Modelagem analítica e experimental da filtração em meios porosos

Deep bed filtration occurs in several industrial and environmental processes like water filtration and soil contamination. In petroleum industry, deep bed filtration occurs near to injection wells during water injection, causing injectivity reduction. It also takes place during well drilling, sand production control, produced water disposal in aquifers, etc. The particle capture in porous media can be caused by different physical mechanisms (size exclusion, electrical forces, bridging, gravity, etc). A statistical model for filtration in porous media is proposed and analytical solutions for suspended and retained particles are derived. The model, which incorporates particle retention probability, is compared with the classical deep bed filtration model allowing a physical interpretation of the filtration coefficients. Comparison of the obtained analytical solutions for the proposed model with the classical model solutions allows concluding that the larger the particle capture probability, the larger the discrepancy between the proposed and the classical models

Modelagem analítica e experimental da filtração em meios porosos

Deep bed filtration occurs in several industrial and environmental processes like water filtration and soil contamination. In petroleum industry, deep bed filtration occurs near to injection wells during water injection, causing injectivity reduction. It also takes place during well drilling, sand production control, produced water disposal in aquifers, etc. The particle capture in porous media can be caused by different physical mechanisms (size exclusion, electrical forces, bridging, gravity, etc). A statistical model for filtration in porous media is proposed and analytical solutions for suspended and retained particles are derived. The model, which incorporates particle retention probability, is compared with the classical deep bed filtration model allowing a physical interpretation of the filtration coefficients. Comparison of the obtained analytical solutions for the proposed model with the classical model solutions allows concluding that the larger the particle capture probability, the larger the discrepancy between the proposed and the classical models

Modelo Estocástico para bloqueio de poros e redução de permeabilidade

Modeling transport of particulate suspensions in porous media is essential for understanding various processes of industrial and scientific interest. During these processes, particles are retained due to mechanisms like size exclusion (straining), adsorption, sedimentation and diffusion. In this thesis, a mathematical model is proposed and analytical solutions are obtained. The obtained analytic solutions for the proposed model, which takes pore and particle size distributions into account, were applied to predict the particle retention, pore blocking and permeability reduction during dead-end microfiltration in membranes. Various scenarios, considering different particle and pore size distributions were studied. The obtained results showed that pore blocking and permeability reduction are highly influenced by the initial pore and particle size distributions. This feature was observed even when different initial pore and particle size distributions with the same average pore size and injected particle size were considered. Finally, a mathematical model for predicting equivalent permeability in porous media during particle retention (and pore blocking) is proposed and the obtained solutions were applied to study permeability decline in different scenarios

Modelo Estocástico para bloqueio de poros e redução de permeabilidade

Modeling transport of particulate suspensions in porous media is essential for understanding various processes of industrial and scientific interest. During these processes, particles are retained due to mechanisms like size exclusion (straining), adsorption, sedimentation and diffusion. In this thesis, a mathematical model is proposed and analytical solutions are obtained. The obtained analytic solutions for the proposed model, which takes pore and particle size distributions into account, were applied to predict the particle retention, pore blocking and permeability reduction during dead-end microfiltration in membranes. Various scenarios, considering different particle and pore size distributions were studied. The obtained results showed that pore blocking and permeability reduction are highly influenced by the initial pore and particle size distributions. This feature was observed even when different initial pore and particle size distributions with the same average pore size and injected particle size were considered. Finally, a mathematical model for predicting equivalent permeability in porous media during particle retention (and pore blocking) is proposed and the obtained solutions were applied to study permeability decline in different scenarios

Computer simulation of random parckings for self-similar particle size distributions in soil and granular materials: porosity and pore size distribution

A 2D computer simulation method of random packings is applied to sets of particles generated by a self-similar uniparametric model for particle size distributions (PSDs) in granular media. The parameter p which controls the model is the proportion of mass of particles corresponding to the left half of the normalized size interval [0,1]. First the influence on the total porosity of the parameter p is analyzed and interpreted. It is shown that such parameter, and the fractal exponent of the associated power scaling, are efficient packing parameters, but this last one is not in the way predicted in a former published work addressing an analogous research in artificial granular materials. The total porosity reaches the minimum value for p = 0.6. Limited information on the pore size distribution is obtained from the packing simulations and by means of morphological analysis methods. Results show that the range of pore sizes increases for decreasing values of p showing also different shape in the volume pore size distribution. Further research including simulations with a greater number of particles and image resolution are required to obtain finer results on the hierarchical structure of pore space.

Determination of pore size distributions by regularization and finite element collocation

The problem of extracting pore size distributions from characterization data is solved here with particular reference to adsorption. The technique developed is based on a finite element collocation discretization of the adsorption integral, with fitting of the isotherm data by least squares using regularization. A rapid and simple technique for ensuring non-negativity of the solutions is also developed which modifies the original solution having some negativity. The technique yields stable and converged solutions, and is implemented in a package RIDFEC. The package is demonstrated to be robust, yielding results which are less sensitive to experimental error than conventional methods, with fitting errors matching the known data error. It is shown that the choice of relative or absolute error norm in the least-squares analysis is best based on the kind of error in the data. (C) 1998 Elsevier Science Ltd. All rights reserved.

Pore size distributions derived from adsorption isotherms, immersion calorimetry, and isosteric heats: A comparative study

We compare the pore size distribution of a well-characterized activated carbon derived from model-dependent, adsorption integral equation (AIE) methods with those from model-independent, immersion calorimetry and isosteric heat analyses. The AIE approach applied to nitrogen gave a mean pore width of 0.57 nm; the CO2 distribution exhibited wider dispersion. Spherical model application to CO2 and diffusion limitations for nitrogen and argon were proposed as primary reasons for inconsistency. Immersion enthalpy revealed a sharp decrease in available area equivalent to a cut-off due to molecular exclusion when the accessible surface was assessed against probe kinetic diameter. Mean pore width was identified as 0.58 ± 0.02 nm, endorsing the underlying assumptions for the nitrogen-based AIE approach. A comparison of the zero-coverage isosteric heat of adsorption for various non-polar adsorptives by the porous test sample was compared with the same adsorptives in contact with a non-porous reference adsorbent, leading to an energy ratio or adsorption enhancement factor. A linear relationship between the energy ratio and probe kinetic diameter indicated a primary pore size at 0.59 nm. The advantage of this enthalpy, model-independent methods over AIE were due to no assumptions regarding probe molecular shape, and no assumptions for pore shape and/or connectivity.

Characterization of pore size distributions of mesoporous materials from adsorption isotherms

In this article, a new hybrid model for estimating the pore size distribution of micro- and mesoporous materials is developed, and tested with the adsorption data of nitrogen, oxygen, and argon on ordered mesoporous materials reported in the literature. For the micropore region, the model uses the Dubinin-Rudushkevich (DR) isotherm with the Chen-Yang modification. A recent isotherm model of the authors for nonporous materials, which uses a continuum-mechanical model for the multilayer region and the Unilan model for the submonolayer region, has been extended for adsorption in mesopores. The experimental data is inverted using regularization to obtain the pore size distribution. The present model was found to be successful in predicting the pore size distribution of pure as well as binary physical mixtures of MCM-41 synthesized with different templates, with results in agreement with those from the XRD method and nonlocal density functional theory. It was found that various other recent methods, as well as the classical Broekhoff and de Beer method, underpredict the pore diameter of MCM-41. The present model has been successfully applied to MCM-48, SBA's, CMK, KIT, HMS, FSM, MTS, mesoporous fly ash, and a large number of other regular mesoporous materials.

Padé approximants for the acoustical properties of rigid frame porous media with pore size distributions

Expressions for the viscosity correction function, and hence bulk complex impedance, density, compressibility, and propagation constant, are obtained for a rigid frame porous medium whose pores are prismatic with fixed cross-sectional shape, but of variable pore size distribution. The lowand high-frequency behavior of the viscosity correction function is derived for the particular case of a log-normal pore size distribution, in terms of coefficients which can, in general, be computed numerically, and are given here explicitly for the particular cases of pores of equilateral triangular, circular, and slitlike cross-section. Simple approximate formulae, based on two-point Pade´ approximants for the viscosity correction function are obtained, which avoid a requirement for numerical integration or evaluation of special functions, and their accuracy is illustrated and investigated for the three pore shapes already mentioned

Organic compounds in sediments and pore waters of ODP Sites 117-723 and 117-724

Total organic carbon, amino compounds, and carbohydrates were measured in pore waters and sediments of Pliocene to Pleistocene age from Sites 723 and 724 (ODP Leg 117) to evaluate (1) relationships between organic matter in the sediment and in the pore water, (2) the imprint of lithological variations on the abundance and contribution of organic substances, (3) degradation of amino compounds and carbohydrates with time and/or depth, and (4) the dependence of the ammonia concentration in the pore water on the degradation of amino compounds in the sediment. Total organic carbon concentrations (TOC) of the investigated sediment samples range from 0.9% to 8.7%, and total nitrogen concentrations (TN) from 0.1% to 0.5%. Up to 4.9% of the TOC is contributed by hydrolyzable amino acids (THAA) which are present in amounts between 1.1 and 21.3 µmol/g dry sediment and decrease strongly downhole. Hydrolyzable carbohydrates (THCHO) were found in concentrations from 1.3 to 6.6 ?mol/g sediment constituting between 0.1% and 2.0% of the TOC. Differences between the distribution patterns of monomers in Sites 723 and 724 indicate higher terrigenous influence for Site 724 and, furthermore, enhanced input of organic matter that is relatively resistant to microbial degradation. Lithologically distinct facies close to the Pliocene/Pleistocene boundary yield different organic matter compositions. Laminated horizons seem to correspond with enhanced amounts of biogenic siliceous material and minor microbiological degradation. Total amounts of dissolved organic carbon (DOC) in pore waters vary between 11 and 131 mg/L. Concentrations of DOC as well as of dissolved amino compounds and carbohydrates appear to be related to microbial activity and/or associated redox zones and not so much to the abundance of organic matter in the sediments. Distributions of amino acids and monosaccharides in pore waters show a general enrichment in relatively stable components in comparison to those of the sediments. Nevertheless, the same trend appears between amino acids present in the sediments from Sites 723 and 724 as well as between amino acids in pore waters from these two sites, indicating a direct relation between the dissolved and the sedimentary organic fractions. Different ammonia concentrations in the pore waters of Sites 723 and 724 seem to be related to enhanced release of ammonia from degradation of amino compounds in Site 723.

Borehole temperature, submarine permafrost methane concentrations and pore water chemistry measured on borehole BK2, central Laptev Sea shelf

Submarine permafrost degradation has been invoked as a cause for recent observations of methane emissions from the seabed to the water column and atmosphere of the East Siberian shelf. Sediment drilled 52 m down from the sea ice in Buor Khaya Bay, central Laptev Sea revealed unfrozen sediment overlying ice-bonded permafrost. Methane concentrations in the overlying unfrozen sediment were low (mean 20 µM) but higher in the underlying ice-bonded submarine permafrost (mean 380 µM). In contrast, sulfate concentrations were substantially higher in the unfrozen sediment (mean 2.5 mM) than in the underlying submarine permafrost (mean 0.1 mM). Using deduced permafrost degradation rates, we calculate potential mean methane efflux from degrading permafrost of 120 mg/m**2 per year at this site. However, a drop of methane concentrations from 190 µM to 19 µM and a concomitant increase of methane d13C from -63 per mil to -35 per mil directly above the ice-bonded permafrost suggest that methane is effectively oxidized within the overlying unfrozen sediment before it reaches the water column. High rates of methane ebullition into the water column observed elsewhere are thus unlikely to have ice-bonded permafrost as their source.

Ba, Al and SO4 concentrations in sediments and pore fluid of ODP Leg 127/128 samples

The barium distribution in sediments and pore fluids from five sites drilled in the Japan Sea have been used to illustrate the geochemical behavior of this element as it pertains paleoproductivity reconstructions, diagenetic remobilization, and barite precipitation in authigenic fronts. Sites where sulfate is depleted in the pore fluids also show high concentrations of dissolved barium, reflecting dissolution of biogenic barite. The high rate of sedimentation at Sites 798 and 799 results in a rapid sulfate depletion, which in turn leads to barite dissolution and reprecipitation in diagenetic fronts. The dissolved barium distribution at these sites has been used to quantify the rate of barite dissolution; we estimate a first-order rate constant for barite dissolution to be 2*10**-6/s at Site 799 and 2*10**-7/s at Site 798. Authigenic barite has been documented in sediments from Site 799 at 323 meters below seafloor by scanning electron microscopy and X-ray fluorescence analysis. These results indicate barite precipitation in a diagenetic front near the zone of sulfate depletion by upward migration of dissolved barium and downward diffusion of sulfate. Barite precipitation has also been inferred at Sites 796 and 798 based on sedimentary and dissolved barium distributions. Sulfate is not depleted in the pore fluids of Site 794. The lack of diagenetic remobilization of biogenic barium at this site preserves the high barium signal associated with the high-productivity sequences deposited during the late Miocene to Pliocene. Significantly, the organic carbon distribution does not indicate high accumulation rates during the periods of high opal and barium deposition. Instead, higher organic carbon accumulations are recorded in the Quaternary and middle Miocene sequences; intervals that are also characterized by deposition of siliciclastic turbidites. The presence of a terrestrial component in the organic carbon record renders barium a more useful indicator than organic carbon for paleoproductivity reconstructions in this marginal sea.

In-situ sediment temperature and pore water chloride concentration at pockmarks of the Nigerian continental margin

A joint research expedition between the French IFREMER and the German MARUM was conducted in 2011 using the R/V 'Pourquoi pas?' to study gas hydrate distributions in a pockmark field (1141-1199 m below sea surface) at the continental margin of Nigeria. The seafloor drill rig MeBo of MARUM was used to recover sediments as deep as 56.74 m below seafloor. The presence of gas hydrates in specific core sections was deduced from temperature anomalies recorded during continuous records of infrared thermal scanning and anomalies in pore water chloride concentrations. In situ sediment temperature measurements showed elevated geothermal gradients of up to 258 °C/km in the center of the so-called pockmark A which is up to 4.6 times higher than that in the background sediment (72 °C/km). The gas hydrate distribution and thermal regime in the pockmark are largely controlled by the intensity, periodicity and direction of fluid flow. The joint interaction between fluid flow, gas hydrate formation and dissolution, and the thermal regime governs pockmark formation and evolution on the Nigerian continental margin.

(Table 1) Chemical compositions of beryllium in sediments and pore waters of ODP Hole 131-808

Studies of Be distributions in subduction zone sediments will help to understand questions regarding the enrichments of cosmogenic Be-10 in arc volcanic rocks. Analyses of Be-10 and Be-9 in sediments of Ocean Drilling Program Site 808, Nankai Trough and Be-9 in porewaters of Site 808 and Sites 671 and 672, Barbados ridge complex, show significant decreases in solid phase Be-10 and large increases of porewater Be-9 at the location of the décollement zone and below or at potential flow conduits. These data imply the potential mobilization of Be during pore fluid expulsion upon sediment burial. Experiments involving reaction between a décollement sediment and a synthetic NaCl-CaCl2 solution at elevated pressure and temperatures were conducted in an attempt to mimic early subduction zone processes. The results demonstrate that Be is mobilized under elevated pressure and temperature with a strong pH dependence. The Be mobilization provides an explanation of Be-10 enrichment in arc volcanic rocks and supports the argument of the importance of the fluid processes in subduction zones at convergent margins.