Search Documents

By S. Skowronski

The melting of cathode copper, ususally containing 95.98+ per cent. • Cu, would appear to be a simple matter. Owing to the well known affinity of copper for sulfur, however, so much sulfur is absorbed by the copper during the operation that a long and expensive refining process is required to remove it, and the final product is inferior in purity and lower in electrical conductivity than the original cathode copper. The furnace operation, as now conducted, includes the following stages: 1. Charging the cathodes into the furnace. 2. Melting the cathodes. 3. Oxidizing period—saturating the copper with cuprous sub-oxide and bringing the metal to the condition known as "set copper;'' this is now done by blowing air into the molten bath of metal. 4. Reduction period, otherwise known as "poling," whereby the oxygen previously added is removed by covering the molten bath completely with coke or charcoal and introducing large poles of green wood; this reduces the cuprous sub-oxide, bringing the copper to the "tough pitch" stage ready for casting. 5. Casting Period. Many experiments have been made to obviate the long periods of oxidation and subsequent reduction, with no success. While the copper first cast will be good, as indicated by the set surface of the bars, it is impossible to hold it to the "tough pitch" condition, and long before the whole charge has been poured the copper will become "overpoled," entailing numerous difficulties. Sulfur has always been blamed by the furnace men as the reason why this refining process is necessary, yet the literature on the subject does not sufficiently emphasize how small a proportion of sulfur will ruin copper for practical purposes. The sulfur absorbed by copper during the melting period comes from two sources: (1) the sulfate left on the cathode sheets in the tank houses; (2) the fuel. The percentage of sulfates on the cathodes is variable, and depends on the care taken in washing the cathodes after removing

Jan 1, 1919

By E. L. Larison

DURING the early years of the present century a notable interest appeared in American industry in the matter of recovering and render-ing profitable byproducts of manufacturing operations. Among the byproducts of reduction of sulfide ores in many plants large amounts of sulfur dioxide gas were available. In certain instances the concentration of SO2 in the gases evolved was, or could be made, sufficient to make them suitable for manufacturing sulfuric acid. At the Anaconda Reduction works such a condition existed. Large tonnages of copper concentrate were being roasted and the roaster gases were available and suitable as a source of sulfuric acid. Earlier work on a large scale at Martinez, Calif., and in the Ducktown region, Tennessee, had shown the feasibility of manufacturing sulfuric acid from the SO2 contained in gases arising from the reduction of copper sulfide ores. In California and Tennessee the acid found a ready market in manufacture of fertilizers, while the situation regarding disposal of the sulfuric acid was quite different at Anaconda. No local use for acid existed, and a commodity of such low value could not stand freight charges to consuming centers. There was a very large accumulation of sand tailings from the gravity concentration mill below the plant at Anaconda. This material, made by the comparatively crude methods in use up to about 1915, contained about 13 lb. of copper per ton, largely as sulfide minerals. In 1912 serious research work toward recovery of this copper was instituted and after about two years of laboratory and pilot-plant development, a process for accomplishing it was perfected. This process involved roast-ing the sand tailings, leaching the roasted tailings with sulfuric acid, and throwing out the copper by passing the solutions over scrap iron. Under this plan each ton of sand required the introduction of about 70 lb. of 60° Be. sulfuric acid.

Jan 1, 1934

By Leland Van Wert

IN 1888, Howard,1 working at the Watertown Arsenal on the tensile properties of ferrous materials at various temperatures, noted the curious fact that the stress-strain diagrams of low-carbon steels tested within a certain temperature range (200° to 350° C.) departed more or less from the normal regularity of such diagrams as secured by testing at either above or below these temperatures. This same jagged appearance of similar diagrams for steels has been observed by at least one other investigator, and de Forest2 has reported similar irregularities in the tensile testing of some nonferrous alloys. Recently again, this anomaly in diagram contour has been shown in a most striking fashion, apparently because of its accentuation by the method of testing employed, by Dr. Albert Sauveur.3 He described (for nonaustenitic steels) two quite distinct types of torsional stress-time diagrams: (1) those with a regular and smooth outline, derived normally by testing at temperatures above 300° C., or below 200° C. (as, for example, Figs. 4a or e); and (2) those presenting a decided "stepped" appearance, which are invariably produced when twisting is done within the 200° to 300° C. range (examples, Figs. 5a and b). The torsion test brings out so much more sharply (and convincingly) the irregularities occurring at 200° and 300° C. than does the tensile test that they can no longer be considered as resulting from simply idiosyncratic or accidental and inconsequential causes. Clearly, from the temperatures involved, the "stepped" type of diagram, or more accurately, the peculiar manner of response to torsional stress which manifests itself in the diagram, is an aspect of the "blue-heat" phenomenon. One's curiosity if, nothing else, prompts an inquiry as to the nature and significance of these "steps." What do they mean? What causes them? To these questions there are no completely satisfactory answers. The following experimental observations are offered as suggestions towards the solution of the problem.

Jan 1, 1931

By Oswald J. Heinrich

The serious objections to the Leblanc soda process may be enumerated as follows: 1st. The total loss of sulphur employed, equal to about one-third of soda produced. Various processes have been proposed to regain this sulphur, but none have come into practical operation on a large scale. 2d. The great balk of waste products, equal to nearly twice the amount of soda, which forms a serious annoyance about the works. 3d. The complicated series of operations necessary. 4th. The large amount of labor and fuel required. 5th. The prodoction of noxious gases which necessitate extensive condensing arrangements. 6th. The large capital necessary for the . erection and maintenance of the plant, These objections have long been recognized, and many attempts have been made during the last thirty or forty years, to discover and introduce a cheaper and more direct method for the manufacture of this important staple. The reaction between bicarbonate of ammonia and common salt, whereby bicarbonate of soda, insoluble in a solution of chloride of ammonium, is precipitated, has been closely studied for the last twentyfour years, on account of its simplicity and the purity of the product it affords. This ammonia-soda process is now so far developed, that while it is not in position to entirely replace the Leblanc process, yet it can successfully compete with it where the conditions and localities are favorable. The advantages of the ammonia-soda process may be summed up as follows : 1st. It is independent of the essential agent in the Leblanc process, via., sulphuric acid, and hence can be established in those localities where salt is abundant, and yet where sulphuric acid could not be made, or where it could not be transported profitably. 2d. The ammonia-soda process being a " wet" process, the evaporation of salt brines to obtain the solid salt required in the Leblanc process, is rendered unnecessary. 3d. The direct conversion of chloride of sodium into bicarbonate of soda, which can readily be converted into the maketable monocar-

Jan 1, 1879

By Arthur E. Hall

Tax operation of "softening" in lead refining is designed, as the word implies, to separate from the bulk of the lead the elements that tend to make lead hard. These elements, which invariably are present in argentiferous lead, interfere with the desilverization, and must be almost entirely absent in refined desilverized lead. They are mainly copper, antimony, arsenic and tin. The properties utilized in accomplishing this separation are the low solubility of copper or copper sulphide in lead at its freezing-point temperature, and the greater and selective affinity for oxygen of the other elements at temperatures of the order of 700° to 900' C., or, in the prcsence of sufficient, alkali, at a temperature of about 500' C. The major problems of softening lead bullion lie in the necessary subsequent treatment of the by-products of the primary operation, which contain, either chemically or mechanically, lead or reagents that must be isolated for market or re-use. Therefore an important objective of the primary operation must be the highest practicable concentration of these elements in the by-products. Within the past three decades, during which the writer has been engaged in lead refining, the technique of softening lead bullion has had as many variations as there were lead refineries. This was the result of the variation in composition and character of lead bullion recived. The writer has received for refining shipments of lead bullion varying as widely as indicated by the following table: Sb, Per CEnt As. Per Cent Sn, Per Cent Cu. Per Cent Ag. Oz. per Ton 1.00 0.05 nil 0.05 70 0.50 2.50 2.00 0.50 200 3.50 0.50 nil 0.30 350 At times these have been received uniformly and at other times irregularly with a variation from week to week as wide as those shown. Under such conditions, establishment of a universal softening technique presented many problems. Such variations existed because refinery tolls too often were based on a ton of bullion, whatever its composition, and

Jan 1, 1937

By Edward A. Sayre

In shaft sinking for cod mines, the cost item greatly influences the method adopted. This holds true especially when soft material must be traversed. The average life of a coal mine is short. This is due either to the limited area of the coal basin or to the great expense of maintenance and haulage underground when the entries are extended a considerable distance from the hoisting shaft. Therefore, the engineer in opening a coal mine is confronted with the fact that the cost must be kept within certain bounds else the venture will prove unprofitable. For this reason he may be prohibited from adopting certain safe, but expensive, methods that are used in sinking caissons for foundations, driving transportation tunnels, or other work of permanent construction. A common method of sinking through difficult ground employs the aid of a steel shoe pushed ahead of the shaft timbers. Another is the drop-shaft method. These two methods were used in sinking the main shaft and the air shaft of the Eagle No. 3 mine, at Des Moines, Ia., and the following data show the relative success and cost of the two methods of sinking under the same conditions. A drill log of the material to be penetrated was as follows (see Plate 1, Fig. 1): Thickness, Total Depth, Ft. In. Ft. In. Drift................................... 38 38 Sand..................................... 2 40 Drift.................................... 2 6 42 6 Jointed clay.............................. 5 6 48 Drift, firm............................... 10 6 58 6 Clay, with sand streaks.................... 3 61 6 Sand.................................... 12 73 6 Shale, with two thin beds of coal and thin strata of rock......................... 86 6 160 Rock.................................... 5 165 Coal..................................... 3 9 168 9 Main Shaft Sunk by Steel-Shoe Method This record shows the first 73 ft. to bc of drift material, the lower 12 or 15 ft. of which was sand. The remaining 92 ft. to the coal was shale and rock, and offered no trouble in sinking.

Jan 1, 1917

By Eugene E. Ayres

The centrifuge has come into general use in the oil fields and in the establishments where lubricating and fuel oils are used. Probably centrifugal machinery will be found more useful in the refinery when the operators are more familiar with'the principles of modern centrifuga-tion and when centrifugal engineers better understand the refinery emulsion problems. It is not generally realized that centrifugal force and gravity have two distinct functions: First, subsidence wherein the suspended globules are brought into contact; second, coalescence (when this is possible) by rupturing the films around the globules. In the case of a water-in-oil emulsion, an exercise of the former function alone would yield: (1) oil, free, or as free as desired, from water; and (2) a concentrated water-in-oil emulsion—concentrated in the sense that it contains a relatively large percentage of the internal phase. An exercise of both functions will yield: (1) water-free oil and (2) oil-free water. Centrifugal force is much better than gravity for subsidence because, in the case of industrial emulsions where the suspended globules are visible under a microscope, subsidence is directly proportional to the force applied. Centrifugal force is only slightly better than gravity for coalescence. A minute trace of a proper reagent will immediately do more to nullify the interfacial surface tension opposing coalescence than an indefinite application of the highest attainable centrifugal force. No mathematical analysis has been made to explain the failure of high centrifugal force to induce a decidedly more rapid and more complete coalescence than is obtained by gravity. The adjustment of the centrifuge rotor depends more on the extent of coalescence that is desired or is possible than on any other factor. One reason for this dependence is to be found in the curious relation between the specific gravity and the hydrostatic pressure of emulsions. The continuous centrifuge works on the U-tube or Florentine flask prin-

Jan 1, 1924

By L. I. Cothern

THE introduction of mechanized mining has created a demand for long working faces. It has also prompted mining men to contest the old theory that longwall methods can be used only where roof conditions are ideal and where pack-wall material is plentiful. "Longwall" as used in this paper means "modified longwall," "semi-longwall," or any of the various "wall" or "long-face" methods of mining. Many mines are now using long conveyor faces that differ only in their methods of development, types of roof support and method of loading coal onto the conveyor. Some types of longwall operations are being carried on successfully under conditions heretofore considered impossible by men experienced in longwall mining. With possibly one or two exceptions, long-face methods in Alabama are a direct result of the need for lower mining costs. The advantages over room-and-pillar systems were clearly expressed in an article by Messrs. Fies and Lacy of the DeBardeleben Coal Corporation1 as follows: (1) increased tonnage per miner; (2) increased percentage of lump coal; (3) reduction in cost of development; (4) elimination of the cost of room yardage; (5) reduction in the cost of haulage, from ability to use larger cars; (6) reduction in the cost of machine cutting; (7) reduction in cost for tracks; (8) reduction in the cost of deadwork; (9) reduction in the cost of supervision. An attempt on the part of the operator to gain these, advantages by changing from room-and-pillar to longwall requires considerable courage, and credit should be given to those men who have done their bit to meet the competition of rival fuels. The initiatory problems to be solved are in reference to: (1) retreating or advancing system, (2) length of wall, (3) method of roof support, (4) method of entry development, (5) type of conveyor or loader, (6) hand vs. machine loading (onto conveyors), (7) hand vs. machine loading in entries, (8) control of roof pressure,

Jan 1, 1940

By Oswald J. Heinrich

THE serious objections to the Leblanc soda process may be enumerated as follows : 1st. The total loss of sulphur employed, equal to about one-third of soda produced. Various processes have been proposed to regain this sulphur, but none have come into practical operation on a large scale. 2d. The great bulk of waste products, equal to nearly twice the amount of soda, which forms a serious annoyance about the works. 3d. The complicated series of operations necessary. 4th. The large amount of labor and fuel required. 5th. The production of noxious gases which necessitate extensive condensing arrangements. 6th. The large capital necessary for the erection and maintenance of the plant. These objections have long been recognized, and many attempts have been made during the last thirty or forty years, to discover and introduce a cheaper and more direct method for the manufacture of this important staple. The reaction between bicarbonate of ammonia and common salt, whereby bicarbonate of soda, insoluble in a solution of chloride of ammonium, is precipitated, has been closely studied for the last twenty-four years, on account of its simplicity and the purity of the product it affords. This ammonia-soda process is now so far developed, that while it is not .in position to entirely replace the Leblanc process, yet it can successfully compete with it where the conditions and localities are favorable. The advantages of the ammonia-soda process may be summed up as follows : 1st. It is independent of the essential agent in the Leblanc process, viz., sulphuric acid, and hence can be established in those localities where salt is abundant, and yet where sulphuric acid could not be made, or where it could not be transported profitably. 2d. The ammonia-soda process being a " wet" process, the evaporation of salt brines to obtain the solid salt required in the Leblanc process, is rendered unnecessary. 3d. The direct conversion of chloride of sodium into bicarbonate of soda, which can readily be converted into the maketable monocar-

Jan 1, 1879

By L. I. Cothern

The introduction of mechanized mining has created a demand for long working faces. It has also prompted mining men to contest the old theory that longwall methods can be used only where roof conditions are ideal and where pack-wall material is plentiful. "Longwall" as used in this paper means "modified longwall," "semi-longwall," or any of the various ''wall" or "long-face" methods of mining. Many mines are now using long conveyor faces that differ only in their methods of development, types of roof support and method of loading coal onto the conveyor. Some types of longwall operations are being carried on successfully under conditions heretofore considered impossible by men experienced in longwall mining. With possibly one or two exceptions, long-face methods in Alabama are a direct result of the need for lower mining costs. The advantages over room-and-pillar systems were clearly expressed in an article by Messrs. Fies and Lacy of the DeBardeleben Coal Corporation1 as follows: (1) increased tonnage per miner; (2) increased percentage of lump coal; (3) reduction in cost of development; (4) elimination of the cost of room yardage; (5) reduction in the cost of haulage, from ability to use larger cars; (6) reduction in the cost of machine cutting; (7) reduction in cost for tracks; (8) reduction in the cost of deadwork; (9) reduction in the cost of supervision. An attempt on the part of the operator to gain these advantages by changing from room-and-pillar to longwall requires considerable courage, and credit should be given to those men who have done their bit to meet the competition of rival fuels. The initiatory problems to be solved are in reference to: (1) retreating or advancing system, (2) length of wall, (3) method of roof support, (4) method of entry development, (5) type of conveyor or loader, (6) hand vs. machine loading (onto conveyors), (7) hand vs. machine loading in entries, (8) control of roof pressure,

Jan 1, 1940

By C. P. Melloy

INTRODUCTION Ventilation practice at Isa Mine has been evolving since underground mining began in 1931. Much fundamental work has been conducted and reported regarding the primary ventilation system [Mathews K.E. et a1 (1967) and Brown J.R., Fisher T.H., Gibson K.L. (1979) 1. However, ventilation networks for subsystems such as open stopes, have evolved with experience. This paper outlines current ventilation practice for open stoping. Mount Isa Mine The mine is located in semi-arid North-West Queensland, Australia, and currently produces 20 000 tonnes of copper ore and 10 000 tonnes of silver-lead-zinc ore daily in each five day working week. Mining extends over a north-south strike length of 3.5 km with a maximum width across dip approaching 1 km, and is to a depth of 960 m (Figure 1). At present approximately 90% of the mine's copper production is from the 1100 Orebody, which contains ore reserves of 121 million tonnes of 3.2% copper. Open stoping is currently the mining method employed, and is used for primary stoping and pillar recovery adjacent to cement fill walls. The development of stoping methods in the 1100 Orebody has been documented by Kirkby R.W., Blair J.R., and Hutton R.C. (19781, Hornsby B. and Sullivan B.J. (1978), and Alexander E.G. and Fabjanczyk M.W (1981). As many as thirteen open stopes may be producing concurrently in the Orebody (Figure 2). The multiple silver-lead-zinc orebodies containing reserves of 54 million tonnes of 150 g/t silver, 6.4% lead and 6.5% zinc, are mined by open stoping, and cut and fill techniques. These methods have been documented by Goddard I.A. and Bridges M.C. (1977 1, and Goddard I. A. (1981 1. Only the ventilation of the 1100 Orebody open stopes will be discussed. However, the same ventilation philosophy is employed in open stope design in the lead orebodies.

Jan 1, 1981

By W. M. Hirthe, E. H. Greener, D. R. McCann

It has been proposed1'2 that, at low temperatures, point defects are a strengthening factor in inter-metallic compounds whereas, at high temperatures, the deformation is diffusion-controlled and, therefore, an increase in the concentration of point defects tends to soften or increase the plasticity of a compound. More recent investigations, including those of Bloem and Kroger' on PbS, Kramers and smith4 on TiO, and Nadeau5 on LiF, have extended this concept to ionic crystals. Rutile (TiO2) is a tetragonal transition metal oxide which has a defect structure over at least the compositional range. The defect in near-stoichiometric rutile is either an oxygen ion vacancys or a titanium ion interstitial.' This investigation does not contribute to resolving the defect question but either defect would satisfy the results obtained. Six specimens having the same orientation, see Fig., 1, utilized in an independent investigation1' were cut with a diamond saw from a single-crystal boule purchased from the Linde Co. Three specimens were annealed in air at 1200°C for 4 hr and slowly cooled to room temperature in a period of 12 hr. The remaining specimens were reduced in a vacuum of l0 mm Hg at 1200°C for 4 hr and cooled at the same rate in vacuum. The reduced specimens were weighed before and after reduction and, assuming the weight loss to be oxygen, the corresponding oxygen-to-metal ratio is 1.998. All specimens were chemically polished and etched utilizing the techniques described by Hirthe, Adsit, and Brittain." The specimens were embedded in acrylic resin and mounted on a leveling vise in a Kentron micro-hardness tester. A 200-g load was applied to a Knoop indenter with a descent time of 18 sec and a dwell time of 20 sec. Eight indentations were made on a near (171) surface, approximately 3 deg from the (lii) plane, for each orientation of the major axis of the indenter relative to the crystal structure. The dependence of microhardness on orienta-

Jan 1, 1963

By L. I. Cothern

The introduction of mechanized mining has created a demand for long working faces. It has also prompted mining men to contest the old theory that longwall methods can be used only where roof conditions are ideal and where pack-wall material is plentiful. "Longwall" as used in this paper means "modified longwall," "semi-longwall," or any of the various ''wall" or "long-face" methods of mining. Many mines are now using long conveyor faces that differ only in their methods of development, types of roof support and method of loading coal onto the conveyor. Some types of longwall operations are being carried on successfully under conditions heretofore considered impossible by men experienced in longwall mining. With possibly one or two exceptions, long-face methods in Alabama are a direct result of the need for lower mining costs. The advantages over room-and-pillar systems were clearly expressed in an article by Messrs. Fies and Lacy of the DeBardeleben Coal Corporation1 as follows: (1) increased tonnage per miner; (2) increased percentage of lump coal; (3) reduction in cost of development; (4) elimination of the cost of room yardage; (5) reduction in the cost of haulage, from ability to use larger cars; (6) reduction in the cost of machine cutting; (7) reduction in cost for tracks; (8) reduction in the cost of deadwork; (9) reduction in the cost of supervision. An attempt on the part of the operator to gain these advantages by changing from room-and-pillar to longwall requires considerable courage, and credit should be given to those men who have done their bit to meet the competition of rival fuels. The initiatory problems to be solved are in reference to: (1) retreating or advancing system, (2) length of wall, (3) method of roof support, (4) method of entry development, (5) type of conveyor or loader, (6) hand vs. machine loading (onto conveyors), (7) hand vs. machine loading in entries, (8) control of roof pressure,

Jan 1, 1940

By S. R. B. Cooke, H. S. Choi, I. Iwasaki

In magnetic taconite of the East Mesabi range, quartz, magnetite, and cummingtonite (OH}(Fe, Mg)(Si4O11)2) are the three major ore-forming minerals.' Fine grinding and magnetic separation of the taconite leads to a concentrate analyzing 64 to 65 pct Fe and 8 to 9 pct insoluble; the gangue content of the concentrate arising from the presence of locked magnetite-gangue particles, and of occluded gangue particles in magnetic floccules. To further upgrade such taconite concentrates, flotation appears to offer a particularly promising approach. To evaluate its effectiveness in separation, a knowledge of the flotation characteristics of each mineral comprising the concentrate becomes desirable. The floatability of magnetite and of quartz have already been reported in a previous paper,2 in which the flotation characteristics of the two minerals were correlated with the electrokinetic properties at the mineral-solution interfaces. Since cummingtonite has somewhat intermediate chemical composition between the above-named oxides, the electrokinetic and the flotation behavior of this mineral becomes of interest for both practical and fundamental reasons. In the present article the results of electrophoretic mobility measurements and of Hallimond tube flotation tests on cummingtonite are reported and are compared with those of quartz and magnetite. MATERIALS AND METHODS A sample of cummingtonite-rich taconite, received from the Mitchell pit, near Babbitt, Minn., was crushed and ground through 100 mesh, and the product was fractionated magnetically into three portions. First, a drum-type laboratory cobber was used to separate a highly magnetic portion, consisting mainly of free, but also containing locked, magnetite particles. The cobber tailing was then passed in two stages through a Franz isodynamic separator. The middle fraction was isolated, and, upon examination petrographically, was ascertained to be principally cummingtonite. The 100 to 150 mesh fraction of this sample was selected for the present study. It was cleaned by leaching briefly with hot, dilute HC1 and then by rinsing repeatedly with demineralized water. A ground and elutriated fraction of -5p cummingtonite was used for the electrophoretic measurements.

Jan 1, 1961

By H. J. Oberson, J. H. Brown

Comminution devices such as rod or ball mills are characteristically nonselective in their operation in that all material fed to a mill is ground to some extent. This is unfortunate when the object of comminution is liberation, for not only is energy expended in breaking pure gangue particles wasted, but, since gangue is frequently the predominant phase, the opportunity for such loss is great. Ideally, in this application a comminuting device should develop fracture only in locked particles. In the present investigation an attempt was made to use the large density difference which may exist between minerals to prevent comminution of one while grinding the other. EXPERIMENTAL MATERIALS AND EQUIPMENT The two minerals used in this work were -8-mesh galena and -8+ 20-mesh quartz. All tests were made on 2000-g charges containing 50 pct by weight of each mineral. Heavy media suspensions consisted of -100-mesh ferrosilicon in water. For grinding, a laboratory mill 10 in. diam by 12 in. long was filled to about 30 pct of its volume with either a ball or a rod charge. The balls ranged in size from 3/8 to 1 1/8 in. in diam; the rods ranged from 5/8 to 1 1/4 in. diam by 11 in. long. EXPERIMENTAL PROCEDURE In all tests employing heavy media, the ground pulps were treated as follows: 1) After recovering the ground charge from the mill but before drying, the pulp was wet screened on 200 mesh. 2) After drying the + 200-mesh product from step 1, the ferrosilicon was removed magnetically. 3) The nonmagnetic quartz and galena product from step 2 was sized on 10-mesh through 200-mesh screens. 4) The mineralogical composition of each screen fraction was determined by measuring its specific gravity. The specific gravity was related to the weight of galena in the fraction through the relationship

Jan 1, 1961

By Grafton M. Thrasher

For the proper discussion of this subject it is necessary to incorporate in this paper the substance of part of an article published by me in Metallurgical and Chemical Engineering for January, 1915. Several years ago, while I was chief chemist for a malleable-iron company, it occurred to me that the mere regulation of silicon was not sufficient to produce the desired degree of chill. But only after repeatedly encountering this fact in both open-hearth and air-furnace, as well as cupola metal, was I led to regard variation in the total carbon as the principal cause of disturbance; and I resolved to determine the total carbon as well as the silicon in every heat, and by a carefully prepared test piece to gauge the approximate degree of chill. The test piece selected was a round plug, 2 in. in diameter and 12 in. long, cast on end

Jan 1, 1916

By C. E. Taylor, L. V. Fegan

With on-stream electrical-resistance measurement as a basis, Bethlehem Steel developed a system for the completely automatic control of moisture in the feed to pelletizing. This system was later successfully adapted to the sintering process, with automatic control of moisture serving to maintain the air permeability required for effective burnthrough. Control of moisture content is an important factor in the agglomeration processes by which iron ores are converted into either pellets or sinter for use in blast furnace burdens. In both pelletizing and sintering the iron ore feed must be mixed with the proper amount of water so that capillary attraction and surface tension forces can be utilized to cause the ore particles to coalesce and form larger agglomerates. The success or failure of the entire pelletizing or sintering process depends on maintaining the proper moisture. Therefore, continuous automatic control of moisture is one of the conditions for the automation and optimum use of both pelletizing and sintering processes. In pelletizing, variation in moisture can cause ball size to change and is a common cause of cycling which results in a fluctuating feed to induration. Excessive moisture can cause lumps to form at the cutter bar and contributes to the formation of buildup on the green pellet screens. Green pellets with excess moisture deform and reduce bed permeability. In sintering, accurate control of moisture is also important because moisture must be within the limits that give the bed the required permeability for good burnthrough. In response to these problems, a moisture meter, based on the principle of electrical resistance measurement, was developed. This moisture meter has been a key factor in the development of systems for providing uniform feed of concentrates in most of Bethlehem's pelletizing and sintering plants. The automatic moisture control system for pelletizing was successfully plant-tested and resulted in the following: (1) Control of moisture in the green pellets to +0.2%. (2) Up to 50% reduction of bentonite consumption. (3) Control of unscreened green pellets so that 85% of the furnace product at Cornwall was within the size range of -5/8 +3/8 in. (4) Improved quality of product with a tumble test of 94 and a "Q" index of 90 as the result of feeding a consistently uniform feed to a shaft furnace. In sintering, where sinter-mix temperature change and variable feed could cause errors in moisture measurement, the system was designed to maintain the correct moisture under virtually all plant operating conditions. It was successfully plant-tested and is now in use in most of Bethlehem's sintering plants. The system achieves: (1) Control of moisture within the desired limits for optimum production. (2) Continuous measurement and control of moisture even with intermittent feeding of mix, so that attention by the operator is seldom required. The two automatic control systems provide smoother startup, minimize upsets and contribute to the consistent control of process variables in pelletizing and sintering. MOISTURE-CONTROL SYSTEM FOR PELLETIZING Fig. 1 shows the general arrangement of the system for automatic control of moisture in pelletizing.1 In this system a bin level controller, using a single probe which regulates filter speed, maintains a uniform low concentrate level in the bin.' The moisture meter, comprised of an analyzer and control components, continuously measures the moisture in the bed and adds water to adjust to the desired level. The meter is placed in an open-loop (feed-forward) control, i.e., water addition occurs downstream from the probes. Filter vacuum must be set so as to produce a filtercake moisture which is below the optimum for pelletizing. Bentonite is added after the

Jan 1, 1969

By W. F. Rogers, J. A. Stewart, P. J. Kalish, E. O. Bennett

Detailed descriptions are given of materials, apparatus and the experimental procedure used to study the effect of bacteria on sandstone permeability. The factors affecting permeability during injection of bacterial suspensions which have been investigated are: (I) concentration of bacteria; (2) core permeability and median pore size; (3) species of bacteria, mode of aggregation and relative size; (4) injection rate or pressure differential; (5) mean pressure; and (6) depth of penetration of bacteria. The investigation demonstrated that bacteria cannot reduce core pertneability to zero and that their effect on permeability is subject to definite limitations. Remedial or permeability restoration studies also were made. Acidization in combination with reverse flow war found to be an effective method for restoring permeability In cores partially plugged with bacteria. The relationship between the bacterial quantities in the laboratory tests and those found in field operations is discussed. The linear laboratory flow data have been translated into terms of field radial systems; these data indicate the most practical methods of maintaining injection rates in the presence of bacteria are to increase injection pressures or hydraulically fracture the formation. INTRODUCTION It has long been known that various bacteria flourish in the above-ground components of oil field water-injection systems. The presence of these bacteria has led to the suspicion that they might enter into the causes for reduction of injection well permeability, but only recently has an attempt been made to describe the effects quantitatively.1 Biocides are used in many cases without a firm knowledge as to whether the bacteria are killed, or if they are, whether the dead cells affect formation permeability. This project was undertaken as part of a study to determine the effect of bacteria, residual oil and precipitated solids such as iron sulfide or calcium carbonate on the permeability of sandstones and to learn whether any of these materials adversely affect brine injectivity in secondary recovery or disposal operations. This report deals with that portion relating to the effect of bacteria. MATERIALS CORES Three different permeability ranges of Berea sandstone cores were used in the study. The range of initial, absolute brine permeabilities kj were: high — 278 to 400 md: medium—130 to 162 md; and low—17.7 to 48.3 md. The permeability data for the cores used in the tests are included in Table 1. All cores were cut to a nominal 1 in. diameter. Following air permeability determinations, they were molded with an epoxy resin in 1.5 in. ID aluminum sleeves. The sleeves had drilled and tapped holes for intermediate pressure connections along the length of the cores. After molding, the high- and medium-permeability cores were trimmed to 4 in. in length and the low-permeability cores to 2 in. These lengths resulted in pore volumes of approximately 10.9, 10.4 and 4.4 ml, respectively, for the high-, medium- and low-permeability cores. Pressure-transmitting channels were drilled through the plastic into the core proper, using the sleeve holes as drill guides. Width and depth of channel penetration into the core proper were approximately 0.03 in. and 0.05 in., respectively. Three pressure taps were used with all cores; for the high- and medium-permeability cores the taps were spaced 1 in. apart; for the low-permeability cores the taps were spaced 0.4, 0.8 and 1.2 in. from the inlet end. Pore size distributions were calculated from restored-state capillary pressure curves for representative cores in each of the three permeability ranges. In each case the pore size range with the greatest percentage of the pore space included the very small pores up to 0.5 micron in radius. The median pore radii were in the 5.5 to 6 micron range for the high-permeability cores; in the 4.5 to 5 micron range for the medium-permeability cores; and in the 3.5 to 4 micron range for the low-permeability cores.

Jan 1, 1965

By J. O. Betterton, D. S. Easton

A detailed investigation was made of the phase diagram of silver-zirconium, particularly in the region 0 to 36 at. pct Ag. The system was found to be characterized by two intermediate phases Zr2Ag and ZrAg and a eutectoid reaction in which the -zirconium solid solution decomposes into a-zirconium and Zr2Ag. It was found that impurities in the range 0.05 pct from the iodide-type zirconium were sufficient to introduce deviations from binary behavior, and that with partial removal of these impurities an increase in the a-phase solid solubility limit from 0.1 to 1.1 at. pct Ag was observed. The phase diagram of the silver-zirconium system is of interest as an example of alloying a transition metal from the left side of the Periodic Table with a Group IB element. Silver would normally act as a univalent metal, its filled 4d-shell remaining undisturbed during the alloying. However, there is a possibility that some of the 4d electrons might transfer to the zirconium. An insight into such a question can occasionally be obtained by comparison of phase diagrams. The silver-zirconium system forms part of a more complete review of various solutes in zirconium in which these valency effects were studied.' Earlier work on the silver-zirconium system was done by Raub and Enge1,2 who investigated the silver-rich alloys. After the start of the present experhents, work on this system was reported by Kemper3 and by Karlsson4 which for the most part agrees with the phase diagram presented here. EXPERIMENTAL PROCEDURE The alloys were prepared by arc casting on a water-cooled, copper hearth with a tungsten electrode and in a pure argon atmosphere. Uniform solute composition was attained by multiple melting on alternate sides of the same ingot. Progressive improvements in the vacuum conditions inside the apparatus during the course of the experiments reduced the Vickers hardness increase of the pure zirconium control ingot from 10 to 20 points, observed initially, to negligible amounts at the end of the experiments. Such hardness changes in zirconium are a well known indication of purity. For example, -01 wt pct additions of oxygen, nitrogen, and carbon increase hardness by 6, 10, and 3 VPN respectively. '9' Further verification that the final casting technique did not add a significant quantity of impurities was obtained when pure zirconium was arc cast and then isothermally annealed in the vicinity of the allotropic transition. The transition was always observed to take place over the same temperature range as in the original crystal bar. The alloy ingots were annealed in sealed silica capsules for times and temperatures which varied between 1 day at 1300°C and 60 days at 700°C. The best method found to prevent the reaction of the zirconium with the silica was foil wrapping of molybdenum or tantalum. With this method, samples of pure zirconium were found to be unchanged in hardness after annealing for 3 days at 1200°C. In most of the experiments the protection of these foils was supplemented by an additional layer of zirconium foil inside the molybdenum or tantalum foil. The alloys, foil, and the capsule were outgassed at pressures in the range 10 to l0-7mm Hg in the temperature range 800" to 1100°C before each anneal in order to remove hydrogen and other impurities, and to provide a suitable container for the high purity, inert atmosphere, which is essential in the annealing of zirconium. The temperature measurements were made with Pt/Pt + 10 pct Rh thermocouples calibrated frequently during the experiments against the melting points of zinc, aluminum, silver, gold, and palladium. For the longer anneals the sum of various temperature errors was generally well within ± 2°C. For short-time anneals and during thermal analysis the overall temperature error is considered to be within ± 0.5°C. The compositions of the alloys from the quenching experiments were determined by chemical analysis at Johnson Matthey and Company, Ltd., under the direction of Mr. F. M. Lever. The actual metallo-graphic samples were individually analyzed in every case, and prior to the analyses two or more sides of each specimen were examined to insure that the specimen was not segregated. The sum of the solute and solvent analyses was in each case within the range 99.9 to 100.1 pct. In the course of the experiments, minor impurities in the range 0 to 500 ppm were found to have significant effects on the zirconium-rich portion of the phase diagram. Similar effects had been encountered previously in other zirconium phase-

Jan 1, 1959

By Irving Cadoff, Kurt Komarek, Edward Miller

Barium can be purified by equilibration with titanium. The melting point of barium was found to be 726.2° i 0.5 °C. The room-temperature lattice parameters of BaTe and Bask are 7.004 * 0.002A and 6.600 * 0.002A. Melting points for BaTe and Base were found to be 1510° * 30°C and 1830° ± 50°C, respectively. HIGH-purity barium and its compounds are difficult to prepare because of the reactivity of barium with the atmosphere and the large heats of formation of the compounds. Purification of barium by vacuum distillation,' and the preparation and properties of barium oxide2 and barium sulfide3 have been reported. However, little has been done on the homologous compounds barium selenide and telluride. PURIFICATION OF BARIUM Distilled barium obtained from King Laboratories was used as the starting material. The analysis supplied with the metal showed the presence of: 0.4 wt pct Sr, 0.001 pct Mg, 0.02 pct F, 0.003 pct Cu, 0.005 pct Na and less than 5 x 10-3 wt pct of any other metallic impurity. Analyses for oxygen and nitrogen were not available. Since there is evidence4 that any barium nitride present in the starting material may decompose on distillation producing nitrogen which can contaminate the distillate, further purification was performed. At elevated temperatures, any nitrogen and oxygen present in barium should be removed by reaction with titanium. Assuming that the solubility of oxygen in liquid barium is negligible near the melting point of barium, any oxygen present will be in the form of BaO. Removal of oxygen from molten barium is expressed by the equation: BaO(S)+ TixOy(S) = Ba(l)+ TixO(y+1)(s) where Ti,Oy and TixO(y+1) are solid solutions of oxygen in titanium. At 1000°C, the change in free energy for this reaction is negative for (y+1)/x +y+1) x (100) 17.5 at. pct O.5 Since reaction with commercially pure titanium (containing 0.07 wt pct oxygen) results in a free energy change for the reaction of -19 kcal per g-atom, slight solubility of oxygen in barium would not hinder the oxygen removal. Since comparable thermodynamic data are not available to permit calculation of the partition of nitrogen between liquid barium and titanium, a similar quantitative relationship cannot be obtained. However, on the basis of work by Kubaschewski and Dench,5 complete removal of nitrogen from liquid barium can be expected. Since the melting point of barium is depressed markedly by small additions of nitrogen,' the change in melting point during reaction of barium with titanium was used to follow the purification reaction. MELTING POINT OF BARIUM A 50-g sample of barium was sealed by arc welding under argon into an all titanium crucible provided with a thermocouple well. The melting point of the sample was determined by thermal analysis, using a Pt/Pt-10 pct Rh thermocouple which was calibrated according to National Bureau of Standards specification6. The crucible was then heated for 48 hr at 950°C in vacuum and the melting point redetermined. This procedure was repeated until three successive thermal analyses agreed within ±0.5oC, the limits of error of the analysis. The melting point increased from an initial value of 720.0°C to a final value of 726.2°C. Analysis on samples quenched from 950°C gave a solubility value of 0.004 wt. pct Ti. Assuming that the titanium-barium phase diagram is similar to those of titanium-magnesium7 and titanium-calcium,8 the solubility of titanium in liquid barium decreases with decreasing temperature. Therefore, the solubility of titanium in liquid barium should be less than 0.004 wt. pctat the melting point (726oC), and the effect of dissolved titanium on the melting point would be negligible. Addition of up to 3 wt pct Sr does not significantly change the melting point of barium,7 so that the effect of the 0.4 wt pct Sr in the starting material will also be negligible. The value of 726.2" ± 0.5C obtained for the melting point of barium can be compared .with a determination carried out by Keller and coworkers in low-carbon steel crucibles,' who obtained a value of 725± 1C, using barium purified by fractional distillation. The higher value obtained in the present investigation is indicative of the effectiveness of titanium in removing traces of nitrogen. PREPARATION OF BaTe AND Base The compounds were prepared by direct reaction

Jan 1, 1961