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By N. R. Morrow, C. C. Harris

The experimental points which describe capillary pressure curves are determined at apparent equilibria which are observed after bydrodynamic flow has ceased. For most systems, the time required to obtain equalization of pressure throughout the discontinuous part of a phase is prohibitive. To permit experimental points to be described as equilibria, a model of capillary behavior is proposed where mass transfer is restricted to bulk fluid flow. Model capillary pressure curves follow if the path described by such points is independent of the rate at which the saturation was changed to attain a capillary pressure point. Aemodified suction potential technique is used to study cyclic relationships between capillary pressure and moisture content for a porous mass. The time taken to complete an experiment was greatly reduced by using small samples. INTRODUCTION Capillary retention of liquid by porous materials has been investigated in the fields of hydrology,l soil science,2 oil reservoir engineering,3 chemical engineering," soil mechanics,5 textiles: paper making: and building materials In studies of the immiscible displacement of one fluid by another within a porous bed, drainage columnsl and suction potential techniques2 have been used to obtain relationships between pressure deficiency and saturation (Fig. 1). Except where there is no hysteresis of contact angle and the solid is of simple geometry, such as a tube of uniform cross section, there is hysteresis in the relationship between capillary pressure and saturation.2 The relationship which has received most attention is displacement of fluid from an initially saturated bed (Fig. 1, Curve R2), the final condition being an irreducible minimum fluid saturation Swr. Imbibition (Fig. 1, Curve A), further desaturation (Fig. 1, Curve R), and intermediate scanning curves have been studied to a lesser but increasing extent.2 ,3,9-12 This paper first considers the nature of the experimental points tracing the capillary pressure curves with respect to the modes and rates of mass transfer which are operative during the course of measurement. There are clear indications that the experimental points which describe these curves are obtained at apparent equilibria which are observed when viscous fluid flow has ceased; and any further changes in the fluid distribution are the result of much slower mass transfer processes, such as diffusion. Unless stated otherwise, this discussion applies to a stable packing of equal, smooth, hydrophilic spheres supported by a suction plate5 with water as the wetting phase and air as the nonwetting phase. The discussion can also be applied, in many

Jan 1, 1966

By Robert B. Johnson

The refraction seismic method has been used as an indirect means of exploring for fluorspar in southern Illinois by the Illinois State Geological Survey. Use of the method has been restricted to those areas where mineralization is associated with faults, a restriction necessitated by the operating principles of the refraction method. The seismic data enable the interpreter to locate fault zones in the subsurface and, under ideal circumstances, to make estimates of dip direction and magnitude and vertical displacement provided the local stratigraphic units are known and are geophysically recognizable. In this instance, refraction seismic exploration has been successful in the surface mapping of well-developed faults, both simple and complex with which fluorspar may or may not be associated. However, less clear results have been obtained where faulting has been less severe and where there are numerous accompanying mineralized joints.

Jan 1, 1964

By D. H. Gurinsky, D. G. Schweitzer

The empirical equilibrium constantsd the heat of reaction for the reduction have been determined from 300° to 500°C. The mechanisms of the oxidation of uranium and magnesium from dilute bismuth solutions have been investigated. The kinetics of some of the reactions were affected by air adsorbed on the uranium oxides. THE Liquid Metal Fuel Reactor studied at Brook-haven National Laboratory uses a solution of uranium in bismuth as the fuel. Corrosion and stability problems require that the fuel solution contain corrosion inhibitors and deoxidants. Of the additives tested, magnesium has been found to be the best deoxidant and zirconium the best corrosion inhibitor in bismuth. Some experiments1 indicate that magnesium may play a secondary role in increasing the effectiveness of zirconium in inhibiting corrosion. The work reported here was intended to determine the relative concentrations of Mg and U required to prevent oxidation of the uranium fuel in the event of an air leak. In addition, an attempt was made to identify some of the mechanisms of the oxidation and reduction reactions occurring in the liquid bismuth solutions. EXPERIMENTAL Apparatus and Procedure—The equipment shown in Fig. 1 was designed so that the reaction kinetics could be studied as functions of temperature, melt composition, pressure, and flow rate. At the start of a run, the 10-liter bell jar (F) is removed by opening the bottom Dresser fitting (L), and the bismuth and additives are placed in a pyrex crystallizing dish (I). The bell jar is replaced, the system is evacuated to 10-5 to 10-6 mm Hg and then the heater (J) is turned on. When the selected temperature is reached, the oxidizing gas is admitted to the system to the desired pressure as read on the manometer (D). Gas is introduced through the slide tube (Q) which has a pyrex frit (R) sealed to its bottom. Stirring is accomplished by immersing the end of the tube in the melt. To maintain a constant pressure under flow the input and evacuation rates must be equalized. To obtain this condition stopcock (C) is closed and flowmeters (B) are matched. The reaction is "stopped" by closing the inlet flowmeter and quickly evacuating the system. To obtain a liquid metal sample, the system is evacuated with the sampler positioned near the surface of the liquid. The sampler, Fig. 2, is then immersed until its thermocouple reading matches thermocouple (G) Fig. 1. The system is then pressurized with helium which forces the solution through the frit. Twenty to 30 min elapsed between the time the system was evacuated and sampled. During evacuation and pressurization of the system, the temperature variations did not exceed ± 5°C. While bubbling occurred the temperature remained constant to within 1/2 oC. The volume of the equipment was determined by adding a known volume of air at atmospheric pressure to the evacuated system and noting the resulting pressure.

Jan 1, 1962

By C. H. Wayman, D. W. Fuerstenau

The effect of bubble size and concentration of certain reagents on the terminal velocity, shape, path, and drag coefficients of single air bubbles in distilled water has been investigated. Bubbles of a certain size range rise considerably faster than Reynolds number-drag coefficient relationships predict, whereas a small amount of frothing agent reduces their terminal velocity. The rapid velocity at which bubbles rise in distilled water appears to result from slip at the boundary and from circulation within the bubbles. Surface-active agents retard bubble motion through prevention of both circulation and slip at the boundary. A surface tension concentration gradient helps maintain bubble sphericity. HE gas phase is one of the indispensible in-gredients in flotation operations. Flotation depends on the collision of an air bubble and a mineral particle in a pulp and their ability to remain in contact long enough for adherence to take place. Before it is possible to understand the mechanics of air bubble-mineral particle encounter, it is necessary to learn more about the nature of bubbles themselves before collision with a mineral particle has taken place. To date, little work has been done on air bubbles in flotation systems. In 1945 Fahren-wald' presented a study of the role of frothers on air bubbles and on aeration in flotation, and recently Wark and Sutherland' discussed the work of Rosenberg- in relation to flotation. The research reported in this present article was undertaken to investigate systematically the effect of bubble size and the concentration of certain reagents on the terminal velocity, shape, path, and drag coefficient of single bubbles in distilled water. Most of the work is concerned with the effect of a-terpineol on bubble motion in water, but studies were made with potassium chloride, potassium hydroxide, potassium ethyl xanthate, and potassium amyl xanthate. Experimental Method and Materials: To obtain free bubble rise and reduce wall and surface effects, the investigators used a tank of 5½x5½x30-in. internal dimensions, filled with water to within 4 % in. of the top.' The tank was made of acrylic plastic so that the walls would have good optical properties. Distilled water, which was re-distilled in a block tin still and saturated with air before each test, was used in all the experiments. All solutions were made with reagent-grade chemicals. During each experiment the water was at room temperature, and during the course of an experiment the temperature did not fluctuate more than 0.5°C. Since the experiments were performed over a period of six months, the temperature varied between 25° and 27°C. The temperature at which each series of experiments was conducted is recorded with the data. The experimental apparatus is presented dia-grammatically in Fig. l. Individual air bubbles were generated from purified compressed air through a capillary of 0.003-cm internal diameter at a rate

Jan 1, 1959

By N. A. D. Parlee, M. M. A. El-Naggar, G. 8. Horsley

The apparatus was of a modified Sieverts type1&apos;2 with a reaction tube designed to function also as the cell component of an oxygen pressure gage. The reaction tube assembly is shown in Fig. 1 and described in Table I. The main body is a 1-in.-OD 15 mol pct calcia-stabilized zirconia tube. The ground-glass joint, g, the male part of which carried a prism for optical pyrometer use, was connected to the remainder of the Sieverts apparatus. The calibration of the cell (at its 1000°K operating temperature) for internal oxygen pressures (PO2in) in the range 0.2 to 10 9 atm was made against internal air pressures measured by mercury manometer and McLeod gage. At very low po2in values down to l<Tn atm the performance was checked by comparing pQ calculated from electromotive force measurement when the apparatus was filled with a) pure CO gas and b) a CO-CO2 mixture of the ratio CO-CO2 = 1:0.398, with Po, values calculated from the equilibrium constants of the following reactions at 1000°K:

Jan 1, 1968

By F. W. Bowdish

Analysis of data on the equilibrium exchange of sodium ions from salt solutions for calcium ions, from various fractions of an oxidized calcareous iron ore from Lorraine, France, strongly suggests that the calcium may be attached to the solid by only one of its bonds. Nearly equal values were found for the equilibrium expression from data covering concentration ranges of 1000 fold for the salt and 235 fold for the ion-exchangeable calcium. Differences indicated between the exchangeable calcium contents of the slime and the sandy portions of the ore, as well as the equilibrium relationship itself, are of importance in the flotation of the ore. During an experimental program on the flotation of oxidized calcareous iron ores from Lorraine, France, ion-exchangeable calcium was found in the ore. Because this source of calcium ions, if not controlled, could thwart all efforts at flotation, an extensive study was made of the phenomenon. The part of that study reported here was to obtain data on the equilibrium established between ore solids and solutions of sodium chloride, and to analyze the data to try to understand better the physical chemistry of the exchange. The ore contains oolites of goethite and quartz grains embedded in a matrix consisting of calcite and a brown cement believed to be the residue from oxidation of the silicate minerals found in fresh unoxidized ore. When ground, a substantial fraction of the ore becomes a fine slime in which is concentrated more than half of the alumina content of the ore. It is believed that the alumina occurs as unidentified clay minerals with which most of the ion-exchange capacity of the ore is associated. A preliminary experiment on the exchange of ions from the ore for sodium ions from solutions of NaCl showed that calcium was about ten times as abundant as magnesium in the exchange solutions. Thus calcium was the predominant ion in causing difficulties with flotation, and it was the only one for which data was obtained in this study. It is believed that the omission of magnesium ion exchange from consideration does not invalidate the results. It is possible, however, that inclusion of magnesium in the analyses and calculations or its prior elimination from the samples would have improved the consistency of the results. EXPERIMENTAL Data about the equilibrium exchange of sodium from solutions for calcium from the solids were obtained using two different samples of material. The solids

Jan 1, 1963

By David Cole

THE appearance of the Wilfley table in 1897 marked an epoch in the art of concentration of ores. The table has merited and received an almost unprecedented measure of public approval, lasting through its whole patent life. It has been very little improved in itself, or improved upon by competitors. The new machines bidding for popular favor have been of the Wilfley family, but without ability to do markedly better work than the parent m:-chine, or to (to more work except by the use of superimposed decks, the latter having obvious disadvantages. FIG. 1.-The- Butchart RIFFLE System. During the past three years there has been developed at Morenci a new type or arrangement of riffles applicable to the Wilfley type of concentrating table which corrects many of the objectionable features or limitations of the older system and obviates most of the difficulties encountered with it, particularly when handling ores having a low ratio of concentration. The new type is known as the Butchart1 riffle system, and its general arrangement is shown in Figs. 1 and 2.

Jan 2, 1915

By L. D. Keller

The application of hydraulic concentration to large scale operations has been effectively accomplished by the use of the SiphonSizer. Operation has been simple, automatic and essentially trouble free. The use of the primary desliming SiphonSizer on magnetic taconites has shown an improvement in grade of concentrate and an increase in recovery over conventional hydroseparators. Magnetic concentrates have been further deslimed and upgraded in SiphonSizers by floating a coarse middling product away from the heavier concentrate. The application of the Siphon-sizer to closed circuit grinding has met with only partial success to date. Hydraulic concentration of minerals has been practiced for a good many years. Until recently, however, the practice has been limited to equipment using a multiplicity of small pockets and relatively low tonnages and flows. The adaptation of the SiphonSizer to the concentration and classification of magnetite has changed this concept. Some fifty commercial units varying in size from a 16-ft diam circular unit to a 25x100-ft rectangular unit are currently in operation on magnetic taconites. Additional units up to 38 ft diam are under construction. Depending upon the application in the flowsheet, upgrading varies from 0.75% to 14% Fe in a single stage. To those not familiar with taconite processing, the importance of the struggle to remove economically as much silica as possible may not be fully appreciated. Perhaps some figures pertaining to transportation costs will underscore this important process. If the silica content of the concentrate from a 10,000,000 ton per year plant could be reduced by I%, a savings in boat freight, at $2.00 per ton, would amount to $200,000 annually! THE SlPHONSlZER The SiphonSizer, as illustrated in Figs. lA, 1B and 2, is a hydraulic classifier in which the hydraulic water is distributed uniformly across the bottom of the vessel by means of a system of headers (1 and 2), jet pipes (3), and nozzles (4). The depth of the teeter bed is automatically maintained by the siphon-float assembly. The feed is introduced through a feed well (5) and separated into two fractions by the effects of rising water and the density of the teetered bed. The magnetite fraction is discharged by the siphon (12) while the fine slime and light middling overflow a peripheral weir (9) to the overflow launder (6). The bed depth is controlled automatically by float valves (7), which are responsive to changes in the height of clear water supported in the superelevation tubes (8) by the density of the teetered bed. On top of the float (7) is a needle valve (10) which permits

Jan 1, 1963

By L. M. Kaas

Production planning techniques, particularly a production scheduling model are proposed for use in taconite mining in Minnesota. Applications of the scheduling model, on a two-year mine plan, which evaluates the equipment involved, are detailed. Data and tables are included. INTRODUCTION Fifty years ago Walter Swart, a mining engineer investigating the Minnesota taconites for the Jackling interests, made this report: "There is no doubt in my mind that this taconite mining is a game worth playing and that it can be played to a successful finish. It seems now only a question of men, money, methods and details."&apos; The prosperous industry envisioned by Swart and other taconite pioneers is today a reality. Its growth has been spurred by technological advances in mining and beneficiation, depletion of natural ore reserves, and improvement of the economic climate. However, the massive problems that were solved to make this development possible are only a foreshadowing of the questions of "men, money, methods and details" that will be encountered in the future. The increasing demands for higher quality taconite pellets have already forced producers to examine better methods of quality control for their operations. THE NEED FOR PRODUCTION SCHEDULING The maintenance of fairly constant crude ore characteristics is of major importance to mill quality control. Through careful mixing of ore from storage bins, the concentrator staff can partially reduce the deviations of the feed analysis from the analysis desired. However, the limited effectiveness of bin mixing systems has caused some mining companies to utilize large capacity blending piles to reduce grade variations. Although the analysis of material being reclaimed from such a pile is relatively uniform, raw materials still must be scheduled from the mine into the pile in such a manner that the average analysis of all material is close to the feed analysis prescribed by the mill. PRODUCTION SCHEDULING MODEL Minnesota taconite mining companies have used three analyses to estimate how a certain ore will react to concentration. These factors are the crude magnetic iron content of the ore, the iron content of the plant concentrate produced from the ore at a standard grind, and the grindability index of the ore. The actual laboratory tests used to determine these factors have been described by Apuli.2 These data are obtained from analysis of diamond drill cores, and are the established criteria used by mine planning engineers to formulate taconite production schedules. Variations in the grade of mine output should be controlled by any production scheduling system. However, to be truly practical, production scheduling methods must also consider many of the less tangible variables that affect mine operation. These include pit layout, available equipment, and ownership of ore leases. The number and scope of the variables inherent in this type of mine planning suggested that a computer simulation could be used to solve the problem. The preparation of information for use with a computer simulation program was the initial phase of this project. Meaningful data was developed from logs of diamond drill cores. Analyses were related to their respective areas of influence by means of mine maps, Fig. 1. The three assay variables and tonnages for each area were punched on cards. In addition to these values, a location code number was punched in the first eight columns of the cards. This code is explained as follows: Column 1 Bench number Column 2 Quadrant location as determined by mine reference lines Columns 3-5 East-west coordinate Columns 6-8 North-south coordinate The heart of any simulation techniques is a well engineered mathematical model. To develop a model for taconite production scheduling, the relationship between the three assay variables had to be established. Because changes in each analysis factor affect the mill circuits in different manners, a weighting system was used to determine the relative im-

Jan 1, 1967

By Thomas C. Wilder

Jan 1, 1965

By R. H. Atkinson, R. N. Rhoda

An improved technique has been developed for the deoxidation of palladium with aluminum which is especially suitable for use in making small castings with an induction-melting and casting machine. The effect of various crucible linings on the efficiency of the residual deoxidizer and accompanying oxide film in protecting palladium against oxidation during remelting also has been examined; the preferred crucible lining consists of zirconia cement. THE objective of this work was to develop a simple method of deoxidizing induction-melted palladium which would be suitable for use by manufacturers of jewelry and other small castings. In a common method of deoxidizing torch-melted palladium a piece of aluminum foil is dropped on the surface of the molten metal. If a film is present, which is usually the case, it must first be removed by oxidizing the molten metal thoroughly because it would interfere with the entry of the aluminum into the melt. Removal of the film is probably facilitated by a mild fluxing action of the silica crucibles which are used for torch-melting. However, removal of an alumina film from molten palladium in the crucibles normally used for induction melting is a much slower process and it became necessary to modify the de-oxidation procedure. In the modified procedure the charge is simply melted and the desired amount of aluminum, crimped to one end of a tungsten wire, is plunged through the film into the palladium and the wire immediately withdrawn. The trace of tungsten which dissolves along with the aluminum can be avoided, if considered objectionable, by using a palladium wire. In view of the persistence of the alumina film under the conditions of induction-melting it also was decided to ascertain the efficiency of this film in protecting palladium against oxidation during repeated remelting and casting. Melting Equipment and Materials The equipment used for melting and casting consisted of an Ecco GC:6, 6 to 8-kva high-frequency converter and an Ecco M34B centrifugal casting machine. This unit is being increasingly used for making jewelry and dental castings and it also has been found useful in making exploratory melts of a variety of nickel alloys, for which purpose it is well suited on account of its speed of melting and economy of material. A description of the machine and its operation will be published elsewhere.&apos; A common palladium jewelry alloy, 95.5 palladi-um-4.5 ruthenium (referred to as "palladium" in the trade), was selected for the deoxidation tests. It was available as melting stock which had been melted in air to free it from oxidizable impurities, and also as clean scrap from previous melts which had been deoxidized with aluminum. The latter was thought to be typical of clean "palladium" scrap to be found in a manufacturing jeweler&apos;s establishment and it is also similar to one brand of "casting palladium." By the same token, the oxidized melting stock corresponds to "casting palladium" after the latter has been melted and thoroughly oxidized: Pure aluminum wire (99.9 pet), 0.032 in. diam; 1 in. = 0.036 g. Scrap tungsten wire, 0.014 to 0.020 in. diam. Argon, commercial water-pumped; 99.9 pet pure Experimental Procedure Samples of about 50 to 75 g of the palladium alloy were melted in a crucible lined with a proprietary refractory alumina cement. Some charges were melted in air, others in argon. The oxidized melting stock was melted and solidified a number of times in order to remove as much oxygen as possible before deoxidizing, but this treatment was unnecessary in the case of scrap. In either case the metal was deoxidized with aluminum (0.01 to 0.05 pet) by the

Jan 1, 1959

By Edward L. Beutner, Robert M. Crump

Benson Mines low-grade iron ore reserve is a replacement deposit within the Grenville gneisses of the Adirondacks. The average grade of the crude ore is about 23 per cent iron. The iron minerals are principally magnetite and hematite disseminated throughout the gneisses as discrete grains about 1 mm in size. Both the ores that are beneficiated by magnetic means and the non-magnetic ores that are treated by a gravity method of concentration are found in stratigraphically different positions but are mined from one open pit, which is about 2.5 miles long and 800 feet wide and are treated separately. The gneisses are described and named according to the distinctive mineralogy of each. Recognition of the gneissic types permits the interpretation of the structure as a northward-plunging syncline overturned to the west. A large subsidiary anticline-syncline complex occurs on the east limb of the major syncline. Iron minerals in sufficient quantity to be considered ore are confined to areas where the footwall rock has been overturned to become the hanging wall.

Jan 1, 1968

By E. H. Boswell, E. M. Cushing

The Mississippi embayment east of the Mississippi River is part of a vast geologic and hydrologic province. The abundance of water available is largely responsible for the agricultural history of the area and is perhaps the key factor in the rapidly accelerating trend toward industrialization. The multiple artesian aquifer systems that underlie the region and the alluvial aquifer along the Mississippi River are virtually undeveloped sources of fresh water in that they are yielding only a fraction of the water available. The potential yield of the 12 aquifer systems is estimated to be about 25,000 mgd (million gpd) of which only about 600 mgd is presently being withdrawn. The amount of water in storage in these systems is about 1600 trillion gal. Ground water having a dissolved-solids content of less than 500 ppm is generally available at depths of less than 1000 ft, and water having a dissolved-solids content of less than 1000 ppm is available in some places to depths of more than 3000 ft. Iron is the most common troublesome chemical constituent in the ground water. Water in varying amounts is also available from streams within the region. The amount of water which originates within the region and which leaves it as streamflow during a year averages about 50 million acre-ft (about 45,000 mgd). An additional 375 million acre-ft (about 340,000 mgd), which originated outside the region, leaves the region as streamflow during an average year. Some streams have considerable flow during periods of no precipitation and the water during these periods generally has a low dissolved-solids content. Large quantities of water from streams and waterbearing sands (aquifers) are available in the Mississippi embayment east of the Mississippi River. Most of the region is underlain by aquifer systems that will yield large quantities of water to wells, making ground water the most readily available source of fresh water. About 90% of the water used in the region is obtained from wells. Streams have been used primarily to dispose of, and dilute, wastes that have been dumped into them. The Mississippi, Ohio and Tennessee rivers, and the lower parts of the Tombigee and Yazoo rivers also serve as a means of transportation. This nominally water-rich region receives from 48 to 56 in. of precipitation in average years and is crossed by several large rivers. The largest, the Mississippi River, is the western boundary of the region discussed in this paper. The economy of the region is basically agricultural, but industry has become increasingly important since World War 11. The diversification and mechanization of agriculture have resulted in a surplus of manpower, most of which is being absorbed by the expansion of industry. Further industrial expansion probably will occur because of the available manpower, natural resources and economical transportation. Increasing demands on available water supplies will be made and the future economic growth of the region will be largely dependent upon wise utilization and management of the water resources.

Jan 1, 1969

Pulverized Fuel Combustion The apparatus shown in the illustration is a complete equipment f r supplying coal to boiler and metallurgical furnaces, cement and lime kilns, dryers, and to all furnaces requiring a temperature and quality of fame under prompt and easy control. It is claimed that the Aero Pulverizer makes practicable the highest efficiency obtainable from burning coal. It makes coal burn like a gas, a flame, the physical and chemical character of which is regulable- a flame that may be elongated or shortened, thus placing the zone of highest temperature where needed- a flame that may be made oxidizing, reducing, or neutral, as occasion may require. The coal is burned as pulverized, and there is no storage of the powder with its attendant hazard. Artificial drying before pulverizing is not necessary if the coal supply be sheltered from rain and snow. Where the Aero is used, it is wholly a furnace question whether a dryer should be installed; it is not at all a pulverizing or storage question. Labor is reduced to a minimum. Slack coal at low cost yields its last B.T.U.

Jan 11, 1915

By L. F. Elkins

Water coming into wells with bottom water present in the Fosterton field, when their oil recovery was only 0.1 to 1.5 per cent of oil in place below the lowest perforation, confirms lack of shale barriers to vertical flow which also are not apparent in cores and electric logy. Low contrast of vertical and horizontal permeability, high mobility ratio betweerz oil and water zone and pos.rible rate effects due to gravity Combine to prevent easy analysis of water invasion pattern and efficiency by analogy or intuition. Theoretical analysis of performance including these factors using a new direct nurnerical .solution of potential distribution in a network led to unanticapted indications that water would under-run the entire oil reservoir with low volumetric coverage if supplied through natural influx or peripheral water injecfion below the oil-water contact. An unusual pattern of water injection is to he adopted in this recently unitized pool to provide more uniform water flooding in that two-thirds of the oil reservoir not underlain by bottom wafer. INTRODUCTION The Fosterton field, Southwestern Saskatchewan, Canada, was discovered in Jan., 1952. It produces at a depth of 3,100 ft from a pinch-out of the Roseray sand at the Lower Cretaceous-Jurassic unconformity. The field, covering 2,500 acres, contains 54 wells on 40-acre spacing. Development was essentially complete in June, 1954, but significant production did not start until May, 1955, when a pipeline outlet became available. Within one year rapid in- creases in gas-oil ratio and early encroachment of water created operating problems in the down-structure eastern half of the field and raised serious questions about reservoir performance and ultimate recovery. This paper describes the unusual behavior of water encroachment—on both well and reservoir bases—and the analyses made to interpret it. The field was unitized July 1, 1958, for water flooding. A somewhat unconventional

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.

By . M. Muskat

A THEORETICAL consideration of the mechanics of various water-flooding systems with the viewpoint of comparing their relative merits involves the study of two fundamental properties of such systems. On the one hand, it is important to determine the efficiency of the flood as measured by the percentage of the total area that is swept out by the encroaching water before water actually reaches the output wells. This is really a measure of the regional tendency of the water to "bypass" the oil. On the other hand, the various systems must be compared from the viewpoint of their resistances which determine the rate of fluid production obtainable for given pressures maintained at the water input wells. The first of these questions has been studied and very definite answers have been obtained by means of simple electrolytic models.1 These models showed that, in an ideal system, the percentages of the areas flooded out before water reaches the output wells are about 57 per cent for the direct line-drive flood (the input and output wells being equally spaced and placed in alternate parallel lines), 74 per cent for the regular five-spot network, and 79 per cent for the seven-spot network. With respect to the efficiency of the usual flooding arrangements, they are, therefore, given quite accurately by the above numbers. With regard to the resistances of the flooding networks, electrical conduction models have also been used successfully2 and are well adapted to the problem of determining experimentally the pressure distribution and streamlines, or over-all resistances of specific flooding networks. However, such models do not permit readily a study of the effect of changing dimensions or configuration within a network, since a new model must be made up for each set of dimensions considered.

Jan 1, 1933

By S. A. Falconer

The benefication of non-sulfide or non-metallic minerals by froth flotation has been practiced commercially for at least 30 years. In the pioneer stages of development of this flotation art, most of the promoters investigated were fatty acids or soaps that had been found to float sulfide minerals. When commercial application of froth flotation started to assume importance in the late 1920&apos; s and 1930&apos;s, a great deal of fundamental research work was done in the laboratory (11-14, 19, 22, 23, 26, 29, 32). Among other subjects, this work included studies of the relative effectiveness of the different fatty acids and their salts on the flotability of various non-sulfide and non-metallic minerals. The successful present-day use of fatty acid and petroleum sulfonate type promoters results from better understanding of the principles of non-sulfide flotation plus the developnent of effective selectivity modifying agents. Many investigators have contributed to a greater appreciation of the numerous interrelated factors involved in fatty acid and soap flotation of non-sulfide minerals. Of these, mention should be made of recent fundamental studies by Tagart and Arbiter (31); Wolstenholme and Schulman (35); Schulman and Smith (28); Wark and his co-workers(3,4) Du FIietz(l5); and J. Leja(24). According to J. Rogers, K. L. Sutherland and E. E. and I. W. Wark(27), "the basic requirements for a &apos;collector&apos; in flotation are that it shall form a film over the surface of the mineral to be floated and that this film should be oriented so that hydrocarbon (non-polar) groups form the effective surface." When modified in that way, the mineral surface possesses some degree of air avidity. All investigators would agree with Taggart, Taylor and Ince (33)that such a film can be produced only if the collector compound contains an active (polar) group to be attracted to the mineral surface, as well as the non-polar group. The commonly used anionic-type promoters for non-sulfide, non-metallic and metallic oxide ores include: 1. Fatty acids, and their soaps and emulsions. 2. Fatty acids residues — "pitches" and "foots." 3. Sulfonated and sulfated fatty acids and so-called "petroleum sulfonates." 4. Paraffin chain salts — sulfonated and sulfated higher alcohols. 5. Cyclic organic acids or salts, such as naph-thenic acid and naphthenates. Certain fatty acids are more effective than others as promoters for particular minerals under certain specified conditions. Some of the more costly fatty acids or collectors of the paraffin chain salt type may give improved selectivity in some instances and are being used commercially in a limited number of operations. Local availability may dictate the choice of the fatty acid used — for example, the use of palmoil fatty acid for flotation of copper carbonate ores in the Belgian Congo. Coconut oil fatty acids have also found limited use.

Jan 1, 1961

By P. J. Closmann

Steam zone growth as a function of time has been calculated for the case of constant rate steam injection into a preheated reservoir. To simplify the calculation a linear temperature profile has been assumed in the cap and base rock at the start of steam injection. The results indicate that at early times augmentation of steam zone growth due to preheating should be greatest. At longer times the steam zone development becomes close to that calculated with no preheating. INTRODUCTION With the increasing application of thermal recovery processes to recover viscous oil, cyclic steam injection has become important in many large-scale projects. In this process, the cycle of steam injection followed by oil production is repeated a number of times. At the beginning of the second and later cycles, steam is injected into a reservoir that has already been heated but that has lost part of its heat both in produced fluids and by conductive heat loss away from the injection zone. In such a case, the temperature level of the injection zone and the temperature distribution of the surrounding rock will affect the growth of the steam zone developed during the subsequent steam injection. Knowledge of the size of steam zone developed is important in determining the amount of oil displaced and the extent of heating in the reservoir. It is also useful to be able to compute the size of the steam zone for cases where thief zones take most of the injected steam. This paper presents a fairly straightforward method of estimating the steam zone developed in a preheated formation, based on certain simplifying assumptions. Some cases of steam injection into a reservoir at its original temperature have already been considered elsewhere.1-3 Because it is difficult or impossible to obtain an accurate representation of the temperature distribution in the reservoir some time after initial heating has taken place, in this work, a linear temperature profile in the cap and base rock is assumed (Figs. 1A and 1B). The linear profile has the advantage of yielding heat flow equations that

Jan 1, 1969

By D. A. Elgillani, M. C. Fuerstenau, J. D. Miller

Adsorption of lead and ferric iron on quartz and alumina is presented as a function of pH. Only the hydrolyzed species of these metal ions, FeOH++ and PbOH+, adsorb significantly on each of these minerals. Zeta potentials of quartz were measured as a function of pH in the presence of various additions of aluminum, lead, and magnesium salts. Sign reversal occurs at the pH values where significant concentrations of hydroxy complexes are formed. Models of adsorption are presented in the absence and presence of collector. The mechanism of adsorption of metal and collector species in the activation of nonmetallic minerals is still the center of considerable discussion in spite of the extensive study given this system. Until recently, the view was widely held that hydrated metal ions were responsible for this phenomenon. This fact is surprising, since it had been shown that the pH range in which flotation is effected corresponds to that in which metal ion hydrolysis occurs.&apos; Additional support of this concept was pro vided by the work of Wolstenholme and Schulman in another system.&apos; Later work has shown that hydroxy complexes of metal ions are the active species. These studies have also indicated that basic aqueous complexes of metal-collector may be necessary for flotation.3-7 Depending on the molecular weight of the collector, formation of these complexes may occur before or after precipitation of the metal-collector salt has occurred. Ion pair formation can occur when low molecular weight collectors are involved because relatively high concentrations of metal hydroxy complex and collector can be present in solution before precipitation occurs. This is not the case when high molecular weight collectors are used. A model of aqueous complex adsorption has been presented6,7 in which it has been assumed that adsorption occurs by the formation of water from adsorbed hydroxyl and hydrogen of the hydroxyl contained in the complex. Other authors8 have suggested that hy-droxy complexes are involved in these systems but that collector adsorption occurs by replacement of the hydroxyl of the adsorbed metal hydroxy complex with a fatty acid anion. All of these investigations have involved mineral surfaces that were negatively charged so that it is not possible to state with certainty whether hydrated metal ions or hydroxy complexes are the active species in this system. Use of a positively charged mineral should be helpful, however, since the hydrated metal ion will be repelled from this surface. On the other hand, if the hydroxy complex adsorbs by splitting out water, surface charge should have no effect because of the free energy decrease that the system will experience when water is formed. In this regard, sapphire is well-suited for study, since its surface is positively charged until approximately pH 9. Electrokinetic studies of quartz in the presence of various metal ions should also be useful in establishing the mechanisms of adsorption in these systems. That is, if the hydroxy complexes adsorb by water formation, drastic changes in the zeta potential should occur in the pH range in which hydrolysis occurs. In this view, adsorption of ions of widely different hydrolysis characteristics on both sapphire and quartz was measured. In addition, zeta potentials of quartz were measured as a function of pH in the presence of various metal ions and compared with flotation responses obtained under similar conditions. Experimental Materials and Techniques Reagent-grade aluminum, ferric and magnesium chlorides, and lead nitrate were used in this investigation. Adjustments in pH were made with reagent-grade HCl or KOH. Conductivity water, made by passing distilled water through an ion exchange column, was used in all of the experiments.

Jan 1, 1971