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By H. J. Ramey

Conventional calculation of total system isothermal compressibility for a system containing a free gas phase involves, among other things, evaluation of the change of oil and gas formation volume factors and the gas in solution with pressure. Preferably, this information should be obtained from laboratory measurements made with particular oils and gases. Often, experimental measurements are not available. In this case, it is necessary to obtain pressure-volume-temperature relationships from general correlations such as those of Standing' for California oils. In order to speed estimates of compressibility, generalized plots have been prepared of the change of both oil formation volume factors and gas in solution, with pressure from Standing's correlations. A generalized plot for estimating the change in the two-phase (oil and gas) formation volume factor with pressure is also presented. Usually, the effect of gas dissolved in reservoir water upon the total system compressibility is neglected for gas saturated systems, due to the low solubility of gas in water. Results of this study indicate that the increase in total system compressibility caused by solution of gas in water is often as large as the compressibility of wafer, and can be magnitudes larger for low pressure systems. Generalized results for estimating the change of gas in solution in water with pressure are presented in tabular and graphical form. INTRODUCTION During the past decade, pressure build-up and drawdown techniques have gained an important place in reservoir engineering. Build-up and drawdown analyses are only two special applications of the broad field of transient fluid-flow theory. All solutions of transient fluid-flow problems contain a parameter called the total system isothermal compressibility. This property of fluids and porous rock is a measure of the change in volume of the fluid content of porous rock with a change in pressure, and it may vary considerably with pressure. Evaluation of total system isothermal compressibility is not difficult, but it is tedious and time-consuming. Often compressibilities are estimated roughly, or transient flow methods are neglected completely. The benefits of using accurate system compressibility in properly-executed build-up or drawdown analyses are: 1. Better planning of pressure build-ups may be achieved to avoid unnecessary loss of revenue due to excessively long shut-in periods, or to shut-in periods too short to yield useable data. 2. Better and more reliable estimates of static formation pressures for reserves estimates and rate performance estimates. 3. Reliable information for evaluation of well completion effectiveness, and planning and interpretation of well stimulation efforts. The purpose of this paper is to clarify the nature of the total system isothermal compressibility, and to present useful methods for estimation of compressibility, particularly for systems containing a gas phase. DEVELOPMENT Numerous publications have presented solutions to transient single-phase flow of slightly compressible fluids, stressing pressure build-up applications. In transient flow, a compressibility* term arises to permit volume content of fluids in porous rock to change as pressure changes. The basic nature of the compressibility term is usually taken for granted. Problems arise in practical applications of transient fluid theory because most published works consider only one flowing fluid—in an ideal porous system containing only one fluid. In 1956, Perrine2 presented an intuitive extension of single-phase flow pressure build-up methods to multiphase flow conditions. Later, Martin- established conditions under which Perrine's multiphase build-up method had a theoretical foundation. Perrine has shown that improper use of single-phase build-up analysis in certain multiphase flow situations can lead to gross errors in estimated static formation pressure, permeability and well condition. It is likely that, much pressure build-up data for oil wells should be analyzed on the basis of multiphase flow. For both single-phase and multiphase build-up analysis, the isothermal compressibility term in dimensionless time groups often should be interpreted as the total system compressibility. All real reservoirs contain one or more compressible fluid phases. In addition, rock compressibility can contribute in an important way to the total system compressibility. The proper total system compressibility expression may contain terms for compressibility of oil, gas, water, reservoir rock and terms for the change of solubility of gas in liquid phases.

Jan 1, 1965

By F. Bonaccorso, G. Venturello, C. Antonione

A study of the effect of small amounts of interstitial impurities on recovery and re crystallization in high-purity iron (99.995 pct) has been undertaken. This paper gives results on the effect of carbon, introduced in small-dosed amounts @om 0.0005 to 0.0086 wt pct) by heating iron specimens of high purity m a static atmosphere of CO + ,. The materials prepared in this way, cold-worked 80 pct and subjected to a series of isochronal and isothermal annealings, were submitted to examinations by X-rays, micrographs, and hardness tests. It was observed that effect of carbon is remarkable in the sense of blocking recovery of mechanical properties up to the temperature at which re crystallization begins. On the contrary, carbon has a negligible effect on primary re crystallization temperature, when compared with the known effect of substitutional impurities. This is in agreement with the high mobility of interstitials. In effect, only a slight decrease, -20 pct, of the grain-boundary motion rate was noted, due to the interaction between the grain boundary and the carbon atoms. On the other hand, in the samples in which the carbon content is above the solubility limit at the temperature at which re crystallization occurs, a slight increase of nucleation frequency is noted due to the presence of precipitated carbides. ThE effect of purity on recovery and recrystalli-zation phenomena has been known for a long time; however, recently, new attention has been given to the problem since new methods for obtaining metals with extremely low impurity contents have become available. Most of this research work essentially concerns the effects of impurities which cause precipitates or give rise to substitutional solid solutions. The works of Bolling and winegard1 and Aust and utter' on lead, and Vandermeer and orddon' on aluminum, 01sen4 on nickel, and Abrahamson and Blakeney on iron should in particular be referred to. On the effect of this type of impurities a quantitative theory has been formulated by Detert and Lucke6 and has lately been discussed critically by Cahn7 and Gordon and vandermeer.' Interstitial solid solutions in iron have not as yet been studied. As the study of the effect of interstitials is of great interest both from a theoretical and practical standpoint, it was deemed useful to examine the effects of carbon, nitrogen, and boron on recovery and primary recrystallization of iron. There already is some work by Chaudron et al.,1-" on the effect of interstitials on iron; their work, however, mainly concerns secondary recrystallization. The present paper refers in particular to the effect of carbon. EXPERIMENTAL PART Preparation of Materials. The pure iron used for this research was obtained from FeCIS recrystal-lized and purified by extraction with isopropylic ether. From the ferric chloride purified in this manner, hydroxide was precipitated with a solution of very pure ammonia, and, by calcination in pure sintered alumina crucibles, oxide was obtained. Reduction of the oxide to iron sponge was performed in sintered alumina tubes with very pure hydrogen at 650°C; at the end of the operation temperature was increased to 900°C. Specimens for the experiments were obtained by sintering the sponge at 1480°C in pure Hz after a pre sinter ing treatment at 900° C. It is important to note that the treatment at 1480°C in Ha produces a further purification from more volatile elements such as zinc, cadmium, arsenic, lead, and tin. Details on the preparation and characteristics of this type of very pure iron are given in a previous work.'' Only the complete analysis performed by neutron-activation methodsz3 is given here, Table I. Some of the specimens prepared in this way were carburized in the 0 region with very low amounts of carbon by treating them at 700°C in a static atmosphere of Ha containing a definite amount of CO. The set-up used is described in Fig. 1. A gas-tight quartz tube containing the specimen to be carburized and an internal friction control specimen, after being evacuated, was filled with Hz

Jan 1, 1963

By W. L. Freyberger, R. B. Booth

Froth flotation is a chemically induced method for beneficiating or up- grading an ore, which utilizes a layer or column of froth as a separating medium to segregate and remove the valuable minerals from the worthless gangue components of a finely ground ore suspended in water. The object of this chapter is to discuss the theoretical aspects of froth formation, the various frothing agents employed in flotation, and the effect of chemical structure on froth formation, and to correlate these factors with flotation technology. The flotation method of separation is conducted in three main steps: 1) selective chemical modification of the surface of specific mineral particles to effect floatability or nonfloatability; 2) contact between air bubbles and mineral particles, the selective adherence of floatable minerals to these bubbles, and the rejection of nonfloatable minerals; and 3) separation of the floatable minerals from the nonfloatable minerals. As indicated above, these three operations are achieved by the use of chemicals. Frothers play their most important role in the second and third steps by influencing particle- bubble contact and by affecting the degree of separation obtained in the froth column. Frothers, as defined by flotation operators, are compounds that are used specifically for the purpose of creating a froth in a flotation separation. How- ever, some collectors produce froths that are adequate for some flotation operations. Although this chapter is chiefly concerned with the specific frothers used in flotation, some discussion of frothing collectors is included. Otherwise, collectors (or promoters) and modifiersare not discussed at length; for information on these types of flotation chemicals, the reader is referred to other sections of this book or to other sources.l HISTORICAL DEVELOPMENT OF FROTHING AGENTS Historically, there are two distinct phases in the development of frothing agents and other flotation chemicals: 1) 1860 to 1920-oil flotation, and 1921 to date-chemical flotati0n.2~3 Early in the first period, large quantities of fatty and oily materials, up to 10 to 20% of the weight of the ore, were used as a means of separating the sulfide and oxide components from the gangue minerals in ore pulps. Later, various gases replaced these large quantities of oil as a buoyant and separating medium, decreasing oil requirements to less than 1% of the weight of the ore. With this reduction in oil

Jan 1, 1962

By S. Edward Drummond, Charles D. Haynes, Stephen H. Stow

This paper is a preliminary report on the occurrence and distribution of economically interesting heavy minerals (kyanite, sillimanite, staurolite, zircon, monazite, ilmenite, leucoxene, rutile) in sands from the sea floor surface of the offshore area, Alabama-Mississippi. Weight percent of heavies derived from the +60 portion of 97 samples is contoured in [Fig. 1]. Five hundred grains from 42 of the heavy mineral separates were identified and sized microscopically; the data were converted to weight percent for each mineral species and are summarized in [Table 1]. Heavy Mineral Distribution In the Gulf, there is a general westward decrease [(Fig. 1)] in maximum abundance of heavies from 2.4% north of Sand Island at the mouth of Mobile Bay to slightly over 1.0% south of Petit Bois Island and a corresponding decrease in the Mississippi Sound from 1.4%, north of Dauphin Island to slightly over 0.25% north of Horn Island. Average concentrations of heavies for different areas are found in Table 1. There is westerly longshore transport in this area; the interaction of the longshore current with discharge from Mobile Bay and disruptions of the current by Sand Island, possibly aided by a shoaling effect, appear to be the cause of the preferential deposition and concentration of heavies (2.4%) north of Sand Island in 10 to 14 ft of water.

Jan 1, 1977

WHEN Georgius Agricola, in 155o, dedicated his now famous De re Metallica to the rulers of Saxony, Thuringia, Meissen, and other, smaller principalities, he included in his review of previous works on similar subjects reference to two books written in German: one, an "anonymous, rather disorganized account of assaying for metallic content and of metals," which must be the Probierbüchlein, the other, "dealing - with veins, written by Calbus of Freiberg, a well-known physician."* Calbus is mentioned a second time-and cited-at the end of the Third Book of De re Metallica. Comparison of the citation with the Bergbüchlein leaves no doubt that Agricola considered Calbus of Freiberg the author of the latter work, although all the editions of the Bergbüchlein known now were published anonymously. It is generally accepted by those who have dealt with the bibliography of the Bergbüchleint that Calbus was Ulrich Rülein von Kalbe, who served the City of Freiberg, in Meissen, as health officer in 1497, as member of the City Council in 1509, and as mayor in 1514 and 1519. He died at Leipzig in 1523. In connection with the very garbled description of the mining compass toward the end of Chapter 3 of the Bergbüchlein it is of interest that von Kalbe is supposed to have been not only a physician of repute but a mathematician, astronomer, mine sur-

Jan 1, 1949

By Blamey Stevens

(San Francisco Meeting, October, 1911.) IN this paper, which is a logical extension of my paper, The Laws of Intrusion, 1 the various pressures of emanation and their mechanical causes and effects on the large scale of nature are determined, .and a classification of emanations is deduced therefrom. The Subterranean Sea. The subterranean sea is here defined as the intercommunicating water contained in the trains of pores and fissures of the rocks down to great depths. Whether the actual amount of water constituting this subterranean sea be large or small, does not enter into the present argument, since the static pressure of this water at any particular depth is not a function of the quantity : it involves only the depth and the density of the water. Densities. The total pressure at depths down to 10 or 15 miles is made up of the rock-stresses investigated in my previous papers, and the pressure of the subterranean sea. The latter component must evidently be equal to the weight of a solid column of the overlying water of unit sectional area. As water expands with heat, it should really be necessary to sum the density at every level. A knowledge of the densities of water under a variety of conditions is therefore needed, but does not seem ever to have been ascertained for such combined pressures and temperatures as we have to consider. The specific gravity of water at 28° C. for various pressures up to 400 atmospheres, has been determined by Barus,2 who

Apr 1, 1912

By O. G. Paasche, Yuan-Shou Shen

THERE is a disagreement among the various authors about the exact manner of transformation of ZrCr2. Rostokerl and others2 stated that ZrCr2 had a C-14 (MgZn2) type of structure below 1000°C and a C-15 (MgCu2) type of structure at temperatures above 1000°C. Alisova3 and others4 reached the opposite conclusion and stated that the transformation temperature is close to the melting point of ZrCr2. A literature survey shows that various investigators3'= who homogenized the specimens at a temperature higher than 1000°C have concluded that ZrCr2 had the C-15 structure at room temperature. Meanwhile, Jordan et al.4 reached similar conclusions without annealing the specimen. Other investigators1,2,6,7 who X-rayed the specimens in the as-cast condition without annealing reached different conclusions. The investigation reported herein was conducted with the aim of exploring the exact manner of transformation of ZrCr2 by various heat treatment tests. The alloys for this examination were prepared from iodide-reduced zirconium crystal bars, 99.9 pct purity, and electrolytic chromium, 99.9 pct purity. They were melted in a nonconsumable electrode arc furnace with water-cooled copper crucible in a helium atmosphere. The melting loss of each alloy was less than 1.5 pct by weight. Chemical analysis of a randomly selected specimen indicated that there was a very close agreement between calculated and analyzed compositions. Before being heat-treated each specimen was encapsulated in a vycor or quartz tube inside which an argon atmosphere was maintained at a pressure of lower than 1 atm. In determining the crystal structure of each specimen with a Debye-Scherrer camera, the standard procedure8 for X-ray quality analysis (Hanawalt method) was followed. The different series of heat treatment tests in this investigation are tabulated in Tables I and 11. The tests in Series I, specimens from 1-1 to 1-9, which were similar to Rostoker's experiment1 indicated that the transformation temperature seemed to fall between 870° and 900°C and that the crystal structure of ZrCr2 at lower temperature seemed to be of the C-14 type. However, once the compound is transformed to C-15 type, it is impossible to reverse the transformation back to the C-14 type by first heating the specimen above 900°C and then annealing it slowly below 900°C as shown in Experiments II-1 to II-3. Thus, it appears that the specimen of ZrCr2 will transform from C-14 to C-15 structure when heated above 900°C but will not transform from C-15 to C-14 when annealed slowly passing 900° C even after the extremely slow cooling process such as indicated in the experiment of Specimen II-3. As a valid transformation temperature is a temperature at which the transformation is reversible, therefore the temperature 900°C (or other temperature close to 900°C) is not the transformation temperature for ZrCr2 and the C-14 structure is not the stable structure of ZrCr2 at lower temperatures. The C-14 structure is retained at room temperature because the transformation to C-15 structure is very sluggish and the fast cooling after melting does not allow enough time for the transformation to take place. Additional energy is required to alter the metastable condition of the C-14 structure. The sluggishness of this transformation was again demonstrated through another series of experiments. Four specimens with C-14 structure were taken. Then they were annealed at 900°C but each specimen was soaked for a different period of time, Table 11. X-ray diffraction patterns of this group indicated that the C-14 structure gradually disappeared as the soaking period was lengthened. The figures listed under the column "C-14 Structure, pct" were estimated from the intensity of the d = 2.330 line of the diffraction pattern corresponding to the structure. Notice that the intensity of this line became weaker for longer soaking periods. To determine the transformation temperature of ZrCr2, specimens with C-14 structure (as-cast condition) were annealed at 1300°, 1400°, 1500°, 1550°, and 1600°C, respectively. A final specimen was first heat-treated to 1500°C in order to transform it to C-15 structure, then heat-treated at 1600°C again. From the X-ray analyses of this series of tests, Specimen Nos. III-1 to III-6, it is evident that a transition from C-15 structure at lower temperatures to the C-14 structure occurs at some temperature between 1550° and 1600°C.

Jan 1, 1969

By T. F. Bower, M. C. Flemings

Results are reported of a study of surface dendrilic structure of an Al- Cu alloy solidified against a chill wall. Most primary and secondary "arms " in the surface dendritic structure are arranged orthogonally, giving the impression of strong preferred orientalion on the surface. However, no such preferred orientation exists and it is therefore evident the arms do not represent (100) directions. The primary arms are shown to be interseclions of a (100) plane wilh the chill plane, or, equally often. the projeclion of a (100) direction on the chill plane. Secondary dendrite arms are usually within a few degrees of 90 deg to the primary arm, independent of grain orientalion. Prirary, secondary, and higher-order surface dendrite arms almost always represenl intersections of (100) platzes with the chill surace, or pvojections of (100) direclions. Growlh of secondary arms is favored on the side of the primary arm where a (100) direclion points toward the chill surfAce a1 a Lou, angle. Surface dendrile arms are often observed to be bent. In these cases, the crystal lallice changes orientation; bending is concave to the chill surface. In a previous paper,' a technique was discussed whereby large grains can be obtained at a chill surface. The technique used involves quickly drawing superheated liquid A1-4.5 pct Cu alloy into a thin copper mold, so that the mold is full well before solidification begins. The chill surfaces employed are polished copper blocks coated with amorphous carbon. Shrinkage during solidification between dendrite arms and grains delineates both, without the need for polishing or etching of the cast surface. The grain structure of the chill surface was discussed in a previous paper;' in this paper, the dendrite arms within each grain are examined. Previous work on surface dendrites includes that of Edmunds, who studied the development of preferred orientation in zinc, cadmium, and magnesium.' In zinc and cadmium, he found that the surface region has a (0001) texture (parallel to the chill surface). Walton and Chalmers reasoned that, since the fast growth (1010) directions are in the basal plane, nuclei which have this plane parallel to the mold wall would produce larger grains than nuclei with other orientations. Hence, the texture observed is as expected.3 The same authors, in measurements on aluminum ingots, found no preferred orientation at the mold wall. However, the X-ray technique they used measured the preferred orientation in terms of grain numbers, not grain areas; larger grains were weighted equally with small ones. No preferred orientation is expected on this basis at the chill surface. In a later paper,' Edmunds stated that experiments show a random grain orientation at the surface in die cast aluminum; his technique, also used in his earlier paper, takes account of grain area. Little work has been published on the dendritic structure of metal chill grains. Recent work of Biloni and Chalmers on "predendritic growth" shows the change in morphology from spherical to dendritic during the initial stages of freezing, 5 but this work did not include detailed examination of the fully developed dendrites. Other pertinent work includes that of Lin-denmeyer, who investigated the growth of ice dendrites. 6 When growth was on a substrate, the dendrite axes were bent. The bend corresponded to a change in orientation of the crystal lattice and occurred in such a way as to align the basal plane to the substrate. DENDRITE STRUCTURE Fig. 1 shows the chill surface of a typical casting poured above the critical temperature necessary to produce coarse grains. A cursory examination of these grains shows that the surface dendrite arms within most of the grains are oriented roughly perpendicular to each other. One is tempted to assume that these are (100) directions and that, therefore, marked preferred orientation exists at the chill face. This, however, is not the case. Each of the grains in the casting of Fig. 1 was separately identified, Fig. 2, and its orientation determined by the Laue back-reflect ion method. Results are given in Fig. 3 and it is seen there that no preferred orientation exists. Even when grain area is accounted for, there is no significant preferred orientation. The relationship between surface grain structure and crystal orientation was then obtained by assigning X and Y axes to the casting surface, Fig. 1, and assigning the same axes to the stereographic projections of each grain. Thus, the visible surface structure could be compared readily with grain orientation. This was done for fifty-five of the grains of Fig. 1. Results of this study on three typical grains are described below, and some general observations given subsequently. Fig. 4 shows the structure and stereographic projection of a grain which lies near the (100) zone (with respect to the casting surface). The X and Y directions are marked on the projection, and the photomicrograph mounted with the same orientation. Poles of the stereographic projection represent crys-tallographic directions in the grain which point out of the casting, toward the chill. Two (100) directions are shown in Fig. 4. A line joining the center of the projection and a pole represents the projection of the pole onto the X-Y plane (chill surface). Two such lines are shown in Fig. 4 (solid lines). A line joining the intersection of a great circle with the circumference of the projection gives the trace of a crystallo-graphic plane in the chill surface; two such traces are shown (dashed lines).

Jan 1, 1968

By S. K. Basu, H. H. Kellogg

THE physical-chemical behavior of the system Pb-S-0 is of prime importance to the understanding of lead smelting processes, yet little accurate information is available on either equilibrium or kinetic behavior in this system. This paper is the first report of a program designed to fill gaps in our knowledge of this system. In the total ternary Pb-S-0, the region of greatest metallurgical interest is that bounded by the compositions Pb-PbS-PbS0,-PbO-Pb. Systems richer in sulfur, or richer in oxygen,* than those essentially pure SO2. This conclusion follows from the fact that all systems are in a highly reduced state, since either PbS or Pb is a constituent of all the equilibria. The content of 02, SO3, S2, S6, S8, and so forth, can be shown to be negligible compared to SO, in all such systems.* corresponding to this region can only be obtained at gas pressures exceeding 1 atm, a condition seldom met in lead smelting practice. Not only is the present study limited to condensed phases within this portion of the total system, but it is limited to temperatures at which all phases are pure solids, except for lead, which is liquid. In this limited system the following seven condensed phases are known to exist: Pb(l), PbS(c), PbO(c), PbSO,(c), PbSO,•PbO(c), PbSO4 • 2PbO(c), and PbSO, -4PbO(c). PbO exists in two crystal modifications,' but only the high-temperature yellow form is considered here. Schenck and co-workers2-4 reported the compound PbSO4 3Pb0 to be stable at high temperature, but the more recent work of Lander,5 and the present work, prove that the tetra-basic sulfate, rather than the tri-basic sulfate is stable. Fig. 1 shows the composition diagram for the binary PbO-PbSO2, based primarily on the work of Lander. In this study the univariant boundaries and invariant points existing among these seven condensed phases and the gas phase have been determined. In a ternary system, the phase rule indicates that an invariant point involves the simultaneous equilibrium of five phases—four condensed phases and the gas phase. A univariant relation involves four phases—three condensed phases and the gas phase. The gas phase in the systems studied is The following stable univariant equilibria between SOz and the condensed phases were identified: (a) PbS + 7PbS04 = 4(PbSO, - PbO) + 4SO2 (b) PbS + l0(PbS04 • PbO) = 7(PbSO4- 2PbO) + 4SO2 (c) PbS + 8(PbSO4 • 2PbO) = 5(PbSO4 . 4PbO) + 4SO2 (d) Pb + PbSO, • 4PbO = 6PbO + SO2 (e) 3PbS + PbSO4 . 4PbO = 8Pb + 4SO2 (f) 3PbS + 16(PbS04 PbO) = 7(PbSO4 . 4PbO)+ 12SO2 (g) 2PbS + PbSO,2PbO = 5Pb + 3SO2 (h) Pb + 3(PbSO4 . 2PbO) = 2(PbSO,. 4PbO) + SO, Of these eight univariant equilibria, five were measured in this work (a, b, c, d, and g) and the behavior of the other three (e, f, and h) was calculated by thermodynamic analysis of the measured data. Two invariant points were found corresponding to simultaneous equilibria as follows: Point 1: PbS, PbSO4PbO, PbSO4.2PbO, PbSO, - 4PbO, and SO2 Point 2: Pb, PbS, PbSO, . 2PbO, PbSO, - 4PbO, and SO2, From the measurements it was also possible to calculate the thermodynamic properties of the three basic sulfates of lead at 298.16°K. EXPERIMENTAL Apparatus—The experimental method consisted of the measurement of the gas pressure exerted by a given reaction mixture at a given temperature. An iridium crucible was used to contain the reaction mixture. There was no evidence of attack of the iridium,* but after use at high temperature for a week

Jan 1, 1961

By Vaughn Moyer

A method for incorporating well drawdown effect into reservoir calculations is presented in detail, together with examples of its use for widely divergent conditions that could be normally encountered in oil reservoir sands. Tentative conclusions as to the effect such factors as permeability, producing interval, well spacing, or well damage caused by completion or repair practice could have upon economic ultimate recovery are reached. It is carefully pointed out that the conclusions reached are subject to limitations indicated in the text, and placed upon all calculations made in the paper. Introduction Papers have been presentedl-3 in which theoretical depletion histories for reservoirs under equilibrium conditions and no appreciable well-bore drawdown pressure are determined. However, except for a limited number of cases, appreciable drawdown Pressures in a well bore exist, and Pressure and saturation gradients consequently vary throughout a reservoir. This Paper is an attempt to incorporate well-pressure drawdown into reservoir history, and to analyze certain factors, such as those involving recovery, well spacing, and productivity index, from the standpoint of permeability and drainage radius. BY incorporation of drawdown into reservoir history, it is believed that theoretical considerations will more closely approxi- mate actual reservoir behavior experienced in an oil field. For purposes of simplification, a solution gas-drive type field1 without primary gas cap, has been selected. Basic Data and Assumptions Details of equilibrium saturation conditions for no drawdown production for various pressures in a reservoir are deter-minable by methods described by several are permitting the construction of a curve of oil saturation vs Pressure for any selected combination of initial interstitial water and hydrocarbon saturation (Fig I). This curve is then a description of equilibrium saturation conditions at any given pressure in a reservoir. Developing the above, details of saturation and flow permeability may thus be determined for any increment or portion of a well drainage area or reservoir. In this manner the effect of pressure differential (drawdown) may be incorporated into reservoir and well drainage considerations. It is pointed out that this method thus makes use of no-drawdown equilibrium production data, superimposing a draw-hwn effect upon them. It also assumes that net flow conditions in any considered increment of reservoir are not materially altered by the entrance of fluids from other increments into them, but approach equilibrium for the existing pressure and saturation (i.e., each increment behaves in more or less independent fashion, dependent largely upon the equilibrium considerations mentioned above)

Jan 1, 1948

By Vaughn Moyer

A method for incorporating well drawdown effect into reservoir calculations is presented in detail, together with examples of its use for widely divergent conditions that could be normally encountered in oil reservoir sands. Tentative conclusions as to the effect such factors as permeability, producing interval, well spacing, or well damage caused by completion or repair practice could have upon economic ultimate recovery are reached. It is carefully pointed out that the conclusions reached are subject to limitations indicated in the text, and placed upon all calculations made in the paper. Introduction Papers have been presentedl-3 in which theoretical depletion histories for reservoirs under equilibrium conditions and no appreciable well-bore drawdown pressure are determined. However, except for a limited number of cases, appreciable drawdown Pressures in a well bore exist, and Pressure and saturation gradients consequently vary throughout a reservoir. This Paper is an attempt to incorporate well-pressure drawdown into reservoir history, and to analyze certain factors, such as those involving recovery, well spacing, and productivity index, from the standpoint of permeability and drainage radius. BY incorporation of drawdown into reservoir history, it is believed that theoretical considerations will more closely approxi- mate actual reservoir behavior experienced in an oil field. For purposes of simplification, a solution gas-drive type field1 without primary gas cap, has been selected. Basic Data and Assumptions Details of equilibrium saturation conditions for no drawdown production for various pressures in a reservoir are deter-minable by methods described by several are permitting the construction of a curve of oil saturation vs Pressure for any selected combination of initial interstitial water and hydrocarbon saturation (Fig I). This curve is then a description of equilibrium saturation conditions at any given pressure in a reservoir. Developing the above, details of saturation and flow permeability may thus be determined for any increment or portion of a well drainage area or reservoir. In this manner the effect of pressure differential (drawdown) may be incorporated into reservoir and well drainage considerations. It is pointed out that this method thus makes use of no-drawdown equilibrium production data, superimposing a draw-hwn effect upon them. It also assumes that net flow conditions in any considered increment of reservoir are not materially altered by the entrance of fluids from other increments into them, but approach equilibrium for the existing pressure and saturation (i.e., each increment behaves in more or less independent fashion, dependent largely upon the equilibrium considerations mentioned above)

Jan 1, 1948

By R. F. Evans, J. M. Avery

MUCH has been written of the glamour of magnesium from sea water, the Aladdin-like creation of a huge magnesium plant in the Nevada desert using cheap hydroelectric power from Boulder Dam; the marvels of the Hansgirg process for the electrothermal reduction of magnesium oxide by carbon, and the ferrosilicon process for producing magnesium from dolomite. This is the story of the production of -magnesium by the electrolytic process, using steam-electric power supplied by a public utility, in a plant at Painesville, Ohio, 30 miles east of Cleveland on the shore 'of Lake Erie. The story is not without interest, since it involves several unique developments that provide the answer to a question frequently asked: How is it possible to produce magnesium metal economically at such a location as Painesville, Ohio? Basically, the answer lies in making use of facilities already in existence for the production of soda ash, which makes it possible to manufacture magnesium chloride, the principal raw material, cheaply enough to offset the high cost of electric power. To this is coupled the successful conversion of by-product chlorine into a product required for the war program. The source of magnesium for this operation is the enormous surface deposit of high-grade dolomite in the region south of Toledo, within reasonable freight haul of Painesville. This same geological stratum underlies the Painesville plant, but unfortunately at a depth of about 3000 ft. apparently too great a depth to permit underground mining to compete with the delivered cost of rock from surface quarries in other areas. The cost of dolomite obviously is an important factor, since the rock contains only some 12 per cent magnesium (20 per cent MgO) so that one dollar on the cost of stone means more than $8 in terms of its magnesium content, and more than that in terms of recoverable magnesium metal. PRODUCTION OF MAGNESIA FROM DOLOMITE In the summer of 1941, the Diamond Alkali Co. was well along with construction of a plant intended for the commercial production of refractory and other grades of magnesia from dolomite. The process to be used was designed to make maximum economic advantage of existing plant and operations by tying the production of magnesia in with the manufacture of soda ash in such a way as to make use of the lime (CaO) value of calcined dolomite. The process finally adopted after a lengthy research and development program has much in common with the old Clerc-Nihoul process, but includes certain innovations found to be necessary or

Jan 1, 1945

By William B. Phillips

It is proposed in this paper to discuss some of the chemical and physical principles involved in the manufacture and use of this important by-product obtained in the manufacture of steel by the basic process. The name, " phosphate slag," is adopted as a sort of compromise between "Thomas slag" and "tetrabasic phosphate." By the first of these latter names, viz., " Thomas slag," it is known in Germany, Austria, France, and the other continental countries, and in England, and is more easily apprehended by those who have no special Knowledge of chemistry, while the name " tetrabasic phosphate," being descriptive of the nature of the slag, is perhaps the best. It is but seldom that a discovery of such moment to two great industries is to be chronicled in the history of technical science. On the one hand, the manufacture of iron and steel has been greatly benefited, while on the other hand, the effects already noticed, and still to follow, to the agriculturalist, are of scarcely less conseqnence. The great majority of iron ores in the world, perhaps 90 per cent. of then), are now available for the steel manufacturer, while the manufacturer, and more especially the consumer, of artificial manures is relieved from the fear of the exhaustion of the crude phosphates. We have in phosphate slag, therefore, a product of the highest importance to those who make and we steel and fertilizers. Two great industries, which heretofore have had but little in common, are thus brought into close connection with each other, and the results sure to follow, if one may judge from the history of the past ten years, cannot fail to be of great and increasing value. These results may be compared with those which followed the introduction of the cupriferous Spanish pyrites into England for the manufacture of sulphuric acid. The copper extracted greatly reduced the cost of the acid, hence that of artificial manures. Cheap manures meant better farming and cheaper farm products, and these meant better and cheaper living to nearly all classes of society. The amount of fertilizers now manufactured in the United States

Jan 1, 1889

By Harrison Everett Ashley

(Pittsburg Meeting, March, 1910.) Slimes are usually defined as all material passing a certain-sized sieve, which is invariably the finest sieve employed by each metallurgist in his tests; 100-mesh and 200-mesh have been taken as the limits by different writers in recent volumes of the Transactions ; 150-mesh is common practice. The reader of the first two volumes of Richards 1 is impressed by the inflexibility with which all grinding-arrangements are praised or condemned according as they make little or much slime. Until recently, one of the principal aims of the mill-man was to keep down the slimes. He was obliged to have separate apparatus for sand- and slime-treatment. The latter was sometimes puzzling and erratic. Often it was found most .economical to omit treatment of the slimes entirely, or to store them in immense basins or heaps, waiting for possible future improvements in methods of treatment. Recently, improved processes of agitation and filtration have made possible the successful extraction of values from many slimes. The tendency, when the metal is exceedingly finely disseminated, is to cut out all sand-treatment and to slime everything. These processes have been almost entirely mechanical in their conception, and it is the object of the present paper to show that certain chemical considerations may greatly hinder or assist their successful operation. It has long been a source of dissatisfaction to chemists that their analyses fail to be of much help to the clay-worker; that it is a matter of common occurrence for clays of closely identical ultimate chemical constitution to show the widest possible divergence in physical properties. * Published by permission of the Director of the U. S. Geological Survey. Ore Dressing (1903).

Aug 1, 1910

By R. E. Zimmerman

Wide attention is being placed upon various methods for cleaning the fine sizes of bituminous coals. The author describes and analyzes the results achieved on wet concentrating tables of modern design on unclassified feeds of —Vz in. particle sizes, including tests on high-sulphur coals. THE increased economic necessity of cleaning the small sizes of coal has forced wide attention upon various methods or processes being used. Although numerous cleaning plants in the past have been cleaning coal smaller than Vz or % in., the large quantities of higher ash fines being produced by mechanical mining and the need for cleaner coal under competitive market conditions have brought about many new installations of fine-coal cleaning plants. Of various methods used, one of the more popular types is the wet concentrating table. Approximately 525 tables have been installed in the United States in the past four years of which 320 have been installed in 20, large new plants. There are now probably 1600 tables of all types in existence in this country for cleaning coal. The purpose of this paper is to describe the cleaning of fine coal by wet concentrating tables. Its scope is confined to a discussion of the theory of tabling and some of the factors entering into tabling action, a description of the Deister SuperDuty diagonal-deck coal table and a discussion of the results of tabling various fine sizes of coals. Al- though tables have been used for cleaning coal as coarse as 2 in. and favorable results are reported, this paper is limited to reporting on the results of cleaning coal fines from 1/2 in. down. Also, although it is well known that the performance of tables is even superior under classified or closely sized feed conditions, this paper concerns itself with the results achieved by tabling unclassified feeds. History of Wet Concentrating Tables The wet concentration of minerals by some form of tabling is quite old, starting originally from fixed, smooth surfaced, tilted boards taking advantage of the laminar flow of liquid films and the separation of minerals according to specific gravity. This was followed by the development of rough deck surfaces

Jan 1, 1951

By R. E. Zimmerman

Wide attention is being placed upon various methods for cleaning the fine sizes of bituminous coals. The author describes and analyzes the results achieved on wet concentrating tables of modern design on unclassified feeds of —Vz in. particle sizes, including tests on high-sulphur coals. THE increased economic necessity of cleaning the small sizes of coal has forced wide attention upon various methods or processes being used. Although numerous cleaning plants in the past have been cleaning coal smaller than Vz or % in., the large quantities of higher ash fines being produced by mechanical mining and the need for cleaner coal under competitive market conditions have brought about many new installations of fine-coal cleaning plants. Of various methods used, one of the more popular types is the wet concentrating table. Approximately 525 tables have been installed in the United States in the past four years of which 320 have been installed in 20, large new plants. There are now probably 1600 tables of all types in existence in this country for cleaning coal. The purpose of this paper is to describe the cleaning of fine coal by wet concentrating tables. Its scope is confined to a discussion of the theory of tabling and some of the factors entering into tabling action, a description of the Deister SuperDuty diagonal-deck coal table and a discussion of the results of tabling various fine sizes of coals. Al- though tables have been used for cleaning coal as coarse as 2 in. and favorable results are reported, this paper is limited to reporting on the results of cleaning coal fines from 1/2 in. down. Also, although it is well known that the performance of tables is even superior under classified or closely sized feed conditions, this paper concerns itself with the results achieved by tabling unclassified feeds. History of Wet Concentrating Tables The wet concentration of minerals by some form of tabling is quite old, starting originally from fixed, smooth surfaced, tilted boards taking advantage of the laminar flow of liquid films and the separation of minerals according to specific gravity. This was followed by the development of rough deck surfaces

Jan 1, 1951

By B. L. Landrum, P. B. Crawford

Theoretical and potentiometric model studies have been made of the effect of non-uniform lateral permeabilities on pattern sweep efficiency and production capacity in waterflood and gas-cycling programs. It is shown that a diflerence in directional permeability by a factor of three may result in a sweep efficiency of only 43 per cent for a five-spot pattern or a sweep of either 79 or 38 per cent for a direct line-drive square pattern, depending on the direction of the line-drive flood. Changes in the pattern conductivity varied from about 0.8 to 1.34 over this same permeability variation, depending on the pattern used. It is suggested that measurements be made to determine the possible magnitude and extent of the directional permeability phenomenon early in the field developinent and certainly prior to the initiation of any fluid-injection progmm. INTRODUCTION Irregularities in reservoir sand properties long have been a major difficulty to anyone attempting to explicitly describe the field characteristics of oil production. In particular, it is well known that vertical and lateral permeabilities often differ appreciably; however, the existence of large regions with lateral permeabflity variation is not widely recognized. A number of years ago, extensive studies were conducted by the Secondary Recovery Research Labcratory of the Pennsylvania Grade Crude Oil Association, primarily on the Bradford field. Johnson and Hughes' reported a permeability trend in the northeast-southwest direction. They indicated that flow in the preferred direction may be 25 to 30 per cent greater in that direction than in the northwest-southeast direction. They also reported that similar effects may be found in other nearby fields. The origin of the permeability variation has been discussed by Griffith Hutchinson' described the results of labora- tory tests on limestone cores, pointing out that per-ferential directional permeabilities were significant in one-half of 10 formations studied and that the average permeability ratio was 16:1. Barfield, Jordan and Moore analyzed the fluid-injection displacement performance in the Spraberry and reported that the effective ratio of permeability parallel to the major axis to the permeability perpendicular to this axis was 144:l and that it inclined along an angle of about 30". To prevent the reduction of sweep efficiency which would normally result from flooding or cycling in such reservoirs, well spacing could be varied from the customary square to a diamond-shaped pattern. Johnson and Hughes' presented a method for determining the desired shape. Another method will be discussed in detail in the next section. It is the purpose of this paper to investigate quantitatively the effect of directional permeability upon the sweep efficiency and production capacity of the five-spot and line-drive well patterns. Information currently in the literature will be applied to this particular problem and augmented by a potentiometric model study. It is stressed that the effects herein discussed may or may not be of great importance because field data on this phenomenon are far too scant to form such an opinion. It is suggested that, if conditions similar to those found by Johnson and Hughes frequently exist (as may well be the case), more consideration cdrtainly should be given to this problem.

By Pei-Yung Huang, C. R. Hayward

In order to understand more fully the actual state of copper lost in copper reverberatory slags, a systematic study on the various reactions between certain metallurgically important copper compounds and synthetic copper reverberatory slags was undertaken by the authors in the Massachusetts Institute of Technology from 1942 to 1945.1 This paper, being only a part of the work completed, is published first because it furnishes the first experimental evidence of the formation of copper ferrite from reactions between cuprous oxide and copper reverberatory slags. Choice of Slag Composition The choice of the composition of the synthetic reverberatory slags to be used was much deliberated. Commercial copper reverberatory slags, neglecting minor constituents, avcrage :2,3 45 to 47 pct FeO; 38 to 42 pct SiO2; 5 to 6 pct CaO; 5 to 6 pct A12O3. Since the ternary system CaO-FeO-SiO2 has been much more thoroughly studied4 and is much simpler than the quaternary system CaO-FeO-SiO2-Al2O3, it was decided to use calcium oxide only instead of calcium oxide and alumina in the synthesis of the slags. Fortunately the composition of the average copper reverberatory slag with calcium oxide substituted for alumina lies in the region of the phase diagram clarified by the investigators. A survey of the phase diagram (Fig I) suggested two compositions: (I) the composition near the invariant point S, which is made up of 46 pct ferrous oxide, 37 pct silica and 17 pct calcium oxide; (2) the composition near the invariant point K with 45.5 pct ferrous oxide, 43 pct silica and 11.5 pct calcium oxide. Composition S has the advantage that the percentages of ferrous oxide and of silica almost exactly coincide with those of the average reverberatory slags, and that of the lowest melting point (1093º ± 3ºC) in the whole ternary system. The calcium oxide content, however, obviously is high. Since we have already substituted calcium oxide for alumina, and since calcium oxide is more basic than alumina, the fulfil- slag is decidedly too basic. Composition K has a slightly higher melting point (1150O + 3OC) and a higher silica content, but this is preferred because the slag is saturated with respect to tri-dymite and thus should not corrode siliceous refractories. Besides, it is less basic than composition S. The filial slag composition, therefore, was chosen to

Jan 1, 1949

By Blamey Stevens

In this paper, which is a logical extension of my paper, The Laws of Intrusion,1 the various pressures of emanation and their mechanical causes and effects on the large scale of nature are determined, and a classification of emanations is deduced therefrom. • The Subterranean. Sea. The subterranean sea is here defined as the intercommnnicating water contained in the trains of pores and fissures of the rocks down to great depths. Whether the actual amount of water constituting this subterranean sea be large or small, does not enter into the present argument, since the static pressure of this water at any particular depth is not a function of the quantity : it involves only the depth and the density of the water. Densities. The total pressure at depths down to 10 or 15 miles is made up of the rock-stresses investigated in my previous papers, and the pressure of the subterranean sea. The latter component must evidently be equal to the weight of a solid column of the overlying water of unit sectional area. As mater expands with heat, it should really be necessary to sum the density at every level. A knowledge of the densities of mater under a variety of conditions is therefore needed, but does not seem ever to have been ascertained for such combined pressures and temperatures as we have to consider. The specific gravity of water at 28' C. for various pressures up to 400 atmospheres, has been determined by Barus, 2 who

Jan 1, 1913

By Harry W. Brown

This paper presents results of static capillary pressure measprements made both by the restored-state and by the mercury-injection methods, and of dynamic capillary pressure measurements made by the Hassler technique. The results indicate a variation from sample to sample of the factor used to convert capillary pressure obtained by mercury injection to those applicable to a water-gas system. Static capillary pressures measured by the restored-state method were found to be in close agreement with dynamic capillary pressures, indicating that data obtained from static measurements may be utilized with confidenre in the solution of dynamic problems of fluid flow. Experimental data are presented on the use of "J-curves" for the correlation of capillary pressure-saturation relations for a number of cores from a particular geologic formation. It is shown that the correlation was improved in some cases by reqtricting it to rertain lithologic classifications. INTRODUCTION The Meaning and Importance of Capillary Pressure The coexistence of two or more immiscible fluids within the voids of a porous medium, such as reservoir rock, gives rise to capillary forces. Because of the interfacial tension existing at the boundary between two immiscible fluids in a pore space, the interface is curved, and there is a pressure difference across the interface. This pressure difference is termed the capillary pressure. The magnitude of the capillary pressure between two immiscible fluids which together fill a porous medium depends upon several factors: the textural properties of the medium, the wettability of the medium, the interfacial tension between the fluids, the respective saturations of the fluids, and the manner in which these saturations are attained. For a given pair of immiscible fluids in a particular sample of reservoir rock, the capillary pressure is a unique function of the fluid saturation, provided that the saturation of the fluid which wets the rock has previously been decreased unidirectionally from an initially complete saturation. Similarly, for a given pair of fluids at a particular saturation which has been achieved by a

Jan 1, 1951