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By G. H. Turner, R. C. Bell, E. Peters

Zinc oxide activities in a typical lead blast furnace slag have been calculated from plant operating data. These activities were used to assess the probable effect of fuel composition, oxygen enrichment, and air preheating on the efficiency and capacity of the slag-fuming operation. THE physical chemistry of zinc fuming has been examined with three objectives in mind: 1—to predict conditions favorable to increasing furnace capacity, 2—to predict the changes required to fume zinc more economically, and 3—to explain reported differences in the efficiencies of various slag-fuming plants. This study, made at ail in the plants and laboratories of The Consolidated Mining and Smelting Co. of Canada Ltd., developed from a program undertaken some three years ago on behalf of the AIME Extractive Metallurgy Div. subcommittee on slag fuming. Lead metallurgists first became interested in the recovery of zinc from lead blast furnace slags in 1905 and 1906. An excellent review of the early experimental work has been made by Courtney,' who described blast furnace, reverberatory furnace, and converter methods of fuming zinc from slag. Some of the investigators did not appreciate the importance of reducing the zinc oxide content of the slag to metal in order to fume it, since they tried compressed air blast without fuel in their earliest attempts. However, by 1908, the importance of reducing the zinc was established.' In 1925, the Waelz process for the recovery of zinc oxide from oxidized zinc ores was developed in Germany.' This process was not readily adaptable to lead blast furnace slags because of the difficulty in handling fusible charges in a kiln. What appears to have been the first slag-fuming operation as it is known was commenced by the Anaconda Copper Mining Co. at East Helena, Mont. in 1927." The first Trail furnace was completed in 1930, and this was followed by the construction of several other slag-fuming plants. During the period in which slag fuming has been extensively employed, little development of the chemistry of this process as a whole has taken place. Several good papers on the petrography of lead blast furnace slags have been published,""= but these studies could do little more than establish the forms in which lead and zinc occur in the initial charge and final products of the slag-fuming operation. In recent years, zinc-smelting problems have been ap- proached from a thermodynamic point of view. Maier has published an excellent thermodynamic treatment of zinc smelting." The important thermodynamic properties of zinc and its compounds have been determined and checked by other investigators.' However, to the best of the authors' knowledge, no thermodynamic treatment of the fuming of zinc from slag has been published. A thermodynamic study of any process requires that the essential chemistry of that process be known. In slag fuming there appear to be some differences of opinion as to whether the active reducing agent is elemental carbon or carbon monoxide. Furthermore, some observers have noted that high volatile coals appear to be more efficient than low volatile coals, indicating that hydrogen is also an important factor in the reducing efficiency of a fuel. That both hydrogen and carbon monoxide are effective reducing agents for the zinc oxide content of lead blast furnace slags can be demonstrated readily by introducing these gases into a slag bath held in a neutral vessel at 2100°F (1150°C). Elemental carbon also will reduce zinc oxide, but it is improbable that much free carbon is available for reduction of zinc, as the reaction between the finely powdered coal and air should be largely completed before the solid coal particles reach the slag. Some large-scale fuming experiments using gaseous hydrocarbons have been carried out by other investigators, but, as far as is known, these have not been developed yet into operating processes. The thermodynamic treatment in this paper is based on the following reactions: 1—to supply the thermal requirements C+V2O2- CO [1] C + 0,-CO, [2] H2+ ~z0,-H,O 131 and 2—to reduce ZnO ZnO + CO + Zn + CO, c41 ZnO + H, e Zn + H,O. [51 The furnace-gas composition also is controlled by the equilibrium constant of the familiar water-gas reaction H,O + CO + CO, + H2. C6l In order for the thermodynamic calculations to be quantitatively applicable, it is necessary that the chemical reactions to which they are being applied

Jan 1, 1956

By P. L. De Bruyn

The adsorption density of dodecylammonium ions at the quartz-solution interface has been Theadsorptiondensitydetermined as a function of collector concentration and pH. A ten thoushasbeenandfold range of amine salt concentration was covered at neutral pH. Experimental results show that over a thousandfold concentration range at neutral pH, the adsorption density (I) is proportional to the square root of collector concentration. Except at high concentrations, I increases with increases with increasing pH, but in general this effect is surprisingly small. . , . . A critical pH curve has been established for the flotation of quartz with dodecylammonium acetate. The conditions along the flotation curve are correlated with the adsorption measurements. THE behavior of collectors at the mineral-solution interfaces is usually explained in terms of an ionic adsorption process. Through the distribution of collector ions between the solid surface and the- co-existing solution phase the mineral is believed to acquire a water-repellent surface coating. Quantitative adsorption studies have been made on simple flotation systems1-4 only within the last few years. Such investigations were made possible by the adoption of the radiotracer method of analysis. As a consequence of these studies a new parameter has been added to aid the understanding of the flotation process. The research investigation to be discussed in this paper was undertaken to obtain a better understanding of the behavior of a cationic-type collector. This objective was approached through the determination of the distribution of dodecylammonium acetate between the quartz-solution interface and the solution as a function of the collector salt concentration and pH. To bring this investigation to focus on the more practical aspect of flotation research, an attempt was also made to correlate the adsorption results with actual flotation tests. Quartz: A —100 mesh ground crystalline quartz was infrasized; the products of the third and fourth cones were mixed together and reserved for experimental purposes. This stock material was cleaned by leaching in boiling concentrated HC1. After leaching the quartz was rinsed with distilled water until the filtrate showed no trace of chloride ian. It was then washed several times and dried. The qwrtz had a specific surface of 1400 cma per g as deterhined by the krypton gas adsorption method. Collector: The distribution of dodecylammonium acetate between the quartz surface and the solution phase was determined by the radiotracer method of analysis with carbon 14 as the tracer element. The radioactive amine salt with C" synthesized into the hydrocarbon chain5 was supplied by Armour and Co. The tracer element was located adjacent to the polar group. The radioactive salt as received had a specific activity of about 0.14 mc per g. When desired, dilution of this activity was effected by addition of non-radioactive dodecylammonium acetate also supplied by Armour and Co. ........ All other inorganic reagents used in this research were of reagent grade. Conductivity water was used for making up all solutions. Adsorption Tests: Two different experimental methods were used. In the first, to be designated as the agitation method, a weighed amount of quartz and a measured volume of amine salt solution were agitated in a 100-ml or 50-ml glass-stoppered pyrex graduated cylinder. The cylinder was filled with solution up to the stopper, since erratic results were obtained when an air space was left over the suspension. Time of agitation varied from 1 to 2 hr. Preliminary tests at different agitation times showed that the amount adsorbed remained constant for all agitation times exceeding 1/2 hr. After this conditioning period, the solids were separated from the solution by filtration through a Buechner fritted-disk funnel. The solution was re-circulated 10 times or more to allow the fused silica disk to come to equilibrium with it. Determinations of the amount of amine adsorbed on the frit itself indicated that this amount was less than 10 pct by weight of the amine acetate abstracted by 10 g of quartz. The funnel with quartz covered by a thin layer of solution was then centrifuged for approximately 5 min, at which time the moisture content of the solids was reduced to about 5 pct by weight. The wet quartz was blown into a tared beaker, re-weighed and allowed to dry at room temperature. A final weighing was then made to determine the moisture content. The second experimental method, similar to the procedure adopted by Gaudinand Bloecher,' will be referred to as the column method. Two liters of solution were passed through a bed of quartz contained in a Buechner funnel attached to a pyrex separatory funnel by means of a ball and socket joint. Preliminary tests showed that increasing the volume of solution above 2 liters does not give a measurable increase in adsorption. From 4 to 4 1/2 hr were required for 2 liters of solution to pass through the column. The moisture content of the quartz was again reduced to a minimum by centrifuging. A slightly modified column apparatus was used for experimenting with alkaline amine solutions. The same basic unit was used, but the underflow from the Buechner funnel was again fed into a Separafory

Jan 1, 1956

By W. Chubb

By measuring the hardness of metals at temperatures just above and just below their allotropic change point, it has been established that crystal structure has a real effect upon the strength of metals. The DPH of cobalt, iron, titanium, uranium, and zirconium have been measured at temperatures up to 1000°C. It was found that the body-centered-cubic crystal structure is always the softer structure when it is involved in an allotropic transformation. The close-packed and more complex structures are inherently harder, and may be expected, therefore, to be better base materials for high strength alloys. IT has been observed that for metals with nearly the same melting point (i.e., tin and lead, magnesium and aluminum) the metal with the more complex crystal structure has a higher tensile strength and hardness. It might be asked whether this effect is really caused by the difference in crystal structure; and, if so, just what is the contribution of crystal structure to the strength of these metals. A qualitative answer to these questions can be obtained by measuring the change in hardness produced by the change in structure in metals exhibiting allotropic forms. The evidence for changes in mechanical properties during allotropic transformations is rather meager. In 1909, Rosenhain and Humfrey' observed that "ß" iron showed much less deformation at the transformation temperature than a iron. By means of a torsion test, Lee found that iron bars were "critically plastic" at the a-7 transformation temperature. Sauerwald and Knehans have shown that the dynamic hardness of iron increases between 900" and 1000°C. In 1930, Albert Sauveur' presented data on the hardness, tensile strength, and torsional strength of pui-e iron up to 1000°C. He concluded, "At 900°C, the a iron transforms into y iron, and this is accompanied by increased strength and stiffness and decreased ductility." The same year, Schischokin" obtained data on the hardness of thallium at temperatures above and below its transformation temperature. His data are replotted on semilogarithmic coordinates as Fig. 1. The fact that his data fall on straight lines in this type of plot is believed to attest to the purity of his metal and the accuracy of his results. In 1941, Nadai and Manjoine" obtained tensile data on pure iron with an indicated increase in strength at about 900°C. These experiments make it quite evident that changes in mechanical properties occur when a metal transforms from one crystal structure to another; but, except for Schischokin's data on thallium, none of the measurements seem accurate enough to determine the relative magnitude of the mechanical property change. Materials The metals that have been examined for changes in hardness during transformation include l—as- deposited commercial electrolytic cobalt about 99.7 pct pure, 2—Armco ingot iron, 3—are-melted iodide titanium of a purity in excess of 99.8 pct, 4—uranium of a purity in excess of 99.5 pct, 5—are-melted iodide zirconium of a purity in excess of 99.8 pct, 6—annealed, 0.08 pct C, rimmed steel, and 7—commercially pure RC55 titanium. While the purity of the first five of these materials leaves something to be desired, it will be noted that the observed hardness discontinuities occurred at the accepted transformation temperatures. (These temperatures are indicated by vertical arrows in Figs. 1 and 3 through 7.) The last two materials are commercial alloys introduced to show the effect of minor alloying elements upon the hot hardness curve. Apparatus Hardnesses at elevated temperatures were determined by means of a vacuum hot hardness machine. A diagram showing the basic features of this machine appears as Fig. 2. This machine is essentially a deadweight hardness .machine in a furnace within a vacuum chamber. The sapphire-tipped indentor

Jan 1, 1956

By Rex E. Cheek, Donald E. Menzie

The fluid mapper, a model relatively new to the petroleum industry, was used to study the effect of various mobility ratios on the areal sweepout efficiency for two typical spacing patterns. The experiments indicated the areal sweepout for the five-spot pattern varied from 51.8 per cent at a mobility ratio of 0.093 to 89.1 per cent for a ratio of 24.4. In the direct line-drive pattern, the areal sweepout varied from 58.7 per cent at a mobility ratio of 0.089 to 92.0 per cent at a ratio of 24.8. The fluid mapper may prove useful to determine quickly the effective areal sweepout for any well spacing. INTRODUCTION The effect of the mobility ratio on the areal sweepout efficiency during primary depletion of a water drive reservoir and during secondary recovery operations has recently become more widely recognized The mobility ratio, M, is defined as: _ kjp (displaced fluid) k/u (displacing fluid) where k = effective permeability u = viscosity When the displacing fluid is miscible with the displaced fluid, the permeabilities are equal and the mobility ratio may be expressed as a ratio of viscosities: u (displacing fluid) u (displaced fluid) The mathematical analysis for calculating the areal sweepout efficiency with mobility ratio other than unity is quite tedious.5,11 An experimental method by using a potentiometric model2 in a step-wise manner and in using an X-ray shadowgraph model3,12 with continuous fluid flow has been published. Several types of models have been used to study oil and gas reservoir performance. These models may be classified as physical, electrolytic, potentiometric, X-ray shadowgraph, and fluid mapper. The X-ray shadowgraph and fluid mapper are models relatively new to petroleum engineering and have not been used extensively for specific applications. The theory of the fluid mapper indicates it may be adapted to a study of areal sweepout efficiencies for various mobility ratios as well as other complex problems in petroleum engineering. The use of the model and results obtained when using displacing and displaced fluids of equal densities but different viscosities are discussed. FLUID MAPPER DEVELOPMENT H. S. Hele-ShawV eveloped a fluid mapper model based on the hydrodynamic theory. This theory is that in the steady flow of a viscous fluid between horizontal parallel plates spaced a very small distance apart, the effect of viscous shear is of such magnitude in the vertical plane that the motion in the horizontal plane is practically undisbrted streamline flow. Techniques developed by Hele-Shaw were not expanded and no additional developments in fluid mapper models were forthcoming until A. D. Moore, University of Michigan, published a series of papers starting in 1949, which describe the construction of a flexible and inexpensive model'h nd the fluid mapper technique for the solution of certain problems.' The essential components of the fluid mapper as developed by Moore are::.ln 1. A base slab. made of dental stone (calcium sulphate and water). which is shaped to represent the prototype. 2. Plate glass slightly larger than the slab and spaced

Jan 1, 1956

By H. Kurushima, S. Tsunoda

An investigation of the hydrometallurgy of Cu-Zn concentrates by The Dowa Mining Co. of Japan is described and a detailed flowsheet of the Kosaka hydro-metallurgical plant is given. Sufficient operating experience has shown that the Dorrco FluoSolids system has proven successful for recovery of both zinc and copper by roasting in a fluidized bed. At present, 2400 metric tons of concentrates per month are being treated and recoveries of 93 pct Cu and 65 pct Zn are being effected. A SURVEY of the Japanese chemical industry in 1949 revealed, among other things, that sulphur-bearing blast furnace gas from the Kosaka smelter of The Dowa Mining Co. Ltd., Kosaka, Japan, was being exhausted to the atmosphere as waste. In addition, it was costing that company an average of ten million yen ($28,000) annually for damages to the surrounding property caused by the sulphur dioxide in the gas. It was recommended by this survey that the gas be utilized for the production of sulphuric acid by the contact process. Mr. Kurushima visited the United States in May 1950 to investigate the engineering, construction, and operation of a contact acid plant. Any acid produced at Kosaka would necessarily have to be 98 pct H,SO, to prevent corrosion in railroad tank cars transporting it to the point of use. However, the production of 98 pct acid requires constant volume and SO, content of the gas. As the converter gas at Kosaka fluctuates in both volume and quality, it was decided to evaluate the smelting process with relation to other methods of recovery. This evaluation revealed a relatively new type of roaster, the Dorrco FluoSolids reactor, which was reported to be capable of roasting the copper sulphide concentrate in an excess of air with the production of an SO1 gas strong enough for acid production and a water-soluble copper sulphate calcine. The copper sulphate then could be leached from the roasted ore and electrolytic copper recovered from the leach solution in much the same manner as practiced by the Chile Exploration CO. for treating naturally occuring copper sulphate ores. Use of a reactor of this type would eliminate the need for a blast furnace and converter and, in addition, would effect savings in labor and fuel. The Kosaka ore is a microscopically fine mixture of copper, zinc, and lead sulphides. The lead and a small amount of the barite present can be separated by flotation, but any separation of copper and zinc proved extremely difficult. In blast furnace operation at Kosaka, zinc had been slagged off until a stockpile of about 12,000,000 tons containing 5 pct Zn had been accumulated. Mr. Kurushima felt that if any of the zinc in the concentrate was sulphat-ized and leached with the copper, it also could be recovered electrolytically. The Dorr Co., sponsors of fluidization technique in the metallurgical field, suggested that sulphate roasting be tested out on a laboratory scale and that, if successful, a commercial Dorrco FluoSolids system be constructed. They indicated that the results from such laboratory tests could be transposed to a commercial scale without pilot planting the roasting operation. It was therefore decided to send samples of flotation concentrate to the West-port Mill, laboratories of The Dorr Co., for testing. The objective of Mr. Kurushima's visit to the United States thus had changed from investigation of sulphuric acid plants to a fundamental examination of the hydrometallurgy of copper and zinc. Testing Program In February 1951, Mr. Tsunoda went to the United States to witness the application of the FluoSolids system to sulphate roasting at The Dorr

Jan 1, 1956

By J. Bruce Clemmer, P. E. Churchward, Carl Rompacek

The paper describes a cyclic method for processing manganese ores using sodium sulphate as the basic reagent. Sodium sulphate is electrolyzed in a diaphragm cell to give an anolyte sodium sulphate acid and a catholyte containing caustic soda, a part of which is carbonated in a cyclic manner to form soda and reduced ore is leached with the anolyte to dissolve the manganese and the impurities are precipitated by addition of catholyte. Manganese in the pregnant solution is precipitated as synthetic rhodochrosite with a carbonated catholyte, and sodium sulphate is regenerated. Calcining the manganese carbonate site a high-grade product and the carbon dioxide is returned to the carbonation step. the results of laboratory tests using cells equipped with synthetic fiber diaphragms and permselective membranes which permit transfer of using or cations during electrolysis are described. The article from which the above abstract is reprinted appears in Trans. AIME (1955) 203, p. 51; Journal op Metals (January 1955).

Jan 1, 1956

OFFICERS OF THE WOMAN'S AUXILIARY AIME President-Mrs Robert D Coombs, 375 Paramus Road, Paramus, N J First Vice-President-Mrs W McG Peirce, Troy Court 73 F, New England Avenue, Sum¬mit, N J Second Vice-President-Mrs Andrew E Beer, Richardson Avenue, Sea Cliff, Long Island, N Y Third Vice-President-Mrs Ira T Hook, 494 Norton Parkway, New Haven, Conn Fourth Vice-President-Mrs John R Kenney, 427 W Wrightwood Avenue, Chicago 14, Ill Fifth Vice-President-Mrs Alfonso Ballon, Montero Rosas 115, Barranco, Lima, Peru Recording Secretary-Mrs Arnold H Miller, 601 West 115th St, New York 25, N Y Assistant Recording Secretary-Mrs R J Mechin, 66 East 79th Street, New York 21, N Y Corresponding Secretary-Mrs Theodore Nagel, 76 Remsen St, Brooklyn 1, N Y Treasurer-Mrs Robert W Rowen, 116 East 68th St, New York 21, N Y Assistant Treasurer-Mrs Samuel H Dolbear, 11 Broadway, New York 4, N Y Assistant Treasurer-Mrs H A Kursell, 12 Murray Hill Road, Scarsdale, N Y

Jan 1, 1956

By W. L. Chu

It was observed that chromized coatings on low carbon steel could be embrittled by cooling slowly through the 475°C range. A higher chromium coating was more susceptible to embrittlement than a lower chromium coating. Coating structure and composition could be correlated with the chromizing process and prior carbon content of the steel. IT was recently observed that during the fabrication of rectangular tubings made with chromized thin gage 1010 steel, a high percentage of these parts were fractured readily in a brittle manner under the light impact-forming load employed. Ensuing investigation indicated the cause for such brittle failures to be the so-called 475°C embrittlement of the chromized coatings. The experimental work and results are briefly reported. Rectangular tube sections of normalized AISI C1010 steel, which had a cross-section of 0.5x1.5 in. and a wall thickness of 0.030 in., were chromized to yield coatings having several ranges of thickness, varying from 0.0005 to 0.002 in. Essentially, the chromizing process is similar to that described by Samuel and Lockington,' which consists of heating the parts in a sealed container at about 955°C for 4 hr in intimate contact with a chromizing mixture* samples in a hydraulic press, and the other employed a simple beam bending test of the flat sides of the tubing walls. Neither, however, was able to differentiate the relative brittleness of samples known to include both the brittle and tough types, since the impact-brittle samples were found to deform readily in a manner similar to the tough ones. Both the tough and brittle samples were studied by reflection microscopy. Observation showed that the microstructures of the steel cores were similar in content and distribution of inclusions as well as in the ferritic grain size. Results of Filar micrometer measurements showed that coating thicknesses+ of the brittle samples averaged 0.0007 in., whereas those of the tough samples averaged 0.0016 in. The micrographs of Fig. 2 illustrate the structural differences between coatings of both types of samples. By dissolving the steel cores in nitric acid, coatings of both the brittle and tough samples were isolated. Simple bending tests showed that coatings of the brittle samples cracked readily at about 90" bend, whereas those of the tough samples could be bent nearly 180° without cracking. The coatings as well as the steel cores were analyzed for carbon and

Jan 1, 1956

By I. J. Bear, H. W. Paxton

Studies have been made of the method of propagation of yield in iron single crystals in the range of 205' to 295OK by microscopic and X-ray techniques. 'The results show yielding in two stages, of which the second corresponds closely to the Lüders extension in polycrystalline iron. IRREGULAR macroscopic markings On the polished surface of a polycrystalline mild steel test piece during the lower yield extension were first observed by Liiders.' The lower yield stress was not very constant. Sylvestrowicz and Hall2 showed that it was possible to obtain a constant lower yield stress by using a specimen in the form of a moderately flexible thin strip; the macroscopic markings in this case then appeared as a band of deformation (Lüders' band) which propagated steadily from one or occasionally

Jan 1, 1956

By Glenn C. Waterman

THE diamond drill is a very important tool in exploration and development testing and its use is increasing. In almost all cases results of diamond drilling are analyzed on the basis of grade and tons. A proper evaluation of core and sludge assays is important if drilling results are to be acceptable as a basis for geologic and engineering appraisal. The relatively wide variation in assay averages as calculated by various well-known combining methods indicates that the engineering choice of a method may affect the outcome of the drilling in terms of ore and waste. The problem of combining assay results from core and sludge samples has been discussed many times in conference and in the literature.'-' Most writers agree that the field of disagreement in methods is large and that the engineer on the job must consider features unique to his drilling, pick one of several combining methods, and depart from the rules when abnormal results come in. All the discussion to date can be summed up by the admission that as yet there is no fairly simple, generally acceptable combining method that is practicable over a wide range of drilling conditions, ground conditions, and ore occurrence. The combining problem is important in evaluating drilling results at Chuquicamata. Recently a reappraisal has been made of recovery variables and their effect on assays, with the result that a new combining method is offered which fits average drilling conditions and is mathematically reasonable. It is simple in application, fundamentally correct, and an improvement over most combining methods. At Chuquicamata diamond drillholes are used to outline the grade and position of blocks of normal and marginal grade oxide, mixed, and sulphide ore. Most holes penetrate all classes of material (and waste), and it is important for mining programs as well as ore reserves to know almost precisely the soluble and insoluble copper content of mineralized ground. At present three classes of ore are mined and treated differently. For an orderly sequence of mining operations which can provide regular daily tonnages of all three ore types and keep grade at certain levels with minimum variation, ore type and its grade must be predicted. Diamond drilling plus geologic mapping and bench sampling are tools for prediction. And drilling data are largely used to calculate grade of material more than a few meters away from bench faces. The orebody at Chuquicamata" is criss-crossed by millions of barren or mineralized weak to fairly strong slips and fault fissures. Mineralization is diverse and encompasses many quartz and oxide or sulphide-bearing copper veins, as well as seams and disseminated grains. Copper occurs in oxide or sulphide minerals or mixtures of these two mineral types. Rock conditions vary from intensely seri-citized (soft and porous) through clay-altered ground to almost fresh granodiorite. The result is an orebody which offers many obstacles to good and consistent core recovery in diamond drilling. Recovery varies considerably in the several alteration zones, the various types of oxide and sulphide ores, and the position and inclination of the drillhole within the complex fracture pattern. As core recovery drops sludge samples must be used with core samples to calculate grade. Many years of drilling at Chuquicamata indicate that in good grade oxide zones and in the sulphide areas core recovery is good and the ground uniformly mineralized. Moderate loss of core, therefore, does not markedly affect grade calculations based on core assays. An early core-sludge combining method used core assays at face value as indicating grade down to 50 pct core recovery, but below this recovery percentage sludge samples were used and weighted according to the standard Longyear chart. This method apparently did not introduce serious errors, but it abruptly used sludge assays with high weighting factors representing 100 pct return irrespective of actual percentage of sludge recovered. Recent drilling activities have been directed toward outlining the marginal ore areas. The non-uniform mineralization and generally poorer core recovery in such ground indicated that a more exact core-sludge combining method was required to equate wide differences between core and sludge assays and recovery. In fringe ore areas at Chuquicamata core recovery averages about 50 pct, from a minimum of 10 to 15 pct to a maximum of 100 pct. Sludge recovery is likewise variable and averages perhaps 80 pct even though holes are cemented as water return falls off. In a homogeneously mineralized area cut by many slips and faults, with hard and soft ribs, loss of core is loss of ground which has a grade similar to that of core recovered, and core assays approximate true grade. In this case sludge samples need not be used. However, it would be unusual to know beforehand that an area is uniformly mineralized, and in fact this condition is probably uncommon. Generally the distribution of valuable minerals in the ground does not exactly compare with their recoverability in core. Thus, in the usual case, loss of core decreases the

Jan 1, 1956

By F. F. Craig

A series of both welter and gas puttern Hoods was made in the laboratory to study the oil recovery performances of .such operations. These tests were contlrrctt~tl on consolidated sandstone models, using oil. water, and gas. The model floods were scaled to reprotlrrce field performance under gas arid water five-spot injection. X-ray shadowgraphs permitted observation of the gross fluid movement within the models. A method was developed for applying the mobility ratio concept to water flooding and dispersed gas drives in a five-spot well pattern. The area1 sweep efficiency. tit breakthrough for dispersed gas drives is much higher than previorsly expected, Iying in the range of 50 to 100 per cent. A method is presented for predictitig the water-oil ratio performance of five-spot pattern water flood., in uniform sands. This method is verified experimentally for the cotidition of 120 free gas initially present and for va1ues of gas saturation normally encountered in fields following depletion operations. Prodrrction perfort?zut~cc for pattern gas injection is also predictable by this method. INTRODUCTION In field pattern hater flooding or dispersed gas injection operations, the displacing fluid (water or gas) is injected and oil is produced through wells which are, area-wise. small openings in a large container or rescrwir of oil. As a result, not all of the area between the injection and producing wells is necessarily contacted by the injected fluid by the time it first reaches the producing wells. The question arises in predicting oil recovery. as to what traction of the pattern area involved is contacted by either the injected water or gas due to the relative position of the injection and producing wells. This is the areal sweep efficiency. It is also desirable to know how well arrangement affects the oil production performance. A solution to this problem has been attempted by many means. Mathematical analysis¹,²,³, and electrolytic models', have been used to establish a breakthrough areal sweep efficiency of 73 per cent for a five-spot pattern in which the ability of the oil to flow ahead of the invading fluid is equal to the ability of the invading fluid to flow in the invaded zone. All of these studies simulate only one of many field conditions. Improved studies of areal sweep efficiency at breakthrough were made using the fluid mapper5, poten-tiometric models" and X-ray shadowgraph techniques. In these it was possible to study the effect of variations in mobility of the injected and displaced fluids, and so to cover a wide range of field conditions. The limitation of these studies is that, with these models, it was not possible to simulate the saturation gradient behind the flood front when oil is displaced by gas or water. In the most recent published technical paperS on the subject, a method was presented for predicting the oil recovery performance after breakthrough in a five-spot pattern water flood. The method involved correlations which were obtained experimentally using miscible fluids. One limitation of this work was that a saturation gradient, usually found in immiscible fluid displacement, was absent in these studies. Also the laboratory studies did not cover the situation of a water flood following oil recovery by depletion drive. as is the situation in most field water floods. The tests reported in this paper were made using oil. water, and gas, thus eliminating the simplifications of former studies. Also reported are laboratory studies on

Jan 1, 1956

Jan 1, 1956

By Murray F. Hawkins

One problem of reservoir engineering is the early estimation of the size of newly discovered reservoirs. Often these reservoirs are the expansion type in which sizeable pressure drops occur incident to the production of small fractions of the oil reserve, above the bubble point, and a material balance equation may be solved to find the reserve. The early form of this equation' considered only the compressibility of the oil. Later Hall2 showed that the compressible nature of the formation rock is a significant factor in production above the bubble point, and he presented a new equation which includes a formation (rock) compressibility term. This note presents a further extension of the material balance equation as applied to volumetric, unsat-urated reservoirs above the bubble point by including a term for the presence and compressible nature of the interstitial water. DERIVATION OF EQUATION During a decline in average reservoir pressure, ?p ?p, — p1 the initial reservoir volume V,, will decrease to some value V, due to the reduction in pore volume as a result of a decline in the hydrostatic pressure within the formation, and v, = V,, [l — cr ?p]......(1) The formation compressibility c, is expressed in terms of change in pore volume per unit pore volume per psi. Simultaneously the connate water within the formation expands from an original volume V,, = S,V,, to a new volume V,, V, = s,v,, [I + c,npl.....(2) The difference [Vp — V,] is the hydrocarbon pore volume at pressure p and may be equated to the volume of the remaining oil, or [N — N,] B, = V,,, [I - C~A;] - S,.Vpi [l + cwnjl.........(3) But the initial oil in place in terms of the initial reservoir volume, connate water, and formation volume factor is Ilividing Equation 3 by Equation 4 eliminates V,, to give,

Jan 1, 1956

By J. S. Ll. Leach, L. R. Rubin, M. B. Bever

The energies of formation of ordered and disordered solid solutions of composition CusAu and the energy of ordering in this alloy were determined by tin solution calorimetry. The degree of order was measured by X-ray diffraction and electrical resistance and microhardness measurements were made on ordered and disordered specimens. AMONG the phenomena associated with the order-disorder transformation of a solid solution, the change in internal energy is of special interest because of the part it plays in the various theories of ordering. Published values for the decrease in internal energy accompanying the formation of a superlattice from a disordered solid solution of composition CuAu range from —370 to —2260 cal per gram-atom. Some of these values represent calculations based on theory and others are the results of experimental measurements. The distinction between the change in internal energy, AE, and the change in enthalpy, AH, can here be neglected, because they are approximately equal for solid-state reactions at normal pressure. An analysis of ordering by Bragg and Williams' predicts an energy change of —605 cal per gram-atom for the formation of a superlattice in the alloy Cuau from a completely random solution. Peierls" application to Cuau of Bethe'sb earest-neighbor theory yields —560 cal per gram-atom for the formation of a superlattice from a matrix which initially contains short-range order. Cowley' extended the nearest-neighbor approach to include as many as five shells of neighbors; on this basis a change in energy of —500 cal per gram-atom is expected. Eguchi," using a quantum-mechanical treatment, calculated a value of —2260 cal per gram-atom for the difference in the energy of completely disordered and completely ordered Cu,Au. Sykes and Jones- eated a completely ordered alloy and measured its heat capacity as a function of temperature. This measured heat capacity agrees closely with the corresponding value found by the Kopp-Neumann (or mixture) rule up to about 250°C and above this temperature exceeds it, especially near the critical temperature for ordering. The difference between the integrals with respect to temperature of the observed and the Kopp-Neumann heat capacities was considered to be the energy of ordering. By this method Sykes and Jones found a value of —530 cal per gram-atom. This value is not adjusted for the short-range order remaining above the critical temperature. The pres- ence of such short-range order is suggested by the difference between the measured heat capacity and the extrapolated Kopp-Neumann heat capacity immediately above the critical temperature. Values reported by Weibke and von Quadt' and by Hirabayashi, Nagasaki, and Maniwaa were obtained in the course of investigations primarily aimed at other objectives. Weibke and von Quadt measured the temperature coefficient of the electromotive force of a Cu-CuAu cell. They obtained a value of —1010 cal per gram-atom for the heat of formation of the alloy at 500°C, at which temperature there is no long-range order. They also obtained —1380 cal per gram-atom as the heat of formation of the ordered alloy at 370°C. Considering the heat of formation of the disordered alloy to be independent of temperature, they estimated the energy of ordering at 370°C as —370 cal per gram-atom. At this temperature long-range order is incomplete and the degree of order changes rapidly with temperature. Hirabayashi, Nagasaki, and Maniwa," using an annealing calorimeter, investigated an alloy containing 23.4 rather than 25.0 atomic pct Au and thus could not obtain complete order. Thelr value of the energy of ordering was —490 cal per gram-atom. Orianis has recently investigated the Au-Cu system by the galvanic emf technique. He reports values for the heats of formation of Cu-Au alloys, from which the heat of formation at 427 OC of an alloy of composition CuAu may be found by interpolation. This value is —1080 cal per gram-atom. In the work here reported, disordered and ordered alloys of composition CuAu and corresponding mixtures of gold and copper were dissolved in liquid tin and the heat effects measured. These heat effects are small, since the dissolution of gold in tin is exothermic and the dissolution of copper is endothermic. The method, therefore, yields fairly precise values of the heats of formation of disordered and ordered alloys and of the energy of ordering. Experimental Procedure The calorimeter consisted of a long-necked Dewar flask immersed in a constant temperature salt bath and has been described by Ticknor and Bever." The chief changes in this equipment were an improvement in vacuum and the replacement of the mercury thermoregulator by a resistance thermometer control circuit. The solvent, which was maintained at a constant temperature near 350°C, consisted of 500 grams of 99.99 pct pure tin. The solute samples were mixtures of gold and copper in the proportion corresponding to the composition Cu,Au or solid solutions

Jan 1, 1956

By C. S. Matthews, H. C. Lefkovits

The purposes of this study are (a) to determine the accuracy of a previously proposed method for calclrlating average reservoir pressure and (b) to find a method for estimating the shape of the drainage area of each well in a bounded reservoir. Both numerical and experimental methods are used to determine the pressure distribution and the location of drainage bounrlaries in idealized reservoirs at steady state. A number of photographs are included which show flowlines and drainage areas in reservoir models of various shapes. Results from these studies are then compared with those from the previously proposed method for calculating average reservoir pressure.' It is concluded that the previously proposed method is sufficiently accurate for most reservoir engineering purposes. In addition, some simple methods are given for estimation of .shapes of drainage boundaries. INTRODUCTION A method for the determination of the average Pressure in a bounded reservoir was previously developed by Matthews, Brons, and Hazebroek,1 and presented at the Petroleum Branch Fall Meeting in 1953.† In aP- plying this method, the reservoir was first divided into drainage volumes; second, the average pressure in each drainage volume was calculated; and third, these drainage volume pressures were averaged volumetrically to give the average pressure in the reservoir. It was shown that each well's individual drainage volume, at steady state, is proportional to the well's production rate; however. the question of how to estimate accurately the shape of these drainage volumes could not be answered. Furthermore, in calculating the average pressure for each drainage area, the actual drainage areas, which are in general quite asymmetric in shape, are replaced with one of the symmetric prototypes given in T.P. 3876. A question may then be raised as to how accurately the symmetrical figures depict the pressure behavior of the actual unsymmetrical drainage areas. The study reported on in the present paper was made in an attempt to shed light on the above questions. METHODS It was shown in T.P. 3876 that after a period of steady rate of withdrawal the rate of pressure decline becomes constant at every point in a bounded reservoir containing a single-phase fluid whose compressibility is small and constant and whose viscosity is con-

Jan 1, 1956

By R. L. Hadley, G. Derge

The amounts of oxygen in liquid iron-titanium alloys up to 50 pct Ti were measured and the oxide phases in equilibrium with these alloys were determined by using TiO² crucibles. A minimum of about 0.003 pct 0 occurs at less than 1 pct Ti. The various liquid and solid oxide phases can be arranged on a ternary isotherm. THREE characteristics of titanium contribute to the interesting aspects of its reaction with oxygen in liquid iron: 1—It forms a number of stable oxides. 2—All oxides have large negative free energies of formation. 3—The pure metal exhibits high solubility for oxygen. In addition, the use of titanium as a stabilizing and strengthening element in alloys suggests a need for investigation of its reactions in amounts greater than those normally required for deoxidation. These higher compositions are also of interest because they occur during the addition of ferroalloys and produce deoxidation products before dilution is achieved. Titanium Deoxidation in the Literature While the use of titanium as an alloying element and deoxidizer has been common for several decades, the first detailed study of its deoxidizing characteristics was carried out by Wentrup and Hieber' in 1939. These authors determined the extent of deoxidation possible with titanium and identified, by microscopic examination, the products formed. They found that titanium in excess of 0.2 pct did not reduce the oxygen content of iron below 0.004 pct at 1600°C. They identified the spinel FeO-TiO² at low titanium concentrations and Ti2O³ in melts containing more than 0.2 pct Ti. A portion of the area surveyed by Wentrup and Hieber has been investigated recently by Evans and Sloman² using X-ray diffraction for inclusion identification. They concurred in general with the findings of Wentrup and Hieber, but reported the existence of Ti³O5 as a deoxidation product in the range near 0.1 pct Ti. Comstock, Urban, and Cohen³ discussed the deoxidation of iron with titanium, correlating the data of Wentrup and Hieber with free-energy data for the titanium oxides. Scatter at high titanium values was considered attributable either to the formation of an oxide exhibiting high solubility in liquid iron or to the entrainment of solid oxide particles leading to high apparent solubility. Chipman' has calculated the deoxidation curves for titanium based on free-energy data for titanium oxides. These calculations (Fig. 1) and those of Comstock, Urban, and Cohen involve assumptions as to the activity coefficients of oxygen and titanium in liquid iron, since such data have not been determined. Investigation of the deoxidizing characteristics of chromium" and vanadium0 have shown that these elements decrease the activity coefficient of oxygen in liquid iron, leading to a tendency toward relatively high oxygen values and experimental scatter in highly alloyed melts. Experimental This investigation involved two major objectives: 1—determination of the composition of the oxide phases in equilibrium with liquid Fe-Ti alloys, and 2—establishing the pattern of oxygen solubility in liquid Fe-Ti alloys at titanium concentrations in excess of that required for attainment of minimum oxygen content. Raw Materials Ingot iron was used having the following composition: 0.02 pct C, 0.017 pct Mn, 0.01 pct Si, 0.02 pct S, 0.006 pct P, and 0.03 pct 0. The titanium used

Jan 1, 1956

By G. Derge, R. E. Grace

Diffusivity of bismuth in liquid Pb-Bi alloys has been measured by the capillary reservoir method as a function of temperature and composition. Fair agreement between theory and experiment is found for the measured diffusion coefficients and activation energies of diffusivity and viscosity in dilute lead alloys. The measured diffusion coefficients in the high bismuth alloys describe mass transport in special concentration gradients. THE study of diffusion in liquid metals has been restricted largely to the amalgams over small ranges of temperature and composition. In contrast to this, diffusion and transport of ions and molecules in aqueous and organic solvents have been studied extensively for the past 50 years. The general difficulty of measuring diffusion coefficients in both gases and liquids at high temperatures has been that of eliminating convection currents. Measuring techniques based on freezing and sectioning after the diffusion period1 are not particularly satisfactory because of the volume changes and segregation which occur during freezing. The most promising technique which is currently being developed for liquid metals is the capillary reservoir method. This eliminates convection currents from the diffusion zone and requires measurements only of the length and initial and final compositions of the alloy within the capillary. Anderson and Saddington' have measured the diffusion coefficient of tungstate anions in aqueous Na,W04; Wane4' and Hoffman- ave studied structure and self-diffusion in water and self-diffusion in mercury, respectively, by similar techniques. Selection of the Pb-Bi system for initial study was made for several reasons: I—It afforded a low temperature system for development of techniques which would be suitable for high temperature measurements in liquid iron. This research on diffusion in liquid iron is now in progress as a part of a general program on the rates and mechanisms of slag-metal reactions. 2—Activity data on liquid Pb-Bi alloys of all compositions are available from the emf meas- urements of Strickler and Seltz.9 3—Some data are available on the diffusion of bismuth into solid lead. The measurements on solid alloys were made by von Hevesy and Seith7 for the concentration range of 0 to 2 pct Bi. An appropriate solution to Fick's law (unsteady state) for the capillary reservoir has been found by considering the mass flow which passes through a unit area of surface on a slab of infinite thickness as a function of time. This is the first application of this solution to diffusion measurements, although a similar solution is available for identical boundary conditions.' By analogy with heat conduction, the problem reduces to a perfectly insulated infinite slab at temperature C,, one surface of which is quenched to C, for all times, t. Heat is permitted to flow from quenched surface of the slab to an infinite supply of coolant at C.' (see Appendix). For the corresponding solution for diffusion in liquids, these terms become Where Cu is the initial concentration of component A" in entire capillary at t - 0, C, is the final con- In this case. component A is bismuth, and C, = 0. centration of component A in entire capillary at t = t, C, is the concentration of component A in bath for all t, 1 is the length of the capillary in centimeters, t is the time of diffusion period in seconds, and D is the diffusion coefficient in square centimeters per second. By comparison with solutions to Fick's law used in the solid state, this solution for liquids is similar to the Grube solution for solids, where the change in D with chemical composition is not taken into consideration. Difficulty is to be expected if large concentration gradients are employed and if the concentration gradients extend over an appreciable length of the capillary.

Jan 1, 1956

By J. D. Lindner, Gene E. Roark

Waterflooding operations in the Langston-Kleiner field. Young County, Tex., are described. Widespread application of formation fracturing has been practiced in both producing and injection wells. Field performance data arc cited which indicate than no detrimental effect on sweep efficiencies and that probable benefits in imectivily have resulted from the fracture treatments. I N T R O D U C I O N This paper is a report on a waterflood operation which is being carried out in the Lanpston-Kleiner field located in Young County, Tex. The oil reservoir aflected by this flood operation occurs in a Strawn sand member at an approximate depth of 3.550 ft subsurl'ace. The operators of' the project are Kleiner Estate. Turncr. Fiske. and West who are hereinafter collectively referred to as the Operators. Although the operation is unusual in several respects, the distinctive feature of this flood has been the widespread application of hydraulic formation fracturing treatments as a means to improve productivity and injectivity of the wells. It shall he the purpose of this paper to present basic information regarding the reservoir characteristics. op- craling practices, and waterflood behavior so that conclusions may be drawn concerning the effects which the fracture treatments have had on the performance of this water flood to datc. DEVELOP MENT Development of the 3,550 ft Strawn sand reservoir occurred during 1951 and 1952. The early development occurred on the Langston and Davis leases which arc in the northern region of the Operators' holdings and the wells were drilled on 20-acre proration units according to the field rules. However, studies of the economics of this program. coupled with the decision to proceed with pressure maintenance by water injection. resulted in the adoption of wider spacing in the later stages of development. This variation in spacing is apparent upon inspection of Fig. I upon which only the 3,550-ft Strawn sand producing and injection wells have been located on the Operators' properties. The development to the north of the operators leases is Ihe Garvey Strawn field and that to the south is the Taylor Strawn field. It wits determined that unitization of the leases to he involved in the waterflood program was not feasihle. Consequently. a system of offset injection wells, or lease line injection wells, was adopted from place to place as required to protect correlative rights in the program. This resulted in a dispersed array of injection and producing wells with relatively close proximity of wells along lease line areas and wider spacing toward

Jan 1, 1956

By G. W. Tracy

The material balance equation has been used for many years by engineers to determine reservoir performance. The use of this equation in general has been twofold: first, to determine the oil-in-place in a reservoir; and second, to predict the future performance. The Schilthuis form of the material balance equation, or one equivalent to it, has been used by many of the engineers. The use of the Schilthuis form in predicting future performance has proved to be laborious in that one generally must make several estimates at each step of the trial and error calculation before arriving at a check of the oil-in-place. A method is presented for expediting the calculations. The Schilthuis form of the material balance has been rearranged into a more useable form. In using the material balance to predict the future performance of a reservoir, it has become common practice to estimate the incremental oil production for each step of the calculation which corresponds to a given pressure reduction. Instead of estimating the incremental oil production, the method outlined in this paper better lends itself to estimating the instantaneous gas-oil ratio. A check of oil-in-place is more easily accomplished by estimating gas-oil ratio since it is less sensitive to small inaccuracies. This method incorporates the same self-checking feature inherent in the Schilthius form. DEVELOPMENT OF SIMPLIFlED EQUATION In the development of the simplified equation, the Schilthuis form of the material balance equation will he used. Substituting in Equation 1 for and rearranging terms In Equation 2, the cumulative oil production (n) is multiplied by a factor which is uniquely a function of pressure. Also, the cumulative gas production (G) and net water influx are also multiplied by factors which are a function of pressure alone. These factors are called and are defined as follows: Using these factors, Equation 2 becomes The equation in this form is easier to manipulate mathematically than any of the previous forms which, have been used. Sources of data for the pressure factors are a bottom-hole fluid analysis and the ratio of initial gas cap volume to oil volume in the reservoir. AID IN DETERMlNING THE ORIGINAL OIL-IN-PLACE Each of the curves and +, have a similar shape. Each is infinite at the bubble point pressure. As lhe pressure is reduced below the bubble point, the

Jan 1, 1956

By Otto W. Nuttli

THE magnetic method of prospecting is well suited to determination of faulting in the basement rock. In addition to establishing the horizontal position of the fault, it often furnishes valuable information concerning the depth and amount of faulting. Consider a simple case of a vertical fault, represented in cross-section in Fig. 1. Let A A' represent the plane of observation (ordinarily the surface of the earth), and BB'B"B"' the upper surface of the basement. Assume that the sedimentary rocks are nonmagnetic, so that the magnetic susceptibility of the material above the basement is zero. Let k indicate the susceptibility of the basement rock, c the density contrast between it and the neighboring sedimentary rocks, and the amount of vertical displacement. Fig. 1 shows the material, indicated by cross- hatching, which gives rise to the magnetic anomaly. In most cases it can be assumed that is small compared to the thickness of the sedimentary rocks. The semi-infinite, rectangular slab of rock of susceptibility k, density contrast , and thickness t may then be replaced by a semi-infinite sheet CC' of mass t per unit area at depth 2 (the mean depth of the slab). Nettleton 1 states that this approximation results in an error of less than 2 pct for the computed gravitational field intensity when t is as great as 2/2 and decreases rapidly for smaller values of t. By a theorem of Poisson, the magnetic field intensity can be determined readily from the gravitational field. The theorem states that W = (I/) • (U/i) i1 [1] where W is the magnetic potential associated with the structure, I is the intensity of magnetization which is assumed to have the direction of the inducing field, ? is the constant of gravitation, the density contrast, U the gravitational potential associated with the structure, i the direction of the inducing magnetic field, and i1 a unit vector in that direction. The multiplication indicated in Eq. 1 is

Jan 1, 1956