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By Henry A. Stiff, Lawrence E. Davis

A graphic method was developed which can be used to predict the tendency of oil field waters to precipitate calcium Sulfate under a variety of conditions. Application of this method is made to the prediction of sulfate scale formation in heater treaters. boilers. oil wells. cooling systems and water injection wells. INTRODUCTION A solution may be said to be in equilibrium with respect to a given salt when the concentration of that silt in equal to its solubility. If for any reason the concentration of the salt is increased or its solubility decreased. the equilibrium is upset and precipitation of the salt takes place. Thus, if the concentration of a salt in a particular solution is known and its solubility can be calculated for a given set of conditions, the tendency of this salt to form a precipitate under these conditions can be predicted. Based on these principles a method has been developed for determining the tendency of oil field waters to form calcium Sulfate precipitates under various conditions. THE SOLUBILITY DIAGRAM Calcium sulfate precipitation most frequently occurs when two waters are mixed: one containing calcium ions. and the other sulfate ions. As one of these waters is added to the other a point may be reached where the concentration of calcium Sulfate is greater than its solubility. thus causing the formation of a precipitate. The solubility diagram is a graphic device for determining the location of such points, thereby making possible a prediction of the tendency of such a system to deposit sulfate scale. A similar diagram can be used to solve many other problems involving the precipitation of calcium sulfate. Fig. 1 shows a solubility diagram representing the mixing of two waters. Water "A" contains a high concentration of odium, magnesium, and sulfate ions together with a small amount of calcium. Water "B" contains a high concentration of calcium ions together with sodium, magnesium and a small amount of sulfate ions. The percentage mixture of these waters is plotted along the abscissa of a system of rectangular coordi-

Jan 1, 1952

By S. R. B. Cooke, Iwao Iwasaki, Hyung Sup Choi

John Dasher (Materials and Processes Engineer, Crucible Steel Co. of America, Pittsburgh, Pa.) The authors are to be congratulated for their excellent work, dramatic results, and persuasive explanation on the neglected subject of the temperature variable in soap flotation. The explanation includes why heat is helpful in conditioning and why heat is helpful in flotation. This is a fine start, but I hope the work will be continued to show which is the major effect. In the work of Noman and Dash er(1) it was found that substantially all the benefit of heat came from the conditioning step, and that results were much better if a thick pulp was conditioned hot and then diluted with unheated (or less heated) water for flotation (or agglomerate tabling) than if the same quantity of heat was used to condition and float at some intermediate temperature. In other words, heat for conditioning gives a Rood return, but additional heat for dilution water is near or beyond the point of diminishing return. Strathmore R. B. Cooke, lwao lawsaki, and Hyung Su0p Choi (Authors' Reply) Mr. Dasher'skind comments on our paper are appreciated. In view of the relative simplicity of empirical investigationsof the temperature variable upon conditioning and flotation, it ispuzzling why the subject is so neglected. Our work, being sub sidiary to the main investigation of the effect of structure of fatty acid collectorsupon iron ore flotation, was quite restricted, but we intend to return to the subject as soon as possible. Mr. Dasher's point, that given a certain number of calories it is better to invest them for conditioning in a thick pulp rather than to spread them out for both conditioning and flotation operations, is well taken and cannot be argued. On the other hand there is no question that high temperature during the flotation of iron ores induces superior frothing characteristics, and, in particular, greatly augments the rate of flotation and markedly decreases the time required for "difficult" particles to float.

Jan 1, 1961

By Wilhelm Rohn

IN discussing the influence of a content of gases on metals and alloys we should probably first consider the physical and chemical conditions under which these gases may be present. By a chemical analysis, such as the total extraction of gases from the liquid metal by melting in a graphite crucible in vacuo, we find only the sum of gaseous chemical elements contained in the metal in any form and no reference is made to the special form under which they have been present previously. CONDITION OF GASES IN METALS In considering. gases in metals we may first turn our attention to gases simply dissolved. Because the solubility of almost, any gas decreases suddenly at the freezing point, most of them are released during solidification, developing rise of ingots and blowholes. If only a little gas is dissolved in the molten metal the size of such blowholes may be miscroscopical, or even submicroscopical, resulting in, a certain reduction of the notched-bar impact test values. Hydrogen is believed to become less soluble as the temperature is lowered and therefore increasing quantities of this gas may be evolved during cooling between the freezing point and room temperature, leading to unsoundness of the ingot at weak spots; i.e., at the grain boundaries. This gas at the grain boundaries probably is present at high pressure and therefore impairs the mechanical properties to a degree similar to that found in the hydrogen embrittlement of copper. Usually we may trace such gases by observing rising ingots, or at least by the formation of a characteristic pattern of small grooves upon etching. Another condition of gases present within metals is that of chemical compounds, the most common being oxides and mostly present as slag inclusions of various kinds. If such oxides are insoluble in the liquid metal and emulsify with it, we find microscopical or submicroscopical slag inclusions distributed homogeneously throughout the metal and spread through the whole mass of the crystals. This special form does little harm to the mechanical properties. Some oxides are somewhat soluble

Jan 1, 1932

Jan 1, 1879

By Ira B. Joralemon

Neighboring mines, like men who live in the same environment, often assume similar characteristics. In the Bridge River area of the Lillooet district in central British Columbia there is a remarkable exception to this rule. The Pioneer mine has a simple fissure over 3000 ft. long, with no faults of more than a few feet and with only minor variations in width; the Bralorne mine, 2½ miles away at the other end of the same intrusion, has developed one of the most intricate vein and fault systems in the West. Hinged faults displace the main vein for hundreds of feet, and sometimes become valuable veins themselves. The width of ore varies in a few yards from 2 to 60 ft. Changes in grade of ore are just as abrupt. The rocks that follow the veins or are cut by them often grade into one another or into the ore with no definite contacts. Although the complexity of the structure has left many problems unsolved, the development has indicated a fascinating geological pattern. The Bralorne is in the eastern portion of the Coast Range, 55 miles by spectacular mountain road from the Pacific Great Eastern Railway station of Bridge River. The adit tunnel runs easterly from Cadwallader Creek, a tributary of Bridge River that flows into the Fraser River. Steep mountains rise from 3300 ft. elevation above sea level at the creek to peaks and ridges at 8000 to 9000 ft. altitude. The lower slopes are heavily wooded while above 5000 ft. bare rocks, glaciers and snow-fields extend far above timber line. See Fig. 1. Story of the Bralorne The Lorne claim, staked in 1897, was one of the earliest lode locations in the Bridge River district. At that time it was 70 miles by steep and treacherous trail from the railway. For the next 15 years Arthur Noel, Will Haylmore and other local prospectors mined the small, irregular, oxidized quartz veins to a maximum depth of 200 ft., and treated the ore in arrastres and later a five-stamp mill. The total production to 1912 was only $55,000. Noel and associates later formed the Lorne Amalgamated Mines Co., which they worked in a desultory way until 1925. Increasing sulfide and arsenide content in the veins

Jan 1, 1935

By Ira B. Joralemon

Neighboring mines, like men who live in the same environment, often assume similar characteristics. In the Bridge River area of the Lillooet district in central British Columbia there is a remarkable exception to this rule. The Pioneer mine has a simple fissure over 3000 ft. long, with no faults of more than a few feet and with only minor variations in width; the Bralorne mine, 2½ miles away at the other end of the same intrusion, has developed one of the most intricate vein and fault systems in the West. Hinged faults displace the main vein for hundreds of feet, and sometimes become valuable veins themselves. The width of ore varies in a few yards from 2 to 60 ft. Changes in grade of ore are just as abrupt. The rocks that follow the veins or are cut by them often grade into one another or into the ore with no definite contacts. Although the complexity of the structure has left many problems unsolved, the development has indicated a fascinating geological pattern. The Bralorne is in the eastern portion of the Coast Range, 55 miles by spectacular mountain road from the Pacific Great Eastern Railway station of Bridge River. The adit tunnel runs easterly from Cadwallader Creek, a tributary of Bridge River that flows into the Fraser River. Steep mountains rise from 3300 ft. elevation above sea level at the creek to peaks and ridges at 8000 to 9000 ft. altitude. The lower slopes are heavily wooded while above 5000 ft. bare rocks, glaciers and snow-fields extend far above timber line. See Fig. 1. Story of the Bralorne The Lorne claim, staked in 1897, was one of the earliest lode locations in the Bridge River district. At that time it was 70 miles by steep and treacherous trail from the railway. For the next 15 years Arthur Noel, Will Haylmore and other local prospectors mined the small, irregular, oxidized quartz veins to a maximum depth of 200 ft., and treated the ore in arrastres and later a five-stamp mill. The total production to 1912 was only $55,000. Noel and associates later formed the Lorne Amalgamated Mines Co., which they worked in a desultory way until 1925. Increasing sulfide and arsenide content in the veins

Jan 1, 1935

Neighboring mines, like men who live in the same environment, often assume similar characteristics. In the Bridge River area of the Lillooet district in central British Columbia there is a remarkable exception to this rule. The Pioneer mine has a simple fissure over 3000 ft. long, with no faults of more than a few feet and with only minor variations in width; the Bralorne mine, 2½ miles away at the other end of the same intrusion, has developed one of the most intricate vein and fault systems in the West. Hinged faults displace the main vein for hundreds of feet, and sometimes become valuable veins themselves. The width of ore varies in a few yards from 2 to 60 ft. Changes in grade of ore are just as abrupt. The rocks that follow the veins or are cut by them often grade into one another or into the ore with no definite contacts. Although the complexity of the structure has left many problems unsolved, the development has indicated a fascinating geological pattern. The Bralorne is in the eastern portion of the Coast Range, 55 miles by spectacular mountain road from the Pacific Great Eastern Railway station of Bridge River. The adit tunnel runs easterly from Cadwallader Creek, a tributary of Bridge River that flows into the Fraser River. Steep mountains rise from 3300 ft. elevation above sea level at the creek to peaks and ridges at 8000 to 9000 ft. altitude. The lower slopes are heavily wooded while above 5000 ft. bare rocks, glaciers and snow-fields extend far above timber line. See Fig. 1. Story of the Bralorne The Lorne claim, staked in 1897, was one of the earliest lode locations in the Bridge River district. At that time it was 70 miles by steep and treacherous trail from the railway. For the next 15 years Arthur Noel, Will Haylmore and other local prospectors mined the small, irregular, oxidized quartz veins to a maximum depth of 200 ft., and treated the ore in arrastres and later a five-stamp mill. The total production to 1912 was only $55,000. Noel and associates later formed the Lorne Amalgamated Mines Co., which they worked in a desultory way until 1925. Increasing sulfide and arsenide content in the veins

Jan 1, 1935

By Ira B. Joralemon

Neighboring mines, like men who live in the same environment, often assume similar characteristics. In the Bridge River area of the Lillooet district in central British Columbia there is a remarkable exception to this rule. The Pioneer mine has a simple fissure over 3000 ft. long, with no faults of more than a few feet and with only minor variations in width; the Bralorne mine, 2½ miles away at the other end of the same intrusion, has developed one of the most intricate vein and fault systems in the West. Hinged faults displace the main vein for hundreds of feet, and sometimes become valuable veins themselves. The width of ore varies in a few yards from 2 to 60 ft. Changes in grade of ore are just as abrupt. The rocks that follow the veins or are cut by them often grade into one another or into the ore with no definite contacts. Although the complexity of the structure has left many problems unsolved, the development has indicated a fascinating geological pattern. The Bralorne is in the eastern portion of the Coast Range, 55 miles by spectacular mountain road from the Pacific Great Eastern Railway station of Bridge River. The adit tunnel runs easterly from Cadwallader Creek, a tributary of Bridge River that flows into the Fraser River. Steep mountains rise from 3300 ft. elevation above sea level at the creek to peaks and ridges at 8000 to 9000 ft. altitude. The lower slopes are heavily wooded while above 5000 ft. bare rocks, glaciers and snow-fields extend far above timber line. See Fig. 1. Story of the Bralorne The Lorne claim, staked in 1897, was one of the earliest lode locations in the Bridge River district. At that time it was 70 miles by steep and treacherous trail from the railway. For the next 15 years Arthur Noel, Will Haylmore and other local prospectors mined the small, irregular, oxidized quartz veins to a maximum depth of 200 ft., and treated the ore in arrastres and later a five-stamp mill. The total production to 1912 was only $55,000. Noel and associates later formed the Lorne Amalgamated Mines Co., which they worked in a desultory way until 1925. Increasing sulfide and arsenide content in the veins

Jan 1, 1935

By J. H. Bowden

The water-hoisting tanks herewith illustrated have been designed for removing large quantities of water from recently-flooded mines, through their hoisting-slopes, with rapidity proportional to the capabilities of the hoisting machinery available, the tanks being adaptable to slopes of small sectional areas and varying pitches. The following features may be of interest to those operating mines liable to be flooded. 1. The arrangement of doors on each tank by which it may be automatically filled by immersion at any point on the varying pitch of a slope, the water being retained while hoisting on the flat as well as on the steep pitches, and quickly and autoniatically discharged at the top. 2. The arrangement, in connection with the above-mentioned doors, of side-wheels over the rear wheeh of each tank and of sidedumping tracks at the top of the hoist, for the automatic emptying and quick return of the tank. 3. The arrangement of two or more tanks, one in front of the other, so as to give as large a capacity in a single hoist as the enginepower will permit, yet without making any tank too large for the sectional area of the slope, or of unwieldlp length, or of such a shape that it cannot easily pass over vertical curves; and without concentrating too much weight on any one pair of wheels or on any point of the track. The details of construction and method of operating are shown by the accompanying sketches (Figs. 1 and 2), and the following more detailed description. At the end of each tank is a large iron door of almost the full size of the end of the tank, opening inwards, so that when immersed the tanks fill almost instantly. To provide for holding the water while it is hoisted up flat pitches, a wooden door is attached to the front of each tank, opening outward. Each front door is attached to the

Jan 1, 1892

By Charles Camsell

MORE than one-third of all Canada is embraced in the federal domain known as the Northwest Territories. Its most northern point, Cape Columbia, on Ellesmere Island, is only 500 mi. from the Pole. It includes parts of the main physiographic divisions of the North American continent. In the West there is a strip of 30.000 sq. mi. lying in the Cordilleran region, where peaks in the Mackenzie Mountains rise as high as 8500 ft. East of this strip and extending roughly to a line through Great Bear and Great Slave lakes to the Arctic coast is a section of the interior plains. This section, known as the Mackenzie Lowlands, contains the great artery, the most striking feature of the Northwest Territories-the Mackenzie and Slave river waterway impressive in its width, almost two miles in places, and in it's navigability for 1357 miles without obstruction to the sea. Adjoining the Mackenzie Lowlands on the East is the greater portion of the mainland of the Territories, which, as well as a large share of the island area, is in the Canadian Shield.

Jan 1, 1937

By A. J. McEvily, R. C. Boettner, C. Laird

The processes leading to fatigue failure in the low-cycle range were studied to obtain an understanding of the basis of Coffin's law. Particular attention was paid to the manner of mack nucleation and to the determination of the portion of the total lifetime spent in crack propagation. It was observed that cracks are nucleated at surface notches meated during reversed plastic deformation, Principally at grain boundaries, and that crack growth occupies greater than 75 pct of the fatigue life. When inclusions are present, they are often the primary sites of crack initiation. From consideration of the incremental distances advanced by a crack in each cycle and of the lifetimes of different materials, it appears that the universality of Coffin's law arises from the similarity of crack-tip strain for a given applied strain amplitude, irrespecti7:e of material. STUDIES of low-cycle fatigue have been particularly rewarding in that a simple correlation between fatigue lifetime and plastic-strain range has been shown to exist. This empirical relationship takes the forml,2 Nner=C [1] where N is the number of cycles to failure, Er is the plastic-strain range defined as the total plastic strain per cycle (the sum of the tensile plastic strain plus the compressive plastic strain), n, the exponent, is a constant independent of the material to a first-order approximation and often has a value of about 0.5, and C is a constant which for a number of ductile and metallurgically stable materials is approximately 0.65 for fully reversed strain.3 This relationship has been shown to be valid for a wide variety of metals and alloys and is often referred to as Coffin's law. However, it is yet not clear why so many different metals and alloys exhibit the same over-all behavior in the low-cycle range. Less is known about the mechanisms of fatigue failure in the low-cycle range than in the high-cycle range, but it is expected that the processes would have much in common. For example, an important characteristic common to both high-and low-cycle ranges is that fatigue crack propagation can occupy a considerable portion of the total lifetime. This has been shown by Laird and smith4 by a count of the number of ripples present on the fracture surface of copper specimens, each ripple corresponding to one cycle of load. On the other hand, some marked differences have been noted. For example, in copper,5 nickel, and aluminum4 there is a greater tendency for grain boundary cracking to occur as the strain amplitude is increased. The purpose of the present work was to study further the processes leading to fatigue failure in the low-cycle range and to obtain an understanding of the basis for the validity of Coffin's law. Particular attention has been paid to the manner of crack initiation and to the determination of the portion of total lifetime spent in crack propagation. MATERIALS A number of metals and alloys were tested, although more attention was focused on a particular few, once general trends had become apparent. Alloys were selected so as to investigate the effects of crystal structure, number of phases, stacking-fault energy, and impurity content. The materials in this grouping were: high-purity copper OFHC copper 1100 aluminum (commercially pure) 70-30 brass (Cu-30 wt pct Zn)

Jan 1, 1965

By Boyd Guthrie, J. D. Lankford

A progress report on the oil-shale and shale-oil processing research program at the U. s. Bureau of Mines Oil-Shale Demonstration Plant. Legislation providing for the program and aims are briefly noted. The remoteness and rugged nature of the terrain at the plant site are important factors in construction and operations. Large-scale units now in operation are the crushing plant and two 40-ton N-T-U retorts. These are described in detail. Under construction are several retorting pilot plants and a 200 bbl per day refinery. The refineiy incorporates several types of thermal operation, three-stage low-temperature acid treating, doctor sweetening and rerunning. Data are presented on typical N-T-U retort runs. Yields of 90 to loo pct of assay are realized on 30 gal to the ton shale with a retort cycle time of 18 hr. Data also are presented showing a comparison of a Mid-Continent petroleum and N-T-U shale oil. This comparison indicates that shale oil has a high pour point, low API gravity, and contains about 0.8 pct sulphur and 2 pct nitrogen. The naphtha fraction contains 3 pct tar acids, 9 pct tar bases and jo pct olefins. The problems involved in refining shale oil into usable products are discussed in detail. Introduction The Bureau of Mines oil-shale program now under way at Rifle, Colo., was begun in July 1944 under the provisions of the Synthetic Liquid Fuels Act, which was passed in the spring of that year under the sponsorship of Senator Joseph C. O'Ma-honey of Wyoming and Congressman Jennings Randolph of West Virginia, aided by Michael W. Straus, former Assistant Secretary of the Interior, and others. The oil-shale plant is only a part of the Office of Synthetic Liquid Fuels, Bureau of Mines, which has under way projects to develop synthetic liquid fuels from coal and other solid materials at Pittsburgh and Bruceton, Pa., Morgantown, W. Va., Louisiana, Mo., as well as the Petroleum and Oil-Shale Experiment Station at Laramie, Wyo., and the oil-shale demonstration plant at Rifle. The oil-shale program is entirely experimental. It is not intended that oil will be produced in great quantities. Production will be limited to the volume obtained from plant-scale experimental operations, which will be kept to the minimum size needed to develop techniques and processes and to demonstrate costs. After the passage of the enabling act in the summer of 1944 a survey of the oil-shale resources of the Nation was made to determine the most suitable general area in which to establish the demonstration plant. The most suitable area was found to be in the Rifle-De Bequearea in Garfield County, western Colorado. Bureau of Mines field parties covered this entire area thoroughly

Jan 1, 1949

By M. C. Chang, J. Dasher

The Crucible mine in Pennsylvania, operating on Pittsburgh seam coal, is rated at 5000 tpd. The washing plant, built in 1943, is rated at about 400 tph, using hydroseparator boxes to wash the coarse coal (4 x 5/16 in.) and hydrotator units for the fine coal (5/16 x 0). It is generally acknowledged that gravity concentration equipment cannot be used efficiently to bene-ficiate coal finer than about 65 mesh. Before the present flotation circuit was installed, Crucible recovered its fine coal slurry, predominantly —24 mesh material, by passing it through a battery of five 14-in. and one hundred and ten 3-in. Hey1 & Patterson cyclones in parallel with a 75-ft Dorr thickener. About two thirds went to the cyclones and one third to the thickener. Underflows from cyclones and thickener were filtered, respectively, in one 12-disk Eimco and two 4-disk Oliver filters fitted with stainless steel cloth. The resulting cakes were added to the coarse metallurgical coal. The filtrates, overflow from the 3-in. cyclones, and thickener overflow were recycled to the coarse coal plant. The three major problems encountered in this system became acute when the mine switched from track-mounted machinery to the more economical off-track equipment. The quality and uniformity of product declined, too much slime accumulated in the circuit, and waste pond disposal became highly impracticable. Lowering of Quality and Uniformity: Since the filter cake was not beneficiated in any way, addition of this material, which contained about 18 pct ash. would certainly lower the quality of metallurgical coal. Difficulties of handling the high-ash, high-moisture cake were compounded by the lack of adequate blending facilities at the mine, making it impossible to maintain uniform feed for the coke ovens. For a two-month test period, to verify the source of trouble, all filter cake was excluded from the metallurgical coal. The excluded filter cake was stocked in the yard. Slime Buildup: The moisture retained in the coarse coal products and the filter cake provided daily the only means of slime bleed from the circuit. As this bleed was not enough to offset the incoming fines in the raw coal feed, there was excessive buildup of slimes. To operate at all, it was necessary to purge the system each weekend by pumping all the solids from the thickener to a waste pond. The slimes built up during the week progressively increased the apparent viscosity and density of the circulating plant water, so that hydroseparators and hydrotator units had to be constantly adjusted. Uniformity, yield, and quality of the metallurgical coal suffered in consequence, and the filter cake ash and moisture contents increased from Monday to Friday. Limited Waste Disposal: Location of the plant does not permit unlimited waste pond area. Maintenance of a waste pond for the purpose of emptying the thickener during weekends became a costly burden that could not be tolerated. HOW THE PROBLEMS WERE SOLVED The flowsheet (Fig. 1) chosen to overcome these difficulties is considered the one most economical to install and operate. In a preliminary change made before the flotation circuit was installed, the cyclones and thickener were first operated in series, the overflow from the 3-in. cyclones, after flocculation, being discharged into the thickener and the thick-

Jan 1, 1960

By Stephen G. Dardaganian

Pore volume compresibilitieu measured in the laborutory on core .samples are reported for typical reservoir .sarrrl.rtorres at reservoir pressure. These cornpressibilities ore different for each reseriloir sample and cannot be correlated to porosity. The compressihilities are a1so functions of presslire. In recent years several authors have pointed out the importance of including pore volume compressibility of the reservoir rock in certain reservoir engineering calculations. Hall' showed that in calculating the hydrocarbon volume of an undersaturated reservoir from the production per unit change in reservoir pressure, the neglect of rock compressibility could, in the extreme case of low porosity rock, lead to results in error by a factor of two. Hawkinsl' and Hobson and Mrosovsky showed that both rock and interstitial water compressibilities must be included to achieve satisfactory accuracy in this calculation. Although rock compressibility is an important reservoir property in these calculations, very few data are available. Hall' made compressibility measurements on a few samples in a small pressure range. No other direct pore volume compressibility measurements have been reported. Geertsma' discussed the elasticity of reservoir rock but did not present any new data. In this paper, rock compressibilities suitable for reservoir calculations are reported for a variety of sandstones typical of U. S. reservoirs. The measurements were made through a range of pressures which is also typical of reservoirs. EXPERIMENTAL PROCEDURE Plugs 1 in. in diameter and 2- to 3-in. long were diamond drilled, 14 from cores from seven oil-bearing or potentially oil-bearing sandstone, one from a quarried sandstone, and another from a shallow, oil-free, pure orthoquartzite. The plugs were extracted in toluene, vacuum dried, and then weighed. The plugs were then saturated with kerosene and reweighed. This gave pore volume. They were then again extracted in toluene. vacuum dried, and jacketed in 0.004-in. thick copper foil. A short length of -in high pressure tubing led from the jacket. The jacketed sample was then saturated with kerosene and placed in the hydraulic pressure cell as shown in Fig. 1. Movement of the mercury slug showed the change in pore volume of the sample under a given pressure change. Temperature was about 72" F for all measurements. Before taking any measurements, the external pressure on the sample was raised to 10,000 psig and kept there for several hours. This formed the thin copper jacket around the plug. 7-he pressure was then removed and the sample left at least overnight, during which time it recovered its original pore volume. An external pressure of 12,000 psig was then applied and held constant. The change in pore volume was noted as the internal pressure was raised in 1,000 psig increments to 10,000 psig. The internal pressure was then reduced to zero, again noting pore volume changes,

By C. R. Dodson, D. Goodwill, E. H. Mayer

The paper summarizes the historical background of the pressure-volume-temperature analyses of reservoir fluids, the errors involved in both the sampling and testing of reservoir fluids, the type of information required of a PVT determination, and the field conditions that limit the application of any one analysis. Particular emphasis is placed on the necessity for approximating as closely as possible the liberation sequence occurring in the producing formation, flow string, and surface separators. A combined differential and flash or "composite" liberation is suggested as the best means of approximating this liberation sequence. HISTORICAL BACKGROUND Petroleum reservoir engineering commonly is considered to be one of the newest fields of petroleum science, yet much work of a theoretical and intuitive nature was done many years before the modern techniques of reservoir analyses were developed. The period 1910-1924 saw considerable work in the field of reservoir behavior done by the U. S. Bureau of Mines. This work:.' although entirely theoretical, pointed out the importance of gas in the recovery of oil from the reservoir. The statement by J. 0. Lewis that 20 per cent or less of the oil originally in place in a pool was recovered from the ground under uncurtailed production conditions caused some operators to re-examine and modify their production methods. However, though these works showed methods of production that have subsequently resulted in greater oil recoveries, they in general went unnoticed, even though there was a fear that the nation's petroleum resources were being exhausted. The period 1924-1933 saw the industry take considerably more interest in reservoir behavior because of an unfounded fear of its inability to replace oil reserves, the possibility of government regulation, and the energy of one man, Henry L. Doherty. Doherty aroused heated discussions in the industry concerning conservation. To prove or disprove his theories the first experimental work on the reservoir behavior of petroleum was undertaken. The papers of Dow and Calkin,' Beecher and Parkhurst," and Mills and Heitheckere are classics although their experimental procedures were crude. These papers proved that the properties of petroleum in the reservoir are quite dissimilar to the properties measured at the well head. Gas dissolved in the oil phase was recognized as having considerable importance as had been predicted by the earlier theorists. Slightly later Miller and his co-workers assembled the first text correlating all the known data on the reservoir behavior of petroleum and used, these data to show the economic value of conservation. Quantitative application of pressure-volume-temperature analyses of reservoir fluids was given in the paper of Coleman, Wilde, and Moore"; this work showed that with sufficient laboratory and production data prediction of reservoir behavior was possible. The refined sampling and labora-

Jan 1, 1953

By W. R. Seyfried

The problem of extracting alumina from clay and low-grade bauxites has been the subject of considerable interest for some time. The basic reason, of course, lies in the fact that known reserves of high-grade bauxite are not inexhaustible and that the present commercial process cannot successfully cope with low-grade bauxites or clay. Ultimately it may be necessary to use these poorer raw materials for all commercial operations. An unprecedented demand for aluminum during the war emergency and the constantly threatened shortage of imported bauxite caused the United States Government to take an active role in this problem. Through the National Academy of Sciences, the War Production Board and the Defense Plant Corporation, it investigated processes and finally selected four to be used in the construction and operation of four experimental plants. Each plant was to be designed in such a way as to facilitate its incorporation into a larger commercial plant should the need arise. The Chemical Construction Corporation process, or "Chemico" ammonium sulphate process as it is better known, was one of the four selected. The extensive literature and patents on record before the war generally follow one of two process-types depending upon the extracting reagent used. One group uses an acid reagent, the other an alkali. The Chemico process uses an acid reagent. For those interested in other processes described in literature, there is a short bibliography at the end of this paper. The basic steps of all acid extraction processes are: (I) to make the aluminum silicates acid soluble, (2) to separate the released alumina from impurities and insoluble gangue, and (3) to recover the reagent for re-use. The Process as Planned In April 1941, a group of chemists and engineers of the Chemical Construction Corp. became interested in the problem of extracting alumina from clays and low-grade bauxites and, under the leadership of Mr. Blakeslee Barnes, Vice President and General Manager of the company, first drafted a process in July of that year—five months prior to Pearl Harbor. The work continued in our research laboratories and with a small pilot plant. By June 1943, the work had progressed to a point where it was possible to apply for a patent on the process which was U.S. patent 2,405,426, granted August 6, 1946. Immediately prior to the development of the Salem plant, the process was envisaged to be as follows: I. The first step was to make the aluminum silicates acid soluble. It was planned: (a) Clay or lour-grade bauxite would be roasted at 700 to 800°C (1292° to 1472°F). (b) The roasted ore would then be leached with hot aqueous ammonium bi-sulphate to form a slurry. In this way the

Jan 1, 1949

By W. R. Seyfried

THE problem of extracting alumina from clay and low-grade bauxites has been the subject of considerable interest for some time. The basic reason, of course, lies in the fact that known reserves of high-grade bauxite are not inexhaustible and that the present commercial process cannot successfully cope with low-grade bauxites or clay. Ultimately it may be necessary to use these poorer raw materials for all commercial operations. An unprecedented demand for aluminum during the war emergency and the constantly threatened shortage of imported bauxite caused the United States Government to take an active role in this problem. Through the National Academy of Sciences, the War Production Board and the Defense Plant Corporation, it investigated processes and finally selected four to be used in the construction and operation of four experimental plants. Each plant was to be designed in such a way as to facilitate its incorporation into a larger commercial plant should the need arise. The Chemical Construction Corporation process, or "Chemico" ammonium sulphate process as it is better known, was one of the four selected. The extensive literature and patents on record before the war generally follow one of two process-types depending upon the extracting reagent used. One group uses an acid reagent, the other an alkali. The Chemico process uses an acid reagent. For those interested in other processes described in literature, there is a short bibliography at the end of this paper. The basic steps of all acid extraction processes are: (I) to make the aluminum silicates acid soluble, (2) to separate the released alumina from impurities and insoluble gangue, and (3) to recover the reagent for re-use. THE PROCESS AS PLANNED In April 1941, a group of chemists and engineers of the Chemical Construction Corp. became interested in the problem of extracting alumina from clays and low-grade bauxites and, under the leadership of Mr. Blakeslee Barnes, Vice President and General Manager of the Company, first drafted a process in July of that year-five months prior to Pearl Harbor. The work continued in our research laboratories and with a small pilot plant. By June 1943, the work had progressed to a point where it was possible to apply for a patent on the process which was U.S. patent 2,405,426, granted August 6, 1946. Immediately prior to the development of the Salem plant, the process was envisaged to be as follows: I. The first step was to make the aluminum silicates acid soluble. It was planned: (a) Clay or low-grade bauxite would be roasted at 700 to 800°C (1292° to 1472°F), (b) The roasted ore would then be leached with hot aqueous ammonium bisulphate to form a slurry. In this way the

Jan 1, 1947

By John P. Bryant

Plant nutrients are obtained by plants from both the air and the soil. Carbon dioxide, a gaseous form of carbon and oxygen, supplies the carbon which usually makes up 50% or more of plant structure. Plants are capable of absorbing carbon dioxide directly from the air. Most of this nutrient comes from the air, although some carbon dioxide is absorbed by soil water and taken into the plant as liquid. Growing plants use more water than any other substance. Plant nutrients in the soil dissolve in soil water; soil water entering the plant carries nutrients into the plant structure. Water is then given off into the air as the plant breathes or transpires. The inorganic or mineral portion of the nutrients which plants require comes from the soil. Inorganic or mineral composition of plants is usually less than 5% of their weight, and this mineral requirement, usually lacking in the soil, must be provided by fertilizers. Proper fertilization of a soil to improve its mineral level and productivity is the basis for the fertilizer industry (Thomas, 1960). There are 13 essential plant nutrients which often must be added to soils or plants and are generally considered as fertilizer minerals. These nutrients are divided into the categories: primary minerals (nitrogen, phosphorus, potassium); secondary minerals (calcium, magnesium, sulfur); and micro or trace minerals (boron, iron, manganese, copper, zinc, molybdenum, chlorine). Further, cobalt is often added to fertilizers. Although it is not considered to be an essential plant nutrient, it is essential to animal health and is often applied to forages as a fertilizer constituent. One point of major significance to the fertilizer industry is that not all nutrient carriers supply that nutrient in a chemical form which will be available to the plant. Thus, a product which may be considered a fertilizer mineral may require substantial processing or treatment before it becomes useful as a nutrient carrier. Fertilizer Industry Scope Until about 1900 demands for higher crop yields were met simply by bringing new agricultural lands into cultivation. Since that time great progress has been made in increasing yields through fertilization and improved varieties and cultural practices. The importance of the fertilizer industry to the economy and welfare of the U.S. is widely recognized. [Fig. 1] illustrates the relationship of lime and fertilizers to crop yields. In terms of tons of fertilizer products, the growth of the industry has been phenomenal, particularly between 1950 and 1970. Table 1 shows the increase in fertilizer usage. Primary Plant Nutrients in Fertilizers Primary minerals (nitrogen, phosphorus, potassium) are designated as such because of their significance to plant growth. Practically all soils are deficient in both nitrogen and phosphorus, and most of them are also deficient in potassium. Consequently, these nutrients

Jan 1, 1975

By L. C. De Jong, J. F. Shirley, M. L. Campbell

At the Southern Peru Copper operation in Toque-pala, Peru, a new process flowsheet for the recovery of byproduct molybdenite has proved successful in dealing with complex and highly variable ores. This paper describes the process and the functions of each of the chemicals used. The Toquepala concentrator of the Southern Peru Copper Corp., located approximately 720 miles southeast of Lima near the Chilean border, processes a daily 36,500 tons of ore containing between 0.50 and 3.00% copper. The molybdenite content in the ore also varies greatly ranging from essentially nothing to as high as 0.15%. The 1966 yearly averages were approximately 1.20% copper and 0.03% molybdenite. The Toquepala porphyry deposit is a mushroom-shaped ore body consisting of a flat-lying enriched zone of predominant chalcocite with a stem-like extension of hypogene chalcopyrite ore in depth within and around a large breccia pipe.1 The underlying chalcopyrite ore has not been reached; however, due to the presence of a major post orebody fault, predominantly chalcopyrite ore is present in the north side of the pit. Most of the molybdenite occurs either as small, fine granular, pulverulent masses in vugs or empty voids of breccia, or as thin foliated masses and narrow thread-like filling in rock joints and fractures. The normal occurrence of quartz gangue with the molybdenite gives some basis for correlating the molybdenite mineralization to some later periods of silicification. On April 18, 1962, the molybdenite recovery plant at Toquepala went on stream, approximately 27 months after the copper concentrator had been in production. The plant was designed and built by Southern Peru Copper Corp.'s engineering and mechanical departments. The basic method chosen for separating the molybdenite from the copper concentrate was the sodium hypochlorite-sodium ferrocyan-ide process. The selection of this process was based on the results of an extensive testing program performed by the Colorado School of Mines Research Foundation, Inc. and the economic conditions of the area. The originally designed process could never be fully implemented due to a lack of sodium hypo-chlorite and has had to be continually modified to satisfy the requirements of the kaleidoscope of ores from the mine. The three basic problems that plague the operation of any molybdenite recovery plant are all present at Toquepala in large measure. Both the quantity of plant feed and the quantity of molybdenite contained in the plant feed are continuously changing. Even more detrimental to an efficient operation is the fact that the copper mineralization in the feed frequently changes once in every 24 hours and occasionally once a shift. From the point of view of the molyb-

Jan 1, 1968

By A. Madrazo

The Standing-Katz method for predicting liquid densities of reservoir fluids has been tested using experimental data of 154 bottom-hole or recombined reservoir fluid samples. New pressure- and temperature-correction curves for the Standing-Katz type correlation are presented which improve the accuracy of prediction. INTRODUCTION The present study was undertaken to investigate the known methods of determining liquid densities and to select one of them which might yield a better correlation if additional data were employed. An appropriate correlation would incorporate the following characteristics: (1) ease of handling in the computations, (2) results within engineering accuracy and (3) data easily accessible. After careful investigation of the different methods, the Standing-Katz correlation1 appeared to have these characteristics. The Standing-Katz correlation for liquid densities of hydrocarbon systems is based upon limited data. The original work, which employs apparent densities for methane and ethane, was based on data of 15 saturated crude oils in equilibrium with natural gas. Therefore, a test of the correlation using additional experimental data would serve either to validate the Standing-Katz correlation or to form a basis for corrections if such were necessary. PROCEDURE AND GRAPHICAL SOLUTION The data of 154 bottom-hole or recombined reservoir fluid samples were employed to calculate the densities at 14.7 psia and 60°F by the method described in Table 1. Volume contributions for methane and ethane were assigned from the pseudo liquid density plot (Fig. I), but volume contributions for N2, CO2 and HzS were not considered. The densities computed at reference conditions of 14.7 psia and 60°F were then elevated to their respective temperatures and pressures by the use of the correction curves proposed by Standing.' The percentage differences between the experimental values and the calculated values were determined; these samples were grouped into temperature, pressure and density ranges to determine a possible trend. It appeared that, at temperatures above 160°F, the calculated density values were consistently larger than the experimental density values; however, no obvious trend was found for the density and pressure ranges. There is a relationship between the pressure-correction and temperature-correction curves. This relationship, embodied in the temperature-correction curve, can be expressed as follows. The experimental densities of 125 samples above their bubble points were known. From these isothermal data, it was possible to determine an experimental-density difference between two pressures; and (from Fig. 2*), a calculated density difference between the same two pressures was determined. The relative effect of temperature must be considered in the calculated-density values. The effect of temperature can be determined by entering Fig. 3* at the two densities in consideration and obtaining the change in density at constant temperature. This change, or delta density, must be added