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By K. Leutwyler

The key to realistic casing stress analysis in thermal recovery installations is accurate knowledge of the temperatures involved. Much information leading to prediction of heat losses from tubing string to wellbore has been published. This .same information permits calculation of casing temperature under certain conditions. This paper reviews the basis for most of the published work, the line source solution to the diflusivity equation and examines some of its application criteria in the light of unsteady-state conditions. An alternate finite differences method is presented for correlation, and experimental data pertaining to the heat transfer mechanism in the annulus is reported. In the light of the information presented in the paper, it appears that the assumption of a line source for the tubing-wellbore system is valid even for reasonably short periods of heat flow, .such as "steam soak" operations. The empirically modified equation presented earlier matches computer derived results of the finite differences approach lor periods as short as 50 hours. Previously predicted cas ing temperatures and the associated stress levels are thus verified based on these correlative computations and the reported experimental information. Fall out from the computer output resulting in some studies of the influence of insulating cement properties on casing temperature, and experimentally studied effects of nitrogen placed in the annulus at various pressures., are described. INTRODUCTION Generally speaking, predictions of average casing temperatures have been based on an idealized model involving a centralized tubing string at uniform constant temperature radiating energy towards the casing under steady-state conditions.'. ' Heat is transferred away from the casing to the formation by unsteady-state conduction across thermal barriers consisting of cement and the mud sheath. Heat balances written on the casing permit prediction of instantaneous casing temperatures. During early periods of injection, casing temperature varies appreciably as a function of time; however, for long injection times this variation decays as heat flow from the wellbore to the formation stabilizes, and it becomes virtually negligible as conditions surrounding the wellbore become quasi-steady-state (Fig. 1). Carslaw and Jaeger -escribe a solution to the diffusivity equation for a line source (Fig. 2). A constant supply of heat is introduced into the medium from the line placed into the origin of the x-y coordinate system and parallel to the z-axis. Heat spreads outward in the infinite cylindrical solid and the temperature increase on a line going through point (x, y) parallel to the z-axis at a distance r can be predicted by: The following criterion must be considered: the Carslaw and Jaeger equation is obtained on the basis of a large

Jan 1, 1967

By R. M. Waterstrat

X-ray diffraction and metallographic examination of binary Mn-rich alloys with Ti revealed the presence of intermediate phases in this system. A binary R phase has been identified and also a phase having an a-Mn type structure. The X-ray pattern of the phase TiMn3 is presented and a tentative phase diagram for the Mn-rich portion of this binary system has been constndcted. MANGANESE-rich alloys with titanium have been subjected to thermal analysis at temperatures down to 1100°C by Hellawell and Hume-Rothery.1 Their results indicate the existence of an intermediate phase TiMn3 in this binary system. This phase appears to coexist with the Laves phase TiMn2, and with terminal solid solutions based on the allotropes of manganese, at least down to 1100°C. The above investigators did not attempt to determine the crystal structure of this phase, however. Since, by analogy to the binary systems Mn-V and Mn-Cr3 one might expect to find a phase in this region of the diagram, it seemed desirable to obtain X-ray diffraction patterns of alloys in the concentration range in question, in order to ascertain whether the sigma phase or related structures occur. EXPERIMENTAL PROCEDURES Alloys were prepared by arc-melting electrolytic manganese and iodide titanium in a water-cooled copper crucible under a helium atmosphere. Excess manganese was added to each melt in order to allow for losses incurred during melting. The alloys were then wrapped in molybdenum foil and sealed in evacuated quartz tubes for annealing at various temperatures, as shown in Table I, followed by quenching in cold water. Although the inside of the tubes showed evidence for some loss of manganese from the specimen during annealing, there was no evidence of any reaction between the specimen and either the molybdenum foil or the quartz tube at these temperatures. It was later found that the manganese loss was considerably reduced by annealing these alloys in sealed quartz tubes containing one atmosphere of purified argon. As an added precaution the surface of each specimen was ground off before crushing the alloys to -270 mesh powder, using a hardened steel mortar and pestle. X-ray powder patterns were obtained using either FeKa or CrKa radiation in an asymmetrical focusing camera, which gave excellent dispersion of the closely spaced lines. Pictures were also obtained using a Debye camera of 5-cm radius which provided data in the angular region not covered by the focusing camera. The alloy specimens were polished and examined metallographically, using an etchant consisting of 60 pct glycerine, 20 pct nitric acid, and 20 pct hydrofluoric acid. The 10-g buttons were in each case broken in half and found to be well-melted and free of any gross segregation. One half of certain alloy buttons was submitted to chemical analysis in the "as-cast" condition. No appreciable change in composition seemed to occur during annealing . RESULTS The X-ray pattern of alloy Ti1.17Mn0.83 was found to agree well with that of the ternary R phase which was first found in the Mo-Cr-Co system,' and re-

Jan 1, 1962

By H. O. McLeod, J. M. Campbell

Data analysis of pentane and hexane adsorption from natural gas in a fixed bed of silica gel shows that constant length mass transfer zones form, the curvature of the adsorption isotherm controls the growth of the mass transfer zone and surface diffusion of molecules inside the silica gel particle controls the mass transfer rate. Curvature of the hexane isothem is more than the curvature of the pentane isotherm. Because of this curvature the hexane adsorption zones reached a constant length. In contrast, the pentane adsorption zones were always increasing in length during each run. A procedure was developed to obtain correct mass transfer coefficients using effluent curve slopes. These transfer roefficients increase with the amount of hydrocarbon adsorbed on the silica gel particle. The characteristic shape of the hexane effluent curves also show that molecular diffusion inside the silica gel particle controls the adsorption rate of pentane and hexane. INTRODUCTION The purpose of this study was to determine the mechanisms that control the dynamic adsorption of hydrocarbons from a natural gas onto silica gel. Before one can deal effectively with multicomponent adsorption, the transfer mechanisms by which a single hydrocarbon component is adsorbed from the gas stream must be defined. Two principal investigations of this system have been published ' and indicate that diffusion through the gas around the particle controls the adsorption rate. Some of the experimental observations in each study either do not support this transfer mechanism or are inconsistent with the mathematical model used in analysis. In this study surface diffusion of molecules inside the particle controls the mass transfer rate of pentane and hexane. This mechanism is indicated by the effluent curve shape for a constant length transfer zone and by the variation of the mass transfer coefficient with concentration of the adsorbed hydrocarbon. THEORY AND DEFINITIONS — MATHEMATICAL MODELS Mathematical solutions for the isothermal adsorption of a trace component from a carrier gas are derived from three relationships: the mass balance or continuity equation, the equilibrium relationship between the gas and solid phases, and a mass transfer rate equation. The transfer rate is proportional to the adsorbate concentration gradient within either the gas or solid phase. Mathematical solutions of these equations usually give the adsorbate concentration as a function of time and distance from the bed inlet. That part of the bed in which the adsorbate concentration changes from a maximum to a minimum value is called the transfer zone. This transfer zone is directly related to a plot of the effluent concentration vs time which has a characteristic S-shape. This general shape is determined by the continuity equation and occurs in many processes of diffusional transfer.

Jan 1, 1967

By R. P. Harvey, J. E. Walstrom, A. A. Brown

In view of the large number of wells directionally drilled from offshore platforms and urban drillsites, greater interest is being focused on the directional survey and on the uncertainty inherent in calculating the position of the bottom of the hole, or other benchmarks in the wellbore. Of the two methods presented here for evaluating this uncertainty, the first is analytical and uses the principles of probability and statistics. The second method uses Monte Carlo simulation to generate a pattern of the scatter of possible bottom-hole locations. Both methods are based on a model for which the usual assumption is made that the curvilinear axis of the wellbore is adequately represented by a large number, M, of linear segments joined end to end from the top to the bottom of the hole and closely following the course of the hole. The errors due to this approximation are assumed to be negligible and are not studied here. One form of the model is to consider that for a given hole there exists a perfect set of data describing it, of the above form. Each linear segment has an angle of inclination with the vertical 7, in radians, an azimuthal angle from true north xi in radians, and a length Si, in feet. The subscript variable, i, extends from 1 to M. Each of the M linear segments representing the axis of the wellbore has three components in the X, Y, and Z directions. These components are calculated from the equations: The bottom-hole coordinates as determined from the reference set of data for the wellbore are given by the following for i = 1 to M: X=SX, Y = Sy, Z=SZ; . (2) A directional survey instrument, lowered into the wellbore to the M segments, or stations, measures the values of the 7; and the 3,. In general, because of errors from various sources, the resulting angular measurements will not be precisely equal to the 7" and xi. Random variables l, and Ai are therefore considered with associated probability density functions fi(li) and gi(Ai), respectively, which represent the distributions of potential survey measurements for this hole. Since it is assumed that the values Si are accurately measured they are treated deterministically. The random variables corresponding to the surveyed bottom-hole coordinates are given, for i = 1 to M, by:

Jan 1, 1970

By T. G. Sieber, T. D. Tiemann

The extraction of quartz from siliceous iron ores by dissolution in sodium hydroxide solution has been described in detail in AIME Transactions. l923 data reported covered the temperature range from 230-416°F, where a continuous increase in the amount of silica extracted with increase in temperature was found. It is the purpose of this paper to describe some unexpected results of more recent work exploring principally the range of 500600°F where higher rates and greater amounts of silica extraction were antici-p ted. In brief, the experimental procedure consists in digesting the ore under pressure in solutions of sodium hydroxide, filtering the suspension and weighing and analyzing the dried residue for iron content. The amount of extraction is calculated from the weight loss or from the iron analysis of the residue and that of the original ore.

Jan 1, 1969

By B. A. Eaton

The subject of many discussions and technical papers in the last 20 years has been the prediction of the well-bore pressure gradients that are required to induce or extend fractures in subsurface formations. The subject merits this attention because of the frequently recurring problems that arise from an inability to predict fracture pressure gradients. Encountered in several common types of operations in the oil industry are problems associated with the prediction of formation fracture pressure gradients. When wells are being drilled in both new and old fields, lost circulation is often a very troublesome and expensive problem. Complete loss of circulation has been disastrous in some cases. Many times, such disasters could have been avoided if techniques for calculating fracture pressure gradient had been employed in the well plans, and if casing strings had been set, and mud weight plans had been followed accordingly. In areas of abnormally pressured formations, the prediction of fracture gradients during the well-planning stage is extremely important. In fact, it is as important as the prediction of formation pressure gradients, which has received a great deal of attention in recent years. There are several published methods used to determine fracture pressure gradients. However, none of these methods appears to be general enough to be used with much reliability in all areas. In 1957, Hub-bert and Willis published a classical paper that included the development of an equation used to predict the fracture extension pressure gradient in areas of incipient normal fau1ting.l Overburden stress gradient, formation pore pressure gradient and Poisson's ratio of rocks were the independent variables that were shown to control fracture pressure gradient, the dependent variable. In 1967, Matthews and Kelly published another fracture pressure gradient equation that is different from that of Hubbert and Willis in that a variable "matrix stress coefficient" concept was utilized.3 Later the same year, Costley wrote about a similar idea.5 Goldsmith and Wilson used a least-squares curve-fitting technique and field data from the Gulf Coast area to correlate fracture pressure gradient with formation pore pressure gradient and formation depth.' They noted that the fracture pressure gradient increased with increasing depth while the pore pressure gradient remained constant. In each of these cases, the problem for which a solution was sought was to determine the bottom-hole pressure gradient required to initiate or extend a fracture. Results of the previous work show that fracture pressure gradient is a function primarily of overburden stress gradient, pore pressure gradient, and the ratio of horizontal to vertical stress. There is argument for a fourth variable in that in many cases breakdown fracture pressure gradient is greater than the fracture extension pressure gradient. However, if the fracturing fluid is able to penetrate the formation through the pores or existing cracks, there is very little

Jan 1, 1970

By M. F. Trice

PYROPHYLLITE is a hydrous aluminum silicate (A12Si4010(OH)2)1 that occurs in both the foliated and the massive forms. The foliated variety resembles talc in that it has a greasy feel, a pearly luster, perfect basal cleavage, and usually is white, although in some deposits apple green, gray, brown, russet, and nearly black specimens may be found. The massive deposits of pyrophyllite yield pearl gray to light tan aggregates, some of which are so friable that they may be crushed with the hands into a fine gritty powder. Frequently specimens of the massive variety are studded with crystals of radial structure. The mineral has a specific gravity of about 2.7 and a hardness of 1 on Mobs' scale.1 The chemical composition of commercial pyrophyllite reflects the mineralogy of the deposits, which, according to Stuckey,2 contain pyro-phyllite and quartz, together with chloritoid, sericite, and a few other minerals of negligible importance. The latter, he says, "are noticed in but small quantities to the extent they might occur as accessory constitu-ents of an igneous rock or as products of regional metamorphism or weathering. . . . Quartz is abundant everywhere except in the very best grades of pyrophyllite." Analyses of specimens from several deposits are listed in Table 1, showing that the silica content varies from 57 to 73 percent and the alumina from 22 to 33 percent. Oxides of iron and the alkaline metals are collectively present, with one exception, to an extent of about 1 to 1.5 per cent.

Jan 1, 1940

By R. R. Joseph, K. A. Gschneidner

The solid solubility of magnesium in the close-packed modifications of lanthanum, cerium, praseodymium, neodymium, gadolinium, dysprosium, and lutetium was determined from approximately 250°C to the eutectoid temperature by the X-ray parametric technique. The maximum solubility at the eutectoid temperature was found to be 9.4 at. pet in La, 8.2 in Ce, 9.2 in Pr, 8.2 in Nd, 14.1 in Gd, 13.5 in Dy, and 11.5 in Lu. The solubility when compared at a homologous temperature was found to increase in a smooth manner with decreasing size factor from lanthanum to lutetium. It was found that the apparent atomic radius of magnesium when dissolved in the lanthanide solvent was constant and could be accounted for by consideration of several models dealing with departures from Vegard's law. The eutectoid temperatures for the lanthanide-rich La-Mg, Ce-Mg, and Nd-Mg systems were found to be 544", 505°, and 551°c, respectively. A study of the solid solubility of magnesium in the lanthanide metals was initiated because the valency and electron egativity difference are essentially constant and favorable for solid-solution formation, and thus one could examine the effect of size on terminal solid solutions. The size factors based on metal radii range from 14.6 pet for lanthanum to 7.5 pet for lutetium. Since the electronegativity difference is small, 0.06 unit or less, application of the Hume-~othery' and Darken and Gurry2 criteria for solid-solution formation indicates that the solubility of magnesium would be expected to be small for lanthanum (between 5 and 10 at. pet) and to increase as we proceed along the lanthanide series. A search of the literature revealed no data on the solubility of magnesium in the lanthanide metals except for the solubility of magnesium in cerium at 450oCA typical phase diagram for the lanthanide-rich end of the lanthanide-magnesium phase diagram is shown in Fig. 1. EXPERIMENTAL PROCEDURES Preparation of Alloys. The lanthanide metals used in the preparation of alloys for this investigation were prepared from the corresponding fluoride by metallothermic reduction techniques previously described by Daane.4 The chemical analyses of the metals used are listed in Table I.

Jan 1, 1965

By P. Somasundaran, D. W. Fuerstenau

This article presents the results of an analysis of grinding of 1:1 mixtures of 4x8-mesh quartz and limestone in laboratory ball and rod mills. From these experiments, the amount of energy consumed in grinding each component of the mixture was determined. In the ball mill, limestone consumes slightly more energy than quartz in the initial stages of grinding, but as the grinding proceeds quartz begins to consume a slightly greater fraction of the energy. The postulate that the fraction of energy consumed by any material in a ball mill is proportional to its volume fraction has been shown to be approximately true. On the other hand, in a rod mill energy consumption by quartz and limestone is equal only in the initial stages of grinding, with energy consumption by quartz greatly exceeding that by limestone as rod milling proceeds. Preferential energy consumption in tumbling mills has been discussed in a number of papers. For example, from an analysis of the kinetics of comminu- tion in ball mills, Arbiter and Bhrany' obtained rate equations based on the postulate that only coarse particles are ground, indicating that fine particles are protected from the action of the balls by coarser particles. In rod mills this protective action is much more pronounced than in ball mills. Recent studies on the rod milling of limestone-quartz mixtures have shown that this protective action causes the mineral with the lowest grindability (quartz in this instance) to consume the greater fraction of energy. 2 However, in the ball milling of mixtures it has been postulated that the consumption of energy by one of the constituents is determined by its volume fraction within the mill. 3 Possibly this hypothesis may be a simplification of the ball milling of mixtures since the protective action suggested by Arbiter and Bhrany may result in some preferential energy consumption by one of the constituents of a mixture. The objective of this study has been to determine preferential energy consumption in laboratory ball and rod mills by analyzing size distributions of each material in the products obtained from grinding 1:l mixtures of quartz and limestone. MATERIALS AND METHOD The procedure for carrying out the tests on wet grinding quartz-limestone mixtures has already been described.'r3 In the present investigation, 1:l mix-

Jan 1, 1963

By Don K. Smith

The Reclamation Program for the Northern Zone of the Indus Plains in West Pakistan involves the construction of 30,000 irrigation wells to serve 20 million acres with an annual pumpage of nearly 40 million acre-ft. Detailed hydrologic studies indicated that mild steel would be satisfactory for casing; however, within two years after construction, about 10% of the wells began to fail due to encrustation and corrosion of the casing. A search to find a noncor-rosive substitute for the steel casing disclosed that only fiberglass-reinforced plastic pipe satisfied all requirements. The results of initial use of fiberglass have been highly satisfactory and have resulted in a lower over-all well cost. Advances in technology pomise further reduction in prices and improvement in performance. The northern zone of the Indus Basin comprises a vast area of essentially level land in West Pakistan which is irrigated by means of a complex system of canals that distribute more water to more land than any other irrigation system in the world. In spite of the development of this extensive irrigation system, production of food and fiber has not met the requirements of the country. The major reasons that crop production has not reached anticipated levels are the lack of adequate irrigation supplies and effective subsurface drainage. As a result, yields per acre are among the lowest in the world for areas where irrigation is practiced, and many thousands of acres of valuable crop land have been removed from production or seriously affected by salinity and waterlogging. To rectify the problems of irrigation supply and drainage the Government of Pakistan has undertaken a program of Salinity Control and Reclamation which is being administered by the Water and Power Development Authority. The Authority retained Tipton and Kalmbach, Inc., of Denver, Colo., as engineers for the program in the northern zone of the Indus Basin. This program consists of the construction of about 30,000 irrigation wells to provide drainage for waterlogged lands and full irrigation supplies, including leaching requirements, for all cultivated lands. The program will ultimately ensure the productivity of 20 million acres and involve an annual pumpage from groundwater storage of nearly 40 million acre-ft of

Jan 1, 1970

By G. T. Engel, W. G. Gruzensky

Jan 1, 1960

By J. Douglas, W. T. Ford, G. E. Henderson, I. F. Roebuck

An implicit numerical method is presented for simulating the differential and algebraic relations governing one-dimensional three-phase flow in porous media. The method is based upon compositional representation of the hydrocarbon system. Variable physical properties and water-oil capillary forces are included in the formulation; however, the effect of gravity is ignored. The effects of changing composition and mass transfer are considered through the use of known phase behavior concepts and correlations. The differential and algebraic equations and the numeric approximations to these equations are presented, and the computing algorithm is discussed in detail. This method is used to simulate a single-phase, two hydrocarbon-component gas displacement laboratory experiment. The method is also applied in simulating a solution gas drive and a gas injection problem using a reservoir oil represented as a nine-component mixture. For comparative purposes, the latter two problems also are examined with a one-dimensional volumetric model. The results of the simulation of the laboratory experiment demonstrate the relevance of this method to problems wherein the effects of mass transfer significantly enter the displacement process. The comparison of the results of the volumetric and compositional methods applied to a reservoir system illustrates not only the advantages and benefits derived from examining the hydrocarbon system composition, but also the necessity of this approach in application to a general reservoir problem. INTRODUCTION The advent of large memory, high-speed digital computers enabled reservoir engineers and mathematicians to pool their knowledge in the development of sophisticated techniques for the prediction of oil and gas reservoir performance. These techniques have progressed from volumetric and trend analysis calculations to the development of "mathematical models", or reservoir simulators. These latter models, in general, utilize finite difference approximations to the rather complex partial differential equations that mathematically describe the physics and thermodynamics of fluid flow in porous media. Many forms of this "model" type are available today, and much of the recent literature has been devoted to either improving known methods or developing new techniques for use in these prediction methods. The more advanced techniques in use at this time consist of the solution of differential and algebraic relations that describe a reservoir geometry in one, two or three dimensions and that incorporate reservoir hydrocarbon and water fluid systems that obey specified physical laws, having properties that might easily be measured in the laboratory. This type of model utilizes formation volume factors and other volumetric data, expressed directly as functions of pressure, to represent the reservoir fluid system. Experience gained with this type of simulator, commonly known as a "beta-factor model", has indicated that the approach has many outstanding defects, most of them due to the assumption that those properties measured in the laboratory completely describe the behavior of the fluid system throughout the life of the project under study. The effects of varying hydrocarbon composition and mass transfer between the phases of this hydrocarbon system must, by definition, be ignored. These defects, which may often be ignored in

Jan 1, 1970

Jan 1, 1963

By A. W. Ruff

The seismic wave produced by an explosive is very important in blasting. A true understanding of the wave is only important when considering possible structural damage to buildings located near the blast, but it is also of primary importance when considering rock fragmentation. Because of the importance of the seismic wave to fragmentation, a finda-mental study of the seismic wave and its effect was made at the Cananea Consolidated Copper Co.'s mine at Cananea, Sonora, Mexico. Strain gages were used to measure the strain in the rock when nearby explosive charges were detonated. The variance in the circuit voltage caused by changes in the resistance of the strain gage was measured with an oscilloscope and recorded with a Polaroid camera. CONFINED DRILLHOLE CHARGES To record the seismic wave from a confined drillhole explosive charge, a gage was cemented to the bottom of a 4-in diam drillhole. The horizontal gage hole and nine horizontal charge holes were drilled perpendicular to the center line of the 2-39 drift and 4 ft above the floor. The gage hole was 29 in. deep, and the charge holes were drilled so that each bottomed 1 in. deeper than the gage hole. The gage was installed with its axis horizontal and parallel to the 2-39 drift. The charge holes had the following horizontal distances from the gage: hole 3, 3 ft; hole 4, 4 ft; hole 5, 5 ft; hole 9, 9 ft; hole 10, 10 ft; hole 14, 14 ft; and hole 15, 15 ft. Figs. 1 and 2 show the relationships of the gage and the charge holes. Charges of 80 pct special gelatin, which weighed 50, 100, and 150 g were exploded in the charge holes and the seismic waves were recorded. All charges were stemmed with 200 g of mud and detonated with an electric blasting cap. Fig. 3 shows the recorded seismic waves. The reflected components of the waves were too weak to be objectional on these records. Table I shows the data taken from the wave forms. The approximate average velocity of a wave with a 9-ft travel distance was 12,900 fps. Since different charge weights were used, it was necessary to scale the data. The scaled maximum compress ion-strain data and the scaled maximum tens ion-strain data are shown in Figs. 4 and 5, respectively. Figs. 6 and 7 show the strain-distance data from Figs. 4 and 5 converted to a 1-lb charge. The results showed that the wave consisted of an initial compression pulse followed by a tension pulse. The amplitude of the tension pulse approached the amplitude of the compression pulse as the distance between the gage and the shot increased. The decay rate of the seismic wave is very important in the evaluation of the blasting characteristics of a rock. When high-amplitude stresses are produced, as in rock fragmentation, the rate of decay is much more rapid than when small amplitude stresses are produced. In underground mine blasting, the burdens are usually not greater than 6 ft and the decay is very rapid. The rapid seismic-wave decay rate in the fragmentation range means that in practice, if the minimum weight of powder is used to break a specified burden, only a very

Jan 1, 1961

By F. W. Jessen, C. C. Patton

Adsorbed films were formed on polished stainless steel specimens from dilute benzene solutions of two crude oil distillation residua. Although the two residua were extremely dissimilar in composition, contact angle measurements showed that the two films increased the wettability of the steel specimens to oil by equal amounts. Furthermore, the wettability of the films was essentially unaffected by the desorption techniques used. Paraffin deposits were formed from heptane-wax solutions on the same stainless steel specimens. These deposits definitely adhered to the surface. Presence of an adsorbed crude oil film on the metal surface increased its free surface energy and resulted in increased deposition of paraffin. The addition to the heptane - wax solution of small amounts of the same distillation residua that were used to form the adsorbed films resulted in decreased cohesive strength in the deposits formed, which resulted in decreased deposition. The presence of a crude oil fraction both in the solution and as a preadsorbed film eliminated the adherence of a deposit of any kind. A mechanism of deposition is proposed which explains the results obtained. INTRODUCTION The natural formation of any predominantly organic accumulation in oilwell tubing, surface flow lines or other production and storage facilities is called a paraffin deposit. These deposits restrict the production of crude oil, causing a substantial increase in production costs because of decreased flow capacity, expense for periodic deposit removal and unproductive downtime. The conditions under which such deposits form, their physical characteristics and the nature and severity of the problem created are extremely varied. Over the past several years, much progress has been made in developing and utilizing methods to remove accumulated paraffin deposition. However, like so many other problems, the basic stumbling block appears to be a lack of understanding of the fundamental mechanism involved in the formation of such deposits. Crude petroleum is known to contain considerable quantities of polar, surface active substances which Doddl has shown to be present at the oil-water interface. Denekas, Mattax and Davis2 observed that the wettability of reservoir rocks was drastically altered by exposure to crude oil fractions; and Zisman, et a1.3 showed that the nature of the compounds adsorbed on a surface would determine its wettability characteristics. Cole and Jessen4 and Ehrig5showed that surface wettability can have a profound effect on the magnitude of paraffin deposition, and Parks6 demonstrated chat the presence of certain adsorbed films on a metal surface would reduce the adherence of paraffin to that surface. Zisman7 has since advanced the theory that the conditions for adhesion are the same as for wetting. Therefore, it was felt that there was adequate evidence to support the supposition that adsorption of compounds from a crude oil might play an important part in paraffin deposition. ADSORPTION-WETTABILITY EXPERIMENTS Initial experiments were conducted to determine the effects of adsorption from solution of crude oil residua on the wettability of a polished stainless steel surface. Distillation residua with initial atmospheric boiling points of 700F were used in preference to the whole crudes in order to concentrate on the molecular weight range of interest, and to eliminate the possibility of composition change due to evaporation of the light ends. Also, these high boiling materials would be expected to be adsorbed from the whole oil in preference to similar compounds of lower molecular weight.

Jan 1, 1966

By R. F. Shurtz

The problem of estimating the precision of systematic samples from a mineral deposit is attacked by interpolating the quality, or other attribute measured, by using Fourier approximation. Such approximation using trigonometric functions yields a particularly simple expression for the variance of the mean value of the attribute sampled. The increasing volume of publication in which the science of statistics has been applied to the problem of predicting the quality of an ore deposit from sets of samples taken from it might lead one to believe that engineering judgment can be replaced by statistics. There is, in fact, an implicit application of the principle of indifference or of "no advance knowledge" which has been discredited in modern statistical theory and practice. These pages will show that it is not always advantageous, efficient, or safe to apply this principle. This problem will be dealt with by using series of orthonormal functions to describe the distribution of the quality of ore in space as contrasted with the more commonly used distribution of quality as a frequency function. Mining engineers are rarely well acquainted with the use of such series or of the functions comprising them. These uses are commonplace in the fields of communication and information theory and it is not surprising that applications taken from these fields should be found appropriate for the analysis of the information contained in a set of samples from an ore deposit. It is hoped that presentation of the following basic, but incomplete, results will generate wider interest in this method and a fuller development of it as well as of the necessary computational techniques. FUNDAMENTAL PREMISES Random variables in the strictest sense are not very common in mine sampling. The sets of samples are almost always taken systematically and are, hence, not subject to all the laws governing random events. Therefore, unless there is indeed random experimental error in the determinations of quality, the treatment of systematic samples of n members as though they were random samples of n members often leads to calculation of confidence limits for the mean quality which are larger than they should be with the result that unnecessary additional sampling is done. The reason for this will emerge in the following discussion leading to Eq. 24 and its generalization. In order to inquire into such questions on a rigorous basis and at the same time avoid arithmetic complications that would obscure the concepts involved, a one dimensional distribution of quality will be assumed. The quality, Q, in suitable units is expressed as a function of the distance, x, along some straight traverse of the deposit. Such a function

Jan 1, 1967

By H. H. Bein

Most western industrial sands are feldspathic and contain feldspars in variahle amounts. A few deposits will show alumina contents of less than one per cent while others will contain over twelve per cent alumina. Some industries are not especially concerned with the amount of contained feldspar but are interested only in color and in size gradations. Other industries, however, are very much interested in alumina content and set up quite rigid specifications as to this content. Several western plants are beneficiating crude sands both to reduce the iron content and to control the feldspar content. At present, most of these plants are using flotation processes for both controls although a few plants do use magnetic separators for the reduction of iron content. Some work has also been done with electrostatic separators for the feldspar-quartz splits. The Sand Division of Del Monte Properties Company, Pebble Beach, California, has been operating a flotation plant for iron removal and the separation of quartz and feldspar since 1950. As mentioned before, control of alumina, especially in the quartz product, is very important. Some users require an alumina content of less than two per cent and others will demand a product of less than one per cent Al2,O3,. The standard Quinolate method for determining alumina is lengthy and time consuming. The HF —H2SO4 evaporation step is especially critical and, if forced, spattering is apt to occur with a resulting loss of sample. Standard procedure is to evaporate to dry ness overnight at a low temperature. Even with forcing under optimum conditions the procerlnre will take two or three hours to complete. A new method has been developed which allows an alumina determination to be made, in 10 or 15 minutes, on a sample of the quartz product as it is being produced. This pocedure, although simply an approximation, has been most helpful in showing whether or not the product being formed is meeting specifications. This procedure has also allowed a great reduction in samples formerly taken and analysed by the orthodox method. Whether a sample assays 1.75% A12O3, or 1.95% .41,0, is not so important as the fact that it is below the allowable maximum of 2.00%. Similar thinking would apply to products required to contain less than 1.00% A1,0,. The step by step procedures for the method are as follows: 1. Collect sample, drain or filter, and dry. 2. Split sample through standard Jones sample cutter to quarter or eighth sample, depending on size of original sample taken, then split down to about 5 grams through Sepor micro-splitter. 3. Screen through 50 mesh sieve (U.S. Series) and reject undersize. 4. Weigh out 2 grams and place in platinum crucible. 5. Etch with 3-5 mls 38.40% HF for 1 minute at room temp. 6. Decant and wash. 7. Stain for two minutes in same crucible with a 1% water solution of Nigrosene dye. 8. Decant and wash well. 9. Dry.

Jan 1, 1961

By W. V. Long, D. H. Reynolds, R. B. Bhappu

Equilibrium distribution coefficients were determined for some monovalent and polyvalent ions for several absorbing and exchanging media as functions of pH and initial ion concentration. Among ions studied were NH4 (I), K(I), Ni(II), Ce(III), Th(IV), and Mo(VI). Absorbents used were: ion exchange resins; a tertiary, and a quaternary amine in an inert solvent; and some activated carbons. The ions studied were in aqueous HCI, HNO3, H2SO4, or HC104 solutions. The classical mass action expression proved of little value in describing the variations observed. The data indicate that the determining factors in absorption and ion exchange may be the ionic species in the aqueous solution, which in turn depend upon pH, dilution, and perhaps other conditions. Three sorption processes have become prominent in recovering values from leach solutions. These are: 1) ion exchange, 2) solvent extraction (liquid ion exchange), and 3) physical adsorption by materials of high specific surface. In the first two of these processes the exchange reaction is considered chemical in nature, and is discussed in terms of the mass action principle. The third is considered a surface phenomenon and is discussed in terms of surface areas and various forms (Gouy, Stern, Grahame, etc.) of the Helmholtz double-layer theory. Generally speaking, we have found in chemical analysis and hydrometallurgical studies that there are close similarities between the three sorption processes, and also differences which are difficult to reconcile with any of the usual theoretical treatments. That others have experienced the same troubles is shown by the fact that usable processes, in chemical analysis as well as in hydrometallurgy, generally are discovered by empirical procedures. EXPERIMENTAL CONSlDERATlONS The gaps between theory and practice have allowed many conflicting statements to appear in the litera- ture. To learn, in particular, the behavior of some metallic ions on a cation exchange resin at a constant pH, equilibration studies were made over a wide range of concentrations.' Results are shown in Fig. 1 for four metals in hydrochloric acid solution on a strongly acidic cation exchange resin, AG 50W-X8 (Bio-Rad). The distribution coefficient, defined as D = amount of metal extracted per g of resin/amount of metal unextracted per ml of solution is seen to vary in a way to support all manner of reports about its behavior with changes in solution concentration. The metals used were chosen from those least likely to form stable chloro-complexes. The changes of slope in the various isotherms may reflect formation of unsuspected chloro-complexes of low stability (ion-pairing for example) whose concen-

Jan 1, 1967

By Douglas D. Donald

The New Jersey Zinc Co. successfully holed through a 2 1/2-mile haulage tunnel connecting its new Ivanhoe shaft with the Van Mater Shaft at Austinville, Va. This 8x 10-ft cross-section tunnel was driven from both ends and met at a point approximately a mile from one shaft and a mile and a half from the other. In order to make certain that the faces met accurately on line and grade it was necessary to refine conventional mine surveying practices. The mines that are serviced by these shafts are located in the southwestern part of Virginia approximately midway between Roanoke and Bristol at the west foot of the Blue Ridge. While the presence of lead-zinc sulfide ores has been known in this area for more than 200 years, it was in 1902 that New Jersey Zinc Co. acquired the Austinville property, which has been in constant operation since that time. About ten years ago the company undertook an extensive diamond drilling program at Ivanhoe several miles to the southwest. This program was successful in locating sufficient ore to justify the purchase of a number of the properties in this area and plans were made to develop the new orebodies. The discovery of this ore as well as substantial addi- tional reserves at Austinville resulted in a decision by the company to increase its daily milling capacity to 3000 tons, of which about 1000 tons would be supplied from the Ivanhoe mine. After careful consideration of all possible methods of transporting this volume of ore from Ivanhoe to the mill, it became evident that diesel locomotive haulage through a 2½-mile tunnel between the two mines would best suit prevailing conditions. Since the lowest operating level, known as the 1100 level, of each mine would be at approximately the same elevation, it was obvious that such a tunnel should be driven on this level. Not only would this tunnel facilitate feeding Ivanhoe ore into the underground crusher and skip loading installation at Austinville, but it would also open up a known orebody 5000 ft southwest of the Van Mater shaft. In addition it would provide a valuable diamond drilling base from which a large and a potentially favorable but untested block of ground might be explored. In order to hasten the completion of the tunnel, it was felt that it should be driven from both ends. ENGINEERING CONTROL PROCEDURES It was vital that the tunnel junction be made accurately on line and grade; thus it was felt that engineering control of an unusually high degree of reliability was required to prevent an accumulation

Jan 1, 1959

By S. Ramachandran, N. J. Grant, T. B. King

MANY investigations of the rate of the sulfur transfer reaction between carbon-saturated iron and blast furnace type slags have been made." It is evident that the reaction is complex, the rate being affected by the presence of elements dissolved in the metal that are readily oxidized and therefore capable of existing in the slag phase. Thus Goldman, Derge, and Philbrook- have shown that carbon, silicon, manganese, and aluminum, in order of increasing effectiveness, accelerate sulfur transfer from iron containing these elements to blast furnace type slags. Quantitative information is still, however, not available on the relation between what have been termed side reactions, such as silicon transfer and CO evolution, and the sulfur transfer reaction itself. In other words, the stoichiometry of the reaction has not been investigated. In the present investigation, the transfer of all reacting elements and the evolution of CO have been measured simultaneously in order to establish the mechanism of the reaction which occurs in practice. Information of this nature cannot be deduced from equilibrium studies. It should be pointed out that in kinetic studies of this type quantitative conclusions are applicable only to the system studied. This restriction should be borne in mind when attempts are made to compare results from different investigations. Apparatus The apparatus used enables slag and metal samples to be taken at frequent intervals and also provides a continuous record of the amount of gas evolved. A sketch of the apparatus is given in Fig. 1. It may be considered in three sections: 1) furnace section, 2) blank volume section, and 3) pressure measuring section. The furnace section is shown in detail in Fig. 2. It consists of two graphite crucibles, C and D, super-

Jan 1, 1957