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Jan 1, 1915

By Miguel Bustamente

In 1890 I mas manager of a mining enterprise in the State of Michoacan. The ores were composed principally of iron pyrites (much decomposed), in a quartz matrix, with native gold in very irregular grains. Some portions, however, carried their metallic value in a matrix of calcite arid siderite. The mill in which the ores were treated consisted of two 800-lb. stamps, two amalgamating-plates, four pans, two automatic washers, two Frue vanners, and the necessary accessories for assaying, retorting and refining gold. The plant, originally erected with American capital, and directed by competent Americans, passed in 1890 into the hands of Mexican owners. On taking charge of the business I found on hand a large amount of ore assaying 35 grammes of gold per metric ton (about 1 oz. Troy per ton of 2000 lbs.); but the company was losing money, and was about to abandon the business. Obviously, the difficulty lay in the treatment of the ore. The extraction of gold scarcely reached one-tenth of the assayvalue ; the loss of mercury was considerable; and high freight; charges excluded the alternative of exporting the ores. This situation naturally suggested that amalgamation was not applicable to these ores, and that a more appropriate method must be adopted. The cyanide- and chlorination-methods had been tried already, without practically satisfactory results. For the first few months I employed a combined system, extracting a part of the gold by direct amalgamation, and cyaniding the concentrates. This saved 32 per cent. of the assay-value, but the cost of milling still exceeded the proceeds. Meanwhile I observed

Jan 1, 1902

By Thomas R. Couzens

Jan 1, 1985

By A. J. Lyon

THE stability and permanence of any structural material used in aircraft are of paramount importance. The spontaneous hardening, or age-hardening; which takes place in some of the aluminum alloys under ordinary conditions of temperature and atmosphere, is accompanied by an increase in tensile strength and proportional limit and a decrease in elongation or ductility. Within the last few years the introduction of a number of strong and ductile casting alloys led to a study by the Materiel Division, Air Corps, of the permanence of the physical properties in several of these alloys. It has been found that even though some alloys have good properties directly after casting or heat treatment, they are not satisfactory for stressed parts that require a combination of strength and ductility. It has also led to the conclusion that all alloys that can be hardened by artificial aging-heating in a temperature range below 170° C. (340° F.)-will harden spontaneously if allowed to stand for a sufficient length of time. It follows that, in aircraft work where the factors of safety are limited on account of the necessity of keeping the weight of the structures as low as possible consistent with their safe operation, the properties of the alloys in the stable or final condition should be used as a basis for design rather than the properties obtained on the material directly after casting. The work of Wilm in Germany, Hanson and Gayler at the National Physical Laboratory in England, and Merica, Jeffries, and others in the United States, has shown that the spontaneous hardening is characteristic to a greater or less extent in all aluminum-base alloys in which the solubility in the solid state of the alloying constituents decreases with the temperature. It has been shown that, by heating to a temperature as near as possible to the melting point of the material and soaking at that temperature for a sufficient length of time and then quenching or cooling rapidly, a maximum amount of the soluble constituents can be retained in solution and the condition of maximum hardening effect upon aging can be obtained. Also, in ordinary sand and chill castings, without heat treatment, a sufficient amount of the alloying constituents is held in solution to cause important changes in the final physical properties.

Jan 1, 1928

By C. A. Hartnagel

During- the past 10 years the annual production of petroleum in New York has averaged close to 5,000,000 bbl., the total for the period being 49,881,000 bbl. In 6 of the 10 years, the production was slightly in excess of the 5,000,000 mark. The 1944 production of 4,697,000 bbl. represents a 7 per cent decline from the previous year. Of the total 1944 output, the Allegany County district, which includes two small areas of Steuben County, contributcd 3,614,065 bbl., a decline of 5 per cent from 1943, and the contribution of Cattaraugus County, which represents the northern extension of the Bradford pool of Pennsylvania into New York was 1,082,935 bbl., a decline of more than 14 per cent. Since March 1942, the posted price of New York crude oil has remained at $3.00 per bbl. On lug. I, 1944, a Federal subsidy of 75¢ per bbl. was granted to oil producers, thus making the price actually $3.75 per bbl. Since all of the oil produced in New York comes under the designation "stripper well operations," it is entitled to the Federal subsidy. During the last few years there has been little change in the number of wells drilled annually. In the Allegany field, which accounts for three fourths of the oil produced in the state, 1240 wells, including water-intake wells, were drilled during 1944 as compared with 1223 in 1943. There was no marked increase in the number of wells drilled after granting the subsidy of 75¢ per bbl. of oil on Aug. I, the increase being but 14 wells during the last half of the year over the preceding six months. In flooding operations it is not to be expected that even a substantial increase in the price of crude oil will be reflected quickly in an increase of the number of wells drilled or in a marked increase in production of crude oil. In flooded areas, oil is obtained through a program extending over a number of years. This program involves the drilling of the water or input pressure wells, drilling of the oil wells, building up the oil flood to maximum production, and finally the watering out of the well when the amount of oil produced in proportion to the water becomes so small that pumping is no longer profitable. The various operations may extend over a period of 10 years or more, during which time the price of crude may have fluctuated greatly. Although the rate of production can be controlled to a limited extent, it is evident that a flood when once begun must be continued regardless of the price of crude. During the past seven years New York crude has had a price range from $1.68 per bbl. in 1938 to the present price of $3.75 per barrel The field pattern now in general use for wells in a flood project is the "five-spot." Under this arrangement, the lease is divided into squares with a water well at each corner and an oil well in the center. In the all-over pattern of the lease each oil well is acted upon by four water wells and each water well supplies part of the pressure to four oil wells. Spacing between the input water wells and the oil wells usually varies from zoo to 225 ft. or, on an acre basis, there is one oil well and one water well for each 2 1/2 acres. In recent years there has been a tendency to increase

Jan 1, 1945

By Isaac Vera, Hans Ruge

The El Soldado copper mineralization occurs as relatively high-grade irregular ore bodies with assay contacts and with frequent inclusions of barren rock. The sampling methods must be timely for production grade control purposes, as well as accurate and inexpensive. Sampling techniques evolved from sampling dump cars at the haulage level to sampling Scooptrams at the loading pockets. These methods were abandoned in favor of sampling production blastholes. Several sampling alternatives are discussed. These involve the selection of optimum volumes and sampling frequencies while taking into consideration geological parameters and statistical analyses of sampling data.

Jan 1, 1985

By Derek C. Shelton

This chapter covers the preparation of specifications for a dry crushing and wet grinding comminution circuit.

Jan 1, 1982

By R. P. Thomas

Secondary fertilizer minerals are the mineral materials used to supply directly and indirectly the secondary and trace plant food nutrient needs of a fertilizer. Since few soils contain sufficient availability of all plant nutrients for their proper growth, man has prepared mixtures of plant food materials to correct these nutrient deficiencies. These mixtures or fertilizers, when added correctly to a soil, make it possible for abundant and economic crop growth. Many kinds of materials are used as sources of these needed nutrients. They come from natural and synthetic materials and minerals including many beneficiated byproduct compounds. A fertilizer consists largely of carriers of one or more of the three major plant foods, namely nitrogen (N), phosphorus-phosphorus pentoxide (P2O5) and potassium-potash (K2O). Many other nutrients are just as essential for plant growth as the three major plant foods. In fact, the efficient use of fertilizers today depends upon an adequate supply of all these other nutrients. Since these additional materials are usually removed from the soil by plants and supplied in fertilizer in less quantities than the major nutrients, they are called secondary and minor nutrients. In the early days these special nutrients were contained as impurities in the primary nutrient carriers. Today, fertilizers are made primarily from concentrated and synthetic materials which carry very few of these other essential nutrients. Consequently, many secondary and trace nutrient carriers, as salts, byproduct compounds and even minerals have to be added to fertilizers. Secondary Nutrient Carriers The secondary plant foods in fertilizer are next to the major nutrients in abundance. They are calcium, magnesium, sulfur, chlorine, silicon and sodium. Although many of these elements are added to a fertilizer as part of the major nutrient carriers, they are also added in special carriers. The large tonnage of these secondary nutrient carriers used in fertilizers represents only a small percentage of the total production of these materials. A fertilizer producer thinks in terms of materials which supply nutrients instead of minerals. Therefore, these materials will be discussed by elements. CALCIUM Soils need calcium to supply the nutrient needs of plants and maintain the desired physical and biological conditions in the soil. The available calcium is usually 40 to 80 pct of the exchangeable bases. (These bases are ones which can be displaced by other cations and determined quantitatively. They are then expressed as milliequivalents per hundred grams of soil-me.) Direct applications of lime materials such as burnt, ground or hydrated limes are the important sources of calcium for the soil. Most crops, especially legumes, have a high requirement for calcium. The average farmer does not use enough lime to maintain the proper level of available calcium. Hence, it is necessary for many fertilizers to contain soluble calcium materials for efficient use of the major nutrients. The following major nutrient carriers supply some calcium: calcium nitrate, ammonium nitrate mixtures and cyanamid, and many of the phosphates. Both synthetic and natural gypsum are used in fertilizer production. Some crops such as peanuts require a large amount of soluble calcium. Gypsum is the important supplier of this soluble calcium. It is not applied with the fertilizer

Jan 1, 1960

By O. Vartiainen, R. T. Hukki

A preliminary investigation of the collecting effects of various fatty acids in tall oil has led to a conclusion that the collecting power of fatty acids used in flotation increases with increasing unsaturation of the hydrocarbon chain, Linoleic acid was found to be an excellent collector for oxide minerals.

Jan 8, 1953

By Donald E. Grimes

In conjunction with Inland Steel&apos;s development of lead-bearing steels possessing improved machin-ability because of tellurium and/or selenium additions, it was decided to determine liquidus and solidus temperatures in the Pb-PbTe-PbSe sub-ternary system. With the exception of alloys in the PbTe-PbSe system, it is believed that no previous study of this subternary has been performed. Thermal analysis was employed in a general survey of the subternary. In addition to PbTe, PbSe, and pure lead, ten ternary compositions were selected at intervals of ten at. pct. Sixty-gram alloys were prepared by sealing an appropriate mixture of the elements in quartz crucibles with a central thermocouple-well under a vacuum of less than 10 p. All three elements were 99.999+ pct pure with only trace impurities detected by spectroscopic examination. After the alloys had been heated at least 20°C above the liquidus in a Kanthal furnace, cooling and heating curves were obtained. Two or more cooling curves were employed both for the determination of each alloy liquidus and for the solidus of those al- loys containing greater than 50 at. pct Pb. Cooling rates were 0.5° to 3.5°C per min during the 5 min immediately prior to the start or end of solidification. For those ternary alloys containing 50 at. pct Pb, the solidus was determined from heating curves. Temperatures were measured with a Pt/Pt-10 pct Rh thermocouple which was calibrated in the same apparatus against the freezing points of zinc (A. D. MacKay—99.999 pct), antimony (A. D. MacKay-99.999 pct), and copper (ASARCO—99.999+ pct) both before and after the experimentation. The only interruptions in the continuous strip-chart recording of the temperature occurred for brief periods at significant points of interest when direct readings were made with a Rubicon Type B potentiometer sensitive to * 1 µv. The average liquidus and solidus temperatures obtained in this investigation are listed in Table I together with probable errors based on the accuracy of the thermocouple calibration and the reproduci-bility of the data. No chemical analyses of the alloys were performed because the synthetic or as-charged compositions were felt to be reliable. The melting points obtained for PbTe (924.7° ± 0.7°C) and PbSe (1084.0° ± 0.6°C) compare favorably with recent findings of other investigators.&apos;-&apos; As indicated in Table I, both the liquidus and solidus temperatures increase as selenium replaces tellurium for a constant atomic percent lead. As a result, the ternary liquidus and solidus temperatures for a given percent lead lie between the corresponding binary temperatures published in the literature. It should be noted that those ternary alloys containing 50 at. pct Pb exhibit a relatively narrow liquid-plus-solid region (<80°C) when compared with alloys containing greater than 50 at. pct Pb. Alloys with 60, 70, or 80 at. pct Pb not only have a much wider liquid-plus-solid region (>500°C) but also exhibit considerably lower and approximately constant solidus temperatures which thus form a virtually isothermal solidus "plane" slightly below the melting point of pure lead (327.3°C). For these alloys

Jan 1, 1965

By W. R. Hamilton

The knowledge of the existence of petroleum in Southern California dates back to the days of the missions. The presence of asphaltum and semisolid bitumen was reported at Santa Barbara in 1792, but no serious attempt was made to develop oil until Professor Silliman&apos;s optimistic report in 1865 started California&apos;s first oil boom. Wells were drilled in many counties of the State, but the equipment was unsuitable and the drilling difficult and no production was obtained except in Ventura County. Even there the production was of little importance commercially, and not until the early &apos;80s did it become sufficient to again attract attention. In 1888 the production for the State had reached a total of about 700,000 bbl. per year, practically all light oil produced in Ventura County, Pico Canyon, Los Angeles County and in the Puente Hills. The production of petroleum attained the dignity of an industry in 1895 when the Los Angeles City and Coalinga fields were discovered. The subsequent development has been remarkable, and in 20 years the production has increased from 1,000,000 to 100,000,000 bb1. per year. The refining industry has kept pace with the production of oil. The Pacific Coast Oil Co., the predecessor of the Standard Oil Co. of California, was the virtual pioneer refining company of the State, having built a refinery at Alameda about 1880. When purchased by the Standard, about 1902, it was dismantled and the refinery at Point Richmond was built. The Richmond refinery is now one of the largest in the world, having a capacity in excess of 60,000 bbl. per day. A small refinery was built by the Union Oil Co. at Santa Paula in the early days of the industry and later many asphalt refineries were in operation in Southern California. The Pacific Coast Oil Co. was then, as has been its successor, the Standard Oil Co. of California, the principal refiner and marketer of light products, the most valuable of which was kerosene. Before the opening of the twentieth century, gasoline of excellent quality was produced, though it was always a drug on the market and was produced for the simple reason that its presence rendered the flash and fire tests of the kerosene too low. The user of kerosene at the present

Jan 1, 1917

By J. H. Keeler

AN alloy of zirconium containing 18 atomic pct Cb was found to be body-centered-cubic and readily deformable at room temperature. The behavior of this alloy provided an opportunity to determine if

Jan 1, 1957

By C. H. Bushell, M. Malnarich

REAGENT control in flotation is more an art than a science. Operators vary the amount of reagents used according to the metallurgy obtained. The amount of collector may be increased, for example, if tailings losses are high and decreased if concentrate grades are low. Often control decisions are based on only one assay, such as the tailings analysis by microscopic or quick assaying techniques. This method of control has given reasonably satisfactory results but is clearly far from perfect. No adjustment in reagent addition can be made until information is received that metallurgy has deteriorated, that is, until the optimum time for adjustment has already passed. The first adjustment probably will be an overcorrection or an undercor-rection, and time will be required to establish the best new addition rates. The seriousness of the problem depends on variability of the ore. In ore of continually shifting composition and complexity, mill results will shift back and forth from excessively high concentrate grades and high tailings losses to excessively low concentrate grades and low tailings losses. Economic incentive for improved control also increases with increasing size of mill. Even a small improvement in percentage recovery in a large mill pays for expensive control equipment. The Sullivan concentrator of The Consolidated Mining & Smelting Co. of Canada Ltd. at Kimberley, B. C., treats 11,000 tpd of complex lead-zinc ore, a scale of operations which justifies an extensive research program on automatic control. Work has followed two separate lines: 1) development of faster analytical methods for pulps, and 2) study of metallurgical control by measurement and control of reagent concentrations in flotation solutions. Although work is incomplete in both phases, a progress report can be given on the development of reagent control. The primary requirement in flotation is selective attachment of particles of one mineral to air bubbles while the other minerals remain detached. Hydrophobicity of mineral surfaces is established by the collector, which coats the minerals by adsorption. The requirement of selective affinity for air bubbles is therefore equivalent to requiring selective adsorption of a collector. Adsorption theory, supported by abundant experimental evidence, shows that the amount of a reagent adsorbed at a surface must be a function of its residual concentration in solution. As the concentration in solution rises, the amount adsorbed increases, usually following some type of logarithmic curve. Selective adsorption must depend on a natural difference in the minerals, but ordinarily the differences in affinity are not great enough to obtain complete coverage of one mineral while the others are completely uncoated. An optimum concentration will exist, below which coverage will not be great enough to float enough of the valuable mineral, and above which too much unwanted mineral will float. All other reagents, except some frothers, affect the amount of collector adsorbing at constant residual collector concentration in solution, either by adsorbing competitively with the collector, or by a

Jan 1, 1957

By Samuel Frantz

THE purpose of this paper is to relate briefly the development of magnetic separation and its extension from the separation of iron into its present use in the nonmetallic field, to suggest possible future exten-sions of its field of usefulness and its possible cooperation with other separating methods. The engineering design of separating machines, and statistics as to the number of machines in operation, types, their location and production are outside the scope of this paper. Specific data will be given, however, on certain selected applications. A large part of human endeavor consists in separating one thing from another; the good from the bad, the desired from the undesired. In fact, a philosopher might plausibly claim that separating things into categories and choosing between them is the object of thought itself. In dealing with matter, separation is nowhere more inherently necessary to attain our objects than in mining and metallurgy. Both our desire and our ability to make separations are results of the physical differences between things. Gross separations such as removing ore from worthless rock or coal from slate are usually made visually and depend upon form and color, which are physical properties. When the desired and the undesired things are intimately mixed, however, it becomes impractical to select visually even if the individual particles are readily recognizable to the eye, and some automatic way of making the particles separate themselves on the basis of their own inherent differences in physical properties must be resorted to. Some of the physical properties which have been used as a basis of separation are: color, shape, hardness, size, density, elasticity, surface properties (surface tension in contact with liquids, etc.), electrical conductivity, dielectric constant, and magnetic susceptibility. Differences in these properties are used in the following methods of separation: color sorting, sifting, settlement in air and in liquids, floatsink methods, flotation, electrostatic and magnetic separation.

Jan 1, 1932

By Alfonso Rizo-Patrón, A.M. Gaudin

Previous studies of activation in flotation have directed attention to the action of the activator on the mineral to be floated rather than to the relationship of the activator to the collector. The latter phase of the problem, however, seems to have definite scientific, if not also practical, interest. In the investigation reported in this paper, experiments were carried out, largely with quartz as subject, barium as activator, and oleate as collector. The results obtained indicate that a I: I ratio of collector ion to activator ion gives optimum results, and that a 2:1 ratio almost fails to achieve activation and flotation. Yet, a 2:I ratio would have been expected on stoichiometric grounds, had the coating been a normal salt of the activator ion with the collector ion, since barium is a divalent cation and oleate a monovalent anion. To interpret and rationalize the observations, considerations of the crystal chemistry of quartz are helpful. The point of view to which these considerations lead may be of general applicability to systems involving suspensions of solids in liquids; they confirm that an adsorbed coating is inescapable. Apparatus and Supplies The experimental work consisted in barium-ion abstraction tests, hydrogen-ion and hydroxyl-ion abstraction tests, flotation tests, and determinations of the surface of the crushed quartz. The flotation machine was built according to the design of D. W. McGlashan.* It consists of a drill press in which the bit has been replaced by a stainless-steel impellor surrounding a stainless-steel sta-tor, as in the Fagergren laboratory machine. The air intake is controlled by a valve, and the cell consists of a beaker. The quartz was obtained from vein quartz stored in large chunks. It was first crushed to 20 mesh, then sized on a 28-mesh screen. The 20 to 28-mesh size alone was retained for use. This size was freed of coarse iron by passage through a Ball-Norton magnetic separator, bleached with boiling hydrochloric acid to remove residual abraded iron, washed with distilled water until the washings were thoroughly free of ferrous, ferric, and excess hydrogen ion, and stored in covered Pyrex beakers under water until used. The barium was used as barium chloride, Baker&apos;s analyzed C. P. The oleate was used as sodium oleate. It was prepared from sodium hydroxide, Baker&apos;s analyzed C. P., and oleic acid purified by R. R. de Arellano3 in the laboratories at the Massachusetts Institute of Technology. The purification procedure was elaborated from the recent $researches of Brown and Shinowara.2 It consisted in: (I) saponification of olive oil with potassium

Jan 1, 1943

By Alfonso Rizo-Patrón, A. M. Gaudin

Previous studies of activation in flotation have directed attention to the action of the activator on the mineral to be floated rather than to the relationship of the activator to the collector. The latter phase of the problem, however, seems to have definite scientific, if not also practical, interest. In the investigation reported in this paper, experiments were carried out, largely with quartz as subject, barium as activator, and oleate as collector. The results obtained indicate that a I: I ratio of collector ion to activator ion gives optimum results, and that a 2:1 ratio almost fails to achieve activation and flotation. Yet, a 2:I ratio would have been expected on stoichiometric grounds, had the coating been a normal salt of the activator ion with the collector ion, since barium is a divalent cation and oleate a monovalent anion. To interpret and rationalize the observations, considerations of the crystal chemistry of quartz are helpful. The point of view to which these considerations lead may be of general applicability to systems involving suspensions of solids in liquids; they confirm that an adsorbed coating is inescapable. Apparatus and Supplies The experimental work consisted in barium-ion abstraction tests, hydrogen-ion and hydroxyl-ion abstraction tests, flotation tests, and determinations of the surface of the crushed quartz. The flotation machine was built according to the design of D. W. McGlashan.* It consists of a drill press in which the bit has been replaced by a stainless-steel impellor surrounding a stainless-steel sta-tor, as in the Fagergren laboratory machine. The air intake is controlled by a valve, and the cell consists of a beaker. The quartz was obtained from vein quartz stored in large chunks. It was first crushed to 20 mesh, then sized on a 28-mesh screen. The 20 to 28-mesh size alone was retained for use. This size was freed of coarse iron by passage through a Ball-Norton magnetic separator, bleached with boiling hydrochloric acid to remove residual abraded iron, washed with distilled water until the washings were thoroughly free of ferrous, ferric, and excess hydrogen ion, and stored in covered Pyrex beakers under water until used. The barium was used as barium chloride, Baker&apos;s analyzed C. P. The oleate was used as sodium oleate. It was prepared from sodium hydroxide, Baker&apos;s analyzed C. P., and oleic acid purified by R. R. de Arellano3 in the laboratories at the Massachusetts Institute of Technology. The purification procedure was elaborated from the recent $researches of Brown and Shinowara.2 It consisted in: (I) saponification of olive oil with potassium

Jan 1, 1943

By Ö. Valla, A. Muan, K. Grjotheim

The solid miscibility gap between CaO and "FeO" in the system CaO-"FeO" in contact with metallic iron gradually closes as MnO is added as a third component. On the liquidus surface of the system CaO-"FeO"-MnO, this situation gives rise to a boundary curve which originates in the bounding system CaO-&apos;&apos;FeO", proceeds a short distance into the composition triangle of the ternary system, and then vanishes. A new approach has been used to follow the course of this boundary curve. It is shown that the curve vanishes at a much lower temperature and at much lower MnO contents than has been inferred previously. The oxides CaO, "FeO", and MnO together with SiO2 are the major components of the slag phase formed in the basic oxygen process. Hence, the system CaO-"Fe0"-MnO is of considerable technological interest. In addition, the system is theoretically interesting. The three oxides above all have sodium chloride structure. The size differences among the cations are such that in the bounding "binary"* systems CaO-MnO and "FeO"-MnO complete solid-solution series are formed,1,2 whereas in the system CaO-"FeO" there is only limited mutual solubility in the solid state,3 see Fig. 1. Hence, a solid miscibility gap exists in a part of the "ternary"* system Ca0-"Fe0"-Mn0, and a liquidus boundary curve originates at the peritectic point, point a in the insert in Fig. 1, in the system CaO-"FeO", extends a certain distance into the ternary system, and then vanishes. Very little quantitative information on the system Ca0-"Fe0"-Mn0 is available in previous literature. Fischer and Feischer4 sketched isothermal sections at 1600° and 1700°C, and estimated that the vanishing boundary curve extends to approximately 1650°C and a composition of 42 wt pct MnO. The work to be described in the following was aimed at locating experimentally the "vanishing" liquidus boundary curve, determining its end point, and deriving representative isothermal sections below and above the temperature of the end point of this curve. EXPERIMENTAL METHODS The phase relations were determined by the well-known quenching method. (For a description of this method as applied to oxide systems, see the original paper of Shepherd, Rankin, and wright.5) Prereacted oxide mixtures of desired compositions were contained in iron crucibles and heated in a vertical tube furnace in an atmosphere of purified nitrogen. After equilibrium was judged to have been attained, the samples were quenched to room temperature, the phases present were identified by microscopic and X-ray examination, and total iron oxide contents were determined by chemical analysis. "Fisher Certified" reagents (MnCO3, CaCO3, Fe2O3, and Fe) served as starting materials. The calcium carbonate and ferric oxide were heated in air at 400° and 800°C, respectively, for 24 hr prior to use. Manganese oxide was prepared by decomposing the carbonate in a graphite crucible in hydrogen atmosphere at 1000°C. The product was ground under acetone to -100 mesh. The iron powder was used directly without any preparation. Dicalcium ferrite was used as a starting material for some mixtures. It was made by mixing some of the above prepared CaCO3 and Fe2O3 in proportions corresponding to the formula 2CaO. Fe2O3. This mixture was then fired in air for

Jan 1, 1969

By H. K. Work

THE Bessemer process is one of the most interesting methods of making steel. At one time it was by far the most important. In recent years, however, it has steadily lost ground to the open-hearth process. The forces working against this method of steelmaking are partly economic and partly metallurgical.&apos; In this paper, dealing as it does with the control of the process, the metallurgical factors alone will be considered, although it is obvious that economic factors must play a part in determining the ultimate status of the Bessemer process. This discussion has been limited in another respect-it deals primarily with the acid Bessemer process in bottom-blown converters, although much of the information is applicable to basic and side-blown converters. The fact that open-hearth steel has superseded Bessemer steel to a large extent has tended to create an impression that Bessemer steel is inferior. As a matter of fact, Bessemer steel is actually superior to open-hearth for many applications.2 There are, however, definite metallurgical limitations to the use of Bessemer steel, resulting largely from two factors: (I) the physical properties conferred by nitrogen and phosphorus, and (2) the variability from blow to blow. These, of course, are not entirely independent, since some of the variability covered in the second item is undoubtedly due to nitrogen. But the variability is also caused by other factors. One of these is the relatively small size of the Bessemer heats. Because of this, a given shipment of Bessemer steel is more likely than a shipment of open-hearth steel to contain the product of several heats, each with its own distinctive and slightly different characteristics. Added to this is the fact that the refining of Bessemer steel proceeds so rapidly that the timing of the end point is limited to a matter of seconds, whereas the finishing period in the open hearth extends over a period of one or two hours and the timing of the end point may vary by several minutes without seriously affecting the product. There is no doubt that this has contributed to the variability of Bessemer steel and has led to the use of open-hearth steel in many optional applications. That Bessemer steel may vary is not necessarily objectionable, and it may even prove an advantage, providing a precise control is available to secure the desired qualities for any specific application. With this in mind, a comprehensive research program was undertaken, one phase of which was directed toward securing more accurate control of the blow. The results have been encouraging, and it is the purpose of this paper to describe a method in which modern scientific instruments, based on photocells, are currently being employed to assist the blower. THE CONTROL PROBLEM In this day of scientific control of technical processes, where the operating

Jan 1, 1941

By R. F. Krueger, L. C. Vogel, P. W. Fischer

Previous studies have shown that the permeabilities of sandstone cores are markedly reduced following exposure to drilling fluid and subsequent clean-up with oil at high-pressure gradients. Laboratory experiments reported in this paper indicate that permeability damage from drilling mud or water can be substantially avoided through use of an initial low-pressure gradient followed by gradually increasing gradients during clean-up by reverse oil flow. On the other hand, attempts to improve the permeability of damaged Berea and oil formation cores with high-rate oil backflush (simulated well stimulation) and low-rate clean-up gave erratic results. Essentfully complete permeability repair was achieved in most of the fresh water-damaged cores from Miocene and Pliocene oil-producing formations; only minor improvement was noted generally in tests with both water-and mud-damaged Berea sandstone. Field well stimulation treatments using high-rate back-flush resulted in long-term productivity improvement when production was brought in at gradually increasing production rates and then restricted to a steady value less than the maximum possible rate. Wellbore plugging at high production rates correlated with increasing solids content in the produced oil. Observations and results from these tests agree with current concepts that formation damage in water-sensitive rocks results from movement and bridging of formation fines, rather than from clay swelling alone. INTRODUCTION Many laboratory studies1-g have shown that the permeabilities of sandstone cores are often markedly reduced following exposure to fresh water or water-base drilling mud filtrate. However, work with cores in the restored state has demonstrated that, although permeabilities to water may be very low for sandstones containing hy-dratable clays, flow of oil can often restore a substantial portion of the effective permeabilities to oi1.Neverthe- less, water invasion into water-sensitive sandstone cores results in varying degrees of permanent reduction in permeability to oil.24&apos; Based on field data, Wade&apos;s statistical study" of well completion effectiveness also indicated a correlation between productivity damage and water invasion during completion. Similar damage can result from fluid invasion during workover. Nowak and Krueger&apos; and Bertness4 observed in their early work (1951-53) that formation damage in water-sensitive sandstones was associated not only with swelling of expandable clays but also with movement of dispersed particles. Subsequent work by Monaghan et al." (1959), Atwood&apos;&apos; (19641, Mungan" (1965) and Gray and Rex&apos;" (1965) has led to general acceptance of the hypothesis that permeability damage in water-sensitive formations is caused by migration of finely dispersed minerals and bridging in "brush heap" arrangements at pore constructions. In laboratory studies, Monaghan et al.&apos; found the use of chemicals to be of only minor value for repairing formation damage. Atwood? however, was successful in substantially repairing damage in a number of low-permeability cores using an n-hexanol flush. In the field, except for treatments with acids, the use of chemical washes to reduce wellbore damage has had limited and sporadic success and generally is unpredictable. A statistical analysis of stimulation treatments in silt-blocked wells has shown that physical manipulation of wash materials is more important than chemical composition." The recent work reported on formation damage in water-sensitive sands brings to mind the results of some unpublished exploratory work done in 1954 in connection with drilling fluid studies.&apos; This laboratory work and subsequent field stimulation treatments indicated a beneficial effect of controlled pressure drawdown and the associated production rate on formation clean-up. This paper reports the results of this work and more recent supplemental experiments on the clean-up of water-sensitive sandstones damaged by water or filtrate invasion. PERMEABILITY RECOVERY AFTER DAMAGE BY DRILLING MUD APPARATUS AND TEST SAMPLES A drilling mud circulating system was used to expose cores to simulated wellbore conditions. The mud flow system is the same as that described by Krueger and Voge17 except that no provision was made for scraping

By E. T. Turkdogan, W. L. Worrell

The rate of reaction of hydrogen sulfide with ferrous sulfide was studied by measuring the initial rates of sulfidation of iron strips in hydrogen sulfide-hydrogen-argon mixtures at 670°, 800°, and 900" C. The time-dependent surface sulfur activity is derived from the instantaneous rate of sulfidation with the assumption that diffusion in the sulfide layer is in a pseudo-steady state with the gas-sulfide chemical reaction. The rate of sulfur transfer from hydrogen sulfide to the surface of iron sulfide is proportional to the partial pressure of hydrogen sulfide and inversely proportional to the activity of sulfur at the surface of the sulfide layer. The derived rate equation is based on the assumption that most of the surface sites on the chemisorbed layer of iron sulfide are occupied by sulfur atoms and that the slow rate-controlling reaction is the dissociation of hydrogen sulfide on the chemisorbed layer. The experimental results are in reasonable accord with this reaction model. 1 HE slow approach to parabolic growth rate in the sulfidation of iron in hydrogen sulfide-hydrogen mixtures is a manifestation of slow approach to surface equilibrium between the gas and the surface of the sulfide layer. For example, at 800°C and Fig. 7 in Part I, the parabolic growth rate begins after approximately 1 day of sulfidation time. With decreasing temperature and decreasing partial pressure of hydrogen sulfide, the time necessary to reach gas-sulfide surface equilibrium is much longer. These observations are similar to those reported previously by Turkdogan et al.&apos; on the oxidation of iron to wustite in hydrogen-water vapor mixtures. The slow approach to gas-sulfide equilibrium is well-demonstrated by the results in Fig. 1 where the square of the weight gain per unit area, ( g S per sq cmI2, is plotted against time for gas mixtures having PH g//>H = 1.0 with 0, 25, 50, and 67 pct Ar at 800°C. The value of 1.5 X lo-&apos; (g S per sq cm)&apos; corresponds to almost complete sulfidation of the iron strip (- 0.05 cm thick) to iron sulfide. The points fall on S-shaped curves. If the inflection parts of the curves are considered to be linear, thus indicating parabolic growth rate and the establishment of gas-sulfide equilibrium, their slopes would have to be the same for a fixed ratio in the gas mixture. Such is not the case, and the slopes for the "linear" parts of the S-shaped curves are lower than the value when gas-sulfide surface equilibrium is established. The subject matter of this paper is the kinetics of the surface reaction of hydrogen sulfide with iron sulfide during the early stages of sulfidation of an iron strip. EXPERIMENTAL RESULTS The apparatus and materials used were the same as those discussed in Part I. In the present experiments of relatively short duration, a purified iron strip, 5 by 2 by 0.05 cm, which was suspended in the uniform hot zone of a vertical zircon tube, reacted with a flowing gas mixture of hydrogen sulfide-hydrogen-argon. The sample was suspended from a gold chain attached to a calibrated silica spring. The amount of sulfur picked up by the iron, which formed a layer of iron sulfide, was determined by measuring the displacement of a reference point on the silica spring, using a cathetom-eter. In all cases, the degreased sample was first annealed in a stream of oxygen-free dry hydrogen for several hours to remove any impurities such as oxygen, nitrogen, or carbon which might have been present on the surface of the sample.&apos; The rate measurements were carried out at 670°, 800°, and 900° C in hydrogen sulfide-hydrogen-argon mixtures with pH2 s/Ph2 ratios from 4 to 0.1. In a few experiments of short duration no sulfur deposition was observed in gas mixtures with (comments concerning sulfur deposition at high pH s/ph ratios were made in Part I.) Typical examples of the results obtained are shown in Fig. 2 for two temperatures and two gas compositions. With the present experimental technique, reproducible rate data could be obtained only after a uniform

Jan 1, 1969