Thermodynamic and Kinetic Aspects of Argillaceous Sandstone Acidizing

1975 ◽  
Vol 15 (02) ◽  
pp. 117-128 ◽  
Author(s):  
Jean Claude Labrid

Abstract The thermodynamic aspect of sandstone acidizing by hydrofluoric acid (HF) is examined. It is shown that silica dissolution, with a first order in HF concentration leads almost exclusively to the formation of fluosilicic acid. Clay and feldspar dissolution is much more complex; after a uniform alteration of the crystalline lattice, partial precipitation of silicic species occurs when the precipitation of silicic species occurs when the acid is spent. An approach to the kinetic aspect is made by defining, for a naturally complex medium, a reactivity profile that is a characteristic of the medium instead of a single reaction-rate constant. Experimental data enable a correlation between permeability, porosity, and reactivity. Also, a permeability, porosity, and reactivity. Also, a qualitative interpretation of acid response curves is given. The numerical simulation of the acidizing process satisfactorily reproduces the experimental process satisfactorily reproduces the experimental results. When extended to radial flow, the model shows the influence of stimulation parameters, injection rate, concentration, and time. Introduction Use of acids for increasing well productivity has been well established since the description of the first acid treatment appeared at the end of the last century. However, commercial development of acidizing as a stimulation technique became widespread around 1930. Since then, extensive research has broadened the number of techniques and chemical additives that not only improve the operation, but also extend applications to more complex reservoirs under severe pressure and temperature conditions. These applications are extended by the use of special corrosion inhibitors and organic acids for deep well treatment (with or without the cool-down technique) by the handling of high-strength acids recommended in offshore operations where it is advisable to use small volumes, and by the development of acid mutual-solvent technique to prevent fine particles from migrating near the wellbore, improving stimulation response. In As present state, the acidizing process largely involves empirical methods primarily because of insufficient understanding of the physical, chemical, and physicochemical phenomena involved. As a result, the anomalous behavior of some acid-response curves used for predicting treatment efficiency has not yet received a satisfactory explanation. The chemistry of the dissolution of detritic materials by acids is, in fact, not entirely understood because of the great number of equilibria between the reagent and the different species in solution derived from the native rock. The thermodynamic aspect of the problem is examined first giving a qualitative and quantitative description of chemical phenomena and attaining the solubilization mechanism of silica, feldspars, and clays. Conclusions of this study enable interpretation of the phenomena observed when an acid flows through a natural porous sandstone (dynamic experiment). The kinetic aspect is considered, along with the definition and the measurement of the matrix reactivity, a concept as characteristic of this matrix as porosity and permeability. THERMODYNAMIC CONSIDERATIONS Sandstone acidizing is based on the unique quality of HF to attack silica and alumina-silicates. Although this property has long been known (since HF is used in the glass-engraving method), its application to well stimulation quickly revealed the complexity of the problem, especially the possibility of side reactions that may affect formation permeability. The thermodynamic aspect is permeability. The thermodynamic aspect is approached in the following manner. The system formed by HF in water solution and a mineral occuring in a sandstone, such as silica, clay, or feldspar, is considered. There is a chemical reaction; that is, a consumption of the reagents and a solubilization of the mineral constituents (silicon, aluminum, potassium, etc.), which are then involved in a great number of chemical equilibria. SPEJ P. 117

1963 ◽  
Vol 18 (1) ◽  
pp. 135-151 ◽  
Author(s):  
Shuichi Karasaki

The yolk platelets of mature eggs and young embryonic cells of all amphibian species studied (Rana pipiens, Triturus pyrrhogaster, Diemictylus viridescens, Rana nigromaculata, and Bufo vulgaris) have a superficial layer of fine particles or fibrils (ca. 50 A in diameter), a central main body with a crystalline lattice structure, and an enclosing membrane approximately 70 A in thickness. Electron micrographs of the main body reveal hexagonal net (spacing ca. 70 A), square net (spacing ca. 80 A), and parallel band (spacing from 35 to 100 A but most frequent at ca. 70 A) patterns. The crystalline structure is believed to be a simple hexagonal lattice made of closely packed cylindrical rods. Each rod is estimated to be about 80 A in diameter and 160 A in length.


2003 ◽  
Vol 17 (10) ◽  
pp. 2005-2022 ◽  
Author(s):  
JAY MITTENTHAL ◽  
BERTRAND CLARKE ◽  
ALEXANDER SCHEELINE

We examine features of intracellular networks that make errors less probable and beneficial responses more probable. In a false negative (F-) error, a network does not respond to input. A network is reliable if it operates with a low probability of a F- error. Features that promote reliability include fewer reactions in sequence, more alternative pathways, no side reactions and negative feedback. In a false positive (F+) error, a network produces output without input. Here, a network is specific if it has a low probability of a F+ error. Conjunctions of signals within or between pathways can improve specificity through sigmoid steady-state response curves, kinetic proofreading and checkpoints. Both reliability and specificity are important in networks that regulate the fate of a cell and in networks with hubs or modules, and this includes scale-free networks. Some networks discriminate among several inputs by responding to each input through a different combination of pathways.


1976 ◽  
Vol 16 (05) ◽  
pp. 248-260 ◽  
Author(s):  
H.S. Fogler ◽  
K. Lund ◽  
C.C. McCune

Abstract An extensive theoretical and experimental analysis of the acidization of linear sandstone cores has been carried out. The relative rates of reaction of common minerals found in sandstone, which were determined from rotating-disk-experiments, are presented and discussed along with the underlying presented and discussed along with the underlying reaction mechanisms. A lumped-parameter mathematical model developed from this information predicts the movements of acid and permeability predicts the movements of acid and permeability changes through the porous sandstone cores as a function of acid concentration and flow rate. Two acid core flood experiments are needed to determine the characteristic parameters of the model (the Damkohler number and the acid capacity number). However, this paper also shows how, in the absence of these experiments, one can extend the model to make predictive calculations for various sandstones from a porosity measurement and an X-ray analysis of the sandstone. In carrying out this latter analysis, a comparison of the experimental results of other investigators with the model shows the theory and experiment to be in excellent agreement. Introduction The stimulation of petroleum wells by acid injection is accomplished by selective dissolution of part of the formation rock to reduce the resistance to fluid flow in the vicinity of the wellbore. Because of the radial flow geometry, the productivity of the well may be increased greatly. Field and laboratory data have been gathered through years of applying the process to allow the design of an acid treatment for a particular formation. The complexity of the porous media and the reactions occurring during the acidization have made it difficult to predict a priori the exact results of the stimulation. A large step forward in the technology was made by the introduction of permeameters to permit the testing of cores at permeameters to permit the testing of cores at conditions similar to those existing in the reservoir. A series of experiments then can be carried out using different acid strengths, volumes, and flow rates to determine the best conditions for acidization. In recent years, the acidization process has been investigated in detail experimentally and theoretically. This has led to a better understanding of acidization and the development of mathematical models of the process. The application of a model allows a successful acidization treatment to be designed on the basis of few or no laboratory experiments. Even though differences exist in the manner by which the treatment is carried out in practice, the basic processes occurring during practice, the basic processes occurring during acidization are the same: homogeneous reactions in the fluid phase, heterogeneous reactions between the fluid and the solid phase, mass transfer, fluid flow, and changes in the pore structure of the porous media. porous media. This paper is primarily concerned with matrix acidization of sandstones, but the results will be of interest for other forms of acidization. Although emphasis is placed on the results of studies by the authors, it is seen that by comparing these results with the work of other investigators a uniform theory of acidization may be proposed. HOMOGENEOUS REACTIONS In the acidization of sandstones, and also of carbonates, a large number of product species are released to the acid solution. Since these may react with each other and with the acid, it is necessary to understand the equilibria between the different chemical species to determine the reaction stoichiometry. Carbonic acid formed by the dissolution of carbonates may participate in several reactions. However, since strong acids or acid mixtures are generally used, these side reactions usually may be neglected. SPEJ P. 248


Author(s):  
Robert F. Dunn

Receptor cells of the cristae in the vestibular labyrinth of the bullfrog, Rana catesbiana, show a high degree of morphological organization. Four specialized regions may be distinguished: the apical region, the supranuclear region, the paranuclear region, and the basilar region.The apical region includes a single kinocilium, approximately 40 stereocilia, and many small microvilli all projecting from the apical cell surface into the lumen of the ampulla. A cuticular plate, located at the base of the stereocilia, contains filamentous attachments of the stereocilia, and has the general appearance of a homogeneous aggregation of fine particles (Fig. 1). An accumulation of mitochondria is located within the cytoplasm basal to the cuticular plate.


Author(s):  
Sumio Iijima

We have developed a technique to prepare thin single crystal films of graphite for use as supporting films for high resolution electron microscopy. As we showed elsewhere (1), these films are completely noiseless and therefore can be used in the observation of phase objects by CTEM, such as single atoms or molecules as a means for overcoming the difficulties because of the background noise which appears with amorphous carbon supporting films, even though they are prepared so as to be less than 20Å thick. Since the graphite films are thinned by reaction with WO3 crystals under electron beam irradiation in the microscope, some small crystallites of WC or WC2 are inevitably left on the films as by-products. These particles are usually found to be over 10-20Å diameter but very fine particles are also formed on the film and these can serve as good test objects for studying the image formation of phase objects.


Author(s):  
W. D. Cooper ◽  
C. S. Hartley ◽  
J. J. Hren

Interpretation of electron microscope images of crystalline lattice defects can be greatly aided by computer simulation of theoretical contrast from continuum models of such defects in thin foils. Several computer programs exist at the present time, but none are sufficiently general to permit their use as an aid in the identification of the range of defect types encountered in electron microscopy. This paper presents progress in the development of a more general computer program for this purpose which eliminates a number of restrictions contained in other programs. In particular, the program permits a variety of foil geometries and defect types to be simulated.The conventional approximation of non-interacting columns is employed for evaluation of the two-beam dynamical scattering equations by a piecewise solution of the Howie-Whelan equations.


Author(s):  
John R. Porter

New ceramic fibers, currently in various stages of commercial development, have been consolidated in intermetallic matrices such as γ-TiAl and FeAl. Fiber types include SiC, TiB2 and polycrystalline and single crystal Al2O3. This work required the development of techniques to characterize the thermochemical stability of these fibers in different matrices.SEM/EDS elemental mapping was used for this work. To obtain qualitative compositional/spatial information, the best realistically achievable counting statistics were required. We established that 128 × 128 maps, acquired with a 20 KeV accelerating voltage, 3 sec. live time per pixel (total mapping time, 18 h) and with beam current adjusted to give 30% dead time, provided adequate image quality at a magnification of 800X. The maps were acquired, with backgrounds subtracted, using a Noran TN 5500 EDS system. The images and maps were transferred to a Macintosh and converted into TIFF files using either TIFF Maker, or TNtolMAGE, a Microsoft QuickBASIC program developed at the Science Center. From TIFF files, images and maps were opened in either NIH Image or Adobe Photoshop for processing and analysis and printed from Microsoft Powerpoint on a Kodak XL7700 dye transfer image printer.


Author(s):  
James F. Hainfeld ◽  
Frederic R. Furuya

Glutaraldehyde is a useful tissue and molecular fixing reagents. The aldehyde moiety reacts mainly with primary amino groups to form a Schiff's base, which is reversible but reasonably stable at pH 7; a stable covalent bond may be formed by reduction with, e.g., sodium cyanoborohydride (Fig. 1). The bifunctional glutaraldehyde, (CHO-(CH2)3-CHO), successfully stabilizes protein molecules due to generally plentiful amines on their surface; bovine serum albumin has 60; 59 lysines + 1 α-amino. With some enzymes, catalytic activity after fixing is preserved; with respect to antigens, glutaraldehyde treatment can compromise their recognition by antibodies in some cases. Complicating the chemistry somewhat are the reported side reactions, where glutaraldehyde reacts with other amino acid side chains, cysteine, histidine, and tyrosine. It has also been reported that glutaraldehyde can polymerize in aqueous solution. Newer crosslinkers have been found that are more specific for the amino group, such as the N-hydroxysuccinimide esters, and are commonly preferred for forming conjugates. However, most of these linkers hydrolyze in solution, so that the activity is lost over several hours, whereas the aldehyde group is stable in solution, and may have an advantage of overall efficiency.


Author(s):  
Chihiro Kaito ◽  
Yoshio Saito

The direct evaporation of metallic oxides or sulfides does not always given the same compounds with starting material, i.e. decomposition took place. Since the controll of the sulfur or selenium vapors was difficult, a similar production method for oxide particles could not be used for preparation of such compounds in spite of increasing interest in the fields of material science, astrophysics and mineralogy. In the present paper, copper metal was evaporated from a molybdenum silicide heater which was proposed by us to produce the ultra-fine particles in reactive gas as shown schematically in Figure 1. Typical smoke by this method in Ar gas at a pressure of 13 kPa is shown in Figure 2. Since the temperature at a location of a few mm below the heater, maintained at 1400° C , were a few hundred degrees centigrade, the selenium powder in a quartz boat was evaporated at atmospheric temperature just below the heater. The copper vapor that evaporated from the heater was mixed with the stream of selenium vapor,and selenide was formed near the boat. If then condensed by rapid cooling due to the collision with inert gas, thus forming smoke similar to that from the metallic sulfide formation. Particles were collected and studied by a Hitachi H-800 electron microscope.Figure 3 shows typical EM images of the produced copper selenide particles. The morphology was different by the crystal structure, i.e. round shaped plate (CuSe;hexagona1 a=0.39,C=l.723 nm) ,definite shaped p1 ate(Cu5Se4;Orthorhombic;a=0.8227 , b=1.1982 , c=0.641 nm) and a tetrahedron(Cu1.8Se; cubic a=0.5739 nm). In the case of compound ultrafine particles there have been no observation for the particles of the tetrahedron shape. Since the crystal structure of Cu1.8Se is the anti-f1uorite structure, there has no polarity.


Author(s):  
N. V. Larcher ◽  
I. G. Solorzano

It is currently well established that, for an Al-Ag alloy quenched from the α phase and aged within the metastable solvus, the aging sequence is: supersaturated α → GP zones → γ’ → γ (Ag2Al). While GP zones and plate-shaped γ’ are metastable phases, continuously distributed in the matrix, formation of the equilibrium phase γ takes place at grain boundaries by discontinuous precipitation (DP). The crystal structure of both γ’ and γ is hep with the following orientation relationship with respect to the fee α matrix: {0001}γ′,γ // {111}α, <1120>γ′,γ, // <110>α.The mechanisms and kinetics of continuous matrix precipitation (CMP) in dilute Al-Ag alloys have been studied in considerable detail. The quantitative description of DP kinetics, however, has received less attention. The present contribution reports the microstructural evolution resulting from aging an Al-Ag alloy with Ag content higher than those previously reported in the literature, focusing the observations of γ' plate-shaped metastable precipitates.


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