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By Henry A. Stiff, and Lawrence E. Davis

The authors previously presented a method for predicting the tendency of oil field waters to deposit calcium sulfate. The present paper gives a similar method for calcium carbonate. Methods for predicting calcium carbonate scaling tendencies in fresh waters have been available for some time, but these could not be used for brines. By experimentally deriving the value of the K term in the Langelier equation, a method has been developed which applies to waters of high salt content. A statistical study is included which shows that the experimentally derived values of K are in good agreement with actual conditions. Several applications of the final equation to production practice are given. INTRODUCTION The authors previously presented a method for predicting the formation of calcium sulfate scale in oil field waters.' Although calcium sulfate deposition is important in production operations, the majority of scale problems involve calcium carbonate. The present communication discusses a method by which the formation of this type of scale in oil field waters can be predicted. Calcium carbonate precipitation is caused by a shift toward carbonate in the carbonate-bicarbonate-carbon dioxide equilibrium. When equilibrium shifts in the other direction, the precipitate goes back into solution. Since there is usually considerable delay between the establishment of an equilibrium and the precipitation or solution of calcium carbonate, unstable conditions exist in which a water will precipitate or dissolve calcium carbonate on standing. Tillmans? who did a major part of the early work on carbonate scaling, pointed out that the condition of equilibrium not only indicates the tendency of a water to scale but also is an indication of its corrosive properties. Previously precipitated calcium carbonate combines with iron to form a dense crust which inhibits corrosion. If the water tends to dissolve carbonate, the scale becomes porous, and electrolytic corrosion takes place. Tillmans1 work was extended by several investigators until in 1934 Langeliers developed an equation setting forth the conditions of carbonate equilibrium. By the use of this equation the pH of a water at equilibrium can be calculated. If the actual pH is higher than the calculated pH, the water has a tendency to form scale. If it is lower. the water has a tendency to be corrosive. Langelier's equation can be expressed in a simple form as follows: SI = pH-pCa-pA lk-K where: SI is the stability index. A positive index indicates scale formation. A negative index indicates corrosion. pH is the pH of the water sample, as actually determined. pCa is the negative logarithm of the calcium concentration. pAlk is the negative logarithm of the total alkalinity. K is a constant, the value of which depends on the total salt concentration and the temperature. This equation has been shown to apply to waters with totaI solid concentrations as high as 4.000 ppm. In fact, control of fresh water treatment by means of this equation has been standard text-book practice for a number of years. Nomographs have been worked out so that the stability index of a fresh water sample can be determined in a matter of minutes. Most oil field waters, however, contain well over 4,000 ppm of salts and for this reason the usual application of Langelier's equation can not be made. By an empirical method we have extended the application of the Langelier equation to waters of high salt concentration. By the use of this equation the tendency of oil field waters to deposit calcium carbonate can be predicted.

Jan 1, 1952

[ ] S. H. Ash (Mining Industry Continues with Lower Fatal-Injury Rates, P. 257) was born in Roslyn, Wash. and attended Lehigh University and University of Washington. He received a B.S. and E.M. degree in mining engineering. Mr. Ash was supervising engineer in charge of work of Safety Div., Bureau of Mines, eastern Pennsylvania and the states of N. Y., Del., N. J. and the New England states. He was appointed chief engineer of Metal and Nonmetal Mining Section of the Mineral Production Security Div., Bureau of Mines, July 1942. At present he is chief engineer, Safety Branch, U. S. Bureau of Mines. Besides holding membership in AIME, he is a member of National Honorary Engineering Society, Society of American Military Engineers, Tau Beta Pi and many other societies.

Jan 1, 1952

By C. W. Merrill

The cyanide process in the United States, notwithstanding numerous failures made under the direction of the owners of the patent-rights, and others, has now passed its experimeiital stage, and can, undoubtedly, be made successful when intelligently applied to suitable material. Much, however, remains to be known as to the exact conditions under which this process is applicable to the treatment of gold-bearing ores. If the owners of the patent-rights in this country have ever scientifically investigated the matter, they have never published any valuable informatioil on the subject. Other parties who are now using the process (often independently of the patentees), have nothing to gain by publishing their experience; and, moreover, many of the chemical reactions described in the text-books refer to the use of solutions of potassium cyanide many times stronger than are used in the metallurgical process.

Jan 1, 1896

E. B. WILSON, Scranton, Pa. (written 'discussion *).-Prof. Young's paper shows another application of electricity in solving problems in coal mining, and suggests that it may be possible to utilize the data he has collected in developing an electric firedamp detector. If electric lamps are to be adopted in gassy coal mines, the use of an electric firedamp detector becomes almost imperative, for safety lamps and electric lamps in the same mine are not always conducive to safety, and Liveings electric firedamp detector, is too cumbersome to meet with general approval. Three well understood facts are verified in a new way by Prof. Young's experiments: - 1. The temperature at which methane ignites. 2. The more inflammable gas present in an atmosphere, the hotter will be the flame, and the longer the cap in a safety lamp. 3. As the temperature at the source of ignition varies, the length of the gas-cap flame varies. Prof. H. B. Dixon collaborating with Mr. H. F. Coward, some years ago, made experiments on the ignition of various gases to find the tem-perature of their kindling points.1 From the results of their experiments, the writer has culled the ignition temperatures of some hydrocarbon gases, and has tabulated them with other data, in Table 1.

Jan 10, 1919

By B. Yarar

Jan 1, 1985

By E. L. Swarts

In the course of a program on high-temperature processing and electrowinning of uranium at the Knolls Atomic Power Laboratory,'' it became necessary to give attention to the interaction of molten uranium with graphite. Although it is known3 that a protective interface layer may form, details of this reaction have not been reported. Unfortunately it was impossible to complete the planned experimental program. However, the general problem is considered of sufficient interest to warrant reporting those preliminary results actually obtained. EXPERIMENTAL PROCEDURE Interface carbide layers were formed by melting samples of cleaned uranium metal in small closed graphite crucibles. Equilibrations were conducted in vacuo or in an atmosphere of dry helium at temperatures ranging from 1150" to 1400°C and for periods of from 24 to 240 hr.

Jan 1, 1960

By T. Chen

One of the limitations of the 3-dimensional Lerchs-Grossmann pit optimisation algorithm has been the difficulty in calculating an optimum pit with variable wall slopes. The difficulties have been related to establishing various wall slopes without changing the sizes of the blocks used in the normal computation, but still retaining an optimum solution.

Jan 1, 1977

By Raphael D. Schilz, Michael F. Dunn, Edward D. Thimons, Francis S. Kendorski

During a mine fire or other emergency, it may be desirable to reverse the air flow in order to provide an escapeway or to control a fire. Also, in colder areas, the air flow may be reversed to prevent ice build-ups. When reversing main mine fans, the operator usually does not know what operating characteristics of flow and pressure to expect. Laboratory testing of vane axial main mine fans has been completed in order to establish forward and reverse performance characteristics under controlled conditions, with the results presented here. Preliminary tests under field conditions have also been conducted. The data obtained suggest that reverse performance characteristics are dependent upon the blade angle and the hub to tip ratio. There is also evidence that reverse performance can he predicted for a family of blade angles in a given hub to tip ratio. In general, the air quantity delivered by the fan is 30% to 60% less in reverse than when operating in the normal forward mode.

Jan 1, 1982

By A. Patton

Introduction THE use of roll scale in the Bessemer process dates back, to the "best of our knowledge, at least 20 years. It was first used by the Ohio Steel Co.; Youngstown, Ohio (now the Ohio Works of the Carnegie Steel Co.) under the direction of Sam, MacDonald, Superintendent of the Bessemer Department at these works. Two 10-ton vessels and one blowing engine capable of blowing one heat at a time were employed. The object of using the scale was to -shorten the length of the blow; or in other words, to increase the production with the same equipment. Various means were tried out for introducing the roll scale into the bath of molten iron: It was shoveled into the vessel before the heat was charged, so that the metal would flow over the scale; it was shoveled into the bath after the vessel was turned up; it Was dumped into the empty iron ladle by the wheelbarrow-load, and at times wars dumped on top of the molten metal in the iron ladle. But the practice of introducing the scale into the iron ladle had to be abandoned on account of danger from explosions and of skulling the -ladles. It was soon learned that the proper place to charge the scale was in the empty vessel, so that when the molten iron was poured into the vessel it flowed over the scale, causing a considerable reaction to take place before the heat was turned up. Eventually, cylindrical chutes similar to those now in use were installed. Into these chutes the scale is dumped and carried into the empty vessel. Before this convenient means of introducing the scale was adopted, the Ohio Works had satisfactorily demonstrated that roll scale would increase production, by blowing 107 heats in one 12-hr. turn (1,087 tons) with one blowing engine, blowing one heat at a time; whereas, prior to the use of scale, the best practice at these works was about 80 heats under the same conditions.

Jan 2, 1917

By F. W. Bloecher, A. M. Gaudin

THIS paper describes the results of a series of tests carried out to determine the partition of dodecylamine between distilled water and the surface of quartz at various concentrations of dodecylamine acetate in solution. An adsorption-column technique was utilized for this purpose. Ralston and Harwood, of Armour and Co., had synthesized marked dodecylamine acetate for us.' In their preparation which we employed, 0.0007 pct of the total carbon was the radioactive isotope, carbon fourteen. Unmarked dodecylamine acetate of high purity was also prepared by them for our use. The presence of carbon fourteen in the dodecylamine enabled us to analyze quantitatively for dodecylamine on the surface of quartz, using a radioactive-tracer technique. The method used was that known as internal gas counting of carbon dioxide, formed by oxidation of the amine. This method has already been described, "3 ' and the reader is referred to these papers for details of the analytical method and procedures. and surrounding liquor, a technique analogous to chromatographic columns was utilized. The experimental setup is shown in fig. 1. The dodecylamine-acetate solution was made up in a volumetric flask and poured into the glass funnel shown. It was allowed to drip slowly onto the quartz bed, the rate of flow from the funnel reser- voir being controlled by a hose clamp. The quartz column was contained in a small, fritted-glass filter (size 20 mm, C). The beaded top edge of the filter was cut off to enable the holder and contents to fit into the open end of the 30/45 joint on the combustion tube. This combustion tube is used in the analytical train described in a previous paper.' A piece of gum-rubber tubing joins the bottom of the fritted-glass filter to a filter flask, which in turn is connected to a vacuum line, or water aspirator. The rate of flow of amine solution through the bed was

Jan 1, 1951

By John Jan

Iodine is a soft, lustrous, grayish-black non- metallic element with a density of 4.9. It is the least active of the four members of the halogen family. The other members are, in order of increasing activity, bromine, chlorine, and fluorine. Iodine is a solid at ordinary temperatures, while bromine is a liquid and chlorine and fluorine are gases. Iodine melts at 113°C and volatilizes at 184.4°C to a blue- violet gas with an irritating odor. It occurs in nature only as iodates and iodides or other combined forms. It was discovered by Bernard Courtois in France in 1811, who noticed its presence as an unknown substance in crude soda ash obtained from burning seaweed. Gay-Lussac recognized it as a new element and named it iode, from the Greek word "ioeides or iodes" for violet color (MacMillan, 1970). The world production is not known with any great certainty, but it is probably between 20 and 25 million lb per year, of which about 25% is consumed in the United States. Geology and Mineralogy Iodine compounds occur as a minor constituent as a mineral in the Chilean nitrate deposits and in solution in brines and sea- water. According to the U.S. Geological Survey, it is the 47th most abundant element in the earth's crust. The minerals lautarite, Ca (10,) (calcium iodate), and dietzeite, Ca, (10,) , (CrO,) , (calcium iodate-chromate) are found in Chilean nitrate deposits which are located in Antofagasta and Tarapach provinces on the eastern slope of the coast range in a desert area. Various brines contain iodine compounds. Seawater contains about 0.05 ppm of iodine and some seaweeds will extract and accumulate it up to 0.45% on a dry basis. Some coals in West Germany also contain iodine compounds. The known and potential sources of iodine reported in 1968 are given in [Table 1]. Iodine has been recovered from brines in Java, Indonesia, France, England, and the USSR. Iodine has also been recovered from seaweed in Ireland, Scotland, France, Japan, Norway, and the USSR. The indicated re- serves and future resources of iodine are large but have never been adequately measured. Analysis Iodine as the free element can be detected by the characteristic blue color it gives to a starch solution. Quantitatively it is determined as the free element by titration with standard thiosulfate solutions using starch as an indicator. Colorimetric methods are also applicable.

Jan 1, 1975

By F. W. Bloecher, A. M. Gaudin

THIS paper describes the results of a series of tests carried out to determine the partition of dodecylamine between distilled water and the surface of quartz at various concentrations of dodecylamine acetate in solution. An adsorption-column technique was utilized for this purpose. Ralston and Harwood, of Armour and Co., had synthesized marked dodecylamine acetate for us.' In their preparation which we employed, 0.0007 pct of the total carbon was the radioactive isotope, carbon fourteen. Unmarked dodecylamine acetate of high purity was also prepared by them for our use. The presence of carbon fourteen in the dodecylamine enabled us to analyze quantitatively for dodecylamine on the surface of quartz, using a radioactive-tracer technique. The method used was that known as internal gas counting of carbon dioxide, formed by oxidation of the amine. This method has already been described, "3 ' and the reader is referred to these papers for details of the analytical method and procedures. and surrounding liquor, a technique analogous to chromatographic columns was utilized. The experimental setup is shown in fig. 1. The dodecylamine-acetate solution was made up in a volumetric flask and poured into the glass funnel shown. It was allowed to drip slowly onto the quartz bed, the rate of flow from the funnel reser- voir being controlled by a hose clamp. The quartz column was contained in a small, fritted-glass filter (size 20 mm, C). The beaded top edge of the filter was cut off to enable the holder and contents to fit into the open end of the 30/45 joint on the combustion tube. This combustion tube is used in the analytical train described in a previous paper.' A piece of gum-rubber tubing joins the bottom of the fritted-glass filter to a filter flask, which in turn is connected to a vacuum line, or water aspirator. The rate of flow of amine solution through the bed was

Jan 1, 1951

By R. E. Ogilvie, H. C. Gatos, R. E. Hanneman

The ejj-ect of high pressures on chemical inter-diffusion in the Fe-V system was determined by analyses of concentration vs distance profiles of atmospheric and high-pressure diffusion couples. Diffusion data were obtained as a function of tern -perature and composition. Activation energies, activation volumes, and frequency factors were determined at 1 atm, 20 kbars, and 40 kbars as a function concentration in the a and y phases. The A great deal of research has been carried out in the measurement and understanding of binary chemical inter diffusion in solids. Studies of the effects of high pressure on interdiffusion in binary systems, however, have been virtually nonexistent until the present work. This paper gives a detailed account of the effect of high pressure on interdiffusion and the Kirkendall effect in the Fe-V system. The present data are compared to existing theo- Kirkendall effects were measured at 1 atm and 40 kbars. At 1 atm Dy > DFe at the marker concentration; however, Dv approaches DFe under pressure, and at 40 kbars the values are approximately equal. The high-pressure and atmospheric diffusion data are evaluated on the basis of theoretical models. Chemical analyses of the diffusion -couple profiles were made using an electron microbeam probe. retical treatments of pressure dependence of diffusion which are based upon self-diffusion studies. THEORY The rates of atomic migration in metals and alloys are regulated by the repulsive forces exerted on an atom during its motion from one equilibrium lattice site to another and by the availability of a jump site. Application of high pressure is expected to decrease diffusion rates because it decreases interatomic distances as well as defect concentrations. A number of theoretical treatments have been focused on the problem of calculating self-diffusion coefficients in solids under atmospheric pressure. In general, the vacancy mechanism of diffusion appears to be dominant at high temperatures in most metallic systems. The migration of an atom by this

Jan 1, 1965

By W. G. Pfann

Formation and slow solidification of a molten zone in a homogeneous ingot produces a discontinuity in solute concentration at the boundary of the zone and a gradient of concentration within the zone. By using two solutes, one a donor, the other an acceptor, step or graded pn barriers can be produced. EXPLOITATION of the difference in concentration between a molten solution and the solid which freezes from it is continued in this paper. The normal segregation which results from this difference has been used for purification'.'2 and for pn barrier-formation in semiconductors."4 By means of traveling molten zones this difference has been used to effect multistage separations and to eliminate segregation in ingots." a It will be shown here that by means of stationary molten zones this difference can be used to produce discontinuities in concentration. In particular it will be shown that a pn or npn barrier can be made by the simple act of melting and refreezing a portion of a block of semiconductor, provided that the block contains proper concentrations of a donor and an acceptor in solid solution. Assumptions The operation of melting and slow refreezing will be called remelting and the interface between liquid and solid at the start of refreezing will be called the remelt bormdary. While remelting may be done for various shapes of starting crystal and remelt zone it will be assumed that the remelt zone is cylindrical, its length being measured in the direction of freezing, which is normal to the remelt boundary, and

Jan 1, 1955

By Richard McCaffery

THIS paper considers certain aspects of the acid Bessemer process, particularly in its relations to the duplex process-that combination in which the pig iron is first desiliconized and decarburized in acid Bessemer converters and then dephosphorized in basic open-hearth furnaces. The acid Bessemer process employs an acid-lined converter and produces an acid slag. The blow is usually thought to eliminate the silicon and manganese as oxides and then to burn off the carbon as carbon monoxide. On account, however, of the relatively large amount of metallic iron present in the converter, compared with the relatively small amount of the impurities it is desired to oxidize, the first reaction in the converter probably is the formation of iron oxide, which dissolves in the bath and acts as an oxygen carrier for the silicon and carbon. As soon as iron oxide is dissolved throughout the bath, the oxidation of silicon commences; but in the early stages of the blow the mass law would indicate that iron oxide must form first, and this oxide probably increases up to some saturation point. The molten metal in the converter from the early stages of the blow right through to its completion remains basic, while the slag produced is siliceous. This fact is shown by the corrosion of the acid bottom and the tuyeres, which is greatest at the tuyere orifice where oxidation is most active and where there is the most iron oxide. Why does this acid bottom corrode? Because it is attacked by a base. The thought, therefore, suggests itself, why not make the bottoms of basic or neutral material?1 As the converter slag is acid, those parts of the converter coming in contact with the slag should be acid; but those parts of the converter that are in contact with the molten metal saturated with metallic oxides should be basic or neutral. Bessemer operators have for some time tacitly admitted this condition, for the blast pressures have steadily increased with the object of keeping the metal in suspension, and so preventing bottom corrosion; if the molten metal were not basic, it would not attack an acid bottom. In addition, the tuyeres are bunched together at the middle of the bottom and a clear space is left around the outside of the bottom; if tuyeres are placed too near the side walls the

Jan 8, 1920

Jan 1, 1957

By R. Gatewood

The solution here offered is at once simple and important in its direct and indirect bearings. According to the principles of surface-tension, which will be found sufficiently enlarged upon for present purposes in Clerk Maxwell's excellent little treatise on The Theory of Heat, a mechanical mixture of liquids will frequently of itself divide into groups, consisting of liquids mixing among themselves but withdrawing from the other liquids. The following simple and familiar illustration will suffice: " If we mix water with alcohol, the liquids diffuse into each other. If we now attempt to mix oil with the alcohol and water, the two liquids separate from each other of themselves, and in the act of separation sufficient force is brought into play to set in motion considerable masses of the fluids." Maxwell goes on to show that this relative energy is one of arrangement, depending on the nature of the fluids and the area of the surface of contact, the act of separation tending to reduce this surface to a minimum consistent with equilibrium; that this surface-tension exists between a solid and touching fluid, either liquid or gaseous, being of one sign or the other, in the case of a liquid, according as it tends to draw itself up into a drop on its surface or to spread and wet the solid. After considering various cases, lie states that which particularly interests us, thus : " When a solid body is in contact with two fluids, then, if the

Jan 1, 1885

By A. S. Richardson

The design of mine airways receives, in general, very little engineering treatment. To a large extent this is, of course, due to the fact that information upon which to base calculations is seldom available in definite form. In many rnines the extent of the workable deposits may not be known at the time an air course is planned, and the length of service is indeterminable. Volume of air required for ventilation rnay also increase with extension of the life of a property, and natural obstacles, such as heavy ground, often place limitations upon the size of opening that can be maintained. Perhaps most of the shafts used in the ventilation of metal mines were originally intended as hoisting shafts, and many of the tunnels and crosscuts similarly used, were also designed as haulage ways or for other operating purposes. Even when a shaft is sunk solely for ventilation, custom usually dictates a size and shape consistent with the type commonly used for ordinary operations, because experience has demonstrated it can be excavated and maintained. In fact, most ventilation openings were never made with any consideration as to economic design for such use. When an air course is required to pass air between different parts of mine workings under a fixed pressure, the size of opening required for a given volume of flow, is, of course, determined by the resistance factor of the air course. It is then impossible to proportion the opening with reference to economics of power consumption, and this paper is limited to the design of openings where ventilation pressure or power consumption may he varied for economic advantage. As the size of an air course is increased, the expense involved in excavation and support is, of course, also increased, but the charge for power is decreased. In the case of a mine that has only a short assured operating life, it would not be ecouomical to provide large openings in order to reduce power bills; but when operations are likely to continue for a long time, the power charge becomes a very important economic factor. Although lack of definite information on such factors as service life and costs of excavation and support affects the design of an air course, it appears, from a mathematical analysis of the problem, that considerable variations may be made in estimating these factors, without greatly

Jan 1, 1927

By W. J. McGee

Most nations and states have conducted geological surveys, generally with the view of discovering and developing natural resources, sometimes with the aim of promoting science. In some cases, as in the first survey of Pennsylvania, the official geologist so far preceded the prospector and miner as to guide the discovery and exploitation of the commoner ores, mineral fuels and structural materials; but in most instances statesmen have only been awakened to the need of such a survey by the successful extraction of minerals;

Jan 1, 1893

By C. G. McLachlan

ONE phase of the treatment in sulphide flotation, covered generally in a review of pulp pretreat-ment by S. A. Falconer,' is the matter of grinding mills as conditioners, a subject on which further study could be advantageous. Flotation with few exceptions is preceded by grinding, and the grinding and flotation capacity required for the treatment of an ore is based generally on laboratory or pilot mill tests. The results of such tests, it then is assumed, will be duplicated in practice, and a flowsheet is prepared on that basis. This assumption may be too broad, because in several instances laboratory flotation tests made on massive sulphide copper ores could not be duplicated in plant operation without the introduction of an aeration step, either in closed circuit with the grind-inging mills, or between grinding and flotation.~' " The differences between laboratory and plant grinding practice are considerable, and may be summarized as follows: 1—In the laboratory a relatively fine charge is ground in a batch mill. In the plant, the feed, usually considerably coarser than the ore tested in the laboratory, enters the grinding mill continuously and more often than not, oversize material in the mill discharge is retained in the grinding circuit by a classifier until the required degree of reduction has been effected. 2—The rate of grinding in the laboratory is slower than in plant practice. 3—The percentage of volume occupied by the pulp in a laboratory mill rarely approaches that of a continuous overflow type mill. This does not apply if the comparison is made with grate type mills, but in that case an even wider discrepancy between the relative rates of laboratory and mill grinding almost invariably exists. The present trend in grinding is toward larger mills to reduce the number of operating units. This accentuates the foregoing differences. It is believed that the trend toward larger mills is sound, but that when large mills are used, metallurgists should check their flotation circuits carefully to determine whether laboratory tests are being reproduced in

Jan 1, 1952