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By L. P. Durham

DuRing the early mine development period, 1929 and the first part of 1930, a 300-ton pilot-plant concentrator was built at Nkana mine of the Rhokana Corporation, Northern Rhodesia. This plant operated from May 26, 1930 until Oct. 26, 1931, treating 101,080 tons of Nkana ores and producing 4372 tons of concentrate. The plant was built, primarily, as a test unit to determine the grinding characteristics, floatability, etc. of the Nkana ores and other ores of the Rhodesian copper belt and to supply sufficient data on which to base the design of a 5000-ton concentrating plant at Nkana mine. The test unit operated wholly on development ores and no attempt was made to grade or select the ores from any section of the mine. The average assays for the 17 months of operation are given in Table 1. The first ground was broken for the 5000-ton concentrator during June, 1930, and the construction of the plant was completed in November, 1931. The plant started on Dec. 10 and has operated continuously since that date: The whole of the concentrating plant is compact and closely connected, yet with sufficient space for expansion of all sections up to 20,000 to 25,000 tons per day capacity. Mining operations are carried on along a length of about four miles on the easterly limb of the Nkana syncline. This length includes the North orebody, from which all production has thus far originated, and the Mindola orebody, now being developed for production. The ore-bearing measures in the North orebody are leached for some 75 ft. below the surface; the oxidized zone varies in vertical extent from 100 to 150 ft. Practically all the ore below the 200-ft. level is sufficiently

Jan 1, 1935

By W. W. Wirth

RESEARCH looking toward the reduction of the cost of roof support by substitution of longer-life materials for wooden timber is fully justified by the fact that roof support is an important element of all production costs. Permanent or semipermanent roof support will reduce the expense of timber-maintenance crews during steady operations, but even more markedly during idle periods. The management, therefore, is faced with the important problem of timber renewals, which in times of regular operation are frequently obscured by more urgent problems of production. Increased use of timber in the Anthracite Region of Pennsylvania is caused mainly by increased percentage of coal obtained from robbing areas, which requires more timber for safety than develop-ment work, and maintenance of long haulageways through crushed ground despite the fact that less coal is transported over them. The timber reserve in the immediate vicinity of the mines has been depleted to such an extent that it is necessary to secure 70 per cent of the timber requirements from distant sources. Originally, mine timbering in this region was done by largely utilizing round props or legs with round collars. The whole cross section of the tree from which timber was cut was utilized by forming the joints between the legs and the collars with saw and adze, using plank or round saplings for lagging behind the legs and over the collars to prevent material falling between them. The Mine Inspectors' report of 1898 records an important digression from the use of round timber, when two tunnels at the Babylon colliery, near Pittston, Pa., were timbered with 12 by 12-in. square timber sets with mud sills, through quicksand for distances of 425 and 160 ft., respectively. The timbers were lagged with 3-in. plank to control sand.

Jan 1, 1940

By David B. Reger

New discoveries of gas in the southern counties featured the petroleum industry in West Virginia during 194;. Drilling for oil increased slightly over 1944 and a small increase of initial production resulted. Out of 28 wildcats drilled, there were 16 gas discoveries and 12 dry holes. No commercial oil was found in the 28 wells.

Jan 1, 1946

By William E. Ford, Edward Salisbury Dana

5. Crystallography. - The subject of Crystallography includes the description of the characters of crystals in general; of the various forms of crystals and their division into classes and systems; of the methods of studying crystals, including the determination of the mathematical relations of their faces, and the measurement of the angles between them; finally, a description of compound or twin crystals, of irregularities in crystals, of crystal- line aggregates, and of pseudomorphous crystals. 6. Definition of a Crystal.- A crystal * is the regular polyhedral form, bounded by smooth surfaces, which is assumed by a chemical compound, under the action of its intermolecular forces, when passing, under suitable conditions, from the state of a liquid or gas to that of a solid. As expressed in the foregoing definition, a crystal is characterized, first, by its definite internal molecular structure, and, second, by its external form. A crystal is the normal form of a mineral species, as of all solid chemical com- pounds; but the conditions suitable for the formation of a crystal of ideal perfection in symmetry of form and smoothness of surface are never fully realized. Further, many species usually occur not in distinct crystals, but in massive form, and in some exceptional cases the definite molecular structure is absent. 7. Molecular Structure in General.- By definite molecular structure is meant the special arrangement which the physical units, called molecules, assume under the action of the forces exerted between them during the formation of the solid. Some remarks are given in a later article (p. 22 et seq.) in regard to the kinds of molecular arrangement theoretically possible, and their relation to the symmetry of the different systems and classes of crystals.

Jan 1, 1922

By A. A. Berk

LAGGING technology and the slow spread of information have been the chief obstacles to widespread participation in minimizing the industrial pollution load. These obstacles can be conquered by fact finding and applied research. There are three aspects to the problem of water-borne mineral waste: to minimize the amount being thrown away, to select a predisposal treatment, and to use the products or dispose of them. It is often possible to minimize the waste by making very minor changes in the process that produces it. For example, a manufacturer of automobile bumpers greatly reduced the dragout 'from a plating bath by modifying the design and position of two boltholes.' A plater of automobile hubcaps installed a drainage bar and decreased the loss of chrome-plating solution to the rinse water by about 80 pct.' The mill at a western mine found it possible to discard 60 to 70 pct of an ore with minimum treatment," so that the processing effort could be concentrated on a high-graded slime, with significant reduction in costs and improvement in recovery. The possibilities for waste reduction through process changes are limited only by the imagination. A recent patent points out the advantages of using No. 1 fuel oil instead of water in wet-process cement making;& the fuel oil presumably has better properties than water for this purpose and is said to be almost com'pletely recovered or utilized, so that there is no waterborne waste. Recycling to reduce wastes and improve process economy is very well illustrated in vanadium and uranium recoveries from relatively low grade ore. Ores containing 6 pct calcium carbonate were found to give poor vanadium recovery by the salt-roasting process because the vanadium was converted to water-insoluble calcium vanadate. Following the salt-roasting process, sulfuric acid was used to leach the uranium. Enough calcium sulfate was formed

Jan 1, 1958

By W. L. III McMorris, R. E. Zimmerman, Michael Sokaski, E. R. Palowitch, M. R. Geer, C. E. Capes, A. W. Deurbrouck, S. C. Sun

PART 1: DENSE MEDIUM SEPARATION by M. SOKASKI, M. R. GEER, and W. L. MCMORRIS III INTRODUCTION In the early days of coarse-coal treatment by the dense-medium process in Europe, loess was one of the materials used for medium solids. Newly developed cyclones were used to reclaim and thicken the loess suspension. On occasion, when the cyclone thickener at the Maurits mine in the Nether- lands plugged, the overflow was found to be filled with clean coal free of impurity. From this observation stemmed the concept of the cyclone as a cleaning device. Development took place during World War I1 in the lab- oratory of the Dutch State Mines under the direction of M. G. Driessen. A 15 tph (13.6 mt) pilot plant was in operation in the laboratory by 1945, when, in September, Driessen made the first public disclosure of the process in a paper presented to the Institute of fie1 in London. In April 1945 operation of this pilot plant was observed by H. F. Yancey, who was so

Jan 1, 1979

By R. A. Wyman

KYANITE schists in the Sudbury area have been generally described by Haw,' who has also given particuLar information on preliminary treatment of three large samples from Dryden township, Ontario.' Kyanite, garnet, biotite, quartz, and feldspar comprise the main ingredients of this ore. Kyanite is the valuable mineral. About 5½ tons of —35 +200 mesh product, made by dry rod milling, screening, and separation on the Exolon magnetic separator, were available for treatment by flotation. Magnetic separation had effectively reduced garnet and biotite so that flotation feed consisted essentially of kyanite, quartz, and feldspar, the kyanite content averaging 32 pct and representing about 86 pct of the kyanite in the original ore. Earlier work on kyanite at the Mines Branch, Ottawa, s-c employed an acid circuit, but to avoid production difficulties in the use of acids and at the same time take advantage of the fact that industrial minerals respond somewhat to soap flotation, it was decided first to investigate the higher pH levels. Exploratory tests using —65 +200 mesh feed ended with production of 96.6 pct kyanite concentrate rep-

Jan 1, 1959

By R. S. Shoemaker, F. W. McQuiston

BENGUET EXPLORATION, Inc. Tuba, Benguet, Philippines 1970 Operating Data ORE DESCRIPTION: Complex ore mostly sulfides and composed mainly of sphalerite and pyrite with minor amounts of chalcopyrite, galena, arsenopyrite, hematite, magnetite, chlorite, calcite, garnet and quartz. TYPE OF MINE: Underground, cut and fill method ORE HAULAGE TO MILL: Mine rail cars with electric locomotives. CAPACITY in TONS/24 HRS: 130 ASSAYS: Mill Heads Mill Tails Au = 0.65 oz per ton Au = 0.096 oz per ton Cu = 0.75% CU = 0.27 % Zn = 10.50 % Zn = 0.64 % Ag = 3.20 oz per ton Ag = 0.33 oz per ton Cd = 0.01 % PRODUCT: Au, Ag, Cu, Zn and Cd RECOVERIES: = 90% ~g = 89% Cu = 60% Zn = 94% SCREEN ANALYSIS OF MILL FEED: 90% -200 mesh POWER: Grinding 25.4 Kwh/T Copper Flotation 14.5 Zinc Flotation 13.3 Cyanidation 20.4 Others 25.0 TOTAL POWER: 98.6 KwH/T WATER: Pumped from riverside and underground 50 to 100 meters distance. Consumption of about 700 gallons per ton of new water.

Jan 1, 1975

"Located at Canyon Ferry on the Missouri River, 17 miles from Helena and 63 miles from Butte. River drainage area 15,570 sq. miles. Built in 1898.DAM: Rock-filled, wooden crib, 490' long and 39' feet at maximum head; also masonry core, earth bulk-head 300' long and granite masonry abutments.SPILLWAY: 473' long, crest elevation 3660.5; steel flashboard system 10' high.PENSTOCKS: 10 main penstocks, 12' diam., about 40' long, leading from canal to turbines, each supplying 1 pair turbines.WHEELS: 4 main center discharge, horizontal units, each 1 pr. of 42"" wheels made by Dayton Globe Iron Works, and 6 main units, each 1 pr. of 45"" wheels made by S. Morgan Smith Co., all 157 r. p. m., normal head 34', and direct coupled to generators.GENERATORS: 10 W. E. & M. Co., Kodak Type, revolving armature, 750 k-w., 157 r. p. m., 550 v., 3 phase, 60 cycle alternators.OPERATION: The plant has large water storage and can carry peak loads to 12,000 h-p. It is the central control station for the system."

Jan 1, 1913

By F. H. Daniels

IN this paper it is my intention to call your attention to a few of the many producers using blast, now in common use in Sweden, and also those constructed by the Washburn & Moèn Manufacturing Company at their Quinsigamond Works. During a prolonged stay in Sweden the writer had an opportunity

Jan 1, 1881

C. Q. Payne, New York City: Prof. Blake's inference that magnetic separation may be successfully employed upon smithsonite and iron oxide, after a preliminary roasting, is confirmed by the fact that this separation has been carried on with entire success for over a year at the works of the Wythe Lead and Zinc Mine Co., Austinville, Va. The ore mined on this property is a mixture consisting chiefly of galenite, smithsonite and limonite. The crude material is crushed, screened and washed in log washers for the removal of clay, and then jigged for the separation of the galenite. The zinc-and iron-ores are then roasted in reverberatory furnaces, being turned and moved towards the bridge-end of the hearth by manual labor. The roasted material contains from 20 to 26 per cent. of metallic iron. The slight difference in the specific gravities and the friable condition of the ores after roasting prevent the separation of the oxides by means of jigging. It was therefore the practice, previous to the use of magnetic separation, to charge the roasted material directly into the retorts of the zinc-furnaces. The rapid cutting of the retorts under this practice proved a serious inconvenience and expense. In the spring of 1892, the writer built for the Wythe Lead and Zino Mine Co. a magnetic separator which embodied several novel features and which was designed to treat the roasted zinc- and ironoxides. This separator has proved entirely successful for the purpose for which it was designed. During the first nine months of its operation, 1415 tons of 2240 pounds of roasted material were passed through the separator, producing about 675 tons of heads carrying from 50 to 55 per cent, of metallic iron, which are sold to a neighboring blast-furnace. The tailings, which contain the zinc, carry from 4 to 6 per cent. of metallic iron. For magnetizing the iron-ore previous to separating it from the zinc-ore, no change whatever mas made in the form of the reverberatory furnace previously employed. It was found that, by charging near the bridge-end of the hearth, toward the end of the roast-

Jan 1, 1894

By Edward C. Stephens, Robert R. Coats

High-grade copper ore was discovered in 1932 in the long-dormant Mountain City (Cope) mining district, Elko County, Nevada. From 1932 to 1947, the one producing mine in the district, the Mountain City Copper Mine, produced 1,109,878 short dry tons of ore averaging 9.745 per cent copper, 0.274 ounces of silver, and 0.0057 ounces of gold per ton. The Mountain City Copper Mine is developed in eugeosynclinal rocks of Ordovician age, the Valmy Formation, which is part of the upper plate of the Roberts Mountains thrust. On the Valmy were deposited unconformably first, a elastic formation of Devonian or Mississippian age, the Grossman Formation, succeeded unconformably by a ·sequence of three conformable formations, the Banner, the Nelson, and the Mountain City. The Banner Formation probably is early Late Mississippian in age; the ages of the Nelson and Mountain City are not known precisely but are believed to be of Late Mississippian and Carboniferous(?) age, respectively. A thick formation of elastic rocks, limestone, and volcanics, the Reservation Hill Formation, has been thrust over the Mountain City. The age of the Reservation Hill is unknown but is presumed to be Pennsylvanian(?) and Permian(?). Several plutons of Cretaceous quartz monzonite intrude the Paleozoic formations; they and the intruded formations have been laid bare by erosion, and several sequences of volcanic rocks of Miocene and Pliocene age, and perhaps in part older, have been successively deposited on irregular erosion surfaces. The primary mineralization of the Mountain City Copper Mine is believed to postdate the deposition of the Nelson Formation and to predate the intrusion of the quartz monzonite. The primary ore bodies are lenticular in shape and are composed largely of quartz, pyrite, and chalcopyrite. The ore lenses, in general, strike northwestward and dip northward. They occur in the Valmy Formation within a definite stratigraphic sequence composed largely of shales with associated minor quartzite lenses. The ore is epigenetic. The principal ore body, the "200," was completely leached to the 200 level. Abruptly beneath the barren gossan was supergene copper sulfide ore, much of which assayed 50 per cent copper. The secondary copper minerals are sooty and massive chalcocite, bornite, and covellite. The supergene enrichment of the ore may have required a large part of Tertiary time.

Jan 1, 1968

By J. H. Swisher

ALUMINUM deoxidation equilibrium in liquid iron has been the subject of many investigations. Sawamura and Sano1 have written a critical survey of the literature on this subject and consider the data of Gokcen and chipman2 and of d'Entremont, Guernsey, and Chip-man3 to be most reliable. The present study was undertaken to check these data and extend the range of the experiments to lower temperature. The experiments consisted of equilibrating 5-lb Fe-Al melts with recrystallized alumina crucibles at 1580o + 10oC, and analyzing the solidified ingots for aluminum and oxygen. The electrolytic iron stock contained 100 ppm C, 20 ppm 0, and trace amounts of other elements.* The stock was induction-melted in an atmosphere of 5 pet H2 in argon to attain equilibrium between the melt and the crucible. The temperature was measured with a W, 3 pet Re/W, 26 pet Re thermocouple, and the equilibration time was about 4 hr. The results are plotted in Fig. 1 along with curves obtained from the data of d'Entremont et al.,3 for temperatures of 1740o and 1910°C. The present results can be seen to be consistent with the previously reported high-temperature data. The reaction under study is AI2O3 (s) = 2 Al (l) +3O [1] for which the deoxidation product is Kl =[% Al]2 [%O]3 [2] (Under the experimental conditions, Fe A12O4 is not expected to form.4) In Fig. 2, values of log Ki evaluated at 0.01 pet A1 are plotted against 1/T, using data obtained from all the investigations under consideration. The deoxidation product is plotted in Fig. 2 in lieu of the equilibrium constant (normally obtained by evaluating Ki as pet A1 — 0) because of the uncertainty involved in extrapolating to zero concentration. The difficulty in extrapolating the present data for 1580°C is apparent curvature in the log Ki vs pet Al plot. This curvature is perhaps due to the uncertainty in oxygen analysis for concentrations of 5 ppm and below. For the data of Gokeen and chipman,' the extrapolation is also difficult because of experimental scatter. The line drawn through the points plotted in Fig. 2 may be represented by the equation:

Jan 1, 1968

Jan 1, 1933

By Paul F. Kerr

The uranium-producing areas near Marysvale, Utah provide an unusual group of veins and replacement deposits associated with a Pliocene-Oligocene intrusive and extrusive igneous complex. Aside from several scattered occurrences in older volcanics, uranium-bearing veins occur in intrusive quartz monzonite or granite and in nearby rhyolite. The veins in general trend within a few degrees of N55-65°E, are more or less vertical, and are found along the western margins of a quartz monzonite intrusive. The replacement deposits are found in rhyolite intrusives and also in the lower portions of rhyolite flows close to places where veins forming solutions rising through quartz monzonite came into contact with the rhyolite. At least 14 veins have been mined since uranium mining operations began at Marysvale some 16 years ago, while ore has been extracted through about 10 miles of underground workings. The active mmmg area is approximately 3000 feet long and in the central portion 1500 feet wide. Ores have been found over a vertical spread of almost 2000 feet, between the highest occurrence on Jungfrau Hill ( ca. 7200 feet) and the deepest discovery of ore in a drill hole near the Prospector Mine (ca. 5200 feet). Under existing mining and marketing conditions, mining along the veins in the main area appears to have reached an economic limit at about 500-600 feet below the surface. However, orebodies in the rhyolite and in the upper portions of veins close to the rhyolite are subject to active mining. Isotopic dates indicate that the uraninitebearing veins and replacements are late Miocene or Pliocene (ca. 10-13 m.y.), the rhyolite is Miocene (avg. 17.5 m.y.), and the quartz monzonite and granite intrusives are late Oligocene (23.6 to 26.0 m.y.). The older Bullion Canyon Volcanic Series which encircles the area is Oligocene (28 to 31.1 m.y.). Two generations of alteration occur: ( 1) Earlier alunitic veins and replacement bodies are found in the Bullion Canyon Volcanic Series, none of which have produced uranium; (2) Later argillic alteration associated with the introduction of uranium is found along veins, replacing glassy rhyolite dikes and replacing phases of the rhyolite.

Jan 1, 1968

By T. H. Alden

BaCKOFEN, Avery, and Turner have shown"2 that the large tensile elongation in superplastic metals is correlated with a high strain-rate sensitivity of the flow stress. At present, the reported superplastic materials are complex eutectic or eutectoid systems with a large solubility range in at least one of the terminal phases. This note describes the behavior of a solid-solution alloy (at 22°C)5,= Sn-1 wt pct Bi, which has been processed in order to produce a fine grain size.2,3,6 The chill-cast, 1/2-in.-diam ingot was homogenized for 1 week at 130°C, extruded at O°C to 0.083 in. diam, quenched within 15 sec, and stored at -196°C. Samples were warmed to room temperature 16 hr prior to mechanical testing or metallography. During tension testing at room temperature, it was found that the flow stress reached a steady-state value which depended on the imposed elongation rate and was independent of strain to an error of about ±5 pct. In Fig. 1 is plotted log a vs log e where a is the measured steady-state flow stress and i the imposed strain rate. These quantities were calculated using "instantaneous" area and length to an accuracy in the sample diameter of ±5 x 10-4 in. The log a-log 1 curve is sigmoidal. The strain-rate sensitivity, which may be given by d log old log 6,' has a maximum value of about 0.48 between i = 5 x 10-4 and 5 x 10-3 per min. The value is well above frequently measured values for metals at creep temperatures (0.1 to 0.3) and comparable to the rate sensitivity for Pb-Sn solder: which has been shown to be superplastic.2,3 Note, however, that below or above the strain rate of 10-3 per min the rate sensitivity of Sn-1 pct Bi decreases and at high rates is more nearly like that of conventional metals. The grain size of this material is relatively uniform, Fig. 2, and may be specified by an average linear intercept i.' Grain growth occurs at room temperature but after 16 hr, L = 5. Tensile elongation was measured on finer-grain-size specimens, which had been at room temperature 15 min prior to testing. After 15 min, the samples are fully recrystallized. Three strain rates, 5 x 10-3, 10-2, and 2.5 x 10-2 per min, were employed for which the measured elongations varied from 425 to 500 pct. These results would seem to justify the term superplastic, applied to this alloy, although the ductility is inferior to that of the Sn-Bi eutectic.3 The Sn-1 pct Bi alloy, which is a single-phase material with equiaxed, fine grains, is an excellent one on which to make an estimate of the Nabarro-Herring9 creep rate. According to the model of Avery and Backofen2 a substantial part of the deformation must be accomplished by N-H creep in the strain rate-temperature regime in which d log a/d log 1 = 0.5. The maximum N-H creep rate is given by9 L2kT where v is the atomic volume and D the self-diffusion coefficient. For this test v = 3.O x 10-23 cu cm, D = 1.4 e-23,300/RT = 2.5 x 10-l7 sq cm per sec,7 L = 5x 10+4 cm, T = 295°K, and a = 2000 lb per sq in. = 1.38 x 10' dyne per sq cm. The calculated creep rate is E= 4 x 10-11 per sec which may be compared with the measured creep rate at this stress, Fig. 1, of 6.7 x 10-5 per sec. The N-H creep rate is seen to be negligible. Earlier consideration2 of this question was in error because incorrect diffusion coefficients were used. The assistance of R. R. Russell in metallography is acknowledged gratefully.

Jan 1, 1967

[Aamot, Clav Crone, (Member '29) Met., Det Norske Aktieselskab for Elektrokemisk, Industri, Inc., Oslo, Norway. Aamot, 0, Crone, (Member '29) c/o Elektrokemisk, Radhusgaten 23, Oslo, Norway. Aase, Glenn D., (Junior Member '40) Jr. Met., American Smelt. & Refin. Co., Selby, Calif. Abadie, Henry G., (Junior Member '43) Div. Petr. Engr., Union Pacific R.R. Co., 422 W. 6th St., Los Angeles 14, Calif. Abbott, Clarence E., (Member '04) Civil Engr., V.P., Tennessee Coal, Iron & R.R. Co., 1542 Brown Marx Bldg., Birmingham, Ala. Abbott, Fred E., Jr., (Member '44) Petr. Engr., c/o Arabian American Oil Co., A.P.O. 816, c/o Postmaster, New York, N. Y. Abel, Raymond L., (Member '28) Chem. Engr., 0. 0., Pittsburgh Chem. Warfare Procurement Dist., American Bank Bldg., Pittsburgh, Pa.]

Jan 1, 1946

By T. H. Oxnam

INTRODUCTION. THE predominating value of the ores now being treated by the Palmarejo and Mexican Gold Fields, Ltd., is silver, although some gold is also carried. The present method of treatment consists of wet-crushing and concentrating, followed by the cyanidation of the unroasted sands and slimes. The sands are treated by leaching and the so-called accumulated slimes by a system of agitation and decantation. It is only within very recent years that the cyanidation of unroasted silver-ores has been commercially successful. In fact, at the time operations were begun at the cyanide-plant at Chinipas, February, 1902, I knew of no other leaching-plant treating similar ores successfully. The cyanide treatment of the Palmarejo ores differs but little from the ordinary practice in cyaniding gold-ores; and perhaps but little, if any, new information concerning the metallurgy of silver is to be gleaned from it. PALMAREJO MINE. The Palmarejo mines are located in the southwestern part of the State of Chihuahua, Mexico, on the foothills of the Sierra Madre mountains, at an elevation of 3,200 feet. The mills, 12. miles distant, are situated on the Chinipas river, near the town of Chinipas, which is about 150 miles northeast of Agiabampo, on the Gulf of California. Supplies are shipped via this port as this route is the best and most direct to the property. The ore-bodies in the Palmarejo mines have been deposited. along a series of rock-fractures, caused by an intrusion of eruptive rock. The most important of these fractures or fissures, both in width and value, are the Prieta and Blanca veins, which.

Jul 1, 1905

By P. D. I. Honeyman

DURING 1938 many copper companies again felt the economic pinch and smelter operations were often on a reduced basis which some- times resulted in intermittent operations and complete shutdowns. During the last half of the year production was stepped up and smelting operations resumed a more normal appearance. One of the present-day trends in reverberatory sme1ting is definitely toward high-tonnage operations. i\ t the Phelps Dodge Corporation's Douglas plant, the reconstructed 107 by 26- ft. reverberatory furnaces are operated at the rate of 1000 tons of solid charge per day. The arch, all of silica brick; is sufficiently high above the bath to give

Jan 1, 1939

By W. M. McKewan

Magnetite pellets were reduced in flowing hydrogen at pressures up to 40 atm over a temperature range of 350° to 500°C. The rate of weight loss of oxygen per unit area of the reaction surface was found to be constant with time at each temperature and pressure. The reaction rate was found to be directly proportional to hydrogen pressure up to 1 atm and to approach a maximum rate at high pressures. The results can be explained by considering the reaction surface to be sparsely occupied by adsorbed hydrogen at low pressures and saturated at high pressures. PREVIOUS investigation1,2 have shown that the reduction of iron oxides in hydrogen is controlled at the reaction interface. Under fixed conditions of temperature, hydrogen pressure, and gas composition, the reduction rate is constant with time, per unit surface area of residual oxide, and is directly proportional to the hydrogen pressure up to one atmosphere. The reduction rate of a sphere of iron oxide can be described3 by the following equation which takes into account the changing reaction surface area: where ro and do are the initial radius and density of the sphere; t is time; R is the fractional reduction; and R, is the reduction rate constant with units mass per area per time. The quantityis actually the fractional thickness of the reduced layer in terms of fractional reduction R. It was found in a previous investigation2 of the reduction of magnetite pellets in H2-H,O-N, mixtures, that the reaction rate was directly proportional to the hydrogen partial pressure up to 1 atm at a constant ratio of water vapor to hydrogen. Water vapor poisoned the oxide surface by an oxidizing reaction and markedly slowed the reduction. The enthalpy of activation was found to be + 13,600 cal per mole. It was also found that the magnetite reduced to meta-stable wüstite before proceeding to iron metal. The following equation was derived from absolute reaction-rate theory4,8 to expfain the experimental data: where Ro is the reduction rate in mg cm-2 min-'; KO contains the conversion units; Ph2 and PH2O are the hydrogen and water vapor partial pressures in atmospheres; Ke is the equilibrium constant for the Fe,O,/FeO equilibrium; Kp is the equilibrium constant for the poisoning reaction of water vapor; L is the total number of active sites; k and h are Boltzmann's and Planck's constants; and AF is the free energy of activation. Tenenbaum zind Joseph5 studied the reduction of iron ore by hydrogen at pressures over 1 atm. They showed that increasing the hydrogen pressure materially increased the rate of reduction. This is in accordance with the work of Diepschlag,6 who found that the rate of reduction of iron ores by either carbon monoxide or hydrogen was much greater at higher pressures. He used pressures as high as 7 atm. In order to further understand the mechanism of the reduction of iron oxide by hydrogen it was decided to study the effect of increasing the hydrogen pressure on rebduction rates of magnetite pellets. EXPERIMENTAL PROCEDURE The dense magnetite pellets used in these experiments were made in the following manner. Reagent-grade ferric oxide was moistened with water and hand-rolled into spherical pellets. The pellets were heated slowly to 550°C in an atmosphere of 10 pct H2-90 pct CO, and held for 1 hr. They were then heated slowly to 1370°C in an atmosphere of 2 pct H2-98 pct CO, then cooled slowly in the same atmosphere. The sintered pellets were crystalline magnetite with an apparent density of about 4.9 gm per cm3. They were about 0.9 cm in diam. The porosity of the pellets, which was discontinuous in nature, was akrout 6 pct. The pellets were suspended from a quartz spring balance in a vertical tube furnace. The equipment is shown in Fig. 1. Essentially the furnace consists of a 12-in. OD stainless steel outer shell and a 3-in. ID inconel inner shell. The kanthal wound 22 in. long, 1 1/2, in. ID alumina reaction tube is inside the inconel inner shell. Prepurified hydrogen sweeps the reaction tube to remove the water vapor formed during the reaction. The hydrogen is static in the rest of the furnace. The sample is placed at the bottom of the furnace in a nickel wire mesh basket suspended by nickel wire from the quartz spring. The furnace is then sealed, evacuated, and refilled with argon several times to remove all traces of oxygen. It is then evacuated, filled with

Jan 1, 1962