Les objectifs de la thèse sont d'étudier le transport de fluide et le transfert de chaleur dans les pores micro et nanométriques. Les expériences et les simulations ont révélé des preuves de l'augmentation du flux provoquée par la vitesse de glissement à la paroi solide. D'autre part, la résistance thermique finie à l'interface fluide-solide est responsable de la différence de température des deux phases. Ces deux phénomènes d'interface peuvent avoir un impact considérable sur la perméabilité et la diffusivité thermique des milieux poreux constitués de micro et nanopores. La contribution se concentre sur l'étude des trois problèmes suivants. Premièrement, nous examinons les effets de glissement des liquides confinés dans un canal de graphème en utilisant le formalisme de Green Kubo et la méthode de la dynamique moléculaire. On montre que lorsque la surface solide est soumise à une contrainte mécanique uniaxiale, la friction présente une anisotropie due à la modification de l'énergie potentielle et de la dynamique des molécules composant le fluide. Les formes moléculaires jouent également un rôle important sur les écarts de frottement entre les deux directions principales. Deuxièmement, nous étudions le régime des gaz raréfiés. Dans ce cas, la vitesse de glissement et le saut de température sont régis par les collisions entre les atomes de gaz et la paroi solide. Ces effets peuvent être déterminés à l’aide d’un modèle statistique qui peut être construit à partir des vitesses incidente et réfléchie des molécules de gaz. A cette fin, différentes méthodes basées sur des techniques d'apprentissage statistique ont été proposées. Enfin, la méthode des éléments finis est utilisée pour calculer la perméabilité et la diffusivité thermique des milieux poreux sous l'influence des effets d'interface / The objectives of the thesis are to study the fluid transport and heat transfer in micro and nano-scale pores. Both experiments and simulations revealed evidence of an enhancement of flow-rate, originated from slip velocity at the solid boundary. On the other hand, the finite thermal resistance at the fluid-solid interface is responsible for the temperature difference between the two phases. These two interface phenomena can have a considerable impact on the permeability and thermal diffusivity of porous media constituted of micro and nano-pores. This contribution focuses on studying the following three issues. First, we examine the slip effects of liquids confined in graphene channel using Green Kubo formalism and Molecular Dynamics method. It is shown that when the solid surface is subject to mechanical uniaxial strain, the friction exhibits anisotropy due to the modification of the potential energy and the dynamics of the fluid molecules. The molecular shapes also play an important factor on the friction discrepancies between two principal directions. The quantification of both effects is addressed. Second, we investigate the rarefied gas regime. In this case, the velocity slip and temperature jump are governed by the collisions between the gas and the solid boundary. Those effects can be determined via the study of scattering kernel and its construction from MD simulation data. To this end, different methods based on statistical learning techniques have been proposed including the nonparametric (NP) kernel and Gaussian mixture (GM) kernel. Finally, the finite element method is used to compute the permeability and the thermal diffusivity of porous media under the influence of the interface effects

Novel anode catalysts have been developed for sour natural gas solid oxide fuel cell (SOFC) applications. Sour natural gas comprises light hydrocarbons, and typically also contains H2S. An alternative fuel SOFC that operates directly on sour natural gas would reduce the overall cost of plant construction and operation for fuel cell power generation. The anode for such a fuel cell must have good catalytic and electrocatalytic activity for hydrocarbon conversion, sulfur-tolerance, resistance to coking, and good electronic and ionic conductivity. The catalytic activity and stability of ABO3 (A= La, Ce and/or Sr, B=Cr and one or more of Ti, V, Cr, Fe, Mn, or Co) perovskites as SOFC anode materials depends on both A and B, and are modied by substituents. The materials have been prepared by both solid state and wet-chemical methods. The physical and chemical characteristics of the materials have been fully characterized using electron microscopy, XRD, calorimetry, dilatometry, particle size and area, using XPS and TGA-DSC-MS. Electrochemical performance was determined using potentiodynamic and potentiostatic cell testing, electrochemical impedance analysis, and conductivity measurements. Neither Ce0.9Sr0.1VO3 nor Ce0.9Sr0.1Cr0.5V0.5O3 was an active anode for oxidation of H2 and CH4 fuels. However, active catalysts comprising Ce0.9Sr0.1V(O,S)3 and Ce0.9Sr0.1Cr0.5V0.5(O,S)3 were formed when small concentrations of H2S were present in the fuels. The oxysuldes formed in-situ were very active for conversion of H2S. The maximum performance improved from 50 mW cm2 to 85 mW cm2 in 0.5% H2S/CH4 at 850 oC with partial substitution of V by Cr in Ce0.9Sr0.1V(O,S)3 . Selective conversion of H2S offers potential for sweetening of sour gas without affecting the hydrocarbons. Perovskites La0.75Sr0.25Cr0.5X0.5O3, (henceforth referred to as LSCX, X=Ti, Mn, Fe, Co) are active for conversion of H2, CH4 and 0.5% H2S/CH4. The order of activity in the different fuels depends on the substituent element: CH4, X=Fe>Mn>Ti; H2,X = Fe>Mn>Ti; and 0.5% H2S/CH4, X = Fe>Ti>Mn. The electrocatalytic activity for methane oxidation in a fuel cell correlates with ex-situ temperature programmed catalytic activity. A process is proposed to explain the difference in catalyst order and enhanced activities in H2S/CH4 as fuel compared to CH4 alone. The maximum power density of 250 mW cm2 was attained using a fuel cell with a composite anode, LSCFe-GDC | YSZ(0.3 mm) | Pt, operated at 850 oC (GDC is Ce0.9Gd0.1O3, a good mixed conductor under reducing conditions). / Materials Engineering

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No description available.

Abstract Methane (CH4) and nitrous oxide (N2O) are not only important but also long-lived greenhouse gases. Unfortunately, in Taiwan, although there are some data on CH4 emission from rivers and lakes there is no data about N2O emission from rivers, lakes and coasts. So this study investigated CH4 and N2O distribution in natural waters around Taiwan. In Taiwan, the average CH4 concentration in rivers is about 3082¡Ó12399nM (n=152). The average CH4 concentration in mountain lakes is about 2899¡Ó7291nM (n=51). The average CH4 concentration in lower elevation lakes and reservoirs is about 1825¡Ó2755nM ppmv (n=95). The average CH4 concentration in near-shore waters is about 36.7¡Ó285nM (n=476). The CH4 distribution is rivers> mountain lakes>low-elevation lakes and reservoirs >seawater. In southeastern China, the average CH4 concentration in rivers is about 1029¡Ó2487nM ppmv (n=36). The average CH4 concentration of samples taken from rivers in southeastern China is lower than Taiwan rivers. But the highest CH4 concentration of all samples is in Chih-Kan river of southeastern China (14914nM), due to uneven population distribution as well as different levels of development among cities and suburbs. In Taiwan, the average N2O concentration in rivers is about 32.8¡Ó69.1nM (n=58). In southeastern China, the average N2O concentration in rivers is about 29.7¡Ó9.05nM (n=36). The average N2O concentration in Taiwanese rivers is higher than found in southeastern China. This is likely because farmers in Taiwan use more synthetic fertilizers so the soil becomes full of N element, and then rivers and rains rinse the soil. This process has increased the concentration of N and N2O in rivers. In summer, the average CH4 and N2O concentrations in northern Taiwan Strait are about 3.27¡Ó2.42nM and 7.22¡Ó0.62nM (n=7), respectively; and the average CH4 and N2O fluxes are about 0.17¡Ó0.43£gmol/m2/h and 0.14¡Ó0.26 £gmol/m2/h, respectively. The average CH4 and N2O concentrations in southern Taiwan Strait are about 3.35¡Ó1.97nM and10.31¡Ó2.51nM (n=30), respectively; and the average CH4 and N2O fluxes are about 0.04¡Ó0.09£gmol/m2/h and 0.19¡Ó0.22 £gmol/m2/h, respectively. In winter, the average CH4 and N2O concentrations in northern Taiwan Strait are about 4.74¡Ó1.43nM and 8.41¡Ó0.46nM (n=9), respectively; and the average CH4 and N2O fluxes are about 0.10¡Ó0.14£gmol/m2/h and 0.008¡Ó0.033 £gmol/m2/h, respectively. The average CH4 and N2O concentrations in southern Taiwan Strait are about 4.70¡Ó2.42nM and 8.36¡Ó0.97nM (n=17), respectively; and the average CH4 and N2O fluxes are about 0.17¡Ó0.46£gmol/m2/h and 0.11¡Ó0.12 £gmol/m2/h, respectively. Taiwan Strait is a source of CH4 and N2O regardless of whether it is summer or winter. In summer, the average CH4 and N2O concentrations in the South China Sea are about 4.34¡Ó2.33nM and 8.23¡Ó1.5nM (n=55), respectively; and the average CH4 and N2O fluxes are about 0.33¡Ó0.35£gmol/m2/h and 0.20¡Ó0.24 £gmol/m2/h, respectively. It is a source of CH4 and N2O to the atmosphere. In summer, the average CH4 and N2O concentrations in the West Philippines Sea are about 3.18¡Ó1.57nM and 4.64¡Ó0.39nM (n=60), respectively; and the average CH4 and N2O fluxes are about 0.23¡Ó0.33£gmol/m2/h and -0.28¡Ó0.30 £gmol/m2/h, respectively. It is a source of CH4 but a sink of N2O to the atmosphere.

Most natural gas fields in Saudi Arabia contain around 10 mol.% carbon dioxide. The present technology to remove carbon dioxide is performed by chemical absorption, which has many drawbacks. Alternatively, membrane-based gas separation technology has attracted great interest in recent years due to: (i) simple modular design, (ii) potential cost effectiveness, (iii) ease of scale-up, and (iv) environmental friendliness. The state-of-the-art membrane materials for natural gas sweetening are glassy cellulose acetate and polyimide, which were introduced in the 1980s. In the near future, the kingdom is planning to boost its production of natural gas for power generation and increase the feedstock for new petrochemical plants. Therefore, the kingdom and worldwide market has an urgent need for better membrane materials to remove carbon dioxide from raw natural gas. The focus of this dissertation was to design new polyimide membrane materials for CO2/CH4 separation exhibiting high permeability and high selectivity relative to the standard commercial materials tested under realistic mixed-gas feed conditions. Furthermore, this study provided a fundamental understanding of structure/gas transport property relationships of triptycene-based PIM-polyimides. Optimally designed intrinsically microporous polyimide (PIM-PIs) membranes in this work exhibited drastically increased CO2/CH4 selectivities of up to ~75. In addition, a novel triptycene-based hydroxyl-containing polyimide (TDA1-APAF) showed 5-fold higher permeabilities over benchmark commercial materials such as cellulose acetate. Furthermore, this polyimide had a N2/CH4 selectivity of 2.3, thereby making it possible to simultaneously treat CO2- and N2-contaminated natural gas. Also, TDA1-APAF showed a CO2 permeability of 21 Barrer under binary 1:1 CO2/CH4 mixed-gas feed with a selectivity of 72 at a partial CO2 pressure of 10 bar which are significantly better than cellulose triacetate. These results suggest that TDA1-APAF polyimide is an excellent candidate membrane material for removal of CO2 and N2 from natural gas. Moreover, based on the collected data for CO2/CH4 mixed-gas experiments from this work and previously published reports, a new mixed-gas 2017 CO2/CH4 permeability/selectivity upper bound curve was initiated to reflect the actual performance including plasticization phenomena at high feed pressure and 10 bar CO2 partial pressure to simulate the real conditions of the wellhead pressure.

The presented dissertation assesses the technological and economical use of high-pressure hydrolysis of wheat straw with sulfuric acid (H2SO4) for biogas producing. The theoretical part is focusing to the structure of lignocellulosis phytomass, on technology of mechanical treatment and acid hydrolysis. The experimental part is based on the production of neutralized hydrolyzate obtained by using technology of high-pressure hydrolyse by pressure 1,5 MPa, in retention time of 500 seconds and 190 °C. Data, generated by operation server Linode Platform Manager, emerges, that the area with the best polynormal cubic function, which is aproximated by the smallest mistake. The local extremes, where are the verification of the cumulative CH4 by anaerobic fermentation (in thermophilic area by temperature 51 °C) in relation on dry matter, are calculated of tha data obtained of Maple 14. The highest yeld of CH4 production was found by pressure of high-pressure hydrolyser 2,37 MPa. The maximum value of production of biogas (CH4) was 190 m3. t-1 of dry phytomass. Based on the optimalization, was maximum yeld of CH4 (of biochemical aspects) found about dry matter 8,57 % and pH 4,84. From the managerial point of view, which takes into account technological limitations and financial indicator, are the optimal conditions by dry matter from 3,92 to 5,12 % and a pH of 3,2 to 5,1.

No description available.

Methane (CH4) is guaranteed to affect climate change and is essential in rising temperatures. Scientists have known for over two decades that wetlands emit CH4 to such an extent that it affects our climate. Tropical trees that grow in wetlands tend to emit or act as a conduit of CH4, to the extent that it has a negative environmental impact. However, until this study, no one has examined whether wetland species growing in another environment have the same effects. Hence, this thesis aimed to collect data from wetland-adapted tropical trees in a non-wetland environment, namely the Botanical Garden in Rio de Janeiro. The results showed a difference in the sampling height of the stem, namely that a decrease in emission is seen with an increased height. All the species except one (Pseudobombax munguba) showed both assimilation and emission from the day-to-day measurements of CH4, which speaks for the trees acting both as a sink and a source of CH4. This suggests that the species are more robust than the environmental stressors in a non-wetland environment. Previous studies have found that increased CH4 emissions can be seen with different meteorological parameters. The results presented in this thesis show the opposite, that some species tend to emit less or assimilate more CH4 during days with increased rainfall, humidity, and temperature.

Master of Science / Department of Biological and Agricultural Engineering / Zifei Liu / This study reviewed state-of-the-art cattle enteric methane (CH4) emissions with three reported measuring units: g/head/d, g/kg DMI (dry matter intake), and %GEI (gross energy intake). Cattle emissions studies included in this meta-analysis were reported from 1995 to 2013. Fifty-five published studies were analyzed with specific objectives: (1) to gain basic information regarding magnitudes and distributions of enteric CH4 emission rates with various units, regions, cattle types and feed situations; (2) to identify and evaluate effects of influence factors or diet mitigation techniques on enteric CH4 emissions; and (3) to evaluate Intergovernmental Panel on Climate Change (IPCC) approaches to estimate enteric CH4 emissions. Emissions data (n=165) with the unit of g/head/d had large variances and non-normal distribution, and were not homogeneous across the studies. Emissions data (n=134) with the unit of g/kg DMI were not homogeneous across the studies, while emissions data (n=76) with the unit of %GEI had small variances and normal distribution, and were homogeneous across the studies. Therefore, data with the unit of %GEI may be better for meta-analysis compared to data with the units of g/head/d and g/kg DMI; however, the number of data with the unit of %GEI was small relative to the number of data with the units of g/head/d and g/kg DMI. Enteric CH4 emissions with the unit of g/head/d are significantly influenced by geographic region, cattle classification, sub-classification, humidity, temperature, body weight, and feed intake. Emissions and feed intake had a strong positive linear relationship with R2 of 0.75 (n=148). Emissions with the unit of g/kg DMI are significantly affected by humidity, body weight, and feed intake. The relationship between emissions and feed intake is positive. Emissions with the unit of %GEI are significantly associated with humidity, production stage, and body weight. IPCC Tier 1 and Tier 2 estimated emissions were approximate to most of the measured enteric CH4 emissions; however, the residuals were not normally distributed. Based on results from PRD method and paired t-tests, IPCC Tier 1 overestimated emissions in Asian studies, underestimated emissions in European studies for beef cattle, and underestimated emissions in Oceanian studies for dairy cattle. IPCC Tier 2 underestimated emissions in Asian studies for beef cattle. The underestimated emissions of IPCC Tier 2 in Asian studies might result from no consideration of effects from production stage and body weight.