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By Robert B. Fulton, Gill Montgomery

Fluorspar is the commercial name for fluorite, a mineral that is calcium fluoride, CaF2. The name, derived from the Latin word fluere (to flow), refers to its low melting point and its early use in metallurgy as a flux. It is the principal industrial source of the element fluorine. Cryolite, sodium aluminum fluoride, Na3AlF6, is a rare mineral which has been found in commercial quantities only in Greenland. The natural material has been supplanted by synthetic cryolite for its principal industrial use in the manufacture of aluminum. History Fluorspar was used by the early Greeks and Romans for ornamental purposes as vases, drinking cups, and table tops. Various peoples, including the Chinese and the American Indians, carved ornaments and figurines from large crystals. Its usefulness as a flux was known to Agricola in sixteenth century Europe. Fluorspar mining began in England about 1775 and at various places in the United States between 1820 and 1840. Production grew substantially following the development of basic open-hearth steelmaking, wherein it is used as a flux. Use was stimulated by growth of the steel, aluminum, chemical, and ceramic industries, particularly during World Wars I and II. Fluorocarbons entered the picture in 1931. The use of anhydrous hydrogen fluoride (HF) as a catalyst in the manufacture of alkylate for high octane fuel began in 1942. Differential flotation for separating fluorspar from galena, sphalerite, and common gangue minerals in the 1930s, and the application of heavy-media concentrating methods to the treatment of low-grade ores in the 1940s were outstanding technological advances that facilitated increased production. Recently, pelletizing and briquetting of flotation concentrates for use in steel furnaces and the development of flotation schemes for beneficiating ores containing abundant dolomite and barite have been major improvements in the industry. Uses of Fluorspar Fluorspar is used to make hydrogen fluoride, also called hydrofluoric acid, an intermediate for fluorocarbons, aluminum fluoride, and synthetic cryolite. It is used as a flux in the steel and ceramic industries, in iron foundry and ferroalloy practice, and has many minor specialized uses. Hydrogen fluoride (HF) is produced by reacting acid grade (97% CaF2) fluorspar with sulfuric acid in a heated kiln or retort to produce HF gas and calcium sulfate. After purification by scrubbing, condensing, and distillation, the HF is marketed as anhydrous HF, a colorless fuming liquid, or it may be absorbed in water to form the aqueous acid, usually 70% HF. Synthetic cryolite, organic and inorganic fluoride chemicals, and elemental fluorine are made from hydrofluoric acid. The acid itself is important in catalysis in the manufacture of alkylate, which is an ingredient in high-octane fuel for aircraft and automobiles, in steel pickling, enamel stripping, glass etching and polishing, and in various electroplating operations. The manufacture of one ton of virgin aluminum requires about 50 to 60 lb of fluorine content in synthetic cryolite and alumnium fluoride. This quantity, through improved technology and recovery practices, is being lowered significantly.

Jan 1, 1983

By Charles Catlett

While the occurrence of phosphorus in coking-coal has assumed less importance with the development of the opeu-hearth method of steel-making, it may not be without interest to note the form in which phosphorus exists in one particular coal-seam. In the examination of what is known as the Big seam, which outcrops a few miles west of Columbiana, Ala., my attention was called to the distribution through the coal, in the form of minute veins and particles, of a resinous-looking substance. A small amount of this was selected, and was provisionally identified as evansite (Al6 Y2 O14, 18 Aq). Subsequently, through the courtesy of Dr. J. Sharshall Grasty, of the Geological Department of the University of Virginia, I was able to secure an additional amount of material, which was purified down to about 0.3 g. This was examined by Prof. John J. Porter, of the University of Cincinnati, and gave the following partial analysis: Per Cent. Loss on ignition,......... 37.43 Phosphoric anhydride,..10.33 Alumina,..........36.33 There was also a trace of silica, and quite a considerable quantity of lime and magnesia. Professor Porter was led to think that the material was not pure, but a mixture of several of the phosphates of aluminum carrying lime and magnesia. The material available did not permit of the convenient determination of the other ingredients. One form in which phosphorus occurs in coal is evidently as a hydrated phosphate of aluminum; and any coal which shows to the eye the occurrence of a light-colored resinous-looking material should be looked on with suspicion as being high in phosphorus.

Jan 1, 1912

By L. H. JEFFRIES

In the mining operations of The Canyon Corp., Deadwood. S. D., the use of mucking machines has been of definite advantage. The type used is that which depends upon the traction of the motor-driven wheels to crowd the dipper into the muck pile, while the car in which the muck is received is coupled to the mucker and moves forward or back with it. This general arrangement is entirely satisfactory on a substantially level track. The ores which occur in this district are a replacement of dolomite and the beds are now tilted to an inclination of about 7-1/20. In our operations it is necessary to drive inclines down-hill on this slope, which makes a difficult hand-mucking job even if water were not present. With these facts in mind, an attempt was made to use the mucking machine for driving down the in- cline, but as expected, the traction was insufficient to handle the machine and the necessary car. The means used to correct this condition will perhaps impress most readers as too complicated and cumbersome to effect any economy, but the idea may be of service to some who have a similar condition. After considering several s

Jan 1, 1940

By Henry H. Otto

The anthracite industry can be divided into two parts—the underground, or mining, and the outside, or preparation or manufacture. To understand recoveries in the two branches, some of the history of the industry and the changes that have taken place in the past century should be considered. It is a long step from 1807, when 55 tons were produced in the Wyoming field, to 1917, the peak year, when 80,841,223 tons were shipped to market from all the fields. In 1820, the Lehigh Coal Co., the predecessor of the Lehigh Coal & Navigation Co., shipped 365 tons in arks down the canal of the Lehigh Navigation Co. The Schuylkill field was not opened until 1822, when 1480 tons were shipped. The Wyoming field really became a producer in 1829, when 7000 tons were mined and shipped. It is well to note, at this time, the passing of the Coleraine colliery after a life of 88 years; in collieries of this age will be found the romance of the region, as well as the history of the changes to date. Mining Methods In the Lehigh region, the first coal came from the old quarry mines at Summit Hill; a little later the open-cut workings, or quarries, east of Jeansville, and near Beaver Meadow were opened. In the Wyoming field, it was necessary to resort to underground mining almost from the very first. Ashmead1 has described the changes in outside preparation methods, dl tending to increase the percentage of coal shipped to market. A description from the days when the lump coal was raked and screened out in the quarries or mines, to the modern breaker of today, shipping as high as 6000 tons of at least eight sizes of coal in an 8-hr. day is a very interesting story. Each size is a step toward increasing the yield from the property. With the belief that the supply was inexhaustible, the early mining was conducted with the thought of getting the maximum amount of coal on first mining. The superintendent was his own foreman and engineer.

Jan 1, 1925

By William Hurst

This is a presentation of the diffusivity theory for the calculation of the water drive on an oil reservoir in which the history of reservoir pressure with time are the essential parameters for the determination of the rate and cumulative water encroachment into a field. The main body of the paper is essentially the application of the principles underlined here to actual field data. It consists of the work plots of the radial-flow case, and includes a discussion of an illustrated problem for which the water-drive calculations are treated in conjunction with the volumetric-balance equation. The appendix is a mathematical treatment of the linear, radial, and spherical cases of water influx into a reservoir. Introduction The evaluation of oil reserves and the prediction of pressure behavior with different rates of production are related to the volumetric balance of the fluids entering and leaving the space occupied by the oil and gas originally present in the formation; that is to say, important information can be gleaned from a volumetric study of the oil, gas, and water produced from a formation as it affects the extent of change in volume of oil zone, the gas cap, and the amount of water influx from the adjoining water sands. It is not the purpose of this paper to enter into a discussion of the equation of volumetric balance, in which such pertinent information as subsurface sampling and the measurement of reservoir pressures play a predominant part, as this has been discussed in detail by others.1,2 However, there is an inherent difficulty that has limited the general application of this equation to a study of oil reservoirs; that is, the insufficient knowledge of the analytics for expressing the water drive on a field as a function of reservoir pressure. This to a large degree has been overcome and it is the purpose of this paper to present this theory in such form as to be applicable for reservoir calculations. Water Drive If the amount of oil originally in place and the gas space are known, it is a relatively simple matter to determine, by the volumetric equation, the cumulative water influx into a reservoir from the adjoining water sands. Often, however, the oil reserve as well as water influx must be 'determined, and in order to be able to make this calculation it is essential to assign a mathematical relationship for the varying water term that is compatible with conditions known to exist in the formation and gives an accuracy acceptable for engineering calculations. Various equations have been employed empirically by different investigators in making reservoir studies of water drive. One form used by Schilthuis2 expresses the rate of water influx into a reservoir at any time as proportional to the pressure

Jan 1, 1943

By William Hurst

This is a presentation of the diffusivity theory for the calculation of the water drive on an oil reservoir in which the history of reservoir pressure with time are the essential parameters for the determination of the rate and cumulative water encroachment into a field. The main body of the paper is essentially the application of the principles underlined here to actual field data. It consists of the work plots of the radial-flow case, and includes a discussion of an illustrated problem for which the water-drive calculations are treated in conjunction with the volumetric-balance equation. The appendix is a mathematical treatment of the linear, radial, and spherical cases of water influx into a reservoir. Introduction The evaluation of oil reserves and the prediction of pressure behavior with different rates of production are related to the volumetric balance of the fluids entering and leaving the space occupied by the oil and gas originally present in the formation; that is to say, important information can be gleaned from a volumetric study of the oil, gas, and water produced from a formation as it affects the extent of change in volume of oil zone, the gas cap, and the amount of water influx from the adjoining water sands. It is not the purpose of this paper to enter into a discussion of the equation of volumetric balance, in which such pertinent information as subsurface sampling and the measurement of reservoir pressures play a predominant part, as this has been discussed in detail by others.1,2 However, there is an inherent difficulty that has limited the general application of this equation to a study of oil reservoirs; that is, the insufficient knowledge of the analytics for expressing the water drive on a field as a function of reservoir pressure. This to a large degree has been overcome and it is the purpose of this paper to present this theory in such form as to be applicable for reservoir calculations. Water Drive If the amount of oil originally in place and the gas space are known, it is a relatively simple matter to determine, by the volumetric equation, the cumulative water influx into a reservoir from the adjoining water sands. Often, however, the oil reserve as well as water influx must be 'determined, and in order to be able to make this calculation it is essential to assign a mathematical relationship for the varying water term that is compatible with conditions known to exist in the formation and gives an accuracy acceptable for engineering calculations. Various equations have been employed empirically by different investigators in making reservoir studies of water drive. One form used by Schilthuis2 expresses the rate of water influx into a reservoir at any time as proportional to the pressure

Jan 1, 1943

By Persifor Frazer

For various reasons I have not specified the locality where the research indicated in the following pages was undertaken. It will suffice to say that it was on the grounds of a villa once remote from, but now completely surrounded by, its neighboring city, and in close proximity to an industrial establishment of great extent and importance manufacturing many kinds of steel articles and employing upwards of thirty chimney-stacks for power and process work. The problem was to discover the cause or causes of the mortality to trees and plants on the place, and to trace these causes to their origin. Before undertaking this experimental work, the bibliography accompanying this paper was compiled and studied. It appears from an examination of the careful scientific work performed by the ablest French, German, and English chemists during the last 25 years that they are unanimous in assigning the principal—in fact, the overwhelmingly predominant— cause of the destruction of vegetation to sulphur oxides, resulting either from direct oxidation of sulphur in oil of vitriol works, etc., or from the oxidation of the sulphur from the minerals associated with commercial coal. Schroder and Schertel showed in 1884 that the sulphates deposited upon the leaves are not injurious to the plants; and Freytag proved that free sulphuric acid could not be found

Jan 1, 1908

By Y. Oinouye, H. Ries

Of the several interesting physical properties of clay which have claimed the attention of investigators in recent years, none is more important than the behavior of the material when heated to temperatures above those of dehydration. Some of the problems to be solved are: 1. The mineralogical changes that take place in firing. 2. The relation between temperature and change in constitution, shrinkage, porosity, etc. 3. The importance of the time factor, as duration of firing, either in reaching a given temperature, or of exposure to a constant temperature. Mineralogical Changes As a result of fusion, reactions take place between the constituents of a clay, which result in a reorganization of the mass, and the formation of new compounds. Of the new minerals developed, sillimanite is the one usually recorded, and has been referred to by a number of observers.' There appears to be a difference of opinion, however, regarding the temperature at which it is formed. Thus Klein2 notes that sillimanite forms only above 1300" C., while Mellor claims that it can develop below 1200" C., the difference in results being conditioned by the time factor. In Klein's experiments the test pieces were fired in 12 hr., while in Mel-lor's, the temperature rose from 800" to 1180" in 24 hr., and occupied the same time in cooling back to 800".

Jan 1, 1918

By Eleanor Haslem, Carl A. Zapffe

THE present investigation has three principal purposes: I. To develop a method for measuring hydrogen embrittlement that avoids certain errors complicating previously used methods. 2. To explore in a preliminary way some of the fundamental factors controlling embrittlement. 3. To apply the measurements specifically to stainless grades of steel, whose sensitivity or insensitivity to hydrogen embrittlement has never been clearly defined. SELECTING A TEST METHOD Hydrogen embrittlement is a condition of low ductility resulting from excessive absorption of hydrogen by the steel at some period in its history, and may be revealed by almost any test involving cold deformation. Tensile tests, impact tests, and bend tests are commonly used for detecting hydrogen embrittlement; although numerous other tests, such as cold-upsetting or extrusion, could be used. The simplicity of using a wire specimen for cathodic and acid pickling tests, and the especial adaptability of the bend test to wire specimens, led to selection of the bend test for the present research. Bend tests usually have been of three general types: (I) fatigue, (2) reversed bend, and (3) single bend. The first two types, though widely used, are inaccurate because their measurements are counteracted by an aging effect; and the third type has not been developed to its fullest utility. The effect of cold-working in removing hydrogen is well known. During a bend test hydrogen can be observed escaping from the convex side simply by coating the specimen with oil; and any technique employing flexing or reverse bending may therefore have its measurements masked because the mechanical action reduces the embrittlement during the test. This factor is so important that even elastic flexing of a hydrogen-charged wire specimen should be avoided before testing if accurate measurements are desired. DEVELOPING A MACHINE FOR MEASURING HYDROGEN EMBRITTLEMENT As for the single-bend test, its theory is good, and recovery caused by mechanical work is kept to a minimum. With a given degree of hydrogen embrittlement, a specimen will break at a given angle if the bending is applied unidirectionally and uniformly. The radius of the bend must be kept constant; and the rate of bending should be a constant, slow enough to allow reading of the breaking angle, and yet rapid enough to prevent significant recovery from the escape of hydrogen during bending. A simple apparatus (Fig. I) was constructed using a type H Foxboro drive unit A, which is a synchronous motor with a gear-reduction ratio of 600 to I. A cord, fixed at one end to a wooden pulley B on the drive shaft of the motor, follows the pe-

Jan 1, 1946

By H. W. Hockin, D. r. Brandt, R. H. Walsh, P. L. Dietz, P. R. Girardot

New Jersey, Florida, and Canadian ilmenites were reduced with hydrogen or coke under various experimental conditions and the phase changes occurring in the ilmenite upon reduction have been studied by microscopic examination of polished sections and by X-ray diffraction. The products formed were dependent upon the type of ilmenite, temperature, time and reducing agent. Of the reducing agents, hydrogen was the more effective at lower temperatures. 1 HE possible utilization of ilmenite as a source of both iron and titanium has resulted in the development of a number of methods for the separation of the iron and titanium content. Slagging processes as currently used in Canada are typical of such methods. Somewhat less attention has been given industrially to the reduction of the iron content at less than the slagging temperature. Although references maybe found to such work, in general only one type of ilmenite, either natural or synthetic, has been studied by each author. We have attempted to draw some relationship between the results of experimental reduction and the type of deposit from which the ilmenite was derived, as evidenced by phases occurring in the ores and in the reduction products. Ilmenite ores having from 27 to 61 pct titanium dioxide were included in this study and in each case reduction was carried out at such temperatures that only limited coalescence of the particulate iron product occurred within the ilmenite grains. The history of the individual ilmenite samples and the temperature of reduction were found to determine the occurrence of various phases and the mode of distribution of the iron. REVIEW OF EARLIER WORK ON REDUCTION One of the earliest references to the reduction of ilmenite at less than the slagging temperature was made in 1917.' The metallic iron produced was_____ leached out by the action of dilute sulfuric or hydrochloric acid, to leave a product high in titanium dioxide. Subsequent to this, numerous patents2-'? and other references13"21 have appeared concerning reduction of ilmenite by carbon, hydrogen, carbon monoxide, methane, coal gas, water gas, or the like in the absence of fluxing agents. Mineragraphic examinations were not reported, and in the main, the only examinations made were chemical analyses. However, in two cases3,13, titanium suboxides were reported in the products and in one case2' rutile was reported, in addition to metallic iron. Both were identified by X-ray diffraction. While reductions in the absence of fluxing agents were generally followed by either a wet or dry chemical process for removal of the metallic iron, a Canadian source17 reported removal of the metallic iron by magnetic separation. By the addition of fluxing agents during reduction, the metallic iron has been coalesced into "pearls." Each reference to such a process23-28 has shown that the coalesced iron could be removed by magnetic or gravity means after the product was crushed. In the absence of fluxes, the coalescence did not generally occur. The major part of the present study has been limited to reductions without fluxing agents in order to determine the primary reactions of naturally occurring ilmenites. Titaniferous iron ores have also been studied,29-33 17, l9 their reduction having been used as the basis of a commercial process for beneficiation of such ores in Norway29 and more recently considered in the United States34,35. The ease of reduction of titaniferous iron ores relative to that of hematite or magnetite has been referred to,33 with the conclusion that the more

Jan 1, 1961

By Ramesh Malhotra, Hubert E. (Deceased) Risser

THE WORLD Coal, as a source of energy and as a source of coke for the smelting of iron ore, has contributed significantly to the development of every major industrial nation of the world A number of other materials-oil, natural gas, wood, waste materials, water, and, in some applications, nuclear materials -can be used satisfactorily for the generation of heat and energy, but no generally acceptable and economic substitute has been found to supplant coke in iron ore smelting in conventional blast furnaces. In the development of many nations, coal provided the initial source of energy for industrialization Although coal provided more than 60% of the world's energy each year between 1902 and 1929, oil and natural gas have surpassed it as a source of energy in more recent years (Ref. 38, pp. 439, 441). Despite the rapid rise in importance of other fuels, a considerable amount of the total energy consumed is still supplied by coal. In 1972, coal supplied 32.1 % of the total world energy (Ref. 49, pp. 2-3). To produce this energy, 2.4 billion metric tons of coal were consumed-a 16.0% increase over the amount consumed in 1962. A further worldwide increase in the amount of coal used to supply energy is projected. According to Dr. Karlheinz Bund (Ref. 37, p 145), by the year 2000 world coal consumption could amount to 5 billion mt. Coal Resources and Production The world's coal resources are estimated to be about 10,872 billion mt. Of this amount, 1,297 billion mt are classified as measured reserves (Ref. 50, p. 57). In Table 13.A.1 the estimates of measured reserves and total resources, recent production, and the ratio of measured reserves to production of major coal-producing countries are shown. About 90% of the world's total coal resources are estimated to be in the USSR, the United States, and China. The United States ranks second in the world in coal resources, but in measured reserves, it ranks first. Because of the difference in rate at which available coal resources are being exploited, the ratio of measured reserves to actual production varies widely among areas and countries. France and East Germany have the lowest reserve to production ratios, 49.5 and 60.1, respectively. In Mexico, where currently less than 5 million mtpy of coal are produced, the ratio is 1257 For all countries producing more than 200 million mtpy of coal (except East Germany), the ratio ranges from 350 to 670. For the United States, the ratio is 669.7. In Table 13.A.2, distribution of the world's coal resources by area is shown. More than 97% of the total resources lie in the northern hemisphere, with Asia, including European USSR, having 63.4%. Only 1.9% of the total coal resources are estimat-

Jan 1, 1976

By Donald W. Scott, L. A. Roe, B. J. Sweo

INTRODUCTION THIS paper describes the application of ore-dressing methods to the reclamation of milled frit from over-spray, or waste, porcelain enamel. Frit is the name given by enamelers to a granulated glass produced by the smelting and subsequent water quenching of various ingredients capable of forming a glass, usually including a compound to produce opacity. It is the major component of porcelain enamel, and normally commands a price ranging from 7 to 12 cents a pound. In the preparation of a white enamel slip, usually 6 or 7 parts of clay, 2 parts of opacifier, small amounts of electrolytes, in some cases inorganic color stabilizers and organic dyes, and 35 parts of water are added to loo parts of frit; the mixture then is milled to a fineness of the order of 92 to 95 pct through a 200-mesh sieve. The frit forms the base of the enamel; the opacifier imparts opacity or reflectance; the clay suspends the frit while in slip form and serves as a binder' in bisque form (dry and unfired); and the electrolytes control the workability. Spraying is used commercially, in many cases, to apply the finish coat of enamel to the ware, prior to drying and firing. In the spraying operation, only about 50 pct, by dry weight, of the enamel slip adheres to the surface of the ware, the remainder forms the over-spray. From 1/2 to 2/3 of the overspray goes up the flue where it is lost or recovered, depending on whether the plant is equipped with a dust-collecting installation; the coarser portion of the overspray is collected in the spray booth. The former product is termed flue reclaim enamel, and the latter booth reclaim enamel. Although the spraying operation is done in specially constructed booths, which are partially or completely enclosed, it is extremely difficult to keep out contaminating dirt, which joins the reclaim. Some present-day large enameling plants use 20 tons of frit a day, of which 10 tons go into reclaim with a potential value of $1400 to $2400. When two-coat finish enamels were common, the reclaim was used satisfactorily for the undercoat, but the relatively recent advent of one-coat finish enamels prevented use of the reclaim because, even when blended with first-run enamels, it gave dirty finishes with poor gloss. It was thought that the pitting and specking encountered with reclaimed enamels were caused by the contaminating dirt, and that the poor gloss was caused, primarily, by the high clay content; more clay usually was added to give proper suspension properties to the slip when the reclaim was used. A clay content in excess of about 10 pct usually imparted refractoriness to porcelain enamels. Present-day one-coat porcelain enamels must combine high gloss and opacity with freedom from surface defects. Methods of beneficiating the over-spray,

Jan 1, 1947

By Samuel S. Wyer

The art of natural-gas compressing is now over 25 years old, and has grown at practically the same rate as the increase in domestic natural-gas consumers. There are now over 200 natural-gas compressing stations in North America, aggregating more than 320,000 hp. of compressor capacity and representing a property value of more than $22,000,000, and compressing more than 85 per cent. of all the gas used. The age and magnitude of the art make it evident that the use of gas compressors is a recognized integral part and universal custom of the natural-gas business. The public also is not without its rights and vital interests in this problem. Approximately 1,700,000 domestic natural-gas consumers in North America are dependent upon gas compressors for their natural-gas service. That is, if the use of compressors were to be prohibited, the majority of these consumers would be unable to secure adequate natural-gas service. Each consumer represents between four and five persons, and it therefore follows that the comfort and well-being—as far as natural-gas service is concerned—of at least 8,000,000 persons would be affected if the use of natural-gas compressors should be prohibited. These 1,700,000 consumers have invested, in services, house piping, fixtures, and appliances, an average of about $90 each, or an aggregate of $153,000,000, which is much more than the companies' investment in gas compressors. Furthermore, in all cases where the rate paid by the consumers is fair to the gas company—considering the value of the service rendered by the gas company—the consumers are entitled to continued service and protection of the investment they have made on the faith that the gas service would be continued in the future. Since "Customs adopted and acquiesced in, if not in conflict with federal or State legislation, have the force of positive law,"l and ('Courts will take notice of whatever ought to be generally known withxn the limits of their jurisdiction,"2 there ought to be no question as to the un-

Jan 1, 1916

By D. G. Hartley, P. C. Hayward, K. R. Weller, U. J. Sterns

The major copper loss at Mount Lyell is in the coarsest particles presented to flotation. An analysis of data collected from the five Primary and six secondary ball mill circuits showed that grinding was limited by low breakage rates in secondary mills, possibly due to oversize balk. For five months, the make-up ball size for one secondary mill was reduced from 50 to 30 mm (2 to 1.1 in.). Frequent steady-state tests indicated that overall average breakage rates could be increased by about 70% using smaller balk. A mathematical simulation of the whole circuit with increased breakage rates showed that the resultant finer grind was likely to improve copper recoveries by about 2%.

Jan 1, 1984

By M. E. Wadsworth, T. L. MacKay

Sintered UO, samples were leached in sulfuric acid solutions of various concentrations. A pressurized system was used so that it was possible to investigate the kinetics of the reaction to 270°C with oxygen overpressures as high as 900 psi. The rate was observed to be a function of the concentration of hydrogen ions and directly proportional to the partial pressure of oxygen. Evidences are presented which indicate that a UO2 surface site reacts with a molecule of water to form a hydroxyl complex which in turn can dissociate with the characteristics of a weak acid. A rate determining step has been proposed which involves the reaction between an oxygen molecule and the hydroxyl complex on the surface of UO,. ThE 2 principal methods for uranium dissolution are carbonate and acid leaching. The sulfuric acid leach is the more popular and is used for the treatment of the majority of the ores of Africa, Canada, and the United States. Low recoveries in basic leach circuits led investigators at the University of British columbia1 to study leaching of uranium ores in pressurized vessels. Early in the study of dissolution of uranium it was found that only uranium in the hexava-lent state could be leached in acid or basic circuits. Therefore, the use of oxygen over-pressure in an autoclave offered an interesting approach to solving the low recovery problems of carbonate leaching. UO, was used in this study because it could be obtained in high purity and also because it is representative of the most refractory of the primary uranium minerals. A pressurized system was used to provide a means whereby important temperature and pressure parameters could be varied for the evaluation of the kinetic processes. The mechanism for the dissolution of UO2 should be similar for any of the uraninite type minerals. At the present all of the kinetic studies that have been conducted have been in carbonate media. Peters and Halpern2 carried out a kinetic study of the leaching of pitchblende. Their specimens were pitchblende ores selected on the basis of high grade and homogeneity. Pearson and wadsworth3 conducted a kinetic study of the dissolution of UO2 in carbonate solutions with results very similar to those obtained by Peters and Halpern. EXPERIMENTAL The UO2 as received* was found by spectroscopic *Mallinckrodt reagent, supplied by the Atomic Energy Commission. analysis to have a purity of 99.94 pct 0.03. It was ground in a mechanical agate mortar and screened through a 400-mesh sieve. Thin flat disks of UO2 were prepared by pressing the sized powder in a specially constructed die at a total pressure of approximately 25 tons per sq in. The pressed disks were approximately 0.25 cm thick, 1.6 cm diam, and 3.5 g in weight. As pressed, the samples were approximately 65 pct of theoretical density. It was essential that a binder such as poly-vinyl alcohol be added before pressing to prevent formation of cracks when fired. It was found by trial and error that pressed disks sintered close to 1870°C in a hydrogen atmosphere, reach densities between 91 and 91.5 pct of the theoretical density. At this density the samples had no measurable porosity based upon a 2-hr emersion in boiling water. An X-ray examination of these sintered UO2 disks showed them to be identical with the original UO2 received. Reaction of UO2 with the alundum furnace core was prevented by placing molybdenum between the samples and the core according to the method of Corwin and Eyerly.4 Leaching studies were carried out in a specially designed autoclave, the details of which have been presented e1sewhere.6 The main features of the equipment as applied to a kinetic study are: 1) solution samples may be removed during the course of a single run; and 2) temperature and agitation are carefully controlled. Two-ml samples removed from the autoclave during the course of a run were analyzed for U3O8 content with a Beckman model DK-2 spectrophotometer by the method of

Jan 1, 1959

A. L. FIELD, Cleveland, Ohio (written discussion*.-)In equation 2, B is used to denote the ratio of bases (lime plus magnesia ) to acids (alumina plus silica) it being stated that this ratio gives more concordant results than the ratio either of bases to silica, or of lime to silica. I find, however, that, by making use of the ratio between true CaO (CaO by analysis minus sulfur calculated to CaS) to acids, equation 2 may he modified to agree with the observed facts within an average error of 0.0041 per cent. sulfur instead of 0.0045 per cent. The revised equation is s = 0.072 + 0.01835 - 0.00061 (t - 1400) - 0.0403B where B is the ratio of true CaO to Al2O3 Plus Si02, and the other symbols have the same significance as before. I would not appear to stress too much this slightly better agreement of the revised equation with the observed sulfur. Yet I believe that the use of this ratio of true CaO to acids is to be preferred, if for no other reason than the fact that it is more in harmony with the previous findings of the Bureau of Mines with regard to the effect of magnesia and other impurities on slag viscosity.1

Jan 12, 1919

By B. H. Sage, W. N. Lacey

The growing background of experimental information concerning the volumetric and phase behavior of binary and ternary hydrocarbon systems is used as the basis for a comparison of these systems with naturally occurring hydrocarbon mixtures under conditions representative of underground petroleum reservoirs. The qualitative and semiquantitative similarities and differences between the two types of systems are considered in reference to the possibilities and limitations of using experimental data on binary and ternary systems for predicting the volumetric and phase behavior of naturally occurring hydrocarbon mixtures of low molecular weight. The possible influence on such phase behavior of water, hydrogen sulphide, nitrogen, and components of relatively high molecular weight is discussed. INTRODUCTION During the past two decades much effort has been devoted to the study of the volumetric and phase behavior of pure paraffin hydrocarbons and of binary and ternary mixtures of these compounds. Many of these studies were carried out with the direct objective of utilizing a knowledge of the detailed characteristics of binary and ternary mixtures of the lighter paraffin hydrocarbons for predicting the behavior of more complex mixtures. The ability to make such predictions with accuracy would be of great value in petroleum production and refining. Although the behavior of the methane-propane system' served at one time as a qualitative illustration of the probable characteristics of the more complex hydrocarbon mixtures found in nature, it' fell far short of requirements for quantitative predictions. The present paper endeavors to indicate the relation of the more recently accumulated information concerning the behavior of binary and ternary hydrocarbons to this problem. In discussing binary and ternary systems as examples pointing toward the behavior of multi-component systems no effort is made to present new methods of predicting the characteristics of natural hydrocarbon mixtures. Preliminary proposals have been made elsewhere for the prediction of volumetric phase equilibrium and thermodynamic data for multicomponent mixtures, utilizing as a basis the behavior of binary and ternary systems. Numerous other proposals have been made. That based upon the concept of a pseudo-critical state" has proved to be of value to the petroleum industry. Concurrently with this study of binary and ternary systems investigations have been made of natural hydrocarbon systems. Of the many publications reporting such experimental information only a few examples will be mentioned. A number of studies of black oil and natural gas have been made and much attention has been directed to extended and detailed investigations of the behavior of fluids in condensate fieldS 16,17,18,19,20. This work has been supplemented by some studies of the separation of bitumen from natural hydrocarbon liquids The over-all behavior of such systems has been used in predicting the volumetric and phase behavior of naturally occurring mixtures This background of experimental and correlated information concerning the behavior of multicomponent hydrocarbon systems also permits a direct comparison of the characteristics of binary and ternary aliphatic systems with those materials produced from underground reservoirs. PRESENTATION OF DATA The primary limitation encountered in using binary and ternary aliphatic hydrocarbon mixtures as examples of the characteristics of the fluids encountered in underground reservoirs lies in the existing lack of knowledge of the quantitative effect upon behavior of the presence of several important constituents, notably hydrocarbons of high molecular weight, water, carbon dioxide, hydrogen sulphide, and nitrogen. The presence of substantial quantities of hydrocarbons of fairly high molecular weight serves to increase the complexity of the phase behavior of natural systems. No simple systems yet studied give adequate guidance in this regard. The influence of such materials of high molecular weight was indicated earlier",?' to an extent which serves to show that definite limitations now exist in the correlation of simple and complex systems. However, significant progress is being made in filling gaps in the information. For example, similarities in the behavior of fluids in condensate fields with that of binary and ternary systems are becoming more systematically evident. A few studies of the behavior of water in paraffin hydrocarbon systems have been made Results of investigations of mixtures of carbon dioxide and the lighter hydrocarbons also are available Limited work has been reported con-

Jan 1, 1949

By W. N. Lacey, B. H. Sage

The growing background of experimental information concerning the volumetric and phase behavior of binary and ternary hydrocarbon systems is used as the basis for a comparison of these systems with naturally occurring hydrocarbon mixtures under conditions representative of underground petroleum reservoirs. The qualitative and semiquantitative similarities and differences between the two types of systems are considered in reference to the possibilities and limitations of using experimental data on binary and ternary systems for predicting the volumetric and phase behavior of naturally occurring hydrocarbon mixtures of low molecular weight. The possible influence on such phase behavior of water, hydrogen sulphide, nitrogen, and components of relatively high molecular weight is discussed. INTRODUCTION During the past two decades much effort has been devoted to the study of the volumetric and phase behavior of pure paraffin hydrocarbons and of binary and ternary mixtures of these compounds. Many of these studies were carried out with the direct objective of utilizing a knowledge of the detailed characteristics of binary and ternary mixtures of the lighter paraffin hydrocarbons for predicting the behavior of more complex mixtures. The ability to make such predictions with accuracy would be of great value in petroleum production and refining. Although the behavior of the methane-propane system' served at one time as a qualitative illustration of the probable characteristics of the more complex hydrocarbon mixtures found in nature, it' fell far short of requirements for quantitative predictions. The present paper endeavors to indicate the relation of the more recently accumulated information concerning the behavior of binary and ternary hydrocarbons to this problem. In discussing binary and ternary systems as examples pointing toward the behavior of multi-component systems no effort is made to present new methods of predicting the characteristics of natural hydrocarbon mixtures. Preliminary proposals have been made elsewhere for the prediction of volumetric phase equilibrium and thermodynamic data for multicomponent mixtures, utilizing as a basis the behavior of binary and ternary systems. Numerous other proposals have been made. That based upon the concept of a pseudo-critical state" has proved to be of value to the petroleum industry. Concurrently with this study of binary and ternary systems investigations have been made of natural hydrocarbon systems. Of the many publications reporting such experimental information only a few examples will be mentioned. A number of studies of black oil and natural gas have been made and much attention has been directed to extended and detailed investigations of the behavior of fluids in condensate fieldS 16,17,18,19,20. This work has been supplemented by some studies of the separation of bitumen from natural hydrocarbon liquids The over-all behavior of such systems has been used in predicting the volumetric and phase behavior of naturally occurring mixtures This background of experimental and correlated information concerning the behavior of multicomponent hydrocarbon systems also permits a direct comparison of the characteristics of binary and ternary aliphatic systems with those materials produced from underground reservoirs. PRESENTATION OF DATA The primary limitation encountered in using binary and ternary aliphatic hydrocarbon mixtures as examples of the characteristics of the fluids encountered in underground reservoirs lies in the existing lack of knowledge of the quantitative effect upon behavior of the presence of several important constituents, notably hydrocarbons of high molecular weight, water, carbon dioxide, hydrogen sulphide, and nitrogen. The presence of substantial quantities of hydrocarbons of fairly high molecular weight serves to increase the complexity of the phase behavior of natural systems. No simple systems yet studied give adequate guidance in this regard. The influence of such materials of high molecular weight was indicated earlier",?' to an extent which serves to show that definite limitations now exist in the correlation of simple and complex systems. However, significant progress is being made in filling gaps in the information. For example, similarities in the behavior of fluids in condensate fields with that of binary and ternary systems are becoming more systematically evident. A few studies of the behavior of water in paraffin hydrocarbon systems have been made Results of investigations of mixtures of carbon dioxide and the lighter hydrocarbons also are available Limited work has been reported con-

Jan 1, 1949

By J. W. Halley, G. L. Plimpton

Because of the two distinct stages in the solidification of rimmed steel, segregation in the rimmed ingot is more complex than that in the killed or semikilled ingot. In the earlier stage, chemical reactions, resulting in evolution of gas and vigorous stirring of the metal, effect a degree of negative segregation unique to rimmed steel. The composition of this zone constitutes the principal quality advantage of this type of steel. In the later stage of solidification, after the evolution of gas has ceased, the segregation follows the general pattern of a more completely deoxidized steel. However, the composition of the liquid remaining after the first solidification stage varies markedly from that of the original melt, some constituents having been partially removed as reaction products while the concentration of others has been intensified by rejection from the metal solidifying in the first zone. The aim, from the standpoint of segregation, in rimmed steel of high quality is to effect a maximum negative segregation in the rim zone without excessive concentration of undesirable elements at the center of the ingot. To achieve this aim, the composition of the melt may be varied and the furnace and pouring practice may be adjusted within certain limits. It is the purpose of this study to discuss segregation in rimmed steel from the standpoint of the mechanisms that produce it and to survey the phases of open-hearth practice that influence those mechanisms. Mechanisms Producing Segregation The mechanisms that determine the degree of segregation in the rimmed ingot are closely interrelated, making it difficult to select the primary factors and to determine a satisfactory order for presenting them. For instance, the question of sulphur segregation is relatively simple, since sulphur is not directly involved in chemical reactions in the ingot; but its concentration in the rim zone is dependent not only on its original analysis in the melt, its segregation coefficient, and the freezing rate, but also on the rate of its removal from the impure film on the solidifying surface. This washing action involves all the factors (such as freezing rate, the carbon-oxygen product, pressure, etc.) that determine the rate of gas evolution and hence the efficiency of film removal. Sulphur distribution between the rim and core is affected by the volumetric ratio between the two zones, and its segregation in the core is a function not only of the freezing rate of the core but also of all the foregoing factors that determine its concentration in the metal when solidification of the core starts. To simplify the presentation, it is proposed to treat the mechanisms affecting segregation independently in this section, reserving a discussion of their over-all effects for the section in which actual segregation data are given. The factors affecting segregation will be treated in the following order: (I) differential solidification, (2) removal of constituents as

Jan 1, 1945

By T. E. Scott, D. H. Sherman, C. V. Owen

It has been established' that vanadium exhibits a ductile to brittle transition temperature which increases with increasing hydrogen content. Optical microscopic examination at room temperature revealed no evidence of hydride precipitate in fractured specimens containing 100 ppm H, but hydrides were present in samples with 800 ppm H. More recently2 the strain rate and temperature dependences of the ductility drop in vanadium containing 6 ppm H were reported. It was argued that the ductile-brittle transition, while dependent on the presence of hydrogen, probably could not be explained by the precipitation of hydride. The bases of the argument were that 6 ppm H would not produce sufficient hydride to alter the ductility to the extent observed and no visual evidence of hydride was obtained. However, the data were not sufficient in these investigations 1,2 to define accurately the ductile-brittle transition temperature. Also, no information was available concerning the terminal solubility of hydrogen in vanadium at the low concentrations employed. westlake 3 has studied the electrical resistivity of vanadium at several hydrogen concentrations. He was able to detect the precipitation of hydride and to extend the hydrogen solvus to the composition and temperature range pertinent to the observed ductile-brittle transition behavior, Westlake compared his

Jan 1, 1968