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By Donald L. Katz, Marshall B. Standing

Density data are reported on 16 saturated hydrocarbon vapors at Pressures ranging from 1000 to 8220 Ib. per sq. in. and at temperatures ranging from 35° to 250°F. These data have been used to extend the compressibility-factor chart for natural gases up to 10,000 lb. per sq. in. The relatively large quantity of high-boiling constituents present in high-pressure vapors in equilibrium with crude oils makes it necessary to include in the analysis of the gas the molecular weight, density, and possibly boiling range of the heptanes and heavier fraction. Relationships have been presented by which the density of gases may be obtained directly from the temperature, pressure, and gas gravity provided the gases have a common source or are similar in composition. Introduction The densities of natural gases are necessary in many engineering in in petroleum production and utilization, Gas reserves, changes in reservoir pressure, gradients in gas wells, metering of gases, pipeline flow, and compression of gases are typical problems requiring the density of the gas. A decade ago, engineering computations used ideal gas laws with deviations up to 500 Ib. per sq. in.4 Recent discoveries of pools having Pressures UP to 7500 lb. Per sq. in., and installation of pressure-maintenance and recycling plants, have increased the need for data On gas density at high pressures. Methods of Computation The accepted method of computing the density or specific volume of natural gases is the use of the ideal gas law corrected by a compressibility factor. The method proposed by Kay7 of correlating compressibility factors for gaseous mixtures on pseudocritical properties5 appears to be satisfactory for natural gases.2 The meth-me-compressibility factor has been shown to deviate systematically from the behavior of natural gases2 and a chart giving these corrected factors is available. A method of computing specific volume of gaseous mixtures from partial molal volumes has been reported by sage and Lacey.8 Complete data for the computation are not yet available for all hydrocarbon gases. Most- of the reported data on gas densities have been in the single-phase region removed from the dew point or saturation condition. Since most gases in the reservoir Or while on contact with liquid '''ring flow are saturated, the determination of densities under conditions of saturation is particularly important. Although there is no reason to believe that the saturated gases differ in behavior from those consider. ably removed from their dew points, the usual experimental determinations find difficulty on approaching the dew-point conditions, This paper reports the density of I6 saturated gases in equilibrium with crude oils. The relationships developed to compute the density of gases to high pressure' have been modified and enlarged. A simpli-fied method of obtaining gas density is presented in the Form of charts, which apply for specific groups of gases.

Jan 1, 1942

By E. H. Burdick

The difficulties inherent in table concentration operations as applied to gold, silver, lead and zinc ores, are accentuated in the scheelite mill, which has a flowsheet that is similar in general principles. The narrow "spread" in the specific gravity between scheelite and the usual gangue in which it occurs often makes its clean separation extremely difficult and in some cases impracticable. The problem is further complicated by the extreme friability of the mineral and its inordinate tendency to "slime," particularly where fine grinding is necessary and wet grinding methods are employed. The physical aspect of the occurrence of scheelite in the ores, the kind and character of the rock in which the mineral is present, its hardness, friability and the specific gravity of its constituents, as well as like characteristics of the associated minerals— pyrite, pyrrhotite, sphalerite, and others, all have a bearing on the successful milling of crude ores and the production of a concentrate that is marketable with minimum price penalty or none at all. Most tungsten deposits are considered low grade when the limiting factor of low percentage recovery by gravity methods is borne in mind. The great majority of deposits developed or in process of development carry from 0.4 to 1.0 per cent tungstic oxide. Ore carrying I per cent is considered good grade; 0.7 to 0.8 per cent, fair, and below that figure, low grade. Steady mill feed averaging upward of I .o per cent WO3 is exceptional. Inasmuch as buying specifications demand a 60 per cent W03 content, the mineral content of the ores as mined must be concentrated to at least that degree. A few companies have constructed chemical plants for the treatment of their complex concentrates and low-grade flotation product, but the smaller operator must rely on table concentration, borrowing the tools and to a large extent the methods of his predecessors in the gold, silver, lead and zinc mills. Whether these are the best tools and methods that can be devised is an open question. Except in rare instances, table concentration, however carefully conducted, does not yield a satisfactory final recovery of the mineral content in headings as indicated by chemical determinations of tungstic oxide content. A saving of 60 to 65 per cent is considered fair, and an average 80 per cent recovery, exceptional. Each scheelite ore body is a separate problem. Details of handling that give best results in one case may not be successfully operative at a property on the same contact zone and but a short distance removed. Supplementary treatment of tailings by flotation may be successful in producing a low-grade concentrate of around 15 per cent W03, which is adapted to further treatment chemically at a given property and entirely unsuccessful at another. This problem constitutes another of the unanswered questions. The following paragraphs relate solely to the beneficiation of scheelite ores by table concentration and supplementary methods.

Jan 1, 1943

By William T. Schneider, Taylor Cole

Drilling in West Texas during 1941 was more active than in any year since 1937, a total of 2325 wells having been drilled. Pre-Permian exploration was the greatest in the history of the area; 106 wells tested pre-Permian formations during the year. Wildcatting reached the peak since 1937, with 135 wildcats, of which 20 per cent were producers. The wells were drilled to a greater average depth than in any previous year. Slim-hole drilling was the common practice, using drilling equipment that is largely portable. Because of deeper drilling, more attention was paid to mud fluids, especially the use of materials to reduce water filtration. There has been slight improvement in the protection of the pay horizons while drilling by the use of reverse circulation, and drilling-in with oil as well as low water-filtration muds. The practice of setting and cementing the oil strings through the producing formation and perforating opposite the pay zones has increased in the fields producing from sands. It is doubtful whether this practice is of unusual value in dolomitic limestone fields. There have been few if any technological improvements in obtaining necessary information on the pay sections penetrated, by coring, core analyses, better sampling, and more detailed drilling time. However, more operators are beginning to realize the necessity of good samples. For a proper study of the reservoirs in West Texas, it is essential that better samples be obtained, that more core analyses be run, and that better methods of obtaining drilling time be initiated. It should be noted that increased drilling speeds and slim-hole drilling have tended to reduce coring and core recovery and have not aided in obtaining good subsurface samples. In fact, fast drilling speeds and slim-hole drilling have reduced the cost of drilling operations, but with the sacrifice of much needed subsurface information. Larger quantities of slower-reacting acid are being used per well. There has been improvement in shooting, in that a greater number of quarts per foot have been used and an attempt has been made to concentrate the shots opposite the pay zone. The use of mud logging to determine the characteristics of the pay section increased considerably over the year 1940. There has been a slight increase in obtaining reservoir information in the new fields, such as bottom-hole sampling, bottom-hole pressures, and records of gas, oil, and water withdrawals. However, there is great need for more data on these subjects, particularly accurate information regarding gas and water volumes. There are three repressuring projects and a fourth is nearly ready for operation in the Kermit field. There is one repressur-ing project in the Payton field and one in the North Ward field. So far, the gas-injection projects have not shown very impressive results. As yet, there are no water-flooding projects or water-disposal projects in West Texas. Not including gathering lines within the fields, 222 miles of feeder pipe lines were

Jan 1, 1942

By A. D. Dorenfeld

Factorial design is a mathematical method of drawing valid conclusions from a series of tests made in a predetermined pattern. It is applied to flotation ore testing using, in this case, five variables, each varied twice, requiring a total of 32 tests. Representative conclusions are checked by repeat testing. THE factorial design method of testing is particu-J- larly applicable to mill-scale plant tests because 1—the conclusions take into consideration all variabilities of the plant, 2—there are no subjective guesses as to the conclusions, 3—the number of tests necessary to check large numbers of variables are at a minimum, and 4—interactions between variables can be discerned. It is equally applicable to laboratory testing because once the variables to be investigated have been decided upon, as well as the number of levels for each variable, a well-trained assistant can run the tests, since the test work follows a predetermined mathematical pattern, leaving the conclusions to be found by the person in charge. The conclusion takes into consideration all errors of the tests. To illustrate the use of factorial design, a sample of copper porphyry ore was tested, the copper content of the batches not being uniform. Five variables were investigated, each at two levels, requiring only 32 tests. After suitable arithmetical analysis, conclusions for copper recovery and concentrate grade are arrived at. Four cases of these conclusions are checked by repeat testing. Testing Methods Reproducibility of flotation tests varies widely, depending on the experimenter, the process, the equipment, and probably a host of unknown and perhaps interacting variables. If the reproducibility of tests is good, let us say to 0.2 pct recovery of a certain metal, and the minimum difference between tests upon the variation of the interested variables is, say 1 pct, then simple averaging and inspection is ample in interpreting results. However, often such a happy situation is not the case. This is particularly true in mill-scale operations where the ores are variable, and a host of minor operating fluctuations common to most milling, and familiar to all mill operators, is the normal state of affairs. Yet, mill scale tests are run, the results averaged, and conclusions drawn therefrom. The trustworthiness of such results should be measured by comparison to the experimental error—the measure of the degree of reproducibility of the results. This comparison is a test of significance. Thus, if daily results of recoveries average 80.0 pct, and a spread of 78.0 pct to 82.0 pct, is recorded, then, clearly, on changing mill operations, an 81 pct recovery cannot be construed as significant by using averages, since it is well within the previous test limits. By using rigorous statistical tests of significance, conclusions arrived at by inspection or simple averaging may be shown to be based on inadequate evidence or even wrong. In any event, a plant super-

Jan 1, 1952

By I. J. Logan, Warren L. Baker

By 1950 or soon thereafter facilities will be available in foreign countries for the production, transportation, and refining of about 4,305,000 bbl per day of crude oil—a volume not far short of current United States output. This is indicated by announced plans for foreign expansion, - some of the work being already under way. The projected potential production is about 1,500,000 bbl per day or 50 pct above the record-setting foreign production of 2,810,000 bbl daily in 1946. The scheduled new foreign facilities are equivalent to almost one third of the present facilities of the United States. Fears that so much additional foreign oil may flood world markets and disrupt the domestic industry of the United States are not justified. The projected foreign expansion apparently has been planned on a sound business basis, with careful consideration of the world's actual need for all the projected additional production. Materially increased world demand for petroleum promises to absorb the increased supplies without ill effect upon the domestic industry. Even by applying conservative estimates of both foreign and domestic demand, it is indicated that world requirements can absorb the projected larger foreign output and still permit continued increase in United States production. World demand would have to increase only 5.7 pct per year in the 1947 to 1950 period to absorb the prospective supply. Such an increase may be conservatively projected, in view of past and current trends. Introduction Recent announcements of plans for expanding petroleum facilities in the Middle East and Venezuela foreshadow an unusually sharp increase in foreign production in the immediate future. Therefore, the next few years will bring far-reaching changes in world petroleum affairs, with foreign petroleum production and other activities assuming much greater importance than formerly. Tabulation of figures on development already under way or planned indicates that in the next several years facilities will be available for producing, transporting and refining twice the prewar production of foreign fields and about 50 pct or nearly 1,500,000 bbl a day above their record-level output of 1946. To say that foreign fields may be producing such an enlarged quantity by 1950 is, of course, a statement of great significance to everyone connected .with the oil industry and especially to those of the American petroleum industry. A production of 1,500,000 bbl daily is equal to the combined yield of the states of Oklahoma, Kansas, Illinois, Louisiana, Arkansas, Mississippi and New Mexico. This means that within the next several years foreign petroleum facilities will undergo a new expansion equivalent to one third of the present facilities of the United States. To think of such an expansion in foreign production is to raise at this meeting the question of what this prospective foreign development means for the United States, the American petroleum industry in general, and the American engineer and technologist in particular. It is only logical to question whether or

Jan 1, 1948

By Taylor Cole, William T. Schneider

Drilling in West Texas during 1941 was more active than in any year since 1937, a total of 2325 wells having been drilled. Pre-Permian exploration was the greatest in the history of the area; 106 wells tested pre-Permian formations during the year. Wildcatting reached the peak since 1937, with 135 wildcats, of which 20 per cent were producers. The wells were drilled to a greater average depth than in any previous year. Slim-hole drilling was the common practice, using drilling equipment that is largely portable. Because of deeper drilling, more attention was paid to mud fluids, especially the use of materials to reduce water filtration. There has been slight improvement in the protection of the pay horizons while drilling by the use of reverse circulation, and drilling-in with oil as well as low water-filtration muds. The practice of setting and cementing the oil strings through the producing formation and perforating opposite the pay zones has increased in the fields producing from sands. It is doubtful whether this practice is of unusual value in dolomitic limestone fields. There have been few if any technological improvements in obtaining necessary information on the pay sections penetrated, by coring, core analyses, better sampling, and more detailed drilling time. However, more operators are beginning to realize the necessity of good samples. For a proper study of the reservoirs in West Texas, it is essential that better samples be obtained, that more core analyses be run, and that better methods of obtaining drilling time be initiated. It should be noted that increased drilling speeds and slim-hole drilling have tended to reduce coring and core recovery and have not aided in obtaining good subsurface samples. In fact, fast drilling speeds and slim-hole drilling have reduced the cost of drilling operations, but with the sacrifice of much needed subsurface information. Larger quantities of slower-reacting acid are being used per well. There has been improvement in shooting, in that a greater number of quarts per foot have been used and an attempt has been made to concentrate the shots opposite the pay zone. The use of mud logging to determine the characteristics of the pay section increased considerably over the year 1940. There has been a slight increase in obtaining reservoir information in the new fields, such as bottom-hole sampling, bottom-hole pressures, and records of gas, oil, and water withdrawals. However, there is great need for more data on these subjects, particularly accurate information regarding gas and water volumes. There are three repressuring projects and a fourth is nearly ready for operation in the Kermit field. There is one repressur-ing project in the Payton field and one in the North Ward field. So far, the gas-injection projects have not shown very impressive results. As yet, there are no water-flooding projects or water-disposal projects in West Texas. Not including gathering lines within the fields, 222 miles of feeder pipe lines were

Jan 1, 1942

By Marshall B. Standing, Donald L. Katz

DENSITY data are reported on 16 saturated hydrocarbon vapors at pressures ranging from 1000 to 8220 lb. per sq. in. and at temperatures ranging from 35° to 250°F. These data have been used to extend the compressibility-factor chart for natural gases up to 10,000 lb. per sq. in. The relatively large quantity of high-boiling constituents present in high-pressure vapors in equilibrium with crude oils makes it necessary to include in the analysis of the gas the molecular weight, density, and possibly boiling range of the heptanes and heavier fraction. Relationships have been presented by which the density of gases may be obtained directly from the temperature, pressure, and gas gravity provided the gases have a common source or are similar in composition. INTRODUCTION The densities of natural gases are necessary in many engineering computations in petroleum production and utilization. Gas reserves, changes in reservoir pressure, gradients in gas wells, metering of gases, pipeline flow, and compression of gases are typical problems requiring the density of the gas. A decade ago, engineering computations used ideal gas laws with deviations up to 500 lb. per sq. in.4 Recent discoveries of pools having pressures up to 7500 lb. per sq. in., and installation of pressure-maintenance and recycling plants, have increased the need for data on gas density at high pressures. METHODS OF COMPUTATION The accepted method of computing the density or specific volume of natural gases is the use of the ideal gas law corrected by a compressibility factor. The method proposed by Kay7 of correlating compressibility factors for gaseous mixtures on pseudocritical properties5 appears to be satisfactory for natural gases.2 The methane-compressibility factor has been shown to deviate systematically from the behavior of natural gases2 and a chart giving these corrected factors is available. A method of computing specific volume of gaseous mixtures from partial molal volumes has been reported by Sage and Lacey.8 Complete data for the computation are not yet available for all hydrocarbon gases. Most of the reported data on gas densities have been in the single-phase region removed from the dew point or saturation condition. Since most gases in the reservoir or while on contact with liquid during flow are saturated, the determination of densities under conditions of saturation is particularly important. Although there is no reason to believe that the saturated gases differ in behavior from those considerably removed from their dew points, the usual experimental determinations find difficulty on approaching the dew-point conditions. This paper reports the density of 16 saturated gases in equilibrium with crude oils. The relationships developed to compute the density of gases to high pressure' have been modified and enlarged. A simplified method of obtaining gas density is presented in the form of charts, which apply for specific groups of gases.

Jan 1, 1941

By Warren L. Baker, I. J. Logan

By 1950 or soon thereafter facilities will be available in foreign countries for the production, transportation, and refining of about 4,305,000 bbl per day of crude oil—a volume not far short of current United States output. This is indicated by announced plans for foreign expansion, - some of the work being already under way. The projected potential production is about 1,500,000 bbl per day or 50 pct above the record-setting foreign production of 2,810,000 bbl daily in 1946. The scheduled new foreign facilities are equivalent to almost one third of the present facilities of the United States. Fears that so much additional foreign oil may flood world markets and disrupt the domestic industry of the United States are not justified. The projected foreign expansion apparently has been planned on a sound business basis, with careful consideration of the world's actual need for all the projected additional production. Materially increased world demand for petroleum promises to absorb the increased supplies without ill effect upon the domestic industry. Even by applying conservative estimates of both foreign and domestic demand, it is indicated that world requirements can absorb the projected larger foreign output and still permit continued increase in United States production. World demand would have to increase only 5.7 pct per year in the 1947 to 1950 period to absorb the prospective supply. Such an increase may be conservatively projected, in view of past and current trends. Introduction Recent announcements of plans for expanding petroleum facilities in the Middle East and Venezuela foreshadow an unusually sharp increase in foreign production in the immediate future. Therefore, the next few years will bring far-reaching changes in world petroleum affairs, with foreign petroleum production and other activities assuming much greater importance than formerly. Tabulation of figures on development already under way or planned indicates that in the next several years facilities will be available for producing, transporting and refining twice the prewar production of foreign fields and about 50 pct or nearly 1,500,000 bbl a day above their record-level output of 1946. To say that foreign fields may be producing such an enlarged quantity by 1950 is, of course, a statement of great significance to everyone connected .with the oil industry and especially to those of the American petroleum industry. A production of 1,500,000 bbl daily is equal to the combined yield of the states of Oklahoma, Kansas, Illinois, Louisiana, Arkansas, Mississippi and New Mexico. This means that within the next several years foreign petroleum facilities will undergo a new expansion equivalent to one third of the present facilities of the United States. To think of such an expansion in foreign production is to raise at this meeting the question of what this prospective foreign development means for the United States, the American petroleum industry in general, and the American engineer and technologist in particular. It is only logical to question whether or

Jan 1, 1948

By W. S. Pellini, F. N. Rhines

IN many of the otherwise well established alloy phase diagrams the solidus curves (temperatures at which liquid first appears upon melting) have not been located accurately, chiefly because the experimental techniques that have been most popular for determining solidus temperatures have been both cumbersome and subject to large errors. C. E. Homer and H. Plummer1 have described a sensitive and at the same time a very simple technique for locating the solidus curves in a number of alloys of tin. Their method consists simply in noting the temperature at which a specimen of the alloy ruptures under the influence of a light bending force. Although this method is not new, it has been little used for this purpose in the past; nevertheless, it appears so attractive in its possibilities of speed, simplicity, and precision that the investigations presently to be described were undertaken to verify its merits. The redetermination of the solidus and eutectic temperatures of the lead-antimony system was employed as a medium 0f experimentation. New values obtained in this way are believed to be sufficiently precise to warrant a revision of the currently accepted lead-antimony phase diagram (Fig. I). Determinations of the solidus of the lead-rich lead-antimony alloy series have been published by R. S. Dean2 and by E. E. Schumacher and F. C. Nix.3 Their points are represented in Fig. I. In their work the solidus was not located at antimony concentrations greater than 2 per cent; the curve was presumed to meet the eutectic horizontal at an antimony concentration of about 2.5 per cent. In the present studies the solidus has been traced to 3.5 per cent, where the eutectic horizontal is intersected (Table I and Fig. I). Within the range investigated by Dean and by Schumacher and Nix the agreement with their values is good. H. Seltz and B. De Witt,4 on the basis of activity measurements, have calculated that the intersection of the solidus and the eutectic reaction horizontal should lie at 3.86 per cent of antimony. The following determinations of the eutectic temperature have been reported: Roland-Gosselin,5 228°C.; Ewen,6 228°C.; J. E. Stead,7 247°C.; Campbell,8 228°C.; W. Gontermann,9 245° to 252°C.; R. Loebe,10 245°C.; E. Heyn and 0. Bauer,11 245°C.; H. Endo,12 250°C.; R. S. Dean,2 249° to 258°C.; E. Abel, 0. Redlich, and J. Adler,13 245°C.; W. Broniewski and L. Sliwowski,14 250° to 252°C.; H. Seltz and B. De Witt,4 250°C. A temperature of 249°C- appears to have been generally accepted in recent years; it is the value most frequently obtained by the method of cooling curves. Values below 249°C. have usually been obtained by inferior cooling-curve techniques; those above 250°C., by the method of heating

Jan 1, 1942

By C. E. Lesher

Two processes for agglomerating fine sized ores with low temperature coke are described. One process (Orcarb) agglomerates ores with limited amounts of carbon; the other (ore-carbon pellets) pelletizes fine sized ores, using low temperature cokes as the binder. Data are presented on the products obtained when taconite, magnetite, and hematite concentrates and several titanium oxide ores were used. REDUCTION of finely divided oxide ores has long been a major metallurgical problem. Various methods of agglomerating, notably briquetting, sintering, nodulizing, and pelletizing, have been developed and are in industrial use. Carbon is the usual reducing agent for oxide ores and attempts have been made to agglomerate fine ores with coking coal in order to get the metallurgical advantages of intimate contact and increased particle sizes suitable for subsequent smelting or reduction.1-3 For the past three years, research has been in progress on two processes for combining fine sized ores with reactive carbon in the form of low temperature coke. By one process, designated Orcarb, the ore is coated with coke carbon in amounts limited to that required for reduction and the result is an appreciable but limited increase in product particle size over that of the original ore. The second process, called ore-carbon pellets, produces pellets of fine ore bound by low temperature coke. The first objective was to develop a process for combining an oxide ore with only enough carbon for its reduction, the amount being that derived from the simple reduction equations. The carbon (that amount theoretically required for the reduction of the oxides in an agglomerate with ore), calculated to CO, ranges from 10 pct for zinc calcines or phosphate ores to 21 pct for rutile and 26 pct for silica. The carbon required for reducing iron oxides falls between the extremes—10 and 26 pct. When the carbon in the agglomerate is low temperature coke, reduction by hydrogen may be expected to take place, thus modifying the calculated carbon require- ment. On the other hand, in practice, an excess of reducing agent over that required in theory is normally used. Screen sizes of three iron ores on which the greater part of the experimental work was performed are given in Table I. Most of the testing was done with Freeport (Renton Mine) coal, but Pittsburgh and Elkhorn bed coals were also used. The first objective was to agglomerate the ore with sufficient low temperature coke to provide carbon for reduction, i.e., in the range from 10 to 25 pct. This was accomplished by preheating the ore, mixing with pulverized coking coal, and completing the coal carbonization in a plain steel rotating retort. The pilot retort, as it is now constituted, is shown by diagram in Fig. 1 and photograph, Fig. 2. Ore is fed into the upper kiln by a screw; it is heated to 900" to 1100°F by direct flame and it is then discharged into an insulating hopper from which it goes

Jan 1, 1956

By E. H. Burdick

The difficulties inherent in table concentration operations as applied to gold, silver, lead and zinc ores, are accentuated in the scheelite mill, which has a flowsheet that is similar in general principles. The narrow "spread" in the specific gravity between scheelite and the usual gangue in which it occurs often makes its clean separation extremely difficult and in some cases impracticable. The problem is further complicated by the extreme friability of the mineral and its inordinate tendency to "slime," particularly where fine grinding is necessary and wet grinding methods are employed. The physical aspect of the occurrence of scheelite in the ores, the kind and character of the rock in which the mineral is present, its hardness, friability and the specific gravity of its constituents, as well as like characteristics of the associated minerals— pyrite, pyrrhotite, sphalerite, and others, all have a bearing on the successful milling of crude ores and the production of a concentrate that is marketable with minimum price penalty or none at all. Most tungsten deposits are considered low grade when the limiting factor of low percentage recovery by gravity methods is borne in mind. The great majority of deposits developed or in process of development carry from 0.4 to 1.0 per cent tungstic oxide. Ore carrying I per cent is considered good grade; 0.7 to 0.8 per cent, fair, and below that figure, low grade. Steady mill feed averaging upward of I .o per cent WO3 is exceptional. Inasmuch as buying specifications demand a 60 per cent W03 content, the mineral content of the ores as mined must be concentrated to at least that degree. A few companies have constructed chemical plants for the treatment of their complex concentrates and low-grade flotation product, but the smaller operator must rely on table concentration, borrowing the tools and to a large extent the methods of his predecessors in the gold, silver, lead and zinc mills. Whether these are the best tools and methods that can be devised is an open question. Except in rare instances, table concentration, however carefully conducted, does not yield a satisfactory final recovery of the mineral content in headings as indicated by chemical determinations of tungstic oxide content. A saving of 60 to 65 per cent is considered fair, and an average 80 per cent recovery, exceptional. Each scheelite ore body is a separate problem. Details of handling that give best results in one case may not be successfully operative at a property on the same contact zone and but a short distance removed. Supplementary treatment of tailings by flotation may be successful in producing a low-grade concentrate of around 15 per cent W03, which is adapted to further treatment chemically at a given property and entirely unsuccessful at another. This problem constitutes another of the unanswered questions. The following paragraphs relate solely to the beneficiation of scheelite ores by table concentration and supplementary methods.

Jan 1, 1943

By C. E. Lesher

Two processes for agglomerating fine sized ores with low temperature coke are described. One process (Orcarb) agglomerates ores with limited amounts of carbon; the other (ore-carbon pellets) pelletizes fine sized ores, using low temperature cokes as the binder. Data are presented on the products obtained when taconite, magnetite, and hematite concentrates and several titanium oxide ores were used. REDUCTION of finely divided oxide ores has long been a major metallurgical problem. Various methods of agglomerating, notably briquetting, sintering, nodulizing, and pelletizing, have been developed and are in industrial use. Carbon is the usual reducing agent for oxide ores and attempts have been made to agglomerate fine ores with coking coal in order to get the metallurgical advantages of intimate contact and increased particle sizes suitable for subsequent smelting or reduction.1-3 For the past three years, research has been in progress on two processes for combining fine sized ores with reactive carbon in the form of low temperature coke. By one process, designated Orcarb, the ore is coated with coke carbon in amounts limited to that required for reduction and the result is an appreciable but limited increase in product particle size over that of the original ore. The second process, called ore-carbon pellets, produces pellets of fine ore bound by low temperature coke. The first objective was to develop a process for combining an oxide ore with only enough carbon for its reduction, the amount being that derived from the simple reduction equations. The carbon (that amount theoretically required for the reduction of the oxides in an agglomerate with ore), calculated to CO, ranges from 10 pct for zinc calcines Or phosphate Ores to 21 pct for rutile and 26 pct for silica. The carbon required for reducing iron oxides falls between the extremes—10 and 26 pet' When the carbon in the agglomerate is low temperature coke, reduction by hydrogen may be expected to take place, thus modifying the calculated carbon require- ment. On the other hand, in practice, an excess of reducing agent over that required in theory is normally used. Screen sizes of three iron ores on which the greater part of the experimental work was performed are given in Table I. Most of the testing was done with Freeport (Renton Mine) coal, but Pittsburgh and Elkhorn bed coals were also used. The first objective was to agglomerate the ore with sufficient low temperature coke to provide carbon for reduction, i.e., in the range from 10 to 25 pct. This was accomplished by preheating the ore, mixing with pulverized coking coal, and completing the coal carbonization in a plain steel rotating retort. The pilot retort, as it is now constituted, is shown by diagram in Fig. 1 and photograph, Fig. 2. Ore is fed into the upper kiln by a screw; it is heated to 900° to 1100°F by direct flame and it is then discharged into an insulating hopper from which it goes

Jan 1, 1956

By Marshall B. Standing, Donald L. Katz

Density data are reported on 16 saturated hydrocarbon vapors at Pressures ranging from 1000 to 8220 Ib. per sq. in. and at temperatures ranging from 35° to 250°F. These data have been used to extend the compressibility-factor chart for natural gases up to 10,000 lb. per sq. in. The relatively large quantity of high-boiling constituents present in high-pressure vapors in equilibrium with crude oils makes it necessary to include in the analysis of the gas the molecular weight, density, and possibly boiling range of the heptanes and heavier fraction. Relationships have been presented by which the density of gases may be obtained directly from the temperature, pressure, and gas gravity provided the gases have a common source or are similar in composition. Introduction The densities of natural gases are necessary in many engineering in in petroleum production and utilization, Gas reserves, changes in reservoir pressure, gradients in gas wells, metering of gases, pipeline flow, and compression of gases are typical problems requiring the density of the gas. A decade ago, engineering computations used ideal gas laws with deviations up to 500 Ib. per sq. in.4 Recent discoveries of pools having Pressures UP to 7500 lb. Per sq. in., and installation of pressure-maintenance and recycling plants, have increased the need for data On gas density at high pressures. Methods of Computation The accepted method of computing the density or specific volume of natural gases is the use of the ideal gas law corrected by a compressibility factor. The method proposed by Kay7 of correlating compressibility factors for gaseous mixtures on pseudocritical properties5 appears to be satisfactory for natural gases.2 The meth-me-compressibility factor has been shown to deviate systematically from the behavior of natural gases2 and a chart giving these corrected factors is available. A method of computing specific volume of gaseous mixtures from partial molal volumes has been reported by sage and Lacey.8 Complete data for the computation are not yet available for all hydrocarbon gases. Most- of the reported data on gas densities have been in the single-phase region removed from the dew point or saturation condition. Since most gases in the reservoir Or while on contact with liquid '''ring flow are saturated, the determination of densities under conditions of saturation is particularly important. Although there is no reason to believe that the saturated gases differ in behavior from those consider. ably removed from their dew points, the usual experimental determinations find difficulty on approaching the dew-point conditions, This paper reports the density of I6 saturated gases in equilibrium with crude oils. The relationships developed to compute the density of gases to high pressure' have been modified and enlarged. A simpli-fied method of obtaining gas density is presented in the Form of charts, which apply for specific groups of gases.

Jan 1, 1942

By F. N. Rhines, W. S. Pellini

In many of the otherwise well established alloy phase diagrams the solidus curves (temperatures at which liquid first appears upon melting) have not been located accurately, chiefly because the experimental techniques that have been most popular for determining solidus temperatures have been both cumbersome and subject to large errors. C. E. Homer and H. Plummerl have described a sensitive and at the same time a very simple technique for locating the solidus curves in a number of alloys of tin. Their method consists simply in noting the temperature at which a specimen of the alloy ruptures under the influence of a light bending force. Although this method is not new, it has been little used for this purpose in the past; nevertheless, it appears so attractive in its possibilities of speed, simplicity, and precision that the investigations presently to be described were undertaken to verify its merits. The redetermination of the solidus and eutectic temperatures of the lead-antimony system was employed as a medium of experimentation. New values obtained in this way are believcd to be sufficiently precise to warrant a revision of the currently accepted lead-antimony phase diagram (Fig. I). Determinations of the solidus of the lead-rich lead-antimony alloy series have been published by X. S. Dean2 and by E. E. Schumacher and F. C. Nix. Their points are represented in Fig. I. In their work the solidus was not located at antimony collcentrations greater than 2 per cent; the curve was presumed to meet the eutectic horizontal at an antimony concentration of about 2.5 per cent. In the present studies the solidus has been traced to 3.5 per cent, where the eutectic horizontal is intersected (Table I and Fig. I). Within the range investigated by Dean and by Schumacher and Nix the agreement with their values is good. H. Seltz and B. De Witt,4 on the basis of activity measurements, have calculated that the intersection of the solidus and the eutectic reaction horizontal should lie at 3.86 per cent of antimony. The following determinations of the eutectic temperature have been reported: Roland-Gosselin,5 228°C.; Ewen,6 228OC.; J. E. Stead,7 24g°C.; Campbell,8 228°C.; W. Gontermann,9 245' to 252°C.; R. Loebe,lo 245°C.; E. Heyn and 0. Bauer,ll 245°C.; H. Endo,12 250°C.; R. S. Dean,= 247' to 258°C.; E. Abel, O. Redlich, and J. Adier,13 245°C.; W. Broniewski and L. Sliwowski,14 250' to 252°C.; H. Seltz and B. De Witt,4 25o°C. A temperature of 247°C. appears to have been generally accepted in recent years; it is the value most frequently obtained by the method of cooling curves. Values below 247°C. have usually been obtained by inferior cooling-curve techniques; those above 250°C., by the method of heating

Jan 1, 1943

By Junius D. Edwards

WHEN Charles Martin Hall invented the electrolytic process for the production of aluminum, one basic requirement was a supply of pure alumina. Now, more than 50 years later, the same requirement still holds, and there are no technical straws in the wind to indicate that this situation is likely to change. Long ago, Aluminum Company of America took a number of steps to see that this country should not face shortages of alumina and aluminum in time of emergency. As one step to this end, the Company developed and used a supply of bauxite in South America in order to conserve dwindling Arkansas reserves. Another, and more a program than a step, was to investigate every type of process that might bear the possibility of utilizing the low-grade ores of aluminum that are more plentiful than bauxite. It is a long story, but the investigation included electric-furnace processes, acid extraction processes and alkaline extraction processes, with or without preliminary furnace and sinter treatments. Some of the processes developed were operated in commercial production. This work has been continuous since the first World War. The turn of the wheel came sooner than was expected when, in 1942, bauxite shipments through the Caribbean became uncertain and hazardous through the operation of submarines. The tremendous requirements of aluminum for the war effort were consuming high-grade bauxite at an alarming rate and a national search for substitutes began. High-grade bauxites, for technical and economic reasons, have been defined as those containing about 7 per cent or less of silica. While bauxite of this grade was limited in amount in the United States, there was in sight a substantially greater volume of low-grade, high-silica bauxite not amenable to economic treatment by the Bayer process, but richer in alumina than the clays or other available low-grade ores. It was at this point, and after several years of intensive research on this particular phase of the problem, that Aluminum Research Laboratories brought to completion the invention of one of its research staff, which made practical the utilization of large reserves of low-grade bauxite in America. BAYER PROCESS The Bayer process has been almost universally used for the 'production of alumina from bauxite. This process, in outline, comprises the digestion of finely ground bauxite in a solution of caustic soda (NaOH) under pressure and at an elevated temperature. Alumina in the bauxite goes into solution as sodium aluminate and the impurities-oxides of iron, titanium and silicon-remain undissolved. The undissolved residue, known as "red mud," from its color, is separated and run to waste. Aluminum hydrate (A1202.3H20) is precipitated from the solution of sodium aluminate, and the liquor containing the caustic soda and some alumina is returned to the process for digesting more bauxite. The aluminum hydrate, after washing, is calcined at a high temperature to produce

Jan 1, 1945

By W. S. Pellini, F. N. Rhines

In many of the otherwise well established alloy phase diagrams the solidus curves (temperatures at which liquid first appears upon melting) have not been located accurately, chiefly because the experimental techniques that have been most popular for determining solidus temperatures have been both cumbersome and subject to large errors. C. E. Homer and H. Plummerl have described a sensitive and at the same time a very simple technique for locating the solidus curves in a number of alloys of tin. Their method consists simply in noting the temperature at which a specimen of the alloy ruptures under the influence of a light bending force. Although this method is not new, it has been little used for this purpose in the past; nevertheless, it appears so attractive in its possibilities of speed, simplicity, and precision that the investigations presently to be described were undertaken to verify its merits. The redetermination of the solidus and eutectic temperatures of the lead-antimony system was employed as a medium of experimentation. New values obtained in this way are believcd to be sufficiently precise to warrant a revision of the currently accepted lead-antimony phase diagram (Fig. I). Determinations of the solidus of the lead-rich lead-antimony alloy series have been published by X. S. Dean2 and by E. E. Schumacher and F. C. Nix. Their points are represented in Fig. I. In their work the solidus was not located at antimony collcentrations greater than 2 per cent; the curve was presumed to meet the eutectic horizontal at an antimony concentration of about 2.5 per cent. In the present studies the solidus has been traced to 3.5 per cent, where the eutectic horizontal is intersected (Table I and Fig. I). Within the range investigated by Dean and by Schumacher and Nix the agreement with their values is good. H. Seltz and B. De Witt,4 on the basis of activity measurements, have calculated that the intersection of the solidus and the eutectic reaction horizontal should lie at 3.86 per cent of antimony. The following determinations of the eutectic temperature have been reported: Roland-Gosselin,5 228°C.; Ewen,6 228OC.; J. E. Stead,7 24g°C.; Campbell,8 228°C.; W. Gontermann,9 245' to 252°C.; R. Loebe,lo 245°C.; E. Heyn and 0. Bauer,ll 245°C.; H. Endo,12 250°C.; R. S. Dean,= 247' to 258°C.; E. Abel, O. Redlich, and J. Adier,13 245°C.; W. Broniewski and L. Sliwowski,14 250' to 252°C.; H. Seltz and B. De Witt,4 25o°C. A temperature of 247°C. appears to have been generally accepted in recent years; it is the value most frequently obtained by the method of cooling curves. Values below 247°C. have usually been obtained by inferior cooling-curve techniques; those above 250°C., by the method of heating

Jan 1, 1943

By V. V. Valleroy, A. J. Cornelius, B. T. Willman, G. W. Runberg, L. W. Powers

This paper reports the results of an investigation into the use of steam as a recovery agent. High oil recoveries by steam, as much as 100 per cent greater than by water flood, were demonstrated in laboratory linear cores. The principal mechanisms responsible for the additional oil have been identified as (1) thermal expansion of the oil, (2) viscosity reduction and (3) steam distillation. Although the first two also enhance recovery by hot water flood, they are effective with steam injection at lower volumes of produced fluids. Steam-zone residual oil saturation is independent of initial saturation. Recovery by steam is greater for lighter oils because they contain a greater fraction of steam-distillable components. Equations for the steam-zone advance in a radial homogeneous system are presented; these show the effect of reservoir parameters. The displacement in the hot liquid region moving ahead of the steam front can be estimated by a calculative procedure which is suggested. The method which takes account of the temperature gradient is applicable also to a regullar hot water flood. INTRODUCTION Considerable industry interest in the application of heat to petroleum reservoirs as a means of increasing oil recovery has been evident in the past few years. Three thermal methods which have attracted interest are (1) the injection of saturated steam, (2) the injection of hot water and (3) the injection of air into a formation to support combustion within the reservoir. Much has been published in recent years on underground burning, and there have been several papers on hot water injection. Although there are several early reports1,2 on steam injection, no recent experimental studies have been published on this recovery method. In our early thermal methods research, a marked improvement was found in oil recovery by steam injection compared with recovery by water injection in the same system. An investigation subsequently was undertaken to obtain quantitative information from which to evaluate steam injection as an oil recovery method. In addition, it was desired to investigate the recovery mechanism of hot water as compared with that of "cold" water and steam injection. An understanding of the mechanisms by which these processes operate would generally define favorable field conditions for their successful application. This paper reports the results of the laboratory study and suggests calculative approaches to estimate the field behavior of the steam-injection process. EXPERIMENTAL METHOD EQUIPMENT A schematic diagram of the equipment used for the displacement tests is shown in Fig. 1. Essentially, it consisted of a core with suitable means for recording temperatures, a feed system for injecting steam or cold or hot water, and a receiving train for condensing, cooling and measuring produced fluids. For the steam experiments, air-free saturated steam was piped from the boiler to the core face in insulated lines that were provided with steam traps and bleeds to remove any condensate formed in the lines due to heat losses. A 12-in. section of the line immediately ahead of

By L. S. Castleman, H. A. Froot

A study was made of the growth kinetics of B-brass layers in a-brass us y-brass diffusion couples in which both phases were saturated in the 6 phase. It was found that useful estimates can be made of the difhsion coefficients at the ß-phase interfaces from interface displacement data, which are relatively easy to measure experimentally; also, a useful estimate can be made of the mean heat of activation for diffusion from layer growth data. The effects of pressure on layer growth kinetics were explored and found to be consistent with a vacancy model for diffusion in 6 brass in both the disordered and ordered temperature range. 1 HE study of multiphase diffusion receives relatively little attention in comparison with that devoted to diffusion in homogeneous materials. Of the hundred or so papers on diffusion written each year,' only a few are devoted to the subject, and it is the rare review article2,3 that devotes any space to multiphase diffusional phenomena. This is unfortunate, since the metallurgist frequently encounters practical situations involving cementation processes such as cladding, protective coating of metals, and so forth in which he needs guidance of a fundamental nature. The investigation of multiphase diffusion phenomena is complicated by the fact that one must consider reactions at phase interfaces as well as the migration of atoms within the individual phases; these reactions cause the interfaces to be displaced within the diffusion zone. The relative displacement of two adjacent interfaces corresponds to the growth of an intermetallic layer, and it is not difficult to determine experimentally the kinetics of layer growth. In the past few years it has been pointed out4,5 that valuable fundamental information may be gained about diffusion coefficients and the concentrations at interfaces through a study of their motion. Accordingly, it is the purpose of this paper to report the results of an investigation of interface motion in a simple multiphase binary system. In the work reported herein, attention was focussed on the growth of a 6 -brass layer in a diffusion couple prepared from a- and y-brass compositions saturated with respect to the 6 phase. This particular system was chosen for a number of reasons. First, the bcc ß-brass phase is disordered for all compositions at temperatures above 468°C and becomes increasingly long-range ordered for all compositions at temperatures below 454° C;6,7 thus, the effects of a variation in order on interface displacement could be determined. Second, diffusion coefficients have already been obtained as a function of temperature in the ß phase both in the ordered and disordered Re- and a theoretical picture of the mechanism of diffusion in this and other ordered solutions is emerging.11'12 Third, some thermodynamic data are available for the a-, ß-, and ?-brass phases,13,4 and these data could be used to gain insight into questions of phase equilibria and concentrations at phase interfaces.

Jan 1, 1963

By T. S. West

Completion and production data presented for three wells in the Oakville area of Live Oak County, Texas, which were completed near the gas-oil or water-oil contact, indicate that coning may not be as prevalent a cause of failure in such cases as is commonly assumed. Failure in the cases discussed is indicated to be due instead to: (I) erosion of the formation, (2) flowing out of mud filter cake, or (3) failure of the cement. An open-hole gravel-pack type of completion procedure is proposed for preventing failures of this kind by preventing movement of all solid material in the space in which completion is made. Various combinations of layers of gravel, sand, and cement are utilized for this purpose. Experimental results and theoretical discussion as to the applicability of gravel pack completion are included. Introduction This paper is primarily a study of the reasons for failure of oil-well completions near the gas-oil or oil-water contact, and suggests a procedure for increasing the efficiency of this type of completion. The value of improvement in completion effectiveness near the gas or water zone is not confined, however, to wells of relatively thin oil columns. Thick oil columns become thin as depletion progresses. It would seem to follow that the minimum distance from the gas or water zone at which completion can be made in a new well indicates the limit to which depletion may be carried in a well having an oil column of any initial magnitude. Only four ways can be postulated in which high gas-oil or water-oil ratio can initially occur if the zone exposed for production is within the oil column: 1. Failure of the cementing material. 2. Vertical coning. 3. Failure along the boundary between the cement and the wall of the well. 4. Failure of the formation comprising the wall of the well. Cementing materials such as portland cement and plastics have reached a high stage of development. Failures of this type are probably due almost always to extraneous causes such as mud contamination rather than to faulty cementing material. Vertical coning can and obviously does occur. However, the usual occurrence of thin impermeable streaks in sand sections and the success with which open-hole drill-stem tests can be made near the gas-oil contact suggest that over-all effective vertical permeability, and in turn vertical coning, is less prevalent than frequently is assumed. Much has been written on failure by flowing out of the mud filter cake between cementing material and the formation. A filter cake is always present if, prior to cementing, mud has come in contact with a permeable formation at pressures exceeding the pressure head of the fluid it contains. Mechanical methods are in use for removing filter cake during the cementing operation? which undoubtedly are of

Jan 1, 1947

By T. S. West

Completion and production data presented for three wells in the Oakville area of Live Oak County, Texas, which were completed near the gas-oil or water-oil contact, indicate that coning may not be as prevalent a cause of failure in such cases as is commonly assumed. Failure in the cases discussed is indicated to be due instead to: (I) erosion of the formation, (2) flowing out of mud filter cake, or (3) failure of the cement. An open-hole gravel-pack type of completion procedure is proposed for preventing failures of this kind by preventing movement of all solid material in the space in which completion is made. Various combinations of layers of gravel, sand, and cement are utilized for this purpose. Experimental results and theoretical discussion as to the applicability of gravel pack completion are included. Introduction This paper is primarily a study of the reasons for failure of oil-well completions near the gas-oil or oil-water contact, and suggests a procedure for increasing the efficiency of this type of completion. The value of improvement in completion effectiveness near the gas or water zone is not confined, however, to wells of relatively thin oil columns. Thick oil columns become thin as depletion progresses. It would seem to follow that the minimum distance from the gas or water zone at which completion can be made in a new well indicates the limit to which depletion may be carried in a well having an oil column of any initial magnitude. Only four ways can be postulated in which high gas-oil or water-oil ratio can initially occur if the zone exposed for production is within the oil column: 1. Failure of the cementing material. 2. Vertical coning. 3. Failure along the boundary between the cement and the wall of the well. 4. Failure of the formation comprising the wall of the well. Cementing materials such as portland cement and plastics have reached a high stage of development. Failures of this type are probably due almost always to extraneous causes such as mud contamination rather than to faulty cementing material. Vertical coning can and obviously does occur. However, the usual occurrence of thin impermeable streaks in sand sections and the success with which open-hole drill-stem tests can be made near the gas-oil contact suggest that over-all effective vertical permeability, and in turn vertical coning, is less prevalent than frequently is assumed. Much has been written on failure by flowing out of the mud filter cake between cementing material and the formation. A filter cake is always present if, prior to cementing, mud has come in contact with a permeable formation at pressures exceeding the pressure head of the fluid it contains. Mechanical methods are in use for removing filter cake during the cementing operation? which undoubtedly are of

Jan 1, 1947