Potencial uso de serpentinito no armazenamento mineral do CO2

Rising anthropogenic CO2 emissions are considered a major contributor to the greenhouse effect. There are several options for reducing atmospheric CO2 levels, and among these alternatives, Carbon Capture and Storage (CCS) has been identified as an effective and promising approach. This work investigated the feasibility of using serpentinite as a vehicle for carbon storage presenting a source-sink match. The main results of the work confirmed that serpentinite is appropriate for the carbonation process due to the high concentration of Mg in its composition.

Nanopartículas de poli-hidroxibutirato-co-valerato como suporte para a imobilização da lipase de Candida antarctica fração B

This work evaluates the immobilization of Candida antarctica lipase (Fraction B) using poly(hydroxybutyrate-co-hydroxyvalerate) (PHBV) nanoparticles as support. The effects of immobilization time (30-150 min) and pH (5-10) on lipase loading were evaluated. The stability of the immobilized enzyme towards temperature (40, 60, and 80 ºC), reuse and storage (at 4 ºC) were also determined. Furthermore, to assess its potential application in a system of interest, the immobilized lipase was used as a catalyst in the esterification of geraniol with oleic acid. The results indicated a time of 120 minutes and pH of 7 as optimal for immobilization. A 21 hour exposure of the PHBV-lipase derivative to 60 ºC showed a 33% reduction of the initial activity while storage at 4 ºC led to a residual activity (5% of the original activity). The derivative was used without significant loss of activity for 4 successive cycles. The use of the immobilized lipase as a catalyst in the production of geranyl oleate led to about 88% conversion of the initial reactants to products.

METODOLOGIAS DE COLETA, PRESERVAÇÃO E ARMAZENAMENTO DE AMOSTRAS DE ÁGUA PARA ANÁLISE DE MERCÚRIO - UMA REVISÃO

Knowing the mercury levels of an environment allows a diverse array of biogeochemical studies into the mercury cycle on a local or global scale. Among matrices commonly evaluated, water remains a challenge for research because its mercury levels can be very low, requiring development of complex analytical protocols. Currently, sample preservation methods, protocols that avoid contamination, and analytical techniques with low detection limits allow analysis of mercury in pristine waters. However, different protocols suggest different methods depending on a range of factors such as the characteristics of water sampled and storage time. In remote areas, such as oceanic and Amazonian regions, sample preservation and transport to a laboratory can be difficult, requiring processing of the water during the sampling expedition and the establishment of a field laboratory. Brazilian research on mercury in water can be limited due to difficulty obtaining reagents, lack of laboratory structure, qualified personnel, and financial support. Considering this complexity for analyzing water, we reviewed methodologies for sampling, preservation, and storage of water samples for analysis of the most commonly evaluated mercury species (dissolved gaseous mercury, reactive mercury, methylmercury and total mercury).

ADAPTAÇÃO DA METODOLOGIA DE ANÁLISE DE METEMOGLOBINA COMO BIOMARCADOR DE EFEITO DA EXPOSIÇÃO AO AGROTÓXICO DIFLUBENZURON

This work aimed to adapt the analysis of methemoglobin recommended by Evelyn - Malloy (visible spectrophotometry), in order to facilitate its application in the field, or to analysis in clinical laboratory, of existing sites of diflubenzuron application. The parameters changed included: centrifuge rotation speed; time between the collection of biological sample and analysis, and storage temperature of the samples; and the volume of reagents. The comparison of the rotation speed (rpm) of the reference methodology with the rpm of a "clinical centrifuge" did not reveal a statistically significant difference in the levels of methemoglobin. The time between the collection of biological sample and analysis was extended for a period of up to 48 hours for both conservation by refrigeration and ambient temperature, producing no statistically significant difference when compared to the standard duration of 2 hours. Regarding the reagents, the reference methodology already uses the volume necessary to ensure complete reaction, whereas a wider range from the recommended volume to a 5-fold reduction in comparison to the reference methodology could be used. It was concluded that the proposed changes to the methodology for adapting the analysis are applicable to studies of field / workplace exposure and ensure the reliability of results. The adapted methodology was inter-laboratory validated and the parameters changed can be selected according to the requirements of the laboratory at which the methemoglobin is to be measured.

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.

Development of chemical looping combustion process

Chemical looping combustion (CLC) provides a promising technology to help cut carbon dioxide emissions. CLC is based on separated oxidation and reduction processes. Oxygen carrier, which is made from metal and supporting material, is in continuous recirculation between the air and fuel reactors. The CLC process does not require separation unit for carbon dioxide. The fuel reactor can produce an almost pure carbon dioxide feed which decrease costs of carbon capture and storage (CCS). The CLC method is one of the most promising ones for energy efficient carbon capture. A large amount of literature was examined for this study and from it the most promising methods and designs were chosen. These methods and designs were combined as reactor system design which was then sized during the making of this thesis. Sizing was done with a mathematical model that was further improved during the study.

Polymer surface modification by atomic layer deposition

Current industrial atomic layer deposition (ALD) processes are almost wholly confined to glass or silicon substrates. For many industrial applications, deposition on polymer substrates will be necessary. Current deposition processes are also typically carried out at temperatures which are too high for polymers. If deposition temperatures in ALD can be reduced to the level applicable for polymers, it will open new interesting areas and applications for polymeric materials. The properties of polymers can be improved for example by coatings with functional and protective properties. Although the ALD has shown its capability to operate at low temperatures suitable for polymer substrates, there are other issues related to process efficiency and characteristics of different polymers where new knowledge will assist in developing industrially conceivable ALD processes. Lower deposition temperature in ALD generally means longer process times to facilitate the self limiting film growth mode characteristic to ALD. To improve process efficiency more reactive precursors are introduced into the process. For example in ALD oxide processes these can be more reactive oxidizers, such as ozone and oxygen radicals, to substitute the more conventionally used water. Although replacing water in the low temperature ALD with ozone or plasma generated oxygen radicals will enable the process times to be shortened, they may have unwanted effects both on the film growth and structure, and in some cases can form detrimental process conditions for the polymer substrate. Plasma assistance is a very promising approach to improve the process efficiency. The actual design and placement of the plasma source will have an effect on film growth characteristics and film structure that may retard the process efficiency development. Due to the fact that the lifetime of the radicals is limited, it requires the placement of the plasma source near to the film growth region. Conversely this subjects the substrate to exposure byother plasma species and electromagnetic radiation which sets requirements for plasma conditions optimization. In this thesis ALD has been used to modify, activate and functionalize the polymer surfaces for further improvement of polymer performance subject to application. The issues in ALD on polymers, both in thermal and plasma-assisted ALD will be further discussed.

Carbonation of Mg(OH)2 in a pressurised fluidised bed for CO2 sequestration

I takt med den ekonomiska tillväxten har CO2-utsläppen till atmosfären ständigt ökat, och utan kraftiga åtgärder kommer de att fortsätta att öka i allt snabbare takt. Konsekvenserna av en påtagligt förhöjd atmosfärisk CO2-halt är fortfarande osäkra (men eventuellt katastrofala) och fenomenet går under namnet global uppvärmning eller klimatförändring. CCS från engelskans ”carbon dioxide capture and storage” framstår som ett alternativ för att bekämpa de ständigt ökande CO2-utsläppen. Ett av de mer intressanta, och för Finlands del ända CCS-alternativet, baserar sig på naturens egna sätt att begränsa atmosfärisk CO2, nämligen vittring. Naturlig vittring, som förenklat innefattar nedbrytningen av sten/berg (även känd som erosion) och de därpå följande reaktionerna med CO2-mättat regnvatten. Slutresultatet är en utfällning av fasta mineraler som nu bundit CO2 i form av kalcium- och magnesiumkarbonat. Kalciumkarbonat är även bättre känt som kalksten, d.v.s. CO2 blir bundet i sten. Det gäller dock att snabba upp denna process, som i naturen är ytterst långsam, på ett ekonomiskt och miljömässigt hållbart sätt. Hittills har ett antal metoder för att påskynda naturlig vittring, eller med andra ord öka CO2-upptagningsförmågan av olika mineraler föreslagits. De mera etablerade uttrycken (lånade från engelskan) talar om mineralkarbonatisering och CO2-mineralisering. Till skillnad från många andra CO2-mineraliseringsalternativ är det alternativ som behandlas i denna avhandling i hög grad baserat på möjligheten att utnyttja den värme som frigörs vid karbonatisering. I teorin är det möjligt att föreställa sig en mineraliseringsprocess som inte kräver extern energi, men tillsvidare har man dock inte lyckats uppnå detta mål. Den process som presenteras i denna avhandling går ut på att man utvinner magnesium ur i naturen vanligt förekommande magnesiumrika mineraler, konverterar det till magnesiumhydroxid och därefter karbonatiserar det till magnesiumkarbonat. I rätta förhållanden kan magnesiumhydroxid reagera med CO2 mycket snabbt och i nuläget har processen potential att minska CO2-utsläppen från industri där spillvärme finns till förfogande (t.ex. cement- och stålindustrin). Fortsatt forskning är dock ett måste för att kunna påverka CO2-utsläppen i en globalt signifikant skala.

Rakennustarkastuksen mobiilityökalun suunnittelu ja toteuttaminen

Rakennusteollisuuden prosessit ovat vielä usein paperipohjaisia, mikä aiheuttaa työmaiden luonteesta johtuen tiedon hajaantumista, hidastaa tiedon siirtymistä ja vaikeuttaa tiedon käsittelyä. Työmaiden väliaikaisilla konttoreilla tiedon määrä voi nousta hallitsemattoman suureksi, mikä haittaa ja hidastaa työnjohdon päätöksentekoa. Käyttämällä sähköisiä työkaluja tiedon keräämistä, keskittämistä ja siirtoa voidaan tehostaa. Projektin tavoitteeksi otettiin teollisuuden laadunvalvonnan tarkastusprosessin tehostaminen ajallisesti käyttämällä tarkastustyöhön sähköistä tarkastuspöytäkirjaa. Tätä varten suunniteltiin sähköinen tarkastusjärjestelmä, joka koostuu kolmesta erillisestä osasta: Tarkastajan mukana kulkeva mobiililaite, jolle tallennetaan suoraan tarkastuksen laatutietoa, palvelinkone avustamaan tiedonsiirrossa ja –varastoinnissa sekä työpöytäsovellus työnjohdon tarpeisiin. Järjestelmää testattiin sähköalan asennuksia tekevässä yrityksessä osana yrityksen normaalia tarkastustyötä. Verrattuna paperiseen pöytäkirjaan sähköinen tarkastusjärjestelmä nopeutti prosessia moninkertaisesti. Nopeustesteissä havaittiin kuitenkin, että valittu tiedon synkronointikirjasto oli järjestelmän tarpeisiin liian hidas. Järjestelmä saavutti sille asetetut tavoitteet tehostamalla prosessia ajallisesti, mutta järjestelmässä on vielä osa-alueita, jotka tarvitsevat jatkokehittämistä.

Silting in the dense reservoir network of the Pereira de Miranda catchment

This study aims to analyze the impacts of the reservoir network within Pereira de Miranda - CE catchment (also called Pentecoste) over sediment transport and storage capacity of the system. The survey of the "damming" was carried out using satellite images. We identified 502 erosion units, derived from overlaying maps of the Universal Soil Loss Equation parameters, which allowed the estimation of localized erosion in the basin and identification of areas potentially generating sediment. In order to estimate silting in Pentecoste reservoir, different system structure scenarios were considered. An average erosion rate of 59 t ha-1year-1 was estimated. According to the model, the silting of Pentecoste reservoir may vary from 1.1 to 2.6% per decade, depending on the scenario considered. It is also observed that the reservoirs upstream can retain up to 58% of the sediment that would reach the Pentecoste reservoir. Very small reservoirs with a capacity of up to 100,000 m³, although representing only 1.83% of the system water availability, are able to retain almost 8% of total sediment produced.

Determination of physical properties of crambe fruits during drying

The Knowledge of the physical properties of agricultural products has great importance for the construction and operation of equipment for drying and storage, to achieve increased efficiency in post-harvest operations. The aim was to determine and analyze the physical properties of crambe fruits during drying at different temperatures. Crambe fruits with an initial moisture content of 0.36 (decimal d.b.) which was reduced by drying at 37.0; 58.8 and 83.5 ºC and relative humidity of 29.4; 11.2 and 3.2%, respectively, to 0.09 ± 1 (decimal d.b.). At different levels of moisture contents (0.36; 0.31; 0.26; 0.21; 0.17; 0.13 and 0.09 decimal d.b.), was evaluated the intergranular porosity, the bulk density, the true density as well as the volumetric shrinkage and the fruit mass. The study was installed by the factorial 3 x 7, and three drying temperatures and seven moisture contents in a randomized design. Data were analyzed using regression. The bulk density and the true density decreases along the drying process; the volumetric shrinkage and the mass increased with lower moisture content and the intergranular porosity decreased sharply with the increasing drying temperature.

Modelling of calciner in post-combustion carbon capture process

Climate change has given an impetus to research and developed new technologies to reduce significantly carbon dioxide emissions in energy production in the developed countries. The major pollution source, fossil fuels, will be used as an energy source for many decades, which provides the demand for carbon capture and storage technologies. Over recent years many new technologies has been developed and one of the most promising is calcium-looping in post-combustion carbon capture process, which use carbonation-calcination cycle to capture carbon dioxide from the flue gas of a combustion process. First pilot plant for calcium-looping process has been built in Oviedo, Spain. In this study, a three-dimensional model has been created for the calciner, which is one of the two fluidized bed reactors needed for the process. The calciner is a regenerator where the captured carbon dioxide is removed from the calcium material and then collected after the reactor. Thesis concentrates in creating the calciner 3D-model frame with CFB3D-program and testing the model with two different example cases. Used input parameters and calciner geometry are Oviedo pilot plant design parameters. The calculation results give information about the process and show that pilot plant calciner should perform as planned. This Master’s Thesis is done in participation to EU FP7 project CaOling.

Pulsed corona discharge as an advanced oxidation process for degradation of organic

Advanced oxidation processes (AOPs) have been studied and developed to suffice the effective removal of refractory and toxic compounds in polluted water. The quality and cost of wastewater treatment need improvements, and electric discharge technology has a potential to make a significant difference compared to other established AOPs based on energy efficiency. The generation of active oxidant species such as ozone and hydroxyl radicals by high voltage discharge is a relatively new technology for water treatment. Gas-phase pulsed corona discharge (PCD), where a treated aqueous solution is dispersed between corona-producing electrodes free of the dielectric barriers, was developed as an alternative approach to the problem. The short living radicals and ozone formed in the gas phase and at the gas-liquid interface react with dissolved impurities. PCD equipment has a relatively simple configuration, and with the reactor in an enclosed compartment, it is insensitive towards gas humidity and does not need the gas transport. In this thesis, PCD was used to study and evaluate the energy efficiency for degrading various organic compounds, as well as the chemistry of the oxidation products formed. The experiments investigate the aqueous oxidation of phenol, humic substances, pharmaceutical compounds (paracetamol, ibuprofen, indomethacin, salicylic acids, -estradiol), as well as lignin degradation and transformation to aldehydes. The study aims to establish the influence of initial concentration of the target pollutant, the pulsed discharge parameters, gas phase composition and the pH on the oxidation kinetics and the efficiency. Analytical methods to measure the concentrations of the target compounds and their by-products include HPLC, spectrophotometry, TOC and capillary electrophoresis. The results of the research included in this summary are presented in the attached publications and manuscripts accepted for publication. Pulsed corona discharge proved to be highly effective in oxidizing each of the target compounds, surpassing the closest competitor, conventional ozonation. The increase in oxidation efficiencies for some compounds in oxygen media and at lower pulse repetition frequencies shows a significant role of ozone. The role of the ·OH radicals was established in the surface reactions. The main oxidation products, formation of nitrates, and the lignin transformation were quantified. A compound specific approach is suggested for optimization of the PCD parameters that have the most significant impact on the oxidation energy efficiency because of the different characteristics and responses of the target compound to the oxidants, as well as different admixtures that are present in the wastewater. Further studies in the method’s safety (nitration and nitrosation of organic compounds, nitrite and nitrate formation enhancement) are needed for promoting the method.

Hiilidioksidin talteenoton mahdollistavat polttotekniikat

Kandidaatintyössä esitellään eri teknologioita hiilidioksidin talteenottamiseksi. Teknologioista esitellään niiden toimintaperiaate, pääpiirteet, heikkoudet ja vahvuudet, sekä nykytila. Työssä käsiteltiin kuutta teknologiaa: hiilidioksidin erotus polton jälkeen, hiilidioksidin erotus ennen polttoa, hiilidioksidin erotus happipoltolla, kemikaalikiertopoltto, kalsiumkiertoprosessi ja yhdistetty kolmen reaktorin kalsium- ja kemikaali kiertopolttoprosessia. Polton jälkeinen hiilidioksidin talteenotto sopii hyvin käytössä olevien laitoksien muuntamiseen niin kuin happipolttokin, mutta erotus ja talteenotto ennen polttoa ei sovellu kun vain uusiin laitoksiin. Kolme viimeisintä käsiteltyä teknologiaa ovat nuoria, kypsymättömiä, niissä paljon etuja ja niiden voi olettaa kehittyvän hyviksi teknologioiksi.

Video transcoding in a distributed cloud computing environment

Video transcoding refers to the process of converting a digital video from one format into another format. It is a compute-intensive operation. Therefore, transcoding of a large number of simultaneous video streams requires a large amount of computing resources. Moreover, to handle di erent load conditions in a cost-e cient manner, the video transcoding service should be dynamically scalable. Infrastructure as a Service Clouds currently offer computing resources, such as virtual machines, under the pay-per-use business model. Thus the IaaS Clouds can be leveraged to provide a coste cient, dynamically scalable video transcoding service. To use computing resources e ciently in a cloud computing environment, cost-e cient virtual machine provisioning is required to avoid overutilization and under-utilization of virtual machines. This thesis presents proactive virtual machine resource allocation and de-allocation algorithms for video transcoding in cloud computing. Since users' requests for videos may change at di erent times, a check is required to see if the current computing resources are adequate for the video requests. Therefore, the work on admission control is also provided. In addition to admission control, temporal resolution reduction is used to avoid jitters in a video. Furthermore, in a cloud computing environment such as Amazon EC2, the computing resources are more expensive as compared with the storage resources. Therefore, to avoid repetition of transcoding operations, a transcoded video needs to be stored for a certain time. To store all videos for the same amount of time is also not cost-e cient because popular transcoded videos have high access rate while unpopular transcoded videos are rarely accessed. This thesis provides a cost-e cient computation and storage trade-o strategy, which stores videos in the video repository as long as it is cost-e cient to store them. This thesis also proposes video segmentation strategies for bit rate reduction and spatial resolution reduction video transcoding. The evaluation of proposed strategies is performed using a message passing interface based video transcoder, which uses a coarse-grain parallel processing approach where video is segmented at group of pictures level.