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By G. Nabi, W-K. Lu

Cylindrical specimens of natural dense hematite were reduced to magnetite at atmospheric pressure in H2-H2O mixtures of known composition over the temperature range 1084° to 1284°K. The rate of reduction was measured by the rate of movement of the interface between hematite and magnetite. The diffusion of gases through the gaseous boundary layer, the magnetite layer, and the interfacial chemical reaction were all considered in the interpretation of experimental data. The mass transfer coefficient through the boundary layer was calculated using accepted correlations. Values of the chemical reaction rate constant and the diffusivity of hydrogen in the magnetite phase were determined. THE present investigation is concerned with the reduction kinetics of natural hematite to magnetite by H2-H2O mixtures in the temperature range 1084" to 1284°K at atmospheric pressure. This reaction is the first step in the series of topochemical reactions in the process of reducing hematite to iron. Kinetic information of the simple steps such as hematite-magnetite transformation is necessary in order to have a better understanding of the complex processes of hematite reduction in iron-making. It also has direct industrial significance because magnetic roasting is one of the most important methods in benefication of lean ore.&apos; Although many technical papers have been published on the process of magnetic roasting and iron oxide reduction, very little information is available in the literature concerning the fundamental nature of hematite reduction to magnetite by reducing gases. Hansen et al.2 reduced the dense synthetic pellets of high-purity oxide in CO-CO2 mixtures and determined the reaction rate by weight-loss method. They were able to interpret most of their results by applying the interfacial area control theory developed by Mckewan.3 In contrast, Wilhelm and St. Pierre,4 who studied reduction of hematite to magnetite in H2-H2O mixtures by weight-loss method, stressed that the resistance of the porous magnetite layer to the diffusion of gases cannot be neglected in consideration of the overall reaction rate. In the present study the contributions of interfacial chemical reaction, diffusion of gases through the magnetite phase, and the gaseous boundary layer to the overall reaction rate will be considered. APPARATUS AND PROCEDURE Hematite Specimens Preparation. Natural hematite ore from Vermillon range of Northern Minnesota was selected for the present investigation because of its high purity and thermal stability. Chemical analysis of five samples gave the following average values: 67.52 pct total iron (96.62 pct Fe2O3, 0.28 pct FeO, 0.03 pct metallic iron), 2.53 pct SiO2, <0.07 pct MgO, 0.03 pct CaO, 0.05 pct combined mixture, 0.07 pct loss on ignition, and 0.34 pct other. Cylindrical specimens of 0.93 cm in diam and 2.7 cm in length were drilled from slabs of ore with a water-cooled diamond core drill. These specimens were heated to 1000°C and furnace-cooled. Specimens with silica pockets developed large cracks. The uncracked specimens were heated a second time, and their surfaces were carefully examined with a microscope. Those with hairline cracks or surface inhomoaenitv-- were rejected. Preparation of H2-H2O Mixtures. H2-H2O mixtures were prepared by the combustion of H2-O2, mixtures in a pyrex glass chamber in the presence of a catalyst. Alumina pellets coated with palladium, supplied by Englehard Industries, were used as the catalyst. Purified grades of hydrogen and oxygen were used which were repurified by usual techniques. Hydrogen before entering the combustion chamber was passed through an activated alumina H2O absorption bulb, with copper turning at the top. The cover of this bulb was not made pressure-tight so that any pressure development in the hydrogen line would cause the cover to blow off and also the copper turnings would act as a flame arrester in the case of a flashback from the combustion flame. Oxygen flow rates were measured with a bubble flow meter after purification with 1 pct accuracy. Hydrogen flow rates were measured by "precision wet test meter" and the amount of unburnt hydrogen was accurately measured by a bubble flow meter, after condensing water vapor in the gaseous stream. The Pyrex glass bulb contained concentric Vycor glass tubes as shown in Fig. 1. Oxygen was prevented from diffusing into the hydrogen line by threading platinum wire through pores at the combustion end of gas inlet tube. The glass bulb was heated with a Kanthal heating wire pasted in asbestos paper. The surface temperature of the bulb was measured with a thermocouple and adjusted to remain at approximately 350°C. The gaseous reaction chamber also served as a preheater for gases to avoid thermal segregation. The following sequence of operation was adopted. 1) Nitrogen was passed through the outer concentric tube to purge the catalyst bulb of oxygen. 2) Hydrogen was introduced through the inner tube until a steady flow was obtained. 3) Oxygen was then introduced into the nitrogen stream passing through the outer tube. 4) When combustion had commenced and a flame was visible over the platinum wire, the N2 was turned off.

Jan 1, 1969

By T. W. Harris

This paper was written in conjunction with the work being undertaken by the Technical Committees on Classification of Coal, and an effort has been made to compile information relative to the use of coal for stationary steam generation in order to use this information to assist the Committee on Classification of Coal for the ultimate purpose of elimination of losses both by the reduction of individual effort and waste in the consumption of material. Under the auspices of the National Association of Purchasing Agents, a questionnaire was drawn up to develop this information from stationary steam plants throughout the United States in order to consolidate the information developed from the many hundreds of boiler tests on coals consumed by various coal-burning equipment. These questionnaires covered: 1. The company reporting, location and method of delivery to the plant. 2. Complete coal data, including description of coals used (with sufficient space to include first, second and third preference) on source of coal used, complete analysis and factors affecting choice of coal used. 3. Plant data, divided into: (a,) hand-fired, (b) overfeed stokers, (c) underfeed stokers, (d) traveling grate stokers, (e) pulverized coal; and included complete description of furnace data, draft data, coal-burning rate, type of stoker, type of pulverizer, efficiency data and remarks. The questionnaire was drawn up by consultation with various combllstion engineers, including B. J. Cross, Test Engineer of the Combustion Engineering Co., W. H. Fulweiler, of the United Gas Improvement Co. and the U. S. Bureau of Mines. In all, 11,538 copies of the questionnaire have been distributed, of which 4369 were sent in duplicate. Our estimate of the total volume of bituminous coal consumed in stationary steam boilers over the 12 months of 1930 is approximately

Jan 1, 1934

By R. C. Padfield

Experience over a 3-year period in Bethlehem Steel Corporation&apos;s plants has demonstrated the reliability of open-hearth roofs of bonded sprung-arch constructzon with burned basic brick. The design principles lor constructing these roofs include a minimum hot-strength requirement for the basic brick, expansion allowances that extend the full roof thickness, structural members to control arch contour, and a specified minimum roof rise. The greater stability of bonded roofs is explained in terms of the basic stress patterns of ring constrution and bonded construction. PRIOR to the development of successful sprung-arch roofs of basic brick, the majority of open-hearth furnaces in the United States were operated with sprung-arch roofs built of silica brick. Although many silica roofs used on open-hearth furnaces were ring-arch construction, Bethlehem Steel Corp. used bonded-arch construction because of its greater stability. In ring construction, each ring of brick is separately keyed and comprises an independent arch with the straight joints between rings traverse to the longitudinal axis of the furnace. In bonded construction, the bricks are laid in rows starting from the skewbacks so that the straight joints run parallel to the longitudinal axis of the furnace. Each brick in a given row is laid so that it spans the joint between two bricks in the row beneath it. Thus, the transverse joints across the arch are broken and the arch rings are thereby interlocked or bonded. When basic roofs were first being developed, the basic brick that were available had low hot strength. Such brick could not be safely used in sprung-arch construction without some means of suspending them. With the development of higher firing techniques by brick manufacturers and the recently introduced direct bonded bricks with high hot strength, the use of burned basic brick in sprung-arch roofs became feasible. The availability of high hot strength basic brick coupled with the potentially lower cost and proven stability of bonded construction prompted Bethlehem&apos;s Research Department to study the possibility of using basic brick in bonded roofs. With the full cooperation of plant ceramic engineers and open-hearth superintendents, particularly in 3 years of fur-nace trials, we developed the design criteria for bonded roofs and the corresponding property requirements for the basic brick that are discussed in this paper. DESIGN PRINCIPLES OF SPRUNG-ARCH BRICK ROOFS Stresses in Fixed Arches. A sprung-arch open-hearth furnace roof is generally built on rigidly held skewbacks. The constraint of the fixed support at each end adds a bending moment to the horizontal and vertical reactions at the ends of the arch. Fig. 11 shows the positive direction of forces acting on an arch fixed at both ends. Fixed arches can be analyzed when the members are continuous and have elastic properties. However, brick are inelastic, and arches built with individual brick segments cannot carry tensile stresses. Therefore, for practical solution of brick arches, empirical formulas have been derived from elastic theory that place design restrictions on arch dimensions to avoid development of tensile stresses. McDowell2 cites three main conditions for stability in sprung brick arches: 1) the thrust line of the arch should be maintained in the middle third of the thickness to avoid tensile stresses and resulting open joints in inner and outer curves of the arch; 2) the angle between the line of thrust at any joint and a line perpendicular to the joint must not exceed the angle of repose between brick; and 3) the maximum pressure at any point must not exceed the strength of the arch materials at furnace operating temperatures. The first and third conditions are particularly important in designing sprung-arch basic roofs because of the comparatively low hot strength of basic brick. According to McDowell&apos;s equation, if the thrust line is maintained within the middle third of the arch thickness, the unit pressure is obtained as follows: where p = unit pressure in psi, F, = resultant thrust normal to skewback in pounds per foot, t = arch thickness in inches, and z = distance in inches of thrust line from arch axis. When the resultant thrust normal to the skewback acts along the arch axis, z equals zero and unit pressure is simply the thrust divided by the cross-sectional area. If the thrust line moves to the limits of the middle third of the arch thickness, beyond which tensile forces would develop, z then equals one-sixth of the arch thickness and the unit pressure is double that when the thrust line is acting

Jan 1, 1968

By Carl Henrich

While the size of the blast-furnaces used for smelting leadand copper-ores has constantly increased, during late years, the manner of removing the slag from the furnace to the slag-dump has (until quite recently, at least) practically remained the same. The only appliance in practical use has been the two-wheeled slag-pot, holding about 300 to 400 pounds of slag, or as much as one man could manage to pull or push on a smooth, hard surface. When these slag-pots on wheels were first introduced, the daily capacity of a lead or copper blast-furnace hardly reached 30 tons of smelting-charge. With furnaces of this size, and even when the capacity had been doubled, this kind of slag-pot answered well enough. All the improvements made were in the construction of these pots and not in an increase of their size, which was limited by the weight which one man could handle. But the size of the furnace went on increasing. The daily consumption of one furnace rose gradually to 75 tons, 100 tons, and even more. The writer had occasion to construct some of these furnaces, which, in their day, were among the largest, if not the largest, of the water-jacketed kind then in existence. A water-jacketed furnace will always smelt more in the same time than a furnace with brick walls. Already, in those days, the slag-removal from these enlarged furnaces received due attention by the writer. The removal of 60 tons of slag in 24 hours, in pots holding only 300 pounds each, will require 400 pots to be filled in 24 hours; and when the amount.of slag increases to 90 tons, 600 pots will be required. That is to say, in the last case, 25 pots in each hour, or 1 pot each 24 minutes, will have to be put under the slagspout, filled, pulled away, and replaced with another. This will involve too much hurry for any degree of comfort, convenience

Jan 1, 1896

By George L. Heath

This paper is devoted chiefly to the coal-fields of the western part of the province of Chili and the eastern part of the province of Shansi; but the outline of this belt will give some idea of the extension of the coal-fields over northeastern China. This part of China is topographically divided into: (1) the mountainous peninsula of eastern Shantung; (2) the coastal plains, extending W. and SW. from the gulf of Pechili; and (3) the mountains and table-lands N. and W. of the coastal plains. The plains extend N. and W. from the gulf to within from 10 to 25 miles of the Great Wall, while their SW. extension covers western Shantung and reaches W. along the Yellow river almost to the southern boundary of Shansi. A line joining the mapped coal-fields, shown in Fig. 1, almost gives the western boundary of the plains; since these areas lie on the border of the plains—except the Tsê Chou field, which is on the table-land, 20 to 25 miles from that border. The coal-fields which have been mapped and investigated by the author are shown in Fig. 1. The one at and around Tongshan is known as the K&apos;ai-p&apos;ing coal-field; the one W. of Peking has been called the Wang-p&apos;ing coal-basin; the one SW. of Pao-ting and N. of Chêng-ting may be called the Lingshan coal-field; and the one at and around Tsê Chou is known as the Tsê Chou coal-field. I. The K&apos;ai-p&apos;ing Coal-Field. As is shown in Fig. 2, most of this field lies in the coastal plains, and is therefore covered by alluvium and loess, which have buried the older rock-beds, and the more gentle and older topographic outlines, to such an extent that most of the re-

Jan 1, 1902

By P. Chiotti, E. R. Stevens

The electromotive force between pure magnesium and Mg-Zn alloys in a fused KC1-LiCl-MgC12 cell was measured over the temperature range 360° to 730°C and for alloy compositions of 0.052 to 0.635 atom fraction magnesium. The calculated activity coefficients of magnesium in the liquid alloys may he represented by the relation These data and the phase diagram were employed in calculating the standard free energy of formation for the compounds MgZn, MgZn2, and MgZn2, In the temperature range from 25° to 590°C the relation ZINC-rich magnesium alloys have been shown to be very effective in reducing various solute chlorides or oxides from fused salts such as KC1-LiC1 eutectic. Such reactions are of interest in the developinent of pyrometallurgical methods for reprocessing nuclear reactor fuels.&apos; As the conceniration of the magnesium is increased beyond 5 to 10 wt pct the extent to which solutes, such as yttrium, lanthanum, cerium, and other rare earths, can be reduced or removed from the salt decreases. This effect is due to the resulting change in the activity of the solutes in the Zn-Mg alloy as well as the change in the activity of both the zinc and mag- nesium. The purpose of the present investigation was to determine the thermodynamic properties of the Zn-Mg system which, in addition to yielding information on the alloying behavior of these two elements, would permit a more quantitative understanding of the above reactions. Since this investigation was initiated several publications have appeared in the literature giving results on the thermodynamic properties for the liquid alloys of this system. 2-4 Kozuka, Moriyama, and Kushima3 measured the vapor pressure of zinc over four different alloy compositions by a carrier-gas technique. Eremenko and Tukashenko2 and Terpilowski4 measured the electromotive force between pure magnesium and various alloys in a fused salt cell. Earlier work has been summarized by Hultgren, Orr, Anderson, and Kelley.5 In the present investigation electromotive-force measurements were made on a cell of the type The temperature range covered for the lower-melting alloys was roughly 375° to 730°C. These data were employed in calculating the thermodynamic properties for the liquid alloys and in conjunction with the phase diagram,&apos; reproduced in Fig. 1, were used in calculating the standard free energy of formation of the compounds MgZn, MgZn2, and Mg2 Zn11. The results obtained are compared with available data from the literature. MATERIALS AND EXPERIMENTAL PROCEDURES Materials employed were: Bunker Hill slab zinc, 99.99 pct pure; Ames Laboratory magnesium containing 13 ppm N, 195 ppm C, and trace amounts of calcium, copper, nickel, and silicon; reagent grade KC1, LiC1; and high-purity MgC12 obtained from Dow Chemical Co. The electrolyte consisting of KC1-LiCl eutectic (44.4 wt pct LiC1) to which was added 15 wt pct MgCl2, was dried in a quartz tube by heating to 340° C under vacuum for a period of 4 to 5 hr, and then passing HC1 through the salt as the temperature was slowly raised to above the melting point of the salt. After about 3 hr the HC1 was shut off and the system flushed with argon and then vacuum applied for 1 hr. The salt was finally siphoned through a sintered glass filter and cast into a Pyrex container which was sealed and

Jan 1, 1965

By K. J. Brondyke, P. D. Hess

Lack of correlation between densities of aluminum alloy samples solidified under reduced pressure (vacuum gas test) and hydrogen content of the metal is explained on the basis of inclusions serving as nuclei for hydrogen bubble formation. As a result of these findings, the vacuum gas test is suggested as a practical tool to indicate metal cleanliness and the potential effects of hydrogen. Visual obseroation of the sample during solidification under vacuum provides more useful information than that obtained either from density meas -urements or sectioning of the solidified sample. A rapid, practical method of detecting and measuring gas in molten-aluminum alloys has been sought for many years. The development of the vacuum gas test appeared to solve this problem. However, the vacuum gas test is subject to certain limitations, and the results must be interpreted mindful of these limitations, as described herein. Since the only gas which is appreciably soluble in aluminum is hydrogen, the terms gas and hydrogen will be used interchangeably in this paper. In the early days of the aluminum industry, when techniques were not as refined as they are today, it was customary to pour small "pancakes" of alumi- num on a metal plate. These were allowed to solidify under atmospheric pressure. Excessive gas in the metal was evidenced by the appearance of small bubbles on the surface of the "pancake".&apos; It is obvious that such a method would only show very high gas levels far above any which could be tolerated by today&apos;s standards of quality required for most applications. Various attempts were made to develop methods which would be more sensitive. Among these were measurements of density of aluminum alloys solidified under controlled conditions, radiography of cast slabs, and examination of fractures. The method which showed the greatest promise and appeared most practical was the solidification of a sample of the molten aluminum alloy under vacuum. The samples so solidified are evaluated either by observation for bubble emission during solidification, by sectioning the solidified sample and examining for porosity, or by determining the density of the solidified sample. This test is known internationally as the Straube-Pfeiffer test or the reduced-pressure solidification test, but in America it is commonly referred to as the vacuum gas test2-&apos; and will be so designated in this paper. The determination of density appeared an attractive and convenient means of providing a numerical rating for the samples. Attempts were made in some instances to correlate densities to hydrogen contents. Unfortunately, the visible loss of gas during solidification of samples with high gas contents precluded a correlation of vacuum gas test densities with the observed gas evolution. This led to Alcoa&apos;s use of two different pressures; 50 mm of

Jan 1, 1964

By T. M. Chance

The first bituminous coal cleaning-plant to use the sand-flotation process1 was placed in operation on Oct. 1, 1925, at the tipple of the East Broad Top Railroad & Coal Co., at Mt. Union, Pa. The general principles governing the design of plants of this type and typical operating results of anthracite sand-flotation units have been previously outlined.2 I will, therefore, confine myself to a description of this particular plant and to some of the elements of design it incorporates. The Original Mt. Union Tipple The plant was installed to transfer coal.from steel narrow-gage cars of 60,000 and 70,000 lb. capacity to standard-gage equipment. The coal was hauled about 30 miles from the East Broad Top field. This coa1, mined by the Rockhill Coal & Iron Co. and other operators, is a low-volatile slow-coking coal with ash of high-fusion point. It is normally a high-grade coal that does not contain an excessive amount of free impurities, but it requires careful handling to secure a fair domestic yield, and, naturally, the need for narrow-gage transshipment increases the difficulty of the problem. The narrow-gage cars were discharged into an 8-car track hopper equipped with two feeders passing the coal to two 42-in. apron intake conveyors. Twin units were installed throughout the original plant, two lump-and-egg shaking screens, two lump picking-tables, two egg picking-tables and two stoker conveyors. The stoker coal was loaded without cleaning. The loading tracks and booms were in duplicate and, with the layout as originally installed, either unit could be run independently, each unit shipping a different class of coal or both units making the same product.

Jan 1, 1927

By T. C. Atchison, W. I. Duvall

Over the past ten years a series of investigations have been conducted to determine some of the pnysical processes involved in breaking rock with confined concentrated charges. Detailed discussions of many of these investigations have been published elsewhere.1-6 Laboratory experiments made by other investigators using Hopkinson pressure-bar techniques have shown that solid materials are fractured in tension by the reflection of an incident compressive stress pulse at a free surface.7-12 In these tests a small charge of explosive is placed in contact with one end of a bar. Detonation produces some plastic flow and crushing of the bar near the charge and generates a compressive stress pulse that travels along the length of the bar. At the free end of the bar the compressive stress pulse is reflected back into the bar as a tensile stress pulse. If the tensile strength of the bar is exceeded during this reflection process, a tensile fracture normal to the length of the bar is produced, and the broken end of the bar moves forward with a constant velocity equal to the average particle velocity trapped in the broken fragment. The new surface formed by the fracture becomes the new free end of the bar that reflects the remaining portion of the incident compressive stress pulse. This process is repeated any number of times until all of the incident stress pulse is reflected. Hino has demonstrated this kind of breakage for three rock types—marble, granite, and sandstone." He has defined a blastibility coefficient, B, as the ratio of compressive strength, C, to tensile strength, T, thus: C The quantity B is the maximum number of slabs that can be produced by reflection breakage. Normally fewer slabs are produced because of loss of energy as the stress pulse travels through the rock. Fig. 1 illustrates reflection-type fracture for a triangular compressive stress pulse. The number of slabs produced by the reflection breakage process is the first whole number less than the ratio of the peak stress of the incident pulse to the tensile breaking stress of the solid. Thus the number of slabs is given by the thickness of each slab is given by and the total length of rock broken is given by N = number of slabs S - peak stress in incident pulse T = tensile strength of the rock F = fall length of incident stress pulse h = thickness of each slab D = total length of rock broken During the reflection process the particle velocity at the free surface is twice the particle velocity in the incident stress pulse. Thus the velocity with which the broken fragments move forward is given by where v, = velocity of broken fragment, and v = average particle velocity contained in that portion of the incident pulse trapped in the broken fragment. Results of these laboratory experiments cannot be applied directly to rock blasting where the explosive charge is placed in a drillhole. In laboratory tests the charge is unconfined and in contact with the rock in only one direction. In a drillhole additional confinement is offered by the rock surrounding the charge and by the stemming placed above it. This additional confinement may be enough to allow the explosive gases to do additional work on the rock during their expansion. Other writers have discussed possible effects of gas expansion&apos;on rock breakage.13-10 However, very few experimental data are available to determine to what extent expansion of the gases is responsible for rock fragmentation. The USBM has studied the physical processes involved in breaking rock with confined concentrated charges by using simple crater tests breaking to one free surface. Crater tests have been performed in four rock types: granite, sandstone, marlstone, and chalk. Table I gives some physical properties of these rocks. Fig. 2 shows plan and section drawings of two typical crater tests and illustrates some of the test variables measured. For these tests the charge was placed at the bottom of the drillhole and primed with an electric cap. The hole was stemmed to the collar with sand and the charge detonated. Size and shape of the crater were measured after it was cleared of broken rock. As a given charge size was buried deeper in a drillhole, the crater depth usually was equal to or

Jan 1, 1960

By C. W. MacGregor

IN the testing of materials there exist various methods of recording graphically the behavior of a material subjected to tensile stress. Prob-ably the most common method is to plot the tensile stress So, obtained by dividing the load P by the original area of cross section AO at the start of the test, as a function of the strain ?o, which is obtained by dividing the ?Lo or the change in the gauge length by the original gauge length Lo. A list of the symbols used here is given in Table 1. This method, while it has proved useful in the routine testing and comparison of various materials, does not have a very sound physical basis, as was first pointed out by P. Ludwik1, and consequently does not afford a very deep insight into the true physical behavior of the material under stress. Among the objections to this method may be mentioned: (1) that by dividing the load P at any stage of the test by the original area Ao a fictitious stress is obtained, which does not actually exist; (2) that the strain ?o = ?Lo /Lo is not an exact expression for the true strain for large values of ?Lo in per cent of Lo; (3) that when necking starts the strain varies considerably along the gauge length and the above expression no longer gives the true strain existing at any point on the outside of the bar; and (4) that the axial strain varies over the cross section of the necked portion and ?o does not represent an average of these strains over the cross section. Stresses taken from such a diagram would be only approximate and, if used to compare results of a test on a given material under simple tension with results obtained under combined stresses, certain errors would he thus introduced. In order to overcome some of these objections, various methods have been suggested, both as to the quantities to be measured and as to their graphical representation. In some cases the so-called "true stress," obtained by dividing the load P by the actual area of cross section A existing when the load P was applied, is plotted as a function of the strain

Jan 1, 1937

By J. F. Pierce, S. M. Enterline

Since January 1959 a zinc refiner of novel design has been in operation at Blackwell, Okla., producing 99.995+ zinc from the output of the Blackwell horizontal retort smelter. The refiner is a continuously operated, pyro-metallurgical unit with principal dimensions horizonhl permitting one floor operation. It is very ruggedly constructed. Furthermore it is not subjected to deterioration from high concentrations of iron in the feed metal because the boiling units are separate from the rectification columns and constructed with silicon carbide brick arches through which the heat is transferred radiantly to the zinc. A zinc refiner of novel design has been in operation since January 1959 at the Blackwell, Okla. plant of the Blackwell Zinc Co., Inc., a wholly owned subsidiary of American Metal Climax, Inc. Developed by the company&apos;s technical and operating staffs, the new refiner produces special high-grade zinc (nominally 99.995+ pct Zn) from the prime western1 slab output of the Blackwell horizontal retort smelter. The refiner is a continuously operated, pyromet-allurgical, high-capacity unit employing fractional distillation to separate zinc from its impurities, consisting principally of lead, cadmium, and iron. In prime western slab, these elements may vary in concentration from 0.005 to 1.6 pct. Table I shows the impurities usually encountered in the Blackwell prime western metal fed to the refiner together with their boiling points and vapor pressures at 907oC. The commercial pyrometallurgical smelting processes for extracting zinc from ore include distillation from retorts and a limited degree of refining can be accomplished by redistillation in similar retorts. To achieve special high-grade purity, an impractical number of batch redistillations would be required, however, with an accompanying loss of much metal. A continuously operated and integrated unit is required in which fractional vaporization and condensation can take place in a large number of stages. The first commercial continuously operated unit was developed by the New Jersey Zinc Co.4 In the separation of any two substances the degree of separation is limited if a mixture exists having a constant boiling point. The Zn-cd5 and Zn-pb6 systems contain no constant boiling points and hence these metals may be separated to any degree of purity. Basically, the pyrometallurgical refining of zinc involves three steps: a) iron, copper, and other metals having no appreciable vapor pressures at 907ºC concentrate in the bath when the impure zinc is boiled, b) lead, bismuth, antimony, and other metals having boiling points above but closer to that of zinc are selectively condensed from the vapor boiled from the bath, and c) cadmium and other metals having lower boiling points than zinc are fractionally distilled by reboiling and subsequent condensation of the zinc from the vapor. The boiling and condensation of zinc must be conducted in vessels constructed of materials which are refractory at the temperature involved (907 ºC) and it is highly desirable that they also be resistant to attack by the various metals. This requirement dictates construction from relatively small, simply shaped pieces which limits the pressures which may be employed to avoid leakage through the numerous joints. Stresses induced must be limited essentially to compressive ones and suitable provision must be made to permit thermal expansion of the components in order to minimize these stresses. Where heat is to be added for boiling or removed for condensation, refractory material through which the heat flows must have a high thermal conductivity. Silicon carbide is highly conductive but is subject to attack by iron and is expensive compared to other commonly employed refractories. A hard, dense aluminous fireclay is well suited to contain these metals where high thermal conductivity is not required. Zinc will penetrate the pores of fireclay brick but only to a limited depth in an exterior wall and has little effect other than an increase in weight and conductivity. The design objectives of the Amax refiner were: a) to achieve a long life by heavy, rugged construction and by employing silicon carbide refractories only where required for heat conductivity and not in contact with liquids of high iron concentrations, b) to simplify operation, manning and control by essentially horizontal construction, and c) to obtain high capacity in a single unit. DESCRIPTION Flow of metal through the Amax refiner is shown diagrammatically in Fig. 1 and schematically in Fig. 2.

Jan 1, 1963

By Godfrey T. Vivian

Very often important discoveries are made in one industry that may be used to advantage in another, but, owing to the rarity that men step out of one industry into another, these discoveries remain unknown outside of the trade or profession in which they are made. The present paper is written solely with the object of bringing to the notice of mining and metallurgical engineers a centrifugal ore-concentrator which eventually may have a great application. Ore- Grading. Fig. 1 represents the action which takes place when solids of different dimensions are stirred up in a box and allowed to settle as minerals of the same size but of different specific gravity. This principle is applied practically in grading china-clay and in enriching tin-slimes. In the latter case the slimes are stirred around in a tub with water and allowed to settle while at the same time the side of the tub is struck with a hammer. The colloidal slimes are then poured off and various slices taken off horizontally. The great drawback of this process is that the particles are deposited horizontally and all the colloids are lost. Fig. 2 represents the action in which the particles are deposited side by side. Here the drawback is the great length of the box needed in order to prevent excessive loss. The alternative to lengthening the box is to increase the force of gravity. Centrifugal force may be regarded practically as the force of gravity augmented. Fig. 3 illustrates the Gee centrifugal machine for grading ores. The drum, A, fitted with a box, B, is mounted on a shaft or spindle, C, the whole being suspended from a ball-bearing of special design at D, supported between girders, E. Rota-

Jan 1, 1913

By W. C. Coffin

The refractory linings of open-hearth steel furnaces above the bath line are subject to severe wear not only from the heat caused by the combustion of the fuel and the reactions of the bath, but also from the melting action of the gases when not controlled and directed, and from the scouring of the oxides, etc. with which the products of combustion are charged. The framework that encases or binds the furnace is made up primarily of an iron or steel pan in which the furnace proper is built, side and end buckstays, and tie-rods. The expansion and contraction are so great and variable that the bindings may be subjected to severe stresses unless the tie-rods are carefully adjusted in heating up the furnace, but they are most affected by direct heat and usually become deformed from that cause when the lining is worn thin and, sometimes, when sections of the lining fall in and expose some of the framework. A deformed framework displaces the skewback of the roof arch and tends to distort or crush the roof. Bent buckstays deform the front wall, causing the door frames to stand away from the lining so that the gases burn between the lining and the frames, destroying both of them. Frequently the frames are attached to the buckstays; then when the latter bend the frames usually break. Preventing the distortion of the framework and maintaining the economy of the refractories are real factors in the cost of steel making. Nat only does the cost of general repairs and reconstruction add directly to the cost of steel produced, but the time lost in making repairs cuts down the steel production and increases the overhead expense of both the furnace shop and its allied foundry or mills. Many years ago water-cooled equipment applied to iron blast furnaces made it possible to increase greatly not only the size and production of the furnaces but also the life of the lining. It also cut down the loss from frequent repairs. The open-hearth furnace is a much later invention, especially as a commercial factor; for though it dates from the Fred Siemens patent of 1856, much more progress was made in the Bessemer process until the latter eighties and most of the development

Jan 1, 1920

By L. G. Austin

If S (x) is the specific rate of breakage of size x and B (x, y) (see Table 1 for Nomenclature) is the cumulative breakage distribution function, the Herbst Fuerstenau2 assumption is that Inserting this assumption into first-order grinding equations it has been shown" that there are then simple analytical solutions to the grinding equations, as shown in Table 2. In this context "plug flow" is defined as all material passing through the mill in the same length of time, the residence time t. The term "n fully-mixed" means that the mill has a residence time distribution" which can be treated as if the mill were n equal fully mixed sections in series. In addition it has been shown that the assumption of Eq. 1 also leads to simple analytical solutions for closed-circuit, steady-state grinding with an ideal classifier at the mill exit returning oversize to the mill feed. The solutions are also given in Table 2, with µ as the ideal classifier cut size, C the circulation ratio, and Q (x) the size distribution of the circuit product. The specific surface area of these size distributions is where the density-shape factor k. is assumed to be constant with size. In practice, most methods of size analysis or area [ ] measurement have a finite lower limit, so that the integration is really performed from xm, to xm, For a realistic degree of grinding the value of So is dominated by the fine sizes because of the 1/x factor. Consider batch grinding of a feed of size y to y + dy. The batch grinding solution given in Table 2 is then [ ] The fresh surface area produced is the area of the fines plus the area of the original material remaining minus the area of the original material, [ ] Little error is introduced by neglecting the last term on the right-hand side since at t = 0 it is zero, and when t is significant the first term dominates because of the fine sizes produced. In addition, the form of P (x, t) for [ ] realistic values of S (x) 2t ax° is such that the major fraction of fresh surface produced is contained within the bottom 10% of weight of broken material, that is, for sizes for which P(x, t) < 0.1 (providing y is not near x.,). Thus for surface area purposes Eq. 3 can be approximated by [ ] becomes providing again that the feed sizes are coarse relative to xmi. Then the fresh area production is and W is the mass in the mill. The rate of surface production is WK, and the specific surface is Kt. From Table 2, the specific energy is mt/W so surface production per unit energy is [ ] Surface produced per unit energy input = KW/m (8) where m is the energy input of the mill. Clearly, identical reasoning applies to open-cycle, plug-flow grinding, with t replacing t, and Eq. 8 is obtained again. Considering open-cycle, fully mixed grinding, similar reasoning gives P(x) - t S(x) for surface area purposes, and

Jan 1, 1974

By G. V. Jere, C. C. Patel

Chlorination of the various constituents of ilmenite by different chlorinating agents in presence of various reducing agents, have been considered on the basis of the standard free energy and standard enthalpy changes as a function of temperature. The standard free energy change considerations show that it is beneficial to chlorinate ilmenite by chlorine in the presence of carbon and also that iron constituent of ilmenite can be preferentially chlorinated by clzlorine, titanium tetrachloride or their mixture. These findilzgs have been corroborated from the published work. METALLURGICAL processes involving the use of titanium tetrachloride have gained in importance because of the use of the latter in the manufacture of titanium metal. Since ilmenite is more abundant in nature than any other titanium mineral, the future of the metallurgical processes depends on the utilization of ilmenite for the production of titanium tetrachloride. In these laboratories, investigations have been carried out on the chlorination of ilmenite under a variety of conditions.1&apos;2 During these studies, it was noticed that 1) preferential chlorination of iron was effected at low temperatures (400° to 600°C) and at low carbon content (6 to 7 pct), 2) carbonyl chloride retarded the chlorination of iron oxides and titania perceptibly, while 3) carbon-tetrachloride, compounds of sulphur and some other catalysts favored the chlorination. Moles3 has found that oxides of iron are chlorinated in preference to titania at high temperatures, while wilcox4 has claimed the preferential chlorination of titania between 1200" and 1500°C. It has been shown in this paper that preferential chlorination of titania claimed by Wilcox is not likely to occur. Daubenspeck and coworkers5,6 have claimed the preferential chlorination of iron by chlorine or by a mixture of titanium tetrachloride and chlorine between 700° and 1050°C in the absence of carbon. Even when plain titanium tetrachloride is employed as the chlorinating agent, pascaud7 noticed the preferential chlorination of iron and other oxides. The purpose of this paper is to explain from thermodynamical considerations, the various chlorination reactions studied so far. ILMENITE CONSTITUENTS AND THEIR CHLORINATION PRODUCTS Although the general composition of the ilmenite mineral is represented as FeTiO,, most of the ilmenites found in nature have variable quantities of TiO2 (44.6 to 64 pct), FeO (4.7 to 36 pct) and Fe2O3 (6.9 to 28 pct).8 The higher content of ferric iron in ilmenites was attributed by Millerg to the presence of arizonite (Fe2O3.3TiO2). But the X-ray studies by Overholt, Vaw, and odd" have shown that arizonite is a mixture of haematite, ilmenite, anatase, and rutile. Except for the anatase, similar views have been advanced by Lynd, Sigurdson, North, and Anderson8 from magnetic, X-ray, and optical and electron microscope studies. The ilmenite ores can, therefore, be assumed to consist of mineral aggregates of ilmenite, rutile and haematite. From the free energy of formation of ilmenite (FeTiO3), it has been shown by Kelley, Todd, and King11 that ilmenite is stable even up to its melting point (1367°C) and would not undergo decomposition into its constituent oxides. Schomate, Naylor, and Boericke12 have found that in the presence of a reducing agent the iron constituent of ilmenite is selectively reduced. The reaction of chlorine with ilmenite in presence of a reducing agent can, therefore, be synonymous with that of the reaction of chlorine with the constituents of ilmenite, viz., TiO2, FeO, and Fe2O3. Most of the reaction products of chlorination of ilmenite in the presence of reducing agents will be in equilibrium with their dissociation products, depending on the temperature. The titanium tetrachloride is, however, quite stable up to 1500°C due to its covalent nature. The equilibrium for the ferric chloride system has been investigated by Kangro and Bernstorff, 13, schafer14 and Kangro and petersen,15 and the results are summarized in Fig. 1, curves a, b, and c respectively. From these results, it is clear that the ferric chloride disociates as follows: 324° to 700°C FeaCl6(g) ?2FeCl2(c) + Cl2(g) [1] 324°to 900°C Fe2Cl6(g) =2 Fe Cl2 Reaction [I] (curve a) occurs in the forward direction to about 6 pct at 400°C but falls off very rapidly with increase in temperature and beyond 600°C, it is practically negligible, perhaps due to the formation of the stable monomer, FeC13(g). As the temperature is further increased, the amount of FeCl,(g) in-

Jan 1, 1961

By C. V. Millikan

When a flowing oil well is being drilled in with cable tools, it is difficult to determine when an additional streak of pay sand is drilled. By placing a gas meter on the gas-release line from the oil and gas separator, any increase in volume of gas that comes with oil production is recorded. In addition to the better knowledge of sand conditions, these data are a valuable aid in determining the size and depth of shots, plugging off water, and estimating ultimate production. The meter also gives a record of operation while the well is drilling in; and if allowed to remain on the well after completion will give information that may lead to a more efficient recovery of the oil from the sand. A VERTICAL cross section of any oil sand will show great variation in porosity and oil content. In some sands, the entire thickness contains oil, the variation being only the degree of porosity or oil content, but more often the pay streaks are distinctly separated by shells or barren streaks. These pay strata vary in number and may be thin or thick. The total thickness of the sand may be several tens of feet while the part containing oil may be only 1 or 2 ft. thick. The amount of production is not proportional to the thickness of the sand but rather the thickness of the pay streaks. If the total thickness of the sand or the amount that can be drilled is small, or if the initial production is small, the depth at which each stratum of pay is encountered can be determined sufficiently accurately for all present economic purposes. However, when drilling through sand of considerable thickness, giving large initial production, especially where conditions necessitate that the production go through the same gas trap with that from one or more wells already producing, it is difficult to determine the depth at which the pay strata are encountered even accurately enough to guide the placing of shots, and small pay streaks are apt not to be recognized at all.

Jan 9, 1925

By S. G. Gibbs

A new method for predicting the behavior of sucker-rod pumping systems is presented. The pumping system is described by a flexible mathematical model which is solved by means of partial diflerence equations with the aid of computers. Polished rod and intermediate-depth dynamometer cards can be calculated for various bottom-hole pump conditions. The technique permits simulation of a wide variety of operating conditions, both normal and abnormal. The data generated with the new technique are useful in refining the criteria for design and operation of sucker-rod systms. INTRODUCTION Sucker-rod pumping systems are used in approximately 90 per cent of artificially lifted wells. In view of this wide application, it behooves the industry to have a fundamental understanding of the sucker-rod pumping process. Oddly enough, our understanding has been rather superficial. This is evidenced by the semi-empirical formulas which have been used as the basis for design and operation of sucker-rod installations. Thoueh- we have realized the limitations of our methods for many years, it has not been computationally feasible to use more refined techniques. With the advent and widespread use of digital computers, it is now possible to handle the mathematical problems associated with sucker-rod pumping. This paper summarizes a computer-oriented method which can provide greater insight into the sucker-rod pumping process. It is hoped that this technique, and techniques which may evolve from it, will prove to be the tool needed by industry to obtain the most efficient use of rod pumping equipment. THE MATHEMATICAL MODEL Prediction of sucker-rod system behavior involves the solution of a boundary value problem. Such a problem includes a differential equation and a set of boundary conditions. For the sucker-rod problem, the wave equation is used, together with boundary conditions which describe the initial stress and velocity of the sucker rods, the motion of the polished rod and the operation of the down-hole pump. Of these items, the wave equation, the polished rod motion condition and the down-hole pump conditions are of primary importance. Discussion of the mathematical model centers about these factors. ROD STRING SIMULATION WITH THE WAVE EQUATION The one-dimensional wave equation with viscous damp- is used in the sucker-rod boundary value problem to simulate the behavior of the rod string. This equation describes the longitudinal vibrations in a long slender rod and, hence, is ideal for the sucker-rod application. Its use incorporates into the mathematical model the phenomenon of force wave reflection, which is an important characteristic of real systems. The viscous damping effect postulated in Eq. 1 yields good solutions, even though nonviscous effects such as coulcomb friction and hysteresis loss in the rod material are present. Fortunately, the nonviscous effects are relatively small, so the viscous damping approximation used in the wave equation is adequate. The coefficient v is a dimensionless damping factor which is found in field measurements to vary over fairly narrow limits. For mathematical convenience the gravity term is omitted in Eq. 1. The effect of gravity on rod load and stretch can be treated separately, as will be noted later. Since Eq. 1 is linear, the legitimacy of this procedure is easy to demonstrate. POLlSHED ROD MOTION SIMULATION The motion of the polished rod is determined by the geometry of the surface pumping unit and the torque-speed characteristics of its prime mover. By determining the motion of the polished rod, we formulate an important boundary condition. From trigonometrical considerations it can be shown that the position of the polished rod vs crank angle 0 is given by (see Fig. 1) These equations are obtained from the general solution of the "four-bar" linkage problem and can be used to describe the kinematics of any modern beam pumping unit.&apos; If prime mover speed variations are disregarded, the angular velocity of the crank is constant, and Eq. 2 can be used to predict the position of the polished rod vs time. However, the constant-speed condition leading to constant crank angular velocity is only approached in practice: hence, it is better to make provisions for prime mover speed variations in the mathematical model. The speed at which the prime mover runs is determined by its torque-speed characteristics and the torque imposed upon it. The torque that the prime mover "feels" is the net torque arising from the polished rod load and the opposing torque from the counterbalance effect. The

By J. L. Huitt

Some of the problems associated with the acid treatment of oil wells are related to the control of the composition of formation treating acid. One test usually made at the well site is the determination of the acid concentration. Heretofore, the concentration of the acid delivered to the well site usually has been interpreted from a hydrometer measurement of the specific gravity of the acid solution. Experience has shown that this indirect measurement of acid concentration can give erroneous results. More reliable results are, of course, obtainable by the titration method; however, this method is not easily adapted to well-site testing. To overcome these objections, a device was developed for use in the field which permits determination of the concentration of treating acid both quickly and accurately at the time of the acid treatment. Its purpose was three-fold, namely, to determine: (1) the concentration of the fresh treating acid, (2) the concentration of the spent acid returning from the well, and (3) the solubility of formation samples in treating acid. The device was designed to operate on the principle of the stoichiometric relation between the calcium carbonate—hydrochloric acid reaction and the carbon dioxide gas resulting from the reaction. By confining the carbon dioxide gas within a reaction cell of the type shown in Fig. 1, the pressure inside the cell is increased. Since the pressure is an indication of the quantity of carbon dioxide gas produced, it may be used to estimate the concentration of the acid, provided an excess of calcium carbonate is used. From information on the volume of the reaction cell, the volume of acid used, and the pressure and temperature of the gas after the completion of the reaction, the concentration of the treating acid may be computed. The reaction cell is essentially a pressure vessel equipped with a pressure gage, temperature indicator. pressure release valve, and a special sample holder. Plastic and metal construction makes the cell both rugged and acid-resistant. The sample holder is so designed that a sample of calcium carbonate (or sample of carbonate rock) can be dropped into the acid

Jan 1, 1956

By Roscoe C. Clark, Henry F. Coffer, J. J. Reynolds

A cement slurry lightweight additive has been adapted in the Conoco laboratories for use in oil well cements. This additive makes possible the use of air to lighten oil well cement slurries. Specifically, the additive consists of small clay bubbles of air having sufficient strength to resist crushing by bottom hole pressures. Clay bubble cement slurry weights can be safely reduced to 10 Ibs/gal. In addition, the clay bubbles tend to act as lost circulation materials and to provide a cement texture which should produce good perforating characteristics. Clay bubble cement is relatively impermeable. INTRODUCTION In many areas in Oklahoma, Texas, Wyoming, and California, difficulties are experienced during casing cementing operations with lost returns caused by the high density of the cement slurries. Wells in these areas are ordinarily drilled with 9 to 11 lbs/gal. drilling mud while neat cement slurries may range in densities from 14.5 to 17 lbs/gal. In these areas, cement slurry weights are at present being successfully reduced to around 12 lbs/gal. (under bottom-hole conditions) by the use of additives in the cement. Since the use of additives will decrease the strength which the cement will develop, the amount of additives which can be used must be based on the minimum cement strength which is acceptable; and thus the maximum slurry weight can be reduced. At present, the minimum tensile strength generally acceptable is 50 lbs/sq in. cured for 24 hours under bottom-hole temperature. This figure is based on laboratory tests1 and on a large number of cement jobs which have been conducted using cement which will not develop more than 50 psi tensile strength in 24 hours under bottom-hole conditions. Two additives are now in use for decreasing cement slurry weights. These are expanded perlite and/or bentonite. The density of both of these materials is greater than that of the cement slurry; however, large quantities of water may be added with these materials without producing a slurry which will settle out of suspension. It is these large quantities of water which contribute to the reduction in the slurry weight. The minimum slurry weight at present obtainable with expanded perlite and/or bentonite is approximately 12 lbs/gal. using a standard Portland cement slurry. In many areas, this weight reduction is insufficient; and returns are still lost during casing cementing operations. In many cases, the pay formation itself is fractured; and a considerable quantity of this cement is lost to the pay zone. It is therefore believed that if cement slurry weights can be reduced to as low as 10 lbs/gal., two advantages will accrue: 1. The lighter densities (10 to 12 lbs/gal.) should mitigate or eliminate lost returns during casing cementing operations. 2. Cement slurries above 12 Ibs/gal. (the present minimum limit ) should develop considerably more strength than is now being obtained. A tensile strength of 100 psi is desirable.&apos; It is the object of this paper to describe a cement slurry having a weight of 10 lbs/gal. and capable of

Jan 1, 1955

By Charles Himrod

IN presenting this paper it is not intended to enter into any discussion of the theory of the blast-furnace, but simply to give the results of a number of determinations of CO and CO2 in furnace gases, and some conclusions arrived at, and the result of an experiment made in hopes of increasing the production of CO2. In the first table, on page 198, is given the averages of a number of analyses of gases of different furnaces, and in the second, of two stacks of different sizes under varying circumstances. The conclusions arrived at as to what influences the production of CO2 are as follows: 1st. Kind of fuel. Bituminous coal not permitting the formation of as much CO2 as coke. 2d. Kind of ores. Rolling-mill cinder being much less favorable to formation of CO2 than hematite ores, magnetites probably less than hematites, but more than cinder. 3d. Length of time of contact of gases with ore. Small furnaces and too rapid driving both waste fuel by not allowing enough time for conversion of CO into CO2. 4th. The temperature of blast. The hotter the greater the quantity of CO2. 5th. Regularity of passage of stock through the furnace. The hanging and dropping of the stock, however slight, seems to pack it more solidly in the hearth, increases the resistance to the blast, and decreases the quantity of CO,. These are the most common causes noticed which influence the production of CO2, unless we except the one that might be considered the greatest of all, the one that has spoiled so many tons of iron, and the amiability of so many furnacemen, the one most dreaded, the great unknown. It would seem a self-evident proposition that the better the contact of the gases with the ore and the less with the fuel, the greater would be the amount of CO2 produced. To prolong the contact of gas with the ore furnaces are enlarged with advantage, and pains are taken to charge the stock in such a, manner as will best promote it. Still, with furnaces of most approved construction and most skilful manipulation, the gases leave the furnace so rich in CO, that not half the heating power of the fuel is obtained, and the highest

Jan 1, 1877