932 resultados para H2 oxy-reforming water-gas-shift ceramic-membranes Pd


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River structure and functioning are governed naturally by geography and climate but are vulnerable to natural and human-related disturbances, ranging from channel engineering to pollution and biological invasions. Biological communities in river ecosystems are able to respond to disturbances faster than those in most other aquatic systems. However, some extremely strong or lasting disturbances constrain the responses of river organisms and jeopardise their extraordinary resilience. Among these, the artificial alteration of river drainage structure and the intense use of water resources by humans may irreversibly influence these systems. The increased canalisation and damming of river courses interferes with sediment transport, alters biogeochemical cycles and leads to a decrease in biodiversity, both at local and global scales. Furthermore, water abstraction can especially affect the functioning of arid and semi-arid rivers. In particular, interception and assimilation of inorganic nutrients can be detrimental under hydrologically abnormal conditions. Among other effects, abstraction and increased nutrient loading might cause a shift from heterotrophy to autotrophy, through direct effects on primary producers and indirect effects through food webs, even in low-light river systems. The simultaneous desires to conserve and to provide ecosystem services present several challenges, both in research and management.

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[EN] This PhD work started in March 2010 with the support of the University of the Basque Country (UPV/EHU) under the program named “Formación de Personal Investigador” at the Chemical and Environmental Engineering Department in the Faculty of Engineering of Bilbao. The major part of the Thesis work was carried out in the mentioned department, as a member of the Sustainable Process Engineering (SuPrEn) research group. In addition, this PhD Thesis includes the research work developed during a period of 6 months at the Institut für Mikrotechnik Mainz GmbH, IMM, in Germany. During the four years of the Thesis, conventional and microreactor systems were tested for several feedstocks renewable and non-renewable, gases and liquids through several reforming processes in order to produce hydrogen. For this purpose, new catalytic formulations which showed high activity, selectivity and stability were design. As a consequence, the PhD work performed allowed the publication of seven scientific articles in peer-reviewed journals. This PhD Thesis is divided into the following six chapters described below. The opportunity of this work is established on the basis of the transition period needed for moving from a petroleum based energy system to a renewable based new one. Consequently, the present global energy scenario was detailed in Chapter 1, and the role of hydrogen as a real alternative in the future energy system was justified based on several outlooks. Therefore, renewable and non-renewable hydrogen production routes were presented, explaining the corresponding benefits and drawbacks. Then, the raw materials used in this Thesis work were described and the most important issues regarding the processes and the characteristics of the catalytic formulations were explained. The introduction chapter finishes by introducing the concepts of decentralized production and process intensification with the use of microreactors. In addition, a small description of these innovative reaction systems and the benefits that entailed their use were also mentioned. In Chapter 2 the main objectives of this Thesis work are summarized. The development of advanced reaction systems for hydrogen rich mixtures production is the main objective. In addition, the use and comparison between two different reaction systems, (fixed bed reactor (FBR) and microreactor), the processing of renewable raw materials, the development of new, active, selective and stable catalytic formulations, and the optimization of the operating conditions were also established as additional partial objectives. Methane and natural gas (NG) steam reforming experimental results obtained when operated with microreactor and FBR systems are presented in Chapter 3. For these experiments nickel-based (Ni/Al2O3 and Ni/MgO) and noble metal-based (Pd/Al2O3 and Pt/Al2O3) catalysts were prepared by wet impregnation and their catalytic activity was measured at several temperatures, from 973 to 1073 K, different S/C ratios, from 1.0 to 2.0, and atmospheric pressure. The Weight Hourly Space Velocity (WHSV) was maintained constant in order to compare the catalytic activity in both reaction systems. The results obtained showed a better performance of the catalysts operating in microreactors. The Ni/MgO catalyst reached the highest hydrogen production yield at 1073 K and steam-to-carbon ratio (S/C) of 1.5 under Steam methane Reforming (SMR) conditions. In addition, this catalyst also showed good activity and stability under NG reforming at S/C=1.0 and 2.0. The Ni/Al2O3 catalyst also showed high activity and good stability and it was the catalyst reaching the highest methane conversion (72.9 %) and H2out/CH4in ratio (2.4) under SMR conditions at 1073 K and S/C=1.0. However, this catalyst suffered from deactivation when it was tested under NG reforming conditions. Regarding the activity measurements carried out with the noble metal-based catalysts in the microreactor systems, they suffered a very quick deactivation, probably because of the effects attributed to carbon deposition, which was detected by Scanning Electron Microscope (SEM). When the FBR was used no catalytic activity was measured with the catalysts under investigation, probably because they were operated at the same WHSV than the microreactors and these WHSVs were too high for FBR system. In Chapter 4 biogas reforming processes were studied. This chapter starts with an introduction explaining the properties of the biogas and the main production routes. Then, the experimental procedure carried out is detailed giving concrete information about the experimental set-up, defining the parameters measured, specifying the characteristics of the reactors used and describing the characterization techniques utilized. Each following section describes the results obtained from activity testing with the different catalysts prepared, which is subsequently summarized: Section 4.3: Biogas reforming processes using γ-Al2O3 based catalysts The activity results obtained by several Ni-based catalysts and a bimetallic Rh-Ni catalyst supported on magnesia or alumina modified with oxides like CeO2 and ZrO2 are presented in this section. In addition, an alumina-based commercial catalyst was tested in order to compare the activity results measured. Four different biogas reforming processes were studied using a FBR: dry reforming (DR), biogas steam reforming (BSR), biogas oxidative reforming (BOR) and tri-reforming (TR). For the BSR process different steam to carbon ratios (S/C) from 1.0 to 3.0, were tested. In the case of BOR process the oxygen-to-methane (O2/CH4) ratio was varied from 0.125 to 0.50. Finally, for TR processes different S/C ratios from 1.0 to 3.0, and O2/CH4 ratios of 0.25 and 0.50 were studied. Then, the catalysts which achieved high activity and stability were impregnated in a microreactor to explore the viability of process intensification. The operation with microreactors was carried out under the best experimental conditions measured in the FBR. In addition, the physicochemical characterization of the fresh and spent catalysts was carried out by Inductively Coupled Plasma Atomic Emission Spectroscopy (ICP-AES), N2 physisorption, H2 chemisorption, Temperature Programmed Reduction (TPR), SEM, X-ray Photoelectron Spectroscopy (XPS) and X-ray powder Diffraction (XRD). Operating with the FBR, conversions close to the ones predicted by thermodynamic calculations were obtained by most of the catalysts tested. The Rh-Ni/Ce-Al2O3 catalyst obtained the highest hydrogen production yield in DR. In BSR process, the Ni/Ce-Al2O3 catalyst achieved the best activity results operating at S/C=1.0. In the case of BOR process, the Ni/Ce-Zr-Al2O3 catalyst showed the highest reactants conversion values operating at O2/CH4=0.25. Finally, in the TR process the Rh-Ni/Ce-Al2O3 catalyst obtained the best results operating at S/C=1.0 and O2/CH4=0.25. Therefore, these three catalysts were selected to be coated onto microchannels in order to test its performance under BOR and TR processes conditions. Although the operation using microreactors was carried out under considerably higher WHSV, similar conversions and yields as the ones measured in FBR were measured. Furthermore, attending to other measurements like Turnover Frequency (TOF) and Hydrogen Productivity (PROD), the values calculated for the catalysts tested in microreactors were one order of magnitude higher. Thus, due to the low dispersion degree measured by H2-chemisorption, the Ni/Ce-Al2O3 catalyst reached the highest TOF and PROD values. Section 4.4: Biogas reforming processes using Zeolites L based catalysts In this section three type of L zeolites, with different morphology and size, were synthesized and used as catalyst support. Then, for each type of L zeolite three nickel monometallic and their homologous Rh-Ni bimetallic catalysts were prepared by the wetness impregnation method. These catalysts were tested using the FBR under DR process and different conditions of BSR (S/C ratio of 1.0 and 2.0), BOR (O2/CH4 ratio of 0.25 and 0.50) and TR processes (at S/C=1.0 and O2/CH4=0.25). The characterization of these catalysts was also carried out by using the same techniques mentioned in the previous section. Very high methane and carbon dioxide conversion values were measured for almost all the catalysts under investigation. The experimental results evidenced the better catalytic behavior of the bimetallic catalysts as compared to the monometallic ones. Comparing the catalysts behavior with regards to their morphology, for the BSR process the Disc catalysts were the most active ones at the lowest S/C ratio tested. On the contrary, the Cylindrical (30–60 nm) catalysts were more active under BOR conditions at O2/CH4=0.25 and TR processes. By the contrary, the Cylindrical (1–3 µm) catalysts showed the worst activity results for both processes. Section 4.5: Biogas reforming processes using Na+ and Cs+ doped Zeolites LTL based catalysts A method for the synthesis of Linde Type L (LTL) zeolite under microwave-assisted hydrothermal conditions and its behavior as a support for heterogeneously catalyzed hydrogen production is described in this section. Then, rhodium and nickel-based bimetallic catalysts were prepared in order to be tested by DR process and BOR process at O2/CH4=0.25. Moreover, the characterization of the catalysts under investigation was also carried out. Higher activities were achieved by the catalysts prepared from the non-doped zeolites, Rh-Ni/D and Rh-Ni/N, as compared to the ones supported on Na+ and Cs+ exchanged supports. However, the differences between them were not very significant. In addition, the Na+ and Cs+ incorporation affected mainly to the Disc catalysts. Comparing the results obtained by these catalysts with the ones studied in the section 4.4, in general worst results were achieved under DR conditions and almost the same results when operated under BOR conditions. In Chapter 5 the ethylene glycol (EG) as feed for syngas production by steam reforming (SR) and oxidative steam reforming (OSR) was studied by using microchannel reactors. The product composition was determined at a S/C of 4.0, reaction temperatures between 625°C and 725°C, atmospheric pressure and Volume Hourly Space Velocities (VHSV) between 100 and 300 NL/(gcath). This work was divided in two sections. The first one corresponds to the introduction of the main and most promising EG production routes. Then, the new experimental procedure is detailed and the information about the experimental set-up and the measured parameters is described. The characterization was carried out using the same techniques as for the previous chapter. Then, the next sections correspond to the catalytic activity and catalysts characterization results. Section 5.3: xRh-cm and xRh-np catalysts for ethylene glycol reforming Initially, catalysts with different rhodium loading, from 1.0 to 5.0 wt. %, and supported on α-Al2O3 were prepared by two different preparation methods (conventional impregnation and separate nanoparticle synthesis). Then, the catalysts were compared regarding their measured activity and selectivity, as well as the characterization results obtained before and after the activity tests carried out. The samples prepared by a conventional impregnation method showed generally higher activity compared to catalysts prepared from Rh nanoparticles. By-product formation of species such as acetaldehyde, ethane and ethylene was detected, regardless if oxygen was added to the feed or not. Among the catalysts tested, the 2.5Rh-cm catalyst was considered the best one. Section 5.4: 2.5Rh-cm catalyst support modification with CeO2 and La2O3 In this part of the Chapter 5, the catalyst showing the best performance in the previous section, the 2.5Rh-Al2O3 catalyst, was selected in order to be improved. Therefore, new Rh based catalysts were designed using α-Al2O3 and being modified this support with different contents of CeO2 or La2O3 oxides. All the catalysts containing additives showed complete conversion and selectivities close to the equilibrium in both SR and OSR processes. In addition, for these catalysts the concentrations measured for the C2H4, CH4, CH3CHO and C2H6 by-products were very low. Finally, the 2.5Rh-20Ce catalyst was selected according to its catalytic activity and characterization results in order to run a stability test, which lasted more than 115 hours under stable operation. The last chapter, Chapter 6, summarizes the main conclusions achieved throughout this Thesis work. Although very high reactant conversions and rich hydrogen mixtures were obtained using a fixed bed reaction system, the use of microreactors improves the key issues, heat and mass transfer limitations, through which the reforming reactions are intensified. Therefore, they seem to be a very interesting and promising alternative for process intensification and decentralized production for remote application.

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Based on the well known sea ice phase diagram, equations are derived for determining the brine and gas content of sea Ice for high temperatures (range 0 to -2 °C) and low salinities. The presently widely used equations of Cox and Weeks (1982) are valid only for temperatures below -2°C. Fresh-water ice is used as a boundary condition for the equations. The relative salt concentrations in brine are_assumed to be the same as in normal (or standard) seawater. Two sets of equations are presented: 1) accurate formulae based on UNESCO standard sea water equations, and 2) approximate formulae based on general properties of weak solutions. The approximate formulae are not essentially different from the classical system which basically assumes the freezing point to be a linear function of fractional salt content. The agreement between the two approaches is excellent and the approximate system is good enough for most applications.

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To investigate the possibility that oil and gas platforms may reduce recruitment of rockfishes (Sebastes spp.) to natural habitat, we simulated drift pathways termed “trajectories” in our model) from an existing oil platform to nearshore habitat using current measurements from high-frequency (HF) radars. The trajectories originated at Platform Irene, located west of Point Conception, California, during two recruiting seasons for bocaccio (Sebastes paucispinis): May through August, 1999 and 2002. Given that pelagic juvenile bocaccio dwell near the surface, the trajectories estimate transport to habitat. We assumed that appropriate shallow water juvenile habitat exists inshore of the 50-m isobath. Results from 1999 indicated that 10% of the trajectories represent transport to habitat, whereas 76% represent transport across the offshore boundary. For 2002, 24% represent transport to habitat, and 69% represent transport across the offshore boundary. Remaining trajectories (14% and 7% for 1999 and 2002, respectively) exited the coverage area either northward or southward along isobaths. Deployments of actual drifters (with 1-m drogues) from a previous multiyear study provided measurements originating near Platform Irene from May through August. All but a few of the drifters moved offshore, as was also shown with the HF radar-derived trajectories. These results indicate that most juvenile bocaccio settling on the platform would otherwise have been transported offshore and perished in the absence of a platform. However, these results do not account for the swimming behavior of juvenile bocaccio, about which little is known.

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O vapor dágua está presente na exaustão veicular em quantidades significativas e, nas condições de operação do catalisador automotivo, essa espécie pode promover uma série de fenômenos térmicos que podem reduzir a vida útil do sistema. Dentro desse contexto, essa dissertação tem como objetivo estudar os efeitos da desativação hidrotérmica nas propriedades físico-químicas e estruturais, e no desempenho de três catalisadores automotivos comerciais à base de Pd/Rh, designados A, C e E. Esses sistemas foram submetidos a tratamento térmico a 1000C por 12 horas, sob três tipos de correntes gasosas, com a seguinte composição: N2, 14% H2O/N2 e 18% H2O/N2. A caracterização dos catalisadores consistiu das seguintes técnicas: FRX, ICP-OES, ATG-ATD, fisissorção de N2, TPD-H2 e TPR. A partir dos resultados obtidos para as amostras envelhecidas, foram constatados vários fenômenos característicos da degradação térmica, como sinterização da alumina e do óxido misto CeO2-ZrO2, transições de fases cristalina na alumina e segregação de fases no óxido misto. A avaliação da atividade catalítica foi realizada com base na reação de redução do NO pelo CO, e nas reações de oxidação do CO e do C3H8. Para os catalisadores C e E, os envelhecimentos acarretaram em perda de atividade, e os resultados da avaliação catalítica apresentaram uma boa correlação com as propriedades texturais e a redutibilidade desses catalisadores. Em contrapartida, para o catalisador A, os tratamentos térmicos o ativaram para todas as reações. Apesar de os três sistemas terem apresentado boa atividade frente à redução do NO pelo CO, foi observada, para todas as amostras, a formação indesejável de N2O em quantidades significativas, indicando que eles foram pouco seletivos na faixa de temperatura analisada

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The impact response of laminated composites consisting of alternate layers of AI ahoy foam and Al2O3 was studied experimentally in low and intermediate velocity regimes. Low velocity impacts (1.2-2.8 m s(-1)) were conducted using an instrumented falling weight apparatus and were compared with static indentation tests (0.2 x 10(-4) m s(-1)). Intermediate velocity impacts were carried out by means of both Hopkinson bar (60 m s(-1)) and gas gun (200 m s(-1)) tests, Post-impact damage was assessed using X-ray radiography and microscopy, It was found that there is good correlation between low velocity impact and quasi-static responses. In both cases, penetration of the layered targets resulted in the formation of a distinctive plug. Increasing impact velocity (intermediate velocity range) snitched the penetration mode from plugging to fragmentation, giving rise to an increase in the absorbed energy. In this range, impacts led to localisation of damage in the region under the projectile, Furthermore, a comparison has been made between the penetration response of foam laminates and dense metal laminates of equivalent areal density. Preliminary results suggest that the dense metal laminates are superseded by the foam laminates on an energy absorption basis.

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This paper presents the characterisation of self-excited oscillations in a kerosene burner. The combustion instability exhibits two different modes and frequencies depending on the air flow rate. Experimental results reveal the influence of the spray to shift between these two modes. Pressure and heat release fluctuations have been measured simultaneously and the flame transfer function has been calculated from these measurements. The Mie scattering technique has been used to record spray fluctuations in reacting conditions with a high speed camera. Innovative image processing has enabled us to obtain fluctuations of the Mie scattered light from the spray as a temporal signal acquired simultaneously with pressure fluctuations. This has been used to determine a transfer function relating the image intensity and hence the spray fluctuations to changes in air velocity. This function has identified the different role the spray plays in the two modes of instability. At low air flow rates, the spray responds to an unsteady air flow rate and the time varying spray characteristics lead to unsteady combustion. At higher air flow rates, effective evaporation means that the spray dynamics are less important, leading to a different flame transfer function and frequency of self-excited oscillation. In conclusion, the combustion instabilities observed are closely related with the fluctuations of the spray motion and evaporation.

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Although increasing the turbine inlet temperature has traditionally proved the surest way to increase cycle efficiency, recent work suggests that the performance of future gas turbines may be limited by increased cooling flows and losses. Another limiting scenario concerns the effect on cycle performance of real gas properties at high temperatures. Cycle calculations of uncooled gas turbines show that when gas properties are modelled accurately, the variation of cycle efficiency with turbine inlet temperature at constant pressure ratio exhibits a maximum at temperatures well below the stoichiometric limit. Furthermore, the temperature at the maximum decreases with increasing compressor and turbine polytropic efficiency. This behaviour is examined in the context of a two-component model of the working fluid. The dominant influences come from the change of composition of the combustion products with varying air/fuel ratio (particularly the contribution from the water vapour) together with the temperature variation of the specific heat capacity of air. There are implications for future industrial development programmes, particularly in the context of advanced mixed gas-steam cycles.

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This report gives the baseline information specifically on water quality (physical/chemical, nutrient and phytoplankton biomass status) of the open part of the lake, a river flowing into the lake and a lagoon, within Butiaba-Wanseko area. Oil and gas exploration in the Albertine Graben are on-going activities by Tullow Oil Plc, and Heritage Oil and Gas (Heritage). Part of the activities involve 2-D TZ seismic surveys in exploration area Block 2 (Butiaba-Wanseko area) in Buliisa District. A study of the transition zone (basically along the shoreline was undertaken by National Fisheries Resources Research Institute (NaFIRRI) on behalf of Environmental Assessment Consult Ltd (EACL) during September 2007. A major objective of the study was to carry out a baseline survey of the fisheries and water quality of the lake shore between Wanseko and Butiaba prior to the proposed 2-D Seisimic investigation.

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Water service providers (WSPs) in the UK have statutory obligations to supply drinking water to all customers that complies with increasingly stringent water quality regulations and minimum flow and pressure criteria. At the same time, the industry is required by regulators and investors to demonstrate increasing operational efficiency and to meet a wide range of performance criteria that are expected to improve year-on-year. Most WSPs have an ideal for improving the operation of their water supply systems based on increased knowledge and understanding of their assets and a shift to proactive management followed by steadily increasing degrees of system monitoring, automation and optimisation. The fundamental mission is, however, to ensure security of supply, with no interruptions and water quality of the highest standard at the tap. Unfortunately, advanced technologies required to fully understand, manage and automate water supply system operation either do not yet exist, are only partially evolved, or have not yet been reliably proven for live water distribution systems. It is this deficiency that the project NEPTUNE seeks to address by carrying out research into 3 main areas; these are: data and knowledge management; pressure management (including energy management); and the associated complex decision support systems on which to base interventions. The 3-year project started in April of 2007 and has already resulted in a number of research findings under the three main research priority areas (RPA). The paper summarises in greater detail the overall project objectives, the RPA activities and the areas of research innovation that are being undertaken in this major, UK collaborative study. Copyright 2009 ASCE.

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The stability of a plane liquid sheet is studied experimentally and theoretically, with an emphasis on the effect of the surrounding gas. Co-blowing with a gas velocity of the same order of magnitude as the liquid velocity is studied, in order to quantify its effect on the stability of the sheet. Experimental results are obtained for a water sheet in air at Reynolds number Rel = 3000 and Weber number W e = 300, based on the half-thickness of the sheet at the inlet, water mean velocity at the inlet, the surface tension between water and air and water density and viscosity. The sheet is excited with different frequencies at the inlet and the growth of the waves in the streamwise direction is measured. The growth rate curves of the disturbances for all air flow velocities under study are found to be within 20 % of the values obtained from a local spatial stability analysis, where water and air viscosities are taken into account, while previous results from literature assuming inviscid air overpredict the most unstable wavelength with a factor 3 and the growth rate with a factor 2. The effect of the air flow on the stability of the sheet is scrutinized numerically and it is concluded that the predicted disturbance growth scales with (i) the absolute velocity difference between water and air (inviscid effect) and (ii) the square root of the shear from air on the water surface (viscous effect).

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The stability of a plane liquid sheet is studied experimentally and theoretically, with an emphasis on the effect of the surrounding gas. Co-blowing with a gas velocity of the same order of magnitude as the liquid velocity is studied, in order to quantify its effect on the stability of the sheet. Experimental results are obtained for a water sheet in air at Reynolds number Rel = 3000 and Weber number We = 300, based on the half-thickness of the sheet at the inlet, water mean velocity at the inlet, the surface tension between water and air and water density and viscosity. The sheet is excited with different frequencies at the inlet and the growth of the waves in the streamwise direction is measured. The growth rate curves of the disturbances for all air flow velocities under study are found to be within 20% of the values obtained from a local spatial stability analysis, where water and air viscosities are taken into account, while previous results from literature assuming inviscid air overpredict the most unstable wavelength with a factor 3 and the growth rate with a factor 2. The effect of the air flow on the stability of the sheet is scrutinized numerically and it is concluded that the predicted disturbance growth scales with (i) the absolute velocity difference between water and air (inviscid effect) and (ii) the square root of the shear from air on the water surface (viscous effect).

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Electrolysis is the most mature form of hydrogen production. Unfortunately, water electrolysis has not yet achieved the efficiency and the cost levels required for any practical application. In order to enhance the current density, modification of the electrolyte and the electrode morphology are the most popular approaches. Recently there have been numerous reports on how to improve the efficiency of hydrogen production by water splitting [1-3]. On the electrode side, the use of non-platinum high efficiency electrode materials for water splitting will provide a promising future for the hydrogen economy. An ideal electrode for water electrolysis should have good permeability to water and gas. It should also offer good electrical properties with a long life. A porous graphite plate, when coated with titania, for example, is known to provide a simple and economical electrode for water electrolysis [4]. © 2010 IEEE.

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Methane hydrate, which is usually found under deep seabed or permafrost zones, is a potential energy resource for future years. Depressurization of horizontalwells bored in methane hydrate layer is considered as one possible method for hydrate dissociation and methane extraction from the hosting soil. Since hydrate is likely to behave as a bonding material to sandy soils, supported well construction is necessary to avoid wellcollapse due to the loss of the apparent cohesion during depressurization. This paper describes both physical and numerical modeling of such horizontal support wells. The experimental part involves depressurization of small well models in a large pressure cell, while the numerical part simulates the corresponding problem. While the experiment models simulate only gas saturated initial conditions, the numerical analysis simulates both gas-saturated and more realistic water-saturated conditions based on effective stress coupled flow-deformation formulation of these three phases. © 2006 Taylor & Francis Group, London.