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By Walter Miller

During the second year of America's active ia in the war the inain objectives of the petroleum-refining industry were again to provide the four most important product needs for war: 100-octane aviation gasoline, toluene for T.N.T. production, high-quality lubricating oils for the needs of aviation and the armed forces, and petroleum chemicals for synthetic rubber manufacture. All other materials supplied by the petroleum industry took an inferior priority ranking, depending on the degree of essentiality. To accomplish the above objectives the industry initiated and carried on a building program during 1942 and 1943 which will put those two years down in petroleum-refining history as the greatest construction years of all time, a record which will hold for decades to come. Led by an estimated total of $ 900,000,000 going into 100-octane and contributory plant investment, it is easy to picture a total of two billion dollars and more going into additional refining-industry plant investment during 1942 and 1943, most of it privately paid for, but a substantial part covered by R.F.C. Government money financing. Some of the new plants will not be completed until 1944, but a large proportion of the program was finished and put into operation, adding substantially to the output of the four principal products during 1943- lne most important and spectacuiar activity of the refining industry is of course the 100-octane gasoline program necessitated by the fact that nearly 90 per cent of the requirements of the United Nations is being furnished by the United States. Recent P.A.W. figures mention $goo,-ooo,ooo as the cost of the construction looking to increasing the output of this all-important munition. Thirty-four major plants have been completed, 11 of them during the last quarter of the year. Thirty-eight more will be completed and put into operation during the first four or five months of 1944. Twenty-two additional plants authorized during 1943 are already well under way and scheduled for production late in 1944. Early in 1942 the aim was to treble the capacity for making 100-octane gasoline then existing; later, plans were to make it five times as great, to match the increased warplane building program; and toward the end of the year the sights had been set at a still higher but unannounced target, representing six to seven times the early 1942 figure. Comparative figures issued at the end of 1943 enable one to guess a program by the middle of 1944 of eight to nine times the former production, with an ultimate production in 1944 of eleven or more times the early 1942 output. It became obvious in 1943 that building of new units would be materially slowed because of delay in getting construction materials and that they would reach operation at considerably later dates than

Jan 1, 1944

By Walter Miller

During the second year of America's active ia in the war the inain objectives of the petroleum-refining industry were again to provide the four most important product needs for war: 100-octane aviation gasoline, toluene for T.N.T. production, high-quality lubricating oils for the needs of aviation and the armed forces, and petroleum chemicals for synthetic rubber manufacture. All other materials supplied by the petroleum industry took an inferior priority ranking, depending on the degree of essentiality. To accomplish the above objectives the industry initiated and carried on a building program during 1942 and 1943 which will put those two years down in petroleum-refining history as the greatest construction years of all time, a record which will hold for decades to come. Led by an estimated total of $ 900,000,000 going into 100-octane and contributory plant investment, it is easy to picture a total of two billion dollars and more going into additional refining-industry plant investment during 1942 and 1943, most of it privately paid for, but a substantial part covered by R.F.C. Government money financing. Some of the new plants will not be completed until 1944, but a large proportion of the program was finished and put into operation, adding substantially to the output of the four principal products during 1943- lne most important and spectacuiar activity of the refining industry is of course the 100-octane gasoline program necessitated by the fact that nearly 90 per cent of the requirements of the United Nations is being furnished by the United States. Recent P.A.W. figures mention $goo,-ooo,ooo as the cost of the construction looking to increasing the output of this all-important munition. Thirty-four major plants have been completed, 11 of them during the last quarter of the year. Thirty-eight more will be completed and put into operation during the first four or five months of 1944. Twenty-two additional plants authorized during 1943 are already well under way and scheduled for production late in 1944. Early in 1942 the aim was to treble the capacity for making 100-octane gasoline then existing; later, plans were to make it five times as great, to match the increased warplane building program; and toward the end of the year the sights had been set at a still higher but unannounced target, representing six to seven times the early 1942 figure. Comparative figures issued at the end of 1943 enable one to guess a program by the middle of 1944 of eight to nine times the former production, with an ultimate production in 1944 of eleven or more times the early 1942 output. It became obvious in 1943 that building of new units would be materially slowed because of delay in getting construction materials and that they would reach operation at considerably later dates than

Jan 1, 1944

By R. C. Craze

During the past 20 years. research and development in the study of reservoir behavior have dealt principally with flow of oil through sandstones. Many reservoir studies of sand fields have proved valuable in promoting recovery efficiency. This paper discusses fundamental principles governing oil and gas production from sandstone and limestone alike and presents the results of investigations relating to the application of analytical techniques used for sandstone reservoir studies to the study of limestone reservoir performance. The characteristics of limestone porous systems, porosity-permeability relationships, distribution and occurrence of oil, and characteristics of flow through such systems are discussed. Recognition is made of the similarities or differences which these factors exhibit in limestone and sandstone systems. Comparisons between operating data for typical limestone and sand reservoirs are presented. It is indicated that the distribution and movement of fluids in and through porous limestones follow the same fundamental principles underlying such processes in sandstones. This fundamental similarity may readily be discernible in the performance of many limestone reservoirs. The volumetric balance and unsteady state radial flow equation, the fluid displacement equation, use of electrical analogue devices, and other analytical techniques to study the behavior of limestone fields appear fundamentally applicable, but do require thorough understanding of the properties of the formation, of the fluids, their behavior during flow, and adequate production operating data. Need for more complete coring and comprehensive examination of core properties is stressed. The results of "active oil" studies, and of flow and interference tests are presented. Well spacing, well completion, and efficient rates of production in limestone reservoirs are briefly discussed. INTRODUCTION Limestone and dolomite reservoirs constitute the largest source of supply of crude oil in the world. an estimated 60 per cent of present production coming from carbonate reservoirs. In many large geologic provinces such as Mexico. the Middle East, and more recently Canada, almost all the oil is found in this type of rock. In the United States, all of the major oil-producing areas except California and Pennsylvania contain oil-bearing carbonate formations. The discovery in recent years of large oil reserves in the Silurian, Devonian, and Ordo-vician formations in West Texas, in addition to the large reserves in the Permian, has accentuated the interest of operators, geologists, and engineers in limestone formations and in the many problems associated with understanding the performance of these reservoirs. The rapid increase in discovery of oil in limestone formations and the present-day position of prominence held by these fields in the production and reserve picture in all parts of the world emphasize the horizons opened to the reservoir technologist in the field of geological and production research. Pertinent to an interpretation of the behavior of limestone reservoirs are the methods of analysis which may be utilized and a possession of full knowledge of the many factors which influence the analytical procedures. During the past 20 years a well-developed science of reservoir engineering has been built upon the research of many workers who studied the fundamental nature of oil reservoirs, characteristics of the porous media, properties and behavior of the contained fluids, and the mechanics of flow. Application of these studies to production practice has resulted in greater recoveries and more efficient field operation. The major portion of this evolutionary process has been founded upon studies of sand fields. The applicability of these more thoroughly developed techniques for studying sand fields to the study of the behavior of limestone fields becomes a factor of technical and practical significance. In the light of the technological background available to the reservoir analyst, this paper discusses fundamental principles governing oil and gas production from sandstone and limestone alike and presents the results of investigations relating to the application of analytical techniques used for sandstone studies to the study of limestone reservoir performance. LIMESTONE RESERVOIR CHARACTERISTICS The characteristics of limestone and sandstone reservoirs are similar in many respects and they both may occur under similar structural conditions. Fundamentally, the distribution and movement of fluids in and through the porous limestone media follow the same basic principles which dictate such processes in sandstones. Herein lies a fundamental similarity, which may readily be discernible in the performance of many limestone reservoirs. In some limestone fields, as in many sand fields, widely varying formation properties and distribution may reveal themselves in deviations in the performance of the reservoir, in the behavior of wells, and in fluid flow through the rock, and make difficult the delineation of reservoir behavior. Only by reservoir studies, core analyses, and coordinated laboratory and field experimentation can the effects of the many influencing factors upon the nature of limestone production be determined. FORMATION CHARACTERISTICS The chief difference between limestone and sandstone, aside from their chemical compositions, is the difference in the geometry and origin of the porous systems in the two kinds of rock. In sandstone the porous system results entirely from the openings among individual sand grains which occur during deposition. The geometry of the openings between the sand

Jan 1, 1950

By R. D. MacDonald, John Dasher, A. M. Gaudin

ION exchange is a widely used unit operation in water treatment and elsewhere in chemical industries. It has occasionally been used in hydro-metallurgy for treating plating, pickling, and rayon wastes Concerning ion exchange in extractive hydrometallurgy—for treating ore leach solutions— the literature prior to the Geneva Conference has given only hints."-" Yet most of the ore leach plants now being built or completed in the last three years use ion exchange for this purpose. Most of these plants are used for extracting uranium. The overall process for leaching low grade uranium ores and the history of its development have been given in the authors' previous papers.',' The object of this paper is to discuss certain engineering aspects of the new application of ion exchange to recover dissolved values from ore leach solutions. Necessarily the illustrations will be taken from the first application—to uranium metallurgy. Although ion exchange processes have been devised in which separation of spent residue from pregnant liquor is not required, as in the RIP process,"-'I only ion exchange operation, in which the resin is contacted with a clear solution, will be discussed in this paper. Uranium exists in acid leach liquors mainly as the cation UO," and can be adsorbed completely by cation exchange resins, but the adsorption is not selective as other cations such as Fe++, Fe+++, Al+++, Mg++, Mn", and Ca++ are also adsorbed. Uranium, however, forms complex anions with sulfate, phosphate," Carbonate"~"~ and even with chloride if the solution is strong enough.15 These anions can be adsorbed by anion exchange resins. The strong base anion exchangers have a very strong preference for these complexes and hence this adsorption is very selective. In this paper, the examples concern acid sulfate leach liquors from which uranium is adsorbed as UO,(SO,),-% and UO,(SO,),". Materials and Equipment Ion Exchange Material—Ion exchange materials include natural and synthetic; organic and inorganic; cationic and anionic; and weak, intermediate, and strong varieties. They consist of fragments or beads normally in the size range —16 to $50 mesh. The newer varieties have been developed to have greater stability, chemical strength, and/or capacity than earlier varieties. The resin used for uranium recovery is a strong base anion exchanger.* To make * Such as Rohm and Haas Amberlite IRA-400 series, British Permutit DeAcidite FF. Permutit lonac SE. and Dow Nalcite SAR. this resin, styrene plus a few percent divinyl benzene are polymerized into long chains with occasional cross links. This resin in bead form is then reacted to introduce quaternary amine groups onto most of the aromatic rings.' These resins are water-avid gels of specific gravity of about 1.1, which shrink and swell by osmosis when the ionic content of the surrounding solution is changed. The beads which are shown in Fig. 1 can be broken like an onion by rapidly replacing 15 pct H,SO, with water. This organic gel can also be broken by mechanical handling as by a centrifugal pump. Otherwise it is remarkably stable. It is unharmed by fairly strong acid or alkali, oxidizing or reducing agents, and heat up to 70°C. The strong base resin when completely in the chloride form (with a chloride anion on each quaternary amine group) holds over 107 g of C1- per dry kg. As all these chloride ions can be displaced by other anions, the resin has an exchange capacity of over 3 g equivalents per dry kg. However, the resin is sold and used by moist volume. The moist resin contains about 50 pct water, weighs about 43 lb per cu ft, has 40 pct voids, and an exchange capacity of over 1 g equivalent per liter of bed volume. Ion Exchange Equipment—Ion exchange equipment used for recovery of uranium from leach solutions is substantially identical to that developed for water treatment and other applications.'" The resin beds are held in closed tanks or columns which, in the uranium plants, have been standardized at 7 ft diam and 12 ft high. The resin bed

Jan 1, 1958

By Clarence Zener

The heat-treatment of steels will not pass from the stage of an art into that of a science until the mechanism of the phase transformations associated therewith is thoroughly understood. Such an understanding will involve two distinct types of inquiry: (I) the direction of the transformation, (2) the speed of the transformation. The first type of inquiry, which involves only the equilibrium relations between the various phases in steel, is the subject of the present and of a succeeding article; the second type, which involves the kinetics of transformations, will be the subject of a later article. In order that a theory of equilibrium relations may give useful information, certain experimental data must be put into the theory. It is customary for these data to be of a thermal nature. In the system discussed herein—steel—such thermal data are very scarce. In medium-alloy steels another type of data might possibly be used. In these steels the concentration of solute is so low that it may be possible to use the approximation of dilute solutions, an approximation that leads to linear relationships. The unknown functions, or constants, may then be determined in some cases from the binary iron-alloy system and in other cases from the ternary iron-carbon-alloy system. From the functions, or constants, so determined may then be computed the equilibrium relations in more complex medium-alloy steels. In the present article this second approach is used, the necessary experimental data 'being obtained from the simple binary and ternary equilibrium diagrams. Fundamental Equations In this article are derived the equilibrium relations between the gamma, alpha and cementite phases. In these three phases all important alloying elements except carbon form substitutional solutions, each alloying atom occupying a potential site for an iron atom. Carbon, on the other hand, forms an interstitial solution. In the face-centered cubic gamma phase, the interstitial positions are at the center of the unit cube and at the centers of the cube edges. There are therefore four interstitial positions per unit cell, or one per iron atom. In the body-centered cubic alpha phase, the interstitial positions are probably at the face centers, and also at the centers of the edges, which are crystallographically equivalent to the face centers. There are therefore six interstitial positions per unit cube, or three per iron atom. In cementite, (Fe, Alloy)3C, the carbon atoms may. be regarded as filling all the lattice positions of a given type. The introduction of the fundamental the of equilibrium has presented the author with a quandary. These equations are formally so similar to other equations that have been derived1,2 for related systems that they may appear to some readers

Jan 1, 1947

By Clarence Zener

The heat-treatment of steels will not pass from the stage of an art into that of a science until the mechanism of the phase transformations associated therewith is thoroughly understood. Such an understanding will involve two distinct types of inquiry: (I) the direction of the transformation, (2) the speed of the transformation. The first type of inquiry, which involves only the equilibrium relations between the various phases in steel, is the subject of the present and of a succeeding article; the second type, which involves the kinetics of transformations, will be the subject of a later article. In order that a theory of equilibrium relations may give useful information, certain experimental data must be put into the theory. It is customary for these data to be of a thermal nature. In the system discussed herein—steel—such thermal data are very scarce. In medium-alloy steels another type of data might possibly be used. In these steels the concentration of solute is so low that it may be possible to use the approximation of dilute solutions, an approximation that leads to linear relationships. The unknown functions, or constants, may then be determined in some cases from the binary iron-alloy system and in other cases from the ternary iron-carbon-alloy system. From the functions, or constants, so determined may then be computed the equilibrium relations in more complex medium-alloy steels. In the present article this second approach is used, the necessary experimental data 'being obtained from the simple binary and ternary equilibrium diagrams. Fundamental Equations In this article are derived the equilibrium relations between the gamma, alpha and cementite phases. In these three phases all important alloying elements except carbon form substitutional solutions, each alloying atom occupying a potential site for an iron atom. Carbon, on the other hand, forms an interstitial solution. In the face-centered cubic gamma phase, the interstitial positions are at the center of the unit cube and at the centers of the cube edges. There are therefore four interstitial positions per unit cell, or one per iron atom. In the body-centered cubic alpha phase, the interstitial positions are probably at the face centers, and also at the centers of the edges, which are crystallographically equivalent to the face centers. There are therefore six interstitial positions per unit cube, or three per iron atom. In cementite, (Fe, Alloy)3C, the carbon atoms may. be regarded as filling all the lattice positions of a given type. The introduction of the fundamental the of equilibrium has presented the author with a quandary. These equations are formally so similar to other equations that have been derived1,2 for related systems that they may appear to some readers

Jan 1, 1947

By T. E. Leontis, D. H. Feisel

MAGNESIUM alloys containing rare earth metals have received considerable attention during the past several years because of the need for light alloys having high strength and creep resistance at elevated temperatures. Although much of the work reported earlier has dealt with alloys containing Mischmetal, it has been shown in two previous papersl, V hat distinctly different effects are produced by various rare earth metals and rare earth metal mixtures on the properties of magnesium. For example, much higher strengths are obtained in magnesium alloys containing didym-ium (essentially neodymium plus praseodymium) than in alloys made with Mischmetal, which contains all the rare earth metals in the proportions in which they occur naturally in the monazite ore. Mg-rare earth metal alloys are characterized by a relatively coarse grain size, which greatly impairs castability. The addition of zirconium as a second alloying ingredient has been shown8,7 to refine the grain size, which also produces a distinct improvement in the strength properties. Certain Mg-Mischmetal-Zr and Mg-Mischmetal-Zn-Zr alloy compositions which are currently being produced commercially have been discussed in dytail by Nelson and Strieter,8,4 who also present some in- formation on a Mg-low Ce-Mischmetal-Zr alloy, and by Nelson.8 A patent issued to Jessup, Emley, and Fisher9 emphasizes the superiority of Mg-didymium-Zn-Zr alloys over the corresponding alloys made with Mischmetal. The purpose of this paper is to present the results of an extensive investigation concerned with the effect of increasing amounts of zirconium on magnesium sand casting alloys containing several different rare earth metal mixtures in varying amounts. The effect of the addition of zinc to some of these alloys is also being reported. Preparation and Testing of Alloys The alloys studied in this investigation were prepared in small laboratory melts according to the melting procedures described by Nelson1" as the Crucible Method. Electrolytic magnesium having the composition shown in Table I was used as the starting material. The rare earth metal alloying ingredients used in preparing these alloys were essentially of the compositions listed in Table 11. Some of the didymium-containing alloys were prepared using a Mg-didymium hardener. The rare earth metal content of this hardener analyzed 1.2 pct Ce, 10.4 pct Pr, 80.8 pct Nd, and 7.6 pct La. The zirconium was added in one of three forms: 1) as sponge zirconium obtained from the Bureau of Mines; 2) as a fused salt consisting of 50 pct ZrCl, and 50 pct alkali chlorides from which the zirconium is reduced by the magnesium; or 3) as a Mg-Zr hardener. The alloying procedures and melt hand-

Jan 1, 1958

By R. O. Leach, O. W. Wagner

Because of unfavorable wetting conditions much residual oil is left when a porous material is Pushed by water. Methods suggested to change reservoir wetting to improve oil displncernrnt efficiency are generally expensitlr. The present 1aborator.y study was undertaken to gain an under.standinx of the factors which determine reservoir wettability, arid to find out if oil displacement efficiency might be improved by a wettahility change accomplished at low cost in on oil reservoir. Contact angle measurements were made on mineral surfaces using sevc.r~zl sets of reservoir oil and water samp1es. Results of the contact angle studies suggest that reservoir wetta-hility may he primarily determined by natural surface-active substances present in the reservoir fluids. The effect of changing sa1inity and pH of the water phase was studied. The re.suits suggest that gross changes in preferential wettability might be acc~o~npli.shed by injection of water containing simple chernicnls to alter pH or salinity in the reservoir. Such treatment could he much less expensive than injection of commercial surface-active agents. Waterflood tests have also been made using synthetic cores and oil and water having wening characteristics similar to those of reservoir fluids. Cores initially oil-wet were flooded in such a way that they were made prefermtial1y water-wct by the advancing flood water. This reversal in preferential wettability achieved greater oil displacement efficiency than when either oil-wet or water-wet conditions were maintained throughout the flood. For the systems studied, the higher the oil viscosity the greater the percentage improvement obtained over conventional waterflood recovery. This suggests that a flooding process making use of wettability-reversal may extend the oil viscosity range over which water flooding is attractive. Because a precise adjustment of reservoir wettability does not seem to be required, and because altering the pH or salinity in some reservoirs may be inexpensive, it appears that a waterflooding process employing wet-[ability-reversal could find .succesful field application. I NTRODUCTION The efficiency with which water will displace oil from a porous material is related to the nature of the capillary forces present. These in turn are controlled by the preferential wetting of the solid by the two fluids. Because of unfavorable wetting conditions, 30 per cent or more of the original oil in place may remain unrecovered in that portion of a reservoir flushed by water. This paper is concerned with the possibility of improving waterflood oil displacement efficiency by alterations in the wettability of the porous material. A laboratory study was made to gain a better understanding of the factors which control reservoir wettability, and to determine if the oil displacement efficiency could be improved by some inexpensive means of manipulating wettability of the porous medium. Contact angle measurements were made with several natural and synthetic oil, water and solid systems (1) to obtain a better understanding of how to duplicate reservoir wettability in the laboratory, and (2) to discover possible means for changing preferential wettability of natural reservoir systems. Flooding tests were also made in synthetic systems to determine if oil displacement efficiency could be improved by those wettability manipulations suggested by the contact angle measurements. Based on these studies a possible method for improving waterflood oil displacement efficiency is presented. This method involves causing an originally oil-wet porous material to become preferentially water-wet during the course of a water flood. The purpose of this paper is to present results of the laboratory studies. THEORY Rock surfaces in some oil reservoirs are believed to be covered with a firmly attached bituminous or other organic coating. Such surfaces would be preferentially oil-wet in the presence of both oil and water, regardless of composition of reservoir fluids. Other reservoirs are believed to contain rock surfaces not permanently coated with such materials, and which would be preferentially wet by water in the presence of water and oil free from surface-active substances. However, when the reservoir fluids do contain certain natural surface-active materials in sufficient quantity, rock surfaces acquire a degree of preferential oil wettability caused by adsorption of these natural surface-active materials on the solid. The equilibrium amount of these materials adsorbed per unit surface area is believed to depend upon their concentration in the bulk liquid phases.

INTRODUCTION The preceding chapters have brought us to a point in the mineral appraisal process where the composited sample values can now be used to estimate the grade and tonnage of the total mineral deposit. There are many techniques whereby drill hole composites and/or other sample data are used to assign grade and estimates to the surrounding rock. Matheron and his students have properly called such techniques extension functions. Before embarking upon a detailed discussion of extension functions, it is necessary that we take time to consider the concept of geostatistics as advocated by George Matheron who developed the "Theory of Regionalized Variables," which he published in 1962 (Matheron, 1971). The concept of regionalized variables has important application in the techniques of mineral appraisal. The position or location of a mineral sample within a deposit can be almost as important as its value. Geostatistics, when defined as "the application of the theory of regionalized variables* to the study of mineralized volumes of rock," takes into consideration the position as well as the magnitude of the value of the sample. The principles of geostatistics, as outlined by Matheron, represent a major step forward in the mineral evaluation process, because they provide a sound theoretical and practical basis for quantifying the geological concepts of (1) area of influence of a sample, (2) the continuity or lack of continuity of mineralization within the ore body, and (3) the lateral changes in mineralization according to the trend direction of an ore body and its orthogonal components; or in other words, a measure of the anisotropy of the deposit. Royle (1971) has defined the objects of geostatistic as being: "1. To estimate the most likely value of blocks of ore, or the values of the whole deposit; and 2. to estimate the errors of such estimates. This latter is important as, in addition to providing a check on unwarranted optimism, it shows where more valuation work may be needed." Because of the great importance of these concepts in mineral evaluation, an introduction into the theory of regionalized variables, and the study of a practical approach to its application is outlined here. REGIONALIZED VARIABLES VS. RANDOM VARIABLES Classical statistics, as discussed in earlier chapters, grew out of the study and application of probability theory. Probability is concerned with the outcome of random events and therefore classical statistics is built upon the theory of random variables, i.e., the probability of independent events. The validity of most statistical inferences depends upon sample randomness being assured for unbiased results. Where independent events cannot be assumed the results of statistical inference becomes suspect. On the other hand, geostatistics is concerned with variables that have position in space as well as magnitude, hence the term regionalized variables. Mineral deposits are not the only field to which the theory of regionalized variables is applicable. Many natural phenomena that demonstrate a relationship between change in magnitude and position in space are amenable to application of geostatistical techniques. Mineral deposits vary greatly in their geosta-

Jan 1, 1980

By E. Stamboliadis

Dithiophosphates are reaction products of phosphorous pentasulfide with various organic compounds such as phenols, alcohols, mercaptans, dioalcohols, amines, and nitrides. The products with alcohols are commercially known as "aerofloats" and these are investigated in this presentation. It appears that the formation of insoluble metal dithio phosphates is responsible for their collecting properties with minerals." In this aspect they are very similar to xanthates.3 The solubility of metal dithiophosphates depends on the number of carbon atoms in the organic chain of the corresponding alcohol. An empirical mathematical model is presented here. It allows one to predict the number of carbon atoms necessary to ensure that a certain metal dithiophosphate will form at a selected pH value of the water solution. The Nature of Dithiophosphates Dithiophosphoric acid is the product of the reaction of phosphorus pentasulfide with an alcohol, as shown in the following equation: [P2S3 + 4 ROH - 2 (RO)2 PS2H + H2S (1)] where R stands for a hydrocarbon chain. The acid so produced can be neutralized by a base to produce the corresponding salt as shown in the following: [(RO), PS2H + NH- (RO)2 PS, NH,. (2)] In this aspect dithiophosphates are similar to xanthates, the only difference being the substitution of the tetravalent carbon atom in the xanthate polar group by a pentavalent phosphorus atom in the dithiophosphate group. This difference implies at least two characteristics: (1) that there are two hydrocarbon chains associated with the polar group so that an increase in the number of carbons of the single chain is expected to have a pronounced effect on the flotation properties, and (2) that the bond between the sulfur and the central atom is stronger than in the xanthate group. This probably leads to a decrease in both the polarizability of the electronic cloud of the sulfur and the interaction with cations.3 However, what is lost in the dithiophosphates by having a weak polar group can be gained by an increase in the number of carbons as will be seen later. Taking into account the size of the atoms involved in a dithiophosphate molecule, as listed in Table 1, It is possible to draw an approximate diagram of its structure as shown in [Fig. 1]. It is assumed here that the length of the single hydrocarbon chain is equal to that of the corresponding alcohol. Preparation and Purification Acid dithiophosphates can be prepared, as previously mentioned, in accordance with Eq. 1. The rate of this reaction is too slow at room temperature and can be improved by increasing the temperature to about 60° or 80°C7 or by evacuating the system. In our investigation evacuation was performed by a water aspiration pump. The dithiophosphoric acid so produced is liquid and dissolves in the alcohol. At the end of the reaction the product is filtered from the remaining P2S3; and dissolved in petroleum ether. By blowing anhydrous ammonia gas into the ether phase the ammonium salt forms as a white precipitate and can be sepa-

Jan 1, 1977

I. THE ENERGY CRISIS STILL EXISTS A. ALTHOUGH IMMEDIATE SHORTAGE IS NOW ALLEVIATED BY: 1. Increased imports through lifting of Arabian embargo; a. Imports were 6.5 million bpd during the week ended January 17, or 1.3 million bpd higher than last year. b. 1.7 million bpd higher than March '74. 2. Decreased demand resulting from higher prices and conservation. a. January 1975 demand was 17.9 million bpd, 0.1 million bpd lower than January 1973 and … b. 2.0 million bpd, or 10% under originally projected demands for January 1975. c. Gasoline (excluding tax) went up 59% from 27d/gal in August 1973 to 43c/gal in September 1974. d. Gasoline demand for January 1975 was 6.3 million bpd, 0.1 million bpd higher than 1973 but 0.7 million bpd ( 10% ) under projected demand. 3. Increased crude and major product inventories. a. January 17, 1975 crude and major product inventory was 794 million bbl, 99 million bbl higher than the same date in 1973. b. 105 million bbl increase since April 12, compared to only 38 million bbl increase during the same period in 1973.

Jan 5, 1975

By H. A. Hoffman

Competition from an all-flotation plant, with demonstrated economies and efficiencies, plus a change in smelting contract and introduction of improved cyclones lead to conversion from gravity-flotation. Detailed descriptions are given of equipment installed and procedures used at St. Joseph Lead's Federal mill. Future plans include further quality control by instrumentation in all aspects of the mill operation. Also planned are improvements in materials handling systems. Competitive conditions will continue to dictate improvements and changes in the mill flowsheet. The advent of all-flotation mills in the Lead Belt was introduced by the Indian Creek mill in late 1953. This modern and efficient plant then became a pattern for the other mills in this area to re-evaluate their circuits in an effort to develop flowsheets that would improve operating conditions and metallurgy. The Indian Creek mill demonstrated that all-flotation would require considerably less operating and maintenance labor than the combination of tabling and flotation that was common in the Lead Belt at that time. Two significant changes occurred in recent years to allow all-flotation to be seriously considered in other Lead Belt mills. One was a change in the smelting contract which did not require gravity concentrate. Another was the development of cyclones which provided classification of the flotation feed in a very small space. Since the Federal mill was the largest concentrating plant in the Lead Belt it was felt that the greatest savings could be made by investigating the all-flotation possibilities at this mill. Interest was stimulated by the milling and ore dressing Depts. to determine if this mill would be converted without undue cost, provided the metallurgy could be improved. Accordingly, laboratory tests were initiated to learn what metallurgical benefit could be derived. Numerous tests were run which indicated that grinding to all-flotation would improve the tailing by as much as 0.02 pct Pb. This was quite significant when multiplied by the tonnage of ore treated. Projecting the added cost of power for extra grinding and flotation, and the additional flotation reagents required, plus additional new equipment that would have to be purchased, it would still add up to a considerable saving. The all-flotation mill would reduce man power by some 30 pct, and make a metallurgical improvement. Operating costs could be reduced bv 2$ per ton. The metallurgical improvement would amount to 4$ per ton, for a total of 6$ per ton of ore milled. An estimate of the cost of the conversion was set at $250,000. With the savings as estimated this could be paid off in about two years. On paper it therefore seemed attractive enough to justify a mill test. MILL TESTING One section of the Federal mill was made available for use as a separate test circuit. Cyclones and density controllers were borrowed from the Viburnum and Indian Creek mills. Denver flotation cells were obtained from the Desloge mill that was then shut down. Two 10-cell groups of Fagergren flotation machines, consisting of eight roughers and two cleaners in each bank, were segregated from the remainder of the plant. The 9x12-ft rod mill was continued as a primary grinding mill. The two 6%x12-ft mills on this section were converted from rods to balls, and the speed increased to 22.0 rpm. Cyclones were installed to close the circuit of these ball mills. The ground pulp from each of the ball mills was fed separately to its own bank of flotation cells so that two completely separated test circuits could be run in parallel. This test circuit operated on a three-shift basis from Dec. 22, 1959 to Mar. 21, 1960. The first few weeks were occupied in developing conditions for proper metallurgy and trouble-free operations. Results were rather erratic but as the ore dressing laboratory and the mill operators became more familiar with conditions they were able to obtain expected results, which could be duplicated day after day. The last five weeks of testing indicated the best results and are tabulated in Table I. During the first two weeks a Denver unit cell was used on No. 1 flotation circuit. Even though it recovered almost one half of

Jan 1, 1962

By A. H. Shoemaker

THE shutdown of Homestake by Government order L-208, with its consequent disruption of a very stable and trained working force, coupled with postwar inflation and the coincidence that a mining depth had been reached that posed problems of ventilation, access to exploration areas, and choice of mining methods that would be applicable to zones of greater rock pressures made a very searching analysis of every phase of Homestake's operations a necessity. Any changes to be made had not only to meet the problems of deeper mining but also had to provide greater efficiency so that the mine might operate at a substantial profit until such time as a gold price adjustment might be forthcoming that would offset post-1945 inflation. Geology and Mining Situation The Homestake mine lies in the northern Black Hills in an area of Pre-Cambrian rocks exposed by the erosion of the paleozoic formations which covered the Black Hills. The Pre-Cambrian rocks in the vicinity of Lead comprise metamorphosed sediments with a total thickness of about 20,000 ft. The oldest formation, the Poorman, is ankeritic carbonate schist. The next oldest, the Homestake formation, host rock for all Homestake orebodies, is a siliceous iron-magnesium carbonate schist. The younger formations are dom-inantly argillaceous with some quartzites. Tertiary intrusive rocks cut all formations. The Pre-Cambrian rocks have undergone extreme isoclinal folding. Superimposed on this intricate folding are zones of shear folding which cross the isoclinal folds at small angles. The Homestake orebodies are pipelike replacements of the Pre-Cambrian Homestake formation where certain cross folds intersect some earlier isoclinal folds. These orebodies plunge flatly to the southeast at variable angles locally as steep as 45". The orebodies are replacement areas where numerous vein quartz of irregular shape have formed with surrounding zones of chlorite alterations containing disseminated sulfides and metallic gold. Where the numerous individual quartz veins with the sulfide and gold-bearing alteration zones are close together, large irregular orebodies with a roughly elliptical plan outline result. These ore zones may be more than 200 ft wide and 700 ft long in plan area. They have followed down the plunge of certain severely folded structures with great persistence. Two vertical operating shafts, the Ross and Yates, serve the mine, one with rope capacity to reach the 4850 level, the other to the 5000 level.

Jan 1, 1959

By C. H. Benedict

1. Shaking Tables 2. Fine Grinding 3. Hydraulic Classification 4. Mechanical Thickeners 5. Flotation ENTERING the profession of minerals beneficiation (it was plain garden variety "ore dressing" . in those days) I was fortunate that at that time the first major innovation in modern ore dressing practice was being introduced. I refer to the Wilfley table. You youngsters that came into the game only 30 years ago or even more recently, with flotation machines and reagents as your very ready tool in time of trouble, do not realize what the invention of the Wilfley table meant to us. We had but one physical property of ores to reckon with-specific gravity- and when there was but little difference in specific gravity between the mineral and the gangue, we were in trouble. The jig and the revolving table were our only mechanical equipment for recovering values and so that we might make even a reasonably satisfactory extraction, we had to classify and reclassify, and jig and rejig, and worry about the laws and advantages of free settling vs hindered settling and just tire the minerals out.

Jan 10, 1954

By E. D. Gardner

Apparently the widespread agitation for the codification of our mining laws has had its effect, and it is quite possible that Congress will take up the question during this present session. The greatest objection to our present statutes pertaining to metalliferous deposits seems to be directed against the law of the apex. Those who are not in favor of changing this law are very far in the minority and they apparently realize that it is useless to urge its retention. Next in importance to the repeal of the law of the apex, seems to be a widespread advocacy for the repeal of the law requiring discovery of mineral before a valid location of a mining claim can be made. To a lesser extent there appears to be a desire to have the law changed so as to allow patent for claims without mineral discoveries. The purpose of this article is to review the arguments in favor of the proposed change of the discovery requirement, to show some of the evils that may be expected to result therefrom, and to consider whether a system may be devised to correct the undesirable features of the present law in this respect and at the same time not expose the mining fraternity and the general public to the evils which would result from the repeal of this fundamental requirement. Under the law as at present framed, the validity of a mining location is dependent upon the fact of discovery of mineral within the boundaries of the land claimed. " * * * but no location of a mining claim shall be made until the discovery of the vein or lode within the limits of the claim located" (Sec. 2,320, U. S. Rev. Stat.). All authorities agree that discovery is the source of the miners' title. Lindley, in his valuable work on Mines (3d Ed., Sec. 335), lays down the rule in part as follows: "Discovery is the initial fact. Without that no right can be acquired. * * * Such discovery must precede the location, or be in advance of intervening rights. The proof of recording and marking a claim will not authorize the court to presume a discovery." As is well stated by the U. S. Supreme Court in Erhard v. Boaro (113 U.S. 536):

Jan 1, 1917

By H. R. Collins

The purpose of pulverizing coal before burning it is to make available every heat unit it contains. Machinery has been developed which will pulverize coal in one operation, delivering it to bins in front of the furnaces at an expenditure of about 17 hp.-hr. per ton, in a medium-sized plant. The cost of the operation depends upon the amount of moisture that must be expelled before pulverizing, the cost of labor, and the cost of coal delivered at the plant. At a small plant, requiring a pulverizer with a capacity of only 1/2 ton per hour, the cost per ton pulverized will naturally be greater than at a plant requiring the largest pulverizer, with a capacity of 7 tons per hour. :The first step is to reduce large lumps to a size suitable for drying uniformly, before passing to the pulverizing mills; this is done in rolls, at a single pass. The second step is the elimination of moisture, in order to facilitate pulverizing to great fineness, while also increasing the heating effect and the temperature attainable when the coal is burned. There are other mechanical advantages in the handling of dried coal. Driers are now manufactured which are able to eliminate moisture without distilling any of the volatile combustible matter in the coal; they are fired by hand or with pulverized fuel. The heat first surrounds the shell of the drier, being confined within a chamber where complete combustion takes place; the heated gases are then led through a duct to the discharge end of the drier and enter the inside of the shell at a temperature not exceeding 300" F. This temperature is maintained by the operator and is indicated by a pyrometer. Volatile combustible matter is not likely to be distilled until the temperature rises above 400" F. On discharging from the drier, the coal is usually passed over a magnetic separator in order to prevent pieces of iron from going to the pulverizer. Two types are used: a magnetic pulley which automatically discharges its collection of iron, and a lifting type, from which the iron is removed by hand when convenient. In the operation of pulverizing, the coal should preferably be reduced until 95 per cent. will pass through a 100-mesh and 70 per cent. through a 300-mesh sieve. Such a product is obviously an almost impalpable powder.

Jan 1, 1920

By N. A. Ziegler

THE present publication is a continuation of the work on gas analysis, described in a paper presented before the Institute of Metals Division a year ago.1 While that paper was largely descriptive in character, dealing with the various parts of the apparatus and method of operations, the present one gives numerical data obtained as a result of a series of experiments with iron-carbon alloys. The apparatus and the methods applied are essentially the same as previously described, changes being only in minor details. Attention should be called to the fact that in the present work we are dealing with the gaseous mixtures obtained as a result of vacuum melting of various ferrous alloys. It should be understood that when the terms "degasified sample" and "products of degasification" are used, they refer to the sample remaining after the vacuum fusion of the alloy and the gaseous products removed therefrom, respectively. The writer does not wish to create the impression that the metallic products of this process are absolutely free from any gaseous elements, nor that the gases obtained are present as such in the original sample. These two points are not yet definitely known and are subjects for future investigation. The point, however, which has been established beyond doubt, is that all the gases dealt with come from the metallic charge and are present either in the charge as such, or are produced as a result of chemical reactions going on within the charge.. The suggestion that the gases are due to the reactions between the metallic charge and the refractory materials has no valid basis.

Jan 1, 1929

By W. H. Forbes

As permissible explosives and electric detonators are now generally recognized as the only safe means of blasting in coal mines, this paper is limited to their use. Causes of Misfires There are many different causes of misfires, but the principal ones are as follows: 1. Explosives which have deteriorated through improper storage either at the storage magazine, the distributing magazine, or at the working face. This is not only true of the explosive itself, but also of its detonating agent. 2. Improper priming and charging at the working face. This commonly occurs when the explosives are handled by inexperienced persons. 3. Improper methods of tamping; the leg wires of the detonator may be abraded or broken by the tamping bar or stick, thereby causing a short or broken circuit. 4. Faulty leading wire, or electrical apparatus of insufficient strength to explode the detonator. Prevention of Misfires Storage is an important factor, especially with permissibles of a nitrate or ammonia base. Both explosives and detonators should be stored in substantially built, fire-resisting magazines and should be situated so that the minimum amount of moisture and heat is present. They should be so constructed that a constant supply of fresh air enters; the floor of the magazine should be raised to permit the circulation of air under the stored explosives. Boxes should be stored top side up and in such a manner that the old explosives are used before those of a later delivery. This eliminates chance of deterioration from lengthy storage. Detonators should be similarly handled and stored. The distributing magazine stock should be regulated so that not more than one day's supply is on hand.

Jan 1, 1930

By F. C. Sturges

[CONTENTS PAGE ................. Introduction-Grouting in Mines. By F. C. STURGES. I Use and Technique of Pressure Grouting in the Construction Industry. By V. L. MINEAR . 3 Technique of Pressure Cementing in the Petroleum, Mining, and Construction Industries. By WY. D. OWSLEY and R. E. MOELLER. ..................... 9 An Example of Controlled Pre-grouting in Shaft Sinking. By R. H. ALLEN and J. W. GALPIN. 15 ........ Solidifying Mines and Shafts Areas by Pressure Grouting. By B. H. MOTT 17 .............. Grouting in Southeast Missouri District. By W. W. WEIGEL 20] Introduction-Grouting in Mines By definition the word "grout" means a thin mortar, or a kind of plaster or cement, and "grouting" means to fill up or finish with grout. The words "cement," "plaster" and "mortar" mean a substance that is used in a soft state which subsequently hardens. Thus, grouting is the filling of void space with a substance that hardens. Construction cements are the most common substances used, either by themselves or in mixtures, but the term grouting is applied quite correctly when other substances such as plastics and certain chemicals are used. Also, the use of the term grouting to cover the filling of voids with materials that do not actually become hard, such as the flotation tailings used in grouting in the southeast Missouri lead district, should be considered correct, as some stiffening does take place and, anyway, it is a better descriptive term than any substitute. Engineers are interested in grouting because some of the materials with which they must work contain voids, and certain conditions can be improved if these voids can be filled with something solid and permanent. Grouting is done to accomplish several purposes: I. To stop the passage of fluids and gases, 2. To cement materials together to make them stronger, and 3. To prevent consolidation of materials by filling void space with something solid as a replacement for the air and water that could be forced out under load. The construction industry uses grouting extensively for all three purposes. Grouting is used to stop water percolation under and around dams. It is used to control water flow in tunnel driving and in shaft sinking. It is used to improve foundation conditions under civil engineering structures by permanently filling void space and thereby reducing settlement, or by cementing broken rock together and increasing its supporting strength. The oil and gas industry does a lot of grouting, primarily to stop the passage of gases and fluids. The search for oil at increasingly greater depths has meant greater investment per well, and the oil industry has spent large sums on development of improved drilling methods. This

Jan 1, 1947

By W. O. Philbrook, K. Natesan

The oxidation kinetics of spherical pellets of zinc sulfide made from Santander concentrates were studied using a thermogravimetric technique. The experiments covered a temperature range-. of 740" to 102O°C, 0-N mixtures varying from 20 to LOO pct O2, and pellet diameters between 0.4 and 1.6 cm. Mathematical models were formulated to Predict the reaction rate on the assumption that a single transport or interface reaction step was rate -controlling. Analysis of the data indicated that the process of oxidation was predominantly controlled by transport through the zinc oxide reaction-Product layer. ROASTING processes, which are reactions between solids and gases, are very important because they are employed in the production of a number of basic metals. These processes are highly complicated, and one needs to consider the transport phenomena of heat and mass between the solids and gases in addition to the kinetics of various chemical reactions involved. Because of such complications there is a lack of knowledge concerning the rate-limiting factors, which may strongly depend on temperature, particle size, gas composition, and solid structure. The oxidation of zinc sulfide, which is of commercial importance in zinc production, falls into this class of reactions. The major goal of this work was to elucidate the roles played by different process variables, such as reaction temperature, gas composition, pellet size, and pellet porosity, on the kinetics of oxidation of single pellets of zinc sulfide. Roasting of zinc sulfide single particles has been a subject of both experimental and theoretical investigations.&apos;-&apos; The reaction is exothermic and may be considered to be irreversible. Such a reaction has been found to proceed in a topochemical manner. In other words, as the reaction proceeds, a progressively thicker outer shell of zinc oxide is formed, while the inner core of unreacted sulfide decreases. It has been found experimentally, both in the present work and in the previous investigations,1-9 that the particle retains its original dimensions and the process requires transport of gaseous oxygen across the porous product layer for continued reaction. The reaction may be represented by ZnS(s) + 3/2 O2(g) = ZnO(s) + SO2(g) [1] The solid product considered here is only zinc oxide, since the diffraction patterns of zinc sulfide pellets oxidized partially at &apos;798" and 960°C showed K. NATESAN, Junior Member AIME, formerly St. Joseph Lead Fellow, Department of Metallurgy and Materials Science, Carnegie-Mellon University, Pittsburgh, Pa., is now at Argonne National Laboratory, Argonne, Ill. W. 0. PHILBROOK, Member AIME, is Professor of Metallurgy and Materials Science, Carnegie-Mellon University. This paper is based on a them submitted by K. NATESAN in partial fulfillment of the requirements for the Ph.D. degree in Metallurgy and Materials Science at Carnegie-Mellon University. Manuscript submitted December 2, 1968. EMD lines corresponding to original zinc sulfide and the newly formed zinc oxide. OXIDATION MODEL The generalized model for gaseous oxidation of zinc sulfide is illustrated in Fig. 1. This depicts a partially oxidized sphere of zinc sulfide in a gas stream surrounded by a laminar film of gas. The spherical sample of zinc sulfide of unchanging external radius r0 is suspended in a flowing gas stream of total pressure PT and composition specified by the partial pressures of the individual components. Partial pressures of the gaseous species in the bulk gas phase, at the exterior surface of the pellet, at the ZnS/ZnO interface, and at equilibrium for Reaction [I] are identified by the superscripts b, o, i, and eq, respectively. The overall reaction involves the following ~te~s:&apos;~&apos;~&apos; Step 1. Transfer of reactant gas (oxygen) from the bulk gas stream across the gas boundary layer to the exterior surface of the pellet and the reverse transfer of the product gas (sulfur dioxide). Step 2. Diffusion and bulk flow of oxygen from the pellet surface through the product shell (ZnO) onto the ZnS/ZnO interface and the reverse transfer of sulfur dioxide. Step 3. Chemical reaction at the interface, which results in consumption of oxygen gas and generation of sulfur dioxide gas and heat; at the same time the _________ PARTICLE SURFACE / x^^^^n^X / MOVING INTERFACE core-----/ sJSNxy " /T^T^02 \ V\V$\ ^NWX/ "*/— GAS BOUNDARY x. \\ZnO SHELLV/ / \^ . / &apos; ^ BULK GAS --------N_______ _____,------p£ w \ P« / (f> \ / a \ <i) / <----------------- _(o) ^^--------------(b) °- pso, pso2 ro ri 0 ri ro RADIAL POSITION Fig. 1—Generalized model for oxidation of a sphere of zinc sulfide.

Jan 1, 1970