Search Documents

By H. T. Kennedy, J. E. Little

An empirical equation for the prediction of the viscosity of several pure paraffin hydrocarbons and nitrogen is presented. It involves temperature, pressure and six constants of the material, and it applies reliably to both liquids and gases. The equation is similar in form to van der Waal's equation of state. For the paraffin hydrocarbons methane through r-hexane and nitrogen, an average absolute deviation of 1.9 percent was obtained on 1,006 data points described in the literature by 14 authors. When this equation is extended to complex, liquid hydrocarbon mixtures, a correlation was obtained with an average absolute deviation of 9.9 percent. INTRODUCTION Equations describing the flow of gas and liquid through porous media contain the viscosity coefficient of the fluid. If other pertinent variables remain constant, the volume rate of flow is inversely proportional to this coefficient. In dealing with condensate fluids and volatile oils, however, the compositional effects resulting from changing pressure materially affect the viscosity. The effect of compositional changes also may be significant in certain secondary recovery or pressure maintenance processes, notably miscible displacement or gas injection. Early attempts to describe the performance of reservoirs utilized a volumetric material balance method wherein gas and liquid in the reservoir were identified as produced gas and liquid at the surface. This method of analysis proved adequate for reservoirs at moderate temperature and pressure that contained gas with moderately low amounts of condensable materials. The volumetric material balance procedures for "black oil" reservoirs leave much to be desired when applied to condensate and volatile oil reservoirs because phase behavior and compositional changes are relatively more important in these cases. The alternative is a compositional material balance, which in turn, requires a correlation of properties of the reservoir fluid with composition. This paper supplies this correlation in regard to viscosity, for reservoir crude oils. REVIEW OF LITERATURE The literature contains many empirical equations describing the effects of composition, temperature and pressure on the viscosities of pure liquids and binary liquid mixtures. However, the applicability of a majority of these equations is limited to very low pressures and to a small number of systems. Most of them, when applied to complex hydrocarbon systems, are of little value. The lack of utility of the majority of equations results from the fact that they were developed to show the separate effect of temperature, pressure or composition on viscosity, but not to predict the viscosity as a function of all three variables. And with the few exceptions noted below, they were developed to apply to much simpler systems than hydrocarbon mixtures. Eakin1 developed an equation for the viscosity of pure light hydrocarbons applicable in the gas, liquid and dense fluid regions, and in its most general form is written as µ - µo =A(ebP - e-cpk) The pure component viscosity at atmospheric pressure and temperature T, µo, was calculated using the Sutherland equation: µo = BT3/2/T + S The constants in Eakin's equation permitted the term e-CPk to become quite small at high densities (above 0.215 gm/cc), and the general equation would simplify to

Jan 1, 1969

By W. J. Verner, J. R. Lucas

Billions of tons of bulk solid materials are processed through our industrial plants each year, and the tonnage is steadily rising. It has been estimated that for every dollar spent in industry as a whole, approxinlately 30 cents is consumed in the handling of bulk solid materials. It is in this category that tremendous savings are possible through the use of improved techniques. Since World War 11, the mining, steel, chemical, and grain industries, among others have made use of increased materials-handling automation in order to gain some of these savings. However, in a chain of automatic operations, every link must be completely reliable, for if there is a single failure, the whole system immediately becomes ineffective. Only too often the weak link in the chain proves to be the flow of bulk solids from bins. To contribute to the fundamental knowledge in this area, a research study has been continuing at The Ohio State University. The principal objective of the investigation has been to study the internal stresses existing in confined bulk solids. LITERATURE SURVEY Literature studies have revealed that many outstanding people have made contributions to the field of bulk solids. For instance, C. F. Jenkin,1 suggested: a. The pressure on a bin wall is not directly proportional to the depth beneath the surface of material in the bin. b. The vertical pressure distribution on the base of a bin is not actually uniform but is a variable. c. Arches form in bins as a result of very small deformations of the material in the bin. This deformation causes a series of gaps to appear, and consequently causes the disappearance of diagonal forces that cannot act across these gaps. The removal of the diagonal forces causes horizontal forces to be introduced which seem to be the chief cause of arching. 11. A. Janssen,4 in 1895 in connection with his experiments on bins, derived a differential equation to describe both the lateral and vertical pressure in bins with vertical sides. This represents a significant contribution to bulk solid theory, and thus its solution is reproduced as follows: L = KV = RW/U' [l-e -U'KY/R] I where L is the lateral pressure of the bulk solid in psf., V is the vertical pressure of the bulk solid in psf., K is the ratio of the lateral pressure to the vertical pressure at any point, R is the hydraulic radius of the bin in feet, W is the density of the bulk solid in lbs. per cubic feet, U' is the coefficient of friction between the stored material and the bin wall, and Y is the head of material above the point in question in feet. In 1903, Jamieson,6 in an elaborate series of experiments on full sized bins measured vertical and lateral pressures by hydraulic diaphragms. He determined many values for mediums of corn, wheat, peas, and flaxseed. In 1951, Caughey, Tooles, and scheer3 measured both lateral and vertical pressure in deep bins by using strain guages on steel bands. Values were calculated for cement, gravel, sand, soy beans, shelled corn

Jan 1, 1961

By L. L. Seigle

Free energies, heats, and entropies of mixing of solid Fe-Au alloys have been measured by the galvanic cell method between 800° and 900°C. A positive deviation from Raoult's law and a large excess entropy of mixing were observed, both attributable to lattice distortion caused by the disparity in component atom sizes. Since the terminal solid solutortiontions are not regular, thermodynamic properties computed from the location of the mis-cibility gap do not agree well with measured quantities. The electromotive force data suggest some changes in the existing Fe-Au phase diagram. ALTHOUGH a considerable amount of information has been accumulated about the thermodynamic properties of metal solid solutions which exhibit negative deviation from Raoult's law, particularly those in which ordering occurs, relatively few experimental measurements have been made on solutions with positive deviation. This is due to the infrequency of broad homogeneous regions suitable for experimental measurement in solutions of this type, since any marked positive deviations from ideality lead to restricted solubility and the formation of miscibility gaps. Thermodynamic data reported in the literature for such systems have usually been calculated from the location of the miscibility gap boundaries under the assumption that the entropies of mixing are ideal, i.e., the terminal solutions are regular.' One of the few binary systems with both positive deviation and a wide homogeneous range in the solid is the Ni-Au system. A recent investigation of solid Ni-Au alloys' revealed that the entropies of mixing were much larger than ideal and consequently thermal data computed from the phase boundaries assuming regular solutions were seriously in error. Theoretical considerations put forward by Zener indicated that high entropy values should generally be associated with systems possessing a miscibility gap in the solid, when this is due to differences in the size of component atoms. These facts suggest that the regular solution assumption is a poor approximation for many solid solutions with positive deviation and that reliable thermodynamic data generally cannot be obtained by conventional methods from the location of miscibility gap boundaries. The Fe-Au system, Fig. 1, resembles the Ni-Au system in certain respects. The presence of a miscibility gap in the solid indicates a large positive deviation from ideality, but there is nevertheless an extensive single phase region suitable for experimental measurement. The following investigation of solid Fe-Au alloys was carried out in order to obtain additional data on the thermodynamic properties of metal solid solutions with positive deviation from Raoult's law and to further compare thermodynamic data computed from miscibility gap boundaries with those measured experimentally. Experimental Method The thermodynamic properties were derived from measurements of the potential developed between pure solid iron and Fe-Au alloys in a high temperature galvanic cell. The experimental apparatus and technique were the same as those used for the Ni-Au alloys and described in a previous report.' Cell electrodes were 1/16 in. diam rods swaged from chill-cast ingots and annealed for one week at 850°C. The alloys were prepared by melting fine gold granules under argon with pure iron obtained from the National Research Co. The cell electrolyte was

Jan 1, 1957

By R. B. Booth, W. F. Linke

The continuous interest of the American Cyanamid Company in producing superior polymeric flocculants and dispersants for the mining industry has resulted in a broad, general study of the physical chemistry of mineral-polymer systems. The aim of this program has been to establish a sound theoretical basis on which practical problems could be analyzed, and which would lead to the development of new and improved flocculating and dispersing agents. This study has required the cooperative effort of physical, analytical, and polymer chemists, as well as engineers familiar with mining problems. This report summarizes the results of some of our investigations over the past two years. Further studies along these and other lines are in progress and will be reported in the near future. MEASURING FLOCCULATION IN THE LABORATORY The foremost problem in studying flocculation in the laboratory has been to establish reproducible methods of comparing and evaluating the effectiveness of various reagents. Previous workers have measured settling -rates 1,8 filtration rates2 , and sediment volumes3 . Direct observations of the floc size, or the clarity of the supernatant liquid, can also be used. AIthough these parameters are all interrelated, they do not always measure the same physical properties of the suspensions, and hence are not equally useful or reliable. Whatever the method of comparison selected. the testing procedure must be carefully defined and standardized. The results must be satisfactorily reproducible, and for practical purposes must accurately reflect the results obtained in mill use. In order to compare the data obtained in these various types of test, the physical nature of the flocculated system must be examined in some detail. In an unflocculated system, only the larger or denser particles (the "sands") settle at a useful rate. The sediment can be observed to build up from the bottom of the cylinder, while the fines remain in suspension for a long period of time. If the system is not disturbed, even the microscopic fines can be seen to classify themselves as they fall over a period of days. When a high molecular weight polymer is added to the system, the colloidal particles are tied together randomly in flocs, and the sands and fines settle together. The line of demarkation between solid and liquid phases moves downward from the top of the cylinder. The settling rate of the flocs depends on their size and on their effective density. For a given mineral sample, the larger the flocs, the faster the settling. Since the large flocs cannot pack as closely as small ones, they produce a sediment with more pore spaces, and hence of larger volume, which is easier to pump and to agitate. Although it is nearly impossible to measure individual floc sizes, it is relatively easy to determine settling rates and sediment volumes. Of these two, the settling rate is simpIer to measure, and hence generally more practical. Reproducible sediment volumes can only be obtained by allowing the solids to pack for a rather long period of time (e.g., hours to days), and although the volumes thus observed are directly related to the degree of flocculation (average floc size), it is often impractical to wait so long for the results.

Jan 1, 1961

By J. D. Rice, S. C. Pitzer, C. E. Thomas

Interpretation of pressure build-up data obtained in the conventional manner has often been difficult because of the deviation from theoretical behavior. Major causes of this deviation have been attributed to damage and afterflow, and to fluid redistribution in the wellbore which, in extreme cases, can result in a pressure hump in the early portion of the build-up curve. Theoretical investigations show that bottom-hole pressure is definitely influenced by phase redistribution in the tubing column during surface shut-in tests, and that the magnitude of the effect is sensitive to the producing gas-oil ratio and stabilized rate of flow in the well. For field experiments a wire-line tubing packer, which can be run in the tubing against a stabilized flow rate, was developed for bottom-hole shut-in tests. By use of this bottom-hole .shut-in method, pressure humps previously observed in surface shut-in tests were completely eliminated and the effects of afterflow minimized. Analog and digital computer studies have been made to obtain theoretical curves for comparison with field curves, and remarkable agreement between the results of bottom-hole shut-in tests and theoretical curves has been obtained. INTRODUCTION Pressure build-up data from shut-in wells have been used by the petroleum industry to determine the permeability of the formation, to estimate wellbore damage, to evaluate the static reservoir pressure and to speculate reservoir volume. Calculation of these factors is based on methods of analysis developed for theoretical systems whose build-up curves have a charac- teristic shape when the wells are shut-in at the sand faCe.1,2,3,5,8,10 However, field curves obtained by conventional surface shut-in methods do not always exhibit this characteristic. Such factors as stratification, rock heterogeneities and irregular reservoir geometry can cause the character of a build-up curve to deviate from that predicted by theory for a simple system. In addition, all field build-up data are affected by the methods utilized in obtaining the measurements. Conventional surface shut-in techniques allow two effects to occur which contribute directly to the manner in which pressure builds up at the sand face. The first, afterflow, has been recognized for some time and methods are available for estimating the magnitude of its effect and for correcting its influence.' The second, phase segregation in the tubing column after shut-in, has been reported only recently and appears to exert a considerable influence on the character of field build-up curves.!' In extreme cases, phase segregation can produce "pressure humps" in the early portion of the build-up curve. Such curves have been considered anomalous and have defied analysis. It is the purpose of this paper to discuss the effect of phase segregation in the tubing string during build-up and to present a bottom-hole shut-in technique for obtaining field build-up data which minimizes the influence of afterflow and eliminates phase segregation effects. It will be shown that reliable reservoir information can be calculated from build-up measurements obtained using this method, even though conventional surface shut-in tests on the same wells yield anomalous data. DISCUSSION OF PHASE REDISTRIBUTION EFFECTS Some of the effects of phase redistribution on pressure build-up curves have been described previously by Matthews and Stegemeier" who have presented evidence that phase segregation is responsible for the pres-

By R. H. Winn

A method for the selection of the most suitable corrosion inhibitor for a particular system is given. The method involves the evaluation of surface passivity by means of copper ion displacement after the metal surface has been subjected to the corrosive atmosphere. The application of the method to the selection of suitable inhibitors for use in producing wells is described. Correlation with recognized laboratory tests has beet1 found to be good within the limitations of the test. The use of the test to evaluate inhibitor persistencc is described. INTRODUCTION Corrosion as it is associated with the industry shows wide variations in its qualitative as well as its quantitative aspects. This complicates the work of the corrosion engineer. In the past few years the efforts of the corrosion engineer have been further taxed by the large numbers of products being marketed as corrosion inhibitors by various manufacturers. These products are submitted to him together with a limited amount of data to support their use as inhibitors. The data are usually authentic and reliable yet all too often when these products are applied to an actual corrosive system the results are disappointing due to the ineffectiveness of the inhibitor and the corrosive system. The corrosion engineer must select a comparatively limited number of inhibitors for field trial from the large number available. The selection is usually made on the basis of a standardized laboratory test such as that adopted by the National Association of Corrosion Engineers or by field experience in an area; however, testing of this type is discouraging on large numbers of compounds, particularly in view of the specificity of environment. It has been an object of this work to devise a method which will allow the corrosion engineer to select the best inhibitor for a specific environment under field conditions. The test would of necessity be rapid and inexpensive. It would preferably eliminate the need for expensive and delicate instruments. STATEMENT OF THEORY The test as developed makes use of the fact that metal ions will be displaced from solution by metals having a more positive electrode potential. Thus, if an active iron surface is exposed to a solution of a copper salt, free copper will plate spontaneously on the iron surface as it is displaced from the salt solution by iron ions. If the iron surface is passified, as by coating with an insulating-type organic corrosion inhibitor, it is no longer capable of displacing the copper ions due to its own limited ionization. The result will be a change in the amount of copper plated upon exposure to a neutral copper salt solution. In practice it has been found possible to measure the magnitude of the alteration of the cell potential by determining the copper deposited on a standard iron surface under controlled conditions. This means that, as the film builds up, the resulting shift in the electrode potential tends to cause the iron surface to act more like a noble metal, resulting in a reduction in the cell potential to a point that copper will no longer plate spontaneously. Obviously, the salts of other metals such as silver, gold or platinum might be used for this operation; however, copper was selected because of the color difference of the plate, the comparatively low cost of copper salts and the ease of evaluation of the plated copper. Furthermore, its high cell potential provides a substantial driving energy. The determination of the copper is readily done colorimetrically by dissolving it in 5 per cent ammonium hydroxide solution containing 2 per cent potassium per-sulfate. The blue color of the copper ammonic complex ion so developed may be compared with standards prepared by dissolving known quantities of copper powder in the same reagent. In routine screening it is seldom desirable to determine the amount of copper plated. It is usually more important to determine the concentration of inhibitor required to prevent the plating of copper.