Extraction of polymeric galactoglucomannans from spruce wood by pressurized hot water

The major type of non-cellulosic polysaccharides (hemicelluloses) in softwoods, the partly acetylated galactoglucomannans (GGMs), which comprise about 15% of spruce wood, have attracted growing interest because of their potential to become high-value products with applications in many areas. The main objective of this work was to explore the possibilities to extract galactoglucomannans in native, polymeric form in high yield from spruce wood with pressurised hot-water, and to obtain a deeper understanding of the process chemistry involved. Spruce (Picea abies) chips and ground wood particles were extracted using an accelerated solvent extractor (ASE) in the temperature range 160 – 180°C. Detailed chemical analyses were done on both the water extracts and the wood residues. As much as 80 – 90% of the GGMs in spruce wood, i.e. about 13% based on the original wood, could be extracted from ground spruce wood with pure water at 170 – 180°C with an extraction time of 60 min. GGMs comprised about 75% of the extracted carbohydrates and about 60% of the total dissolved solids. Other substances in the water extracts were xylans, arabinogalactans, pectins, lignin and acetic acid. The yields from chips were only about 60% of that from ground wood. Both the GGMs and other non-cellulosic polysaccharides were extensively hydrolysed at severe extraction conditions when pH dropped to the level of 3.5. Addition of sodium bicarbonate increased the yields of polymeric GGMs at low additions, 2.5 – 5 mM, where the end pH remained around 3.9. However, at higher addition levels the yields decreased, mainly because the acetyl groups in GGMs were split off, leading to a low solubility of GGMs. Extraction with buffered water in the pH range 3.8 – 4.4 gave similar yields as with plain water, but gave a higher yield of polymeric GGMs. Moreover, at these pH levels the hydrolysis of acetyl groups in GGMs was significantly inhibited. It was concluded that hot-water extraction of polymeric GGMs in good yields (up to 8% of wood) demands appropriate control of pH, in a narrow range about 4. These results were supported by a study of hydrolysis of GGM at constant pH in the range of 3.8 – 4.2 where a kinetic model for degradation of GGM was developed. The influence of wood particle size on hot-water extraction was studied with particles in the range of 0.1 – 2 mm. The smallest particles (< 0.1 mm) gave 20 – 40% higher total yield than the coarsest particles (1.25 – 2 mm). The difference was greatest at short extraction times. The results indicated that extraction of GGMs and other polysaccharides is limited mainly by the mass transfer in the fibre wall, and for coarse wood particles also in the wood matrix. Spruce sapwood, heartwood and thermomechnical pulp were also compared, but only small differences in yields and composition of extracts were found. Two methods for isolation and purification of polymeric GGMs, i.e. membrane filtration and precipitation in ethanol-water, were compared. Filtration through a series of membranes with different pore sizes separated GGMs of different molar masses, from polymers to oligomers. Polysaccharides with molar mass higher than 4 kDa were precipitated in ethanol-water. GGMs comprised about 80% of the precipitated polysaccharides. Other polysaccharides were mainly arabinoglucuronoxylans and pectins. The ethanol-precipitated GGMs were by 13C NMR spectroscopy verified to be very similar to GGMs extracted from spruce wood in low yield at a much lower temperature, 90°C. The obtained large body of experimental data could be utilised for further kinetic and economic calculations to optimise technical hot-water extractionof softwoods.

Silicon-containing species in used lube oil re-refining

Nowadays, the re-refining of the used lube oils has gained worldwide a lot of attention due to the necessity for added environmental protection and increasingly stringent environmental legislation. One of the parameters determining the quality of the produced base oils is the composition of feedstock. Estimation of the chemical composition of the used oil collected from several European locations showed that the hydrocarbon structure of the motor oil is changed insignificantly during its operation and the major part of the changes is accounted for with depleted oil additives. In the lube oil re-refining industry silicon, coming mainly from antifoaming agents, is recognized to be a contaminant generating undesired solid deposits in various locations in the re-refining units. In this thesis, a particular attention was paid to the mechanism of solid product formation during the alkali treatment process of silicon-containing used lube oils. The transformations of a model siloxane, tetramethyldisiloxane (TMDS), were studied in a batch reactor at industrially relevant alkali treatment conditions (low temperature, short reaction time) using different alkali agents. The reaction mechanism involving solid alkali metal silanolates was proposed. The experimental data obtained demonstrated that the solids were dominant products at low temperature and short reaction time. The liquid products in the low temperature reactions were represented mainly by linear siloxanes. The prolongation of reaction time resulted in reduction of solids, whereas both temperature and time increase led to dominance of cyclic products in the reaction mixture. Experiments with the varied reaction time demonstrated that the concentration of cyclic trimer being the dominant in the beginning of the reaction diminished with time, whereas the cyclic tetramer tended to increase. Experiments with lower sodium hydroxide concentration showed the same effect. In addition, a decrease of alkali agent concentration in the initial reaction mixture accelerated TMDS transformation reactions resulting in solely liquid cyclic siloxanes yields. Comparison of sodium and potassium hydroxides applied as an alkali agent demonstrated that potassium hydroxide was more efficient, since the activation energy in KOH presence was almost 2-fold lower than that for sodium hydroxide containing reaction mixture. Application of potassium hydroxide for TMDS transformation at 100° C with 3 hours reaction time resulted in 20 % decrease of solid yields compared to NaOH-containing mixture. Moreover, TMDS transformations in the presence of sodium silanolate applied as an alkali agent led to formation of only liquid products without formation of the undesired solids. On the basis of experimental data and the proposed reaction mechanism, a kinetic model was developed, which provided a satisfactory description of the experimental results. Suitability of the selected siloxane as a relevant model of industrial silicon-containing compounds was verified by investigation of the commercially available antifoam agent in base-catalyzed conditions.

An EDTA-β-cyclodextrin adsorbent for the adsorption of rare earth elements and its application in preconcentration of ultratrace rare earth elements from seawater

The objectives of this work were synthesizing an EDTA-β-CD adsorbent and investigating its adsorption potential and applications in preconcentration of REEs from aqueous phase. The adsorption capacity of EDTA-β-CD was investigated. The adsorption studies were performed by batch techniques both in one- and multi-component systems. The effects of pH, contact time and initial concentration were evaluated. The analytical detection methods and characterization methods were presented. EDTA-β-CD adsorbent was synthesized successfully with high EDTA coverage. The maximum REEs uptake was 0.310 mmol g-1 for La(III), 0.337 mmol g-1 for Ce(III) and 0.353 mmol g-1 for Eu(III), respectively. The kinetics of REEs onto EDTA-β-CD fitted well to pseudo-second-order model and the adsorption rate was affected by intra-particle diffusion. The experimental data of one component studies fitted to Langmuir isotherm model indicating the homogeneous surface of the adsorbent. The extended Sips model was applicable for the isotherm studies in three-component system. The electrostatic interaction, chelation and complexation were all involved in the adsorption mechanism. The preconcentration of RE ions and regeneration of EDTA-β-CD were successful. Overall, EDTA-β-CD is an effective adsorbent in adsorption and preconcentration of REEs.

Arvometallien selektiivinen erottaminen kloridiliuoksista

Työssä tutkittiin jalometallien selektiivistä erottamista kloridiliuoksista synteettisten polymeerihartsien avulla. Laboratoriokokeissa keskityttiin tutkimaan kullan erottamista hydrofiilisen polymetakrylaattipohjaisen adsorbentin avulla. Lähtökohtana oli platinarikaste, joka sisälsi kullan lisäksi platinaa, palladiumia, hopeaa, kuparia, rautaa, vismuttia, seleeniä ja telluuria. Mittauksissa tutkittiin eri metallien ja puolimetallien adsorptiota hartsiin tasapaino-, kinetiikka- ja kolonnikokeilla. Työssä käytettiin myös adsorption simulointiin monikomponenttierotuksen dynaamiseen mallintamiseen tarkoitettua tietokoneohjelmaa, johon tarvittavat parametrit estimoitiin kokeellisen datan avulla. Tasapainokokeet yhtä metallia sisältäneistä liuoksista osoittivat, että hartsi adsorboi tehokkaasti kultaa kaikissa tutkituissa suolahappopitoisuuksissa (1-6 M). Kulta muodostaa hartsiin hyvin adsorboituvia tetrakloroauraatti(III)ioneja, [AuCl4]-, jotka ovat erittäin stabiileja pieniin kloridipitoisuuksiin saakka. Suolahappopitoisuudella oli merkitystä ainoastaan raudan adsorptioon, joka kasvoi huomattavasti suolahappopitoisuuden noustessa johtuen raudan taipumuksesta muodostaa hyvin adsorboituvia [FeCl4]--ioneja väkevissä suolahappopitoisuuksissa. Muiden tutkittujen alkuaineiden adsorptiot jäivät alhaisiksi kaikilla suolahappopitoisuuksilla. Rikasteliuoksella tehdyt tasapainokokeet osoittivat, että adsorptiokapasiteetti kullalle riippuu voimakkaasti muista läsnäolevista komponenteista. Kilpaileva adsorptio kuvattiin Langmuir-Freundlich-isotermillä. Kolonnikokeet osoittivat, että hartsi adsorboi kullan lisäksi hieman myös rautaa ja telluuria, jotka saatiin kuitenkin eluoitua hartsista täysin 5 M suolahappopesulla ja sitä seuraavalla 1 M suolahappopesulla. Tehokkaaksi liuokseksi kullan desorboimiseen osoittautui asetonin ja 1 M suolahapon seos. Kolonnierotuksen eri vaiheet pystyttiin tyydyttävästi kuvaamaan simulointimallilla.

Oxygen adsorption on clean and oxygen precovered Cu(100)

Kuparipinnan hapettumisen alkuvaiheet ovat vielä nykyisin tutkijoille epäselviä. Kuitenkin, jotta hapettumisprosessia voitaisiin säädellä, on sangen tärkeää ymmärtää mistä varsinainen hapettuminen lähtee liikkeelle ja mitkä ovat hapettumisen seuraavat vaiheet. Tähän kysymykseen haetaan vastauksia tässä työssä käyttäen puhtaasti teoreettisia menetelmiä pinnan käsittelyssä. Aikaisempien teoreettisten ja kokeellisten tutkimusten välillä on pieni ristiriita liittyen hapen tarttumistodennäköisyyteen. Teoreettisten tutkimusten mukaan happi ei puhtaalle pinnalle tullessaan näe potentiaalivallia, mutta kokeelliset tutkimukset osoittavat sellaisen kuitenkin olevan. Tuohon ristiriitaan pureudutaan käyttäen aikaisemmista laskuista poikkeavaa kvanttimekaaniseen molekyylidynamiikkaan perustuvaa lähestymistapaa. Työssä havaitaan, että aikaisemmin yleisesti käytetty menetelmä hukkaa huomattavan määrän tietoa ja siten tutkijat eivät voi ainoastaan tyytyä tarkastelemaan kyseisellä menetelmällä saatuja tuloksia. Kuparipinnalle havaittiin, että korkeilla molekyylin kineettisen energian arvolla aikaisemmin suoritetut laskut hajottavista trajektoreista pitävät paikkansa, mutta matalilla kineettisen energian arvoilla molekyyli kohtaa erittäin voimakkaan ``steering'' vaikutuksen ja trajektorit joiden piti olla hajottavia johtavatkin molekulaariseen adsorptioon. Kun hapen konsentraatio pinnalla on suurempi kuin 0.5 ML, pinta rekonstruoituu. Myös rekonstruktion jälkeistä pintaa on tutkittu samanlaisilla menetelmillä kuin puhdasta pintaa. Rekonstruoituneelle pinnalle ei löydetty hajottavia trajektoreita ja havaittiin, että hapelle annetun kineettisen energian matalilla arvoilla myös tässä tapauksessa on erittäin voimakas ``steering'' vaikutus.

Gas-phase photocatalytic oxidation of volatile organic compounds

Substances emitted into the atmosphere by human activities in urban and industrial areas cause environmental problems such as air quality degradation, respiratory diseases, climate change, global warming, and stratospheric ozone depletion. Volatile organic compounds (VOCs) are major air pollutants, emitted largely by industry, transportation and households. Many VOCs are toxic, and some are considered to be carcinogenic, mutagenic, or teratogenic. A wide spectrum of VOCs is readily oxidized photocatalytically. Photocatalytic oxidation (PCO) over titanium dioxide may present a potential alternative to air treatment strategies currently in use, such as adsorption and thermal treatment, due to its advantageous activity under ambient conditions, although higher but still mild temperatures may also be applied. The objective of the present research was to disclose routes of chemical reactions, estimate the kinetics and the sensitivity of gas-phase PCO to reaction conditions in respect of air pollutants containing heteroatoms in their molecules. Deactivation of the photocatalyst and restoration of its activity was also taken under consideration to assess the practical possibility of the application of PCO to the treatment of air polluted with VOCs. UV-irradiated titanium dioxide was selected as a photocatalyst for its chemical inertness, non-toxic character and low cost. In the present work Degussa P25 TiO2 photocatalyst was mostly used. In transient studies platinized TiO2 was also studied. The experimental research into PCO of following VOCs was undertaken: - methyl tert-butyl ether (MTBE) as the basic oxygenated motor fuel additive and, thus, a major non-biodegradable pollutant of groundwater; - tert-butyl alcohol (TBA) as the primary product of MTBE hydrolysis and PCO; - ethyl mercaptan (ethanethiol) as one of the reduced sulphur pungent air pollutants in the pulp-and-paper industry; - methylamine (MA) and dimethylamine (DMA) as the amino compounds often emitted by various industries. The PCO of VOCs was studied using a continuous-flow mode. The PCO of MTBE and TBA was also studied by transient mode, in which carbon dioxide, water, and acetone were identified as the main gas-phase products. The volatile products of thermal catalytic oxidation (TCO) of MTBE included 2-methyl-1-propene (2-MP), carbon monoxide, carbon dioxide and water; TBA decomposed to 2-MP and water. Continuous PCO of 4 TBA proceeded faster in humid air than dry air. MTBE oxidation, however, was less sensitive to humidity. The TiO2 catalyst was stable during continuous PCO of MTBE and TBA above 373 K, but gradually lost activity below 373 K; the catalyst could be regenerated by UV irradiation in the absence of gas-phase VOCs. Sulphur dioxide, carbon monoxide, carbon dioxide and water were identified as ultimate products of PCO of ethanethiol. Acetic acid was identified as a photocatalytic oxidation by-product. The limits of ethanethiol concentration and temperature, at which the reactor performance was stable for indefinite time, were established. The apparent reaction kinetics appeared to be independent of the reaction temperature within the studied limits, 373 to 453 K. The catalyst was completely and irreversibly deactivated with ethanethiol TCO. Volatile PCO products of MA included ammonia, nitrogen dioxide, nitrous oxide, carbon dioxide and water. Formamide was observed among DMA PCO products together with others similar to the ones of MA. TCO for both substances resulted in the formation of ammonia, hydrogen cyanide, carbon monoxide, carbon dioxide and water. No deactivation of the photocatalyst during the multiple long-run experiments was observed at the concentrations and temperatures used in the study. PCO of MA was also studied in the aqueous phase. Maximum efficiency was achieved in an alkaline media, where MA exhibited high fugitivity. Two mechanisms of aqueous PCO – decomposition to formate and ammonia, and oxidation of organic nitrogen directly to nitrite - lead ultimately to carbon dioxide, water, ammonia and nitrate: formate and nitrite were observed as intermediates. A part of the ammonia formed in the reaction was oxidized to nitrite and nitrate. This finding helped in better understanding of the gasphase PCO pathways. The PCO kinetic data for VOCs fitted well to the monomolecular Langmuir- Hinshelwood (L-H) model, whereas TCO kinetic behaviour matched the first order process for volatile amines and the L-H model for others. It should be noted that both LH and the first order equations were only the data fit, not the real description of the reaction kinetics. The dependence of the kinetic constants on temperature was established in the form of an Arrhenius equation.

Simulation methods in the modelling of bioaffinity assays

Computational model-based simulation methods were developed for the modelling of bioaffinity assays. Bioaffinity-based methods are widely used to quantify a biological substance in biological research, development and in routine clinical in vitro diagnostics. Bioaffinity assays are based on the high affinity and structural specificity between the binding biomolecules. The simulation methods developed are based on the mechanistic assay model, which relies on the chemical reaction kinetics and describes the forming of a bound component as a function of time from the initial binding interaction. The simulation methods were focused on studying the behaviour and the reliability of bioaffinity assay and the possibilities the modelling methods of binding reaction kinetics provide, such as predicting assay results even before the binding reaction has reached equilibrium. For example, a rapid quantitative result from a clinical bioaffinity assay sample can be very significant, e.g. even the smallest elevation of a heart muscle marker reveals a cardiac injury. The simulation methods were used to identify critical error factors in rapid bioaffinity assays. A new kinetic calibration method was developed to calibrate a measurement system by kinetic measurement data utilizing only one standard concentration. A nodebased method was developed to model multi-component binding reactions, which have been a challenge to traditional numerical methods. The node-method was also used to model protein adsorption as an example of nonspecific binding of biomolecules. These methods have been compared with the experimental data from practice and can be utilized in in vitro diagnostics, drug discovery and in medical imaging.

Ammoniumin, fosfaatin ja nitraatin poisto adsorption avulla

Kiinnostus ravinneionien ammoniumin, fosfaatin ja nitraatin poistoon liittyy niiden ne-gatiivisiin ympäristövaikutuksiin ja niiden poistoon jätevesistä on olemassa erilaisia tekniikoita. Tässä työssä ionien poistoa tutkittiin adsorptiotekniikan avulla. Siinä perus-ajatuksena on ionin kiinnittyminen adsorbentin pintaan, jolloin sen poistaminen käsitel-tävästä vedestä on mahdollista. Tässä diplomityössä tutkittiin eri adsorbentteja ammoniumin, fosfaatin ja nitraatin poistoon, ja päämääränä oli niiden yhtäaikainen poistaminen. Kokeita tehtiin niin laboratoriossa valmistetuille ravinneliuoksille kuin Yara Suomi Oy:n Siilinjärven (Yara) toimipaikalta toimitetuille vesille. Yaran vesien osalta pääpaino oli ammoniumin poistossa. Tutkimuksen haasteina olivat ionien erilaiset varaukset, jolloin esimerkiksi positiivisesti varautunut ammoniumioni kiinnittyi negatiivisesti varautuneen adsorbentin pintaan hel-poiten. Toisaalta negatiivisesti varautuneet anionit fosfaatti ja nitraatti suosivat positiivi-sesti varautuneita adsorbentteja. Myös muiden ionin läsnäolo joko edisti tai esti adsorboitumista ja joissain tapauksissa pH:lla oli suuri merkitys prosessin onnistumiseen. Saatuja tuloksia tarkasteltiin tutkittujen ionien poistoprosenttien ja isotermimallinnuksien kautta unohtamatta muita esille tulleita seikkoja. Saatujen tulosten mukaan etenkin kalsinoitu hydrotalsiitti poisti fosfaattia ja nitraattia, mutta se ei mainittavasti toiminut ammoniumille. Ammoniumille sen sijaan toimi par-haiten zeoliitit ja bentoniitti, jotka vähensivät myös Yaran vesien ammoniumpitoisuutta. Ionien yhtäaikainen poistaminen oli haastavaa ja sen parempi ymmärtäminen edellyttää jatkotutkimuksia. Yksi jatkotutkimuskohde voisi olla eri adsorbenttien yhdistäminen keskenään, ja tästä saatiin jo alustavia, rohkaisevia tuloksia.

Treatment of Fe-containing Acid Mine Waters in Fixed Bed Adsorption Column with Calcite Side-Stone

The acid mining drainage is considered the most significant environmental pollution problem around the world for the extensive formation acidic leachates containing heavy metals. Adsorption is widely used methods in water treatment due to it easy operation and the availability of a wide variety of commercial adsorbent (low cost). The primary goal of this thesis was to investigate the efficiency of neutralizing agents, CaCO3 and CaSiO3, and metal adsorption materials with unmodified limestone from Company Nordkalk Oy. In addition to this, the side materials of limestone mining were tested for iron adsorption from acidic model solution. This study was executed at Lappeenranta University of Technology, Finland. The work utilised fixed-bed adsorption column as the main equipment and large fluidized column. Atomic absorption spectroscopy (AAS) and x-ray diffraction (XRD) was used to determine ferric removal and the composition of material respectively. The results suggest a high potential for the studied materials to be used a low cost adsorbents in acid mine drainage treatment. From the two studied adsorbents, the FS material was more suitable than the Gotland material. Based on the findings, it is recommended that further studies might include detailed analysis of Gotland materials.

Investigation of adsorption of dyes onto modified titanium dioxide

Titanium dioxide (TiO2) nanoparticles with different sizes and crystalloid structures produced by the thermal method and doped with silver iodide (AgI), nitrogen (N), sulphur (S) and carbon (C) were applied as adsorbents. The adsorption of Methyl Violet (MV), Methylene Blue (MB), Methyl Orange (MO) and Orange II on the surface of these particles was studied. The photocatalytic activity of some particles for the destruction of MV and Orange II was evaluated under sunlight and visible light. The equilibrium adsorption data were fitted to the Langmuir, Freundlich, Langmuir-Freundlich and Temkin isotherms. The equilibrium data show that TiO2 particles with larger sizes and doped with AgI, N, S and C have the highest adsorption capacity for the dyes. The kinetic data followed the pseudo-first order and pseudo-second order models, while desorption data fitted the zero order, first order and second order models. The highest adsorption rate constant was observed for the TiO2 with the highest anatase phase percentage. Factors such as anatase crystalloid structure, particle size and doping with AgI affect the photocatalytic activity significantly. Increasing the rutile phase percentage also decreases the tendency to desorption for N-TiO2 and S-TiO2. Adsorption was not found to be important in the photocatalytic decomposition of MV in an investigation with differently sized AgI-TiO2 nanoparticles. Nevertheless C-TiO2 was found to have higher adsorption activity onto Orange II, as the adsorption role of carbon approached synchronicity with the oxidation role.

0 AND 02 ADSORPTION ON Ag/Cu[100]

In this work the adsorption mechanisms of atomic and molecular oxygen on Cu(100) surface are studied using ab initio simulation methods. Through the atomistic scale under-standing of the elementary oxidation processes we can further understand the large-scale oxidation. Copper is a material widely used in industry which makes it an interesting subject, and also understanding the oxidation of copper helps us understand the oxidation mechanism of other metals. First we have a look on some theory on surface alloys in general and behaviour of Ag on Cu(100) surface. After that the physical background there is behind the methods of density functional calculations are discussed, and some methods, namely potential energy surfaces and molecular dynamics, are introduced. Then there is a brief look on the numerical details used in the calculations, and after that, the results of the simulations are exhibited.

Kinetics of selective oxidation of lactose to lactobionic acid over Pd-active carbon catalyst

Laktoosi eli maitosokeri on tärkein ainesosa useimpien nisäkkäiden tuottamassa maidossa. Sitä erotetaan herasta, juustosta ja maidosta. Laktoosia käytetään elintarvike- ja lääketeollisuuden raaka-aineena monissaeri tuotteissa. Lääketeollisuudessa laktoosia käytetään esimerkiksi tablettien täyteaineena. Hapettamalla laktoosia voidaan valmistaa laktobionihappoa, 2-keto-laktobionihappoa ja laktuloosia. Laktobionihappoa käytetään biohajoavien pintojen ja kosmetiikkatuotteiden valmistuksessa, sekä sisäelinten säilöntäliuoksissa, joissa laktobionihappo estää happiradikaalien aiheuttamien kudosvaurioiden syntymistä. Tässä työssä laktoosia hapetettiin laktobionihapoksi sekoittimella varustetussa laboratoriomittakaavaisessa panosreaktorissa käyttäenkatalyyttinä palladiumia aktiivihiilellä. Muutamissa kokeissa katalyytin promoottorina käytettiin vismuttia, joka hidastaa katalyytin deaktivoitumista. Työn tarkoituksena oli saada lisää tietoa laktoosin hapettamisen kinetiikasta. Laktoosin hapettumisessa laktobionihapoksi havaittiin selektiivisyyteen vaikuttavan muunmuassa reaktiolämpötila, paine, pH ja käytetyn katalyytin määrä. Katalyyttiä kierrättämällä eri kokeiden välillä saatiin paremmat konversiot, selektiivisyydet ja saannot. Parhaat koetulokset saatiin hapetettaessa synteettisellä ilmalla 60 oC lämpötilassa ja 1 bar paineessa. Tehdyissä kokeissa pH:n säätö tehtiin manuaalisesti, joten pH ei pysynyt koko ajan haluttuna. Laktoosin konversio oli parhaimmillaan 95 %. Laktobionihapon suhteellinen selektiivisyys oli 100% ja suhteellinen saanto 100 %. Kinetiikan matemaattinen mallinnus tehtiin Modest-ohjelmalla käyttäen kokeista saatuja mittaustuloksia.Ohjelman avulla estimoitiin parametreja ja saatiin matemaattinen malli reaktorille. Tässä työssä tehtiin kineettinen mallinnus myös ravistelureaktorissa tehdyille laktoosin hapetuskokeille, missä pH pysyi koko ajan haluttuna 'in-situ' titrauksen avulla. Työn yhteydessä selvitettiin myös mahdollisuutta käyttää monoliittikatalyyttejä laktoosin hapetusreaktiossa.

Oxygen adsorption on Cu(510)

Tässä työssä on tutkittu kuparin (510)-askelpinnan reaktiivisuutta käyttäen apuna kvanttimekaanisia ab initio laskentamenetelmiä. Tutkimus on toteutettu laskemalla happiatomin adsorptioenergia ja tilatiheys erilaisissa potentiaalisissa adsorptiopaikoissa pinnalla. Myös happimolekyylin adsorptiota ja hajoamista ontarkasteltu laskemalla pintaa lähestyvälle molekyylille potentiaalienergiapintoja. Energiapintojen tuloksia on myös täydennetty kvanttimekaanisilla molekyylidynamiikkalaskuilla. Metallisia askelpintoja pidetään yleisesti sileitä pintoja reaktiivisempina happea kohtaan, johtuen askeleen reunan pienentävästä vaikutuksesta molekyylin hajoamisen tiellä olevaan energiavaliin. On kuitenkin olemassa myös tuloksia, jotka osoittavat hapen tarttumisprosessin olevan hallitseva juuri terassialueella, askeleen reunan sijasta. Tässä työssä on todettu hapen adsorboituvan Cu(510)-pinnalla tehokkaimmin juuri terassilla olevaan hollow-paikkaan. Myös adsorptioenergiat ovat tällä pinnalla pienempiä kuin sileällä (100)-pinnalla. Potentiaalienergiapintojen perusteella Cu(510)-pinnan todetaan myös olevan vähemmän reaktiivinen kuin askelpintojen yleisesti odotetaan olevan, vaikka askeleen reunan todetaankin pienentävän happiatominhajoamisen esteenä olevaa energiavallia.

Oxygen adsorption on Cu(211) and structurally and chemically modified Cu(100)

Kuparipinnan hapettuminen on viimevuosina ollut suosittu tutkimuskohde materiaalitieteissä kuparin laajan teollisuuskäytön vuoksi. Teollisuussovellusten, kuten suojaavien pintaoksidien kehittäminen vaatii kuitenkin syvällistä tuntemusta hapettumisprosessista ja toisaalta myös normaaliolosuhteissa materiaalissa esiintyvien hilavirheiden vaikutuksesta siihen. Tässä työssä keskitytäänkin tutkimaan juuri niitä mekanismeja, joilla erilaiset pintavirheet ja porrastettu pintarakenne vaikuttavathapen adsorptioprosessiin kuparipinnalla. Tutkimus on tehty käyttämällä laskennallisia menetelmiä sekä VASP- ja SIESTA-ohjelmistoja. Työssätutkittiin kemiallisia ja rakenteellisia virheitä Cu(100)-pinnalla, joka on reaktiivisin matalanMillerin indeksin pinta ja porrastetun pinnan tutkimuksessa käytettiin Cu(211)-pintaa, joka puolestaan on yksinkertainen, stabiili ja aiemmissa tutkimuksissa usein käytetty pintarakenne. Työssä tutkitut hilavirheet, adatomit, vähentävät molekyylin dissosiaatiota kuparipinnalla, kun taas vakanssit toimivat dissosiaation keskuksina. Kemiallisena epäpuhtautena käytetty hopeakerros ei estä kuparin hapettumista, sillä happi aiheuttaa mielenkiintoisen segregaatioilmiön, jossa hopeatyöntyy syvemmälle pinnassa jättäen kuparipinnan suojaamattomaksi. Porrastetulla pinnalla (100)-hollow on todennäköisin paikka molekyylin dissosiaatiolle, kun taas portaan bridge-paikka on suotuisin molekulaariselle adsorptiolle. Lisäksi kuparin steppipinnan todettiin olevan reaktiivisempi kuin tasaiset kuparipinnat.

Wet Oxidation of Concentrated Wastewaters: Process Combination and Reaction Kinetic Modeling

The accumulation of aqueous pollutants is becoming a global problem. The search for suitable methods and/or combinations of water treatment processes is a task that can slow down and stop the process of water pollution. In this work, the method of wet oxidation was considered as an appropriate technique for the elimination of the impurities present in paper mill process waters. It has been shown that, when combined with traditional wastewater treatment processes, wet oxidation offers many advantages. The combination of coagulation and wet oxidation offers a new opportunity for the improvement of the quality of wastewater designated for discharge or recycling. First of all, the utilization of coagulated sludge via wet oxidation provides a conditioning process for the sludge, i.e. dewatering, which is rather difficult to carry out with untreated waste. Secondly, Fe2(SO4)3, which is employed earlier as a coagulant, transforms the conventional wet oxidation process into a catalytic one. The use of coagulation as the post-treatment for wet oxidation can offer the possibility of the brown hue that usually accompanies the partial oxidation to be reduced. As a result, the supernatant is less colored and also contains a rather low amount of Fe ions to beconsidered for recycling inside mills. The thickened part that consists of metal ions is then recycled back to the wet oxidation system. It was also observed that wet oxidation is favorable for the degradation of pitch substances (LWEs) and lignin that are present in the process waters of paper mills. Rather low operating temperatures are needed for wet oxidation in order to destruct LWEs. The oxidation in the alkaline media provides not only the faster elimination of pitch and lignin but also significantly improves the biodegradable characteristics of wastewater that contains lignin and pitch substances. During the course of the kinetic studies, a model, which can predict the enhancements of the biodegradability of wastewater, was elaborated. The model includes lumped concentrations suchas the chemical oxygen demand and biochemical oxygen demand and reflects a generalized reaction network of oxidative transformations. Later developments incorporated a new lump, the immediately available biochemical oxygen demand, which increased the fidelity of the predictions made by the model. Since changes in biodegradability occur simultaneously with the destruction of LWEs, an attempt was made to combine these two facts for modeling purposes.