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By K. I. Savage, S. C. Sun

This paper describes a process developed to recover coal, clays and pyrite from coal wastes. The process consists of fine grinding followed by coal and pyrite flotation which leaves the clays in the flotation pulp. A bituminous coal refuse containing 10% sulfur and 30% carbonaceous material was treated by this method to yield a coal product containing 4% sulfur, 10% ash; a pyrite product containing 45% sulfur (84% FeS2), 1% carbonaceous material; and a clay product containing 2% sulfur (3.5% FeS2). The coal yield was about 89%. The pyrite yield was about 77%. The process steps may be entirely flotation, or gravity separation (hydrocycloning) may be used to increase the pyrite : coal ratio in the flotation feed. Cost estimates for the process show a profit of $2.28 per ton of low pyrite grade refuse, but these do not include labor, maintenance, overhead and plant depreciation. The development of this process consisted of three parts: (1) exploratory tests, (2) op-timazation tests and (3) confirmatory tests. The objectionable qualities that sulfur imparts to coal have been commented upon from early times, and they have become more objectionable as the uses of coal have grown. In whatever form coal takes — raw, carbonized or gasified —the sulfur content remains objectionable, and therefore its compounds are removed as completely as possible. It has long been known that sulfur occurs in coal in different forms. In 1861, sulfur was said to exist in the state of sulfuric acid in combination with a base; in combination with iron as iron pyrites; as bisulfides of iron; and in combination with the organic elements of coal.' Pyritic sulfur is a term loosely used to cover the sulfur associated with iron in its various forms. The mineralogically recognized forms are pyrite (FeS2), pyrrhotite (Fe 1-x S) and marcasite (FeS2). The particle sizes of pyrites vary widely. Isolated grains of marcasite smaller than 15 microns have been found disseminated through coal.2 Hair-like "veins" of pyrite filling cracks in vitrain have been found. At the other extreme, lumps or nodules of pyrites large enough for removal by hand picking have been encountered. Organic sulfur, unlike pyritic sulfur, does not exist as discrete particles, but is instead intimately associated with the coal structure and thus it is impossible to remove it or reduce its concentration by physical or mechanical means.2 In the preparation of coal for its various markets, the pyrite minerals (pyrites) are separated from the raw coal feed. This separation process concentrates the pyrites in the tailings or other waste products. It would be desirable to recover these pyrites for three reasons: (1) Pyrites are potential sources of sulfur and iron. In 1967, for the fifth consecutive year, Free World consumption of sulfur exceeded production.3 Propelled by the shortage, the domestic price of sulfur has risen from $24 to $38 per long ton (bright). (2) The refuse, when placed in piles, becomes ignited. The pyrites (FeS2) bum, giving off SO,. Thus, the pyrites are a cause of air pollution. (3) Also, the pyrites undergo chemical reaction when exposed to air. The refuse is leached by waters which result in stream pollution due to the water-soluble iron and acidic reaction products. Coal refuse also contains coal minerals and clay minerals. Therefore, any process for recovering the pyrites must successfully separate them from the coal and clay minerals. In the study discussed here, ten different bituminous coal refuse samples were successfully upgraded in pyrite content. These samples represented a wide variety of coal waste materials from Pennsylvania and other states. The variabilities of the sulfur and coal contents are shown in Table I. The extremes are Sample J, a high sulfur-low coal, and Sample B, a low sulfur-high coal. Definitions of some of the symbols or terms used in this report are given below: Mesh size—Tyler standard mesh screen sieves with an opening based on the square root of two. Fe —Indicates iron, as determined by a stannous reduction-dichromatic oxidation method. S—Indicates sulfur, as determined by the ASTM "Eschka" method for sulfur in coal.

Jan 1, 1969

By Frank Calvin Roberts

An examination of the various devices employed for operating blast-furnace charging-bells has led me to design the arrangement slrown in the accompanying figure. In order to contribute to the even distribution of stock, the movement of the bell should be in a vertical line, since any tendency to side-thrust which may be in-

Jan 1, 1888

By Max Boehmer

The first and most lasting impression made upon the mind of him who examines a mine or a mining district consists in the observation that in each and every case there is an intimate association of the ores with the eruptive rocks in the dietrict. The mines in the Mississippi valley seem to be the only excep-

Jan 1, 1904

By K. A. Slagle, D. K. Smith

weight obtained. Additives used in conjunction with salt in these slurries have included silica flour, calcium ligno-sulfonate and cellulose retarders, granular lost-circulation materials, bentonite and selected low-water-loss additives that are not significantly deteriorated by the presence of the chloride ion. In some other areas of South Texas, the salt-saturated slurries have been used quite extensively for improvement of the flow properties of slurries and attainment of better circulation characteristics at lower displacement rates. Concurrently with this property, the protection of shales and shaly sands is also realized, as well as useful retardation of the slurry. Resultant superior cementing jobs have been indicated by both communication tests and acoustic logs for bonding to pipe and formation.' In one section of Louisiana, a major oil company has been using salt-saturated API Class A cement with calcium lignosulfonate retarder for cementing through the Miocene at 9,000 to 10,000 ft. This is another of the situations where interbedding of sands and shales exists, creating difficulty in maintaining formation competency when a fresh-water slurry contacts the clay minerals of the formation. Further work has also been done in the shaly Miocene formation at 13,000 to 15,000 ft where fairly close water or gas contacts are encountered. Indications thus far are that better segregation of these various fluids is obtained by use of the saturated salt slurries because of their improved formation bonding characteristics. In addition to the properties of salt in this situation, attainment of turbulent flow at minimum displacement rates has also been accomplished by use of an additive to help provide exceptional dispersion and viscosity reduction of the slurry. Another oil company was encountering considerable expense in completing wells in Southwestern Louisiana due to extensive block squeeze requirements for effective separation of zones. A very effective mud program was being used to minimize washout in the shale sections and, apparently, a nearly gauge-size hole was being obtained. However, primary cementing results with fresh-water slurries were generally poor. On a few occasions when slurry was actually circulated to the surface, large pieces of shale formation were brought out of the hole with the slurry, indicating a severely water-sensitive, sloughing formation. Inhibition of shale heaving was being accomvlished in the drilling program, and immediately indone ipon circulation of the fresh-water slurry even though it contained a low-fluid-loss additive to reduce filtrate damage in the sands. The subsequent change to salt-saturated slurry yielded 11 successful primary cement jobs out of 12, compared to the previous success ratio of practically zero. Since these were deep, high-temperature wells in the range of 13,000 ft with high-pressure zones necessitating 17.5-lb/gal fluid densities, the slurry used was API Class E cement, silica flour, weight material, retarder, salt saturation (which also reduced the amount of weight material) and maintenance of low fluid loss by use of a salt-compatible additive. Other salt slurries have been used to a limited extent in this same general area for similar problems at depths ranging from 5,000 to 17,000 ft. In the shallower wells, the cement has usually been API Class A where the salt functions as a retarder, and in the deeper wells API Class E cement is used with the additional salt advantage being its increased slurry weight and inability to dissolve salt stringers. A considerable number of squeeze jobs have also been done on older wells using the salt-saturated slurries with very good results. MID-CONTINENT In North Texas, salt-water slurries have been used for cementing the Woodbine sand, Strawn sand, KMA sand and Pettit lime. Shales surrounding these formations have created the same difficulty in obtaining separation of producing zones that has been the problem in other areas. Depths in this area range from 3,400 ft for the Strawn to 7,400 ft for the Woodbine, and concentration of salt has varied accordingly. In the deeper wells, where retardation is desired, saturated salt-water cement is used; for the shallower wells, in order to provide shorter waiting-on-cement times, the amount of salt has been 18 per cent by weight of the mixing water. Results have been excellent with no reported failures on any of the salt cement jobs; where acoustic bond logs have indicated indifferent bonds previously, they are indicating very good bonding for the salt slurries. In Oklahoma various shales of Pennsylvanian age exhibit a high degree of sloughing in the presence of fresh water, causing severe washouts above and below sand formations which it is desired to isolate. This situation exists to some degree in practically all parts of Oklahoma and includes formations of other ages such as the Wood-ford shale. For the past few years, salt-saturated cements and displacement rates as high as practical have been used as a remedy for this problem, with very good results. The Layton and Bartlesville formations are two examples of shaly sands where saturated slurries have been helpful. In one area where five wells were drilled through this type of problem shale without obtaining a satisfactory primary cement job, a change was made to salt-saturated cement preceded by a suitable chemical wash for the drilling mud involved. Acoustic bond logging indicated excellent bonding, and final completion bore out this result by being trouble-free. This type of slurry has also been used extensively on squeeze jobs where shales have been heaving around the producing formations. Predominantly, the basic slurry has been either API Class A cement or a pozzolan cement—although, as deeper wells are being drilled, the use of salt in Class E cement is also increasing. Salt cement in West Texas has been used primarily to help prevent channeling through the shales around the Delaware sand, Queens dolomite and Hope lime. Many of the shaly and dirty sands of this area are sensitive to the filtrate from a fresh-water cement. Salt at 16 to 18 per cent by weight of mixing water has been added to centent, and has been effective in controlling formation damage and communication between zones in these formations. Use of these lower salt concentrations is dictated in this area by the relatively low formation temperatures where retardation of the slurry would create unduly long waiting-on-cement times. Also, quite a bit of cementing has been done in this area using salt concentrations in the accelerating range— that is, 2 to 5 per cent by weight of water. Specifically, these concentrations have been used in coiljunction with high percentages of gel to overcome the retarding effect of the calcium lignosulfonate dispersant, although there are probably several shales where these concentrations could provide some degree of formation stability. On several occasions, the salt has also been used to lower the critical velocity or rate for turbulence with the slurry, particularly in the pozzolan cements. On wells in the Hope lime, it has usually been necessary to squeeze the shale above and below the lime to get a water-free completion. Use of salt-saturated slurries has largely eliminated this

By Wolfgang O. Gluschke

INTRODUCTION Virtually all countries have general legislation covering most aspects of mining and mineral processing, including investment and tax laws, safety and health regulation, and specific rules applying to exploration reporting procedures. Yet most developing countries negotiate individual agreements with foreign investors for major mineral projects, in particular when all or part of the expected output is exported. Such agreements are known under several different names, as for example concession agreement; technical assistance agreement or service contract; management agreement; production sharing contract; joint venture; or contract of work. The objectives and conditions governing such contracts are as diverse as these titles are. While a mining project is only one among a large mumber of similar undertakings in industrial countries, in most developing countries such projects usually have a dominating position within the country's economy. The general legislation is often inadequate and insufficiently detailed to cover all aspects of large projects with extensive foreign inputs and international markets. Therefore, the need for specific arrangements. Specific arrangements may also become necessary due to the complexity of markets for mineral products, the large number of participants - equity partners, suppliers, financial institutions, buyers, etc. - or economic and political conditions in the host country and fiscal regulations in the home country of the investors. Most agreements are concluded between governments, or government agencies, in developing countries and private industry headquartered in developed market economies - Canada and the United States of America in North America, Western European countries, Japan, South Africa and Australia - or, in some instances, with state-owned firms in these countries. There are fewer agreements between developing countries and the centrally planned economy countries - Eastern Europe and the USSR - which cannot be considered here because of absence of adequate information. Agreements can be concluded at any of the different stages from exploration through closing of a mine. While most contracts are negotiated at the time when a potentially viable ore body has been delineated and investigated sufficiently to anticipate a realistic time for commencement of production, other agreements start with "grass-roots" exploration, during operation of a mine, smelter or refinery or, exceptionally, after a temporary shutdown. While several major provisions are included in all types of agreements, others are covered in much more detail (or not at all) in some contracts reflecting the specific work programme of each project. While it is realized that subdivision and classification of complex contractual relations is necessarily arbitrary to a certain extent, such grouping is useful in practical terms, especially for the non-specialist. The following discussion, therefore, will start with a description of the major forms of contractual relation - concession, investment contract, joint venture, management agreement, service and production sharing contracts. Major issues covered in all, or almost all, agreements will then be dealt with. These include stages of development, corporate structure and control, fiscal arrangements, infrastructure development and environmental law, and dispute settlement and renegotiation. FORMS OF CONTRACT RELATIONS There has been marked change in the type of agreement entered into during the 1960s (and before) and the early 1970s and the period thereafter. While straight "concessions" - granting of exclusive rights to foreign investors over a certain deposit or areas with little restriction or well-defined obligations - were the rule during the first half of this century, more complex agreements have evolved since. Some of these cover every conceivable aspect, foreseen or only possible, and define rights and obligations of all partners to the last detail. Over the years, agreements have without doubt become more beneficial for the developing host countries, in part as a result of well-publicized nationalizations, as for example in Chile, and in part due to changed attitudes in all countries

Jan 1, 1985

By W. van der Knapp

A theoretical and experimental ana1ysis is given of the change in volume of a porous medium due to changes in external and internal pressures. The result enable one to deduce directly the effect of large increlents in stresses. It is shown that the three-dimensional representation of the volume of a nonlinear porous system is a cylindrical rules surface, the generating lines of Which have a slope according to the solid rock compressibility. Analytical expression for such a ,surface is very simple. It follows that the bulk and pore compressihilities depend only on the difference between pore fluid and external hydrostatic pressure, i.e., the effective rock frame pressure. From measurements on a number of sandstones as well as limestones it can be conduded that for practical values of this effective frame pressure the pore compressibility falls in the range between the compressibility of water and that of undersaturated crude oil. In general, pore compressibility is found to be higher the lower the porosity. For a particular limestone reservoir pore compressibility and porosity could he related by means of a simple empirical formula. Results from the described study find a direct applicxtion in material balance calculations and in prob1ems of liquid flow through porous media. Since the elastic constants of the rock bulk material enter into equatiorls for velocity of acoustic waves, the results are also of importance for calculating rates of wave propagation in these media. It is shown for sandstones with 1.5 to -10 prr cent porosity that laboratory measured porosities may differ from those lender reservoir conditions by about I per cent of their value. The difference for low porosity limestotnes can be of the order of 10 per cent. The subsidence caused by elastic deformation of reservoir rock is shown to he very small. General formulas relating pore and bulk volume to external and internal pressure can be derived, as has been shown by Biot1, Gassmann2 and Geertsma.2 Their theories describe the differential change in volume caused by a variation in pore fluid tension and external hydrostatic tension. It has been known for a long timei that the stress-strain relations of a packing of spheres are essentially noninear. Our experiments show that for almost all reservoir rocks which arc elastically deformable the relation between volume and loading is also a nonlinear one, resembling that of a packing of spheres very closely. The behavior of these media is often described by using the linear stress-strain relations for small incremental stresses and strains in the vicinity of a pre-stressed condition." The present study differs from these considerations in that it enables one to deduce the effect of large increments in the stresses directly. In analogy to the stress tensor for a homogeneous body the stress tensor for a porous body can be written in the conventional way: where the tensor components, o, and t, represent the total forces acting on the faces of a unit cube of porous material. This tensor can be split into two parts. a hydrostatic and a deviatoric part, as follows2,3,1 where the component of the hydrostatic stress system, a. equals The hydrostatic stress causes a change in volume whereas the deviatoric stress system gives rise to a change in shape only. One of the difficulties in describing changes of volume occurring in reservoir rocks is that the relations connecting these volume changes with external and internal stresses are essentially non-linear. A complete description requires the bulk volume, V,,, as well as the pore volume,V,,. to be known as a function of both the changes in pore fluid tension (v) and the hydrostatic tension on the outer boundary.

By G. A. Stamboltzis, N. Arbiter, C. C. Harris

Fracture under low-velocity free-fall and double impact and under slow compression have been investigated. The pattern of breakage and the size distribution of resulting fragments of sand-cement and glass spheres have been determined. Photoelasticity methods were used to simulate the stress distributions in free-fall impact in order to explain the observed patterns of breakage. Oblique fracture planes, occurring only in free-fall impact, develop along lines which coincide with the trajectories of maximum compression as determined by mathematical analysis. Breakage efficiencies for different modes of fracture were compared for both types of spheres. For the same specimen and loading system, static loading and low-velocity dynamic loading induce geometrically similar stress fields resulting in reasonably similar fracture patterns and shapes of fragments. This work had its origin in a desire to understand three fundamental processes involved in autogenous comminution: namely; free-fall impact, double impact, and slow compression. To simplify the investigation, it is preferable to reduce the entire multi-stage fracture process to its most elementary form; that is, to study products resulting from a single-stage operation, such as the breakage of a specimen under single fracture conditions. The goal of this research is to study the energy utilization in the single fracture of brittle specimens and to relate the pattern of breakage and the resultant fragment size distribution with the nature of the material, the specimen size, the manner of load application, and the rate of loading. Published works on single fracture have mainly been concerned with tests on large (> 1-in.) irregular mineral pieces, especially coal and coke. These were mainly friability tests employing a single blow on closely sized pieces. More recently, small mineral specimens in the sieve range and glass spheres have been investigated.5-7 Kick8 has reported free-fall and double impact tests with large large cast-iron, cement, and clay spheres. The establishment of a minimum breaking height independent of size in the free-fall impact tests, and the direct proportionality between the minimum work required for fracture and the volume of the specimen in double impact tests were used by Kick as an experimental proof of his classical law of "Proportional Resistances." In the present work, spherical shapes were chosen because of their simple body geometry and consequent impact and stress field symmetry. Because the study involves several physical principles in connection with brittle-fracture, it may be of interest in fields where the strength of materials is of importance. APPARATUS The equipment for the free-fall impact testing is illustrated in Figs. 1 and 2. This consisted of a massive (17 x 17 x 3-in.) hard steel plate onto which specimens were dropped and a specimen release mechanism which could be set at any desired height up to 10 ft above the plate so that the impact velocity could be varied up to about 25 ft per sec. Double impact breakage is characterized by two points of loading situated at opposite poles. For this mode of breakage the apparatus was modified (Figs. 3, 4 and 5) so that a falling mass provided an impact of predetermined magnitude on a specimen resting on the plate. A spring-loaded device operated immediately after fracture to arrest the falling mass and to record its residual kinetic energy. Precautions were taken to avoid secondary breakage. Slow compression tests were performed on a conventional hydraulic testing machine, the specimen being held between two hardened parallel bearing blocks. In the case of glass spheres, carbide bits were used. Photoelasticity studies were performed on two-dimensional models held in a loading frame equipped with a force gauge (Fig. 6). The models were viewed in a polariscope and isochromatic fringe patterns were recorded photographically. SPECIMENS Sand-Cement Spheres: A series of sand-cement spheres were prepared by molding in spherical glass flasks.

Jan 1, 1970

By W. D. Haentjens, A. P. Pipilen, M. Weintraub, A. A. Orning

W. D. Haentjens (Barrett, Haentjens and Co., Hazleton, Pa.) — The authors are to be complimented on undertaking a project which has little available experimental data. There are so many variables in the hydraulic transport of solid materials that it is difficult to correlate the experimental information from one series of tests into usable data involving other materials or even similar materials but of different size consists. The friction data is of particular interest to those involved in pipeline design. Most such pipelines, however, involve portions which are not level and the effect of sloping or vertical lines might also be considered in extensions of this test work. Pump manufacturers are concerned about criticism resulting from the stated amount of degradation occurring in a pump. The amount of degradation is affected somewhat by pump design and this should be taken into consideration. The pump which was loaned for this work was a modification of a standard medium duty slurry pump. This modification was for maximum particle size, however if minimum degradation is the object, then other design changes would be indicated. Although there is a tendency to be less concerned with degradation in industrial applications, it is nevertheless an important factor in many uses and further studies should be made. In particular, the amount of degradation could possibly be segregated into more classifications, rather than charge some losses to the pump which apparently are occurring in other handling. It seems difficult to evaluate the degradation which occurs in handling the coal into the pump sump and in removing it from the line into the tank. Each handling, of course, contributes some degradation, as does the screening operation itself. These are all charged to the pump, or to the pipe line and pump together; and, although they may be small, they could possibly be evaluated. It is interesting to note the verification of the old rule of thumb of maximum particle size equal to approximately one-third of the pipe size. Our experience has shown size distribution to have an effect on the flow characteristics and if this data is available for the tests which were run, it would be interesting supplementary information. A. P. Pipilen, M. Weintraub and A. A. Orning (Authors' Reply) — In this paper the authors have attempted to outline some of the major factors affecting a rational design for a solids-liquid transport system. They are grateful to Mr. Haentjens for pointing out several other equally important considerations. Pump manufacturers, in general, should be complimented on the strides that have been made in decreasing particle degradation within the pump. Considerable research and a great deal of mathematical analysis is required before pump design in this field can become a science rather than an art, for each system requires a different set of compromises. As Mr. Haentjens indicates, maximum-particle-size handling capability may be inconsistent with minimum degradation; even more important, the rotor profile for the most efficient transfer of energy to the fluid may have to be compromised to reduce particle breakage, for, whenever particle density differs from fluid density, the two phases will have different trajectories. Some evidence of this geometric factor is provided by a cursoy analysis in the Bureau of Mines Report of Investigations now in preparation, where it is indicated that, for the pump used, degradation decreased when the tangential velocity was decreased and when the radial velocity was increased. This relation, itself, is probably a function of particle size and concentration. Some data on particle size distribution, as requested by Mr. Haentjens, will be provided in the Report of Investigations referred to above in addition to that already presented in Table II of the original paper. However, in the limited number of tests it is difficult to distinguish between cause and effect, for not only did the particle size distribution alter the flow characteristics, but, through the medium of degradation, the operating conditions rapidly altered the particle size distribution.

Jan 1, 1965

By Wayne L. Worrell

Thermodynamic data for the stable carbides and oxides of chromium, molybdenum, and tungsten have been critically eualuuted and are used to determine the stable condensed phases at 1 atm total pressure in each metal-carbon-oxygen system. Pourbaix-Ellingham diagrams have been constructed and are used to estimate the minimum temperatures neces.see)*y to oblain these metals by corbolhermic redlrction under reduced pressures. USING recently reported data for the carbides and oxides of chromium, molybdenum, and tungsten, the stable phases in the Group VI metal-carbon-oxygen systems at specific temperatures and pressures can be determined. The thermodynamically stable regions in each metal-carbon-oxygen system can be completely pictured using a Pourbaix-Ellingham diagram in which the two coordinates are oxygen potential (-RT In Po2) and temperature. Worrell and chipman' have described and constructed such diagrams for the metal-carbon-oxygen systems of vanadium, columbium, and tantalum. Downing2 has used similar diagrams to provide a description of the reactions in submerged arc furnaces. One of the examples which he cited was the Cr-C-O system; however, an improved diagram is presented in this paper using recently obtained data for the carbides of chromium. Although some of the oxides and carbides of the Group VI metals exist over slight ranges of composition,3 all solid phases are represented as stoi-chiometric compounds in the subsequent diagrams. Any error introduced into the calculated equilibria by neglecting the compositional variation of these phases is less than the uncertainty in the thermodynamic data. In a Pourbaix-Ellingham diagram for a three-component system, the phase rule requires that at equilibrium four condensed phases specify a point, three condensed phases determine a line, and two condensed phases define an area. To obtain a well-defined area at high oxygen potentials and teniperatures, the initial carbon to oxygen mole ratio is specified to be more than sufficient to reduce the oxide but not enough to convert all the metal to carbide. Thus, the lowest regions in the subse- quent Pourbaix-Ellingham diagrams represent areas in which the metal and its carbide are the stable condensed phases. Cr-C-O SYSTEM A) Thermodynamic Data. To simplify the subsequent calculations, all thermodynamic data are presented in the form of linear Gibbs-energy-of-formation* equations which were derived for the temperature range 505° to 2000°K and are reasonably accurate over the entire temperature ranges of the diagrams. The thermodynamic data for the compounds occurring in the Cr-C-O system are summarized in Table I. Several volatile chromium oxides have been reported,4 but their influence is negligible in the Cr-C-O system. Thermodynamic data for CO and CO2 were taken from the compilation of Coughlin.5 The only solid chromium oxide sufficiently stable to exist below 1800°K in the Cr-C-O system is Cr2Os.11 The Gibbs-energy-of-formation equation for Cr2O3 was obtained by revising the data tabulated in Coughlin,5 using the heat of formation of ah' and the high-temperature thermal data for chromium.7 In 1953 Richardson8 re-evaluated the original work of Kelley and coworkers,9 who measured the thermodynamic properties of the chromium carbides. However, the high-temperature equilibrium results of Boericke9 yield values for ?G°f of Cr2O3 which are 2 kcal more positive than the accepted data. His results for the chromium carbides are based on the same questionable equilibria. Gleiser10 recently determined the Gibbs energy of formation of Cr3C2 and the equation in Table I was calculated from her data and the thermal data of Kelley and coworkers.9 Thermodynamic data for the Cr7C3 and Cr23C6 carbides were obtained by combining the Cr3C2 data

Jan 1, 1965

By Herbert W. Huse

Nitrogen, and its compounds, unique among the materials described in this volume, is absolutely essential to the existence of the human race. Almost all minerals are important and the absence of any one of them would be sorely felt; but nitrogen is an integral part of the cycle of life itself. Man cannot live without nitrogen which, as an inert gas, composes the major part of the air he breathes; as compounds, nourishes the vegetation which he eats; and, as protein, forms a part of his very flesh and blood. Nature originally provided man with a vast reserve of usable nitrogen compounds in the form of fertile soil. She constantly replenishes the supply by "fixing" nitrogen in the air at the estimated rate of 400,000,000 tons per year (an insignificant 6 lb per acre) during electrical storms. She has also placed certain microorganisms in the soil which are able to "fix" nitrogen and convert it into forms which plants can use. Legumes like cow peas, soy beans, clover, and alfalfa have extraordinary roots which serve as stimulating hosts to these bacteria which, in turn, nourish the plant. By plowing in all or part of such crops, their above-average nitrogen content can be returned to the soil for other more useful crops. The mechanism for this recycle is supplied by "denitrifying" bacteria which attack the dead plant tissue and liberate nitrogen and ammonia. However, since one crop of grain, sugar beets, potatoes, tomatoes, etc., takes out a major portion of the nitrogen which a plowed-in legume crop can supply, this method of fertilization is obviously inadequate. Drastic intervention by man has become necessary to support the ever-growing population of the world.9,15,20 Old civilizations with a high population density, such as the Chinese, were able to exist for centuries by carefully tilling the soil, rotating crops, and returning to the soil all the nitrogen in vegetable wastes plus human and animal excreta. But the lack of a means for augmenting their supply of nitrogen placed a ceiling on further development and kept the mass of the population in a chronic state of undernourishment, frequently punctuated by famine. Nitrogen plays another important role in the life of mankind. In the form of explosives, nitrogen helps to wrest from the earth many materials needed for our material well-being. Also, in the form of explosives and propellants, nitrogen increased the destructiveness of wars to a point only exceeded by the fantastic power of atomic energy. Man's first really effective efforts to improve his position with respect to nitrogen began in the 18th Century with the mining of sodium nitrate. By the late 1880's this had become a big industry serving a large part of the world. In the late 1890's nitrogen, in the form of ammonia, was being recovered from coke-oven operations. In 1900 nitrogen, in the form of nitric oxide, was being obtained from the air by an electric-arc process. About 1904 another "fixation" process based on the reaction of nitrogen with calcium carbide to form cyanamide was commercialized. By 1913 the Haber-Bosch process of "fixing" atmospheric nitrogen by reacting it with hydrogen to produce synthetic ammonia was successfully applied on a large scale, first in Germany and then throughout the industrial areas of the world.9 All the above methods of obtaining nitrogen compounds are still in use and, between them, they assure mankind of adequate supplies for all time. While this fortunate situation is not unique amongst industrial raw materials, all too few of man's needs are so well in hand.

Jan 1, 1960

By W. M. Myers

Certain minerals possess inherent color and other properties that make them suitable for the pigmentation of paints, mortar, plaster, concrete, face brick, and other materials. Their production is one of the most ancient of mineral industries and their use by primitive man is well known. These natural pigments have some economic factors in their favor, particularly wide geographic distribution, low cost of production, ease of preparation, chemical stability, and permanence in use so that they continue to form the basis of a small but useful industry. When used in paints such pigments act as a filler and supply body and opacity in addition to color. Natural mineral pigments are prepared for the market by the comparatively simple operations of washing, grinding, blending, and calcining. Any one, or all of these processes may be applied to a single pigment. The development of synthetic pigments and the use of byproduct materials have introduced competition with the products of nature and are having a growing influence on the economic position of the mined minerals. Development of the Industry The industry developed to commercial stature in Pennsylvania largely because of the presence of beds of ocher extending from Easton in a southwesterly direction toward Reading, and a variety of small iron mines in the region. The mining of paint ores in the Lehigh Valley was active as early as 1850 and shortly after the Civil War the establishment of mills expanded production and led to the development of new products and eventually the manufacture of synthetic pigments. Pennsylvania continues to maintain it.s leadership as a producer of mineral colors. Production is recorded also in New Jersey, Illinois, Virginia, Ohio, and Georgia. Iron as a Pigment Iron in various compounds is the most important pigment in nature. The iron pigments are characterized by stability, light fastness, good covering power, high index of refraction, and economy in production. Ferrous compounds display a typical green coloration. This has not been employed as a commercial pigment to any great extent except incidentally in such greenstones as have been used in construction, or crushed and sized for application as a granule to roofing. Ferric oxides are characteristically red and form an important group of industrial pignents. Hydrated ferric oxides exhibit various shades of yellow and are present in such familiar pigments as ocher and sienna. The addition of small amounts of manganese oxide or carbon as organic matter to the yellows produces the brown umbers. Magnetite is one of the few black minerals that grinds to a black powder. The mineral pigments vary from earth colors of low intensity and great dilution of iron content to almost pure iron compounds with high tinting strength and correspondingly greater value. There has been some relationship between the mining of iron ores and the production of mineral pigments; although the production of colors is not carried on appreciably as a byproduct of iron mining. A number of mineral pigment producers, particularly in the eastern states, have operated mines which in the past were small producers of hematite, bog ore, or carbonate ore. The knowledge of the location of the deposit and its possibilities as a producer of pigment are due to its past history as a producer of metallic ore. Many iron compounds may be changed in color by calcination, the end product being Fe2O3, a stable red oxide. The yellow hydrated oxides may be changed to red. The gray carbonate, found in Carbon County, Pa., calcines to a fine red product. Ferrous sulphate (copperas) often available in tonnage as a byproduct of the steel industry, breaks down under heat or chemical action leaving a residual red oxide. Pigments produced by calcination or dissassociation of compounds possess the advantage of fine particle size and ease of grinding. Mineral Pigments MINERAL BLACKS Many black minerals grind to a light colored powder. This characteristic is familiar to the mineralogist as the white streak produced by a black

Jan 1, 1950

By George W. Crawford, W. P. Aycock, E. W. Hough

Forty oilfield brines have been examined so far by a polarographic technique new in petroleum engineering called the "tensatnmetric method" by the team of biochemists who perfected its use in their field. Samples of brine were obtained from various oil fields in which the wells were known to be producing fluid from oil productive zones in well-known geologic formations. Most of the reservoirs from which the samples were obtained are believed to have an active water drive under the prevailing conditions of operation. The 40 samples represent brines produced front 16 different formations of various geologic ages. Graphs have been prepared of the data obtained in the testing of each sample, and the distinctive waife-like curves so obtained are characterized by reproducible profiles, called "response curves." Careful comparison of the response curves of salt water coming from different fields producing from the same geologic formation reveals that the curves are similar. The response curves of salt water coming from productive zones of different geologic formations are characteristically different. Preliminary work offers the further hope that response curves of an oilfield brine indigenous to a particular oil-bearing formation and hence representative of a particular geologic environment, such as deposit-ional and all subsequent morphological conditions, may be of value in reservoir engineering in the interpretation of surface and interfacial phenomena. For example, the wettability of the rock matrix and more specifically, the classification of productive oil-bearing strata as hydrophyllic or hydrophobic may be determinable. However, many more brines must be examined and the resulting response curves analyzed in comparison to known causal phenornena before this objective is achieved. INTRODUCTION One of the perennial moot questions in the literature of petroleum engineering is whether the reservoir rock is oil- or water-wet. Possibly an answer to this question could come from a careful examination of oilfield brines. None of the conventional methods of examining brines (chemical analysis, pH and electrical conductivity measurements, and the like) answer the question. Careful analysis of reservoir behavior observed in the exploitation of oil fields, particularly in the application of fluid injection, has been fruitful to the extent that a few reservoirs are believed to be properly classified. Physical chemistry suggests the behavior of reservoir brine and rock may be due to something in the brine in small amount. The ever increasing development and modification of theory in the general field of surface and interfacial chemistry has, and is, contributing to a better understanding of the problem, particularly as theory is verified by data. The work herein reported was begun in 1953 by Hough and Roebuck 1,2 who employed a new form of alternating current polarography, i.e., tensammetry, developed by Breyer, et a13,4 and who studied eight oilfield brines in adapting tensammetry to petroleum engineering needs. THEORY AND DEFINITIONS Tensammetry is a new technique of inquiry into surface phenomena. Specifically, a weak alternating current voltage is superimposed upon the direct current voltage applied to a dropping mercury electrode in contact with an electrolyte containing a small amount of a surfactant. The resultant alternating current can be measured and provides the experimental data for this new area of research. Under the influence of the direct current voltage, polar molecules arrange themselves in a double layer at the electrode. This double layer may be compared to a variable condenser, the capacitance of which is a function of the imposed direct current voltage. The direct current voltage determines the degree of adsorption of the surface active molecule on the electrode. Whenever the molecules are strongly adsorbed on the electrode, the capacitance of the double layer is low and the alternating current through the cell is low. Desorption occurs at some values of the direct current voltage, and at these voltages the capacitance of the double layer is high, resulting in an increase in the alternating current through the cell. The direct current

Jan 1, 1958

By S. R. Maloof, W. R. Mitchell, J. A. Mullendore

Preliminary experimental evidence is presented to show that the metallic impurities aluminum, iron, and silicon, and beryllium oxide as found in commercially pure hot-pressed beryllium powder can be reduced to lower Concentrations by Zone -Purification techniques. The reduction in the concentration of aluminum to extremely low levels (10 PPm) is noteworthy, since earlier work demonstrated that aluminum is a major factor contributing to the hot-tearing of beryllium during fusion welding. On the basis of present findings, a method is suggested for producing beryllium metal of improved weldability. EXPERIMENTAL research now being conducted on the purification of beryllium indicates that several of the metallic impurities and beryllium oxide can be reduced to lower concentrations by employing standard horizontal zone-refining techniques. For the preliminary work, commercially-pure hot-pressed beryllium having a purity of 97.84 pct was used. The chemical composition is given in Table I. The hot-pressed beryllium was machined into bars 5/8 by 5/8 by 4 to 6 in. in length. Beryllium-oxide boats which had been conditioned by prior heating in a vacuum of 10"5 mm of Hg at 1100°C for 3 hr were used to hold the beryllium while it was zone melted. The boat with its charge, along with a smaller beryllium-oxide boat containing scrap beryllium to be used for gettering purposes, was loaded into a quartz tube and evacuated to 10-6 mm of Hg. Alter alternately evacuating and flushing three times with purified argon, the furnace tube was backfilled to a pressure of 1/6 atm of A and sealed off by means of a vacuum-tight stopcock. It was then removed from the pumping equipment and mounted on the traveling carriage of the zone-refining apparatus. Heating was accomplished with a 10 kw 450 kc induc- tion heating unit using an induction coil consisting of two turns of 3/16-in. diam copper tubing. Before starting to zone melt, the atmosphere in the furnace tube was gettered by heating the scrap beryllium in the smaller boat to above its melting point and holding at temperature for several minutes. The carriage was then shifted so as to locate one end of the beryllium ingot in the large boat within the induction coil. A molten zone approximately 3/4 to 1 in. was established by loading directly into the ingot. The molten zone was moved very slowly along the length of the ingot. Before each pass was made the procedure for evacuating, flushing, and backfilling, and so forth was repeatedI' Speeds of 1 1/2 and 3 in- per hr were used with up to twelve zone passes. The appearance of a typical zone-refined ingot is shown in Fig. 1. After zone refining, the grains in the ingot appear to be elongated in the direction of zone travel, whilst before, they are essentially equi-axed. A microexamination revealed the presence of a network in the beryllium grains as seen in Fig. 2. Laue spots in back reflection pictures taken of the sample were not sharp, indicating the presence of subgrains in the structure. As can be seen, however, many of the network boundaries cross beryllium grain boundaries. It has been shown by Martin and Moore1 that beryllium solidifies as a bcc structure which then transforms to the hexagonal structure at about 1250oC.It is believed that the observed network is merely the outline of the bcc structure which formed from the melt and are not subgrain boundaries. In order to eliminate surface contaminants, approximately 1/16 of an inch of material was removed from the outer skin of each ingot after zone refining.

Jan 1, 1962

By J. L. Wyatt

THE smelting of ilmenite to produce a slag rich in titanium, with pig-iron as a byproduct, introduces new concepts in electric smelting metallurgy. Titanium slags are characterized by low electrical resistance, thereby requiring a different type of electric furnace operation, and power supply sources substantially different from those encountered in normal steel melting and siliceous ore smelting furnaces. This paper describes special apparatus for determining specific electrical resistivity of titanium slags, and reports the values obtained on slags encountered in the process of smelting ilmenite ores. In an induction furnace under conditions approximating normal furnacing operation, 25 general heats and 6 special standardization and comparison heats were run. Results indicate relatively low resistivity. Resistivity depends primarily on slag composition, and, to a lesser degree, on temperature. During the summer of 1947 a cooperative project between the National Lead Co. and the Bureau of Mines was conducted at Boulder City, Nevada, in the Electrometallurgical Laboratories of the Bureau. The project involved smelting of ilmenite ores in electric furnaces, and has been reported in detail.' The author participated as a member of the staff of the National Lead Co. during the entire campaign. One outstanding characteristic of the titaniferous slags, their apparently excellent and variable electrical conductivity, was considered sufficiently important to warrant further study. Although little electric smelting of iron ores has been done in the United States, a certain amount of information is available for comparative purposes. Personal experience in smelting siliceous iron ores in electric furnaces furnished further information for comparison. In general, silicate slags are relatively poor conductors of electricity. Current flow during smelting operations may be maintained through a floating layer of coke on top of the slag bath, or through a bath of molten iron, beneath the slag. Silicate slags are not sufficiently conductive to furnish a path for current passage when normal furnace voltages are used. Experimental smelting of a silicate iron ore was undertaken for comparative purposes. A fluid melt was not obtained until the FeO content was reduced to 15 pct. The resistivity increased as the FeO content decreased, FeO compounds being the most conductive of the various oxides in such a normal slag system. The converse appears to be true in slags containing large percentages of TiO2. It has been found that titanium slags become molten with FeO percentages in excess of 30 pct, and that the conductivity becomes generally better as the FeO con-tent of the slag diminishes. This phenomenon was demonstrated in the furnacing operations at Boulder City. During the initial smelting period furnace electrodes could be held immersed several inches in the slag, with tap selectors set for a no-load voltage of 70 v. As the FeO content decreased, the furnace electrodes would "walk up," until at one point in the process the tips would break the surface and arc on top of the slag. This was undesirable since direct arcing caused losses of important flux additions. The slag compositions under study at that time were such that losses due to surface arcing sometimes caused viscous slags to be formed. Forcing the electrodes into the slag bath by manual control to prevent surface arcing resulted in excessive power input and lack of control. Suitable low voltages were not available. Measurement of the electrical resistivity of titanium slags at various operating temperatures and slag compositions was undertaken. It was believed that this information would be of use in the design of electric furnaces suitable for smelting ilmenite, with voltages, electrode sizes, and electrode spacing adapted specifically to titanium slags.

Jan 1, 1951

By W. W. Anderson

WEBSTER'S dictionary gives the following definition for "efficiency": "Effective operation as measured by a comparison of actual and possible results." Engineers think of this definition in terms of the ratio of output to input, and since they learn early in their careers that output cannot be greater than input, they usually consider a machine to be 100 pct efficient if it operates perfectly, and to be 0 pct efficient if it performs no function at all. Hence, values of efficiency between 0 and 100 pct reflect how well or how poorly a machine has performed; and any method of calculation for determining efficiency that does not show 0 pct when no function has been performed, and 100 pct when a perfect job has been done, is looked upon with skepticism. The literature on performance of coal cleaning equipment contains many references to efficiency of performance, but there is no unanimous agreement among the authors as to how the efficiency should be determined. Numerous methods of calculation have been proposed from time to time, most of which attempt to fulfill the definition of efficiency by comparing output to input, using float and sink data or some other characteristic, such as dry ash content, as a measure. However, to the best of our knowledge, none of the methods advocated in the past meets the requirements of a practical engineer in judging cleaning plant performance, because the formulas previously advocated do not confine numerical values of efficiency between 0 and 100 pct, and the literature does not contain an explanation of the meaning of the formulas under various conditions of operation. Therefore, the following formula, based on Yancey's concept of misplaced material,' is proposed as a measure of efficiency which will conform with the requirement that the values of efficiency must be confined between 0 and 100 pct: Quantitative Efficiency = 100.0 — (pct wt sink* in cleaned coal + pct wt float* in refuse)t • At gravity of separation effected by cleaning equipment. t Total product basis of the size of material under study. It will be noted from this formula that an actual separation between cleaned coal and refuse must be effected by the cleaning equipment before the formula can be used; also, that improperly distributed material in the products must be determined at the gravity of separation, rather than at some arbitrary test gravity. It will further be noted from this formula that the weight of cleaned coal recovered and the weight of refuse rejected by the equipment have their proper influence, because the sink in the cleaned coal and the float in the refuse are expressed in the equation as a per cent weight of the total products of a definite size discharged from the plant. This formula has one other important characteristic, in that it requires no knowledge of the feed to the cleaning unit. Comparison of data on the products from a cleaning unit with the feed to the unit can lead to many worthwhile conclusions. but not in regard to the efficiency of separation effected by the equipment. The reason for this is that mechanical fracture of many pieces of the feed occurs during the cleaning process; and in some processes crushers are deliberately incorporated in the flow to produce size degradation to free impurities from cleaned coal, thereby altering the washability characteristics of the material while in process. When such size degradation occurs in a cleaning process, it is quite possible that this crushing will result in a reduction in ash content in the finer sizes of cleaned coal when compared with the raw coal feed, even though no true separation has been effected. This is due to the fact that the finer sizes have been "sweetened" by the crushing of cleaned coal from some coarser size. Many formulas advocated in the past show high cleaning efficiencies

Jan 1, 1951

By W. W. Mullins

The development, by the mechanism of volume diffusion, of a grain boundary groove on an interface separating a solid phase and a saturated fluid phase is calculated under the following assumptions: 1) isotropy of the interfacial free energy 's, 2) applicability of the Gibbs-Thompson formula relating curvature and chemical potential, 3) a nearly planar groove surface. The groove profile is found to have a .fixed shape and linear dimensions that are proportional to (time)1/3. The constant of proportionality is evaluated and involves ?s in such a way that the latter my be evaluated from grooving kinetics. A grain boundary that intersects an interphase interface will tend to produce a groove along the line of intersection (Fig. 1). The ultimate motivation for the formation of the groove is the reduction in interfacial free energ that occurs as the grain boundary contracts. Smith has discussed the way in which the free energy of the interfaces determines their dihedral angles at the groove root and has given a detailed analysis of the effect of the dihedral angles upon the nature the microstructures developed in polyphase alloys. Herring2 has extended the considerations to the case in which the free energy of an interface depends on its orientation and has thus added torque terms to the condition for interface equilibrium. Although the grain boundary and the interphase interface may quickly achieve the proper equilibrium angles where they intersect, as determined by the balance of equivalent tensions and torques,"2 the groove will generally continue to grow (though with decreasing speed). Thermodynamically, this continued growth reflects the fact that the lowest free energy cannot be achieved until the entire grain boundary has been eliminated; mechanistically, the growth occurs in response to inhomogeneities of chemical potential that are caused by the constraint of fixed dihedral angles at the groove root. The latter point is illustrated in Fig. 1, which shows that atoms* near the groove are on the convex side of a cylindrically curved surface and therefore have a higher chemical potential than atoms on the flat interface beyond. Thus atoms tend to leave the curved groove shoulders and force the groove to deepen. When both phases are solid additional chemical potential gradient may arise from whatever strain fields are necessary to insure continuity of material across the interface. In the discussion that follows, this complication due to strain will not occur since we always assume one phase to be a fluid and the other a solid. The transport processes that may operate to permit growth of the groove are surface (interface)* diffusion, volume diffusion in the phase on either side of the interface, and evaporation-condensation when one phase is gaseous. (Also a melting-freezing process is responsible for groove enlargement on a solid-melt interface as discussed in Sec. VI). The theory of grain boundary grooving has been discussed in detail for the processes of surface diffusion and of one type of evaporation-condensation.3'4 The theoretical predictions for the mechanism of surface diffusion have been confirmed in an experimental study of grooving kinetics in copper.5 In this paper, the theory of groove development by volume diffusion will be presented. Volume diffusion can occur either by atomic migration in the solid S or by diffusion of S atoms in the fluid phase, or solvent, adjacent to the groove surface. As discussed in Sec. V, volume diffusion in the solid should be less important than surface diffusion in forming a groove. Apart from verifying this statement then, the main interest of the present analysis centers on diffusion in an external solvent. The solvent may be either a liquid (e.g., water, or-

Jan 1, 1961

By S. T. Yuster

An analysis has been made of the factors responsible for tilted fluid contacts in petroleum reservoirs. The factors are static and dynamic with the former being controlled by those variables responsible for the capillary rise of fluids, and the latter include rate of formation tilt and hydraulic circulation. The explanation that rate of formation tilt may be responsible for tilted contacts appears untenable. The role of some of these factors in the migration, fractionation. accumulation and possibly the prospecting for oil is indicated. INTRODUCTION While it is generally considered that the segregation of gas, oil, and water in a petroleum reservoir results in approximately horizontal planes separating these phases. there are factor; which modify this simplified picture to a very great extent. Some of these factors are static. and the departure of the fluid interfaces from horizontal may represent a static equlibriun. Some of these factors may be dynamic and the interface positions may be non-equilibrium and represent a steady .state condition. Of course combinations of these two situations may also exist. The reasons most commonly given for this behavior are hydraulic circulation of fluids, change in character of the formation, and a rate of tilt of the formations more rapid than the rate at which the fluids may re-establish an equilibrium. Russell's Principles of Petroleum Geology' contains an extensive discussion of tilted fluid interfaces and their importance in the migration and accumulation of petroleum. Russell cites examples of tilted water tables at Lance Creek, Wyo.; Rock River, Wyo.: Cut Bank. Mont.; Cushing, Okla.: and Graham; Okla. Also given was the Wasson Field of West Texas which has saucer shaped oil-water and gas-oil interfaces with the saucer being deeper in the case of the oil-water contact. The Bradford Field in Pennsylvania has a tilted water table. San Ardo. Coalinga None and some other California field.; have tilled contacts. A recent paper by King Hubbert discuses the effect of hydraulic circulation of the water underlying the oil in a given stratun and it- implications in the accumulation of and drilling for the oil. The foregoing would indicate that tilted fluid interfaces are not uncommon and that it would be of importance to underbtand the forces which are responsible. Further. it would be of interest to examine certain idealized models of situations which may cause tilting with the thought in mind of deriving relatinnships between the important variables. These relationships may only hold exactly for the model* assumed but the results may apply semi-quantitatively to actual formations and at least indicate trends. The discussion will be divided into the effect of static factors and the effect of dynamic factors. STATIC FACTORS It has already been mentioned that one reason given for tilted contacts is a variation in formation properties. Specifically this is a change in the pore size of the formation capilaries. If the internal surface of the reservoir is preferetially wet by water, capillarity will cause the water 10 rise to a greater extent above the free water table in a small capillary than in a large one. Consequently the water-oil contact will be higher in the lower permeability sands than in the higher permeability sand.;. The free water table may be defined as the position the oil-water interface would take if capillarity were absent. Since the phenomenon is the capillary rise of water in an oil environment, a derivation of this shold give a relationship between the variables. Fig. 1 is an idealized model of the situation with a uniform bore circular capillary ubstitttting for the tortuous non.circular formation pore. The upward force.; on the column of water will be equated to the forces downward to give the equilibrium situation. forces upward = force downward where r is the radius of the capillary in ceritimetera. a is the interfacial ten4on oil-water in dynes per centimeter, 0 is the

Jan 1, 1953

By W. W. Anderson

WEBSTER'S dictionary gives the following definition for "efficiency": "Effective operation as measured by a comparison of actual and possible results." Engineers think of this definition in terms of the ratio of output to input, and since they learn early in their careers that output cannot be greater than input, they usually consider a machine to be 100 pct efficient if it operates perfectly, and to be 0 pct efficient if it performs no function at all. Hence, values of efficiency between 0 and 100 pct reflect how well or how poorly a machine has performed; and any method of calculation for determining efficiency that does not show 0 pct when no function has been performed, and 100 pct when a perfect job has been done, is looked upon with skepticism. The literature on performance of coal cleaning equipment contains many references to efficiency of performance, but there is no unanimous agreement among the authors as to how the efficiency should be determined. Numerous methods of calculation have been proposed from time to time, most of which attempt to fulfill the definition of efficiency by comparing output to input, using float and sink data or some other characteristic, such as dry ash content, as a measure. However, to the best of our knowledge, none of the methods advocated in the past meets the requirements of a practical engineer in judging cleaning plant performance, because the formulas previously advocated do not confine numerical values of efficiency between 0 and 100 pct, and the literature does not contain an explanation of the meaning of the formulas under various conditions of operation. Therefore, the following formula, based on Yancey's concept of misplaced material,' is proposed as a measure of efficiency which will conform with the requirement that the values of efficiency must be confined between 0 and 100 pct: Quantitative Efficiency = 100.0 — (pct wt sink* in cleaned coal + pct wt float* in refuse)t • At gravity of separation effected by cleaning equipment. t Total product basis of the size of material under study. It will be noted from this formula that an actual separation between cleaned coal and refuse must be effected by the cleaning equipment before the formula can be used; also, that improperly distributed material in the products must be determined at the gravity of separation, rather than at some arbitrary test gravity. It will further be noted from this formula that the weight of cleaned coal recovered and the weight of refuse rejected by the equipment have their proper influence, because the sink in the cleaned coal and the float in the refuse are expressed in the equation as a per cent weight of the total products of a definite size discharged from the plant. This formula has one other important characteristic, in that it requires no knowledge of the feed to the cleaning unit. Comparison of data on the products from a cleaning unit with the feed to the unit can lead to many worthwhile conclusions. but not in regard to the efficiency of separation effected by the equipment. The reason for this is that mechanical fracture of many pieces of the feed occurs during the cleaning process; and in some processes crushers are deliberately incorporated in the flow to produce size degradation to free impurities from cleaned coal, thereby altering the washability characteristics of the material while in process. When such size degradation occurs in a cleaning process, it is quite possible that this crushing will result in a reduction in ash content in the finer sizes of cleaned coal when compared with the raw coal feed, even though no true separation has been effected. This is due to the fact that the finer sizes have been "sweetened" by the crushing of cleaned coal from some coarser size. Many formulas advocated in the past show high cleaning efficiencies

Jan 1, 1951

By V. A. Josendal, J. W. Wilson, B. B. Sandiford

Two radioactive tracers have been tested as a means of determining core saturation in multiphase flow studies. Cesium chloride was tried as a water-phase tracer, but complications in its use in low permeability cores resulted from sorption of cesium by the core or water-wet pads. IodoI3'ben-zene proved very satisfactory as an oil-phase tracer. The synthesis of iodobenzene from the sodium iodide as received from Oak Ridge is simple and direct. The tracer is insoluble in water and there was no evidence of sorption by any of the core materials used. use of the method to determine saturation profiles during capillary and dynamic desaturations and relative permeability measurements on oil-water and oil-gas systems is described. Comparisons of the dynamic and capillary methods of relative permeability determination were made using the tracer to check core saturation and saturation distribution. Other experiments are also described in which mobility of the oil phase at various saturations was measured by displacing labeled oil by flowing inactive oil. Similar experiments were made using water labeled with cesium 134. INTRODUCTION To be fundamentally sound. any laboratory method of determining relative permeability must meet, among others, the following requirements: (1) the core saturation between the pressure taps must be uniform, and (2) there must be uniform pressure difference between the phases in the region between the pressure taps. In practice it may eventually be shown that appreciable departure from either or both of these conditions may be permitted without introducing sensible error. but the magnitude of such error remains to be established. There is need then for methods of saturation determina- tion which will determine the saturation profile in a core as well as the overall average saturation given by the gravimetric or material balance methods usually employed. Methods which have received consideration include resistivity, X-ray absorption, gamma ray absorption, neutron diffraction, and radioactive tracers. The resistivity method has use in the determination of profile, but needs checking by independent means.' The X-ray method has been used successfully, but requires elaborate equipment and calibration.23 4 At present gamma ray absorption is practical only for very large cores. The neutron methodo does not appear adaptable to measurement of saturation variations in short cores since it is a scattering method. Russell, Morgan and Muskat' employed radiovanadium in a study of the mobility of interstitial water. Coomber and Tiratsook used radioiodine as an oil-phase tracer and measured profiles in unconsolidated sand packs. ADVANTAGES OF RADIOACTIVITY METHOD A thorough discussion of the theory of radioactive tracers and the technique of using them to study the movement of fluids in sands is given by Coomber and Tiratsoos and need not be detailed here. The method requires less equipment than the X-ray method; the counting problem is similar, but the generation and regulation of the radiation, which is a major problem in the X-ray method, is not required in the radioactivity method. In the X-ray method it is customary to add up to 20 per cent of absorber, usually an iodine compound, to the phase to be labeled. while in the radioactivity method a mere trace is sufficient. A possible disadvantage of the radioactivity method is that a disproportionate amount of the activity comes from the portion of the core nearest the counter, whereas the X-ray gives a true average saturation in the region traversed by the beam. 011 the other hand, this characteristic of the radioactivity method renders it peculiarly adaptable to study of certain types of radial variations in saturation. As with the X-ray method, a tracer may be added to either the oil or water-phase. An oil-phase tracer is more generally useful. however. since it permits work on oil and gas in the

Jan 1, 1952

By N. A. Warner

Dense cylindrical specimens of artificial hematite were reduced in hydrogen over a range 0-f total pressures between 0.1 and 1.0 atm and temperatures between 650" and 950°C. Hydrogen reduction at a total pressure of 1.0 atm in the presence of a chemically inert diluent and reduction in hydrogen/water mixtures were also studied Znter.face movement during reduction was followed using metallographic techniques. Substantiu1 partial-pressure gradients are shown to exist in both the gas film and the reduced iron layer. The results are consistent with a mixed-control mechanism involving an interaction of gaseous-difusion effects with a first-order reversible chemical reaction at the iron/wüstite interface. Over the hydrogen-pressure range of 0.1 to 1.0 atm, the rate is not directly proportional to the hydrogen pressure in the bulk gas stream. Nitrogen dilution of the reducing gas masks the true effect of hydrogen partial pressure by influencing the effective molecular dif-fusivity and gives an apparent first-order relationship. The transport of hydrogen and water vapor across the iron layer is consistent with molecular gaseous diffusion rather than a Knudsen diffusion mechanism. ALTHOUGH the literature on the reduction of iron oxides is very extensive, it is only comparatively recently that a definite quantitative model for the reduction of hematite has been proposed. This development has been largely due to the work of McKewan. An extensive literature review of previous work has recently been compiled by Themelis and Gauvin. Exclusive control by gaseous diffusion in the reduction of hematite has been recently advocated by Kawasaki and coworkers.' Although the results of the latter workers are of considerable practical significance, the extreme porosity (approximately 30 pct) of their specimens precludes their application to a kinetic evaluation of the reduction of dense polycrystalline hematite. The salient features of the kinetic model used by McKewan for the gaseous reduction of dense hematite at temperatures in excess of 560°C (when FeO is stable) are: 1) The reduction is a topochemical reaction taking place through 'the series FeO/FesO4/FeO/ Fe; 2) The gas-solid type of reaction takes place only at the FeO/Fe interface and the internal reduction: FeO proceeds by solid state diffusion; 3) The iron layer formed is quite porous and offers negligible impedance to gaseous diffusion; 4) The rate-controlling step in the reduction is a chemical process occurring at the Fe/FeO interface. In view of the relatively fast reaction rates involved when hematite is reduced in a stream of hydrogen, it seemed possible that the simplifying assumptions of negligible diffusional resistance in both the bulk gas phase and the reduced iron layer could introduce serious errors in the interpretation of experimental reduction data. The present work was initiated to elucidate the effect of gaseous diffusion on the reduction rate and to determine its possible influence in the formulation of the reaction mechanism at the metal/oxide interface. EXPERIMENTAL Procedure and Apparatus. Dense cylindrical compacts of artificial hematite were prepared by sintering pressed compacts of reagent-grade ferric oxide, containing 99.6 pct FezO, in air at 1200°C for 80 hr. The resulting compacts had a final porosity of less than 2 pct and a height and diameter of approximately 1 cm. Variations in sintering atmosphere from air to pure oxygen, in sintering time from 20 to 80 hr, and temperature from 1150" to 1250°C had no effect on the subsequent reduction behavior. The reduction of the samples took place in a vertical tube furnace in which was placed a 1-in. transparent silica tube. The 24-in. heated length

Jan 1, 1964