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By Stanley C. Herold

A few hates on the occurrence and significance of mud volcanoes in Colombia may be of interest at the present time, owing to the renewed activity in geological exploration of the coastal regions bordering the Caribbean Sea. The best-known volcanoes are found a few miles from the seacoast. One is situated to the south of Puerto Colombia; the second, to the east of Cartagena near the village of Turbaco; and the third, near the village of Puerto Escondido south of the Sinu River. Others are reported in more inaccessible localities. Usually they stand 2 1/2 or 3 ft. (0.762 or 0.914 m.) above the surrounding ground at the crater, though several craters from 10 to 20 ft. -(3.04 to 6.09 m.) "apart will often build up an extensive mound at low gradient. The shallow mound may cover 1/2 or 3/4 acre (0.2 to 0.3 ha.) with an elevation of 12 or 15 ft. (3.65 or 4.57 m.) at the, center. The craters are formed of hardened blue clay; the inside diameters vary from 14 to 24 in. (35.56 to 60.96 cm.). The rim is continuous, except on one side where there is usually a cut 3 or 4 in. deep, thus allowing an overflow. The craters are filled to the' rim-cut with a thick mixture of blue clay mud and water, which is kept in agitation by escaping gas. Fig. 1 shows the bubble in the act of bursting and Fig. 2 the appearance of the surface of the viscous fluid a second or so later. The frequency of the explosions is determined by the weight of the column of fluid in the neck of the volcano, consequently, such explosions are not synchronous in a group of craters. Ordinarily, there arc two or three explosions in about 3 minutes. The supply of gas is small but steady and sufficient pressure must accumulate before the bubble can enter the column of fluid. The water is derived from the surface and enters the scdirnentary strata not far distant from the volcano. During long dry seasons, as the supply of water fails the volcano dries and geyser action ceases. The temperature of the muddy fluid is normal; the gas is dry and inflammable. - No petroleum products come with the gas. On the surface of the fluid, there is sometimes a dark brown streaky scum, which

Jan 1, 1920

By Waldemar Lindgren

During the last 15 years much attention has been given to the " contact-metamorphic" ore deposits which mainly occur in limestone close to intrusive contacts. In general, these deposits are characterized by the association of magnetite and simple sulphides with the so-called L'contact-metamorphic" silicates. These silicates comprise garnet, epidote, vesuvianite, tremolite, wollastonite, diopside, hedenbergite, ilvaite, and many other rarer forms. The contact-metamorphic zones contain also in places minerals with boron, fluorine, and chlorine, like axinite, tourmaline, danburite, fluorite, and scapolite. There is also more or less quartz and coarsely recrystallized calcite. The simple sulphides embrace pyrite, pyrrhotite, chalcopyrite, galena, zincblende, more rarely arsenopyrite. On the whole, sulphantimonides and sulph-arsenides are rare. Deposits of magnetite or chalcopyrite or of both are most common. The deposits have an irregular or rudely tabular form, following main contacts, dike contacts, or stratification planes; they rarely extend for more than 1,500 or 2,000 ft. from the contact; far more commonly they only reach a distance of a few hundred feet from that surface. The deposits are usually formed by replacement of limestone, or allied calcareous rock. Apparently they are found both in relatively pure and in impure carbonate rock. The deposits are geoiogical bodies of a chemical and mineralogical character differing greatly from the adjoining intrusive rock and from the unaltered limestone. They are rich in silica and iron, with more or less of lime, magnesia, alumina, sulphur, and rarer metals like copper. The so-called contact-metamorphic silicates which form the gangue usually are coextensive with the metallic minerals, though of course not necessarily with the merchantable ore. All opinions agree in holding the deposits of epigenetic origin, later than the inclosing limestone. Regarding the origin of the metals and the genesis of the ores there are several opinions. 1. There are those who see in these deposits the result of concentration of material contained in the intrusive rocks by means of hot circulating

Jan 1, 1915

By E. V. Foran

AMONG the many newer disclosures that have accompanied the petroleum industry's progressively deeper exploratory drilling is the increased frequency with which the operators are encountering reservoirs of which the products at the time of discovery exist wholly or predomi-nantly in the gas phase. The popular term "distillate pool" is most often used within the industry when referring to this type of reservoir, and in this paper the term is used in that sense. These pools have been observed in many different surroundings. In some places the entire reservoir is filled with the wet gas containing its water-white condensible products in the gas phase but apparently with no dark oil or other hydrocarbon liquids in the reservoir. The 8200-ft. horizon in the Big Lake field in West Texas is a good example of this type. At other places the wet, or distillate-bearing, gas may form a large gas cap directly overlying and in contact with an extensive reserve of dark oil. Oklahoma City, Kettleman Hills, the 8500-ft. horizon in the Big Lake field, and many others are examples of this type. There are also many places in which the wet distillate-bearing gas fills nearly the entire reservoir space, while the dark oil occupies only a narrow, bandlike zone, which marks the boundary of the reservoir along its lowest productive contour. The heavier components of these deep pool gases are generally water white in color, a large portion of which are condensible in a conventional oil and gas separator, when operated under pressures of the order of 400 to 800 lb. per sq. in. Although the water-white products recovered in the separator sometimes have end points of 650° F. and higher on standard Engler distillation, they occur only in the gas phase in the reservoir. It is entirely possible that even some small amounts of dark colored reservoir components may occur in the gas phase when the temperature is 300° F. and pressures exceed 6000 lb. per sq. in. Close approaches to these conditions have been encountered in the deepest producing wells. The condensible content of the deep reservoir gases of the many pools that have been tested or produced to date shows a wide variation in both condensible content, per 1000 cu. ft. of gas, and physical character.

Jan 1, 1939

By Willard Ide Pierce

THE native methods of mining and milling gold-ores in Korea may not present any specially new features, but are chiefly interesting as primitive practices, still followed at the present day. In mining where the rock is hard, wood is piled up near the face of the tunnel or drift and then set on fire. The fire bums for twenty-four hours, after which, three or four days are given for the rocks to cool, before the miners go in and extract the loosened material. The only tools in use are a hammer, a steel gad about five inches long, and a flat spoon-shaped basket. The pay-streak or chute is closely followed, and in places the workings are very small and intricate. Rock not yielding more than $6 per ton is not extracted. The manner of opening a mine is to begin on the outcrop, where the rock pays, sink a shaft or run a tunnel on the vein, and follow the pay-streak and more easily worked ore. When this is exhausted, or the influx of water interferes, the opening is abandoned and operations are begun again at a new spot on the outcrop. The place usually selected is as high up on the mountain as possible, and in no instance is advantage taken of the topography by running a cross-tunnel to tap the vein. The ore is brought in baskets to the surface, and there placed in sacks, holding about 150 1bs. each, and taken to be crushed. The rock is first crushed between two stones, as shown in Fig. 1. The upper stone is oval and rounded on the bottom, so that it can be readily rocked on the under stone. Two pieces of wood, used for handles, are placed, one on each side, in grooves in the upper stone, and held in position by means of straw rope. The lower stone is not smooth on top, but exhibits three elevations running lengthwise, with shallow depressions between them. The middle elevation acts as a fulcrum on which the upper stone may be rocked. From two to ten men, according to the weight and size of the stone used, are employed in rocking. With four men, from 300 to 350 lbs. of rock can be crushed per day, the stone making 50 complete oscillations per minute. The men squat on each side of the stone and move it to and fro by means of the wooden handles. The ore is fed, in pieces up to the size of an egg or even larger, by one of the men. During the crushing one man on each side, as the stone rocks from

Jan 1, 1890

By R. R. Knuckey

HAVING been associated with the operation of the de Vooys process for coal, which has treated 13,000,000 tons per annum, and recognizing the process as of value in ore sorting, Huntington, Heberlein and Co. Ltd. (Great Britain) in 1936 made an examination of all other existing methods. In none of the pioneer applications had recognition been given to the necessity for maintaining certain conditions that are essential for sorting certain ores if a truly efficient separation by gravity alone is to be assured. Consequently, in 1936-1937 Huntington, Heberlein and Co. Ltd., with Pearson, employing certain ideas connected with the de Vooys application, commenced the development of a separator that would allow conformance with optimum conditions in the zone where separation is effected. Later, Holt and Wade added to the value of the original application by Wuensch, Rakowsky and others, whose conceptions are being successfully operated today. Meantime, Trostler had enhanced the value of the original H-H. process by improvements that are now embodied in operating plants, and today the process incorporates an improved apparatus and a stable medium that produce the optimum conditions for separation. These conditions are: 1. Elimination of disturbing currents in the separating zone; 2. Reduction to a minimum of medium-density differences throughout. the separating zone; 3. Stable medium of minimum viscosity to permit the unretarded fall of mineralized particles; 4. Removal of products of separation with minimum disturbance to the separating zone. DESIGN OF SEPARATOR The H-H. sink-and-float separator consists of a pyramidal tank in which the separation actually takes place, connected at the bottom with an inclined bucket elevator. The tank and the elevator are filled with medium to within a few inches of the top of the tank. Medium is fed into the separator at a variety of points, according to the type of ore being treated, and it is withdrawn from the separator at two points: (1) together with the float product, by means of a variable-speed paddle, at the surface of the medium, and (2) by flowing over an adjustable weir cut in the side of the elevator casing. The prepared ore is fed onto the surface of the medium. The intermediate paddles, which revolve at a slow speed of 2 to 5 r.p.m., move the floating ore across the bath from feed end to float-discharge end. The ore, which is heavier than the medium, sinks below the sweep of the paddles and reaches the boot of the bucket elevator, which discharges it without disturbance of the separating zone. These arrangements for withdrawing medium from the separator allow the use of minimum flows, which connote minimum

Jan 1, 1943

By R. W. Raymond

ChaRles William HenRy Kirchhoff was born March 28, 1853, at San Francisco, Cal., where his father, Charles Kirchhoff, was at that time consul for his native country, Germany. A few years later, the family moved' to Hoboken, K. J., in which city the son received his preliminary education at the Hoboken Academy, proceeding later to Germany, where he was graduated in 1874 as mining engineer and metallurgist at the Prussian Royal Mining Academy of Clausthal, in the Harz. Upon his return to the United States, he became chemist of the Delaware Lead Refinery at Philadelphia, and retained that position for three years. But in 1877 he began what was to be an almost uninterrupted life-long association with David Williams, the publisher of The Iron Age, of New York, who established in that year, and continued for a brief period, a journal entitled the Metallurgical Review, on the editorial staff of which Mr. Kirchhoff received a place. The enterprise was doubtless an attempt to cover a wide metallurgical field outside of that which properly belonged to The Iron Age. But it was soon abandoned, and Mr. Williams wisely concentrated his energies upon the older journal, which, under his vigorous and skillful management, and the labors of the able editors and correspondents whom he selected, became one of the greatest institutions of its class in the world. From 1878 to 1881, Mr. Kirchhoff was assistant editor of The Iron Age. From 1881 to 1884, he was managing editor of the Engineering and Mining Journal; in 1884 he returned to The Iron Age, to become for five years its associate editor, and in 1889, on the retirement of James C. Bayles, editor-in-chief. This list of dates and employments, without further comment, sufficiently indicates, at least to the eye of an expert, that Mr. Kirchhoff had found his congenial career in trade journalism. His qualifications for this profession were somewhat exceptional. He possessed the scientific training, the knowledge of foreign languages and literatures, and the power of making and keeping friends, which enabled him to get early notice of technical novelties; he had the taste for statistics which made him both industrious and intelligent in their collection and use; and to these traits he added a mastery of the meaning of such accumulated data, and a sane, critical judgment of the situations which they represented, as well as of the sources and the figures themselves, which made his opinion weighty

Jan 1, 1917

By Maurice Rey, H. Beavers

THROUGH circumstances connected with the war, the senior author lost his records, therefore it has been impossible to include numerical data in this paper. The arsenical quicksilver ore investigated had been roasted, with poor metallurgical results. The vapor-tension temperature curves of mercury and arsenious trioxide are similar, and the arsenical compound hampers the coalescence of mercury drops in the condenser and is the cause of large stack losses. The ore was a gray limestone carrying small amounts of carbon and mineralized with cinnabar and two arsenic minerals, realgar (As2S2) and arsenopyrite (FeAsS). The proportion of realgar often exceeded that of cinnabar; the proportion of arsenopyrite was smaller. The grade of the ore varied between 0.8 and 4 per cent Hg. The problem was to make a high-grade mercury concentrate, as free from arsenic as possible. The water used throughout the testing was hard, having a pH of about 8. FLOTATION OF REALGAR Realgar showed a very strong tendency to float. It formed a film at the surface of the pulp and floated in abundance with only pine oil. Therefore an attempt was made to float the realgar before the cinnabar, but this was not very successful; the percentage of mercury in the realgar concentrate could never be brought below 2 or 3 per cent. Cinnabar slimed easily and floated with pine oil, so that some of it always accompanied the realgar. There was also the question of the cinnabar-arsenopyrite separation. On further investigation it was found that realgar can be floated not only with pine oil but even better with a combination of hydrocarbons and pine oil. Washing the ore with ether revealed that it contained hydrocarbons, which helped to float the realgar. In this connection it belongs to the same class as carbon, sulphur and talc. It can be floated also with a xanthate, when activated by a heavy-metal salt. The conditions favoring the two types of flotation are opposed, as activation by a copper salt facilitates xanthate flotation (in fact, is even necessary to it), whereas it hinders pine oil and petroleum flotation. One type of flotation can be termed nonpolar and the other polar, a distinction that has been stressed in a previous paper.1 DEPRESSION OF REALGAR AND FLOTATION OF CINNABAR 'Many chemicals were tested in an attempt to float the cinnabar and depress the realgar. Finally starch rendered soluble with caustic soda was tried, also several grades of commercial soluble starch, and dextrin was found to be the best and the most convenient reagent. Several of these starch preparations have a strong flocculating effect on the pulp, which is a distinct disadvantage. Dextrin, with its low flocculating power, is excellent. It is noteworthy that starch preparations are also depressants for carbon and talc, so that the fact apparently has a general

Jan 1, 1941

By E. A. Nichols

The purpose of this paper is to present a contour map that shows the geographical variation in geothermal gradients in the Mid-Continent and Gulf Coast oil fields. Introduction Frequently there arises the need for an estimation of the temperature to be expected at a predetermined depth in working with a wildcat or in deepening old production into 'Ones that are relatively unknown. The study of geothermal gradients in oil fields has been made previously by many investigators. One of the pioneers in this work was C. E. Van Orstrand,' who, as well as most of the other investigators, was primarily interested in the relation between temperature and depth in a given locality. Between 192r and 1929, American Petroleum Institute Research Project NO. 25 fostered a thorough study of earth temperatures.2 K. IV. French did some work in California, the results of which were published in 1939.3 In most of these studies, an attempt was made to correlate temperatures in a rather localized area. This paper will show the results of an attempt to correlate temperature gradients over rather large Portions of the Mid-Continent and Gulf Coast area. Method of Obtaining Data It has been found that for complete thermal equilibrium to be established in a well, the well must stand undisturbed for a period of several hours to several weeks, depending upon the way the well was produced prior to the shut-in period. The data in this paper were obtained in conjunction with running pressures in wells or in taking samples of reservoir fluid. Glass maximum recording thermometers were used in all but a few instances. The wells had been shut in from one hour up to I. or 12 days. Since the wells were normal producing wells, some of the shut-in times undoubtedly were insufficient for complete thermal equilibrium to have been established and the temperatures measured do not necessarily represent the true earth temperatures. They do represent the temperature conditions that will be encountered in a well that is producing oil. The data, therefore, can be useful in working with or in estimating the temperatures to be expected in producing reservoirs. In obtaining a thermal gradient by dividing the difference in temperature of the formation and the mean annual surface temperature by the depth of the formation, one is assuming the depth-temperature line to be straight. Depth-temperature curves are almost straight lines (Fig. I). However, on close examination of accurate data, a slight curvature usually is observed. Most wells yield curves with slopes increasing with increasing depth. These curves are believed to be from wells that are in and are underlain by sedimentary material. Some few curves have slopes that decrease with increasing depth. These curves are believed to be from wells that are underlain rather closely by granite or some other igneous rock. Most investigators

Jan 1, 1947

By E. A. Nichols

The purpose of this paper is to present a contour map that shows the geographical variation in geothermal gradients in the Mid-Continent and Gulf Coast oil fields. Introduction Frequently there arises the need for an estimation of the temperature to be expected at a predetermined depth in working with a wildcat or in deepening old production into 'Ones that are relatively unknown. The study of geothermal gradients in oil fields has been made previously by many investigators. One of the pioneers in this work was C. E. Van Orstrand,' who, as well as most of the other investigators, was primarily interested in the relation between temperature and depth in a given locality. Between 192r and 1929, American Petroleum Institute Research Project NO. 25 fostered a thorough study of earth temperatures.2 K. IV. French did some work in California, the results of which were published in 1939.3 In most of these studies, an attempt was made to correlate temperatures in a rather localized area. This paper will show the results of an attempt to correlate temperature gradients over rather large Portions of the Mid-Continent and Gulf Coast area. Method of Obtaining Data It has been found that for complete thermal equilibrium to be established in a well, the well must stand undisturbed for a period of several hours to several weeks, depending upon the way the well was produced prior to the shut-in period. The data in this paper were obtained in conjunction with running pressures in wells or in taking samples of reservoir fluid. Glass maximum recording thermometers were used in all but a few instances. The wells had been shut in from one hour up to I. or 12 days. Since the wells were normal producing wells, some of the shut-in times undoubtedly were insufficient for complete thermal equilibrium to have been established and the temperatures measured do not necessarily represent the true earth temperatures. They do represent the temperature conditions that will be encountered in a well that is producing oil. The data, therefore, can be useful in working with or in estimating the temperatures to be expected in producing reservoirs. In obtaining a thermal gradient by dividing the difference in temperature of the formation and the mean annual surface temperature by the depth of the formation, one is assuming the depth-temperature line to be straight. Depth-temperature curves are almost straight lines (Fig. I). However, on close examination of accurate data, a slight curvature usually is observed. Most wells yield curves with slopes increasing with increasing depth. These curves are believed to be from wells that are in and are underlain by sedimentary material. Some few curves have slopes that decrease with increasing depth. These curves are believed to be from wells that are underlain rather closely by granite or some other igneous rock. Most investigators

Jan 1, 1947

By M. L. Lissberger

entirely suitable for certain uses and even possess advantages over present solders at high temperatures, but they are certainly not suitable for all uses. However, it is conceivable that their use in many places will effect a material conservation of tin. It will probably be wiser to use cadmium in solders where good results have been obtained than in brass where this element will be a source of possible trouble. F. F. Colcord,* New York, N. Y.-—The cadmium-lead solder has a higher conductivity than the lead-tin alloy, which ought to make it advantageous in the manufacture of electrical machinery. In the case of solder for tin-can work, one of the high officials of the American Can Co. said that he fully intended to .give it a good trial, and I do not believe they are going to reach hasty conclusions and run the risk of poisoning the public. Solder, Its Use and Abuse Milton L. LissbeRgeR,† New York, N. Y.—Solder is a mechanical mixture of tin and lead, a fact which is susceptible of very simple demonstration. A bar of solder of a grade even as low as 30 per cent. tin and 70 per cent. lead, passed through a buffing machine, will show a surface practically identical with that of a bar of second-quality or reclaimed tin. The buffings, on chemical analysis, will prove to be almost pure lead. According to the best practice, solder is made in the following manner. Virgin pig lead is first melted, and when it is thoroughly liquefied, virgin pig tin is added, together with a small amount of flux; the latter is for the purpose of bringing to the surface the so-called "liver," consisting of impurities that may have remained in either the lead or the tin as a result of incomplete refining. The combined material, when completely liquid, is thoroughly stirred for some hours, and is then cast into small pigs. Just before casting, and continuously during this operation, the molten metal yields dross, consisting largely of the oxides of lead and tin; this should be carefully skimmed off. After the pigs have cooled, they are taken to a smaller kettle, re-melted, and cast into the desired shape for use; or if wires, ribbons, etc., are to be made, the solder is cast into slugs suitable for extrusion and rolling. During this second operation, the skimming of dross should be even more carefully done than at first. Hand mixing has proved to be the only reliable method for the production of the best quality of solder, irrespective of its percentages of lead and tin. The best quality of solder is not necessarily that which contains the highest percentage of tin, but rather is that composition which performs best on the required piece of work. In order to produce

Jan 1, 1919

By L. P. Davidson

THE new electrolytic zinc plant of the American Zinc Company of Illinois commenced operation in April 1941. The simple flowsheet using the standard current density and the economic reasons that dictated it are given herewith. The Evans-Wallower Zinc Co. built an electrolytic zinc plant at Monsanto, Ill., in 1929 and operated it for about two years. The plant stood idle from 1932 and was purchased by the American Zinc Co. in 1940. Because of the condition of the equipment, excepting the motor generator set, a complete rebuilding was necessary. The Fairmont City plant of the American Zinc Co. could treat the leach residues, the purification cake and the skimmings from the melting furnace in its various plants. This possibility permitted a simple flowsheet with good economic results. The flowsheet is shown in Fig. I. The calcined concentrates are leached in mechanically agitated tanks with spent electrolyte and such ferric iron solution as necessary. When the acid has been neutralized and the iron coagulated, the fluid is discharged to settling tanks. The underflow from these thickeners is filtered on a Moore filter; the filter cake leaves the plant for retreatment and the filtrate joins the thickener overflow. Zinc dust is added to this solution until the copper and cadmium are precipitated. The pulp is filtered through Shriver presses, which deliver the purified solution to storage tanks, and the copper-cadmium-zinc cake is shipped for retreatment and recovery of these three metals. The purified solution is electrolyzed; the regenerated acid is returned for use in the leaching plant and the cathode zinc, after stripping, goes to the melting furnace, from which it is cast in slabs. The skimmings from the melting furnace are shipped to the Fairmont City plant for reduction to metal in the retort furnaces. The choice of this simple flowsheet was made possible only because of the facilities of the Fairmont City plant. The long leaching period, with high acid content and high temperature which characterize the high-density process, gives a higher zinc extraction but also dissolves more impurities, which must be removed. The same is true to a lesser degree of the multi-step leaching of the western low-density plants. By the sacrifice of some initial extraction, solutions can be obtained that are relatively easy to purify and give good ampere efficiency. This loss in initial extraction is made up in the retreatment of the residues in the Waelz plant. The impurities that accompany the zinc thus extracted are inconsequential when the Waelz product is treated in a distillation plant. It was recognized that this flowsheet would require a somewhat greater amount of sulphuric acid-either as acid or as sulphate sulphur in the calcine-because of poorer washing. The sulphuric acid plant at Fairmont City could deliver 60° Bé. acid to compensate for the sulphate loss and the cost would be less than the cost of more intensive washing.

Jan 1, 1942

By H. L. Talbot, A. J. Hall, R. S. Young

A METHOD for the chemical differentiation of oxidized cobalt from sulphide cobalt in complex mine and concentrator products is of considerable interest to a number of mining companies throughout the world. At Rhokana Corporation, in Northern Rhodesia, for instance, cobalt is found chiefly in the sulphide form, as carrollite, but a cobalt oxide mineral also occurs irregularly underground, and relatively small quantities in the mill feed from time to time are difficult to detect it visually at the concentrator. The oxide cobalt is not amenable to the sulphide flotation process used at Rhokana and nearly all of it passes into the tailing. The occasional. period when high tailing losses occur with no appreciable change in the cobalt content of the mill feed has naturally been disturbing to the concentrator staff, who had no means of determining whether an influx of cobalt oxide ore or laxity on the part of the mill flotation operators were responsible for these results. A procedure for determining oxidized copper minerals, based on their solubility in dilute sulphuric acid saturated with SO2, has been used for many years in the copper industry. In the presence of cuprite the procedure fails, but otherwise it gives results quite satisfactory for control purposes. Empirical methods for determining oxidized forms of zinc and lead have been proposed, but they are generally unsatisfactory except in isolated cases of a very simple ore. No published procedure for determining oxidized forms of cobalt or similar elements has come to the authors' notice. EXPERIMENTAL PROCEDURE There are obviously two alternatives in attacking a problem of this nature. One is to employ a solvent for oxide cobalt that will not dissolve cobalt sulphide. The other is, to find a substance capable of oxidizing the cobalt sulphide to sulphate, which of course is water-soluble and can then be leached from the water-insoluble oxide cobalt. A representative sample of Rhokana cobalt oxide ore was secured, ground to minus 200-mesh, and carefully rolled to furnish a standard sample for this work. The analysis of this material gave the following percentages: Co, 0.55; Cu, 1.64; Fe, 2.98; S, 0.08; SiO2, 41.42; A1203, 11.20; CaO, 13.82; MgO, 3.80. As a source of cobalt sulphide a similar large sample of carrollite was prepared, analyzing Co, 23.36 per cent; Cu, 27.32; and S, 31.13. This sample of course was not pure carrollite, but was the best obtainable in quantities sufficient for a standard intended for considerable work. It was a pure sulphide sample, microscopic examination showing only carrollite, a little bornite, and gangue, with no visible sign of oxidized ore present. A wide variety of reagents were used in an effort to selectively dissolve oxide cobalt or to oxidize sulphide cobalt to

Jan 1, 1946

By G. H. Matheson, J. M. W. Mackenzie

The coal concentrates studied contained clay slimes which would not flocculate on the addition of a polymer flocculent alone. The mechanism of the flocculation process is interpreted on the basis of the flocculation of lyophobic colloids. The filtration rate characteristics are shown to deviate slightly from certain basic filtration equations. Cake moisture was shown to decrease with cake drying time and vacuum, and increase with cake thickness. Filtration is a commonly accepted method of dewa-tering the fine coal concentrates produced in coal cleaning operations. Dewatering of these concentrates, using drum or disc vacuum filters, usually presents few technical difficulties and will result in the production of a filter cake containing some 20 to 25 pct moisture. In many coal cleaning operations it is common practice to add flocculants to the coal concentrates prior to filtration to increase the filtration rate. The mechanism whereby flocculation increases filtration rate has been summarized by Gaudin,4 while Geer, et a15 have compared the effectiveness of starch and synthetic flocculants as filter aids for a variety of coal concentrates. Coal concentrates, containing appreciable quantities of expanding lattice clays of the montmorillonite-illite group, sometimes prove impossible to filter without flocculation of the pulp prior to filtration. The fine coal concentrates produced at the Newcastle washery of The Broken Hill Proprietary Co. Ltd. fall into this group. Coals mined in this district contain appreciable quantities of expanding lattice clays which break down in the washery circuit waters and, by processes of mechanical inclusion, contaminate the coal concentrate thickener feed. Despite the classifying action of this thickener, the underflow which is pumped to the filters contains sufficient clay slimes to render filtration of the unflocculated pulp impossible. Filtration leaf and plant tests were carried out to develop effective and economic flocculant combinations and to determine the filtration characteristics of the flocculated coal concentrates. The determination, by leaf testing, of the filtration characteristics, and the analysis of these characteristics in the light of the equations of Brown2 resulted in the successful trial operation of the filters in the Newcastle washq. Although the filtration characteristics are not entirely in agreement with the theoretical treatment of Brown, the equations developed made it possible to predict, from leaf tests, the effect in the plant filters of pulp density, form vacuum, and form time on filtration rate and filtrate volume. EXPERIMENTAL PROCEDURES The sample used for leaf testing was the coal concentrate thickener underflow, which in plant operations would form the feed to the two 12-disk Dorr-Oliver filters. The feed to the coal concentrate thickener comprises the undersize produced by dewatering the Diester table concentrate on 5-mm dewatering screens and the overflow produced by cycloning of the froth flotation concentrate. At the time of testing these filters were inoperative because of the difficulties in filtration, arising from contamination of the

Jan 1, 1962

By E. D. Hummer, J. A. Younkins. J. P. Proctor

Comparatively little has been published relating practical experience with the control of the solid content of washery water systems that must be "closed." A "closed" system is one that for some reason may not be cleaned by the emission Of any effluent Of high ''lid 'content to be rep1aced by 'lean water in Order to hold the solid content of the waste water within reasonable bounds for efficient washing. It is the Purpose of this Paper to describe practical experience with such a water system and to present data that it is hoped may be of some use to those who are faced with a similar problem. The washery clarification system described comprises three thickeners and three filters, and although it is admitted that each of the fields of water settling and thickening and filtration offers a wide scope for investigation, the authors are not attempting to present the answers to these problems but to set down the results of some experience along these lines, making no claims as to the ultimate solution of the problems in hand. The subject of water clarification has vast ramifications; for example, the science of flocculation as applied to water settlillg and filtering opens up fields of wide possibilities of which as yet little is known. A comparatively recent entry into the field of water treatment, which may offer possibilities of practical application, is the use of "wetting" agents such as "Aerosol." General Arrangement of Water System So that the reader may obtain a comprehensive picture of the factors concerned in the control of a closed water system, it is necessary to give a brief description of the washing plant that is serviced by the water system to be described in the following pages. As we are not primarily concerned with the washing plant in detail, only a brief description of the flow of coal as it relates to the water system will be given here. For a more detailed account of this type of washer, the reader is referred to earlier papers,1,2 The washer, which handles o to 4-in, raw coal (750 tons per hour) is an American Rheolaveur plant of two complements; the coarse coal or sealed discharge plant and the fine coal or free discharge plant. The sealed discharge plant (Fig. I) consists of twin 48.in. primary launders, each having two washing boxes, supplemented by one 32-in. rewash launder, which also has two washing boxes. "Push" water for washing and conveying coal in these launders is supplied from a constant-head tank under pressure head of 10½ ft. at the point of introduction at the feed end of the launder. This tank also supplies water for upward or vertical currents used in the Rheolaveur or washing boxes. Each box discharges into a sealed boot elevator (Fig. I).

Jan 1, 1942

By J. A. Younkins. J. P. Proctor, E. D. Hummer

Comparatively little has been published relating practical experience with the control of the solid content of washery water systems that must be "closed." A "closed" system is one that for some reason may not be cleaned by the emission Of any effluent Of high ''lid 'content to be rep1aced by 'lean water in Order to hold the solid content of the waste water within reasonable bounds for efficient washing. It is the Purpose of this Paper to describe practical experience with such a water system and to present data that it is hoped may be of some use to those who are faced with a similar problem. The washery clarification system described comprises three thickeners and three filters, and although it is admitted that each of the fields of water settling and thickening and filtration offers a wide scope for investigation, the authors are not attempting to present the answers to these problems but to set down the results of some experience along these lines, making no claims as to the ultimate solution of the problems in hand. The subject of water clarification has vast ramifications; for example, the science of flocculation as applied to water settlillg and filtering opens up fields of wide possibilities of which as yet little is known. A comparatively recent entry into the field of water treatment, which may offer possibilities of practical application, is the use of "wetting" agents such as "Aerosol." General Arrangement of Water System So that the reader may obtain a comprehensive picture of the factors concerned in the control of a closed water system, it is necessary to give a brief description of the washing plant that is serviced by the water system to be described in the following pages. As we are not primarily concerned with the washing plant in detail, only a brief description of the flow of coal as it relates to the water system will be given here. For a more detailed account of this type of washer, the reader is referred to earlier papers,1,2 The washer, which handles o to 4-in, raw coal (750 tons per hour) is an American Rheolaveur plant of two complements; the coarse coal or sealed discharge plant and the fine coal or free discharge plant. The sealed discharge plant (Fig. I) consists of twin 48.in. primary launders, each having two washing boxes, supplemented by one 32-in. rewash launder, which also has two washing boxes. "Push" water for washing and conveying coal in these launders is supplied from a constant-head tank under pressure head of 10½ ft. at the point of introduction at the feed end of the launder. This tank also supplies water for upward or vertical currents used in the Rheolaveur or washing boxes. Each box discharges into a sealed boot elevator (Fig. I).

Jan 1, 1942

By J. J. Jakosky

The strategic importance of the metallic minerals in our industrial economy, and the declining rates of discovery have focused attention on means of exploration for new mineral deposits. A consideration of exploration techniques leads to an attempt to evaluate the effectiveness of geophysics as a tool for mining exploration. One means of evaluation will be to compare the use of geophysics in petroleum exploration with its possible uses in mining. Geophysics in Petroleum Exploration During the past twenty years, the petroleum industry has established an effective exploration technique. Geology is the basic tool in those areas where reliable predictions can be made from surface conditions. In the other areas, where the geological studies are inadequate, they must be supplemented with geophysics or direct exploration, such as drilling. Since geophysical work is far less costly than any form of direct explbration, it is used almost exclusively as the means for obtaining the desired subsurface information. The geological and geophysical techniques are credited with locating sites which yielded one producer for three dry holes during the year 1947.' For the wells located without geology or geophysics, there is a ratio of one producing well to sixteen dry holes. From these figures it is seen that the geological and geophysical techniques are more than four times as successful as the nontechnical exploration. It will be in order to consider further this ratio of one producer to three dry holes. The geophysical methods in use today† do not pretend to locate oil directly; their function is to locate anomalies or structures favorable for the accumulation of oil. For a producing oil well we must have not only structure, but also other favorable conditions, namely: petroliferous source beds, the required porosity and permeability in the reservoir rocks, an impermeable cap rock over the reser- voir, and the necessary water or gravity drive to force the oil into the bore hole. Since the geophysical work can only detect and sometimes delimit the anomaly, these other necessary conditions can be determined only by direct exploration. The success of modern geophysical work in locating and limiting the structure itself is remarkably high, probably over 95 pct accurate. Geophysical work renders an important service in the delineation of the structurally unfavorable areas and their elimination from the drilling phase of the exploration program. When attempting to locate any material of scarce occurrence in the earth, it is of paramount importance to know where not to dig. This elimination of barren areas is the least appreciated but is of great economic importance. For illustration, the difference between one producer to three dry holes, and one producer to sixteen dry holes, represents a saving of thirteen drilled wells, which would require an expenditure many times the cost of the geophysical work that might have revealed the nonfavorable structural conditions. The percentage of geophysically-located wells necessarily will continue to increase in the statistics of future years, as the search for oil is extended

Jan 1, 1950

By R. G. Powell, R. Schuhmann, E. J. Michal

Liquidus surfaces in the ternary system FeO-Fe2O3-SiO2, were determined from 1250' to 1450°C by the procedure of equilibrating small samples in platinum crucibles, quenching, and microscopic examination. The experimental results were combined with previously published information to construct a ternary diagram for the system showing the entire temperature-composition range of stability of iron silicate slags. Metallurgical applications of the diagram, especially in copper smelting, are discussed briefly. IRON oxides are almost unique among the common oxide constituents of metallurgical slags in that the iron occurs in two different states of oxidation, ferrous and ferric. Moreover, in liquid slags the degree of oxidation of the iron is readily changed by reactions of the slags with oxidizing agents or reducing agents. This behavior of iron oxides in slags accounts, for example, for the effective transfer of large quantities of oxygen through slag layers in open hearth steelmaking. In this process, oxygen supplied by reactions at the gas-slag interface is dissolved in the slag with the oxidation of ferrous iron to ferric. Ferric oxide is transported across the slag layer by convection, and at the slag-metal interface the oxygen reacts with liquid metal while the ferric iron is reduced back to the ferrous state. Another group of processes in which variation in degree of oxidation of iron has great practical importance is in copper smelting. In matte smelting and converting, such large proportions of the iron are oxidized to the ferric state that problems are encountered in preventing or controlling the formation of solid magnetite. The ferrous-ferric relationship also affects the attack of iron oxides on high-SiO2 refractories, which appears to be most severe under reducing conditions for which ferrous iron predominates. Darken and Gurry' determined the chemical properties and phase equilibria of pure iron oxide slags. Their data show that iron oxide melts can have compositions ranging almost all the way from FeO to Fe2O3. The melts of lowest oxygen contents, which exist in equilibrium with metallic iron, approach ferrous oxide in composition but still have a small percentage of ferric oxide. The melts of highest oxygen contents, which have oxygen dissociation pressures of 1 atm, are above magnetite in oxygen content, with over two-thirds of the iron in the ferric state. The previously established phase diagrams for silicate slag systems all show FeO as the iron oxide component. However, Bowen and Schairer? who determined the FeO-SiO2 diagram and many of the other diagrams used by slag chemists, have been careful to point out that their systems always contained both ferrous and ferric iron. Thus, their data are for limiting mixtures with minimum contents of ferric iron, obtained by melting and equilibration in iron crucibles. Under these conditions, the Fe2O3 percentages found by analysis were small enough to justify simplification of the published phase diagrams by calculating the Fe2O3 to equivalent FeO and ignoring Fe2O3 as an additional component. On the basis of experimental measurements of melting points of iron oxides on silica in the presence of various gas mixtures, Darken3 worked out phase diagrams for the Fe-Si-0 system which show the important phase equilibria in terms of temperature and gas composition. This study clarified many aspects of the application of the phase rule to the FeO-Fe2Oa-SiO2 system and was an important basing

Jan 1, 1954

By Pedro Bolsaitis, Paul M. Sullivan

The activities of zinc in liquid Zn-A1 alloys in the temperature range of 1000' to 1160°K were determined by means of the isopiestic technique. The results are in reasonable agreement with the previous values determined by the radioactive tracer dew point method. Slightly negative excess entropies of mixing were found. The measured activities suggest that the a function for these alloys is not a constant, as has frequently been assumed, but is better represented by two straight line segments of different slopes. THE thermodynamic data of Al-Z alloys have been the subject of investigation by many authors. However, in the recent compilation of such data by Hult-gren et al.,5 the conclusion is reached that none of the previous measurements are reliable or consistent with each other. Since then two new sets of measurements have been reported,2, 8 both laying claim to good accuracies, yet showing very significant disagreement in the measured activity coefficients of zinc in Zn-A1 alloys and in the magnitude and sign of the excess entropies of mixing. Information on the thermodynamics of the system is of particular interest for interpreting results of the Bureau of Mines research on refining of zinc by distillation of die cast scrap. The present study was undertaken as an independent check on the recent values obtained from dew point measurements 8 and electromotive force measurements.' The isopiestic method, first introduced by Herasy-menko,' was chosen because it is one of the few thermodynamic techniques which, in principle at least, is carried out under perfect equilibrium conditions. The disadvantage of the method is that data are obtained at various random compositions and temperatures, which makes the interpretation somewhat cumbersome. The random errors arising from temperature gradients and fluctuations appear to be comparable to those of other techniques, as evidenced by the magnitude of the estimated uncertainties in the calculated integral thermodynamic quantities. An advantage of the method is that each run provides a relatively large amount of data; thus, it is less time consuming than those methods where samples of each composition must be measured individually. EXPERIMENTAL PROCEDURE The activities of zinc in liquid Zn-A1 alloys were measured by the isopiestic method which uses the principle of the tendency toward equilibrium of a series of samples at various temperatures under an imposed vapor pressure of the more volatile component (i.e., zinc, in this case). The basic apparatus is shown in Fig. 1. The small graphite crucibles that contained the metal samples were 15 mm ID and 13 mm deep with approximately 3 mm wall thickness. Each crucible was notched at the top and bottom to allow easy passage of vapor from one to another. At the beginning of an experiment each crucible was weighed on an analytical balance. Zinc and aluminum of spectrographic purity (99.999 pct) were then weighed into the crucibles. The amounts of each metal added were such that initial compositions varied above and below equilibrium values. One crucible contained only pure zinc. After weighing, the crucibles were stacked with the pure zinc on the bottom (corresponding to the lowest temperature in the furnace) and richest aluminum alloys at the top. The entire stack of crucibles was then placed in the silica glass container "E" which was then sealed under vacuum. Sixteen to twenty calibrated Chromel-Alumel thermocouples were attached by wire along the length of the silica tube, one or more adjacent to each sample.

Jan 1, 1970

By Paul Gordon

The distribution coefficient, k, of interest in zone refining is generally defined as the ratio of the solid to the liquid solubilities of one element in another at the normal melting point of the solvent. In practice, distribution coefficients are frequently calculated from solubilities at temperatures well below the melting point of the solvent, e.g., at a eutectic temperature. This is done because of the general lack of accurate data on the liquidus and solidus curves in most phase diagrams. The practice is equivalent to assuming that the liquidus and solidus curves are straight lines in the temperature range between the melting point of the solvent and the temperature at which data for the solubilities are known. It is recognized that the k values so derived may be in serious error; we have found evidence in recent zone-refining operations that a case in point is silicon in aluminum. The phase diagram found in the literature for silicon in aluminum indicates a eutectic on the aluminum-rich side at 12.5 at. pct Si and at 577°C,1 and a solid solubility of silicon in aluminum at this temperature of 1.59 pct.2 It also shows the liquidus and solidus as nearly straight lines from 577°C to the melting point of aluminum (660°C)1,2 The k value obtained from this data is 0.13. This is almost exactly the same as the k value (about 0.14)' obtained in a similar way for copper in aluminum. Yet we have found by mass-spectrograph analyses* of three bars of zone-refined aluminum that copper is efficiently removed from aluminum by zone refining but silicon is not. Two of the three bars of aluminum were zone-refined in our laboratories, the other in the laboratories of AIAG Metals, Inc. The former two bars, designated bars PG2 and PG3, were 30 in. long by 1 in. in diameter during refining; each was processed in a high-purity graphite boat* and kept under refining stage of the process consisted of thirty unidirectional zone traverses at rates of about 1 to 2 in. per hr, with a zone length of 1 to 2 in. At approximately the middle of the refining period a 6-in. piece of the impurity-laden finishing end of the bar* was cut off and replaced with new start- ing material. Following refining, the purest 20-in. section of the bar (obtained by discarding approximately 2 in. of the starting end and 8 in. of the finishing end of the bar) was leveled and then analyzed. The AIAG bar was 16 in. long and about 1.2 in. in diameter; it was purified by eight passes of a 2-in. zone at a rate of 1.6 in. per hr, the bar being contained in a sintered alumina boat lined with loose alumina powder of the highest purity. Data for the silicon and copper contents of the three refined bars are given in Table I. Derived data for the efficiencies of the zone-refining operations are listed in Table 11. It is clear from these two tables that the copper is removed much more efficiently—by a factor of 10 to 50 times—from aluminum during zone refining than is silicon. For example, in bar PG3 the thirty zone passes reduced the copper content from 10 to 0.02 ppm, i.e., by 500 times, whereas the same treatment lowered the silicon content by only a factor of about 16. It seem virtually certain, therefore, that the distribution co efficient, k, for silicon in aluminum is well above that for copper and is very likely not much below unity. This also implies that the solidus line on the aluminum-rich side of the A1-Si phase diagram is very probably appreciably curved near the aluminum melting point since the phase-diagram data indicate such curvature is unlikely in the liquidus.

Jan 1, 1965

By R. V. Lundquist

Leaching manganese-bearing materials with NaOH to remove caustic-soluble silica has been demonstrated as a method for upgrading manganese. Those materials containing opaline varieties of silica respond most readily. Spent leach liquors are regenerated by treatment with lime to precipitate calcium silicate and to reactivate the NaOH for leaching. ALL of our larger domestic deposits of manganese are very low grade, but estimated tonnages in these deposits are large enough to constitute a potential strategic reserve of manganese for emergency periods, provided these ores can be upgraded sufficiently to meet industrial specifications. Many types of processes have been suggested for upgrading these ores, several have been studied in pilot plants, and a few have attained limited commercial production for special purposes. The hydrometallurgical process to be described below proposes a leaching operation for removing caustic-soluble silica and other gangue minerals and consequently upgrading a manganese ore or flotation concentrate to a commercially acceptable moduct. It is known that some forms of silica and some silicate minerals are soluble in NaOH solutions under suitable conditions. This new process proposes to use NaOH for removing the soluble materials from manganese ores or concentrates and, as a result, upgrade the manganese content. Since spent leach liquors are not efficient leaching agents the liquor must be treated with lime to precipitate calcium silicate and reactivate the NaOH. Experimental Procedure Manganese-ore samples ground to —35 mesh were leached in iron containers into which the ore sample and appropriate NaOH solutions were placed. Flotation concentrates were already ground to —200 mesh. The slurries were then placed on a hot plate or into a pressure digester and stirred continuously during the period of digestion. Where the- digestion was performed at atmospheric pressures, water lost by evaporation was replaced at regular intervals to maintain approximately a constant volume of slurry. In the pressure digester, volume changes were not controlled. After digestion, the slurry was allowed to cool enough for easy handling, but it was filtered hot, 50" to 70°C, on a Buechner filter. Filtration under these conditions was satisfactory. The resulting filter cake was washed and dried. In most instances, a single leach would not produce maximum extraction of silica from the ore sample; consequently, the dried tailing was treated again in the same manner with a fresh solution of NaOH to obtain an additional extraction of silica. This procedure was repeated a number of times to get the maximum extraction of silica. Usually three or at most four stages of leaching were adequate for this purpose. This leaching procedure was used for obtaining the data reported in this paper on the effects of NaOH concentration, pulp dilution, temperature, and time of digestion on the efficiency of extraction of silica from the ore sample. The experimental procedure does not match industrial methods. consequently tests for counter-current leaching were set up. Data from these tests are not yet complete, but in a qualitative way they indicate that thickeners between stages of leaching will be satisfactory and that the quantity of silica in a leach liquor moving forward to a new solid has only a minor effect on the quantity of silica extracted from the new solid. A pilot plant is now being designed for operation in the near future to test and evaluate the merits of this process.

Jan 1, 1954