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By P. Somasundaran

An experimental and theoretical treatment of the depressing effect of inorganic electrolytes on the amine flotation of quartz is presented. Experimental data obtained for the amine flotation of quartz as a function of pH with potassium nitrate as depressant was used to test the models for the effectiveness of inorganic ions as depressants. The validity of commonly used assumptions are examined. The surface tension data obtained for dodecylammonium acetate solutions as a function of KNO3, concentration indicated that the collector adsorption on bubble cannot be neglected in the treatments, since this adsorption changes significantly with the addition of the inorganic electrolyte. It also indicated the possibility of significant changes in the specific adsorption potential of the collector occurring with the addition of inorganic electrolytes.

Jan 1, 1975

The Institute has no available copies of Bulletin No. 7, January, 1906, and Bulletin No. 105, September, 191.5. The sum of 30.50 per copy will be paid for these Bulletins.

Jan 6, 1917

The Library of the above-named Societies is open from 9 A.M to 10 P. M. except on holidays. It contains about 70,000 volumes and 90,000 pamphlets, including sets of technical periodicals and publications of scientific and technical societies. Members of the Institute, with few exceptions, are forced to spend a portion of their time in localities isolated from sources of information. To these the Library, through its Library Service Bureau, can render valuable service through correspondence; letters requesting information will receive especial attention. The Library is prepared to furnish references and photographic copies of articles on mining and metallurgical subjects; to determine the existence of mining maps, and to furnish general information on the geology and mineral resources of all countries. All communications should he made as definite as possible so that the information received may he what is desired and not include collateral matter which may not be of interest. The time spent in searching for such collateral matter will be saved, and the information will be sent more promptly and in more usable shape.

Jan 6, 1918

By Giovanni B. Barla, Stefan H. Boshkov

The block caving method is examined in this paper on the basis of experimental results and observations in the field, and through the use of numerical modeling by the Finite Element Method. The Grace Mine, developed by a panel caving method, served as a reference case. However, the results obtained and the simulation techniques which have been developed may find useful application in more general conditions as encountered in other mining operations by block caving. Following a brief description of the Grace Mine and of the mining method, the problems associated with the behavior of underground drifts at the production levels, during undercutting and caving, are addressed. The most important results obtained through monitoring of strains and loads in the supports of a runway are discussed, while giving relevance to the sequence of mining operations in the immediate vicinity. The most important geomechanical data, as provided for subsequent modeling, are described with reference to: (a) rock mass characterization and (b) in situ state of stress. Then, the numerical modeling procedures, developed by the Finite Element Method in order to predict the caving phenomena and the behavior of underground openings during undercutting, are discussed. Finally, an attempt is made to compare the pre- dictions of the numerical analyses with, the measurements carried out at the instrumented site. Suggestions as to how to improve the results both qualitatively and quantitatively are also given.

Jan 1, 1984

[NUMERICAL CODE TO MAPS (Region Listed in Roman Numerals after Each Petroleum Section) 1 Alaska 2 Arizona 3 Black Hills 4 Boston 5 Carlsbad Potash 6 Central Appalachia 7 Chicago 8 Cleveland 9 Colorado 10 Columbia 11 Connecticut 12 Delta (VIII) 13 Detroit 14 East Texas (VI) 15 El Paso 16 Gulf Coast (VII) 17 Kansas (IX) 18 Lehigh Volley 19 Mid-Continent (IX) 20 Minnesota 21 Montana 22 Nevada 23 New York]

Jan 1, 1961

By K. H. Coats

This paper presents the development and solution of a mathematical model for aquifer water movement about bottom-water-drive reservoirs. Pressure gradients in the vertical direction due to router flow are taken into account. A vertical permeability equal to a fraction of the horizontal permeability is also included in the model. The solution is given in the form of a dimensionless pressure-drop quantity tabulated as a function of dimensionless time. This quantity can be used in given equations to compute reservoir pressure from a known water-influx rate, to predict water-influx rate (or cumulative amount) from a reservoir-pressure schedule or to predict gas reservoir pressure and pore-volume performance from a given gas-in-place schedule. The model is applied in example problems to gas-storage reservoirs, and the difference between reservoir performances predicted by the thick sand model of this paper and the horizontal, radial-flow model is shown to be appreciable. INTRODUCTION The calculation of aquifer water movement into or out of oil and gas reservoirs situated on aquifers is important in pressure maintenance studies, material-balance and well-flooding calculations. In gas storage operations, a knowledge of the water movemenr is especially important in predicting pressure and pore-volume behavior. Throughout this paper the term "pore volume" denotes volume occupied by the reservoir fluid, while the term "flow model" refers to the idealized or mathematical representation of water flow in the reservoir-aquifer system. The prediction of water movement requires selection of a flow model for the reservoir-aquifer system. A physically reasonable flow model treated in detail to date is the radial-flow model considered by van Everdingen and Hurst.1 In many cases the reservoir is situated on top of the aquifer with a continuous horizontal interface between reservoir fluid and aquifer water and with a significant depth of aquifer underlying the reservoir. In these cases, bottom-water drive will occur, and a three-dimensional model accounting for the pressure gradient and water flow in the vertical direction should be employed. This paper treats such a model in detail — from the description of the model through formulation of the governing partial differential equation to solution of the equation and preparation of tables giving dimensionless pressure drop as a function of dimensionless time. The model rigorously accounts for the practical case of a vertical permeability equal to some fraction of the horizontal permeability. The pressure-drop values can be used in given equations to predict reservoir pressure from a known water-influx rate or to predict water-influx rate (or cumulative amount) when the reservoir pressure is known. The inclusion of gravity in this analysis is actually trivial since gravity has virtually no efFect on the flow of a homogeneous, slightly compressible fluid in a fixed-boundary system subject to the boundary conditions imposed in this study. Thus, if the acceleration of gravity is set equal to zero in the following equations, the final result is unchanged. The pressure distribution is altered by inclusion of gravity in the analysis, but only by the time-constant hydrostatic head. The equations developed are applied in an example case study to predict the pressure and pore-volume behavior of a gas storage reservoir. The prediction of reservoir performance based on the bottom-water-drive model is shown to differ significantly from that based on van Everdingen and Hurst's horizontal-flow model. DESCRIPTION OF FLOW MODEL The edge-water-drive flow model treated by van Everdingen and Hurst1 is shown in Fig. la. The aquifer thickness b is small in relation to reservoir radius rb. water invades or recedes from the field at the latter's edges, and only horizontal radial flow is considered as shown in Fig. 1b. The bottom-water-drive reservoir-aquifer system treated herein is sketched in Fig. 2a and 2b. Here the aquifer

By Will Clark

HE who enters a mining claim within an Indian reservation of the United States of America acquires no rights thereby, because of the fact that the lands within such Indian reservation are not a part of the public domain, and cannot be located or acquired as mineral land. However, where such an entry is authorized as to a particular reservation by an Act of Congress, such claims as may be entered under such authorization are thereby segregated from the reservation, and the Indian title is extinguished. Under the Choctaw Constitution, any citizen of that nation, in other words any Choctaw Indian, who discovered a coal mine, acquired an exclusive right to all coal within a radius of 1 mile. The laws of the Chickasaw nation provided for the formation of corporations to develop coal and other mines, with authority to contract with others to develop and work the mines. Under these laws, leases were made; but Congress subsequently abrogated all existing leases, prohibited all persons from receiving royalties from such mines, and provided that all coal within the nation should remain the common property of the tribes. Such leases are now expressly prohibited by an Act of Congress (32 United States Statutes at Large, 655). All leases of mineral lands upon Indian reservations must now be made under regulations promulgated by the Secretary of the Interior, and the royalties must be paid into the United States Treasury for the benefit of the tribes. In Canada the Indians have no rights to the royal mines and minerals, and the government can make no stipulation with the Indians which would affect the rights of the Province in which the lands are situated. Therefore, while it is true that under our present law no rights can be acquired to a mining claim within an Indian reservation, it seems to be fully within the authority of Congress to make laws, giving such rights to mineral locators as it may deem necessary or expedient.

Jan 6, 1914

By James A. Lewis

It is the purpose of this paper to show the importance of sand characteristics, when combined with other physical data, in evaluating production obtained by secondary recovery operations, and to indicate the benefits to be gained from the application of these principles to primary production.

Jan 1, 1942

By F. H. Daniels

IN this, paper it is my intention to, call your attention to* a few of the many producers using blast, now, in common use in Sweden, and also those constructed by the Washburn & Moen Manufacturing Company at their Quinsigamond Works. During a prolonged stay in Sweden the writer had an opportunity

Jan 1, 1881

By R. G. Charles, E. A. Gulbransen, S. Barnartt

KINETICS of the reaction of zirconium with pure oxygen at elevated temperatures have been studied by several workers for periods of time up to 6 hr.1-1 In two cases,3-4 . the experimental values of oxygen uptake, w, as a function of time, t, were best fitted to the parabolic rate law w2 = kPt + constant. In others,3,4 the cubic rate law w3 = kot + constant, showed better agreement. The most recent data of Gulbransen and Andrew4 indicate that the choice between the parabolic and cubic laws for empirical representation of the data will often be arbitrary. This is particularly true if the first few minutes of the reaction with a clean zirconium surface is attributed to a different oxidation mechanism, for deviations from either rate law were found primarily during the initial period. Thus, the kinetics of this reaction have been too uncertain to permit safe extrapolation to oxidation periods of practical interest (many hundreds of hours). The data to be described are of interest, for they indicate that the cubic rate law applies over long oxidation times. The reaction of zirconium with oxygen at 1 atm pressure was followed at 350" and 450°C for 500 and 200 hr, respectively. Abraded test specimens of pure zirconium sheet' 3.0 X 2.0 X 0.012 cm in size were oxidized by the procedure previously described,3 which included periodic cooling to room temperature for weighing. The surfaces were polished to a 4/0 finish using polishing paper wet with kerosene, then wiped with petroleum ether and washed in redistilled acetone. Fig. 1 shows plots of log ? vs log t. Each curve represents the average of duplicate measurements, and deviations from the average were generally less than 3 pet. The cubic rate law (slope = 1/3) is closely followed. The rate constants, 5.2, x 10 -6 and 2.4, X 10- (mg cm-2)3 per hr at 350" and 450 oC, respectively, are plotted as log k, vs 1/T in Fig. 2, together with cubic constants calculated from the data of Gulbransen and Andrew4 for abraded specimens from the same lot of zirconium. Their data refer to runs of 6-hr duration at a pressure of 0.1 atm 0 and under conditions of uninterrupted heating. In spite of these differences, the latter data yield a straight line which appears to apply equally well to the new extended time data. The energy of activation for the oxidation process, calculated from the slope of this line, i.s 38 keal per mole. This may be compared with the value of 47 keal per mole found by Belle and Mallett3 at higher temperatures. It may be concluded tentatively that extrapolation of short-term oxidation data for zirconium to obtain the long-term behavior is best done through the cubic equation ?3 = kpt + constant. References ' E. A. Gulbransen and K. F. Andrew: AIME Trans., 1949, vol. 185, p. A.515; JouRNal OF Metals, August 1949. 'D.p. Cubicciotti Journal Amer Chemical August1949.Soc., 1950, Vol. 72, P. 3 V. Belle and M. W. Mallett: Joulnal Electro chemical Soc., 1954, ' E. A. Gulbransen 339.and K. F. Andrew: Oxidation of Zirconium Between 400" Gulbransenand 800'C.and AIME Trarzs.. 1957, vol. 209, p. 394; JOUR-Nal of Metals, April 1957. IS Barnartt, B G. Charles, and E. A. Gulbransen: Oxidation of 50 weight pet uranium-zirconium alloy, Journul Electrochemical SOC., 1957, vol. 104, p. 218.

Jan 1, 1959

By S. H. Ash

Mass production methods, although increasingly important for economic reasons, create new hazards, remove many hazards, and improve health and safety by reducing exposure and obtaining better supervision. Such methods must be efficient or be discarded. Skilled workmen are required who must be trained to utilize equipment that replaces picks, shovels, and explosives. The effects of working conditions on the health of workmen have long been evaluated in noncoal mines. Studies and action programs relating to environmental health hazards in the mineral industry have placed particular emphasis on dusts. The anthracite industry is conducting an action program on the problem of dust. Segments of the bituminous industry are now conducting similar investigations. An industrial hygiene survey of coal mining in the State of Washington has been conducted and the results published in 1949. (State of Washington, Department of Health, I. H. Bul letin 4.) Chest X rays were obtained from miners in the six major coal-producing counties. State Health Department mobile X-ray equipment was set up at most large mines. Participation was on a voluntary basis, and response was obtained from 70 percent. Important in successful mining safety programs are training programs for supervisors and workmen alike. These programs recognize that the employe is the focal point in injury prevention and are planned and function around him. During the war, industries had to compete with each other for workers and to obtain and hold good workers, working conditions had to be made attractive. The average age of the mine worker increased, and, contrary to what many expected, mining injury rates decreased rather than increased. To attract competent workers, risks to life and limb, as well as laborious tasks, have to be reduced, and an experienced worker is indispensable for safety. Young men are returning to modernized mines. Mass production methods and equipment are more to their liking; jobs are more remunerative, demand action, and require special training and skill that give them the mark of a craftsman. Such workmen can be taught safe methods.

Jan 1, 1950

By AIME AIME

AS director of Battelle Memorial Institute and as Chairman of the important O.P.M. advisory committee on metals and minerals, Clyde E. Williams numbers his acquaintances in the mineral industries by the thousands and h because his principal hobby is liking human beings, most of his acquaintancs are also his friends. Clyde is one of the many outstanding metallurgist, in the United States who started as a chemist. After graduating from the University of Utah in 1915 he was successively chemist for U.S. Smelting Refining and Mining Co., and at the Bureau of Mines station at Ithaca, N.Y. He then got into, metallurgical work and in 1920 he was appointed superintendent of the Northwest Station of the Bureau of Mines at, Seattle. Subsequently he was assistant to H. Foster Bain in metallugical work for the

Jan 1, 1942

By R. L. Templin, D. A. Paul

The modulus of elasticity is defined as the ratio of stress within the proportional limit to corresponding strain. This property, as thus defined, is a constant for each kind of material; and in tension or compression is usually designated by the symbol E. The modulus of elasticity serves as an index of the stiffness of a material or a measure of its ability to resist change of shape under stresses not higher than the proportional limit. In view of the frequency with which the modulus of elasticity is used in engineering calculations, it is surprising to note the uncertainty that exists as to authentic values, and the marked lack of published information relating to the variation of the constant E within individual alloy systems. A value of 10,000,000 Ib. per sq. in. has been quoted as representative of aluminum and its alloys. This value has been found to be approximately corrcct for pure aluminum and aluminum alloys in which the total percentage of the alloying elements is low, but seriously in error in the case of alloys that contain relatively large amounts of the alloying elements. a National Metals Handbook. b Intcrnatiunal Critical Tables. '' Aluminum Co. of America. " Based on density of alurminum (2.70). c Smithsonian Pliysical Tables.

Jan 1, 1931

By A. J. Lanea

INDUSTRIAL MEDICINE bids fair to become one of the most important and highly developed branches of medical science. Mining companies, even in remote districts, have developed large and efficient medical organizations that comprise the best types of physicians and surgeons. Not infrequently, however, company medical departments have been influenced too much by local conditions-including the compensation laws, which differ widely in the various states. The possibilities of industrial medicine are just beginning to be generally understood, and the variations in the organization and aims of medical departments of mining companies are no more pronounced than in industry as a whole. The industrial physician should be as much a part of the organization as any other official and he should know intimately the various types and phases of work in the plant and should look at his work from the viewpoint of the needs and requirements of his particular industry and company. He should not-be on the outside looking in, but on the inside, working hand in hand with the superintendent, manager, foremen, employment director, safety director, and anybody else with whom in his work he might associate. In any industry it is essential that the doctor be-familiar with working conditions. The mine doctor who never goes underground must remain ignorant of the factors causing many of the disorders he treats as well as miss the best opportunity of gaining the respect and cooperation of the men he. serves. If the mine doctor remains unfamiliar with underground working conditions he bars himself from valuable preventive medical work. It is estimated that the time lost by industrial workers, as a whole, because of illness is about four times as great as that lost because of accidents. While the effort to determine the responsibility of working conditions for illness is often futile, there is a wide field, both for study and practice, in the lessening of sickness among industrial workers. The first step in this direction must be a knowledge of the factors involved.

Jan 2, 1921

By Fred W. Gordon

Apart from the character of pig-iron to be manufactured, other than that it shall be well reduced and open-grained, the selection of the materials should be such as to produce it at the lowest cost. As a rule, the sources of fuels and limestones are not so extensively varied as those of the ores. Many Eastern furnaces are now using Lake Superior ores, and but recently a part of the supply came from foreign ports. It is, however, of the highest importance that the character of fuels and limestones, as well as ores, should be carefully considered in determining their value and making judicious selection among those available. The formulas here offered are based upon the assumption that the heat-requirements for a given mixture are measured by a constant required by the oxide of iron, added to that required for a unit of slag, multiplied by the weight of that slag per unit of iron. The heat-requirements for oxide of iron per unit of pig-iron made are assumed to be 2854 centigrade units. This is taken from the careful analysis of Sir Lowthian Bell, and, so far as the writer is able to determine, is very nearly correct. Dividing this by the quantity of heat that may be evolved and utilized within the furnace per unit of carbon, determines the quantity of carbon required per unit of pigiron ; and if to this be added the quantity of carbon absorbed by the pig-iron, the total requirements in carbon are determined, on the assumption that pure oxide of iron is reduced with pure carbon by the ordinary process of the blast-furnace. Calculating the quantity of slag that would be made from a given mixture of ores, smelted with a given impure fuel and fluxed with a given impure limestone, multiplying this weight of slag by the heat-requirements of its unit (taken at 1050 C. H. U.), and dividing the product by the heat-units evolved and utilized within the furnace per unit of carbon, will determine the quantity of carbon required per unit of pig-iron for the slag.

Jan 1, 1893

By J. J. Forbes

THE Federal Coal Mine Safety Act (Public Law 552, 82nd Congress) was approved on July 16, 1952. It incorporates, as Title I, the Coal Mine Inspection and Investigation Act of May 7, 1941 (Public Law 49, 77th Congress), which gave Federal inspectors only the right to enter coal mines for inspection and investigation purposes but no power to require compliance with their recommendations. Title II contains the enforcement provisions of the act; its purpose is to prevent major disasters in coal mines from explosions, fires, inundations, and man-trip or man-hoist accidents. At this point a brief account of events that pre- ceded the enactment of the Federal Coal Mine Safety Act seems appropriate. The hazardous nature of coal mining was recognized by the Federal Government as long ago as 1865, when a bill to create a Federal Mining Bureau was introduced in Congress. Little was done, however, until a series of appalling coal- mine disasters during the first decade of this century provoked a demand for Federal action. As a result an act of Congress established a Bureau of Mines in the Department of the Interior on July 1, 1910. The act made it clear that one of the foremost activities of the Bureau should be to improve health and safety in the mineral industries. One of the first projects selected by the small force of engineers and technicians then employed was to determine the causes of coal-mine explosions and the means to prevent them. By investigations after mine disasters the fundamental causes and means of prevention were soon discovered, and the coal mining industry was informed accordingly. However, despite this knowledge and the enactment of State laws and the Federal Coal Mine Inspection and Investigation Act of 1941, mine disasters continued to occur with disheartening frequency and staggering loss of life. The devastating explosion at the Orient No. 2 mine on December 21, 1951, resulted in the death of 119 men. The Orient disaster rekindled the memory of the Centralia, I11., disaster of March 25, 1947, which caused the death of 111 coal miners. These two tragedies ultimately brought about enactment of the Federal Coal Mine Safety Act.

Jan 1, 1954

By Blandford C. Burgess

Mica is an orchid among minerals. It is formed in pegmatites, one of the most bizarre of igneous formations, and is exceeded by few other minerals in the perfection it may attain as to size, color, and cleavage. First used for window glazing, as an ornament and article of trade, it has become one of the most essential insulators of electricity, heat, and shock. Most internal combustion engines use mica condensers or capacitors and such machines of war as planes, tanks, and submarines are immobile without it. The original manuscript of this guide was written in April 1943 at the peak of war emergency. It was not used because shortly thereafter a decision was made to buy on a one price basis eliminating differentials for both quality and size. This is now presented with the thought that from the standpoint of preparedness we can only consider another war imminent and every effort should be made to set up in usable form the experience gained during the Second Morld War. Colonial Mica Corp. was set up by Metals Reserve Co. as a wholly owned government agency to encourage production of domestic mica and to purchase it. It soon became the exclusive buyimg agency for such mica. The writer as Southern Manager called on all the private agencies buying mica to assist in formulating buying policies, methods, and prices. A meeting was held for that purpose in Asheville, N. C., July 20, 1942. In the general discussion the first two hours of the meeting it was decided that the following factors should be considered in pricing strategic mica: clearness, flatness, trimming, color, classification (size and quality), free splitting, hardness, and air inclusions. Most of the mica miners have been buying strategic mica, according to the mine, as No. 1, No. 2, or Nos. 1 and 2 combined. In addition to these grades of strategic mica they have been buying three lower grades of mica, electric (vegetable-stained), black-spotted and black-stained. A number of mines were named one by one and the buyers present gave their opinions as to the basis they would use in buying the sheet mica from each. It was suggested that in addition to the prices already published, prices be posted up to 10 pct higher for special quality and preparation and prices be posted 25 pct lower than the published prices for the lowest acceptable grades of strategic mica, giving the buyers authority to make intermediate prices according to the quality and preparation. It was thought desirable at the same time to announce prices for nonstra-tegic mica where such quality is being obtained in mines producing strategic mica and where it would be necessary to take the output in order to get the strategic mica. It was also suggested that the price of electric and black-spotted mica be 50 pct below the price of the lowest grade of strategic mica and the price of black-stained mica be 60 pct below the price of lowest grade strategic mica. The few experienced buyers available were employed but they were inadequate for the job and others had to be trained. All needed a guide or primer of some kind to attain systematic procedure and consistent prices in their respective buying areas. The Mica Buyers Guide was formulated for that purpose based on experience gained in the first six months of buying. The Preface to the original guide was as follows: The purpose of this guide is to serve as a text in training beginners and as a handbook for experienced buyers of the instructions which have been issued up to this time. At the meeting of prospective buyers last summer, it developed that the first essential to attain uniformity must be some kind of check sheet. Our "Mica Buyers Report" was developed for this purpose and forms the backbone of this guide. Price is determined according to size, quality and preparation. Size can be measured, but no system of measurement or machine has been devised which can be substituted for the trained eye of the buyer to deterrnine quality and preparation. Although the "One Price" system was instituted and the "Guide" not used, the buyers were required to continue making out a "Mica Buyers Report" (Fig1) with each lot of mica purchased. The form proved its value and there is no doubt that in another such emergency some similar form should be

Jan 1, 1950

By Richard A. Sheppard

Zeolites-crystalline hydrated aluminosilicates of the alkalis and alkaline earths-are important rock-forming constituents in sedimentary rocks and are potentially valuable industrial minerals. They have a framework structure that encloses interconnected cavities occupied by the relatively large cations and water molecules. The cations, chiefly sodium, potassium, and calcium, and the water have considerable freedom of movement within the structure and give the zeolite their cation- exchange and reversible-dehydration properties. Some zeolites have essential contents of barium, strontium, or magnesium. The basic structure

Jan 1, 1975

By N. F. Dyson, T. R. Scott

The iilzfluence of catalytic agents on the oxidation of ZnS has been studied under pressure leaching conditions, using a chemically prepared sample of ZnS which was substantially unreactive on heating at 113°C with dilute sulfuric acid and 250 psi oxygen. Nurnerous prospective catalysts were added at the ratio of 0.024 mole per mole ZnS in the above reaction but pvonounced catalytic activity was confined to copper, bismuth, rutheniuwl, molybdenum, and iron in order of. decreasing effectiveness. In the absence of acid, where sulfate was the sole product of oxidation, catalysis was exhibited by copper and ruthenium only. Parameters affecting the oxidation rate were catalyst concentration, temperature, time, oxygen pressure, and a7riount of acid, the first two being most important. The main product of oxidation in the acid reaction was sulfur, with trinor amounts of sulfate. An electrochemical (galvanic) mechanism has been suggested for the sulfuv-forming reaction, whereby the relatively inert ZnS is "activated" by incorporation of catalyst ions in the lattice and the same catalysts subsequently accelerate the reduction of dissolved oxygen at cathodic sites on the ZnS surface. Insufficient data was obtained to Provide a detailed mechanism for sulfate fornzation, which is favored at low acidities and probably proceeds th'rough intermediate transient species not identified in the preseni work. THE oxidation of zinc sulfide at elevated temperatures and pressures takes place according to the following simplified reactions: ZnS + io2 + H2SO4 — ZnSO4 + SG + HsO [i] ZnS + 20,-ZSO [21 In dilute acid both reactions occur but Reaction [I] is usually predominant, whereas in the absence of acid only Reaction [2] can be observed. Both proceed very slowly with chemically pure zinc sulfide but can be greatly accelerated by the addition of suitable catalysts, as suggested by jorling' in 1954. Nevertheless, an initial success in the pressure leaching of zinc concentrates was achieved by Forward and veltman2 without any deliberate addition of catalytic agents and it was only later that the catalytic role of iron, present in concentrates both as (ZnFe)S and as impurities, was recognized and eventually patented.3 It is now apparent that another catalyst, uiz., copper, may have also played a part in the successful extraction of zinc, since copper sulfate is almost universally used as an activator in the flotation of sphalerite and can be adsorbed on the mineral surface in sufficient amount The importance of catalysis in oxidation-reduction reactions such as those cited above has been emphasized by various writers and Halpern4 sums up the situation when he writes that "there is good reason to believe that such ions (e.g., Cu) may exert an important catalytic influence on the various homogeneous and heterogeneous reactions which occur during leaching, particularly of sulfides, thus affecting not only the leaching rates but also the nature of the final products." Nevertheless relatively little work has appeared on this topic, one of the main reasons being that sufficiently pure samples of sulfide minerals are difficult to prepare or obtain. When it is realized that 1 part Cu in 2000 parts of ZnS is sufficient to exert a pronounced catalytic effect, the magnitude of the purity problem is evident. An incentive to undertake the present work was that an adequate supply of "pure" zinc sulfide became available. When preliminary tests established that the material, despite its large surface area, was substantially unreactive under pressure leaching conditions, the inference was made that it was sufficiently free from catalytic impurities to be suitable for studies in which known amounts of potential catalytic agents could be added. The first objective in the following work was to identify those ions or compounds which accelerate the reaction rate and, for practical reasons, to determine the effects of parameters such as amgunt of catalyst, temperature, time, acid concentration, and oxygen pressure. The second and ultimately the more important objective was to make use of the experimental results to further our knowledge of the reaction mechanisms occurring under pressure leaching conditions. The fact that catalysts can dramatically increase the reaction rate suggests that physical factors such as absorption of gaseous oxygen, transport of reactants and products, and so forth, are not of major importance under the experimental conditions employed and an opportunity is thereby provided to concentrate on the heterogeneous reaction on the surface of the sulfide particles. As will appear in the sequel, the first of these objectives has been achieved in a semiquantitative fashion but a great deal still remains to be clarified in the field of reaction mechanisms. EXPERIMENTAL a) Materials. The white zinc sulfide used was a chemically prepared "Laboratory Reagent" material (B.D.H.) and X-ray diffraction tests showed it to contain both sphalerite and wurtzite. The specific surface area, measured by argon absorption at 77"K, varied between 3.9 and 4.6 sq m per g. Analysis gave 65.0 pct Zn (67.1 pct theory) and 31.9 pct S (32.9 pct theory). Other metallic sulfides (CdS, FeS, and so forth) used in the experiments were also chemical preparations of "Laboratory Reagent" grade. Samples of mar ma-

Jan 1, 1969

By H. R. Crawford, P. B. Crawford, A. F. Tragesser

A method has been developed to calculate wellbore temperatures during mud circulation and the actual cementing operation to aid in the design of cement slurries. The method agrees within 10F with previously measured values. The calculation technique provides temperatures, as functions of time, at varying depths in both the casing and annulus. The technique also provides this information if a relatively cool cement slurry is pumped into the well immediately following circulation of hot mud. Circulating bottom hole temperatures of brine and a bentonite mud were measured. INTRODUCTION As wells are drilled deeper, greater demands are being made on all phases of the industry, and new technology has been developed to provide satisfactory well completions. However, little or no work has been conducted on accurately determining bottom-hole, static and circulating temperatures.. In designing a cement slurry, such factors as density, fluid loss control, viscosity, deterioration from ternperature, compressive strength and pumping time must be considered. Individual well conditions often make it necessary to include still other factors. Pumping time is a primary consideration and, as wells are drilled deeper, encountering higher bottom-hole temperatures, this property becomes even more important. Cement slurries must be designed with sufficient pumping time to provide safe placement in the well; however, the slurry cannot be overly retarded as this will prevent the development of satisfactory compressive strength. The pumping time of a specific cement is currently obtained by subjecting the cement to simulated conditions of temperature and pressure. A reasonably accurate bottom-hole pressure may be obtained by considering hydrostatic heads of fluids, friction pressure and wellhead pressures. However, accurately determining bottom-hole temperatures is much more difficult. Bottom-hole static temperatures are estimated by considering several sources of information, including logging temperatures, published temperature gradient maps and field experience. This information is usually questionable due to disagreement of data from the various sources. Temperature gradient maps were constructed based on temperatures recorded many years ago while running bottom-hole pressure tests. These thermal gradients then represent an average of well conditions and cannot always apply to a specific well. Also, logging temperatures may be affected by the time since fluid was last circulated, rate of penetration, circulating rate and many other factors. Therefore, even though logging temperatures are available, the question still exists as to the correction factor that should be applied to obtain an accurate static temperature. After obtaining static bottom-hole temperature, it is then necessary to relate this to circulating temperatures actually encountered by the cement slurry. This is accomplished by selecting a test schedule from the API RP-10B corresponding to the estimated well conditions.' The API-recommended practice for testing oilwell cement provides testing schedules for various well depths and conditions. These schedules are intended to simulate down-hole conditions during cementing. They provide a rate at which both temperature and pressure are increased until the estimated circulating conditions are reached. These testing schedules represent circulating temperatures for an average well and, although there is flexibility in choosing the test schedule that most accurately simulates the temperature of an individual well, it still is not possible to consider all the well conditions that will affect the bottom-hole temperature. Many factors affect cement temperatures; for example, the length of time a well has remained static prior to running casing and cementing, the circulation time, the temperature of fluids used in cementing, fluid density and flow properties of fluids. The pumping time for a typical retarded cement could vary from 2 to 4 hours with a 10F change in testing temperature. Variations in pumping time are the most critical in highly retarded cements used in deep, hot wells; yet, predicting bottom-hole circulating temperatures is more difficult in these wells. This work was conducted to develop a means of calculating circulating temperatures as a function of well depth, casing and hole size, pumping rate and time, fluid and reservoir physical properties and thermal status of the well. PREVIOUS WORK In 1941 Farris reported on a study to develop information leading to a more practical laboratory evaluation of oilfield cementing mixtures and performance.' It was then recognized that the pressure factor was being neglected,