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By F. J. Chernosky

Most previous studies of coal flotation utilized chemically pure reagents. Since such reagents are not available in quantity, a study of various wmmercially available reagents as frothers was undertaken. Flotation procedures similar to those used in a large number of commercial coal flotation plants were employed. The reagents used were compared on yield-selectivity-wst basis. The selectivity was found to be relatively constant with yields above 70% but the reagent cost varied greatly. The types of reagents available were compared. In the past, a number of papers have been written on the use of various reagents as coal flotation frothers. For the most part, these have been an attempt to correlate the intrinsic chemical and physical proper- ties of the reagents or reagent groups to the floata-bility of various fine coals. Because of the type or nature of evaluations made, chemically pure reagents were normally used. Generally, these reagents are unavailable in commercial quantities. Therefore, the results obtained with these reagents were usually limited in usefulness to the plant operator or metallurgist. This paper presents the results of a study in which commercially available forms of various reagents were used as flotation frothers. Flotation procedures which would conform in general to those employed in a large number of commercial coal flotation plants were utilized. The objective of the test was to compare these reagents on yield-selectivity-cost basis, that is, 1) the yields obtained, 2) the ash levels obtained and 3) the reagent cost relating to these results. REAGENTS The reagents employed have been grouped into the following chemical classes: 1) aliphatic alcohols, 2) terpines, 3) glycols (synthetic water-soluble

Jan 1, 1963

By L. F. Elkins

Water coming into wells with bottom water present in the Fosterton field, when their oil recovery was only 0.1 to 1.5 per cent of oil in place below the lowest perforation, confirms lack of shale barriers to vertical flow which also are not apparent in cores and electric logy. Low contrast of vertical and horizontal permeability, high mobility ratio betweerz oil and water zone and pos.rible rate effects due to gravity Combine to prevent easy analysis of water invasion pattern and efficiency by analogy or intuition. Theoretical analysis of performance including these factors using a new direct nurnerical .solution of potential distribution in a network led to unanticapted indications that water would under-run the entire oil reservoir with low volumetric coverage if supplied through natural influx or peripheral water injecfion below the oil-water contact. An unusual pattern of water injection is to he adopted in this recently unitized pool to provide more uniform water flooding in that two-thirds of the oil reservoir not underlain by bottom wafer. INTRODUCTION The Fosterton field, Southwestern Saskatchewan, Canada, was discovered in Jan., 1952. It produces at a depth of 3,100 ft from a pinch-out of the Roseray sand at the Lower Cretaceous-Jurassic unconformity. The field, covering 2,500 acres, contains 54 wells on 40-acre spacing. Development was essentially complete in June, 1954, but significant production did not start until May, 1955, when a pipeline outlet became available. Within one year rapid in- creases in gas-oil ratio and early encroachment of water created operating problems in the down-structure eastern half of the field and raised serious questions about reservoir performance and ultimate recovery. This paper describes the unusual behavior of water encroachment—on both well and reservoir bases—and the analyses made to interpret it. The field was unitized July 1, 1958, for water flooding. A somewhat unconventional

By M. Felsenthal

Engineers are frequently faced with the problem of having to predict oil recovery from a solution gas drive reservoir in the early life of a field. This is often the time when actual laboratory or field-derived gas-oil permeability (kg/k0) data are not yet available. Although excellent collections of k0/k0 data for various types of rocks may be found in the literature,1,2,3 a need exists for a more detailed correlation of k0/k0 data with core properties such as porosity, permeability, clay content or pore-size distribution. It is the purpose of this article to present this type of correlation for sandstone material. The correlation is based on laboratory tests performed on over 300 core samples from 19 reservoirs in the United States and Canada. EXPERIMENTAL Cores were analyzed by routine procedures, using samples of conventional size (7/8-in. diameter, 7/8-in long) cut parallel to the bedding planes. Air permeability was measured at 1.67 atm mean pressure in a Hassler-type apparatus. Porosity was determined with the aid of a Ruska bulk volume meter and a Boyle's Law rock volume meter, An evaporation method' was used to evaluate irreducible water saturations. Core samples were saturated with 25,000 ppm NaCl brine. The brine was reduced to the irreducible saturation, and the remainder of the pore space was filled with kerosene. This was followed by multiphase flow tests using the so-called "dispersed feed" technique.5 n this technique, gas and oil (kerosene and kerosene-saturated air) were dispersed with the aid of a porous Alun-durn feed head, the face of which contained a waffle-shaped system of Lucite-lined grooves. Oil entered the back side of the feed head and emerged at the raised areas of the front face. Gas was introduced directly into the system of grooves at the front face. The gas-oil mixture then entered the test core which was kept in capillary contact with the feed head. Permeabilities were determined from rate and pressure measurements and saturations from weights. All determinations were performed at equilibrium or steady-state conditions. Pore-size distributions were determined on selected samples by a mercury injection technique.6 GENERAL CORRELATIVE TRENDS When examining data from a given reservoir, it was noted that k0/k0 vs saturation curves became generally less steep as specific air permeability increased, a development that has a favorable effect on oil displacement efficiency by solution gas drive. This trend has also been reported by others in the literature.' An effect of porosity on k0/k0 data was also noted. This effect was not generally discernible in a study of relative permeability data for a given reservoir but became apparent when data for sandstone reservoirs of similar lithology but differing average porosity were compared. For instance, in a comparison of argillaceous and/or calcareous sandstones from 11 reservoirs ranging in average porosities from 14 to 28 per cent, a definite trend was noted, indicating that for a given permeability k0/k0 curves became less favorable (i.e., steeper) as porosity increased. A similar trend was observed for a group of comparatively clean sandstones from five reservoirs ranging in average porosities from 15 to 21 per cent. For a given permeability and porosity, comparatively clean sandstones gave more favorable k0/k0 curves than argillaceous and/or calcareous sandstone or chert reservoirs. The laboratory studies also showed that least favorable k0/k0 curves were exhibited by shaly sandstone, conglomerate, and sandstone containing carbon inclusions. Table 1 lists the various source reservoirs classified by lithology types. To facilitate a correlation of k0/k0 data with core characteristcis, it was found expedient to work with

By D. A. Elgillani, M. C. Fuerstenau, J. D. Miller

Adsorption of lead and ferric iron on quartz and alumina is presented as a function of pH. Only the hydrolyzed species of these metal ions, FeOH++ and PbOH+, adsorb significantly on each of these minerals. Zeta potentials of quartz were measured as a function of pH in the presence of various additions of aluminum, lead, and magnesium salts. Sign reversal occurs at the pH values where significant concentrations of hydroxy complexes are formed. Models of adsorption are presented in the absence and presence of collector. The mechanism of adsorption of metal and collector species in the activation of nonmetallic minerals is still the center of considerable discussion in spite of the extensive study given this system. Until recently, the view was widely held that hydrated metal ions were responsible for this phenomenon. This fact is surprising, since it had been shown that the pH range in which flotation is effected corresponds to that in which metal ion hydrolysis occurs.' Additional support of this concept was pro vided by the work of Wolstenholme and Schulman in another system.' Later work has shown that hydroxy complexes of metal ions are the active species. These studies have also indicated that basic aqueous complexes of metal-collector may be necessary for flotation.3-7 Depending on the molecular weight of the collector, formation of these complexes may occur before or after precipitation of the metal-collector salt has occurred. Ion pair formation can occur when low molecular weight collectors are involved because relatively high concentrations of metal hydroxy complex and collector can be present in solution before precipitation occurs. This is not the case when high molecular weight collectors are used. A model of aqueous complex adsorption has been presented6,7 in which it has been assumed that adsorption occurs by the formation of water from adsorbed hydroxyl and hydrogen of the hydroxyl contained in the complex. Other authors8 have suggested that hy-droxy complexes are involved in these systems but that collector adsorption occurs by replacement of the hydroxyl of the adsorbed metal hydroxy complex with a fatty acid anion. All of these investigations have involved mineral surfaces that were negatively charged so that it is not possible to state with certainty whether hydrated metal ions or hydroxy complexes are the active species in this system. Use of a positively charged mineral should be helpful, however, since the hydrated metal ion will be repelled from this surface. On the other hand, if the hydroxy complex adsorbs by splitting out water, surface charge should have no effect because of the free energy decrease that the system will experience when water is formed. In this regard, sapphire is well-suited for study, since its surface is positively charged until approximately pH 9. Electrokinetic studies of quartz in the presence of various metal ions should also be useful in establishing the mechanisms of adsorption in these systems. That is, if the hydroxy complexes adsorb by water formation, drastic changes in the zeta potential should occur in the pH range in which hydrolysis occurs. In this view, adsorption of ions of widely different hydrolysis characteristics on both sapphire and quartz was measured. In addition, zeta potentials of quartz were measured as a function of pH in the presence of various metal ions and compared with flotation responses obtained under similar conditions. Experimental Materials and Techniques Reagent-grade aluminum, ferric and magnesium chlorides, and lead nitrate were used in this investigation. Adjustments in pH were made with reagent-grade HCl or KOH. Conductivity water, made by passing distilled water through an ion exchange column, was used in all of the experiments.

Jan 1, 1971

By Leo F. Reinartz

It was with humility that I accepted the invitation of the Board of Directors of our Institute to deliver the Twentieth Howe Memorial Lecture. Many previous lecturers could speak from personal experience of the great work done by Professor Howe. It was not my privilege to be one of his students but, indirectly, I came under the influence of his work many years ago. My mentor in Metallurgy at Carnegie Institute of Technology, Prof. Fred Crab tree, was an ardent admirer of Professor Howe and his work. Professor Crabtree taught me early to appreciate Professor Howe's love of truth and keen desire to find a scientific reason for every metallurgical phenomenon. In this early search, Professor Howe encountered many unexplainable facts. Nevertheless, in the classic text, "The Metallurgy of Steel," published in 1891, he indicated that he believed Research could light the way. Under the heading of "The Treachery of Steel" he said: "In the early use of Bessemer and Open Hearth Steel, many then unexplained and hence mysterious failures occurred. With our present knowledge, an easy explanation of most of them would probably have been seen. But even today certain unexplained and apparently inexpli- cable failures occur in steel; inexplicable in spite of full and intelligent investigation." Then Professor Howe continued to talk about "the trustworthiness of steel" in the following manner: First, the steel-maker has learned by experience. He knows today far better the effects of a high percentage of carbon or of phosphorus; of cracks, pipes and blow-holes; of segregation and imperfect mixing; of over-heating; of finishing too hot or too cold. Knowing, he guards against them more effectually, and keeps at home much steel that he would formerly have sent into the market. Those who would not, or could not learn and do, have been driven out of the business; the conditions necessary for producing good sound steel by the acid Bessemer and the acid Open Hearth processes have been mastered. By and by, the basic process came along with new conditions, new liabilities to unsoundness, a great hue and cry about mysterious fractures followed, and Lloyd's register provisionally forbade the use of basic steel. Much basic steel was irregular and brittle throughout; too much carbon, too much phosphorus, too cold teemings—imperfect mixing. Still there was little doubt that, with further experience, these difficulties of the basic process would be mastered as those of the acid process had been. This shows that Professor Howe could not take anything for granted. Believing that careful research would find the answer to all mysterious phenomena, he was several generations ahead of the practical acceptance and adoption of this principle.

Jan 1, 1943

By Leo F. Reinartz

It was with humility that I accepted the invitation of the Board of Directors of our Institute to deliver the Twentieth Howe Memorial Lecture. Many previous lecturers could speak from personal experience of the great work done by Professor Howe. It was not my privilege to be one of his students but, indirectly, I came under the influence of his work many years ago. My mentor in Metallurgy at Carnegie Institute of Technology, Prof. Fred Crab tree, was an ardent admirer of Professor Howe and his work. Professor Crabtree taught me early to appreciate Professor Howe's love of truth and keen desire to find a scientific reason for every metallurgical phenomenon. In this early search, Professor Howe encountered many unexplainable facts. Nevertheless, in the classic text, "The Metallurgy of Steel," published in 1891, he indicated that he believed Research could light the way. Under the heading of "The Treachery of Steel" he said: "In the early use of Bessemer and Open Hearth Steel, many then unexplained and hence mysterious failures occurred. With our present knowledge, an easy explanation of most of them would probably have been seen. But even today certain unexplained and apparently inexpli- cable failures occur in steel; inexplicable in spite of full and intelligent investigation." Then Professor Howe continued to talk about "the trustworthiness of steel" in the following manner: First, the steel-maker has learned by experience. He knows today far better the effects of a high percentage of carbon or of phosphorus; of cracks, pipes and blow-holes; of segregation and imperfect mixing; of over-heating; of finishing too hot or too cold. Knowing, he guards against them more effectually, and keeps at home much steel that he would formerly have sent into the market. Those who would not, or could not learn and do, have been driven out of the business; the conditions necessary for producing good sound steel by the acid Bessemer and the acid Open Hearth processes have been mastered. By and by, the basic process came along with new conditions, new liabilities to unsoundness, a great hue and cry about mysterious fractures followed, and Lloyd's register provisionally forbade the use of basic steel. Much basic steel was irregular and brittle throughout; too much carbon, too much phosphorus, too cold teemings—imperfect mixing. Still there was little doubt that, with further experience, these difficulties of the basic process would be mastered as those of the acid process had been. This shows that Professor Howe could not take anything for granted. Believing that careful research would find the answer to all mysterious phenomena, he was several generations ahead of the practical acceptance and adoption of this principle.

Jan 1, 1943

By L. J. Health

Synthetic rock with predictable porosity and permeability has been Prepared from mixtures of sand, cement and water. Three series of mixes were investigated primarily for the relation between porosity and permeability for certain grain sizes and proportions. Synthetic rock prepared of 65 per cent large grains, 27 per cent small grains and 8 per cent Portland cement, gave measurable results ranging in porosity from 22.5 to 40 per cent and in permeability from 0.1 darcies to 6 darcies. This variation in porosity and permeability was caused by varying the amount of blending water. Drainage-cycle relative permeability characteristics of the synthetic rock were similar to those of natural reservoir rock. INTRODUCTION The fundamental behavior characteristics of fluids flowing through porous media have been described in the literature. Practical application of these flow characteristics to field conditions is too complicated except where assumptions are overly simplified. The use of dimensionally scaled models to simulate oil reservoirs has been described in the literature. 1-3 These and other papers have presented the theoretical and experimental justification for model design. Others have presented elements of model construction and their operation. In most investigations the porous media have consisted of either u ncon soli da ted sand, glass beads, broken glass or plastic-impregnated granular substances—materials in which the flow behavior is not identical to that in natural reservoir rock. The relative permeability curves for unconsoli-dated sands differ from those for consolidated sandstone. The effect of saturation history on relative permeability measurements is discussed by Geffen, et a1.4 Wyga15 has shown quite conclusively that a process of artificial cementation can be used to render un consolidated packs into synthetic sandstones having properties similar to those of natural rock. Many theoretical and experimental studies have been made in attempts to determine the structure and properties of unconsolidated sand, the most notable being by Naar and Wygal.6 Others have theorized and experimented with the fundamental characteristics of reservoir rocks. This study was conducted to determine if some general relationship could be established between the size of sand grains and the porosity and permeability in consolidated binary packs. This paper presents the results obtained by changing some of the factors which affect the porosity and permeability of synthetically prepared sandstone. In addition, drainage relative permeability curves are presented. EXPERIMENTAL PROCEDURE Mixtures of Portland cement with water and aggregate generally are designed to have certain characteristics, but essentially all are planned to be impervious to water or other liquids. Synthetic sandstone simulating oil reservoir rock, however, must be designed to have a given permeability (sometimes several darcies), a porosity which is primarily the effective porosity but quantitatively similar to natural rock, and other characteristics comparable to reservoir rock, such as wettability, pore geometry, tortuosity, etc. Unconsolidated ternary mixtures of spheres gave both a theoretically computed and an experimentally observed minimum porosity of about 25 per cent.7 By using a particle-distribution system, one-size particle packs had reproducible porosities in the reproducible range of 35 to 37 per cent.6 For model reservoir studies of the prototype system, a synthetic rock having a porosity of 25 per cent or less and a permeability of 2 darcies was required. The rock had to be uniform and competent enough to handle. Synthetic sandstone cores were prepared utilizing the technique developed by Wygal.5 Some slight variations in the procedure were incorporated. The sand was sieved through U. S. Standard sieves. A 18-20 sand denotes that the sand passed the Number

Jan 1, 1966

By H. H. Bein

Most western industrial sands are feldspathic and contain feldspars in variahle amounts. A few deposits will show alumina contents of less than one per cent while others will contain over twelve per cent alumina. Some industries are not especially concerned with the amount of contained feldspar but are interested only in color and in size gradations. Other industries, however, are very much interested in alumina content and set up quite rigid specifications as to this content. Several western plants are beneficiating crude sands both to reduce the iron content and to control the feldspar content. At present, most of these plants are using flotation processes for both controls although a few plants do use magnetic separators for the reduction of iron content. Some work has also been done with electrostatic separators for the feldspar-quartz splits. The Sand Division of Del Monte Properties Company, Pebble Beach, California, has been operating a flotation plant for iron removal and the separation of quartz and feldspar since 1950. As mentioned before, control of alumina, especially in the quartz product, is very important. Some users require an alumina content of less than two per cent and others will demand a product of less than one per cent Al2,O3,. The standard Quinolate method for determining alumina is lengthy and time consuming. The HF —H2SO4 evaporation step is especially critical and, if forced, spattering is apt to occur with a resulting loss of sample. Standard procedure is to evaporate to dry ness overnight at a low temperature. Even with forcing under optimum conditions the procerlnre will take two or three hours to complete. A new method has been developed which allows an alumina determination to be made, in 10 or 15 minutes, on a sample of the quartz product as it is being produced. This pocedure, although simply an approximation, has been most helpful in showing whether or not the product being formed is meeting specifications. This procedure has also allowed a great reduction in samples formerly taken and analysed by the orthodox method. Whether a sample assays 1.75% A12O3, or 1.95% .41,0, is not so important as the fact that it is below the allowable maximum of 2.00%. Similar thinking would apply to products required to contain less than 1.00% A1,0,. The step by step procedures for the method are as follows: 1. Collect sample, drain or filter, and dry. 2. Split sample through standard Jones sample cutter to quarter or eighth sample, depending on size of original sample taken, then split down to about 5 grams through Sepor micro-splitter. 3. Screen through 50 mesh sieve (U.S. Series) and reject undersize. 4. Weigh out 2 grams and place in platinum crucible. 5. Etch with 3-5 mls 38.40% HF for 1 minute at room temp. 6. Decant and wash. 7. Stain for two minutes in same crucible with a 1% water solution of Nigrosene dye. 8. Decant and wash well. 9. Dry.

Jan 1, 1961

By Leslie C. Richards

Sooner or later the potential miner of industrial minerals reaches the conclusion that of the various factors he must consider, the marketing of his product is. the most important. The sooner he realizes this the better, as successful industrial mineral producers .will confirm. Herein lies a difference between i.ndustria1 mineral mining and metal mining. Often in the latter, technical problems of mining or concentrating are equal to or even surpass those of marketing. This is not meant to imply that there are no problems in mining and beneficiation of industrial minerals, but these usually are outweighed by the problem of marketing. Recentlv. an official of a nationally known corporation :i the elecl.ro-metallurgical industry made an industrial mineral survey in the Pacific Northwest. In the course of his investigation he interviewed producers and potential producers of the various industrial minerals scheduled for use in the plant now being constructed in this area. He stated that he was interested in only three factors: namely, (1) Can your product meet our specifications? (2) Are you able to supply our tonnage requirements? and (3) What will be the delivered price? If there are several sources of supply of sufficient grade and tonnage, as is often the case in the Northwest, then the third factor becomes the important and deciding one. While industrial minerals are usually sold f.0.b. cars with the freight being paid by the buyer, it is the delivered and riot the f.0.b. price that determines the competitive position of the producer and his industrial mineral product. Unfortunately for both the consumers and producers of industrial minerals in the Northwest, the sources are generally a considerable distance from the markets. This necessitates long rail hauls, for which transportation charges make up the largest share of the delivered cost and the delivered price of the product. Is it any wonder then, that rail rates play such an important part in the marketing of industrial minerals? In order to sell his product, the producer must be able to deliver to the market at a competitive price. It must be remembered that his largest cost factor is rail transportation, and that he is limited to markets that he can reach competitively. Since the cost of rail transportation is so important, let us compare various freight rates in the Northwest and attempt to determine their influence on marketing. A study of all rates on all industrial minerals transported in this area, is beyond the scope of this paper. For the purposes of comparison, let us consider limestone (broken, crushed, or ground), and silica rock. These are widely used industrial minerals, and are carried by several different rail routes from.the sources of supply to the centers of consumption in the Pacific Northwest. Markets and Sources of Supply: Limestone has a number of uses in western Oregon and Washington. Among them are agricultural lime for the soils of the Willamette Valley and southwestern Washington; paper rock for the mills in such cities as West Linn, Oregon City, Newberg, St. Helens, and Salem, Oregon, and Camas and Everett, Wash.; chemical and metallurgical-grade limestone for the metallurgical plants centering around Portland, and the Tacoma-Seattle areas'; and sugar rock for the sugar refineries at Toppenish, Wash., and Nyssa, Oregon. Since limestone for cement manufacture is generally processed near the quarry, transportation

Jan 1, 1951

By Leslie C. Richards

The competitive position of producers of industrial minerals depends upon the delivered price of their product. Freight charges are a major factor in the sales to consumers. A comparison of freight rates on movements of limestone and silica rock in the Pacific Northwest shows a wide variance in mills per ton mile for like hauls, thereby favoring some localities over others. Introduction: Sooner or later the potential miner of industrial minerals reaches the conclusion that of the various factors he must consider, the marketing of his product is. the most important. The sooner he realizes this the better, as successful industrial mineral producers .will confirm. Herein lies a difference between i.ndustria1 mineral mining and metal mining. Often in the latter, technical problems of mining or concentrating are equal to or even surpass those of marketing. This is not meant to imply that there are no problems in mining and beneficiation of industrial minerals, but these usually are outweighed by the problem of marketing. Recentlv. an official of a nationally known corporation :i the elecl.ro-metallurgical industry made an industrial mineral survey in the Pacific Northwest. In the course of his investigation he interviewed producers and potential producers of the various industrial minerals scheduled for use in the plant now being constructed in this area. He stated that he was interested in only three factors: namely, (1) Can your product meet our specifications? (2) Are you able to supply our tonnage requirements? and (3) What will be the delivered price? If there are several sources of supply of sufficient grade and tonnage, as is often the case in the Northwest, then the third factor becomes the important and deciding one. While industrial minerals are usually sold f.0.b. cars with the freight being paid by the buyer, it is the delivered and riot the f.0.b. price that determines the competitive position of the producer and his industrial mineral product. Unfortunately for both the consumers and producers of industrial minerals in the Northwest, the sources are generally a considerable distance from the markets. This necessitates long rail hauls, for which transportation charges make up the largest share of the delivered cost and the delivered price of the product. Is it any wonder then, that rail rates play such an important part in the marketing of industrial minerals? In order to sell his product, the producer must be able to deliver to the market at a competitive price. It must be remembered that his largest cost factor is rail transportation, and that he is limited to markets that he can reach competitively. Since the cost of rail transportation is so important, let us compare various freight rates in the Northwest and attempt to determine their influence on marketing. A study of all rates on all industrial minerals transported in this area, is beyond the scope of this paper. For the purposes of comparison, let us consider limestone (broken, crushed, or ground), and silica rock. These are widely used industrial minerals, and are carried by several different rail routes from.the sources of supply to the centers of consumption in the Pacific Northwest. Markets and Sources of Supply: Limestone has a number of uses in western Oregon and Washington. Among them are agricultural lime for the soils of the Willamette Valley and southwestern Washington; paper rock for the mills in such cities as West Linn, Oregon City, Newberg, St. Helens, and Salem, Oregon, and Camas and Everett, Wash.; chemical and metallurgical-grade limestone for the metallurgical plants centering around Portland, and the Tacoma-Seattle areas'; and sugar rock for the sugar refineries at Toppenish, Wash., and Nyssa, Oregon. Since limestone for cement manufacture is generally processed near the quarry, transportation

Jan 1, 1951

By E. T. Turkdogan

Jan 1, 1962

By C. C. Harris Discussion by B. K. Loveday

B. K. Loveday (National Institute for Metallurgy, Johannesburg, Republic of South Africa) - The paper and subsequent technical note' describing a method of determining the parameters of the three-parameter size-distribution equation developed in the paper were read with much interest. This equation was also used at National Institute for Metallurgy (NIM) to describe size distributions in grinding tests, because it was necessary to have a single equation to describe the size distribution at any time during a test. A graphical method also was used to determine the three parameters, and the use of this method as an alternative to Professor Harris's latest method is discussed here. The three-parameter model can be expressed as follows: Eq. 1 can be rearranged and transformed to Yield a linear reiationship between Y and X (transformed) log

Jan 1, 1970

By R. H. Winn

A method for the selection of the most suitable corrosion inhibitor for a particular system is given. The method involves the evaluation of surface passivity by means of copper ion displacement after the metal surface has been subjected to the corrosive atmosphere. The application of the method to the selection of suitable inhibitors for use in producing wells is described. Correlation with recognized laboratory tests has beet1 found to be good within the limitations of the test. The use of the test to evaluate inhibitor persistencc is described. INTRODUCTION Corrosion as it is associated with the industry shows wide variations in its qualitative as well as its quantitative aspects. This complicates the work of the corrosion engineer. In the past few years the efforts of the corrosion engineer have been further taxed by the large numbers of products being marketed as corrosion inhibitors by various manufacturers. These products are submitted to him together with a limited amount of data to support their use as inhibitors. The data are usually authentic and reliable yet all too often when these products are applied to an actual corrosive system the results are disappointing due to the ineffectiveness of the inhibitor and the corrosive system. The corrosion engineer must select a comparatively limited number of inhibitors for field trial from the large number available. The selection is usually made on the basis of a standardized laboratory test such as that adopted by the National Association of Corrosion Engineers or by field experience in an area; however, testing of this type is discouraging on large numbers of compounds, particularly in view of the specificity of environment. It has been an object of this work to devise a method which will allow the corrosion engineer to select the best inhibitor for a specific environment under field conditions. The test would of necessity be rapid and inexpensive. It would preferably eliminate the need for expensive and delicate instruments. STATEMENT OF THEORY The test as developed makes use of the fact that metal ions will be displaced from solution by metals having a more positive electrode potential. Thus, if an active iron surface is exposed to a solution of a copper salt, free copper will plate spontaneously on the iron surface as it is displaced from the salt solution by iron ions. If the iron surface is passified, as by coating with an insulating-type organic corrosion inhibitor, it is no longer capable of displacing the copper ions due to its own limited ionization. The result will be a change in the amount of copper plated upon exposure to a neutral copper salt solution. In practice it has been found possible to measure the magnitude of the alteration of the cell potential by determining the copper deposited on a standard iron surface under controlled conditions. This means that, as the film builds up, the resulting shift in the electrode potential tends to cause the iron surface to act more like a noble metal, resulting in a reduction in the cell potential to a point that copper will no longer plate spontaneously. Obviously, the salts of other metals such as silver, gold or platinum might be used for this operation; however, copper was selected because of the color difference of the plate, the comparatively low cost of copper salts and the ease of evaluation of the plated copper. Furthermore, its high cell potential provides a substantial driving energy. The determination of the copper is readily done colorimetrically by dissolving it in 5 per cent ammonium hydroxide solution containing 2 per cent potassium per-sulfate. The blue color of the copper ammonic complex ion so developed may be compared with standards prepared by dissolving known quantities of copper powder in the same reagent. In routine screening it is seldom desirable to determine the amount of copper plated. It is usually more important to determine the concentration of inhibitor required to prevent the plating of copper.

By P. Sanchez-Mejorada

GEOLOGISTS who are acquainted with the mines of northeastern Mexico realize that the most important lead-silver replacement deposits of the province are confined to a single formation. But since the formation is several hundred meters thick, the author has determined the relative position of the lead mantos in the belief that this information will prove useful in the search for new mines. This article describes the stratigraphic location of lead-silver replacement deposits known in several mines situated in a region comprising part of the states of Coahuila and Nuevo Leon. The area studied extends for 200 km* (125 miles) from east to west and 70 km (45 miles) north to south. Metallogenic Province: The most important metallic deposits of the region have the following common characteristics: 1) The orebodies occur as manto replacements of calcareous sediments. 2) The horizons that have contributed large tonnages of ore are in similar positions in the corresponding stratigraphic columns (as it will be shown later on). 3) Lead is the most important metal in the ores. Silver is commonly present in small amounts. Occurrence of zinc is dependent on the degree of oxidation of the primary sulfides. 4) A large proportion of the total production has been in the form of oxidized ores. 5) The deposits are located on anticlines. Rocks of Cretaceous age crop out over large areas of the states of Nuevo Leon and Coahuila. forming part of a belt that extends to the south along the eastern Sierra Madre. The sediments are cut by a small number of intrusive stocks ranging in characteristics from rhyolite to diorite. The most prominent structural feature of the region is a series of folds trending northwest-southeast. Faulting is not conspicuous in the region, although a major fault zone is found farther East.' The physiography closely reflects structural features, with mountains formed by anticlines and valleys conforming with intermediate synclines. Narrow valleys have also been developed along the axes of many anticlines, where solution of limy sedi- ments and erosion have proceeded along axial tension fractures. Stratigraphy: Rocks of the Upper Cretaceous are exposed in only a small percentage of the total area. Generally they have been eroded away from the mountains and are covered by recent talus and alluvium in the valleys. Humphrey' has published an excellent paper describing the Cretaceous formations of the Sierra de los Muertos, a short distance west of Monterrey. A brief summary of these formations is given below to convey an overall picture of the stratigraphic sequence that prevails just south of the area under consideration. Upper Cretaceous Indidura: Essentially thin shaly sediments. Cuesta del Cura: Limestone in thin wavy beds

Jan 1, 1959

By K. E. Gray, M. S. Seth

In Part I of this work,1 equations of elasticity were formulated for transversely isotropic, axisymmetric, homogeneous, porous media exhibiting pore fluid pressure. Equations of elasticity and the thermal analogy method were used to determine transient horizontal, tangential, and vertical stresses and radial displacement in a semi-infinite cylindrical region when either a constant rate of pressure or a constant rate of flow is maintained at the wellbore. In this paper, the approach presented earlier is extended to finite reservoirs for the cases of (1) steady-state flow, (2) constant pressures at the well bore and outer boundary and (3) constant pressure at the wellbore and no flow at the outer boundary. Results of this work show that radial and tangential stress gradients are high near the wellbore but diminish rapidt; away from the well; the vertical stress gradient behaves in the same way but is less severe. Radial stresses are compressive or neutral, whereas tangential and vertical stresses may be tensile, neutral or com-pressive, depending upon the boundary conditions, the physical Properties of the system and the radial distance involved (vertical stresses are always compressive in an unbounded system1. For constant boundary pressures, both radial and tangential stresses increase with time whereas they both decrease for a closed outer boundary and constant pressure at the wellbore. The vertical stress decreases with time for both systems. For steady-state systems, radial displacement may be positive or negative, depending upon the dimensions of the system, the pressure differential and the porosity. Radial displacement may be positive or negative for a closed outer boundary but is positive for constant pressures at both boundaries. INTRODUCTION The importance, utility and complexity of a realistic appraisal of the stress state at and local to a wellbore were indicated in Part I. In this paper the analytical approach presented earlier is extended to finite, cylindrical reservoir geometry for the cases of (1) steady-state flow, (2) constant pressures at wellbore and outer boundary and (3) constant pressure at the wellbore and no flow at the outer boundary. Other than the outer boundary of the reservoir being finite, the physical system and assumptions pertinent thereto are the same as before. The reader may wish to review the mathematical development through Eq. 49 of Part I before proceeding here. SOLUTION FOR GENERAL BOUNDARY CONDITIONS THERMAL STRESSES AND DISPLACEMENTS Since normal stresses do not exist at the free boundaries of a system subjected to thermal stresses, the boundary conditions are

Jan 1, 1969

By John Nunes, Frank R. Larson

Temperature-dependent functions of various ten-sile flour stress and fracture parameters were investigated on iron and low composition alloys of Fe-C, Fe-Cr, Fe-Mn, and Fe-Ni. Data were obtained over a range of test temperatures from 200" to -196"C at an initial strain rate of 0.01 min". It was found that the strain-hardening exponent, n, for the Fe-Ni alloys increased significantly at very low testing temperatures with increased alloy addition. Also, the stress and strain at fracture followed a predictable transitional type of behavior. The flour stress-temperature dependence was evaluated employing the relation: M where it is shown that composition can strongly influence the constant M. An empirical formula describing this effect is as follows: M = MI (equivalent at. pct Ni)-'" Some preliminay, tests were run on several commercial steels to test the generality of this relationship. One of the phenomenological explanations of the ductile-to-brittle transition encountered in bcc metals is based upon the difference in the temperature dependence of the flow and fracture stresses.' It states simply that the fracture stress is relatively insensitive to temperature and that the yield or flow stress rises rapidly with decreasing temperature so that, when the flow stress reaches the fracture stress, brittle fracture occurs without appreciable plastic deformation. This behavior is illustrated schematically in Fig. 1 where the ductile-to-brittle transition is shown to occur at two possible temperatures. The lowest temperature, TB, represents essentially completely brittle behavior while the higher temperature, TN, represents "notch" brittle behavior. Support for this theory is obtained when it is observed that fcc metals, which do not commonly have a ductile-to-brittle transition, also do not commonly exhibit any strong temperature de- pendence of the yield stress. This relationship of yield or flow stress behavior with the ductile-to-brittle transition has been generally observed for most metals representative of these two crystallo-graphic structures. One exception to this generalization appears in the case of tantalum where no apparent ductile-to-brittle transition has been observed. However, this may simply be an indication that this type of behavior is not directly related to the flow stress and that some other mechanism such as twinning must also be operative. A comparison of the typical temperature dependence of the yield stress of some representative metals is shown in Fig. 2. In the study of the temperature dependence of the strength of metallic materials, considerable ef-

Jan 1, 1963

By F. D. Wright, H. D. Fara

The solution to the plastic and elastic stresses around a circular shaft in a hydrostatic stress field that has appeared in two editions of a widely used book on rock mechanics1 is in error. Although this is a relatively minor matter, the correct solution was not found by a literature survey, so it appears worthwhile to present it. For a homogeneous, isotropic, rigid plastic-elastic body in plane strain which obeys Tresca's yield criterion the following equations must be satisfied:'," In the plastic zone,

Jan 1, 1963

By C. S. Samis, D. P. Seraphim

In the presence of oxygen, galena is oxidized in an aqueous medium containing ammonium acetate in accordance with the following reaction: PbS + 1/2 0, + 2 NH~Ac -» PbAc, + So + 2 NH: + H2O. This reaction was studied in an autoclave under oxygen pressure by polarographic measurement of the concentration of lead ion in solution. Oxidation rate is parabolic. The reaction products are lead acetote and elemental sulfur, the latter forming a film on the galena crystal. Reaction kinetics appear to be determined by the diffusion of lead from the galena phase to the solution interface through the film of sulfur. RECENT applications of pressure leaching on a commercial scale have emphasized the metallurgical importance of the oxidation of sulfide minerals in aqueous media by oxygen under pressure. Research experience has shown that sulfates, thio-nates, and metal oxides are the products of humid oxidation of sulfide minerals in basic solutions. The metal oxides may be solubilized in the presence of a complexing ion.' Certain oxide minerals are also amenable to treatment by this type of oxidation.' Several kinetic studies have been made of reactions of this type. Stenhouse' found that pyrite (FeS?) oxidized in a sodium hydroxide solution to produce a soluble sulfate and an insoluble layer of iron oxide and that the kinetics of the reaction were controlled by oxygen diffusion through the oxide layer. Andersen' studied the oxidation of galena (PbS) in a sodium hydroxide solution under oxygen pressure. He found the lead and sulfur to be simultaneously oxidized to produce plum bite ions and sulfate ions, and that the reaction rate was proportional to the surface area of the galena. The kinetics appeared to be determined by the reaction of oxygen and water with the galena surface. In each of the above reactions the metal and sulfur components of the mineral were oxidized simultaneously and at equal rates. In the present study the alkaline medium has been replaced by an approximately neutral solution of ammonium acetate in which lead sulfate is soluble. Under the conditions no sulfate was produced and no sulfur could be detected in the solution. The metal component of the mineral was solubilized and the liberated sulfur remained as a film of elemental sulfur on the surface of the galena crystal. A kinetic study of this reaction was undertaken to establish the kinetic mechanism and to determine the rate controlling step. Specific reaction rates were determined by oxidizing crystals of galena of measured surface areas in an autoclave maintained at the desired temperature and oxygen pressure. The rate of reaction was followed by measuring the concentration of lead in the ammonium acetate solution with a cathode ray polarograph, employing stationary platinum electrodes incorporated in the autoclave. Experimental Materials and Equipment Crystals of galena obtained from Violamac Mines, Retallack, B. C., were selected for oxidation because

Jan 1, 1957

By G. Thodos, D. E. Matschke

Cansiderable time and effort frequently are expended to establish, with a degree of confidence, the PVT behavior of pure substances. In particular, a great deal of experimental information contributed by a number of investigators is available in the literature. The data of each investigator, although significant in themselves, cannot be used with a high degree of confidence until they are compared with the continuum of information presented by others. Current interest in thermodynamic and transport properties, for not only the gaseous state but the con-densed state as well, requires that PVT infarmation be presented for both regions. The density dependence on temperature and pressure, when presented as a continuum, is of considerable value in itself, especially since the available equations of state fail to properly account for the PVT behavior in the condensed state. For this reason and to incorporate PVT data recently presented in the literature, this investigation was carried out. In their studies concerned with the thermodynamic properties of methane, Matthews and Hurd in 1946 utilized the data of Kvalnes and Gaddy and Olds, Reamer, Sage and Lacey to establish the PVT behavim of methane in the superheated region and the saturated liquid densities of Keyes, Taylor and Smithl in conjunction with the Clapeyron equation to develop the densities for the saturated envelope. Current activity sponsored by API Project No. 44 under the direction of F. D. Rossini has led to a tabular presentation of compressibility factors for gaseous methane in the superheated region.la These values were obtained by using smoothed residuals, developed from experimental data and the Ben edict-Webb-Rubin equation,' to establish internally consistent compressibility factors for the real gas. This approach offers probably the most precise presentation of PVT information for gaseous methane to date. The PVT behavior of methane also can be represented accurately by equations of state such as the Benedict-Webb-Rubin equation or the Martin-Hoa equation.' These equations, although valuable for analytically representing the PVT behavior, lack precision in the compressed-liquid region. The PVT data available in the literature for methane were utilized to obtain reduced densities that are presented in Figs. 1 and 2 as functions of reduced temperature with parameters of reduced pressure. The critical constants utilized for methane are those reported by Kobe and Lynn." These critical values, T, = 191.1°K, PC = 45.8 atm and p, = 0.162 gm/cc, produce a critical compressibility factor, z, = 0.289. The PVT information, as obtained from the literature, in many instances was not presented in an immediately

By Mazany, M. S.

THE Caletones copper smelter of the Braden Copper Co. is in the " Teniente" mining district about SO km. (49.7 mi.) southeast of Santiago, Chile. From the seaports of San Antonio and Tralparaiso, the property is reached via the Chilean State Railway (66-in. gage) to Rancagua, whence the Braden railroad (30-in. gage) leads to the smelting plant at Caletones, 60 km. away at 5100 ft. elevation, and continues on to the mine and concentrator at Sewell, at 7000 ft. elevation, 12 km. farther into the Andes. The smelting plant was completed and put into commission in February, 1922. At the start, it smelted daily 750 tons of concentrates produced at Sewell from 10,000 tons of ore; later, its capacity was increased to 900 tons of concentrates from 12,000 tons of ore per day; and it is now being increased to 1100 tons of concentrates from 15,000 tons of ore per day. The smelting plant production is governed chiefly by the

Jan 1, 1925