Development of an Autonomous Robot for Gas Storage Spheres Inspection

Inspection for corrosion of gas storage spheres at the welding seam lines must be done periodically. Until now this inspection is being done manually and has a high cost associated to it and a high risk of inspection personel injuries. The Brazilian Petroleum Company, Petrobras, is seeking cost reduction and personel safety by the use of autonomous robot technology. This paper presents the development of a robot capable of autonomously follow a welding line and transporting corrosion measurement sensors. The robot uses a pair of sensors each composed of a laser source and a video camera that allows the estimation of the center of the welding line. The mechanical robot uses four magnetic wheels to adhere to the sphere's surface and was constructed in a way that always three wheels are in contact with the sphere's metallic surface which guarantees enough magnetic atraction to hold the robot in the sphere's surface all the time. Additionally, an independently actuated table for attaching the corrosion inspection sensors was included for small position corrections. Tests were conducted at the laboratory and in a real sphere showing the validity of the proposed approach and implementation.

Adsorbent density impact on gas storage capacities

In the literature, different approaches, terminologies, concepts and equations are used for calculating gas storage capacities. Very often, these approaches are not well defined, used and/or determined, giving rise to significant misconceptions. Even more, some of these approaches, very much associated with the type of adsorbent material used (e.g., porous carbons or new materials such as COFs and MOFs), impede a suitable comparison of their performances for gas storage applications. We review and present the set of equations used to assess the total storage capacity for which, contrarily to the absolute adsorption assessment, all its experimental variables can be determined experimentally without assumptions, ensuring the comparison of different porous storage materials for practical application. These material-based total storage capacities are calculated by taking into account the excess adsorption, the bulk density (ρbulk) and the true density (ρtrue) of the adsorbent. The impact of the material densities on the results are investigated for an exemplary hydrogen isotherm obtained at room temperature and up to 20 MPa. It turns out that the total storage capacity on a volumetric basis, which increases with both, ρbulk and ρtrue, is the most appropriate tool for comparing the performance of storage materials. However, the use of the total storage capacities on a gravimetric basis cannot be recommended, because low material bulk densities could lead to unrealistically high gravimetric values.

Gas Storage Scale-up at Room Temperature on High Density Carbon Materials

In relation to the current interest on gas storage demand for environmental applications (e.g., gas transportation, and carbon dioxide capture) and for energy purposes (e.g., methane and hydrogen), high pressure adsorption (physisorption) on highly porous sorbents has become an attractive option. Considering that for high pressure adsorption, the sorbent requires both, high porosity and high density, the present paper investigates gas storage enhancement on selected carbon adsorbents, both on a gravimetric and on a volumetric basis. Results on carbon dioxide, methane, and hydrogen adsorption at room temperature (i.e., supercritical and subcritical gases) are reported. From the obtained results, the importance of both parameters (porosity and density) of the adsorbents is confirmed. Hence, the densest of the different carbon materials used is selected to study a scale-up gas storage system, with a 2.5 l cylinder tank containing 2.64 kg of adsorbent. The scale-up results are in agreement with the laboratory scale ones and highlight the importance of the adsorbent density for volumetric storage performances, reaching, at 20 bar and at RT, 376 g l-1, 104 g l-1, and 2.4 g l-1 for CO2, CH4,and H2, respectively.

Applications for CO2-Activated Carbon Monoliths: I. Gas Storage

Carbon monoliths with high densities are studied as adsorbents for the storage of H2, CH4, and CO2 at ambient temperature and high pressures. The starting monolith A3 (produced by ATMI Co.) was activated under a CO2 flow at 1073 K, applying different activation times up to 48 h. Micropore volumes and apparent surface areas were deduced from N2 and CO2 adsorption isotherms at 77 K and 273 K, respectively. CO2 and CH4 isotherms were measured up to 3 MPa and H2 up to 20 MPa. The BET surface area of the starting monolith (941 m2/g) could be significantly increased up to 1586 m2/g, and the developed porosity is almost exclusively comprised of micropores <1 nm. Total storage amounts take into account the compressed gas in the void space of the material, in addition to the adsorbed gas. Remarkably, high total storage amounts are reached for CO2 (482 g/L), CH4 (123 g/L), and H2 (18 g/L). These values are much higher than for other sorbents with similar surface areas, due to the high density of the starting monolith and of the activated ones, for which the density decreases only slightly (from 1.0 g/cm3 to 0.8 g /cm3 upon CO2 activation). The findings reveal the suitability of high density activated carbon monoliths for gas storage application. Thus, the amounts of stored gas can be increased by more than a 70 % in the case of H2 at 20 MPa, almost 5.5 times in the case of CH4 at 3 MPa, and more than 7.5 times in the case of CO2 at 3 MPa when adsorbents are used for gas storage under the investigated conditions rather than simple compression. Furthermore, the obtained results have been recently confirmed by a scale-up study in which 2.64 kg of high density monolith adsorbent was filled a tank cylinder of 2.5 L (Carbon, 76, 2014, 123).

Design and Off-design modelling of advanced Power-to-Gas energy storage systems

Power-to-Gas storage systems have the potential to address grid-stability issues that arise when an increasing share of power is generated from sources that have a highly variable output. Although the proof-of-concept of these has been promising, the behaviour of the processes in off-design conditions is not easily predictable. The primary aim of this PhD project was to evaluate the performance of an original Power-to-Gas system, made up of innovative components. To achieve this, a numerical model has been developed to simulate the characteristics and the behaviour of the several components when the whole system is coupled with a renewable source. The developed model has been applied to a large variety of scenarios, evaluating the performance of the considered process and exploiting a limited amount of experimental data. The model has been then used to compare different Power-to-Gas concepts, in a real scenario of functioning. Several goals have been achieved. In the concept phase, the possibility to thermally integrate the high temperature components has been demonstrated. Then, the parameters that affect the energy performance of a Power-to-Gas system coupled with a renewable source have been identified, providing general recommendations on the design of hybrid systems; these parameters are: 1) the ratio between the storage system size and the renewable generator size; 2) the type of coupled renewable source; 3) the related production profile. Finally, from the results of the comparative analysis, it is highlighted that configurations with a highly oversized renewable source with respect to the storage system show the maximum achievable profit.

Proposta metodológica para avaliação preliminar de jazigos de shale gas

O potencial de um reservatório de shale gas e influenciado por um grande número de fatores, tais como a sua mineralogia e textura, o seu tipo e maturação de querogénio, a saturação de fluidos, os mecanismos de armazenamento de gás, a profundidade do reservatório e a temperatura e pressão de poros. Nesse sentido, o principal objetivo desta tese foi estabelecer uma metodologia de avaliação preliminar de potenciais jazigos de shale gas (estudo de afloramentos com base numa litoestratigrafia de alta resolução), que foi posteriormente aplicada na Formação de Vale das Fontes (Bacia Lusitânica, Portugal). Esta tese tem a particularidade de contribuir, não só para o aprofundamento da informação a nível geoquímico do local, mas também na abordagem inovadora que permitiu a caracterização petrofísica da Formação de Vale das Fontes. Para a aplicação da metodologia estabelecida, foi necessária a realização dos seguintes ensaios laboratoriais: Rock-Eval 6, picnometria de gás hélio, ensaio de resistência a compressão simples, Darcypress e a difracção de raios-X, aplicando o método de Rietveld. Os resultados obtidos na análise petrofísica mostram uma formação rochosa de baixa porosidade que segundo a classificação ISRM, e classificada como ”Resistente”, para alem de revelar comportamento dúctil e elevado índice de fragilidade. A permeabilidade média obtida situa a Formação no intervalo correspondente as permeabilidades atribuídas aos jazigos de tigh gas, indicando a necessidade de fracturação hidráulica, no caso de uma eventual exploração de hidrocarbonetos, enquanto a difracção de raios-X destaca a calcite, o quartzo e os filossilicatos como os minerais mais presentes na Formação. Do ponto de vista geoquímico, os resultados obtidos mostram que apesar do considerável teor médio de carbono orgânico total, a natureza da matéria orgânica analisada e maioritariamente imatura, composta, principalmente, por querogénio do tipo IV, o que indica a incapacidade de a formação gerar hidrocarbonetos em quantidades economicamente exploráveis.

Molecular simulation of gas adsorption equilibria in nanoporous materials

This work is divided into two distinct parts. The first part consists of the study of the metal organic framework UiO-66Zr, where the aim was to determine the force field that best describes the adsorption equilibrium properties of two different gases, methane and carbon dioxide. The other part of the work focuses on the study of the single wall carbon nanotube topology for ethane adsorption; the aim was to simplify as much as possible the solid-fluid force field model to increase the computational efficiency of the Monte Carlo simulations. The choice of both adsorbents relies on their potential use in adsorption processes, such as the capture and storage of carbon dioxide, natural gas storage, separation of components of biogas, and olefin/paraffin separations. The adsorption studies on the two porous materials were performed by molecular simulation using the grand canonical Monte Carlo (μ,V,T) method, over the temperature range of 298-343 K and pressure range 0.06-70 bar. The calibration curves of pressure and density as a function of chemical potential and temperature for the three adsorbates under study, were obtained Monte Carlo simulation in the canonical ensemble (N,V,T); polynomial fit and interpolation of the obtained data allowed to determine the pressure and gas density at any chemical potential. The adsorption equilibria of methane and carbon dioxide in UiO-66Zr were simulated and compared with the experimental data obtained by Jasmina H. Cavka et al. The results show that the best force field for both gases is a chargeless united-atom force field based on the TraPPE model. Using this validated force field it was possible to estimate the isosteric heats of adsorption and the Henry constants. In the Grand-Canonical Monte Carlo simulations of carbon nanotubes, we conclude that the fastest type of run is obtained with a force field that approximates the nanotube as a smooth cylinder; this approximation gives execution times that are 1.6 times faster than the typical atomistic runs.

40 K Neon liquid energy storage unit

Cryocoolers have been progressively replacing the use of the stored cryogens in cryogenic chains used for detector cooling, thanks to their higher and higher reliability. However, the mechanical vibrations, the electromagnetic interferences and the temperature fluctuations inherent to their functioning could reduce the sensor’s sensitivity. In order to minimize this problem, compact thermal energy storage units (ESU) are studied, devices able to store thermal energy without significant temperature increase. These devices can be used as a temporary cold source making it possible to turn the cryocooler OFF providing a proper environment for the sensor. A heat switch is responsible for the thermal decoupling of the ESU from the cryocooler’s temperature that increases when turned OFF. In this work, several prototypes working around 40 K were designed, built and characterized. They consist in a low temperature cell that contains the liquid neon connected to an expansion volume at room temperature for gas storage during the liquid evaporation phase. To turn this system insensitive to the gravity direction, the liquid is retained in the low temperature cell by capillary effect in a porous material. Thanks to pressure regulation of the liquid neon bath, 900 J were stored at 40K. The higher latent heat of the liquid and the inexistence of triple point transitions at 40 K turn the pressure control during the evaporation a versatile and compact alternative to an ESU working at the triple point transitions. A quite compact second prototype ESU directly connected to the cryocooler cold finger was tested as a temperature stabilizer. This device was able to stabilize the cryocooler temperature ((≈ 40K ±1 K) despite sudden heat bursts corresponding to twice the cooling power of the cryocooler. This thesis describes the construction of these devices as well as the tests performed. It is also shown that the thermal model developed to predict the thermal behaviour of these devices, implemented as a software,describes quite well the experimental results. Solutions to improve these devices are also proposed.

40 K neon liquid energy storage unit

Cryocoolers have been progressively replacing the use of the stored cryogens in cryogenic chains used for detector cooling, thanks to their higher and higher reliability. However, the mechanical vibrations, the electromagnetic interferences and the temperature fluctuations inherent to their functioning could reduce the sensor’s sensitivity. In order to minimize this problem, compact thermal energy storage units (ESU) are studied, devices able to store thermal energy without significant temperature increase. These devices can be used as a temporary cold source making it possible to turn the cryocooler OFF providing a proper environment for the sensor. A heat switch is responsible for the thermal decoupling of the ESU from the cryocooler’s temperature that increases when turned OFF. In this work, several prototypes working around 40 K were designed, built and characterized. They consist in a low temperature cell that contains the liquid neon connected to an expansion volume at room temperature for gas storage during the liquid evaporation phase. To turn this system insensitive to the gravity direction, the liquid is retained in the low temperature cell by capillary effect in a porous material. Thanks to pressure regulation of the liquid neon bath, 900 J were stored at 40K. The higher latent heat of the liquid and the inexistence of triple point transitions at 40 K turn the pressure control during the evaporation a versatile and compact alternative to an ESU working at the triple point transitions. A quite compact second prototype ESU directly connected to the cryocooler cold finger was tested as a temperature stabilizer. This device was able to stabilize the cryocooler temperature ((≈ 40K ±1 K) despite sudden heat bursts corresponding to twice the cooling power of the cryocooler. This thesis describes the construction of these devices as well as the tests performed. It is also shown that the thermal model developed to predict the thermal behaviour of these devices,implemented as a software, describes quite well the experimental results. Solutions to improve these devices are also proposed.

Sviluppo di una metodologia per la modellazione geologica-geomeccanica ed il monitoraggio di reservoir adibiti a siti di stoccaggio di gas naturale

La valutazione dei rischi associati all’operatività dei sistemi di stoccaggio, quali la sismicità indotta e la subsidenza, è requisito basilare per una loro corretta gestione e progettazione, e passa attraverso la definizione dell’influenza sullo stato tensionale delle variazioni di pressione di poro nel sottosuolo. Principale scopo di questo progetto è lo sviluppo di una metodologia in grado di quantificare le deformazioni dei reservoir in funzione della pressione di poro, di tarare i modelli utilizzati con casi studio che presentino dati di monitoraggio reali, tali da consentire un confronto con le previsioni di modello. In questa tesi, la teoria delle inomogeneità è stata utilizzata, tramite un approccio semianalitico, per definire le variazioni dei campi elastici derivanti dalle operazioni di prelievo e immissione di fluidi in serbatoi geologici. Estensione, forma e magnitudo delle variazioni di stress indotte sono state valutate tramite il concetto di variazione dello sforzo critico secondo il criterio di rottura di Coulomb, tramite un’analisi numerica agli elementi finiti. La metodologia sviluppata è stata applicata e tarata su due reservoir sfruttati e riconvertiti a sistemi di stoccaggio che presentano dataset, geologia, petrofisica, e condizioni operative differenti. Sono state calcolate le variazioni dei campi elastici e la subsidenza; è stata mappata la variazione di sforzo critico di Coulomb per entrambi i casi. I risultati ottenuti mostrano buon accordo con le osservazioni dei monitoraggi, suggerendo la bontà della metodologia e indicando la scarsa probabilità di sismicità indotta. Questo progetto ha consentito la creazione di una piattaforma metodologica di rapido ed efficace utilizzo, per stimare l’influenza dei sistemi di stoccaggio di gas sullo stato tensionale della crosta terrestre; in fase di stoccaggio, permette di monitorare le deformazioni e gli sforzi indotti; in fase di progettazione, consente di valutare le strategie operative per monitorare e mitigare i rischi geologici associati a questi sistemi.

The Domestic Natural Gas Shortage in China

This thesis analyzes the domestic shortage in the Chinese natural gas market. Both the domestic supply and demand of natural gas are growing fast in China. However, the supply cannot catch up with the demand. Under the present pricing mechanism, the Chinese natural gas market cannot get the equilibrium by itself. Expensive imports are inadequate to fill the increasing gap between the domestic demand and supply. Therefore, the shortage problem occurs. Since the energy gap can result in the arrested development of economics, the shortage problem need to be solved. This thesis gives three suggestions to solve the problem: the use of Unconventional Gas, Natural Gas Storage and Pricing Reform.

Gas composition, concentration and stable isotope ratios (Table 2, 3, 4)

The deployment of CCS (carbon capture and storage) at industrial scale implies the development of effective monitoring tools. Noble gases are tracers usually proposed to track CO2. This methodology, combined with the geochemistry of carbon isotopes, has been tested on available analogues. At first, gases from natural analogues were sampled in the Colorado Plateau and in the French carbogaseous provinces, in both well-confined and leaking-sites. Second, we performed a 2-years tracing experience on an underground natural gas storage, sampling gas each month during injection and withdrawal periods. In natural analogues, the geochemical fingerprints are dependent on the containment criterion and on the geological context, giving tools to detect a leakage of deep-CO2 toward surface. This study also provides information on the origin of CO2, as well as residence time of fluids within the crust and clues on the physico-chemical processes occurring during the geological story. The study on the industrial analogue demonstrates the feasibility of using noble gases as tracers of CO2. Withdrawn gases follow geochemical trends coherent with mixing processes between injected gas end-members. Physico-chemical processes revealed by the tracing occur at transient state. These two complementary studies proved the interest of geochemical monitoring to survey the CO2 behaviour, and gave information on its use.

Recuperación secundaria en campos de petróleo y su conversión en almacenamientos subterráneos de gas natural

El objetivo de este proyecto es estudiar la recuperación secundaria de petróleo de la capa sureste Ayoluengo del campo Ayoluengo, Burgos (España), y su conversión en un almacenamiento subterráneo de gas. La capa Ayoluengo se ha considerado como una capa inclinada de 60 km por 10 km de superficie por 30 m de espesor en el que se han perforado 20 pozos, y en donde la recuperación primaria ha sido de un 19%. Se ha realizado el ajuste histórico de la recuperación primaria de gas, petróleo y agua de la capa desde el año 1965 al 2011. La conversión a almacenamiento subterráneo de gas se ha realizado mediante ciclos de inyección de gas, de marzo a octubre, y extracción de gas, de noviembre a febrero, de forma que se incrementa la presión del campo hasta alcanzar la presión inicial. El gas se ha inyectado y extraído por 5 pozos situados en la zona superior de la capa. Al mismo tiempo, se ha realizado una recuperación secundaria debido a la inyección de gas natural de 20 años de duración en donde la producción de petróleo se realiza por 14 pozos situados en la parte inferior de la capa. Para proceder a la simulación del ajuste histórico, conversión en almacenamiento y recuperación secundaria se utilizó el simulador Eclipse100. Los resultados obtenidos fueron una recuperación secundaria de petróleo de un 9% más comparada con la primaria. En cuanto al almacenamiento de gas natural, se alcanzó la presión inicial consiguiendo un gas útil de 300 Mm3 y un gas colchón de 217,3 Mm3. ABSTRACT The aim of this project is to study the secondary recovery of oil from the southeast Ayoluengo layer at the oil field Ayoluengo, Burgos (Spain), and its conversion into an underground gas storage. The Ayoluengo layer is an inclined layer of 60 km by 10km of area by 30 m gross and with 20 wells, which its primary recovery is of 19%. The history matching of the production of oil, gas and water has been carried out from the year 1965 until 2011. The conversion into an underground gas storage has been done in cycles of gas injection from March to October, and gas extraction from November to February, so that the reservoir pressure increases until it gets to the initial pressure. The gas has been injected and extracted through five well situated in the top part of the layer. At the same time, the secondary recovery has occurred due to de injection of natural gas during 20 years where the production of oil has been done through 14 wells situated in the lowest part of the layer. To proceed to the simulation of the history match, the conversion into an underground gas storage and its secondary recovery, the simulator used was Eclipse100. The results were a secondary recovery of oil of 9% more, compared to the primary recovery and concerning the underground gas storage, the initial reservoir pressure was achieved with a working gas of 300 Mm3 and a cushion gas of 217,3 Mm3.

Criterios de selección de una estructura favorable para un almacenamiento de gas natural : Aplicación a escala de cuenca en la Península Ibérica

RESUMEN Este proyecto ha tenido por objetivo el estudio de la viabilidad de instalar un nuevo almacenamiento subterráneo de gas natural en España. Dentro de las diferentes posibilidades para emplazar el almacenamiento de gas natural se escogió el domo salino por ser la estructura geológica más favorable desde el punto de vista técnico y económico. Una vez escogido el domo salino, el estudio se centró en localizar una ubicación lo más favorable posible siendo el domo salino de Salinas de Añana el elegido. Una vez elegido el domo se procedió al estudio de la viabilidad técnica de la instalación; para ello se utilizaron estudios geológicos, gavimétricos y sondeos. Tras estos estudios se concluyó que en el domo salino de Salinas de Añana es posible la instalación de un almacenamiento subterráneo de gas natural y se procedió a la caracterización del almacenamiento. ABSTRACT This project has considered of installing a new underground natural gas storage in Spain. Among the different possibilities to place a natural gas storage, the salt dome was chosen because it was the geological strucutrure where the project was easier and more interesting economically. After that the study focused on looking for the location as favorable as possible. The best place was the salt dome of Salinas de Añana. Before the salt dome of Salinas de Añana was chosen this project tried to know if the setting-up of a natural gas storage is technical feasibility. For that were used geological studies, gravity studies and drillings. These studies concluded that is possible the setting-up and the study tried to describe technically this storage.

High-Pressure Methane Storage in Porous Materials: Are Carbon Materials in the Pole Position?

Natural gas storage on porous materials (ANG) is a promising alternative to conventional on-board compressed (CNG) or liquefied natural gas (LNG). To date, Metal–organic framework (MOF) materials have apparently been the only system published in the literature that is able to reach the new Department of Energy (DOE) value of 263 cm3 (STP: 273.15 K, 1 atm)/cm3; however, this value was obtained by using the ideal single-crystal density to calculate the volumetric capacity. Here, we prove experimentally, and for the first time, that properly designed activated carbon materials can really achieve the new DOE value while avoiding the additional drawback usually associated with MOF materials (i.e., the low mechanical stability under pressure (conforming), which is required for any practical application).