecosystems in Finland

Selostus: Hiilidioksidin kulku lumipeitteisessä ja paljaassa maassa

Management of Metals in the Pulping Process

Diplomityön tarkoituksena oli löytää keino korkean mangaanipitoisuuden hallintaan ECF-valkaisussa. Kirjallisuusosassa käsiteltiin eri metallien ja kuidun vuorovaikutuksia sekä niiden vaikutuksia prosessiin. Lisäksi käytiin läpi sellunvalmituksen yleisimpiä metallienhallintamenetelmiä. Työn kokeellisessa osassa tehtiin esikokeina laboratoriokokeita, jotta löydettiin oikeat kelatointistrategiat tehdasmittakaavan koeajoille. Laboratoriovalkaisut suoritettiin kuudella eri kemikaalilla käyttäen DD3-pesurin jälkeistä massaa ja samanlaisia parametrejä kuin tehdasvalkaisussa. Kolmesta eri valkaisusekvenssistä paras tulos saavutettiin D0-QEP-sekvenssillä. Tehdasmittakaavan koeajojen tavoitteena oli saavuttaa alle 1 mg/kg jäännösmangaanipitoisuus valkaistussa massassa ja korkeampi vaaleus EOP-vaiheessa pienemmällä klooridioksidin kulutuksella. Koeajoissa käytettiinDTPA:ta ja EDTA:ta kahdeksassa eri koepisteessä. Pienimpiin jäännöspitoisuuksiin päästiin koepisteissä, joissa kelatointiaine annosteltiin ennen valkaisun viimeistä pesuvaihetta tai sen jälkeen. Samanlaisia tuloksia saavutettiin koepisteissä, joissa kelatointiaine lisättiin suoraan EOP-vaiheeseen. Tällöin kelatointiaineen käyttö johti myös korkeampaan vaaleuteen EOP-vaiheessa pienemmällä kappakertoimella kuin referenssissä. Säästöt klooridioksidin kulutuksessa eivät olleet kuitenkaan tarpeeksi suuret kattaakseen kelatointiaineiden käytön kustannuksia. Kustannustehokkain tapa kontrolloida jäännösmangaanipitoisuutta oli EDTA:n annostelu D2 DD-pesurin jälkeen. Haittapuolena tälläisessä kelatoinnissa oli metallikompleksien palautuminen valkaisuun kuivauskoneen kiertoveden mukana. Tärkeimmät onnistuneeseen kelatointiin vaikuttavat parametrit olivat lajittelussa käytetyn rikkihapon annos, D0-vaiheen pH ja D0 DD-pesurin pesutehokkuus.

Separation of ammonia and carbon dioxide by adsorption

Tässä työssä on tutkittu ammoniakin ja hiilidioksidin erottamista adsorptio prosessilla ja suunniteltiin paineen muunteluun perustuvan adsorptioprosessin (PSA) käyttöä. Työn tarkoituksena oli laskea adsorptioon perustuvan prosessin kannattavuus melamiinitehtaan poistokaasujen erotuksessa. Tätä varten työssä suunniteltiin tehdasmitta-kaavainen prosessi ja arvioitiin sen kannattavuus. Työssä mitattiin adsorptiotasapainot, joiden perusteella sovitettiin sopiva kokeellinen adsorptioisotermi. Adsorptioisotermi lisättiin simulointiohjelmaan, jonka avulla suunniteltiin kaksi vaihtoehtoista pilot laitteistoa kaasujen erottamiseksi. Toisella pilot laitteistolla saadaan mitattua vain läpäisykäyrät, mutta paremmalla versiolla saadaan myös tietoa erotettujen komponenttien puhtaudesta. Suunnittelun tärkeimpiä lähtökohtia on molempien komponenttien mahdollisimman korkea puhtaus ja talteenottoaste. Täysimittakaavainen tehdas suunniteltiin simulointiohjelmiston avulla kahdelle eri kapasiteetille ja arvioitiin niiden kustannukset ja kannattavuus. Adsorptioprosessit osoittautuivat kannattaviksi kaasuseoksen erottamisessa kummassakin tapauksessa

Kaivosteollisuudessa syntyvän kipsin hyödyntäminen

Diplomityön tarkoituksena oli tutkia ja kehittää käyttökohde kaivosteollisuudessa syntyvälle märälle kipsisivuvirralle, joka sisältää metalliepäpuhtauksina alumiinia, rautaa ja mangaania ja jonka määrä on noin 1 000 000 t/a. Kirjallisuuden pohjalta tutkittiin aluksi mahdollisuutta hyödyntää kipsiaines asfaltti- ja sementtiteollisuuden raaka-aineena. Sementin joukkoon lisätään tavallisesti noin 5 p-% kipsiä, mutta harvinaisimpiin sementtilaatuihin sitä voidaan lisätä jopa 30 p-%. Tästä huolimatta vain pieni osa tutkimuksen kohteessa syntyvästä kipsisivuvirrasta voitaisiin hyödyntää tässä sovelluksessa. Lisäksi kipsisivuvirran sisältämät epäpuhtaudet täytyisi poistaa tai saattaa inaktiiviseen muotoon. Myöskään sen kosteuspitoisuus ei saisi olla suuri. Näin ollen tämän kipsisivuvirran hyödyntäminen asfaltti- ja sementtiteollisuuden lisäaineena ei ole mahdollista Seuraavaksi harkittiin kipsin kierrättämistä, jolloin yhtenä vaihtoehtona oli hajottaa kipsi termisesti rikkioksideiksi ja valmistaa niistä rikkihappoa. Taloudellisista syistä hajoamistuotteen on oltava rikkitrioksidia, josta voitaisiin veteen imeyttämällä valmistaa rikkihappoa. Kipsin hajottaminen termovaa´alla osoitti, että kipsi vaatii noin 1400 ºC:n lämpötilan ja haihtuvat komponentit ovat H2O, SO ja SO2, muttei SO3. Alempien oksidien muuttaminen rikkihapoksi vaatisi katalyyttisen hapetuksen, mikä olisi käytännössä liian kallista. Toisena vaihtoehtona kipsin kierrättämiseksi tutkittiin sen biologista pelkistämistä rikkivedyksi ja kalsiumhydroksidilietteeksi. Laboratoriossa Ca(OH)2-lietteestä valmistettiin hiilidioksidin avulla kalsiumkarbonaattia, jolloin päästiin 90 %:n kalsiumhydroksidin konversiossa. Lisäksi alumiinihydroksidi saatiin erotettua kipsilietteestä kokeellisesti hydrosyklonin avulla. Diplomityössä päädyttiin siihen, että sulfaatin biologinen pelkistäminen ja alumiinihydroksidin mekaaninen erotus jatkuvatoimisesti on varteenotettava vaihtoehto kipsisivuvirran hyödyntämiseksi.

Identification of Turning Points in the Research on Titanium Dioxide Production and Application

This dissertation "Identification of turning points in the research on titanium dioxide production and application" aims at detecting in scientific literatures emerging trends and sudden changes in titanium dioxide production and application. These key changes are then studied to determine its transient patterns and its effect on the research on titanium dioxide production and application The source of information is from bibliographic data which discussed titanium dioxide production and application. These bibliographic data where obtained from ISI Web of Knowledge and then formed into a network of clusters by applying software called Citespace.

Nocturnal Transcutaneous Carbon Dioxide and Early Changes in Atherosclerosis in Pre- and Postmenopausal Women

The risk of cardiovascular diseases and sleep-disordered breathing increases after menopause. This cross-sectional study focuses on overnight transcutaneous carbon dioxide (TcCO₂) measurements and their power to predict changes in the early markers of cardiovascular and metabolic diseases. The endothelial function of the brachial artery, the intima-media thickness of the carotid artery, blood pressure, glycosylated hemoglobin A1C and plasma levels of cholesterols and triglycerides were used as markers of cardiovascular and metabolic diseases. The study subjects consisted of healthy premenopausal women of 46 years of age and postmenopausal women of 56 years of age. From wakefulness to sleep, the TcCO₂ levels increased more in postmenopausal women than in premenopausal women. In estrogen-users the increase in TcCO₂ levels was even more pronounced than in other postmenopausal women. From the dynamic behaviour of the nocturnal TcCO₂ signal, several important features were detected. These TcCO₂ features had a remarkable role in the prediction of endothelial dysfunction and thickening of the carotid wall in healthy premenopausal women. In addition, these TcCO₂ features were linked with blood pressure, lipid profile and glucose balance in postmenopausal women. The nocturnal TcCO₂ profile seems to contain significant information, which is associated with early changes in cardiovascular diseases in middle-aged women. TcCO₂ might not only measure the tissue carbon dioxide levels, but the TcCO₂ signal variation may also reflect peripheral vasodynamic events caused by increased sympathetic activity during sleep.

Magnetic and transport properties of II-V diluted magnetic semiconductors doped with manganese and nickel

This thesis is devoted to investigations of three typical representatives of the II-V diluted magnetic semiconductors, Zn1-xMnxAs2, (Zn1-xMnx)3As2 and p-CdSb:Ni. When this work started the family of the II-V semiconductors was presented by only the compounds belonging to the subgroup II3-V2, as (Zn1-xMnx)3As2, whereas the rest of the materials mentioned above were not investigated at all. Pronounced low-field magnetic irreversibility, accompanied with a ferromagnetic transition, are observed in Zn1-xMnxAs2 and (Zn1-xMnx)3As2 near 300 K. These features give evidence for presence of MnAs nanosize magnetic clusters, responsible for frustrated ground magnetic state. In addition, (Zn1-xMnx)3As2 demonstrates large paramagnetic response due to considerable amount of single Mn ions and small antiferromagnetic clusters. Similar paramagnetic system existing in Zn1-xMnxAs2 is much weaker. Distinct low-field magnetic irreversibility, accompanied with a rapid saturation of the magnetization with increasing magnetic field, is observed near the room temperature in p- CdSb:Ni, as well. Such behavior is connected to the frustrated magnetic state, determined by Ni-rich magnetic Ni1-xSbx nanoclusters. Their large non-sphericity and preferable orientations are responsible for strong anisotropy of the coercivity and saturation magnetization of p- CdSb:Ni. Parameters of the Ni1-xSbx nanoclusters are estimated. Low-temperature resistivity of p-CdSb:Ni is governed by a hopping mechanism of charge transfer. The variable-range hopping conductivity, observed in zero magnetic field, demonstrates a tendency of transformation into the nearest-neighbor hopping conductivity in non-zero magnetic filed. The Hall effect in p-CdSb:Ni exhibits presence of a positive normal and a negative anomalous contributions to the Hall resistivity. The normal Hall coefficient is governed mainly by holes activated into the valence band, whereas the anomalous Hall effect, attributable to the Ni1-xSbx nanoclusters with ferromagnetically ordered internal spins, exhibits a low-temperature power-law resistivity scaling.

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.

Recovery and refining of manganese as by-product from hydrometallurgical processes

The consumption of manganese is increasing, but huge amounts of manganese still end up in waste in hydrometallurgical processes. The recovery of manganese from multi-metal solutions at low concentrations may not be economical. In addition, poor iron control typically prevents the production of high purity manganese. Separation of iron from manganese can be done with chemical precipitation or solvent extraction methods. Combined carbonate precipitation with air oxidation is a feasible method to separate iron and manganese due to the fast kinetics, good controllability and economical reagents. In addition the leaching of manganese carbonate is easier and less acid consuming than that of hydroxide or sulfide precipitates. Selective iron removal with great efficiency from MnSO4 solution is achieved by combined oxygen or air oxidation and CaCO3 precipitation at pH > 5.8 and at a redox potential of > 200 mV. In order to avoid gypsum formation, soda ash should be used instead of limestone. In such case, however, extra attention needs to be paid on the reagents mole ratios in order to avoid manganese coprecipitation. After iron removal, pure MnSO4 solution was obtained by solvent extraction using organophosphorus reagents, di-(2-ethylhexyl)phosphoric acid (D2EHPA) and bis(2,4,4- trimethylpentyl)phosphinic acid (CYANEX 272). The Mn/Ca and Mn/Mg selectivities can be increased by decreasing the temperature from the commonly used temperatures (40 –60oC) to 5oC. The extraction order of D2EHPA (Ca before Mn) at low temperature remains unchanged but the lowering of temperature causes an increase in viscosity and slower phase separation. Of these regents, CYANEX 272 is selective for Mn over Ca and, therefore, it would be the better choice if there is Ca present in solution. A three-stage Mn extraction followed by a two-stage scrubbing and two-stage sulfuric acid stripping is an effective method of producing a very pure MnSO4 intermediate solution for further processing. From the intermediate MnSO4 some special Mn- products for ion exchange applications were synthesized and studied. Three types of octahedrally coordinated manganese oxide materials as an alternative final product for manganese were chosen for synthesis: layer structured Nabirnessite, tunnel structured Mg-todorokite and K-kryptomelane. As an alternative source of pure MnSO4 intermediate, kryptomelane was synthesized by using a synthetic hydrometallurgical tailings. The results show that the studied OMS materials adsorb selectively Cu, Ni, Cd and K in the presence of Ca and Mg. It was also found that the exchange rates were reasonably high due to the small particle dimensions. Materials are stable in the studied conditions and their maximum Cu uptake capacity was 1.3 mmol/g. Competitive uptake of metals and acid was studied using equilibrium, batch kinetic and fixed-bed measurements. The experimental data was correlated with a dynamic model, which also accounts for the dissolution of the framework manganese. Manganese oxide micro-crystals were also bound onto silica to prepare a composite material having a particle size large enough to be used in column separation experiments. The MnOx/SiO2 ratio was found to affect significantly the properties of the composite. The higher the ratio, the lower is the specific surface area, the pore volume and the pore size. On the other hand, higher amount of silica binder gives composites better mechanical properties. Birnesite and todorokite can be aggregated successfully with colloidal silica at pH 4 and with MnO2/SiO2 weight ratio of 0.7. The best gelation and drying temperature was 110oC and sufficiently strong composites were obtained by additional heat-treatment at 250oC for 2 h. The results show that silica–supported MnO2 materials can be utilized to separate copper from nickel and cadmium. The behavior of the composites can be explained reasonably well with the presented model and the parameters estimated from the data of the unsupported oxides. The metal uptake capacities of the prepared materials were quite small. For example, the final copper loading was 0.14 mmol/gMnO2. According to the results the special MnO2 materials are potential for a specific environmental application to uptake harmful metal ions.

Growth, magnetic and transport properties of InSb and II-IV-As2 semiconductors doped with manganese

This thesis is devoted to growth and investigations of Mn-doped InSb and II-IV-As2 semiconductors, including Cd1-xZnxGeAs2:Mn, ZnSiAs2:Mn bulk crystals, ZnSiAs2:Mn/Si heterostructures. Bulk crystals were grown by direct melting of starting components followed by fast cooling. Mn-doped ZnSiAs2/Si heterostructures were grown by vacuum-thermal deposition of ZnAs2 and Mn layers on Si substrates followed by annealing. The compositional and structural properties of samples were investigated by different methods. The samples consist of micro- and nano- sizes clusters of an additional ferromagnetic Mn-X phases (X = Sb or As). Influence of magnetic precipitations on magnetic and electrical properties of the investigated materials was examined. With relatively high Mn concentration the main contribution to magnetization of samples is by MnSb or MnAs clusters. These clusters are responsible for high temperature behavior of magnetization and relatively high Curie temperature: up to 350 K for Mn-doped II-IV-As2 and about 600 K for InMnSb. The low-field magnetic properties of Mn-doped II-IV-As2 semiconductors and ZnSiAs2:Mn/Si heterostructures are connected to the nanosize MnAs particles. Also influence of nanosized MnSb clusters on low-field magnetic properties of InMnSb have been observed. The contribution of paramagnetic phase to magnetization rises at low temperatures or in samples with low Mn concentration. Source of this contribution is not only isolated Mn ions, but also small complexes, mainly dimmers and trimmers formed by Mn ions, substituting cation positions in crystal lattice. Resistivity, magnetoresistance and Hall resistivity properties in bulk Mn-doped II-IV-As2 and InSb crystals was analyzed. The interaction between delocalized holes and 3d shells of the Mn ions together with giant Zeeman splitting near the cluster interface are respond for negative magnetoresistance. Additionally to high temperature critical pointthe low-temperature ferromagnetic transition was observed Anomalous Hall effect was observed in Mn doped samples and analyzed for InMnSb. It was found that MnX clusters influence significantly on magnetic scattering of carriers.

The laser weldability of lean duplex stainless steels

Ruostumattomien terästen hinta on kasvanut maailman laajuisen kysynnän kasvun seurauksena. Samoin on käynyt myös ruostumattomien terästen valmistukseen käytettävien seosaineiden hinnalle. Terästen valmistajat ovatkin kehittäneet lean duplex teräksiä vastatakseen hintatietoisten markkinoiden kysyntään. Näissä lean duplex teräksissä kalliita seosaineita kuten nikkeliä ja molybdeenia on korvattu typellä ja mangaanilla. Houkutteleviksi vaihtoehdoiksi perinteisille ruostumattomille teräksille lean duplex laadut tekee myös niiden hyvät lujuus- ja korroosio-ominaisuudet. Kirjallisuus osio esittelee lasereiden toimintaperiaatteen. Myös avaimenreikähitsauksen periaate on esitetty. Ruostumattomien terästen yleisimmät seosaineet ovat esitelty, kuten myös syy niiden seostamiseen. Ruostumattomat duplex-teräkset on esitelty samoin kuin lean duplex teräkset. Kokeellisen osion koehitsit hitsattiin osin samalla tuotantolinjalla lopputuotteen kanssa ja osin laboratoriossa. Koemateriaaleina olivat lean duplex teräkset 1.4162 ja 1.4362 joiden materiaalipaksuudet olivat 1.2 mm ja 1.5 mm. Hitsatuille lamelleille tehtiin painetestaus. Makroskopiaa ja valomikroskopiaa käytettiin koehitsien arvioinnissa kuten myös ristivetokoetta. Kiinnostavimmista hitseistä määritettiin myös faasisuhde. Lean duplex teräs 1.4362 havaittiin sopivammaksi laaduksi tämän kaltaisessa sovelluksessa, mutta myös laatu 1.4162 täyttää sovelluksen hitsille asetetut vaatimukset, tosin huomattavasti pienemmässä parametri ikkunassa. Valittu menetelmä faasisuhteen määrittämiseen osoittautui epätarkaksi, joten faasisuhteen osalta tämän tutkimuksen tulokset ovat vain suuntaa-antavia.

Model based analysis of the post-combustion calcium looping process for carbon dioxide capture

This thesis presents a one-dimensional, semi-empirical dynamic model for the simulation and analysis of a calcium looping process for post-combustion CO2 capture. Reduction of greenhouse emissions from fossil fuel power production requires rapid actions including the development of efficient carbon capture and sequestration technologies. The development of new carbon capture technologies can be expedited by using modelling tools. Techno-economical evaluation of new capture processes can be done quickly and cost-effectively with computational models before building expensive pilot plants. Post-combustion calcium looping is a developing carbon capture process which utilizes fluidized bed technology with lime as a sorbent. The main objective of this work was to analyse the technological feasibility of the calcium looping process at different scales with a computational model. A one-dimensional dynamic model was applied to the calcium looping process, simulating the behaviour of the interconnected circulating fluidized bed reactors. The model incorporates fundamental mass and energy balance solvers to semi-empirical models describing solid behaviour in a circulating fluidized bed and chemical reactions occurring in the calcium loop. In addition, fluidized bed combustion, heat transfer and core-wall layer effects were modelled. The calcium looping model framework was successfully applied to a 30 kWth laboratory scale and a pilot scale unit 1.7 MWth and used to design a conceptual 250 MWth industrial scale unit. Valuable information was gathered from the behaviour of a small scale laboratory device. In addition, the interconnected behaviour of pilot plant reactors and the effect of solid fluidization on the thermal and carbon dioxide balances of the system were analysed. The scale-up study provided practical information on the thermal design of an industrial sized unit, selection of particle size and operability in different load scenarios.

The Combined treatment of UV Light and Titanium Dioxide (TiO2) in Grease Filtration Technique

The aim of this thesis was to identify the best grease removal technique with the application of low power of UV light to TiO2 coated grease filters. The treatment with various power series of ozone generating and ozone free lamps to normal grease filters and TiO2 coated grease filters were examined and the obtained results are compared to each other in this paper. The effect of ozone reaction was observed and compared with the effect of TiO2. The experiments were solely based on the photo oxidation and photo catalytic oxidation reactions. TiO2 is a green catalyst used in the photocatalytic reaction. Sunflower oil was used for grease production and tetracholoroethylene as a solvent. Grease samples were collected from the ventilation duct connected to the cooking hood system. Sample extraction was done in ultrasonic bath with the principle of sonication. The sample analysis was done by FTIR machine. The result determining the concentration of grease was the quantification of saturated C-H bonds in the chosen peak group of the spectrum. A very low power of UVC light functions perfectly with the Titanium dioxide. The experimental results have shown the combined treatment of titanium dioxide and UV light is an effective method in grease removal process. The photocatalytic reaction with titanium dioxide is better than photo oxidation reaction with ozone treatment. Photocatalytic reaction is environmentally friendly, energy efficient and economical.