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By G. S. Scott, G. W. Jones

Economic waste caused by mine fires may become considerable,l5 especially if a fire is allowed to spread or temporarily to get beyond control. It is important, therefore, to act promptly whenever a fire is suspected and to make every action count. To contribute toward its extinction effectively it is necessary to know at the earliest possible moment, and continuously thereafter, what is happening at the seat of the fire, which may be in a remote or inaccessible area, and also to recognize what may be expected as a result of any proposed combative measure. In combatting a fire the mining engineer and the chemist should cooperate, first deciding upon the course of action to be taken and then drawing upon the mining engineer's intimate knowledge of the physical structure of the fire area, the cost and time required to carry out proposed operations, and the probable efficiency with which these operations could be performed, and upon the chemist's knowledge for the results to be expected therefrom. After the initial steps to be taken have been decided, it devolves upon the mining engineer to see that they are carried out and upon the chemist to evaluate the results and to keep the mining engineer continuously informed in regard to a variety of matters—such as the composition and toxic or asphyxiating properties of the atmosphere in which the men may be working, whether the fire is increasing or decreasing in intensity and its probable temperature, the quantity of air leakage and the explosion hazards of the fire area. The purpose of this paper is to discuss what the chemist can and cannot contribute as a member of the fire-fighting personnel. The technical literature contains several hundred papers relating directly and indirectly to mine fires, and this fact alone is testimony to the complex nature of the phenomena involved in the birth, life, and final demise of a fire. A fire may be stopped (I) by preventing oxygen from reaching the coal or (2) by removing the conditions necessary for the rapid reaction of coal with oxygen; i.e., decreasing the temperature. All methods of prevention or control necessarily must be based upon one or the other, or both, of these two principles. The chemistry of a fire may be understood readily if the low-temperature oxidation of coal is considered as a starting point; then oxidation at higher temperatures (or combustion); and with these, the composition of the solid and gaseous products resulting from the oxidation or from the effects of the heat liberated. This discussion refers particularly to Pennsylvania anthracite, although much of the material applies equally well to coals of lower rank. Oxidation of Coal Oxidation of coal fundamentally is confined to the surface; that is, the rate at which oxygen penetrates into the interior of a solid block of coal is so slow that it may be ignored."16 Oxidation starts when a fresh surface is exposed, and the rate is

Jan 1, 1942

By M. A. Steinberg, J. Wulff, R. Kamm

In a previous paper1 from this laboratory, the development of a lead grid method for exploring the distribution of strain and density within metal powder compacts was described. In that work thin lead foil with rectangular holes cut at regular intervals was inserted with the powder fill, the arrangement pressed and then radiographed to permit measurement of the deformation of the lead grid. Densities at each grid element obtained in this manner were plotted as a function of the die dimensions. From such plots it was found that the densest part of a compact pressed from one side (the top) is at the top outer region and the least dense at the bottom outer region of the specimen. The axial density maximum occurs more often nearer the bottom than at the top. As a result of such exploratory measurements, it appeared reasonable to conclude that variations in density could be attributed in the main to die wall friction. Thus compacts of large diameter appeared relatively uniform in density except where the die fill had been uneven. Finally it was found that lubrication of the finely finished die cavity contributed more to magnitude and uniformity of density within the compact than interparticle lubrication. Since publication of the above results, it was found that circular-hole grids could be more accurately made and, when deformed within the powder, more readily measured and analyzed. Much of the former work was repeated and new results which include the effect of lubrication, compact height, pressure, speed of pressing and vacuum pressing are reported in the present paper. Circular-hole Grids and Analyses OF Radiographs Commercial lead sheet 0.008 in. in thickness was used in all the work reported. The 0.0938-in. diam holes were punched in the sheet on 1/8-in. centers to an accuracy of 0.001 in. The finished grid used contained eight or more holes in a row and from I to 24 rows. The lead sheet was clamped between two pairs of brass strips bolted to a small milling machine table which was itself bolted to a bench in correct position near a vise which held the punch. Travel of the lead grid in two dimensions was controlled by two steel lead screws calibrated in 0.001-in. divisions. A stripper plate was used on the punch to avoid distortion of the lead foil. A high carbon-high chromium (chrocar) one-piece steel die was used throughout the work. The die cavity was 1.125 in. in diam and the clearance between plungers and die wall was 0.001 in. The die was also used for pressing from both ends with two long plungers. Finally, lapping of die and plungers gave a surface whose rms value On an Abbot profilometer was 5 micro-in. The die walls and plungers were, except where otherwise noted, lubricated with a stearic acid suspension in benzene. This was put on in multiple layers and allowed to dry before filling the die.

Jan 1, 1949

By M. C. Leverett

KNOWLEDGE of the theory underlying the behavior of mixtures of fluids in reservoir rocks is essential to the proper solution of certain types of problems in petroleum pro-duction, but is as yet incompletely devel-oped. The object of this paper is to show the application of well established thermody-namic and physical principles to these prob-lems, and thus to assist in the development of the basic theory. For convenience the problems to be considered here may be divided into two groups: I. Static problems, involving only the static balance between capillary forces and those due to the difference in densities of the fluids; i.e., gravitational forces. 2. Dynamic problems, involving analysis of the motion of mixtures of immiscible fluids in porous media under the influence of forces due to gravity, capillarity, and an impressed external pressure differential. CAPILLARY EQUILIBRIUM IN SANDS Under this heading the static type of problem will be discussed and the results of experimental investigations on the capillary properties of unconsolidated sands will be presented. Although the discussion of this section is, in a sense, prefatory to the treat-ment of problems of mixture flow, the con-cepts developed here have considerable intrinsic importance apart from their ap-plication to flow problems. For, it is reason-able to postulate that the reservoir fluids are, owing to their long existence in undis-turbed mutual contact prior to exploitation, in substantial equilibrium. It follows that their distribution in the reservoir at the time of tapping should be entirely predict-able from the theory of capillary equi-librium, provided certain experimentally measurable properties of the reservoir rock are known. Knowledge of the distribution of the several fluids in the reservoir is, of course, helpful in the estimation of reserves and in other problems. It is to be emphasized that throughout the discussion of capillary statics it is as-sumed that the fluids are in equilibrium from the capillary standpoint. Thus, water, where it is referred to as being in a reser-voir, will be understood to be interstitial water, present at the time of drilling the reservoir, commonly termed "connate" water. The theory developed here is perfectly general for any porous solid, whether a carefully prepared unconsolidated sand or a natural sandstone from an oil reservoir. At present, however, only problems in-volving clean, unconsolidated sands can be made to yield numerical solutions, since only such sands have been adequately in-vestigated experimentally. Experimental evaluation of the pertinent properties of natural reservoir rocks will permit the ex-tension of the numerical treatment to prob-lems involving these materials. We shall now consider in some detail the static equilibrium of fluid mixtures in porous solids; that is, the manner in which the reservoir fluids are distributed vertically when the forces due to capillarity are just balanced by those due to gravitation.

Jan 1, 1940

By H. l. Burghoff, J. S. Porter

This paper presents the results of an investigation of the effect of cold-working and annealing treatments upon the occurrence of preferred orientation in annealed brass wire. The subject has received less consideration than has the same phenomenon in annealed brass sheet or strip, and perhaps very properly so in view of the obvious and undesired results obtained in the forming or drawing of strip having preferred orientation, which results are in contrast with the lack of any spectacular visual evidence in wire. The factors of cold-working and annealing that control preferredness in strip are naturally expected to function similarly in wire. Indeed, one might expect the condition to be commoner in annealed wire, because the severity of the cold-working between anneals in commercial Practice is usually much greater for wire than for strip. For example, a wire that is to be finished in the annealed condition on a diameter of 0.040 in. is commonly subjected to a final reduction of 90 per cent between the last two anneals, the large reduction being accomplished in the successive drafts of a multiple-die machine. Wire for rivets, for instance, on 0.125-in. diameter, although given a slight reduction of about Io per cent after the final anneal, may have been given a prior reduction of 75 to 80 per cent. Barrettl states the fiber axis of annealed 70-30 brass wire to be [111], with some indication of [IOO] as a secondary fiber axis. Croft and Sachs2 have reported briefly on some differences in brass wire with random and with preferred orientations. They showed statistical plots of the twin-band angles with respect to the wire axis or direction of drawing as observed on an axial plane. They also pointed out that the resistance of the wire to corrosion-cracking when externally stressed and exposed to a mercurous nitrate solution decreased as the degree of the preferred orientation increased. Material and PRocedure All the wire for the investigation was processed from one portion as cut for extrusion from a cast billet of the following analysis: 70.13 per cent copper; 0.01 lead; 0.01 iron; 0.02, nickel; 29.83 zinc (by difference). The billet section, 8 in, in diameter, was extruded hot to 3/4-in. diameter, after which it was processed by alternate cold-drawing and annealing treatments as indicated in Fig. I. The earliest anneals in process were at about 1100°F. and the next to the last reductions by drawing were 58 per cent. The diameter of the finally annealed wire was 0.132 in. Semifinal anneals were at 800°F., 950°F. and 1100°F. and reductions of 47.5, 74, 83.5 and 89.5 per cent were employed in drawing to 0.132 in. The final anneals were at 87s°F., 1050°F. and 1250°F. and were

Jan 1, 1944

By J. B. Pullen

THE United Verde mine is in the north central part of Arizona, on the. north-easterly slope of the Black Hills, near the town of Jerome. Ore was first discovered in the district about 1875, and the first mining claims were located by M. A. Ruffner and associates in 1877. In 1888 the late Senator William A. Clark secured control of the property and under his ownership it developed into one of the country's most important copper producers. The property was sold to the Phelps Dodge Corporation in 1935, and since then has been under this Corporation's management. Except for shutdowns caused by general world-market conditions, production has been continuous from 189o to date. GEOLOGY The mineralized zone ranges in area from approximately 12 acres to less than 5 acres. All mineralization occurs in the pre-Cambrian intrusives. The first intrusion, according to geologic records, was the quartz porphyry, which later was intruded by augite diorite. Following the diorite intrusion through a series of intrusions of lesser magnitude, a pipelike mass of massive sulphide, quartz and rock was formed. The diorite forms the hanging wall of this mass, and the porphyry the footwall. Between the footwall and the sulphide a band of chlorite schist was formed, probably owing to metamorphic conditions. Commercial ore occurs along the contact of the schist and sulphide extending into the sulphide, sometimes entirely through the schist, and fingering out into the porphyry. The ore deposit was formed by replacement similar to deposits formed in limestone areas. Faulting and deformation occurred in pre-Cambrian times and again in the Tertiary period, removing approximately 2000 ft. from the top of the main United Verde ore body, forming the United Verde Extension ore body, the only other major ore body in the district. Major development work has shown that the sulphide mass extends to the 3300-ft. level, and diamond drilling below this level has indicated that the mass might extend below the 3700-ft. level, but in a diminished quantity. While many copper minerals exist in the mine, the chief commercial mineral is chalcopyrite. A plan and vertical section of the mineralized zone showing the principal geological features is shown in Figs. I and 2. GENERAL DESCRIPTION AND PHYSICAL CONDITION OF MINE After over 50 years of active production, ore still exists on almost every level of the mine. This condition is due to many causes -mine fires, which broke out as early as 1894, caused the abandonment of certain areas; subsidence and ground movements retarded the cleaning up of others. Furthermore, in the early days there was such an abundance of ore that when mining became difficult it was a simple matter to replace the production by going to a deeper level. Several attempts were made to recover the ore in the fire zone, both by glory-holing

Jan 1, 1941

By L. S. Darken

THE manufacture and treatment of metals comprises operations whose effectiveness depends in large measure upon diffusion phenomena. The significance of such phenomena has, for a few simple cases, long been understood, but in more complex cases it has not been adequately recognized. This paper presents a mathematical analysis of some of the cases in which diffusion leads to the formation of a new phase within the metal, and this analysis provides a basis for interpreting quantitatively many apparently diverse experimental observations recorded in the literature, some of which are outlined in the following pages. OBSERVATIONS RECORDED IN LITERATURE An outstanding instance is the general type of phenomenon in which diffusion of an element into an alloy is followed by a phase change, which most frequently is a reaction (precipitation) of the diffusing element with one or more components of the alloy to form a compound. Thus in certain alloys heated in contact with oxygen not only the usual oxide scale appears but, in addition, beneath the surface, a well-defined zone in which free oxide particles are dispersed with notable uniformity. This zone, commonly referred to as the subscale or zone of internal oxidation, is remarkable in that the visible boundary between it and the unaltered metal is usually sharp. Such a subscale, which appears to have been recognized first in oxidized copper alloys, has been described and studied by C. S. Smith,1 by Rhines,2 and by Rhines, Johnson and Anderson;3 but it appears also in other alloys when they are exposed to conditions that bring about the precipitation of some compound, not necessarily an oxide. Another clear case of this same kind is the diffusion of carbon into a steel containing an element such as molybdenum, chromium, vanadium or tungsten, whose carbide is less soluble in iron than iron carbide, the result being that some part of that element is precipitated as a dispersed carbide. A similar phenomenon may occur on the welding of two alloys each of which contains one of a pair of elements that react to form a compound or a new phase of any sort. But in addition to the precipitation of a compound formed from the diffusing element, other effects may result merely from the presence of the diffusing element. For instance, if homogeneous austenite, nearly saturated with respect to carbon, is heated in contact with silicon in the absence of oxygen, one would expect to find, behind the several iron-silicon phases analogous to a scale, a zone of austenite containing dispersed carbide, because of the fact that silicon decreases the solubility of carbon in iron. As still another example, oxidation of an alloy may result in diffusion toward the surface of one or more of the constituents; for instance, during oxidation of a steel containing an element such as copper, which is less prone to oxidation than iron, there is a notable enrichment of copper just beneath the scale-metal interface. As an example of a yet more

Jan 1, 1942

By H. l. Burghoff, J. S. Porter

THIS paper presents the results of an investigation of the effect of cold-working and annealing treatments upon the occurrence of preferred orientation in annealed brass wire. The subject has received less consideration than has the same phenomenon in annealed brass sheet or strip, and perhaps very properly so in view of the obvious and undesired results obtained in the forming or drawing of strip having preferred orientation, which results are in contrast with the lack of any spectacular visual evidence in wire. The factors of cold-working and annealing that control preferredness in strip are naturally expected to function similarly in wire. Indeed, one might expect the condition to be commoner in annealed wire, because the severity of the cold-working between anneals in commercial practice is usually much greater for wire than for strip. For example, a wire that is to be finished in the annealed condition on a diameter of 0.040 in. is commonly subjected to a final reduction of 96 per cent between the last two anneals, the large reduction being accomplished in the successive drafts of a multiple-die machine. Wire for rivets, for instance, on 0.125-in. diameter, although given a slight reduction of about 10 per cent after the final anneal, may have been given a prior reduction of 75 to 80 per cent. Barrett1 states the fiber axis of annealed 70-30 brass wire to be [111] with some indication of [100] as a secondary fiber axis. Croft and Sachs2 have reported briefly on some differences in brass wire with random and with preferred orientations. They showed statistical plots of the twin-band angles with respect to the wire axis or direction of drawing as observed on an axial plane. They also pointed out that the resistance of the wire to corrosion-cracking when externally stressed and exposed to a mercurous nitrate solution decreased as the degree of the preferred orientation increased. MATERIAL AND PROCEDURE All the wire for the investigation was processed from one. portion as cut for extrusion from a cast billet of the following analysis: 70.13 per cent copper; 0.01 lead; 0.01 iron; 0.02 nickel; 29.83 zinc (by difference). The billet section, 8 in. in diameter, was extruded hot to 3/4 -in. diameter, after which it was processed by alternate cold-drawing and annealing treatments as indicated in Fig. I. The earliest anneals in process were at about 1100°F. and the next to the last reductions by drawing were 58 per cent. The diameter of the finally annealed wire was 0.132 in. Semifinal anneals were at 800°F., 950°F. and 1100°F. and reductions of 47.5, 74, 83.5 and 89.5 per cent were employed in drawing to 0.132 in. The final anneals were at 875°F., 1050°F. and 1250°F. and were

Jan 1, 1944

By Henry J. Welge

The approximate methods which are now in use for calculating oil displacement from reservoirs by gas-cycling or gravity-drainage at constant gas pressure, or by water flooding, make use of fundamental relationships derived by Leverett' and Buckley and Leverett.2 The mathematical equations needed are derived by applying Darcy's law to the flowing phases, and by material balance considerations. ln general, any treatment of this type gives. for any particular exploitation time considered, a plot of oil saturation against distance in the reser-voir. The oil recovery must then be obtained by integrating in some manner the area under the plot. A useful analytical method has been derived for computing the average saturation, and hence the oil recovery. Use of this method simplifies the calculations because it makes unnecessary any numerical integrations. and even the saturation distribution plots are not needed. A further advantage of the method is that knowledge of the relative permeabilities is required only for a limited and intermediate saturation range. In both the Buckley and Leverett method and the method discussed here, a linear sand section is assumed, and in the case of gas drive the gas pressure is assumed sufficiently constant both with respect to reservoir position and time so that changes in gas density. solubility, or reservoir volume factor are negligiklle. Thus, the exploitation contemplates oil displacement as by an immiscible phase. Examples are given to illustrate how the new method can be used. INTRODUCTION AND THEORETICAL BACKGROUND This paper treats a simplified method for computing oil recovery when the oil is displaced, from the reservoir sand by a fluid which, within the limits of accuracy desired, can be assumed to be incompressible and immiscible with the oil. The method makes use of two basic relations originally developed for the case of water displacing oil. However, the case of gas displacing oil saturated with gas at a constant (or nearly constant) pressure may also be considered a displacement by an immiscible fluid. This is possible for the reason that the concentration of the gas in the oil never changes if tile pressure is fixed. consequently, any additional free gas must remain undissolved in the oil, and so must act essentially as an immiscible phase. For convenience, the cape of gas drive will be considered first. Both of the two basic relations needed refer to a linear reservoir, or one which may be somewhat idealized so that a constant cross-section is exposed to fluid flow. Further, the displacing phase is injected at one end, or face; of the reservoir, while the produced fluids are understood to emerge at one point only. which is the opposite face of the reservoir. As indicated in Fig. 1, the reservoir may he inclined by some angle 8. The first of the required equations may be derived by applying Darcy's law to both displacing and displaced phases, and subtracting the two equations. The result for water drive has been given previously, as Equation (13) of the reference by

Jan 1, 1952

By F. W. Jessen, F. W. Rols-Hausen

It is the purpose of this paper to present data on brines occurring in the Frio formation of the Texas Gulf Coast, and to show how their composition varies, (1) with depth below the surface, (2) with depth below the top of the formation, and (3) along the approximate strike. The brines vary in chloride content from 3,180 to 73,000 p.p.m., though the average salinity of the salt waters is shown to vary with total depth; the concentration being 35,000 to 40,000 p.p.m. at 3500 to 5500 ft., slightly less than 50,000 p.p.m. chloride at 5500 to 6500 ft. and average 38,000 to 40,000 below 6500 feet. From the analyses available, it appears that the highest concentration of salts occurs in the upper 300 ft. of the formation, while lower salinity is found with increasing depth below this point. The salt waters from wells in Starr County show less concentration of dissolved salts than in any other group of wells farther north along the strike. In all, 116 analyses from 63 fields and 14 wildcats, from depths ranging from 1300 to 11,400 ft. below the surface and from z to 3240 ft. below the top of the Frio, are recorded. Introduction Brines have been studied for many Years in an attempt to solve some of the geologic and production problems associated with the production of oil and gas. One practical application of study of . water analyses is the correlation of waters occurring above, in, or below the producing sand in the same field or throughout the same formation. The Frio formation, the series of sands and shales occurring below the Marginulina zone and above the Vicksburg, is one of the major oil and gas-producing formations in the Texas Gulf Coast. Fossils are rare or absent in the upper Frio throughout most of the area. When available, cuttings and cores, and electric logs were used to determine the top of the Frio. A change in lithology was used to determine this point in most of the wells, and fossils were used in some of the deep wells. It is realized that a change in lithology is not perfect for correlation purposes over long distances and some of the trends may be influenced by the inability to differentiate between the nonfossiliferous Marginulina zone and the Frio. It underlies virtually all the area shown on the accompanying map (Fig. I). Although it is not productive in the updip facies, it has been explored to a limited degree below I2,000 ft. Further more, toward the coast line future drilling to deeper depths should encounter this formation. Although thousands of wells have penetrated or drilled entirely through the formation, very few water samples have been secured from the many sands occurring in this formation and analyzed. Previous Investigation No previous published study has been made of the chemical composition and concentration of waters from the Frio formation. However, one water analysis

Jan 1, 1944

By Leendert de Witte

A review is given of the principles on which recently proposed methods of electric log interpretation in shaly sands are based and of the evidence brought up in support of the theoretical derivations. It is. pointed out that the qualitative techniques suggested to date have a tendency to be too pessimistic in the prediction of the presence of commercial hydrocarbon accumulations. In the quantitative treatment, a new concept is introduced, namely that of strongly reduced activity of the double layer counter ions which are present near the negatively charged rock surfaces. This lemmu when applied to the calculation of the equilibrium concentratiotls of interstitial waters yields a set of very simple relations. The resulting expressions for electrochemical potentials across rock samples appear in satisfactory agreement with laboratory experiments. The formulae obtained for the electrical conductivity of shaly formatioris are of the same form as those arrived at empirirally by previous workers. Combination of the expres.riorls for potentia1s and conductivities gives a direct proof of the Tixier relation which states that for shaly water sands the product of apparent formation water resistivity and apparent formation factor equals the resistivity of the sand 100 per cent .saturated with formalion water and which was verified by the work of Wyllie and Perkins and their co-workers. The relations for the resistivities and spontaneous porer11inI.s have been extended to the case of hydrocarbon hearing shaly formations, thus laying a formal basis for the quantitative interpretation of electric logs in shaly oil sands. INTRODUCTION The presence of disseminated clays in porous rocks saturated with electrolytic solutions has a strong influence on the transference of ions taking place under electrical or chemical potential gradients. Both the electrochemical emf's in evidence on the SP curves of electric logs and the electrical conductivity measured on resistivity logs arc directly dependent on the ionic transference in the interstitial waters of the formations traversed by boreholes. A large number of researches have been carried out on the nature and magnitude of the effects of clays on ionic transference. The most recent of these have been described in papers by McCardell and Winsauer,1 2 Wyllie and Southwick,3 poupon, Loy, and Tixier,4 and by Perkins et al.5 Most of these authors consider the effects of the clays as due to the fixed negative charges on the clay lattice. These charges cause the formation of diffuse surface layers with a high concentration of positive ions. The internal solution of the shaly reservoir rock has therefore a different ionic composition and concentration than the electrolyte with which it is in equilibrium (connate water produced from the formation or mud filtrate by which the formation is invaded). To calculate the equilibrium concentration of the internal solution, use is made of the Donnan6 relation, which states that the mean ionic activities of the internal solution and of the external electrolyte must be equal. From this and the

Jan 1, 1956

By B. A. Rogers, K. O. Stamm

BECAUSE it is the basis of the economically important operation of hardening steel by quenching, the A3 transformation in iron has been the subject of numerous investigations. Although the contributions to this subject are interesting, no general review will be given here. Readers who care to follow the matter further are referred to the comprehensive summary by Cleaves and Thompson,1 which covers the literature to about 1935. Their references to 53 papers on the subject suggest that further investigation is hardly justifiable. However, considerable interest has developed recently concerning the reversibility of the transformation. From thermodynamic considerations, the transition ought to occur at the same point on heating or cooling, if the change of temperature is sufficiently slow. Yet all of the earlier investigators found a difference of several degrees. Burgess and Crowe,2 who used thermal methods, obtained average temperatures of 912° for Ac3 and 900°C. for Ar3 on electrolytic iron. Their data indicate a considerable range of temperature over which the change occurs, both on heating and on cooling. Terry3 measured the susceptibility in the critical range and estimated from the steepest parts of his curves that Ac3 came at 9180 and Ar3 at 903°C. Ishiwara4 was one of the first investigators to report a shorter interval between the temperature of the change in the two directions. He measured the change of susceptibility of kaolin-coated samples of steel, in a hydrogen atmosphere, at rates of heating and cooling so low that about 3 or 4 hr. were required for the transformation to complete itself. His results show some variability between samples, but indicate that the difference between Ac3 and Ar3 is in the vicinity of 6°C. Roberts and Davey5 measured the space lattice in pure iron in the vicinity of 900°°C. and concluded that a change occurs reversibly between 907° ± 3° and 9100 ± 3°C., probably between 907° and 910°C. Wells, Ackley, and Mehl6 made dilatometric determinations of the Ac3 and Ar3 points in samples of hydrogen-treated carbonyl iron maintained under a vacuum. They used three rates of heating and cooling: 2°, '1/2°, and 1/8°C. per min. and found the spread between the two points decreased with low rates. At the slowest rate, the Ac3 transition occurred at 909° to 909.5°C. and the Ar3 change at 907°C. in three of the samples believed to contain the lowest percentages of alien elements. They concluded that if the rate of temperature change and the content of alien elements were low enough, the A3 transformation would be completely reversible at 909.5° ± I°C. The question of reversibility is an interesting one and when some iron with especially small percentages of alien elements became available the opportunity to conduct an investigation was welcomed. This iron was prepared by the Division of

Jan 1, 1941

By H. M. Beatty, T. L. Joseph, Gust Bitsianes

SUCCESSFUL blast-furnace operation depends upon securing an optimum balance between a number of important variables. This balance will vary somewhat from furnace to furnace in the same plant and with raw materials available in different plants. It is difficult to isolate the effect of any one variable unless it has a rather pronounced effect upon the efficiency of operation. The physical properties of iron ore and coke are known to affect the process, yet it is difficult to set up any definite yardstick by which these differences can be appraised. In recent years, whenever practicable, operators have taken steps to obtain better control over the absolute size and uniformity of size of the ore and coke. The size and physical character of the stone, however, have received comparatively little attention, emphasis being placed upon chemical composition, fluxing efficiency, and action as a desulphurizing agent. Since the stone occupies only about 10 per cent of the volume of the stock column, its influence upon permeability is less than that of the ore and the coke. The large pieces now used have a tendency to roll to the center and thus increase the permeability of this part of the stock column. Smaller pieces would be more effective in promoting the permeability of denser portions of the stock. The size and physical properties of blast- furnace stone are important also for reasons best understood by considering the results obtained by the crushing and the sizing of iron ore. Crushing ore to about 2 in. at Provo, Utah, and to about I in. in Alabama produced material somewhat less permeable to gases, even though sized. In spite of some sacrifice in permeability, the efficiency of the process was improved by crushing and sizing the ore, as indicated by a substantial saving in fuel and increased output. This saving in fuel is due in large measure to more thorough reduction of ore in the upper part of the furnace and to a corresponding decrease in the amount of carbon consumed prematurely above the tuyeres by the reaction CO2 + C = 2CO ? 70,080 B.t.u. [I] The physical properties of stone, its size and rate of calcination are important because they influence the rate at which C02 is released and the completeness of calcination before reaching a level in the furnace where the temperature does not exceed 1050°C. (1920°F.). Briefly, carbon dioxide from the limestone or from the reduction of ore may cause premature com- bustion of carbon above the tuyeres. Assuming that 1000 lb. of limestone is used per ton of pig iron, about 435 lb. of C02 will be liberated during calcination of a good grade of stone. If all this CO2 from the stone were to oxidize carbon prematurely, about 120 lb. would be consumed above the tuyeres in a heat-absorbing reaction. The amount of carbon thus consumed when a

Jan 1, 1942

By W. Hurst, A. F. van Everdingen

A distillate-bearing sand complex is often made up of sand stringers of different permeabilities. In order to take into account the influence of the different permeabilities, "parallel flow" is defined, and this concept is used to compute the recovery efficiency of recycling such a sand complex. In the first approximation the position of the wells with respect to one another is not considered. In order to compute the effect on the recovery efficiency of the position of the wells, the area of a field is considered to be made up of rectangles; each rectangle containing one input well in the center and two producers located symmetrically with respect to the input well. Formulas are given from which to obtain the pressure and streamlines in a steady-state flow. A method is devised to compute rapidly the successive positions of the dry gas front. If the field is irregular in shape, pressure and streamlines can be obtained by a potentio-metric electrical model study. By using the concept of "parallel flow" and the results obtained by mathematical analysis or by electrical model study for a homogeneous formation, the effects of different permeabilities and of the location of the wells can be established. From these studies it is apparent that the efficiency of recycling can be profoundly influenced by differences in permeability among the various parallel strata. Introduction With the discovery of an increasing number of gas-distillate fields in the Gulf Coast, engineers have had occasion to give more thought to the performance of these reservoirs, as evidenced by the literature published in recent years. In the majority of studies published so far the formations are considered to consist of uniform, homogeneous sand. In this paper the authors wish to bring out the effect of variations in the permeability of the formations on the over-all recovery efficiency of wet gas in cycling operations. The importance of the permeability profile is clearly indicated by the fact that in gas cycling, highly permeable stringers in an otherwise tight sand can allow complete displacement of wet by dry gas in these stringers long before the wet gas in the tight portions of the sand is displaced. This by-passing will be reflected by a reduction in the condensate content of the production sooner than can be anticipated from a mathematical analysis or an electrical model study on uniform sands. Electrical model studies or mathematical analyses cannot take into consideration the manifold variations of permeability within the reservoir. Experimental as well as analytical difficulties make it necessary to consider the prototype for either of these studies as a perfectly uniform sand. Mathematical analyses are applicable only when a reservoir can be divided into units of simple geometrical form, of uniform thickness throughout. Electric model studies are capable of giving information on reservoirs of any shape or thickness, but it is essential that the sand be considered homogeneous, so that three-dimensional flow can take place. The method of approach in the following

Jan 1, 1946

By Andrew B. Crichton

The oft repeated statements of the United States Geological Survey and the Bureau of Mines that the coal reserves in the United States are sufficient for 3000 yr have given us all a sense of security hard to disturb. If we discount that statement 66 pct, which to the uninformed seems drastic, we would still have 1000 yr supply, and why should mortal man worry about the difference between 1000 and 3000 yr supply of coal. That is exactly the attitude which many who should be better informed have taken toward the problem. A recent brochure "How Strong is America," by the New York Herald Tribune, states there is "no end to coal * * The truth is staggering * * U. S. has enough coal to last 4000 years." What the statement actually means is that the calculator got as high as 4000 yr and decided it was pointless to go on. The President's ERP Committee on Natural Resources and others in high places continue to assure the country of our superabundance of coal. In the past few days the "Wall Street Journal" carried an item from Director Boyd of the Bureau of Mines saying that within a hundred years we would need to triple our annual coal production of 600,000,000 tons, making it 1,800,000,000 tons annually, and at that rate we had coal reserves sufficient for 1000 yr. In my humble opinion, we cannot now or ever produce 1,800,000,000 tons annually, because we do not have the reserves in the producing districts to do it. Past reckoning in geology may be, as in the Psalms, a thousand years are as yesterday, but the future must be considered more realistically, and " a thousand years" is really a "heck" of a long time. In most developed areas, mining engineers can count the coal reserves in terms of a hundred years or less, and in some important areas now producing large annual tonnages in much under fifty years. They think when they hear of thousands of years coal reserves, reference is made to distant fields and "the fields are always green far away." The estimates of our coal reserves upon which we are relying were made in 1907 under the direction of Marius R. Campbell, Director of the United States Geological Survey. It is apparent this work was not well done. It was necessarily based on rather meager data because of the little development and prospecting as of that date. There were mistakes in the correlation of seams, and they assumed the continuity of thick seams throughout large coal bearing areas where coal often did not exist. The overstatement of coal bearing areas in the Campbell figures are common. The 1907 survey includes all coals over 14 in. in thickness to a depth of 3000 it. The total coal reserves according to Campbell were 3157.2 billion tons. The production and mining losses that year would amount to 570 million tons and

Jan 1, 1949

By R. M. Leibrock, R. P. Vincent, C. W. Ziemer

The Stanolind flowmeter, which employs a hot-wire anemometer connected in a Wheat-stone bridge circuit, has proved useful for determining the relative productive ability of individual sand members of gas wells. The operation of this instrument in measuring gas velocities in the well bore above each producing member has provided both a direct and accurate means of analyzing reservoir performance. Results of tests conducted with the well flowmeter in the Hugoton gas field of western Kansas have indicated some rather unusual production characteristics. In two cases it was found that all or the greater part of the total gas produced was coming from one section in wells where four "pay" sections had been perforated individually. These actual measurements contradict in many instances the indications of data obtained from electric logs and from core analysis; the fact that these latter sources often give incorrect results, demonstrates the necessity of a method, such as is provided by the well flowmeter, for accurately determining the amount of gas coming from each producing member. Introduction In any gas well where a number of pay sections have been perforated individually and are producing to a common outlet, the question arises as to the relative amounts of gas being passed through each set of perforations. In the past it has been the policy to depend on core analysis to estimate relative productivities, or, where the sections were not cored, to obtain some idea of production characteristics from electric-log studies. The weaknesses in these methods are readily apparent and indicate the need for more reliable means of measuring gas flow from each zone. The Stano-lind flowmeter* was developed for this purpose. Preliminary tests were made with the instrument in the Katy gas field near Houston; however, the bulk of the routine work with the well flowmeter has been confined to the Hugoton gas field in western Kansas, where results obtained have been encouraging. A description of the instrument, the field technique employed in testing, and a few of the results obtained in the Hugoton area are discussed in this paper. Description or Instrument The well flowmeter is 1¾ in. od and 7 ft long; it is entirely self-contained, can be run through tubing as small as 2 in. id in wells with high pressure (4500 psi) and temperature (210°F) and is lowered on a wire line commonly used for other instruments of the bottom-hole type at falling rates up to 500 ft per minute. It will detect gas flow as low as 10 ft per minute linear velocity, and yet withstand and record velocities of 1000 ft per minute without damage to the detecting element. Killing the well is not required nor desirable for running a production profile when using the instrument, and it is necessary to stop flow for only a short time. The detecting element of the instrument is a hot-wire anemometer connected in a

Jan 1, 1948

By C. D. Rugen

Ground raw material as fed to the cement kiln generally is a mixture of two to four components, each of which may have widely varying physical and grinda-bility characteristics. Chemically similar materials found in the same or different deposits may also differ appreciably in physical properties, depending on their crystalline structure. The calcareous or principal cement raw material may vary from a soft chalky limestone or friable cement rock at one plant to a hard limestone or oyster shell at another plant. Argillaceous materials include clays, shales and granulated slag. Siliceous and/or iron-bearing material, including sand, 'iron ore and cinders, may also be required in addition for certain types of mixes. Frequently differences in grindability characteristics are not given the attention they deserve in comparing grinding results at one plant with those at another or in selecting suitable circuits or equipment. Many types of crushing and grinding units are used, with numerous open and closed circuit arrangements. Both wet and dry processes are used successfully. When rebuilding or installing a new grinding department, the choice of process or circuit in some cases may be dictated by the nature of the materials being ground but in other cases it may be the result of good salesmanship or a compromise. An over-all evaluation of wet process vs. dry process grinding should not be made without considering the effects on all other *producing departments in the plant. In general, the more recent grinding installations, both wet and dry, have employed closed circuits, but many older open circuits are still in successful operation. In our experience, closed-circuit raw grinding pays, because of lower power consumption and less operating labor per ton of product. However, some dry open-circuit mills with improved equipment and operating methods compare favorably in performance with dry closed-circuit units. Character of Ground Raw Mix (Kiln Feed) Grinding in the cement plant in general requires a considerably finer product than in most ore-grinding operations. A distinction between fineness of kiln feed and of cement may be made in that kiln feed preferably should be ground to a limiting size,whereas finished cement should include a range of size fractions including sufficient fine flours to give a product with satisfactory physical qualities. Grinding raw mix for kiln feed therefore is more comparable to ore grinding, although the limiting size is smaller. Most kiln feeds are ground from 85 to 95 per cent passing 200-mesh, depending on mix composition. Some cement chemists believe that raw materials cannot be too fine, since her particles theoretically combine more readily and intimately in the kiln. However, there are certain definite practical objections to extremely he kiln feed, such as loss of kiln dust, unstable material flow through the kiln and greater difficulty in control of chemical composition due to dust loss, and the disproportion of fines from the more easily ground component. Our

Jan 1, 1948

By B. M. Harra, F. G. McCutcheon, O&apos

Until about 1930, the universal practice of horizontal-retort zinc smelters in the United States, as far as the writers are aware, was to operate the retort furnaces on a 24-hr cycle; that is, the retorts were charged in the early morning of one day, and in the early morning of the following day the residues were cleaned out, the retorts recharged, and a new cycle started. During the business depression of the early thirties, zinc production fell off to the extent that zinc smelters had idle retort capacity. Rather than continue to run some of the retort furnaces on a 24-hr cycle and shut down the remainder, a few companies decided to try out a longer cycle. Although the output of zinc per retort per day is lower, the longer cycle permits a larger charge per retort and improved zinc recovery. Advantages of the longer cycle were soon evident, and the practice spread rapidly. Various lengths of cycle were used, typical examples being 28-hr, 32-hr, 36-hr, and 48-hr. The 48-hr cycle fits in best with the standard routine of smelter practice that was built up on the basis of the 24-hr cycle; that is, the retort furnace "maneuver" always comes at the same time of day, and can be performed in the cool hours of the early morning. Under some conditions, particularly in some of the older plants, where the retorts are smaller than in newer plants, a 48-hr cycle is longer than necessary, and some intermediate length of cycle may theoretically be most economical. Use of an intermediate cycle, however, means that the maneuver comes at different times on consecutive days, and that sometimes it comes during the hottest part of the day. The work on the retort furnaces is extremely hot and arduous at best, and it is much worse, of course, if it is done during the heat of a summer day. When labor was plentiful and tractable, many plants were able to operate on cycles of intermediate length, but the workmen did not like the working hours. Under present labor conditions, it is hardly practicable to operate with a cycle of intermediate length, so the choice has narrowed down to the alternatives of 24-hr or 48-hr cycles. In any discussion of economics, too comprehensive generalization is not warranted, because local conditions affecting economics vary greatly. The best economic practice at one plant at any given time may be uneconomical at another plant, or even at the same plant at another time. To determine the length of cycle that is the better practice at a given plant at a given time requires a weighing of the advantages and disadvantages of each cycle, taking into consideration all the local conditions. some of the factors that must be considered in making the comparison are discussed briefly in the following paragraphs.

Jan 1, 1949

By C. A. Hartnagel

The production of petroleum in New York in 1940, totaling 4,999,000 bbl., was only slightly under the amount produced in each of the previous three years. The year 1940 started auspiciously with a posted price on Jan. I of $2.75 a barrel. Four price reductions, beginning in May, resulted in August in a low of $1.85 a barrel, after which two increases brought the year's closing price to $2.15 a barrel. The favorable crude price at the beginning of the year stimulated an increased drilling program, especially in the water-flooding districts. In the Allegany County region, which accounts for about two-thirds of the state's oil production, 886 wells, including water-intake wells, were drilled; 200 more than in the preceding Year. During the closing months of the Year there was a marked decline in the number of wells drilled. The unfavorable position in which the industry found itself before midsummer was due largely to the loss of export markets for its high-grade lubricants, constituting approximately 25 per cent of its business. As a result of this situation, runs to refineries were curtailed as much as 30 Per cent at the middle of the Year. Improvement in market conditions toward the end of the Year found the stocks of available crude at an almost record low. Deep DRILLING with the gradual exhaustion of some of the important natural and flood-oil-produc-ing areas of the Allegany and Bradford pools, overproduction will not be a serious problem in the future. The possibility of finding new territory or deeper producing sands has been further lessened by the drilling of additional deep wells for gas in and about the present oil fields. Many of these wells drilled to the Oriskany sand-stone were over 4000 ft. deep and have tested the entire thickness of the Devonian formation, the upper 2000 ft. of which contain all the important oil-producing strata in the state. Water-flooding It is thus evident that the problem of the New york oil producers is not one of find-ing new supplies but of obtaining as much 6 oil as possible from the old developed fields that during the 60 years of their life have 1 produced I 3o,ooo,ooo bbl. of oil. Although a few floods were in operation before I9I9, when the production of oil by flooding was 1 made legal, the output for that year amounted to only 85I,000 bbl. From 1919 I on there has been an almost constant increase, which during the past four years has averaged well above 5,000,000 bbl. annually. During the last 22 years, which constitutes the period of important flooding operations, 651337,000 bbl. of oil have been produced in the state. Careful estimates indicate that between one-third and one-half of the oil fields are being flooded or are already watered out. Some of the flooded and watered-out areas include territory with unusually thick sands, which were highly productive during the early history of the fields. From a recent study of operations in the New York oil fields, it is estimated that about 65,ooo,oo bbl. of oil

Jan 1, 1941

By C. A. Hartinagel

During 1941, the total production of crude oil in New York state was 5,185,000 bbl. This represents a small increase over the average for the past five years. From 1921, when the annual production of the state amounted to only 988,000 bbl., there was a regular annual increase in production (excepting one or two years) until the 5,000,000-bbl. mark was reached in 1937, After more than 20 years of oil recovery by flooding methods, it was generally believed, until a few months ago, that the rate of production was nearly at its peak and within a few years the fields would experience a gradual decline as the thicker sands became exhausted and the thinner ones could be worked only at increasing costs. As a result of the present emergency, however, unusual efforts are being made, in spite of higher costs of operation, to increase the output of Pennsylvania grade oil, to which the New York product belongs. Since most of any increased production would be obtained by flooding, and since floods travel slowly, no large increase in production can be expected for some months to come. During the first year, 10 or 15 per cent increase could be obtained, but maximum production, an increase of perhaps 40 per cent, could not be expected until some time during the second or third year. In the Allegany fields, which account for two thirds of the state's oil production, 1246 wells, including water-intake wells, were drilled during the year; 390 more than in the preceding year and 590 more than in 1939. It is evident that much of the best oil territory has already been developed. As producers move toward edge properties and thinner sands, returns will be smaller, whereas costs remain the same or, under war conditions, become higher. It is estimated that at least 60 million barrels of oil is in sight and will be produced from the thicker sands by present recovery methods. In the thinner sands and edge properties, some 35 million additional barrels can be produced at a profit only if prices become higher. In view of the fact that there is little hope of finding new oil pools in New York, one of the future problems of the oil producer will be to obtain adequate returns for increased production costs. The year started with a posted price of $2.15 per barrel of crude. There were five successive price increases until the high of the year was reached at $2.98 on Aug. 14. Eight days later the Office of Price Administration directed that the price be reduced to the June level of $2.75 a barrel, which remained in effect to the end of the year. With rising costs of operation, it is feared that many of the smaller properties cannot continue production unless the Federal price cut is revoked. During the year, Allegany Refiners Inc., a local enterprise founded in 1933, with plant at Bolivar, western Allegany County, increased its refining capacity from 1000 to 1500 bbl. daily. At the same time equipment was added to make the plant a complete lubricating-oil refinery, including facilities for the refining of wax into the finished product. Previous to the enlargement, it was necessary to sell the wax

Jan 1, 1942

By C. A. Hartnagel

The production of petroleum in New York state in 1942 amounted to 5,410,000 bbl. This represents an increase over each of the four preceding years, and, with the exception of 1937, is the largest production since the peak of over six million barrels in 1882, shortly after the discovery of oil in Allegany County. The oil industry in New York is virtually stabilized and there has been little or no exploration for new sources of supply in recent years. The boundaries of the present fields were established more than 30 years ago and since then no additional reserves have been found. Deep drilling for natural gas during the past 10 years both within and without the oil fields has failed to find oil in quantity below the present producing sands of Devonian age. Oil Since 1882, the New York fields have produced approximately 140 million barrels of oil. Of this amount, 65 million was produced up to the year 1919 by ordinary pumping methods; that is, without flooding by water or the use of other secondary-recovery methods. In the year 1919, when a law was passed making the use of water-flooding methods legal, the oil production, of the state amounted to only 851,000 bbl. In the 23 years since 1919, there have been produced in the state 75 million barrels, or 10 million more than in the previous 37 years, which included the period of flush production. Price.—On March 26, the price of crude oil was raised from $2.75 to $3.00 per barrel, hut this increase had little or no effect on the number of wells drilled. In the Allegany field, which accounts for three fourths of the state's oil production, 1259 wells were completed in 1942, 7 less than in 1941. The smaller number of wells drilled was not only due to the shortage of labor but also was caused by the fact that in water-flooding territory a definite program for drilling wells is followed, and the flush period of an oil well is not usually reached in time to profit by any given price increase. Daily Production.—All of the oil wells in New York state, some 21,000 in number, are small producers. The average daily oil production is 7/10 bbl. per well. Under good flooding conditions, a maximum production of 5 to 8 bbl, a day is reached about one year after the flood begins to act on the well. In 5 years the daily production usually is less than one barrel. Although most of the oil in New York is produced by flooding, an estimated 2500 old wells produce without flooding. Some of these produce as little as 1/20 bbl. a day and are pumped only at intervals. The small producing Wells are mostly on lands leased to the larger oil companies and later will be included in a flooding program. At present, they are pumped only because the owners of the land insist on the royalty. Government Aid Needed.—Because of its good lubricating qualities, New York oil is one of those for which there is an insistent and growing demand, but even at its present price of $3.00 per barrel, many of the operators are producing at a loss.

Jan 1, 1943