Dissertationen zum Thema „Carbon dioxide (CO2)“

The average energy consumption of one ice rink is around 1000MWh/year, which approximately69% is occupied by the refrigeration unit and heating demand. With the aim of decreasing theenergy consumption, a new concept of refrigeration system with CO2 as a refrigerant has beendeveloped and it is promising to become a high potential next generation for refrigeration systemin ice rink.This thesis is to evaluate a new refrigerant application in ice rink refrigeration system underthree different aspects; energy performance, heat recovery potential and economic efficiency. Inorder to make this evaluation, three main tasks are executed. Firstly, literature review and marketstatistic are processed to give a general picture of the CO2 development as a refrigerant. Secondly, asoftware Pack Calculation II is used for the simulations of CO2 refrigeration system and traditionalice rink refrigeration system. Älta ice rink located in Sweden, is chosen as a reference case forsimulation’s input data. The simulation results is to compare these system in terms of energyperformance and heat recovery potential. Finally, life cycle cost of these systems is calculated toinvestigate the economic benefits from this new application.Results from this study show good benefits of the new CO2 application in ice rink. Fromthe market statistics, CO2 has become a successful refrigerant in supermarket food and beverageindustry with 1331 CO2 refrigeration system installed until 2011 in Europe (Shecco2012). In icerink industry, 24 ice rinks have been applied CO2 in the second cycle of refrigeration system; oneice rink in Canada applied a refrigeration system with only CO2 in the first cycle and the distributionsystem.From the simulation’s result, CO2 full system has been proven as the most efficiency sys-tem with the lowest energy consumption (30% lower than NH3/Brine system and 46% lower thanCO2/Brine system) and the highest COP (6.4 in comparison with 4.9 of NH3/Brine system and4.37 of CO2/Brine system). Regarding heat recovery potential, CO2 full system has highest energysaving in comparison with the other two systems.Due to lower energy cost and service cost, the life cycle cost of CO2 full system is loweraround 13% than the traditional NH3/Brine system, furthermore, the component cost of CO2 sys-tem is promising to decrease in the next years thanks to the rapid development of this market insupermarket industry.To conclude, CO2 full system has high potential to become a next generation of refrigerationsystem in ice rink, however, because of its transcritical working, this application can be restrictedin the regions of warm climate.

L'augmentation des émissions de dioxyde de carbone force l'implémentation de différentes stratégies de réduction des émissions de CO2 qui peuvent être divisées en deux groupes principaux: (i) Le captage du carbone et stockage (CCS) and (ii) le captage du carbone et utilisation (CCU). Un des procédés convertissant le CO2 en un produit à valeur ajoutée est le reformage à sec du méthane (DRM). Cependant le procédé de DRM n'a pas été commercialisé en raison de la forte endothermicité de la réaction et par manque de catalyseur actif, stable et bon marché à ce jour. Les matériaux possédant des propriétés bénéfiques pour la réaction de DRM et pouvant inclure les composants catalyseurs désirés à savoir Ni, MgO et Al2O3 sont les hydrotalcites. L'objectif principal de cette thèse est d'évaluer la performance catalytique de différents systèmes catalytiques à base d'hydrotalcite contenant du nickel lors de DRM. Cette thèse a été divisée en trois parties: (i) l'influence de l'introduction de nickel dans un système catalytique à base d'hydrotalcite, (ii) l'évaluation de la teneur en nickel des couches de brucite de l'hydrotalcite sur les propriétés catalytiques du matériau et (iii) l'évaluation de l'effet des promoteurs Ce et/ou Zr. Afin de répondre à ces problématiques, plusieurs catalyseurs à base d'hydrotalcite ont été synthétisés par la méthode de co-précipitation. Les propriétés physico-chimiques des matériaux préparés ont été évalués au moyen d'analyse élémentaire (XRF ou ICP-MS), XRD, FTIR, N2-sorption à basse température, H2-TPR, CO2-DPT, TEM, expériences SEM et TG. Les matériaux ont ensuite été testés dans la réaction de DRM à 550, 650 et 750°C
The growing emissions of carbon dioxide forced implementation of different CO2 emissions reduction strategies, which may be divided into two main groups: (i) carbon capture and storage (CCS) and (ii) carbon capture and utilization (CCU) technologies. The latter approach allows to recycle CO2. One of the processes that converts CO2 into added-value products is dry reforming of methane (DRM). The DRM process has not yet been commercialized due to the high endothermicity of the reaction and lack of cheap, active and stable catalysts.The materials which have beneficial properties in DRM reaction and may include desired catalysts components i.e. Ni, MgO and Al2O3 are hydrotalcites. The main goal of this PhD thesis was to evaluate catalytic performance of different hydrotalcite-based catalytic systems containing nickel in methane dry reforming process. This PhD was divided into three parts: (i) the comparison of the influence of nickel introduction into HTs-based catalytic system, (ii) the evaluation of wide range of nickel content in hydrotalcite brucite-like layers on materials catalytic properties and (iii) the evaluation of the effect of Ce and/or Zr promoters. In order to address these issues a number of different hydrotalcite-based catalysts was synthesized by co-precipitation. The physico-chemical properties of the prepared materials were evaluated by means of elemental analysis (XRF or ICP-MS), XRD, FTIR, low temperature N2 sorption, H2-TPR, CO2-TPD, TEM, SEM and TG experiments. The materials were subsequently tested in the DRM reaction. Most of catalytic tests were carried out at 550°C, but higher temperatures (650 and 750°C) were also studied

Silylated amines, also known as reversible ionic liquids (RevILs), have been designed and structurally modified by our group for potential use as solvents for CO₂ capture from flue gas. An ideal CO₂ capture ionic liquid should be able to selectively and reversibly capture CO₂ and have tolerance for other components in flue gas, including SO₂, NO₂, and O₂. In this project, we study the reactivity, selectivity, uptake capacity, and reversibility of RevILs in the presence of pure SO₂ and mixed gas streams tosimulate flue gas compositions. Tripropylsilylamine (TPSA), a candidate CO₂ capture RevIL, reacts with pure SO₂ to form an ionic liquid consisting of an ammonium group and a salfamate group, supported by IR and NMR results. The resulting IL with pure SO₂ partially reverses when heated to temperatures of upto 500 C in the TGA. TGA analysis of the ionic liquid formed from a 4 vol% SO₂ in CO₂ mixture indicates a possible reversal temperature in the 86-163 C range.

La utilització del diòxid de carboni com a substrat s'ha convertit en una estratègia popular des d'una perspectiva ambiental i econòmica per mitigar les emissions de CO2 a l'atmosfera i, al mateix temps, reduir la dependència del petroli per proporcionar substrats amb carboni. L'activació del diòxid de carboni és un procés complicat a causa de la seva estabilitat. El disseny de nous catalitzadors és una tasca complexa que requereix la combinació de tècniques experimentals i teòriques. Una d'aquestes és la modelització molecular, que permet descriure detalladament el sistema i comprendre com es comporta, o com té lloc un mecanisme de reacció. La combinació de dos factors, com l'augment de la potència computacional i la millora de l'eficiència dels algoritmes, ens permet estudiar grans sistemes amb un nivell raonable de precisió, imitar les condicions experimentals i, en conseqüència, obtenir informació crucial. En aquesta Tesi estudiem computacionalment diverses reaccions on es fa servir diòxid de carboni com a substrat. Descrivim detalladament el mecanisme de reacció tenint en compte els resultats experimentals proporcionats pels nostres col·laboradors. Els nostres resultats contribueixen a entendre millor com funcionen les reaccions de fixació de CO2 i, en conseqüència, pot ajudar al disseny racional de nous i més actius catalitzadors per a reaccions que involucren CO2 o substrats similars.
La utilización del dióxido de carbono como sustrato se ha convertido en una popular estrategia desde una perspectiva ambiental y económica para mitigar las emisiones de CO2 a la atmósfera y, al mismo tiempo, reducir la dependencia del petróleo para proporcionar sustratos con carbono. La activación del dióxido de carbono es un proceso complicado debido a su estabilidad. El diseño de nuevos catalizadores es una tarea compleja que requiere la combinación de técnicas experimentales y teóricas. Una de estas es la modelización molecular, que permite describir detalladamente el sistema y comprender cómo se comporta, o cómo tiene lugar un mecanismo de reacción. La combinación de dos factores, como el aumento de la potencia computacional y la mejora de la eficiencia de los algoritmos, nos permite estudiar grandes sistemas con un nivel razonable de precisión, imitar las condiciones experimentales y, en consecuencia, obtener información crucial. En esta Tesis estudiamos computacionalmente varias reacciones en las que se usa dióxido de carbono como sustrato. Describimos detalladamente el mecanismo de reacción teniendo en cuenta los resultados experimentales proporcionados por nuestros colaboradores. Nuestros resultados contribuyen a comprender mejor cómo funcionan las reacciones de fijación de CO2 y, en consecuencia, puede ayudar en el diseño racional de nuevos y más activos catalizadores para reacciones que involucran CO2 o sustratos similares.
The utilization of carbon dioxide as chemical substrate has become a popular strategy from an environmental and economic perspective to mitigate CO2 emissions to the atmosphere and, at the same time, reduce the petroleum dependency to provide carbon based substrates. The activation of carbon dioxide is not a straightforward process. The design of new catalysts is a complex task that requires the combination of several experimental and theoretical techniques. One of the most relevant is molecular modelling, which allow to describe the system in detail and to understand how the system behaves or how a reaction mechanism takes place. Nowadays, the combination of two factors, being the increase of the computational power and the improved efficiency of the theoretical algorithms, enable computational chemists to study large systems at a reasonable level of accuracy, to mimic the experimental conditions, and consequently, obtain crucial information on the studied system. In this Thesis we studied computationally several reactions where carbon dioxide was used as substrate. We described in detail the reaction mechanism for all cases, taking into consideration the experimental results provided by our collaborators. The results collected in this Thesis contribute to understand better how important CO2 fixation reactions work and consequently, these results may help in the rational design of new and more active catalysts for this type of reactions involving CO2 or substrates of similar properties.

Atmospheric concentrations of carbon dioxide (CO2) are significantly increasing since the industrial revolution at an accelerating rate causing environmental impact such as global warming and climate change. Projections indicate that CO2 concentrations will continue to rise to unsustainable levels. This highlights the scale of the challenge our scientists are facing in order to reduce CO2 emissions and underpins the importance of promoting green process engineering for the utilisation of CO2 as a valuable commodity in the process industry. The transformation of CO2 to value-added chemicals such as organic carbonates provides a promising technological advancement aimed at reducing CO2 atmospheric concentrations to sustainable levels. Dimethyl carbonate (DMC) is a promising green compound that exhibits versatile and excellent chemical properties and therefore finds applications as an intermediate in the chemical and pharmaceutical industries. DMC has a high oxygen content and can be used as an oxygenate additive to gasoline to improve its performance and reduce exhaust emission. The conventional method for DMC synthesis involves the utilisation of phosgene as a toxic feedstock. Thus, greener and more sustainable synthetic processes for the synthesis of DMC are required. Recently, non-toxic synthetic routes have been explored; these include, oxidative carbonylation of carbon monoxide (CO), oxygen (O2) and MeOH, direct synthesis from MeOH and CO2 and the transesterification of cyclic carbonates and methanol (MeOH). The oxidative carbonylation route suffers from the use of expensive raw materials and corrosive reagents as well as being hazardous due to the explosive potential of CO. The direct production of DMC from MeOH and CO2 offers an attractive and green synthetic route for DMC synthesis. Also, the synthesis of DMC via the transesterification of cyclic carbonates and MeOH, where cyclic carbonates can be synthesised from their corresponding epoxides and CO2, makes the synthesis of DMC via transesterification route more environmentally friendly and desirable in terms of green chemistry and sustainable development. Therefore, in this research new greener catalytic processes for DMC synthesis via addition of MeOH to CO2 route and transesterification route have been explored. In this work, several commercially available heterogeneous catalysts such as ceria and lanthana doped zirconia (Ce–La–Zr–O), ceria doped zirconia (Ce–Zr– O), lanthana doped zirconia (La–Zr–O), lanthanum oxide (La–O) and zirconium oxide (Zr–O) have been extensively assessed for the synthesis of DMC. Strongly coupled graphene based inorganic nanocomposites represent an exciting and new class of functional materials and therefore the utilisation of graphene oxide (GO) as a suitable support for metal oxide catalysts has been explored. Ceria doped zirconia graphene nanocomposites (Ce–Zr/GO) have been synthesised using conventional wet impregnation methods. Samples of Ce–Zr/GO have been subjected to heat treatment at various temperatures (773 K, 873 K, 973 K and 1073 K) in an attempt to enhance their catalytic performance. As-prepared Ce– Zr/GO sample and the corresponding heat treated samples have been assessed for the direct synthesis for DMC from MeOH and CO2. Furthermore, a new innovative approach has been employed for synthesising advanced, highly efficient and active heterogeneous catalysts via utilisation of a continuous hydrothermal flow synthesis (CHFS) reactor. Tin doped zirconium oxide (Zr–Sn– O) and tin doped zirconia/graphene nanocomposite (Zr–Sn/GO) have been assessed as suitable heterogeneous catalysts for the synthesis of DMC via the transesterification route. The catalysts were characterised using various analytical techniques such as scanning electron microscopy (SEM), transmission electron microscopy (TEM), powder X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), Raman spectroscopy and Brunauer-Emmett-Teller (BET) surface area measurement. A heterogeneous catalytic process for the synthesis of DMC has been investigated using a high pressure reactor. The effect of various reaction parameters such as the reactant molar ratio, catalyst loading, reaction temperature, CO2 pressure, reaction time and the use of a dehydrating agent was studied for the optimisation of DMC synthesis. Reusability studies were conducted to evaluate the long term stability of the heterogeneous catalysts by recycling and reusing the catalyst several times for the synthesis of DMC. Tin doped zirconia graphene oxide (Sn–Zr/GO) nanocomposite catalyst has been found to be the best performed catalyst for the synthesis of DMC as compared to other catalysts evaluated in this research work. This can be attributed to the phase composition and crystallinity of the catalyst along with the defects on the graphene sheet such as, holes, acid/basic groups and presence of residual which can provide additional active catalytic sites. Catalyst reusability studies evidently showed that Sn–Zr/GO nanocomposite can be easily recovered and reused without any significant reduction in the catalytic performance. Response Surface Methodology (RSM) has track record in helping researchers in modeling and optimisation of the experimental design for various applications in food industry, catalysis and chemical reaction engineering. Therefore, it has been employed to evaluate the relationship between multiple process variables in order to optimise a specified response (i.e. yield of DMC). RSM using Box-Behneken design (BBD) was carried out for process modeling and optimisation, with an aim to better understand the relationship between five operating variables (i.e. MeOH:PC molar ratio, catalyst loading (w/w), reaction temperature, reaction time and stirring speed) and their impact on the yield of DMC. A model for the synthesis of DMC by transesterification of PC and MeOH has been developed using BBD to compare the experimental data and the predicted results by the BBD model. Furthermore, regression analysis was applied to establish the optimum reaction conditions for a maximising DMC synthesis. The BBD model predicted values are in good agreement with the experimental results.

In order to combat climate change there is a need to achieve negative emissions. Bio-energy with carbon capture and storage (BECCS) is a promising technology that offers the possibility to remove carbon dioxide (CO2) emissions from the atmosphere. However, this also implies that the BECCS process needs to store more CO2 than it emits. The purpose of this study is to examine the liquefaction, intermediate storage, transportation and long term storage of CO2 and evaluate the climate impact of the energy use and the leakage of CO2. This thesis is based on data collected through an extensive literature study and several interviews that were performed with relevant actors and informants. A key finding in this thesis is that the energy use through the examined steps of BECCS is responsible for the bulk of the CO2 emissions. Liquefaction and the transportation plays an essential role as it has the highest energy usage. Unfortunately the energy use of injecting CO2 into the geological formation remains unknown because of lack of data. The leakages found throughout the process were often negligible or even zero. However the leakages from injecting CO2 through pipeline and the CO2 leakage from long term storage was found to be of some significance. The total BECCS related carbon dioxide equivalent (CO2e) emissions, are summarised in three scenarios ranging from approximately 49-58 kg CO2e per stored tonne of CO2. In these scenario calculations, some assumptions have had to be made. In order to evaluate the true and total environmental impact of BECCS, further research will be needed.
Dagens samhälle står inför avsevärda miljömässiga utmaningar, inte minst då mängden växthusgaser (GHG) i atmosfären kommer behöva reduceras drastiskt för att undvika två graders uppvärmning. Bio-energy with carbon capture and storage (BECCS) är en teknologi med potential att avlägsna koldioxid (CO2) inte bara från nya utsläpp, utan även i bästa fall från atmosfären. I det specifika fall som denna rapport tittar närmare på, förbränns biomassa för att skapa fjärrvärme, men istället för att CO2 släpps ut i luften så fångas den upp och komprimeras till flytande form. Därefter kan CO2 transporteras till en injektionsanläggning för att slutligen pumpas ner i en geologiskt lämplig berggrund. Denna process kan resultera i negativa utsläpp om mer CO2 lagras än vad processen skapar och släpper ut. Målet med detta kandidatexamensarbete är att undersöka energianvändningen och läckaget av CO2 under förvätskningen, den kortsiktiga lagringen, transporten samt den långsiktiga lagringen av CO2. Kandidatexamensarbetet är framförallt baserat på data insamlad i form av en litteraturstudie. Denna data har även kompletterats med data från flertalet intervjuer med forskare och anställda på företag som arbetar med BECCS. Flera antaganden har varit nödvändiga då det i dagsläget finns en brist på information angående energianvändningen och läckaget av CO2 i processens delsteg. Energianvändningen för injektionen av CO2 förblir okänd då det inte fanns någon relevant information att tillgå. Då läckaget visade sig vara försumbart eller noll i flera delsteg, utgör energianvändningen en signifikant andel av de totala utsläppen. De största utsläppen av CO2 inom ramen för BECCS processen orsakas därför av förvätskningsprocessen och transporten av CO2 då dessa delar är mest energikrävande. Resultatet av kandidatexamensarbetet kan sammanfattas i tre scenarion, ett lågt scenario, ett median scenario och ett högt scenario. Slutsatsen var att samtliga inkluderade steg av BECCS resulterar i ett utsläpp mellan 49-58 kg koldioxidekvivalenter (CO2e) per ton CO2 som lagras. För att kunna kvantifiera den totala klimatpåverkan av BECCS finns ett behov av ytterligare studier som tar hänsyn till alla delsteg under processen.

In order utilise geological carbon dioxide storage (GCS) at an industrial scale predictions of reservoir scale behaviour, both chemical and physical must be made. In order to ground-truth the geochemical data underlying such predictions, laboratory experiments at temperatures and CO2 pressures relevant to GCS are essential. Mineral dissolution rate, CO2 solubility and pH data has been collected from batch experiments carried out on quartz, K-feldspar, albite, calcite, dolomite and Sherwood Sandstone materials. These experiments were designed to assess the influence of a variety of factors on dissolution rates: changes in grain size from 125μm - 180μm to 500μm - 600μm; changes in fluid composition from deionised water to 1.36M NaCl solution; changes in CO2 pressure from 4 bar to 31 bar; changes in temperature from 22°C to 70°C. Experiments carried out on the Sherwood Sandstone material also included work on consolidated rock, rather than the powder used in other experiments. Calculated dissolution rates for silicates were found to agree well with values calculated from literature-sourced dissolution equations and the USGS-produced general rate equation (USGS 2004) was found to be suitable for predicting these rates. Calculated dissolution rates for the carbonate minerals was found to be strongly retarded due to transport effects, with literature-sourced equations significantly over-predicting dissolution rates. Dissolution of the sandstone material was found to be dominated by K-feldspar and dolomite dissolution, rates of which compare favourably with those obtained from the single mineral experiments. A significant increase in porosity was observed in the core flow-through experiment, associated with dolomite dissolution. Several experiments were carried out using a Hele-Shaw cell in order to visualise the formation and migration of density plumes which form as CO2 dissolved into unsaturated fluids. Introduction of NaCl and decreases in permeability were found to significantly retard migration of CO2 saturated fluid, while minor heterogeneities in the cells served to focus and accelerate plume movement. Modelling work suggests that predictive models currently underestimate the rapidity of formation and migration of these plumes.

With the emission of carbon dioxide (CO2) becoming an international worry due its role in climate change, solutions such as CO2 capture and storage technologies are needed to decrease the emissions. The main proportion of CO2 gas emissions is from fossil fuel combustion in a range of industries, including power generation. To develop the CO2 capture system for these operations, new materials are needed for CO2 capture. Metal-organic framework (MOF) materials have porous crystal structures containing organic molecules (organic ligands) linked to each other by metalcontaining nodes. The large internal surface area can be exploited for the adsorption of small gas molecules, and for this reason MOFs may be ideal candidate materials for CO2 capture and gas separations. Thousands of MOF materials have been reported, with different combinations of the ligands and metals and with the capability of forming many different network topologies. Experimentally it is very difficult to study the gas absorption dynamics, interaction and gas adsorption capacity for the large number of materials. This problem can be solved by simulations. The aim of the thesis is to develop a systematic simulation method to screen the MOF properties and CO2 adsorption capacity and interaction dynamics at different environment. The molecular dynamics (MD) method with parameterised force fields was used to study the interactions between CO2 molecules and one class of the MOFs, zeolitic imidizolate frameworks (ZIFs) with zinc as the metal cation. To develop the model, the atom charges have been developed by using the distributed multipole analysis (DMA) method based on ab initio DFT calculations for molecules and clusters. The intermolecular forces were developed by fitting against the MP2 calculations of small clusters of the metal cations and molecular ligands. In order to evaluate the models I simulated the gas-liquid coexistence curve of CO2 and showed that it is consistent with experiments. I also simulated the pure ZIF structures on changing both temperature and pressure, demonstrating the stabilities of the structures but also showing the existence of displacive phase transitions. I have used this approach to successfully study CO2 absorption in a number of ZIFs (from ZIF-zni, ZIF-2, ZIF-4, ZIF-8 and ZIF-10) using MD. The gas absorption capacity and dynamics have been investigated under 25 bar and 30 bar, 200 , showing a promising uptake of CO2. The results have shown that CO2 capacity is mainly determined by the pore sizes and pore surfaces, in which a higher capacity is associated with a higher pore surface. The intermolecular distance of CO2 inside the pores and channels have been investigated in the saturation state. It has been shown that the distance is approximately 4 Å. The attraction force is from the interaction between CO2 and the imidazolate ligands. In addition, the systematic studies of the saturated ZIF system gave the minimum diameters for CO2 adsorption which is approximately 4.4 Å. This interaction has caused the gate opening effects, with the imidazolate ligands being pushed to be parallel to the CO2 molecules and opening up to allow more gas molecules go through the channels that connect the pore structures. This gate opening effect also explains the phase transition in ZIF-10 caused by CO2 molecules in our simulation, and can be applied to predict phase transitions in other materials with similar structure such as ZIF-7 and ZIF-8. The dynamics have also shown that the gas diffusion velocity is determined by the pore structure as well and by the accumulated layers of CO2 on the surface prior to being pushed in toward the centre of the material layer by layer. The de-absorption processes have also been studied in these materials by decreasing the pressure from 25 bar to 1 bar under at same temperature. The results indicate that the de-absorption is a reverse process of absorption. The structure of ZIF-10 went through a phase transition induced by CO2 recovered after the guest molecules had been released. The de-absorption can be accelerated by increasing the temperature.

Thesis (Ph.D)--Chemical Engineering, Georgia Institute of Technology, 2008.
Committee Chair: Dr. Charles A. Eckert; Committee Co-Chair: Dr. Charles L. Liotta; Committee Member: Dr. Amyn Teja; Committee Member: Dr. Dennis W. Hess; Committee Member: Dr. Victor Breedveld.

This project aims at investigating the effect of CO2 enrichment on the growth and gas exchange of C3, C3-C4 and C4 Panicum grasses. Potted plants were grown in soil under well watered conditions, in artificially lit environmentally controlled cabinets or naturally lit greenhouses at varying levels of CO2 enrichment. CO2 enrichment enhanced the dry weight of C3 and C4 Panicum species under optimal light and N supplies, but had no effect on the total leaf N or TNC concentrations. The high-CO2 induced photosynthetic reaction in the C3 species was accompanied by a reduced Rubisco concentration and was related to the conservation of the relative growth rate of the plant. Elevated CO2 had no effect on the photosynthetic capacity of the C4 species, but enhanced its CO2 assimilation rates under high light and N supplies. The effect of elevated CO2 on the leaf and stem anatomy reflected increased carbon supply at high CO2 in the C3 grass, and reduced transpiratory demand at high CO2 in C4 grasses. Consequently, it is clear that both C3 and C4 grasses are likely to be more productive under rising atmospheric CO2 concentrations.
Doctor of Philosophy (PhD)

Today’s society strives to eliminate the carbon dioxide (CO2) emissions, which is the main greenhouse gas emitted through anthropogenic activities and contributes to climate change. In this project utilization of CO2 emissions from waste to energy plants to carbohydrates via photocatalytic reduction with water and further carbon coupling reactions is investigated. Two routes for the synthesis of carbohydrates have been investigated. Both methods use photocatalytic reduction of carbon dioxide to methanol and then proceed via different steps to produce carbohydrates or their precursors. The first route uses aldol condensation as the main method for the formation of carbon-carbon bonds and the second route is based on the formose reaction that uses formaldehyde as a reactant. The waste incineration plant selected for this study was the one located in Kil, Sweden. This plant processes 15590 tons of waste per year and emits 16366.5 tons of carbon dioxide per year. In order to separate carbon dioxide from the flue gas stream, MEA absorption was chosen as the best option due to its high efficiency. The presented processes have negative carbon dioxide emissions due to the fact that they convert of 16.4% of the waste incineration CO2 emissions into useful products and do not generate any emissions of their own. The aldol condensation pathway exhibits an efficiency of 1.3% when considering only food industry products and 2.5% when including other products that are useful to manufacture solvents, lubricants, or pharmaceuticals. The total amount of food industry products obtained is 3.9 kg/h with the energy requirements being was 159550 kJ/kgproduct. The formose reaction route yields 15.4 kg/h of only food industry products, mainly glucose, and exhibits an efficiency of 5%. The power requirements equal to 90099 kJ/kgproduct. The formose route was found to have higher yield and efficiency, and to be more energy consuming but also more energy efficient. Economic data was difficult to find due to the fact that photocatalytic processes are not commercial yet.
Dagens samhälle strävar efter att eliminera koldioxidutsläppen (CO2), som är den viktigaste växthusgasen som släpps ut genom antropogena aktiviteter och påverkar klimat. Den här projekten undersöker användning av koldioxidutsläpp från avfall till energianläggningar till produktion av kolhydrater via fotokatalytisk reduktion med vatten och ytterligare kolkopplingsreaktioner. Projekten utforskar två vägar för syntes av kolhydrater. Båda metoderna använda fotokatalytisk reduktion av koldioxid till metanol. Kolhydrater eller deras ursprungsmaterial syntetiseras via olika steg nedströms den fotokatalitiska processen. Den första vägen använder aldolkondensation som huvudmetod av kol-kolbindningar och den andra vägen baseras på formosreaktionen som använder formaldehyd som reaktant. Den avfallsförbränningsanläggning som valts ut för denna studie var den i Kil, Värmland, Sverige. Denna anläggning behandlar 15590 ton avfall per år och släpper ut 16366,5 ton koldioxid per år. För att separera koldioxid från rökgasströmmen valdes MEA-absorption som det bästa alternativet på grund av dess höga effektivitet. De presenterade processerna har negativa koldioxidutsläpp på grund av att de omvandlar 16,4% av koldioxid från avfallsförbränning till användbara produkter och inte genererar  egna utsläpp. Aldolkondensationsvägen uppvisar en effektivitet på 1,3% om man endast beaktar livsmedelsindustrins produkter och 2,5% om man gör andra produkter som är användbara för att tillverka lösningsmedel, smörjmedel eller läkemedel. Den totala mängden av livsmedelsprodukter är 3,9 kg / h och energibehovet är lika med 159550 kJ / kg produkt. Formosreaktionsvägen ger 15,4 kg / h av livsmedelsindustrin produkt, huvudsakligen glukos, och uppvisar en effektivitet på 5%. Effektkraven är lika med 90099 kJ / kg produkt. Formosvägen visade sig ha högre utbyte och effektivitet och vara mer energikrävande men också mer energieffektiv. Ekonomiska data var svåra att hitta på grund av att fotokatalytiska processorn ännu inte är kommersiell.

Carbon Capture and Storage (CCS) technology could help reduce anthropogenic CO2 emissions to the atmosphere. So far, CCS has failed to attract government support in the UK due to high costs of implementation. The broad deployment of CO2-EOR could aid the development of CCS by providing additional revenue streams for investors. The success of the CO2- EOR in the United States has raised the question of whether this success could be replicated in the UKCS. This thesis answers these questions by introducing two distinct models, which analyse the similarities and differences between the two oil provinces from the subsurface and economic perspectives. The first model integrates into the economic framework the behaviour of oil and CO2 in a reservoir. The model is applied to an oil field in the North Sea. It analyses whether the screening criteria developed based on the onshore US experience to screen for oil field candidates for the CO2 would be suitable for the oil fields in the UKCS. The second model is a theoretical CO2-EOR with storage model, which analyses how the inclusion of permanent storage changes the economics of CO2-EOR. The CO2-EOR with storage model allows for an endogenous switching point between the CO2-EOR and the permanent CO2 storage phase depending on the various economic factors, such as oil prices, sequestration subsidies and fees, CO2 price, and oil and gas tax rates. The CO2-EOR with storage model shows different behaviour compared to the case without permanent storage. On the policy level, the main difference between the two countries revealed that the UK strongly focuses on cutting CO2 emissions while the U.S. on boosting domestic oil production. Therefore, the third study in this thesis investigates the net carbon footprint of the CO2-EOR activity in the North Sea.

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Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)
Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)
O presente estudo avaliou a reação do tecido conjuntivo irradiado com os lasers de CO2 e de Er:YAG em feridas confeccionadas no dorso de ratos. Foram confeccionadas 2 feridas no dorso de 30 ratos com um punch de 3mm de diâmetro. Os animais foram divididos em três grupos de 10: no Grupo I as feridas foram irradiadas com o laser de CO2, l 10,6 mm, (1,5 W -50 Hz); no Grupo II as feridas foram irradiadas com o laser de Er:YAG, l 2,94 mm (300 mJ -10 Hz), tempo de irradiação de 23 segundos em ambos os grupos; e no grupo III as feridas não foram submetidas à irradiação. Após o ato operatório, todas as feridas foram forradas com MTA. Os animais foram mortos em períodos de 1 dia e 7 dias e as peças removidas, processadas, coradas com hematoxilina / eosina e analisadas no microscópio óptico. Aos 7 dias, no grupo do Er:YAG foi observada a presença de tecido de granulação, porém no grupo do CO2 ainda houve uma severa reação inflamatória com áreas de necrose tecidual. No grupo controle não houve inflamação aos 7 dias na maioria dos casos. Conclusão: os resultados obtidos no presente estudo nos permitem afirmar que o tecido conjuntivo reagiu de forma mais favorável à irradiação laser de Er:YAG do que à irradiação do laser de CO2, independentemente do tempo pós-operatório.
The present study assesed the connective tissue reaction after irradiation with CO2 and Er:YAG lasers in in the back of rats. Two wounds were practiced in the back of tirthy rats with a 3mm diameter punch. The animals were divided into three groups of ten specimens each: In Group I the wounds were irradiated with a CO2 laser, l 10,6mm, (1,5 W -50 Hz) ; In Group II the wounds were irradiated with a Er:YAG laser, l 2,94m, (300 mJ -10 Hz), in both groups the irradiation time was of 23 seconds; Group III received no irradiation. After the intervention, all wounds were covered with MTA. The specimens were killed after intervals of 1 to 7 days and samples collected, proccesed and stained with hematoxilin/eosin, and analized under the ligth microscope. At seven days period the Er:YAG group exhibited granulation tissue proliferation, while in the CO2 group a severe inflamatory reaction persisted with areas of necrosis. In the control group there was no inflamation in most of the cases after 7 days period. Conclusions: The results yielded by the present study lead us to assure that the reaction of the connective tissue was most favorable to irradiation with Er:YAG laser than with CO2 laser, regardless the time elapsed after the intervention.

S’han dut a terme estudis teòrics amb la finalitat d’avaluar mecanismes de reacció per a processos de fixació de CO2, catalitzats per complexos de metalls de transició. D’aquesta forma, s’han descrit detalladament els passos del mecanisme de reacció (reaccions d’opertura d’anell, inserció de CO2 i tancament de l’anell) per la formació de carbonats cíclics a partir de CO2 i diferents epòxids, sota l’acció catalítica de complexos de Zn(salen), conjuntament amb Nbu4X (X = I, Br). Les energies d’activació calculades DFT calculationsmitjançant DFT són qualitatives, seguint la línea dels resultats experimentals. Per altra banda, es va considerar un catalitzador d’alumini realment actiu per estudiar aquesta reacció però des d’un punt de vista quantitatiu. D’aquesta forma, es va examinar l’activitat del sistema catalític mitjançant el càlcul teòric de les freqüències de repetició (TOFs). Els resultats obtinguts es varen trobar en el mateix ordre de magnitud que en el cas dels experiments. L’últim mecanimse estudiat involucra la eracció de copolimerització entre CO2 i òxid de ciclohexè, catalitzat per un sistema binari format per l’esmentat complex d’alumini i NBu4I. Es van suposar tres possibles rutes per descriure la reacció depenent del nombre de catalitzadors involucrats en la reacció de propagació. Els resultats sugereixen que la copolimerització alternada és més favorable respecte la formació de carbonat cíclic. A més dels estudis anteriors, es van utilitzar mètodes d’espectrometria de masses de mobilitat d’ions (IM-MS) per a proporcionar informació estructural sobre una sèrie de complexos de metalls de transició involucrats en catàlisi homogènia. Es varen determinar les seccions eficaces de col•lisió (CCS) teòriques i es van ser comparades amb les resultants dels experiments de IM-MS. El resultat obtingut concordava perfectament entre ambdues metodologies.
Se han llevado a cabo estudios teóricos con el fin de evaluar mecanismos de reacción para procesos de fijación de CO2 catalizados por complejos de metales de transición. De este modo, se describieron detalladamente los pasos del mecanismo de reacción (reacciones de apertura de anillo, de inserción de CO2 y de cierre de anillo) para la formación catalítica de carbonatos cíclicos a partir de CO2 y diferentes epóxidos, basada en complejos de Zn(salen), conjuntamente con NBu4X (X = I, Br). Se encontró que las energías de activación DFT calculadas están de manera cualitativa en línea con los resultados experimentales. Por otra parte, se consideró un catalizador de aluminio altamente activo para estudiar la misma reacción, pero desde un punto de vista cuantitativo. Así pues, se examinó la actividad del sistema catalizador mediante el cálculo teórico de las frecuencias de repetición (TOFs). Estas últimas resultaron en el mismo orden de magnitud que los experimentos. El último de los mecanismos estudiados aquí involucra la reacción de copolimerización entre CO2 y óxido de ciclohexeno catalizada por el sistema binario compuesto por dicho complejo de aluminio y NBu4I. Se encontraron tres posibles rutas para describir la reacción dependiendo el número de catalizadores involucrados en la reacción de propagación. Los resultados sugieren que la copolimerización alternada es más favorable con respecto a la formación del carbonato cíclico. Además de los estudios anteriores, se usaron métodos de espectrometría de masas de movilidad iónica (IM-MS) para proporcionar información estructural sobre una serie de complejos de metales de transición involucrados en catálisis homogénea. Se determinaron las secciones eficaces de colisión (CCS) teóricas y se compararon con las resultantes de los experimentos IM-MS. Se encontró un excelente acuerdo entre el resultado de ambas metodologías.
Theoretical studies have been conducted in order to evaluate reaction mechanisms for CO2 fixation processes catalyzed by transition metal complexes. Thus, detailed mechanistic steps (ring-opening, CO2 insertion and ring-closing reactions) were described for the catalytic formation of cyclic carbonates from CO2 and a series of epoxides based on Zn(salen) complexes, in conjunction with NBu4X(X=I, Br). The computed DFT activation energies were found to be qualitatively in line with the experimental findings. Moreover, a highly active Al catalyst (derived from amino triphenolate ligands) was considered to study the same reaction, but from a quantitative point of view. In light of this, the activity of this catalyst system was examined by means of the theoretical calculation of frequencies (TOFs). The latter resulted in the same order of magnitude as the experiments. The last mechanism studied here comprises the copolymerization reaction between CO2 and cyclohexene oxide mediated by the binary system composed of the aforementioned Al complex species and NBu4I. Three possible pathways were found to describe the reaction depending on the number of Al complexes involved in the propagation step. Results suggest that the alternating copolymerization should be the most favorable pathway over the formation of the five-membered cyclic carbonate product. In addition to the above studies, methods of ion mobility mass spectrometry (IM-MS) have been employed to provide structural information on a series of transition metal complexes involved in homogeneous catalysis. Theoretical collision cross sections (CCSs) were determined and compared with those resulting from IM-MS experiments. The outcome from both methodologies yielded excellent agreement.

A cleaner use of fossil fuels supported by Carbon Capture and Storage (CCS) techniques is considered to be one of the main short-term strategies for addressing the global climate change problem. However, potential CO2 or CO2/SO2 seepage during some of the phases of a CCS project not only reduces its performing efficiency, but also impacts the local environment, which could have further impacts on human health. It is therefore essential to assess the potential risks and provide evidence that the impacts are well understood. Moreover, studying the effects of CO2 leakage is useful for identifying monitoring parameters if the leakage does happen, leading to the development of new approaches in detecting CO2 leaks. Accordingly, this research is carried out to assess the relevant impacts on the local environment of CO2 leakage, focusing on the environmental impacts caused by CO2 seepage associated with various soil types, mostly on the soil geochemical changes, which is currently lacked. As a cost effective approach, this research was carried out with two types of well controlled laboratory experiments: Stage I- Closed reactor experiments and Stage II- A flow through column system (designed by the author). As a supplementary study to the research of the ASGARD site, Stage I experiments were carried out with soil samples collected from the ASGARD site and gave directions for Stage II column system design. Stage II experiments were carried out with two contrasting mono-mineral sediments considering sensitivity to CO2 gas, Trucal 5 and Trucal 6 (limestone sand of different particle size) and silica sand. Certain limitations of this research have to be considered. Firstly, highly idealised samples were used in the experiments instead of true soils and there was no heterogeneity in the samples used, which is not representative of the full complexity of a natural system. Secondly, the scale limitation of the laboratory work would lead to a higher gas/mineral ratio compared with field conditions. Therefore, results from the laboratory work cannot simply represent all the soils in the field, except the specific soil related problem and the results are better to be used to demonstrate the conditions where the soils/sediments are surrounded by high levels of CO2, such as the ones nearby a leaking injection well or along a fracture/fault. Nevertheless, this study is believed to provide a step towards understanding the potential impacts of CO2 seepage in soil, and potentially to be useful as a mean of identifying indicators of related problems when applying to the full-scale design, leading to the development of new approaches in detecting CO2 leaks. Throughout the experiments, the experimental apparatus (the continuous column system) newly designed by the author was run successfully, providing an alternative way in respect to the majority of soil-column studies for assessing issues of CO2 seepage. The main impact of CO2 emissions on soil properties is to drop the pH which triggers metals mobilisation from soils (all within safety limits to plant growth). The change of pH associated with both limestone and silica sand indicates that pH is an excellent parameter to indicate the CO2 intrusion into sediments once the background is set. The response of calcium (Ca) to CO2 flux highlights that carbonate minerals are sensitive to CO2 increase and could possibly be used as a parameter to monitor CO2 leakage once the baseline for the pre-injection concentration is set.

CoordenaÃÃo de AperfeÃoamento de Pessoal de NÃvel Superior
Adsorption processes involving carbon dioxide (CO2) capture and sequestration have been objects of different studies. A typical problem is the separation of CO2 from fuel gases emitted in power plants in order to mitigate the global warming effects. Recently, Pressure Swing Adsorption (PSA) technology is being applied to this separation. However, design and analysis of adsorption processes are a difficult task due to the large number of parameters involved. This work studies the dynamics of this separation in activated carbons C141 and WV 1050 through commercial software Aspen Adsorption (AspenTechÂ). First, we evaluated the ability of the software reproducing experimental fixed bed data in C141 reported on literature, considering the mixture 10% of helium (carrier gas), 15% dioxide carbon and 75% nitrogen, molar basis. The results showed satisfactory resemblance to the literature. From a scale-up of the analyzed system, it was sized a PSA apparatus at 298 K operating with two columns and four steps: adsorption, depressurization, purge and repressurization (Skarstrom cycle). High-pressure step was at 3.0 bar and regeneration at 1.1 bar. Fuel gas mixture simulated was composed only of CO2 and N2; the molar fraction of the first component at the feed stream was 15%. The product stream in C141 showed purity and recovery of carbon dioxide from approximately 23% and 60% on a molar basis, respectively. The productivity was 0.72 t CO2 kg-1 year-1. Through the study of design variables such as column diameter and length, feed and purge flow rate, feed composition and step times, the product purity exceeded 30 % and the recovery bordered 75%, with maximum productivity of 1.02 t CO2 kg-1 year-1 for some process settings. The process yields in WV 1050 were 26.5 % purity, 47 % recovery and 0.53 t CO2 kg-1 year-1.
Processos de adsorÃÃo envolvendo a captura e o sequestro de diÃxido de carbono (CO2) vÃm sendo objetos de diferentes estudos. Um dos problemas tÃpicos analisados à a separaÃÃo do CO2 a partir dos gases de queima emitidos em plantas energÃticas com o intuito de mitigar os efeitos do aquecimento global. Recentemente, a tecnologia Pressure Swing Adsorption (PSA) està sendo aplicada para este tipo de separaÃÃo. Entretanto, o projeto e a anÃlise de processos de adsorÃÃo sÃo uma tarefa difÃcil devido à grande quantidade de parÃmetros envolvidos. Este trabalho estuda a dinÃmica dessa separaÃÃo nos carbonos ativados C141 e WV 1050 atravÃs do software comercial Aspen Adsorption da AspenTechÂ. Inicialmente, foi avaliada a capacidade do software no que diz respeito à reproduÃÃo de dados experimentais de leito fixo reportados na literatura, que consideram a mistura como sendo, em base molar, 10 % de hÃlio (gÃs de inerte), 15 % de diÃxido de carbono e 75 % de nitrogÃnio. Os resultados obtidos apresentaram semelhanÃa satisfatÃria aos da literatura para o sÃlido C141. A partir de um scale-up desse sistema analisado, foi dimensionada uma PSA a 298 K de duas colunas e quatro passos: adsorÃÃo, despressurizaÃÃo, purga e repressurizaÃÃo (ciclo Skarstrom). A etapa de maior pressÃo ocorre a 3,0 bar e a regeneraÃÃo a 1,1 bar. Considerou-se que o gÃs de queima à composto apenas por CO2 e N2, sendo a fraÃÃo molar de alimentaÃÃo do componente de interesse de 15%. Para C141, a corrente de produto apresentou pureza e recuperaÃÃo de diÃxido de carbono de aproximadamente 23 % e 60 % em base molar, respectivamente, com produtividade de 0,72 t CO2 kg-1 ano-1. AtravÃs do estudo de variÃveis de projeto como diÃmetro e comprimento da coluna, vazÃo de alimentaÃÃo e de purga, composiÃÃo de alimentaÃÃo e tempos das etapas do ciclo, a pureza do produto ultrapassou os 30 %, a recuperaÃÃo se aproximou de 75 % e a produtividade mÃxima foi de 1,02 t CO2 kg-1 ano-1 para algumas configuraÃÃes do processo. Os rendimentos para o adsorvente WV 1050 foram: pureza de 26,5 %, recuperaÃÃo de 47 % e produtividade de 0,53 t CO2 kg-1 ano-1.

Senior Honors Thesis (Chemical Engineering)--Ohio State University, 2005.
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The current atmospheric CO2 partial pressure of 36 Pa is expected to nearly double by the end of the 21st Century.Increases of this magnitude are likely to profoundly change the biochemistry, growth and morphology of plants, particularly C3 species.The research in this thesis focuses on the micronutrient Zinc (Zn), because this element is associated with a number of macromolecules which play key roles in plant growth and development, particularly on the shoot apex.The main objective of the work was to study the influence of elevated CO2 Zn nutrition of rice in the vegetative phase.A second objective was to investigate whether high CO2 reduced Zn concentrations in grain of cv. Jarrah and a Japanese cultivar, Akitakomachi, grown in either controlled environments, or in the field in a FACE (Free Air CO2 Enrichment) experiment. The greater Zn use efficiency of cvv. IR8 and Jarrah at elevated CO2, and the fact that high CO2 completely overcame chronic Zn deficiency at low Zn supplies, indicates that it may be possible , under future CO2 scenarios, to produce rice in areas where low soil Zn availability currently limits yield.
Master of Science (Hons)

Inland waters have long been neglected in the global carbon cycle. They represent only 2,8% of the land area, but it has come clear that inland waters play a key role in the transformation of terrestrial fixed carbon to the atmosphere. Human activities do have an impact on the carbon cycling and it is important to understand how these changes affects natural biogeochemical and climatological processes. The purpose of this report was to investigate how forestry impacts the emission of carbon dioxide from boreal lakes and to evaluate which role lakes play in the global carbon cycle. The study was accomplished as a literature study and the search words that have been used are carbon cycling, carbon dioxide, forestry, boreal lakes, dissolved organic carbon and pCO2. The results show that in many studies does forestry increase the export of dissolved organic carbon from terrestrial environments to boreal lakes. This increase subsidies the net heterotrophy in boreal lakes, making them net sources of carbon dioxide to the atmosphere. The processes behind increased concentrations and emissions are however complex and factors like local topography, hydrology and climate are thought to have impacts on how much carbon dioxide that is produced at a given level of dissolved organic carbon. Forestry seems to have an increasing effect on the carbon dioxide emissions, but the key drivers behind this process are expressed differently between regions and the reasons underlying these differences remain to be explored in order to make precise global carbon models.

Carbon Capture and Storage (CCS) is recognised as having a significant role to play in tackling climate change and reducing carbon dioxide (CO2) emissions. In CCS schemes, CO2 is captured from anthropogenic sources, and transported to suitable sites either for EOR (Enhanced Oil Recovery) or storage. The transport of such huge amount of CO2 causes new challenges. The main concern is in the difference between natural gas and CO2 transportation pipelines. CO2 phase behaviour during decompression, existence of different impurities and very high operating pressure are some of the new challenges for pipeline designer and operators. This PhD study has taken a systematic approach to understand the mechanics involved in the fracture of pipes containing high pressure flue-gas CO2. The work involved the development of a novel weight function stress intensity factor solution that can be used with complex stress fields induced by residual and/or thermal stresses in addition to applied pressure. In addition, the thesis reports a substantial experimented test programme which involved low temperature fracture toughness tests linked to a detailed finite element based stress analysis. Overall, the thesis presents an integrated engineering criticality means to assess the suitability or otherwise of a pipeline system to transport high pressure flue-gas CO2.

Dans le monde actuel, le dioxyde de carbone (CO2) est le déchet majoritaire issu de l’utilisation des ressources fossiles mais il est encore peu utilisé dans les applications à grande échelle. Afin de tirer parti de son abondance, le développement de nouvelles transformations chimiques du CO2 pour accéder à des produits de chimie fine connait un intérêt croissant au sein de la communauté scientifique. Tout particulièrement, la formation de liaison(s) C-N à partir du CO2 et d’un substrat azotés permet d’accéder à des produits à hautes valeurs énergétiques et commerciales. Un second type de transformation désirable est la formation de liaison C-C à partir du CO2 afin de synthétiser des dérivés d’acides carboxyliques comme des esters. L’utilisation d’hydrosilanes, réducteurs doux, permet de travailler sous 1 bar de CO2 avec des catalyseurs à base de métaux peu coûteux et abondants tels que le fer et le zinc ou bien avec des organocatalyseurs. Les synthèses de formamides, de méthylamines ou d’aminals à partir du CO2 ont ainsi été développées par hydrosilylation. Enfin, la carboxylation des carbosilanes à partir du CO2 a été développée pour la première fois avec un catalyseur à base de cuivre. Dans le cas des 2-pyridylsilanes, l’utilisation de sels de fluorures pentavalents permet d’activer le substrat efficacement sans catalyseur
In the current world, carbon dioxide (CO2) is the major waste of the massive utilization of fossil resources but only few applications have been developed using this compound. In order to take advantage of its abundancy, the development of novel chemical transformation of CO2 to produce fine chemicals is of high interest in the scientific community. In particular, the formation of C-N bond(s) from CO2 and amine compounds unlocks a new way to access high energy and value-added. A second type of highly desirable transformation is the formation of C-C bonds with CO2 so as to synthesize carboxylic acid derivatives. The utilization of hydrosilanes as mild reductants allows the reactions to proceed under 1 bar of CO2 with abundant and cheap metal-based catalysts (iron, zinc) or with organocatalysts. The synthesis of formamides, methylamines and aminals from CO2 are described herein. Ultimately, the catalytic carboxylation of carbosilanes has been achieved for the first time using copper-based complexes. In the specific case of 2-pyridylsilanes, the use of pentavalent fluoride salts allowed us to perform the reaction without catalyst

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Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)
O impacto da elevação da concentração de CO2 do ar sobre a brusone do arroz foi avaliado em estufas de topo aberto (OTCs) na Embrapa Meio Ambiente, Jaguariúna/SP, por dois anos. Foram realizados ensaios com cultivares de arroz em estufas com injeção de CO2, estufas sem injeção de CO2, e campo aberto, sem injeção de CO2 e sem estufa. Avaliaram-se as características de desenvolvimento das plantas, a incidência e a severidade da brusone do arroz, a caracterização química e microbiológica da rizosfera de plantas de arroz, e o teor de silício acumulado na parte aérea das plantas. No primeiro ensaio foi avaliada também a ocorrência de bactérias diazotróficas endofíticas nas raízes das plantas. A concentração média de CO2 atmosférico do tratamento em campo aberto foi 459,4 e 447,4 μmol mol-1 na safra 2007/08 e safra 2008/09, respectivamente. Por outro lado, as concentrações médias de CO2 foram 490,1 e 480,4 μmol mol-1 para o tratamento em estufa sem injeção de CO2 e 531,9 e 608,6 μmol mol-1 para o tratamento com estufa com injeção de CO2 na safra 2007/08 e safra 2008/09, respectivamente. Nos resultados obtidos, verificou-se o aumento significativo na altura de plantas das cultivares Agulha Precoce e Shao Tiao Tsao, na safra 2008/09, no tratamento com injeção do gás. Nas cultivares Caloro e Agulha Precoce, nas safras 2007/08 e 2008/09, respectivamente, o ambiente com a concentração de CO2 do ar elevada aumentou a severidade da brusone nas folhas das plantas. A análise química e microbiológica da rizosfera não apresentou diferenças entre os ambientes com e sem injeção do gás. A massa seca da parte aérea das plantas, a massa das panículas e a massa dos grãos não sofreram alteração devido à elevação do CO2 atmosférico. O aumento da concentração de CO2 do ar pode alterar o crescimento das plantas e a severidade da brusone, acarretando...
The impact of elevated atmospheric CO2 concentration on rice blast disease was evaluated in open-top chambers (OTCs) in Embrapa Meio Ambiente, Jaguariúna /SP, for two years. Trials were developed under OTCs with injection of CO2, OTCs without injection of CO2, and field, without injection of CO2 and without OTC. The characteristics of rice plants growth, the incidence and severity of rice blast, chemical and microbial characterization of rizosphere of rice plants, and leaf silicon content were evaluated. On the first trial it was also examined the occurrence of diazotrophic bacteria in rice plant´s root. Actual season-long average CO2 concentration in field without injection of CO2 and without OTC were 459,4 e 447,4 μmol mol-1 in 2007/08 and 2008/09, respectively. For the other hand, actual season-long average CO2 concentration were 490,1 and 480,4 μmol mol-1 in OTCs without injection of CO2 and 531,9 and 608,6 μmol mol-1 for the treatment under OTCs with CO2 enrichment in 2007/08 and 2008/09, respectively. As results, Agulha Precoce and Shao Tiao Tsao, in 2008/09, it was found a significant increase on rice growth, on treatment with CO2 injection. On Caloro and Agulha Precoce, in 2007/08 and 2008/09, respectively, the atmosphere with elevated CO2 increased the severity of leaf blast. No significant difference was detected on rizhosphere chemical and microbiological analysis in the atmosphere with injection of the gas. CO2 enrichment resulted in a non-significant increase in grain weight, plant dry weight and the panicles weight. The increase of CO2 atmospheric concentration may alter the rice plant´s growth and the severity of rice blast, and consequently, the strategies of disease management.

Orientador: Telma Teixeira Franco
Tese (doutorado) - Universidade Estadual de Campinas, Faculdade de Engenharia Química
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Resumo: O uso de microalgas em processos de mitigação ambiental e produção de energia renovável vêm ganhando destaque, mas a otimização das etapas de "upstream" e "downstream" são essenciais para que a viabilidade técnica e econômica seja alcançada e o processo implementado em escala industrial. As condições que maximizam o crescimento celular, a mitigação de CO2, o acúmulo de lipídios e proporcionam um perfil de ácidos graxos, compatível com a produção de biodiesel de elevada qualidade, foram avaliados em função de diferentes temperaturas (18-42 ºC), disponibilidade de carbono na forma de CO2 (ar-40%), disponibilidade de luz (4-192 ?mol.m-2.s-1) e disponibilidade de nitrogênio na forma de NaNO3 (0,25-1,00 g.L-1). A recuperação da biomassa a partir do processo de floculação foi avaliada em função do tipo de floculante (orgânico e inorgânico), dose do floculante (0,005-0,300 g.L-1), pH (4-11) e concentração celular (0,1-1,0 g.L-1). As condições de cultivo selecionadas foram: 108 ?mol.m-2.s-1, 26,5 ºC, 0,25 g.L-1 de NaNO3 e 8,05 % de CO2, sendo obtidos os seguintes resultados: Xmax/X0=14,78 (razão da concentração celular máxima pela concentração inicial); ?max=1,02 d-1 (máxima velocidade específica de crescimento); ?=0,50 d (duração da fase lag); Pmax=0,58 g.L-1.d-1 (produtividade máxima); Pmean=0,31 g.L-1.d-1 (produtividade média); CBmax=1,06 g.L-1.d-1 (Máxima taxa de incorporação de carbono); CBmean=0,55 g.L-1.d-1 (média da taxa de incorporação de carbono); 50% de lipídios e 90% dos FAMES (ésteres metílicos de ácidos graxos) correspondendo aos principais FAMES do biodiesel (C16:0, C18:0, C18:1, C18:2 e C18:3). A predição da qualidade do biodiesel produzido a partir do óleo de microalga forneceu os seguintes resultados: CN=56 (número de cetano), CFPP = 0,8 °C (ponto de entupimento de filtro a frio), ? = 863 kg/m³ (densidade), II = 97 gI2/100g (índice de iodo), ?HC = 39,2 kJ/g (calor de combustão), OSI = 13,8 h (índice de estabilidade oxidativa), e ? = 3,93 mm².s (viscosidade) estando dentro dos valores especificados pelas normas ANP255/2003, EN14213-14214 e ASTM6751. As condições para eficiências de recuperação (RE) da biomassa superiores a 95% foram: intervalos de pH 4,0 a 11,0 (floculante orgânico); 5,0 a 7,0 (FeCl3) e de 7,0 a 8,0 (Al2(SO4)3; razão de gfloculante/gbiomassa de: 0,08 gorgânico/gbiomassa, 0,40gAl2(SO4)3/gbiomassa. O impacto da disponibilidade de luz no interior de fotobiorreatores foi estimada para diferentes disponibilidades de luz (108-700 ?mol.m-2.s-1) e a partir de dados de concentração celular, concentração de pigmentos e geometria do reator, sendo verificada a perda de aproximadamente 85% da luz disponível na superfície para cultivos com concentração celular de até 2 g.L-1 em fotobiorreatores de 8 cm de diâmetro. A produção de biomassa e bicombustíveis em software comercial SuperPro designer v8.5 fomos simuladas e associadas à análise econômica
Abstract: The use of microalgae in environmental carbon dioxide mitigation processes and renewable energy production are gaining attention, but the optimization of "upstream" and "downstream" process is essential to promote technical and economic feasibility and make with the industrial scale became true. The conditions that maximize biomass growth, carbon dioxide mitigation, lipid content, and produce a fatty acid profile suitable for a high quality biodiesel was evaluated as function of different temperatures (18-42 ºC), carbon availability as CO2 (air-40%), light intensity (4-192 ?mol.m-2.s-1), and nitrogen availability as NaNO3 (0.25-1.00 g.L-1). Biomass harvesting using flocculation process was evaluated as function of flocculant type (organic and inorganic), flocculant dosage (0.005-0.3 g.L-1), pH (4-11), and biomass concentration (0.1-1.0 g.L-1). The selected conditions were: 108 ?mol.m-2.s-1, 26.5 ºC and 8.05% de CO2, with the following results: Xmax/X0=14.78 (maximum and initial cell concentration ratio); ?max=1.02 d-1 (maximum specific growth rate), ?=0.50 d (lag phase duration); Pmax=0.58 g.L-1.d-1 (maximum productivity); Pmean=0.31 g.L-1.d-1 (mean productivity); CBmax=1.06 g.L-1.d-1 (maximum carbon incorporation rate); CBmean=0.55 g.L-1.d-1 (mean carbon incorporation rate); 50% of lipid content, and 90% of samples FAMES (fatty acid methyl ester) corresponding to the mainly biodiesel FAMES (C16:0, C18:0, C18:1, C18:2 e C18:3). Biodiesel quality prediction using samples of microalgae oil show the following results: CN=56 (cetane number), CFPP = 0.8 °C (could filter plugging point), ? = 863 kg/m³ (density), II = 97 gI2/100g (iodine index), ?HC = 39.2 kJ/g (heat of combustion), OSI = 13.8 h (oil stability index), and ? = 3.93 mm².s (viscosity), and the values were compatible with different quality standards ASTM-D6751, EN14214/14213, and ANP 255/2003. Recovery efficiency (RE) of 95% or more can be obtained with pH 4,0 to 11,0 (organic flocculant); 5,0 to 7,0 (FeCl3), and 7,0 to 8,0 (Al2(SO4)3; gflocculant/gbiomass of: 0,08gorganic/gbiomass, 0,40gAl2(SO4)3/gbiomass). The impact of light availability in the center of photobioreactor was predicted as function of cell concentration, pigments concentration and photobioreactor design, being observed approximately 85% of loss in the incident light availability in cultures is less than 2 g.L-1. Biomass production process and biofuels production process were simulated using a commercial software SuperPro Designer v8.5 followed by economic analysis
Doutorado
Processos em Tecnologia Química
Doutora em Engenharia Quimica

Dans le contexte du réchauffement climatique et de l’usage abusif de combustibles fossiles, la recherche de sources d’énergie propres et durables est l’un des défis les plus importants de notre époque. Récemment, le stockage d’énergie solaire par la réduction de CO2 a fait l’objet d’un nouvel intérêt. Bien que la réduction de CO2 en carburants liquides ou gazeux soit une question à la fois fascinante et fondamentale, sa mise en œuvre dans les dispositifs technologiques reste très difficile à cause de la grande stabilité de CO2 et du caractère endergonique de sa transformation. On outre, les réactions impliquent multiples électrons et protons et ainsi demandent des catalyseurs efficaces et stables pour diminuer les barrières cinétiques importantes.Cette comprend deux parties. Après une introduction, la première partie décrit des études sur des catalyseurs homogènes en combinaison avec un photosensibilisateur, soit séparément soit connecté par liaison covalente. Grâce à la possibilité de les modifier par synthèse et à leur facile caractérisation, les photosystèmes moléculaires homogènes sont plus modulables et peuvent permettre un meilleur contrôle de la sélectivité des réactions et l’étude des mécanismes réactionnels.Cependant, les catalyseurs moléculaires ne peuvent être facilement transposés pour des applications à plus large échelle dans un contexte industriel. En effet, les catalyseurs homogènes sont moins stables et plus difficilement recyclables que les catalyseurs hétérogènes. Dans ce contexte, l’intégration de catalyseurs moléculaires au sein d’un support solide a l’avantage de maintenir leur activité catalytique tout en permettant une séparation et un recyclage plus faciles. La deuxième partie de cette thèse porte donc sur l’immobilisation de catalyseurs moléculaires dans les matériaux. Le but ultime de cette thèse est d’incorporer à la fois le catalyseur et le photosensibilisateur dans le support solide
In the context of global warming and the necessary substitution of renewable energies (solar and wind energy) for fossil fuels, efficient energy-storage technologies need to be urgently developed. Recently, energy storage via the reduction of CO2 has seen renewed interest. Although reduction of CO2 into energy-dense liquid or gaseous fuels is a fascinating fundamental issue, its practical implementation in technological devices is highly challenging due to the high stability of CO2 and thus the endergonic nature of its transformation. Furthermore, the reactions involve multiple electrons and protons and thus require efficient catalysts to mediate these transformations.The objective of this thesis is to investigate different strategies for the storage of solar energy in chemical compounds, through visible-light-driven CO2 reduction. This thesis comprises of two main parts. After an introduction, the first part describes the investigation of homogeneous catalysts in combination with a photosensitizer, either separately or connected covalently. Due to the easily-tunable synthesis and facile characterization of molecular catalysts, homogeneous photosystems are more controllable and can give deep insight into product selectivity and mechanistic issues.With regards to future applicability, however, homogeneous catalysis often suffers from additional costs associated with solvents, product isolation and catalyst recovery, amongst other factors. The integration of molecular catalysts into solid platforms offers the possibility to maintain the advantageous properties of homogeneous catalysts while moving towards practical system designs afforded by heterogeneous catalysis. The second part of this thesis is therefore the immobilization of molecular catalysts within solid materials, namely MOFs and PMO. The ultimate goal of this thesis is to incorporate both catalyst and photosensitizer into the solid support

Australia is recognising that carbon capture and storage (CCS) may be a feasible pathway for addressing increasing levels of CO2 emissions. This thesis presents a preliminary economic assessment and comparison of the capture costs for different Australian CO2 emission sources. The capture technologies evaluated include solvent absorption, pressure swing adsorption (PSA), gas separation membranes and low temperature separation. The capture cost estimated for hydrogen production, IGCC power plants and natural gas processing is less than A$30/tonne CO2 avoided. CO2 capture cost for iron production ranges from A$30 to A$40 per tonne CO2 avoided. Higher costs of A$40 to over A$80 per tonne CO2 avoided were estimated for flue gas streams from pulverised coal and NGCC power plants, oil refineries and cement facilities, and IDGCC synthesis gas. Based on 2004 and 2005 EU ETS carbon prices (A$30 to A$45 per tonne CO2 avoided), the cost of capture using current commercially available absorption technology may deter wide-scale implementation of CCS, in particular for combustion processes. A sensitivity analysis was undertaken to explore the opportunities for reducing costs. The high cost for capture using solvent absorption is dependent on the energy needed for solvent regeneration and the high capital costs. Cost reductions can be achieved by using new low regeneration energy solvents coupled with recycling the waste heat from the absorption process back to the steam cycle, and using low cost ???fit-for-purpose??? equipment. For membrane and PSA technologies, the capture costs are dominated by the flue gas and post-capture compressors. Operating the permeate or desorption stream under vacuum conditions provides significant cost reductions. Improvements in membrane and adsorbent characteristics such as the adsorbent loading or membrane permeability, CO2 selectivity, and lower prices for the membrane or adsorbent material provide further cost benefits. For low partial pressure CO2 streams, capture using low temperature ???anti-sublimation??? separation can be an alternative option. Low costs could be achieved by operating under low pressures and integrating with external sources of waste heat. Applying the cost reductions achievable with technology and process improvements reduces the capture and CCS costs to a level less than current carbon prices, making CCS an attractive mitigation option.

Forest soil is an important source of atmospheric CO2. Emission of CO2 from soil is the result of respiration of plant roots and soil organisms (Autotrophic and Heterotrophic respiration). This soil CO2 emission has a variation throughout the year with maximum emissions being in the summer. However, the seasonal variation affected by the external factors is not fully known. The aim of this thesis is to analyze a relationship between concentration of CO2 in the soil-atmosphere and CO2 emissions to the aboveground atmosphere. When knowing the relationship between CO2 concentration in the soil-atmosphere and the emission of CO2 from the soil atmosphere, a function (equation) can be established. Usually, the best fit is considered to establish the relationship. With the equations obtained, it is possible to calculate CO2 emissions using data different projects, where only soil-atmosphere CO2 concentrations were determined. Using the relationships, emissions rates in different soil types and in forest transect have been analyzed for a large number of samples. The effect of nitrogen deposition on CO2 emissions and seasonal variation of CO2 emission has also been studied. The sampled sites chosen for this study were located in different parts of Southern Scandinavia and Germany. A closed chamber was used to measure CO2 emission from soil. Soil CO2 concentrations were measured at every station and the equations were established. Finally, these relationships were used for analyses and comparison of the sites. An equation (best fit) obtained was used to calculate the emission values of CO2. The soil texture had a great influence on the CO2 from the soil besides the atmospheric pressure and temperature variations during the seasons. It is concluded that, therefore the soil texture and had a great influence on the CO2 emission from the soil besides the atmospheric pressure and temperature variations during the season. When knowing the equation between CO2 concentration and emission for a special type of soil, it is possible to estimate emissions based on CO2 concentrations. Therefore large scale sampling of CO2 concentrations could be done and this will facilitate the inventories carried out in e.g. global change studies.

The use of supercritical carbon dioxide (scCO2) as a processing aid to help exfoliate nano-clays and improve their dispersion during melt blending in polymer matrices has been reported in the literature. One of the best processes in terms of improving the degree of nano-clay dispersion and composite mechanical properties was developed in our laboratory. This process allows the clay to be in direct contact with scCO2 and expanding the clay-CO2 mixture via rapid depressurization into a two-stage screw extruder to mix with the polymer pellets. However, composites with clay loading higher than 6.6 wt % were not reported. In addition, the scCO2 aided processing method has not been applied to carbon nanotube (CNT) based composites. This dissertation initially focused on applying the scCO2 aided processing technique to the field of CNT expansion and CNT/polymer composite preparation. The relationship with the expanded CNT morphology and the experimental conditions of the expansion procedure (including pressures, temperatures, exposure time, and depressurization rates) was studied. Microscopy results showed improved CNT dispersion in the polymer matrix and more uniform networks formed with the use of scCO2, which indicated that CO2 expanded CNTs are easier to disperse into the polymer matrix during the blending procedure. The CNT/ poly(phenylsulfone) (PPSF) composites prepared with scCO2 aided method provided continuous improvements in Youngâ s modulus up to the addition of 7 wt % CNTs. However, the Youngâ s modulus of the composite prepared by means of conventional direct melt blending failed to increase beyond the addition of 1 wt % CNT. The second part of this work is concerned with the development of a semi-continuous process using scCO2 to process polymer-clay composites with clay loading higher than 6.6 wt % (i.e. 10 wt %). Two major modifications are involved in the new procedure: exfoliating the nano-clay directly into the hopper filled with pellets followed by processing the composite immediately and sequentially mixing the clay into the melt. Transmission electron microscopy (TEM) and wide angle X-ray diffraction (WAXD) results show that this modified procedure help to reduce the clay collapse when processing the composites with high clay loadings. Surface modified montmorillonite (MMT) nano-clay/polypropylene (PP) composite at 10 wt % nano-clay with improved clay dispersion was obtained with increased modulus and tensile strength of 63 % and 16%, respectively, compared to the pure PP matrix. Additional mechanical property improvements for nano-clay based composites are then obtained with the use of high crystallinity polypropylene (HCPP) and polypropylene grafted with maleic anhydride (PP-g-MA). HCPP has higher crystallinity and stiffness than conventional PP and, therefore, composites made from HCPP have better mechanical properties to start with. PP-g-MA has polar groups grafted on the PP chains that promote the intercalation of PP with clay. By using the newly developed procedure, the HCPP nanocomposite at 10 wt % of nano-clay has a Youngâ s modulus as high as 3.236 GPa, and the modulus of the 10% MMT/PP-g-MA sample is found to be 2.595 GPa, both higher than that of the composite prepared by the direct blending method and that of a composite based on a conventional PP matrix.
Ph. D.

Although there are some carbon capture and storage (CCS-CO2 sequestration) projects in all over the world, feasibility problems exist due to the high economical issues. The aim of this study is to evaluate the feasibility of a potential CCS project where the source of CO2 is Afsin Elbistan Thermal Power Plant. Selection of candidate sites in the vicinity of Diyarbakir, Batman and Adiyaman regions depends on sequestration criteria. According to sequestration criteria, CCS can be applied to Ç
aylarbasi mature oil field, Midyat saline aquifer and Dodan CO2 gas field. Disposing of CO2 from the source of Afsin Elbistan Thermal Power Plant is analyzed by pipeline and tanker. CO2 capturing technologies are determined from published literature. CO2 transportation can be applied by pipeline or tanker. CO2 transportation cost by pipeline and tanker are compared. It has been calculated that, transportation by pipeline is more economical compared to tanker transportation. It is further found that the number of boosting pump stations, the length of the pipeline and CO2 mass flow rate are the issues that alter the economical aspect in the pipeline transportation. The transportation costs by tankers depend on fuel cost, distance, tanker storage capacity, pin-up cost and CO2 storage facilities. The final part of CCS project is injection and storage of CO2 to the candidate areas. Reservoir parameters which are reservoir temperature, viscosity, permeability, reservoir pressure, reservoir thickness, CO2 density mass flow rate and injection pipe diameter determine the number and cost of the injection wells.

El CO2 en la atmósfera aumenta a raíz del empleo de combustibles fósiles. La hidrogenación de CO2 ofrece una ruta única para transformar esta molécula en productos químicos o combustibles como el metanol. El uso de alta presión en el ratio CO2:H2 = 1:>3 permite incrementar la cinética de la reacción, alcanzando así la conversión termodinámica como ya se ha reportado. No obstante, el mayor inconveniente del mencionado proceso es el tratamiento del hidrógeno sin reaccionar. Por ello, se evaluaron las ventajas de realizar la reacción a alta presión en condiciones estequiométricas (CO2:H2=1:3) examinando diferentes parámetros. Una vez optimizados, se alcanzó el límite termodinámico y se obtuvo un valor de conversión de CO2 cercano al 90% con una selectividad para metanol > 95% a 280 °C y 442 bar empleando Cu/ZnO/AlO3 como catalizador. Al minimizar las limitaciones de transferencia de masa, el rendimiento fue de 15.6 gMeOH gcat-1 h-1, aproximadamente un orden de magnitud mayor comparado con los de bibliografía. Adicionalmente, los mecanismos de la reacción en condiciones de alta presión se estudiaron mediante análisis espacial de la fase gas por CG y espectroscopía Raman. El estudio mostró que el CO2 se convierte directamente a metanol a baja temperatura, mientras que a alta temperatura la reacción water-gas shift es predominante generando CO, que produce metanol posteriormente. estructura core-shell. Este material mostró un recubrimiento uniforme del ZnO en los cores de Cu, y el espesor del shell se optimizó. Dichos nanomateriales mostraron alta actividad catalítica, útil para comprender la interacción entre Cu y Zn y en concreto, las exclusivas fases de Zn formadas durante la reacción a alta presión mediante operando DRX a alta presión.
Carbon dioxide concentration in the atmosphere is continuously increasing as a consequence of the combustion of fossil fuels. CO2 hydrogenation offers a unique path to transform the chemically stable CO2 to useful chemicals or fuel such as methanol. High-pressure advantages under over-stoichiometric CO2:H2 ratio (1:>3) has been reported previously by drastically increasing the reaction kinetics and even reaching the thermodynamic conversion. However, the major drawback of such processes is the treatment of unreacted hydrogen. Reflecting this background, the advantages of the high pressure approach in stoichiometric CO2:H2 (1:3) ratio were critically evaluated by examining different reaction and process parameters. When optimized, we could reach the thermodynamic limit and obtained about 90% CO2 conversion with >95% methanol selectivity at 280 °C and 442 bar using Cu/ZnO/Al2O3 catalyst. When the mass transfer limitation was minimized, an outstanding weight time yield was achieved with 15.6 gMeOH gcat-1 h-1, which is about one order of magnitude higher than the state-of-the-art values. Furthermore, the reaction mechanisms under high-pressure reaction conditions were studied by spatially-resolved gas phase analysis through the axial direction of the catalytic reactor by GC and Raman spectroscopy.

Resumo: O presente estudo avaliou a reação do tecido conjuntivo irradiado com os lasers de CO2 e de Er:YAG em feridas confeccionadas no dorso de ratos. Foram confeccionadas 2 feridas no dorso de 30 ratos com um punch de 3mm de diâmetro. Os animais foram divididos em três grupos de 10: no Grupo I as feridas foram irradiadas com o laser de CO2, l 10,6 mm, (1,5 W -50 Hz); no Grupo II as feridas foram irradiadas com o laser de Er:YAG, l 2,94 mm (300 mJ -10 Hz), tempo de irradiação de 23 segundos em ambos os grupos; e no grupo III as feridas não foram submetidas à irradiação. Após o ato operatório, todas as feridas foram forradas com MTA. Os animais foram mortos em períodos de 1 dia e 7 dias e as peças removidas, processadas, coradas com hematoxilina / eosina e analisadas no microscópio óptico. Aos 7 dias, no grupo do Er:YAG foi observada a presença de tecido de granulação, porém no grupo do CO2 ainda houve uma severa reação inflamatória com áreas de necrose tecidual. No grupo controle não houve inflamação aos 7 dias na maioria dos casos. Conclusão: os resultados obtidos no presente estudo nos permitem afirmar que o tecido conjuntivo reagiu de forma mais favorável à irradiação laser de Er:YAG do que à irradiação do laser de CO2, independentemente do tempo pós-operatório.
Abstract: The present study assesed the connective tissue reaction after irradiation with CO2 and Er:YAG lasers in in the back of rats. Two wounds were practiced in the back of tirthy rats with a 3mm diameter punch. The animals were divided into three groups of ten specimens each: In Group I the wounds were irradiated with a CO2 laser, l 10,6mm, (1,5 W -50 Hz) ; In Group II the wounds were irradiated with a Er:YAG laser, l 2,94m, (300 mJ -10 Hz), in both groups the irradiation time was of 23 seconds; Group III received no irradiation. After the intervention, all wounds were covered with MTA. The specimens were killed after intervals of 1 to 7 days and samples collected, proccesed and stained with hematoxilin/eosin, and analized under the ligth microscope. At seven days period the Er:YAG group exhibited granulation tissue proliferation, while in the CO2 group a severe inflamatory reaction persisted with areas of necrosis. In the control group there was no inflamation in most of the cases after 7 days period. Conclusions: The results yielded by the present study lead us to assure that the reaction of the connective tissue was most favorable to irradiation with Er:YAG laser than with CO2 laser, regardless the time elapsed after the intervention.
Orientador: Fábio Luiz Camargo Villela Berbert
Coorientador: Lizeti Toledo de Oliveira Ramalho
Banca: Elói Dezan Junior
Banca: Ivaldo Gomes de Moraes
Mestre

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O petróleo ainda continua sendo a maior fonte de energia não renovável do planeta. No seu estado bruto tem pouca utilidade. No entanto, seus derivados apresentam alto valor econômico. Nas etapas de processamento primário do petróleo alguns compostos de ocorrência natural são indesejáveis, como os ácidos naftênicos, resinas, asfaltenos, compostos sulfurados e metálicos. O poder corrosivo dos ácidos naftênicos preocupa as indústrias petrolíferas devido ao prejuízo causado nas tubulações e refinarias. Estudos recentes indicam que uma parcela desses ácidos quando submetidos a elevadas temperaturas (>280°C) pode sofrer reações de descarboxilação e degradação térmica, originando dióxido de carbono (CO2) e ácidos de cadeias menores como produtos de degradação. Os ácidos de cadeias menores juntamente com os ácidos naftênicos que se mantiveram preservados são corrosivos e o CO2 ao entrar em contato com água forma o ácido carbônico (H2CO3), podendo contribuir nas taxas de corrosão nos equipamentos do refino. Assim, o presente trabalho consistiu no desenvolvimento de uma metodologia para quantificação online do CO2 liberado no processo de destilação de petróleo. A metodologia desenvolvida foi baseada na técnica de microcromatografia gasosa. Os dados quantitativos de concentração de CO2 gerados pela microcromatografia foram relacionados com os valores de temperaturas de destilação, obtendo-se assim uma variação na concentração de CO2 de acordo com a temperatura de destilação do óleo. Com os resultados obtidos observou-se que para todos os petróleos destilados houve uma tendência na formação do gás CO2 partir de temperaturas superiores a 200°C. Na tentativa de elucidar a possível origem deste gás, supôs um mecanismo de descarboxilação para tais ácidos

Los procesos termo-hidro-mecánicos relacionados con el almacenamiento geológico de carbono deben ser entendidos y cuantificados para demostrar a la opinión pública de que la inyección de dióxido de carbono (CO2) es segura. Esta Tesis tiene como objetivo mejorar dicho conocimiento mediante el desarrollo de métodos para: (1) evaluar la evolución tanto de la geometría de la pluma de CO2 como de la presión de los fluidos; (2) definir un ensayo de campo que permita caracterizar la presión de inyección máxima sostenible y los parámetros hidromecánicos de las rocas sello y almacén; y (3) proponer un nuevo concepto de inyección que es energéticamente eficiente y que mejora la estabilidad de la roca sello en la mayoría de escenarios geológicos debido a efectos termo-mecánicos. modelo viscoplástico. Las simulaciones ilustran que, dependiendo de las condiciones de contorno, el momento más desfavorable ocurre al inicio de la inyección. Sin embargo, si los contornos son poco permeables, la presión de fluido continúa aumentando en todo el acuífero, lo que podría llegar a comprometer la estabilidad de la roca sello a largo plazo. Para evaluar dichos problemas, proponemos un ensayo de caracterización hidromecánica a escala de campo para estimar las propiedades hidromecánicas de las rocas sello y almacén. Obtenemos curvas para la sobrepresión y el desplazamiento vertical en función del término de la deformación volumétrica obtenido del análisis adimensional de las ecuaciones hidromecánicas. Ajustando las medidas de campo a estas curvas se pueden estimar los valores del módulo de Young y el coeficiente de Poisson del acuífero y del sello. Los resultados indican que la microsismicidad inducida tiene más probabilidades de ocurrir en el acuífero que en el sello. El inicio de la microsismicidad en el sello marca la presión de inyección máxima sostenible para asegurar un almacenamiento permanente de CO2 seguro. Finalmente, analizamos la evolución termodinámica del CO2 y la respuesta termohidro- mecánica de las rocas sello y almacén a la inyección de CO2 líquido (frío). Encontramos que inyectar CO2 en estado líquido es energéticamente más eficiente porque al ser más denso que el CO2 supercrítico, requiere menor presión en cabeza de pozo para una presión dad en el acuífero. De hecho, esta presión también es menor en el almacén porque se desplaza un volumen menor de fluido. La disminución de temperatura en el entorno del pozo induce una reducción de tensiones debido a la contracción térmica del medio. Esto puede producir deslizamiento de fracturas existentes en acuíferos formados por rocas rígidas bajo contrastes de temperatura grandes, lo que podría incrementar la inyectividad de la roca almacén. Por otro lado, la estabilidad mecánica de la roca sello mejora cuando la tensión principal máxima es la vertical. Primero, investigamos numérica y analíticamente los efectos de la variabilidad de la densidad y viscosidad del CO2 en la posición de la interfaz entre la fase rica en CO2 y la salmuera de la formación. Introducimos una corrección para tener en cuenta dicha variabilidad en las soluciones analíticas actuales. Encontramos que el error producido en la posición de la interfaz al despreciar la compresibilidad del CO2 es relativamente pequeño cuando dominan las fuerzas viscosas. Sin embargo, puede ser significativo cuando dominan las fuerzas de gravedad, lo que ocurre para tiempos y/o distancias largas de inyección. Segundo, desarrollamos una solución semianalítica para la evolución de la geometría de la pluma de CO2 y la presión de fluido, teniendo en cuenta tanto la compresibilidad del CO2 como los efectos de flotación dentro del pozo. Formulamos el problema en términos de un potencial de CO2 que facilita la solución en capas horizontales, en las que hemos discretizado el acuífero. El CO2 avanza inicialmente por la porción superior del acuífero. Pero a medida que aumenta la presión de CO2, la pluma crece no solo lateralmente, sino también hacia abajo, aunque no tiene porqué llegar a ocupar todo el espesor del acuífero. Tanto la interfaz CO2-salmuera como la presión de fluido muestran una buena comparación con las simulaciones numéricas. En tercer lugar, estudiamos posibles mecanismos de rotura, que podrían llegar a producir fugas de CO2, en un sistema acuífero-sello con simetría radial, utilizando un
Els processos termo-hidro-mecànics relacionats amb l’emmagatzematge geològic de carboni han de ser entesos i quantificats per tal de demostrar a l’opinió pública de que la injecció de diòxid de carboni (CO2) és segura. Aquesta Tesi té com a objectiu millorar aquest coneixement mitjançant el desenvolupament de mètodes per a: (1) avaluar l'evolució tant de la geometria del plomall de CO2 com de la pressió dels fluids; (2) definir un assaig de camp que permeti caracteritzar la pressió d'injecció màxima sostenible i els paràmetres hidromecànics de les roques segell i magatzem; i (3) proposar un nou concepte d'injecció que és energèticament eficient i que millora l'estabilitat de la roca segell en la majoria d’escenaris geològics a causa d'efectes termo-mecànics. Primer, investiguem numèricament i analítica els efectes de la variabilitat de la densitat i viscositat del CO2 en la posició de la interfície entre la fase rica en CO2 i la salmorra de la formació. Introduïm una correcció per tal de tenir en compte aquesta variabilitat en les solucions analítiques actuals. Trobem que l'error produït en la posició de la interfície en menysprear la compressibilitat del CO2 és relativament petit quan dominen les forces viscoses. Malgrat això, l’error pot ser significatiu quan dominen les forces de gravetat, la qual cosa té lloc per a temps i/o distàncies llargues d'injecció. Segon, desenvolupem una solució semianalítica per a l'evolució de la geometria del plomall de CO2 i la pressió de fluid, tenint en compte tant la compressibilitat del CO2 com els efectes de flotació dins del pou. Formulem el problema en termes d'un potencial de CO2 que facilita la solució en capes horitzontals, en les quals hem discretitzat l'aqüífer. El CO2 avança inicialment per la porció superior de l'aqüífer. Però a mesura que augmenta la pressió de CO2, el plomall de CO2 no només creix lateralment, sinó que també ho fa cap avall, encara que no té perquè arribar a ocupar tot el gruix de l'aqüífer. Tant la interfície CO2-salmorra com la pressió de fluid mostren una bona comparació amb les simulacions numèriques. En tercer lloc, estudiem possibles mecanismes de trencament, que podrien arribar a produir fugues de CO2, en un sistema aqüífer-segell amb simetria radial, utilitzant un model viscoplàstic. Les simulacions il·lustren que, depenent de les condicions de contorn, el moment més desfavorable té lloc a l'inici de la injecció. Tot i això, si els contorns són poc permeables, la pressió de fluid continua augmentant en tot l'aqüífer, la qual cosa podria arribar a comprometre l'estabilitat de la roca segell a llarg termini. Per a avaluar aquests problemes, proposem un assaig de caracterització hidromecànica a escala de camp per a estimar les propietats hidromecàniques de les roques segell i magatzem. Obtenim corbes per a la sobrepressió i el desplaçament vertical en funció del terme de la deformació volumètrica obtingut de l'anàlisi adimensional de les equacions hidromecàniques. Ajustant les mesures de camp a aquestes corbes es poden estimar els valors del mòdul de Young i el coeficient de Poisson de l'aqüífer i del segell. Els resultats indiquen que la microsismicitat induïda té més probabilitats d'ocórrer en l'aqüífer que en el segell. L'inici de la microsismicitat en el segell marca la pressió d'injecció màxima sostenible per tal d’assegurar un emmagatzematge permanent de CO2 segur. Finalment, analitzem l'evolució termodinàmica del CO2 i la resposta termo-hidromecànica de les roques segell i magatzem a la injecció de CO2 líquid (fred). Trobem que injectar CO2 en estat líquid és energèticament més eficient perquè al ser més dens que el CO2 supercrític, requereix una pressió menor al cap de pou per a una pressió donada a l’aqüífer. De fet, aquesta pressió també és menor a l’aqüífer perquè es desplaça un volum menor de fluid. La disminució de temperatura a l'entorn del pou indueix una reducció de tensions a causa de la contracció tèrmica del medi. Això pot produir lliscament de fractures existents en aqüífers formats per roques rígides sota contrastos de temperatura grans, la qual cosa podria incrementar la injectivitat de la roca magatzem. D’altra banda, l'estabilitat mecànica de la roca segell millora quan la tensió principal màxima és la vertical.
Coupled thermo-hydro-mechanical (THM) effects related to geologic carbon storage should be understood and quantified in order to convince the public that carbon dioxide (CO2) injection is safe. This Thesis aims to improve such understanding by developing methods to: evaluate the CO2 plume geometry and fluid pressure evolution; define a field test to characterize the maximum sustainable injection pressure and the hydromechanical (HM) properties of the aquifer and the caprock; and propose an energy efficient injection concept that improves the caprock mechanical stability in most geological settings due to thermo-mechanical effects. First, we investigate numerically and analytically the effect of CO2 density and viscosity variability on the position of the interface between the CO2-rich phase and the formation brine. We introduce a correction to account for this variability in current analytical solutions. We find that the error in the interface position caused by neglecting CO2 compressibility is relatively small when viscous forces dominate. However, it can become significant when gravity forces dominate, which is likely to occur at late times and/or far from the injection well. Second, we develop a semianalytical solution for the CO2 plume geometry and fluid pressure evolution, accounting for CO2 compressibility and buoyancy effects in the injection well. We formulate the problem in terms of a CO2 potential that facilitates solution in horizontal layers, in which we discretize the aquifer. We find that when a prescribed CO2 mass flow rate is injected, CO2 advances initially through the top portion of the aquifer. As CO2 pressure builds up, CO2 advances not only laterally, but also vertically downwards. However, the CO2 plume does not necessarily occupy the whole thickness of the aquifer. Both CO2 plume position and fluid pressure compare well with numerical simulations. Third, we study potential failure mechanisms, which could lead to CO2 leakage, in an axysimmetric horizontal aquifercaprock system, using a viscoplastic approach. Simulations illustrate that, depending on boundary conditions, the least favorable situation may occur at the beginning of injection. However, in the presence of low-permeability boundaries, fluid pressure continues to rise in the whole aquifer, which may compromise the caprock integrity in the long-term. Next, we propose a HM characterization test to estimate the HM properties of the aquifer and caprock at the field scale. We obtain curves for overpressure and vertical displacement as a function of the volumetric strain term obtained from a dimensional analysis of the HM equations. We can then estimate the values of the Young¿s modulus and the Poisson ratio of the aquifer and the caprock by introducing field measurements in these plots. Results indicate that induced microseismicity is more likely to occur in the aquifer than in the caprock. The onset of microseismicity in the caprock can be used to define the maximum sustainable injection pressure to ensure a safe permanent CO2 storage. Finally, we analyze the thermodynamic evolution of CO2 and the THM response of the formation and the caprock to liquid (cold) CO2 injection. We find that injecting CO2 in liquid state is energetically more efficient than in supercritical state because liquid CO2 is denser than supercritical CO2. Thus, the pressure required at the wellhead is much lower for liquid than for gas or supercritical injection. In fact, the overpressure required at the aquifer is also smaller because a smaller fluid volume is displaced. The temperature decrease close to the injection well induces a stress reduction due to thermal contraction of the media. This can lead to shear slip of pre-existing fractures in the aquifer for large temperature contrasts in stiff rocks, which could enhance injectivity. In contrast, the mechanical stability of the caprock is improved in stress regimes where the maximum principal stress is the vertical.

The interest in utilizing the energy in low‐grade heat sources and waste heat is increasing. There is an abundance of such heat sources, but their utilization today is insufficient, mainly due to the limitations of the conventional power cycles in such applications, such as low efficiency, bulky size or moisture at the expansion outlet (e.g. problems for turbine blades). Carbon dioxide (CO2) has been widely investigated for use as a working fluid in refrigeration cycles, because it has no ozonedepleting potential (ODP) and low global warming potential (GWP). It is also inexpensive, non‐explosive, non‐flammable and abundant in nature. At the same time, CO2 has advantages in use as a working fluid in low‐grade heat resource recovery and energy conversion from waste heat, mainly because it can create a better matching to the heat source temperature profile in the supercritical region to reduce the irreversibility during the heating process. Nevertheless, the research in such applications is very limited. This study investigates the potential of using carbon dioxide as a working fluid in power cycles for low‐grade heat source/waste heat recovery. At the beginning of this study, basic CO2 power cycles, namely carbon dioxide transcritical power cycle, carbon dioxide Brayton cycle and carbon dioxide cooling and power combined cycle were simulated and studied to see their potential in different applications (e.g. low‐grade heat source applications, automobile applications and heat and power cogeneration applications). For the applications in automobile industries, low pressure drop on the engine’s exhaust gas side is crucial to not reducing the engine’s performance. Therefore, a heat exchanger with low‐pressure drop on the secondary side (i.e. the gas side) was also designed, simulated and tested with water and engine exhaust gases at the early stage of the study (Appendix 2). The study subsequently focused mainly on carbon dioxide transcritical power cycle, which has a wide range of applications. The performance of the carbon dioxide transcritical power cycle has been simulated and compared with the other most commonly employed power cycles in lowgrade heat source utilizations, i.e. the Organic Rankin Cycle (ORC). Furthermore, the annual performance of the carbon dioxide transcritical power cycle in utilizing the low‐grade heat source (i.e. solar) has also been simulated and analyzed with dynamic simulation in this work. Last but not least, the matching of the temperature profiles in the heat exchangers for CO2 and its influence on the cycle performance have also been discussed. Second law thermodynamic analyses of the carbon dioxide transcritical power systems have been completed. The simulation models have been mainly developed in the software known as Engineering Equation Solver (EES)1 for both cycle analyses and computer‐aided heat exchanger designs. The model has also been connected to TRNSYS for dynamic system annual performance simulations. In addition, Refprop 7.02 is used for calculating the working fluid properties, and the CFD tool (COMSOL) 3 has been employed to investigate the particular phenomena influencing the heat exchanger performance.
QC 20111205

Soil CO2 efflux (F-soil) represents a significant source of ecosystem CO2 emissions that is rarely quantified with high-temporal-resolution data in carbon flux studies. F-soil estimates can be obtained by the low-cost gradient method (GM), but the utility of the method is hindered by uncertainties in the application of published models for the diffusion coefficient. Therefore, to address and resolve these uncertainties, we compared F-soil measured by 2 soil CO2 efflux chambers and F-soil estimated by 16 gas transport models using the GM across 1year. We used 14 published empirical gas diffusion models and 2 in situ models: (1) a gas transfer model called Chamber model obtained using a calibration between the chamber and the gradient method and (2) a diffusion model called SF6 model obtained through an interwell conservative tracer experiment. Most of the published models using the GM underestimated cumulative annual F-soil by 55% to 361%, while the Chamber model closely approximated cumulative F-soil (0.6% error). Surprisingly, the SF6 model combined with the GM underestimated F-soil by 32%. Differences between in situ models could stem from the Chamber model implicitly accounting for production of soil CO2, while the conservative tracer model does not. Therefore, we recommend using the GM only after calibration with chamber measurements to generate reliable long-term ecosystem F-soil measurements. Accurate estimates of F-soil will improve our understanding of soil respiration's contribution to ecosystem fluxes.