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By J. Chipman, H. R. Larson

The data previously reported for the quantity as a function of oxygen pressure at 1550°C have been used to compute the activities of Fe, FeO, Fe2O3, and COO in slags of the ternary system. Activities of the first three have been obtained also for two quasi-ternaries involving fixed CaO:SiO2 ratios. IN a previous paper1' the authors reported the results of an investigation into the effects of oxygen pressure on the composition of various simple slags analogous to some of those which are found in steel-making practice. The ratio of ferric iron to total iron was studied at 1550°C in iron oxide melts to which lime, magnesia, lime-plus-silica, and other oxides were added. The oxygen pressures involved those of air, carbon dioxide, and carbon dioxide plus carbon monoxide in several proportions. Although very low oxygen pressures could not be used, the slag-metal equilibrium studies of Fetters and Chip-man' permitted extending the results to slags in equilibrium with iron. For the ternary system CaO-FeO-Fe,O, the oxygen pressure-composition relationship has been determined from zero percent lime to lime saturation over an oxygen pressure range from air to that represented by equilibrium with liquid iron. Lime and silica were added to iron oxide in the ratios 0.54, 1.306, and 2.235 to form three quasi-ternary systems which were also studied over the entire region of liquid melts at 1550°C. Ternary Gibbs-Duhem Equation Wagner" has developed a method by which the activities of two components of a ternary system can be calculated if' the activity of the third component is known throughout the composition range being considered. The fundamental form of the Gibbs-Duhem equation for ternary systems is N, d In a, + N2 d In a, + N3 d In a3 — 0. Wagner has developed a usable form of this equation by introducing the term y = N3/(N3 + N1) and rearranging the equation to give (? In a1/?N2)x = -y/(1-N2)2 (? In a2/?y) x2 N2/1-N2 (? In a2/?N2) y To apply this equation to the slag system CaO-FeO-Fe,O,, the activity of one of these components must be known. However, the only activity which is known from the experimental data is the activity or pressure of oxygen in the gas phase with which the slag is in equilibrium. The activity of oxygen in the slag can be defined as the square root of the oxygen pressure. In order to use oxygen as one component, the composition of the slags must be converted to the basis Fe-O-CaO. Oxygen, exclu-sive of that contained in CaO, then becomes com-ponent 2 in Eq. 1, Fe is selected as 1 and CaO as 3. Then y = Ncao/(Ncao + NFe). Eq. 1 then becomes (? In a fe/? Nx) y = -y/(1-No)2 (? In ao/?y) xp - No/ 1- No (? In ao/ O No) y. In order to evaluate Eq. 2, the boundary conditions must be known. The obvious choice of a standard state for iron is to assign slags in equilibrium with iron an activity of one. Then In a,., or log aFe, which is substituted for convenience, is determined by integrating along a line of constant y from the slag in equilibrium with iron to the composition at which log a,, is to be determined. Mathematically this can be expressed as log aFe (Nlog y) = log a'Fe + (? log a Fe/? No) dNo where the primes indicate equilibrium with liquid iron and a'Fe = 1. When Eq. 3 is integrated along a line of constant y, the following is obtained: log a Fe (No, y) = - y No ?/ No ? y ( log ao/(1- No)2) No d No - No/1-No d log ao. Lime-Iron Oxide Slags Iron Activity: The oxygen pressure of lime-iron oxide slags is shown in Fig. 1 as a function of j, de-fined as j = Fe+++/(Fe++ + Fe +++) for various constant mol percentages of lime. The j values at 0 to 60 pct lime were then determined for oxygen pressures of 1, 10-1, etc. to 10-" atm. For purposes of calculation, the line for zero percent lime was extrapolated to

Jan 1, 1955

The selection of a particular machine for production drilling is the most critical drill evaluation the pit engineer is called upon to make. It is a true engineering design problem requiring value judgments. Generally, the procedure follows these steps: (1) Determine and specify the conditions under which the machine will be used, including such service factors as labor, site, weather, etc. (2) State the objectives for the rock-breakage phases of the production cycle of operations--considering excavation and haulage restrictions, crushing capacity, production quota, and pit geometry-in terms of tonnage, fragmentation, throw, etc. (3) On the basis of blasting requirements, design the drill-hole pattern (hole size and depth, in- clination, burden, spacing, etc.) (4) Determine the drillability factors and select the drilling methods which appear feasible for the kind of rock anticipated. (5) Specify the operating variables for each system under study, considering drill, rod, bit and circulation fluid factors. (6) Estimate and compare performance parameters, including costs. Major cost items are bits, drill depreciation, labor, maintenance, power and fluids. (7) Select the drilling system that best satisfies all requirements with the lowest over-all cost.

Jan 10, 1967

By H. Kahata, I. Iwasaki, Y. Takahasi

A combined process of segregation roasting-flota-tion or magnetic separation was developed to recover nickel from lateritic iron ores and oxidized nickel ores. An ore was mixed with a halide, such as sodium or calcium chloride, and a solid reductant, and roasted, whereby the nickel content was segregated out as discrete metallic particles. Either by magnetic separation, or by flotation using a sulfhydryl collector together with a heavy metal salt as an activator, the metallic nickel could be concentrated, Effects of such variables as the types and amounts of the halide and solid reductant addition and of the roasting conditions were extensively investigated. The concentration results on several types of ores from Japan, the Philippines, and New Caledonia are presented. Laterite is a residual product of rock decay in tropical and subtropical regions, and consists mainly of hydrated oxides of iron and alumina. Those derived from serpentine sometimes become enriched in nickel, cobalt, and chromium contents. Oxidized nickel ores are of the similar origin, but their nickel as well as silica contents are higher due to gamierite-type silicates. Apparently, nickel enrichment is more pronounced in the transition region between the surface layer of iron laterite and the underlying serpentine. Iron laterites often contain over 50% iron, and their reserve is reported to exceed 22 billion tons, corresponding approximately to 20% of the world iron ore reserve.1 It is readily apparent, therefore, why the iron laterites have attracted much attention of the steel industry as a potential source of iron ores. Numerous attempts to remove nickel and chromium as byproducts, have been reported in literature.' Worldwide discoveries of high-grade iron ore deposits in recent years have inevitably lessened the interests in iron laterites. However, in view of the tremendous potential for their gross value and supplies of nickel, cobalt, chromium, and alumina along with iron, the problem remains as a challenge. Much of the chromium in laterites is present in the form of relatively coarse particles of chromite, and various classification methods have successfully been applied for its removal.2,3 The nickel, however, is intimately associated with limonite, and ordinary concentration techniques are totally ineffective. Much attention has, therefore, been given to hydro-metallurgical or pyrometallurgical means. Yet, all the known processes appear to have limitations either economically or for the use of products as iron raw materials due to a high residual content of nickel. Some attempts have been made to pre-roast laterites or oxidized nickel ores, particularly with sulfidizing agents, and to remove nickel either by magnetic separation,' or by flotation.4 It is apparent that any such concentration process would require grain growth of nickel during roasting for effective separation. Oxidized copper ores are reported to be concentrated by the segregation roasting-flotation process,5 in which the ores are roasted with a chloridizing agent and a carbonaceous reductant in order to promote the growth of metallic copper through repeated cycles of copper chloride volatilization and its reduction on the solid reductant surfaces. Examination of a vapor pressure-temperature diagram of various metal chlorides indicates that a separation of nickel from iron may be effected by a similar process. In fact, the segregation roasting of laterites was reported to increase the extraction of nickel by the ammonia leach process, as compared to the ordinary reduction roasting.6 In the present article some of the preliminary experimental results of the segregation roasting, followed by either flotation or magnetic separation, on laterites and oxidized nickel ores are reported. The effects of various parameters in the roasting as well as in the concentration steps are discussed. MATERIALS AND METHODS An oxidized nickel ore from Thio, New Caledonia, and three laterites from Homonhon, the Philippines, Wakasa and Miyagawa, Japan, were selected for the

Jan 1, 1967

By Russell S. Sage

THE electric motor has steadily replaced the steam and air engine for use in mine hoists, until today a new installation with other than electric drive is a rarity. Much existing steam-driven equipment has been changed over to electric drive. Driving power has grown in capacity since the initial electric unit rated 10 hp installed at Aspen, Colorado, in 1888, to 3000 hp and 4000 hp in the United States, and to 5500 hp in Canada-the largest in the Western Hemisphere. Electric installations now total in the thousands of units, a growth largely made possible by the development of large central electric-power stations and the extension of electric-power service to more mining areas.

Jan 1, 1949

By WOOLSEY MCA JOHNSON

INDEPENDENTLY of the recognized chemical reactions involved in the production of metallic zinc, the process is affected by physical conditions in efficiency, and by commercial as well as technical economy. To offer some observations concerning these conditions is the purpose of the present paper. Among the important elements of this problem is the physical nature of the particles constituting the mass of zinc oxide to be reduced. This may be the result, either of the manner of the original deposition of the mineral, or of the treatment to which it has been subjected in the roasting-furnace. The physical character of the reducing-agent is another important factor, since the carbon of some coals is much more active in reduction than that of others. The degree of fineness, whether of ore or coal, or both, likewise plays a significant part. These factors, together with the physical admixture of foreign substances with the ore, may give rise also to chemical "side-reactions," sometimes hindering or retarding, and sometimes accelerating, the reduction. Finally, thermal conditions, including the relative conductivity of the materials, deserve to be taken into account. In firing a furnace with retorts charged with a mixture of roasted ore and coal, the first reaction is naturally the boiling-off of the contained water ; the next is the distillation of the light hydrocarbons from the coal; the next is the reduction of the iron oxide to protoxide and sub-oxide successively, and then to metallic sponge; and the final reaction is the reduction of the zinc oxide in the ore by the carbon to metallic zinc. This reaction commences at 1,022° to 1,060° C., according to the physical nature and condition of the coal and ore. Since the retort and the charge are far from being good con-

Sep 1, 1907

By NEWTON B. KNOX

THE Guianas region is a geological unit, consisting of the northern lobe of the Brazilian Shield, but political accident and the fact that rivers act as the principal means of transportation have divided the region between five separate sovereignties. Brazilian and Venezuelan Guiana have already been considered. The French, Dutch, and British colonies consist of a coastal plain some fifty miles wide, which, together with the lower reaches of the principal rivers, support the greater part of the population. Inland from this tidewater region is a wide area of low, forest-covered hills, under-lain by gneisses, schists, granites, and pegmatites of the Shield. As in Venezuelan Guiana, these rocks are overlain by a thick series of horizontal continental sediments intruded by moderately basic magmas. Gold, bauxite and diamonds have been the principal products of the colonies. The first metal is quite widespread in the hill country. The quartz mines are small, though occasionally rich; probably the greater number of veins remain undiscovered because of the thick mantle of decomposition product that covers the schists and gneisses. The greater proportion of the gold, therefore, is derived from placers which are exploited in all three colonies. Some geologists claim that they occur in two belts parallel to the coast; whether this feature has its origin in the location of the primary mineralization or in the gradients of the rivers is not clear. In some instances the river gravels grade into auriferous laterite. The laterites are well developed in the Guianas and represent the weathering products of the more basic rocks.

Jan 1, 1946

By C. K. Leith

CERTAIN ideas on iron and steel sanctions to follow originated in a series of conferences held under the joint auspices of the War Department and Brookings Institute in Washington last spring. The views presented may be regarded as those of substantial segments of the steel industry. In view of the fact that steelmaking capacity can be so quickly converted to the production of armament, any effective control must necessarily include the entire steel industry and not solely the parts devoted to the production of implements of war. It must also be exercised all the way from production and shipment of raw materials through their ultimate conversion into finished products and use. Control will be dis- cussed under two main headings: (I) control of raw materials at the source; (2) control of steel capacity within the Axis countries.

Jan 1, 1944

By John V. Beall

Since the U. S. Metals Refining Co. works was established, around the turn of the century, near the town which is now called Carteret, N. J., it has grown to be a major producer of refined copper and the main source of that special brand known as "oxygen-free high-conductivity copper." Owing to the complex metallurgical problems arising from handling a variety of raw materials such as copper concentrate from Matahambre, Cuba, copper and brass scrap from the New York area, and domestic blister copper, the organization is geared from top management down through its 2000 employes to maintain a high degree of flexibility in plant operation. The Company is a subsidiary of The American Metal Co. Charges for the smelter furnaces, one reverberatory furnace and one blast furnace, are made up in. bedding bins so that they may be tailored to the production of a constant grade of blister copper. The reverberatory furnace smelts the .sulphide charge, which may be a blend of ten different materials but principally the Cuban concentrate, and the matte from the process is poured into a converter. This reverberatory is 80 by 20 ft, silica lined with a slag bottom, fired by pulverized coal, and continuously side-charged from the top by bottom-dump cars which keep the side walls covered. It produces a 40 to 50 per cent copper matte. The fuel-charge ratio is 4.35 tons of solid charge per ton of coal. The furnace has a capacity of 10,000 tons of charge per month and produces from 5000 to 6000 tons of slag per month which must be disposed of. About 5000 tons of converter slag is produced monthly and returned molten to the reverberatory furnace. The converter gases go through a spray chamber to a Cottrell precipitator and thence to the flue system. Smoke from the

Jan 1, 1948

By Philip B. Bucky

WITH the exhaustion of the sections of iron ore bodies amenable to opencut mining the iron ore miners raise the question: "How can we mine the extensions of these ore bodies in depth with the same costs as obtained in opencut work?" This question brings to the fore the relationship between mineral exploration and research on mining procedures. The iron miners must either find new de? posits amenable to their known methods of mining or develop new mining methods for deep deposits. It is understood that the oil companies will spend $30,000,000 next year in the search for new oil fields. How much the metal mining companies will spend in the search for new ore bodies is unknown, but without doubt the amount will run into several millions of dollars. If the mining companies that concern themselves with metals, nonmetallics, and fuels will set aside a substantial sum for fundamental and applied research in mining methods, they can not only lower their costs but increase their reserves thereby. Any increases in mining efficiency automatically result in increased ore reserves at no cost.

Jan 1, 1947

By R. W. Raymond

FOUR portraits have recently been hung in the rooms of the Institute, in recognition of four illustrious men with whom we, as mining engineers and metallurgists, may claim fellowship. LUTHER. Martin Luther is often spoken of as a miner's son; but it is less generally known that John Luther, his father, was, in a small way, a metallurgist as well as a miner, and that Martin Luther himself, in his youth, worked in a forge or bloomary established by his father at Mansfeld, Saxony. Since this is the only manual occupation on his part of which we have any record, it is fair to assume that the great scholar and reformer derived from his work in this department the practical familiarity with the conditions of human labor so abundantly evinced in the homely illustrations which accompany even his serious arguments, and in the witty apothegms of his famous "table-talk." At the same time, I must confess that 1 have not been able to find in any of the works of Luther distinct allusions to mining or metallurgy. KÖRNER. Theodor Körner, a student at the Mining Academy of Freiberg, Saxony, threw himself into the German War of Freedom in the first decade of the 19th Century. He was a poet of no mean rank ; and his " Song of the Sword " is one of the great lyrics of literature. This poem was written but a few days before he died in battle. In many respects, Körner may be compared with our American hero Theodore Winthrop, who similarly met a glorious fate, and left behind him prophetic indications of genius, of which his premature death prevented the complete fulfillment. I am informed by a member of the Institute that Körner's admirable collection of minerals is still preserved at Dresden.

Nov 1, 1908

By W. J. Keep

Cast-iron, or pig-iron, is iron which contains all the carbon that it could absorb during its reduction in the blast-furnace. As is well-known to chemists, carbon exists in cast-iron in two distinct forms. In chemical union, as "combined" carbon, it cannot be discerned, except as it may increase the whiteness of the fracture, in so-called white iron, or carburetted iron (sp. gr. about 7.72). Carbon mechanically mixed with the iron as graphite is visible, varying in color from gray to black, while the fracture of the iron, according to the color and amount of graphite it contains, ranges from a light to a very dark gray. The specific gravity of graphitic iron is about 7.40. Silicon in cast-iron is evidently to some extent combined with the iron and the carbon ; but whether it exists also in a form corresponding with graphitic carbon, mechanically mixed with the remaining mass, is a question still in dispute, which we have not in this paper endeavored to answer. It has been the opinion of many writers on metallurgy, and many foundry men, that silicon is in every way injurious to cast-iron. Yet

Jan 1, 1889

By Charles White Merrill

Mankind's progress is measured in minerals. Man's emergence from prehistory is marked by passage through a Stone Age and a Bronze Age and into the present era, sometimes called the Iron Age or the Age of Metals. With the evolution of civilization and the development of a modem industrial economy, minerals become more and more important. Structures, roads, and machines are built largely of minerals; the energy to heat the structures and to drive the machines is mostly mineral; agricultural fertility is maintained by mineral fertilizers and water; and military strength is provided by fortresses, armaments, and munitions, largely of mineral origin. Thus in the material world, in the productivity of the economy, access to minerals has paramount importance. Every evidence indicates increasing dependence on minerals in the modem economy, particularly on the mineral fuels as energy sources to provide the power base for advancing industrialization. Both the total and the per capita consumption of almost every mineral is increasing in the industrialized nations. Moreover, nations with predominantly agrarian economies call themselves underdeveloped and universally strive to industrialize. Most mineral consumption trends in the more advanced economies have been greatly exceeding population growth-which itself has been advancing at an accelerating rate-and sometimes have surpassed the growth in real income. Some minerals have only recently been adopted or grown to importance in use. Titanium metal did not appear as a commercial product until 1948, and even coal seriously displaced wood as a source of heat less than two centuries ago. On the other hand, minerals have always played an important role in construction. The prehistoric megaliths that form the dolmens of Salisbury Plain are stone; the pyramids are andesite faced with limestone; and many other ancient structures are built of mineral materials. In modem times the whole course of architecture has been redirected by new building materials, mostly mineral. Most conspicuous is the sky-

Jan 1, 1964

By E. Parthe, J. P. Pemsler

TWO references can be found in the literature concerning the ternary system uranium-tantalum -carbon. C. H. Schramm, P. Gordon, and A. R. Kaufmam reported in this Journal1 on the existence of the ternary carbide "UTa10C4." They also report a second face-centered-cubic carbide phase in the system U-Ta-C, which they denote as "white" phase. The publication includes a reproduction of a Debye-Scherrer powder photograph of "UTa10C4" and a list of the sin2 0 values of this compound. H. Nowotny, R. Kieffer, F. Benesovsky, and E. Laube2 report the complete solid solubility between TaC and UC with a B1 structure. Since the ternary phase "UTa10C4" lies very close to the binary system Ta-C, and the established phase Ta2C with a C27 structure had not been mentioned by Schramm et al., it was thought worthwhile to compare the patterns of "UTa10C4" with Ta2C. The strong lines of the given pattern were indexed on a hexagonal unit cell with the approximate cell parameters a = 3.09A and c = 4.93A. These are the values reported for Ta2C in the literature.3 The correspondence between reported and calculated sin2 8 values may be studied in columns 4 and 5 of Table I. The agreement is fair, but there remain weak lines which cannot be assigned to the hexagonal unit cell. The extinctions correspond to those of Ta2C, but a comparison of the calculated and observed intensities of the Ta2C lines (columns 2 and 3) with those of the corresponding lines of "UTa10C4" (column 6) show occasional deviations. To clarify this situation, four new samples were prepared. The compositions of these samples were chosen in such a way as to observe any existing ternary phase in the system TaC-UC-U-Ta. The samples were arc melted in an inert atmosphere and annealed at 1100°C for 36 to 72 hr. Compositions of the samples determined by chemical analysis are given along with the results of X-ray investigations in Table 11. The following conclusions may be drawn from these data: a) No ternary compounds occur in the section TaC-UC-U-Ta of the ternary system Ta-U-C. The "white" phase reported by Schramm et al. corresponds to a solid solution between TaC and UC. Only one three-phase field exists: C27-B1-A2. (Both tantalum and ? uranium have body-centered-cubic A2 structures.) The a uranium observed in sample 4 transformed from the high-temperature ? phase on cooling. b) The phase Ta2C with a C27 structure extends into the ternary system. "UTa10C4" is, therefore, a uranium-enriched Ta2C. Good agreement is ob-

Jan 1, 1960

By Homer Griffield Turner

The nature and comparative features of anthracite and bituminous coals have been discussed by the writer in two previous papers.' Although this paper is offered as a further contribution to the subject, it seems desirable at the outset to repeat some of the descriptive matter of the early works in order to show the actual connection between various constituents of both coals and the new photomicrographs and other physical and chemical properties. Structure of Anthracite and Bituminous Coals A lump of bituminous coal (Fig. 1) is readily seen to be composed of layers differing from one another in texture, luster and thickness. There are, in general, three kinds of layers, although only two are usually seen. One is deep black, very compact, and has a bright luster; another is grayish black, has a duller luster and is less compact; the third is black, dull and porous in appearance, but because of its thinness is not often seen except on parting surfaces. This last material is charcoal. American students of coal morphology use the names anthraxylon, attritus, and fusain to designate these three constituents of laminated coal. Anthraxylon refers to the brightest bands, attritus to the duller layers, and fusain to the charcoal. Close examination of a lump of bituminous coal shows the brightest deep black layers to be embedded in the duller grayish black laminae. These deep black layers are lens-shaped and vary in thickness from thin sheets to over half an inch. They are often so continuous through the lump that their tapering terminae are not noticeable. On careful examination the duller grayish black laminae (Fig. 7) are seen to contain many very thin sheets of this very bright black material. The charcoal

Jan 1, 1930

By Leo Horvitz

PETROLEUM and natural gas are composed principally of the saturated hydrocarbons ranging from methane, the lightest, to nonvolatile liquids and solids containing approximately thirty-five carbon atoms. A technique for locating buried accumulations of these hydrocarbons before drilling obviously requires that some of the hydrocarbons leave the deposit and migrate toward the surface of the earth where they may be detected in their original form. Earliest attempts to link near surface hydrocarbons to petroleum at depth were apparently made by Laubmeyer1 in Germany and by Sokolov2 in Russia. These investigators collected samples of soil air from boreholes one to two meters deep and analyzed them for traces of hydrocarbons. They found that soil air over producing areas is richer in these constituents than is soil air over barren areas.

Jan 12, 1954

By A. Patton, F. N. Speller

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

Jan 1, 1917

By R. A. Pallanch

IN his recent paper, "The Controversial Art of Flotation," (Mining Technology, March, 1944) E. H. Rose states that "flotation is a science in so many variables that only art can blend them." This statement is apt. It contains meat. In other words, a valid scientific reason is behind every flotative effect. Some of these reasons we understand, but much the greater number of them still escape us. This does not prevent us from "going places," as familiarity and experience with the problems result in an increasingly intelligent and artful handling of these effects. Hypotheses are built up by the individuals concerned to explain certain happenings. Many of these hypotheses have to be abandoned when placed under the glaring scrutiny of actual trial. A few survive the severest of tests, come through unscathed, and are elevated to the rank of theories, something susceptible of certain chemical and physical explanation, under the conditions of the particular plant concerned. If these theories continue to hold water under all the variations existing in most milling plants, they gradually become accepted as facts in the minds of the plant operators. But-and here is a big BUT-these so-called facts may fall down completely in another plant working under an entirely different set of conditions. In other words, each plant tends gradually to build up its own facts, which may or may not be facts at another operation.

Jan 1, 1945

By Cyril Stanley Smith

Jan 1, 1949

By Cyril Stanley Smith

Jan 1, 1949

By P. L. Weston, S. E. Khalafalla

A systematic study was made by the Bureau of Mines on the effect of so me hypothesized accelerators for the process of wustite reduction in carbon monoxide. When small concentrations of promoter materials in the order of 0.69 at. pct were added to the reducible charge, the rate of reduction to iron was increased. Promotion phenomenon prediction was made in light of a suyface reduction mechanism with the aid of Vol'kenshtein's effect regarding the propagation of crystal lattice disturbances by small amounts of relatively larger interstitial ions. The acceleration produced by a typical promotor, such as potassiunl, increases with protnoter concentration up to a maximum, beyond which the reduction rate decreases. Concentration for maximum promotion depends on the nature and physicochemical properties of the promoter. The extent of reduction rate enhancement is found to be directly proportional to the atomic volume and electronic charge of the additive. DESPITE the enormous volume of literature on iron oxide reduction, very little is reported concerning additive or impurity effects on this important metallurgical process. The beneficial effect bf calcium compound additions on the reducibility of iron oxide sinters has been reported by Tigerschiold,1 vor dem Esche,2 and Edstrom. Doi and Kasai~ found that the addition of lime or limestone to iron ores helps to break up any unreducible compounds, such as fayalite or ilmen-ite. and thus free the combined iron for reduction. Schenck et al. 5 suggested that the increased reduction rate obtained when adding lime could be accounted for by the instability of wustite in the presence of lime. Acid-base slagging reactions resulted in wustite disproportionation according to The dicalcium ferrite formed will yield iron and calcium oxide during reduction. Regenerated calcium oxide dissociates more wustite. This mechanism has been used by Seths and white7 to explain their experimental results. Recently, Strangway and ROSS' attributed the calcium carbonate acceleration of iron oxide agglomerate reduction to increased porosity, both initial as well as that developed during reduction. Aside from calcium carbonate, or oxide, no other promoter was noted in the literature, except for a brief mention by Barrett and woodg on the effect of sodium carbonate and aluminate as activators for the hydrogen reduction of magnetite at 600°C. The present investigation systematically studied a host of other promoters, including calcium and sodium, in an attempt to elucidate the mechanism by which promotion takes place and to fit the results into a simple chemical model. To attain this goal, the effect of promoter physical properties, such as atomic volume, electronic charge, and concentration are related to wustite reduction kinetics in this paper. Wustite reduction to iron, rather than the overall hematite reduction, was chosen since this reaction is known to be the slowest, and hence the rate-deter mining step for the overall iron oxide reduction process. EXPERIMENTAL PROCEDURE Raw Materials and Their Preparation. The pure or impregnated wustite pellets were prepared from minus 400-mesh chemically pure hematite powders. A known weight of hematite was thoroughly and uniformly mixed with a calculated weight of the additive. The mixed paste containing 35 wt pct water was gradually heated from 400" to 1200° C and fired at 1200°C for approximately 4 hr in an air atmosphere. After cooling, the sinter was pulverized to minus 100 mesh and pelletized into minus 4- plus 5-mesh spheres. Pellets were fired, similarly to the paste mix, air-cooled, sized, and stored. An appropriate weight of the charge (20 g) was placed in a zirconia reduction tube maintaining a uniform oxide bed height of 1 cm and a cross section of 7.1 sq cm for all of the test runs. The samples were supported in the vertical reaction tube by a bed of fragmented insulating firebrick plus 3- to 6-mesh alumina beads. The hematite was then transformed to wustite by reduction with a 30 pct CO2-70 pct CO gas mixture at 1000°C in a globar furnace. Complete conversion to wustite was ascertained by a continuous infrared gas analyzer recording the CO-CO2 content of the effluent gas until no carbon monoxide was absorbed from the inlet gas, and inlet-outlet gas analysis remained constant for 30 min. The wustite sample was then reduced with 100 pct CO at 100WC. From the recorded data, an initial rate of reduction was determined by the initial slope of the graph percent reduction vs time. In order to estimate the accuracy of the data, five separate determinations of the reduction curve of pure wustite, under otherwise identical conditions, were performed. The maximum deviation from the average reduction at 14 min amounted to 2 2 pct reduction. This deviation corresponds to 3.8 pct variation based on the percent reduction of the sample. Aiiy impurity effect below the limits of this maximum deviation was considered a spurious result. If the effect exceeded + 4 pct, then it was considered as a positive one. Considerable care was exercised in determining the initial rate from the slope of the initial segments of the curve. Each reduction curve was examined separately on large graph paper and the best tangent to the curve at zero time was drawn. The slope of this tangent was taken as a measure of the initial fractional reduction per minute. Although the time required to reach 50 pct reduction may be of special practical significance, initial rate measurements are invaluable in fundamental studies. These rates provide a measure of the process kinetics on the initial

Jan 1, 1968