Käänteisosmoosin esikäsittelymenetelmät

Käänteisosmoosisuodatusta käytetään erityisesti teollisuuden jätevesien loppupuhdistuksessa. Suodatuksen ongelmana on kalvojen likaantuminen ja tukkiutuminen. Tässä työssä on aiempia tutkimuksia hyväksikäyttäen tutkittu käänteisosmoosiin tulevan veden esikäsittelemistä niin, että kalvojen likaantumiselta vältyttäisiin. Menetelmien vertailussa on käytetty erilaisia veden laadusta kertovia parametreja. Ongelmallisimmiksi aineksiksi huomattiin orgaaninen aines ja jotkin veteen liuenneet ionit. Kiintoaineen erottaminen ei ole ollut suuri ongelma, sillä sen saa poistettua tavallisesti käytetyillä rakeissuodatuksella, laskeutuksella, flotaatiolla ja kalvosuodatuksella. Orgaanista ainesta on saatu erotettua erityisesti hapettamalla, aktiivilieteprosessilla ja biologisella aktiivihiilisuodattimella. Mikro- ja ultrasuodatusta käytetään usein juuri ennen käänteisosmoosia poistamaan erityisesti kolloidista materiaalia ja joitain liuenneita ioneja. Flokkien muodostaminen koagulaatiossa ja flokkulaatiossa parantaa lähes kaikkien menetelmien toimivuutta selvästi. Veden puhdistuksessa käytetyt kemikaalit voivat myös liika-annosteltuina liata kalvoja. Vesien pitoisuuksissa eri ainesten osalta on huomattavia eroja, joten puhdistettava vesi on hyvä analysoida etukäteen parhaiden käsittelymenetelmien valitsemiseksi.

Pressure filtration characteristics of enzymatically hydrolyzed biomass suspensions

Enzymatic hydrolysis of lignocellulosic polymers is likely to become one of the key technologies enabling industrial production of liquid biofuels and chemicals from lignocellulosic biomass. Certain types of enzymes are able to hydrolyze cellulose and hemicellulose polymers to shorter units and finally to sugar monomers. These monomeric sugars are environmentally acceptable carbon sources for the production of liquid biofuels, such as bioethanol, and other chemicals, such as organic acids. Liquid biofuels in particular have been shown to contribute to the reduction of net emissions of greenhouse gases. The solid residue of enzymatic hydrolysis is composed mainly of lignin and partially degraded fibers, while the liquid phase contains the produced sugars. It is usually necessary to separate these two phases at some point after the hydrolysis stage. Pressure filtration is an efficient technique for this separation. Solid-liquid separation of biomass suspensions is difficult, because biomass solids are able to retain high amounts of water, which cannot be readily liberated by mechanical separation techniques. Most importantly, the filter cakes formed from biomaterials are compressible, which ultimately means that the separation may not be much improved by increasing the filtration pressure. The use of filter aids can therefore facilitate the filtration significantly. On the other hand, the upstream process conditions have a major influence on the filtration process. This thesis investigates how enzymatic hydrolysis and related process conditions affect the filtration properties of a cardboard suspension. The experimental work consists of pressure filtration and characterization of hydrolysates. The study provides novel information about both issues, as the relationship between enzymatic hydrolysis conditions and subsequent filtration properties has so far not been considered in academic studies. The results of the work reveal that the final degree of hydrolysis is an important factor in the filtration stage. High hydrolysis yield generally increases the average specific cake resistance. Mixing during the hydrolysis stage resulted in undefined changes in the physical properties of the solid residue, causing a high filtration resistance when the mixing intensity was high. Theoretical processing of the mixing data led to an interesting observation: the average specific cake resistance was observed to be linearly proportional to the mixer shear stress. Another finding worth attention is that the size distributions of the solids did not change very dramatically during enzymatic hydrolysis. There was an observable size reduction during the first couple of hours, but after that the size reduction was minimal. Similarly, the size distribution of the suspended solids remained almost constant when the hydrolyzed suspension was subjected to intensive mixing. It was also found that the average specific cake resistance was successfully reduced by the use of filter aids. This reduction depended on the method of how the filter aids were applied. In order to obtain high filtration capacity, it is recommended to use the body feed mode, i.e. to mix the filter aid with the slurry prior to filtration. Regarding the quality of the filtrate, precoat filtration was observed to produce a clear filtrate with negligible suspended solids content, while the body feed filtrates were turbid, irrespective of which type of filter aid was used.

Turbulenssimallien soveltuminen syklonien numeeriseen virtauslaskentaan

Tässä työssä tutkittiin miten totuudenmukaisia tuloksia syklonierottimen virtauskentästä saadaan numeerisella laskennalla, kun käytetään eri turbulenssimalleja. Tarkoitus oli myös selvittää yleisesti syklonin toimintaperiaatteita, haasteita sen käytössä sekä syklonin numeerisen virtauslaskennan perusteita. Numeerisen virtauslaskennan teoria selitetään pääpiirteittäin, samoin turbulenssin mallinnus. Työn laskentaosiossa simuloitiin Fluent-ohjelmalla syklonin virtauskenttää kuumalla ilmalla sekä kahdella eri turbulenssimallilla ja verrattiin tuloksia kirjallisuudesta löytyviin mittaustuloksiin. Simuloinnit suoritettiin sekä ajasta riippuvana että ajasta riippumattomana ja kahdella eri laskentahilalla. Simulointien tulokset osoittivat, että RNG k-ε turbulenssimalli ei kykene tuottamaan totuu-denmukaista virtauskenttää. Toisen käytetyn turbulenssimallin, Reynolds-jännitysmallin tulokset vastasivat enemmän mittaustuloksia. Reynolds-jännitysmallia voidaan pitää käyttökelpoisena syklonin simuloinnissa tämän työn ja kirjallisuuden perusteella. Mallissa oli yksinkertaistuksia, esimerkiksi kiinteää ainetta ei otettu huomioon lainkaan.

Integrating Student Learning into the Repository Ecosystem

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

Big Data Processing in the Cloud: a Hydra/Sufia Experience

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

Arktisissa olosuhteissa käytettäville materiaaleille ja hitsatuille rakenteille asetetut vaatimukset

Diplomityössä tarkastellaan kohdeyrityksen hitsatuille teräsrakenteille asetettuja vaatimuksia Norjan ja Venäjän arktisilla alueilla. Teknisten vaatimusten lisäksi tutkitaan terästen kylmäkäyttäytymistä ja hitsaustuotannolle kohdistettuja vaatimuksia. Tutkimuksen lopussa käsitellään Venäjän ja Norjan markkinoiden erityispiirteitä ja keinoja markkinoille pääsemiseksi. Tutkimuksen perusteella havaitaan, että kohdeyritys voi suunnitella ja valmistaa sekä Norjan että Venäjän vaatimusten mukaisia rakenteita ilman suuria muutoksia rakenteisiin tai hitsaustuotantoon. Materiaalien ja valmistuksen laadun sekä niiden valvonnan merkitys korostuu arktisissa hankkeissa. Yrityksellä on käytössään standardit EN 1090, ISO 9001, ISO 3834 ja ISO 14122, jotka edesauttavat yrityksen kansainvälistymistä. Hitsattujen rakenteiden haurasmurtumariski kasvaa kylmissä olosuhteissa. Haurasmurtuman ydintymistä edesauttavat tekijät täytyy tunnistaa ja niitä on vältettävä suunnittelussa ja valmistuksessa. Lujempien ja sitkeämpien terästen käyttäminen kylmissä olosuhteissa on perusteltua, mutta ne asettavat omat haasteensa hitsaukselle.

Utilization of steelmaking waste materials for production of calcium carbonate (CaCO3)

The steel industry produces, besides steel, also solid mineral by-products or slags, while it emits large quantities of carbon dioxide (CO2). Slags consist of various silicates and oxides which are formed in chemical reactions between the iron ore and the fluxing agents during the high temperature processing at the steel plant. Currently, these materials are recycled in the ironmaking processes, used as aggregates in construction, or landfilled as waste. The utilization rate of the steel slags can be increased by selectively extracting components from the mineral matrix. As an example, aqueous solutions of ammonium salts such as ammonium acetate, chloride and nitrate extract calcium quite selectively already at ambient temperature and pressure conditions. After the residual solids have been separated from the solution, calcium carbonate can be precipitated by feeding a CO2 flow through the solution. Precipitated calcium carbonate (PCC) is used in different applications as a filler material. Its largest consumer is the papermaking industry, which utilizes PCC because it enhances the optical properties of paper at a relatively low cost. Traditionally, PCC is manufactured from limestone, which is first calcined to calcium oxide, then slaked with water to calcium hydroxide and finally carbonated to PCC. This process emits large amounts of CO2, mainly because of the energy-intensive calcination step. This thesis presents research work on the scale-up of the above-mentioned ammonium salt based calcium extraction and carbonation method, named Slag2PCC. Extending the scope of the earlier studies, it is now shown that the parameters which mainly affect the calcium utilization efficiency are the solid-to-liquid ratio of steel slag and the ammonium salt solvent solution during extraction, the mean diameter of the slag particles, and the slag composition, especially the fractions of total calcium, silicon, vanadium and iron as well as the fraction of free calcium oxide. Regarding extraction kinetics, slag particle size, solid-to-liquid ratio and molar concentration of the solvent solution have the largest effect on the reaction rate. Solvent solution concentrations above 1 mol/L NH4Cl cause leaching of other elements besides calcium. Some of these such as iron and manganese result in solution coloring, which can be disadvantageous for the quality of the PCC product. Based on chemical composition analysis of the produced PCC samples, however, the product quality is mainly similar as in commercial products. Increasing the novelty of the work, other important parameters related to assessment of the PCC quality, such as particle size distribution and crystal morphology are studied as well. As in traditional PCC precipitation process, the ratio of calcium and carbonate ions controls the particle shape; a higher value for [Ca2+]/[CO32-] prefers precipitation of calcite polymorph, while vaterite forms when carbon species are present in excess. The third main polymorph, aragonite, is only formed at elevated temperatures, above 40-50 °C. In general, longer precipitation times cause transformation of vaterite to calcite or aragonite, but also result in particle agglomeration. The chemical equilibrium of ammonium and calcium ions and dissolved ammonia controlling the solution pH affects the particle sizes, too. Initial pH of 12-13 during the carbonation favors nonagglomerated particles with a diameter of 1 μm and smaller, while pH values of 9-10 generate more agglomerates of 10-20 μm. As a part of the research work, these findings are implemented in demonstrationscale experimental process setups. For the first time, the Slag2PCC technology is tested in scale of ~70 liters instead of laboratory scale only. Additionally, design of a setup of several hundreds of liters is discussed. For these purposes various process units such as inclined settlers and filters for solids separation, pumps and stirrers for material transfer and mixing as well as gas feeding equipment are dimensioned and developed. Overall emissions reduction of the current industrial processes and good product quality as the main targets, based on the performed partial life cycle assessment (LCA), it is most beneficial to utilize low concentration ammonium salt solutions for the Slag2PCC process. In this manner the post-treatment of the products does not require extensive use of washing and drying equipment, otherwise increasing the CO2 emissions of the process. The low solvent concentration Slag2PCC process causes negative CO2 emissions; thus, it can be seen as a carbon capture and utilization (CCU) method, which actually reduces the anthropogenic CO2 emissions compared to the alternative of not using the technology. Even if the amount of steel slag is too small for any substantial mitigation of global warming, the process can have both financial and environmental significance for individual steel manufacturers as a means to reduce the amounts of emitted CO2 and landfilled steel slag. Alternatively, it is possible to introduce the carbon dioxide directly into the mixture of steel slag and ammonium salt solution. The process would generate a 60-75% pure calcium carbonate mixture, the remaining 25-40% consisting of the residual steel slag. This calcium-rich material could be re-used in ironmaking as a fluxing agent instead of natural limestone. Even though this process option would require less process equipment compared to the Slag2PCC process, it still needs further studies regarding the practical usefulness of the products. Nevertheless, compared to several other CO2 emission reduction methods studied around the world, the within this thesis developed and studied processes have the advantage of existing markets for the produced materials, thus giving also a financial incentive for applying the technology in practice.

AQUAREL CONCEPT Aquatic resources for green energy realization

The AQUAREL project studied the availability and optional utilization methods for fish processing side streams and other aquatic biomaterial in the Republic of Karelia. Additionally processing aquatic biomaterial with manure and sewage sludge was studied. Based on the results, the most feasible option today is to process fish side streams to fish oil and dewatered oil-free residue and to use them for fish or animal feed production. However, it is necessary to highlight, that changes in e.g. economic environment, energy prices and demand may require re-evaluating the results and conclusions made in the project. Producing fish oil from fish processing side streams is an easy and relatively simple production process generating a valuable end product. The functionality of the process was confirmed in a pilot conducted in the project. The oil and solids are separated from the heated fish waste based on gravity. The fish oil separating on top of the separator unit is removed. Fish oil can as such be utilized for heating purposes, fish meal or animal feed production, but it can also be further processed to biodiesel. However, due to currently moderate energy prices in Russia, biodiesel production is not economically profitable. Even if the fish oil production process is not complicated, the operative management of small-scale fish oil production unit requires dedicated resources and separate facilities especially to meet hygiene requirements. Managing the side streams is not a core business for fish farmers. Efficient and economically profitable fish oil production requires a centralized production unit with bigger processing capacity. One fish processing unit needs to be designed to manage side streams collected from several fish farms. The optimum location for the processing unit is in the middle of the fish farms. Based on the transportation cost analysis in the Republic of Karelia, it is not economically efficient to transport bio-wastes for more than 100 km since the transportation costs start increasing substantially. Another issue to be considered is that collection of side streams, including the dead fish, from the fish farms should be organized on a daily basis in order to eliminate the need for storing the side streams at the farms. Based on AQUAREL project studies there are different public funding sources available for supporting and enabling profitable and environmentally sustainable utilization, research or development of fish processing side streams and other aquatic biomaterial. Different funding programmes can be utilized by companies, research organizations, authorities and non-governmental organizations.

Feasibility study of submerged membrane bioreactor (MBR) as an alternative to conventional activated sludge process (CASP) for municipal wastewater treatment: A pilot scale study

The conventional activated sludge processes (CAS) for the treatment of municipal wastewater are going to be outdated gradually due to more stringent environmental protection laws and regulations. The Membrane bioreactors (MBRs) are the most promising modern technology widely accepted in the world of wastewater treatment due to their highly pronounced features such as high quality effluent, less foot print and working under high MLSS concentration. This research project was carried out to investigate the feasibility and effectiveness of MBR technology compare to the CAS process based on the scientific facts and results. The pilot scale MBR pilot plant was run for more than 150 days and the analysis results were evaluated. The prime focus of the project was to evaluate the correlation of permeate flux under different operating MLSS concentrations. The permeate flux was found almost constant regardless of variations in MLSS concentrations. The removal of micropollutant such as heavy metals, PCPPs, PFCs, steroidal hormones was also studied. The micropollutant removal performance of MBR process was found relatively effective than CAS process. Furthermore, the compatibility of submerged membranes within the bioreactor had truly reduced the process footprint.

Behavior of black liquor nitrogen in combustion : formation of cyanate

The Kraft pulping process is the dominant chemical pulping process in the world. Roughly 195 million metric tons of black liquor are produced annually as a by-product from the Kraft pulping process. Black liquor consists of spent cooking chemicals and dissolved organics from the wood and can contain up to 0.15 wt% nitrogen on dry solids basis. The cooking chemicals from black liquor are recovered in a chemical recovery cycle. Water is evaporated in the first stage of the chemical recovery cycle, so the black liquor has a dry solids content of 65-85% prior to combustion. During combustion of black liquor, a portion of the black liquor nitrogen is volatilized, finally forming N2 or NO. The rest of the nitrogen remains in the char as char nitrogen. During char conversion, fixed carbon is burned off leaving the pulping chemicals as smelt, and the char nitrogen forms mostly smelt nitrogen (cyanate, OCN-). Smelt exits the recovery boiler and is dissolved in water. The cyanate from smelt decomposes in the presence of water, forming NH3, which causes nitrogen emissions from the rest of the chemical recovery cycle. This thesis had two focuses: firstly, to determine how the nitrogen chemistry in the recovery boiler is affected by modification of black liquor; and secondly, to find out what causes cyanate formation during thermal conversion, and which parameters affect cyanate formation and decomposition during thermal conversion of black liquor. The fate of added biosludge nitrogen in chemical recovery was determined in Paper I. The added biosludge increased the nitrogen content of black liquor. At the pulp mill, the added biosludge did not increase the NO formation in the recovery boiler, but instead increased the amount of cyanate in green liquor. The increased cyanate caused more NH3 formation, which increased the NCG boiler’s NO emissions. Laboratory-scale experiments showed an increase in both NO and cyanate formation after biosludge addition. Black liquor can be modified, for example by addition of a solid biomass to increase the energy density of black liquor, or by separation of lignin from black liquor by precipitation. The precipitated lignin can be utilized in the production of green chemicals or as a fuel. In Papers II and III, laboratory-scale experiments were conducted to determine the impact of black liquor modification on NO and cyanate formation. Removal of lignin from black liquor reduced the nitrogen content of the black liquor. In most cases NO and cyanate formation decreased with increasing lignin removal; the exception was NO formation from lignin lean soda liquors. The addition of biomass to black liquor resulted in a higher nitrogen content fuel mixture, due to the higher nitrogen content of biomass compared to black liquor. More NO and cyanate were formed from the fuel mixtures than from pure black liquor. The increased amount of formed cyanate led to the hypothesis that black liquor is catalytically active and converts a portion of the nitrogen in the mixed fuel to cyanate. The mechanism behind cyanate formation during thermal conversion of black liquor was not clear before this thesis. Paper IV studies the cyanate formation of alkali metal loaded fuels during gasification in a CO2 atmosphere. The salts K2CO3, Na2CO3, and K2SO4 all promoted char nitrogen to cyanate conversion during gasification, while KCl and CaCO3 did not. It is now assumed that cyanate is formed when alkali metal carbonate or an active intermediate of alkali metal carbonate (e.g. -CO2K) reacts with the char nitrogen forming cyanate. By testing different fuels (bark, peat, and coal), each of which had a different form of organic nitrogen, it was concluded that the form of organic nitrogen in char also has an impact on cyanate formation. Cyanate can be formed during pyrolysis of black liquor, but at temperatures 900°C or above, the formed cyanate will decompose. Cyanate formation in gasifying conditions with different levels of CO2 in the atmosphere was also studied. Most of the char nitrogen was converted to cyanate during gasification at 800-900°C in 13-50% CO2 in N2, and only 5% of the initial fuel nitrogen was converted to NO during char conversion. The formed smelt cyanate was stable at 800°C 13% CO2, while it decomposed at 900°C 13% CO2. The cyanate decomposition was faster at higher temperatures and in oxygen-containing atmospheres than in an inert atmosphere. The presence of CO2 in oxygencontaining atmospheres slowed down the decomposition of cyanate. This work will provide new information on how modification of black liquor affects the nitrogen chemistry during thermal conversion of black liquor and what causes cyanate formation during thermal conversion of black liquor. The formation and decomposition of cyanate was studied in order to provide new data, which would be useful in modeling of nitrogen chemistry in the recovery boiler.

Kunnallisen jätevedenkäsittelyn tehostaminen membraanitekniikan avulla – esimerkkinä Savitaipaleen jätevedenpuhdistamo

Työssä tutkittiin mahdollisuutta tehostaa kunnallista jätevedenpuhdistusta membraanitekniikkaa käyttäen. Teoriaosassa perehdyttiin kunnallisen jäteveden omi-naisuuksiin ja perinteiseen puhdistusprosessiin. Tämän lisäksi membraanien yleisiä ominaisuuksia, membraanityyppien kykyä erottaa jäteveden sisältämiä yhdisteitä sekä erilaisia mahdollisuuksia membraanisuodatukselle perinteisen jäteve-denpuhdistusprosessin yhteydessä käytiin läpi. Kokeellisessa osassa keskityttiin Savitaipaleen puhdistamon puhdistetun jäteveden laadun parantamiseen membraanisuodatukseen perustuvalla jälkikäsittely-yksiköllä eli tertiäärisuodatuksella. Erilaisia paineavusteisia membraanitekniikoita (MF, UF, NF ja RO) tutkittiin jäteveden puhdistamiseksi ja erotustehokkuuden vertailemiseksi. Tavoitteena oli löytää tehokas ja käytännössä toimiva tapa poistaa fosforia ja typpeä puhdistetusta jätevedestä. Tasomaisilla membraaneilla tehdyissä suodatuksissa MF-membraanit poistivat tehokkaasti fosforia (97 – 98 %) sekä kiintoainesta (100 %) jätevedestä. RO-membraanit alensivat fosfori- (100 %) ja typpipitoisuutta (90 – 94 %) tehokkaasti, poistaen myös liuenneita orgaanisia yhdisteitä (DOC, 90 – 94 %). Mikrosuodatukseen perustuvilla onttokuitumembraaneilla saavutettiin tehokkaan fosforinpoiston lisäksi tasainen kapasiteetti suodatuksen aikaista puhdistusmene-telmää optimoimalla. Pitoisuusalenemat olivat myös erittäin korkeita fosforille (97 – 99 %), kiintoaineelle (100 %), sameudelle (96 – 99 %) sekä COD:lle (38 – 55 %). Tulosten perusteella membraanitekniikkaan perustuva onttokuitusuodatus olisi tehokas ja toimiva jälkikäsittelyprosessi fosforinpoistoon ja jäteveden laadun pa-rantamiseen. Typen poistamiseen parhaiten toimi RO-membraani.

Entsyymien talteenotto ja kierrätys selluloosaetanolin valmistuksessa

Bioetanolin valmistus selluloosapitoisista raaka-aineista vaatii selluloosapolymeerien pilkkomisen liukoisiksi sokereiksi. Tämä voidaan toteuttaa entsymaattisella hydrolyysillä. Selluloosan pilkkomiseen tarkoitetut entsyymit, sellulaasit, ovat entsymaattisen hydrolyysin jälkeen sitoutuneet joko kiintoainefaasiin tai ovat nestemäisessä faasissa ns. vapaina entsyymeinä. Prosessin taloudellisuuden kannalta on erityisen tärkeää minimoida siinä käytettävien entsyymien tarve, sillä tehokkaat entsyymivalmisteet ovat suhteellisen kalliita. Yksi varteenotettava vaihtoehto bioetanoliprosessin saamiseksi taloudellisemmaksi on käytettyjen entsyymien talteenotto ja kierrätys. Työn tarkoituksena oli selvittää kirjallisuudesta, millaisia menetelmiä on kehitetty entsyymien talteenottoon ja kierrätykseen lignoselluloosasta valmistettavan bioetanolin valmistuksessa. Työssä on keskitytty tuoreisiin tutkimuksiin ja menetelmien käyttökelpoisuuteen ja taloudellisuuteen. Viime vuosina sellulaasien talteenotto- ja kierrätysmenetelmiä koskevat tutkimukset ovat keskittyneet pääasiassa käsittelemään nanopartikkelien avulla tapahtuvaa entsyymien immobilisointia, ultrasuodatusta, erilaisia desorptiomenetelmiä, kiinteän hydrolyysijäännöksen kierrättämistä, tuoreen substraatin lisäämistä sekä myös tislausvaiheen jälkeistä entsyymien kierrättämistä. Jotta kierrätysmenetelmä olisi tehokas, tulisi sen pyrkiä säilyttämään entsyymien aktiivisuuksia, sokerisaantoa menettämättä ja sisältää sekä neste-, että kiintoainefaasista tapahtuva kierrätys. Jokaisella kierrätysmenetelmällä on hyvät ja huonot puolensa. Entsyymien talteenottoastetta saadaan kuitenkin parannettua yhdistämällä erilaisia menetelmiä. Useista tutkimuksista huolimatta, taloudellisinta ja käyttökelpoisinta entsyymien talteenotto- ja kierrätysmenetelmää ei ole vielä saavutettu.

Suspension esikäsittelyn vaikutus kiintoaineen laskeutumisnopeuteen

Laskeutus on yksinkertainen ja teollisuudessa paljon käytetty erotusmenetelmä. Laskeutusta käytetään yleisimmin metalliteollisuudessa ja jätevesienkäsittelyssä. Laskeuttimen erotustehokkuutta voidaan parantaa esikäsittelemällä laskeutettavaa suspensiota. Laskeutusta on tutkittu hyvin laajasti teollisuudessa, koska laskeutus on menetelmänä helposti toteutettava ja energiatehokas. Työn kirjallisuusosassa käsitellään perusteet kiintoaineen laskeutumisesta fluidissa, tutustutaan laskeuttimiin ja esitellään suspension esikäsittelymenetelmät. Työn kokeellisessaosassa tutkitaan esikäsittelymenetelmien vaikutusta kalsiumkarbonaattilietteen laskeutumisnopeuteen. Tutkittavia esikäsittelymenetelmiä työn kokeellisessaosassa ovat flokkulaatio, lämpötilan ja pH:n muuttaminen. Laskeutuskokeet suoritettiin tilavuusosuudella 10 % olevalla kalsiumkarbonaattilietteellä. Tutkimuksen tarkoituksena oli tutkia tutkittavien esikäsittelymenetelmien vaikutusta lietteen laskeutumisnopeuteen ja löytää optimiolosuhteet työssä käytettävän kalsiumkarbonaattilietteen laskeutumisessa. Koetuloksista havaitaan, että flokkulaatio ja lämpötilan muuttaminen vaikuttavat tehoikkaimmin lietteen laskeutumisnopeuteen. Flokkulaatio ja lämpötilan kohottaminen lisäävät huomattavasti kiintoaineen laskeutumista. Lisätutkimusta tarvitaan laajemmalta pH alueelta optimiolosuhteiden löytämiseksi. Lisäksi jatkotutkimuksia eri flokkulanteilla tarvitaan lisää, jotta voidaan löytää paras flokkulantti laskeutumisprosessin tehostamiseksi.

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.